PREFACE

ThesecondeditionofChemistrycontinuesthesubstantialcommitmentofJohnWileyandSons
Australiatolocalchemistryeducation.Studentstodayrequirevariousmultimediaactivities,online
resourcesandtestingtomaintainengagement.Withthisedition,theauthorsandWileyhavecontinued
toexpandthediverseancillaryresourcesavailablethroughWileyPLUSwhichcomplementthetext.In
additiontothetextitself,WileyhasdevelopedextensivenewmediacontentforChemistry,2ndedition.
Writtenincloseconsultationwiththeauthorsandspecificallydesignedforthenewversion5of
WileyPLUS,thetextandresourcesprovidelecturersandstudentsthecompleteandintegratedtoolsto
helpteachersteach,andstudentslearn.

Chemistry,2ndeditioncontinuestoprovidetheappropriateamountoforganic,inorganicandphysical
chemistryforthemajorityofAustralasianfirstyearChemistrycourses.Inthiseditionanewchapterhas
beenaddedtothetext,chapter14Thepblockelements,forthosecoursesthatincludemoreofthis
inorganicchemistrytopic.TheauthorswouldliketoacknowledgetheassistanceofTonyWeddfrom
theUniversityofMelbourneinthepreparationofthischapter.

Additionallymorethanhalfofthechaptershavesignificantnewcontent,andallchaptershavebeen
revised.Chapter8Chemicalthermodynamicshasbeenbrokenintosmallersectionsallowing
mathematicalcontenttobeignoredifnotrequired,andthethermodynamicsmaterialhasbeenrewritten.
Newendofchapterquestionshavealsobeenaddedthroughout,includinganumberofvisual
problems,whileallfiguresandartworkhavebeencloselyscrutinisedandfurtherenhanced.

Thefirsteditionintroducedtwofeatures,ChemicalConnectionsandChemistryResearch,that
provedpopularandhavebeenretained.TheChemicalConnectionsfeatureshighlighttheconnections
betweenthechemicalconceptswithinthechapterandapplicationsofthatchemistryintheworldaround
youchemistrydoesnotstopatthelaboratorydoor.Inadditiontotheapplicationsdiscussedthroughthe
bodyofthetext,theseseparatepagesgivemoreindepthdescriptionsofapplicationsandcovermany
diversesubjects,includingDNAprofiling,desalinationandnanotechnology.Complementingthis,
ChemistryResearchshowcasesinspirationalworkperformedinresearchlaboratoriesinAustraliaand
NewZealandrelatedtotopicsineachchapter.NewcontributionstoChemistryResearchinChemistry,
2ndeditionincludeproteinrecognition,computationalchemistryandphotoelectronspectroscopy.

Ourthanksgoestothefollowingresearchersandcontributors,whohaveprovidedinformationand/or
materialsfortheChemicalConnectionsandChemistryResearchfeatures.
PaulVBernhardt,UniversityofQueensland
MargaretBrimble,UniversityofAuckland
SallyBrooker,UniversityofOtago
MarkBuntine,CurtinUniversity
SamCarroll,CSIRO
JohnCarver,UniversityofAdelaide
MichelleCoote,AustralianNationalUniversity
DeannaD'Allessandro,UniversityofSydney
JamesDeVoss,UniversityofQueensland
ChrisEaston,AustralianNationalUniversity
EmilioGhisalberti,UniversityofWesternAustralia
PaulHaddad,UniversityofTasmania
 TrevorHambley,UniversityofSydney
JasonHarper,UniversityofNewSouthWales
RichardHartshorn,UniversityofCanterbury
CraigHawker,UniversityofCalifornia,SantaBarbara
TesseHoekstra,CSIRO
FrancaJones,CurtinUniversity
ScottKable,UniversityofSydney
CameronKepert,UniversityofSydney
SimonWLewis,CurtinUniversity
MaxLu,UniversityofQueensland
MarcelMaeder,UniversityofNewcastle
KathrynMcGrath,VictoriaUniversityofWellington
MarkOgden,CurtinUniversity
RogerRead,UniversityofNewSouthWales
CarlHSchiesser,UniversityofMelbourne
TimSchmidt,UniversityofSydney
FrancesSeparovic,UniversityofMelbourne
DanielSoutham,CurtinUniversity
ClaudineStirling,UniversityofOtago
JeffTallon,MacDiarmidInstituteandIndustrialResearchLtd
JohnTsanaktsidis,CSIRO
MarkvonItzstein,GriffithUniversity
GordonWallace,UniversityofWollongong
JacquelineAnneWilce,MonashUniversity
(Richard)MingWahWong,UniversityofSingapore
ZhiPing(Gordon)Xu,UniversityofQueensland

Muchofthepopularityofthefirsteditioncanbeattributedtotheconsultativenatureoftheauthorial
process.Thesecondeditionhasalsobeenthroughanextensive,thoroughandrigorousreview.
UndertakenbyacademicsteachingundergraduateChemistryinAustraliaandNewZealand,morethan
50contributedtheirtimeincarefullyreviewingdraftchaptersandmakingsuggestionstotheauthors.In
thiscontexttheauthorsandpublisherswouldliketoacknowledgetheimportanceofthecontributions
madeby:
BelindaAbbott,LaTrobeUniversity
PhilAndrews,MonashUniversity
StuartBailey,CurtinUniversity
StephenBest,UniversityofMelbourne
JoanneBlanchfield,UniversityofQueensland
SuzanneBoniface,VictoriaUniversityofWellington
DavidBrown,CurtinUniversity
RonClarke,SydneyUniversity
JamesCrowley,UniversityofOtago
MurrayDavies,JamesCookUniversity
 GregDicinoski,UniversityofTasmania
PeterFredericks,QueenslandUniversityofTechnology
LawrieGahan,UniversityofQueensland
BobGilbert,UniversityofQueensland
LisbethGrondhal,UniversityofQueensland
JasonHarper,UniversityofNewSouthWales
HughHarris,UniversityofAdelaide
TobyHudson,SydneyUniversity
GeoffJameson,MasseyUniversity
LynneJones,CurtinUniversity
RichardKeene,JamesCookUniversity
TrevorKitson,MasseyUniversity
GeraldLaurence,UniversityofAdelaide
KieranLim,DeakinUniversity
MaxMassi,CurtinUniversity
RossMcGeary,UniversityofQueensland
CarlaMeledandri,UniversityofOtago
JulieNiere,RMITUniversity
AlanPayne,CurtinUniversity
SbastienPerrier,SydneyUniversity
StephenRalph,UniversityofWollongong
MarkRiley,UniversityofQueensland
TrevorRook,RMITUniversity
DavidSalter,UniversityofAuckland
GarySchenk,UniversityofQueensland
TimSchmidt,SydneyUniversity
MadeleineSchultz,QueenslandUniversityofTechnology
TrevorSmith,UniversityofMelbourne
DanielSoutham,CurtinUniversity
ChrisSumby,UniversityofAdelaide
MattheusTimmer,VictoriaUniversityofWellington
MarkWaterland,MasseyUniversity
TonyWedd,UniversityofMelbourne
NatalieWilliamson,UniversityofAdelaide
DavidWilson,LaTrobeUniversity
DannyWong,MacquarieUniversity
AllanBlackman,SteveBottle,SiggiSchmid,MauroMocerino,andUtaWilleaddthefollowing:
WewouldliketothanktheteamatWiley,especiallyJasonGray,whohaveallworkedsotirelessly
inthedevelopmentofthistext.Wewouldalsoliketogiveparticularthankstothemanyfriendsand
professionalcolleagueswhosenamesappearinthisprefacewhohavealsomadesignificant
contributionstothisproject.Ourgoaltocreateatextthatisrichinlocalcontextsandexamplesand
whichmatchestheneedsandexpectationsofchemistsinAustraliaandNewZealandwouldnothave
beenpossiblewithoutthiscrucialinputandforthatwethankyouandlookforwardtoyourfurther
 feedbackandfuturesupport.

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RESOURCES
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students'confidencesotheyknowwhattodo,howtodoit,andthattheyhavedoneitcorrectly.Ithasbeendevelopedasaresult
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Relatedmedia,examplesandsamplepracticeitemsreinforcethelearningobjectives.

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Thesehelpthestudentunderstand'howtodoit'.WhenthelecturercomestoteststudentswithinWileyPLUS,theycanchoose
whatscaffoldinghelpcanbemadeavailabletothestudentsforeveryquestion.
Newlywrittenvisualisationsgivestudentsanengagingformattogainbothvisualandconceptualunderstandingofkeytopics.
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Throughouteachstudysession,studentscanassesstheirprogressandgainimmediatefeedback.WileyPLUSprovidesprecise
reportingofstrengthsandweaknesses,aswellasindividualisedquizzes,sothatstudentsareconfidenttheyarespendingtheirtime
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WileyPLUSprovidesreliable,customisableresourcesthatreinforcecoursegoalsinsideandoutsideoftheclassroomaswellas
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Customisablecourseplan:WileyPLUScomeswithaprecreatedcourseplandesignedbyasubjectmatterexpertuniquelyforthis
course.Simpledraganddroptoolsmakeiteasytoassignthecourseplanasisormodifyittoreflectyourcoursesyllabus.

Precreatedactivitytypesinclude:
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Readingsandresources
ConceptMasteryassignmentstestkeyconceptsfrommultiplepointsofview(visual,symbolic,graphical,quantitative).
Additionally,manyorganicquestionsincludethosewhichrequirestudentstodrawusingMarvinSketch.
ReactionExplorerisaninteractivesystemforlearningandpractisingreactions,synthesesandmechanismsinorganic
chemistry,withadvancedsupportfortheautomaticgenerationofrandomproblemsandcurvedarrowmechanismdiagrams.
WileyPLUSgradebook:WileyPLUSprovidesinstantaccesstoreportsontrendsinclassperformance,studentuseofcourse
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TheInstructors'SolutionsManualcontainsworkedsolutionstotheendofchapterproblemsinthetext.
TheTestBankisavailableinWord,Blackboard,WebCTandMoodle.Thisisaseparatetestbankfromthatfoundin
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TheComputerisedTestBankallowslecturerstoproducehardcopytestsfromthetestbank.
TheArtFilesprovidesallimagesfromthetextinaformatthatallowseasyintegrationintothelecturers'ownresources.

ContributorstoChemistry,2ndEditionResources
TheauthorsandpublisherswouldliketothankJohnHill,LaTrobeUniversity,forhissubstantialcontributioninprovidingthe
WileyPLUSconceptmodulesandConceptBasics.

Theywouldalsoliketothankthefollowingfortheirtimeandcontributiontotheinstructorresources:
SolutionsManual:JohnHill,LaTrobeUniversity
 PowerPoint:MelissaLatter,UniversityofWesternAustralia
TestBank:JohnHill,LaTrobeUniversityFlorenceLaibe,MonashUniversityJosephLane,WaikatoUniversityMelissa
Latter,UniversityofWesternAustraliaShannanMaisey,UniversityofWesternAustralia.
www.wileyplus.com

Poweredbyproventechnologyandbuiltonafoundationofcognitiveresearch,WileyPLUShasenrichedtheeducationofmillions
ofstudentsinover20countriesaroundtheworld.

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ACKNOWLEDGEMENTS
Theauthorsandpublisherwouldliketothankthefollowingcopyrightholders,organisationsand
individualsfortheirpermissiontoreproducecopyrightmaterialinthisbook.

Images
AAP:/AndreaRobinson/UnderlicenseofAAPONEImages489/AFP/GenyaSavilov1167
(bottom)/APPhoto/STR286(bottom)ReprintedwithpermissionfromJournaloftheAmerican
ChemicalSociety,RCoulstonetal.,Harnessingtheenergyofmolecularrecognitioninananomachine
havingaphotochemicalon/offswitch,Vol.128,No.46,20062011AmericanChemicalSociety
1035,1036(bottom),1037CourtesyofANSTO12(2images)ANTPhoto.com.au:/DaveWatts
1080(top)/FredyMercay1080(bottom)/KelvinAitken1081(bottom)AssociateProfessor
TrevorAppleton747(right3images)ArmfieldLimited,www.armfield.co.uk234Australian
Synchrotron114(top)BBarnsley,AustralianNationalBotanicGardens839(top)Reproduced
withpermission.FromAllanMTorresetal.,1999,JournalofBiochemistry,341,78594.
BiochemicalSociety1081(top)BIPM.ReproducedwithpermissionoftheBIPM(Bureau
internationaldespoidsetmesures)35(top)AllanBlackman75(top),90(right),93(left),246,257,
258,365,516,566,589(top),605,762(left),763,1120(3images),1152(bottom)SteveBottle747
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SallyBrooker577(2images)CengageLearningInc.:/FromBettleheim,Brown,Campbell,Farr,
IntroductiontoOrganicandBiochemistry(withPrintedAccessCardThomsonNOW(T))6E,fromFig.
14.142007byBrooks/Cole,Reproducedbypermission,www.cengage.com/permissions1079/
(quaternary)/Fig.12.8,p.578,fromZumdahl&Zumdahl,Chemistry6E,2003byBrooks/Cole,
Reproducedbypermission,www.cengage.com/permissions651Corbis:/GeorgeSteinmetz427/
JohnCarnemolla362/JonathanBlair226/Bettmann5(left),1167(top)/Construction
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380DigitalVision92(left)Elsevier:/ThismaterialwaspublishedinJournalofMolecular
Biology,340,Rekasetal,InteractionofthemolecularchaperoneaBcystallinwithasynuclein:effects
onamyloidfibrilformation,116783,20041077(2images)/ReprintedfromBiochemicaland
BiophysicalResearchCommunications,Vol.335(2),HastingsAF,OttingG,FolmerRH,DugginIG,
WakeRG,WilceMC,WilceJA1098,1099LarsOliverEssen672FairfaxPhotoLibrary:/James
Davies809/JasonSouth824(bottom)/RobertPearce370FundamentalPhotographs:/Larry
Stepanowicz439(farright)/RichardMegna125(left),203,235,634(2images)Illustrations,
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PaulHaddad157DavidAHardy,www.astroart.org1173(bottom)HughesMedicalInstitute.
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Research,AlmadenResearchCenter.Unauthorizedusenotpermitted.125(right)Image1001149
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689(6images)/AmandaMurfitt708(top)/JasonGray745(2images)/KariAnnTapp79,462,710,
778,746,811,824(top),832,906,933,1020,1038,1040,1125,1133,1150(left)/ReneeBryon988,
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SonsLtd,WestSussex,England929(3images),930(3images),931(2images)JohnWiley&Sons,
Inc.283,1074,1075/AdaptedfromMcCann,MC,Roberts,K,1991,Architectureoftheprimarycell
wall,InCliveWLloyd(ed.),TheCytoskeletalBasisofPlantGrowthandForm,AcademicPressand
Hopkins,Hner,WG,2009,IntroductiontoPlantPhysiology,4e,JohnWiley&Sons,Inc.995/Andy
Washnik98,254(top),275(2images),395,432,475(4images),513,547/DHallidayandRResnick,
FundamentalsofPhysics,2nded.,Revised1986,JohnWiley&Sons,Inc.Usedbypermission1163
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Essentialbiochemistry,JohnWiley&Sons,Inc.ReprintedwithpermissionofJohnWiley&Sons,
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DrLawrenceKobilinsky1110LawrenceBerkeleyNationalLaboratory613(2images)Simon
Lewis874(2images)MaxLu1100(2photos)/ReprintedfromBiochemicalandBiophysical
ResearchCommunications,Vol.335(2).HastingsAF,OttingG,FolmerRH,DugginIG,WakeRG,
WilceMC,WilceJA,InteractionofthereplicationterminatorproteinofBacillussubtiliswithDNA
probedbyNMRspectroscopy,3616,September23,2005,withpermissionfromElsevier1100
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Takahara286(top)/PhotoResearchers/TomHollyman168/RayNelson326(centre)/SPL5(right),
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ofTheRoyalSocietyofChemistry47CarlSchiesser515SiegbertSchmid114(bottom),279
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Bezergheanu770(shell)/MoisesFernandezAcosta995(top)/Mopic1087(background)/
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Frank295(centre)/RynioProductions770(screw)/SebastianDuda295(right)/Sebastian
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Boyes630(right)/VibrantImageStudio169(top)/Viktor1448/Vlad61345(background)/
Yarygin269/yuri4u80603(right)/Zart129(right)ClaudineStirling1173(top)
nirnac/stock.xchng1143(left)JeffTalon285UnitedStatesDepartmentofAgriculture,
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ScienceBooks,1989138(left)USDepartmentofEnergy1179/NationalEnergyTechnology
Laboratory685ReprintedwithpermissionofVarian,Inc.885VisualsUnlimited125(centre)/
ScienceVU/LBL280(top)GordonWallace1145(3images)PeterWasserscheid534CharlesD
Winters719,816,959

Text
AustralianSynchrotron11415Table12.6,p.577,fromZumdahl&Zumdahl,Chemistry6E,
2003byBrooks/Cole,apartofCengageLearning,Inc.,Reproducedbypermission.
www.cengage.com/permissions651FromWeiser,ME,Atomicweightsoftheelements2005,Pure
Appl.Chem.,Vol.78,No.11,pp.205166,IUPAC2006,andWieser,ME&Berglund,M,Atomic
weightsoftheelements2007,PureAppl.Chem.,Vol.81,No.11,pp.213156IUPAC2009front
endpapersTimSchmidtandScottKable907

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PROLOGUE
Itislikelythatyouarereadingthesewordsbecauseyouhaveenrolledinafirstyearchemistrycourseat
university.Itmaybethatyouarestartingonacareerinchemistry,oryoumaybeplanningtostudy
anothersubjectforwhichchemistryisaprerequisite.Someofyouwillhavestudiedchemistry
throughouthighschool,while,forothersamongyou,thismaywellbethefirsttimeyouhave
encounteredchemistry.Butregardlessofyourbackgroundinchemistry,orthereasonsyouarestudying
thesubject,youareallgoingtohavetolearnsomechemistryoverthecomingmonths,andwesincerely
hopethatreadingthisbookwillmakethattaskeasier.Eachmemberoftheauthorteamhasbeenexactly
whereyouarenowweallsurvivedfirstyearchemistryandweallknowwhichteachingandlearning
approachesworkedforus.Itisouraimtobringthoseapproachestothisbooksothattheymayassist
youinyourstudies.
Thoseofyouwithyoursightssetonacareerinchemistrywillalreadyknowtheimportanceofthe
subjectandthekindofworkthatchemistsdo.Chemistsarepeopletrainedinthescienceofchemistry,
andtheyareinterestedinmanydifferentaspectsofmatter.Somechemistsareprimarilyconcernedwith
chemicalsynthesis,thepreparationofnewtypesofmatterthathavenotpreviouslyexisted.Examples
includenewdrugsforthetreatmentofdiseasenewstrong,lightweightmaterialsforuseinconstructing
everythingfromyachtstoskyscrapersandplasticsthatcanconductelectricityoremitlight.Other
chemistsareprimarilyinterestedinmeasuringthepropertiesandamountsofmatterforexample,how
muchheataparticularmaterialcanholdorhowmuchcarbondioxideisintheatmosphere.Agrowing
numberofchemistsneverevenventureintothechemicallaboratory,preferringtousecomputersto
predict,withgreataccuracy,propertiesofmatterthathasyettobemade.Theseexamplesserveto
illustratethefactthatchemistryisanexpandingsubject.Inthenottoodistantpast,chemistrywas
viewedasanarrowlydefinedsciencecarriedoutbymen(alwaysmen)inwhitecoats(alwayswhite
coats)whoinhabitedlabsfilledwithflaskscontainingallkindsofnoxiouschemicals.Thankfully,thisis
nolongerthecasenowadays,therearelikelytobemorewomenthanmeninafirstyearchemistry
class,andthescopeofchemistryhasincreasedenormously.Indeed,chemistrynowoverlapswithmany
othersciencestothepointwherethemarginsbetweenthedifferentdisciplineshavebecome
significantlyblurred.Thisisshownbythefollowingstatisticsconcerningthemostprestigiousawardin
chemistry,theNobelPrize.Ofthe25awardeesovertheperiod20002009,fewerthanhalfofthemhad
aPhDinchemistry.ManyhadamedicaldegreeorPhDinthebiologicalsciences,onehadaPhDin
physics,while,remarkably,twohadnoPhDatall.Theprizeswereawardedfortopicsasdiverseas
discoveriesabouthowwaterandothersmallmoleculescanpassthroughthewallsofcells,howproteins
aredegradedincells,thestructureandfunctionoftheribosome,thediscoveryanddevelopmentofa
proteininjellyfishthatglowsgreen,andthedevelopmentofmethodstodeterminethestructureoflarge
molecules.Manyofthesesubjectswouldusuallybethoughtofasthedomainofbiologicalscientists,
buttheirbasisisundeniablychemistry.Andhereinliesthereasonthatchemistryisaprerequisitefora
largenumberofsciencecourses.

Considermedicine,forexample.Ifyouaretrainingtobeadoctor,aknowledgeofchemistryiscrucial
weare,afterall,madeupofatoms.Thehumanbodyplayshosttoadizzyingvarietyofchemical
reactions,allofwhichplayaparticularroleinaqualitythatwecalllife.Weareabletosee,thanksin
parttoamoleculecalledretinal,whichundergoesachemicalreactionwhenitisexposedtolight.We
maintainabodytemperatureofapproximately37Cprimarilyduetoamoleculecalledadenosine
triphosphate,whichundergoesachemicalreactioninthebodythatreleasesenergy.Ournervesfunction
astheydobecauseoftheverydelicatebalanceofsodiumandpotassiumionsinthebody.Current
medicalresearchisnotjustaboutbettersurgicaltechniquesitaimstofindcuresfordiseasessuchas
cancer,HIV/AIDSandAlzheimer'sthroughanunderstandingofthemolecularbasisofsuchdiseases.
Medicalstudentsmustlearnaboutthemyriadprocessesthatenablethehumanbodytofunctionand
appreciatetherolethatchemistryplaysinmanyofthem.
Ifyouarehopingtobecomeadentist,youwillneedtobefamiliarwiththechemistryofcalcium
hydroxyapatite,animportantcomponentoftoothenamel.Dentistsneedtoappreciatetheusesand
possibledangersofmercuryfillingsmoreandmorepeoplearechoosingtohavemercuryfillings
replacedwithwhitefillingsbecauseofthepossiblehealthrisk,andanydentistmustbeabletoadvise
patientsonthissubject.Alsoofcurrentinterestisthequestionoffluoridationofwatersuppliestoreduce
theincidenceoftoothdecay,particularlyinyoungchildren.Whataretherisksandwhatarethe
benefits?Whatistheroleoffluorideinreducingtoothdecay?Whatformoffluorideisaddedtocity
watersupplies?Again,dentistsneedtohaveanunderstandingofthisveryemotiveissue.Asadentist,
youwillencounteralargenumberofnewpolymericmaterialsusedinfillings,implantsandprostheses,
andyouwillhavetounderstandthechemistryofthesetomakeappropriatechoicesofmaterialfor
particularapplications.

Thoseofyoustudyingtobepharmacistsandpharmacologistswillencountersignificantamountsof
chemistryinyourcourses.Obviously,drugsandthewayinwhichtheyaremanufacturedareimportant
inthesedisciplines,buthowthesedrugsinteractwithmoleculesinthebodyalsoconstitutesa
significantportionofyourstudy,andyouwillcertainlyrequireanappreciationofchemicalkineticsto
understandthedifferentratesatwhichparticulardrugsact.

BiochemistryandgeneticsareconcernedmainlywithhugemoleculessuchasDNA,RNAandproteins,
andtheimportanceofchemistryinthesedisciplinesisselfevident.Tounderstandhowthesemolecules
function,biochemistsandgeneticistsneedaknowledgeofchemicalprinciplessuchasacidbase
chemistry,hydrogenbondingandmolecularrecognition,aswellasanappreciationofthebasicsbehind
themethodsusedforstructuraldeterminationofthesemolecules.Biochemicalapplicationsinforensics,
mostnotablyDNAfingerprinting,havesignificantchemistrycomponentssamplesmustbekept
scrupulouslycleantoavoidcontamination,andhighlypurereagentsandstringentlycontrolled
techniquesmustbeusedtoobtainusableevidence.People'slivesdependontheskillandunderstanding
ofthepersoncarryingouttheseanalyses.

Thechemistryoftheenvironmentcontinuestoincreaseinimportanceaswegrowtoappreciatethe
significantimpactsthatmankindishavingontheEarth.Recognitionandconfirmationofthedamaging
consequencesofgreenhousegasesintheatmosphere,forexample,areduetothecarefuland
painstakingmeasurementsbyscientistsallaroundtheglobe.Becauseofthis,wenowusetermssuchas
carbonfootprintandfoodmiles,whichwereunheardofonlytwodecadesago.Likewise,
chlorofluorocarbons(CFCs)havenowbeenallbutbannedbecauseoftheircapacitytodestroythe
ozonelayer,afactrecognisedasaresultofexperimentsinthechemistrylaboratory.Itisbecauseofthis
workthattheozoneholeinthevicinityofAustraliaandNewZealandhassloweditsgrowthandis
showingsomesignsofrecovery.
Itiscertainthatwewillrunoutofaccessiblefossilfuelsatsomestage,possiblyinyourlifetimewhat
weurgentlyneedisnotmoreefficientuseofthisdwindlingresourcebutanentirelynewsourceof
energy.BothAustraliaandNewZealandareperfectlysituatedtoexploitsolarpower.Chemistsareat
theforefrontofresearchinthisareaandaredevelopingnewmaterialsthatcancleanlyandefficiently
convertsunlighttoelectricity.Again,thoseofyoustudyingenvironmentalscienceorecologywilllearn
aboutthesesubjectsandthechemistrybehindthem.

Inshort,themajorityofscienceshavesomechemistrycomponentindeed,youwillfindchemical
names,chemicalformulaeandchemicaldiagramsinmostscientifictextbooks.Butchemistryalsocrops
upinquiteunexpectedplaceslaw,forexample.Scientificdiscoverieswithanycommercialpotential
areusuallyimmediatelypatented,andthisprocessiscarriedoutbypatentattorneys.Giventhatmanyof
themostvaluablepatentsconcerndrugs,itisobviouslyvitalthatthepatentattorneysinvolvedhavean
appreciationofchemistry,andgraduateswhotrainedinbothpatentlawandchemistryarecurrentlyin
greatdemand.Similarly,anunderstandingofbothchemistryandcommerceisamajoradvantagein
manufacturingindustries,andasignificantnumberofcommercestudentsnowopttoincludesome
scienceunitsintheirdegrees.Giventheimportanceofchemistryinourmodernworld,wewouldhope
thatourleaderswouldhaveatleastsomeappreciationofthesubject.Thesubjectofclimatechange,for
example,mustbeaddressedonthebasisofscience,ratherthaneconomics,and,inanidealworld,
politicianswouldbesufficientlyversedinthechemistryofclimatechangetobeabletomakeinformed
decisions.Afterall,thefutureoftheplanetisatstake.

Butwhatofchemistryasadisciplineinitself?Whydopeoplechoosetobechemists?Thereisno
simpleanswertothisquestion,butitisprobablytruetosaythatmostchemistsarefascinatedbythe
natureofmatterandseekanunderstandingofitusingchemicalprinciples,suchasthesynthesisofnew
molecules,determinationofthestructuresofchemicalspeciesandstudiesofthereactivityofa
particularmolecule.Trainedchemistsgoontoaremarkablevarietyofjobs,notnecessarilyinchemistry
labs,andthedemandforchemistrygraduatesisalwaysstrong.

Sonowthatyouhaveanappreciationofjustwhatchemistryis,itistimetobeginourstudy.Wewill
startwithafundamentalconceptwhichunderpinsallofchemistrytheatom.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

1 TheAtom
Chemistryisthescienceconcernedwiththestudyofmatter.Matterisanythingthattakesup
spaceandhasmasseverythingyoucansee,smell,touchortaste.Centraltotheworkof
chemistsisthestructureofmatterinotherwords,thewaysinwhichmatterisconstructed
fromthefundamentalbuildingblock,theatom.

Althoughatomsaretrulytiny,andcannotbeseenusingconventionalmeansof
magnification,moderntechnologyallowsvisualisationofindividualatoms.Forexample,the
electronmicroscopeimageatrightshowsasheetofgraphene,amaterialcomposedentirely
ofcarbonatoms.Eachhexagoncomprisessixcarbonatomsandthewholesheetisjusta
singleatomthick,asshownintheaccompanyingballandstickmodel.Suchatomicscale
imagescanaidunderstandingofthepropertiesofgraphene,includingitsunusualstrength
andconductivity.
 NASAOzoneHoleWatch,http://ozonewatch.gsfc.nasa.gov

IncontrasttoAndreGeimandKonstantinNovoselov,whowereawardedtheNobelPrizein
physicsin2010fortheirworkongraphene,theearlytwentiethcenturypioneersdidnothave
recoursetoourmodernhitechmethods.Ourunderstandingofthestructureoftheatom,and
thewayinwhichatomspacktogetherinthreedimensionalspace,owesmuchtoexperiments
carriedoutbytwoAustralasianbornscientists,ErnestRutherford(18711937,NobelPrize
inchemistry1908)andWilliamLawrenceBragg(18901971,NobelPrizeinphysics1915),
usingequipmentthatwouldnowbeconsideredprimitive.TheNewZealandbornRutherford
wasthefirsttoshowthattheatomconsistsofapositivelychargednucleussurroundedby
tinynegativelychargedelectrons,whileBragg(borninAustralia),togetherwithhisBritish
bornfatherWilliamHenryBragg,developedthetechniqueofXraycrystallography,in
whichXraysareusedtodeterminethethreedimensionalstructureofsolidmatteronthe
atomicscale.ThecontributionoftheBraggswillbeoutlinedfurtherinchapter7.This
chapterisprimarilyconcernedwiththeatom.ItwillexaminethecontributionofRutherford
andotherstothedeterminationofthestructureoftheatom,andwillshowhowaparticular
 structuralfeatureoftheatomformsthebasisoftheperiodictableoftheelements.

KEYTOPICS

1.1Atoms,molecules,ions,elementsandcompounds
1.2Theatomictheory
1.3Thestructureoftheatom
1.4Theperiodictableoftheelements
1.5Electronsinatoms

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.1Atoms,Molecules,Ions,Elementsand
Compounds
Chemistryisthestudyofmatter.Chemistsviewmatterasbeingcomposedofvariouschemicalentities.
Beforeweembarkonourstudyofchemistry,wewillbrieflydefinesometermsusedtodescribethese
entities.Thiswillaidourunderstandingofthematerialinthischapterwewilllookattheseconcepts
again,ingreaterdetail,insubsequentchapters.Atomsarediscretechemicalspeciescomprisinga
centralpositivelychargednucleussurroundedbyoneormorenegativelychargedelectrons.Atomsare
alwayselectricallyneutral,meaningthatthenumberofelectronsisequaltothenumberofprotonsinthe
nucleus.Chemistsregardtheatomasthefundamentalbuildingblockofallmatter,soitmaysurprise
youtolearnthatindividualatomsarerarelyofchemicalinterestfreeatoms(withtheexceptionofthe
elementshelium,neon,argon,krypton,xenonandradon)areusuallyunstable.Ofmuchgreaterinterest
tochemistsaremolecules,whicharecollectionsofatomswithadefinitestructureheldtogetherby
chemicalbonds.Thesmallestmoleculescontainjusttwoatoms,whilethelargestcanconsistofliterally
millions.Mostgasesandliquidsconsistofmolecules,andmostsolidsbasedoncarbon(organicsolids)
arealsomolecular.Likeatoms,moleculesareelectricallyneutralandare,therefore,uncharged.
Moleculesareheldtogetherbycovalentbonds,whichinvolvethesharingofelectronsbetween
neighbouringatoms.

Ionsarechemicalspeciesthathaveeitherapositiveornegativeelectriccharge.Thosewithapositive
chargearecalledcationsthosewithanegativechargearecalledanions(respectivelydesignatedbya+
or).Ionscanbeformallyderivedfromeitheratomsormoleculesbytheadditionorremovalofoneor
moreelectrons.Forexample,removinganelectron(e)fromasodium,Na,atomgivestheNa+cation.

Addinganelectrontoanoxygenmolecule,whichconsistsoftwooxygenatomsbondedtogetherandis
designatedO2,givesthesuperoxideanion.

Elementsarecollectionsofonetypeofatomonly,andthe118elementsknownatthetimeofwriting
arelistedintheperiodictableontheinsidefrontcover.Compoundsaresimplysubstancescontaining
twoormoreelementsinadefiniteandunchangingproportion.Compoundsmaybecomposedof
molecules,ionsorcovalentlybondednetworksofatoms.Notethatwedonothaveindividual
moleculesofanioniccompoundsuchassodiumchloride.Thechemicalformulaofsodiumchloride,
NaCl,simplyrepresentsthesmallestrepeatingunitinanenormousthreedimensionalarrayofNa+ions
andClions.Thesameappliestocertaincovalentlybondedstructures.Forexample,quartz,whichis
composedofaninfinitethreedimensionalnetworkofcovalentlyboundSiandOatoms,hasthe
chemicalformulaSiO2,whichrefersnottoindividualSiO2moleculesbuttothesmallestrepeatingunit
inthenetwork.

Alloftheabovechemicalentities(atoms,molecules,ions,elementsandcompounds)maybeinvolved
asreactantsinchemicalreactions,processesinwhichtheyundergotransformationsgenerally
involvingthemakingand/orbreakingofchemicalbonds,andwhichusuallyresultintheformationof
differentchemicalspeciescalledproducts.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.2TheAtomicTheory
Today,wetaketheexistenceofatomsforgranted.Wecanexplainmanyaspectsofthestructureofthe
atomand,infact,currenttechnologyallowsustoseeandevenmanipulateindividualatoms.
However,scientificevidencefortheexistenceofatomsisrelativelyrecent,andchemistrydidnot
progressveryfaruntilthatevidencewasfound.

Theconceptofatomsbegannearly2500yearsagowhentheGreekphilosopherLeucippusandhis
studentDemocritusexpressedthebeliefthatmatterisultimatelycomposedoftinyindivisibleparticles
thewordatomisderivedfromtheGreekwordatomos,meaningnotcut.Thephilosophers'
conclusions,however,werenotsupportedbyanyscientificevidencetheywerederivedsimplyfrom
philosophicalreasoning.Theconceptofatomsremainedaphilosophicalbelief,havinglimitedscientific
usefulness,untilthediscoveryoftwolawsofchemicalcombinationinthelateeighteenthcenturythe
lawofconservationofmassandthelawofdefiniteproportions.Thesemaybestatedasfollows:
thelawofconservationofmass:Nodetectablegainorlossofmassoccursinchemicalreactions.
Massisconserved.
thelawofdefiniteproportions:Inagivenchemicalcompound,theelementsarealwayscombined
inthesameproportionsbymass.
TheFrenchchemistAntoineLavoisier(17431794)proposedthelawofconservationofmassasa
resultofhisexperimentsinvolvingtheindividualreactionsoftheelementsphosphorus,sulfur,tinand
leadwithoxygen.HeusedalargelenstofocustheSun'sraysonasampleofeachelementcontainedin
aclosedjar,andtheheatcausedachemicalreactiontotakeplace.Heweighedtheclosedjarandits
contentsbeforeandafterthechemicalreactionandfoundnodifferenceinmass,leadinghimtopropose
thelaw.(LavoisierwasbeheadedfollowingtheFrenchRevolution,thejudgeathistrialreputedly
sayingtheRepublichasnoneedofscientists.)Thelawofconservationofmasscanbealternatively
statedasmassisneithercreatednordestroyedinchemicalreactions.

AnotherFrenchchemist,JosephLouisProust(17541826),wasresponsibleforthelawofdefinite
proportions,followingexperimentsthatshowedthatcoppercarbonatepreparedinthelaboratorywas
identicalincompositiontocoppercarbonatethatoccursinnatureasthemineralmalachite.Healso
showedthatthetwooxidesoftin,SnOandSnO2,andthetwosulfidesofiron,FeSandFeS2,always
containfixedrelativemassesoftheirconstituentelements.Thelawstatesthatchemicalelementsalways
combineinadefinitefixedproportionbymasstoformchemicalcompounds.Thus,ifweanalyseany
sampleofwater(acompound),wealwaysfindthattheratioofoxygentohydrogen(theelementsthat
makeupwater)is8to1bymass.Similarly,ifweformwaterfromoxygenandhydrogen,themassof
oxygenconsumedwillalwaysbe8timesthemassofhydrogenthatreacts.Thisistrueevenifthereisa
largeexcessofoneofthem.Forinstance,if100gofoxygenismixedwith1gofhydrogenandthe
reactiontoformwaterisinitiated,allthehydrogenwouldreactbutonly8gofoxygenwouldbe
consumedtherewouldbe92gofoxygenleftover.Nomatterhowwetry,wecannotalterthechemical
compositionofthewaterformedinthereaction.

WORKEDEXAMPLE1.1

ApplyingtheLawofDefiniteProportions
Theelementmolybdenum,Mo,combineswithsulfur,S,toformacompoundcommonly
calledmolybdenumdisulfidethatisusefulasadrylubricant,similartographite.Itisalso
usedinspecialisedlithiumbatteries.Asampleofthiscompoundcontains1.50gofMofor
each1.00gofS.Ifadifferentsampleofthecompoundcontains2.50gofS,whatmassof
 Modoesitcontain?

Analysis

ThelawofdefiniteproportionsstatesthattheproportionsofMoandSbymassmustbethe
sameinbothsamples.Tosolvetheproblem,wewillsetupthemassratiosforthetwo
samples.Intheratioforthesecondsamplethemassofmolybdenumwillbeanunknown
quantity.Wewillequatethetworatiosandsolvefortheunknownquantity.

Solution

ThefirstsamplehasaMotoSmassratioof:

WeknowthemassofSinthesecondsample,butthemassofMoisunknown.Wedoknow,
however,thattheMotoSmassratioisthesameasthatinthefirstsample.Wesetuptheratio
forthesecondsampleusingxfortheunknownmassofMo.Therefore,fromthelawof
definiteproportions,wecanwrite:

Wecansolveforxbymultiplyingbothsidesoftheequationby2.50gS,togive:

Isouranswerreasonable?

Toavoiderrors,itisalwayswisetodoaroughcheckoftheanswer.Usually,somesimple
reasoningisallweneedtoseeiftheanswermakessense.Thisishowwemightdosucha
checkhere:Noticethatthemassofsulfurinthesecondsampleismorethantwicethemass
inthefirstsample.Therefore,weshouldexpectthemassofMointhesecondsampletobe
somewhatmorethantwicewhatitisinthefirst.Theanswerweobtained,3.75gMo,ismore
thantwice1.50gMo,soouranswerseemstobereasonable.

PRACTICEEXERCISE1.1
Cadmiumsulfideisayellowcompoundthat
isusedasapigmentinartists'oilcolours.A
sampleofthiscompoundiscomposedof
1.25gofcadmium,Cd,and0.357gof
sulfur,S.Ifasecondsampleofthesame
compoundcontains3.50gofsulfur,what
massofcadmiumdoesitcontain?

Thelawsofconservationofmassanddefiniteproportionsservedastheexperimentalfoundationforthe
atomictheory.Theypromptedthequestion,Whatmustbetrueaboutthenatureofmatter,giventhe
truthoftheselaws?Inotherwords,Whatismattermadeof?Atthebeginningofthenineteenth
century,JohnDalton(17661844),anEnglishscientist,usedtheGreekconceptofatomstomakesense
ofthelawsofconservationofmassanddefiniteproportions.Daltonreasonedthat,ifatomsreallyexist,
theymusthavecertainpropertiestoaccountfortheselaws.Hedescribedsuchproperties,andthe
followinglistconstituteswhatwenowcallDalton'satomictheory.
1.Matterconsistsoftinyparticlescalledatoms.
2.Atomsareindestructible.Inchemicalreactions,theatomsrearrangebuttheydonotthemselves
breakapart.
3.Inanysampleofapureelement,alltheatomsareidenticalinmassandotherproperties.
4.Theatomsofdifferentelementsdifferinmassandotherproperties.
5.Whenatomsofdifferentelementscombinetoformagivencompound,theconstituentatomsin
thecompoundarealwayspresentinthesamefixednumericalratio.

Dalton'stheoryeasilyexplainedthelawofconservationofmass.Accordingtothetheory,achemical
reactionissimplyareorderingofatomsfromonecombinationtoanother.Ifnoatomsaregainedorlost,
andifthemassesoftheatomscan'tchange,themassafterthereactionmustbethesameasthemass
before.Thisexplanationofthelawofconservationofmassallowsustouseanotationsystemof
chemicalequationstodescribechemicalreactions.Achemicalequationcontainsthereactantsonthe
lefthandsideandtheproductsontherighthandside,separatedbyaforwardarrow,asdemonstratedin
thefollowingchemicalequationfortheformationofliquidwaterfromitsgaseouselements.

Thelawofconservationofmassrequiresustohavethesamenumberofeachtypeofatomoneachside
ofthearrowthisbeingthecase,thechemicalequationaboveisdescribedasbalanced.Wewilldiscuss
thisconceptindetailinchapter3.Notethatthischemicalequationalsospecifiesthephysicalstatesof
thereactantsandproduct.Gases,liquidsandsolidsareabbreviatedas(g),(l)and(s),respectively,after
eachreactantandproduct.

ThelawofdefiniteproportionscanalsobeexplainedbyDalton'stheory.Accordingtothetheory,a
givencompoundisalwayscomposedofatomsofthesameelementsinthesamenumericalratio.
Suppose,forexample,thatelementsXandYcombinetoformacompoundinwhichthenumberof
atomsofXequalsthenumberofatomsofY(i.e.theatomratiois1to1).IfthemassofaYatomistwice
thatofanXatom,theneverytimeweencounterasampleofthiscompound,themassratio(XtoY)
wouldbe1to2.Thissamemassratiowouldexistregardlessofthesizeofthesampleso,insamplesof
thiscompound,elementsXandYarealwayspresentinthesameproportionbymass.

StrongsupportforDalton'stheorycamewhenDaltonandotherscientistsstudiedelementsthatcan
combinetogiveatleasttwocompounds.Forexample,sulfurandoxygencancombinetoformboth
sulfurdioxide,SO2,andsulfurtrioxide,SO3.Theformercontainsoneatomofsulfurandtwoatomsof
oxygen,whilethelattercontainsoneatomofsulfurandthreeatomsofoxygen.Althoughtheyhave
similarchemicalformulae,theyaredifferentchemicallyforexample,atroomtemperature,SO2isa
colourlessgaswhileSO3,whichmeltsat16.8C,isasolidorliquid,dependingonthetemperatureof
theroom.IfweanalysesamplesofSO2andSO3inwhichthemassesofsulfurarethesame,weobtain
theresultsshownintable1.1.
TABLE1.1 MassCompositionofSulfurDioxideandSulfurTrioxide
Compound Massofsulfur Massofoxygen
SO2 1.00g 1.00g

SO3 1.00g 1.50g

Notethattheratioofthemassesofoxygeninthetwosamplesisoneofsmallwholenumbers.

Similarobservationsaremadewhenwestudyotherelementsthatformmorethanonecompoundwith
eachother.Theseobservationsformthebasisofthelawofmultipleproportions,whichstatesthat:
Whenevertwoelementsformmorethanonecompound,thedifferentmassesofoneelementthat
combinewiththesamemassoftheotherelementareintheratioofsmallwholenumbers.

Dalton'stheoryexplainsthelawofmultipleproportionsinaverysimpleway.Supposeamoleculeof
sulfurtrioxidecontains1sulfurand3oxygenatoms,andamoleculeofsulfurdioxidecontains1sulfur
and2oxygenatoms(figure1.1).Ifwehadjustonemoleculeofeach,oursampleswouldeachhave1
sulfuratomand,therefore,thesamemassofsulfur.Then,comparingtheoxygenatoms,wefindthey
areinanumericalratioof3to2.Butbecauseoxygenatomsallhavethesamemass,themassratiomust
alsobe3to2.ThelawofmultipleproportionswasnotknownbeforeDaltonpresentedhistheory,and
itsdiscoverydemonstratesscienceinaction.ExperimentaldatasuggestedtoDaltontheexistenceof
atoms,andtheatomictheorysuggestedtherelationshipsthatwenowcallthelawofmultiple
proportions.Whenfoundbyexperiment,theexistenceofthelawofmultipleproportionsaddedgreat
supporttotheatomictheory.Infact,formanyyears,itwasoneofthestrongestargumentsinfavourof
theexistenceofatoms.

FIGURE1.1Compoundscontainingoxygenandsulfurdemonstratethelawofmultipleproportions.
Representedherearemoleculesofsulfurtrioxide,SO3 ,andsulfurdioxide,SO2 .Eachhasone
sulfuratom,andthereforethesamemassofsulfur.Theoxygenratiois3to2,bothbyatomsand
bymass.

AsoutlinedintheChemicalConnectionsfeatureonthenextpage,wearenowabletoseeandeven
manipulateindividualatoms,therebyprovidingproofoftheatomicnatureofmatter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.3TheStructureoftheAtom
Eventhoughabsoluteproofoftheexistenceofatomswasnotavailablearoundtheturnofthetwentieth
century,scientistswereinterestedinthestructureoftheatom.WhileDalton'stheorysaidthatatoms
wereindestructibleandcouldnotbebrokenapart,experimentsaroundthistimeshowedthiswasnot
necessarilytrue.Inparticular,thediscoveryofradiationintheformofXraysbyWilhelmRntgen
(18451923)in1895(seefigure1.2)andradioactivitybyAntoineHenriBecquerel(18521908,
picturedinfigure1.3)in1896ledscientiststobelievethattheatomwascomposedofdiscreteparticles,
asbothformsofradiationinvolvethereleaseofparticlesfromatoms,thoughtatthattimetobe
indivisible.

FIGURE1.2AreproductionofoneofthefirsteverXrayimages,takenbyWilhelmRntgen(NobelPrizein
physics,1901)on22December1895.Thehandisthatofhiswife.
 FIGURE1.3AntoineHenriBecquerel(NobelPrizeinphysics,1903)discoveredradioactivity.

ChemicalConnections

Nanotechnology:ControllingStructureattheMolecularLevel

Nanotechnologyisawordthatisfindingincreasinguse,especiallyinthepopularmedia.As
weshallseeinchapter2,theprefixnanomeans10 9,andnanotechnologycanthereforebe
broadlydefinedasthescienceofobjectshavingdimensionsonthenanometre(10 9m)scale.
Individualatomshavediametersoftheorderof10 10minotherwords,fractionsofa
nanometre.Nanoscaleobjectsthereforehavedimensionsofperhapstenstohundredsof
atoms.

Nanotechnologydealswithusingsuchsmallscaleobjectstoaccomplishusefultasks.Oneof
thegoalsofnanotechnologyistobuildmaterialsfromtheatomup.Thereareseveralreasons
forthegreatinterestinnanotechnology.Forone,thepropertiesofmaterialsarerelatedto
theirstructures.Bycontrollingstructuresattheatomicandmolecularlevel,wecan(in
principle)tailormaterialstohavespecificproperties.Drivingmuchoftheresearchinthisarea
arethecontinuingeffortsbycomputerandelectronicsdesignerstoproduceeversmaller
circuits.Thereductionsinsizeachievedthroughtraditionalmethodsareneartheirlimit,so
newwaystoachievesmallercircuitsandsmallerelectricaldevicesarebeingsought.

Anotherareaofresearchofmuchinteresttodayisthefieldofmolecularselfassembly,in
whichcertainmolecules,whenbroughttogether,spontaneouslyarrangethemselvesinto
desirablestructures.Biologicalsystemsemploythisstrategyinconstructingstructuressuchas
cellularmembranes.Thegoalofscientistsistomimicbiologybydesigningmoleculesthat
willselfassembleintospecificarrangements.

Visualisingandmanipulatingnanoscaleobjects
Wecannotuseopticalmicroscopestoobservenanoscaleobjects,becausetheirdimensions
aresmallerthanthewavelengthofvisiblelight.However,theinventionofboththescanning
tunnellingmicroscope(STM)andtheatomicforcemicroscope(AFM)inthelatetwentieth
centuryhasallowedustoseeand,moreremarkably,manipulateindividualatoms.TheSTM
andAFMoperateusingthesamebasicprinciplemovingthetipofanextremelyfinestylus
acrossasurfaceatadistanceofatomicdimensions.InthecaseoftheSTM,thesurfacemust
beelectricallyconducting,andthiscausesacurrenttoflowbetweenthesurfaceandthetip.
Themagnitudeofthiscurrentdependsonthedistancebetweenthetipandthesurface,soas
thetipismovedacrossthesurface,computercontrolofthecurrentataconstantvaluewill
causethetiptomoveupanddown,therebygivingamapofthesurface.Becauseofitstiny
size,thetipcanalsobeusedtomoveindividualatoms.Oneofthefirstdemonstrationsof
nanotechnologycamein1989whenDonEigler,ascientistatIBM,manipulated35atomsof
xenononanickelsurfaceusinganSTMtospellthenameofhisemployer(figure1.4).

FIGURE1.4IndividualXeatoms(bluedots)onanickelsurfacemanipulatedbyanSTMtip.

AnAFM(illustratedinfigure1.5)isusedtostudynonconductingsamples.Thestylusis
movedacrossthesurfaceofthesampleunderstudy.Forcesbetweenthetipoftheprobeand
thesurfacecausetheprobetoflexasitfollowstheupsanddownsofthebumpsthatarethe
individualmoleculesandatoms.Amirroredsurfaceattachedtotheprobereflectsalaser
beamatanglesproportionaltotheamountofdeflectionoftheprobe.Asensorpicksupthe
signalfromthelaserandtranslatesitintodatathatcanbeanalysedbyacomputertogive
threedimensionalimagesofthesample'ssurface.

FIGURE1.5InanAFM,asharpstylusattachedtotheendofacantileverproberidesupand
downoverthesurfacefeaturesofthesample.Alaserbeam,reflectedoffamirrored
surfaceattheendoftheprobe,changesangleastheprobemovesupanddown.A
photodetectorreadsthesechangesandsendstheinformationtoacomputer,which
translatesthedataintoanimage.

AtypicalAFMimageisshowninfigure1.6.Itinvolvesmanipulatingsingleatomstogive
 whatisprobablythesmallestknownwriting.

FIGURE1.6Theworld'ssmallestwriting?Theelementsymbolforsilicon,Si,isspelledoutwith
individualsiliconatoms(dark)amongtinatoms(light).Thesiliconatomswere
manipulatedwiththetipofanAFM.

Furtherevidenceforthepresenceofdiscreteparticlesinatomscamefromexperimentswithgas
dischargetubes,suchasthatshowninfigure1.7.Whenthetubewasfilledwithalowpressuregasand
ahighvoltagewasappliedbetweentheelectrodes,negativelychargedparticlesflowedfromthe
negativeelectrode(cathode)tothepositiveelectrode(anode).

FIGURE1.7Diagramofagasdischargetube.

Becausetheyemanatedfromthecathode,theparticleswerecalledcathoderays.In1897,theBritish
physicistJJThomsonpassedcathoderaysthroughamagneticfieldusingthemodifieddischargetube
showninfigure1.8.Themagneticfieldcausedthepathofthecathoderaystobend.Analysisofthis
effectallowedThomsontodeterminethechargetomassratioofthecomponentsofcathoderays,what
wenowknowaselectrons.
 FIGURE1.8DiagramoftheapparatususedbyJJThomsontodeterminethechargetomassratioofthe
electron.Thecathoderaybeampassesbetweenthepolesofamagnetandbetweenapairof
metalelectrodesthatcanbegivenelectriccharges.Themagneticfieldtendstobendthebeam
inonedirection(topoint2)whilethechargedelectrodesbendthebeamintheoppositedirection
(topoint3).Byadjustingthechargeontheelectrodes,thetwoeffectscanbemadetocancel
eachother(point1).Theamountofchargeontheelectrodesrequiredtobalancetheeffectofthe
magneticfieldcanbeusedtocalculatethechargetomassratio.

In1909,theAmericanchemistRobertMillikandeterminedthechargeonanindividualelectronby
measuringtheratesatwhichchargedoildropsfellbetweenelectricallychargedplates.This,combined
withThomson'sresults,allowedcalculationofthemassofanelectronas9.0910 31kg.The
knowledgethatatomswereelectricallyneutralmeantthattheelectronmusthaveapositivelycharged
counterpart,butitsexactnaturewasnotknownbytheearlyyearsofthetwentiethcentury.Itwasthe
workoftheNewZealandbornscientistErnestRutherford(18711937)thatshedlightnotonlyonthe
positivelychargedcomponentoftheatom,butalsoonthestructureoftheatomitself.Around1909,
Rutherford,whohadalreadywontheNobelPrizeinchemistryin1908forhisworkonthetheoryof
radioactivity,devisedhisfamousgoldfoilexperimentdepictedinfigure1.9.Rutherfordtookan
incrediblythinsheetofgold(onlyafewatomsthick)andbombardeditwithastreamofpositively
chargedparticlescalledalphaparticles.
 FIGURE1.9SchematicviewofRutherford'sgoldfoilexperiment.Whenabeamofpositivelychargedalpha
particleswasshotatathingoldfoil,mostofthempassedstraightthroughthefoil.Some,
however,weredeflectedstraightbacktowardsthesource.

Mostoftheparticleswentstraightthroughthefoilessentiallyundisturbed,someweredeflectedthrough
variousangles,andabout1in8000wasdeflectedalmoststraightbacktowardsthesource.Ofthis
amazingobservation,Rutherfordsaid,Itwasalmostasincredibleasifyouhadfiredafifteeninch
[38.1centimetre]shellatapieceoftissuepaperanditcamebackandhityou.Toexplainhis
observations,Rutherfordproposedanewmodeloftheatom.Hesuggestedthateveryatomhasatiny
positivelychargedcentralcore,whichhecalledthenucleus,thatconstitutesmostofthemassofthe
atom.Thepositivechargeinthenucleusisduetoparticles,whichhecalledprotons,andthenumberof
theseinthenucleusdeterminestheidentityoftheatom.Theelectricalneutralityoftheatomrequires
thatthereisthesamenumberofelectronsinanatomasthereareprotonsinthenucleus,andthese
surroundthecentralcore,asshownschematicallyinfigure1.10.

FIGURE1.10Diagram(nottoscale)showingthenucleusandthevolumeoccupiedbythesurrounding
electrons.Ifthisweredrawntoscale,thenucleuswouldbeinvisible.
Electronsoccupyavolumethatishugecomparedwiththesizeofthenucleus,buteachelectronhas
suchasmallmassthatalphaparticlesarenotdeflectedbytheelectrons.Consequently,analphaparticle
isdeflectedonlywhenitpassesverynearanucleus,anditbouncesstraightbackonlywhenitcollides
headonwithanucleus.Becausemostofthevolumeofanatomisessentiallyemptyspace,mostalpha
particlespassthroughthefoilwithoutbeingaffected.Fromthenumberofparticlesdeflectedandthe
patternofdeflection,Rutherfordcalculatedthatthepositivenucleusoccupieslessthan0.1%ofthetotal
atomicvolume.Togiveyouanideaofwhatthatmeans,anatomthesizeofarugbystadiumwould
haveanucleusthesizeofapea.WhenRutherfordcalculatedthenuclearmassbasedonthenumberof
protonsinthenucleus,thevaluealwaysfellshortoftheactualmass.Infact,Rutherfordfoundthatonly
abouthalfofthenuclearmasscouldbeaccountedforbyprotons.Thisledhimtosuggestthattherewas
anotherparticleinthenucleusthathadamassclosetoorequaltothatofaproton,butwithnoelectric
charge.Thissuggestioninitiatedasearchthatfinallyendedin1932withthediscoveryoftheneutron
byJamesChadwick(18911974),aBritishphysicist.Becausetheyarefoundinthenucleus,protons
andneutronsaresometimescallednucleons.Table1.2summarisesthesubatomicparticlespresentin
thismodeloftheatom.
TABLE1.2 PhysicalDatafortheElectron,ProtonandNeutron
Particle Symbol Charge(C) Mass(kg) Mass(u)
electron e 1.602210 19 9.109410 31 5.485810 4
proton p +1.602210 19 1.672610 27 1.0073
neutron n 0 1.674910 27 1.0087

Note:Thechargeismeasuredincoulombs(C).Thefinalcolumngivesthemassinatomicmass
units(u)1u=1.6605410 27kg( themassofthe12Catom)(p.10).

Overtheinterveningyears,ithasbeenshownthatprotonsandneutronsarethemselvescomposedof
stillsmallerparticlescalledquarks.Theexistenceofquarkshashelpedusunderstandhowtheatomic
nucleuscanstaytogetherdespitethepresenceofpositivelychargedprotonsincloseproximity.
However,quarksareveryunstableoutsidetheconfinesoftheatomicnucleusandareofmoreinterestto
physiciststhanchemists.

Toexaminehowatomsareconstructed,wewillconsiderthesimplestpossibleatom,hydrogen,withthe
chemicalsymbolH.Ahydrogenatomconsistsofasingleprotoninthenucleus,andasingleelectron.
Wedesignatethisas .WeusethisterminologyforanychemicalelementXasfollows:

whereAisthemassnumber,ZistheatomicnumberandXisthechemicalsymbolofthechemical
element.Theatomicnumber(Z)isthenumberofprotonsinthenucleus.Themassnumber(A)isthe
numberofprotonsinthenucleusplusthenumberofneutrons(N)inthenucleus.

Notethattheatomicnumberisalsoequaltothenumberofelectronsinaneutralatom(i.e.oneinwhich
thenumberofprotonsandthenumberofelectronsisthesame).Achemicalelementisdefinedbyits
atomicnumberallatomshavingthesameatomicnumberareatomsofthesameelement.Therefore,the
symbol tellsusthatanatomofhydrogencontains1proton(Z=1),1electronand0neutrons(A=
1).

Ifweweretoanalyseasampleofhydrogenatoms,wewouldfindthatroughly1atominevery6600
wouldhaveapproximatelytwicethemassofa atom.Theseheavieratomsbelongtoanisotopeof
hydrogencalleddeuterium.Isotopesareatomsofanelementwiththesamenumberofprotons(i.e.the
samevalueofZ)butdifferentnumbersofneutrons(i.e.differentvaluesofA).Deuteriumatomsare
symbolisedas ,meaningthatthereis1proton(Z=1)and1neutron(A=2)inthenucleus.The
atomissometimescalledprotiumtodistinguishitfromdeuterium.Inchemicalterms,deuteriumatoms
behaveessentiallyidenticallytohydrogenatoms,buttherearesomeimportantdifferencesinreactivity
whentheyarebondedtootheratoms.Inaddition,hydrogenalsohasathirdisotopecalledtritium, ,
whichhas1protonand2neutronsinthenucleus.Itistheleastabundantisotopeofhydrogen,withonly
1to10atomsoftritiuminevery10 18atomsofhydrogen.Tritiumisradioactive,meaningthatthe
nucleusisunstableandundergoesspontaneousdecaytogiveanatomofhelium,He,aprocesswewill
lookatingreaterdetailinchapter27.Heliumatomsarecharacterisedbyhaving2protonsinthe
nucleus(Z=2).Heliumhastwostableisotopes, and ,with1and2neutrons,respectively,in
thenucleus.Theelementwith3protonsinthenucleus,lithium(Z=3),hasthestableisotopes and
with3and4neutrons,respectively.AnyatomofaspecifiedAandZiscalledanuclide.A
radionuclideisaradioactivenuclide.

WORKEDEXAMPLE1.2

TheCompositionofAtoms
Thefollowingradioactiveisotopeshavemedicalapplications.Determinethenumberof
protons,neutronsandelectronsineachisotope.
(a) Dy(usedinthetreatmentofarthritis)
(b) (usedtoimagethethyroidgland)
(c) (usedinstudiesofironmetabolism)

Analysis

Thenumberofprotonsisequaltotheatomicnumber(Z),thenumberofneutronsisfound
fromZandthemassnumber(A),andthenumberofelectronsinaneutralatommustequal
thenumberofprotons.

Solution
(a)Dyisthechemicalsymbolfordysprosium.Thesubscript66isZ,whichisthenumber
ofprotonsinthenucleus.Thesuperscript165isA.Wefindthenumberofneutrons
bysubtractingZfromA:AZ=16566=99neutrons.Becausethisisaneutral
atom,thenumberofelectronsmustequalthenumberofprotons. has66
protons,99neutronsand66electrons.
(b)Iisthesymbolforiodine.Z=53andA=131.Ztellsusthatthenucleuscontains53
protons.SubtractingZfromA,wefindthatthereare78neutronsinthisisotope.
Finally,theatomisneutral,sothereare53electrons.
(c) Iron,Fe,hasZ=26.Aneutralatomof has26protons,26electrons,and5926
=33neutrons.

Isouranswerreasonable?

Inallcases,thenumberofprotonsisequaltothenumberofelectrons,asrequiredforneutral
atoms.Wehavefollowedtherulesforcalculatingthenumberofneutronsandhavecarried
 outthecalculationsproperly.Ouranswersshouldthereforebecorrect.

PRACTICEEXERCISE1.2
Thefollowingradioactiveisotopeshave
medicalapplications.Determinethenumber
ofprotonsandneutronsineach.
(a) (usedasanimagingand
therapeuticagent)
(b) (usedinstudiesofthelungs)
(c) (usedintheformofawirefor
internalcancertreatment)

Inclusionoftheatomicnumberinthisterminologyisalmostredundantwhenthechemicalsymbolis
included,soitiscommontoseeashorthandversionthatexcludesthis.Thus,weoftenwrite as
simply1H,asweknowthatallatomsofhydrogenhaveZ=1.Usingthesameshorthandversion,
deuteriumwouldbewrittenas2Handtritiumas3H.

AtomicMass

Wesawintable1.2thatthe12Cisotopeisusedasthebasisbywhichatomicmassismeasured.The
atomicmassunit(u)isthemass(1.6605410 27kg)equalto themassofoneatomof12C,and
themassesofallatomsaremeasuredrelativetothis.TheatomicmassunitisalsoknownastheDalton
(Da),particularlyinbiochemistry.Usingthisscale,wefindthatthemassofasingle19Fatomis18.998
4032uandthatofasingle31Patomis30.973762u.Becausebothfluorineandphosphorushaveonly
onenaturallyoccurringisotope,wecanbesurethatanyfluorineatomwechosefromamacroscopic
sampleoffluorinewouldhaveamassof18.9984032u,whileanyphosphorusatomchosenfroma
macroscopicsampleofphosphoruswouldhaveamassof30.973762u.Wethereforesaythatthe
atomicmassoffluorineis18.9984032uandtheatomicmassofphosphorusis30.973762u.
However,themajorityofelementsintheperiodictablecomprisetwoormoreisotopes,andthemassof
asingleatomchosenatrandomfromamacroscopicsampleoftheseelementswouldnotbeconstant
itwoulddependonwhichisotopewaschosen.Wethereforedefinetheatomicmassoftheseelementsas
theaveragemassperatomofanaturallyoccurringsampleofatomsoftheelement.Consider,for
example,bromine,Br.TherearetwonaturallyoccurringisotopesofBr,namely and ,eachof
whichcontains35protonsinthenucleus.Nucleioftheformercontain44neutronswhilethoseofthe
lattercontain46.Anynaturallyoccurringsampleofbrominewillbecomposedof50.69%ofthe
isotopeand49.31%ofthe isotope.Giventheatomicmassesoftheseisotopes( ,
)wecancalculatetheaverageatomicmassofBrbytakingthesumoftheatomicmass
ofeachisotopemultipliedbyitsabundanceasfollows.

TheaverageatomicmassofBr,79.90u,isjustlessthantheaverageofthemassesofthetwoisotopes
(79.9173u)becausethelighter isotopeisslightlymoreabundantthantheheavier isotope.
Figure1.11illustratestherangeofisotopiccompositionsfoundinfourelements,oneofwhichistin,the
elementwiththelargestnumberofstableisotopes.

FIGURE1.11Thenaturalabundancesoftheisotopesofchlorine,Cl,chromium,Cr,germanium,Ge,andtin,
Sn,illustratethediversityofisotopicdistributions.Themassnumberandrelativeabundanceof
eachisotopeareindicated.

Whilethedistributionofisotopesinsamplesofmostelementsisessentiallyconstant,thereareten
elements(H,Li,B,C,N,O,Si,S,ClandTl)whichshowsubstantialvariationintheirisotopic
compositions,dependingonthesourceoftheelement.Consider,forexample,hydrogen.Aswehave
seen,thiselementhasthreeisotopes,1H,2Hand3H,thelastofwhichwewillneglectinthisdiscussion
becauseofitsnegligibleabundance.Ifweanalysedsamplesofatmosphericmethaneandnaturalgas,
wewouldfindthattheproportionofthe2Hisotopeinthehydrogenatomsoftheformerwouldbe
greaterthanthatinthelatter,andhencetheaverageatomicmassofHinthetwosampleswouldbe
different.Therefore,insteadofquotingasinglevaluefortheaverageatomicmassofhydrogen,arange
ofvaluesofatomicmassisgiven[1.00784u1.00811u],whichcorrespondstothelowestandhighest
valuesmeasuredinnaturalsamples.Table1.3givestherangeofatomicmassvaluesfortheseten
elements,togetherwiththeconventionalatomicmasseswhichcanbeusedwhenthesourceofthe
sampleisunknown.
TABLE1.3 AtomicMassRangesandConventionalAtomicMassesforH,Li,B,C,N,O,Si,S,ClandTl
Element Atomic Atomicmassrange Conventionalatomicmass
name Symbol number (u) (u)
hydrogen H 1 [1.007841.00811] 1.008
lithium Li 3 [6.9386.997] 6.94
 boron B 5 [10.80610.821] 10.81
carbon C 6 [12.009612.0116] 12.011
nitrogen N 7 [14.0064314.007 14.007
28]
oxygen O 8 [15.9990315.999 15.999
77]
silicon Si 14 [28.08428.086] 28.085
sulfur S 16 [32.05932.076] 32.06
chlorine Cl 17 [35.44635.457] 35.45
thallium Tl 81 [204.382204.385] 204.38

Inthisbook,wewillusetheconventionalatomicmasseslistedintable1.3inanycalculationsinvolving
thesetenelements.

WORKEDEXAMPLE1.3

CalculatingAverageAtomicMassesfromIsotopic
Abundances
Naturallyoccurringtitanium,Ti,isamixtureoffiveisotopesandhasthefollowingisotopic
composition:

Theatomicmassesoftheisotopesareasfollows:

Usethisinformationtocalculatetheaverageatomicmassoftitanium.

Analysis

Inasamplecontainingmanyatomsoftitanium,8.25%ofthetotalmassiscontributedby
atomsof46Ti,7.44%byatomsof47Ti,73.72%byatomsof48Ti,5.41%byatomsof49Ti
and5.18%byatomsof50Ti.Thismeansthat,whenwecalculatethemassofthehypothetical
averageatomofTi,wehavetoweightitaccordingtoboththemassesoftheisotopesand
theirrelativeabundance.(Keepinmind,ofcourse,thatsuchanatomdoesnotreallyexist.
Thisisjustasimplewaytoseehowwecancalculatetheaverageatomicmassofthis
element.)

Solution
 Wewillcalculate8.25%ofthemassofanatomof46Ti,7.44%ofanatomof47Ti,73.72%of
anatomof48Ti,5.41%ofanatomof49Tiand5.18%ofanatomof50Ti.Addingthese
contributionsgivesthetotalmassoftheaverageatom.Therefore:

Isouranswerreasonable?

Byfarthemostabundantisotopeis48Ti,sowewouldexpecttheaverageatomicmasstobe
closetothemassofthisisotope.Ourcalculatedaverageatomicmass,47.867u,isindeedjust
lessthanthemassofthe48Tiisotope(47.9479463u),becausethelighter46Tiand47Ti
isotopesareslightlymoreabundantthantheheavier49Tiand50Tiisotopes.Hence,wecan
feelconfidentouransweriscorrect.

ChemistryResearch

TheOpenPoolAustralianLightWaterReactor

Aswehaveseeninthischapter,someatomicnucleiareradioactiveanddecayspontaneously
togivelighternuclei.Theenergyproducedinsuchradioactivedecayprocessescanbe
harnessedinnuclearreactorstogenerateelectricity.However,theOpenPoolAustralianLight
WaterReactor(OPAL)inSydney,theonlynuclearreactorinAustralasia,producesno
electricityandisusedonlyforscientificapplicationsundertheauspicesoftheAustralian
NuclearScienceandTechnologyOrganisation(ANSTO).Someoftheseapplicationsare
outlinedbelow.

TheOPALreactor,picturedinfigures1.12and1.13,usesuraniumenrichedintheisotope
asitsnuclearfuel,andconsumesabout30kgofuraniumperyear.Whena
nucleusundergoesradioactivedecay,freeneutronsareproduced.Neutronsinteractwith
matterinspecificways,andanalysisoftheresultsoftheseinteractionscanprovideextensive
informationaboutthematterbeingstudied.BeamsofneutronsfromtheOPALreactorare
usedastheradiationsourceinanumberofinstrumentsdesignedtoinvestigateavarietyof
propertiesofmatter.Theseinstrumentsincludediffractometersdesignedtoinvestigatethe
threedimensionalarrangementofatoms(particularlyhydrogenatoms)insolids,measure
stressinmaterials,studythemagneticpropertiesofsubstances,andrecordthemotionsof
atomsinchemicalreactionsonthemillisecondtimescale.
FIGURE1.12TheblueglowduetoCherenkovradiation.Thisradiationisemittedwhencharged
particlessuchashighenergyelectronstravelataspeedfasterthanthespeedof
lightinthemediumthroughwhichtheytravel(inthiscase,water).

FIGURE1.13AviewoftheOPALreactor.Thereactorcoreliesatthebottomofthecircular
 section.

Neutronscanalsobeusedtopreparemacroscopicamountsofspecificisotopes.Aswehave
seeninworkedexample1.2,someradioactiveisotopesareusefulinmedicaldiagnosisand
treatment.However,theseoftendonotoccurnaturallyinusablequantitiesowingtotheir
shortlifetimes.Forexample,the (Tc=technetium,m=metastable)isotope,whichis
usedinover80%ofnuclearmedicineimagingprocedures,mustbepreparedviathedecayof
the (Mo=molybdenum)isotope,whichisitselfradioactiveandhasahalflifeof66
hours.ThelatterispreparedintheOPALreactorbytheirradiationofauraniumtargetwith
neutronsand,followingpurification,isthenshippedtohospitalsthroughoutAustralasia.
OthermedicalisotopesproducedbytheOPALreactorare , , and .

InadditiontotheOPALreactor,ANSTOisalsoequippedwithparticleacceleratorsand
cyclotrons,bothofwhichinvolveelementaryparticlestravellingatveryhighspeeds.The
ANTARES(AustralianNationalTandemAcceleratorforAppliedResearch)particle
acceleratorhasbeenusedtodetermine,amongotherthings,theageofanimportantEuropean
historicalartefact.AcrownmadeofironandgoldatthecathedralinMonza,Italywas
thoughttobethatofCharlemagne(c.742814),thefirstHolyRomanEmperor,buthistorical
documentscouldonlydateittosometimebetweenthelateRomanandtheMiddleAges,a
timespanofseveralhundredyears.Fortunately,thepreciousstonesinthecrownwere
attachedusingamixtureofbeeswaxandclay,andthisallowedtheuseofradiocarbondating,
aprocesswheretheamountoftheradioactiveisotope inthebeeswaxcouldbemeasured.
Analysisoflessthan1mgofthemixtureusingANTARESplacedthedateofthecrown's
manufacturebetweentheyears700and780,atimeperiodthatcoincideswiththelifeof
Charlemagne.

PRACTICEEXERCISE1.3
Aluminiumatomshaveamassthatis2.248
45timesthatofanatomof12C.Whatisthe
atomicmassofaluminium?

PRACTICEEXERCISE1.4
Naturallyoccurringcopperiscomposedof
69.15%63Cuand30.85%65Cu.Atomsof
63Cuhaveamassof62.9296uandthoseof
65Cuhaveamassof64.9278u.Calculate
theaverageatomicmassofcopper.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.4ThePeriodicTableoftheElements
WehavealreadyseenthattheelementsH,HeandLicanbeorderedonthebasisofincreasingatomic
number(Z=1,2and3,respectively).Ifwecontinuesuchanordering,weobtaintheperiodictableofthe
elements.TheperiodictableweusetodayisbasedprimarilyontheeffortsofaRussianchemist,Dmitri
IvanovichMendeleev(18341907,picturedinfigure1.14),andaGermanphysicist,JuliusLotharMeyer
(18301895).Workingindependently,thesescientistsdevelopedsimilarperiodictablesonlyafewmonths
apartin1869.Mendeleevisusuallygiventhecredit,however,becausehepublishedhisversionfirst.

FIGURE1.14DmitriIvanovichMendeleevdevelopedtheperiodictable./SPL/RussellKightley

TheextraordinarythingabouttheworkofMendeleevandMeyerwasthattheyknewnothingofthe
structureoftheatom,sowereunawareoftheconceptofatomicnumber,whichisthebasisofthemodern
periodictable.Whattheydidknow,however,weretheatomicmassesofmanyoftheelements.Bearin
mindalsothatnotalloftheelementshadbeendiscoveredatthistime.Mendeleevwaspreparingachemistry
textbookforhisstudentsattheUniversityofStPetersburgand,lookingforsomepatternamongthe
propertiesoftheelements,hefoundthat,whenhearrangedtheminorderofincreasingatomicmass,similar
chemicalpropertieswererepeatedoverandoveratregularintervals.Forinstance,theelementslithium,Li,
sodium,Na,potassium,K,rubidium,Rb,andcaesium,Cs,aresoftmetalsthatreactvigorouslywithwater.
Similarly,theelementsthatimmediatelyfolloweachofthesealsoconstituteasetwithsimilarchemical
properties.Thus,beryllium,Be,followslithiummagnesium,Mg,followssodiumcalcium,Ca,follows
potassiumstrontium,Sr,followsrubidiumandbarium,Ba,followscaesium.Alloftheseelementsform
compoundswithoxygenhavinga1:1metaltooxygenratio.Mendeleevusedsuchobservationsto
constructhisperiodictable,whichisillustratedinfigure1.15.
 FIGURE1.15Mendeleev'soriginalperiodictable,takenfromtheGermanchemistryjournalZeitschriftfrChemie,
1869,12,4056.

Atfirstglance,Mendeleev'soriginaltablelookslittlelikethemoderntablegiveninfigure1.16.However,
acloserlookrevealsthattherowsandcolumnshavebeeninterchanged.TheelementsinMendeleev'stable
arearrangedinorderofincreasingatomicmass.Whenthesequenceisbrokenattherightplacesand
stacked,theelementsfallnaturallyintocolumns.
 FIGURE1.16Theperiodictableoftheelements.Atthetimeofwriting,118elementswereknown.

Mendeleevplacedelementswithsimilarpropertiesinthesamerowevenwhenthisleftoccasionalgapsin
thetable.Forexample,heplacedarsenic,As,inthesamerowasphosphorusbecausetheyhadsimilar
chemicalproperties,eventhoughthisleftgapsinotherrows.Inastrokeofgenius,Mendeleevreasoned,
correctly,thattheelementsthatbelongedinthesegapshadsimplynotyetbeendiscovered.Infact,onthe
basisofthelocationofthesegaps,Mendeleevcouldpredict,withastonishingaccuracy,thepropertiesofthe
yettobefoundelements,andhispredictionshelpedserveasaguideinthesearchforthem.

Theelementstellurium,Te,andiodine,I(notethattheGermanforiodineisjod,whichhasthe
abbreviationJinMendeleev'soriginaltable),causedMendeleevsomeproblems.Accordingtothebest
estimatesatthattime,theatomicmassoftelluriumwasgreaterthanthatofiodine.Yet,iftheseelements
wereplacedinthetableaccordingtotheiratomicmasses,theywouldnotfallintotheproperrowsrequired
bytheirproperties.Therefore,Mendeleevswitchedtheirorder,believingthattheatomicmassoftellurium
hadbeenincorrectlymeasured(ithadnot),andinsodoingviolatedhisorderingsequencebasedonatomic
mass.

ThetablethatMendeleevdevelopedisthebasisoftheoneweusetoday,butoneofthemaindifferencesis
thatMendeleev'stablelackstheelementshelium,He,neon,Ne,argon,Ar,krypton,Kr,xenon,Xe,and
radon,Rn.InMendeleev'stime,noneoftheseelementshadyetbeendiscoveredbecausetheyarerelatively
rareandbecausetheyhavevirtuallynotendencytoundergochemicalreactions.Whentheseelementswere
finallydiscovered,beginningin1894,anotherproblemarose.Twomoreelements,argon,Ar,and
potassium,K,didnotfallintotherowsrequiredbytheirpropertiesiftheywereplacedinthetableinthe
orderrequiredbytheiratomicmasses.Anotherswitchwasnecessaryandanotherexceptionhadbeenfound.
Itbecameapparentthatatomicmasswasnotthetruebasisfortheperiodicrepetitionofthepropertiesofthe
elements.WithRutherford'sdiscoveryofthestructureoftheatom,itbecameapparentthattheelementsin
theperiodictablewerearrangedinorderofincreasingatomicnumber,notatomicmass,andwhenthiswas
realiseditbecameobviousthatTeandI,andArandK,wereinfactinthecorrectpositions.

TheModernPeriodicTable
Theperiodictableinusetodayisshowninfigure1.16,andalsoontheinsidefrontcoverofthisbook.The
horizontalrowsarecalledperiodsandarenumbered1to7,whiletheverticalcolumnsarecalledgroups
andarenumbered1to18.Theelementsarearrangedinorderofincreasingatomicnumberacrosseach
period,andanewperiodbeginsaftereachgroup18element.Theatomicmassesaregiven(generallyto
foursignificantfigures)beloweachchemicalsymbol.Whiletheatomicmassusuallyincreaseswithatomic
number,youcanseetheexceptionswementionedpreviously(TeandI,andArandK)aswellasCoand
Ni.Whiletheisotopiccompositionand,therefore,theatomicmassesofmostelementsarewellestablished,
therearesomeunstableelementsthatundergospontaneousradioactivedecay(seechapter27).Giventhat
theisotopiccompositionofsuchelementscannotbeknown,itisusualtosimplyquotethemassnumberof
thelongestlivedisotopeoftheelement,andthesearegiveninparenthesesintheperiodictable.Notethat
therearediscontinuitiesintheperiodictablebetweenelements56and72,andbetweenelements88and
104,andthesetwosetsofelementsaregivenbelowthetableitself.Theelementsfrom57to71arecalled
thelanthanoids(or,lesscommonly,therareearthelements).Elements89to103arecalledtheactinoids.
Thelanthanoidsandactinoidsaregenerallysituatedbelowtherestoftheperiodictable,simplytosave
spaceandtomakethetableeasiertoreadnotethatthelanthanoidandactinoidelementsarechemically
distinctfromtherestoftheelementsintheperiodictable,anddonotbelongtoanyofthegroups1to18.
Thelanthanoidsandactinoidsaresometimescalledthefblockelements,andasimilarterminologyisalso
usedelsewhereinthetableelementsingroups1and2arecalledthesblockelements,elementsingroups
3to12arecalledthedblockelements,andelementsingroups13to18arecalledthepblockelements.As
wewillsee,s,p,dandfrefertoorbitals,particularregionsinspaceintheatomwhereelectronshaveahigh
probabilityofbeingfound.Thedblockelementsarealsocalledtransitionmetals.

Individualgroupswithintheperiodictablearealsoknownbyparticularnames,althoughthispracticeisless
prevalentthaninthepast.Group1elementsarecalledalkalimetals,group2elementsarecalledalkaline
earthmetals,group15elementsarecalledpnictogens,group16elementsarecalledchalcogens,group17
elementsarecalledhalogensandgroup18elementsarecallednoblegases.Ofthese,onlytheterms
halogensandnoblegasesareincommonusage.

Allelementsontheperiodictablebelongtooneofthreecategoriesmetals,nonmetalsandmetalloids
andthegroupingsareshownbythedifferentshadingsontheperiodictableinfigure1.16.Metalsare
generallygoodconductorsofheatandelectricity,aremalleable(canbebeatenintoathinsheet)andductile
(canbedrawnoutintoawire),andhavetheusualmetalliclustre.Elementsthatdonothavethese
characteristicsarecallednonmetals,andthemajorityofthesearegasesatroomtemperatureandpressure.
Thepropertiesofmetalloidsliesomewherebetweenthemetalsandnonmetals.Themostnotablepropertyof
theseelementsisthefactthattheytendtobesemiconductors,andmetalloidssuchassilicon,Si,and
germanium,Ge,havethereforefoundwideuseinsiliconchipsandtransistors.Notethattheclassificationof
therecentlypreparedelements116,117and118issomewhatarbitrary,asweighablequantitiesofthese
havenotyetbeenobtained.

NamingtheElements
Alloftheelementsintheperiodictablehaveone,twoorthreeletterabbreviationsoftheirnames.The
abbreviationsofmanyelementsaresimplythefirstoneortwolettersoftheirnames(e.g.carbon,C,oxygen,
O,lithium,Li)buttherearequiteanumberofelementsforwhichthederivationoftheabbreviationisnot
quitesoobvious:forexample,potassium,K,tin,Sn,lead,Pb,andiron,Fe.Suchapparentanomaliesoccur
becauseofthewaythattheelementswereoriginallynamed.Whenanewelementisdiscovered,the
discovererusuallygetstosuggestanamefortheelement,whichisthenratifiedbyIUPAC,theInternational
UnionofPureandAppliedChemistry.

Ofalltheelementsontheperiodictable,C,S,Fe,Cu,As,Ag,Sn,Sb,Au,Hg,PbandBiwereknownto
ancientcivilisationssothedateoftheirdiscoveryisnotknown.Ofthese,Fe,Cu,Ag,Sn,Sb,Au,Hgand
PbareabbreviationsfortheLatinnamesferrum,cuprum,argentum,stannum,stibium,aurum,hydrargyrum
andplumbum.Theearliestknowndiscoveryofanelementwasthatofphosphorus,P.Itwasisolatedin1669
byHennigBrandfromthedistillationofurine(hewasapparentlytryingtomakesilverorgold
unsuccessfully,ofcourse!)andwasnamedaftertheGreekwordphosphoros,meaningbringeroflight,as
theelementglowsinthedark.Elementshavebeennamedaftercountries(germanium,francium,americium,
polonium)andevenaftertheplacestheywerefirstdiscoveredtheSwedishtownofYtterbyhasthe
distinctionofhavingfourelements(erbium,Er,ytterbium,Yb,yttrium,Y,andterbium,Tb)namedafterit,
asthesewerefirstfoundindepositsclosetothetown.Surprisinglyfewelementshavebeennamedafter
peopleatpresent,only15peoplehavebeenimmortalisedontheperiodictable,andtheyarelistedintable
1.4.Itisinterestingtonotethatnoneofthepeoplelisteddiscoveredtheelementnamedafterthem.
TABLE1.4 Peopleafterwhomelementshavebeennamed
Element
Name Briefbiography named
VasiliiYefrafovich ChiefofstaffoftheRussianCorpsofMiningEngineers samarium,Sm
vonSamarski (element62)
Bykhovets(1803
1870)
JohanGadolin(1760 Finnishchemistfirstpersontoisolatealanthanoid gadolinium,
1852) element Gd(element
64)
Pierre(18591906) HusbandandwifescientificteamPierreFrenchandMarie curium,Cm
andMarie(1867 PolishbybirthjointlywontheNobelPrizeinphysicsin (element96)
1934)Curie 1903
AlbertEinstein(1879 Mostfamousscientistofthetwentiethcentury,ifnotall einsteinium,
1955) timeGermanbybirthwontheNobelPrizeinphysicsin Es(element
1921 99)
EnricoFermi(1901 Italianphysicistmadegreatadvancesinthestudyof fermium,Fm
1954) nuclearreactionswontheNobelPrizeinphysicsin1938 (element100)
DmitriMendeleev Russianchemistrenownedforthedevelopmentofthe mendelevium,
(18341907) periodictable Md(element
101)
AlfredNobel(1833 SwedishinventorofdynamiteandpatronoftheNobel nobelium,No
1896) Prizes (element102)
ErnestLawrence AmericaninventorofthecyclotronwontheNobelPrize lawrencium,
(19011958) inphysicsin1939 Lr(element
103)
ErnestRutherford NewZealandphysicist/chemistmadeseminal rutherfordium,
(18711937) contributionstounderstandingthestructureoftheatom Rf(element
wontheNobelPrizeinchemistryin1908 104)
GlennSeaborg(1912 Americanchemistfirstpreparedmanyoftheelements seaborgium,
1999) beyonduraniumintheperiodictablewontheNobelPrize Sg(element
inchemistryin1951 106)
NielsBohr(1885 Danishphysiciststudiedelectronicenergylevelswithin bohrium,Bh
1962) atoms,whichaidedourunderstandingoftheatomwon (element107)
theNobelPrizeinphysicsin1922
LiseMeitner(1878 Austrianphysicistmadefundamentaldiscoveries meitnerium,
1968) concerningnuclearfissioncontroversiallyneverawarded Mt(element
aNobelPrize 109)
WilhelmRntgen GermanphysicistdiscovererofXrayswinnerofthe rntgenium,
(18451923) inauguralNobelPrizeinphysicsin1901 Rg(element
111)
NicolausCopernicus PolishastronomerproposedthattheSun,ratherthanthe copernicium,
(14731543) Earth,wasthecentreofthesolarsystem Cn(element
 112)

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1.5ElectronsinAtoms
Whilewehavetouchedbrieflyontheconceptofelectrons,wehavetothispointconcentratedprimarily
onthenucleusoftheatomandthewayinwhichthenumberofprotonsinthenucleusdeterminesthe
chemicalidentityoftheatom.However,manyofthechemicalpropertiesofanatomand,most
importantly,itschemicalreactivityaredeterminednotbythenucleusbutbytheelectrons.

Oneofthemostinterestingthingsaboutelectronsisthatwecannotreallysayexactlywheretheyareat
anyparticulartime,soweusuallytalkabouttheirmostprobablelocations.Electronsoccupyregionsof
spacecalledorbitalsinatoms.Eachorbitalhasacharacteristicelectrondistributionandenergy.For
example,thelowestenergysituationforahydrogenatom,thegroundstate,occurswhenthesingle
electronoccupiesanorbitalinwhichitsmostprobabledistancefromthenucleusis5.291011m.
Thisorbitalhasasphericalelectrondistribution.Ifthegroundstatehydrogenatomabsorbsaspecific
amountofenergy,theelectroncanbepromotedtoahigherenergyorbitaltoformanexcitedstatein
whichtheelectronlies,onaverage,furtherfromthenucleus.Suchaprocessiscalledanelectronic
transition,andtheelectrondistributioninthehigherenergyorbitalisdumbbellshaped.Similarly,the
electroninanexcitedstatehydrogenatomcanmovetoalowerenergyorbitalthroughtheemissionof
energy,oftenintheformoflight.Indeed,aswewillseeinchapter4,suchprocessesarethebasis
behindbothneonandsodiumvapourlights.Orbitalshavedefiniteenergies,sotheenergyofany
electronisdictatedbytheenergyoftheorbitalitoccupiestherefore,anelectroninanatomcanhave
onlycertainwelldefinedenergies.Thisisafundamentalprincipleofthescienceofquantummechanics
calledquantisation,aphenomenonfirstproposedbytheGermanphysicistMaxPlanck(18581947,
NobelPrizeinphysics,1918)in1900.Wewilllearnmoreaboutthequantisationofenergyinchapter4.

Electronshaveasinglenegativecharge,andtheoverallchargeonanychemicalspeciesisdetermined
bythenumberofelectronsrelativetothenumberofprotonsforexample,theperoxideion,O22,hasa
2chargebecausetherearetwomoreelectronsthanprotonsintheion.Similarly,theLi+ioncontains
threeprotonsandtwoelectrons,soithasasinglepositivecharge.Inadditiontotheirnegativecharge,
allelectronshaveanintrinsicpropertycalledspin.Thiscanhaveoneoftwovalues,whichare
commonlycalledspinupandspindownandareoftendepictedasfollows:

Eachorbitalwithinanatomcancontainamaximumoftwoelectrons,oneofwhichmustbespinupand
theotherspindown.

Chemistsareinterestedinelectronsbecausetheyconstitutethechemicalbondsthatholdatomstogether
inmolecules.Covalentchemicalbondsusuallyconsistofone,twoorthreepairsofelectronsshared
betweenatoms,eachpaircontainingelectronsofoppositespin.Foramoleculetoundergoachemical
reaction,thesebondsmustusuallybebrokenandnewonesmadethisrequiresareorganisationofthe
electronpairsbetweenthereactantandproductmolecules,andtheeasewithwhichthiscanbedone
determineshowfastthereactionoccurs.Reactionsinwhichoneormoreelectronsaretransferred
betweenchemicalspeciesarealsoknownsuchreactions,knownasredoxreactions,areimportantina
hugenumberofchemicalandbiochemicalprocessesinfact,asyouarereadingthis,ironionsand
oxygenmoleculesarebusyexchangingelectronsinyourbloodtotransportoxygenaroundyourbody.

Becauseoftheirimportanceinbothchemicalstructureandchemicalreactivity,electronsoccupya
centralplaceinchemistry.Intheremainingchaptersofthisbook,wewilllearnmoreofthepropertiesof
atomsandmoleculesthatarepredominantlydictatedbyelectrons.

WehavelearnedmuchabouttheatomintheyearssinceRutherford'sseminalexperiment.Indeed,we
havedetailedonlytheverybasicsofatomicstructureintheprecedingpageslaterchapterswilloutline
someoftheamazingcomplexityoftheatom.Forthemoment,itissufficientforyoutoappreciatethat
theatomiscomposedofapositivelychargedcentralnucleuscontainingprotonsandneutrons,whichis
surroundedbynegativelychargedelectronsthatcanundergotransitionsonlybetweenwelldefined
energylevels.Andwithonly118differenttypesofthesebuildingblocks,wecanconstructthe
universe.

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 SUMMARY
Atoms,Molecules,Ions,ElementsandCompounds
Atomsareafundamentalbuildingblockofallmatter.Unchargedcollectionsofatomsbondedtogether
inadefinitestructurearecalledmolecules.Theseareheldtogetherbycovalentbondsthatshare
electronsbetweenadjacentatoms.Ionsarechargedchemicalspeciesthatmaybederivedfromboth
atomsandmolecules.Cationsarepositivelycharged,whileanionsarenegativelycharged.Elements
compriseonlyasingletypeofatom,whilecompoundsaremadeupoftwoormorechemicalelements.
Allofthesedifferentchemicalentitiescanbeinvolvedasreactantsinchemicalreactions,inwhichthey
aretransformedtoproducts.

TheAtomicTheory
Allmatteriscomposedofatoms.Theexistenceofatomswasproposedonthebasisof:
thelawofconservationofmass.Massisconservedinchemicalreactions.
thelawofdefiniteproportions.Elementsarecombinedinthesameproportionsbymassinany
particularcompound.
thelawofmultipleproportions.Whentwoelementsformmorethanonecompound,thedifferent
massesofoneelementthatcombinewiththesamemassoftheotherelementareintheratioof
smallwholenumbers.

Dalton'satomictheorywasthefirsttoproposetheexistenceofatomsonthebasisofscientific
observations.Thebasictenetsofhistheoryare:
1.Matterconsistsoftinyparticlescalledatoms.
2.Atomsareindestructible.Inchemicalreactions,theatomsrearrangebuttheydonotthemselves
breakapart.
3.Inanysampleofapureelement,alltheatomsareidenticalinmassandotherproperties.
4.Theatomsofdifferentelementsdifferinmassandotherproperties.
5.Whenatomsofdifferentelementscombinetoformagivencompound,theconstituentatomsin
thecompoundarealwayspresentinthesamefixednumericalratio.

Dalton'stheoryallowsustousechemicalequations,inwhichreactantsandproductsareseparatedbyan
arrow,todescribechemicalreactions.Suchequationsarebalancedwhentheycontainthesamenumber
ofeachtypeofatomoneachsideofthearrow.

Modernapparatusenablesustoseeindividualatoms,andatomictheoryisnowatomicfact.

TheStructureoftheAtom
AlthoughDaltonproposedtheatomtobeindivisible,experimentsinthelatenineteenthcenturyshowed
thiswasnotthecase.Thenegativelychargedelectronwasthefirstsubatomicparticletobediscovered,
whileRutherford'sgoldfoilexperiment,inwhichathingoldsheetwasbombardedwithalphaparticles,
gaveevidenceforasmall,positivelychargednucleus.Thepositivechargeisduetosubatomicparticles
calledprotons,andthenumberoftheseinthenucleusdeterminestheidentityoftheatominquestion.
Thethirdcomponentoftheatom,theneutron,waspredictedbyRutherfordandfoundbyChadwick.
Theatomthuscomprisesthreesubatomicparticles,theelectron,protonandneutron,thelattertwo
collectivelybeingcallednucleons.Eachtypeofatomisdesignatedbyachemicalsymbol,whichis
determinedbyitsatomicnumber(Z),thenumberofprotonsinthenucleus.Themassnumber(A)is
equaltothenumberofprotonsplusthenumberofneutronsinthenucleus.Theterminologyusedto
depictanatomofanyelementXis .AllatomswiththesameZareofthesameelementhowever,
atomsofthesameelementcandifferinthenumberofneutronsinthenucleus,andthisgivesriseto
isotopes.Isotopescanbeeitherradioactive(i.e.theydecayspontaneously)orstable.Aradioactive
nucleusiscalledaradionuclide,whileanuclideisthenamegiventoanyatomicnucleus.Wecan
measureatomicmassinatomicmassunits(u),where1u=1.6605410 27kg,andisequalto of
themassofoneatomof12C.Theatomicmassofanysampleofatomsistheweightedaverageofthe
massesoftheisotopespresentinthesample.

ThePeriodicTableoftheElements
Theperiodictableoftheelementscontainsthe118knownelementsarrangedinorderofincreasing
atomicnumber,andwasdevelopedbybothMendeleevandMeyer.Thehorizontalrowsarecalled
periodsandtheverticalcolumnsgroups.Elementsinthesamegrouptendtohavesimilarchemical
properties.Theperiodictableisdividedintosectionsaccordingtotheelectronconfigurationofthe
elements,namelythesblockelements,thepblockelements,thedblockelementsandthefblock
elements.Thefblockelementsaredividedintothelanthanoids(alsosometimescalledtherareearth
elements)andtheactinoids,whilethedblockelementsarealsocalledthetransitionmetals.The
elementsincertaingroupsintheperiodictablehavespecialnames:group1elementsarecalledalkali
metals,group2elementsarecalledalkalineearthmetals,group15elementsarecalledpnictogens,
group16elementsarecalledchalcogens,group17elementsarecalledhalogensandgroup18elements
arecallednoblegases.Theelementsoftheperiodictablecanbeclassifiedasmetals,nonmetals,or
metalloids.

ElectronsinAtoms
Electronsoccupyregionsofspacecalledorbitals.Thelowestenergyarrangementofelectronsinthe
orbitalsofanatomiscalledthegroundstate.Electronscanbepromotedtohigherenergyorbitalsby
absorptionofenergytogiveexcitedstatesconversely,electronsinhigherenergyorbitalscanmoveto
lowerenergyorbitalswiththeemissionofenergy,oftenaslight.Suchprocessesarecalledelectronic
transitions.Theenergiesofelectronsinatomsaredeterminedbytheenergiesoftheorbitalswithinthe
atom,soelectronsinatomscanhaveonlycertainwelldefinedenergies.Thisiscalledquantisation,a
fundamentalprincipleofquantummechanics.Electronshaveasinglenegativecharge,andoneoftwo
possiblespins.Anorbitalinanatomcanholdamaximumoftwoelectrons,whichmustbeofopposite
spin.Covalentbondscompriseone,twoorthreepairsofelectrons.Chemicalreactionsofteninvolve
reorganisingtheseelectronsinbondmakingandbondbreakingprocesses.Redoxreactionsinvolvethe
transferofoneormoreelectronsbetweenchemicalspecies.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Thelawofconservationofmass(section1.2)
Thetotalmassofreactantspresentbeforeareactionstartsequalsthetotalmassofproductsafterthe
reactionisfinished.Wecanusethislawtocheckwhetherwehaveaccountedforallthesubstances
formedinareaction.

Thelawofdefiniteproportions(section1.2)
Ifweknowthemassratiooftheelementsinonesampleofacompound,theratiowillbethesameina
differentsampleofthesamecompound.

Thelawofmultipleproportions(section1.2)
Indifferentcompoundscontainingthesametwoelements,thedifferentmassesofoneelementthat
combinewiththesamemassoftheotherelementareinaratioofsmallwholenumbers.

Atomicmass(section1.3)
Thisisusedtodeterminethemassofanyatomrelativetothatofthe12Cisotope.

Periodictableoftheelements(section1.4)
Thisisatableofthechemicalelementsarrangedinorderofincreasingatomicnumber.Wecanusethe
periodictabletofigureoutwhetheraparticularelementisametal,nonmetalormetalloid,predictits
chemicalreactivity,calculateitsnumberofprotonsandelectrons,obtainitsatomicmassandsoon.In
fact,allofchemistryiscontainedwithintheperiodictable.

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 REVIEWQUESTIONS
Atoms,Molecules,Ions,ElementsandCompounds
1.1Definethefollowingterms:atom,covalentbond,ion,cation,anion,element,compound,reactant,
chemicalreaction,product.
TheAtomicTheory
1.2Nameandstatethethreelawsofchemicalcombinationdiscussedinthischapter.
1.3WhichpostulateofDalton'satomictheoryisbasedonthelawofconservationofmass?Whichis
basedonthelawofdefiniteproportions?
1.4Whichofthelawsofchemicalcombinationisusedtodefinethetermcompound?
1.5Inyourownwords,describehowDalton'satomictheoryexplainsthelawofconservationofmass
andthelawofdefiniteproportions.
TheStructureoftheAtom
1.6Writethesymbolfortheisotopethatformsthebasisoftheatomicmassscale.Whatisthemassof
thisatomexpressedinatomicmassunits?
1.7Whatarethenames,symbols,electricchargesandmasses(expressedinu)ofthethreechemically
importantsubatomicparticlesintroducedinthischapter?
1.8Whereinanatomisnearlyallofitsmassconcentrated?Explainyouranswerintermsofthe
particlesthatcontributetothismass.
1.9Whatisanucleon?Whichoneshavewestudiedinthischapter?
1.10Definethetermsatomicnumberandmassnumber.
1.11Intermsofthestructuresofatoms,howareisotopesofthesameelementalike?Howdothey
differ?
1.12Considerthesymbol ,whereXstandsforthechemicalsymbolforanelement.What
informationisgivenby(a)Aand(b)Z?
1.13Writethesymbolsoftheisotopesthatcontainthefollowing.(Usethetableofatomicnumbers
printedinsidethefrontcover,asneeded.)
(a)anisotopeofiodinehavingatomswith78neutrons
(b)anisotopeofstrontiumhavingatomswith52neutrons
(c)anisotopeofcaesiumhavingatomswith82neutrons
(d)anisotopeoffluorinehavingatomswith9neutrons
ThePeriodicTableoftheElements
1.14Whatisthechemicalsymbolforeachofthefollowingelements?
(a)chlorine,
(b)sulfur,
(c)iron,
(d)silver,
(e)sodium,
(f) phosphorus,
(g)iodine,
(h)copper,
(i) mercury,
 (j) calcium
1.15Whatisthenameofeachofthefollowingelements?
(a)K,
(b)Zn,
(c)Si,
(d)Sn,
(e)Mn,
(f) Mg,
(g)Ni,(h)Al,
(h)C,
(i) N
1.16OnwhatbasisdidMendeleevconstructhisperiodictable?Onwhatbasisaretheelements
arrangedinthemodernperiodictable?
1.17Intheperiodictable,whatisaperiod?Whatisagroup?
1.18WhydidMendeleevleavegapsinhisperiodictable?
1.19Whichisbetterrelatedtothechemistryofanelement:itsmassnumberoritsatomicnumber?Give
abriefexplanationintermsofthebasisfortheperiodictable.
1.20Onthebasisoftheirpositionsintheperiodictable,whyisitnotsurprisingthat90Sr,adangerous
radioactiveisotopeofstrontium,replacescalciuminnewlyformedbones?
1.21Intherefiningofcopper,sizableamountsofsilverandgoldarerecovered.Whyisthisnot
surprising?
1.22Whywouldyoureasonablyexpectcadmiumtobeacontaminantinzincbutnotinsilver?
1.23Basedondiscussionsinthischapter,explainwhyitisunlikelythatscientistswilldiscoveranew
element,neverbeforeobserved,havinganatomicmassofapproximately73.
1.24Ineachofthefollowingsetsofelements,statewhichfitsthedescriptioninparentheses.
(a)Ce,Hg,Si,O,I(halogen)
(b)Pb,W,Ca,Cs,P(transitionmetal)
(c)Xe,Se,H,Sr,Zr(noblegas)
(d)Th,Sm,Ba,F,Sb(lanthanoidelement)
(e)Ho,Mn,Pu,At,Na(actinoidelement)
1.25Whichpropertyofmetalsallowsthemtobedrawnintowire?
1.26Goldcanbehammeredintosheetssothinthatsomelightcanpassthroughthem.Whichproperty
ofgoldallowssuchthinsheetstobemade?
1.27Whichnonmetalsoccurasmonatomicgases(gasesthatexistassingleatoms)?
1.28Whichtwoelementsexistasliquidsatroomtemperatureandpressure?
1.29Whichphysicalpropertyofmetalloidsdistinguishesthemfrommetalsandnonmetals?
1.30Sketchtheshapeoftheperiodictableandmarkoffthoseareaswherewefind
(a)metals,
(b)nonmetalsand
(c)metalloids.
ElectronsinAtoms
1.31Whatisanorbital?
1.32Whenelectronsofoppositespinsoccupyanorbital,wesaythattheirspinsarepaired.Molecules
withoddnumbersofelectrons,therefore,cannothavealloftheelectronspinspaired,andwesay
thattheyhaveunpairedspins.Whichofthefollowingmoleculesmusthaveunpairedspins:N2,F2,
CO,NO,NO2?
1.33Whatisthedifferencebetweenanatominitsgroundstateandanatominitsexcitedstate,given
thatthenumbersofprotons,neutronsandelectronsinbothsituationsarethesame?
1.34Quantisationisveryimportantontheatomicscalebut,inthelargescaleofoureverydaylives,we
barelynoticeit.Whydoyouthinkthismightbeso?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
1.35Laughinggasisacompoundformedfromnitrogenandoxygeninwhichthereis1.75gof
nitrogenforevery1.00gofoxygen.Thecompositionsofseveralnitrogenoxygencompounds
follow.Whichoftheseislaughinggas?
(a)6.35gnitrogen,7.26goxygen
(b)4.63gnitrogen,10.58goxygen
(c)8.84gnitrogen,5.05goxygen
(d)9.62gnitrogen,16.5goxygen
(e)14.3gnitrogen,40.9goxygen
1.36Oneofthesubstancesusedtomelticeonfootpathsandroadsincoldclimatesiscalciumchloride.
Inthiscompound,calciumandchlorinearecombinedinaratioof1.00gofcalciumto1.77gof
chlorine.Whichofthefollowingcalciumchlorinemixtureswillproducecalciumchloridewithno
calciumorchlorineleftoverafterthereactioniscomplete?
(a)3.65gcalcium,4.13gchlorine
(b)0.856gcalcium,1.56gchlorine
(c)2.45gcalcium,4.57gchlorine
(d)1.35gcalcium,2.39gchlorine
(e)5.64gcalcium,9.12gchlorine
1.37Ammoniaiscomposedofhydrogenandnitrogeninaratioof9.33gofnitrogento2.00gof
hydrogen.Ifasampleofammoniacontains6.28gofhydrogen,whatmassofnitrogendoesit
contain?
1.38Acompoundofphosphorusandchlorineusedinthemanufactureofaflameretardanttreatment
forfabricscontains1.20gofphosphorusforevery4.12gofchlorine.Supposeasampleofthis
compoundcontains6.22gofchlorine.Whatmassofphosphorusdoesitcontain?
1.39Refertothedataaboutammoniainquestion1.37.If4.56gofnitrogencombinedcompletelywith
hydrogentoformammonia,whatmassofammoniawouldbeformed?
1.40Refertothedataaboutthephosphoruschlorinecompoundinquestion1.38.If12.5gof
phosphoruscombinedcompletelywithchlorinetoformthiscompound,whatmassofthe
compoundwouldbeformed?
1.41MoleculesofacertaincompoundofnitrogenandoxygencontainoneatomeachofNandO.In
thiscompound,thereis1.143gofoxygenforeach1.000gofnitrogen.Moleculesofadifferent
compoundofnitrogenandoxygencontainoneatomofNandtwoatomsofO.Whatmassof
oxygenwouldbecombinedwitheach1.000gofnitrogeninthesecondcompound?
1.42Tinformstwocompoundswithchlorine.Inoneofthem(compound1),therearetwoClatomsfor
eachSnatomintheother(compound2),therearefourClatomsforeachSnatom.When
combinedwiththesamemassoftin,whatwouldbetheratioofthemassesofchlorineinthetwo
compounds?Incompound1,0.597gofchlorineiscombinedwitheach1.000goftin.Whatmass
ofchlorinewouldbecombinedwith1.000goftinincompound2?
1.43Themasscorrespondingto1atomicmassunitis1.6605410 24g.Usethisvaluetocalculate
themassingramsof1atomof12C.
1.44Usethemasscorrespondingtotheatomicmassunitgiveninquestion1.43tocalculatethemass
of1atomofsodium.
1.45Thechemicalsubstanceinnaturalgasisacompoundcalledmethane.Itsmoleculesarecomposed
ofcarbonandhydrogenandeachmoleculecontainsfouratomsofhydrogenandoneatomof
carbon.Inthiscompound,0.33597gofhydrogeniscombinedwith1.0000gof12C.Usethis
 informationtocalculatetheatomicmassoftheelementhydrogen.
1.46ElementXformsacompoundwithoxygeninwhichtherearetwoatomsofXforeverythree
atomsofO.Inthiscompound,1.125gofXiscombinedwith1.000gofoxygen.Usetheaverage
atomicmassofoxygentocalculatetheaverageatomicmassofX.Useyourcalculatedatomic
masstoidentifyelementX.
1.47Ifanatomof12Chadbeenassignedarelativemassof24.0000u,determinetheaverageatomic
massofhydrogenrelativetothismass.
1.48Anatomof109Aghasamassthatis9.0754timesthatofa12Catom.Whatistheatomicmassof
thisisotopeofsilverexpressedinatomicmassunits?
1.49Naturallyoccurringmagnesiumiscomposedof78.99%of24Mg(withanatomicmassof23.9850
u),10.00%of25Mg(withanatomicmassof24.9858u)and11.01%of26Mg(withanatomic
massof25.9826u).Usethisinformationtocalculatetheaverageatomicmassofmagnesium.
1.50Givethenumbersofneutrons,protonsandelectronsintheatomsofeachofthefollowing
isotopes.(Usetheperiodictableprintedinsidethefrontcover,asneeded.)
(a) 226Ra
(b)14C
(c)
(d)
1.51Givethenumbersofelectrons,protonsandneutronsintheatomsofeachofthefollowing
isotopes.(Consulttheperiodictableprintedinsidethefrontcoverasnecessary.)
(a) 137Cs
(b)131I
(c)
(d)
1.52FromtheelementsNe,Cs,Sr,Br,Co,Pu,InandO,chooseonethatfitseachofthefollowing
descriptions.
(a)agroup2metal
(b)anelementwithpropertiessimilartothoseofaluminium
(c)atransitionmetal
(d)anoblegas
(e)anactinoid
1.53Writethenamesandchemicalsymbolsforthreeexamplesofeachofthefollowing:
(a)halogens,
(b)alkalimetals,
(c)actinoidsand
(d)noblegases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
1.54Anatomofanelementhas25protonsinitsnucleus.
(a)Istheelementametal,anonmetalorametalloid?
(b)Onthebasisoftheaverageatomicmass,writethesymbolfortheelement'smostabundant
isotope.
(c)Howmanyneutronsareintheisotopeyoudescribedin(b)?
(d)Howmanyelectronsareinanatomofthiselement?
(e) Howmanytimesheavierthan12Cistheaverageatomofthiselement?
1.55ElementsXandYformacompoundinwhichthereisoneatomofXforeveryfouratomsofY.
Whentheseelementsreact,itisfoundthat1.00gofXcombineswith5.07gofY.When1.00gof
Xcombineswith1.14gofO,itformsacompoundcontainingtwoatomsofOforeachatomofX.
CalculatetheatomicmassofY.
1.56Anironnailiscomposedoffourisotopeswiththepercentageabundancesandatomicmasses
giveninthefollowingtable.Calculatetheaverageatomicmassofiron.

Isotope Percentageabundance Atomicmass(u)

54Fe 5.80 53.9396
56Fe 91.72 55.9349
57Fe 2.20 56.9354
58Fe 0.28 57.9333

1.57Rustcontainsanironoxygencompoundinwhichtherearethreeoxygenatomsforeachtwoiron
atoms.Inthiscompound,theirontooxygenmassratiois2.325:1.000.Anothercompoundof
ironandoxygencontainstheseelementsintheratioof2.616:1.000.Whatistheratioofironto
oxygenatomsinthesecondironoxygencompound?
1.58Oneatomicmassunitcorrespondstoamassof1.6605410 24g.Calculatethemass,ingrams,
ofoneatomofmagnesium.Whatisthemassofoneatomofiron,expressedingrams?Usethese
twoanswerstodeterminehowmanyatomsofMgarein24.305gofmagnesiumandhowmany
atomsofFearein55.847gofiron.Compareyouranswers.Whatconclusionscanyoudrawfrom
theresultsofthesecalculations?Withoutactuallyperforminganycalculations,howmanyatoms
doyouthinkwouldbein40.078gofcalcium?
1.59Thediameterofatypicalatomis10 10m,andthediameterofatypicalnucleusis10 15m.
Calculatethetypicalatomicandnuclearvolumesanddeterminewhatfractionofthevolumeofa
typicalatomisoccupiedbyitsnucleus.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
actinoids element nucleon
alkalimetals excitedstate nucleus
alkalineearthmetals fblockelements nuclide
alphaparticle groundstate orbital
anion group pblockelements
atomicmass halogens periodictableoftheelements
atomicmassunit(u) ion period
atomicnumber(Z) isotopes pnictogens
atom lanthanoids product
cation lawofconservationofmass proton
chalcogens lawofdefiniteproportions quantisation
chemicalequation lawofmultipleproportions radioactive
chemicalreaction massnumber(A) radionuclide
chemicalsymbol matter rareearthelements
compound metalloids reactant
covalentbond metals redoxreaction
dblockelements molecule sblockelements
Dalton'satomictheory neutron spin
electronictransition noblegases subatomicparticles
electron nonmetals transitionmetals

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

2 TheLanguageof
Chemistry
Chemistry,likeanyspecialistdiscipline,hasalanguageallitsown.Thelanguageof
chemistryisnotmerelyaboutwordsitisalsoaboutsymbols,diagrams,formulae,
abbreviations,equationsandpictures.Aworkingknowledgeofthislanguageisneededtobe
abletodescribeanddepictchemicalelements,compoundsandprocesses,andto
communicateandappreciatemanyoftheimportantconceptsofthisscience.Inthischapter
wewillconcentrateonthreeimportantareaswithinthebroadfieldofthelanguageof
chemistry:
measurementandunits
representationsofmolecules
nomenclature,thewayinwhichwenamechemicalspecies.
 KEYTOPICS

2.1Measurement
2.2Representationsofmolecules
2.3Nomenclature

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.1Measurement
Chemistryisascienceofmeasurement.Wheneverweweighacertainmassofaparticularsubstance,evaluatetherateofachemical
reactionordeterminethecellpotentialofanelectrochemicalcell,wearemakingmeasurements.Measurementsalwayshaveaunit
andalwayshaveanassociateduncertainty.Ameasurementthatismissingeitheroftheseismeaningless.

SIUnits
On23September1999,NASA,theNationalAeronauticsandSpaceAdministrationoftheUSA,lostcontactwithitsMarsClimate
Orbiterspacecraft(figure2.1)asitwasabouttoenterorbitaroundMars.Theorbitereventuallycrashedintotheplanet.Theloss
wasattributedtoanerrorthatresultedfromanincorrectuseofunitsoneteamofscientistsworkingontheprojectusedimperial
units(feet,pounds)whileothers,workinginadifferentlocation,usedSIunits(metres,kilograms)incalculatingthethrustnecessary
toplacethespacecraftintoorbitaroundMars.Similarly,on23July1983,AirCanadaflight143,aBoeing767with69peopleon
board,ranoutoffuelat12000mbecausethefuelhadbeenmeasuredinincorrectunits.Thankfully,thepilotswereabletoglideto
asuccessfullanding.

FIGURE2.1NASA'sMarsClimateOrbitercrashedintoMarsaftercalculationsweremadeusinginconsistentunits.

Thesetwoexamplesillustratethesignificanceofunitsinourmodernworld.Aunitisaspecificstandardquantityofaparticular
property,againstwhichallotherquantitiesofthatpropertycanbemeasured.Forexample,wecanmeasurealllengthswithrespect
tothelengthof1metre,andmetreisthereforeaunitoflength.Humanshaverecognisedtheimportanceofunitsofmeasurementfor
thousandsofyears.Oneoftheearliestdocumentedunitsofmeasurementwasthecubit,aunitoflengthusedinancientEgyptequal
tothedistancebetweenthetipofthemiddlefingerandtheelbow.Infact,manyunitsusedbytheancientEgyptianswerebasedon
partsofthehumanbody,suchasthedigit,thepalm,thehandandthespan.Obviouslypeoplecomeinalldifferentshapesandsizes,
sothissystemwasfarfromsatisfactory.Overtime,ajumbleofmeasuringsystemsandstandardsdeveloped.Forexample,itis
believedthatinaroundtheyear1100,England'sKingHenryIdefinedtheyardasthedistancefromtheendofhisnosetothetipof
histhumb,while200yearslaterKingEdwardIIdecreedthatthreebarleycornslaidendtoendconstitutedaninch.ItwasinFrance,
followingtheFrenchRevolutionin1789,thataseriousattemptwasfirstmadetodevelopaninternationalsystemofunits.On22
June1799,twopiecesofplatinum,oneweighingexactly1kilogramandtheotherexactly1metreinlength,weredepositedinthe
ArchivesdelaRpubliqueinParis,markingtheintroductionofwhatiscommonlyknownasthemetricsystemandwhatscientists
callSI(SystmeInternational)units.TheSIhasasetofbaseunitsforsevenmeasuredquantities.Thesearegivenintable2.1
alongwiththeirdefinitions(noticethatthedefinitionofthemetrehaschangedsince1799themetreisnowexpressedmore
precisely,intermsunimaginable200yearsago).
TABLE2.1 TheSevenSIBaseUnits
Measurement Unit Symbol Derivation
length metre m Themetreisthelengthofthepathtravelledbylightinavacuumduringatimeinterval
of ofasecond.

mass kilogram kg Thekilogramisequaltothemassoftheinternationalprototypeofthekilogram.

time second s Thesecondisthedurationof9192631770periodsoftheradiationcorrespondingto
thetransitionbetweenthetwohyperfinelevelsofthegroundstateofthe133Csatom.
temperature kelvin K Thekelvinisthefraction ofthethermodynamictemperatureofthetriplepoint
ofwater.
amountof mole mol Themoleistheamountofsubstanceofasystemwhichcontainsasmanyelementary
substance entitiesasthereareatomsin0.012kilogramsof12C.

Whenthemoleisused,theelementaryentitiesmustbespecifiedandmaybeatoms,
molecules,ions,electrons,otherparticlesorspecifiedgroupsofsuchparticles.
 electric ampere A Theampereistheconstantcurrentwhich,ifmaintainedintwostraightparallel
current conductorsofinfinitelength,ofnegligiblecrosssectionandplaced1metreapartina
vacuum,wouldproduce,betweentheseconductors,aforceof210 7newtonsper
metreoflength.
luminous candela Cd Thecandelaistheluminousintensity,inagivendirection,ofamonochromatic
intensity radiationoffrequency54010 12hertzandthathasaradiantintensityinthatdirection
of wattpersteradian.

Aworkingknowledgeoftheunitsandsymbolsgivenintable2.1isessentialinchemistry.However,theprecisedefinitionsare
generallycomplicated,anditisnotnecessarytomemorisetheirderivations,whicharegivenforinterestonly.Itshouldbenoted
that,atthetimeofwriting,proposalshavebeenmadetoredefineboththemoleandthekilogram.Theinternationalprototypeofthe
kilogram(whichiskeptinavaultattheInternationalBureauofWeightsandMeasuresnearParis)hasbeenfoundtohavelostabout
50govertime,andadefinitionwhichdoesnotinvolveaphysicalobjectthatissubjecttochangeisthoughttobepreferable.
Similarly,adefinitionofthemolethatdoesnotinvolvemasshasbeenproposed.Suchredefinitionswillmakenodifferencetothe
useofSIunitsineverydaylife,andwillhaveonlyaminisculeimpactonallbutthemostprecisescientificmeasurements.

WeareallfamiliarwiththeSIunitsforlength(metre,m),mass(kilogram,kg)andtime(second,s).TheSIunitoftemperature
(kelvin,K)hasabsolutezero(273.15C),thecoldestpossibletemperature,asitszeropoint.Temperatureismorecommonly
measuredindegreesCelsiusatemperatureinCelsiusmaybeconvertedtodegreeskelvinbyadding273.15.Thismeansthatthe
freezingpointofwater,0C,isequalto273.15K,whiletheboilingpointofwater,100C,is373.15K.Notethatatemperature
differenceof1kelvin(wedonotsay1degreekelvin)isthesameasatemperaturedifferenceof1degreeCelsius.

TheSIunitofamountofsubstance,aconceptthatwillbediscussedinchapter3,isthemole(mol),whiletheunitofelectrical
current,theampere,willbediscussedwhenwestudyelectrochemistryinchapter12.TheSIunitofluminousintensity(the
brightnessoftheradiationemittedbyphosphorescentandfluorescentcompounds)isthecandela.

TheSIunitsforanyphysicalquantitycanbebuiltfromthesesevenbaseunits.Forexample,thereisnoSIbaseunitforarea,butwe
knowthattocalculatetheareaofarectangularroomwemultiplyitslengthbyitswidth(i.e.itslengthinonedimensionbyitslength
intheother).Therefore,theSIunitforareaisderivedbymultiplyingtheunitforlength(m)bytheunitforlength(m)togivem2
(metresquared,orsquaremetre).Table2.2listsseveralderivedSIunitsthatareimportantinchemistry.
TABLE2.2 SIDerivedUnitsCommonlyUsedinChemistry
Expressionintermsofsimpler ExpressionintermsofSIbase
Measurement quantities Unit units
area lengthwidth (a) squaremetre m2
volume lengthwidthheight(a) cubicmetre m3
speed,velocity distance(b)/time metrepersecond ms1
acceleration velocity/time metrepersecond ms2
squared
density mass/volume kilogrampercubicmetre kgm3
specificvolume volume/mass cubicmetreperkilogram m3kg 1
force massacceleration newton,N 1N=1kgms2
pressure force/area pascal,Pa

energy forcedistance(b) joule,J

power energy/time watt,W

electriccharge electriccurrenttime coulomb,C 1C=1As

electric energy/electriccharge volt,V
potential

(a)Widthandheightaresimplylengthindifferentdirections.
(b)Distanceisanothernameforlength.
Theunitsforareaandvolume,squaremetreandcubicmetre,respectively,areprobablyfamiliartoyou,asaretheirsymbols,m2
andm3.However,whileyouarealsoprobablyfamiliarwiththeunitofvelocity,metrepersecond,youmayperhapswonderhow
thesymbolms1isobtained.Toobtainavelocity,wedividelengthbytime,andweobtaintheunitforvelocitybydividingtheunit
oflength(m)bytheunitoftime(s).Wecanwritethesymbolfortheresultingunitintwoways:asm/s,or,asweshalldo
throughoutthisbook,asms1.Recallthatx1issimplyanotherwayofwriting ,andso,whenwewritems1,thisisthesameas
.Similarly,weobtainanaccelerationbydividingvelocitybytime,andtheunitisthenderivedfromtheunitofvelocity

(ms1)dividedbytheunitoftime(s).Theunitistherefore (metrepersecondsquared),wheres2isthesameas .
Thisillustratesaveryimportantconceptthatisusedthroughoutthisbookwhenweperformcalculations:unitsundergothesame
kindsofmathematicaloperationsasthenumberstowhichtheyareattached.Wedemonstratethisinworkedexample2.1.

WORKEDEXAMPLE2.1

DerivingSIunits
Heatcapacity,whichwewillmeetinchapter8,isameasureoftheheatrequiredtoraisethetemperatureofaparticular
substanceby1K.Wecanobtainheatcapacityvaluesbydividingtheheatprovidedbythetemperaturechangeobtained.
WhatisthederivedSIunitofheatcapacity?

Analysis

Asweobtainheatcapacityvaluesbydividingheatbytemperaturechange,wewillobtaintheunitforheatcapacityby
dividingtheunitsofheatbytheunitsoftemperaturechange.

Solution

TheSIunitofheatisthejoule(J)andtheSIunitoftemperature,andthereforetemperaturechange,isthekelvin(K).
Therefore,theunitofheatcapacityis:

PRACTICEEXERCISE2.1
Thekineticenergyofanobjectofmassmmovingat
velocityuis .WhatisthederivedSIunitofkinetic
energy?

SometimesitisinconvenienttouseSIbaseorderivedunits.Forexample,wewouldnotwanttousemetrestomeasurethetiny
lengthofanatomicradiusortheenormousdistancetotheneareststar.TheSIsystemaddressesthisproblembytheuseofprefixes
thatdivideormultiplytheunitbyaparticularpoweroften.Forexample,theprefixcentimeansthefollowingunitisdividedby
100,whiletheprefixkilosignifiesthatthefollowingunitismultipliedby1000.Table2.3liststhemostcommonprefixes.
TABLE2.3 CommonPrefixesforSIUnits
Prefix Symbol Factor
tera T 10 12
giga G 10 9
mega M 10 6
kilo k 10 3
deci d 10 1
centi c 10 2
milli m 10 3
 micro 10 6
nano n 10 9
pico p 10 12
femto f 10 15

Eachprefixhasanassociatedsymbol,whichisplacedimmediatelybeforethebaseunit.Therefore,kmreferstokilometre,aunitof
10 3m,whilecm(centimetre)isaunitof10 2m.

WORKEDEXAMPLE2.2

UsingSIprefixes

Objectsthataresmallerthanabout210 7mcannotbeseenunderanopticalmicroscope.Couldweuseanoptical
microscopetoobserveavirusthatis20nmlong?

Analysis

Weneedtoconvert20nmtometres,andcompareitwith210 7m.TheSIsymbolnstandsfornanoandmeans10 9,
sowewillusethisconversionfactor.

Solution

Weknowfromtable2.3that1nm=110 9m,andtherefore20nm=2010 9m=210 8m.Thisislessthan2

10 7mandhencewewillnotbeabletoseethisvirususinganopticalmicroscope.

Isouranswerreasonable?

Wecancheckourresultbyconvertingthesizeofthesmallestvisibleobject(210 7m)tonanometressothatitcanbe
compareddirectlywiththesizeofthevirus210 7misequalto20010 9m,or200nm.Thevirusis20nmlongthe
smallestobjectthatcanbeseenunderthemicroscopeis200nm,soagainweconcludethattheviruswillnotbevisible.

PRACTICEEXERCISE2.2

1.Givetheabbreviationfor:
a.microgram
b.micrometre
c.nanosecond.
2.Howmanymetresarein:
a.1nm
b.1cm
c.1pm?
3.Whatsymbolisusedtorepresent:
a.10 2g
b.106m
c.10 6s?

NonSIunits
AlthoughSIunitshavebeenadoptedinnearlyallcountries(USA,MyanmarandLiberiabeingtheonlyexceptions),therearemany
nonSIunitsincommonusagethroughouttheworld.Forexample,wesawonp.25thattemperaturesaremuchmorelikelytobe
measuredindegreesCelsius(ordegreesFahrenheitintheUSA,MyanmarandLiberia)thanintheSIunitkelvin.Evenchemistsare
notimmunetothisweoftenusethelitre,aunitofvolumeequalto1000cm3,ratherthanthemorecorrect(butinconveniently
large)m3.Themillilitre(1cm3)isalsooftenused.VariousnonSIunitsofpressure(atmosphere,millimetreofmercury,torr,bar),
ratherthantheSIunitpascal,arestillregularlyseeninthechemicalliterature.AslongasuseofnonSIunitspersists,itwill
occasionallybenecessaryforyoutobeabletoconvertbetweennonSIandSIunits.Todothis,weneedtoknowtheconversion
factorbetweentheunits.Thenwecanobtainanequationtoconvertbetweenthetwo.Thisisillustratedinworkedexample2.3.

WORKEDEXAMPLE2.3

Unitconversions
Thelawsofcricketstatethatacricketpitchis22yardsinlength.Howlongisacricketpitchinmetresgiventhat1metre
=1.0936yards?

Analysis

Wearetoldthat1metrecorrespondsto1.0936yardsinotherwords,thereare1.0936yardsineverymetreor,toputit
yetanotherway,1.0936yardspermetre.Therefore,theconversionfactor,intermsofyardspermetre,is
.

However,weareaskedtoconvertfromyardtometre,andthereforeneedtheconversionfactorintermsofmetresper
yard(metreyard 1).Weobtainthisknowingthat:

Wecannowsolvetheproblembymultiplyingthisconversionfactorby22yards.

Solution

22yard0.9144metreyard 1=20.12metre

Isouranswerreasonable?

Weknowthat1metreisslightlylongerthan1yard,sowewouldexpectournumericalanswertobeslightlylessthan22,
whichitis.Noticealso,aswewillseeonpp.289,thattheunitsinoursolutionareconsistentyardmetreyard 1=
metre.

PRACTICEEXERCISE2.3
Usethegivenconversionfactorstocarryoutthefollowing
conversionsinvolvingpressureunits.
1.Convert0.3bartopascal(1pascal=110 5bar).
2.Convert451millimetresofmercurytopascal(1
pascal=7.5010 3millimetresofmercury).
3.Convert3.81atmospherestopascal(1pascal=9.87
10 6atmosphere).

Noticethatthemethodofunitconversiondescribedonp.27canalsobeusedforconversionbetweenSIunits.Forexample,
supposewewantedtoexpress418cm3inm3wewouldneedtheconversionfactorintermsofm3cm3.Fromtheunitprefixc,we
knowthat:
Theconversionfactoristherefore ,andwecarryouttheconversionasfollows:

DimensionalAnalysis
OneofthequestionsmostcommonlyaskedbystudentsisWhatequationsdoIneedtolearnforthefinalexam?Ifyoureadthis
bookfromcovertocover(orindeed,ifyoujustgototheglossaryofequationsattheendofthebook),youwillfindalargenumber
ofequations,allofwhichareimportanttothesubjectofchemistryinonesenseoranother,andyoumightthinkthatitisnecessary
foryoutolearnthemallbyheart.You'llbehappytoknowthatthisisnotthecase.

Dimensionalanalysisinvolvesusingtheunitsofaphysicalquantitytoderivetheequationusedtodetermineitsvalue.Wefirst
encounteredthisonp.26whenwestatedthatunitsundergothesamekindsofmathematicaloperationsasthenumberstowhich
theyareattached.Wethenwentontoillustratethisinworkedexample2.1(p.26)whenwedeterminedtheunitsofheatcapacity
(JK1)throughknowledgeofthefactthatheatcapacityisequaltoheat(J)dividedbytemperaturechange(K).Wewillnowlookat
thisprinciplemoreclosely,usingthestoichiometricequations and ,whichwillbeintroducedinchapter3.Theseare
twoofthemostusedequationsinchemistryand,withoutdoubt,theseequationsarethetwomostoftenwrittenincorrectly.Yet,all
youneedtoknowtodeterminethecorrectformsoftheseequationsaretheunitsofmolarmass(M),gmol1,andconcentration(c),
molL1.

Theunitofmolarmass,gmol1,isobtainedbydividingaphysicalquantityhavingtheunitgrambyaphysicalquantityhavingthe
unitmole.Thesephysicalquantitiesaremass(m)andamount(n),respectively.Knowingthisallowsustowritetheequationrelating
mass,amount,andmolarmassasfollows:

Therefore,

Andthereyouhaveittheequationisgivenbytheunits.Thecorrectunitsofmolarmass(gmol1)areobtainedonlyifwedivide
mass(g)byamount(mol).Noothercombinationofmassandamountwillgivethecorrectunitsofmolarmass.

Asimilarsituationoccursinthecaseofconcentration.TheunitofconcentrationismolL1,andisthereforeobtainedbydividinga
physicalquantityhavingtheunitmolebyaphysicalquantityhavingtheunitlitre.Weknowthatmoleistheunitofamount(n)and
litreistheunitofvolume(V).Therefore,wecanwrite:

Therefore,

Again,noothercombinationofamountandvolumewillgivethecorrectunitsofconcentration.

Dimensionalanalysisassistsyounotonlyinrememberingthecorrectformofanequation,butalsoinensuringyouhaverearranged
anequationcorrectly.Consider,forexample,rearrangingtheaboveequationforconcentration,tomakenthesubject.Thecorrect
rearrangement,obtainedbymultiplyingbothsidesoftheequationbyV,gives

andwecaneasilycheckthisbecauseweknowthattheunitsonbothsidesoftheequationmustbethesame.Onthelefthandside,
wehaveunitsofmolandontherighthandsidewehaveunitsofmolL1L=mol.Therefore,wecanbeconfidentthatwehave
rearrangedtheequationcorrectly.

Ifwehadarrangedthevariablesincorrectly,e.g. or ,wecouldquicklyseefromtheunitsthatwehadmadeamistake
givesunitsofmolL1/L=molL2,while givesunitsofL/molL1=L2mol1.Neithercanbecorrectastheydonotgivethe
unitsofmol.
Thisisalwaysagoodcheckwheneveryourearrangeanequationiftheunitsarenotthesameonbothsidesoftherearranged
equation,youhavemadeamistake.

Therearesituationswheredimensionalanalysismight,atfirstglance,appearnottowork.Consider,forexample,theidealgas
equation,pV=nRT,whichwewillencounterinchapter6.Giventhatpressure(p)ismeasuredinPa,volume(V)inm3,amount(n)
inmolandtemperature(T)inK,andthegasconstant(R)hasunitsofJmol1K1,wecanworkouttheunitsonbothsidesofthe
equation:
TheunitsofpV(lefthandside)arePam3=Pam3.
TheunitsofnRT(righthandside)aremolJmol1K1K=J.
Thisdoesnotappeartobecorrect,asitlooksasthoughwehavedifferentunitsoneachsideoftheequation.However,remember
thatbothPaandJarederivedunitsfromtable2.2(p.25)wecanseethat1J=1kgm2s2and1Pa=1kgm1s2.Therefore

andwecanseethattheunitsonbothsidesoftheequationare,infact,thesame.

Dimensionalanalysisisnotlimitedtotheserelativelysimpleequations.Itworksforanyequation.Thisisbecausethenumbersand
theunitsonbothsidesofanequationmustbethesame.Asworkedexample2.4shows,dimensionalanalysiscanalsobeusedto
determinethecorrectformofanequationifyouknowtheunitsofalltheconstituentcomponents.

WORKEDEXAMPLE2.4

DimensionalAnalysis
Anaqueoussugarsolutionwillboilatatemperatureslightlygreaterthan100C,dependingonhowmuchsugarthe
solutioncontains.Themagnitudeofthisboilingpointelevation(T)canbecalculatedfromsomecombinationofthe
molalboilingpointelevationconstant(Kb)andthemolality(b)ofthesolution.Giventhattheunitsofbaremolkg 1and
thoseofKbareKmol1kg,whatequationshouldbeusedtocalculateTwhenthisismeasuredinK?

Analysis

WeneedtocombinetheunitsofbandKbtogiveunitsofKinourfinalanswer.Therearethreepossibilities:

WeneedtodeterminethefinalunitsforTthatresultfromeachofthesethreepossibilities.Thecorrectequationwill
givefinalunitsofK.

Solution

Weinserttheappropriateunitsintoeachofthethreeexpressionsabove.

Therefore,thecorrectequationtocalculatetheboilingpointelevationisT=Kbb.

Isouranswerreasonable?

GiventhatthereisonlyonewayofcombiningtheunitsofKbandbtogiveunitsofK,wecanbeconfidentouransweris
correct.

Wewilllearnmoreaboutboilingpointelevationinchapter10.
 PRACTICEEXERCISE2.4
Deducethecorrectformofeachofthefollowing
equationsbyconsideringtheunitsofallthecomponents
oftheequation.
(a)Obtainanequationformass(m,g)intermsof
molarmass(M,gmol1)andamount(n,mol).
(b)Obtainanequationforthegasconstant(R,Jmol1
K1)intermsofpressure(p,Pa),volume(V,m3),
amount(n,mol)andtemperature(T,K).
(c) Obtainanequationforthespeedoflight(c,ms1)
intermsofenergy(E,J),Planck'sconstant(h,Js)
andwavelength(,m).

UncertaintiesandSignificantFigures
Everymeasurementhasanassociateduncertainty,whichresultsfromthelimitationsofthemethodsweusetomakethe
measurement.Consider,forexample,aquantitythatyouprobablyknowwell:yourweight.Ifyouusedananaloguesetofbathroom
scaleswhichcanweightothenearestkilogramtoweighyourself,youmightfindthatyourweightliesalmostexactlyhalfway
betweenthedivisionscorrespondingto71kgand72kg.Doyouquoteyourweightas71kgor72kg?Thereisobviouslysome
uncertaintyoverthelastfigureinthemeasurement.Youthereforeinvestinamoreexpensivesetofdigitalscaleswhichcanweigh
tothenearest0.1kilogramusingthese,youfindyouweigh71.6kg.However,ifyouwaitlongenough,younoticethatthedisplay
fluctuatesbetween71.5kgand71.7kg.Again,thelastfigureintheanswerisuncertain.Youcouldkeepbuyingscalesthatweigh
toeversmallerfractionsofakilogram,butyouwouldalwaysfindthattherewouldbesomeuncertaintyinthefinalfigureofthe
measurement.Wecanillustratethisconceptfurtherbyconsideringthetwothermometersinfigure2.2,whichdisplaythesame
temperature.
 FIGURE2.2Thermometerswithdifferentscalesgivereadingswithdifferentprecision.Thethermometeronthelefthasdivisionsthatare1C
apart,allowingthetemperaturetobeestimatedtothenearest0.1C.Thethermometerontherighthasdivisionsevery0.1C,
thereforepermittingestimationofthetemperatureto0.01C.

Thedivisionsontheleftthermometerare1Capartanditisthereforecertain,barringanyimperfectionsinthemanufactureofthe
thermometer,thatthetemperatureisgreaterthan24Candlessthan25C.Itcanbeestimatedthatthetopofthefluidcolumnfalls
about0.3ofthewaybetweenthedivisionsfor24Cand25C,sothemeasurementcanberecordedas24.3C.However,we
cannotsaythatthetemperatureisexactly24.3C,asthelastfigureisonlyanestimate,andtheleftthermometermightbereadas
24.2Cbyoneobserverand24.4Cbyanother.Thethermometerontherightisgraduatedindivisionsof0.1Candmaytherefore
bereadtoagreaterprecisionthantheotherthermometer.Readingthethermometerontheright,itisnowcertain,againassumingno
flawsinthethermometer,thatthetemperatureliesbetween24.3Cand24.4C,andanotherfigureinthemeasurementcanbe
estimatedbynotingthatthetopofthefluidliesabout0.2ofthewaybetweenthedivisions.Therefore,thetemperatureaccordingto
thethermometerontherightwouldbestatedas24.32C.Byconventioninscience,allfiguresinameasurementuptoand
includingthefirstestimatedfigurearerecorded.Thefiguresrecordedaccordingtothisconventionarecalledsignificantfigures.
Thethermometerontherightcanbereadtoagreaterprecision,andthemeasurementmadecontainsacorrespondinglylarger
number(4)ofsignificantfigures.Thenumberofsignificantfiguresinameasurementisequaltothenumberofdigitsknownfor
certain,plusonethatisestimated.Therefore,therewillalwaysbeuncertaintyinthelastsignificantfigureofanymeasurement.In
theaboveexample,thefinalfiguresofboth24.3Cand24.32Careuncertain.

Itisusuallyeasytodeterminethenumberofsignificantfiguresinanumbersimplycountthefigures.However,ambiguitiesmay
arisewhenzerosarepresentforexample,doesthenumber0.0023containtwo(23),four(0023)orfive(0.0023)significant
figures?Suchproblemscanbeavoidedbywritingnumbersinscientificnotation,whichimmediatelyshowshowmanysignificant
figuresarepresent.Scientificnotationexpressesnumbersintermsofpowersoftenforexample,thenumber15becomes1.510 1
inscientificnotation,362becomes3.6210 2,andsoon.Inscientificnotation,0.0023iswrittenas2.310 3,anditcanbeseen
thatthenumbercontainsonlytwosignificantfigures.Similarly,themoreprecisenumber0.00230wouldbewrittenas2.3010 3,
andthisthenhasthreesignificantfigures.Notethatthenumberofsignificantfiguresinameasurementisthesameregardlessofthe
units.Forexample,alengthof2.310 3mcanbeexpressedinmillimetres(2.3mm)ornanometres(2.310 6nm),butineach
casethevaluesmusthavethesamenumberofsignificantfigures,astheprecisionofthemeasurementdoesnotdependontheunits
inwhichitisexpressed.
 WORKEDEXAMPLE2.5

SignificantFigures
Determinethenumberofsignificantfiguresinthefollowingnumbers.
(a)0.004136
(b)0.1060
(c)10.01

Analysis

Weneedtowritetheabovenumbersinscientificnotation.Wecanthendeterminethenumberofsignificantfiguresfrom
thenumberoffiguresinthescientificnotation.

Solution

Thenumberswritteninscientificnotationareasfollows.
(a) 4.13610 3
(b)1.06010 1
(c) 1.00110 1

Therefore,allthreenumbershavefoursignificantfigures.

Isouranswerreasonable?

Theambiguityinsignificantfigurescomeswithzeros.Aretheysignificant,oraretheyplaceholders?Inthenumber
0.004136,allthezerosareplaceholders,andwritingthisinscientificnotation(4.13610 3)makesthisclearnoneof
thezerosappearinthescientificnotationofthisnumber,sotheycannotbesignificant.Theothertwonumberscontain
zerosthataresignificant,becausetheyappearinthescientificnotation.Takingtheserulesintoaccount,ouransweris
reasonable.

PRACTICEEXERCISE2.5
Howmanysignificantfiguresdothefollowingnumbers
contain?
(a)1.000405
(b)0.001000
(c)1000010.0

Theuncertaintyinanymeasurementgenerallydependsontheprecisionoftheinstrumentusedtomakethatmeasurement.For
example,a20mLpipettemayhaveanuncertaintyof0.05mL(meansplusorminus).Wewouldthereforequotethepipetteas
measuring20.000.05mL(seefigure2.3).
 FIGURE2.3The0.1mLgraduationsonthispipetteimplyanuncertaintyof0.05mL.

Thismeansthatthepipettedeliversbetween19.95mLand20.05mLwheneveritisused.Thistypeofuncertaintyiscalledan
absoluteuncertaintyinotherwords,theuncertaintyhasthesameunitsasthequantitybeingmeasured.Wecanalsoquotethe
percentageuncertaintyforaninstrument.Inthiscase,wewouldcalculatethepercentageuncertaintyforthepipetteasfollows:

Aswewillseebelow,percentageuncertaintiesareimportantwhenwearedoingcalculationsinvolvingeithermultiplicationor
division.

Itshouldbenotedthattherearetwotypesofuncertaintiesinanymeasurement.Randomuncertaintiesrefertothereproducibilityof
ameasurement,andaregenerallytakenaccountofinthequoteduncertaintyoftheapparatususedtomakethemeasurement.These
arewhatgiverisetothetotaluncertaintythatwereportattheendofacalculation(seebelow).Systematicuncertaintiesusually
resultfromdeficienciesinthemeasuringequipmentorfromhumanerror,forexample,whenusingapipettewhichdeliversonly
19.00mLratherthanthestated20.00mL,orusingapHmeterwhichhasbeenincorrectlycalibrated.Theseuncertaintiescanbe
eliminatedthroughcarefulexperimentaltechnique.

UncertaintiesandSignificantFiguresinCalculations
Wehaveshownabovehowtodeterminethenumberofsignificantfiguresinanindividualnumber.Butwhenweusenumbersina
calculation,howmanysignificantfiguresdoestheanswercontain?Andhowdouncertaintiesinnumericalmeasurementstranslate
toanuncertaintyinthefinalanswerwhenthesemeasurementsareusedincalculations?Moreoftenthannot,youwillberelyingon
yourcalculatortocarryoutcalculationsthiswillgenerallygiveananswercontainingmanymoresignificantfiguresthanare
justifiedandwilltellyounothingabouttheuncertaintyinthatanswer.Youthereforeneedtomakeuseofsomerulestoappreciate
whatsortofprecisionyoushouldgiveinyourfinalanswer.

Todeterminetheappropriatenumberofsignificantfiguresintheanswerofacalculation,thefollowingrulesapply:
Whenanumericalmeasurementismultipliedbyaconstant,thenumberofsignificantfiguresintheanswerwillbethesameas
thatinthenumericalmeasurement.
Whentwoormorenumericalmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswershould
notbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whentwoormorenumericalmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthemeasurementwiththefewestnumberofdecimalplaces.

Wecanillustratetheserulesasfollows.Ifwecalculate:

onatendigitcalculator,theansweris13.49709375,anumberwithtenfigures.Buthowmanyofthesefiguresaresignificant?The
numbersinthenumerator(topline)containthreeandfoursignificantfiguresrespectively,whilethedenominator(bottomline)
containstwosignificantfigures(the0atthestartofthenumberisnotsignificant)andsoitmakesnosensetohaveananswerthatis
manyordersofmagnitudemoreprecisethananyofthenumbersfromwhichitisderived.Theruleatthebottomoftheprevious
pageformultiplicationanddivisionstatesthatwecanhaveonlyasmanysignificantfiguresinourfinalanswerasthereareinthe
leastprecisemeasurement.Therefore,inthisexample,wecanexpressouranswertoonlytwosignificantfigures,soourfinalanswer
becomes:
Ifwecalculatethesum:

acalculatorwillgivetheansweras169.807.However,lookingatthelayoutofthesumabove,weseethattherearenofigures
beneaththe7of3.247orthe6of41.36inotherwords,thefirstfigureafterthedecimalpointistheonlyonethatisknownforall
threenumbers.Addinganunknownfiguretothe6or7willgiveananswerthatisalsounknown,soforthissumwearenotjustified
inwritingfiguresinthesecondandthirdplacesafterthedecimalpoint.Thefirstfigureafterthedecimalpointistheonlyonethatis
knownforallthreenumbersand,therefore,weroundtheanswertothefirstdecimalplace,giving169.8.

Differentrulesapplywhenworkingwithlogarithms,aswewilldoextensivelyinchapter11whenconsideringpH.
Thelogarithmofanumbercanhavethesamenumberoffigurestotherighthandsideofthedecimalpointasthereare
significantfiguresinthenumber.

Forexample,thenumber0.00321hasthreesignificantfigures(thisbecomesmoreobviouswhenitiswritteninscientificnotation
as3.2110 3).Usingacalculatortodeterminethelogarithmgives2.4934949676.Thisshouldthenbequotedas2.493.

Thereverseisalsotruegivenalogarithm,youdeterminethecorrectnumberofsignificantfiguresintheantilogarithmfromthe
numberoffigurestotherightofthedecimalpoint.Hence,usingacalculator,wefindthattheantilogarithmof4.18is6.60693448
10 5.Thisshouldbequotedtotwosignificantfigures,namely6.610 5.

Theaboverulesforlogarithmsapplytobothcommon(log 10)andnatural(lnorlog e )logarithms.

Whilesignificantfiguresanduncertaintiesarerelated,therulesfordeterminingtheuncertaintyintheanswerofacalculationare
somewhatdifferentfromthoseforsignificantfiguresonthepreviouspage.Theyareasfollows:
Whentwoormorenumericalmeasurementsareaddedorsubtracted,theuncertaintyinthefinalansweristhesumofthe
absoluteuncertaintiesinthemeasurements.
Whentwoormorenumericalmeasurementsaremultipliedordivided,theuncertaintyinthefinalansweristhesumofthe
percentageuncertaintiesinthemeasurements.

Itisusualtoquotethefinaluncertaintyasanabsoluteuncertainty,soitisnecessarytobeabletoconvertfromapercentagetoan
absoluteuncertainty.

Wewillillustratetheserulesinworkedexample2.6.

WORKEDEXAMPLE2.6

Calculatinguncertainties
Aswewillseeinsection2.2,manysimplesaltsareobtainedashydratesfromaqueoussolutionthatis,theycrystallise
withadefinitenumberofwatermolecules(sometimescalledwaterofcrystallisation).Suchsaltshavethegeneralformula
MaXbcH2O,wherea,bandcaregenerallyintegers.Thewaterofcrystallisationcanoftenberemovedbyheating,togive
theanhydroussaltMaXb.

Inanexperiment,2.400gofCoSO47H2Owasheatedtoremovethewaterofcrystallisationuntilnofurthermasslosswas
observed.Atthispoint,themassofanhydrousCoSO4obtainedwas1.323g.Usethesefigurestocalculatethe
percentage,bymass,ofH2OinCoSO47H2O,andgivetheuncertaintyinyourfinalanswer.Notethatthebalanceusedto
weighthesampleshasanabsoluteuncertaintyof0.001g.

Analysis

Wearegiventhemassofthehydratedandanhydroussalts,sothemassdifferencebetweenthesemustcorrespondtothe
massofwaterinthehydratedsalt.Wethendividethisbythemassofthehydratedsaltandmultiplyby100toobtainthe
percentagebymassofwater.Wemustalsodeterminetheuncertaintyinthefinalanswer.Thiswillderivefromthe
uncertaintiesintheweighings.

Solution
Wewillfirstcalculatethepercentagebymassofwaterinthehydratedsalt,andthendeterminetheuncertaintyinthe
answer.

Notethat,becauseeachmasshasfoursignificantfigures,wecanquotetheansweratthisstagetofoursignificantfigures.

Nowwewillcarryouttheuncertaintyanalysis.Westatedonthepreviouspagethatthebalanceusedhasanabsolute
uncertaintyof0.001g,soyoumightthinkthateachmeasuredmasshasthisuncertainty.Infact,theuncertaintyineach
measuredmassis0.002g.Thisisbecauseeverymeasurementwemakeusingthebalanceisinfactthedifference
betweentworeadingsthefinalbalancereading,andtheinitial(zero)balancereading,bothofwhichhaveanabsolute
uncertaintyof0.001g.Becauseweareessentiallysubtractingtwovalues,wemustaddtheirabsoluteuncertainties,for
example:

Wecannowdeterminetheuncertaintyinthemassofwaterinthehydratedsalt.

Again,becausewearesubtractingtwomeasurements,weaddtheirabsoluteuncertainties.

Becausethenextstepinthecalculation,thedeterminationofthepercentagebymassofwaterinthehydratedsalt,
involvesadivision,wemustconverttheabsoluteuncertaintiesinboththemassofthehydratedsaltandthemassofwater
inthehydratedsalttopercentageuncertainties,andthenaddthemtogether.

Notethatwehaveretainedtwosignificantfiguresinthepercentageuncertaintyinthemassofwater.Itisoftenadvisable
tocarryextrafiguresintheuncertaintythroughoutthecalculationandthenroundtoasinglefigureattheend.

Nowwemustconvertourcalculatedpercentageuncertaintytoanabsoluteuncertainty.Wedothisasfollows.

Therefore,ourfinalanswerlooksasthoughitis(44.880.20)%.However,somethoughtwillshowusthatthisisnot
quitecorrect.Itisusualtoquoteuncertaintiestoasinglesignificantfigurethisisbecauseouranswerisgenerally
uncertainonlyinitsfinalfigure.Sowewouldthenamendouransweraboveto(44.880.2)%.However,thisstillposes
problemsastheuncertaintyrefersnottothefinalfigurebuttothefirstfigureafterthedecimalpoint.Aswehaveshown
that0.2istheminimumuncertaintyinouranswer,thisthendictatesthenumberofsignificantfigurestowhichthe
answercanbegiveninotherwords,thesecondfigureafterthedecimalpointintheanswerisnotsignificant,giventhe
magnitudeoftheuncertainty.

Thus,ourfinalanswer,includingtheuncertainty,is(44.90.2)%.

Isouranswerreasonable?

Themassloss(1.077g)ingoingfromCoSO47H2OtoCoSO4issolelyduetothewatermoleculesintheformer.This
 massisalittleunderhalfthetotalmassofCoSO47H2Oandthuswewouldexpectthatwatershouldmakeupjustunder
50%ofthetotalmassofCoSO47H2O.Ournumericalanswer(44.9%)isthereforelikelytobecorrect.Checkingthatour
uncertaintyisreasonableissomewhatmoredifficult.However,weknowthatthetotaluncertaintyresultsfromtwo
weighings,andthateachofthesehasanuncertaintyofmuchlessthan1%.Therefore,ourfinaluncertaintyof0.2%
appearsreasonable.

PRACTICEEXERCISE2.6
Givetheanswersofthefollowingcalculationstothe
correctnumberofsignificantfigures.
(a)4.196+8.3492+14.73
(b)5.361.259
(c)6.38(2.514+5.4)
(d)thetotalmassoftwobeakersofwater,eachof
whichweighs37.50g
(e)log(2.1855.48)
(f)

PRACTICEEXERCISE2.7
Performthefollowingcalculationsinvolving
measurements.Givetheanswerstothecorrectnumberof
significantfigures,andusetheappropriateunits.
(a)21.0233g+21.0g
(b)32.02mL2.0mL
(c)54.183g0.0278g
(d)10.0g+1.03g+0.243g
(e)

(f) 1.03m2.074m3.9m

PRACTICEEXERCISE2.8

Astudentwantedtoprepare100mLofa1.000gL1
solutionofNaClanddevisedthefollowingmethod.The
studentweighed0.100gofsolidNaClonabalanceand
transferredthistoa100mLvolumetricflask.Sufficient
waterwasthenadded,withstirring,togiveafinalvolume
of100mLaccordingtothemarkonthevolumetricflask.

Giventhattheuncertaintiesinthebalanceandvolumetric
flaskwere0.001gand1mL,respectively,calculatethe
finaluncertaintyintheconcentrationoftheNaClsolution.
Didthestudentsucceedinpreparinga1.000gL1
solution?Ifnot,whatwastheconcentration,includingthe
uncertainty,ofthesolution?

Thewordprecisehasbeenusedinthissection,withoutbeingdefined.Itisimportanttoappreciatethedifferencebetween
accuracyandprecisionwhenmakingmeasurements.Ameasurement'saccuracyreferstohowclosethevalueistothecorrect
value,whileprecisionsignifieshowreproducibleaparticularmeasurementiswhenmadeanumberoftimesand,therefore,how
manysignificantfiguresitcanbequotedto.Thetwoconceptsareillustratedinfigure2.4.
FIGURE2.4Thedifferencebetweenprecisionandaccuracyinthegameofgolf.Golfer1hitsshotsthatareprecise(becausetheyaretightly
grouped),buttheaccuracyispoorastheballsarenotnearthetarget(thetruevalue).Golfer2needshelp.Theshotsareneither
precisenoraccurate.Golfer3winswithshotsthatareprecise(tightlygrouped)andaccurate(inthehole).

PRACTICEEXERCISE2.9
Fourworkersweigha10.000gmassthreetimeson
severaldifferentkitchenscalesandobtainthefollowing
results.
WorkerA:10.022g,9.976g,10.008g
WorkerB:9.836g,10.033g,9.723g
WorkerC:10.230g,10.231g,10.232g
WorkerD:9.632g,9.835g,9.926g
Whichsetofdatahasthebestprecision?Whichhasthe
bestaccuracy?

ChemicalConnections

TheNationalMeasurementInstitute

TheNationalMeasurementInstitute(NMI)istheorganisationresponsibleforprovidingunitandmeasurementstandards
andservicesinAustralia.Ithasfourmainsections:
legalmetrologyandbusinessservices
physicalmetrology
analyticalservices
chemicalandbiologicalmetrology.

Wementionedearlierinthischapterthattheprimarystandardofmassistheinternationalprototypeofthekilogram,
whichisaplatinumiridiumcylinderheldattheInternationalBureauofWeightsandMeasures.TheNMIholdsCopy
No.44(figure2.5)oftheinternationalprototypeofthekilogram.ItservesastheAustralianstandardofmassandthe
NMIusesittocalibrateasetof1kgstainlesssteelstandards.Thosestandardsarethenusedtocalibratestandardswith
massesfrom0.5mgto20kg,whichareusedforallcalibrationworkonmassandthemeasurementofvariousother
quantities.
 FIGURE2.5Australia'sCopyNo.44oftheinternationalprototypeofthekilogram.Thisismadeofa90%platinum10%iridium
alloy.

Whilemeasurementmightseemasomewhatesotericfield,itisofgreatimportanceinmanydisciplines,including
chemistryandbusiness.Forexample,oneofthekeyaimsoftheNMIistopromoteuniformmeasurementpolicyand
practicetohelpinternationaltrade.OneareainwhichtheNMIhasbeenactiveisthewineindustry.

Australiaexportshundredsofmillionsoflitresofwineeachyear.Awineconnoisseurwilltellyouthattaste,bouquetand
colourarethequalitiesthatcharacteriseawine(figure2.6).Ametrologist(someonewhospecialisesinmeasurement)
mighttalkmoreaboutthelevelsofchemicalresidues,contaminantsandpreservatives.Inadditiontohealthandquality
concerns,manyinternationalmarketshavestrictregulationsonacceptablelevelsofethanol,sulfitesandheavymetalsin
wines.Exportersmustcomplywiththeseregulationstoensuretheycanselltheirwinesintothosemarkets.
 FIGURE2.6Chemicalanalysiscanquantifywhatawineexpertdetectsusingthesenses.

NMIprovidesthewineindustrywithanalyticalchemistryservicestodeterminepesticide,insecticideandherbicide
residues,foreignmatter,alcoholcontentandotherimportantinformation.Thetechniquesusedhavebeenvalidated
againstthoseusedinothercountriestoensurethemeasurementsareacceptedbyexportmarkets.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.2RepresentationsofMolecules
Thelanguageofchemistryisnotonlyaboutthemeaningofwords,butalsoabouthowwecanrepresent
chemicalspeciesusingparticularcombinationsofletters,numbers,symbolsandpictures(seefigure2.7).In
thissectionwewilldescribesomeofthemanydifferentwaysinwhichwecandepictmolecules,aswellas
thebondmakingandbondbreakingprocessesthatoccurinchemicalreactions.

FIGURE2.7 Differentwaysofrepresentingthechemicalspeciesmethane:
(a)chemicalformula,
(b)structuralformula,
(c)3Dstructuralformula,
(d)ballandstickmodeland
(e)spacefillingmodel.

ChemicalFormulae
Thesimplestwaytodescribethecompositionofanysubstanceistowriteitschemicalformula.Thisshows
thenumberofeachtypeofatompresentinasubstance.Achemicalformulacontainselementalsymbolsto
representatomsandsubscriptednumberstoindicatethenumberofatomsofeachtype.Itmaybeassimple
aswater,H2O,orascomplicatedasC30H34AuBClF3N6O2P2PtW,thecompoundwhichcurrentlyholdsthe
recordforcontainingthemostelements.Aswehaveseeninchapter1,eachchemicalelementisdescribed
byaone,twoorthreelettersymbol,andtheseformthebasisforallchemicalformulae.Thesimplest
chemicalformulaedescribepureelementsandareusuallyjusttheirelementalsymbolsaslistedonthe
periodictableforexample,heliumisHe,siliconisSiandcopperisCu.Suchformulaeimplythatthebulk
elementsarecomposedofeitherindividualatomswhichdonotinteract(suchasHe)orinfinitethree
dimensionalarraysofbondedatoms(suchasSiandCu).However,thisisnotthecaseforsomeelements
andwemustwritemorecomplexchemicalformulaeforthese.Forexample,sevenelements(hydrogen,
nitrogen,oxygen,fluorine,chlorine,bromineandiodine)occurnaturallyneitherasindividualatomsnoras
threedimensionalarraysbutasmoleculescontainingtwoatoms(diatomicmolecules).Tosignifythis,their
chemicalformulaearewrittenasH2,N2,O2,F2,Cl2,Br2andI2respectively.Someotherelementsoccuras
largermoleculesaphosphorusmoleculecontainsfourPatomsandasulfurmoleculecontainseightSatoms
sotheirchemicalformulaeareP4andS8respectively.Achemicalformulathatreferstoadiscretemolecule
isoftencalledamolecularformulaasitdescribesthetypesandnumbersofatomspresentinthemolecule.
Notethatasubscriptednumeralreferseitheronlytotheatomimmediatelyprecedingit,or,ifitfollowsa
groupofatomsenclosedinparentheses,totheentiregroupofenclosedatoms.Forexample,thechemical
formulaB(OH)3showsthatthecompoundcontainsoneboronatom,threeoxygenatomsandthree
hydrogenatoms.

Chemicalcompoundscontainmorethanoneelement.Therefore,thereispotentiallymorethanonewayto
writetheformulaofanycompound.Forexample,hydrogenchlorideisadiatomicmoleculewithoneatom
eachofhydrogenandchlorine.ItschemicalformulamightthereforebewrittenasHClorClH.Toavoid
possibleconfusion,chemistshavestandardisedthewritingofchemicalformulae.Forbinarycompounds
(compoundscontainingonlytwoelements)thefollowingguidelinesapply:
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
ExamplesareKCl,PCl3,Al2S3andFe3O4.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.Forexample,wewritehydrogenlastinLiH,NH3,B2H6andCH4,butfirstinH2O2,
H2S,HClandHI.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst,for
exampleSiCandBrF3.
4.Ifthecompoundisionic,wewritethecation(thepositivelychargedion)first,followedbytheanion
(thenegativelychargedion).ExamplesareNaBrandMgCl2.

Writingchemicalformulaeforcompoundscontainingmorethantwoelementsrequiressomeknowledgeof
thebondingwithinthecompound.Aswewilldiscussingreaterdetailinchapter5,chemicalcompounds
canbedividedbroadlyintotwoclassesioniccompoundsandcovalentcompoundswhichare
distinguishedbythetypeofbonding.Ioniccompoundsarecomposedsolelyofions,andtheattractive
forcesbetweenionsofoppositechargeresultintheformationofinfinitethreedimensionallattices.Onthe
otherhand,covalentcompoundsarecharacterisedbybondinginvolvingthesharingofelectronsbetween
adjacentatoms.Towritethechemicalformulaofanioniccompoundcontainingmorethantwoelements,we
againwritethecationfollowedbytheanion.Forexample,theformulaofsodiumnitrate,whichcontains
positivelychargedsodiumions,Na+,andnegativelychargednitrateions,NO3,isNaNO3.Notethatthe
orderingoftheelementsintheNO3ionconformstotherulesgivenabove.Notealsothatwemustalways
ensurethatthetotalchargeontheioniccompoundiszero,sothenumberofNa+andNO3ionsmustbethe
same,andweneverincludetheindividualionicchargesintheoverallformula.Writingthechemical
formulaforcalciumnitrateisalittlemorecomplicated.TheformulaofthecalciumionisCa2+,whilethatof
thenitrateionisNO3.Wecanseethat,toachieveanoverallchargeofzero,wewillrequireoneCa2+ion
andtwoNO3ions,anditiswiththelatterthatapotentialproblemarises.Wesignifythepresenceoftwo
NO3ions,aswedoforanyion,byusingasubscripted2immediatelyfollowingtheion.However,you
canseethat,ifwedothis,wewillhavetwosubscriptednumbersimmediatelyadjacenttoeachother,
therebyleadingtopossibleconfusion.Incasessuchasthis,weenclosetheioninparentheses,andplacethe
subscripted2outsidetheparentheses.Puttingthecationfirst,wethereforewritethechemicalformulaas
Ca(NO3)2.Asstatedonthepreviouspage,itisunderstoodthatthesubscripted2referstotheentiregroup
ofatomswithintheparenthesesthatis,thechemicalformulaimpliesoneCa2+ionandtwoNO3ions.

Toillustratethedifferencebetweentheuseofsubscriptednumbersandnumbersofnormalcase,consider
thefollowingchemicalreaction,whichdescribessolidCa(NO3)2dissolvinginwatertoformitsconstituent
ions.
Notethatsubscriptsareusedonlywhenwearereferringtothenumberofconstituentatomsorionswithin
anelementorcompoundinotherwords,theyappearinchemicalformulaeonly.Conversely,normalcase
numbersareusedascoefficientstodescribethenumberofatoms,ionsormoleculespresentinaparticular
chemicalreaction.Thiswillbecoveredinmuchgreaterdetailinchapter3.

PRACTICEEXERCISE2.10
Writethechemicalformulaeforthecompoundsresultingfromall
possiblecombinationsofthefollowingcationsandanions(16
compoundsintotal).

Ifcalciumnitrate,awhitecrystallinesolid,isexposedtomoistair,itabsorbswaterandformsahydrate.
ThishydrateisalsoawhitecrystallinesolidbutithasthechemicalformulaCa(NO3)24H2O.Thisprocess
canbereversedbyheatingthehydrateundervacuumtoremovethewatermolecules,whichresultsinthe
formationofanhydrousCa(NO3)2(anhydrousmeansthatthecompoundcontainsnowatermolecules).The
formationofhydratesisrelativelycommonamongioniccompounds,anditisusualtowritethewater
moleculesinsuchcompoundsattheendofthechemicalformula.

Themajorityofcovalentcompoundsarecarbonbasedorganiccompounds,thechemicalformulaeofwhich
areoftenwrittenwithcarbonfirst,followedbyhydrogenandthentheremainingelementsinalphabetical
order(e.g.C2H6O,C4H9BrO,CH3Cl).Themajorshortcomingofachemicalformulaisthatittellsuslittleor
nothingaboutthestructureofthecompoundinquestion.Toobtainthisinformation,werequirestructural
formulae.

StructuralFormulae
Chemistsareinterestedinthewayinwhichatomsarebondedtogethertoformmolecules.Whilemolecular
formulaeareusefulintellingusthechemicalmakeupofmolecules,theyonlyrarelygiveusanyideaof
whichatomisbondedtowhich.Forexample,themolecularformulaofwaterisalwayswrittenasH2O,but
thistellsusnothingabouthowtheatomsarearrangedinthemolecule.Wecannottellfromthemolecular
formulaalonewhichofthethreepossiblearrangementsofatomsbelowisthecorrectoneforH2O.

Structuralformulaeattempttoshowthewayinwhichtheatomsinamoleculearebondedtogether,
therebygivingussomestructuralinformation.Thechemicalsymbolsarestillusedforeachelementpresent,
butnowtheconstituentatomsareplacedintheorderinwhichtheyarebondedtogetherandthebonds
betweenneighbouringatomsarerepresentedaslines.Asinglelinerepresentsasinglebond,which,aswe
willseeinchapter5,consistsofapairofelectrons.Considerforexampletheammoniamolecule,NH3.We
canshowthewayinwhichthefouratomsarebondedtogetherinthismoleculebydrawingthestructural
formulaasfollows.
Fromthisdepiction,itisobviousthatthenitrogenatomisbondedtothreeHatomsbysinglebonds.Itis
alsocommontoseeammoniadepictedas:

whichgivesusthesamestructuralinformationasthepreviousdiagram(theNatomisbondedtothreeH
atomsbysinglebonds),butshowsthemoleculeapparentlyadoptingaslightlydifferentgeometry.This
illustratesanimportantpointaboutstructuralformulae:structuralformulaedonotnecessarilyshowthe
correctgeometryofacompound,simplybecauseitisdifficulttoaccuratelyrepresentthreedimensional
moleculesintwodimensions.Whilebothofthedepictionsonthepreviouspagecorrectlyshowallofthe
bondsinthemolecule,neitherisstrictlycorrectfromastructuralpointofviewastheydonotshowthe
actualthreedimensionalarrangementoftheatoms.Bothofthemalsoneglectthefactthatthereisapairof
electronsontheNatomwhichdoesnotparticipateinbonding.Thisistermedalonepairofelectrons.While
suchelectronsareoftenignoredindepictionsofmolecules(theirpresenceisusuallyimpliedbythe
chemicalformula),theycanhavesignificantstructuralconsequences.Wherenecessary,theycanbeshown
asfollows.

Inlaterchapters,youwillfinditcanbeimportanttoshowlonepairsonatoms,especiallywhenyoudraw
organicreactionmechanisms,whichshowthemovementofelectronsinbondmakingandbondbreaking
processes.Evenwiththeinclusionofthelonepair,thisisstillnotanaccuratedepictionoftheammonia
moleculeinathreedimensionalsense,butitshowsthecorrectconnectionsbetweentheconstituentatomsof
themolecule.Wewillseelaterhowtointroducethreedimensionalelementsintostructuralformulae.

Itisintheworldoforganicchemistrythatstructuralformulaeareparticularlyuseful.Whilemanycovalent
inorganiccompoundstendtobesmallmoleculesinwhichasinglecentralatomisjoinedto2,3,4,5or6
surroundingatoms,organicmoleculestendtoexistasringsandchains,andhaveahugevarietyofpossible
geometries.Thisisduetotheunusualpropensityofcarbonatomstobondtothemselves,apropertycalled
catenation,whichcanleadtotheformationofmassivemolecules.Eachcarbonatominamoleculecan
formbondstoasmanyasfourothercarbonatoms,whichmeansthatevenrelativelysmallorganic
moleculeshavemanydifferentpossiblewaysinwhichtheconstituentatomscanbebondedtogether.
Structuralformulaeallowustodepictthesepossibilities.

Carbonisatetravalentelement,meaningthatitpreferstoformatotaloffourbondswithinamolecule.
Thesebondsmaybesingle,doubleortriple.Thismeansthattherearefourdifferentwaysthatacarbon
atomcanformatotaloffourbonds:foursinglebonds,twodoublebonds,adoublebondandtwosingle
bonds,oratriplebondandasinglebond.Hydrogen,ontheotherhand,ismonovalent,meaningthatit
usuallyformsonlyonesinglebondtoanotheratomand,inanorganicmolecule,thisismostoftentoa
carbonatom.Thiscanbeillustratedbythepropanemolecule,whichhasthechemicalformulaC3H8.Given
thateachCatommustformfourbondsandeachhydrogenatommustformone,thereisonlyonepossible
wayofattachingalltheelementsthisisshowninastructuralformulabelow.

Wecanseefromthisthatthethreecarbonatomsofapropanemoleculelinktoformachaininwhicheach
carbonattheendofthechain(calledaterminalcarbon)issinglybondedtothreehydrogenatoms,andthe
innercarbonissinglybondedtotwohydrogenatoms.Noticethatthestructuralformulaofpropanecontains
moreinformationthanthechemicalformula.Bothformulaeidentifythenumberofatoms(threeCatoms
andeightHatoms),butthestructuralformulaalsoshowshowtheatomsareconnected.

ThepropanemoleculecontainsonlyCCandCHsinglebonds.Itisalsopossibletohavedoublebonds
andtriplebondsinorganicmolecules,whichwedesignatebytwoandthreelinesrespectively,asshownin
figure2.8.

FIGURE2.8Depictionsofsingle,doubleandtriplebondsbetweencarbonatoms.

Structuralformulaecanremoveambiguitiesinherentinchemicalformulae.Forexample,theethanoland
dimethylethermoleculeshavethesamechemicalformula,C2H6O.However,thestructuralformulae
depictedinfigure2.9clearlyshowthedifferencesinthewaytheatomsareconnectedwithinthemolecules.

FIGURE2.9Structuralformulaeofdimethyletherandethanol.Bothmoleculeshavethesamechemicalformula,
C2 H6 O.

Moleculessuchasthesethathavethesamechemicalformulabutdifferentchemicalstructuresarecalled
isomers.Structuralformulaeareaconvenientwaytodistinguishbetweenisomers.

Twotypesofshorthandstructuralformulaearecommonlyused.Theconstituentatomsincondensed
structuralformulaearearrangedinbondedgroups,andtheactualbondsarenotdrawn.Forexample,we
wouldwritethecondensedstructuralformulaeofdimethyletherandethanolasCH3OCH3andCH3CH2OH
respectively,whichessentiallygivesusthesamestructuralinformationasthestructuralformulae,butwitha
significantsavingofspace.Notethatthecondensedstructuralformulaeattempttoshowtheorderinwhich
theatomsarebondedtogether,anddifferfromthechemicalformula,whichisC2H6Oinbothcases.
Condensedstructuralformulaecanalsobedrawnformorecomplexmoleculessuchas2methylpropane,
C4H10.

ThecondensedstructuralformulaofthismoleculecanbewrittenasCH3CH(CH3)CH3,(CH3)2CHCH3or
(CH3)3CH,allofwhichareequivalent.Inthesecases,anyCH3groupinparenthesesisunderstoodtobe
bondedtothemiddlecarbonofthelongestcarbonchain.

Wecanalsouselinestructures,inwhichCatomsarenotdrawnexplicitly,todepictmolecules.Line
structuresareconstructedaccordingtothefollowingguidelines:
1.AllbondsexceptCHbondsareshownaslines.
2.CHbondsandHatomsattachedtocarbonarenotshowninthelinestructure.
3.Singlebondsareshownasonelinedoublebondsareshownastwolinestriplebondsareshownas
threelines.
 4.Carbonatomsarenotlabelled.Allotheratomsarelabelledwiththeirelementalsymbols.Following
theseguidelines,wewouldthenwritethelinestructureofpropane,C3H8,as:

Inthisdiagramacarbonatomisimpliedateachendofthechainandatthekinkinthechain.Thecarbon
atomsaresinglybondedtoeachotherand,astherearenootherelementalsymbolsinthestructure,itis
assumedthateachcarbonatombondstotheappropriatenumberofhydrogenatomssothatitformsatotal
offourbonds.Thismeanstheterminalcarbonatomswillbondtothreehydrogenatomsandthecentral
carbonatomwillbondtotwohydrogenatoms.Weillustratehowtodrawlinestructuresfurtherinworked
example2.7.

WORKEDEXAMPLE2.7

Drawinglinestructures
Constructlinestructuresforcompoundswiththefollowingstructuralformulae.

Analysis

Weareaskedtoconvertthestructuralformulaeabovetolinestructures.Todothis,wesimply
applytheguidelinesgivenpreviously.

Solution

Usingguidelines1and2,weremoveallCHbondsandHatomsattachedtoCatomsfromthe
structure,therebyleavingthecarbonbasedframeworkofeachmolecule(rememberthatMe=
CH3).Guideline3statesthatdoublebondsremainastwolines.Thisgivesusthefollowing:

ThefinalguidelinetellsustoremovethelabelsforallCatoms.Thisgivestheanswer:

Isouranswerreasonable?
 Tocheckthatthelinestructuresrepresentthecorrectsubstances,countthenumberof
intersectionsandlineends,whichshouldequalthenumberofCatomsinthecompound.Thefirst
linestructurehasfive,thesecondhasthreeandthethirdhasfive,matchingthechemical
formulae.Thereforeouranswersappearcorrect.

Youshouldbefamiliarwithlinestructures,andyoushouldbeabletoconvertfromastructuralformulatoa
linestructure,andfromalinestructuretoastructuralformula.Todothelatter,keepinmindthatcarbon
atomsarenotshowninalinestructure,sothefirststepistoplaceaCateverylineintersectionorkinkand
attheendofeveryline.Thenaddsinglybondedhydrogenatoms(H)untileverycarbonatomhasfour
bonds.

WORKEDEXAMPLE2.8

ConvertingLineStructures
Drawthestructuralformulaeanddeterminethechemicalformulaeofthemoleculesinthe
followinglinestructures.

Analysis

WeknowthatlinestructuresshowallstructuralfeaturesexceptcarbonatomsandCHbonds.
Wecanthereforeconvertalinestructureintoastructuralformulaintwosteps.First,placeaCat
anyunlabelledlineendandateachlineintersectionorkink.Second,addhydrogenatomsuntil
eachcarbonatomhasfourbonds.Thechemicalformulaisthenobtainedbycountingthenumber
ofatomsofeachelement.

Solution

BeginbyplacingaCateachintersection,kinkandlineend.

Nowaddhydrogenatomsuntileachcarbonatomhasatotaloffourbonds.Eachcarbonatomin
thefirststructurealreadyhastwobonds,soeachneedstwohydrogenatoms.Thisgivesthe
structuralformula:

andthechemicalformulaC2H4Cl2.

Thesecondstructurehasfourcarbonatoms.Thetwoterminalcarbonatomshavejustonebond,
soeachneedsthreehydrogenatoms.Thecarbonwiththedoublebondtooxygenalreadyhasits
 completesetoffourbonds.TheotherinnercarbonatomhasabondtoCandabondtoO,soit
needstwohydrogenatoms.Thisgivesthestructuralformula:

andthechemicalformulaC4H8O2.

Thethirdstructurecontainsatriplebond.Theterminalcarbonatomneedsonehydrogenatom,
buttheothercarbonatomofthetriplebondalreadyhasfourbonds.Thenextcarbonatomhas
twobonds,onetocarbonandonetooxygen.Twohydrogenatomsareneededtogivethisatom
fourbonds,andthisgivesthestructuralformula:

andthechemicalformulaC3H4O.

Isouranswerreasonable?

Checktheconsistenciesofthestructuralformulaebycountingthenumberofbondsassociated
witheachcarbonatom.Ifyouhaveconvertedthelinestructurecorrectly,eachcarbonatomwill
havefourbonds.

PRACTICEEXERCISE2.11
Convertthefollowinglinestructureinto
structuralandchemicalformulae.

Whilelinestructuresarethebasisforthedepictionofmostmoleculesinthechemicalliterature,itis
commontoseevariationsontheruleswehaveoutlinedpreviously.Forexample,wemightseebutane,
C4H10,writtenasanyofthefollowing:

Alloftheseareacceptablealternativesforthestrictlycorrectdepictionshownbelow.

Noticealsothatinmoleculeswithnodoubleortriplebonds,thecarbonchaincanbedrawninany
orientation.Thefollowingequivalentlinestructurescanbedrawnforpentane,C5H12:
butthefirsttwoofthesewouldbemostcommonlyseen.

Thedepictionofmoleculesaslinestructurescangiverisetosomeveryinterestingshapes,andsomeof
thesehaveservedasinspirationsforthesynthesisofparticularmolecules.Consider,forexample,the
moleculesbelow,allofwhichhavebeensynthesised.

Probablythemostremarkableexampleofmolecularsynthesisinspiredbylinestructuresistheseriesof
moleculescalledNanoputians,whichwerereportedin2003byDrStephanieChanteauandProfessorJames
TourfromRiceUniversityintheUSA.Thesearemoleculesthat,whendrawnaslinestructures,resemblethe
humanform.TwoexamplesofNanoputians(namedaftertheLilliputiansinJonathanSwift'sGulliver's
Travels)areshowninfigure2.10.Hadwechosentodescribethesewiththeirchemicalformulae(C39H42O2
andC38H44O2forNanoKidandNanoBalletDancerrespectively)wewouldhavenoideaofthedelightful
shapesthatrepresentationsofthesemoleculesdisplay.
 FIGURE2.10 Linestructuresof:
(a)NanoKid
(b)NanoBalletDancer.

ThreedimensionalStructures
Whilethestructuralformulaeencounteredsofargivemorestructuralinformationthanchemicalformulae,
theydonotnecessarilygiveacompleterepresentationofamolecule.Forexample,noneofthemolecules
shownpreviouslyareflat,butyouwouldnotknowthisfromlookingatthestructuralformulae.Wemust
thereforeattempttointroducesomeaspectsofthreedimensionalityinourrepresentations.Therearea
numberofwaysthiscanbedone.

ThreedimensionalStructuralFormulae
Thesimplestwayofdrawingathreedimensionalstructureintwodimensionsistouseastructuralformula
orlinestructureasabase,andthenaddsomeperspective.Thisisillustratedbelowusingthemolecule1,2
dimethylcyclopentane.Thisisacyclicmoleculeconsistingofapentagonofcarbonatoms,withCH3
groupsattachedtotwoadjacentcarbons.Wecandrawthelinestructureasfollows.

However,whenthismoleculeisviewedinthreedimensionsfromsideon,wecanimmediatelyseethatthe
flatlinestructureisnotanadequaterepresentationeachcarbonatomintheringhastwoattachedatoms,
eithertwoHatomsoraHatomandtheCatomofaCH3group,whichpointeitheraboveorbelowthe
planeofthering.ThisleadstotwopossiblerelativearrangementsoftheCH3groupswithinthemolecule
eitherbothonthesamesideofthering,oronoppositesidesandhencetwopossibleisomersnamed
usingtheprefixescisandtrans(seefigure2.11).

FIGURE2.11Representationsofthetwopossibleisomersof1,2dimethylcyclopentane.ThetwoCH3 groups
maybearrangedsothattheyareoneitherthesameoroppositesidesofthering.Inreality,the
cyclopentaneringsarenotflatbutslightlypuckered.

ThecisisomerhasbothCH3groupsonthesamesideofthering.(Notethatitdoesnotmatterwhether
theyarebothonthetoporbottomsideoftheringthesamecompoundresults.)TheCH3groupsareon
oppositesidesoftheringinthetransisomer.Wecanshowthisinourlinestructurebydrawingthebondsto
thesegroupsaswedges.Asolidwedge( )representsabondcomingoutofthepagetowardsthe
observer,whileahashedwedge( )representsabondgoingbackintothepage.Anormallineisusedfor
bondsintheplaneofthepage.Thereforethetwoisomerscanbedrawnaslinestructuresasfollows:
anditcanbeeasilyseenthattheyaredifferentcompounds.

Whencarbonisbondedtofouratoms,thoseatomsgenerallyadoptatetrahedralarrangementaroundthe
carbonatom,asthisarrangementplacesthemasfaraspossibleawayfromeachother.Itisconventionalto
drawthethreedimensionalnatureofthefourbondsaroundasinglecarbonatomasfollows:

whereXisanyatom.Inthisrepresentation,onebondgoesintotheplaneofthepage,onecomesoutofthe
planeofthepage,andtwolieintheplaneofthepage.Wecanshowthethreedimensionalityofmolecules
containingmorethanonecarbonatombyjoiningtheseindividualunitstogether.Suchthreedimensional
depictionsarenotlimitedtoorganiccompoundswewillseeinchapter13thattransitionmetalcomplexes
candisplayawidevarietyofgeometries,andwecanuseanalogousdiagramstoportraythese.Forexample,
itiscommontohavesixatomsboundtoatransitionmetaliontogiveacomplexofgeneralformulaML6.
EachLatomsitsatthecornerofanimaginaryoctahedroninwhatiscalledanoctahedralgeometry.We
woulddrawsuchanarrangementasfollows.

Inthiscasewehavethetwoverticalbondsintheplaneofthepage,whiletwobondsgointotheplaneand
twobondscomeoutoftheplane.Whileitispossibletomakeremarkablydetailedthreedimensional
drawingsusingonlyapenandpaper,itiseasiertousecomputerstodrawsomewhatmorerealistic
depictionsofmolecules.

BallandstickModels
Inaballandstickmodel,ballsofarbitrarysizerepresentatomsandsticksrepresentchemicalbonds.Figure
2.12showsaballandstickmodelofpropane.Theballsareusuallydrawnindifferentcolourstodistinguish
betweendifferentelementspresentinthemolecule(seefigure2.13).Suchmodelsgenerallyenabletheeasy
visualisationofthreedimensionalfeaturesofthemolecule.

FIGURE2.12Ballandstickmodelofpropane,C3 H8 .
 FIGURE2.13Thecoloursandsizesofballsusedtorepresentatomsinthisbook.

SpacefillingModels
Whileballandstickmodelsareuseful,theyarefarremovedfromrealitychemicalbondsarenotsticks,
andthesizeofatomsisbynomeansarbitrary.Aspacefillingmodelrecognisesthatamoleculeisdefined
bythespaceoccupiedbyitselectrons,andattemptstorepresenttherelativesizeofatomswithinamolecule
byshowingthesizeofeachatom'selectroncloud.RecallfromRutherford'sgoldfoilexperiment(pp.78)
thatelectroncloudsmakeupnearlytheentirevolumeofanyatom.Eachatominaspacefillingmodelis
shownasadistortedsphererepresentingthevolumeoccupiedbyitselectrons.Thesespheresmergeintoone
anothertobuilduptheentiremolecule.Aspacefillingmodelcantellusataglancewhethertheelectron
cloudsofatomsinamoleculeoverlap,andthereforewhetherthoseatomsarebondedtogetherornot.Figure
2.14showsaspacefillingmodelofpropanenoticethatthespheresoftheneighbouringCatomsoverlapto
asignificantextent,implyingtheseatomsarebondedtogether.ThepresenceofCHbondsisalsoobvious
fromtheoverlapofthespheresrepresentingCandH.Figure2.15showsballandstickandspacefilling
modelsofseveralchemicalcompoundscommonineverydaylife.

FIGURE2.14Spacefillingmodelofpropane,C3 H8 .

FIGURE2.15Differentrepresentationsofsomecommoncompounds.
OtherRepresentations
Itisofteninconvenient,ifnotimpossible,toshoweveryatominalargemoleculesuchasaproteinor
nucleicacid,anditisusualtodrawcartoontypestructuresofsuchmolecules.Figure2.16showssucha
viewofhaemoglobin,theironcontainingproteinthatcarriesoxygeninhumanblood.Insteadofshowing
eachindividualatominthemolecule(C2952H4664N812O832S8Fe4isthemolecularformulaofoneformofthe
protein),theproteinchainsareshownasribbonswhichfoldinparticularwaysdependingontheir
chemicalenvironment.

FIGURE2.16Arepresentationofthestructureofhaemoglobinshowingfourhaemgroups(colouredspheres).The
differentcolouredribbonsdenotedifferentpartsoftheprotein.

Stereoviewsareoftenhelpfulinvisualisinglargemolecules,astheyallowtheimagetobeviewedinthree
dimensions,althoughviewingthemproperlyrequiressomepractice.AnexampleofastereoviewofDNAis
showninfigure2.17.
 FIGURE2.17StereoviewofDNA.

Toviewstereoviews(whicharethreedimensionalimages),youmustbeabletogocrosseyed.Youwill
eventuallyfindthat,withlotsofpractice,athreedimensionalimageappearsinthemiddleofthetwo
structuresinfigure2.17.Ifyoudonotgetitthefirsttime,keeptrying!

Whichofourvariousdepictionsisthecorrectone?Theanswerisnoneofthem.Atomsarenotfinite
colouredspheresandbondsarenotsticksattachedtoatoms.Therepresentationsweuseinchemistryare
merelyattemptstovisualisethingsthat,inallprobability,areimpossibletodepict.However,thisisnotto
saythatourrepresentationsareuseless.Aswewillseethroughoutthisbook,wecanunderstandmany
importantfacetsofmolecularstructurethroughstudyingtheserepresentations.Butkeepinmindatalltimes
thattherepresentationsaremodelsnothingmoreandnothingless.

MechanisticArrowsinChemicalReactions
Inadditiontorepresentingthestructuresofmolecules,wealsowanttobeabletodepictthewayinwhich
chemicalbondsarebrokenandformedwithinandbetweenchemicalspeciesaschemicalreactionsoccur.
Wedothisbymeansofmechanisticarrows,whichshowthemovementofelectronsinbondbreakingand
bondmakingprocesses.

Atwoheadedmechanisticarrowshowsthemovementofapairofelectrons.Theelectronsmovefromthe
tailtotheheadofthearrow,resultinginanumberofpossiblechemicalprocesses,someofwhichare
detailedbelow.

BondBreaking
Considerthefollowingbondbreakingprocess:

Inthiscase,thearrowstartsatthemiddleofthebond.Thebondbreaksinaheterolyticfashion,withboth
electronsendingupontheClatom.ThisgivesrisetotheformationofanH+cation(proton)andaClanion.

BondMaking
Considerthefollowingbondmakingprocess:

Here,abondisformedbetweenthecarbonylOatomandtheH+ion,withthetwoelectronsinthebond
comingfromoneofthelonepairsofelectronsonthecarbonylOatom.Thisleavesaformalpositivecharge
ontheOatom.

ChargeNeutralisation
Considerthefollowingchargeneutralisationprocess:

ThepositivelychargedcarbonylOatomcanbeneutralisedbytakingtwoelectronsfromthedoublebond
andlocatingthemonthecarbonylOatom.ThearrowstartshalfwayalongthebondandfinishesattheO
atom.ThisprocessleavesthecarbonylCatompositivelycharged.

Inthefollowingchargeneutralisationprocess

protonlosstogiveaneutralcompoundoccursbytakingthetwoelectronsfromanNHbondandlocating
themontheNatom.ThetailofthearrowthereforeissituatedhalfwayalongtheNHbondandthehead
pointstotheNatom.
Theseexamplesillustratesomeimportantfactsaboutmechanisticarrows.Firstly,thetailofthearrowmust
besituatedatasourceofanelectronpair:thatis,eitherhalfwayalongabondoronalonepairofelectrons.
SomethoughtwillconvinceyouthatthismeansamechanisticarrowcanneverstartateitherH+oranH
atom(averycommonmistake!).Similarly,theheadofthearrowmustbesituatedinaregionabletoaccept
apairofelectrons.Thusitwouldbeunlikely,forexample,fortheheadofanarrowtobeatanegatively
chargedatomorion.Itisimportanttorememberthattotalchargemustbeconservedinanymechanistic
process.Thus,inalltheexamplesabove,bothsidesoftheequationshavethesametotalcharge.Itshould
alsobenotedthatwecanusemorethanonearrowtorepresentmultiplesimultaneousbondmakingand
bondbreakingprocesses.Thisisillustratedbelow.

Here,threeprocessesoccuressentiallysimultaneously.
1.OHremovesaprotonfromaCH group,resultingintheformationofH O.
3 2
2.ThepairofelectronswhichwereintheCHbondmovesoastogiveaC Cdoublebond.
3.TheCBrbondbreaksheterolytically,withbothelectronsinthebondmovingtotheBr,togiveaBr
ion.

Asingleheadedarrowshowsthemovementofasingleelectron.Sucharrowsareusuallyfoundonlyin
reactionsinvolvingradicals,chemicalspecieswhichcontainoneormoreunpairedelectrons.Anexampleis
givenbelow,inwhichtheBrBrsinglebondisbrokeninahomolyticfashion,suchthateachofthe
bondedatomsreceivesanelectron,givingtwobromineradicals.

Youwillmakeextensiveuseofmechanisticarrowsinthelaterchaptersofthisbook,especiallyinwriting
organicreactionmechanisms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.3Nomenclature
Representingmoleculesasimagesallowsustoimpartagreatdealofinformationconcerningmolecularstructure.
Butmoleculescanalsobenamed,andthereareoccasionswhenthisismoreconvenientthandrawingapicture.In
theearlydaysofchemistry,thelistofknowncompoundswasshort,andchemistscouldmemorisethenamesofall
ofthem.Newcompoundswereoftennamedbytheirdiscovereraftertheirplaceoforigin,physicalappearanceor
properties.Today,morethan50millioncompoundsareknownandmillionsmorearesynthesisedeachyear.
Chemistsconsequentlyneedsystematicproceduresfornamingchemicalcompounds.TheInternationalUnionof
PureandAppliedChemistry(IUPAC)hasestablisheduniformguidelinesfornamingvarioustypesofchemical
substances,andchemistsincreasinglyuseIUPACapprovednamesratherthantheircommoncounterparts.Inthis
sectionwewillintroducetherulesfornomenclature,thesystemforthenamingofcompounds.Youwillencounter
manychemicalnamesinsubsequentchapters,andthebasicsthatyoulearninthissectionwillaidyourinterpret
ationofthesenames.Wewillinvestigatethenamingoftransitionmetalcomplexesinchapter13.Youshouldbe
awarethattherearesomecompoundsthatarebetterknownbytheircommon,unsystematicname,andnottheir
systematicIUPACname.Thebestexampleofthisiswater,thesystematicnameofwhichisoxidane.Unsystematic
namesforasmallnumberofcommoncompoundsareacceptedbyIUPAC.

ChemistryResearch

IUPAC

AssociateProfessorRichardHartshorn,UniversityofCanterbury

TheInternationalUnionofPureandAppliedChemistry(IUPAC)istheorganisationresponsiblefor
helpingchemiststalktoeachotherabouttheirscience.Itdoesthisbydevelopingandsystematisingthe
nomenclature,symbolsandterminologythatarerequiredforchemistry.Thenamesandformulaeof
chemicalcompoundsarecentraltothelanguageofchemists,andrulesarerequiredtotellpeoplehowto
putthemtogetherandworkoutwhattheymean.Therulesareregularlyupdated,bothtomakethem
simpler,andtoprovidewaysofnamingnewkindsofmoleculesthatwerenotenvisagedwhentherules
werefirstwritten.

Differentsetsofrulesarerequiredfordifferentkindsofcompounds.Forexample,organiccompounds
andmetalcomplexesarenamedindifferentways.ThedifferentsetsofrulesappearinIUPAC'scolour
books,including:
theRedBook(NomenclatureofInorganicChemistry)(figure2.18)
 FIGURE2.18TheRedBookisoneofIUPAC'srulebooksfornomenclature,symbolsandterminology.
theBlueBook(NomenclatureofOrganicChemistry)
theGreenBook(Quantities,UnitsandSymbolsinPhysicalChemistry)
thePurpleBook(CompendiumofMacromolecularNomenclature)
theGoldBook(CompendiumofChemicalTerminology).
RichardHartshorn,AssociateProfessorintheDepartmentofChemistryattheUniversityofCanterbury,
Christchurch,workswithIUPACtodevelopnomenclatureforinorganiccompoundsnomenclature
rulesarenotdevisedsolelybychemistsfromthenorthernhemisphere!

Hartshorndescribeshimselfasacoordinationchemistbyinclinationandbytraining.Hesayshelikes
makingnewcompounds(prettycolours!)andfindingoutwhatreactionscanbedoneonthem.Inhisown
words:

Ofcourse,oncecompoundshavebeenmade,wehavetonamethem.Asacoordination
chemist,thismeansknowinghowbothorganiccompoundsandinorganiccompoundsare
named.WorkingwithIUPACallowsmetohavesomeinputintotherecommendationsfor
namingcompounds.

Igotintonomenclaturethroughoneofmyresearchprojects,whichinvolvedpreparingand
studyingcomplexesofnewaminoacids.Itturnedoutthattheconventionalnomenclature
thatwasavailablewasnotparticularlyconvenienttohighlightthedifferencesandsimilarities
betweenthevariouscomplexesthatwehadmade.Thesimpleanswerwastoinvent
somethingnew,andwepublishedanarticleshowinghowthisnomenclaturecouldbeused
moregenerallyforanylinearorbranchedchainligandswrappedaroundanoctahedral
centre.ThearticlewasseenbysomeofthepeopledoingnomenclatureworkwithIUPAC.
Theywereonthelookoutforanyoneshowinganinterestinnomenclatureandits
 development,andapproachedmetoseeifIwasinterestedinjoiningtheirgroup.

Verysoonafterthat,IfoundmyselfpartofthesmallteampreparingtherevisionoftheRed
Book.Ittookmorethanfiveyears'ofconsultation,andwritingandrevisingthetext,in
responsetocommentsfromnomenclatureexperts,beforethenewrecommendationswere
completedandreadyforpublication.Tofindit,lookupNomenclatureofInorganic
Chemistry,Recommendations2005byNGConnelly,TDamhus,RMHartshornandAT
Hutton,RoyalSocietyofChemistry,Cambridge,inyourlibrarycatalogue.Ifitisnotthere,
tellyourlibrarianthatitshouldbe!Isaythatbecauseitreallyshouldbe,notbecauseIhavea
vestedinterestIdon'tgetanyroyalties!

Youcanalsofinditonline,throughtheIUPACwebsite:
www.iupac.org/publications/books/rbook/Red_Book_2005.pdf.

Newnomenclatureisbeingdevelopedallthetimefornewcompounds,andsometimesevenforoldones.
IUPACiscurrentlydevelopingrecommendationsforpreferredIUPACnames(PINs).Mostcompounds
canbenamedinmorethanonesystematicway.ThePINsrecommendationsarebeingdevelopedtohelp
insituationswhereitisreallyimportantthateveryoneusesthesamename(suchasinhealthandsafety,
patentlaw,taxationandotherregulatoryareas).Chemistswillstillbefreetousethecurrentrangeof
systematicnomenclatures,butPINsmayberequiredforparticularsituations.

NamingInorganicCompounds
Thewayinwhichwenameinorganiccompounds(i.e.thosenotcomposedprimarilyofcarbonandhydrogen)
dependstosomeextentontheexactnatureofthecompoundinquestion.Wewillexaminethedifferentpossible
typesofinorganiccompoundsinthefollowingpages.Youshouldappreciatethatwhatfollowsis,ofnecessity,an
abbreviatedversionoftheIUPACrulesfornaminginorganiccompounds.Thefullversionmaybefoundatthe
IUPACwebsite(www.iupac.org).

NonmetallicBinaryCompounds
Thewrittennameofacompoundincludesthenamesoftheelementsitcontainsandinformationaboutthenumber
ofatomsofeachelementpresent.Theelementshavetooccurinsomeorder,andthisissetbythesameguidelines
asforthechemicalformula(seep.36).Namescancontainelementalnames,rootsderivedfromelementalnames
andprefixesindicatingthenumberofatomsofeachelement.Tables2.4and2.5listthemoreimportantrootsand
prefixesthatappearinthenamesofnonmetallicbinarycompounds,compoundsthatcontainonlytwoelements,
neitherofwhicharemetals.
TABLE2.4 CommonRootsforNamingCompounds
Element Fullname Root
As arsenic arsen
Br bromine brom
C carbon carb
Cl chlorine chlor
F fluorine fluor
H hydrogen hydr
I iodine iod
N nitrogen nitr
O oxygen ox
 P phosphorus phosph
S sulfur sulf

TABLE2.5 NumberPrefixesforChemicalNames
Number Prefix Example Name
1 mono CO carbonmonoxide(a)
2 di SiO2 silicondioxide
3 tri NI3 nitrogentriiodide
4 tetra SnCl4 tintetrachloride
5 penta PCl5 phosphoruspentachloride
6 hexa SF6 sulfurhexafluoride
7 hepta IF7 iodineheptafluoride

(a)Thefinalooftheprefixisomittedinthiscase.

Wecansummarisetherulesfornamingnonmetallicbinarycompoundsinfourguidelines:
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthesamegroupof
theperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffixide.Some
commonrootsarelistedintable2.4.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelementusuallycontains
aprefixthatspecifiesthenumberofatomspresent.Commonprefixesaregivenintable2.5.

Numericalprefixesareessentialinnamingsimilarbinarycompounds.Forexample,nitrogenandoxygenformthe
sixdifferentcompoundsshownasspacefillingmodelsinfigure2.19:NO,nitrogenmonoxideNO2,nitrogen
dioxideN2O,dinitrogenoxideN2O3,dinitrogentrioxideN2O4,dinitrogentetraoxideandN2O5,dinitrogen
pentaoxide.

FIGURE2.19Spacefillingmodelsofthesixcompoundsformedbetweennitrogenandoxygen.

WORKEDEXAMPLE2.9

Namingbinarycompounds
Namethefollowingbinarycompounds:SO2,CS2,BCl3andBrF5.

Analysis

Noneofthesecompoundscontainsametallicelement,soweapplytheguidelinesfornonmetallicbinary
compoundnomenclature.

Solution
 Namethefirstelement,usearootplusideforthesecondelementandindicatethenumberofatomswith
prefixes.Therefore,weobtain:

SO2:sulfurdioxide

CS2:carbondisulfide

BCl3:borontrichloride

BrF5:brominepentafluoride.

PRACTICEEXERCISE2.12
Namethecompoundsthatcontain:
(a)Fouratomsofbromineandoneatomof
silicon
(b)Threeatomsofoxygenandoneatomof
sulfur
(c)Threeatomsoffluorineandoneatomof
chlorine.

BinaryCompoundsofHydrogen
Hydrogenrequiresspecialconsiderationbecause,aswesawearlier,itmayappearfirstorsecondinthechemical
formulaofacompoundand,asaresult,itmayappearfirstorsecondinthename.Thisisparticularlyevidentinthe
diatomicmoleculesthathydrogenformswithelementsfromgroups1and17,whicharenamedaccordingtothe
guidelinesonthepreviouspage.Forexample,LiHislithiumhydride,andHFishydrogenfluoride.Withelements
fromgroups2and16,hydrogenformscompoundscontainingtwoatomsofhydrogen.Exceptforoxygen,thereis
onlyonecommonlyoccurringbinarycompoundforeachoftheseelements,sotheprefixdiisomitted.Examples
areH2S,hydrogensulfide,andCaH2,calciumhydride.Oxygenformstwobinarycompoundswithhydrogen.These
haveunsystematicnames:oneiswater,H2O(systematicnameoxidane),andtheotherishydrogenperoxide,H2O2
(systematicnamedioxidane).Binarycompoundsofhydrogenwithelementsfromgroups13,14and15have
unsystematicnamesincommonuseB2H6isdiborane,CH4ismethane,SiH4issilane,NH3isammonia(systematic
nameazane)andPH3isphosphine(systematicnamephosphane).Infact,carbon,boronandsiliconformmany
differentbinarycompoundswithhydrogen,andonlythesimplestofthesearelistedhere.

IonicCompounds
Binarycompoundswhichcontainmetalionsareoftenionic,consistingofacationandananion(seechapter1,p.2).
Wenamebinaryioniccompoundswiththecationfirstandtheanion,whichtakesthesuffixide,last.Forexample,
NaClisnamedsodiumchloride,whileKIisnamedpotassiumiodide.CompoundssuchasCaF2,inwhichthe
numbersofcationsandanionsarenotthesame,donotrequiretheactualnumberofcationsandanionstobe
specified.ThusCaF2isnamedcalciumfluoride,notcalciumdifluoride.Thereasonforthisisthatcalciumisagroup
2element,andwillthereforeformonlya2+cation.Thiswillalwayscombinewithtwo1anionstoformaneutral
ioniccompound,andthereforeweneednotspecifydifluoride.Usingthesamereasoning,wecanseethatNa2Sand
MgI2arenamedsodiumsulfideandmagnesiumiodiderespectively.Ioniccompoundscontainingpolyatomicions
suchasNH4+,NO3andSO42areagainnamedwiththecationfollowedbytheanion,butyouwillneedtolearn
boththenamesandthechargesofthecommonpolyatomicionstobeabletoname,andwritechemicalformulaefor,
compoundscontainingtheseions.Table2.6liststhemorecommonpolyatomicions.
 TABLE2.6 Namesandchemicalformulaeofsomecommonpolyatomicions
Formula Name
Cations
NH4+ ammonium

H3O+ hydronium(oxonium)

Hg 22+ dimercury(2+)

Diatomicanions
OH hydroxide

CN cyanide

Anionswithcarbon
CO32 carbonate

HCO3 hydrogencarbonate(bicarbonate)

CH3COO acetate

C2O42 oxalate

Oxoanions
SO42 sulfate

SO32 sulfite

NO3 nitrate

NO2 nitrite

PO43 phosphate

MnO4 permanganate

CrO42 chromate

Cr2O72 dichromate

ClO4 perchlorate

ClO3 chlorate

ClO2 chlorite

ClO hypochlorite

Youcanseefromthistablethatthereareasignificantnumberofanionscontainingacentralatomsurroundedby
oxygenatoms.Suchionsarecalledoxoanions,andtheirnamescanbededucedusingthefollowingrules:
1.Thenamehasaroottakenfromthenameofthecentralatom(forexample,carbonate,CO 2,andnitrite,
3
NO2).
2.Whenanelementformstwodifferentoxoanions,theonewithfeweroxygenatomsendsinite,andtheother
endsinate(forexample,SO32,sulfite,andSO42,sulfate).
3.Chlorine,bromineandiodineeachformfourdifferentoxoanionsthataredistinguishedbyprefixesand
suffixes.Thenomenclatureoftheseionsisillustratedforbromine,butitappliestochlorineandiodineaswell:
 BrO,hypobromiteBrO2,bromiteBrO3,bromateandBrO4,perbromate.
4.Apolyatomicanionwithachargemorenegativethan1mayaddH+togiveanotheranion.Theseanionsare
namedfromtheparentanionbyaddingthewordhydrogen.Forexample,HCO3ishydrogencarbonate,
HPO42ishydrogenphosphateandH2PO4isdihydrogenphosphate.

NamingOrganicCompounds
Organiccompoundsarecomposedprimarilyofcarbonandhydrogenatoms,andthenamingsystemusedisbased
onthenumberofcarbonatomsintheparticularmolecule.Notsurprisingly,thereareanenormousnumberofrules
fornamingorganiccompoundsandatthisstagewewillrestrictourselvestothebasics.Indeed,computerprograms
arenowabletogeneratenamesfromnearlyanystructuraldiagram,providingahelpfulsupplementtoknowledgeof
therulesofIUPACnomenclature.

FunctionalGroups
Theconceptoffunctionalgroupsunderpinsalloforganicchemistryandmakesitthesystematicdisciplinethatitis.
Afunctionalgroupissimplyagroupofoneormoreatomswithinamolecule,bondedtogetherinaparticular
fashion,andisusuallythepointofreactionwithinamolecule.Organicmoleculesarealsonamedprimarily
accordingtothefunctionalgrouporgroupstheycontain.Thepowerofthefunctionalgroupconceptisthat
moleculescontainingthesamefunctionalgrouptendtobehaveinchemicallysimilarways,andthisallowsusto
predicttheirreactivitytowardsparticularreagentswithsomeconfidence.Forexample,althoughthetwomolecules
belowlookquitedifferent,theybothcontainthealdehydefunctionalgroup,CHO.

Wecanthereforepredictthatbothmoleculeswillundergoareactioncalledoxidation,inwhichtheCHOgroupis
convertedtoaCOOH(carboxylicacid)functionalgroup.Similarly,bothcompoundswillreactwithspeciescalled
reducingagents,whichwillconverttheCHOgrouptoaCH2OH(primaryalcohol)group.(Wewilllearnalot
moreaboutthespecificreactionsinvolvedlaterinthistextbook.)

Itthereforemakessensetonameorganiccompoundsaccordingtotheirfunctionalgroups,andwewilllearnhow
thisisdoneonthefollowingpages.Butfirst,thecommonfunctionalgroupsthatyouwillencounterareoutlinedin
table2.7.NotethatRisacommonlyusedsymboltodenoteeitheraHatom,oranalkylgroup(table2.9,p.55).
Youshouldbeabletoidentifythepresenceofeachofthesefunctionalgroupsinanymolecule.
TABLE2.7 CommonFunctionalGroups
Functionalgroup Nameofgroup Foundin R=

hydroxyl alcohols C

carbonyl aldehydes CorH

carbonyl ketones C
 carboxyl carboxylicacids CorH

Alcohols

TheOH(hydroxyl)groupispresentinallalcohols.Itisattachedtoacarbonatom,whichitselfmaybeattachedto
one,twoorthreeothercarbonatoms(theexceptionismethanol,CH3OH,whichcontainsonlyonecarbonatom).
Alcoholsareclassifiedasprimary(1),secondary(2)ortertiary(3)accordingtothisnumber,asshowninfigure
2.20.

FIGURE2.20Structuralformulaeofprimary,secondaryandtertiaryalcohols.

Wecanalsoclassifycarbonatomswithinmoleculesaccordingtothisscheme.Thusacarbonatomattachedtoone
carbonatom(asinaprimaryalcohol)iscalledaprimarycarbonatom,acarbonatomattachedtotwocarbon
atoms(asinasecondaryalcohol)iscalledasecondarycarbonatom,andacarbonatomattachedtothreecarbon
atoms(asinatertiaryalcohol)iscalledatertiarycarbonatom.

WORKEDEXAMPLE2.10

Writingpossiblestructuresforalcohols
WritecondensedstructuralformulaeforthetwoalcoholswiththemolecularformulaC3H8O.Classify
eachasprimary,secondaryortertiary.

Analysis

WeknowthatalcoholscontaintheOHgroup.Wemustthereforedrawthetwopossiblestructuresof
theformulaC3H8OwhichcontainanOHgroup,rememberingthateachcarbonatominthemolecule
musthavefourbonds.Inproblemslikethis,itisgenerallyeasiesttodrawthestructuralformula,andthen
convertittothecondensedform.

Solution

Wehaveathreecarbonchaininthemolecule,andsotheOHgroupcanbeattachedonlytoeitherthe
terminalcarbon(itdoesnotmatterwhichonethesamecompoundresultsregardlessofwhichendwe
attachthefunctionalgroupto)orthecentralcarbon.Therefore,webeginbydrawingthecarbonchain,
thenattachtheOHgroupinthetwopossiblepositions,andfillinthehydrogenatoms.Doingthisgives
usthefollowingtwocompounds.
 ThecompoundaboveisaprimaryalcoholastheOHgroupisattachedtoacarbonatomdirectly
bondedtoonlyoneothercarbon.

Incontrasttothefirststructure,theabovecompoundisasecondaryalcohol,thecentralcarboninthe
chainbeingbondedtotwoothercarbonatoms.

PRACTICEEXERCISE2.13
Writecondensedstructuralformulaeforthefour
alcoholswiththemolecularformulaC4H10O.
Classifyeachasprimary,secondaryortertiary.

AldehydesandKetones

Aldehydesandketonesbothcontainthesamefunctionalgroup,thecarbonylgroup(C O),buttheydifferinthe
waythatthecarbonylgroupisbondedtotherestofthemolecule.Aldehydesalwayshavethecarbonatomofthe
carbonylgroupbondedtoatleastonehydrogenatom,andthismeansthatthecarbonylgroupofanaldehydemust
alwaysbeattheendofacarbonchain.Conversely,thecarbonatomofthecarbonylgroupinketonesisalways
bondedtotwoothercarbonatoms,andthereforecanneverbeattheendofacarbonchain.Wecanwritethe
aldehydeeitherexplicitlyas:

orasRCHOinacondensedstructuralformula.Thedifferencesbetweenaldehydesandketonesareshowninfigure
2.21.
 FIGURE2.21Structuralformulaeandballandstickmodelsofanaldehydeandaketone.

WORKEDEXAMPLE2.11

Writingpossiblestructuresforaldehydes
WritecondensedstructuralformulaeforthetwoaldehydeswiththechemicalformulaC4H8O.

Analysis

Weknowthatthefunctionalgroupinaldehydescanbeonlyattheendofacarbonchain.Inthiscase,we
havefourcarbonatoms,andtherearetwopossiblewaysofconnectingthesesothattheCHOgroup
liesattheendofachain.

Solution

BeginbywritingtheCHOgroupandthenattachingtheremainingthreecarbonatoms.Wecanconnect
thefourcarbonatomsinastraightchainorabranchedchain.Thetwopossibilitiesareshownbelow.
 PRACTICEEXERCISE2.14
Writecondensedstructuralformulaeforthethree
ketoneswiththemolecularformulaC5H10O.

CarboxylicAcids

Thefunctionalgroupfoundinallcarboxylicacidsisthecarboxylgroup,COOH.Wecanwritethisexplicitlyas:

or,morecommonly,asRCOOH.Asthecarbonatomofacarboxylgroupcanbondtoonlyoneotheratom,carboxyl
groupsarealwaysfoundattheendofacarbonchain.

WORKEDEXAMPLE2.12

Writingpossiblestructuresforcarboxylicacids
WriteacondensedstructuralformulaforthecarboxylicacidwiththemolecularformulaC3H6O2.

Analysis
 Thereisonlyonepossiblecompoundwecandrawhere.Itmustcontainathreecarbonchainwitha
COOHgroupontheend.

Solution

BeginbydrawingtheCOOHgroupandthenattachtheremainingcarbonatoms.Finishbyadding
hydrogenatomssothatallthecarbonatomshavefourbonds.Thisgivesusthecompoundshownonthe
nextpage.

PRACTICEEXERCISE2.15
Writecondensedstructuralformulaeforthetwo
carboxylicacidsthathavethemolecularformula
C4H8O2.

TheNomenclatureofAlkanes
Thenamesofsomeorganiccompoundshavealreadybeenusedinthischapter,butwehavenotyetlearnedhow
thesenamesarederived.Organiccompounds,asmentionedpreviously,arenamedaccordingtotheirfunctional
group.Thefirststepinnamingmostorganiccompoundsistoidentifythefunctionalgroupthattheycontain.
However,wewillbeginbylookingataseriesofcompoundsthatarenotconsideredtocontainanyfunctionalgroup
atall:thealkanes.

Alkanesaremoleculesthatcontainonlycarbonandhydrogenandinwhichcarbonatomsarejoinedbysinglebonds
only.Alkanescanbedividedintotwoclasses,dependingontheoverallgeometryofthecarbonatoms.Alkanesin
whichthecarbonatomsarejoinedinchainsarecalledacyclicalkanesandhavethegeneralformulaCnH2n+2.The
carbonatomsinalkanescanalsobejoinedtogethertoformoneormorerings,andsuchcompoundsarecalled
cycloalkanes.Allalkanesbelongtoagroupoforganiccompoundscalledhydrocarbons,whicharemolecules
composedsolelyofcarbonandhydrogen.Alkanesaresometimescalledsaturatedhydrocarbons,todenotethefact
thatallthecarboncarbonbondsaresingle.Astherearenofunctionalgroupsinalkanes,wenamethemaccording
tothelengthofthelongestcarbonchain.Therearetwopartstothenameofanalkane:aprefix,indicatingthe
numberofcarbonatomsinthechain,andtheendingane.Theprefixesforcarbonchainlengthsupto10carbon
atomsareshownintable2.8.
TABLE2.8 PrefixesUsedintheIUPACSystemforChainLengthsof1to10CarbonAtoms
Prefix Numberofcarbonatoms
meth 1
eth 2
prop 3
but 4
pent 5
hex 6
 hept 7
oct 8
non 9
dec 10

Thesimplestalkaneismethane,whichcontainsonecarbonatomandhastheformulaCH4.Notethatthesuffixand
prefixarenothyphenated,butarewrittentogetherasoneword.Thealkanewithsixcarbonatomsinastraightchain
(CH3CH2CH2CH2CH2CH3)islikewisecalledhexane.Namesforthestraightchainalkanesarestraightforward,but
thingsbecomemorecomplexforalkanesinwhichthecarbonchainisbranched.Inordertonamesuchalkanes,
identifythelongeststraightcarbonchain(theparentchain),andthentreatanygroupswhichbranchoffthischain
assubstituents.TheIUPACnameofanalkanewithabranchedchainconsistsofarootnamethatindicatesthe
longestchainofcarbonatomsinthecompound,substituentnamesthatindicatethegroupsbondedtotheparent
chain,andnumbersthatindicatethecarbonatomtowhichthesubstituentsareattached.Thisisillustratedbelowfor
4methyloctane,C9H20,inwhichthelongestcarbonchaincontainseightcarbonatoms(henceoctane)andthe
CH3(methyl)groupbondedtoC(4)isasubstituent(hence4methyl).

Thesubstituentsinalkanesarenamedaccordingtothealkanefromwhichtheyarederived.Forexample,aCH3
substituentisderivedfrommethane,CH4,throughtheremovalofoneHatom.Similarly,aC2H5substituentis
derivedfromethane,C2H6,byremovalofoneHatom.Asubstituentderivedfromanalkanebytheremovalofone
HatomiscalledanalkylgroupandiscommonlyrepresentedbythesymbolR.Alkylgroupsarenamedby
droppingtheanefromthenameoftheparentalkaneandaddingthesuffixyl.Therefore,aCH3substituentis
calledmethyl,andaC2H5substituentethyl.Table2.9givesnamesandstructuralformulaeforeightofthemost
commonalkylgroups.Notethat,whenalkylsubstituentscontainthreeormorecarbonatoms,thereismorethanone
possiblearrangementofthecarbonatomsinthesubstituent.Wedifferentiatebetweenthesepossibilitiesusingthe
prefixesiso,secandtert.IsoimpliesthepresenceofaCH(CH3)2groupattheendofthesubstituentcarbon
chain(theonlypossibilityforathreeatomchain),whiletheprefixessecandtertimplythatthesubstituentis
bondedtothelongestcarbonchainviaasecondaryortertiarycarbonatom,respectively.Whensecandtertare
partofaname,theyarealwaysitalicisedandhyphenated.However,iso,asusedinbothisopropylandisobutyl,is
nottreatedasaprefixlikesecandtert,andisneitheritalicisednorhyphenated.
TABLE2.9 Names,formulaeandabbreviationsofthemostcommonalkylgroups
Name Condensedstructuralformula Abbreviation
methyl CH3 Me

ethyl CH2CH3 Et
propyl CH2CH2CH3 Pr

isopropyl iPr

butyl CH2CH2CH2CH3 Bu

isobutyl iBu

secbutyl sBu
 tertbutyl tBu

ThecompleteIUPACrulesfornamingalkanesare:
1.Thenameforanalkanewithanunbranchedchainofcarbonatomsconsistsofaprefixshowingthenumberof
carbonatomsinthechain(table2.8)andtheendingane.
2.Forbranchedchainalkanes,thelongestchainofcarbonatomsistheparentchain,anditsnamebecomesthe
rootname.
3.Foranalkanewithonesubstituent,numbertheparentchainsothatthecarbonatombearingthesubstituentis
giventhelowestpossiblenumber.Forexample,wenumberthefivecarbonchaininthefollowingcompound
fromtherighthandend.

4.Givethesubstituentontheparentchainanameandanumber.Thenumbershowsthecarbonatomofthe
parentchaintowhichthesubstituentisbonded.Useahyphentoconnectthenumbertothename.Forexample,
themethylgroupin2methylpropaneisattachedtoC(2),asshownbelow.

5.Iftherearetwoormoreidenticalsubstituents,numbertheparentchainfromtheendthatgivesthelower
numbertothesubstituentclosesttotheendofthechain.Iftherearetwoormoreidenticalsubstituents,the
numberoftimestheyoccurisindicatedbytheprefixesdi,tri,tetra,penta,hexaandsoon.Acommais
usedtoseparatepositionnumbers.Ofthetwopossibilitiesbelow,wechoosetheonethatnumbersthecarbon
atomstowhichthemethylgroupsareattachedas2and4,ratherthan3and5.

6.Ifstep5leadstomorethanonepossibility,numbertheparentchainsuchthatthefirstpointofdifferencehas
thelowestpossiblenumber.Ofthetwopossibilitiesbelow,wechoosetheonethatnumbersthemethylgroup
showninred3ratherthan4.

7.Iftherearetwoormoredifferentsubstituents,listtheminalphabeticalorder,and(asusual)numberthechain
fromtheendthatgivesthelowernumbertothesubstituentencounteredfirstorthatprovidesthefirstpointof
difference.Iftherearedifferentsubstituentsinequivalentpositionsonoppositeendsoftheparentchain,the
substituentofloweralphabeticalorderisgiventhelowernumber.Theimportanceofalphabeticallyorderingthe
substituentsisshowninthefollowingexample.
8.Theprefixesdi,tri,tetraandsoon,andthehyphenatedprefixessecandtertaredisregardedforthe
purposesofplacingthesubstituentsinalphabeticalorder.Notethatbothisobutylandisopropylsubstituentsare
treatedasbeginningwiththeletteri.Putthenamesofthesubstituentsinalphabeticalorderfirst,andthen
inserttheprefix.Inthefollowingexample,thesubstituentsareorderedasethylandmethyl,notdimethyland
ethyl.

WORKEDEXAMPLE2.13

WritingIUPACnamesforalkanes
WriteIUPACnamesforthefollowingalkanes.
(a)

(b)

Analysis

Weneedtofollowtherulesfornamingalkanesoutlinedpreviously.Whennamingalkanes,startby
identifyingthelongestcarbonchain,andthenidentifyandnumberthesubstituents.

Solution

Wewillconsidereachalkaneinturn.Thelongestcarbonchainin(a)containsfourcarbonatomsand
thereforewillbenamedasasubstitutedbutane.Wethennumbertheparentchaintogivethemethyl
substituentthelowestpossiblenumber.Thisisdoneineitherofthetwoequivalentwaysshownbelow
(notethatthesubstituentisatC(2)inbothcases).

(a)

Wenownamethesubstituentandspecifyitspositionontheparentchaintoobtainthefullname.This
alkaneisthereforenamed2methylbutane.

Thelongestcarbonchainin(b)containssevencarbonatoms,andthereforeitwillbenamedasa
substitutedheptane.Therearetwosubstituentsinthismolecule:amethylgroupandanisopropylgroup,
andthereforewemustnumberthechaintogivethesubstituentclosesttotheendofthechainthelowest
 number.Thisisshowninthefollowingdiagram,whereweagainhavetwoequivalentpossibilities.

(b)

Tonamethealkane,listthesubstituentsinalphabeticalorderandspecifytheirpositionsontheparent
chain.Asisopropylcomesbeforemethyl,thisalkaneisnamed4isopropyl2methylheptane.

Isouranswerreasonable?

Theeasiestwaytochecktheanswerstothistypeofquestionistoworkbackwardsfromthenamewe
havededuced,andderivethechemicalstructure.Ifwedothatinthiscase,wefindthatouranswersare
correct.

PRACTICEEXERCISE2.16
WritetheIUPACnamesforthefollowingalkanes.
(a)

(b)

ConstitutionalIsomerisminAlkanes

Theconceptofisomerismwasmentionedpreviouslywithrespecttotherelativepositioningofthetwomethyl
groupsin1,2dimethylcyclopentane.Thealkanesprovideanexcellentexampleofthedifferentwaysinwhicha
particularnumberofcarbonandhydrogenatomsmaybejoined.Thereisonlyoneorderofattachment,andhence
onewayofwritingCH4(methane),C2H6(ethane)andC3H8(propane).However,whenwecometoC4H10two
ordersofattachmentofatomsarepossible.
Inoneofthese,butane,thefourcarbonatomsarebondedinastraightchainintheother,2methylpropane,three
carbonatomsarebondedinastraightchain,withthefourthcarbonatomasabranch.Butaneand2methylpropane
areconstitutionalisomers.Constitutionalisomersarecompoundswiththesamechemicalformulabutadifferent
orderofattachmentoftheconstituentatoms.Constitutionalisomerscanusuallybedistinguishedbytheirdiffering
physicalpropertiesbutaneand2methylpropaneprovideagoodexampleofthisbutaneboilsat0.5C,while2
methylpropaneboilsat11.6C.IfweconsiderC5H12,wecanobtainthethreeconstitutionalisomersshownbelow.

Thenumberofpossibleconstitutionalisomersbecomesverylargeveryquickly.Forexample,thealkanewiththe
chemicalformulaC25H52hasastaggering36797588possibleconstitutionalisomers.Constitutionalisomersarenot
uniquetoalkanes,andcanbefoundthroughoutorganicchemistryindeed,workedexamples2.10and2.11
involveddrawingconstitutionalisomersofalcoholsandaldehydesrespectively.

WORKEDEXAMPLE2.14

Recognisingconstitutionalisomers
Dothestructuralformulaeineachofthefollowingpairsofmoleculesrepresentthesamecompoundor
constitutionalisomers?
(a)

(b)

Analysis

Todeterminewhetherthesestructuralformulaerepresentthesamecompoundorconstitutionalisomers,
wemustfirstfindthelongestchainofcarbonatoms.Notethatitmakesnodifferencewhetherthechainis
drawnstraightorbent.Wethennumberthelongestchainfromtheendnearestthefirstbranchand
comparethelengthsofeachchain,andthesizesandlocationsofanybranches.Structuralformulaethat
havethesameorderofattachmentofatomsrepresentthesamecompoundthosewhichhavedifferent
ordersofattachmentofatomsrepresentconstitutionalisomers.Notethatsimilaritiesordifferences
betweenstructuralformulaearesometimesmadecleareriftheyaredrawnaslinestructures.

Solution
(a)Eachstructuralformulahasanunbranchedchainofsixcarbonatoms.Thetwostructuresare
identicalandrepresentthesamecompound.

(b)Eachstructuralformulahasachainoffivecarbonatomswithtwobranches.Althoughthe
branchesareidentical,theyareatdifferentlocationsonthechains.Therefore,thesestructural
formulaerepresentconstitutionalisomers.

PRACTICEEXERCISE2.17
Dothestructuralformulaeineachofthefollowingpairsof
moleculesrepresentthesamecompoundorconstitutional
isomers?
(a)

(b)
 WORKEDEXAMPLE2.15

Drawingconstitutionalisomers
DrawstructuralformulaeforthefiveconstitutionalisomerswiththemolecularformulaC6H14.

Analysis

Therearesixcarbonatomsinthemolecule,sowecanexpectconstitutionalisomerswithlongestcarbon
chainlengthsofsix,five,fourandpossiblythree.Wemustdrawallpossibleisomerswiththesechain
lengths.

Solution

TheconstitutionalisomersofC6H14areasfollows.

NotethatwefindthatthereisnowayofwritingC6H14withonlythreecarbonatomsinthelongestchain.

Isouranswerreasonable?

Therearenootherpossiblearrangementsofsixcarbonatomsandfourteenhydrogenatoms,eachsingly
bondedtoeachother.Therefore,wecanbeconfidentouranswersarecorrect.

PRACTICEEXERCISE2.18
Drawthenineconstitutionalisomerswiththe
formulaC7H16.

GeneralOrganicNomenclature
TheprinciplesofIUPACnomenclatureasappliedtoalkanescanbeextendedtothenamingofanyorganic
compound.Thenamewegivetoanycompoundwithachainofcarbonatomsconsistsofthreeparts:aprefix,an
infixandasuffix.Eachpartprovidesspecificinformationaboutthestructuralformulaofthecompound.
1.Theprefixshowsthenumberofcarbonatomsintheparentchain.Prefixesthatshowthepresenceof1to10
carbonatomsinachainweregivenintable2.8.
2.Theinfixshowsthenatureofthecarboncarbonbondsintheparentchain.Thethreepossibilitiesaregivenin
table2.10.
 TABLE2.10 TheThreePossibleInfixesandTheirMeanings
Infix Natureofcarboncarbonbondsintheparentchain

an allsinglebonds
en oneormoredoublebonds
yn oneormoretriplebonds

3.Thesuffixshowstheclassofcompoundtowhichthesubstancebelongs,andthereforethefunctionalgroup(s)
presentinthecompound.Thesuffixesfortheclassesofcompoundwehavealreadymetareasshownintable
2.11.
TABLE2.11 SomeSuffixesandtheClassofCompoundthattheyDesignate
Suffix Classofcompound
e hydrocarbon
ol alcohol
al aldehyde
one ketone
oicacid carboxylicacid

Wecanillustratetheuseofprefixes,infixesandsuffixeswithrespecttothefollowingfourorganiccompounds.We
willdivideeachnameintoaprefix,aninfixandasuffix,andspecifytheinformationaboutthestructuralformula
thatiscontainedineachpartofthename.
(a)

Theprefixpropmeansthreecarbonatomsintheparentchain.Theinfixenreferstothepresenceofoneor
moreC Cdoublebondsinthemolecule,whilethesuffixemeansthatthecompoundisahydrocarbon,
composedofonlycarbonandhydrogenatoms.
(b)

Theprefixethmeanstwocarbonatomsintheparentchain.Theinfixanmeanstherearenocarbon
carbonmultiplebondsinthemolecule,andthesuffixolmeansthatthereisanalcoholfunctionalgroupin
themolecule.
(c)

Theprefixpentmeansfivecarbonatomsintheparentchain.Theinfixanmeanstherearenocarbon
carbonmultiplebondsinthemolecule,andthesuffixoicacidreferstothepresenceofacarboxylicacidin
themolecule.
(d)
(d)

Theprefixethmeanstwocarbonatomsintheparentchain.Theinfixynmeansthatthereareoneormore
C Ctriplebondsinthemolecule.Thesuffixemeansthatthecompoundisahydrocarbon,composedof
onlycarbonandhydrogenatoms.

Wecansummarisethisinformationinthefollowingdiagram.
(a)
 (b)

(c)

(d)

Noticethat,ineachoftheseexamples,thereisnoambiguityaboutthepositionofthefunctionalgroup.Wewilldeal
laterwithexampleswherethepositionisnotasclear.

PRACTICEEXERCISE2.19
Combinetheproperprefix,infixandsuffix,and
writetheIUPACnameforeachofthefollowing
compounds.
(a)

(b)

Theexamplesgiveninthissectionserveonlyasanintroductiontoorganicnomenclatureyouwillfindmore
detailedexamplesintheappropriatechapterslaterinthebook.

Wehaveseeninthischapterthatsuchapparentlydisparatetopicsasunits,nomenclatureandrepresentationsof
moleculesareallpartofthelanguageofchemistry.Thereisstillmuchofthislanguageforyoutolearn,butthis
chapterhasintroducedmanyofthefundamentalsthatyouwillneedinordertounderstandandappreciatethe
followingchapters.Indeed,itislikelythatyouwilloftenneedtoreferbacktothischapterwhenyoucomeacross
examplesofmeasurement,representationsofmoleculesornomenclaturelaterinthisbook.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Measurement
Allmeasurementshaveanassociatedunitanduncertainty.Theunitsusedformeasurementsarebased
onthesetofsevenSIbaseunits,whichcanbecombinedtogivevariousderivedunits.TheSIbase
unitsarethemetre,kilogram,second,kelvin,mole,ampereandcandela.Prefixescanbeusedtodenote
multiplicationoftheseunitsbypowersof10.Dimensionalanalysis,whichusesthefactthatunits
undergothesamekindsofmathematicaloperationsasthenumberstowhichtheyareattached,canbe
usedasanaidtodeterminingthecorrectformofanequation.SomenonSIunitsareincommonusage
butcanbeconvertedtoSIunitsusingaconversionfactor.

Uncertaintiesariseinanymeasurementfromthelimitationsoftheapparatususedtomakethe
measurement.Someideaoftheuncertaintyandthereforeprecisioninameasurementcanbeobtained
fromthenumberofsignificantfigurestowhichthemeasurementisquoted.

Expressinganumberinscientificnotationcanmakeiteasiertodeterminethenumberofsignificant
figures.Therewillalwaysbeuncertaintyinthefinalfigureofanymeasurement.Theaccuracyofa
measurementshowshowclosetothetruevaluethemeasurementis,whiletheprecisionofa
measurementrepresentshowreproducibleitis.

Whenmeasurementsaremanipulatedinequations,thefollowingrulesapply:
Whenmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswer
shouldnotbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whenmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthequantitywiththefewestnumberofdecimalplaces.

RepresentationsofMolecules
Thechemicalformulaofasubstanceshowstherelativenumberofeachtypeofatompresent,butgives
nostructuralinformation.Therulesforwritingchemicalformulaeofbinarycompoundsareasfollows:
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst.

Thechemicalformulaeofioniccompoundsarewrittenwiththecationfollowedbytheanion,while
organiccompoundshaveCandHfirst,followedbytherestoftheelementsinalphabeticalorder.

Structuralformulaeattempttoshowparticularaspectsofmolecularstructureinbothtwoandthree
dimensions.Suchdepictionsareespeciallyimportantinorganicchemistrywherecatenationleadstoan
enormousnumberofpossiblecarbonbasedmolecules.Structuralformulaearedrawnusingonelineto
representsinglebonds,twolinesfordoublebondsandthreelinesfortriplebonds.Carbonatomsatthe
endofacarbonchainarecalledterminalcarbonatoms.Structuralformulaecanhelpdistinguish
betweenisomers.Twotypesofshorthandstructuralformulaearewidelyusedcondensedstructural
formulaedonotincludeexplicitdepictionsofbondsbetweenatoms,whilelinestructuresremoveatom
labelsforcarbonatomsandallhydrogenatomsthatarebondedtocarbonatoms.Threedimensional
aspectscanbeintroducedintostructuralformulaethroughtheuseofhashedandsolidwedges,which
showbondsgoingawayfromandcomingtowardstheobserverrespectively.

Ballandstickmodelsandspacefillingmodelsaretwoothermethodswherethreedimensionalitymay
beshown.
Mechanisticarrowscanbeusedtoshowthemovementofelectronsinchemicalprocesses.Thetailof
thearrowissituatedattheelectronsourceandthearrowheadshowsthedestination.

Nomenclature
ChemicalspeciescanbenamedaccordingtosetsofrulesprescribedbyIUPAC.Therulesfornaming
nonmetallicbinarycompoundsareasfollows:
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthe
samegroupoftheperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffix
ide.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelement
usuallycontainsaprefixthatspecifiesthenumberofatomspresent.

Binarycompoundscontaininghydrogencanbenamedwithhydrogeneitherfirstorsecond,depending
onthepositionoftheotherelementintheperiodictable,accordingtotheaboverules.

Ioniccompoundsarenamedwiththecationfirst,followedbytheanion,whileoxoanionsarenamed
accordingtoanextensivesetofrules.

Organiccompoundsarenamedprimarilyaccordingtotheirfunctionalgroupthoseofimportanceinthis
chapteraretheOHgroupfoundinalcohols,theCHOgroupfoundinaldehydes,theC Ogroup
foundinketonesandtheCOOHgroupfoundincarboxylicacids.Alkanesbelongtothegroupof
compoundscalledhydrocarbonsandaresometimescalledsaturatedhydrocarbons.Thoseconsisting
solelyofchainsofcarbonatomsarecalledacyclicalkanes,whilethosecontainingoneormoreringsof
carbonatomsarecalledcycloalkanes.Theirnomenclatureisbasedonthelongestcarbonchainwithin
themolecule,withaprefixdenotingthelengthofthatchain.Substituentsonthechainarenumbered
suchthatthesumofthenumbersforthesubstituentspresentisthelowestpossiblenumber.Namesof
organiccompoundsgenerallycompriseaprefix,infixandsuffix.Theprefixshowsthenumberof
carbonatomsintheparentchain,theinfixshowsthenatureofthecarboncarbonbondsintheparent
chain,andthesuffixshowstheclassofcompoundtowhichthesubstancebelongs,andthereforethe
functionalgroup(s)presentinthecompound.

Constitutionalisomersofalkaneshavethesamechemicalformulaebutdifferentstructuralformulaeand
hencedifferentnames.Theseisomersgenerallyhavedifferentphysicalproperties.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
SIunits(section2.1)
ThebaseSIunits:metre,kilogram,second,kelvin,mole,ampereandcandelaareusedeitherdirectlyor
toderiveunitsforanymeasurementinchemistry.

SIprefixes(section2.1)
SIprefixesareusedtocreatelargerandsmallerunits.Theprefixeshelpustoconvertbetween
differentlysizedunits.

Dimensionalanalysis(section2.1)
Dimensionalanalysisassistsindeterminingthecorrectformofanequationthroughknowledgeofthe
unitsofallcomponentsoftheequation.

Rulesforsignificantfiguresincalculations(section2.1)
Thefollowingrulesareusedtoroundanswerstothecorrectnumberofsignificantfigures.
Whenmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswer
shouldnotbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whenmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthequantitywiththefewestnumberofdecimalplaces.

Rulesforwritingchemicalformulaeofbinarycompounds(section2.2)
Thefollowingrulesareusedtowritethecorrectchemicalformulaeforcompoundscontainingonlytwo
elements.
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst.
4.Ifthecompoundisionic,wewritethecationfirst,followedbytheanion.

Rulesfordrawinglinestructures(section2.2)
Theserulesareusedforconvertingstructuralformulaetolinestructures,andcanalsobeusedtocarry
outthereverseoperation.
1.AllbondsexceptCHbondsareshownaslines.
2.CHbondsandHatomsattachedtocarbonarenotshowninthelinestructure.
3.Singlebondsareshownasonelinedoublebondsareshownastwolinestriplebondsareshown
asthreelines.
4.Carbonatomsarenotlabelled.Allotheratomsarelabelledwiththeirelementalsymbols.

Hashedandsolidwedges(section2.2)
Theseareusedtointroducethreedimensionalaspectsintostructuralformulae.

Asolidwedge( )representsabondcomingoutofthepage,whileahashedwedge( )representsa

bondgoingbackintothepage.Anormallineisusedforbondsintheplaneofthepage.

Mechanisticarrows(section2.2)
Theseareusedtoshowthemovementofelectronsinchemicalprocesses.Singleheadedarrowsshow
themovementofasingleelectron,whiletwoheadedarrowsshowthemovementofelectronpairs.The
directionofelectronmovementisfromthetailofthearrowtothehead.

Namingnonmetallicbinarycompounds(section2.3)
Theserulesareusedtonamecompoundscontainingonlytwononmetallicelements.
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthe
samegroupoftheperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffix
ide.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelement
usuallycontainsaprefixthatspecifiesthenumberofatomspresent.

Namingoxoanions(section2.3)
Theserulesareusedtonameanionscontainingoxygenandatleastoneotherelement.
1.Thenamehasaroottakenfromthenameofthecentralatom.
2.Whenanelementformstwodifferentoxoanions,theonewithfeweroxygenatomsendsinite
andtheotherendsinate.
3.Chlorine,bromineandiodineeachformfourdifferentoxoanionsthataredistinguishedby
prefixesandsuffixes.
4.Apolyatomicanionwithachargemorenegativethan1mayaddH+togiveanotheranion.
Theseanionsarenamedfromtheparentanionbyaddingthewordhydrogen.

Functionalgroups(section2.3)
Functionalgroupsarethebasisfornamingorganiccompounds.
Alcoholscontainahydroxylgroup.
Aldehydescontainaterminalcarbonylgroup.
Ketonescontainanonterminalcarbonylgroup.
Carboxylicacidscontainacarboxylgroup.

Namingalkanes(section2.3)
Therearetwopartstothenameofanalkane:aprefix,indicatingthenumberofcarbonatomsinthe
chain,andthesuffixane.

Prefixesforcarbonchainlength(section2.3)
Knowledgeoftheseprefixesisnecessaryfornaminganyorganiccompound:1,meth2,eth3,prop
4,but5,pent6,hex7,hept8,oct9,non10,dec.

Generalorganicnomenclature(section2.3)
Theprefix,infixandsuffixofthenameofanorganiccompoundreflectthestructureofthatcompound.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Measurement
2.1Whymustmeasurementsalwaysbewrittenwithaunit?
2.2WhatdoestheabbreviationSIstandfor?
2.3WhichSIbaseunitisdefinedintermsofaphysicalobject?
2.4WhatistheonlySIbaseunitthatincludesadecimalprefix?
2.5Newton'ssecondlawstatesthatforceisequaltomasstimesacceleration.WhatistheSIderived
unitforforce?(Theunitiscalledthenewton,abbreviatedN.)
2.6Whatisthemeaningofeachofthefollowingprefixes?
(a)centi
(b)milli
(c)kilo
(d)micro
(e)nano
(f) pico
(g)mega
2.7Whatabbreviationisusedforeachoftheprefixesnamedinquestion2.6?
2.8Whatunitsaremostusefulinthelaboratoryformeasuringthefollowing?
(a)length
(b)volume
(c)mass
2.9Definethetermsignificantfigures.
2.10Whatisthedifferencebetweenaccuracyandprecision?
2.11Aconcentrationof1.5gmL1ofatoxinisfoundinasampleofapatient'sblood.Howhigh
mighttheconcentrationactuallyhavebeen?Supposethatthemeasurementhadbeenwrittenas
1.50gmL1ofblood.Howhighmighttheconcentrationhavebeeninthiscase?
2.12Thereare3600sin1hour.Bywhatconversionfactorwouldyoumultiply250stoconvertitto
hours?Bywhatconversionfactorwouldyoumultiply3.84htoconvertittoseconds?
RepresentationsofMolecules
2.13Listtherulesfortheconversionofstructuralformulaetolinestructures.
2.14Whatmustbetrueabouttwosubstancesiftheyaretobecalledisomersofeachother?
2.15Writethechemicalformulaforeachofthefollowingsubstances.
(a)stearicacid,whichcontains36hydrogenatoms,18carbonatomsand2oxygenatoms
(b)silicontetrachloride,whichcontains1siliconatomand4chlorineatoms
(c)Freon113,whichcontains3atomseachoffluorineandchlorineand2atomsofcarbon
2.16Thelinestructuresthatfollowrepresentstartingmaterialsformakingplastics.Foreachofthem,
drawthestructuralformulaandgivethechemicalformula.
(a)
 (b)

(c)

2.17Writelinestructuresforcompounds(a)to(f).
(a)

(b)

(c)(CH3)2CHCH(CH3)2
(d)

(e)(CH3)3CH
(f) CH3(CH2)3CH(CH3)2
2.18Writethechemicalformulaandthecondensedstructuralformulaforeachofthefollowing
alkanes.
(a)

(b)
 (c)

2.19Provideanevenmoreabbreviatedformulaforeachofthefollowingcondensedstructural
formulae,usingparenthesesandsubscripts.
(a)

(b)

(c)

Nomenclature
2.20Writechemicalformulaeforthefollowingcompounds.
(a)chlorinemonofluoride
(b)seleniumtrioxide
(c)hydrogenbromide
(d)silicontetrachloride
(e)sulfurdioxide
(f) hydrogenperoxide
2.21Namethefollowingcompounds.
(a)ClF3
(b)H2Se
(c)ClO2
(d)SbCl3
(e)PCl5
(f) N2O5
(g)N2Cl4
(h)NH3
2.22Drawthestructuralformulaeofthefollowingmolecules.
(a)butane
(b)3methylpentane
(c)2,3dimethylhexane
2.23Whydowenothavetolabelaldehydesasprimaryorsecondary,orcarboxylicacidsasbeing
primary,secondaryortertiary?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
2.24Whatnumbershouldreplacethequestionmarkineachofthefollowing?
(a)1cm=?m
(b)1km=?m
(c)1m=?pm
(d)1dm=?m
(e)1g=?kg
(f) 1cg=?g
(g)1nm=?m
(h)1g=?g
(i) 1kg=?g
(j) 1Mg=?g
(k)1mg=?g
(l) 1dg=?g
2.25Converteachofthefollowingmeasurementstothegivenunits.
(a)60CtoK
(b)30CtoK
(c)273KtoC
(d)299KtoC
(e)40CtoK
2.26Naturalgasismostlymethane,asubstancethatboilsatatemperatureof111K.Whatisitsboiling
pointinC?
2.27Heliumhasthelowestboilingpointofanyliquid.Itboilsat4K.WhatisitsboilingpointinC?
2.28Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)37.53cm
(b)37.240cm
(c)202.0g
(d)0.00024kg
(e)0.07080m
(f) 2400mL
2.29Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)0.0230g
(b)105.303m
(c)0.007kg
(d)614.00mg
(e)10L
(f) 3.8105mm
2.30Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)1.0230kg
(b)3.0200m
 (c)0.0030L
(d)27.300g
(e)0.04320mm
2.31Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)2.303ng
(b)0.04030kg
(c)20030mL
(d)9200g
(e)0.0101dL
2.32Performthefollowingarithmeticandroundtheanswerstothecorrectnumberofsignificant
figures.
(a)0.0023m315m
(b)84.25kg0.01075kg
(c)(84.45g94.45g)/(31.4mL9.9mL)
(d)(23.4g+102.4g+0.003g)/(6.478mL)
(e)(313.44cm209.1cm)8.2234cm
2.33Performthefollowingarithmeticandroundtheanswerstothecorrectnumberofsignificant
figures.
(a)3.58g/1.739mL
(b)4.02mL+0.001mL
(c)(22.4g8.3g)/(1.142mL0.002mL)
(d)(1.345g+0.022g)/(13.36mL8.4115mL)
(e)(74.335m74.332m)/(4.75s1.114s)
2.34Expressthefollowingnumbersinscientificnotationtothreesignificantfigures.
(a)4340
(b)32000000
(c)0.003287
(d)42000
(e)0.00000800
(f) 324300
2.35Expressthefollowingnumbersinscientificnotation.Assume,inthisproblem,thatonlythenon
zerodigitsaresignificantfigures.
(a)489
(b)0.00375
(c)82300
(d)0.01225
(e)2.43
(f) 27320
2.36Writethefollowingnumbersinstandard(nonscientific)form.
(a) 3.110 5
(b)4.3510 6
(c) 3.910 3
 (d)4.410 12
(e) 35.610 7
(f) 8.810 8
2.37Writethefollowingnumbersinstandard(nonscientific)form.
(a) 5.2710 8
(b)7.1210 5
(c) 43.510 9
(d)2.3510 2
(e) 4.000010 7
(f) 37.210 2
2.38Performthefollowingarithmeticandexpresstheanswersinscientificnotation.
(a) (4.010 7)(2.110 5)
(b)(3.010 2)+(3.2110 5)
(c) (2.110 7)(2.110 5)
(d)(3.010 4)(8.210 5)
(e) (9.1010 12)/(2.010 3)2
2.39Performthefollowingarithmeticandexpresstheanswersinscientificnotation.
(a) (3.010 4)(2.110 5)
(b)(8.010 12)/(2.010 3)2
(c) (6.710 5)(8.210 5)
(d)(1.410 5)(3.010 4)
(e) (3.310 4)+(2.5210 2)
2.40Converteachofthefollowingmeasurementstothegivenunits.
(a)32.0dmtokm
(b)8.2mgtog
(c)75.3mgtokg
(d)137.5mLtoL
(e)0.025LtomL
(f) 342pmtodm
2.41Converteachofthefollowingmeasurementstothegivenunits.
(a)92dLtomL
(b)22ngtog
(c)83pLtonL
(d)230kmtom
(e)87.3cmtokm
(f) 238mmtonm
2.42Converteachofthefollowingmeasurementstothegivenunitsandexpressyouranswersin
scientificnotation.
 (a)230kmtocm
(b)423kgtomg
(c)423kgtoMg
(d)430LtomL
(e)27ngtokg
(f) 730nLtokL
2.43Converteachofthefollowingmeasurementstothegivenunitsandexpressyouranswersin
scientificnotation.
(a)183nmtocm
(b)3.55gtodg
(c)6.22kmtonm
(d)33dmtomm
(e)0.55dmtokm
(f) 53.8ngtopg
2.44Whichfunctionalgroupdoeseachofthefollowingcompoundscontain?
(a)CH3CH CH2
(b)CH3CH2OH
(c)CH3CH2CH2COOH
(d)HOCH2CH2CH3
2.45Whichfunctionalgroupdoeseachofthefollowingcompoundscontain?
(a)CH3C CH
(b)

(c)

2.46Decidewhetherthemembersofeachpairareidentical,isomersorunrelated.
(a)

(b)

(c)CH3CH2OHandCH3CH2CH2OH
(d)

(e)

(f)
 (g)CH3CH2CH2NH2andCH3CH2NHCH3
2.47Examineeachpairanddecideiftheyareidentical,isomersorunrelated.
(a)

(b)

(c)

(d)

(e)

2.48WritetheIUPACnamesofthefollowinghydrocarbons.
(a)CH3CH2CH2CH2CH3
(b)

(c)

(d)

2.49Writestructuralformulaeforallofthesaturatedalcoholswiththreeorfewercarbonatomsper
molecule.
2.50WritestructuralformulaeforallofthepossiblealcoholswiththegeneralformulaC4H10O.
2.51Writechemicalformulaeforthemoleculeswhoseballandstickmodelsfollow.
(a)

(b)

(c)

(d)

(e)

(f)

(g)
2.52Writechemicalformulaeforthemoleculeswhoseballandstickmodelsfollow.
(a)

(b)

(c)

(d)

(e)

(f)

(g)
2.53Writestructuralformulaeforthemoleculesinquestions2.51and2.52.
2.54Convertthefollowingstructuralformulaeintolinestructures.
(a)

(b)

(c)

(d)

(e)

(f)
2.55Convertthefollowingstructuralformulaeintolinestructures.
(a)

(b)

(c)

(d)

(e)

(f)

2.56Convertthefollowinglinestructuresintostructuralformulae.
(a)

(b)

(c)
(d)
 (e)

(f)

(g)

(h)

(i)

2.57Convertthefollowinglinestructuresintostructuralformulae.
(a)

(b)

(c)

(d)

(e)

(f)

(g)

2.58Whichofthefollowingstatementsaretrueaboutconstitutionalisomers?
(a)Theyhavethesamechemicalformula.
(b)Theyhavethesameatomicmass.
(c)Theyhavethesameorderofattachmentofatoms.
(d)Theyhavethesamephysicalproperties.
2.59Eachmemberofthefollowingsetofcompoundsisanalcohol.
i.
 ii.

iii.

iv.

v.

vi.

vii.

viii.

Whichstructuralformulaerepresent:
(a)thesamecompound?
(b)differentcompoundsthatareconstitutionalisomers?
(c)differentcompoundsthatarenotconstitutionalisomers?
2.60Eachmemberofthefollowingsetofcompoundsiseitheranaldehydeoraketone.
i.

ii.

iii.

iv.

v.
 vi.

vii.

viii.

Whichstructuralformulaerepresent:
(a)thesamecompound?
(b)differentcompoundsthatareconstitutionalisomers?
(c)differentcompoundsthatarenotconstitutionalisomers?
2.61Foreachofthefollowingpairsofcompounds,determinewhetherthestructuralformulaeshown
represent:
i. thesamecompound
ii. differentcompoundsthatareconstitutionalisomers
iii.differentcompoundsthatarenotconstitutionalisomers.
(a)

(b)

(c)

(d)

(e)

(f)
2.62Whichsetsofcompoundsareconstitutionalisomers?
(a)CH3CH2OHandCH3OCH3
(b)

(c)

(d)

(e)

(f)

2.63Drawlinestructuresfor:
(a)fouralcoholswithchemicalformulaC4H10O
(b)twoaldehydeswithchemicalformulaC4H8O
(c)oneketonewithchemicalformulaC4H8O
(d)threeketoneswithchemicalformulaC5H10O
(e)fourcarboxylicacidswithchemicalformulaC5H10O2.
2.64Writechemicalformulaeforthesecompounds.
(a)methane
(b)hydrogeniodide
(c)calciumhydride
(d)phosphorustrichloride
(e)dinitrogenpentaoxide
(f) sulfurhexafluoride
(g)borontrifluoride
2.65Writechemicalformulaeforthesecompounds.
(a)ammonia
(b)hydrogensulfide
(c)2chloropropane
(d)silicondioxide
(e)molecularnitrogen
(f) sulfurtetrafluoride
(g)brominepentafluoride
2.66Namethefollowingcompounds.
(a)S2Cl2
(b)IF7
(c)HBr
(d)N2O3
(e)SiC
(f) (f)CH3OH
2.67Namethefollowingcompounds.
(a)GeCl4
(b)N2F4
(c)LiH
(d)SeO2
(e)CH3CH2OH
2.68Writethechemicalformulaofeachcompound.
(a)hydrogenfluoride
(b)calciumfluoride
(c)aluminiumsulfate
(d)ammoniumsulfide
2.69Writethechemicalformulaofeachcompound.
(a)sodiumhypochlorite
(b)lithiumperiodate
(c)magnesiumbromide
2.70Nameeachofthefollowingcompounds.
(a)CaO
(b)K2CO3
(c)HBr
(d)Na2HPO4
2.71Nameeachofthefollowingcompounds.
(a)(NH4)2SO4
(b)KBr
(c)H2S
(d)Na2S
2.72Writechemicalformulaeforthesecompounds.
(a)sodiumsulfate
(b)potassiumsulfide
(c)potassiumdihydrogenphosphate
(d)sodiumhydrogencarbonate
(e)lithiumperbromate
2.73Writechemicalformulaeforthesecompounds.
(a)potassiumchlorate
 (b)ammoniumhydrogencarbonate
(c)aluminiumchloride
(d)potassiumoxide
2.74Namethefollowingcompounds.
(a)K2CO3
(b)NaClO
(c)CuSO4
(d)KH2PO4
(e)NaNO3
(f) CaSO3
(g)KMnO4
2.75Nameeachofthefollowingcompounds.
(a)NaNO2
(b)Mg 3(PO4)2
(c)KHSO4
(d)CsBr
(e)Al(ClO4)3
2.76WriteIUPACnamesforthesealkanes.
(a)

(b)

(c)

(d)

2.77Drawlinestructuresforthesealkanes.
(a)2,2,4trimethylhexane
(b)2,2dimethylpropane
(c)3ethyl2,4,5trimethyloctane
(d)5butyl2,2dimethylnonane
(e)4isopropyloctane
(f) 3,3dimethylpentane
2.78ExplainwhyeachofthefollowingnamesisanincorrectIUPACname,andwritethecorrect
IUPACnamefortheintendedcompound.
(a)1,3dimethylbutane
(b)4methylpentane
 (c)2,2diethylbutane
(d)2ethyl3methylpentane
(e)2propylpentane
(f) 2,2diethylheptane
(g)2,2dimethylcyclopropane
(h)1ethyl5methylcyclohexane
2.79Drawastructuralformulaforeachofthefollowingcompounds.
(a)ethanol
(b)ethanal
(c)ethanoicacid
(d)butanone
(e)butanal
(f) butanoicacid
(g)propanal
2.80WritetheIUPACnameforeachcompound.
(a)

(b)

(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
2.81Whenanobjectisheatedtoahightemperature,itglowsandgivesofflight.Thecolourbalanceof
thislightdependsonthetemperatureoftheglowingobject.Photographiclightingisdescribed,in
termsofitscolourbalance,asatemperatureinkelvin.Forexample,acertainelectronicflashgives
acolourbalance(calledcolourtemperature)ratedat5800K.Whatisthistemperatureexpressed
inC?
2.82TheIUPACsystemdividesthenameofacompoundintoaprefix(showingthenumberofcarbon
atoms),aninfix(showingthepresenceofcarboncarbonsingle,doubleortriplebonds),anda
suffix(showingthepresenceofanalcohol,analdehyde,aketoneoracarboxylicacid).Assume
forthepurposesofthisproblemthat,tobeanalcohol(ol),thehydroxyloraminogroupmustbe
bondedtoacarbonatomwhichhasonlysinglebondstootherattachedatoms.

Giventhisinformation,writethestructuralformulaofacompoundwithanunbranchedchainof
fourcarbonatomsthatisan:
(a) alkane
(b) alkene
(c) alkyne
(d) alkanol
(e) alkenol
(f) alkynol
(g) alkanal
(h) alkenal
(i) alkynal
(j) alkanone
(k) alkenone
(l) alkynone
(m)alkanoicacid
(n) alkenoicacid
(o) alkynoicacid.
(Note:Thereisonlyonestructuralformulapossibleforsomepartsofthisproblem.Forotherparts,
twoormorestructuralformulaearepossible.Wheretwoormorearepossible,wewilldealwith
howtheIUPACsystemdistinguishesbetweenthemwhenwecometothechaptersonthose
particularfunctionalgroups.)
2.83Ineverydaylife,weencounterchemicalswithunsystematicnames.Whatisthenameachemist
woulduseforeachofthefollowingsubstances?
(a)dryice,CO2
(b)saltpetre,KNO3
(c)salt,NaCl
(d)bakingsoda,NaHCO3
 (e)sodaash,Na2CO3
(f) lye,NaOH
(g)lime,CaO
(h)milkofmagnesia,Mg(OH)2
2.84AmineralisachemicalcompoundfoundintheEarth'scrust.Whatarethechemicalnamesofthe
followingminerals?
(a)TiO2(rutile)
(b)PbS(galena)
(c)Al2O3(bauxite)
(d)CaCO3(limestone)
(e)BaSO4(barite)
(f) HgS(cinnabar)
(g)Sb 2S3(stibnite)
2.85Thelinestructuresofthreedifferentplantgrowthhormonesaregivenbelow.Writethechemical
formulaforeachcompound.
(a)

(b)

(c)

2.86Thefollowingmoleculesareknownfortheircharacteristicfragrances.Converteachlinestructure
intoacompletestructuralformula.
(a)
 (b)

(c)

(d)

(e)

2.87Thecompoundsinthefollowingpairsofsubstancesarequitedifferentfromeachotherdespite
havingsimilarnames.Writecorrectformulaeforeachpair.
(a)sodiumnitriteandsodiumnitrate
(b)potassiumcarbonateandpotassiumhydrogencarbonate
(c)iodineandiodideion
(d)sodiumchlorideandsodiumhypochlorite
(e)nitrogenoxideandnitrogendioxide
(f) potassiumchlorateandpotassiumperchlorate
(g)ammoniaandammoniumion
2.88ProvideIUPACapprovednamesforeachofthefollowingcompounds.
(a)NH4Cl
(b)BrF5
(c)SO2
2.89ProvideIUPACapprovednamesforeachofthefollowingcompounds.
(a)KClO3
(b)KClO2
(c)KClO
(d)KCl
(e)Na2HPO4
2.90Expresstheresultsofthefollowinglogarithmiccalculationstothecorrectnumberofsignificant
figures.
(a) log(2.7510 5)
(b)antilog(2.53)
(c)ln(2.0)
(d)log(1.56+0.254)
(e) e7.21
(f)

2.91Surfacetension(),thephenomenonthatallowssmallinsectstowalkonwater,canbedefined
bythefollowingequation.

GiventhatE(energy)ismeasuredinJ,andA(area)ismeasuredinm2,determinetheunitsof
surfacetension.
2.92RememberingthatJisaderivedunit(seetable2.2),expressyouranswertoquestion2.91using
onlySIunits.
2.93Theratelawforthegasphasereaction

is

Determinetheunitsoftherateconstantk,giventhattherateofreactionhasunitsofmolL1s1
andtheconcentrationsofNOandH2aremeasuredinmolL1.
2.94Fromknowledgeoftheirgivenunits,determineanequationrelatingeachofthefollowinggroups
ofvariablesandconstants.
(a) volume(V,L),concentration(c,molL1)andamount(n,mol).Makeamountthesubject.
(b)speedoflight(c,ms1),energy(E,J),Planck'sconstant(h,Js)andwavelength(,m).
Makeenergythesubject.
(c) specificheat(c,Jg 1K1),temperaturechange(T,K),mass(m,g)andheat(q,J).Make
massthesubject.
(d)gasdensity(p,kgm3),pressure(p,Pa),molarmass(M,kgmol1),thegasconstant(R,J
mol1K1)andtemperature(T,K).Makepressurethesubject.(Hint:RecallthatPaisa
derivedunit.)
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
absoluteuncertainty hashedwedge precision
accuracy heterolytic primarycarbonatom
acyclicalkanes homolytic saturatedhydrocarbon
alkane hydrate scientificnotation
alkylgroup hydrocarbon second
ampere(A) isomers secondarycarbonatom
anhydrous kelvin SI(SystmeInternational)
ballandstickmodel kilogram units
binarycompound linestructure significantfigures
candela mechanisticarrows solidwedge
catenation metre spacefillingmodel
chemicalformula mole structuralformula
condensedstructuralformula molecularformula substituent
constitutionalisomers nomenclature terminalcarbon
cycloalkane oxoanion tertiarycarbonatom
dimensionalanalysis parentchain unit
functionalgroup percentageuncertainty

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

3 ChemicalReactionsand
Stoichiometry
Chemicalplantsproducelargequantitiesofbasicchemicalsusedineverydayconsumergoods,industrial
processesandresearchlaboratories.However,ifyoumanageaplantliketheQueenslandAluminaRefinery
(pictured)andwanttorunitefficiently,youmustknowhowmuchstartingmaterialisneededtosynthesisea
productwiththebestpossibleyield.Someoftheinformationcomesfromchemicalequations.Chemical
equationsconvenientlyandsuccinctlysummariseinformationaboutchemicalreactions.Theyshowthe
substancesyoustartwithandthesubstancesyouendupwith.Theyalsoshowtherelativeamountsofeach
substance.Inthischapter,youwilllearnhowtousebalancedchemicalequationsandtherulesof
stoichiometrytoworkoutthemassofthesubstancesrequiredtoformadesiredmassofaproduct.Agood
understandingofstoicinvolvedhiometryisessentialforindustrialscaleproduction,pharmaceutical
manufactureandcontrollingreactionsinresearchlaboratories.Itisalsoessentialforstudentswantingto
understandbasicchemistry.

KEYTOPICS

3.1Chemicalequations
3.2Balancingchemicalequations
3.3Themole
3.4Empiricalformulae
 3.4Empiricalformulae
3.5Stoichiometry,limitingreagentsandpercentageyield
3.6Solutionstoichiometry

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.1ChemicalEquations
Theproductionofnewsubstancesfromoneormorechemicalspeciesiscalledachemicalreaction.A
chemicalequation,aconceptwebrieflyintroducedinchapter1,maybeusedtodescribewhathappens
whenachemicalreactionoccurs.Ituseschemicalformulaetoprovideabeforeandafterpictureofthe
chemicalsubstancesinvolved.Consider,forexample,thereactionbetweenhydrogenandoxygen(a
combustionreaction)togivewater.Thechemicalequationthatdescribesthisreactionis:

Thetwoformulaethatappeartotheleftofthearrowarethoseofthereactants,hydrogenandoxygen,
i.e.thesubstancesthatreacttoformtheproduct.Theformulaoftheproduct,water,iswrittentothe
rightofthearrow.Productsarethesubstancesthatareformedinthereaction.Thearrowmeansreact
toproduce.Thus,thisequationtellsusthathydrogenandoxygenreacttoproducewater.Thereverse
process,thereactionofwatertoformhydrogenandoxygen,canalsooccur,butonlytoaverysmall
extent.Reactionsinwhichboththeforwardandreversereactionsoccurarecalledreversiblereactions.
Themajorityofchemicalreactionsarereversibletosomeextent,but,fornow,wewillbeconcerned
onlywiththeforwardreaction.Wewilllearnmoreaboutreversiblereactionsinchapter9.

Inthisexample,onlyonesubstanceisformedinthereaction,sothereisonlyoneproduct.Aswewill
see,however,inmostchemicalreactionsthereismorethanoneproduct.Ifweareconcernedonlywith
determiningtheidentityoftheproducts,weareengagedinqualitativeanalysiswesimplydetermine
whichsubstancesarepresentinasamplewithoutmeasuringtheiramounts.Bycontrast,inquantitative
analysis,ourgoalistomeasuretheamountsofthevarioussubstancesinasample.

Stoichiometry(fromtheGreekstoicheionmeaningelementandmetreinmeaningmeasuring)is
concernedwiththerelativeamountsofreactantsandproductsinachemicalreaction.Intheequationfor
thereactionofhydrogenandoxygen,thenumber2precedestheformulaeofhydrogenandwater.The
numbersinfrontoftheformulaearecalledstoichiometriccoefficients,andtheyindicatethenumberof
moleculesofeachkindamongthereactantsandproducts.Thus,2H2means2moleculesofH2,and
2H2Omeans2moleculesofH2O.Whennonumberiswritten,thestoichiometriccoefficientis1(sothe
coefficientofO2equals1).Stoichiometriccoefficientscanalsorefertoionsoratoms.

Stoichiometriccoefficientsarerequiredtoensuretheequationconformstothelawofconservationof
mass(section1.2).Becauseatomscannotbecreatedordestroyedinachemicalreaction,wemusthave
thesamenumberofatomsofeachkindpresentbeforeandafterthereaction(i.e.onbothsidesofthe
arrow),asshowninfigure3.1.Thisisanexampleofabalancedchemicalequation.Anotherexample
isshowninfigure3.2:theequationforthereactionofbutane,C4H10,withoxygen,O2.Butanecanbe
usedasthefuelincampingstoves.

FIGURE3.1Thereactionbetween2moleculesofhydrogenand1moleculeofoxygengives2moleculesof
waterasdepictedbythespacefillingmodelsandchemicalequationshownhere.
 FIGURE3.2Thechemicalequationforthecombustionofbutane,C4 H10 .Theproductsarecarbondioxide
andwatervapour.

The2beforeC4H10tellsusthat2moleculesofbutaneareinvolvedinthereaction.Thisinvolvesatotal
of8carbonatomsand20hydrogenatoms(seefigure3.3).Noticethatwehavemultipliedthenumbers
ofatomsofCandHin1moleculeofC4H10bythecoefficient2.The13infrontofO2meansthat13
moleculesofO2arerequiredforcompletereactionof2moleculesofC4H10.Ontheright,wefind8
moleculesofCO2,whichcontainatotalof8carbonatoms.Similarly,10watermoleculescontain20
hydrogenatoms.Finally,wecancount26oxygenatomsonbothsidesoftheequation.

FIGURE3.3Understandingcoefficientsinanequation.Theexpression2C4 H10 describes2moleculesof

butane(depictedhereasballandstickmodels),eachofwhichcontains4carbonand10
hydrogenatoms.Thisgivesatotalof8carbonand20hydrogenatoms.

SpecifyingStatesofMatter
Inachemicalequation,itisusefultospecifythephysicalstatesofthereactantsandproducts,i.e.
whethertheyaresolids,liquidsorgases.Thisisdonebywriting(s)forsolid,(l)forliquidor(g)forgas
afterthechemicalformula.Forexample,theequationforthecombustionofcarboninacharcoal
briquettecanbewrittenas:

Attimes,wewillalsofinditusefultoindicatethataparticularsubstanceisdissolvedinwater.Wedo
thisbywriting(aq),meaningaqueoussolution,aftertheformula.Forinstance,thereactionbetween
stomachacid(anaqueoussolutionofHCl)andCaCO3,theactiveingredientinsomeantacids,is:

Thistypeofchemicalequationiscalledamolecularequation.Itshowsallreactantsandproducts,with
molecularsubstanceswrittenasdiscretemoleculesandioniccompoundswrittenintermsoftheir
empiricalformulae(seesection3.4).Ifioniccompoundsareinvolvedwecanalsowritenetionic
equationsthatonlyshowtheionsinvolvedintheactualreaction(seep.97).

PRACTICEEXERCISE3.1
 Howmanyatomsofeachelementappearon
eachsideofthearrowinthefollowing
equation?

PRACTICEEXERCISE3.2
Rewritetheequationinpracticeexercise3.1
toshowthatMg(OH)2isasolid,HCland
MgCl2aredissolvedinwater,andH2Oisa
liquid.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.2BalancingChemicalEquations
Wehavelearnedthatachemicalequationisashorthand,quantitativedescriptionofachemicalreaction.
Anequationisbalancedwhentheatomspresentamongthereactantsarealsopresentinthesame
numberamongtheproducts.Aswelearned,stoichiometriccoefficients(thenumbersinfrontof
formulae)aremultipliernumbersfortheirrespectiveformulae,andthevaluesofthecoefficients
determinewhetheranequationisbalanced.

Alwaysapproachthebalancingofanequationasatwostepprocess.
Step1:Writetheunbalancedequation.Organisetheformulaeinthepatternofanequationwith
plussignsandanarrow.
Step2:Adjustthecoefficientssothatthereareequalnumbersofeachkindofatomoneachsideof
thearrow.Applythefollowingguidelinesinsequence:
a.BalanceelementsotherthanHandO.
b.Balanceasagroupthosepolyatomicions(ionsconsistingoftwoormorecovalentlybonded
atomsseechapter2)thatappearunchangedonbothsidesofthearrow.
c.Balanceionssothattheoverallchargeisthesameonbothsidesofthearrow.
d.Balancethosespeciesthatappearontheirown(aselementsorions).
e.BalancethenumberofHandOatomsonbothsides(e.g.byusingH OorOH).
2
Theguidelinesarederivedfromexperience,butarenothardandfastrules.Thesequenceofrulesis
chosensothatthespeciesthataremostdifficulttobalancearehandledfirstandtheeasiestoneslast(H
andOareeasilybalancedinaqueoussolutions).

Whenyoucarryoutstep2,makenochangesintheformulae,eitherintheatomicsymbolsortheir
subscripts.Ifyoudo,theequationwillinvolvedifferentsubstancesfromthoseintended.Itmaystill
balance,buttheequationwillnotbeforthereactionyouwant.

Wewillbeginwithsimpleequationsthatcanbebalancedbyinspection.Anexampleisthereactionof
aluminiummetalwithhydrochloricacid(seefigure3.4).First,weneedthecorrectformulaeandthe
correctphysicalstates.Inthisexample,weusethemolecularequation(seeabove)eventhoughboth
HClandAlCl3existasionsinaqueoussolution.Thereactantsarealuminium,Al(s),andhydrochloric
acid,HCl(aq).Wealsoneedformulaefortheproducts.Thereactionresultsintheformationofaqueous
aluminiumchloride,whichwewriteasAlCl3(aq),andhydrogengas,H2(g).Recallfromthechemical
equationonp.4thathydrogennormallyexistsasdiatomicmoleculesandnotasindividualatoms.
 FIGURE3.4Aluminiumandhydrochloricacidreacttoformaluminiumchlorideandhydrogengas.

Step1:Writeanunbalancedequation.

Step2:Adjustthecoefficientstogetequalnumbersofeachkindofatomonbothsidesofthearrow
byapplyingtheguidelinesintheordergivenabove.Usingtheguidelines,wewilllookatClfirstin
ourexample.Becausethereare3Clatomstotherightofthearrowbutonly1totheleft,weputa3
infrontoftheHClontheleftside.Theresultis:

Sincetherearenopolyatomicionsinthisexample,welooknextatspeciesthatappearontheirown
(AlandH2,inthisexample).YoucanseethatAllooksbalanced,butthereare3Hatomsontheleft
andonly2ontheright.Wecanbalancethesebyputtingacoefficientof3infrontofH2andthen
doublingthecoefficientforHCl.

However,Clisnownotbalancedthereare6Clatomsontheleftandonly3ontheright.Therefore,
weneedacoefficientof2infrontofAlCl3.

EverythingisnowbalancedexceptforAlthereis1Alatomontheleftbut2ontheright.Weputa
coefficientof2infrontofAltogive:

Nowthereare2Al,6Hand6Clatomsoneachsideoftheequationandeverythingisbalanced.
Notethattheequation4Al(s)+12HCl(aq)4AlCl3(aq)+6H2(g)isalsobalanced,butitisusualto
writebalancedequationsusingthesmallestwholenumbercoefficients.

WORKEDEXAMPLE3.1

WritingaBalancedEquation
Aqueoussolutionsofcalciumhydroxide,Ca(OH)2,andphosphoricacid,H3PO4,reactto
givecalciumphosphate,Ca3(PO4)2,andwater.Thecalciumphosphateprecipitatesfrom
solution.Writethebalancedequationforthisreaction.

Analysis

First,writeanunbalancedequationthatincludesthereactantformulaeonthelefthandside
andtheproductformulaeontheright.Includethedesignation(aq)forallsubstances
dissolvedinwaterand(l)forH2Oitselfwhenitisinitsliquidstate.Thenadjust
stoichiometriccoefficients(neversubscripts!)untilthereisthesamenumberofeachtypeof
atomontheleftandrightsidesoftheequation.

Solution

Thereareseveralthingsnotinbalance,butourguidelinessuggestthatweworkwithCafirst,
ratherthanwithOandHatoms,orthePO43polyatomicions,whichremainunchangedon
bothsidesoftheequation.Thereare3Caatomsontherightside,soweputa3infrontof
Ca(OH)2ontheleft,asatrial.

NowtheCaatomsareinbalance.ThePO43anionsarenotbalancedthereare2ontheright
sideandonly1ontheleftside.Weputa2infrontofH3PO4asthenextstep.

NotcountingthePO43anions,wehaveontheleft6Oand6Hatomsin3Ca(OH)2plus6H
atomsinH3PO4,foranettotalof6Oand12Hatomsontheleft.Ontheright,inH2O,we
have1Oand2Hatoms.Theratioof6Oto12Hatomsontheleftisequivalenttotheratio
of1Oto2Hatomsontheright,sowewritethemultiplier(coefficient)6infrontofH2O.

Wenowhaveabalancedequation.

Isouranswerreasonable?

Acountofthetotalnumberofatomsoneachsideoftheequationshowsthattheyarethe
same.Oneachsidewehave3Ca,12H,2Pand14Oatoms.Thecoefficientsusedcannot
bereducedtosmallerwholenumbersandsowehaveanequationbalancedwiththesmallest
wholenumbercoefficients.

PRACTICEEXERCISE3.3
Whenaqueoussolutionsofbariumchloride,
BaCl2,andaluminiumsulfate,Al2(SO4)3,are
 mixed,areactionoccursinwhichsolid
bariumsulfate,BaSO4,precipitatesfromthe
solution.TheotherproductisAlCl3(aq).
Writethebalancedequationforthisreaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.3TheMole
Intheprecedingsections,youhaveseenthatchemicalformulaetellusabouttherelativenumerical
proportionsofatomsinmoleculesorioniccompounds,andthatchemicalequationsareaconvenient
waytosummarisewhathappensinchemicalreactions.Inthisandthefollowingsections,youwill
investigatethequantitativerelationshipsfurtherandfindthatthesearegovernedbytherulesof
stoichiometry.

Inachemicalreaction,therelativeratiosofreactantsresultinginagivenratioofproductsaregivenby
thechemicalequationsthatwelookedatinearliersectionsofthischapter.That,however,isonan
atomicormolecularlevel.Forexample:

tellsyouthat1moleculeofAreactswith2moleculesofBtoform1moleculeofAB2.Supposethatwe
wantedtocarryoutthisreactioninthelaboratory.Giventhatwecannotseeorcountindividualatoms,
ionsormolecules,weneedtoweighoutandworkwithlargerquantities,buthowdoweknowwhat
massesofAandBtouse?Itturnsoutthatsomeoftheinformationweneedtoanswerthisquestionis
giveninthebalancedchemicalequation.

Thinkaboutitthisway.Ifyouneed50000sheetsofwhitephotocopypaperandyouorderthemfroma
papermill,themillwillweighthemoutratherthancountingtheindividualsheets.Thisprocedureis
muchsimplerandquickerandreliesonthefactthatweknowthemassofonesheetofpaper,andthat
everysheetofpaperweighsthesame(atleasttoaverygoodapproximation).Itis,therefore,easyto
calculatetheweightthatcorrespondsto50000sheetsofpaper.Thesameprincipleappliestocounting
largenumbersofcoinsifyouwanttodepositthematabank.

Wecantakeasimilarapproachtocountingions,atomsandmolecules.Everyatomhasacertainmass.
Aswesawinchapter1,themassesofindividualatomscanbemeasuredinatomicmassunits(u),where
1u=1.6605410 24g,exactly ofthemassofa12Catom.Ifwereversethisdefinition,weseethat
6.0221410 23u=1g,so12gof12Ccontainsexactly6.0221410 23atoms.Itisclearthatevena
smallmassofasubstancecontainsaverylargenumberofatoms.Therefore,weuseaquantitycalled
themole.Themole(unitsymbol:mol)istheSIunitofamountofsubstance.Onemoleistheamountof
substancethatcontainsthesamenumberofspecifiedentitiesasthereareatomsinexactly12gof12C.
ThisnumberiscalledtheAvogadroconstant(NA),anditunderpinsallofchemistry.

WewillgenerallyquotetheAvogadroconstanttofoursignificantfigures.Whenwetalkaboutan
amount,wemeananamountofsubstanceinmoles.ThenumericalvalueoftheAvogadroconstantis
almostbeyondcomprehension.Forexample,6.02210 23grainsofsandwouldcoverAustraliaand
NewZealandtoadepthofabout1.3metres.However,becauseatomsaresoincrediblysmall,amoleof
atoms,moleculesorionstakesupcomparativelylittlespace(seefigures3.5and3.6).Onemoleof
anythingcontains6.02210 23entities.Inchemistryterms,theseentitiesareusuallyatoms,ionsor
molecules,butthedefinitionofamoledoesnotrestrictthenatureoftheseentities.Forexample,one
moleofeggswouldcontain6.02210 23eggs.Wecaninfactthinkofthemoleasbeingthechemist's
dozenjustas12eggsconstituteadozen,6.02210 23eggsconstituteamole.Mostimportantly,the
moleconvenientlylinksatomicmassandmacroscopicamountswhateveranythingweighsinatomic
massunits,amoleofitwillweighingrams.
 FIGURE3.5Onemoleofdifferentelements(clockwisefromtopleft:sulfur,aluminium,mercuryandcopper).
Eachsampleoftheseelementscontains6.0221023 atoms.

FIGURE3.6Onemoleofdifferentcompounds(clockwisefromtopleft):coppersulfatepentahydrate,water,
sodiumchromateandsodiumchloride.

Itisimportantthatwespecifyexactlywhichparticularspecieswearediscussingwhenweusethemole.
Forexample,thephrase1moleofoxygenisambiguous,becausewehavenotspecifiedwhetherwe
aretalkingabout1moleofoxygenatoms,O,oroxygenmolecules,O2,soitisusualtoincludea
chemicalformulawheneverthemoleisused.

Ofparticularinteresttousinchemistryisthemassof1mole.Wesawinthedefinitionofthemole
abovethat1molof12Cweighs12g,butitstandstoreasonthat1molofeggsisgoingtoweighrather
morethanthis.Therefore,whilethenumberofspecifiedentitiesinamoleisconstant,themassof1
moleofthoseentitiesdependsonthemassoftheindividualentities.Wecallthemassof1molofany
specifiedentitythemolarmass(M).Thisservesasthelinkbetweenmass(m)andamountofsubstance
(n)throughtheequation:

TheSIunitofmolarmassisactuallykgmol1,butthisisrarelyusedinpractice.Molarmassvaluesare
almostalwaysquotedinunitsofgmol1thatis,thenumberofgramspermoleofsubstance.
Inchapter1,weintroducedtheconceptofatomicmass,themassofasingleatomofanelement,which
wemeasuredinatomicmassunits.Themolarmass,whichasthemassof1moleofatomsofan
element,isnumericallyequaltotheatomicmass,buttheunitsdiffer.Valuesofmolarmassforthe
elementsaretabulatedinsidethefrontcoverofthisbook,anditisinformativetolookatsomeofthese.
Notethatthesevaluesrefertoamoleofatomsoftheelements,regardlessofwhethertheelements
themselvesexistinatomicform.Forexample,thetabulatedmolarmassofHis1.00794gmol1even
thoughelementalhydrogenexistsasH2molecules,notHatoms.ThemolarmassofCis12.0107g
mol1,avaluethatmightsurpriseyou,giventhatwestatedpreviouslythat1moleof12Cweighsexactly
12g.Weneedtoappreciatethatthemolarmassofanelementisdeterminedbytheisotopicmakeupof
thatelement.Carbon,forexample,hastwomajornaturallyoccurringisotopes,namely12Cand13C,and
anysampleofcarbonwillcontaintheseisotopesin98.89%and1.11%abundance,respectively.This
meansthatthemolarmassofnaturallyoccurringcarbonisnotexactly12gmol1,butjustalittle
greater,reflectingthesmallamountoftheheavier13Cisotopepresent.Themolarmassesofallelements
withmorethanonenaturallyoccurringisotopereflecttherelativemassandabundanceofeachisotope.

Becausenoelementhasamolarmassexactlyequaltoaninteger(eventhosewithasingleisotope,as
wesawonp.10),forsimplicityofcalculationsinthisbookwewillusuallyusemolarmassestofour
significantfigures.Thereisnoneedtolearnthevaluesofmolarmass(theywillalwaysbeavailable),
butitisimportanttolearnhowtousethem.Theequation:

whichdefinesmolarmass,isoneofthemostimportantinallofchemistry,andwewilluseitoften.With
it,andjustoneotherequation(whichwewillencounterlaterinthischapter),wehaveeverythingwe
needtosolveanystoichiometryproblem.Theapproachtodoingstoichiometryproblemsisdeciding
howtoapplythesetwoequations.

WORKEDEXAMPLE3.2

CalculatinganAmountfromaMass
TheGoldenJubileediamondisthelargestfaceteddiamondintheworld.Ithasamassof
109.13g.Ifthestoneconsistsofpurecarbon,whatamountofCdoesthestonecontain,
giventhatthemolarmassofCis12.01gmol1?

Analysis

Agoodmethodtofollowwhenbeginninganystoichiometryproblemistoasktwoquestions:
Whatvaluedoesthequestionwantmetodetermine?,andWhatdatahaveIbeengiven?.
Writedowntheanswerstothesequestionsandthenlookforanequationthatcontainsas
manyaspossibleofthese.Inthiscase,weareaskedtodetermineanamount(n),andwe
havebeengivenamolarmass(M)andamass(m).Theequationthatcontainsalloftheseis
.

Solution

Werearrange tosolveforn: Hence:

 Therefore,thisdiamondcontains9.087molesofcarbon.

Isouranswerreasonable?

Wehave109.13gofcarboninthediamond.Giventhat1moleofChasamassof12.01g,
10moleswouldhaveamassof120.1g.Weshouldthereforeexpectananswerofslightly
fewerthan10moles,whichwehave.Ouranswerthereforeseemsreasonable.

PRACTICEEXERCISE3.4
Whatamountofsulfurmolecules,S8,is
presentin35.6gofsulfur?Themolarmass
ofatomicsulfur,S,is32.06gmol1.

Whensolvingthistypeofproblem,alwayschecktheunitsoftheanswer.Thisisespeciallyimportantif
itisnecessarytorearrangetheequationtosolvetheproblem.Theunitswillalwaysbecorrectifyou
haverearrangedtheequationcorrectly.Inworkedexample3.2,wearedividingmassbymolarmass.
Gramsinthenumerator(thetopline)willcancelgramsinthedenominator(thebottomline),leaving

asourfinalunit.Thisisthesameas ,whichismol,meaningthatourunitsarecorrect.As

wesawonp.28,unitsarealsoverypowerfulinhelpingyoutorememberequations.Theequation
iseasytorememberifyouknowthattheunitsofmolarmassaregmol1:inotherwords,grams
(theunitofmass)dividedbymoles(theunitofamount).Thisthengivesthecorrectformofthe
equation.

WORKEDEXAMPLE3.3

CalculatingaMassfromanAmount
Calciumphosphate,Ca3(PO4)2,isoftenusedtocoatsomeofthesurfacesofboneordental
implantstopermitbonetobondwiththeimplantsurface.Aschematicisshowninfigure3.7.
 FIGURE3.7Somesurfacesonboneimplantsarecoatedwithcalciumphosphatetopermitbone
tobondtothesurface.

Ifacoatingprocedurecandeposit0.115molofpureCa3(PO4)2onanimplant,whatisthe
massofthecoating?ThemolarmassofCais40.08gmol1,ofPis30.97gmol1andofOis
16.00gmol1.

Analysis

Weareaskedtocalculateamass(m)andwearegivenanamount(n)andthemolarmasses
(M)ofCa,PandO.Wewillthereforeuse again,butwewillhavetocalculatethe
molarmassofCa3(PO4)2fromtheindividualmolarmassesoftheelementsbeforewecan
substitutethedataintotheequation.

Solution

Wenowrearrange tomakemthesubject:

Substitutionofthedatagives:

Therefore,thecoatingofCa3(PO4)2weighs35.7g.

Isouranswerreasonable?

Thecoatingcontainsalittleover0.1ofamoleofCa3(PO4)2.Since0.1of310gis31g,and
ouranswerof35.7gisslightlymorethan31g,itmakessense.

PRACTICEEXERCISE3.5
Whatmassofsodiumcarbonate,Na2CO3,
correspondsto0.125molofNa2CO3?

PRACTICEEXERCISE3.6
DeterminetheamountofH2SO4ina45.8g
sampleofH2SO4.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.4EmpiricalFormulae
Wheneveranewcompoundisprepared,itisusuallyanalysedtodeterminethemasspercentagesoftheelementsit
contains.Fromthesemasspercentages,itispossibletoobtainanempiricalformulaofthecompound.Theempirical
formulaisthesimplestwholenumberratioofatomswithinthatcompound.Forexample,theempiricalformulaof
butane(chemicalformulaC4H10)isC2H5.Ifweknowtheratiobymassofeachelementwithinacompound,wecan
determineitsempiricalformulausingtherelationship .

ChemicalConnections

CampbellMicroanalyticalLaboratory

Arguablythemostimportantaspectofchemistryisthesynthesisofnewcompounds.Chemistsaroundthe
worldprepareatleastonemillionneverbeforemadecompoundseveryyear,andeveryoneofthesemustbe
characterisedinsomeway.Oneofthefundamentaltechniquesusediselementalanalysis,inwhichthemass
percentagesofelementsinthenewcompoundaredetermined.Aswewillseeinthischapter,masspercentage
dataallowustoobtainanempiricalformulaforthecompoundwecanusethis,incombinationwithavariety
ofothermethods,whichwewillmeetinlaterchapters,todetermineitsstructure.

TheCampbellMicroanalyticalLaboratoryintheDepartmentofChemistryattheUniversityofOtagoisoneof
theveryfewmicroanalyticalservicesavailableinAustralasia.Ithasover50yearsofexpertiseinelemental
analysisandcarriesoutanalysesformanyuniversitiesinNewZealandandAustralia.

RoutineelementalanalysesinvolvedeterminationofthemasspercentagesofC,H,NandSinacompound,
andareoftencarriedoutusinganautomatedelementalanalysersuchastheoneshownintheschematic
diagraminfigure3.8.Thesamplesarecombustedwithoxygenathightemperature(oxidation)inthe
presenceofacatalyst.Theresultinggasesarethenpassedoveracatalystlayerandthroughcoppertoremove
excessO2andtoreducenitrogenoxidestonitrogen(reduction).Thegases,CO2,H2O,SO2andN2,arethen
separatedbyinjectionontoachromatographycolumn,andtheamountofeachismeasuredusingavery
sensitivethermalconductivitydetector.ThesedataarethenconvertedtomasspercentagesofC,H,NandS,
respectively.
 FIGURE3.8Diagramofanautomatedelementalanalysissystemforcarbon,hydrogen,nitrogenandsulfur.The
diagramillustratesthecombustionchamber,thechromatographycolumn,athermalconductivity
detector,andasampleofachromatogramwithpeaksforN2 ,CO2 ,H2 OandSO2 .

ElementsotherthanC,H,NorSinasamplemustbeanalysedmanually,andstandardmethodsareavailable
forthese.NotethatOisnotusuallyanalyseddirectly,anditsmasspercentageinanorganiccompoundis
generallyobtainedbysubtractingthetotalmasspercentagesofalltheotherelementsfrom100.

MoleRatiosfromChemicalFormulae
Considerthechemicalformulaforwater,H2O:
1moleculeofwatercontains2Hatomsand1Oatom.
2moleculesofwatercontain4Hatomsand2Oatoms.
1dozenmoleculesofwatercontain2dozenHatomsand1dozenOatoms.
1moleofmoleculesofwatercontains2molesofHatomsand1moleofOatoms.

Whetherwearedealingwithatoms,dozensofatomsormolesofatoms,thechemicalformulatellsusthattheratioof
HatomstoOatomsinH2Oisalways2to1.Forchemicalcompounds,moleratiosarethesameastheratiosofthe
individualatoms.

Thisfactletsuspreparemoletomoleconversionfactorsinvolvingelementsincompoundsasweneedthem.For
example,intheformulaP4O10,thesubscriptsmeanthatthereare4molesofPforevery10molesofOinthis
compound.Wealsoknowthat1moleofP4O10contains4molesofPand10molesofO.

Inthelaboratory,stoichiometryiscommonlyusedtorelatethemassesoftwostartingmaterialsthatareneededto
synthesiseacompoundandtodeterminereactionyields,aswewillseelaterinthischapter.

WORKEDEXAMPLE3.4

CalculatingAmountsofElementsWithinaCompound
Leaveshaveacharacteristicgreencolour(figure3.9)duetothepresenceofthegreenpigmentchlorophyll,
whichhastheformulaC55H72MgN4O5.Aparticularsampleofchlorophyllwasfoundtocontain0.0011g
ofMg.Whatmassofcarbonwaspresentinthesample?(M C=12.01gmol1M Mg=24.31gmol1)

FIGURE3.9Thecharacteristicgreencolourofleavesisimpartedbythepresenceofthepigmentchlorophyll.

Analysis

Weareaskedtocalculateamassofcarbon(mC)andaregivenamassofmagnesium(mMg)andmolar
massesofbothcarbonandmagnesium.Thedatagivenallowustocalculatetheamountofmagnesium(n)
inthesampleusing wethenusethemoleratiobetweenMgandC,whichisimplicitintheformula
ofchlorophyll,todeterminetheamountofCpresent.

Oncewehavethisamount,wethenuse againtoconvertittomass.

SolutionFirst,wecalculatetheamountofMgcorrespondingto0.0011gofMg:

Wenowlookattheformulaofchlorophyll,C55H72MgN4O5,toobtainthemoleratiobetweenMgandC.In
1moleculeofchlorophyll,wehave1atomofMgand55atomsofC.Therefore,in1moleofchlorophyll,
wehave1moleofMgand55molesofC.ThemoleratiobetweenMgandCistherefore1:55,meaning
thatthereis55timestheamountofCasthereisMginchlorophyll.Inthisproblem,wehave4.510 5mol
Mg,soweobtaintheamountofCfrom:

Nowweknowtheamountofcarbon,wecanconvertthistomass:

Therefore,0.030gCwaspresentinthesample.

Isouranswerreasonable?
 ThemolarmassofmagnesiumisabouttwicethatofC.Sinceweneed55molCforevery1molMg,the
massofCwerequireshouldbeabout30timesthatofMg.Ouranswerwas0.030gCfor0.0011gMg,so
themassofCwegotisabout30timesthemassofthemagnesiumwestartedwith.Thisseemsreasonable.

PRACTICEEXERCISE3.7
Whatmassofironisina15.0gsampleofFe2O3?

PRACTICEEXERCISE3.8
Whatmassofironisrequiredtoreactwith25.6gof
OtoformFe2O3?Assumethatthereaction
proceedstocompletion.

TheDeterminationofChemicalFormulae
Inresearchlaboratories,chemistsoftensynthesiseentirelynewcompoundsorisolatepreviouslyunknowncompounds
fromplantandanimaltissues.Theymustthendeterminetheformulaandstructureofthecompound.Thisusually
involvesmassspectrometry(seechapter20),whichgivesanexperimentalvalueforthemolarmass.Thecompound
canalsobedecomposedchemicallytofindthemassesofelementswithinagivenamountofcompound,aprocess
calledelementalanalysis(seeChemicalConnectionsonp.78).Letusseehowexperimentalmassmeasurementscan
beusedtodeterminethecompound'sformula.

Theusualformfordescribingtherelativemassesoftheelementsinacompoundisalistofpercentagesbymasscalled
thecompound'smasspercentagecomposition.Ingeneral,apercentagebymassisfoundbyusingthefollowing
equation:

WORKEDEXAMPLE3.5

CalculatingaPercentageCompositionfromChemicalAnalysis
Asampleofaliquidwithamassof8.657gwasfoundtocontain5.217gofcarbon,0.9620gofhydrogen
and2.478gofoxygen.Whatisthepercentagecompositionofthiscompound?

Analysis

Wemustapplythepercentagecompositionequationforeachelement.Themassofwholesamplehereis
8.657g,sowetakeeachelementinturnanddothecalculations.

Solution
 Oneoftheusefulthingsaboutapercentagecompositionisthatitallowsustoworkoutthemassofeachof
theelementsin100gofthesubstancewithoutfurthercalculation.Forexample,theresultsinthisproblem
tellusthatin100.00goftheliquidthereis60.26gofcarbon,11.11gofhydrogenand28.62gofoxygen.

Isouranswerreasonable?

Thecheckisthatthepercentagesmustaddupto100%iftheindividualmassesadduptothetotalmass,
allowingforsmalldifferencescausedbyroundingandexperimentalerror.

PRACTICEEXERCISE3.9
From0.5462gofacompound,0.1417gof
nitrogenand0.4045gofoxygenwasisolated.
Whatisthepercentagecompositionofthis
compound?Areanyotherelementspresent?

Elementscancombineinmanydifferentways.Nitrogenandoxygen,forexample,formallofthefollowing
compounds:N2O,NO,NO2,N2O3,N2O4andN2O5.Toidentifyanunknownsampleofacompoundofnitrogenand
oxygen,wecomparethepercentagecompositionfoundbyexperimentwiththecalculatedpercentagesforeach
possibleformula.

WORKEDEXAMPLE3.6

CalculatingaTheoreticalPercentageCompositionfromaChemical
Formula
Arethemasspercentagesof25.92%Nand74.09%OconsistentwiththeformulaN2O5?(M N=14.01g
mol1M O=16.00gmol1)

Analysis

Essentially,weareaskedtocalculatethemasspercentagesofNandOinthecompoundN2O5.Thedatawe
aregivenarethemolarmasses(M)ofNandO.Theonlyequationweknowthatcontainsmolarmassis
sowewillhavetousethisatsomestage.TocalculatethetheoreticalpercentagesbymassofN
andOinN2O5,weneedthemassesofNandOinaspecificsampleofN2O5.Ifwechoose1moleofthe
givencompoundasthesample,calculatingtherestofthedatawillbeeasier.

Solution

Weknowthat1moleofN2O5contains2molesofNand5molesofO.ThecorrespondingmassesofNand
Oarefoundusing asfollows:
 Themassof1moleofN2O5will,therefore,bethesumofthemassofNandthemassofOin1moleofthe
moleculethatis,28.02g+80.00g=108.02g.

Wecannowcalculatethepercentagesbymassaswedidinworkedexample3.5:

ThereforetheexperimentaldataareconsistentwiththeformulaN2O5.

Isouranswerreasonable?

Wegetagoodmatchbetweenthecalculatedandexperimentalvalues,whichisalwaysencouraging!In
problemslikethis,youshoulddoublecheckyourcalculationsandmakesurethatthepercentagesofallthe
elementspresentaddupto100%iftheindividualmassesadduptothetotalmass,withinroundingand
experimentalerror.

PRACTICEEXERCISE3.10
CalculatethepercentagecompositionofN2O4.

DeterminationofEmpiricalFormulae
ThecompoundthatformswhenphosphorusburnsinoxygenconsistsofmoleculeswiththeformulaP4O10.Whena
formulagivesthecompositionofonemolecule,itiscalledthemolecularformula.Notice,however,thatboththe
subscripts4and10aredivisibleby2,sothesmallestnumbersthattellustheratioofPtoOis2to5.Asimpler(but
lessinformative)formulathatexpressesthisratioisP2O5.Thisissometimescalledthesimplestformulaforthe
compound.Itisalsocalledtheempiricalformulabecauseitcanbeobtainedfromanexperimentalanalysisofthe
compound.

Toobtainanempiricalformulaexperimentally,weneedtodeterminethemassofeachelementinasampleofthe
compound.Frommass,wethencalculateamount,fromwhichweobtainthemoleratiosoftheelements.Becausethe
ratiobymolesisthesameastheratiobyatoms,wecanconstructtheempiricalformula.

Onlyrarelyisitpossibletoobtainthemassesofeveryelementinacompoundbytheuseofjustoneweighedsample
twoormoreanalysesondifferentsamplesmayberequired.Forexample,supposeananalystisgivenacompound
knowntoconsistexclusivelyofcalcium,chlorineandoxygen.Themassofcalciuminoneweighedsampleandthe
massofchlorineinanothersamplewouldbedeterminedinseparateexperiments.Thenthemassdataforcalciumand
chlorinewouldbeconvertedtopercentagesbymass(equivalenttothemassofeachoftheseelementsinasampleof
100g).Thisallowsthedatafromdifferentsamplestobecompareddirectly.Themasspercentageofoxygenwould
thenbecalculatedbydifferencebecause%Ca+%Cl+%O=100%.Eachmasspercentagecanberelatedtothe
correspondingamountoftheelement.Themoleproportionsareconvertedtowholenumbersaswehavejuststudied,
givingusthesubscriptsfortheempiricalformula.

Therefore,thethreestepsnecessarytodetermineanempiricalformulaare:
1.Assumewearestudying100gofthecompound.Therefore,theindividualmasspercentagescorrespondtothe
actualmassesoftheelementsin100gofthecompound.
2.Converttheratioofelementsbymasstoaratiobyamount,bydividingthemassofeachelementbyitsmolar
mass.
3.Dividetheresultingnumbersbythesmallestone,whichwillgivethesmallestratiooftheelementsinthe
compound.Ifthisgivesanynumbersthatarenotintegers,multiplyallnumbersintheratiobythesmallestfactor
thatwillresultinallnumbersbeingintegers.

WORKEDEXAMPLE3.7

CalculatingAnEmpiricalFormulafromPercentageComposition
Awhitepowderusedinpaints,enamelsandceramicshasthefollowingmasspercentagecomposition:Ba,
69.6%C,6.09%andO,24.3%.Whatisitsempiricalformula?(M Ba =137.3gmol1M C=12.01gmol
1M 1)
O=16.00gmol

Analysis

Weareaskedtocalculateanempiricalformula,andwearegivenmasspercentagecompositionsandmolar
mass(M)values.Wecanconvertmasspercentagetomass(m)simplybychoosing100gofcompoundto
study.WecanthencalculateamountsofBa,CandObyusing ,andusethesetoobtainthe
necessarymoleratiosfortheempiricalformula.

Solution

A100gsampleofthecompoundwillcontain69.6gBa,6.09gCand24.3gO.Wefirstrelatethese
massestoamounts:

OurratioofBa:C:Oistherefore0.507:0.507:1.52.However,chemicalformulaecontainwhole
numbers,sowedivideeachamountbythesmallestamount.Theratiothenbecomes:

Therefore,ourmoleratiois1Ba:1C:3O,andtheempiricalformulaisBaCO3.

Isouranswerreasonable?

Iftheformulaiscorrect,thereare3molesofoxygenforevery1moleofcarboninthecompound.So,for
every1mole(12g)ofcarboninthecompound,thereshouldbe3moles(48g)ofoxygen.Thecarbonto
oxygenmassratiois12:48,or1:4.Thisisconsistentwiththeratioofcarbonandoxygenpercentages
(6.09:24.31:4).

PRACTICEEXERCISE3.11
Awhitesolidusedtowhitenpaperhasthe
followingmasspercentagecomposition:Na,32.4%
S,22.6%.Therestofthemassisoxygen.Whatis
theempiricalformulaofthecompound?
Inpractice,acompoundisseldombrokendowncompletelytoitselementsinaquantitativeanalysis.Instead,the
compoundischangedintoothercompounds.Thereactionsseparatetheelementsbycapturingeachoneentirely
(quantitatively)inaseparatecompoundwithaknownformula.

Inthefollowingexample,weillustrateanindirectanalysisofacompoundmadeentirelyofcarbon,hydrogenand
oxygen.Suchcompoundsburncompletelyinpureoxygenthereactioniscalledcombustionandthesole
productsarecarbondioxideandwatervapour.Thecompletecombustionofethanol,CH3CH2OH,forexample,occurs
accordingtothefollowingequation.

Thecarbondioxideandwatercanbeseparatedandthentheirmassesdetermined.Noticethatallofthecarbonatoms
intheoriginalcompoundendupamongtheCO2moleculesandallofthehydrogenatomsareinH2Omolecules.In
thiswayatleasttwooftheoriginalelements,CandH,areentirelyseparated.

ModernmicroanalyticaltechniquesallowthesimultaneousdeterminationofC,H,NandS,asdescribedinChemical
Connectionsonp.78.Initialcombustionofthesampleandsubsequentpassageoftheresultinggasmixtureovera
catalystresultsintheconversionofallCinthesampletoCO2,alltheHtoH2O,alltheNtoN2andalltheStoS2.The
massofeachgas,andhencethemassofeachelement(C,H,NandS),isthendetermined.Weconvertthemassesof
theelementsintopercentagesoftheelementbymassinthecompound.Wethenaddupthepercentagesandsubtract
from100togetthepercentageofO.Wethencalculatetheempiricalformulafromthepercentagecompositionas
describedearlier.

Theempiricalformulaisallthatweneedforioniccompounds.Formolecularcompounds,however,chemistsprefer
molecularformulaebecausetheygivethenumberofatomsofeachtypeinamolecule,ratherthanjusttheratioofthe
elementsinacompound,astheempiricalformuladoes.

Sometimesanempiricalformulaandamolecularformulaarethesame.TwoexamplesareH2OandNH3.Moreoften,
however,thesubscriptsofamolecularformulaarewholenumbermultiplesofthoseintheempiricalformula.The
subscriptsofthemolecularformulaP4O10,forexample,areeachtwotimesthoseintheempiricalformula,P2O5,aswe
sawearlier.ThemolarmassofP4O10islikewisetwotimesthemolarmassofP2O5.Thisobservationhelpsusfindthe
molecularformulaforacompound,providedwehaveawayofexperimentallydeterminingthemolarmassofthe
compound.Iftheexperimentalmolarmassequalsthecalculatedmassofanempiricalformula,theempiricalformula
itselfisalsoamolecularformula.Otherwise,theexperimentalmolarmasswillbesomewholenumbermultipleofthe
valuecalculatedfromtheempiricalformula.Whateverthewholenumberis,itisacommonmultiplierforthe
subscriptsoftheempiricalformula.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.5Stoichiometry,LimitingReagentsandPercentageYield
Sofarwehavefocusedonrelationshipsbetweenelementswithinasinglecompound.Wehaveseenthatthecriticallinkbetween
amountsofelementswithinacompoundisthemoletomoleratioobtainedfromtheformulaofthecompound.Inthissection,wewill
seethatthesametechniquescanbeusedtorelateamountsofsubstancesinvolvedinachemicalreaction.Thecriticallinkbetween
amountsofsubstancesinvolvedinareactionisamoletomoleratioobtainedfromthechemicalequationthatdescribesthereaction.

Toseehowachemicalequationcanbeusedtoobtainmoletomolerelationships,considertheequationthatdescribestheburningof
octane,C8H18,inoxygen,O2,togivecarbondioxideandwatervapour:

Thisequationcanbeinterpretedonamolecularscaleasfollows:forevery2moleculesofliquidoctanethatreactwith25moleculesof
oxygengas,16moleculesofcarbondioxidegasand18moleculesofwatervapourareproduced.

Wecanalsointerprettheequationonamolarscaleasfollows2molesofliquidoctanereactwith25molesofoxygengastoproduce
16molesofcarbondioxidegasand18molesofwatervapour.

Tousetheserelationshipsinastoichiometryproblem,theequationmustbebalanced.Wemustalwayschecktoseewhetherthisisso
foragivenequationbeforewecanusethecoefficientsintheequationtocalculatestoichiometricratios.

First,letusseehowmoletomolerelationshipsobtainedfromachemicalequationcanbeusedtorelatetheamountofonesubstance
totheamountofanotherwhenbothsubstancesareinvolvedinachemicalreaction.

WORKEDEXAMPLE3.8

StoichiometryofChemicalReactions
Whatamountofsodiumphosphate,Na3PO4,canbemadefrom0.240molofNaOHbythefollowingreaction?

Analysis

Weuseasimilarapproachtothatusedinworkedexample3.4but,inthiscase,werequirethemoleratiobetweendifferent
compounds.Weobtainthismoleratiodirectlyfromthestoichiometryofthebalancedchemicalequation.

Solution

Wecanseefromthestoichiometriccoefficientsthat3molesofNaOHwillreacttogive1moleofNa3PO4.Therefore,ifwe
startwith0.240molNaOH,wewillobtain:

Isouranswerreasonable?

Therearereallyonlytwopossibleanswerswecouldgettothisproblemthecorrectone(0.0800mol)andtheincorrect
one(0.720mol),whichwouldbeobtainedbymultiplyingratherthandividingby3.Lookingatthebalancedchemical
equation,wecanseethattheamountofNa3PO4producedislessthantheoriginalamountofNaOH.Inthiscase,our
answershouldbelessthan0.240mol,anditis.

PRACTICEEXERCISE3.12
Whatamountofsulfuricacid,H2SO4,isneededtoreact
completelywith0.366molofNaOHaccordingtothe
followingreaction?

PRACTICEEXERCISE3.13
 If0.575molofCO2isproducedbythecombustionof
propane,C3H8,whatamountofoxygenisconsumed?The
balancedchemicalequationisasfollows:

MoleRatiosinChemicalReactions
Weoftenneedtorelatemassofonesubstancetomassofanotherinachemicalreaction.Consider,forexample,thereactionof
glucose,C6H12O6,oneofthebody'sprimaryenergysourceswithoxygen.Thebodycombinesglucoseandoxygentogivecarbon
dioxideandwater.Thebalancedequationfortheoverallreactionis:

Whatmassofoxygenmustthebodytakeintocompletelyprocess1.00gofglucose(thatis,1.00gC6H12O6)?

Thefirstthingweshouldnoticeaboutthisproblemisthatwearerelatingamountsoftwodifferentsubstancesinareaction.Thelink
betweentheamountsofsubstancesisthemoletomolerelationshipbetweenglucoseandO2givenbythechemicalequation.Inthis
case,theequationtellsusthat1moleofC6H12O6willreactcompletelywith6molesofO2.

Ifweinsertthemoletomoleconversionbetweenourstartingpoint(1.00gC6H12O6)andthedesiredquantity(gO2),wecutthe
problemintothreesimplesteps:

WeobtaintheamountofC6H12O6fromthemassofC6H12O6usingthemolarmassofC6H12O6.Wethenobtaintheamountof
C6H12O6fromtheamountofO2,usingthestoichiometryofthebalancedequation.Finally,weobtainthemassofO2fromtheamount
ofO2usingthemolarmassofO2.Ifwehavecarriedoutthesemanipulationscorrectly,theanswershouldbe1.07gO2.

Oneofthemostcommonmistakesmadeinstoichiometryproblemslikethisistheincorrectdeterminationanduseofthemoleratios
forsubstancesinthereaction.

Considerthegeneralchemicalreaction:

whereA,B,CandDarereactantsandproductsinthereaction,anda,b,canddarethestoichiometriccoefficientsofeach.Forthis
reaction,thefollowingalwaysholds:

Applyingthistotheexampleabove,wefindthat:

and,ifwelimitourselvestothemoleratiobetweenglucoseandoxygen,wefind:

Havingcalculatedtheamountofglucose,weknowfromthepreviousequationthatthisisequalton O2/6.Wethenrearrangethis
equationtomaken O2thesubject:

andwefindthatwemustmultiply by6toobtainouranswer.

WORKEDEXAMPLE3.9

StoichiometricMassCalculations
Metallicironcanbemadebythethermitereaction,thespectacularreactionofaluminiumwithironoxide,Fe2O3.Somuch
heatisgeneratedthattheironformsintheliquidstate.Theequationis:

Assumethatyouneedtoproduce86.0gofFeinaweldingoperation.

WhatmassofbothFe2O3andaluminiummustbeusedforthisoperation,assumingalltheFe2O3isconvertedtoFe?(M Fe =
55.85gmol1M O=16.00gmol1M Al=26.98gmol1)
 Analysis

WeareaskedtofindthemassesofAlandFe2O3requiredtoprepare86.0gofFe.WearegivenamassofFe(m)andthe
molarmassofFe(M)sowecancalculatetheamountofFe(n)using .Wethenusethemoleratiosinthebalanced
chemicalequationtocalculatetheamountsofAlandFe2O3.Thefinalstepistouse toobtainthemassesfrom
theseamounts.

Insummary:

Solution

Firstly,wecalculatetheamountofFein86.0g:

Usingthestoichiometriccoefficientsfromthebalancedchemicalequation,wecanseethat:

Therefore,theformationof2molesofFerequires2molesofAland1moleofFe2O3.Inotherwords,wewillrequirethe
sameamountofAl,buthalftheamountofFe2O3.Therefore:

Thus,n Al=n Fe .Wethenuse toobtainthemassesfromtheseamounts:

Isouranswerreasonable?

AstheformationofFefromFe2O3involveslossofoxygenfromFe2O3,wewouldexpectthemassofFe2O3requiredtobe
greaterthanthemassofFeproduced.Giventhat2molesofAlgive2molesofFe,wewouldexpectthemassofAl
requiredtobelessthanthemassofFeproduced(86.0g),asthemolarmassofAlislessthanthatofFe.Hence,our
answersappearreasonable.

PRACTICEEXERCISE3.14
Whatmassofaluminiumoxideisalsoproducedwhen86.0
gofFeisformedbythereactiondescribedinworked
example3.9?

LimitingReagents
Wehaveseenthatbalancedchemicalequationscantellushowtomixreactantstogetherinjusttherightproportionstogetacertain
amountofproduct.Forexample,ethanol,CH3CH2OH,ispreparedindustriallyasfollows:

Theequationtellsusthat1moleofethenewillreactwith1moleofwatertogive1moleofethanol.Wecanalsointerprettheequation
onamolecularleveleverymoleculeofethenethatreactsrequires1moleculeofwatertoproduce1moleculeofethanol:
Ifwehave3moleculesofethenereactingwith3moleculesofwater,3ethanolmoleculesareproduced:

Whathappensifwemix3moleculesofethenewith5moleculesofwater?Theethenewillbecompletelyusedupbeforeallthewater,
andtheproductmixturewillcontain2unreactedwatermolecules,asshownbelow.

Thissituationcanbeaprobleminthemanufactureofchemicalsbecausewewasteoneofourreactants(water,inthiscase)andalso
obtainaproductthatiscontaminatedwithunusedreactant.Conversely,thiscanbeusedtoadvantageinsituationswhereoneofthe
reactantsischeapandeasilyrecoverable.Aswewillseeinchapter9,wecansometimesforcereactionstofavourtheformationof
productsbyaddinganexcessofoneofthereactants.AnexampleofthisisthepreparationofmargarinefromthereactionofH2with
animalorvegetableoilsuseofexcessH2makestheoilthelimitingreagentandensurescompleteconversionoftheoilto
margarine,andtheexcessH2canbeeasilyrecoveredandreused.

Inthereactionmixtureatthebottomofthepreviouspage,etheneiscalledthelimitingreagentbecauseitlimitstheamountofproduct
(ethanol)thatcanform.Wateriscalledanexcessreagentbecausewehavemoreofitthanisneededtocompletelyconsumeallthe
ethene.

Topredicttheamountofproductwemaytheoreticallyobtaininareaction,weneedtoknowwhichofthereactantsisthelimiting
reagent.Inthepreviousexample,wesawthatweneededonlythreeH2OmoleculestoreactwiththreeC2H4moleculeswehadfive
H2Omolecules,soH2OispresentinexcessandC2H4isthelimitingreagent.
Oncewehaveidentifiedthelimitingreagent,itispossibletocalculatetheamountofproductthatmightformandtheamountofexcess
reagentthatwouldbeleftover.

WORKEDEXAMPLE3.10

LimitingReagent
Gold(III)hydroxide,Au(OH)3,isusedforelectroplatinggoldontoothermetals.Itcanbemadebythefollowingreaction:

ToprepareafreshsupplyofAu(OH)3,achemistatanelectroplatingplantmixed20.00gofKAuCl4with25.00gof
Na2CO3(bothdissolvedinalargeexcessofwater).

WhatisthemaximummassofAu(OH)3thatcanform?(
)

Analysis

WeareaskedtodeterminethemaximummassofAu(OH)3thatcanbeformed.Wearegivenmasses(m)ofbothKAuCl4
andNa2CO3andtheirmolarmasses(M).ThisallowsustocalculatetheamountsofbothKAuCl4andNa2CO3using
.Wethenhavetousetheratiosofamountstostoichiometriccoefficientsinthebalancedchemicalequationto
determineifeitherKAuCl4orNa2CO3ispresentinexcess.Theothersubstancewouldthenbethelimitingreagent.

Solution

BeginbycalculatingtheamountsofKAuCl4andNa2CO3using :

Weknow,fromthestoichiometryofthereaction,that2molesofKAuCl4require3molesofNa2CO3forcompletereaction.
Inotherwords:

Ifwefindthatthisisthecase,thenthereactantsarepresentinexactlythecorrectstoichiometricamounts.Iftheratiosare
unequal,thesmallernumberindicatesthelimitingreagent.Intheexperiment,weuse:

ThismeansthatwehavetoomuchNa2CO3,soKAuCl4isthelimitingreagent.TheamountofKAuCl4nowdeterminesthe
amountofAu(OH)3thatcanbeformed.TocalculatehowmuchAu(OH)3willbeformed,weagainusethestoichiometric
coefficientsfromthebalancedchemicalequation.Weseethat2molesofKAuCl4willform2molesofAu(OH)3so:

ConvertingthisamountofAu(OH)3tomassgives:

Therefore,usingthereactionconditionsgiven,weobtainamaximumof13.13gofAu(OH)3.

Isouranswerreasonable?

Themainthingincalculationsofthistypeistogetthemoleratioscorrectand,indeed,tointerpretthemcorrectly.Wecan
 seethatthemolarmassofKAuCl4ismorethanthreetimesthatofNa2CO3.SinceweareusingalargermassofNa2CO3in
thereaction,wewillhaveasignificantlylargeramountofNa2CO3thanKAuCl4,andourcalculationsbearthisout.The
molarmassofAu(OH)3isabouttwothirdsthatofKAuCl4and,giventhattheirmoleratiointhebalancedchemical
equationis1:1,wewouldexpectthemassofAu(OH)3tobeabouttwothirdstheinitialmassofKAuCl4,whichitis.The
answerisreasonable.

PRACTICEEXERCISE3.15
Inanindustrialprocessforproducingnitricacid,thefirst
stepisthereactionofammoniawithoxygenathigh
temperatureinthepresenceofaplatinumgauzetoform
nitrogenmonoxideasfollows:

Whatisthemaximummassofnitrogenmonoxidethatcan
formfromaninitialmixtureof30.00gofNH3and40.00g
ofO2?

PercentageYield
Inmostchemicalsyntheses,theamountofaproductactuallyisolatedfallsshortofthecalculatedmaximumamount.Lossesoccurfor
severalreasons.Somearemechanical,suchasmaterialsstickingtoglassware.Insomereactions,lossesoccurbytheevaporationofa
volatileproduct.Inothers,asolidproductseparatesfromthesolutionasitformsbecauseitislargelyinsoluble.Thesolidisremoved
byfiltration.Whatstaysinsolution,althoughrelativelysmall,contributestosomelossofproduct.

Oneofthecommoncausesofobtaininglessthanthestoichiometricamountofaproductistheoccurrenceofareactionorreactions
thatcompetewiththemainreaction.Acompetingreactionproducesabyproduct,i.e.asubstanceotherthantheproductthatwe
wanttoobtain.(Note:Asecondproductofthemainreactionisalsocalledabyproducthowever,itdoesnotreducetheyield.)The
synthesisofphosphorustrichloridefromPandCl2,forexample,givessomephosphoruspentachlorideaswell,becausePCl3canreact
furtherwithCl2.

ThecompetitionisbetweennewlyformedPCl3andunreactedphosphorusforchlorine.Anothercauseoflowerthantheoreticalyields
isareversiblereaction,wheretheforwardandbackwardreactionsoccurconcurrently.

Thetheoreticalyieldofaproductiswhatwouldbeobtainedifthemaximumamountofproductwasformedandnolossesoccurred.
Itiscalculatedbasedonthebalancedchemicalequationandtheamountsofthereactantsavailable.Theactualyieldoftheproductis
simplyhowmuchhasbeenisolatedinpractice.Chemistscalculatethepercentageyieldofproducttodescribehowsuccessfulthe
preparationwas.Thepercentageyieldistheactualyieldcalculatedasapercentageofthetheoreticalyield:

Boththeactualandtheoreticalyieldsmust,ofcourse,beinthesameunits.

Itisimportanttorealisethattheactualyieldisanexperimentallydetermined(ratherthancalculated)quantity.Thetheoreticalyieldis
alwaysacalculatedquantitybasedonachemicalequationandtheamountsofthereactantsavailable.

WORKEDEXAMPLE3.11

CalculatingaPercentageYield
Achemistsetupasynthesisofphosphorustrichloride,PCl3,bymixing12.0gofPwith35.0gofCl2andobtained42.4g
ofPCl3.Theequationforthereactionis:

Calculatethepercentageyieldofthiscompound.( )
 Analysis

Weareaskedtocalculateapercentageyield.Wearegivenmassesofallthreecomponentsinthereactionandtheirmolar
masses(M).Thismeanswecancalculatetheamountsofallthreeusing .Tocalculatethepercentageyield,wemust
firstdecideonwhichreactanttobaseourcalculations.Wemustcalculatetheamountsofeachbeforewecanmakethat
decision.Ifwefindthatoneofthereactantsisalimitingreagent,thepercentageyieldisbasedonthatreactant.Tocalculate
thepercentageyield,wemustfirstcalculatethetheoreticalyield:inotherwords,howmuchproductwouldhavebeen
formedifthereactionwenttocompletion.Wedoallofthisusing andthestoichiometryofthebalancedchemical
equation.

Solution

WebeginbycalculatingtheamountsofbothPandCl2used.

Fromthebalancedchemicalequation,weknowthatPreactswithCl2inthemoleratio2:3.Therefore,forcomplete
reaction,theoretically:

Theexperimentalratiosare0.494mol/3=0.165forCl2and0.387mol/2=0.194forP.Thismeansthatwedonothave
sufficientCl2toreactwithallthePpresent,soCl2isthelimitingreagent.Wenowbaseoursubsequentcalculationsonthis.
Fromthebalancedchemicalequation,weknowthat:

Therefore,0.165mol ,so .Convertingthistomass,weobtain:

Theactualmassobtainedwas42.4g,sothepercentageyieldisgivenby:

Isouranswerreasonable?

Theobviouscheckisthattheactualyieldcanneverbemorethanthetheoreticalyield.So,onthisscore,ouransweris
reasonable.Again,themostcommonplacewhereerrorsaremadeisintheuseofthemoleratios.Inthisexample,wemust
endupwithfewermolesofrPCl3thanCl2,sowemustmultiplyn Cl2by ,not .Weappeartohavedonethecalculations
correctly,sotheanswerisreasonable.

PRACTICEEXERCISE3.16
Ethanol,CH3CH2OH,canbeconvertedtoaceticacid(theacidinvinegar),CH3COOH,bytheactionofsodiumdichromate,
Na2Cr2O7,inaqueoussulfuricacidaccordingtothefollowingequation:

Inoneexperiment,24.0gofCH3CH2OH,90.0gofNa2Cr2O7andaknownexcessofsulfuricacidwasmixed,and26.6gof
aceticacidwasisolated.CalculatethepercentageyieldofCH3COOH.

Anotherwaytolookattheyieldofareactionistotakeintoaccountthesocalledatomefficiency.Bythiswemeanthatthereisa
differencebetweenareactionwheremostoftheatomsofthestartingmaterial(s)endupformingthedesiredproductandareaction
wherealargefractionoftheatomsinthestartingmaterialendupasunwantedbyproducts.Thereclearlyisatradeoffbetweenthe
percentageyieldofareactionandtheatomefficiency.Concernsaboutpollutionandcostcertainlyfavourreactions(atleastonthe
industrialscale)thatproducetheleastamountofwastematerial.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.6SolutionStoichiometry
Chemicalreactionsaremostoftencarriedoutinsolutionbecausethisallowsintimatemixingofthereactants,whichleadstomorerapidreaction.Asolution
isahomogeneousmixtureinwhichtheatoms,moleculesorionsofthecomponentsfreelyintermingle(seefigure3.10).Whenasolutionforms,atleasttwo
substancesareinvolved.Oneiscalledthesolventandalloftheothersarecalledsolutes.Thesolventisusuallytakentobethecomponentpresentinlargest
amountandisthemediumintowhichthesolutesaremixedordissolved.Liquidwaterisatypicalandverycommonsolvent,butthesolventcanactuallybe
inanyphysicalstatesolid,liquid,orgas.Unlessstatedotherwise,wewillassumethatanysolutionswementionareaqueoussolutions,sothatliquid
waterisunderstoodtobethesolvent.

FIGURE3.10Inthephotoontheleft,acrystalofiodine,I2 ,thatwasaddedtoabeakercontainingethanolstarteddissolvingonitswaytothebottomofthebeaker,the
purplishiodinecrystalformingareddishbrownsolution.Thephotoontherightshowshowafterstirringthemixturewithaspatulathesolutiontakesona
homogeneousreddishbrowncolour,duetotheiodinemoleculesdissolvedinthesolventasindicatedintheschematicbelowthepicture.Calledtinctureof
iodine,suchsolutionswereoncewidelyusedasantiseptics.

Asoluteisanysubstancedissolvedinthesolvent.Itmightbeagas,likethecarbondioxidedissolvedincarbonateddrinks.Somesolutesareliquids,like
theethyleneglycoldissolvedinwatertostopitfromfreezinginacar'sradiator.Solids,ofcourse,canbesolutes,likethesugardissolvedinlemonadeorthe
saltdissolvedinseawater.

TheConcentrationofSolutions
Weusetheconcentrationofasolutiontodescribeitscomposition.Theconcentrationisdefinedastheamountofsolutedissolvedinaparticularvolumeof
solution.TheconcentrationofasubstanceXisoftenrepresentedas[X].Whentheamountisgiveninmolesandthevolumeinlitres,itiscalledthemolarity
ormolarconcentrationandhastheunitsmolL1(oftenabbreviatedm,nottobeconfusedwiththeabbreviationformolarmass,M).Theequationthat
definesconcentration(c)is:

Westatedearlierthattherewereonlytwoequationsneededtosolveanystoichiometricproblem. wasthefirst,andthisisthesecond.Again,we
mustcommitthistomemory,butitiseasytorememberwhenweconsidertheunitsofconcentrationmolL1impliesamountdividedbyvolume(inL).

Thus,a1.00Lsolutionthatcontains0.100molofNaClhasamolarityof0.100M,andwewouldrefertothissolutionas0.100molarNaCloras0.100M
NaCl.A0.100Lsolutioncontaining0.0100molofNaClwouldhavethesameconcentrationbecausetheratioofamountofsolutetovolumeofsolutionis
thesame.

Concentrationisparticularlyusefulbecauseitletsusobtainagivenamountofasubstancesimplybymeasuringavolumeofapreviouslypreparedsolution,
andthismeasurementisquickandeasytodointhelaboratory.Ifwehadastocksupplyof0.100MNaClsolution,forexample,andweneeded0.100mol
ofNaClforareaction,wewouldsimplymeasureout1.00Lofthesolutionbecausethereis0.100molofNaClinthisvolume.

Weneednot(andseldomdo)workwithwholelitresofsolutions.Itistheratiooftheamountofsolutetothevolumeofsolution,notthetotalvolume,that
matters.Suppose,forexample,thatwedissolved0.0200molofsodiumchromate,Na2CrO4,insufficientsolventtogiveafinalvolumeof0.250L.The
concentrationofthesolutionwouldbefoundby:

Suchasolutioncanbeaccuratelypreparedinavolumetricflask,whichisanarrowneckedcontainerwithanetchedmarkhighonitsneck.Whenfilledup
tothemark,theflaskcontainsthevolumegivenbytheflask'slabel.Figure3.11showshowtousea250mLvolumetricflasktoprepareasolutionof
knownconcentration.

FIGURE3.11 Thepreparationofasolutionofknownmolarity:
(a)A250mLvolumetricflask,oneofanumberofsizesavailableforpreparingsolutions.Whenfilledtothelineetchedarounditsneck,thisflask
containsexactly250mLofsolution.Theflaskherealreadycontainsaweighedamountofsolute.
(b)Waterisbeingadded.
(c)Thesoluteisbroughtcompletelyintosolutionbeforethelevelisbroughtuptothenarrowneckoftheflask.
(d)Morewaterisaddedtobringthelevelofthesolutiontotheetchedlineoruptothemark.
(e)Theflaskisstopperedandtheninvertedmanytimestomixitscontentsthoroughly.

Wheneverwehavetodealwithaproblemthatinvolvesanamountofachemicalandavolumeofasolutionofthatsubstance,wewillusetheequation
.

WORKEDEXAMPLE3.12

CalculatingtheConcentrationofaSolution
AstudentpreparedasolutionofNaClbydissolving1.461gofNaClinwaterandmakinguptothefinalvolumeof250.0mLinavolumetric
flasktostudytheeffectofdissolvedsaltontherustingofanironsample.Whatistheconcentrationofthissolution?

Solution

Firstly,weconvertthemassofNaCltoamountusing:

Wethensubstitutethedatainto andsolveforc:

Therefore,theconcentrationoftheNaClsolutionis1.00010 1molL1.

Isouranswerreasonable?

A1molL1solutionofNaClwouldcontain58.44gofNaClin1litre,soa0.1molL1solutionwouldcontainabout6gin1L.Wehave0.25L,
sowewouldexpectabout(0.256g)=1.5gin0.25L,whichisroughlywhatwehave.Theansweriscertainlyreasonable.Aneasymistaketo
makeinproblemsofthistypeistoforgettoconvertmLtoL.RememberthattheunitsofconcentrationmustalwayscomeoutasmolL1so,if
thesolutionvolumeisgiveninmL,wemustdivideby1000toconverttoL.

PRACTICEEXERCISE3.17
AspartofastudytodetermineifjustthechlorideioninNaCl
acceleratestherustingofiron,astudentdecidedtoseeifironrustedas
 rapidlywhenexposedtoasolutionofNa2SO4.Thissolutionwasmade
bydissolving3.550gofNa2SO4inwaterandmakingupthefinal
volumeto100.0mLinavolumetricflask.Whatistheconcentrationof
thissolution?

Noticethatworkedexample3.12usesboth and .Aswehavestressed,withthesetwoequations,thereisnostoichiometricproblemwe

cannotsolve!

Inthelaboratory,weoftenmustprepareasolutionwithaspecificconcentration.Usually,weselectthevolumeofsolutionthatwewillmakeandthen
calculatehowmuchsolutemustbeused.Dependingontheaccuracythatyourequirefortheconcentration,youwillneedtouseabalancethatallowsyou
toweighyoursampletotherequirednumberofsignificantfigures.Figure3.12showsarangeofbalancesandglasswareusedinthepreparationofsolutions
ofknownconcentration.Workedexample3.13illustratesthekindofcalculationrequiredandalsodemonstratesthefollowingusefulrelationship:whenever
weknowboththevolumeandtheconcentrationofasolution,wecancalculatetheamountofsolutefrom .

FIGURE3.12 (a)Glasswarethatcanbeusedformeasuringvolumestodifferentaccuraciesand
(b)ananalyticalbalancethatcanbereadto1107 g.

WORKEDEXAMPLE3.13

PreparingaSolutionofKnownConcentration
Strontiumnitrate,Sr(NO3)2,isusedinfireworkstoproducebrilliantredcolourslikethoseshowninfigure3.13.Whatmassofstrontiumnitrate
wouldachemistneedtoprepare250.0mLofa0.100MSr(NO3)2solution?

FIGURE3.13Theredcolourinsomefireworksisaresultofthepresenceofstrontiumnitrate,Sr(NO3 )2 .

Analysis

Weareaskedtocalculateamass(m)ofstrontiumnitrateandwearegiventhevolume(V)andconcentration(c)ofastrontiumnitratesolution,as
wellasthemolarmass(M)ofstrontiumnitrate.Theconcentrationandvolumewillallowustocalculatetheamount(n)ofstrontiumnitrateusing
,andwecanthenusethisamountintheequation tocalculatethemassofstrontiumnitrate.

Solution

Werearrange tosolveforn:
 Wecannowuse toobtainthemass:

Therefore,thechemistwouldrequire5.29gofSr(NO3)2topreparethesolution.

Isouranswerreasonable?

In1litreof0.100MSr(NO3)2,therewouldbe0.1molofSr(NO3)2,about20g.Therefore,in0.25Lofthissolution,wewouldhaveroughly
(0.2520g)=5g.Theanswer,5.29g,isclosetothis,soitmakessense.

PRACTICEEXERCISE3.18
WhatmassofAgNO3isneededtoprepare250mLof0.0125M
AgNO3solution?

DilutingaSolution
Itisnotalwaysnecessarytobeginwithasoluteinpureformtoprepareasolutionwithaknownconcentration.Thesolutecanalreadybedissolvedina
solutionofrelativelyhighconcentration,oftencalledthestocksolution,andthiscanbedilutedwiththesamepuresolventtomakeasolutionofthedesired
lowerconcentration.Dilutionisaccomplishedbyaddingmoresolventtothesolution,whichcausestheconcentration(theamountperunitvolume)to
decrease(figure3.14).Thechoiceofapparatususeddependsontheprecisionrequired.Ifhighprecisionisnecessary,pipettesandvolumetricflasksare
used(figure3.12a).Ifwecandowithlessprecision,wemightusegraduatedcylindersinstead.Workedexample3.14showshowwecanuse to
calculatethefinalconcentrationofadilutedsolution.

FIGURE3.14Dilutingasolution.Whensolventisaddedtoasolution,thesoluteparticlesbecomemorespreadoutandthesolutionbecomesmoredilute.The
concentrationofthesoluteinthesolutionbecomeslower,whilethetotalamountofsoluteremainsconstant.

WORKEDEXAMPLE3.14

PreparingaSolutionofKnownConcentrationbyDilution
Howcouldweprepare100.0mLof0.0400MK2Cr2O7fromasolutionof0.200MK2Cr2O7?

Analysis

Weareaskedhowtodiluteaconcentratedsolutiontogiveasolutionofaparticularconcentration.Weknowboththevolume(V)andthe
concentration(c)ofthefinalsolution,souseof willallowustocalculatenfromthesedata.Asweknowtheconcentrationoftheinitial
solution,andwehavecalculatedtherequiredn, willallowustocalculateV,thevolumeoftheinitialsolutionrequired.

Solution

Wearegoingtouse twice,tocalculatetwodifferentthings.Firstly,wecalculate inourfinalsolution:

ThisistheamountofK2Cr2O7that,whendissolvedin100.0mL,willgiveaconcentrationof0.0400M.Wenowturnourattentiontotheinitial
solutionandusethiscalculatedamount,inconjunctionwiththeconcentration,tocalculateV,thevolumeoftheinitialsolutionrequired.
 Therefore,wetake20.0mLoftheoriginalsolution,pouritintoa100.0mLvolumetricflaskandmakeituptothemarkwithwatertogeta0.0400
MsolutionofK2Cr2O7(figure3.15).

FIGURE3.15 Preparingasolutionbydilution:
(a)Thecalculatedvolumeofthemoreconcentratedsolutioniswithdrawnfromthestocksolutionbymeansofavolumetricpipette.
(b)Thesolutionisallowedtodrainentirelyfromthepipetteintothevolumetricflask.
(c)Waterisaddedtotheflask,thecontentsaremixedandthefinalvolumeisbroughtuptothemarkonthenarrowneckoftheflask.

Isouranswerreasonable?

Thinkaboutthemagnitudeofthedilution,from0.2Mto0.04M.Noticethattheconcentratedsolutionisfivetimesasconcentratedasthedilute
solution(50.04=0.2).Toreducetheconcentrationbyafactoroffiverequiresthatweincreasethevolumebyafactoroffive,andweseethat
100mLis520mL.Theanswerappearstobecorrect.

Inadilution,theamountofsubstanceintheconcentratedsolutionisthesameasinthedilutedsolution.Thisallowsustouseashortcutforthecalculation
thatwecarriedoutinworkedexample3.14.

Ifwedefinec1andV1astheconcentrationandvolumeoftheinitialsolutionandc2andV2asthoseofthefinalsolution,becausenisthesameinboth
solutionswecanwriten=c1V1andn=c2V2.Astheamount,n,isthesameforbothsolutions,wecanthencanceloutn,togivetheequationc1V1=c2V2.If
weknowtheinitialconcentrationandthefinalvolumeandconcentrationwecansolvefortheinitialvolume:

Thatis,ifwemultiplythefinalvolumebytheratiooffinaltoinitialconcentration,weobtaintherequiredvolumeoftheinitialsolution.Forworked
example3.14,wecouldwrite:
 PRACTICEEXERCISE3.19
Howcould0.1mLof0.125MH2SO4solutionbemadefroma0.500
MH2SO4solution?

ApplicationsofSolutionStoichiometry
Whenwedealquantitativelywithreactionsinsolution,weoftenworkwithvolumesofsolutionsandconcentrations.

WORKEDEXAMPLE3.15

StoichiometryInvolvingReactionsinSolution
Beforetheadventofdigitalcameras,silverbromide,AgBr,wasusedextensivelyinphotographicfilm.Thiscompoundisessentiallyinsolublein
water,andonewaytoprepareitistomixsolutionsofthewatersolublecompounds,silvernitrateandcalciumbromide(seefigure3.16).

FIGURE3.16AdditionofCaBr2 (aq)toAgNO3 (aq)resultsinprecipitationofcreamywhiteAgBr(s).

SupposewewishedtoprepareAgBrbythefollowingprecipitationreaction:

Whatvolumeof0.125MCaBr2solutionwouldberequiredtoreactcompletelywith50.0mLof0.115MAgNO3?

Analysis

WeareaskedtocalculateavolumeofCaBr2solution,andwearegiventhevolume(V)andconcentration(c)ofaAgNO3solution.Wecan
calculatetheamount(n)ofAgNO3using .Wearealsogivenabalancedchemicalequation,andwewillneedtousethistoobtainthemole
ratiobetweenAgNO3andCaBr2.Wethenusethestoichiometriccoefficientsfromthebalancedchemicalequationtocalculate .Finally,
wewilluse alongwiththeconcentrationoftheCaBr2solutiontocalculatethevolumeoftheinitialsolutionrequired.
 Solution

Westartbycalculatingn AgNO3:

Fromthebalancedchemicalequation,weknowthat2molesofAgNO3willreactwith1moleofCaBr2.Therefore:

Wenowknow andtheconcentrationoftheCaBr2solution,sowecansubstitutethesevaluesinto tocalculateV,thevolumeofthe

CaBr2solutionrequired.

Therefore,23.0mLoftheCaBr2solutionwillreactcompletelywith50.0mLofthe0.115MAgNO3solution.

Isouranswerreasonable?

Themolaritiesofthetwosolutionsareaboutthesame,butonly1moleofCaBr2isneededforevery2molesofAgNO3.Therefore,thevolume
ofCaBr2solutionneeded(23.0mL)shouldbeabouthalfthevolumeofAgNO3solutiontaken(50.0mL),whichitis.

PRACTICEEXERCISE3.20
Whatvolumeof0.124MNaOHisrequiredtoreactcompletelywith
15.4mLof0.108MH2SO4accordingtothefollowingequation?

StoichiometryofSolutionsContainingIons
Inworkedexample3.15,weusedanequationinvolvingioniccompoundstosolveastoichiometryproblem.Ioniccompoundsdissociateintotheir
constituentionsiftheydissolveinwaterandthiscanhaveimportantconsequencesinstoichiometriccalculationsinvolvingsuchsolutions.Forexample,in
workedexample3.15,weusedcalciumbromide,CaBr2,asareactant.Supposeweareworkingwithanaqueoussolutionlabelled0.10MCaBr2.This
meansthereis0.10moleofCaBr2dissolvedineachlitreofthissolutiondissociatedintoCa2+andBrions.

Fromthestoichiometryofthedissociation,weseethat1moleofCa2+(aq)and2molesofBr(aq)areformedfromeachmoleofCaBr2(s).Therefore,0.10
moleofCaBr2(s)willyield0.10moleofCa2+(aq)and0.20molesofBr(aq).In0.10MCaBr2,then,theconcentrationofCa2+(aq)is0.10Mandthe
concentrationofBr(aq)is0.20M.Noticethattheconcentrationofaparticularionequalstheconcentrationofthesaltmultipliedbythenumberofionsof
thatkindintheformulaofthesalt.

Weusethetermdissolutiontodescribetheprocessofasolutedissolvinginasolvent,anditisimportantthatyouunderstandthedifferencebetweenthe
termsdissolutionanddissociation.Whenanioniccompoundundergoesdissolution(dissolves)inasolvent,itundergoesdissociationintoitsconstituent
ions.WeshowedtheequationforthisprocesswithreferencetoCaBr2(s)above,andassumedthatthesaltdissociatesfully.However,dissociationreactions
donotnecessarilydothat,andtheextentofsuchreactionsdependsonthenatureoftheioniccompound.Wewillassume100%dissociationofallionic
compoundsintheremainingexamplesinthischapter.Wewillinvestigatepartialdissociationinchapter10.

Initiallyyoumayfinditdifficulttoknowexactlywhichionicspeciesdissolveinwaterandwhichonesdonot,butwithexperienceyouwillbeabletomake
reasonableassessments.Inthefirstinstanceatableofsolubilityrulescanbeagreathelp.Table3.1summarisestherulesforthesolubilitiesofmany
commonioniccompoundsandyoumayfindithelpfultobefamiliarwiththese.
TABLE3.1 Solubilityofcommonbinaryioniccompoundsinwater
Iftheanionis thecompoundisusually exceptfor

F soluble Mg 2+,Ca2+,Sr2+,Ba2+andPb 2+(Al3+)

Cl soluble Ag +andHg 22+(Pb 2+)

Br soluble Ag +andHg 22+(Hg 2+andPb 2+)

I soluble Ag +,Hg 2+,Hg 22+andPb 2+

NO3 soluble none

SO42 soluble Sr2+,Ba2+,Hg 22+andPb 2+(Ag +andCa2+)

CH3COO soluble none(Ag +andHg 22+)

 OH insoluble Li+,Na+,K+andBa2+(Ca2+andSr2+)

SO32 insoluble Li+,Na+,K+,NH4+andMg 2+

PO43 insoluble Na+,K+andNH4+

CO32 insoluble Li+,Na+,K+andNH4+

C2O42 insoluble Li+,Na+,K+andNH4+

Note:Forthepurposesofthistable,insolublecompoundsarearbitrarilydeemedtohavemolarsolubilitiesoflessthan110 2Minwater,slightly
solublecompoundshavemolarsolubilitiesinwaterbetween110 1Mand110 2M,whilesolublecompoundshavemolarsolubilitiesgreaterthan
110 1Minwater.Cationsinparenthesesformslightlysolublecompoundswiththespecifiedanion.Mostoxidesandsulfidesareinsolubleinwater
apparentexceptionstothisrule(e.g.Li2OandMgS)aregenerallycomplicatedbyhydrolysisreactionsandarethereforenotlisted.

Notethat,inworkedexample3.15,wewrotethebalancedchemicalequationasthemolecularequation:

Wecanalsowritethisintermsoftheionspresentastheionicequation:

Thenetreactionthatoccurredwas:

andtheNO3andCa2+tooknopartinthereaction,remainingsimplyasaqueousionsthroughout.Wecallsuchionsspectatorions.Balancedionic
equationswrittenwithouttheinclusionofspectatorionsarecallednetionicequations.Thatis,netionicequationsshowonlythoseionsthatparticipatein
thereaction.

WORKEDEXAMPLE3.16

CalculatingtheConcentrationsofIonsinaSolution
Whataretheconcentrationsoftheionsina0.20MsolutionofAl2(SO4)3(aq)?

Analysis

Theconcentrationsoftheionsaredeterminedbytheconcentrationofthesaltanditsstoichiometry.Weneedtowriteabalancedchemical
equationforthedissolutionofthesaltinwaterfromthis,wecandeterminetheconcentrationofeachioninthesolutionusingthegiven
concentrationofthesalt.

Solution

WhenAl2(SO4)3dissolves,itdissociatesasfollows:

EachmoleofAl2(SO4)3yields2molesofAl3+ionsand3molesofSO42ionsondissolution,assumingcompletedissociation.Therefore,ifwe
consider1litreofsolution,the0.20molofAl2(SO4)3willyield0.40molAl3+and0.60molSO42.Hence,theconcentrationsoftheionsinthe
solutionwillbe0.40MAl3+and0.60MSO42.

PRACTICEEXERCISE3.21
Whatarethemolarconcentrationsoftheionsin0.40MFeCl3(aq)?

PRACTICEEXERCISE3.22

InanaqueoussolutionofNa3PO4,thePO43concentrationwas
determinedtobe0.250M.Whatwasthesodiumionconcentrationin
thesolution?

Wehaveseenthatanetionicequationisconvenientforfocusingonthenetchemicalchangeinreactionsinvolvingions.Letusstudysomeexamplesthat
illustratehowsuchequationscanbeusedinstoichiometriccalculations.

WORKEDEXAMPLE3.17

StoichiometryCalculationsUsingNetIonicEquations
 WhenaqueoussolutionsofAgNO3andCaCl2aremixed,awhiteprecipitateofAgCl(s)isformed(seefigure3.17).Thenetionicequationforthe
formationofthisprecipitateis:

Whatvolumeof0.100MAgNO3solutionisneededtoreactcompletelywith25.0mLof0.400MCaCl2solutiontoformAgCl(s)?

FIGURE3.17AsolutionofAgNO3 (aq)isaddedtoasolutionofCaCl2 (aq),producingaprecipitateofAgCl(s).

Analysis

WeareaskedtocalculateavolumeofAgNO3solution.Thevolume(V)andconcentration(c)oftheCaCl2solutiongiveninthequestionallow
ustocalculaten CaCl2andhence using .Fromthestoichiometryofthereaction,wecanthendeterminetherequired .Wecan
thencalculatetherequiredvolumeusingthegivenconcentrationoftheAgNO3solution.

Solution

WearegivenavolumeandaconcentrationoftheCaCl2solution,sowesubstitutethesevaluesinto .

Weknowthat1moleofCaCl2willgive2molesofClondissolutioninwater(assumingcompletedissociation),so:

ThestoichiometryofthebalancedchemicalequationforthereactionofAg +andClshowsthat1moleofClwillreactwith1moleofAg +.
Therefore,wecansaythat:

Beforewecalculatetherequiredvolume,weneedtolookatthestoichiometryofAgNO3.Because1moleofAgNO3willgiveus1moleofAg +
whendissolvedinsolution:

Nowweobtain:

Thus,werequire200mLof0.100MAgNO3solution.

Isouranswerreasonable?

Silverionsreactwithchlorideionsina1:1ratio.CaCl2solutionisfourtimestheconcentrationoftheAgNO3solutionand,as1moleofCaCl2
dissolvestogive2molesofCl,theClconcentrationinthissolutioniseighttimestheconcentrationoftheAgNO3solution.Therefore,wewould
expectavolumeofAgNO3solutioneighttimesthevolumeoftheCaCl2solution.As825=200,ouranswerappearscorrect.

PRACTICEEXERCISE3.23
Whatvolumeof0.500MKOHisneededtoreactcompletelywith60.0
mLofa0.250MFeCl2solutiontoprecipitateFe(OH)2?

Earlierinthischapter(pp.868),welearnedhowtorecogniseandsolvelimitingreagentproblems.Similarproblemscanbeencounteredwhenworking
withnetionicequations.

WORKEDEXAMPLE3.18
CalculationInvolvingtheStoichiometryofAnIonicReaction

AsuspensionofMg(OH)2inwaterissometimesusedasanantacid.ItcanbemadebyaddingNaOHtoasolutioncontainingMg 2+.Supposethat
40.0mLofa0.200MNaOHsolutionisaddedto25.0mLofa0.300MMgCl2solution.Thenetionicequationforthereactionis:

WhatmassofMg(OH)2willbeformed,andwhatwilltheconcentrationsoftheionsinthesolutionbeafterthereactioniscomplete?(M Mg(OH)2=
58.33gmol1)

Analysis

WeareaskedtocalculatethemassofMg(OH)2andtheconcentrationsofionsinsolutionattheendofthereaction.Wearegivenconcentrations
(c)andvolumes(V)ofboththeNaOHandMgCl2solutions,whichallowustocalculateamounts(n)oftheseusing .Wearealsogiventhe
molarmass(M)ofMg(OH)2,whichallowsustouse tocalculatethemass(m)ofMg(OH)2.Thisproblemissimilartoworkedexample
3.17,butslightlymorecomplex.WemustcalculatetheamountsofMg 2+andOHpresentinitially,andworkoutwhichofthesewillbelimiting.
Wethenproceedinthesamewayaswehavedoneinotherlimitingreagentproblems,using tocalculatethemassofMg(OH)2formed.
Weobtaintheconcentrationsoftheionsleftinsolutionbydifference.

Solution

WebeginbycalculatingtheamountsofbothNaOH(aq)andMgCl2(aq),andthencalculatingn Mg2+and fromthese.

As1moleofNaOHgives1moleofOHondissolutioninwater:

Similarly:

Since1moleofMgCl2gives1moleofMg 2+ondissolutioninwater:

Lookingatthebalancedchemicalequation,weseethat1moleofMg 2+willreactwith2molesofOHso forcomplete

reaction.Therefore,wewouldrequire1.5010 2molofOH,butwehaveonly8.0010 3mol,meaningthatOHisthelimitingreagent.
Therefore,fromthebalancedchemicalequation,8.0010 3molOHwillreactwith4.0010 3molMg 2+togive4.0010 3molMg(OH)2.We
canobtainthemassofthisamountusing andthegivenmolarmassofMg(OH)2.

Therefore,thereactionforms0.233gMg(OH)2(s).

Westillhavetocalculatetheconcentrationsoftheionsinsolutionattheendofthereaction.TheionspresentwillbeMg 2+,ClandNa+.We
havealreadycalculatedtheamountofNaOHas8.0010 3mol,so .Thefinalvolumeofthesolutionis65.0mL(40.0
mLofNaOHsolutionplus25.0mLofMgCl2solution),so:

WehavealsocalculatedtheamountofMgCl2as7.5010 3mol,and,as1moleofMgCl2gives2molesofClondissolutioninwater,
.Wecanthenobtaintheconcentrationfrom:

WewillassumethatalloftheOHinsolutionhasprecipitatedasMg(OH)2sothefinalconcentrationofOHwillbe0.00molL1(infact,in
chapter10,wewillseethataverysmallamountofOHwillremaininsolution,butnotenoughtomakeasignificantdifferencetoourcalculation
here).ThefinalconcentrationweneedtocalculateisthatofMg 2+.Thisisslightlymoreinvolvedthantheothers,asweneedtorememberthat
someoftheMg 2+hasbeenprecipitatedasMg(OH)2.Earlier,wecalculatedtheinitialamountofMg 2+as7.5010 3mol.Wealsocalculatedthat
4.0010 3molofMg 2+hasprecipitatedasMg(OH)2,sowecanobtaintheamountofMg 2+insolutionbydifference.

Therefore,theconcentrationofMg 2+insolutionis:

Isouranswerreasonable?

Thiswasafairlycomplexproblemandtherearenosimplecalculationswecanmaketoverifyouranswers.However,thereareacoupleofkey
stepswemightdoublecheck.First,wecancheckthatwehaveidentifiedthelimitingreagentcorrectly.Inthepreviouscalculation,weselected
Mg 2+anddeterminediftherewasenoughOHtoreactwithit.Asacheck,letuslookatOHtoseeifthereisenoughMg 2+.Webeganwith8
10 3molofOH,whichrequireshalfthatamountofMg 2+(410 3molMg 2+)toreactcompletely.TheamountofMg 2+available(7.510 3
 mol)ismorethanenough,soMg 2+willbeleftoverandOHislimiting.Ouranalysisconfirmsthatwehaveselectedthecorrectlimitingreagent.

Anotherplacetobecarefulisinthecalculationofthefinalconcentrationsoftheionsinthereactionmixture.Wheneverweaddoneaqueous
solutiontoanother,themixturewillhaveafinalvolumethatisthesumofthevolumesofthetwosolutionscombined.Whencalculatingthe
concentrationsofanythinginthefinalmixture,wehavetousethefinalcombinedvolumeofthemixture.Weseethatwehavetakenthisinto
account,sowecanfeelconfidentwe'vedonethispartofthecalculationcorrectly.

PRACTICEEXERCISE3.24
WhatamountofBaSO4willformif20.0mLof0.600MBaCl2is
mixedwith30.0mLof0.500MMgSO4?Determinetheconcentration
ofeachioninthefinalreactionmixture.

Theworkedexamplesinthischaptersofarhavespecifiedthereactantsandproductsinvolved.Therewillbeoccasionswhenwedonotknowthe
compositionofoneofthese,butstoichiometrycanstillhelptodeterminetheamountofaparticularelementinanunknowncompound.Thecalculations
requiredforthesekindsofproblemsarenotnewtheyaresimplyapplicationsofthestoichiometriccalculationswehavealreadylearned.

WORKEDEXAMPLE3.19

CalculationInvolvinganUnknownCompound
Acompoundusedasaninsecticidecontainscarbon,hydrogenandchlorine.Reactionswerecarriedoutona1.340gsampleofthecompound
thatconvertedallofitschlorinetochlorideionsdissolvedinwater.ThisaqueoussolutionwastreatedwithanexcessofAgNO3solution,andthe
AgClprecipitatewascollectedandthenweighed.Itsmasswas2.709g.WhatwasthepercentagebymassofClintheoriginalinsecticide
sample?(M Cl=35.45gmol1M AgCl=143.32gmol1)

Analysis

Weareaskedtocalculateapercentagebymass.Wearegiventhemass(m)andmolarmass(M)ofAgClsowecancalculatetheamountofAgCl
using .Wecanobtaintherestofthenecessarydatausingmoleratios.Theimportantpointtounderstandinthisproblemisthatallthe
chlorineintheAgClthatwascollectedoriginatedfromtheinsecticidesample.Thestrategy,therefore,istodeterminethemassofClin2.709gof
AgCl.Wethenassumethatthisisthemassofchlorineintheoriginal1.340gsampleofinsecticideandcalculatethepercentageClasfollows:

Solution

WebeginbycalculatingtheamountofAgClusing .

As1moleofAgClcontains1moleofCl,theamountofClintheoriginalinsecticidesamplemustbe1.89010 2mol.Wecalculatethemassof
thisamountusing .

Wecannowcalculatethe%Clbymass.

Isouranswerreasonable?

LetusconsiderthemolarmassesofAgClandCl(143.32gmol1and35.45gmol1,respectively).Ifweroundtheseto140and35,wecansay
thatAgClisapproximately25%ofClbymass(35/140=0.25).Approximately3gofAgClwasobtained25%of3gequals0.75gofCl,which
isclosetothevalueweobtained.Theoriginalsampleweighed1.34g,whichisnearlytwice0.75g(themassofCl),soananswerof50%Clby
massseemsreasonable.

PRACTICEEXERCISE3.25
AsampleofamixturecontainingCaCl2andMgCl2weighed2.000g.
Thesamplewasdissolvedinwater,andH2SO4wasaddeduntilthe
precipitationofCaSO4wascomplete.TheCaSO4wasfiltered,dried
completelyandweighed.Atotalof0.736gofCaSO4wasobtained.
WhatamountofCa2+wasintheoriginal2.000gsample?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
ChemicalEquations
Achemicalreactionistheformationofnewsubstances(products)fromoneormorestartingmaterials
(reactants).Achemicalequationisabeforeandafterdescriptionofachemicalreaction.Aqualitative
analysisisconcernedonlywithwhichsubstancesarepresent.Aquantitativeanalysisisconcernedwith
theamountsofallthevarioussubstances.Stoichiometryisconcernedwiththerelativeamountsof
productsandreactantsinareaction.Stoichiometriccoefficientsarewritteninfrontofformulaein
chemicalequationstoindicatethenumberofspecifiedentitiesofeachkindamongthereactantsand
products.Abalancedchemicalequationhasthesamenumberofatomsofeachkindintheproductsand
reactants,thusconformingtothelawofconservationofmass.Thephysicalstatesofreactantsand
productscanbeshowninchemicalequationsusing(s)forsolid,(l)forliquidand(g)forgas.Weuse
(aq)toindicateanaqueoussolution(thatis,whenasubstanceisdissolvedinwater).

BalancingChemicalEquations
Achemicalequationisbalancedwhenallatomspresentamongthereactantsarealsosomewhereamong
theproducts.Tobalanceanequation,wefirstwritetheunbalancedequationandthenadjustthe
stoichiometriccoefficientstogetequalnumbersofeachkindofatomoneachsideofthearrow.

TheMole
Themole(mol)isthebaseSIunitforamount.Itistheamountofanysubstancewiththesamenumber
ofatomsormoleculesasthereareatomsinexactly12gof12C.TheAvogadroconstant,NA,is6.022
10 23mol1andgivesthenumberofspecifiedentitiesin1molofasubstance.Themolarmass,M,isthe
massof1molofasubstance.

EmpiricalFormulae
Theactualcompositionofamoleculeisgivenbyitsmolecularformula.Anempiricalformulagivesthe
ratioofatoms,butinthesmallestwholenumbers,anditisgenerallytheonlyformulawewriteforionic
compounds.Themolarmassofamolecularcompoundisequaltothatcalculatedfromthecompound's
empiricalformulaortoasimplemultipleofit.Whenthetwocalculatedmassesarethesame,the
molecularformulaisthesameastheempiricalformula.

Anempiricalformulacanbefoundfromthemassesoftheelementsobtainedbythequantitative
analysisofaknownsampleofthecompound,oritcanbecalculatedfromthepercentagecomposition
(thepercentageofanelementinacompoundisthesameasthenumberofgramsoftheelementin100
gofthecompound).IfthereisJ%ofXinXx Zz,then100gofXx ZzcontainsJgofX.TheamountsofX
andZcanbecalculatedfromthemassesofXandZ.Thesubscriptsintheempiricalformulaare
obtainedbyadjustingtheseamountstotheircorrespondingwholenumberratios.

Stoichiometry,LimitingReagentsandPercentageYield
Achemicalformulaisatoolforstoichiometriccalculations,becauseitssubscriptstellusthemoleratios
inwhichthevariouselementsarecombined.In1moleofXx Zz,xmolesofXarecombinedwithzmoles
ofZ.

Abalancedequationisatoolforreactionstoichiometrybecauseitscoefficientsdisclosethe
stoichiometricrelationships.Allproblemsofreactionstoichiometrymustbesolvedatthemolelevelof
thesubstancesinvolved.Ifmassesaregiven,theymustfirstbechangedtoamounts.

FromthegenericbalancedequationaA+bBcC+dD,itfollowsthatthemoleratiosforexact
stoichiometricreactionare:

Incaseswherethisequationdoesnothold,thereactantpresentinthesmallestmoleratioiscalledthe
limitingreagent.Theotherreactantiscalledtheexcessreagent.Thetheoreticalyieldofaproductcanbe
nomorethanthatpermittedbythelimitingreagent.Sometimes,competingreactions(sidereactions)
thatproducebyproductsreducetheactualyield.Theratiooftheactualyieldtothetheoreticalyield,
expressedasapercentage,isthepercentageyield.

SolutionStoichiometry
Asolutionisahomogeneousmixtureinwhichoneormoresolutesaredissolvedinasolvent.
Concentrationistheratiooftheamountofsolutetothevolumeofsolution.Solutionsofknown
concentrationcanbepreparedbyweighingaccuratemassesofcompoundsusingananalyticalbalance
andthenmakingthemuptoaparticularvolumewithsolventinavolumetricflask.Concentrated
solutionsofknownconcentrationcanbedilutedquantitativelyusingvolumetricglasswaresuchas
pipettesandvolumetricflasks.Molarityisausefulconcentrationunitforanycalculationinvolvingthe
stoichiometryofreactionsinsolution.Inionicreactions,theconcentrationsoftheionsinasolutionofa
saltcanbederivedfromthemolarconcentrationofthesalt,takingintoaccountthenumberofions
formedondissolutionofthesalt.Forreactionsinvolvingionstherearethreepossiblewaystowrite
reactionequations.Amolecularequationusestheempiricalformulaforeachcompoundtoaid
stoichiometriccalculations.Theionicequationshowsalltheionsthatareformedinsolution,whilethe
netionicequationshowsonlythoseionsthatareactuallyinvolvedinthenetreaction(i.e.excluding
spectatorions).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Chemicalformula(section3.1)
Weusesubscriptsinaformulatoestablishatomratiosandmoleratiosbetweentheelementsinthe
substance.

Balancedchemicalequation(section3.2)
Weusecoefficientstoestablishstoichiometricequivalenciesthatrelatetheamountofonesubstanceto
theamountofanotherinachemicalreaction.Thecoefficientsalsoestablishtheratiosofreactantsand
productsinvolvedinthereaction.

Themole(section3.3)
Themoleprovidesthebasisfordeterminationoftheamountofsubstance.

Avogadroconstant(NA)(section3.3)
TheAvogadroconstantrelatesmacroscopicquantitiesusedinalaboratorytonumbersofindividual
atomicsizedparticles,suchasatoms,moleculesandions.

Molarmass(M)(section3.3)
Molarmasscanbeusedtocalculatethemassof1moleofanysubstanceortoconvertbetweenamount
andmassusing .

(section3.3)
Thisequationrepresentstherelationshipbetweenmass(m),amount(n)andmolarmass(M).

Percentagecomposition(section3.4)
Weusepercentagecompositiontorepresentthecompositionofacompoundandasthebasisfor
calculatingtheempiricalformula.Comparingexperimentalandtheoreticalpercentagecompositionscan
helptoestablishtheidentityofacompound.

Theoretical,actualandpercentageyields(section3.5)
Weusethesevaluestoestimatetheefficiencyofareaction.Rememberthattheoreticalyieldis
calculatedfromthelimitingreagentusingthebalancedchemicalequation.Thepercentageyieldisgiven
bytheequation:percentageyield=(actualyield/theoreticalyield)100%.

Balancedequationsandmoleratios(section3.5)
Forthegenericbalancedequation:

themoleratiosforexactstoichiometricreactionare:

(section3.6)
Thisequationrepresentstherelationshipbetweenconcentration(c),amount(n)andvolume(V).
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
ChemicalEquations
3.1Whatdowemeanwhenwesayachemicalequationisbalanced?Whydowebalancechemical
equations?
3.2Inachemicalreaction,whatdowemeanbythetermreactants?Whatdowemeanbytheterm
products?
3.3Whatdowecallthenumbersthatarewritteninfrontoftheformulaeinabalancedchemical
equation?
3.4Thecombustionofathinwireofmagnesiummetal,Mg,inanatmosphereofpureoxygenproduces
thebrilliantlightofaflashbulb,oncecommonlyusedinphotography.Afterthereaction,athinfilm
ofmagnesiumoxideisseenontheinsideofthebulb.Theequationforthereactionis:

(a)Stateinwordshowthisequationisread.
(b)Givetheformulaeofthereactants.
(c)Givetheformulaoftheproduct.
(d)RewritetheequationtoshowthatMgandMgOaresolidsandO2isagas.
BalancingChemicalEquations
3.5Whengiventheunbalancedequation:

andaskedtobalanceit,studentAwrote:

andstudentBwrote:

(a)Bothequationsarebalanced,butwhichstudentiscorrect?
(b)Explainwhytheotherstudent'sanswerisincorrect.
TheMole
3.6Definethetermmole.
3.7Whyaremolesusedwhenallstoichiometryproblemscouldbedoneusingonlyatomicmassunits?
3.8Whatinformationisrequiredtocalculatetheamountofasubstancefromagivenmassofthatsame
substance?
3.9Givetheequationthatrelatesmolarmass,amountandmass.
3.10Howwouldyouestimatethenumberofatomsinagramofiron,usingatomicmassunits?
3.11Whichcontainsmoremolecules:2.5molesofH2Oor2.5molesofH2?
3.12Whatamountofironatomsisin1molofFe2O3?Howmanyironatomsarein1molofFe2O3?
3.13Whyistheexpression1.0molofoxygenambiguous?
EmpiricalFormulae
3.14Ingeneral,whatfundamentalinformation,obtainedfromexperimentalmeasurements,isrequired
tocalculatetheempiricalformulaofacompound?
3.15Whyisthechangingofsubscriptsnotallowedwhenbalancingachemicalequation?
3.16GiveastepbystepprocedureforestimatingthemassofArequiredtocompletelyreactwith10
 molesofB,giventhefollowinginformation:
i. AandBreacttoformA5B2.
ii. Ahasamolarmassof100.0gmol1.
iii.Bhasamolarmassof200.0gmol1.
iv.Thereare6.02210 23moleculesofAin1moleofA.Whichofthesepiecesofinformation
wasnotneeded?
Stoichiometry,LimitingReagentsandPercentageYield
3.17Whatinformationisrequiredtodeterminethemassofsulfurthatwouldreactwith1gramof
arsenic?
3.18Amixtureof0.020molofMgand0.020molofCl2reactedcompletelytoformMgCl2according
totheequation:

(a)Whatinformationdescribesthestoichiometryofthisreaction?
(b)Whatinformationgivesthescaleofthereaction?
3.19Inareporttoasupervisor,achemistdescribedanexperimentinthefollowingway:0.0800mol
ofH2O2decomposedinto0.0800molofH2Oand0.0400molofO2.Expressthechemistryand
stoichiometryofthisreactionbyaconventionalchemicalequation.
SolutionStoichiometry
3.20Givetheequationthatrelatesconcentration,volumeandamount.
3.21Whatisthedefinitionofmolarity?Showthattheratioofmillimoles(mmol)tomillilitres(mL)is
equivalenttotheratioofmolestolitres.
3.22Whatarespectatorions?
3.23Whenasolutionlabelled0.50MHNO3isdilutedwithwatertogive0.25MHNO3,whathappens
totheamountofHNO3inthesolution?
3.24SolutionsAandBarelabelled0.10MCaCl2and0.20MCaCl2,respectively.Bothsolutions
containthesameamountofCaCl2.IfsolutionAhasavolumeof50mL,whatisthevolumeof
solutionB?
3.25Whatisthedifferencebetweenaqualitativeanalysisandaquantitativeanalysis?
3.26Thefollowingequationshowstheformationofcobalt(II)hydroxide,acompoundusedtoimprove
thedryingpropertiesoflithographicinks:

Whicharethespectatorions?Writethenetionicequation.
3.27Whyisthefollowingequationnotbalanced?Findtheerrorsandfixthem.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
3.28Considerthebalancedequation:

(a)HowmanyatomsofNaareoneachsideoftheequation?
(b)HowmanyatomsofCareoneachsideoftheequation?
(c)HowmanyatomsofOareoneachsideoftheequation?
3.29Whensulfurimpuritiesinfuelsburn,theyproducepollutantssuchassulfurdioxide,amajorcontributortoacidrain.Thefollowingisaballand
stickmodelofatypicalreaction.

Ontheleftarereactantmoleculesandontherightareproductmoleculesinachemicalreaction.Writethebalancedchemicalequationforthis
reaction,usingthestoichiometriccoefficientsthatgivethesmallestwholenumberofproductmolecules
3.30Writetheequationthatexpressesinacceptablechemicalshorthandthefollowingstatement:Ironcanbemadetoreactwithmolecularoxygen,
O2,togiveironoxidewiththeformulaFe2O3.
3.31Racecardriverscangetextrapowerbyburningmethylalcoholwithnitrousoxide.Belowontheleftarethereactantmoleculesandontheright
areproductmoleculesofthechemicalreaction.Writethebalancedchemicalequationforthisreaction,usingthestoichiometriccoefficientsthat
givethesmallestwholenumberofproductmolecules.

3.32Isthefollowingchemicalequationbalanced?Thisreactionisusedfortheproductionofnitricacid,HNO3,andisoneofthereactionsresponsible
foracidrain.

Iftheequationisnotbalanced,findcoefficientsthatwouldmakeitbalanced.
3.33Writethebalancedchemicalequationforthechemicalreactiondepictedbythespacefillingmodelsbelow.
3.34Writethebalancedchemicalequationforthechemicalreactiondepictedbythespacefillingmodelsbelow.

3.35Balancethefollowingequations:
(a)Ca(OH)2+HClCaCl2+H2O
(b)NaHCO3+H2SO4Na2SO4+H2O+CO2
(c)AgNO3+CaCl2Ca(NO3)2+AgCl
(d)C4H10+O2CO2+H2O
(e)Fe2O3+CFe+CO2
3.36Giventhebalancedchemicalequation

determinethenumberofmoleculesofSO2thatwouldbeformedstartingfromtheactualnumberofmoleculesofC2H5SHandO2shownbelow.

3.37Usingthebalancedchemicalequationfromquestion3.35,whichofC2H5SHorO2wasthelimitingreagentiftheproductdistributionforthe
reactionwasthatshownbelow?

3.38InwhatsmallestwholenumberratiomustNandOatomscombinetomakedinitrogentetroxide,N2O4?Whatisthemoleratiooftheelementsin
thiscompound?
3.39Whatamountofsodiumatomscorrespondsto1.5610 21atomsofsodium?
3.40WhatamountofAlatomsareneededtocombinewith1.58molofOatomstomakealuminiumoxide,Al2O3?
3.41WhatamountofH2andN2canbeformedbythedecompositionof0.145molofammonia,NH3?
3.42WhatamountofUF6wouldhavetobedecomposedtoprovideenoughfluorinetoprepare1.25molofCF4?(Assumesufficientcarbonis
available.)
3.43Quantitativeanalysisofa0.896gsampleofsodiumpertechnetatefound0.111gofsodiumand0.477goftechnetium.Theremainderwas
oxygen.Calculatetheempiricalformulaofsodiumpertechnetate.(Radioactivesodiumpertechnetateisusedasabrainscanningagentin
medicine.)
3.44Thecompositionofadrycleaningfluid,composedofonlycarbonandchlorine,wasfoundtobe14.5%Cand85.5%Cl(bymass).Whatisthe
3.44Thecompositionofadrycleaningfluid,composedofonlycarbonandchlorine,wasfoundtobe14.5%Cand85.5%Cl(bymass).Whatisthe
empiricalformulaofthiscompound?
3.45When0.684gofanorganiccompoundcontainingonlycarbon,hydrogenandoxygenwasburnedinoxygen,1.312gCO2and0.805gH2Owas
obtained.Whatistheempiricalformulaofthecompound?
3.46Asampleofacompoundofmercuryandbrominewithamassof0.389gwasfoundtocontain0.111gbromine.Itsmolarmasswasfoundtobe
561gmol1.Whatareitsempiricalandmolecularformulae?

3.47Determinethemassingramsofeachofthefollowing:
(a)1.35molFe,
(b)24.5molO,
(c)0.876molCa.
3.48Whatisthemass,ingrams,of2.0010 12atomsofpotassium?
3.49Whatamountofnickelisin17.7gofNi?
3.50Calculatethemolarmassofeachofthefollowing:
(a)NaHCO3,
(b)K2Cr2O7,
(c)(NH4)2CO3,
(d)Al2(SO4)3,
(e)CuSO4.5H2O.
3.51Calculatethemassingramsofeachofthefollowing:
(a)1.25molCa3(PO4)2,
(b)0.625molFe(NO3)3,
(c)0.600molC4H10,
(d)1.45mol(NH4)2CO3.
3.52Calculatetheamountofthecompoundineachofthefollowingsamples:
(a)21.5gCaCO3,
(b)1.56gNH3,
(c)16.8gSr(NO3)2,
(d)6.98gNa2CrO4.
3.53Whatmassofafertilisermadeofpure(NH4)2CO3wouldberequiredtosupply1kgofnitrogentothesoil?
3.54Calculatethepercentagecompositionbymassofallelementsineachofthefollowing:
(a)NaH2PO4,
(b)NH4H2PO4,
(c)(CH3)2CO,
(d)CaSO4,
(e)CaSO42H2O.
3.55WhatmassofOiscombinedwith7.1410 21atomsofNinthecompoundN O ?
2 5
3.56Chlorineisusedbytextilemanufacturerstobleachcloth.Excesschlorineisdestroyedbyitsreactionwithsodiumthiosulfate,Na2S2O3,as
follows:

(a)WhatamountofNa2S2O3isneededtoreactwith0.12molofCl2?
(b)WhatamountofHClcanformfrom0.12molofCl2?
(c)WhatamountofH2Oisrequiredforthereactionof0.12molofCl2?
(d)WhatamountofH2Oreactsif0.24molHClisformed?

3.57Thefollowingreactionisusedtoextractgoldfrompretreatedgoldore:

(a) WhatmassofZnisneededtoreactwith0.11molofAu(CN) ?
2
(b)WhatmassofAucanformfrom0.11molofAu(CN) ?
2
(c) WhatmassofAu(CN) isrequiredforthereactionof0.11molofZn?
2
3.58TheincandescentwhiteofafireworksdisplayiscausedbythereactionofphosphoruswithO2togiveP4O10.
(a)Writethebalancedchemicalequationforthereaction.
(b)WhatmassofO2isneededtocombinewith6.85gofP?
(c)WhatmassofP4O10canbemadefrom8.00gofO2?
(d)WhatmassofPisneededtomake7.46gofP4O10?
3.59Oxygengascanbeproducedinthelaboratorybydecompositionofhydrogenperoxide,H2O2:

WhatmassofO2canbeproducedfrom1.0kgofH2O2?
3.60Thereactionofpowderedaluminiumandiron(III)oxide:

producessomuchheatthattheironthatformsismolten.Becauseofthis,thereactionisusedwhenlayingrailwaytrackstoprovidemoltensteel
toweldsteelrailstogether.Supposethat,inonebatchofreactants,4.20molofAlwasmixedwith1.75molofFe2O3.
(a)Whichreactant,ifeither,wasthelimitingreagent?
(b)Calculatethemassofironthatcanbeformedfromthismixtureofreactants.
3.61Silvernitrate,AgNO3,reactswithiron(III)chloride,FeCl3,togivesilverchloride,AgCl,andiron(III)nitrate,Fe(NO3)3.Asolutioncontaining
18.0gofAgNO3wasmixedwithasolutioncontaining32.4gofFeCl3.Whatmassofwhichreactantremainsafterthereactioniscomplete?
3.62Bariumsulfate,BaSO4,ismadebythefollowingreaction:

Anexperimentwasbegunwith75.00gofBa(NO3)2andanexcessofNa2SO4.Aftercollectinganddryingtheproduct,64.45gofBaSO4was
obtained.CalculatethetheoreticalyieldandpercentageyieldofBaSO4.
3.63Thepotassiumsaltofbenzoicacid(potassiumbenzoate,C6H5COOK),canbemadebytheactionofpotassiumpermanganate,KMnO4,on
toluene,C6H5CH3,asfollows:

Iftheyieldofpotassiumbenzoatecannotrealisticallybeexpectedtobemorethan71%,whatistheminimummassoftolueneneededtoachieve
thisyieldwhileproducing11.5gofpotassiumbenzoate?
3.64Calculatetheconcentrationofasolutionpreparedbydissolving:
(a)4.00gofNaOHin100.0mLofsolution
(b)16.0gofCaCl2in250.0mLofsolution
(c)14.0gofKOHin75.0mLofsolution
(d)6.75gofHO2CCO2Hin500mLofsolution.
3.65Calculatethemassofeachsoluteneededtomakeeachofthefollowingsolutions.
(a)125mLof0.200MNaCl(aq)
(b)250mLof0.360MC6H12O6(aq)(glucose)

(c)250mLof0.250MH2SO4(aq)
3.66If25.0mLof0.56MH2SO4isdilutedtoavolumeof125mL,whatistheconcentrationoftheresultingsolution?
3.67Towhatvolumemust25.0mLof18.0MH2SO4bedilutedtoproduce1.50MH2SO4(aq)?
3.68Calculatetheamountsofeachoftheionsinthefollowingsolutions.
(a)35.0mLof1.25MKOH(aq)
(b)32.3mLof0.45MCaCl2(aq)
(c)50.0mLof0.40MAlCl3(aq)
3.69Calculatetheconcentrationsofeachoftheionsin:
(a)0.25MCr(NO3)2(aq),
(b)0.10MCuSO4(aq),
(c)0.16MNa3PO4(aq),
(d)0.075MAl2(SO4)3(aq).
3.70InasolutionofAl (SO ) (aq),theAl3+concentrationis0.12M.WhatmassofAl (SO ) isin50.0mLofthissolution?
2 43 2 43
3.71Whatvolumeof0.25MNiCl2(aq)solutionisneededtoreactcompletelywith20.0mLof0.15MNa2CO3(aq)solution?WhatmassofNiCO3will
beformed?Thereactionis:

3.72Whatvolumeof0.150MFeCl3(aq)solutionisneededtoreactcompletelywith20.0mLof0.0450MAgNO3(aq)solution?WhatmassofAgCl
willbeformed?Thenetionicequationforthereactionis:

3.73Considerthereactionofaluminiumchloridewithsilveracetate.Whatvolumeof0.250MAlCl3(aq)wouldbeneededtoreactcompletelywith
20.0mLof0.500MAgOOCCH3(aq)solution?Thenetionicequationforthereactionis:

3.74Supposethat25.0mLof0.440MNaCl(aq)isaddedto25.0mLof0.320MAgNO3(aq).
(a)WhatamountofAgClwouldprecipitate?
(b)Determinetheconcentrationofeachoftheionsinthereactionmixtureafterthereaction.
3.75Amixtureispreparedbyadding25.0mLof0.185MNa3PO4(aq)to34.0mLof0.140MCa(NO3)2(aq).
(a)WhatmassofCa3(PO4)2willbeformed?
 (a)WhatmassofCa3(PO4)2willbeformed?
(b)Determinetheconcentrationofeachoftheionsinthemixtureafterreaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
3.76Writethenetionicequationsforthefollowingreactions.Includethedesignationsforthestates
solid,liquid,gasandaqueoussolution.(Foranysubstancesolubleinwater,assumethatitisused
asanaqueoussolution.)
(a)CaCO3+2HNO3Ca(NO3)2+CO2+H2O
(b)CaCO3+H2SO4CaSO4+CO2+H2O
(c)FeS+2HBrH2S+FeBr2
(d)2KOH+SnCl22KCl+Sn(OH)2
3.77A0.113gsampleofamixtureofsodiumchlorideandsodiumnitratewasdissolvedinwater,and
enoughsilvernitratesolutionwasaddedtoprecipitateallofthechlorideions.Themassofsilver
chlorideobtainedwas0.277g.Whatmasspercentageofthesamplewassodiumchloride?
3.78Inanexperiment,40.0mLof0.270MBa(OH)2(aq)wasmixedwith25.0mLof0.330M
Al2(SO4)3(aq).
(a)Writethenetionicequationforthereactionthattakesplace.
(b)Whatisthetotalmassofprecipitatethatforms?
(c)Whatarethemolarconcentrationsoftheionsthatremaininthesolutionafterthereaction
iscomplete?
3.79Whatvolumeof0.10MHCl(aq)mustbeaddedto50.0mLof0.40MHCl(aq)togiveafinal
solutionthathasamolarityof0.25M?
3.80AnswerthefollowingquestionsaboutaninsecticidewiththechemicalformulaC12H11NO2.
(a)Whatamountofcarbonatomsistherein8.3gofthecompound?
(b)Whatmassofoxygenistherein4.5gofthecompound?
(c)Thelabelona75mLbottleofgardeninsecticidestatesthatthesolutioncontains0.010%
insecticideand99.99%inertingredients.Whatamountandhowmanymoleculesofthe
insecticideareinthebottle?(Assumethatthedensityofthesolutionis1.00gmL1.)
(d)Theinstructionsonthebottleofinsecticidein(c)aretodilutetheinsecticidebyadding1.0
mLofthesolutionto4.0litresofwater.Ifyouspray60litresofthedilutedinsecticide
mixtureonyourrosegarden,Whatamountoftheactiveingredientisdispersed?
3.81SolutionAispreparedbydissolving90.0gofNa3PO4inenoughwatertomake1.5Lofsolution.
SolutionBis2.5Lof0.705MNa2SO4(aq).
(a)WhatisthemolarconcentrationofNa3PO4insolutionA?
(b)WhatvolumeofsolutionAcontains2.50gofNa3PO4?
(c)A50.0mLsampleofsolutionBismixedwitha75.00mLsampleofsolutionA.Calculate
theconcentrationofNa+ionsinthefinalsolution.
3.82Policeofficersconfiscateapacketofwhitepowderthattheybelievecontainsheroin.Purification
byaforensicchemistyieldsa38.70mgsampleforcombustionanalysis.Thissampleproduces
97.46mgCO2and20.81mgH2Ooncompletecombustion.Asecondsampleisanalysedforits
nitrogencontent,whichis3.8%.Showbycalculationswhetherthesedataareconsistentwiththe
formulaforheroin,C21H22NO5.
3.83WhenanunknowncompoundisburnedcompletelyinO2,1.23gofCO2and97.02gofH2Ois
recovered.Whatadditionalinformationisneededbeforethemolecularformulaoftheunknown
compoundcanbedetermined?
3.84Asulfurcontainingoreofcopperreleasessulfurdioxidewhenheatedinair.A5.26gsampleof
theorereleases2.12gofSO2onheating.Assumingthattheorecontainsonlycopperandsulfur,
whatistheempiricalformula?
3.85ThemineralturquoisehastheformulaCuAl6(PO4)4(OH)84H2O.
(a)Whatmassofaluminiumisina7.25gsampleofturquoise?
(b)Howmanyphosphateionsareinasampleofturquoisethatcontains5.5010 3gof
oxygen?
(c)Whatisthechargeofthecopperioninturquoise?
3.86Achemistneedsasolutionthatcontainsaluminiumions,sodiumionsandsulfateions.Inthe
laboratoryshefindsalargevolumeof0.355Msodiumsulfatesolutionandabottleofsolid
Al2(SO4)318H2O.Thechemistputs250mLofthesodiumsulfatesolutionand5.13gof
aluminiumsulfatehydrateina500mLvolumetricflask.Theflaskismadeuptothemarkwith
water.Determinethemolarityofaluminiumions,sodiumionsandsulfateionsinthesolution.
3.87Adenosinetriphosphate(ATP)isusedtogeneratechemicalenergyinplantandanimalcells.The
molecularformulaofATPisC10H16N5O13P3.AnswerthefollowingquestionsaboutATP.
(a)WhatisthepercentagecompositionbymassofeachelementinATP?
(b)HowmanyPatomsarein1.75gofATP?
(c)Ifacellconsumes3.0pmolofATP,whatmasshasitconsumed?
(d)WhatmassofATPcontainsthesamenumberofatomsofHasthenumberofNatomsin
37.5mgofATP?
3.88Thewatersoftheoceanscontainmanyelementsintraceamounts.Rubidium,forexample,is
presentatthelevelof2.2nM(nanomolar).Howmanyionsofrubidiumarepresentin1.00Lof
seawater?Howmanylitreswouldhavetobeprocessedtorecover1.00kgofrubidium,assuming
therecoveryprocesswas100%efficient?
3.89VitaminB12isalargemoleculecalledcobalamin.Thereis1atomofcobaltineachmoleculeof
vitaminB12,andthemasspercentageofcobaltis4.34%.Calculatethemolarmassofcobalamin.
3.90ElementEformsacompoundwiththeformulaECl5.Elementalanalysisshowsthatthecompound
is85.13%chlorinebymass.IdentifyelementE.
3.91Pureaceticacid,CH3COOH,hasaconcentrationof17.4M.Alaboratoryworkermeasuredout
100.0mLofpureaceticacidandaddedenoughwatertomake500.0mLofsolution.A75.0mL
portionoftheaceticacidsolutionwasthenmixedwithenoughwatertomake1.50Lofdilute
solution.Whatwasthefinalmolarityofaceticacidinthedilutesolution?
3.92Aworkerinabiologicallaboratoryneededasolutionthatwas0.30Minsodiumacetate,
NaOOCCH3,and0.15Minaceticacid,CH3COOH.Onhandwerestocksolutionsof5.0M
sodiumacetateand5.0Maceticacid.Describehowtheworkerprepared1.5Lofthedesired
solution.
3.93Thethyroidglandproduceshormonesthathelpregulatebodytemperature,metabolicrate,
reproduction,synthesisofredbloodcellsandmore.Iodinemustbepresentinthediettoproduce
thesethyroidhormones.Iodinedeficiencyleadstosluggishnessandweightgain,andcancause
severeproblemsinthedevelopmentofafoetus.Onethyroidhormoneisthyroxine,withthe
chemicalformulaC15H11I4NO4.Whatmassofthyroxinecanbeproducedfrom210mgofiodine
atoms,theamountatypicaladultconsumesperday?Howmanymoleculesisthis?
3.94Asampleofacomponentofpetroleumwassubjectedtocombustionanalysis.Anemptyvialof
mass2.7534gwasfilledwiththesample,afterwhichthevialplussamplehadamassof2.8954g.
ThesamplewasburnedandtheresultingCO2andH2Owerecollectedinseparatetraps.Before
combustion,theCO2traphadamassof54.4375gandtheH2Otraphadamassof47.8845g.At
theendoftheanalysis,theCO2traphadanewmassof54.9140gandtheH2Otraphadanew
massof47.9961g.Determinetheempiricalformulaofthiscomponentofpetroleum.
3.95Aluminiumsulfateisusedinthemanufactureofpaperandinthewaterpurificationindustry.In
thesolidstate,aluminiumsulfateisahydratewiththeformulaAl2(SO4)318H2O.
(a)Whatmassofsulfuristherein0.570molesofsolidaluminiumsulfate?
(b)Howmanywatermoleculesarethereina5.1gsampleofsolidaluminiumsulfate?
(c)Whatamountofsulfateionsisthereinasampleofsolidaluminiumsulfatethatcontains
12.5molesofoxygenatoms?
(d)Anaqueoussolutionofaluminiumsulfatecontains1.25%aluminiumbymassandhasa
densityof1.05gmL1.Whatisthemolarityofaluminiumionsinthesolution?
3.96IntheHabersynthesisofammonia,N2andH2reactathightemperature,buttheyneverreact
completely.Inatypicalreaction,24.0kgofH2and84.0kgofN2reacttoproduce68kgofNH3.
Findthetheoreticalyield,thepercentageyieldandthemassesofH2andN2thatremainunreacted,
assumingthatnootherproductsform.
3.97Silicontetrachlorideisusedintheelectronicsindustrytomakeelementalsiliconforcomputer
chips.Silicontetrachlorideispreparedfromsilicondioxide,graphiteandchlorinegasaccordingto
theequation:

Ifthereactionachieves95.7%yield,howmuchsilicontetrachloridecanbepreparedfrom75.0g
ofeachstartingmaterial,andhowmuchofeachreactantremainsunreacted?
3.98Silverjewelleryisusuallymadefromsilverandcopperalloys.Theamountofcopperinanalloy
canvaryconsiderably.Thefinestqualityalloyissterlingsilver,whichis92.5%silverbymass.To
determinethecompositionofasilvercopperalloy,ajewellerdissolved0.135gofmetalshavings
in50mLofconcentratednitricacidandthenadded1.00MKClsolutionuntilnomoreprecipitate
formed.Filtrationanddryingyielded0.156gofAgClprecipitate.Whatwasthemasscomposition
ofthesilveralloy?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
actualyield empiricalformula product
amountofsubstance excessreagent qualitativeanalysis
Avogadroconstant(NA) limitingreagent quantitativeanalysis
balancedchemicalequation mainreaction reactant
byproduct masspercentagecomposition reversiblereaction
chemicalequation molarmass(M) solute
chemicalreaction molarity(c) solution
combustion mole solvent
competingreaction molecularformula spectatorion
concentration netionicequation stoichiometriccoefficients
dissociation percentagebymass stoichiometry
elementalanalysis percentageyield theoreticalyield

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

4 AtomicEnergyLevels
Intherightcombination,atomsandlightcombinetocreateoneofthemostremarkabletools
ofmoderntechnology,thelaser.Laserlightismorehighlyorganisedthannormallight.
Laserlightismonochromatic(hasasinglewavelength)andishighlydirectional,whereas
conventionallightsourcestypicallyproducedisperselightofmanywavelengths.The
picturesonthispagedemonstratethesedifferences.Inthetoptwofiguresweseeredand
greenlaserlightwithwavelengthsof650and532nm,respectivelypassthroughaprism.
Whilethelightisdiffracted,thereisnosplittingintodifferentcolours,asweseeforwhite
lightinthebottomfigure.Thisconfirmsthatlaserlightconsistsofonlyonewavelength
whilenormalwhitelightcomprisesmanywavelengths.Manyoftheapplicationsoflasers
takeadvantageofthehighdegreeoforganisation.

Lasersarealsousedin,forexample,DVDscanners,eyesurgeryandfibreoptics
communications.Lasershavealsobecomeversatiletoolsforscientificresearch.For
example,finelytunedlasershavebeenusedtodepositvapourphaseatomsonsolidsurfaces
inregularpatterns.Theabilitytomanipulateindividualatomsislikelytohaveimportant
applicationsinnanotechnology.

Everylaserisbasedontheinteractionsbetweenlightandatomsormolecules.Inthischapter,
wedescribethepropertiesofatomsandlightandtheenergychangesthataccompanythe
interactionsbetweenthem.Thenwedescribethepropertiesofelectronsboundtoatomsand
howthesecontributetoatomicstructure.Weexplorethedetailsoforbitalenergiesandrelate
themtotheorderingofatomsthatleadstothefamiliarformandstructureoftheperiodic
table.Orbitalenergylevelshaveconsequencesthatarefarreaching.Orbitalenergies
determinethestabilityofatomsandhowatomsreact.Theperiodictableisbasedonorbital
energylevelsandprovidesthefoundationforinterpretingpatternsofchemicalbehaviour
relatedtoanelement'spositioninthetable.

KEYTOPICS

4.1Characteristicsofatoms
4.2Characteristicsoflight
4.3Propertiesofelectrons
4.4Quantisationandquantumnumbers
4.5Atomicorbitalelectrondistributionsandenergies
4.6Structureoftheperiodictable
4.7Electronconfigurations
4.8Periodicityofatomicproperties
4.9Ionsandchemicalperiodicity
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.1CharacteristicsofAtoms
Weintroducedtheconceptoftheatominchapter1,andstatedthatitwasthefundamentalbuilding
blockofallmatter.Inthischapter,wewillinvestigatethepropertiesofatomsinmoredetail.Wewill
startbyoutliningthebasiccharacteristicsofatomswereadaboutmanyofthesecharacteristicsin
chapter1.

Atomspossessmass,mostofwhich,asRutherfordshowed,isconcentratedinthenucleus.Thenucleus
ofanatomissmallandpositivelycharged,andallnuclei,exceptthatofthehydrogenatom1H,consist
ofbothpositivelychargedprotonsandneutralneutrons.Thepositivechargeofthenucleusisexactly
balancedbynegativelychargedelectrons,whichoccupytheregionofspacearoundthenucleus.A
neutralatomcontainsequalnumbersofprotonsandelectrons.Atomsoccupyvolume,themajorityof
whichistakenupbytheelectroncloud.Thechemicalpropertiesofelementsaredeterminedtoalarge
extentbyboththeiratomicsizeandtheirnumberofaccessible(valence)electrons.Finally,atomscan
attractoneanother,and,asaresult,cancombinetoformmolecules.

Thischapterexaminesindetailhowboththenumberofelectronsandtheirspecificarrangement
influencechemicalproperties.Sincetherearesimilaritiesbetweenthepropertiesoflightandelectrons,
andlightisanessentialtoolforprobingthepropertiesofelectrons,wewillbeginourdiscussionby
describinglightanditsinteractionwithatoms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.2CharacteristicsofLight
Themostusefultoolforstudyingthestructureofatomsiselectromagneticradiation.Whatwecalllightisoneformofthis
radiation,withotherformsincludingradiowaves,microwavesandXrays.Weneedtoknowaboutthefundamental
propertiesoflighttounderstandwhatelectromagneticradiationrevealsaboutatomicstructure.

WavelikePropertiesofLight
Lighthaswavelikeproperties.Awaveisaregularoscillationinsomeparticularproperty,suchastheupanddown
variationinpositionofwaterwaves.Waterwavesvarywithtime.Asurferwaitingforabigonebobsupanddownas
smallonespassby.Lightwavesvarywithtimetoo,inamoreregularmannerthanwaterwaves.Thisvariationis
characterisedbythewave'sfrequency(),whichisthenumberofwavecrestspassingapointinspacein1second(sothe
unitiss1,alsodesignatedhertzorHz).Waterwavesalsovaryinheightasyoumoveawayfromthebeachthatis,the
heightofthewavevarieswithposition.Lightwavesvaryinspaceinamannerillustratedinfigure4.1.Thisvariationin
spaceischaracterisedbythewavelength(),whichisthedistancebetweensuccessivewavecrests.Wavelengthsare
measuredinunitsoflength,suchasmetresornanometres.Aswewillseebelow,frequencyandwavelengtharenot
independentvariables,butareinverselyproportionaltoeachother.

FIGURE4.1Alightwavecanbedescribedbyitswavelengthorfrequency.Aswavelengthincreases,frequencydecreases,andvice
versa.

Amplitudeisthemaximumdisplacementofawavefromitscentre.Theamplitudeofalightwavedeterminestheintensity
ofthelight.Asfigure4.2shows,abrightlightismoreintensethanadimoneasitswaveshavehigheramplitudes.Itis
importanttonotethattheintensityoflightisproportionaltothesquareofitsamplitude.Theamplitudeitselfhasno
physicalmeaningbecauseatanymomentintimetheamplitudeofthewavecanbenegativeorpositive,whilethesquareis
alwayspositiveandequivalenttophotondensity.
 FIGURE4.2Theamplitudeofalightwavedeterminestheintensityofthelight.Abrightlightismoreintenseandhasahigher
amplitudethanadimlight.

Wavescanalsobedescribedintermsoftheirphase.Phasereferstothestartingpositionofawavewithrespecttoone
wavelength.Wecanseethatwavesinfigures4.3aand4.3bhavethesameamplitudeandwavelengths,butdifferent
startingpoints.Wesaythatthetwowaveshavedifferentphases.Wecanseethismoreclearlyinfigure4.3cwhichshows
thetwowavessuperimposed.Iftheyhadthesamephase(andthesameamplitudeandwavelength),theywouldlineup
perfectly.Aswewillseeonp.189,whenwavesinteract,theoutcomeisinfluenced,amongotherthings,bytheirrelative
phases.

FIGURE4.3Phasereferstothestartingpositionofawavewithrespecttoonewavelength.Thewavesin(a)and(b)havedifferent
phases(c)showsanoverlapof(a)and(b).

Lightwaves,andallothertypesofelectromagneticradiation,alwaysmovethroughavacuumatthesamespeed.Thespeed
oflightisafundamentalconstant,denotedbythesymbolc:c=2.9979245810 8ms1(wewillrounditto2.99810 8
ms1).Foranywave,itsfrequency()(inunitsofs1)multipliedbyitswavelength()(inunitsofm)equalsitsspeedc(m
s1),i.e.

WORKEDEXAMPLE4.1

WavelengthfrequencyConversion
AnFMradiostationtransmitsitssignalat88.1MHz.Whatisthewavelengthofthesignal?

Analysis

Thelinkbetweenwavelength()andfrequency()isgivenbyc=.

Solution

First,wesummarisethedata.

Next,werearrangetheequationtosolveforwavelength.

Toobtainequivalentunits,convertthefrequencyunitsfromMHztoHz.TheprefixMstandsformega,which
isafactorof10 6.RememberthatHzisequivalenttos1.
 Isouranswerreasonable?

Thewavelengthof3.40mmayseemratherlong,butradiowavesareknownaslongwavelengthradiation.See
figure4.4forasenseofthewavelengthsofelectromagneticradiation.

FIGURE4.4Theelectromagneticspectrum,showingitsvariousregionsandtheassociatedwavelengthsand
frequencies.

PRACTICEEXERCISE4.1
Whatisthefrequencyofelectromagneticradiation
thathasawavelengthof1.40cm?

Thewavelengthsorfrequenciesofelectromagneticradiationcoveranimmenserange.Figure4.4showsthatthevisible
spectrumcoversthewavelengthrangefromabout380nm(violet)to780nm(red).Thecentreofthisrangeisyellowlight,
withawavelengthofabout580nmandafrequencyaround5.210 14s1.Althoughvisiblelightisextremelyimportantto
livingcreaturesforvision,thegammaray,Xray,ultraviolet,infrared,microwaveandradiofrequencyportionsofthe
electromagneticspectrumalsohavediverseeffectson,andusesin,ourlives.

Radiationwithshortwavelengths,intheXrayandgammarayregions,cangenerateionsbyremovingelectronsfrom
atomsandmolecules.Theseionsarehighlyreactiveandcancauseseriousdamagetothematerialthatabsorbsthe
radiation.However,undercloselycontrolledconditions,Xraysareusedinmedicalimaging,andgammaraysareusedto
treatcancer.Thewavelengthofultraviolet(UV)radiationliesbetweenthatofXraysandvisiblelight.Ultravioletradiation
canalsodamagematerials,especiallyinhighdoses.HighratesofskincancerinAustraliaandNewZealandareadirect
resultofexposuretodamagingUVradiationinsunlight.

Radiationwithlongwavelengthsfallsintheinfrared,microwaveorradiofrequencyregions.Heatlampsmakeuseof
infraredradiation,microwaveovenscookwithmicrowaveradiation,andradioandtelevisionsignalsaretransmittedby
radiowaves.

Whatweperceiveaswhitelightactuallycontainsarangeofwavelengths.Thisbecomesapparentwhensunlightpasses
throughaprism(seep.109)orthroughraindrops(whichcreatesarainbowasshowninfigure4.5).Theseobjectsdiffract
differentwavelengthsoflightthroughdifferentangles,sothelightthatpassesthroughspreadsoutinspace,witheach
wavelengthappearingatitsowncharacteristicangle.
 FIGURE4.5Lightraysbendastheypassthroughraindrops,causingwhitelighttoseparateintoitsrainbowofcolours.

ParticlePropertiesofLight
Lightcarriesenergy.Whenourbodiesabsorbsunlight,forexample,wefeelwarmbecauseenergyfromthesunlighthas
beentransferredtoourskin.Aphenomenonknownasthephotoelectriceffectshowshowtheenergyoflightdependson
itsfrequencyandintensity.Thephotoelectriceffectisthebasisformanylightsensingdevices,suchasautomaticdoor
openersandcameraexposuremeters.Figure4.6illustratesaphotoelectricexperimentinwhichabeamoflightstrikesthe
surfaceofametal.Undertherightconditions,thelightcauseselectronstobeejectedfromthemetalsurface.Adetailed
studyofthephotoelectriceffectrevealshowthebehaviouroftheseelectronsisrelatedtothecharacteristicsofthelight:
1.Belowacharacteristicthresholdfrequency,0,noelectronsareobserved,regardlessofthelight'sintensity.

FIGURE4.6Adiagrammaticviewofthephotoelectriceffect.Whenlightofahighenoughfrequencystrikesametal,electrons
areejectedfromthesurface.

2.Abovethethresholdfrequency,themaximumkineticenergyofejectedelectronsincreaseslinearlywiththe
frequencyofthelight,asshowninfigure4.7.(Kineticenergyisafunctionoftheelectron'sspeed.Wewilllearn
moreaboutkineticenergywithreferencetogasesinchapter6.)
 FIGURE4.7Variationinthemaximumkineticenergyofelectronsejectedfromtwodifferentmetalsurfaces(aandb)asa
functionofthefrequencyofincominglight.

3.Abovethethresholdfrequency,thenumberofemittedelectronsincreaseswiththelight'sintensity,butthekinetic
energyperelectrondoesnotdependonthelight'sintensity.
4.Allmetalsexhibitthesamebehaviour,but,asfigure4.7shows,eachmetalhasadifferentthresholdfrequency.

In1905,AlbertEinsteinpostulatedthatlightcomesinpacketsorbundles,calledphotons.Eachphotonhasanenergy
thatisdirectlyproportionaltoitsfrequency.

Inthisequation,Eistheenergyofaphotonoflightandisitsfrequency.Theproportionalityconstantbetweenenergyand
frequencyisknownasPlanck'sconstant(h)andhasavalueof6.6260693(11)10 34Js(wewilluse6.62610 34Js).
The11inparenthesesreferstotheuncertaintyinthefinaldigitstherefore,h=(6.62606930.0000011)10 34Js.

WORKEDEXAMPLE4.2

Theenergyoflight
Whatistheenergyofaphotonofredlightwithawavelengthof655nm?

Analysis

Thisconversionproblemrequirestwosteps.WedonothaveanequationthatwillcalculateEbasedonthedata
wehave,but,bycombiningthetwoequationswedoknow,wecanrelatetheenergyofaphotontoitsfrequency
andwavelength.

Solution

First,wesummarisethedata.

Thenwecombinetheequationsintoanequationthatrelatesenergytowavelength.

Substitutingourdata,wefind:

Isouranswerreasonable?

Anenergyof10 19Jseemsverysmall,butwemustrememberthatthisistheenergyofasinglephoton.Ifwe
wanttocalculatetheenergyofamoleofthesephotons,weneedtomultiplyourresultbytheAvogadro
constant,i.e.Eonemoleofphotons=EphotonNA=(3.0310 19J)(6.02210 23mol1)=18210 3Jmol1=
182kJmol1.Thisenergyiscomparabletotheenergiesofchemicalbonds.

PRACTICEEXERCISE4.2
Whatistheenergyofaphotonwithawavelengthof
254nm(UVradiation)?
Einsteinconcludedthattheenergyofaphotonthathasthethresholdfrequency(0)correspondstothebindingenergyof
theelectron.Energybeyondthethresholdfrequencyincreasestheelectron'skineticenergyasshowninfigure4.8.Thiscan
bedescribedby:

FIGURE4.8Diagramoftheenergybalanceforthephotoelectriceffect.

Einstein'sexplanationaccountsfortheobservedpropertiesofthephotoelectriceffect.Whentheenergyofthephotonisless
thanh0(lowfrequencylight),noelectronscanescapefromthemetalsurface,nomatterhowintensethelight.Whenthe
energyofthephotonisgreaterthanh0,anelectronisejectedandanyexcessenergyistransferredtothatelectronas
kineticenergy.Theintensityofalightbeamisameasureofthenumberofphotonsperunittimelightofahigher
amplitudecarriesmorephotonsthanlightofloweramplitude.Theintensityofthelightdoesnotdeterminetheamountof
energyperphoton.Morephotonsstrikingthemetalresultinmoreelectronsbeingejected,buttheenergyofeachphoton
andeachelectronisunchanged.Finally,thefactthateachmetalhasitsowncharacteristicthresholdfrequencysuggeststhat
electronsareboundmoretightlytosomemetalsthantoothers.

ChemistryResearch

TheAustralianSynchrotron

Electromagneticradiationinitsmanyformsisfrequentlyusedtoprobethenatureofchemicalcompounds,
whethertheyareemployedasmaterialsforelectronicdevices,newlydevelopeddrugsoranythinginbetween.
Theintensity,coherenceandwavelengthoftheavailableradiationstronglyinfluencethedetailedinformation
thatcanbeextractedandwhichisneededtoadvancechemistryinallitsforms.Importantpropertiesof
electromagneticradiationcanbemaximisedusingasynchrotronsourceand,inthiscontext,theopeningofthe
AustralianSynchrotroninMelbournein2007hasbeenahighlightfortheadvancementofAustralasianscience
(figure4.9).Theopeningofthefacilityhasbroughtthesynchrotronhome,inasense,sinceitwasAustralian
physicistSirMarcusOliphantwhoiscreditedwiththeoriginalideaforaprotonsynchrotron(thefacilityin
Melbourneisactuallyanelectronsynchrotron).Whilescientistsfromourregionhavepreviouslyused
synchrotronsaroundtheglobe(therearenowabout50ofthesefacilitiesintheworld),thesynchrotronin
MelbourneallowscurrentandfutureAustralianandNewZealandscientistsunprecedentedaccesstosucha
facility.Figure4.10showsabeamlinescientistandtwostudentsfromtheUniversityofSydneyaligningasample
onthepowderdiffractionbeamlineattheAustralianSynchrotron.Sofarabout2000scientists,mainlyfrom
AustraliaandNewZealand,haveusedbeamlinesattheAustralianSynchrotronfortheirresearch.Manyofthese
usersarestudentsworkingontheirHonoursorPhDtheses,andonedayyoumightusethefacilityyourself.
 FIGURE4.9AerialviewoftheAustralianSynchrotronbuildinglocatedinClayton,Victoria.
AustralianSynchrotron

FIGURE4.10Beamlinescientist(middle)helpingpostgraduatestudentsusingtheAustralianSynchrotronfacilitiesto
assisttheirstudies.

Australianscientistshaveusedsynchrotronsforapplicationsasdiverseasestablishingthepresenceofarsenicin
theracehorsePharLapunderstandinghowsomenativeplantsimmobiliseheavymetalsandhencecanbeused
toremediatecontaminatedsoilsstudyingtheuptakeofleadinteethwithaviewtoenhancingneonatalcare
aroundBrokenHilldesigningdrugs,includingtheantiviraldrugRelenzabytheAustralianbiotechnology
companyBiotaanddevelopingcopperbasedantiinflammatorydrugsfortreatingarthritisinhorsesanddogs.
Synchrotronradiationcanalsobeusedinlessobviousareassuchasstudyingtheearlystagesoflung
developmentinnewborntammarwallabies,inarchaeologybothtoidentifytheoriginsofartefactsandto
understandhowtheyweremade,aswellasinfoodsciencetodeveloplowfatpotatochips.Recenthighlightsof
theworkbymanyvisitingscientistsattheAustralianSynchrotronincludeinvestigationsofchemicalcompounds
forthedevelopmentofanticancerdrugs,scanninganentireArthurStreetonpaintingtoidentifyindividual
brushstrokesofdifferentcoloursbasedonthedistributionofdifferentelementsonthecanvas,andinvestigation
ofadvancedmaterialsforincorporationintorechargeableLiionbatteries.

Inordertoimproveourunderstandingofsynchrotronscienceweneedtodiscusstheoriginoftheradiation.
Whenelectronsareforcedtotravelinacircularorbitatspeedsapproachingthespeedoflight,theyemitradiation
intheformofphotonsofvariouswavelengths,rangingfrominfraredtohardXrays(wavelengthsof10 6to10
11m,respectively,seefigure4.4).Thisradiationiscalledsynchrotronradiationandischaracterisedbyitshigh
intensity(figure4.11),makingitveryusefulforstudyingtheabsorption,reflectionanddiffractionpropertiesof
matter.Thegenerationofsynchrotronradiationisnotatrivialmatter,and,aswehaveseenabove,thereisa
limitednumberoffacilitiesaroundtheworldinwhichsynchrotronexperimentscanbecarriedout.
 FIGURE4.11Comparisonofbrightness(intensity)ofradiationfromarangeofsources.

Figure4.12showsaschematicoftheAustralianSynchrotron.Electronsaregeneratednearthecentre(electron
gun)andacceleratedtoalmostthespeedoflightbythelinearaccelerator(linac)andtheboosterring.Theyare
thentransferredtotheouterstoragering.Theelectronsareconfinedtothecircularorbitbyaseriesofbending
magnetsseparatedbystraightsections.Astheelectronsaredeflectedthroughthemagneticfieldcreatedbythe
bendingmagnets,theygiveoffelectromagneticradiation,sothatabeamofsynchrotronradiationisproducedat
eachbendingmagnet.Theseintensebeamsofwhiteradiation(i.e.withaspectrumofwavelengthsfrominfrared
tohardXrays)canbecapturedanddirectedtoabeamlineendstationwhereaspecificwavelengthappropriate
foraparticulartechniqueorspecificexperimentcanbeselected.

FIGURE4.12SchematicoftheAustralianSynchrotron.
Source:IllustratorMichaelPayne.ImagesuppliedcourtesyofAustralianSynchrotron.

AtthisstagetheAustralianSynchrotronhasatotalofninebeamlines,ofwhicheightareoperational.Eachof
thesebeamlinesisdedicatedtothespecificpurposesoutlinedinthetablebelow.

Beamlinename Capabilities
Beamline1 Dedicatedfacilityforcrystallographyoflargeproteincrystals,setupwithrobotic
loadingandcentring,andforremoteoperation
Highthroughput
protein
crystallography
 Beamline2 FacilitywithfinelyfocusedXraybeamfordeterminingthecrystalstructureand
electrondensitymapsofsmall,hardtocrystalliseproteins,nucleicacids,andfor
Proteinmicrocrystal smallmolecules
andsmallmolecule
diffraction
Beamline3 Versatile,highresolutionpowderdiffractionfacilityequippedwithsample
chambersforawiderangeofinsituexperiments
Powderdiffraction
Beamline4 Measurementoflongrangeorderincomplexmoleculesandmaterials

Smallandwide
angleXray
scattering
Beamline5 Measurementofshortandmediumrangeorder,bondlengths,coordination
numbersandlocalcoordinationgeometry,andtheoxidationstateofatomsfrom
Xrayabsorption atomicnumberZ=20upwards
spectroscopy
Beamline6 Asforbeamline5,forthelightelements,Z<20alsofortheanalysisofsurfaces
andthinfilms
SoftXray
spectroscopy
Beamline7 Analysisofbondsincomplexmolecules,biologicalmaterials,mineralsandband
structuresincertainsemiconductors
Infrared
spectroscopy
Beamline8 Forproductionofhighresolutionmapsofelementaldistributioninasamplealso
fordeterminationoftheoxidationstateandcoordinationgeometryofatomsin
Microspectroscopy particlesdowntosubmicronsize
Beamline9 Veryflexiblebeamlineforresearchintohighcontrastimagingofobjectsfrom
smallanimalsthroughtoengineeringcomponentsalsoforresearchintothe
Imagingand physicsandbiophysicsofcancertherapytechniques
medicaltherapy

Theintensityoftheradiationcanbefurtherincreasedbytheuseofinsertiondevicesinthestraightsectionsof
thering.Therearetwoclassesofinsertiondevices,multipolewigglersandundulators.Current(third
generation)designsofsynchrotronsaimtooptimisetheintensitythatcanbeobtainedfrominsertiondevices.In
particular,attentionisgiventothesizeandpositioningofthestraightsectionsthataccommodatetheinsertion
devices.TheAustralianSynchrotronisanadvancedthirdgenerationdesign.Itaccommodatesthethreedifferent
typesoflightsources(bendingmagnets,multipolewigglersandundulators)toenableawiderangeofadvanced
experimentsandmeasurementstobecarriedout.

Einstein'sexplanationofthephotoelectriceffectshowedthatlighthassomepropertiesofparticles.Acompletedescription
oflightincludesbothwavelikeandparticlelikeproperties.Whenlightinteractswitharelativelylargebodysuchasa
raindroporaprism,itswavepropertiesdominatetheinteraction.Ontheotherhand,whenlightinteractswithasmallbody
suchasanatomoranelectron,particlepropertiesdominatetheinteraction.Eachviewprovidesdifferentinformationabout
thepropertiesoflight,and,whenwethinkaboutlight,wemustthinkofparticlewavesthatcombinebothtypesoffeatures.

AbsorptionandEmissionSpectra
Inthephotoelectriceffect,whenphotonsstrikeametalsurface,theenergyabsorbedprovidesinformationaboutthe
bindingenergiesofelectronstometalsurfaces.Whenlightinteractswithfreeatoms,theinteractionrevealsinformation
aboutelectronswithinindividualatoms.
LightandAtoms
Attractiveelectrostaticforcesholdanelectronwithinanatom.Energymustbesuppliedtoremovetheelectronfromthe
atom.Thelowertheatom'senergystate,themoreenergyisrequiredtoremoveitselectron.Theenergyrequiredis
measuredrelativetotheenergyofafreeelectron.Wedefinetheenergyofahypotheticalfreestationaryelectrontobezero.
Asfigure4.13indicates,thekineticenergyofafreelymovingelectronispositiverelativetothisconventionalzeropoint.In
contrast,boundelectronsarelowerinenergythanthehypotheticalfreestationaryelectron,soweassignthemnegative
energyvalues.

FIGURE4.13Byconvention,afreestationaryelectronhaszeroenergy,andboundelectronshavenegativeenergies.

Theabsorptionofphotonsbyfreeatomshastwopossibleresults,dependingontheenergyofthephoton.Whenanatom
absorbsaphotonofsufficientlyhighenergy,anelectronisejected(i.e.theatomionises).Thisprocessisdescribedlaterin
thischapter.Here,wefocusonthesecondtypeofresult,inwhichtheatomgainsenergy,butdoesnotionise.Instead,the
atommovesfromthelowestenergyorgroundstatetoahigherenergystatecalledanexcitedstate.Aswesawinchapter
1,thisprocessiscalledanelectronictransition.Excitedstatesarenotstableandatomsinexcitedstatessubsequentlygive
uptheirexcessenergytoreturntolowerenergystates,andeventuallythegroundstate.Theylosetheirexcessenergyin
collisionswithotheratomsorbyemittingphotons.

Thekeyfeatureintheexchangeofenergybetweenatomsandlight(photons)isthatenergyisconserved.Thisrequiresthat
thechangeinenergyoftheatomexactlyequalstheenergyofthephoton.

Whenanatomabsorbsaphoton,theatomgainsthephoton'senergy,soEatomispositive.Whenanatomemitsaphoton,
theatomlosesthephoton'senergy,soEatomisnegative.Asanatomreturnsfromanexcitedstatetothegroundstate,it
mustloseexactlytheamountofenergythatitoriginallygained.However,excitedatomsusuallyloseexcessenergyin
severalstepsinvolvingsmallenergychanges,sothefrequenciesofemittedphotonsareoftenlowerthanthoseofabsorbed
photons.

WORKEDEXAMPLE4.3

EmissionEnergies
Asodiumvapourstreetlampemitsyellowlight(figure4.14)atawavelengthof589nm.Whatistheenergy
changeforasodiumatominvolvedinthisemission?Howmuchenergyisreleasedpermoleofsodiumatoms?
 FIGURE4.14Sodiumvapourlampsemityellowlight.

Analysis

Thisproblemrelatesenergiesofphotonstoenergychangesofatoms.Thesolutionrequiresaconversion
involvingwavelengthandenergy.

Solution

Sodiumatomsloseenergybyemittingphotonsoflight(=589nm).Wecanrelatethewavelengthofoneof
thesephotonstoitsenergy.

Energyisconserved,sotheenergyoftheemittedphotonmustexactlyequaltheenergylostbytheatom.

Theequalityincludesanegativesignbecausetheatomlosesenergy.

Tocalculatetheenergyofaphoton,weneedthefollowingdata.

Thiscalculationgivestheenergychangeforonesodiumatomemittingonephoton.Wemultiplythisvalueby
theAvogadroconstanttoconvertfromenergyperatomtoenergypermole.

Rememberingthatthenegativesignsimplymeansthattheatomislosingenergy,theactualenergyreleasedis
theabsolutevalueofthis,i.e.203kJmol1.

PRACTICEEXERCISE4.3
Mercurylampsemitphotonswithawavelengthof436
nm.Calculatetheenergychangeofthemercuryatoms
inJatom1andkJmol1.

AtomicSpectra
Whenalightbeampassesthroughatubecontainingagasconsistingofatomsofasingleelement,theatomsabsorb
specificfrequenciesoflightcharacteristicofthatelement.Asaresult,thebeamemergingfromthesampletubehasfewer
photonsatthesespecificfrequencies.Thefrequencieswithdiminishedintensityinthevisibleportionofthespectrumcan
bedetectedbypassingtheemerginglightthroughaprism.Theprismdiffractsthelight,withdifferentfrequencies
diffractingthroughdifferentangles.Afterleavingtheprism,thebeamstrikesascreen,wherethefrequencieswith
diminishedintensityappearasgapsordarkbandscalledlines,whichareimagesoftheslit.Thesearethefrequenciesof
lightabsorbedbytheatomsinthesampletube.Theresultingpattern,shownschematicallyinfigure4.15,iscalledan
absorptionspectrum.

FIGURE4.15Schematicrepresentationofanapparatusthatmeasurestheabsorptionspectrumofamonatomicgas.Thegasinthe
tubeabsorbslightatspecificwavelengths,calledlines,sotheintensityoftransmittedlightislowand,therefore,dark
linesappearattheseparticularwavelengths.

Anabsorptionspectrumisusedtodeterminethefrequenciesofthephotonsthatanatomabsorbs.Asimilarexperimentcan
measuretheenergiesofthephotonsemittedbyatomsinexcitedstates.Figure4.19outlinesthefeaturesofanapparatusthat
measurestheseemittedphotons.Anelectricaldischargeexcitesacollectionofatomsfromtheirgroundstateintohigher
energystates.Theseexcitedatomsthenloseall,orpartof,theirexcessenergybyemittingphotons.Thisemittedlightcan
beanalysedbypassingitthroughaprismtogiveanemissionspectrum.Thisisaplotoftheintensityoflightemittedasa
functionoffrequency.Theemissionspectrumforatomichydrogen,showninfigure4.22,showsseveralsharpemission
linesofhighintensity.Thefrequenciesoftheselinescorrespondtophotonsemittedbythehydrogenatomsastheyreturn
totheirgroundstate.

Eachelementhasuniqueabsorptionandemissionspectra.Thatis,eachelementhasasetofcharacteristicfrequenciesof
lightthatitcanabsorboremit.Itisimportanttonotethatfigures4.15,4.19,4.20and4.22showonlythevisibleportionsof
theabsorptionandemissionspectra.Electronictransitionsalsotakeplaceinregionsoftheelectromagneticspectrumthat
thehumaneyecannotdetect.Instrumentsallowscientiststoobserveelectromagneticradiationintheseregions.

ChemicalConnections

PhotoelectronSpectroscopy

DrDanielSoutham,DepartmentofChemistry,CurtinUniversity

Therelativeenergiesofelectronswithinatomscanbemeasuredusingasuiteoftechniquescalledphotoelectron
spectroscopy(PES).PESexploitsthephotoelectriceffect(seepp.11213)tomeasurethekineticenergyof
ejectedelectronsfromatomsandmolecules.InPES,anatomisexcitedbyamonochromaticbeamofphotons
withaknownenergy(Ephoton).Theenergyoftheincidentphotonbeamiswellinexcessoftheionisation
energiesofelectronswithinallvalenceandsomecoreshellsofmanyatoms.Whenanincidentphotonexcitesthe
atomormolecule,anelectronabsorbsenergyandisejectedfromitsorbital(seefigure4.16).Theejected
electronsarecalledphotoelectrons.
 FIGURE4.16 (a)TheprocessofionisationofanelementMcausedbytheincidentphotonejectingaphotoelectron.
(b)Anillustrationoftheatomicscaleprocessshowinganincidentphotonexcitinganelectronwhich
isejectedfromtheatomwithameasurablekineticenergy.

Thekineticenergyofthephotoelectroncanbecomparedwiththeenergyoftheincidentphotontogiveits
bindingenergy.Thebindingenergyofeachelectronischaracteristicnotonlyoftheatomandtheorbitalin
whichtheelectronresides,butalsooftheoxidationstateoftheatomorionandthesurroundingchemical
bondingenvironment.PESgivesstrongexperimentalevidenceforthequantisednatureoftheatomandthe
existenceofatomicandmolecularorbitals(seesection5.7).Forexample,infigure4.17,thephotoelectron
spectraofelementsfromthesecondperiodoftheperiodictableconfirmsthat,astheatomicnumberincreases,
thecore1selectronsalsoincreaseinenergy.Theirbindingenergiesthereforeincrease,andtheybecomemore
difficulttoremove.

FIGURE4.17Photoelectronspectraofelementsfromthesecondperiodoftheperiodictable.Theregionofthespectra
correspondingtoionisationof1selectronsisshownforeachelement.

TheincidentphotonsusedinPESareoftenderivedfromXrayemissionsofmagnesium(121.0MJmol1)and
aluminium(143.4MJmol1),makingXrayphotoelectronspectroscopy(XPSalsocalledelectronspectroscopy
forchemicalanalysis,ESCA)themostfrequentlyencounteredtechniqueofthesuite.XPSismostoftenusedfor
theanalysisofsurfaces,suchassemiconductors,polymers,ceramicsandmetalalloys.XPSallowsthe
quantitativedeterminationofelementalabundance,andsomeinstrumentscanachievespatialelementalmapping,
whichisusefulinawiderangeofdisciplinessuchasmaterialsscienceandgeology.Arecentexampledisplays
theutilityofXPSinmodernscientificresearch.Theinvestigatorsdepositedatomicallyprecisenanoribbonsof
graphenesheetsinachevronpatternontoagoldsurface,asshowninfigures4.18a,bandusedXPStoensure
thatthegraphenedidnotsufferanyoxidationduringthisprocess.Asshowninfigure4.18c,thecarbon1speak
hasachemicalbondingenvironmentcharacteristicoftheabsenceofoxygen.
 FIGURE4.18 (a)Thechemicalstructureofagraphenenanoribbon,
(b)ascanningtunnellingmicrograph(seechapter1)illustratingdepositionofnanoribbonsonagold
surfaceand
(c)aphotoelectronspectrumofthesurfaceindicatingthelackofoxidationofgraphene.

FIGURE4.19Schematicrepresentationofanapparatusthatmeasurestheemissionspectrumofagaseouselement.Emissionlines
appearbrightagainstadarkbackground.Thespectrumshownistheemissionspectrumforhydrogenatoms.

FIGURE4.20Emissionpatternsforhydrogen,neon,sodiumandmercury.Eachelementhasauniqueemissionpatternthat
providesvaluablecluesaboutitsatomicstructure.

Eachfrequencyabsorbedoremittedbyanatomcorrespondstoaparticularenergychangefortheatom.These
characteristicpatternsofenergygainsandlossesprovideinformationaboutatomicstructure.Figure4.20showsthe
emissionspectraforselectedatoms.

QuantisationofEnergy
Whenanatomabsorbsaphotonoflightoffrequency,thelightbeamlosesenergyequaltoh,andtheatomgainsthat
amountofenergy.Whathappenstotheenergythattheatomgains?Aclueisthat,whenthefrequencyoftheincoming(or
absorbed)lightishighenough,itproducescationsandfreeelectrons.Inotherwords,aphotonwithhighenoughenergy
cancauseanatomtoloseoneofitselectrons,i.e.ionise.Thisimpliesthatabsorptionofaphotonresultsinanenergygain
foranelectronintheatom.Statedasanequation:

Theatomicspectraofmostelementsarecomplexandshowlittleapparentregularity.However,in1885,theSwiss
mathematicianandphysicistJohannBalmerwasabletoproposeasingleequationthatcoulddescribetheemission
spectrumofthehydrogenatom.Theequationwas:

inwhichn 1andn 2areintegers(1,2,3etc.).In1913,theDanishphysicistNielsBohrusedEinstein'spostulate(E=h)to

interpretBalmer'sobservations.Combiningthetwoequations,Bohrwasabletodescribetheenergylevelsoftheelectronin
thehydrogenatomwiththefollowingequation,wherenisapositiveinteger.

Thenegativesignintheequationreflectsthefactthatboundelectronsarelowerinenergythanastationaryfreeelectron
(withitsenergydefinedaszero).

Bohrrealisedthattheemissionfrequencieshavespecificvaluesbecausetheelectroninahydrogenatomisrestrictedto
specificenergies.Bohr'sideaofrestrictedenergylevelswasrevolutionarybecausescientistsatthattimethoughtthatthe
electroninahydrogenatomcouldhaveanyenergy.Incontrast,Bohrinterpretedthehydrogenemissionspectrumtomean
thatelectronsboundtoatomscanhaveonlycertainspecificenergyvalues.HewontheNobelPrizeinphysicsin1922for
thisinterpretation.Apropertythatcannotchangecontinuously,andisrestrictedtospecificvalues,issaidtobequantised.
Theatomicenergylevelsofhydrogen(andotherelements)arequantised.Eachintegervalueofndescribesoneofthe
allowedenergylevelsofthehydrogenatom.Forexample,theenergyofanelectroninhydrogen'sfourthlevelis:

Whenanelectronchangesenergylevels,thechangeisanelectronictransitionbetweenquantisedlevels.Whenahydrogen
atomabsorbsoremitsaphoton,itselectronmovesfromoneenergyleveltoanother.Thus,thechangeinenergy(E)of
theatomistheenergydifferencebetweenthetwolevels.

Photonsalwayshavepositiveenergies,butenergychanges(E)canbepositiveornegative.Whenaphotonisabsorbed,
anelectronispromotedtoahigherenergylevel,theatomgainsenergyandEfortheatomispositive.

Whenaphotonisemitted,anelectronfallsfromahigherenergyleveltoalowerone,theatomlosesenergyandEforthe
atomisnegative.

Wecancombinethesetwoequationsbyusingabsolutevalues.

WORKEDEXAMPLE4.4

EnergylevelsoftheHydrogenAtom
Whatistheenergychangewhentheelectroninahydrogenatomundergoesatransitionfromthefourthenergy
leveltothesecondenergylevel?Whatisthewavelengthofthephotonemitted?

Analysis

Thequestionasksaboutenergyandthewavelengthofaphotonemittedbyahydrogenatom.Wavelengthis
 relatedtoenergy,andphotonenergyisdeterminedbythedifferenceinenergybetweenthetwolevelsinvolved
inthetransition.Inthiscase,theelectronmovesfromthefourthtothesecondenergylevel.Theenergy
differencebetweenthesetwostatesisgivenby:

Solution

Asshownabove,E4=1.3610 19J.Asimilarcalculationgivestheenergyofthesecondlevel.

Thisenergychangeisnegativebecausetheatomlosesenergy.Theenergydifferencebetweenthetwolevelsis:

Thenegativesignfortheenergychangeisconsistentwiththeatomlosingenergy.Thislostenergyappearsasa
photonwithenergyof:

Todeterminethewavelengthofthephoton,weuse:

Solvingforgives:

Isouranswerreasonable?

Thesignsoftheenergiesareconsistenttheatomlosesenergyandthephotonemittedhaspositiveenergy.
Fromfigure4.4(p.112)wecanseethatlightwithawavelengthof486nmhasabluegreencolour.Cross
checkingagainsttheemissionspectrumofhydrogen(figure4.20),wecanseethatithassuchabluegreenline.
Therefore,wecanbeconfidentthatouransweriscorrect.

PRACTICEEXERCISE4.4
Whatenergyandwavelengthmustaphotonhaveto
exciteahydrogenatomfromitsgroundstate,i.e.n=
1,tothen=4level?

EnergyLevelDiagrams
Electronictransitionsinatomscanberepresentedusinganenergyleveldiagramsuchastheoneshowninfigure4.21b.
Energyleveldiagramsareaconcisewaytosummariseinformationaboutatomicenergies.Theyshowenergyalongthe
verticalaxisandeachenergystateoftheatomisrepresentedbyahorizontalline.
 FIGURE4.21 (a)Aballonastaircaseshowssomeofthepropertiesofquantisedenergylevels.
(b)Quantisedenergylevelscanbedepictedusinganenergyleveldiagram.
(c)Electronictransitionsoccurbetweenquantisedenergylevelsthrougheitherabsorptionoremissionof
photons.

Wecanbegintounderstandthequantumlevelsofanelectronboundtoanatombypicturingaballonastaircase.As
illustratedinfigure4.21,aballmaysitonanyofthesteps.Tomoveaballfromthebottomofthestaircasetostep5
requirestheadditionofaspecificamountofenergy,E=E5E1.Iftoolittleenergyissupplied,theballcannotreachthis
step.Conversely,ifaballmovesdownthestaircase,itreleasesspecificamountsofenergy.Ifaballmovesfromstep5to
step3,itlosesenergy,E=E3E5.Althoughaballmayrestsquarelyonanystep,itcannotbesuspendedbetweenthe
steps.Electronsinatoms,likeballsonsteps,cannotexistbetweensteps,butmustoccupyoneofthespecific,quantised
energylevels.Rememberthatthisisananalogyatomicenergylevelsarenotatallsimilartostaircasesexceptinbeing
quantised.

Ahydrogenatomhasaregularprogressionofquantisedenergylevels.Figure4.22showstheenergyleveldiagramfor
hydrogenatomsarrowsrepresentsomeofthepossibleabsorptionandemissiontransitions.Noticethattheenergiesof
absorptionfromthelowestenergylevelareidenticaltotheenergiesofemissiontothelowestenergylevel.Thismeansthat
thewavelengthsoflightabsorbedintheseupwardtransitionsareidenticaltothewavelengthsoflightemittedinthe
correspondingdownwardtransitions.
 FIGURE4.22Energylevelsforthehydrogenatomandsomeofthetransitionsthatoccurbetweenlevels,aswellastheresulting
emissionspectrum.Upwardarrowsrepresentabsorptiontransitions,anddownwardarrowsrepresentemissions.

Elementsotherthanhydrogenalsohavequantisedenergylevels,butaswewillseelaterinthischaptertheycannotbeso
simplydescribedbecausetheyhavemorethanoneelectron.Inthesecases,scientistsuseexperimentalvaluesforobserved
absorptionandemissionlinestocalculatetheallowedenergylevelsforeachdifferentelement.

WORKEDEXAMPLE4.5

EnergyLevelDiagrams

RubylasersusecrystalsofAl2O3.ThecrystalscontainsmallamountsofCr3+ions,whichabsorblightbetween
400and560nm.Theexcitedstateionslosesomeenergyasheat.Afterlosingheat,theCr3+ionsreturntothe
groundstatebyemittingredlightwithawavelengthof694nm.
(a) CalculatetheenergyinkJmol1ofthe500nmradiationusedtoexcitetheCr3+ions.
(b)CalculatetheenergyinkJmol1oftheemittedlight.
(c)Calculatethefractionoftheexcitationenergyemittedasredphotonsandthefractionlostasheat.
(d)Drawanenergyleveldiagramthatsummarisestheseprocesses.

Analysis

Thisproblemasksaboutenergies,lightandions.Withmultipartproblems,thebeststrategyistoworkthrough
thepartsoneatatime.Parts(a)and(b)concernthelinkbetweenlightandenergyasdiscussedearlierinthis
section.Oncethetransitionenergieshavebeendetermined,wecancalculatethefractionoftheexcitedstate
energylostasheatforpart(c),andwecanalsodrawanenergyleveldiagramthatshowshowthelevelsare
relatedforpart(d).

Solution

Wesolve(a)usingthefollowingequationsandtheAvogadroconstant.
Thisistheenergychangeperion.Tocalculatethechangepermole,wemultiplybytheAvogadroconstant.We
alsoneedtoconvertfromJtokJ.

Applythesamereasoningto(b).Theresultgivestheenergyoftheredphoton.

Tosolve(c),rememberthatenergyisconserved.Thesumoftheemittedheatandtheemittedphotonmustequal
theenergyabsorbedbytheion.

Because239kJmol1isabsorbedand172kJmol1isemitted,thefractionoftheexcitationenergyreemittedis
.Thefractionconvertedtoheatisthedifferencebetweenthisvalueand1.000,whichis0.280.In
otherwords,72.0%oftheenergyabsorbedbythechromiumionisemittedasredlight,andtheother28.0%is
lostasheat.

Part(d)asksforanenergyleveldiagramforthisprocess.Theelectronstartsinthegroundstate.Onabsorption
ofaphoton,theelectronmovestoanenergylevelthatishigherby239kJmol1.Thechromiumionloses
28.0%ofitsexcitedstateenergyasheatastheelectronmovestoalevelthatis172kJmol1abovetheground
state.Finally,emissionoftheredphotonreturnstheCr3+iontothegroundstate.Thenumericalvaluesallowus
toconstructanaccuratediagram.

Isouranswerreasonable?

WhenCr3+ionsabsorblight,theyarepromotedtoanenergylevelhigherthantheenergythattheylateremit.If
calculationshadshownthattheemittedlighthadalargerenergythantheabsorbedlight,theresultwouldhave
beenunreasonablebecausethesystemwouldviolatethelawofconservationofenergy.

PRACTICEEXERCISE4.5
Afterexcitationinanelectricdischarge,anatomof
Hgreturnstothegroundstatebyemittingtwophotons
 withwavelengthsof436nmand254nm.Calculate
theexcitationenergyoftheexcitedstateinkJmol1.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.3PropertiesofElectrons
Theenergiesofelectronsinatomsplayacentralroleindeterminingchemicalbehaviour.Severalother
propertiesofelectronsalsoinfluencethephysicalandchemicalcharacteristicsofatomsandmolecules.
Somepropertiesarecharacteristicofallelectrons,butothersariseonlywhenelectronsareboundto
atomsormolecules.Inthissection,wedescribethepropertiescharacteristicofallelectrons.

Everyelectronhasamassof9.10910 31kgandachargeof1.60210 19C.Electronshavemagnetic

propertiesthatarisefromapropertycalledspin,whichwemetbrieflyinchapter1andwilldescribein
moredetailinsection4.4.

TheFrenchphysicistLouisdeBroglie(18921987,NobelPrizeinphysics,1929)wasthefirsttosuggest
that,likephotons,electronsalsodisplaywaveparticleduality,whichmeansthattheyhavebothparticle
andwaveproperties.

Experimentshadshownthatabeamoflightshiningonanobjectexertsapressure,whichimpliesthata
photonhasmomentum.Quantitativemeasurementsofthepressureexertedbylightshowedthatasimple
equationrelatesthemomentumoflight(p)toitsenergy.

Aswehavealreadydescribed,lightenergyisalsorelatedtoitswavelength.

Combiningthesetwoenergyexpressionsgivesanexpressionrelatingpto.

Thespeedoflightcancels,leavinganequationthatdeBrogliesuggestedshouldapplytoelectronsand
otherparticlesaswellastophotons.

Themomentumofaparticleistheproductofitsmassandvelocity(u),p=mu.Substitutingthisand
solvingforgivesaformofthedeBroglieequationthatlinksthewavelengthofaparticlewithitsmass
andvelocity.

DeBroglie'stheorypredictedthatelectronsarewavelike.Howmightthisbeconfirmed?Figure4.23
showsexamplesofthecharacteristicintensitypatternsdisplayedbywaves.Infigure4.23a,waterwaves
radiateawayfromtwobobbingfloatsandformastandingpattern.Infigure4.23b,diffractedXrays
formasimilarwavepattern.Highenergyphotonshavepassedthroughtheregulararrayofatomsina
crystal,whoseelectroncloudsscatterthephotonwaves.Ifelectronshavewaveproperties,theyshould
displayregularwavepatternslikethese.
 FIGURE4.23 Examplesofwavepatterns:
(a)Floatsproducestandingwaterwaves,
(b)Xraysgeneratewaveinterferencepatternsand
(c)protrudingatomsonametalsurfacegeneratestandingelectronwaves.

In1927,AmericanphysicistsClintonDavissonandLesterGermer,andBritishphysicistGeorge
Thomson,separatelycarriedoutexperimentsinwhichtheyexposedmetalfilmstoelectronbeamswith
welldefinedkineticenergies.Bothexperimentsgeneratedpatternslikethoseshowninfigure4.23b,
confirmingthevalidityofthedeBroglieequationforelectronwavelengths.Thisestablishedthewave
natureofelectrons.DavissonandThomsonwereawardedtheNobelPrizeinphysicsin1937forthis
discovery.

Inrecentyears,scanningtunnellingelectronmicroscopeshaveproducedimagesofelectronwaves,an
exampleofwhichappearsinfigure4.23c.Here,twoatomsonanotherwisesmoothmetalsurfaceact
likethefloatsinfigure4.23a,andcausetheelectronsinthemetaltosetupastandingwavepattern.

Bothphotonsandelectronshavewaveandparticleproperties,butdifferentequationsdescribetheir
properties.Table4.1summarisesthepropertiesofphotonsandfreeelectrons.
TABLE4.1 Equationsforphotonsandfreeelectrons
Property Photonequation Electronequation
energy

wavelength

speed

h:Planck'sconstant:frequencym:massu:velocity

WORKEDEXAMPLE4.6

Wavelengths
Thestructureofacrystalcanbestudiedbyobservingthewaveinterferencepatternsthat
resultfrompassingparticlewavesthroughthecrystal.Togeneratewelldefinedpatterns,the
wavelengthoftheparticlewavemustbesimilartothedistancebetweenatomsinthecrystal.
Determinetheenergyofaphotonparticlewavebeamwithawavelengthof0.25nmandthe
energyofanelectronparticlewavebeamwiththiswavelength.

Analysis

Thisproblemhastwoparts,onedealingwithphotonsandtheotherwithelectrons.Weare
askedtorelatethewavelengthsoftheparticlewavestotheircorrespondingenergies.Table
4.1emphasisesthatphotonsandelectronshavedifferentrelationshipsbetweenenergyand
wavelength.Thus,weusedifferentequationsforthetwocalculations.

Solution

PhotonenergyisgivenbyE=h=hc/.Wesubstituteandevaluate,beingcarefulwithunits.

Foranelectron,weneedtoworkwithtwoequations.ThedeBroglieequationlinksthe
velocityofanelectronwithitswavelength.

Thekineticenergyequationlinksthevelocityofanelectronwithitskineticenergy.

Beginbydeterminingthevelocityoftheelectron,recallingfromchapter2that1J=1kgm2
s2.

Next,usethevelocitytofindthekineticenergyoftheelectron.

Isouranswerreasonable?

Theenergyofthephotonishigherthanthekineticenergyoftheelectron,whichisreasonable
sincetheelectronhasamass.

PRACTICEEXERCISE4.6
Inaphotoelectriceffectexperiment,a
photonwithanenergyof1.2510 18Jis
absorbed,causingtheejectionofanelectron
withakineticenergyof2.510 19J.
Calculatethewavelength(innm)associated
witheach.
ThedeBroglieequationpredictsthateveryparticlehaswavecharacteristics.Thewavepropertiesof
subatomicparticlessuchaselectronsandneutronsplayimportantrolesintheirbehaviour,butforlarger
objects,suchastabletennisballsorcars,theydonot.Thereasonisthescaleofthewaves.Forallexcept
subatomicparticles,thewavelengthsinvolvedaresoshortthatweareunabletodetectthewave
properties.

WORKEDEXAMPLE4.7

MatterWaves

Calculatethewavelengthsofanelectrontravellingat1.0010 5ms1andatabletennisball
withamassof11gtravellingat2.5ms1.

Analysis

Thisproblemdealswithparticlewavesthathavemass.ThedeBroglieequationrelatesthe
massandspeedofanobjecttoitswavelength.

Solution

Fortheelectron:melectron=9.10910 31kg,u=1.0010 5ms1

Forthetabletennisball:mball=11g,u=2.5ms1

Isouranswerreasonable?

Thewavelengthoftheelectronisintheorderoftheatomicsize,whichisconsistentwiththe
factthatelectronshaveparticlewaveduality.Thewavelengthofthetabletennisballis
extremelysmall,whichisexpectedaswedonotobservewavecharacteristicsforthetable
tennisball.

PRACTICEEXERCISE4.7
Calculatethewavelengthassociatedwitha
protonthatismovingataspeedof2.85
10 5ms1.
TheHeisenbergUncertaintyPrinciple
Aparticleoccupiesaparticularlocation,butawavehasnoexactposition.Awaveextendsoversome
regionofspace.Becauseoftheirwaveproperties,electronsarealwaysspreadoutratherthanlocatedin
oneparticularplace.Asaresult,thepositionofamovingelectroncannotbepreciselydefined.We
describeelectronsasdelocalisedbecausetheirwavesarespreadoutratherthanpinpointed.

Mathematically,thepositionandmomentumofaparticlewavearelinked.WernerHeisenberg(1901
1976,NobelPrizeinphysics,1932),aGermanphysicist,showedinthe1920sthatthemomentumand
positionofaparticlewavecannotbesimultaneouslydetermined.Ifaparticularparticlewavecanbe
pinpointedinaspecificlocation,itsmomentumcannotbeknownaccurately.Conversely,ifthe
momentumofaparticlewaveisknownprecisely,itslocationcannotbeidentified.Heisenberg
summarisedthisuncertaintyinwhathasbecomeknownastheuncertaintyprinciple:themore
accuratelyweknowposition,themoreuncertainweareaboutmomentum,andviceversa.Uncertaintyis
afeatureofallobjects,butitbecomesimportantonlyforverytinyobjectslikeelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.4QuantisationandQuantumNumbers
Thepropertiesofelectronsmentionedsofar(mass,charge,spinandwavenature)applytoallelectrons.
Electronstravellingfreelyinspace,electronsmovinginacopperwireandelectronsboundtoatomsall
havethesecharacteristics.Boundelectrons,thoseheldinaspecificregionofanatombyelectrostatic
forces,haveadditionalimportantpropertiesrelatingtotheirenergiesandtheshapesoftheirwaves.These
additionalpropertiescanhaveonlycertainspecificvalues,i.e.theyarequantised.

Asdescribedinsection4.2,atomsofeachelementhaveunique,quantisedelectronicenergylevels(see
figures4.21and4.22).Thisquantisationofenergyisapropertyofboundelectrons.Theabsorptionand
emissionspectraofatomsconsistofspecificdiscreteenergiesbecauseelectronsundergotransitionsfrom
oneboundstatetoanother.Incontrast,ifanatomabsorbsenoughenergytoremoveanelectron
completely,theelectronisnolongerboundandcantakeonanyamountofkineticenergy.Bound
electronshavequantisedenergiesfreeelectronscanhaveanyamountofenergy.

Experimentalvaluesforthequantisedenergiesofatomicelectronscanbecalculatedfromabsorptionand
emissionspectra.Thetheoryofquantummechanicsprovidesamathematicalexplanationthatlinks
quantisedenergiestothewavecharacteristicsofelectrons.Thesewavepropertiesofatomicelectronsare
describedbytheSchrdingerequation:

where istheHamiltonianoperator(containingtermsforthekineticandpotentialenergy)forthesystem,
Eistheenergyofthesystemandisthewavefunctionforthesystem.Inparticular,istheamplitudeof
theelectron'smatterwave.Aswithlight,theamplitudeitselfdoesnothaveanyphysicalmeaning,butits
squarerepresentstheelectrondensitydistributionorprobabilityoffindinganelectron.Awavefunctionis
amathematicalfunctionthatgivesusinformationaboutanelectron'spositioninanatom.Thesolutionof
theSchrdingerequationgivesusboththeenergiesandtheassociatedwavefunctionsofachemical
system.Despiteitsconciseform,theSchrdingerequationcanbesolvedexactlyonlyforsystems
containingoneelectron.

TheSchrdingerequationhassolutionsonlyforspecificenergyvaluesbecausetheenergyofanatomis
quantised.Foreachquantisedenergyvalue,theSchrdingerequationgeneratesawavefunctionthat
describeshowtheelectronsaredistributedinspace.Aoneelectronwavefunctioniscalledanorbital.We
willdescribethepropertiesoforbitalsinsection4.5.

Eachdescribedpropertycanbeidentified,orindexed,usingaquantumnumber.Thesearenumbersthat
specifythevaluesoftheelectron'squantisedproperties.Eachelectroninanatomhasthreequantum
numbersthatspecifyitsthreevariableproperties:energy(ororbitalsize),angularmomentum(ororbital
shape)andorbitalorientation.Afourthquantumnumberdescribesthespinofanelectron.Todescribean
atomicelectroncompletely,chemistsspecifyavalueforeachofitsfourquantumnumbers:theprincipal
quantumnumber,azimuthalquantumnumber,magneticquantumnumberandspinquantumnumber.

PrincipalQuantumNumber(n)
Themostimportantquantisedpropertyofanatomicelectronisitsenergy.Thequantumnumberthat
indexesenergyforanatomorioncontainingonlyasingleelectronistheprincipalquantumnumber(n).
Forthesimplestatom,hydrogen,wecanuse tocalculatetheenergyofthe
electronifweknown(asseeninsection4.2).However,thatequationappliesonlytothehydrogenatom
orotheroneelectron,hydrogenic(hydrogenlike)ions(suchasHe+andLi2+).
Noknownequationprovidestheexactenergiesofanatomthathasmorethanoneelectron.Nevertheless,
eachelectroninamultielectronatomcanbeassignedavalueofnthatisapositiveintegerandwhich
broadlycorrelateswiththeenergyoftheelectron.Thelowestenergyforanatomicelectroncorresponds
ton=1,andeachsuccessivelyhighervalueofndescribesahigherenergystate.Theprincipalquantum
numbermustbeapositiveinteger:n=1,2,3etc.

Theprincipalquantumnumberalsotellsussomethingaboutthesizeofanatomicorbital,becausethe
energyofanelectroniscorrelatedwithitsdistributioninspace.Thehighertheprincipalquantumnumber,
themoreenergytheelectronhasandthegreaterisitsaveragedistancefromthenucleus.

Summarising,theprincipalquantumnumber(n)canhaveanypositiveintegervalue.Itindexestheenergy
oftheelectronandiscorrelatedwithorbitalsize.Asnincreases,theenergyoftheelectronincreases,its
orbitalgetsbiggerandtheelectronislesstightlyboundtotheatom.

AzimuthalQuantumNumber(l)
Asecondquantumnumberindexestheangularmomentumofanatomicorbital.Thisquantumnumberis
theazimuthalquantumnumber(l).ThesolutionsfortheSchrdingerequationandexperimental
evidenceshowthattheelectrondistributionassociatedwithorbitalscanbedescribedbyavarietyof
shapes.Notethatitistechnicallyincorrecttotalkabouttheshapeofanorbitalitself.Aswehaveseen,
anorbitalismerelyamathematicalfunction.Anorbitalistheamplitudeofanelectron'sthreedimensional
matterwave.Becausetheamplitudecanfluctuatebetweenpositiveandnegativevalues(justlikeany
otherwave),ithasnophysicalmeaningbyitself.Wecan,however,talkabouttheshapeoftheelectron
distributionassociatedwithaparticularorbital,andthistellsuswherewearemostlikelytofindan
electronwithinthisorbital.

Wecancategorisetheshapesofobjects,suchasthesoccerball,rugbyballandfourleafclovershownin
figure4.24,accordingtotheirpreferredaxes.Apreferredaxisisalinethroughthecentreofmassofan
objectorshape,aboutwhichtheshapecanbealignedordistributed.Asoccerballhasnopreferredaxis
becauseitsmassisdistributedequallyinalldirectionsaboutitscentre.Arugbyballhasonepreferred
axis,withmoremassalongthisaxisthaninanyotherdirection.Afourleafcloverhastwopreferredaxes,
atrightanglestoeachother.Inananalogousfashion,electrondensityinanorbitalcanbeconcentrated
alongpreferredaxes.

FIGURE4.24Someeverydayobjectshavetheirmassesconcentratedalongpreferredaxes.Asoccerballhasno
suchaxis,butarugbyballhasoneandafourleafcloverhastwo.

Thevalueoflcorrelateswiththenumberofpreferredaxesinaparticularorbitalandtherebyidentifiesthe
shapeoftheelectrondistributionwithintheorbital.Accordingtoquantumtheory,theseshapesarehighly
restricted.Theserestrictionsarelinkedtoenergy,sothevalueoftheprincipalquantumnumber(n)limits
thepossiblevaluesofl.Thesmallerthevalueofnis,themorecompacttheorbitalandthemorerestricted
itspossibleelectrondistributions.Theazimuthalquantumnumber(l)canbezerooranypositiveinteger
smallerthann:l=0,1,2,,(n1)i.e.therearenvaluesofl.

Historically,orbitalshavebeenidentifiedwithlettersratherthannumbers.Theseletterdesignations
correspondtothevaluesoflasshownbelow.

Anorbitalisnamedbylistingthenumericalvalueforn,followedbytheletterthatcorrespondstothe
numericalvalueforl.Thus,a3sorbitalhasquantumnumbersn=3,l=0.A5forbitalhasn=5,l=3.
Noticethattherestrictionsonlmeanthat,whenn=1,lcanbeonlyzero.Inotherwords,1sorbitalsexist,
butthereareno1p,1d,1for1gorbitals.Similarly,thereare2sand2porbitalsbutno2d,2for2gorbitals.

MagneticQuantumNumber(ml)

Aspherehasnopreferredaxis,soithasnodirectionalityinspace.Whenthereisapreferredaxis,asfora
rugbyball,figure4.25showsthattheaxiscanpointinmanydifferentdirectionsrelativetoanxyz
coordinatesystem.Thus,objectswithpreferredaxeshavedirectionalityaswellasshape.

FIGURE4.25Arugbyballhasdirectionalityandshape.Thefigureshowsthreeofthemanywaysinwhicha
rugbyballcanbeorientedrelativetoasetofx,yandzaxes.

Theelectrondistributionwithinansorbitalissphericalandhasnodirectionality.Electrondistributionsin
otherorbitalsarenonsphericalandthereforehaveadirectionaldependence.Likeenergyandorbital
electrondistribution,thisdirectionaldependenceisquantised.Unlikerugbyballs,theelectron
distributionswithinp,dandforbitalshaverestrictednumbersofpossibleorientations.Themagnetic
quantumnumber(ml)indexestheserestrictions.

Justasorbitalsize(n)limitsthenumberofpreferredaxes(l),thenumberofpreferredaxes(l)limitsthe
possibleorientationsofthepreferredaxes(ml).Whenl=0,thereisnopreferredaxisandthereforeno
preferredorientation,soml=0forsorbitals.Onepreferredaxis(l=1)canorientinanyofthree
directions,givingthreepossiblevaluesforml:+1,0and1.Twopreferredaxes(l=2)canorientinanyof
fivedirections,givingfivepossiblevaluesforml:+2,+1,0,1and2.Eachtimelincreasesinvalueby
oneunit,twoadditionalvaluesofmlbecomepossible,andthenumberofpossibleorientationsincreases
bytwo.Themagneticquantumnumber(ml)canbeanypositiveornegativeintegerbetween0andl:ml=
0,1,2,,li.e.thereare(2l+1)valuesofml.

SpinQuantumNumber(ms)

Aswesawinsection1.5,allelectronshaveapropertycalledspin.Thismeansthatelectronscanbehave
inoneoftwowayswhenplacedinamagneticfield.Whenabeamofsilveratomsispassedthrougha
magneticfield(similartotheexperimentcarriedoutbyOttoSternandWalterGerlachin1921,seefigure
4.26),theatombeamissplit,someatomsaredeflectedinonedirectionandtherestaredeflectedinthe
oppositedirection.Sinceclassicalphysicsassociatesaspinningelectricchargewithamagneticfield,the
experimentalobservationwasexplainedbytheDutchphysicistsGeorgeUhlenbeckandSamuel
Gouldsmitwithapropertytheycalledelectronspin.(Note:(Thereisnophysicalevidencethatanelectron
actuallyspins.)Thefactthatonlytworesponsesareobserveddemonstratesthatspinisquantised.The
spinquantumnumber(ms)indexesthisbehaviour.Thetwopossiblevaluesofmsare and .

FIGURE4.26TheSternGerlachmagneticfieldexperiment.

ThePauliExclusionPrinciple
Acompletedescriptionofanatomicelectronrequiresasetoffourquantumnumbers:n,l,mlandms,
whichmustmeetalltherestrictionsmentionedearlier,assummarisedintable4.2.Eachelectroninan
atomhasauniquesetofquantumnumbersnotwoelectronsinanatomhaveexactlythesamesetof
quantumnumbers.ThiswasfirstpostulatedbytheAustrianphysicistWolfgangPauli(19001958,Nobel
Prizeinphysics,1945)andisknownasthePauliexclusionprinciple.Theprincipleisderivedfrom
quantummechanicsandsupportedbyallexperimentalevidence.
TABLE4.2 Restrictionsonquantumnumbersforelectronsinatoms
Quantumnumber Restrictions Range
n positiveintegers 1,2,,
l positiveintegerslessthann 0,1,,(n1)
ml integersbetweenlandl l,,1,0,+1,,+l

ms

Thenumberofpossiblesetsofquantumnumbersincreasesrapidlyasnincreases.Anatomicorbitalis
designatedbyitsnandlvalues,suchas1s,3d,4pandsoon.Whenl>0,thereismorethanoneorbitalof
eachdesignationthatis,whenl=1,therearethreeporbitalsandforl=2therearefivedorbitals.An
electroninanyorbitalcanhaveaspinquantumnumber(ms)ofeither or .Thus,therearemany
setsofvalidquantumnumbers.Anelectronina3porbital,forexample,canhaveanyoneofsixvalidsets
ofquantumnumbers.
AdirectconsequenceofthePauliexclusionprincipleisthatanyorbitalcancontainamaximumoftwo
electrons(wesaythatanorbitalcontainingtwoelectronsisfull)andthatthetwoelectronsinafullorbital
mustbeofoppositespin.

WORKEDEXAMPLE4.8

ValidQuantumNumbers
Howmanyvalidsetsofquantumnumbersexistfor4dorbitals?Givetwoexamples.

Analysis

Thequestionasksforthesetsofquantumnumbersthathaven=4andl=2.Eachsetmust
meetalltherestrictionslistedintable4.2.Theeasiestwaytoseehowmanyvalidsetsthereare
istolistallthevalidquantumnumbers.

Solution

Becausethisisa4dorbital,nandlarespecifiedandcannotvary.Theothertwoquantum
numbers,however,haveseveralacceptablevalues.Foreachvalueofml,eithervalueofmsis
acceptable,sothetotalnumberofpossibilitiesistheproductofthenumberofpossiblevalues
foreachquantumnumber.Thisisshownonthenextpage.

Quantumnumber n l ml ms

Possiblevalues 4 2 2,1,0,1,2

Numberofpossiblevalues 1 1 5 2
Possiblesetsofvaluesfora4delectron:(1)(1)(5)(2)=10

Thereare10setsofquantumnumbersthatcandescribea4dorbital.Twoofthemareshown
below.

Youshouldbeabletolisttheothereightsets.

Isouranswerreasonable?

Ifyouwritedownallthepossiblesets,youwillfindthatthereare10.Noticethatthereare
always2l+1possiblevaluesofmland2possiblevaluesofms,soeveryndsetoforbitalshas
10possiblesetsofquantumnumbers.
 PRACTICEEXERCISE4.8
Writeallthevalidsetsofquantumnumbers
ofthe5p

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.5AtomicOrbitalElectronDistributionsand
Energies
Thechemicalpropertiesofatomsaredeterminedbythebehaviouroftheirelectrons.Becauseatomic
electronsaredescribedbyorbitals,theinteractionsofelectronscanbedescribedintermsoforbital
interactions.Thetwocharacteristicsoforbitalsthatdeterminehowelectronsinteractaretheirelectron
distributionsinthreedimensionalspaceandtheirenergies.

OrbitalElectronDistributions
Wavelikepropertiescauseelectronstobesmearedoutratherthanlocalisedatanexactposition.This
smearedoutdistributioncanbedescribedusingelectrondensity.Whereelectronsaremostlikelytobe
found,thereishighelectrondensity.Lowelectrondensityoccursinregionswhereelectronsarelesslikely
tobefound.Eachelectron,ratherthanbeingapointcharge,isathreedimensionalparticlewavethatis
distributedoverspaceasanorbital.Orbitalsdescribethedelocalisationofelectrons.Moreover,whenthe
energyofanelectronchanges,thesizeandshapeofitsdistributioninspacechangeaswell.Eachatomic
energylevelisassociatedwithaspecificthreedimensionalatomicorbital.

Anatomthatcontainsmanyelectronscanbedescribedbysuperimposing(addingtogether)theorbitalsfor
allofitselectronstoobtaintheoverallsizeandshapeoftheatom.

Thequantumnumbersnandldeterminethesizeandelectrondistributionofanorbital.Asnincreases,the
sizeoftheorbitalincreases,and,aslincreases,theelectrondistributionoftheorbitalbecomesmore
elaborate.Thesecanbenodalplanesorradialnodes,andthenumberofthesedependsonnandli.e.for
everyorbital,therearen1nodes,ofwhichlarenodalplanesandtheremainderarespherical(radial)
nodes.

OrbitalDepictions
Weneedwaystovisualiseelectronsasparticlewavesdelocalisedinthreedimensionalspace.Orbital
picturesprovidemapsofhowanelectronwaveisdistributedinspace.Thereareseveralwaystorepresent
thesethreedimensionalmaps.Eachoneshowssomeimportantorbitalfeatures,butnoneshowsallofthem.
Weusethreedifferentrepresentations:electrondensityplots,electrondensitypicturesandboundary
surfacediagrams.

Anelectrondensityplotrepresentstheelectrondistributioninanorbitalasatwodimensionalgraph.These
graphsshowelectrondensityalongtheyaxisanddistancefromthenucleus,r,alongthexaxis.Figure
4.27ashowsanelectrondensityplotforthe2sorbital.
 FIGURE4.27 Differentdepictionsofthe2sorbital:
(a)Anelectrondensityplotversusdistancefromthenucleus,
(b)anelectrondensitypictureand
(c)aboundarysurfacediagram.

Electrondensityplotsareusefulbecauseplotsforseveralorbitalscanbesuperimposedtoindicatethe
relativesizesofvariousorbitals.Electrondensityplotsdonot,however,showthethreedimensionalityof
anorbital.

Electrondensitypicturescanindicatethethreedimensionalnatureoforbitals.Onetypeoforbitalpicture
isatwodimensionalcolourpatterninwhichthedensityofcolourrepresentselectrondensity.Figure4.27b
showssuchanelectrondensitypictureofthe2sorbital.Thistwodimensionalpatternofcolourdensity
showsacrosssectionalslicethroughthemiddleoftheorbital.Figures4.27a,4.27bshowthatthe2sorbital
hasonesphericalnode,aswediscussedonthepreviouspage.

Aboundarysurfacediagramprovidesasimplifiedorbitalpicture.Inthisrepresentation,wedrawasolid
surfacethatenclosesmost(usually90%)oftheelectrondensity.Thus,theelectrondensityishighinside
theboundarysurfacebutverylowoutside.Figure4.27cshowsaboundarysurfacediagramofthe2s
orbital.Onedrawbackofboundarysurfacediagramsisthattheydonotshowdetailsofelectrondensity
belowthesurface,includingsphericalnodes.Theydo,however,showallplanarnodes,andfromthoseitis
possibletodeducethenumberofhiddensphericalnodes.

Ausefulanalogyforunderstandingthevalueofboundarysurfacesisaswarmofbeesaroundahive.At
anyonetime,somebeeswillbeoffforagingfornectar,soaboundarysurfacedrawnaroundallthebees
mightcoverseveralhectares.Thiswouldnotbeaveryusefulmapofbeedensity.Aboundarysurface
containing90%ofthebees,ontheotherhand,wouldbeonlyslightlybiggerthanthehiveitself.This
wouldbeaveryusefulmapofbeedensity,becauseanyoneinsidethatboundarysurfacewouldsurely
interactwithbees.

Anotherdrawbackofboundarysurfacediagramsisthatalldetailsofelectrondensityinsidethesurfaceare
lost.Thus,ifwewanttoconveythemaximuminformationaboutorbitals,wemustusecombinationsofthe
variousdepictions.

Theadvantagesanddisadvantagesofthethreetypesofplotscanbeseenbyhowtheyshowone
characteristicfeatureoforbitals.Figure4.27ashowsclearlythatthereisavalueforrwheretheelectron
densityfallstozero.Aplacewhereelectrondensityiszeroiscalledanode.Figure4.27bshowsthenode
forthe2sorbitalasawhitering.Inthreedimensions,thisnodeisasphericalsurface.Figure4.27cdoesnot
showthenode,becausethesphericalnodalsurfaceishiddeninsidethe90%boundarysurface.Thetwo
dimensionalgraphshowsthelocationofthenodemostclearly,theelectrondensitypicturegivesthebest
senseoftheshapeofthenode,whiletheboundarysurfacediagramfailstoshowitatall.

OrbitalSize
Experimentsthatdetermineatomicradiiprovideinformationaboutthesizesoforbitals.Inaddition,
theoreticalmodelsoftheatomcanpredicthowtheelectrondensityofaparticularorbitalchangeswith
distancefromthenucleus.

Inanyparticularatom,orbitalsgetlargerasthevalueofnincreases.Then=2orbitalsarelargerthanthen
=1orbital,then=3orbitalsarelargerthanthen=2orbitals,andsoon.Theelectrondensityplotsin
figure4.28showthistrendforthefirstthreesorbitalsofthehydrogenatom.Thisplotalsoshowsthatthe
numberofnodesincreasesasnincreases.

FIGURE4.28Electrondensityplotsforthe1s,2sand3satomicorbitalsofthehydrogenatom.Theverticallines
indicatethevaluesofrwherethe90%boundarysurfacewouldbelocated.

Inanyparticularatom,allorbitalswiththesameprincipalquantumnumberaresimilarinsize.Asan
example,figure4.29showsthatthen=3orbitalsofthecopperatomhavetheirmaximumelectron
densitiesatsimilardistancesfromthenucleus.Thesameregularityholdsforallotheratoms.Thequantum
numbersotherthannaffectorbitalsizeonlyslightly.Wedescribethesesmalleffectsinthecontextof
orbitalenergieslaterinthissection.
 FIGURE4.29Electrondensityplotsforthe3s(redline),3p(blueline),and3d(greenline)orbitalsforthecopper
atom.Allthreeorbitalsarenearlythesamesize.

Aspecificorbitalbecomessmallerastheatomicnuclearchargeincreases.Asthepositivechargeofthe
nucleusincreases,theelectrostaticforceexertedbythenucleusonthenegativelychargedelectrons
increasesandelectronsbecomemoretightlybound.Thisreducestheradiusoftheorbital.Asaresult,each
orbitalshrinksinsizeasatomicnumberincreases.Forexample,figure4.30showsthatthe2sorbital
steadilydecreasesinsizeacrossthesecondrowoftheperiodictablefromLi(Z=3)toNe(Z=10).The
atomicnumber,Z,isequaltothenumberofprotonsinthenucleus,soincreasingZmeansincreasing
nuclearcharge.

FIGURE4.30Theradiusofthe2sorbitaldecreasesasZincreases.Thenumberatthebottomofeachcolumnis
theradiusofthe2sorbitalinpm(picometres).

DetailsofOrbitalElectronDistributions
Theelectrondistributionsoforbitalsstronglyinfluencechemicalinteractions.Hence,weneedtohave
detailedpicturesoftheseelectrondistributionstounderstandthechemistryoftheelements.

Thequantumnumberl=0correspondstoansorbital.Accordingtotherestrictionsonquantumnumbers,
thereisonlyonesorbitalforeachvalueoftheprincipalquantumnumber.Theelectrondistributionofs
orbitalsisspherical,withradiiandnumberofnodesthatincreaseasnincreases.Figure4.31showsa
boundarysurfacediagramofthe1sorbital.

FIGURE4.31Boundarysurfacediagramofthe1sorbital.

Weintroducedtheconceptofthephaseofawaveinsection4.2,andthisconceptalsoappliestoorbitals.
Ansorbitalhasasinglephase,whichwerefertoaseitherpositive(+)ornegative().Wegenerallydepict
differentphasesusing+andsignssuperimposedontheorbitalelectrondistribution,orbyusingdifferent
colourscorrespondingto+andphases.
Thequantumnumberl=1correspondstoaporbital.Anelectroninaporbitalcanhaveanyofthree
valuesforml,soforeachvalueofntherearethreedifferentporbitals.Thenonsphericalelectron
distributionofporbitalscanbeshowninvariousways.Themostconvenientrepresentationshowsthethree
orbitalswithidenticalelectrondistributionsbutpointinginthreedifferentdirections.Figure4.32shows
boundarysurfacediagramsofthe2porbitals.Eachporbitalhashighelectrondensityinoneparticular
direction,perpendiculartotheothertwoorbitals,withthenucleusatthecentreofthesystem.Thethree
differentorbitalscanberepresentedsothateachhasitselectrondensityconcentratedonbothsidesofthe
nucleusalongapreferredaxis.Wecanwritesubscriptsontheorbitalstodistinguishthethreedistinct
orientations:p x ,p y andp z.Eachporbitalalsohasanodalplanethatpassesthroughthenucleus.Thenodal
planeforthep x orbitalistheyzplane,forthep y orbitalthenodalplaneisthexzplaneandforthep zorbital
itisthexyplane.Thetwolobesofasingleporbitalhaveoppositephasesthisisshowninfigure4.32by
usingadifferentcolourforeachlobe.

FIGURE4.32Boundarysurfacediagramsofthethree2porbitals.Thethreeorbitalshavethesameoverallelectron
distribution,buteachisorientedperpendiculartotheothertwo.Thenodalplaneineachcaseis
illustratedbythegreyhatchedsurface.

Asnincreases,thenumberofnodeswithineachporbitalincreases,justasforsorbitals.Nevertheless,the
directionalityoftheelectrondistributiondoesnotchange.Eachporbitalisperpendiculartotheothertwoin
itssetandhasitslobesalongitspreferredaxis,whereelectrondensityishigh.Toanapproachingatom,
therefore,anelectronina3porbitalpresentsthesamecharacteristicsasoneina2porbital,exceptthatthe
3porbitalisbigger.Consequently,theelectrondistributionsandrelativeorientationsofthe2porbitalsin
figure4.32representtheprominentspatialfeaturesofallporbitals.

Thequantumnumberl=2correspondstoadorbital.Anelectroninadorbitalcanhaveanyoffivevalues
forml(2,1,0,+1and+2),sotherearefivedifferentorbitalsineachset.Eachdorbitalhastwonodal
planes.Consequently,theelectrondistributionsofthedorbitalsaremorecomplicatedthantheirsandp
counterparts.Theboundarysurfacediagramsinfigure4.33showtheseorbitalsinthemostconvenient
way.Inthesedrawings,threeorbitalshaveelectrondistributionsthatlooklikethreedimensional
cloverleaveslyinginaplanewiththelobespointedbetweentheaxes.Asubscriptidentifiestheplanein
whicheachlies:d xy ,d xzandd yz.Afourthorbitalhasanelectrondistributionthatisacloverleafinthexy
plane,butitslobespointalongthexandyaxes.Thisorbitalisdesignated .Ineachofthese
cloverleaforbitals,thelobessituatedoppositeeachotherhavethesamephases,asshowninfigure4.33.
Theelectrondistributioninthefifthorbitalisquitedifferent.Itsmajorlobespointalongthezaxis,butthere
isalsoadoughnutofelectrondensityinthexyplane.Thisorbitalisdesignated .Thetwolobeshave
thesamephase,whilethedoughnutisofoppositephase.
 FIGURE4.33Boundarysurfacediagramsofthedorbitals.Fourofthefivehavethesamecloverleafshapewithtwo
nodalplanesatrightanglestoeachother.The orbitalhasthezaxisasitspreferredaxis.Ithas
twonodesthatareshapedlikecones,oneaboveandonebelowthexyplane.

Thequantumnumberl=3correspondstoanforbital.Thepossiblevaluesofml(3,2,1,0,+1,+2and
+3)meanthattherearesevenforbitals,butastheybecomeimportantonlyforthelanthanoidelementsand
beyond,wewillnotdetailtheirpropertieshere.

OrbitalEnergies
Ahydrogenatomcanabsorbaphotonandchangefromitsmoststable,lowestenergystate(groundstate)
toalessstable,higherenergystate(excitedstate),asdescribedinsection4.2.Wecanexplainthisprocess
usingatomicorbitals.Whenahydrogenatomabsorbsaphoton,itselectroncanundergoatransitiontoan
orbitalthathasalargerprincipalquantumnumber,i.e.ahigherenergy.Figure4.34illustratesthisprocess
forthe1s2ptransitioninthehydrogenatom.
 FIGURE4.34Whenahydrogenatominitsgroundstateabsorbslightofwavelength121.6nm,itisconvertedto
anexcitedstate,inwhichtheelectronoccupiesa2porbital.

Electronictransitionscannotnecessarilyoccurbetweenanysetoforbitalsinthehydrogenatom,andother
oneelectronsystems,theyaregovernedbythefollowingselectionrules:
1.n=anything.Thereisnorestrictiononthevaluesoftheinitialandfinalprincipalquantum
numbers.
2.l=1.Theazimuthalquantumnumbermustincreaseordecreaseby1.Thismeansthatwecannot
haveatransitionfromansorbitaltoanothersorbital,orfromaporbitaltoanotherporbital.
3.ml=0,1.Themagneticquantumnumbermaystaythesame,oritcanincreaseordecreaseby1.

Theatomicorbitalmodelexplainsthespectraandenergylevelsofthehydrogenatomperfectly.Foraone
electronsystemlikethehydrogenatom,theenergylevelsforallorbitalsdependonlyontheprincipal
quantumnumber,n.Allorbitalshavingthesamevalueofnhavethesameenergyandaresaidtobe
degenerate.Formultielectronsystems,experimentsshowthattheunderlyingprinciplesarethesame,
althoughthedetailsforeachkindofatomaredifferent.Variationsinnuclearchargeandthenumberof
electronschangethemagnitudesoftheelectricalforcesthatholdelectronsintheirorbitals.Differencesin
forcescausechangesinorbitalenergiesthatcanbeunderstoodqualitativelyusingforcesofelectrical
attractionandrepulsion,aswedescribelaterinthischapter.Asaconsequence,thedegeneracyoforbitals
foreachlevelofnispartiallyremoved.
TheEffectofNuclearCharge
Ahelium+1cation,likeahydrogenatom,hasoneelectron.Absorptionandemissionspectrashowthat
He+hasenergylevelsthatdependonnonly,justlikethehydrogenatom.Nevertheless,figure4.35shows
thattheemissionspectraofHe+andHdiffer,whichmeansthatthesetwospeciesmusthavedifferent
energylevels.Weconcludethatsomethingbesidesninfluencesorbitalenergy.

FIGURE4.35TheemissionspectraofHe+andHrevealtransitionsatcharacteristicenergies.Mostoftheemitted
photonshavedifferentenergiesbecauseHe+hasquantisedenergylevelsthataredifferentfrom
thoseofH.

ThedifferencebetweenHe+andHisintheirnuclei.Ahydrogennucleusisasingleprotonwitha+1
charge,whereasaheliumnucleuscontainstwoprotons(andtwoneutrons)andhasachargeof+2.The
largernuclearchargeofHe+attractsitssingleelectronmorestronglythanthesmallerchargeofH.Asa
result,He+bindstheelectronwithastrongerforce.Thus,anygivenenergylevelintheheliumionislower
inenergythanthecorrespondinglevelinthehydrogenatom.

Theenergyofanorbitalcanbedeterminedbymeasuringtheamountofenergyrequiredtoremovean
electroncompletelyfromthatorbital.Thisistheionisationenergy(Ei).

TheionisationenergyofHe+isfourtimesthatofH.Thus,thegroundstateorbitalforHe+mustbefour
timeslowerinenergythanthegroundstateorbitalforH.Spectralanalysisshowsthateachorbitalofa
heliumcationisfourtimeslowerinenergythanitscounterpartorbitalinahydrogenatom,showingthat
orbitalenergydependsonZ2inaoneelectronsystem.WhiletheenergylevelsinHandHe+aredifferent
forcorrespondingorbitalsduetotheZ2relationship,therearesomeorbitalenergiesthatcoincideandhence
wecangetemissionenergiesthatareidenticalforbothspecies(seefigure4.35).Figure4.36showsthe
relationshipbetweentheenergylevelsofHe+andH.Thediagramisinexactagreementwithcalculations
basedontheSchrdingerequation.
 FIGURE4.36AnenergyleveldiagramforHe+andH.Eachspecieshasoneelectron,butthedifferentnuclear
chargesmakeeachHe+orbitalfourtimeslowerinenergythanthecorrespondingHorbital.

TheEffectofOtherElectrons
Ahydrogenatomoraheliumcationarerareexamplesofoneelectronsystemsmostotheratomsandions
containcollectionsofelectrons.Inamultielectronatom,electronsaffecteachother'sproperties.These
electronelectroninteractionsmaketheorbitalenergiesofeveryelementunique.

Agivenorbitalisofhigherenergyinamultielectronatomthanitisinthesingleelectronionwiththe
samenuclearcharge.Forinstance,figure4.37showsthatittakesmorethantwiceasmuchenergyto
removetheelectronfromHe+(oneelectron)asitdoestoremoveoneoftheelectronsfromaneutralHe
atom(twoelectrons).Thisdemonstratesthatthe1sorbitalinHe+ismorethantwotimeslowerinenergy
thanthe1sorbitalinneutralHe.Thenuclearchargeofbothspeciesis+2,sothesmallerionisationenergy
forHemustresultfromthepresenceofthesecondelectron.Anegativelychargedelectroninamulti
electronatomisattractedtothepositivelychargednucleus,butitisrepelledbytheothernegatively
chargedelectrons.Thiselectronelectronrepulsioncontributestothelowerionisationenergyofthehelium
atom.
 FIGURE4.37Ionisationenergies.

Shielding

Figure4.38showsafreeelectronapproachingaHe+cation.The+2chargeofthenucleusattractsthe
incomingelectron,butthenegativechargeoftheHe+1selectronrepelsit.Aselectronshavealikecharge,
electronelectronrepulsioncancelsaportionoftheattractionbetweenthenucleusandtheincoming
electron.Chemistscallthispartialcancellationshielding.

FIGURE4.38AsafreeelectronapproachesaHe+cation,itisattractedtothe+2chargeonthenucleusbut
repelledbythe1chargeonthe1selectron.Whenitisfarfromthecation,thefreeelectron
experiencesanetchargeof+1.

Withits1charge,aboundelectroncouldreducethetotalchargebyamaximumof1chargeunit.Indeed,
whenanapproachingelectronisfarenoughawayfromaHe+ion,itfeelsanattractionduetothenet
chargeontheion,+1.However,the1sorbitalisspreadoutallaroundthenucleus.Thismeansthat,asan
approachingelectrongetscloseenough,the1selectronshieldsonlypartofthetotalnuclearcharge.
Consequently,anapproachingelectronissubjecttoanetattractionresultingfromsomeeffectivenuclear
charge(Zeff)lessthan+2butgreaterthan+1.

Incompleteshieldingcanbeseenintheionisationenergiesofhydrogenatoms,heliumatomsandhelium
ions(figure4.37).Withoutshielding,theionisationenergyofaheliumatomwouldbethesameasthatofa
heliumionbothwouldbe8.7210 18J.Withcompleteshielding,oneheliumelectronwouldcompensate
foroneoftheprotonsinthenucleus,makingZeff=+1.Theenergyrequiredtoremoveanelectronfroma
heliumatomwouldthenbethesameastheenergyrequiredtoremoveanelectronfromahydrogenatom,
2.1810 18J.Theactualionisationenergyofaheliumatomis3.9410 18J,abouttwicethefully
shieldedvalueandabouthalfthetotallyunshieldedvalue(figure4.39).Shieldingisincompletebecause
bothelectronsinheliumoccupyanextendedregionofspace,soneitheriscompletelyeffectiveatshielding
theotherfromthe+2chargeofthenucleus.
 FIGURE4.39Ionisationenergiesofaheliumatomwithdifferentamountsofshielding.

Electronsincompactorbitalspackaroundthenucleusmoretightlythanelectronsinlarge,diffuseorbitals.
Asaresult,theeffectivenessinshieldingnuclearchargedecreasesasorbitalsizeincreases.Becausethe
sizeofanorbitalincreaseswithn,anelectron'sabilitytoshielddecreasesasnincreases.Inamultielectron
atom,lowernelectronsareconcentratedbetweenthenucleusandhighernelectrons.Thenegativecharges
oftheseinnerelectronscounteractmostofthepositivechargeofthenucleus.

Theefficientshieldingbyelectronswithsmallvaluesofncanbeappreciatedbycomparingtheionisation
energiesofelectronsinthe2porbitalsinfigure4.37.Consideranexcitedstateheliumatomthathasoneof
itselectronsinthe1sorbitalanditsotherelectronina2porbital.Ittakes0.58510 18Jtoremovethe2p
electronfromthisexcitedstateheliumatom.Thisvalueisclosetothatofanexcitedhydrogenatomwithits
loneelectronina2porbital,0.54510 18J.Itismuchlessthanthe2porbitalionisationenergyofan
excitedHe+ion,2.1810 18J.ThesedatashowthatZeffisquitecloseto+1forthe2porbitalofanexcited
atom.IntheexcitedHeatom,theelectroninthe1sorbitalisveryeffectiveatshieldingtheelectroninthe
2porbitalfromthefull+2chargeofthenucleus.

Inmultielectronatoms,electronswithagivenvalueofngenerallyprovideeffectiveshieldingfororbitals
withalargervalueofn.Thatis,n=1electronsshieldthen=2,n=3andlargerorbitals,whereasn=2
electronsprovideeffectiveshieldingforthen=3,n=4andlargerorbitalsbutprovidelittleshieldingfor
then=1orbital.Theamountofshieldingalsodependsontheelectrondistributionoftheshieldedorbital
anddecreaseswithincreasingazimuthalquantumnumber,l.Theshadedareaoftheelectrondensityplotin
figure4.40emphasisesthatthe2sorbitalhasaregionofsignificantelectrondensitynearthenucleus.A2p
orbitallacksthisinnerlayer,sovirtuallyallofitselectrondensityliesoutsidetheregionoccupiedbythe1s
orbital.Consequently,a1sorbitalshieldsthe2porbitalmoreeffectivelythanthe2sorbital,eventhough
bothn=2orbitalsareaboutthesamesize.Thus,a2selectronissubjecttoalargereffectivenuclearcharge
thana2pelectron.Thisresultsinstrongerelectrostaticattractiontothenucleus,whichmakesthe2sorbital
lowerinenergythanthe2porbitals.The2porbitalsofanymultielectronatomarealwaysslightlyhigherin
energythanthe2sorbital.
 FIGURE4.40Electrondensityplotsforthe1s,2sand2porbitals.Unlikethe2porbital,the2sorbitalhas
significantelectrondensityverynearthenucleus(shadedregion).

Theshieldingdifferencesexperiencedbythe2sand2porbitalsalsoextendtolargervaluesofn.The3s
orbitalisoflowerenergythanthe3p,the4sorbitalisoflowerenergythanthe4p,andsoon.Orbitalswith
higherlvaluesshowsimilareffects.The3dorbitalsarealwayshigherinenergythanthe3porbitals,and
the4dorbitalsarehigherinenergythanthe4porbitals.Theseeffectscanbesummarisedinasingle
generalstatement:Thehigherthevalueofthelquantumnumber,themorethatorbitalisshieldedby
electronsinsmaller,lowerenergyorbitals.

Inaoneelectronsystem(H,He+,Li2+andsoon)theenergyoftheorbitalsdependsonlyonZandn.In
multielectronsystems,orbitalenergydependsprimarilyonZandn,butitalsodependssignificantlyonl.
Inasense,lfinetunesorbitalenergiesandasaconsequencetherearefewerdegenerateorbitals.

Therelativeorbitalenergiesforamultielectronatomareshowninfigure4.41.Itcanbeseenthat,whereas
inaoneelectronsystemthens,npandndorbitalsaredegenerate,thisisnotthecaseinamultielectron
atom.

FIGURE4.41Anenergyleveldiagram(nottoscale)foramultielectronatom.Theorbitalenergiesnowdepend
onlinadditiontobothZandn,andso,incontrasttooneelectronsystems(figure4.36),orbitals
havingthesameprincipalquantumnumbernarenolongerdegenerate.

Electronswiththesamelvaluebutdifferentvaluesofmldonotshieldoneanothereffectively.For
example,whenelectronsoccupydifferentporbitals,theamountofmutualshieldingisslight.Thisis
becauseshieldingiseffectiveonlywhenmuchoftheelectrondensityofoneorbitalliesbetweenthe
nucleusandtheelectrondensityofanother.Recallfromfigure4.32(p.133)thattheporbitalsare
perpendiculartooneanother,withhighelectrondensitiesindifferentregionsofspace.Theelectrondensity
ofthe2p x orbitaldoesnotliebetweenthe2p y orbitalandthenucleus,sothereislittleshielding.Thed
orbitalsalsooccupydifferentregionsofspacefromoneanother,somutualshieldingamongelectronsin
theseorbitalsissmallaswell.

WORKEDEXAMPLE4.9

Shielding
Drawaqualitativeelectrondensityplotshowingthe1s,2pand3dorbitalstoscale.Labelthe
plotinawaythatsummarisestheshieldingpropertiesoftheseorbitals.

Analysis

Thisisaqualitativeproblemthatasksustocombineinformationaboutthreedifferentorbitalson
asingleplot.Weneedtofindelectrondensityinformationanddrawasinglegraphtoscale.
 Solution

Figures4.28,4.29and4.40showelectrondensityplotsofthen=1,n=2andn=3orbitals.We
extracttheelectrondistributionsofthe1s,2pand3dorbitalsfromthesegraphs.Thenweadd
labelsthatsummarisetheshieldingpropertiesoftheseorbitals.Shieldingisprovidedbysmall
orbitalswhoseelectrondensityisconcentratedclosertothenucleusthanthatoflargerorbitals.
Inthiscase,1sshieldsboth2pand3d2pshields3d,butnot1sand3dshieldsneither1snor
2p.Theshieldingpatternscanbelabelledasshown.

Isouranswerreasonable?

Weknowthatthemostimportantfactorfororbitalsizeisthevalueofnandthatsmallorbitals
shieldbetterthanlargeones,sotheshieldingsequencemakessense.

PRACTICEEXERCISE4.9
Constructandlabelagraphillustratingthatthe
2sorbitalshieldsthe3sorbitalmore
effectivelythanthe3sshieldsthe2s.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.6StructureofthePeriodicTable
Aswehaveseeninchapter1,theperiodictableliststheelementsinorderofincreasingatomicnumber.
Becausethenumberofelectronsinaneutralatomisthesameasitsatomicnumber,thislistisalsoinorder
ofincreasingnumberofatomicelectrons.Theperiodictableorganisesatomsinrows(periods)andgroups
suchthatatomswiththesamevalenceelectronconfiguration,leadingtosimilarchemicalproperties,are
locatedinthesamegroup.Wehavesincelearnedthattheelectronsaremainlyresponsibleforanatom's
chemicalproperties,andequippedwiththeknowledgeoforbitalelectrondistributionsandenergieswecan
nowstarttounderstandthereasonsfortheplacementofatomsintheperiodictable.

TheAufbauPrincipleandOrderofOrbitalFilling
Thegroundstateofanatomis,bydefinition,themoststablearrangementofitselectrons.Moststablemeans
thattheelectronsoccupythelowestenergyorbitalsavailable.Weconstructthegroundstateconfiguration
ofanatombyplacingelectronsintheorbitalsstartingwiththelowestinenergyandmovingprogressively
upward.Wehaveseenearlierthatshieldingcausestheorbitalswiththesameprincipalquantumnumberto
increaseinenergyaslincreases.Consequently,the2sorbital,beingoflowerenergythanthe2porbital,fills
first.Similarly,3sfillsbefore3p.Theenergydifferencesbetweenorbitalsbecomelesspronouncedthe
furtherawaytheorbitalsarefromthenucleus.Theconsequenceofthisisthat,fororbitalswithprincipal
quantumnumberslargerthann=2,theorderoforbitalenergiesisnotnecessarilyasexpected.Forexample,
the4sorbitalfillsbeforethe3dorbitals.Therefore,theorderoforbitalfillingisasgiveninfigure4.42a.At
higherlevels,thereareanumberofexceptionstothisfillingsequence.Thesewillbediscussedonpp.145
6.InaccordancewiththePauliexclusionprinciple,eachsuccessiveelectronisplacedinthelowestenergy
orbitalwhosequantumnumbersarenotalreadyassignedtoanotherelectron.ThisiscalledtheAufbau
principle(AufbauisaGermanwordliterallymeaningbuildup).
 FIGURE4.42 (a)Theorderoffillingorbitalswithelectrons
(b)Aneasywaytorememberthegeneralorderofelectronfilling.Orbitalsfillinorderof
increasing(n+l).Whereorbitalshavethesamevalueof(n+l),theonewiththelowestnwill
fillfirst,followedbytheothersinincreasingorderofn.Note,however,forhighervaluesofn,
thereareanumberofexceptionstothisgeneralorder(seetheelectronconfigurationsgiven
infigure4.44).

InapplyingtheAufbauprinciple,rememberthatafulldescriptionofanelectronrequiresfourquantum
numbers:n,l,mlandms.Eachcombinationofnandldescribesonequantisedenergylevel.Moreover,each
levelwithl>1includesmultipleorbitals,eachwithadifferentvalueofml.Foranycombinationofnandl,
allorbitalswiththesamevalueoflaredegenerate,i.e.inanatomtheyhavethesameenergy.Forexample,
the2penergylevel(n=2,l=1)consistsofthreedistinctporbitals(ml=1,0and+1),allwiththesame
energy.Inaddition,thespinquantumnumber,ms,describesthetwopossibledifferentspinorientationsof
anelectron.

Inotherwords,the2penergylevelconsistsof3orbitalswithdifferentmlvaluesthatcanholdasmanyas6
electronswithoutviolatingthePauliexclusionprinciple.Thesameistrueofeverysetofporbitals(3p,4p
etc.).Eachsetcanbedescribedby6differentsetsofquantumnumbersandcanthereforehold6electrons.
Asimilaranalysisforothervaluesoflshowsthateachsenergylevelcontainsasingleorbitalandcanhold
upto2electrons,eachdenergylevelconsistsof5differentorbitalsthatcanholdupto10electrons,and
eachfenergylevelconsistsof7differentorbitalsthatcanholdupto14electrons.

ThePauliexclusionandAufbauprinciplesdictatethelengthoftheperiodsintheperiodictable.After2
electronshavebeenplacedinthe1sorbital(He),thenextelectronmustgoinahigherenergy2sorbital(Li).
After8additionalelectronshavebeenplacedinthe2sand2porbitals(Ne),thenextelectronmustgoina
higherenergy3sorbital(Na).Theperiodictableorganisesatomsinrows(periods)andgroupssuchthat
atomswithsimilarchemicalproperties,asindicatedbytheirvalenceelectronconfiguration,arelocatedin
thesamegroup.Becausetheperiodictablestartswiththefillingofthe1sorbital,everyrowhastofinish
beforethenextsorbitalwithhigherprincipalquantumnumberhastobefilled.Thestartofthenextrowis
anatomwithoneelectroninthatsorbital.

Hereisasummaryoftheconditionsforatomicgroundstates:
1.Theelectronsintheatomoccupythelowestenergyorbitals(seefigure4.42a).
 2.Notwoelectronscanhaveidenticalsetsofquantumnumbers.
3.Orbitalcapacitiesareasfollows:shas2electronspsethas6electronsdsethas10electronsfset
has14electrons.

Armedwiththeseconditions,wecancorrelatetherowsandcolumnsoftheperiodictablewithvaluesofthe
quantumnumbersnandl.Thisisshownintheperiodictableinfigure4.43.Rememberthattheelementsare
arrangedsothatZincreasesoneunitatatimefromlefttorightacrossarow.Attheendofeachrow,we
movetothenexthighervalueofZonerowdownontheleftsideoftheperiodictable.

FIGURE4.43Theperiodictableinblockform,showingthefillingsequenceoftheatomicorbitals.Fillingproceeds
fromlefttorightacrosseachrowandfromtherightendofeachrowtotheleftendofthesucceeding
row.

Thenumberofelementsperrowincreasesasweincreasen.Thefirstperiodcontainsonlyhydrogenand
helium.Thentherearetwo8elementperiods,followedbytwo18elementperiods,andfinallytwo32
elementperiods.

Infigure4.44,eachrowislabelledwiththehighestprincipalquantumnumberofanyofitsoccupied
orbitals.Forexample,elementsofthethirdrow(NatoAr)haveelectronsinorbitalswithn=3(inaddition
toelectronswithn=1and2).Eachcolumnislabelledwithitsgroupnumber,startingwithgroup1onthe
leftandproceedingtogroup18ontheright(thefblockdoesnothavegroupnumbers).Ingeneral,elements
inthesamegroupoftheperiodictablehavethesamearrangementofelectronsintheirhighestenergy
occupiedorbitals,givingrisetotheirsimilarchemicalproperties.
 FIGURE4.44Theperiodictablewithitsrowsandblockslabelledtoshowtherelationshipbetweensectorsofthe
tableandgroundstateconfigurations.Rowsarelabelledwiththehighestprincipalquantumnumber
oftheoccupiedorbitals,andeachblockislabelledwiththeletter(s,p,d,f)indicatingtheorbitalset
thatisfilling.Electronconfigurationsforelements103118aretentative,andarebasedonthe
electronconfigurationsofotherelementsinthesamegroup.

Everyperiodendsattheendofthepblock.Thisindicatesthat,whenthenporbitalsarefull,thenextorbital
toacceptelectronsisthe(n+1)sorbital.Forexample,afterfillingthe3porbitalsfromAl(Z=13)toAr(Z=
18),thenextelement,potassium,hasitsfinalelectroninthe4sorbitalratherthaninoneofthe3dorbitals.
Thisconfirms(seefigure4.42a)thatthe4sorbitalofthepotassiumatomisoflowerenergythanthe3d
orbital.AccordingtotheAufbauprinciple,the3dorbitalsfillafterthe4sorbitalisfull,startingwith
scandium(Z=21).

Asimilarsituationexistsattheendofthenextrow.Whenthe4porbitalisfull(Kr,Z=36),thenextelement
(Rb,Z=37)hasanelectroninthe5sorbitalratherthaneithera4dor4forbital.Infact,electronsarenot
addedtothe4forbitalsuntilelement58,afterthe5s,5pand6sorbitalshavefilled.

Thesevenforbitalscanhold14electrons,andthereforethereshouldbe14fblockelements.However,the
periodictableshowninfigure4.44shows15elementsinboththelanthanoidandactinoidseries.This
reflectsthedebateoverwhetherthefirstelementineachrow(LaandAc,respectively)ispartofthedblock
orfblock.OlderversionsoftheperiodictableplaceLaandAcdirectlybeneathScandY,giving14
lanthanoidandactinoidelements.However,itisclearthatthechemistryofbothLaandAcresemblesthatof
thelanthanoidsandactinoidsrespectively,morethanmaingrouportransitionelements,despitetheirf0
electronconfigurations(indeed,thetermslanthanoidsandactinoidsderivefromlanthanumandactinum,
respectively).

WORKEDEXAMPLE4.10
 OrbitalFillingSequence
Whichorbitalsarefilled,andwhichsetoforbitalsispartiallyfilled,inagermaniumatom?

Analysis

Forthisqualitativeproblem,usetheperiodictabletodeterminetheorderoforbitalfilling.Locate
theelementinablockandidentifyitsrowandcolumn,thenusefigure4.43toestablishthe
sequenceoffilledorbitals.

Solution

Germaniumiselement32.Consultfigure4.43todeterminethatGeisingroup14,row4ofthep
block.

Startingfromthetopleftoftheperiodictableandworkinglefttorightacrosstherowsuntilwe
reachGe,weidentifythefilledorbitals:1s,2s,2p,3s,3p,4sand3d.Germaniumisinrow4of
thepblock,sothe4psetoforbitalsispartiallyfilled.

Isouranswerreasonable?

GehasZ=32,meaningitsneutralatomscontain32electrons.Wecancounthowmanyelectrons
eachorbitalcanhold:2foreachsorbital,6foreachporbitalsetand10foreachdorbitalset.
2(1s)+2(2s)+6(2p)+2(3s)+6(3p)+2(4s)+10(3d)=30electrons,leaving2inthepartially
filled4porbitalset.

PRACTICEEXERCISE4.10
Determinewhichorbitalsarefilledandwhich
setispartiallyfilledfortheelementZr.

ValenceElectrons
Thechemicalbehaviourofanatomisdeterminedbyitssizeandtheelectronsthatareaccessibletoan
approachingchemicalreagent.Accessibilityhasaspatialcomponentandanenergeticcomponent.An
electronisaccessiblespatiallywhenitoccupiesoneofthelargestorbitalsoftheatom.Electronsonthe
perimeteroftheatom,farthestfromthenucleus,arethefirstonesencounteredbyanincomingchemical
reagent.Anelectronisaccessibleenergeticallywhenitoccupiesoneofthehighestenergyoccupiedorbitals
oftheatom.Electronsinhighenergyorbitalsaremorechemicallyactivethanelectronsinlowerenergy
orbitals.

Similarelectronaccessibilitygeneratessimilarchemicalbehaviour.Forexample,iodinehasmanymore
electronsthanchlorine,butthesetwoelementsdisplaysimilarchemicalbehaviour,asreflectedbytheir
placementinthesamegroupoftheperiodictable.Thisisbecausethechemistryofchlorineandiodineis
determinedbythenumberofelectronsintheirlargestandhighestenergyoccupiedorbitals:3sand3pfor
chlorine,and5sand5pforiodine.Eachoftheseelementshassevenaccessibleelectrons,andthisaccounts
fortheirchemicalsimilarities.

Accessibleelectronsarecalledvalenceelectrons,andinaccessibleelectronsarecalledcoreelectrons.
Valenceelectronsmayparticipateinchemicalreactions,whilecoreelectronsdonot.Ingeneral,valence
electronsarethosethathavebeenaddedintheperiodoftheperiodictable(seefigure4.44)thattheatomis
locatedin.Forexample,carbonwithZ=6islocatedinperiod2,soitsvalenceelectronsarethoseinthe2s
and2porbitals(totalling4).Thesituationissimilarforphosphorusinperiod3,whichhas3sand3pvalence
electrons(totalling5).Manganeseinperiod4hasvalenceelectronsinthe4sand3dorbitals(totalling7).

Thenearlyequalenergiesofnsand(n1)dorbitalscreatesomeambiguityaboutvalenceandcoreelectrons
forelementsinthedandfblocks.Forexample,titaniumformsachlorideandanoxidewithchemical
formulaeconsistentwithfourvalenceelectrons:TiCl4andTiO2.Thisshowsthatthetwo3delectronsof
titaniumparticipateinchemicalreactions.Ontheotherhand,zincformscompounds,suchasZnCl2and
ZnO,withonlytwoelectronsinvolvedinitschemistry.Thischemicalbehaviourindicatesthatzinc'sten3d
electrons,whichcompletelyfillthe3dorbitals,areinaccessibleforchemicalreactions.Whenthedorbitals
arepartiallyfilled,thedelectronsparticipateinchemicalreactions,but,whenthedorbitalsarecompletely
filled,thedelectronsdonotgenerallyparticipateinreactions(seebelowforafewexceptions).The
predominantoxidationstateof3+throughoutthefblockelementsalsosuggeststhatgenerallyonlyonedor
felectron(seegroundstateconfigurationsinfigure4.44)isaccessibleforchemicalreactions.The
definitionsofcoreandvalenceelectronsdonotdependonwhethertheelectronsareusedinchemical
reactions,butratherwhethertheyareinanaccessibleenergylevelornot.

Wefindthatthenumberofvalenceelectronscanbedeterminedeasilyfromgroupnumbersintheperiodic
table.Forgroups110,thenumberofvalenceelectronsequalsthegroupnumber.Asexamples,potassium
andrubidium,membersofgroup1,havejustonevalenceelectroneach.Tungsten,ingroup6,hassix
valenceelectrons:two6selectronsandfour5delectrons.Forgroups1218,thenumberofvalence
electronsequalsthegroupnumberminus10(thenumberofelectronsittakestofillthedorbitals).Thus,
antimonyandnitrogen,ingroup15,have1510=5valenceelectronseach(twosandthreep).Forgroup
11,thenumberofvalenceelectronsisexpectedtobe1(theoneselectron).However,oftencompoundsof
theseelementsinvolvetheirdelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.7ElectronConfigurations
Acompletespecificationofhowanatom'selectronsaredistributedinitsorbitalsiscalledanelectron
configuration.Therearethreecommonwaystorepresentelectronconfigurations.Oneisacomplete
specificationofquantumnumbers.Thesecondisashorthandnotationfromwhichthequantum
numberscanbeinferred.Thethirdisadiagrammaticrepresentationoforbitalenergylevelsandtheir
occupancies.

Alistofthevaluesofallquantumnumbersiseasyforthesingleelectroninahydrogenatom:

Eitherdesignationisequallyvalid,becauseundernormalconditionsthesetwostatesareequalin
energy.Inalargecollectionofhydrogenatoms,halftheatomshaveonedesignationandtheotherhalf
havetheotherdesignation.

Asthenumberofelectronsinanatomincreases,alistingofallquantumnumbersquicklybecomes
tedious.Forexample,iron,with26electrons,wouldrequirethespecificationofatleast26setsoffour
quantumnumbers.Tosavetimeandspace,chemistshavedevisedashorthandnotationtowriteelectron
configurations.Theorbitalsymbols(1s,2p,4detc.)arefollowedbysuperscriptsdesignatinghowmany
electronsareineachsetoforbitals.Thecompactconfigurationforahydrogenatomis1s1,indicating1
electroninthe1sorbital.Foranironatomthecompactconfigurationis1s22s22p 63s23p 64s23d 6.

Thethirdwaytorepresentanelectronconfigurationusesanenergyleveldiagramtodesignateorbitals.
Eachorbitalisindicatedbyahorizontallinearrangedverticallyinorderofincreasingenergy.Each
electronisrepresentedbyanarrowandisplacedontheappropriatehorizontalline(orbital).The
directionofthearrowindicatesthevalueofms.Byconvention,wefillorbitalsstartingfromtheleft
handside,andthearrowpointsupwardfor anddownwardfor .Theconfiguration
ofhydrogencanberepresentedbyasinglearrowina1sorbital.

Aneutralheliumatomhastwoelectrons.TowritethegroundstateelectronconfigurationofHe,we
applytheAufbauprinciple.Oneuniquesetofquantumnumbersisassignedtoeachelectron,moving
fromthelowestenergyorbitalupwarduntilallelectronshavebeenassigned.Thelowestenergyorbital
isalways1s(n=1,l=0,ml=0).Bothheliumelectronscanoccupythe1sorbital,providedoneofthem
has andtheotherhas .Belowarethethreerepresentationsofhelium'sground
stateelectronconfiguration.

Thetwoelectronsinthisconfigurationaresaidtobepairedelectrons,meaningthattheyareinthesame
orbital,withopposingspins.Opposingspinscancel,sopairedelectronshavezeronetspin.

Alithiumatomhasthreeelectrons.Thefirsttwoelectronsfilllithium'slowestpossibleenergylevel,the
1sorbital,andthethirdelectronoccupiesthe2sorbital.Thethreerepresentationsforthegroundstate
electronconfigurationofalithiumatomareshownbelow.

Thesetn=2,l=0,ml=0, isequallyvalidforthethirdelectron.

Thenextatomsoftheperiodictableareberylliumandboron.Youshouldbeabletowritethethree
differentrepresentations(thesetofquantumnumbers,theshorthandnotationandtheenergylevel
diagram)forthegroundstateconfigurationsoftheseelements.Thefillingprinciplesarethesameaswe
movetohigheratomicnumbers.

WORKEDEXAMPLE4.11

AnElectronConfiguration
Constructanenergyleveldiagramandtheshorthandnotationofthegroundstate
configurationofaluminium.Provideonesetofvalidquantumnumbersforthehighest
energyelectron.

Analysis

Firstconsulttheperiodictabletolocatealuminiumanddeterminehowmanyelectronsare
presentinaneutralatom.Thenconstructtheelectronconfigurationusingthepatternsofthe
periodictable.

Solution

AluminiumhasZ=13,soaneutralatomofAlhas13electrons.Placethe13electrons
sequentially,usingarrows,intothelowestenergyorbitalsavailable.Then=1orbitalisfilled
bytwoelectrons,eightelectronsfillthen=2orbitals,twoelectronsfillthe3sorbital,and
oneelectrongoesina3porbital.

Thelastelectroncouldbeplacedinanyofthe3porbitals,becausethesethreeorbitalsare
equalinenergy.Thefinalelectroncouldalsobegiveneitherspinorientation.Byconvention,
weplaceelectronsinunfilledorbitalsstartingwiththelefthandside,withspinspointedup.

Theshorthandnotationis1s22s22p 63s23p 1.
 Thehighestenergyelectronisina3porbital,meaningn=3andl=1.Thevalueofmlcan
beanyofthreevalues:+1,1or0.Thespinquantumnumber,ms,canbe or .One
validsetofquantumnumbersis:

Youshouldbeabletowritetheotherfivepossiblesets.

Isouranswerreasonable?

Aluminium,ingroup13,hasthreevalenceelectrons.Theconfigurationsshowthree
electronswithn=3,sotheconfigurationisconsistentwiththevalenceelectroncount.

PRACTICEEXERCISE4.11
Determinetheenergyleveldiagramand
shorthandnotationfortheelectron
configurationofthefluorineatom.

Electronconfigurationsbecomelongerasthenumberofelectronsincreases.Tomakethewritingofa
configurationevenmorecompact,chemistsmakeuseoftheregularpatternfortheelectronswithlower
principalquantumnumbers.Comparetheconfigurationsofneonandaluminiumshownbelow.

Thedescriptionofthefirst10electronsintheconfigurationofaluminiumisidenticaltothatofneon.
Wecantakeadvantageofthispatternandrepresentthatportionas[Ne].Withthisnotation,the
configurationofAlbecomes[Ne]3s23p 1.Theelementattheendofeachrowoftheperiodictablehasa
noblegasconfiguration.Theseconfigurationscanbewritteninthefollowingshorthandnotation.

Notation Configuration Element

[He] 1s2 He(2electrons)

[Ne] [He]2s22p 6 Ne(10electrons)

[Ar] [Ne]3s23p 6 Ar(18electrons)

[Kr] [Ar]4s23d 104p 6 Kr(36electrons)

[Xe] [Kr]5s24d 105p 6 Xe(54electrons)

[Rn] [Xe]6s25d 104f14f6p 6 Rn(86electrons)

Towritetheconfigurationofanyotherelement,wefirstconsulttheperiodictabletofinditslocation
relativetothenoblegases.Thenwespecifytheconfigurationoftheprecedingnoblegasandbuildthe
remainingportionoftheconfigurationaccordingtotheAufbauprinciple.
WORKEDEXAMPLE4.12

AShorthandElectronConfiguration
Determinetheelectronconfigurationofindium,firstinshorthandformandtheninfullform.

Analysis

Locatetheelementintheperiodictable,andfindthenearestnoblegaswithasmalleratomic
number.Startwiththeelectronconfigurationofthatnoblegas,andaddenoughadditional
electronstothenextfillingorbitalstogivetheneutralatom.

SolutionIndium,In,(Z=49)isinrow5,group13.ThenearestnoblegasofsmallerZisKr
(Z=36).Thus,theconfigurationofInhas36electronsintheKrconfigurationand13
additionalelectrons.ThelastorbitaltofillinKris4p,andtheperiodictableshowsthatthe
nextorbitalstofillarethe5s,4dand5porbitals.
Configurationofindium:[Kr]5s24d 105p 1
Towritethefullconfiguration,expandthekryptonconfiguration.
[Kr]=[Ar]4s23d 104p 6=1s22s22p 63s23p 64s23d 104p 6
FullconfigurationofIn(49electrons):1s22s22p 63s23p 64s23d 104p 65s24d 105p 1

Notethatitisusualtoindicateemptyorbitalsinanenergyleveldiagramwhentheyarepart
ofasetofdegenerateorbitals.Forexample,intheenergyleveldiagramabove,weshowthe
twoemptyporbitalsofthe5psetbecauseoneofthesetcontainsasingleelectron.

Isouranswerreasonable?
 Indium,ingroup13,hasthreevalenceelectrons.Theconfigurationsshowthreeelectrons
withn=5,sotheconfigurationisconsistentwiththevalenceelectroncount.

PRACTICEEXERCISE4.12
Determinethecompactnotationforthe
electronconfigurationofthecadmiumatom.

ElectronelectronRepulsion
TheAufbauprincipleallowsustoassignquantumnumberstoaluminium's13electronswithout
ambiguity.Thefirst12electronsfillthe1s,2s,2pand3senergylevels,andthelastelectroncanoccupy
any3porbitalwitheitherspinorientation.Butwhathappenswhenmorethanoneelectronmustbe
placedinapenergylevel?Carbonatoms,forexample,havesixelectrons,twoofwhichoccupy2p
orbitals.Howshouldthesetwoelectronsbearrangedinthe2porbitals?Asfigure4.45shows,three
differentarrangements(ofthe15possible)oftheseelectronsobeythePauliexclusionprinciple:
1.Theelectronscouldbepairedinthesame2porbital(samemlvaluebutdifferentmsvalues).
2.Theelectronscouldoccupydifferent2porbitalswithoppositespinorientations(differentml
valuesanddifferentmsvalues).
3.Theelectronscouldoccupydifferent2porbitalswiththesamespinorientation(differentml
valuesbutthesamemsvalue).

FIGURE4.45Threedifferentarrangementsoftwo2pelectronsthatobeythePauliexclusionprinciple.

Thesethreearrangementshavedifferentenergiesbecauseelectronsthatareclosetogetherrepeleach
othermorethanelectronsthatarefarapart.Asaresult,fortwoormoredegenerateorbitals,thelowest
energysituationresultswhenelectronsoccupytheorbitalsthatkeepthemfurthestapart.Placingtwo
electronsindifferentporbitalskeepsthemrelativelyfarapart,soanatomisoflowerenergywiththe
twoelectronsindifferentporbitals.Thus,arrangements2and3areoflowerenergythanarrangement
1.

Arrangements2and3lookspatiallyequivalent,butexperimentsshowthataconfigurationthatgives
unpairedelectronsthesamespinorientationisalwaysoflowerenergythanonethatgivesthemopposite
orientations.Hund'srulesummarisesthewayinwhichelectronsoccupyorbitalsofequalenergies.The
lowestenergyconfigurationinvolvingorbitalsofequalenergiesistheonewiththemaximumnumberof
electronswiththesamespinorientation.

AccordingtoHund'srule,arrangement3offigure4.45isconsistentwiththegroundstateconfiguration
forcarbonatoms.
WORKEDEXAMPLE4.13

ApplyingHund'sRule
Writetheshorthandelectronconfigurationanddrawthegroundstateorbitalenergylevel
diagramforthevalenceelectronsinasulfuratom.

Analysis

Fromtheperiodictable,weseethatsulfurhas16electronsandisinthepblock,group16.
Tobuildthegroundstateconfiguration,applytheAufbauandthePauliexclusionprinciples
andthenapplyHund'sruleifneeded.

Solution

Thefirst12electronsfillthefourlowestenergyorbitals.

Sulfur'sremainingfourelectronsoccupythethree3porbitals.Thecompleteconfigurationis
1s22s22p 63s23p 4or[Ne]3s23p 4.

Tominimiseelectronelectronrepulsion,putthreeofthe3pelectronsindifferentorbitals,all
withthesamespin,andthenplacethefourthelectron,withoppositespin,inthefirstorbital.
InaccordwithHund'srule,thisgivesthesamevalueofmstoallelectronsthatarenotpaired.
Belowistheenergyleveldiagramforsulfur'svalenceelectrons.

Isouranswerreasonable?

Sulfur,inrow3andgroup16,hassixvalenceelectrons.Theconfigurationsshowsix
electronswithn=3,sotheconfigurationisconsistentwiththevalenceelectroncount.The
electronsarespreadamongthethree3porbitals,whichminimiseselectronelectron
repulsion.

PRACTICEEXERCISE4.13
Determinethecompactelectron
configurationforthenitrogenatomand
writeonevalidsetofquantumnumbersfor
itsvalenceelectrons.
OrbitalswithNearlyEqualEnergies
Thefillingorderembodiedintheperiodictablepredictsaregularprogressionofgroundstate
configurations.Experimentsshow,however,thatsomeelementshavegroundstateconfigurations
differentfromthepredictionsoftheregularprogression.Amongthefirst40elements,thereareonly
twoexceptions:copperandchromium.Chromium(Z=24)isingroup6,fourelementsintothedblock.
Wewouldpredictthatthegroundstatevalenceconfigurationofchromiumshouldbe4s23d 4.Instead,
experimentsshowthatthegroundstateconfigurationofthiselementis4s13d 5.Likewise,the
configurationofcopper(Z=29)is4s13d 10ratherthanthepredicted4s23d 9.

Lookagainatfigure4.42a,whichshowsthatthesetwosetsoforbitalsarenearlythesameinenergy.
Each(n1)dorbitalhasnearlythesameenergyasitsnscounterpart.Inaddition,each(n2)forbital
hasnearlythesameenergyasits(n1)dcounterpart.Table4.3liststheseorbitalsandtheatomic
numbersforwhichthefillingsequencediffersfromtheexpectedpattern.Theseconfigurationsarealso
indicatedinfigure4.44.
TABLE4.3 Atomicorbitalswithnearlyequalenergies
Orbitals Atomicnumbersaffected Example
4s,3d 24,29 Cr:[Ar]4s13d 5
5s,4d 41,42,44,45,46,47 Ru:[Kr]5s14d 7
6s,5d,4f 57,58,64,78,79 Au:[Xe]6s14f145d 10
6d,5f 89,9193,96 U:[Rn]7s25f3f6d 1

Often,ansorbitalcontainsonlyoneelectronratherthantwo.Fiveoftheexceptionalgroundstate
configurationshaveacommonpatternandareeasytoremember:CrandMoares1d 5,andCu,Agand
Auares1d 10.Theotherexceptionalcasesfollownorecognisablepatterns,becausetheyaregenerated
bysubtleinteractionsbetweenalltheelectrons.Amongelementswithvalenceelectronsfillingorbitals
withnearlyequalenergies,severalfactorshelptodeterminethegroundstateconfiguration.Thedetails
arebeyondthescopeofthisbook,exceptthatyoushouldrecognisethatevenasubtlechangecancause
variationsinthefillingpatternpredictedbytheperiodictable.

ConfigurationsofIons
Theelectronconfigurationsofatomicionsarewrittenusingthesameprocedureasforneutralatoms,
takingintoaccountthepropernumberofelectrons.Ananionhasoneadditionalelectronforeachunit
ofnegativecharge.Acationhasonefewerelectronforeachunitofpositivecharge.
Formostatomicions,theelectronconfigurationcanbededucedeasilyfromthatofthecorresponding
neutralatom.Forexample,Na+,NeandFallcontain10electrons,andeachhastheconfiguration
1s22s22p 6.Atomsandionsthathavethesamenumberofelectronsaresaidtobeisoelectronic.

Ingeneral,youwouldexpectthatthelastelectrontobeaddedwouldbethefirstelectrontobeloston
ionisation.Thenearlyequalenergiesofnsand(n1)dorbitalscausestheconfigurationsofsome
cationstodifferfromtheconfigurationspredictedbythefillingpatternoftheperiodictable.Remember
thattheenergyrankingoforbitalssuchas4sand3ddependsonabalanceofseveralfactors,andthat
evenasmallvariationinthatbalancecanchangetheorderoftheorbitals.Thisfeatureisparticularly
importantforthetransitionmetals,forwhichthedorbitalsareoccupied.Experimentsshowthatin
transitionmetalcationsthe(n1)dorbitalsarealwaysoflowerenergythanthensorbitalstherefore,
thefirstelectronsarelostfromthesorbitalbeforethoseindorbitals.Forexample,anFe3+cation
contains23electrons.Thefirst18electronsfillthe1s,2s,2p,3sand3porbitals,aspredictedbythe
periodictable.However,thefiveremainingelectronspopulatethe3dset,leavingthe4sorbitalempty.
ThustheconfigurationoftheFe3+cationis[Ar]3d 5.

Vanadium,V,atoms([Ar]4s23d 3)andFe3+cations([Ar]3d 5)havedifferentconfigurations,eventhough

eachhas23electronsasshowninfigure4.46.

FIGURE4.46Transitionmetalatomsandcationshavedifferentvalenceelectronconfigurations,evenwhen
thespeciescontainthesamenumberofelectrons.

WORKEDEXAMPLE4.14

ConfigurationofaCation

WhatisthegroundstateelectronconfigurationofaCr3+cation?

Analysis

UsetheAufbauprinciple,rememberingthatbecauseCrisatransitionmetal,its4sorbitalwill
beemptiedbeforethe3dorbital.

SolutionAneutralchromiumatomhas24electrons,sothecorrespondingCr3+cationhas
21electrons.Thefirst18electronsfollowtheusualfillingordertogivetheargoncore
configuration:1s22s22p 63s23p 6,or[Ar].Placetheremainingthreeelectronsinthe3dsetof
orbitals,followingHund'srule:[Ar]3d 3.
 Isouranswerreasonable?

Foranytransitionmetalcation,theempty4sorbitalisslightlyhigherinenergythanthe
partiallyfilled3dorbital.Thus,theisoelectronicV2+andCr3+cationsbothhavethe[Ar]3d 3
configuration.Ontheotherhand,theisoelectronicneutralatomscandiumhasthe
configuration[Ar]4s23d 1.

PRACTICEEXERCISE4.14
Determinethegroundstateelectron
configuration(compactform)ofaRu 3+
cation.

Wecansummarisethediscussioninthissectionintoguidelinesforbuildingatomicorionicelectron
configurations:
1.Countthetotalnumberofelectrons.
a.Addelectronsforanions.
b.Subtractelectronsforcations.
2.Fillorbitalstomatchthenearestnoblegasofsmalleratomicnumber.
3.AddremainingelectronstothenextorbitalstobefilledaccordingtothePauliexclusionand
Aufbauprinciples,aswellasHund'srule.
a.Forneutralatomsandanions,placeelectronsinnsbefore(n1)dand(n2)f).
b.Forcations,determinetheelectronconfigurationfortheneutralatomandremovethe
requirednumberofelectronswiththehighestenergy.
4.Lookforexceptionsandcorrecttheconfigurationifnecessary.

MagneticPropertiesofAtoms

HowdoweknowthatanFe3+ioninitsgroundstatehastheconfiguration[Ar]3d 5ratherthanthe
[Ar]4s23d 3configurationpredictedbytheorbitalfillingsequence?Rememberthatelectronspingives
risetomagneticproperties.Consequently,anyatomorionwithunpairedelectronshasnonzeronet
spinandisattractedbyastrongmagnet.Wecandividetheelectronsofanatomorionintotwo
categorieswithdifferentspincharacteristics.Infilledorbitals,alltheelectronsarepaired.Eachelectron
withspinorientation hasapartnerwithspinorientation .Thespinsoftheseelectronscancel
eachother,givinganetspinofzero.Anatomorionwithallelectronspairedisnotattractedbystrong
magnetsandistermeddiamagnetic.Incontrast,spinsdonotcancelwhenunpairedelectronsare
present(inthegroundstateofanatomwithspinsalignedinthesamedirection).Anatomorionwith
unpairedelectronsisattractedtostrongmagnetsandiscalledparamagnetic.Moreover,thespinsofall
theunpairedelectronsareadditive,sotheamountofparamagnetismshownbyanatomorionis
proportionaltothenumberofunpairedspins.

InFe3+,Hund'sruledictatesthatthefivedelectronsallhavethesamespinorientation.Forthesefive
electrons,thespinsallacttogether,givinganetspinof .Thealternativeconfigurationfor
Fe3+,[Ar]4s23d 3,isparamagnetic,too,butitsnetspinis asithasonlythreeunpaired
electrons.ExperimentsshowthatFe3+hasanetspinof .Infact,magneticmeasurementsonawide
rangeoftransitionmetalcationsareallconsistentwiththe(n1)dorbitalsbeingoccupiedratherthan
thensorbital.

WORKEDEXAMPLE4.15

UnpairedElectrons

Whichofthesespeciesisparamagnetic:F,Zn 2+orTi?

Analysis

Paramagnetismresultsfromunpairedspins,whichexistonlyinpartiallyfilledsetsoforbitals.
Weneedtobuildtheconfigurationsandthenlookforanyorbitalsthatarepartiallyfilled.

Solution

F:Afluorineatomhas9electrons,soFhas10electrons.Theconfigurationis1s22s22p 6.
Therearenopartiallyfilledorbitals,sothefluorideionisdiamagnetic.

Zn 2+:Theparentzincatomhas30electrons,andthecationhas28,sotheconfigurationfor
Zn 2+is[Ar]3d 10.Again,therearenopartiallyfilledorbitals,sothisionisalsodiamagnetic.

Ti:Aneutraltitaniumatomhas22electrons.Thegroundstateconfigurationis[Ar]4s23d 2.
Thespinsofthe4selectronscancel,butthetwoelectronsin3dorbitalshavethesamespin
orientation,sotheireffectisadditive.Thisionisparamagnetic,withanetspinof .

Isouranswerreasonable?

Filledorbitalsalwayshaveallelectronspaired,andtwoofthesethreespecieshaveno
partiallyfilledorbitals.OnlyTihasapartiallyfilledorbitalset.

PRACTICEEXERCISE4.15
 Mosttransitionmetalcationsare
paramagnetic.Whichcationsinthefirst
transitionmetalserieshavenetchargesless
than+4andareexceptionstothis
generalisation?

Thegroundstateconfigurationsofmostneutralatomsandmanyionscontainunpairedelectrons,sowe
mightexpectmostmaterialstobeparamagnetic.Onthecontrary,mostsubstancesarediamagnetic.This
isbecausestablesubstancesseldomcontainfreeatoms.Instead,inmolecularsubstances,atomsare
bondedtogetherthroughpairingofelectronstogivemolecules(seechapter5),andsuchbonding
resultsinthecancellationofoverallspin.Asaresult,paramagnetismisobservedprimarilyamong
compoundsofthetransitionandlanthanoidmetals,whosecationshavepartiallyfilleddandforbitals.
Wewillexaminethemagneticpropertiesoftransitionmetalcomplexesindetailinchapter13.

ExcitedStates
Thegroundstateconfigurationisthelowestenergyarrangementofelectrons,soanatomorionwill
usuallyhavethisconfiguration.Whenanatomabsorbsenergy,however,itcanreachanexcitedstate
withanewelectronconfiguration.Forexample,sodiumatomsnormallyhavethegroundstate
configuration[Ne]3s1,butwhensodiumatomsareinthegasphase,anelectricaldischargecaninduce
transferofthe3selectrontoahigherenergyorbital,suchas4p.Excitedatomsareunstableand
spontaneouslyreturntothegroundstateconfiguration,givinguptheirexcessenergyintheprocess.

Excitedstateconfigurationsareperfectlyvalidaslongastheymeettherestrictionsgivenintable4.2.In
theelectricaldischargeofasodiumvapourlamp,forinstance,wefindsomesodiumatomsinexcited
stateswithconfigurationssuchas1s22s22p 63p 1or1s22s22p 53s2.Theseconfigurationsusevalidorbitals
andareinaccordwiththePauliexclusionprinciple,buttheydescribeatomsthatareofhigherenergy
thanthoseinthegroundstate.ItshouldbenotedthatboththeAufbauprincipleandHund'srulecanbe
violatedwhenwritingexcitedstateelectronicconfigurations,butthePauliexclusionprinciplemust
alwaysbeobeyed.

Excitedstatesplayimportantrolesinchemistry.Propertiesofatomscanbestudiedbyobservingexcited
states.Infact,chemistsandphysicistsusethecharacteristicsofexcitedstatesextensivelytoprobethe
structureandreactivityofatoms,ionsandmolecules.Excitedstatesalsohavepracticalapplications.For
example,sodiumvapourlamps,whichareusedforstreetlighting,usetheemissionsfromexcited
sodiumatomsreturningtotheirgroundstates,andthedazzlingcoloursofafireworksdisplaycome
fromphotonsemittedbyvariousmetalionsinexcitedstates.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.8PeriodicityofAtomicProperties
Theperiodicityofphysicalandchemicalproperties,whichissummarisedintheperiodictableofthe
elements,isoneofthemostusefulorganisingprinciplesinchemistry.Theregularperiodictrendscanbe
explainedusingelectronconfigurationsandnuclearcharges.Themostimportantofthosetrendsisthe
atomicradius,whichwewilldiscussfirst,sinceitinfluencesallotherperiodictrends.

AtomicRadii
Thesizeofanatomisdeterminedbyitselectroncloudandthereforebythesizesofitsorbitals.Aswehave
seenearlier,thesesizesaredeterminedbyanumberoffactors,includingeffectivenuclearcharge(Zeff),
orbitalenergyandelectrondistribution.

Assumeyouaremovingfromlefttorightacrossperiod2oftheperiodictable(n=2).WhileZincreases,the
electronsthatareaddeddonotshieldtheincreasingnuclearchargeeffectively,soZeffincreases.Alarger
Zeffexertsastrongerelectrostaticattractionontheelectroncloud,andthisresultsinsmallerorbitals.Moving
fromlefttorightacrossthatperiod,orbitalsbecomesmallerandoflowerenergy.

Nowassumeyouproceeddowngroup1oftheperiodictable.Asnincreases,wewouldexpectorbitalsto
increaseinenergyandbecomelarger.However,asZincreases,wewouldexpectorbitalstobecomesmaller
anddecreaseinenergy.Whichtrenddominateshere?Recallthatthenumberofcoreelectronsincreasesas
wemovedownanygroup.Forexample,sodium(Z=11)has10coreelectronsand1valenceelectron.In
thenextperiod,potassium(Z=19)has18coreelectronsand1valenceelectron.Theshieldingprovidedby
potassium'sadditional8coreelectronslargelycancelstheeffectoftheadditional8protonsinitsnucleus.
Consequently,increasedshieldinglargelyoffsetstheincreaseinZvaluefromoneperiodtothenextand,
therefore,valenceorbitalsbecomelargerandincreaseinenergyfromtoptobottomofagroup.

Insummarywecansaythatatomicsizedecreasesfromlefttorightandincreasesfromtoptobottomofthe
periodictable(figure4.47).

FIGURE4.47Representationoftheperiodictableshowingthatatomicradiusdecreasesfromlefttorightwithina
rowandincreasesfromtoptobottomwithinagroup.

Aconvenientmeasureofatomicsizeistheradiusoftheatom.Figure4.48showsthetrendsinatomicradii.
Forexample,theatomicradiusdecreasessmoothlyacrossthethirdperiod,from186pmforsodiumto97
pmforargon(bluearrow).Theatomicradiusincreasessmoothlydowngroup1,from152pmforlithiumto
265pmforcaesium(redarrow).Notice,however,thattheatomicradiuschangesverylittleacrossthedand
fblocks.Thisisduetoshielding.Fortheseelements,thelargestorbitalisthefillednsorbital.Movingfrom
lefttorightacrossarow,Zincreases,butelectronsaddtothesmaller(n1)dor(n2)forbitals.Anincrease
inZby1unitismatchedbytheadditionof1shieldingelectron.Fromtheperspectiveoftheoutlyings
orbital,theincreasesinZarebalancedbyincreasedshieldingfromtheaddeddorfelectrons.Thus,the
electronintheoutermostoccupiedorbital,ns,issubjecttoaneffectivenuclearchargethatchangesvery
littleacrosstheseblocks.Asaconsequence,therelativechangesinatomicsizeacrossthedandfblocksare
muchsmallerthanthosefoundinthesandpblocks.
 FIGURE4.48Theradiiofatomsvaryinperiodicfashion(dataareforatomsinthegasphase).Atomicradius
decreasesfromlefttorightwithinanyrow(bluelines)andincreasesfromtoptobottomwithinany
group(redlines).

Aknowledgeofperiodictrendsinphysicalandchemicalpropertiesandanunderstandingoftheprinciples
thatgiverisetothesetrendsareimportantsincetheyenableyou,forexample,topredictcertainchemical
behaviours,evenifyouarenotfamiliarwithaparticularelement.

WORKEDEXAMPLE4.16

TrendsinAtomicRadii
Foreachofthefollowingpairs,predictwhichatomislargerandexplainwhy:
(a)SiorCl,
(b)SorSeand
(c)MoorAg.

Analysis

Qualitativepredictionsaboutatomicsizecanbemadeonthebasisofanatom'spositioninthe
periodictable.

Solution
(a)Siliconandchlorineareinthethirdrowoftheperiodictable.

Chlorine'snuclearcharge(+17)islargerthansilicon's(+14),sochlorine'snucleusexertsa
 strongerpullonitselectroncloud.Chlorinealsohasthreemoreelectronsthansilicon,
whichincreasesthepossibilitythatshieldingeffectscouldcountertheextranuclear
charge.Remember,however,thatelectronsinthesametypeoforbitaldoapoorjobof
shieldingoneanotherfromthenuclearcharge.ForSiandCl,shieldingcomesmainly
fromthecoreelectrons,notfromtheelectronsinthe3porbitals.Becauseshieldingeffects
aresimilarfortheseelements,theeffectivenuclearchargeincreasesfromSitoCl.
Therefore,weconcludethatchlorine,withitsgreaternuclearattractionfortheelectron
cloud,isthesmalleratom.
(b)Sulfurandseleniumareingroup16oftheperiodictable.Althoughtheybothhavethe
s2p 2valenceconfigurations,selenium'sleaststableelectronsareinorbitalswithalargern
value.Orbitalsizeincreaseswithn.Seleniumalsohasagreaternuclearchargethansulfur,
whichraisesthepossibilitythatnuclearattractioncouldoffsetincreasedn.

Remember,however,thatmuchofthisextranuclearchargeisoffsetbytheshielding
influenceofthecoreelectrons.Seleniumhas18coreelectronsandsulfurhas10.Thus,
weconcludethatselenium,withitslargernvalue,islargerthansulfur.
(c)Molybdenumandsilverareinthesamerowofthedblock.

Theyhavethefollowingconfigurations.

Ineachcase,5sisthelargestoccupiedorbital(seep.132foranexplanation.)The4d
orbitalsaresmaller,withtheirelectrondensitylocatedmostlyinsidethe5sorbital.
Consequently,4diseffectiveatshielding5s.Thenuclearchargeofsilverisfiveunits
largerthanthatofmolybdenum,butsilveralsohasfiveextrashieldingelectronsind
orbitals.Theseoffsettheextranuclearcharge,makingMoandAgnearlythesamesize.

Isouranswerreasonable?

Thetrendsinfigure4.48confirmtheresults.Chlorineliestotherightofsiliconinthesamerow
oftheperiodictable.Sizedecreasesfromlefttorightinanyrowthus,chlorineissmallerthan
silicon.Seleniumisimmediatelybelowsulfurinthesamecolumnoftheperiodictable.Size
increasesdownacolumnthus,seleniumislargerthansulfur.Molybdenumandsilveroccupythe
samerowofthedblockoftheperiodictable,acrosswhichsizechangesrelativelylittlethus,
molybdenumandsilverarenearlythesamesize.

PRACTICEEXERCISE4.16
Useperiodictrendstodeterminewhichofthe
 followingaresmallerthanAsandwhichare
larger:P,Ge,SeandSb.

IonisationEnergy
Whenanatomabsorbsaphoton,thegaininenergypromotesanelectrontoahigherenergyorbitalinwhich
theelectronis,onaverage,furtherfromthenucleusandthereforeexperienceslesselectricalattractiontothe
nucleus.Iftheabsorbedphotonhasenoughenergy,anelectroncanbeejectedfromtheatom.

Theminimumamountofenergyneededtoremoveanelectronfromaneutralatomisthefirstionisation
energy(Ei1).Ionisationenergiesaremeasuredforgaseouselementstoensurethattheatomsareisolated
fromoneanother.

Variationsinionisationenergymirrorvariationsinorbitalenergy,becauseanelectroninahigherenergy
orbitaliseasiertoremovethanoneinalowerenergyorbital.

Figures4.49and4.50showhowthefirstionisationenergiesofgaseousatomsvarywithatomicnumber.
Noticethegeneraltrendsinionisationenergy.Ionisationenergyincreasesfromlefttorightacrosseach
period(thirdperiod:496kJmol1forNato1520kJmol1forAr)anddecreasesfromtoptobottomofeach
group(group18:2372kJmol1forHeto1037kJmol1forRn).Aswithatomicradius,ionisationenergy
changeslessforelementsinthedandfblocks,becauseincreasedshieldingfromthedandforbitalsoffsets
increasesinZ.Asaruleofthumb,thetrendintheionisationenergiesisinversetothatoftheatomicradii,
i.e.smalleratomshavehigherionisationenergies.Therefore,thetrendintheionisationenergiescanbe
rationalisedinsimilarfashion.

FIGURE4.49Representationoftheperiodictableshowingthatfirstionisationenergyincreasesfromlefttoright
withinarowanddecreasesfromtoptobottomwithinagroup.
 FIGURE4.50Thefirstionisationenergygenerallyincreasesfromlefttorightacrossaperiod(bluearrow)and
decreasesfromtoptobottomdownagroup(redarrow)oftheperiodictable.

HigherIonisations
Amultielectronatomcanlosemorethanoneelectron,butionisationbecomesmoredifficultascationic
chargeincreases.Thefirstthreeionisationenergiesforamagnesiumatominthegasphaseprovidean
illustration.

Process Configurations Ei

Noticethatthesecondionisationenergyofmagnesiumisalmosttwiceaslargeasthefirst,eventhougheach
electronisremovedfroma3sorbital.ThisisbecauseZeffincreasesasthenumberofelectronsdecreases.
Thatis,thepositivechargeonthemagnesiumnucleusremainsthesamethroughouttheionisationprocess,
butthenetchargeoftheelectronclouddecreaseswitheachsuccessiveionisation.Asthenumberof
electronsdecreases,eachelectronfeelsagreaterelectrostaticattractiontothenucleus(duetominimised
electronelectronrepulsion),resultinginalargerionisationenergy.

Thethirdionisationenergyofmagnesiumismorethan10timesthefirstionisationenergy.Thislarge
increaseoccursbecausethethirdionisationremovesacoreelectron(2p)ratherthanavalenceelectron(3s).
Removingcoreelectronsfromanyatomrequiresmuchmoreenergythanremovingvalenceelectrons.The
secondionisationenergyofanygroup1metalissubstantiallylargerthanthefirstionisationenergythe
thirdionisationenergyofanygroup2metalissubstantiallylargerthanthefirstorsecondionisationenergy,
andsoon.AppendixGgivesthefirstthreeionisationenergiesforthefirst36elements.

IrregularitiesinIonisationEnergies
Ionisationenergiesdeviatesomewhatfromsmoothperiodicbehaviour.Thesedeviationscanbeattributedto
shieldingeffectsandelectronelectronrepulsion.Aluminium,forexample,hasasmallerfirstionisation
energythaneitherofitsneighboursinrow3(seefigure4.48).

Element Z Atomconfiguration Ei1 Cationconfiguration

Mg 12 [Ne]3s2 738kJmol1 [Ne]3s1
Al 13 [Ne]3s23p 1 577kJmol1 [Ne]3s2
Si 14 [Ne]3s23p 2 786kJmol1 [Ne]3s23p 1

Theconfigurationsoftheseelementsshowthata3selectronmustberemovedtoionisemagnesium,
whereasa3pelectronmustberemovedtoionisealuminiumorsilicon.Shieldingmakesthe3porbitalsof
significantlyhigherenergythana3sorbital,andthisdifferenceinenergymorethanoffsetstheincreasein
nuclearchargeingoingfrommagnesiumtoaluminium.Asecondelectroninadifferent3porbitaldoesnot
contributetotheshieldingoftheother3pelectronandthustheincreasedZeffmeansthatitisharderto
removeanelectronfromSithanfromAl.

Asanotherexample,oxygenhasasmallerionisationenergythaneitherofitsneighboursinrow2.

Element Z Atomconfiguration Ei1 Cationconfiguration

N 7 1s22s22p 3 1402kJmol1 1s22s22p 2
O 8 1s22s22p 4 1314kJmol1 1s22s22p 3
F 9 1s22s22p 5 1681kJmol1 1s22s22p 4

Rememberthatelectronelectronrepulsionhasadestabilisingeffect.Theionisationenergyofoxygenisless
thanthatofnitrogen,despitetheincreasednuclearcharge,becausethep 4configurationintheOatomhas
significantlygreaterelectronelectronrepulsionthanthep 3configurationintheNatom.

ElectronAffinity
Aneutralatomcanaddanelectrontoformananion.Theenergychangewhenanelectronisaddedtoan
atominthegasphaseiscalledtheelectronaffinity(Eea).Bothionisationenergy(Ei)andelectronaffinity
measurethestabilityofaboundelectron,butfordifferentspecies.Below,forexample,arethevaluesfor
fluorine.

Energyisreleasedwhenanelectronisaddedtoafluorineatomtoformafluorideanion.Thismeansthata
fluorideanionisoflowerenergythanafluorineatomplusafreeelectron.Anotherwayofsayingthisisthat
fluorineatomshaveanaffinityforelectrons.

Theenergyassociatedwithremovinganelectrontoconvertananiontoaneutralatom(thatis,thereverseof
electronattachment)hasthesamemagnitudeastheelectronaffinity,buttheoppositesign.Removingan
electronfromF,forexample,requiresenergy,givingapositiveenergychange.

TheAufbauprinciplemustbeobeyedwhenanelectronisaddedtoaneutralatom,sotheelectrongoesinto
thelowestenergyorbitalavailable.Hence,weexpecttrendsinelectronaffinitytoparalleltrendsinorbital
energy.However,electronelectronrepulsionandshieldingaremoreimportantfornegativeionsthanfor
neutralatoms,sothereisnocleartrendinelectronaffinitiesasnincreases.Thus,thereisonlyonegeneral
pattern:Electronaffinitytendstobecomemorenegativefromlefttorightacrossaperiodoftheperiodic
table.

Theplotinfigure4.51showshowelectronaffinitychangeswithatomicnumber.Thebluelinesrevealthe
trend:Electronaffinityincreasesinmagnitudeacrosseachperiodoftheperiodictable.Thistrendisdueto
increasingeffectivenuclearcharge,whichbindstheaddedelectronmoretightlytothenucleus.Noticethat,
incontrasttothepatternforionisationenergies(figure4.50),valuesforelectronaffinitiesremainnearly
constantamongelementsoccupyingthesamegroupoftheperiodictable.

FIGURE4.51Theelectronaffinityofatomsvarieswithatomicnumber.Inmovingacrossanyperiod(bluelines),
theelectronaffinitybecomesmorenegative,butthisistheonlycleartrend.

Theelectronaffinityvaluesformanyoftheelementsshowninfigure4.51appeartolieonthexaxis.
Actually,theseelementshavepositiveelectronaffinities,meaningtheresultinganionisofhigherenergy
thantheneutralatom.Moreover,thesecondelectronaffinityofeveryelementislargeandpositive.Positive
electronaffinitiescannotbemeasureddirectly.Instead,thesevaluesareestimatedusingothermethods.

Althoughelectronaffinityvaluesshowonlyonecleartrend,thereisanotherrecognisablepatterninthe
valuesthatarepositive.Whentheelectronthatisaddedmustoccupyaneworbital,theresultinganionis
unstable.Thus,alltheelementsofgroup2havepositiveelectronaffinitiesbecausetheirvalencensorbitals
arefilled.Similarly,allthenoblegaseshavepositiveelectronaffinitiesbecausetheirvalencenporbitalsare
filled.Elementswithhalffilledorbitalsalsohavelessnegativeelectronaffinitiesthantheirneighbours.As
examples,N(halffilled2porbitalset)hasapositiveelectronaffinity,andsodoesMn(halffilled3dorbital
set).

SizesofIons
Anatomiccationisalwayssmallerthanthecorrespondingneutralatom.Conversely,anatomicanionis
alwayslargerthantheneutralatom.Figure4.52illustratesthesetrends,andelectronelectronrepulsion
explainsthem.Acationhasfewerelectronsthanitsparentneutralatom.Thisreductioninthenumberof
electronsmeansthatthecation'sremainingelectronsexperiencelesselectronelectronrepulsion.Ananion
hasmoreelectronsthanitsparentneutralatom.Thisincreasemeansthatthereismoreelectronelectron
repulsionintheanionthanintheparentneutralatom.
 FIGURE4.52Comparisonofthesizes(radius,r,inpm)ofneutralatoms(brown)andtheirions(cationsyellow
anionsblack)forsomeelements.Thebluehighlightindicatesisoelectronicions.

Figure4.52alsohighlightstherelationshipsbetweenisoelectronicspecies,i.e.thosethatpossessequal
numbersofelectrons.Asnotedearlier,theFanionandtheNa+cationareisoelectronic,eachhaving10
electronsandtheconfiguration[He]2s22p 6.Forisoelectronicspecies,propertieschangeregularlywithZ.For
example,table4.4showstwopropertiesofthe10electronisoelectronicsequence.Aprogressiveincreasein
nuclearchargeresultsinacorrespondingdecreaseinionicradius,aresultofstrongerelectricalforce
betweenthenucleusandtheelectroncloud.Forthesamereason,asZincreases,itbecomesprogressively
moredifficulttoremoveanelectron.
TABLE4.4 Trendsinanisoelectronicsequence
Species
Property O2 F Na+ Mg2+
Z 8 9 11 12
radius(pm) 140 133 102 72

ionisationenergy(kJmol1) 322(Eea ) 4560(Ei2) 7730(Ei3)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.9IonsandChemicalPeriodicity
Theelementsthatformioniccompoundsarefoundinspecificplacesintheperiodictable.Atomicanionsarerestrictedto
elementsontherightsideofthetable:thehalogens,oxygenandsulfur.Alltheelementsinthes,dandfblocksform
compoundscontainingatomiccations.

CationStability
Knowingthattheenergycostofremovingcoreelectronsisalwaysverylarge,wecanpredictthattheionisationprocesswill
stopwhenallvalenceelectronshavebeenremoved.Thus,aknowledgeofgroundstateconfigurationsisallthatweneedto
makequalitativepredictionsaboutcationstability.

Eachelementingroup1oftheperiodictablehasonevalenceelectron.TheseelementsformioniccompoundscontainingM +
cations.ExamplesareKClandNa2CO3.Eachelementingroup2oftheperiodictablehastwovalenceelectronsandforms
ioniccompoundscontainingM 2+cations.ExamplesareCaCO3andMgCl2.

Beyondthesetwogroups,theremovalofallvalenceelectronsisusuallynotenergeticallypossible.Forexample,ironhaseight
valenceelectronsbutformsonlytwostablecations,Fe2+andFe3+.Compoundsofironcontainingtheseionsareabundantin
theEarth'scrust.Pyrite,FeS2,andiron(II)carbonate,FeCO3,orsiderite,areexamplesofFe2+salts.Iron(III)oxide,Fe2O3,or
haematite,canbedescribedasanarrangementofFe3+cationsandO2anions.Oneofthemostabundantironores,magnetite,
hasthechemicalformulaFe3O4andcontainsa2:1ratioofFe3+andFe2+cations.Theformulaofmagnetitecanalsobe
writtenasFeOFe2O3toemphasisethepresenceoftwodifferentcations.

Othermetallicelementsformioniccompoundswithcationchargesrangingfrom+1to+3.Aluminiumnitratenonahydrate,
Al(NO3)39H2O,(thewordnonahydratemeansninewatermoleculesareassociatedwiththecompound)iscomposedofAl3+
cations,NO3anions,andwatermolecules.Silvernitrate,AgNO3,whichcontainsAg +cations,isawatersolublesilversaltthat
isusedinsilverplating.

AnionStability
Halogens,theelementsingroup17oftheperiodictable,havethelargestelectronaffinitiesofalltheelements.Sohalogen
atoms(ns2np 5)readilyacceptelectronstoproducehalideanions(ns2np 6).Thisallowshalogenstoreactwithmanymetalsto
formbinarycompounds,calledhalides,whichcontainmetalcationsandhalideanions.ExamplesincludeNaCl(chloride
anion),CaF2(fluorideanion),AgBr(bromideanion)andKI(iodideanion).

Isolatedatomicanionswithchargesmorenegativethan1arealwaysunstable,butoxide(O2,1s22s22p 6)andsulfide(S2,
[Ne]3s23p 6)arefoundinmanyionicsolids,suchasCaOandNa2S.Thelatticeenergies(seepp.1701)ofthesesolidsare
largeenoughtomaketheoverallreactionenergyreleasingdespitethelargepositivesecondelectronaffinityoftheanions.In
addition,threedimensionalarraysofsurroundingcationsstabilisethe2anionsinthesesolids.

Metals,NonmetalsandMetalloids
Ionformationisonlyonepatternofchemicalbehaviour.Manyotherchemicaltrendscanbetracedtovalenceelectron
configurations,butweneedthedescriptionofchemicalbondingfromchapter5toexplainsuchperiodicproperties.
Nevertheless,wecanrelateimportantpatternsinchemicalbehaviourtotheabilityofsomeelementstoformions.Oneexample
isthesubdivisionoftheperiodictableintometals,nonmetalsandmetalloids,firstintroducedinchapter1.

Theelementsthatcanformcationsrelativelyeasilyaremetals.Allmetalshavesimilarproperties,inpartbecausetheir
outermostselectronsarerelativelyeasytoremove.Allelementsinthesblockhavens1orns2valenceconfigurations.Thed
blockelementshaveoneortwonselectronsandvariousnumbersof(n1)delectrons.Examplesaretitanium(4s23d 2)and
silver(5s14d 10).Elementsinthefblockhavetwonselectronsandanumberof(n2)felectrons.Samarium,forexample,has
thevalenceconfiguration6s24f6.Themetallicbehaviouroftheseelementsoccurspartlybecausetheselectronsareshared
readilyamongallatoms.Metalsformionicsaltsbecauseselectrons(andsomep,danddfelectrons)canbereadilyremoved
fromthemetalatomstoformcations.

Whereastheotherblockscontainonlymetals,elementalpropertiesvarywidelywithinthepblock.Wehavealreadynotedthat
aluminium(3s23p 1)canloseitsthreevalenceelectronstoformAl3+cations.Thesixelementswithinthetriangleinfigure4.53
alsolosepelectronseasilyandthereforehavemetallicproperties.Examplesaretin(5s25p 2)andbismuth(6s26p 3).

FIGURE4.53Thesesixelementslosepelectronseasilyandsohavemetallicproperties.

Incontrast,thehalogensandnoblegasesontherightofthepblockaredistinctlynonmetallic.Thenoblegases,group18ofthe
periodictable,aremonatomicgasesthatresistchemicalattackbecausetheirelectronconfigurationsinvolvecompletelyfilleds
andporbitals.

Elementsinanyintermediatecolumnofthepblockdisplayarangeofchemicalpropertieseventhoughtheyhavethesame
valenceconfigurations.Carbon,silicon,germaniumandtinallhavens2np 2valenceconfigurationsyetcarbonisanonmetal,
siliconandgermaniumaremetalloids,andtinisametal.

Qualitatively,wecanunderstandthisvariationbyrecallingthat,astheprincipalquantumnumberincreases,thevalenceorbitals
increaseinenergy.Intin,thefourn=5valenceelectronsareboundrelativelylooselytotheatom,resultinginthemetallic
propertiesassociatedwithelectronsthatareeasilyremoved.Incarbon,thefourn=2valenceelectronsareboundrelatively
tightlytotheatom,resultinginnonmetallicbehaviour.Silicon(n=3)andgermanium(n=4)fallinbetweenthesetwo
extremes.

WORKEDEXAMPLE4.17

ClassifyingElements
Nitrogenisacolourlessdiatomicgas.Phosphorushasseveralelementalforms,onebeingaredsolidthatisusedin
matchtips.Arsenicandantimonyaregreysolids,andbismuthisasilverysolid.Classifytheseelementsofgroup15
asmetals,nonmetalsormetalloids.

Analysis

Allelementsexceptthoseinthepblockaremetals.Group15,however,ispartofthepblock,withinwhich
elementsdisplayallformsofelementalbehaviour.Todecidetheclassificationsoftheseelements,wemustexamine
thisgrouprelativetothediagonalarrangementofthemetalloids.
 Solution

Weseethatgroup15passesthroughallthreeclassesofelements.TheelementswiththelowestZvalues,nitrogen
andphosphorus,arenonmetals.TheelementwithhighestZvalue,bismuth,isametal,andthetwoelementswith
intermediateZvalues,arsenicandantimony,aremetalloids.

Isouranswerreasonable?

Astheprincipalquantumnumberincreases,valenceelectronsbecomeprogressivelyeasiertoremove,andmetals
arethoseelementswithvalenceelectronsthatareeasilyremoved.

PRACTICEEXERCISE4.17
Classifythe4psetofelements,fromGatoKrasmetals,
nonmetalsormetalloids.

sblockElements
Theelectronconfigurationofanyelementingroups1and2oftheperiodictablecontainsacoreoftightlyboundelectronsand
oneortwoselectronsthatarelooselybound.Thegroup1metals(ns1configuration)andthegroup2metals(ns2
configuration)formstableionicsaltsbecausetheirvalenceelectronsareeasilyremoved.Nearlyallsaltsofgroup1metalsand
manysaltsofgroup2metalsdissolvereadilyinwater,sonaturallyoccurringsourcesofwaterfrequentlycontaintheseions.

ThefourmostabundantsblockelementsintheEarth'scrustaresodium,potassium,magnesiumandcalcium(table4.5).These
elementsarefoundinnatureinsaltssuchasNaCl,KNO3,MgCl2,MgCO3andCaCO3.Portionsofthesesolidsaltsdissolvein
rainwaterasitpercolatesthroughtheEarth'scrust.Theresultingsolutionofanionsandcationseventuallyfindsitswaytothe
oceans.Whenwaterevaporatesfromtheoceans,theionsareleftbehind.Overmanyaeonsthecontinualinfluxofriverwater
containingtheseionshasbuiltupthesubstantialsaltconcentrationsfoundintheoceans.
TABLE4.5 Abundanceofsblockelements
AbundanceinEarth'scrust(%by Abundanceinseawater(mol Abundanceinhumanbloodplasma
Element mass) L1) (mol1)
Na 2.27 0.462 0.142
K 1.84 0.097 0.005
Mg 2.76 0.053 0.003
Ca 4.66 0.100 0.005

Table4.5showsthateachofthefourcommonsblockionsisabundantnotonlyinseawaterbutalsoinbodyfluids,where
theyplayessentialbiochemicalroles.Sodiumisthemostabundantcationinfluidsthatareoutsideofcells,andproper
functioningofbodycellsrequiresthatsodiumconcentrationsbemaintainedwithinanarrowrange.Oneofthemainfunctions
ofthekidneysistocontroltheexcretionofsodium.Whereassodiumcationsareabundantinthefluidsoutsidecells,potassium
cationsarethemostabundantionsinthefluidsinsidecells.Thedifferenceinionconcentrationacrosscellmembranesis
responsibleforthegenerationofnerveimpulsesthatdrivemusclecontraction.Ifthedifferenceinpotassiumionconcentration
acrosscellmembranesdeteriorates,muscularactivity,includingtheregularmusclecontractionsoftheheart,canbeseriously
disrupted.

ThecationsMg 2+andCa2+aremajorcomponentsofbones.Calciumoccursinhydroxyapatite,Ca5(PO4)3(OH).Thestructural
functionofmagnesiuminbonesisnotfullyunderstood.Inadditiontobeingessentialingredientsofbone,thesetwocations
playkeyrolesinvariousbiochemicalreactions,includingphotosynthesis,transmissionofnerveimpulses,musclecontraction
andtheformationofbloodclots.

Berylliumbehavesdifferentlyfromtheothersblockelementsbecauseitsn=2orbitalsaremorecompactthanorbitalswith
higherprincipalquantumnumbers.Thefirstionisationenergyofberyllium,899kJmol1,iscomparablewiththoseof
nonmetals,soberylliumdoesnotformcompoundsthatareclearlyionic.

Somecompoundsofthesblockelementsareimportantindustrialandagriculturalchemicals(figure4.54).Forexample,K2CO3
(potassiumcarbonateorpotash)isobtainedfrommineraldepositsandisthemostcommonsourceofpotassiumforfertilisers.
Potassiumisessentialforhealthyplantgrowth.However,potassiumsaltsarehighlysolubleinwater,sopotassiumquickly
becomesdepletedfromthesoil.Consequently,agriculturallandrequiresfrequentadditionofpotassiumfertilisers.

FIGURE4.54Potassium,anothersblockelement,isessentialforhealthyplantgrowthandisaddedtoagriculturalsoilinfertilisers.

Threeothercompoundsofsblockelementscalciumoxide,CaOorlime,sodiumhydroxide,NaOH,andsodium
carbonate,Na2CO3aremajorindustrialchemicals.Forexample,limeisthekeyingredientinconstructionmaterialssuchas
concrete,cement,mortarandplaster.Twoothercompounds,calciumchloride,CaCl2,andsodiumsulfate,Na2SO4,arealsoof
industrialimportance.

Manyindustrialprocessesmakeuseofanionssuchashydroxide,OH,carbonate,CO32,andchlorate,ClO3.Theseanions
mustbesuppliedaschemicalcompoundsthatincludecations.Sodiumismostfrequentlyusedasthisspectatorcationbecause
itisabundant,inexpensiveandrelativelynontoxic.Thehydroxideionisindustriallyimportantbecauseitisastrongbase(see
chapter11).Sodiumhydroxideisusedtomanufactureotherchemicals,textiles,paper,soapsanddetergents.Sodiumcarbonate
andsandarethemajorstartingmaterialsinthemanufactureofglass.Glasscontainssodiumandothercationsembeddedina
matrixofsilicate,SiO32,anions.Abouthalfthesodiumcarbonateproducedintheworldisusedinglassmaking.

pblockElements
Thepropertiesofelementsinthepblockvaryacrosstheentirespectrumofchemicalpossibilities.Theelementsingroup13,
withasingleelectroninaporbitalaswellastwovalenceselectrons,displaychemicalreactivitycharacteristicofthreevalence
electrons.Exceptforboron,theelementsofthisgrouparemetalsthatformstable+3cations.ExamplesareAl(OH)3andGaF3.
Metalliccharacterdiminishesrapidlyasadditionalpelectronsareadded.Thischangeculminatesintheelementsingroup18.
Withfilledporbitals,theseelementsaresounreactivethatformanyyearstheywerethoughttobecompletelyinert.Xenonis
nowknowntoformcompoundswiththemostreactivenonmetals:oxygen,fluorineandchlorinekryptonalsoformsafew
highlyunstablecompoundswiththeseelements.

Althoughthenonmetalsdonotreadilyformcations,manyofthemcombinewithoxygentoformpolyatomicoxoanions.These
anionshavevariousstoichiometries,buttherearesomecommonpatterns.Twosecondrowelementsformoxoanionswiththree
oxygenatoms:carbon(fourvalenceelectrons)formscarbonate,CO32,andnitrogen(fivevalenceelectrons)formsnitrate,
NO3.Inthethirdrow,themoststableoxoanionscontainfouroxygenatoms:SiO44,PO43,SO42andClO4.

ManyofthemineralsthatformtheEarth'scrustcontainoxoanions.ExamplesofcarbonatesareCaCO3(limestone)and
MgCa(CO3)2(dolomite).Barite,BaSO4,isasulfatemineral.AnimportantphosphateisCa5(PO4)3F(apatite).Twosilicatesare
zircon,ZrSiO4,andolivine,amixtureofMgSiO4andFeSiO4.

SeveralleadingindustrialchemicalscontainoxoanionsorareacidsresultingfromadditionofH+totheanions.Sulfuricacid,
H2SO4,nitricacid,HNO3,andphosphoricacid,H3PO4,areallindustriallyimportant.HeatingCaCO3drivesoffCO2toform
CaO,theessentialingredientofbuildingmaterialsmentionedearlier.Otherindustriallyimportantsaltsincludeammonium
sulfate,(NH4)2SO4,aluminiumsulfate,Al2(SO4)3,sodiumcarbonate,Na2CO3,andammoniumnitrate,NH4NO3.Wewilllearn
moreaboutthepblockelementsinchapter14.

ChemistryResearch

Counterterrorismusingseparationscience

ProfessorPaulHaddad,Director,AustralianCentreforResearchonSeparationScience,UniversityofTasmania

Animportantaspectincounterterrorismmeasuresistheabilitytorapidlyidentifythetypeofexplosiveusedina
terroristattack.Improvisedexplosivedevices(IEDs,figure4.55)arecommonlychosenbyterroristsinpreferenceto
highexplosives,suchasnitratedorganiccompounds,becauseoftherelativeeasewithwhichthecomponentsusedin
theirmanufacturecanbeprocuredandthelowcostofthesematerials.Typically,IEDsarehomemadeexplosives
createdfromunrestrictedmaterialsandconsistofaninitiationsystemtosupplyanelectricalcharge,adetonatorandan
explosivecharge.
 FIGURE4.55Theabilitytoidentifyatypeofexplosiveisimportantincounterterrorism.

InorganicIEDsemployvigorouschemicalreactionsusingstronginorganicoxidiserscombinedwithasuitablefuel.
Afterdetonation,theseexplosivesleaveresiduescomprisingunconsumedreactantsandarangeofreactionproducts,
mostofwhichareinorganicanionsandcations.ResearchbeingconductedintheAustralianCentreforResearchon
SeparationScienceattheUniversityofTasmaniaisinvestigatingwhethertheseresiduescanbeusedtoidentify
explosivesbymeansofafingerprintofthedifferentionspresentintheresidues.Theanalyticalmethodologyused
forthisprocessmustbeabletobecarriedtoablastsiteandbeoperatedinthefieldratherthaninalaboratory.

Oneoftheanalyticaltechniquesunderinvestigationiscapillaryelectrophoresis(CE).Inthistechnique,amixtureof
sampleionsisintroducedintooneendofaveryfinecapillary(75minternaldiameter)madefromfusedsilica.A
largeelectricalfield(e.g.30000V)isappliedalongthelengthofthecapillaryandthisinducesthesampleionsto
migratetotheappropriateelectrode.Anionsmigratetothepositivelychargedanodeandcationsmigratetothe
negativelychargedcathode.Iftheratesofmigrationdifferbetweenions,theywillreachtheendofthecapillaryat
differenttimesandhencebeseparated.

AfterlookingatthepossibleresiduesfromawiderangeofIEDs,atargetsetof15anionsand12cationswaschosen.
SeparationofallthesespeciesallowsauniquefingerprinttobeobtainedforeachIED.Typicaloutputs(called
electropherograms)areshowninfigure4.56forthetypeofIEDusedinthe2002Balibombing.Theanionand
cationfingerprintsaredisplayed.OtherIEDsgivedifferentfingerprintsandcanbeidentifiedeasily.Theanalyses
shownwereperformedonaportableCEinstrumentthatisaboutthesizeofabriefcaseandcanthereforebe
transportedeasily.

FIGURE4.56Typicalelectropherogramsfromanalysisofresiduesfromimprovisedexplosivedevices(IEDs).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
CharacteristicsofAtoms
Allatomsdisplaycertainbasiccharacteristics.Theypossessmass,occupyvolume,attractoneanother
andcancombinewithoneanother.Atomscontainpositivelychargednucleiandnegativelycharged
electrons,andthepropertiesofelementsaredeterminedbyvariationsinnuclearchargesandnumbers
ofelectrons.

CharacteristicsofLight
Electromagneticradiationintheformoflightmaybeusedtoprobethestructureofatoms.Lighthas
bothwaveandparticlelikeproperties.

Thewavepropertiesarecharacterisedby:
frequency():thenumberofwavecrestspassingagivenpointin1second
wavelength():thedistancebetweensuccessivewavecrests
amplitude:theheightofthewave
phase:thestartingpositionofthewavewithrespecttoonewavelength.

Theintensity(orbrightness)oflightisproportionaltothesquareoftheamplitude.

Lightwavesmoveatthespeedoflight,c(approx.2.99810 8ms1)inavacuum.Therelationship
betweenspeed,frequencyandwavelengthoflightisc=.Visiblelighthaswavelengthsbetween380
and780nm.Theenergyoflightisinverselyrelatedtoitswavelengththeshorterthewavelength,the
highertheenergy.

Theparticlepropertiesoflightaredemonstratedbythephotoelectriceffect,wherelightstrikingthe
surfaceofametalcauseselectronstobeejectedfromthemetal.Einsteinpostulatedthatthisbehaviour
couldbeexplainedbypacketsorbundlesoflightcalledphotons.Theenergyofaphotonisgivenby
theequationEphoton=hphoton,wherehisPlanck'sconstant(approximately6.62610 34Js).Anatom
canabsorbaphotonofaparticularenergyandformahigherenergyexcitedstate.Theexcitedstate
atomcanthenreleasetheexcessenergybyemittingaphotonandreturningtoitsgroundstate.These
photonabsorptionandemissionprocessescanbeobservedinatomicspectra.Anabsorptionspectrum
givesdarklinesinthevisiblespectrumwherelightofaparticularwavelengthhasbeenabsorbed,while
anemissionspectrumgivescolouredlinesonadarkbackgroundwhichcorrespondtoemissionof
photons.Atomscanabsorboremitphotonsofonlycertaindefiniteenergies,meaningthattheelectrons
inatomshaveonlycertainspecificenergyvaluesthatis,theirenergiesarequantised.Weshowthe
quantisedenergylevelswithinanatombymeansofanenergyleveldiagram.

PropertiesofElectrons
Likeatoms,allelectronsdisplaycertainbasiccharacteristics.Everyelectronhasamassof9.10910 31
kgandachargeof1.60210 19C.Electronshavemagneticpropertiesand,likelight,electronsalso
displayparticlewaveduality.Thewavelengthassociatedwithanelectronisgivenbytheequation
.TheHeisenberguncertaintyprinciplestatesthatwecannotsimultaneouslyknowboththe
positionandthemomentumofanyparticle,andthisisparticularlyimportantforelectrons.

QuantisationandQuantumNumbers
Electronsboundtoatomshavequantisedenergies,whilefreeelectronscanhaveanyenergy.The
quantisedenergiesofboundelectronsarelinkedtotheirwavepropertiesbytheSchrdingerequation
 ,whichgivesboththeenergiesandwavefunctionsofachemicalsystem.Thisequationcanbe
solvedexactlyonlyforsystemscontainingoneelectron,andaoneelectronwavefunctioniscalledan
orbital.

Quantisedpropertiesofanatomcanbeindexedusingquantumnumbers.Theprincipalquantum
number(n)canhaveonlypositiveintegervalues,andindexesboththeenergyoftheelectronand
orbitalsize.Thesizeofanorbitalincreasesasnincreases.Theazimuthalquantumnumber(l)indexes
theangularmomentumofanatomicorbitalandidentifiestheshapeoftheelectrondistributionofan
orbitalitcanbezerooranypositiveintegervaluesmallerthann.Atomicorbitalsarelabelledaccording
totheirlvaluesorbitalshavel=0,porbitalshavel=1,dorbitalshavel=2andforbitalshavel=3.
Themagneticquantumnumber(ml)indexesthedifferentpossibleorientationsoftheelectron
distributionofanorbitalitcanhaveanypositiveornegativeintegervaluefrom0tol.Thespin
quantumnumber(ms)haspossiblevaluesof and ,correspondingtothetwopossiblespinstates
ofanelectron.Allelectronswithinanatomcanbedescribedusingsetsofthesefourquantumnumbers,
andthePauliexclusionprinciplestatesthateachelectronhasauniqueset.

AtomicOrbitalElectronDistributionsandEnergies
Theelectrondistributionofanorbitalcanbedepictedinavarietyofways.Anelectrondensityplot
showsthedistributiongraphicallyintwodimensions,anelectrondensitypictureshowsacrosssection
ofthedistribution,whileaboundarysurfacediagramshowsthesurfacewhichencompasses(usually)
90%oftheelectrondensity.Areasofzeroelectrondensitywithinanorbitalarecallednodes,andthe
numberoftheseincreaseasnincreases.Theelectrondistributionofansorbitalisspherical,whilethose
ofporbitalsandfourofthefivedorbitalsaredumbbellandcloverleafshaped,respectively.The
electrondistributionofthe orbitalresemblesthatofaporbitalsurroundedbyadoughnut.Thetwo
lobesofporbitalshaveoppositephases,whilethephasesofthefourlobesofacloverleafshapedd
orbitalalternate.Thedoughnutofa orbitalisofoppositephasetotherestoftheorbital.

TheenergyofanorbitalinaoneelectronsystemisdeterminedbyboththeatomicnumberZandthe
principalquantumnumbern.Allorbitalsinaoneelectronsystemwiththesamevalueofnhavethe
sameenergytheyaredegenerate.Thisdegeneracyisdestroyedinmultielectronatoms.Theenergy
ofanorbitalcanbedeterminedbymeasuringtheionisationenergy,whichistheenergyrequiredto
removeanelectroncompletelyfromthat(usuallyvalence)orbital.Ionisationenergiesaredependenton
manyfactors,oneofwhichistheshieldingofthevalenceelectronsfromthenuclearchargebycore
electrons.Consequently,avalenceelectroninamultielectronatomexperiencesachargelessthanthe
fullnuclearchargethisiscalledtheeffectivenuclearcharge(Zeff).Electronswithalowernshield
electronsofhighernveryefficiently,while,withingroupsofelectronsofthesamen,thosehavingthe
lowestvalueoflshieldthoseofhigherl.

StructureofthePeriodicTable
Thegroundstateconfigurationofanatomisthelowestpossibleenergyarrangementoftheelectrons.
Theorderoffillingatomicorbitalswithelectronsisdictatedby:theAufbauprinciple,whichstatesthat
orbitalsarefilledinorderofincreasingenergythePauliexclusionprinciple,whichstatesthatnotwo
electronsinanatomcanhaveidenticalsetsofthefourquantumnumbersandHund'srule,whichstates
thatelectronsoccupysetsofdegenerateorbitalssoastogivethemaximumnumberofunpairedspins.
Ansorbitalcanaccommodate2electrons,asetofporbitals6andasetofdorbitals10.

Theshapeoftheperiodictableoftheelementsderivesfromtheseorbitaloccupanciesandtheorderin
whichtheorbitalsarefilled.Elementswiththesamevalenceelectronconfigurationslieinthesame
groupoftheperiodictableandhavesimilarchemicalproperties.Valenceelectronslargelydetermine
thechemistryofanelement,whilecoreelectronsusuallydonotparticipateinchemicalreactions.
ElectronConfigurations
Theelectronconfigurationofanatomcanbewrittenbyrecordingquantumnumbersforallelectronsin
theatom,usingacompactconfigurationwhichshowstheelectronoccupancyofeachorbitaltype,or
throughanenergyleveldiagramwhichshowstheenergyandoccupancyofeachorbital.Inthelatter,
electronsaredepictedasarrowspointingeitherup( )ordown( ).Wecanalsousea
shorthandnotationthatdoesnotexplicitlyincludethecoreelectrons,butabbreviatesthemusingthe
noblegasconfigurationofthenearestnoblegaswithlowerZ.Someexceptionstotheorderoforbital
fillingoccur,mostnotablyforCrandCu.Theorderoforbitalfillingforionsisthesameasthatfor
atoms,asshownbythesameelectronconfigurationsfortheisoelectronicseriesNa+,NeandF.Atoms
orionshavingunpairedelectronsareparamagneticandwillbeattractedtoamagneticfield,while
specieshavingallelectronspairedarediamagneticandarenotattractedtoamagneticfield.The
electronconfigurationsofexcitedstatescanviolateHund'sruleandtheAufbauprinciplebutnotthe
Pauliexclusionprinciple.

PeriodicityofAtomicProperties
Thesizeofanatomisdeterminedbyfactorssuchasnuclearcharge,orbitalenergyandelectron
distribution,andshielding.Atomicradiigiveusameasureofthesizesofatoms.Atomicradiibecome
smalleracrossaperiodandlargerdownagroupoftheperiodictable.Thefirstionisationenergiesofthe
elementsgenerallyincreaseacrossaperiodanddecreasedownagroupoftheperiodictable.Exceptions
tothesegeneraltrendsoccurwhenporbitalsareoccupiedby1or4electrons.Electronaffinities
becomemorenegativeacrossaperiod,butthereisnocleartrenddownagroupoftheperiodictable.
Atomiccationsarealwayssmallerthantheneutralatomandatomicanionsarealwayslargerthanthe
neutralatom.

IonsandChemicalPeriodicity
Thenatureofcationsandanionsisdeterminedbytheelectronconfigurationoftheneutralatom.Group
1andgroup2elementsform1+and2+cationsrespectively,whilegroup17elementsform1anions.
Isolatedatomicanionswithchargesmorenegativethan1arealwaysunstable,andO2andS2are
foundonlyincombinationwithcationsinionicsolids.Metalsgenerallyformcationsreadilythrough
lossofsordelectrons.Thepblockelementsmaybemetals,metalloidsornonmetals.Thesblock
elementsarefoundintheEarth'scrustandalsoinlivingsystems,andpblockelementsdisplayawide
varietyofchemicalproperties.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Wavelengthfrequencyrelationship(section4.2)
Theproductofwavelength()andfrequency()isthespeedoflight(c).

Energyofaphoton(section4.2)
Thisequationisusedtocalculatetheenergycarriedbyaphotonoffrequency.Also,canbe
calculatedifEisknown.

deBroglieequation(section4.3)
Thislinksthewavelengthofaparticlewithitsspeedandmass.

Quantumnumbersforatoms(section4.4)
Eachelectroninanatomisdescribedbyauniquesetoffourquantumnumbers.Theallowedvaluesof
thesequantumnumbersareasfollows:

Quantumnumber Range
principalquantumnumber(n) 1,2,,
azimuthalquantumnumber(l) 0,1,,(n1)
magneticquantumnumber(ml) l,,1,0,+1,,+l
spinquantumnumber(ms)

Periodictable(section4.6)
Theperiodictableisanaidinwritingelectronconfigurationsoftheelements.Anelement'slocationin
thetableisrelatedtopropertiessuchasatomicradius,ionisationenergyandelectronaffinity.

Electronconfigurations(section4.7)
Theseguidelineshelpustowriteelectronconfigurationsforatomsorions.
1.Countthetotalnumberofelectrons.
a.Addelectronsforanions.
b.Subtractelectronsforcations.
2.Fillorbitalstomatchthenearestnoblegasofsmalleratomicnumber.
3.AddremainingelectronstothenextorbitalstobefilledaccordingtoHund'srule.
a.Forneutralatomsandanions,placeelectronsinnsbefore(n1)d.
b.Forcations,placeelectronsin(n1)dbeforens.
4.Lookforexceptionsandcorrecttheconfigurationifnecessary.
Periodictrendsinatomicandionicsize(section4.8)
Periodictrendsareevidentin,forexample:
atomicandionicsize
ionisationenergy
electronaffinity.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
CharacteristicsofAtoms
4.1Thedensityofsilveris1.05010 4kgm3,andthedensityofleadis1.13410 4kgm3.Foreach
metal:
(a)calculatethevolumeoccupiedperatom,
(b)estimatetheatomicdiameterand
(c) usingthisestimate,calculatethethicknessofametalfoilcontaining6.510 6atomiclayers
ofthemetal.
4.2Describeevidencethatindicatesthatatomshavemass.
4.3Describeevidencethatindicatesthatatomshavevolume.
CharacteristicsofLight
4.4Calculatethefrequencies(Hz)correspondingtothefollowingwavelengths,usingpoweroften
notation:
(a)4.33nm,
(b)2.3510 10m,
(c)735mm,
(d)4.57m.
4.5Calculatethewavelengthscorrespondingtothefollowingfrequencies,expressingtheresultinthe
indicatedunits:
(a)4.77GHz(m),
(b)28.9kHz(cm),
(c)60Hz(mm),
(d)2.88MHz(m).
4.6Calculatetheenergyinjoulesperphotonandinkilojoulespermoleofthefollowing:
(a)bluegreenlightwithawavelengthof490.6nm,
(b)Xrayswithawavelengthof25.5nm,
(c) microwaveswithafrequencyof2.543710 10Hz.
4.7Whatarethewavelengthandfrequencyofphotonswiththefollowingenergies?
(a) 745kJmol1
(b)3.5510 19Jphoton 1
4.8Whenlightoffrequency1.3010 15s1shinesonthesurfaceofcaesiummetal,electronsare
ejectedwithamaximumkineticenergyof5.210 19J.Calculate:
(a)thewavelengthofthislight,
(b)thebindingenergyofelectronstocaesiummetaland
(c)thelongestwavelengthoflightthatwillejectelectrons.
4.9Aphototubedeliversanelectricalcurrentwhenabeamoflightstrikesametalsurfaceinsidethe
tube.Phototubesdonotrespondtoinfraredphotons.Drawanenergyleveldiagramforelectronsin
themetalofaphototubeanduseittoexplainwhyphototubesdonotrespondtoinfraredlight.
4.10Refertofigure4.4toanswerthefollowingquestions.
(a)Whatisthewavelengthrangeforradiowaves?
 (b)Whatcolourislightwithawavelengthof5.810 7m?
(c) Inwhatregiondoesradiationwithfrequencyof4.510 8Hzlie?
4.11Determinethewavelengthsofradiationthathydrogenatomsabsorbtoreachthen=8andn=9
statesfromthegroundstate.Inwhatregionoftheelectromagneticspectrumdothesephotonslie?
PropertiesofElectrons
4.12Whatisthechargeincoulombsofonemoleofelectrons?
4.13Determinethewavelengthsofelectronswiththefollowingkineticenergies:
(a) 1.1510 190J,
(b)3.55kJmol1,
(c) 7.4510 3Jmol1.
4.14Determinethekineticenergiesinjoulesofelectronswiththefollowingwavelengths:
(a)3.75nm,
(b)4.66m,
(c)8.85mm.
QuantisationandQuantumNumbers
4.15Listallthevalidsetsofquantumnumbersfora6p6electron.
4.16Ifyouknowthatanelectronhasn=3,whatarethepossiblevaluesforitsotherquantum
numbers?
4.17Forthefollowingsetsofquantumnumbers,determinewhichdescribeactualorbitalsandwhich
arenonexistent.Foreachonethatisnonexistent,listtherestrictionthatforbidsit.

n l ml ms

(a) 3 1 1

(b) 3 1 1

(c) 3 1 2

(d) 3 2 2

AtomicOrbitalElectronDistributionsandEnergies
4.18Refertofigure4.27.Drawtheanalogoussetofthreedepictionsforanorbitalthathasn=2,l=1.
4.19Shownbelowareelectrondensitypicturesandelectrondensityplotsforthe1s,2s,2pand3p
orbitals.Assignthevariousdepictionstotheirrespectiveorbitals.
(a)

(b)
 (c)

(d)

4.20Whatarethelimitationsofplotsofelectrondensityversusr?
4.21Theconventionalmethodofshowingthethreedimensionalelectrondistributionofanorbitalisan
electroncontoursurface.Whatarethelimitationsofthisrepresentation?
4.22Foreachofthefollowingpairsoforbitals,determinewhichismorestableandexplainwhy.
(a)He1sandHe2s
(b)Kr5pandKr5s
(c) He2sandHe+2s
4.23Inahydrogenatomthe3s,3p3and3dorbitalsallhavethesameenergy.Inaheliumatom,
however,the3sorbitalislowerinenergythanthe3porbital,whichinturnislowerinenergythan
the3dorbital.Explainwhytheenergyrankingsofhydrogenandheliumaredifferent.
4.24Theenergyofthen=2orbitaloftheHe+ionisthesameastheenergyofthen=1orbitalofthe
Hatom.Explainthisfact.
4.25Refertofigure4.37toanswerthefollowingquestions.Ineachcase,provideabriefexplanationof
yourchoice.
(a)Whichionisationenergiesshowthatanelectronina1sorbitalprovidesnearlycomplete
shieldingofanelectronina2porbital?
(b)Whichionisationenergiesshowthatthestabilityofn=2orbitalsincreaseswithZ2?
StructureofthePeriodicTable
4.26Drawtheperiodictableinblockform,andoutlineandlabeleachofthefollowingsets:
(a)elementsthatare1electronshortoffilledporbitals,
(b)elementsforwhichn=3orbitalsarefilling,
(c)elementswithhalffilleddorbitals,
(d)thefirstelementthatcontainsa5selectron.
4.27Howmanyvalenceelectronsdoeseachofthefollowingatomshave?
(a)O,
 (b)V,
(c)Rb,
(d)Sn,
(e)Cd
ElectronConfigurations
4.28Writethecompleteelectronconfiguration,andlistacorrectsetofquantumnumbersforeachof
thevalenceelectronsinthegroundstateconfigurationsof:
(a)Be,
(b)O,
(c)Ne,
(d)P.
4.29Whichoftheatomsfromquestion4.28areparamagnetic?Draworbitalenergyleveldiagramsto
supportyouranswer.
4.30Thefollowingarehypotheticalconfigurationsforaberylliumatom.Whichusenonexistent
orbitals,whichareforbiddenbythePauliprinciple,whichareexcitedstates,andwhichoneisthe
groundstateconfiguration?
(a) 1s32s1
(b)1s12s3
(c) 1s12p 3
(d)1s22s12p 1
(e) 1s22s2
(f) 1s21p 2
(g)1s22s12d 1
4.31Writethecorrectgroundstateelectronconfigurations,inshorthandnotation,forC,Cr,SbandBr.
PeriodicityofAtomicProperties
4.32Arrangethefollowingatomsinorderofdecreasingfirstionisationenergy(smallestlast):Ar,Cl,
CsandK.
4.33Oneelementhastheseionisationenergiesandelectronaffinity(allinkJmol1):E =376,E =
i1 i2
2420,Ei3=3400,Eea =45.5.Inwhichcolumnoftheperiodictableisthiselementfound?Give
yourreasoning.
4.34AccordingtoappendixG,eachofthefollowingelementshasapositiveelectronaffinity.Foreach
one,constructitsvalenceorbitalenergyleveldiagramanduseittoexplainwhytheanionis
unstable.
(a)N,
(b)Mg,
(c)Zn
4.35Fromthefollowinglist,selecttheelementsthatformioniccompounds:Ca,C,Cu,Cs,ClandCr.
Indicatewhethereachformsastablecationorastableanion.
IonsandChemicalPeriodicity
4.36Classifyeachoftheelementsfromgroup16oftheperiodictableasametal,anonmetalora
metalloid.
4.37Classifyeachoftheelementslistedinquestion4.35asametal,anonmetalorametalloid.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
4.38Listthepropertiesofelectronsandofphotons,includingtheequationsusedtodescribeeach.
4.39Writeashortdescriptionof:
(a)thephotoelectriceffect,
(b)particlewaveduality,
(c)electronspinand
(d)theuncertaintyprinciple.
4.40Describeanatomicenergyleveldiagramandtheinformationitincorporates.
4.41Redrawthefirstlightwaveinfigure4.3toshowawavewhosefrequencyistwiceaslargeasthat
showninthefigure,butwhoseamplitudeisthesame.
4.42Aminimumof216.4kJmol1isrequiredtoremoveanelectronfromapotassiummetalsurface.
Whatisthelongestwavelengthoflightthatcandothis?
4.43Inaphotoelectriceffectexperiment,theminimumfrequencyneededtoejectelectronsfroma
metalis7.510 14s1.Supposethata366nmphotonfromamercurydischargelampstrikesthe
metal.Calculate:
(a)thebindingenergyoftheelectronsinthemetal,
(b)themaximumkineticenergyoftheejectedelectronsand
(c)thewavelengthassociatedwiththoseelectrons.
4.44Microwaveovensuseradiationwithawavelengthof12.5cm.Whatisthefrequency,andenergy
inkJmol1,ofthisradiation?
4.45Bariumsaltsinfireworksgenerateayellowgreencolour.Ba2+ionsemitlightwith=487,514,
543,553and578nm.ConvertthesewavelengthsintofrequenciesandintoenergiesinkJmol1.
4.46Ahydrogenatomemitsaphotonasitselectronchangesfromn=5ton=1.Whatisthe
wavelengthofthephoton?Inwhatregionoftheelectromagneticspectrumisthisphotonfound?
4.47Writebriefexplanationsof:
(a)shielding,
(b)thePauliexclusionprinciple,
(c)theAufbauprinciple,
(d)Hund'sruleand
(e)valenceelectrons.
4.48Constructanorbitalenergyleveldiagramforallorbitalswithn<8andl<4.Usetheperiodic
tabletohelpdeterminethecorrectorderoftheenergylevels.
4.49Describeperiodicvariationsinelectronconfigurationsexplainhowtheyaffectionisationenergy
andelectronaffinity.
4.50WritetheelectronconfigurationfortheMn 2+groundstate,andgiveasetofquantumnumbersfor
allelectronsintheleaststableoccupiedorbital.
4.51Arrangethefollowinginorderofdecreasingsize(radius):Cl,K+,ClandBr.Explainyour
rankingsintermsofquantumnumbersandelectricalinteractions.
4.52DrawenergyleveldiagramsthatshowthegroundstatevalenceelectronconfigurationsforCu +,
Mn 2+andAu 3+.
4.53Writeabriefexplanationforeachofthefollowing.
 (a)Inahydrogenatom,the2sand2p2orbitalshaveidenticalenergy.
(b)Inaheliumatom,the2sand2porbitalshavedifferentenergies.
4.54Refertofigure4.50toanswerthefollowingquestionsaboutfirstionisationenergies.
(a)WhichelementshowsthegreatestdecreasefromitsneighbourofnextlowerZ?
(b)Whatistheatomicnumberoftheelementwiththelowestvalue?
(c)IdentifythreerangesofZacrosswhichthevaluechangestheleast.
(d)Listtheatomicnumbersofallelementswhosevaluesarebetween925and1050kJmol1.
4.55Whichhasthemostunpairedelectrons,S+,SorS?Useelectronconfigurationstosupportyour
answer.
4.56Noneofthefollowingelectronenergydiagramsdescribesthegroundstateofasulfuratom.For
each,statethereasonwhyitisnotcorrect.
(a)

(b)

(c)

(d)
4.57Identifytheioniccompoundsthatbestfitthefollowingdescriptions:
(a)thegroup2cationwiththesecondsmallestradiuscombinedwithagroup16anionthatis
isoelectronicwiththenoblegasfromrow3
(b)a+1ionthatisisoelectronicwiththenoblegasfromrow3,combinedwiththeanion
formedfromtherow2elementwiththehighestelectronaffinity
(c)thegroup2metalwiththehighestsecondionisationenergythatcombinesina1:2ratio
withanelementfromrow3.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
4.58Thephotoelectriceffectformagnesiummetalhasathresholdfrequencyof8.9510 14s1.Can
Mgbeusedinphotoelectricdevicesthatsensevisiblelight?Doacalculationtosupportyour
answer.
4.59Energeticfreeelectronscantransfertheirenergytoboundelectronsinatoms.In1913,James
FranckandGustavHertzpassedelectronsthroughmercuryvapouratlowpressuretodetermine
theminimumkineticenergyrequiredtoproducetheexcitedstatethatemitsultravioletlightat
253.7nm.Whatisthatminimumkineticenergy?Whatwavelengthisassociatedwithelectronsof
thisenergy?
4.60Thediameterofatypicalatomis10 10m,andthediameterofatypicalnucleusis10 15m.
Calculatetypicalatomicandnuclearvolumesanddeterminewhatfractionofthevolumeofa
typicalatomisoccupiedbyitsnucleus.
4.61Neutrons,likeelectronsandphotons,areparticlewaveswithdiffractionpatternsthatcanbeused
todeterminethestructuresofmolecules.Calculatethekineticenergyofaneutronwitha
wavelengthof75pm.
4.62Thehumaneyecandetectaslittleas2.3510 18Jofgreenlightwithawavelengthof510nm.
Calculatetheminimumnumberofphotonsofgreenlightthatcanbedetectedbythehumaneye.
4.63Gaseouslithiumatomsabsorblightwithawavelengthof323nm.Theresultingexcitedlithium
atomslosesomeenergythroughcollisionswithotheratoms.Theatomsthenreturntotheirground
statebyemittingtwophotonswith=812.7and670.8nm.Drawanenergyleveldiagramthat
showsthisprocess.Whatfractionoftheenergyoftheabsorbedphotonislostincollisions?
4.64Calculatethewavelengthsassociatedwithanelectronandaproton,eachtravellingat5.000%of
thespeedoflight.
4.65Onehydrogenemissionlinehasawavelengthof486nm.Identifythevaluesforn finalandn initial
forthetransitiongivingrisetothisline.
4.66Anatomicenergyleveldiagram,showntoscale,follows.

Anexcitedstateatomemitsphotonswhentheelectronmovesinsuccessionfromleveldtolevel
c,fromlevelctolevelb,andfromlevelbtothegroundstate(levela).Thewavelengthsofthe
emittedphotonsare565nm,152nmand121nm(notnecessarilyinthepropersequence).Match
 eachemissionwiththeappropriatewavelengthandcalculatetheenergiesoflevelsb,candd
relativetolevela.
4.67Smallheliumneonlasersemit1.0mJs1oflightat634nm.Howmanyphotonsdoessuchalaser
emitinoneminute?
4.68Theargonionlaserhasmajoremissionlinesat488and514nm.Eachoftheseemissionsleaves
theAr+ioninanenergylevelthatis2.7610 18Jabovethegroundstate.
(a)Calculatetheenergiesofthetwoemissionwavelengthsinjoules.
(b)Drawanenergyleveldiagram(injoulesperatom)thatillustratesthesefacts.
(c) WhatfrequencyandwavelengthradiationisemittedwhentheAr+ionreturnstoitslowest
energylevel?
4.69Theseriesofemissionlinesthatresultsfromexcitedhydrogenatomsundergoingtransitionstothe
n=3leveliscalledthePaschenseries.Calculatetheenergiesofthefirstfivelinesinthisseriesof
transitions,anddrawanenergyleveldiagramthatshowsthemtoscale.
4.70Ittakes486kJmol1toremoveelectronscompletelyfromsodiumatoms.Sodiumatomsabsorb
andemitlightofwavelengths589.6and590.0nm.
(a) CalculatetheenergiesofthesetwowavelengthsinkJmol1.
(b)Drawanenergyleveldiagramforsodiumatomsthatshowsthelevelsinvolvedinthese
transitionsandtheionisationenergy.
(c)Ifasodiumatomhasalreadyabsorbeda590.0nmphoton,whatisthewavelengthofthe
secondphotonasodiumatommustabsorbinordertoremoveanelectroncompletely?
4.71Thegraphbelowshowstheresultsofphotoelectronexperimentsontwometals,usinglightofthe
sameenergy.

(a)Calculatethebindingenergyofeachmetal.Whichhasthehigherbindingenergy?Explain.
(b)Calculatethekineticenergiesofelectronsejectedfromeachmetalbyphotonswith
wavelengthof125nm.
(c)Calculatethewavelengthrangeoverwhichphotonscanejectelectronsfromonemetalbut
notfromtheother.
4.72Writetheelectronconfigurationforthelowestenergyexcitedstateofeachofthefollowing:Be,
O2,Br,Ca2+andSb 3+.
4.73WritethegroundstateconfigurationsfortheisoelectronicspeciesCe2+,La+andBa.Aretheythe
same?Whatfeaturesoforbitalenergiesaccountforthis?
4.74Theionisationenergyoflithiumatomsinthegasphaseisabouthalfaslargeastheionisation
energyofberylliumatomsinthegasphase.Incontrast,theionisationenergyofLi+isaboutfour
 timeslargerthantheionisationenergyofBe+.Explainthedifferencebetweentheatomsandthe
ions.
4.75ThefiguresbelowshowCl,Ar,andK+drawntoscale.Decidewhichfigurecorrespondstowhich
speciesandexplainyourreasoning.
(a)

(b)

(c)

4.76Makeanelectrondensityplotthatshowshowthe3sand3porbitalsareshieldedeffectivelybythe
2porbitals.Provideabriefexplanationofyourplot.
4.77UsethedatainappendixGtoexplainwhythenoblegasesseldomtakepartinchemicalreactions.
4.78Fromitslocationintheperiodictable,predictsomeofthephysicalandchemicalpropertiesof
francium.Whatelementdoesitmostcloselyresemble?
4.79Whatwouldbethenexttwoorbitalstofillafterthe7porbital?
4.80Whichhasthemorestable2sorbital,alithiumatomoraLi2+cation?Explainyourreasoning.
4.81Thefirstfourionisationenergiesofaluminiumareasfollows:E =577kJmol1,E =1817kJ
i1 i2
mol1,Ei3=2745kJmol1andEi4=11578kJmol1.
(a)Explainthetrendinionisationenergies.
(b)Rankionsofaluminiuminorderofionicradius,fromlargesttosmallest.
(c)Whichionofaluminiumhasthelargestelectronaffinity?
4.82Theideaofanatomicradiusisinherentlyambiguous.Explainwhythisisso.
4.83Useelectronelectronrepulsionandorbitalenergiestoexplainthefollowingirregularitiesinfirst
ionisationenergies:
(a)Boronhasalowerionisationenergythanberyllium.
(b)Sulfurhasalowerionisationenergythanphosphorus.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
absorptionspectrum energyleveldiagram Pauliexclusionprinciple
amplitude excitedstate phase
atomicradius frequency() photoelectriceffect
Aufbauprinciple groundstate photons
azimuthalquantumnumber(l) groundstateconfiguration Planck'sconstant(h)
coreelectrons Hund'srule principalquantumnumber(n)
degenerate intensity quantised
diamagnetic ionisationenergy(Ei) quantumnumber
effectivenuclearcharge(Zeff) isoelectronic shielding
electromagneticradiation light spin
electronaffinity(Eea ) magneticquantumnumber spinquantumnumber(ms)
electronconfiguration (ml) uncertaintyprinciple
electrondensitypicture noblegasconfiguration valenceelectrons
electrondensityplot node wavelength()
emissionspectrum orbital
paramagnetic

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

5 ChemicalBondingand
MolecularStructure
Australia'sSamanthaStosurreturnsavolley.Thehightechfibresinhertennisracquetthatareresponsible
forsomeofthepowerareheldtogetherbychemicalbonds.Producingsuchhightechfibresrequiresa
thoroughunderstandingofchemicalbonding,becausethefibresareconstructedofpolymers,large
moleculesthatareheldtogetherbycovalentbondsinwhichelectronsaresharedbetweenatoms.Theways
inwhichchemicalbondsareformeddependonthenatureoftheelementsinvolved,andchemicalbonds
showavarietyofformsandstrengths.

Thischapterdescribeschemicalbondinganditsrelationshiptomolecularstructure.Wediscussthetwo
extremesofchemicalbonding:ionic,inwhichelectrostaticforcesholdionicarrangementstogether,and
covalent,wheresharedelectronpairsdictatethebondingandgeometryofindividualmolecules.Weshow
howsimpleLewistheorygivesagoodapproximationofthedistributionofelectronswithinmolecules,and
howwecanusethistopredictmoleculargeometryusingvalenceshellelectronpairrepulsiontheory.We
thenconsiderindetailthetwopredominanttheoriesusedtodescribecovalentbonding:valencebondtheory
andmolecularorbitaltheory.
 KEYTOPICS

5.1Fundamentalsofbonding
5.2Ionicbonding
5.3Lewisstructures
5.4Valenceshellelectronpairrepulsion(VSEPR)theory
5.5Propertiesofcovalentbonds
5.6Valencebondtheory
5.7Molecularorbitaltheory:diatomicmolecules

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.1FundamentalsofBonding
Welearnedinchapter4thatthesize,energylevelsandelectronconfigurationofanatomdetermineits
chemicalproperties.Inmolecularcompounds,electronsonatomsinteractandaresharedbetweenatoms.In
ioniccompounds,electronsaretransferredcompletelybetweenatomstoformpositivelyandnegatively
chargedions.Sinceelectronshavebothparticleandwavelikeproperties,bondinginteractionscanbe
describedfromeitherviewpoint.Keepinmind,though,thatthesemodelsdonotnecessarilyreflectreality
exactly.

Theelectrostaticenergybetweentwochargedspeciesisproportionaltothemagnitudesofthechargesand
inverselyproportionaltothedistancebetweenthem.Chargesofoppositesignattractoneanother,butlike
chargesrepel.TherelationshipisgivenbyCoulomb'slawas:

where:

Theequationdescribesthepotentialenergyofonepairofcharges.Molecules,however,containtwoor
morenucleiandtwoormoreelectrons.Toobtainthetotalpotentialenergyofamolecule,theequationmust
beappliedtoeverypossiblepairofchargedspecies.Thesepairwiseinteractionsareofthreetypes(see
figure5.1):
1.Electronsandnucleiattractoneanother.Attractiveinteractionsareenergeticallyfavourable,soan
electronattractedtoanucleusisatalowerenergythanafreeelectron.
2.Electronsrepeleachother,raisingtheenergyandreducingthestabilityofamolecule.
3.Nucleirepeleachother,sotheseinteractionsalsoreducethestabilityofamolecule.

FIGURE5.1Whenelectronsareintheregionbetweentwohydrogennuclei,attractiveelectrostaticforcesexceed
repulsiveelectrostaticforces,leadingtothestablearrangementofachemicalbond.

Inanymolecule,thesethreeinteractionsarebalancedtogivethemoleculeitsgreatestpossiblestability.This
balanceisachievedwhentheelectrondensityissituatedbetweenthenucleiofbondedatoms.Weviewthe
electronsasbeingsharedbetweenthenucleiandcallthissharedelectrondensityacovalentbond.Inany
covalentbond,theattractiveenergybetweennucleiandelectronsexceedstherepulsiveenergyarisingfrom
nuclearnuclearandelectronelectroninteractions.
TheHydrogenMolecule
Theseconceptsaredemonstratedbelowforthesimpleststableneutralmolecule,molecularhydrogen.A
hydrogenmoleculecontainsjusttwonucleiandtwoelectrons.

Considerwhathappenswhentwohydrogenatomscometogetherandformacovalentbond.Astheatoms
approach,eachnucleusattractstheoppositeelectron,pullingthetwoatomsclosertogether.Atthesame
time,thetwonucleirepeleachother,asdothetwoelectrons.Theserepulsiveinteractionstendtodrivethe
atomsapart.

ForH2tobeastablemolecule,thesumoftheattractiveenergiesmustexceedthesumoftherepulsive
energies.Figure5.1showsastaticarrangementofelectronsandnucleiinwhichtheelectronnucleus
distancesareshorterthantheelectronelectronandnucleusnucleusdistances.Asthechargesonthe
hydrogennucleiandelectronsare1+and1respectively,thedistancesbetweenthembecomecrucialin
determiningtheenergyofthisarrangement.Inthiscase,attractiveinteractionsexceedrepulsiveinteractions,
leadingtoastablemolecule.Noticethatthetwoelectronsoccupytheregionbetweenthetwonucleiwhere
theycaninteractwithbothnucleiatoncethatis,theatomssharetheelectronsinacovalentbond.

Anactualmoleculeisdynamic,notstatic,andboththeelectronsandnucleimovecontinuously.Ina
covalentbond,themostprobableelectronlocationsarebetweenthenuclei,where,inthismodel,theycan
beviewedasbeingsharedbetweenthebondedatoms.

BondLengthandBondEnergy
Astwohydrogenatomscometogethertoformamolecule,attractiveforcesbetweennucleiandelectrons
makethehydrogenmoleculemorestablethantheindividualhydrogenatoms.Theamountofincreased
stabilitydependsonthedistancebetweenthenuclei,asshowninfigure5.2.Atdistancesgreaterthan300
pm(30010 12m),thereisalmostnointeractionbetweentheatoms,sothetotalenergyisthesumofthe
energiesofthetwoindividualatoms.Atcloserdistances,theattractionbetweentheelectronofoneatomand
thenucleusoftheotheratomincreases,andthecombinedatomsbecomemorestable.Movingtheatoms
closertogethergeneratesgreaterstabilityuntilthenucleiare74pmapart.Atthisdistance,weobtainthebest
possiblebalancebetweentheattractiveandrepulsiveforcesinthemolecule.Atdistancescloserthan74pm,
thenucleusnucleusrepulsionbeginstodominateandtheenergyofthesystemincreasesrapidly.Thus,ata
separationdistanceof74pm,thehydrogenmoleculehasthemaximumenergeticadvantage(7.2210 19J)
overtwoseparatedhydrogenatoms.Experimentalstudiesofmolecularmotionrevealthatnucleiwithin
moleculesmovecontinuously,oscillatingabouttheirlowestenergyseparationdistanceliketwospheres
attachedtooppositeendsofaspring.
 FIGURE5.2Theinteractionenergyoftwohydrogenatomsdependsonthedistancebetweenthenuclei.

Figure5.2showstwocharacteristicfeaturesofcovalentbonds.Theseparationdistanceatwhichthe
moleculehasthemaximumenergeticadvantageovertheseparatedatoms(74pmforH2)isknownasthe
bondlength.Theenergydifferencebetweenthemoleculeandtheseparatedatomsatthisseparationdistance
iscalledthebondenergy.Bondenergyisdefinedastheenergyrequiredtobreakthebondandthereforeis
alwayspositive.Bondlengthsandenergiesareimportantpropertiesofchemicalbondsand,aswewillsee,
theyarerelated.ItisusualtoquotebondenergiesinunitsofkJmol1.Wecanobtainthisvalueforthe
hydrogenmoleculebymultiplyingtheenergyofasingleHHbond(7.2210 19J)byNA(6.02210 23
mol1).ThisgivesaHHbondenergyof435kJmol1.Eachdifferentchemicalbondhasacharacteristic
bondlengthandbondenergy.

Themostprobablepositionoftheelectronsinthehydrogenmoleculeisbetweenthenuclei.Ifwerotatethe
moleculeaboutitsinternuclearaxis(animaginarylinejoiningthetwonuclei)wefindthattheelectron
distributionbetweenthenucleilooksexactlythesame,regardlessoftheanglethroughwhichitwasrotated.
Inotherwords,thebondissymmetricwithrespecttorotationabouttheinternuclearaxis.Bondsforwhich
thisistruearecalledsigma()bonds.

OtherDiatomicMolecules:F2

BondformationinH2isrelativelyeasytodescribebecauseweneedtoconsiderjusttwoelectrons.
However,evenwhentheatomswithinamoleculecontainmanyelectrons,wecanstillconsiderbond
formationasthesharingofonlytwoelectrons.Wewillillustratethiswiththefluorinemolecule,F2.

Astwofluorineatomsapproacheachother,theelectronsofeachatomfeeltheattractionofthenucleusof
theotheratom,justasinH2.Inthiscase,thevalence2pelectronsareclosesttotheneighbouringnucleus
andexperiencethestrongestattraction.Thesingleelectroninoneofthe2porbitalsapproachestheopposite
nucleus.Consequently,wecandescribetheFFbondasthesharingoftwoelectronsfromthefluorine2p
orbitalsthatpointdirectlytowardseachother(seefigure5.3).Notethattheresultingbondisabond.

FIGURE5.3ThechemicalbondinF2 formsfromstrongelectrostaticattractionoftheelectroninthefluorine2p
orbitalthatpointsdirectlyattheneighbouringnucleus.
UnequalElectronSharing
Eachnucleuswithinahydrogenmoleculeandeachwithinafluorinemoleculehasthesamecharge.
Consequently,bothnucleiattractelectronsequally.Theresultisasymmetricaldistributionoftheelectron
densityaroundtheatoms.Inachemicalbondbetweenanytwoidenticalatoms,thenucleisharethebonding
electronsequally.

IncontrasttothesymmetricalforcesinH2andF2,thebondingelectronsinHFexperienceunsymmetrical
attractiveforces.Theeffectivenuclearchargeofafluorineatomissignificantlygreaterthantheeffective
chargeofahydrogenatomduetothegreaternumberofprotons,sotheelectronssharedbetweenHandF
feelastrongerattractiontotheFatom.Unequalattractiveforcesleadtoanunsymmetricaldistributionofthe
bondingelectrons.TheHFmoleculeismoststablewhenitsbondingelectronsareconcentratedclosertothe
fluorineatomandawayfromthehydrogenatom.Thisunequaldistributionofelectrondensitygivesthe
fluorineendofthemoleculeasmallnegativechargeandthehydrogenendasmallpositivecharge
however,themoleculeasawholeremainselectricallyneutral.Thesepartialchargesarelessthanonecharge
unitandareequalinmagnitude.Toindicatesuchpartialcharges,weusethesymbols+and(isthe
lowercaseGreekletterdelta)oranarrowpointingfromthenegativeendtowardsthepositiveendofthe
molecule,oranelectrondensitysurface,whichshowsthespreadofchargeusingcolours,withbluebeing
positiveandredbeingnegativeasshownforHFinfigure5.4.Thisunequalsharingofelectronsresultsina
polarcovalentbond.Wedescribebondpolarityanditsconsequencesinsection5.5.

FIGURE5.4UnequalsharingofelectrondensityinHFresultsinapolarcovalentbond.Thecolourgradient
representsthevariationinelectrondensitysharedbetweentheatoms.

Notethat,despitebeingpolar,theHFbondisstillabond,becauseitremainsunchangedaswerotate
themoleculeabouttheHFbondaxis.

Aselementsdifferintheireffectivenuclearcharges,atomsofeachelementhaveacharacteristicabilityto
attractelectronswithinacovalentbond.Thisabilityiscalledelectronegativityandissymbolisedby(the
lowercaseGreekletterchi).Abondbetweentwoelementsofdifferentelectronegativitieswillbepolar,and
thegreaterthedifference(),themorepolarthebond.

Electronegativitygivesanumericalvaluetohowstronglyanatomattractstheelectronsinachemicalbond.
Thispropertyofanatominvolvedinabondisrelatedto,butdistinctfrom,ionisationenergyandelectron
affinity.(Asdescribedinchapter4,ionisationenergymeasureshowstronglyanatomattractsoneofitsown
electrons.Electronaffinityspecifieshowstronglyanatomattractsafreeelectron.)

Electronegativities,whichhavenounits,areestimatedbyusingcombinationsofatomicandmolecular
properties.Theperiodictableshowninfigure5.5presentscommonlyusedvalues,developedbytheUS
scientistLinusPauling(figure5.6),basedonbondenergies.ThesevaluesareoftencalledthePaulingscale.
FIGURE5.5Electronegativitiesoftheelementsvaryperiodically.Whiletherearesomeexceptions,thegeneraltrend
isthatelectronegativityincreasesfromlefttorightanddecreasesfromtoptobottomoftheperiodic
table.ThePaulingscaleomitsgroup18elements(thenoblegases)becausetheyareveryunreactive
and,withveryfewexceptions,donotformcovalentbonds.Someotherelectronegativityscalesdo
assignvaluestotheseelements.
 FIGURE5.6LinusPauling(19011994)wasoneofthemostinfluentialthinkersoftwentiethcenturychemistryand
wasawardedtheNobelPrizeinchemistryin1954forhisresearchintothenatureofthechemical
bond.HewasalsooneofthefewpeopletobeawardedtwoNobelPrizes,receivingthepeaceprize
in1962forhisstandagainstnuclearweapons,whichledtheUSgovernmenttorevokehispassportin
1952.

Figure5.5showsthatelectronegativityisaperiodicproperty.Electronegativitiesgenerallyincreasefromthe
lowerlefttotheupperrightoftheperiodictable.Theelementsfranciumandcaesium(=0.7)havethe
lowestvalue,andfluorine(=4.0)hasthehighestvalue.Electronegativitiesalsogenerallydecreasedown
mostgroupsandincreasefromlefttorightacrossthesandpblocks.Aswithionisationenergiesand
electronaffinities,variationsineffectivenuclearchargeandprincipalquantumnumberexplain
electronegativitytrends.Metalsgenerallyhavelowelectronegativities(=0.7to2.4)andnonmetalshave
highelectronegativities(=2.1to4.0).Asexpectedfromtheirintermediatecharacterbetweenmetalsand
nonmetals,metalloidshaveelectronegativitiesthatarelargerthanthevaluesformostmetalsandsmaller
thanthoseformostnonmetals.

Electronegativitydifferences()betweenbondedatomsindicatewhereaparticularbondliesonthe
continuumofbondpolarities.Threefluorinecontainingsubstances,F2,HFandCsF,representtherangeof
variation.(Notethat,asnoweighablequantityoffranciumhaseverbeenisolated,thecompoundFrFis
unknown.)Atoneendofthecontinuum,thebondingelectronsinF2aresharedequallybetweenthetwo
fluorineatoms(=4.04.0=0).Attheotherlimit,CsF(=4.00.7=3.3)isacompoundinwhich
electronshavebeenfullytransferredtogiveCs+cationsandFanions.Wecallsuchcompoundsionic
compounds,andtheywillbediscussedinmoredetailinthenextsection.Mostbonds,includingthebondin
HF(=4.02.1=1.9),fallbetweentheseextremes.Thesearepolarcovalentbonds,inwhichtwoatoms
shareelectronsunequally.

ChemicalConnections

ElectromagneticRadiationandCancer

Theabilityoflighttoprovidetheenergyforchemicalreactionsenableslifetoexistonourplanet.
Greenplantsabsorbsunlightand,withthehelpofchlorophyll,convertcarbondioxideandwater
intocarbohydrates(e.g.sugarsandcellulose),whichareessentialconstituentsofthefoodchain.
However,notalleffectsofsunlightaresobeneficial.

Aswesawinchapter4,lighthasenergythatisproportionaltoitsfrequency,and,ifthephotons
thatareabsorbedbyasubstancehaveenoughenergy,theycanrupturechemicalbondsandinitiate
chemicalreactions.Thecarboncarbonandcarbonhydrogencovalentbondsfoundinorganic
moleculestypicallyhaveenergiesofatleast350kJmol1.Visiblelight,whichrangesfrom780nm
to380nminwavelength,hasacorrespondingenergyrangeofapproximately153to315kJmol1,
andthereforephotonsofvisiblelightarenotsufficientlyenergetictobreaksuchbonds.However,
ultravioletradiation,whichhasshorterwavelengthsandhencehigherenergies,canbedangerous
inthisrespect,particularlylightofwavelengthlessthan340nm,whichhasenergygreaterthan
350kJmol1.ThesunlightilluminatingtheEarthcontainssubstantialamountsofUVradiation.
Fortunately,alayerofozone(O3)inthestratosphere,aregionoftheatmosphereextendingfrom
about45to55kmaltitude,absorbsmostoftheincomingUV,protectinglifeonthesurface.
However,someUVradiationdoesgetthrough,andthepartofthespectrumofmostconcernis
calledUVBwithwavelengthsbetween280and320nm.

WhatmakesUVBsodangerousisitsabilitytoaffecttheDNAinourcells.(ThestructureofDNA
anditsreplicationisdiscussedinchapter25.)AbsorptionofUVradiationcausesconstituentsof
theDNA,calledpyrimidinebases,toundergoreactionsthatformbondsbetweenthem.Thiscauses
transcriptionerrorswhentheDNAreplicatesduringcelldivision,givingrisetogeneticmutations
thatcanleadtoskincancers.Theseskincancersfallintothreeclasses:basalcellcarcinomas,
squamouscellcarcinomas,andmelanomas,thelastbeingthemostdangerous.Eachyearmore
than1millioncasesofskincancerarediagnosedworldwide.Itisestimatedthatmorethan90%of
skincancersareduetoabsorptionofUVBradiation(figure5.7).

FIGURE5.7Dawnofanewdaybringstheriskofskincancertothoseparticularlysusceptible.
Fortunately,understandingtheriskallowsustoprotectourselveswithclothingand
sunblockcreams.

Inrecentyears,concernhasbeenexpressedinsomesectionsofthemediaoverapossiblelink
betweentheuseofmobilephonesandbraincancerithasbeenproposedbysomethatradiation
frommobilephones(figure5.8)cancausebraintumours,althoughalargenumberofstudieshave
failedtofindacausalrelationship.Thisisnotsurprising,giventhatmobilephonesusemicrowave
radiation,whichisofmuchlongerwavelengththanultravioletlight,andhenceinsufficiently
energetictocausemutationofDNAbybreakingcovalentbonds.
 FIGURE5.8Alargenumberofstudieshavefailedtofindacausalrelationshipbetweenmicrowave
radiationandbraintumours.MicrowaveradiationisnotenergeticenoughtomutateDNA.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.2IonicBonding
Compoundsformedbetweenelementsofverydifferentelectronegativitiesareoftenpredominantlyionic
incharacter.Forexample,ioniccompoundstendtoformbetweencationsfromgroups1and2and
anionsfromgroups16and17.Mostioniccompoundsaresolidswithrelativelyhighmeltingpoints,
particularlyiftheionicsolidsarecomposedofatomicorsmallmolecularions.Apartfromthesehigh
meltingpointionicsolids,thereisalsoaclassofcompoundscalledionicliquids,compoundsoflarge
molecularions.Theseare,bydefinition,ioniccompoundsthathavemeltingpointbelow100C.There
aresomeionicliquidsthatareliquidevenatroomtemperature,andthosehaveimportantapplications.

Thebondinginioniccompoundsdiffersfundamentallyfromthatincovalentcompoundsitdoesnot
involvethesharingofpairsofelectrons.Instead,ioniccompoundsareheldtogetherbythenon
directionalattractiveforcesbetweenoppositelychargedions,leadingtothreedimensionalarrangements
ratherthandistinctmolecules.

Consider,sodiumchloride,NaCl.ThestructureofthiscompoundhaseachNa+cationsurroundedby
sixClanionsandeachClanionsurroundedbysixNa+cations,asshowninfigure5.9.

FIGURE5.9Representationofpartofthestructureofsodiumchloride,NaCl.NotethateachNa+cationis
surroundedbysixClanions,andeachClanionissurroundedbysixNa+cations.

ThisarrangementofNa+cationsandClanionswasfirstdeterminedin1913byAustralianbornSir
WilliamLawrenceBragg,usingXrayequipmentdesignedbyhisfather,SirWilliamHenryBragg
(figure5.10).NaClwasthefirstcompoundwhosestructurewasdeterminedbyXraycrystallography
(seechapter7),afieldinwhichtheBraggswerepioneers.TheywerejointlyawardedtheNobelPrizein
physicsin1915,andWilliamLawrenceBraggbecametheyoungesteverawardeeattheageof25.
CrystalstructuresdeterminedthroughanalysisofXraydiffractiondatashowthepreciselocationsof
atomswithinachemicalspeciesandgiveatomicseparationsaccuratetoabout110 12m.Xray
crystallographyisavitalpartofmodernchemistryandisthesourceofmuchofthestructural
informationthatyouwillencounterinlaterchapters.
 FIGURE5.10SirWilliamLawrenceBragg(left)andhisfatherSirWilliamHenryBraggwereawardedthe
NobelPrizeinphysicsin1915fortheirworkonXraycrystallography.

ThedistancebetweentheionsinNaClisdeterminedbyabalanceoftheCoulombic(electrostatic)
attractionsandrepulsionsandtheshortrangerepulsiveinteractionsbetweenboththeelectrondensities
andnucleiofneighbouringions.Atroomtemperature,thedistancebetweenthecentresofneighbouring
ionsis2.8210 10m.Usingthisnumber,wecancalculatethemagnitudeoftheattractiveforces
betweentwoneighbouringNa+andClionsusingtheequationintroducedatthestartofthischapter.

Giventhatq 1is+1.6010 19C,q 2is1.6010 19C(1.6010 19Cisthefundamentalchargeofa

singleelectron)andk=9.0010 9Nm2C2,weobtainavalueof8.1710 19J,whichequatesto492
kJmol1whenmultipliedbytheAvogadroconstant.Thiscorrespondstotheenergyreleased(hencethe
negativesign)when1moleofgaseousNa+andgaseousClionsarebroughtfromaninfinitedistance
toaseparationof2.8210 10m.However,thisvaluetakesintoaccountonlytheattractiveforcesto
onenearestneighbour,whereaseachioninthecrystalhassix.Ifwetakeallsixinteractionsinto
account,aswellasrepulsiveinteractionsbetweenionsofthesamechargeinthestructure,weobtaina
valueof769kJmol1.Thisisasubstantialamountofenergy,andmeansthat,inordertobreak1mole
ofthecompoundintoitsconstituentgaseousions,wewouldhavetosupply769kJofenergy.Thisis
calledthelatticeenergyofthecompound.Amongotherfactors,thelatticeenergyofacompoundis
dependentonthechargesoftheionsasthechargesincrease,thelatticeenergybecomesmorepositive
andtheionsbecomehardertoseparatefromoneanother.Wealsoexpectlatticeenergyvaluesto
decreaseastheionsgetlarger,becauser,thedistancebetweenthem,willincrease.Thesetrendsare
illustratedintable5.1,whichgivessomelatticeenergyvaluesforionicspecies.
TABLE5.1 Latticeenergiesforanumberofioniccompounds.AllvaluesareinkJmol1
Anion
Cation F Cl Br I O2

Li+ 1030 834 788 730 2799

Na + 910 769 732 682 2481

K+ 808 701 671 632 2238

Rb+ 774 680 651 617 2163

 Mg 2+ 2913 2326 2097 1944 3795

Ca 2+ 2609 2223 2132 1905 3414

Sr2+ 2476 2127 2008 1937 3217

Ba 2+ 2341 2033 1950 1831 3029

Theeffectofionicsizeonlatticeenergyisshownbythefactthatthelatticeenergiesofthegroup1
chloridesdecreaseasthesizeofthecationincreasesfromLi+toRb +,andthelatticeenergiesofthe
sodiumhalidesdecreaseasthesizeoftheanionincreasesfromFtoI.Theeffectofionicchargeis
seenbycomparingthelatticeenergiesofthecompoundsformedfromthe2+ionswithhalideanions.In
allcases,theselatticeenergiesaremuchlargerthanthoseforthe1+/1combinations.Thevaluesfor
compoundscontaining2+and2ionsareevenlarger,withthelatticeenergyofMgObeingalmostfour
timesthelatticeenergyofLiF.However,itisimportanttonotethatmeaningfulcomparisonsoflattice
energyvaluescanbemadeonlybetweencompoundswiththesamestructuretype.

Whiletheionicmodeldescribesanumberofmetalhalides,oxidesandsulfideswell,itdoesnotdescribe
mostotherchemicalsubstancesadequately.CompoundssuchasCaO,NaClandMgF2behavelike
simplecationsandanionsheldtogetherbyelectrostaticattraction,butcompoundssuchasCO,Cl2and
HFdonot.Wemustdescribethebondingintheselattercompoundsintermsofthesharingofelectrons
betweenatoms.Therearetwopredominanttheoriesofbondingwhichdothis.Beforewestudythese,
wewilllookatasimplewayofdeterminingtheelectrondistributioninmoleculesandhowwecanuse
thistopredicttheshapeofaparticularmolecule.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.3LewisStructures
Inthissection,wedevelopaprocessformakingschematicdrawingsthatshowhowtheatomsina
moleculearebonded.Inaddition,thesedrawings,knownasLewisstructures,differentiatebetween
bondingandnonbondingvalenceelectronsinamolecule.Fromthisperspective,writingaLewis
structureisthefirststepindevelopingabondingdescriptionofamolecule.Lewisstructuresarenamed
aftertheiroriginator,GilbertNewtonLewis(18751946),formerProfessorofChemistryatthe
UniversityofCalifornia,Berkeley,USA.

TheConventions
Lewisstructuresaredrawnaccordingtothefollowingconventions:
1.Eachatomisrepresentedbyitselementalsymbol.Inthisrespect,aLewisstructureisan
extensionofthechemicalformula.
2.OnlythevalenceelectronsappearinaLewisstructure.Recallfromchapter4thatonlyvalence
electronsareaccessibleforbonding.
3.Alinejoiningtwoelementalsymbolsrepresentsonepairofelectronsthatissharedbetweentwo
atoms.Twoatomsmayshareuptothreepairsofelectronsinsinglebonds(2sharedelectrons,1
line),doublebonds(4sharedelectrons,2lines)andtriplebonds(6sharedelectrons,3lines).
4.Dotsplacednexttoanelementalsymbolrepresentnonbondingelectronsonthatatom.
Nonbondingelectronsusuallyoccurinpairswithopposingspins(seechapter4).

TheuseoftheseconventionsisshownfortheHFmoleculeinfigure5.11.

FIGURE5.11TheLewisstructureconventionsforhydrogenfluoride.

Theseconventionsdivideelectronsinmoleculesintothreegroups.Coreelectronsdonotappearin
Lewisstructures.Bondingvalenceelectronsaresharedbetweenatomsandappearaslines.Nonbonding
valenceelectronsarelocalisedonatomsandappearasdots.

WeuseafivestepproceduretodrawLewisstructures:
Step1:Countthevalenceelectrons.
Step2:Assemblethebondingframeworkusingsinglebonds.
Step3:PlacethreenonbondingpairsofelectronsoneachouteratomexceptH.(Note:Outeratoms
arethosethatarebondedtoonlyoneotheratom,whileinneratomsarethosebondedtomorethan
oneotheratom.)
Step4:Assigntheremainingvalenceelectronstoinneratoms.
 Step5:Minimiseformalchargesonallatoms.

BuildingLewisStructures
LearninghowtodrawLewisstructuresisbestdonethroughexamples.Wewillworkthroughthefive
stepsusingthesulfurdioxidemolecule,SO2.

Step1:Countthevalenceelectrons.Ifthespeciesisanion,addorsubtractoneelectronforeach
negativeorpositivecharge,respectively.Sulfur(group16)hasthevalenceelectronconfiguration
3s23p 4,whiletheconfigurationofoxygen(alsogroup16)is2s22p 4.Hence,thereisatotalof(6+[2
6])=18valenceelectronsfromtheatomsthemselves.Themoleculeisuncharged,sothetotalnumber
ofvalenceelectronsis18.

Step2:Assemblethebondingframeworkusingsinglebonds.Thisstepisstraightforwardfororganic
molecules,whichconsistpredominantlyofCandHatoms,asthereisnoambiguityastothepossible
placementofatoms.However,caremustbetakenwhendrawingstructuresofinorganicmolecules.
Structureswillgenerallyconsistofaninner(central)atomconnectedtotwoormoreother(outer)atoms.
Theouteratomswillgenerallybeeitherhydrogen,orthemostelectronegativeoftheatomspresent,and
willbebondedonlytotheinneratom.Inthecaseofsulfurdioxide,oxygenisthemostelectronegative
elementpresent,sosulfurwillbetheinneratom.Thebondingframeworkwillthereforebeasfollows.

Aseachsinglebondintheframeworkconsistsoftwoelectrons,wehaveusedfouroftheoriginal18
valenceelectronssofar.

Step3:PlacethreenonbondingpairsofelectronsoneachouteratomexceptH.Withtheexceptionof
hydrogen,allouteratomsareassociatedwitheightelectrons(fourpairsinthevalencesandporbitals),
whichmaybebondingornonbonding.Suchasetoffourpairsofelectronsassociatedwithanatomis
oftencalledanoctet.

Thenonbondingpairsarecalledlonepairs.EachOatomisassociatedwiththreelonepairsandone
bondingpairandthereforehasacompleteoctet.Weused(26)=12electronsinthisstep.Combined
withthefourusedinthepreviousstep,thismeans16oftheoriginal18electronshavebeenused.

Step4:Assigntheremainingvalenceelectronstoinneratoms.Therearetworemainingvalence
electrons.TheseareplacedontheinnerSatomasalonepairasfollows.

WehavenowaccountedforallthevalenceelectronsofSO2.

Step5:Minimiseformalchargesonallatoms.Atthispoint,weneedtoanalysethestructureobtained
andcheckthatitmakeschemicalsense.Todothis,calculatetheformalchargeoneachatom,andthen
minimiseitbyadjustingtheelectrondistribution.Formalchargeisdefinedasthedifferencebetweenthe
numberofvalenceelectronsinthefreeatomandthenumberofelectronsassignedtothatatominthe
Lewisstructure.
Assumethatlonepairelectronsbelongtotheatomonwhichtheyarelocated,whileelectronsinbonds
aresharedequallybetweenthetwoatoms.Ausefulfeatureofformalchargesisthatthesumofthe
formalchargesonallatomsequalsthechargeofthespecies.Foraneutralmolecule,thesumofthe
formalchargesmustbezero.Foracationoranion,thesumoftheformalchargesequalsthechargeon
theion.

Theformalchargesoftheatomsinthestructureobtainedinstep4arecalculatedasfollows:

S Valenceelectronsoffreeatom 6
Lonepairelectrons 2
Sharedelectrons 4
Formalcharge

O Valenceelectronsoffreeatom 6
Lonepairelectrons 6
Sharedelectrons 2
Formalcharge

WecanminimisetheformalchargesbyconvertingalonepairofelectronsoneachOatomtoabonding
pair.Wecanrepresentthisprocessdiagrammaticallyasfollows.

Ifweanalysetheformalchargesontherighthandstructure,wefindthattheyareallzero.Therefore,
therighthandstructureisthebestLewisstructuralrepresentationoftheSO2molecule.

Inthisstructureeachoxygenatomissurroundedbyeightelectrons,andthereforehasanoctet,while
theinnersulfuratomissurroundedby10electrons.Wegenerallyfindoctetssurroundingatomsfrom
thesecondperiodoftheperiodictable,especiallyC,N,OandF,assuchatomscanaccommodatea
maximumofeightelectronsintheavailableorbitals.However,thelargeratomsfromthethirdand
subsequentperiodsoftenaccommodatemorethaneightelectrons,asobservedforthesulfuratom.This
isduetothefactthattheseatomshavemorethanfourorbitalsavailableforvalenceelectrons.

WORKEDEXAMPLE5.1

LewisStructureofClf3

Chlorinetrifluoride,ClF3,isusedtorecoveruraniumfromnuclearfuelrodsinahigh
temperaturereactionthatproducesgaseousuraniumhexafluoride.

DeterminetheLewisstructureofClF3.
 Analysis

WefollowthefivestepsoutlinedpreviouslyfordrawingaLewisstructure.

Solution
1.Allfouratomsarehalogens(group17,ns2np 5),soClF has28valenceelectrons.
3
2.Chlorine,withlowerelectronegativitythanfluorine,istheinneratom.Makeasingle
bondtoeachofthethreefluorineatoms.

3.Addthreenonbondingpairstoeachfluorineatom.

4.Fourelectronsremainunassigned.Placetwoelectronpairsonthechlorineatom.

5.Determinetheformalchargesonalltheatomsandadjusttheelectrondistributionif
necessary.Inthiscase,eachatomhasaformalchargeofzero,andsonoredistribution
ofelectronsisrequired.

Isouranswerreasonable?

Step4resultsin10electronsaroundthechlorineatom.However,chlorineisathirdrow
elementandisthereforeabletoaccommodatemorethaneightelectrons.Wehavefollowed
therulesandobtainedthestructurewithformalchargesofzerooneveryatom,soouranswer
isreasonable.

PRACTICEEXERCISE5.1
DeterminetheLewisstructureofsulfur
tetrafluoride,SF4.

NotethatsomemoleculesandallionswillhavepreferredLewisstructuresinwhichtheformalcharges
arenotallzero.Inthesecases,ensurethatnegativeformalchargesaresituatedonthemostelectro
negativeatomsandpositiveformalchargesontheleastelectronegativeatoms(forexample,thenitrate
ioninfigure5.12,wherethemoreelectronegativeOatoms,ratherthantheNatom,haveanegative
formalcharge).Itisalsoimportanttorealisethatformalchargesarenotthesameasthepartialcharges
inducedasaresultofbondpolarity.Forexample,inClF3,thechlorineatomwouldhavea+charge,
despitethefactthatitsformalchargeiszero.
 FIGURE5.12Therearethreepossiblewaystominimisetheformalchargesinthenitrateionanyofthethree
oxygenatomscansupplyapairofelectrons.

ResonanceStructures
Incompletingstep5oftheLewisstructureprocedure,theremightbemorethanonewaytominimise
theformalchargesontheatomsthatis,morethanoneLewisstructureispossibleforaparticular
moleculeorion.Thisisshownbelowwiththenitrateanion,NO3.

Theanionhas24valenceelectrons,andnitrogenistheinneratom.ThreeNObondsusesixelectrons,
andassigningsixelectronstoeachofthethreeouteroxygenatomsusestheremaining18electrons.
ThisgivesaLewisstructureinwhichtheOatomshaveformalchargesof1andtheNatomhasa
formalchargeof+2.Wecanminimisetheformalchargesbyconvertingthelonepairononeoxygen
atomtoabondingpair.However,asfigure5.12shows,alonepairfromanyofthethreeoxygenatoms
canbemovedtoformthisdoublebond.

WhichoftheseoptionsisthecorrectLewisstructure?Actually,nosingleLewisstructureisanaccurate
representationofNO3.AnysinglestructureoftheanionshowsnitratewithoneN Odoublebond
andtwoNOsinglebonds.Experiments,however,showthatallthreeNObondsareidentical(we
cannotformtwodoublebondssincenitrogencanaccommodateonlyeightelectronsinitsorbitals).To
showthatthenitrateNObondsareallalike,weuseacompositeofthethreeequivalentLewis
structures.Thesearethencalledresonancestructures.Resonancestructuresareconnectedbydouble
headedarrowstoemphasisethatacompletedepictionrequiresallofthem.

Itisessentialtorealisethatelectronsinthenitrateaniondonotflipbackandforthamongthethree
bonds,asimpliedbyseparatestructures.Noneofthesestructuresactuallyexist.Thetruecharacterof
theanionisablendofthethree,inwhichallthreenitrogenoxygenbondsareequivalent.Notealsothat
resonancestructuresdifferonlyinthepositionoftheelectronsyoucannotmoveatomswhendrawing
resonancestructures.Theneedtoshowseveralequivalentstructuresforspeciessuchasthenitrateion
reflectsthefactthatLewisstructuresareapproximaterepresentationsofstructureswithdelocalised
electrons.Whiletheyrevealmuchabouthowelectronsaredistributedinamoleculeorion,theycannot
describetheentirestoryofchemicalbonding.

WORKEDEXAMPLE5.2

ResonanceStructuresofanOxoanion

Determinethepossibleresonancestructuresofthephosphateanion,PO43.

Analysis

WemustfirstdeterminetheLewisstructurebyfollowingthefivestepprocedureoutlined
previously.Instep5,wedeterminethedifferentwayswecanminimisetheformalcharges
withintheion,therebyobtainingtheresonancestructures.

Solution

Wehave32electronstobeused(rememberthattheionhasa3charge).Followingtherules
outlinedpreviously,wearriveatthefollowingstructure,inwhichalltheelectronsareused
afterstep4.

Inthisstructure,theOatomsallhaveformalchargesof1,whilethePatomhasaformal
chargeof+1.Turningonelonepairfromanoxygenatomintoabondingpairmakesthe
formalchargeonthePatomzeroandalsomakestheformalchargeontheOatominvolved
equaltozero,therebyminimisingtheformalchargesintheion.Wecanshiftelectronsfrom
anyoftheouterOatoms,sotherearefourpossibleresonancestructuresasshownbelow.
(Notethatwehaveomittedthe3chargeoneachstructureforclarity.)

Isouranswerreasonable?
 Therearefourpossiblewaystominimisetheformalcharges,sowemusthavefour
resonancestructures.Thefourstructuresdifferonlyinthepositionofadoublebond,and
thereforewecanbeconfidentthatouransweriscorrect.

PRACTICEEXERCISE5.2
DeterminetheLewisstructureoftheacetate
anion,CH3COO.

Intheexamplespresentedsofar,alltheresonancestructuresareequivalentinenergy,butresonance
structuresarenotalwaysequivalent.Resonancestructuresthatarenotequivalentoccurwhenstep5
requiresshiftingelectronsfromatomsofdifferentelements.Insuchcases,differentpossiblestructures
mayhavedifferentformalchargedistributions,andtheoptimalsetofresonancestructuresincludes
thoseformswiththelowestpossibleformalchargeoneachatom.

WORKEDEXAMPLE5.3

ResonanceStructuresofN2O

Determinethepossibleresonancestructuresofdinitrogenoxide,N2O,agasusedasan
anaesthetic,afoamingagentandapropellantforwhippedcream.

Analysis

Onceagain,wefirstdeterminetheLewisstructure,andtheninspectanypossibleresonance
structures.

Solution

WemustfirstchoosewhetherNorOwillbetheinneratom.AsOismoreelectronegative
thanN,thestructurewillhaveaninnerNatombondedtoanOatomandanotherNatom.
Thestructureweobtainfollowingthefirstfourstepsis:

Thisstructurehasformalchargesof2ontheouterNatom,+3ontheinnerNatomand1
ontheOatom.WecanconvertlonepairsontheendNatomortheOatomintobonding
pairstoreducetheformalcharges,butwemustensurethattheinnerNatomhasnomore
thanfourelectronpairs.Thisleavesuswiththefollowingpossibilities,inwhichthenumbers
denotetheformalcharges.
 Theformalchargesofthefirsttwostructuresareidentical,andlessthanthoseonthethird
structure.Thus,theoptimalLewisstructureoftheN2Omoleculeisacompositeofthefirst
twostructures,whichareformallyinequivalent,butnotthethird.

Isouranswerreasonable?

Wehavechosenthetwostructuresinwhichtheformalchargesareminimised,andsoour
answershouldbecorrect.Infact,experimentalstudiesshowthatthenitrogenoxygenbond
inN2OissomewherebetweenanNOsingleandanN Odoublebond.

PRACTICEEXERCISE5.3
DeterminetheLewisstructureofozone,O3,
inwhichthethreeoxygenatomsarelinked
inarow.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.4ValenceshellelectronpairRepulsion(VSEPR)
Theory
TheLewisstructureofamoleculeshowshowthevalenceelectronsaredistributedamongtheatoms.Itdoes
not,however,showthethreedimensionalstructure,whichplaysanessentialroleindeterminingchemical
reactivity.However,wecanusetheLewisstructureasastartingpointtodeterminetheshapeofamolecule
orion.Thevalenceshellelectronpairrepulsion(VSEPR)theoryconsidersthatmolecularshapeis
determinedprimarilybytherepulsionsbetweenpairsofelectronsinthemoleculeormolecularion,bethey
bondingpairsorlonepairs.Therefore,tominimisetheserepulsions,electronpairsaroundaninneratom
withinamoleculewillbesituatedasfarapartaspossibleinthepreferredthreedimensionalstructure.

TodeterminetheshapeofamoleculeusingVSEPRtheory,weusethefollowingprocedure:
1.DetermineanddrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,anduse
table5.2todeterminetheoptimumgeometryofthesesets.
NotethatVSEPRtheorymakesnodistinctionbetweenelectronpairsinsingle,doubleandtriple
bonds.Eachistreatedasbeingoneset.
TABLE5.2 Optimumgeometryofsetsofelectronpairs
Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs(BP)or
lonepairs(LP).Therepulsionsareintheorder:

Therefore,twoneighbouringlonepairsonaninneratomwillrepeleachothertoagreaterextentthanwill
twoneighbouringbondingpairs.Thisisbecauselonepairsoccupyalargervolumethanbondingpairs.Note
thatdoublebondsoccupyalargervolumethansinglebonds,andsomestructuresmayhavetobemodified
forthis.

Itisimportanttomakethedistinctionbetweenthegeometryofthesetsofelectronpairs,andtheshapeof
themolecule.Theformerreferstothewayinwhichsetsofelectronpairsarearrangedaroundaninneratom
ofthemolecule,whilethelatterreferstothearrangementoftheatomsbondedtothatinneratom.Aswewill
see,whenlonepairsarepresent,thetwoarenotthesame.

WewillnowillustrateVSEPRusingexamplesofeachdifferentgeometryofsetsofelectronpairs.

TwoSetsofElectronPairs:LinearGeometry

BerylliumHydride,BeH2

TheLewisstructureofBeH2is:
Inthiscase,wehavetwosetsofelectronpairsaroundtheinneratomthatweneedtosituateasfaraway
fromeachotheraspossible.Thisissatisfiedbyplacingthetwosetsinalineararrangement(table5.2)and
resultsinalinearshapeforthismolecule,withaHBeHbondangleof180.Notethatwedonotadjust
theoptimumgeometryoftheelectronpairs,sincethereareonlytwosinglebondingpairsandnolonepairs.

CarbonDioxide,CO2

TheLewisstructureofCO2showsaninnerCatombondedtotwoouterOatoms.

ThisissimilartoBeH2becausewehavetwosetsofelectronpairsagain.Eventhougheachsetcomprisesthe
twoelectronpairsofadoublebond,theprincipleisstillthesame.Weplacethetwosetsasfarapartas
possible,i.e.inalineararrangement,andthisleadstoalinearshape.NoticethatthelonepairsontheO
atomsdonotaffecttheoverallshapeofthemoleculeonlysetsofelectronsthatareeitherbondedto,orlie
completelyon,aninneratomdeterminemolecularshape.

ThreeSetsofElectronPairs:TrigonalPlanarGeometry

BoronTrifluoride,BF3

TheLewisstructureofBF3showsaninnerBatomsinglybondedtothreeFatoms.Wehavethreesetsof
electronpairsabouttheinneratom.

Theoptimalgeometryforthreesetsofelectronpairsistrigonalplanar(table5.2).Inthisarrangement,the
setsareorientedat120toeachotherandarecoplanar.ThisleadstoatrigonalplanarshapefortheBF3
molecule,withallatomscoplanarandallFBFbondanglesof120.Notethat,again,asallthesetsof
electronpairsinvolvedareequivalent,wedonothavetoadjusttheiroptimalgeometry.

TheNitriteIon,NO2

Twopossibleresonancestructurescanbedrawnforthenitriteion,whichareasfollows.

Thisisthefirstexamplewehaveencounteredinwhichtheinneratombearsalonepair,andthishas
importantimplicationswhenapplyingVSEPRtheory.Notethatwecanchooseeitherresonancestructure
andendupwiththesameresult.Therearethreesetsofelectronpairs,twosetsofbondingpairsandalone
pair.Theidealisedgeometryistrigonalplanar.However,inthiscase,notalltherepulsionsbetweenthesets
ofelectronpairsarethesamethereareBPBPrepulsionsandBPLPrepulsions.TheBPLPrepulsionsare
stronger,whichmeansthatthetwobondingpairswillbepushedslightlyclosertogetherthananexact
trigonalplanararrangement.TheresultisthattheONObondangleisabout115,ratherthan120.This
examplealsoillustratesthedifferencebetweengeometryandshape.Thesetsofelectronpairshavean
approximatelytrigonalplanargeometry,butwewoulddescribetheshapeoftheNO2ionasbent,because
shaperefersonlytothepositionsoftheatomsandnottheelectrons.

FourSetsofElectronPairs:TetrahedralGeometry

Methane,CH4

TheLewisstructureofmethane,CH4,showsthatthemoleculecontainsfourCHsinglecovalentbonds,
andthereforefoursetsofequivalentelectronpairs.

Theoptimalgeometryforfoursetsofelectronpairsistetrahedral(table5.2).Thismeansthatthemethane
moleculeistetrahedralinshape,withHCHbondanglesof109.5,andtheHatomssituatedatthefour
verticesofatetrahedron.

Ammonia,NH3

TheLewisstructureofammonia,NH3,showsatotaloffoursetsofelectronpairs,threebondingpairsanda
lonepair.

Theidealisedarrangementoffoursetsofelectronpairsistetrahedral.ButwenowhaveBPBPandBPLP
repulsionstoconsider.ThesinglelonepairontheNatomtakesupmorespacethaneachofthethree
bondingpairs,andthisdistortstheidealisedarrangementsuchthattheHNHanglesinammoniaare
about107.Ammoniaadoptsatrigonalpyramidalshape,withtheNatomlyingoutoftheplaneofthethree
Hatoms.
Water,H2O

Likemethaneandammonia,waterhasfoursetsofelectronpairs,asshowninitsLewisstructure,andthe
idealisedarrangementisagaintetrahedral.

However,inthiscasewehavetwosetsofbondingpairsand,significantly,twolonepairs.TheLPLP
repulsiondominates,andtherearealsoBPLPrepulsionstoconsider.Theresultisthattheidealised
tetrahedralgeometryofthefoursetsofelectronpairsissignificantlydistorted,suchthattheHOHbond
angleinwaterisabout104.5.Wateradoptsabentshape.

Figure5.13showsthedifferentshapesofmethane,ammoniaandwater.Theimportanteffectoflonepairs
ontheshapesofthemoleculesisevidentinthesethreediagrams.

FIGURE5.13Representationsofthedifferentshapesofmethane,ammoniaandwatermolecules,eachwithfour
setsofelectronpairs.

WORKEDEXAMPLE5.4

ShapeoftheHydroniumIon

Determinetheshapeofthehydroniumion,H3O+,usingVSEPRtheory.Makeasketchoftheion
thatshowsthethreedimensionalshape,includinganylonepairsthatmaybepresent.

Analysis

Followthethreestepprocessdescribedpreviously.BeginwiththeLewisstructure,andthenuse
thistodeterminethenumberofsetsofelectronpairsandthereforethegeometryofthese.Finally,
takeintoaccountanylonepairstodeducethemolecularshape.

Solution
1.DeterminetheLewisstructure.Ahydroniumionhaseightvalenceelectrons.Sixareused
tomakethreeOHsinglebonds,andtwoareplacedasalonepairontheoxygenatom.
 2.Therearefoursetsofelectronpairs,threebondingpairsandonelonepair.Theidealised
geometryisthereforetetrahedral.
3.Thepresenceofalonepairmeansthattheidealisedtetrahedralgeometryofthesetsof
electronpairswillbedistorted,owingtoLPBPrepulsions.Wewouldthereforeexpectthe
HOHbondanglestobesomewhatlessthanthe109.5.Theshapeofthehydronium
ionistrigonalpyramidal,asoutlinedinthefollowingdiagram.

Isouranswerreasonable?

Thehydroniumionhasthesamenumberofelectronsandatomsastheammoniamolecule,soit
isreasonableforthesespeciestohaveasimilarshape.

PRACTICEEXERCISE5.4
Determinetheshapeofchloromethane,CH3Cl.
Makeasketchofthemoleculethatshowsits
threedimensionalshape.

FiveSetsofElectronPairs:TrigonalBipyramidalGeometry

PhosphorusPentachloride,Pcl5

TheLewisstructureofPCl5showsfivesetsofequivalentelectronpairsaroundaphosphorusatom.

Thegeometrywhichplacestheseasfarapartaspossibleistrigonalbipyramidal(table5.2).Atrigonal
bipyramidissocalledbecauseitcanbeviewedastwopyramidsthatshareatriangularbase,asshownin
figure5.14a.Incontrasttothegeometriesencounteredsofar,thefivepositionsinatrigonalbipyramidare
notallequivalent.Threepositionslieatthecornersofanequilateraltrianglearoundtheinneratom,
separatedby120bondangles.Atomsinthetrigonalplaneareinequatorialpositions.Theothertwo
positionsliealonganaxisaboveandbelowthetrigonalplane,separatedfromequatorialpositionsby90
bondangles.Atomsinthesesitesareinaxialpositions.Thesedifferencesareoutlinedinfigure5.14b.
 FIGURE5.14 (a)Modelrepresentingtheequatorialplaneandopposingpyramidsthatmakeupatrigonal
bipyramid.PCl5 adoptsaregulartrigonalbipyramidalshape.
(b)Ballandstickmodelrepresentingatrigonalbipyramidwithaxialandequatorialsites
labelled.

AsPCl5containsonlybondingpairsofelectrons,wewouldexpectittoadoptaregulartrigonalbipyramidal
shape,asshowninfigure5.14.

Whenlonepairsarepresentinmoleculeswithfivesetsofelectronpairs,theconsequencesofthe
inequivalenceoftheaxialandequatorialsitesbecomemoreapparent.WewillillustratethiswithSF4.

SulfurTetrafluoride,SF4

TheLewisstructureofSF4(figure5.15)showsfourSFbondsandonelonepairofelectronsonthesulfur
atom.Wewouldexpectatrigonalbipyramidalgeometryforthesefivesetsofelectronpairs,butthe
presenceofthelonepairmeanstherewillbesomeslightdistortion.

FIGURE5.15 Viewsofsulfurtetrafluoride:
(a)Lewisstructure
(b)ballandstickmodelofthetrigonalpyramidand
(c)ballandstickmodelshowingtheseesawform.

Inaddition,becausetheequatorialandaxialpositionsofatrigonalbipyramiddiffer,wecandrawtwo
possiblestructuresforSF4withthelonepairineitheraxialorequatorialposition.Asfigure5.15shows,
placingthelonepairinanaxialpositiongivesatrigonalpyramidalshape,whereasplacingthelonepairin
anequatorialpositiongivesaseesawshape.

ExperimentsshowthatSF4hastheseesawshape,whichmeansthatthisismorestablethanthetrigonal
pyramid.ThiscanbeexplainedbynotingthatthetrigonalpyramidstructurehasthreeLPBPrepulsionsat
90,whiletheseesawhastwoat90andtwoat120.Minimisingthenumberoflowestanglerepulsive
interactionsinvolvinglonepairsgivesthelowestenergystructureandconsequentlytheseesawshapeis
preferred.Notethat,becauseoftheLPBPrepulsionsbetweenthelonepairandtheaxialbondpairs,the
axialFSFbondangleisslightlylessthan180.

Chlorinetrifluoride,ClF3

TheLewisstructureofClF3showsfivesetsofelectronpairs:threebondingpairsandtwolonepairs.

Weagainexpectadistortedtrigonalbipyramidalgeometryofthefivesetsofelectronpairs,butnowwe
mustdeterminewhetherthetwolonepairsoccupyaxialorequatorialpositions.

Wecanimmediatelydiscountplacingonelonepairaxialandtheotherequatorial,asthiswouldleadtoa
LPLPrepulsion,thelargestpossible,at90.Youmightimaginethatplacingthelonepairsintheaxial
positionswouldbepreferred,asitplacesthemfurthestaway,butitalsoleadstoatotalofsixLPBP
repulsionsat90.Infact,experimentsshowthatthetwolonepairsareequatorialthisleadstofourLPBP
repulsionsat90andisenergeticallypreferred,despitethefactthatthereisaLPLPrepulsionat120.Thus,
ClF3isTshapedwithtwoequatoriallonepairs.

ItissometimesdifficulttodeterminewhichofthepossiblestructuresiscorrectusingsimpleVSEPRtheory,
andwemustthenresorttoexperimentalresultsfordefinitiveanswers.

TheTriiodideIon,I3

TheLewisstructureshowsfivesetsofelectronpairsaroundtheinnerIatom:twobondingandthreelone
pairs.

Wehaveseeninthepreviousexamplesthatlonepairsprefertobeinequatorialpositionsintrigonal
bipyramidalgeometries,andthesameprincipleapplieshere.Allthreelonepairsareequatorial,asthisisthe
onlywaytoavoidanyhighlydestabilisingLPLPrepulsionsat90.
Figure5.16summarisesthedifferentpossibleshapesofspecieswithfivesetsofelectronpairs.

FIGURE5.16Thedifferentpossibleshapesofspecieswithfivesetsofelectronpairs.

SixSetsofElectronPairs:OctahedralGeometry

SulfurHexafluoride,SF6

TheLewisstructureofSF6,showninfigure5.17a,indicatesthatsulfurhassixSFbondsandnolone
pairs,andthereforehassixsetsofelectronpairsaroundtheinnerSatom.Anoctahedralgeometryofthesix
sets(table5.2)placesthemasfarapartaspossible,asshowninfigure5.17b.Thisgivesanoctahedral
shapeeachFatomliesatoneofthesixverticesofanoctahedron,withpossibleFSFbondanglesof
90and180.Anoctahedronissocalledbecauseithaseighttriangularfaces,asshowninfigure5.17c.

FIGURE5.17 Viewsofsulfurhexafluoride:
(a)Lewisstructure
(b)ballandstickmodeland
(c)ballandstickmodelshowingthetriangularfacesoftheoctahedron.
Allsixpositionsaroundanoctahedronareequivalent,asfigure5.18demonstrates.Replacingonefluorine
atominSF6withachlorineatomgivesSF5Cl.Nomatterwhichfluorineisreplaced,theSF5Clmoleculehas
fourfluorineatomsinasquare,withthefifthfluorineandthechlorineatomonoppositesides,atright
anglestotheplaneofthesquare.

FIGURE5.18ReplacinganyofthefluorineatomsofSF6 withachlorineatomgivesamoleculewithasquareof
fluorineatomscappedbyonefluorineandonechlorine.Thisshowsthatallsixpositionsofthe
octahedronareequivalent.

ChlorinePentafluoride,ClF5

TheLewisstructureofClF5showsatotalofsixsetsofelectronpairs:fivebondingpairsandonelonepair.

Weagainexpectanoctahedralgeometryofthesixsetsofelectronpairs,and,inthiscase,allsixpossible
positionsofthelonepairareequivalent.Therefore,ClF5adoptsasquarepyramidalshape.

XenonTetrafluoride,XeF4

TheLewisstructureofthismoleculeshowssixsetsofelectronpairs:fourbondingpairsandtwolonepairs.
Wethereforeexpectanoctahedralgeometryofthesetsofelectronpairs,but,asalways,wemustdetermine
howtoarrangethelonepairs.InXeF4,bothlonepairsmustbeoppositeeachtotherbecauseanyother
arrangementwouldleadtohighlydestabilisingLPLPrepulsionsat90.Thisleavesthefourfluorineatoms
inasquareplanearoundxenon.

Figure5.19summarisestheshapesofmoleculeswithsixsetsofelectronpairs.Thiscompletesourinventory
ofmolecularshapes.

FIGURE5.19Thedifferentpossibleshapesofsomemoleculeswithsixsetsofelectronpairs.

ThemostcommonmistakemadewhendeterminingamolecularshapeusingVSEPRtheoryistocountthe
numberofatomssurroundinganinneratom,ratherthanthenumberofsetsofelectronpairs.Forexample,a
moleculesuchasSF4maybeeasilymistakenastetrahedral,byanalogywithtetrahedralCH4,asboth
moleculeshavefourouteratomssurroundinganinneratom.However,wehaveshownpreviouslythatSF4
hasfivesetsofelectronpairsanditsshapeisbasedonatrigonalbipyramidalarrangementofthese.While
VSEPRtheoryoftengivesremarkablyaccurateresults,itdoesnotnecessarilyworkforallmolecules.In
caseswhererepulsionbetweentheelectronpairsisnotthedominantfactorindeterminingmolecular
geometry,VSEPRtheoryfails.Youwillencountersomeexamplesofthisinchapter13.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.5PropertiesofCovalentBonds
HavingdevelopedideasaboutLewisstructuresandshapesofmolecules,wecannowexploresomeofthe
importantfeaturesofcovalentbonds.Thesefeaturesproviderevealinginformationaboutmolecular
shapes.

DipoleMoments
Asdescribedinsection5.1,mostchemicalbondsarepolar,meaningthatoneendofthebondisslightly
negative,andtheotherisslightlypositive.Bondpolaritiescanleadtomoleculeswithnegativeendsand
positiveends.Amoleculewiththistypeofelectrondensitydistributionissaidtohaveadipolemoment,
(thelowercaseGreeklettermu).

Thedipolemomentofapolarmoleculecanbemeasuredbyplacingasampleinanelectricfield.For
example,figure5.20showsaschematicdiagramofhydrogenfluoride,HF,moleculesbetweenapairof
metalplates.Intheabsenceofanappliedfield,themoleculesareorientedrandomlythroughoutthe
volumeofthedevice.Whenanelectricpotentialisappliedacrosstheplates,theHFmoleculesalign
spontaneouslyaccordingtotheprinciplesofelectrostaticforce.Thepositiveendsofthemolecules(the
hydrogenatoms)pointtowardsthenegativeplate,andthenegativeends(thefluorineatoms)point
towardsthepositiveplate.Theextentofalignmentdependsonthemagnitudeofthedipolemoment.The
SIunitforthedipolemomentisthecoulombmetre(Cm).Bonddipolemomentsspantherangefrom0to
about710 30Cm.Hydrogenfluoridehas=5.9510 30Cm,whileanonpolarmoleculelikeF2has
nodipolemoment,=0Cm.Experimentalvaluesarealsooftenreportedinunitsofdebyes,D(1D=
3.3410 30Cm).

FIGURE5.20AnappliedelectricfieldcausesanalignmentofpolarHFmolecules.Theextentofalignment
dependsonthemagnitudeofthedipolemoment.

Dipolemomentsdependonbondpolarities.Forexample,thetrendindipolemomentsforthehydrogen
halidesfollowsthetrendinelectronegativitydifferencesthemorepolarthebond(indicatedbythe
differenceinelectronegativity,,thelargerthedipolemoment,.
Dipolemomentsalsodependonmolecularshape.Anydiatomicmoleculecomposedofatomswith
differentelectronegativitieshasadipolemoment.Formorecomplexmolecules,wemustevaluatedipole
momentsusingbothbondpolarityandmolecularshape.Amoleculewithpolarbondswillhavenodipole
momentifitsshapecausesthedipolemomentsofindividualbondstocanceloneanother,whichismore
likelyforsmallsymmetricalmolecules.

Figure5.21illustratesthedramaticeffectofshapeonthedipolemomentsoftriatomicmolecules.Recall
fromsection5.1thatanarrowcanbeusedtorepresentadipolemoment.Theheadofthearrowpointsto
thepartialpositiveend(+)ofthepolarbond.Figure5.21ashowsthat,althoughbothbondsinlinearCO2
arepolar(=1.0),thetwoarrowsindicatingindividualbondpolaritiespointinexactlyopposite
directions.Thus,theeffectofonepolarbondexactlycancelstheeffectoftheother.ForbentH2O,in
contrast,figure5.21bshowsthattheeffectsofthetwopolarbondsdonotcancel.Waterhasapartial
negativechargeonitsoxygenatomandpartialpositivechargesonitshydrogenatoms.Theresulting
dipolemomentofthemoleculeis=6.1810 30Cm,withthedirectionofthedipolemomentshownby
thecolouredarrowinfigure5.21b.

FIGURE5.21 (a)Whenidenticalpolarbondspointinoppositedirections,asinCO2 ,theirpolarityeffects

cancel,givingzeronetdipolemoment.
(b)Whentwoidenticalpolarbondsdonotpointinexactlyoppositedirections,asinH2 O,
thereisanetdipolemoment.

Moleculescontainingpolarbondswhosedipolemomentscanceleachotherdonothaveoveralldipole
moments.Suchmoleculestendtohavehighlysymmetricalgeometries.Phosphoruspentachloride,for
example,has=0Cm.ThetwoaxialPClbondspointinoppositedirections,and,althoughthreeP
Clbondsarrangedinatrigonalplanehavenocounterpartspointinginoppositedirections,trigonometric
analysisshowsthatthepolareffectsofthreeidenticalbondsinatrigonalplanecancelexactly.Likewise,
thebondsinatetrahedronarearrangedsothattheirpolaritiescancelexactlyi.e.thetetrahedralmolecule
CCl4hasnodipolemoment.

Theperfectsymmetryofthesegeometricformsisdisruptedwhenalonepairreplacesabond,givinga
moleculewithadipolemoment.ExamplesincludeSF4(seesaw),ClF3(Tshape),NH3(trigonalpyramid)
andH2O(bent),allofwhichhavedipolemoments.Replacingoneormorebondswithabondtoa
differentkindofatomalsointroducesadipolemomentbecausethesymmetryislowered.Thus,
chloroform,CHCl3,hasadipolemomentbutCCl4doesnot.Thecarbonatomofchloroformhasfour
bondsinanearregulartetrahedron,butthefourbondsarenotidentical.TheCClbondsaremorepolar
thantheCHbond,sothepolaritiesofthefourbondsdonotcancel.Figure5.22showsthemagnitude
anddirectionofthedipolemomentinchloroform(=3.4710 30Cm).

FIGURE5.22Carbontetrachloride,CCl4 ,isasymmetricaltetrahedralmolecule,sotheindividualbond
polaritiescancel.Chloroform,CHCl3 ,isalsoatetrahedralmolecule,butthefourbondsarenot
identical,sothebondpolaritiesdonotcancel.

InasymmetricaloctahedralsystemsuchasSF6,eachpolarSFbondhasacounterpartpointinginthe
oppositedirection.Thebondpolaritiescancelinpairs,leavingthismoleculewithoutadipolemoment.

WORKEDEXAMPLE5.5

PredictingDipoleMoments
DoeseitherClF5orXeF4haveadipolemoment?

Analysis

Moleculescomposedofatomswithdifferentelectronegativitieshavedipolemomentsunless
theirsymmetriesaresufficienttocanceltheirbondpolarities.Therefore,wemustexamineeach
molecularstructureandtheorientationofthebondsineachmolecule.

Solution

Themolecularstructuresofchlorinepentafluorideandxenontetrafluorideareshowninfigure
5.19.Eachhassixsetsofelectronpairsaroundaninneratom,buttheseincludelonepairs.As
aresult,ClF5hasasquarepyramidalshape,whereasXeF4hasasquareplanarshape.Pictures
canhelpusdeterminewhetherornotthebondpolaritiescancel.
 Eachmoleculehasfourfluorineatomsatthecornersofasquare.TheXeFbondpolarities
cancelinpairs,leavingXeF4withoutadipolemoment.Fourbondpolaritiesalsocancelin
ClF5,butthefifthClFbondhasnocounterpartintheopposingdirection,soClF5hasa
dipolemomentthatpointsalongtheaxiscontainingthelonepairandthefifthClFbond.

Isouranswerreasonable?

Anymoleculeinwhichindividualdipolemomentsdonotcancelwillhaveanoveralldipole
moment.ItisthereforereasonablethatXeF4willhavenodipolemomentwhiletheless
symmetricClF5moleculewill.

PRACTICEEXERCISE5.5
Determinewhetherethane,C2H6,and
ethanol,C2H5OH,havedipolemoments.

BondLength
Aswedescribedinsection5.1,thebondlengthofacovalentbondisthenuclearseparationdistanceat
whichthemoleculeismoststable.TheHHbondlengthinmolecularhydrogenis74pm.Atthis
distance,attractiveinteractionsaremaximisedrelativetorepulsiveinteractions(seefigure5.2).Having
developedideasaboutLewisstructuresandmolecularshapes,wecannowexaminebondlengthsinmore
detail.

Table5.3listsaveragebondlengthsforthemostcommonchemicalbonds.Thetabledisplaysseveral
trends.Onetrendisthatbondsbecomelongerasatomsizeincreases,asshownbybondlengthsofthe
diatomichalogens.

TABLE5.3 Averagebondlengths(allvaluesareinpicometres,1pm=1012 m)

na(a) nb(a) Bondlengths

 HXbonds
1 1 HH 74
1 2 HC 109 HN 101 HO 96 HF 92
1 3 HSi 148 HP 144 HS 134 HCl 127
1 4 HBr 141
Secondrowelements
2 2 CC 154 CN 147 CO 143 CF 135
2 2 NN 145 OO 148 FF 142
2 3 CSi 185 CP 184 CS 182 CCl 177
2 3 OSi 166 OP 163 OS 158 NCl 175
2 3 FSi 157 FP 157 FS 156
2 4,5 FXe 190 CBr 194 CI 214
Largerelements
3 3 SiSi 235 PP 221 SS 205 ClCl 199
3 3 SiCl 202 PCl 203 SCl 207
4 4 BrBr 228
5 5 II 267
Multiplebonds
C C 133 C N 138 C O 120 O O 121
P O 150 S O 143
C C 120 C N 116 C O 113 N N 110

(a)n a istheprincipalquantumnumberforthefirstnamedatomandistheprincipalquantum
numberforthefirstnamedatomandn bisforthesecondatom.isforthesecondatom.

Thetrendisconsistentwithourintroductiontoorbitaloverlap.Recallthatbondinginvolvesvalence
orbitals,anditistheoccupiedvalenceorbitalsthatdeterminethesizeofanatom.

Bondpolarityalsocontributestobondlengthbecausepartialchargesgenerateelectrostaticattractionthat
pullstheatomsclosertogether.Forexample,noticeinTable5.3thatCNbondsareslightlyshorterthan
theaverageofCCandNNbonds.ThisisaresultofthepolarityoftheCNbond.

ThebondlengthsinTable5.3showonefinalfeature:amultiplebondisshorterthanthesinglebond
betweenthesametwoatoms.Thisisbecauseplacingadditionalelectronsbetweenatomsdecreases
internuclearrepulsion,leadingtoanincreaseinnetattraction,therebyallowingtheatomstocomecloser
together.Thus,triplebondsaretheshortestofallbondsamongsecondrowelements.

Becausebondlengthsdependonthenumberofelectronsinvolvedinthebond,wecanusebondlengths
todecidewhichLewisstructurebestrepresentstheactualelectrondistributioninamolecule.Sulfur
oxygenbondsprovideagoodexample.Figure5.23showstwopossiblesetsofLewisstructuresfor
speciesthatcontainsulfuroxygenbonds.Oneset,theunoptimisedstructures,placesoctetsofelectrons
ontheinnersulfuratom,whiletheotherset,theoptimisedstructures,reducestheformalchargeonsulfur
tozeroattheexpenseofexceedingtheoctetontheSatom.Asthefigureshows,thetwosetsofstructures
predictdifferentbondtypes.
 FIGURE5.23Unoptimisedstructuresandoptimisedstructurespredictdifferentbondtypesforsulfuroxygen
bonds.

WecanuseexperimentalbondlengthvaluestosupporttheoptimisedLewisstructures.Insulfuricacid,
therearetwodistinctlydifferentbondtypeswithbondlengthsof157pmand142pm.Inthesulfate
anion,allthebondlengthsare147pm,whilethebondlengthsinSO2andSO3are143pmand142pm,
respectively.Thesevaluesindicatethatabondlengthof157pmisconsistentwithanSOsinglebond,
and142pmwithanS Odoublebond.Abondlengthof147pmindicatesanintermediatebond
character(seeTable5.3).ThesevaluessupporttheoptimisedLewisstructures,asshowninfigure5.22,
whichpredictdoublebondsonlyforSO2andSO3,doubleandsinglebondsforH2SO4andintermediate
bondsforSO42.

Tosummarise,generallythefollowingfactorsinfluencebondlengths:
1.Foragivenpairofatoms,themoreelectronsinthebondbetweenthem,theshorterthebond.
2.Fortwoatomsjoinedbythesametypeofbond(single,doubleortriple),thelargerthe
electronegativitydifferencebetweenthebondedatoms,theshorterthebond.

WORKEDEXAMPLE5.6

BondLengths
Whatfactoraccountsforeachofthefollowingdifferencesinbondlength?
(a)I2hasalongerbondthanBr2.
(b)CNbondsareshorterthanCCbonds.
(c)HCbondsareshorterthantheC Obond.
(d)Thecarbonoxygenbondinformaldehyde,H2C O,islongerthanthebondincarbon
monoxide,C O.

Analysis

Bondlengthsarecontrolledbythreefactors,someofwhicharemoreinfluentialthanothers.
Toexplainadifferenceinbondlength,weneedtodeterminethewaythatthefactorsare
 balanced.

Solution
(a)II>BrBr.Iodineisjustbelowbromineintheperiodictable,sothevalenceorbitals
ofiodinearelargerthanthevalenceorbitalsofbromine.Thus,theI2bondislonger
thantheBr2bondbecauseiodinehasalargeratomicradius.
(b)CN<CC.Carbonandnitrogenarebothsecondrowelements.However,nitrogen
hasahighereffectivenuclearchargethancarbon,sonitrogenhasthesmallerradius.
ThismakesCNbondsshorterthanCCbonds.Inaddition,aCNbondispolar,
whichcontributestotheshorteningoftheCNbond.
(c)HC<C O.Here,wearecomparingbondsinwhichtheatomicradiiandthe
amountofmultiplebondinginfluencebondlength.TheexperimentalfactthatHC
bondsareshorterthanthetripleC Obondindicatesthatthesizeofthehydrogen
orbitalisamoreimportantfactorthanthepresenceofmultiplebondinginthiscase.
(d)C O>C O.Bothbondsarebetweencarbonandoxygen,son(theprincipal
quantumnumber,whichdeterminessize),atomicnumber(Z)andelectronegativity
difference()arethesame.However,carbonmonoxidecontainsatriplebond,
whereasformaldehydehasadoublebond.ThetriplebondinCOisshorterthanthe
doublebondinH2CObecausemoresharedelectronsmeansashorterbond.

Isouranswerreasonable?

Whenfactorsworkinthesamedirection(effectivenuclearchargeandbondpolarityinthe
caseofCN<CC),wecanmakeconfidentpredictions.Whenfactorsworkintheopposite
direction(nvalueandbondmultiplicityinthecaseofHC<C O),wecanexplainthe
observedvaluesbutcannotconfidentlypredictthem.

PRACTICEEXERCISE5.6
Whatfactoraccountsforeachofthe
followingdifferencesinbondlength?(a)The
C CbondislongerthantheC Cbond.
(b)TheCClbondisshorterthantheSiCl
bond.(c)TheCCbondislongerthantheO
Obond.

BondEnergy
Bondenergiesaredefinedastheamountofenergythatmustbesuppliedtobreakaparticularchemical
bond.Bondenergies,likebondlengths,varyinwaysthatcanbetracedtoatomicproperties,andthere
arethreeconsistenttrendsinbondenergies:
1.Bondenergiesincreaseasmoreelectronsaresharedbetweentheatoms.Sharedelectronsarethe
glueofchemicalbonding,sosharingmoreelectronsstrengthensthebond.
2.Bondenergiesincreaseastheelectronegativitydifference()betweenbondedatomsincreases.
Polarbondsgainstabilityfromtheelectrostaticattractionbetweenthenegativeandpositivepartial
 chargesaroundthebondedatoms.Bondsbetweenoxygenandothersecondperiodelements
exemplifythistrend(notethatthebondlengthsalsochangeslightly).

Bond Differenceinelectronegativity() Bondenergy(kJmol1)

OO 0.0 145
ON 0.5 200
OC 1.0 360

3.Bondenergiesdecreaseasbondsbecomelonger.Asatomsbecomelarger,theelectrondensityofa
bondisspreadoverawiderregion.Thisdecreasesthenetattractionbetweentheelectronsandthe
nuclei.Thefollowingtableofbondenergiesillustratesthiseffect(notethattheelectronegativity
differencealsochanges,strengtheningthetrend).

Bond Bondlength(pm) Bondenergy(kJmol1)

HF 92 565
HCl 127 430
HBr 141 360
HI 161 295

Likebondlengths,bondenergiesresultfromtheinterplayofseveralfactors,includingeffectivenuclear
charge,principalquantumnumber,electrostaticforcesandelectronegativity.Thus,itisnotsurprisingthat
therearenumerousexceptionstothesethreetrendsinbondenergiesas,inmostcases,morethanoneof
thedeterminingfactorschangesatthesametime(seetablesabove)andoftennotwiththesameinfluence
onbondenergies.Althoughitispossibletoexplainmanydifferencesinbondenergy,itfrequentlyisnot
possibletopredictdifferenceswithconfidence.t

SummaryofMolecularShapes
Table5.4summarisestherelationshipsbetweennumberofsetsofelectronpairs,thegeometryofthesets
ofelectronpairsandmolecularshape.Ifyourememberthegeometryassociatedwitheachnumberofsets
ofelectronpairs,youcandeducemolecularshapes,bondanglesandtheexistenceofdipolemoments.
TABLE5.4 Featuresofmoleculargeometries
Number
ofsets Geometry
of Number ofsetsof
electron ofouter Lone electron Molecular Bond Dipole
pairs atoms pairs pairs shape angles moment(a) Example
2 2 0 linear linear 180 no

CO2

3 3 0 trigonal trigonal 120 no

planar planar

BF3

2 1 trigonal bent <120 yes

 planar

NO2(plusother
resonance
structures)
4 4 0 tetrahedral tetrahedral 109.5 no

CH4

3 1 tetrahedral trigonal <109.5 yes

pyramidal

NH3

2 2 tetrahedral bent <109.5 yes

H2O
5 5 0 trigonal trigonal 90, no
bipyramidal bipyramidal 120

PCl5
4 1 trigonal seesaw <90, yes
bipyramidal <120

SF4
3 2 trigonal Tshaped <90, yes
bipyramidal <120

ClF3
2 3 trigonal linear 180 no
bipyramidal
I3

6 6 0 octahedral octahedral 90 no

SF6
5 1 octahedral square <90 yes
pyramidal

ClF5

4 2 octahedral square 90 no
planar
 XeF4

(a)Appliesonlytomoleculeswithidenticalouteratoms.

Thisrelativelysmallcatalogueofmolecularshapesaccountsforaremarkablenumberofmolecules.Even
complicatedmoleculessuchasproteinsandotherpolymershaveshapesthatcanbetracedbacktothese
relativelysimpletemplates.Theoverallshapeofalargemoleculeisacompositeoftheshapesassociated
withitsinneratoms,withtheshapearoundeachinneratomdeterminedbythenumberofsetsof
surroundingbondingelectronpairsandthenumberoflonepairs.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.6ValenceBondTheory
Lewisstructuresareblueprintsthatshowthedistributionofvalenceelectronsinmolecules.However,the
dotsandlinesofaLewisstructuredonotshowhowbondsform,howmoleculesreactortheshapeofa
molecule.Inthisrespect,aLewisstructureisliketheelectronconfigurationofanatombothtellusabout
electrondistributions,butneitherprovidesdetaileddescriptions.Justasweneedatomicorbitalsto
understandhowelectronsaredistributedinanatom,weneedanorbitalviewtounderstandhowelectrons
aredistributedinamolecule.

Intheremainderofthischapterwedescribetwowaystothinkaboutcovalentbonding:valencebond
theory,whichuseslocalisedbonds,andmolecularorbitaltheory,whichusesdelocalisedbonds.The
valencebondapproachtomoleculesassumesthatelectronsareeitherlocalisedinbondsbetweentwoatoms
orlocalisedonasingleatom,usuallyinpairs.Accordingly,thelocalisedbondingmodeldevelopsorbitals
oftwotypes.Onetypeisabondingorbitalthathashighelectrondensitybetweentwoatoms.Theothertype
isanorbitallocatedonasingleatom.Inotherwords,anyelectronisrestrictedtotheregionaroundasingle
atom,eitherinabondtoanotheratomorinanonbondingorbital.

Localisedbondsareeasytoapply,eventoverycomplexmolecules,andtheydoanexcellentjobof
explainingmuchchemicalbehaviour.Inmanyinstances,however,localisedbondsareinsufficientto
explainmolecularpropertiesandchemicalreactivity.Wethereforealsoshowhowtoconstructdelocalised
bondsthatspreadoverseveralatomsusingmolecularorbitaltheory.Delocalisationrequiresamore
complicatedanalysis,butitexplainschemicalpropertiesthatlocalisedbondscannot.

OrbitalOverlap
Asdescribedearlierinthischapter,theelectronsinahydrogenmoleculearelocatedbetweenthetwonuclei
inawaythatmaximiseselectronnucleusattraction.Tounderstandchemicalbonding,wemustdevelopa
neworbitalmodelthataccountsforsharedelectrons.Inotherwords,weneedtodevelopasetofbonding
orbitals.

Themodelofbondingusedbymostchemistsisanextensionoftheatomictheorythatincorporatesa
numberofimportantideasfromchapters1and4.Bondingorbitalsarecreatedbycombiningatomic
orbitals.Rememberthatorbitalshavewavelikeproperties.Wavesinteract,resultinginadditionoftheir
amplitudes.Twowavesthatoccupythesameregionofspacewillbesuperimposed,generatinganewwave
thatisacompositeoftheoriginalwaves.Inregionswheretheamplitudesofthesuperimposedwaveshave
thesamephase,additionoftheamplitudesofthewavesleadstoconstructiveoverlap.Thisgivesanew
waveamplitudethatislargerthaneitheroriginalwaveinthatregion,asfigure5.24ashows.Inregions
wheretheamplitudeshaveoppositephases,additionoftheamplitudesofthewavesleadstodestructive
overlap,givinganewwaveamplitudethatissmallerthaneitheroftheoriginalwaves,asillustratedinfigure
5.24b.
 FIGURE5.24 (a)Whentwowaves(dashedlines)haveamplitudesofthesamephase,additiongivesanew
wave(solidline)withalargeamplitudeintheoverlapregion.
(b)Whentwowaves(dashedlines)haveamplitudesofoppositephases,additiongivesanew
wave(solidline)withasmallamplitudeintheoverlapregion.

Becauseelectronshavewavelikeproperties,orbitalinteractionsinvolvesimilaradditionorsubtractionof
wavefunctions.Whentwoorbitalsofthesamephasearesuperimposed,theresultisaneworbitalthatisa
compositeoftheoriginals,asshownformolecularhydrogeninfigure5.25.Thisinteractioniscalledorbital
overlap,andisthefoundationofthebondingmodelswewilldescribe.

FIGURE5.25Astwohydrogenatomsapproacheachother,theoverlapoftheir1satomicorbitalsincreases.The
waveamplitudesaddtogenerateaneworbitalwithhighelectrondensitybetweenthenuclei.

ConventionsoftheOrbitalOverlapModel
Orbitaloverlapmodelsproceedfromthefollowingassumptions:
1.Eachelectroninamoleculeisassignedtoaspecificorbital.
2.NotwoelectronsinamoleculehaveidenticaldescriptionsbecausethePauliexclusionprinciple
(chapter4)appliestoelectronsinmoleculesaswellasinatoms.
3.TheelectronsinmoleculesobeytheAufbauprinciple(chapter4),meaningthat,inthegroundstate,
theyoccupythelowestenergyorbitalsavailabletothem.
4.Onlythevalenceorbitalsareneededtodescribebonding.

Bondinginvolvesthevalenceorbitalsexclusivelyinthismodel,becausetheseorbitalshavetheappropriate
sizesandenergiestointeractstrongly.Wehavealreadyseenexamplesoftheoverlapofvalenceatomic
orbitalsintheH2andF2moleculesearlierinthischapter,andthissimpleapproachisperfectlyadequatefor
thesesmalldiatomicmolecules.Thereare,however,instanceswherethissimplemodeldoesnotreproduce
theexperimentallydeterminedstructuresofcertainmolecules.Forexample,ifweconsiderthebondingina
watermoleculetoarisefromoverlapofthevalenceatomicorbitalsonOandH,wefindthatwecannot
reproducethe104.5HOHbondangle.Thetwosinglyoccupiedporbitalsonoxygenlieat90toeach
other,andoverlapofthesewiththeH1sorbitalsshouldgiveabondangleof90.
Valencebondtheoryrecognisesthisproblem,andattemptstosolveitbyconstructinghybridorbitalsfrom
valenceatomicorbitals.Thisapproachgivesmuchbetteragreementwithexperiments,andisoutlinedin
detailonthefollowingpages,withparticularemphasisonthetetrahedralmoleculemethane.

HybridisationofAtomicOrbitals
Theexperimentallydeterminedstructureofmethaneisshowninfigure5.26.Methaneadoptsatetrahedral
moleculargeometrywithHCHbondanglesof109.5andtheHatomssituatedattheverticesofa
tetrahedron.Ifweconsiderthebondinginmethanesolelyintermsoftheoverlapofatomicvalenceorbitals,
wequicklycometotheconclusionthatsuchamodelcouldnotreproducethesebondanglesthethree2p
orbitalsonCareat90toeachother,whilethe2sorbitalhasnodirectionalpreference,andwewould
thereforeexpectastructurewiththreeofthefourCHbondsat90toeachother.Obviouslythissimple
modelisinadequatetodescribethebondinginmethane.Wecan,however,usetheindividualvalence
atomicorbitalsasastartingpointtoconstructhybridorbitals.Thesearecombinationsofatomicorbitals
andtheprocessbywhichwecombinethemiscalledhydridisation.Weillustratethiswithmethane.

FIGURE5.26Theexperimentallydeterminedstructureofmethane.Themoleculehasatetrahedralgeometrywith
109.5bondangles.

Methane:sp3HybridOrbitals
Toconstructhybridorbitals,wefirstneedtoidentifythevalenceatomicorbitalsthatwewilluse.Carbon
hastheelectronconfiguration1s22s22p 2,whichmeansthatthevalenceorbitalsofinterestaretheone2sand
three2porbitals.Wethenmixthesefouratomicorbitalstoformfournewhybridorbitalsthatarecalled
sp 3hybridorbitals.Recallfromchapter4thataporbitalhastwolobesofoppositephase(indicatedin
figure5.27aaspinkandbluelobes).Ifweimagineplacingansandaporbitalsuchthattheircentres
coincide,oneoftheselobeswillinteractconstructivelywiththesorbitalandwillthereforebeenhanced,
whiletheotherwillinteractdestructivelyandbediminished.Thenamesp 3referstothefactthatthefour
hybridorbitalsareconstructedfromonesandthreepatomicorbitals.Equally,andpossiblymore
instructively,itcanalsobeinterpretedaseachindividualsp 3hybridorbitalhaving characterand
character.Figure5.27ashowstheshapeofsp 3hybridorbitals,andalsoshowsdiagrammaticallythe
processbywhichtheyareformed.
 FIGURE5.27 (a)Theformationoffoursp3 hybridorbitalsfromonesorbitalandthreeporbitals.
(b)Thetetrahedralarrangementofthefoursp3 hybridorbitals.Thesmallerlobesofopposite
phasehavebeenomittedforclarityastheyarenotsignificantlyinvolvedinanymajor
bondinginteractions.

Theenergyleveldiagramforthisprocessisshowninfigure5.28.

FIGURE5.28Energyleveldiagramfortheformationoffoursp3 hybridorbitalsfromone2sandthree2patomic
valenceorbitals.

Becausewecanneithercreatenordestroyenergy,thetotalenergyofthefouratomicorbitalsmustequalthe
totalenergyofthefourhybridorbitals.Thismeansthattheenergyofthesp 3hybridorbitalsmustlie
betweentheenergiesofthe2sand2patomicorbitals.Specifically,theenergyofeachsp 3hybridorbital
mustbe .Asthefourhybridorbitalsaredegenerate,eachofthemaccommodatesonevalence
electron.

Thefoursp 3hybridorbitalsarearrangedsuchthattheirelectronsundergotheminimumrepulsion.This
resultsinatetrahedralarrangementinwhicheachhybridorbitalpointstowardsadifferentcornerofa
tetrahedron.Everyhybridorbitalisdirectional,withalobeofhighelectrondensitypointinginonespecific
direction,asshowninfigure5.27b.

Wecannowcompleteourmodelofmethane.Weoverlapeachsinglyoccupiedsp 3hybridorbitalwithone
singlyoccupied1sorbitalofaHatom.Thisleadstotheformationoffouridenticalbondsandaregular
tetrahedralshapeforthemolecule,asshowninfigure5.29.
 FIGURE5.29Methaneformsfromorbitaloverlapbetweenthehydrogen1sorbitalsandthesp3 hybridorbitalsofthe
carbonatom.Note:Thelargelobesofthesp3 orbitalsandthehydrogensorbitalsshownareofthe
samephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephaseforthe
sp3 hybridorbitalshavebeenomitted.

Notethatsp 3hybridisationisnotlimitedtoCatoms.Infact,anyatomwhichexhibitsatetrahedral(ornearly
so)arrangementofelectronpairscanbeconsideredtobesp 3hybridised.Thisisillustratedinworked
example5.7forthehydroniumioninwhichtheOatomissp 3hybridised.

WORKEDEXAMPLE5.7

BondingintheHydroniumIon

Describethebondingofthehydroniumion,H3O+,intermsofhybridorbitals.

Analysis

DeterminetheLewisstructuretoconfirmthattheinnerOatomissurroundedbyfoursetsof
electronpairs,whichwilladoptanearlytetrahedralgeometry.Thissuggestssp 3hybridisationof
theOatom.Thenconstructthefoursp 3hybridorbitalsfromtheappropriateatomicorbitalson
theOatom.

Solution

WehavedeterminedtheLewisstructureofthehydroniumionbefore(workedexample5.4).
AstheinneratomisO,weusethe2sand2patomicorbitalstoconstructthesp 3hybridorbitals.
Thesewillcontainatotalofsixelectrons.

Wehavetwohalfoccupiedsp 3hybridorbitalsthatcanoverlapwithtwohalfoccupied1sorbitals
onHtoformtwoOHbonds.Weformthethirdbondbyoverlappingoneofthefullsp 3
orbitalswithanempty1sorbitalonanH+ion.Althoughbothelectronsinthisbondderive
formallyfromtheOatom,thebondisidenticaltotheothertwoOHbonds.Thisleavesansp 3
hybridorbitalnotinvolvedinbonding,whichcontainstwoelectrons.Theseelectronsconstitutea
lonepairontheOatom.Wecanvisualisethebondingsituationas:

Note:Thelargelobesofthesp 3orbitalsandthehydrogensorbitalsshownareofthesamephase.
Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephaseforthesp 3
hybridorbitalshavebeenomitted.

Isouranswerreasonable?

Ourbondingdescriptionaccountsforthetrigonalpyramidalshapeofthehydroniumion.This
exampleprovidesanexcellentillustrationofhowvalencebondtheorycanaccountforthe
presenceoflonepairsinamolecule.TheactualHOHbondanglesinthehydroniumionwill
beslightlylessthantheidealised109.5 oduetothepresenceofthelonepair.
 PRACTICEEXERCISE5.7
Describethebondinginawatermoleculein
termsofhybridorbitals.

Notethat,inmethane,thenumberofhybridisedvalenceatomicorbitalsequalsthenumberofvalence
atomicorbitalsparticipatinginhybridisation.Thisisalwaysthecase,regardlessofthenatureofthe
hybridisation.Forexample,aswewillseelater,hybridisationofthreeatomicorbitalsgivesthreesp 2hybrid
orbitals,whilehybridisationoftwoatomicorbitalsgivestwosphybridorbitals.

Tothispoint,wehaveconsideredonlymoleculesinwhichhybridorbitalsontheinneratomoverlapwithH
1satomicorbitals.Incaseswheretheouteratomsarenothydrogen,wealsohybridisetheseatomstoobtain
abetterdescriptionofthegeometryofanylonepairspresent.Wecanillustratethiswithreferencetothe
dichloromethanemolecule,CH2Cl2,theLewisstructureofwhichis:

WehybridisetheinnerCatomtogeneratefoursinglyoccupiedsp 3hybridorbitals,andwecangeneratetwo
CHbondsbyoverlappingthesewithtwosinglyoccupiedH1sorbitals.WecouldalsoformtheCCl
bondsbyoverlappingtheremainingtwohybridorbitalswiththesinglyoccupiedporbitaloneachoftwoCl
atoms.However,theproblemwiththisapproachisthesameasthatwhichledustohybridiseatomicorbitals
inthefirstplaceitleadstoanincorrectgeometryofelectronpairs(inthiscase,thethreelonepairson
eachClatom).WecanhybridisethevalenceorbitalsonClinthesamewayaswehavedonepreviouslyfor
C,asshowninfigure5.30.

FIGURE5.30Energyleveldiagramfortheformationofsp3 hybridorbitalsonClfromthe3sand3pvalence
atomicorbitals.

Thishybridisationgivesonesinglyoccupiedsp 3hybridorbitaloneachClatom,whichcanoverlapwiththe
sp 3hybridorbitalsonthecarbonatomtoformtwoCClbonds.Giventhatthesp 3hybridorbitalsonthe
chlorineatomaretetrahedrallydisposed,thethreelonepairswillbeatapproximately109.5toeachother.
sp2hybridorbitals
Borontrifluorideappearsinsection5.4asanexampleofamoleculewheretheinneratomhasthreesetsof
electronpairsinatrigonalplanargeometry,with120anglesseparatingthethreeBFbonds.Ifwewereto
treatthebondinginBF3solelyintermsofoverlapofatomicvalenceorbitals,wewouldpredictbondangles
closeto90.Asetofsp 3hybridsisalsonotappropriate,becausethesewouldgiveFBFbondanglesof
109.5ratherthan120.Weneedadifferentsetofhybridorbitalstorepresentanatomwithtrigonalplanar
geometry.Inthiscasewecangenerateasetofthreesp 2hybridorbitalsbymixingthe2sorbitalwithtwo
2porbitalsontheboronatom.Werepresentthisprocessinfigure5.31,inwhicheachresultingsp 2hybrid
orbitalhas and character.

FIGURE5.31 (a)Theformationofthreesp2 hybridorbitalsfromonesorbitalandtwoporbitals.

(b)Theorientationofthethreesp2 hybridorbitals.Theylieinthesameplaneatanangleof
120toeachother.Thesmallerlobesofoppositephasehavebeenomittedforclarityasthey
arenotinvolvedinthemajorbondinginteraction.

Althoughanindividualsp 2hybridorbitallooksverymuchlikeitssp 3counterpart,theenergeticsofthe

hybridisationprocessarequitedifferent,asshowninfigure5.32.
 FIGURE5.32Energyleveldiagramfortheformationofsp2 hybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonaBatom.

Thethreesp 2hybridorbitalsarecoplanar,andarepositionedatanglesof120toeachotheraroundtheB
atom.Asweuseonlytwoofthethree2porbitalsinconstructingthesp 2hybridorbitals,thisleavesone
orbital(byconvention,thep z)unhybridised.Figure5.33showsthearrangementofalltheorbitals.

FIGURE5.33Ansp2 hybridisedatomhasthreecoplanarhybridorbitalsseparatedby120angles.One
unchangedporbitalisperpendiculartotheplaneofthehybridorbitals.Note:Apartfromonehalf
(pinkorblue)oftheunhybridisedpzatomicorbital,allorbitalsareofthesamephase.Thedifferent
coloursareusedforclarityonly.Diminishedlobesofoppositephasehavebeenomitted.

WealsohybridisetheFatoms.EachFatomissurroundedbyfourelectronpairs,whichmeanstheatoms
willbesp 3hybridised,andtheprocessisentirelyanalogoustothatusedpreviouslyfortheClatomsin
CH2Cl2.Wenowoverlapeachofthethreesinglyoccupiedsp 2hybridorbitalswithasinglyoccupiedsp 3
hybridorbitalonafluorineatomtoformthethreeidenticalBFbonds.

Thepresenceoftheunoccupiedp zorbitalontheBatomhassignificantconsequencesforthereactivityof
BF3.BF3oftenreactsveryeasilywithmoleculesthathavealonepairofelectrons,suchasNH3.Thep z
orbitalservestoacceptthepairofelectronsfromsuchmolecules,therebygivingtheBatomanoctetand
convertingittosp 3hybridisationintheprocess.
spHybridOrbitals
Berylliumhydrideappearsinsection5.4asanexampleofamoleculewithlineargeometry.Therearetwo
bondstotheberylliumatomandaHBeHbondangleof180.Todescribelinearorbitalgeometry,we
needahybridisationschemethatgeneratestwoorbitalspointinginoppositedirections.Wedothisby
hybridisingthe2sorbitalofBewithoneofthe2porbitalstogenerateapairofsphybridorbitals.We
representthisprocessinfigure5.34,inwhicheachsphybridorbitalhas characterand character.

FIGURE5.34 (a)Theformationoftwosphybridorbitalsfromonesorbitalandoneporbital.
(b)Theorientationofthetwosphybridorbitals.Theylieatanangleof180toeachother.The
smallerlobeshavebeenomittedforclarityastheyarenotinvolvedinthemajorbonding
interaction.

Figure5.35showstheenergeticsofthehybridisationprocess.Inthiscase,weuseonlyoneoftheporbitals,
whichleavestwoofthemunhybridised.

FIGURE5.35Energyleveldiagramfortheformationofsphybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonBe.

Thetwosphybridorbitalsareorientedat180fromeachother,whichleadstoalinearshapeforthe
molecule.WeformtwoidenticalBeHbondsbyoverlappingeachhalffilledhybridorbitalwithone
halffilled1sorbitalonaHatom.NotethatwecannothybridisetheouterHatoms,astheyhaveonlya1s
orbitaleach.Figure5.36showsadiagramofthebondingforBeH2.Notethatthetwounoccupiedand
unhybridisedporbitalslieperpendiculartoeachother.Wewillseehowsuchorbitalscanparticipatein
bondingwhenweconsidertriplybondedmoleculeslaterinthischapter.
 FIGURE5.36ThebondinginBeH2 .Note:Thelargelobesofthesp3 orbitalsandthehydrogensorbitalsshown
areofthesamephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofopposite
phaseinthesphybridorbitalshavebeenomitted.

Table5.5summarisesthehybridisationschemeswehaveencounteredsofar.Whileotherhybridisation
schemesarerequiredtodescribethebondinginmoleculeswithcoordinationnumbershigherthan4,sp,sp 2
andsp 3arebyfarthemostuseful,particularlytodescribethebondinginorganicmolecules.Multiple
bondingisoneofthefeaturesofmanyorganicmolecules.Onthefollowingpages,wewilllookatthis
phenomenonfromavalencebondpointofview.
TABLE5.5 Asummaryofvalenceorbitalhybridisation
Numberof Numberof
Numberofsetsof Electrongroup hybrid unusedp
electronpairs geometry Hybridisation orbitals orbitals Diagram(a)
2 linear sp 2 2

3 trigonalplanar sp 2 3 1

4 tetrahedral sp 3 4 0

(a)Apartfromonehalf(pinkorblue)oftheunhybridisedp zatomicorbital,allorbitalsareofthe
samephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephase
havealsobeenomitted.

MultipleBonds
ManyoftheLewisstructuresinthisbookrepresentmoleculesthatcontaindoubleandtriplebonds.From
simplemoleculessuchasetheneandethyne,tocomplexcompoundssuchaschlorophyllandvitaminB12,
multiplebondsareabundantinchemistry.Doubleandtriplebondscanbedescribedbyextendingthe
valencebondmodel.Webeginwithethene,asimplehydrocarbonwiththeformulaC2H4.

BondinginEthene
Ethene(ethylene)isacolourless,flammablegaswithaboilingpointof104Cthatispredominantlyusedin
themanufactureofplasticssuchaspolyethylene(seechapter26).Becauseethenestimulatesthebreakdown
ofcellwalls,itisusedcommerciallytospeeduptheripeningoffruit,particularlybananas.

EverydescriptionofbondingstartswithaLewisstructure.Ethenehas12valenceelectrons.Thebond
frameworkofthemoleculehasoneCCbondandfourCHbonds,requiring10oftheseelectrons.Ifwe
placethefinaltwoelectronsasalonepairononeofthecarbonatoms,thisgivesaformalchargeof1on
onecarbonatomand+1ontheother.Thesechargescanbeminimisedbyformingadoublebondbetween
thecarbonatoms,leavingthembothwithanoctetofelectrons.

Eachcarbonatomisthussurroundedbythreesetsofelectronpairs,whichimpliesthatthecarbonatomsare
sp 2hybridised,withatrigonalplanargeometry.(Recallfromp.176thatdoublebondsandtriplebondsare
treatedasbeingasinglesetofelectronpairs.)

Todevelopabondingpictureformoleculeswithmultiplebonds,westartbyconsideringonlythesingly
bondedframeworkofthemolecule,whichweconstructusinghybridorbitals.Theorbitaldiagramforan
sp 2hybridisedCatomisshowninfigure5.37andtheframeworkisshowninfigure5.38.Notethatthe
electronconfigurationontherighthandsideoffigure5.37violatestheAufbauprinciple.Thisisjustifiedas
theenergydifferencebetweenthesp 2orbitalsandthep zorbitalissmall,andthereforetheenergyrequired
topopulatethep zorbitalissmallerthanthespinpairingenergythatwouldotherwiseberequiredtooccupy
oneofthehybridorbitalswithtwoelectrons.Suchanelectronconfigurationprovidesuswithresultsthat
agreewithexperiments.

FIGURE5.37Energyleveldiagramfortheformationofsp2 hybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonC.

FIGURE5.38Theframeworkoftheethenemolecule.

Fortheframework,wemustformfourCHbondsandoneCCbond.Wecandothis,asshownin
figure5.39,byusingtwosp 2hybridorbitalsoneachcarbontoformtwoCHbonds,withtheCC
bondformedbyoverlapoftheremainingsp 2hybridorbitaloneachCatom.
 FIGURE5.39Orbitaloverlapsusedtoformtheframeworkofethene.Notethatallorbitalsshownareofthesame
phaseandcoloursareusedforclarityonly.

Havingconstructedtheframework,weareleftwithonehalfoccupiedp zorbitaloneachCatom,whichis
usedtoconstructthedoublebond.Aswehaveseenearlier,abondhasitsmaximumelectrondensity
alongtheinternuclearaxisbetweenthetwonuclei.Toconstructthedoublebond,weoverlapthetwop z
orbitalsinasidebysidefashiontoformapi()bond,asshowninfigure5.40.Abondhasitsmaximum
electrondensityaboveandbelowtheplaneofthenuclei,andhaszeroelectrondensityalongtheinter
nuclearaxisbetweenthenuclei.Adoublebondalwaysconsistsofonebondandonebond.Thebond
formsfromtheendonoverlapoftwohybridorbitals,andthebondformsfromthesidebysideoverlapof
twoatomicporbitals.Asthesidebysideoverlapisnotasefficientastheendonoverlap,doublebondsare
nottwiceasstrongassinglebondsbetweenthesameatoms.Figure5.40showsthecompleteorbitalpicture
ofthebondinginethene.Etheneisthesimplestofaclassofmolecules,thealkenes,whichcontainC C
doublebonds.

FIGURE5.40 Orbitalpicturesofthebondinginethenefromthreeperspectives:
(a)viewofthepzatomicorbitalswhichoverlaptoformthebond,
(b)viewofthebondformedfromtheoverlapofthepzatomicorbitalsand
(c)thebondsuperimposedontheframework.Notethatthepinkandbluelobestogether
representasinglebond,whichisoccupiedbytwoelectrons.

Theavailabilityofanunhybridisedvalenceporbitaltoformbondsischaracteristicofsp 2hybridisation
andisnotrestrictedtocarbonatoms.ManyorganicmoleculescontainC NandC Odoublebondsand
wecandescribethebondinginsuchcompoundsinasimilarfashiontotheabovedescriptionofaC C
doublebond.

Tosummarise,wecanconstructthevalencebonddescriptionofanydoublebondusingthefollowingfour
stepprocedure:
1.DeterminetheLewisstructure.
2.UsetheLewisstructuretodeterminethetypeofhybridisation.
3.Constructthebondframework.
4.Addthebonds.
BondinginEthyne
Theethynemoleculemaybefamiliartoyoubyitsmorecommonnameacetylene,thegasusedin
oxyacetyleneweldingtorches.Ethynehas10valenceelectrons,andweusesixofthesetoformoneCC
bondandtwoCHbonds.ThisleaveseachCatominthemoleculewithashareofonlyfourelectrons.We
cancompletetheoctetofoneoftheCatomsbyallocatingtheremainingfourelectronstoitintheformof
twolonepairs.However,thisleadstoa2chargeonthisandaformalchargeof+2ontheotherCatom.
ConvertingthetwolonepairsontheCatomtotwobondingpairssituatedbetweenthetwoCatoms,we
obtainformalchargesofzeroforallatomsinthemolecule.ThisproducesthefollowingLewisstructurein
whichthecarbonatomsarejoinedbyatriplebond.

Eachcarbonatomissurroundedbytwosetsofelectronpairs,andwewouldpredictalineargeometryfor
thismolecule.Wecanthereforeusesphybridorbitalstodescribethebondinginethyne.

Aswedidforethene,wefirstconstructthesinglybondedframeworkusingthehybridorbitals.Theorbital
diagramforansphybridisedCatomisshowninfigure5.41,andtheframeworkofethyneisshownin
figure5.42.

FIGURE5.41Energyleveldiagramfortheformationofsphybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonC.

FIGURE5.42Theframeworkoftheethynemolecule.

WeformtheframeworkbyformingtwoCHbondsandoneCCbondusingthesphybridorbitals,as
showninfigure5.43.

FIGURE5.43Orbitaloverlapsusedtoformtheframeworkofethyne.Allorbitalsareinthesamephasedifferent
coloursareusedforclarityonly.

ThisthenleavestwosinglyoccupiedporbitalsoneachCatom.Wecanformtwobondsbyoverlapping
thep y andp zorbitalsoneachCatominasidebysidefashion,asshowninfigure5.44.
 FIGURE5.44Overlappingnonhybridisedporbitalsformtheframeworkofethyne.

Thus,eachtriplebondhasoneCCbondandtwoCCbondsperpendiculartoeachother,whichis
alwaysthecaseinanyalkyne.Workedexample5.8treatsanothermoleculewithbondingthatcanbe
describedbysphybridorbitals.

WORKEDEXAMPLE5.8

OrbitalOverlapinTripleBonds
Hydrogencyanide,HCN,isanextremelypoisonousgas.Approximatelyhalfamilliontonnesof
HCNisproducedeachyear,mostofwhichisusedtopreparestartingmaterialsforpolymers.
ConstructacompletebondingpictureforHCNandsketchthevariousorbitals.

Analysis

Usethefourstepproceduredescribedpreviously.BeginwiththeLewisstructureforthe
molecule,andthenidentifytheappropriatehybridorbitals.Constructabondframework,and
completethebondingpicturebyassemblingthebondsfromtheunhybridisedporbitals.

Solution

ThefivestepsofourprocedureforwritingLewisstructuresleadtoatriplebondbetweencarbon
andnitrogen.

TheinnerCatomissurroundedbytwosetsofelectronpairs,asistheNatom.Theseatomscan
thereforebeconsideredtobesphybridised.Wehavederivedtheorbitaldiagramforansp
hybridisedCatompreviously,whilethatforanspNatomisshownbelow.

Weformthelinearsinglybondedframeworkshownbelowbyoverlappingoneofthesphybrid
 orbitalsonCwiththe1sorbitalontheHatomtogiveaCHbond.Similarly,weformaCN
bondbyoverlappingtheothersphybridorbitalontheCatomwiththesinglyoccupiedsp
hybridorbitalontheNatom.

ThisleavestwosinglyoccupiedporbitalsonCandtwosinglyoccupiedporbitalsontheNatom
withwhichwecanconstructtheC Ntriplebond,inthesamewayasdescribedpreviouslyfor
ethyne.WearethenleftwithansphybridorbitalcontainingtwoelectronssituatedontheN
atom.Thisisanonbondinglonepairandisshowninthediagrambelowingold,forclarity.

Isouranswerreasonable?

Wehavealreadyshownthatatriplebondconsistsofoneandtwobonds,whichiswhatwe
havederived.OurbondingschemealsoaccountsforthepresenceofalonepairontheNatom,
soitisconsistentwiththeexperimentallydeterminedstructure.

PRACTICEEXERCISE5.8
Describethebondinginthebut2yne
molecule,CH3C CCH3,usingvalencebond
theory,andsketchtheorbitalsinvolved.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.7MolecularOrbitalTheory:DiatomicMolecules
Hybridorbitalsandlocalisedbondsprovideamodelofbondingthatcanbeeasilyappliedtoawiderangeof
molecules.Usingthismodelwedoanexcellentjobofrationalisingandpredictingchemicalstructures,butlocalised
bondscannotpredictorinterpretallaspectsofbondingandreactivity.Forexample,whilevalencebondtheory
predictsthegeometryofthemethanemoleculeperfectly,itcannotexplainthefactthatthefourvalenceorbitalsinthis
moleculearenotdegenerate.ItalsofailstoexplainwhythereareunpairedelectronsinamoleculeofO2.Inthis
sectionweintroducemolecularorbitaltheory,apowerfultheoryofbondingthatismoresuccessfulthanvalence
bondtheoryinpredictingandexplainingmolecularproperties.Molecularorbitaltheorydiffersfundamentallyfrom
valencebondtheoryinthattheelectronswithinamoleculearenotlocalisedeitherononeatomorbetweentwoatoms
insteadtheyoccupymolecularorbitals(MOs)thatcancovertheentiremolecule.

Althoughmolecularorbitaltheoryismorecomplexthanthehybridorbitalapproach,wecanillustratethe
fundamentalsofthetheorywithreferencetosimplediatomicmolecules.

MolecularOrbitalsofH2andHe2

Molecularorbitaltheoryconsiderstheformationofmolecularorbitalsfromtheoverlapofatomicorbitalsonallofthe
individualatomsinthemolecule.TheoverlapofNatomicorbitalswillalwaysleadtotheformationofNmolecular
orbitals.Becauseofthelargenumberofpossibleoverlapsinevenquitesmallmolecules,wewillrestrictour
discussiontodiatomicmolecules,andwillfirstconsiderthemolecularorbitaltreatmentoftheH2molecule.

WecanconsidertheMOsofH2tobeformedfromtheoverlapofthe1sorbitalsontheHatoms.Aseachatomic
orbitalcanhaveeitherapositiveornegativephase,therearetwopossiblewaysinwhichtheseatomicorbitalscan
overlapbothorbitalscanhavethesamephase(inphaseoverlap)ortheycanhaveoppositephases(outofphase
overlap).Inphaseoverlapisconstructiveandresultsintheformationofamolecularorbitalwithalargeamplitude,
andconsequentlyhighelectrondensity,betweenthenuclei.Outofphaseoverlapisdestructiveandgivesamolecular
orbitalwithzeroamplitude,andthereforezeroelectrondensity,exactlyhalfwaybetweenthenuclei.Asforatomic
orbitals,thispositionwheretheamplitudechangesphaseiscalledanode.Theseoverlapsandtheresultingmolecular
orbitalsareshowninfigures5.24and5.45.

FIGURE5.45Whentwohydrogen1satomicorbitalsinteract,theygeneratetwomolecularorbitals,onebonding(1s)and
oneantibonding .

Constructiveoverlapgivesabondingmolecularorbital,inwhichelectrondensityismaximisedbetweenthetwo
nuclei.Suchanarrangementofelectronsminimisesinternuclearrepulsions.Theorbitaliscompletelysymmetricwith
respecttorotationaroundtheinternuclearaxisandisthereforeaorbital.Weusea1ssubscripttoshowthatit
derivesfromtheoverlapoftwo1satomicorbitals,andthecompletedescriptionofthisorbitalistherefore1s.

Destructiveoverlapgivesanantibondingmolecularorbitalinwhichelectrondensityisminimisedbetweenthe
nucleiandiszeroatthenodebetweenthenuclei(allantibondingorbitalshavemorenodesthanthecorresponding
bondingorbitalsandarethereforeofhigherenergy.).Internuclearrepulsionsarethereforesignificantastheyarenot
mediatedbytheelectrons.Astheorbitaliscompletelysymmetricwithrespecttorotationabouttheinternuclearaxis,it
isaorbital.Weuseasuperscriptasterisk(*)todenoteitsantibondingnatureandagainuseasubscript1stoshow
thatitisderivedfromtwo1satomicorbitals.Thecompletedescriptionofthisorbitalistherefore .
Therelativeenergiesofatomicorbitalsandthemolecularorbitalstheyformareshowninamolecularorbital
diagram.Figure5.46showsthemolecularorbitaldiagramforH2.Itshowsthatthebondingorbitalisoflowerenergy
thantheorbitalsfromwhichitisformed,whereastheantibondingorbitalisofhigherenergy.Whenahydrogen
moleculeforms,itstwoelectronsobeythesameprinciplesfordistributingelectronsasdescribedinchapter4.The
lowestenergyarrangementofelectronsrequiresadherencetotheAufbauprinciple,thePauliexclusionprincipleand
Hund'srule,nomatterwhattypesoforbitalstheyoccupy.Thetwovalenceelectronsofmolecularhydrogentherefore
fillthelowestenergyorbital,the1sorbital,withtheirspinspaired,leavingthe orbitalempty.

FIGURE5.46Molecularorbitaldiagramformolecularhydrogen.

Themolecularorbitaldiagramshowninfigure5.46appliestoalldiatomicspeciesfromthefirstrowoftheperiodic
table,exceptthattheelectronoccupancyandtheabsoluteenergiesinvolvedaredifferent.Wecan,forinstance,use
molecularorbitaltheorytorationalisewhytwoheliumatomsdonotcombinetoformamoleculeofHe2.Theelectron
configurationofHeis1s2andthereforethehypotheticalHe2moleculewouldhavefourelectrons.Twoofthesewould
populatethebonding1sorbital,whiletheremainingtwoelectronswouldhavetooccupytheantibonding orbital,
asshowninfigure5.47.ThetotalelectronicenergyoftheHe2moleculewouldthereforebeexactlythesameasthat
oftwoisolatedHeatoms,asthedestabilisingeffectoftheelectronsintheantibondingorbitalcancelsoutany
stabilisationduetotheelectronsinthebondingorbital.Asthereisnoenergeticadvantage,amoleculeisnotformed
(seethediscussionofentropyinchapter8foranexplanation).Aconvenientwaytosummarisethisargumentisby
calculatingthebondorder,whichrepresentsthenetamountofbondingbetweentwoatoms.

FIGURE5.47DiatomicHe2 doesnotexistbecausethestabilityimpartedbytheelectronsinbondingorbitalsisoffsetbythe
destabilisationduetotheelectronsinantibondingorbitals.

Bondordersusuallyhaveintegerorhalfintegervalues:thelargerthebondorder,thestrongerthebond(forthesame
typeofatom).

Formolecularhydrogen,withtwobondingelectronsandnoelectronsintheantibondingorbitals,thebondorderis
.Abondorderof1correspondstoasinglebond,consistentwiththeLewisstructureofH2.Forthe

hypotheticalHe2molecule,twobondingandtwoantibondingelectronsgiveabondorderof ,sono
bondformsandheliumdoesnotformstablediatomicmolecules.

WORKEDEXAMPLE5.9

DoesHe2+Exist?

UseamolecularorbitaldiagramtopredictifitispossibletoformtheHe2+cation.

Analysis

TheschematicMOdiagramshowninfigure5.46canbeappliedtoanyofthepossiblediatomicmolecules
orionsformedfromthefirstrowelements,hydrogenandhelium.CounttheelectronsofHe2+,placethe
electronsinthemolecularorbitaldiagramandcalculatethebondorder.Ifthebondorderisgreaterthan
zero,thespeciescanpotentiallyformundertherightconditions.

Solution

OneHeatomhastwoelectrons,soaHe2+cationhasthreeelectrons.FollowingtheAufbauprinciple,two
electronsfillthelowerenergy1sorbital,sothethirdmustbeplacedintheantibonding orbitalin
eitherspinorientation.

Thebondorderofthecationistherefore .Althoughabondorderof mightsoundunusual,

itisgreaterthanzeroandthereforewepredictthatHe2+,withanetbondorderof ,canbepreparedinthe
laboratoryunderappropriateconditions.

Isouranswerreasonable?

Upuntilthispoint,wehavediscussedonlysingle,doubleandtriplebonds,andhavenotencountered
bondswithnonintegerorders.Infact,suchbondsarequitecommoninchemistry.He2+canbeprepared
bypassinganelectricaldischargethroughasampleofheliumgas.TheHe2+ionisunstablebutsurvives
longenoughtoallowitsstudy.ThebonddissociationenergyofHe2+is250kJmol1,approximately60%
asstrongasthebondintheH2molecule,whichhasabondorderof1.
 PRACTICEEXERCISE5.9

Whichspecieshasthestrongerbond,H2orH2?
Useamolecularorbitaldiagramtosupportyour
answer.

MolecularOrbitalsofO2

Thenextstepinthedevelopmentofmolecularorbitaltheoryistoconsiderthemolecularorbitalsformedby
constructiveanddestructiveoverlapofatomicporbitals.Weusemolecularoxygen,O2,asacasestudy.

TheLewisstructureofO2showsthetwoatomsconnectedbyadoublebond,withtwononbondingelectronpairson
eachatom.NotethattherearenounpairedelectronsintheLewisstructure.

WederivethemolecularorbitaldiagramfortheO2moleculebyconsideringoverlapofonlythevalenceatomic
orbitalsonthetwooxygenatomsanexacttreatmentwouldalsoincludethecore1sorbitals,butwewillignorethese
intheinterestsofclarity.Eachoxygenatomhasfourvalenceorbitals,sothemolecularorbitaldiagramforO2will
containeightmolecularorbitals.Thefirstinteractioninvolvesthe2satomicorbitals.Thispairinteractsinexactlythe
samewayasthe1sorbitalsdescribedpreviouslyforH2.Theconstructiveoverlapgeneratesabondingsorbital,and
thedestructiveoverlapformsanantibonding orbital.Becauseofthelargersizeofthe2satomicorbitals,thesetwo
molecularorbitalsarelargerthantheirhydrogen1sand counterparts,buttheiroverallappearancesaresimilar.

Figure5.48showstheconstructionofthe2pbasedmolecularorbitals.Onepairofmolecularorbitalsformsfromend
onconstructiveanddestructiveoverlapofthep zorbitalsthatpointtowardseachotheralongthebondaxis(by
convention,thebondaxisischosentobethezaxis).Theseendonoverlapsgiveapairoforbitals,thebondingp
andtheantibonding asshowninfigure5.48a.(Notethatherewehavesimplylabelledthemolecularorbitalsasp
and ,ratherthan2pand forreasonswewillexplainonp.203.)Theremainingsetsofporbitalsundergo
constructiveanddestructiveoverlapinasidebysidefashiontoformpairsofmolecularorbitalswithelectrondensity
locatedprimarilyaboveandbelowtheinternuclearaxis.Suchmolecularorbitalsarecalledorbitals.Constructive
overlapgivesabondingorbital,whiledestructiveoverlapgivesanantibonding*orbital.Oneofthesepairscomes
fromoverlapofthep y orbitals,whiletheothercomesfromoverlapofthep x orbitals.Figure5.48bshowsonlythep y
pairoforbitals,whichwelabely thex pairoforbitalsderivedfromthep x atomicorbitalshasthesame
appearance,butisperpendiculartothey orbitals.Notethattheantibonding*orbitalcontainsanodebetweenthe
twoOatoms.
 FIGURE5.48 Constructiveanddestructiveoverlapofporbitalsleadtobondingandantibondingorbitals
(a)Endonoverlapofthepzorbitalsgivesorbitals.
(b)Sidebysideoverlapofthep atomicorbitalsgives and molecularorbitals.Similarcombinations
y y
ofpxorbitalswouldgivexand MOs.

TodrawthemolecularorbitaldiagramforO2,wemustfirstdeterminetherelativeenergiesofthemolecularorbitals.
Wecandothiswiththefollowingrules:
1.Thecoresand orbitalsderivedfromtheoverlapofthe1satomicorbitalsareoflowestenergyand
contributelittletobonding.Forthisreason,theyarenotshownexplicitly.
2.Thebondingsandantibonding orbitalsderivedfromtheoverlapofthe2sorbitalsareoflowerenergy
thananyofthesixmolecularorbitalsderivedfromthe2porbitals.Thisisbecausethe2sorbitalsthatgenerate
thesand orbitalsareoflowerenergythanthe2patomicorbitals.
3.Thex andy bondingorbitalsaredegenerate,becausethecorrespondingatomicporbitalsfromwhichtheyare
derivedaredegenerate.The and orbitalsaredegenerateforthesamereason.
 4.Theantibondingorbitalsformedfromtheatomic2porbitalsarehighestinenergy,withthe orbitalhigher
thanthedegenerate and pairoforbitals.

Afterapplyingthesefeatures,weareleftwiththebondingpandmolecularorbitals.Thesemustbeplacedbetween
and*,butwhichofthemislowerinenergy?Itcanbeshownmathematicallythatendonoverlapismore
efficientthansidebysideoverlap,whichsuggeststhattheporbitalshouldbeoflowerenergythantheorbitals.
ThisisthecasefortheO2moleculeandfigure5.49showsthecompletediagram.Toobtainthegroundstateelectron
configuration,weplacethe12valenceelectronsinthemolecularorbitalsinaccordancewiththePauliandAufbau
principlesandHund'srule.Wecandescribetheresultingelectronconfigurationbynamingtheorbitals(s,x etc.),
andusingsuperscriptstoshowhowmanyelectronseachorbitalcontains.Therefore,theconfigurationfortheground
stateofO2is:

FIGURE5.49ThemolecularorbitaldiagramforO2 .TheenergyorderingoftheMOsappliestosecondrowdiatomic
moleculeswithZ>7.

Notethat,tosatisfyHund'srule,wemustplaceoneelectronineachofthetwo*orbitalswithparallelspins.
Therefore,thismodelofbondingpredictsthatO2shouldcontaintwounpairedelectrons,incontrasttoboththeLewis
structureandthevalencebondtheory.Whichmodelagreeswithexperiment?

Figure5.50showsthatliquidoxygenadherestothepolesofamagnet.Attractiontoamagneticfieldshowsthat
molecularoxygenisparamagnetic.Recallfromchapter4thatparamagnetismariseswhentheelectronconfiguration
includesunpairedelectrons.NeithertheLewisstructureofO2northevalencebondmodelpredictsthepresenceof
unpairedelectrons.However,themolecularorbitaldescriptionshowsthatthetwohighestenergyelectronsofthe
oxygenmoleculeoccupythetwodegenerate and antibondingorbitals(figure5.50).So,molecularorbital
theorygivesusamoreappropriatemodelofthebondinginO2thaneithertheLewisorthevalencebondtheories.
Thisdoesnotnecessarilymeanthatthemolecularorbitaltheoryiscorrect,justthatitgivesbetteragreementwith
experimentthantheothermodels.

FIGURE5.50Molecularoxygenisparamagnetic,soitclingstothepolesofamagnet.

Bondlengthandbondenergymeasurementsonoxygenanditscationprovideevidencethatthe*orbitalsareindeed
antibonding.ThebondorderoftheO2moleculeis .IfweremoveanelectronfromO2,weformtheO2+
cation.ExperimentalmeasurementsshowthatthisspecieshasalargerbondenergyandshorterbondlengththanO2,
bothobservationsconsistentwithanincreasedbondorder.Thisindicatesthattheelectronremovedmustbe
antibondingincharacter,asitsremovalhasreducedtheamountofantibondingandstrengthenedthebond.

Species Bondlength Bondenergy Configuration Bondorder

O2 121pm 496kJmol1 (p)2(x )2(*x )1(*y )1 2

O2+ 112pm 643kJmol1 (p)2(x )2(y )2(*x,y )1 2.5

Molecularorbitaltheorypredictstheobservedincreaseinbondorder,withthecalculatedbondorderofO2+being
.TheexperimentaldatashowthatthehighestenergyorbitalofO2isantibondingincharacterandthe
theoreticalmolecularorbitalpredictionsareingoodagreement.

OurtreatmentofO2showsthattheextracomplexityofthemolecularorbitalapproachexplainsfeaturesthatasimpler
descriptionofbondingcannot.TheLewisstructureofO2doesnotrevealitstwounpairedelectrons,butamolecular
orbitalapproachdoes.ThesimpledescriptionofthedoublebondinO2doesnotpredictthatthebondinO2+is
strongerthanthatinO2,butamolecularorbitalapproachdoes.Wenowextendourdiscussiontoincludeallofthe
homonucleardiatomicmoleculesformedbyelementsinthesecondrowoftheperiodictable.

HomonuclearDiatomicMolecules

WesawpreviouslythatverysimilarmolecularorbitaldiagramscandescribethebondinginH2,He2+andHe2.Can
weusethemolecularorbitaldiagramforO2toexplainthebondinginallofthesecondrowdiatomicmolecules(Li2,
Be2,B2,C2,N2,O2,F2andNe2)?ConsidertheB2molecule,whichcanbeformedinthegasphasebystrongheating
ofsolidboron.IfweusethemolecularorbitaldiagramforO2andinsertthesixvalenceelectronsofB2,wewould
predicttheelectronconfiguration(s)2(s*)2(p)2forthismolecule.Withallitselectronspaired,B2shouldbe
diamagnetic.However,experimentsshowthatB2moleculesareparamagnetic,withtwounpairedelectrons.When
theoryandexperimentconflict,theorymustberevised.ThemolecularorbitaldiagramweusedforO2mustberevised
toaccountfortheparamagnetismofB2.

Theviewofmolecularorbitaltheorythatleadstothemolecularorbitaldiagraminfigure5.49assumesthatthe2sand
2porbitalsactindependently.Amorerefinedtreatmentconsidersinteractionsbetweenthe2sand2porbitals.Recall
fromchapter4thatthe2sand2porbitalshavesimilarradii.Consequently,whentwoatomsapproacheachother,the
2sorbitalononeatomwilloverlapnotonlywiththe2sorbital,butalsowiththe2p2zorbitaloftheotheratom.This
mixedinteractionof2sand2p2zstabilisesthesmolecularorbitalanddestabilisesthepmolecularorbital.Inother
words,orbitalmixingcausesthesandpmolecularorbitalstomovefurtherapartinenergy.Inthismorerefined
treatment,theresultingmolecularorbitalsarethereforenotderivedsolelyfromtwoatomicorbitals,andhencewedo
notusespecificlabels,suchas1s,aswedidforthehydrogenandheliumcases.Labelsofthetypesandy show
thepredominanttypeofoverlapthatcontributestothetmolecularorbital.Theamountofmixingdependsonthe
differenceinenergybetweenthe2sand2patomicorbitals.Mixingislargestwhentheenergiesoftheorbitalsare
nearlythesame.Asfigure5.51shows,theenergiesofthe2sand2patomicorbitalsdivergeasZincreasesacrossthe
secondrow,somixingislargeforB2butsmallforF2.Figure5.52showshowmixingaffectstheenergiesofthes
andpmolecularorbitals.

FIGURE5.51Energiesofthen=2valenceorbitalsasafunctionofZ.
 FIGURE5.52Mixingofthe2sand2pzorbitalscausesthesMOstobecomelowerinenergyandthep MOstoincreasein
energy.Theamountofmixingdecreasesacrossthesecondrowoftheperiodictable.ForB2 ,C2 andN2 ,the
MOsareoflowerenergythanthep orbitals.ForO2 andF2 ,theoppositeistrue.

Themaineffectofmixingistomakethepmolecularorbitalofhigherenergythanthedegenerateorbitalsforthe
B2,C2andN2molecules.Therefore,accordingtotheAufbauprinciple,wefirstfilltheorbitalsandthenthep
orbitalforthesemolecules.FollowingHund'srule,thismeansthatB2isparamagnetic,asithastheelectron
configuration ,inagreementwithexperiment.Noticethatcrossoverofthepandenergy
levelstakesplacebetweenmolecularnitrogenandmolecularoxygen.Becauseoforbitalmixing,wethereforerequire
twogeneralisedmolecularorbitaldiagramsfordiatomicmolecules,oneforB2,C2andN2,andtheotherforO2and
F2.Figure5.52showsbothdiagrams.

Thesemolecularorbitaldiagramshelptorationaliseexperimentalobservationsaboutmolecules.

WORKEDEXAMPLE5.10

TrendsinBondEnergy

Usemolecularorbitaldiagramstoexplainthetrendinthefollowingbondenergies:B2=290kJmol1,C2=
600kJmol1andN2=942kJmol1.

Analysis

Thedatashowthatbondenergiesforthesethreediatomicmoleculesincreaseaswemoveacrossthe
secondrowoftheperiodictable.Wemustconstructmolecularorbitaldiagramsforthethreemoleculesand
usetheresultstointerpretthetrend.

Solution

Thecrossoverpointforthep/energylevelstakesplacebetweenN2andO2,sothegeneraldiagramforZ
7infigure5.52appliestoallthreemolecules.ThevalenceelectroncountsareB2=6e,C2=8e,andN2
=10e.PlacetheseelectronsintheMOdiagramfollowingthePauliexclusionandAufbauprinciplesand
Hund'srule.Herearetheresults.
 Thediagramsshowthattheincreasingelectroncountsasweprogressfromborontocarbontonitrogen
resultinthefillingofbondingmolecularorbitals.Thisisrevealedmostclearlybycalculatingthebond
ordersforthethreemolecules: , and .
Increasingbondordercorrespondstostrongerbondingbetweentheatomsandthereforegreaterbond
energies.

Isouranswerreasonable?

Ourpredictedbondorderscorrelateperfectlywiththeexperimentalbondenergies,andthereforeour
answerisreasonable.Ofthesethreediatomicmolecules,onlyN2existsundernormalconditions.Boron
andcarbonformnonmolecularsolidsratherthanisolateddiatomicmolecules.However,molecularorbital
theorypredictsthatB2andC2mayexistundertherightconditions,andinfactbothmoleculescanbe
generatedinthegasphasebyvaporisingsolidboronorsolidcarbon.

PRACTICEEXERCISE5.10
Usemolecularorbitaldiagramstoexplainthetrend
inbondenergiesforthefollowingdiatomic
molecules:N2=942kJmol1,O2=495kJmol1
andF2=155kJmol1.

HeteronuclearDiatomicMolecules
Nitrogenoxide(NO)isanexampleofaheteronucleardiatomicmolecule.Thisinterestingmoleculehasbeeninthe
newsinrecentyearsbecauseofimportantdiscoveriesabouttheroleofNOasabiologicalmessenger.Amolecular
orbitaldiagramofNOisshowninfigure5.53.

FIGURE5.53MolecularorbitaldiagramofNO.
Becausethequalitativefeaturesoforbitaloverlapdonotdependontheidentityoftheatoms,thebondinginNOcan
bedescribedbythesamesetsoforbitalsthatdescribehomonucleardiatomicmolecules.WhichofthetwogeneralMO
diagramsfordiatomicmoleculesappliestonitrogenoxide?Thecrossoverpointfortheenergyrankingsofthepand
molecularorbitalsfallsbetweenNandO,soweexpecttheorbitalenergiestobenearlyequal.Experimentshave
shownthatthepMOisslightlymorestablethantheMO.Consequently,theMOconfigurationforthe11valence
electronsofNOmirrorsthatforthe12valenceelectronsofO2,exceptthatthereisasingleelectroninthe*orbital:

Thereareeightbondingelectronsandthreeantibondingelectrons,sothebondorderofNOis2.5.Thisbondis
strongerandshorterthanthedoublebondofO2butweakerandlongerthanthetriplebondofN2.

Species Bondlength Bondenergy Configuration Bondorder

O2 121pm 495kJmol1 2

NO 115pm 605kJmol1 2.5

N2 110pm 945kJmol1 (x )2(y )2(p)2 3

Electronconfigurationsforthesemoleculesleadtoaguidelineformolecularorbitalconfigurationsbasedonaverage
nuclearcharge,Zaverage :

Forsecondrowdiatomicmoleculesandions:
pislowerinenergythan x , y whenZaverage >7
x , y islowerinenergythanpwhenZaverage 7.

Workedexample5.11comparestheionisationenergiesofthreediatomicmoleculesandusesMOtheorytoexplain
thedifferences.

WORKEDEXAMPLE5.11

ComparingIonisationEnergies

ThefirstionisationenergyofNOis891kJmol1,thatofN2is1500kJmol1,andthatofCOis1350kJ
mol1.UseelectronconfigurationstoexplainwhyNOionisesmoreeasilythaneitherN2orCO.

Analysis

Recallfromchapter4thationisationenergyreferstotheremovalofanelectronfromanatom,or,inthis
case,fromamolecule.Wemustcountthevalenceelectrons,choosethecorrectMOdiagram,followthe
Aufbauprincipleinplacingtheelectrons,andthenusetheconfigurationstoexplaintheionisationenergy
data.

Solution

Beginwithasummaryoftheimportantinformationforeachmolecule:NOhas11valenceelectronsand
Zaverage =7.5N2has10valenceelectronsandZaverage =7COhas10valenceelectronsandZaverage =7.
ApplyingthegeneraldiatomicMOdiagramsoffigure5.52givesthefollowingconfigurations:
 COandN2areisoelectronicspecies,meaningtheyhavethesamenumberofelectrons(seep.145),and
eachhasabondorderof3.Itmakessensethatthesetwomoleculeshavecomparableionisationenergies.
NOhasoneelectronmorethanN2andCO,andthiselectronoccupiesoneoftheantibonding*orbitals.It
ismucheasiertoremovethisantibondingelectronfromNOthanitistoremoveabondingelectronfrom
eitheroftheothertwospecies.

PRACTICEEXERCISE5.11
Useelectronconfigurationstopredictwhichofthe
followingisthemoststablediatomiccombination
ofcarbonandnitrogen:CN,CNorCN+.

Fordiatomicmoleculescomposedofatomsthathaveverydifferentenergiesoftheiratomicorbitals,theMOdiagram
becomesslightlymorecomplicated.WewilluseHFasanexampleandshowtheenergylevelsforbothatomic
orbitalsandmolecularorbitalsinfigure5.54.

FIGURE5.54ThemolecularorbitaldiagramofHF.

Generally,orbitalsareoflowerenergyinamoreelectronegativeatomandorbitalswiththesamedesignationare
lowerinenergyifthenuclearchargeislarger.Armedwiththeseruleswecanunderstandthatthe1sorbitalintheF
atomismuchlowerinenergythanthe1sorbitalofH.

Molecularorbitalscanformonlywhenthereisnetoverlapbetweentheconstituentatomicorbitalsandwhenthe
atomicorbitalsarerelativelycloseinenergy.Wecanillustratethisbyconsideringtheapproachofthehydrogen1s
orbitalwitheitherthe2p x or2p y orbitalofthefluorineatom.
Astheseorbitalsapproacheachotherinasideonmanner,therewillbeconstructiveinterference,andhencea
bondinginteraction,betweenthesorbitalandthesamephasedlobeoftheporbital,buttherewillbeanequaland
oppositedestructiveinterference,andhenceanantibondinginteraction,betweenthesorbitalandtheoppositephased
lobeoftheporbital(figure5.54).Therefore,thereisnonetoverlapbetweenansorbitalandap x orp y orbitalwhen
theyapproachinthismanner,andnomolecularorbitalsareformed.Instead,the2p x and2p y orbitalsarelocated
primarilyonthefluorineatomasessentiallynonbondingmolecularorbitals.Whileoverlapofthehydrogen1sand
fluorine2sorbitalscan,intheory,occur,theenergiesoftheorbitalsaretoodifferenttopermiteffectiveoverlap,and
forthisreason,thefluorine2sorbitalremainsessentiallynonbonding.The1sorbitalofhydrogenandthe2p zorbital
offluorineoverlapeffectivelyandformtwoMOs.The3orbitalismuchcloserinenergytothe2p y orbitaloffluorine
andthereforehasmore2p y characterandisclosertothefluorinenucleus,whiletheantibonding4orbitalhasmore
hydrogen1scharacter.TheMOdiagraminfigure5.54showsthesequenceofthevalencemolecularorbitals.

TheCOmoleculeisanotherheteronucleardiatomicmoleculethatcanservetoillustratefeaturesofMOtheory.BothC
andOhave2sand2pvalenceorbitalsandthereforecanformbonds.GiventhatOismoreelectronegativethanC,
thevalenceorbitalsonOwillbeoflowerenergythanthecorrespondingorbitalsonC.

Figure5.55showstheenergyleveldiagramforCO.The2sandthe2p zorbitalsonbothCandOoverlaptoformfour
molecularorbitals,whiletheothertwoporbitalsonCandOoverlaptoformtwobondingandtwoantibonding
orbitals.Thebondingorbitalsarelowerinenergythanthebondingorbitalwithmainlypcharacterduetosp
mixing,whichisgenerallylargeinheteronucleardiatomicmolecules.
 FIGURE5.55ThemolecularorbitaldiagramofCO.

Wehavebarelyscratchedthesurfaceofmolecularorbitaltheory.Morecomplicatedsystems(threeormoreatoms)
requiretheuseofpowerfulcomputerstoadequatelytreatthebonding.Indeed,eventhesimplediatomicsystemswe
havediscussedhaveinvolvedhugesimplificationsitis,infact,currentlyimpossibletoexactlydescribeamolecule
containingmorethanoneelectron,asthemathematicsofsuchasystemhavesofardefiedsolution.Wehave
discussedanumberofwaystodescribethebondinginmoleculesalthougheachofthemhasparticularshortcomings,
ifappliedappropriately,wecanusethemtosatisfactorilyexplainthebondinginvirtuallyallchemicalsystems.

ChemistryResearch

AsymmetricOrganocatalysisacomputationalapproach

Professor(Richard)MingWahWong,NationalUniversityofSingapore

Inthischapterwehavediscussedhowtheelectronsonatomsinmolecularcompoundscaninteractandbe
sharedbetweenatomstoformbonds.Understandinghowelectronsinspecificorbitalsinagroupofatoms
interactwithotherelectronsfromanothergroupofatomscanassistusindeterminingmethodsbywhich
complexmoleculesmightbesyntesised.Thiscanbecarriedoutusingtheprinciplesofquantummechanics
andsolutionsoftheSchrdingerequation(seechapter4).However,practicalmeanstoachievethishave
onlyrecentlybecomeavailablethroughthedevelopmentofsophisticatedcomputersandintelligent
programs.Withthelatestadvancesincomputerhardwareandcomputationalmethodologies,highlyaccurate
theoreticalcalculationsofchemicalprocessescannowbecarriedoutroutinely.

Professor(Richard)MingWahWongisoneresearcherwhousescomputationalmethodstostudyhow
moleculesreact.Histheoreticalstudiesshowedforthefirsttimethatargonandheliumarecapableofforming
chemicalbondsandpredictedthattheircompoundscanexistinthegasphase.Thesepredictionshave
subsequentlybeenconfirmedbyexperimentalchemistsandthisshowshowusingacomputercanguide
practicalresearchtowardsnewdiscoveries.

ProfessorWong'srecentresearchhasfocusedonunderstandingthedetailedpathwaysinvolvedinreactions
wheretwosmallermoleculesjointomakemorecomplicatedstructures.Importantly,someofthesereactions
canbeinfluencedbythepresenceofothersmallmolecules.Theseadditivescancontrolthespeedofthe
reactionandinfluencetheorientationofthereactants.Forinstance,Wongandcoworkershaveinvestigated
theuseofBF3asacatalystforareactionbetweentwoalkenemoleculesthatcreatesanewcyclicstructure.
Figure5.56isarepresentationofhowBF3bindstopropenaltocontroltheorientationoftheorbitaloverlap
betweenpropenalandbuta1,3diene,whichleadsultimatelytothecyclicproduct.Thediagramalsoshows
thetransitionstate,whichisthemomentaryarrangementofbondsandatomsthatexistsasreactantsare
convertedtoproducts.Youwillseeinchapter15thattransitionstateshavenomeasurablelifetimeand
consequentlytheirnaturecannotbedeterminedexperimentallybutmustbeinferredfromotherobservations.
Wong'stheoreticalcalculationsalsogiveinsightintothenatureofthetransitionstateandallowusto
understandhowthereactionoccursandpredictthenatureoftheobservedproduct.
 FIGURE5.56Agraphicaldescriptionofthemannerbywhichbuta1,3dieneandpropenalareconvertedintoa
cyclicalkene.Thetransformationgoesthroughanenergypeak,whichiscalledthetransitionstate,
wheretheorbitalsinthealkenesbegintooverlaptoformthenewcarboncarbonbondsfoundinthe
product.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
FundamentalsofBonding
Covalentbondsareformedasaresultofthesharingofelectronsbetweennucleiinawaythatbalances
attractiveandrepulsiveforces.Inthehydrogenmolecule,H2,thisleadstoalowestenergyinternuclear
separationof74pm.Thisdistanceiscalledthebondlength,andtheenergydifferencebetweenthe
moleculeatthisdistanceandtheseparatedatomsiscalledthebondenergy.ThesinglebondinH2isan
exampleofabond,abondthatistotallysymmetricwithrespecttorotationabouttheinternuclearaxis.
InsimplediatomicmoleculessuchasH2andF2wecandescribebondingintermsofoverlapofatomic
orbitalscontainingsingleelectrons.Whenthetwoatomsinadiatomicmoleculearedifferent,the
electronpairwilltendtobeattractedmoretooneatom,resultinginunequalsharingoftheelectronsand
apolarcovalentbond.Theunequalsharingisaconsequenceofthedifferentelectronegativityvaluesof
theatomsinthemoleculethegreatertheelectronegativitydifferencebetweentheatoms,themorepolar
thebond.Electronegativitiesgenerallyincreaseacrossaperiodanddecreasedownagroupinthe
periodictable.

IonicBonding
Compoundsformedbetweenelementswithverydifferentelectronegativitiesareoftenionicin
character.Ioniccompoundsgenerallyconsistofalternatingpositivelyandnegativelychargedionsthat
areheldtogetherbyattractiveelectrostaticforcesbetweentheoppositelychargedions.Themagnitude
oftheattractiveforcesisdependentonthechargeoftheionsandtheseparationbetweenthem,aswell
asanumberofotherfactors.Thetotalenergythatmustbesuppliedtobreakthecrystallatticeintoits
gaseousionsiscalledthelatticeenergy.Trendsinlatticeenergyvaluesforioniccompoundscanbe
explainedintermsofionicchargeandseparation.

LewisStructures
Lewisstructuresshowthedistributionofvalenceelectronswithinamolecule.Bondingelectronsare
foundinsinglebonds(1electronpair),doublebonds(2electronpairs)ortriplebonds(3electronpairs)
andthesearerepresentedas1,2and3linesrespectivelybetweenthebondedatoms.Nonbonding
electrons,calledlonepairs,areindicatedasdotsnexttotheelementalsymbolfortheatomonwhich
theyarelocated.Lewisstructuresmaybedrawnusingthefollowingfivestepprocedure:
Step1:Countthevalenceelectrons.
Step2:Assemblethebondingframeworkusingsinglebonds.
Step3:Placethreenonbondingpairsofelectronsoneachouteratom,exceptH.
Step4:Assigntheremainingvalenceelectronstoinneratoms.
Step5:Minimiseformalchargesonallatoms.

Anatomhasanoctetifitissurroundedbyfourpairsofelectrons.Thisarrangementisoftenfoundfor
elementsinthesecondperiodoftheperiodictable.Whenthereisachoiceofelectronarrangement,the
onewhichminimisestheformalchargeonallatomswillbepreferred.Insomecases,twoormore
energeticallyequivalentLewisstructuresforamoleculecanbedrawnwhichdifferonlyintheposition
ofoneelectronpair.Suchstructuresarecalledresonancestructures.Wecanalsohaveenergetically
inequivalentresonancestructuresinthesecases,thepreferredstructurewillagainbethatwiththe
lowestpossibleformalchargeoneachatom.

ValenceShellElectronPairRepulsion(Vsepr)Theory
VSEPRtheorystatesthatamoleculewilladoptashapeinwhichelectronpairrepulsionsareminimised.
Thisisachievedbyplacingelectronpairsasfarapartaspossible.Wecanpredictthestructureofa
moleculebyusingthefollowingthreestepprocedure:
 1.DrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,and
usethefollowingtabletodeterminetheoptimumgeometryofthesesets.

Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs
(BP)orlonepairs(LP).Therepulsionsareintheorder:

Theidealisedelectronpairgeometrieswillbeslightlydistortedwheneverlonepairsarepresent,because
lonepairsoccupymorespacethanbondingpairs.

PropertiesofCovalentBonds
Moleculeswherethecentresofpartialnegativeandpartialpositivechangesdonotcoincidehavea
dipolemoment.ThemagnitudesofdipolemomentsaremeasuredinCm(coulombmetres).Molecules
containingpolarbondsdonotnecessarilyhaveadipolemoment,asthepolaritiesofsuchbondscan
canceleachother.Carbondioxideprovidessuchanexample.

Bondlengthsinmoleculesaredependentontheatomicradiiofthebondedatoms,whichthemselvesare
dependentoneffectivenuclearcharge.Amultiplebondbetweentwoatomsisshorterthanasinglebond
betweenthesameatoms.Bondenergiesincreaseasthenumberofelectronsinthebondincreases,and
alsoastheelectronegativitydifferencebetweenthebondedatomsincreases.Thelengthofabondis
inverselyproportionaltoitsbondenergyasabondlengthens,itsenergybecomesless.

ValenceBondTheory
Valencebondtheorydescribesbondinginmoleculesusinglocalisedbondsformedfromorbitaloverlap
ofhybridorbitals.Asthenamesuggests,valencebondtheoryconsidersonlyvalenceorbitalsinthe
formationofbonds.Valenceatomicorbitalsundergohybridisationtoformhybridorbitals,withthe
orbitalsinvolveddependingonthetypeofhybridorbitalrequired.Hybridisationofonesandthreep
orbitalsgivesfoursp 3hybridorbitals,hybridisingonesandtwoporbitalsgivesthreesp 2hybrid
orbitals,andhybridisingonesandoneporbitalgivestwosphybridorbitals.Theseprocessesleave
zero,oneandtwoporbitals,respectively,unhybridised.Thesp 3hybridorbitalsarepositioned
tetrahedrally,sp 2hybridorbitalsarearrangedinatrigonalplane,andsphybridorbitalsadoptalinear
arrangement.Thehybridorbitalsformbondsbyoverlappingwitheitheratomicorbitalsorhybrid
orbitalsonadjacentatoms.Multiplebondscanbedescribedintermsofonebondplusonebond
(doublebond)oronebondplustwobonds(triplebond)bondsareformedbyoverlapofthe
unhybridisedporbitalsonadjacentsp 2orsphybridisedatoms.

MolecularOrbitalTheory:DiatomicMolecules
Molecularorbitaltheoryconsidersallpossibleoverlapsbetweenatomicorbitalsinamoleculeand
describesbondingintermsofdelocalisedbonds.Overlapoftwoatomicorbitalsgivestheformationof
molecularorbitalsthatcancovertheentiremolecule.Atomicorbitalscanoverlapinphase(constructive
overlap)togivealowenergybondingmolecularorbital,oroutofphase(destructiveoverlap)togivea
highenergyantibondingmolecularorbital.Electrondensityismaximisedbetweenthenucleiinbonding
MOs,whileantibondingMOscontainanode,apositionwheretheamplitudechangessign,betweenthe
nuclei.Therelativeenergiesoftheresultingorbitalsareshownonamolecularorbitaldiagram.
Electronsareplacedintoamolecularorbitaldiagramfollowingthesamerulesasusedinanatomic
energyleveldiagram.Thebondorderofasimplediatomicmoleculecanbecalculatedfromthe
expression:

Whilebondordersaregenerally1,2or3,itispossibletohavenonintegerbondorders.Molecular
orbitaltheorycanaccountfortheobservedparamagnetismofO2whilevalencebondtheorycannot.
However,toaccountfortheobservedpropertiesofotherdiatomicmolecules,orbitalmixing,the
overlapofsatomicorbitalswithp zatomicorbitals,mustbeconsidered.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Periodictrendsinelectronegativity(section5.1)
Thesetrendsallowustousethepositionsofelementsintheperiodictabletoestimatethedegreeof
bondpolarityandtoestimatewhichatominabondisthemostelectronegative.

MethodfordrawingLewisstructures(section5.3)
Lewisstructuresshowthedistributionofvalenceelectronsinamoleculeorionandaredrawnaccording
tothefollowingconventions.
1.Eachatomisrepresentedbyitselementalsymbol.
2.OnlythevalenceelectronsappearinaLewisstructure.
3.Alinejoiningtwoelementalsymbolsrepresentsonepairofelectronssharedbetweentwoatoms.
4.Dotsplacednexttoanelementalsymbolrepresentnonbondingelectronsonthatatom.

Formalcharges(section5.3)
Byassigningformalcharges,wecanselectthebestLewisstructureforamoleculeorpolyatomicion.

Methodfordeterminingresonancestructures(section5.3)
Bydistributingmultiplebondsoveratomsinamolecule,weobtainabetterdescriptionofthebonding.

VSEPRtheory(section5.4)
ThistheoryenablesustopredicttheshapeofamoleculeorpolyatomicionwhenitsLewisstructureis
known.
1.DrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,and
usethefollowingtabletodeterminetheoptimumgeometryofthesesets.

Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs
(BP)orlonepairs(LP).Therepulsionsareintheorder:

Hybridorbitals(section5.6)
Hybridorbitalshelptoexplainthebondinginmolecules,andinparticularcanbeusedtorationalisethe
shapesofmolecules.

Molecularorbitaldiagrams(section5.7)
Byplacingelectronsinmolecularorbitaldiagramsweareabletoobtainbondordersthatagreewith
experimentsforsimplediatomicmolecules.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
FundamentalsofBonding
5.1Forthefollowingatoms,writethecompleteelectronconfigurationandidentifywhichofthe
electronswillbeinvolvedinbondformation:
(a)O
(b)P
(c)B
(d)Br.
5.2DescribebondformationbetweenahydrogenatomandaniodineatomtoformamoleculeofHI,
andincludeadiagramoftheoverlappingorbitals.
5.3Givethegroupnumberandthenumberofvalenceelectronsforthefollowingelements:
(a)aluminium
(b)arsenic
(c)fluorine
(d)tin.
5.4Hydrogenformsdiatomicmoleculeswithelementsfromgroup1oftheperiodictable.Describethe
bondinginLiHandincludeadiagramoftheoverlappingorbitals.
5.5Foreachofthefollowingpairs,identifywhichelementtendstoattractelectrondensityfromthe
otherinacovalentbond:
(a)CandN
(b)SandH
(c)ZnandI
(d)SandAs.
5.6Showthedirectionofbondpolarityforthefollowingbondsusing+/notation:
(a)SiO
(b)NC
(c)ClF
(d)BrC.
5.7Arrangethefollowingmoleculesinorderofincreasingbondpolarity:H2O,NH3,PH3andH2S.
IonicBonding
5.8Fromthefollowinglist,selecttheelementsthatformioniccompounds:Ca,C,Cu,Cs,ClandCr.
Indicatewhethereachformsastablecationorastableanion.
5.9Fromthefollowinglist,selecttheelementsthatformioniccompounds:B,Ba,Be,BiandBr.
Indicatewhethereachformsastablecationorastableanion.
5.10Considerthreepossibleioniccompoundsformedbybariumandoxygen:Ba+O,Ba2+O2and
Ba3+O3.
(a)Whichwouldhavethegreatestlatticeenergy?
(b)Whichwouldrequiretheleastenergytoformtheions?
(c)Whichcompoundactuallyexists,andwhy?
LewisStructures
5.11Countthetotalnumberofvalenceelectronsinthefollowingspecies:
 (a)H3PO4
(b)(C H ) C+
6 53
(c)(NH2)2CO
(d)SO 2.
4
5.12Convertthefollowingformulaeintomolecularframeworks.Foreachmolecule,calculatehow
manyvalenceelectronsarerequiredtoconstructtheframework:
(a)(CH3)3CBr
(b)(CH3CH2CH2)2NH
(c)HClO3
(d)OP(OCH3)3.
5.13DeterminetheLewisstructuresof:
(a)NH3
(b)NH +
4
(c) H N.
2
5.14DeterminetheLewisstructuresof:
(a)PBr3
(b)SiF4
(c) BF .
4
5.15UsethestandardprocedurestodeterminetheLewisstructuresof:
(a)H3CNH2
(b)CF2Cl2
(c)OF2.
5.16DeterminetheLewisstructuresof:
(a)IF5
(b)SO3
(c)OPCl3
(d)XeF2.
5.17DeterminetheLewisstructureofeachofthefollowingpolyatomicions.Includeallresonance
structuresandformalchargeswhereappropriate.
(a) NO
3
(b)HSO
4
(c) CO 2
3
(d)ClO
2
ValenceshellelectronpairRepulsion(VSEPR)Theory
5.18Sketchthefollowingmolecularshapesandgivethevariousbondanglesinthestructures:
(a)trigonalplanar,
(b)tetrahedral,
 (c)octahedral.
5.19Sketchandnametheshapesofthefollowingmolecules:
(a)CF2Cl2
(b)SiF4
(c)PBr3.
5.20Drawaballandstickmodelthatshowsthegeometryof1,2dichloroethane,ClH2CCH2Cl.
5.21WritetheLewisstructureofdimethylamine,(CH3)2NH.Determineitsgeometry,anddrawaball
andstickmodelofthemoleculeshowitasanammoniamoleculewiththetwohydrogenatoms
replacedbyCH3groups.
5.22Iodineformsthreecompoundswithchlorine:
(a)ICl
(b)ICl3
(c)ICl5.
DeterminetheLewisstructure,describetheshapeanddrawaballandstickmodelofeach
compound.
5.23Determinethemolecularshapeandtheidealbondanglesforeachofthefollowing:
(a)SO2
(b)SbF5
(c) ClF +
4
(d)ICl .
4
PropertiesofCovalentBonds
5.24DeterminetheLewisstructuresofthefollowingcompounds,anddeterminewhichhavedipole
moments.Foreachmoleculethathasadipolemoment,drawaballandstickmodelandinclude
anarrowtoindicatethedirectionofthedipolemoment.
(a)SiF4
(b)H2S
(c)XeF2
(d)GaCl3
(e)NF3
5.25Carbondioxidehasnodipolemoment,butsulfurdioxidehas=5.4410 30Cm.UseLewis
structurestoaccountforthisdifferenceindipolemoments.
5.26Whichofthefollowingmoleculeswouldyouexpecttohavebondanglesthatdeviatefromthe
idealVSEPRvalues?Forthemoleculesthatdo,makesketchesthatillustratethedeviations.
(a)PF5
(b)CH3I
(c)BrF5
5.27UseTable5.3toarrangethefollowingbondsinorderofincreasingbondstrength(weakestfirst).
Listthesinglemostimportantfactorforeachsuccessiveincreaseinstrength.

C C,HN,C O,N NandCC

ValenceBondTheory
5.28DescribethebondingbetweenfluorineandchlorineatomsinthemixedhalogenFCl.
5.29DescribethebondingbetweenhydrogenandchlorineatomsinHClandincludeapictureofthe
overlappingorbitals.
5.30Thebondanglesinantimonytrifluorideare87.DescribethebondinginSbF3,includingapicture
oftheorbitaloverlapinteractionthatcreatestheSbFbonds.
5.31Determinethehybridisationofaninneratominamoleculethathaseachofthefollowing
characteristics:
(a)2lonepairsand2ligands
(b)3ligandsand1lonepair
(c)3ligandsandnolonepairs.
5.32Namethehybridorbitalsformedbycombiningeachofthefollowingsetsofatomicorbitals:
(a)3sandthree3porbitals
(b)2sandone2porbital.
5.33Identifythehybridisationoftheboldedatomineachofthefollowingspecies:
(a)(CH3)2NH
(b)SO2
(c)CS2.
5.34Describethebondinginthechloroformmolecule,CHCl3.Sketchanorbitaloverlapdiagramofthe
molecule.
5.35Describethebondinginthehydrazinemolecule,H2NNH2.Sketchanorbitaloverlapdiagramof
themolecule.
5.36Describethebondinginthecommonsolventacetone,(CH3)2CO,andincludesketchesofallthe
bondingorbitals.

5.37Thecarboncompoundspenta1,4diene,pent1yneandcyclopenteneallhavethemolecular
formulaC5H8.Usethenumberofsetsofelectronpairsandhybridisationtodevelopbonding
picturesofthesethreemolecules.
(a)

(b)

(c)

5.38Decideifthefollowingpairsoforbitalsoverlaptoformabond,bond,ornobondatall.
Explainyourreasoningineachcase,includingasketchoftheorbitals.Assumethebondlies
 alongthezaxis.
(a)2p zand2p z
(b)2p y and2 px
(c) sp 3and2p
z
(d)2p y and2p y
MolecularOrbitalTheory:DiatomicMolecules
5.39Usemolecularorbitaldiagramstorankthebondenergiesofthefollowingdiatomicspeciesfrom
weakesttostrongest:H2,H2andH22.
5.40WhichofN orN +hasthestrongerbond?Useorbitalconfigurationstojustifyyourselection.
2 2
5.41Foreachofthefollowinginteractionsbetweenorbitalsoftwodifferentatoms,sketchtheresulting
molecularorbitals.Assumethatthenucleiliealongthezaxis,andincludeatleasttwocoordinate
axesinyourdrawing.LabeleachMOasbondingorantibondingandor.
(a)2sand2p z
(b)2p x and2p x
5.42Belowisanillustrationshowingtwo3dorbitalsabouttooverlap.Thedrawingsalsoshowthe
algebraicsignsofthewavefunctionsforbothorbitalsinthiscombination.Willthiscombinationof
orbitalsproduceabondingoranantibondingMO?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
5.43Determinethemoleculargeometriesofthefollowingmolecules:
(a)SiCl4,
(b)SeF4and
(c)CI4.
5.44Determinethemoleculargeometriesofthefollowingions:
(a) ClF ,
2
(b)BF and
4
(c) PF +.
4
5.45Howmanydifferentstructuralisomersarethereforoctahedralmoleculeswiththegeneralformula
AX3Y3?Drawthreedimensionalstructuresofeach.
5.46UsinginformationinTable5.1,determinetheaveragedifferenceinlatticeenergybetweengroup
1fluoridesandgroup1chlorides,andtheaveragedifferenceinlatticeenergybetweengroup1
bromidesandgroup1iodides.Isthereatrendintheindividualvalues?Ifso,describeandexplain
it.
5.47Carbon,nitrogenandoxygenformtwodifferentpolyatomicions:thecyanateion,NCO,andthe
isocyanateion,CNO.WriteLewisstructuresforeachanionincludenearequivalentresonance
structuresandindicateformalcharges.
5.48SpecieswiththegeneralchemicalformulaXY4canhavetheshapesshowninthefollowing
diagrams.Foreach,namethemoleculargeometry,identifytheidealVSEPRbondangles,givethe
numberoflonepairspresentinthestructureandprovideaspecificexample.
(a)

(b)

(c)

5.49SpecieswiththegeneralchemicalformulaXY3Ycanhavetheshapesshowninthefollowing
diagrams.Foreach,namethemoleculargeometry,identifytheidealVSEPRbondangles,givethe
numberoflonepairspresentinthestructureandprovideaspecificexample.
(a)
 (b)

(c)

5.50Intheloweratmosphere,NO2participatesinaseriesofreactionsinairthatisalsocontaminated
withunburnedhydrocarbons.Oneproductofthesereactionsisperoxyacetylnitrate(PAN).The
skeletalarrangementoftheatomsinPANappearsbelow.

(a)CompletetheLewisstructureofthiscompound.
(b)Determinethegeometryaroundeachatommarkedwithanasterisk.
(c)Givetheapproximatevaluesofthebondanglesindicatedwitharrows.
5.51TheHOHbondangleinawatermoleculeis104.5.TheHSHbondangleinhydrogen
sulfideisonly92.2.Explainthesevariationsinbondanglesusingorbitalsizesandelectron
electronrepulsionarguments.Drawspacefillingmodelstoillustrateyourexplanation.
5.52ListthefollowingXHbondsfromsmallestbondpolaritytolargestbondpolarity:CH,FH,
NH,OHandSiH.
5.53Sulfurformstwostableoxides,SO2andSO3.Describethebondingandgeometryofthese
compounds.
5.54Capsaicinisthemoleculeresponsibleforthehotspicinessofchillies:

(a)Howmanybondsdoescapsaicinhave?
(b)Whichorbitalsareusedforbondingbyeachofthelabelledatoms?
(c)Whatarethebondanglesaroundeachofthelabelledatoms?
(d)Redrawthestructureofcapsaicinaddingthelonepairs.
5.55Useelectronconfigurationstodecideifthefollowingspeciesareparamagneticordiamagnetic:
(a) N +
2
(b)O +.
2
5.56Determinethetypeoforbitals(atomic,sp 3orsp 2)usedbyeachatominthemoleculesshown
below.
(a)

(b)H3CNH2
(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
5.57DeterminetheLewisstructuresforthetwopossiblearrangementsoftheN2Omolecule:NNO
andNON.Experimentsshowthatthemoleculeislinearandhasadipolemoment.Whatisthe
arrangementofatoms?Justifyyourchoice.
5.58Theinneratomofatriatomicmoleculecanhaveanyoffourdifferentgeometriesforthe
surroundingsetsofelectronpairs.Identifythefour,describetheshapeassociatedwitheachand
giveaspecificexampleofeach.
5.59BothPF3andPF5areknowncompounds.NF3alsoexists,butNF5doesnot.Whyisthereno
moleculewiththeformulaNF5?
5.60Phosphorusacid,H3PO3,isanexceptiontotherulethathydrogenalwaysbondstooxygenin
oxoacids.Inthiscompound,oneofthehydrogenatomsbondstophosphorus.Determinethe
Lewisstructureofphosphorusacidanddeterminethegeometryaroundthephosphorusatom.
Drawaballandstickmodelofthemolecule.
5.61Nitrogenmoleculescanabsorbphotonstogenerateexcitedstatemolecules.Constructanenergy
leveldiagramandplacethevalenceelectronssothatitdescribesthemoststableexcitedstateofan
N2molecule.IstheNNbondinthisexcitedstateN2moleculestrongerorweakerthantheN
Nbondingroundstatenitrogen?Explainyouranswer.
5.62Chlorineformsoneneutraloxide,ClO2.Describethebondinginthisunusualcompound.Explain
whyitisconsideredunusual.
5.63Dilithiummoleculescanbegeneratedbyvaporisinglithiummetalatverylowpressure.Doyou
thinkitispossibletopreparediberyllium?ExplainyourreasoningusingMOdiagramsforLi2and
Be2.
5.64Whenanoxalateanion,C O 2,addstwoprotonstoformoxalicacid,twoCObondsbecome
2 4
longerandtwobecomeshorterthanthebondsinoxalateanions.Whichbondsgetlongerand
whichshorter?Usebondingprinciplestoexplainthechanges.
5.65Considerthebondlengthsofthefollowingdiatomicmolecules:N2,110pmO2,121pmF2,143
pm.Explainthevariationinlengthintermsofthemolecularorbitaldescriptionsofthese
molecules.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
antibondingmolecularorbital ioniccompounds polarcovalentbond
bondenergy latticeenergy resonancestructure
bondlength Lewisstructure seesawshape
bondorder linear sigma()bond
bondingmolecularorbital localisedbond singlebond
bondingorbital lonepair sphybridorbitals
covalentbond molecularorbitaldiagram sp 2hybridorbitals
delocalisedbond molecularorbitaltheory
sp 3hybridorbitals
dipolemoment molecularorbital(MO)
tetrahedral
doublebond node
trigonalbipyramidal
electronegativity octahedral
trigonalplanar
formalcharge orbitalmixing
triplebond
hybridorbital orbitaloverlap
valenceshellelectronpair
hydration pi()bond
repulsion(VSEPR)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

6 Gases
Weareallfamiliarwiththethreecommonstatesofmattergas,liquidandsolidin,forexample,theair
webreathe,thewateroftheoceanandthesandofthebeach.Allthreestatesarecomposedofatoms,ionsor
molecules.Thestrengthoftheattractiveforcesbetweentheseconstituentsinfluenceswhichparticularstateof
matteracompounddisplays.Inthischapterwewillfocusonthecharacteristicsandbehaviourofgases,and
inchapter7wewilldealwithliquidsandsolids.

Althoughfewchemicalelementsoccurnaturallyasgases,wespendalmostallofourtimeimmersedinthem.
TheEarth'satmosphereismadeupmainlyofnitrogen,N2,(78%)andoxygen,O2,(21%)withsomeother
speciesintraceamounts.Theexactcompositionandtemperatureofthisgasmixtureisresponsibleforour
weather.ThephotoonthispageshowshotairballoonsovertheMelbourneCricketGround(MCG)and
remindsusthathotairballoonistsexploitthefactthathotairrises.

Webeginthischapterwithadiscussionofthevariablesthatcharacterisegases.Thenwedevelopamolecular
descriptionthatexplainsgasbehaviour.Next,weexploreadditionalgaspropertiesandshowhowtocarryout
stoichiometriccalculationsforreactionsinvolvinggasphasespecies.Wethenexplorethekindsofattractions
thatexistbetweenmoleculesandhowtheseattractionsaffectthephysicalpropertiesofgases.

KEYTOPICS

6.1Thestatesofmatter
6.2Describinggases
6.3Molecularviewofgases
 6.4Gasmixtures
6.5Applicationsoftheidealgasequation
6.6Gasstoichiometry
6.7Realgases
6.8Intermolecularforces

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.1TheStatesofMatter
Itisremarkablethatessentiallyallofthematterintheuniverseexistsinonlythreestates:solid,liquidor
gas.Afourthstateofmatter,plasma,existsonlyunderextremeconditionssuchasthosefoundinthe
interiorsofstars,whiletheBoseEinsteincondensate,arecentlydiscoveredstateofmatter,isfound
onlyattemperaturesapproachingabsolutezero.Wewillalsoencountersupercriticalfluids,whichhave
propertiesofbothliquidsandgases,inchapter7.

Itisalsointerestingthatmostsubstancescanexistinanyofthesethreestates,andwecanchangethe
moststablestateofaparticularsubstancebyvaryingthetemperatureand/orpressureforexample,
coolingliquidwatertobelow0Catambientpressurewillproducesolidwater(ice).

Why,at25Candatmosphericpressure,doeswaterexistasaliquid,whileoxygenisagasandgoldis
asolid?Theanswerliesintheforcesthatoccurbetweenindividualatoms,moleculesorionsina
substance.Solidsareheldtogetherbyrelativelystrongforcesbetweentheircomponents,whilethe
correspondingforcesingasesarerelativelyweak.Thischapterandchapter7focusonthedifferent
possiblestatesofmatter.Inthischapter,weconcentrateonthegaseousstateofmatter,andinvestigate
thedifferenttypesofforcesthatcanoccurbetweenatoms,ionsandmolecules.Chapter7isprimarily
concernedwithliquidsandsolids(thesocalledcondensedphases),andalsolooksattheprocesses
involvedwhensubstancesundergochangesofstate.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.2DescribingGases
Gasesarecharacterisedbythefactthat,incontrasttoliquidsandsolids,theyexpandtooccupyallthe
spaceoftheircontainer.Forexample,gaseouswater(watervapour)willbefoundinallpartsofany
flaskitisin,but,ifthetemperatureislowered,theresultingliquidwateroccupiesonlythebottomofthe
flask.Loweringthetemperaturefurthertobelowthefreezingpointproducesice,whichalsooccupies
onlythebottomoftheflask.Thefactthatgasesfillallavailablespaceimpliesthattheindividualgas
atomsormoleculesarefreetomoveanywherewithintheircontainer(figure6.1),andthereforethe
forcesbetweenthemmustbeveryweak.Oneofthedefiningcharacteristicsofgasesisthepressurethey
exert.Thisresultsfromtherapidmotionofindividualgasatomsormoleculesandtheircollisionswith
thewallsofthecontainer.Thepressure(p)exertedbyagasisdependentontheamountofgaspresent
(n),thevolumeinwhichitiscontained(V!)anditstemperature(T).Onthefollowingpages,wederivea
relationshiprelatingallofthesevariables.

FIGURE6.1Moleculesoratomsofagasmovefreelythroughouttheentirevolumeofacontainer,changing
directionwhenevertheycollidewithothermoleculesoratomsorwithawall.Thelinetracesa
possiblepathofasinglemoleculeoratom.

Pressure(p)
Anyobjectthatstrikesasurfaceexertsaforceagainstthatsurface.Inthesamewaythataballexertsa
forceagainstthegroundwhenitstrikesit,thegasmoleculesinsidetheballalsoexertpressurethrough
collisionswiththewallsoftheball.Atanytemperatureaboveabsolutezero,atomsandmoleculesare
alwaysinmotion.Atthemolecularlevel,atomsandmoleculesexertforcesthroughneverending
collisionswitheachotherandwiththewallsoftheircontainer(e.g.theinsidesurfaceoftheball).The
collectiveresultofthesecollisionsiswhatwecallpressure.Weexperiencepressureasamacroscopic
property.

WecangetafeelforthemacroscopiccharacteristicsofgaspressurebyexaminingtheEarth's
atmosphere.Theatmosphereisahugereservoirofgasthat,duetoEarth'sgravity,exertspressureonthe
Earth'ssurface.Thepressureoftheatmospherecanbemeasuredwithaninstrumentcalleda
barometer.Figure6.2showsaschematicviewofasimplemercurybarometer.Alongglasstube,
closedatoneend,isfilledwithliquidmercury.Thefilledtubeisinvertedcarefullyintoadishthatis
partiallyfilledwithmoremercury.Theforceofgravitypullsdownwardsonthemercuryinthetube.
Withnoopposingforce,allthemercurywouldrunoutofthetubeandmixwiththemercuryinthedish.
Themercurydoesfall,buttheflowstopsatacertainheight.Thecolumnofmercurystopsfalling
becausetheatmosphereexertspressureonthemercuryinthedish,pushingthecolumnupthetube.
Whentheheightofthemercurycolumngeneratesadownwardforceontheinsideofthetubethat
exactlybalancestheforceexertedbytheatmosphereontheoutsideofthetube,thecolumnofmercury
willremainsteady.
 FIGURE6.2Amercurybarometer.Thepressureoftheatmosphereonthesurfaceofthemercurybalances
thepressureofthecolumnofmercury.

Atsealevel,atmosphericpressuresupportsamercurycolumnapproximately760mmhigh.Changesin
altitudeandweathercausefluctuationsinatmosphericpressure.Atsealeveltheheightofthemercury
columnseldomvariesbymorethan10mm,exceptunderextremeconditions,suchasintheeyeofa
cyclone,whenitmayfallbelow740mm.

Amanometerissimilartoabarometer,butinamanometergasesexertpressureonbothliquid
surfaces.Consequently,amanometermeasuresthedifferenceinpressuresexertedbytwogases.A
simplemanometer,showninfigure6.3,isaUshapedglasstubecontainingmercury.Onesideofthe
tubeisexposedtotheatmosphereandtheothertoagaswhosepressurewewanttomeasure.Infigure
6.3,thepressureexertedbytheatmosphere(p atm)islessthanthepressureexertedbythegasinthebulb
(p gas).Thedifferenceinheightsofmercurybetweenthetwosidesofthemanometerdependsonthe
differenceinthepressuresexertedbythegasandtheatmosphere(equaltop Hg).

FIGURE6.3Thedifferenceinheightsofliquidonthetwosidesofamanometerisameasureofthedifference
ingaspressuresappliedtothetwosides.

Aswelearnedinchapter2,theSIunitforpressureisthepascal(Pa).Pressureisdefinedasforceper
unitarea,sothepascalisexpressedbycombiningtheSIunitsforthesetwovariables.TheSIunitof
forceisthenewton(N),andtheunitofareaissquaremetres(m2).Thus1Pa=1Nm2=1kgm1s2=
1Jm3(with1N=1kgms2and1J=1kgm2s2).

AnumberofnonSIunitsforpressurearealsocommonlyused:
Onestandardatmosphere(1atm)isthepressurethatwillsupportacolumnofmercury760mmin
height(i.e.averageatmosphericpressureatsealevel)1atm=1.0132510 5Pa.
Onetorristhepressureexertedbyacolumnofmercury1mminheight1atm=760torr.
1bar=110 5Pa.
InthistextbookwewillalwaysexpresspressureintheSIunit:thepascal(Pa).Inchapter8,wewill
encounterstandardpressure, ,whichis110 5Pa,veryslightlydifferentfromonestandard
atmosphere.Itisimportantnottoconfusethetwo.

TheGasLaws
Thevolumeoccupiedbyagaschangesinresponsetochangesinpressure,temperatureandamountof
gas.Therelationshipsamongtheseareknownasthegaslaws.

Boyle'SLaw:theRelationshipBetweenVolumeandPressure
Figure6.4aillustratesexperimentsconductedatconstanttemperaturebytheEnglishscientistRobert
Boyleinabout1660.BoyleaddedliquidmercurytotheopenendofaJshapedglasstube,trappinga
fixedamountofairontheclosedside.WhenBoyleaddedadditionalmercurytotheopenendofthe
tube,thepressureexertedbytheweightoftheadditionalmercurycompressedthetrappedgasintoa
smallervolume.Forexample,asshowninfigure6.4a,Boylefoundthatdoublingthetotalpressureon
thetrappedairbytheadditionofmercuryhalveditsvolume.Inmoregeneralterms,Boyle's
experimentsshowedthatthevolumeofthetrappedairwasinverselyproportionaltothetotalpressure
appliedbythemercuryplustheatmosphere.

or,alternatively:

wherekisaconstant.Thisisshowngraphicallyinfigure6.4b.

FIGURE6.4 (a)SchematicillustrationofBoyle'sexperimentsonairtrappedinJshapedtubes.The
pressureontheenclosedgasintherighthandtubeistwicethatinthelefthandtube,
andthevolumeoftheenclosedgasishalved.
(b)
GraphshowingthelinearvariationofVversus .
Charles'Law:theRelationshipBetweenVolumeandTemperature
Boylealsoobservedthatheatingagascausesittoexpandinvolume,butmorethanacenturypassed
beforeJacquesAlexandreCsarCharlesreportedthefirstquantitativestudiesofgasvolumeasa
functionoftemperature.Charlesfoundthat,forafixedamountofgas,agraphofgasvolumeversus
temperaturegivesastraightline,asshowninfigure6.5.Inotherwords,thevolumeofagasisdirectly
proportionaltoitstemperature.

FIGURE6.5Plotsofvolumeversustemperaturefor1moleofairatthreeconstantpressures.Thedots
representexperimentaldata,withdashedlinesofbestfitextrapolatedto0K.

or,alternatively:

wherekisaconstant.

Avogadro'sLaw:theRelationshipBetweenVolumeandAmount
Thevolumeofagasalsochangeswhentheamountofthegaschanges.Ifwedoubletheamountofa
gaswhilekeepingthetemperatureandpressurefixed,thegasvolumedoubles.Inotherwords,gas
volumeisproportionaltotheamountofgas.

or,alternatively:

wherekisaconstant.

TheIdealGasEquation
TheworkofBoyle,Charles,Avogadroandotherearlyscientistsshowedthatthevolumeofanygasis
proportionaltothetemperatureandamountofthegas,andinverselyproportionaltothepressureofthe
gas.Combiningtheseobservations,wefindthat:

Thisproportionalityisconvertedintoanequalitybyintroducingthegasconstant,representedbythe
symbolR.IntroducingRandmultiplyingbothsidesoftheequationbypgives:

Thisisknownastheidealgasequation,becauseitdescribesthebehaviourofanidealgas.Whileno
gasistrulyideal,theidealgasequationisadequatetodescribemostrealgasesprovidedthattheir
pressureisrelativelylow.Thetemperatureintheidealgasequationisexpressedinkelvin,withT(K)=
T(C)+273.15.ThegasconstantisdefinedinSIunitsasR=8.314Jmol1K1.Pressureisexpressed
inPa,volumeisexpressedinm3(1m3=110 3L)andamount(n)isexpressedinmoles.Thereisa
secondversionofthegasconstantthatisexpressedinnonSIunits:R=0.08206Latm1K1mol1.
Thisisusedfrequentlyandsoitisimportanttoalwaysconfirmthatthevalueandunitsofthegas
constantarechosenappropriatelyforagivenproblem.Workedexample6.1showsthecalculationsfor
bothgasconstants.

Itfollowsnaturallyfromtheidealgasequationthatallidealgaseshavethesamemolarvolumeundera
givensetofstandardconditions.Inchemistry,thegenerallyacceptedstandardconditionsare0Cand1
10 5Pa,leadingtoamolarvolumeundertheseconditionsof22.71L.

WORKEDEXAMPLE6.1

CalculationofGasPressure

A1.00010 3Lsteelstoragetankcontains88.5kgofmethane,CH4.Ifthetemperatureis25
C,whatisthepressureinsidethetank?

Analysis

Theproblemasksforthepressureexertedbyagas.Thegasisstoredinasteeltank,sothe
volumeofthegascannotchange.Nochemicalchangesaredescribedintheproblem.We
canthereforesolvethisproblemusingtheidealgasequation.

Solution

Wearetoldthat:

Wecancalculatethepressureofthegasusingtheidealgasequation,butweneedtomake
sureallthevariablesareexpressedinappropriateunits.Temperaturemustbeinkelvin,
amountofmethaneinmoles,andvolumeinm3.

WerearrangetheidealgasequationbydividingbothsidesbyV,thusmakingpressurethe
subjectoftheequation.

Add273.15tothetemperatureinCtoconverttokelvin.
 Notethat,whenweaddnumbers,theresulthasthesamenumberofdecimalplacesasthe
numberwiththefewestdecimalplaces(zerointhisexample).

Usethemolarmassofmethanetocalculatetheamountofgas.

Nowsubstitutethisintotherearrangedidealgasequationandcalculatethepressure.

IfweusethenonSIversionofthegasconstant,0.08206LatmK1mol1,weneedto
expressthevolumeinlitres(L):

Isouranswerreasonable?

Itisimportanttocheckthattheunitscancelproperly,givingaresultinpressureunits(recall
that1Pa=1Jm3).Theproblemdescribesalargeamountofmethaneinarelativelysmall
volume,soahighpressure(over100timesatmosphericpressure)isreasonable.Thishigh
valueindicateswhygasesmustbestoredintanksmadeofmaterialssuchassteelthatcan
withstandhighpressures.

PRACTICEEXERCISE6.1
Determinethenewpressureifthetankin
workedexample6.1isstoredinahotshed
wherethetemperaturereaches42C.

Duringchemicalandphysicaltransformations,anyofthefourvariablesintheidealgasequation(p,V,
n,T)maychange,andanyofthemmayremainconstant.Theidealgasequationcanberearrangedas:

Then,fordifferentinitialandfinalconditions,wehave:

WORKEDEXAMPLE6.2

PressureVolumeVariations
Asampleofheliumgasisheldatconstanttemperatureinsideacylinderwithavolumeof
0.80Lwhenapistonexertsapressureof1.510 5Pa.Iftheexternalpressureonthepiston
isincreasedto2.110 5Pa,whatwillthenewvolumebe?

Analysis

Wecanvisualisetheconditionsbydrawingaschematicdiagramoftheinitialandfinal
conditions(p=initialpressure,p f=finalpressure,Vi=initialvolume,Vf=finalvolume).

Solution

Gasbehaviourisinvolved,sotheequationthatappliesistheidealgasequation,pV=nRT.
RearrangingthegasequationtosolveforVwillnothelpbecausewedonotknown,the
amountofHepresent,orT,thetemperatureofthegas.Wedoknow,however,thatnandT
remainunchangedasthepressureincreases.

Todeterminethefinalvolumeoftheheliumgas,applytheidealgasequationtotheinitial
andfinalconditions(shownwithsubscriptsiandf,respectively).

Inthisproblem,thequantityofHeinsidethecylinderandthetemperatureofthegasare
constant:

Therefore:

NoticethatwecansolvethisforVfwithoutknowingthevaluesofnandT.

Nowwerearrangetheaboveequation,substitutetheappropriatevaluesandcalculatethe
finalvolume.

Isouranswerreasonable?
 Thisanswerisreasonablebecauseanexternalpressureincreasehascausedavolume
decrease.

PRACTICEEXERCISE6.2
Thepistoninworkedexample6.2is
withdrawnuntilthegasvolumeis2.55L.
Calculatethefinalpressureofthegas.

Inworkedexample6.2,thequantitiesontherighthandsideoftheidealgasequation(pV=nRT)are
fixed,whereasthequantitiesontheleftarechanging.Ausefulstrategyfororganisinggascalculationsis
torearrangethegasequationtoplaceallvariablesthatdonotchangeononeside.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.3MolecularViewofGases
Tounderstandwhyallgasescanbedescribedbyasingleequation,weneedtoexplorehowgases
behaveatthemolecularlevel.Asgasesarecharacterisedbyrapidmotionoftheirconstituentatomsor
molecules,themostimportantenergycomponenttoconsideristheirkineticenergy,Ekinetic .Thekinetic
energyofanobjectisgivenbytheequation:

wheremisthemassoftheobject(inthiscaseanindividualgasatomormolecule)anduisitsspeed.
Wecaneasilyobtainthemassofasingleatomormoleculefromthemolarmassofthegas,butinorder
tocalculateEkinetic wemustmeasurethespeedwithwhichanatomormoleculeismoving.Astheatoms
ormoleculesinanysampleofgasareconstantlyundergoingcollisionswithotheratomsormolecules
andwiththewallsofthecontainer,theymightnotnecessarilyallbemovingatthesamespeed.Onthe
followingpages,wedescribeamethodofmeasuringthespeedsofgasatomsormoleculestogivean
overalldistributionofspeedsforagassample.Thisallowsustodeterminethekineticenergy
distributionoftheatomsormoleculesinasampleofgas.

MolecularSpeeds
Thespeedsofmoleculesinagascanbemeasuredusingamolecularbeamapparatus,whichisshown
schematicallyinfigure6.6.Gasmoleculesinanovenescapethroughasmallholeintoachamberwith
verylowmoleculardensity:thatis,highvacuum.Asetofslitsblocksthepassageofallmolecules
exceptthosemovingintheforwarddirection.Theresultisabeamofmolecules,allmovinginthesame
direction.Arotatingdiscblocksthebeampathexceptforasmallslitthatallowsapacketofmolecules
topassthrough.Eachmoleculemovesdownthebeamaxisatitsownspeedundergoingminimal
collisionswithothermoleculesinthepacket.Thefasteramoleculemoves,thelesstimeittakestotravel
thelengthofthechamber.Adetectorattheendofthechambermeasuresthenumberofmolecules
arrivingasafunctionoftime,givingaprofileofspeeds.
 FIGURE6.6 (a)Schematicdiagramofamolecularbeamapparatusdesignedtomeasurethespeedsof
gasmolecules.
(b)Distributionofmoleculesobservedbythedetectorasafunctionofthetimeafterapacket
ofmoleculesreachestheslitinthedisc.

Whenthespeedprofileofagasismeasuredinthisway,theresultsgiveadistributionliketheone
showninfigure6.6b.Ifallthemoleculestravelledatthesamespeed,theywouldallreachthedetector
atthesametime,inasingleclump.Instead,fastermoleculesmoveaheadofthemainpacket,and
slowermoleculesfallbehind.Thisexperimentshowsthatmoleculesinagashaveadistributionof
speeds.

Apatternemergeswhenthismolecularbeamexperimentisrepeatedforvariousgasesatacommon
temperaturemoleculeswithsmallmassesmove,onaverage,fasterthanthosewithlargemasses.Figure
6.7showsthisforH2,CH4andCO2.Ofthesemolecules,H2hasthesmallestmassandCO2thelargest.
Theverticallinedrawnforeachgasshowsthespeedatwhichthereisthelargestnumberofmolecules.
Moremoleculeshavethisspeedthananyother,sothisisthemostprobablespeedformoleculesofthat
gas.Themostprobablespeedforamoleculeofhydrogenat300Kis1.5710 3ms1or5.6510 3km
h 1.
FIGURE6.7GraphshowingmolecularspeeddistributionsforCO2 ,CH4 andH2 atatemperatureof300K.

WORKEDEXAMPLE6.3

AMolecularBeamExperiment
Thefiguresbelowrepresentmixturesofneonatomsandhydrogenmolecules.

Oneofthegasmixtureswasusedinamolecularbeamexperiment.Theresultofthe
experimentisshownbelow.Whichofthetwogassamples,AorB,wasusedforthis
experiment?

Analysis

Examinethetwosamples,andthendecidehoweachofthemwouldbehaveinabeam
experiment.

Solution

SampleAcontainseightH2moleculesandfourNeatoms,andsampleBcontainsfourH2
 moleculesandeightNeatoms.Inamolecularbeamexperiment,bothsampleswouldgive
twopeaksinrelativeareasof2:1.Atomsormoleculeswithasmallmassmovefasterthan
thosewithalargemass,soweexpectH2(M=2.02gmol1)toreachthedetectorbeforeNe
(M=20.2gmol1).Thedatashowthatthefirstsubstancetoreachthedetectorispresentin
thesmalleramount.Consequently,thesampleusedinthebeamexperimentistheonewith
thesmalleramountofhydrogenmoleculessampleB.

Isouranswerreasonable?

H2movesfasterthanother,heaviersubstances,soitmakessensethattheH2molecules,
whicharelighterthanNeatoms,gettothedetectorfaster.H2moleculesarepresentina
smalleramountthanNeatoms,andtheexperimentaldataareconsistentwiththat.

PRACTICEEXERCISE6.3
Supposethat,inworkedexample6.3,
sampleAisusedandthatthesecondgasis
heliuminsteadofneon.Sketchagraph,
similartotheoneinworkedexample6.3,
showingthenumberofmolecules/atoms
versustime.

ChemicalConnections

MetalOrganicFrameworksforGreenhouseGasSeparationandHydrogen
StorageApplications

DeannaMD'Alessandro,UniversityofSydney

Theprospectofaworseningclimaticsituationduetoglobalwarmingisoneofthemost
pressingenvironmentalconcernsforourgeneration.Theurgentneedforstrategiestoreduce
atmosphericconcentrationsofgreenhousegaseshaspromptedactionfrommany
governmentsandindustries,andanumberofhighprofilecollaborativeprogramshavebeen
establishedtotackletheissue.Twoofthecentralstrategiesintheseinitiativesincludethe
captureandsequestrationofcarbondioxide,thepredominantgreenhousegas,fromlarge
stationarysourcessuchaspowerplants,andtheintroductionofhydrogenasacleanburning
alternativetofossilfuelsinmobileapplicationssuchascars.

Amongseveralcandidategroupsofmaterialsforgasstorageandseparation,highlyporous
threedimensionalsolidsknownasmetalorganicframeworks(MOFs,whicharealsoknown
asporouscoordinationpolymers,figure6.8)showexceptionalpromise.Believeitornot,one
teaspoonofoneofthesematerialscanhaveasurfaceareathatisequivalenttoafootball
field!Thesemicroporouscrystallinesolidsarecomposedoforganicbridgingligandsor
strutscoordinatedtometalbasednodestoformathreedimensionalextendednetworkwith
uniformporediameterstypicallyintherangeof3to20.Thenodesgenerallyconsistofone
ormoremetalions(e.g.Al3+,Cr3+,Cu 2+,Zn 2+)towhichtheorganicbridgingligands
coordinateviaaspecificfunctionalgroup(e.g.carboxylate,pyridyl).

FIGURE6.8RepresentationofCO2 diffusingthroughamicroporousMOFstructure.

TheintensecurrentresearchefforttowardsindustrialapplicationsofMOFsingasstorage,
separationandcatalysisisattributedtotheiruniquestructuralproperties,including:
robustness,highthermalandchemicalstabilities,unprecedentedinternalsurfaceareas(upto
6000m2g 1),highvoidvolumes(5590%)andlowdensities(from0.21to1.00gcm3),
whichcanbemaintainedevenuponevacuationoftheguestmoleculesfromthepores.The
regularmonodispersenatureofthecrystallinearrayofmicroporesisakeyfeaturethat
distinguishesMOFsfromotherporousmaterials(e.g.polymers,mesoporoussilicas,activated
carbon).Inaddition,theabilitytosystematicallymodulatetheporedimensionsandsurface
chemistrywithinMOFsisafeaturethatwaspreviouslylargelyabsentinzeolitematerials.

TheCO2captureproblem:GasstreamsfrompowerstationchimneysconsistprimarilyofN2,
H2OandCO2ina13:2:2ratiobymass.Usingconventionaltechnologies,theseparationof
CO2fromthishighvolumeofeffluentgas,whichisatapproximatelyatmosphericpressure,
wouldrequireapproximately2535%oftheenergygeneratedbyapowerstation.Itisthere
foreobviouswhysofewlargescalepowerstationsworldwide(andnoneinAustraliaorNew
Zealand)performpostcombustioncarboncapture.Clearly,thereisanurgentneedforcheaper
alternativestotheconventionalwetscrubbingmethodsthatarebasedontheabsorptionof
CO2byaqueousaminesolutions.

MOFsofferapotentialsolutiontothisgasseparationproblemastheirporevolumesand
surfacefunctionalitiescanbetunedtopreferentiallyseparateonegasfromanother(figure
6.9).ThereareotherapplicationswhereCO2captureusingMOFscanalsobeenvisagedfor
example,thesweeteningofnaturalgasrequirestheseparationofmixturesofN2,CO2and
 CH4fromgasfields.

FIGURE6.9RepresentationofpartofthecrystalstructureofamagnesiumbasedMOFalongthe
onedimensionalchannels.Theinsetshowsthechargeinducedinteractionbetween
oneoftheopenMg2+coordinationsitesandaCO2 molecule.

TheH2storageproblem:Hydrogenisanidealenergycarrierfortransportationbecauseitis
lightweight,canbeproducedusingrenewableresourcessuchassunlight,andtheonly
byproductiswater.Commercialapplicationisproblematic,though,ashydrogenishardto
storewithouttakingupaverylargeamountofspace.Onesolutiontothisstorageissueisto
useMOFswhich,byvirtueoftheirextraordinarilyhighsurfaceareas,couldonedaystore
enoughhydrogenatnormaloperatingtemperaturesandpressuresinfuelcellstodrivemore
than1000kilometres.

SpeedandEnergy
Theenergyofamoleculeisrelatedtoitsspeed.Aswelearnedonp.218,anymovingobjecthaskinetic
energy(Ekinetic )withamagnitudegivenby:

wheremistheobject'smassanduisitsspeed.Themostprobablespeedofhydrogenmoleculesat300
Kis1.5710 3ms1(seep.219).WeneedthemassofoneH2moleculetobeabletocalculateitsmost
probablekineticenergy.TheSIunitofenergyisthejoule(J),whichequals1kgm2s2.Thus,weneed
themass(m)inkilograms.Themolarmassgivesthemassof1moleofmolecules,sodividingmolar
massbytheAvogadroconstant(NA)givesthemassof1molecule.
Nowapply:

Themostprobablespeedsofmethaneandcarbondioxideareslowerthanthemostprobablespeedof
hydrogen(seefigure6.7),butCH4andCO2moleculeshavelargermassesthanH2.Whenkinetic
energycalculationsarerepeatedforthesegases,theyshowthatthemostprobablekineticenergyisthe
sameforallthreegases.

ForaCH4molecule(m=2.66410 26kg):

ForaCO2molecule(m=7.30810 26kg)

Eventhoughthespeeddistributionsforthesethreegasespeakatdifferentvalues,themostprobable
kineticenergiesareidentical.Wecanalsoshowthat,atagiventemperature,allgaseshavethesame
molecularkineticenergydistribution.

Molecularbeamexperimentsshowthatmoleculesmovefasterasthetemperatureincreases.Molecules
escapingfromtheovenat900Ktakelesstimetoreachthedetectorthanmoleculesescapingat300K.
Asthemolecularspeedincreases,sodoesthekineticenergy.Figure6.10showsthemolecularkinetic
energydistributionsat300Kand900K.Bycomparingthisfigurewithfigure6.7,weseethatthe
molecularenergiesshowawidedistributionthatissimilartothedistributioninmolecularspeeds.
Unlikespeeds,however,themolecularenergydistributionsarethesameforallgasesatanyparticular
temperature.Thedistributionsshowninfigure6.10applytoanygas.

FIGURE6.10Graphofdistributionofmolecularenergiesforanygasat300Kand900K.
AverageKineticEnergyandTemperature
Themostprobablekineticenergyisnotthesameastheaveragekineticenergy.Tofindtheaverage
kineticenergypermolecule( ,thebaroveravariableindicatesthatitisanaveragevalue),we
mustaddalltheindividualmolecularenergiesanddividebythetotalnumberofmolecules.Theresult
describeshowtheaveragekineticenergyofgasmoleculesisrelatedtothetemperatureofthegas.

Inthisequation,Tisthetemperatureinkelvin,NAistheAvogadroconstantandRisthegasconstant
(8.314Jmol1K1).

Theaveragekineticenergyexpressedbytheequationiskineticenergypermolecule.Wefindthetotal
kineticenergyof1mole(Ekinetic,molar)ofgasmoleculesbymultiplyingbytheAvogadroconstant.

Thus,1moleofagashasatotalmolecularkineticenergyof RTindependentofthenatureofthatgas.
Whiletheequationisusuallystatedinthisway,itisworthwhiletonotethatitisthetemperaturethatisa
measureofaveragekineticenergy.

WORKEDEXAMPLE6.4

MolecularKineticEnergies
Determinetheaveragemolecularkineticenergyandmolarkineticenergyofgaseoussulfur
hexafluoride,SF6,at150C.

Analysis

Theproblemasksforacalculationofkineticenergiesandprovidesatemperature.Wehave
twoequationsforthekineticenergyofagas.

Tocarryoutthecalculations,weneedtoknowtheconstantsR(8.314Jmol1K1)andNA
(6.02210 23mol1)aswellasTinkelvin.

Solution

ConvertthetemperaturefromCtoKbyadding273.15.

Nowsubstitutethisintothekineticenergyequationandcalculate.

Forasinglemolecule:
 For1moleofmolecules:

Isouranswerreasonable?

Wehaveshownthattheaveragekineticenergyisindependentofthenatureofthegas.
Figure6.10showsthemolecularenergydistributionsforatemperatureof300Kand900K.
Thetemperatureof423Kisinbetweentheseandthemolecularenergythatwecalculatedis
alsobetweenthevaluesat300Kand900K.Thisanswer,therefore,seemsreasonable.

PRACTICEEXERCISE6.4
Theatmospherictemperatureatthealtitudes
wherecommercialjetsflyisaround35C.
Calculatetheaveragemolecularandmolar
kineticenergiesofN2atthistemperature.

RatesofGasMovement
Theaveragespeedofthemoleculesinagasdeterminesitstemperature.Tostatethisdependence
quantitatively,westartwith:

and:

Wesetthetwoexpressionsforkineticenergyequaltoeachother.

Nowsolvethisequalityforu,notingthattheproductmNANisequaltothemolarmassofthegasinkg
mol1.

Thisspeediscalledtherootmeansquarespeedbecauseitisfoundbytakingthesquarerootof .
Theaveragespeedofgasmoleculesisdirectlyproportionaltothesquarerootofthetemperatureandis
inverselyproportionaltothesquarerootofthemolarmassofthegasinkgmol1.Thisequationcanbe
applieddirectlytothemovementofmoleculesescapingfromacontainerintoavacuum.Thisprocessis
oneexampleofeffusion(moregenerally,effusionistheflowofmoleculesthroughanopeningwithout
collisionsbetweenmolecules).Effusionisexemplifiedbytheescapeofmoleculesfromtheovenshown
infigure6.6a.
Asecondtypeofgasmovementisdiffusion,themovementofonetypeofmoleculethroughmolecules
ofthesameoranothertype.Diffusionisexemplifiedbyairescapingfromapuncturedtyre.The
escapingmoleculesmustdiffuseamongthemoleculesalreadypresentintheatmosphere.Diffusing
moleculesundergofrequentcollisions,sotheirpathsaresimilartothatshowninfigure6.1.
Nevertheless,theiraveragerateofmovementdependsontemperatureandmolarmass.Figure6.11
showsamolecularlevelcomparisonofeffusionanddiffusion.

FIGURE6.11Effusionisthemovementofagasintoavacuum.Diffusionisthemixingoftwoormoregases.

Anexampleofdiffusionisshowninfigure6.12,inwhichconcentratedaqueoussolutionsof
hydrochloricacid,HCl,andammonia,NH3,areplacedatoppositeendsofaglasstube.Moleculesof
HClgasandNH3gasescapefromthesolutionsanddiffusethroughtheairinthetube.Whenthetwo
gasesmeet,theyundergoareactionthatproducesammoniumchloride,awhitesolidsalt.

ThelighterNH3moleculesdiffusemorerapidlythantheheavierHClmolecules,sothewhitebandof
saltformsclosertotheHClendofthetube,ascanbeseeninfigure6.12.
 FIGURE6.12NH3 diffusesthroughaglasstubefasterthanHCl.Whenthetwogasesmeet,theyformsolid
ammoniumchloride,NH4 Cl(s),whichappearsasawhitebandclosertotheendofthetubethat
containsHCl.

Fromthediscussionofrootmeansquarespeedonthepreviouspage,itfollowsthattheratioof
distancesthatHClandNH3travel,respectively,isinverselyrelatedtothesquarerootofthemolar
masses:

Ratesofmolecularmotionaredirectlyproportionaltomolecularspeeds,so,foranygas,ratesof
effusionanddiffusionincreasewiththesquarerootofthetemperatureinkelvin.Also,atanyparticular
temperature,ratiosofeffusionanddiffusionarefasterformoleculeswithsmallmolarmasses.

IdealGases
Aswehaveseeninthischapter,gasescanconsistofeitheratomsormolecules.Inwhatfollows,wewill
usethetermmoleculesexclusivelyforbrevity'ssake,butyoumustrememberthateverythingsaid
aboutmoleculesinthissectionappliesequallytoatoms.

Thebehaviourofgasessuggeststhatgasmoleculeshavelittleeffectononeanother.Gasesareeasyto
compress,showingthatthereislotsofemptyspacebetweenmolecules.Gasesalsoescapeeasily
throughanyopening,indicatingthattheirmoleculesarenotstronglyattractedtooneanother.Anideal
gasisdefinedasagasforwhichboththevolumeofmoleculesandtheforcesbetweenthemolecules
aresosmallthattheyhavenoeffectonthebehaviourofthegas.Wecanassumethatthisisthecase
whenmolecularsizesarenegligiblecomparedwiththevolumeofthecontainer,andtheenergies
generatedbyforcesbetweenmoleculesarenegligiblecomparedwithmolecularkineticenergies.

Aswedescribelaterinthischapter,smallmoleculesusuallyhavesmallattractiveforceswithrespectto
theirkineticenergies,orwithrespecttoRT,oftencalledthethermalenergy.Table6.1liststhe
substancesthatexistasgasesunderambientconditions(notethatabinarygasisonethatcontains
moleculesformedfromtwoelements).Thesegasesaremostlysmallmoleculeswithmolarmassesless
than50gmol1.Therearesomenotableexceptionstothis,however.Tungstenhexafluoride,WF6(M=
297.8gmol1),andtheelementradon,Rn(M=222gmol1),areexamplesofgaseshavingmolar
massesgreaterthan200gmol1.Uraniumhexafluoride,UF6(M=334gmol1),asolidcompoundused
intheseparationofthefissionableuraniumisotope235Ufromthemoreabundant238Uisotope(see
chapter27),sublimes(changesdirectlyfromasolidtoagas)at56.5CtogiveUF6(g)atatmospheric
pressure.
TABLE6.1 Molarmassesofsomegaseoussubstances(at298Kand1.013105 Pa)
Elementalgases Binarygases
Substance Formula M(gmol1) Substance Formula M(gmol1)
hydrogen H2 2.016 methane CH4 16.04

helium He 4.003 ammonia NH3 17.03

neon Ne 20.18 carbonmonoxide CO 28.01

nitrogen N2 28.02 nitrogenoxide NO 30.01

oxygen O2 32.00 ethane C2H6 30.07

fluorine F2 38.00 hydrogensulfide H2S 34.09

argon Ar 39.95 hydrogenchloride HCl 36.46

ozone O3 48.00 carbondioxide CO2 44.01

chlorine Cl2 70.90 nitrogendioxide NO2 46.01

Howdoesanidealgasbehave?Wecananswerthisquestionbyconsidering,forexample,howchanges
inV,Tornaffectthepressure,p.Eachtimeamoleculestrikesawall,itexertsaforceonthewall.
Duringeachsecond,manycollisionsexertmanysuchforces.Pressureisthesumofalltheseforcesper
unitareaandunittime.Inanidealgas,eachmoleculeisindependentofallothers.Thisindependence
meansthatthetotalpressureisthesumofthepressurecreatedbyeachindividualmolecule.

ToseehowpressuredependsonV,Torn,weconsidertheeffectofchangingonepropertywhile
holdingtheotherpropertiesconstant.Weanalysewhathappenstothemolecularcollisionsaseach
propertychanges.

First,considerincreasingtheamountofgaswhilekeepingthetemperatureandvolumefixed.Doubling
theamountofgasinafixedvolume(figure6.13)doublesthenumberofcollisionswiththewalls.Thus,
aspressureisessentiallyameasureofthenumberofcollisionsofthemoleculeswiththewallsofthe
container,pressureisdirectlyproportionaltotheamountofgas.Thisagreeswiththeidealgasequation.
 FIGURE6.13Schematicviewoftheeffectofdoublingthenumberofgasmoleculesinafixedvolume.The
containerin(b)hastwiceasmanymoleculesasitdoesin
(a)Consequently,themoleculardensityistwiceaslargein
(b)withtwiceasmanycollisionspersecondwiththewalls.

Next,considerkeepingthetemperatureandamountfixedandchangingthevolumeofthegas.Figure
6.14showsthatcompressingagasintoasmallervolumehasthesameeffectasaddingmoremolecules.
Theresultismorecollisionswiththewalls.Ifthemoleculesactindependently,cuttingthevolumein
halfwilldoublethepressure.Inotherwords,pressureisinverselyproportionaltovolume,againin
agreementwiththeidealgasequation.

FIGURE6.14Schematicviewoftheeffectofcompressingafixedquantityofgasintoasmallervolumeat
constantT.Decreasingthevolumeincreasesthemoleculardensity,whichincreasesthe
numberofcollisionspersecondwiththewalls.

Tocompleteouranalysis,wemustdeterminetheeffectofachangeintemperature,keepingvolumeand
amountfixed.Recallthatkineticenergyisproportionaltothesquareofthemolecularspeed(a
microscopicvariable),andtemperature(amacroscopicvariable)isameasureofaveragemolecular
kineticenergy.Thus,thesquareofthemolecularspeedisproportionaltotemperature.Wecan
summarisetheserelationshipsby:

Molecularspeedaffectspressureintwoways,whichareillustratedinfigure6.15.First,fastermoving
moleculeshitthewallsmoreoftenthanslowermovingmolecules.Thenumberofcollisionseach
moleculemakeswiththewallisproportionaltothemolecule'sspeed.Second,theforceexertedwhena
moleculestrikesthewallalsodependsonthemolecule'sspeed.Afastmovingmoleculeexertsalarger
forcethanthesamemoleculemovingmoreslowly.Forcepercollisionandnumberofcollisions
increasewithspeed,sothetotaleffectofasinglemoleculeonthepressureofagasisproportionaltothe
squareofitsspeed.

FIGURE6.15Schematicviewoftheeffectofincreasingmolecularspeeds(asmeasuredbyanincreasein
temperature),resultinginmorewallcollisionsandmoreforcepercollision,andthereforean
increaseinpressure.

Pressureisproportionaltomolecularspeedsquared,whichinturnisproportionaltotemperature.Foran
idealgas,then,thepressureisdirectlyproportionaltotemperature,andaplotofpversusTyieldsa
straightline.Again,thisagreeswiththeidealgasequation.

Agaswillobeytheidealgasequationifitsmolecularsizesarenegligiblecomparedwiththevolumeof
thecontainer,andtheenergiesgeneratedbyforcesbetweenmoleculesarenegligiblecomparedwith
molecularkineticenergies.Thebehaviourofanyrealgasdepartssomewhatfromidealitybecausereal
moleculesoccupyvolumeandexertforcesononeanother.Nevertheless,departuresfromidealityare
smallenoughtoneglectundermanycircumstances,andrealgasesapproximateidealbehaviourunder
conditionsoflowpressureandhightemperature.Weconsiderdeparturesfromidealgasbehaviourlater
inthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.4GasMixtures
Theatmosphere,whichcontainsnitrogen,oxygenandvarioustracegases,isanobviousexampleofa
gasmixture.Anotherexampleisthegasusedbydeepseadivers,whichcontainsamixtureofhelium
andoxygen(figure6.16).Theidealgasmodelprovidesguidanceastohowtodescribemixturesof
gases.

FIGURE6.16Deepseadiversusemixturesofheliumandmolecularoxygenintheirbreathingtanks.

Allconstituentsofanidealgas,whetheratomsormolecules,actindependently.Thisnotionappliesto
gasmixturesaswellastopuregases.Gasbehaviourdependsonthenumberofgasatomsormolecules
butnotontheiridentity.Theidealgasequationappliestoeachgasinthemixture,aswellastothe
entirecollectionofatomsormolecules.

Supposeweintroduce0.1molofheliumintoanevacuated20Lflask.Ifweaddanother0.1molofHe,
thecontainernowcontains0.2molofgas.Thepressurecanbecalculatedusingtheidealgasequation,
withn=0.1mol+0.1mol=0.2mol.Supposethatweadd0.1molofmolecularoxygen.Nowthe
containerholdsatotalof0.3molofgas.Accordingtotheidealgasmodel,itdoesnotmatterwhether
weaddthesamegasoradifferentgasbecauseallatomsormoleculesinasampleofanidealgas
behaveindependently.Thepressureincreasesinproportiontotheincreaseinthetotalamountofgas.
Thus,wecancalculatethetotalpressurefromtheidealgasequation,usingn=0.2mol+0.1mol=0.3
mol.

Howdoesa1:2mixtureofO2andHeappearonthemolecularlevel?AsO2isaddedtothecontainer,
itsmoleculesmovethroughoutthevolumeandbecomedistributeduniformly.Diffusioncausesgas
mixturestobecomehomogeneous.Figure6.17illustratesthis.
 FIGURE6.17 (a)0.2molofHeareaddedtoacontainer.
(b)Theatomsquicklybecomedistributeduniformlythroughoutthecontainer.
(c)0.1molofO2 areaddedtothiscontainer.
(d)ThemoleculesmoveaboutindependentlyoftheHeatoms,causingthegasestomix
uniformly.

Dalton'sLawofPartialPressures
Thepressureexertedbyanidealgasmixtureisdeterminedbythetotalamount(n total)ofgas.

Wecanexpressthetotalamountofgasasthesumoftheamountsoftheindividualgases.FortheHe
andO2mixture:

Substitutiongivesatwotermequationforthetotalpressure.
Noticethateachtermontherightresemblestheidealgasequationrearrangedtoexpresspressure.Each
termthereforerepresentsthepartialpressureofoneofthegases.Asfigure6.18illustrates,partial
pressureisthepressurethatwouldbepresentinagascontainerifonegaswerepresentbyitself.

FIGURE6.18SchematicrepresentationofasampleofO2 ,asampleofHeandamixtureofthetwogases.
Bothcomponentsaredistributeduniformlythroughoutthegasvolume.Eachgasexertsthe
samepressure,whetheritispureorpartofamixture.

Thetotalpressureinthecontaineristhesumofthepartialpressures.

WehaveusedHeandO2toillustratethebehaviourofamixtureofidealgases,butthisrelationshipcan
beextendedfromamixtureoftwoidealgasestomixtureswiththreeormoresubstancesbehavingas
idealgases.Inamixtureofgasesinwhichnochemicalreactionoccurs,eachgascontributestothe
totalpressuretheamountthatitwouldexertifthegaswerepresentinthecontainerbyitself.Thisis
Dalton'slawofpartialpressures.Toobtainatotalpressure,simplyaddthecontributionsfromall
gasespresent.

Whendoingcalculationsonamixtureofgases,wecanapplytheidealgasequationtoeachcomponent
tofinditspartialpressure(p i).Alternatively,wecantreattheentiregasasaunit,usingthetotalamount
todeterminethetotalpressureofthemixture(p).

DescribingGasMixtures
Thereareseveralwaystodescribethechemicalcompositionofamixtureofgases.Thesimplestmethod
istolisteachcomponentwithitspartialpressureoramount.Twootherdescriptions,molefractionsand
partspermillion,arealsousedfrequently.

Chemistsoftenexpresschemicalcompositioninfractionalterms,statingtheamountofasubstanceasa
fractionoftheamountofallsubstancesinthemixture.Thiswayofstatingcompositionisthemole
fraction(x).
Molefractionsprovideasimplewaytorelatethepartialpressureofonecomponenttothetotalpressure
ofthegasmixture.

Dividingp Abyp totalgives:

or:

Thepartialpressureofacomponentinagasmixtureisitsmolefractionmultipliedbythetotalpressure.

WORKEDEXAMPLE6.5

GasMixtures
Exactly8.00gofO2and2.00gofHewasplacedina5.00Ltankat298K.Determinethe
totalpressureofthemixture,andfindthepartialpressuresandmolefractionsofthetwo
gases.

Analysis

Wehaveamixtureoftwogasesinacontainerwithknownvolumeandtemperature.The
problemasksforpressuresandmolefractions.Assumingthatmolecularinteractionsare
negligible,eachgascanbedescribedindependentlybytheidealgasequation.Asusual,we
needmolaramountsforthecalculations.

Solution

Beginwiththedataprovided.

Convertthemassofeachgasintoanamountinmoles.

Next,usetheidealgasequationtocalculatethepartialpressureofeachgas.

ThesamecalculationforO2gives Pa.

Thetotalpressureisthesumofthepartialpressures.
 Molefractionscanbecalculatedfromamountsorpartialpressures.

Isouranswerreasonable?

Themolefractionscalculatedfromthepartialpressuresmustsumto1.00.Theydointhis
case,suggestingthatouranswerisreasonable.

PRACTICEEXERCISE6.5
A5.00Ltankischargedwith7.50gofO2
and2.50gofHe.Calculatethemole
fractionsandthepartialpressuresofthe
gasesat25C.

Whenreferringtolowerconcentrationsinagasmixture,scientiststypicallyusepartspermillion(ppm)
orpartsperbillion(ppb).Molefractions,partspermillionandpartsperbillioncanalldescriberatiosof
amountofaparticularsubstancetototalamountofasample.Molefractionismolesperamounts,ppm
ismolespermillionmolesandppbismolesperbillionmoles.Aconcentrationof1ppmisamole
fractionof10 6,and1ppbisamolefractionof10 9.

WORKEDEXAMPLE6.6

WorkingWithPartsPerMillion(ppm)
Theexhaustgasfromanaveragecarcontains206ppmofthepollutantnitrogenoxide,NO.
Ifacaremits0.125m3ofexhaustgasat1.0010 5Paandexactly350K,whatmassofNO
hasbeenaddedtotheatmosphere?

Analysis

ThequestionasksforthemassofNO.Informationaboutconcentrationinppmtellsusthe
amountofNOpresentin1moleofexhaustgas.Wecanusetheidealgasequationto
determinethetotalamountofgasemitted,thenusetheconcentrationinformationtofindthe
amountofNO,andusethemolarmassofNOtoobtaintherequiredmass.

Solution
 Isouranswerreasonable?

ThemassofNOisrathersmall,only27mg,butthemolefractionisalsosmall,sothisisa
reasonableresult.

PRACTICEEXERCISE6.6
IfthemaximumNOemissionallowedin
workedexample6.6is762ppm,whatmass
ofNOisallowedperlitreofexhaustemitted
atatemperatureofexactly50C?

Thedescriptionpresentedinthissectionappliestoagasmixturethatisnotundergoingchemical
reactions.Aslongasreactionsdonotoccur,theamountofeachgasisdeterminedbytheamountofthat
substanceinitiallypresent.Whenreactionsoccur,theamountsofreactantsandproductschangeas
predictedbytheprinciplesofstoichiometry.Changesincompositionmustbetakenintoaccountbefore
thepropertiesofthegasmixturecanbecalculated.Gasstoichiometryisdescribedinsection6.6.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.5ApplicationsoftheIdealGasEquation
Theidealgasequationandthemolecularviewofgasesleadtoseveralusefulapplications.Wehavealready
describedhowtocarryoutcalculationsinvolvingpVnTrelationships.Inthissection,weexaminetheuse
ofthegasequationtodeterminemolarmassesandgasdensity.

DeterminationofMolarMass

Theidealgasequationcanbecombinedwiththeequation (fromchapter3)tofindthemolarmassof
anunknowngas.

Ifweknowthepressure,volumeandtemperatureofagassample,wecanusethisinformationtocalculatethe
amountinmolesoftheunknowngasinthesample.

Ifwealsoknowthemassofthegassample,wecanusethatinformationtodeterminethemolarmassofthe
gas.

WORKEDEXAMPLE6.7

MolarMassDetermination
Purecalciumcarbide,CaC2,isahard,colourlesssolidthatwasusedincavinglamps.Ithasa
meltingpointof2160C,anditreactsvigorouslywithwatertoproduceagasandasolution
containingOHions.

A12.8gsampleofCaC2wastreatedwithexcesswaterandtheresultinggaswascollectedinan
evacuated5.00Lglassbulbwithamassof1254.49g.Thefilledbulbhadamassof1259.70gand
thepressureofthegasinsidewas1.0010 5Pawhenthetemperaturewas26.8C.Calculatethe
molarmassofthegasanddetermineitsformula.(Assumethattheproductgasisinsolubleinwater
andthatthevapourpressureofwaterisnegligibleinrelationtothepressureoftheproductgas.)

Analysis

Wecanusetheidealgasequationtocalculatethemolarmass.Thenwecanusethemolarmassto
identifythecorrectmolecularformulafromagroupofpossiblecandidates,astheproductsmay
containonlythesameelementsasthereactants.Theprobleminvolvesachemicalreaction,sowe
mustmakeaconnectionbetweenthegasmeasurementsandthechemistrythattakesplace.Because
thereactantsandoneproductareknown,wecanwriteapartialequationthatdescribesthechemical
reaction.

Inanychemicalreaction,atomsmustbeconserved,sothegasmoleculescancontainonlyH,O,C
and/orCaatoms.Todeterminethechemicalformulaofthegas,wemustfindthecombinationof
theseelementsthatgivestheobservedmolarmass.
theseelementsthatgivestheobservedmolarmass.

Solution

Usethedatatodeterminethemolarmass.Theproblemgivesthefollowingdataabouttheunknown
gas.

WeuseV,T,pandtheidealgasequationtofindtheamountofgasinmoles.Then,withthemassof
thegassample,wecandeterminethemolarmass.

WecouldrearrangethisexpressionandsolvetheequalityforMdirectly,but,inproblemslikethis,it
isoftenbettertocarryouteachstepexplicitly.Therefore,wewillfirstdeterminenandthensolvefor
M.

Toidentifythegas,weexaminetheformulaeandmolarmassesofknowncompoundsthatcontain
onlyH,O,CorCa.

Formula M Comment
Ca 40 AgaswithM=26.0gmol1cannotcontainCa.

CO 28 Thisisclosebuttoohigh.
O2 32 Thisisalsotoohigh.
H2O 18 Thisistoolow,andH2Oisareactantnotaproduct.
CH4 16 Thisistoolow.
C2H2 26 Thissubstancehastheobservedmolarmass.

ConsiderationofthesepossibilitiesleadstothemolecularformulaC2H2,ethyne(commonlyknown
asacetylene).

Isouranswerreasonable?

KnowingtheformulaofthegaseousproductandthatOHisanotherproduct,wecanwritea
balancedequationforthegenerationofethyne.

Thebalancedequationsuggeststhattheresultisreasonable.Asystematicevaluationofallpossible
gasesfromthereagentsthatinvolveonlyoneortwoatomsotherthanhydrogenshowsthatthereare
nootherpossibilitiesformolarmass26gmol1.

PRACTICEEXERCISE6.7
 Theglassbulbinworkedexample6.7isfilled
withanunknowngasuntilthepressureis1.03
10 5Paatatemperatureof24.5C.Themass
ofthebulbpluscontentsis1260.33g.
Determinethemolarmassoftheunknowngas.

DeterminationofGasDensity
Onecharacteristicofgasesisthatthedensityofagasvariessignificantlywiththeconditions.Toseethis,we
combinetheidealgasequationand andrearrangetoobtainanequationfordensity .

Setthetwoexpressionsfornequaltoeachother.

Now,multiplybothsidesoftheequalitybyManddividebothsidesbyV.

Thisequationrevealsthreefeaturesofgasdensity:
1.Thedensityofanidealgasincreaseslinearlywithincreasingpressureatfixedtemperature.Thereason
isthatincreasingthepressurecompressesthegasintoasmallervolumewithoutchangingitsmass.

2.Thedensityofanidealgasdecreaseslinearlywithincreasingtemperatureatfixedpressure.Thereason
isthatincreasingthetemperaturecausesthegastoexpandwithoutchangingitsmass.

3.Thedensityofidealgasesincreaseslinearlywithincreasingmolarmassatagiventemperatureand
pressure.Thereasonisthatequalamountsofdifferentgasesoccupyequalvolumesatagiven
temperatureandpressure.

Therearepracticalapplicationsofallthesefeatures:
SCUBAdiversusehighpressurecylinders,wherethehighdensityofthegasgivesthemmoredivetime
pervolume(figure6.19).
 FIGURE6.19ThehighdensityofairinsideaSCUBAtankincreasesthetimethatadivercanremainunder
water.

Balloonsinflatedwithheliumriseintheatmospherebecausethemolarmassofheliumissubstantially
lowerthantheaveragemolarmassofair(figure6.20).Consequently,thedensityofaheliumfilled
balloonislessthanthedensityofair,andtheballoonrises,justasacorkreleasedunderwaterrisesto
thesurface.

FIGURE6.20Aheliumfilledballoonfloatsbecauseheliumislessdensethanair.
Whentheairwithinahotairballoonisheated,itsdensitydecreasesbelowthatoftheoutsideair.With
sufficientheating,theballoonrisesandfloats(figure6.21).Incontrast,coldairisdenserthanwarmair,
socoldairsinks.Forthisreason,valleysoftenarecolderthanthesurroundinghillsides.
 FIGURE6.21Ahotairballoonrisesbecausetheairinsideisheatedtoreduceitsdensity,sothatitisless
densethantheoutsideair.

Whenagasisreleasedintotheatmosphere,whetheritrisesorsinksdependsonitsmolarmass.Ifthemolar
massofthegasisgreaterthantheaveragemolarmassofair,thegasremainsneartheground.Carbondioxide
fireextinguishersareeffectiveforcertainfiresbecauseofthisfeature.ThemolarmassofCO2(44.0gmol1)
isgreaterthanthatofN2(28.0gmol1)orO2(32.0gmol1),andsoaCO2fireextinguisherlaysdowna
blanketofthisgasthatexcludesoxygenfromthefire.

WORKEDEXAMPLE6.8

GasDensity
Acertainhotairballoonwillrisewhenthedensityofitsairis15.0%lowerthanthatofthe
surroundingatmosphericair.Calculatethedensityofairat295Kand1.0010 5Pa(assumethat
dryairis78.0%N2and22.0%O2),anddeterminetheminimumtemperatureofairinsidethe
balloonthatwillcausetheballoontorise.

Analysis

Theproblemhastwoparts.First,wemustcalculatethedensityofatmosphericair.Todothis,we
needtodeterminethemolarmassofdryair,whichistheweightedaverageofthemolarmassesof
itscomponents.Thenwemustcalculatethetemperatureneededtoreducethedensityby15.0%.
Forbothcalculations,weusetheidealgasequationasrearrangedtogivegasdensity.

Solution

Beginbycalculatingthemolarmassofdryair.Multiplythefractionofeachcomponentbyits
molarmass.

Theotherconditionsarestatedintheproblem.
 Recallthat,becausetheunitPaisdefinedintermsofNm2,andthat1N=1kgms2,wemustuse
amolarmassinkgmol1inthisequation.Substitutingtheseintotheequationforgasdensity
gives:

Theballoonwillrisewhenthedensityofitscontentsis15%lessthanthedensityofthe
surroundingair.

Rearrangethedensityequationtosolvefortemperature,thensubstituteandcalculate.

Isouranswerreasonable?

Atemperatureof348Kor75Cisareasonableresultasitishigherthanthetemperatureofthe
surroundingair.Noticethatthemolarmassandgasconstantappearinbothcalculations,sowecan
alsofindthetemperaturerequirementbysimpleproportions(comparingtheairinsideandoutside
theballoon).

PRACTICEEXERCISE6.8
Heliumisusedforlighterthanairblimps,
whereasargonisusedtoexcludeairfrom
flasksinwhichairsensitivesynthesesare
performed.Calculatethedensitiesofthesetwo
group18gasesat295Kand1.0010 5Pa,
andexplainwhythetwogaseshavedifferent
uses.

Gasdensityhasasignificanteffectontheinteractionsbetweenmoleculesofagas.Asmoleculesmoveabout,
theycollideregularlywithoneanotherandwiththewallsoftheircontainer.Figure6.22showsthatthe
frequencyofcollisionsdependsonthedensityofthegas.Atlowdensity,amoleculemaymoveasignificant
distancebeforeitencountersanothermolecule.Athighdensity,amoleculetravelsonlyashortdistance
beforeitcollideswithanothermolecule.
 FIGURE6.22Asthemoleculardensitydecreases,theaveragedistancetravelledbetweenmolecularcollisions
increases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.6GasStoichiometry
Theprinciplesofstoichiometryapplyequallytosolids,liquidsandgases.Nomatterwhatphase
substancesarein,theirchemicalbehaviourcanbedescribedinmolecularterms,andtheir
transformationsmustbevisualisedandbalancedusingmoleculesandmoles.

Theidealgasequationrelatestheamountofgastothephysicalpropertiesofthatgas.Whenachemical
reactioninvolvesagas,theidealgasequationprovidesthelinkbetweenpVTdataandmolar
amounts.

Stoichiometriccalculationsalwaysrequireamountsand,forgases,theseareusuallycalculatedfromthe
idealgasequation.

WORKEDEXAMPLE6.9

GasStoichiometry
Workedexample6.7describedtheformationofethyne,C2H2,fromcalciumcarbide,CaC2.
Modernindustrialproductionofethyneisbasedonareactionofmethane,CH4,undercare
fullycontrolledconditions.Attemperaturesgreaterthan1600K,twomethanemolecules
rearrangetogivethreemoleculesofhydrogenandonemoleculeofethyne.

A50.0Lsteelvessel,filledwithCH4toapressureof10.010 5Paat298K,isheatedto
exactly1600KtoconvertCH4intoC2H2.WhatisthemaximumpossiblemassofC2H2that
canbeproduced?Whatpressuredoesthereactorreachat1600K?AssumethatbothCH4
andC2H2behaveasidealgasesundertheconditionsofthereaction.

Analysis

Thisisastoichiometryprobleminvolvinggases.Themassofaproductandthefinalpres
suremustbecalculated.Wecandrawadiagramshowingtheprocessandlistingthedata.

Solution

Inanystoichiometryproblem,weworkwithamounts.Thisprobleminvolvesgases,sowe
usetheidealgasequationtoobtainamountsinmolesfromthepVTinformation.Usethe
idealgasequationtocalculatetheamountofCH4presentinitially.
 Fromthestoichiometryofthebalancedchemicalequation,wecandeterminethatcomplete
conversionof20.18molofCH4intoC2H2andH2willgive molC2H2

and molH2.

Nowwedeterminethemassofethyneformed.

Usingtheidealgasequationandthetotalamountpresentattheendofthereaction,and
assumingalltheCH4hasreacted,wecancalculatethefinalpressure.

Isouranswerreasonable?

Fromtheinitialamountofmethane,wecancalculatetheinitialmassofmethane,whichis
323g.Themassofethyne,263g,islessthanthis,areasonableresultgiventhatH2isalso
produced.Thefinalpressure,1.0710 7Pa,seemshigh,butthetemperatureofthereactor
hasincreasedsubstantiallyandtheamountofproductsistwicetheamountofreactants,soa
largepressureincreaseistobeexpected.

PRACTICEEXERCISE6.9
Calculatethevolumeofhydrogengas
generatedwhen1.52gofMgreactswithan
excessofaqueousHCl,ifthegasis
collectedat1.0010 5Paand22.5C.The
balancedchemicalequationforthereaction
is:

Anyofthetypesofproblemsdiscussedinchapter3caninvolvegases.Thestrategyfordoing
stoichiometriccalculationsisthesamewhetherthespeciesinvolvedaresolids,liquidsorgases.Inthis
chapter,weaddtheidealgasequationtoourequationsforrelatingmeasuredquantitiestoamounts.

WORKEDEXAMPLE6.10
LimitingReagentsinaGasMixture
Margarinecanbemadefromnaturaloilssuchascoconutoilbyhydrogenation.

Ahydrogenator(figure6.23)withavolumeof2.5010 2Lischargedwith12.0kgofoil.
Theremainingvolumeisthenfilledwith7.0010 5Paofhydrogen,H2,at473K.The
reactionproducesthemaximumamountofmargarine.WhatisthefinalpressureofH2,and
whatmassofmargarinewillbeproduced?AssumethatH2doesnotdissolveincoconutoil
ormargarine,thatitbehavesasanidealgasunderthereactionconditionsandthatthe
coconutoilandmargarineoccupyanegligiblevolumeinthehydrogenator.

FIGURE6.23Ahydrogenatoravailablecommerciallyforsmallscaleuse,e.g.inaresearch
laboratory.

Analysis

Wehavedatafromwhichwecancalculatetheamountsofbothstartingmaterials.Giventhe
chemicalequation,thefirststepinastoichiometryproblemistodeterminetheinitialamount
ofeachstartingmaterial.Next,calculateratiosofamountstocoefficientstoidentifythe
limitingreagent.Afterthat,usetheidealgasequationandthestoichiometricprincipleswe
learnedinchapter3toobtainthefinalanswers.

Solution

Theidealgasequationisusedforthegaseousstartingmaterial.

Weobtaintheamountofoilfromthemassandthemolarmass.
Nowwedivideeachamountbythestoichiometriccoefficienttoidentifythelimitingreagent.

Thereactantwiththesmallerratio,oil,islimiting.(Excesshydrogeniseasilyrecoveredfrom
agasphasereactor,somargarinemanufacturersmaketheoilthelimitingreagenttoensure
completeconversionofoilintomargarine.TheexcessH2gasisrecoveredandreused.)

Fromthebalancedchemicalequation,13.55molofoilwillreactwith40.65mol(313.55)
ofH2togive13.55molofmargarine.Therefore,theamountofunreactedH2willbe(44.50
40.65)=3.85mol.Notethatwehavecarriedanextrafigurethroughthecalculation.We
thereforeneedtoroundtothecorrectnumberofsignificantfiguresatthispoint,so13.6mol
ofmargarinewillbeproducedand3.9molofH2willremainunreacted.

Usingtheidealgasequation,wecalculatethepressureofhydrogenattheendofthereaction.

Nowwecalculatethemassofmargarine.

Isouranswerreasonable?

Inthisexample,oilisthelimitingreagentandnotalltheH2willreact.Therefore,someH2
willbeleft,butweexpectthepressureofH2attheendofthereactiontobelowerthanatthe
start,whichitis.Noticethatthemassofmargarineproduced(12.1kg)isonlyslightlygreater
thanthemassofoilwestartedwith(12.0kg).Thisistobeexpected,asthemolarmassesof
coconutoilandmargarineareverysimilar.

PRACTICEEXERCISE6.10
Intheindustrialproductionofnitricacid,
onestepistheoxidationofnitrogenoxide:
2NO(g)+O2(g)2NO2(g).Areaction
chamberischargedwith5.0010 5Paeach
ofNOandO2.Ifthereactiongivesthe
maximumpossibleamountofNO2(g)
withoutachangeintemperatureorvolume,
 calculatethefinalpressuresofeachreagent.

SummaryofMoleConversions
Onthemicroscopiclevel,molesarethecurrencyofchemistrytherefore,allstoichiometriccalculations
requireamounts.Onthemacroscopiclevel,wemeasuremass,volume,temperatureandpressure.Table
6.2liststhreeequationsthatcanbeusedtoconvertbetweenthemicroscopicandmacroscopiclevels.
Eachoftheseequationsappliestoaparticularcategoryofchemicalsubstances.Youshouldhavea
workingknowledgeofthesethreeequations,alongwiththecategoryofsubstancestowhichtheyapply.
TABLE6.2 Summaryofstoichiometricrelationships
Substance Relationship Equation
puresolid,liquid
orgas

solution

gas

Workedexample6.11usesallthreerelationships.Viewedasawhole,theexamplemayseem
complicated.However,asthesolutionillustrates,breakingtheproblemintoseparatepartsallowseach
parttobesolvedusingsimplechemicalandstoichiometricprinciples.Complicatedproblemsareoften
simplifiedconsiderablybylookingatthemonepieceatatime.

WORKEDEXAMPLE6.11

GeneralStoichiometry
Reactionofmagnesiummetalwithacid(figure6.24)generateshydrogengasandanaqueous
solutionofions.Supposethat3.50gofmagnesiummetalisdroppedinto0.150Lof6.00M
HClina5.00Lcylinderat25.0C.Theinitialgaspressureofthecylinderis1.0010 5Pa,
anditisimmediatelysealed.Findthefinalpartialpressureofhydrogen,thetotalpressurein
thecontainerandtheconcentrationofMg 2+insolution.
 FIGURE6.24MagnesiumreactingwithaqueousHCl.

Analysis

Dataaregivenforallreactants.Wemustfirstwriteabalancedchemicalequationandthen
usetheequationsintable6.2,alongwiththestoichiometryofthereaction,tocalculatethe
requiredpressuresandconcentrations.

Solution

Webeginbywritingthebalancedchemicalequation,whichwehaveseenpreviouslyin
practiceexercise6.9.

Theproblemasksforpressuresandionconcentrations.Thefinalpressurecanbedetermined
frompVTdataandn H2.Theamountofhydrogencanbefoundfromthemassof
magnesiumandthestoichiometricratio.Hereisasummaryofthedata.

Nowweanalysethestoichiometryofthereaction.ThestartingmassofMgandthevolume
andconcentrationofHClaregiven,andwecanusethesedatatofindthelimitingreactant.

Wedividebythestoichiometriccoefficientstoshowthatmagnesiumisthelimitingreagent.

Fromthestoichiometryofthebalancedchemicalequation,wecanshowthat0.144molof
Mgwillform0.144molH2.WethereforeusethisamounttocalculatethepressureofH2.
However,beforedoingthis,wemustvisualisethereactionvessel.Thecontainer'stotal
volumeis5.0010 3m3,but0.15010 3m3isoccupiedbytheaqueoussolution.This
 leaves4.8510 3m3forthegasmixture.Thepartialpressureofhydrogeniscalculated
usingtheidealgasequationandassumingthatnoH2remainsinsolutionthisisagood
assumptionbecausehydrogengasisnotverysolubleinwater.

Assumingthattheamountofairoriginallypresentdoesnotchangeinthereaction,the
pressureexertedbytheairremainsconstantat1.0010 5Pa.Thefinaltotalpressureisthe
sumofthepartialpressures.

WecancalculatethefinalconcentrationofMg 2+usingtheinitialamountofMgandthe
volumeofthesolution.

PRACTICEEXERCISE6.11
Repeatthecalculationsfromworked
example6.11withallconditionsthesame
exceptthat14.0gofMgisaddedtotheHCl
solution.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.7RealGases
Inchapter5welookedatwhatholdsatomsandionstogether,andwelistedthreetypesofbonding
forces:ionic,covalentandmetallic.Inadditiontotheserelativelystrongbondingforces,therearemuch
weakerforcesthatexistbetweenatoms,ionsandmolecules.Intheprevioussectionsofthischapterwe
lookedatidealgases,assumingthattherearenoattractiveforcesbetweeneitheratomsormolecules.
However,weakattractiveforcesdooccurinrealgases,andmuchstrongerforcesarepresentinliquids
andsolids.Intheabsenceoftheseintermolecularforces,allmoleculeswouldmoveindependently,
andallmolecularsubstanceswouldbegases.Theseintermolecularforcesareessentiallydueto
attractionsbetweenpolarisedmolecules,buttheyalsoincludepolarinteractionsbetweenionsand
moleculesaswellasatoms.Thename,intermolecularforces,isthereforesomewhatinaccurate,butit
canbejustifiedbythefactthatanoverwhelmingnumberofallchemicalcompoundsaremolecules.

TheHalogens
Thehalogens,theelementsfromgroup17oftheperiodictable,provideanintroductiontointer
molecularforces.Theseelementsexistasdiatomicmolecules:F2,Cl2,Br2andI2.Eachmolecule
containstwoatomsheldtogetherbyasinglecovalentbondthatcanbedescribedbyendonoverlapof
valenceporbitals.

Althoughtheyhavesimilarcovalentbonding,bromineandiodinedifferfromchlorineandfluorinein
theirmacroscopicphysicalappearanceandintheirmolecularbehaviour.Asfigure6.25shows,atroom
temperatureandpressure,chlorine(likefluorine)isagas,bromineisaliquidandiodineisasolid.

Undernormalconditions,chlorineisapaleyellowgreengas,bromineisadarkredliquid,and
 FIGURE6.25iodineisadarkcrystallinesolid.

Gasesandcondensedphases(atermusedtocollectivelydescribeliquidsandsolids)lookverydifferent
atthemolecularlevel.MoleculesofF2orCl2movefreelythroughouttheirgaseousvolume,travelling
manymoleculardiametersbeforecollidingwithoneanotherorwiththewallsoftheircontainer.
Becausemuchofthevolumeofagasisemptyspace,samplesofgaseousF2andCl2readilyexpandor
contractinresponsetochangesinpressure.Thisfreedomofmotionexistsbecausetheintermolecular
forcesbetweenthesemoleculesaresmallwithrespecttotheirkineticenergy.

Moleculesofliquidbrominealsomoveaboutrelativelyfreely,butthereisnotmuchemptyspace
betweenmolecules.Aliquidcannotbecompressedsignificantlybyincreasingthepressure,becauseits
moleculesarealreadyinclosecontactwithoneanother.Neitherdoesaliquidexpandsignificantlyifthe
pressureisreduced,becausetheintermolecularforcesinaliquidarestrongenoughtopreventthe
moleculesfrombreakingawayfromoneanother.

Solidiodine,likeliquidbromine,haslittleemptyspacebetweenmolecules.Likeliquids,solidshave
sufficientlystrongintermolecularforcesthattheyneitherexpandnorcontractsignificantlywhenthe
pressurechanges.Insolids,theintermolecularforcesarestrongenoughtopreventmoleculesfrom
movingfreelypastoneanother.Instead,theI2moleculesinthesolidphasearearrangedinordered
arrays.Eachmoleculevibratesbackandfortharoundasinglemoststableposition,butitcannotslide
easilypastitsneighbours.

Thebalancebetweenmolecularkineticenergiesandintermolecularattractiveforcesaccountsforthese
strikingdifferences(figure6.26).Recallfromsection6.2thatmoleculesarealwaysmoving.
Intermolecularattractiveforcestendtoholdmoleculestogetherinacondensedphase,butmolecules
thataremovingfastenoughcanovercometheseforcesandmovefreelyinthegasphase.Whenthe
averagekineticenergyislargeenough,moleculesremainseparatedfromoneanother,andthe
substanceisagas.Conversely,whenintermolecularattractiveforcesarelargeenough,molecules
remainclosetooneanother,andthesubstanceisaliquidorsolid.

FIGURE6.26Asubstanceexistsinacondensedphasewhenitsmoleculeshavetoolittleaveragekinetic
energytoovercomeintermolecularforcesofattraction.

Thebarsinfigure6.27comparetheattractiveenergiesarisingfromintermolecularforcesactingonthe
halogens.Thefigurealsoshowstheaveragemolecularkineticenergyatroomtemperature.Forfluorine
andchlorine,theattractiveenergygeneratedbyintermolecularforcesissmallerthantheaverage
molecularkineticenergyatroomtemperature.Thus,theseelementsaregasesundertheseconditions.In
contrast,brominemoleculeshaveenoughkineticenergytomovefreelyabout,buttheirenergyis
insufficienttoovercometheintermolecularforcesoftheliquidphase.Finally,attractiveforcesiniodine
arestrongenoughtolocktheI2moleculesinpositioninthesolidstate.
 FIGURE6.27Thebalanceofaveragekineticenergy(redline)andintermolecularenergiesofattraction
favoursthegasphaseforF2 andCl2 ,andthecondensedphasesforBr2 andI2 .

PropertiesofRealGases
Aswedescribedinsection6.3,theidealgasmodelmakestwoassumptions:agashasnegligibleforces
betweenitsconstituentatomsormolecules,andgasatomsormoleculeshavenegligiblevolumes.
Neitheroftheseassumptionsistrueforarealgas.Atsufficientlyhighpressuresandsufficientlylow
temperatures,allgasescanbeliquefied.

Howclosedorealgasescometoidealbehaviour?Toanswerthisquestion,werearrangetheidealgas
equationtoexaminetheratio .Figure6.28showshowthe ratiovarieswithpressurefor

chlorinegasatroomtemperature.Ifchlorinewereanidealgas,the ratiowouldalwaysbe1,as
shownbytheredlineonthegraph.Instead,chlorineshowsdeviationsfrom1asthepressureincreases.
 FIGURE6.28Thevariationin withpressureshowsthatchlorineisnotanidealgas.

Noticeintheinsetoffigure6.28thatchlorineisnearlyidealatpressuresaround110 5Pa.Infact,
deviatesfrom1.0bylessthan4%atpressuresbelow410 5Pa.Asthepressureincreases,

however,thedeviationsbecomeincreasinglysignificant.Withincreasingpressure,the ratiofor
chlorinedropsbelow1.Thisisbecausethechlorinemoleculesarecloseenoughtogetherforattractive
forcestoplayasignificantrole.Theseintermolecularattractionsholdmoleculestogetherandreducethe
forcesexertedwhenthemoleculesstrikethewallsofthecontainer.Intermolecularattractionstendto
makethepressureofarealgaslowerthantheidealvalue.

Figure6.28alsoshowsthatatpressuresgreaterthan37510 5Pa, becomeslargerthan1.Thisis

duetotheeffectofmolecularsize.Athighenoughpressure,themoleculesarepackedsoclosetogether
thatthetotalvolumeofthemoleculesisnolongernegligiblecomparedwiththeoverallvolumeofthe
container.Theresultisthatthecontainervolumeiseffectivelydecreasedbythemolecules'volumeand
thepressureoftherealgastendstobegreaterthanthatoftheidealgas.

Everygasshowsdeviationsfromidealbehaviourathighpressure.Figure6.29shows forHe,F2,

CH4andN2,allofwhicharegasesatroomtemperature.Noticethat forheliumincreasessteadily
aspressureincreases.Interatomicforcesforheliumaretoosmalltoreducetheratiobelow1,butthe
finitesizeoftheheliumatomgeneratesdeviationsfromidealbehaviourthatbecomesignificantat
pressuresabove10010 5Pa.

FIGURE6.29Variationsin forHe,N2 ,F2 andCH4 at300K.

Giventhateverygasdeviatesfromidealbehaviourtosomedegree,canweusetheidealgasmodelto
discussthepropertiesofrealgases?Theanswerisyes,aslongasconditionsdonotbecometoo
extreme.Thegaseswithwhichchemistsoftenwork,suchaschlorine,heliumandnitrogen,arenearly
idealatroomtemperatureatpressuresbelowabout1010 5Pa,but,atveryhighpressuresornearthe
condensationpointsofsubstances,deviationsfromtheidealgasequationbecomelarge.

TheVanDerWaalsEquation
Itwouldbeusefultohaveanequationthatdescribestherelationshipbetweenpressureandvolumefora
realgas,justas describesanidealgas.Onewaytoapproachrealgasbehaviouristomodifythe
idealgasequationtoaccountforattractiveforcesandmolecularvolumes.Theresultisthevander
Waalsequation,namedafterthescientistwhofirstproposeditin1873,JohannesvanderWaals(1837
1923,NobelPrizeinphysics,1910).

ThevanderWaalsequationaddstwocorrectiontermstotheidealgasequation.Eachcorrectionterm
includesaconstantthathasaspecificvalueforeverygas.Thefirstcorrectionterm, ,adjustsfor
attractiveintermolecularforces.ThevanderWaalsconstantareflectsthestrengthofintermolecular
forcesforthegasthestrongertheforces,thelargerthevalueofa.Thesecondcorrectionterm,nb,
adjustsformolecularsizes.ThevanderWaalsconstantbreflectsthesizeofgasatomsormoleculesthe
largertheyare,thelargerthevalueofb.

ThevanderWaalsconstantsforanumberofgasesappearintable6.3,andthemagnitudeofvander
Waalscorrectionsisexploredinworkedexample6.12.
TABLE6.3 ValuesofvanderWaalsconstantsforavarietyofgases
a b

Substance (m6Pamol2) (m3mol1)

He 3.45710 3 2.3710 5
Ne 2.13510 2 1.70910 5
Ar 1.36310 1 3.21910 5
H2 2.47610 2 2.66110 5
N2 1.40810 1 3.91310 5
O2 1.37810 1 3.18310 5
CO 1.50510 1 3.98510 5
F2 1.15610 1 2.9010 5
Cl2 6.57910 1 5.62210 5
CO2 3.64010 1 4.26710 5
H2O 5.53610 1 3.04910 5
NH3 4.22510 1 3.70710 5
 CH4 2.28310 1 4.27810 5
C2H6 5.56210 1 6.380 5
C6H6 1.82410 1 1.15410 5

WORKEDEXAMPLE6.12

MagnitudesofVanDerWaalsCorrections
Gasessuchasmethanearesoldandshippedincompressedgascylinders(figure6.30).A
typicalcylinderhasavolumeof15.0Land,whenfull,contains62.0molofCH4.After
prolongeduse,0.620molofCH4remainsinthecylinder.

FIGURE6.30Gasessuchasmethane,butaneandpropanearesoldincompressedgas
cylinders.

UsethevanderWaalsequationtocalculatethepressuresinthecylinderwhenfullandafter
use,andcomparethevalueswiththoseobtainedfromtheidealgasequation.Assumea
constanttemperatureof25C.

Analysis

WeareaskedtocalculateandcomparethepressuresofmethanegasusingthevanderWaals
equationandtheidealgasequation.VanderWaalsconstantsaandbmustbelookedupina
datatablesuchastable6.3.Tocalculatepressures,werearrangethevanderWaalsequation
andtheidealgasequation.

Solution
ThevanderWaalsconstantsforCH4are:

Whenthetankisfull,n=62.0mol.

Afteruse,n=0.620mol.

Organisetheresultstomakeacomparison.

NoticethatthevanderWaalscorrectionisappreciable(15.4%)athighpressure,butis
negligibleatatmosphericpressure(1.01310 5Pa).

Isouranswerreasonable?

Weknowthatmethaneisnormallyagasat298Kandatmosphericpressure,soitmakes
sensethatthegasbehavesideallyundertheseconditions.Apressureabove10010 5Pais
substantiallyhigherthannormalconditions,soweexpecttoseedeviationsfromideal
behaviour.

PRACTICEEXERCISE6.12
Methaneboilsat164C.Usetheidealgas
equationtocalculatethemolarvolumeof
 methanegasatthistemperatureat1.013
10 5Papressure.ThenusethevanderWaals
equationtocalculatethepressureexertedby
1.00moleofthegasifitoccupiesthis
volumeat164C.

MeltingandBoilingPoints
Meltingpointsandboilingpointscanbeusedasindicatorsofthestrengthsofintermolecularforces.
Rememberthatthetemperatureincreaseswiththeaveragekineticenergyofmolecularmotion.The
boilingpointofasubstanceisthetemperatureatwhichtheaveragekineticenergyofmolecularmotion
balancestheattractiveenergyofintermolecularattractions.Whenthepressureis1.01310 5Pa,that
temperatureisthenormalboilingpoint.Forexample,thenormalboilingpointofbromineis332K(59
C).Abovethistemperature,theaveragekineticenergyexceedstheattractiveenergiescreatedby
intermolecularforcesofattraction,andbromineexistsasvapour.Underatmosphericpressure,bromine
isaliquidattemperaturesbelow332K.Notethat,becauseboilingpointsaredeterminedprimarilyby
intermolecularattractiveforces,factorsotherthanthemolarmassofthemoleculemaybeimportant.For
example,carbontetrachloride,CCl4,(M=153.81gmol1)hasalowerboilingpoint(77C)thanthe
lightermoleculephenol,C6H5OH,(M=94.12gmol1,bp=182C)becauseofthemuchstronger
intermolecularforcesinphenol.

Theconversionofaliquidintoagasiscalledvaporisation.Aliquidvaporiseswhenmoleculesleave
theliquidphasefasterthantheyarecapturedfromthegas.Condensationisthereverseprocess.Agas
condenseswhenmoleculesleavethegasphasemorerapidlythantheyescapefromtheliquid.We
exploretheseprocessesinmoredetailinchapter7.

Themoleculesinaliquidareabletomoveaboutfreely.Whenaliquidiscooled,however,thekinetic
energiesdecrease.Attemperaturesbelowthefreezingpoint,themoleculesbecomelockedinplaceand
theliquidsolidifies.Whenthepressureis1.01310 5Pa,thattemperatureisthenormalfreezingpoint.
Aliquidfreezeswhenliquidmoleculeshavetoolittlekineticenergytoslidepastoneanother.
Conversely,asolidmeltswhenitsmoleculeshaveenoughkineticenergytomovefreelypastone
another.Justasintermolecularforcesdeterminethenormalboilingpoint,theseforcesalsodeterminethe
freezingpoint.Thestrongertheintermolecularforces,thehigherthefreezingpointfluorinefreezesat
53.5K,chlorineat172Kandbromineat266K.

Boilingpointsandmeltingpointsdependonthestrengthsofintermolecularforces.Thisisbecausethe
ratesofescapeandcapturefromaphasedependonthebalancebetweenmolecularkineticenergiesand
intermolecularforcesofattraction.Asubstancewithlargeintermolecularforcesmustberaisedtoahigh
temperaturebeforeitsmoleculeshavesufficientkineticenergiestoovercomethoseforces.Asubstance
withsmallintermolecularforcesmustbecooledtoalowtemperaturebeforeitsmoleculeshavesmall
enoughkineticenergiestocoalesceintoacondensedphase.Table6.4liststheboilingandmelting
pointsofsomeelementalsubstances.
TABLE6.4 Normalmeltingandboilingpointsofselectedelements
Substance mp(K) bp(K)
He 0.95 (a) 4.2

H2 14.0 20.3
 N2 63.3 77.4
F2 53.5 85.0

Ar 83.8 87.3
O2 54.8 90.2

Cl2 172 239

Br2 266 332

I2 387 458

P4 317 553

Na 371 1156
Mg 922 1363
Si 1683 2628
Fe 1808 3023

(a)Underhighpressure,asheliumcannotbesolidifiedatatmosphericpressure.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.8IntermolecularForces
Inchapter5weencounteredionic,covalentandmetallicbondingthatholdatomsandionstogether.In
addition,socalledintermolecularforcesexistbetweenallmolecules(hencethename),buttheyalsoinclude
attractiveforcesbetweenatoms,ionsandmoleculesotherthanbondingforces.Intermolecularforcesare
typicallymuchweakerthanbondingforcesandgenerallyinfluencephysicalpropertiesofcompounds(e.g.
whethertheyaregaseous,liquidorsolidatambientconditions)ratherthantheirchemicalproperties.As
statedearlierinthischapter,intermolecularforcesarecausedbydifferencesinpolarity(permanentor
temporary)betweenentities(seebelow).Inthissection,wewilltalkonlyaboutmolecules,butthe
discussionalsoencompassesionsandatoms.

Differentintermolecularforcescanbethoughtofaspointsalongabondingcontinuumallofthemrelyon
theattractionbetweenpositivelyandnegativelychargedpartsofneighbouringmolecules(i.e.electron
cloudsandnuclei),andthedistinctionbetweenthemisinsomecasesratherfluid.Forcesinorderof
increasingstrengthare:
instantaneousdipoleinduceddipoleforces(alsocalleddispersionforces)
dipoleinduceddipoleforces
dipoledipoleforces(includinghydrogenbonds,whicharetypicallyrelativelystrongdipoledipole
interactions).Thesearealsocalleddipolarforces.

Analogousforcesalsoexistbetweenionsandbothdipolesandinduceddipoles.Iondipoleforcesandion
induceddipoleforcesarestrongerthantheintermolecularforcesabove.

Dispersionforcesaretheattractionsbetweenthenegativelychargedelectroncloudofonemoleculeand
thepositivelychargednucleiofneighbouringmolecules.Allsubstancesdisplaydispersionforces.Theyare
causedbytheusuallysymmetricalelectrondistributionaroundamoleculenotbeingsymmetricalatevery
instantoftime.Thiscreatesaninstantaneousdipole,whichinturncaninduceadipoleinaneighbouring
molecule.

Dipoleinduceddipoleforcesaresomewhatstrongerthandispersionforcesthedifferenceisthat,inthis
case,amoleculewithapermanentdipoleinducesadipoleinaneighbouringmolecule.

Dipoledipoleforcesaretheattractionsbetweenthenegativelychargedendofapolarmoleculeandthe
positivelychargedendsofneighbouringpolarmolecules.Dipoledipoleforcesexistonlyforcompounds
thatpossesspermanentdipolemoments(seesection5.5).

Ifthesedipoledipoleforcesinvolveahydrogenatom,theyarecalledhydrogenbonds.Theyoccurmainly
betweenalonepairofelectronsonasmall,highlyelectronegativeatom(usuallyN,OorF)andahydrogen
atombondedtoahighlyelectronegativeatom.Stronghydrogenbondsoccurprimarilywithmoleculesthat
containOH,NHandFHcovalentbonds.

Dispersionforces,dipoledipoleforcesandhydrogenbondsareallmuchweakerthanintramolecular
covalentbonds.Forexample,theaverageCCbondenergyis345kJmol1,whereasdispersionforcesare
just0.1to5kJmol1forsmallalkanessuchaspropane.Dipoledipoleforcesbetweenpolarmoleculessuch
asacetonerangebetween5and20kJmol1,andhydrogenbondsrangebetween5and50kJmol1.This
generalisation,however,needstobetreatedwithcare.Inalargemolecule,thesumofalltheweak
dispersionforcesmaybemuchstrongerthanadipoledipoleinteractioninadifferentmolecule,leadingto
ahighermeltingorboilingpoint.

DispersionForces
Dispersionforcesexistbecausetheelectroncloudsofmoleculescanbedistorted.Forexample,consider
whathappenswhentwohalogenmoleculesapproacheachother.Eachmoleculecontainspositivenuclei
surroundedbyacloudofnegativeelectrons.Astwomoleculesapproach,thenucleusofonemolecule
attractstheelectroncloudoftheother.Electronsarehighlymobile,sotheelectroncloudschangeshapein
responsetothisattraction.Atthesametime,thetwoelectroncloudsrepeleachother,whichleadstofurther
distortiontominimiseelectronelectronrepulsion.Asfigure6.31indicates,thisdistortionoftheelectron
cloudcreatesachargeimbalance,givingthemoleculeaslightpositivechargeatoneendandaslight
negativechargeattheother.Dispersionforcesarethenetattractiveforcesbetweenmoleculesgeneratedby
alltheseinducedchargeimbalances.

FIGURE6.31Exaggeratedviewofhowdispersionforcesarise.

Themagnitudeofdispersionforcesdependsonhoweasyitistodistorttheelectroncloudofamolecule.
Thiseaseofdistortioniscalledthepolarisabilitybecausedistortionofanelectroncloudgeneratesa
temporarypolarity,calledaninstantaneousdipole,withinthemolecule.Wecanexplorehowpolarisability
variesbyexaminingboilingpointsofthehalogens,asshowninfigure6.32.Thedatarevealthatboiling
pointsincreasewiththetotalnumberofelectrons.Fluorine,with18totalelectrons,hasthelowestboiling
point(85K).Iodine,with106electrons,hasthehighestboilingpoint(458K).Thelargeelectroncloudof
I2distortsmorereadilythanthesmallelectroncloudofF2.Figure6.33showsschematicallyhowalarge
electronclouddistortsmorethanasmallone,generatinglargerdispersionforcesandleadingtoahigher
boilingpoint.

FIGURE6.32Boilingpointsofthehalogensincreasewiththenumberofelectrons.
 FIGURE6.33Withmanymoreelectrons,theelectroncloudofiodineismuchlargerandmorepolarisablethan
thatoffluorine.

Molecularsizeincreaseswiththenumberaswellaswiththesizeofindividualatoms.Figure6.34shows
howtheboilingpointsofalkanesincreaseasthecarbonchaingetslonger.Asalkanesgetlonger,their
electroncloudsbecomelargerandmorepolarisable,makingdispersionforceslargerandraisingtheboiling
point.Asexamples,methane(CH4,10electrons)isagasat298K,pentane(C5H12,42electrons)isalow
boilingpointliquid,decane(C10H22,82electrons)isahighboilingpointliquidandicosane(C20H42,162
electrons)isawaxysolid.Theboilingpointincreasesprogressivelyasmoleculesbecomelargerandmore
polarisable.

FIGURE6.34Theboilingpointsofalkanesincreasewiththelengthofthecarbonchain,becausealargeelectron
cloudismorepolarisablethanasmallone.

Dispersionforcesincreaseinstrengthwiththenumberofelectronsbecauselargerelectroncloudsaremore
polarisablethansmallerelectronclouds.Formoleculeswithcomparablenumbersofelectrons,theshapeof
themoleculemakesanimportantsecondarycontributiontothemagnitudeofdispersionforces.For
example,figure6.35showstheshapesofpentaneand2,2dimethylpropane.Bothofthesemoleculeshave
theformulaC5H12,with72totalelectrons.Noticethat2,2dimethylpropanehasamorecompactstructure
thanpentane.Thiscompactnessresultsinalesspolarisableelectroncloudandsmallerdispersionforces.
Accordingly,pentanehasaboilingpointof309K,while2,2dimethylpropaneboilsat283K.
 FIGURE6.35Theboilingpointofpentaneishigherthantheboilingpointof2,2dimethylpropanebecausean
extendedelectroncloudismorepolarisablethanacompactone.

DipolarForces
Dispersionforcesexistbetweenallmolecules,butsomesubstancesremainliquidatmuchhigher
temperaturesthancanbeaccountedforbydispersionforcesalone.Consider2methylpropaneand
propanone(acetone),whosestructuresareshowninfigure6.36.Thesemoleculeshavesimilarshapesand
nearlythesamenumberofelectrons(34versus32).Theyaresosimilarthatwemightexpectthetwoto
havenearlyequalboilingpoints,butacetoneisaliquidatroomtemperature,whereas2methylpropaneisa
gas.

FIGURE6.36Acetoneand2methylpropanehavesimilarmolecularshapes,butacetonehasalargedipole
momentresultingfromitspolarC Obond.

Whydoesacetoneremainaliquidattemperatureswellabovetheboilingpointof2methylpropane?The
reasonisthatacetonehasalargedipolemoment.Rememberfromchapter5thatchemicalbondsare
polarisedtowardthemoreelectronegativeatom.Thus,theC Obondofacetoneishighlypolarised,with
apartialnegativechargeontheOatom(=3.5)andapartialpositivechargeontheCatom(=2.5).The
CHbondsinthesemolecules,incontrast,areonlyveryslightlypolar,becausetheelectronegativityof
hydrogen(=2.1)isonlyslightlysmallerthanthatofcarbon.

Whentwopolaracetonemoleculesapproacheachother,theyalignsothatthe+endofonemoleculeis
closetotheendoftheother(figure6.36).Inaliquidarray,thisrepeatingpatternofheadtotail
alignmentcreatessignificantnetattractivedipolarforcesbetweenthemolecules.

Thesedipolarforcesinadditiontodispersionforces,whicharenearlythesameinacetoneand2
methylpropane,makethetotalamountofintermolecularattractionbetweenacetonemoleculessubstantially
greaterthanbetweenmoleculesof2methylpropane.Consequently,acetoneboilsataconsiderablyhigher
temperaturethan2methylpropane.

WORKEDEXAMPLE6.13

BoilingPointsandStructure
Thelinestructuresofbutane,methoxyethaneandacetoneareshownbelow.Explainthetrendin
boilingpoints:butane(273K),methoxyethane(281K)andacetone(329K).

Analysis

Theseboilingpointscanbeexplainedintermsofdispersionanddipolarforces.First,assessthe
magnitudesofdispersionforces,whicharepresentinallsubstances,andthenlookforpolarity
withinthemolecules.

Solution

Atablehelpstoorganisetheavailableinformation.

Substance Boilingpoint Totalelectrons

butane 273K 34
methoxyethane 281K 34
acetone 329K 32

Thetableshowsthatdispersionforcesalonecannotaccountfortherangeinboiling
temperatures.Methoxyethaneandbutanehavethesamenumberofelectronsandsimilarshapes
yettheirboilingpointsaredifferent.Acetone,whichhasfewerelectronsthantheother
compounds,hasslightlysmallerdispersionforces,yetitboilsatahighertemperature.Theorder
ofboilingpointsindicatesthatacetoneisamorepolarmoleculethanmethoxyethane,whichin
turnismorepolarthanbutane.

Weexpectbutanetobenonpolarbecauseofthesmallelectronegativitydifferencebetween
carbonandhydrogen.Acetoneandmethoxyethane,ontheotherhand,bothcontainpolar
carbonoxygenbonds.Moleculargeometryrevealswhyacetoneismorepolarthanmethoxy
ethane.Thefullstructuresofthesemoleculesshowthattheoxygenatomintheetherhasfour
setsofelectronpairsandabentgeometry.ThetwoCObonddipolesinmethoxyethane
partiallycanceleachother,leavingarelativelysmallmoleculardipolemoment.Ontheother
 hand,thepolarC Obondinacetoneisunopposed,soacetonehasalargerdipolemomentand
ismorepolarthanmethoxyethane.

Isouranswerreasonable?

Forthemoleculesinthisexample,wewouldexpectthosecontainingelectronegativeoxygen
atomstohavehigherboilingpointsthanbutanebecauseofthepresenceofsignificantpermanent
dipoles.AnOatombondedtoonlyoneatomresultsinalargedipolemomentforthemolecule
asexplainedpreviously,andthereforeweexpectacetonetohaveahigherboilingpointthan
methoxyethane.Experimentalvaluesforthedipolemomentsare:butane,0Cmmethoxyethane,
3.7410 30Cmandacetone,9.6210 30Cm.

PRACTICEEXERCISE6.13
Acetaldehyde,CH3CHO,hasastructure
similartoacetonebutwithaCH3group
replacedbyH.Thissubstanceboilsat294K.
Explainitsboilingpointrelativetothethree
compoundsdescribedinworkedexample
6.13.

Althoughnotstrictlyclassedasanintermolecularforce,theinteractionbetweenanionandthepermanent
dipoleofamoleculecanbesignificant.Suchinteractionsarecallediondipoleinteractions,andthesecan
beviewedaslyingbetweendipoledipoleinteractionsandpureionicinteractions.Inaddition,ionspolarise
neighbouringmolecules,leadingtoinduceddipoleinteractions,whicharemuchweakerthaniondipole
interactions.

HydrogenBonds
Methoxyethaneisagasatroomtemperature(boilingpoint=281K),butpropan1ol,showninfigure6.37,
isaliquid(boilingpoint=370K).Thecompoundshavethesamemolecularformula,C3H8O,andeachhas
achainoffourinneratoms,COCCandOCCC.Consequently,theelectroncloudsofthese
twomoleculesareaboutthesamesize,andtheirdispersionforcesarecomparable.Eachmoleculehasan
sp 3hybridisedoxygenatomwithtwopolarsinglebonds,sotheirdipolarforcesshouldbesimilar.Thevery
differentboilingpointsofpropan1olandmethoxyethanemakeitclearthatdispersionanddipolarforces
donotrevealtheentirestoryofintermolecularattractions.
 FIGURE6.37Thestructuralformulaandaballandstickmodelofpropan1ol.

Theforcesofattractionbetweenpropan1olmoleculesarestrongerthanthosebetweenmethoxyethane
moleculesbecauseofanintermolecularinteractioncalledahydrogenbond.Ahydrogenbondoccurs
betweenasmall,highlyelectronegativeatomwithalonepairofelectronsandapositivelypolarised
hydrogenatom.Theseinteractionscanbeconsideredaspecialexampleofdipoledipoleinteractions,and
theirstrengthsgenerallyliebetweenthoseofdispersionforcesandcovalentbonds.

Therearetworequirementsforhydrogenbondformation.First,theremustbeanelectrondeficient
hydrogenatomthatcanbeattractedtoanelectronpair.HydrogenatomsinOH,FHandNHbonds
meetthisrequirement.Second,theremustbeasmall,highlyelectronegativeatomwithanelectronpairthat
caninteractwiththeelectrondeficienthydrogenatom.Threesecondrowelements,O,NandF,meetthis
requirement,andthereisevidencethatSandClatomscanalsoformhydrogenbonds,butthesearemuch
weakerthanthoseinvolvingF,OandNatoms.Figure6.38showsrepresentativeexamplesofhydrogen
bonding.Thehydrogenbondsareshownasdottedlinestoindicatetheweakbondingnatureofthese
interactions.

FIGURE6.38Examplesofhydrogenbonding.

Noticefromtheexamplesshowninfigure6.38thathydrogenbondscanformbetweendifferentmolecules
(forexample,H3NH2O)orbetweenidenticalmolecules(forexample,HFHF).Alsonoticethat
moleculescanformmorethanonehydrogenbond(glycine,forexample)andthathydrogenbondscan
formbetweenmoleculesaswellaswithinamolecule(salicylicacid,forexample).

WORKEDEXAMPLE6.14

FormationofHydrogenBonds
Inwhichofthefollowingsystemswillhydrogenbondingplayanimportantrole:CH3F,
(CH3)2CO(acetone),CH3OH,andNH3dissolvedin(CH3)2CO?

Analysis

HydrogenbondsrequireelectrondeficienthydrogenatomsinpolarHXbondsandsmall,
highlyelectronegativeatomswithnonbondingpairsofelectrons.Uselinestructurestodetermine
whethertheserequirementsaremet.

Solution

Herearethestructuralformulaeofthefourmoleculeswithnonbondingelectronpairsindicated.

AcetoneandCH3Fcontainelectronegativeatomswithnonbondingpairs,butneitherhasany
highlypolarHXbonds.Thus,themagnitudeofanyhydrogenbondingbetweenmoleculesof
thesesubstanceswillbesmall.

TheOHbondinCH3OHmeetsbothoftherequirementsforhydrogenbonding.TheOH
hydrogenatomononemoleculeinteractswiththeoxygenatomofaneighbouringmolecule.

Forasolutionofammoniainacetone,wemustexaminebothcomponents.Acetonehasan
electronegativeoxygenatomwithnonbondingpairs,whereasNH3hasapolarNHbond.
Consequently,amixtureofthesetwocompoundsdisplayshydrogenbondingbetweenthe
hydrogenatomsofammoniaandoxygenatomsofacetone,and,dependingonthe
concentration,therewillalsobehydrogenbondsbetweenammoniamolecules.
 Isouranswerreasonable?

Methanolhasaconsiderablyhigherboilingpointthanthealkanes,methaneandethane,
consistentwithsignificantintermolecularforces.Ammoniadissolvesreadilyinacetone,also
consistentwithsignificantintermolecularforces.

PRACTICEEXERCISE6.14
Drawapicturethatshowsthehydrogen
bondinginteractionsofanacetonemolecule
dissolvedinwater.

Hydrogenbondingisparticularlyimportantinbiochemicalsystems,becausebiomoleculescontainmany
oxygenandnitrogenatomsthatparticipateinhydrogenbonding.Themostimportantexampleofbiological
hydrogenbondingisseeninDNA,wherehydrogenbondsholdthetwostrandsofDNAtogetherina
doublehelixgeometry.Likewise,theaminoacidsfromwhichproteinsaremadecontainNH2(amino)and
CO2H(carboxylicacid)groups,andfourdifferenttypesofhydrogenbondsexistinthesesystems:OH
N,NHO,OHOandNHN.WhenbiologicalmoleculescontainSatoms,SHOandSH
Nhydrogenbondscanalsoform.Figure6.38includesaviewofhydrogenbondingbetweenmolecules
oftheaminoacidglycine.Moredetailsofhydrogenbondinginbiomoleculesareexaminedinchapters24
and25.

chemicalConnections

MethaneHydrates

Youareallprobablyawareofthepotentialdangerthatcarbondioxideposesasagreenhousegas
intheEarth'satmosphere.However,youmightbelessfamiliarwiththefactthatmethane,CH4,
is,onamassbasis,amuchmorepotentgreenhousegasthancarbondioxide,andlargescale
emissionsofthisgascouldhaveasignificantwarmingeffect.TheNewZealandgovernmentwas
oneofthefirstintheworldtoattempttotakeactiontolimitmethaneemissionsfromfarm
animalshowever,theirsocalledfarttax,whichwouldhaveleviedataxoneveryNewZealand
farmanimal,wasneverimplemented,owingtosubstantialpublicopposition.

Whilefarmanimalsdoindeedemitsignificantquantitiesofmethane,theEarth'soceans,
somewhatsurprisingly,provideafarlargerandpotentiallydevastatingstoreofmethaneinthe
formofanunusualchemicalspeciescalledmethanehydrate.Whenmethanedissolvedinwateris
subjectedtothehighpressuresand(relatively)lowtemperaturesfoundattheseabottom,itforms
methanehydrate,asolidspeciesthatlookslikeice,andcontainsbothmethaneandwater.There
arelargedepositsofmethanehydrateontheseafloorinmanypartsoftheworld,andonesuch
depositliesofftheeastcoastoftheNorthIslandofNewZealand.

Methanehydrateisanexampleofachemicalspeciescalledaclathrate,inwhichgasmolecules
aretrappedinsideanarrayofwatermoleculesthatareheldtogetherinahighlysymmetrical
arrangementbyhydrogenbonds.Figure6.39showsamodelofsuchahydrate,withthemethane
 moleculerepresentedinthecentralcavity(theCatomisgrey,Oatomsareredandhydrogen
atomswhite).Methaneisnotaloneinformingsuchclathratesgroup18gasesinparticularare
knowntoformsimilarspecies.

FIGURE6.39Representationofthestructureofmethanehydrate.

Theformationofmethanehydraterequiresparticularconditionsoftemperatureandpressure.Itis
stableatdepthsgreaterthan300m,wherethewatertemperatureisaround2C.However,arise
inthetemperatureoftheEarth'soceansbyonlyafewdegreescouldleadtoconditionsunder
whichmethanehydrateisnolongerstable.Inthiscase,itwoulddecomposetoliquidwaterand
gaseousmethane,leadingtothereleaseofavastamountofgaseousmethane(someestimatesput
thefigureataround10 16kgofcarbon)intotheatmosphere.Thiswouldalmostcertainlyresultin
significantwarmingoftheatmosphere,and,indeed,suchascenariohasbeenpostulatedasthe
causeofpreviouswarmingeventsonplanetEarth.

Theminingofmethanehydrateasapotentialfuelforpowerstationshasbeenproposed,and,ifit
wasreleasedintotheatmosphere,theCO2formedfromburningtheevolvedmethanewouldhave
lessofaneffectasagreenhousegasthanwouldthegaseousmethaneitself.

BinaryHydrogenCompounds
Boilingpointsofbinaryhydrogencompoundsillustratetheinterplaybetweendifferenttypesof
intermolecularforces.Figure6.40showsthatthereareperiodictrendsintheboilingpointsofthese
compounds.Ingeneral,theboilingpointsofthebinaryhydrogencompoundsincreasefromtoptobottom
ofeachcolumnoftheperiodictable.Thistrendisduetoincreasingdispersionforcesthemoreelectrons
themoleculehas,thestrongerarethedispersionforcesandthehigheristheboilingpoint.Ingroup16,for
example,H2S(18electrons)boilsat213K,H2Se(36electrons)at232KandH2Te(54electrons)at269K.

FIGURE6.40Periodictrendsintheboilingpointsofbinaryhydrogencompounds.NoticethatH2 O,HFandNH3
areexceptionstothetrends.

Asfigure6.40shows,ammonia,waterandhydrogenfluoridedepartdramaticallyfromtheperiodic
behaviour.Thisisbecausetheirmoleculesexperienceparticularlylargeintermolecularforcesresultingfrom
hydrogenbonding.Inhydrogenfluoride,forinstance,hydrogenbondsformbetweenthehighly
electronegativefluorineatomofoneHFmoleculeandtheelectrondeficienthydrogenatomofanotherHF
molecule.SimilarinteractionsamongmanyHFmoleculesresultinchainsofhydrogenbondedHF
moleculesleadingtoaboilingpointmuchhigherthanthoseofHCl,HBrandHI.Note,however,thateven
theboilingpointofHClishigherthanifitwereonatrendlineparalleltothoseforgroups15and16,
indicatingthatweakhydrogenbondsmaybeformed.

Fluorinehasthehighestelectronegativityofanyelement,sothestrongestindividualhydrogenbondsare
thoseinHF.EveryhydrogenatominliquidHFisinvolvedinahydrogenbond,butthereisonlyonepolar
hydrogenatompermolecule.Thus,eachHFmoleculemayparticipateintwohydrogenbondswithtwo
otherHFpartners.Thereisonehydrogenbondinvolvingthepartiallypositivehydrogenatomandasecond
involvingthepartiallynegativefluorineatom,leadingtotheformationofHFchains.

Waterhasasubstantiallyhigherboilingpointthanhydrogenfluoride,whichindicatesthattheoverall
hydrogenbondinginH2OisstrongerthanthatinHF,eventhoughtheindividualhydrogenbondsinHFare
stronger.Thehigherboilingpointofwaterreflectsthefactthatitformsmorehydrogenbondsofsignificant
strengthpermoleculethanhydrogenfluoride.Awatermoleculehastwohydrogenatomsthatcanform
hydrogenbondsandtwononbondingelectronpairsoneachoxygenatom.Thispermitseverywater
moleculetobeinvolvedinfourhydrogenbondstofourotherH2Opartners,asshowninfigure6.41a.
 FIGURE6.41Tworepresentationsofstructureofice.
(a)Eachoxygenatomisatthecentreofadistortedtetrahedronofhydrogenatoms.The
tetrahedroniscomposedoftwoshortcovalentOHbondsandtwolongHOhydrogen
bonds.
(b)Watermoleculesiniceareheldinanetworkofthesetetrahedra.

Hydrogenbondinginicecreatesathreedimensionalnetwork(figure6.41)thatputseachoxygenatomat
thecentreofadistortedtetrahedron.TwoarmsofthetetrahedronareregularcovalentOHbonds,
whereastheothertwoarmsofthetetrahedronarehydrogenbondstotwodifferentwatermolecules.

Therefore,boththestrengthandnumberofhydrogenbondsthatabinaryhydrogencompounddcanform
determineitsboilingpoint.Wewilldiscusstheroleofhydrogenbondinginsolidsinthenextchapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
TheStatesofMatter
Thethreemostimportantstatesofmatteraresolid,liquidandgas.Mostsubstancescanexistinanyof
thesestates,andthestateadoptedbyaparticularsubstanceunderdefinedconditionsisdeterminedby
themagnitudeoftheforcesbetweenindividualatoms,moleculesorionsinthesubstance.

DescribingGases
Gasesoccupyallofthespaceinwhichtheyarecontained.Thepressureexertedbyagasisduetothe
collisionsofrapidlymovinggasatomsormoleculeswiththewallsofthecontainer.TheSIunitof
pressureisthepascal(Pa).Atmosphericpressureismeasuredwithabarometerinwhichapressureof1
standardatmosphere(1atm)willsupportacolumnofmercury760mmhigh.Thisisapressureof760
torr.Bydefinition,1atm=1.0132510 5pascals(Pa),andstandardpressure .
Manometersareusedtomeasurethepressureoftrappedgases.Boyle'sLaw,Charles'Lawand
Avogadro'sLawdescribetherelationshipsbetweenvolumeandpressure,volumeandtemperature,and
volumeandamountofagas,respectively.Thecombinationofthesethreelawsgivestheidealgas
equation:

wherep=pressure(Pa),V=volume(m3),n=amount(mol),R=thegasconstant(8.314Jmol1K1)
andTistemperature(K).

MolecularViewofGases
Inordertodeterminethekineticenergyofagasmolecule,itisnecessarytomeasurethespeedwith
whichitismoving.Thiscanbedoneusingamolecularbeamapparatus.Thisshowsthatallmolecules
withinaparticulargassampledonotmovewiththesamespeedandthatsmallmoleculesmove,on
average,fasterthanlargemolecules.However,themostprobablekineticenergyofagasmoleculeisthe
same,regardlessofitsmass,andallgaseshaveanidenticalmolecularkineticenergydistribution.The
averagekineticenergyofamoleofanygasisrelatedtothetemperatureinkelvinthroughtheequation:

Anidealgasisoneforwhichthevolumeofthemoleculesandtheforcesbetweenthemoleculesareso
smallastobeinsignificant.Anidealgasobeystheidealgasequationexactly.Realgasesapproximate
idealbehaviourunderconditionsoflowpressureandhightemperature.

Therootmeansquarespeedofagas canbefoundfromtheequation:

Themovementofgasmoleculescanbedescribedaseithereffusion(themovementofmoleculesintoa
vacuum)ordiffusion(themovementofonetypeofmoleculethroughmoleculesofthesameoranother
type).

GasMixtures
Eachgaseouscomponentinamixtureofidealgasesexertsapartialpressure.Thesumofpartial
pressuresofallgasesinamixtureequalsthetotalpressure.ThisisastatementofDalton'slawofpartial
pressures,whichcanalsobeexpressedas:
Themolefraction(xA)ofasubstanceAequalstheratiooftheamountofA(n A),tothetotalamount
(n total)ofallthecomponentsofamixture,i.e. .Intermsofmolefractions,p A=xAp total.The
compositionofagasmixturecanalsobeexpressedintermsofpartspermillionorpartsperbillion.

ApplicationsoftheIdealGasEquation
Combinationoftheidealgasequationwiththestoichiometricequation, ,allowsdeterminationof
themolarmassanddensityofanunknowngas.

GasStoichiometry
Theidealgasequationcanbeusedtodetermineamounts,throughrearrangementintotheform
,andcanthereforebeusedinstoichiometriccalculationsinvolvingpuregasesandgas
mixtures.

RealGases
Intermolecularforcesarepartiallyresponsibleforthefactthatrealgasesdonotexactlyobeytheideal
gaslaws.Thevariationfromidealbehaviourcanbeshownbyplotting versuspressureforan

idealgas, shouldalwaysequal1.Valueslessthan1arearesultofsignificantintermolecular
interactionsbetweenindividualgasmolecules,whilevaluesgreaterthan1arisefromthenonzero
volumeofthegasmolecules.Everygasshowsdeviationfromidealbehaviourathighpressuresandat
temperaturesnearthecondensationpoint.ThevanderWaalsequationforarealgas:

makescorrectionsforthevolumeofthegasmoleculesandfortheattractiveforcebetweenthem.The
vanderWaalsconstantareflectstheattractiveforcesbetweenmolecules,whereastheconstantb
reflectstherelativesizeofthegasmolecules.Meltingpointsand,especially,boilingpointsgivegood
indicationsofthestrengthsofintermolecularforces.Thenormalboilingpointisthetemperatureat
whichtheaveragekineticenergyofmolecularmotionbalancestheattractiveenergyofintermolecular
attractionsatapressureof1.01310 5Pa.Undertheseconditions,thesubstanceisconvertedfroma
liquidtoagasinaprocesscalledvaporisation.Thereverseprocessiscalledcondensation.Thenormal
freezingpointisthetemperatureatwhichaliquidsolidifiesatapressureof1.01310 5Pa.

IntermolecularForces
Therearethreegeneraltypesofintermolecularforces:dispersionforces,dipoleinduceddipoleforces
andhydrogenbonds.Theserangeinstrengthfrom0.15kJmol1,520kJmol1and550kJmol1
respectively.

Dispersionforcesresultfromtheasymmetricaldistributionofamolecule'selectronsatanyinstantof
time,leadingtotheformationofinstantaneousdipoleswithinthemolecule.Theeaseofdistortionofan
electroncloudiscalledthepolarisabilityofthemoleculemoleculeswithlargeelectroncloudshave
highpolarisabilitiesandconsequentlydisplaylargedispersionforces.Dispersionforcesoccurinall
molecules.

Polarmoleculesattracteachotherbydipolarforces,whicharisebecausethepositiveendofa
permanentdipoleattractsthenegativeendofadipoleinaneighbouringmolecule.
Hydrogenbonding,aspecialcaseofdipoledipoleattractions,occursbetweenmoleculesinwhich
hydrogeniscovalentlybondedtoasmall,veryelectronegativeatomprincipally,nitrogen,oxygenor
fluorineandmoleculescontainingatomsthathavelonepairsofelectrons(againmainlynitrogen,
oxygenorfluorine).Hydrogenbondingismuchstrongerthantheothertypesofintermolecular
attractionsandisthereasonfortheanomalousbehaviourofwater,ammoniaandhydrogenfluoride
whencomparedwithotherbinaryhydrogencompounds.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Idealgasequation(section6.2)
Thiscanbeusedwhenanythreeofthefourvariablesp,V,Torn,areknownandwewishtocalculate
thevalueofthefourth.

Dalton'slawofpartialpressures(section6.4)
Weusethislawtocalculatethepartialpressureofonegasinamixtureofgases.Thisrequiresthetotal
pressureandeitherthepartialpressuresoftheothergasesortheirmolefractions.Ifthepartialpressures
areknown,theirsumisthetotalpressure.

Molefractions(section6.4)
Giventhecompositionofagasmixture,wecancalculatethemolefractionofacomponent.Themole
fractioncanthenbeusedtofindthepartialpressureofthecomponentgiventhetotalpressure.Ifthe
totalpressureandpartialpressureofacomponentareknown,wecancalculatethemolefractionofthe
component.

Relationshipbetweenintermolecularforcesandmolecularstructure(section6.8)
Fromthemolecularstructure,wecandeterminewhetheramoleculeispolarandwhetherithasNHor
OHbonds.Thisletsuspredictandcomparethestrengthsofintermolecularattractions.Youshouldbe
abletoidentifywhendispersionforces,dipolarforcesorhydrogenbondingoccur.

vanderWaalsequation(section6.8)

Boilingpointsofsubstances(section6.8)
Theseallowustocomparethestrengthsofintermolecularforcesinsubstancesbasedontheirboiling
points.

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 REVIEWQUESTIONS
DescribingGases
6.1Describewhatwouldhappentothebarometerinfigure6.2ifthetubeholdingthemercuryhada
pinholeatitstop.
6.2Describehowthedifferencebetweenaninflatedandaflatcartyreshowsthatagasexertspressure.
6.3Expressthefollowinginunitsofpascal:
(a)455torr
(b)2.45atm
(c)0.46torr
(d)1.3310 3atm.
6.4Asampleofairwascompressedtoavolumeof20.0L.Thetemperaturewas298Kandthe
pressurewas5.0010 5Pa.Whatamountofgaswasinthesample?Ifthesamplewascollected
fromairatapressureof1.0010 5Pawithatemperatureof298K,whatwastheoriginalvolume
ofthegas?
6.5Rearrangetheidealgasequationtogivethefollowingexpressions.
(a)Anequationthatrelatesp i,Ti,p fandTfwhennandVareconstant
(b)V=?
(c)Anequationthatrelatesp i,Vi,p fandVfwhennandTareconstant
6.6Itrequires0.255Lofairtofillametalfoilballoonto1.00010 5Papressureat25C.Theballoon
istiedoffandplacedinafreezerat15C.Whatisthenewvolumeofairintheballoon?
6.7Underwhichofthefollowingconditionscouldyouusetheequationp fVf=p iVi?
(a)AgasiscompressedatconstantT.
(b)Agasphasechemicalreactionoccurs.
(c)Acontainerofgasisheated.
(d)AcontainerofliquidiscompressedatconstantT.
MolecularViewofGases
6.8Redrawfigure6.6btoshowthedistributionofmoleculesifthetemperatureoftheovenisdoubled.
6.9DrawasinglegraphthatshowsthespeeddistributionsofN2at200K,N2at300KandHeat300
K.
6.10Calculatetherootmeansquarespeedandaveragekineticenergypermoleforeachofthe
following.
(a)Heat627C
(b)O2at27C
(c)SF6at627C
6.11Explaininmoleculartermswhyeachofthefollowingstatementsistrue.
(a)Atveryhighpressure,nogasbehavesideally.
(b)Atverylowtemperature,nogasbehavesideally.
6.12Thefigurebelowrepresentsanidealgasinacontainerwithamovablefrictionfreepiston.
 (a) Theexternalpressureonthepistonexertedbytheatmosphereis1.01310 5Pa.Ifthe
pistonisnotmoving,whatisthepressureinsidethecontainer?Explainintermsof
molecularcollisions.
(b)Redrawthesketchtoshowwhatwouldhappenifthetemperatureofthegasinthe
containerisdoubled.Explainintermsofmolecularcollisions.
6.13Describethemolecularchangesthataccountfortheresultinquestion6.6
6.14DeterminetherootmeansquarespeedofSF moleculesat1.0110 5Paand27C.
6
6.15AstudentproposestoseparateCOfromN2byaneffusionprocess.Isthislikelytowork?Whyor
whynot?
GasMixtures
6.16TheconcentrationofNO2inasmoggyatmospherewasmeasuredas0.78ppm.Thebarometric
pressurewas1.01110 5Pa.CalculatethepartialpressureofNO2inPa.
6.17Indryatmosphericair,thefourmostabundantcomponentsareN2,x=0.7808O2,x=0.2095
Ar,x=9.3410 3andCO2,x=3.2510 4.Calculatethepartialpressuresofthesefourgases,in
Pa,understandardatmosphericconditions.
6.18Thefiguresshownbelowrepresentverysmallportionsofthreegasmixtures,allatthesame
volumeandtemperature.

(a)WhichsamplehasthehighestpartialpressureofgasA?
(b)WhichsamplehasthehighestmolefractionofgasB?
(c)InsampleIII,whatistheconcentrationofgasAinppm?
6.19Asampleofcarexhaustisanalysed.Thegascontains487.4ppmCO2,10.3ppbNOand4.2ppb
CO.Calculatethepartialpressuresofthesegasesiftheexhaustisemittedat113.1kPapressure.
ApplicationsoftheIdealGasEquation
6.20Whatisthedensity(gL1)ofSF gasat1.0110 5Paand27C?
6
GasStoichiometry
6.21Humansconsumeglucosetoproduceenergy.TheproductsofglucoseconsumptionareCO2and
 H2O.

WhatvolumeofCO2isproducedunderbodyconditions(37C,1.01310 5Pa)duringthe
consumptionof4.65gofglucose?
6.22Sodiummetalreactswithmolecularchlorinegastoformsodiumchloride.Aclosedcontainerof
volume3.0010 3mLcontainschlorinegasat27Cand1.6710 5Pa.Then6.90gofsolid
sodiumisintroduced,andthereactiongoestocompletion.Whatisthefinalpressureifthe
temperaturerisesto47C?
6.23AmmoniaisproducedindustriallybyreactingN2withH2atelevatedpressureandtemperaturein
thepresenceofacatalyst.

Assuming100%yield,whatmassofammoniawouldbeproducedfroma1:1moleratiomixture
inareactorthathasavolumeof8.7510 3L,underatotalpressureof27510 5Paat455C?
6.24Inpractice,thereactionofquestion6.23givesayieldofonly13%.Repeatthecalculationtaking
thisintoaccount.
RealGases
6.25Predictwhethertheeffectsofmolecularvolumeandintermolecularattractionsbecomemoreor
lesssignificantwhenthefollowingchangesareimposed.
(a)Agasexpandsintoalargervolumeatconstanttemperature.
(b)Moregasisintroducedintoacontainerofconstantvolumeatconstanttemperature.
(c)Thetemperatureofagasincreasesatconstantpressure.
6.26Fromthefollowingexperimentaldata,calculatethepercentagedeviationfromidealbehaviour:
1.00molCO2ina1.20Lcontainerat40.0Cexerts19.710 5Papressure.
6.27Chlorinegasiscommerciallyproducedbyelectrolysisofseawaterandisstoredunderpressurein
metaltanks.Atypicaltankhasavolumeof15.0Landcontains1.25kgofCl2.Usethevander
Waalsequationtocalculatethepressureinthistankifthetemperatureis295K,andcomparethe
resultwiththeidealgasvalue.
IntermolecularForces
6.28Arrangethefollowinginorderofeaseofliquefaction:CCl4,CH4andCF4.Explainyourranking.
6.29Arrangethefollowinginorderofincreasingboilingpoint:Ar,He,NeandXe.Explainyour
ranking.
6.30Listethanol,CH3CH2OH,propane,CH3CH2CH3,andpentane,CH3CH2CH2CH2CH3,inorderof
increasingboilingpoint,andexplainwhatfeaturesdeterminethisorder.
6.31Whichofthefollowingwillformhydrogenbondswithanothermoleculeofthesamesubstance?
Drawmolecularpicturesillustratingthesehydrogenbonds.
(a)CH2Cl2
(b)H2SO4
(c)H3COCH3
(d)H2NCH2COOH
6.32Whichofthefollowingmoleculesformhydrogenbondswithwater?Drawmolecularpictures
 illustratingthesehydrogenbonds.
(a)CH4
(b)I2
(c)HF
(d)H3COCH3
(e)(CH3)3COH

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
6.33Nitrogengasisavailablecommerciallyinpressurised9.50Lsteelcylinders.Ifatankhasa
pressureof14510 5Paat298K,whatamountofN2isinthetank?WhatisthemassofN2inthe
tank?
6.34Thefigurebelowshowsthreechamberswithequalvolumes,allatthesametemperature,
connectedbyclosedvalves.Eachchambercontainsheliumgas,withamountsproportionaltothe
numberofatomsshown.

Answereachofthefollowingquestions,brieflystatingyourreasoning.
(a)Whichofthethreehasthehighestpressure?
(b)IfthepressureinBis1.010 5Pa,whatisthepressureinA?
(c) IfthepressureinAstartsat1.010 5Pa,andthenalloftheatomsfromBandCare
transferredtoA,whatwillbethenewpressure?
(d)IfthepressureinBis0.5010 5Pa,whatwillthepressurebeafterthevalvesareopened?
6.35Atanaltitudeof40kmabovetheEarth'ssurface,thetemperatureisabout25C,andthe
pressureisabout4.010 2Pa.Calculatetheaveragemolecularspeedofozone,O3,atthisaltitude.
6.36Molecularcloudscomposedmostlyofhydrogenmoleculeshavebeendetectedininterstellar
space.Themoleculardensityinthesecloudsisabout10 10moleculesperm3,andtheir
temperatureisaround25K.Whatisthepressureinsuchacloud?
6.37Describeagasexperimentthatwouldshowthattheelementoxygenexistsnaturallyasdiatomic
molecules.
6.38Amixtureofcyclopropanegas,C3H6,andoxygen,O2,ina1.00:4.00moleratioisusedasan
anaesthetic.Whatmassofeachofthesegasesispresentina2.00Lbulbat23.5Cifthetotal
pressureis1.0010 5Pa?
6.39Considertwogasbulbsofequalvolume,onefilledwithH gasat0Cand210 5Pa,theother
2
containingO2gasat25Cand110 5Pa.Whichbulbhas(a)moremolecules(b)agreatermass
(c)ahigheraveragekineticenergyofmoleculesand(d)ahigheraveragemolecularspeed?
6.40Molecularbeamexperimentsonammoniaat425Kgivethespeeddistributionshowninthefigure
below.
 (a)Whatisthemostprobablespeed?
(b)Whatisthemostprobablekineticenergy?
6.41Asampleofgasisfoundtoexertapressureof7.0010 4Pawhenitisina3.00Lflaskat0.00
C.Calculate:
(a) thenewvolumeifpbecomes1.0110 5PaandTisunchanged
(b)thenewpressureifVbecomes2.00LandTisunchanged
(c)thenewpressureifthetemperatureisraisedto50.0CandVisunchanged.
6.42Determinewhethereachofthefollowingstatementsistrueorfalse.Iffalse,rewritethestatement
sothatitistrue.
(a)AtconstantTandV,pisinverselyproportionaltotheamountofgas.
(b)AtconstantV,thepressureofafixedamountofgasisdirectlyproportionaltoT.
(c)AtfixednandV,theproductofpandTisconstant.
6.43A3.00gsampleofanidealgasat22Cand0.96910 5Paoccupies0.963L.Whatisitsvolume
at15Cand1.0010 5Pa?
6.44Recently,carbondioxidelevelsattheSouthPolereached374.6partspermillionbyvolume.(The
1958readingwas314.6ppmbyvolume.)ConvertthisreadingtoapartialpressureinPa.Atthis
level,howmanyCO2moleculesaretherein1.0Lofdryairat45C?
6.45Listthedifferentkindsofforcesthatmustbeovercometoconverteachofthefollowingfroma
liquidtoagas.
(a)NH3
(b)CHCl3
(c)CCl4
(d)CO2
6.46Foreachofthefollowingpairs,identifywhichhasthehigherboilingpoint,andidentifythetype
offorcethatisresponsible.
(a)H3COCH3andCH3OH
(b)SO2andSiO2
(c)HFandHCl
(d)Br2andI2
6.47Whichgasdeviatesmorefromideal behaviour,F2orCl2?

Explainyourchoice.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
6.48Twochambersareconnectedbyavalve.Onechamberhasavolumeof15LandcontainsN2gas
atapressureof2.010 5Pa.Theotherhasavolumeof1.5LandcontainsO2gasat3.010 5Pa.
Thevalveisopened,andthetwogasesareallowedtomixthoroughly.Thetemperatureis
constantat300Kthroughoutthisprocess.
(a)WhatamountofeachofN2andO2ispresent?
(b)WhatarethefinalpressuresofN2andO2,andwhatisthetotalpressure?
(c)WhatfractionoftheO2isinthesmallerchamberaftermixing?
6.49Liquidoxygen,usedinsomelargerockets,isproducedbycoolingdryairto183C.Howmany
litresofdryairat25Cand1.0010 5Pahavetobeprocessedtoproduce150Lofliquid
oxygen(density=1.14gmL1)?Assumethatairis21%O2byvolume.
6.50Inanexplosion,acompoundthatisasolidoraliquiddecomposesveryrapidly,producinglarge
volumesofgas.Theforceoftheexplosionresultsfromtherapidexpansionofthehotgases.For
example,TNT(trinitrotoluene)explodesaccordingtothefollowingbalancedequation.

(a)Whatamountofgasisproducedintheexplosionof1.0kgofTNT?
(b)Whatvolumewillthesegasesoccupyiftheyexpandtoatotalpressureof1.010 5Paat
25C?
(c) Calculatethepartialpressureofeachgasat1.010 5Patotalpressure.
6.51TheHabersynthesisofammoniaoccursinthegasphaseathightemperature(400to500C)and
pressure(100to30010 5Pa).ThestartingmaterialsfortheHabersynthesisareplacedinsidea
container,inproportionsshowninthefigurebelow.

Assuming100%yield,sketchthesystemattheendofthereaction.
6.52Peopleoftenremarkthattheairisthinathigherelevation.Explainthiscommentinmolecular
termsusingthefactthattheatmosphericpressureatthetopofMountEverestisabout3.3310 4
Pa.
6.53Thefiguresshownbelowrepresentmixturesofargonatomsandhydrogenmolecules.Thevolume
 ofcontainerBistwicethevolumeofcontainerA.

(a)Whichcontainerhasahighertotalgaspressure?Explain.
(b)Whichcontainerhasahigherpartialpressureofmolecularhydrogen?Explain.
(c)Oneofthetwogasmixtures(AorB)wasusedinapulsedmolecularbeamexperiment.
Theresultoftheexperimentisshownbelow.Whichofthetwogassamples,AorB,was
usedforthisexperiment?Explain.

6.54A0.1054gmixtureofKClO3andacatalystwasplacedinaquartztubeandheatedvigorouslyto
driveoffalltheoxygenasO2.TheO2wascollectedat25.17Candapressureof1.01210 5Pa.
Thevolumeofgascollectedwas22.96mL.
(a)WhatamountofO2wasproduced?
(b)WhatamountofKClO3wasintheoriginalmixture?
(c)WhatwasthemasspercentofKClO3intheoriginalmixture?
6.55DoestheboilingpointofHCl(seefigure6.40)suggestthatitmayformhydrogenbonds?Explain
youransweranddrawamolecularpicturethatshowsthepossiblehydrogenbondsbetweenHCl
molecules.
6.56Molecularhydrogenandatomicheliumbothhavetwoelectrons,butHeboilsat4.2K,whereas
H2boilsat20K.Neonboilsat27.1K,whereasmethane,whichhasthesamenumberof
electrons,boilsat114K.Explainwhymolecularsubstancesboilatahighertemperaturethan
atomicsubstanceswiththesamenumberofelectrons.
6.57Inthetwofiguresshownbelow,thegreenmoleculeisabouttostrikethewallofitscontainer.
Assumingallotherconditionsareidentical,whichcollisionwillexertgreaterpressureonthewall?
Explainintermsofintermolecularinteractions.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
barometer hydrogenbonding partsperbillion(ppb)
condensation idealgas partspermillion(ppm)
Dalton'slawofpartial idealgasequation pascal(Pa)
pressures intermolecularforces polarisability
diffusion manometer pressure
dipoleinduceddipoleforce molefraction(x) rootmeansquarespeed
dipoledipoleforce normalboilingpoint vanderWaalsequation
dispersionforce normalfreezingpoint vaporisation
effusion partialpressure
gasconstant

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

7 CondensedPhases:Liquids
andSolids
Inthepreviouschapter,welearnedaboutgases,oneofthethreecommonstatesofmatter.The
icebergsshownonthispage,picturedoffDunedinin2006,exemplifytheothertwocommonstates
ofmatter,liquidandsolid.Iceisextremelyunusualbecauseitislessdensethanitsliquidphaseand,
therefore,floatsonthesurfaceofwater.ThishaswiderangingconsequencesforlifeonEarthit
meansthaticewillaccumulateatthesurfaceofabodyofwater,ratherthanatthebottom,ensuring
thataquaticlifecansurviveevenincoldwinters.Italsomeansthatafullbottleofdrinkthatyouput
intothefreezermightcrackbecausewaterexpandswhenitchangesphasefromliquidtosolid.

Inthischapterwewillinvestigateliquidsandsolids,thetwocondensedphasesofmatter.Wewill
alsolookatwhathappenswhensubstanceschangephasebetweensolid,liquidandgas,andhow
thesephasechangesdependonbothtemperatureandpressure.Finallywewillexamineorderin
solidsandsomeapplicationsofmodernmaterials.
 KEYTOPICS

7.1Liquids
7.2Solids
7.3Phasechanges
7.4Orderinsolids
7.5Xraydiffraction
7.6Amorphoussolids
7.7Crystalimperfections
7.8Modernceramics

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.1Liquids
Inthepreviouschapter,wesawthat,althoughmanygasesbehavelikeanidealgasunderambient
conditions,allofthemhaveintermolecularforceswhichmaycausedeviationsfromidealbehaviour.One
consequenceoftheseintermolecularforcesingasesisthatagascondensestoaliquidifitiscooled
sufficiently.Condensationoccurswhentheaveragekineticenergyofthemoleculesfallsbelowthevalue
neededforthemtomoveaboutindependently.Inaliquid,intermolecularforcesarestrongenoughto
confinethemoleculestoaspecificvolume,butnotstrongenoughtokeepmoleculesfrommovingfreely
withintheliquid.Asaconsequence,likegases,liquidsarefluid,andmostfloweasilyfromplacetoplace.
Unlikegases,however,liquidsarecompact,sotheycannotexpandorcontractmuch.

PropertiesofLiquids
Intermolecularforcesinliquidsleadtothreeimportantproperties:surfacetension,capillaryactionand
viscosity.

Surfacetensionisameasureoftheresistanceofaliquidtoanincreaseinitssurfacearea.Thispropertyis
causedbyattractiveintermolecularforcesbetweenthemoleculesinaliquid.Theseattractiveforcesare
knownascohesiveforces.

Figure7.1illustratesatthemolecularlevelwhyliquidsexhibitsurfacetension.Amoleculeintheinteriorof
aliquidiscompletelysurroundedbyothermolecules.Amoleculeataliquidsurface,ontheotherhand,has
othermoleculesbesideitandbeneathit,butveryfewaboveitinthegasphase.Thisdifferencemeansthat
thereisanetattractiveforceonmoleculesatthesurfacethatpullsthemtowardstheinterioroftheliquid,
resultinginasfewparticlesaspossibleatthesurface.Aliquidwillthereforeadoptashapewiththe
minimumpossiblesurfacearea.Smallamountsofaliquidwilladoptasphericalshapebecausesphereshave
lesssurfaceareaperunitvolumethananyothershape.Forexample,waterdripsfromatapinnearly
sphericalliquiddroplets.Largedropsaredistortedfromidealspheresbytheforceofgravity.

FIGURE7.1Intheinteriorofaliquid(bottom),eachmoleculeexperiencesequalforcesinalldirections
(representedbythearrows).Amoleculeatthesurfaceofaliquid(top)ispulledbackintotheliquidby
intermolecularforces.

Moleculesincontactwiththesurfaceoftheircontainerexperiencetwosetsofintermolecularforces.
Cohesiveforcesattractmoleculesintheliquidtooneanother.Adhesiveforcesattractmoleculesintheliquid
tothewallsofthecontainer.

Oneresultofadhesiveforcesisthecurvedsurfaceofaliquid,calledameniscus.Waterinaglasstube
formsaconcavemeniscusthatincreasesthenumberofwatermoleculesincontactwiththewallsofthe
tube.Thisisbecausetheadhesiveforcesbetweenwaterandglassarestrongerthanthecohesiveforces
betweenwatermolecules.

Figure7.2showsanotherresultofadhesiveforces.Inatubeofsmallenoughdiameter,wateractually
climbsthewallsbecausetheadhesiveforcesbetweenwaterandglassarestrongerthantheforceofgravity.
Thisupwardmovementofwateragainstthedownwardforceofgravityiscalledcapillaryactionandisdue
toattractionsbetweenpolarwatermoleculesandoxygenatomsinSiO2(glass).Similarly,capillaryaction
involvingsapandthecellulosewallsofwoodfibreplaysaroleinhowtreestransportsapfromtheirrootsto
theirhighestbranches.

FIGURE7.2Waterrisesinsideasmalldiametertubebecauseofcapillaryaction.Thewaterinthisphotohasbeen
colouredtoshowtheeffectofcapillaryactionmoreclearly.

Watercanbepouredveryquicklyfromonecontainertoanother,whileoilpoursmoreslowly,andhoney
sometimesseemstotakeforever.Aliquid'sresistancetoflowiscalleditsviscositythegreatertheviscosity,
themoredifficulttheliquidistopour.Viscosityisameasureofhoweasilymoleculesslidebyoneanother.
Viscosityis,therefore,affectedbyacombinationofmolecularshapeandthestrengthoftheintermolecular
forces.Thegreaterthecontactareaofeachmoleculeinaliquid,thehighertheviscosityoftheliquid.The
moleculesinliquidssuchaswater,acetoneandbenzenearesmallandcompacttheyhavesmallcontact
areasandthuslowviscosity.Incontrast,moleculeswithalargesurfacearea,suchasthesugarsinhoney
andthehydrocarbonsfoundinoils,havelargeareasofcontactandthushighviscosity.

Viscosityisaffectedbytemperature.Thisdependenceisquitenoticeableforhighlyviscoussubstancessuch
ashoneyandsyrup,whicharemucheasiertopourwhenhotthanwhencold.Athighertemperature,the
averagekineticenergyofthemoleculesintheliquidishigher,whichallowsthemtoovercomethe
intermolecularforcesmoreeasily.Thus,viscositydecreasesastemperatureincreases.

VapourPressure
Oursensestellusthatmoleculesescapefromaliquid.Forexample,boththesmellofpetrolaroundanopen
tankandtheevaporationofarainpuddleinthesunshinesuggestthatmoleculesescapefromtheliquidinto
thevapourphase.Theredvapourphasethatcanbeobservedaboveliquidbrominesuggeststhatbromine
moleculesarepresentinbothphases.
Recallfromsection6.3thatanycollectionofmoleculeshasadistributionofkineticenergies.Inaliquid,the
distributionofkineticenergiesissuchthatmoleculescanmoveaboutwithintheliquid,butonaveragethey
donothavesufficientkineticenergytoescapeintothegasphase.Nevertheless,thedistributionof
molecularenergiesguaranteesthatsomeofthemoleculesinanyliquidhaveenoughkineticenergyto
overcometheintermolecularforcesthatconfinetheliquid.Thesemoleculesescapeintothevapourphase
whenevertheyareatthesurfaceoftheliquid.Ifthesurfaceofaliquidisincontactwithagasphase,some
ofitsmoleculeswillescapeintothegasphase.

Thenumberofmoleculesofaliquidthathaveenoughenergytoescapeintothevapourphasedependsboth
onthestrengthofintermolecularforceswithintheliquidandthetemperature.Asfigure7.3shows,ata
particulartemperaturemoremoleculescanescapefromliquidbrominethanfromliquidwater.Thisis
becausetheintermolecularforcesbetweenwatermoleculesarestrongerthanthosebetweenbromine
molecules.Awatermoleculeneedsmorekineticenergytoescapetheliquidphase.Figure7.3billustrates
that,whenthetemperaturerises,thefractionofmoleculeshavingenoughenergytoescapeincreases.

FIGURE7.3 Thefractionofmoleculeswithenoughkineticenergytoescapealiquiddependsonthestrengthof
intermolecularforcesandtemperature.
(a)At300K,morebrominemoleculescanescapethanwatermoleculesbecausebrominehas
weakerintermolecularforcesthanwater.
(b)Morebrominemoleculescanescapeat320K(areaunderorangecurvetotherightofescape
energy)thanat300K(areaunderthebluecurvetotherightofescapeenergy)becausethere
aremoremoleculeswithatleasttheescapeenergy.

Aliquidinanopencontainercontinuallylosesmoleculesuntileventuallyithasevaporatedcompletely.
However,inaclosedcontainersuchastheoneshowninfigure7.4,thepartialpressureofthevapour
increasesasmoreandmoremoleculesenterthegasphase.Asthispartialpressurebuilds,increasing
numbersofmoleculesfromthevapourstriketheliquidsurfaceandreturntotheliquid.Eventually,asfigure
7.4illustrates,thenumberofmoleculesescapingfromtheliquidexactlymatchesthenumberofmolecules
beingcapturedbytheliquid.Thereisnonetchangeinthetotalnumberofmoleculesinthegasandthe
liquid,andwecallthisadynamicequilibrium.Thepressureatwhichthisequilibriumexistsisthevapour
pressureoftheliquid.Thevapourpressureofanyliquidriseswithincreasingtemperaturebecausemore
moleculeshavesufficientkineticenergytoescapetheliquidphaseintothegasphase.
 FIGURE7.4Asthepartialpressureofasubstanceinthegasphaseabovealiquidinaclosedcontainerincreases
(asindicatedbythenumberofredarrows),thedifferencebetweenthenumberofmoleculesescaping
intothegasphaseandthenumberreenteringtheliquidphasedecreasesuntil,atthevapour
pressureofthesubstance,equilibriumisestablished.

Oncethevapourpressureoftheliquidinanopencontainerreachestheexternalpressure,theliquidstartsto
boil.Water,forinstance,boilsat100Cataverageatmosphericpressureatsealevel(1.01310 5Pa).As
welearnedinchapter6,thetemperatureatwhichaliquidboilsatthispressureisknownasthenormal
boilingpoint.Atlowerpressure,suchaswewouldfindontopofahighmountain,theboilingpointislower
becausetherequiredvapourpressureisreachedatalowertemperature.Forexample,ontopofNew
Zealand'sAoraki/MountCook,whichis3754mhigh,averageatmosphericpressureis0.63710 5Paand
waterboilsatabout85C.Conversely,apressurecookerworksontheprinciplethatifyouincreasethe
externalpressuretheboilingpointincreases.Forinstance,atnormalatmosphericpressure,youcannotheat
liquidwatertoabove100C,whereasinahouseholdpressurecookertemperaturesofupto120Ccanbe
reached.Figure7.5showsthedependenceofvapourpressureontemperatureforarangeofliquids.The
variationbetweenvapourpressuresofdifferentsubstancesisduetothedifferentstrengthsofintermolecular
forces.

FIGURE7.5Vapourpressureasafunctionoftemperaturefordiethylether,water,aceticacidandpropane1,3
diol.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.2Solids
Thevastmajorityofcompoundsaresolidsunderambientconditions.Asubstanceisasolidwhenitsions,atomsormoleculesareheldtogetherso
stronglythattheycannoteasilymovepasteachother.Unlikegasesandliquids,solidsarecharacterisedbyrigidity,whichgivesthemthestable
shapesthatweseeinstructuresrangingfrombonestoaeroplanewings.Oneofthemostactiveareasofresearchinchemistry,physicsand
engineeringisthedevelopmentofneworimprovedsolidmaterials.Solidscontinuetoplayalargeroleinsociety,fromcapacitorsandsolidstate
batterycomponentsinmobilephonesandlaptopstonewtissuecompatiblesolidsforsurgicalimplants.Inthissection,wedescribethevarioustypes
ofsolids.

MagnitudesofForces
Inchapter6,wesawthatthemeltingpointsofsolidsspananimmenserange,e.g.from0.95K(He)to1808K(Fe)forthosepresentedintable6.4(p.
240).Thesevaluesindicatethattheforcesinsolidsrangefromverysmalltoextremelylarge.Thisisbecausetheions,atomsormoleculesinsolids
canbeboundtogetherbyvariousattractiveforces:intermolecularforces,metallicbonding,covalentbondsandionicinteractions.

Themoleculesofamolecularsolidareheldinplacebyintermolecularforces:dispersionforcesanddipolarinteractions,includinghydrogenbonds.
Theatomsofametallicsolidareheldinplacebydelocalisedbondinginvolvingmobileelectrons(p.259).Anetworksolidcontainsanarrayof
covalentbondslinkingeveryatomtoitsneighbours.Anionicsolidcontainscationsandanions,attractedtooneanotherbyelectrostaticforcesas
describedinsection5.2.Table7.1contraststheforcesandenergiesassociatedwiththesefourtypesofsolids.
TABLE7.1 Characteristicsofdifferenttypesofsolids
Solidtype atomic/molecular molecular molecular metallic network ionic
Attractive dispersion dispersion+dipolar dispersion+dipolar delocalised covalent electrostatic
forces +hydrogen bonding
bonding
Energy 0.0540 525 550 751000 150500 4004000
(kJmol1)
Example Ar HCl H2O Cu SiO2 NaCl

Melting 189 114 0 1088 1713 801

point(C)
Schematic
diagram

MolecularSolids
Molecularsolidsareaggregatesofmoleculesboundtogetherbyintermolecularforces.Theforcescanbedispersionforces,dipolarforces,hydrogen
bondingoracombinationofthese.

Manylargermoleculeshavesufficientdispersionforcestoexistassolidsatroomtemperature.Oneexampleisnaphthalene,C10H8,theactive
substanceinmothballs.Naphthaleneisawhitesolidthatmeltsat80C.Naphthalenehasaplanarstructurewithacloudof10electronsdelocalised
aboveandbelowthemolecularplane(figure7.6).Naphthalenemoleculesareheldinthesolidstatebystrongdispersionforcesinvolvingthesehighly
polarisableelectrons.Themoleculesincrystallinenaphthalenearearrangedtomaximisethesedispersionforces,thusleadingtotheformationof
platelikemacroscopiccrystals.

FIGURE7.6 (a)Naphthalene,
(b)thelinestructureofnaphthaleneand
(c)aballandstickmodel,overlaidwiththelowestenergybondingmolecularorbital.

Dimethyloxalate,CH3OC(O)C(O)OCH3(figure7.7)isanexampleofamolecularsolid(mp=52C)inwhichneighbouringmoleculesareheld
togetherpredominantlybydipolarinteractions.ThetwocarbonylCatomshavesignificant+character,duetothefactthateachisbondedtotwo
electronegativeOatoms.The+CatomsareinvolvedinattractivedipolarinteractionswiththeOatomsofneighbouringmolecules.
 FIGURE7.7Structuralformulaofdimethyloxalate.

Inadditiontodispersionanddipolarforces,molecularsolidsofteninvolvehydrogenbonding.Benzoicacid,C6H5COOH,whosesodiumsaltisa
commonfoodpreservative,providesagoodexample,asillustratedinfigure7.8.Moleculesofbenzoicacidareheldinplacebyacombinationof
dispersionforcesbetweentheelectronsandhydrogenbondingbetweentheCOOHgroups.Withfewerelectrons,benzoicacidhasweaker
dispersionforcesthannaphthalene,butitshydrogenbondinggivesbenzoicacidahighermeltingpointof122C.

FIGURE7.8 (a)Crystalsofbenzoicacidcontain
(b)pairsofmoleculesheldtogetherheadtoheadbyhydrogenbonds.Thesepairsthenstackinplanesthatareheldtogetherbydispersion
forces.

Theeffectofextensivehydrogenbondingisrevealedbytherelativelyhighmeltingpointofglucose,C6H12O6,thesugarfoundinbloodandhuman
tissue.Glucosemeltsat155CbecauseeachofitsmoleculeshasfiveOHgroupsthatformhydrogenbondstoneighbouringmolecules(figure
7.9).Althoughglucoselacksthehighlypolarisableelectronsfoundinnaphthaleneandbenzoicacid,itsextensivehydrogenbondinggivesthis
sugarthehighestmeltingpointofthesethreecompounds.

FIGURE7.9Thestructuralformulaofglucose,C6 H12 O6 .

NetworkSolids
Insharpcontrasttomolecularsolids,networksolidshaveveryhighmeltingpoints.Comparethebehaviourofphosphorusandsilicon,thirdrow
neighboursintheperiodictable.Whitephosphorusmeltsat44C,butsiliconmeltsat1410C.Whitephosphorusisamolecularsolidthatcontains
individualP4molecules(seefigure7.10),butsiliconisanetworksolidinwhichcovalentbondsconnecteverySiatomtoeachofitsfourneighbours
(seefigure7.11).
 FIGURE7.10RepresentationofaP4 moleculeinwhitephosphorus.

FIGURE7.11Partofthestructuralmodelofsilicon,showingsiliconatomsconnectedtoeachothertoformathreedimensionalnetwork.

Thecauseofthegreatdifferenceinthemeltingpointsofthesetwoelementsisevidentfromtable7.1.Covalentbondsaremuchstrongerthan
intermolecularforces.Forsolidsilicontomelt,asignificantfractionofitsSiSicovalentbondsmustbreak.TheaverageSiSibondenergyis225
kJmol1,whereasattractiveenergiesduetointermolecularforcesinP4aremuchlower(asshownintable7.1,intermolecularforcesaregenerallyless
than50kJmol1)soittakesamuchhighertemperaturetomeltsiliconthanwhitephosphorus.

Bondingpatternsdeterminethepropertiesofnetworksolids.Diamondandgraphite,thetwoformsofelementalcarbonthatoccurnaturallyonEarth,
haveverydifferentphysicalandchemicalproperties.Diamondcontainsathreedimensionalarrayofbonds,witheachsp 3hybridisedcarbonatom
linkedtoeachofitsfourneighbouringcarbonatomsthroughcovalentbondsresultinginatetrahedralgeometryaroundeachcarbonatom(identical
totheSistructurementionedabove,seefigure7.12a).Itisthusanetworksolid.Itsthreedimensionalnetworkofstrongcovalentbondsmakes
diamondextremelystrongandabrasive.Covalentbondsconnectingatomsinthreedimensionsmakenetworksolidsextremelydurable.Thesp 2
hybridisedcarbonatomsingraphite,incontrast,areconnectedtoonlythreeneighbouringcarbonatomsviacovalentbondsinaplanararrangement.
Thebondingissupplementedbydelocalisedbondingaboveandbelowtheplaneofthebonds(seefigure7.12b).Eachtwodimensionallayeris
attractedtoitsneighbouringlayersonlybydispersionforcesbetweentheelectrons.Asaresult,planesofcarbonatomseasilyslidepastone
another,makinggraphiteabrittlelubricant.

FIGURE7.12 Partofthestructuralmodelsof
(a)diamondshowingcarbonatomsconnectedtoeachothertoformathreedimensionalnetwork,and
(b)graphite,showingthetwodimensionallayers.

Compoundssuchassilica(silicondioxide,SiO2)mayalsoexistasnetworksolids.Opalsarecomposedofnanosizedsilicaspheroids.Theirprized
colourisduetothewaytheydiffractlight,ratherthantheimpuritiesthatgivemostothergemstonestheircolour.Anotherexampleissiliconcarbide,
SiC,whichhasasimilarstructuretodiamondandisusedasanabrasiveinsandpaperandasanedgeoncuttingtoolsasitislessexpensiveto
produce.Thesesubstanceshaveveryhighmeltingpointsbecausetheiratomsareheldtogetherbynetworksofstrongcovalentbonds.

MetallicSolids
Thebondinginsolidmetalsdiffersfromthatinothertypesofsolidsbecauseitderivesprimarilyfromelectronsinhighlydelocalisedvalenceorbitals.
Recallfromthemolecularorbitaltheorydiscussedinchapter5thatoverlapofnvalenceatomicorbitalsgivesrisetonmolecularorbitals.Whennis
verylarge,asisthecasein1moleofasolidmetal,thenalargenumberofmolecularorbitalsareformed.Theenergiesofthesemolecularorbitalsare
soclosetogetherthattheyessentiallyformacontinuumofenergies,calledaband,whichextendsoveralloftheatomsinthemetal.Therefore,an
electroninapartiallyfilledorbitalisdelocalisedoveralltheatoms,andisconsequentlyabletomovethroughouttheentiremetal.Hence,wecanview
ametalasconsistingofaregulararrayofmetalatomcoresembeddedinaseaofmobilevalenceelectrons(seefigure7.13).Thepropertiesof
metals,suchaselectricalandthermalconductivity,canbeexplainedonthebasisofthismodel.

FIGURE7.13Adiagrammaticrepresentationofmetallicbonding.Themetalatomsareembeddedinaseaofmobilevalenceelectrons.

Metalsdisplayawiderangeofmeltingpoints,indicatingthatthestrengthofmetallicbondingisvariable.Thegroup1metalsarequitesoftandmeltat
relativelylowtemperatures(seefigures7.14a,c).Sodium,forexample,meltsat98Candcaesiummeltsat28.5C.Bondingisweakinthesemetals
becauseeachatomofagroup1metalcontributesonlyonevalenceelectrontothebondformingenergyband.Metalsnearthemiddleofthedblock,
ontheotherhand,areveryhardandhavesomeofthehighestknownmeltingpoints:tungstenmeltsat3407C(figure7.14b),rheniumat3180C
andchromiumat1857C.Atomsofthesemetalscontributeseveraldelectronstobondformation,leadingtoextremelystrongmetallicbonding.
 FIGURE7.14 (a)Sodium,Na,canbecutwithaknife.
(b)Tungsten,W,canbeheatedtoincandescencewithoutmelting,whichiswhyitisusedasthefilamentinlightbulbs.
(c)Group1metalsmeltatrelativelylowtemperatureswhereasmetalsnearthemiddleofthedblockhavesomeofthehighestknownmelting
points.

Metalsareductile,meaningtheycanbedrawnintowires,andmalleable,meaningtheycanbehammeredintothinsheets.Whenapieceofmetal
formsanewshape,itsatomschangeposition.However,becausethebondingelectronsarefullydelocalised,changingthepositionsoftheatomsdoes
notcausecorrespondingchangesintheenergylevelsoftheelectrons.Theseaofelectronsislargelyunaffectedbythepatternofmetalatoms,as
figure7.15illustrates.Thus,metalscanbeforcedintomanyshapes,includingsheetsandwires,withoutdestroyingtheirbondingnature.

FIGURE7.15Whenametalchangesshape,itsatomsshiftposition.However,becausethevalenceelectronsarefullydelocalised,theenergyoftheseelectronsis
unaffected.

Thedblockmetalsdisplayarangeofproperties.Copperandsilveraremuchbetterelectricalconductorsthanchromium.Tungstenhasverylow
ductility.Mercuryisaliquidatroomtemperature.Thesedifferencesariseinpartbecauseofvariationsinthenumberofvalenceelectrons.Thed
blockmetalsvanadiumandchromiumhavefiveorsixvalenceelectronsperatomrespectively,allofwhichoccupybondingorbitalsinthemetal
atoms.Asaresult,therearestrongattractiveforcesbetweenthemetalatoms,andvanadiumandchromiumarestrongandhard.Beyondthemiddleof
thedblockseries,theadditionalvalenceelectronsoccupyantibondingorbitals,whichreducesthenetbonding.Thiseffectismostpronouncedatthe
endofthedblock,wherethenumberofantibondingelectronsnearlymatchesthenumberofbondingelectrons.Zinc,cadmiumandmercury,withs2
andd 10configurations,havemeltingtemperaturesthataremorethan600Clowerthanthoseoftheirimmediateneighbours.

IonicSolids
Asdescribedinchapter5,ionicsolidscontaincationsandanionsstronglyattractedtoeachotherbyelectrostaticforces.Ionicsolidsmustbe
electricallyneutral,sotheirstoichiometriesaredeterminedbythechargescarriedbythepositiveandnegativeions.

Manyionicsolidscontainmetalcationsandpolyatomicanions.Hereagain,thestoichiometryofthesolidisdictatedbythechargesontheionsand
theneedforthesolidtomaintainelectricalneutrality.Someexamplesof1:1ionicsolidscontainingpolyatomicanionsareNaOH,KNO3,CuSO4,
BaCO3andNaClO3.Somemetallicoreshave1:1stoichiometry,suchasscheelite,CaWO4(containsWO42),zircon,ZrSiO4(containsSiO44)and
ilmenite,FeTiO3(containsTiO32).IlmeniteisthesourceofTiO2,whichisusedasawhitepigmentinpaperandpaints.

Mineralsoftencontainmorethanonecationoranion.Forexample,apatite,Ca5(PO4)3OH,themainsubstanceintoothenamel,containsboth
phosphateandhydroxideanions.Beryl,Be3Al2Si6O18,containsberylliumandaluminiumcationsaswellastheSi6O1812polyatomicanion.Berylis
thesubstancethatmakesupemeralds.Anevenmorecomplicatedmineralisgarnierite,(Ni,Mg)6Si4O10(OH)2,whichhasavariablecompositionof
Ni2+andMg 2+cations.AlthoughtherelativeproportionsofMg 2+andNi2+vary,garnieritealwayshassixcationsandtwoanionsofOHforevery
anionofSi4O1010.

Somemixedoxidesthatcontainrareearthmetalsaresuperconductors.Belowacertaintemperature,asuperconductorcancarryanimmenseelectrical
currentwithoutincurringlossesfromresistance.Optimalsuperconductingbehaviouroftenrequiresaslightdeviationfromstoichiometric
composition,whichwewilllearnmoreaboutinsection7.8.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.3PhaseChanges
Inchapter6andthefirsttwosectionsofthischapter,wehaveexaminedthethreemostcommonphasesof
matter(gas,liquidandsolid)inisolation.Wewillnowinvestigatewhatgovernsaphasechangethe
transitionofasubstancefromonephasetoanother.Substancescanundergophasechangesgiventhe
appropriateconditions.Phasechangesdependontemperature,pressure,andthemagnitudesofbonding
andintermolecularforces.

Weareallfamiliarwiththephasechangesofwateratambientpressure,whichareillustratedinfigure
7.16.Considertakingicecubesfromthefreezerat18Candplacingtheminacontaineratroom
temperature.Atfirstthewaterisinthesolidphase(stage1).Outsidethefreezer,thetemperatureoftheice
cubesbeginstoincrease.Whenthetemperatureoftheicecubesreaches0C,theybegintomeltandwe
getamixtureofsolidandliquidwater(stage2).Thetemperatureofthismixturedoesnotincreaseuntilall
theicehasmelted.Oncetheicehascompletelymelted,thetemperatureoftheliquidwillstartincreasing
(stage3).Ifweapplyheattothecontainertheliquidwillincreaseintemperature(stage3)untilitreaches
100C.Thewaterthenstartstoboil(stage4)andwegetwatervapour.Thesystemremainsat100Cuntil
allofthewaterhasevaporated.Continuedheatingofthewatervapouronceallofthewaterhasevaporated
willresultinitstemperatureincreasingabove100C(stage5).Thetemperatureofthecontainerwillalso
increaseonceallthewaterhasevaporated,whichiswhyitisnotagoodideatoallowasaucepantoboil
dryonahotplate.

FIGURE7.16WhenheatissuppliedtoasampleofH2 Oataconstantpressureof1.013105 Pa,phasechanges

occurat0Cand100C.Thexaxisrepresentstheheatrequiredforeachindividualprocess.It
shouldbenotedthattherearemoleculesinthevapourphaseabovebothsolidandliquidwater,but
thesehavebeenomittedinstages1,2and3forclarity.
Adaptedfrom:Chemistry:Themolecularnatureofmatterandchange,3rdedition,MartinS
Silberberg,p.424,2003TheMcGrawHillCompanies,Inc.

Phasechangesrequirethatenergy(usuallyintheformofheat)beeithersuppliedtoorremovedfromthe
substanceundergoingthephasechange.Restrictingourselvestomolecularsubstances,butrecognising
thatsimilarargumentsholdforatomicandionicsubstances,amolecularperspectiverevealswhythisisso.
Anyphasechangethatresultsinincreasedmolecularmobilityrequiresthatintermolecularforcesbe
overcome.Forexample,hydrogenbondsinicemustbebrokentochangetheicetoliquidwater,and
hydrogenbondsinliquidwatermustbebrokentoconvertittowatervapour.About41kJofheatmustbe
suppliedtotransfer1moleofwatermoleculesfromtheliquidphaseintothevapourphase.Similarly,41
kJofheatmustberemovedtoliquefy1moleofwatervapour.Asfigure7.16indicates,theheatrequired
tochangebetweentheliquidandsolidphasesisconsiderablyless.

Asyouwillseeinmoredetailinchapter8,theamountofheattransferredatconstantpressureisequaltoa
quantitycalledtheenthalpychange(H).Themagnitudeofthechangedependsonthestrengthof
intermolecularforcesinthesubstanceundergoingthephasechange.

Theamountofheatrequiredtovaporiseasubstancealsodependsontheamountinthesample.The
energyrequiredtovaporise2molesofwateristwicethatneededfor1mole.Theheatneededtovaporise
1moleofasubstanceatitsnormalboilingpointiscalledthemolarenthalpyofvaporisation(vapH).For
example,vapHofwaterisabout41kJmol1.

Energymustalsobeprovidedtomeltasolidsubstance.Thisenergyisusedtoovercomethe
intermolecularforcesthatholdmoleculesinfixedpositionsinthesolidphase.Theheatneededtomelt1
moleofasubstanceatitsnormalmeltingpointiscalledthemolarenthalpyoffusion(fusH).For
example,fusHofwaterisabout6kJmol1.

Phasechangesbetweensolidandliquid,andbetweenliquidandgas,arethemostcommon,butaphase
changeinwhichasolidconvertsdirectlytoagaswithoutpassingthroughtheliquidphaseisalsopossible.
Thistransitionisknownassublimation(depositionistheoppositetransition).Dryice(solidCO2)
sublimesat195Kwiththemolarenthalpyofsublimation(subH)=25.2kJmol1.Mothballscontain
naphthalene,C10H8(sub=73kJmol1),acrystallinewhitesolidthatsublimestoproduceavapourthat
repelsmoths.Thepurplecolourofthegasaboveiodinecrystalsinaclosedcontainer(figure7.17)
providesvisibleevidencethatthissolidalsosublimesatroomtemperature(subH=62.4kJmol1).Both
naphthaleneandiodinemeltatambientpressure(at80Cand114C,respectively),indicatingthat,while
asmallamountcansublimeatambientpressure,itisnotathermodynamicequilibrium.

FIGURE7.17ThepurplecolourofthevapourabovesolidiodineisduetoI2 moleculesinthegasphase.

Phasechangescangoineitherdirectionicemeltsuponaddingheat,andliquidwaterfreezesonremoving
heatfromthesystem.Heatisabsorbedasasolidmeltstoaliquidandisreleasedasaliquidfreezestoa
solid.Tomakeicecubes,forinstance,waterisplacedinafreezerthatabsorbstheheatreleasedduringthe
formationofice.Theheatreleasedwhenliquidwaterchangestoiceisequalinmagnitudetotheheat
requiredtochangeicetoliquidwater.

Byconvention,tabulatedvaluesofenthalpiesofphasechangesarealwaysspecifiedintermsofthephase
changethatrequirestheadditionofheat.Thereverseprocesseshavethesamemagnitudebuttheopposite
sign.

Table7.2listsvaluesoffusH,vapH,meltingpointsandboilingpointsforselectedchemicalsubstances.

TABLE7.2 Phasechangedataforselectedchemicalsubstances

Substance Formula mp(K) fusH(kJmol1) bp(K) vapH(kJmol1)

argon Ar 83 1.3 87 6.3
oxygen O2 54 0.45 90 9.8

methane CH4 90 0.84 112 9.2

ethane C2H6 90 2.85 184 15.5

diethylether (C2H5)2O 157 6.90 308 26.0

bromine Br2 266 10.8 332 30.5

ethanol C2H5OH 156 7.61 351 39.3

benzene C6H6 278 10.9 353 31.0

water H2O 273 6.01 373 40.79

mercury Hg 234 23.4 630 59.0

WORKEDEXAMPLE7.1

EnthalpyofPhaseChange
Aswimmeremergingfromapooliscoveredwithafilmcontainingabout75gofwater.How
muchheatmustbesuppliedtoevaporatethiswater?

Analysis

Energyintheformofheatisrequiredtoevaporatethewaterfromtheswimmer'sskin.The
energyneededtovaporisethewatercanbefoundusingthemolarenthalpyofvaporisationand
theamountofwater.

Solution

vapHofwateris40.79kJmol1(seetable7.2).Themolarmassofwateris18.02gmol1,so
75gofwateris4.16mol.Therefore,theheatthatmustbesuppliedis:
 Isouranswerreasonable?

Iftheswimmer'sbodymustsupplyallthisheat,asubstantialchillingeffectoccurs.Thus,
swimmersusuallytoweloff(toreducetheamountofwaterthatmustbeevaporated)orlieinthe
sun(toletthesunprovidemostoftheheatrequired).

PRACTICEEXERCISE7.1
Determinehowmuchheatisinvolvedin
freezing125gofwaterinanicecubetray.
Whatisthedirectionofheatflowinthis
process?

Recallfromourdiscussionoffigure7.16thataddingheattoboilingwaterdoesnotcausethetemperature
ofthewatertoincrease.Instead,theaddedenergyisusedtoovercomeintermolecularattractionsasmore
moleculesleavetheliquidphaseandenterthegasphase.Othertwophasesystemsshowsimilar
behaviour.Thiscanbeusedtoholdachemicalsystematafixedtemperature.Atemperatureof100C
canbemaintainedbyaboilingwaterbath,andanicebathholdsasystemat0C.Lowertemperaturescan
beachievedwithothersubstances.Dryice(solidCO2)suspendedinliquidacetonemaintainsa
temperatureof78C(195K)abathofliquidnitrogenhasaconstanttemperatureof196C(77K)and
liquidhelium,whichboilsat4.2K,isusedforresearchrequiringultracoldtemperatures.

Atthestartofthissectionwementionedthatpressureisalsoinvolvedinphasechanges.Theeffectof
pressureismainlyseenforphasetransitionsinvolvinggases.Recallfromchapter6thatgasdensity
increaseswithpressure.Agasatconstanttemperaturecanbeliquefiedbyincreasingthepressure.Thisis
importantinthestorageofliquefiedpetroleumgas(LPG),amixtureofpropaneandbutanethatisusedas
afuelforcars,barbecuesandheaters.Propaneandbutanearegasesatroomtemperatureandnormal
atmosphericpressure.Tomakethestorageandtransportofthefuelpracticable,itisliquefiedbyplacingit
underpressure.Thepressureatwhichagasliquefiesataspecifictemperatureisknownasthe
condensationpoint.

SupercriticalFluids
Wehavelearnedaboutthethreephaseswearefamiliarwithfromeverydaylife:solids,liquidsandgases.
Wehaveseenthatwecanliquefygasesbycoolingorincreasingthepressure.Asthepressureonagas
increases,thegasiscompressedintoaneversmallervolume.Ifthetemperatureislowenough,this
compressioneventuallyresultsinliquefaction.Athighenoughtemperature,however,noamountof
compressioncancauseliquefactionthatis,theliquidgastransitionisnolongerpossible.Instead,the
substancebecomesasupercriticalfluid.Asupercriticalfluidisafluidthathascertaincharacteristicsof
bothliquidsandgasesbutisneither.

Imaginethatyouhavealiquidinasealedcontainer.Onheating,thevapourpressureincreasesasmore
moleculesfromtheliquidescapeintothegasphase,thusincreasingthedensityinthegasphasewhilealso
decreasingthedensityintheliquidphase.Aswecontinueheatingthecontainer,thedensitiesinthegas
phaseandtheliquidphaseapproachthesamevalue.Atthepointwheretheybecomeequalwecanno
longerdistinguishbetweentheliquidandgasphases,i.e.wecannotobserveaphaseboundary.The
temperatureatwhichthisoccursiscalledthecriticaltemperature(Tc )theassociatedpressureiscalled
thecriticalpressure.Thecombinationofthecriticaltemperatureandthecriticalpressureiscalledthe
criticalpoint.Thesubstanceisnowinitssupercriticalstate(figure7.18).Ithastheviscositytypicalofa
liquid,butitisabletoexpandorcontractlikeagas.

FIGURE7.18 (a)BelowthecriticaltemperatureforCO2 youcanclearlyseethephaseboundarybetween

theliquidandthegasphase.
(b)Asthetemperaturerisestheliquidbecomeslessdense,thevapourphasebecomesmore
dense,andthephaseboundaryblurs.
(c)Abovethecriticaltemperaturethephaseboundaryhasdisappearedandonlya
supercriticalfluidexists.

ThecriticalpointofwaterisT=647K,p=22110 5Pa,thatofCO2isT=304K,p=73.910 5Pa,and

thatofN2isT=126K,p=33.910 5Pa.Althoughcriticalpressuresaremanytimesgreaterthan
atmosphericpressure,supercriticalfluidshaveimportantcommercialapplications.Themostimportantof
theseistheuseofsupercriticalcarbondioxideasasolvent.SupercriticalCO2diffusesthroughasolid
matrixrapidly,andittransportsmaterialswellbecauseithasalowerviscositythanliquids.Supercritical
CO2iscurrentlyusedasasolventfordrycleaning,forpetroleumextraction,fordecaffeinationandfor
polymersynthesis.Comparedwithsolventsusedpreviouslyforsomeoftheseprocesses,suchas
dichloromethane,CH2Cl2,andtetrachloromethane,CCl4,supercriticalCO2isamuchbetterchoice.

PhaseDiagrams
Thephasebehaviourofasubstancecanbeconvenientlysummarisedinaphasediagramasafunctionof
temperatureandpressure.Anexampleisprovidedinfigure7.19.Pressureisplottedalongtheyaxis,and
temperatureisplottedalongthexaxis.IntheregionoflowTandhighp,thesubstanceexistsasasolid.In
theregionofhighTandlowp,thesubstanceexistsasagas.InsomeintermediaterangeofTandp,the
substanceexistsasaliquid.
 FIGURE7.19Thegeneralformofaphasediagram.Anypointonthediagramcorrespondstoaspecific
temperatureandpressure.Boundarylinestraceconditionswhereneighbouringphasesexistin
equilibrium,andthebluearrowsshowsixtypesofphasetransitions.Theredarrowshighlighta
sequenceofphasechangesonchangingtemperatureatconstantpressure,oronchanging
pressureatconstanttemperature.

Figure7.19illustratesmanyofthecharacteristicfeaturesofphasediagrams:
1. Boundarylinesbetweenphasesseparatetheregionswhereeachphaseisthermodynamically
stable.(Substancescanexistasametastablephaseoutsidetheirthermodynamicallydetermined
boundaries,e.g.carboncanexistasdiamond,ratherthangraphite,underambientconditions.
2. Movementacrossaboundarylinecorrespondstoaphasechange.Thebluearrowsonthefigure
showsixdifferentphasechanges:sublimationanditsreverse,depositionmeltinganditsreverse,
freezingandvaporisationanditsreverse,condensation.
3. Onaboundaryline,thetwoneighbouringphasescoexistinadynamicequilibrium.Inaddition,at
agivenpressure,forexample,whenheatisaddedorremoved,thetemperatureofthistwophase
systemdoesnotchangeuntilallofonephasehasconvertedtotheother.Thenormalmeltingpoint
andnormalboilingpointofasubstance(shownbyreddots)arethepointswherethephase
boundarylinesintersectthehorizontallinethatrepresentsp=1.01310 5Pa.
4. Threeboundarylinesmeetatasinglepoint(shownbyanotherreddot),calledatriplepoint.All
threephasesarepresentsimultaneouslyatthisuniquecombinationoftemperatureandpressure.
Noticethat,althoughtwophasesarestableunderanyoftheconditionsspecifiedbytheboundary
lines,threephasescanbesimultaneouslystableonlyatatriplepoint.
5. Abovethetemperaturespecifiedbythecriticalpoint(againshownbyareddot),thegascannotbe
liquefiedunderanypressure.Insteadifthepressureishighenoughasupercriticalfluidforms.It
hastheviscositytypicalofaliquid,butitisabletoexpandorcontractlikeagas.
6. Whathappenstoasubstanceastemperaturechangesatconstantpressurecanbedeterminedby
drawingahorizontallineattheappropriatepressureonthephasediagram(shownasahorizontal
redline).
7. Whathappenstoasubstanceaspressurechangesatconstanttemperaturecanbedeterminedby
drawingaverticallineattheappropriatetemperatureonthephasediagram(shownasaverticalred
line).
8. Thetemperatureforconversionbetweenthegasphaseandacondensedphasedependsstronglyon
pressure.Qualitatively,thisisbecausecompressingagasincreasesthecollisionrateandmakes
condensationmorefavourable.
 9. Themeltingtemperatureisalmostindependentofpressure,makingtheboundarylinebetween
solidandliquidnearlyvertical.Qualitatively,thisisbecausemoderatepressurehashardlyany
effectonthecondensedliquidandsolidphases.
10.Thesolidgasboundarylineextrapolatestop=0PaandT=0K.Thisisaconsequenceofthe
directlinkbetweentemperatureandenergy.At0K,atoms,ionsandmoleculeshaveminimum
energy,sotheycannotescapefromthesolidlattice.At0K,thevapourpressureofeverysolid
substancewouldbe0Pa.

Thephasediagramforwater,showninfigure7.20,illustratesthesefeaturesforafamiliarsubstance.The
figureshowsthatliquidwaterandsolidicecoexistatthenormalmeltingpoint(mp),T=273.15Kandp=
1.01310 5Pa.Liquidwaterandwatervapourcoexistatthenormalboilingpoint(bp),T=373.15Kand
p=1.01310 5Pa.Thetriplepoint(tp)ofwateroccursatT=273.16Kandp=0.006110 5Pa.The
figureshowsthatwhenpislowerthan0.006110 5Pa,thereisnotemperatureatwhichwaterisstableas
aliquid.Atthoselowpressures,icesublimesbutdoesnotmelt.

FIGURE7.20Thephasediagramforwater.ThecriticalpointisatT=647K,p=221105 Pa,welloutsidethis
diagram.

Thedashedlinesonfigure7.20showtwopathsthatinvolvephasechangesforwater.Thehorizontal
dashedlineshowswhathappensasthetemperatureincreasesataconstantpressureof1.01310 5Pa.As
icewarmsfromalowtemperature,itremainsinthesolidphaseuntilthetemperaturereaches273.15K.At
thattemperature,solidicemeltstoliquidwater,andwaterremainsliquidasthetemperatureincreases,until
itreaches373.15K.At373.15K,liquidwaterchangestowatervapour.Whenthepressureis1.01310 5
Pa,waterexistsinthegasphaseatallhighertemperatures.Theverticaldashedlineshowswhathappensas
thepressureonwaterisreducedataconstanttemperatureof298K(approximatelyroomtemperature).
Waterremainsintheliquidphaseuntilthepressuredropsto3.0410 3Pa.At298K,waterexistsinthe
gasphaseatanypressurelowerthanthis.Noticethatat298Kthereisnopressureatwhichwaterexistsin
thesolidstate.

Giventhatthetemperatureofthetriplepointisslightlyhigherthanthetemperatureofthenormalmelting
point,wecanconcludethattheslopeoftheboundarylinebetweenthesolidandliquidphaseshastobe
negative.Asshowninthemagnifiedsectionoffigure7.20,ifyoustartwithsolidH2Oatatemperaturejust
belowthetriplepointandincreasethepressureatconstanttemperatureyouwilleffectaphasechange
fromsolidtoliquid(dashedline).Thisshows,aswediscussedintheopeningparagraphofthischapter,
thatthedensityoftheliquidishigherthanthedensityofthesolid,whichiswhyicefloatsonwater.Ice
skatersmakeuseofthispressureinducedphasetransition.Thethinbladesoftheiriceskatesputpressure
ontheice,changingittoliquidwaterwhichrefreezesoncethepressureisremoved.Thispropertyofwater
isrelativelyuncommonamongsubstances.Mostsolidshavehigherdensitythantheircorresponding
liquids.Forwater,thelowerdensityiscausedbythelargernumberofhydrogenbondsperwatermolecule
inicecomparedwithliquidwater.
Allphasediagramsofpuresubstancessharethe10commonfeatureslistedpreviously.However,the
detailedappearanceofaphasediagramisdifferentforeachsubstance,asdeterminedbythestrengthof
theinteractionsbetweenitsconstituents.Figure7.21showstwoexamples,thephasediagramsfornitrogen
andcarbondioxide.Bothofthesesubstancesaregasesundernormalconditions.IncontrasttoH2O,which
hasatriplepointcloseto298K,N2andCO2havetriplepointsthatarewellbelowroomtemperature.
Althoughbotharegasesatambienttemperatureandpressure,theybehavedifferentlywhencooledat
atmosphericpressure.Molecularnitrogenliquefiesat77.4Kandthensolidifiesat63.29K,whereas
carbondioxidecondensesdirectlytothesolidphaseat195K.Thisdifferenceinbehaviourarisesbecause
thetriplepointofCO2,incontrasttothetriplepointsofH2OandN2,occursatapressuregreaterthan
1.01310 5Pa.ThephasediagramofCO2showsthatatapressureof1.01310 5Pa,thereisno
temperatureatwhichCO2existsintheliquidphase.

FIGURE7.21Phasediagramsfornitrogenandcarbondioxide,twosubstancesthataregasesatroom
temperatureandpressure(sp=normalsublimationpoint).

Phasediagramsareconstructedbymeasuringthetemperaturesandpressuresatwhichphasechanges
occur.Approximatephasediagramssuchasthoseshowninfigures7.20and7.21canbeconstructedfrom
thetriplepoint,normalmeltingpointandnormalboilingpointofasubstance.

WORKEDEXAMPLE7.2

ConstructingaPhaseDiagram
Ammoniaisagasunderambientconditions.Itsnormalboilingpointis239.8K,anditsnormal
meltingpointis195.5K.ThetriplepointforNH3isp=0.061210 5PaandT=195.4K.Use
thisinformationtoconstructanapproximatephasediagramforNH3.

Analysis

Thenormalmeltingandboilingpointsandthetriplepointgivethreepointsonthephase
boundarycurves.Toconstructthecurvesfromknowledgeofthesethreepoints,usethe
commonfeaturesofphasediagrams:thegasliquidandgassolidboundariesofphase
diagramsslopeupwards,theliquidsolidlineisnearlyvertical,andthegassolidlinebeginsat
T=0Kandp=0Pa.

Solution

Beginbychoosingappropriatescales,drawingthep=1.01310 5Palineandlocatingthe
givendatapoints.Anuppertemperaturelimitof300Kencompassesallthedata.

Next,connectthepointsandlabelthedomains.

Isouranswerreasonable?

Checkthatpressureisontheyaxisandtemperatureisonthexaxisandthatyouhavenot
accidentallyinterchangedthesolid,liquidandgasphases.Alsocheckthattheslopeofthe
solidgasphaseboundaryislesssteepthanthatoftheliquidgasphaseboundarynearthetriple
pointandthatthesolidliquidphaseboundaryisnearlyvertical.
 PRACTICEEXERCISE7.2
Molecularchlorinemeltsat172K,boilsat
239Kandhasitstriplepointat0.01410 5
Paand172K.Sketchthephasediagramfor
thiscompound.

Phasediagramscanbeusedtodeterminewhichphaseofasubstanceisstableatanyparticularpressure
andtemperature.Theyalsosummarisehowphasechangesoccuraseitherconditionisvaried.

WORKEDEXAMPLE7.3

InterpretingaPhaseDiagram

Achemistwantstoperformasynthesisinavesselatp=0.5010 5PausingliquidNH3asthe
solvent.Whattemperaturerangewouldbesuitable?Whenthesynthesisiscomplete,the
chemistwantstoboiloffthesolventwithoutraisingTabove220K.Isthispossible?

Analysis

ThephasediagramforNH3(refertoworkedexample7.2)showstheboundarylinesforthe
liquiddomain.Theseboundarylinescanbeusedtodeterminetheconditionsunderwhich
phasechangesoccur.

Solution

Becausethechemistwantstoworkatp=0.5010 5Pa,drawahorizontallineacrossthephase
diagramatp=0.5010 5Pa.Hereisanexpandedviewofthephasediagrambetween150and
300K.
Thehorizontallineintersectstheboundarylinesatabout235Kand195K.LiquidNH3is
stablebetweenthesetemperaturesatthispressure.

Atthecompletionofthesynthesis,thechemistwantstoremovethesolventwithoutraisingT
above220K.Averticallineat220Konthephasediagramrepresentsthiscondition.

Thelineintersectstheliquidgasboundaryatabout0.3510 5Pa.Avacuumpumpcapableof
reducingpbelow0.3510 5PacanbeusedtovaporiseandremovetheNH3whilekeepingthe
temperaturebelow220K.

Isouranswerreasonable?

Checkthatthelinesforpressureandtemperatureareenteredcorrectly.SinceNH3(l)boilsat
235Kand0.510 5Pa,forNH3(l)toboilatthelowertemperatureof220Kweneedareduced
pressure,aswehavedetermined.
 PRACTICEEXERCISE7.3

AsampleofN2gasisatp=0.110 5Paand
T=63.1K.Usefigure7.21todeterminewhat
willhappentothissampleifthetemperature
remainsfixedwhilethepressureslowly
increasesto110 5Pa.

Thephasediagramswehavestudiedarethesimplestonesthatoccurforpuresubstances.However,many
substanceshavemorethanonesolidphase(thereare14differentknownformsofice!).Phasediagramsof
solidsareparticularlyusefulingeology,becausemanymineralsundergosolidsolidphasetransitionsat
thehightemperaturesandpressuresfounddeepintheEarth'scrust.Figure7.22isthephasediagramfor
silica(silicondioxide,SiO2),animportantgeologicalsubstance.Noticethatthescalereflectsgeological
pressuresandtemperatures.Noticealsothattherearesixdifferentformsofcrystallinesilica,eachstablein
adifferenttemperaturepressureregion.Ageologistwhoencountersasampleofstishovitecanbe
confidentthatitsolidifiedunderextremelyhighpressureconditions.

FIGURE7.22Thephasediagramforsilicashowssixdifferentformsofthesolid,eachstableunderdifferent
temperatureandpressureconditions.

Ifwehavemorethanonecomponentinamixture,phasediagramsbecomeevenmorecomplicated,and
treatmentoftheseisbeyondthescopeofthisbook.

ChemicalConnections

ChemistryandCoolJackets
ResearchersatRMITUniversityhavedevelopedanadvancedcoolingjackettohelpathletes
reducetheirbodytemperaturesbeforemajorevents.Coolingthebodypriortoanevent
enhancestheathlete'sperformanceanddelaystheonsetofexhaustionbyminimisingthestress
andstrainonthebody,whichreducestherelianceonthebody'sstoreofsugar.Athleteshave
longusedicejacketstoreducetheirbodytemperaturebeforebigracestotakeadvantageof
thesebenefits,buttheyhaveoftensufferedundesirablesideeffectssuchasshivering,iceburn
andheadaches.TheRMITteam,ledbyProfessorDavidMainwaring,andincludingProfessor
RobertShanks,developedajacketthatisfilledwithsolidphasechangematerial(PCM,figure
7.23).Inordertoeffectcooling,aPCMmustundergoanendothermicphasechange(onethat
requiresheatfromthesurroundingstooccur).Manycompoundsdoofcoursedothis,most
notablywater(theicejacketsmentionedaboveoperateonthisprinciple)butinorderforthe
wearertobecomfortable,thephasechangeneedstooccurataroundroomtemperature.The
PCMdevelopedbyRMITconsistsofamixtureoftwoormorestraightchainalkanes.While
lowmolarmassalkanesareeithergasesorliquids,thosewithmorethanabout12carbonatoms
havemeltingpointsabove0C.Theactualalkanesusedarechosensoastogivethemost
desirablethermalproperties,and,inthiscase,atleast90%ofthealkaneshavebetween14and
18carbonatoms.Attemperaturesbelowabout18C,thePCMexistsasawaxysemisolidin
whichthechainsofthealkanemoleculesarealigned.Whenthejacketisworn,thebodyheatof
thewearercausesaphasechangetooccurinthePCMfromasemisolidtoaliquidatabout20
C.Thisisanendothermicprocessthatremovesheatfromthesurroundings,therebyleadingto
acoolingeffectforthewearer.Thejacketcanberegeneratedforusesimplybycoolingittoa
temperaturebelowabout18Cin,forexample,anairconditionedroom.Thiscausesan
exothermicphasechange(onethatgivesoutheattothesurroundings)ofthePCMbacktoa
semisolidandthejacketisagainreadyforuse.
 FIGURE7.23Anicejacketthatusessolidphasechangematerial(PCM)whichchangesfroma
semisolidtoafluidatabout20C.
2005RMITUniversity,EducationalTechnologyAdvancementGroup.Photographer
MargundSallowsky.

Becauseheatiswithdrawnfromthebodyatclosetonormalskintemperature,andnotatice
temperature,thecoolingprocessesaremorecomfortable,efficientandeffective.

ThejacketsweredevelopedinconjunctionwiththeAustralianInstituteofSportandareusedby
manyofAustralia'seliteathletesinpreparationformajorsportingeventssuchastheOlympic
Games.

Thevestsalsohavepotentialinthetreatmentofmedicalconditions.Applicationsmightinclude
controlofheatinducedhandtremorsanddizzinessinpeoplewithmultiplesclerosis,aswellas
theeffectiveandsafecoolingofpeoplewhohavesufferedbraininjuriesorcardiactrauma.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.4OrderinSolids
Incontrasttomoleculesingasesandliquids,whichcanmoverelativelyfreely,theatoms,moleculesorions
inasolidareinfixedpositions.Generally,theirmotionsarerestrictedtovibrationsaboutthesefixed
positions.Inthissection,weexaminetheprinciplesthatgoverntherelativearrangementsofatoms,
moleculesandionsinsolids.Tostartourexplorationoforderinsolidswewilllookatsomesimplecases.

ClosepackedStructures
Mostelementsintheperiodictablearemetalsand,apartfrommercury,allmetalsaresolidsatstandard
conditions.Inordertodevelopapictureofmetalstructures,wewillassumethatwecanapproximateametal
atomwithasphere.Figure7.24showsbothsquareandhexagonalarrangementsofidenticalspheres.We
canseethatthehexagonalarrangementisabletofitmorespheresintothesameareaeverysphereinthe
hexagonalarrangementhassixdirectneighbours,butonlyfourinthesquarearrangement.Thishexagonal
arrangementofidenticalspheresisthemostdensepackingthatyoucanachieveinonelayerofspheres.
Youcanseethiswhenyouplacepoolballsinthetriangleatthestartofthegame(figure7.25).Onlyifyou
arrangethemthiswaycanalloftheballsfitintothetriangle.

FIGURE7.24Comparisonof(a)squareand(b)hexagonalarrangementofidenticalspheres.Youcanseethatboth
squaresfit16spheres(movingthespheresoutsidethesquarein(b)intotheemptyspaceattheother
sideofthesquare(lightershadedspheres).In(b),thereisspaceleftoveratthetopofthesquare,
whilein(a)thereisnospaceleftover,indicatingthatthespheresinthehexagonalarrangementare
closertogether.
 FIGURE7.25Poolballsfitintothetriangleinahexagonalarrangement.

Nowaddasecondlayerofspherestothehexagonalarrangement.Let'scallthefirstlayerlayerAandthe
secondlayerlayerB.Toachievethemostcompactarrangement,eachsphereinlayerBsitsinoneofthe
dimplesbetweenatrioofspheresinlayerA.TherearesixdimplesaroundanysphereinlayerA.Youcan
seethatthecentresoftwoneighbouringdimplesareclosertogetherthanthediameterofthespheres.Hence,
itisimpossibletoplaceasphereovereverydimple.Forexample,ifweplacespheresasindicatedbythered
ringsinfigure7.26,wecanseethatitisimpossibletoplacespheresinthepositionsindicatedbytheblue
ringsatthesametime.

FIGURE7.26Itisimpossibletoplaceasphereovereverydimple.Wecanplacespheresonlyintheredpositions
orbluepositions,notbothatthesametime.

Ifwefillallthedimplescorrespondingtotheredringsinfigure7.26a,wecreateasecondlayerasshownin
figure7.27b.ThisaddsthreemoreadjoiningspheresforeachsphereinlayerA,oneineachsetofthree
neighbouringdimples.Asadditionalspheresareadded,layerBeventuallylooksidenticaltolayerA,except
thatitisoffsetslightlytoallowthespherestonestleinthedimplesformedbythelayerbelow.Thereisno
differencebetweenfillingalldimplescorrespondingtotheredringsortheblueringstheresulting
arrangementsofspheresareindistinguishable.

Nowconsideraddingathirdlayerofspheres.Thisnewlayercanbeplacedintwodifferentwaysbecause
therearetwosetsofdimplesinlayerB.Figure7.28showsacloseupoffigure7.27b.Noticeinfigure7.28
thattheviewthroughonesetofdimples(highlightedinorange)revealstheorangespheresoflayerA.The
viewthroughtheothersetofdimples(highlightedinblue)revealstheunfilleddimplesoflayerA.
 FIGURE7.27 (a)Spheresclosepackedinalayergenerateahexagonalpattern.
(b)Whenasecondlayerispackedontopofthefirst,eachsphereinthesecondlayernestlesin
thedimpleformedbetweenthreeadjacentspheresinthelowerlayer.

FIGURE7.28Athirdlayerofspherescanbeplacedintwodifferentways.

Ifspheresinthethirdlayerlieinthedimpleshighlightedinorange,thethirdlayerisdirectlyabovethefirst,
andthestructureiscalledhexagonalclosepacked(hcp).Ifthespheresofthethirdlayerlieinthedimples
highlightedinblue,thethirdlayerisoffsetfrombothofthelowerlayers.Thisarrangementiscalledcubic
closepacked(ccp).Figure7.29showsthatinthehexagonalclosepackedstructurethepositioningofthe
thirdlayercorrespondstothatoflayerAandthereforewealsolabelitA.Inthecubicclosepacked
structure,thepositioningisdifferentandsowelabelthethirdlayerlayerC.Comparingthetwodiagrams,
wecanseethatinthehexagonalclosepackedstructureonesetofdimplesisnevercovered,whileinthe
cubicclosepackedstructure,theyare.Ifwecontinuethislayeringpattern,wefindthatahexagonalclose
packedstructurehasthepatternABABetc.,whileacubicclosepackedstructurehasthepatternABCABC
etc.
 FIGURE7.29 Topdownviewsofhexagonalandcubicclosepackedarrangements:
(a)ThehexagonalclosepackedstructurehasalayerrepeatingpatternABABetc.
(b)ThecubicclosepackedstructurehasalayerrepeatingpatternABCABCetc.

Thetwostructuretypesdescribedarecalledclosepackedstructuresbecausetheyachievemaximumspace
fillingforidenticalspheres.Ineitherofthesearrangements,74%ofthetotalspaceisfilled,andeachsphere
has12nearestneighbours(i.e.neighbourswiththesameshortestdistancetothatsphere):sixinthesame
plane,threeinthedimplesaboveandthreeinthedimplesbelow.Thisisshownforthehexagonalandcubic
closepackedstructuresinfigure7.30.Thenumberofnearestneighboursisalsocalledthecoordination
number,andthereforespheresinclosepackedstructureshaveacoordinationnumberof12.

FIGURE7.30Inclosepackedstructures,eachspherehas12nearestneighbours:sixinthesameplane,threein
thedimplesaboveandthreeinthedimplesbelow.

Manymetalsformcrystalswithhexagonalorcubicclosepackedgeometries,sincemetalbondingthat
involvessharingvalenceelectronsbenefitsfromclosecontactbetweenparticipatingmetalatoms.For
instance,magnesiumandzinccrystallisewiththeiratomsinahexagonalclosepackedarray,whilesilver,
aluminiumandgoldcrystalliseinthecubicclosepackedarrangement.Othersphericalentities,suchas
argonatoms,andmethaneandC60molecules,alsoformclosepackedarrangements.Argonsolidifiesatlow
temperatureasacubicclosepackedcrystal,andneoncansolidifyineitherthehcporccpform.
TheCrystalLatticeandtheUnitCell
Inasolid,thenumberofatoms,ionsormoleculesisenormous.Ifyoucouldimaginebeingatthecentreof
evenasmallsampleofasolid,youwouldfindthattheatoms,ionsormoleculesgoonasfarasyoucansee
ineverydirection.Describingalltheindividualpositionsisimpossibleand,fortunately,unnecessaryifwe
areabletoidentifyarepeatingpatternwithinthesolid.

Thereareanumberofrulestoconsiderwhendefiningsucharepeatingpattern,andtostartoffwewilllook
atexamplesintwodimensions.Wecanrecognisearepeatingmotifinthewallpaperdesignoffigure7.31a.
Howcanwedescribethispattern?Inordertoconcentrateontherepeatingfeaturesofthepattern,westart
byrandomlyselectingapointandthenmarkeveryotherpointonthewallpaperthathasanidentical
environment(tomakethateasiertoseewechoosetheeyeoftherearmostofthethreefish)asshownin
figure7.31b.

FIGURE7.31 Definingarepeatingpattern:
(a)Thereisarepeatingpatterninthewallpaperdesign.
(b)Thepatterncanbedescribedbyasetofpointswithidenticalenvironments.
(c)Theresultingpatternisalatticeandeachblackdotisalatticepoint.

Figure7.31bshowsthissetofpoints,whichhavebeenconnectedbylines.Infigure7.31cwetakeawaythe
wallpaper,leavingjusttheconnectedpoints.Wecallthispatternofpointsalattice,andeveryindividual
pointisalatticepoint.Sinceweselectedasetofpointsbyrequiringeachonetohaveanidentical
environment,thissetofpointsrepresentstherepeatingfeatureofourwallpaperdesign,andeverylattice
pointrepresentsonerepeatingmotif.

Inthenextstep,wemustfindthesmallestrepeatingunitwithinourlattice,whichinthiscaseisoneofthe
rectanglesinfigure7.31c.Wecallthesmallestuniquerepeatingunitofalatticetheunitcell(therearea
numberofrulesforthecorrectchoiceofunitcell,buttheyarebeyondthescopeofthisbook).Repeating
theunitcellintwodimensionswillcreatethelattice.Therefore,allweneedtodescribeanypatternisthe
latticeandthecontentoftheunitcell.

Animportantfactaboutlatticesisthatthesamelatticecanbeusedtodescribemanydifferentdesignsor
structures.Forexample,takethesquarelatticeandunitcellinfigure7.32a.Infigure7.32b,weseeadesign
formedbyassociatingablueheartwitheachlatticepoint.Usingasquarelattice,wecouldformanynumber
ofdesignsjustbyusingdifferentdesignelements(forexample,aroseoradiamond),orbychangingthe
lengthsoftheedgesoftheunitcell.Theonlyrequirementisthatthesamedesignelementmustbe
associatedwitheachlatticepointthatis,eachlatticepointmusthaveanidenticalenvironment.Thereisno
requirement,however,thatthelatticepointiscentredontheobject,asillustratedinfigure7.32c,d.Youare
allowedtoshifttheentirelatticeaslongasyoustillendupwithalllatticepointshavingidentical
environments.

FIGURE7.32 Atwodimensionallattice:
(a)asimplesquarelattice,forwhichtheunitcellisasquarewithlatticepointsatthecorners,
(b)awallpaperpatternformedbyassociatingadesignelement(blueheart)witheachlattice
point.Thexcentredoneachheartcorrespondstoalatticepoint.Noticethattheunitcell
containsportionsofaheartateachcorner.(Therestofeachheartliesinadjacentunitcells.)
(c)and
(d)Thereisnorequirementthatthelatticepointiscentredonanyobject.In(a),(b),(c)and(d),
alltheinformationneededtogeneratetheentirearrayispresentintheunitcell,whichis
repeatedoverandover.

AnotherexampleisshowninthepicturebytheDutchartistMCEscher(18981972)reproducedinfigure
7.33.Escheroftenusedsymmetricalpatternsalignedtogethertocreateanoveralldesign.Therepeating
unitscanbevisualisedastilesplacededgetoedge.Thefacesofunitcellscanbesquares,rectanglesor
parallelograms.Infigure7.33aeachtileisaparallelogram.Onceyouhavechosenthesizeandshapeofthe
unitcell,youcanmoveitsoriginandstillcreatethesameoverallpattern(figure7.33b).
 FIGURE7.33AdrawingbyMCEscherthatcontainsarepeatingpattern.Atwodimensionalunitcellishighlighted
in(a).In(b),theunitcellhasbeenshiftedanditisshownhowrepeatingitintwodimensionswill
producetheentirepattern.(Source:M.C.Escher'sSymmetryDrawingE18,2007TheM.C.
EscherCompanyHolland.Allrightsreserved.www.mcescher.com)

Forthesakeofsimplicitywehavelookedatlatticesandunitcellsintwodimensions.Wecanalsoapply
theseconceptstothreedimensionalpatterns.Theions,atomsormoleculesinmanysolidsarearrangedin
regularthreedimensionalpatterns.Suchsolidsareclassifiedascrystallinesolids.Diamondsarean
example.Wecandescribecrystallinesolidsusingtheconceptsofacrystallattice,thatis,thelatticeofa
crystallinesolidandaunitcell.Itispossibletodescribelimitlessnumbersofdifferentcompoundswithjusta
limitedsetofthreedimensionallattices.Infact,ithasbeenshownmathematicallythatthereareonly14
differenttypesofthreedimensionallatticespossible,whichmeansthatessentiallyallcrystallinechemical
substancesmustformcrystalswithoneofthese14latticetypes,albeitwithdifferentunitcelldimensions.
Onthefollowingpages,wedescribesomemetalstructureswithcubicunitcells.Thesecrystalstructurescan
bedescribedsuchthatalltheatomsinaunitcellareassociatedwiththelatticepoints,i.e.thenumberof
atomsintheunitcellandthenumberoflatticepointswillbeidentical.Thisisbecauseallmetalatomsin
eachoftheseverysimplestructureshaveidenticalsurroundingsandthereforeallcanbeassociatedwith
latticepoints.Thisisnotsoformostothercrystallinesolidstructures.

CubicStructures
Theeasiestthreedimensionalstructuretovisualisehasasimplecubeastheunitcell.Inasimplecubic
crystal,layersofatomsstackonedirectlyaboveanother,sothatallatomsliealongstraightlinesatright
angles,asfigure7.34shows.Eachatominthisstructurehasacoordinationnumberof6therearefour
nearestneighbourswithinthesameplane,oneabovetheplaneandonebelowtheplane.Withinonelayerof
thecrystal,anysetoffouratomsformsasquare.Addingfouratomsdirectlyaboveorbelowthefirstfour
formsacube.Thisstructureiscalledtheprimitivecubicstructure,becauseithasaprimitivecubiclattice.
(Inthiscontext,primitivemeansthatthereisonlyonelatticepointperunitcell.Amethodfordetermining
thenumberoflatticepointsisdescribedbelow.)Theunitcelloftheprimitivecubicstructureisshowninthe
cutawayportionoffigure7.34.Tocalculatehowmanyatomsareintheunitcell,wecountonlythat
proportionoftheatomthatiswithintheunitcellboundaries.Anatomthatislocatedonthecornerofacube
issharedbyeightcubesintotal.Therefore,only ofthatatomcountsforanyoneofthosecubes.Theunit
cellcontains ofanatomateachoftheeightcornersofacube.Thetotalnumberofatomsintheunitcellis

thus .Thesameappliestocountinglatticepointsaunitcellwithlatticepointsonlyonthecorners
endsupwithonelatticepoint,i.e.aprimitivelattice.Thefractionofspacethatisfilledbytheatomsinthis
primitivecubicunitcellisonly52%.Thisismuchlessthanthemostefficientpacking,whichachieves74%
spacefilling(seep.270).Consequently,thisstructureisadoptedbyonlyonemetal:polonium.
 FIGURE7.34Thesimplecubicstructureisbuiltfromsquarelayersofspheresstackedonedirectlyaboveanother.
Thecutawayviewshowsoneunitcell.

Wheneightatomsformacube,thereisacavityatthecentreofthecube.Thecavityisnotlargeenoughto
holdanadditionalatom,butmovingtheeightcorneratomsslightlyawayfromeachotherdoesallowthe
structuretoaccommodateanotheratomofthesametypeinthecentre.Theresultisthebodycentredcubic
structure,describedbyabodycentredcubiclattice(bcc),whichnowhastwolatticepoints:oneonacorner
andoneinthecentreofthecube.Eachatominabodycentredcubiclatticeisatthecentreofacubeand
contactseightneighbouringcorneratoms(seefigure7.35).Inotherwords,everyatominthestructurecan
beviewedasthecentreatomofonebodycentredcubeorasacorneratominanothercube.Theunitcellof
abodycentredcubecontainsatotalof atoms.Theviewsoftheironcrystalstructurein
figure7.35onthenextpageillustratethisarrangement.
 FIGURE7.35 Viewsofthearrangementofatomsiniron:
(a)aviewofthebodycentredcrystallatticeand
(b)theunitcell.

Althoughthecorneratomsarefurtherapartinabodycentredcubethaninaprimitivecube,theextraatom
inthecentreofthestructuremakesthebodycentredcubicstructuremorecompactthantheprimitivecubic
structure.Itfills68%ofthetotalspace,whichisclosetothemaximumpossible.Allofthegroup1metals,
aswellasironandthetransitionmetalsfromgroups5and6,formcrystalswithbodycentredcubic
structures.

Anothercommoncubiccrystalstructureisthefacecentredcubicstructure(fcc),whichisthesameasthe
cubicclosepackedstructurethatweencounteredonp.270.Whenfouratomsformasquare,thereisopen
spaceatthecentreofthesquare.Afifthatomcanfitintothisspacebymovingtheotherfouratomsaway
fromoneanother.Additionalatomscanbeplacedinthecentresofallsixfacesofthesimplecube,asfigure
7.36shows.

FIGURE7.36 Thefacecentredcubiclatticecanbeviewedas:
(a)asimplecube,
(b)witheachfaceexpandedjustenoughtofitanadditionalatominthecentre,
(c)givingeightatomsatthecornersandsixatomsembeddedinthefaces.
(d)
Theunitcellhas ofanatomatthecentreofeachfaceand ofanatomateachcorner.
(Allatomsinthisarrangementarethesame.Differentcoloursareusedonlyforclarity.)

Theunitcellofthefacecentredcubeconsistsofsix atomsembeddedinthefacesofthecubeandeight

atthecornersofthecube.Thisunitcellcontains atoms.Eachatominaface
centredcubecontacts12neighbouringatoms.Consequently,thefacecentredcubeismorecompactthan
eitheroftheothercubicstructuresandfills74%ofthetotalspace.Thecubicclosepackedstructurethatwe
encounteredatthebeginningofsection7.4canbedescribedbythisfacecentredcubicunitcell.

Figure7.37showstherelationshipbetweenasetofhexagonallayersandafacecentredcubicunitcell.
Figure7.37ashowsatopdownviewofthehexagonallayers.Infigure7.37bwehaveremovedallbutone
oftheatomsfromthetopandbottomlayers,andhaveremovedallbutsixatomsineachofthetwomiddle
layers.Wecanseefromfigure7.37cthatalinedrawnbetweentheorangeatoms(fromthetopandbottom
layers)representsthebodydiagonalofacube.Eachfaceofthecubehasanatomateachcornerandone
atominthecentre,asshownbyfigure7.37c.Sincealltheatomsareidentical,thisisafacecentredcubic
arrangementasrevealedintheperspectivesoffigures7.37cand7.37d.

FIGURE7.37 Fourviewsofthehexagonallayerscontainedwithinafacecentredcubicarrangement:
(a)atopdownviewofthehexagonallayers,withanaxisshownasablackdot,
(b)asideviewshowingfourlayersalongtheaxis,
(c)tilting(b)leadstothearrangementshownhere,withtheverticalblacklinein(b)nowthe
bodydiagonalofthiscube,and
(d)theunitcell.(Allatomsinthisarrangementarethesame.Differentcoloursareusedforclarity
only.)

WecannowseethatthearrangementofhexagonallayersinanABCABCfashioniscalledacubicclose
packedstructure,becausethestructurecanbedescribedbyafacecentredcubicunitcell(thetermscubic
closepackedstructureandfacecentredcubicstructureareoftenusedsynonmously).Equally,the
hexagonalclosepackedstructuregetsitsnamebecauseitcanbedescribedbyahexagonalunitcellas
showninfigure7.38.
 FIGURE7.38 Threeviewsofthehexagonallayerscontainedwithinahexagonalclosepackedstructure:
(a)atopdownviewofthehexagonallayerswiththeunitcellshown,
(b)asideviewshowingthreelayersand
(c)theunitcell.Thisunitcellcontainstwoatomsandfills74%ofthespace.(Allatomsinthis
arrangementareofthesametype.Differentcoloursareusedforclarityonly.)

Uptonow,wehavedescribedthecrystallinearrangementsfavouredbysphericalobjectssuchasatoms,but
mostmoleculesarefarfromspherical.Nonsphericalobjectsrequiredifferentarraystoachievemaximal
stability.Toillustrate,compareastackofbananaswithastackoforanges(figure7.39).Justasthestacking
patternforbananasislesssymmetricalthanthatfororanges,thestructuralpatternsformostmolecular
crystalsarelesssymmetricalthanthoseforcrystalsofsphericalatoms,reflectingthelowersymmetryofthe
molecules.
 FIGURE7.39Nonsphericalbananasrequiredifferentpackingschemesfromsphericaloranges.

IonicSolids
Wewillnowshowhowtheprinciplesdiscussedpreviouslyrelatetotheactualstructuresofionicsolids.
Recallfromfigure7.28thattwosetsofdimplesarecreatedwhenweaddtwohexagonallayersofspheres.
Thisisshownagaininfigure7.40a.Onesetofdimpleshasanatomdirectlybelow(showninorange),while
theothersetdoesnot(showninblue).Theopenspacebetweenthetwolayersofspheresdirectlybelowthe
firstsetofdimplesissurroundedbyfourspheres(onebelowandthreeabove),whiletheopenspace
betweenthetwolayersofspheresdirectlybelowthesecondsetofdimplesissurroundedbysixspheres
(threebelowandthreeabove).Figure7.40bshowsthatthefourspheresassociatedwiththefirstsetof
dimplesformatetrahedron,whilefigure7.40cshowsthatthesixspheresassociatedwiththesecondset
formanoctahedron.Thespacebetweenthespheresiscalledaninterstitialhole.Theinterstitialholestake
upmuchlessspacethanthespheresthatsurroundthem.Ingeneral,themorespheresthatsurroundan
interstitialhole,thelargertheholeis,thatis,anoctahedralholeislargerthanatetrahedralhole.Thenumber
ofoctahedralholesequalsthenumberofspheresthatformthestructure,whilethenumberoftetrahedral
holesistwicethenumberofspheresthatformthestructure.
 FIGURE7.40 (a)Twosetsofdimplesarecreatedwhentwohexagonallayersofspheresarecombined.
(b)Thefourspheresassociatedwitheachdimpleshowninorangesurroundatetrahedralhole.
(c)Thesixspheresassociatedwitheachdimpleshowninredsurroundanoctahedralhole.

Thepackinginioniccrystalsrequiresthationsofoppositechargealternatewithoneanothertomaximise
attractionsandminimiserepulsions.Thecationsandanionsareusuallydifferentsizes(oftenthecationsare
smaller).Wecanunderstandionicstructuresbyassumingthattheclosepackedstructureisformedbythe
largerions,whilethesmallerionsfilltheinterstitialsites.Wecanidentifyacrystallatticeforthelargerions,
andthendescribehowthesmallerionspackwithinthatlattice.Becausethecrystalismadeupofahuge
numberofidenticalunitcells,thestoichiometrywithintheunitcellmustmatchtheoverallstoichiometryof
thecompound.

Ioniccompoundsadoptavarietyofstructuresthatdependonthestoichiometryandrelativesizesofthe
ions.Formany1:1ioniccrystalssuchasNaCl,themoststablearrangementisafacecentredcubicarrayof
anions(Cl)withthecations(Na+)packedintotheoctahedralholesbetweentheanions.Thisstructure
appearsinfigure7.41a.Noticethateverycationissurroundedbysixanionsandeveryanionissurrounded
bysixcations.TheunitcellbasedonclosepackingofClisshown.Inadditiontothefacecentredcubic
arrangementofchlorideions,theunitcellinfigure7.41bshows ofasodiumcationalongeachedgeof
thecell,andthereisanadditionalsodiumcationinthecentreoftheunitcell.Summingthecomponents
revealsthateachunitcellcontainsfourcompleteNaClunits,thusgivingthecorrect1:1stoichiometry.

FIGURE7.41 (a)Thestructureofsodiumchloridecanbedescribedasafacecentredcubicarrangementof
Clanions(green),withtheNa+cations(orange)occupyingtheinterstitialoctahedralsites.
(b)BecauseClanionsareconsiderablylargerthanNa+cations,thecommonlyusedunitcell
 placesanionsatthecorners.Thereisacationatthecentreofthisunitcell.

Manyionicsolidshavethesamestructuretypeassodiumchloride.ExamplesareallthehalidesofLi+,Na+,
K+andRb +,aswellastheoxidesofMg 2+,Ca2+,Sr2+andBa2+.

Caesiumchloride,inwhichtherelativesizeofthecationismuchlargerthaninsodiumchloride,formsa
differenttypeofstructure.Becauseitscationandanionareclosetothesamesize,caesiumchlorideismost
stableinaprimitivecubiclattice.ThereareClanionsatthecornersofthecube,withaCs+inthecentre,as
figure7.42shows.Theunitcellcontains chlorideionand1caesiumion.Thecaesiumchloride
structuretypeisalsofoundforCsBr,CsIandseveralother1:1ioniccrystalsinwhichthecationsand
anionshavesimilarsizes.

FIGURE7.42Thecaesiumchloridestructureconsistsofaprimitivecubicarrayofchlorideanionswithacaesium
cationatthecentreofeachunitcell.

Inzincsulfide,ZnS,therelativesizeratiosaresuchthatthezinccationistoosmallforoctahedralsitesand
insteadoccupiestetrahedralholesinthestructure.Sincetherearetwiceasmanytetrahedralsitesasspheres
thatformthestructure,onlyhalfwillbeoccupiedbyZn 2+cationsinaregularfashion.Wehaveseen
previouslythatafacecentredarrangementofanionsleadstofouranionsintheunitcell.Wecanseein
figure7.43thattherearealsofourcationswithintheunitcell,resultinginthecorrect1:1stoichiometry.In
thisstructure,asseeninfigure7.43b,everycationissurroundedbyfouranions,andeveryanionis
surroundedbyfourcationsinatetrahedralarrangement.

FIGURE7.43 Zincsulfide.
(a)Theunitcellofcubiczincsulfidehasanionsinafacecentredcubicarrangement.
 (b)Eachcationissurroundedbyfouranionsintheformofatetrahedron.

Manyioniccompoundshavestoichiometriesthatdifferfrom1:1.Togiveanexample,thefluoritestructure
isnamedforthenaturallyoccurringformofCaF2andiscommonforsaltsofthegeneralformulaMX2X.Itis
easiesttodescribethisstructurebythinkingoftheCa2+cationsarrangedinafacecentredcubicstructure.In
thisarrangement,theFanionsfillallthetetrahedralholesinthelattice,formingasimplecubeofeight
anionsintheinteriorofthefacecentredcube.Thisisincontrasttozincsulfide,whereonlyhalfofthe
tetrahedralholeswerefilled.Figure7.44ashowstheunitcellofthefluoritestructure,whichcontainsatotal
offourCa2+cationsandeightFanions(consistentwiththenumberoftetrahedralholesbeingtwicethe
numberofspheresthatformthestructure).
 FIGURE7.44 (a)Theunitcellofthefluoritestructurehascationsinafacecentredcubicarrangement,witha
simplecubeofanionswithintheunitcell.
(b)Allfluorideionsaresurroundedbyfourcalciumionsinatetrahedralarrangement.

Thisgivesthecorrect1:2stoichiometry,resultinginelectricalneutrality.

Thecalciumionsarearrangedinatetrahedronaboutthefluorideionsasshowninfigure7.44b.Wehave
brieflymentionedfoursimpleioniclattices,buttherearemanyothers.Moreover,thestructuresofmany
crystallinenetworksolidscanalsobedescribedbythemethodswehaveintroducedhereforNaCl,CsCl,
ZnSandCaF2.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.5XrayDiffraction
Xraydiffractioncanbeusedtodeterminethearrangementofatoms,moleculesorionsinacrystalline
structure.WhenatomsareexposedtoXrays,theyactliketinyXraysources.Ifwelookatradiationfrom
twosuchatoms(seefigure7.45),wefindthattheXraysareinphaseinsomedirectionsbutoutofphasein
others.Inchapter4youlearnedaboutconstructive(inphase)anddestructive(outofphase)interferencesof
waves,andthesecreateaphenomenoncalleddiffraction.Xraydiffractionbycrystalshasenabledscientists
todeterminethestructuresofextremelycomplexcompoundsinaparticularlyelegantway.

FIGURE7.45DiffractionofXraysfromatomsinacrystal.Xraysemittedfromatomsareinphaseinsome
directionsandoutofphaseinotherdirections.

Inacrystal,thereareenormousnumbersofatoms,andthesecanbedescribedbyalatticeandaunitcell.
WhenthecrystalisexposedtoXrays,diffractedbeamsduetoconstructiveinterferenceappearonlyin
specificdirections.Inotherdirections,noXraysappearbecauseofdestructiveinterference.TheXrays
comingfromthecrystalarerecordedandformadiffractionpattern(seefigure7.46).

FIGURE7.46 Xraydiffraction:
(a)schematicsetupforrecordinganXraydiffractionpatternand
(b)anXraydiffractionpattern.
In1913,WilliamHenryBraggandhisAustralianbornsonWilliamLawrenceBraggdiscoveredthatjusta
fewvariablescontroltheappearanceofanXraydiffractionpattern.Figure7.47illustratestheconditions
necessarytoobtainconstructiveinterferenceoftheXraysfromsuccessivelayers(planes)ofatomsina
crystal.AbeamofXrayswithawavelengthstrikesthelayersatanangle.Forcertaindistances,d,
betweenthelayers,constructiveinterferencecausesanintensediffractedbeamtoemergeatthesameangle,
.

FIGURE7.47DiffractionofXraysfromsuccessivelayersofatomsinacrystal.Thelayersofatomsareseparated
byadistanced.TheXraysofwavelengthenterandemergeatananglerelativetothelayersof
theatoms.FortheemergingbeamofXraystohaveanyintensity,theconditionn=2dsinmust
befulfilled,wherenisaninteger.

TheBraggequationrelates,andthedistancebetweentheplanesofatoms,d:

wherenisanyinteger.TheBraggequationisthebasictoolusedbyscientistsinthestudyofsolidstructures.
Letusbrieflyseehowitisused.

Inanycrystal,manydifferentsetsofimaginaryplanescanbepassedthroughthestructure.Figure7.48
illustratesthisideaintwodimensionsforasimplepatternofpoints.WhenacrystalisexposedtoXrays,
manydiffractedbeamsareproducedbecauseofthediffractionfromthemanysetsofplanes.Anapparatus
calledadiffractometer(figure7.49)isusedtorecordthediffractionpatternandallowsthedeterminationof
theanglesatwhichthediffractedbeamsemergefromeachdistinctsetofplanes.UsingtheBraggequation,
wecancalculatethedistancesbetweenplanesofatomsfromthemeasuredanglesofdiffraction,the
wavelengthoftheXrays(sourcedependent)andthevalueofn(usually1).Thenextstepistousethe
calculatedinterplanardistancestodeducetheunitcellofthelattice.Thelocationsoftheatomswithinthe
unitcellarethendeterminedfromtherelativeintensitiesofthediffractedbeams.Ifthissoundslikea
difficulttask,itis!Forallbutthesimplestcrystallinestructures,sophisticatedmathematicsandcomputers
areneededtoaccomplishit.Theefforts,however,arewellrewardedbecausethecalculationsgivevery
accuratelocationsfortheatomswithintheunitcell.Thisenablesustounderstandthebonding,
intermolecularinteractionsandpropertiesofcrystallinematerials.
FIGURE7.48Atwodimensionalpatternofpointswithmanypossiblesetsofparallellines.Inathreedimensional
crystallatticetherearemanysetsofparallelplanes.

FIGURE7.49AmodernXraydiffractometer.

WORKEDEXAMPLE7.4

UsingCrystalStructureDatatoCalculateAtomicSizes
Xraydiffractionmeasurementsrevealthatcoppercrystalliseswithafacecentredcubiclatticein
whichtheunitcelllengthis3.6210 10m.Whatistheradiusofacopperatom?Whatisthe
coppercopperbondlength?

Analysis

Copperatomsareincontactalongafacediagonal(thedashedlineatright)thatrunsfromone
cornerofafacetoanothercorner.
 Usinggeometry,wecancalculatethelengthofthisdiagonal,whichequalsfourtimestheradius
ofacopperatom.

Solution

Fromgeometry,thelengthofthediagonalis timesthelengthoftheedgeoftheunitcell.

IfwecalltheradiusofthecopperatomrCu,thenthediagonalequals4rCu.Therefore:

Thecalculatedradiusofthecopperatomis1.2810 10m.

Thecoppercopperbondlengthistwicethisnumber:i.e.2.5610 10m.

Isouranswerreasonable?

Dependingonthesizeoftheatom,youshouldknowfromchapter5thatbonddistancesbetween
atomsareabout1310 10mandatomicradiiareabouthalfofthis.ThecalculatedCuradius
andCuCubondlengthfallwithinthisrange,soouranswerisreasonable.

Xraydiffractionhashadaprofoundimpactonthestudyofbiochemistry.BiochemistsoftenuseXray
diffractiontodeterminethestructuresofenzymesandotherlargemoleculesproducedbylivingsystems.
ThemostfamousexampleistheexperimentaldeterminationofthemolecularstructureofDNA.DNA(see
chapter25)isfoundinthenucleiofcells,andservestocarryanorganism'sgeneticinformation.In1953,
usingXraydiffractionphotographsofDNAfibres(figure7.50)obtainedbyRosalindFranklinandNew
ZealandbornMauriceWilkins,JamesWatsonandFrancisCrickcametotheconclusionthattheDNA
structureconsistsofthenowfamousdoublehelix(seefigure7.51).Watson,CrickandWilkinssharedthe
1962NobelPrizeinphysiologyormedicinefortheirdiscovery(Franklinhaddiedofcancerin1958,andit
wasnotpossibletonominateherfortheNobelPrizeposthumously).
 FIGURE7.50XraydiffractionphotographofDNA.

FIGURE7.51AcomputergeneratedmodeloftheDNAdoublehelix.

Xraydiffractioncontinuestobeoneofthemaintoolsusedtodeterminethestructuresofcomplexproteins
andenzymes.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.6AmorphousSolids
Whenapureliquidorameltiscooledslowly,itoftensolidifiesasawellorderedcrystallinesolid.
Whensolidsformrapidly,ontheotherhand,theiratoms,moleculesorionsmaybecomelockedinto
positionsotherthanthoseofaregularcrystal,givingmaterialsthatareamorphous,meaningwithout
form.Forexample,ordinarycanesugariscrystalline,butrapidlycoolingmeltedsugargivesfairy(or
candy)floss,whichcontainslongthreadsofamorphoussugar(figure7.52).Whileamorphoussolids
canbeformedinavarietyofwaysandbydifferentmechanisms,onefeaturethatclearlydistinguishes
themfromcrystallinesolidsisthefactthattheydonotdiffractXrays(seesection7.5).

FIGURE7.52 (a)Fairyflossisamorphous,while
(b)ordinarycanesugariscrystalline.

Whatwecallglassisanentirefamilyofamorphoussolidsbasedonsilica,SiO2.PureSiO2isusually
foundasacrystallinesolidcontainingaregulararrayofSiandOatoms.Thisisknownasquartz.When
quartzismeltedandthenquicklycooled,itformsfusedsilica,anamorphoussolidglass.Silicaglasshas
manydesirableproperties.Itresistscorrosion,transmitslightwellandwithstandswidevariationsin
temperature.Unfortunately,puresilicaisverydifficulttoworkwithbecauseofitshighmeltingpoint
(1983K).Consequently,silicaglassisusedonlyforspecialapplications.
Mixingsodiumoxide,Na2O,withsilicaresultsinaglassthatcanbeshapedatalowertemperature.
Sodiumoxygenbondsareionic,andincorporatingsodiumionsintothemixturebreakstheSiOSi
chainofcovalentbonds.Thisweakensthelatticestrengthoftheglass,lowersitsmeltingpointand
reducestheviscosityoftheresultingliquid.However,theweakenedlatticealsomeansthatglassmade
frommixedsodiumandsiliconoxidesisvulnerabletochemicalattack.

Adesirableglassmeltsatareasonabletemperature,iseasytoworkwithandyetischemicallyinert.
Suchaglasscanbepreparedbyaddingathirdcomponentthathasbondingcharacteristicsbetween
thoseofpurelyionicsodiumoxideandpurelycovalentsilicondioxide.Severaldifferentcomponents
areused,dependingonthepropertiesrequiredfortheglass.

Theglassusedforwindowpanesandbottlesissodalimesilicaglass,amixtureofsodiumoxide,
calciumoxideandsilicondioxide.TheadditionofCaOstrengthensthelatticeenoughtomaketheglass
chemicallyinerttomostcommonsubstances(strongbasesandHF,however,attackthisglass).Pyrex ,
theglassusedincoffeepotsandlaboratoryglassware,isamixtureofB2O3,CaOandSiO2.Thisglass
canwithstandrapidtemperaturechangesthatwouldcracksodalimesilicaglass.Lensesandother
opticalcomponentsaremadefromglassthatcontainsPbO.Lightraysarestronglybentastheypass
throughlensesmadeofthisglass.Colouredglassescontainsmallamountsofcolouredmetaloxides
suchasCr2O3(amber),NiO(green)orCoO(brown).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.7CrystalImperfections
Thetwoextremesoforderinginsolidsareperfectcrystalswithcompleteregularityandamorphous
solidsthathavelittleorder.Manysolidmaterialsarecrystallinebutcontaindefects.Crystallinedefects
canprofoundlyalterthepropertiesofasolidmaterial,ofteninwaysthathaveusefulapplications.
Dopedsemiconductorsaresolidsintowhichimpuritydefectsareintroduceddeliberatelyinorderto
modifyelectricalconductivity.Somegemstonesarecrystalscontainingimpuritiesthatgivethemtheir
colour.SapphiresandrubiesareimperfectcrystalsofcolourlessAl2O3Ti3+orFe3+makessapphires
blue,andCr3+makesrubiesred(figure7.53).

FIGURE7.53 (a)Sapphiresareblue
(b)rubiesarered.

Yttriumbariumcopperoxidesuperconductorshaveoptimalpropertieswhentheyhaveaslight
deficiencyofoxygen,asindicatedbythesignintheformulaYBa2Cu 3O7.Thisdeparturefrom
stoichiometriccompositionisaccommodatedbydefectsinthecrystalstructure.Thesuperconductor
crystalhasoxygenanionsmissingfromsomepositionsinthecrystallattice,andthenumberofmissing
anionscanvarysufficientlytogivethematerialavariablecomposition.Thesolidremainselectrically
neutralwhenitsanioncontentisvariedbecausesomeofthecationstakeondifferentcharges.The
coppercationsinthesuperconductorcanhavea+2or+3charge.TherelativenumberofCu 3+ions
decreasesasoxygenanionsareremovedfromthestructure.

Substitutionalimpuritiesreplaceoneatomwithanother,whileinterstitialimpuritiesoccupythespaces
betweenregularatoms.Interstitialimpuritiescreateimperfectionsthatplayimportantrolesinthe
propertiesofmetals.Forexample,smallamountsofimpuritiesaredeliberatelyaddedtoirontoimprove
itsmechanicalproperties.Pureironisrelativelysoft,easilydeformedandcorrodesreadily,butthe
additionofasmallamountofcarboncreatessteel,amuchhardermaterial.Carbonatomsfillsomeof
theopenspacesbetweenironatomsinthecrystallinestructureofsteel.Althoughcarbonatomsfiteasily
intothesespaces,theirpresencereducestheabilityofadjacentlayersofironatomstoslidepasteach
other,asfigure7.54illustrates.
 FIGURE7.54Thepresenceofevenafewcarbonatoms(blackspheres)intheinterstitialholesinaniron
latticepreventsadjacentlayersofironatomsfromslidingpastoneanotherandhardensthe
ironintosteel.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.8ModernCeramics
Ceramicsarematerialscomposedofinorganiccomponentsthathavebeenheattreated.Theyhavea
longhistory,datingtoprehistorictimes.Examplesofpotteryabout13000yearsoldhavebeenfoundin
severalpartsoftheworld.Today,ceramicsincludecommoninorganicbuildingmaterialssuchasbrick,
cementandglass.Wefindceramicsaroundthehomeasporcelaindinnerware,tiles,sinks,toilets,and
artisticpotteryandfigurines.Wealsofindceramicsinplaceswemightnotexpect,suchasmobile
phones,dieselenginesandbulletproofvests.

Manymanufacturedceramicsaremadefrominorganicmineralssuchasclay,silica(sand)andother
silicates(compoundscontaininganionscomposedofsiliconandoxygen),whicharetakenfromthe
Earth'scrust.Inrecenttimes,anentirelynewsetofmaterialswithhightechapplications,generally
referredtoasadvancedceramics,hasbeenpreparedbychemists.Wewillfocusourdiscussionsmainly
onthese.

PropertiesofCeramics
Therearesomepropertiesthatceramicshaveincommon,andthereareothersthatcanbetailoredby
controllingtheceramic'scompositionandmethodofpreparation.Forexample,manyceramicmaterials
areveryhardandhaveveryhighmeltingpoints.Table7.3containsalistofsomeadvancedceramic
materialsandtheirproperties,alongwiththepropertiesofsomemetalsincommonuse.Thehardest
substanceknownisdiamond,andsomeceramicshavehardnessesthatapproachdiamond.Silicon
carbide,whichisrelativelyinexpensivetomakeinbulk,haslongbeenusedasanabrasiveinsandpaper
andgrindingwheels.
TABLE7.3 Somepropertiesofceramicmaterials,diamond,steelandaluminium

Hardness((a)) Meltingpoint Elasticmodulus((b)) Density(g

Ceramicmaterial (GPa) (C) (GPa) mL1)
diamond,C 80 3800 910 3.52
boronnitride,BN 50 2730 660 3.48
titaniumcarbide,TiC 28 3067 470 4.93
siliconcarbide,SiC 26 2760 480 3.22
zirconiumcarbide,ZrC 25 3445 400 6.63
tungstencarbide,WC 23 2776 720 15.72
titaniumnitride,TiN 21 2950 590 5.40
aluminiumoxide,Al2O3 21 2047 400 3.98
(alumina)
berylliumoxide,BeO 15 2550 390 3.03
(beryllia)
zirconiumoxide,ZrO2 12 2677 190 5.76
(zirconia)
aluminiumnitride,AlN 12 2250 350 3.36
titaniumdioxide,TiO2 11 1867 205 4.25
(titania)
 stainlesssteel 2.35 1420 200 7.89
aluminium 1.51 658 69 2.70
(a)Pressurerequiredtodentthematerial:thelargerthevalue,theharderthematerial.
(b)Forceperunitcrosssectionalarearequiredtoelongate(stretch)thesolid:thelargerthevalue,
thestrongerthematerialandthemoreitresistsstretching.

Noticethatallofthelistedceramicsareharderthansteelandalsohavelowerdensitiesandveryhigh
meltingpoints.Thosewithhighstrengthandrelativelylowdensityareuseful,forexample,for
applicationsinspace.

Becauseoftheirhighmeltingpoints,weoftenfindceramicsusedasrefractories(heatresistant
materials)forliningfurnacesandrocketengineexhausts.Whengivenaglassyporcelainsurface,
ceramicsareimpervioustowater,butundertherightconditionstheycanbemadeporousandusedas
filtersinapplicationswherehightemperatureswoulddestroyothermaterials.

Mostceramicsdonotconductelectricity,sotheyareusedasinsulatorsforhighvoltagepowerlines,car
sparkplugsandinTVsets.However,someceramicmaterialsbecomeexcellentconductorsofelectricity
whencooledtoverylowtemperatures.Thereisawholeclassofthesematerialsthatare
superconductorswithmanypotentialapplications(seepp.2836).

Table7.3showsthatceramicsgenerallycontainmetalsinrelativelyhighpositiveoxidationstates,
combinedwithsmallnonmetals(e.g.O,NandC)withhighnegativeoxidationstates.Aswediscussed
earlier,theassignmentofaformaloxidationstatedoesnotmeanthattheelectronshavecompletely
transferredfromonebondingpartnertoanotheri.e.itallowsforallformsofchemicalbonding.

Actually,theceramiccompoundslistedintable7.3possesssubstantialcovalentbondingbetweenthe
atoms.Imaginingthatthecompoundswerepurelyionic,smallcationswithhighchargeswouldbeable
topullelectrondensityfromhighlychargedanionsintotheregionbetweentheions,causingthebonds
tobecomesubstantiallycovalent.Furthermore,elementssuchasoxygen,nitrogenandcarbonareable
toformcovalentbondsbetweentwoormoreatoms.Therefore,amixtureofionicandcovalentbonding
betweentheatoms,i.e.verypolarcovalentbonds,causesboththestrengthandhighmeltingpointsof
ceramicmaterials.

ApplicationsofAdvancedCeramics
Thefieldofhightechceramicsisverycompetitivenewmaterialswithnewapplicationsarecontinually
beingdeveloped.Theirusesareextremelyvariedandafewexamplesaregivenonthefollowingpages.

Thinceramicfilmsareusedasantireflectivecoatingsonopticalsurfacesandasfiltersforlighting.Tools
suchasdrillbitsaregiventhincoatingsoftitaniumnitride,TiN,tomakethemmorewearresistant
(figure7.55).
 FIGURE7.55Adrillbitwithathingoldencoatingoftitaniumnitride,TiN,willretainitssharpnesslongerthan
steeldrillbits.

Partiallystabilisedzirconia(ZrO2withsmallamountsofothermetaloxides)isusedtomakeportionsof
hipjointreplacements.Thisapplicationispossiblebecauseofthetoughnessoftheceramic.

Oneformofboronnitridepowder,BN,iscomposedofflat,platelikecrystalsthatcaneasilyslideover
oneanother.Itisusedincosmetics,whereitgivesasilkytexture.Anotherboroncontainingceramic,
boroncarbide,isusedalongwithKevlartmpolymertomakebulletproofvests.Whenabulletstrikesthe
vest,itiseithershatteredbytheceramic,oritcrackstheceramic,whichthenabsorbsmostofthekinetic
energy.ResidualenergyisabsorbedbytheKevlarbacking.

Siliconnitride,Si3N4,isusedtomakeenginecomponentsfordieselenginesbecauseitiswearresistant
andextremelyhard.Ithasahighstiffnesswithlowdensity,andcanwithstandextremelyhigh
temperaturesandharshchemicalenvironments.

Piezoelectricceramicsproduceanelectricpotentialwhentheirshapeisdeformed.Theyalsodeform
whenanelectricpotentialisappliedtothem.Acompanymakessmartskisthatincorporate
piezoelectricdevicesthatusebothproperties.Vibrationsintheskisaredetectedbythepotential
developedwhentheydeform.Apotentialisthenappliedtocancelthevibration.Smartmaterialspossess
bothsensingandactioncapability.Theyadaptivelyrespondtochangingstimuli.

ChemistryResearch

MolecularMaterials

ProfessorCameronKepert,UniversityofSydney

Onceregardedaslittlemorethanarrangementsofdiscretemolecules,overthepastdecade
molecularsolidshavebeenrecognisedasextendedlatticesthatcanhaveinterestingand
usefulcooperativeeffects.Thediversityofmolecularsolidsallowsapotentiallylimitless
degreeofcomplexityand,therefore,theabilitytodesignmaterialstoperformspecific
functions.
Researchintomolecularmaterialsaimstoimproveourunderstandingofhowchemical
structureleadstoamaterial'sspecificfunction.Byexploitingthisknowledgeinthedesignof
newsystemswithnewproperties,weareseekingtheanswerstoquestionssuchas:
Canwecreatematerialsthatchangecolour,shape,magnetismetc.inresponseto
changesintheirenvironmentand,therefore,actassensorsordatastoragemedia?
Canwestorehydrogengasefficientlyinnanoporousmaterials?

NanoporousMolecularFrameworks

AprincipalfocusoftheKepertresearchgroupattheUniversityofSydneyisthesynthesisof
newmaterialsthatdisplaynanoporosity,i.e.theyretaintheirstructurefollowingthe
absorptionanddesorptionofguestmoleculesfromwithinporesinthehostmaterials.
Nanoporosityandtheabilitytocustomisethetypesofgueststhatcanbeplacedinthepores
ofmaterialshaveexcitingpracticalimplicationsincludinguseinchemicalsensing,molecular
separations,catalysis,hydrogenstorageandcontrolledrelease.

ElectronicSwitching

Thegrouphasdevelopedsmartnanoporousmaterialsthatcanswitchbetweendifferent
electronicstates.Thisoccursinresponsebothtotheexchangeofguestmolecules,aneffect
thatprovidesanewmechanismforchemicalsensing,andtochangesintemperature,pressure
andirradiation.Thecouplingoftheseeffectsisexpectedtoleadtohighlyunusualhostguest
propertiesandtoinstanceswhereguestexchangeprocessescanbestimulatedexternally,e.g.
byshiningalightonthematerial.

Magnetism

Materialsdisplayingbothnanoporosityandmagneticorderingpropertiesthataregenerally
mutuallyexclusivehavelongbeensoughtforsystematicinvestigationsofmolecular
magnetismandmagnetichostguestinteractions.TheKepertresearchgrouphasrecently
createdthefirsttrulynanoporousmagnetsbybridginginorganicchainsandlayersthrough
shortmolecularlinkers.Ofparticularinterestisamaterialthatconvertstoamagnetwhen
dehydrated,despitetherebeingnoassociatedchangetotheframeworkstructure(seefigure
7.56).Effortsareunderwaytodeterminetheinfluenceofotherguestsonthemagnetic
propertiesofsuchhostlattices.
 FIGURE7.56Thenanoporousmolecularframeworkmaterial[CoII3 (OH)2 (C4 O4 )2 ]consistsof
Co(II)ions(transparentblueoctahedraconnectededgetoedge)linkedby
squarate(C4 O4 2)andhydroxideunits.Thematerialconvertsfromaferromagnetto
anantiferromagnet(seechapter13)uponinclusionofwatermoleculesintothe
nanopores.

HydrogenStorage

Recentresultshaveshownthatnanoporousmolecularframeworks(seefigure7.57)are
outstandingcandidatesfortheefficientstorageofhydrogengas,anessentialstepifhydrogen
istobeusedtoreplacefossilfuels.Currentmethodsforhydrogentransportandstorage
requireveryhighpressuresorverylowtemperatures.TheKepertresearchgrouphasrecently
shownthatmaterialscanbedesignedinwhichhydrogenbindsdirectlytobaremetalsiteson
theinteriorporesurfaces.Thisadvancepointsthewaytopossiblefuturetechnologiesin
whichhydrogenisstoredandreleasedundernonextremetemperaturesandpressures.
 FIGURE7.57Thenanoporousmolecularframeworkmaterial[CuII3 (btc)2 ](btc=1,3,5
benzenetricarboxylate)isabletostorelargequantitiesofhydrogengaswithinits
openporestructure.Frameworkatomsareshownassticksandthelocationsof
hydrogenmoleculesareshownascolouredspheres.

ChemistryResearch

HightemperatureSuperconductorsanOngoingRevolution

JeffTallon,MacDiarmidInstituteandIndustrialResearchLtd,NewZealand

Superconductivityrepresentsthepointwherequantummechanicsmeetstheeverydayworld.
Itoffersatechnologythat,throughoutthetwentyfirstcentury,willhaveanimpactonour
worldincountlesspracticalways.

Superconductors,firstdiscoveredin1911bytheNobelPrizeawardedDutchphysicistHeike
KamerlinghOnnes,becomeperfectelectricalconductorswhencooledbelowacritical
temperature,referredtoasTc inotherwords,theyshownoresistancetotheflowofelectrical
currentbelowTc andthereforesuperconductingwirescanpotentiallybeusedtocarry
electricitywithnoloss.Superconductivityisaquantummechanicaleffectthatoccurswhen
electronsofoppositemomentumandoppositespinpairuptoformamacroscopicwave
functionthatextendsacrosstheentiresuperconductor,whichcouldbeametreorevena
kilometreinsize.

Until1986,allknownsuperconductorshadtobecooledusingliquidhelium.TherecordTc at
thetimewas23K.Thatyear,BednorzandMllerdiscoveredthefirstofthesocalledhigh
temperaturesuperconductors(HTS)withTc 30K.Thiswasraisedto52Kunderhigh
pressureandsetinmotionaninternationalracetodiscoverHTSwithstillhigherTc values.
Overthenextfewyears,Tc increasedanastoundingsevenfold.

Todaytherearemorethan70knownHTS.Theyarebasedontheperovskitestructure(see
question7.11,p.288)andallhavealayeredstructurewithtwodimensionalcopperoxide
sheets.However,onlytwooftheseHTSmaterialshaveprovenamenabletomanufactureinto
wires,asthemajorityofHTSarebrittleceramics.ThemostusefulisBi2Sr2Ca2Cu 3O10,often
referredtoasBSCCO(figure7.58).ItsTc of108Kmeansthatitcanbecooledusingliquid
nitrogen,whichismuchcheaperthanliquidhelium.Itwasfirstidentifiedbyagroupworking
inNewZealandatIndustrialResearchLtd,agovernmentresearchinstitute.Theirworkwas
publishedinNaturein1988andtheywereeventuallyawardedUSandEuropeanpatentsfor
thismaterialaftermanyyearsofpatentbattlesamongsomeoftheworld'slargest
corporations.
 FIGURE7.58 BSCCOwires:
(a)precursormaterialsareloadedintoasilverbillet,extruded,
(b)rebundledinto55hexagonaltubes,reextruded,
(c)drawndowntoabout1mmdiameter,andthen
(d)rolledflattoformamultifilamentarytape.Thisisthenreactedathigh
temperaturetocompletetheformationofthefinalBSCCOproduct.

ThisgroupspunoutthebusinessHTS110Ltd,whichmanufacturesHTSbasedproducts.
Theseproductsincludemagnetsforionimplantation,research,testingofcomputerhard
drives,synchrotrondipolemagnets,coilsformotorsandgenerators,andNMRinstruments.
EachofthesedeviceshasitsownrefrigeratorandismadeusingBSCCO.AsecondNew
Zealandcompany,GeneralCableSuperconductors,manufacturessuperconductingcablefor
ACandlargecurrentapplicationssuchasgridscalegeneratorsandtransformers.

TherearemanyaspectsofHTSscienceyettobeunderstoodandthisisanongoingresearch
focusforDrTallon'sgroup.Theultimategoalistheproductionofroomtemperature
superconductors,adiscoverywhichwouldrevolutionisetheproductionanduseofelectricity
onplanetEarth.TheHTSrevolutionisnotfinishedyet!

Hightemperaturesuperconductors
Asuperconductorisamaterialwhichoffersnoresistancetotheflowofelectricity.Manycompounds
aresuperconductorsatverylowtemperatures,whichcanbereachedonlybyusingliquidheliumfor
cooling.Becauseliquidheliumisveryexpensive,materialshavebeensoughtwithcriticaltemperatures,
Tc (thetemperatureatwhichtheybecomesuperconductors),above77.4K,theboilingpointofliquid
nitrogen.Therefrigerationtechnologyforproducingandhandlingliquidnitrogeniswellknownand
relativelysimple,andliquidnitrogencostsaboutasmuchasmilkororangejuice.In1987,aceramic
mixedmetaloxide,YBa2Cu 3O7,wasdiscoveredwithaTc of93K.MaterialsthathaveTc valuesabove
about30Karecalledhightemperaturesuperconductors.MaterialswithTc valuesabove130K(at
atmosphericpressure)havebeenfound.

Thechiefproblemwithceramicsuperconductorsisthattheyarebrittle,butduringthe1990sscientists
andengineerssuccessfullymadewirelikesuperconductingmaterialsthatcouldbeusedtobuild
electricalcables.Thecablescancarryuptothreetimesmoreelectricitythanstandardelectricalcables.
Newgenerationmagnetsmadewithhightemperaturesuperconductingwiresarenowcommercially
available.

Oneofthemostfascinatingpropertiesofsuperconductingmaterialsisthattheycanbelevitatedbya
magneticfield.Besideszeroelectricalresistance,asubstanceinitssuperconductingstatepermitsno
magneticfieldwithinitself.Aweakmagneticfieldisactuallyrepelledbyasuperconductor(theMeisner
effect),andthisiswhatmakesthelevitationofsuperconductorspossible(figure7.59).Corporationsin
GermanyandJapanhavebeeninvestigatingtheuseofthispropertytodevelopnewtraintechnology.
Theyhavesuccessfullylevitatedentiretrainsandpropelledthemathighspeedwithnomorefrictional
resistancethanthatofferedtoaeroplanesbythesurroundingair.Prototypesofsuchmaglevtrainsare
stillbeingtested.ThefirstcommercialmaglevtrainbeganoperatinginChinain2002,whilea
superconductingJapaneseversionsettheworldspeedrecordforatrain(581kmh 1)in2003.
 FIGURE7.59 (a)Levitationofamagnetaboveasuperconductor.WhenaceramiciscooledbelowTc,it
becomessuperconductingandrepelsamagneticfield.Thatrepulsionissufficientto
holdamagnetsuspendedaboveit.
(b)Thisprincipleisusedbymaglevtrains.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Liquids
Liquids,likegases,arefluid,butcannotexpandorcontractmuch.Threepropertiesofliquids,viscosity,
surfacetensionandcapillaryaction,dependmostlyonthestrengthsofintermolecularattractionswithin
theliquid.Cohesiveforcesoccurbetweenmoleculesinaliquidandareresponsibleforsurfacetension.
Adhesiveforcesoccurbetweentheliquidmoleculesandthewallsofthecontainerandgiverisetoa
curvedmeniscusatthesurfaceofaliquid.Adhesiveforcesarealsoresponsibleforcapillaryaction.
Viscosityisrelatedtoboththeshapeofthemoleculesandthemagnitudeoftheintermolecularforcesin
aliquid.

Liquidsevaporatewhentheirmoleculeshavesufficientenergytoovercomeattractiveintermolecular
forces.Theequilibriumvapourpressureofaliquidisthepressureatwhichthenumberofmolecules
escapingfromtheliquidexactlymatchesthenumberbeingcapturedbytheliquid.Vapourpressure
increaseswithincreasingtemperatureuntilthenormalboilingpoint,thepointwherethevapourpressure
equalstheexternalatmosphericpressure,isreached.

Solids
Solidsarerigid,meaningthattheirconstituentatoms,moleculesorionsoccupywelldefinedpositions
relativetooneanother.Solidsmaybeclassifiedasmolecular,metallic,networkorionicsolids
accordingtothenatureoftheirconstituents.Eachcategoryhascharacteristicinteractionsbetweenits
constituents.Molecularsolidsareheldtogetherbydispersionforces.Insomesolidsandliquids,dipolar
andhydrogenbondingforcesmayalsooccurdependingonthenatureoftheindividualmolecules.In
networksolids,theconstituentsarecovalentlybondedtogether,whileionicsolidsareheldtogetherby
electrostaticattractionsbetweenoppositelychargedions.Thebondinginmetallicsolidsisduetoa
delocalisedseaofelectrons.

PhaseChanges
Aphasechangeoccurswhenasubstanceundergoesatransitionfromonephasetoanother.Energy
mustbeeithersuppliedto,orremovedfrom,asubstanceundergoingaphasechange.Thiscanbe
quantifiedbyconsideringthevaluesofthemolarenthalpyofvaporisationvapHorthemolarenthalpy
offusionfusH,whicharetheenthalpychangesthatoccuronvaporisingormelting1moleof
substance,respectively.Inadditiontothesephasechanges,sublimation,thedirectconversionofasolid
toagas,canalsooccur,andithasanassociatedmolarenthalpyofsublimation,subH.Thereverseof
thisprocessiscalleddeposition.

Heatingaliquidinaclosedcontainerresultsingradualevaporationandacorrespondingincreasein
pressure.Eventually,apointmaybereachedatwhichtheliquidandgasphasescannotbedistinguished
andthesubstanceexistsasasupercriticalfluid.Thetemperatureandpressureatwhichthisoccursare
calledthecriticaltemperatureandcriticalpressure.

Temperaturesandpressuresatwhichequilibriacanexistbetweenphasesareshowngraphicallyina
phasediagram.Threeequilibriumlinesintersectatthetriplepoint.Theliquidgaslineterminatesatthe
criticalpoint.Abovethecriticalpoint,aliquidphasecannotbeformedthesinglephasethatexistsisa
supercriticalfluid.Theequilibriumlinesalsodivideaphasediagramintotemperaturepressureregions
inwhichasubstanceexistsinjustasinglephase.Waterisdifferentfrommostsubstancesinthatits
meltingpointdecreaseswithincreasingpressure,albeitveryslightly.

OrderinSolids
Approximatingatomsasspheresallowsustodeterminetheirpossibleclosepackedarrangements.A
hexagonalarrangementismore.Theefficientthanasquarearrangementforasinglelayerofspheres.
AdditionallayersmaybeaddedtogiveeitheranABABABorABCABCarrangement,dependingon
howtheadditionalatomsarearrangedrelativetotheoriginallayer.Theformeriscalledahexagonal
closepacked(hcp)arrangementandthelatterisacubicclosepacked(ccp)arrangement.Bothare
calledclosepackedstructuresastheyfill74%ofthespace,whichisthemaximumpossibleforidentical
spheres.

Theoverallstructureofanycrystallinesolidcanbedescribedintermsofarepeatingthreedimensional
arrayoflatticepoints,whichiscalledalattice.Thesimplestportionofalatticeisitsunitcell.Many
structurescanbedescribedbythesamelatticebychangingthecontentsanddimensionsoftheunitcell.
Threepossiblecubicunitcellsare:primitivecubic,facecentredcubicandbodycentredcubic.Ina
latticeofspheres,thespacesbetweenthespheresarecalledinterstitialholes.

Sodiumchlorideandmanyotheralkalimetalhalidescrystalliseinafacecentredcubicarrangement,
whichcontainsfourNaClunitsperunitcell.Therelativesizesofthecationsandanionsinioniccrystals
determinethestructureadoptedhenceCsCl,inwhichthecationsandanionsarenearlythesamesize,
crystallisesinaprimitivecubicstructure.Theratioofcationstoanionsisalsoimportantforexample,
CaF2adoptsastructureinwhichtheCa2+ionsarearrangedinafacecentredcubicarray,withtheF
ionsfillingallthetetrahedralholes.

XrayDiffraction
Xraydiffractioncanbeusedtodeterminethestructureofcrystallinesolids.ThediffractionofXrays
fromacrystallinesolidresultsinconstructiveinterferenceoftheXraysinparticulardirectionsas
determinedbytheBraggequation.Thisgivesadiffractionpattern,whichcanbeanalysedtoallowthe
calculationofthestructureofthesolid.

AmorphousSolids
Somesolids,whenformedbyrapidcooling,donotcrystallisewiththeirconstituentatoms,moleculesor
ionsinaregulararrangement.Theseareknownasamorphoussolids.Themostimportantexampleis
glass,afamilyofamorphoussolidsbasedonsilica.RapidcoolingofmoltenSiO2givesanamorphous
solidglass,whiletheadditionofcompoundssuchasNa2O,B2O3andCaOgivesdifferentglasseswith
particularphysicalandchemicalproperties.

CrystalImperfections
Crystallinedefectscansignificantlyalterthepropertiesofasolid.Theintroductionofsmallimpurity
defectscanchangetheelectricalconductivityofasolid,andevenitscolour.Substitutionalimpurities
arisefromthereplacementofoneatomwithanotherofadifferenttype,whileinterstitialimpurities
resultfromtheplacementofatomsininterstitialholes.

ModernCeramics
Ceramicsarecomposedofinorganiccomponentssuchasmetaloxidesornitridesthathavebeenheat
treated.Mostceramicshavehighmeltingpointsandareveryhard.Thisisaresultofsignificant
covalentbonding,whichgivesrisetonetworktypesolids.Modernceramicsareusedinsuchdiverse
areasascoatings,filters,cosmeticsandbulletproofvests.Piezoelectricceramicscandeforminresponse
toanelectricpotentialandcanbeusedinsmartmaterials.Hightemperaturesuperconductorsare
ceramicsandareusedinrapidmaglevtrains.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Boilingpointsofsubstances(section7.1)
Thestrengthsofintermolecularforcesinsubstancescanbecomparedbasedontheirboilingpoints.

Phasediagram(section7.3)
Weuseaphasediagramtoidentifytemperaturesandpressuresatwhichequilibriumcanexistbetween
phasesofasubstanceandtoidentifyconditionsunderwhichonlyasinglephasecanexist.

Unitcell(section7.4)
Aunitcellshowshowtheconstituentatoms,moleculesorionsarearrangedinthreedimensionsina
crystallinesolid.Itisthesmallestrepeatingunitofacrystallinestructure.

TheBraggequation(section7.5)
TheBraggequationrelates,andthedistancebetweentheplanesofatoms,d,andallowsthe
determinationofthestructuresofsolidsfromXraydiffractionpatterns.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Liquids
7.1PentaneisaC5hydrocarbon,gasolinecontainsmostlyC8hydrocarbons,andfueloilcontains
hydrocarbonsintheC12range.Listthesethreehydrocarbonsinorderofincreasingviscosity,and
explainwhatmolecularfeatureaccountsforthevariation.
7.2Aluminiumtubinghasathinsurfacelayerofaluminiumoxide.Whatshapemeniscuswouldyou
expecttofindforwaterandformercuryinsidealuminiumtubing?Explainyouranswersintermsof
intermolecularforces.
7.3Waterformsbeadsonthesurfaceofafreshlywaxedcar,butformsafilmontheclean
windscreen.Whyisthis?
7.4Foreachofthefollowingpairsofliquids,choosewhichhasthelowervapourpressureatroom
temperatureandexplainyourreasoning.
(a)water,H2O,ormethanol,CH3OH
(b)pentan1ol,C5H12OH,orhexan1ol,C6H13OH
(c)chloromethane,CH3Cl,orchloroform,CHCl3
Solids
7.5Classifyeachofthefollowingasanionic,network,molecularormetallicsolid:Sn,S8,Se,SiO2and
Na2SO4.
7.6Describethedifferencesbetweenmolecularandionicsolidsinrelationto:
(a)interparticleforcesand
(b)macroscopicproperties.
7.7Indicatewhichtypeofsolid(ionic,network,metallicormolecular/atomic)eachofthefollowing
formsonsolidification.
(a)Br2
(b)KBr
(c)Ba
(d)SiO2
(e)CO2
Phasechanges
7.8Fromtable7.2,determinewhichofeachofthefollowingpairshasthehighervalue.Use
intermolecularforcestoexplainthedata.
(a)enthalpiesofvaporisationofmethaneandethane
(b)enthalpiesofvaporisationofethanolanddiethylether
(c)enthalpiesoffusionofargonandmethane
7.9SketchtheapproximatephasediagramforBr2fromthefollowinginformation:normalmelting
pointis265.9K,normalboilingpointis331.9K,triplepointisatp=5.8710 3PaandT=265.7
K.Labeltheaxesandtheareawhereeachphaseisstable.
7.10Usingthephasediagramfromquestion7.9,describewhathappenstoasampleofBr2asthe
followingprocessestakeplace.Drawlinesonthephasediagramshowingeachprocess.
(a) AsampleatT=400Kiscooledto250Katconstantp=1.01310 5Pa.
(b)
 Asampleiscompressedfromp=1.01310 2Patop=1.01310 8PaatconstantT=
265.8K.
(c) Asampleisheatedfrom250Kto400Katconstantp=2.02610 3Pa.
OrderinSolids
7.11Theunitcellofthemineralperovskiteisshownbelow.Whatistheformulaofperovskite?

7.12Forthepatternshownbelow,drawatilethatrepresentsaunitcellforthepatternandcontainsonly
completefish.Drawasecondtilethatisaunitcellbutcontainsnocompletefish.

7.13Intheunitcellofcalciumoxide,theoxideionsadoptafacecentredcubicarrangement.The
calciumionsareintheholeswithinthefacecentredcubicunitcell.Howmanycompletecalcium
ionsmustbepackedwithineachfacecentredcubefortheunitcelltobechargeneutral?
XrayDiffraction
7.14WritetheBraggequationanddefinethesymbolsused.
7.15ExplainingeneraltermshowanXraydiffractionpatternofacrystalandtheBraggequation
provideinformationthatallowschemiststodeterminethestructuresofmolecules.
AmorphousSolids
7.16Whatdoesthewordamorphousmean?
7.17Whatisanamorphoussolid?Comparewhathappenswhencrystallineandamorphoussolidsare
brokenintopieces.
7.18Amorphoussilicahasadensityofaround2.3gmL1andcrystallinequartzhasadensityof2.65g
mL1.Describethebondingfeaturesthatcausethesetwoformsofthesamesubstancetohave
differentdensities.
CrystalImperfections
7.19Whataresubstitutionalimpurities?
7.20Whatareinterstitialimpurities?
ModernCeramics
7.21Whatareceramics?
7.22Whataretwophysicalpropertiesthatmakeceramicsusefulmaterials?
7.23Whatarerefractories?Givetwousesforrefractories.
7.24Whataresuperconductors?Whyisitveryexpensivetousetypicalsuperconductorsinpractical
applications?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
7.25Listthedifferentkindsofforcesthatmustbeovercometoconverteachofthefollowing
compoundsfromaliquidtoagas.
(a)NH3
(b)CHCl3
(c)CCl4
(d)CO2
7.26Listalltheintermolecularforcesthatstabilisetheliquidphaseofeachofthefollowing.
(a)Xe
(b)SF4
(c)CF4
(d)CH3COOH(aceticacid)
7.27Manganeseformscrystalsineitherbodycentredcubicorfacecentredcubicgeometry.Which
geometryhasthehigherdensity?Explainyourchoice.
7.28Berylliumformscrystalsineitherbodycentredcubicorhexagonalclosepackedgeometry.Which
solidphasehasthehigherdensity?Explainyourchoice.
7.29Foreachofthefollowingpairs,identifywhichhasthehigherboilingpoint,andidentifythetype
offorcethatisresponsible.
(a)H3COCH3andCH3OH
(b)SO2andSiO2
(c)HFandHCl
(d)Br2andI2
7.30Refertofigure7.21.Describeindetailwhatoccurswheneachofthefollowingprocessesis
carriedout.
(a) AsampleofCO gasiscompressedfrom1.01310 5Pato5.06510 6PaatT=298K.
2
(b)Dryiceat195Kisheatedto350Katp=6.07810 5Pa.
(c) AsampleofCO gasatp=1.01310 5Paiscooledfrom298Kto50K.
2
7.31Whydothetwoisomersshownbelowhaveverydifferentmeltingpoints?

7.32Withreferencetofigure7.22,describewhathappenstosilicaasitisslowlyheatedfromroom
 temperatureto2000Catatmosphericpressure(1.01310 5Pa).
7.33Howmanytriplepointsappearonthephasediagraminfigure7.22?Foreachone,describethe
conditionsandnamethethreephasesthatcoexistundertheseconditions.
7.34Solidsodiummetalcanexistintwodifferentcrystallineforms,bodycentredcubicandhexagonal.
Oneisstableonlybelow5Katrelativelylowpressuretheotherisstableunderallother
conditions.Drawatomicpicturesofbothphases,identifythephasethatisstableonlyatlow
temperatureandpressure,andexplainyourchoice.
7.35Thefigurebelowshowsthephasediagramforelementalsulfur(nottoscale).Useittoanswerthe
followingquestions.

(a)Underwhatconditionsdoesrhombicsulfurmelt?
(b)Underwhatconditionsdoesrhombicsulfurconverttomonoclinicsulfur?
(c)Underwhatconditionsdoesrhombicsulfursublime?
7.36Usethefigureinquestion7.35toanswerthefollowing.
(a)Howmanytriplepointsarethereinthediagram?
(b)Whichphasescoexistateachtriplepoint?
(c)Ifsulfurisatthetriplepointat153C,whathappensifthepressureisreduced?
7.37Sketchthephasediagramforasubstancethathasatriplepointat15.0Cand0.3010 5Pa,
meltsat10.0Cat110 5Pa,andhasanormalboilingpointof90C.
7.38Basedonthephasediagraminquestion7.37,belowwhatpressurewillthesubstanceundergo
sublimation?Howdoesthedensityoftheliquidcomparewiththedensityofthesolid?
7.39Theunitcellofrheniumoxideappearsinthefigurebelow.

(a)Namethecubiclatticecompatiblewiththisarrangementoftheatoms.
(b)Calculatethenumberofrheniumandoxygenatomsintheunitcellandidentifythe
 formulaofrheniumoxide(thechemicalsymbolforrheniumisRe).
7.40Oneformofniobiumoxidecrystallisesintheunitcellshownbelow.Calculatethenumberof
niobiumandoxygenatomsintheunitcell,andidentifytheformulaofniobiumoxide(the
chemicalsymbolforniobiumisNb).

7.41Tungstendoesnotmeltevenwhenheatedtoincandescence.Howdointeratomicforcesin
tungstencomparewiththoseinmoretypicalmetalssuchasgoldornickel?
7.42Silverformsfacecentredcubiccrystals.Theatomicradiusofasilveratomis144pm.Drawthe
faceofaunitcellwiththenucleiofthesilveratomsatthelatticepoints.Theatomsareincontact
alongthediagonal.Calculatethelengthofanedgeofthisunitcell.
7.43Theatomicradiusofnickelis124pm.Nickelcrystallisesinafacecentredcubiclattice.Whatis
thelengthoftheedgeoftheunitcellexpressedinpicometres?
7.44Potassiumionshavearadiusof133pm,andbromideionshavearadiusof195pm.Thecrystal
structureofpotassiumbromideisthesameassodiumchloride.Estimatethelengthoftheedgeof
theunitcellinpotassiumbromide.
7.45Theunitcellinsodiumchloridehasanedgelengthof564.0pm.Thesodiumionhasaradiusof
95pm.Whatisthediameterofachlorideion?
7.46Caesiumchloride,CsCl,crystalliseswithacubicunitcellofedgelength412.3pm.Thedensityof
CsClis3.99gmL1.Showthattheunitcellcannotbebodycentredcubicorfacecentredcubic.
7.47Tin(IV)chloride,SnCl4,hassoftcrystalswithameltingpointof30.2C.Theliquidis
nonconducting.Whattypeofsolid(ionic,molecular,covalentormetallic)isformedbySnCl4?
7.48Elementalboronisasemiconductor,isveryhardandhasameltingpointofabout2250C.What
typeofsolidisformedbyboron?
7.49Galliumcrystalsareshinyandconductelectricity.Galliummeltsat29.8C.Whattypeofsolid
doesgalliumform?
7.50Titanium(IV)bromideformssoftorangeyellowcrystalsthatmeltat39Ctogivealiquidthat
doesnotconductelectricity.Theliquidboilsat230C.WhattypeofsoliddoesTiBr4form?
7.51Titanium(IV)bromideformssoftorangeyellowcrystalsthatmeltat39Ctogivealiquidthat
doesnotconductelectricity.Theliquidboilsat230C.WhattypeofsoliddoesTiBr4form?

Theelementniobiumisshiny,softandductile.Itmeltsat2468Candthesolidconducts
electricity.Whattypeofsoliddoesitform?
7.52Elementalphosphorusconsistsofsoft,white,waxycrystalsthatareeasilycrushedandmeltat44
C.Thesoliddoesnotconductelectricity.Whattypeofsoliddoesphosphorusform?
7.53Indicatewhichtypeofsolideachofthefollowingwouldformwhenitsolidifies:
(a)Br2,
 (b)LiF,
(c)MgO,
(d)Mo,
(e)Si,
(f) PH3,
(g)NaOH.
7.54Indicatewhichtypeofsolideachofthefollowingwouldformwhenitsolidifies:
(a)O2,
(b)H2S,
(c)Pt,
(d)KCl,
(e)Ge,
(f) Al2(SO4)3,
(g)Ne.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
7.55Molecularhydrogenandatomicheliumbothhavetwoelectrons,butHeboilsat4.2K,whereas
H2boilsat20K.Neonboilsat27.1K,whereasmethane,whichhasthesamenumberof
electrons,boilsat114K.Explainwhymolecularsubstancesboilatahighertemperaturethan
atomicsubstanceswiththesamenumberofelectrons.
7.56DrawtheunitcelloftheNaClcrystalanddeterminethenumberofnearestneighboursofopposite
chargeforeachioninthisunitcell.
7.57Belowisanillustrationofaherringbonepatternforpatiopavers.Identifytheunitcellforthis
pattern.

7.58Constructaqualitativegraphsimilartotheoneinfigure7.16thatsummarisestheenergychanges
thataccompanythefollowingprocess:Asampleofwaterat35Cisplacedinafreezeruntilthe
temperaturereaches25C.Plottemperaturealongtheyaxisandkilojoulesofheatremoved
alongthexaxis.
7.59Asagas,aceticacid,CH3COOH,existsasamixtureofindividualmoleculesandpairsof
moleculesheldtogetherbyhydrogenbonds.
(a)DrawaLewisstructurethatshowshowtwoaceticacidmoleculescanformapairby
hydrogenbonding.
(b)Doesthefractionofpairedaceticacidmoleculesincreaseordecreaseasthetemperature
rises?Explain.
7.60Goldcrystallisesinafacecentredcubiclattice.Theedgeoftheunitcellhasalengthof407.86
pm.Thedensityofgoldis19.31gmL1.
(a)UsethesedataandtheatomicmassofgoldtocalculatethevalueoftheAvogadro
constant.
(b)Calculatetheatomicradiusofgoldinunitsofpicometres.
7.61Silverhasanatomicradiusof144pm.WhatwouldthedensityofsilverbeingmL1ifitwereto
crystallisein:
(a)asimplecubiclattice
(b)abodycentredcubiclattice
(c)afacecentredcubiclattice?
Theactualdensityofsilveris10.6gmL1.Whichcubiclatticedoessilverhave?
7.62Whichofthefollowingmoleculeswouldyouexpecttowetagreasyglasssurfacemore
effectively?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
amorphous diffractionpattern networksolid
bodycentredcubiclattice facecentredcubicstructure phasechange
(bcc) (fcc) phasediagram
Braggequation glass primitivecubicstructure
capillaryaction hexagonalclosepacked(hcp) refractory
ceramics interstitialhole sublimation
closepackedstructures ionicsolid superconductor
criticalpoint lattice supercriticalfluid
criticalpressure latticepoint surfacetension
criticaltemperature(Tc ) meniscus triplepoint
crystallattice metallicsolid unitcell
crystallinedefects molarenthalpyoffusion vapourpressure
crystallinesolid (fusH) viscosity
cubicclosepacked(ccp) molarenthalpyofsublimation
deposition (subH)
molarenthalpyofvaporisation
(vapH)
molecularsolid

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

8 ChemicalThermodynamics
Thereactionofhydrogen,H2,withoxygen,O2,isspontaneousoncethegasisignited,it
reactstoformwater,H2O,givingoutalargeamountofheatintheprocess.Yetwecannot
carryoutthisreactioninreverseinotherwords,H2Ounderthesameconditionsdoesnot
givespontaneousformationofH2andO2.Whydochemicalreactionsproceedinonedirection
only,andwhatdeterminesthedirectioninwhichtheyproceed?Inthischapter,wewillstudy
chemicalthermodynamicsandwewillfindthatafunctioncalledGibbsenergyiscentralto
determiningthespontaneityofaparticularchemicalreactionorphysicalprocessunder
preciselydefinedconditions.Wewillalsolearnaboutenthalpyandentropy,twofunctionsthat
areintimatelylinkedtoGibbsenergy.Chemicalthermodynamicsiscrucialtounderstanding
chemicalequilibriaandformsthebasisofthischapterandchapters9,10,11and12.Itisan
essentialpartnotonlyofchemistry,butalsooflifeitself.
KEYTOPICS

8.1Introductiontochemicalthermodynamics
8.2Thermodynamicdefinitions
8.3Thefirstlawofthermodynamics
8.4Enthalpy
8.5Entropy
 8.5Entropy
8.6Thesecondlawofthermodynamics
8.7Thethirdlawofthermodynamics
8.8Gibbsenergyandreactionspontaneity

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.1IntroductiontoChemicalThermodynamics
Whenalumpofsolidsodiummetalisplacedinwater,avigorouschemicalreactionoccursthatforms
hydrogengasandaqueoussodiumhydroxide(figure8.1):

However,ifwetrytocarryoutthereversereactionbybubblinghydrogengasthroughanaqueoussolution
ofsodiumhydroxide,nochemicalreactionisobserved:

FIGURE8.1Metallicsodiumreactsviolentlywithwater.Inthereaction,sodiumisconvertedtoNa+,andwater
giveshydrogengasandhydroxideions.Whenthereactionisover,thesolutioncontainssodium
hydroxide.

Similarly,ifablockoficeisleftatroomtemperatureandatmosphericpressure,itwilleventuallymeltto
giveliquidwater:

butliquidwaterunderthesameconditionswillneversolidifyintoice:

Theseexamplesshowthatbothchemicalreactionsandphysicalchangesoccurinoneparticulardirection
onlyunderparticularconditionsoftemperatureandpressure,andwesaythatsuchchangesare
spontaneousinotherwords,oncestartedtheyproceedwithouttheinvolvementofanyoutsidefactors.The
reactionofsodiumwithwaterandthemeltingoficedescribedaboveareexamplesofspontaneous
processesthatproceedtocompletion.However,manyspontaneouschemicalreactionsdonotgivecomplete
conversionofreactantstoproducts.Anexampleofaspontaneousreactionthatdoesnotgotocompletionis
thereactionofN2O(laughinggas)withoxygenatroomtemperatureandatmosphericpressuretogive
NO2(g).Althoughwecanwritethebalancedchemicalequationforthisreactionas:

thisdoesnotmeanthat,ifwemixed2molesofN2O(g)with3molesofO2(g)inacontaineratroom
temperatureandpressure,wewouldobtain4molesofNO2(g).Infact,wewouldfindthat,nomatterhow
longwewaited,nomorethanabout2molesofNO2(g)wouldformandtherewouldalwaysbesignificant
amountsofthestartingmaterialspresentinthereactionmixture.Itisimportantforyoutoappreciatethata
balancedchemicalequationtellsusnothingaboutwhetherornotaparticularreactionproceedsto
completionitsimplytellsusthemoleratiosinwhichreactantsreacttogiveproducts.

Wecanforcenonspontaneousreactionstoproceedprovidedthatwecouplethemtoaspontaneousprocess.
Forexample,waterdoesnotspontaneouslydecomposeintohydrogengasandoxygengas,but,bypassing
anelectriccurrent(aspontaneousflowofelectrons)throughwater,wecanforcethereaction:

toproceed(figure8.2).Thisprocessiscalledelectrolysis.Productionofhydrogenandoxygenwillcontinue,
however,onlyaslongastheelectriccurrentismaintained.Assoonasthesupplyofelectricityiscutoff,the
decompositionceases.Thisexampledemonstratesthedifferencebetweenspontaneousandnonspontaneous
changes.Onceaspontaneouseventbegins,ittendstocontinueuntilitstopsofitsownaccord(figure8.3).
Anonspontaneousevent,ontheotherhand,cancontinueonlyaslongasitreceivessomesortofoutside
assistance.Youshouldalsonotethattheelectrolysisofwaterrequiressomesortofspontaneousmechanical
orchemicalchangetogeneratetheneededelectricity.Inshort,allnonspontaneouseventsoccuratthe
expenseofspontaneousones.Everythingthathappenscanbetraced,eitherdirectlyorindirectly,to
spontaneouschanges.

FIGURE8.2TheelectrolysisofwaterproducesH2 andO2 gases.Itisanonspontaneouschangethatcontinues

onlyaslongaselectricityissupplied.
 FIGURE8.3Threecommonspontaneouseventsironrusts,fuelburnsandanicecubemeltsatroomtemperature.

Aschemists,weareinterestedinpredictingwhetherareactionisspontaneousunderourconditionsof
interest,and,ifitis,howfaritwillproceedtowardscompletionunderthoseconditions.Thescienceof
chemicalthermodynamicsallowsustopredictboththedirectionandextentofspontaneouschemicaland
physicalchangeunderparticularconditions.WedothisusingapropertycalledGibbsenergy,G.Wecan
likenaspontaneouschangetoaballatthetopofahilloncepushed,itwillrollspontaneouslydownthe
hilluntilitreachesthebottom,thepointofminimumenergy.Inthesameway,wewillseethatchemical
reactionsproceedinthedirectionthatleadstoadecreaseintheGibbsenergyofthesystem.Wewillalsosee
thatoverallchemicalandphysicalchangewillceaseoncetheGibbsenergyofthesystemisminimised,and
that,undertheseconditions,thesystemisatequilibrium.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.2ThermodynamicDefinitions
Beforewebeginourstudyofchemicalthermodynamics,weneedtodefinesomeimportant
thermodynamicterms.

HeatandTemperature
Arguablythemostimportantandindeedmostfamiliarthermodynamicterm,heat,isperhapsthemost
conceptuallydifficult.Heatisatransferofenergyduetoatemperaturedifference.Iftwobodieshaving
differenttemperaturesarebroughtintodirectcontact,therewillbeheatflowfromthehottertothe
colderbody,untilbothareatthesametemperature.Aswewillsee,wecannotactuallymeasureheat
directly.Thedefinitionoftemperaturealsofollowsfromtheabovetwobodieshavethesame
temperatureiftheyareinthermalequilibriumi.e.thereisnoheatflowbetweenthemwhentheyarein
directcontact.Itisimportanttonotethatthethermodynamictemperature(sometimescalledthe
absolutetemperature)scaleisusedinnearlyallthermodynamiccalculations.Thethermodynamic
temperatureismeasuredinkelvin(K),andathermodynamictemperaturecanbeconvertedtoa
temperatureindegreesCelsiusbysubtracting273.15.Youshouldnotethatatemperaturedifferenceof
1Kisnumericallyequaltoatemperaturedifferenceof1C,so,forcalculationsinvolvingatemperature
change,thenumericalvalueofthischangewillbethesame,regardlessofwhethertheindividual
temperaturesareexpressedinKorC.

System,SurroundingsandUniverse
Wewillusethewordsystemtorefertotheparticularpartoftheuniverse(generallyoneormore
chemicalspecies)thatwearestudying,whileeverythingelseisthesurroundings.Together,thesystem
andsurroundingsconstitutetheuniverse(figure8.4).Asweareusuallyinterestedinheatflowbetween
thesystemandsurroundings,itisveryimportanttospecifytheboundaryacrosswhichheatflows.The
boundarymightbevisible(suchasthewallsofabeaker)orinvisible(suchastheboundarythat
separateswarmairfromcoldairalongaweatherfront).Threetypesofsystemarepossible,depending
onwhethermatterorenergycancrosstheboundary.

FIGURE8.4Inthermodynamics,itisimportanttodefinethesystem,surroundings,universeandthe
boundary.

Opensystems.cangainorlosemassandenergyacrosstheirboundaries.Thehumanbodyisan
exampleofanopensystem.
Closedsystems.canabsorborreleaseenergy,butnotmass,acrosstheboundary.Themassofa
 closedsystemisconstant,nomatterwhathappensinside.Alightbulbisanexampleofaclosed
systemasitcanreleaseenergyasbothheatandlight,butitsmassisconstant.
Isolatedsystems.cannotexchangematterorenergywiththeirsurroundings.Becauseenergy
cannotbecreatedordestroyed,theenergyofanisolatedsystemisconstant,nomatterwhat
happensinside.Astopperedvacuumflaskisagoodapproximationofanisolatedsystem.
Processesthatoccurwithinanisolatedsystemwithnoheattransfertothesurroundingsarecalled
adiabatic,fromtheGreekwordsaanddiabatosmeaningnotpassable.

Units
Wemustbeawareoftheunitsusedinchemicalthermodynamics.TheSIunitofenergy,work(motion
againstanopposingforce)andheatisthejoule(J).Recallthatthejouleisaderivedunit(table8.2,p.
25)andcanbeexpressedintermsofSIbaseunitsas:

Ajouleistheamountofkineticenergypossessedbya2kilogramobjectmovingataspeedof1metre
persecond,or,touseanotherexample,1jouleisapproximatelytheenergyofasinglehumanheartbeat.
Thejouleisactuallyarathersmallamountofenergyandinmostcaseswewillusethelargerunit,the
kilojoule(kJ):

ThermodynamicFunctions
Therearefourimportantthermodynamicfunctionswhichwewillstudyindetail:internalenergy(U,
section8.3),enthalpy(H,section8.4),entropy(S,section8.5)andGibbsenergy(G,section8.8).Very
briefdefinitionsoftheseareasfollows.

Internalenergy(U)isthesumofallthenuclear,electronic,vibrational,rotational,translational
andinteractionenergiesofalloftheindividualparticlesinasampleofmatter.
Enthalpy(H)isafunctionrelatedtotheheatabsorbedorevolvedbyachemicalsystemandmay
bedeterminedbymeasuringthetemperaturechangethatoccursduringachemicalreactionor
physicalchangeunderconditionsofconstantpressure.
Entropy(S)isameasureofthenumberofwaysenergyisdistributedthroughoutachemical
system.ItsvalueisrelatedtotheenthalpyofthesystemataparticulartemperatureT.
Gibbsenergy(G),namedaftertheAmericanmathematicalphysicistJosiahWillardGibbs(1839
1903),isdefinedas:

whereTisthethermodynamictemperature.Aswewillsee,theGibbsenergyofachemicalsystem
maybethoughtofastheenergythatisavailabletodowork.

Wewilllookattheseingreaterdetail,andprovideexactdefinitions,intheappropriatesectionsofthis
chapter.

X:thechangeinX
WearegenerallyinterestedinthechangeinthevaluesofU,H,SandGastheresultofeithera
chemicalreactionorachangeinphase,ratherthantheirabsolutevalues.Wedenotesuchachange
using(theuppercaseGreekletterdelta).Therefore,foranythermodynamicquantityX:

Weoftenusetheterminologywhendiscussingchangesintemperature.Thus,anychangein
temperature,T,isdefinedas:

Notethat,ifTfinalislessthanTinitial,Tisthen,bydefinition,negative.

ThethermodynamicfunctionsU,H,SandG,canrefertobothchemicalandphysicalchanges.
Chemicalchangesgenerallyoccurasaresultofchemicalreactionsinthese,thereactantsandproducts
arechemicallydifferent,astheresultofthemakingand/orbreakingofchemicalbonds,orthetransfer
ofelectrons.Physicalchangesreferprimarilytochangesofphase.Here,thechemicalidentitiesofthe
reactantsandproductsarethesame,buttheirphysicalstatesaredifferent:e.g.liquidwaterfreezingto
giveice,andsolidiodinesublimingtogivegaseousiodine.Ontheoccasionswhenwearereferringto
thevaluesofthesethermodynamicfunctionsspecificallyforchemicalreactions,wedenotethisusing
thesymbolsrU,rH,rSandrG.

StateFunctions
Aswewillsee,U,H,SandGareallexamplesofastatefunction.Thismeansthatthevalueof
eachdependsonlyonthecurrentstateofthesystemanditdoesnotmatterhowthesystemcametobe
initscurrentstateorhowthesystemwillbehaveinthefuture.Wecanusuallydefinethestateofa
chemicalsystembyspecifyingtheamountandtypeofsubstancespresentinthesystem,andthe
pressure,temperatureandvolumeofthesystem.Whenwethenchangethestateofthesystemby
changingoneormoreoftheabovevariables,thechangeinthevalueofanystatefunctionXofthe
systemisgivenby:

anddependsonlyontheinitialandfinalstatesofthesystemandnotonthepathtakenduringthe
changeinthestateofthesystem.Thisconceptisillustratedinfigure8.5.
 FIGURE8.5ThelatitudeofDarwinairportis1224'S,whilethatofDunedinairportis4555'S.Asthereareno
directflightsbetweenDarwinandDunedin,ifwewishtotravelbetweenthem,wemustflyvia
Brisbane(blueline,atotalof5401km),Sydney(greenline,5244km)orMelbourne(orangeline,
5410km).Theactualdistancetravelledisdifferentineachcase,andisthereforenotastate
functionasitdependsonthepathtaken.However,thechangeinlatitudethatoccurs,3331',is
thesame,regardlessofwhichroutewetake,andisthereforeastatefunction.

Aswewillseelater,theadvantageofrecognisingthataparticularpropertyisastatefunctionisthat
manycalculationsbecomemucheasier.

GandSpontaneity
Theprimaryaimofthischapteristoshowthatthespontaneityofachemicalorphysicalprocessat
constanttemperatureandpressurecanbepredictedfromthesignoftheGibbsenergychangeforthe
process(G),whichitselfdependsonthevaluesofHandSviatheequation:

Thisisoneofthemostimportantequationsinallofchemistry.AnegativevalueofGmeansthatthe
productsareoflowerGthanthereactantstheprocessmustproceedinthedirectionofdecreasingGso
itisspontaneous.Conversely,ifGispositive,theproductsareofhigherGthanthereactantsthe
processwillnotbespontaneousasithastoproceedinthedirectionofincreasingG(figure8.6).
 FIGURE8.6DiagramsshowingtheoriginofthesignofG.(a)GproductsislessthanGreactants,soG(=
GproductsGreactants)isnegative,andtheprocessreactantsproductsisspontaneousinthe
directionofdecreasingG.(b)Conversely,whenGproductsisgreaterthanGreactants(righthand
diagram),Gispositive,andtheprocessreactantsproductsisnotspontaneousasitinvolves
anincreaseinG.

IfG=0,thesystemisatequilibrium,astateinwhichnooverallchemicalorphysicalchangeis
observed.Inshort,wecansaythat,foraprocessoccurringatconstanttemperatureandpressure:
ifG<0,theprocessisspontaneous
ifG>0,theprocessisnonspontaneous
ifG=0,thesystemisatequilibrium.
ThemagnitudeofGunderpreciselydefinedconditionsisalsoimportantintellingushowfara
reactiongoestowardscompletion,aswewillseeinchapter9.Obviously,todeterminethevalueofG,
weneedtoknowthevaluesofbothHandS.Wewilldefinetheformerbywayofthefirstlawof
thermodynamics.Insodoing,wewillintroducetheconceptsofheatq,workandinternalenergy.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.3TheFirstLawofThermodynamics
WestatedearlierthattheequationforGibbsenergycontainedtermsinvolvingbothenthalpyand
entropy.Inthissection,wewillinvestigatewhatismeantbythetermenthalpy.Indoingthis,wewill
introducesomenewconcepts:internalenergy(U),work(w)andheat(q),aswellasthefirstlawof
thermodynamics.

Ifyouhaveeverdissolvedalargeamountofsodiumchloride,NaCl,inwater,youwillhavenoticedthat
theresultingsolutiongetscolderasthesaltdissolves.However,ifyoudissolvethechemicallysimilar
saltlithiumchloride,LiCl,inwater,youwillfindthattheresultingsolutionbecomessurprisinglyhot.
Thefirstprocessabsorbsheatfromitssurroundingswhilethesecondgivesoutheattoitssurroundings.

Theenergythatistransferredasheatcomesfromanobject'sinternalenergy.Internalenergyisthesum
ofenergiesforalloftheindividualparticlesinasampleofmatterandisgiventhesymbolU.In
studyingbothchemicalandphysicalchanges,weareinterestedinthechangeininternalenergy(U)
thataccompaniestheparticularprocess:

Forachemicalreaction,Ufinalcorrespondstotheinternalenergyoftheproducts,sowewillwriteitas
Uproducts.Similarly,wewillusethesymbolUreactantsforUinitial.Soforachemicalreactionthechangein
internalenergyisgivenby:

Thus,whenwedissolvesodiumchlorideinwater,thesystemabsorbsenergyfromitssurroundingsits
finalenergyisthereforegreaterthanitsinitialenergy,sorUispositive.Conversely,whenwedissolve
lithiumchlorideinwater,thesystemgivesoutenergytoitssurroundingsitsfinalenergyistherefore
lessthanitsinitialenergy,sorUisnegative.

Achemicalsystemcanexchangeenergywithitssurroundingsintwoways.Thefirst,aswehaveseen
above,isbyeitherabsorbingheatfromoremittingheattothesurroundings.Thesecondisbydoing
workonthesurroundings,orhavingthesurroundingsdoworkonit.Workmaybedefinedsimplyas
motionagainstanopposingforce.Forexample,liftingaweightagainsttheforceofgravityiswork,as
isstretchingorcompressingaspring.Whilethereareanumberofdifferenttypesofworkpossiblein
chemicalsystems(suchaselectricalworkandosmoticwork),wewillconsideronlytheworkassociated
withthecompressionorexpansionofagastoillustrateanumberofimportantthermodynamicconcepts.
ThistypeofworkisoftencalledpressurevolumeorpVwork,asitinvolvesachangeinpressureand
volumeofagassample.Whenagasiscompressedatconstanttemperature,thesurroundingsaredoing
workonthesystem,whiletheexpansionofagasatconstanttemperatureisanexampleofasystem
doingworkonthesurroundings(figure8.7).
 FIGURE8.7Pressurevolumework:
(a)Agasisconfinedunderpressureinacylinderfittedwithapistonthatisheldinplacebya
slidingpin.
(b)Whenthepistonisreleased,thegasinsidethecylinderexpandsandpushesthepiston
upwardsagainsttheopposingpressureoftheatmosphere.Asitdoesso,thegasdoes
somepressurevolumeworkonthesurroundings.

Themagnitudeoftheworkdoneduringavolumechange,V,againstanopposingpressure,p,isgiven
bytheequation:

AsV(VfinalVinitial)ispositivefortheexpansionofagas,workisnegativeforthisprocessatconstant
temperature,whilesimilarreasoningshowsthatworkispositiveforthecompressionofagas.

Asheatandworkaretheonlywaysbywhichaclosedchemicalsystemcanexchangeenergywithits
surroundings,itfollowsthatthechangeininternalenergyofachemicalsystemduringachemicalor
physicalchangemustbeequaltothesumoftheheatabsorbedoremittedbythesystemandthework
doneonorbythesystem.Inmathematicalterms,thisbecomes:

whereq=heatandw=work.Thisequationisknownasthefirstlawofthermodynamics.Insimple
terms,itmeansthatenergycanbetransferredbetweenasystemanditssurroundingsaseitherheator
work,butitcanneverbecreatedordestroyed.Analternativestatementofthefirstlawof
thermodynamicsisthattheenergyofanisolatedsystemisconstant.Bothformulationsareessentially
alternativeversionsofthelawofconservationofenergy,whichsaysthatenergycannotbecreatedor
destroyed.AswithH,SandG,wearenotinterestedintheabsolutevalueofU,butratherthechangein
U(U)thatoccursastheresultofachemicalorphysicalchange.

WhileUisastatefunction,thevaluesofqandwdependonwhathappensbetweentheinitialandfinal
statesofanychangeinotherwords,qandwarenotstatefunctions.Forexample,considerthe
dischargeofacarbatterybytwodifferentpaths(figure8.8).Bothpathstakeusbetweenthesametwo
states,onebeingthefullychargedstateandtheotherthefullydischargedstate.BecauseUisastate
functionandbecausebothpathshavethesameinitialandfinalstates,Umustbethesameforboth
paths.Butwhataboutqandw?
 FIGURE8.8Internalenergy,heatandwork.Thecompletedischargeofabatteryalongtwodifferentpaths
yieldsthesametotalamountofinternalenergy,U.However,ifthebatteryissimplyshort
circuitedwithaheavyspanner,asshowninpath1,thisenergyappearsentirelyasheat.Path2
givespartofthetotalinternalenergyasheat,butmostoftheinternalenergyappearsaswork
donebythemotor.

Inpath1offigure8.8,wesimplyshortcircuitthebatterybyplacingaheavyspanneracrossthe
terminals.Ifyouhaveeverdonethis,evenbyaccident,youknowhowviolenttheresultcanbe.Sparks
flyandthespannerbecomesveryhotasthebatteryquicklydischarges.Lotsofheatisgivenoff,butthe
systemdoesnowork(w=0).AllofUistransferredtothesurroundingsasheat.

Inpath2,wedischargethebatterymoreslowlybyusingittooperateamotor.Alongthispath,mostof
theenergyrepresentedbyUappearsaswork(runningthemotor)andonlyarelativelysmallamount
appearsasheat(fromthefrictionwithinthemotorandtheelectricalresistanceofthewires).

Therefore,neitherqnorwisastatefunction.Theirvaluesdependentirelyonthepathbetweenthe
initialandfinalstates.

HeatCapacity
Itisimportanttorealisethatheatandtemperaturearenotthesamething.Ifwetaketwoobjectsthatare
initiallyatdifferenttemperaturesandbringthemintocontact,bothobjectswilleventuallycometothe
sametemperature,providedwewaitlongenough.Thiscomesaboutthroughthetransferofheatfrom
thehotterobjecttothecolderobject,sowecansaythatheatisatransferofenergyduetoa
temperaturedifference.Wecannotmeasureheatdirectly,butwecancalculateitusingthetemperature
changethatoccurswhenheatflowsfromonebodytoanother.Thereis,infact,alinearrelationship
betweenheatandtemperaturechangegivenbytheequation:

whereqisheatandCistheheatcapacityoftheobjectinquestion.Theunitsofheatcapacity(JK1)
helpustounderstandwhatitisitcanbethoughtofastheamountofheatrequiredtoincreasethe
temperatureofanobjectbyaparticularamount,inthiscase1K.

WORKEDEXAMPLE8.1

ExperimentaldeterminationofheatCapacity
Centralprocessingchipsincomputersgenerateatremendousamountofheatenoughto
damagethemselvespermanentlyifthechipisnotcooledsomehow.Aluminiumheatsinks
areoftenattachedtothechipstocarryawayexcessheat.Wecanmeasuretheheatcapacity
ofsuchheatsinksbyplacingthem(hot)intoaknownvolumeofwaterandmeasuringthe
temperatureriseofthewater.Supposethataheatsinkat71.3Cisdroppedintoastyrofoam
cupcontaining100.0gofwaterat25.0C.Thetemperatureofthewaterrisesto27.4C.
Giventhatittakes4.18Jtoraisethetemperatureof1gofwaterby1K,whatistheheat
capacityoftheheatsink?

Analysis

Wewanttofindtheheatcapacity,C.Wecansolveq=CTforCbydividingbothsidesby
thetemperaturechange,T:

Wemustfindthetemperaturechangeoftheheatsinkandtheamountofheat,q,thatit
exchangeswiththewaterinthecup.

Solution

Tofindq,wecanassumethattheheatlostbytheheatsinkwillbegainedbythemuch
coolerwater,sowestartbycalculatingtheheatgainedbythewater:

Thetemperatureofthewaterrisesfrom25.0Cto27.4C,ariseof2.4K(recallthata
temperaturedifferencehasthesamenumericalvalueinbothKandC).Itwouldtake2.4K
4.18JK1=1.010 1Jofheattoraisethetemperatureofeachgramofwaterby2.4K,soit
wouldtake100.01.010 1J=1.010 3Jtoraisethetemperatureof100.0gofwaterby
2.4K.

Thetemperatureoftheheatsinkdropsfrom71.3Cto27.4C,so:

Theheatgainedbythewateris1.010 3J.Theheatlostbytheheatsinkwillbe1.010 3J
(noticethatthenegativesignmeansheatwaslostbytheobject).Theheatcapacityis:
 Isouranswerreasonable?

Inanycalculationinvolvingenergytransfer,wefirstchecktoseethatallquantitieshavethe
correctsigns.Thewatergainedabout1000Jandwarmedupby2.4K,sothewater'sheat
capacityis1000J/2.4K,orabout400JK1.Thisisabout20timesthecalculatedheat
capacityoftheheatsink.Wewouldexpect,then,thetemperatureriseofthewatertobe
about1/20ofthetemperaturedropoftheheatsink,sinceitabsorbs20timesasmuchheatas
theheatsinkbeforeitstemperaturewillrise1degree.Thetemperatureoftheheatsink
droppedby43.9K,andthetemperatureofthewaterroseby2.4K,whichagreewiththis
prediction.

PRACTICEEXERCISE8.1
Aballbearingat220Cisdroppedintoa
styrofoamcupcontaining250gofwater.
Thewaterwarmsfrom25.0to30.0C.
Whatistheheatcapacityoftheballbearing,
inJK1?

Heatcapacitydependsonthesizeofthesample.Ifittakes4.184Jtoraisethetemperatureof1gof
waterby1K,itwilltaketwicethatamountofenergy(8.368J)toobtainthesametemperaturerisein2
gofwater.Anypropertywithavaluethatdependsonthesizeofthesampleiscalledanextensive
property,whileonewithavaluethatisthesameregardlessofthesizeofthesampleiscalledan
intensiveproperty.Forexample,thevolumeofasystemisanextensiveproperty,whereasits
temperatureisanintensiveproperty.Wecanturnheatcapacity,anextensiveproperty,intoanew
intensivepropertycalledspecificheatcapacitybydividingbythemassofthesample.Specificheat
capacity(oftencalledspecificheat)issimplytheheatcapacitypergramofsubstance.Ithasthesymbol
candisdefinedas:

givingctheunitsofJg 1K1.Theadvantageofusingtheintensivepropertyspecificheatisthatwecan
easilycomparevaluesforthesamemassofdifferentsubstancesbyinspection.Aswecanseeintable
8.1,thespecificheatofwaterisapproximatelyninetimesthatofiron,meaningthatittakesninetimes
asmuchheattoraisethetemperatureofwaterbyaspecifiedamountasitdoesforthesamemassof
iron.Theheatrequiredtoraisethetemperatureof1moleofasubstanceby1Kiscalledthemolarheat
capacityandhasunitsofJmol1K1.
TABLE8.1 SpecificHeatsofSelectedSubstancesat25C
Substance Specificheat(Jg1K1) Molarheatcapacity(Jmol1K1)
lead 0.128 26.5

gold 0.129 25.4

 gold 0.129 25.4
silver 0.235 25.4
copper 0.387 24.6
iron 0.4498 25.1
carbon(graphite) 0.711 8.5
oxygen(gas) 0.920 29.4
neon(gas) 1.03 20.8
nitrogen(gas) 1.04 29.1
ethanol 2.45 113
water(liquid) 4.18 75.3

Wecancalculatetheheatabsorbedoremittedbyanobjectgivenitsmass(m),temperaturechange(T)
andspecificheat(c)by:

WORKEDEXAMPLE8.2

CalculatingHeatfromaTemperatureChange,Massand
SpecificHeat
Ifagoldringwithamassof5.50gchangesintemperaturefrom25.0to28.0C,howmuch
heathasitabsorbed?

Analysis

Thequestionasksustoconnecttheheatabsorbedbytheringwithitstemperaturechange,
T.Wedon'tknowtheheatcapacityofthering.Wedoknowthemassoftheringandthatit
ismadeofgold,sowecanlookupthespecificheat.Wewillusethevalueofthespecific
heatofgoldgivenfor25Cintable8.1,thatis,0.129Jg 1K1.

Solution

Themass,m,oftheringis5.50g,thespecificheat,c,is0.129Jg 1K1,andthetemperature
increasesfrom25.0to28.0C,soTis3.0C.Usingthesevaluesgives:

Thus,just2.1Jraisesthetemperatureof5.50gofgoldby3.0C.BecauseTispositive,so
istheheat,2.1J.Thus,thesignofqsignifiesthattheringabsorbsheat.

Isouranswerreasonable?

Iftheringhadamassofonly1ganditstemperatureincreasedby1C,we'dknowfromthe
 specificheatofgold(let'srounditto0.13Jg 1K1)thattheringwouldabsorb0.13J.Fora
3degreetemperatureincrease,theanswerwouldbethreetimesasmuch,or0.39J,nearly
0.4J.Foraringalittleheavierthan5g,theheatabsorbedwouldbefivetimesasmuch,or
about2.0J.Soouranswer(2.1J)isclearlyreasonable.Noticealsothatanalysisofunitscan
beveryhelpfulinproblemslikethese.Wewantourfinalanswerinjoules,andthereisonly
onepossiblewayofcombiningheatcapacity(Jg 1K1),mass(g)andT(K)togivethisunit
namelymultiplyingthemtogether.Ifyoucannotremembertheformoftheequation,you
canalwaysfigureitoutusingunits(seesection2.2).

PRACTICEEXERCISE8.2
Thetemperatureof250gofwaterwas
changedfrom25.0to30.0C.Howmuch
heatwastransferredintothewater?

Thedeterminationofheat
Nowthatweknowtherelationshipbetweentemperaturechangeandheat,wecanusethistodetermine
theheatlostorgainedinachemicalreactionorphysicalprocess.Wecarryoutthereactionorprocess
inacalorimeter,whichisapieceofapparatusespeciallydesignedtominimiseheatlossbetweenthe
systemandsurroundings.Therearetwomaintypesofcalorimeterthosethatoperateunder
conditionssuchthatthesystemremainsatconstantvolumeandthosethatcontainthesystematconstant
pressure.Whilethedistinctionmayappearsmall,wewillseethatthereareimportantimplications.Let
usfirstconsidercombustionreactionswhereasubstanceundergoesreactionwithoxygeninaconstant
volumebombcalorimeter,anexampleofwhichisshowninfigure8.9.Becausethevolumeofthe
systemcannotchangeduringthereaction,Vforthesystemwillbe0.ThismeansthatpVmustalso
be0.Rememberthatw=pVtherefore,noworkcanbedonebyoronthesystem.Recallthat:

so,forareactioncarriedoutunderconstantvolumeconditionsinabombcalorimeter,itfollowsthat:

whereq vistheheatofreactionatconstantvolume.
 FIGURE8.9Abombcalorimeter.ThesampleisplacedinthesteelbombwhichisthenfilledwithO2 (g).The
initialtemperatureofthestirredwaterismeasured,andthecombustionreactionistheninitiated
electrically.Thereactiongivesoutheat,whichisabsorbedbythesteelcalorimeterandthe
surroundingwater.Measurementofthetemperatureriseofthewater,togetherwithknowledgeof
theheatcapacitiesofthebombcalorimeterandthewater,allowtheheatofreactionatconstant
volume,qv,andthereforetheinternalenergyofthereaction,rU,tobecalculated.

Foodscientistsdeterminetheinternalenergyoffoodsandfoodingredientsbyburningtheminabomb
calorimeter.Thereactionsthatbreakdownfoodsinthebodyarecomplex,buttheyproducethesame
productsasthecombustionreactionforthefood.

Itisimportantthatyouusethecorrectsignoftheheatchangeinanycalculationsbasedoncalorimetric
measurements.Consider,forexample,acombustionreactioncarriedoutinabombcalorimeterofthe
typeshowninfigure8.9.Theheatgivenoutbythechemicalreactionisabsorbedbythecalorimeter
andthesurroundingwater,leadingtoameasuredtemperatureriseofthewater.Insimpleterms,the
chemicalreactiongivesoutanamountofheat(q reaction),whichisgainedbythecalorimeterandits
surroundings(q calorimeter).Thesetwoamountsofheatarenumericallyequal,butoppositeinsign.Itis
alwaystruethat:

regardlessofwhetherthereactiongivesout,ortakesin,heat.

WORKEDEXAMPLE8.3

BombCalorimetry

(a)When1.000gofoliveoiliscompletelyburnedinpureoxygeninabombcalorimeter
liketheoneshowninfigure8.9,thetemperatureofthewaterbathincreasesfrom
22.000Cto22.241C.Theheatcapacityofthecalorimeteris9.032kJK1.How
 muchheatisproducedonburning1.000gofoliveoil?
(b)Oliveoilisalmostpureglyceryltrioleate,C57H104O6.Theequationforthe
combustionofglyceryltrioleateis:

Whatisthechangeininternalenergy,rU,inkJforthecombustionof1moleof
glyceryltrioleate?Assumetheoliveoilburnedin(a)waspureglyceryltrioleate.

Analysis

In(a),wearegiventheheatcapacityofthecalorimeteranditstemperaturechangeandwe
areaskedfortheheatproducedbyburning1.000gofoliveoil.Thecalorimeterabsorbsthe
heatreleasedbytheburningoliveoil.Wecancalculatetheheatabsorbedbythecalorimeter
(q calorimeter)fromitstemperaturechangeandheatcapacity,andtheheatreleasedbytheoil
(q reaction)willbethenegativeofthis.SincetheheatcapacityisinkJK1,theheatreleased
willbeinkJ.

In(b),weareaskedforthechangeininternalenergy,rU.Bombcalorimetrymeasuresheat
atconstantvolume,whichisequaltotheinternalenergychangeforthereaction.Thus,the
heatcalculatedin(a)isequaltorUfor1gofglyceryltrioleate.Wecanusethemolarmass
ofglyceryltrioleatetoconvertrUpergramtorUpermole.

Solution
(a)Wecalculatetheheatabsorbedbythecalorimeterwhen1.000gofoliveoilisburned
using:

Theheatabsorbedbythecalorimetercomesfromthecombustionoftheoliveoili.e.
q calorimeter=q reaction.Therefore,q reactionforburning1.000gofoliveoilis2.18kJ,
andtheenergycontentoftheoliveoilonamassbasisisthus2.18kJg 1.
(b)Weconverttheheatproducedpergramtotheheatproducedpermole,usingthe
molarmassofC57H104O6,885.4gmol1:

Sincethisisheatatconstantvolume,wehaverU=q v=1.9310 3KJfor

combustionof1moleofC57H104O6.

Isouranswerreasonable?

Alwayscheckthesignsofcalculatedheatsincalorimetry.Thecombustionreactionreleases
heat,sothesignmustbenegative.Weappeartohavedonethenumericalcalculations
correctly,sowecanassumeouransweriscorrect.
 PRACTICEEXERCISE8.3
A1.50gsampleofcarbonisburnedina
bombcalorimeterwithaheatcapacityof
8.930kJK1.Thetemperatureofthewater
jacketrisesfrom20.00Cto25.51C.What
isrUforthecombustionof1moleof
carbon?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.4Enthalpy
Inchemistry,wearemostoftenconcernedwithreactionsthatoccurinsolution,anditismoreconvenienttocarryoutsuchreactionsin
abeaker,flaskortesttubeopentotheatmospherethaninsideametalbomb.Inthesecases,weareworkingunderconditionsof
constantatmosphericpressure.Hence,thesystemisfreetoexpandorcontractandthismeansthatitcanpotentiallydowork.Thuswe
canseethatwewillnotbeabletomakethesamesimplificationsaswedidunderconstantvolumeconditions.Aswehavealready
seen,whenasystemexpandsagainstaconstantpressure,p,theworkdoneisgivenby:

where:

Underconditionswherethesystemexpands,Vispositiveandsowisnegative,meaningthatthesystemhasdoneworkonthe
surroundingsandconsequentlylowereditsinternalenergy.Theoppositeistrueifthesystemiscompressed.Wenowrewrite:

underconditionsofconstantpressureas:

whereq pistheheatofreactionatconstantpressure.However,thisequationisinconvenientasweneedtoknowthevalueofVif
wewishtocalculateU.Atthispoint,wedefineanewthermodynamicfunctioncalledenthalpy,whichhasthesymbolH,as:

Thus,underconditionsofconstantpressure:

SubstitutingU=q ppVintothisgives:

so:

Thus,theheatofreactionatconstantpressureisequaltorH,inthesamewaythattheheatofreactionatconstantvolumeisequalto
rU.LikerU,rHisastatefunction,meaningthattheenthalpychangeforareactiondependsonlyontheinitialandfinalstatesof
thesystem.Ifthefinalenthalpyofthesystemisgreaterthantheinitial,thesystemhasabsorbedheatfromitssurroundings,sorH
willbepositiveandthereactionissaidtobeendothermic.Conversely,ifthesystemhaslostheattothesurroundings,theenthalpyof
thesystemhasdecreased,sorHwillbenegativeandthereactionissaidtobeexothermic.

ThedifferencebetweentheenthalpychangeandtheinternalenergychangeforareactionispV.ThedifferencebetweenrUand
rHcanbeverylargeforreactionsthatproduceorconsumegases,becausethesereactionscanhaveverylargevolumechanges.Ifa
reactioninvolvesonlysolidsandliquids,though,thevaluesofVaretiny,sorUandrHforthesereactionsarenearlyidentical.

Averysimpleconstantpressurecalorimeter,dubbedthecoffeecupcalorimeter,comprisestwonestedandcappedcupsmadeof
styrofoam,averygoodinsulator(figure8.10).Areactionoccurringinsuchacalorimeterexchangesverylittleheatwiththe
surroundings,particularlyifthereactionisfast,underwhichconditionsthetemperaturechangeisrapidandeasilymeasured.Wecan
findtheheatofreactionifwehavedeterminedtheheatcapacityofthecalorimeteranditscontentsbeforethereaction.Thestyrofoam
cupandthethermometerabsorbonlyatinyamountofheat,andwecanusuallyignoretheminourcalculations.

FIGURE8.10Acoffeecupcalorimeterusedtomeasureheatsofreactionatconstantpressure.
WORKEDEXAMPLE8.4

ConstantPressureCalorimetry
Thereactionofhydrochloricacidandsodiumhydroxideisveryrapidandexothermic.Thebalancedchemicalequationis:

Inoneexperiment,50.0mLof1.00MHClat25.5Cwasplacedinacoffeecupcalorimeter.Tothiswasadded50.0mLof
1.00MNaOHsolution,alsoat25.5C.Themixturewasstirred,andthetemperaturequicklyincreasedtoamaximumof
32.2C.Thedensityof1.00MHClis1.02gmL1andthatof1.00MNaOHis1.04gmL1.Whatistheheatevolvedin
joulespermoleofHCl?Assumethatthespecificheatsofthesolutionsarethesameasthatofwater,4.18Jg 1K1.(Wewill
neglecttheheatlosttothestyrofoam,thethermometerandthesurroundingair.)

Analysis

Beforewecanuseq=cmTtofindtheheatevolved,wehavetocalculatethesystem'stotalmassandthetemperature
change.Themassherereferstothetotalmassofthecombinedsolutions,butweweregivenvolumes.Sowehavetouse
theirdensitiestocalculatetheirmasses,usingtheequation:

FortheHClsolution,thedensityis1.02gmL1so:

FortheNaOHsolution,thedensityis1.04gmL1so:

Themassofthefinalsolutionisthusthesum,103.0g.

Solution

ThereactionchangesthetemperatureofthecalorimeterbyTfinalTinitial,so:

Nowwecancalculatetheheatabsorbedbythecalorimeter,q calorimeter:

Knowingthatq reaction=q calorimeter,weobtainq reaction=2.910 3J.

Thisistheheatevolvedforthespecificmixtureprepared.However,theproblemcallsforjoulespermoleofHCl.We
calculatetheamountofHClusingtheequation:

Neutralising0.0500molofacidgaveq reaction=2.910 3J.So,onapermolebasis:

Thus,theenthalpychangeforthisreactionis58kJmol1.(Thenegativesignshowsthatthereactionisexothermic.)

Isouranswerreasonable?

Let'sfirstreviewthelogicofthestepsweused.Noticehowthelogicisdrivenbydefinitions,whichcarryspecificunits.
Workingbackwards,knowingthatwewantunitsofjoulespermoleintheanswer,wemustcalculateseparatelytheamount
ofacidneutralisedandtheamountofheatevolved.Thelatterwillemergewhenwemultiplythesolution'smass(g)and
specificheat(Jg 1K1)bythetemperatureincrease(K).

Thestepinthecalculationthatinvolvesthemassofthefinalsampleisstraightforward.Becausethedensitiesarecloseto1
gmL1,thecombinedmassesareabout50gpersolutionoratotalof100g.
 Thespecificheatisaround4.2Jg 1K1,whichmeansthat,ifthefinalsolutionweighed1g,itsheatcapacitywouldbe4.2
JK1.Ifthemassis100g,theheatcapacityis100timesasmuch,or420JK1.

Thetemperatureincreasedbyabout7Kso,whenwemultiply420JK1by7,wegettheheatabsorbedbythecalorimeter,
about2940Jor2.910 3J,whichisthesameas2.9kJq reactionisthenegativeofthis.

Thismuchheatisassociatedwithneutralising0.0500molHCl,sotheheatpermoleis2.9kJdividedby0.0500mol,or
58kJmol1.

PRACTICEEXERCISE8.4
Whenpuresulfuricaciddissolvesinwater,alargeamount
ofheatisgivenoff.Tomeasureit,175gofwaterwas
placedinacoffeecupcalorimeterandchilledto10.0C.
Then4.90gofsulfuricacid,H2SO4,alsoat10.0C,was
added,andthemixturewasquicklystirredwitha
thermometer.Thetemperatureroserapidlyto14.9C.
Assumethatthevalueofthespecificheatofthesolutionis
4.18Jg 1K1andthatthesolutionabsorbsalltheheat
evolved.Calculatetheheatevolvedinkilojouleson
formationofthissolution.(Remembertousethetotalmass
ofthesolution:thewaterplusthesolute.)Calculatealsothe
heatevolvedpermoleofsulfuricacid.

Standardenthalpychange
Theamountofheatareactionproducesorabsorbsdependsontheamountsofreactantswecombine.Itmakessensethat,ifweburn2
molesofcarbon,wewillgettwiceasmuchheatasifwehadburned1mole.Forheatsofreactiontohavemeaning,wemustdescribe
thesystemcompletely.Ourdescriptionmustincludeamountsandconcentrationsofreactants,amountsandconcentrationsof
products,temperatureandpressure,becauseallofthesethingscaninfluenceheatsofreaction.

Chemistshaveagreedonasetofstandardstatestomakeiteasiertoreportandcompareheatsofreaction.Mostthermochemical
equationsarewrittenforreactantsandproductsatapressureof10 5Paor,forsubstancesinaqueoussolution,aconcentrationof1M.
Atemperatureof25C(298K)isoftenspecifiedaswell,althoughtemperatureisnotpartofthedefinitionofstandardstatesin
thermochemistry.Theuseofstandardstatesisdenotedbythesuperscriptsymbol .

Thestandardenthalpyofreaction attemperatureTisthevalueofHforareactioninwhichthepure,separatedreactantsin
theirstandardstatesareconvertedtothepureseparatedproductsintheirstandardstates,allattemperatureT,andinwhichthe
stoichiometriccoefficientsinthebalancedchemicalequationrefertoactualnumbersofmoles.WhiletheSIunitof isJmol1,
valuesareusuallyquotedinkJmol1.

Toillustrateclearlywhatwemeanby ,letususethereactionbetweengaseousnitrogenandhydrogenthatproducesgaseous
ammonia:

When1.000molofN2(g)and3.000molofH2(g)reacttoform2.000molofNH3(g)at25Cand10 5Pa,thereactionreleases92.38
kJ.Hence,forthereactionasgivenbytheprecedingequation, .Often,theenthalpychangeisgiven
immediatelyaftertheequation,forexample:

Anequationthatalsoshowsthevalueof iscalledathermochemicalequation.Italwaysgivesthephysicalstatesofthe
reactantsandproducts,anditsassociated valueistrueonlywhenthecoefficientsofthereactantsandproductsarenumerically
equaltotheamountsofthecorrespondingsubstances.Theequationabove,forexample,showsareleaseof92.38kJif2molesof
NH3form.Ifweweretomaketwiceasmuch,or4.000mol,ofNH3(from2.000molofN2and6.000molofH2),thentwiceasmuch
heat(184.8kJ)wouldbereleased.Ontheotherhand,ifonly0.5000molofN2and1.500molofH2weretoreacttoformjust1.000
molofNH3,thenonlyhalfasmuchheat(46.19kJ)wouldbereleased.Forthevariousreactionsjustdescribed,forexample,wewould
havethefollowingthermochemicalequations:

Becausethecoefficientsofathermochemicalequationalwaysmeanmoles,notmolecules,wemayusefractionalcoefficients.

Youmustwritedownphysicalstatesforallreactantsandproductsinthermochemicalequations.Thecombustionof1moleof
methane,forexample,hasdifferentvaluesof ifthewaterproducedisinitsliquidoritsgaseousstate:

Thedifferencein valuesforthesetworeactionsisthequantityofenergythatwouldbereleasedbythephysicalchangeof2
molesofwatervapourat25Cto2molesofliquidwaterat25C.

WORKEDEXAMPLE8.5

WritingaThermochemicalEquation
Thefollowingthermochemicalequationisthatfortheexothermicreactionofhydrogenandoxygenthatproduceswater
(seefigure8.11):

Whatisthethermochemicalequationforthisreactionwhenitiscarriedouttoproduce1.000molH2O?

FIGURE8.11TheairshipHindenburgusedhydrogen,agasthatislighterthanairbutalsoflammable,toprovidelift.On6May1937,
atLakehurst,NewJersey,USA,itcaughtfirewhilemooring,probablyasaresultofbuildupofstaticelectricity,andthe
explosivereactionofhydrogenwithoxygendestroyedtheairshipinminutes.

Analysis

Thegivenequationisfortheproductionof2.000molofH2O,andanychangesinthecoefficientforwatermustbemade
identicallytoallothercoefficients,aswellastothevalueof .

Solution

Wedivideeverythingby2toobtain:

Isouranswerreasonable?

Comparetheequationjustfoundwiththeinitialequationtoseethatthecoefficientsandthevalueof arealldivided
by2.
 PRACTICEEXERCISE8.5
Whatisthethermochemicalequationfortheformationof
2.500molofH2Oinworkedexample8.5?

Oncewehavethethermochemicalequationforagivenreaction,wecanwritetheequationforthereversereaction,regardlessofhow
harditmightactuallybetomakeithappen.Forexample,thethermochemicalequationforthecombustionofcarboninoxygentogive
carbondioxideis:

Thereversereaction,whichisextremelydifficulttocarryout,wouldbethedecompositionofcarbondioxidetocarbonandoxygen:

Despitehowharditwouldbetocarryoutthisreaction,wecanstilldetermineitsvalueof .Itmustbe+393.5kJmol1,thatis,
equalinsizebutoppositeinsignto forthereactionwrittenintheoppositedirection.Thelawofconservationofenergyrequires
thisremarkableresult.Ifthevaluesof fortheforwardandthereversereactionswerenotequalbutoppositeinsign,then
perpetualmotionmachineswouldbepossible.(Despitenumerousclaims,suchmachineswillalwaysbeanunattainabledream.)Thus,
regardlessofthedifficultyofdirectlydecomposingCO2intoitselements,wecanstillwriteathermochemicalequationforit:

Torepeat,ifweknow foragivenreaction,thenwealsoknow forthereversereactionithasthesamenumericalvalue,

buttheoppositealgebraicsign.Thisextremelyusefulfactmakesthermochemicaldataavailablethatwouldotherwisebeimpossibleto
measure.

Hess'sLaw

Hess'slawisamethodforcombiningknownthermochemicalequationsinawaythatallowsustocalculate foranotherreaction.
Thisrequiresexperienceinotherkindsofmanipulationsofequations.Wewillillustratethisusingthecombustionofcarbon.

Wecanimaginetwopathsleadingfrom1moleeachofcarbonandoxygento1moleofcarbondioxide.

Onesteppath

LetCandO2reacttogiveCO2directly:

Twosteppath

LetCandO2reacttogiveCO,andthenletCOreactwithO2togiveCO2:
Step1:

Step2:

Overall,thetwosteppathconsumes1moleeachofCandO2tomake1moleofCO2,justliketheonesteppath.Theinitialandfinal
statesforthetworoutestoCO2areidentical.

If isastatefunctiondependentonlyontheinitialandfinalstatesandindependentofpath,thevaluesof forbothroutes
shouldbeidentical.Wecanseethatthisistruesimplybyaddingtheequationsforthetwosteppathandcomparingtheresultwiththe
equationfortheonesteppath:
NotethatwecancancelCO(g)asitappearsidenticallyonoppositesidesofthearrowinsteps1and2.Suchacancellationispermitted
onlywhenboththeformulaandthephysicalstateofaspeciesareidenticalonoppositesidesofthearrow.Thenetthermochemical
equationforthetwostepprocess,therefore,is:

Theresults,chemicallyandthermochemically,areidenticalforbothroutestoCO2,demonstratingthat isastatefunction.The
aboveexampleisamanifestationofHess'slaw,whichstatesthattheoverallenthalpychangeforanychemicalreactionisconstant,
regardlessofhowthereactioniscarriedout.

ThechiefuseofHess'slawistocalculatetheenthalpychangeforareactionforwhichsuchdatacannotbedeterminedexperimentally
orareotherwiseunavailable.Becausethisrequiresthatwemanipulateequations,let'srestatethefewrulesthatgovernthese
operations.

RulesforManipulatingThermochemicalEquations

1.Whenanequationisreversedwrittenintheoppositedirectionthesignof mustalsobereversed.Toillustrate,the
reverseoftheequation:

isthefollowingequation:

2.Substancescanbecancelledfrombothsidesofanequationonlyifthesubstanceisinanidenticalphysicalstate.
3.Ifallthecoefficientsofanequationaremultipliedordividedbythesamefactor,thevalueof mustlikewisebemultiplied
ordividedbythatfactor.

WORKEDEXAMPLE8.6

UsingHess'sLaw
Carbonmonoxideisoftenusedinmetallurgytoremoveoxygenfrommetaloxidestogivethefreemetal.The
thermochemicalequationforthereactionofCOwithiron(III)oxide,Fe2O3,is:

UsethisequationandtheequationforthecombustionofCO:

tocalculatethevalueof forthefollowingreaction:

Analysis

Wecannotsimplyaddthetwogivenequations,becausethiswillnotproducetheequationwewant.Wefirsthaveto
manipulatetheseequationssothatwhenweaddthemwewillobtainthetargetequation.

Solution

Wecanmanipulatethetwogivenequationsasfollows:
Step1:Webeginwiththeironatoms.Thetargetequationmusthave2Feontheleft,butthefirstequationinthis
workedexamplehas2Fetotherightofthearrow.Tomoveittotheleft,wemustreversetheentireequation,
rememberingalsotoreversethesignof .ThisputsFe O totherightofthearrow,whichiswhereithastobeafter
2 3
weaddouradjustedequations.Afterthesemanipulations,andreversingthesignof ,wehave:

Step2:Theremustbe ontheleft,andwemustbeabletocancel3COand3CO whentheequationsareadded.If

2
 wemultiplythesecondequationinthisworkedexampleby3,wewillobtainthenecessarycoefficients.Wemustalso
multiplythevalueof forthisequationby3,becausethreetimestheamountofsubstancesarenowinvolvedinthe
reaction.Whenwehavedonethis,wehave:

Wenowputourtwoequationstogetherandfindtheanswer:

Thus,thevalueof fortheoxidationof2molFe(s)to1molFe2O3(s)is822.3kJmol1.(Thereactionisvery
exothermic.)

Isouranswerreasonable?

Thereisnoshortcuttocheckthatweareright.But,foreachstep,doublecheckthatyouhavefollowedtherulesfor
manipulatingthermochemicalequations.

PRACTICEEXERCISE8.6

Ethanol,C2H5OH,ismadeindustriallybythereactionofwaterwithethene,C2H4.Calculatethevalueof forthe
reaction:

giventhefollowingthermochemicalequations:

StandardEnthalpyofFormation
Enormousdatabasesofthermochemicalequationshavebeencompiledtoallowthecalculationofanyenthalpyofreactionusing
Hess'slaw.Themostfrequentlytabulateddataarethoseforformationreactions.

Thestandardenthalpyofformation ofasubstanceistheenthalpychangewhen1moleofthesubstanceisformedat10 5Pa

andthespecifiedtemperaturefromitselementsintheirstandardstates.Anelementisinitsstandardstatewhenitisinitsmoststable
formandphysicalstate(solid,liquidorgas)at10 5Paandthespecifiedtemperature.Oxygen,forexample,isinitsstandardstateata
temperatureof25Conlyasagasat10 5PaandonlyasO2molecules,notasOatomsorO3(ozone)molecules.Carbonmustbeinthe
formofgraphite,notdiamond,tobeinitsstandardstateatatemperatureof25Cbecausethegraphiteformofcarbonisthemost
stableformatthistemperatureunderstandardconditions(10 5Pa).

Standardenthalpiesofformationforavarietyofsubstancesaregivenintable8.2,andamoreextensivetablecanbefoundin
appendixA.Noticeinparticularthatallvaluesof fortheelementsintheirstandardstatesare0forminganelementfromitself,
ofcourse,wouldyieldnochangeinenthalpy.Forthisreason,valuesof fortheelementsaregenerallynotincludedintables.

TABLE8.2 StandardEnthalpiesofFormationofSelectedSubstancesat25C

(kJmol1)
Substance
Ag(s) 0
AgBr(s) 100.4
AgCl(s) 127.0
Al(s) 0
1669.8
Al2O3(s)

C(s,C60) 2320
C(s,diamond) 1.9
C(s,graphite) 0

CH3Cl(g) 82.0
CH3I(g) 14.2
CH3OH(l) 238.6
CH3COOH(l) 487.0
CH4(g) 74.848
C2H2(g) 226.75
C2H4(g) 52.284
C2H6(g) 84.667
C2H5OH(l) 277.63
CO(g) 110.5
CO2(g) 393.5
CO(NH2)2(s) 333.19

Ca(s) 0
CaBr2(s) 682.8
CaCO3(s) 1207
CaCl2(s) 795.0
CaO(s) 635.5
Ca(OH)2(s) 986.59
CaSO4(s) 1432.7
1575.2

CaSO42H2O(s) 2021.1
Cl2(g) 0
Fe(s) 0
Fe2O3(s) 822.3
H2O(g) 241.8
H2O(l) 285.9

H2(g) 0
H2O2(l) 187.6
HBr(g) 36
HCl(g) 92.30
HI(g) 26.6
HNO3(l) 173.2

H2SO4(l) 811.32

Hg(l) 0
Hg(g) 60.84
I2(s) 0
K(s) 0

KCl(s) 435.89
K2SO4(s) 1433.7
N2(g) 0
NH3(g) 46.19
NH4Cl(s) 315.4
NO(g) 90.37
NO2(g) 33.8
N2O(g) 81.57

N2O4(g) 9.67
N2O5(g) 11
Na(s) 0
NaHCO3(s) 947.7
Na2CO3(s) 1131
NaCl(s) 411.0
NaOH(s) 426.8
Na2SO4(s) 1384.5
O2(g) 0
Pb(s) 0
PbO(s) 219.2
S(s,rhombic) 0
SO2(g) 296.9
SO3(g) 395.2

Itisimportanttorememberthemeaningofthesubscriptfinthesymbol .Itisappliedonlywhen1moleofthesubstanceis
formedfromitselementsintheirstandardstates.Consider,forexample,thefollowingfourthermochemicalequationsandtheir
correspondingvaluesof :

Onlyinthefirstequationis giventhesubscriptf.Itistheonlyreactionthatsatisfiesbothoftheconditionsspecifiedforstandard
enthalpiesofformation.Thesecondequationshowstheformationof2molesofwater,ratherthan1mole.Thethirdinvolvesa
compoundasthereactant.Thefourthinvolvestheelementsasatoms,whicharenotstandardstatesfortheseelements.Wecanobtain
forthesecondequationsimplybymultiplyingthe valueofthefirstequationby2.

WORKEDEXAMPLE8.7

WritinganEquationforaStandardEnthalpyofFormation

Writetheequationtowhich refers.

Analysis
 Theequationmustshowonly1moleoftheproduct.Webeginwithitsformulaandtakewhateverfractionsofmolesofthe
elementsareneededtomakeit.Wealsoremembertoincludethephysicalstates.Table8.2givesthevalueof for
HNO3(l)as173.2kJmol1.

Solution

Thethreeelements,H,NandO,alloccurasdiatomicmoleculesinthegaseousstate,sothefollowingfractionsofmoles
supplyexactlyenoughtomake1moleofHNO3:

Isouranswerreasonable?

Theanswercorrectlyshowsonly1moleofHNO3,andthisgovernsthecoefficientsforthereactants.Sosimplycheckthat
theequationisbalanced.

PRACTICEEXERCISE8.7
Writethethermochemicalequationthatwouldbeusedto
representthestandardenthalpyofformationofsodium
bicarbonate,NaHCO3(s).

StandardenthalpiesofformationareusefulbecausetheyprovideaconvenientmethodforapplyingHess'slawwithouthavingto
manipulatethermochemicalequations.Thisispossiblebecause,aswewilldemonstrate, forareactionequalsthesumofthe
standardenthalpiesofformationoftheproductsminusthesumofthestandardenthalpiesofformationofthereactants,witheach
valuemultipliedbytheappropriatestoichiometriccoefficientgivenbythethermochemicalequation.Inotherwords,forthe
reaction:

or,inmoregeneralterms:

wheremeansthesumoverandviandvjarethestoichiometriccoefficientsfortheproductsandreactants,respectively,inthe
balancedchemicalequationforthereaction.

Althoughthetwoexpressionsabovefor lookverydifferent,theyaremerelyalternativeformulationsoftheHess'slawequation.
Whilebotharegivenintermsofstandardenthalpiesofformation, ,theyalsoapplytostandardenthalpiesofcombustion,
(seep.313).However,youneedtoensureyouuseonlyeitherstandardenthalpiesofformationorstandardenthalpiesofcombustion
whencalculating usingtheaboveequationsyoumustnevermixthem.

WewillnowdemonstratethattheHess'slawequationworks.Considerthereactiongivenbythefollowingequation:

Wewishtocalculatetheenthalpyofreactionusingstandardenthalpiesofformation.

Ifweusethefirstmethodwelearned,namely,themanipulationofthermochemicalequations,wewouldneedtoimagineapathfrom
thereactanttotheproductsthatinvolvesfirstdecomposingSO3(g)intoitselementsintheirstandardstatesandthenrecombiningthe
elementstoformtheproducts.Thispathisshowninfigure8.12.Thefirststepwiththeenthalpychangeindicatedas ,
correspondstothedecompositionofSO3(g)intosulfurandoxygen.ThisisjustthereverseoftheequationfortheformationofSO3(g),
sowecanwrite:

Weuseanegativesignbecause,whenwereverseaprocess,wechangethesignofitsrH.
 FIGURE8.12Enthalpydiagramforthereaction:

Thepathofthereactioninthisdiagraminvolvesthereactantbeingdecomposedintoitselementsintheirstandardstates(red
arrow),andthentheelementsbeingrecombinedtoformtheproducts(downwardbluearrow).Thedifferenceinthelengthsof
thesetwoarrowsisproportionaltothenetenthalpychange(upwardbluearrow).

Thesecondstepinfigure8.12,withtheenthalpychangeindicatedas ,istheformationofSO2(g)plus moleofO2(g)from

sulfurandoxygen.Therefore,wecanwrite:

Thesumofthesetwostepsgivesthenetchangewewant,sothesumof and mustequalthedesired :

Bysubstitution:

Thiscanberewrittenas:

Thechangeofsigngives:

Noticecarefullythenetresult. forthereactionequalsthesumoftheenthalpiesofformationoftheproductsminustheenthalpy
offormationofthereactant,eachmultipliedbytheappropriatecoefficient.So,wecouldhaveobtainedtheidenticalresultbyusingthe
Hess'slawequationdirectly,insteadofbythemorelaboriousmethodofmanipulatingthermochemicalequations.

WORKEDEXAMPLE8.8

UsingHess'sLawandStandardEnthalpiesofFormation
Somechefskeepbakingsoda,NaHCO3,handytoputoutfatandoilfires.Whenthrownonthefire,bakingsodapartly
smothersthefireandtheheatdecomposesittogiveCO2,whichfurthersmotherstheflame.Theequationforthe
decompositionofNaHCO3is:

Usethedataintable8.2tocalculate forthisreaction.

Analysis
 TheHess'slawequationisnowourbasictoolforcalculatingvaluesof .Sowecalculatethesumofthe values
fortheproducts(table8.2),eachmultipliedbytheappropriatestoichiometriccoefficient,anddothesameforthereactants.
Thenwesubtractthelatterfromtheformertocalculate .

Solution

TheHess'slawequationgivesus:

Wenowusetable8.2tofindthevaluesof foreachsubstanceinitsproperphysicalstate.

Thus,understandardconditions,thereactionisendothermicby129kJmol1.(Noticethatwedidnothavetomanipulate
anyequations.)

Isouranswerreasonable?

Doublecheckthatallofthecoefficientsfoundinthegivenequationarecorrectlyappliedasmultipliersinthesolution.Be
surethatthesignsofthevaluesof haveallbeencarefullyused.Haveyouusedtheorderofsubtractingspecifiedin
theHess'slawequation?Keepingtrackofnegativesignsrequiresparticularcare.

PRACTICEEXERCISE8.8

Calculate forthefollowingreactions:
(a)2NO(g)+O2(g)2NO2(g)
(b)NaOH(s)+HCl(g)NaCl(s)+H2O(l)

StandardEnthalpyofCombustion

Thestandardenthalpyofcombustion ofasubstanceattemperatureTistheenthalpychangewhen1moleofthesubstanceis
completelyburnedinpureoxygengas,withallreactantsandproductsbroughttotemperatureTand10 5Papressure.Allcarboninthe
substancebecomescarbondioxidegas,andallhydrogenbecomesliquidwater.Combustionreactionsarealwaysexothermic,so
isalwaysnegative.Theunitsof areusuallykJmol1.

WORKEDEXAMPLE8.9

WritinganEquationforaStandardEnthalpyofCombustion
Whatamountofcarbondioxidegasisproducedbyagasfiredpowerplantforevery1.0MJ(megajoule)ofenergyit
produces?Theplantburnsmethane,CH4(g),forwhich is890kJmol1.

Analysis

Weneedtolinktheamountofcarbondioxidewiththeamountofheatproduced.Todothis,werequireabalanced
thermochemicalequation.Asthisisacombustionreaction,thereactantswillbethefuel,CH4(g),andoxygen,O2(g),and
theproductswillbecarbondioxidegas(becausethefuelcontainscarbon)andliquidwater(becausethefuelcontains
hydrogen).Wemustthereforebalancethefollowingequationforcombustionof1moleofCH4(g):
 ThecoefficientinfrontofCO2(g)willbetheamountofCO2producedwhen890kJofheatisreleased.Usingthis,wecan
thenobtainaconversionfactortorelatemegajoulesofheattotheamountofCO2(g).Tolinkmegajouleswithkilojoules,
we'llneedtorememberthemeaningsoftheSIprefixeskiloandmega:

ThesethreerelationsareallweneedtolinkmegajoulesofheatwiththeamountofCO2(g).

Solution

Webalancetheequationfor1moleofCH4asfollows:

so1molCO2isreleasedforevery890kJofheatreleased.Knowingthat1MJ=1000kJ,theamountofCO2produced
when1MJofheatisreleasedis:

Isouranswerreasonable?

Wecanseethattheequationhasbeencorrectlybalancedfor1molCH4eachsidehasoneCatom,fourHatomsandfour
Oatoms.Wecanalsoseethatitmakessensethatonlyslightlymorethan1moleofCO2isproducedwith1MJ(1000kJ)of
heat,because1000kJisonlyslightlymorethan890kJ,theamountofheatproducedonformationof1moleofCO2.

PRACTICEEXERCISE8.9
A60litrecarfueltankcanholdabout507molesofn
octane,C8H18(l),whichhasastandardenthalpyof
combustionof5450.5kJmol1.Howmuchheatcouldbe
producedbyburningafulltankofnoctane?

BondEnthalpies
Chemicalreactionsgenerallyinvolvethebreakingofchemicalbondsinthereactantsandthemakingofchemicalbondsinthe
products.Theobservedenthalpychangeforanychemicalreactionispredominantlyaresultofthesebondbreakingandbondmaking
processesenergyisrequiredtobreakachemicalbondandenergyisliberatedonformationofachemicalbond.Therefore,a
knowledgeofindividualbondenergiescanprovideuswithameanstoestimatetheoverallenthalpychangeinachemicalreaction.

Abondenthalpyistheenthalpychangeonbreaking1moleofaparticularchemicalbondtogiveelectricallyneutralfragmentsinthe
gasphaseattemperatureT.Youshouldappreciatethatthebondenergieswehaveencounteredinpreviouschaptersareassociated
withUandrefertoconditionsofconstantvolume.Bondenthalpiesareusefulinrationalisingchemicalreactivity,astheyprovidea
measureoftheeasewithwhichaparticularchemicalbondcanbebroken.Elementalnitrogen,forexample,hasaverylowdegreeof
reactivity,whichisgenerallyattributedtotheverystrongtriplebondinN2.Reactionsthatinvolvebreakingthisbondinasinglestep
simplydonotoccur.WhenN2doesreact,itisbyastepwisebreakingofitsthreebonds,oneatatime.

BondEnthalpiesandHess'sLaw
ThebondenthalpiesofsimplediatomicmoleculessuchasH2,O2andCl2areusuallymeasuredspectroscopically,usingtechniques
similartothosewediscussedinchapter4(p.123).Anelectricdischargeisusedtoexcitethemolecules,causingthemtoemitlight.An
analysisofthespectrumoftheemittedlightallowscalculationoftheamountofenergyneededtobreakthebond.

Formorecomplexmolecules,thermochemicaldatacanbeusedtocalculatebondenthalpiesusingHess'slaw.Wewillusethestandard
enthalpyofformationofmethanetoillustratehowthisisaccomplished.However,beforewecanattemptsuchacalculation,wemust
firstdefineathermochemicalquantitycalledtheatomisationenthalpy(atH).Thisistheenthalpychangethatoccursonrupturingall
thechemicalbondsin1moleofgaseousmoleculestogivegaseousatomsasproducts.Forexample,theequationfortheatomisation
ofmethaneis:
andtheenthalpychangefortheprocessis understandardconditions.Forthisparticularmolecule, correspondstothe
totalenthalpychangeonbreakingalltheCHbondsin1moleofCH4understandardconditionstherefore,divisionof by4
wouldgivetheaverageCHbondenthalpyinmethane.

Figure8.13showshowwecanusethestandardenthalpyofformation, ,tocalculatetheatomisationenthalpy.Acrossthebottom
wehavethechemicalequationfortheformationof1moleofCH4fromitselementsintheirstandardstates.Theenthalpychangefor
thisreactionis .Inthisfigure,wealsocanseeanalternativethreesteppaththatleadstoCH4(g).OnestepisthebreakingofH
HbondsintheH2moleculestogivegaseoushydrogenatomsanotheristhevaporisationofcarbontogiveagaseouscarbonatom,
andthethirdisthecombinationofthegaseousatomstoformaCH4molecule.Thesechangesarelabelled1,2and3inthefigure.

FIGURE8.13Twopaths(equations)fortheformationofmethanefromitselementsintheirstandardstates.Asdescribedinthetext,steps1,2
and3oftheupperpatharetheformationofgaseousatomsoftheelementsandthentheformationofthebondsinCH4 .Thelower
pathisthedirectcombinationoftheelementsintheirstandardstatestogiveCH4 .BecauseHisastatefunction,thesumofthe
enthalpychangesalongtheupperpathmustequaltheenthalpychangeforthelowerpath,

Sinceenthalpyisastatefunction,thenetenthalpychangefromonestatetoanotheristhesameregardlessofthepaththatwefollow.
Thismeansthatthesumoftheenthalpychangesalongtheupperpathmustbethesameastheenthalpychangealongthelowerpath,
.PerhapsthiscanbeseenmoreeasilyinHess'slawtermsifwewritethechangesalongtheupperpathintheformof
thermochemicalequations.

Steps1and2haveenthalpychangesthatarestandardenthalpiesofformationofgaseousatoms.Valuesforthesequantitieshavebeen
measuredformanyoftheelements,andsomearegivenintable8.3.Step3istheoppositeofatomisation,anditsenthalpychange
will,therefore,bethenegativeof (recallthatifwereverseareaction,wechangethesignofitsH).

TABLE8.3 StandardEnthalpiesofFormationofSelectedGaseousAtomsfromtheElementsintheirStandardStatesat25C

Atom (kJmol1)(a)

B 560
Be 324.3
Li 161.5
Br 112.38
C 716.67
Cl 121.47
F 79.14

H 217.89
I 107.48
N 472.68
O 249.17
P 332.2
S 276.98
Si 450
Allvaluesarepositivebecauseformationofthegaseousatomsfromtheelementsinvolvesbondbreaking,whichrequiresan
inputofenergy.
Noticethat,byaddingthefirstthreeequations,wegettheequationfortheformationofCH4fromitselementsintheirstandardstates.
Thismeansthataddingthe valuesofthefirstthreeequationsshouldgive forCH4:

Wewillsubstitutefor , , ,andthensolvefor .First,wesubstituteforthe quantities:

Next,wesolvefor( ):

Changingsignsandrearrangingtherighthandsideoftheequationgives:

Nowallweneedarethe valuesontherighthandside.Weobtain and fromtable8.3and from

table8.2androundthesetothenearest0.1kJmol1:

Substitutingthesevaluesgives:

GiventhateachCH4moleculecontainsfourCHbonds,divisionby4givesanestimateoftheaverageCHbondenthalpyinthis
molecule:

Thisvalueisquiteclosetotheoneintable8.4,whichisanaverageoftheCHbondenthalpiesinmanydifferentcompounds.The
otherbondenthalpiesintable8.4arealsobasedonthermochemicaldataandwereobtainedbysimilarcalculations.
TABLE8.4 SomeAverageBondEnthalpiesat25C

Bond Bondenthalpy(kJmol1) Bond Bondenthalpy(kJmol1) Bond Bondenthalpy(kJmol1)

CC 348 CF 484 HH 436
C C 612 CCl 338 HF 565
C C 960 CBr 276 HCl 431
CH 412 CI 238 HBr 366
CN 305 HI 299
C N 613 HN 388
C N 890 HO 463
CO 360 HS 338
C O 743 HSi 376

Aremarkablethingaboutmanycovalentbondenthalpiesisthattheyareverynearlythesameinmanydifferentcompounds.This
suggests,forexample,thataCHbondisverynearlythesameinCH4asitisinalargenumberofothercompoundsthatcontainthis
kindofbond.Alsonotethat,ingeneral,triplebondenthalpies(e.g.C C)aregreaterthandoublebondenthalpies(C C),whichin
turnaregreaterthansinglebondenthalpies(CC).

Becausethebondenthalpydoesnotvarymuchfromcompoundtocompound,wecanusetabulatedbondenthalpiestoestimatethe
enthalpiesofformationofsubstances.Wewillillustratethisbycalculatingthestandardenthalpyofformationofmethanolvapour,
CH3OH(g).Thestructuralformulaformethanolis:
Tocarryoutthiscalculation,wesetuptwopathsfromtheelementstothecompound,asshowninfigure8.14.Thelowerpathhasan
enthalpychangecorrespondingto whiletheupperpathtakesustothegaseouselementsandthenthroughtheenthalpy
changewhenthebondsinthemoleculeareformed.Thislatterenthalpycanbecalculatedfromthebondenthalpiesintable8.4.As
before,thesumoftheenthalpychangesalongtheupperpathmustbethesameastheenthalpychangealongthelowerpath,andthis
allowsustodetermine .

FIGURE8.14Twopathsfortheformationofmethanolvapourfromitselementsintheirstandardstates.Thenumberedstepsarediscussedinthe
text.

Steps1,2and3infigure8.14involvetheformationofthegaseousatomsfromtheelements,andtheirenthalpychangesareobtained
fromtable8.3:

Thesumofthesevalues,+1837.5kJmol1,isthenet forthefirstthreesteps.

TheformationoftheCH3OHmoleculefromthegaseousatomsisexothermicbecauseenergyisalwaysreleasedwhenatomsbecome
joinedbycovalentbonds.Inthismolecule,wecancountthreeCHbonds,oneCObondandoneOHbond.Theirformation
releasesenergyequaltothesumoftheirbondenthalpies,whichweobtainfromtable8.4.

Bond Bondenthalpy(kJmol1)
3(CH) 3412=1236
CO 360
OH 463

Addingthesegivesatotalof2059kJmol1.Therefore, is2059kJmol1becauseitinvolvesbondformation,andsoitis
exothermic.Nowwecancalculatethetotalenthalpychangefortheupperpath.

Thevaluejustcalculatedshouldbeequalto forCH3OH(g).Forcomparison,ithasbeenfoundexperimentallythat for

thismolecule(inthevapourstate)is201kJmol1.Atfirstglance,theagreementdoesnotseemverygood,butonarelativebasisthe
calculatedvalue(222kJ)differsfromtheexperimentalvaluebyonlyabout10%.

LatticeEnthalpiesandHess'sLaw
Hess'slawcanbeusedincombinationwithparticularthermodynamicdatatocalculatethevaluesoflatticeenthalpiesforionicsolids.
WewillillustratethisusingNaCl(s).Recallfromchapter5(p.170)thatthelatticeenthalpy(or,aswecalleditthen,latticeenergy)of
anionicsolidistheenthalpychangefortheconversionof1moleoftheionicsolidintoitsconstituentgaseousions.ForNaCl(s)we
wouldrepresentthisprocessbytheequation:

Wecanbreakthisprocessintosmallersteps,eachwithanassociatedenthalpychange,asshowninfigure8.15.
 FIGURE8.15AnenthalpydiagramthatcanbeusedtocalculatethelatticeenthalpyofNaCl(s).Notethattheenthalpychangesarenotdrawnto
scale.

Theunknownlatticeenthalpy,H6,isshownatthebottomoffigure8.15.Thisisanendothermicprocessthatrequiresenergytoturn
NaCl(s)intoitsgaseousionsNa+(g)andCl(g).FromHess'slaw,weknowthatH6=H1+H2+H3+H4+H5.Aseachof
H1toH5isatabulatedthermodynamicquantity,wecancalculateH6,thelatticeenthalpyofNaCl(s).Noticethatwehave
definedH1astheenthalpychangefortheprocess:

ThisisthereverseoftheequationdefiningtheenthalpyofformationofNaCl(s):

sowemustusethenegativeoftheenthalpyofformationofNaCl(s)inourcalculations.

Thecalculationisthen:

ThelatticeenthalpyofNaCl(s)isthus786kJmol1.

Thisapproachgivesvaluesclosetotheexperimentallymeasuredlatticeenthalpiesforionicsolidscontainingrelativelysmallions.As
thesizesoftheionsincrease,thevaluesbecomelessaccuratebecausethebondinginsuchsolidsisnolongerpurelyionic.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.5Entropy
Intheprevioussection,wedefinedenthalpy,showinghowitisrelatedtoheat.Wewillnowdiscussthethermodynamicfunctionentropy.
Whiletherearemanydifferenttextbookdefinitionsofentropy,herewewillconcentrateonitsstatisticalbasis.

Entropyandprobability
Earlierinthischapter,youlearnedthat,whenahotobjectisplacedincontactwithacolderone,heatwillflowspontaneouslyfromthehot
objecttothecolderone.Butwhy?Energywillbeconservednomatterwhatthedirectionoftheheatflowis.Andifwebelievethatthe
loweringofenergyisthedrivingforcebehindspontaneouschange,wemightwonderwhytheloweringoftheenergyofthehotobjectis
favouredoverthegaininenergythatresultsforthecolderone.

Wewillbuildasimplemodeltoexplainthedirectionofheatflow.Imaginethatwehavetwoobjectsmadeofmoleculesthathavealowenergy
groundstateandahighenergyexcitedstate.Theywillactuallyhavemanydifferentexcitedstates,butwewillkeepthingssimpleandassume
thatthemoleculescanbeeitherlowenergyinthegroundstateorhighenergyinjustoneexcitedstate.Wewilluseabluedottorepresenta
lowenergycoldmolecule,andareddottorepresentahighenergyhotmolecule.Ifweplacethreehighenergymoleculesincontactwiththree
lowenergymolecules,weinitiallyhaveaconfigurationliketheoneshownontheright.Wherethethreemoleculesontheleftrepresentan
objectthatishotandthethreeontherightrepresentacoldobject.Aftertheobjectsareplacedincontact,energycanbetransferredbetween
moleculesinthetwoobjects.Thetotalenergyofthetwoobjectsmustbethesamebeforeandaftercontact.Becauseourmoleculescanhave
onlyhighenergy(red)orlowenergy(blue)states,thetotalnumberofredmoleculesmustbethesamebeforeandaftercontact.Hereareall
possibledistributionsofenergyamongthesixmoleculesaftertheobjectshavebeenplacedintocontact:

Wecanseefourpossibleoutcomes0,1,2or3unitsofenergycanbetransferredfromthehotbodytothecolderone.Whichismostlikelyto
occur?

Noticethatsomeoftheoutcomescanbeproducedinanumberofdifferentways.Forexample,arrangements2to10representwaysenergy
canbedistributedamongthemoleculesafter1unitofenergyistransferred.Themorewaysthatastatecanbeproduced,themorelikelyitisto
occur.Wecanusethisfacttoestimatetheprobabilityofthestateoccurring.Thereare20possiblearrangementsofenergyamongtheparticles
afterthehotandcoldobjectsarebroughtintocontact.Let'sassumethatallofthesearrangementsareequallyprobable.Theprobabilityofa
particularoutcomecanbecalculatedas:

Forexample,thereareninearrangementsthatcorrespondtoatransferof1energyunitand20arrangementsinall,sotheprobabilitythat1
energyunitwillbetransferredis9/20=0.45or45%.

Unitsofenergytransferred Numberofequivalentwaystoproducetheenergytransfer Probabilityofenergytransfer

0 1 1/20=5%
1 9 9/20=45%
2 9 9/20=45%
3 1 1/20=5%
Inthismodelsystem,thereisa19/20or95%chancethatsomeamountofenergytransferwilloccur.Thisagreeswithourexpectationthatheat
shouldflowspontaneouslyfromthehotobjecttothecolderone.

Toshowtheimportanceofprobabilityindeterminingthedirectionofheatflow,considerthepossibleoutcomesiftheinitialstateofthesystem
wasgivenbyarrangement2onthepreviouspage,asshownontheright.Here,thehotobjectcontainstwohighenergymoleculesandone
lowenergymolecule,whilethecoldobjectcontainstwolowenergymoleculesandonehighenergymolecule.Ifwebringtheobjectsinto
contact,thefinalpossiblestatesarestillgivenbyarrangements1to20onthepreviouspage.Noticethoughthat,ifthefinalstateofthesystem
isarrangement1,asshownbelowright,thenthisformallyinvolvesthehotobjectgettinghotterandthecoldobjectgettingcolder,
somethingalientooureverydayexperience.However,asthisisonlyoneof20possiblefinalarrangements,theprobabilityofthisoccurringis
only5%.Ifwerepeatthisanalysiswithobjectsthatcontainmoreandmoreparticles,theprobabilityofenergytransferbecomessohighthat
wecanbequitecertainthatheatwillflowfromahotobjecttoacolderone.Ifwearedealingwithhotandcoldobjectsthatcontainmolesof
particles,thechancethatnoenergytransferwouldoccuroncetheywereplacedintocontactisnegligible.

Althoughourmodelforheattransferisverysimple,itdemonstratestheroleofprobabilityindeterminingthedirectionofaspontaneous
process.Spontaneousprocessestendtoproceedfromstatesoflowprobabilitytostatesofhigherprobability.Thehigherprobabilitystatesare
thosethatallowmoreoptionsfordistributingenergyamongthemolecules,sowecanalsosaythatspontaneousprocessestendtodisperse
energy.

Entropyandentropychange
Becausestatisticalprobabilityissoimportantindeterminingtheoutcomeofchemicalandphysicalevents,thermodynamicsdefinesaquantity,
calledentropy(S),thatdescribesthenumberofequivalentwaysthatenergycanbedistributedinthesystem.Thelargerthevalueofthe
entropy,themoreenergeticallyequivalentversionsthereareofthesystemand,therefore,thehigherisitsstatisticalprobability.In
mathematicalterms:

whereWisthenumberofwaysofdispersingafixedamountofenergyinasystemoffixedsize,andkistheBoltzmannconstant(1.38065
10 23JK1).

Inchemistry,weusuallydealwithsystemsthatcontainverylargenumbersofparticles.Itisusuallyimpracticaltocountthenumberofways
thattheparticlescanbearrangedtoproduceasystemwithaparticularenergy,aswedidinoursimplemodelforenergyflowbetweenahot
andcoldobject.Fortunately,wedonotneedtodoso.Theentropyofasystemcanberelatedtoexperimentalheatandtemperature
measurements.Wecanalsorecogniseincreasesanddecreasesinentropywithoutexplicitlycountingthenumberofwaysthesystemcanbe
realised.

Likeenthalpy,entropyisastatefunction.Itdependsonlyonthestateofthesystem,soachangeinentropy,S,isindependentofthepath
fromstarttofinish.Aswithotherthermodynamicquantities,Sisdefinedasfinalminusinitialorproductsminusreactants.Thus:

or,forachemicalreaction:

TheunitsofrSareJmol1K1.

Asyoucansee,whenS finalislargerthanS initial(orwhenS productsislargerthanS reactants),thevalueofSispositive.ApositivevalueforS

meansanincreaseinthenumberofenergyequivalentwaysthesystemcanbeproducedwehaveseenthatthiskindofchangetendstobe
spontaneous(seefigure8.16).Thisleadstoageneralstatementaboutentropy:Anyeventthatisaccompaniedbyanincreaseintheentropyof
anisolatedsystemhasatendencytooccurspontaneously.

FIGURE8.16 ApositivevalueforrSmeansanincreaseinthenumberofwaysenergycanbedistributedamongasystem'smolecules.Considerthe
reaction3A3B,whereAmoleculescantakeonenergiesthataremultiplesof10energyunits,andBmoleculescantakeonenergies
thataremultiplesof5units.Supposethatthetotalenergyofthereactingmixtureis20units.
(a)Therearetwowaystodistribute20unitsofenergyamongthreemoleculesofA.
(b)Therearefourwaystodistribute20unitsofenergyamongthreemoleculesofB.TheentropyofBishigherthantheentropyofA
becausetherearemorewaystodistributethesameamountofenergyinBthaninA.Thereaction3A3Bisthereforespontaneous.

FactorsthatAffectEntropy
ItisoftenpossibletopredictwhetherSispositiveornegativeforaparticularchange.Thisisbecauseseveralfactorsinfluencethemagnitude
oftheentropyinpredictableways.

Volume
Forgases,theentropyincreaseswithincreasingvolume,asillustratedinfigure8.17.Attheleftweseeagasconfinedtoonesideofa
container,separatedfromavacuumbyaremovablepartition.let'ssupposethepartitioncouldbepulledawayinaninstant,asshowninfigure
8.17a.Nowwefindasituationinwhichallthemoleculesofthegasareatoneendofalargercontainer.Therearemanymorepossibleways
thatthetotalkineticenergycanbedistributedifwegivethemoleculesgreaterfreedomofmovementandspreadthemthroughoutthelarger
volume.Thatmakestheconfigurationinfigure8.17bextremelyunlikely.Therefore,thegasexpandsspontaneouslytoachieveamore
probable(higherentropy)particledistribution(figure8.17c).

FIGURE8.17 Theexpansionofagasintoavacuum:
(a)agasinacontainerseparatedfromavacuumbyapartitionand
(b)thegasatthemomentthepartitionisremoved.
(c)Thegasexpandstoachieveamoreprobable(higherentropy)particledistribution.

Temperature
Entropyisaffectedbytemperature:thehigherthetemperature,thehighertheentropy.Forexample,whenasubstanceisasolidattemperatures
closetoabsolutezero,itsparticlesareessentiallymotionless.Thereisrelativelylittlekineticenergywithfewwaystodistributekineticenergy
amongtheparticles,theentropyofthesolidisrelativelylow(figure8.18a).Ifsomeheatisaddedtothesolid,thekineticenergyofthe
particlesincreasesalongwiththetemperature.Thiscausestheparticlestovibratewithinthecrystal,soataparticularmoment(figure8.18b)
theparticlesarenotfoundexactlyattheirequilibriumlatticesites.Thereismorekineticenergyandmorefreedomofmovement,sothereare
morewaystodistributetheenergyamongthemolecules.Atastillhighertemperature,thereismorekineticenergyandmorepossiblewaysto
distributeit,sothesolidhasastillhigherentropy(figure8.18c).
 FIGURE8.18Variationofentropywithtemperature.

Physicalstate
Oneofthemajorfactorsthataffectstheentropyofasystemisitsphysicalstate,whichisdemonstratedinfigure8.19.Supposethatthe
contentsofthethreecontainersareice,liquidwaterandwatervapouratthesametemperature.Thereisgreaterfreedomofmolecular
movementinliquidwaterthaniniceatthesametemperature,andsotherearemorewaystodistributekineticenergyamongthemoleculesof
liquidwaterthanthereareinice.Watervapourmoleculesarefreetomovethroughtheentirecontainer,sotherearemanymorepossibleways
todistributethekineticenergyamongthegasmoleculesthanthereareinliquidorsolidwater.Infact,anygashassuchalargeentropy
comparedwithaliquidorsolidthatchangeswhichproducegasesfromliquidsorsolidsarealmostalwaysaccompaniedbyincreasesin
entropy.

FIGURE8.19Comparisonoftheentropiesofthesolid,liquid,andgaseousstatesofwater.Thecrystallinesolidhasaverylowentropy.Theliquidhasa
higherentropybecauseitsmoleculescanmovemorefreelyand,therefore,therearemorewaystodistributekineticenergyamongthem.All
themoleculesarestillfoundatthebottomofthecontainer.Thegashasthehighestentropybecausethemoleculesarerandomlydistributed
throughouttheentirecontainer,sotherearemanywaystodistributethekineticenergy.

Forreactionsthatinvolvegases,wecansimplycalculatethechangeintheamountofgas,n gas,ongoingfromreactantstoproducts.

Whenn gasispositive,soistheentropychange.

Whenachemicalreactionproducesorconsumesgases,thesignofitsentropychangeisusuallyeasytopredict.Thisisbecausetheentropyof
agasissomuchlargerthanthatofeitheraliquidorsolid.Forexample,thethermaldecompositionofsodiumbicarbonateproducestwogases,
CO2andH2O:

Becausetheamountofgaseousproductsislargerthantheamountofgaseousreactants,wecanpredictthattheentropychangeforthereaction
ispositive.Ontheotherhand,thereaction:

whichcanbeusedtoremovesulfurdioxide,anatmosphericpollutant,fromagasmixture,hasanegativeentropychangeasn gas<0.
Numberofparticles
Forchemicalreactions,anothermajorfactorthataffectsthesignofrSisanincreaseinthetotalnumberofmoleculesasthereaction
proceeds.Whenmoremoleculesareproducedduringareaction,morewaysofdistributingtheenergyamongthemoleculesarepossible.
Whenallotherthingsareequal,reactionsthatincreasethenumberofparticlesinthesystemtendtohaveapositiveentropychange,asshown
infigure8.20.Thisisparticularlytruewhentheproductsaregases,owingtotheirinherentlylarge,positiveentropies.

FIGURE8.20Entropyisaffectedbythenumberofparticles.Addingparticlestoasystemincreasesthenumberofwaysthatenergycanbedistributedin
thesystemso,withallotherthingsbeingequal,areactionthatproducesmoreparticleshasapositivevalueofrS.

WORKEDEXAMPLE8.10

PredictingtheSignofrS

PredictthealgebraicsignofrSforthereactions:
(a)2NO2(g)N2O4(g)
(b)C3H8(g)+5O2(g)3CO2(g)+4H2O(g)
(c)CO(g)+H2O(g)H2(g)+CO2(g)

Analysis

Asweexaminetheequations,welookforchangesinthenumberofmoleculesofgasandchangesinthenumberofparticleson
goingfromreactantstoproducts.

Solution

Inreaction(a),weareformingoneN2O4moleculefromthetwoNO2molecules.Sinceweareformingfewermolecules,thereare
fewerwaystodistributeenergyamongthem,whichmeansthattheentropymustbedecreasing.Therefore,rSmustbenegative.

Forreaction(b),wecancountthenumberofmoleculesonbothsides.Ontheleftoftheequationwehavesixmoleculesonthe
rightthereareseven.Therearemorewaystodistributekineticenergyamongsevenmoleculesthanamongsix,soforreaction(b)
weexpectrStobepositive.

Forreaction(c),thereisthesamenumberofmoleculesonbothsides.WecannotthereforepredictthesignofrSwithconfidence,
butweexpectitsmagnitudetobesmall.

Isouranswerreasonable?

Wereachthesameconclusionbycountingthenumberofmolesofgasonbothsidesoftheequation.Inreaction(a),1moleof
gaseousproductisformedfrom2molesofgaseousreactant.Whenthereisadecreaseinthenumberofmolesofgas,thereaction
tendstohaveanegativerS.Inreaction(b),thereare6molesofgasonthereactantsideoftheequationand7molesofgasonthe
productside.Becausethenumberofmolesofgasisincreasing,weexpectrStobepositive.

Inreaction(c),thereisthesamenumberofmolesofgasonbothsides,sowecannotpredictthesignofrS.

PRACTICEEXERCISE8.10
Predictthesignoftheentropychangefor(a)thecondensation
ofsteamtoliquidwaterand(b)thesublimationofasolid.
 PRACTICEEXERCISE8.11
PredictthesignofrSforthefollowingreactions.
(a)2SO2(g)+O2(g)2SO3(g)
(b)CO(g)+2H2(g)CH3OH(g)

PRACTICEEXERCISE8.12
WhatistheexpectedsignofrSforthefollowingreactions?
Justifyyouranswers.
(a)2H2(g)+O2(g)2H2O(l)
(b)N2(g)+3H2(g)2NH3(g)
(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.6TheSecondLawofThermodynamics
Thesecondlawofthermodynamicscanhelpusappreciatetheimportanceofentropy.Thislawstates
that,wheneveraspontaneouseventtakesplaceinouruniverse,thetotalentropyoftheuniverse
increases(S total>0).Noticethattheincreaseinentropyreferredtohereisforthetotalentropyofthe
universe(systemplussurroundings),notjustthesystemalone.Thismeansthattheentropyofasystem
candecrease,aslongasthereisalargerincreaseintheentropyofthesurroundingssothattheoverall
entropychangeispositive.Theconsequenceofthisisthatwecannotusetheentropychangeofthe
systemaloneasacriterionforspontaneityofaparticularchemicalreaction.Becauseeverythingthat
happensreliesonspontaneouschangesofsomesort,theentropyoftheuniverseisconstantlyrising.

Nowlet'sexaminemorecloselytheentropychangefortheuniverse.Aswehavesuggested,this
quantityequalsthesumoftheentropychangeforthesystemplustheentropychangeforthe
surroundings:

Itcanbeshownthattheentropychangeforthesurroundingsisequaltotheheattransferredtothe
surroundingsfromthesystem,q surroundings,dividedbythethermodynamictemperature,T,atwhichitis
transferred:

Thelawofconservationofenergyrequiresthattheheatgainedbythesurroundingsequalsthenegative
oftheheatlostbythesystem,sowecanwrite:

Inourstudyofthefirstlawofthermodynamicswesawthat,forchangesatconstanttemperatureand
pressure,q system=Hforthesystem.Bysubstitution,therefore,wearriveattherelationship:

andourexpressionfortotalentropychangethereforebecomes:

MultiplyingthroughbyTgives:

or:

WestatedabovethatS totalis>0foraspontaneousprocess,and,becauseTisalwayspositive,theleft
handsideofthisequationwillbepositive.Tomaketherighthandsideofthisequationpositiverequires
thatthequantityinparenthesesisnegative.Inotherwords,foraspontaneousprocess:

WenowformallydefinethethermodynamicfunctionGibbsenergy(G)as:

ForchangesatconstantTandp,wecanthereforewrite:

whereG=GfinalGinitial

WeshowedonthepreviouspagethatHsystemTS system<0foraspontaneousprocess.AsG=H
TS,itfollowsfromthisthat,ifG<0forachemicalprocessinasystematconstantTandp,that
processwillbespontaneous.Wewillinvestigatethisconceptfurtherinsection8.8.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.7TheThirdLawofThermodynamics
Earlierwedescribedhowtheentropyofasubstancedependsontemperature,andwenotedthatattemperatures
approachingabsolutezerotheorderwithinacrystalincreasesandtheentropydecreases.Thethirdlawof
thermodynamicsgoesonestepfurtherbystatingthat,atabsolutezero,theentropyofaperfectlyorderedpure
crystallinesubstanceiszero.

Becauseweknowthepointatwhichentropyhasavalueof0,itispossiblebyexperimentalmeasurementand
calculationtodeterminetheentropyofasubstanceattemperaturesabove0K.Iftheentropyof1moleofa
substanceisdeterminedunderstandardconditions,wecallitthestandardentropy .Table8.5liststhe
standardentropiesofanumberofsubstancesat25C.
TABLE8.5 StandardEntropiesofSelectedSubstancesat25C

Substance
Ag(s) 42.55
AgCl(s) 96.2
Al(s) 28.3
Al2O3(s) 51.00
C(s,diamond) 2.4
C(s,graphite) 5.69
CH3Cl(g) 234.2
CH3OH(l) 126.8
CH3COOH(l) 160
CH4(g) 186.2
C2H2(g) 200.8
C2H4(g) 219.8
C2H6(g) 229.5
C2H5OH(l) 161
C8H18(l) 466.9
CO(g) 197.9
CO2(g) 213.6
CO(NH2)2(s) 104.6
Ca(s) 41.4
CaCO3(s) 92.9
CaCl2(s) 114
CaO(s) 40
Ca(OH)2(s) 76.1

CaSO4(s) 107
131

CaSO42H2O(s) 194.0
Cl2(g) 223.0
 Cl2(g) 223.0
Fe(s) 27
Fe2O3(s) 90.0
H2(g) 130.6
H2O(g) 188.7
H2O(l) 69.96
HCl(g) 186.7
HNO3(l) 155.6
H2SO4(l) 157
Hg(l) 76.1
Hg(g) 175
K(s) 64.18
KCl(s) 82.59

K2SO4(s) 176
N2(g) 191.5
NH3(g) 192.5
NH4Cl(s) 94.6
NO(g) 210.6
NO2(g) 240.5
N2O(g) 220.0
N2O4(g) 304
Na(s) 51.0
Na2CO3(s) 136
NaHCO3(s) 102
NaCl(s) 72.38
NaOH(s) 64.18
Na2SO4(s) 149.4
O2(g) 205.0
PbO(s) 67.8
S(s,rhombic) 31.9

SO2(g) 248.5

SO3(g) 256.2

Oncewehavetheentropiesofavarietyofsubstances,wecancalculatethestandardentropyofreaction
forchemicalreactionsinmuchthesamewayaswecalculated earlier.Forthereaction:
or:

Ifthereactionweareworkingwithhappenstocorrespondtotheformationof1moleofacompoundfromits
elements,the thatwecalculatecanbereferredtoasthestandardentropyofformation .Valuesof
arenottabulated,howeverifweneedthemforsomepurpose,wecancalculatethemfromtabulatedvaluesof
.

WORKEDEXAMPLE8.11

Calculating fromstandardentropies

Urea(acompoundfoundinurine)ismanufacturedcommerciallyfromCO2andNH3.Oneofitsusesis
asafertiliser,whereitreactsslowlywithwaterinthesoiltoproduceammoniaandcarbondioxide:

Theammoniaprovidesnitrogenforgrowingplants.Whatisthestandardentropyofreactionwhen1
moleofureareactswithwaterat298K?

Analysis

Wecancalculatethestandardentropyofreactionforthereactionusingthestandardentropies, ,of
eachreactantandproduct.Thedataweneedcanbefoundintable8.5andarelistedbelow.

Substance (Jmol1K1)
CO(NH2)2(s) 104.6
H2O(l) 69.96
CO2(g) 213.6
NH3(g) 192.5

Solution

Thestandardentropyofreactioncanbecalculatedfromtheequation:

Thus,thestandardentropyofreactionforthisreactionis+424.0Jmol1K1.
 Isouranswerreasonable?

Inthereaction,gasesareformedfromliquidreactants.Sincegaseshavemuchlargerentropiesthan
liquids,weexpect tobepositive,whichagreeswithouranswer.

PRACTICEEXERCISE8.13

Calculatethestandardentropyofreaction, ,
foreachofthefollowingreactions.
(a)CaO(s)+2HCl(g)CaCl2(s)+H2O(l)
(b)C2H4(g)+H2(g)C2H6(g)

Asthereisnostandardtemperature,thetemperatureisspecifiedasasubscriptonthesymbolforstandard
thermodynamicquantities:forexample, .Asyouwillseelater,therearetimeswhenitisdesirabletoindicate
thetemperatureexplicitly.

ChemicalConnections

AirconditioningandtheSecondLawofThermodynamics

Regardlessofwhereyoulive,Queensland,Queenstownorbeyond,chancesareitwillbeeithertoohotor
toocoldinsideyourhouseatsomestageofthedayornight.Whileitiseasytoheattheinteriorofahouse
usingcentralheatingoraradiantheater,coolingitpresentsuswithamoredifficultproblemsomehow
weneedtogetridofunwantedheat,andthisisdifficultwhenit'shotteroutsidethaninside.Ofcourse,we
allknowthattheinteriorofahousecanbecooledbyusinganairconditioner(figure8.21),butlet'sstop
andthinkaboutwhatactuallyhappenswhenwedothis.

FIGURE8.21Airconditionersuseelectricalenergytocompressandexpandafluidthatcarriesheatfromthe
 insideofabuildingtotheoutside.Indoingso,theairconditionerprovidesanentropycontribution
tothesystem,andtheoverallentropyoftheuniverseincreases.

Let'sassumethatit'sascorching45Coutsidewhiletheinsidetemperatureofourhouseisatropical35
C.Thenormaldirectionofheatflowwillbefromtheoutsidetotheinsideifweweretoopenallthe
windows,theinsidetemperaturewouldincreaseandeventuallybecomethesameasthatoutside,a
spontaneousprocesspreciselyinaccordwithwhatwehavelearnedinthischapter.Thereverseprocess,
heatflowingfromthe35Cinteriorofthehouse(thesystem)tothe45Cexterior(thesurroundings),is
nonspontaneous,andwemustthereforeuseanairconditionertodrivethis.Intermsofentropy,wecan
show,fromtheequation ,thataddingheatto,orremovingheatfrom,acoolsystemgivesa
greaterentropychangethantheanalogousprocesswithahottersystem.Thismeansthatcoolingthehouse
willlowertheentropyoftheinsidebymorethanitwillincreasetheentropyoftheoutsideitmaythere
foreappearthattheoverallprocessleadstoadecreaseinentropyoftheuniverse,violatingthesecondlaw
ofthermodynamics.Ofcourse,thisisnotthecase,aswehaveneglectedtoincludetheairconditioneritself
inthisdiscussion.Ituseselectricalenergytodoworkbycompressingandexpandingafluidthatcarries
theheatfromtheinsidetotheoutside.Insodoing,theairconditioneritselfprovidesanentropy
contribution,andthesumofthisandtheentropyincreaseofthesurroundingsisgreaterthantheentropy
decreaseofthesystem,therebyensuringthattheoverallentropyoftheuniverseincreasesandthatthe
secondlawofthermodynamicsremainsintact.

Heatpumpsoperateonthesameprinciplebutintheoppositedirection,takingheatfromthechillyoutside
anddeliveringittothewarmerinside,andthesameargumentsconcerningthetotalentropychangeapply.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
8.8GibbsEnergyandReactionSpontaneity
Nowthatwehavedefinedenthalpyandentropy,wearereadytolookindetailatGibbsenergy.Insection
8.2,westatedthataprocessisspontaneousifGfortheprocessisnegativeatconstanttemperatureand
pressure.WewillbeginbylookingatthefactorsthatdeterminethesignofG.

ThesignofG
Wemightnaivelyexpect,asdidanumberofnineteenthcenturyscientists,thatanychemicalprocessthat
evolvesheatwillbespontaneous,asitwillleadtoaloweringinenergy.However,wecanshowthatthisis
notthecasebyconsideringthemeltingoficeunderstandardconditionsat25.0C,aprocessthatis
spontaneous. forthisprocessisapproximately6kJmol1,meaningitisendothermic.Recallingour
expressionfor :

andrememberingthat mustbenegativefortheprocesstobespontaneous,wecanseethat,inthiscase,
if ispositive,theproductofTand mustbemorepositivetoensurethat isnegative.AsTis
alwayspositive, mustbepositiveforthemeltingoficetobespontaneous.(Wehaveseeninsection8.5
thatliquidsgenerallyhavelargerentropiesthansolids,sowewouldexpect forthemeltingoficetobe
positive.)Youcanseefromthisexamplethatthesignsof and arecrucialindeterminingthe
spontaneityofphysicalandchemicalprocessesunderstandardconditions.

Thecombustionofoctane,likeallcombustionreactions(p.313),isexothermic.Thereisalsoalarge
increaseinentropysincethenumberofparticlesinthesystemincreases.Forthischange,Hisnegative
andSispositive,bothofwhichfavourspontaneity:

Noticethat,regardlessofthethermodynamictemperature,whichmusthaveapositivevalue,Gwillbe
negative.Thismeansthatsuchachangemustbespontaneousatanytemperature.Infact,oncestarted,fires
continuetoconsumeallavailablefueloroxygenbecausecombustionreactionsarealwaysspontaneous(see
figure8.22a).

FIGURE8.22 ProcessspontaneitycanbepredictedifH,SandTareknown.
(a)WhenHisnegativeandSispositive,asinanycombustionreaction,thereactionis
spontaneousatanytemperature.
(b)WhenHispositiveandSisnegative,theprocessisnotspontaneous.Wooddoesnot
 spontaneouslyreformfromash,carbondioxideandwater.
(c)WhenHandShavethesamesign,temperaturedetermineswhethertheprocessis
spontaneous.Waterspontaneouslybecomesicebelow0C,andicespontaneouslymeltsinto
liquidwaterabove0C.

Whenachangeisendothermicandisaccompaniedbyaloweringoftheentropy,bothfactorsworkagainst
spontaneity:

Now,nomatterwhatthetemperatureis,Gwillbepositiveandthechangemustbenonspontaneous.An
examplewouldbecarbondioxideandwaterrecombiningtoformwoodandoxygenafterafire.Ifyousaw
suchathinghappenonafilm,experiencewouldtellyouthatthefilmwasbeingplayedbackwards.

WhenHandShavethesamealgebraicsign,thetemperaturebecomesthedeterminingfactorin
controllingspontaneity.IfHandSarebothpositive:

Gisthedifferencebetweentwopositivequantities,HandTS.Thisdifferencewillbenegativeonlyif
thetermTSislargerthanH,andthiswillbetrueonlywhenthetemperatureishigh.(Note:Weassume
thatthevaluesofHandSchangenegligiblywithchangeintemperature.)Inotherwords,whenH
andSarebothpositive,thechangewillbespontaneousathightemperaturebutnotatlowtemperature.
Anexamplewehavealreadyseenisthemeltingofice:

Thisisanendothermicchangethatisaccompaniedbyanincreaseinentropy.Weknowthatathigh
temperature(above0C)meltingisspontaneous,butatlowtemperature(below0C)itisnot.

Forsimilarreasons,whenHandSarebothnegative,Gwillbenegative(andthechangespontaneous)
onlyatlowtemperature:

OnlywhenthenegativevalueofHislargerthanthenegativevalueofTSwillGbenegative.Sucha
changeisspontaneousonlyatlowtemperature.Anexampleisthefreezingofwater:

Thisisanexothermicchangethatisaccompaniedbyadecreaseinentropyitisspontaneousonlyatlow
temperatures(below0C).

Figure8.23summarisestheeffectsofthesignsofHandSonG,andhenceonthespontaneityof
physicalandchemicalevents.
 FIGURE8.23SummaryoftheeffectsofthesignsofHandSonspontaneity.

StandardGibbsEnergyChange

WhenGisdeterminedat10 5Pa,wecallitthestandardGibbsenergychange .Thereareseveral

waysofobtaining forareaction.Oneistocalculate from and :

WORKEDEXAMPLE8.12

Calculating from and

Calculate forthereactionofureawithwaterat25.0Cfromvaluesof and at

thistemperature:

Analysis

Wecancalculate usingtheequation:

Thedataneededtocalculate comefromtable8.2andrequireaHess'slawcalculation.To
obtain ,wewouldnormallyneedtodoasimilarcalculationwithdatafromtable8.5.
However,wealreadycalculatedthisinworkedexample8.11.

Solution
 Firstwecalculate fromdataintable8.2:

Inworkedexample8.11,wefound tobe+424.0Jmol1K1.Tocalculate ,wealso

needtoexpress25.0Casathermodynamictemperaturebyadding273K.Thus,25.0C=298
K.Also,wemustbecarefultoexpress and inthesameenergyunits,sowechange
theunitsoftheenthalpychangetoJmol1togive Jmol1.Substituting
intotheequationfor :

Therefore,forthisreaction, kJmol1.

Isouranswerreasonable?

There'snotmuchwecandotocheckthereasonablenessoftheanswer.Wejustneedtobesure
we'vedonethecalculationscorrectlyandthattheunitsareconsistent.Notethat,insteadof
changingtheunitsof toJmol1,wecouldalsohavechangedtheunitsof tokJmol1
K1bydividingby10 3.Themostcommonmistakemadeincalculationslikethisisforgettingto
changetheunitsofeither or toensuretheunitsareconsistent.

PRACTICEEXERCISE8.14
Usethedataintables8.2and8.5tocalculate
fortheformationofiron(III)oxide(the
ironoxideinrust).Theequationforthe
reactionis:

Earlierinthischapteryoulearnedthatitisusefultohavetabulatedstandardenthalpiesofformation, ,
becausetheycanbeusedwithHess'slawtocalculate formanydifferentreactions.Standardfree
energiesofformation, ,canbeusedinsimilarcalculationstoobtain .Forthereaction:
or:

The valuesforsometypicalsubstancesarefoundintable8.6.Workedexample8.13showshowwe
canusethemtocalculate forareaction.

TABLE8.6 StandardGibbsEnergiesofFormationofSelectedSubstancesat25C

(kJmol1)
Substance
Ag(s) 0
AgCl(s) 109.7
Al(s) 0
Al2O3(s) 1576.4
C(s,diamond) 2.9
C(s,graphite) 0
CH3Cl(g) 58.6
CH3OH(l) 166.2
CH3COOH(l) 392.5
CH4(g) 50.79
C2H2(g) +209
C2H4(g) +68.12
C2H6(g) 32.9
C2H5OH(l) 174.8
C8H18(l) +17.3
CO(g) 137.3
CO2(g) 394.4
CO(NH2)2(s) 197.2
Ca(s) 0
CaCO3(s) 1128.8
CaCl2(s) 750.2
CaO(s) 604.2
Ca(OH)2(s) 896.76

CaSO4(s) 1320.3
1435.2

1795.7
CaSO42H2O(s)
Cl2(g) 0
Fe(s) 0
Fe2O3(s) 741.0
H2(g) 0
H2O(g) 228.6
H2O(l) 237.2
HCl(g) 95.27
HNO3(l) 79.91
H2SO4(l) 689.9
Hg(l) 0
Hg(g) +31.8
K(s) 0
KCl(s) 408.3

K2SO4(s) 1316.4
N2(g) 0
NH3(g) 16.7
NH4Cl(s) 203.9
NO(g) +86.69
NO2(g) +51.84
N2O(g) +103.6
N2O4(g) +98.28
Na(s) 0
Na2CO3(s) 1048
NaHCO3(s) 851.9
NaCl(s) 384.0
NaOH(s) 382
Na2SO4(s) 1266.8
O2(g) 0
PbO(s) 189.3
S(s,rhombic) 0

SO2(g) 300.4
SO3(g) 370.4

WORKEDEXAMPLE8.13

Calculating from

Ethanol,C2H5OH,ismadefromgrainbyfermentationandcanbeaddedtopetroltoproducea
productcalledgasoholorE10.Whatis ofthecombustionofliquidethanoltogiveCO2(g)
andH2O(g)?

AnalysisWecanusetheequation:

tocalculatethestandardGibbsenergychangeforthereaction.WewillneedthestandardGibbs
energychangesofformationforeachreactantandproduct.Thesedatacanbefoundintable8.6
onthenextpage.

Solution

First,weneedthebalancedequationforthereaction:

Aswith , foranyelementinitsstandardstateis0.Therefore,usingthedatafrom
table8.6:

ThestandardGibbsenergychangeforthereactionis1299.8kJmol1.

Isouranswerreasonable?

There'snoquickwaytoestimatetheanswer,althoughwecouldcalculate from and

followingthemethodusedinworkedexample8.12forathoroughcheck.Weknowthat
ethanolisquiteflammableunderstandardconditions,soweexpectthiscombustionreactionto
proceedspontaneously.ThelargenegativestandardGibbsenergychangemakessense.

PRACTICEEXERCISE8.15

Calculate forthefollowingreactions
usingthedataintable8.6.
 (a)2NO(g)+O2(g)2NO2(g)
(b)Ca(OH2)(s)+2HCl(g)CaCl2(s)+
2H2O(g)

Gibbsenergyandwork
Oneofthechiefusesofspontaneouschemicalreactionsistheproductionofusefulwork.Forexample,fuels
areburnedinpetrolanddieselenginestopowercarsandheavymachinery,andchemicalreactionsin
batteriespowereverythingfrommobilephonestolaptopcomputers.

Whenchemicalreactionsoccur,however,theirenergyisnotalwaysharnessedtodowork.Forinstance,if
petrolisburnedinanopendish,theenergyevolvedislostentirelyasheatandnousefulworkis
accomplished.Engineers,therefore,seekwaystocaptureasmuchenergyaspossibleintheformofwork.
Oneoftheirprimarygoalsistomaximisetheefficiencywithwhichchemicalenergyisconvertedtowork
andtominimisetheamountofenergytransferredunproductivelytothesurroundingsasheat.

Themaximumconversionofchemicalenergytoworkoccursifareactioniscarriedoutunderconditions
thataresaidtobethermodynamicallyreversible.Aprocessisdefinedasthermodynamicallyreversibleifits
drivingforceisopposedbyanotherforcethatisjustslightlyweaker,sothattheslightestincreaseinthe
opposingforcewillcausethedirectionofthechangetobereversed.Anexampleofanearlyreversible
processisillustratedinfigure8.24,wherewehaveacompressedgasinacylinderpushingagainstapiston
thatisheldinplacebyliquidwateraboveit.Ifawatermoleculeevaporates,theexternalpressuredrops
slightlyandthegascanexpandjustabit.Gradually,asonewatermoleculeafteranotherevaporates,thegas
insidethecylinderslowlyexpands.Atanytime,however,theprocesscanbereversedbythecondensation
ofawatermolecule.

FIGURE8.24Areversibleexpansionofagas.Aswatermoleculesevaporateoneatatime,theexternalpressure
graduallydecreasesandthegasslowlyexpands.Theprocesswouldbereversedifamoleculeof
waterweretocondenseintotheliquid.Theabilityoftheexpansiontobereversedbytheslightest
increaseintheopposingpressureiswhatmakesthisareversibleprocess.

Aswewillseeinchapter9,thermodynamicreversibilityimpliesthatthesystemisveryclosetoequilibrium
(astateinwhichthereisnodrivingforceforchemicalorphysicalchange)ateverystageofaprocess.While
wesometimessaythatareactionsuchasdissociationofaweakacidinwater(chapter11)isreversible,
simplybecauseitrunsinboththeforwardandreversedirections,wecannotsaythereactionis
thermodynamicallyreversibleunlesstheconcentrationsareonlyinfinitesimallydifferentfromtheir
equilibriumvaluesasthereactionoccurs.
Althoughwecouldobtainthemaximumworkbycarryingoutachangereversibly,athermodynamically
reversibleprocessrequiressomanystepsthatitproceedsatanextremelyslowspeed.Iftheworkcannotbe
doneatareasonablerate,itisoflittlevaluetous.Ourgoal,then,istoapproachthermodynamicreversibility
formaximumefficiency,buttocarryoutthechangeatapacethatwilldeliverworkatacceptablerates.

Therelationshipofusefulworktothermodynamicreversibilitywasillustratedearlier(section8.3,p.299)in
ourdiscussionofthedischargeofacarbattery.Recallthat,whenthebatteryisshortcircuitedwithaheavy
spanner,noworkisdoneandalltheenergyappearsasheat.Inthiscase,thereisnothingopposingthe
discharge,anditoccursinthemostthermodynamicallyirreversiblemannerpossible.However,whenthe
currentispassedthroughasmallelectricmotor,themotoritselfoffersresistancetothepassageofthe
electricityandthedischargetakesplaceslowly.Inthisinstance,thedischargeoccursinamorenearly
thermodynamicallyreversiblemannerbecauseoftheoppositionprovidedbythemotor,andarelatively
largeamountoftheavailableenergyappearsintheformofworkaccomplishedbythemotor.

Theprecedingdiscussionleadsnaturallytothequestion,Istherealimittotheamountoftheavailable
energyinareactionthatcanbeharnessedasuseful(i.e.nonpV)work?Theanswertothisquestionisyes.
ThelimitistheGibbsenergyforthereaction.

ThemaximumamountofenergyproducedbyareactionthatcanbetheoreticallyharnessedasnonpVwork
isequaltorG.Thisistheenergythatneednotbelosttothesurroundingsasheatandis,therefore,
availabletobeusedforwork.Thus,bydeterminingthevalueofrG,wecanfindoutwhetheragiven
reactionwillbeaneffectivesourceofusefulenergy.Also,bycomparingtheactualamountofnonpVwork
derivedfromagivensystemwiththerGvaluesforthereactionsinvolved,wecanmeasuretheefficiency
ofthesystem.

WORKEDEXAMPLE8.14

CalculatingMaximumnonpVwork
CalculatethemaximumnonpVworkavailablefromtheoxidationof1moleofoctane,C8H18(l),
byoxygentogiveCO2(g)andH2O(l)at25Cand10 5Pa.

Analysis

ThemaximumnonpVworkisequaltorGforthereaction.Standardthermodynamicconditions
arespecified,soweneedtocalculate .

Solution

Firstweneedabalancedequationforthereaction.Forthecombustionof1moleofC8H18we
have:

Referringtotable8.6:
 Thus,at25Cand10 5Pa,wecanexpectnomorethan5307kJofnonpVworkfromthe
oxidationof1moleofC8H18.

Isouranswerreasonable?

Besuretocheckthealgebraicsignsofeachofthetermsinthecalculation.Thisisacombustion
reaction,sowewouldexpectittobespontaneousandhencehaveanegativerGvalue,whichit
does.

PRACTICEEXERCISE8.16
CalculatethemaximumnonpVworkthat
couldbeobtainedat25Cand10 5Pafrom
theoxidationof1.00moleofaluminiumby
O2(g)togiveAl2O3(s).(Aluminiumwasone
ofthecomponentsoftheboosterrocketthat
wasusedtolaunchtheworld'sfirstsuccessful
scramjetflightinAustralia.)

Gibbsenergyandequilibrium
Wehaveseenthat,whenthevalueofGforagivenchangeisnegative,thechangeoccursspontaneously.
WehavealsoseenthatachangeisnonspontaneouswhenGispositive.However,whenGisneither
positivenornegative,thechangeisneitherspontaneousnornonspontaneousthesystemisinastateof
equilibrium.ThisoccurswhenGisequalto0.Whenasystemisinastateofdynamicequilibriumat
constanttemperatureandpressure:

Let'sagainconsiderthefreezingofwateratp=1.01310 5Pa:

Below0C,Gforthischangeisnegativeandfreezingisspontaneous.Ontheotherhand,above0Cwe
findthatGispositiveandfreezingisnonspontaneous.Whenthetemperatureisexactly0C,G=0and
anicewatermixtureexistsinaconditionofequilibrium.Aslongasheatisnotaddedorremovedfromthe
system,neitheroverallfreezingnormeltingisspontaneousandtheiceandliquidwatercanexisttogether
indefinitely.Inthisstateofdynamicequilibrium,therateatwhichliquidwaterfreezestogiveiceisexactly
equaltotherateatwhichicemeltstogiveliquidwater.

WehaveidentifiedGasaquantitythatspecifiestheamountofnonpVworkavailablefromasystem.
SinceG=0atequilibrium,theamountofnonpVworkavailableis0also.Therefore,whenasystemisat
equilibrium,nononpVworkcanbeextractedfromit.Asanexample,wewillconsideragainthecommon
leadstoragebatterythatweusetostartacar.
Whenabatteryisfullycharged,therearevirtuallynoproductsofthedischargereactionpresent.The
chemicalreactants,however,arepresentinlargeamounts.Therefore,thetotalGibbsenergyofthereactants
farexceedsthetotalGibbsenergyofproductsand,since:

therGofthesystemhasalargenegativevalue.ThismeansthatalotofenergyisavailabletodononpV
work.Asthebatterydischarges,thereactantsareconvertedtoproductsandGproductsgetslargerwhile
GreactantsgetssmallersorGbecomeslessnegative,andlessenergyisavailabletodononpVwork.
Finally,thebatteryreachesequilibrium.Thetotalfreeenergiesofthereactantsandtheproductshave
becomeequal,so:

NofurthernonpVworkcanbeextractedandwesaythebatteryisflat.

Whenwehaveequilibriuminanysystem,weknowthatG=0.Foraphasechangesuchas
H2O(1)H2O(s),equilibriumcanbeestablishedonlyatoneparticulartemperatureatatmosphericpressure.
Inthisinstance,thattemperatureis0C.Above0C,onlyliquidwatercanexist,andbelow0Callthe
liquidwillfreezetogiveice.ThisyieldsaninterestingrelationshipbetweenHandSthatappliesnotonly
tophasechangesbutalsotochemicalreactions.SinceG=0:

Therefore:

and

Thus,ifweknowHforachemicalreactionorphasechangeandthetemperatureatwhichequilibriumis
established,wecancalculateS.Wecanalsorearrangetheaboveequationtogive:

Thus,ifweknowHandS,wecancalculatethetemperatureatwhichequilibriumwillbeestablished.

WORKEDEXAMPLE8.15

CalculatingtheEquilibriumTemperatureforaPhaseChange

ForthephasechangeBr2(l)Br2(g), kJmol1and Jmol1K1at25

C.AssumingthatHandSaretemperatureindependent,calculatetheapproximate
temperatureatwhichBr2(l)willbeinequilibriumwithBr2(g)at10 5Pa(i.e.thenormalboiling
pointofliquidBr2).

Analysis

Thetemperatureatwhichequilibriumexistsisgivenby:

Weareworkingunderstandardconditions(10 5Pa),sowecanuse and inthis

equation.Thatis:
 Solution

Substitutingthedatagivenintheproblem:

Noticethatwemustexpress inJmol1,notkJmol1,sotheunitscancelcorrectly.Itisalso
interestingthattheboilingpointwecalculateisquiteclosetothemeasurednormalboilingpoint
of58.8C.

Isouranswerreasonable?

equals30900and equalsapproximately100,whichmeansthetemperatureshouldbe
about310K.Ourvalue,332K,isnotfarfromthat,sotheanswerisreasonable.

PRACTICEEXERCISE8.17
Theenthalpyofvaporisationofmercuryis
60.7kJmol1.ForHg(l), Jmol1

K1forHg(g), Jmol1K1.
Estimatethenormalboilingpointofliquid
mercury.

Wecanalsousetheequation todeterminethetemperatureatwhichanonspontaneousreaction
firstbecomesspontaneous.Toillustratethis,considerthedecompositionofcalciumcarbonateat25C,
whichoccursaccordingtotheequation:

Usingthe and dataintables8.2and8.5,orthe dataintable8.6,wecancalculatethat

=130kJmol1forthisreactionat25C.Therefore,thereactionisnonspontaneousatthistemperature.
However,weshowedonp.327thatthespontaneityofreactionswithpositiveHandSvaluesdepends
onthetemperature,andthatsuchreactionsaregenerallyspontaneousathightemperature.Wecansubstitute
thevaluesof kJmol1and Jmol1K1forthisreactionintotheequation:

Thisshowsthatthesystemwillbeinequilibriumat1110Kunderstandardconditions(assumingthat
and areindependentoftemperature)andwillbespontaneousatanytemperaturegreaterthanthis.We
summarisethisinfigure8.25.

FIGURE8.25Diagramshowingtherelativevaluesof and forthedecompositionofcalcium

carbonate.Atlowtemperatures, (blueline)isgreaterthan (redline).Thismeansthat

willbepositiveundertheseconditionsandthereactionwillbenonspontaneous.Asthe

temperatureincreases,thevalueof increasesandeventually,atT=1.11103 K,

andthesystemisatequilibrium.Atanytemperaturegreaterthan1.11103 K,

islessthan .Undertheseconditions, willbenegativeandthedecomposition

reactionwillbespontaneous.

Inthischapter,wehaveshownthatGcanbeusedasthecriterionforspontaneityofachemicalreactionor
phasechange.Furthermore,wehaveshownthatthesignofGdependsonthesignsofbothHandS
andthat,whenG=0,thereisnodrivingforceforchemicalorphysicalchangeandthesystemisat
equilibrium.Wewillinvestigatechemicalequilibriuminmoredetailinthenextchapter,andwewillseehow
thevalueofrGmeasuredunderstandardconditions, ,isrelatedtotheextentofreaction.

ChemistryResearch

TheThermodynamicsofCrystallisationtheRoleinBiology

ProfessorKathrynMcGrath,VictoriaUniversityofWellington

Weoftentakeforgrantedmanythingsthatthebiologicalworldsetsupandmakesavailableto
us:theabilitytostanduprighttheabilitytochewourfoodthefactthateggsandseafoodcomein
thetidypackageofashellandthatbutterflieshaveintricatelyandbeautifullycolouredwings.

Organismsbuildbones,teeth,shellsandothersuchstructuresbyinitiatingandcontrollingthe
crystallisationofinorganicmaterials,suchascalciumcarbonateandsilica.Thisprocessisknown
asbiomineralisation.Theseorganismsusespecificmolecules,suchasproteinsandcarbohydrates
tomanipulatethecrystallisationenvironment,enablingprecisecontrolovertheformationof
biomineralsthesemoleculesalsobecomeanintegralcomponentofthefinalmaterials.

Atthefoundationofcrystallisationisthermodynamics,whichallowsustounderstandboththe
initialformationoftheseedcrystalanditssubsequentgrowthintothefinalmaterial.Aseed
crystalwillformonlyifthereactionconditionsareenergeticallyfavourable:thatis,iftheGibbs
energyofnucleationisnegative.Aswithallchemicalprocesses,anegativeGibbsenergymeans
thatthecrystallisationprocesswillbespontaneous.IfGispositive,thematerialwillremainin
solutionandnoseedcrystalwillform.

Oncetheseedcrystalhasformed,thermodynamicsmakesitpossibletopreciselycontrolthe
synthesisofthematerial.Forexample,let'slookatelectronmicrographsoftwoverydifferent
crystalsofcalciumcarbonate.

Bothelectronmicrographsrepresentthethermodynamicproductofthecrystallisationprocess
betweencalciumionsandcarbonateions.Thecrystalshowninfigure8.26wasgrownina
laboratorywithnosubsequentintervention.Thecrystalsshowninfigure8.27weregrownbya
seaurchinthatmanipulatedthecrystallisationthermodynamicsateverystage(seefigure8.27).
Thepreciselypatternedmaterial(seefigure8.28)madebytheseaurchinisseveraltimesstronger
thanthematerialmadeinthelaboratory.Itisalsomuchmoreresistanttofracture.

FIGURE8.26Electronmicrographimageofcalciumcarbonategrowninacrystallisationdishina
laboratory.
FIGURE8.27Electronmicrographsatvariousresolutionsofdifferentpartsofaseaurchinspine,
whichiscomposedofcalciumcarbonate.
 FIGURE8.28Crystalstructureofcalcite,i.e.theformofcalciumcarbonategrownbothinthe
laboratoryandbyseaurchins.Thespheresrepresentcalciumionswhiletheredtipped
triangularspeciesrepresentcarbonateions(theredendsareoxygenatomsandthe
greycentralpartsarecarbonatoms).

VictoriaUniversityofWellingtonisstudyingbiomineralisationintheseaurchinEvechinus
chloroticustodevelopabetterunderstandingofthefactorsthatallowanorganismtocontrolthe
thermodynamicsofcrystallisation.Tounderstandthiscontrol,weneedtoknowwhatis
controllingthesignofG.UnderlyingtheGibbsenergyofthecrystallisationprocessarethe
enthalpyofcrystallisation,H,andtheentropyofcrystallisation,S.Forformationofcalcium
carbonate,CaCO3(s),Sisnegativeasitchangesfromasolutionstatetoasolidstate.Thismeans
thatanincreaseintemperaturewillresultintheformationoffewercrystalsandeventualcessation
ofcrystallisation,sincetheinfluenceoftheentropyonthetotalGibbsenergyisviathetermT
S.

Thus,forcrystallisationtooccur,theenthalpyofcrystallisationmustbenegative.Energyis
releasedastheconstituentmoleculesorionscometogethertoformthecrystal(i.e.theprocessis
exothermic).Hence,manipulationofthegrowingcrystaloccursthroughtheorganism'sabilityto
locallymanipulatebothSandH,whichitdoeswiththehelpofkinetics(seechapter15).
 Sowhat'sthepointofallthis?

Growinghardspinesthatresistfracturingis,ofcourse,veryimportantfromtheseaurchin's
perspective,butthestudyofbiomineralisationisn'tjustabouttryingtounderstandhowasea
urchingrowsitsskeleton,orthatG=HTS!Itismuchmoreaboutwhatwecandoonce
weunderstandthedifferentcontrolfactorsthattheorganismuses.Imaginebeingabletotrigger
thebodytogrowanewtoothwhenitlosesonenomoremushyfoodinourolderyears.Or
beingabletomakeopticalfilters(photoniccrystals)thatcanbetriggeredtochangetheexact
wavelengthsbeingfiltered.Orgeneratingamaterialthathasalltheincrediblechemicalfeaturesof
ahightemperaturesemiconductor,butthatisstrong,lightweight,mouldableanddurablebecause
ofitsspecificallydesignedthreedimensionalstructure,ratherthanbeingthedense,brittlematerial
wecurrentlyhavetoworkwith.Finelytunedmanipulationofcrystallisationcrystal
engineeringorcrystaltectonics,asitisknownthatcanmakematerialswithspecificchemical
andphysicalcharacteristicsliesopenandachievable,butfirstyouhavetounderstand
thermodynamics!

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
IntroductiontoChemicalThermodynamics
Aspontaneouschangeoccurswithoutoutsideassistance,whereasanonspontaneouschangerequires
continuoushelpandcanoccuronlyifitisaccompaniedby,andlinkedto,someotherspontaneous
event.

Thescienceofchemicalthermodynamicsallowsustopredictboththedirectionandextentof
spontaneouschemicalandphysicalchangeunderparticularconditions.

ThermodynamicDefinitions
Wecalltheobjectweareinterestedinthesystem,whichisenclosedbyaboundary.Everythingelse
intheuniverseisthesystem'ssurroundings.

ChemicalthermodynamicsusestheSIunitofenergy,workandheat,thejoule(J)orthekilojoule(kJ).
Manythermodynamicequationsrequirethetemperaturetobeexpressedinkelvin.

Gibbsenergy,G,isdefinedbytheequationG=HTS,whereHistheenthalpyofthesystem,Sisthe
entropyofthesystemandTisthethermodynamictemperature.WeuseGtosymbolisethechangein
Gibbsenergythatoccurswhenachemicalsystemchangesfromonestatetoanotherduetoareactionor
physicalchangeatconstanttemperatureandpressure.ThevalueofGallowsustodeterminewhether
aparticularchemicalreactionorphysicalchangeisspontaneousandhowfaritwillproceedtowards
completion.

TheFirstLawofThermodynamics
Theinternalenergyofasystem,U,isthesumofitsmolecularkineticandpotentialenergies.Itisan
extensiveproperty,andthechangeininternalenergy,U,forachemicalprocessisgivenbythe
equation:

Thevalueofthestatefunction,internalenergy,dependsonlyonthecurrentconditionorstateofthe
system.Temperatureisanintensivepropertythatdeterminesthedirectionofspontaneousheatflow.
Heat,q,isatransferofenergyfromanobjectatahightemperaturetooneatalowertemperatureand
canbedeterminedbymeasuringtemperaturechanges,T,usingtheequation:

whereCistheheatcapacityofthesystem:thatis,theheatneededtochangethetemperatureofthe
systemby1kelvin.Thespecificheat(c)ofapuresubstanceisdefinedas:

Heatcapacityisspecificheatmultipliedbymass.Heatcapacitycalculatedonapermolebasisiscalled
molarheatcapacity.Whenthemassandspecificheatofanobjectareknown,heatcanbecalculated
usingtheequation:

Heatsofreactionaremeasuredatconstantvolumeoratconstantpressure.Whenagasevolvesand
pushesagainsttheatmosphereorcausesapistontomoveinacylinder,pressurevolumeworkisbeing
done.Whenthevolumechange,V,occursatconstantopposingpressure,p,theassociatedpressure
volumeworkisgivenbyw=pV.Theenergyexpendedindoingthispressurevolumeworkcauses
heatsofreactionmeasuredatconstantvolume,q v,todiffernumericallyfromheatsmeasuredatconstant
pressure,q p.
Thefirstlawofthermodynamicsstatesthat:

Thealgebraicsignsforqandwarenegativewhenthesystemgivesheattoordoesworkonthe
surroundings.Thesignsarepositivewhenthesystemabsorbsheatorreceivesworkenergydonetoit.
Whenasystemhasrigidwalls,nopressurevolumeworkcanbedonetoorbytheatmospheresoU=
q v.Valuesofq varedeterminedusingabombcalorimeter.

Enthalpy
Whenasystemisunderconstantpressure(e.g.opentotheatmosphere),pressurevolumeworkis
possibleandanewthermodynamicpropertycalledenthalpy,H,canbedefined:

LikeU,absolutevaluesofHcannotbeeasilymeasuredorcalculated,butadifferenceinenthalpy
betweenreactantsandproductscanbedetermined.Theheatofreactionisnowcalledtheenthalpy
change,H.Underconstantpressure:

WhileHisastatefunction,itsvaluediffersfromthatofUbytheworkinvolvedininteractingwith
theatmospherewhenthechangeoccursatconstantatmosphericpressure.Ingeneral,thedifference
betweenUandHisquitesmall.

ExothermicreactionshavenegativevaluesofrHendothermicchangeshavepositivevalues.A
balancedchemicalequationthatincludesboththeenthalpychangeandthephysicalstatesofthe
substancesiscalledathermochemicalequation.Thesecanbeadded,reversed(reversingalsothesign
oftheenthalpychange)ormultipliedbyaconstantmultiplier(doingthesametotheenthalpychange).
Ifsubstancesarecancelledoradded,theymustbeinidenticalphysicalstates.

Thermochemicalequationscanbeaddedbecauseenthalpyisastatefunction.Valuesof canbe
determinedbythemanipulationofanycombinationofthermochemicalequationsthatadduptothe
finalnetequation.

Standardconditionsreferto10 5Paandanenthalpychangemeasuredundertheseconditionsatthe
specifiedtemperatureTiscalledthestandardenthalpyofreaction, .Thevalueof isa
functionoftheamountsofsubstancesinvolvedinthereaction.Iftheamountofreactantsisdoubled,the
standardenthalpyofthereactiondoubles.Thereisnostandardtemperature,butthermodynamicdata
areoftentabulatedat25C.

Theenthalpychangefortheformationof1moleofasubstanceunderstandardconditionsfromits
elementsintheirstandardstatesiscalledthestandardenthalpyofformation, ,anditisgenerally
giveninunitsofkilojoulespermole(kJmol1).Hess'slawofheatsummationispossiblebecause
enthalpyisastatefunction.Thevalueof forareactioncanbecalculatedasthesumofthe
valuesoftheproductsminusthesumofthe valuesofthereactants,eachmultipliedbythe
correspondingstoichiometriccoefficientintheequation.

Theenthalpychangeforthecompletecombustionof1moleofapuresubstanceunderstandard
conditionsiscalledthestandardenthalpyofcombustion, .

Thebondenthalpyistheenthalpychangeonbreaking1moleofaparticularchemicalbondtogive
electricallyneutralfragments.Thesumofallthebondenthalpiesinamoleculeistheatomisation
enthalpy,atH,and,onamolebasis,itcorrespondstotheenergyneededtobreak1moleofmolecules
intoindividualatoms.

Entropy
Spontaneityisassociatedwithstatisticalprobabilityspontaneousprocessestendtoproceedfromlower
probabilitytohigherprobabilitystates.Thethermodynamicquantityassociatedwiththeprobabilityofa
stateisentropy,S.Entropyisameasureofthenumberofenergeticallyequivalentwaysastatecanbe
realised.

TheSecondLawofThermodynamics
Thesecondlawofthermodynamicsstatesthattheentropyoftheuniverseincreaseswhenevera
spontaneouschangeoccurs.

Ingeneral,gaseshavemuchhigherentropiesthanliquids,whichhavesomewhathigherentropiesthan
solids.Entropyincreaseswithvolumeforagasandwiththetemperature.Duringachemicalreaction,
theentropytendstoincreaseifthenumberofmoleculesincreasesongoingfromreactantstoproducts.

TheThirdLawofThermodynamics
Thethirdlawofthermodynamicsstatesthattheentropyofapurecrystallinesubstanceisequalto0at
absolutezero(0K).Becauseweknowwherethezeropointisontheentropyscale,itispossibleto
measureabsoluteentropies.Standardentropies, ,arecalculatedat10 5Pa(table8.5)andcanbeused
tocalculate forchemicalreactions.

GibbsEnergyandReactionSpontaneity
GibbsenergyisdefinedasG=HTS.Achemicalorphysicalchangeatconstanttemperatureand
pressureisspontaneousonlyiftheGibbsenergyofthesystemdecreases(Gisnegative).WhenH
andShavethesamealgebraicsign,thetemperaturebecomesthecriticalfactorindetermining
spontaneity.

WhenGismeasuredat10 5Pa,itisthestandardGibbsenergychange, .Aswithenthalpy

changes,thestandardGibbsenergiesofformation, ,(table8.6)canbeusedtoobtain for
chemicalreactionsbyaHess'slawtypeofcalculation.

Foranysystem,thevalueofGisequaltothemaximumamountofenergythatcanbeobtainedinthe
formofusefulnonpVwork.Thismaximumworkcanbeobtainedonlyifthechangetakesplace
reversibly.Allrealchangesareirreversibleandwealwaysobtainlessworkthanistheoretically
availabletherestislostasheat.

Whenasystemreachesequilibrium,G=0andnousefulworkcanbeobtainedfromit.Atany
particularpressure,anequilibriumbetweentwophasesofasubstance(e.g.liquidsolidorsolid
vapour)canoccuratonlyonetemperature.Theentropychangecanbecalculatedas .The
temperatureatwhichtheequilibriumoccurscanbecalculatedfrom .

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Heatcapacityandspecificheat(section8.3)
Theequation:

(q=heat,C=heatcapacity,T=temperaturechange)canbeusedtocalculatetheheatofareaction.
Specificheat(c)isdefinedas:

Thermochemicalequations(section8.4)
Wecanusethermochemicalequationsforonesetofreactionstowriteathermochemicalequationfor
somenetreaction.

Hess'slaw(section8.4)
Hess'slawstatesthattheoverallenthalpychangeforareactionisthesameregardlessofhowitis
carriedout.Thisenablesustousestandardenthalpiesofformationtocalculatetheenthalpyofa
reaction.

and (sections8.4,8.7)

Standardenthalpiesofformationandstandardentropiescanbeusedtocalculate,respectively,
and forareaction.

Gasapredictorofspontaneity(section8.8)
IfrGforareactionisnegative,thereactionisspontaneousunderthedefinedconditions.

Calculating from and (section8.8)

valuescanbecalculatedfromvaluesof , andTthroughtheequation:

Using values(section8.8)

StandardGibbsenergyofformationvaluescanbeusedtocalculate forareaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Introductiontochemicalthermodynamics
8.1Whatistheoriginofthenamethermodynamics?
Thermodynamicdefinitions
8.2Whatisthenameofthethermalpropertythatcanhavevalueswitheachofthefollowingunits?
(a) Jg 1K1
(b)Jmol1K1
(c) JK1
8.3Whatisthedifferencebetweenanisolatedsystemandaclosedsystem?
8.4Whatisastatefunction?Givetwoexamples.
Thefirstlawofthermodynamics
8.5Whichkindofsubstanceneedsmoreenergytoundergoanincreaseof5C,somethingwithahigh
oralowspecificheat?Explain.
8.6Howdoheatcapacityandspecificheatdiffer?
8.7Whichkindofsubstanceexperiencesthelargerincreaseintemperaturewhenitabsorbs100J,
somethingwithahighoralowspecificheat?
8.8Ifthespecificheatvaluesintable8.1wereinunitsofkJkg 1K1,wouldthevaluesbenumerically
different?Explain.
8.9Ifanamountofheat,q,isappliedtoanobject,anditstemperaturechangesbyT,howmuchheat
mustbeappliedtochangethetemperatureby10T?
8.10Whattwopiecesofinformationarenecessarytodeterminetheheatcapacityofanobject?What
additionalpieceofinformationisnecessarytodetermineitsspecificheat?
8.11SupposeobjectAhastwicethespecificheatandtwicethemassofobjectB.Ifthesameamountof
heatisappliedtobothobjects,howwillthetemperaturechangeofAberelatedtothetemperature
changeinB?
8.12Writetheequationthatstatesthefirstlawofthermodynamics.Whatdoesthisstatementmeanin
termsofenergyexchangesbetweenasystemanditssurroundings?
8.13Ifasystemcontaininggasesexpandsandpushesbackapistonagainstaconstantopposing
pressure,whatequationdescribestheworkdoneonthesystem?
8.14Whatkindsofenergycontributetotheinternalenergyofasystem?
8.15Howisachangeintheinternalenergydefinedintermsoftheinitialandfinalinternalenergies?
8.16Statethefirstlawofthermodynamicsinwords.Whatequationdefinesthechangeintheinternal
energyintermsofheatandwork?Definethemeaningofthesymbols,includingthesignificance
oftheiralgebraicsigns.
8.17Whichquantitiesinthestatementofthefirstlawofthermodynamicsarestatefunctionsandwhich
arenot?
8.18WhataretheunitsofpVifpressureisexpressedinpascalsandvolumeisexpressedincubic
metres?
8.19HowarerUandrHrelatedtoeachother?
8.20WhenarerUandrHnumericallyequaltoeachother?
8.21Ifasystemdoes45Jofworkandreceives28Jofheat,whatisthevalueofUforthischange?
8.22Ifasystemabsorbs48Jofheatanddoes22Jofwork,whatisthevalueofUforthischange?
Enthalpy
8.23Howisenthalpydefined?
8.24WhatequationdefinesHingeneralterms?Howisthisexpressedwhenthesysteminvolvesa
chemicalreaction?Ingeneral,whyarechemistsandbiologistsmoreinterestedinvaluesofH
thanU?
8.25WhatisthesignofHforanexothermicchange?
8.26Whatdistinguishesathermochemicalequationfromanordinarychemicalequation?
8.27Inathermochemicalequation,whatdothecoefficientsrepresentintermsoftheamountsofthe
reactantsandproducts?
8.28Whyarefractionalcoefficientspermittedinabalancedthermochemicalequation?Ifa
thermochemicalequationhasacoefficientof foraformula,whatdoesitsignify?
8.29WhatfundamentalfactaboutHmakesHess'slawpossible?
8.30Whattwoconditionsmustbemetbyathermochemicalequationsothatitsstandardenthalpy
changecanbegiventhesymbol ?

8.31WhatisHess'slawexpressedintermsofstandardenthalpiesofformation?
8.32WriteHess'slawintermsofstandardenthalpiesofcombustion.
Entropy
8.33Whatisentropy?
8.34Willtheentropychangeforeachofthefollowingbepositiveornegative?
(a)Moisturecondensesontheoutsideofacoldglass.
(b)Raindropsforminacloud.
(c)Airispumpedintoatyre.
(d)Frostformsonthewindscreenofyourcar.
(e)Sugardissolvesincoffee.
8.35Onthebasisofourdefinitionofentropy,suggestwhyentropyisastatefunction.
8.36Howcanyouestimatetheprobabilityofastateofthesystem?
Thesecondlawofthermodynamics
8.37Statethesecondlawofthermodynamics.
8.38Inanimatedcartoons,visualeffectsareoftencreated(foramusement)thatshoweventsthat
ordinarilydon'toccurinreallifebecausetheyareaccompaniedbyhugeentropydecreases.Can
youthinkofanexampleofthis?Explainwhythereisanentropydecreaseinyourexample.
8.39Howcanaprocesshaveanegativeentropychangeforthesystemandstillbespontaneous?
Thethirdlawofthermodynamics
8.40Whatisthethirdlawofthermodynamics?
8.41Wouldyouexpecttheentropyofanalloy(asolutionoftwometals)tobe0at0K?Explainyour
answer.
8.42Whydoesentropyincreasewithincreasingtemperature?
8.43DoesS=0at0Kforglass?Explain.
Gibbsenergyandreactionspontaneity
8.44Whatisaspontaneouschange?
8.45Listfivechangesthatyouhaveencounteredrecentlythatoccurredspontaneously.Listfive
changesthatarenonspontaneousthatyouhavecausedtooccur.
8.46Howdotheprobabilitiesoftheinitialandfinalstatesinaprocessaffectthespontaneityofthe
process?
8.47Aninstantcoldpackpurchasedinapharmacycontainsapacketofsolidammoniumnitrate,
NH4NO3,surroundedbyapouchofwater.WhenthepacketofNH4NO3isbroken,thesolid
dissolvesinwaterandthemixturecoolsbecausethesolutionprocessforNH4NO3inwateris
endothermic.Explain,intermsofwhathappenstothemoleculesandions,whythismixingoccurs
spontaneously.
8.48WhatistheequationexpressingthechangeintheGibbsenergyforareactionoccurringat
constanttemperatureandpressure?
8.49Foreachofthefollowingconditions,stateintermsofthealgebraicsignsofHandSthe
circumstancesunderwhichachangewillbespontaneous.
(a)atalltemperatures
(b)atlowtemperaturesbutnotathightemperatures
(c)athightemperaturesbutnotatlowtemperatures
8.50Underwhatcircumstanceswillachangebenonspontaneousregardlessofthetemperature?
8.51Isitpossibletorunacombustionreactioninreverse,sothatfuelandoxygenareproducedfrom
carbondioxideandwater?
8.52HowisGibbsenergyrelatedtousefulwork?
8.53Whatisathermodynamicallyreversibleprocess?Howistheamountofworkobtainedfroma
changerelatedtothermodynamicreversibility?
8.54Howistherateatwhichenergyiswithdrawnfromasystemrelatedtotheamountofthatenergy
thatcanappearasusefulwork?
8.55Whyarereal,observablechangesnotconsideredtobethermodynamicallyreversibleprocesses?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
8.56Acertainsystemabsorbs300Jofheatandhas700Jofworkdoneonit.WhatisthevalueofUforthechange?Is
theoverallchangeexothermicorendothermic?
8.57ThevalueofUforacertainchangeis1455J.Duringthechange,thesystemabsorbs812Jofheat.Didthesystem
dowork,orwasworkdoneonthesystem?Howmuchwork,expressedinjoules,wasinvolved?
8.58Howmuchheatmustberemovedfrom175gofwatertoloweritstemperaturefrom25.0Cto15.0C?
8.59Howmuchheatisneededtobring1.0kgofwaterfrom25Cto99C(comparabletomakingfourcupsofcoffee)?
8.60Howmuchheatisneededtoincreasethetemperatureof15.0gofFefrom20.0Cto40.0C?
8.61If250Jisaddedto30.0gofcopper,initiallyat22C,whatisitsfinaltemperature?
8.62A5.00gmassofametalwasheatedto100Candthenplungedinto100gofwaterat24.0C.Thetemperatureof
theresultingmixturewas28.0C.
(a)Howmuchheatdidthewaterabsorb?
(b)Howmuchheatdidthemetallose?
(c)Whatistheheatcapacityofthemetalsample?
(d)Whatisthespecificheatofthemetal?
8.63Asampleofcopperwasheatedto120Candthenplungedinto200gofwaterat25.00C.Thefinaltemperatureof
themixturewas26.50C.
(a)Howmuchheatwasabsorbedbythewater?
(b)Howmuchheatwaslostbythecoppersample?
(c)Whatwasthemassofthecoppersample?
8.64Calculatethemolarheatcapacityofiron.(Thespecificheatofironis0.4498Jg 1K1.)
8.65Avatof4.54kgofwaterunderwentadecreaseintemperaturefrom60.25Cto58.65C.Howmuchenergyleftthe
water?(Forthisrangeoftemperatures,usethevalueof4.18Jg 1K1forthespecificheatofwater.)
8.66Acontainerfilledwith2.46kgofwaterunderwentatemperaturechangefrom25.24Cto27.31C.Howmuchheat
didthewaterabsorb?
8.67Nitricacid,HNO3,reactswithpotassiumhydroxide,KOH,asfollows:

Astudentpoured55.0mLof1.3MHNO3intoacoffeecupcalorimeter,notedthatthetemperaturewas23.5Cand
added55.0mLof1.3MKOH,alsoat23.5C.Themixturewasstirredquicklywithathermometer,andits
temperatureroseto31.8C.Calculatetheenthalpyofreaction.Assumethatthespecificheatsofallsolutionsare4.18
Jg 1K1andthatalldensitiesare1.00gmL1.Calculatetheenthalpyofreactionpermoleofacid.
8.68Adilutesolutionofhydrochloricacidwithamassof610.29gandcontaining0.33183molofHClwasexactly
neutralisedinacalorimeterbythesodiumhydroxidein615.31gofacomparablydilutesolution.Thetemperature
increasedfrom16.784Cto20.610C.ThespecificheatoftheHClsolutionwas4.031Jg 1K1andthatofthe
NaOHsolutionwas4.046Jg 1K1.Theheatcapacityofthecalorimeterwas77.99JK1.Usethisinformationto
calculatetheenthalpychangeforthefollowingreaction:

WhatistheenthalpyofneutralisationpermoleofHCl?Assumethattheoriginalsolutionsmadeindependent
contributionstothetotalheatcapacityofthesystemfollowingtheirmixing.
8.69A0.100molsampleofpropane,agasusedforcookinginmanyruralareas,wasplacedinaconstantpressurewith
excessoxygenandignited.Thereactionwas:

Theinitialtemperatureofthecalorimeterwas25.000Canditstotalheatcapacitywas97.1kJK1.Thereactionraised
thetemperatureofthecalorimeterto27.282C.
(a)Howmuchheatwasliberatedinthisreaction?
(b)Whatistheenthalpyofreactionofpropanewithoxygen?
8.70Toluene,C7H8,isusedinthemanufactureofexplosivessuchasTNT(trinitrotoluene).A1.500gsampleofliquid
toluenewasplacedinabombcalorimeteralongwithexcessoxygen.Whenthecombustionofthetoluenewas
initiated,thetemperatureofthecalorimeterrosefrom25.000Cto26.413C.Theproductsofthecombustionwere
CO2(g)andH2O(l),andtheheatcapacityofthecalorimeterwas45.06kJK1.Thereactionwas:
 CO2(g)andH2O(l),andtheheatcapacityofthecalorimeterwas45.06kJK1.Thereactionwas:

(a)Howmuchheatwasliberatedbythereaction?
(b)Howmuchheatwouldbeliberatedundersimilarconditionsif1.00moloftoluenewasburned?
8.71Onethermochemicalequationforthereactionofcarbonmonoxidewithoxygenis:

(a)Writethethermochemicalequationforthereactionusing2molofCO.
(b)(b)Whatis fortheformationof1molofCO2bythisreaction?

8.72Ammoniareactswithoxygenasfollows:

(a)Calculatetheenthalpychangeforthecombustionof1molofNH3.
(b)Writethethermochemicalequationforthereactioninwhich1molofH2Oisformed.
8.73Aluminiumandiron(III)oxide,Fe2O3,reacttoformaluminiumoxide,Al2O3,andiron.Foreachmoleofaluminium
used,426.9kJofenergyisreleasedunderstandardconditions.Writethethermochemicalequationthatshowsthe
consumptionof4molofAl.(Allofthesubstancesaresolids.)
8.74Liquidbenzene,C6H6,burnsinoxygentogivecarbondioxidegasandliquidwater(whenallproductsarereturnedto
25Cand10 5Pa).Thecombustionof1.00molofbenzeneliberates3271kJ.Writethethermochemicalequationfor
thecombustionof3.00molofliquidbenzene.
8.75Magnesiumburnsinairtoproduceabrightlightandisoftenusedinfireworksdisplays.Thecombustionof
magnesiumfollowsthethermochemicalequation:

Howmuchheatisliberatedbythecombustionof6.54gofmagnesium?
8.76Methanolisthefuelincannedheatcontainersthatareusedtoheatfoodsatcocktailparties.Thecombustionof
methanolfollowsthethermochemicalequation:

Whatistheenthalpychangeforthecombustionof46.0gofmethanol?
8.77Showhowtheequations:

canbemanipulatedtogive forthefollowingreaction:

8.78Wecangeneratehydrogenchloridebyheatingamixtureofsulfuricacidandpotassiumchlorideaccordingtothe
equation:

Calculate forthisreactionfromthefollowingthermochemicalequations:

8.79Calculate forthefollowingreaction,thepreparationofnitrousacid,HNO2,whichisunstable:

Usethefollowingthermochemicalequations:
8.80Bariumoxidereactswithsulfuricacidasfollows:

Calculate forthisreaction.Thefollowingthermochemicalequationscanbeused:

8.81Coppermetalcanbeobtainedbyheatingcopperoxide,CuO,inthepresenceofcarbonmonoxide,CO,accordingto
thefollowingreaction:

Calculate usingthefollowingthermochemicalequations:

8.82Calciumhydroxidereactswithhydrochloricacidaccordingtothefollowingequation:

Calculate inkilojoulesforthisreaction,usingthefollowingequationsasneeded:

8.83Giventhefollowingthermochemicalequations:

calculatethevalueof forthereaction:

8.84Giventhefollowingthermochemicalequations:

calculatethestandardenthalpyofformationofCuO(s).
8.85Giventhefollowingthermochemicalequations:

calculatethevalueof forthereaction:

8.86Giventhefollowingthermochemicalequations:
8.86Giventhefollowingthermochemicalequations:

calculate forthereaction:

8.87UsethefollowingthermochemicalequationstocalculatethestandardenthalpyofformationofMg(NO3)2(s).

8.88Giventhefollowingthermochemicalequations:

calculate forthereaction:

8.89Whichofthefollowingequationshasavalueof thatwouldproperlybelabelledas ?
(a)CaCO3(s)CaO(s)+CO2(g)
(b)

(c)2Cu(s)+O2(g)2CuO(s)
(d)2Fe(s)+O2(g)2FeO(s)
(e)

(f)

8.90Writethethermochemicalequations,includingvaluesof (fromtable8.2),fortheformationofeachofthe
followingcompoundsfromtheirelements,withallsubstancesintheirstandardstates.
(a)CH3COOH(l),aceticacid
(b)NaHCO3(s),sodiumbicarbonate
(c)CaSO42H2O(s),gypsum
(d)CO(NH2)2(s),urea
(e) ,plasterofParis

(f) CH3OH(l),methanol
8.91Usingthedataintable8.2,calculate inkilojoulesforeachofthefollowingreactions.
(a)2H2O2(l)2H2O(l)+O2(g)
(b)HCl(g)+NaOH(s)NaCl(s)+H2O(l)
(c)CH4(g)+Cl2(g)CH3Cl(g)+HCl(g)
(d)2NH3(g)+CO2(g)CO(NH2)2(s)+H2O(l)
8.92Writethethermochemicalequationsthatwouldbeassociatedwiththestandardenthalpyofformationofeachofthe
followingcompounds.
(a)HCl(g)
(b)NH4Cl(s)
 (b)NH4Cl(s)
(c)CH3COOH(l)
(d)Na2CO3(s)
8.93Sucrose,C H O ,hasa valueof5.6510 3kJmol1.Thesoleproductsofthecombustionofsucroseare
12 22 11
CO2(g)andH2O(l).Writethethermochemicalequationforthecombustionof1molofsucroseandcalculatethevalue
of forthiscompound.
8.94Thethermochemicalequationforthecombustionofethyne(acetylene)gas,C2H2(g),is:

Usingthedataintable8.2,determinethevalueof forethyne(acetylene)gas.
8.95Usethedataintable8.4tocalculatetheapproximateatomisationenthalpyofNH3.
8.96Thestandardenthalpyofformationofethanolvapour,C H OH(g),is235.3kJmol1.Usethedataintable8.3and
2 5

theaveragebondenthalpiesforCC,CHandOHbondstoestimatetheCObondenthalpyinthismolecule.
Thestructureofthemoleculeis:

8.97Thestandardenthalpyofformationofethene,C H (g),is+52.284kJmol1.CalculatetheC Cbondenthalpyinthis

2 4
molecule.
8.98Carbondisulfide,CS2,hastheLewisstructure:

ForCS2(g), kJmol1.Usethedataintable8.3tocalculatetheaverageC Sbondenthalpyinthis

molecule.
8.99Gaseoushydrogensulfide,H S(g),has KJmol1.Usethedataintable8.3tocalculatetheaverageS
2
Hbondenthalpyinthismolecule.
8.100ForSF (g), kJmol1.Usethedataintable8.3tocalculatetheaverageSFbondenthalpyinthis
6
molecule.
8.101Usetheresultsofquestion8.100andthedataintable8.2tocalculatethestandardenthalpyofformationofSF4(g).
Themeasuredvalueof forSF4(g)is718.4kJmol1.Whatisthepercentagedifferencebetweenyour
calculatedvalueof andtheexperimentallydeterminedvalue?
8.102Usethedataintables8.3and8.4toestimatethestandardenthalpyofformationofethyne(acetylene),HC C
H,inthegaseousstate.
8.103CalculatetheapproximateenthalpyofformationofCCl vapourat25Cand10 5Pa.
4
8.104Whichsubstanceshouldhavethemoreexothermicenthalpyofformation,CF4orCCl4?
8.105Wouldyouexpectthevalueof forbenzene,C6H6,calculatedfromtabulatedbondenthalpies,tobeveryclose
totheexperimentallymeasuredvalueof ?Justifyyouranswer.
8.106Usethedatafromtable8.2tocalculate foreachofthefollowingreactions.
(a)CaO(s)+CO2(g)CaCO3(s)
(b)C2H2(g)+2H2(g)C2H6(g)
(c)3CaO(s)+2Fe(s)3Ca(s)+Fe2O3(s)
(d)Ca(OH)2(s)CaO(s)+HO(l)
(e)2NaCl(s)+H2SO4(l)Na2SO4(s)+2HCl(g)
(f) 2C2H2(g)+5O2(g)4CO2(g)+2H2O(g)
 (f) 2C2H2(g)+5O2(g)4CO2(g)+2H2O(g)
(g)C2H2(g)+5N2O(g)2CO2(g)+H2O(s)5N2(g)
(h)Fe2O3(s)2Al(s)Al2O3(s)+Fe(s)
(i) NH4Cl(s)NH3(g)+HCl(g)
(j) Ag(s)+KCl(s)AgCl(s)+(K(s)
8.107Predictthealgebraicsignoftheentropychangeforeachofthefollowingreactions.
(a)PCl3(g)+Cl2(g)PCl5(g)
(b)SO2(g)+CaO(s)CaSO3(s)
(c)CO2(g)+H2O(l)H2CO3(aq)
(d)Ni(s)+2HCl(aq)H2(g)+NiCl2(aq)
(e)I2(s)I2(g)
(f) Br2(g)+3Cl2(g)2BrCl3(g)
(g)NH3(g)+HCl(g)NH4Cl(s)
(h)CaO(s)+H2O(l)Ca(OH)2(s)
8.108Calculate foreachofthefollowingreactionsfromthedataintable8.5.
(a)N2(g)+3H2(g)2NH3(g)
(b)CO(g)+2H2(g)CH3OH(l)
(c)2C2H6(g)+7O2(g)4CO2(g)+6H2O(g)
(d)Ca(OH)2(s)+H2SO4(l)CaSO4(s)+2H2O(l)
(e)S(s)+2N2O(g)SO2(g)+2N2(g)
(f)

(g)

(h)

(i) CaCO3(s)+H2SO4(l)CaSO4(s)+H2O(g)+CO2(g)
(j) NH3(g)+HCl(g)NH4Cl(s)
8.109Calculate foreachofthefollowingcompounds.
(a)C2H4(g)
(b)N2O(g)
(c)NaCl(s)
(d)CH3COOH(l)
(e)CaSO42H2O(s)
(f) Al2O3(s)
(g)CaCO3(s)
(h)N2O4(g)
(i)

(j) NH4Cl(s)
8.110Nitrogendioxide,NO2,anairpollutant,dissolvesinrainwatertoformadilutesolutionofnitricacid.Theequation
forthereactionis:

Calculate forthisreaction.

8.111Goodwinewillturntovinegarifitisleftexposedtoairbecausethealcoholisoxidisedtoaceticacid.Theequation
forthereactionis:
 Calculate forthisreaction.

8.112Aluminiumoxidisesrathereasilybutformsathin,protectivecoatingofAl2O3thatpreventsfurtheroxidationofthe
aluminiumbeneath.Usethedatafor (table8.2)and tocalculate forAl2O3(s).
8.113Calculate foreachofthefollowingreactions,usingthedataintable8.6.
(a)SO3(g)+H2O(l)H2SO4(l)
(b)2NH4Cl(s)+CaO(s)CaCl2(s)+H2O(l)+2NH3(g)
(c)CaSO4(s)+2HCl(g)CaCl2(s)+H2SO2(l)
(d)C2H4(g)+H2O(g)C2H5OH(l)
(e)Ca(s)+2H2SO4(l)CaSO4(s)+SO2(g)+2H2O(l)
(f) 2HCl(g)+CaO(s)CaCl2+H2O(g)
(g)H2SO4(l)+2NaCl(s)2HCl(g)+Na2SO4(s)
(h)3NO2(g)+H2O(l)2HNO3(l)+NO(g)
(i) 2AgCl(s)+Ca(s)CaCl2(s)+2Ag(s)
(j) NH3(g)+HCl(g)NH4Cl(s)
8.114PlasterofParis, ,reactswithliquidwatertoformgypsum,CaSO42H2O(s).Writeachemical
equationforthereactionandcalculate ,usingthedataintable8.6.

8.115Giventhefollowinginformation:

Calculate forthisreaction.

8.116Giventhesereactionsandtheir values:

calculatethevalueof forthereaction:

8.117GasoholorE10isamixtureofpetrolandethanol,C2H5OH.Calculatethemaximumworkthatcouldbeobtainedat
25Cand10 5Pabyburning1molofC2H5OH:

8.118Whatisthemaximumamountofusefulworkthatcouldtheoreticallybeobtainedat25Cand10 5Pafromthe

combustionof48.0gofnaturalgas,CH4(g),togiveCO2(g)andH2O(g)?
8.119Chloroform,CHCl3,wasformerlyusedasananaestheticandisnowbelievedtobeacarcinogen(cancercausing
agent).Ithasanenthalpyofvaporisation(vapH)of31.4kJmol1.Thechange,CHCl3(l)CHCl3(g),has
Jmol1K1.AtwhattemperaturedoweexpectCHCl3toboil(i.e.atwhattemperaturewillliquidand
vapourbeinequilibriumat10 5Pa)?
8.120Isooctane,animportantconstituentofpetrol,hasaboilingpointof99.3Candanenthalpyofvaporisationof37.7
kJmol1.WhatisSforthevaporisationof1molofisooctane?
8.121Acetone,(CH3)2CO,hasaboilingpointof56.2C.Thechange(CH3)2CO(l)(CH3)2CO(g)has kJ
mol1.Whatis forthischange?
 mol1.Whatis forthischange?
8.122Determinewhetherthefollowingreactionwillbespontaneous.Doweexpectappreciableamountsofproductsto
form?

8.123Whichofthefollowingunbalancedequationsrepresentareactionthatwouldbeexpectedtobespontaneousat25C
and10 5Pa?
(a)PbO(s)+NH3(g)Pb(s)+N2(g)+H2O(g)
(b)NaOH(s)+HCl(g)NaCl(s)+H2O(l)
(c)Al2O3(s)+Fe(s)Fe2O(s)+Al(s)
(d)2CH4(g)C2H6(g)+H2(g)
8.124Calculatethevalueof forthefollowingreactions,usingdataintables8.2and8.5.Assumethat and
areindependentoftemperature.
(a)C2H4(g)+H2(g)C2H6(g)
(b)5SO3(g)+2NH3(g)2NO(g)+5SO2(g)+3H2O(g)
8.125Howmuchworkisaccomplishedbythefollowingchemicalreactionifitoccursinsideabombcalorimeter?

Howmuchworkisdoneifthereactioniscarriedoutat10 5Pa,withallreactantsandproductsat25C?(For
C4H10(g), kJmol1.)

8.126Acylinderfittedwithapistoncontains5.00Lofagasatapressureof4105Pa.Theentireapparatusismaintained
ataconstanttemperatureof25C.Thepistonisreleasedandthegasexpandsuntilthepressureinsidethecylinder
equalstheatmosphericpressureoutside,whichis10 5Pa.Assumeidealgasbehaviourandcalculatetheamountof
workdonebythegasasitexpandsatconstanttemperature.
8.127Theexperimentdescribedinquestion8.126isrepeated,butthistimeaweight,whichexertsapressureof210 5Pa,
isplacedonthepiston.Whenthegasexpands,itspressuredropstothis210 5Papressure.Thentheweightis
removedandthegasisallowedtoexpandagaintoafinalpressureof10 5Pa.Throughoutbothexpansions,the
temperatureoftheapparatuswasheldataconstant25C.Calculatetheamountofworkdonebythegasineach
step.Howdoesthecombinedtotalamountofworkinthistwostepexpansioncomparewiththeamountofwork
donebythegasintheonestepexpansiondescribedinquestion8.96?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
8.128Abodyofwaterwithamassof750gchangedintemperaturefrom25.50Cto19.50C.
(a)Whatwouldhavetobedonetocausesuchachange?
(b)Howmuchenergyisinvolvedinthischange?
8.129Abarofhotironwithamassof1.000kgandatemperatureof100.00Cwasplungedintoaninsulatedvatofwater.The
massofthewaterwas2.000kg,anditsinitialtemperaturewas25.00C.Whatwasthetemperatureoftheresultingsystem
whenitstabilised?
8.130Sulfurtrioxidereactswithwatertoproducesulfuricacidaccordingtothefollowingequation:

Calculate forthereaction.

8.131Ironmetalcanbeobtainedfromironore,whichwecanassumeforthisquestiontobeFe2O3,byitsreactionwithhot
carbon:

Whatis forthisreaction?Isthereactionexothermicorendothermic?

8.132Intherecoveryofironfromironore,thereductionoftheoreisactuallyaccomplishedbyreactionsinvolvingcarbon
monoxide.Usethefollowingthermochemicalequations:

tocalculate forthereaction:

8.133Usetheresultsofquestion8.132andthedataintable8.2tocalculatethevalueof forFeO.
8.134Phosphorusburnsinairtogivetetraphosphorusdecaoxide:

Theproductcombineswithwatertogivephosphoricacid,H3PO4:

Usingtheseequations(andanyothersinthechapter,asneeded),writethethermochemicalequationfortheformationof1
molofH3PO4(l)fromtheelements,andcalculate .

8.135Theaminoacidglycine,H2NCH2COOH,isoneofthecompoundsusedbythebodytomakeproteins.Theequationforits
combustionis:

Foreachmoleofglycinethatburns,973.49kJofheatisliberated.Usethisinformationplusvaluesof forthe
productsofcombustiontocalculate forglycine.
8.136Calculate forthereaction:

usingthefollowingthermochemicalequations:

8.137Calculate forthefollowingreaction:

Usethefollowingthermochemicalequationsasneeded:
 Also,useanyotherequations,asneeded,alongwiththermodynamicdatafoundeitherinthischapterorinappendixA.
8.138Thevalueof forHBr(g)wasfirstevaluatedusingthefollowingstandardenthalpyvaluesobtainedexperimentally:

Usethisinformationtocalculatethevalueof forHBr(g).
8.139Thereactionforthemetabolismofsucrose,C12H22O11,inthebodyisthesameasforitscombustioninoxygentoyield
CO2(g)andH2O(l).Thestandardenthalpyofformationofsucroseis2230kJmol1.Usedataintable8.2tocalculatethe
amountofenergyreleasedbymetabolising28.4gofsucrose.
8.140Considerthefollowingthermochemicalequations:

(8.1)

(8.2)

(8.3)

Supposeequation1isreversedanddividedby2,equations2and3aremultipliedby ,andthenthethreeadjusted
equationsareadded.Whatisthenetreaction,andwhatisthevalueof forthenetreaction?

8.141Giventhefollowingthermochemicalequations:

calculate forthereaction:

8.142WhatisthealgebraicsignofrSforeachofthefollowingchanges?
(a) 2Ag +(aq)+CrO 2(aq)Ag CrO (s)
4 2 4
(b)NaCl(s)Na+(aq)+Cl(aq)
(c)NH(g)NH3(aq)
(d)naphthalene(g)naphthalene(s)
(e)Agasbeingcooledfrom40Cto25C
(f) Agasbeingcompressedatconstanttemperaturefrom4.0Lto2.0L
8.143ThereactionCl (g)+Br(g)2BrCl(g)hasaverysmallvaluefor (+11.6JK1).Why?
2

8.144Foraphasechangeatagivenpressure,whyisthereonlyonetemperatureatwhichtherecanbeanequilibriumbetweenthe
phases?
 phases?
8.145Theenthalpyofcombustion, ,ofoxalicacid,H2C2O4(s),is246.05kJmol1.Considerthefollowingdata:

Substance (kJmol1) (Jmol1K1)

C(s) 0 5.69
CO2(g) 393.5 213.6
H2(g) 0 130.6
H2O(l) 285.9 69.96
O2(g) 0 205.0
H2C2O4(s) ? 120.1

(a)Writethebalancedthermochemicalequationthatdescribesthecombustionof1molofoxalicacid.
(b)Writethebalancedthermochemicalequationthatdescribestheformationof1molofoxalicacid.
(c) Usetheinformationinthetableandyourequationsinand(b)tocalculate foroxalicacid.
(d)Calculate foroxalicacidand forthecombustionof1molofoxalicacid.
(e) (e)Calculate foroxalicacidand forthecombustionof1molofoxalicacid.
8.146Manybiochemicalreactionshavepositivevaluesfor andsoshouldnotbeexpectedtobespontaneous.Theyoccur,
however,becausetheyarechemicallycoupledwithotherreactionsthathavenegativevaluesof .Anexampleisthe
setofreactionsthatbeginsthesequenceofreactionsinvolvedinthemetabolismofglucose,asugar.Giventhesereactions

andtheircorresponding values:

calculate forthecoupledreaction:

8.147Cars,trucksandothermachinesthatusepetrolordieselenginesforpowerhavecoolingsystems.Intermsof
thermodynamics,whatmakesthesecoolingsystemsnecessary?
8.148Ethanol,C H OH,hasbeensuggestedasanalternativetopetrolasafuel.Inworkedexample8.13,wecalculated for
2 5
combustionof1molofC2H5OHinworkedexample8.14,wecalculated forcombustionof1molofoctane.Wewill
assumethatpetrolhasthesamepropertiesasoctane(oneofitsconstituents).ThedensityofC2H5OHis0.7893gmL1the
densityofoctane,C8H18,is0.7025gmL1.Calculatethemaximumworkthatcouldbeobtainedbyburning1Leachof
C2H5OHandC8H18.Onavolumebasis,whichisabetterfuel?Explainyouranswer.
8.149Usethedataintable8.3tocalculatethebondenthalpyinthenitrogenmoleculeandintheoxygenmolecule.
8.150Theenthalpyofvaporisationofcarbontetrachloride,CCl ,is29.9kJmol1.Usingthisinformationanddataintables8.3
4
and8.4,estimatethestandardenthalpyofformationofliquidCCl4.
8.151Ammoniumnitrate,NH4NO3,isawhite,crystallinesubstancemanufacturedonanenormousscale,foruseasafertiliser,
fromthereactionofanhydrousammoniawithconcentratednitricacid.However,ammoniumnitratemustbehandledwith
careasitispotentiallyexplosive.
(a) Thestandardenthalpyofformation( )ofNH4NO3(s)is365.56kJmol1.Writethebalancedchemical
equationtowhichthisvaluerefers.Specifythestandardstateforeachspeciesinthisreaction.
(b)WritethebalancedchemicalequationfortheformationofNH NO (s)fromNH (g)andHNO (l).Calculate
4 3 3 3
forthisreaction.
(c)Whengentlyheated,NH4NO3(s)candecomposeaccordingtothefollowingequation:

Calculate forthisreaction.
(d)Whenvigorouslyheated,NH4NO3candecomposeexplosivelyaccordingtothefollowingequation:
 (d)Whenvigorouslyheated,NH4NO3candecomposeexplosivelyaccordingtothefollowingequation:

Calculatetheenthalpychangeif1.000kgofNH4NO3decomposescompletelyaccordingtothisequationunder
standardconditions.
(e)Iftheenergyreleasedfromthereactionin(d)wasusedtoheat100kgofwater,initiallyat25.0C,whatwouldbe
thefinaltemperatureofthewater?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
atomisationenthalpy(atH) heatcapacity(C) standardenthalpyofreaction
bombcalorimeter heatofreactionatconstant
bondenthalpy pressure(qp)
standardentropy
boundary heatofreactionatconstant
calorimeter volume(qv) standardentropyofformation
chemicalthermodynamics Hess'slaw .Valuesof
combustionreaction intensiveproperty
internalenergy(U) standardentropyofreaction
endothermic
enthalpy(H) joule(J)
entropy(S) kilojoule(kJ) standardGibbsenergychange
exothermic molarheatcapacity
extensiveproperty secondlawof
firstlawofthermodynamics thermodynamics standardstates
Gibbsenergy(G) specificheat(c) statefunction
heat(q) specificheatcapacity(c) surroundings
spontaneous system
standardenthalpyof thermochemicalequation
combustion thermodynamictemperature
thirdlawofthermodynamics
standardenthalpyofformation universe
work(w)

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CHAPTER

9 ChemicalEquilibria
TheEarth'soceansareextremelycomplexchemicalsystems,comprisingvastquantitiesofdissolved
inorganicsalts,dissolvedorganicmatteranddissolvedgases.Ofthegases,carbondioxideisveryimportant
becauseitprovidesasourceofcarbonateionsforthegrowthofcoral,theexoskeletonofwhichiscomposed
ofcalciumcarbonate.Therateatwhichcoralreefsgrowthereforedependscriticallyontheamountof
dissolvedcarbondioxideintheocean,andanyprocesswhichaltersthisamountwillaffectcoralreefs.

WeknowthatcarbondioxidelevelsintheEarth'satmospherearecurrentlyincreasingandthepHofthe
Earth'soceansisdecreasing.ItisalsobecomingincreasinglyapparentthattheEarth'saveragetemperatureis
rising.Allofthesefactorscaninfluencethechemicalequilibriumbetweensolidanddissolvedcalcium
carbonateintheoceans,therebypotentiallyputtingcoralreefs,suchastheGreatBarrierReef,atrisk.
 Thischapterwillintroducetheconceptofchemicalequilibrium,thefactorsthatcanaffectthebehaviourof
chemicalsystemsatequilibriumandhowasysteminwhichequilibriumhasbeenperturbedmustrespondto
reestablishequilibrium.Anunderstandingofchemicalequilibriumisnecessaryinallformsofchemistry,
andwewillstudyimportantapplicationsofchemicalequilibriumindetailinchapters10,11and12.

KEYTOPICS

9.1Chemicalequilibrium
9.2Theequilibriumconstant,K,andthereactionquotient,Q
9.3EquilibriumandGibbsenergy
9.4Howsystemsatequilibriumrespondtochange
9.5Equilibriumcalculations

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9.1ChemicalEquilibrium
Inchapters8,welearnedhowtousethevalueofGtopredictwhetheraparticularchemicalreaction
orphysicalchangewouldbespontaneousunderthespecifiedconditions.Wealsobrieflyintroducedthe
conceptofequilibriumandshowedthatasystemisatequilibriumwhenG=0undertheseconditions,
nononpVworkcanbeextractedfromthesystem,andthereisnodrivingforceforchemicalor
physicalchange.Inthischapter,wewilldeveloptheideaofequilibriumfurthermostimportantly,we
willshowthatequilibriainchemicalreactionscanbequantifiedusingtheequilibriumconstant,K,and
thatthisisrelatedtothethermodynamicfunctionsweencounteredinchapter8.

ItisimportanttorealisethatanegativevalueofGforaparticularchemicalreactionunderspecific
conditionstellsusonlythatspontaneouschemicalchangewilloccurintheforwarddirectionitdoes
notnecessarilymeanthatcompleteconversionofreactantstoproductswilloccur.Infact,many
chemicalreactionsproceedonlypartwaytocompletionandgiveamixtureofreactantsandproducts.
WewillillustratethisusingtheHaberBoschprocess,thecatalysedformationofgaseousammonia,
NH3,fromthereactionofnitrogengas,N2,andhydrogengas,H2:

Thestoichiometriccoefficientstellusthat:
N2(g)alwaysreactswithH2(g)ina1:3moleratio.
TheamountofNH3(g)formedinthisreactionistwicetheamountofN2(g)andtwothirdsthe
amountofH2(g)thathasreacted.

Wecannot,however,concludefromthebalancedchemicalequationthatmixing1moleofN2(g)with3
molesofH2(g)willproduce2molesofNH3(g).Ifwemixed1moleofN2with3molesofH2at
elevatedtemperatureandpressureoveracatalyst(theuncatalysedreactionisveryslow)andmonitored
thecompositionofthereactionmixtureovertime,wewouldindeedseetheconcentrationofNH3(g)
increaseandtheconcentrationsofN2(g)andH2(g)decreaseeventually,however,theconcentrationsof
N2(g),H2(g)andNH3(g)wouldstopchanging,andwewouldendupnotwithpureNH3(g)butwitha
mixtureofreactantsandproducts.Wesaythatthereactionmixturehascometochemicalequilibrium
andwedistinguishthisbyusingadoubleheadedarrow (calledanequilibriumarrow):

Theequilibriumarrowhighlightsaveryimportantpointachemicalreactioncanproceedinboththe
forwardandreversedirectionsatthesametime.Atequilibrium,N2andH2arestillreactingtogiveNH3,
andNH3isalsoreactingtogiveN2andH2,buttheratesoftheforwardandreversereactionsare
equal.Thismeansthattheconcentrationsofthereactantsandproductsinthereactionmixtureremain
constantandthereisnonetchangeintheoverallcompositionofthereactionmixture.Sinceboththe
forwardandreversereactionsarestilloccurring,wesaythatthesystemisinastateofdynamic
equilibrium.

Inachemicalequilibrium,thetermsreactantsandproductsdonothavetheusualsignificance
becausethereactionisproceedinginbothdirectionssimultaneously.Instead,weusereactantsand
productssimplytoidentifythesubstancesontheleftandrighthandsides,respectively,ofthe
equationfortheequilibrium.

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9.2TheEquilibriumConstant,K,andtheReaction
Quotient,Q
Aclassicexperimentthatdemonstratesmanyimportantconceptsofequilibriumisthedecompositionof
N2O4(g)(dinitrogentetroxide)togiveNO2(g)(nitrogendioxide)(figure9.1):

FIGURE9.1EquilibriummixturesofN2 O4 (g)andNO2 (g)atdifferenttemperatures.Inice(righthandside),

colourlessN2 O4 predominatesandthemixtureispale.Athightemperature(lefthandside),dark
brownNO2 predominates.Atroomtemperature(middle),thereisamixtureofthegases,withN2 O4
inthelargeramount.

Thisreactioniseasilymonitoredbyobservingthecolourofthereactionmixture.PureN2O4(g)is
colourless,whilepureNO2(g)isbrownasN2O4decomposes,themixturebecomesmoreandmore
brown.Figure9.2showshowtheconcentrationsofthetwogaseschangeovertimeaspureN2O4(g)is
convertedtoanequilibriummixtureofN2O4(g)andNO2(g).

FIGURE9.2Theapproachtoequilibrium.InthedecompositionofN2 O4 (g)intoNO2 (g),N2 O4 (g)N2 O4

2NO2 (g),theconcentrationsofN2 O4 andNO2 changerelativelyquicklyatfirst.Astimepasses,the
 concentrationschangemoreandmoreslowly.Whenequilibriumisreached,theconcentrationsof
N2 O4 andNO2 nolongerchangewithtimetheyremainconstant.Notethattheconcentration
changeofNO2 overthecourseofthereactionistwicetheconcentrationchangeofN2 O4 .

Supposewesetupthetwoexperimentsshowninfigure9.3atconstanttemperature.Inthefirst1litre
flask,weput0.0350molN2O4.SincenoNO2ispresent,someN2O4mustdecomposeforthemixtureto
reachequilibrium,sothereactionwillproceedintheforwarddirection(i.e.fromlefttoright).When
equilibriumisreached,wefindtheconcentrationofN2O4hasdroppedto0.0292molL1andthe
concentrationofNO2hasbecome0.0116molL1.

FIGURE9.3Reactionreversibilityfortheequilibrium

Thesameequilibriumcompositionisreachedfromeithertheforwardorreversedirection,provided
theoverallsystemcompositionisthesame.BecausepureNO2 isbrownandpureN2 O4 iscolourless,
theambercolouroftheequilibriummixtureindicatesthatbothspeciesarepresentatequilibrium.

Inthesecond1litreflaskweput0.0700molofNO2(preciselytheamountofNO2thatwouldformif
0.0350molofN2O4theamountplacedinthefirstflaskdecomposedcompletely).Inthissecond
flask,thereisnoN2O4presentinitially,soNO2moleculesmustcombine,followingthereversereaction
(righttoleft)shownabove,togiveN2O4.Whenwemeasuretheconcentrationsatequilibriuminthe
secondflask,wefind,onceagain,0.0292molL1ofN2O4and0.0116molL1ofNO2.(Inpractice,these
experimentsaredifficult,ifnotimpossible,tocarryout,becauseN2O4(g)andNO2(g)arealwaysin
equilibrium,sotheycannotbeobtainedabsolutelypure.)

Weseeherethatthesameequilibriumcompositionisreached,whetherwebeginwithpureNO2orpure
N2O4,aslongasthetotalamountofNandOtobedividedbetweenthesetwosubstancesisthesame.
Similarobservationsapplytootherchemicalsystemsaswell,whichleadstothefollowinggeneralisation:
Foragivenoverallsystemcompositionatconstanttemperature,wealwaysreachthesameequilibrium
concentrationswhetherequilibriumisapproachedfromtheforwardorreversedirection.

Foranyreactioninvolvingonlygasesorspeciesinsolution(generallyaqueous)inwhichamolesof
substanceAreactwithbmolesofsubstanceBtogivecmolesofsubstanceCanddmolesofsubstanceD:

thefollowingholdswhenequilibriumisestablished:
Kc iscalledtheequilibriumconstant(or,occasionally,theconcentrationbasedequilibriumconstant)and
theaboveexpressioniscalledtheequilibriumconstantexpression.Thesquarebracketsreferto
concentrationsinmolL1,and ,thestandardconcentration,equals1molL1.

Becauseeachconcentrationtermisdividedby1molL1,eachterminparenthesesisdimensionless,and
thismeansthatKc hasnounits.Althoughtheexpressiononp.347looksratherdaunting,youwillbe
pleasedtoknowthat,inpractice,itisusuallysimplified.Becausetheyarenumericallyequalto1,the
termsareoftenomittedhowever,itisstillunderstoodthateachtermisdimensionless.Thesubscripteis
alsogenerallyomitted,asitisimplicitthattheconcentrationsusedinanequilibriumconstantexpression
mustbeequilibriumconcentrations.Havingmadethesesimplifications,weobtainthemorecommon
versionoftheequilibriumconstantexpression:

Notethatwewillusethisformthroughoutthebook,andallequilibriumconstantswillbedimensionless.
Thisexpressionisderivedfromthebalancedchemicalequationasfollows:

Noticethattheproducts(thespeciestotherightoftheequilibriumarrow)alwaysappearonthetoplineof
theexpression(thenumerator),andthereactantsalwaysappearonthebottom(thedenominator).Each
reactantandproductisraisedtothepoweroftheappropriatestoichiometriccoefficient(a,b,cord)from
thebalancedchemicalequation(i.e.thecoefficientsbecometheexponents).Notethatwearenotrestricted
toreactionsinvolvingtwoproductsandtworeactantswesimplyincludeallgaseousoraqueousreactants
andproductsintheequilibriumconstantexpression.Forexample,theequilibriumconstantexpressionfor
thereactionintheexperimentonpp.3467:

is:

ThevalueofKc foraparticularreactiondependsonthetemperature,soitisimportantthatthetemperature
isalwaysspecifiedwhenKc isreported.TabulatedvaluesofKc generallyreferto25.0Cand
concentrationsinmolL1.

Table9.1givestheresultsoffourfurtherexperimentsusingdifferinginitialconcentrationsofN2O4(g)and
NO2(g).ThefinalcolumnshowsthatthevalueofKc isconstant(withinexperimentalerror).Wecan,
therefore,saythattheequilibriumconstantforthisreaction:
TABLE9.1 EquilibriummixturecompositionsforvariousinitialconcentrationsofNO2 (g)andN2 O4 (g)
Initialconcentration Equilibriumconcentration
 [N2O4](molL1) [NO2](molL1) [N2O4](molL1) [NO2](molL1)

0.0450 0 0.0384 0.0133

0.0150 0 0.0114 0.00724

0 0.0600 0.0247 0.0107

0 0.0500 0.0202 0.00964

ThevaluesofKc areequalwithinexperimentalerror.

is:

Similarly,ifweweretostudythereaction:

atdifferentinitialconcentrationsofH2(g),I2(g)andHI(g)at400C,wewouldfindthat,whenthesystem
cametoequilibrium:

Wecanapplytheequilibriumconstantexpressiontoanysystematequilibrium.Wecanalsowritean
expressionforsystemsthatarenotatequilibrium.Wecallthisthereactionquotient(Q).For:

wecanwritethereactionquotientexpression:

NotethattheexpressiontakesasimilarformtothatforKc ,andwehavemadethesamesimplificationsfor
Qc aswedidforKc .Qc andKc differinthat:
Kc involvesequilibriumconcentrationsandsoreferstoasystematequilibrium
Qc referstosystemsthatarenotnecessarilyatequilibrium.
Kc canhaveonlyonepositivevalueataparticulartemperature,whileQc canhaveanypositivevalue.

Itisimportanttorealisethatallchemicalsystemswilleventuallycometoequilibrium.Whenequilibriumis
established,Qc =Kc .InsystemswhereQc Kc ,acomparisonoftheirvaluescantellushowasystem
mustchangetoestablishequilibrium,asshowninfigure9.4.
 FIGURE9.4Howasystemmustchangetoestablishequilibrium.

IfQc >Kc ,thesystemreactstouseupproductsandgeneratemorereactants,therebydecreasingQc tothe

pointwhereitequalsKc thatis,thesystemisatequilibrium.IfQc <Kc ,theoppositeoccursthesystem
reactstouseupreactantsandformmoreproducts,therebyincreasingQc tothepointwhereitequalsKc ,
againmeaningthesystemisatequilibrium.Wewilldiscussthisinmoredetailinsection9.4

ThesubscriptcinbothQc andKc referstothefactthatweareexpressingthecompositionofthereaction

mixturesintermsofconcentration.Forequilibriainvolvinggases,wecanalsoexpressthecompositionof
theequilibriummixtureintermsofpartialpressure(p.226),ratherthanconcentration.Whenwedothis,
theequilibriumconstantexpressiontakestheform:

wherep A,p B,p Candp DaretheequilibriumpartialpressuresofA,B,CandD,respectively,and isthe

standardpressure.Because Pa,wecannotmakethesimplificationthatwemadeearlierfor
Kc as,inthiscase,the termsaffecttheactualvalueofKp.Therefore,expressionsforKpmustbewritten
infull,includingthe termswhenpressuresaremeasuredinPa.LikeKc ,Kphasnounits.

WORKEDEXAMPLE9.1

WritingExpressionsforKc

Interestisgrowinginthepotentialuseofhydrogenasanalternativefueltoreplacefossilfuels.
Currently,muchofthehydrogenproducedintheworldisderivedfrommethane,CH4,in
naturalgasusingtheforwardreactionoftheequilibrium:
 WritetheexpressionforKc forthisreaction.

Analysis

Towritetheequilibriumconstantexpression,weplacetheconcentrationsoftheproductsinthe
numeratorandtheconcentrationsofthereactantsinthedenominator,eachraisedtothevalue
oftheappropriatestoichiometriccoefficient.Asstatedearlier,itisusualtoignorethe terms
asthesedonotaffectthevalueofKc .

Solution

Theequilibriumconstantexpressionis:

Isouranswerreasonable?

Checktoseethatproductsareonthetoplineandthatreactantsareonthebottom.Alsocheck
thesuperscriptsandbesurethattheyarethesameasthoseinthebalancedchemicalequation.
Noticethatweomittheexponentwhenitisequalto1.

PRACTICEEXERCISE9.1
WritetheequilibriumconstantexpressionKc
foreachofthefollowingreactions.
(a)2H2(g)+O2(g) 2H2O(g)
(b)CH4(g)+2O2(g) CO2(g)+
2H2O(g)

WORKEDEXAMPLE9.2

WritingExpressionsforKp

Mostoftheworld'ssupplyofmethanol,CH3OH,isproducedbythefollowingreaction:

WritetheexpressionforKpforthisequilibrium.
 Analysis

ForKp,weusepartialpressuresintheequilibriumconstantexpression.Weputtheequilibrium
partialpressuresoftheproductsinthenumeratorandtheequilibriumpartialpressuresofthe
reactantsinthedenominator.Thecoefficientsintheequationbecomeexponentsofthe
pressures.BecauseweareworkinginSIunits,inwhich Pa,wemustexplicitly
divideeachtermby tocalculateKp.

Solution

TheexpressionforKpforthisreactionis:

Isouranswerreasonable?

Checktomakesureyouhavewrittentheexpressionintermsofproductsoverreactants,and
nottheotherwayaround.Checkeachsuperscriptagainstthecoefficientsinthebalanced
chemicalequation.

PRACTICEEXERCISE9.2
Usingpartialpressures,writetheequilibrium
constantexpressionforthereaction:

TheRelationshipBetweenKpandKc

Recallfromchapter6thatpressure(p)mayberelatedtoconcentration(c)throughtheidealgasequation:

whereVisvolume(inm3),nisamount,Risthegasconstant(8.314Jmol1K1),Tistemperature(inK)
andthepressureisinPa.

Wecanrearrangethisequationtogive:

wherecisinmolm3.ToobtainconcentrationsinthemoreusualunitsofmolL1,wemustmodifythis
expressiontogive:
(Thefactorof1000arisesfromthefactthat1m3=1000L.)Wecanusethisequationtoobtainthe
relationshipbetweenKpandKc foraparticularreaction.Knowingthatp=1000cRT,Kpcanbechangedto
Kc byreplacingeachpartialpressuretermintheexpressionforKpwiththeproduct1000cRT.Similarly,
because ,Kc canbechangedtoKpbysubstituting foreachconcentrationterm.
Thissoundslikealotofwork,anditis.Fortunately,thereisageneralequationderivedfromthese
relationshipsthatwecanusetomaketheseconversionssimpler:

Notethat,as ,thiscanalsobewrittenas:

Inthisequation,thevalueofn gisequaltothechangeintheamountofgasingoingfromthereactants
totheproducts:

Weusethecoefficientsofthebalancedequationforthereactiontocalculatethenumericalvalueofn g.
Forexample,intheequation:

thereare2molesofgaseousproductsand4molesofgaseousreactants.Therefore,forthisreaction,n g=
24=2.

Forsomereactions,thevalueofn gisequalto0.AnexampleisthedecompositionofHI:

Noticethatthereare2molesofgasoneachsideoftheequation.Thismeansthatn g=0.Because
raisedtothepowerof0isequalto1,Kp=Kc .Thiswillbethecaseforallreactionsinwhich
n g=0.

WORKEDEXAMPLE9.3

ConvertingFromKctoKp

At500C,thereactionbetweenN2andH2toformammonia:

hasKc =6.010 2.WhatisthenumericalvalueofKpforthisreaction?

Analysis

Theequationthatwewishtouseis:
Inthediscussiononthepreviouspage,wesawthatn g=2forthisreaction.Weusethis
equationwithtemperature,T,inkelvinandR=8.314Jmol1K1.

Solution

Beginbylistingthedata:

SubstitutingtheseintotheequationforKpgives:

Inthiscase,KphasanumericalvaluequitedifferentfromthatofKc .

Isouranswerreasonable?

Youshouldnote(and,indeed,proveforyourself)thatunderallreasonableconditionsof
temperature(above12K)theterm:

willbelessthan1whenn gisnegative.Thereforetheproduct:

willalwaysgiveananswerthatislessthanKc .Therefore,insituationswheren gisnegative,

wewouldalwaysexpectthevalueofKptobelessthanthatofKc .Ouranswerisinagreement
withthis.

PRACTICEEXERCISE9.3
Nitrousoxide,N2O,isagasusedasan
anaestheticitissometimescalledlaughing
gas.Thiscompoundhasastrongtendencyto
decomposeintonitrogenandoxygen
accordingtotheequation:

butthereactionissoslowthatthegasappears
tobestableatroomtemperature(25C).The
decompositionreactionhasKc =7.310 34at
25C.WhatisthevalueofKpforthis
reactionat25C?
WORKEDEXAMPLE9.4

CONVERTINGFromKptoKc

At25C,Kpforthereaction:

hasavalueof0.114.CalculatethevalueofKc forthisreaction.

Analysis

Theequationweneedis:

andn g=21=+1.

Solution

Tabulatingthedata,wehave:

SolvingtheequationforKc gives:

Substitutingvaluesintothisequationyields:

Asinworkedexample9.3,thereisasignificantdifferencebetweenthevaluesofKpandKc .

Isouranswerreasonable?

Inthiscase,youcanshowthat,providedthetemperatureisabove12K,theterm:

willbegreaterthan1whenn gispositive.Thereforetheproduct:

willalwaysgiveananswerthatisgreaterthanKc .Therefore,insituationswheren gis

positive,wewouldalwaysexpectthevalueofKptobegreaterthanthatofKc .Providingwe
 havemadenoarithmeticalerrors,ouranswerislikelytobecorrect.

PRACTICEEXERCISE9.4
Methanol,CH3OH,isapromisingfuelthat
canbesynthesisedfromcarbonmonoxide
andhydrogenaccordingtotheequation:

Kp=3.810 2forthisreactionat200C.Do
youexpectKptobelargerorsmallerthanKc ?
CalculatethevalueofKc atthistemperature.

Theexactthermodynamictreatmentofequilibriumusesactivities,ratherthanconcentrations,inthe
equilibriumexpression.Activitiesaredimensionlessquantitiesthattakeaccountofthefactthatneither
gasesingasmixturesnorspeciesinsolutionbehaveideallyatoms,moleculesandionsinthegasor
solutionphasetendtointeractwitheachother,withthemagnitudeoftheinteractionincreasingasthe
concentrationincreases.Activitiescan,therefore,bethoughtofaseffectiveconcentrationsand,asthey
aredimensionless,thisleadstoequilibriumconstantshavingnounits.Providingthatweworkatlowgas
pressuresorwithdilutesolutions,activitiesapproximateconcentrationstoanacceptabledegree.
Equilibriumconstantsobtainedusingactivities,ratherthanpressuresorconcentrations,areoftencalled
thermodynamicequilibriumconstants.

ManipulatingEquilibriumConstantExpressions
Sometimesitisusefultobeabletocombinechemicalequilibriatoobtaintheequationforsomeother
reactionofinterest.Indoingthis,weperformvariousoperationssuchasreversinganequation,
multiplyingthecoefficientsbysomefactorandaddingtheequationstogivethedesiredequation.Inour
discussionofthermochemistry,youlearnedhowsuchmanipulationsaffectHvalues.Somedifferent
rulesapplytoequilibriumconstantexpressions.

ChangingtheDirectionofanEquilibrium
Whenthedirectionofanequationisreversed,thenewequilibriumconstantisthereciprocalofthe
original.Asanexample,whenwereversetheequilibrium:

weobtain:

Theequilibriumconstantexpressionforthesecondreactionisthereciprocalofthatforthefirst,so
.
MultiplyingtheCoefficientsbyaFactor
Whenthecoefficientsinanequationaremultipliedbyafactor,theequilibriumconstantisraisedtoa
powerequaltothatfactor.Forexample,ifwemultiplythecoefficientsoftheequation:

by2,thisgives:

Comparingequilibriumconstantexpressions,weseethat .

AddingChemicalEquilibria
Whenchemicalequilibriaareadded,theirequilibriumconstantsaremultiplied.Forexample,supposewe
addthefollowingtwoequations:

Wehavenumberedtheequilibriumconstantsjusttodistinguishbetweenthem.Ifwemultiplythe
equilibriumconstantexpressionforKc1bythatforKc2,weobtaintheequilibriumconstantexpressionfor
Kc3:

Therefore,Kc3=Kc1Kc2.

PRACTICEEXERCISE9.5

At25C,Kc =7.010 25forthereaction:

WhatisthevalueofKc forthereaction

PRACTICEEXERCISE9.6
At25C,theequilibriumconstantsforthe
followingreactionsareasshown.
 UsethesedatatocalculateKc forthereaction:

TheMagnitudeoftheEquilibriumConstant
Becausetheconcentrationsoftheproductsarealwaysonthetoplineoftheequilibriumconstant
expressionKc ,thevalueoftheequilibriumconstantgivesusameasureofhowfarthereactionhas
proceededtowardscompletionwhenequilibriumisreached.Forexample,thereaction:

hasKc =9.110 80at25C.Thismeansthatwhenthereisanequilibriumbetweenthesegases:

BywritingKc asafraction, ,weseethatthetopline(numerator)oftheequilibriumconstant

expressionisenormouscomparedwiththebottomline(denominator),whichmeansthattheconcentration
ofH2OhastobeenormouscomparedwiththeconcentrationsofH2andO2.Atequilibrium,therefore,
mostofthehydrogenandoxygenatomsinthesystemarefoundinH2OandveryfewarepresentinH2
andO2.TheenormousvalueofKc tellsusthatthereactionbetweenH2andO2goesessentiallyto
completionandthattheproductsarestronglyfavouredatequilibrium.

ThereactionbetweenN2andO2togiveNO:

hasaverysmallequilibriumconstant:Kc =4.810 31at25C.Theequilibriumconstantexpressionfor

thisreactionis:

Since ,wecanwritethisas:

Herethebottomlineishugecomparedwiththetopline,sotheconcentrationsofN2andO2mustbevery
muchlargerthantheconcentrationofNOatequilibrium.Thismeansthat,inamixtureofN2andO2atthis
temperature,theamountofNOthatisformedisnegligible.Thereactionhardlyproceedsatalltowards
completionbeforeequilibriumisreached,sothereactantsarefavouredatequilibrium.

Therelationshipbetweentheequilibriumconstantandthepositionofequilibriumissummarisedinfigure
9.5.Considerthereaction:

WhenKc isverylarge(Kc >>1),thereisalargeamountofproductandverylittlereactantinthereaction

mixtureatequilibrium,sowesaythepositionofequilibriumliestotheright.WhenKc 1,similar
amountsofreactantandproductarepresentatequilibrium.WhenKc <<1,thereactionmixturecontainsa
largeamountofreactantatequilibriumandverylittleproduct,sowesaythepositionofequilibriumliesto
theleft.

FIGURE9.5ThemagnitudeofKcandthepositionofequilibrium.

Oneofthewaysthatwecanuseequilibriumconstantsistocomparetheextentstowhichtwoormore
reactionsproceedtocompletion.Takecareinmakingsuchcomparisons,however,because,unlesstheK
valuesaregreatlydifferent,thecomparisonisvalidonlyifbothreactionshavethesamenumberof
reactantandproductmoleculesappearingintheirbalancedchemicalequations.Notealsothatthe
magnitudeoftheequilibriumconstanttellsusnothingabouthowrapidlyasystemreachesequilibrium.For
example,wesawonp.354thatKc fortheformationofwaterfromH2andO2isenormous,yetamixture
ofH2andO2isstablealmostindefinitelyatroomtemperature.However,onceinitiatedbyaspark,the
reactionproceedsrapidlytocompletionwithexplosiveforce.

PRACTICEEXERCISE9.7
Whichofthefollowingreactionstendstoproceedfurthesttowards
completion?
(a)

(b)

(c)

EquilibriumConstantExpressionsforHeterogeneousSystems
Inahomogeneousreactionorahomogeneousequilibriumallofthereactantsandproductsarein
thesamephase.Equilibriaamonggasesarehomogeneousbecauseallgasesmixfreelywitheachother,so
asinglephaseexists.Therearealsomanyequilibriainwhichreactantsandproductsaredissolvedinthe
sameliquidphase.

Whenmorethanonephaseexistsinareactionmixture,wecallitaheterogeneousreaction.Acommon
exampleisthecombustionofwood,inwhichasolidfuelreactswithgaseousoxygen.Anotheristhe
thermaldecompositionofsodiumbicarbonate(bakingsoda),whichoccurswhenthecompoundis
sprinkledonafire:

Safetymindedcookskeepaboxofbakingsodanearbybecausethisreactionmakesitanexcellentfire
extinguisherforburningfatsoroil.Thefireissmotheredbytheproductsofthereaction.

Heterogeneousreactionsreachequilibriumjustashomogeneousreactionsdo.IfNaHCO3isplacedina
sealedcontainersothatnoCO2orH2Ocanescape,thegasesandsolidscometoaheterogeneous
equilibrium.

Whenwewritetheequilibriumconstantexpressionforthis,andinfactanyheterogeneousequilibrium,we
donotincludeconcentrationsofpuresolidsorpureliquids.Therefore,theequilibriumconstant
expressionbecomes:

Ifweconsiderthereversereaction:

theequilibriumconstantexpressionis:

Thereasonwedonotincludepuresolidsandpureliquidsisthattheconcentrationofapureliquidorsolid
isunchangeableatagiventemperature.Foranypureliquidorsolidatconstanttemperature,theratioof
amountofsubstancetovolumeofsubstanceisconstant.Forexample,at25.0Cand1.01310 5Pa,1
moleofNaHCO3willoccupyavolumeof38.9mLand2molesofNaHCO3willoccupytwicethis
volume,77.8mL,buttheratiooftheamounttovolume(i.e.themolarconcentration)remainsthesame
(figure9.6).
 FIGURE9.6Theconcentrationofasubstanceinthesolidstateisconstant.Doublingtheamountalsodoubles
thevolume,buttheratioofamounttovolumeremainsthesame.
ForNaHCO3,theconcentrationofthesolidis:

ThisistheconcentrationofNaHCO3inthesolid,regardlessofthesizeofthesolidsample.Inotherwords,
theconcentrationofNaHCO3(s)isconstant,providedthereissomeofitpresentinthereactionmixture.
EventhoughneitherNaHCO3(s)norNa2CO3(s)appearsintheequilibriumconstantexpressionforthe
reaction:

itisimportanttorealisethatsomeNaHCO3(s)andNa2CO3(s)mustbepresentinthereactionmixturein
orderforequilibriumtobeestablished.Inanyequilibrium,thepresenceofallreactantsandproductsinthe
balancedchemicalequationisnecessaryatalltimesafterthereactionisinitiatedinorderforthesystemto
reachequilibrium.

WORKEDEXAMPLE9.5

WritingtheEquilibriumConstantExpressionfora
HeterogeneousReaction
Theairpollutantsulfurdioxidecanberemovedfromagasmixturebypassingitovercalcium
oxide.Theequationforthisreactionis:
 WritetheequilibriumconstantexpressionforKc forthisreaction.

Analysis

Theconcentrationsofthetwosolids,CaOandCaSO3,areincorporatedintotheequilibrium
constant,Kc ,forthereaction.Theonlyconcentrationthatshouldappearintheequilibrium
constantexpressionisthatofSO2(g).

Solution

Theequilibriumconstantexpressionissimply:

Isouranswerreasonable?

Thereisnoeasywaytocheckthisresultwithouttestingitexperimentally,butthisequilibrium
constantexpressionistypicalforreactionsthatinvolvesolidsorliquids.Pureliquids,pure
solidsandthesolventsindilutesolutionsarebuiltintotheequilibriumconstantanddonot
appearintheequilibriumconstantexpression.

PRACTICEEXERCISE9.8
Writetheequilibriumconstantexpressionfor
eachofthefollowingheterogeneous
reactions.
(a)2Hg(l)+Cl2(g) Hg 2Cl2(s)
(b)NH3(g)+HCl(g) NH4Cl(s)
(c)Na(s)+H2O(l) NaOH(aq)+H2(g)
(d)Ag CrO (s) 2Ag +(aq)+
2 4
CrO42(aq)
(e)CaCO3(s)+H2O(l)+CO2(aq)
Ca2+(aq)+2HCO3(aq)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
9.3EquilibriumandGibbsEnergy
Inchapter8weintroducedtheconceptofGibbsenergy.Inthissection,wewilldetailtherelationship
betweenGibbsenergyandchemicalequilibrium.

GibbsEnergyDiagrams
Wehaveseeninchapter8thatthesignofGtellsusthedirectionofspontaneouschangeinachemicalor
physicalsystem,andinthischapterwehaveseenthattheequilibriumconstant,K,givesusameasureof
howfaraspontaneousprocesswillproceedtowardscompletion.Whatthenistherelationshipbetween
GibbsenergyandK?Toanswerthisquestion,wewillfirstconsiderphasechangesandthenlookatchemical
reactions.

PhaseChanges
InaphasechangesuchasH2O(l)H2O(s),equilibriumcanexistforagivenpressureonlyatoneparticular
temperatureforwateratapressureof1.01310 5Pa(atmosphericpressure),thistemperatureis0C,the
normalfreezingpoint.Atothertemperatures,thephasechangeproceedstocompletioninonedirectionor
theother.OnewaytogainabetterunderstandingofthisisbystudyingGibbsenergydiagrams,which
depicthowtheGibbsenergychangesasweproceedfromthereactantstotheproducts.

Letusconsiderthephasechange:

atthreedifferenttemperatures:below0C,at0Candabove0C.Weknow,fromexperiencethatbelow0
Cthisprocesswilloccurspontaneously,whileabove0Cthisprocesswillnotoccurinfact,thereverse
processwillbespontaneous.At0C,wewillobtainanequilibriummixtureoficeandwater.Whyisthis?
InspectionofthethreeGibbsenergydiagramsinfigure9.7,whichcorrespondtothesethreesituations,
providesananswer.EachdiagramshowshowtheGibbsenergy,G,ofthesystemvarieswiththe
compositionofthesystem,frompureliquidwaterontheleftofeachdiagramtopuresolidwater(ice)onthe
right.Ineachcase,GforthephasechangeH2O(l)H2O(s)isequaltoG(H2O,s)G(H2O,l).

FIGURE9.7Gibbsenergydiagrams(nottoscale)forthephasechangeH2 O(l) H2 O(s)at1.013105 Pa.The

horizontalaxisrepresentstheamountofH2 O(l)andH2 O(s)present.Attheleftofeachdiagramthe
systemconsistsentirelyofH2 O(l),whileattherightofeachdiagramonlyH2 O(s)ispresent.Thegreen
lineshowsthedirectionofdecreasingG,andhencespontaneouschange,ineachcase.

Below0C,weseethattheGibbsenergyoftheliquidishigherthanthatofthesolid.Youhavelearnedthat
aspontaneouschangeoccursiftheGibbsenergycandecrease.Therefore,thefirstdiagramtellsusthatthe
liquidphase,oranymixtureofliquidorsolid,below0Cfreezesuntilonlythesolidispresent.Thisis
becausetheGibbsenergydecreasescontinuouslyuntilalltheliquidhasfrozen.Atthispoint,Gis
minimised.Inotherwords,GforthereactionH2O(l)H2O(s)isnegativeatthistemperature.

Above0C,wehavetheoppositesituation.TheGibbsenergyofthesolidisgreaterthanthatoftheliquid.It
thereforedecreasesinthedirectionofH2O(s)H2O(l),anditcontinuestodropuntilallthesolidhas
melted.Thismeansthatice,oranymixtureoficeandliquidwater,above0Ccontinuestomeltuntilonly
theliquidispresent.Gforthemeltingoficeatthistemperatureisthereforenegative.

Aboveorbelow0C,thesystemisunabletoestablishanequilibriummixtureofliquidandsolid.Meltingor
freezingoccursspontaneouslyuntilonlyonephaseispresent.However,at0C,theGibbsenergiesofboth
H2O(l)andH2O(s)arethesame.Therefore,thereisnochangeinGibbsenergyifeithermeltingorfreezing
occurs,sothereisnodrivingforceforeitherchange.Therefore,aslongasasystemoficeandliquidwateris
insulatedfromwarmerorcoldersurroundings,anyparticularmixtureofthetwophasesisstableandastate
ofequilibriumexists.Rememberthatthisisadynamicequilibriumtheicemeltsandthewaterfreezes,but
bothprocessesoccuratthesamerate,sonooverallchangeisobserved.

ChemicalReactions
TheGibbsenergychangesthatoccurinmostchemicalreactionsaremorecomplexthanthoseinphase
changes.Asanexample,let'sstudyareactionyou'veseenbeforethedecompositionofN2O4intoNO2:

Inourpreviousdiscussionofchemicalequilibrium,wenotedthatequilibriuminthissystemcanbe
approachedfromeitherdirection,withthesameequilibriumconcentrationsbeingachievedprovidedwe
beginwiththesameoverallsystemcomposition.

Figure9.8showstheGibbsenergydiagramforthereaction.Noticethat,ingoingfromreactanttoproduct,
theGibbsenergyhasaminimum,incontrasttothediagramsinfigure9.7itdropsbelowthatofbothpure
N2O4andpureNO2.

FIGURE9.8GibbsenergydiagramforthedecompositionofN2 O4 (g).Theminimumonthecurveindicatesthe
compositionofthereactionmixtureatequilibrium.Because ispositive,thepositionof
equilibriumliesclosetothereactants.Notmuchproductformsbythetimethesystemreaches
equilibrium.

Whyisthis?Let'ssupposewestartwithpureN2O4(g)andallowthereactiontocometoequilibrium.Asthe
reactionproceeds,NO2(g)moleculesstarttoform,andtheymixspontaneouslywiththeremainingN2O4(g)
moleculessothatthereactionmixtureishomogeneousatalltimes.Thisspontaneousmixinghasan
associatedGibbsenergychange,mixG,thatisnegativeatallpossiblereactionmixturecompositionsthis
simplymeansthat,nomatterwhattheproportionsofNO2andN2O4areinthereactionmixture,thetwo
gasesalwaysmixspontaneouslyasthisleadstoanincreaseinentropyofthesystemrelativetotheunmixed
gases.Hence,thetotalGibbsenergychangeforthesystembecomestheGibbsenergychangeforthe
chemicalreactionplustheGibbsenergychangeofmixing.Surprisingly,itisthecontributionfrommixG
thatleadstotheminimumintheGibbsenergydiagram(figure9.9).

FIGURE9.9GibbsenergydiagramformixingA(g)andB(g)inthehypotheticalreactionA(g)B(g).Theminimum
correspondstoanequimolarmixtureofA(g)andB(g).

IftheNO2(g)moleculesformedinthereactiondidnotmixwiththeN2O4(g)molecules,wewouldfindthat
theGibbsenergydiagramwouldsimplybeastraightlinejoining with ,similartothat
shownontherightoffigure9.7(H2O(l)andH2O(s)aredifferentphasesandhencecannotmix).However,
whenweaddthecontributionfrommixG,wealwaysfindthataminimumexistsintheGibbsenergycurve,
withitspositiondependingprimarilyonthesignandmagnitudeof ,thestandardGibbsenergychange
forthereaction.

WesaidinthepreviouschapterthatG=0atequilibrium.Let'snowlookatthisstatementwithreferenceto
figure9.10.

FIGURE9.10GibbsenergydiagramforthedecompositionofN2 O4 (g).Gforanychangeincompositionofthe
reactionmixtureisgivenbyGfinalGinitial.

Again,letusimagineareactionmixturehavingthecompositionindicatedbypoint1onthecurveandsee
whathappenswhenthesystemchangestothecompositionindicatedbypoint2.rGforthischangeisG2
G1andisnegativethus,weexpectthesystematpoint1toundergoaspontaneousreactiontouseup
N2O4(g)andgivemoreNO2(g).Thereversereaction,wherethesystematpoint2changestogivethesystem
atpoint1doesnotoccurasrGforthischange,G1G2,ispositive.Similarly,wecanseethatthesystemat
point3changesspontaneouslytopoint4asrGforthischange,G4G3,isnegativeinotherwords,
NO2(g)isconsumedandN2O4(g)isproduced.Asweapproachtheminimuminthecurvefromeither
direction,rGforanysmallchangeincompositionofthereactionmixturestartsbecominglessnegative,
until,whenwereachtheminimum,rGforanyinfinitesimallysmallchangeincompositionofthereaction
mixturebecomes0,sothesystemisatequilibrium.Obviously,whenthesystemhasacomposition
correspondingtotheminimumintheGibbsenergydiagram,rGforanychangeincompositionispositive,
sonochangeincompositionoccurs.

ItisveryimportantthatyouappreciatethedifferencebetweenrGand Youwillnoticefromfigure
9.8that forthereactionN2O4(g)2NO2(g)ispositivesoyoumightaskwhythereactionproceedsin
theforwarddirectionatall.Toanswerthisquestion,weneedtorememberthat istheGibbsenergy
changefortheconversionofreactantsintheirstandardstatetoproductsintheirstandardstateinthis
case,thestandardstateisthepuregas,eachat .AsampleofN2O4(g)at reactsspontaneouslytogive
someNO2(g)however,thepressureofNO2(g)atequilibriumismuchlessthanp oosoN2O4(g)predominates
intheequilibriummixture.Amorefamiliarexampleisthevaporisationofwater,forwhich is+8.6kJ
mol1at25.0C.Youknowfromexperiencethatwaterevaporatesspontaneouslyat25.0Cinthiscase,the
positivevalueof simplymeansthatthepartialpressureofwaterneverreaches underthese
conditionswhenthesystemisatequilibrium.Similarly,anegativevalueof simplymeansthatthe
productsarepresentinalargeamountatequilibrium,buttherearealsosomereactantsintheequilibrium
mixture.Hence,wecanseethatthesignof tellsusaboutthecompositionofthereactionmixtureat
equilibrium shouldnotbeusedasacriterionofspontaneityexceptintheveryrarecasewhenthe
reactioniscarriedoutunderstandardconditions.ItistheoneofthemostimportantequationssignofrG
thattellsuswhetheraparticularchangeincompositionofthereactionmixtureisspontaneous.

Youmightalsoaskwhyboththeforwardandreversereactionsoccurspontaneouslyatequilibriumwhenthe
factthatrG=0mightsuggestthatnospontaneousreactionshouldoccur.Thisapparentcontradictionis
possiblymoreamatterofsemanticsthananythingelse.AlthoughitiscustomarytotalkofthevalueofrG
foraparticularreaction,itismorecorrect,andindeedprobablymoreinstructive,totalkofrGfora
particularchangeinthecompositionofthereactionmixture.WhenrGisnegative,itmeansthatthe
reactionmixtureundergoesaspontaneouschangesuchthatreactantsareusedupandmoreproductsare
formedinordertominimisetheGibbsenergyofthesystem.Likewise,thetermspontaneousreactioncan
beconfusingwhenanysystemisatdynamicequilibrium,theforwardandreversereactionsbothoccur
spontaneously,withtheirratesbeinggovernedbyboththeirrespectiveactivationenergiesandthe
temperature,aswewillseeinchapter15.However,thereisnospontaneouschangeinthecompositionofthe
reactionmixtureatequilibrium,andwearereferringtothiswhenwetalkaboutwhetheraparticular
reactionisspontaneous.

Theextenttowhichareactionproceedsisverysensitivetothemagnitudeof .Ifthe valuefora

reactionisreasonablylargeabout20kJmol1ormoreandpositive,almostnoobservablereaction
occursatroomtemperature.Ontheotherhand,thereactioneventuallygoesalmosttocompletionunderthe
sameconditionsif isbothlargeandnegative.Fromapracticalstandpoint,then,thesizeandsignof
indicatewhetheranobservablespontaneousreactionoccurs.

WORKEDEXAMPLE9.6

Using asapredictoroftheoutcomeofareaction

Wouldweexpecttobeabletoobserveformationofproductsinthefollowingreactionat25C?
 Analysis

Weneedtodeterminethemagnitudeandsignof forthereaction.If isreasonably

largeandpositive,thereactionwon'tbeobserved.Ifitisreasonablylargeandnegative,wecan
expecttoseethereactiongonearlytocompletion.

Solution

First,let'scalculate forthereactionusingthedataintable8.6onp.329.Theprocedureis
thesameasthatdiscussedonpp.3278.

Because islargeandpositive,weexpecttoobservethespontaneousformationofonly
extremelysmallamountsofproductsatthistemperature.

Isouranswerreasonable?

Besuretocheckthealgebraicsignsofeachterminthecalculation.

PRACTICEEXERCISE9.9
Usethedataintable8.6todeterminewhether
thereaction:

shouldproducemeasurableamountsofSO3(g)
at25C.

PRACTICEEXERCISE9.10
Usethedataintable8.6todeterminewhetherweshould
expecttoseetheformationofCaCO3(s)inthefollowing
reactionat25C:

TheRelationshipBetween andK
Intheprecedingdiscussion,welearnedinaqualitativewaythatthepositionofequilibriuminareactionis
determinedbythesignandmagnitudeof .Wealsolearnedthatthedirectioninwhichareaction
proceedsdependsonwherethesystemcompositionstandsrelativetotheminimumontheGibbsenergy
curve.Thus,thereactionproceedsspontaneouslyintheforwarddirectiononlyifitlowerstheGibbsenergy
(i.e.ifrGisnegative).

Quantitatively,therelationshipbetweenrGand isexpressedbythefollowingequation,whichis
derivedfromtheidealgasequation(chapter6,p.216):

whereRisthegasconstant(8.314Jmol1K1),TisthetemperatureinkelvinandlnQisthenatural
logarithmofthereactionquotient.Forgaseousreactions,Qpiscalculatedusingpartialpressuresexpressed
inPa,while,forreactionsinsolution,Qc iscalculatedfrommolarconcentrations.Thisequationallowsusto
predictthedirectionofthespontaneouschangeinareactionmixtureifweknow andthecomposition
ofthemixture,asillustratedinworkedexample9.7.

WORKEDEXAMPLE9.7

DeterminingtheDirectionofaSpontaneousReaction

Thereaction2NO2(g) N2O4(g)has at298K.Attheinstantof

mixingsamplesofthetwogases,thepartialpressureofNO2is0.2510 5Paandthepartial
pressureofN2O4is0.6010 5Pa.Howmustthecompositionofthereactionmixturechangeto
reachequilibrium?

Analysis

Sinceweknowthatreactionsproceedspontaneouslytowardsequilibrium,wearereallybeing
askedtodeterminewhetherthereactionproceedsspontaneouslyintheforwardorreverse
direction.WecancalculaterGfortheforwardreaction.IfrGisnegative,theforwardreaction
isspontaneous.However,ifthecalculatedrGispositive,thereversereactionisspontaneous.

Solution

First,weneedthecorrectformforthereactionquotientexpression.Expressedintermsofpartial
pressuresinPa,thisis:

Therefore,theequationweuseis:

Next,let'sassemblethedata:
 Noticethatwemustchangetheunitsof toJmol1sotheyarecompatiblewiththoseofR.
Substitutingquantitiesgives:

SincerGispositive,theforwardreactionisnonspontaneoussothereversereactionoccursto
reachequilibrium,thecompositionofthereactionmixturechangestoincreasetheamountofNO2
anddecreasetheamountofN2O4.

Isouranswerreasonable?

Thereisnosimplecheck.However,wecancheckthattheenergyunitsinbothtermsontheright
arethesame.Noticethatherewehavechangedtheunitsfor toJmol1,tomatchthoseof
R.Alsonoticethatthetemperatureisexpressedinkelvin,tomatchthetemperatureunitsinR.

PRACTICEEXERCISE9.11
Inwhichdirectionwillthereactiondescribed
inworkedexample9.7proceedtoreach
equilibriumifthepartialpressureofNO2is
0.6010 5PaandthepartialpressureofN2O4
is0.2510 5Pa?

Atthispoint,wehavetwoseeminglyseparatecriteriafordeterminingwhetherornotasystemisat
equilibrium.Weknowthat,whenrG=0foraninfinitesimalchangeincompositionofareactionmixture,
orwhenQ=Kforaparticularsetofreactionconditions,thesystemisatequilibrium.Wewillnowsubstitute
theseconditionsintotheequation:

IfrG=0,Q=K,andthus:

andtherefore:
Thisisoneofthemostimportantequationsinthermodynamics,ifnotallofchemistry.Itallowsustouse
tabulatedvaluesof tocalculatetheequilibriumconstantforaparticularreaction,and,conversely,we
canusemeasuredvaluesoftheequilibriumconstanttodetermine forareaction.Kinthereactionas
writtencorrespondstoKpforreactionsinvolvinggasesandKc forreactionsinvolvingspeciesinsolution.

Fromthisequationyoucanseethat,if forareactionislargeandnegative,lnKislargeandpositive,
andhenceKislargetheequilibriumpositionliestowardsproducts.Similarly,if islargeand
positive,lnKisnegative,andhenceKissmalltheequilibriumpositionliestowardsreactants.

WORKEDEXAMPLE9.8

EquilibriumConstants
Thebrownishhazeassociatedwithairpollutioniscausedbynitrogendioxide,NO2,aredbrown
gas(figure9.11).Nitricoxide,NO,isformedincarenginesandsomeofitescapesintotheair,
whereitisoxidisedtoNO2byoxygen:

FIGURE9.11Theatmosphericpollutantnitrogendioxide,NO2 ,producesacharacteristicbrownhaze.

ThevalueofKpforthisreactionis1.710 12at25C.Whatis forthereactionatthis

temperature?

Analysis

Wecancalculate fromthegivenvalueofKpusingthefollowingrelationship:

We'llneedthefollowingdata:
 Solution

Substitutingthesevaluesintotheequation,wehave:

Expressedinkilojoulespermole, .

Isouranswerreasonable?

ThevalueofKptellsusthatthepositionofequilibriumliesfartotheright,whichmeans
mustbelargeandnegative.Therefore,theanswer,70kJmol1,seemsreasonable.

WORKEDEXAMPLE9.9

EquilibriumConstants
Sulfurdioxide,whichissometimespresentinpollutedair,reactswithoxygenwhenitpassesover
thecatalystinacar'scatalyticconverter,producingtheveryacidicoxideSO3.

forthisreactionat25C.WhatisthevalueofKpatthis
temperature?

Analysis

Asinworkedexample9.8,weusetheequation:

Ourdataare:

TocalculateKp,itiseasiesttorearrangetheequationandsolveforlnKp.

Solution

Substitutingvaluesgives:
 TocalculateKp,wetaketheantilogarithm:

Noticethatwehaveexpressedtheanswertoonlyonesignificantfigure.Thisisbecause,aswesaw
inchapter2,whentakingalogarithm,thenumberofdigitswrittenafterthedecimalplaceequals
thenumberofsignificantfiguresinthenumber.Conversely,thenumberofsignificantfiguresin
theantilogarithmequalsthenumberofdigitsafterthedecimalinthelogarithm.

Isouranswerreasonable?

Thevalueof islargeandnegative,sothepositionofequilibriumshouldfavourtheproducts.
ThelargevalueofKpisthereforereasonable.

PRACTICEEXERCISE9.12
ThereactionN2(g)+3H2(g) 2NH3(g)has
Kp=6.910 5at25.0C.Calculate for
thisreaction.

PRACTICEEXERCISE9.13
ThereactionH2(g)+I2(g) 2HI(g)has
at25.0C.Whatis
thevalueofKpatthistemperature?

Wecanusethermodynamicdatacollectedat25Ctocalculategoodapproximationsofthevaluesof
equilibriumconstantsattemperaturesotherthan25C.Thisisbecausethevaluesof and donot
changemuchwithtemperature,sowecanusethesetocalculate and,hence,Katthenewtemperature.

WORKEDEXAMPLE9.10

calculatingKatTemperaturesOtherthan25C
Nitrousoxide,N2O,isananaestheticknownaslaughinggasbecauseitsometimesrelieves
patientsoftheirinhibitions.ThedecompositionofnitrousoxidehasKp=1.810 36at25C.The
equationis:
Forthisreaction, and .Whatistheapproxi
matevalueofKpforthisreactionat40C?

Analysis

Weneedavalueof at40C(313K),whichwecanrepresentas .Wecanestimate

usingthevaluesof and measuredat25Candtheequation

.Hence:

Solution

Substitutingthevaluesof and providedinthequestiongives:

NoticethatwehaveconvertedkJmol1toJmol1.Performingthearithmeticgives:

Thenextstepistousethisvalueof tocalculateKp.First,let'ssolveforlnKp.

SubstitutingwithR=8.314Jmol1K1andT=313Kgives:

Takingtheantilogarithm:

Noticethat,atthishighertemperature,N2O(g)isactuallyslightlymorestablewithrespectto
dissociationintoitselementsthanat25C,asreflectedintheslightlysmallervalueforthe
equilibriumconstantforitsdecomposition.

Isouranswerreasonable?

Aswewilllearninthenextsection,theequilibriumconstantforanexothermicreactiondecreases
withincreasingtemperature.Therefore,theanswerisreasonable.

PRACTICEEXERCISE9.14
ThereactionN2(g)+3H2(g) 2NH3(g)has
 astandardenthalpyofreactionof92.4kJ
mol1andastandardentropyofreactionof
198.3Jmol1K1.EstimatethevalueofKpfor
thisreactionat50C.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
9.4HowSystemsatEquilibriumRespondto
Change
WehaveseenthatthecompositionofareactionmixturechangesinthedirectionofdecreasingGibbs
energyuntilitreachesequilibrium.Whatwehavenotyetdiscussedishowasystematequilibrium
behaveswhenachangeismadethatperturbsthesystem.Suchachangemightbeachangein
temperature,volumeorpressureofthesystem,additionorremovalofchemicalspeciestoorfromthe
system,oradditionofacatalyst.Suchknowledgeisimportantasitmayallowustooptimisereaction
conditionstoobtainthemaximumamountofadesiredproduct.

LeChtelier'SPrinciple
OneofthefirsttostudyindetailtheeffectofchangeonasystematequilibriumwastheFrenchchemist
HenriLeChtelier(18501936)whoproposedwhatcametobeknownasLeChtelier'sprinciple.
Thisstatesthat,ifanoutsideinfluenceupsetsanequilibrium,thesystemundergoesachangeina
directionthatcounteractsthedisturbinginfluenceand,ifpossible,returnsthesystemtoequilibrium.
Thisisofteninterpretedasmeaningthat,ifachemicalspeciesisaddedtoonesideofanequilibrium,
theequilibriumpositionwillshifttouseuptheaddedspecies.LeChtelier'sprincipleisusefulasa
predictivetoolinmanycircumstances.Consider,forexample,theequilibrium:

forwhichtheforwardreactionisexothermicunderstandardconditions.AccordingtoLeChtelier's
principle,additionofNO2(g)tothereactionmixtureatequilibriumwillresultintheproductionofmore
N2O4(g),astheequilibriumpositionwillmovetotherighttouseuptheaddedNO2(g).Usingsimilar
reasoning,wecanseethatadditionofN2O4(g)tothereactionmixtureatequilibriumwillresultinthe
productionofmoreNO2(g).Ifwetakethesystemonthepreviouspageatequilibriumandincreasethe
volumeofthecontainerinwhichthereactionisoccurring,thiswillhavetheeffectofdecreasingthe
pressureinthecontainer.Tocounteractthisdisturbinginfluence,wewouldpredict,fromLeChtelier's
principle,thattheequilibriumpositionwillmovetothelefttoproducemoreNO2(g),asthiswill
minimisethepressuredecreasebymaximisingtheamountofgasinthecontainer.Finally,asthe
forwardreactionisexothermic,itgivesoutheat,whichwecanthereforeconsiderasbeingaproduct
ofthereactioninotherwords,wecanwritetheequation:

Ifwenowtakethesystematequilibriumandincreaseitstemperature,theequilibriumpositionwillshift
tothelefttouseuptheaddedheat,resultingintheproductionofmoreNO2(g).

However,predictionsmadeonthebasisofLeChtelier'sprinciplecanbeincorrectifitisnotapplied
correctlyinfact,addingareactantorproducttoasystematequilibriumdoesnotnecessarilyresultina
shiftoftheequilibriumposition.Forexample,additionofAgCl(s)toasaturatedaqueoussolutionof
AgClinequilibriumwithexcessAgCl(s)doesnotresultinanincreasein[Ag +(aq)]and[Cl(aq)]inthe
solution(wewillseethereasonwhyonp.366).Mostimportantly,LeChtelier'sprincipledoesnot
explainwhytheequilibriumpositiondoesordoesnotchangeonperturbationoftheequilibrium.
Therefore,itisbettertoconsidertheperturbationofsystemsatequilibriumbycomparisonofthevalues
oftheequilibriumconstant,K,andthereactionquotient,Q,foraparticularchemicalprocess.Westart
withasystematequilibriumforwhichQ=K.Wethenperturbthesystemandconsiderhowthisalters
thevalueofQandhowthesystemmustaltertomakeQagainequaltoK.Wewillconsideranumberof
differentscenariosusingthismethod.
AddingorRemovingaProductorReactant
Theadditionorremovalofaproductorreactantinstantaneouslyalterstheconcentrationofthatspecies
inthereactionmixture,providedthatthereactantorproductinquestionisnotapuresolidorliquid.
Whenthishappens,thevalueofQchangessothatQKandthesystemisnolongeratequilibrium.We
willillustratethisusingtheequilibrium:

[Cu(H2O)4]2+isblueand[CuCl4]2isyellowmixturesofthetwohaveanintermediatecolourand,
therefore,appearbluegreen,asillustratedinfigure9.12.

FIGURE9.12Theeffectofconcentrationchangesonthepositionofequilibrium.Thesolutioninthecentre
containsamixtureofblue[Cu(H2 O)4 ]2+andyellow[CuCl4 ]2,soithasabluegreencolour.The
tubeontherightcontainssomeofthesamemixtureaftertheadditionofconcentratedHCl.It
hasamorepronouncedgreencolourbecausetheequilibriumisshiftedtowards[CuCl4 ]2.At
theleftissomeoftheoriginalmixtureafterremovalofsomeClasinsolubleAgCland
subsequentfiltering.Itisbluebecausetheequilibriumhasshiftedtowards[Cu(H2 O)4 ]2+.

Whathappenswhenweincreasethechlorideionconcentrationbyaddingasmallvolumeofa
concentratedaqueoussolutionofHCltothesolutionatequilibrium?Toanswerthisquestion,weneed
towritetheexpressionforQ,thereactionquotient.Recallingfromthesectiononheterogeneous
systems(p.356)thatH2OdoesnotappearintheexpressionforQbecauseitisapureliquid,wecan
write:

OnlyreactantsandproductsthatappearintheexpressionforQcaninfluencethepositionofthe
equilibrium.Wecanseethat,immediatelyafteraddingtheHClsolution,the[Cl]ofthesolution
increases.ThishastheeffectofdecreasingthevalueofQ,because[Cl]appearsonthebottomlineof
thequotient.Thus,wenowhavethesituationwherethesolutionisnolongeratequilibriumandQ<K.
Obviously,torestoreequilibrium,wemustaltertheconcentrationsofthereactantsandproductsto
increaseQsothatitagainequalsK(rememberthatKisaconstantatconstanttemperature,sowemust
alterthevalueofQ).WithreferencetotheexpressionforQ,therearetwowaysthatwecanincreaseits
valuewecanmakethetoplinelarger,byincreasingtheamountand,therefore,concentrationof
[CuCl4]2,orwecanmakethebottomlinesmaller,bydecreasingtheamountsand,therefore,
concentrationsof[Cu(OH2)4]2+andCl.These,infact,equatetothesamethingashiftofthe
equilibriumpositiontowardsproducts.Thepronouncedgreencolourofthesolutionattherightof
figure9.12showsthatthisisinfactwhathappensthereismoreyellow[CuCl4]2andlessblue
[Cu(OH2)4]2+presentinthesolutionafterthesystemreestablishesequilibriumfollowingadditionof
concentratedHCl(aq).

Wecanusethesamereasoningtopredicttheeffectofremovingareactantfromthesystem.Ifwetake
thesystematequilibriumandaddasmallvolumeofaconcentratedsolutionofsilverperchlorate,
AgClO4,theAg +ionsreactwithfreeClionstoforminsolubleAgCl(s),thuseffectivelyremovingCl
ionsfromthemixture.Again,lookingatourexpressionforQ,wecanseethatlowering[Cl]makesthe
bottomlineofthequotientsmaller,whichleadstoaninstantaneousincreaseinthevalueofQ.The
systemisnolongeratequilibrium,andQisgreaterthanK.Theconcentrationsofreactantsandproducts
must,therefore,changetodecreasethevalueofQsothatitagainisequaltoK.Thismaybeachieved
byeitherdecreasingthetoplineofthequotient(loweringtheamountand,therefore,concentrationof
[CuCl4]2)orincreasingthebottomline(increasingtheamountsand,therefore,concentrationsof
[Cu(OH2)4]2+andCl).Again,figure9.12showsthatthecolourofthesolutionbecomesmoreblue
followingremovalofsomeClasinsolubleAgCl(andsubsequentfiltering),consistentwiththe
productionofmore[Cu(OH2)4]2+.

Thetreatmentonp.365ispurelyqualitativebutallowsustopredictthemannerinwhichanequilibrium
shiftswithouthavingtoknowtheactualvaluesofKandQ.

Animportantexamplealreadyalludedto(p.365)isthatofasparinglysolubleionicsaltinequilibrium
withitsconstituentaqueousions.Consider,forinstance,asaturatedaqueoussolutionofsilverchloride,
AgCl,inthepresenceofsolidAgCl.Thebalancedchemicalequationforthisis:

andwewritethereactionquotientas:

NotethatpuresolidsandpureliquidsdonotappearintheexpressionsforeitherKorQ.Whatwouldbe
theeffectofaddingmoresolidAgCltotheequilibriummixture?AgCl(s)doesnotappearinthe
expressionforQsoadditionofAgCl(s)hasnoeffectonthepositionofequilibrium.LeChtelier's
principlecanleadtoincorrectpredictionsinproblemsofthistype(inthiscase,itwouldpredictan
increasein[Ag +]and[Cl]),anditispreferabletousethecomparisonofQandKtodeterminetheeffect
ofaddingorremovingreactantsorproducts.

Wewillseemoreofthesesortsofproblemsinchapter10.

ChangingthePressureinGaseousReactions
Therearetwowaysofchangingthetotalpressureinagaseousreactionmixtureatequilibrium:
changingthevolumeofthesystem
addinganinertgas.
Wewilllookattheseinturn.

ChangingtheVolumeoftheSystem
Changingthevolumeofagasmixtureatequilibriumchangesboththeconcentrationsandpartial
pressuresofthereactantandproductgases,therebyalteringQ.Increasingthevolumewilldecreasethe
partialpressuresofallgasesandthereforedecreasethetotalpressure,whereasdecreasingthevolume
willhavetheoppositeeffect.Wewillconsidertheeffectofincreasingthevolumeofthereactionvessel
ontheequilibriumpositionfortheformationofammoniafromnitrogenandhydrogen:

Forthisreaction,wewouldnormallywriteQpas:

However,inthiscase,itismoreconvenienttouseQc todeterminetheeffectofchangingthevolumeof
thereactionmixture.Hence,wecanwrite:

Rememberingthat ,wecanrewritethisas:

As isthesameasnV1,wecansimplifythisexpressionasfollows:

Whilethismaylooksomewhatdaunting,theimportantpointisthatwehaveshownthatQc is
proportionaltoV2inotherwords,whenweincreaseV,weincreaseQ.Usingthesamereasoningas
onp.366,wecansaythatincreasingthevolumeofthereactionvessel,V,willincreaseQ,makingQ>
K.ThesystemwillthenchangeinawaythatmakesQsmaller:thatis,makingthetoplineofthe
quotientsmallerbyreducingn NH3ormakingthebottomlinelargerbyincreasingn N2andn H2.This
meansthat,whenthevolumeofthereactionmixtureisincreased,thereactionmixturecomposition
shiftstowardsreactants,resultingintheproductionofmoreN2andH2.Increasingthevolumeofthe
reactionvesselingasphasereactionswhichhavealargernumberofreactantmoleculesthanproduct
moleculeswillalwaysresultinashiftofthereactionmixturecompositiontowardsreactants.

Ifweconsidertheequilibrium:
asimilartreatmenttothataboveshowsthat:

Inthiscase,Qc doesnotdependonV.Thus,increasingordecreasingthevolumeofthisreaction
mixturehasnoeffectonthepositionoftheequilibrium.Thisisalwaysthecasewhenthereisthesame
amountofgasoneachsideoftheequationinagasphasereaction.

Thefinalexampleusesthefamiliarequilibrium:

Tolookattheeffectofincreasingthevolumeofthesystematequilibrium,weusethesametreatmentas
abovetogive:

andwecanseethatQc isproportionaltotheinverseofVinotherwords,asthevolumeincreases,Qc
decreasessoQ<K.Toreestablishequilibrium,thesystemwillrespondtoincreaseQ:thatis,making
thetoplineofthequotientlargerbyincreasing ormakingthebottomlinesmallerbydecreasing
.Bothscenarioscorrespondtoanequilibriumshifttowardsproductsfollowinganincreasein
volumeofthereactionmixture.Increasingthevolumeofthereactionvesselingasphasereactions
whichhavealargernumberofproductmoleculesthanreactantmoleculeswillalwaysresultinashiftof
theequilibriumtowardsproducts.

Insummary,wehaveshownthatQc isproportionaltoVng,wheren gisdefinedthesamewayason

p.351,namelyasthenumberofmolesofgaseousproductsminusthenumberofmolesofgaseous
reactants.Knowingthisproportionalityallowsustodeterminetheeffectofchangingthevolumeofthe
reactionvesselonanysystematequilibrium.

AddinganInertGasatConstantVolume
Addinganinertgas(which,bydefinition,isunreactive)toagaseousreactionmixtureatequilibrium
increasesthetotalpressureofthesystem,butdoesnotalterthepositionofequilibrium.Toprovethis,
let'sconsideraddingtheinertgasheliumtotheN2O4/NO2equilibriummixture.Asheliumdoesnot
reactwitheitherthereactantorproduct,ourexpressionsforbothQc andQpforthisequilibriumremain
unchangedinthepresenceofhelium.Hence,asthereisnotermfor[He]orp He inQc orQp,
respectively,additionofheliumcannothaveanyeffectonthepositionofequilibriumasitcannotalter
thevalueofQ.Thisistrueinallcaseswherethetotalpressureofthereactionmixtureisalteredby
additionofaninertgas.

ChangingtheTemperatureofaReactionMixture
Thevalueoftheequilibriumconstant,K,foranyreactioncanbechangedonlybyalteringthe
temperatureofthereactionmixture.Wecanpredicttheeffectofchangingthetemperatureofareaction
mixtureatequilibriumfromthesignof fortheforwardreaction.Thevan'tHoffequation.
(figures9.13and9.14)states:

FIGURE9.13JacobusHenricusvan'tHoff(18521911),aDutchchemist,wasthefirstwinneroftheNobel
Prizeinchemistryin1901forhissignificantcontributionstochemicalthermodynamics.
However,possiblyhismostremarkableachievementwasinorganicchemistry,withhis
realisationthatcarbonatomsbearingfourattachedatomsadoptatetrahedral,ratherthana
squareplanar,arrangement.Whatmadethissoremarkablewasthathepublishedthisworkat
theageof22notmucholderthanmostofyoureadingthis.

FIGURE9.14PlotsoflnKversusTforsituationswhere is(a)positiveand(b)negative.

andthismeansthattheslopeoftheplotoflnKversusThasthesamesignasthatof .Forexample,
thereactionofnitrogenandhydrogentoformammoniaisexothermic:

sothegraphoflnKversusTshouldhaveanegativeslope.Thismeansthat,asweincreasethe
temperature,lnK,andhenceK,shoulddecrease.Thus,theproductionofammoniabecomesless
favourableasweincreasethetemperatureofthereactionmixture.Wecanmakethefollowing
generalisationsabouttheeffectoftemperaturechangesonthepositionofequilibrium:
Foranendothermicreaction(rHispositive),increasingthetemperatureincreasesthe
equilibriumconstant,soproductsarefavoured(figure9.14a).
Foranexothermicreaction(rHisnegative),increasingthetemperaturedecreasestheequilibrium
constant,soreactantsarefavoured(figure9.14b).
Figure9.15demonstratesthetemperaturedependenceoftheequilibriuminvolvingcomplexesofCu 2+
discussedpreviously(p.365),forwhichtheforwardreactionisendothermic.Coolingthereaction
mixturedecreasestheequilibriumconstant,givingashifttowardsthereactantsheatingthemixture
increasestheequilibriumconstant,somoreproductisformed.

FIGURE9.15Theeffectoftemperatureontheequilibrium[Cu(H2 O)4 ]2++4Cl [CuCl4 ]2+4H2 OThe

tubeinthecentreshowsanequilibriummixtureofthetwocomplexes.Whenthesolutionis
cooledinice(left),theequilibriumshiftstowardstheblue[Cu(H2 O)4 ]2+.Whenheatedinboiling
water(right),theequilibriumshiftstowardstheyellow[CuCl4 ]2.Thisbehaviourindicatesthat
thereactionisendothermicintheforwarddirection.

Thisillustratesthequalitativeuseofthevan'tHoffequation.Wecanalsouseitquantitativelyifwe
knowthevalueofanequilibriumconstant,K,ataparticulartemperature,T1,wecanusethefollowing
formofthevan'tHoffequationtodeterminethevalueoftheequilibriumconstantatanother
temperature,T2:

Thisassumesthat isconstantoverthetemperaturerangeT1toT2.

AdditionofaCatalyst
Catalystsaresubstancesthataffecttheratesofchemicalreactionswithoutactuallybeingusedup.While
additionofacatalysthelpsbringasystemtochemicalequilibriummorerapidly,thepositionof
equilibriumisnotaffected.Thisisbecausecatalystsarenotincludedintheoverallbalancedchemical
equationforthereaction,andsodonotappearintheexpressionforthereactionquotient,Q.
WORKEDEXAMPLE9.11

PredictingEquilibriumShifts

ThereactionN2O4(g) 2NO2(g)isendothermic,with .Ifwe

startwithanequilibriummixtureofN2O4(g)andNO2(g),howistheamountofNO2inthe
mixtureaffectedby(a)addingN2O4,(b)loweringthepressurebyincreasingthevolumeof
thecontainer,(c)raisingthetemperatureand(d)addingacatalysttothesystem?Whichof
thesechangesaltersthevalueofKc ?

Analysis

WearetakinganequilibriummixtureofN2O4(g)andNO2(g)andmakingvariouschangesto
thesystem.Wemustdetermine,viacomparisonofQandK,whetherthesechangesalterthe
equilibriumpositionand,therefore,howthisaffectstheamountofNO2(g).

Solution

Toanswerthesequestions,firstwritetheexpressionforQandthenuseittodeterminethe
effectofthechangemade:

(a)AddingN2O4(g)instantaneouslydecreasesQc soQc <Kc .TomakeQc =Kc ,the

equilibriumshiftstotherighttoincreaseQc ,resultingintheproductionofmore
NO2(g).TheamountofNO2(g)increases.
(b)Wehaveseenonpp.3668thatincreasingthevolumeofthecontainerreducesQc
becauseQc isinverselyproportionaltoV.Hence,tomakeQc =Kc ,theequilibrium
shiftstotherighttoincreaseQc ,resultingintheproductionofmoreNO2(g).The
amountofNO2(g)increases.
(c) Theforwardreactionisendothermic,meaningthat ispositivebyapplyingthe
van'tHoffequation,aplotoflnKcversusThasapositiveslope.ThuslnKc,and
thereforeKc ,increaseswithincreasingtemperature,soQc <Kc .TomakeQc =Kc ,Qc
mustincrease,resultingintheproductionofmoreNO2(g)atequilibrium.Theamount
ofNO2(g)increases.
(d)Asstatedabove,acatalystcanhavenoeffectonthepositionofequilibrium.The
amountofNO2(g)remainsunchanged.
Finally,theonlychangethataltersKc isachangeintemperature.

Isouranswerreasonable?

Compareeachofouranswerswithexamplesgiveninthissectiontoconfirmthattheyare
logicallyconsistent.
PRACTICEEXERCISE9.15

ConsidertheequilibriumPCl3(g)+Cl2(g) PCl5(g),forwhich .
HowistheamountofCl2atequilibriumaffectedby(a)addingPCl3,(b)addingPCl5,(c)
raisingthetemperatureand(d)decreasingthevolumeofthecontainer?How(ifatall)does
eachofthesechangesaffectKpforthereaction?

ChemicalConnections

AirPollutionandEquilibrium

Carsareoneofthemostserioussourcesofairpollution(figure9.16).Every
momentacarengineruns,potentiallyharmfulcompoundssuchascarbon
monoxide,CO,carbondioxide,CO2,andanumberofnitrogenoxidesleaveits
engineasexhaustgases.
 FIGURE9.16Airpollutionfromcarexhaustemissionscanposeahealthhazard.
Thiscanbeparticularlysevereinlargecitieswhereheavytrafficand
atmosphericconditionscancombinetoproducedangerouslevelsof
smog.

Whenairisdrawnintoacar'sengine,bothN2andO2arepresent.During
combustionofthepetrolordiesel,oxygenreactswiththehydrocarbonsinthefuel
toproduceCO2throughcompletecombustion,COthroughincomplete
combustion,andH2O.However,N2andO2canalsoreacttoformnitricoxide,
NO,attheseelevatedtemperatures,accordingtotheequation:

Althoughnitricoxideisanimportantbiologicalmolecule(itisinvolvedin
signallinginthebody),italsoreactsrapidlywithoxygenintheatmosphereto
formthetoxicbrowngasnitrogendioxide,NO2.Atroomtemperature,Kc forthe
formationofNOfromN2andO2is4.810 31.Itssmallvaluetellsusthatthe
 equilibriumconcentrationofNOshouldbeverysmall.Therefore,wedon'tfindN2
reactingwithO2underambientconditions.

ThereactionofN2andO2toformNOisendothermic.Thevan'tHoffequation(p.
368)tellsusthatathightemperatures,suchasthosefoundinthecylindersofa
petrolordieselengineduringcombustion,thisequilibriumshouldbeshiftedtothe
right,andsomeNOdoesindeedformathightemperatures.Unfortunately,when
theexhaustgasesleavetheengine,theycoolsorapidlythatthereactionrate
becomestooslowfortheNOtodecomposebacktoN2andO2.Asaresult,some
NOispresentamongtheexhaustgases.Onceintheatmosphere,thisNOreacts
withoxygentogiveNO2,whichisresponsibleforthebrownishhazeoften
associatedwithsevereairpollution.

Variousmethodshavebeendevisedtominimisetheamountofnitrogenoxides
thatentertheatmosphere.Forinstance,almostallmoderncarsareequippedwith
catalyticconverters.Thesedevicescatalysethedecompositionofnitrogenoxides
toN2andO2.Catalyticconvertersareexpensive,however,asthecatalystsusedin
thesearebasedonpreciousmetalssuchasplatinum,palladiumandrhodium.
Othermethodsofaccomplishingthesamegoalsarebeingstudied.

OnewaytoreducetheamountofNO2pollutionoftheatmosphereistoreducethe
amountofNOthatisformedincarengines.Sincetheextenttowhichthereaction
proceedstowardstheformationofNOincreasesasthetemperatureincreases,the
amountofNOformedcanbereducedsimplybyrunningthecombustionreaction
atalowertemperature.Thiscanbeaccomplishedbyloweringthecompression
ratiooftheenginethisistheratiobetweenthevolumeofthecylinderwhenthe
pistonisatthebottomofitsstrokeanditsvolumeafterthepistonhascompressed
theairfuelmixture.Athighcompressionratios,theairfuelmixtureisheatedtoa
hightemperaturebeforeitisignited.Aftercombustion,thegasesareveryhot,
whichfavourstheproductionofNO.Loweringthecompressionratiolowersthe
maximumcombustiontemperature,whichdecreasesthetendencyforNOtobe
formed.Unfortunately,loweringthecompressionratioalsolowerstheefficiency
oftheengine,whichreducesfueleconomy.

AnothermethodforcontrollingNOemissionsthathasbeentrialledistomixwater
withtheairfuelmixture.Someoftheheatfromthecombustionisabsorbedbythe
watervapour,sothemixtureofexhaustgasesdoesnotgetashotasitwould
otherwise.Attheselowertemperatures,theconcentrationofNOintheexhaustis
greatlyreduced.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
9.5EquilibriumCalculations
Youhaveseenthatthemagnitudeofanequilibriumconstantgivesussomefeelforthecompositionofareaction
mixtureatequilibrium.Sometimes,however,itisnecessarytohavemorethanmerelyaqualitativeknowledgeof
equilibriumconcentrations.Thisrequiresthatwebeabletousetheequilibriumconstantexpressionforquantitative
calculations.

EquilibriumcalculationsforgaseousreactionscanbeperformedusingeitherKporKc ,butforreactionsinsolution
wemustuseKc .Whetherwedealwithconcentrationsorpartialpressures,however,thesamebasicprinciplesapply.

Overall,wecandivideequilibriumcalculationsintotwomaincategories:
1.calculatingequilibriumconstantsfromknownequilibriumconcentrationsorpartialpressures
2.calculatingoneormoreequilibriumconcentrationsorpartialpressuresusingaknownvalueofKc orKp,
giveninitialconcentrationsofreactantsandproducts.

CalculatingKcfromEquilibriumConcentrations

OnewaytodeterminethevalueofKc istocarryoutthereaction,measuretheconcentrationsofreactantsand
productsafterequilibriumhasbeenreached,andthensubstitutetheseequilibriumvaluesintotheequilibrium
constantexpressiontocalculateKc .Asanexample,let'slookagainatthedecompositionofN2O4:

Insection9.2,wesawthat,if0.0350molofN2O4isplacedintoa1Lflaskat25C,theconcentrationsofN2O4
andNO2atequilibriumare:

TocalculateKc forthisreaction,wesubstitutetheequilibriumconcentrationsintotheequilibriumconstant
expression:

Therefore:

Althoughcalculatinganequilibriumconstantinthiswayisusuallystraightforward,sometimeswehavetodosome
stoichiometricmanipulations,asshowninworkedexample9.12.Thisexampleintroducestheuseofa
concentrationtable,anextremelyusefultoolforsolvingequilibriumproblems.

WORKEDEXAMPLE9.12

CalculatingKcfromEquilibriumConcentrations

Atacertaintemperature,amixtureofH2andI2waspreparedbyplacing0.200molofH2and0.200mol
ofI2intoa2.00Lflask.Afteraperiodoftime,theequilibrium:
wasestablished.ThepurplecolouroftheI2vapourwasusedtomonitorthereaction,anditwas
determinedthat,atequilibrium,theI2concentrationhaddroppedto0.020molL1.Whatisthevalueof
Kc forthisreactionatthistemperature?

Analysis

Thefirststepinanyequilibriumproblemistowritethebalancedchemicalequationandtheequilibrium
constantexpression.Theequationisalreadygiven,anditscorrespondingequilibriumconstant
expressionis:

TocalculatethevalueofKc ,wemustsubstitutetheequilibriumconcentrationsofH2,I2andHIintothe
equilibriumconstantexpression.Butwhatarethey?Wehavebeengivenonlyonedirectly,thevalueof
[I2].Toobtaintheothers,wehavetodosomestoichiometriccalculations.

Thesystemstartswithasetofinitialconcentrations,andachemicalchangeoccurstoreachequilibrium.
ThereisnoHIpresentinitially,sothereactionabovemustproceedtotheright,becausetherehastobe
someHIpresentforthesystemtobeatequilibrium.ThischangeincreasestheHIconcentrationand
decreasestheconcentrationsofH2andI2.Ifwecandeterminewhatthechangesare,wecancalculatethe
equilibriumconcentrations.Infact,thekeytosolvingalmostallequilibriumproblemsisdetermining
howtheconcentrationschangeasthesystemcomestoequilibrium.

Tohelpusinouranalysis,wewillconstructaconcentrationtablebeneaththechemicalequation.Wewill
dothisformostoftheequilibriumproblemsweencounterfromnowon,solet'sexaminethegeneral
formofthetable.

Inthefirstrow,wewritetheinitialmolarconcentrationsofthereactantsandproducts.(Strictlyspeaking,
weshoulduseamounts,ratherthanconcentrations,inthesecalculations.However,aslongasthesystem
remainsatconstantvolume,thecalculationswillbethesame,regardlessofwhetherweuseamountsor
concentrations.)Inthesecondrow,weenterthechangesinconcentration,usingapositivesignifthe
concentrationisincreasingandanegativesignifitisdecreasing.Finally,addingthechangestotheinitial
concentrationsgivestheequilibriumconcentrations:

Tosetuptheconcentrationtable,itisessentialthatyourealisethatthechangesinconcentrationmust
beinthesameratioasthecoefficientsofthebalancedequation.Thisisbecausethechangesarecaused
bythechemicalreactionproceedinginonedirectionortheother.Inthisproblem,thecoefficientsofH2
andI2arethesame,so,asthereactionproceedstotheright,theconcentrationsofH2andI2must
decreasebythesameamount.Similarly,becausethecoefficientofHIistwicethatofH2orI2,the
concentrationofHImustincreasebytwiceasmuch.Now,let'slookatthefinishedconcentrationtable,
howtheindividualentriesareobtainedandthesolutiontotheproblem.

Solution

Toconstructtheconcentrationtable,webeginbyenteringthedatagiveninthestatementoftheproblem.
TheseareshownintherowlabelledInitialconcentration.Theothervaluesarethenderivedas
describedbelow.Notethat,inallconcentrationtables,wewillhighlighttheknownconcentrationdata.

H2(g) + I2(g) 2HI(g)

Initialconcentration(molL1) 0.100 0.100 0

Changeinconcentration(molL1) 0.080 0.080 +2(0.080)

Equilibriumconcentration(molL1) 0.020 0.020 0.160

 Initialconcentration:NoticethatwehavecalculatedtheratioofamounttovolumeforbothH2andI2,
i.e.0.200mol/2.00L=0.100m.BecausenoHIwasplacedintothereactionmixture,itsinitial
concentrationhasbeensettoexactly0attheinstantofmixingH2andI2.Changeinconcentration:We
havebeengivenboththeinitialandequilibriumconcentrationsofI2,so,bydifference,wecancalculate
thechangeforI2(0.080m).Theotherchangesarethencalculatedfromthemoleratiosspecifiedinthe
chemicalequation.Asnotedabove,becauseH2andI2havethesamecoefficients(i.e.1),theirchanges
areequal.ThecoefficientofHIis2,soitschangemustbetwicethatofI2.Reactantconcentrations
decrease,sothechangeisnegative,whileproductconcentrationsincrease,sothechangeinHI
concentrationispositive.

Equilibriumconcentration:ForH2andHI,wejustaddthechangetotheinitialvalue.

Nowwecansubstitutetheequilibriumconcentrationsintotheequilibriumconstantexpressionand
calculateKc .

Isouranswerreasonable?

First,carefullyexaminetheequilibriumconstantexpression.Asalways,productsmustbeplacedinthe
numeratorandreactantsinthedenominator.Besurethateachexponentcorrespondstothecorrect
coefficientinthebalancedchemicalequationforthereaction.

Nowchecktheconcentrationtable.Noticethatthechangesforbothreactantshavethesamesign,and
thissignistheoppositeofthatoftheproduct.Thisrelationshipbetweenthesignsofthechangesis
alwaystrueandcanserveasausefulcheckwhenyouconstructaconcentrationtable.

Finally,checkthateachoftheequilibriumconcentrationsisproperlyplacedintheequilibriumconstant
expression.Theequilibriumconstantweobtainedisgreaterthan1.Thatimpliesthatasignificantamount
ofproductshouldbepresentatequilibrium,andexaminationoftheconcentrationtableshowsthatthisis
so.

TheConcentrationTableaSummary
Letusreviewsomekeypointsthatapplynotonlytoworkedexample9.12butalsotoothersthatdealwith
equilibriumcalculations.
1.Theonlyvaluesthatwecansubstituteintotheequilibriumconstantexpressionareequilibriumconcentrations
thevaluesthatappearinthelastrowofthetable.
2.Whenweenterinitialconcentrationsintothetable,theyshouldbeinunitsofmolesperlitre(molL1).The
initialconcentrationsarethosepresentinthereactionmixturewhenitispreparedweimaginethatnoreaction
occursuntileverythingismixed.
3.Thechangesinconcentrationsalwaysoccurinthesameratioasthecoefficientsinthebalancedequation.For
example,ifwearedealingwiththeequilibrium:

andwefindthattheN2(g)concentrationdecreasesby0.10Mduringtheapproachtoequilibrium,theentries
intheChangeinconcentrationrowwouldbeasfollows:
 3H2(g) + N2(g) 2NH3(g)

Changeinconcentration(molL1) 3(0.10) 1(0.10) +2(0.10)

=0.30 =0.10 =+0.20

4.InconstructingtheChangeinconcentrationrow,besurethatthereactantconcentrationsallchangeinthe
samedirectionandthattheproductconcentrationsallchangeintheoppositedirection.Iftheconcentrations
ofthereactantsdecrease,alltheentriesforthereactantsintheChangeinconcentrationrowshouldhavea
negativesignandalltheentriesfortheproductsshouldbepositive.

Keepthesepointsinmindasweconstructtheconcentrationtablesforotherequilibriumproblems.

PRACTICEEXERCISE9.16
Thewatergasshiftreaction:

isusedinindustrytopreparehydrogen.At
equilibrium,thefollowingconcentrationswere
foundforthisreactionat500C:[CO]=0.180M,
[H2O]=0.0411M,[CO2]=0.150Mand[H2]=
0.200M.WhatisthevalueofKc forthisreaction?

PRACTICEEXERCISE9.17
Inaparticularexperiment,itwasfoundthat,when
O2(g)andCO(g)weremixed,theyreacted
accordingtotheequation:

andtheO2concentrationhaddecreasedby0.030
molL1whenthereactionreachedequilibrium.
HowhadtheconcentrationsofCOandCO2
changed?

PRACTICEEXERCISE9.18
Astudentplaced0.200molofPCl3(g)and0.100
molofCl2(g)intoa1.00Lcontainerat250C.
Afterthereaction:

cametoequilibrium,itwasfoundthatthe
containercontained0.120molofPCl3.
(a)Whatweretheinitialconcentrationsofthe
reactantsandproduct?
(b)Byhowmuchhadtheconcentrations
changedwhenthereactionreached
equilibrium?
(c)Whatweretheequilibriumconcentrations?
(d)WhatisthevalueofKc forthisreactionat
 thistemperature?

CalculatingEquilibriumConcentrationsfromInitialConcentrations
AmorecomplextypeofcalculationinvolvestheuseofinitialconcentrationsandKc tocalculateequilibrium
concentrations.Althoughsomeoftheseproblemscanbesocomplicatedthatacalculatorisneededtosolvethem,
wecanlearnthegeneralprinciplesinvolvedbyworkingonsimplecalculations.Eventhese,however,requirealittle
appliedalgebra.Thisiswheretheconcentrationtablecanbeveryhelpful.

WORKEDEXAMPLE9.13

UsingKctoCalculateEquilibriumConcentrations1

Thewatergasshiftreaction:

hasKc =4.06at500C.If0.100molofCOand0.100molofH2O(g)areplacedina1.00Lreaction
vesselatthistemperature,whataretheconcentrationsofthereactantsandproductswhenthesystem
reachesequilibrium?

Analysis

Thekeytosolvingthiskindofproblemisrecognisingthat,atequilibrium:

Wemustfindvaluesfortheconcentrationsthatsatisfythiscondition.

Becausewedon'tknowwhattheseconcentrationsare,werepresentthemalgebraicallyasunknowns.
Thisiswheretheconcentrationtableisveryhelpful.Tobuildthetable,weneedquantitiestoenterinto
theInitialconcentration,ChangeinconcentrationandEquilibriumconcentrationrows.

Initialconcentration:TheinitialconcentrationsofCOandH2Oareboth0.100molL1=0.100m.Since
noCO2orH2isinitiallyplacedintothereactionvessel,theirinitialconcentrationsarebothexactly0at
theinstantofmixingCOandH2O.

Changeinconcentration:SomeCO2andH2mustformforthereactiontoreachequilibrium.Thisalso
meansthatsomeCOandH2Omustreact.Buthowmuch?Ifweknewtheanswer,wecouldcalculatethe
equilibriumconcentrations.Therefore,thechangesinconcentrationareourunknownquantities.

LetusallowxtorepresenttheamountofCOperlitrethatreacts.Noticethatwecouldjustaseasilyhave
chosenxtobetheamountofH2OperlitrethatreactsortheamountofCO2orH2perlitrethatforms.
ThereisnothingspecialabouthavingchosenCOtodefinex.ThechangeintheconcentrationofCOis
thenx(itisnegativebecausetheapproachofthesystemtoequilibriumdecreasestheCO
concentration).BecauseCOandH2Oreactina1:1moleratio,thechangeintheH2Oconcentrationis
alsox.Since1moleeachofCO2andH2isformedfrom1moleofCO,theCO2andH2O
concentrationsbothincreasebyx(theirchangesare+x).

Equilibriumconcentration:Weobtaintheequilibriumconcentrationsas:
Solution

Hereisthecompletedconcentrationtable.

CO(g) + H2O(g) CO2(g) + H2(g)

Initialconcentration(molL1) 0.100 0.100 0 0

Changeinconcentration(molL1) x x +x +x

Equilibriumconcentration(molL1) 0.100x 0.100x x x

NotethatthelastlineinthetabletellsusthattheequilibriumCOandH2Oconcentrationsareequaltothe
amountperlitrethatwaspresentinitiallyminustheamountperlitrethathasreacted.Theequilibrium
concentrationsofCO2andH2equaltheamountperlitreofeachthatforms,sincenoCO2orH2ispresent
initially.

Next,wesubstitutethequantitiesfromtheEquilibriumconcentrationrowintotheequilibriumconstant
expressionandsolveforx:

whichwecanwriteas:

Inthisproblem,wecansolvetheequationforxrmosteasilybytakingthesquarerootofbothsides:

Rearranginggives:

Collectingtermsinxgives:

Nowthatweknowthevalueofx,wecancalculatetheequilibriumconcentrationsfromthelastrowof
thetable.

Isouranswerreasonable?

First,weshouldcheckthatallconcentrationsarepositivenumbers.Theyare.Onewaytocheckthe
answersistosubstitutetheequilibriumconcentrationswe'vefoundintotheequilibriumconstant
expressionandevaluatethereactionquotient.Ifouranswersarecorrect,Qc shouldequalKc .Letusdo
this:
 RoundingKc totwosignificantfiguresgives4.1,sothecalculatedconcentrationsarecorrect.

WORKEDEXAMPLE9.14

UsingKctoCalculateEquilibriumConcentrations2

Inworkedexample9.13,itwasstatedthatthereaction:

hasKc =4.06at500C.Suppose0.0600molofCOand0.0600molofH2Oaremixedwith0.100mol
ofCO2and0.100molofH2ina1.00Lreactionvessel.Determinetheconcentrationsofallthe
substanceswhenthemixturereachesequilibriumatthistemperature.

Analysis

Wewillproceedinmuchthesamewayasinworkedexample9.13.However,thistime,determiningthe
algebraicsignsofxfwillnotbequitesosimplebecausenoneoftheinitialconcentrationsis0.Thebest
waytodeterminethealgebraicsignsistousetheinitialconcentrationstocalculatetheinitialreaction
quotient.ThenwecancompareQc andKc ,andthenbyreasoningwewilldeterminewhichwaythe
reactionmustproceedtomakeQc equaltoKc .

Solution

Theequilibriumconstantexpressionforthereactionis:

Let'susetheinitialconcentrations,shownintheconcentrationtablebelow,todeterminethevalueofthe
reactionquotientimmediatelyaftermixing.

Asindicated,Qc islessthanKc ,sothesystemisnotatequilibrium.Toreachequilibrium,Qc must

becomelarger,whichrequiresanincreaseintheconcentrationsofCO2andH2andacorresponding
decreaseintheconcentrationsofCOandH2O.Thismeansthat,forCO2andH2,thechangemustbe
positive,and,forCOandH2O,thechangemustbenegative.

Hereisthecompletedconcentrationtable.

CO(g) + H2O(g) CO2(g) + H2(g)

Initialconcentration(molL1) 0.0600 0.0600 0.100 0.100

Changeinconcentration(molL1) x x +x +x
Equilibriumconcentration(mol 0.0600 0.0600 0.100+ 0.100+

L1) x x x x
 L1) x x x x

Substitutingequilibriumquantitiesintotheequilibriumconstantexpressiongivesus:

Takingthesquarerootofbothsidesyields:

Tosolveforx,wefirstmultiplyeachsideby(0.0600x)toobtain:

Collectingtermsinxtoonesideandtheconstantstotheothergives:

Nowwecancalculatetheequilibriumconcentrations:

Isouranswerreasonable?

Asacheck,wecanevaluatethereactionquotientusingthecalculatedequilibriumconcentrations.

ThisisacceptablyclosetothevalueofKc .(ItisnotexactlyequaltoKc becauseoftheroundingof

answersduringthecalculations.)

Inworkedexamples9.13and9.14,wewereabletosimplifythesolutionbytakingthesquarerootofbothsidesof
thealgebraicequationobtainedbysubstitutingequilibriumconcentrationsintotheequilibriumconstantexpression.
Suchsimplificationsarenotalwayspossible,however,asillustratedinworkedexample9.15.

WORKEDEXAMPLE9.15

UsingKctoCalculateEquilibriumConcentrations3

Atacertaintemperature,Kc =4.50forthereaction:

If0.300molofN2O4isplacedintoa2.00Lcontaineratthistemperature,calculatetheequilibrium
concentrationsofbothgases.

Analysis
Asinworkedexample9.14,wefirstwritetheequilibriumconstantexpression:

Wewillneedtofindalgebraicexpressionsfortheequilibriumconcentrationsandsubstitutethemintothe
equilibriumconstantexpression.Toobtainthese,wesetuptheconcentrationtableforthereaction.

Initialconcentration:TheinitialconcentrationofN2O4is0.300mol/2.00L=0.150M.SincenoNO2was
placedinthereactionvessel,itsinitialconcentrationisexactly0.Changeinconcentration:Thereis
initiallynoNO2inthereactionmixture,soweknowitsconcentrationmustincrease.Thismeansthe
N2O4concentrationmustdecreaseassomeoftheNO2isformed.Let'sallowxtorepresenttheamountof
N2O4perlitrethatreacts,sothechangeintheN2O4concentrationisx.Becauseofthestoichiometryof
thereaction,theNO2concentrationmustincreaseby2xsoitschangeinconcentrationis2xEquilibrium
concentration:Asbefore,weaddthechangetotheinitialconcentrationineachcolumntoobtain
expressionsfortheequilibriumconcentrations.

Solution

Hereistheconcentrationtable.

N2O4(g) 2NO2(g)

Initialconcentration(molL1) 0.150 0

Changeinconcentration(molL1) x +2x

Equilibriumconcentration(molL1) 0.150x 2x

Nowwesubstitutetheequilibriumquantitiesintotheequilibriumconstantexpression:

Thistimetheleftsideoftheequationisnotaperfectsquare,sowecannotjusttakethesquarerootof
bothsidesasinworkedexample9.14.However,becausetheequationinvolvestermsinx2andxanda
constant,wecanusethequadraticformula.Foraquadraticequationoftheformax2+bx+c=0:

Expandingtheaboveequation,weget:

Arrangingtermsinthestandardordergives:

Therefore,thequantitieswewillsubstituteintothequadraticformulaare:a=4,b=4.50andc=0.675.
Makingthesesubstitutionsgives:
 Becauseoftheterm,therearetwovaluesofxfthatsatisfytheequation:x=0.134andx=1.26.
However,onlythefirstvalue,x=0.134,makesanysensechemically(seebelow).Usingthisvalue,the
equilibriumconcentrationsare:

Noticethat,ifwehadusedthenegativeroot,1.26,theequilibriumconcentrationofNO2wouldbe
negative.Negativeconcentrationsareimpossible,sox=1.26isnotacceptableforchemicalreasons.In
general,wheneveryouusethequadraticequationinachemicalcalculation,onerootwillbesatisfactory
andtheotherwillleadtoananswerthatdoesnotmakesensechemically.

Isouranswerreasonable?

Onceagain,wecanevaluatethereactionquotientusingthecalculatedequilibriumvalues.Whenwedo
this,weobtainQ=4.49,whichisacceptablyclosetothegivenvalueofKc .

PRACTICEEXERCISE9.19
Duringanexperiment,0.200molofH2and0.200
molofI2wereplacedintoa1.00Lvesselwhere
thereaction:

cametoequilibrium.Forthisreaction,Kc =49.5at
thetemperatureoftheexperiment.Whatwerethe
equilibriumconcentrationsofH2,I2andHI?

Equilibriumproblemscanbemuchmorecomplexthanworkedexample9.15.However,whenKiseitherverylarge
orverysmall,simplifyingassumptionscanbemadethatallowanapproximatesolutiontobeobtained.Thisis
illustratedinworkedexample9.16.

WORKEDEXAMPLE9.16

SimplifyingApproximationsinEquilibriumCalculations
Thethermaldecompositionofwatertoitselementsoccursonlytoaverysmallextent,evenathigh
temperaturesat1000C,Kc =7.310 18forthereaction:

Ifwaterataninitialconcentrationof0.100misallowedtoreactat1000C,whatwillbetheH2
concentrationwhenthereactionreachesequilibrium?

Analysis
Webegin,asalways,bywritingtheequilibriumconstantexpression,Kc :

andwethensetuptheconcentrationtableandproceedaswehavedonebefore.However,wewillfind
thatwecanmakesimplifyingassumptionsinthisproblembecauseoftheextremelysmallvalueofthe
equilibriumconstant.

Solution

Hereistheconcentrationtable.

2H2O(g) 2H2(g) + O2(g)

Initialconcentration(molL1) 0.100 0 0

Changeinconcentration(molL1) 2x +2x +x

Equilibriumconcentration(molL1) 0.1002x 2x x

Wenowsubstitutetheequilibriumconcentrationsintotheequilibriumconstantexpression:

Thisisacubicequationandthemathematicsrequiredtosolvesuchequationsexactlyarewellbeyond
thescopeofthisbook.However,inthiscase,themagnitudeofKc allowsustomakesimplificationsto
thisequationthatallowitsstraightforwardsolution.BecauseKc issoincrediblysmall,weknowthat,at
equilibrium,notmuchH2Owillhavereacted.Thismeansthat,toaverygoodapproximation,the
concentrationofH2OatequilibriumequalstheinitialconcentrationofH2O.Inotherwords,thetermxin
theconcentrationtableistiny,so0.1002x20.100.Makingthisassumptionsimplifiesthecubic
expressionasfollows.

Hence:

WecannowobtaintheH2concentration,whichisequalto2x(fromtheconcentrationtable).

Isouranswerreasonable?

Wemustfirstshowthattheassumptionwemadewasjustified.Wedothisbyshowingthat(0.1002x)is
indeedessentiallyequalto0.100.

Whenweround0.09999948tothreesignificantfigures,itis0.100.Thisshowsthatourassumptionis
justified.
 Wecannowshowthatouranswerisreasonable.ThetinyvalueofKc leadsustoexpectthatthe
equilibriumconcentrationofhydrogenisverysmall,whichitis.Wecanalsosubstituteourequilibrium
valuesintotheexpressionforQc (rememberthat[O2]=x)andconfirmthatQc =Kc .Itshouldalsobe
notedthattheexactsolutionoftheoriginalcubicequationusingacalculatorgivesx=2.610 7,again
showingthatourassumptionleadstoareasonableanswer.

PRACTICEEXERCISE9.20

Inairat25Cand1.01310 5Pa,theN2
concentrationis0.033MandtheO2concentration
is0.00810M.Thereaction:

hasKc =4.810 31at25C.TakingtheN2and

O2concentrationsgivenaboveasinitialvalues,
calculatetheequilibriumNOconcentrationthat
shouldexistinouratmospherefromthisreaction
at25C.

Thesimplifyingassumptionmadeinworkedexample9.16isvalidbecauseaverysmallnumberwassubtracted
fromamuchlargerone.Wecouldalsohaveneglectedx(or2x)ifitwereaverysmallnumberthatwasbeingadded
toamuchlargerone.Rememberthatyoucanneglectxonlyifitisaddedorsubtractedyoucanneverneglectxifit
occursasamultiplyingordividingfactor.

Asanarbitraryruleofthumb,youcanexpectthesesimplifyingassumptionstobevalidiftheconcentrationfrom
whichxissubtracted,ortowhichxisadded,isatleast400timesgreaterthanK.Forinstance,inworkedexample
9.16,2xwassubtractedfrom0.100.Since0.100ismuchlargerthan400(7.310 18),weexpecttheassumption
0.1002x0.100tobevalid.However,eventhoughthesimplifyingassumptionisexpectedtobevalid,always
checktoseeifitreallyisafterfinishingthecalculation.Iftheassumptionprovesinvalid,thensomeotherwayto
solvethealgebramustbefound.

ChemicalConnections

EquilibriaandCO2Sequestration

AssociateProfessorMarcelMaeder,UniversityofNewcastle

Onthefirstpageofthischapter,wediscussedtheincreasingCO2levelsintheatmosphereandhowthese
canadverselyaffecttheequilibriathatoccurintheEarth'soceans.Itisapparentthat,ifwecannotreduce
CO2emissions,wemustatleastfindawayofsequesteringtheemittedCO2sothatitwecanreduceits
effectontheEarth'sdelicateecosystems.

OnepotentiallypromisingwayofreducingtheCO2outputispostcombustioncapture(PCC),which
capturesCO2fromcoalfiredpowerplantsandthensequestersit.Theessenceofthisprocessisthe
separationofCO2fromtheotherfluegases,whicharemainlyN2,O2andH2Oandsomeminor
contaminantssuchasSO2.EquilibriainvolvingCO2playacrucialroleintheseseparationprocesses.

CO2isabsorbedintoanaqueoussolutionofanorganicamine,RNH2,andisthentransformedinto
carbonicacid,H2CO3.Thisdonatesaprotontotheamine,formingmainlyhydrogencarbonate,HCO3,
andprotonatedamine,RNH3+.Therelevantequilibriaare:
Therecanbeparallelreactions,inparticulartheformationofotherorganiccompoundscalledcarbamates
whichcomplicatethematter,buttheprinciplesarethesame.Crucially,theseequilibria,likethemajorityof
equilibria,aretemperaturedependent,andathightemperaturesomeoftheabsorbedCO2isreleasedfrom
theaminesolution.ThisistheprincipleofPCC.

ThePCCprocessisshownschematicallyinfigure9.17thefluegasfromthepowerplantispassed
upwardsthroughtheabsorbercolumnthroughwhichtheaminesolutionisflowingdown.CO2isabsorbed
whiletheothergases,whichdonotreactwiththeamine,escapeatthetopofthecolumn.Thesaturated
aminesolutionispumpedintothestrippercolumnwhereathighertemperaturesomeoftheCO2isreleased
inapureform,readyforsequestration,andthedepletedaminesolutionispumpedbackintotheabsorber.
Figure9.18showstheCSIROPCCpilotplantattheTarongpowerstationinQueensland.

FIGURE9.17SchematicofthePCCprocess.
 FIGURE9.18TheCSIROPCCpilotplantattheTarongpowerstationinQueensland.

Itisobviousthatthisprocessisveryenergyintensive,anditiscrucialthattheenergyconsumptionis
minimisedinordertomakePCCaviableprocess.Forthisreason,itisimportanttofullyunderstandthe
kineticsandthermodynamicsaswellasthetemperaturedependenceofthecompleteprocess.Thisisnot
easy,asthereactionscanbefastandspectroscopicdetectionisdifficult.Appropriateexperimentation
togetherwiththecomputationalanalysisaredevelopedattheNewcastleresearchgroupincollaboration
withtheCSIROEnergyTechnologydivision.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
ChemicalEquilibrium
Chemicalequilibriumoccurswhenthechemicalcompositionofasystemdoesnotchangewithtime.
Whentheforwardandreversereactionsinachemicalsystemoccuratequalrates,adynamic
equilibriumexistsandtheconcentrationsofthereactantsandproductsremainconstant.Foragiven
overallchemicalcomposition,theamountsofreactantsandproductsthatarepresentatequilibriumare
thesameregardlessofwhethertheequilibriumisapproachedfromthedirectionofpurereactants,pure
productsoranymixtureofthem.

TheEquilibriumConstant,K,andtheReactionQuotient,Q
Theequilibriumconstantexpressionisafraction.Theconcentrationsoftheproductsatequilibrium,
eachdividedby raisedtoapowerequaltoitsstoichiometriccoefficientinthebalancedchemical
equation,aremultipliedtogetherinthetopline(numerator).Thebottomline(denominator)is
constructedinthesamewayfromtheconcentrationsofthereactantsatequilibrium,eachdividedby
andraisedtoapowerequaltoitsstoichiometriccoefficient.Thenumericalvalueoftheequilibrium
constantexpressionistheequilibriumconstant,Kc .Ifpartialpressuresofgases,dividedby and
raisedtotheirstoichiometriccoefficients,areusedintheequilibriumconstantexpression,Kpis
obtained.Thethermodynamicequilibriumconstantisobtainedwhenactivities,ratherthanpressuresor
concentrations,areusedintheequilibriumconstantexpression.Theequilibriumconstantisconstantat
constanttemperature.Themagnitudeoftheequilibriumconstantreflectstheextenttowhichtheforward
reactionhasproceededtocompletionwhenequilibriumisreached.

Thereactionquotient,Q,hasthesameformasK,buttheconcentrationsorpressuresarenonequilibrium
values.PuresolidsandpureliquidsdonotappearintheexpressionsforKandQ.

Whenanequationismultipliedbyafactorntoobtainanewequation,weraiseitsKtothepowerofn
toobtainKforthenewequation.Whentwoequationsareadded,wemultiplytheirvaluesofKtoobtain
thenewK.Whenanequationisreversed,wetakethereciprocalofitsKtoobtainthenewK.

ThevaluesofKpandKc areequalonlyifthesamenumberofmolesofgasarerepresentedonboth
sidesofthechemicalequation.Whenthenumbersofmolesofgasaredifferent,KpisrelatedtoKc by
theequation:

whereR=8.314Jmol1K1,T=absolutetemperatureandn gisthedifferencebetweenthenumberof
molesofgaseousproductsandthenumberofmolesofgaseousreactantsinthebalancedequation.

Anequilibriumwhereallsubstancesareinthesamephaseiscalledahomogeneousequilibrium,while
onewithsubstancesinmorethanonephaseisaheterogeneousequilibrium.Theequilibriumconstant
expressionforaheterogeneousequilibriumomitsconcentrationtermsforpureliquidsandpuresolids.

EquilibriumandGibbsEnergy
GibbsenergydiagramsforchemicalreactionsshowthevariationinGibbsenergyofasystemasa
reactionmixtureproceedsfrompurereactantstopureproducts.Thesediagramsshowaminimum,due
totheGibbsenergyofmixingofreactantsandproducts,andthisminimumcorrespondstothe
equilibriumcompositionofthereactionmixture.Thepositionoftheminimumwithrespecttothe
proportionofproductstoreactantsisrelatedtothesignandmagnitudeof fortheforward
reaction:if islargeandnegative,theforwardreactionproceedsessentiallytocompletionandthe
equilibriummixtureconsistspredominantlyofproductsif islargeandpositive,theforward
reactionproceedsonlytoaverysmallextentandnegligibleamountsofproductsarepresentat
equilibrium. isrelatedtotheequilibriumconstantforachemicalreactionbytheequation:

ThespontaneityofanychangeincompositionofareactionmixtureisgivenbythesignofrGforthat
change.rGisrelatedto bytheequation:

HowSystemsatEquilibriumRespondtoChange
Theresponseofasystematequilibriumtoachemicalorphysicalchangecanbepredictedby
determiningtheeffectofsuchachangeonthevalueofQ,thereactionquotientfortheforwardreaction.
AnychangethataffectsQinstantaneouslyremovesthesystemfromequilibriumbecauseQKtheway
inwhichQmustchange(increaseordecrease)toagainmakeQ=Kdeterminesthedirectionof
spontaneouschangeinthereactionmixture.TemperaturealonecanchangethevalueofKfora
chemicalequilibrium,andthedirectioninwhichspontaneouschangemustoccurtoreestablish
equilibriuminthesecasesmaybedeterminedbythesignof fortheforwardreaction,viathevan't
Hoffequation:

Puresolids,pureliquids,inertgasesandcatalystsdonotappearintheexpressionforQsoadditionof
thesecanhavenoeffectonthepositionofequilibrium.

EquilibriumCalculations
Givenasetofequilibriumconcentrationorpressureconditions,wecancalculatethevalueofthe
equilibriumconstantforareaction,andwecanalsousethegivenvalueofanequilibriumconstantto
calculateequilibriumconcentrationsorpressures.Wecanuseaconcentrationtabletoassistinsuch
calculations.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Equilibriumconstantexpression(section9.2)
Thisexpressiondefinestherelationshipbetweentheequilibriumconcentrationsorpartialpressuresof
thereactantsandproductsinachemicalreaction.Forthereaction:

Reactionquotientexpression(section9.2)
Thisexpressionhasthesameformastheequilibriumconstantexpression,andisusedtocharacterise
systemsthatarenotatequilibrium.Theconcentrationsorpartialpressuresintheexpressioncanhave
anyvalue.Forthereaction

ComparisonofQandK(section9.2)
Atequilibrium,Q=K.IfthesystemisdisturbedsuchthatQ>K,thereactionmustshifttowards
reactantstorestoreequilibriumifQ<K,thereactionmustshifttowardsproductstorestoreequilibrium.

(section9.2)

ThisequationconvertsbetweenthevalueofKpandKc n gisthechangeinthenumberofmolesof
gas,whichiscalculatedusingthecoefficientsofgaseousproductsandreactants.

Manipulationofequilibriumequations(section9.2)
1.Whenthedirectionofanequationisreversed,thenewequilibriumconstantisthereciprocalof
theoriginal.
2.Whenthecoefficientsaremultipliedbyafactor,theequilibriumconstantisraisedtoapower
equaltothatfactor.
3.Whenchemicalequilibriaareadded,theirequilibriumconstantsaremultiplied.

Magnitudeoftheequilibriumconstant(section9.2)
1.WhenKc isverylarge,theequilibriumpositionliestowardstheproducts.
2.WhenKc 1,theconcentrationsofreactantsandproductsaresimilaratequilibrium.
3.WhenKc isverysmall,theequilibriumpositionliestowardsthereactants.
Valueof forareaction(section9.3)

Themagnitudeandsignof indicatequalitativelywhetherornotasignificantamountofproducts
willform.If isreasonablylargeandnegative,thereactionwillproceedlargelytowardsproducts.
If isreasonablylargeandpositive,theequilibriummixturewillcontainmainlyreactants.

(section9.3)
Thisequationrelatesthereactionquotient,Q,torG,whichenablesustodeterminewhetherareaction
isatequilibriumand,ifnot,thedirectionofspontaneouschangerequiredtoreachequilibrium.

(section9.3)

Thisequationrelates totheequilibriumconstant,K.

Concentrationtable(section9.5)
Thismaybeusedinproblemsinvolvingequilibriatodeterminetheconcentrationsofreactantsand
productsatequilibrium.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
ChemicalEquilibrium
9.1Sketchagraphshowinghowtheconcentrationsofthereactantsandproductsofatypicalchemical
reactionvarywithtimeduringthecourseofthereaction.Assumenoproductsarepresentatthe
startofthereaction.
9.2Whatismeantwhenwesaythatchemicalreactionsarereversible?
TheEquilibriumConstant,K,andReactionQuotient,Q
9.3Howisthetermreactionquotientdefined?
9.4UnderwhatconditionsarethevaluesofQandKthesame?
9.5Whenachemicalequationanditsequilibriumconstantaregiven,whyisitnotnecessarytoalso
specifytheformoftheequilibriumconstantexpression?
9.6At225C,K =6.310 3forthereaction:
p

Wouldweexpectthisreactiontogonearlytocompletion?
9.7Herearesomereactionsandtheirequilibriumconstants.
(a)

(b)

(c)
Arrangethesereactionsinorderoftheirincreasingtendencytogotowardscompletion.
9.8StatetheequationrelatingKptoKc anddefineallterms.
9.9Usetheidealgaslawtoshowthatthepartialpressureofagasisdirectlyproportionaltoitsmolar
concentrationatconstanttemperature.Whatistheproportionalityconstant?
9.10Whatisthedifferencebetweenaheterogeneousequilibriumandahomogeneousequilibrium?
9.11Whydoweomittheconcentrationsofpureliquidsandsolidsfromtheequilibriumconstant
expressionsofheterogeneousreactions?
EquilibriumandGibbsEnergy
9.12SketchagraphtoshowhowGibbsenergychangesduringaphasechangesuchasthemeltingofa
solid.
9.13SketchtheshapeoftheGibbsenergycurveforachemicalreactionthathasapositive .
Indicatethecompositionofthereactionmixturewhenitisatequilibrium.
9.14Manyreactionsthathavelarge,negativevaluesof arenotactuallyobservedtooccurat25
Cand10 5Pa.Why?
9.15Supposeareactionhasanegative .Willmoreorlessproductbepresentatequilibriumasthe
temperatureisraised?Assumethat and areindependentoftemperature.
9.16WritetheequationthatrelatestheGibbsenergychangetothevalueofthereactionquotientfora
reaction.
9.17HowistheequilibriumconstantrelatedtothestandardGibbsenergychangeforareaction?(Write
theequation.)
9.18Whatisathermodynamicequilibriumconstant?
9.19Whatisthevalueof forareactionforwhichK=1?

HowSystemsatEquilibriumRespondtoChange
9.20Howwilltheequilibrium:

beaffectedbythefollowing?
(a)additionofCH4(g)
(b)additionofH2(g)
(c)removalofCS2(g)
(d)decreasingthevolumeofthecontainer
(e)increasingthetemperature(theforwardreactionisendothermic)
9.21ThereactionCO(g)+2H (g) CH3OH(g)has .Howwilltheamount
2
ofCH3OHpresentatequilibriumbeaffectedbythefollowing?
(a)addingCO(g)
(b)removingH2(g)
(c)decreasingthevolumeofthecontainer
(d)addingacatalyst
(e)increasingthetemperature
9.22Considertheequilibrium:

Inwhichdirectionwillthisequilibriumbeshiftedbythefollowingchanges?
(a)additionofN2O(g)
(b)removalofNO2(g)
(c)additionofNO(g)
(d)increasingthetemperatureofthereactionmixture
(e)additionofheliumgastothereactionmixtureatconstantvolume
(f) decreasingthevolumeofthecontaineratconstanttemperature
9.23Inquestions9.21and9.22,whichchange(s)willalterthevalueofK?
9.24Considertheequilibrium2NO(g)+Cl (g) 2NOCl(g)forwhich .
2
HowwilltheamountofCl2atequilibriumbeaffectedbythefollowing?
(a)removalofNO(g)
(b)additionofNOCl(g)
(c)raisingthetemperature
(d)decreasingthevolumeofthecontainer
EquilibriumCalculations
9.25Inordertostudythefollowingreaction:

amixtureofNO(g),NO2(g)andH2O(g)waspreparedina10.0Lglassbulbat20Cwiththe
 followinginitialconcentrations:[NO]=[NO2]=2.5910 3M,[H2O]=9.44q0 4Mand
[HNO2]=0.0M.Whenequilibriumwasreached,[HNO2]was4.010 4M.Explainindetailhow
tocalculatetheequilibriumconstant,Kc ,forthisreaction.
9.26Two1.00LbulbsarefilledwithF (g)andPF (g)toapressureof5.0010 4Pa,asillustratedin
2 3
thefigurebelow.Ataparticulartemperature,Kp=4.0forthereactionofthesegasestoform
PF5(g):

(a)Thestopcockbetweenthebulbsisopenedandthepressurefalls.Sketchthisapparatus
showingthegascompositiononcethepressureisstable.
(b)Listanychemicalreactionsthatcontinuetooccuroncethepressureisstable.
(c)Supposeallthegasintheleftbulbisforcedintothebulbontherightandthenthe
stopcockisclosed.Makeasecondsketchtoshowthecompositionofthegasmixtureafter
equilibriumisreached.Commentonhowthecompositionoftheonebulbsystemdiffers
fromthatofthetwobulbsystem.
9.27Cl2reactswithBr2inCCl4solutiontoformBrClaccordingtotheequation:

Iftheinitialconcentrationswere[Br2]=0.6M,[Cl2]=0.4Mand[BrCl]=0.0M,whichofthe
followingconcentrationversustimegraphscouldrepresentthisreaction?Explainwhyyou
rejectedeachoftheotherfourgraphs.
(a)

(b)
 (c)

(d)

(e)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
9.28Writetheequilibriumconstantexpressionforeachofthefollowingreactionsintermsofmolar
concentrations.
(a)2PCl3(g)+O2(g) 2POCl3(g)
(b)2SO3(g) 2SO2(g)+O2(g)
(c)N2H4(g)+2O2(g) 2NO(g)+2H2O(g)
(d)N2H4(g)+6H2O2(g) 2NO2(g)+8H2O(g)
(e)SOCl2(g)+H2O(g) SO2(g)+2HCl(g)
(f) 3Cl2(g)+NH3(g) NCl3(g)+3HCl(g)
(g)PCl3(g)+PBr3(g) PCl2Br(g)+PClBr2(g)
(h)NO(g)+NO2(g)+H2O(g) 2HNO2(g)
(i) H2O(g)+Cl2O(g) 2HOCl(g)
(j) Br2(g)+5F2(g) 2BrF5(g)
9.29Writetheequilibriumconstantexpressionforthereactionsinquestion9.28intermsofpartial
pressures.
9.30Writetheequilibriumconstantexpressionforeachofthefollowingreactionsinaqueoussolution.
(a) Ag +(aq)+2NH (aq) [Ag(NH3)2]+(aq)
3
(b)Cd 2+(aq)+4SCN(aq) [Cd(SCN)4]2(aq)
(c) HClO(aq)+H O(l) H3O+(aq)+ClO(aq)
2
(d)CO 2(aq)+HSO (aq) HCO3(aq)+SO42(aq)
3 4
9.31At25C,K =110 85forthereaction:
c

WhatisthevalueofKc forthefollowingreaction?

9.32Usethefollowingequilibria:

tocalculateKc forthereaction:

9.33Writetheequilibriumconstantexpressionforeachofthefollowingreactionsintermsofmolar
concentrations.
(a)H2(g)+Cl2(g) 2HCl(g)
(b)

HowdoesKc forreaction(a)comparewithKc forreaction(b)?

9.34Writetheequilibriumconstantexpressionforthereaction:
 HowdoesKc forthisreactioncomparewithKc forreaction(a)inquestion9.33?
9.35A345mLcontainerholdsNH atapressureof9.9310 4Paandatemperatureof45C.Whatis
3
themolarconcentrationofammoniainthecontainer?
9.36Theconcentrationofwatervapouris0.0200Minacertaincontainerat145C.Whatisthepartial
pressureofH2Ointhecontainer?
9.37ForwhichofthefollowingreactionsdoesKp=Kc ?
(a)2H2(g)+C2H2(g) C2H6(g)
(b)N2(g)+O2(g) 2NO(g)
(c)2NO(g)+O2(g) 2NO2(g)
(d)CO2(g)+H2(g) CO(g)+H2O(g)
(e)PCl3(g)+Cl2(g) PCl5(g)
(f) N2O4(g) 2NO2(g)
9.38ThereactionCO(g)+2H (g) CH3OH(g)hasKp=6.310 3at225C.Whatisthevalueof
2
Kc atthistemperature?
9.39ThereactionHCOOH(g) CO(g)+H2O(g)hasKp=1.610 6at400C.Whatisthevalueof
Kc forthisreactionatthistemperature?
9.40ThereactionN O(g)+NO (g) 3NO(g)hasKc =4.210 4at500C.WhatisthevalueofKp
2 2
atthistemperature?
9.41OnepossiblewayofremovingNOfromtheexhaustofapetrolengineistocauseittoreactwith
COinthepresenceofasuitablecatalyst:

At300C,thisreactionhasKc =2.210 59.WhatisKpat300C?

9.42At773C,thereactionCO(g)+2H (g) CH3OH(g)hasKc =4.010 1.WhatisKpatthis
2
temperature?
9.43ThereactionCOCl (g) CO(g)+Cl2(g)hasKp=4.610 2at395C.WhatisKc atthis
2
temperature?
9.44Calculatethemolarconcentrationofwaterin(a)18.0mLofH2O,(b)100.0mLofH2Oand(c)
1.00LofH2O.Assumethatthedensityofwateris1.00gmL1.
9.45Thedensityofsolidsodiumchlorideis2.164gcm3.WhatisthemolarconcentrationofNaClina
12.0cm3sampleofpureNaCl?WhatisthemolarconcentrationofNaClina25.0gsampleof
pureNaCl?
9.46Writetheequilibriumconstantexpression,Kc ,foreachofthefollowingheterogeneousreactions.
(a)2C(s)+O2(g) 2CO(g)
(b)2NaHSO3(s) Na2SO3(s)+H2O(g)+SO2(g)
(c)2C(s)+2H2O(g) CH4(g)+CO2(g)
(d)CaCO3(s)+2HF(g) CaF2(s)+H2O(g)+CO2(g)
(e)CuSO45H2O(s) CuSO4(s)+5H2O(g)
9.47Theheterogeneousreaction:

hasKc =1.610 34at25C.Suppose0.100moleachofHClandsolidI2areplacedina1.00L

container.CalculatetheequilibriumconcentrationsofHIandCl2inthecontainer.
9.48At25C,Kc =360forthereaction:

IfsolidAgClisaddedtoasolutioncontaining0.10MBr,calculatetheequilibriumconcentrations
ofBrandCl.
9.49Calculatethevalueofthethermodynamicequilibriumconstantforthefollowingreactionsat25
C.(RefertothedatainappendixA.)
(a)2PCl3(g)+O2(g) 2POCl3(g)
(b)2SO3(g) 2SO2(g)+O2(g)
(c)N2H4(g)+2O2(g) 2NO(g)+2H2O(g)
(d)N2H4(g)+6H2O2(g) 2NO2(g)+8H2O(g)
9.50ThereactionNO (g)+NO(g) N2O(g)+O2(g)has .A1.00L
2
reactionvesselat1273Kcontains0.0200molNO2,0.040molNO,0.015molN2Oand0.0350
molO2.Isthereactionmixtureatequilibrium?Ifnot,inwhichdirectionwillspontaneouschange
occurtoreachequilibrium?
9.51ThereactionCO(g)+H O(g) HCOOH(g)has .Ifamixtureat
2

400Ccontains0.040molCO,0.022molH2Oand3.810 3molHCOOHina2.50Lcontainer,
isthereactionmixtureatequilibrium?Ifnot,inwhichdirectionwillspontaneouschangeoccur?
9.52Areactionthatcanconvertcoaltomethane(thechiefcomponentofnaturalgas)is:

forwhich .WhatisthevalueofKpforthisreactionat25C?Doesthis
valueofKpsuggestthatitisworthstudyingthisreactionasameansofmethaneproduction?
9.53Oneoftheimportantreactionsinlivingcellsfromwhichtheorganismdrawsenergyisthe
reactionofadenosinetriphosphate(ATP)withwatertogiveadenosinediphosphate(ADP)anda
freephosphateion:

Thevalueof forthisreactionat37C(normalhumanbodytemperature)is33kJmol1.
Calculatethevalueoftheequilibriumconstantforthereactionatthistemperature.
9.54Whatisthevalueoftheequilibriumconstantforareactionforwhich Whatwould
happentothecompositionofthesystemifwebeginthereactionwiththepureproducts?
9.55Methanol,apotentialreplacementforpetrolasafuelincars,canbemadefromH2andCObythe
reaction:

At500K,thisreactionhasKp=6.2510 3.Calculate forthisreaction.

9.56Refertothedataintable8.6onp.329todetermine forthereaction:
 WhatisthevalueofKpforthisreactionat25C?
9.57UsethedatainappendixAtocalculate forthefollowingreaction:

WhatisthevalueofKpforthereactionatthistemperature?
9.58Atacertaintemperature,Kc =0.18fortheequilibrium:

Supposeareactionvesselatthistemperaturecontainedthesethreegasesatthefollowing
concentrations:[PCl3]=0.0420M,[Cl2]=0.0240M,[PCl5]=0.00500M.
(a)Isthesysteminastateofequilibrium?
(b)Ifnot,inwhichdirectionwillaspontaneouschangeoccurtorestoreequilibrium?
9.59At460C,thereaction:

hasKc =85.0.Areactionflaskat460Ccontainsthesegasesatthefollowingconcentrations:
[SO2]=0.00250m,[NO2]=0.00350m,[NO]=0.0250m,[SO3]=0.0400m.
(a)Isthereactionatequilibrium?
(b)Ifnot,inwhichdirectionwillaspontaneouschangeoccurtorestoreequilibrium?
9.60Atacertaintemperature,thereaction:

hasKc =0.500.Ifareactionmixtureatequilibriumcontains0.180mCOand0.220mH2,whatis
theconcentrationofCH3OH?
9.61Kc =64forthereaction:

atacertaintemperature.Supposeitwasfoundthatanequilibriummixtureofthesegases
contained0.360MNH3and0.0192MN2.WhatwastheequilibriumconcentrationofH2inthe
mixture?
9.62At773C,amixtureofCO(g),H2(g)andCH3OH(g)wasallowedtocometoequilibrium.The
followingequilibriumconcentrationswerethenmeasured:[CO]=0.105M,[H2]=0.250M,
[CH3OH]=0.00261M.CalculateKc forthereaction:

9.63Ethene,C2H4,andwaterreactunderappropriateconditionstogiveethanol.Thereactionis:

Anequilibriummixtureofthesegasesatacertaintemperaturehadthefollowingconcentrations:
[C2H4]=0.0148M,[H2O]=0.0336M,[C2H5OH]=0.180M.WhatisthevalueofKc ?
9.64Atahightemperature,2.00molofHBrwasplacedina4.00Lcontainerwhereitdecomposed
accordingtotheequation:

Atequilibrium,theconcentrationofBr2wasmeasuredtobe0.0955M.WhatisKc forthis
reactionatthistemperature?
9.65A0.050molsampleofformaldehydevapour,CH2O,wasplacedinaheated500mLvesseland
someofitdecomposed.Thereactionis:

Atequilibrium,theHCHO(g)concentrationwas0.066molL1.CalculatethevalueofKc forthis
reaction.
9.66ThereactionNO2(g)+NO(g) N2O(g)+O2(g)reachedequilibriumatacertainhigh
temperature.Originally,thereactionvesselcontainedthefollowinginitialconcentrations:[N2O]=
0.184M,[O2]=0.377M,[NO2]=0.0560M,[NO]=0.294M.TheconcentrationofNO2,the
onlycolouredgasinthemixture,wasmonitoredbyfollowingtheintensityofthecolour.At
equilibrium,theNO2concentrationwas0.118M.WhatisthevalueofKc forthisreactionatthis
temperature?
9.67At25C,0.0560molO2and0.020molN2Owereplacedina1.00Lcontainerwherethe
followingequilibriumwasthenestablished:

Atequilibrium,theNO2concentrationwas0.020M.WhatisthevalueofKc forthisreaction?
9.68At25C,Kc =0.145forthefollowingreactioninthesolventCCl4:

IftheinitialconcentrationofBrClinthesolutionis0.050M,calculatetheequilibrium
concentrationsofBr2andCl2.
9.69At25C,Kc =0.145forthefollowingreactioninthesolventCCl4:

IftheinitialconcentrationsofBr2andCl2areboth0.0250M,calculatetheirequilibrium
concentrations.
9.70Theequilibriumconstant,Kc ,forthereaction:

wasfoundtobe0.500atacertaintemperature.If0.240molofSO3and0.240molofNOare
placedina2.00Lcontainerandallowedtoreact,calculatetheequilibriumconcentrationofeach
gas.
9.71Forthereactioninquestion9.70,areactionmixtureispreparedinwhich0.120molNO2and
0.120molofSO2areplacedina1.00Lvessel.Whataretheconcentrationsofallfourgasesat
equilibrium?Howdotheseequilibriumvaluescomparewiththosecalculatedinquestion9.70?
Accountforyourobservation.
9.72Atacertaintemperature,thereaction:

hasKc =0.400.Exactly1.00molofeachgaswasplacedina100Lvesselandthemixture
underwentreaction.Whatwastheequilibriumconcentrationofeachgas?
9.73Thereaction2HCl(g) H2(g)+Cl2(g)hasKc =3.2 10 34at25C.Ifareactionvessel
initiallycontains0.0500molL1ofHCl,whataretheconcentrationsofH2andCl2atequilibrium?
9.74At200C,K =1.410 10forthereaction:
c

If0.200molofN2Oand0.400molNO2areplacedina4.00Lcontainer,whatistheNO
 concentrationatequilibrium?
9.75At2000C,thedecompositionofCO2:

hasKc =6.410 7.Ifa1.00Lcontainerholding1.010 2molofCO2isheatedto2000C,

whatistheconcentrationofCOatequilibrium?
9.76At500C,thedecompositionofwaterintohydrogenandoxygen:

hasKc =6.010 28.WhatamountsofH2andO2arepresentatequilibriumina5.00Lreaction

vesselatthistemperatureifthecontaineroriginallyheld0.015molH2O?
9.77Atacertaintemperature,Kc =0.18fortheequilibrium:

If0.026molofPCl5isplacedina2.00Lvesselatthistemperature,whatistheconcentrationof
PCl3atequilibrium?
9.78At460C,thereaction:

hasKc =85.0.Suppose0.100molofSO2,0.0600molofNO2,0.0800molofNOand0.120mol
ofSO3areplacedina10.0Lcontaineratthistemperature.Whataretheconcentrationsofallthe
gaseswhenthesystemreachesequilibrium?
9.79Atacertaintemperature,Kc =0.500forthereaction:

If0.100molSO3and0.200molNOareplacedina2.00Lcontainerandallowedtocometo
equilibrium,whataretheNO2andSO2concentrations?
9.80At25C,Kc =0.145forthefollowingreactioninthesolventCCl4:

Asolutionwaspreparedwiththefollowinginitialconcentrations:[BrCl]=0.0400m,[Br2]=
0.0300m,[Cl2]=0.0200m.Whataretheirequilibriumconcentrations?
9.81Atacertaintemperature,K =4.310 5forthereaction:
c

If0.200molofHCOOHisplacedina1.00Lvessel,whataretheconcentrationsofCOandH2O
whenthesystemreachesequilibrium?
9.82ThereactionH (g)+Br (g) 2HBr(g)hasKc =2.010 9at25C.If0.100molofH2and
2 2
0.200molofBr2areplacedina10.0Lcontainer,whataretheequilibriumconcentrationsofall
componentsat25C?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
9.83ThereactionN2O4(g) 2NO2(g)hasKp=0.114at25C.Inareactionvesselcontainingthese
gasesinequilibriumatthistemperature,thepartialpressureofN2O4was2.5310 4Pa.
(a)WhatwasthepartialpressureoftheNO2inthereactionmixture?
(b)Whatwasthetotalpressureofthemixtureofgases?
9.84ThefollowingreactioninaqueoussolutionhasK =110 85atatemperatureof25C:
c

Whatistheequilibriumconstantexpressionforthisreaction?
9.85Atacertaintemperature,Kc =0.914forthereaction:

Amixturewaspreparedcontaining0.200molNO2,0.300molNO,0.150molN2Oand0.250mol
O2ina4.00Lcontainer.Whataretheequilibriumconcentrationsofeachgas?
9.86At400C,K =2.910 4forthereaction:
c

Amixturewaspreparedwiththefollowinginitialconcentrations:[CO]=0.20m,[H2O]=0.30m.
Noformicacid,HCOOH,wasinitiallypresent.Whatwastheequilibriumconcentrationof
HCOOH?
9.87At27C,K =1.510 18forthereaction:
p

If0.030molofNOisplacedina1.00Lvesselandequilibriumisestablished,whatarethe
equilibriumconcentrationsofNO,N2OandNO2?
9.88Considertheequilibrium:

Howisthepositionofequilibriumaffectedbythefollowing?
(a)addingNaHSO3tothereactionvessel
(b)removingNa2SO3fromthereactionvessel
(c)addingH2Otothereactionvessel
(d)increasingthevolumeofthereactionvessel
9.89Atacertaintemperature,Kc =0.914forthereaction:

Amixturewaspreparedcontaining0.200molofeachgasina5.00Lcontainer.Calculatethe
equilibriumconcentrationofeachgas.Howwilltheconcentrationschangeif0.050molofNO2is
addedtotheequilibriummixture?
9.90Atacertaintemperature,Kc =0.914forthereaction:

EqualamountsofNOandNO2areplacedina5.00LcontaineruntiltheN2Oconcentrationat
equilibriumis0.050m.WhatamountsofNOandNO2mustbeplacedinthecontainer?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
activities Gibbsenergydiagrams reactionquotient(Q)
chemicalequilibrium heterogeneousequilibrium reactionquotientexpression
concentrationtable heterogeneousreaction thermodynamicequilibrium
dynamicequilibrium homogeneousequilibrium constants
equilibriumconstant(K) homogeneousreaction van'tHoffequation
equilibriumconstant LeChtelier'sprinciple
expression

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

10 SolutionsandSolubility
ThediscoveryofXraysin1895enableddoctorstotakeimagesoftheinsideoftheliving
humanbodyforthefirsttime,andthistechniqueisstillusedoveronehundredyearslater.It
reliesontheabsorptionofXraysbyconstituentsofthebody.Whileobjectssuchasbone
giveclearimages,softtissueismoredifficulttosee.Therefore,tocreateanXrayimageof
areassuchasthegastrointestinaltract,itisnecessarytouseacontrastagentwhichabsorbs
Xrayswellandwhichcanbedeliveredspecificallytotherequiredpartofthebody.Barium
sulfate,BaSO4,isonesuchcontrastagent.Thisisingestedbythepatientintheformofa
bariummeal,therebycoatingthegastrointestinaltract,andanXrayistakenshortly
thereafter.ThisphotoisanexampleofanXrayofthegastrointestinaltractusingBaSO4asa
contrastagent.

ItmaysurpriseyoutolearnthattheBa2+ionishighlytoxic,andthatswallowingabarium
saltwouldgenerallyendindeath.However,bariumsulfateisonlyslightlysolublein
aqueoussolution,meaningthattheconcentrationofBa2+neverapproachestoxiclevels.

Inthischapter,wewillexaminevariousaspectsofsolutionsandsolubility.Inadditionto
outliningthedifferentpossibletypesofsolutions,wewillinvestigatetheenergeticsbehind
theformationofsolutions,quantifythesolubilityofslightlysolublesaltsusingthesolubility
product,Ksp,andshowthatphysicalpropertiessuchasthefreezingandboilingpointsof
solutionsdependonthenumberofsoluteparticlesinthesolution.
 KEYTOPICS

10.1Introductiontosolutionsandsolubility
10.2Gaseoussolutions
10.3Liquidsolutions
10.4Quantificationofsolubility:thesolubilityproduct
10.5Colligativepropertiesofsolutions

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
10.1IntroductiontoSolutionsandSolubility
Theabilityofchemicalsubstancestomixwitheachotherisaveryimportantaspectofchemistry.We
arefamiliarwithmanyexamplesfromeverydaylifeforexample,dissolvinginstantcoffeeinacupof
hotwater,addingdetergenttowaterandcleaningausedpaintbrushwithturpentineareallsituations
wherewerequiretwosubstancestomixcompletely.However,therearealsosubstancesthatwecannot
gettomixnomatterhowhardwetry,theprimeexamplebeingoilandwater(sowedon'tusewaterto
cleanapaintbrushcoveredinoilbasedpaint).Manyaspectsofchemicalsynthesis,inparticularthe
purificationofproductsfollowingachemicalreaction,relyonthefactthatparticularsubstancesdon't
mix.Anunderstandingoftheprinciplesinvolvedintheformationofsolutionsisimportantinmany
areasofchemistry.Inthischapter,wewillfocusontheenergeticsofformationofsolutionsandthe
quantificationofphysicalpropertiesofsolutions.

Asolutioncanbedefinedasahomogeneousmixtureoftwoormorepuresubstances(homogeneous
meansthatallregionsofthesolutionhaveexactlythesamecomposition).Despitethefactthatweoften
thinkofasolutionasinvolvingsometypeofliquid,wecanhavegaseoussolutionscomprisingtwoor
moregases(e.g.air)andevensolidsolutionscomprisingtwoormoresolids(e.g.alloyssuchasbrass
andpewter)inadditiontotheusualsolutionscontainingagas,liquidorsoliddissolvedinaliquid.In
thecaseofliquidsolutions,wecalltheliquidthesolvent,whilethedissolvedsubstanceiscalledthe
solutethesoluteispresentinsmalleramountsthanthesolvent.Asoluteissaidtobesolubleina
particularsolventifitdissolvescompletelyinthatsolventatthespecifiedtemperature.Wedefinethe
solubilityofthesoluteinaparticularsolventasthemaximumamountofthesolutethatdissolves
completelyinagivenamountofthesolventataparticulartemperature,T,andaparticularpressure,P,
whileasaturatedsolutionisoneinwhichnomoresolutewilldissolve.

Themostcommontypeofsaturatedsolutionwewillencounteristhatillustratedinfigure10.1,inwhich
excesssolidsoluteisinequilibriumwithitsdissolvedform.

FIGURE10.1Asaturatedsolution.Inasaturatedsolution,adynamicequilibriumexistsbetweenthe
undissolvedsoluteandthedissolvedsoluteinthesolution.

Theprocessofdissolvingasoluteinasolventtogiveahomogeneoussolutioniscalleddissolution.We
thereforetalkofthedissolutionofasoluteinaparticularsolvent.

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10.2GaseousSolutions
Wewillbeginourinvestigationofsolutionsbylookingatmixingtwogasestoformagaseoussolution.
Westartwiththesituationdepictedinfigure10.2,wheretwodifferentpuregasesareseparatedbya
divider.Whenweremovethedivider,wefindthatthetwogasesmixspontaneouslytogivea
homogeneousgaseoussolution.Thisisnotsurprisinggiventhatthegasmoleculesaremoving
randomlyathundredsofmetrespersecond.Evenifwecoolthetwogases,theywillstillmix,albeit
moreslowly.Infact,aswesawinchapter9,allgasesmixcompletelywithallothergasesinall
proportions.Thefactthatthetwogasesinfigure10.2mixspontaneouslymeansthatGforthemixing
process(mixG)mustbenegative.Recallingfromchapter8that:

andgiventhattheenthalpychangewhentwogasesaremixedisusuallysmall,itisthelargepositive
mixStermthatensuresthatmixGisnegative.Thecompletelymixedstateisfarmorestatisticallylikely
and,therefore,ofhigherentropythantheunmixedstatethisleadstoalargeentropyincreaseon
mixing,andacorrespondinglylargepositivemixSvalue.Infact,wesaythatthemixingprocessis
entropydriven.Whenweconsiderthegasesatthemolecularlevel(orindeedtheatomiclevelfor
monatomicgasessuchasHe,Ne,Ar,Kr,XeandRn),wecanseethatthereisnoimpedimenttomixing
thegases,astheintermolecularforcesbetweenindividualgasmoleculesaretiny,andthegasmolecules
arefarapart.However,whenweconsidercondensedphasesolutions(i.e.solutionsinvolvingliquids
and/orsolids),wewillseethatthemagnitudeofinteratomicorintermolecularattractionsinthe
condensedphasecandeterminewhetherornottwosubstancescanmix.Inthesecases,theenthalpyof
mixingbecomesimportant.

FIGURE10.2Mixinggases.Whentwogases,initiallyinseparatecompartments(a)suddenlyfindthemselves
inthesamecontainer(b),theymixspontaneously.

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10.3LiquidSolutions
Asmentionedonthepreviouspage,therearemanypossibletypesofsolutions.Inthissection,wewilldiscuss,indetail,thesolutionsthatresult
fromdissolutionofagas,liquidorsolidinaliquid.

GasliquidSolutions
Ascanbeseenintable10.1,gasesdisplayawiderangeofsolubilitiesinwater.MoleculessuchasO2andN2haveverylimitedsolubilityatroom
temperature,whilethesolubilityofthepolarmoleculeammoniaisaquiteremarkable51.8gper100gofwaterat20C.Foragastodissolvein
aliquid,thegasmoleculesmustbeabletodispersethemselvesevenlythroughoutthesolvent.Suchaprocessdiffersfromthatforformationofa
gaseoussolutioninthattheintramolecularforcesbetweenthesolventmoleculesarenotnegligible,andneitherthereforeisthevalueofsolH,the
enthalpyofsolution.
TABLE10.1 Solubilitiesofcommongasesinwater
Temperature
Gas 0C 20C 50C
nitrogen,N2 0.0029(a ) 0.0019 0.0012
oxygen,O2 0.0069 0.0043 0.0027

carbondioxide,CO2 0.335 0.169 0.076

sulfurdioxide,SO2 22.8 10.6 4.3

ammonia,NH3 89.9 51.8 28.4

aSolubilitiesareingramsofsoluteper100gofwaterwhenthegaseousspaceovertheliquidissaturatedwiththegasandthetotal
pressureis10 5Pa.

Theenthalpychangewhenagasdissolvesinaliquidhasessentiallytwocontributions,asshowninfigure10.3onthenextpage.
1.Energyisrequiredtoopenpocketsinthesolventthatcanholdgasmolecules.Thesolventmustbeexpandedslightlytoaccommodate
themoleculesofthegas.Thisisanendothermicprocesssinceattractionsbetweensolventmoleculesmustbeovercome.Waterisaspecial
caseitalreadycontainsopenholesinitsnetworkofloosehydrogenbondsaroundroomtemperature.Forwater,verylittleenergyis
requiredtocreatepocketsthatcanholdgasmolecules.
2.Energyisreleasedwhengasmoleculesenterthesepockets.Intermolecularattractionsbetweenthedissolvedgasmoleculesandthe
surroundingsolventmoleculeslowerthetotalenergy,andenergyisreleasedasheat.Thestrongertheattractionsare,themoreheatis
released.Watercanformhydrogenbondswithsomegases,suchasNH3,whereasmanyorganicsolventscannot.Moreheatisreleased
whensuchagasmoleculeisplacedinapocketinwaterthaninorganicsolvents.

FIGURE10.3Amolecularmodelofgassolubility:
(a)Agasdissolvesinanorganicsolvent.Energyisabsorbedtoopenpocketsinthesolventthatcanholdthegasmolecules.Inthesecond
step,energyisreleasedwhenthegasmoleculesenterthepockets,wheretheyareattractedtothesolventmolecules.Here,thesolution
processisshowntobeendothermic.
(b)Aroundroomtemperature,water'sloosenetworkofhydrogenbondsalreadycontainspocketsthatcanaccommodategasmolecules,so
littleenergyisneededtopreparethesolventtoacceptthegas.Inthesecondstep,energyisreleasedasthegasmoleculestaketheir
placeinthepocketswheretheyexperienceattractionstothewatermolecules.Inthiscase,thesolutionprocessisexothermic.
Enthalpiesofsolutionforgasesinorganicsolventsareoftenendothermicbecausetheenergyrequiredtoopenuppocketsisgreaterthanthe
energyreleasedbyattractionsformedbetweenthegasandsolventmolecules.Enthalpiesofsolutionforgasesinwaterareoftenexothermic
becausewateralreadycontainspocketstoholdthegasmolecules,andenergyisreleasedwhenwaterandgasmoleculesattracteachother.

Whilewestatedearlierthatgaseoussolutionsformmainlybecauseofthelargeentropyofthecompletelymixedstate,thesituationisnotso
straightforwardwithsolutionsofagasinaliquid.Liquidwaterhasasurprisinglyorderedstructure,andtheadditionofgasmoleculesdoesnot
necessarilydisruptthisstructureinfact,thereisexperimentalevidencethatentropydecreasesonformationofsomegaswatersolutions.Thus
thesolubilityofaparticulargasinwaterisasubtlebalanceofenthalpicandentropiceffects,anditisoftendifficulttodeterminewhichfactor
predominates.

Wecanalsoseefromtable10.1thatthesolubilityofgasesinwatervariessignificantlywithtemperature,withalltheexamplesgivenbecoming
lesssolubleasthetemperatureincreases.ThedecreasingsolubilityofO2withincreasingtemperaturehasobviousimplicationsforaquaticlife,
giventhegradualwarmingoftheEarth'soceans.

Ifwewritethedissolutionprocessasanequilibriumbetweentheundissolvedgasandthedissolvedgas:

wecanseethattheequilibriumconstantforthisprocessdecreaseswithincreasingtemperaturefortheexamplesintable10.1.Recallingthe
relationshipbetweenHandKfromchapter9(p.368),wecanconcludethatthedissolutionprocessforthesegasesisexothermic.However,
notallgasesbecomelesssolubleasthetemperatureincreasesforexample,thesolubilitiesofH2,N2,CO,HeandNeincommonorganic
solvents,suchastolueneandacetone,actuallyincreasewithincreasingtemperature.Youcanseefromtheseexamplesthatpredictingsolubilities
eveninsimplesystemsisfraughtwithdifficulty!

Thesolubilityofagasinaliquidisaffectednotonlybytemperaturebutalsobypressure.Forexample,thegasesinair,chieflynitrogenand
oxygen,whilenotverysolubleinwaterunderordinarypressures,becomeincreasinglysolubleatelevatedpressures(seefigure10.4).

FIGURE10.4Solubilityinwaterversuspressurefornitrogenandoxygen.Theamountofgasthatdissolvesincreasesasthepressureisraised.

Wecanrationalisethisobservationbyagainconsideringtheequilibrium:

andlookingattheeffectofincreasingthepressureonthepositionofthisequilibrium.Thereactionquotientexpressionforthisequilibriumcan
bewritteninaformthatinvolvesboththepressureoftheundissolvedgasandtheconcentrationofthedissolvedgas:

WecanseefromthisthatQisinverselyproportionaltop(gasundissolved).Thus,ifweincreasethepressureoftheundissolvedgasatconstant
temperature,wedecreaseQsothatQ<K.TorestoreequilibriumandmakeQ=K,theequilibriumpositionshiftstowardstherighthandsideto
increaseQbyincreasing[gasdissolved].Ofcourse,theconverseisalsotrueifwedecreasethepressureaboveagasliquidsolution,weincrease
Q,andsomeofthedissolvedgasleavesthesolutioninordertodecreaseQandrestoreequilibrium.Weseethismostoftenwheneverweopena
bottleofanythingfizzywhenthetopisremoved,bubblesofCO2emergefromthesolutioninresponsetothesuddenloweringofpressure
(figure10.5).
 FIGURE10.5Bottledcarbonatedbeveragesfizzwhenthebottleisopenedbecausethesuddendropinpressurecausesasuddendropingassolubility.

Toseehowpressureaffectsgassolubilityonamolecularlevel,imagineaclosedcontainerwithapiston,partlyfilledwithasolutionofagasina
liquid.Figure10.6ashowsthesystematequilibriumgasmoleculesmoveatequalratesbetweenthedissolvedandundissolvedstates.Gas
moleculesenterthesolutionatarateproportionaltothefrequencywithwhichtheycollidewiththesurfaceofthesolution.Thisfrequency
increaseswhenweincreasethepressureofthegas(figure10.6b)becausethegasmoleculesaresqueezedclosertogether.Becauseliquidsand
liquidsolutionsareincompressible,theincreasedpressurealonehasnoeffectonthefrequencywithwhichgasmoleculescanleavethesolution.
Thatmeansthatincreasingthepressurefavoursdissolutionofthegas.

FIGURE10.6 Howpressureincreasesthesolubilityofagasinaliquid:
(a)Atsomespecificpressure,equilibriumexistsbetweenthevapourphaseandthesolution.
(b)Anincreaseinpressureputsstressontheequilibrium.Moregasmoleculesaredissolvingthanareleavingthesolution.
(c)Moregashasdissolvedandequilibriumisrestored.

Asmoregasdissolves,however,therateoftheforwardprocesstogivedissolvedgassteadilyslowsandthereverserateincreases.Itincreases
because,atahigherconcentrationofdissolvedgas,therearesimplymoregasmoleculesinsolutionateachunitofsurfacearea.Theirfrequency
ofescapeisproportionaltothisconcentration.Butthedissolutionprocessdominatesuntilenoughadditionalgashasdissolvedtoequalisethe
opposingrates.Weagainhaveequilibrium(figure10.6c),butnowmoregasmoleculesaredissolvedinthesolutionthaninitially.

Henry'sLaw
Forgasesthatdonotreactwiththesolvent,Henry'slawgivestherelationshipbetweengaspressureandgassolubility.Henry'slawstatesthat
theconcentrationofagasdissolvedinaliquidatanygiventemperatureisdirectlyproportionaltothepartialpressureofthegasabovethe
solution:

Intheequation,cgasistheconcentrationofthedissolvedgasandp gasisthepartialpressure(pp.2267)ofthegasabovethesolution.The
proportionalityconstant,kH,calledtheHenry'slawconstant,isuniquetoeachgas.Theequationistrueonlyatlowconcentrationsandpressures
and,aswesaid,forgasesthatdonotreactwiththesolvent.

Analternative(andcommonlyused)expressionofHenry'slawis:

wherec1andp 1refertoinitialconditionsandc2andp 2tofinalconditions.

WORKEDEXAMPLE10.1

UsingHenry'sLaw
 At20C,thesolubilityofN2inwater,expressedintermsofmassofdissolvedgaspervolumeofsolution,is0.0150gL1whenthe
partialpressureofnitrogenis7.6310 4Pa.UsethesedatatocalculatetheHenry'sLawconstantforN2inwateratthistemperature.
WhatisthesolubilityofN2inwaterat20Cwhenitspartialpressureis1.0510 5Pa?

Analysis

Thisproblemdealswiththeeffectofgaspressureongassolubility,soHenry'slawapplies.WemustfirstconvertthesolubilityofN2
ingL1toasolubilityinmolL1tocalculatetheHenry'sLawconstant.Wethenusethistocalculatethesolubilityatthehigher
pressure.

Solution

WeusestoichiometrytodeterminethesolubilityofN2inmolL1.Weknowthat0.0150gofN2willdissolvein1.00Lofwater.
Therefore:

ThisistheamountofN2thatwilldissolvedin1.00L.ThusthesolubilityofN2is5.3510 4molL1.

Gatheringdata,wenowhavecgas=5.3510 4molL1andp gas=7.6310 4Pa.WeusethesetocalculatekHbyrearrangingcgas=

kHp gas:

WenowusethiscalculatedvalueofkHtodeterminethesolubilityathigherpressure:

ThereforethesolubilityofN2at1.0510 5Pais7.3610 4molL1.

Isouranswerreasonable?

AsHenry'sLawstatesthatgassolubilityisproportionaltogaspressure,wewouldexpectN2tobemoresolubleathigherpressure.
Ouranswershowsthistobethecase.

PRACTICEEXERCISE10.1

At1.010 5Papressureand20C,thesolubilityofoxygenin
wateris0.00134molL1.UsethesedatatocalculatekHforO2
undertheseconditions.Giventhataircomprises21%O2,what
massofO2wouldbedissolvedinwaterwhenthewateris
saturatedwithair?

LiquidliquidSolutions
TheformationofaLiquidLiquidsolutionrequiresthatweovercometheattractiveforcespresentbetweenthemoleculesofthetwopureliquids
togettheliquidstomixcompletely.Thisisanevenmorecomplicatedsituationthanformationofagasliquidsolution,yetwecanpredictthe
abilityofanytwoliquidstomix,withsomeconfidence,simplybyconsideringthepolaritiesofthetwoliquids.Forexample,wefindthatethanol
andwatermixcompletelyinallproportionswesaytheyaremisciblewhilehexaneandwaterareessentiallyimmiscibleandformtwo
layersonadditionofoneliquidtotheother(figure10.7).
 FIGURE10.7Likedissolveslike.
(a)Ethanolissolubleinwaterbecausethemixedethanolwaterattractionsarenotsignificantlyweakerthanthewaterwaterorethanol
ethanolattractions.
(b)Hexaneisnotsolubleinwaterbecausethemixedhexanewaterattractionismuchweakerthanthewaterwaterandhexanehexane
attractions.Thestrongerattractionsinthepureliquidsconstituteanenergybarriertomixing.

Bothwaterandethanolarepolarmolecules,whilehexaneisessentiallynonpolarthesefactsarecentraltoexplainingthebehaviourofthese
liquidsonmixing.TheOHfunctionalgroupintheethanolmoleculeleadstoextensivehydrogenbondinginteractionsbetweenethanolmol
eculesandbetweenethanolandwatermolecules(figure10.8).Thus,theintermolecularattractiveforcesinthetwopureliquidscanbe
compensatedforonmixingbythehydrogenbondinginteractionsbetweentheethanolandwatermoleculesthesystem,therefore,adoptsthe
entropicallyfavouredmixedstate.Conversely,hexanemoleculesarenonpolarandsocannotinteractstronglywithwatermoleculesthismeans
thattheenergyrequiredtodisruptthehydrogenbondingnetworkinwatercannotbecompensatedforbywaterhexaneinteractionsonmixing.
Evenifwecoulddispersewatermoleculesinhexane,eachtimetwowatermoleculescollided,theywouldtendtosticktogetherthrough
hydrogenbondinginteractions.Thiswouldcontinuetooccuruntilallthewatermoleculeshadstucktogetherandthesystemwouldeventually
becometwophases.

FIGURE10.8Hydrogenbondsinaqueousethanol.Ethanolmoleculesformhydrogenbondstowatermolecules.

Wecanusesimilarargumentstoexplainwhynonpolarliquidstendtomixwitheachother.Theintermolecularinteractionsinthepureliquidsare
low,sothereisnoenergeticimpedimenttomixing.

Ingeneral,whentwoliquidsareofsimilarpolarity,theytendtobemiscible,whereasliquidsofwidelydifferingpolaritiesareoftenfoundtobe
immiscible.Thislikedissolveslikeruleworkswellinpredictingsolubilities,but,asalways,thereareexceptions.ThepresenceofapolarOH
functionalgroupdoesnotguaranteethatallalcoholsarewatersolublewhilemethanol,CH3OH,ethanol,CH3CH2OH,andpropan1ol,
CH3CH2CH2OH,aremisciblewithwaterinallproportions,butan1ol,CH3CH2CH2CH2OH,isonlypartiallymiscibleandpentan1ol,
CH3CH2CH2CH2CH2OH,isimmiscible.

Thedifferingmiscibilitiesoftheabovealcoholswithwatercannotbeexplainedintermsofdifferingpolaritiesastheyallhaveverysimilardipole
moments(5.610 30Cm).Wemustthereforeconsidertherelativeenergeticmagnitudesofthehydrogenbondinginteractionsbetweenthe
polarOHfunctionalgroupsandwater,andthedispersionforcesbetweenthenonpolarhydrocarbontailsofneighbouringalcoholmolecules.
Formethanol,ethanolandpropan1ol,thehydrogenbondinginteractionsbetweentheOHgroupsandwaterdominate,leadingtowater
miscibility.However,asthehydrocarbontailsonthealcoholmoleculesincreaseinlengthbeyondthreecarbonatoms,thedispersionforces
betweenthesebecomesignificant.Thiscausesthealcoholmoleculestoclustertogetherasasinglephase,leadingtoimmiscibilitywithwater.

Wecanusesimilarargumentstoexplainthesolubilitiesofalcoholsinnonpolarsolvents.Forexample,eventhoughlongchainalcoholsare
appreciablypolarmolecules,theyaremisciblewithhexanebecauseofthedispersionforcesbetweenthehydrocarbonchainonthealcoholand
thehexanemolecules.Thesedispersionforcesdiminishasthechainlengthofthealcoholdecreases,andwefindthattheshortestchainalcohol,
methanol,isimmisciblewithhexane.

Thelongchainalcoholsdiscussedaboveareexamplesofmoleculeswithbothpolarandnonpolarregionswemightthereforeexpectthe
differentregionsofsuchmoleculestodisplaydifferentaffinitiestowardsbothpolarandnonpolarsolvents.Indeed,wemakeuseofthis
behavioureverydaywhenweusesoapsanddetergentstomakeoilsandwatermix.Bothdetergentsandsoapsconsistofmoleculescalled
surfactants(acontractionofthetermsurfaceactiveagents),whichcomprisepolarandnonpolarpartsthepolarpartsgenerallyresultfromafull
positiveornegativecharge.Thestructureofacommonsurfactantfoundinshampoosandtoothpastes,sodiumlaurylsulfate,isshowninfigure
10.9.Asthepolargroupisnegativelycharged,wecallthisananionicsurfactant.Whenaddedtoamixtureoftwoimmiscibleliquids,thepolar
endofasurfactantmoleculepreferentiallyorientsitselfinthepolarliquid,whilethenonpolarendissituatedinthenonpolarliquid.Thishelps
bringthetwoimmisciblephasestogether.Thisprocesswillbediscussedinmoredetailinchapter23.

FIGURE10.9Thestructureofsodiumlaurylsulfate.

LiquidsolidSolutions
Inmovingtosolutionsofsolidsinliquids,thebasicprinciplesremainthesame.Wewilllookfirstatwhathappenswhensodiumchloride,a
crystallinesalt,dissolvesinwater.

Figure10.10depictsasectionofacrystalofNaClincontactwithwater.Thedipolesofwatermoleculesorientthemselvessothatthenegative
endsofsomepointtowardsNa+ionsandthepositiveendsofotherspointatClions.Inotherwords,iondipoleattractionsoccurthattendtotug
andpullionsfromthecrystal.Atthecornersandedgesofthecrystal,ionsareheldbyfewerneighbourswithinthesolidsotheyaremorereadily
dislodgedthanthoseelsewhereonthecrystal'ssurface.Aswatermoleculesdislodgetheseions,newcornersandedgesareexposed,andthe
crystalcontinuestodissolve.

FIGURE10.10Hydrationofionsinvolvesacomplexredirectionofforcesofattractionandrepulsion.Beforethesolutionforms,watermoleculesareattracted
onlytoeachother,andNa+andClionsareattractedonlytoeachotherinthecrystal.Inthesolution,theionshavewatermoleculestotake
theplacesoftheiroppositelychargedcounterpartsinaddition,watermoleculesareattractedtoionsevenmorethantheyaretootherwater
molecules.

Astheyarefreed,theionsbecomecompletelysurroundedbywatermolecules(figure10.10).Thisphenomenoniscalledthehydrationofions.
Thegeneraltermforthesurroundingofasoluteparticlebysolventmoleculesissolvation,sohydrationisjustaspecialcaseofsolvation.
Ioniccompoundscandissolveinwaterwhentheattractionsbetweenwaterdipolesandionsovercomeboththeattractionsoftheionsforeach
otherwithinthecrystalandtheattractiveforcesbetweenwatermoleculesinbulkwater.Similareventsexplainwhysolidscomposedofpolar
molecules,suchasthoseofsugar,dissolveinwater(seefigure10.11onthenextpage).Attractionsbetweenthesolventandsolutedipoleshelp
todislodgemoleculesfromthecrystalandbringthemintosolution.Againweseethatlikedissolveslikeapolarsolutedissolvesinapolar
solvent.

FIGURE10.11Hydrationofapolarmolecule.Apolarsoliddissolvesinwaterbecauseitsmoleculesareattractedtotheverypolarwatermolecules,causing
thesolutemoleculestobecomehydrated.Noticethatthewatermoleculesorientthemselvessotheirpositiveendsarenearthenegativeends
ofthesolutedipolesandtheirnegativeendsarenearthepositiveendsofthesolutedipoles.

Thesamereasoningexplainswhynonpolarsolids,suchaswax,aresolubleinnonpolarsolvents,suchasbenzene.Waxisasolidmixtureof
longchainhydrocarbonsheldtogetherbydispersionforces.

Theattractionsbetweenthemoleculesofthesolvent(benzene)andthesolute(wax)arealsoduetodispersionforcesofcomparablestrength.

Whenintermolecularattractiveforceswithinsoluteandsolventaresufficientlydifferent,thetwodonotformasolution.Forexample,ionicsolids
orverypolarmolecularsolids(suchassugar)areinsolubleinnonpolarsolventssuchasbenzeneandhexane.Themoleculesofthese
hydrocarbonsolventsareunabletoattractionsorverypolarmoleculeswithenoughforcetoovercomethemuchstrongerattractionsthattheions
orpolarmoleculesexperienceinthesolidstate.

Wehavealreadyseenthat,whiletheenthalpychangesonmixinginsimplegaseoussolutionsareminimal,thesameisnotnecessarilytruein
LiquidLiquidsolutions.Theenthalpychangesonformationofasolutioncontainingadissolvedionicsolidcanbesubstantialandwewillnow
considerthesechangesinsomedetail.Recallingfromchapter8thatenthalpyisastatefunction,andthereforedoesnotdependonthewayin
whichwegetfromtheinitialstatetothefinalstate,wecanmodelthedissolutionofanionicsoluteinasolventasahypotheticaltwostep
process,asshowninfigure10.12.

FIGURE10.12Enthalpydiagramforasoliddissolvinginaliquid.Intherealworld,thesolutionisformeddirectly,asindicatedbythepurplearrow.Wecan
analysetheenthalpychangebyimaginingthetwoseparatesteps,becauseenthalpychangesarestatefunctionsandsoareindependentof
thepath.Theenthalpychangealongthedirectpathisthealgebraicsumofthoseforstep1andstep2.

Asyoucanseefromfigure10.12,thefirststepisendothermic.Theparticlesinthesolidattracteachother,andsoenergymustbesuppliedto
separatethem.Theamountofenergyrequiredisthelatticeenthalpy.Recallfromchapter8thatthelatticeenthalpyistheenthalpyrequiredto
separate1moleofacrystallinecompoundintogaseousparticles.Forioniccompounds,thegaseousparticlesareionsformolecularcompounds,
theyaremolecules.Forexample,thelatticeenthalpyofpotassiumiodide,KI,istheenthalpychangefortheprocess:
Inthesecondstep,gaseoussoluteparticlesenterthesolventandaresolvated.Thisstepisexothermic.Theenthalpychangewhengaseoussolute
particles(obtainedfrom1moleofsolute)aredissolvedinasolventiscalledthesolvationenthalpy.Ifthesolventiswater,thesolvationenthalpy
canalsobecalledthehydrationenthalpy.Forexample,thehydrationenthalpyofKIistheenthalpychangefortheprocess:

Theenthalpyofsolution(solH)istheenthalpychangewhen1moleofacrystallinesubstanceisdissolvedinasolventitisequaltothe
enthalpydifferencebetweentheendothermicstep1andtheexothermicstep2Forexample,theenthalpyofsolutionofKIcalculatedfromthe
datagivenonthepreviouspageisthesumoftheenthalpychangesforsteps1and2,namely:

Thisprocessisshownindetailinfigure10.13.

FIGURE10.13Enthalpyofsolutiontheformationofaqueouspotassiumiodide.

Whentheenergyrequiredforstep1exceedstheenergyreleasedinstep2,thesolutionformsendothermicallywhenmoreenergyisreleasedin
step2thanisneededforstep1,thesolutionformsexothermically.

Wecantestthisanalysisbycomparingtheexperimentalenthalpiesofsolutionofsomesaltsinwaterwiththosecalculatedfromlatticeand
hydrationenthalpies(table10.2).Thecalculationsaredescribedinfigures10.13and10.14usingenthalpydiagramsfortheformationofaqueous
solutionsoftwosalts,KIandNaBr.
TABLE10.2 Latticeenthalpies,hydrationenthalpiesandenthalpiesofsolutionforsomegroup1metalhalidesat25C
solH(a)
Calculated Latticeenthalpy(kJmol1) Hydrationenthalpy(kJmol1) CalculatedsolH(kJmol1)(b) MeasuredsolH(kJmol1)
LiCl +833 883 50 37.0
NaCl +766 770 4 +3.9
KCl +690 686 +4 +17.2
LiBr +787 854 67 49.0
NaBr +728 741 13 0.602
KBr +665 657 +8 +19.9
KI +632 619 +13 +20.33

(a)Enthalpiesofsolutionrefertotheformationofextremelydilutesolutions.
(b)CalculatedsolH=latticeenthalpy+hydrationenthalpy.
 FIGURE10.14Enthalpyofsolutiontheformationofaqueoussodiumbromide.

Theagreementbetweencalculatedandmeasuredvaluesintable10.2isnotparticularlyclose.Thisispartlybecausepreciselatticeandhydration
enthalpiesarenotknownandpartlybecausethemodelusedinouranalysisisevidentlytoosimple.Noticehoweverthat,whentheorypredicts
relativelylargeenthalpiesofsolution,theexperimentalvaluesarealsorelativelylargeandbothvalueshavethesamesign(exceptforNaCl,
wherethevaluesarecloseto0andfalleithersideofit).Noticealsothatthechangesinvaluesshowthesametrendswhenwecomparethethree
chloridesaltsLiCl,NaClandKClandthethreebromidesaltsLiBr,NaBrandKBr.

Temperaturecanhaveasignificanteffectonthesolubilityofasolidsoluteinaliquid.Figure10.15showsaplotofsolubilityversustemperature
foranumberofionicsaltsitisobviousthatallbutoneoftheseexamplesbecomemoresolubleasthetemperatureincreases,whichwemight
expectintuitively(therearefewgenuineexamplesofsaltsthatbecomelesssolubleasthetemperatureincreases).
 FIGURE10.15Solubilityinwaterversustemperatureforseveralsubstances.Mostsubstancesbecomemoresolublewhenthetemperatureofthesolution
increases,buttheamountofthisincreasedsolubilityvariesconsiderably.

However,noteverythingisasstraightforwardaswewouldwish.ManyofyouwillhavedissolvedsolidNaOHinwaterandnoticedthatthe
solutiongetsquitehotasthesoliddissolves,meaningthattheprocessisexothermic.Fromthevan'tHoffequation(chapter9,p.368)wemight
thereforepredictthattheequilibriumconstantforthedissolutionofNaOHshoulddecreaseasthetemperatureincreaseshence,NaOHshould
becomelesssolublewithincreasingtemperature.Asyoucanseeinfigure10.15,theoppositetrendisobserved,andthiscanbeexplainedbythe
natureofsolidNaOHinasaturatedsolution.NaOHgenerallyexistsasananhydroussolidinotherwords,thecrystallinesolidcontainsno
watermoleculesand,aswehavestatedearlier,thisdissolvesexothermically.However,whenweprepareasaturatedsolutionofNaOHby
addingexcessNaOHtowater,analysisofthesolidphaseshowsittoconsistnotofanhydrousNaOH,butratherthesolidhydrate,NaOHH2O,in
whichonewatermoleculeisassociatedwitheachNaOHunit.Infact,thisspeciesdissolvesendothermically,soitismoresolubleathigher
temperatures.Youshouldalsoappreciatethatthevan'tHoffequationuses values,sosolHdatameasuredundernonstandardconditions
areoflimiteduseinpredictingthevariationofsolubilitieswithtemperature.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
10.4QuantificationofSolubility:theSolubility
Product
Ionicsaltsaregenerallyclassifiedasbeingeithersolubleorinsolubleinwater.Thewordinsoluble
suggeststhatsaltsclassifiedassuchdonotdissolveatallinwater,butthisisnotthecase.Ifwemix
aqueoussolutionscontainingequalamountsofthesolublesaltssilvernitrateandsodiumchloride
(figure10.16),weseeimmediateprecipitationoftheinsolublesaltAgCl,accordingtotheequation:

However,ifwecarefullyanalysethesolutionabovetheprecipitate,wefindthatitcontainsverysmall
amountsofbothAg +(aq)andCl(aq)ionsthismeansthatAgCldoesinfacthaveaverylimited
solubility(about0.19milligramsper100mLat25.0C)inaqueoussolution.WewouldclassifyAgCl
asaslightlysolublesalt.Asisthecasewithanysaturatedsolutionincontactwiththeundissolvedsolid,
adynamicequilibriumexists,withtherateofdissolutionofAgCl(s)beingthesameastherateof
precipitationofAg +(aq)andCl(aq).Wecan,therefore,quantifythesolubilityofAgCl(s)withreference
tothemagnitudeoftheequilibriumconstantforthedissolutionequilibrium:

Theequilibriumconstantforthedissolutionofaslightlysolublesaltiscalledthesolubilityproductand
isabbreviatedKsp.Fortheaboveequilibrium,wewriteKspas:

Recallfromchapter9thatpuresolidsneverappearinanequilibriumconstant.Therefore,aswewillsee
onthenextpage,theexpressionforKspforanyionicsolidalwaysconsistsonlyoftheproductofthe
aqueousionsraisedtotheirstoichiometricpowers.Wecanderiveanexpressionforthesolubility
productofanysaltMaXb(s)byconsideringtheequilibriumconstantforitsdissolutioninwater:

ForAgCl,Ksp=1.810 10at25.0C,meaningthatthesolubilityofAgClinwaterisindeedsmallbut
notzero.SaltsthatwegenerallyclassifyasslightlysolublehaveKspvaluesoftheorderof10 5orless,
andtable10.3givesKspdataforavarietyofsuchsalts(amorecomprehensivelistisgiveninappendix
C).Ingeneral,thesmallerthevalueofKsp,thelesssolubleisthesalt.However,youshouldappreciate
thatdirectcomparisonofKspvaluescanbemadeonlyforsaltswiththesameratioofanionstocations.
Forexample,CaF2ismoresolubleonamolarbasisthanAgClinwater,eventhoughKspforCaF2is
smallerthanthatforAgCl.Thisisbecausetheequilibriumconstantexpressionsforthetwosaltsdonot
haveidenticalformstheequationfordissolutionofCaF2is:

andthisleadstotheequilibriumconstantexpression:

whichobviouslydiffersfromthatonthepreviouspageforAgCl.Wewillexplorethisinmoredetailon
thefollowingpages.
FIGURE10.16PrecipitationofAgCl(s)onmixingaqueoussolutionsofAgNO3 andNaCl.

TABLE10.3 Solubilityproductsforselectedslightlysolublesaltsat25C
Salt Dissolvedions Ksp
halides
PbCl2(s) Pb 2+(aq)+2Cl(aq) 1.710 5
PbBr2(s) Pb 2+(aq)+2Br(aq) 2.110 6
PbF2(s) Pb 2+(aq)+2F(aq) 3.610 8
PbI2(s) Ag +(aq)+Cl(aq) 7.910 9
AgCl(s) Pb 2+(aq)+2I(aq) 1.810 10
CaF2(s) Ca2+(aq)+2F(aq) 3.910 11
AgBr(s) Ag +(aq)+Br(aq) 5.010 13
AgI(s) Ag +(aq)+I(aq) 8.310 17
hydroxides
Ca(OH)2(s) Ca2+(aq)+2OH(aq) 6.510 6
Mg(OH)2(s) Mg 2+(aq)+2OH(aq) 7.110 12
Fe(OH)2(s) Fe2+(aq)+2OH(aq) 7.910 16
Zn(OH)2(s) Zn 2+(aq)+2OH(aq) 3.010 16(a)
Al(OH)3(s) Al3+(aq)+3OH(aq) 310 34(b)
Fe(OH)3(s) Fe3+(aq)+3OH(aq) 1.610 39
carbonates
 NiCO3(s) Ni2+(aq)+CO32(aq) 1.310 7
MgCO3(s) Mg 2+(aq)+CO32(aq) 3.510 8
BaCO3(s) Ba2+(aq)+CO32(aq) 5.010 9
CaCO3(s) Ca2+(aq)+CO32(aq) 4.510 9(c)
SrCO3(s) Sr2+(aq)+CO32(aq) 9.310 10
CoCO3(s) Co 2+(aq)+CO32(aq) 1.010 10
ZnCO3(s) Zn 2+(aq)+CO32(aq) 1.010 10
Ag 2CO3(s) 2Ag +(aq)+CO32(aq) 8.110 12
chromates
Ag 2CrO4(s) 2Ag +(aq)+CrO42(aq) 1.210 12
PbCrO4(s) Pb 2+(aq)+CrO42(aq) 2.510 13
sulfates
CaSO4(s) Ca2+(aq)+SO42(aq) 2.410 5
PbSO4(s) Pb 2+(aq)+SO42(aq) 6.310 7
SrSO4(s) Sr2+(aq)+SO42(aq) 3.210 7
BaSO4(s) Ba2+(aq)+SO42(aq) 1.110 10
oxalates
MgC2O4(s) Mg 2+(aq)+C2O42(aq) 8.610 5
FeC2O4(s) Fe2+(aq)+C2O42(aq) 2.110 7
BaC2O4(s) Ba2+(aq)+C2O42(aq) 1.210 7
CaC2O4(s) Ca2+(aq)+C2O42(aq) 2.310 9
PbC2O4(s) Pb 2+(aq)+C2O42(aq) 2.710 11

AmorecomprehensivelistisgiveninappendixC.
(a)Existsinmorethanonesolidformdatagivenfortheamorphousform
(b)Existsinmorethanonesolidformdatagivenforthealphaform
(c)Existsinmorethanonesolidformdatagivenforthecalciteform

TheRelationshipBetweenKspandSolubility

OnewaytodeterminethevalueofKspforaslightlysolublesaltistomeasureitssolubility,i.e.how
muchofthesaltisrequiredtomakeasaturatedsolutionofaspecifiedvolume.Themolarconcentration
ofasaltinitssaturatedsolutioniscalledthemolarsolubility(s)thisequalstheamountofsalt
dissolvedin1litreofthesaturatedsolutionatthespecifiedtemperature.Themolarsolubilitycanbeused
tocalculateKsp,assumingthatallofthesaltthatdissolvesis100%dissociatedintoitsions.This
assumptionworksreasonablywellforslightlysolublesaltsmadeofunivalentions,suchassilver
bromide.Forsimplicity,andtoillustratethenatureofcalculationsinvolvingsolubilityequilibria,wewill
workontheassumptionthatallsaltsbehaveasthoughtheyare100%dissociated.Thisisnotentirely
true,especiallyforsaltsofpolyvalentions,sotheaccuracyofourcalculationsislimited.

WORKEDEXAMPLE10.2

CalculatingKspfromSolubilityData

Inthetimebeforedigitalphotography,silverbromide,AgBr,wasthelightsensitive
compoundusedinnearlyallphotographicfilm.ThesolubilityofAgBrinwateris1.310 4
gL1at25C.CalculateKspforAgBratthistemperature.

Analysis

WebeginbywritingthebalancedchemicalequationforthedissolutionofAgBrandusethis
todeterminetheexpressionforthesolubilityproduct,Ksp:

TocalculateKsp,werequiretheconcentrationsofAg +andBrinthesaturatedsolution
expressedinmolL1,sowemustconvertthegivenvalueof1.310 4gL1tomolL1.We
theninsertthesevaluesintotheaboveexpressionforKsp.

Solution

Weknowthat1.310 4gofAgBrisdissolvedineverylitreofthesaturatedsolution,sowe
convert1.310 4gofAgBrtoamountinmoles:

Fromthebalancedchemicalequationforthedissolutionreaction,weknowthat,when6.9
10 7molofAgBr(s)dissolvesinwater,itproduces6.910 7molofAg +(aq)ionsand6.9
10 7molofBr(aq)ions.Hence,themolarconcentrationsofAg +andBrareboth6.910 7
molL1.InsertingthesevaluesintotheexpressionforKspgives:

Asisusualwithequilibriumconstants,Kspisdimensionless.

Isouranswerreasonable?

Wehavedividedroughly110 4byanumberthatisabout210 2,whichgivesavalueof

about510 7,soourmolarsolubilityseemsreasonable.(Also,weknowAgBrhasavery
lowsolubilityinwater,soweexpectthemolarsolubilitytobeverysmall.)Theamountof
eachionformedperlitremustequaltheamountofAgBrthatdissolves.Finally,ifweround
 6.910 7to710 7andsquareit,weobtain4910 14=4.910 13.Ouranswerof4.8
10 13thereforeseemsreasonable.

PRACTICEEXERCISE10.2
Thesolubilityofthallium(I)iodide,TlI,in
waterat20Cis1.810 5molL1.
CalculateKspforTlIassumingthatitis
100%dissociatedinthesolution.

PRACTICEEXERCISE10.3

TheconcentrationofPb 2+,i.e.[Pb 2+],ina

saturatedsolutionofPbF2at25Cis2.15
10 3molL1.CalculatethevalueofKspfor
PbF2.

Obviously,ifwecancalculateKspfrommolarsolubilitydata,weshouldalsobeabletocalculatethe
molarsolubilityfromKsp.Workedexample10.3showshowthisisdone.

WORKEDEXAMPLE10.3

CalculatingMolarSolubilityfromKsp

Calculatethemolarsolubilityofleadiodide,PbI2,giventhatKsp(PbI2)=7.910 9at25C.

Analysis

Westart,asusual,bywritingthebalancedchemicalequationforthedissolutionofPbI2(s)
andwritetheKspexpressionfromthis:

Inthiscase,weknowthevalueofKspandmustdetermine[Pb 2+]and[I].However,wehave
oneequationcontainingtwounknowns.Tosolvethis,wemustmakeuseofthe
stoichiometricrelationshipbetween[Pb 2+]and[I]inthesaturatedsolution.

Solution

Asthisisanequilibriumproblem,wecansolveitusingaconcentrationtableinasimilar
mannertotheexamplesinchapter9(pp.3718).Wesetuptheconcentrationtableinthe
usualfashion,recognisingthattheinitialconcentrationsoftheionswillbe0m.Asthesalt
dissolves,smolesofPbI2willdissolvetoincreasetheconcentrationsofPb 2+andIbysand
2s,respectively.Notethatweusesratherthanxinthisconcentrationtable,assisdefinedas
themolarsolubilityinotherwordstheamountofthesaltdissolvedin1litreofsolution.

Hereistheconcentrationtable.

PbI2(s) Pb2+(aq) + 2I(aq)

Initialconcentration(m) 0 0
Changeinconcentration(m) +s +2s
Equilibriumconcentration(m) s 2s
Wenowsubstitutetheequilibriumconcentrationsintotheequilibriumconstantexpression,
Ksp.

Wehavenowgonefromoneequationwithtwounknownstooneequationwithasingle
unknown,s,whichwecansolve:

Thus,themolarsolubilityofPbI2(s)inwaterat25Cis1.310 3molL1.

Isouranswerreasonable?

Amolarsolubilityof10 3molL1islow,implyingthatthesaltisnotverysolubleandthat
ouranswerisatleastreasonable.Wecanquicklycheckouranswerbycarryingoutthe
reversecalculation,cubingsandmultiplyingtheanswerby4.ThisshouldequalKsp
(allowingforroundingerrors).

PRACTICEEXERCISE10.4
UsetheKspdataintable10.3tocalculate
themolarsolubilityof(a)AgBrand(b)
Ag 2CO3inwaterat25C.
Wehaveseeninworkedexample10.3thatsolubility,s,canberelatedtoKsp.Theexactnatureofthis
relationshipdependsonthechemicalformulaofthesalt.Asweshowedfora1:2electrolyte(withthe
formulaMX2orM2X),Ksp=4s3.Youshouldbeabletoderivethecorrespondingexpressionsfora1:1
electrolyteMX(Ksp=s2),a1:3electrolyte(MX3orM3X,Ksp=27s4)anda2:3electrolyte(M2X3or
M3X2,Ksp=108s5).

TheCommonionEffect
Untilnow,wehaveconsideredthesolubilityonlyofslightlysolubleionicsaltsinpurewater.Doesthe
solubilityofsuchsaltsdifferifthesolventisnotpurewaterbutasolutionthatalreadycontainsoneof
theionsintheslightlysolublesalt?Likewise,whathappensifwetakeasaturatedsolutionofaslightly
solublesaltandaddasolutionofanothersaltthathasoneionincommonwiththefirstsalt?

WecananswerthesequestionswithreferencetoasaturatedsolutionofPbCl2(s)(Ksp=1.710 5)at
equilibrium.TothissaturatedsolutionweaddasmallvolumeofaconcentratedsolutionofPb(NO3)2,a
solubleleadsalt,andlookattheeffectontheequilibriumpositionbycomparingQspandKsp.Webegin
bywritingthebalancedchemicalequationforthedissolutionofPbCl2andderivetheexpressionforKsp
fromthis,recallingthattheexpressionsforKspandQsphavethesameform.(Inchapter9,wecalledQ
thereactionquotient.InthecaseofQsp,thatnameisratherincongruous,giventhattheexpressionfor
Qspisneverafraction.Insometexts,Qspiscalledtheionicproduct.)

AddingasmallvolumeofconcentratedPb(NO3)2(aq)tothesaturatedsolutioninstantaneouslyincreases
[Pb 2+]andthereforeQsp.ThismeansthatQsp>Kspandtherefore,torestoreequilibrium,Qspmustbe
decreased.ThesystemachievesthisbyprecipitatingPbCl2(s),whichreducesboth[Pb 2+]and[Cl],
therebydecreasingQsptothepointwheretheequilibriumconditionQsp=Kspisagainsatisfied.Ifwe
weretoanalysethesaturatedsolutionatthispoint,wewouldfind[Cl]tobelessthanitwasinthe
originalsolution.AsalltheClinsolutioncomesfromdissolutionofPbCl2,thismeansthatPbCl2(s)is
lesssolubleinthepresenceofanothersourceofPb 2+.Thisisamanifestationofthecommonioneffect,
whichstatesthatanyionicsaltislesssolubleinthepresenceofacommonion,anionthatisa
componentofthesalt.

WehaveshownabovethatPbCl2islesssolubleinthepresenceofPb 2+thanitisinpurewater,andwe
canalsoshowbythesamereasoningthatitislesssolubleinthepresenceofanothersourceofCl.The
commonioneffectisnotlimitedtosolutionsofslightlysolublesaltsforexample,figure10.17shows
thateventherelativelysolublesaltNaClcanbeprecipitatedfromsolutiononadditionofconcentrated
HCl,asourceofthecommonionCl.Theadditionorpresenceofacommonionalwayslowersthe
solubilityofasaltprovidingthatnofurtherchemicalreactionispossible.Anexampleofasituation
whereachemicalreactionoccursisprovidedbytheslightlysolublesaltAgCl(s),whichcanreactwith
excessCltoformthecomplexanion[AgCl2],which,inturn,formssolublesaltswithavarietyof
cations.
FIGURE10.17Thecommonioneffect.ThetesttubeshownhereinitiallyheldasaturatedsolutionofNaCl,
wheretheequilibrium hadbeenestablished.Addition
ofafewdropsofconcentratedHCl,withahighconcentrationofthecommonionCl,forced
theequilibriumtoshifttotheleft.ThiscausedsomewhitecrystalsofsolidNaCltoprecipitate.

WORKEDEXAMPLE10.4

CalculationsInvolvingtheCommonIonEffect
WhatisthemolarsolubilityofPbI2ina0.10MNaIsolutionat25C?

Analysis

Asusual,webeginwiththebalancedchemicalequationandtheexpressionforKspderived
fromit:

Inthiscase,weconstructaconcentrationtableaswedidinchapter9(p.372).Theinitial
concentrationofPb 2+is0weassumethatNaIdissociatescompletelysotheinitial
concentrationofIis0.10M.Asinworkedexample10.3,werepresentthemolarsolubility
ofPbI2(s)intheNaIsolutionassmolL1.Therefore,whenthePbI2(s)dissolves,[Pb 2+]
changesby+smolL1and[I]by+2smolL1.Wecanthencalculatetheequilibrium
concentrationsofPb 2+andIbysummingtheinitialconcentrationsandthechanges.Hereis
theconcentrationtable.

PbI2(s) Pb2+(aq) + 2I(aq)

Initialconcentration(m) 0 0.10
Changeinconcentration(m) +s +2s
Equilibriumconcentration(m) s 0.10+2s
 Solution

SubstitutingequilibriumvaluesintotheKspexpressiongives:

Abriefinspectionrevealsthatsolvingthisexpressionforswillbedifficultifwecannot
simplifythemaths.Fortunately,asimplificationispossible,becausethesmallvalueofKsp
forPbI2tellsusthatthesalthasaverylowsolubility.Wealsoknowthatthepresenceofthe
commonionImakesPbI2evenlesssoluble.Thismeansverylittleofthesaltwilldissolve,
sos(oreven2s)isquitesmall.Let'sassumethat2sismuchsmallerthan0.10,inasimilar
fashiontosimplificationswemadeinworkedexample9.16onpp.3789.Ifthisisso:

Substituting0.10MfortheIconcentrationgives:

Thus,themolarsolubilityofPbI2in0.10MNaIsolutionis7.910 7M.

Isouranswerreasonable?

Checktheentriesinthetable.TheinitialconcentrationscomefromtheNaIsolution,which
containsnoPb 2+butdoescontain0.10MI.Bylettingsequalthemolarsolubility,the
coefficientsofsintheChangeinconcentrationrowequalthecoefficientsintheequationfor
theequilibrium.Weshouldalsochecktoseeifoursimplifyingassumptionisvalid.Notice
that2s,whichequals1.610 6,isindeedvastlysmallerthan0.10,justasweanticipated.(If
weadd1.610 6to0.10androundcorrectly,weobtain0.10.)

Inworkedexample10.3wefoundthatthemolarsolubilityofPbI2inpurewateris1.310 3M.In
waterthatcontains0.10MNaI(workedexample10.4),thesolubilityofPbI2is7.910 7M,wellover
1000timessmaller.Aswesaid,thecommonioneffectcancausehugereductionsinthesolubilitiesof
slightlysolublecompounds.

PRACTICEEXERCISE10.5
CalculatethemolarsolubilityofAgIin0.20
MNaIsolutionat25C.Comparethe
answerwiththecalculatedmolarsolubility
ofAgIinpurewater.
 PRACTICEEXERCISE10.6
CalculatethemolarsolubilityofFe(OH)3in
asolutionwheretheOHconcentrationis
initially0.050Mat25C.Assumethatany
dissolvedFe(OH)3dissociatescompletely
intoitsionsFe3+and3OH.

WillaPrecipitateForm?
WecanuseKspvaluestopredictwhetheraprecipitatewillformwhensolutionscontainingionicsalts
aremixed.WecalculateQspbydeterminingthemolarconcentrationoftheappropriateionsimmediately
aftermixingandcomparethisvaluewithKsp.IfQsp>Kspattheinstantthesolutionsaremixed,the
equilibriumpositionwillmovetothelefttomakeQsp=Ksp.Thiswillresultintheformationofa
precipitate.Conversely,ifQsp<Ksponmixingthesolutions,theequilibriumpositionwillmovetothe
right,thedissolvedionswillbefavoured,andnoprecipitatewillform.

WORKEDEXAMPLE10.5

PredictingWhetheraPrecipitateWillform

WillaprecipitateofAgCl(s)formonmixing50.0mLof1.010 4MNaCl(aq)with50.0mL
of1.010 6MAgNO3(aq)at25C?

Analysis

WehavetocalculateQspforthesolutionimmediatelyaftermixingandcompareitsvalue
withKspforAgCl.Thus,werequirethemolarconcentrationsofAg +(aq)andCl(aq),
rememberingthatthereisadilutionfactoronmixingthetwosolutions.

Solution

WebeginbywritingthebalancedchemicalequationforthedissolutionofAgCl(s)and
derivingtheexpressionforKspfromit:

WethencalculatethemolarconcentrationsofAg +andClinthefinalmixedsolutionby
determiningtheamountofeachanddividingitbythevolumeofthefinalsolution:
 WenowsubstitutethesevaluesintotheexpressionforQsp:

ThusQsp<Ksp,sowepredictthatnoprecipitateofAgCl(s)willformwhenthesolutionsare
mixed.

Isouranswerreasonable?

Asthisisessentiallyastoichiometricproblem,itishardtotellwhethertheanswermakes
sense.Incaseslikethese,youshouldcheckyourarithmeticandensureyouhavetranscribed
thecorrectnumbersintoyourcalculations.Themostcommonmistaketomakeinthistypeof
problemistoforgettotakeaccountofthefinalvolumeofthemixedsolution.Wehaveused
thecorrectnumbers,andwehavefactoredinthedilution,soouranswershouldbecorrect.
ThisexampleclearlyshowsthatAgCl(s)isnotinsoluble.

PRACTICEEXERCISE10.7
WillaprecipitateofPbSO4(s)formifwemix
100.0mLof1.010 3MPb(NO3)2(aq)and
100.0mLof2.010 3MMgSO4(aq)at25
C?

PRACTICEEXERCISE10.8
WillaprecipitateofPbCl2(s)formifwemix
50.0mLof0.10MPb(NO3)2(aq)and20.0
mLof0.040MNaCl(aq)at25C?

ChemistryResearch

ScaleCrystalsCausingProblemsforIndustry

DrFrancaJonesandProfessorMarkOgden,CurtinUniversity
Nexttimeyouareabouttoboilthekettle,havealookinside.Moreoftenthannot,youwill
seeabuildupofsolidmaterialonandaroundtheheatingelement.Thisisscalean
undesirablesolid(usuallycrystalline)material(figure10.18).Whilecleaningoutthekettleis
aneasytask,imaginehavingtoremovetonnesofcrystallinesolidfromahugeindustrial
plant,ortryingtounclogaboreholedeliveringoilfrombelowtheseabed.Thesearethe
challengesfacedbyindustrywhentryingtodealwiththeverycostlyproblemofscale
formation.

FIGURE10.18Scaleinsideametalpipe.

Considerasolutionflowingthroughapipe.Thethermodynamicsofasystemtellsusifcrystal
growthfwilloccur(seeChemistryResearchonp.334).Ifthesolutionissupersaturated(in
otherwords,Qsp>Ksp),weexpectcrystallisationtooccurbutwillittakeplacebeforeour
solutiongetstotheendofthepipe?Thisiswherethekinetics(seechapter15)oftheprocess
isimportanttherateofcrystallisationdetermineshowrapidlyourpipemaybeblockedby
scaleformation.

Chemistscantacklethisproblembychangingthethermodynamicsofthesystemorby
controllingthekinetics.Ifwehaveasupersaturatedsolutionofcalciumsulfate,thesolution
canbestabilisedbyaddingenoughEDTA(ethylenediaminetetraaceticacid,seefigure13.4)
toformacomplexwithmostofthecalciumcations.Thismethodaltersthethermodynamics
ofthesystemtoensurenocrystallisationoccurs.Unfortunately,thisrequiresasmanymoles
ofEDTAasthereisexcesscalcium,andistooexpensiveformostindustrialsituations.A
viablealternativeistochangetherateofcrystalgrowthbyintroducingacompounddesigned
todockontothecrystalsurfacebyblockingtheactivegrowthsitesonthecrystalsurface,
theadditivecompoundslowsdowntherateatwhichthecrystalcangrow.Thesurfaceis
usuallyonlyaverysmallfractionofthetotalmaterialpresent,andthemostactivesitesfor
crystalgrowthareasmallfractionofthecrystalsurface,andhenceaverysmallamountof
compoundcanhaveahugeimpactonthecrystalgrowthprocesses.

CurtinUniversityisstudyingthedesignandimpactofmoleculesthatwillcontrolcrystal
growth.Usingcomputationalchemistryincombinationwithexperimentalwork,molecules
canbedesignedtobindtocrystals,andeventospecificcrystalfaces.Forexample,additives
suchastheethylenediaminetetraphosphonateanioncansubstituteforsulfateanionsatthe
surfaceofabariumsulfatecrystalthesystemcanbemodelledinthecomputer(figure10.19)
todeterminethemostfavourablebindingsites.Experimentally,weusuallyobservechanges
inthecrystalshapeaclearsignthattheadditiveisbindingtothecrystalsurfaceand
changingtherelativeratesofgrowthofdifferentcrystalfaces(figures10.20and10.21).The
additivealsoslowscrystalgrowthandhelpstostopthosepipesgettingblocked.
 FIGURE10.19Acomputationalmodelofanethylenediaminetetraphosphonateaniondocked
intothesurfaceofabariumsulfatecrystal.Theanionicadditivesubstitutesfor
sulfateanionsatthesurface.

FIGURE10.20Scanningelectronmicrographofbariumsulfatecrystalsgrownintheabsenceof
anyadditives.

FIGURE10.21Scanningelectronmicrographofbariumsulfatecrystalsgrowninthepresenceof
ethylenediaminetetraphosphonateanion.

Butthat'sjustthestart.Welldesignedadditivemoleculescanbeusedtoallowthe
crystallisationofadesiredproductbyblockingthegrowthofanimpurity.Itisexcitingthat
controllinghownanometresizedmoleculesinteractwithagrowingcrystalcanhelpcontrol
thefateofakilometresizedindustrialplant.Therightbalanceofthermodynamicsand
kineticsmakesallthedifference!
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
10.5ColligativePropertiesofSolutions
Whenweprepareasolutionbydissolvingasmallamountofanonvolatilesoluteinasolvent,wefindthatparticular
propertiesoftheresultingsolutiondifferquitesignificantlyfromthoseofthepuresolvent.Forexample,theboiling
pointofthesolutionishigherthanthatofthepuresolventandthefreezingpointislower.Interestingly,the
magnitudesoftheboilingpointelevationandthefreezingpointdepressiondonotnecessarilydependontheidentity
ofthesoluteifwepreparedseparateaqueoussolutionsofNaClandNaBrbydissolving1moleofeachsaltin1kgof
water,wewouldfindthattheboilingpoints(about101C)andfreezingpoints(about3.4C)ofbothsolutionswould
bethesame.Propertiessuchasvapourpressure,boilingpointelevation,freezingpointdepressionandosmotic
pressure,whichdependonlyonthenumberofsoluteparticlesinthesolution,arecalledcolligativepropertiesandcan
beveryusefulinelucidatingtheexactnatureofsoluteparticlesinasolution.

ThewordcolligativeisderivedfromtheLatincolligaremeaningtobindtogether.Suchaderivationisappropriate
ascolligativepropertiesdoinfactarisefromtheattractiveinteractionsbetweensoluteparticlesandsolventmolecules.

Colligativepropertiesareimportantineverydaysituations.Addingantifreezetoacar'sradiatorlowersthefreezing
pointofthecoolantsolutiontowellbelow0Cthisreducestheprobabilityofdamagetotheenginecausedbythe
expansionthatoccursonformationofice.Antifreezealsoraisestheboilingpointoftheradiatorcoolant.Reverse
osmosis,aprocessthatreliesoncolligativeproperties,isusedextensivelyinthefoodindustryasamethodof
concentratingheatsensitivematerials,suchasfruitandvegetablejuices,asitrequiresonlytheapplicationofpressure.
Itisalsousedfordesalinationofseawaterandtoremoveaceticacidfromfermentingwine.

Tobeabletoquantifytheeffectsofcolligativeproperties,wemustfirstlookatwaysinwhichwecanexpressthe
compositionofsolutions.

Molarity
Themostcommonmethodofexpressingtheconcentrationofasolution,andtheonewehaveusedthroughoutthe
bookthusfar,isinmolL1i.e.theamountofsubstanceinaparticularvolumeofsolution.Thisismoreproperly
calledthemolarconcentrationormolarityofasolutionandhasthesymbolc:

However,becausesolutions(usually)increasetheirvolumewhenthetemperatureisraised,andviceversa,the
molarityofasolutionchangesasthetemperaturechanges.Forexample,asalinesolutionofknownmolarityprepared
at25Chasadifferentmolaritywhenitiswarmedtobodytemperaturethismakesmolarityalessthanidealmeasure
ofconcentrationinsituationsinvolvingcolligativeproperties.

Molality
Molalityisthepreferredmethodofexpressingsolutioncompositioninsituationsthatinvolvecolligativeproperties,as
thesepropertiesareproportionaltomolality.Wedefinethemolalconcentrationormolalityofasolutionasthe
amountofsoluteperkilogramofsolvent,andusethesymbolb:

Themolalityofasolutionistemperatureindependentasmassdoesnotdependontemperature.Themolarityand
molalityofaqueoussolutionsarenumericallydifferentbut,asaqueoussolutionsbecomemoreandmoredilute,the
numericalvalueofthemolarityapproachesthatofthemolality.

WORKEDEXAMPLE10.6

CalculationtoPrepareaSolutionofaGivenMolality
 WhatmassofNaClwouldhavetobedissolvedin500.0gofwatertoprepareasolutionofmolality0.150
molkg 1?

Analysis

Rearrangingtheequationformolalitygivenabove,weobtain:

Knowingtheamountofsolute,NaCl,wethenrelateamounttomassthroughthemolarmassofNaCl.

Solution

Therefore,4.38gofNaClneedstobedissolvedin500.0gofwatertogiveasolutionofmolality0.150
molkg 1.

Isouranswerreasonable?

IfweroundthemolarmassofNaClto60,0.1molis6gand0.2molis12g.Wealsonoticethat0.150mol
kg 1ishalfwaybetween0.1and0.2molkg 1.So,for1kilogramofwater,we'dneedhalfwaybetween6g
(0.1mol)and12g(0.2mol)ofNaCl.Forhalfasmuchwater(500g),wecuttheselimitsintwo,soweneed
halfwaybetween3and6gofNaCl.Ouranswerisinthisrange.

PRACTICEEXERCISE10.9
Waterfreezesatalowertemperaturewhenit
containssolutes.Tostudytheeffectofmethanolon
thefreezingpointofwater,wemightbeginby
preparingaseriesofsolutionsofknownmolalities.
Calculatethemassofmethanol,CH3OH,neededto
preparea0.250molkg 1solutionusing2000gof
water.

PRACTICEEXERCISE10.10
Ifweprepareasolutionbydissolving4.00gof
NaOHin250gofwater,whatisthemolalityofthe
solution?

MoleFraction
Inchapter6weintroducedthemolefractionasamethodofexpressingthecompositionofgasmixtures.Wecanalso
useitforliquidsolutions.Wedefinethemolefraction(x)ofaparticularcomponentofasolutionastheamountof
thatcomponentdividedbythetotalamountofmaterialinthesolution.Forexample,themolefractionofA,xA,ina
solutioncontainingsubstancesA,BandCwouldbedefinedas:
Molefractionisalsotemperatureindependent.

Wewillnowseehowthesealternativemeasuresofsolutioncompositionareusedwhenquantifyingcolligative
properties.

Raoult'sLaw
Asmentionedearlier,theboilingpointofasolutioncontaininganonvolatilesoluteishigherthanthatofthepure
solvent.Theboilingpointofasolventisthetemperatureatwhichthevapourpressureofthesolventisequaltothe
atmosphericpressuretherefore,theobservationofahigherboilingpointmustmeanthatthesolutionhasalower
vapourpressurethanthepuresolvent,asitnowtakesgreaterenergyinputtoraisethevapourpressureofthesolution
toequaltheatmosphericpressure.Providingthatthesolutionissufficientlydilute(i.e.xsolventiscloseto1),Raoult's
lawdescribestherelationshipbetweenthevapourpressureofthesolution(p solution),themolefractionofsolventinthe
solution(xsolvent)andthevapourpressureofthepuresolvent inasimpletwocomponentsystem:

Thisequationdescribesastraightlineandsoaplotofp solutionversusxsolventislinear,asshowninfigure10.22.
Becausexsolventandxsolute arerelatedinatwocomponentsystem:

wecanalsowriteRaoult'slawintermsofxsolute :

Thisexpressioncanberearrangedtogivethefollowingrelationshipforthepressuredifference(p)betweenthepure
solventandthesolution:

FIGURE10.22ARaoult'slawplot.Whenthevapourpressureofasolutionisplottedagainstthemolefractionofthesolvent,a
straightlineresults.Itshouldbestressedthatsuchbehaviourisobservedonlyindilutesolutions,i.e.thosein
whichxsolventiscloseto1.

WORKEDEXAMPLE10.7

CalculationUsingRaoult'sLaw
Whatisthevapourpressureofasolutionof10.0gofcandlewaxin40.0goftetrachloromethane,CCl4,at
23C?ThemolecularformulaofcandlewaxisC22H46andthevapourpressureofpureCCl4at23Cis
 1.3210 4Pa.

Analysis

WeuseRaoult'slawsowemustcalculatethemolefractionofsolvent,xsolvent,fromthedatagivenby
calculatingtheamountofbothC22H46andCCl4.

Solution

Therefore,n total=0.260mol+0.0322mol=0.292mol.Wecannowcalculatethemolefractionofsolvent:

WeusethisvalueinRaoult'slaw:

Hence,dissolving10.0gofcandlewaxin40.0gofCCl4lowersthevapourpressurebyabout11%.

Isouranswerreasonable?

Thepressureweobtainedislessthanthevapourpressureofthepuresolvent,whichiswhatwewould
expectfromRaoult'slaw.Barringarithmeticerrors,ouranswerlookssensible.

PRACTICEEXERCISE10.11
Dibutylphthalate,C16H22O4(molarmass278.34g
mol1),isanoilsometimesusedtosoftenplastic
articles.Itsvapourpressureisnegligibleatroom
temperature.Thevapourpressureofpureoctaneat
20Cis1.3810 3Pa.Whatisthevapourpressure
at20Cofasolutionof20.0gofdibutylphthalate
in50.0gofoctane,C8H18(molarmass114.22g
mol1)?

WhileRaoult'slawshowsthatasolutionhasalowervapourpressurethanthepuresolvent,itdoesnotexplainwhy
thisisthecase.Ifwecompareapuresolventwithasolutioncontaininganonvolatilesolute,weseethatthesurfaceof
thesolutioncomprisesamixtureofsolventandsolutemolecules,whilethesurfaceofthesolventconsistsonlyof
solventmolecules(figure10.23).
 FIGURE10.23Effectofanonvolatilesoluteonthevapourpressureofasolvent:
(a)Equilibriumbetweenapuresolventanditsvapour.Withahighnumberofsolventmoleculesatthe
surfaceoftheliquid,therateofevaporationisrelativelyhigh.
(b)Inthesolution,someofthesolventmoleculesatthesurfacehavebeenreplacedbysolutemolecules
sotherearefewersolventmoleculesavailabletoevaporatefromthesurfaceofthesolution.This
lowerstheevaporationrate,so,whenequilibriumisestablished,therearefewermoleculesinthe
vapour.Thevapourpressureofthesolutionisthereforelessthanthatofthepuresolvent.

Therefore,therearefewermoleculesofsolventatthesurfaceofasolutionthanofapuresolvent.Thismeansthat,in
thesolution,therearefewersolventmoleculesavailabletoevaporate,soweexpectthevapourpressureexertedbythe
solventmoleculestobelowerthaninthepuresolvent.

AsolutionthatobeysRaoult'slawiscalledanidealsolution.Suchsolutionsaregenerallydiluteandhaveverysmall
valuesofenthalpyofmixing,implyingthatthereareonlysmallinteractionsbetweentheirconstituentmolecules.We
canthinkofanidealsolutionasbeinganalogoustoanidealgas.

SolutionsContainingMorethanOneVolatileComponent
Whentwo(ormore)componentsofaliquidsolutioncanevaporate,thevapourcontainsmoleculesofeach.Each
volatilecomponentcontributesitsownpartialpressuretothetotalpressure.ByRaoult'slaw,thepartialpressureofa
particularcomponentisdirectlyproportionaltothecomponent'smolefractioninthesolution,andthetotalvapour
pressureisthesumofthepartialpressures.Tocalculatethesepartialpressures,weuseRaoult'slawforeach
component.ForcomponentA:

andforcomponentB:

ThetotalpressureaboveasolutionofliquidsAandBisthenthesumofp Aandp B.

Figure10.24showshowthevapourpressureofanideal,twocomponentsolutionofvolatilecompoundschangeswith
composition.

FIGURE10.24Thevapourpressureofanideal,twocomponentsolutionofvolatilecompounds.
 WORKEDEXAMPLE10.8

CalculatingtheVapourPressureofaSolutionofTwoVolatileLiquids

At20C,acetonehasavapourpressureof2.1310 4Pa.Thevapourpressureofwaterat20Cis2.30
10 3Pa.AssumingthatthemixtureobeysRaoult'slaw,calculatethevapourpressureofasolutionofacetone
andwatercontaining80.0mol%ofwater.

Analysis

Tofindp total,weneedtocalculatetheindividualpartialpressuresandthenaddthem.

Solution

Aconcentrationof80.0mol%watercorrespondstoamolefractionof0.800forwaterand0.200for
acetone,so:

Isouranswerreasonable?

Thevapourpressureofthesolution(6.1010 3Pa)hastobehigherthanthatofpurewater(2.3010 3Pa),

becauseofthevolatileacetone,butlessthanthatofpureacetone(2.1310 4Pa),becauseofthehighmole
fractionofwater.Theanswerseemstobereasonable.

PRACTICEEXERCISE10.12
At20C,thevapourpressureofcyclohexane(a
hydrocarbonsolvent)is8.8010 3Paandthatof
toluene(anothersolvent)is2.7810 3Pa.Whatis
thevapourpressureofasolutionofthetwoat20C
whentolueneispresentatamolefractionof0.700?

Becausesolutesinfluencethevapourpressuresofsolutions,theyalsoaffecttheirboilingandfreezingpoints.The
boilingpointofasolutionofanonvolatilesolute,forexample,ishigherthanthatofthepuresolvent,andthefreezing
pointofthesolutionislowerthanthatofthesolvent.Wecanexplainthisforaqueoussolutionsbyconsideringthe
phasediagramforwater(seefigure7.19,p.263).

BoilingPointElevationandFreezingPointDepression
Wehaveseenhowthepresenceofanonvolatilesoluteinasolutionincreasestheboilingpointofthesolutionrelative
tothatofthepuresolvent.Suchsolutionsalsohavelowerfreezingpointsthanthoseofthepuresolvents,meaningthat
theattractiveforcesbetweensolventmoleculesinthesolutionmustbesmallerthanthoseinthepuresolventatagiven
temperature.Thisisduetothepresenceofsolutemoleculesandthecorrespondingsolutesolventinteractions,which
arenotpresentinthepuresolvent.

Wecanillustratethechangesinboilingandfreezingpointsinsolutionsusingaphasediagram.Figure10.25showsa
phasediagramforanaqueoussolutioncontaininganonvolatilesolute(redlines)superimposedonthephasediagram
forpurewater(bluelines).Weknowthat,atanytemperature,theaqueoussolutionhasalowervapourpressurethan
purewater,sotheLiquidgasequilibriumlineliesbelowthatforpurewater.Thishastheeffectofloweringthe
pressureandtemperatureatthetriplepoint,sotheiceliquidequilibriumlineisalsodisplaced.Wecanseefromthe
phasediagramthattheboilingpointofthesolutionisincreasedbyTb,relativetowater,andthefreezingpointis
depressedbelow0CbyTf.TbiscalledtheboilingpointelevationandTfiscalledthefreezingpointdepression
andbothareadirectconsequenceofloweringthevapourpressureinthesolution.Theyarecolligativepropertiesas
theirmagnitudesaredirectlyproportionaltothenumberofsoluteparticlesinthesolution.WecancalculateTband
Tffromtheequations:

whereKbandKfarethemolalboilingpointelevationconstantandthemolalfreezingpointdepressionconstant,
respectively,andbisthemolalityofthesolutioninmolkg 1.KbandKfarepropertiesofthesolventonlyandare
independentoftheidentityofthesolutetable10.4givesvaluesofKbandKfforanumberofsolvents.Thesevalues
applyexactlytoverydilutesolutionsonly,butwecanusethemtoestimatethefreezingpointsandboilingpointsof
fairlyconcentratedsolutionswithreasonableprecision.

FIGURE10.25Phasediagramforanaqueoussolutionofanonvolatilesolute.

TABLE10.4 Molalboilingpointelevationandfreezingpointdepressionconstants
Solvent Kb(Kmol1kg) Kf(Kmol1kg)
water 0.51 1.86
aceticacid 3.07 3.57
benzene 2.53 5.07
chloroform 3.63
camphor 37.7
cyclohexane 2.69 20.0

WORKEDEXAMPLE10.9
 EstimatingaFreezingPointUsingaColligativeProperty

Estimatethefreezingpointofasolutionmadefrom10.00gofurea,CO(NH2)2(molarmass60.06gmol1),
in100.0gofwater.

Analysis

Tf=Kfbrelatesconcentrationtofreezingpointdepression.Tousetheequation,wemustfirstcalculatethe
molalityofthesolution.

Solution

ThisistheamountofCO(NH2)2in100.0gor0.1000kgofwater.Therefore:

Forourestimate,wemustnextuseTf=Kfb.Fromtable10.4,Kfforwateris1.86Kmol1kg.

Rememberingthatatemperaturedifferenceof3.10Kisequalto3.10C,thesolutionshouldfreezeat3.10
Cbelow0C,orat3.10C.

Isouranswerreasonable?

Forasolutionofmolality1molkg 1,thefreezingpointdepressionis:

Therefore,foreveryunitofmolality,thefreezingpointmustbedepressedbyabout2C.Themolalityof
thissolutionisbetween1molkg 1and2molkg 1,soweexpectthefreezingpointdepressiontobe
betweenabout2Cand4C.Itis.

PRACTICEEXERCISE10.13
Atwhattemperaturedoesa10%(bymass)aqueous
solutionofsugar,C12H22O11,boilat1.01310 5
Pa?

Wehavedescribedthepropertiesoffreezingpointdepressionandboilingpointelevationascolligativethatis,they
dependontherelativenumbersofparticles,ratherthantheiridentities.Becausetheeffectsareproportionaltomolal
concentrations,experimentalvaluesofTforTbcanbeusefulforcalculatingthemolarmassesofunknownsolutes.
We'llseehowthisworksinworkedexample10.10.

WORKEDEXAMPLE10.10

CalculatingaMolarMassfromFreezingPointDepressionData
Asolutionmadebydissolving5.65gofanunknownmolecularcompoundin110.0gofbenzenefrozeat
4.39C.Giventhatthenormalmeltingpointofbenzeneis5.45C,calculatethemolarmassofthesolute.
 Analysis

WecanuseTf=Kfbtocalculatetheamountofsoluteinthegivensolution.Thenwecandividethemass
ofsolutebytheamountofsolutetofindthemolarmass.

SolutionFromtable10.4,thevalueofKfforbenzeneis5.07Kmol1kg.Themagnitudeofthefreezing
pointdepressionis:

WenowuseTf=Kfbtofindthemolalityofthesolution:

Thismeansthatthereis0.209molofsoluteforeverykilogramofbenzeneinthesolution.Butwehave
only110.0gor0.1100kgofbenzene.Sotheactualamountofsoluteinthegivensolutionis:

Wecannowobtainthemolarmass:

Themassof1moleofthesoluteis246g.

Isouranswerreasonable?

Theeasiestwaytocheckouransweristodothereversecalculation,startingwith5.65gofacompound
havingamolarmassof246gmol1,anddeterminingtheresultantfreezingpointdepressionwhendissolved
in110.0gofbenzene.Ifyoudothis(it'sgoodpractice!),you'llfindthattheansweriscorrect.

PRACTICEEXERCISE10.14
Asolutionmadebydissolving3.46gofan
unknowncompoundin85.0gofbenzenefrozeat
4.13C.Whatisthemolarmassofthecompound?

OsmosisandOsmoticPressure
Inlivingthings,membranesofvariouskindskeepmixturesandsolutionsorganisedandseparated.Yetsome
substanceshavetobeabletopassthroughmembranessothatnutrientsandproductsofchemicalreactionscanbe
distributedcorrectly.Inotherwords,thesemembranesmusthaveaselectivepermeability.Theymustkeepsome
substancesfromgoingthroughwhileallowingotherstopass.Suchmembranesaresaidtobesemipermeable.

Thedegreeofpermeabilityvarieswiththekindofmembrane.Cellophane,forexample,ispermeabletowaterand
smallsoluteparticlesionsormoleculesbutimpermeabletoverylargemolecules,suchasthoseofstarchor
proteins.Specialmembranescanevenbepreparedthatarepermeableonlytowaterbutnottoanysolutes.

Dependingonthekindofmembraneseparatingsolutionsofdifferentconcentration,twosimilarphenomena,dialysis
andosmosis,canbeobserved.Botharefunctionsoftherelativepopulationsofparticlesinthedissolvedmaterialson
eithersideofthemembrane,sotheyarecolligativeproperties.

Whenamembraneiscapableofallowingbothwaterandsmallsoluteparticlestopassthrough,suchasmembranes
foundinlivingsystems,theprocessiscalleddialysis,andthemembraneiscalledadialysingmembrane.Itdoesnot
permithugemoleculestopassthrough,suchasthoseofproteinsandstarch.Artificialkidneymachinesusedialysing
membranestohelpfilterandremovethesmallermoleculesofwastesfromthebloodwhilethelargerprotein
molecules,whichcannotpassthroughthemembrane,areretainedintheblood.

Osmosisisanetshiftofonlysolventthroughamembrane,inadirectionfromthesidelessconcentratedinsoluteto
thesidemoreconcentrated.Thespecialmembranerequirediscalledanosmoticmembrane.Suchmembranesare
rare,buttheycanbemade.

Thedirectioninwhichosmosisoccurs,namely,thenetmovementofsolventfromthemoredilutesolution(orpure
solvent)intothemoreconcentratedsolution,maybeexplainedwiththehelpoffigure10.26.Watermoleculesmove
freelyacrossthemembrane.Theconcentrationofwaterintheaqueoussolution(B)islowerthantheconcentrationin
purewater(A).MorewatermoleculesareavailabletocrossthemembranefromAtoB,sotheflowofwatermolecules
intothesolutionissomewhatgreaterthantheflowoutofthesolution.Infigure10.26b,thenetflowfofwaterintothe
solutionhasvisiblyincreasedthevolumeofB.

FIGURE10.26Osmosisandosmoticpressure.

Ifwepushonthesolution,wecanforcewaterbackthroughthemembrane(fromBtoA).Theweightoftherisingfluid
columninfigure10.26bprovidesapushoropposingpressurethateventuallystopsosmosis.Ifweapplyfurther
pressure(figure10.26c),wecanforceenoughwaterbackthroughthemembranetorestorethesystemtoitsoriginal
condition.Theexactopposingpressureneededtopreventanyosmoticflowwhenoneoftheliquidsispuresolventis
calledthetosmoticpressureofthesolution.

Byexceedingtheosmoticpressure,osmosiscanbereversedandwerefertothissituationasreverseosmosis.Reverse
osmosisallowspurewatertobeobtainedfromanaqueoussaltsolutionsimplybyforcingitthroughamembrane
underhighpressure.Itisthereforewidelyusedtoobtaindrinkingwaterfromseawater.Therearecurrentlythree
reverseosmosisdesalinationplantsoperatinginAustralia,withafurtherthreeunderconstruction.

Tofurtherillustratetheprinciplesinvolvedinosmosis,considerthesituationinfigure10.27wehaveabeakerof
waterinanenclosedspacealreadysaturatedinwatervapour,andwehavejustaddedabeakerofanaqueoussolution
ofanonvolatilesolute.Watermoleculestendtoescapeintothevapourphasefrombothbeakers,buttheirrateof
escapefromthepurewater(largerupwardarrow)isgreaterthantheirrateofescapefromthesolution(smallerupward
arrow).Thismustbesobecausethevapourpressureofpurewaterisgreaterthanthatofthesolution,aspredictedby
Raoult'slaw.Therateatwhichwatermoleculesreturntothesolutionfromthesaturatedvapourstateisnotdiminished
bythepresenceofthesolute.Atthesolutionvapourinterface,morewatermoleculesreturntothesolutionthanleave
it,andthistakeswaterfromthevapourstate.Tokeepthevapourphasesaturated,moreofthepurewatermust
evaporate.Theneteffectisthatwatermovesfromthebeakerofpurewaterintothevapourspaceandthenintothe
solution.Inosmosis,anosmoticmembraneinsteadofbeakersseparatestheliquids,butthesameprinciplesareat
work.

FIGURE10.27Principlesatworkinosmosis.Here,beakers,insteadofasemipermeablemembrane,separatethepure
solvent(water)fromanaqueoussolutioncontaininganonvolatilesolute.Becausethevapourpressureofpure
waterisgreaterthanthevapourpressureoftheaqueoussolution,moleculestransferfromthebeakerofpure
watertotheaqueoussolution.

Thehighertheconcentrationofthesolution,themorewateristransferredtoit(figure10.27).Inotherwords,the
osmoticpressureofasolutionisproportionaltotherelativeconcentrationsofitssoluteandsolvent.

Thesymbolusedforosmoticpressureis,thecapitalGreekletterpi.Inadiluteaqueoussolution,(Pa)is
proportionalbothtotemperature,T(K),andmolarconcentration,c(molm3):

Theproportionalityconstantturnsouttobethegasconstant,R,soforadiluteaqueoussolutionwecanwrite:

Thisisthevan'tHoffequationforosmoticpressureandisanalogoustotheidealgaslaw.Notethatweworkinterms
ofconcentrationratherthanmolalityheretoemphasisethesimilarityofthisequationtotheidealgaslaw.Recallfrom
p.408that,providedthesolutionissufficientlydilute,themolalityandconcentrationarenumericallyessentiallyequal.

ChemicalConnections

Desalination

BothAustraliaandNewZealandaresusceptibletodrought.Recordlowrainfallsintheearlyyearsofthis
centuryledoneexperttostatethatAustraliawasinthegripofa1in1000yeardrought,whileNewZealand
experienceditsworstdroughtin100yearsinthe1990s.Asmajorcitiesinbothcountriesrelyonregular
rainfallfordrinkingwater,droughtconditionsthreatentheveryexistenceoftheselargepopulationcentres.
Climatechangemayalsoexacerbatetheproblemsassociatedwithdrought.

Asbothcountriesaresurroundedbywater,onepossiblesolutionliesintheconversionofseawaterto
drinkingwaterthroughdesalination.Thereareanumberofwaysinwhichthiscanbedone,butallofthem
requiresignificantquantitiesofenergy.Thesimplestwayofdesalinatingseawateristoboilitandcondense
thepurewatervapourthatresults.Thehighheatcapacityofwatermakesthismethodeconomically,
environmentallyandenergeticallyinfeasibleonalargescale.However,carryingouttheprocessatlow
pressuremeansthatthewaterboilsatalowertemperature,solessenergyisrequiredtoheatthewater.Of
course,theenergyrequiredtolowerthepressurealsoneedstobetakenintoaccountintheoveralleconomics
oftheprocess.SeveraldesalinationplantsintheMiddleEastuseavariantofthistechnologyandsomehave
capacitiesofover250millionlitresperday.

Currently,themostpopularmethodofdesalinationisreverseosmosis(seefigure10.29).Aswehaveseenin
thischapter,purewaterwillflowspontaneouslythroughasemipermeablemembranefromadiluteelectrolyte
solutiontoaconcentratedelectrolytesolution,therebyexertinganosmoticpressure.Ifapressuregreaterthan
thisisexertedonthemoreconcentratedsolution,thedirectionofflowcanbereversed,andpurewaterresults.
TheKurnelldesalinationplantinSydney,whichwasopenedin2010,operatesusingthisprinciple(figure
10.28).Itwasdesignedtoprovideaminimumof15%ofSydney'swaterneeds.Theelectricityrequiredto
generatetherequiredhighpressurescomesfromawindfarm,meaningthatthisplantrunsentirelyon
renewableenergy.Inaddition,researchersatMurdochUniversityhaveinventedtheSolarflow,aportable,
solarpowereddesalinationunitcapableofproducing400litresofwateradayusingreverseosmosis.Sucha
unitappearsidealforsmallcommunitiesinremoteareas.

FIGURE10.28KurnelldesalinationplantinSydney,NewSouthWales.
 FIGURE10.29Thefourmajorstepsinconversionofseawatertodrinkingwaterusingreverseosmosis.

Onelessthanobviousproblemwiththeuseofreverseosmosisplantsthatmustbeovercomeisthedisposal
oftheconcentratedsaltsolutionsthatareformed.Pumpingthesewastesbackintotheoceanatsourcecan
leadtohighlevelsofsaltinthelocalmarineenvironment,especiallyinshallowandslowmovingestuarine
waters,andthiscanhaveaharmfuleffectonmarinelife.Apossiblesolutionistopumpthewasteintodeep
offshorewaterswheretheseacurrentsdispersethesaltthishoweverdoeshaveattendantenergycosts.
Anothersolutionistheharvestingofsaltfromtheconcentratedresidues,andthismayindeedbeeconomically
viable.

Osmoticpressureisoftremendousimportanceinbiologyandmedicine.Cellsaresurroundedbymembranesthat
restricttheflowofsaltsbutallowwatertopassthroughfreely.Tomaintainaconstantamountofwater,theosmotic
pressureofsolutionsoneithersideofacellmembranemustbeidentical.Forexample,asolutionthatis0.9%NaClby
masshasthesameosmoticpressureasthecontentsofredbloodcells,andredbloodcellsbathedinthissolutioncan
maintaintheirnormalwatercontent.Thesolutionissaidtobeisotonicwithredbloodcells.Bloodplasmaisan
isotonicsolution.

Ifacellisplacedinasolutionwithasaltconcentrationhigherthantheconcentrationwithinthecell,osmosiscauses
watertoflowoutofthecell.Suchasolutionissaidtobehypertonic.Thecellshrinksanddehydrates,andeventually
dies.Thisprocesskillsfreshwaterfishandplantsthatarewashedouttosea.

Ontheotherhand,waterflowsintoacellifitisplacedintoasolutionwithanosmoticpressurethatismuchlowerthan
theosmoticpressureofthecell'scontents.Suchasolutioniscalledahypotonicsolution.Acellplacedindistilled
water,forexample,swellsandbursts.Theeffectsofisotonic,hypertonicandhypotonicsolutionsonredbloodcells
areshowninfigure10.30.

FIGURE10.30Effectsonredbloodcellsthathavebeenplacedinisotonic,hypertonicandhypotonicsolutions,allatthesame
magnification:
(a)Inanisotonicsolution(0.9%NaClbymass),solutionsoneithersideofthecellmembranehavethe
sameosmoticpressure,sothereisnonetflowofwaterinonedirectionacrossthemembrane.
(b)Inahypertonicsolution(5.0%NaClbymass),waterflowsfromanareaoflowersaltconcentration
(insidethecell)tohigherconcentration(thehypertonicsolution),causingthecelltodehydrate.
(c)Inahypotonicsolution(0.1%NaClbymass),waterflowsfromanareaoflowersaltconcentration(the
hypotonicsolution)tohigherconcentration(insidethecell).Thecellswellsandbursts.

Obviously,themeasurementofosmoticpressurecanbeveryimportantinpreparingsolutionsusedtoculturetissuesor
toadministermedicinesintravenously.Osmoticpressurescanbemeasuredbyaninstrumentcalledanosmometer,
illustratedandexplainedinfigure10.31.Osmoticpressurescanbeveryhigh,evenindilutesolutions,asworked
example10.11shows.

FIGURE10.31Simpleosmometer.Whensolventmovesintothesolutionbyosmosis,thelevelofthesolutioninthecapillary
rises.Theheightreachedisrelatedtotheosmoticpressureofthesolution.

WORKEDEXAMPLE10.11

CalculatingOsmoticPressure

Asolutionof1.0010 3Msugarinwaterisseparatedfrompurewaterbyanosmoticmembrane.What
osmoticpressure(inPa)developsat25C?

Analysis

Wecanuse=cRT.RecallthatR=8.314Jmol1K1.Rememberthat,whenweusethisequation,the
concentrationmustbeexpressedinmolm3togiveananswerinPa(1Pa=1Jm3,p.29).

Solution

Wemultiplytheconcentrationby1000toconvertfrommolL1tomolm3thus,c=1.00molm3.

Thus,theosmoticpressureof1.0010 3Msugarinwateris2.4810 3Pa.

Isouranswerreasonable?

Theunitsarethegreatestcauseoferrorincalculationslikethis.RemembertoexpressTinKandcinmol
m3,notmolL1.ThiswillgiveananswerinPa.

PRACTICEEXERCISE10.15
Whatistheosmoticpressureofa0.0115Mglucose
solutionatbodytemperature(37C)?
Inworkedexample10.11,yousawthata1.0010 3Msolutionofsugarhasanosmoticpressureof2.4810 3Pa.
Thispressurewouldsupportacolumnofthesolutionroughly25cmhigh.Ifthesolutionhadbeen100timesas
concentrated(0.100Msugarstillrelativelydilute),theheightofthecolumnsupportedwouldberoughly25m.

Anosmoticpressuremeasurementofadilutesolutioncanbeusedtodeterminethemolarconcentrationand,therefore,
themolarmassofamolecularsolute.Determinationofmolarmassbyosmoticpressureismuchmoresensitivethan
determinationbyfreezingpointdepressionorboilingpointelevation.Workedexample10.12showshowexperimental
measurementsofosmoticpressurecanbeusedtodeterminemolarmass.

WORKEDEXAMPLE10.12

CalculatingMolarMassfromOsmoticPressure
Anaqueoussolutionwithavolumeof100mLandcontaining0.122gofanunknownmolecularcompound
hasanosmoticpressureof2.1110 3Paat20.0C.Whatisthemolarmassofthesolute?

Analysis

Amolarmassistheratioofmasstoamount.Wearegiventhemassofthesolutetocalculatetheratio,we
needtofindtheamountequivalenttothismass.

Tofindtheamountofsolute,wemustfirstuse=cRTtofindtheconcentrationofthesolutioninmolm3.
Thenwecanusethegivenvolumeofthesolutionandtheconcentrationtocalculatetheamountthat
correspondsto0.122gofsolute.Finally,wecancalculatethemolarmassbydividingthemassofsoluteby
theamountofsolute.

Solution

First,calculatethesolution'sconcentrationusingtheosmoticpressure.Thetemperature,20.0C,
correspondsto293K.Recallthat1Pa=1Jm3.

Therefore,in100mLor0.100Lofsolution,wehave:

Themolarmassofthesoluteisthenobtainedintheusualway:

Isouranswerreasonable?

Allwecandoisdoublecheckthecalculationoftheamount,whichturnsouttobealittlelessthan10 4
mol.Dividingthemass,roughly0.12g,by10 4molgives0.1210 4gmol1,or1.210 3gmol1,which
isveryroughlywhatwefound.
 PRACTICEEXERCISE10.16
Asolutionofacarbohydratepreparedbydissolving
72.4mgin100mLofsolutionhasanosmotic
pressureof3.2910 3Paat25.0C.Whatisthe
molarmassofthecompound?

MeasurementofSoluteDissociation

Themolalfreezingpointdepressionconstantforwateris1.86Kmol1kg,andthereforeyoumightthinkthata1.00
molkg 1solutionofNaClwouldfreezeat1.86C.Instead,itfreezesatabout3.37C.Thisgreaterdepressionofthe
freezingpointbythesalt,whichisalmosttwice1.86C,isnothardtounderstandifwerememberthatcolligative
propertiesdependonthenumberofsoluteparticles.NaCl(s)undergoescompletedissociationintoitsconstituentions
inwateraccordingtotheequation:

Therefore,ifwedissolve1moleofNaCl(s)(58.5g)in1kgofwater,theresultingsolutionhasatotalmolalityof
dissolvedsoluteparticlesof2molkg 1:1molkg 1ofNa+ionsand1molkg 1ofClions.Theoretically,a1.00mol
kg 1NaClsolutionshouldfreezeat2(1.86C)or3.72C.(Whyitactuallyfreezesalittlehigherthanthis,at3.37
C,willbediscussedshortly.)

Ifwemadeupa1.00molkg 1solutionof(NH4)2SO4,wewouldhavetoconsiderthefollowingdissociation:

So,1moleof(NH4)2SO4givesatotalof3molesofions(2molesofNH4+and1moleofSO42).Weexpectthe
freezingpointofthissolutionof(NH4)2SO4tobe3(1.86C)=5.58C.

Youshouldensureyouunderstandthedistinctionbetweendissolutionanddissociation.Aslightlysolubleionicsolid
suchasAgCldissolvesonlytoaverysmallextent(i.e.itdoesnotundergocompletedissolution),butthesmallamount
ofresultingAg +andClionsinsolutionareessentiallycompletelydissociated(i.e.theyshowlittletendencytostick
together).

Whenwewanttoestimateacolligativepropertyofasolutionofanelectrolyte,werecalculatethesolution'smolality
assumingthatthesaltdissociatescompletely.Thisisillustratedinworkedexample10.13.

WORKEDEXAMPLE10.13

EstimatingtheFreezingPointofaSaltSolution

Estimatethefreezingpointofanaqueoussolutionof0.106molkg 1MgCl2,assumingthatitdissociates
completely.

Analysis

Theequationthatrelatesachangeinfreezingtemperaturetomolalityis:

Fromtable10.4,Kfforwateris1.86Kmol1kg.Wecannotsimplyuse0.106molkg 1forthemolarity
becauseMgCl2isanioniccompoundthatdissociatesinwaterwemustusethetotalmolalityofionsinthe
equation.
 Solution

WhenMgCl2dissolvesinwater,itdissociatesasfollows:

Because1moleofMgCl2gives3molesofions,theeffective(assumed)molalityofwhatwehavecalled
0.106molkg 1MgCl2isthreetimesasgreat:

NowwecanuseTf=Kfb:

Thefreezingpointisdepressedbelow0.000Cby0.591C,sowecalculatethatthissolutionfreezesat
0.591C.

Isouranswerreasonable?

Themolality,asrecalculated,isroughly0.3,so0.3of1.86(callit2)is0.6,which,afterweaddtheunitC
andsubtractfrom0C,gives0.6C,whichisclosetotheanswer.

PRACTICEEXERCISE10.17
Calculatethefreezingpointofanaqueoussolution
of0.237molkg 1LiClontheassumptionthatitis
100%dissociated.Calculateitsfreezingpoint
assuming0%dissociation.

Experimentsshowthatneitherthe1.00molkg 1(NH4)2SO4northe1.00molkg 1NaClsolutiondescribedaboveand

onthepreviouspagefreezesataslowatemperatureascalculated.Ourassumptionthatanelectrolyteseparates
completelyintoitsionsisincorrect.Someoppositelychargedionsexistasverycloselyassociatedpairs,calledion
pairs,whichbehaveassinglemolecules.Clusterslargerthantwoionsprobablyexistalso.Theformationofionpairs
andclustersmakestheactualparticleconcentrationina1.00molkg 1NaClsolutionsomewhatlessthan2.00mol
kg 1.Asaresult,thefreezingpointdepressionof1.00molkg 1NaClisnotquiteaslargeasthatcalculatedonthe
basisof100%dissociation.

Assolutionsofelectrolytesaremademoredilute,theobservedandcalculatedfreezingpointscomeclosertogether.At
evergreaterdilutions,theassociationofionsislessofacomplicationbecausetheionsarefurtherapart,sothesolutes
behavemoreandmoreasiftheywere100%separatedintotheirions.

Chemistscomparethedegreesofdissociationofelectrolytesatdifferentdilutionsbyaquantitycalledthevan'tHoff
factor(i).Thisistheratiooftheobservedfreezingpointdepressiontothevaluecalculatedontheassumptionthatthe
solutedissolvesasanonelectrolyte:

Thetheoreticalvan'tHofffactor,i,is2forNaCl,KClandMgSO4,whichbreakupintotwoionson100%dissociation.
ForK2SO4,thetheoreticalvalueofiis3becauseeachK2SO4unitgivesthreeions.Theactualvan'tHofffactorsfor
severalelectrolytesatdifferentdilutionsaregivenintable10.5.Noticethatwithdecreasingconcentration(i.e.at
higherdilutions)theexperimentalvan'tHofffactorsagreebetterwiththeircorrespondingtheoreticalvan'tHofffactors.
TABLE10.5 Effectofconcentrationonvan'tHofffactor
van'tHofffactor(i)
 Molalconcentration(molsalt/kgwater) If100%dissociationoccurred
Salt 0.1 0.01 0.001
NaCl 1.87 1.94 1.97 2.00
KCl 1.85 1.94 1.98 2.00
K2SO4 2.32 2.70 2.84 3.00

MgSO4 1.21 1.53 1.82 2.00

Theincreaseinthepercentageofcompletedissociationthatcomeswithgreaterdilutionisnotthesameforallsalts.In
goingfrommolalitiesof0.1to0.001molkg 1,theincreasein%dissociationofKCla,asmeasuredbythechangeini,
isonlyabout7%.ForK2SO4,theincreaseforthesamedilutionisabout22%,adifferencecausedbytheanionSO42.
ThisanionhastwicethechargeoftheanioninKCl,sotheSO42ionattractsK+morestronglythancanCl.Hence,
lettinganionof2chargeandanionof1+chargegetfartherapartbydilutionhasagreatereffectontheiracting
independentlythangivingionsof1and1+chargemoreroom.Whenbothcationandanionaredoublycharged,the
improvementin%dissociationwithdilutionisevengreater.Wecanseefromtable10.5thatthereisanalmost50%
increaseinthevalueofiforMgSO4aswegofroma0.1toa0.001molkg 1solution.

Therearemanysubstancesinwhichdissociationisfarfromcomplete.Forexample,in1.00molkg 1aqueousacetic
acid(aweakacid),thefollowingequilibriumexists:

Thesolutionfreezesat1.90C.Thisisonlyalittlelowerthanthatexpected(1.86C)ifnoionisationoccurred,
whichisevidenceforonlyasmallamountofionisation.Wecanestimate%ionisationbythefollowingcalculation.

Wefirstusethedatatocalculatetheapparentmolalityofthesolution:i.e.themolalityofalldissolvedspecies,
CH3COOH,CH3COOandH3O+.WeagainuseTf=Kfb,butnowlettingbstandfortheapparentmolality.Kfis1.86
Kmol1kgso:

Ifthereis1.02molofallsolutespeciesin1kgofsolvent,wehave0.02molofsolutespeciesmorethanwestarted
with,becausewebeganwith1.00molofaceticacid.Sincewegetjustoneextraparticleforeachaceticacidmolecule
thationises,theextra0.02molofparticlesmusthavecomefromtheionisationof0.02molofaceticacid.So:

Inotherwords,thisprocedureestimatesthe%ionisationin1.00molkg 1aceticacidtobe2%.(Otherkindsof
measurementsofferbetterprecision,andthe%ionisationofaceticacidatthisconcentrationisactuallylessthan1%.)
Wewilldiscusstheionisationofacidsingreaterdetailinchapter11.

Somemolecularsolutesproducesmallercolligativeeffectsthantheirmolalconcentrationswouldleadustopredict.
Thisisoftenevidencethatsolutemoleculesareclusteringorundergoingassociationinsolution.Forexample,when
dissolvedinbenzene,benzoicacidmoleculesassociateasdimersheldtogetherbyhydrogenbonds:
Becauseofassociation,thedepressionofthefreezingpointofa1.00molkg 1solutionofbenzoicacidinbenzeneis
onlyabouthalfofthecalculatedvalue.Byformingadimer,benzoicacidhasaneffectivemolecularmasstwicethat
normallycalculated.Thelargereffectivemolarmassreducesthemolalconcentrationofparticlesbyafactoroftwo,
andtheeffectonthefreezingpointdepressionishalved.

Itisappropriatethatwehavefinishedthischapterwithtwoexamplesinvolvingacids.Inthenextchapter,wewilllook
atthesolutionpropertiesofacidsandbasesindetail,andwewillseethatthebehaviourofthesecompoundsin
solutionisgovernedbytheprincipleswehaveoutlinedinthisandtheprevioustwochapters.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
IntroductiontoSolutionsandSolubility
Asolutionisahomogeneousmixtureoftwoormorepuresubstancesthatcanbegases,liquidsor
solids.Theliquidinaliquidsolutioniscalledthesolvent,andthedissolvedsubstanceisthesolute.A
saturatedsolutioncontainsthemaximumpossibleamountofdissolvedsoluteatthegiventemperature
andpressure.

GaseousSolutions
Allgasesmixspontaneouslyinallproportions.Astheenthalpychangeformixingisusuallysmall,
owingtotheverylowinteratomicorintermolecularforcesbetweenthegasatomsormolecules,the
mixingprocessisessentiallyentropydriven.

LiquidSolutions
Incontrasttogaseoussolutions,liquidsolutionshavesignificantintermolecularinteractionsinvolving
solventmoleculessotheygenerallyhavesignificantenthalpiesofsolution,solH.Thetwocontributions
tosolHwhenagasdissolvesinaliquidaretheenergyrequiredtoopenpocketsinthesolventandthe
energyreleasedwhengasmoleculesoccupythesepockets.solHvaluesareusuallypositiveforgases
inorganicsolventsandnegativeforgasesinwater.Thesolubilitiesofgasesinwaterusuallydecrease
withincreasingtemperature.Henry'slaw,cgas=kHp gas,statesthattheconcentrationofagasinaliquid
atconstanttemperatureisdirectlyproportionaltothepartialpressureofthegasabovethesolution.

Twoliquidsthatmixcompletelyinallproportionsaresaidtobemiscible,whilethosethatdonotmix
areimmiscible.Liquidsofsimilarpolaritiesareoftenmiscibleinotherwords,likedissolveslike.
Dissolutionofanioniccompoundinwatergivesthehydratedfreeions,aspecificformofsolvation.
Polarmoleculesaregenerallysolubleinpolarsolventsandviceversa.

Themolarenthalpyofsolutionofasolidistheenthalpychangewhen1moleofacrystallinesubstance
isdissolvedinasolvent.Thesolubilityofasolidinaliquidistemperaturedependentandgenerally
increaseswithincreasingtemperature.

QuantificationofSolubility:theSolubilityProduct
Thesolubilityproduct,Ksp,istheequilibriumconstantforthedissolutionofaslightlysolublesaltina
solvent(usuallywater).Forthegeneralequilibrium:

itiswrittenasKsp=[Mb b+]a [Xa]b.Themolarsolubility(s)ofasaltataspecifiedtemperatureisthe

amountofthesaltdissolvedin1litreofasaturatedsolutionatthattemperature.Therelationship
betweensandKspdependsonthenatureofthesalt.Fora1:1salt,Ksp=s2,fora1:2salt,Ksp=4s3,for
a1:3salt,Ksp=27s4and,fora2:3salt,Ksp=108s5.

Theeffectofaddingacommoniontoasaturatedsolutionofaslightlysolublesaltcanbecalculatedby
comparingQsp(sometimescalledtheionicproduct)withKsp.Wecanusethesamemethodtopredictif
aprecipitatewillformwhentwosolutionsaremixed.Thecommonioneffectshowsthatsaltsarealways
lesssolubleinthepresenceofacommonion,providingnofurtherchemicalreactionispossible.

ColligativePropertiesofSolutions
Asolutioncontaininganonvolatilesoluteboilsatahighertemperatureandfreezesatalower
temperaturethanthepuresolvent.Thiscanbeexplainedintermsofthecolligativepropertiesofthe
solvent.Insodoing,insteadofexpressingsolutioncompositionintermsofmolarconcentrationor
molarity,itisnecessarytousemolalconcentrationormolality(b),whichisdefinedas:

Weusemolefractions,x,whenexplainingtheeffectofasoluteonboilingandfreezingpoints.Raoult's
law, ,showsthatthepressureaboveasolutionisproportionaltothemole
fractionofthesolventinadilutesolution.Thisisduetoareductioninthenumberofmoleculesof
solventatthesurfaceofthesolution,whichleadstoalowervapourpressureforthesolutionthanforthe
puresolvent.AnidealsolutionobeysRaoult'slaw.Eachcomponentofanidealsolutionconsistingof
twovolatileliquidsAandBobeysRaoult'slaw,suchthat .Theboilingpoint
elevationandfreezingpointdepressionofasolutioncontaininganonvolatilesoluteisduetothe
reducedvapourpressureofthesolutionrelativetothatofthepuresolvent.Themagnitudesofthese
effectscanbedeterminedusingtheequationsTb=KbbandTf=Kfb,whereKbandKfarethemolal
boilingpointelevationconstantandthemolalfreezingpointdepressionconstantofthesolvent,
respectively,andbisthemolalityofthesolution(molkg 1).

Dialysisisthepassageofwaterandsmallsoluteparticlesthroughasemipermeablemembrane,while
osmosisisthepassageofsolventonly.Osmosisoccursthroughanosmoticmembraneandresultsina
netshiftofsolventfromthesidelessconcentratedinsolutetothesidemoreconcentrated.Theosmotic
pressure()isthatrequiredtostopthisnetflowofsolventwhenoneoftheliquidsispurewater.The
van'tHoffequationforosmoticpressureisV=nRTandisanalogoustotheidealgasequation.

Freezingpointdepressioncanbeusedtoestimatethedegreeofdissociationofionicsaltsinsolution.
Theseresultsoftenshowthatsuchsaltsdonotdissociatecompletelybutexisttoacertainextentasion
pairsinsolution.Thevan'tHofffactor(i)measuresthedegreeofdissociationofanelectrolytein
solution.Asasolutionbecomesmoredilute,thedegreeofdissociationincreases.Freezingpoint
depressionalsogivesevidencefortheassociationofmolecularsolutesinsolution.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Henry'slaw(section10.3)
Thislaw:

allowscalculationofthesolubilityofagasinasolventatagivenpressurefromitssolubilityatanother
pressure.

Likedissolveslikerule(section10.3)
Thisruleuseschemicalcompositionandstructuretopredictwhethertwosubstancescanforma
solution.

Solubilityproductconstant,Ksp(section10.4)
WeuseKsptocalculatethemolarsolubilityofasalt,eitherinpurewaterorinasolutionthatcontainsa
commonion.ComparisonofKspwithQspallowsustodecidewhetheraprecipitatewillformonmixing
ionicsolutions.

Molarsolubility(section10.4)
WecanusemolarsolubilitytocalculatethevalueofKspforaslightlysolublesalt.

Commonioneffect(section10.4)
Thepresenceofacommonioninasolutionlowersthesolubilityofasaltcontainingthatcommonion
inthesolution.

Molalconcentration(molality)(section10.5)
Thelaw:

providesatemperatureindependentconcentrationexpressionforusewithcolligativeproperties.

Raoult'slaw(section10.5)
Thisexpression:

isusedtocalculatetheeffectofasoluteonthevapourpressureofasolution.

Freezingpointdepression(Tf)andboilingpointelevation(Tb)(section10.5)
Theexpressions:

and:

enableustoestimatefreezingandboilingpoints,molarmassesand%dissociationofaweak
electrolyte.

Equationforosmoticpressure(section10.5)
Weusethisequation:
toestimatetheosmoticpressureofasolutionortocalculatemolarmassesfromosmoticpressureand
concentrationdata.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
IntroductiontoSolutionsandSolubility
10.1Definethefollowingterms.
(a)solution
(b)solvent
(c)solute
(d)solubility
(e)saturatedsolution
(f) dissolution
GaseousSolutions
10.2Whydotwogasesmixspontaneouslywhentheyarebroughtintocontact?
LiquidSolutions
10.3Whensubstancesformliquidsolutions,whattwofactorsdeterminethesolubilityofthesolutein
thesolvent?
10.4Methanol,CH3OH,andwateraremiscibleinallproportions.Whatdoesthismean?Explainhow
theOHunitinmethanolcontributestothis.
10.5Petrolandwaterareimmiscible.Whatdoesthismean?Explainwhytheyareimmiscibleinterms
ofstructuralfeaturesoftheirmoleculesandforcesofattractionbetweenthem.
10.6Iodine,I2,isonlyveryslightlysolubleinwaterbutdissolvesreadilyintetrachloromethane,a
nonpolarsolvent.Whydoyouthinkthisis?
10.7Iodinedissolvesfarbetterinethanol(toformtinctureofiodine,anoldantiseptic)thaninwater.
Whatdoesthistellusaboutthealcoholmoleculescomparedwithwatermolecules?
10.8Thevalueof Hforaparticularsolublecompoundis+26kJmol1.Ifanearlysaturated
sol
solutionispreparedinaninsulatedcontainer(e.g.acoffeecupcalorimeter),willthesystem's
temperatureincreaseordecreaseasthesolutedissolves?
10.9Whichwouldbeexpectedtohavethelargerhydrationenthalpy,Al3+orLi+?Why?(Bothionsare
aboutthesamesize.)
10.10ThevalueofsolHfortheformationofanacetonewatersolutionisnegative.Explainthisin
termsofintermolecularforcesofattraction.
10.11ThevalueofsolHfortheformationofanethanolhexanesolutionispositive.Explainthisin
termsofintermolecularforcesofattraction.
10.12IfthevalueofsolHfortheformationofamixtureoftwoliquidsAandBis0,whatdoesthis
implyabouttherelativestrengthsofAA,BBandABintermolecularattractions?
10.13IfasaturatedsolutionofNH4NO3in100gofsolventat70Ciscooledto10C,whatmassof
solutewillprecipitate?(Usedatainfigure10.15.)
10.14AhotconcentratedsolutioninwhichequalmassesofNaIandNaBraredissolvedisslowly
cooledfrom50C.Whichsaltprecipitatesfirst?(Usedatainfigure10.15.)
10.15Fishermenknowthat,onhotsummerdays,thelargestfisharefoundindeepsinksinlake
bottoms,wherethewateriscoolest.Usethetemperaturedependenceofoxygensolubilityin
watertoexplainwhy.
10.16WhatisHenry'slaw?
10.17Mountainstreamsoftencontainfewerlivingthingsthanequivalentstreamsatsealevel.Interms
 ofoxygensolubilityatdifferentpressures,giveonereasonwhythismightbetrue.
10.18Whydoesabottledcarbonatedbeveragefizzwhenyoutakethecapoff?
QuantifiCationofSolubility:theSolubilityProduct
10.19WhatisthedifferencebetweenQspandKsp?
10.20UsethefollowingequilibriumtodemonstratewhytheKspexpressiondoesnotincludethe
concentrationofBa3(PO4)2inthedenominator.

10.21Whatisthecommonioneffect?UsethesolubilityequilibriumforAgCltoillustratethecommon
ioneffect.
10.22WithrespecttoKsp,whatconditionsmustbemetbeforeaprecipitateformsinasolution?
10.23WhatlimitstheaccuracyandreliabilityofsolubilitycalculationsbasedonKspvalues?
ColligativePropertiesofSolutions
10.24Howdoesthemolalityofasolutionvarywithincreasingtemperature?Howdoesthemolarityof
asolutionvarywithincreasingtemperature?
10.25Supposea1.0molkg 1solutionofasoluteismadeusingasolventwithadensityof1.15g
mL1.Isthemolarityofthissolutionnumericallylargerorsmallerthan1.0?Explain.
10.26Whatspecificfactaboutaphysicalpropertyofasolutionmustbetruetocallitacolligative
property?
10.27Viewedatamolecularlevel,whatcausesasolutioncontaininganonvolatilesolutetohavea
lowervapourpressurethanthesolventatthesametemperature?
10.28Whatkindsofdataareneededtofindoutifasolutionoftwomiscibleliquidsisalmostexactly
anidealsolution?
10.29Whenoctaneismixedwithethanol,thevapourpressureoftheoctaneoverthesolutionishigher
thanwhatwewouldcalculateusingRaoult'slaw.Why?Explainthediscrepancyintermsof
intermolecularattractions.
10.30Whenanaqueoussolutionofsodiumchloridestartstofreeze,whydon'ttheicecrystalscontain
ionsofthesalt?
10.31Explainwhyanonvolatilesolutedissolvedinwatergivesthesystem:
(a)ahigherboilingpointthanwater
(b)alowerfreezingpointthanwater.
10.32Whydowecalldialysingandosmoticmembranessemipermeable?Whatistheoppositeof
permeable?
10.33Whatisthekeydifferencebetweendialysingandosmoticmembranes?
10.34Whatismeantbydialysis?
10.35Atamolecularlevel,explainwhyinosmosisthereisanetmigrationofsolventfromthesideof
themembranelessconcentratedinsolutetothesidemoreconcentratedinsolute.
10.36Twoglucosesolutionsofunequalmolarityareseparatedbyanosmoticmembrane.Which
solutionloseswater,theonewiththehigherorthelowermolarity?
10.37Whatisthedifferencebetweenahypertonicsolutionandahypotonicsolution?
10.38Whyarecolligativepropertiesofsolutionsofioniccompoundsusuallymorepronouncedthan
thoseofsolutionsofmolecularcompoundsofthesamemolalities?
10.39Whatisthevan'tHofffactor?Whatisitsexpectedvalueforallnondissociatingmolecular
 solutes?Ifitsmeasuredvalueisslightlylargerthan1.0,whatdoesthissuggestaboutthesolute?
Whatissuggestedbyavan'tHofffactorofapproximately0.5?
10.40Whichaqueoussolution,ifeither,islikelytohavethehigherboilingpoint,0.50molkg 1NaIor
0.50molkg 1Na2CO3?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
10.41Considertheformationofasolutionofaqueouspotassiumchloride.Writethethermochemical
equationsforthe:
(a)conversionofsolidKClintoitsgaseousions
(b)subsequentformationofthesolutionbyhydrationoftheions.
ThelatticeenthalpyofKClis690kJmol1,andthehydrationenthalpyoftheionsis686
kJmol1.
(c) CalculatetheenthalpyofsolutionofKClinkJmol1.
10.42SupposethelatticeenthalpyofKClwasjust2%greaterthanthevaluegivenintable10.2.What
thenwouldbethecalculatedsolH(inkJmol1)?HowwouldthisnewvalueofsolHcompare
withthatgiveninthetable?Bywhatpercentageisthenewvaluedifferentfromthevalueinthe
table?(Theaimofthiscalculationistoshowthatsmallpercentageerrorsintwolargenumbers,
suchaslatticeenthalpyandhydrationenthalpy,cancauselargepercentagechangesinthe
absolutedifferencebetweenthem.)
10.43Iftheenthalpyofsolutionofanioniccompoundinwateris+14kJmol1,andthelatticeenthalpy
is630kJmol1,estimatethehydrationenthalpyoftheionsinthecompound.
10.44Iftheenthalpyofsolutionofanioniccompoundinwateris50kJmol1,andthehydration
enthalpyis890kJmol1,estimatethelatticeenthalpyoftheioniccompound.
10.45Thesolubilityofmethane,thechiefcomponentofnaturalgas,inwaterat20Cand110 5Pa
pressureis0.025gL1.Whatisitssolubilityinwaterat1.510 5Paand20C?
10.46At9.7410 4Paand20C,nitrogenhasasolubilityinwaterof0.018gL1.At8.1610 4Pa
and20C,itssolubilityis0.015gL1.ShowthatnitrogenobeysHenry'slaw.
10.47Ifthesolubilityofagasinwateris0.010gL1at25C,andthepartialpressureofthegasover
thesolutionis1.010 5Pa,predictthesolubilityofthegasatthesametemperaturebutatdouble
thepressure.
10.48If100.0mLofwaterisshakenwithoxygengasat1.010 5Pa,0.0039gofO willdissolve.
2
EstimatetheHenry'slawconstantforoxygengasinwater.
10.49WritetheKspexpressionsforeachofthefollowingcompounds:(a)CaF2,(b)Ag 2CO3,(c)
PbSO4,(d)Fe(OH)3,(e)PbI2,(f)Cu(OH)2,(g)AgI,(h)Ag 3PO4,(i)PbCrO4,(j)Al(OH)3,(k)
ZnCO3,(l)Zn(OH)2.
10.50Bariumsulfate,BaSO4,issoinsolublethatitcanbeswallowedwithoutsignificantdanger,even
thoughBa2+istoxic.At25C,1.00Lofwaterdissolvesonly0.00245gofBaSO4.Calculate
KspforBaSO4.
10.51Astudentfoundthatamaximumof0.800gAgOOCCH3candissolvein100mLofwater.What
arethemolarsolubilityandtheKspforthissalt?
10.52ItwasfoundthatthemolarsolubilityofBaSO in0.10mBaCl is8.010 6M.Whatisthevalue
3 2
ofKspforBaSO3?
10.53AstudentpreparedasaturatedsolutionofCaCrO4andfoundthat,when156mLofthesolution
evaporated,0.649gofCaCrO4wasleftbehind.WhatisthevalueofKspforthissalt?
10.54At25C,themolarsolubilityofAg PO is1.810 5molL1.CalculateK forthissalt.
3 4 sp
10.55ThemolarsolubilityofBa (PO ) inwaterat25Cis1.410 8molL1.WhatisthevalueofK
3 42 sp
forthissalt?
10.56Usethedataintable10.3todeterminethemolarsolubilitiesofthefollowingcompoundsin
water:(a)PbBr2,(b)Ag 2CrO4,(c)PbI2.
10.57At25C,thevalueofK forLiFis1.710 3andthatforBaF is1.710 6.Whichsalt,LiFor
sp 2
BaF2,hasthelargermolarsolubilityinwater?CalculatethesolubilityofeachinunitsofmolL1.
10.58At25C,thevalueofK forAgCNis2.210 16andthatforZn(CN) is310 16.Intermsof
sp 2
gramsper100mLofsolution,whichsaltisthemoresolubleinwater?
10.59AsaltwithaformulaintheformMXhasavalueofK equalto3.210 10.Anotherslightly
sp
solublesalt,MX3,musthavewhatvalueofKspifthemolarsolubilitiesofthetwosaltsaretobe
identical?
10.60Calciumsulfateisfoundinplaster.At25C,thevalueofK forCaSO is2.410 5.Whatisthe
sp 4
calculatedmolarsolubilityofCaSO4inwater?
10.61Copper(I)chloride,CuCl,hasK =1.910 7at25C.CalculatethemolarsolubilityofCuClin
sp
(a)purewater,(b)0.0200MHClsolution,(c)0.200MHClsolutionand(d)0.150MCaCl2
solutionat25C.
10.62Gold(III)chloride,AuCl ,hasK =3.210 25at25C.CalculatethemolarsolubilityofAuCl
3 sp 3
in(a)purewater,(b)0.010MHClsolution,(c)0.010MMgCl2solutionand(d)0.010M
Au(NO3)3solutionat25C.AssumethatAuCl3doesnotreactwithanyofthecompoundsin(b),
(c)or(d).
10.63CalculatethemolarsolubilityofAg 2CrO4at25Cin(a)0.200MAgNO3and(b)0.200M
Na2CrO4.(ForAg 2CrO4at25C,Ksp=1.210 12.)
10.64WhatisthemolarsolubilityofMg(OH)2in0.20MNaOHat25C?(ForMg(OH)2,Ksp=7.1
10 12at25C.)
10.65CalculatethemolarsolubilityofCaSO4in0.015MCaCl2at25C.
10.66CalculatethemolarsolubilityofAgClin0.050MAlCl3at25C.
10.67Inanexperiment,2.20gofNaOH(s)isaddedto250mLof0.10MFeCl2solutionat25C.
WhatmassofFe(OH)2isformed?WhatisthemolarconcentrationofFe2+inthefinalsolution?
10.68Supposethat1.75gofNaOH(s)isaddedto250mLof0.10MNiCl2solutionat25C.What
mass,ingrams,ofNi(OH)2isformed?
10.69WhatisthemolarsolubilityofCa(OH)2in(a)0.10MCaCl2and(b)0.10MNaOHat25C?
10.70DoesaprecipitateofPbCl2formwhen0.0150molofPb(NO3)2and0.0120molofNaClis
dissolvedin1.00Lofsolutionat25C?
10.71Silveracetate,AgOOCCH ,hasK =2.310 3at25C.Doesaprecipitateformwhen0.015
3 sp
molofAgNO3and0.25molofCa(OOCCH3)2isdissolvedinatotalvolumeof1.00Lof
solutionat25C?
10.72DoesaprecipitateofPbBr2formif50.0mLof0.0100MPb(NO3)2ismixedwith(a)50.0mLof
0.0100MKBrand(b)50.0mLof0.100MNaBrat25C?
10.73Doesaprecipitateofsilveracetate,AgOOCCH3,formif22.0mLof0.100MAgNO3isaddedto
 45.0mLof0.0260MNaOOCCH3at25C?(ForAgOOCCH3,Ksp=2.310 3at25C.)
10.74BothAgClandAgIareveryslightlysolublesalts,butthesolubilityofAgIismuchlessthanthat
ofAgCl,ascanbeseenbytheirKspvalues.SupposethatasolutioncontainsbothClandIwith
[Cl]=0.050Mand[I]=0.050Mat25C.IfsolidAgNO3isaddedto1.00Lofthismixture(so
thatnoappreciablechangeinvolumeoccurs),whatisthevalueof[I]whenAgClfirstbeginsto
precipitate?
10.75SupposethatNa SO isaddedgraduallyto100mLofasolutionthatcontainsbothCa2+ions
2 4
(0.15M)andSr ions(0.15M)at25C.(a)WhatistheSr2+concentration(inmolL1)when
2+
CaSO4justbeginstoprecipitate?(b)Whatpercentageofthestrontiumionhasprecipitatedwhen
CaSO4justbeginstoprecipitate?
10.76WhatisthemolalityofNaClinasolutionthatis3.000MNaClwithadensityof1.07gmL1?
10.77Asolutionofaceticacid,CH3COOH,hasaconcentrationof0.143Mandadensityof1.00g
mL1.Whatisthemolalityofthissolution?
10.78Whatisthemolalconcentrationofglucose,C6H12O6,(asugarfoundinmanyfruits)inasolution
madebydissolving24.0gofglucosein1.00kgofwater?Whatisthemolefractionofglucose
inthesolution?
10.79Anaqueoussolutionofpropan2ol,CH3CH(OH)CH3,(rubbingalcohol)hasamolefractionof
alcoholequalto0.250.Whatisthemolalityofthealcohol?
10.80AnaqueoussolutionofNaNO hasaconcentrationof0.363molkg 1andadensityof1.0185g
3
mL1.CalculatethemolarconcentrationofNaNO3andmolefractionofNaNO3inthesolution.
10.81Thevapourpressureofwateris3.1310 3Paat25C.Whatisthevapourpressureofasolution
preparedbydissolving65.0gofC6H12O6(anonvolatilesolute)in150gofwater?(Assumethe
solutionisideal.)
10.82At25C,thevapourpressuresofbenzene,C H ,andtoluene,C H ,are1.2310 4and3.54
6 6 7 8
3
10 Pa,respectively.Asolutionispreparedbymixing60.0gofbenzeneand40.0goftoluene.
Atwhatpressurewillthissolutionboil?
10.83Pentane,C5H12,andheptane,C7H16,aretwohydrocarbonliquidspresentinpetrol.At20C,the
vapourpressureofpentaneis5.5310 4Paandthevapourpressureofheptaneis4.7410 3Pa.
Whatisthetotalvapourpressureofasolutionpreparedbymixingequalmassesofthetwo
liquids?
10.84Thevapourpressureofpuremethanol,CH OH,at30Cis2.1110 4Pa.Whatmassofthe
3
nonvolatilesoluteglycerol,HOCH2CH(OH)CH2OH,mustbeaddedto100gofmethanolto
obtainasolutionwithavapourpressureof1.8410 4Pa?
10.85Asolutioncontaining8.3gofanonvolatile,nondissociatingsubstancedissolvedin1moleof
chloroform,CHCl3,hasavapourpressureof6.7210 4Pa.ThevapourpressureofpureCHCl3
atthesametemperatureis6.9210 4Pa.Calculate(a)themolefractionofthesolute,(b)the
amountofsoluteinthesolutionand(c)themolarmassofthesolute.
10.86At21.0C,asolutionof18.26gofanonvolatile,nonpolarcompoundin33.25gof
bromoethane,CH3CH2Br,hasavapourpressureof4.4210 4Pa.Thevapourpressureofpure
bromoethaneatthistemperatureis5.2610 4Pa.Whatisthemolarmassofthecompound?
10.87Estimatetheboilingandfreezingpointsofa2.00molkg 1solutionofsugarinwater.(Itis
 largelythesugarinicecreamthatmakesitdifficulttokeepicecreamfrozenhard.)
10.88Glycerol,HOCH CH(OH)CH OH(M=92gmol1),isessentiallyanonvolatileliquidthatisvery
2 2
solubleinwater.Asolutionismadebydissolving46.0gofglycerolin250gofwater.Calculate
theapproximatefreezingpointofthesolutionandtheboilingpointofthesolution.
10.89Whatmassofsucrose,C12H22O11,isneededtolowerthefreezingpointof100gofwaterby
3.00C?
10.90Whatistheboilingpointofthesolutiondescribedinquestion10.89?
10.91Asolutionof12.00gofanunknownnondissociatingcompounddissolvedin200.0gof
benzenefreezesat3.45C.Calculatethemolarmassoftheunknown.
10.92Asolutionof14gofanonvolatile,nondissociatingcompoundin1.0kgofbenzeneboilsat81.7
C.Calculatethemolarmassoftheunknown.
10.93AnondissociatingmolecularcompoundhastheempiricalformulaC4H2N.If3.84gofthe
compoundin500gofbenzenegivesafreezingpointdepressionof0.307C,whatareitsmolar
massandmolecularformula?
10.94Benzenereactswithhotconcentratednitricaciddissolvedinsulfuricacidtogivechiefly
nitrobenzene,C6H5NO2.Abyproductisoftenobtained,whichcomprises42.86%C,2.40%H
and16.67%N(bymass).Theboilingpointofasolutionof5.5gofthebyproductin45gof
benzenewas1.84Chigherthanthatofbenzene.
(a)Calculatetheempiricalformulaofthebyproduct.
(b)Calculateamolarmassofthebyproductanddetermineitsmolecularformula.
10.95Anaqueoussolutionofacompoundwithaveryhighmolarmasswaspreparedata
concentrationof2.0gL1at25C.Itsosmoticpressurewas2.76Pa.Calculatethemolarmassof
thecompound.
10.96Asaturatedsolutionof0.400gofapolypeptidein1.00Lofanaqueoussolutionhasanosmotic
pressureof4.9210 2Paat27C.Whatistheapproximatemolarmassofthepolypeptide?
10.97Thevapourpressureofwaterat20Cis2.3010 3Pa.Calculatethevapourpressureat20Cof
asolutionmadebydissolving10.0gofNaClin100gofwater.(Assumecompletedissociation
ofthesoluteandanidealsolution.)
10.98WhatmassofAlCl3wouldhavetobedissolvedin150mLofwatertogiveasolutionthathasa
vapourpressureof5.0910 3Paat35C?(Assumecompletedissociationofthesoluteandideal
solutionbehaviour.At35C,thevapourpressureofpurewateris5.5510 3Pa.)
10.99Belowaretheconcentrationsofthemostabundantionsinseawater.

Ion Molality(molkg1)
chloride 0.566
sodium 0.486
magnesium 0.055
sulfate 0.029
calcium 0.011
potassium 0.011
hydrogencarbonate 0.002
Usethesedatatoestimatetheosmoticpressureofseawaterat25C.Whatistheminimum
 pressureneededtodesalinateseawaterbyreverseosmosis?
10.100Whatistheexpectedfreezingpointofa0.20molkg 1solutionofCaCl ?(Assumecomplete
2
dissociation.)
10.101Thefreezingpointofa0.10molkg 1solutionofmercury(I)nitrateisapproximately0.27C.
Showhowthissuggeststhattheformulaofthemercury(I)ionisHg 22+.
10.102A1.00molkg 1aqueoussolutionofHFfreezesat1.91C.Whatisthepercentageionisation
ofHFinthesolution?
10.103Anaqueoussolutionofaweakelectrolyte,HX,withaconcentrationof0.125molkg 1hasa
freezingpointof0.261C.Whatisthepercentageionisationofthecompound(totwo
significantfigures)?
10.104Thevan'tHofffactorforthesolutein0.100molkg 1NiSO (aq)is1.19.Whatwouldthisfactor
4
beifthesolutionbehavedasifitwere100%dissociated?
10.105Whatistheexpectedvan'tHofffactorforK2SO4inanaqueoussolution,assuming100%
dissociation?
10.106A0.118molkg 1solutionofLiClhasafreezingpointof0.415C.Whatisthevan'tHoff
factorforthissoluteatthisconcentration?
10.107Whatistheapproximateosmoticpressureofa0.118molkg 1solutionofLiClat10C?(Use
thedatainquestion10.106.)

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 ADDITIONALEXERCISES
10.108Thebendsisamedicalemergencycausedwhenascubadiverrisestooquicklytothesurface
fromadeepdive.Theoriginoftheproblemisseeninthecalculationsinthisquestion.At37C
(normalbodytemperature),thesolubilityofN2inwateris0.015gL1whenitspressureoverthe
solutionis1.010 5Pa.Airisapproximately78mol%N2.WhatamountofN2isdissolvedper
litreofblood(essentiallyanaqueoussolution)whenadiverinhalesairatapressureof1.0
10 5Pa?WhatamountofN2dissolvesperlitreofbloodwhenthediverissubmergedtoadepth
ofapproximately30m,wherethetotalpressureoftheairbeingbreathedis4.010 5Pa?Ifthe
diversurfacesquickly,howmanymillilitresofN2gas,intheformoftinybubbles,arereleased
intothebloodstreamfromeachlitreofblood(at37Cand1.010 5Pa)?
10.109Deepseadiverssometimessubstituteheliumfornitrogenintheairthattheycarryintheirtanks
topreventthebends,becauseheliumismuchlesssolubleinbloodthannitrogen.Usethe
simplemolecularmodelofgassolubilitydiscussedonpp.3912toexplainwhyheliumis
relativelyinsolubleinwater.
10.110Usethesimplemolecularmodelofgassolubilitydiscussedonpp.3912toexplainwhyN2gas
solubilityinwaterdecreasesasthetemperatureofthesolutionrisesfromroomtemperatureto
about70C,andthenbeginstoincrease.
10.111Thevapourpressureofamixtureof400goftetrachloromethaneand43.3gofanunknown
compoundis1.8010 4Paat30C.Thevapourpressureofpuretetrachloromethaneat30C
is1.8810 4Pa,whilethatofthepureunknownis1.1210 4Pa.Whatistheapproximate
molarmassoftheunknown?
10.112Magnesiumhydroxide,Mg(OH) ,foundinsomeantacids,hasasolubilityof7.0510 3gL1
2
at25C.CalculateKspforMg(OH)2.
10.113SolidMn(OH)2isaddedtoasolutionof0.100MFeCl2.Afterreaction,whatarethemolar
concentrationsofMn 2+andFe2+inthesolution?(ForMn(OH)2,Ksp=1.610 13.)
10.114Supposethat50.0mLof0.12MAgNO3isaddedto50.0mLof0.048MNaClsolution.
(a)WhatmassofAgClforms?
(b)Calculatethefinalconcentrationsofalloftheionsinthesolutionthatisincontactwith
theprecipitate.
(c) WhatpercentageoftheAg +ionsprecipitates?
10.115Asampleofhardwaterwasfoundtohave278ppm(partspermillion)Ca2+ions.A1.00g
sampleofNa2CO3wasdissolvedin1.00Lofthiswater.WhatisthenewconcentrationofCa2+
inppm?(AssumethattheadditionofNa2CO3doesnotchangethevolume,andassumethatthe
densitiesoftheaqueoussolutionsinvolvedareall1.00gmL1.)
10.116Whatistheosmoticpressureofa0.010Maqueoussolutionofamolecularcompoundat25C?
10.117Theosmoticpressureofadilutesolutionofaslightlysolublepolymerinwaterwasmeasured
usingtheosmometerinfigure10.31.Thedifferenceintheheightsoftheliquidlevelswas1.26
cmat25C.Assumethesolutionhasadensityof1.00gmL1.
(a)Whatistheosmoticpressureofthesolution?
(b)Whatisthemolarityofthesolution?
(c)Atwhattemperaturewouldthesolutionfreeze?
 (d)Useyouranswersto(a)(c)toexplainwhyfreezingpointdepressioncannotbeusedto
determinethemolecularmassesofcompoundscomposedofverylargemolecules.
10.118Consideranaqueous1.00molkg 1solutionofNa PO ,acompoundwithusefuldetergent
3 4
properties.Calculatetheboilingpointofthesolutionassumingthat:
(a)itdoesnotioniseatallinsolution
(b)thevan'tHofffactorforNa3PO4reflects100%dissociationintoitsions.

The1.00molkg 1solutionboilsat100.83Cat1.010 5Pa.

(c)Calculatethevan'tHofffactorforthesoluteinthissolution.
10.119InanaqueoussolutionofKNO3,theconcentrationis0.9159mol%ofthesalt.Thesolution's
densityis1.0489gmL1.Calculatethe(a)molalconcentrationofKNO3,(b)percentage(w/w)
ofKNO3and(c)molarityoftheKNO3inthesolution.

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 KEYTERMS
association idealsolution molefraction(x)
boilingpointelevation(Tb) immiscible nonvolatile
colligativeproperty insoluble osmosis
commonion ionpair osmoticmembrane
commonioneffect ionicproduct osmoticpressure(II)
dialysis isotonic Raoult'slaw
dimers latticeenthalpy saturatedsolution
dissociation likedissolveslikerule solubility
dissolution miscible solubilityproduct(Ksp)
enthalpyofsolution(solH) molalboilingpointelevation soluble
freezingpointdepression constant(Kb) solute
(Tf) molalconcentration(b) solution
Henry'slaw molalfreezingpoint solvation
hydration depressionconstant(Kf) solvationenthalpy
hydrationenthalpy molality(b) solvent
hypertonic molarconcentration(c) van'tHofffactor(i)
hypotonic molarsolubility(s)
molarity(c)

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CHAPTER

11 AcidsandBases
Ofalltheplanetsandmoonsinoursolarsystem,theEarthistheonlyonewhichhasbeenfoundtosupport
lifeasweknowit.Thisisduetoacombinationoffactors,includingthedistancefromtheSun,an
atmospherecontainingoxygen,andthepresenceofplentifulamountsofwaterthatisneithertooacidicnor
toobasic.Formanyyears,itwaswonderediflifeexistedonVenus,ourclosestplanetaryneighbour,asitis
aboutthesamesizeasEarthandhasanatmosphere.However,anumberofprobeshaveshownthat,in
additiontotheenormoussurfacepressure(about100timesthatonEarth)andhighsurfacetemperature(460
C),theupperatmospherecontainssignificantamountsofsulfuricacid,astrong,corrosiveacid,inhalation
ofwhichwouldbefataltoanypioneeringastronauts.AttentionhasthereforeturnedtoMarsasatargetfor
humanexploration.

However,therearesomeformsoflifeonEarth,calledacidophiles,whichcanexist,andindeedthrive,in
highlyacidicenvironmentswithpHvaluesapproaching0.Theseareoftenfoundingeothermalareasin
whichtheconcentrationofsulfurcontainingcompoundsishigh.OnesuchacidophileisthealgaCyanidium
caldarium,whosegreencolourisoftenseenaroundNewZealand'sthermalareas.Thephotographshowsthe
craterlakeonNewZealand'sWhiteIsland,withthegreencolourarising,inpart,fromthepresenceofthis
alga.Cyanidiumcaldariumhasmanagedtoadapttothehighlyacidicconditionsbybeingabletopumpacid
outofitscellsandusingacidresistantpolysaccharidemoleculestoprotectthecellsfromtheacidic
environment.

Inthischapter,wewilldiscussanumberofaspectsofacidsandbases.Wewillinvestigatethevarious
definitionsofacidsandbases,showthatthereisanenormousrangeofacidandbasestrengthsandthatthese
canberationalisedonthebasisofmolecularstructure,quantifyBrnstedLowryacidandbasebehaviour
usingtheconceptsofpH,Ka andKb,andstudytitrationsofacidsandbases.
 KEYTOPICS

11.1TheBrnstedLowrydefinitionofacidsandbases
11.2Acidbasereactionsinwater
11.3Strongacidsandbases
11.4Weakacidsandbases
11.5Themolecularbasisofacidstrength
11.6Buffersolutions
11.7Acidbasetitrations
11.8Lewisacidsandbases

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11.1TheBrnstedlowryDefinitionofAcidsand
Bases
Inchapter10,welookedatthenatureofsolutesandshowedhowfreezingpointdepression
measurementsgiveusinformationaboutthedegreeofdissociationofaparticularsolute.Similar
informationcanalsobeobtainedbymeasurementoftheconductivityofasolution,andthistechniqueis
bothsimplertocarryoutandmoresensitivethanfreezingpointdepression.Itiseffectivebecauseonly
solutionsthatcontainionswillconductanelectriccurrent.Themagnitudeoftheelectriccurrent
dependsontheconcentrationandnatureoftheionsinthesolution.Ahighconcentrationofionsallows
thepassageofalargercurrent,andthereforegivesalargerconductivitythanalowconcentration,while
apuresolventthatcontainsnoionswillhaveaconductivityofzero.

WetendtothinkofwaterasconsistingsolelyofH2Omolecules.Eachmoleculecomprisesacentral
oxygenatomthatiscovalentlyboundtotwohydrogenatoms,andwemightthereforeexpectthatliquid
waterwouldhavenoioniccharacter.However,measurementsshowthatpurewaterdoesexhibitasmall
conductivity,consistentwiththepresenceofions.(Thisisthereasonthat,unliketheunfortunateFrench
singerClaudeFranois,writerofthesongMyWay,youshouldnevertrytochangealightbulbwhile
standinginthebath.)Theseionsarisefromthereactionofwaterwithitself,accordingtothefollowing
equation.

Thenetresultofthisreactionisthetransferofaproton(H+,ahydrogenatomminusanelectron)from
onemoleculeofwatertoanother,andformationoftheionicspeciesH3O+(thehydroniumion(H3O+))
andOH(thehydroxideion(OH)).Reactionssuchasthis,whichinvolvethetransferofasingleproton
fromonespeciestoanotherarecalledacidbasereaction.Thereactionofwaterwithitselfrepresents
arguablythesimplestexampleofsuchareaction.Inthiscase,wateractsasbothanacidandabase.

Theconceptofacidsandbaseshasbeenknownforhundredsofyears,butitisonlyrelativelyrecently
thatdefinitionsofthewordsacidandbasehavebeenagreedupon.Thewordacidderivesfromthe
Latinacidus,meaningsouracidsdoindeedtastesour,butitisnotagoodideatotastetheminthe
laboratory.Thewordalkali,whichissynonymouswithbase,comesfromtheArabicalqaliy,literally
theashes,referringtotheashesofthesaltwortplantthatgrowsinalkalinesoils.Thefirst
comprehensivetheoryconcerningacidsandbasesappearedin1884inthePhDthesisoftheSwedish
chemist,SvanteArrhenius(18591927,NobelPrizeinchemistry,1903),whowasnearlyfailedfor
proposingthationscouldexistinsolution.HedefinedanacidasasubstancethatreleasedH+ionswhen
dissolvedinwater,andabaseasasubstancethatgaverisetoOHionsondissolutioninwater.This
definitionissimilartothemoregeneralBrnstedLowrydefinitionofacidsandbases,whichwewill
usefromthispoint.ThiswasproposedbyJohannesBrnsted,aDanishchemist,andThomasLowry,an
Englishchemist,independentlyofeachotherin1923.Theyconsideredthatacidbasereactions
involvedproton(H+)transferbetweenanacidandabase,whichtheydefinedasfollows:
Anacidisaprotondonor.
Abaseisaprotonacceptor.
Inotherwords,aBrnstedLowryacidwilldonateaprotontoaBrnstedLowrybase,whichwill
acceptit.Fromnowon,wewillrefertoBrnstedLowryacidsandbasessimplyasacidsandbases.To
illustratetheBrnstedLowryconcept,let'sreturntotheexampleinvolvingwaterthatweintroduced
previously.Westatedthatwateractedasbothanacidandabase,andwecannowexplainthiswith
referencetotheBrnstedLowrydefinition.

Onewatermoleculeactsasaprotondonor,andisthereforeanacid.ThiswatermoleculebecomesOH
ontherighthandsideoftheequation.Theotherwatermoleculeacceptsthedonatedproton,and
thereforeactsasabase.ThiswatermoleculeisconvertedtoH3O+ontherighthandsideofthe
equation.Itisinstructivetoconsiderthisreactionintermsofthestructuresshowninfigure11.1.

FIGURE11.1Amechanisticviewoftheacidbasereactionofonewatermoleculewithanother.

Obviously,inorderforH2Otoactasanacid,itmust,accordingtotheBrnstedLowrydefinition,have
aprotontodonate.However,themerepresenceofhydrogenatoms,whicharepotentialprotons,isnot
sufficientforachemicalspeciestoactasanacid.Forexample,methane,CH4,containsfourhydrogen
atomsbutshowsessentiallynoacidicproperties.Forahydrogenatomtobemeasurablyacidic,itmust
beboundtoanotheratomviaanappreciablypolarbond,andthereforeacidstendtocontainhydrogen
atomsboundtogroup16or17elements.Figure11.1alsoshowsthat,forH2Otoactasabaseand
acceptthedonatedproton,itmusthavealonepairofelectronstowhichthedonatedprotoncan
covalentlybond.Thepresenceofoneormorelonepairsisaprerequisiteforaspeciestoactasabase,
butnotallspeciescontaininglonepairsactasbasesforexample,thechlorideion,Cl,containsfour
lonepairs,butdisplaysnegligiblebasicproperties.Basesusuallycontaingroup15or16elements,the
atomsofwhich(especiallygroup16)areoftendeprotonatedandhencenegativelycharged.Table11.1
listsanumberofcommonacidsandbasesthatwouldbefoundinanychemistrylaboratory.Youcan
seethattheacidscontainaverypolarHXbond,whilethebasescontainNanddeprotonatedOatoms
withoneandthreelonepairsrespectively.
TABLE11.1 Somecommonacidsandbases
Formula Name Structure
Acids
HCl hydrochloricacid (a)

HNO3 nitricacid

H2SO4 sulfuricacid

CH3COOH aceticacid

H3PO4 phosphoricacid
 Bases
NaOH sodiumhydroxide

NH3 ammonia(b)

C5H5N pyridine

Na2CO3 sodiumcarbonate

(a)PureHClisagasatroomtemperature,andiscalledhydrogenchloride.Hydrochloricacid
referstoasolutionofHClinwater.
(b)PureNH3isagasatroomtemperature.Inthelaboratory,itisoftenusedasanaqueous
solution.

Itcanbeseenfromthestructuresoftheacidsintable11.1that,insomecases,thereismorethanone
verypolarHXbond,andtheseacidscandonatemorethanoneproton.Suchacidsarecollectively
calledpolyproticacid.Hydrochloricacid,nitricacidandaceticacid,eachofwhichcandonateonly
oneproton,areexamplesofmonoproticacids.Sulfuricacidcandonatetwoprotonsandiscalleda
diproticacidwhereasphosphoricacid,whichcandonatethreeprotons,isatriproticacid.

Similarly,somebasescanacceptmorethanoneprotonandarecollectivelycalledpolyproticbase.
Sodiumhydroxide,ammoniaandpyridineareexamplesofmonoproticbases,whereascarbonateionis
adiproticbase.

Wenowconsiderthereactionsthatoccurwhenweplaceanacidorabaseinwater.Webeginbyusing
achemicalequationandamechanisticdiagramtoseewhathappenswhenwedissolvegaseous
hydrogenchlorideinwater.
Here,HClistheacidandH2Oisthebase.HCldonatesaprotontoH2O,therebybecomingCl,while
H2O,onacceptingtheproton,becomesH3O+,thehydroniumion.Thisreactiongoesessentiallyto
completionandwesaythatHCldissociatescompletelyinaqueoussolution.

Similarly,ifwedissolvegaseousammonia,NH3,inwater,weobtainaqueousammonia,NH3(aq),in
whichthefollowingreactionoccurs.

Inthisreaction,H2Oactsasanacid,donatingaprotontoNH3andthusbecomingOH,whileNH3acts
asabasebyacceptingtheprotonfromH2OtogiveNH4+.However,thisreactiondiffersfromthatfor
HClinthatitproceedsalmostnegligiblyintheforwarddirection,andthereactionofammoniawith
wateristhereforefarfromcomplete.Notethatwater,thesolventinbothreactions,actsasabaseinthe
formerreactionandanacidinthelattercompoundssuchasthisthatcanactaseitheranacidorabase
arecalledamphiprotic.

ConjugateAcidbasePairs
ItisinformativetowritethereverseequationsforthereactionsofHClandNH3withwater.

Wecanseethatthereversereactionsalsoinvolvetransferofaproton,andarethereforethemselves
acidbasereactions.Inthereaction:

H3O+actsasanacid,donatingaprotontoCl,whichactsasabasebyacceptingit.Similarly,inthe
reaction:

NH4+actsasanacid,donatingaprotontothebaseOH.Thisillustratesageneralfeatureofall
BrnstedLowryacidbasereactions:boththeforwardandreversereactionsareacidbasereactions.
Furthermore,therearealwaystwosetsofspeciesoneithersideoftheequationthatdifferonlybya
proton,andwecalltheseconjugateacidbasepair.Inthereaction:

bothHClandCl,andH2OandH3O+differonlybyaproton.WeshowedthatHClactsasanacidinthe
forwardreactionandClactsasabaseinthereversereaction.Therefore,Clistheconjugatebaseof
HCl,andHClistheconjugateacidofCl.Usingthesamereasoning,wecanseethatH2Oisthe
conjugatebaseofH3O+,andH3O+istheconjugateacidofH2O.
Asboththeforwardandreversereactionsareacidbasereactions,andoccurtosomeextent,itisusual
towriteacidbasereactionsasequilibria.Wewilllookathowwequantifytheseequilibrialaterinthis
chapter.

WORKEDEXAMPLE11.1

DeterminingtheConjugateBasesofBrnstedLowryAcids

Whataretheconjugatebasesofnitricacid,HNO3,andthehydrogensulfateion,HSO4?

Analysis

Themembersofaconjugateacidbasepairdifferbyoneproton,withtheacidhavingthe
greaternumberofprotons.Tofindtheformulaofthebase,weremoveoneprotonfromthe
acid.

Solution

RemovingoneprotonfromHNO3leavesNO3.Thenitrateion,NO3,isthustheconjugate
baseofHNO3.RemovingaprotonfromHSO4leavesitsconjugatebase,SO42.

Isouranswerreasonable?

Asacheck,wecancomparethetwoformulaeineachpair.

Ineachcase,theformulaontherighthasonefewerprotonthantheformulaontheleft,soit
istheconjugatebase.Wehaveansweredthequestioncorrectly.

PRACTICEEXERCISE11.1
Writetheformulaoftheconjugatebaseof
eachofthefollowingBrnstedLowry
acids.
(a)H2O
 (b)HI
(c)HNO2
(d)H3PO4
(e) H PO
2 4
(f) HPO 2
4
(g)H2SO4
(h)NH +
4
(i) CH3COOH
(j) C6H5OH
(k)(CH ) NH+
33

WORKEDEXAMPLE11.2

IdentifyingConjugateAcidbasePairsinaBrnstedlowry
AcidbaseReaction

Theanionofsodiumhydrogensulfate,HSO4,reactsasfollowswiththephosphateion,
PO43.

Identifythetwoconjugateacidbasepairs.

Analysis

Therearetwothingsthathelpustoidentifytheconjugateacidbasepairsinanequation.
Oneisthatthemembersofaconjugatepairdifferbyaproton.Thesecondisthatthe
membersofeachpairmustbeonoppositesidesofthereactionarrow.Ineachpair,theacid
hasthelargernumberofprotons.

Solution

TwooftheformulaeintheequationcontainPO4,sotheymustbelongtothesameconjugate
pair.Theonewiththemostprotons,HPO42,istheacid,andtheother,PO43,isthebase.
Therefore,oneconjugateacidbasepairisHPO42andPO4.Theothertwoions,HSO4and
SO42,belongtothesecondconjugateacidbasepairHSO4istheconjugateacidandSO42
istheconjugatebase.
 Isouranswerreasonable?

Achecksatisfiesusthatwehavefulfilledtherequirementsthateachconjugatepairhasone
memberoneachsideofthearrowandthatthemembersofeachpairdifferfromeachother
byone(andonlyone)proton.

PRACTICEEXERCISE11.2
Onekindofbakingpowdercontainssodiumbicarbonateand
calciumdihydrogenphosphate.Whenwaterisadded,the
followingreactionoccurs.

Identifythetwoacidsandthetwobasesinthisreaction.(The
H2CO3decomposestoreleaseCO2,whichcausesthecaketorise.)

PRACTICEEXERCISE11.3
Whensomeofthestrongcleaningagenttrisodiumphosphateis
mixedwithhouseholdvinegar,whichcontainsaceticacid,the
followingreactionoccurs.Identifythepairsofconjugateacidsand
bases.

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11.2AcidbaseReactionsinWater
Inmanyoftheexampleswehaveconsideredsofar,waterhasactedasboththesolvent,andeithertheacidor
thebase.However,acidbasereactionscanoccurinanysolvent,andcanevenoccurintheabsenceof
solvent,asshowninfigure11.2.

FIGURE11.2ThereactionofgaseousHClwithgaseousNH3 .Aseachgasescapesfromitsconcentratedaqueous
solutionandmingleswiththeother,acloudoftinycrystalsofNH4 Cl(s)formsabovethebottles.
AndyWashnik

Thisisalsoaprotontransferreaction,inwhichgaseousHCldonatesaprotontogaseousNH3,asshowninthe
mechanisticdiagram.Giventhatmostacidbasereactionsofinterestoccurinaqueoussolution,wewill
concentrateonwaterasthesolventforthemajorityofourdiscussions.

TheAutoprotolysisofWater
Wehaveshownthatwatercanreactwithitselftogeneratehydroniumandhydroxideionsaccordingtothe
equation:

Thisreaction,inwhichaprotonistransferredbetweenidenticalmolecules,iscalledautoprotolysis
(sometimescalledautoionisation).Theextentoftheautoprotolysisofwatercanbedeterminedusingthe
equilibriumconstantforthisprocess.Usingthemethodsdevelopedinchapter9,andrememberingthatpure
liquidsdonotappearinanequilibriumconstantexpression,wewritetheequilibriumconstantforthereaction
as:

Theextraordinaryimportanceofthisequilibriummeansthattheequilibriumconstantisgiventhespecial
symbolKwandiscalledtheautoprotolysisconstantofwater.Itsverysmallvalueshowsthatthe
autoprotolysisofwaterproceedsonlytoaverysmallextentandthattheequilibriumconcentrationsofH3O+
andOHinpurewateraresmall.WecancalculatejusthowsmallbyusingthevalueofKwandrealisingfrom
thestoichiometryofthereactionthattheequilibriumconcentrationsofH3O+andOHinpurewatermustbe
thesame.

If[H3O+]=[OH],then:

Therefore,the[H3O+]and[OH]inpurewaterat25.0Careboth1.010 7molL1.Likemostequilibrium
constants,thevalueofKwistemperaturedependentandincreasesasthetemperatureincreases.Forexample,
at40.0C,Kw=3.010 14andpurewateratthistemperaturehas[H3O+]=[OH]=1.710 7molL1.Table
11.2listsvaluesofKwatanumberoftemperatures.

TABLE11.2 Kwatvarioustemperatures
Temperature(C) Kw
0 1.510 15
10 3.010 15
20 6.810 15
25 1.010 14
30 1.510 14
40 3.010 14
50 5.510 14
60 9.510 14

Wesaythatpurewaterisneutral,becauseitcontainsequalconcentrationsofH3O+andOH.Aqueous
solutionsinwhich[H3O+]>[OH]aretermedacidic,whilebasic(oralkaline)solutionshave[H3O+]<[OH].
Thereisaninverserelationshipbetween[H3O+]and[OH]inaqueoussolutionatconstanttemperatureasone
increases,theothermustdecreaseinordertokeepKwconstant.Ifweknowthevalueofonlyoneof[H3O+]
or[OH]inasolution,wecanuseKwtocalculatetheother,asillustratedinworkedexample11.3.

WORKEDEXAMPLE11.3

Finding[H3O+]from[OH]or[OH]from[H3O+]
 Inasampleofbloodat25C,[H3O+]=4.610 8M.Find[OH]anddecideifthesampleisacidic,
basicorneutral.

Analysis

Weknowthatthevaluesof[H3O+]and[OH]arerelatedtoeachotherthroughKwat25Cas
follows.

Ifweknowoneconcentration,wecanalwaysfindtheother.

Solution

Wesubstitutethegivenvalueof[H3O+]intothisequationandsolvefor[OH].

Solvefor[OH],rememberingthatitsunitsaremolL1orM.

Whenwecomparea[H3O+]of4.610 8Mwitha[OH]of2.210 7M,weseethat[OH]>

[H3O+].Ouranswer,then,isthatthebloodisslightlybasic.

Isouranswerreasonable?

WeknowKw=1.010 14=[H3O+][OH].Soonecheckistonotethat,if[H3O+]isslightlyless
than110 7,[OH]willbeslightlymorethan110 7,asitis.

PRACTICEEXERCISE11.4
Anaqueoussolutionofsodiumbicarbonate,
NaHCO3,has[OH]=7.810 6M.Whatis
[H3O+]?Isthesolutionacidic,basicorneutral?

TheConceptofpH

Aswehaveseenpreviously,theconcentrationsofH3O+andOHinpurewaterareverysmall,andthesameis
oftentrueof[H3O+]and[OH]inaqueoussolutionsofacidsandbases.Toavoidworkingwithsuch
inconvenientlysmallnumbers,wecommonlyexpress[H3O+]intermsofthepHofthesolution.This
approachwasdevelopedbytheDanishchemistSrenSrensen(18681939)in1909.pHisdefinedasthe
negativelogarithmoftheconcentrationofH3O+inasolution,or,inequationform:

WecanalsodefinethepOHofasolutionas:
Inbothcases,pissimplyanabbreviationforlog(pisderivedfromtheGermanwordPotenzmeaning
power).Itisimportanttorealisethatlogmeanslog 10,ratherthannaturallogarithm(lnorlog e ).Itisvitalthat
youappreciatethedifferencebetweenthetwotypesoflogarithmsforexample,log(110 2)=2,whereas
ln(110 2)4.605.Youshouldalsoensurethatyouknowunderwhichcircumstancesthedifferenttypesof
logarithmsareusedyougenerallyuselogonlyincalculationsinvolvingpHor(aswewillsee)pKa .

Havingshownthat[H3O+]=1.010 7molL1inpurewaterat25.0C,wecannowcalculatethepHofpure
waterundertheseconditions.

Therearetwothingstonotehere.Firstly,youcannottakethelogarithmofaquantitythathasunits,and
thereforewemusteitherimplicitlydroptheconcentrationunitsof[H3O+]beforetakingthelogarithmortreat

theterm[H3O+]asbeingthedimensionlessquantity ,aswedidinsimilarsituationsinchapter9.
Secondly,thenumberofdecimalplacesinalogarithmofanynumberisequaltothenumberofsignificant
figuresinthatnumber.ThusourpHisgiventotwodecimalplaces,7.00.

ThefactthatpurewaterhasapHof7at25.0Cisprobablyafamiliarresulttomanyofyou.Notsofamiliar
perhapsisthepOHofpurewaterat25.0C.Again,wehaveshownthat[OH]=1.010 7underthese
conditionsandtherefore:

Inbothcases,youcanseethatitismuchmoreconvenienttowrite7.00than1.010 7(orindeed0.000000
10).

Weshowedpreviouslythatsolutionswith[H3O+]>[OH]areacidic,whilethosewith[H3O+]<[OH]are
basic.Thismeansthat(at25.0C)solutionswithpH<7areacidic,andthosewithpH>7arebasic(or
alkaline).

Itisimportantthatyouareproficientindealingwithlogarithmsonyourcalculatorandareabletoconvert
from[H3O+]topHandfrompHto[H3O+]withoutanytrouble.Thelatterinvolvestakingtheantilogarithmof
thenegativeofthepH,i.e.[H3O+]=10 pH.

AsimplerelationshipbetweenpHandpOHcanbederived,startingfromtheKwexpression.Todothis,we
makeuseofthepropertyoflogarithmswhichsaysthatthelogarithmoftheproductoftwonumbersisequalto
thesumofthelogarithmsofthosenumbers,i.e.log(ab)=log(a)+log(b).

Weknowthat[H3O+][OH]=Kw.Ifwenowtakethenegativelogarithmofbothsides,weobtain:

Butlog[H3O+]=pH,log[OH]=pOHandlogKw=pKw.

Therefore:

wherepKwisthenegativelogarithmofKw.At25.0C,Kw=1.010 14andthereforethisbecomes:

Notethatthisequationappliesonlyat25.0Candwewillassumethistemperatureincalculationsthroughout
thischapter.BecausepHandpOHarerelatedbysuchasimpleexpression,itisusualtotalkalmost
exclusivelyintermsofthepHofasolution,andpOHisrarelyused.
ItshouldbenotedthatourdefinitionofpH:

isanapproximation.Theexactdefinitioninvolvestheuseofactivity(a),aconceptwehavemetbrieflyin
chapter9(p.353),ratherthanconcentration,andiswrittenas:

However,providedthatweworkunderdiluteconditions,concentrationisanacceptableapproximationto
activity,andwewillusetheequationpH=log[H3O+]throughouttherestofthebook.

Workedexamples11.4,11.5and11.6illustratethetypesofproblemsyoumayencounterconcerningthe
manipulationsofpH,pOH,[H3O+]and[OH].

WORKEDEXAMPLE11.4

CalculatingpHandpOHfrom[H3O+]

ThedunelakesonFraserIsland,offtheQueenslandcoast,areappreciablyacidicduetothe
presenceofnaturalorganicacidsfromplantmaterial.ThewaterinLakeBarga(figure11.3),the
mostacidiclake,wasfoundtohaveanH3O+concentrationof7.110 5Mat25C.Whatarethe
pHandpOHvaluesofthelake'swater?

FIGURE11.3LakeBarga,themostacidiclakeonFraserIsland,Queensland.

Analysis
 Ifweknowthevalueof[H3O+],wecanusepH=log[H3O+]tofindthepH.

Solution

Wesubstitute[H3O+]=7.110 5Mintothisexpressiontogive:

Wefirsttakethelogarithmofthisnumberandthentakethenegativeofthelogarithm.Usinga
calculatortofindthelogarithmof7.110 5givesthevalue4.15(notethenegativesign).Tofind
thepH,wechangeitsalgebraicsign.

OnceweknowthepH,thepOHiseasilyfoundbyusingtheequationpH+pOH=14.00at25C.
Therefore,thepOHofthelakewateris:

Isouranswerreasonable?

Thevalueof[H3O+]isbetween110 5and110 4,sothepHhastobebetween5and4(the

antilogarithmsof110 5and110 4,respectively),whichitis.Therefore,thepOHmustbe
between9and10,asitis.

PRACTICEEXERCISE11.5

AsoftdrinkhasaH3O+concentrationof3.67
10 4molL1.WhatarethepHandpOHvalues
ofthisdrink?Isitacidic,basicorneutral?

WORKEDEXAMPLE11.5

CalculatingpHfrom[OH]
WhatisthepHofasodiumhydroxidesolutionat25Cinwhichthehydroxideionconcentrationis
0.0026M?

Analysis

Therearetwowaystosolvethisproblem.WecouldusetheKwexpression:

andthegivenvalueofthehydroxideionconcentrationtofind[H3O+]andthencalculatethepH
usingpH=log[H3O+].
 ThesecondwayistocalculatethepOHfromthehydroxideionconcentration(pOH=log[OH])
andthensubtractthepOHfrom14.00tofindthepH.Whilebothmethodsarevalidandgivethe
sameanswer,thesecondpathrequireslesseffort,solet'sproceedthatway.

Solution

Weusetheequation:

andsubstitute[OH]=0.0026Mintothistogive:

Takingthelogarithmgives2.59.Therefore:

ThenwesubtractthispOHvaluefrom14.00tofindthepH.

NoticethatthepHinthisbasicsolutioniswellabove7.

Isouranswerreasonable?

Themolarconcentrationofthehydroxideionisbetween110 3and110 2,sothepOHmustbe

between3and2(theantilogarithmsof110 3and110 2,respectively)whichitis.Thus,thepH
shouldbebetween11and12.

PRACTICEEXERCISE11.6

TheconcentrationofOHinthewaterinwhich
asoilsamplehassoakedovernightis1.47
10 9molL1.WhatisthepHofthesolution?

WORKEDEXAMPLE11.6

Calculating[H3O+]frompH

Calcareoussoilissoilrichincalciumcarbonateandisparticularlyabundantalongthesouthcoast
ofAustralia.ThepHofthemoistureinsuchsoilgenerallyrangesfromjustover7toashighas8.3.
Afteroneparticularsoilsamplewassoakedinwater,thepHofthewaterwasmeasuredtobe8.14.
Whatvalueof[H3O+]correspondstoapHof8.14?Isthesoilacidicorbasic?

Analysis

Theequationweusetocalculate[H3O+]frompHis[H3O+]=10 pH.

Solution
 WesubstitutethepHvalue,8.14,intotheequationabove,whichgives:

Wethereforeneedtocalculate10tothepowerof8.14.Theeasiestwaytodothisonacalculator
istopressthe10 x keyandthenenter8.14.(Notethat,onsomecalculators,youmayhavetodo
theseintheoppositeorder.)BecausethepHhastwodigitsfollowingthedecimalpoint,weobtain
twosignificantfiguresintheH3O+concentration.Therefore,theanswer,correctlyrounded,is:

BecausepH>7and[H3O+]<110 7M,thesoilisbasic.

Isouranswerreasonable?

ThegivenpHvalueof8.14isbetween8and9,sotheH3O+concentrationmustliebetween10 8
and10 9molL1,aswefound.

PRACTICEEXERCISE11.7

Findthevaluesof[H3O+]and[OH]that
correspondtoeachofthefollowingpHvalues.
Statewhethereachsolutionisacidicorbasic.
(a)2.30(theapproximatepHoflemon
juice)
(b)3.85(theapproximatepHofsauerkraut)
(c)10.81(thepHofmilkofmagnesia,a
laxativeandanantacid)
(d)3.50(thepHoforangejuice,on
average)
(e)11.61(thepHofdilute,household
ammonia)

ThepHscalerangesfrom0to14formostpracticalapplications,althoughnegativevaluesofpHcanbe
obtainedinveryacidicsolutionsandpHvaluesgreaterthan14occurinconcentratedaqueousbases.A0.10
molL1solutionofHCl(aq)hasapHof1.00,whilea0.10molL1solutionofNaOH(aq)hasapHof13.00.
Figure11.4showsthepHvaluesofsomecommonaqueoussolutions.AccuratepHvalues(0.01pHunits)
canbeeasilydeterminedwithapHmeter,whichusesaglasselectrodethatissensitivetoH3O+ions(see
figure11.5).LessaccuratevaluescanbeobtainedusingpHpaper(figure11.6),whileblueandredlitmus
paperisusedonlyinaqualitativemannertodeterminewhetherasolutionisacidicorbasic.
 FIGURE11.4ThepHscale.
AirphotoAustralia/PeterHarrison

FIGURE11.5ApHmeterhasaspecialcombinationelectrodethatissensitivetohydrogenionconcentration.After
theinstrumenthasbeencalibratedusingsolutionsofknownpH,theelectrodeisdippedintothe
solutiontobetestedandthepHisreadfromthemeter.ThepHmeterdetectsthedifferencebetween
theH3 O+concentrationsinthetestedsolutionandthesolutioninsidetheelectrodeasavoltage,which
isthenconvertedtoapHvalue.
CharlesDWinters

FIGURE11.6ApHtestpaper.ThecolourofthisHydrionteststripchangedtogreenwhenadropoftheorange
juicewasplacedonit.Accordingtothecolourcode,thepHofthejuiceisapproximately3.
TheStrengthofAcidsandBases

WestatedpreviouslythatthepHofa0.10MsolutionofHCl(aq)is1.00.Thismeansthat[H3O+]inthis
solutionis0.10Mand,therefore,impliesthatthereaction:

proceedstocompletioninotherwords,HCliscompletelydissociatedinwater.However,ifwemeasurethe
pHofa0.10MaqueoussolutionoftheseeminglysimilaracidHF,wefindthatitisnot1.00but2.10.Youcan
showthereforethat[H3O+]intheHFsolutionisnot0.10M,but7.910 3M,andthismeansthatthereaction:

doesnotproceedtocompletion.Infact,atanyparticulartime,onlyabout1in13moleculesofHFhave
reactedwithwatertoformH3O+andF,withthemajorityremainingundissociated.Wefindasimilarsituation
witha0.10Maqueoussolutionofaceticacid,CH3COOH.ThemeasuredpHofthissolutionisagainnot1.00
but2.88,whichcorrespondsto[H3O+]=1.310 3Mandagainmeansthattheequilibrium:

liesverymuchtowardsthereactants.ObviouslythereisafundamentaldifferencebetweenHClandbothHF
andCH3COOH.HClisabletotransferitsprotoncompletelytowater,whileHFandCH3COOHareverypoor
protondonorstowardswater.Thismeanstheyexistpredominantlyasmoleculesinaqueoussolution,withthe
resultbeingalowconcentrationofionsinsolution.Thiscanbeillustratedusingconductivity,theconceptwe
usedtoopenthischapter(p.427).Figure11.7showsthedifferentconductivitiesofaqueoussolutions
containingHClandCH3COOH.Thisbehaviourshowsthedifferentstrengthsoftheacids.WesaythatHClisa
strongacid,whereasbothHFandCH3COOHareweakacids.Ageneraldefinitionofthesetermsisas
follows:
AstrongacidreactscompletelywithwatertogivequantitativeformationofH O+.
3
AweakacidreactsincompletelywithwatertoformlessthanstoichiometricamountsofH O+.
3
Thereareanalogousdefinitionsforbases:
AstrongbasereactscompletelywithwatertogivequantitativeformationofOH.
AweakbasereactsincompletelywithwatertoformlessthanstoichiometricamountsofOH.
NotethatthesedefinitionsstrictlyapplyonlytoBrnstedLowryacidsinaqueoussolution.
 FIGURE11.7 Electricalconductivityofsolutionsofstrongandweakacidsatequalconcentrations.Thewires
leadtoabattery(notshown),whichprovideselectricalpowertolightthebulb:
(a)HClreactscompletelywithwatertogiveH3 O+andCl,resultinginhighconductivity,thus
enablingthelighttoglowbrightly.
(b)CH3 COOHreactswithwatertogiveonlyverysmallamountsofH3 O+andCH3 COO,sothe
lightisdimmer.
MichaelWatson

Theuseofthewordsstrongandweakissomewhatunfortunate,asitimpliesthatthereisadistinctcutoff
pointbetweenstrongandweakacids.Thisisnotthecase.Ourdefinitionofstrongacidsandbasesimpliesthat
theyarecompletelydissociatedinwaterandshouldthereforehavecomparablestrengthsthisistrueonlyif
werestrictourselvestorelativelydiluteaqueoussolutions.However,weakacidsandbasesshowanenormous
rangeofstrengthsinaqueoussolutionratherthanrelyingonthequalitativeconceptweaktodescribetheir
behaviour,itismoreinformativetoquantifytheirabilitytoeitherdonateoracceptaprotonbylookingatthe
valueoftheequilibriumconstantfortheirreactionwithwater,andwedothisinsection11.4(p.443).Wewill
firstlookatthenatureofstrongacidsandbasesinaqueoussolution.

ChemicalConnections

SwimmingPoolsandSoil

SwimmingpoolsandsoilarejusttwoexamplesofmanysituationswherepHisimportant.Thewater
inswimmingpoolsismorethanjustwateritisadilutesolutionofcompoundsthatpreventthe
growthofbacteriaandstabilisethepoolliningwhileallowingustoswimsafelyinthepool.ThepH
ofaswimmingpoolshouldbebetween7.2and7.6.

ThepHcanalsoaffecttheavailabilityofsubstancesthatplantsneedforgrowth(figure11.8).ApH
of6to7isbestformostplantsmostnutrientsaremoresolublewhenthesoilisslightlyacidicthan
whenitisneutralorslightlybasic.IfthesoilpHistoohigh,metalionsthatplantsneed,suchasiron
andmanganese,willprecipitateandnotbeavailableinthegroundwater.AverylowpHisnotgood
eitherifthepHdropsto45,metalionssuchasaluminium,thataretoxictomanyplants,are
releasedastheircompoundsbecomemoresoluble.AlowpHalsoinhibitsthegrowthofbeneficial
bacteriathatdecomposeorganicmatterinthesoiltoreleasenutrients,especiallynitrogen.

FIGURE11.8Hydrangeasgrowninacidicsoilhaveblueflowers(left),whilethosegrowninalkalinesoils
havepink/redflowers(right).

ItisimportanttobeabletomeasurethepHofthesesystems.CommercialpHtestkitsuseacidbase
indicators.KitsfortestingthepHofpoolwater(figure11.9)usephenolredindicator,whichchanges
colouroverthepHrangeof6.48.2.
 FIGURE11.9Swimmingpooltestkit.ThisapparatusisusedtotestbothpHandchlorineconcentration.
ThecolouroftheindicatortellsusthatthepHofthepoolwaterisapproximately7.6,whichis
slightlybasic.

Thisplacestheintermediatecolouroftheindicatorwithinthedesiredrangeof7.27.6.Tousethekit,
wepoursomepoolwaterintotheplasticcylinderandaddfivedropsoftheindicatorsolution.We
thenshakethemixtureuntilitishomogeneousandcomparethecolourwiththestandardstoestimate
thepH.ThecolourthatmostcloselymatchesthatofthesolutiongivestheapproximatepH.Wecan
thendecidewhetherthepHshouldbeadjustedbyadditionofparticularcompounds.Similartestkits
areavailableforwaterinanaquarium,exceptthattheindicatorusedisbromothymolblue,which
changescolouroverapHrangeof6.07.6.ThismatchesthedesiredpHrangeforsuchwater.

Soiltestkits(figure11.10)useauniversalindicator,whichisamixtureofindicatorsthatenable
estimationofpHoverawiderange.

FIGURE11.10TestingsoilpH.TheindicatorrevealsthatthesoilsamplebeingtestedhasapHof
approximately6.5,whichisslightlyacidic.
GeoffKidd
 Tousethekit,weputasampleofthesoilintheplasticapparatusprovidedandthenaddwater,along
withatabletoftheindicator.Weshakethemixtureandcomparethecolourofthewaterwiththe
colourchart.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.3StrongAcidsandBases
Wehavedefinedastrongacidasanacidthatdonatesaprotoncompletelytowater.Usingthis
definition,foranystrongacidHA,thereaction:

proceedstocompletion.Similarly,ourdefinitionofastrongbasesaysthatOHisformedquantitatively
onreactionwithwater,andthereforethereactionofanystrongbaseBwithwater:

shouldalsoproceedtocompletion.

Alistofsomestrongacidsandbasesisgivenintable11.3.
TABLE11.3 Examplesofstrongacidsandbases
Strongacids(a) Strongbases

HClO4(HOClO3),perchloricacid LiOH,lithiumhydroxide
HCl,hydrochloricacid NaOH,sodiumhydroxide
HBr,hydrobromicacid KOH,potassiumhydroxide
HI,hydroiodicacid Ca(OH)2,calciumhydroxide
HNO3(HONO2),nitricacid RbOH,rubidiumhydroxide

H2SO4((HO)2SO2),sulfuricacid NaOCH3,sodiummethoxide
HCF3SO3(HOSO2CF3),trifluoromethanesulfonicacid CsOH,caesiumhydroxide

(a)Themolecularformulaeoftheacidsinparenthesesemphasisetheactualstructureofeach
acidnotethattheacidicprotonisattachedtoanOatominallcases.

Thefactthatstrongacidsundergocompletedissociationtellsussomethingaboutthebasicityoftheir
conjugatebases.Forexample,theequilibrium:

liesalmostcompletelytotherighthandside,andthereforethereversereactionoccurstoonlya
negligibleextent.ThismeansthatCl,theconjugatebaseofHCl,doesnotreadilyacceptaprotonfrom
H3O+,andconsequentlyClmustbeaveryweakbase.Suchbehaviouriscommontoallstrongacids
andwecanmakethegeneralisationthattheconjugatebaseofastrongacidisveryweak.Wewill
investigatethisconceptfurtherwhenwediscussweakacidsandbases(section11.4).Weshouldalso
notethatH3O+isthestrongestacidandOHisthestrongestbasethatcanexistinaqueoussolution.We
havealreadyseenthatthestrongacidHCldonatesitsprotonalmostcompletelytowatertoformH3O+,
andthesameistrueofallacidsstrongerthanH3O+theyreactcompletelywhendissolvedinwaterto
formH3O+andnoneoftheundissociatedacidispresent.Likewise,anybasestrongerthanOHwill,
whendissolvedinwater,quantitativelydeprotonatewatertogiveOH.Hence,therearelimitstothe
rangeofaciditiesandbasicitiesthatcanbeaccessedinwaterand,ifwewanttogobeyondtheselimits,
wemustuseadifferentsolvent.
pHCalculationsinSolutionsofStrongAcidsandBases
Asstrongacidsandbasesreactwithwateralmostcompletely,thecalculationofpHinsolutions
containingstrongacidsorbasesisarelativelystraightforwardexerciseinstoichiometry.

Whenthesoluteinanaqueoussolutionisastrongmonoproticacid,suchasHClorHNO3,weexpectto
obtain1moleofH3O+foreverymoleoftheacidinthesolution.Thus,a1.010 2MsolutionofHCl
contains1.010 2molL1ofH3O+,anda2.010 3MsolutionofHNO3contains2.010 3molL1of
H3O+.

TocalculatethepHofasolutionofastrongmonoproticacid,weuse[H3O+]obtainedfromthestated
molarconcentrationoftheacid.Thus,the1.010 2MHClsolutionmentionedabovehas[H3O+]=1.0
10 2M,andthereforethepH=log[H3O+]=log(1.010 2)=2.00.

Forstrongbases,calculatingthepHfromtheOHconcentrationissimilarlystraightforward.A5.0
10 2MsolutionofNaOHcontains5.010 2molL1ofOHbecausethebaseisfullydissociatedand
eachmoleofNaOHreleases1moleofOHwhenitdissociates.Therefore,pOH=log(5.010 2)=
1.30,andpH=14.001.30=12.70at25C.

ForbasessuchasBa(OH)2,wehavetorecognisethat2molesofOHarereleasedbyeachmoleofthe
base.

Therefore,ifasolutioncontained1.010 2molBa(OH)2perlitre,theconcentrationofOHwouldbe
2.010 2M.Ofcourse,onceweknowtheOHconcentrationwecancalculatepOH,fromwhichwe
cancalculatethepH.Workedexample11.7illustratesthekindsofcalculationswehavejustdescribed.

WORKEDEXAMPLE11.7

CalculatingpH,pOH,[H3O+]and[OH]foraqueoussolutions
ofstrongacidsorbases

CalculatethepH,pOH,[H3O+]and[OH]ofthefollowingsolutionsat25C:(a)2.010 2
MHCland(b)3.510 4MBa(OH)2.HClisastrongacidandBa(OH)2isastrongbase.

Analysis

Thesolutein(a)isHCl,astrongacid.ItgivesquantitativeformationofH3O+andtherefore
thereaction:

proceedstocompletion.FromeachmoleofHCl,weexpect1moleofH3O+,sowecanuse
themolarconcentrationofHCltoobtain[H3O+],fromwhichwecancalculatethepH,pOH
and[OH].

Thesolutein(b)isBa(OH)2,astrongbase.FromeachmoleofBa(OH)2,2molesofOHare
liberated,accordingtotheequation:

andthisproceedstocompletion.WeusethemolarityofBa(OH)2tocalculatethehydroxide
ionconcentration.From[OH]wecancalculate[H3O+],pOHandpH.

Solution
(a) BecauseHCliscompletelydissociated,in2.010 2MHCl,[H O+]=2.010 2M.
3
Therefore:

Thus,in2.010 2MHCl,thepHis1.70.ThepOHis(14.001.70)=12.30.Tofind
[OH],wecanusethisvalueofpOH.

Noticehowmuchsmaller[OH]isinthisacidicsolutionthanitisinpurewater.This
makessensebecausethesolutionisquiteacidic.
(b)Asnoted,Ba(OH)2isastrongbase,andsoforeachmoleofBa(OH)2weobtain2
molesofOH.Therefore:

ThusthepOHofthissolutionis3.15,andthepH=(14.003.15)=10.85.Wecan
thenobtain[H3O+]fromtheequation:

WewouldexpecttheconcentrationofH3O+tobeverylowbecausethesolutionis
quitebasic.

Isouranswerreasonable?

In(a),theconcentrationofH3O+isbetween10 2Mand10 1MandsothepHmustbe

between1and2,aswefound.In(b),themolarityofOHisbetween10 4Mand10 3M.
Hence,thepOHmustbebetween3and4,whichitis.

PRACTICEEXERCISE11.8

Calculate[H3O+]andthepHofanaqueous
 5.010 3MNaOHsolution.

PRACTICEEXERCISE11.9
Rhododendronsareshrubsthatproduce
beautifulflowersinspring.Theygrowwell
onlyinsoilwithapHof5.5orslightly
lower.WhatistheH3O+concentrationinthe
soilmoistureifthepHis5.5?

SuppressionoftheAutoprotolysisofWater

Intheprecedingcalculations,wehaveassumedthatalloftheH3O+orOHinthesolutionsofstrong
acidorbasecomesfromtheacidorthebaserespectively.However,thereisanotherpotentialsourceof
bothH3O+andOHinanaqueoussolution,namelywater.Wehaveseenthattheautoprotolysisofwater
givesrisetolowconcentrationsofH3O+andOH,andwewillnowshowtheconditionsunderwhich
wearejustifiedinneglectingthesecontributions.Wewillconsideronlyasolutionofstrongacid,but
realisethatanalogousargumentsapplyforasolutionofastrongbase.

Inanaqueoussolutionofanyacid,therearetwosourcesofH3O+theaciditself,andwater.Thus,

Exceptinverydilutesolutionsofstrongacids,theamountofH3O+contributedbywater([H3O+]from
H2O)isnegligiblecomparedwiththeamountofH3O+fromtheacid([H3O+]fromacid).Forinstance,in
workedexample11.7wesawthatin2.010 2MHClthe[OH]was5.010 13M.Theonlysourceof
OHinthisacidicsolutionisfromtheautoprotolysisofwater,andtheamountsofOHandH3O+
formedbytheautoprotolysisofwatermustbeequal.Therefore,[H3O+]fromH2Oalsoequals5.0
10 13M.Ifwenowlookatthetotal[H3O+]forthissolution,wehave:

Inanysolutionofanacid,theautoprotolysisofwaterissuppressedbytheH3O+producedbytheacid.
Thisisademonstrationofthecommonioneffectwefirstdiscussedinchapter10(p.404)inthiscase,
H3O+isthecommonion,andthelargeexcessofH3O+fromtheacidsuppressestheautoprotolysisof
water.

Wecanrationalisethisbyconsideringtheautoprotolysisequilibriumofwater.

IfweaddanothersourceofH3O+towater,weinstantaneouslyincreasethereactionquotientQw(where
Qw=[H3O+][OH]),sothatQw>Kw.Therefore,theequilibriumshiftstowardsthereactantstodecrease
Qw,resultinginloweramountsofbothH3O+andOHfromtheautoprotolysisofwater.Similar
reasoningalsoappliestotheadditionofanothersourceofOHtowater.Therefore,additionofeither
H3O+orOHtowatersuppressestheautoprotolysisofwater.Themaximumpossiblecontributionof
[H3O+]or[OH]fromtheautoprotolysisofwateris1.010 7Mat25.0C,and,inmostcases,
especiallywhenstrongacidsorbasesareinvolved,thiscanbesafelyignored.However,asshownin
workedexample11.8,thereareexceptions.

WORKEDEXAMPLE11.8

CalculatingthepHofVeryDiluteStrongAcidSolutions

CalculatethepHofa1.010 10MsolutionofHCl(aq).

Analysis

Atfirstglance,thisappearsasimplematterofequating[H3O+]totheconcentrationofthe
acid,aswehavedoneinpreviousexamplesconcerningstrongacidsolutions.However,if
wedothis,weobtainapHof10,whichisobviouslyincorrectasitwouldmeanthatthe
solutionofHClisbasic!Inthiscase,weneedtotakebothpossiblesourcesofH3O+into
accountHClandH2Oandseewhichone,ifany,dominates.

Solution

WestartbycalculatingthecontributionofH3O+frombothwaterandHCl.Weknowthatthe
HClsolutionis1.010 10M,andtherefore:

Ordinarily,theadditionofacidtowaterwouldsuppresstheautoprotolysisofwaterthrough
thecommonioneffect(H3O+isthecommonion),meaningthatthecontributionofH3O+
fromthiswouldbelessthan1.010 7M.However,inthiscase,theconcentrationofacidis
verysmallcomparedwiththatresultingfromtheautoprotolysisofwater,andwecan
thereforesay,toaverygoodapproximation:

Hence:

andthecalculatedpHbecomes:
 Isouranswerreasonable?

ApHof7iscertainlymuchmorereasonablethanapHof10.Thestrongacidissodilute
that,inthiscase,wateristhemajorcontributorofH3O+tothesolution.

PRACTICEEXERCISE11.10

CalculatethepHofa1.010 11Msolution
ofNaOH.

Fromnowon,weassumethat,exceptforverydilutesolutions(10 6Morless),theautoprotolysisof
watercanbeneglectedwhencalculatingthepHofstrongacidsorbases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.4WeakAcidsandBases
Earlierinthischapter(p.438),westatedthatweakacidsandweakbasesreactincompletelywithwater
togivelessthanstoichiometricamountsofH3O+andOHrespectively.Wecanquantifytheextentto
whichthesereactionsoccurbylookingatthevaluesoftheirequilibriumconstants.Ifweconsidera
weakmonoproticacidHA,wecanwriteitsreactionwithwateras:

Theequilibriumconstantexpressionforthisistherefore:

Theequilibriumconstantforthedissociationofanacidinaqueoussolutioniscalledtheacidity
constantandisgiventhesymbolKa .WecanseethatthevalueofKa tellsushowfarthereactionhas
proceededtowardscompletionwhenequilibriumisestablished.

Similarly,wecanwritetheequationforthereactionofaweakmonoproticbaseBwithwateras:

andthecorrespondingequilibriumconstantexpressionis:

ThisiscalledthebasicityconstantandisgiventhesymbolKb.

Whenpolyproticacidsorbasesareconsidered,aseparateequilibriumconstantmustbewrittenforeach
protonlossorprotongain.Forexample,thediproticacidH2Awillundergotwoseparateprotonloss
reactionsinwater,oneinvolvingH2Aandtheotherinvolvingitsconjugatebase,HA.Thisgivesriseto
twoseparateKa expressions.

AnalogousKbexpressionscanbewrittenforapolyproticbase.

Becauseweakacidsandweakbasesreactwithwateronlytoaverysmallextent,bothKa andKbvalues
aregenerallysignificantlylessthan1.Forexample,Ka foraceticacidis1.810 5,whileKbfor
pyridineis1.710 9.Toputthesevaluesinperspective,itisagaininstructive(aswedidinchapter9)
towritethesenumbersinanalternativeformforexample,knowingthat ,wecanwrite
Ka foraceticacidas:

Whenwritteninthisfashion,itisevidentthattheconcentrationsonthetoplinearemuchsmallerthan
theconcentrationonthebottom.Inotherwords,theconcentrationofundissociatedacidatequilibrium
isenormouscomparedwith[H3O+]and[CH3COO].Thismeansthataceticacidisindeedaweakacid.
Asimilarapproachcanbeusedtoemphasisetheweaklybasicnatureofpyridine.

BecauseKa andKbvaluesareusuallysignificantlylessthan1,itisoftenmoreconvenienttousepKa
andpKbvalues,where:

BothpKa andpKbareanalogoustopH,andthedefiningequationsarethereforesimilar.Wecanalso
writeeachequationintermsofKa andKbrespectively,andthesethenbecome:

NotethatpolyproticacidsandbaseshavemorethanonepKa orpKbvalue.

ThestrengthofaweakacidisdeterminedbyitsKa value:thelargertheKa ,thestrongertheacidandthe

greaterthedegreeofdissociationatequilibrium.Becauseofthenegativesigninthedefiningequation
forpKa ,thestrongertheacid,thesmallerisitspKa value.ThevaluesofKa andpKa forsometypical
weakacidsaregivenintable11.4.AmorecompletelistislocatedinappendixE.Similararguments
applytoKbandpKbvalues,someofwhicharegivenintable11.5.

TABLE11.4 Ka andpKa valuesforweakmonoproticacidsat25C

Nameofacid Formula Ka pKa
chloroaceticacid ClCH2COOH 1.410 3 2.85

nitrousacid HNO2 7.110 4 3.15

hydrofluoricacid HF 6.810 4 3.17

cyanicacid HOCN 3.510 4 3.46

formicacid HCOOH 1.810 4 3.74

barbituricacid 9.810 5 4.01

aceticacid CH3COOH 1.810 5 4.74

hydrazoicacid HN3 1.810 5 4.74

butanoicacid CH3CH2CH2COOH 1.510 5 4.82

propanoicacid CH3CH2COOH 1.410 5 4.89

hypochlorousacid HOCl 3.010 8 7.52

hydrogencyanide(aq) HCN 6.210 10 9.21

phenol C6H5OH 1.310 10 9.89
hydrogenperoxide 11.74
 H2O2 1.810 12

TABLE11.5 Kb andpKb valuesforweakmolecularbasesat25C

Nameofbase Formula Kb pKb
butylamine C4H9NH2 5.910 4 3.23

methylamine CH3NH2 4.410 4 3.36

ammonia NH3 1.810 5 4.74

hydrazine N2H4 1.710 6 5.77

strychnine 1.010 6 6.00

morphine 7.510 7 6.13

hydroxylamine HONH2 6.610 9 8.18

pyridine C5H5N 1.710 9 8.77

aniline C6H5NH2 4.110 10 9.36

WORKEDEXAMPLE11.9

InterpretingpKaandFindingKa

AcertainacidwasfoundtohaveapKa of4.88.Isthisacidstrongerorweakerthanacetic
acid?WhatistheKa fortheacid?

Analysis

WecancomparetheacidstrengthsbycomparingthepKa values.ThelargerthepKa ,the

 weakeristheacid.FindingKa frompKa involvesthesamekindofcalculationasfinding
[H3O+]frompH,whichyoulearnedtodoearlierinthischapter.

Solution

Fromtable11.4,thepKa ofaceticacidis4.74.TheacidreferredtointheproblemhasapKa
of4.88.BecausetheacidhasalargerpKa thanaceticacid,itisaweakeracid.

TofindKa frompKa ,weusetheequation:

SubstitutingpKa =4.88:

Isouranswerreasonable?

Asaquickcheck,wecancomparetheKa values.Foraceticacid,Ka =1.810 5.Thisis

largerthan1.310 5,whichtellsusthataceticacidisthestrongeracid.Thisagreeswithour
conclusionbasedonthepKa values.

PRACTICEEXERCISE11.11
Twoacids,HXandHY,havepKa valuesof
3.16and4.14,respectively.Whichisthe
strongeracid?WhataretheKa valuesfor
theseacids?

Somemoleculescontainbothanacidicsiteandabasicsite,andthisleadstointerestingstructural
consequences.Consider,forexample,theaminoacidglycine.Wewouldusuallywritethecondensed
structuralformulaofthismoleculeasNH2CH2COOH.However,itactuallyexistsinthesolidstateasa
zwitterion,astructurewhichcontainsbothapositiveandnegativechargebutwhichisoverallneutral.

Wewilldiscusssuchcompoundsinmoredetailinchapter24.

Welearnedinchapter9howtomanipulateequilibriumconstantexpressionsandfoundthat,whentwo
chemicalequationswereaddedtogether,theequilibriumconstantfortheresultingequationwasequalto
theproductoftheequilibriumconstantsforthetworeactions.Thisapproachleadstoanimportantresult
whenappliedtoanacidanditsconjugatebase.Consider,forexample,formicacid,HCOOH,aweak
acidpartlyresponsibleforthestingofsomeants(thewordformicaisLatinforant).Theacidreacts
withwateraccordingtotheequation:
forwhich:

Theconjugatebaseofformicacid,theformateion,HCOO,reactswithwaterasfollows:

andhence:

Ifweaddtheseequations,weobtaintheequationfortheautoprotolysisofwater.

IfwemultiplytheexpressionsforKa andKbtogether,weobtain:

or

Thisrelationshipholdsforanyacidbaseconjugatepair,regardlessofthestrengthoftheacidorbase.

AnotherusefulrelationshipcanbederivedbytakingthenegativelogarithmofeachsideofKa Kb=Kw
andrememberingthatthelogarithmoftheproductoftwonumbersisthesumoftheirlogarithms.

TherearesomeimportantconsequencesoftherelationshipKa Kb=Kw.Oneisthatitisnotnecessaryto
tabulatebothKa andKbforthemembersofanacidbasepairifoneKisknown,theothercanbe
calculated.Forexample,Ka forHCOOHandKbforNH3arefoundinmosttablesofacidbase
equilibriumconstants,butthesetablesusuallydonotcontainKbforHCOOorKa forNH4+.Ifweneed
them,wecancalculatethemusingKa Kb=Kw.

PRACTICEEXERCISE11.12

ThevalueofKa forHCOOHis1.810 4.
WhatistheKbfortheHCOOion?

Anotherinterestingandusefulobservationisthatthereisaninverserelationshipbetweenthestrengths
oftheacidandbasemembersofaconjugatepair.Thisisillustratedgraphicallyinfigure11.11.
BecausetheproductofKa andKbisaconstant,thelargerthevalueofKa ,thesmallerthevalueofKb.In
otherwords,thestrongertheconjugateacid,theweakeritsconjugatebase.Donotmakethemistakeof
assumingthattheconjugatebaseofaweakacidisstrong.Inspectionoffigure11.11anduseofthe
relationshippKa +pKb=14.00showthat,infact,theconjugatebaseofaweakacidisweak.For
example,thepKa ofaceticacid,aweakacid,is4.74.Itsconjugatebase,theacetateion,musttherefore
haveapKbof(14.004.74)=9.26,avalueindicativeofaweakbase.Similarargumentsapplyforthe
conjugateacidofaweakbase.

FIGURE11.11Therelativestrengthsofconjugateacidbasepairs.Thestrongertheacid,theweakerits
conjugatebase.Theweakertheacid,thestrongeritsconjugatebase.

pHCalculationsinSolutionsofWeakAcidsandBases
Insection11.3,welearnedhowtocalculatethepHofsolutionsofstrongacidsandbases.The
calculationsreliedonthefactthat,becausestrongacidsandbasesdissociatecompletelyinwater,the
concentrationofH3O+orOHwasequaltotheinitialconcentrationoftheacidorbase.

However,becauseweakacidsandbasesreactincompletelywithwater,thisisnolongerthecase.For
weakacidsandbases,wemustusethevalueofKa orKbtodetermine[H3O+]or[OH]andhencepH.
WewillillustratethisbycalculatingthepHofa1.0Msolutionofaceticacid,CH3COOH.

Webeginbywritingthebalancedchemicalequationforthereactionoftheacidwithwater,andobtain
theexpressionforKa fromthis.

Wecannotsolvethisequationfor[H3O+]directlyinthisformastherearetwounknowns:[CH3COO]
and[CH3COOH].Thefactthattheseunknownsarerelated(thesumof[CH3COO]and[CH3COOH]
mustbe1.0M,theinitialconcentrationoftheacid)allowstheequationtobesolvedusingarithmetic
manipulations,butthisinvolvessolvingaquadraticequation.However,itisusualtouseaconcentration
tableforcalculationsofthissort.Wesetthisupinthesamewayaswedidinchapter9.Weassumethat
theinitialconcentrationofCH3COOHis1.0MandtheinitialconcentrationsofbothH3O+and
CH3COOare0.(RecallthatthereisasmallnonzeroconcentrationofH3O+arisingfromthe
autoprotolysisofwater,butwecansafelyneglectthisasitisamaximumof1.0.10 7M.)Asthe
reactionproceedstoequilibrium,theconcentrationofCH3COOHdecreasesbyx,andthe
concentrationsofbothH3O+andCH3COOincreaseby+x,owingtothestoichiometryofthereaction.
Atequilibrium,theconcentrationsofCH3COOH,CH3COOandH3O+are(1.0x),xandx,
respectively.Hence,weobtainthefollowingconcentrationtable(asinchapter9,concentrationsgiven
inthequestionarehighlighted).

H2O+CH3COOH H3O+ + CH3COO

Initialconcentration(molL1) 1.0 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(molL1) 1.0x x x

WhenthevaluesinthelastrowofthetablearesubstitutedintotheexpressionforKa weobtain:

Thisequationinvolvesaterminx2,anditcouldbesolvedexactlyusingthequadraticformula.
However,thisandmanyothersimilarcalculationsinvolvingweakacidsandbasescanbesimplified.
Recallfromchapter9(p.379)that,iftheconcentrationfromwhichxissubtractedisatleast400times
aslargeasK,wecanmakesimplifyingassumptions.Inthiscase,theinitialconcentrationof1.0Mis
indeedatleast400timesaslargeasKa ,1.810 5.Therefore,wecanmaketheapproximation(1.0x)
1.0.Ifwenowreplace1.0xwith1.0intheequationabove,weobtain:

Wecannowsolvethisdirectly:

Weseethatthevalueofxisindeednegligiblecomparedwith1.0M(i.e.ifwesubtract4.210 3M
from1.0Mandroundcorrectly,weobtain1.0M).Wealsonotethatthesameanswer(totwosignificant
figures)isobtainedbysolvingthequadraticequationexactly,furtherjustifyingourassumption.This
valuecorrespondstoapproximately1moleculein240ofCH3COOHbeingdissociatedatequilibrium
CH3COOHisindeedaweakacid.Havingcalculatedx,andknowingthatx=[H3O+]atequilibrium,we
canfindthepHofthesolutionbytakingthenegativelogarithmofthisnumber.
Noticethatwhenwemaketheapproximationabove,theinitialconcentrationoftheacidisusedasifit
weretheequilibriumconcentration.Thisapproximationisvalidwhentheequilibriumconstantissmall
andtheconcentrationsofthesolutesarereasonablyhighconditionsthatapplytomostsituationsyou
willencounter.Onpp.4546,wewilldiscusstheconditionsunderwhichtheapproximationisnotvalid.

RecallalsothatweneglectedanycontributionofH3O+fromtheautoprotolysisofwatertothetotal
[H3O+]inthesolution.Wecanshowthatthisassumptionisjustifiedbylookingatthemagnitudeof
[H3O+]duetotheacidcomparedwith[H3O+]fromwater.Themaximumpossible[H3O+]contributed
bywateris1.010 7M,andthiswillbesmallerinrealityowingtothecommonioneffectfromthe
presenceoftheacid.Evenifwecomparethemaximumpossible[H3O+]fromwater(1.010 7M)with
[H3O+]fromtheacid(4.210 3M),weseethatitisnegligiblysmall(4.210 3M+1.010 7M=4.2
10 3M)andsoourassumptionisjustified.

Wewillnowlookatsomeexamplesthatillustratetypicalweakacidandweakbaseequilibrium
problems.

WORKEDEXAMPLE11.10

Calculating[H3O+]andpHValuesforaSolutionofaWeak
AcidfromitsKaValue

Calciumpropanoate,acompoundusedasapreservativeinbakedgoods(figure11.12),isa
saltoftheweakacidpropanoicacid,CH3CH2COOH.Astudentplannedanexperimentthat
wouldusepropanoicacidataconcentrationof0.10M.Calculatethevaluesof[H3O+]and
pHforthissolutionat25C.Forpropanoicacid,Ka =1.410 5at25C.

FIGURE11.12Thecalciumsaltofpropanoicacid,calciumpropanoate,isusedasapreservative
inbakedproducts.

Analysis
First,wewritethebalancedequationforthereactionoftheacidwithwaterandobtainthe
expressionforKa fromthis.

Theinitialconcentrationoftheacidis0.10M,andtheinitialconcentrationsofbothionsare
0M.TheconcentrationofCH3CH2COOHwillchangebyxandthoseofCH3CH2COOand
H3O+willincreaseby+xasthereactionproceedstoequilibrium.Wecannowconstructthe
concentrationtable.

Solution

H2O+ H3O+ + CH3CH2COO

CH3CH2COOH

Initialconcentration 0.10 0 0
(molL1)
Changein x +x +x
concentration(molL1)
Equilibrium 0.10x x x
concentration(molL1)

Aspropanoicacidisaweakacid,itdissociatesonlytoasmallextentandthereforexisvery
small.Wecanthenmakethesimplifyingapproximationthat(0.10x)0.10,sowetakethe
equilibriumconcentrationofCH3CH2COOHtobe0.10M.Substitutingthesequantitiesinto
theKa expressiongives:

Wecannowsolvethisforx:

Weknowthatx=[H3O+]andtherefore:

Finally,wecalculatethepH:

Isouranswerreasonable?
 First,weseethatthecalculatedpHislessthan7.Thistellsusthatthesolutionisacidic,
whichitshouldbeforasolutionofanacid.Also,thepHishigherthanitwouldbeiftheacid
werestrong.(A0.10Msolutionofastrongacidwouldhave[H3O+]=0.10MandpH=1.0.)
Ifwewishtofurtherchecktheaccuracyofthecalculation,wecansubstitutethecalculated
equilibriumconcentrationsintotheexpressionforKa .Ifthecalculatedquantitiesarecorrect,
weshouldobtainthenumericalvalueofKa .

Thecheckworks,sowehavedonethecalculationcorrectly.

PRACTICEEXERCISE11.13
PantothenicacidisalsocalledvitaminB5.Itisalsoa
weakacidwithKa =3.910 5.Calculate[H3O+]and
thepHofa0.050Msolutionofpantothenicacid.

WORKEDEXAMPLE11.11

CalculatingthepHofasolutionofaweakbase
Asolutionofhydrazine,N2H4,aweakbase,hasaconcentrationof0.25M.WhatisthepHof
thesolution?HydrazinehasKb=1.710 6.

Analysis

Thisexampleisanalogoustoworkedexample11.10,exceptthatwearenowdealingwitha
weakbaseandusingKbratherthanKa .

Solution

WebeginwiththebalancedchemicalequationandobtaintheKbexpression.
Again,theconcentrationofN2H4willchangebyxandthoseofN2H5+andOHwill
increaseby+xasthereactionproceedstoequilibrium.Weconstructtheconcentrationtable
asfollows.

H2O N2H4 N2H5+ + OH

+

Initialconcentration(molL1) 0.25 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(mol 0.25 x x
L1) x

Becausehydrazineisaweakbase,itreactswithwateronlytoasmallextent.Wecan
thereforemakethesameapproximationthatwemadeforaweakacidthatis(0.25x)
0.25.WesubstitutethevaluesfromtheconcentrationtableintotheKbexpression.

Wesolvethisforxasfollows.

Thisvaluerepresentsthehydroxideionconcentration,fromwhichwecancalculatethepOH.

ThepHofthesolutioncanthenbeobtainedfromtherelationship:

Isouranswerreasonable?

Asstatedinthequestion,hydrazineisaweakbase,sowewouldexpectapH>7.Wecan
quicklychecktoseewhetherthevalueofxandourassumedequilibriumconcentrationof
N2H4(0.25M)arecorrectbysubstitutingthemintotheexpressionforKbandcomparingthe
resultwiththenumericalvalueofKb.Doingthisgives1.710 6,whichisthesameasKb,so
thevalueofxiscorrect.

PRACTICEEXERCISE11.14
 Pyridine,C5H5N,isatoxic,foulsmelling
liquidforwhichKb=1.710 9.Whatisthe
pHofa0.010Maqueoussolutionof
pyridine?

PRACTICEEXERCISE11.15
Phenol,C6H5OH,isaweaklyacidicorganic
compound,commonlyusedasa
disinfectant,forwhichKa =1.310 10.
WhatisthepHofa0.15Msolutionof
phenolinwater?

Inworkedexamples11.10and11.11,wehavecalculatedthepHgiventhevalueofKa orKb.Wecan
alsousemeasuredvaluesofpHtocalculateKa orKbvalues,asshowninworkedexample11.12.

WORKEDEXAMPLE11.12

CalculatingKaandpKafrompH

Lacticacid,CH3CH(OH)COOH,isamonoproticacidthatispresentinsourmilkand
yoghurt.ThepHofa0.100Msolutionoflacticacidis2.44at25C.CalculateKa andpKa
forlacticacidatthistemperature.

Analysis

InthiscasewearegiventhepHofthesolution,fromwhichwecancalculate[H3O+].In
essence,thisisthereverseofthepreviousexamples.Weusethebalancedchemicalequation
toconstructaconcentrationtableandthensubstitutethecalculatedequilibrium
concentrationsintotheexpressionforKa .

Solution

WebeginbywritingthebalancedchemicalequationandobtainingtheexpressionforKa .

Inthisproblem,theonlysourceoftheionsH3O+andCH3CH(OH)COOistheacid.Asa
result,theequilibriumconcentrationofH3O+mustbeidenticaltothatofCH3CH(OH)COO
becausethereactiongivestheseionsina1:1ratio.However,wedonothavethevaluesof
either[H3O+]or[CH3CH(OH)COO]allwehaveisthepHofthe0.100Msolution.Westart
byfinding[H3O+]fromthepH.Thisgivesustheequilibriumvalueof[H3O+].

Because[CH3CH(OH)COO]=[H3O+],weknowthat[CH3CH(OH)COO]=3.610 3Mat
equilibrium.Wenowsetuptheconcentrationtable,giventhattheinitialconcentrationof
lacticacidis0.100M.

H2O+CH3CH(OH)COOH H3O+ + CH3CH(OH)COO

Initialconcentration 0.100 0 0
(molL1)
Changein 3.610 3 +3.6 +3.610 3
concentration(mol 10 3
L1)
Equilibrium 0.1003.6 3.6 3.610 3
concentration(mol 10 3=0.096 10 3
L1)

Thisproblemdiffersfromthepreviousworkedexamplesinthatweknowthevalueofx(3.6
10 3M)butwedonotknowKa .Weproceedbysubstitutingtheequilibriumvaluesintothe
Ka expression.Weknowthatboth[H3O+]and[CH3CH(OH)COO]=3.610 3M,and,from
theconcentrationtable,that[CH3CH(OH)COOH]=(0.100x)=(0.1003.610 3)=0.096
M.(Notethat,becauseweknowthevalueofxinthiscase,wedonothavetomakethe
assumptionthat(0.100x)0.100.)Therefore:

ThustheKa forlacticacidis1.410 4.TofindpKa ,wetakethenegativelogarithmofKa .

Isouranswerreasonable?

Weakacidshavesmallacidityconstants,sothevalueweobtainedforKa seemstobe
reasonable.Weshouldalsochecktheentriesintheconcentrationtabletobesuretheyare
reasonable.Forexample,thechangesfortheionsarebothpositive,meaningbothoftheir
concentrationsareincreasing.Thisisthewayitshouldbe.Also,wehavetheconcentration
oflacticaciddecreasing,asitmustdo.
 PRACTICEEXERCISE11.16
Fewsubstancesaremoreeffectivein
relievingintensepainthanmorphine.
Morphineisanalkaloidaweaklybasic
compoundobtainedfromplants.ThepHof
a0.010Maqueoussolutionofmorphineis
10.10.CalculatetheKbandpKbfor
morphine.UsethesymbolB,ratherthanthe
chemicalformulaofmorphinegivenintable
11.5,whenyouwritetheequation.

pHCalculationsinSolutionsofSaltsofWeakAcidsandBases

WehaveseenthatCl,theconjugatebaseofthestrongacidHCl,isaveryweakbaseandshows
essentiallynotendencytoreactwithH3O+toformHCl.ThismeansthatClisevenlesslikelytoactasa
basetowardsH2O,andwecansaythatClhasessentiallynobasicproperties.Therefore,anaqueous
solutionofNaClhasapHof7.00at25C.Thisistrueoftheconjugatebasesofallstrongmonoprotic
acids.Thus,diluteaqueoussolutionsofsaltssuchasNaBr,NaI,NaNO3,and,indeed,anysodiumsalt
ofastrongmonoproticacid,havepHvaluesof7.00at25C.However,thisisnotthecaseforthesalt
ofaweakacid,suchasNaOOCCH3,whichhasapH>7,orthesaltofaweakbase,suchasNH4Cl,
whichhasapH<7atthistemperature.Ifwedissolveeachoftheseinwater,wegetcomplete
dissociationintotherespectiveionsasfollows.

TheCH3COOandNH4+ionsaretheninvolvedinthefollowingequilibria:

andthetwosolutionsarethereforeslightlybasicandslightlyacidic,respectively.

Asillustratedinfigure11.11(p.446),conjugatebasestrengthincreasesasacidstrengthdecreases,and
thereforethesaltsofweakacidscanbeappreciablybasic.Similarly,thesaltsofweakbasesare
generallyslightlyacidic.WecanseethatthisisthecasebylookingatpKa andpKbvaluesforconjugate
pairs.Forexample,aswehaveseen,aceticacid,CH3COOH,hasapKa of4.74,andthismeansthatthe
acetateion,CH3COO,hasapKbof14.004.74=9.26.IfweconsiderHCN,anevenweakeracid(pKa
=9.21),wecanseethatthecyanideion,CN,hasapKbof14.009.21=4.79,makingitalmostas
strongabaseasammonia,NH3.WecanusethepKa andpKbvaluestocalculatethepHofaqueous
solutionscontainingthesaltsofweakacidsandbases,asshowninworkedexamples11.13and11.14.

WORKEDEXAMPLE11.13
CalculatingthepHofasaltsolution

WhatisthepHofa0.10MsolutionofNaOClat25C?ForHOCl,Ka =3.010 8.

Analysis

OClistheconjugatebaseoftheweakacidHOCl,andwethereforeexpectthesolutiontobe
slightlybasic.AswearegivenonlyKa forHOClandweareaskedtofindthepH,weuseKb,
whichwecanobtainfromKa ,tosolvethisproblem.Asusual,westartwithabalanced
chemicalequationandobtaintheexpressionfortheappropriateequilibriumconstantfrom
this.

Solution

First,wewritethechemicalequationforthereactionofOClwithwaterandthe
correspondingKbexpression.

ThedataprovidedintheproblemgivetheKa forHOCl,butwecancalculateKbbecause
Ka Kb=Kwforaconjugatepair.

Nowletussetuptheconcentrationtable.TheonlysourceofHOClandOHisthereactionof
OCl,sotheirconcentrationseachincreasebyxandtheconcentrationofOCldecreasesbyx
asthereactionproceedstoequilibrium.

H2O+OCl HOCl + OH

Initialconcentration(molL1) 0.10 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(molL1) (0.10x) x x

Atequilibrium,theconcentrationsofHOClandOHarethesame,x.

AsOClisaweakbase,itreactswithwateronlytoasmallextent,andthereforexissmall.
Wecanthenmaketheapproximationthat(0.10x)0.10andso[OCl]=0.10Mat
equilibrium.WesubstitutethevaluesintotheKbexpressiontogive:

Wesolvethisforxasfollows:
 ThisvalueofxrepresentstheOHconcentration,fromwhichwecancalculatethepOHand
thenthepH.

ThepHofthissolutionis10.26.

Isouranswerreasonable?

Fromthenatureofthesalt,weexpectthesolutiontobebasic.ThecalculatedpHcorresponds
toabasicsolution,sotheanswerseemsreasonable.Wecanalsochecktheaccuracyofthe
answerbysubstitutingthecalculatedequilibriumconcentrationsintotheexpressionforKb.

TheresultisacceptablyclosetothevalueofKb,soouranswersarecorrect.

WORKEDEXAMPLE11.14

CalculatingthepHofasaltsolution
WhatisthepHofa0.20Msolutionofhydraziniumchloride,N2H5Clat25C?Hydrazine,
N2H4,isaweakbasewithKb=1.710 6.

Analysis

Thehydraziniumion,N2H5+,istheconjugateacidoftheweakbasehydrazine,N2H4,and
thereforeweexpectasolutioncontainingthisiontobeslightlyacidic.Weproceedina
similarfashiontoworkedexample11.13,starting,asever,withthebalancedchemical
equationandtheappropriateequilibriumconstantexpression.Aswehaveseen,Clisan
extremelyweakbaseitreactswithwatertoanegligibleextentanddoesnotaffectthepHof
thesolution.Itcanthereforebeneglectedinourcalculations.

Solution
WewillbeginwiththebalancedchemicalequationforthereactionofN2H5+withwaterand
writetheKa expression.

TheproblemhasgivenusKbforN2H4,butweneedKa forN2H5+.Weobtainthisbysolving
theequationKa Kb=KwforKa .

Nowwesetuptheconcentrationtable.TheinitialconcentrationsofH3O+andN2H4areboth
settozero.Next,weindicatethattheconcentrationofN2H5+decreasesbyxandthe
concentrationsofH3O+andN2H4bothincreasebyxasthereactionproceedstoequilibrium.

H2O+N2H5+ H3O++N2H4

Initialconcentration(molL1) 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(molL1) 0.20x x x

Atequilibrium,equalamountsofH3O+andN2H4arepresent,andtheirequilibrium
concentrationsareeachequaltox.

AsN2H5+isaweakacid,itreactswithwatertoasmallextent.Wecanassumethat(0.20x)
0.20because0.2>400Ka ,andtherefore[N2H5+]=0.20Matequilibrium.Wethen
substitutequantitiesintotheequilibriumconstantexpression.

Wesolvethisforxasfollows:

Sincex=[H3O+],thepHofthesolutionis:
 Isouranswerreasonable?

TheactivesolutespeciesinthesolutionisaweakacidandthecalculatedpHislessthan7,
sotheanswerseemsreasonable.Checktheaccuracyyourselfbysubstitutingequilibrium
concentrationsintotheexpressionforKa .

PRACTICEEXERCISE11.17
WhatisthepHofa0.10Msolutionof
NaNO2?UsethepKa ofHNO2fromtable
11.4.

PRACTICEEXERCISE11.18
WhatisthepHofa0.10Msolutionof
NH4Br?UsethepKbofNH3fromtable
11.5.

SolutionsthatContaintheSaltofaWeakAcidandaWeak
Base

WesawpreviouslythatboththeNH4+cationandCH3COOanionaffectthepHofanaqueoussolution.
WenowaddresswhathappenswhenboththecationandanioninasinglesaltareabletoaffectthepH.
WhetherornotthesalthasaneteffectonthepHnowdependsontherelativestrengthsofitsions,one
functioningasanacidandtheotherasabase.Iftheyarematchedintheirrespectivestrengths,thesalt
hasnoneteffectonpH.Consider,forexample,asolutionofammoniumacetate,NH4OOCCH3,in
whichtheammoniumionisanacidiccationandtheacetateionisabasicanion.However,Ka ofNH4+
is5.610 10andKbofCH3COOjusthappenstobethesame,5.610 10.Thecationtendstoproduce
H3O+ionstothesameextentthattheaniontendstoproduceOH.So,inaqueousammoniumacetate,
[H3O+]=[OH],andthesolutionhasapHof7.

Consider,now,ammoniumformate,NH4OOCH.Theformateion,HCOO,istheconjugatebaseofthe
weakacidformicacidandhasKb=5.610 11.Comparingthisvaluewiththe(slightlylarger)Ka ofthe
ammoniumion,5.610 10,weseethatNH4+isslightlystrongerasanacidthantheformateionisasa
base.Asaresult,asolutionofammoniumformateisslightlyacidic.TheexactcalculationofpHinsuch
solutionsisdifficult,andweareconcernedhereonlyinpredictingifthesolutionisacidic,basicor
neutral.
 WORKEDEXAMPLE11.15

PredictinghowasaltaffectsthepHofitssolution
Isa0.20MaqueoussolutionofNH4Facidic,basicorneutral?

Analysis

Thisisasaltinwhichthecationisaweakacid(itistheconjugateacidofaweakbase,NH3)
andtheanionisaweakbase(itistheconjugatebaseofaweakacid,HF).Thequestionis:
HowdothetwoionscompareintheirabilitiestoaffectthepHofthesolution?Wehaveto
comparetheirrespectiveKa andKbvaluestocomparetheirstrengths.

Solution

Ka ofNH4+(calculatedfromtheKbofNH3)is5.610 10.Similarly,KbofFis1.510 11
(calculatedfromtheKa ofHF,6.810 4).Comparingthetwoequilibriumconstants,wesee
thatKa fortheacid,NH4+,isgreaterthanKbforthebase,F.Therefore,thereactionofNH4+
withwatertogiveH3O+proceedstoagreaterextentthanthereactionofFwithwatertogive
OH.Thismeansthat,atequilibrium,[H3O+]>[OH],andweexpectthesolutiontobe
slightlyacidic.

Isouranswerreasonable?

Thereisnotmuchtocheckhereexcepttobesurethatwehavedonethearithmeticcorrectly.

PRACTICEEXERCISE11.19
Isanaqueoussolutionofammonium
cyanide,NH4CN,acidic,basicorneutral?

SituationswhereSimplifyingAssumptionsdonotWork
Onpp.44753,weusedinitialconcentrationsofacidsandbasesasthoughtheywereequilibrium
concentrationswhenweperformedcalculations.Thisisonlyanapproximation,aswediscussedonp.
447,butitworksmostofthetime.Unfortunately,itdoesnotworkinallcases,sowewillnowexamine
thoseconditionsunderwhichsimplifyingapproximationsdonotwork.Wewillalsostudyhowtosolve
problemswhentheapproximationscannotbeused.

WhenaweakacidHAreactswithwater,itsconcentrationisreducedastheionsform.Ifweletx
representtheamountofacidthatreactsperlitre,theequilibriumconcentrationbecomes:
Inpreviousproblems,wehaveassumedthat[HA]equilibrium[HA]equilibrium[HA]initialbecausexis
smallcomparedwith[HA]initial.However,thisisthecaseonlyif[HA]initialisgreaterthan,orequalto,
400timesthevalueofKa .AsthevalueofKa oftheweakacidincreases,ourassumptionbecomesless
validbecausetheextentofdissociationoftheacidincreases,and[HA]equilibriumisnolonger
approximatelyequalto[HA]initial.

Whenourassumptionisnotvalid,wemustsolveaquadraticequationaswedidinchapter9.Wealso
assumedthatwecouldsafelyneglectanycontributionto[H3O+]or[OH]fromtheautoprotolysisof
water.Thisisthecaseonlyifthevalueof[H3O+]or[OH]fromtheacidorbaseisgreaterthan110 5
(i.e.atleast100times110 7,themaximumpossiblecontributionfromwater).Thiswillgenerallybe
thecase,andweassumewecancontinuetoneglecttheautoprotolysisofwaterfromhereon.We
illustrateasituationthatrequiresuseofthequadraticformulainworkedexample11.16.

WORKEDEXAMPLE11.16

UsingtheQuadraticFormulainEquilibriumProducts
Chloroaceticacid,ClCH2COOH,isusedasaherbicideandinthemanufactureofdyesand
otherorganicchemicals.ItisaweakacidwithKa =1.410 3.WhatisthepHofa0.010M
solutionofClCH2COOHat25C?

Analysis

Beforewebeginthesolution,wechecktoseewhetherwecanuseourusualsimplifying
approximation.Wedothisbycalculating400Ka andthencomparingtheresultwiththe
initialconcentrationoftheacid.

TheinitialconcentrationofClCH2COOHislessthan0.56M,soweknowthesimplification
doesnotwork.Wethereforehavetosetupaconcentrationtableandthenuseaquadratic
equationtoobtainthesolution.

Solution

WebeginbywritingthebalancedchemicalequationandtheKa expression.

Theinitialconcentrationoftheacidwillbereducedbyanamount,x,asitreactswithwater
toformtheions.Fromthis,webuildtheconcentrationtable,assuming,asalways,thatthe
initialconcentrationsoftheionsarezero.

H2O+ClCH2COOH H3O++
ClCH2COO

Initialconcentration(molL1) 0.010 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(mol 0.010x x x
L1)

Substitutingequilibriumconcentrationsintotheequilibriumexpressiongives:

Thistimewecannotassume(0.010x)=0.010.Tosolvetheproblem,wefirstrearrangethe
expressiontoobtainthefamiliarformofaquadraticequation.Wedothisbymultiplying
bothsidesby(0.010x).Thisgives:

Thisisageneralquadraticequationoftheform:

Wenowusethequadraticformula:

andmakethesubstitutionsa=1,b=1.410 3andc=1.410 5.Enteringtheseintothe

quadraticformulagives:
Weknowthatxcannotbenegativebecausethatwouldgivenegativeconcentrationsforthe
ions,whichisimpossible,sowechoosethefirstvalueasthecorrectone.Thisyieldsthe
followingequilibriumconcentrations.

Finally,wecalculatethepHofthesolution.

Noticethatxisnotnegligiblecomparedwiththeinitialconcentration,sothesimplifying
approximationwouldnothavebeenvalid.Wecancalculatetheerrorthatwouldbeproduced
ifwemadethesimplifyingapproximationinthiscase.Wewouldobtainthesameequation.

and,makingtheassumptionthat(0.010x)0.010,wewouldthenobtain:

Solvingthisforxwouldgive:

Therefore,makingtheassumptiongives[H3O+]=3.710 3M,comparedwiththecorrect
valueof3.110 3Mfromsolutionofthequadraticequation,approximatelya20%error.

Isouranswerreasonable?
 Asbefore,aquickcheckcanbeperformedbysubstitutingthecalculatedequilibrium
concentrationsintotheequilibriumexpression.

ThevalueweobtainequalsKa ,sotheequilibriumconcentrationsarecorrect.

PRACTICEEXERCISE11.20
CalculatethepHofa0.0010Msolutionof
dimethylamine,(CH3)2NH.Dimethylamine
isaweakbasewithKb=9.610 4.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.5TheMolecularBasisofAcidStrength
Upuntilthispoint,wehavelabelledacidsaseitherstrongorweak,buthavenotexplainedwhat
determinesthestrengthofaparticularacid.Inthissection,wewillshowthatavarietyoffactors
contributetotheoverallstrengthofanacid.

Binaryacids
AbinaryacidisdefinedasanacidcontainingHandonlyoneotherelement,generallyanonmetal.The
simplestbinaryacidsarethemonoproticspeciesHF,HCl,HBrandHIcontaininggroup17elements.
DiproticbinaryacidsincludeH2OandH2S,whereasNH3andCH4areexamplesof,albeitextremely
weak,triproticandtetraproticbinaryacids,respectively.Theobservedorderofacidstrengthsofthese
acidsis(fromweakesttostrongest):

Inorderforeachofthesecompoundstoactasanacid,asingleHXbondmustbebroken,soitmight
beexpectedtherewouldbesomecorrelationbetweentheHXbondenthalpy(whichcanbethought
ofastheeasewithwhichthebondcanbebroken)andtheacidstrength.Ascanbeseenfromtable
11.6,thisisnotthecase.
TABLE11.6 BondenthalpiesforcleavageofsomeHXbonds
Bondenthalpyforhomolyticcleavage(kJ Bondenthalpyforheterolyticcleavage(kJ
Bond mol1) mol1)
CH 412 1744
N 388 1688
H
O 463 1633
H
SH 338 1468
FH 565 1554
Cl 431 1395
H
Br 366 1353
H
IH 299 1314

Thisisperhapsnotsurprisingwhenyouconsiderthedefinitionofbondenthalpy.Recall(p.313)thata
bondenthalpyreferstotheprocess:

inwhichthebondinthegasphasemoleculeundergoeshomolyticcleavage(thebondbreaksevenlyso
thatoneelectronisgiventoeachoftheatomsinvolvedinthebond)togiveelectricallyneutralspecies
suchaprocessisinfactverydifferentfromthatinvolvedinprotondonationfromHXtowater,which
occursviaheterolyticcleavage(thebondbreaksunevenlysothatbothelectronsaregiventooneofthe
atomsinvolvedinthebond)toformsolvatedions,accordingtotheequation:
AgoodcorrelationbetweentheacidityandtheheterolyticHXbondenergiesinthegasphasedoes
exist,ascanbeseenintable11.6thesegasphasedata,however,neglectsolventeffectsanddonot
thereforeconstituteanacceptableapproximationofreality.

AmorerealisticapproachthatdoesincludesolventeffectsusestheHess'slawcycleshowninfigure
11.13.

FIGURE11.13AHess'slawcycleforthedissociationofanacidinaqueoussolution.

ThevalueofHacid,theenthalpychangeforthedissociationoftheacidinitsstandardstate(gasforall
acidsexceptH2O)inwater,canbecalculatedforthebinaryacidslistedintable11.7usingavailable
thermochemicaldatabondHistheHXbondenergy(homolyticcleavage),Ei(H)istheionisation
energyofthegaseoushydrogenatom(1312kJmol1),EEAistheelectronaffinityofX(g),andhydH
(HX)isthehydrationenthalpy(p.397)ofgaseousHX.
TABLE11.7 Enthalpyandenergychangesinvolvedinthedissociationofavarietyofacidsinaqueous
solutionat25C

bondH(kJmol Ei(H)+EEA(X)(kJ hydH(HX)(kJmol Hacid(kJmol

Acid(HX) 1) mol1) 1) 1)

CH4(X= 412 1303 1583 132

CH3)

NH3(X= 388 1241 1603 26

NH2)

H2O(X= 463 1134 1623 15 (a)

OH)
H2S(X=SH) 338 1090 1443 15

HF(X=F) 565 990 1613 58

HCl(X=Cl) 431 963 1470 76
HBr(X=Br) 366 987 1439 86
HI(X=I) 299 1017 1394 78

(a)Toprovideameaningfulcomparisonwiththeotheracids,H2Omustbevaporised,aprocess
whichrequires41kJmol1.Thefinalvalueof15kJmol1includesthiscontribution.

Itcanbeseen,fromthedataintable11.7,thatthetrendsintheHacidvaluescorrelatewellwiththe
acidstrengthsasHacidbecomeslesspositive(morenegative),theacidstrengthincreases.Itcanalso
beseenthatnosinglecontributingfactortoHacidisprimarilyresponsiblefortheobservedtrendin
acidstrengths.Whileitmaybetemptingtoattributetheincreasingacidityinthemonoproticacidsfrom
HFtoHItothesignificantdecreaseinbondH,thisisalmostexactlyopposedbythedecreaseinhydH
values.Similarly,anincreaseinelectronaffinityofXdoesappeartocorrelatewellwithanincreasein
acidity,butthisbreaksdownforHBrandHI.Itshouldalsobenotedthattheaboveapproachneglects
entropiceffects,whichwillundoubtedlycontributetotheoverallenergeticsoftheaciddissociation
process.

Havingsaidthis,twogeneralobservationsconcerningtheacidstrengthofbinaryacidscanbemade:
1.Theacidstrengthofbinaryacidsincreasesgoingacrossaperiod(forexample,CH4<NH3<H2O
<HF).
2.Theacidstrengthofbinaryacidsincreasesgoingdownagroup(forexample,HF<HCl<HBr<
HI).

ThefirstobservationhasbeenattributedtotheincreasingelectronegativityofX,renderingtheHX
bondmorepolar,whilethesecondhasbeenexplainedbytheincreasingsizeofX,makingtheHX
bondlongerand,therefore,weaker.Asthedataintable11.7show,however,suchsimple
interpretationsshouldbetreatedwithcaution,andaregenerallybestavoided.

PRACTICEEXERCISE11.21
Usingonlytheperiodictable,choosethe
strongeracidofeachofthefollowingpairs.
(a)H2SeorHBr,
(b)H2SeorH2Te,
(c)CH3OHorCH3SH

Oxoacids
Acidscomposedofhydrogen,oxygenandsomeotherelementarecalledoxoacids(seetable11.8).
Thosethatarestrongacidsinwateraremarkedinthetablebyasterisks.
TABLE11.8 Someoxoacidsofnonmetalsandmetalloids(a)
Group14
H2CO3 carbonicacid (b)
Group15
*HNO3 nitricacid (a)
HNO2 nitrousacid

H3PO4 phosphoricacid

H3PO3 phosphorousacid (c)

H3AsO4 arsenicacid
 H3AsO3 arsenousacid

Group16
*H2SO4 sulfuricacid

H2SO3 sulfurousacid (d)

*H2SeO4 selenicacid

H2SeO3 selenousacid

Group17
HOF hypofluorousacid (e)
*HClO4 perchloricacid

*HClO3 chloricacid

HClO2 chlorousacid
HOCl hypochlorousacid
*HBrO4 perbromicacid (f)
*HBrO3 bromicacid

HOBr hypobromousacid

HIO4(H5IO6)(g) periodicacid

HOI hypoiodousacid
HIO3 iodicacid

(a)Strongacidsaremarkedwithasterisks.
(b)PredominantlyCO2(aq).
(c)Phosphorousacid,despiteitsformula,isonlyadiproticacid.Itshouldmorecorrectlybe
writtenasHPO(OH)2.
(d)Hypothetical.Anaqueoussolutionactuallycontainsjustdissolvedsulfurdioxide,SO2(aq).
(e)Unstableatroomtemperature
(f)Pureperbromicacidisunstableadihydrateisknown.
(g)H5IO6isformedfromHIO4+2H2O.

AfeaturecommontothestructuresofalloxoacidsisthepresenceofOHgroupsbondedtosome
centralatom.Forexample,thestructuresoftwooxoacidsofthegroup16elementsare:

Aswiththebinaryacids,severalgeneralobservationsabouttheacidstrengthsofoxoacidscanbemade:
1.Withingroupsofoxoacidswiththesamenumberofoxygenatoms,theacidstrengthincreases
goingupagroup.Thisisbestillustratedbyoxoacidscontaininggroup17elements.The
 hypohalousacids,allofwhichareweak,increaseinstrengthintheorderHOI<HOBr<HOCl,
withpKa valuesof10.64,8.68and7.52,respectively(notethatHOFisunstable,decomposing
rapidlyatroomtemperature).Forthestronggroup17oxoacidswiththegeneralformulaHXO4,
theorderofacidstrengthisHIO4<HBrO4<HClO4(notethatHFO4isunknown,asFcannot
accommodatemorethananoctetofelectrons).Similarly,inthegroup16acids,wefindthat
H2SeO4isweakerthanH2SO4(thethirdmemberofthisseries,H2TeO4actuallyexistsas
Te(OH)6anddoesnotthereforeprovideavalidcomparison)ingroup15,H3AsO4(pKa =2.25)is
slightlyweakerthanH3PO4(pKa =2.15).

PRACTICEEXERCISE11.22
Whichisthestrongeracid,HClO3or
HBrO3?

2.Withingroupsofoxoacidswiththesamenumberofoxygenatoms,theacidstrengthincreases
acrossaperiod.Thiscanbeseeninoxoacidscontainingperiod3elements,whereacidstrength
increasesintheorderH3PO4<H2SO4<HClO4.
3.Acidstrengthincreasesasthenumberofloneoxygenatomsincreases.(Aloneoxygenatomis
onethatisbondedonlytothecentralatomandnotahydrogenatom.)Therearenumerous
examplesthatdemonstratethisobservation.Forexample,nitrousacid,HNO2,whichcontainsone
loneoxygenatom,isaweakacid(pKa =3.15)whilenitricacid,HNO3,isastrongacid.

Asimilarsituationisseenwithselenousacid,H2SeO3,andselenicacid,H2SeO4,wherethelatter,
havingtwoloneoxygenatoms,isamuchstrongeracid.

Amongoxoacidsofthehalogens,wefindthesametrendinacidstrengths.Fortheoxoacidsofchlorine,
forinstance,wefindthetrend:

Comparingtheirstructureswehave:
Theacidstrengtheningeffectofloneoxygenatomsisnotlimitedtoinorganicoxoacids.Consider,for
example,ethanolandaceticacid.

Ethanoldisplaysnegligibleacidpropertiesinwater(pKa =15.9).However,incorporationofalone
oxygenatomasareplacementfortwoprotonsyieldsaceticacid,whichiselevenordersofmagnitude
moreacidic(pKa =4.74).Thisenormousincreaseinacidityhasbeenascribedinparttothediffering
stabilitiesoftherespectiveconjugatebases,whichisgovernedbytheirabilitytodelocalisethenegative
chargearisingfromthelossofaproton.

Theacetateioncanbedrawnastwoequivalentresonancestructures(chapter5),withthenegative
chargeoneitherofthecarboxylateOatoms.Theactualstructureoftheacetateionliessomewhere
betweenthesetwoforms,withthenegativechargedelocalisedoverthetwoOatomsandthe
carboxylatecarbonatom.

Thisspreadingoutorresonancestabilisationofthenegativechargeresultsinaloweringinenergy
relativetothesituationwherethechargeislocalisedonasingleatom.Theethoxideioncannotundergo
suchresonancestabilisation,andwethereforeexpectethanoltobeaweakeracidthanaceticacid.An
analogoussituationoccursintheoxoacidsofmaingroupelements.ConsidertheacidsH2SO4and
H3PO4:

Asyoucanseeintheirstructures,H2SO4hastwoloneoxygenatomsandH3PO4hasonlyone.Lossof
aprotonfromeachgivesthefollowingspecies:
Inoxoanionssuchasthese,theloneoxygenatomscarrymostofthenegativecharge,ratherthanthe
oxygenatomsbondedtohydrogenatoms.Thischargeactuallyspreadsovertheloneoxygenatoms.In
,therefore,eachloneoxygenatomcarriesachargeofabout .Bythesamereasoning,in
eachloneoxygenatomcarriesachargeofabout .Thesmallernegativechargeonthe
loneoxygenatomsin makesthisionlessabletoattractH3O+ions,so isaweakerbase
than .Inotherwords, cannotbecomeH2SO4againasreadilyas canbecome
H3PO4.TherearethustwofactorsthatmakeH2SO4astrongeracidthanH3PO4inwater.Oneisthe
greatertendencyofH2SO4todonateaprotonandtheotheristhelessertendencyof toaccepta
proton.

PRACTICEEXERCISE11.23
Ineachpair,selectthestrongeracid.
(a)HIO3orHIO4,
(b)H3AsO3orH3AsO4

ChemistryResearch

TheStrongestAcid

Inthischapter,wehavediscussedtheconceptofacidandbasestrength,
andwehaverelatedthistotheextentofdissociationoftheacidorbaseat
equilibriumforexample,strongacidsarecompletelydissociatedand
weakacidsareincompletelydissociated.Butaresomestrongacidsmore
completelydissociatedthanothers?Or,toputitanotherway,istheresuch
athingasthestrongestacidthatcanbeisolated?Theanswertothis
questionisyes,andthepersonwhomadethisacidisaNewZealander.

ProfessorChristopherReedisProfessorofChemistryattheUniversityof
CaliforniaatRiverside,intheUSA.HewasborninAucklandand,after
completinghisPhDattheUniversityofAuckland,hemovedtotheUSA
tocarryoutpostdoctoralresearchandstayedtherefollowinghis
appointmenttothefaculty.In2004,hepublishedapaperinthe
internationalchemistryjournalAngewandteChemietitledThestrongest
isolableacid,wherehereportedthesynthesisandcharacterisationofa
carboraneacidwiththechemicalformulaH(CHB11Cl11).(Acarboraneisa
moleculeorionthathasaframeworkcomposedofcarbonandboron
atoms.)

Thestructureofthisacidisshowninfigure11.14.Itconsistsofaproton
andananionic(CHB11Cl11)carboraneunitandisasolidatroom
temperature.TheextraordinaryacidstrengthofH(CHB11Cl11)is
evidencedbythefactthatitcanprotonatemoleculesthatareextremely
weakbases.Forexample,reactionwithbenzene,C6H6,givesthe
protonatedbenzeniumionasthesalt(C6H7)+(CHB11Cl11).Theacid
strengthofH(CHB11Cl11)wasquantifiedusingNMR(nuclearmagnetic
resonance)andIR(infrared)spectroscopies(seechapter20)andthese
techniquesshowedittobethestrongestknownacid.ProfessorReedand
hiscoworkershavealsopreparedanumberofsimilarlystrongacidsthat
differinthesubstituentsaroundthecarboranecoretheseinclude
H(CHB11H5Cl6),H(CHB11H5Br6)andH(CHB11H5I6),allofwhichare
slightlyweakeracidsthanH(CHB11Cl11).However,H(CHB11H5Cl6)is
stillasufficientlystrongacidtobeabletoprotonatetheweaklybasicC60
molecule.Thesecarboraneacidsappeartobeatleastonemilliontimes
strongerthansulfuricacid.

FIGURE11.14Representationofthestructureofacarboraneacidwiththe
chemicalformulaH(CHB11 Cl11 ).

Ofcourse,ifH(CHB11Cl11)isthestrongestisolableacid,thismustmean
thatitsconjugatebase, ,mustbeincrediblyweakand
thereforeunreactivetowardsprotonation.Thislowbasicityhasallowed
theisolationandcharacterisationofthehydroniumion,H3O+,inthe
compound[H3O][CHB11Cl11]4C6H6,andtheH5O2+ioninthecompound
[H5O2][CHB11Cl11]C6H6,bothofwhichwereisolatedfrombenzene
solution.Similarcarboraneanionshavebeenusedtoisolateunusual
cationssuchasthetertbutylcarbocation(CH3)3C+,andthefirstexample
ofa3coordinatesiliconcation.Itiscertainthatcarboraneanionswillfind
useintheisolationoffurtherexoticcationsinfuture.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.6BufferSolutions
ThecontrolandmaintenanceofpHiscrucialinmanychemicalandbiologicalsystems.Forexample,if
thepHofyourblood,whichistypically7.35to7.42,weretochangetoeither7.00or8.00,youwould
die.Fortunately,naturehasdevelopedasophisticatedchemicalsystemwhichmaintainsbloodpH
withinthevitallimits.Figure11.15showsanotherapplicationofabuffersolution.

FIGURE11.15Apracticalapplicationofabuffer.Bakingsoda,whichissodiumbicarbonate,issometimes
addedtoswimmingpoolstocontrolthepHofthewater.
KariAnnTapp

Abuffersolutionisonethatcontainsappreciableamountsofbothaweakacidanditsconjugatebase,
oraweakbaseanditsconjugateacid.Asaresultofthis,abuffersolutionresistschangeinpHafterthe
additionofsmallamountsofeitheracidorbase,andalsoonmoderatedilution.ThepHvaluesover
whichabufferiseffectiveatmaintainingthepHaredeterminedbyeitherpKa orpKboftheweakacid
orweakbase,respectively,andtheratiooftheconcentrationsofconjugatepairspresentinthesolution.

pHCalculationsinBufferSolutions
WewillfirstconsiderabuffersolutioncontainingequalamountsofaweakacidHAanditsconjugate
baseA.AbuffersolutionworksbybeingabletoreacttoneutraliseaddedH3O+orOH.Ifweadda
sourceofH3O+totheabovesolution,itwillreactwithAtoformHA.

IfweaddOHtothebuffersolution,itwillreactwithHAtoformA.
Bothreactionsservetomopupanyaddedacidorbase,whichmeansthatthepHofthesolution
remainsrelativelyconstant.WecancalculatethepHofbuffersolutions,bothbeforeandafterthe
additionofeitheracidorbase,byapplicationofthemethodswehavelearnedsofar.Consider,for
example,abuffersolutioncontainingaceticacid,CH3COOH,andsodiumacetate,NaOOCCH3.
Additionofacidtothissolutionwillcausethefollowingreactiontooccur:

whileaddedbasewillbeneutralisedasfollows:

Workedexample11.17showshowwecarryoutcalculationsinvolvingthepHofbuffersolutions.

WORKEDEXAMPLE11.17

CalculatingthepHofaBuffer
Tostudytheeffectsofaweaklyacidicmediumontherateofcorrosionofametalalloy,a
studentpreparedabuffersolutioninwhich[NaOOCCH3]=0.11Mand[CH3COOH]=0.090
M.WhatisthepHofthissolutionat25C?

Analysis

ThebuffersolutioncontainsboththeweakacidCH3COOHanditsconjugatebaseCH3COO,
andwearegiventheconcentrationsofboth.WecansolvetheproblembyusingeitherKa for
CH3COOHorKbforCH3COO.Wewillshowindetailhowtousetheformer,andwilllook
atthelatterinpracticeexercise11.24.WebeginbylookingupthevalueofKa for
CH3COOH,thensetupaconcentrationtableandsolvefor[H3O+]usingthesimplifying
approximationsdevelopedearlier.

Solution

WebeginwiththebalancedchemicalequationandtheexpressionforKa .

WesetuptheconcentrationtableandtaketheinitialconcentrationsofCH3COOHand
CH3COOtobethevaluesgivenintheproblem.Weassumetheinitial[H3O+]=0and
thereforethismustincreaseby+xasthereactionproceedstoequilibrium.Theotherchanges
followfromthat.Thecompletedtableisshownbelow.

H2O+CH3COOH H3O++CH3COO

Initialconcentration(molL1) 0.090 0 0.11

Changeinconcentration(molL1) x +x +x
 Equilibriumconcentration(molL1) 0.090x x 0.11+x

Forbuffersolutions,thequantityxwillbeverysmall.Thisisbecausetheconjugatebaseof
theweakacidisalreadypresentinsolution,sothissuppressesthedissociationoftheweak
acidasaresultofthecommonioneffect.Wecanthereforesafelyassumethat(0.090x)
0.090and(0.11+x)0.11.SubstitutingthesequantitiesintotheKa expressiongives:

Wesolveforxasfollows:

Becausexequals[H3O+],wenowhave[H3O+]=1.510 5M.ThenwecalculatepH:

ThusthepHofthebufferis4.82.

Isouranswerreasonable?

Wecanchecktheanswerintheusualwaybysubstitutingourcalculatedequilibriumvalues
intotheexpressionforKa .

ThisequalsKa ,sothevalueswehaveobtainedarecorrectequilibriumconcentrations.

PRACTICEEXERCISE11.24
CalculatethepHofthebuffersolutioninthe
precedingexamplebyusingtheKbfor
CH3COO.Besuretowritethechemical
equationfortheequilibriumasthereaction
ofCH3COOwithwater.Thenusethe
chemicalequationasaguideinsettingup
theequilibriumexpressionforKb.Ifyou
workthroughtheproblemcorrectly,you
shouldobtainthesameanswerasabove.

WecanrearrangetheexpressionforKa intoaformthatisparticularlyusefulforcalculationsinvolving
buffersolutions,andwhichalsoremovestheneedtowriteaconcentrationtableforeachcalculation.
Weknowthat,fortheequilibrium:

wecanwriteKa as:

Ifwemultiplybothsidesoftheequationby[HA]anddividebothsidesby[A],weobtain:

Ifwetakethenegativelogarithm(p)ofbothsides,realisingthatthelogarithmofaproductoftwo
numbersisthesumofthelogarithmsofthosenumbers,andthat ,weobtain:

ThisrearrangementoftheKa expressioniscalledtheHendersonHasselbalchequation.Thisformof
theKa expressionemphasisesthefactthatthepHofabuffersolutiondependsonboththepKa ofthe
weakacidandtheratioofconjugatebasetoacid.Recallingthat ,wecanrewritetheequationas:

andtherefore:

Thereforewecanexpressthisrelationshipintermsofeitheraconcentrationratiooramoleratio.Note
that,underthespecialconditionwhere[HA]=[A](orn HA=n A), ,log(1)=0,and
thereforepH=pKa .

AfurtherconsequenceoftherelationshipderivedaboveisthatthepHofabuffershouldnotchangeif
thebufferundergoesmoderatedilution.Dilutionchangesthevolumeofasolutionbutitdoesnot
changetheamountsofthesolutes,sotheirmoleratioremainsconstantandsodoes[H3O+].

WORKEDEXAMPLE11.18

CalculatingthepHofanAmmonia/AmmoniumIonBuffer
Tostudytheinfluenceofanalkalinemediumontherateofareaction,astudentprepareda
buffersolutionbydissolving0.12molofNH3and0.095molofNH4Clin250mLofwater.
WhatisthepHofthebufferat25C?
 Analysis

ThepHofthebufferisdeterminedbythemoleratioofthemembersoftheacidbasepairso
tocalculatethepHweusetheamountsofNH3andNH4+directlyintheHenderson
Hasselbalchequation.WealsorequirethepKa ofNH4+.

Solution

GiventhatpKa (NH4+)=9.26,wecaninsertthevaluesdirectlyintotheHenderson
Hasselbalchequation.

Notethatweassumedthattheinitialconcentrationsoftheacidandconjugatebasearethe
equilibriumconcentrations.Weareusuallyjustifiedindoingthis.

Isouranswerreasonable?

Thereismorebasethanacidinthebuffer.Thereforetheratio isgreaterthan1,and
thelogofthisratiowillbepositive.WewouldthereforeexpectapHgreaterthanthepKa ,
whichwehaveobtained.

PRACTICEEXERCISE11.25
DeterminethepHofthebufferinworked
example11.18when[NH3]=0.08Mand
[NH4Cl]=0.15M.

Buffersolutionsfunctionmostefficientlywhentheratio iscloseto1.Whenthisisthecase,the
concentrationsofboththeweakacidanditsconjugatebaseareessentiallyequal,andthebuffercan
thereforeresistchangeinpHontheadditionofeitheracidorbase.Asweshowedabove,when
,pH=pKa ,andthereforethepKa oftheweakaciddetermineswhere,onthepHscale,a
buffercanworkbest.Thus,toprepareaspecificbufferforuseataparticularpH,wefirstselectaweak
acidwithapKa nearthedesiredpH.Then,byexperimentallyadjustingtheratio .wecanmakea
finaladjustmenttoobtainthedesiredpH.

Iftheratio issignificantlydifferentfrom1,thentheconcentrationsoftheweakacidandits

conjugatebaseinsolutionarenolongersimilar.If,forexample,[HA]>[A],thebufferwillresist
changeinpHwellontheadditionofbase,butitwillbelesseffectiveatresistingchangeinpHon
additionofacid,asthereislessApresentfortheaddedacidtoreactwith.OncealltheAhasreacted,
thepHofthesolutionwillchangerapidly.Aslongastheratio inabuffersolutionisbetween
 and ,thebufferwillmaintainpHeffectively.IfwesubstitutethesevaluesintotheHenderson
Hasselbalchequation,weobtainpH=pKa 1andpH=pKa +1,respectively.Thismeansthatthe
operationalrangeofanybufferis1pHuniteithersideofthepKa oftheweakacid,i.e.pH=pKa 1.

WORKEDEXAMPLE11.19

PreparingaBufferSolutionwithaPredeterminedpH
AsolutionbufferedatapHof5.00isneededinanexperiment.Canweuseaceticacidand
sodiumacetatetopreparethebuffer?Ifso,whatamountofNaOOCCH3mustbeaddedto
1.0Lofasolutionthatcontains1.0molNaOOCCH3at25C?

Analysis

Therearetwopartstothisproblem.Toanswerthefirst,wecheckthepKa ofaceticacidto
seeifitisinthedesiredrangeofpH=pKa 1.Ifitis,wecancalculatethenecessarymole
ratio.Oncewehavethis,wecanproceedtocalculatetheamountofCH3COOneededand
thentheamountofNaOOCCH3.

Solution

ThepKa ofaceticacid(4.74)fallsinthedesiredrangeandthereforeaceticacidcanbeused
withtheacetateiontomakethebuffer.

WefindtherequiredmoleratioofsolutesbyusingtheHendersonHasselbalchequation.

Therefore:

andhence:

Weknowthat molandso mol.

BecauseeachmoleofNaOOCCH3contains1moleofCH3COO,werequire1.82mol
NaOOCCH3.

Isouranswerreasonable?

A1:1moleratioofCH3COOtoCH3COOHwouldgivepH=pKa =4.74.ThedesiredpH
 of5.00isslightlymorebasicthan4.74,sotheamountofconjugatebaseshouldbelarger
thantheamountofconjugateacid.Ouranswerof1.82molofNaOOCCH3appearstobe
reasonable.

PRACTICEEXERCISE11.26
Achemistneedsanaqueousbufferwitha
pHof3.90.Wouldformicacid,HCOOH,
anditssalt,sodiumformate,NaOOCH,
makeagoodpairforthispurpose?Ifso,
whatmoleratiooftheacidtotheanionof
thesaltisneeded?WhatmassofNaOOCH
wouldhavetobeaddedtoasolutionthat
contains0.10molHCOOHat25C?

Oncewehavepreparedabuffersolution,wecancalculatethepHchangeonadditionofaspecified
amountofstrongacidorbasebyassumingthattheaddedstrongacidorbasereactsquantitativelywith
theweakacidorbasecomponentofthebuffersolution.Thisisillustratedinworkedexample11.20.

WORKEDEXAMPLE11.20

CalculatingthepHChangeinaBufferSolution
WhatpHchangewilloccuraftertheadditionof0.10Lof0.10MHClto1.0Lofabuffer
solutioncontaining0.10molCH3COOHand0.10molNaOOCCH3at25C?Howdoesthis
comparewiththepHchangethatwouldoccuraftertheadditionofthesameamountofHCl
to1.0Lofpurewater?

Analysis

WeareaskedforapHchange,whichmeanswehavetocalculatethepHoftheinitialbuffer
solution.WethencalculatetheamountofHCladdedandassumethatthisreactscompletely
withCH3COOtoformCH3COOH.WethenusethenewamountsofCH3COOand
CH3COOHintheHendersonHasselbalchequationtocalculatethefinalpH.Thequestion
involvingpurewaterisastraightforwardcalculationofthepHofastrongacid.

Solution

TheinitialpHcanbeobtainedfromtheinitial[CH3COOH]and[CH3COO]valuesusingthe
HendersonHasselbalchequation.
Wenowcarryoutastoichiometriccalculationtodeterminetheequilibrium and
values.Thereactionwhichwilloccuronadditionofthestrongacidis:

Weassumethisreactiongoestocompletion,sothat:

Therefore,0.010molHCl(aq)reactswith0.010molCH3COO(aq)toform0.010mol
CH3COOH(aq).Initiallywehad0.10molCH3COOHand0.10molCH3COO,andsothe
finalamountsare:

WenowsubstitutethesevaluesintotheHendersonHasselbalchequation.

Therefore,thechangeinpHis0.09pHunits,thenegativesignshowingthatthisisa
decreaseinpH.

Whenweadd0.10Lof0.10molL1HClto1.0Lofwater,thefinalsolutioncontains0.010
molHClin1.1L.AsHClisastrongacid,itreactscompletelywithwatertoformH3O+and
hence:

Thus,pH=log[H3O+]=log(0.0091)=2.04.

Westartedwithpurewater,andsotheinitialpHwas7.00.Hence,thepHchangeis4.96
pHunits.

Isouranswerreasonable?

WestartedwiththebuffersolutionatpH4.74andaddedasmallamountofstrongacidtoit.
WeexpectthatthefinalpHshouldbeslightlylessthanthis,whichitis.

PRACTICEEXERCISE11.27
CalculatethepHchangeontheadditionof
0.10Lof0.10MNaOHto1.0Lofabuffer
solutioncontaining0.08molNH3(aq)(pKb
=4.74)and0.12molNH4Cl(aq)at25C.
Workedexample11.20illustratestheeffectivenessofabuffersolution.Whenthestrongacidisadded
towater,thesolutionbecomes4.96pHunitsmoreacidic,whereasthebuffersolutionislittleaffected,
becomingonly0.09pHunitsmoreacidic.

Ifenoughstrongacidisaddedtoreactwithallofthebasecomponentofabuffersolution,themixtureis
nolongerabletoneutraliseanymorestrongacid.Wecanillustratethiswithreferencetoworked
example11.20.Initiallythereis0.10molCH3COOinthebuffersolutionif0.10molHClisadded,this
willreactcompletelywiththe0.10molCH3COOtogive0.10molCH3COOH.Whenthishappens,the
concentrationofCH3COOisverysmall(alloftheCH3COOinsolutionatthispointwillcomefrom
dissociationofCH3COOH)andthesolutionnolongerfunctionsasabuffertowardstheadditionof
moreacid.Similarly,ifweadded0.10molNaOHtotheoriginalbuffersolutionintheexample,itwould
reactcompletelywiththe0.10molCH3COOHpresenttoform0.10molCH3COO,therebyleaving
essentiallynoCH3COOHinthesolutiontoreactwithanyfurtheraddedNaOH.Thismeansthatthereis
alimittotheamountofaddedacidorbasethatabuffersolutioncanabsorb.Thebuffercapacityofany
bufferisameasureoftheamountofH3O+orOHthatcanbeaddedwithoutsignificantchangeinthe
pH.Intheexample,theadditionof0.10molHClor0.10molNaOHwouldexhaustthecapacityofthe
buffersolution.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.7AcidbaseTitrations
Weoftenencountersolutionsofacidorbaseswithunknownconcentrationsinchemistry.Onemethod
ofdeterminingtheconcentrationofanacidorabaseistocarryoutanacidbasetitration(figure
11.16).Thisinvolvesgradualadditionofanacidorbaseofknownconcentration(thetitrant)froma
burettetoanaccuratelyknownvolumeoftheunknownsolution.Anacidbaseindicatorchanges
colourwhentheendpointofthetitrationisreached,and,ifwehavechosentheindicatorcorrectly,the
endpointwillbeagoodapproximationoftheequivalencepointofthetitration.Theequivalencepointis
thepointatwhichthereactionstoichiometryissatisfied,or,inotherwords,wheretheamountoftitrant
addedexactlyequalstheamountofacidorbaseinitiallypresent.Theequivalencepointissometimes
calledthestoichiometricpoint.Inallacidbasetitrations,regardlessofthestrengthsoftheacidorbase
involved,theessentialreactionthatoccursis:

FIGURE11.16Anacidbasetitration.Phenolphthaleinisoftenusedasanindicatortodetecttheendpoint.

Knowledgeofboththestoichiometryofthereactionandthevolumeofacidorbaseaddedallowsusto
calculatetheconcentrationoftheunknownsolution.Wewillnowexamineacidbasetitrationsina
littlemoredetail,withparticularemphasisonthevariationsinpHthatoccurasthetitrationsproceed.
StrongAcidStrongBaseandStrongBaseStrongAcid
Titrations
Figure11.17showsaplotofpHversusvolumeoftitrantaddedforthetitrationof25.00mLof0.200M
HCl(aq)with0.200MNaOH(aq).Wecallsuchaplotatitrationcurve,andithasthesamegeneral
shapeforthetitrationofanystrongacidwithanystrongbase.Likewise,thetitrationcurveforthe
titrationof25.00mLof0.200MNaOHwith0.200MHClisdepictedinfigure11.18,andthistoois
generalforthetitrationofanystrongbasewithanystrongacid.Wewillconsiderthestrongacidstrong
base(notethatthetitrantcomeslastwhendescribingatitration)titrationcurveindetail,realisingthat
analogousargumentsapplyforthestrongbasestrongacidtitration.

FIGURE11.17Titrationcurveforthetitrationofastrongacidwithastrongbase.HerewefollowhowthepH
changesduringthetitrationof25.00mLof0.200MHCl(aq)with0.200MNaOH(aq).

FIGURE11.18Titrationcurveforthetitrationofastrongbasewithastrongacid(25.00mL0.200MNaOH(aq)
with0.200MHCl(aq)).

Therearefourimportantpointsandregionstoconsiderforastrongacidstrongbasetitrationcurve:
1.theinitialpH
2.theacidicregion
3.theequivalencepoint
4.thealkalineregion.
TheinitialpH
TheinitialpHinastrongacidstrongbasetitrationisthepHofthestrongacidbeingtitrated.Because
theacidisstrong,itwillreactcompletelywithwatertogenerateH3O+,andthereforewecancalculate
thepHbytakingthenegativelogarithmoftheacidconcentration.Forthetitrationcurveinfigure11.17,
theinitialpHwillbe:

Theacidicregion

Intheacidicregion,weareaddingOHtoasolutionofH3O+,andtheessentialreactionthatoccursis:

Asyoucanseefromfigure11.17,thepHinitiallychangesveryslowlyonadditionofNaOH(aq),andit
isnotuntiltheequivalencepointisapproachedthatthepHstartstoincreasesignificantly.Intheacidic
region,thesolutioncontainsH3O+andClionsfromtheacid,andNa+ionsfromthebase,andthepHis
governedbytheamountofunreactedH3O+inthesolution.TheconcentrationofH3O+decreasesas
NaOHisadded,and,atanypointinthisregion,itcanbecalculatedfromtheequation:

where istheinitialconcentrationoftheacid, istheconcentrationoftheNaOH

solution,Vinitialistheinitialvolumeoftheacidsolution,VaddedisthevolumeoftheNaOHsolution
addedandVtotalisthetotalvolumeofthesolution(Vtotal=Vinitial+Vadded).Althoughthisequation
lookssomewhatformidable,carefulinspectionrevealsthatitismerely inanotherformthetop
lineistheamountofH3O+inthesolution,calculatedbysubtractingtheamountofOHaddedfromthe
amountofH3O+presentinitially.Noticethat,eventhoughthepHchangeslittleonadditionofNaOHin
theacidicregion,theresultingsolutionisnotabuffersolutionthepHofthissolutionwillchange
significantlyonmoderatedilution,incontrasttoasolutioncontainingsignificantamountsofaweak
acidanditsconjugatebase.

Theequivalencepoint
Wedefinedtheequivalencepointasthepointwherethereactionstoichiometryissatisfied.Thismeans
thatwehaveaddedexactlythesameamountofOHasthereweremolesofH3O+intheinitialsolution
ofacid.Asweoriginallyhad25.00mLof0.200MHCl,thispointoccurswhenwehaveadded25.00
mLof0.200MNaOH.Therefore,atthispointonthetitrationcurve,thereaction:

hasgonetocompletion,andthesolutioncontainsonlyNa+andClionsinwater.ThepHofthesolution
attheequivalencepointisexactly7.00,becauseClistheconjugatebaseofaverystrongacidand
thereforehasessentiallynobasicproperties.ThepHattheequivalencepointwillalwaysbe7.00forthe
titrationofanystrongmonoproticacidwithastrongbase.

Thealkalineregion

Beyondtheequivalencepoint,weareaddingexcessNaOH(aq)toasolutioncontainingNa+(aq)and
Cl(aq),sothereisnochemicalreactionoccurring.ThepHinthisregionisgovernedbytheamountof
excessNaOH(aq)addedtothesolutionandwillalwaysbe>7.TheconcentrationofOH,andhencethe
pH,canbecalculatedfromthefollowingequation:

where istheconcentrationoftheNaOHsolution,VaddedisthetotalvolumeofNaOH
solutionadded,VequivisthevolumeofNaOHsolutionaddedattheequivalencepoint(inthiscase,
25.00mL)andVtotalisthetotalvolumeofthesolution.ThetoplinegivestheamountofOHinexcess
ofthatrequiredtoreachtheequivalencepointthisisobtainedbysubtractingtheamountofOHusedto
reachtheequivalencepointfromthetotalamountofOHadded.

WeakAcidStrongBaseandWeakBaseStrongAcid
Titrations
Figure11.19showsthetitrationcurveforthetitrationof25.00mLof0.200MCH3COOH(aq)with
0.200MNaOH(aq),whilethetitrationcurveforthetitrationof25.00mLof0.200MNH3with0.200M
HClisgiveninfigure11.20.Wewillfocusontheweakacidstrongbasecurve,realisingthatanalogous
argumentscanbemadefortheweakbasestrongacidcase.Asyoucansee,theweakacidstrongbase
curvelooksratherdifferentfromthestrongacidstrongbasecurve(figure11.17),especiallyinthe
acidicregion.Wewillagainconsiderindetailthefourimportantpointsandregionsonthiscurve.
 FIGURE11.19Titrationcurveforthetitrationofaweakacidwithastrongbase.Inthistitration,wefollowthe
pHas25.00mLof0.200MCH3 COOH(aq)istitratedwith0.200MNaOH(aq).

FIGURE11.20Titrationcurveforthetitrationofaweakbasewithastrongacid.HerewefollowthepHas
25.00mLof0.200MNH3 (aq)istitratedwith0.200MHCl(aq).

TheInitialpH
TheinitialpHof2.72inthistitrationissignificantlyhigherthanthatforthestrongacidstrongbase
titration.ThisistobeexpectedasCH3COOHisaweakacidanddissociatesonlytoasmallextent.We
cancalculatetheinitialpHoftheacidsolutioninaweakacidstrongbasetitrationwiththemethodthat
wasusedforthecalculationofthepHofasolutionofaweakacid.Wethereforesetupaconcentration
tablefora0.200MCH3COOHsolution.Thebalancedchemicalequationis:

andtheequilibriumconstantexpressionis:
Theconcentrationtablecanthenbewrittenas:

H2O+CH3COOH H3O++CH3COO

Initialconcentration(molL1) 0.200 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(molL1) 0.200x x x

Wemaketheusualassumptionthatxissmallcomparedwith0.200,andtherefore(0.200x)0.200.
Substitutingtheequilibriumconcentrationsintotheequilibriumconstantexpressiongives:

andsolvingforxgives:

Asx=[H3O+],weobtainthepHofthesolutionby:

TheAcidicRegion
Thegeneralshapeofthetitrationcurveinthisregiondiffersfromthatforthestrongacidstrongbase
titrationinthatthereisaninitialrapidincreaseinpH.ThecurvealsoliesathigherpHvaluesthanthe
analogouspointsofthestrongacidstrongbasetitration.Whiletheonlyreactionofnoteinthestrong
acidstrongbasetitrationwasH3O+(aq)+OH(aq)2H2O(l),thesituationismorecomplicatedwhen
weakacidsorbasesareinvolved.Inthiscase,initialadditionofNaOH(aq)toCH3COOH(aq)forms
CH3COO(aq)accordingtotheequation:

Initially,thepHofthesolutionchangesrapidly,but,oncetheconcentrationofCH3COOhasincreased
sufficiently,thesolutioncontainsappreciableamountsofaweakacidanditsconjugatebaseinother
words,wehaveabuffersolution.ThepHinthisregionwillthereforebegovernedbytheratio
throughtheHendersonHasselbalchequation .Atthepoint
halfwaytotheequivalencepoint,thisratiowillbe1,andthereforepH=pKa .Therefore,atitrationofa
weakacidwithastrongbasetellsusnotonlytheconcentrationoftheweakacidbutalsoitspKa we
simplytakethepHreadingatthevolumehalfwaytotheequivalencepoint.Whilewecancalculatethe
pHatanypointintheacidicregionusingtheHendersonHasselbalchequation,itcanbemore
convenientlywrittenintermsofconcentrationsandvolumesofthesolutionsinvolvedinthetitration.
TheamountofCH3COOisequaltotheamountofNaOHadded,andtheamountofCH3COOHinthe
solutionatanypointisequaltotheinitialamountofCH3COOHminustheamountofNaOHadded,so
wecanrewritethisequationasfollows:
wherecOH(initial)istheinitialconcentrationoftheNaOHsolution, isthevolumeofthe
NaOHsolutionadded,cHA(initial)istheinitialconcentrationoftheacidsolutionandVinitialistheinitial
volumeoftheacidsolution.

Notethatthisequationisnotexact,asitdoesnottakeintoaccountthedissociationoftheacidorthe
reactionoftheconjugatebasewithwater.However,asbothofthesereactionsaresuppressedbythe
commonioneffectinabuffersolution,itgivesaverygoodapproximation,especiallywhenthe
concentrationsoftheacidandconjugatebasearesimilar.Youshouldnotattempttomemorisethe
previousequation,asitcanbederivedfromtheHendersonHasselbalchequation,whichitselfis
derivedfromtheKa expressionforaweakacid.

Asweapproachtheequivalencepointofthetitration,thereaction:

proceedsfurthertowardscompletionandthepHstartstoincreaserapidly.Thisisbecausewehave
exhaustedthecapacityofthebuffersolutionnearlyalltheCH3COOHhasbeenusedup,andthereisno
longersufficientacidpresenttobeabletoreactwithanyaddedOH.

TheEquivalencePoint
Attheequivalencepoint,thereaction:

hasgonetocompletionandthesolutioncontains0.100MNa+(aq)and0.100MCH3COO(aq).Inother
words,atthispointwehavea0.1MaqueoussolutionofNaOOCCH3.Wehaveseenpreviouslythat
CH3COO,beingtheconjugatebaseofaweakacid,isappreciablybasic,andthereforethefollowing
reactionwilloccur:

Thismeansthat,attheequivalencepoint,thereisasmallamountofOHinthesolution,andtherefore
thepHisgreaterthan7.00(inthiscaseitis8.88,asweshowbelow).Inthetitrationofanyweakacid
withanystrongbase,thepHattheequivalencepointisalwaysgreaterthan7,becausetheconjugate
baseoftheweakacidismeasurablybasic.TheexactpHdependsonboththeKbandtheconcentration
oftheconjugatebasetheweakertheacid,thestrongeritsconjugatebase,andthereforethemorebasic
thesolutionattheequivalencepoint.CalculationofthepHattheequivalencepointfollowsthemethod
weoutlinedpreviouslyforthedeterminationofthepHofasaltofaweakacid.Thebalancedchemical
equationweneedtoconsideris:
WewilluseKbtodetermine[OH],andhencepH:

Theconcentrationtableisasfollows.NotethattheinitialconcentrationofCH3COOis0.100mthisis
becauseattheequivalencepointthesolutionhastwiceitsstartingvolumeduetotheaddedNaOH
solution.

H2O+CH3COOH CH3COOH+OH

Initialconcentration(molL1) 0.100 0 0

Changeinconcentration(molL1) x +x +x

Equilibriumconcentration(molL1) 0.100x x x

Wemaketheassumptionthatxwillbesmallcomparedwith0.100,becauseCH3COOisaweakbase.
Therefore(0.100x)0.100.WethensubstitutevaluesintotheKbexpression:

Solvingthisforxgives:

Asx=[OH],weobtainthepHofthesolutionasfollows:

Analogousargumentsapplyforthetitrationofaweakbasewithastrongacid,andthepHatthe
equivalencepointinsuchtitrationsis<7.TheexactpHcanbecalculatedusingtheKa fortheconjugate
acidoftheweakbase.

TheAlkalineRegion

Beyondtheequivalencepoint,wearesimplyaddingexcessOHtoasolutionofaweakbase,andthe
pHinthisregioniscontrolledbytheexcessamountofNaOH.Thetitrationcurveinthisregionis
essentiallyidenticaltothatforastrongacidstrongbasetitration,andthepHatanypointinthisregion
maythereforebecalculatedusingthesamemethodasdescribedpreviouslyforsuchtitrations.
DiproticAcids
Whenaweakdiproticacidsuchasascorbicacid(vitaminC)istitratedwithastrongbase,therearetwo
protonsavailabletoreactwiththebaseandtherearethereforetwoequivalencepoints.Providedthatthe
valuesofpKa1andpKa2differbyseveralpowersof10,theneutralisationtakesplacestepwiseandthe
resultingtitrationcurveshowstwosharpincreasesinpHasshowninfigure11.21.Calculations
involvingacidscontainingtwoormoreacidicprotonscanbedifficult,andlieoutsidethescopeofthis
book.

FIGURE11.21Titrationofadiproticacid,H2 A,byastrongbase.Aseachequivalencepointisreached,there
isasharpriseinthepH.

SpeciationDiagrams
Itisoftenusefultoknowtherelativeamountsofaweakacidanditsconjugatebasethatarepresentin
anaqueoussolutionhavingaparticularpH.Wecandothiswiththeaidofaspeciationdiagram,which
isaplotofmoleratioversuspH.Fromthespeciationdiagramforaceticacidinfigure11.22,wecansee
ataglancethatundissociatedCH3COOHpredominatesatpHvalueslessthan4.74(thepKa ofacetic
acid).AtthepointwherepH=pKa ,thereareequalamountsofCH3COOHandCH3COO,andthetwo
linesthereforeintersect.AthigherpHvalues,theconjugatebase,CH3COO,ispresentingreater
amountsthantheundissociatedacidbeyondpH8,thereisessentiallynoCH3COOHpresentinthe
solution.
 FIGURE11.22SpeciationdiagramforthedissociationofCH3 COOHinaqueoussolution.

Speciationdiagramsarerelativelysimpleformonoproticacids,butbecomesomewhatmore
complicated,andconsequentlysomewhatmoreuseful,forpolyproticacids.Figure11.23showsthe
speciationdiagramforH3PO4,atriproticacid,whichyieldstheanions , and
onsuccessivedeprotonations.ThepKa values:

FIGURE11.23SpeciationdiagramforthedissociationofH3 PO4 inaqueoussolution.

ItcanbeseenthatH3PO4predominatesinveryacidicregions,but,bypH4,ithasmostlybeen
deprotonatedtoform .AsweproceedpastthepKa of ,itsconjugatebase,
 ,ispresentinthelargestamountuntilthepHincreasespast12.3,thepKa of .Under
theseconditions, thenbecomesthedominantspeciesinsolution.

Speciationdiagramsareextremelyusefulnotonlyinsituationsinvolvingpolyproticacids,butalsoin
systemswheremetalionsreactwithligands(seechapter13),whichthemselvescontainacidicprotons.
Thecalculationsinvolvedcanberathercomplex,especiallyinsystemsinvolvinganumberof
components,butcanusuallybecarriedoutsatisfactorilyusingspreadsheets.

AcidbaseIndicators
Theindicatorsusedinacidbasetitrationsarethemselvesweakacids,whichwecanrepresentbythe
formulaHIn.ArequirementofanacidbaseindicatoristhatitsacidformHInandconjugatebase
formIn havedifferentcolours.Insolution,theindicatorisinvolvedinatypicalacidbaseequilibrium.

ThecorrespondingacidionisationconstantKInisgivenby:

Inastronglyacidicsolution,when[H3O+]ishigh,theequilibriumisshiftedtotheleft,andmostofthe
indicatorexistsinitsacidform.Undertheseconditions,thecolourweobserveisthatofHIn.Ifbaseis
addedtothesolution,the[H3O+]dropsandtheequilibriumshiftstotheright,towardsIn .Thecolour
wethenobserveisthatofthebaseformoftheindicator(figure11.24).
 FIGURE11.24Coloursoftheacidformandbaseformofsomecommonacidbaseindicators.
AndyWashnik

HowAcidbaseIndicatorsWork
Inatypicalacidbasetitration,aswepasstheequivalencepoint,thereisasuddenandlargechangein
thepH.Forexample,inthetitrationofHClwithNaOHdescribedearlier(figure11.17),thepHjust
beforetheequivalencepoint(when24.97mLofthebasehasbeenadded)is3.92.Justonedroplater
(when25.03mLofbasehasbeenadded),wehavepassedtheequivalencepointandthepHhasrisento
10.08.ThislargeswinginpHcausesasuddenshiftinthepositionofequilibriumfortheindicator,and
wegofromaconditionwheremostoftheindicatorisinitsacidformtoaconditioninwhichmostisin
thebaseform.Asaresult,thesolutionchangescolourandwesaythattheendpointhasbeenreached.

SelectingtheBestIndicatorforanAcidbaseTitration
Theexplanationintheprecedingparagraphassumesthatthemidpointofthecolourchangerangeofthe
indicatorcorrespondstothepHattheequivalencepoint.Atthismidpoint,weexpectthatthereareequal
amountsofbothformsoftheindicator,whichmeansthat[In ]=[HIn].Ifthisconditionistrue,then
fromtheequation:

wefindthatpKIn=pHattheequivalencepoint.

Thisimportantresulttellsusthat,onceweknowthepHofthesolutionattheequivalencepoint,wealso
knowthepKInthattheindicatorshouldhavetofunctionmosteffectively.Thus,wewantanindicator
withapKInequalto(orascloseaspossibleto)thepHattheequivalencepoint.Thiswillensurethatthe
observedendpointwillbeascloseaspossibletotheequivalencepoint.Phenolphthalein,forexample,
changesasolutionfromcolourlesstopinkasthepHofthesolutionchangesoverarangeof8.2to10.0
(seetable11.9).Phenolphthaleinisthereforeanearlyperfectindicatorforthetitrationofaweakacidby
astrongbase,wherethepHattheequivalencepointisonthebasicside(figure11.19).
TABLE11.9 Commonacidbaseindicators
ApproximatepHrangeforcolour Colourchange(lowertohigher
Indicator change pH)
methylgreen 0.21.8 yellowtoblue
thymolblue 1.22.8 redtoyellow
methylorange 3.24.4 redtoyellow
ethylred 4.05.8 colourlesstored
methylpurple 4.85.4 purpletogreen
bromocresol 5.26.8 yellowtopurple
purple
bromothymolblue 6.07.6 yellowtoblue
phenolred 6.48.2 yellowtored/violet
litmus 4.78.3 redtoblue
cresolred 7.08.8 yellowtored
thymolblue 8.09.6 yellowtoblue
phenolphthalein 8.210.0 colourlesstopink
thymolphthalein 9.410.6 colourlesstoblue
alizarinyellowR 10.112.0 yellowtored
claytonyellow 12.213.2 yellowtoamber

Phenolphthaleinalsoworksverywellforthetitrationofastrongacidwithastrongbase.Asdiscussed
earlier,justonedropoftitrantcanbringthepHfrombelow7tonearly10,whichspansthepHrange
forphenolphthalein.

Whenweperformatitration,wewanttouseaslittleindicatoraspossible.Thereasonforthisisthat
indicatorsareweakacidsandalsoreactwiththetitrant.Ifwewereforcedtousealotofindicator,it
wouldaffectourmeasurementsandmakethetitrationlessprecise.Therefore,thebestindicatorsare
thosewiththemostintensecolours.Then,evenextremelysmallamountscangivestrikingcolour
changeswithoutconsumingtoomuchofthetitrant.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
11.8LewisAcidsandBases
Westatedearlierinthischapterthattherewasmorethanonedefinitionofacidsandbases,and,whilewehaveused
theBrnstedLowrydefinitionthroughoutthischapter,thereisamoregeneraldefinitionfirstproposedbythe
AmericanchemistGilbertLewis.Hestatedthat:
ALewisacidisanelectronpairacceptor.
ALewisbaseisanelectronpairdonor.Toillustratethesedefinitions,wewillconsiderthereactionbetweenBF3
andNH3.

Inthisreaction,NH3formallydonatesanelectronpairtoBF3,resultinginformationofaBNcovalentbond,as
showninfigure11.25.

FIGURE11.25TheLewisacidbasereactionofBF3 withNH3 .AcovalentbondbetweenBandNisformed,withboth

electronsinthebondformallyderivingfromtheLewisbasicNatom.

Thus,BF3isaLewisacidandacceptsanelectronpairfromtheLewisbaseNH3inthisreaction.Compoundssuchas
F3BNH3,whichareproductsofthereactionbetweenaLewisacidandaLewisbase,aresometimescalledLewis
adducts,orsimplyadducts.Aswewillseeinchapter13,thechemistryoftransitionmetalionsisdominatedbyLewis
adductscalledcoordinationcomplexes.TheformationoftheseinvolvesthereactionofaLewisacidictransitionmetal
ionwithoneormoreLewisbasicspeciescalledligands,eachcontaininglonepairsofelectrons.Forexample,the
coordinationcomplex[Ni(NH3)4]2+isformedfromreactionofNi2+withfourNH3ligands,accordingtotheequation:

Organicchemistry,aswewillseefromchapters16to26,isfullofexamplesofLewisacidsandbases.Muchof
organicchemistryisconcernedwiththemakingandbreakingofcovalentbondsinvolvingcarbon,andsuchreactions
canbeconsideredfromaLewisacidLewisbaseperspective.Forexample,thereactionofaketonewithaprimary
aminegivesanimineandinvolvestheformationofaC Nbond(seechapter21,p.953).Thefirststepofthis
reactioninvolvesthereactionoftheLewisbasicaminewiththeLewisacidicketone,asfollows:

ThesimilaritytotheBF3/NH3reactionisobvious.ThenomenclatureoforganicchemistrydictatesthatLewisacidsare
calledelectrophileandLewisbasesarecallednucleophile.

AstheLewisdefinitionofacidsandbasesisthemostgeneralofthethreewehavemetsofar,itfollowsthatall
BrnstedLowryacidsandbasesmustbeLewisacidsandbases.However,thereversedoesnotnecessarilyholdfor
example,theLewisacidBF3hasnoprotonstodonateandthereforecannotbeaBrnstedLowryacid.

ThestrengthsofLewisacidsandbasesarenotasreadilyquantifiedasthoseoftheirBrnstedLowrycounterparts.
Whilethelatteraremeasuredrelativetoasinglesolvent(water),thelargevarietyofsolventsinwhichLewisacidsand
basesareusedmakesasinglescaleofstrengthsdifficulttoachieve.However,itisknownthatamixtureofthe
BrnstedLowryacidHFandtheLewisacidantimonypentafluoride,SbF5,iscapableofprotonatingextremelyweak
bases,suchasalkanes,andisinfactoneofthestrongestacidsknown.Suchmixturesarecalledsuperacids.

TheconceptofLewisacidsandbasesisparticularlyusefulinunderstandingthereactivitiesofpblockelements.As
wewillseeinchapters13and14,innature,pblockelementssuchasoxygen,sulfurandthehalogenstendtobe
foundincombinationwithparticularmetals.Forexample,copper,leadandmercuryaremostoftenfoundassulfide
oressodiumandpotassiumarefoundastheirchloridesaltsmagnesiumandcalciumexistascarbonatesand
aluminium,titaniumandironareallfoundasoxides.Theunderlyingprinciplethatdetermineswhichparticular
combinationisfavouredisthestrengthwithwhichtheatomsinvolvedbindtheirvalenceelectrons.Thisisrelatedto
theLewisacidandbasecharacteristicsoftheatomsandwecanthereforeusetheLewisacidbasemodeltodescribe
themanydifferentaffinitiesthatexistamongelements.Thisnotionnotonlyexplainsthenaturaldistributionof
minerals,butalsocanbeusedtopredictpatternsofchemicalreactivity.

RecognisingLewisAcidsandBases
ALewisbasemusthavevalenceelectronsavailableforbondformation.AnymoleculewithaLewisstructurethat
showsnonbondingelectronpairscanactasaLewisbase.Ammonia,phosphorustrichlorideanddimethylether,each
ofwhichcontainslonepairs,areLewisbases.AnionscanalsoactasLewisbases.

Forexample,inthereaction:

thefluorideion,witheightvalenceelectronsinits2sand2porbitals,actsasaLewisbase.ALewisacidmustbeable
toacceptelectronstoformanewbond.Becausebondformationcanoccurinseveralways,compoundswithseveral
differentstructuralcharacteristicscanactasLewisacids.Nevertheless,mostLewisacidsfallintothefollowing
categories:
1.Amoleculethathasvacantvalenceorbitals.AgoodexampleisBF3,whichusesavacant2porbitalonboronto
formanadductwithammonia.Theelementsinthepblockbeyondperiod2oftheperiodictablehavedorbitals
whichcanpotentiallyacceptanelectronpair,thusallowingthemtoactasLewisacids.ThesiliconatominSiF4
isanexample.
2.Amoleculewithdelocalisedbondsinvolvingoxygen.ExamplesareCO2,SO2andSO3.Eachofthese
moleculescanformabondbetweenitscentralatomandaLewisbase,attheexpenseofabond.For
example,thehydroxideanion,agoodLewisbase,attacksthecarbonatomofCO2toformhydrogencarbonate.

Inthisreaction,theoxygenatomofthehydroxideiondonatesapairofelectronstomakeanewCObond.
BecauseallthevalenceorbitalsofthecarbonatominCO2areinvolvedinbondingtooxygen,oneoftheCO
bondsmustbebrokentomakeanorbitalavailabletooverlapwiththeoccupiedorbitalofthehydroxide
anion.
3.Ametalcation.Removingelectronsfromametalatomalwaysgeneratesvacantvalenceorbitals.Asdescribed
onthepreviouspage,manytransitionmetalcationsformcomplexeswithligandsinaqueoussolution.Inthese
complexes,theligandsactasLewisbases,donatingpairsofelectronstoformmetalligandbonds.Themetal
cationacceptstheseelectrons,soitactsasaLewisacid.MetalcationsfromthepblockalsoactasLewisacids.
Forexample,Pb 2+(aq)(group14)formsaLewisacidbaseadductwithfourCNanions,eachofwhichdonates
apairofelectrons.

Workedexample11.21providespracticeinrecognisingLewisacidsandbases.

WORKEDEXAMPLE11.21
LewisAcidsandBases
IdentifytheLewisacidsandbasesineachofthefollowingreactionsanddrawthestructuresoftheresulting
adducts.
(a) AlCl +ClAlCl
3 4
(b)Co 3++6NH [Co(NH ) ]3+
3 36
(c) SO +OH HSO

2 3

Analysis

EveryLewisbasehasoneormorelonepairsofvalenceelectrons.ALewisacidcanhavevacanciesinits
valenceshell,oritcansacrificeabondtomakeavalenceorbitalavailableforadductformation.Todecide
whetheramoleculeorionactsasaLewisacidorbase,examineitsLewisstructureforthesefeatures.Review
pp.1714inchapter5forproceduresusedtodetermineLewisstructures.

Solution
(a)Bothreactantscontainchlorineatomswithlonepairs,soeithermightactasaLewisbaseifasuitable
Lewisacidispresent.ThealuminiumatomofAlCl3hasavacant3porbitalperpendiculartothe
molecularplane.TheemptyporbitalacceptsapairofelectronsfromtheClaniontoformthefourth
AlClbond.TheLewisacidisAlCl3,andtheLewisbaseisCl.

(b)Asalreadynoted,ammoniaisaLewisbasebecauseithasalonepairofelectronsonthenitrogen
atom.Likeothertransitionmetalcations,Co 3+isaLewisacidandusesvacant3dorbitalstoform
bondstoNH3.

(c)Sulfurdioxidecontainsdelocalisedbonds,indicatingthepotentialforLewisacidity.Thesulfur
atomofSO2hasasetof3dorbitalsthatcanbeusedtoformanadduct.Inthiscase,thehydroxide
ionactsasaLewisbase.Theanionusesonelonepairofelectronstoformanewbondtosulfur.
 Isouranswerreasonable?

TheLewisstructuresverifythateachspeciesidentifiedasaLewisbasepossesseslonepairsofelectronsand
thattheLewisacidshaveorbitalsavailabletoacceptelectrons.

PRACTICEEXERCISE11.28
Drawareactionschemeshowingallelectron
transfersfortheformationoftheSnCl62ionfrom
thereactionofSnCl4withCl.IdentifytheLewis
acidandLewisbaseinthisreaction.

Polarisability
Polarisability,describedinchapter6,isameasureoftheeasewithwhichtheelectroncloudofanatom,ionor
moleculecanbedistortedbyanelectricalcharge.Anelectroncloudispolarisedtowardsapositivechargeandaway
fromanegativecharge,asshowninfigure11.26.Pushingtheelectroncloudtoonesideofanatomcausesa
polarisationofcharge.Thesidewiththeconcentratedelectrondensityhasasmallnegativechargetheprotonsinthe
nucleusgivetheoppositesideasmallpositivecharge.

FIGURE11.26Theelectroncloudofanatomispolarisedtowardsapositivechargeandawayfromanegativecharge.A
smalleratombindsitsvalenceelectronsmoretightlyandislesspolarisablethanalargeratom,whichbindsits
electronsloosely.

Polarisabilityshowsperiodicvariationsthatcorrelatewithperiodictrendsinhowtightlyvalenceelectronsarebound
tothenucleus(figure11.27).
1.Polarisabilitydecreasesfromlefttorightinanyperiodoftheperiodictable.Astheeffectivenuclearcharge
(Zeff)increases,thenucleusholdsthevalenceelectronsmoretightly.
2.Polarisabilityincreasesfromtoptobottominanygroupoftheperiodictable.Astheprincipalquantumnumber
(n)increases,thevalenceorbitalsbecomelarger.Thisreducesthenetattractionbetweenvalenceelectronsand
thenucleus.
 FIGURE11.27Polarisabilitydecreasesacrossaperiodandincreasesdownagroup.

TheHardsoftConcept
Lewisacidsandbasescanbeorganisedaccordingtotheirpolarisability.Ifpolarisabilityislow,thespeciesis
categorisedashard.Ifpolarisabilityishigh,thespeciesissoft.

AhardLewisbasehaselectronpairsoflowpolarisability.Thischaracteristiccorrelateswithhighelectronegativity.
Fluoride,theanionofthemostelectronegativeelement,isthehardestLewisbasebecauseitcontainsasmall,dense
sphereofnegativecharge.Moleculesandionsthatcontainoxygenornitrogenatomsareusuallyalsohardbases,
althoughnotashardasfluorine.ExamplesincludeH2O,CH3OH,OH,NH3andH2NCH3.

AsoftLewisbasehasalargedonoratomofhighpolarisabilityandlowelectronegativity.Theiodideionhasits
valenceelectronsinlargen=5orbitals,makingthisanionhighlypolarisableandaverysoftbase.Othermolecules
andpolyatomicanionswithdonoratomsfromperiods3to6areusuallyalsosoftbases.Tosummarise,thedonor
atombecomessofterfromtoptobottomofagroupoftheperiodictable(figure11.28).

FIGURE11.28Thedonoratombecomessofterdownagroup.

AhardLewisacidhasanacceptoratomwithlowpolarisability.Mostmetalatomsandionsarehardacids.Ingeneral,
thesmallertheionicradiusandthelargerthecharge,thehardertheacid.TheAl3+ion,withanionicradiusofonly67
pm,isaprimeexampleofahardLewisacid.Thenucleusexertsastrongpullonthecompactelectroncloud,giving
theionverylowpolarisability.

Thedesignationofhardacidsisnotrestrictedtometalcations.Forexample,inBF3thesmallboronatominits+3
oxidationstateisbondedtothreehighlyelectronegativefluorineatoms.AlltheBFbondsarepolarisedawayfroma
boroncentrethatisalreadyelectrondeficient.BorontrifluorideisthereforeahardLewisacid.

AsoftLewisacidhasarelativelyhighpolarisability.Largeatomsandlowoxidationstatesoftenconveysoftness.
ContrastthehardacidAl3+withHg 2+,atypicalsoftacid(figure11.29).TheionicradiusofHg 2+is116pm,almost
twicethatofAl3+,becausethevalenceorbitalsofHg 2+haveahighprincipalquantumnumber,n=6.Consequently,
Hg 2+isahighlypolarisable,verysoftLewisacid.TherelativelyfewsoftLewisacidtransitionmetalionsarelocated
aroundgoldintheperiodictable.
 FIGURE11.29TheAl3+ionisaharderLewisacidthanHg2+becauseofitssmallerionicradiusandhighercharge.

Thetermshardandsoftarerelative,sothereisnosharpdividinglinebetweenthetwo,andmanyLewisacidsand
basesareintermediatebetweenhardandsoft.Workedexample11.22showshowtocategoriseLewisacidsandbases
accordingtotheirhardsoftproperties.

WORKEDEXAMPLE11.22

RankingHardnessandSoftness
RankthefollowinggroupsofLewisacidsandbasesfromsoftesttohardest:(a)H2S,H2OandH2Se,(b)
Fe0,Fe3+andFe2+and(c)BCl3,GaCl3andAlCl3.

Analysis

ThefirsttaskistodecidewhetherthemembersofagivengroupareLewisacidsorbases.Thenevaluate
therelativesoftnessandhardnessbasedonpolarisability,takingintoaccountcorrelationswith
electronegativity,sizeandcharge.Refertotheperiodictabletoassessthetrends.

Solution
(a)

Thesethreemoleculeshavelonepairs,sotheyareLewisbases.Thecentralatomsareinthesame
groupoftheperiodictable,sotheirpolarisabilityandthesoftnessofthemoleculesincreases
movingdownthegroup.Thus,H2SeissofterthanH2S,whichissofterthanH2O.
(b)Fe0Fe2+Fe3+MetalatomsandcationsareLewisacids.Asvalenceelectronsareremovedfroma
metalatom,theremainingelectroncloudundergoesaneverlargerpullfromthenuclearcharge.
Thisdecreasesthesizeoftheionaswellasitspolarisability.Thus,Fe0issofterthanFe2+,whichis
softerthanFe3+.
(c)
 Thesethreemoleculeshavetrigonalplanargeometrieswithsp 2hybridisedcentralatoms.Eachhasa
vacantvalenceporbitalperpendiculartothemolecularplane,makingthemoleculesLewisacids.
Thesize,polarisabilityandsoftnessofthecentralacceptoratomincreasesgoingdownthegroup.A
galliumatomislargerandmorepolarisablethananaluminiumatom.Thus,GaCl3issofterthan
AlCl3,whichissofterthanBCl3.WehavealreadynotedthattheAl3+ionisahardLewisacid,and
isthereforelikelytoformcompoundswhicharethemselveshardLewisacids.Thusgallium
trichlorideisasoftLewisacid,whereasAlCl3andBCl3arebothhard.

Isouranswerreasonable?

Hardnessandsoftnessareprimarilydeterminedbyatomicsize,andtheorderofhardnessineachofthese
setsisconsistentwiththesizetrendsamongthespecies.

PRACTICEEXERCISE11.29
IdentifyH2O,NH3,andPH3asLewisacidsor
Lewisbases,andranktheminorderofincreasing
hardness.

ThehardsoftAcidbasePrinciple
Theconceptofhardandsoftacidsandbasescanbeusedtointerpretmanytrendsinchemicalreactivity.Thesetrends
aresummarisedinthehardsoftacidbaseprinciple(HSABprinciple),anempiricalsummaryofresultscollectedfrom
manychemicalreactions:
HardLewisacidstendtocombinewithhardLewisbases.
SoftLewisacidstendtocombinewithsoftLewisbases.

ThegeochemicaldistributionofmetalsconformstotheHSABprinciple.Metalsthatformhardacidcationshave
strongaffinitiesforhardbasessuchasoxide,fluorideandchloride.Mostmetalionsthatarehardacidsarefound
bondedtotheoxygenatomsofvarioussilicateanions.TheseelementsareconcentratedintheEarth'smantle.Hard
acidmetalsalsooccurincombinationswithotherhardbases,includingoxidesor,lessoften,halides,sulfatesand
carbonates.Examplesincluderutile,TiO2,limestone,CaCO3,gypsum,CaSO4,andsylvite,KCl.

Metalsthataresoftacids,suchasgoldandplatinum,havelowaffinitiesforhardoxygenatoms,sotheyarenot
affectedbyO2intheatmosphere.Consequently,thesemetals,includingRu,Rh,Pd,Os,Ir,PtandAu,areoftenfound
inthecrustoftheEarthintheirelementalform.Othersoftmetalsoccurinnatureassulfides.Thesulfideanionisa
softbase,sothiscategoryincludessomesoftacidsandmanyintermediatecases.Softacidsmayalsooccureitherin
elementalformorasarsenideortellurideminerals.Examplesincludegalena,PbS,cinnabar,HgS,chalcopyrite,
CuFeS2,argentite,Ag 2S,calaverite,AuTe2,andsperrylite,PtAs2.

Thegroup13elementsillustratethetrendinhardnessandsoftnessamongLewisacids.Atthetopofthegroup,boron
isahardLewisacidandsoisaluminium.Movingdownthegroup,thevalenceorbitalsincreaseinsizeand
polarisability.Thus,galliumisaborderlineacid,andindiumissoft.Theorderofreactivityforthetrihalidesofthese
elementsdependsontheLewisbase.Forahardbasesuchasammonia,thereactivitytrendforadductformationis:

reflectingthepreferencethatthehardbasehasfortheharderacid.Theorderisreversedwhenthetrihalidesform
adductswithdimethylsulfide,(CH3)2S,asoftbase.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
TheBrnstedLowryDefinitionofAcidsandBases
ABrnstedLowryacidisaprotondonoraBrnstedLowrybaseisaprotonacceptor.Accordingto
theBrnstedLowryapproach,anacidbasereactionisaprotontransferevent.Inanequilibrium
involvingaBrnstedLowryacidandbase,therearetwoconjugateacidbasepairs.Themembersof
anygivenpairdifferfromeachotherbyonlyoneproton.Asolventthatcanbeeitheranacidorabase,
dependingonthenatureoftheotherreactant,isamphiprotic.

AcidbaseReactionsinWater
WaterreactswithitselftoproducesmallamountsofH3O+andOHions.Theconcentrationsofthese
ionsinbothpurewaterandindiluteaqueoussolutionsarerelatedbytheexpression:

Kwistheautoprotolysisconstantofwater.Inpurewater:

ThepHofasolutionisameasureofacidityandisnormallymeasuredwithapHmeter.AsthepH
decreases,theacidityincreases.ThedefiningequationforpHispH=log[H3O+].Inexponentialform,
thisrelationshipbetween[H3O+]andpHisgivenby[H3O+]=10 pH.

ComparableexpressionscanbeusedtodescribelowOHionconcentrationsintermsofpOHvalues:
pOH=log[OH]and[OH]=10 pOH.At25C,pH+pOH=14.00.AsolutionisacidicifitspHisless
than7.00andbasicifitspHisgreaterthan7.00.AneutralsolutionhasapHof7.00.

StrongAcidsandBases
IncalculatingthepHofsolutionsofstrongacidsandbases,weassumethattheyreactcompletelywith
water.Theautoprotolysisofwatercontributesnegligiblyto[H3O+]inasolutionofanacid.Italso
contributesnegligiblytothe[OH]inasolutionofabase.

WeakAcidsandBases
AnacidHAreactswithwateraccordingtothegeneralequation:

Theequilibriumconstantiscalledtheacidityconstant,Ka .

AbaseBreactsbythegeneralequation:

Theequilibriumconstantiscalledthebasicityconstant,Kb.
ThesmallerthevalueofKa orKb,theweakerthesubstancesareasBrnstedLowryacidsorbases.

AnotherwaytocomparetherelativestrengthsofacidsorbasesistousethenegativelogarithmsofKa
andKb,calledpKa andpKb,respectively.

ThesmallerthepKa orpKb,thestrongertheacidorbase.Foraconjugateacidbasepair:

and:

ThevaluesofKa andKbcanbeobtainedfrominitialconcentrationsoftheacidorbaseandthepHof
thesolution.ThemeasuredpHgivestheequilibriumvaluefor[H3O+].

Problemsfallintooneofthreecategories:
1.theonlysoluteisaweakacid(wemustusetheKa expression)
2.theonlysoluteisaweakbase(wemustusetheKbexpression)
3.thesolutioncontainsbothaweakacidanditsconjugatebase(wecanuseeitherKa orKb,orthe
HendersonHasselbalchequation).
Whentheinitialconcentrationoftheacid(orbase)islargerthan400timesthevalueofKa (orKb),itis
safetouseinitialconcentrationsofacidorbaseasthoughtheywereequilibriumvaluesinthe
equilibriumconstantexpression.Whenthisapproximationcannotbeused,weusethequadratic
formula.

Theweakeranacid,thestrongeritsconjugatebase,andviceversa.Anionsofstrongacids,suchasCl
andNO3,aresuchweakBrnstedLowrybasesthattheycannotaffectthepHofasolution.

Ifasaltisderivedfromaweakacidandaweakbase,itsneteffectonpHhastobeestablishedona
casebycasebasisbydeterminingwhichofthetwoionsreactswithwatertoagreaterextent.

TheMolecularBasisofAcidStrength
Binaryacidscontainonlyhydrogenandanothernonmetal.Theirstrengthsincreasefromtoptobottom
withinagroupandlefttorightacrossaperiod.Oxoacids,whichcontainoxygenatomsinadditionto
hydrogenandanotherelement,increaseinstrengthasthenumberofoxygenatomsonthesamecentral
atomincreases.Oxoacidswiththesamenumberofoxygenatomsgenerallyincreaseinstrengthasthe
centralatommovesfrombottomtotopwithinagroupandfromlefttorightacrossaperiod.

BufferSolutions
Asolutionthatcontainsappreciableamountsofbothaweakacidandaweakbase(usuallyanacid
baseconjugatepair)iscalledabuffersolution,becauseitisabletoabsorbH3O+fromastrongacidor
OHfromastrongbasewithoutsufferinglargechangesinpH.

Forthegeneralacidbasepair,HAandA,thefollowingreactionsoccurinabuffersolution:
ThepHofabufferiscontrolledbytheratioofweakacidtoweakbase,expressedeitherintermsof
concentrationoramount.

Becausethe[H3O+]isdeterminedbythemoleratioofHAtoA,dilutiondoesnotchangethepHofa
buffer.Theequation:

canbeusedtocalculatethepHdirectlyfromthepKa oftheacidandtheconcentrationsoftheconjugate
acidHAandbaseA.

Inperformingbuffercalculations,theusuallyvalidsimplificationsare:

BuffersaremosteffectivewhenthepKa oftheacidmemberofthebufferpairlieswithin1unitofthe
desiredpH.

AlthoughthemoleratioofAtoHAdeterminesthepHatwhichabufferworks,theamountsoftheacid
anditsconjugatebasegivethebufferitscapacityfortakingonstrongacidorbasewithlittlechangein
pH.

AcidbaseTitrations
ThepHattheequivalencepointdependsontheionsofthesaltformedduringthetitration.Inthe
titrationofastrongacidwithastrongbase,thepHattheequivalencepointis7becauseneitherofthe
ionsproducedinthereactionaffectsthepHofanaqueoussolution.

Forthetitrationofaweakacidwithastrongbase,theapproachtowardscalculationofthepHvaries
dependingonwhichstageofthetitrationisconsidered.
1.Beforethetitrationbegins,theonlysoluteistheweakacid,andsoKa isused.
2.Afterstarting,butbeforetheequivalencepoint,thesolutionisabuffer.EitherKa orKbcanbe
used.
3.Attheequivalencepoint,theactivesoluteistheconjugatebaseoftheweakacid.Kbforthe
conjugatebasemustbeused.
4.Aftertheequivalencepoint,excessstrongbasedeterminesthepHofthemixture.Noequilibrium
calculationsarerequired.Attheequivalencepoint,thepHisabove7.
Similarcalculationsapplyinthetitrationofaweakbasebyastrongacid.Insuchtitrations,thepHatthe
equivalencepointisbelow7.

TheindicatorchosenforatitrationshouldhavethecentreofitscolourchangerangenearthepHatthe
equivalencepoint.Forthetitrationofastrongorweakacidwithastrongbase,phenolphthaleinisthe
bestindicator.Whenaweakbaseistitratedwithastrongacid,severalindicators,includingmethyl
orange,worksatisfactorily.

LewisAcidsandBases
ALewisacidisanelectronpairacceptor,whileaLewisbaseisanelectronpairdonor.Electrophilesare
LewisacidsandnucleophilesareLewisbases.

ALewisbasemusthaveoneormorepairsofvalenceelectronsavailableforbondformation.ALewis
acidmustbeabletoacceptanelectronpairtoformanewbond.MostLewisacidsareoneofthe
following:amoleculewithvacantvalenceorbitals,amoleculewithdelocalisedbondsinvolving
oxygen,orametalcation.

Thepolarisabilityofanatom,ionormoleculeistheeasewithwhichitselectroncloudcanbedistorted
byanelectricalcharge.Polarisabilitydecreasesfromlefttorightinanyperiodoftheperiodictable(as
theeffectivenuclearcharge,Zeff,increases).Polarisabilityincreasesfromtoptobottomofanygroupof
theperiodictable(astheprincipalquantumnumber,n,increases).

AhardLewisbasehaselectronpairsoflowpolarisabilityandhighelectronegativity.AsoftLewisbase
hasalargedonoratomofhighpolarisabilityandlowelectronegativity.AhardLewisacidhasan
acceptoratomwithlowpolarisability.AsoftLewisacidhasarelativelyhighpolarisability.Thehard
softacidbase(HSAB)principlestatesthathardLewisacidstendtocombinewithhardLewisbases,
whilesoftLewisacidstendtocombinewithsoftLewisbases.Thisisreflectedinnature,wherehard
metalionstendtobefoundbondedtohardbases,andviceversa.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS

Autoprotolysisconstantforwater[H3O+][OH]=Kw(section11.2)
Thisequationisusedtocalculate[H3O+]if[OH]isknown,andviceversa.

pHandpOH(section11.2)
Theseprovideaconvenientmethodforrepresenting[H3O+]and[OH]inaqueoussolution.

RelationshipbetweenpHandpOH:pH+pOH=14.00at25C(section11.2)
ThisrelationshipcanbeusedtocalculatepHifpOHisknown,andviceversa.

KaKb=Kw(section11.4)
ThisequationisusedtocalculateKa givenKb,orviceversa.

Periodictrendsinstrengthsofbinaryacids(section11.5)
PeriodictrendscanbeusedtopredicttherelativeaciditiesofXHbonds,bothforthebinaryhydrids
themselvesandformoleculesthatcontainXHbonds.

Periodictrendsinstrengthsofoxoacids(section11.5)
Periodictrendscanbeusedtopredicttherelativeaciditiesofoxoacidsaccordingtothenatureofthe
centralnonmetalaswellasthenumberofoxygenatomsattachedtoagivennonmetal.Theprinciples
involvedalsoletyoucomparetheaciditiesofcompoundscontainingdifferentelectronegativeelements.

(section11.6)

ThisequationcanbeusedtocalculatethepHofabuffersolution.

Hardsoftacidbaseprinciple(section11.8)
HardLewisacidstendtocombinewithhardLewisbases.SoftLewisacidstendtocombinewithsoft
Lewisbases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
TheBrnstedLowryDefinitionofAcidsandBases
11.1HowisaBrnstedLowryaciddefined?HowisaBrnstedLowrybasedefined?
11.2Howaretheformulaeofthemembersofaconjugateacidbasepairrelatedtoeachother?Within
thepair,howcanyoutellwhichistheacid?
11.3IsH SO theconjugateacidofSO 2?Explainyouranswer.
2 4 4
11.4Definethetermamphiprotic.
11.5Writethestructuralformulaefortheconjugateacidsofthefollowingstructures.
(a)

(b)

(c)

11.6Writethestructuralformulaefortheconjugatebasesofthefollowingstructures.
(a)

(b)

(c)

AcidbaseReactionsinWater
11.7Explainwhy,inpurewaterat25C,theconcentrationofH O+cannotbegreaterthan110 7M.
3
11.8At40.0C,K =3.010 14.CalculatethepHofpurewateratthistemperature.Commentonthe
w
statementpurewateralwayshasapHof7withreferencetoyouranswer.
StrongAcidsandBases
11.9Whatisthedefinitionofastrongacid?
11.10Willtheconjugateacidofastrongbasebeverystrong,strong,weakorveryweak?Giveyour
reasoning.
11.11TheNH ion(sometimescalledtheamideion)isaverystrongbaseitisevenstrongerthan
2
OH.Writeanequationthatshowsthereactionthatoccurswhentheamideionisplacedinwater,
 andusethistoexplainwhytheamideioncannotexistinaqueoussolution.
WeakAcidsandBases
11.12Writethegeneralequationforthereactionofaweakacidwithwater.GivetheexpressionforKa .
11.13Writethechemicalequationforthereactionofeachofthefollowingweakacidswithwaterand
writetheappropriateKa expression.(Somearepolyproticacidsforthese,writeonlytheequation
forthefirststepintheionisation.)
(a)HNO2
(b)H3PO4
(c) HAsO 2
4
(d)(CH ) NH+
33
11.14Writethegeneralequationforthereactionofaweakbasewithwater.GivetheexpressionforKb.
11.15Writethechemicalequationforthereactionofeachofthefollowingweakbaseswithwaterand
writetheappropriateKbexpression.
(a)(CH3)3N
(b)AsO 3
4
(c) NO
2
(d)(CH3)2NNH2
11.16ThepK ofHCNis9.21andthatofHFis3.17.WhichisthestrongerBrnstedLowrybase,CN
a
orF?
11.17Aspirinisacetylsalicylicacid,amonoproticacidwithaK valueof3.2710 4.Isasolutionof
a
thesodiumsaltofaspirininwateracidic,basicorneutral?Explain.
11.18Considerthefollowingcompoundsandsupposethata0.1Msolutionispreparedofeach:NaI,
KF,(NH4)2SO4,KCN,KOOCCH3,CsNO3andKBr.Writetheformulaeofthosethathave
solutionsthatare:
(a)acidic
(b)basic
(c)neutral.
11.19Ammoniumnitrateiscommonlyusedinfertilisermixturesasasourceofnitrogenforplant
growth.Whateffect,ifany,willthiscompoundhaveontheacidityofthemoistureinthe
ground?Explain.
11.20Asolutionofhydraziniumacetateisslightlyacidic.Withoutlookingatthetablesofequilibrium
constants,isKa foraceticacidlargerorsmallerthanKbforhydrazine?Justifyyouranswer.
11.21Whatcriteriondoweusetodeterminewhetherweareabletousetheinitialconcentrationofan
acidorbaseasthoughitweretheequilibriumconcentrationwhenwecalculatethepHofthe
solution?
11.22Forwhichofthefollowingarewepermittedtousetheinitialconcentrationoftheacidorbaseto
calculatethepHofthesolutionspecified?
(a)0.020MCH3COOH
(b)0.10MCH3NH2
(c)0.002MN2H4
 (d)0.050MHCOOH
TheMolecularBasisofAcidStrength
11.23Withintheperiodictable,howdothestrengthsofthebinaryacidsvaryfromlefttorightacrossa
period?Howdotheyvaryfromtoptobottomwithinagroup?
11.24Astatine,At,atomicnumber85,isradioactiveanddoesnotoccurinappreciableamountsin
nature.Basedonwhatyouhavelearnedinthischapter,answerthefollowing.
(a)HowwouldtheacidityofHAtcomparewithHI?
(b)HowwouldtheacidityofHAtO3comparewithHBrO3?
11.25Explainwhynitricacidisastrongeracidthannitrousacid.

11.26ExplainwhyHClO4isastrongeracidthanH2SeO4.
11.27ExplainwhytheNO ionisastrongerbasethantheSO 2ion.
2 3
11.28Thepositionofequilibriumintheequationbelowliesfartotheleft.Identifytheconjugateacid
basepairs.Whichofthetwoacidsisstronger?

11.29Considerthefollowing:CO 2isaweakerbasethanhydroxideion,andHCO isastrongeracid

3 3
thanwater.Intheequationbelow,wouldthepositionofequilibriumlietotheleftortotheright?
Justifyyouranswer.

11.30Aceticacid,CH3COOH,isaweakeracidthannitrousacid,HNO2.Howdothestrengthsofthe
basesCH3COOandNO2compare?
11.31Nitricacid,HNO3,isaverystrongacid.Itis100%ionisedinwater.Inthereactionbelow,would
thepositionofequilibriumlietotheleftorright?

11.32HClO4isastrongerprotondonorthanHNO3,butinwaterbothacidsappeartobeofequal
strengththeyareboth100%ionised.Whyisthisso?Whatsolventpropertywouldbenecessary
inordertodistinguishbetweentheaciditiesofthesetwoBrnstedLowryacids?
11.33Formicacid,HCOOH,andaceticacid,CH3COOH,areclassifiedasweakacids,butinwater
HCOOHismoredissociatedthanCH3COOH.However,ifweuseliquidammoniaasasolvent
fortheseacids,theybothappeartobeofequalstrengthsand100%dissociated.Explainwhythis
isso.
BufferSolutions
11.34Writeionicequationsthatillustratehoweachpairofcompoundsbelowcanserveasabuffer
pair.
(a)H2CO3andNaHCO3(thecarbonatebufferinblood)
(b)NaH2PO4andNa2HPO4(thephosphatebufferinsidebodycells)
(c)NH4ClandNH3
11.35Buffer1isasolutioncontaining0.10MNH4Cland1.0MNH3.Buffer2isasolutioncontaining
1.0MNH4Cland0.10MNH3.WhichbufferisbetterabletomaintainasteadypHonthe
 additionofstrongacid?Explain.
AcidbaseTitrations
11.3611.36Whenaformicacidsolutionistitratedwithsodiumhydroxide,willthesolutionbeacidic,
neutralorbasicattheequivalencepoint?
11.37Whenasolutionofhydrazineistitratedbyhydrochloricacid,willthesolutionbeacidic,neutral
orbasicattheequivalencepoint?
11.38Definethetermsequivalencepointandendpointastheyapplytoanacidbasetitration.
11.39Qualitatively,describehowanacidbaseindicatorworks.Whydowewanttouseaminimum
amountofindicatorinatitration?
11.40Explainwhyethylredisabetterindicatorthanphenolphthaleininthetitrationofdiluteammonia
bydilutehydrochloricacid.
11.41Whatisagoodindicatorfortitratingpotassiumhydroxidewithhydrobromicacid?Explain.
11.42IfyouusemethylorangeinthetitrationofCH3COOHwithNaOH,willtheendpointofthe
titrationcorrespondtotheequivalencepoint?Justifyyouranswer.
LewisAcidsandBases
11.43DefinethetermsLewisacidandLewisbase.
11.44ExplainwhytheadditionofaprotontoawatermoleculetogiveH O+isaLewisacidbase
3
reaction.
11.45MethylaminehastheformulaCH3NH2andthestructure:

UseLewisstructurestoillustratethereactionofmethylaminewithborontrifluoride,BF3.
11.46Explainwhytheoxideion,O2,canfunctionasaLewisbasebutnotasaLewisacid.
11.47DrawtheLewisstructuresofeachofthereactantsinthefollowingreactions.
(a) SO +OHHSO
3 4
(b)SnCl +Cl[SnCl ]
2 3
(c) AsF +SbF [AsF ]+[SbF ]
3 5 2 6
11.48IdentifytheLewisacidandtheLewisbaseineachofthereactionsthatappearsinquestion
11.47.
11.49Drawmechanisticarrowsthatshowthedonationofelectronsthattakesplaceineachreactionin
question11.47anddrawtheLewisstructuresoftheproducts.
11.50Statethehardsoftacidbase(HSAB)principle.Defineandgiveexamplesofhardandsoftacids
andbases.
11.51Rankthethreemoleculesorionsineachofthefollowinggroupsfromsoftesttohardest.
(a)NCl3,NH3andNF3
(b)ClO ,ClO andClO
4 2 3
(c) Pb 2+,Pb 4+andZn 2+
(d)
 PCl3,SbCl3andPF3
11.52Ironisalwaysfoundinnatureincompounds,oftenwithoxygen.Theothermembersofgroup8
intheperiodictable,rutheniumandosmium,occurinelementalform.Explaintheseobservations
usingtheHSABprinciple.
11.53Leadpoisoningcanbetreatedusingthedianionof2,3dimercaptopropanol.Twoionsbindone
Pb 2+ioninasolubletetrahedralcomplexthatcanbeexcretedfromthebody.Usinghardsoft
acidbaseconcepts,drawtheexpectedstructureofthiscomplex.

11.54Theanionpresentinaqueoussolutionsofboricacidis[B(OH) ]ratherthanH BO .Thisis

4 2 3
becauseH3BO3undergoesLewisacidbaseadductformationwithonewatermolecule,andthe
adductthentransfersaprotontoasecondwatermoleculetogenerate[B(OH)4]anda
hydroniumion.DrawLewisstructuraldiagramsillustratingthesetwotransferreactions.Showall
formalcharges,andincludearrowsthatshowthemovementofelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
11.55Writetheformulafortheconjugateacidofeachofthefollowing.
(a) F
(b)N2H4
(c)C5H5N
(d)O 2
2
(e) HCrO
4
11.56Writetheformulafortheconjugatebaseofeachofthefollowing.
(a)NH2OH
(b)HSO
3
(c)HCN
(d)H5IO6
(e)HNO2
11.57Identifytheconjugateacidbasepairsinthefollowingreactions.
(a) HNO +N H NO3+N2H5+
3 2 4
(b)NH +N H + NH4++N2H4
3 2 5
(c) H PO +CO 2 HPO42+HCO3
2 4 3
(d)HIO +HC O IO3+H2C2O4
3 2 4
11.58Identifytheconjugateacidbasepairsinthefollowingreactions.
(a) HSO +SO 2 HSO3+SO42
4 3
(b)S2+H O HS+OH
2
(c) CN+H O+ HCN+H2O
3
(d)H Se+H O HSe+H3O+
2 2
11.59Calculate[H O+]ineachofthefollowingaqueoussolutionsinwhichthehydroxideion
3
concentrationsare:
(a)0.0024M
(b)1.410 5M
(c) 5.610 9M
(d)4.210 13M
11.60Calculate[OH]ineachofthefollowingaqueoussolutionsinwhichtheH O+concentrationsare:
3
(a) 3.510 8M
(b)0.0065M
(c) 2.510 13M
(d)7.510 5M
11.61CalculatethepHofeachsolutioninquestion11.59.
11.62CalculatethepHofeachsolutioninquestion11.60.
11.63Calculate[H O+]and[OH]insolutionsthathavethefollowingpHvalues.
3
(a)8.26
(b)10.25
(c)4.65
(d)6.18
(e)9.70
11.64Whatisthe[H O+]in0.030MHNO ?WhatisthepHofthesolution?WhatistheOH
3 3
concentrationinthesolution?
11.65Asodiumhydroxidesolutionispreparedbydissolving6.0gNaOHin1.00Lofaqueous
solution.WhatisthemolarconcentrationofOHinthesolution?WhatarethepOHandthepH
ofthesolution?WhatistheH3O+concentrationinthesolution?
11.66Anaqueoussolutionwasmadebydissolving0.837gBa(OH)2inwatertogiveafinalvolumeof
100mL.WhatisthemolarconcentrationofOHinthesolution?WhatarethepOHandthepH?
WhatistheH3O+concentrationinthesolution?
11.67Whatvolumeof0.100MKOHisneededtocompletelyneutralisetheHClin300mLofa
hydrochloricacidsolutionthathasapHof2.25?
11.68TheK forHFis6.810 4.WhatisK forF?
a b
11.69Thebarbiturateion,C H N O ,hasK =1.010 10.WhatisK forbarbituricacid?
4 3 2 3 b a
11.70Hydrogenperoxide,H O ,isaweakacidwithK =1.810 12.WhatisthevalueofK forthe
2 2 a b
HO2ion?
11.71Methylamine,CH NH ,resemblesammoniainodourandbasicity.ItsK is4.410 4.Calculate
3 2 b
theKa ofitsconjugateacid.
11.72Lacticacid,CH CH(OH)COOH,isresponsibleforthesourtasteofsourmilk.At25C,itsK =
3 a
1.410 4.WhatistheKbofitsconjugatebase,thelactateion,CH3CH(OH)COO?
11.73Iodicacid,HIO3,hasapKa of0.23.(a)WhataretheformulaandtheKbofitsconjugatebase?
(b)Isitsconjugatebaseastrongerorweakerbasethantheacetateion?
11.74Atthetemperatureofthehumanbody,37C,thevalueofK is2.410 14.Calculatethe
w
[H3O+],[OH],pHandpOHofpurewateratthistemperature.WhatistherelationbetweenpH,
pOHandKwatthistemperature?Iswaterneutralatthistemperature?
11.75Periodicacid,HIO4,isanimportantoxidisingagentandamoderatelystrongacid.Ina0.10M
solution,[H3O+]=3.810 2molL1.CalculatetheKa andpKa forperiodicacid.
11.76Chloroaceticacid,ClCH2COOH,isastrongermonoproticacidthanaceticacid.Ina0.10M
solution,thepHis1.96.CalculatetheKa andpKa forchloroaceticacid.
11.77Hydroxylamine,NH2OH,likeammonia,isaBrnstedLowrybase.A0.15MsolutionhasapH
of10.12.WhatareKbandpKbforhydroxylamine?
11.78Whataretheconcentrationsofallthesolutespeciesin0.150Mlacticacid,CH3CH(OH)COOH?
 WhatisthepHofthesolution?ThisacidhasKa =1.410 4.
11.79WhatisthepHof0.15Mhydrazoicacid,HN ?ForHN ,K =1.810 5.
3 3 a
11.80Phenol,alsoknownascarbolicacid,issometimesusedasadisinfectant.Whatarethe
concentrationsofallofthesolutespeciesina0.050Msolutionofphenol,C6H5OH?Forthis
acid,Ka =1.310 10.
11.81Codeine,acoughsuppressantextractedfromcrudeopium,isaweakbasewithapKbof5.79.
WhatisthepHofa0.020Msolutionofcodeine?
11.82Pyridine,C5H5N,isabadsmellingliquidthatisaweakbaseinwater.ItspKbis8.82.Whatisthe
pHofa0.20Maqueoussolutionofthiscompound?
11.83WhatamountofNH3mustbedissolvedinwatertogive500mLofsolutionwithapHof11.22?
11.84CalculatethepHof0.20MNaCN.WhatistheconcentrationofHCNinthesolution?
11.85CalculatethepHof0.40MKNO2.WhatistheconcentrationofHNO2inthesolution?
11.86CalculatethepHof0.15Mmethylammoniumchloride,CH3NH3Cl.Formethylamine,CH3NH2,
Kb=4.410 4.
11.87CalculatethepHof0.10Mhydraziniumchloride,N2H5Cl.Hydrazine,N2H4,isaweakbasewith
Kb=1.710 6.
11.88A0.18Msolutionofthesodiumsaltofnicotinicacid(alsoknownasniacin)hasapHof9.05.
WhatisthevalueofKa fornicotinicacid?
11.89AweakbaseBformsthesaltBHCl,composedoftheionsBH+andCl.A0.15Msolutionofthe
salthasapHof4.28.WhatisthevalueofKbforthebaseB?
11.90CalculatethemassofNH4Brthathastobedissolvedin1.00Lofwaterat25Ctogivea
solutionwithapHof5.16.
11.91Liquidchlorinebleachisessentiallyasolutionofsodiumhypochlorite,NaOCl,inwater.Usually,
theconcentrationisapproximately5%NaOClbyweight.Usethisinformationtocalculatethe
approximatepHofableachsolution,assumingNaOClistheonlysolute.(Assumethebleachhas
adensityof1.0gmL1.)
11.92WhatisthepHofa0.0050Msolutionofsodiumcyanide?TheK ofNaCNis1.6210 5.
b
11.93WhatisthepHofa0.020Msolutionofchloroaceticacid,forwhichK =1.3610 3?
a
11.94Thecompoundparaaminobenzoicacid(PABA)isapowerfulsunscreeningagentwhosesalts
wereonceusedwidelyinsuntanandsunscreenlotions.Theparentacidisaweakacidwitha
pKa of4.92(at25C).Whatisthe[H3O+]andpHofa0.030Msolutionofthisacid?
11.95Barbituricacid,HC4H3N2O3,wasdiscoveredbytheNobelPrizewinningorganicchemist
AdolphvonBaeyerandnamedafterhisfriendBarbara.Itistheparentcompoundofwidelyused
sleepingdrugs,thebarbiturates.ItspKa is4.01.Whatisthe[H3O+]andpHofa0.020Msolution
ofbarbituricacid?
11.96Choosethestrongeracidineachofthefollowing:
(a)H2SorH2Se,
(b)H2TeorHI,
(c)PH3orNH3.
11.97Choosethestrongeracidineachofthefollowing:
 (a)HBrorHCl,
(b)H2OorHF,
(c)H2SorHBr.
11.98Choosethestrongeracidineachofthefollowing:
(a)HIO3orHIO4,
(b)H3AsO4orH3AsO3.
11.99Choosethestrongeracidineachofthefollowing:
(a)HOClorHClO2,
(b)H2SeO4orH2SeO3.
11.100Choosethestrongeracidineachofthefollowing:
(a)H3AsO4orH3PO4,
(b)H2CO3orHNO3,
(c)H2SeO4orHClO4.
11.101Choosethestrongeracidineachofthefollowing:
(a)HClO3orHIO3,
(b)HIO2orHClO3,
(c)H2SeO3orHBrO4.
11.102WhatisthepHofasolutionthatcontains0.15MCH COOHand0.25MCH COO?K =1.8
3 3 a
10 5forCH3COOH.
11.103Abuffercontains0.25MNH and0.45MNH +.CalculatethepHofthebuffer.
3 4
11.104Suppose25.0mLof0.10MHClisaddedto250mLofabuffercomposedof0.25MNH3and
0.20MNH4Cl.ByhowmuchwilltheconcentrationsoftheNH3andNH4+ionschangeafter
theadditionofthestrongacid?
11.105Astudentadded100mLof0.10MNaOHto250mLofabufferthatcontained0.15M
CH3COOHand0.25MCH3COO.ByhowmuchdidtheconcentrationsofCH3COOHand
CH3COOchangeaftertheadditionofthestrongbase?
11.106WhatmoleratioofNH4CltoNH3wouldbufferasolutionatpH9.25?
11.107Whatmassofsodiumacetate,NaOOCCH3,needstobeaddedto1.0Lof0.15Maceticacid
(pKa 4.74)tomakeabuffersolutionwithpH5.00?
11.108Whatmassofsodiumformate,NaOOCH,needstobedissolvedin1.0Lof0.12Mformicacid
(pKa 3.74)tomakeabuffersolutionwithpH3.80?
11.109Whatmassofammoniumchloridehastobedissolvedin500mLof0.20MNH3topreparea
buffersolutionwithpH10.00?
11.110Whatmassofammoniumchloridehastobedissolvedin125mLof0.10MNH3tomakeita
bufferwithapHof9.15?
11.111Suppose25.00mLof0.100MHClisaddedtoanacetatebuffer,whichwaspreparedby
dissolving0.100molofaceticacidand0.110molofsodiumacetateinwater.Whatarethe
initialandfinalpHvalues?WhatwouldthepHbeifthesamevolumeoftheHClsolutionwas
addedto125mLofpurewater?
11.112Whatvolumeof0.15MHClhastobeaddedto100mLofthebufferdescribedinquestion
11.111tomakethepHdecreaseby0.05pHunits?WhatvolumeofthesameHClsolution
would,ifaddedto100mLofpurewater,makethepHdecreaseby0.05pHunits?
11.113An18.5mLsampleofalacticacidsolutionrequired17.25mLof0.155MNaOHtoreachan
endpointinatitration.Whatamountoflacticacidwasinthesample?
11.114Ascorbicacid(vitaminC)isadiproticacidwiththeformulaH2C6H6O6.Asampleofavitamin
supplementwasanalysedbytitratinga0.1000gsampledissolvedinwaterwith0.0200M
NaOH.Avolumeof15.20mLofthebasewasrequiredtoreactcompletelywiththeascorbic
acid.Whatwasthepercentagebymassofascorbicacidinthesample?
11.115ToamixtureofNaClandNa2CO3,withamassof1.243g,wasadded50.00mLof0.240M
HCl(anexcessofHCl).ThemixturewaswarmedtoexpelalloftheCO2andthentheunreacted
HClwastitratedwith0.100MNaOH.Thetitrationrequired22.90mLoftheNaOHsolution.
WhatwasthepercentagebymassofNaClintheoriginalmixtureofNaClandNa2CO3?
11.116Aspirinisthecommonnameofamonoproticacidcalledacetylsalicylicacid.Itsformulais
HOOCC6H4OCOCH3.Acertainpainrelieverwasanalysedforaspirinbydissolving0.250gof
itinwaterandtitratingitwith0.0300MKOHsolution.Thetitrationrequired29.40mLofbase.
Whatisthepercentagebymassofaspirininthedrug?
11.117When50mLof0.10Mformicacid,HCOOH,istitratedwith0.10Msodiumhydroxide,whatis
thepHattheequivalencepoint?(Besuretotakeintoaccountthechangeinvolumeduringthe
titration.)Selectagoodindicatorforthistitrationfromtable11.9.
11.118When25mLof0.10Maqueousammoniaistitratedwith0.10Mhydrobromicacid,whatisthe
pHattheequivalencepoint?Selectagoodindicatorforthistitrationfromtable11.9.
11.119WhatisthepHofasolutionpreparedbymixing25.0mLof0.180MCH3COOHwith35.0mL
of0.250MNaOH?
11.120WhatisthepHofasolutionpreparedbymixing30.0mLof0.200MCH3COOHwith15.0mL
of0.400MKOH?
11.121Forthetitrationof25.00mLof0.1000Maceticacidwith0.1000MNaOH,calculatethepH:
(a)beforetheadditionofanyNaOHsolution
(b)after10.00mLofthebasehasbeenadded
(c)afterhalfoftheaceticacidhasbeenneutralised
(d)attheequivalencepoint.
11.122Forthetitrationof25.00mLof0.1000Mammoniawith0.1000MHCl,calculatethepH:
(a)beforetheadditionofanyHClsolution
(b)after10.00mLoftheacidhasbeenadded
(c)afterhalfoftheNH3hasbeenneutralised
(d)attheequivalencepoint.
11.123UseLewissymbolstorepresentthereaction:

IdentifytheLewisacidandLewisbaseinthereaction.
11.124UseLewissymbolstorepresentthereaction:

IdentifytheLewisacidandLewisbaseinthereaction.
11.125Aluminiumchloride,AlCl3,formsmoleculeswiththeformulaAl2Cl6.Thestructureofthese
moleculesis:

UseLewisstructurestoshowhowthereaction2AlCl3Al2Cl6isaLewisacidbasereaction.
11.126Ineachofthefollowingreactions,identifytheLewisacidandtheLewisbase.
(a)Ni+4CO[Ni(CO)4]
(b)SbCl +2Cl[SbCl ]2
3 5
(c)(CH3)3P+AlBr3(CH3)3PAlBr3
(d)BF +ClF [ClF ]+[BF ]
3 3 2 4
11.127Ineachofthefollowingreactions,identifytheLewisacidandtheLewisbase.
(a) AlCl +CH ClCH ++[AlCl ]
3 3 3 4
(b)Zn 2++4CN[Zn(CN) ]2
4
(c) I +II
2 3
(d)CaO+CO2CaCO3
11.128Usingliquidammonia,NH3,asasolvent,sodiumamide,NaNH2,reactswithammonium
chloride,NH4Cl,inanacidbaseneutralisationreaction.Assumingthatthesecompoundsare
completelydissociatedinliquidammonia,writemolecular,ionicandnetionicequationsforthe
reaction.Whichsubstanceistheacidandwhichisthebase?
11.129Rankthefollowingionsinorderofincreasingpolarisability,andexplainyourreasoning:Fe3+,
Fe2+,Pb 2+andV3+.
11.130Rankthefollowingionsinorderofincreasingpolarisability,andexplainyourreasoning:
SO32,NO3,CO32andClO3.
11.131RankthethreeLewisacidsineachofthefollowinggroupsfromhardesttosoftest,andexplain
yourreasoning.
(a)BCl3,BF3andAlCl3
(b)Al3+,Tl3+andTl+
(c)AlCl3,AlI3andAlBr3
11.132RankthethreeLewisbasesineachofthefollowinggroupsfromhardesttosoftest,andexplain
yourrankings.
(a)NH3,SbH3andPH3
(b)PO 3,ClO andSO 2
4 4 4
(c) O2,Se2andS
11.133ExplainwhySO3isaharderLewisacidthanSO2.
11.134Explainwhyiodideisasoftbasebutchlorideisahardbase.
11.135DeterminetheLewisstructureofSnCl4andexplainhowitfunctionsasaLewisacid.
11.136DeterminetheLewisstructureofSbF5andexplainhowitfunctionsasaLewisacid.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
11.137Whatistheformulaoftheconjugateacidofdimethylamine,(CH3)2NH?Whatistheformulaof
itsconjugatebase?
11.138Hydrazine,N2H4,isaweakerBrnstedLowrybasethanammonia.Inthefollowingreaction,
wouldthepositionofequilibriumlietotheleftortotheright?Justifyyouranswer.

11.139Suppose38.0mLof0.00200MHClisaddedto40.0mLof0.00180MNaOH.WhatisthepH
ofthefinalmixture?
11.140WhatisthepHofasolutionthatis0.100MinHClandalso0.125MinCH3COOH?Whatisthe
concentrationofacetateioninthissolution?
11.141Asolutionispreparedbymixing300mLof0.500MNH3and100mLof0.500MHCl.
Assumingthatthevolumesareadditive,whatisthepHoftheresultingmixture?
11.142WhatisthepHof0.120MNH4NO3?
11.143PredictwhetherthepHof0.120MNH4CNisgreaterthan,lessthanorequalto7.00.Giveyour
reasons.
11.144Somepeoplewhotakemegadosesofascorbicacidwilldrinkasolutioncontainingasmuchas
6.0gofascorbicaciddissolvedinaglassofwater.Assumingthevolumetobe250mL,
calculatethepHofthissolution.
11.145Forthetitrationof25.00mLof0.1000MHClwith0.1000MNaOH,calculatethepHofthe
reactionmixtureaftereachofthefollowingtotalvolumesofbasehasbeenaddedtotheoriginal
solution.(Remembertotakeintoaccountthechangeintotalvolume.)Constructagraph
showingthetitrationcurveforthisexperiment.
(a)0mL
(b)10.00mL
(c)24.90mL
(d)24.99mL
(e)25.00mL
(f) 25.01mL
(g)25.10mL
(h)26.00mL
(i) 50.00mL
11.146ThefluoridesBF3,AlF3,SiF4andPF5areLewisacids.Theyallformverystablefluoroanions
whentreatedwithlithiumfluoride.Incontrast,threeotherfluorides,CF4,NF3andSF6,donot
reactwithlithiumfluoride.UseLewisacidbaseconceptstoexplainthisbehaviour.
11.147CompleteeachofthefollowingreactionsbyconsideringtheLewisacidandbasecharacteristics
ofthestartingmaterials.
(a)AlCl3+LiCH3?
(b)SO3+excessH2O?
(c)SbF5+LiF?
(d)SF4+AsCl5?
11.148Certainproteolyticenzymesreactinalkalinesolutions.Oneoftheseenzymesproduces1.8
 micromolesofhydrogenionspersecondina2.50mLportionofabuffercomposedof0.25M
NH3and0.20MNH4Cl.ByhowmuchwilltheconcentrationsoftheNH3andNH4+ions
changeafterthereactionhasrunfor35seconds?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
acid conjugateacidbasepair nucleophiles
acidbaseindicator conjugatebase pH
acidbasereactions diproticacid pKa
acidbasetitration diproticbase pKb
acidic electrophile pKw
acidityconstant(Ka) endpoint
pOH
adduct equivalencepoint
polyproticacid
alkaline hardLewisacid
polyproticbase
amphiprotic hardLewisbase
resonancestabilisation
autoprotolysis HendersonHasselbalch
softLewisacid
Kw equation
softLewisbase
base heterolyticcleavage
strongacid
basic homolyticcleavage
strongbase
basicityconstant(Kb) hydroniumion
titrant
BrnstedLowry hydroxideion
titrationcurve
buffercapacity Lewisacid
triproticacid
buffersolution Lewisbase
weakacid
burette monoproticacid
weakbase
conjugateacid monoproticbase
zwitterion
neutral

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

12 OxidationandReduction
Intheprecedingchapters,welearnedaboutsomeimportantreactionsthattakeplaceinaqueoussolutions.In
thischapter,wewillexpandonthatknowledgewithadiscussionofaclassofreactionsthatinvolvethe
transferofoneormoreelectronsfromonechemicalspeciestoanother.Chemistscalltheseelectrontransfer
processesoxidationsandreductionsor,simply,redoxreactions.Redoxreactionsareverycommon.For
example,thephotoonthispageshowsarustyironanchor,allthatremainsoftheMarieGabrielle(1880)on
theShipwreckCoastatMoonlightHeadinVictoria,Australia.TheMarieGabriellewasenroutefrom
Chinawithaloadofteawhenshehitthereefinstrongwinds.Formationofrustisaredoxprocessinwhich
electronsaretransferredfromirontooxygen.

Inthischapter,wewilllearnhowtorecogniseandanalysethechangesthatoccurinthesereactions.Wewill
alsolearnthatredoxreactionscanbeusedtogenerateelectricityingalvaniccells(commonlycalled
batteries)andthat,byreversingthisprocess,electricitycanbeusedtocausenonspontaneousredox
reactions.Becauseelectricityplaysaroleinthesesystems,theprocessesinvolvedareelectrochemical
changes.Thestudyofsuchchangesiscalledelectrochemistry.

KEYTOPICS

12.1Oxidationandreduction
12.2Balancingnetionicequationsforredoxreactions
12.3Galvaniccells
12.4Reductionpotentials
12.5Relationshipbetweencellpotential,concentrationandGibbsenergy
12.6Corrosion
 12.6Corrosion
12.7Electrolysis
12.8Batteries

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.1OxidationandReduction
Amongthefirstreactionsstudiedbyearlyscientistswerethosethatinvolvedoxygen.Accordingtotheoriginaldefinition,oxidationisareaction
withoxygen.IfametalatomMreactswithmolecularoxygen,O2,accordingtotheequation ,formationofthemetaloxideMO
occursthroughtransferofelectrons(e)fromthemetalatom:

totheoxygenatom:

Hence:

Bytakinguptwoelectrons,oxygenacquiresacompletelyfilledvalenceshellwitheightelectrons.Ontheotherhand,thereversereaction
(removalofoxygenfromthemetaloxidetogivethemetalinitselementalform)wasdescribedasreduction.

Onlymuchlaterdidchemistsrealisethatthereactionsofoxygenconstituteaspecialcaseofamoregeneralphenomenon,oneinwhich
electronsaretransferredfromonesubstancetoanother.Forexample,thereactionbetweensodiumandchlorinetogivesodiumchloride
proceedsthroughtransferofelectronsfromsodium(oxidationofsodium)tochlorine(reductionofchlorine):

Noticethattheelectronappearsasaproductiftheprocessisoxidationandasareactantiftheprocessisreduction.

Basedonourunderstandingofthisprocess,wedefineoxidationasthelossofelectrons.Anoxidisingagent(oroxidant)isthenasubstancethat
hastheabilitytoremoveelectronsfromasubstance.Reductionisthegainofelectrons.Areducingagent(orreductant)isasubstancewiththe
abilitytodonateelectronstoanothersubstance.Thus,theoxidisingagentisinfactreduced,andthereducingagentisoxidised.Collectively,
electrontransferreactionsarecalledreductionoxidationreactionsorredoxreactions.

Redoxreactionsaresummarisedinthefollowingequation:

Tohelpremember,thinkofthemnemonicOILRIG,whichstandsforoxidationisloss,reductionisgain.Sincepositiveandnegativecharges
mustalwaysbebalancedinareaction,oxidationandreductionalwaysoccurtogether.Nosubstanceiseveroxidisedunlesssomethingelseis
reduced,andthetotalnumberofelectronslostbyonesubstanceisalwaysthesameasthetotalnumbergainedbytheother.Inthereactionof
sodiumwithchlorine,forexample,theoverallreactionis:

Whentwosodiumatomsareoxidised,twoelectronsarelost,whichisexactlythenumberofelectronsgainedwhenoneCl2moleculeisreduced.

WORKEDEXAMPLE12.1

IdentifyingReductionoxidation
Thebrightlightproducedbythereactionbetweenmagnesiumandoxygenisoftenusedinfireworksdisplays(figure12.1).The
productofthereactionismagnesiumoxide,MgO:

Whichelementisoxidisedandwhichisreduced?Whataretheoxidisingandreducingagents?

FIGURE12.1Thereactionbetweenmagnesiumandoxygenproducesbrightwhitelight.STYiap

Analysis

Magnesiumoxideisanionicsubstanceconsistingofametalandanonmetal.Thelocationsoftheelementsintheperiodictable
(groups2and16)tellusthattheionsinMgOareMg 2+andO2.
 Solution

Whenamagnesiumatombecomesamagnesiumion,itmustlosetwoelectrons:

Becausemagnesiumisoxidised,itmustbethereducingagent.OxygencangainthesetwoelectronstogiveanO2ion:

O2isreducedandsoitmustbetheoxidisingagent.

Isouranswerreasonable?

Therearetwothingswecandotocheckouranswers.First,wecanchecktobesurethatwehaveplacedelectronsonthecorrect
sidesoftheequations.Aswithionicequations,thenumberofatomsofeachkindandnetchargemustbethesameonbothsides.We
seethatthisistrueforbothequations.(Ifwehadplacedtheelectronsonthewrongside,thechargeswouldnotbalance.)As
oxidationreactionsalwayshaveelectronsontherighthandside,andreductionreactionsalwayshaveelectronsonthelefthandside,
byobservingthelocationsoftheelectronsintheequations,wecometothesameconclusionsthatMgisoxidisedandO2isreduced.

Anothercheckisnotingthatwehaveidentifiedonesubstanceasbeingoxidisedandtheotherasbeingreduced.Ifwehadmadea
mistake,wemighthavefoundthatbothwereoxidised,orbothwerereduced.Thatisimpossiblebecause,ineveryreactioninwhich
thereisoxidation,theremustalsobereduction,andviceversa.

PRACTICEEXERCISE12.1
Identifythesubstancesoxidisedandreducedandtheoxidising
andreducingagentsinthereactionofcopperandchlorineto
formCuCl2.

OxidationNumbers
Thereactionofmagnesiumwithoxygeninworkedexample12.1isclearlyaredoxreaction.However,notallreactionswithoxygenproduce
ionicproducts.Forexample,thereactionofsulfurwithoxygenisaredoxreaction,buttheproductsulfurdioxide,SO2,iscovalent.Tohelpus
followelectrontransfersinsuchreactions,weusetheconvenientconceptoftheoxidationnumber.(Notethatoxidationnumbersincovalent
compoundsareusedforconvenienceandshouldnotbemisinterpretedasioniccharges.)Theoxidationnumber(oroxidationstate)isthe
hypotheticalchargethatanatominamoleculewouldpossessifthesharedelectronpairsineachcovalentbondwereassignedtothemore
electronegativeelementinthebond.Thus,theoxidationnumberisthechargethateachatomwouldhaveifthecompoundweredividedinto
monatomicions.

Theoxidationnumberofanelementinaparticularcompoundisassignedaccordingtothefollowingsetofrules.
1.Theoxidationnumberofanyfreeelement(anelementnotcombinedchemicallywithadifferentelement)is0.Forexample,Ar,Fe,Oin
O2,PinP4andSinS8allhaveoxidationnumbersof0.
2.Theoxidationnumberforanysimple,monatomicion(e.g.Na+andCl)isequaltothechargeontheion.
3.Thesumofalltheoxidationnumbersoftheatomsinaneutralmoleculemustequalzero.Thesumofalltheoxidationnumbersina
polyatomicionmustequalthechargeontheion.
4.Inallofitscompounds,fluorinehasanoxidationnumberof1.
5.Inmostofitscompounds,hydrogenhasanoxidationnumberof+1.
6.Inmostofitscompounds,oxygenhasanoxidationnumberof2.

Inadditiontothesebasicrules,someotherchemicalknowledgeisrequired.Asshowninchapter4,theperiodictablecanbeusedtodetermine
thechargesoncertainionsoftheelements.Forinstance,allthemetalsingroup1formionswitha1+charge,andallthoseingroup2formions
witha2+charge.Thismeansthatwhenwefindsodiuminacompound,wecanassignitanoxidationnumberof+1becauseitssimpleion,Na+,
hasachargeof1+.Similarly,calciuminacompoundexistsasCa2+andhasanoxidationnumberof+2.Inbinaryioniccompoundswithmetals,
thenonmetalshaveoxidationnumbersthatareequaltothechargesontheiranions.Forexample,thecompoundFe2O3containstheoxideion,
O2,whichisassignedanoxidationnumberof2.Similarly,Mg 3P2containsthephosphideion,P3,whichhasanoxidationnumberof3.

Itisimportanttorealisethattheoxidationnumberdoesnotactuallyequalachargeonanatom.Todifferentiateoxidationnumbersfromactual
electricalcharges,thefollowingconventionisusedoxidationnumbersaregivenwiththesignbeforethenumber,whereaselectricalcharges
specifythesignafterthenumber.Forexample,thesodiumionhasachargeof1+andanoxidationnumberof+1.Inamolecularformula,
oxidationnumbersareplacedasasmallArabicnumeralabovethecorrespondingelementsymbol:
Sometimesitisconvenienttospecifytheoxidationnumberofanelementwhenitsnameiswrittenout.Thisisdonebywritingtheoxidation
numberasaRomannumeralinparenthesesafterthenameoftheelement.Forexample,iron(III)meansironwithanoxidationnumberof+3.

Thenumberedrulesgivenonthepreviouspageusuallycomeintoplaywhenanelementcanhavemorethanoneoxidationnumber,suchas
transitionmetals.IroncanformFe2+andFe3+ionsso,inanironcompound,theruleshelptodeterminewhichoneispresent.Nonmetalscan
alsoexhibitmorethanoneoxidationnumber,especiallywhentheyarecombinedwithhydrogenandoxygenincompoundsorpolyatomicions,
andtheiroxidationnumbersmustbecalculatedusingtherules.

WORKEDEXAMPLE12.2

AssigningOxidationNumbers
Molybdenumdisulfide,MoS2,hasastructurethatallowsittobeusedasadrylubricant,muchlikegraphite.Whataretheoxidation
numbersoftheatomsinMoS2?

Analysis

Thisisabinarycompoundofametalandanonmetalso,forthepurposesofassigningoxidationnumbers,weassumeittocontain
ions.Molybdenumisatransitionmetal,sothereisnosimpleruletotellwhatitsionsare.However,sulfurisanonmetalingroup16,
anditsionisS2.

Solution

BecauseS2isasimplemonatomicion,itschargeequalsitsoxidationnumber,sosulfurhasanoxidationnumberof2.Nowwecan
userule3(thesummationrule)todeterminetheoxidationnumberofmolybdenum,whichwewillrepresentbyx.

Thevalueofxmustbe+4forthesumtobe0.Therefore,theoxidationnumbersareMo=+4andS=2.

PRACTICEEXERCISE12.2
Assignoxidationnumberstoeachatomin(a)NiCl2,(b)
Mg 2TiO4,(c)K2Cr2O7,(d) ,(e)(NH4)2Ce(NO3)6,(f)
K4[Fe(CN)6]and(g)Na3[Fe(CN)6].

Someclassesofcompoundshaveatomsinoxidationstatesthatareexceptionstotherulesonp.491,butthesearerare.Theusualexamplesare
theoxygenatomsinperoxides(forexample,inhydrogenperoxide,H2O2,whichisusedforbleachinghair,theoxygenatomshaveanoxidation
numberof1,insteadof2)andthehydrogenatomsinhydrides(forexample,incalciumhydride,CaH2,thehydrogenatomshaveanoxidation
numberof1,insteadof+1).Oxidationnumberscalculatedbytherulesonp.491canhavefractionalvalues(forexample,thenitrogenatomsin
theioniccompoundsodiumazide,NaN3(seefigure12.2),haveanoxidationnumberof ).

FIGURE12.2Theairbagsusedassafetydevicesinmoderncarsareinflatedbytheexplosivedecompositionofsodiumazide,whichgiveselemental
sodiumandgaseousnitrogenthroughthereaction:

Sodiummetal,whichishighlyreactive,isconvertedintoaharmlesssilicateglassthroughreactionwithadditives,suchaspotassiumnitrate
andsilicondioxide.Becauseofthehightoxicityofsodiumazide,itisnowsometimesreplacedbylessharmfulnitrogenrichcompounds,such
astetrazoles(fivememberedringswithonecarbonandfournitrogenatoms).RichardOlivier

Usingtheconceptofoxidationnumbers,wecannowviewaredoxreactionasachemicalreactioninwhichchangesinoxidationnumbers
occur.Oxidationisanincreaseinoxidationnumber.Reductionisadecreaseinoxidationnumber.

WORKEDEXAMPLE12.3

UsingOxidationNumberstoAnalyseRedoxReactions
Identifythesubstanceoxidisedandthesubstancereducedaswellastheoxidisingandreducingagentsinthereaction:

Analysis

Toidentifytheredoxspecies,weneedtoconsiderwhatishappeningwiththeoxidationnumbers.Thiswilltelluswhatisoxidised
andreduced.Thenwerecallthatthesubstanceoxidisedisthereducingagent,andthesubstancereducedistheoxidisingagent.

Solution

Toidentifyredoxchangesusingoxidationnumbers,wefirstassignanoxidationnumbertoeachatomonbothsidesoftheequation:

Nextwelookforchanges,keepinginmindthatanincreaseinoxidationnumberisoxidationandadecreaseisreduction.

Thus,theClinKClisoxidisedandtheMninMnO2isreduced.ThereducingagentisKClandtheoxidisingagentisMnO2.(Notice
that,inidentifyingtheoxidisingandreducingagents,wespecifytheentireformulaeforthesubstancescontainingtheatoms
changingoxidationnumbers.)

Isouranswerreasonable?

Therearelotsofthingswecouldcheckhere.Wehavefoundchangesthatleadustoidentifyanoxidationandareductionprocess
thisgivesusconfidencethatwehavedonetherestoftheworkcorrectly.

PRACTICEEXERCISE12.3
Thereactionofconcentratedhydrochloricacid,HCl,with
potassiumpermanganate,KMnO4,isaconvenientmethodof
preparingchlorinegasinthelaboratory:

Identifythesubstancesoxidisedandreducedaswellasthe
oxidisingandreducingagentsinthisreaction.

ChemicalConnections

BiologicalRedoxProcesses

Redoxreactionsareextremelyimportantinmetabolicprocesses.ManyoftheseprocessesinvolvethebreakingofCHbondsandthe
transferoftwoelectronsfromCtoanelectronacceptor.Often,inbiologicalprocesses,theredoxprocessinvolvesenzymesandthe
electronsaretransferredtooxygen.Consider,forexample,theredoxprocessshownbelow.
Inthisprocessglutathionedisulfide(GSSG)isreducedtothetripeptide(seechapter24)glutathione(LglutamylLcysteinylglycine,
GSH).GSHisareducingagent(antioxidant)thathelpstoprotectcellsfrompotentiallydamagingreactiveoxygenspecies,suchas
oxygenradicalsandperoxides.Thisprocessiscatalysedbyglutathionereductase.Glutathionereductasecontainsflavinadenine
dinucleotide(FAD),whichactsastheelectrontransfergroup.Generally,electrontransfersinvolvingflavinscanoccurintwoways:
TwosequentialoneelectrontransferprocessesinvolvingthesemiquinoneorradicalformFADHandthefullyreducedor
hydroquinoneformFADH2,i.e.FADFADHFADH2(theredpathwayshownbelow).
Asimultaneoustwoelectrontransfer,i.e.FADFADH2,whichdoesnotinvolvethesemiquinoneintermediateFADH(the
greenpathwayshownbelow).

Photosynthesis

Anotherimportantbiologicalredoxprocessisphotosynthesis.Theenergywegainfromthefoodweeatandthefossilfuelsweburn
canultimatelybetrackedbacktothecomplicatedbiochemicalprocessofphotosynthesis.Photosynthesisconvertstheenergyin
sunlightintochemicalenergythatbiologicalsystemscanuse.Itoccursinmanyplantsaswellasinsomebacteria.
PhotosynthesisisacomplexseriesofcoordinatedredoxreactionsbuttheoveralleffectistoreducegaseousCO2tocarbohydrates(ifx
=6,thecarbohydrateismostcommonlyglucose)andtooxidiseH2Otooxygen.

Thephotosyntheticprocesstakesplaceincompartments,ororganelles,knownaschloroplasts.Theprocesshastwocomponents:light
reactionsanddarkreactions.Thelightreactionsuseenergyfromlighttocreatethesubstancesrequiredforthedarkreactions.The
absorptionoflightenergyoccursintwotypesofreactioncentresinstructuresknownasthylakoidswithinthechloroplasts.Thereaction
centresarecalledphotosystemI(PSI)andphotosystemII(PSII)(figure12.3).

FIGURE12.3Thisschemeshowshowelectronsareshuttledthroughanelectrontransportchaininthelightdrivencomponentofphotosynthesis.

InPSII,thepigmentchlorophyll(whichiswhatmakesplantsgreen)andseveralotheraccessorypigments,includingcarotenesand
xanthophylls,absorblightandpassitsenergytoacentralchlorophyllcomplexknownasP680.Theenergyoxidisesthecentral
chlorophyllcomplex,releasingelectrons.Thistriggersaseriesofredoxreactions,whereelectronsareshuttledthoughanelectron
transportchain.

Theelectronsreleasedfromthechlorophyllcomplexarereplacedbyelectronsfromtheoxidationofwater.

TheelectronsreleasedfromchlorophyllinPSIIflowtothecytochromeb 6fcomplex(cytb 6f)withinthethylakoidmembranevia

anothercomplexcalledplastoquinone(figure12.4).Thisflowgeneratesaprotongradient(abuildupofpositivechargeononesideof
themembrane).Thechargedifferentialacrossthemembranethenpowersthesynthesisofthehighenergymoleculeadenosine
triphosphate,ATP,fromadenosinediphosphate,ADP,andinorganicphosphate,Pi,catalysedbytheenzymeATPsynthaseaccording
totheequation:

ATPisoneofthesubstancesusedinthedarkreactions.

FIGURE12.4Overviewofphotosyntheticprocessesastheyoccurinplants,algaeandcyanobacteria.

Electronsfromcytb 6faretransferredtoPSI.AtthechlorophyllcomplexinPSI(P700),energyfromlightexcitestheelectronstoa
higherenergystate.TheelectronsreduceNADP+toNADPHinareactioncatalysedbytheenzymeNADPreductaseaccordingtothe
equation:
 Thedarkreactions(alsocalledtheCalvinBensoncycle)thenuseNADPHandATPtoproduceglyceraldehyde3phosphate(G3P)
fromCO2andH2Oaccordingtotheequation:

G3Pisathreecarbonsugarfromwhichothercarbohydrates(suchasglucose)areproducedthroughsubsequentmetabolicprocesses.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.2BalancingNetIonicEquationsforRedox
Reactions
Manyredoxreactionstakeplaceinaqueoussolutionandmanyoftheseinvolveionstheyareionicreactions.
Instudyingredoxreactions,itisoftenhelpfultowriteionicandnetionicequations.Wedothisbydividing
theoxidationandreductionprocessesintoindividualequationscalledhalfequations,whicharethen
balancedseparately.Wecombinethebalancedhalfequationstoobtainthefullybalancednetionicequation.

Toillustratethemethod,wewillbalancethenetionicequationforthereactionofiron(III)chloride,FeCl3,
withtin(II)chloride,SnCl2,inaqueoussolution,whichchangestheFe3+toFe2+andtheSn 2+toSn 4+.Inthe
reaction,thechlorideionisunaffecteditisaspectatorion.

Webeginbywritinganequationthatshowsonlythespeciesinvolvedinthereaction.Inthiscase,the
reactantsareFe3+andSn 2+,andtheproductsareFe2+andSn 4+.Theequationistherefore:

Notethat,whiletheequationisbalancedintermsofmass,itisnotyetbalancedintermsofchargeoneither
sideofthearrow.Tobalancethisequationintermsofbothmassandcharge,wemustfirstidentifythe
reactantandproductofthetwohalfequations:

Next,webalancethehalfequationssothateachobeysbothcriteriaforabalancedionicequationbothatoms
andchargehavetobalance.Obviously,theatomsarealreadybalancedineachequation.Thecharge,
however,isnot.Weaddelectronsasnecessarytobalancethecharges.Forthefirsthalfequation,two
electronsareaddedtotheright,sothenetchargeonbothsideswillbe2+.Inthesecondhalfequation,one
electronisaddedtotheleft,whichmakesthenetchargeonbothsidesequalto2+.

Notethatanoxidationhalfequationwillalwayshavetheelectronsontherighthandsideandareduction
halfequationwillalwayshavetheelectronsonthelefthandside.Therefore,thefirsthalfequation
correspondstoanoxidationreactionandthesecondtoareductionreaction.

Inanyoverallredoxreaction,thenumberofelectronsgainedalwaysequalsthenumberlost.Giventhattwo
electronsarelostbySn 2+intheoxidationprocess:

twoelectronsmustbeusedinthereductionprocess.Therefore,weneedtomultiplyeachofthecoefficients
inthereductionhalfequationby2:

Wecombinethebalancedhalfequationsbyaddingthemtogive:

Finally,wenotethattwoelectronsappearoneachsideoftheequation.Wecancancelthesetogivethefinal
balancedequation:

Noticethatboththechargeandthenumberofeachtypeofatomarenowbalanced.

PRACTICEEXERCISE12.4
Balancethefollowingredoxequation:

RedoxReactionsinAcidicandBasicSolutions

Inmanyredoxreactionsinaqueoussolutions,H3O+orOHionsplayanimportantrole,asdowater
molecules.Forexample,whensolutionsofK2Cr2O7andFeSO4aremixed,theacidityofthemixture
decreasesasthereactionproceeds,asdichromateions,Cr2O72,oxidiseFe2+.Thisisbecausethereaction
usesupH3O+asareactantandproducesH2Oasaproduct.Inotherreactions,OHisconsumed,whileinstill
othersH2Oisareactant.Also,inmanycases,theproducts(oreventhereactants)ofaredoxreactionwill
dependontheacidityofthesolution.Forexample,inanacidicsolution,MnO4isreducedtoMn 2+ions,but
inaneutralorslightlybasicsolutionthereductionproductisinsolubleMnO2,withMnhavinganoxidation
numberof+4.Wewillfirstlearnhowtobalanceacidicsolutions.Balancingbasicsolutionsusesthesame
conceptsbutrequiresanadditionalstepattheendtoensurethatthefinalequationdoesnotshowH+.

AcidicSolutions

Cr2O72(orangered)reactswithFe2+(almostcolourless)inanacidicsolutiontogiveCr3+(green)andFe3+
(orange)asproducts(figure12.5).Therefore,theequationwemustbalanceis:

TheoxidationnumberofCrinCr2O72is+6.
 FIGURE12.5AsolutionofK2 Cr2 O7 beingaddedtoanacidicsolutioncontainingFe2+.Notethegreenorangeswirl
ofproducts.PeterLerman

Thebalancedequationcanbefoundthroughthefollowingsteps.
Step1:Identifythereactantandproductofeachoftheoxidationandreductionprocesses.

Step2:BalanceatomsotherthanHandO.
TherearetwoCratomsontheleftandonlyoneontheright,soweplaceacoefficientof2infrontof
Cr3+.Theoxidationhalfequationisalreadybalancedintermsofatoms.

Step3:BalanceoxygenbyaddingH2O.
Therearesevenoxygenatomsontheleftofthereductionhalfequationandnoneontheright.Therefore,
weadd7H2Ototherightsideofthereductionhalfequation.

Step4:BalancehydrogenbyaddingH+.Notethat,forsimplicity,weuseH+,ratherthanH3O+,when
balancingredoxequations.
Afteraddingthewater,weseethatwehavecreatedanimbalancethefirsthalfequationhas14hydrogen
atomsontherightandnoneontheleft.Tobalancethese,weadd14H+totheleftsideofthehalf
equation.

Noweachhalfequationisbalancedintermsofnumberandtypeofatomsinvolved.Nextwewillbalance
thecharge.
Step5:Balancethechargebyaddingelectrons.
Firstwecalculatethenetchargeoneachside.Forthereductionhalfequation,wehave:

Tobalancethenetcharge,weneedtoaddsixelectronstothelefthandsideofthehalfequation.Recall
that,inbalancedreductionhalfequations,electronsalwaysappearonthelefthandside.

Tobalancetheoxidationhalfequation,weneedtoaddoneelectrontotheright.

Step6:Makethenumberofelectronsgainedequaltothenumberlost.
Atthispointwehavethetwobalancedhalfequations:
Becausesixelectronsaregainedinthereductionprocess,butonlyoneislostintheoxidationprocess,we
multiplyallofthecoefficientsoftheoxidationhalfequationby6.

Step7:Addthebalancedhalfequations.

Step8:Cancelanyspeciesthatisthesameonbothsides.
Cancelsixelectronsfrombothsidestogivethefinalbalancedequation:

Step9:Checkthatthefinalequationisbalancedintermsofnumberandtypeofatomsandcharge.In
step4,weusedH+insteadofH O+.IfyouwanttoexpressyourequationwithH O+,takenoteofthe
3 3
numberofH+inthebalancedequationsandaddthesamenumberofH Otoboth sides.Thencombine
2
H+andH OasH O+.
2 3

Summaryofthestepsforbalancinganequationforaredoxreactioninanacidicsolution
Step1:Identifyreactantsandproductsforeachhalfequation.
Step2:BalanceatomsotherthanHandO.
Step3:BalanceoxygenbyaddingH2O.

Step4:BalancehydrogenbyaddingH+.
Step5:Balancenetchargebyaddinge.
Step6:Makeegainequaleloss.
Step7:Addthebalancedhalfequations.
Step8:Cancelanyspeciesthatisthesameonbothsides.
Step9:Checkthattherearethesamenumberandtypeofatomsandthesamechargeoneachside
ofthereaction.

WORKEDEXAMPLE12.4

BalancingRedoxEquationsinAcidicSolutions
Balancethefollowingequation.Thereactionoccursinacidicsolution.

Solution

Wefollowthestepsjustgiven.TheoxidationnumberofMninMnO4is+7,ofSinH2SO3is+4
andofSinSO42is+6.
Step1:Identifythereactantsandproductsofthereductionandoxidationprocesses.

Step2:Thereisnothingtodoforthisstep.AlltheatomsexceptHandOarealreadybalanced.
Step3:AddH2Otobalanceoxygen.

Step4:AddH+tobalancehydrogen.

Step5:Balancethechargebyaddingelectrons.

Step6:Makeelectronlossequaltoelectrongainbymultiplyingthefirstequationby2andthe
secondequationby5.

Step7:Addthebalancedhalfequations.

Step8:Cancel10e,16H+and5H2Ofrombothsides.Thefinalequationis:

Isouranswerreasonable?

Thisisstep9.Thecheckissimple.Noticethateachsideoftheequationhasthesamenumberof
atomsofeachelementandthesamenetcharge.Thisiswhatmakesitabalancedequationand
confirmsthatwehavecompletedtheproblemcorrectly.

PRACTICEEXERCISE12.5
Theelementtechnetium(atomicnumber43)is
radioactiveoneofitsisotopes,99mTc,isusedin
medicinefordiagnosticimaging.Theisotopeis
usuallyobtainedintheformofthepertechnetate
anion,TcO4,butitsusesometimesrequiresthe
 technetiumtobeinaloweroxidationstate.
ReductioncanbecarriedoutusingSn 2+inan
acidicsolution.Theequationis:

Balancetheequation.

BasicSolutions

Inbasicsolutions,thedominantspeciesareH2OandOH.Strictlyspeaking,theseshouldbeusedtobalance
thehalfequations.However,thesimplestwaytoobtainabalancedequationforabasicsolutionistofirst
balanceitasifitwereinacidicsolution.Webalancetheequationusingtheninestepsjustdescribed,and
thenweusethefourstepproceduredescribedbelowtoconverttheequationtothecorrectformforabasic
solution.TheconversionusesthefactthatH+andOHreactina1:1ratiotogiveH2O.

Additionalstepsforbalancinganequationforaredoxreactioninabasicsolution
Step10:TakenoteofthenumberofH+inthebalancedequationandaddthesamenumberof
OHtoeach side.

Step11:CombineeachpairofH+andOHtoformoneH2O.
Step12:CancelanyH2Omoleculesthatoccuronbothsides.
Step13:Checkthattherearethesamenumberandtypeofatomsandthesamechargeoneach
sideofthereaction.

Asanexample,supposewewantedtobalancethefollowingequationinabasicsolution:

Followingsteps1to9foracidicsolutionsgives:

Conversionofthisequationtooneappropriateforabasicsolutionproceedsasfollows.
Step10:TakenoteofthenumberofH+inthebalancedequationandaddthesamenumberofOHto
eachside.
Theequationforanacidicsolutionhas2H+ontheleft,soweadd2OHtoeachside.

Step11:CombineH+andOHtoformH2O.
Theleftsidehas2OHand2H+,whichbecome2H2O.

Step12:CancelanyH2Omoleculesthatoccuronbothsides.
Inthisequation,oneH2Ocanbeeliminatedfrombothsides.Thefinalequation,balancedinabasic
 solution,is:

Step13:Checkthattheequationisbalancedintermsofnumberandtypeofatomsandcharge.

PRACTICEEXERCISE12.6
Balancethefollowingequationinabasic
solution.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.3GalvanicCells
Fromthepreviousdiscussion,itisobviousthatinchemicalprocessesanoxidationcannotoccurwithouta
simultaneousreduction,andviceversa.Thisisbecauseonesubstancehastoreleaseelectrons(thereducing
agent,whichbecomestheoxidisedspeciesafterthereaction),whichhavetobetakenupbyanother
substance(theoxidisingagent,whichbecomesthereducedspeciesafterthereaction).Becauseaspecific
substancecannotdonateelectronstoortakeupelectronsfromeveryothercompound,noabsoluteoxidising
orreducingagentsactuallyexist.Infact,whetherasubstanceactsasanoxidantorreductantinareaction
dependsonthenatureofthereactionpartnertobeoxidisedorreduced,respectively.Wewillillustratethis
withthreeexamples.

Example1
Ifastripofmetalliczincisdippedintoasolutionofcoppersulfate,areddishbrowndepositofmetallic
copperformsonthezinc(seefigure12.6).Analysisofthesolutionrevealsthatitnowcontainszincions,as
wellassomeremainingunreactedcopperions.

FIGURE12.6 Thereactionofzincwithcopperions:
(a)Apieceofshinyzincnexttoabeakercontainingacoppersulfatesolution.
(b)Whenthezincisplacedinthesolution,copperionsarereducedtoelementalcopperwhilethe
zincdissolves.
(c)Afterawhile,thezincbecomescoatedwitharedbrownlayerofcopper.Thebluecolourofthe
solutionfadesasCu2+isreduced.

Zinctransferselectronstocopperions,andtheresultsofthisexperimentcanbesummarisedbytheequation:

Theterm(aq)expressesthefactthatthemoleculesorionsaredissolvedinwater,wheretheybecome
surroundedbywatermolecules(hydration).

Theredoxchangesbecomeclearifbothhalfequationsareanalysed.Bothcoppersulfateandzincsulfateare
solublesalts,andtheyarecompletelydissociated.Thesulfateionisaspectatorionandnotinvolvedinthe
redoxprocess.

Anatomiclevelviewoftheprocessesatthesurfaceofzincduringthereactionisdepictedinfigure12.7.
 FIGURE12.7 Thereactionofcopperionswithzinc,viewedattheatomiclevel:
(a)Copperions(palebrown)collidewiththezincsurfacewheretheypickupelectronsfromzinc
atoms(grey).Thezincatomsbecomezincions(yellow)andenterthesolution.Thecopper
ionsbecomecopperatoms(redbrown)andsticktothesurfaceofthezinc.(Forclarity,the
watermoleculesofthesolutionandthesulfateionsarenotshown.)
(b)Acloseupviewoftheexchangeofelectronsthatleadstothereaction.

Example2
Incontrasttoexample12.3.1,whenapieceofcopperisdippedintoasolutionofzincsulfate(seefigure
12.8),noreactionoccurs.Coppercannotreducethezincionstometalliczinc.

FIGURE12.8Coppercannotreducezincions.Althoughmetalliczincwilldisplacecopperfromasolutioncontaining
Cu2+ions,metalliccopperwillnotdisplaceZn2+fromitssolutions.Hereweseethatthecopperbaris
unaffectedbybeingdippedintoasolutionofzincsulfate.

Example3
Whenacoilofcopperisdippedintoasolutionthatcontainssilverions,thesearereducedtoelementalsilver
andcopperisoxidised(seefigure12.9).Theredoxprocessesare:
 FIGURE12.9 Reactionofcopperwithasolutionofsilvernitrate.
(a)Acoilofcopperwirestandsnexttoabeakercontainingasilvernitratesolution.
(b)Whenthecopperwireisplacedinthesolution,copperdissolves,givingthesolutionitsblue
colour,andmetallicsilverdepositsasglitteringcrystalsonthewire.
(c)Afterawhile,muchofthecopperhasdissolvedandnearlyallofthesilverhasdepositedinits
elementalform.

Togaininsightsintothedifferentoxidisingandreducingbehavioursofthesesubstances,thedrivingforceof
theelectrontransferneedstobeunderstood.Thefindingthat,inexample12.3.1,anelectricalcurrent
(movingelectrons)flowsbetweenthezincandcoppersystemsmeansthatapotentialdifferenceexists
betweenthetwosystems.(Rememberthatacurrent,e.g.water,heat,gasandelectriccurrent,canflowonly
ifadifferenceinlevelofheight,temperature,pressureorpotentialexists.)

Thepotentialdifferenceisexpressedintheelectricalunitvolt(V),whichisameasureoftheamountof
energy,injoules(J),thatcanbedeliveredperSIunitofcharge,coulomb(C),asthecurrentmovesthrough
acircuit.Thus,acurrentflowingunderapotentialdifferenceof1voltcandeliver1jouleofenergyper
coulomb.

SettingUpaGalvanicCell
Thepotentialdifferencebetweenzincandcoppercannotbedeterminedexperimentallysimplybydipping
zincmetalintoasolutionofcopperions,becausetheelectrontransfertakesplacedirectlybetweenCu 2+and
Zn,asshowninfigure12.7.Instead,ifazincrod(electrode)isdippedintoasolutionofZnSO4andacopper
rod(electrode)isdippedintoasolutionofCuSO4,andthesolutionsareconnectedwithasaltbridge(its
functionwillbedescribedshortly),zinccantransferitselectronstothecopperionsonlythroughanexternal
circuit(seefigure12.10a).Anarrangementwhereametal,M,isdippedintoasolutioncontainingasaltof
therespectivemetalion,Mn+Xn,(ifXisamonoanion)iscalledahalfcell.Inahalfcell,oxidationand
reductioncanoccuraccordingtothisequilibrium:
 FIGURE12.10 Galvaniccells.
(a)Thezinccoppercelland
(b)thesilvercoppercell.At25Cunderstandardconditions(1105 Paandconcentrationof
1Mforallsolutes),thepotentialis1.10Vinthezinccoppercelland0.46Vinthesilver
coppercell.

Thechemicalprocessisidenticaltothatinexample12.3.1(seep.500andfigure12.6).However,inthis
case,theexistingpotentialdifferencecanbemeasuredusingahighlysensitivecurrentmeterorbyinserting
avoltmeterwithaveryhighresistance.Suchacombinationoftwohalfcellsiscalledagalvaniccell(after
LuigiGalvani,17371798,anItaliananatomistwhodiscoveredthatelectricitycancausethecontractionof
muscles).Theoverallreactionthattakesplaceinthegalvaniccellisthecellreaction.

Inthezinccoppersystem,ifthesolutionshaveaconcentrationof1.00MCu 2+and1.00MZn 2+,the

potentialdifference,orelectrochemicalpotential,is1.10V.Thepotentialdifferencebetweentheelectrodes
canbecomparedwiththepressuredifferencebetweentwogascontainersfilledwithgasatdifferent
pressures.Ifbothcontainerswereconnected,thepressureinthesystemwouldbeequalisedbygasflow
fromthecontainerwiththehigherpressuretothecontainerwiththelowerpressure.Inagalvaniccell,the
electrongasflowsfromtheelectrodewiththehigherelectronpressure(zinc)totheelectrodewiththe
lowerelectronpressure(copper),whichisindicatedbythedirectionofthearrowabovethevoltmeterin
figure12.10a.Thus,thepotentialdifferenceisameasureoftheelectronpressuredifferencebetweentwo
electrodes.TheredoxreactionbetweenZnandCu 2+(example12.3.1)isfinishedwhentheelectron
pressuresbetweenzincandcopperareinequilibrium.Inmanytextbooks,thepotentialdifferenceina
galvaniccelliscalledelectromotiveforce.Thistermisdiscouraged,sincepotentialdifferenceisnota
force.Theunitofpotentialdifferenceinagalvaniccellisthevolt(V).

WhenacopperelectrodeinasolutionofCu(NO3)2isconnectedtoasilverelectrodeinasolutionofAgNO3,
thecurrentflowsintheoppositedirection(seefigure12.10b).WhentheconcentrationsoftheCu(NO3)2and
AgNO3solutionsare1.00m,thepotentialdifferenceis0.46V.Likewise,azincelectrodeinasolutionof
ZnSO4connectedtoasilverelectrodeinasolutionofAgNO3willformagalvaniccellwithapotential
differenceof1.56V(thesumofthepotentialdifferencesofthetwopreviouslydiscussedgalvaniccells,1.10
V+0.46V=1.56V)andinwhichtheelectronsflowfromthezincelectrodetothesilverelectrode.Wewill
explainthisfindinglater.

ProcessesinGalvanicCells
Aswehaveseen,aredoxsystemconsistingoftwometalsandsolutionsoftheirsalts(twohalfcells)canbe
combinedtoformagalvaniccell,whichproduceselectricity.Inotherwords,agalvaniccellconsistsofan
oxidisingagentinonecompartment(thefirsthalfcell)thatpullselectronsthroughawirefromareducing
agentintheothercompartment(theotherhalfcell).

Wewillnowhaveacloserlookattheprocessesoccurringingalvaniccells.Theprocessesinvolvedare
describedaselectrochemicalchanges,andthestudyofsuchchangesiscalledelectrochemistry.Figure
12.11showsschematicallytheprocessesthattakeplaceinthetwohalfcellsofthecoppersilvergalvanic
cell.Atthecopperelectrode,Cu 2+ionsenterthesolutionwhencopperatomsareoxidised,leavingelectrons
behindontheelectrode.Thesolutionaroundthecopperelectrodebecomespositivelycharged,unlessCu 2+
ionsmoveawayfromtheelectrodeorNO3ionsmovetowardsit.Atthesilverelectrode,Ag +ionsleavethe
solutionandbecomesilveratomsbyacquiringelectronsfromtheelectrodesurface.Thesolutionaroundthe
silverelectrodebecomesnegativelycharged,unlessmoreAg +ionsmovetowardstheelectrodeorNO3ions
moveaway.
 FIGURE12.11Changesthattakeplaceattheanodeandcathodeinthecoppersilvergalvaniccell(notdrawnto
scale).

Inanyelectrochemicalsystem,theelectrodeatwhichoxidationoccursiscalledtheanodetheelectrodeat
whichreductionoccursiscalledthecathode.Thus,inthecoppersilvergalvaniccell,thesilverelectrodeis
thecathodeandthecopperelectrodeistheanode.Attheanode,Cu 2+isreleasedintothesolution.The
remainingelectronsgivetheanodeaslightnegativechargetheanodehasanegativepolarity.Atthe
cathode,electronsspontaneouslyjoinAg +ionstobecomeapartoftheelectrode.However,thiseffectisthe
sameasifAg +ionsbecomeapartoftheelectrode,sothattheelectrodeacquiresaslightpositivecharge.
Thecathodehasapositivepolarity.

IftheproductionofCu 2+attheanodeanddepositionofAg +atthecathodeweretocontinue,thesolution

aroundtheanodewouldquicklybecomepositivelychargedthesolutionaroundthecathodewouldacquire
anegativechargebecauseconsumptionofpositiveionsfromthesolutionwouldleaveanexcessofnegative
ions.

Naturedoesnotpermitlargeamountsofpositiveandnegativechargetoaccumulate,so,forthereactionsto
continueandforelectricitytocontinuetoflowthroughtheexternalcircuit,theremustbeameansof
balancingthechargesinthesolutionsaroundtheelectrodes.Tounderstandhowthishappens,wewill
examinehowelectricchargeisconductedinthecell.

Intheexternalcircuitofthecell,electricchargeistransportedfromoneelectrodetotheotherbythe
movementofelectronsthroughthewires.Thistypeofconductioniscalledelectronicconductionandis
howmetalsingeneral,andothermaterials,conductelectricity.Inthecell,electronsalwaystravelfromthe
negativelychargedanode,wheretheyareleftbehindbytheoxidationprocess,tothepositivelycharged
cathode,wheretheyarepickedupbythesubstancebeingreduced.
Inelectrochemicalcells,thereisanotherkindofelectricalconductionthatalsotakesplacetobalance
chargesinthetwohalfcells.Inasolutionthatcontainsions(orinamoltenioniccompound),electric
chargeiscarriedthroughtheliquidbythemovementofions,notelectrons.Thetransportofelectriccharge
byionsiscalledelectrolyticconduction.

Foragalvaniccelltowork,thesolutionsinbothhalfcellsmustremainelectricallyneutral.Thisrequiresthat
ionsbepermittedtoenterorleavethesolutions.Forexample,whencopperisoxidised,thesolution
surroundingtheelectrodebecomesfilledwithCu 2+ions,sonegativeionsareneededtobalancetheircharge.
Similarly,whenAg +ionsarereduced,NO3ionsareleftbehindinthesolutionandpositiveionsareneeded
tomaintainneutrality.Thesaltbridgeshowninfigure12.10allowsthemovementofionsrequiredtokeep
thesolutionsneutral.

Asaltbridgeisatubefilledwithasolutionofasaltcomposedofrelativelyinertionsthatarenotinvolved
inthecellreaction.OftenKNO3orKClareused.Inthemostsimplifiedversion,thetubeisfittedwitha
porousplugateachendthatpreventsthesolutionfrompouringoutbut,atthesametime,enablesthe
solutioninthesaltbridgetoexchangeionswiththesolutionsinthehalfcells.

Duringoperationofthecell,negativeionscandiffusefromthesaltbridgeintothecopperhalfcell,orCu 2+
ionscanleavethesolutionandenterthesaltbridge.Bothprocessestogetherkeepthecopperhalfcell
electricallyneutral.Atthesilverhalfcell,positiveionsfromthesaltbridgecanenterornegativeNO3ions
canleavethehalfcellalsotokeepthishalfelectricallyneutral,too.

Withoutthesaltbridge,electricalneutralitycouldnotbemaintainedandnoelectriccurrentcouldbe
producedbythecell.Therefore,electrolyticcontactcontactbymeansofasolutioncontainingions
mustbemaintainedforthecelltofunction.Acloserlookattheoverallionmovementduringtheoperation
ofthegalvaniccellshowsthatnegativeions(anions)moveawayfromthecathode,wheretheyarepresent
inexcess,towardstheanode,wheretheyareneededtobalancethechargeofthepositiveions(cations)
formed.Similarly,cationsmoveawayfromtheanode,wheretheyareinexcess,towardsthecathode,where
theybalancetheanionsleftinexcess.Insummary,ingalvaniccells:
Thecathodeistheelectrodeatwhichreduction(electrongain)occurs.Cationsmoveinthegeneral
directionofthecathode.
Theanodeistheelectrodeatwhichoxidation(electronloss)occurs.Anionsmoveinthegeneral
directionoftheanode.

Figure12.12providesasummaryofthecomponentsof,andprocessesin,abasicgalvaniccell.
 FIGURE12.12Schematicdiagramofagalvaniccell.Electronsalwaysflowfromthenegativeelectrode(anode)to
thepositiveelectrode(cathode).Inthisdiagram,theanodeisthelefthandelectrodeatwhich
oxidationoccurs,andthecathodeistherighthandelectrodewherereductionoccurs.

Afterthistheoreticaldescriptionofgalvaniccells,youmayperhapswonderwhereyouwouldencounter
galvaniccellsinyourdailylife.Basically,agalvaniccellcanbeconsideredasabattery,andwewilldiscuss
batterieslaterinthischapter.(Moreprecisely,abatteryconsistsofseveralgalvaniccells.)Butyoumayhave
alsocreatedanunwantedgalvaniccellinyourmouthifyouhaveoldfillingsinyourteeth,youmayhave
experiencedastrangeandperhapsunpleasantsensation,likeanelectricshock,whileaccidentallybitingona
pieceofaluminiumfoil.Mostoldfillingsaremadeofanamalgamofmercuryandsilver.Whenthe
aluminiumfoiltouchesthefilling,agalvaniccelliscreatedinthemouth,inwhichaluminiumistheanode,
thefillingisthecathodeandsalivaistheelectrolytesaltbridge.Inessence,thecontactshortcircuitsthe
galvaniccellandasmallamountofcurrentflows,whichissensedbythenervesintheteeth.

NotationofGalvanicCellsandCellReactions
Asamatterofconvenience,chemistsuseacelldiagramasashorthandwayofdescribingthemakeupofa
galvaniccell.Thecelldiagram,whichisalsoknownasstandardcellnotation,forthegalvaniccellinfigure
12.12is:

Byconvention,thehalfcellcontainingtheanodeisspecifiedontheleftofacelldiagram,withtheelectrode
materialoftheanodegivenfirst.Thesingleverticallinerepresentsaphaseboundaryhere,betweenthe
solidelectrodeandthesolutionthatsurroundsit.Thedoubleverticaldashedlinesrepresentthesaltbridge,
whichconnectsthesolutionsinthetwohalfcells.Ontheright,thehalfcellcontainingthecathodeis
described,withthematerialofthecathodegivenlast.Thedefinedcellreactionforanycelldiagramis
obtainedbasedonthefactthatreductionoccursattherighthandelectrode(cathode).Therefore,the
definedcellreactionforthecellinfigure12.12is:

Wewillseeinsection12.4howtodeterminewhetherthedefinedcellreactionoccursspontaneously.

Thecoppersilvercelldiscussedonp.503isrepresentedbythefollowingcelldiagram:
Sometimes,theoxidisedandreducedformsofthereactantsinahalfcellarebothinsolution.Forexample,a
galvaniccellcanbemadeusingananodichalfcellcomposedofazincelectrodedippingintoasolution
containingZn 2+andacathodichalfcellcomposedofaninert(nonreacting)platinumelectrodedippinginto
asolutioncontainingbothFe2+andFe3+(figure12.13).Thecellreactionis:

Thecelldiagramforthisgalvaniccellis:

wherewehaveseparatedtheformulaeforthetwoironionsbyacomma.Thisisdonewhenthespeciesare
inthesamephase.Inthiscell,thereductionofFe3+toFe2+takesplaceatthesurfaceoftheinertplatinum
electrode.

FIGURE12.13Thecathodichalfcellforthegalvaniccellrepresentedbythecelldiagramontheleft,showingthe
platinumgauzecathodeinasolutionofFe2+andFe3+.

WORKEDEXAMPLE12.5

DescribingGalvanicCells
Thefollowingspontaneousreactionoccurswhenmetalliczincisdippedintoasolutionofsilver
nitrate:
Describeagalvaniccellthatcouldtakeadvantageofthisreaction.Whatisthereactionineach
halfcell?Whatisthecelldiagram?Sketchthecellandlabelthecathodeandanode,thecharges
oneachelectrode,thedirectionsoftheflowofionsandthedirectionofelectronflow.Also
indicatethepositiveandnegativeelectrodes.

Analysis

Answeringallthesequestionsreliesonidentifyingtheanodeandcathodefromtheequationfor
thecellreaction.Bydefinition,theanodeistheelectrodeatwhichoxidationoccurs,andthe
cathodeiswherereductionoccurs.Thefirststep,therefore,istodeterminewhichreactantis
oxidisedandwhichisreduced.Onewaytodothisistodividethecellreactionintohalfreactions
andbalancethembyaddingelectrons.Then,ifelectronsappearasaproduct,thehalfreactionis
oxidationiftheelectronsappearasareactant,thehalfreactionisreduction.

Solution

Thebalancedhalfequationsare:

Zn(s)loseselectronsandisoxidised,soitistheanode.Theanodichalfcellis,therefore,azinc
electrodedippingintoasolutionthatcontainsZn 2+(e.g.fromdissolvedZn(NO3)2orZnSO4).
Withinthecelldiagram,theanodichalfcelliswrittenonthelefthandsidewiththeelectrode
materialattheleftoftheverticallineandtheoxidationproductattheright:

Silverionsgainelectronsandarereducedtometallicsilver,sothecathodichalfcellconsistsofa
silverelectrodedippingintoasolutioncontainingAg +(e.g.fromdissolvedAgNO3).Withinthe
celldiagram,thesilvercathodichalfcelliswrittenontherighthandside,withtheelectrode
materialtotherightoftheverticallineandthesubstancereducedontheleft:

Inthecelldiagram,thezincanodichalfcell(left)andthesilvercathodichalfcell(right)are
separatedbydoubleverticaldashedlinesthatrepresentthesaltbridge.

Thecellmaybesketchedasshownontheright.

Theanodealwayscarriesanegativechargeinagalvaniccell,sothezincelectrodeisnegative
andthesilverelectrodeispositive.Electronsintheexternalcircuittravelfromthenegative
electrodetothepositiveelectrode(i.e.fromtheZnanodetotheAgcathode).Theanionsmove
towardstheanode,andthecationsmovetowardsthecathode.

Isouranswerreasonable?

Alloftheanswersdependondeterminingwhichsubstanceisoxidisedandwhichisreduced,so
thatiswhattocheck.Oxidationiselectronloss,andZnmustloseelectronstobecomeZn 2+,so
 zincisoxidisedandmustbetheanode.Ifzincistheanode,thensilvermustbethecathode.All
therestfollowsbyreasoning.

PRACTICEEXERCISE12.7
Sketchandlabelagalvaniccellthatmakesuse
ofthefollowingspontaneousredoxreaction:

Writethehalfequationsforthereactionsthat
occurattheanodeandcathode.Givethecell
diagram.Sketchthecellandlabelthecathode
andanode,thechargesoneachelectrode,the
directionsoftheflowofionsandthedirection
ofelectronflow.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.4ReductionPotentials

CellandStandardCellPotentials
Thevoltageorpotentialofagalvaniccellvarieswiththeamountofcurrentflowingthroughthecircuit.Themaximumpotentialthatagivencell
cangenerateiscalleditscellpotential(Ecell),orelectrochemicalpotential,anexpressionintroducedonp.502.Asmentionedpreviously,the
conventioninwritingacelldiagramistoputthecathode(reductionprocess)ontherighthandsideandtheanode(oxidationprocess)ontheleft
handside.Thecellpotentialisthenthepotentialdifferencebetweenthecathodicandanodichalfcells,i.e.theright(R)andtheleft(L)halfcells,
respectively.

Ecelldependsonthecompositionoftheelectrodesandtheconcentrationsoftheionsinthehalfcells,aswellasthetemperatureandpressure.To
comparethepotentialsfordifferentcells,weusethestandardcellpotential .Thisisthepotentialofthecellwhenalloftheion
concentrationsare1Mandanygasesinvolvedinthecellreactionareatapressureof110 5Pa.Thetemperatureisgenerallyassumedtobe298
K(25C),butshouldalwaysbespecified.TheIUPACconventionfordetermining is:

Apositive cellmeansthatreductionoccursattherighthandelectrode,whereasanegative celltellsusthatreductionoccursattheleft

handelectrode.Thecelldiagramforthecellinfigure12.12(p.504)canbewrittenas:

Apositive cellforanycellmeansthatthedefinedcellreactionisspontaneousor,equivalently,thepolarityoftherighthandelectrode
(cathode)ispositive.Therefore,thecellreactionforthedefinedcell:

willbespontaneousandtheBn+ionsintherighthandhalfcellwillbereducedtoB.Ontheotherhand,anegative meansthatthedefined
cellreactionisnotspontaneous,andthereversereactionwillbespontaneous.Inagalvaniccell,thecellpotentialforthespontaneousreactionis
alwayspositive.Ifthecalculatedcellpotentialisnegative,thereactionisspontaneousinthereversedirection.(Thismeansthatthecelldiagram
waswritteninthewrongdirection.)Wewillbediscussingthethermodynamicsofspontaneousandnonspontaneouselectrochemicalprocessesin
section12.5.

Cellpotentialsarerarelylargerthanafewvolts.Asmentionedbefore,thestandardcellpotentialforthegalvaniccellconstructedfromsilverand
copperelectrodesshowninfigure12.10bisonly0.46V.Onecellinacarbatteryproducesonlyabout2V.Batteriesthatgeneratehigher
voltages,suchasacarbattery,areassembliesofcellsarrangedinseriessothattheirpotentialsadduptogivethetotalbatterypotential.Wewill
discussthechemistryofimportantbatteriesindetailinsection12.8.

ReductionandStandardReductionPotentials
Itisusefultoimaginethatthemeasuredoverallcellpotentialarisesfromacompetition,ortugofwar,forelectronsbetweenthetwohalfcells.
Thus,eachhalfcellhasacertainnaturaltendencytoacquireelectronsandproceedasareduction.Themagnitudeofthistendencyisexpressed
bythereductionpotential(Ered)ofthereaction(alsoknownasredoxpotentialoroxidation/reductionpotential).Whendeterminedunder
standardconditions(p=110 5Paandconcentrationsof1Mforallionsundergoingeitheroxidationorreduction),thereductionpotentialis
calledthestandardreductionpotential.Thesevaluesareusuallytabulatedat25C.Torepresentastandardreductionpotential,weadda
subscripttothesymbol thatidentifiesthesubstanceundergoingreduction.Thus,thestandardreductionpotentialforthehalfreaction:

isspecifiedas

Whentwohalfcellsareconnected,theonewiththelargerreductionpotential(thegreatertendencytoundergoreduction)acquireselectronsfrom
thehalfcellwiththelowerreductionpotential,whichisthereforeforcedtoundergooxidation.

Themeasuredcellpotentialrepresentsthemagnitudeandsignofthedifferencebetweenthereductionpotentialofonehalfcellandthereduction
potentialoftheother.Aswehavediscussedbefore,when ispositive,thecellreactionisspontaneousaswritten.Wecanseefrom

that,if ispositive, isgreaterthan .Anexampleofthisisthecoppersilvercelldiscussedpreviously:

Thetwopossiblereductionprocessesinthiscellare:

Aswehaveseeninfigure12.9,thespontaneousprocessinthiscellisreductionofAg +(aq)andoxidationofCu(s)accordingtotheequation:
ThismeansthatthestandardreductionpotentialoftheAg +/AghalfcellmustbelargerthanthestandardreductionpotentialoftheCu 2+/Cuhalf
cell.Inotherwords,ifweknewthevaluesof and andcalculated by:

wewouldfindthat ispositive.

Acommonerroristomultiplythestandardreductionpotentialsbythefactorsusedtobalancethetwohalfreactions.Inthiscase,thetemptationis
tomultiply byafactorof2.However,cellpotentialsaregiveninvolts,energyperunitofcharge.Thus,halfcellpotentialsaresimply
combinedtogivethecellpotentials:

DeterminingStandardReductionPotentials
Unfortunately,wehavenowaytomeasuretheabsolutestandardreductionpotentialofanisolatedhalfcell.Allthatcanbemeasuredarepotential
differenceswhentwohalfcellsareconnected.Therefore,toassignvaluestothevariousstandardreductionpotentials,areferenceelectrodehas
beenarbitrarilychosenanditsstandardreductionpotentialhasbeenassignedavalueofexactly0V.Thisreferenceelectrodeiscalledthe
standardhydrogenelectrode,SHE(seefigure12.14).Gaseoushydrogenatapressureof110 5Paisbubbledoveraplatinumelectrodecoated
withveryfinelydividedplatinum,whichprovidesalargecatalyticsurfaceareaonwhichtheelectrodereactioncanoccur.Thiselectrodeis
surroundedbyasolutioninwhichtheconcentrationofhydrogenions,H+,is1M.Thereactionattheplatinumsurface,writtenasareduction,is:

wherethedoublearrowsindicateonlythatthereactionisreversible,notthatthereistrueequilibrium.Whetherthehalfreactionoccursasa
reductionoranoxidationdependsonthereductionpotentialofthehalfcellwithwhichitispaired.

FIGURE12.14Thestandardhydrogenelectrode(T=298K).

Figure12.15aillustratesthehydrogenelectrodeconnectedtoacopperhalfcelltoformagalvaniccell.Whencalculatingastandardreduction
potential,theconventionistoputthehydrogenhalfcellonthelefthandsideofthecelldiagram.Therefore,thecelldiagramforthiscellis:

Given :

Weknowthat ,so:

Weknowfromourmeasurementinfigure12.15athat so .Thepositivevaluemeansthatreductionis
occurringattherighthandelectrodeinthecelldiagramsothespontaneouscellreactionis:
 FIGURE12.15 Galvaniccellscomposedof
(a)copperandhydrogenhalfcellsand
(b)zincandhydrogenhalfcells.

Nowlet'slookatagalvaniccellsetupbetweenazincelectrodeandahydrogenelectrode(seefigure12.15b).Rememberingthatthehydrogen
electrodebydefinitionappearsonthelefthandside,thecelldiagramis:

Given :

Weknowthat ,so:

Weknowfromourmeasurementinfigure12.15bthat so .Thenegativevalueinthiscasemeansthat
reductionisinfactoccurringatthelefthandelectrodeofthecelldiagramsothespontaneouscellreactionis:

Wecanvisualisetheseresultsinascaledgraphofthereductionpotentials,wherealowerpositionedspeciescandonateelectronstoahigherone
(figure12.16).Fromthis,wecandirectlycalculatetheelectrochemicalpotentialinanygalvaniccell.Youcanseefromthisfigurethatthevalues
of areadditive.Weknowthat ofthezinccoppergalvaniccell=1.10Vand ofthecoppersilvercell=0.46V,so ofthezinc
silvercellisthesumofboth(1.10V+0.46V=1.56V).

FIGURE12.16Choiceofanarbitraryzeropointtodeterminestandardreductionpotentials foragalvaniccell.

However,thissetupenablesustomeasureonlypotentialdifferences.Theabsolutepotentialsoftherespectiveelectrodesarenotknown.Butwe
don'tneedtoknowthesebecauseweareinterestedonlyinthe ofthegalvaniccellitself,soitissufficienttochooseanarbitraryzeropoint.
(Thisissimilartodefiningzeroonthecelsiusscaleasthetemperatureofmeltingice,ortomeasuringelevationrelativetosealevelratherthan
fromthecentreoftheEarth.)
Thestandardreductionpotentialsofmanyhalfreactionscanbecomparedwiththatofthestandardhydrogenelectrodeasdescribedonthe
previouspage.Table12.1listsvaluesobtainedforsometypicalhalfreactions.Theyarearrangedindecreasingorderthehalfreactionsatthe
tophavethegreatesttendencytooccurasareduction,whilethoseatthebottomhavethehighesttendencytooccurasanoxidation.Table12.1
showsthat:
Substanceslocatedtotheleftofthedoublearrowsareoxidisingagents,becausetheybecomereducedwhenthereactionsproceedinthe
forwarddirection.
Thestrongestoxidisingagentsarethosemosteasilyreduced,andtheyarelocatedatthetopleftofthetable(e.g.F2).
Substanceslocatedtotherightofthedoublearrowsarereducingagentstheybecomeoxidisedwhenthereactionsproceedfromrighttoleft.
Thestrongestreducingagentsarethosefoundatthebottomrightofthetable(e.g.Li).
TABLE12.1 StandardReductionPotentials

WORKEDEXAMPLE12.6

CalculatingHalfcellPotentials

Thestandardcellpotential ofthesilvercoppergalvaniccellhasavalueof0.46V.Thecellreactionis:

and .Whatis ?

Analysis
 Because ispositive,weknowthatreductionmustbeoccurringattherighthandelectrode.WeknowfromtheequationthatAg +is

reducedandthereforetheAg +/Aghalfcellmustbeontherighthandside.Wethenusetheequation tocalculate

Solution

Substitutingvaluesfor and :

Thenwesolvefor :

Isouranswerreasonable?

Thehalfcellwiththelarger valuewillalwaysundergoreduction. islargerthan sowepredictthatAg +willbe

reduced,asisobserved.Ourcalculatedreductionpotentialappearstobecorrect.

PRACTICEEXERCISE12.8
Thegalvaniccelldescribedinpracticeexercise12.7hasa
standardcellpotentialof .Giventhat

,calculate .Checkyouranswer
byreferringtotable12.1.

Wecanusethedataintable12.1toshowthatweobtainthesamespontaneousreactionregardlessofhowthecelldiagramiswritten.For
example,writingthesilvercoppercelldiagramwiththesilverhalfcellontherighthandsideandthecopperhalfcellontheleft:

gives:

andthepositivevaluepredictsthatAg +(aq)willbereducedandCu(s)willbeoxidised.Conversely,ifwewritethecelldiagramwiththecopper
halfcellontherighthandsideandthesilverhalfcellontheleft:

then:

Thenegativevaluetellsusthatreductiondoesnotoccurattherighthandelectrodeandthatthereverseofthedefinedcellreactionis
spontaneous.Therefore,Cu(s)isoxidisedandAg +(aq)isreduced.

Thestandardhydrogenelectrode,SHE,isnottheonlyreferenceelectrodeused.Thesaturatedcalomelelectrode(SCE)isalsocommonand
consistsofelementalmercury,mercury(I)chlorideandHg 2Cl2(calomel,ClHgHgCl)inasaturatedKClsolution.Thereaction:

hasareductionpotentialof0.244Vat298KversusSHE.Anotherpopularreferenceelectrodeisthesilver/silverchlorideelectrode,which
containsanAgrodcoatedwithsilverchlorideandbathedinasaturatedKClsolution.Thishasareductionpotentialof0.199Vat298Kversus
SHEforthereaction:
TheseelectrodesarewidelyusedbecausetheyaremorestableandeasiertousethantheSHE.

SpontaneousandNonspontaneousReactions
Oneofthegoalsofchemistryistopredictreactions.Thiscanbedoneforredoxreactionswhethertheyoccurinagalvaniccellorjustina
containerwithallthechemicalscombinedinonereactionmixtureusingthehalfreactionsandstandardreductionpotentialsintable12.1.We
willillustratethiswithsomeexamples.

Thereactantsandproductsofspontaneousredoxreactionsareeasytospotwhenreductionpotentialsarelistedinorderofmostpositivetoleast
positive(mostnegative),asintable12.1.Foranypairofhalfreactions,theonewiththemorepositivereductionpotentialwilloccurasa
reduction.Theotherhalfreactionisreversedandoccursasanoxidation.Itisimportanttonotethat,whenthedirectionofareactionisreversed,
thesignofthereductionpotentialisnotchangedwhencalculating .Theminussignintheequation takescareofthis,
essentiallyreversingthereactionlistedintable12.1.

TheIUPACconventionrequiresthatyounever:
changethesignofareductionpotentialwhencalculatingEcell
multiplybystoichiometriccoefficientswhenbalancingacellequation.
Workedexamples12.7and12.8demonstratethis.

WORKEDEXAMPLE12.7

PredictingtheOutcomeofRedoxReactions

PredictthereactionthatwilloccurwhenbothNiandFeareaddedtoasolutionthatcontainsbothNi2+andFe2+,eachat1M
concentration.

Analysis

Thefirstquestionwouldbe,Whatpossiblereactionscouldoccur?Thesysteminvolvesapossibleredoxreactionthatcanbe
predictedusingdataintable12.1.Onewaytodothisistonotetherelativepositionsofthehalfreactionswhenarrangedastheyarein
table12.1.

Intable12.1,thehalfreactionwiththemorepositive(inthiscase,lessnegative)reductionpotentialwilloccurasareduction.
ThereforeNi2+(aq)willbereducedandFe(s)willbeoxidised.Theproductsarethesubstancesontheoppositesidesofeachhalf
reaction,namelyNi(s)andFe2+(aq).

Solution

Wehavedonenearlyalltheworkinouranalysisoftheproblem.Allthatisleftistowritetheequation.ThereactantsareNi2+andFe
theproductsareNiandFe2+:

Theequationisbalancedintermsofbothatomsandcharges,sothisisthespontaneousreactionthatwilloccurinthesystemspecified
intheproblem.

Isouranswerreasonable?

Ifourpredictionofthespontaneousreactioniscorrect, shouldbepositive.

AsNi2+isbeingreduced,Ni2+/Niwillbetherighthandelectrode(cathode):

Fromtable12.1:

As ispositive,ourpredictioniscorrect.Rememberthat,althoughthereactionFe2++2eFeisreversed,thesignof
(0.44V)isnotchanged.
 PRACTICEEXERCISE12.9
WhatspontaneousreactionoccursifCl2andBr2areaddedtoa
solutionthatcontainsbothClandBr,eachat1Mconcentration?

Ifyouintendtouseaparticularspontaneousredoxreactioninagalvaniccell,thereductionpotentialscanbeusedtopredictwhatthestandard
cellpotentialwillbe,asillustratedinworkedexample12.8

WORKEDEXAMPLE12.8

PredictingtheCellReactionandCellPotentialofaGalvanicCell
Atypicalcellofaleadstoragebatteryofthetypeusedtostartcarsisconstructedusingelectrodesmadeofleadandlead(IV)oxide,
PbO2,andwithsulfuricacidastheelectrolyte.Thehalfreactionsandtheirreductionpotentialsinthissystemare:

Whatisthespontaneouscellreactionandwhatisthestandardpotentialofthiscell?

Analysis

Inthespontaneouscellreaction,thehalfreactionwiththelarger(morepositive)reductionpotentialwilltakeplaceasareduction,
whiletheotherhalfreactionwillbereversedandoccurasanoxidation.Thecellpotentialisthedifferencebetweenthetworeduction
potentials.

Solution

PbO2hasalarger,morepositivereductionpotentialthanPbSO4,sothefirsthalfreactionwilloccurinthedirectionwritten.Thesecond
mustbereversedtooccurasanoxidation.Inthecell,therefore,thehalfreactionsare:

(Hint:Usechangesinoxidationnumberstocheckwhenbalancingcomplexredoxreactions.)Thecellpotentialisobtainedby:

Becausethefirsthalfreactionoccursasareduction,thisbecomestherighthandelectrode.Therefore:

Again,eventhoughwereversedthedirectionofthereaction:

wedidnotchangethesignofthereductionpotentialwhencalculating .Theconvention tookcareofthis.

PRACTICEEXERCISE12.10
Determinethecellreactionandthestandardcellpotentialofa
galvaniccellemployingthefollowinghalfreactions.

Whichelectrode(AlorCu)wouldbetheanode?

Becausethespontaneousredoxreactionthattakesplaceamongamixtureofreactantscanbepredictedfromthestandardreductionpotentials,it
shouldbepossibletopredictwhetheraparticularreaction,aswritten,canoccurspontaneously.Wecandothisbycalculatingthecellpotential
thatcorrespondstothereactioninquestionandseeingifthepotentialispositive.

OxidisingandNonoxidisingAcids

Thestandardreductionpotentialsintable12.1wouldpredictthatacids(representedbyH+(aq)orH3O+)canoxidisecertainmetals,suchasFe,
Zn,SnandMg(seefigure12.17),butnotothermetals,suchasAg,CuandAu.

FIGURE12.17Zincreactswithaqueoussulfuricacid.Bubblesofhydrogenareformedwhenasolutionofsulfuricacidcomesincontactwithmetalliczinc.

Forexample,whendiluteaqueoussulfuricacidreactswithzinc,azincsaltisformedandbubblesofgaseoushydrogenarereleased:

Diluteaqueoussulfuricacidionisesinwatertogivepositivelychargedhydrogenions(protons)andnegativelychargedsulfateions.Theproton
canactasanoxidisingagentbybeingreducedtoH2.Althoughthesulfateioncanbereduced(toSO32,forexample),protonsaremuchmore
easilyreducedunderthesediluteconditions.Therefore,whenametalsuchaszincisaddedtodiluteaqueoussulfuricacid,itisH+,ratherthan
SO42,thatremovestheelectronsfromzinc.

Asimilarsituationcanbefoundwithhydrochloricacid,whichcontainsH+andClions.H+istheoxidisingagent,astheClionshowsno
tendencytogainanelectronunderthese(oranyother)conditions.

Comparedwithmanyotherchemicals,thesolvatedproton,H+(aq),isaratherpooroxidisingagent,sohydrochloricacidanddiluteaqueous
sulfuricacidhaveonlypooroxidisingabilities.Forthisreason,theyareoftencallednonoxidisingacids,eventhoughtheirprotonscanoxidise
certainmetals.Actually,whenwecallsomethinganonoxidisingacid,wearesayingthattheanionoftheacidisaweakeroxidisingagentthanH+
(whichisequivalenttosayingthattheanionoftheacidismoredifficulttoreducethanH+).Examplesofnonoxidisingacidsarelistedintable
12.2.
TABLE12.2 NonoxidisingandOxidisingAcids
Nonoxidisingacid
HCl(aq)

H2SO4(aq)(a)

H3PO4(aq)

mostcarboxylicacids,e.g.CH3COOH(aceticacid),HCOOH(formicacid)

Oxidisingacid Reductionreaction
HNO3 (conc.)NO3(aq)+2H+(aq)+eNO2(g)+H2O(l)

(dilute)NO3(aq)+4H+(aq)+3eNO(g)+2H2O(l)

(verydilute,withstrongreducingagent)NO3(aq)+10H+(aq)+8eNH4+(aq)+3H2O(l)

H2SO4 (hot,conc.)SO42(aq)+4H+(aq)+2eSO2(g)+2H2O(l)
 (hot,conc.withstrongreducingagent)SO42(aq)+10H+(aq)+8eH2S(g)+4H2O(l)

HClO4 ClO4(aq)+8H+(aq)+8eCl(aq)+4H2O

(a)H2SO4isanonoxidisingacidwhencoldanddilute.

NotallacidsarelikeHClanddiluteaqueousH2SO4.OxidisingacidshaveanionsthatarestrongeroxidisingagentsthanH+(seetable12.2).An
exampleisconcentratednitricacid,HNO3.Whendissolvedinwater,nitricacidionisestogiveH+andNO3ions.However,inthissolutionthe
nitrateionisamorepowerfuloxidisingagentthanaproton.Inthecompetitionforelectrons,therefore,thenitrateionwinsand,whennitricacid
reactswithametal,thenitrateionisreduced.

BecausetheNO3ionisastrongeroxidisingagentthanH+,itcanoxidisemetalsthatH+cannot.Forexample,ifacoppercoinisdroppedinto
concentratednitricacid,itreactsviolently(figure12.18).Thereddishbrowngasisthehighlytoxicnitrogendioxide,NO2,whichisformedby
reductionoftheNO3ion.

Noticethattheoxidationnumberofnitrogendecreasesweidentifythesubstancethatcontainsthisnitrogen,theNO3ion,astheoxidisingagent.

FIGURE12.18Acoppercoininconcentratednitricacidshowingtheviolentreaction,formationoftheblueCu2+ionandtheevolutionofreddishbrown
NO2 (g).

Whenoxidisingacidsreactwithmetals,itisoftendifficulttopredicttheproducts.Theparticularreactionthatoccursdependsverymuchonthe
concentrationoftheacidandexperimentalconditions(e.g.whetherthereactionwasperformedwithheating).Reductionofthenitrateion,for
example,canproduceallsortsofcompoundswithdifferentoxidationstatesofnitrogen,dependingonthereducingpowerofthemetalandthe
concentrationoftheacid.Whenconcentratednitricacidreactswithametal,itoftenproducesnitrogendioxide,NO2,asthereductionproduct.
Whendilutenitricacidisusedtodissolveametal,theproductisoftennitrogenmonoxide(alsocallednitricoxide),NO,instead.Copper,for
example,candisplayeitherbehaviourtowardsnitricacid.Thenetionicequationsforthereactionsareasfollows.

ChemistryResearch

AntioxidantsandFreeRadicals

ProfessorCarlHSchiesser,UniversityofMelbourneandDirector,AustralianResearchCouncilCentreofExcellenceforFreeRadical
ChemistryandBiotechnology

Oneofthegreatparadoxesoflifeisthis:whileweneedoxygentolive,oxygencanalsobeinvolvedinourdemise.Ifnotburnedfor
fuel,oxygencancausefreeradicaldamagetocells.Freeradicalsareatomsormoleculesthathaveoneormoreunpairedelectrons.In
biologicalsystems,theyformamajorfunctionincellsignalling,andHund'srule(seechapter4)requiresthatmolecularoxygen,O2,is
itselfafreeradical.Superoxide,O2,isformedduringrespirationthroughthereactionofO2withelectronsthatleakfromthe
electrontransportchainwhenhydrogenperoxide,H2O2,formedbythereactionofO2withsuperoxidedismutase(SOD),reactswith
iron,Fe2+,hydroxylradicals,OH,areformedthroughaprocessknownastheFentonreaction.Thesereactiveoxygenspecies(ROS)
giverisetooxidativestress.

Mammalsareprotectedfromoxidativestressthroughaseriesofelaborateprevention,interceptionandrepairdefencemechanisms
(figure12.19).Glutathioneperoxidase(GPx,figure12.20)andcatalase,forexample,areenzymeswhoseprincipalfunctionisto
converttheproductsofoxidativestress(e.g.H2O2)intoharmlessspecies(e.g.H2O,figure12.21).Muchoftheseleniuminourdiet
endsupasselenocysteineinenzymessuchasglutathioneperoxidase.Unlikesulfur,seleniumhasthecorrectreductionpotentialto
reduceunwantedperoxidesformedinourdailylives.Sincethelate1990s,selenocysteinehasbeenrecognisedasthetwentyfirst
essentialaminoacid.OtherimportantantioxidantmoleculesincludevitaminC(ascorbicacid)andvitaminE(amixtureoftocopherols).
 FIGURE12.19Ribbondiagramofselenoenzymeglutathioneperoxidaseat0.2nmresolution.

FIGURE12.20Antioxidantdefencesinthehumanbody.Hydroxylradicalscanoxidisevirtuallyallorganiccompounds,includingDNA,proteins
andfats.Forthisreason,ithasbeenproposedthattheseandotherfreeradicalsarekeydamagingagentsinsomecancers,the
ageingprocessandcardiacdisease.

FIGURE12.21Howglutathioneperoxidase(GPx)workstoremovereactiveoxygenspeciesundernormalandhypoxicconditions.Notethat
glutathione(GSH)isacoreductant.

ResearchersattheAustralianResearchCouncilCentreofExcellenceforFreeRadicalChemistryandBiotechnologyareadding
antioxidantfunctiontoknownpharmaceuticalmolecules,therebycreatingdualactiondrugsthatwillalsoprotectagainstfreeradical
damageassociatedwithcardiacandhypertensiveevents.Suchadvancesinfreeradicalchemistryhavethepotentialtoimprovethe
healthofmillionsofpeopleworldwide.

ConcentratedHNO3:

DiluteHNO3:
Ifverydilutenitricacidreactswithametalthatisaparticularlystrongreducingagent,suchaszinc,thenitrogencanbereducedallthewaydown
tothe3oxidationstatethatithasinNH4+(orNH3).Thenetionicequationis:

Thenitrateioninthepresenceofprotonsmakesnitricacidapowerfuloxidisingacid.Allmetalsexcepttheveryunreactiveones,suchasplatinum
andgold,areattackedbyit.Nitricacidalsodoesagoodjobofoxidisingorganicsubstances,soitiswisetobeespeciallycarefulwhenworking
withthisacidinthelaboratory.Veryseriousaccidentshaveoccurredwhenconcentratednitricacidhasbeenusedaroundorganicsubstances.It
reactsveryviolentlywithmostorganiccompounds,resultinginheat,gasorfire.

Inadilutesolution,thesulfateionofsulfuricacidhaslittletendencytoserveasanoxidisingagent.However,ifthesulfuricacidisboth
concentratedandhot,itbecomesafairlypotentoxidiser.Forexample,copperdoesnotreactwithcool,diluteH2SO4,butitisattackedbyhot,
concentratedH2SO4accordingtotheequation:

Becauseofthisoxidisingability,hot,concentratedsulfuricacidcanbeverydangerous.Theliquidisviscousandcansticktotheskin,causing
severeburns.

Themixtureobtainedbymixingconcentratednitricacidandconcentratedhydrochloricacid(usuallyinavolumetricratioof1:3)iscalledaqua
regia(figure12.22).Thenamecomesfromthefactthatthestrongoxidisingpowerofthisacidmixturecandissolveeventhesocalledroyal
(regalornoble)metals,goldandplatinum.

FIGURE12.22Aquaregia,obtainedbymixingconcentratednitricacidwithconcentratedhydrochloricacid.

Aquaregiaisusedtoproducechloroauricacid,HAuCl4,whichisusedastheelectrolyteintheWohlwillprocessfortheproductionofgoldwith
99.999%purity.Wewilldiscusselectrolyticprocesseslaterinthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.5RelationshipBetweenCellPotential,
ConcentrationandGibbsEnergy
Thefactthatcellpotentialscanbeusedtopredictthespontaneityofredoxreactionsisnocoincidence.
ThereisarelationshipbetweenthecellpotentialandtheGibbsenergychangeforareaction.Inchapter
8,wesawthatGforareactionisameasureofthemaximumusefulworkthatcanbeobtainedfroma
chemicalreactionatconstanttemperatureandpressure.Specifically,therelationshipis:

TheGibbsEnergyChange,G
Inanelectricalsystem,workissuppliedbytheelectriccurrentthatispushedalongbythepotentialof
thecell.Itcanbecalculatedfromtheequation:

wherezistheamountofelectronstransferred,FisaconstantcalledtheFaradayconstant,whichis
equaltothenumberofcoulombsofchargeequivalentto1moleofelectrons(1F=96485Cmol1),and
Ecellisthepotentialofthecellinvolts.Analysisoftheunitsintheequationshowsthattheanswerwill
beinjoules,theunitofenergy.Recallthat1volt=1JC1,so:

Combiningourtwoequationsgives:

Whatdoesthisequationmean?IttellsusthatthechangeinGibbsenergy,G,betweenthereactants
andproductsofthereactionisdirectlyrelatedtothemaximumpotentialofacell,Ecell.WhenEcellis
positive,Gwillbenegativeandthecellreactionwillbespontaneous.Ontheotherhand,whenEcellis
negative,Gwillbepositiveandthecellreactionwillbespontaneousinthereversedirection.Ifthe
standardcellpotential isused,thestandardGibbsenergychange, ,canbecalculated:

WORKEDEXAMPLE12.9

CalculatingtheStandardGibbsEnergyChange
Calculate forthefollowingreaction,giventhatitsstandardcellpotentialis0.32Vat25
C:

Analysis
 Thisisastraightforwardapplicationof .Because2molesofClare
oxidisedtoCl2and2molesofelectronsarethereforetransferred,theamountz=2mol.We
willalsousetheFaradayconstant,1F=96485Cmol1.

Solution

PRACTICEEXERCISE12.11
Calculate forthereactionsthattake
placeinthegalvaniccelldescribedin
practiceexercise12.10.

EquilibriumConstant,K
Oneusefulapplicationofelectrochemistryisthedeterminationofequilibriumconstants.InChapter9
wesawthat isrelatedtotheequilibriumconstantbytheexpression:

NotethatweuseKc fortheequilibriumconstantbecausetheelectrochemicalreactionsdescribedhere
occurinsolution:Combining:

with:

weget:

so:

Thisequationshowstherelationshipbetween andtheequilibriumconstant.

Inthisequation,thevalueofR=8.314Jmol1K1,Tisthetemperatureinkelvin,F=96485Cper
moleofe,andzistheamountofelectronstransferredinthereaction.

Forhistoricalreasons:
issometimesexpressedusingthecommonlogarithm,log(logarithmwithbase10).Naturaland
commonlogarithmsarerelatedbytheequation:

Forreactionsat298K(25C),alloftheconstants(R,TandF)canbecombinedwiththefactor2.303
togive0.0592JC1.BecauseJC1=V,theequationreducesto:

wherezistheamountofelectronstransferredinthecellreactionasitiswritten.

WORKEDEXAMPLE12.10

CalculatingEquilibriumConstantsfrom

CalculateKc forthereactioninworkedexample12.9.

Analysis

Theproblemsimplyinvolvessubstitutingvaluesinto:

andsolvingfortheequilibriumconstant.

Solution

Thereactioninworkedexample12.9has andz=2.Thetemperatureis25C(298K).
Wecansolve:

forlnKc andthensubstitutevalues:

Substitutingvalues(1V=1JC1):

Takingtheantilogarithm:

Isouranswerreasonable?

Asaroughcheck,wecanlookatthemagnitudeof andapplysomesimplereasoning.

When ispositive, isnegative.Inchapter9welearnedthat,when isnegative,

 thereactionproceedsfartowardscompletionwhenequilibriumisreached.Therefore,we
expectthatKc willbelarge,andthatagreeswithouranswer.

PRACTICEEXERCISE12.12
Thecalculatedstandardcellpotentialforthe
reaction:

is .CalculateKc forthis
reactionat298K.

TheNernstEquation
Whenalloftheionconcentrationsinacellare1M,andthepartialpressuresofanygasesinvolvedin
thecellreactionareat110 5Pa,thecellpotentialisequaltothestandardpotential.Whenthe
concentrationsorpressureschange,however,sodoesthecellpotential.Forexample,inanoperating
cellorbattery,thepotentialgraduallydropsasthereactantsareusedupandasthecellreaction
approachesitsnaturalequilibriumstatus.Atequilibrium,thepotentialhasdroppedto0thebatteryis
dead.

Theeffectofconcentrationonthecellpotentialcanbeobtainedfromthermodynamics.Inchapter9,we
learnedthattheGibbsenergychangeisrelatedtothereactionquotient(Q,seesection9.2)bythe
equation:

(Rememberthatthereactionquotient,Q,isusedwhenthereactantsarenotinequilibriuminother
words,theequilibriumconstant,K,isaspecialcaseofQ,usedwhenthesystemisinequilibrium.)
SubstitutingforGand from:

and:

gives:

DividingbothsidesbyzFgives:

ThisequationiscommonlyknownastheNernstequation,namedafterWalterNernst,aGerman
chemistandphysicistwhowasawardedtheNobelPrizeinchemistryin1920inrecognitionofhiswork
inthermochemistry.Usingcommonlogarithmsinsteadofnaturallogarithmsandcalculatingthe
constantsfor298K(25C)givesanotherformoftheNernstequationthatissometimesused:
InwritingtheNernstequationforagalvaniccell,wewillconstructthereactionquotient(Q)usingmolar
concentrationsforionsandpartialpressuresinpascalsforgases.Thus,foracellusingahydrogen
electrode(withthepartialpressureofH2notnecessarilyequalto110 5Pa)forwhichthecellreaction
is:

theNernstequationis:

(Rememberthatwedonotincludeconcentrationsofpuresolidsorpureliquidsinthereactionquotient,
Q.)

Becauseofinterionicattractions,ionsdonotalwaysbehaveasthoughtheirconcentrationsareequalto
theirmolarities.Strictlyspeaking,effectiveconcentrations(calledactivities,seesection9.2)shouldbe
usedintheexpressionforQ.Effectiveconcentrationsaredifficulttocalculate,soforsimplicitywewill
usemolaritiesandacceptthefactthatourcalculationsarenotentirelyaccurate.

Alternatively,wecouldaddanonreactingbackgroundelectrolyteatamuchhigherconcentrationthan
thereactantsorproductsandreportthisconcentrationwithourresults.Often1MKClor1MLiClO4is
usedasthebackgroundelectrolyte.Thereactionisthenstudiedunderconditionsofconstantionic
strength,andthereaction(andcellpotentials)behavessimplyaccordingtomolarities.Inchapter15,we
willseethatsimilarconsiderationsaremadewhenstudyingthekineticsofionicreactions.Fornow,in
workedexamples,wewillignoreionicstrengtheffects.Inthelaboratory,youshouldtakecareinyour
experimentalsetupstocontroltheseeffects.

WORKEDEXAMPLE12.11

CalculatingtheEffectofConcentrationonEcell

Consideragalvaniccellinvolvingthefollowinghalfreactions:

Calculatethecellpotentialwhen[Ni2+]=1.010 4Mand[Cr3+]=2.010 3M.

Analysis

Becausetheconcentrationsarenot1M,wemustusetheNernstequation.First,weneedthe
cellreactiontodeterminez,thenumberofelectronstransferred,andthecorrectformofthe
reactionquotient,Q.Wemustalsonotethatthereactingsystemisheterogeneoussolid
metalsandaliquidsolutionoftheirdissolvedionsareinvolved,sowehavetorememberthat
Qdoesnotcontainconcentrationtermsforsolids,suchasNi(s)andCr(s).

Solution
Thenickelhalfcellhasthemorepositivereductionpotential,soitshalfreactionwilloccuras
areduction.ThismeansthatCr(s)willbeoxidised.Makingelectrongainequaltoelectron
loss,thecellreactionis:

Inthisreaction,6earetransferred(z=6).TheNernstequationforthesystemistherefore:

Notethatwecalculatethereactionquotientusingtheconcentrationsoftheionsraisedto
powersequaltotheircoefficientsinthenetcellreaction,andthatwehavenotincluded
concentrationtermsforthetwosolids.Thisistheprocedurewefollowedforheterogeneous
equilibriainchapter9(pp.3567).

isdeterminedaccordingto:

Nowwecansubstitutethisvaluefor alongwithR=8.314Jmol1K1,T=298K,z=6,
F=96485Cmol1,[Ni2+]=1.010 4Mand[Cr3+]=2.010 3MintotheNernstequation.
Rememberingthat1V=1JC1,weobtain:

Thepotentialofthecellisexpectedtobe0.42V.

Isouranswerreasonable?

Thereisnosimplewaytochecktheanswer.However,therearecertaincriticalpointstolook
over.First,checkthatthehalfreactionshavebeencombinedcorrectlytogivethebalanced
cellreaction(checktheoxidationnumbers),becauseweneedthecoefficientsoftheequation
toobtainthecorrectsuperscriptsintheNernstequation.Then,checkthatthetemperaturein
kelvinhasbeenused,thatR=8.314Jmol1K1hasbeenused,andthattheother
substitutionshavebeenmadecorrectly.
 PRACTICEEXERCISE12.13
Inacertainzinccoppercell:

theconcentrationsoftheionsare[Cu 2+]=
0.0100Mand[Zn 2+]=1.0M.Usethe
reductionpotentialsintable12.1tocalculate
thecellpotentialat25C.

Oneoftheprincipalusesoftherelationshipbetweenconcentrationandcellpotentialisinthe
measurementofconcentrations.Experimentaldeterminationofcellpotentials,combinedwithmodern
developmentsinelectronics,hasprovidedameansofmonitoringandanalysingtheconcentrationsofall
sortsofsubstancesinsolution,evensomethatarenotthemselvesionicandthatarenotinvolved
directlyinelectrochemicalchanges.Workedexample12.12illustrateshowtheNernstequationis
appliedindeterminingconcentrations.

WORKEDEXAMPLE12.12

UsingtheNernstEquationtoDetermineConcentrations
Inalargenumberofsamplesofwater,inwhichthecopperionconcentrationisexpectedto
bequitesmall,[Cu 2+]wasmeasuredusinganelectrochemicalcell.Thisconsistedofasilver
electrodedippingintoa1.00MsolutionofAgNO3,whichwasconnectedbyasaltbridgeto
asecondhalfcellcontainingacopperelectrode.Thecopperhalfcellwasthenfilledwith
onewatersampleafteranother,andthecellpotentialwasmeasuredforeachsample.Inthe
analysisofoneparticularsample,thecellpotentialat25Cmeasuredwas0.62V,withthe
copperelectrodebeingtheanode.WhatwastheconcentrationofCu 2+inthissample?

Analysis

Inthisproblem,wehavebeengiventhecellpotential,Ecell,andwecancalculate from
thereductionpotentialsintable12.1.Theunknownquantityisoneoftheconcentration
termsintheNernstequation.

Solution

Thefirststepistowritethedefinedcellreaction,becauseweneedittocalculate andto
writetheexpressionforQforuseintheNernstequation.Becausecopperistheanode,itis
beingoxidised.ThisalsomeansthatAg +isbeingreduced.Therefore,theequationforthe
cellreactionis:
Becausetwoelectronsaretransferred,z=2andtheNernstequationistherefore:

Thevalueof canbeobtainedusingthedataintable12.1.Followingourusual
procedureandrecognisingthatsilverionsarereduced:

SubstitutionofthevaluesintotheNernstequation(rememberingthat1V=1JC1)gives:

Solvingforln([Cu 2+]/[Ag +]2)gives:

TakingtheantilogarithmgivesusthevalueofQ:

BecausetheconcentrationofAg +isknown(1.00M):

Isouranswerreasonable?

Weshouldfirstcheckthatwehavewrittenthecorrectchemicalequation,whichtherestof
thesolutiontotheproblemrelieson.Wecantheninsertourcalculatedvalueof[Cu 2+]back
intotheNernstequationandensurethatweobtainEcell=0.62V.Thiswillshowwith
certaintythatouransweriscorrect.

Asafinalpoint,noticethattheCu 2+concentrationisindeedverysmallandthatitcanbe
obtainedveryeasilysimplybymeasuringthepotentialgeneratedbytheelectrochemicalcell.
Determiningtheconcentrationsinmanysamplesisalsoverysimplejustchangethe
aqueoussampleandmeasurethepotentialagain.

PRACTICEEXERCISE12.14
 Agalvaniccellwasconstructedby
connectinganickelelectrodedippinginto
1.20MNiSO4solutiontoachromium
electrodedippingintoasolutioncontaining
Cr3+atanunknownconcentration.The
potentialofthecellwasmeasuredtobe
0.552V,withthechromiumservingasthe
anode.Thestandardcellpotentialforthis
systemwasdeterminedtobe0.487V.What
wastheconcentrationofCr3+inthesolution
ofunknownconcentration?

Itshouldbenotedthattheabilityofcertaincompoundstoactaseitheroxidantorreductantcandepend
stronglyonthepHofthereactionsolution.Forexample,ascanbeseenfromtable12.1,thestandard
reductionpotential, is+1.51Vforthehalfreaction:

TheNernstequationforthissystem(z=5electronsexchanged)canalsobeappliedtohalfcellreactions
sothatweobtain:

Thus,themoreacidicthesolutionbecomes(i.e.thehigherthe[H+]),thegreaterthereductionpotential.
Inotherwords,MnO4isamuchstrongeroxidantinacidicsolutionsthaninneutralorevenbasic
solutions.

ConcentrationCells
Thusfar,wehaveconsideredonlycellswithdifferentchemicalspeciesattherighthandandlefthand
electrodes,andwehaveshownthatacurrentinvariablyresultsfromsuchanarrangementbecauseone
ofthehalfcellshasalarger thantheother.Wecanalsoshowthatcurrentwillflowinan
electrochemicalcellwhenthechemicalspeciesatbothelectrodesarethesame,providingthattheyare
presentatdifferentconcentrations.Suchcellsarecalledconcentrationcells.
Considerthecellontherightat298K.Wecanwritethecelldiagramforthiscellas:

Thetwohalfreactionsare:

andtheoverallcellreactionistherefore:

WecanwritetheNernstequationforthisreactionas:

Sincetheredoxprocessesintheleftandrighthalfcellsareidentical,wehave:

Hence:

Therefore,thereisasmall,butmeasurable,potentialdifferencebetweentheelectrodesthatresultssolely
fromthedifferentconcentrationsofthetwoCu 2+solutions.Asthereactionproceeds,theconcentrations
ofthetwosolutionswilleventuallybecomethesameandtherewillbenopotentialdifferencebetween
theelectrodes.Thisissimilartothespontaneousprocessofmixingthatoccurswhena0.01Msolution
ofCu 2+ispouredintoanequalvolumeofa0.1MsolutionofCu 2+ions(andviceversa).

Interestingly,manybiochemicalprocessesarepoweredbyconcentrationgradients.Forexample,
adenosine5'triphosphate(ATP),whichisthemainenergytransfermoleculeincells,issynthesised
fromadenosinediphosphate(ADP)andinorganicphosphateinmitochondriathisprocessispowered
byaprotongradient(seep.495).
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.6Corrosion
Thecorrosionofironandothermetalsisoneofthemostcommonlyencounteredredoxprocessesinour
dailylife,andithasplaguedhumanityeversincethesemetalswerefirstdiscovered.Atfirstglance,the
rustingofacarorship(seep.489)doesnotseemtobeacomplicatedprocess,sinceironreactswith
oxygentogiveiron(II)oxide:

Theelectronsreleasedwhentheironisoxidisedtravelthroughthemetaltosomeotherplacewherethe
ironisexposedtoair.Thisiswherereductionoccurs.Isthisprocessreallythateasy?Whydoesacar
rustfasterinmoistair?Whydoesn'titrustinpurewaterthatisoxygenfree?Thecorrosionprocessis
apparentlyelectrochemicalinnaturewiththeironactingastheanode,asshowninfigure12.23.

FIGURE12.23Corrosionofiron.IrondissolvesinanodicregionstogiveFe2+.Electronstravelthroughthe
metaltocathodicsiteswhereoxygenisreduced,formingOH.ThecombinationoftheFe2+
andOH,followedbyoxidationinair,givesrust.

Inaqueoussolution,thereductionofoxygenproceedsdifferentlyfromthatshownintheequations
above.Oxideanions,O2,arenotverystableinaqueoussolution.Whentheyreactwithwater,
hydroxideanionsareproduced.Thereductionprocessofoxygeninwateristherefore:

Therustingofironcannowbewrittenas:

However,wearenotfinishedyet.Rustcontainsnotonlyiron(II)ionsbutalsoiron(III)ions.Thus,the
iron(II)ionsformedintheanodicregionsgraduallydiffusethroughthewaterandeventuallycontactthe
hydroxideions.Thiscausesaprecipitateofiron(II)hydroxide,Fe(OH)2,toform,whichisfurther
oxidisedbyoxygentoiron(III)hydroxide,Fe(OH)3.
Wearestillnotfinished.Rustdoesnotconsistofiron(III)hydroxidebutofaremarkablemixedproduct
withtheformulaFeO(OH),whichcanbecalledironoxidehydroxide.FeO(OH)isformedby
dehydrationofFe(OH)3:

Thismechanismofrustingexplainsoneofthemoreinterestingaspectsofthisdamagingprocess.
Perhapsyouhavenoticedthat,whenrustingoccursonthebodyofacar,therustappearsatandaround
abreakorascratchinthesurfaceofthepaint,butthedamageextendsunderthesurfaceforsome
distance.Apparently,theFe2+ionsformedattheanodesitescandiffuseratherlongdistancestothe
holeinthepaint,wheretheyfinallyreactwithairandwatertoformtherust.

Corrosioncanbeinhibitedbyseveraltechniques.Inaprocesscalledgalvanisation,ironobjectsare
coatedwithzinc.SincethereductionpotentialofZn 2+ismorenegativethanthatofFe2+:

theoxidationofzincisfavoured.Thisleadstoformationofaprotectivelayerofazincoxidewhich
lastsuntilallthezinciscorrodedaway.Tinplatingasintincans,incontrast,leadstoaveryrapid
corrosionoftheirononceitssurfaceisscratchedandtheironisexposed,becausetheSn 2+/Snreduction
potential:

isgreaterthanthatofFe2+/Fe,andthereforeSn 2+oxidisesFe.Someoxidesarestableinasensebecause
theyadheretothemetalsurfaceandformanimpermeablelayeroverafairlywidepHrange.Thisis
whyaluminiumreactsonlyveryslowlyinaireventhoughitsreductionpotentialisstronglynegative
.Suchaphenomenoniscalledpassivation.

Anotherprotectingmethodistochangethepotentialofthesubjectbypumpinginelectrons,whichcan
beusedtosatisfythedemandsofoxygenwithoutinvolvingoxidationofthemetal.Cathodicprotection
isaconceptusedtoprotectlargeobjects,suchasships,pipelinesandbuildings,fromrusting(figure
12.24).Theobjectisconnectedtoametalwithamorenegativeelectrodepotential,suchasmagnesium
.Magnesiumactsasasacrificialanodeby

supplyingitselectronstotheiron,whileitisoxidisedtoMg 2+.Youcanseefromthisthattheoccasional
replacementofapieceofmagnesiumismuchcheaperthanreplacinganentireship.
 FIGURE12.24Beforelaunching,ashinynewzincanodediskwasattachedtothebronzerudderofthisboat
toprovidecathodicprotection.Overtime,thezinchascorroded,insteadofthelessreactive
bronze.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.7Electrolysis
Theprecedingsectionshaveshownhowspontaneousredoxreactionscanbeusedtogenerateelectrical
energy.Wenowturnourattentiontotheoppositeprocess:theuseofelectricalenergytoforce
nonspontaneousredoxreactionstooccur.Infact,thesearepreciselythekindsofreactionsthattake
placewhenrechargingbatteries.

WhatisElectrolysis?
Whenelectricityispassedthroughamolten(melted)ioniccompoundorthroughasolutionofan
electrolyte,achemicalreactioncalledelectrolysiscanoccur.Anexampleofanelectrolysisapparatus,
calledanelectrolysiscellorelectrolyticcell,isshowninfigure12.25.Thisparticularcellcontains
moltensodiumchloride.(Asubstanceundergoingelectrolysismustbemoltenorinsolutionsoitsions
canmovefreelyandconductioncanoccur.)Inertelectrodeselectrodesthatwillnotreactwiththe
moltenNaClaredippedintothecellandthenconnectedtoasourceofdirectcurrent(DC)electricity.

FIGURE12.25Electrolysisofmoltensodiumchloride.Thepassageofanelectriccurrentdecomposesmolten
sodiumchlorideintometallicsodiumandgaseouschlorine.

TheDCsourceservesasanelectronpump,pullingelectronsawayfromoneelectrodeandpushing
themthroughtheexternalwiringontotheotherelectrode.Theelectrodefromwhichelectronsare
removedbecomespositivelycharged,whiletheotherelectrodebecomesnegativelycharged.Inthis
example:
Atthepositiveelectrode,oxidationoccursaselectronsarepulledawayfromnegativelycharged
chlorideions.Becauseofthenatureofthechemicalchangeinanelectrolysiscell,thepositive
electrodebecomestheanode,towhichtheanionsmove.
TheDCsourcepumpstheelectronsthroughtheexternalelectriccircuittothenegativeelectrode.
 Here,reductiontakesplaceastheelectronsareforcedontopositivelychargedsodiumions,sothe
negativeelectrodeisthecathode,towhichthecationsmove.
Thechemicalchangesthatoccurattheelectrodescanbedescribedbythefollowingequations:

(AtthemeltingpointofNaCl,801C,metallicsodiumisaliquid.)

ComparisonofElectrolyticandGalvanicCells

Inagalvaniccell,thespontaneouscellreactiondepositselectronsontheanodeandremovesthem
fromthecathode.Asaresult,theanodecarriesaslightnegativechargeandthecathodeaslight
positivecharge.
Inanelectrolyticcell,thesituationisreversed.Here,oxidationattheanodemustbeforcedto
occur,whichrequiresthattheanodeispositivesoitcanremoveelectronsfromthereactantatthat
electrode.

Ontheotherhand,thecathodemustbemadenegativesoitcanforcethereactantattheelectrodeto
acceptelectrons.Byagreementamongscientists,thenamesanodeandcathodearealwaysassigned
accordingtothenatureofthereactiontakingplaceattheelectrode:
Ifthereactionisoxidation,theelectrodeiscalledtheanode.
Ifthereactionisreduction,theelectrodeiscalledthecathode.

Itisimportanttoremember:
Inanelectrolyticcell,thecathodeisnegative(reduction)andtheanodeispositive(oxidation).
Inagalvaniccell,thecathodeispositive(reduction)andtheanodeisnegative(oxidation).

ElectrolysisinAqueousSolutions
Whenelectrolysisiscarriedoutinanaqueoussolution,theelectrodereactionscanbemore
complicatedwemustconsideroxidationandreductionofthesoluteaswellasoxidationandreduction
ofwater.(Itisimportanttonotethatthenatureoftheelectrodematerialitselfcanalsostronglyinfluence
theoutcomeoftheelectrolysis.Wewillnotdiscussthisfurtherhere.)Forexample,electrolysisofa
solutionofpotassiumsulfate(figure12.26)giveshydrogenandoxygen.Atthecathode,wateris
reduced,notK+:

Attheanode,waterisoxidised,notthesulfateion:
 FIGURE12.26Electrolysisofanaqueoussolutionofpotassiumsulfate.Theproductsoftheelectrolysisare
thegaseshydrogenandoxygen.

Wecanunderstandwhytheseredoxreactionsoccurifweexaminereductionpotentialdatafromtable
12.1.Forexample,atthecathodewehavethefollowingcompetingreactions:

WaterhasamuchlessnegativereductionpotentialthanK+,whichmeansH2Oismucheasiertoreduce
thanK+.Duringelectrolysis,themoreeasilyreducedsubstanceisreducedandH2isformedatthe
cathode.

Attheanode,thepossibleoxidationhalfreactionsare:

Intable12.1,wefindthemwrittenintheoppositedirection:

The valuestellusthatS2O82ismoreeasilyreducedthanO2.ButifS2O82isreduced,thenthe
product,SO42,mustbelesseasilyoxidised.Statedanotherway,thehalfreactionwiththesmaller(less
positive)reductionpotentialoccursmoreeasilyasanoxidation.Asaresult,duringelectrolysis,wateris
oxidisedinsteadofSO42,andO2isformedattheanode.

TheoverallcellreactionfortheelectrolysisoftheK2SO4solutionis:
Thenetchangethenis:

Thewordelectrolysisabovethearrowintheequationshowsthatelectricityisthedrivingforceforthis
otherwisenonspontaneousreaction.

Whatistheroleofpotassiumsulfateinthiselectrolysis,giventhatneitherK+norSO42ionsare
changedbythereaction?Iftheelectrolysisisattemptedwithpuredistilledwater,nothinghappens.
Thereisnocurrentflow,andnoH2orO2forms.Apparently,thepotassiumsulfatemusthavesome
purpose.

ThefunctionofK2SO4(oranyotherelectrolyte)istomaintainelectricalneutralityinthevicinityofthe
electrodes.IfK2SO4werenotpresentandtheelectrolysisweretooccuranyway,thesolutionaroundthe
anodewouldbecomepositivelycharged.ItwouldbecomefilledwithH+ions,withnonegativeionsto
balancetheircharge.Similarly,thesolutionsurroundingthecathodewouldbecomenegativelycharged
asitisfilledwithOHions,withnonearbypositiveions.Theformationofpositivelyornegatively
chargedsolutionsrequirestoomuchenergyso,intheabsenceofanelectrolyte,theelectrodereactions
cannottakeplace.

WhenK2SO4isinthesolution,K+ionscanmovetowardsthecathodeandminglewiththeOHionsas
theyareformed.Similarly,theSO42ionscanmovetowardstheanodeandminglewiththeH+ionsas
theyareproducedthere.Inthisway,atanymoment,eachsmallregionofthesolutioncancontainthe
samenumberofpositiveandnegativechargesandtherebyremainneutralinotherwords,theK+and
SO42ionscompletetheelectricalcircuit.

Reductionpotentialscanbeusedtoanticipatetheproductsofanelectrolysis.Thisisillustratedby
workedexample12.13.

WORKEDEXAMPLE12.13

PredictingtheProductsinanElectrolysisReaction
Electrolysisisplannedforanaqueoussolutionthatcontainsamixtureof0.50MZnSO4and
0.50MNiSO4.Onthebasisofreductionpotentials,whatproductsareexpectedtobe
observedattheelectrodes?Whatistheexpectednetcellreaction?

Analysis
Weneedtoconsiderthecompetingreactionsatthecathodeandtheanode.Atthecathode,
thehalfreactionwiththemostpositivereductionpotentialwillbetheoneexpectedtooccur
asareduction.Attheanode,thehalfreactionwiththeleastpositivereductionpotentialisthe
onethatshouldoccurasanoxidation.

Solution

Atthecathode,thecompetingreductionreactionsinvolvethetwocationsandwater.The
reactionsandtheirreductionpotentialsare:

ThemostpositivereductionpotentialisthatofNi2+,soweexpectthisiontobereducedat
thecathodeandsolidnickeltobeformed.

Attheanode,thecompetingoxidationreactionsareforwaterandSO42ions.Intable12.1,
oxidisedsubstancesarefoundontherighthandsideofthehalfreactions.Thetwohalf
reactionswiththeseasproductsare:

Thehalfreactionwiththelesspositive occursmoreeasilyasanoxidation,soweexpect
theoxidationhalfreactiontobe:

Attheanode,weexpectO2tobeformed.

Thepredictednetcellreactionisobtainedbycombiningthetwoexpectedelectrodehalf
reactions,makingtheelectronlossequaltotheelectrongain:

Isouranswerreasonable?

Wecancheckthelocationsofthehalfreactionsintable12.1toconfirmourconclusions.For
thereductionstep,themorepositivethereductionpotential,thegreateritstendencytooccur
asareduction.Amongthecompetinghalfreactionsatthecathode,thereductionpotentialfor
Ni2+ishighest,soweexpectthatNi2+istheeasiesttoreduceandNi(s)shouldbeformedat
thecathode.

Fortheoxidationstep,themorenegativethereductionpotential,theeasieritistooccurasan
oxidation.Onthisbasis,theoxidationofwateriseasierthantheoxidationofSO42,sowe
 expectH2OtobeoxidisedandO2tobeformedattheanode.

PRACTICEEXERCISE12.15
Intheelectrolysisofanaqueoussolution
containingbothCd 2+andCr3+,what
productdoweexpectatthecathode?

StoichiometryofElectrochemicalReactions
Inabout1833,BritishscientistMichaelFaradaydiscoveredthattheamountofchemicalchangethat
occursduringelectrolysisisdirectlyproportionaltotheamountofelectricchargethatispassedthrough
anelectrolyticcell.Forexample,thereductionofcopperionsatacathodeisgivenbytheequation:

Depositionof1molofmetalliccopperrequires2molofelectrons.Therefore,todeposit2molof
copperrequires4molofelectrons,andthattakestwiceasmuchelectricity.Thehalfreactionforan
oxidationorreduction,therefore,relatestheamountofchemicalsubstanceconsumedorproducedto
theamountofelectronsthattheelectriccurrentmustsupply.

TheSIunitofelectriccurrentistheampere(A)andofchargeisthecoulomb(C).Acoulombisthe
amountofchargethatpassesbyagivenpointinawirewhenanelectriccurrentof1ampereflowsfor1
second:

Forexample,ifacurrentof4Aflowsthroughawirefor10s,40Cpassesbyagivenpointinthewire.

Aswenotedearlier,1molofelectronscarriesachargeof96485C.Withthis,laboratorymeasurements
canberelatedtotheamountofchemicalchangethatoccursduringanelectrolysis.Theamountof
productformedcanbecalculatedusingFaraday'slaw:

whereI=current(A),t=time(s),z=numberofelectronstransferredinthebalancedequationandF=
Faradayconstant(Cmol1).Workedexample12.14demonstratestheuseofthisequation.

WORKEDEXAMPLE12.14

CalculationsRelatedtoElectrolysis
Whatmassofcopperisdepositedonthecathodeofanelectrolyticcellifanelectriccurrent
of2.00AisrunthroughasolutionofCuSO4foraperiodof20.0min?
 Analysis

WeobtaintheamountofcopperbyusingFaraday'slaw.Todeterminethemassofcopper,
wemultiplytheamountofcopperbythemolarmassofcopper.

Solution

Firstweconvertminutestoseconds:20.0min=1.2010 3s.WethenuseFaraday'slawto
determinetheamountofcopper(rememberthatF=96485Cmol1or9.648510 4As
mol1):

Weobtainthemassbymultiplyingbythemolarmassofcopper:

Theelectrolysiswilldeposit0.788gofcopperonthecathode.

Isouranswerreasonable?

Checkthatyouhaveinsertedthecorrectnumbersintotheequation.Itisimportantto
remembertoconvertminutestosecondsinthistypeofproblem.

PRACTICEEXERCISE12.16
Electrolysisprovidesausefulwaytodeposit
athinmetalliccoatingonanelectrically
conductingsurface.Thetechniqueiscalled
electroplating.Howmuchtimewouldittake
inminutestodeposit0.500gofmetallic
nickelonametalobjectusingacurrentof
3.00A?Thenickelisreducedfromthe+2
oxidationstate.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
12.8Batteries
Asmentionedearlier,thepotentialproducedbyonegalvaniccellisnotenoughtopowerelectronic
instrumentssuchastoys,torches,electroniccalculators,laptopcomputers,heartpacemakers,video
camerasormobilephones,letaloneacar.Abattery(figure12.27)containsagroupofgalvaniccells
usuallyconnectedinseriessothatthepotentialsoftheindividualcellsaddup.Thesedevicesare
classifiedasbeingeitherprimarycells(cellsnotdesignedtoberechargedtheyarediscardedaftertheir
energyisdepleted)orsecondarycells(cellsdesignedforrepeatedusetheycanberecharged).Inthis
section,wewillfocusonthemostimportanttypesofbatteries,suchascarbatteries,drycellsand
rechargeablebatteries,aswellasfuelcells.

FIGURE12.27Theoldestknownelectricbatteryinexistence(datingfromabout2200yearsago),discovered
in1938inBaghdad,Iraq,consistsofacoppertubesurroundinganironrod.Iffilledwithan
acidicliquidsuchasvinegar,thecellcouldproduceasmallelectriccurrent.

TheLeadStorageBattery
Thecommonleadstoragebattery(figure12.28)usedtostartacariscomposedofanumberof
secondarycells,eachhavingapotentialofabout2V,thatareconnectedinseriessothattheirvoltages
areadditive(seefigure12.29).Mostcarbatteriescontainsixsuchcellsandgiveabout12V,but6,24
and32Vbatteriesarealsoavailable.
 FIGURE12.28Leadstoragebattery.A12voltleadstoragebattery,suchasthoseusedinmostcars,consists
ofsixcellsliketheoneshownhere.Noticethattheanodeandcathodeeachconsistsofseveral
platesconnectedtogether.Thisallowsthecelltoproducethelargecurrentsnecessarytostarta
car.

FIGURE12.29Ifthree2voltcellsareconnectedinseries,theirvoltagesareadditivetoprovideatotalof6
volts.Carsgenerallyuse12voltbatteriescontainingsixcells.

Theanodeofeachcellinatypicalleadstoragebatteryiscomposedofasetofleadplates,thecathode
consistsofanothersetofplatesthatholdacoatingofPbO2,andtheelectrolyteissulfuricacid.Whenthe
batteryisdischarging,theelectrodereactionsare:

Thenetcellreactionistherefore:

Thereactionoccurringinaleadbatteryisanexampleofasymproportionation(orcomproportionation)
reaction,whereachemicalreactionoccursbetweentworeactantsthatcontainthesameelementin
differentoxidationstates.Theproducthasanoxidationnumberintermediatetothetworeactants.Inthis
specificreaction,PbO2(oxidationstateofPb=+4)undergoessymproportionationwithelementalPb
(oxidationstate=0)togivePbSO4(oxidationstateofPb=+2).

Itshouldbenotedthatthereverseofasymproportionationreactionisadisproportionationreaction,
whereaspeciesissimultaneouslyoxidisedandreducedtoformtwodifferentproducts.Anexampleofa
disproportionationreactionisthatofchlorinegas(oxidationnumber=0)withdilutesodiumhydroxide,
whichgivessodiumchloride,NaCl(oxidationstateofCl=1),sodiumchlorate,NaClO3(oxidationstate
ofCl=+5)andwater.Therelevantredoxreactionisgivenby:

Asaleadbatterydischarges,thesulfuricacidconcentrationdecreases,whichprovidesaconvenient
meansofcheckingthestateofthebattery.Becausethedensityofasulfuricacidsolutiondecreasesasits
concentrationdrops,theconcentrationcanbedeterminedverysimplybymeasuringthedensitywitha
hydrometer,whichconsistsofarubberbulbthatisusedtodrawthebatteryfluidintoaglasstube
containingafloat(seefigure12.30).Thedepthtowhichthefloatsinksisinverselyproportionaltothe
densityoftheliquidthedeeperthefloatsinks,theloweristhedensityoftheacidandtheweakeristhe
chargeofthebattery.Thenarrowneckofthefloatisusuallymarkedtoindicatethestateofchargeofthe
battery.
 FIGURE12.30Abatteryhydrometer.Batteryacidisdrawnintotheglasstube.Thedepthtowhichthefloat
sinksisinverselyproportionaltotheconcentrationoftheacidand,therefore,tothestateof
chargeofthebattery.

Theprincipaladvantageoftheleadstoragebatteryisthatthecellreactionsthatoccurspontaneously
duringdischargecanbereversedbytheapplicationofavoltagefromanexternalsource.Inotherwords,
thebatterycanberechargedbyelectrolysis.Thereactionforbatteryrechargeis:

Disadvantagesoftheleadstoragebatteryarethatitisveryheavyandthatitscorrosivesulfuricacidcan
spill.Themostmodernleadstoragebatteriesusealeadcalciumalloyastheanode.Thisreducestheneed
toventindividualcellssothebatterycanbesealed,preventingspillageoftheelectrolyte.

DryCellBatteries
Electronichouseholdinstruments,suchasremotecontrols,wristwatches,DVDandMP3players,torches
andradios,arepoweredbysmall,highlyefficientdrycellbatteries.Theyaremanufacturedindifferent
sizes,namedbytheAclassification,whereAAAandAAarethemostcommonsizesusedinremote
controls,digitalcamerasandDVDplayers.ThelargerCsizeismostoftenusedinportablestereosand
manyelectricaltoys,whereassizeDisthestandardbatteryusedinbatonshapedtorches.

Theordinary,relativelyinexpensive1.5Vdrycellisthezincmanganesedioxidecell,orLeclanchcell
(namedafteritsinventor,GeorgeLeclanch,18391882).Itsoutershellismadeofzinc,whichservesas
theanode(figure12.31).Theexposedoutersurfaceatthebottomofthecellisthenegativeendofthe
battery.Thecathodeconsistsofacarbon(graphite)rodsurroundedbyamoistpasteofgraphitepowder,
manganesedioxideandammoniumchloride.
 FIGURE12.31Acutawayviewofazincmanganesedioxidedrycell(Leclanchcell).

Theanodereactionissimplytheoxidationofzinc:

Thecathodereactioniscomplex,andamixtureofproductsisformed.Oneofthemajorreactionsis:

TheammoniathatformsatthecathodereactswithsomeoftheZn 2+producedfromtheanodetoforma
complexion,Zn(NH3)42+.Becauseofthecomplexityofthecathodehalfcellreaction,nosimpleoverall
cellreactioncanbewritten.

AmorepopularversionoftheLeclanchbatteryusesabasic,oralkaline,electrolyte(generally
potassiumhydroxide)andiscalledanalkalinebatteryoralkalinedrycell.It,too,usesZnandMnO2as
reactantsbutunderbasicconditions(figure12.32).Thehalfcellreactionsare:

andthevoltageisabout1.54V.Thealkalinedrycellhasalongershelflifeandcandeliverhigher
currentsforlongerthanthelessexpensiveLeclanchcellshowninfigure12.31.Overtime,however,
alkalinebatteriesarepronetocorrosionandleaking.Thereleasedcorrosivepotassiumhydroxide,which
canalsoemergefromseamsaroundthebattery,formsafeatherycrystallinestructureontheoutsideofthe
battery(figure12.33).Thedamagecanspreadfurtherthroughthemetalelectrodestocircuitboards
leadingtooxidationofcoppertracesandothercomponents,whichcanresultinpermanentdamagetothe
circuitryanddestructionoftheequipment.
 FIGURE12.32Asimplifieddiagramofanalkalinezincmanganesedioxidedrycell.

FIGURE12.33Alkalinedrycellsarepronetoleakageandcorrosion.

Thenickelcadmiumstoragecell,ornicadbattery,(commonlyabbreviatedtoNiCdornicad)isa
secondarycellthatproducesapotentialofabout1.31.4V.ThecathodeintheNiCdcellisNiO(OH),a
compoundofnickelinthe+3oxidationstate,andtheelectrolyteisasolutionofKOH.Theelectrode
reactionsinthecellduringdischargeare:

Thenickelcadmiumbatterycanberechargedbyreversingtheanodeandcathodereactionsaboveto
remakethereactants.Thebatterycanbesealedtopreventleakage,whichisparticularlyimportantin
electronicdevices.

Nickelcadmiumbatteriesworkespeciallywellinapplicationssuchasportablepowertools,DVDplayers
andevenelectriccars.Theyhaveahighenergydensity(availableenergyperunitvolume),theycan
releaseenergyquickly,andtheycanberechargedrapidly.

ModernHighperformanceBatteries

NickelMetalHydrideBattery
Nickelmetalhydride(NiMH)batteriesaresecondarycellsandhavebeenusedextensivelyinrecent
yearstopowerdevicessuchasmobilephones,videocamerasandevenelectricvehicles.Theyare
similarinmanywaystothealkalinenickelcadmiumcellsdiscussedearlier,exceptfortheanodereactant,
whichishydrogen.Atfirst,thisseemsodd,becausehydrogenisagasatroomtemperatureand
atmosphericpressure.However,inthelate1960s,itwasdiscoveredthatsomemetalalloys(suchas
LaNi5,analloyoflanthanumandnickel,andMg 2Ni,analloyofmagnesiumandnickel)canabsorband
holdsubstantialamountsofhydrogeninitsatomicformandthatthehydrogencouldbemadeto
participateinreversibleelectrochemicalreactions.(Note:Thetermmetalhydridehascometobeusedto
describethehydrogenholdingalloyinwhichhydrogeniscontainedinitsatomicform.Thereare
compoundsofhydrogenwithmetalssuchassodiumthatactuallycontainthehydrideion,H.Themetal
hydridesdescribedherearenotofthattype.)

AsintheNiCdcell,thecathodeinNiMHbatteriesisNiO(OH)andtheelectrolyteisasolutionofKOH.A
diagramofacylindricalcellisshowninfigure12.34.UsingthesymbolMHtostandforthemetal
hydride,thereactionsinthecellduringdischargeare:

Whenthecellisrecharged,thesereactionsarereversed.TheprincipaladvantageoftheNiMHcellover
theNiCdcellisthatitcanstoreabout50%moreenergyinthesamevolume.
 FIGURE12.34Cutawayviewofanickelmetalhydridecell.Theelectrodesandwichisrolledupthisyieldsa
largeeffectiveelectrodeareaandenablesthecelltodeliverlargeamountsofenergyquickly.

LithiumIonCells
Ifyoulookatthelocationoflithiuminthetableofreductionpotentials(table12.1),youwillseethatit
hasthemostnegativereductionpotentialofanymetal.Thismeansthatlithiumisveryeasilyoxidised
electrochemically,anditslargenegativereductionpotentialsuggestsithasalotofappealasananode
material.Furthermore,lithiumisaverylightweightmetal,soacellemployinglithiumasareactantwould
alsobelightweight.

Attemptstomakerechargeablelithiumbatteriescontaininglithiummetalelectrodeshavebeenplagued
withsafetyproblems.Successcamewiththedevelopmentofthelithiumioncell,whichuseslithiumions
ratherthanmetalliclithium.ThetransportofLi+ionsthroughtheelectrolytefromoneelectrodetothe
otherisaccompaniedbythetransportofelectronsthroughtheexternalcircuittomaintainchargebalance.
Thefollowingparagraphsdescribehowlithiumionsareusedinarechargeablecell.

Itwasdiscoveredthat,becausetheyaresmall,Li+ionscanslipbetweenlayersofatomsincertain
crystallinesubstances(aprocesscalledintercalation).Graphiteissuchasubstance.Aswesawinchapter
7,graphiteconsistsoflayersoffusedhexagonalringsofcarbonatoms.Theothermostcommonlyused
compoundabletointercalateLi+ionsisLiCoO2.Thesearethematerialsusedtomaketheelectrodes.

Whenthecellisconstructed,itisinitsunchargedstatewithnoLi+ionsbetweenthelayersofcarbon
atomsinthegraphite.Whenthecellisbeingcharged(figure12.35a),Li+ionsleaveLiCoO2(withxbeing
theamountoftransferredLi+)andtravelthroughtheelectrolytetothegraphite:
 FIGURE12.35 Lithiumioncell.
(a)Duringthechargingcycle,anexternalvoltageforceselectronsthroughtheexternal
circuitandcauseslithiumionstotravelfromtheLiCoO2 electrodetothegraphite
electrode.
(b)Duringdischarge,thelithiumionsspontaneouslymigratebacktotheLiCoO2 electrode,
andelectronsflowthroughtheexternalcircuittobalancethecharge.

Whenthecellspontaneouslydischargestoprovideelectricalpower(figure12.35b),Li+ionsmoveback
throughtheelectrolytetothecobaltoxide,whileelectronsmovethroughtheexternalcircuitfromthe
graphiteelectrode(anode)tothecobaltoxideelectrode(cathode).IfwerepresenttheamountofLi+
transferringbyy,thedischargereactionis:

Thus,thecharginganddischargingcyclessimplysweepLi+ionsbackandforthbetweenthetwo
electrodes,withelectronsflowingthroughtheexternalcircuittokeepthechargeinbalance.

Twotypesoflithiumioncellshavebeendeveloped.Theonemostcommonlyusedtodayinmobile
phonesandlaptopcomputersemploysaliquidelectrolyte(usuallycontainingLiPF6,acompoundwith
Li+andPF6ions).Thecellgeneratesabout3.7V,whichmeansthreeNiCdcellsconnectedinseries
wouldberequiredtoformanequivalentbatterypack.Inaddition,alithiumioncellhasabouttwicethe
energydensityofastandardNiCdcell.

FuelCells
Thegalvaniccellsdiscussedsofarcanproducepoweronlyforalimitedtimebecausetheelectrode
reactantsareeventuallydegraded.Fuelcellsaredifferenttheyareelectrochemicalcellsinwhichthe
electrodereactantsaresuppliedcontinuouslyandcanoperatewithoutatheoreticallimitaslongasthe
supplyofreactantsismaintained.Thismakesfuelcellsanattractivesourceofpowerwherelongterm
generationofelectricalenergyisrequired.

Figure12.36illustratesanearlydesignofahydrogenoxygenfuelcell.Theelectrolyte,ahot(200C),
concentratedsolutionofpotassiumhydroxideinthecentrecompartment,isincontactwithtwoporous
electrodesthatcontainacatalyst(usuallyplatinum)tofacilitatetheelectrodereactions.Gaseoushydrogen
andoxygenunderpressurearecirculatedsoastocomeincontactwiththeelectrodes.Atthecathode,
oxygenisreduced:

Attheanode,hydrogenisoxidisedtowater:

Someofthewaterformedattheanodeleavesassteammixedwiththecirculatinghydrogengas.Thenet
cellreaction,aftermakingelectronlossequaltoelectrongain,is:

FIGURE12.36Ahydrogenoxygenfuelcell.

Amajoradvantageofthefuelcellisthatthereisnoelectrodematerialtobereplaced,asthereisinan
ordinarybattery.Thefuelcanbefedincontinuouslytoproducepower.Infact,hydrogenoxygenfuel
cellswereusedintheGeminiandApollomissionsinthesecondhalfofthetwentiethcenturyandother
spaceprogramsforjustthisreason.

Onereasonfuelcellsaresoappealingistheirthermodynamicefficiency.Inafuelcell,thenetreactionis
equivalenttocombustion.Theproductionofusableenergybythedirectcombustionoffuelsisan
extremelyinefficientprocess.Largelybecauseoftheconstraintssetbyfundamentalthermodynamic
principles,modernelectricalpowerplantsareunabletoharnessmorethanabout35to40%ofthe
potentialenergyinoil,coalornaturalgas.Apetrolordieselenginehasanefficiencyofonlyabout25to
30%.Therestoftheenergyislosttothesurroundingsasheat,whichiswhyavehiclemusthavean
effectivecoolingsystem.
Fuelcellsburnfuelunderconditionsthataremuchmorethermodynamicallyreversiblethansimple
combustion.Theythereforeachievemuchgreaterefficiencies75%isquitefeasible.Inaddition,
hydrogenoxygenfuelcellsareessentiallypollutionfree.Theonlyproductformedbythecelliswater.
However,hydrogenfuelisnotnecessarilyproducedbypollutionfreeprocesses.

Advancesinfuelcelldevelopmenthaveledtoloweroperatingtemperaturesandtheabilitytouse
methanol,aliquidatroomtemperature,asasourceofhydrogen.Thehydrogenisgeneratedfrom
methanolvapour,CH3OH(g),byacatalyticprocess.Thenetreactionis:

DaimlerChrysleroriginallydemonstratedthefeasibilityofsuchasystembydrivingitsNECAR5vehicle,
poweredbyfivefuelcells,5000kilometresacrosstheUnitedStatesin16days.Anonboardfuelreformer
extractedhydrogenfrommethanoltofeedthefuelcells.

Thedevelopmentofefficientfuelcellsisanactiveresearcharea,especiallyforthetransportationmarket.

ChemistryResearch

GreenElectrochemistry

ProfessorAlanMBondisknownworldwideforhisextensiveworkintheareaofelectro
chemistry.HeisR.L.MartinDistinguishedProfessorofChemistryandHeadofthe
ElectrochemistryresearchgroupatMonashUniversityinVictoria.Hismajorresearchinterest
concernsthetheory,instrumentationandapplicationofmodernelectrochemicalmethodsinthe
areaofinorganicandanalyticalchemistry.

Electrochemistryisthestudyoftheformationandseparationofchargeinmatter,andtheways
inwhichsuchchargemovesinmatter.Itiscentraltomanyindustrialprocessesusedinmining
andmanufacturing,whileitseverydayimportanceisevidentinthebatteriesusedtopower
portabledevicessuchasmobilephonesandMP3players.Despiteitslonghistory,thescience
ofelectrochemistryisstilldevelopingaschemistssearchfornewandmorepowerfuldevices.

OneareainwhichProfessorBond'sgroupisfocusingitsresearchisgreenchemistry.Green
chemistryusessocalledgreenchemicalsonesthatdonotadverselyaffectthe
environment.Ionicliquids(figure12.37)areincreasinglybeingadvocatedasgreensolvents
forelectrochemicalapplicationsinmetaldeposition,batteryelectrolytesandelectrosynthesis.
 FIGURE12.37Ionicliquidsdisplayinterestingmiscibilitycharacteristics.Inthisexample,theionic
liquid(bottomlayer)mixeswithneitherwater(middlelayer)noranorganicsolvent
(toplayer).

Ofparticularinterestareroomtemperatureionicliquidsbecauseoftheirnegligiblevapour
pressure,lowtoxicity,highchemicalandthermalstability,highconductivity,significant
electrochemicalstabilityandabilitytodissolveawiderangeofcompounds.However,because
oftheirlowvapourpressure,roomtemperatureionicliquidsarenonvolatileandhencedifficult
topurifyorrecover.ProfessorBond'sgrouphasrecentlyinvestigatedtheelectrochemical
behaviourofthedistillableroomtemperatureionicliquidDIMCARB.Thisionicliquidis
unusualbecauseitcanbereadilypreparedinlargequantitiesandatlowcostbymixing
gaseouscarbondioxide,CO2,withdimethylamine,(CH3)2NH,anditiseasilyrecoveredby
decompositionbacktoitsgaseouscomponents.

TheBondgrouphasshownthatthisionicliquidisausefulsolventinanumberofunusual
electrochemicalprocesses.Forexample,bothAg +andAu 3+ionsundergospontaneous
reductioninDIMCARBtoformdifferenttypesofnanostructures.Overall,Bond'sstudieshave
shownthatcertaingreenionicliquids,suchasDIMCARB,maybeverysuitableforthe
synthesisofchemicalsthatinvolveelectrochemicaltransformations,andtheymaytherefore
finduseasenvironmentallyfriendlyreplacementsforthesolventsusuallyusedinthese
processes.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
OxidationandReduction
Oxidationisthelossofelectronsoranincreaseinoxidationnumberreductionisthegainofelectrons
oradecreaseinoxidationnumber.Bothalwaysoccurtogetherinreductionoxidation(orredox)
reactions.Thesubstanceoxidisedisthereducingagentthesubstancereducedistheoxidisingagent.
Oxidationnumbersareabookkeepingdevicethatweusetofollowchangesinredoxreactions.The
termoxidationstateisequivalenttooxidationnumber.

BalancingNetIonicEquationsforRedoxReactions
Inabalancedredoxequation,thenumberofelectronsgainedbyonesubstanceisalwaysequaltothe
numberlostbyanothersubstance.Tobalancearedoxequation,theskeletonnetionicequationis
dividedintotwohalfequations,whicharebalancedseparatelybeforebeingrecombinedtogivethe
finalbalancednetionicequation.Forreactionsinbasicsolution,theequationisfirstbalancedasifit
occurredinanacidicsolution,andthenthebalancedequationisconvertedtoitsproperformforabasic
solutionbyaddinganappropriatenumberofOHions.

GalvanicCells
Agalvaniccelliscomposedoftwohalfcells,eachcontaininganelectrodeincontactwithanelectrolyte
reactant.Aspontaneousredoxreactionisthusdividedintoseparateoxidationandreductionhalf
reactions,withtheelectrontransferoccurringthroughanexternalelectriccircuit.Reductionoccursat
thecathodeoxidationoccursattheanode.Inagalvaniccell,thecathodeispositivelychargedandthe
anodeisnegativelycharged.Thehalfcellsareusuallyconnectedbyasaltbridgetocompletethe
electriccircuitthispermitselectricalneutralitytobemaintainedbyallowingcationstomovetowards
thecathodeandanionstowardstheanode.

ReductionPotentials
Thepotential(expressedinvolts)producedbyacellisequaltothestandardcellpotentialwhenallion
concentrationsare1Mandthepartialpressureofanygasinvolvedequals110 5Pa.Thecellpotential
canbeconsideredtobethedifferencebetweenthereductionpotentialsofthehalfcells.Inthe
spontaneousreaction,thehalfcellwiththemorepositivereductionpotentialundergoesreductionand
forcestheothertoundergooxidation.Thereductionpotentialsofisolatedhalfcellscannotbe
measured,butvaluesareassignedbychoosingthestandardhydrogenelectrodeasareference
electrodeitsreductionpotentialisassignedavalueofexactly0V.SpeciesmoreeasilyreducedthanH+
havepositivereductionpotentialsthoselesseasilyreducedhavenegativereductionpotentials.
Reductionpotentialscanbeusedtopredictthecellreactionandtocalculate ,aswellastopredict
whetheragivenreactionisspontaneous.

Insolutionscontainingnonoxidisingacids,thestrongestoxidisingagentisH+.Thereactionofametal
withanonoxidisingacidgiveshydrogengasandasaltoftheacid.Onlymetalswithmorenegative
reductionpotentialsthanhydrogenreactthisway.Oxidisingacids,suchasconcentratedHNO3or
concentratedH2SO4,containananionthatisastrongeroxidisingagentthanH+,andtheycanoxidise
manymetalsthatnonoxidisingacidscannot.

RelationshipBetweenCellPotential,ConcentrationandGibbsEnergy
Thevaluesof andKc forareactioncanbecalculatedfrom .TheyallinvolvetheFaraday
constant,F,whichequalsthenumberofcoulombs(C)ofchargepermoleofelectrons(1F=96485C
mol1).TheNernstequationrelatesthecellpotentialtothestandardcellpotentialandthereaction
quotient.Itallowsthecellpotentialtobecalculatedforionconcentrationsotherthan1M.

Corrosion
Metalscorrodebecausetheyoxidiseeasily.Thecorrosionofiron(formationofrust)isan
electrochemicalreactionthatinvolvesbothoxygenandwater.Somemetalsforminsolubleoxides,
whichpreventthemfromfurtheroxidation(passivation).Corrosioncanbecombattedbyprocessessuch
asgalvanisationandcathodicprotection.

Electrolysis
Inanelectrolyticcell,aflowofelectricitycausesanotherwisenonspontaneousreactiontooccur.A
negativelychargedcathodecausesreductionofonereactantandapositivelychargedanodecauses
oxidationofanother.Theelectrodereactionsaredeterminedbywhichspeciesismosteasilyreduced
andwhichismosteasilyoxidisedhowever,inaqueoussolutions,complexsurfaceeffectsatthe
electrodescanalterthenaturalorder.Intheelectrolysisofwater,anelectrolytemustbepresentto
maintainelectricalneutralityattheelectrodes.TheFaradayconstant,F,isequaltothechargecarriedby
1molofelectrons,96485C.Theproductofcurrent(amperes)andtime(seconds)givescoulombs.
Theserelationshipsandthehalfreactionsthatoccurattheanodeorcathodeallowustorelatethe
amountofchemicalchangetomeasurementsofcurrentandtime.

Batteries
Theleadstoragebatteryandthenickelcadmium(nicad)batteryaresecondarycellsandare
rechargeable.Thestateofchargeofaleadstoragebatterycanbetestedwithahydrometer,which
measuresthedensityofthesulfuricacidelectrolyte.Thezincmanganesedioxidecell(theLeclanch
cellorcommondrycell)andthecommonalkalinebattery(whichusesessentiallythesamereactionsas
thelessexpensivedrycell)areprimarycellsandarenotrechargeable.Therechargeablenickelmetal
hydridebattery(NiMH)useshydrogencontainedinametalalloyasitsanodereactantandhasahigher
energydensitythanthenicadbattery.Therechargeablelithiumioncellproducesalargecellpotential
andhasaverylargeenergydensity.Lithiumioncellsstoreandreleaseenergybytransferringlithium
ionsbetweenelectrodeswheretheLi+ionsareintercalatedbetweenlayersofatomsintheelectrode
materials.Fuelcells,whichhavehighthermodynamicefficiencies,canprovidecontinuouspower
becausetheyconsumefuelthatcanbefedcontinuously.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Rulesforassigningoxidationnumbers(section12.1)
Usetheserulestoassignoxidationnumberstotheatomsinachemicalformula.Usechangesin
oxidationnumberstoidentifyoxidationandreduction.
1.Theoxidationnumberofanyfreeelement(anelementnotcombinedchemicallywithadifferent
element)is0.Forexample,Ar,Fe,OinO2,PinP4andSinS8allhaveoxidationnumbersof0.
2.Theoxidationnumberofanysimple,monatomicion(e.g.Na+andCl)isequaltothechargeon
theion.
3.Thesumofalltheoxidationnumbersoftheatomsinaneutralmoleculemustequal0.Thesumof
alltheoxidationnumbersinapolyatomicionmustequalthechargeontheion.
4.Inallofitscompounds,fluorinehasanoxidationnumberof1.
5.Inmostofitscompounds,hydrogenhasanoxidationnumberof+1.
6.Inmostofitscompounds,oxygenhasanoxidationnumberof2.

Balancingredoxequations(section12.2)
Thefollowingstepsareusedtobalanceanequationforaredoxreactioninanacidicsolution.
1.Identifyreactantsandproductsforeachhalfequation.
2.BalanceatomsotherthanHandO.
3.BalanceoxygenbyaddingH2O.
4.BalancehydrogenbyaddingH+.
5.Balancenetchargebyaddinge.
6.Makeegainequaleloss.
7.Addthebalancedhalfequations.
8.Cancelanyspeciesthatisthesameonbothsides.
9.Checkthattherearethesamenumberandtypeofatomsandthesamechargeoneachsideofthe
reaction.
Thefollowingadditionalstepsareusedtobalanceanequationforaredoxreactioninabasicsolution.
10.TakenoteofthenumberofH+inthebalancedequationandaddthesamenumberofOHto
eachside.
11.CombineeachpairofH+andOHtoformoneH O.
2
12.CancelanyH2Othatoccuronbothsides.
13.Checkthattherearethesamenumberandtypeofatomsandthesamechargeoneachsideof
thereaction.

Standardreductionpotentials(section12.4)
Inagalvaniccell,thedifferencebetweentwostandardreductionpotentialsequalsthestandardcell
potential.Comparingreductionpotentialsletsuspredicttheelectrodereactionsinelectrolysis.

Standardcellpotentials(section12.4)
Bycalculating ,wecanpredictthespontaneityofaredoxreaction.Wecanuse tocalculate
andequilibriumconstants.TheyarealsoneededintheNernstequationtorelateconcentrationsof
speciesingalvaniccellstothecellpotential.
 (section12.5)
ThisequationisusedtocalculatestandardGibbsenergychangesfromstandardcellpotentials,andvice
versa.

(section12.5)
Thisequationisusedtocalculateequilibriumconstantsfromstandardcellpotentials.

Nernstequation (section12.5)

Thisequationisusedtocalculatethecellpotentialfrom andconcentrationdatawecanalso

calculatetheconcentrationofaspeciesinsolutionfrom andameasuredvalueof .

Faradayconstant,F=96485Cmol1(section12.5)
Besidesbeingaconstantintheequationsabove,theFaradayconstantrelatescoulombs(obtainedfrom
theproductofcurrentandtime)tomolesofchemicalchangeinelectrochemicalreactions.

Faraday'slaw(section12.7)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
OxidationandReduction
12.1Defineoxidationandreductionintermsof(a)electrontransferand(b)oxidationnumbers.
12.2Inthereaction2Mg+O22MgO,whichsubstanceistheoxidisingagentandwhichisthe
reducingagent?Whichsubstanceisoxidisedandwhichisreduced?
12.3Whymustbothoxidationandreductionoccursimultaneouslyduringaredoxreaction?Whatisan
oxidisingagent?Whathappenstoitinaredoxreaction?Whatisareducingagent?Whathappens
toitinaredoxreaction?
12.4Arethefollowingreactionsredoxreactions?Explain.
(a)2NO2N2O4
(b)2CrO 2+2H+Cr O 2+H O
4 2 7 2
12.5Iftheoxidationnumberofphosphorusinacertainmoleculechangesfrom+3to2duringa
reaction,isphosphorusoxidisedorreduced?Howmanyelectronsaregained(orlost)byeach
phosphorusatom?
12.6Brominegasisusedtomakefireretardantchemicalsusedonchildren'spyjamas.However,to
disposeofexcessbromine,itispassedthroughasolutionofsodiumhydroxide.Theproductsare
NaBrandNaOBr.Whatisbeingreducedandwhatisbeingoxidised?Writeabalancedequation
forthereaction.
BalancingNetIonicEquationsforRedoxReactions
12.7Thefollowingequationsarenotbalanced.Why?Balancethem.
(a) Ag+Fe2+Ag ++Fe
(b)Cr3++ZnCr+Zn 2+
(c) Ag+Au 3+Ag ++Au
(d)Ca+Al3+Ca2++Al
12.8Whatarethenetchargesontheleftandrightsidesofthefollowingequations?Addelectronsas
necessarytomakeeachofthemabalancedhalfreaction.
(a) NO +10H+NH ++3H O
3 4 2
(b)Cl +4H O2ClO +8H+
2 2 2
12.9Inquestion12.8,whichhalfreactionrepresentsoxidation?Whichrepresentsreduction?
12.10Atfirstglance,thefollowingequationmayappeartobebalanced:

Whatiswrongwithit?
GalvanicCells
12.11Whatisagalvaniccell?Whatisahalfcell?
12.12Whatisthefunctionofasaltbridge?
12.13Inthecoppersilvercell,whymusttheCu 2+andAg +solutionsbekeptinseparatecontainers?
12.14Whichredoxprocessestakeplaceattheanodeandcathodeinagalvaniccell?Whatelectric
chargesdotheanodeandcathodecarryinagalvaniccell?
12.15Howdoelectrolyticconductionandmetallicconductiondiffer?
12.16Whyisthemovementoftheionsrelativetotheelectrodesthesameinbothgalvanicand
 electrolyticcells?Explain.
12.17Whenmagnesiummetalisplacedintoasolutionofcoppersulfate,themagnesiumdissolvesto
giveMg 2+,andcoppermetalisformed.Writeanetionicequationforthisreaction.Describehow
youcouldusethereactioninagalvaniccell.Whichmetal,copperormagnesium,isthecathode?
12.18Aluminiumwilldisplacetinfromsolutionaccordingtotheequation:

Whatwouldbetheindividualhalfcellreactionsifthiswerethecellreactioninagalvaniccell?
Whichmetalwouldbetheanodeandwhichthecathode?
12.19Sketchagalvaniccellforwhichthecelldiagramis:

(a)Labeltheanodeandthecathode.
(b)Indicatethechargeoneachelectrode.
(c)Indicatethedirectionofelectronflowintheexternalcircuit.
(d)Writetheequationforthenetcellreaction.
12.20Sketchagalvaniccellinwhichinertplatinumelectrodesareusedinthehalfcellsforthesystem:

Labelthediagramtoindicatethecompositionoftheelectrolytesinthetwocellcompartments.
Showthesignsoftheelectrodesandlabeltheanodeandcathode.Writetheequationforthenet
cellreaction.
ReductionPotentials
12.21Foragalvaniccell,whatisthemeaningofthetermpotential?Whatareitsunits?
12.22Whatisthedifferencebetweenacellpotentialandastandardcellpotential?
12.23Howarestandardreductionpotentialscombinedtogivethestandardcellpotentialfora
spontaneousreaction?
12.24Whatratioofunitsgivesvolts?Whataretheunitsofamperesvoltsseconds?
12.25Isitpossibletomeasurethepotentialofanisolatedhalfcell?Explainyouranswer.
12.26Describethehydrogenelectrode.Whatisthevalueofitsstandardreductionpotential?
12.27Whatdothepositiveandnegativesignsofreductionpotentialstellus?
12.28If hadbeenchosenasthestandardreferenceelectrodeandhadbeenassigneda
potentialof0V,whatwouldthereductionpotentialofthehydrogenelectrodeberelativetoit?
12.29Ifyousetupagalvaniccellusingmetalsnotfoundintable12.1,whatexperimentalinformation
willtellyouwhichistheanodeandwhichisthecathodeinthecell?
12.30Whatisanonoxidisingacid?Givetwoexamples.Whatistheoxidisingagentinanonoxidising
acid?
12.31Whatisthestrongestoxidisingagentinadiluteaqueoussolutionofsulfuricacid?
12.32IfametalcanreactwithasolutionofHCl,isitsreductionpotentialmorenegativeormore
positivethanhydrogen?
12.33Whereintable12.1dowefindthebestreducingagents?Wheredowefindthebestoxidising
agents?
12.34Whichmetalsintable12.1willreactwithwater?Writechemicalequationsforeachofthese
reactions.
RelationshipBetweenCellPotential,ConcentrationandGibbsEnergy
12.35WritetheequationthatrelatesthestandardcellpotentialtothestandardGibbsenergychangefor
areaction.
12.36Whatistheequationthatrelatestheequilibriumconstanttothestandardcellpotential?
12.37Showhowtheequationthatrelatestheequilibriumconstanttothestandardcellpotentialcanbe
derivedfromtheNernstequation.
12.38Youhavelearnedthattheprinciplesofthermodynamicsallowthefollowingequationtobe
derived:

whereQisthereactionquotient.Withoutreferringtothetext,usethisequationandthe
relationshipbetweenGandthecellpotentialtoderivetheNernstequation.
12.39Thecellreactionduringthedischargeofaleadstoragebatteryis:

Thestandardcellpotentialis2.05V.WhatisthecorrectformoftheNernstequationforthis
reactionat25C?
Corrosion
12.40Explainthechemicalprocessesinvolvedintherustingofiron.
12.41Explainhowgalvanisationworks.
12.42Definepassivation.
12.43Whatiscathodicprotection?
Electrolysis
12.44Whatelectricchargesdotheanodeandthecathodecarryinanelectrolyticcell?Whatdoesthe
terminertelectrodemean?
12.45Inagalvaniccell,doelectronstravelfromanodetocathode,orfromcathodetoanode?Explain.
12.46WhymustNaClbemeltedbeforeitiselectrolysedtogiveNaandCl2?Writetheanode,cathode
andoverallcellreactionsfortheelectrolysisofmoltenNaCl.
12.47Writehalfreactionsfortheoxidationandthereductionofwater.
12.48WhathappenstothepHoftheaqueoussolutionnearthecathodeandanodeduringthe
electrolysisofK2SO4?WhatfunctiondoesK2SO4serveintheelectrolysisofaK2SO4solution?
12.49WhatisdescribedbytheFaradayconstant,F?WhatrelationshipsrelateFtocurrentandtime
measurements?
12.50Usingthesamecurrent,whichwillrequiremoretime:depositing0.10molCufromaCu 2+
solutionordepositing0.10molofAufromaAu 3+solution?Explainyourreasoning.
12.51Anelectriccurrentispassedthroughtwoelectrolysiscellsconnectedinseries(sothesame
amountofcurrentpassesthrougheachofthem).OnecellcontainsCu 2+andtheothercontains
Fe2+.Inwhichcellwillthegreatermassofmetalbedeposited?Explainyouranswer.
Batteries
12.52Whataretheanodeandcathodereactionsduringdischargeofaleadstoragebattery?Howcana
batteryproduceapotentialof12Vifthecellreactionhasastandardpotentialofonly2V?
12.53Whatisasymproportionationreaction?
12.54Whataretheanodeandcathodereactionsduringthechargingofaleadstoragebattery?
12.55Whatreactionsoccurattheelectrodesintheordinarydrycell?
12.56Whatchemicalreactionstakeplaceattheelectrodesinanalkalinedrycell?
12.57Givethehalfcellreactionsandthecellreactionthattakeplaceinanicadbatteryduring
discharge.Whatarethereactionsthattakeplaceduringchargingofthecell?
12.58Howishydrogenheldasareactantinanickelmetalhydridebattery?Writethechemical
formulaforatypicalalloyusedinthisbattery.Whatistheelectrolyte?
12.59Whataretheanode,cathodeandnetcellreactionsthattakeplaceinanickelmetalhydride
batteryduringdischarge?Whatarethereactionswhilethebatteryisbeingcharged?
12.60Whataretheelectrodematerialsinatypicallithiumioncell?Explainwhathappenswhenthecell
ischarged.Explainwhathappenswhenthecellisdischarged.
12.61Writethecathode,anodeandnetcellreactioninahydrogenoxygenfuelcell.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
12.62Forthefollowingreactions,identifythesubstanceoxidised,thesubstancereduced,theoxidising
agentandthereducingagent.
(a)2HNO3+3H3AsO32NO+3H3AsO4+H2O
(b)NaI+3HOClNaIO3+3HCl
(c)2KMnO4+5H2C2O4+3H2SO410CO2+K2SO4+2MnSO4+8H2O
(d)6H2SO4+2AlAl2(SO4)3+3SO2+6H2O
(e)Cu+2H2SO4CuSO4+SO2+2H2O
(f) 3SO2+2HNO3+2H2O3H2SO4+2NO
(g)5H2SO4+4Zn4ZnSO4+H2S+4H2O
(h)I2+10HNO32HIO3+10NO2+4H2O
(i) HCl+NaCl+2NaClO42ClO2+2NaCl+NaOH
12.63Assignoxidationnumberstotheatomsindicatedbyboldfacetype.
(a) S2
(b)SO2
(c)P4
(d)PH3
(e) ClO
4
(f) CrCl3
(g)SnS2
(h)Au(NO3)3
(i) CO2
12.64Assignoxidationnumberstoalloftheatomsinthefollowingcompoundsandions:
(a) Na2HPO4
(b) MnO4
(c) Na2S4O6
(d) ClF3
(e) OCl
(f) ClO
2
(g) ClO
3
(h) ClO
4
(i) Ca(VO3)2
(j) SnCl4
(k) MnO 2
4
(l) MnO2
(m)PbS
 (n) TiCl4
(o) Sr(IO3)2
(p) Cr2S3
(q) F2O
(r) HOF
(s) ClO2
(t) F2O2
(u) Bi(NO3)3
12.65Assignoxidationnumberstonitrogeninthefollowing.
(a)NO
(b)N2O5
(c)NH2OH
(d)NO2
(e)N2H4
(f) NH3
(g)N2O3
(h)N2
(i) NaN3
(j) HNO2
(k)N2H2
12.66Whenchlorineisaddedtodrinkingwatertokillbacteria,someofthechlorineisconvertedto
chlorideionsbythefollowingequilibrium:

Intheforwardreaction(thereactiongoingfromlefttoright),whichsubstanceisoxidisedand
whichisreduced?Inthereversereaction,whichistheoxidisingagentandwhichisthereducing
agent?
12.67Nitrogendioxide,NO2,isapollutantinsmog.Thegashasareddishbrowncolourandis
responsiblefortheredbrowncolourassociatedwiththistypeofairpollution.Nitrogendioxide
isalsoacontributortoacidrainbecause,whenrainpassesthroughaircontaminatedwithNO2,it
dissolvesandundergoesthefollowingreaction:

Inthisreaction,whichelementisreducedandwhichisoxidised?
12.68Chlorinedioxide,ClO2,isusedtokillbacteriainthedairy,meatandotherfoodandbeverage
industries.Itisunstable,butcanbemadebythefollowingreaction:

Identifythesubstancesoxidisedandreducedaswellastheoxidisingandreducingagentsinthe
reaction.
12.69Balancethefollowinghalfequationsoccurringinanacidicsolution.Indicatewhethereachisan
oxidationorareduction.
(a) BiO Bi3+
3
 (b)Pb 2+PbO
2
(c) NO NH +
3 4
(d)Cl ClO
2 3
12.70Ineachofthefollowingreactions,indicatetheelementthathasbeenoxidisedandtheelement
thathasbeenreduced.Labeltheoxidationstateofeachbeforeandafterthereaction.
(a)2Na+FeCl22NaCl+Fe
(b)2C2H2+5O24CO2+2H2O
(c)2PbS+3O22SO2+2PbO
(d)H2+Cl22HCl
(e)Zn+2HNO3Zn(NO3)2+H2
(f) 2AgNO3+CuCu(NO3)2+2Ag
12.71Balancethefollowinghalfequationsoccurringinabasicsolution.Indicatewhethereachisan
oxidationorareduction.
(a)FeFe(OH)2
(b)SO Cl SO 2+Cl
2 2 3
(c) Mn(OH) MnO 2
2 4
(d)H IO I
4 6 2
12.72Balancethefollowingequationsforreactionsoccurringinanacidicaqueoussolution.
(a) S O 2+OClCl+S O 2
2 3 4 6
(b) NO +CuNO +Cu 2+
3 2
(c) IO +AsO 3I+AsO 3
3 3 4
(d) SO 2+ZnZn 2++SO
4 2
(e) NO +ZnNH ++Zn 2+
3 4
(f) Cr3++BiO Cr O 2+Bi3+
3 2 7
(g) I +OClIO +Cl
2 3
(h) Mn 2++BiO MnO +Bi3+
3 4
(i) H AsO +Cr O 2H AsO +Cr3+
3 3 2 7 3 4
(j) I+HSO I +SO
4 2 2
(k) Sn+NO SnO +NO
3 2
(l) PbO +ClPbCl +Cl
2 2 2
(m)Ag+NO NO +Ag +
3 2
(n) Fe3++NH OH+Fe2++N O
3 2
(o) HNO +II +NO
2 2
(p) C O 2+HNO CO +NO
2 4 2 2
 (q) HNO +MnO Mn 2++NO
2 4 3
(r) H PO +Cr O 2H PO +Cr3+
3 2 2 7 3 4
(s) VO ++Sn 2+VO2++Sn 4+
2
(t) XeF +ClXe+F+Cl
2 2
(u) OCl+S O 2Cl+SO 2
2 3 4
12.73Balanceequationsforthefollowingreactionsoccurringinabasicaqueoussolution:
(a) CrO 2+S2S+CrO
4 2
(b)MnO +C O 2CO +MnO
4 2 4 2 2
(c) ClO +N H NO+Cl
3 2 4
(d)NiO2+Mn(OH)2Mn 2O3+Ni(OH)2
(e) SO 2+MnO SO 2+MnO
3 4 4 2
(f) CrO +S O 2CrO 2+SO 2
2 2 8 4 4
(g)SO 2+CrO 2SO 2+CrO
3 4 4 2
(h)O2+N2H4H2O2+N2
(i) Fe(OH) +O Fe(OH) +OH
2 2 3
(j) Au+CN+O [Au(CN) ]+OH
2 4
12.74Ozone,O3,isaverypowerfuloxidisingagent,andcanbeusedtotreatwatertokillbacteriaand
makeitsafetodrink.Oneoftheproblemswiththismethodofpurifyingwateristhatany
bromideions(Br)inthewaterareoxidisedtobromateions,BrO3,whichhaveshownevidence
ofcausingcancerintestanimals.Assumingthatozoneisreducedtowater,writeabalanced
chemicalequationforthereaction.(Assumeanacidicsolution.)
12.75Onthebasisofthediscussionsinthischapter,suggestchemicalequationsfortheoxidationof
metallicsilvertoAg +ionswith(a)diluteHNO3and(b)concentratedHNO3.
12.76Whenhotandconcentrated,sulfuricacidisafairlystrongoxidisingagent.Writeabalanced
chemicalequationfortheoxidationofmetalliccoppertocopper(II)ionbyhot,concentrated
H2SO4,inwhichthesulfurisreducedtoSO2.
12.77Usetable12.1topredicttheoutcomeofthefollowingreactionsinaqueoussolution.Ifno
reactionoccurs,writeNR.Ifareactionoccurs,writeabalancedchemicalequationforit.
(a) Fe+Mg 2+
(b) Cr+Pb 2+
(c) Ag ++Fe
(d) Ag+Au 3+
(e) Mn+Fe2+
(f) Cd+Zn 2+
(g) Mg+Co 2+
(h) Cr+Sn 2+
(i) Zn+Sn 2+
 (j) Cr+H+
(k) Pb+Cd 2+
(l) Mn+Pb 2+
(m)Zn+Co 2+
(n) Cu 2++Au
12.78Thefollowingreactionsoccurspontaneously:

ListthemetalsPu,PtandTlinorderofincreasingeaseofoxidation.
12.79Thefollowingreactionsoccurspontaneously:

ListthemetalsBe,GaandPuinorderofincreasingeaseofoxidation.
12.80Itisfoundthatthefollowingreactionoccursspontaneously:

WhatreactionwilloccurifamixtureispreparedcontainingCd(s),Cd(NO3)2(aq),Pt(s)and
PtCl2(aq)?(Refertotheinformationinquestion12.78.)
12.81Writethehalfequationsandthebalancedcellreactionforeachofthefollowinggalvaniccells.
(a) Cd(s)|Cd 2+(aq)||Au 3+(aq)|Au(s)
(b)Pb(s),PbSO (s)|HSO (aq)||H+(aq),HSO (aq)|PbO (s),PbSO (s)
4 4 4 2 4
(c) Cr(s)|Cr3+(aq)||Cu 2+(aq)|Cu(s)
(d)Zn(s)|Zn 2+(aq)||Cr3+(aq)|Cr(s)
(e) Fe(s)|Fe2+(aq)||Br (aq),Br(aq)|Pt(s)
2
(f) Mg(s)|Mg 2+(aq)||Sn 2+(aq)|Sn(s)
12.82Writethecelldiagramsforthefollowinggalvaniccells.Forhalfreactionsinwhichallthe
reactantsareinsolutionoraregases,assumetheuseofinertplatinumelectrodes.
(a) Cd 2+(aq)+Fe(s)Cd(s)+Fe2+(aq)
(b)Cl (g)+2Br(aq)Br (aq)+2Cl(aq)
2 2
(c) Au 3+(aq)+3Ag(s)Au(s)+3Ag +(aq)
(d)NO (aq)+4H+(aq)+3Fe2+(aq)3Fe3+(aq)+NO(g)+2H O(l)
3 2
(e) NiO (s)+4H+(aq)+2Ag(s)Ni2+(aq)+2H O(l)+2Ag +(aq)
2 2
(f) Mg(s)+Cd 2+(aq)Mg 2+(aq)+Cd(s)
12.83Usethedataintable12.1tocalculatethestandardcellpotentialforeachofthefollowing
reactionsat25C.
 (a) Cd 2+(aq)+Fe(s)Cd(s)+Fe2+(aq)
(b)Br (aq)+2Cl(aq)Cl (g)+2Br(aq)
2 2
(c) Au 3+(aq)+3Ag(s)Au(s)+3Ag +(aq)
(d)NO (aq)+4H+(aq)+3Fe2+(aq)3Fe3+(aq)+NO(g)+2H O(l)
3 2
(e) NiO (s)+4H+(aq)+2Ag(s)Ni2+(aq)+2H O(l)+2Ag +(aq)
2 2
(f) Mg(s)+Cd 2+(aq)Mg 2+(aq)+Cd(s)
(g)MnO (aq)+8H+(aq)+5Fe2+(aq)5Fe3+(aq)+Mn 2+(aq)+4H O(l)
4 2
(h)2Ag +(aq)+Fe(s)2Ag(s)+Fe2+(aq)
12.84Usethedataintable12.1todeterminewhichofthefollowingreactionsshouldoccur
spontaneouslyunderstandardconditionsinaqueoussolutionat25C.
(a) 2Au 3++6I3I +2Au
2
(b)3Fe2++2NO+4H O3Fe+2NO +8H+
2 3
(c) 3Ca+2Cr3+2Cr+3Ca2+
(d)Br +2ClCl +2Br
2 2
(e) Ni2++FeFe2++Ni
(f) H SO +H O+Br 4H++SO 2+2Br
2 3 2 2 4
(g)SO 2+4H+2IH SO +I +H O
4 2 3 2 2
12.85Writecelldiagramsusingthefollowingpairsofhalfreactions.Forhalfreactionsinwhichallthe
reactantsareinsolution,assumetheuseofinertplatinumelectrodes.Calculatetheirstandardcell
potentials.Foreachpair,identifytheanodeandcathode.
(a)

(b)

(c)

(d)

(e)

(f)

12.86Fromthehalfequationsbelow,determinethecellreactionandstandardcellpotential.
(a)
 (b)

12.87DeterminethespontaneousreactionbetweenH SO ,S O 2,HOClandCl .Thehalfequations

2 3 2 3 2
involvedare:

12.88DeterminethespontaneousreactionbetweenBr ,I ,BrandIat25C.Usethedataintable
2 2
12.1.
12.89Calculate forthereaction:

forwhich .

12.90Giventhefollowinghalfequationsandtheirstandardreductionpotentials:

calculate(a) ,(b) forthecellreactionand(c)Kc forthecellreaction.

12.91CalculateKc forthefollowingreactions,usingthedataintable12.1.AssumeT=298K.
(a) Ni2++Co Ni+Co 2+
(b)2H O+2Cl 4H++4Cl+O2
2 2
12.92Thesystem2AgI+Sn Sn 2++2Ag+2Ihasacalculated .Whatisthe
valueofKc forthissystem?
12.93Thecellreaction:

has .WhatwillthecellpotentialbeatapHof5.00whentheconcentrations
ofNi2+andAg +areeach0.010M?
12.94 forthereaction:

WhatisEcell,if[Cr2O72]=0.010M,[H+]=0.10M,[IO3]=0.00010Mand[Cr3+]=0.0010M?
12.95Acellhavingthefollowingcellreactionwassetup:
 Themagnesiumelectrodewasdippedintoa1.00MsolutionofMgSO4andthecadmium
electrodewasdippedintoasolutionofunknownCd 2+concentration.Thepotentialofthecell
wasmeasuredtobe+1.54V.WhatwastheunknownCd 2+concentration?
12.96AsilverwirecoatedwithAgClissensitivetothepresenceofchlorideionsbecauseofthehalf
cellreaction:

Astudent,wishingtomeasurethechlorideionconcentrationinanumberofwatersamples,
constructedagalvaniccellusingtheAgClelectrodeasonehalfcellandacopperwiredipped
intoa1.00MCuSO4solutionastheotherhalfcell.Inoneanalysis,thepotentialofthecellwas
measuredtobe+0.0925V,withthecopperhalfcellservingasthecathode.Whatwasthe
chlorideionconcentrationinthewater,assumingatemperatureof25C?Usethedataintable
12.1.
12.97Supposeagalvaniccellwasconstructedat25CusingaCu 2+/Cuhalfcell(inwhichthemolar
concentrationofCu 2+/Cuwas1.00M)andahydrogenelectrodehavingapartialpressureofH2
equalto1.010 5Pa.Thehydrogenelectrodedippedintoasolutionofunknownhydrogenion
concentration,andthetwohalfcellswereconnectedbyasaltbridge.Usethedataintable12.1.
(a)DeriveanequationforthepHofthesolutionwiththeunknownhydrogenion
concentration,expressedintermsofEcelland .Youwillneedtousetheequation:

toanswerthisquestion.
(b)IfthepHofthesolutionwas5.15,whatwouldbetheobservedpotentialofthecell?
(c)Ifthepotentialofthecellwas0.645V,whatwouldbethepHofthesolution?
12.98Howmanycoulombsarepassedthroughanelectrolysiscellby(a)acurrentof4.00Afor600s,
(b)acurrentof10.0Afor20.0minand(c)acurrentof1.50Afor6.00h?Whatamountof
electronscorrespondstotheanswerstoeachpartofthisquestion?
12.99Statetheamountofelectronsrequiredto:
(a) reduce0.20molFe2+toFe
(b)oxidise0.70molCltoCl
2
(c) reduce1.50molCr3+toCr
(d)oxidise1.010 2molMn 2+toMnO
4
(e)produce5.00gMgfrommoltenMgCl2
(f) form41.0gCufromaCuSO4solution.
12.100WhatamountofCr3+wouldbereducedtoCrbythesameamountofelectricitythatproduces
12.0gAgfromasolutionofAgNO3?Ifacurrentof4.00Awasused,howmanyminutes
wouldtheelectrolysistake?
12.101WhatmassofFe(OH)2isproducedatanironanodewhenabasicsolutionundergoes
electrolysisatacurrentof8.00Afor12.0min?
12.102WhatmassofCl2wouldbeproducedintheelectrolysisofmoltenNaClbyacurrentof4.25A
for35.0min?
12.103Howlongwouldittaketoproduce75.0gofmetallicchromiumbytheelectrolyticreductionof
 Cr3+withacurrentof2.25A?
12.104Howlongwouldittaketogenerate35.0gofleadfromPbSO4duringthechargingofalead
storagebatteryusingacurrentof1.50A?Thehalfreactionis:

12.105Howmanyampereswouldbeneededtoproduce60.0gofmagnesiumduringtheelectrolysis
ofmoltenMgCl2in2.00hours?
12.106Theelectrolysisof250mLofabrinesolution(NaCl)wascarriedoutforaperiodof20.00min
withacurrentof2.00A.Theresultingsolutionwastitratedwith0.620MHCl.Whatvolumeof
theHClsolutionwasrequiredforthetitration?
12.107AsolutionofNaClinwaterwaselectrolysedwithacurrentof2.50Afor15.0min.What
volumeofCl2gaswouldbeformedifitwascollectedoverwaterat25Candatotalpressure
of1.010 5Pa?
12.108WhatvolumeofdrygaseousH ,measuredat20Cand1.010 5Pa,wouldbeproducedatthe
2
cathodeintheelectrolysisofdiluteH2SO4withacurrentof0.750Afor15.00min?
12.109Writetheanodereactionfortheelectrolysisofanaqueoussolutionthatcontains
(a) SO 2,
4
(b)Brand
(c) SO 2andBr
4
12.110Writethecathodereactionfortheelectrolysisofanaqueoussolutionthatcontains
(a) K+,
(b)Cu 2+and
(c) K+andCu 2+.
12.111Whatproductswouldweexpectattheelectrodesifasolutioncontaining
(a)bothKBrandCuSO4and
(b)bothBaCl2andCuI2wereelectrolysed?Writetheequationsfortherespectivenetcell
reactions.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
12.112Thefollowingchemicalreactionsareobservedtooccurinaqueoussolution:

ArrangethemetalsAl,Pb,FeandCuinorderofincreasingeaseofoxidation.Wereallthe
experimentsdescribedactuallynecessarytoestablishtheorder?
12.113Whatistheoxidationnumberofsulfurinthetetrathionateion,S O 2?
4 6
12.114Ineachpairbelow,choosethemetalthatwouldmostlikelyreactmorerapidlywitha
nonoxidisingacidsuchasHCl:
(a)aluminiumoriron,
(b)zincorcobalt,
(c)cadmiumormagnesium.
12.115Balancethefollowingequationsinaqueoussolutionunderthespecifiedconditions.
(a) NBr N +Br+HOBr(basicsolution)
3 2
(b)Cl Cl+ClO (basicsolution)
2 3
(c)H2SeO3+H2SS+Se(acidicsolution)
(d)MnO +SO 2Mn 2++S O 2(acidicsolution)
2 3 2 6
(e) XeO +IXe+I (acidicsolution)
3 2
(f) (CN) CN+OCN(basicsolution)
2
(g)KMnO4K2MnO4+MnO2+O2(neutral)
12.116Lead(IV)oxidereactswithhydrochloricacidtogivechlorine.Theequationforthereactionis:

WhatmassofPbO2mustreacttogive15.0gofCl2?
12.117Biodieselisformedfromthereactionofoilswithmethanolorethanol.Oneoftheproductsis
methyloctanoate,C9H18O2,whichburnscompletelyinadieselengine.Giveabalanced
equationforthisreaction.Ifthedensityofmethyloctanoateis0.877gmL1,whatmassofCO2
willbeformedfromtheburningof1litreofmethyloctanoate?
12.118Supposethatagalvaniccellwassetuphavingthenetcellreaction:

TheAg +andZn 2+concentrationsintheirrespectivehalfcellsareinitially1.00M,andeach

halfcellcontains100mLofelectrolytesolution.Ifthiscelldeliverscurrentataconstantrateof
0.10A,whatwillthecellpotentialbeafter15.00h?
12.119TodeterminethereductionpotentialofthePt2+ion,agalvaniccellwassetupinwhichone
 halfcellconsistedofaPtelectrodedippedintoa0.0100MsolutionofPt(NO3)2andtheotherof
asilverwirecoatedwithAgCldippedintoa0.100MsolutionofHCl.Thepotentialofthecell
wasmeasuredtobe0.778V,anditwasfoundthatthePtelectrodecarriedapositivecharge.
Giventhefollowinghalfreactionanditsreductionpotential:

calculatethestandardreductionpotentialforthehalfreaction:

12.120Astudentsetupanelectrolysisapparatusandpassedacurrentof1.22Athrougha3MH2SO4
solutionfor30.0min.TheH2formedatthecathodewascollectedandfoundtohaveavolume,
overwaterat27C,of288mLatatotalpressureof1.010 5Pa.Usethesedatatocalculate
thechargeontheelectron,expressedincoulombs.
12.121Ahydrogenelectrodeisimmersedina0.10Msolutionofaceticacidat25C.Thiselectrodeis
connectedtoanotherconsistingofanironnaildippedinto0.10MFeCl2.Whatwillbethe
measuredpotentialofthiscell?Assumep H2=1.010 5Pa.
12.122Considerthefollowinghalfreactionsat25C.

(a)Usethedataintable12.1todeterminethevalueof:
i.

ii. forthisreaction
iii.Kc forthisreactionat25C.
(b)WritetheNernstequationforthisreaction.
(c) Whatisthepotentialofthecellwhen[MnO ]=0.20M,[Mn 2+]=0.050M,[Cl]=
4
0.0030M,[ClO3]=0.110MandthepHofthesolutionis4.25?
12.123AsolutionofNaClisneutral,withapHof7at25C.Ifelectrolysisiscarriedouton500mLof
anNaClsolutionwithacurrentof0.500A,howlongwouldittakeforthepHofthesolutionto
risetoavalueof9.00?
12.124Considerthefollowinggalvaniccell:

Calculatethecellpotential.Determinethesignoftheelectrodesinthecell.Writetheequation
forthespontaneouscellreaction.
12.125Balancethefollowingequationsforreactionsoccurringinacidicaqueoussolution.
(a) MnO +S O 2Mn 2++S O 2
4 2 3 4 6
(b)ClO +ClCl +ClO
3 2 2
(c) MnO +S2MnS+S
4
(d)Cu 2++PCu+H PO
2 4
(e) PH +I I+H PO
3 2 3 2
 (f) NO NO +NO
2 3
(g)MnO +ClMnCl +Cl
2 2 2
(h)Ni2++IO Ni2++I
4
(i) O +BrH O+Br
2 2 2
(j) Ca+Cr O 2Ca2++Cr3+
2 7
12.126Balancethefollowingequationsforreactionsoccurringinbasicaqueoussolution.
(a) ClO ClO +ClO
2 3 2
(b)Cu(NH ) 2++S O 2SO 2+Cu+NH
34 4 6 3 3
(c) Zn+NO MZn(OH) 2++NH
3 4 3
(d)Al+OHAlO +H
2 2
(e) Cr+CrO 2Cr(OH)
4 3
(f) CN+MnO CNO+MnO
4 2
(g)SO2+I2IM+SO3
(h)K+H OK++H
2 2
12.127Usethefollowinghalfreactionsandaccompanyingstandardreductionpotentialstodetermine
thebestreducingagentunderstandardconditions:Ga3+,Ga,Be2+,Be,Pd 2+orPd.

12.128Answerthefollowingquestionsforthecell:

(a)Identifytheanodeandthecathode.
(b)Writethebalancedoverallreaction.
(c)Whatisthepotentialofthiscellunderstandardconditions(refertotable12.1)?
12.129Consideragalvaniccellinvolvingchromium(III)andgold(III)andthecorrespondingCrand
Auelectrodes.(Usethedataintable12.1.)
(a)Sketchthiscell.
(b)Identifytheanodeandthecathode.
(c)Writethebalancedoverallreaction.
(d)Whichelectrodewilllosemass?
(e)Indicatethedirectionoftheelectronflow.
(f) Indicatetheflowoftheanionsandcations.
(g)Whatisthepotentialofthiscellunderstandardconditions?
(h)Writetheshorthandnotation.
(i) Calculate forthisreaction.
12.130Labeleachofthefollowingreactions(inthedirectionitiswritten)asspontaneousor
 nonspontaneous(usethedatagivenintable12.1).
(a) 2Cr3++3Ni2Cr+3Ni2+
(b)Br +2I2Br+I
2 2
(c) Cl +Sn2Cl+Sn 2+
2
(d)Al+Au 3+Al3++Au
12.131Thesilverylookofwhitegoldresultsfromplatingwithrhodium(Rh).Howmanycoulombs
ofelectricitymustbepumpedthroughanrhodium(III)solutiontoplate1gramofsolid
rhodium?
12.132Calculatethequantityofelectricity(coulombs)necessarytodeposit100.00gofcopperfroma
CuSO4solution.
12.133Howmanyminuteswillittaketoplateout30.00gofNifromasolutionofNiSO4usinga
currentof3.45ampere?
12.134Aconstantelectriccurrentdeposits0.3650gofsilvermetalin12960secondsfromasolution
ofsilvernitrate.Calculatethecurrent.Whatisthehalfequationforthedepositionofsilver?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
alkalinebattery Faradayconstant passivation
alkalinedrycell Faraday'slaw potentialdifference
ampere(A) fuelcell primarycell
anode galvaniccell redoxreaction
battery galvanisation reducingagent
cathode halfcell Reduction
Cathodicprotection halfequation reductionpotential(Ered)
celldiagram hydrometer reductionoxidationreaction
cellpotential(Ecell) intercalation saltbridge
cellreaction joules(J) saturatedcalomelelectrode
concentrationcell leadstoragebattery secondarycell
coulomb(C) Leclanchcell silver/silverchlorideelectrode
disproportionation lithiumioncell standardcellnotation
drycellbattery Nernstequation standardcellpotential
electrochemicalchanges nicadbattery
electrochemicalpotential nickelcadmiumstoragecell standardhydrogenelectrode
electrochemistry nonoxidisingacid (Eored)
electrolysis oxidation symproportionation
electrolysiscell oxidationnumber volt(V)
electrolyticcell oxidationstate voltmeter
electrolyticconduction oxidisingacid zincmanganesedioxidecell
electronicconduction oxidisingagent

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

13 TransitionMetal
Chemistry
Australiaisoneoftheworld'smainsourcesofrubiesandsapphires.Thesepreciousgemstones
areprizedfortheirbeautifulcoloursrubiesarealwaysred,whereassapphirescanexhibitarange
ofcolours.Remarkably,bothrubiesandsapphiresarecomposedprimarilyofcolourless
aluminiumoxide,Al2O3,andtheircoloursareduetothepresenceofsmallamountsoftransition
metalionschromiuminrubies,andtitanium,nickelandironinsapphires.Thecoloursthat
thesetransitionmetalsimpartresultfromboththeenergiesofthedorbitalsofthetransitionmetal
ionsandhowthedelectronsarearrangedintheseorbitals.Inthischapter,wewillinvestigate
whatmakestransitionmetalsuniqueamongtheelementsoftheperiodictablewithrespecttothe
coloursandmagneticbehavioursoftheircompounds.

KEYTOPICS

13.1Metalsintheperiodictable
13.2Transitionmetals
13.3Ligands
13.4
Transitionmetalcomplexes
13.5Transitionmetalionsinbiologicalsystems
 13.5Transitionmetalionsinbiologicalsystems
13.6Isolationandpurificationoftransitionmetals
13.7Applicationsoftransitionmetals

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.1MetalsinthePeriodicTable
Inchapter1,welearnedthatthechemicalelementscanbedividedintothreegroups:metals,metalloids
andnonmetals.Ofthe118knownelements,91or92aremetals(poloniumisvariouslydescribedaseither
ametalormetalloid).Metalscanbeclassifiedintodifferenttypesontheperiodictable,generally
accordingtothenatureoftheirvalenceorbitals(figure13.1)

FIGURE13.1Themetalsintheperiodictableoftheelements.Thetransitionmetalsareshowninyellowand
occupygroups3to12oftheperiodictable.
.

Themetalsingroups1and2havesvalenceorbitals,whereasthoseingroups13to16havepvalence
orbitals.(Theformeraresometimescalledpretransitionmetalsandthelatterposttransitionmetals.)
Collectively,thesemetalsareknownasmaingroupmetals.Thelanthanoidandactinoidmetalsare
characterisedbypartiallyfilledforbitals.Thelanthanoids,withtheexceptionofpromethium,Pm,occur
naturallythemajorityoftheactinoidelementsmustbepreparedbynuclearreactions(seesection27.3).

Themetalsingroups3to12oftheperiodictablearecollectivelycalledthetransitionmetals,andtheir
chemistrycontrastssignificantlywithothermetalsintheperiodictable.Forexample,ifwedissolveany
group1or2metal(carefully!)innitricacid,weobtainacolourlesssolutioninallcases.However,
repeatingtheexperimentusingmetalliccobalt,nickelorcopperproducespurple,greenandbluesolutions,
respectively.Infact,weobtaincolouredsolutionsformanyofthetransitionmetalstherearesome
exceptions(silver,zinc,cadmiumandmercury),andgolddoesnotdissolveinnitricacid.Ifwereducethe
solutionscontainingcobalt,nickelorcoppertodryness,wefindthattheresultingsolidsare
paramagnetic,meaningthattheyareattractedintoamagneticfield,and,indeed,thisisthecaseformany
(butnotall)ofthetransitionmetals.Thecorrespondingsolidsobtainedfromthegroup1and2metals
exhibitdiamagneticbehaviour,beingveryslightlyrepelledfromamagneticfield.

Colourandmagneticbehaviouraretwoofthedefiningcharacteristicsofcompoundscontainingtransition
metals.Aswesawinchapter1,transitionmetalelementsaresometimescalledthedblockelements,
becausethevalenceorbitalsoftheseelementsaredorbitals,andwewillseethatmanyofthespectraland
magneticpropertiesoftransitionmetalcompoundscanberelatedtotheenergiesofthefivedorbitalsof
thetransitionmetalion.

Transitionmetalsaredistinguishedbytheirabilitytoformcomplexes.Inthesechemicalspecies,transition
metalions(usuallypositivelycharged)aresurroundedbyoneormoreions(usuallynegativelycharged)or
neutralmolecules,whicharecalledligands.Whenwritingtheformulaofatransitionmetalcomplex,we
enclosethemetalandtheboundligandsinsquarebrackets(themetalionfirst,followedbytheligandsin
alphabeticalorder),withtheoverallcharge(ifany)superscriptedoutsidethebrackets.

The[Co(OH2)6]2+ionisasimpleexampleofatransitionmetalcomplex,inwhichasinglecobaltionis
bondedtosixwatermolecules.Thestructureofthispinkcomplex,whichresultsfromthedissolutionof
metalliccobaltinnitricacidasdescribedonthepreviouspage,isshowninfigure13.2a.Inthiscomplex,
thecobaltionhasaformalchargeof+2,andissurroundedbysixH2Oligandstogiveanoctahedral
geometryaboutthemetalion.

FIGURE13.2 Thestructuresofthreetransitionmetalcomplexesinwhichthecobaltionhasaformalcharge
of+2:
(a)the[Co(OH2 )6 ]2+complexcation,

(b)the[CoCl4 ]2complexanionand

(c)theneutralcomplex[Co(acac)2 ].

Ifwedissolvemetalliccobaltinhydrochloricacid,ratherthannitricacid,weobtainadeepbluesolution,
duetotheformationofthe[CoCl4]2complexanion.Thecobaltionagainhasaformalchargeof+2,but
inthiscaseissurroundedbyfourchlorideionsinatetrahedralarrangement(figure13.2b).

Finally,ifwereactasuitablecobaltsaltwiththeacetylacetonate(acac)ligand,weobtaintheneutral
complex[Co(acac)2].Asfor[Co(OH2)6]2+and[CoCl4]2,thecobaltionhasaformalchargeof+2,but
hereitisbondedtofouroxygenatomsoftwoacacligands(figure13.2c).Thegeometryaroundthecobalt
ionissquareplanar,andthecomplexisgreen.

Theexamplesabovegivesomeideaofthewiderangeofstructures,chargesandcoloursoftransition
metalcomplexes.Mostimportantly,youcanseethat:
transitionmetalcomplexescanbepositivelyornegativelycharged,orneutral
thenumberofligandsaroundthecentralmetalioncanvary
thereareanumberofdifferentpossiblegeometriesoftheligandsaroundthecentralmetalion.
Inaddition,aswewillsee,thereisusuallyavarietyofoxidationstatesavailabletothetransitionmetalion,
andtransitionmetalcomplexescanoftencontainmorethanonemetalion.

Transitionmetalcomplexesareessentialtomanybiologicalprocessesforexample,oxygenistransported
aroundourbodiesinacomplexcontainingiron,azinccomplexensuresthatwecanprocesspotentially
toxicCO2,andamanganesecomplexingreenplantsfacilitatestheconversionofwatertooxygen.
Transitionmetalcomplexesfindextensiveuseinindustrialprocesses,oftenbeingusedascatalystsforthe
formationofplastics,bulkchemicalsandpharmaceuticals.Theyarealsousedincreasinglyasdrugsin
chemotherapyandphotodynamictherapy.

TransitionmetalcomplexesareformedbyaLewisacidLewisbaseinteractionbetweenatransitionmetal
cationandoneormoreligands,witheachligandformallydonatingoneormoreelectronpairstothemetal
ion.Therefore,wewillinvestigatethetwocomponentpartsofacomplex,thetransitionmetalandthe
ligand,beforeweconsidertransitionmetalcomplexesindetail.Notethattransitionmetalsarenotunique
intheirabilitytoformcomplexes,andotherLewisacidicmetalionsandmaingroupelementsinthe
periodictablecanalsobesurroundedbyoneormoreligandstoformcomplexes.However,we
concentrateontransitionmetalcomplexesinthischapterbecauseoftheirextremelyunusualproperties
mentionedpreviously.Anyuseofthetermcomplexinthischapterreferstoatransitionmetalcomplex.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.2TransitionMetals
Aswesawinchapter4,thetransitionmetalsarecharacterisedbydvalenceorbitals,sotheneutralatoms
generallyhavevalenceelectronconfigurationsof(n+1)s2nd (x2),wherexisthegroupnumberofthemetal
intheperiodictable,andnistheprincipalquantumnumber.Thegroup4elementtitanium,forexample,has
thevalenceconfiguration4s23d2.Recallfromchapter4,however,thatthereareexceptionstothisgeneral
rule,mostnotablyforthefirstrow(3d)elementsCr(4s13d5)andCu(4s13d10).Moreimportantfortransition
metalcomplexesaretheelectronconfigurationsoftheions.Aswelearnedinchapter4,thendorbitalis
alwaysoflowerenergythanthe(n+1)sorbitalintransitionmetalcations,whichthereforealwayshavevacant
(n+1)sorbitals.Knowledgeoftheelectronconfigurationoftransitionmetalionsisimportantasanotherofthe
definingcharacteristicsoftransitionmetalsistheirability,incontrasttomostothermetalsintheperiodictable,
toexistinavarietyofoxidationstates,thevaluesofwhich,fortransitionmetalions,wedenoteusingRoman
numerals.Forexample,theoxidationstateofironinthemajorityofitscomplexesiseitherFe(II)orFe(III),
whilecomplexescontainingmanganeseineveryoxidationstatefromMn(0)toMn(VII)areknown.Table13.1
showsthecommonoxidationstatesencounteredforthefirstrowtransitionmetalions,alongwiththeir
correspondingelectronconfigurations.
TABLE13.1 Commonoxidationstatesandelectronconfigurationsforthefirstrowtransitionmetalions.Themost
importantoxidationstatesofeachmetalarehighlighted

WORKEDEXAMPLE13.1

Determiningdelectronconfigurations

WhatarethedelectronconfigurationsofthetransitionmetalionsMn 2+,Cu 2+,Co 3+,Ti3+and

Cr2+?

Analysis

Althoughtherequireddelectronconfigurationscanbeobtainedfromtable13.1,youshould
determinetheanswersbyfirstcalculatingthenumberofelectronsineachionandthenusingthese
 tofilltheorbitalsineachion.

Solution

Eachtransitionmetalisinthefirstrow,sotheyshareacommon[Ar]coreelectronconfigurationfor
theirfirst18electrons.Recallalsothatthe4sorbitalsareofhigherenergythanthe3dorbitalsin
transitionmetalions,sowestartfillingthe3dorbitalsfirst.Thenumbersofelectronsintheneutral
atomsareobtainedfromtheatomicnumbers,andweremovetheappropriatenumberdependingon
thechargeontheion.Giventhatthefirst18electronsarecoreelectrons,anyelectronsinexcessof
18godirectlyintothe3dorbitals.
Mn:Z=25,sothereare25electronsintheneutralatom.Hence,Mn 2+has23electrons.Mn 2+
hasfivedelectrons(2318),soitselectronconfigurationis[Ar]3d5.
Cu:Z=29,sothereare29electronsintheneutralatom.Hence,Cu 2+has27electrons.Cu 2+
hasninedelectrons(2718),soitselectronconfigurationis[Ar]3d9.
Co:Z=27,sothereare27electronsintheneutralatom.Hence,Co 3+has24electrons.Co 3+
hassixdelectrons(2418),soitselectronconfigurationis[Ar]3d6.
Ti:Z=22,sothereare22electronsintheneutralatom.Hence,Ti3+has19electrons.Ti3+has
onedelectron(1918),soitselectronconfigurationis[Ar]3d1.
Cr:Z=24,sothereare24electronsintheneutralatom.Hence,Cr2+has22electrons.Cr2+
hasfourdelectrons(2218),soitselectronconfigurationis[Ar]3d4.

Isouranswerreasonable?

Alltheanswersindicatethatthe3dorbitalsarepartiallyfilled,aswewouldexpectforatransition
metalion.Ouranswersarethereforelikelytobecorrect,barringarithmeticalerrors.

Onequickwayofdeterminingdelectronconfigurationsistosubtractthechargeontheionfrom
thegroupnumberofthetransitionmetal.Forexample,Coisingroup9oftheperiodictable,sothe
Co 3+ionhas(93)=6delectrons.Usingthismethod,wecanconfirmthatouranswersare
correct.Thismethodisparticularlyusefulindeterminingthedelectronconfigurationsofrow3
transitionmetalions,asthelanthanoidelementsliebetweenthemaingroupmetalsandthese
transitionmetals,therebycomplicatingthecoreelectroncount.Youshouldalsobeawarethatthed
electronconfigurationoftransitionmetalionsbelongingtothesamegroupisthesame.For
example,Co 3+,Rh 3+andIr3+allhavead6electronconfiguration.

PRACTICEEXERCISE13.1
Whatarethedelectronconfigurationsofthe
transitionmetalionsFe3+,Ni2+,Pt2+,Ir+and
Re+?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.3Ligands
TransitionmetalionsareLewisacids(seechapter11),andthereforeactaselectronpairacceptorstowardsoneor
moreligandswhenformingmetalcomplexes.ThewordligandisderivedfromtheLatinligaremeaningtobind.
LigandsareLewisbasesandcandonateanelectronpairtoaLewisacidictransitionmetalion.Theelectronpairis
usuallyalonepairlocatedonanatomorion.Theatomonwhichthelonepairislocatediscalledthedonoratom.
Ligandscanhaveoneormoredonoratoms.Thenecessityforalonepairofelectronsmeansthatrelativelyfew
elementsintheperiodictablecanactasdonoratomsthemostcommonareF,Cl,Br,I,O,S,NandP.

Asstatedearlier,ligandscanbeeitherionsormolecules,andtheycanbenegativelycharged,neutralor,invery
rarecases,positivelycharged.Anionsthatserveasligandsincludemanysimplemonatomicions,suchasthehalide
ions(F,Cl,Br,I)andthesulfideion(S2),eachofwhichcontainsfourlonepairsofelectrons.Common
polyatomicanionsthatareligandsarethenitriteion(NO2),cyanideion(CN),hydroxideion(OH),thiocyanate
ion(SCN)andacetateion(CH3COO)(table13.2).Themostcommonneutralmoleculethatservesasaligandis
water,whichcontainstwolonepairsofelectronsontheOatom.
TABLE13.2 Commonligandsfoundintransitionmetalcomplexes.Rulesfornamingligandsarefoundinsection13.4
Mostofthereactionsoftransitionmetalionsinaqueoussolutionsareactuallyreactionsofcomplexionsinwhich
themetalisattachedtoanumberofwatermolecules,dependingontheidentityofthemetalion.Therefore,the
notationMn+(aq)actuallyreferstoacomplexionwiththeformula[M(OH2)x ]n+Cu 2+(aq),forexample,isbelieved
toexistasthecomplexion[Cu(OH2)5]2+inaqueoussolution,butCo 2+(aq)forms[Co(OH2)6]2+underthesame
conditions.Anothercommonneutralligandisammonia,NH3,whichhasonelonepairofelectronsonthenitrogen
atom.Ifammoniaisaddedtoanaqueoussolutioncontainingthe[Ni(OH2)6]2+ion,forexample,thecolourchanges
almostinstantaneouslyfromgreentoblueasammoniamoleculesbindpreferentiallytothemetalion,displacing
watermolecules(figure13.3)accordingtotheequation:

FIGURE13.3Complexionsofnickel.Additionofammoniatoasolutionofgreen[Ni(OH2 )6 ]2+ions(left)leadstothe
formationofblue[Ni(NH3 )6 ]2+ions(right).
Ligandsthatuseonlyoneatomtobondtoametalionarecalledmonodentate(literallyonetoothed)ligands.
Therearealsomanyligandsthathavetwoormoredonoratoms.Collectivelytheyarereferredtoaspolydentate
ligands.Ligandswithtwodonoratomsarecalledbidentateligands,and,whentheyformcomplexes,bothdonor
atomscanbecomeboundtothesamemetalion.Thebestknownexampleofabidentateligandisethylenediamine,
NH2CH2CH2NH2,whichisusuallyabbreviateden(thisisahistoricalnamebutisusedalmostexclusivelyin
preferencetoitsIUPACname,ethane1,2diamine).Oxalateion,C2O42(ox),isanothercommonbidentateligand,
andthestructuresofbothareshowninfigure13.4.

FIGURE13.4 Thestructuresofthebidentateligands
(a)ethylenediamine(en)and
(b)oxalate(ox),and
(c)and
(d)thefivememberedchelateringsformedonbindingtoametalion,M.

Whenbidentateligandsbindtoametalion,theyformchelaterings(figure13.4).Complexescontainingchelate
ringsareoftencalledchelatecomplexes(thewordchelateisderivedfromtheGreekwordforclaw).Ligands
containingthreeormoredonoratomscanpotentiallyformmorethanonechelateringwiththesamemetalionand
suchligandsoftenhaveparticularlyhighaffinitiesfortransitionmetalions.Anexcellentexampleofthisisthe
polydentateligandethylenediaminetetraaceticacid,abbreviatedH4EDTA(figure13.5).

FIGURE13.5 Representationsofthestructuresof
(a)H4 EDTAand
(b)thetetraanionEDTA4.

TheneutralH4EDTAmoleculelosesfourprotonstobecometheEDTA4tetraanion,whichisahexadentateligand
thatbindsstronglythroughfourOatomsandthetwoNatomstoalargenumberofmetalions.EDTA4isa
particularlyusefulandimportantligand.Itisrelativelynontoxic,whichallowsittobeusedinsmallamountsin
foodstoretardspoilage.Manyshampooscontainthetetrasodiumsalt,Na4EDTA,tosoftenwatertheEDTA4
bindstoCa2+,Mg 2+andFe3+ions,whichremovesthemfromthewaterandpreventsthemfrominterferingwiththe
actionofsoapsintheshampoo.Sometimes,EDTA4isaddedinsmallamountstowholebloodtopreventclottingit
worksbybindingcalciumions,whichtheclottingprocessrequires.EDTA4hasevenbeenusedasatreatmentin
casesofpoisoningbecauseitcanhelpremovepoisonousheavymetalionssuchasPb 2+fromthebodywhenthey
havebeenaccidentallyingested.Figure13.6showshowtheEDTA4ligandwrapsaroundthemetalinatransition
metalcomplex.

FIGURE13.6 Tworepresentationsofthetransitionmetalcomplex[Co(EDTA)]:
(a)ballandstickmodeland
(b)spacefillingmodel(theCo(III)ionisorange).Notethealmostcompleteencapsulationofthemetal
ioninthespacefillingmodel.

Ligandscontainingtwoormoredonoratomscanpotentiallyactasbridgesbetweentwoormoremetalions,
providedthedonoratomsareorientedcorrectly.Anexampleofthisisprovidedbythecopperacetatecomplex,
[Cu 2(OH2)2(OOCCH3)4],inwhichthefouracetateligandsbridgethetwoCu(II)ions,asshowninfigure13.7.

FIGURE13.7Ballandstickmodelof[Cu2 (OH2 )2 (OOCCH3 )4 ](theCuionsarebrown).Hydrogenatomshavebeen

omittedforclarity.

Thereareavastnumberofknownligands,andtable13.2summarisessomeofthemorecommonandimportantof
thoseusedinthesynthesisoftransitionmetalcomplexes.

WORKEDEXAMPLE13.2
 Identifyingligands
Whichofthefollowingspecieswouldbeunlikelytofunctionasaligandinatransitionmetalcomplex?
(a) NH +
4
(b)B(CH3)3
(c) HS

Analysis

Welearnedonp.547that,inordertofunctionasaligand,amoleculeorionmusthaveanavailable
electronpairtodonatetoatransitionmetalion.Therefore,wewillproceedbydrawingtheLewis
structuresof(a),(b)and(c)andlookingforthepresenceofelectronpairs.

TheLewisstructuresof(a),(b)and(c)areasfollows.

Fromthese,itcanbeseenthatonlyHShaselectronpairsavailablefordonationtoatransitionmetalion
andcouldthuspotentiallyactasaligand.

PRACTICEEXERCISE13.2
BydrawingLewisstructures,determinewhichof
thefollowingspeciescouldactasaligandtowards
atransitionmetalionbydonatingalonepairof
electrons:BH3,BH4,CH4,CH3.

ManyAustralianandNewZealandchemistshavebeeninstrumentalinthedevelopmentofnovelligands,andtwo
inparticulardeservespecialmention.NewZealandchemistNeilCurtisandcoworkersatVictoriaUniversityinthe
early1960sreportedthefirstmetalcomplexcontainingamacrocyclicligand,showninfigure13.8.Macrocyclic
ligandsaresimplylargecyclicligandsthatcontainthreeormoredonoratoms.TheworkofCurtishasledtothe
developmentofmacrocyclicchemistryasanimportantsubdisciplineofinorganicchemistry,andliterallythousands
ofcomplexescontainingmacrocyclicligandshavebeenpreparedintheyearssincehispioneeringresearch.
 FIGURE13.8Thefirsttransitionmetalcomplexcontainingamacrocyclicligand,preparedbyNewZealandchemistsinthe
early1960s.

In1977,AustralianchemistAlanSargesonandcoworkersattheAustralianNationalUniversitypreparedthefirst
examplesofgroupsofligandscalledsepulchrates(fromsepulchremeaningtomb)andsarcophagines(from
sarcophagusmeaningcoffin),examplesofwhichareshowninfigure13.9.

FIGURE13.9 (a)Asepulchrateligand,
(b)asarcophagineligandand
(c)aspacefillingmodelofaCo(III)complexofasarcophagineligand.NotethattheorangeCo(III)ionis
completelyenclosedinsidetheligand.

Thesehexadentateligands,whicharetriviallycalledcageligands,completelyencapsulateatransitionmetalion,
and,onceinsertedinsidetheligandcavity,themetalionisextremelydifficulttoremove.Complexesofcage
ligandsshowextremelyinterestingproperties,particularlyinbiologicalsystems.Suchcomplexeshaveeffective
antiviralactionagainstviruses,suchashepatitisandherpes,andworkbyinhibitingtheirreplication.Cage
compoundscanalsokilltapeworms,bothinvitro(inatesttube)andinvivo(inaliveorganism),anddestroy
giardiainvitroatmicromolarconcentrationsofthecomplex.

Alloftheligandsdescribedthusfarcontainadonoratomwithatleastonelonepairofelectrons.Thereisalsoa
varietyoforganicmolecules,thatcanfunctionasligandsintransitionmetalcomplexes,inwhichoneormore
carbonatomsareboundtothetransitionmetalion.Neutralunsaturatedorganicmolecules,includingalkenes,
alkynesandaromaticspeciessuchasbenzene,canbindtometalionsusingelectronsfromtheirorbitals(chapter
16)alkenesandalkynesgenerallydonatetwoelectrons,whilebenzeneusuallydonatessix.Negativelycharged
organicligandscanbegeneratedbydeprotonation,thusallowingcoordinationof,forexample,theanionsof
alkanes,whilethecyclopentadienideanion,C5H5hasalsofoundextensiveuseasaligand.Compoundswhich
containorganicligandsboundtoametalionthroughoneormorecarbonatomsarecalledorganometallic
compounds(figure13.10).

FIGURE13.10 Representationsofthestructuresofsomeorganometalliccomplexes:
(a)
 [Pt(C2 H4 )Cl3 ],theanionofZeise'ssalt,containsamoleculeofetheneboundtothePtion.
(b)[W(CH3 )6 ]containssixCH3 ligands,whichareformallyderivedfromdeprotonationofCH4 .
(c) In[Fe(C5 H5 )2 ],commonlyknownasferrocene,eachC5 H5 liganddonatessixelectronstotheFe
ion.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.4TransitionMetalComplexes
TheinteractionbetweenatransitionmetalionandaligandcanbeunderstoodintermsofaLewisacidLewisbase
interaction,inwhichtheligandformallydonatesanelectronpairtothemetaliontoformacovalentbond.Weusually
thinkofacovalentsinglebondasresultingfromthesharingofanelectronpairbetweentwoatoms,whereeachatom
donatesoneelectrontothebond(chapter5).Intransitionmetalcomplexes,aswellasallLewisacidLewisbase
adducts,bothoftheelectronsinthecovalentbondareformallycontributedbytheligand(Lewisbase).Although
metalligandcovalentbondsinmetalcomplexesandsinglecovalentbondsinorganiccompoundsbothinvolve
sharingapairofelectrons,theformeraresometimescalledcoordinatebonds,donorcovalentbondsordativebonds,
andweoftensaythataligandiscoordinatedtoratherthanboundtoatransitionmetalion.Transitionmetal
complexesingeneralareoftencalledcoordinationcompounds,whilethedisciplineofthestudyoftransitionmetal
complexesiscalledcoordinationchemistry.Coordinatebondsaresometimesdrawnwithanarrowononeendto
showthedirectionofelectrondonation,butitismorecommontodepictsuchbondsinthesamewayasallother
covalentbonds(figure13.11).

FIGURE13.11FormationofacoordinatebondbetweenAg+andNH3 .Notethattheoverallchargeonthecomplexisthe
sameasthesumofthechargesonthemetalionandtheligands.

Whenassigningformalchargestothecoordinatedligandatomsinatransitionmetalcomplex,weassumethatboth
electronsinthedonatedelectronpairbelongtotheliganddonoratom.Thisisillustratedintheexampleabove,
where,in[Ag(NH3)2]+,theNatomsareregardedashavingfiveelectrons,withbothelectronsineachAgNbond
assignedtotheNatom.Therefore,bothNatomsareformallyneutral,ratherthanpositivelycharged.

Whenwritingtheformulaofatransitionmetalcomplex,wealwaysenclosethemetalcontainingsectioninsquare
brackets,withtheoverallchargeonthecomplex(ifany)superscriptedoutsidethebrackets.Forexample,wewould
writetheformulaofthecomplexcontaininganFe(III)ionsurroundedbysixClligandsas[FeCl6]3.Thesodiumsalt
ofthiscomplexanionwouldbewrittenasNa3[FeCl6]withthechargesomitted,asisusualforioniccompounds.Ions
outsidethesquarebracketsaretermedcounterionsandmaybeeithercationsoranions,dependingonthechargeon
thecomplexion.Itisimportantthatyoucandeterminetheoxidationstateofthemetalioninatransitionmetal
complexfromtheformulaofthecomplex,andthiscanusuallybedoneusingtheequation:

oxidationstateoftransitionmetalion=chargeonthecomplexsumofchargesontheligands

WORKEDEXAMPLE13.3

Determiningtheoxidationstateofatransitionmetalioninacomplex
Whatistheoxidationstateofthetransitionmetalionineachofthefollowingcomplexes?
(a)Na3[FeCl6]
(b)[CoCl(NH3)5]Cl2
(c)[Re(CO)5Cl]

Analysis
 Wewillusetheequation:

todeterminetheoxidationstateofthetransitionmetalion.(Rememberthatwedenoteoxidationstateusing
Romannumerals.)Wecalculatethechargeonthecomplexbyremovingthecounterion(s)(ifany),andwe
canusetable13.2toobtainthechargesoftheligands.

(a) RemovingthreeNa+ionsmeansthatthechargeonthecomplexis3i.e.[FeCl ]3.EachoftheCl

6
ligandshasa1charge,sothetotalchargeontheligandsis6.Therefore:

(b)RemovingthetwoClcounterionsleavesachargeonthecomplexof2+i.e.[CoCl(NH ) ]2+.There
35
arefiveNH3ligands,whichareneutral,andoneClligandwitha1charge.Thisgivesatotal
chargeontheligandsof1.Therefore:

(c)Therearenocounterionstoremove,sothechargeonthecomplexmustbe0.TherearefiveCO
ligands,whichareneutral,andoneClligandwitha1charge.Thisgivesatotalchargeonthe
ligandsof1.Therefore:

PRACTICEEXERCISE13.3
Determinetheoxidationstatesofthetransition
metalionsinthefollowingcomplexes:
[Co(NH3)6]Cl3,Na2[MnCl5],[RhCl2(en)2]Cl,
K3[Cr(ox)3],[CoCl(en)(NCS)(NH3)2]NO3.

Whenwritingtheformulaeoftransitionmetalcomplexes,itisusualtowriteligandswiththeirdonoratom(s)first.For
example,wewouldwrite[Fe(OH2)6]2+insteadof[Fe(H2O)6]2+.Inthecaseofpotentiallybidentateligandssuchas
CO32andC2O42,wewritethetwodonoratomsfirst,followedbytherestoftheatoms.Therefore,theformulae
[Co(O2CO)3]3and[Fe(O2C2O2)3]3implythatthecarbonateandoxalateligandsarechelatedtotheCo(III)andFe(III)
centresrespectively.Suchnotationallowsustoeasilydistinguishbetweencomplexesinwhichtheligandsactas
chelatesand,forexample,themonodentatecarbonateligandfoundin[Co(NH3)5OCO2]+.

Structuresoftransitionmetalcomplexes
Transitionmetalcomplexesexhibitahugevarietyofstructures,asistobeexpectedwhenthecentralmetalioncanbe
surroundedbyanythingfromonetoninemonodentateligands.Centraltothestructureadoptedbyanytransition
metalcomplexisthecoordinationnumberofthemetalion.Thisisdefinedasthenumberofdonoratomsdirectly
attachedtothemetalion.Forexample,thecomplex[CuCl4]2hasfourchlorideligandsboundtoaCu(II)ion,sothe
coordinationnumberofthemetalioninthiscomplexis4wealsosaythatthemetalionis4coordinate.Similarly,the
complex[Co(NH3)6]3+containsa6coordinateCo(III)ionbondedtotheNatomsofthesixsurroundingNH3ligands.
Thecoordinationnumberofametalionmaynotbesoobviouswhenthemetalcomplexcontainspolydentate
ligands.Forexample,theNi(II)ionin[Ni(en)3]2+(figure13.12)is6coordinate,not3coordinate,aseachenligand
containstwodonoratoms,meaningthattheNi(II)ionisboundtosixNatoms.Asimilarargumentcanbeusedto
showthattheCo(III)ionin[Co(EDTA)](figure13.6)isalso6coordinate.Themostcommoncoordinationnumber
amongtransitionmetalcomplexesis6,while4coordinatecomplexesarethenextmostcommon.Certaingeometries
areassociatedwitheachcoordinationnumber,andtheseareoutlinedonthefollowingpages.

FIGURE13.12Octahedralcomplexes.Complexeswiththisgeometrycanbeformedwitheithermonodentateligands,such
aswater,orpolydentateligands,suchasethylenediamine(en).Tosimplifydrawingtheethylenediamine
complex,thetwomethylenegroupsjoiningthedonornitrogenatomsintheligand,CH2 CH2 ,are
representedasthecurvedlinebetweentheNatoms.Alsonoticethatthenitrogenatomsofthebidentate
ligandspanadjacentpositionswithintheoctahedron,asthemethylenechainisnotlongenoughtoallow
themtospanoppositepositions.
Coordinationnumber6
Most6coordinatecomplexesadoptanoctahedralgeometry,inwhichthesixliganddonoratomsarepositionedat
theverticesofanoctahedron(figure13.13).Theoctahedronissonamedbecauseitcontainseightfaces.Thetwo
ligandsintheplaneofthepagearecalledtheaxialligands,whiletheremainingfourarecalledtheequatorialligands.

FIGURE13.13 (a)Anoctahedron,
(b)astructuraldiagramand
(c)aballandstickrepresentationofanoctahedralML6 complex.Notethateachligandissituatedatone
ofthesixverticesoftheoctahedron.

Suchanarrangementminimisesligandligandrepulsionsbyplacingtheligandsasfarawayaspossiblefromeach
other,andthisgeometryisinfactthatpredictedbyVSEPRtheory(chapter5,pp.17682).Theoctahedralgeometry
canaccommodatebothmonodentateandpolydentateligands,asshowninfigure13.12.

Coordinationnumber4
VSEPRpredictsthatatetrahedralgeometryisfavouredforacoordinationnumberof4,butbothtetrahedraland
squareplanargeometriesarefoundfor4coordinatecomplexes,andtheseareillustratedinfigures13.14and13.15.

FIGURE13.14Tetrahedralgeometry.[Zn(OH)4 ]2adoptsatetrahedralstructure.

FIGURE13.15Squareplanargeometry.[Cu(NH3 )4 ]2+adoptsasquareplanarstructure.

Tetrahedralgeometriesareoftenobservedforcomplexesofd10metalionssuchasCu(III)andZn(II),whilesquare
planarcomplexesareoftenformedbyNi(II),Pt(II)andAu(III)metalionswithd8electronconfigurations.Infact,a
perfecttetrahedralorsquareplanargeometryisrarelyobserved,andmany4coordinatecomplexesadoptageometry
intermediatebetweenthetwo.

Coordinationnumber5
Thisisprobablythemostimportantcoordinationnumberfollowing6and4.Therearetwopossiblegeometriesfor5
coordinatecomplexes:trigonalbipyramidalandsquarepyramidal,whichareillustratedinfigure13.16.

FIGURE13.16 (a)Trigonalbipyramidaland
(b)squarepyramidalgeometriesfoundin5coordinatecomplexes.

TrigonalbipyramidalgeometryispredictedonthebasisofVSEPR,but,aswefoundfor4coordinatecomplexes,
VSEPRisoflimitedusewhenappliedtotransitionmetalcomplexes,especiallywherethemetaliondoesnothavead
0ord10configuration.Forexample,the[CuCl ]3anionistrigonalbipyramidal,whilethe[Ni(CN) ]3anioninthe
5 5
complex[Cr(en)3][Ni(CN)5]simultaneouslydisplaysbothsquarepyramidalandtrigonalbipyramidalgeometriesin
thesamecompound.

Itiscommontorefertotheligandspointingaboveandbelowthetrigonalplaneinatrigonalbipyramidalcomplexas
axial,whiletheremainingthreeligandsarecalledequatorial.

Isomerismintransitionmetalcomplexes
Wewerefirstintroducedtotheconceptofisomerisminchapter2,wherewediscussedconstitutionalisomersof
alkanes.Thereareanumberofdifferenttypesofisomerismintransitionmetalcomplexes,someofwhicharedetailed
onthefollowingpages.

Structuralisomerism
Structuralisomersaremoleculeswiththesamemolecularformulabutwiththeconstituentatomsjoinedtogetherin
differentways.Incoordinationchemistry,wewillconsiderfourtypesofstructuralisomerism.

Ionisationisomerism

Thepurplecomplex[CoBr(NH3)5]SO4andtheredcomplex[Co(NH3)OSO3]Br(figure13.17)areexamplesof
ionisationisomers.Theformerhasbromideactingasaligandandsulfateasthecounterion,whiletherolesare
reversedinthelatter,withsulfatecoordinatedtothemetalionandbromideactingasthecounterion.
 FIGURE13.17Theionisationisomers[CoBr(NH3 )5 ]SO4 and[Co(NH3 )OSO3 ]Br.

Hydrateisomerism

Thisissimilartoionisationisomerism,andresultsfromthedifferentnumbersofwatermoleculesthatcanbe
coordinatedtoametalion.Forexample,therearethreecomplexeswiththeempiricalformulaCrCl36H2O:
[Cr(OH2)6]Cl3(purple)
[CrCl(OH2)5]Cl2H2O(bluegreen)
[CrCl2(OH2)4]Cl2H2O(green).

Thesecomplexesarehydrateisomers.

Coordinationisomerism

Coordinationisomersresultwhenligandsareexchangedbetweenacomplexcationandacomplexanionofthesame
coordinationcompound.Forexample,[Co(NH3)6][Cr(CN)6]and[Cr(NH3)6][Co(CN)6]arecoordinationisomers.

Linkageisomerism

Ligandscontainingmorethanonedonoratomcanpotentiallyformlinkageisomers,whichresultfromthedifferent
possiblewaysinwhichtheligandcanbindtothemetalion.Forexample,thethiocyanateligand,NCS,canbind
usingalonepaironeithertheNatom,togivethebrickred[CoNCS(NH3)5]2+ion,orontheSatom,togivethe
purplecomplex[Co(NH3)5SCN]2+.Thesecomplexesarecalledlinkageisomers.TheNO2ligandcanalsoform
linkageisomersbybondingtoatransitionmetalioneitherthroughtheNatomoroneoftheOatoms.Ligands,such
asNCSandNO2,withtwoormoredifferentpotentialdonoratomsarecalledambidentate.

Stereoisomerism
Stereoisomersareisomershavingthesameconnectionsbetweentheconstituentatomsbutdifferentarrangementsof
thoseatomsinspace.Wemetanexampleofstereoisomerisminchapter2(p.42)wherewefoundthatthetwomethyl
groupsin1,2dimethylcyclopentanecouldeitherbeonthesamesideordifferentsidesofthefivememberedringwe
designatedthetwopossibleisomersascisandtransrespectively.Asimilartypeofisomerismcanexistintransition
metalcomplexesandistypifiedbythesquareplanarcomplex[PtCl2(NH3)2].Thetwopossiblecistransisomersof
thesquareplanarcomplexwiththeempiricalformula[PtCl2(NH3)2]areshowninfigure13.18.

FIGURE13.18cistransisomersof[Pt(NH3 )2 Cl2 ].

Thecisisomerhastheidenticalligandsadjacenttoeachother,whilethetransisomerhasthemoppositeeachother.
Inidentifyingandnamingisomers,cismeansonthesameside,andtransmeansonoppositesideswecallthese
twoisomerscis[PtCl2(NH3)2]andtrans[PtCl2(NH3)2].Thetwoisomershavedistinctlydifferentchemicalproperties,
mostinterestingofwhichisthefactthatthecisisomer(commonnamecisplatin)isaparticularlyeffective
chemotherapyagentagainstcertaintypesofcancer,whilethetransisomershowslittleactivity(seeChemistry
Researchonthenextpage).ItshouldbenotedthatatetrahedralarrangementoftheligandsaroundthePtionwould
notgiverisetostereoisomers,andthiscanbeusedtodifferentiatebetweensquareplanarandtetrahedralgeometries.

ChemistryResearch

Platinumbasedanticancerdrugs

ProfessorTrevorHambley,UniversityofSydney

Atthebeginningofthe1970s,70%ofthosewhodevelopedtesticularcancerdiedwithinoneyear,butby
theendofthatdecadethisproportionwasdownto10%anditisnoweffectivelyzero.

Theanticancerdrugresponsibleforthisdramaticturnaroundisknownascisplatin,cis[PtCl2(NH3)2],avery
simplecoordinationcomplex(seefigure13.19)butthebasisofthemostwidelyusedgroupofanticancer
drugsintheworld.Abouthalfofthecancerpatientswhoreceivechemotherapyhaveaplatinumbased
drugincludedintheirtreatment.

FIGURE13.19Modelsofcisplatin.
 FIGURE13.20CyclistLanceArmstrongdevelopedtesticularcancerthatspreadtohisbrain.Followingtreatment
withcisplatin,hewentontowinsevenToursdeFrance,makinghimthemostsuccessfulcyclistin
thisfamousrace.

Likenearlyallanticancerdrugs,cisplatincausesserioussideeffectsthatlimititsuseandeffectiveness.The
researchgroupledbyProfessorTrevorHambleyisworkingtodevelopnew,lesstoxicanaloguesofthe
existingdrug.Theyaretakingtwoapproaches:theuseofcomplexesinthemoreinertPt(IV)oxidation
state,andmoreeffectivedeliveryofplatinumdrugstotumoursratherthantohealthytissues.Pt(II)
complexes,suchascisplatin,are4coordinateandgenerallyhighlyreactive,resultinginmanyreactionsin
thebloodstream.Thisleadstosideeffectsandlossofupto95%ofthedrug.Pt(IV)complexesare6
coordinateandmuchlessreactivewithmoleculesinthebloodstream.

ProfessorHambley'sgrouphasbeenworkingtomodifyPt(IV)complexesbyvaryingthetypesofligandso
thatthecomplexesareinertenoughtosurviveinthebloodstreamandbecomeactive(onreductiontoPt(II))
onlyaftertheyhavebeentakenupthroughoutthecellsthatmakeupthetumour.Hisgrouphasalso
attachedfluorescentligandstoplatinumcomplexestomonitortheiruptakeanddistributionintumoursand
tohelpunderstandthelackofanticanceractivityofthegeometricisomerofcisplatin,trans[PtCl2(NH3)2].

Octahedralcomplexescanalsoshowcistransisomerism.Whiletherearenosuchpossibleisomersofcomplexesof
thetype[ML6]and[ML5X],cisandtransisomersarepossiblefor[ML4X2]species,withtheclassicexamplebeing
thecomplexescis[CoCl2(NH3)4]+(violet)andtrans[CoCl2(NH3)4]+(green).Thestructuresofthesecomplexesare
giveninfigure13.21.

FIGURE13.21Thestructuresoftheisomerscis[CoCl2 (NH3 )4 ]+(top)andtrans[CoCl2 (NH3 )4 ]+(bottom).

Notethatthesearetheonlypossibleisomersofthiscomplexanyotherarrangementoftheligandsisidenticaltoone
ofthetwostructuresinfigure13.21.

Isomersarealsopossibleforoctahedralcomplexeswiththeformula[ML3X3]andthesearedepictedinfigure13.22
forthecomplex[CoCl3(NH3)3].
 FIGURE13.22Thefacisomer(left)andmerisomer(right)of[CoCl3 (NH3 )3 ].

Thesetwoisomersaredesignatedmer(meridional)andfac(facial).Themerisomerhasthetwosetsofthree
identicalligandslyinginperpendicularplanesaroundthemeridianofthecomplex,whilethefacisomerhaseachset
ofthreeligandsoccupyingafaceoftheoctahedron,sothatthetwosetsofligandslieinparallelplanes.Again,these
aretheonlypossiblegeometricisomersofthesecomplexes,andthereisnootherarrangementofligandsthatis
differentfromthoseinfigure13.22.

Wewillseeinchapter17thatanothertypeofstereoisomerismexistsintransitionmetalcomplexescontaining
polydentateligands.Thesecomplexes,withmirrorimagesthatarenotsuperimposableoneachother,aresaidtobe
chiral.

WORKEDEXAMPLE13.4

Identifyinganddrawingstereoisomers
Drawallthepossiblestereoisomersofthefollowingtransitionmetalcomplexes.
(a) [Co(NH ) OH ]3+(Thecomplexisoctahedral.)
35 2
(b)[RhBr (NH ) ]+(Thecomplexisoctahedral.)
2 34
(c)[PtBrCl(NH3)(OH2)](Thecomplexissquareplanar.)

Analysis

Weneedtoseeifchangingtherelativepositioningoftheligandsaroundthecentralmetaliongivesriseto
differentcomplexes.Ifso,thenstereoisomersarepresent.

Solution
(a)Inthiscomplex,wehavefiveNH3ligandsandasingleOH2ligandarrangedinanoctahedron
aroundthemetalion.Asallthepositionsinanoctahedronareequivalent,wecanplacetheunique
aqualigandanywhere,anditspositionrelativetothefiveNH3ligandsisthesametherearealways
fourcisneighbouringNH3ligandsandonetransNH3ligandopposite.Thethreedepictionsofthe
cationbelowarethereforeidenticalandhencetherearenostereoisomersofthiscomplex.
(b)Inthiscomplex,wehaveasetoffourNH ligandsandasetoftwoBrligands.Inanoctahedron,
3
wecanplacethetwoBrligandssothattheyareeitheradjacenttoeachother,oronoppositesides
fromeachother.Thisgivesrisetotwodifferentcomplexes,andthereforethesearestereoisomers.
Aninspectionofthedepictionsbelowshouldconvinceyouthatthesearetheonlystereoisomers
possible.

(c)Inthiscomplex,wehavefourdifferentligandsarrangedinasquareplanearoundthemetalion.
Therefore,youcananticipatethatthereshouldbeanumberofpossiblestereoisomers.Beginby
drawingone,andthensystematicallychangethepositionsoftheligandsuntilyouobtainnofurther
differentcomplexes.Todothis,keeponeligandinthesamepositionandlookatthenumberof
differentpossibleligandsthatcanbeplacedtranstothis.Youwillfindthat,nomatterwhichligand
youpick,thereareonlythreepossibledifferentarrangements,asshownbelow.

Youmightthinkthatthefollowingstructureisnotthesameasanyoftheabovethree.

However,ifyourotateit180aroundtheH2OPtNH3axis,youwillobtainthethirdstructure
above.

PRACTICEEXERCISE13.4
Determinethenumberofpossiblestereoisomersof
thefollowingcomplexes,andsketchtheir
structures.
(a) [PtBrCl ]2(Thecomplexissquareplanar.)
3
(b)[CoCl2(PPh 3)2](Thecomplexistetrahedral
notethatPPh 3isshorthandforP(C6H5)3,a
monodentatephosphaneligand.)
(c)
 [CoCl(NH3)3(OH2)2]2+(Thecomplexis
octahedral.)

Thenomenclatureoftransitionmetalcomplexes
Chapter2introducedtheIUPACrulesfornamingsimpleorganiccompoundsandwefoundthatsuchcompounds
werenamedonthebasisofthelongestcarbonchaininthemolecule.Wecannotusetheserulesfornaming
coordinationcompoundssoaseparatenomenclaturesystemisnecessary.Therulesareasfollows:
1.Cationicspeciesarenamedbeforeanionicspecies.Thisisthesamerulethatappliestootherioniccompounds,
suchasNaCl,wherewenamethecationfirstfollowedbytheanion(e.g.sodiumchloride).
2.Thenamesofanionicligandsalwaysendinthesuffixo.Ligandswithnamesendinginide,iteoratehave
thissuffixchangedtoido,itoandato,respectively.

Anion Ligandname
chloride Cl chlorido

bromide Br bromido

cyanide CN cyanido

oxide O2 oxido

carbonate CO32 carbonato

thiosulfate S2O32 thiosulfato

thiocyanate SCN thiocyanatoS(whenbondedthroughsulfur)thiocyanatoN(whenbonded

throughnitrogen)
oxalate C2O42 oxalato
nitrite NO2 nitritoO(whenbondedthroughoxygen)nitritoN(whenbondedthrough
nitrogen)
Whenachoiceofdonoratomexists,thecoordinatedatomisitalicisedandprecededbytheGreekletterkappa,
.
3.Aneutralligandisusuallygiventhesamenameastheneutralmolecule.Thusthemoleculeethylenediamine,
whenservingasaligand,iscalledethylenediamineinthenameofthecomplex.Threeveryimportant
exceptionstothis,however,arewater,ammoniaandcarbonmonoxide.Thesearenamedasfollowswhenthey
serveasligands:
H2Oaqua
NH3ammine(notethedoublem)
COcarbonyl.
4.Whenthereismorethanoneofaparticularligand,theirnumberisspecifiedbytheprefixesdi=2,tri=3,
tetra=4,penta=5,hexa=6etc.Ifthenameoftheligandalreadyincorporatesoneoftheseprefixes(suchas
ethylenediamine),enclosetheligandinparenthesesandusethefollowingprefixesinstead:bis=2,tris=3,
tetrakis=4.Followingthisrule,thepresenceoftwoClligandsinacomplexwouldbeindicatedas
dichlorido.Iftwoethylenediamineligandsarepresent,wewouldwritebis(ethylenediamine).
5.Inthenameofthecomplex,theligandsarenamedfirst,inalphabeticalorderwithoutregardtocharge,followed
bythenameofthemetal.Forexample,theligandsetintheneutralcomplex[Co(CN)Cl2(NH3)3]wouldbe
namedastriamminedichloridocyanido:triammineforthethreeNH3ligands,dichloridoforthetwoCl
ligandsandcyanidofortheCNligand.Noticethat,inalphabetisingthenamesoftheligands,weignorethe
prefixestrianddi.Thustriammineiswrittenbeforedichloridobecauseammineprecedeschlorido
alphabetically.Forthesamereason,dichloridoiswrittenbeforecyanido.
6.Negative(anionic)complexionsalwaysendinthesuffixate.ThissuffixisappendedtotheEnglishnameof
 themetalatominmostcases.However,ifthenameofthemetalendsiniumorese,theendingisdroppedand
replacedbyate.

Metal Metalasnamedinananioniccomplex
chromium chromate
manganese manganate

nickel nickelate
cobalt cobaltate
zinc zincate
platinum platinate
vanadium vanadate
FormetalswithsymbolsderivedfromtheirLatinnames,thesuffixateisappendedtotheLatinstem.

Metal Stem Metalasnamedinananioniccomplex

iron ferr ferrate
copper cupr cuprate
silver argent argentate
gold aur aurate
Mercury,antimonyandtungstenaretheexceptionsinananion,theyarenamedmercurate,antimonateand
tungstate,respectively.Forneutralorpositivelychargedcomplexes,themetalisalwaysspecifiedwiththe
Englishnamefortheelement,withoutanysuffix.
7.TheoxidationstateofthemetalinacomplexmaybewritteninRomannumeralswithinparenthesesfollowing
thenameofthemetal,orthechargeonthecoordinationentitymaybespecifiedinArabicnumbersfollowedby
thechargesign,allenclosedinparentheses.Forexample:
[Co(NH ) ]3+isthehexaamminecobalt(III)ionorthehexaamminecobalt(3+)ion.
36
[CuCl ]2isthetetrachloridocuprate(II)ionorthetetrachloridocuprate(2)ion.
4
Noticethattherearenospacesbetweenthenameoftheligandsandthenameofthemetal,andthereisno
spacebetweenthenameofthemetalandtheparenthesesthatenclosetheoxidationstateexpressedineither
RomanorArabicnumerals.
8.Thenumberofcounterionsneednotbespecified,asitcanbeinferredfromthechargeonthecomplexion.For
example,K4[NiCl6]wouldbenamedpotassiumhexachloridonickelate(II),nottetrapotassium
hexachloridonickelate(II).Notealsothatthereisaspacebetweenthenamesofthecationandanion.
9.Includeanystereochemicaldescriptors(e.g.cis,trans,mer,fac)atthestartofthename,italicisedand
hyphenated.Thefollowingaresomeadditionalexamples.Studythemcarefullytoseehowtherulesgivenon
pp.52830apply,thentryworkedexamples13.5and13.6andpracticeexercises13.5and13.6

[Ni(CN)4]2 tetracyanidonickelate(II)ion

K3[CoCl6] potassiumhexachloridocobaltate(III)

[CoCl2(NH3)4] tetraamminedichloridocobalt(III)ion

[Ag(NH3)2]+ diamminesilver(I)ion

[Ag(S2O3)2]3 dithiosulfatoargentate(I)ion

[Mn(en)3]Cl2 tris(ethylenediamine)manganese(II)chloride

[PtCl2(NH3)2] diamminedichloridoplatinum(II)
 WORKEDEXAMPLE13.5

NamingCoordinationComplexes
WhatistheIUPACnameforeachofthefollowingcoordinationcompounds?
(a)[Ni(OH2)6]SO4
(b)[CrCl2(en)2]Cl
(c)K2[CoCl4]

Analysis

Wesimplyfollowtheguidelinesgivenonpp.52830fornamingcoordinationcompounds.

Solution
(a)Thenickelionissurroundedbysixligands,soweusetheprefixhexa.Theligandsarewater
molecules,whichhavethespecialnameaqua,sotheligandsetisnamedhexaaqua.Thecomplex
iscationic,andthe2chargeonsulfatemeansthatthecationhasa2+charge.Astheaqualigands
areneutral,theoxidationstateofNiisNi(II).Therefore,thenameofthecomplexis
hexaaquanickel(II)sulfate.
(b)ThechromiumioniscoordinatedtotwoenligandsandtwoClligands.Namingtheligands
alphabeticallyputstheClligandsfirst,followedbytheenligands.ThetwoClligandsarenamed
dichlorido,while,aswehaveseenintheguidelines,twoenligandsarenamed
bis(ethylenediamine).Hence,theligandsetisnameddichloridobis(ethylenediamine).Thepresence
ofasingleClcounterionmeansthatthechargeonthecomplexcationis1+theoxidationstateof
themetalionmustbeCr(III),asithastwoClionscoordinatedtoit.Therefore,thenameofthe
complexisdichloridobis(ethylenediamine)chromium(III)chloride.
(c)Thecation,potassium,isnamedfirst.Thecomplexanioncontainsacobaltionsurroundedbyfour
Clligands,sotheligandsetisnamedtetrachlorido.Thecomplexisananionwitha2charge,so
theoxidationstateofthemetalionisCo(II).Sincethecomplexisananion,themetalisgiventhe
suffixate.Therefore,thenameofthecomplexispotassiumtetrachloridocobaltate(II).

Isouranswerreasonable?

Verifythatthenumericalprefixesgivethecorrecttotalnumberofligands,thattheligandsarenamed
alphabeticallyandthattheoverallspeciesischargeneutral.Thisshouldensurethatyouransweriscorrect.

PRACTICEEXERCISE13.5
Namethefollowingcoordinationcompounds.
(a)[Co(NH3)5(OCO2)]NO3
(b)[Mo(CO)3(NH3)3]
(c)[Cr(OH2)5OH]Cl2
(d)K3[Fe(CN)6]
(e)[CrCl2(en)2]2SO4

Havinglearnedhowtonamecoordinationcompounds,youshouldbeabletodeterminetheformulafromthename.
 WORKEDEXAMPLE13.6

WritingaFormulafromtheNameofaCoordinationCompound
Determinetheformulaeofthefollowingcoordinationcompounds.
(a)factriamminetriiodidoruthenium(III)
(b)sodiumhexacyanidoferrate(II)

Analysis

Constructtheformulabybreakingthenamedown,onepieceatatime.Beginbydeterminingthenumber
andtypeofligandsaroundthemetalion.Fromthese,andtheoxidationstateofthemetalion,youcanthen
determinethecorrectnumberofcounterions(ifany).

Solution
(a) TheprefixtriamminecorrespondstothreeNH ligandsandtriiodidotothreeIligands.Therefore,
3
therearesixligandssurroundingtheRu(III)ion.Thefacprefixmeansthateachsetofthreeligands
isarrangedsuchthattheyoccupyafaceofanoctahedron.Theformulaofthecomplexisfac
[RuI3(NH3)3].
(b)TheprefixhexacyanidomeansthattherearesixCNligandsaroundtheFe(II)ion,andthisgives
theanionachargeof4.Sodiumisthecation,sofourofthesearerequiredtobalancethechargeon
thecomplexanion.TheformulaofthecomplexisNa4[Fe(CN)6].

Isouranswerreasonable?

Conversionfromthenametotheformulaisusuallyfairlystraightforward,andouranswersdocorrespond
tothenames.Asshownin(b),makesureyouincludethecorrectnumberofcationsandanionstoensure
chargeneutrality.

PRACTICEEXERCISE13.6
Determinetheformulaeofthefollowing
coordinationcompounds.
(a)tris(ethylenediamine)ruthenium(II)chloride
(b)potassiumhexachloridoplatinate(IV)
(c)ammoniumdiaquatetracyanidoferrate(II)
(d)transdichloridobis(ethylenediamine)
cobalt(III)chloride

Thechelateeffect
Inchapter11,wequantifiedthestrengthofBrnstedLowryacidsusingKa ,theequilibriumconstantfordonationofa
protontowater.Astheformationoftransitionmetalcomplexesfromtheirconstituentmetalionsandligandsisalsoan
equilibriumprocess,wecanuseananalogousmethodtoquantifytheextentofsuchreactions.Consider,forexample,
theformationofahypotheticalcomplex[MLn]x+fromthemetalion,Mx +,andtheligands,nL,inaqueoussolution
accordingtotheequation:
(Notethat,forsimplicity,wehaveassumedthattheligandisneutral.)Theequilibriumconstantforthisprocess,which
wecanwriteinthesamewayaswehavedoneinprecedingchapters,iscalledthecumulativeformationconstant
(n).Therefore,fortheaboveequilibrium:

Obviously,thelargerthevalueofn,thefurthertotherighthandsidetheequilibriumpositionlies,andthereforethe
morecompletetheformationofthecomplex.Table13.3givesvaluesofnforanumberoftransitionmetal
complexes,andyoucanseethat,inallcases,theequilibriumfortheformationreactionliesverymuchtowards
products.However,thereisarangeofnearly44ordersofmagnitudeinthevaluesofn,showingthattheformation
reactionsofsomecomplexesproceedfurthertowardscompletionthanothers.
TABLE13.3 n valuesforavarietyoftransitionmetalcomplexescontainingmonodentateandpolydentateligandsat25
C

Ligand Metal Equilibrium n n

NH3 Co(II) Co 2+(aq)+6NH3(aq) [Co(NH3)6]2+(aq) 6 5.010 4
Co(III) Co 3+(aq)+6NH (aq) [Co(NH3)6]3+(aq) 6 4.610 33
3

Ni(II) Ni2+(aq)+6NH3(aq) [Ni(NH3)6]2+(aq) 6 2.010 8

Cu(II) Cu 2+(aq)+4NH3(aq) [Cu(NH3)4]2+(aq) 4 1.110 13
en Co(II) Co 2+(aq)+3en(aq) [Co(en)3]2+(aq) 3 1.010 14
Co(III) Co 3+(aq)+3en(aq) [Co(en)3]3+(aq) 3 5.010 48

Ni(II) Ni2+(aq)+3en(aq) [Ni(en)3]2+(aq) 3 4.110 17

Cu(II) Cu 2+(aq)+2en(aq) [Cu(en)2]2+(aq) 2 4.010 19

EDTA4 Co(II) Co 2+(aq)+EDTA4(aq) [Co(EDTA)]2(aq) 1 2.810 16

Co(III) Co 3+(aq)+EDTA4(aq) [Co(EDTA)](aq) 1 2.510 41

Inspectionofthedataintable13.3revealssomeinterestingtrends.Forexample,coordinationofthesameligandto
differentmetalionsgivesverydifferentnvalues,showingthatagivenligandbindsmorestronglytosomemetalions
thantoothers.Ligandscanalsoshowdifferentaffinitiesforvariousoxidationstatesofthesamemetalion.For
example,noticetheverydifferentvaluesfortheCo(II)andCo(III)complexeslisted,withCo(III)favouredineach
casebyafactorofupto10 34.OfparticularinterestarethevaluesforcomplexesofthemonodentateligandNH3and
thebidentateliganden.Forexample,[Ni(NH3)6]2+and[Ni(en)3]2+haveverysimilarstructures,withNibondedtosix
Natomsinbothcases,but3for[Ni(en)3]2+islargerthan6for[Ni(NH3)6]2+byafactorof10 9.Thistrendis
repeatedinallofthecomplexesofNH3andethylenediaminelistedintable13.3andisfoundtobefairlygeneralfor
complexescontainingtheseligands.

Thelargervaluesofnforcomplexescontainingpolydentateligandsthanforanalogouscomplexescontaining
monodentateligandsiscalledthechelateeffect,andthisisbestexplainedwithreferencetothedissociation,rather
thanformation,reactionsofthetwoNicomplexesdiscussedabove:
NotethattheexpressionsforKaresimplythereciprocalsofthosefornforeachcomplex.Therefore,thevaluesofK
aresimply1/nfortherespectivecomplexes.

Recallfromchapter9(p.362)that forareactionisrelatedtotheequilibriumconstantforthatreactionbythe
equation .Therefore,alargenegativevalueof leadstoalargeequilibriumconstantforthe
reaction,meaningthattheforwardreactionwillproceedessentiallytocompletion.Wealsolearnedinchapter8(p.
326)that ,andthattherelativemagnitudesandsignsofboth and arecrucialin
determiningthevalueandsignof ,andhencethevalueofK.Ifweexaminethetwodissociationreactionsabove,
wecanseethatbothinvolvebreakingsixNiNbondsandthisshouldresultinsimilarpositivevaluesof forthe
tworeactions.However,thetworeactionsdifferintheirvaluesof .Whiledissociationof[Ni(NH3)6]2+givesno
netchangeinthenumberofspeciesinsolution,andwouldthusbeexpectedtohavea valuearoundzero,
dissociationof[Ni(en)3]2+givesanetdecreaseinthenumberofspeciesinsolution,andhencehasanegative
value.Rememberingthatthe valuesaresimilar,wethereforeexpect fordissociationof[Ni(NH3)6]2+tobe
smallerandlesspositivethanthatfor[Ni(en)3]2+.Thismeansthat shouldbegreaterthan ,
asisindeedfound.

Wecanalsorationalisethechelateeffectbyconsideringthemechanismsofthedissociationreactions.Theinitial
mechanisticprocessthatoccursinbothcasesiscleavageofasingleNiNbondinthecaseof[Ni(NH3)6]2+,this
leadstothelossofoneNH3ligand,whichisimmediatelyreplacedbyawatermolecule:

However,cleavageofanNiNbondin[Ni(en)3]2+leadstoasituationinwhichoneendofoneoftheenligands
becomesdetachedfromthecomplexbutremainsclosetothemetalionbecausetheotherdonoratomoftheenligand
isstillbondedtothemetalion.Therefore,thereisasignificantprobabilitythatthedanglingdonoratomcanreattach
tothemetalionbeforetheotherendoftheliganddetaches(figure13.23)fromthis,itisapparentthatitshouldbe
moredifficulttoloseabidentateligandthanamonodentateligand.

FIGURE13.23Thechelateeffect.BreakingoneNiNbondin[Ni(en)3 ]2+leavestheenliganddanglingbuttetheredtothe
metalbythesecondnitrogenatom(hydrogenatomshavebeenomittedforclarity).
Thelossofaligandbecomesprogressivelymoredifficultasthenumberofdonoratomsincreases.Therefore,in
general,themoredonoratomsaligandcontains,thelargeristhevalueofnforitscomplexes.

Wecanobtainsomeappreciationofthemagnitudesofnvaluesbycarryingoutcalculationssimilartothosewehave
performedforotherequilibriumsystemsinearlierchapters.Forexample,workedexample13.7looksatareaction
usedtoextractgoldfromores.

WORKEDEXAMPLE13.7

CalculationsInvolvingn

Thesmallamountsofgoldinlowgradeores(figure13.24)canbeextractedusingacombinationofoxi
dationandcomplexation.ElementalgoldisoxidisedtoAu +,whichformsacomplexwithcyanideanions
accordingtotheequation:

FIGURE13.24Goldinlowgradeorescanbeextractedusingoxidationandcomplexation.

Supposethatasampleoforecontaining2.510 3molofgoldisextractedwith1.0Lof4.010 2m
aqueousKCNsolutionunderoxidisingconditions.Calculatetheconcentrationsofthethreespecies
involvedinthecomplexationequilibrium.

Analysis

Wetreatthisinasimilarfashiontoproblemswehaveseeninearlierchaptersbyusingaconcentration
table.However,inthiscase,weassumecompleteinitialformationof[Au(CN)2].Wearejustifiedinthis
assumptionbecauseoftheenormousvalueof2.WethenrealisethataverysmallamountofAu +andCN
willbeformedbydissociationof[Au(CN)2]and,usingtheconcentrationtableandthevalueof2,wecan
determinetheequilibriumconcentrations.

Solution

Weassumeallofthegoldisinitiallyconvertedto[Au(CN)2],soourinitialconcentrationsforthe
concentrationtableare:

Weobtainthestarting[CN]from ,so:

Thesystemthencomestoequilibriumthroughdissociationof[Au(CN)2]toformbothAu +andCN.The
concentrationtableisthen:

Au+(aq)+2CN(aq) [Au(CN)2]
 Initialconcentration(m) 0 3.510 2 2.510 3
Changeinconcentration(m) +x +2x 2x
Equilibriumconcentration(m) x 3.510 2+2x 22.510 3x

As2=210 38,weknowthatthedissociationof[Au(CN)2]willproceedonlytoatinyextent.Wecan,
therefore,assumewithconfidencethat(2.510 3x)2.510 3and(3.510 2+2x2)3.510 2.We
cannowsubstitutethesevaluesintotheexpressionfor2andsolvefortheonlyremainingunknown,
[Au +]:

Therefore:

Thetinyvalueof[Au +]showstheextraordinarilyhighaffinityofCNforAu +inaqueoussolution.

Isouranswerreasonable?

Owingtothelargevalueof2,weexpectanextremelylowconcentrationofAu +insolution,whichiswhat
wehavefound.Ourassumptionsarethereforereasonableandformationof[Au(CN)2]isessentially
complete.

PRACTICEEXERCISE13.7
Dissolutionof0.275gofsilvernitratein0.85Lof0.250M
ammoniaresultsintheformationofthecomplex[Ag(NH3)2]+
accordingtotheequation:

Calculatetheequilibriumconcentrationsofallspeciesinvolved
inthecomplexationequilibrium.

Inertandlabiletransitionmetalcomplexes
Themagnitudeofnforacomplexisameasureofhowfartheformationreactionforthatcomplexproceedstowards
completion.Forexample,ifnissmall,thecomplexshowslittletendencytoformfromthefreemetalionand
ligand(s)ifnislarge,thecomplexformsalmostcompletely.

Wemightbetemptedtosaythatthelargerthevalueofn,themorestablethecomplexthisistruefroma
thermodynamicviewpoint,becausethelargerthevalueofn,thelargerandmorenegativethevalueof forthe
formationofaparticularcomplex.However,wefindthatmanycomplexeswithlargenvaluesare,infact,quite
unstablewithrespecttoexchangeofligands.Thisisillustratedbythecomplex[Ni(CN)4]2,forwhich4=3.210 30.
ThisextremelylargevaluemeansthatadditionofCNtoasolutioncontainingNi(II)ionsresultsinessentially
completeformationof[Ni(CN)4]2.However,additionof14CN(cyanidecontainingaradioactive14Clabel)toa
solutionof[Ni(CN)4]2resultsinveryrapidincorporationof14CNintothecomplex,asshowninthefollowing
equation:

Thismeansthatthecyanideligandsin[Ni(CN)4]2arenotbondedstronglytotheNi(II)ion,sotheyexchangevery
rapidlywithaddedCN.Wesaythatthe[Ni(CN)4]2ionislabile,meaningthatitundergoesrapidligandexchange.
[Ni(CN)4]2is,therefore,anexampleofathermodynamicallystable,butkineticallylabile,transitionmetalcomplex.
TheoppositesituationisobservedfortheCo(III)complex[Co(NH3)6]3+.Theequilibriumconstantforthereaction:

isoftheorderof10 25at25C,correspondingtoa valueof143kJmol1.Thismeansthatthe[Co(NH3)6]3+ion

isthermodynamicallyunstablewithrespecttoformationof[Co(OH2)6]3+inacidicsolution.Despitethis,
[Co(NH3)6]3+canberecoveredunchangedafterseveraldaysin1.0MH3O+,meaningthattheNH3ligandscannot
easilyexchangewithH2O.Wesaythat[Co(NH3)6]3+isinerttoligandsubstitutionand,therefore,isanexampleofa
thermodynamicallyunstable,butkineticallyinert,transitionmetalcomplex.Mostfirstrowtransitionmetalcomplexes
arelabile,butcomplexescontainingmetalswithad3ord6electronconfigurationareofteninert,withCr(III)and
Co(III)beingtheclassicexamplesofinertmetalcentres.Itisimportant,therefore,thatyouarecarefulwhenusingthe
wordstable,andthatyourealisethatthermodynamicstabilityandkineticstabilityareentirelyseparateconcepts.

Electrochemicalaspectsoftransitionmetalcomplexes
Electrochemistryprovidesanotherconvenientmethodofquantifyingthethermodynamicstabilityoftransitionmetal
complexes.Aswesawinchapter12(table12.1),thereductionpotentialsofsimpleaqueoustransitionmetalionsspan
awiderangeofvaluesand,therefore,electrochemicalbehaviour.Thus,theAg +(aq)ionismoderatelyoxidising
whiletheCr3+(aq)toionshowsneglibileoxidisingability .However,
coordinationofligandstoaqueoustransitionmetalionscanresultintheformationofcomplexeshavingverydifferent
electrochemicalbehavioursfromthoseoftheparentaqueoustransitionmetalions.Theclassicexampleofthisis
providedbytheCo 3+(aq)(or[Co(OH2)6]3+)ion.Understandardconditionsinaqueoussolution,thisionisextremely
stronglyoxidising ,andasaresultisgenerallystableonlyundericecoldacidicconditions.
However,replacementofthesixH2OligandswithsixNH3orthreeethylenediamine(en)ligandsresultsinenormous
stabilisationoftheresulting and ions.
ThisobservationisgeneralforthemajorityofNdonorligandsand,asaresult,Co(III)complexesinwhichthemetal
ionisbondedtosixoxygenatomsareratherrare.

Whenatransitionmetalionissurroundedbyanionicligands,theresultingcomplexgenerallybecomesmoredifficult
toreduce,asadditionofanelectrontoanegativelychargedcomplexisunfavourableonelectrostaticgrounds.An
exampleofthisistheanionicFe(III)complex[Fe(CN)6]3,forwhich ,

significantlylessthanthatforthecationicFe3+(aq)ion .

Thecorrectchoiceofligandcanassistinstabilisingtransitionmetalionsthatareunstablewithrespectto
disproportionation.Thisisaredoxreactioninwhichthemetalionissimultaneouslyoxidisedandreduced.Themost
celebratedexampleistheCu +(aq)ion,forwhichthefollowing valueshavebeenobtained.
ThedisproportionationofCu +proceedsaccordingtotheequation:

forwhich (assumingthatCu +isreducedattherighthandelectrode).

Thepositivevalueof showsthatthisreactionisspontaneousunderstandardconditions,andaqueoussolutionsof
Cu +areoftenfoundtobeunstable.However,useofstrongfieldligands(seep.572)suchasCNorvarious
phosphanesgivesCu(I)complexeswhichshowsignificantstability.Notethatdisproportionationisnotlimitedto
transitionmetalions,andspeciessuchasO2(superoxide)andHOCl(hypochlorousacid)candisproportionate.

Bondingintransitionmetalcomplexes
Earlierinthischapter,westatedthattwoofthedefiningcharacteristicsoftransitionmetalcomplexesarethattheyare
usuallycolouredandthattheyareoftenparamagnetic.Itisnotunusualforagivenmetaliontoformcomplexeswith
differentligandstogivearainbowofcolours,asillustratedinfigure13.25foraseriesofCo(III)complexes.

FIGURE13.25AqueoussolutionsoftheCo(III)complexes(fromlefttoright)[Co(O2 CO)(en)2 ]+,trans[CoCl2 (en)2 ]+,

[Co(en)3 ]3+,[CoCl(NH3 )5 ]2+and[Co(NH3 )5OH2 ]3+.Asthemetalionisthesameinallcases,thevarietyof
coloursarisesfromthedifferentligandssurroundingtheCo(III)ion.
Also,becausetransitionmetalionsoftenhaveincompletelyfilleddorbitals,weexpecttofindmanyofthemwith
unpaireddelectrons,andsuchcompoundsshouldthereforebeparamagnetic.However,foragivenmetalionina
particularoxidationstate,thenumberofunpairedelectronsisnotnecessarilythesamefromonecomplextoanother.
Consider,forexample,theFe(II)complexes[Fe(OH2)6]2+and[Fe(CN)6]4.AsFe2+hastheelectronconfiguration
[Ar]3d6,bothcontainsixdelectrons,butfouroftheseareunpairedinthe[Fe(OH2)6]2+ion,whileallofthemare
pairedinthe[Fe(CN)6]4ion.Asaresult,the[Fe(OH2)6]2+ionisparamagneticandthe[Fe(CN)6]4ionis
diamagnetic.Wecanexplainboththecoloursandmagneticpropertiesoftransitionmetalcomplexesusingcrystal
fieldtheory,atheoryofbondingthatlooksathowtheenergiesofthedorbitalsonthemetalionareinfluencedbythe
surroundingligands.

Crystalfieldtheoryofbondinginoctahedralcoordinationcomplexes
Crystalfieldtheoryisbasedonthepremisethattheligandssurroundingthemetalioninatransitionmetalcomplex
exertanelectricfieldthataffectstheenergiesofthedorbitalsonthemetaliontodifferentextents.Itassumesthatthe
interactionbetweenthemetalandtheligandsispurelyelectrostatic,anunrealisticsituation,giventhatallmetalligand
bondsexhibitsomedegreeofcovalency.Nevertheless,crystalfieldtheorycanexplainmanyoftheunusualfeatures
oftransitionmetalcomplexesandisconceptuallystraightforward.

Webeginbylookingattheelectrondistributions(figure13.26)andenergiesofthefivedorbitalsinafreetransition
metalion.

FIGURE13.26Thedirectionalpropertiesofthefivedorbitalsinafreetransitionmetalion.

Thed xy ,d xzandd yzorbitalsallhavelobespointingbetweenthex,yandzaxes,whilethelobesofthe and

orbitalspointalongtheaxes.Intheabsenceofanyligands,thefivedorbitalsaredegenerate,meaningtheyare
allofthesameenergy.However,thisisnotthecaseinthepresenceofligands,wherewefindthatthedegeneracyis
removed.Weillustratethisbyconsideringtheformationofanoctahedraltransitionmetalcomplexbytheintroduction
ofsixligandsatbondingdistancealongthex,yandzaxes,asshowninfigure13.27onthenextpage,andlooking
attheeffectofthisontheenergiesofthefivedorbitals.

FIGURE13.27 (a)AnoctahedralML6 complexand

(b)theorientationofthemetalorbitalwithrespecttotheligandsinanoctahedralML6 complex.

Inanisolatedatomorion,allthedorbitalsofagivendsubshellaredegenerate.Therefore,anelectronhasthesame
energyregardlessofwhichdorbitalitoccupies.Inanoctahedralcomplex,however,thisisnolongerthecase.Asthe
lobesofthe orbitalspointdirectlytowardstheligands,anelectronineitheroftheseorbitalsisnearerthe
electronpairsoftheligandsthanifitwasinad xy ,d xzord yzorbital,withlobespointingbetweentheligands.Sincethe
electronitselfisnegativelychargedandisrepelledbytheligandelectrons,anelectroninthe or orbitalis
ofhigherenergythanoneinad xy ,d xzord yzorbital.Therefore,wecanseethatintroductionoftheligandsremoves
thedegeneracyofthefivedorbitals,splittingthemintotwosetsofdegenerateorbitalsthelowerenergysetconsists
ofthed xy ,d xzandd yzorbitals,andthehigherenergysetcomprisesthe and orbitals(figure13.28).The
threelowerenergyorbitalsarecollectivelycalledthet2gorbitalswhilethetwohigherenergyorbitalsarecalledtheeg
orbitals.Theselabelsrefertothesymmetryofthesetsoforbitals,andareobtainedusingabranchofmathematics
calledgrouptheory,whichisdescribedinadvancedchemistrycourses.

FIGURE13.28Thechangesintheenergiesofthedorbitalsofametalionasanoctahedralcomplexisformed.Astheligands
approachthemetalion,theinitiallydegeneratedorbitalssplitintotwonewsetsofdegenerateorbitals.

Figure13.28showsthat,regardlessofwhichorbitaltheelectronoccupies,itsenergyincreasesbecauseitisrepelled
bytheelectronsoftheapproachingligands.However,theelectronisrepelledmore(andhasahigherenergy)ifitisin
anorbitalthatpointsdirectlyattheligandsthanifitoccupiesanorbitalthatpointsbetweenthem.Inanoctahedral
complex,theenergydifferencebetweenthetwosetsofdorbitalenergylevelsiscalledthecrystalfieldsplitting
energy(CFSE).Itisusuallygiventhesymboloinoctahedralcomplexes(deltaoh,theostandingforoctahedral),
anditsmagnitudedependsonthefollowingfactors.
Thenatureoftheligand:Someligandsproducealargersplittingoftheenergiesofthedorbitalsthanothers.For
example,foragivenmetalion,CNnearlyalwaysgivesalargevalueofo,andFalwaysgivesasmallvalue.
ThisisduetothemoreextensiveorbitalinteractionsbetweenthemetalandligandthatoccurinthecaseofCN.
Wewilldiscussthisfurtherlaterinthissection.
Theoxidationstateofthemetal:Foragivenmetalandligand,thesizeofoincreaseswithanincreaseinthe
oxidationstateofthemetal.Aselectronsareremovedfromthemetal,thechargeontheionbecomesmore
positiveandtheionbecomessmaller.Thismeansthattheligandsareattractedtothemetalmorestronglyand
theycanapproachthemetalionmoreclosely.Asaresult,theyalsoapproachthedorbitalsalongthex,yand
zaxesmoreclosely,causinggreaterrepulsion.Thisproducesagreatersplittingofthet2gandegorbitalsanda
correspondinglylargervalueofo.
Thepositionofthetransitionmetalintheperiodictable:Foragivenligandandoxidationstate,themagnitudeof
oincreasesgoingdownagroup.Inotherwords,anionofanelementinthefirstrowoftransitionelementshas
asmallervalueofothantheionofaheaviermemberofthesamegroup.Thus,comparingcomplexesofNi2+
andPt2+withthesameligand,wefindthattheplatinumcomplexeshavethelargercrystalfieldsplitting.The
explanationofthisisthat,inthelargerPt2+ion,thedorbitalsarelargerandmorediffuseandextendfurtherfrom
thenucleusinthedirectionoftheligands.Thisproducesalargerrepulsionbetweentheligandsandtheorbitals
 thatpointatthem.

Thefinalpointtobemadehereconcernstheoverallenergeticsoftheorbitalsplitting.Figure13.28showsanoverall
energyincreaseongoingfromthedegeneratedorbitalsofafreemetaliontothedorbitalsinanoctahedralcomplex,
andthisisprimarilyduetoelectronelectronrepulsion.However,thedominantenergeticcontributionactuallyarises
fromthelargeattractiveelectrostaticinteractionsbetweenthepositivelychargedmetalionandtheligands.Therefore,
despitetheslightoveralldorbitalenergyincreasethatoccursoncomplexformation,themetalcomplexisstillof
muchlowerenergythantheinfinitelyseparatedmetalionandligands.

Electronconfigurationsinoctahedraltransitionmetalcomplexes
Havingshownthatthedorbitalsinatransitionmetalcomplexarenotdegenerate,wenowlookathowtheseorbitals
arepopulatedwithdelectrons.Welearnedinchapter4thatorbitalsarefilledinorderofincreasingenergy(the
Aufbauprinciple)asetofdegenerateorbitalshasasingleelectronplacedineachoftheorbitalsbeforeanypairingof
electronstakesplace(Hund'srule)andnotwoelectronsofthesamespinmayoccupythesameorbital(thePauli
exclusionprinciple).Theserulesgiveusthegroundstateelectronconfigurationofanychemicalspecies.Wewill,
therefore,considerthesituationsoutlinedinfigure13.29foroctahedralcomplexeshavingd1,d2andd3electron
configurations.

FIGURE13.29Orbitaloccupanciesford1 ,d2 andd3 electronconfigurations.

Thereisnoambiguityaboutthewayinwhichtheorbitalsarefilledfortheelectronconfigurationsinfigure13.29the
electronsareplacedinthelowestenergyt2gorbitalswithparallelspins.Ordinarily,wewouldthenplacethefourth
electron,spindown,inoneofthet2gorbitals.However,theenergydifferencebetweenthet2gandegsetsoforbitalsis
relativelysmallintransitionmetalcomplexes,andwemustweightheenergeticadvantageofplacingthefourth
electroninalowenergyt2gorbitalagainsttheenergeticdisadvantagethatresultsfromplacinganelectroninan
alreadyoccupiedorbital.Thislatterenergyiscalledthepairingenergy(P)andisdueprimarilytotheinterelectronic
repulsionsthatresultfromhavingtwoelectronsinthesameorbital.ThemagnitudeofP,comparedwiththecrystal
fieldsplittingenergy,o,determineswhichofthetwopossibleelectronconfigurationsisfavoured.IfP>o,the
energeticallyfavourableelectronconfigurationisthatinwhichthefourthelectronoccupiesanegorbital.Sucha
configurationiscalledthehighspinconfiguration,astheelectronspinsaremaximised.Conversely,whenP<o,the
complexadoptsthelowspinconfigurationinwhichthefourthelectronisaddedtooneofthelowerenergyorbitals
andispairedwithoneofthet2gelectrons.Inthiscase,theelectronspinsareminimisedandthelowestnumberof
unpairedelectronsresults.Thesepossibilitiesareshowninfigure13.30forthed4Cr(II)complexes[Cr(OH2)6]2+and
[Cr(CN)6]4.

FIGURE13.30 Thetwopossibleelectronconfigurationsforad4 complex.

(a)Wheno issmall,asfor[Cr(OH2 )6 ]2+,thehighspinconfigurationisfavoured.
(b)Alargevalueof favoursthelowspinconfiguration,asshownfor[Cr(CN) ]4.
o 6
Becauseofitsrelativelysmallvalueofo,[Cr(OH2)6]2+adoptsthehighspinconfiguration,while[Cr(CN)6]4,which
hasasignificantlylargervalueofo,islowspin.Inoctahedralcomplexes,highspinandlowspinpossibilitiesexist
onlyford4,d5,d6andd7electronconfigurations(figure13.31).Thereisonlyonepossibleconfigurationforeach
ofthed8,d9andd10configurations(figure13.32).

FIGURE13.31Lowspinandhighspinelectronconfigurationsford4d7 octahedraltransitionmetalcomplexes.Notethatthe
numberofunpairedelectronsisdifferentforthelowspinandhighspinconfigurationinallcases.
 FIGURE13.32Electronconfigurationsford8 ,d9 andd1 0octahedraltransitionmetalcomplexes.

Crystalfieldtheoryappliedto4coordinatecomplexes
Asmentionedearlier,4isthesecondmostcommoncoordinationnumberformetalionsincoordinationcompounds.
Wecanapplycrystalfieldtheorytothetwopossible4coordinategeometries,squareplanarandtetrahedral,usingthe
sameprincipleswelearnedearlier.

Squareplanarcomplexes

Wecanformasquareplanarcomplexfromanoctahedralcomplexsimplybyremovingthetwoaxialligandsthatlie
alongthezaxis.Thislowerstheenergyofanyofthedorbitalswithazcomponent( ,d xzandd yz)aselectronic
repulsionbetweentheelectronsintheseorbitalsandtheligandelectronsisreduced.Removingtheaxialligandsalong
thezaxisallowscloserapproachtothemetalbytheligandsinthexyplanethismeansthattheenergiesoftheorbitals
inthisplane( andd xy )areraisedslightly,withtheenergyofthe orbitalbeingmoreaffectedasits
lobespointdirectlytowardstheligands.Figure13.33showstheseenergychangesandtheresultingdorbitalsplitting
diagramforasquareplanarcomplex.
 FIGURE13.33Thederivationofadorbitalsplittingdiagram(nottoscale)forasquareplanarcomplexbyremovalofaxial
ligandsfromanoctahedralcomplex.

Tetrahedralcomplexes

Thederivationofadorbitalsplittingdiagramforatetrahedralcomplexisnotasconceptuallystraightforwardasthat
foranoctahedralorsquareplanarcomplex,asnoneofthefourligandsliesdirectlyalongthex,yorzaxes(figure
13.34).

FIGURE13.34Thedorbitalsplittingdiagramforatetrahedralcomplex.

Noticethattheorderoftheorbitalsisexactlyoppositetothatforanoctahedralcomplex(figure13.28).Ina
tetrahedralcomplex,thecrystalfieldsplittingenergyistermedt,anditcanbeshownthat forthesame
metalionwiththesameligands.Thissmallvalueoftisusuallylessthanthepairingenergy,P,sotetrahedral
complexesalmostalwaysadopthighspinelectronconfigurations.Notethathighspinandlowspinconfigurationsare
theoreticallypossibleford3,d4,d5andd6tetrahedralcomplexes.

Thecoloursoftransitionmetalcomplexes
Wesawinchapter4thatexcitedstateatomsemitphotonsofparticularenergiesonly.Asimilarsituationoccurswhen
atoms,ionsormoleculesabsorblightwefindthatthesespeciesabsorbphotonsofcertainenergiesonly,ratherthan
absorbingallphotonsirrespectiveoftheirenergy.Absorptionofaphotonbyanoctahedraltransitionmetalcomplex
canoccurifitsenergyexactlymatcheso,theenergydifferencebetweenthet2gandegsetsoforbitals.Thisthen
leadstoanelectronictransitionfromat2gorbitaltoahigherenergyegorbital.Suchelectronictransitions,which
involveelectronsinthet2gandegsetsoforbitalsonly,arecalledddtransitions.Inmanyoctahedraltransitionmetal
complexes,theenergydifference,o,correspondstophotonsofvisiblelight,asshowninfigure13.35forthed1
complex[Ti(OH2)6]3+.Thisisthereasonthatmanytransitionmetalcomplexesappearcoloured.
 FIGURE13.35 Absorptionofaphotonby[Ti(OH2 )6 ]3+:
(a)Theelectrondistributioninthegroundstateofthe[Ti(OH2 )6 ]3+ion
(b)Absorptionofaphotonresultsinanelectronictransitionfromthet2g setofdorbitalstothehigher
energyeg set.

Asyouknow,whitelightcontainsphotonswithenergiesthatcorrespondtoallofthecoloursinthevisiblespectrum,
asshowninfigure13.36.

FIGURE13.36Thevisiblespectrum,showingthecoloursasafunctionofwavelength.
Ifweshinewhitelightthroughasolutionofacolouredtransitionmetalcomplex,thelightthatemergesafterpassing
throughthesolutioncontainsallthecoloursexceptthosethathavebeenabsorbed,anditisthesetransmittedcolours
thatweperceivewhenwelookatthesolution.Ifweknowwhatcolourthesolutionappears,wecandeterminewhich
colourisbeingabsorbedbyusingacolourwheel,likethatshowninfigure13.37.
 FIGURE13.37Acolourwheel.Coloursoppositeeachotherarecalledcomplementarycolours.Whenasubstanceabsorbs
lightofaparticularcolour,thelightthatisreflectedortransmittedhasthecolourofitscomplement.Thus,
somethingthatabsorbsredlightappearsgreenblue,andviceversa.

Thecolourlyingoppositeanycolouronthewheeliscalleditscomplementarycolourforexample,redvioletisthe
complementarycolourofgreen,whilegreenblueisthecomplementarycolourofred.Ifasubstanceabsorbsa
particularcolourwhenilluminatedwithwhitelight,theperceivedcolourofthereflectedortransmittedlightisthe
complementarycolour.Inthecaseofthe[Ti(OH2)6]3+ion,theelectronictransitionfromthet2gsettotheegsetoccurs
onabsorptionofgreenlightandthisiswhyasolutionofthisionappearsredviolet.Wecanquantifytheabsorptionof
visiblelightusingaUV/visiblespectrophotometer,adevicethatdeterminesboththewavelengthandintensityoflight
absorbedbychemicalspecies.Spectrophotometersoutputaplotofabsorbance(A)versuswavelength,where
absorbanceisdefinedas:

withIobeingtheintensityoftheincidentlightandItheintensityofthetransmittedlight.Notethatabsorbanceisa
dimensionlessquantity.

Figure13.38showstheUV/visiblespectrumoftheredviolet[Ti(OH2)6]3+ion,andwecanseethatthisdisplaysa
singlepeak,withamaximumabsorbanceat514nm.

FIGURE13.38TheUV/visiblespectrumofthe[Ti(OH2 )6 ]3+ion.Thepeakcorrespondstoanelectronictransitionofthesingle
delectronfromthet2g totheeg orbitalset.

AsTi(III)isad1transitionmetalion,weknowthatthisabsorbancebandisduetothepromotionofthesingled
electronfromthet2gsetoforbitalstotheegsetoforbitals,andwecanusethehighestpointonthepeaktocalculate
theenergydifferencebetweenthesesetsoforbitalsinotherwords,wecancalculatethevalueofofor
[Ti(OH2)6]3+fromthisspectrum.Recallfromchapter4thatthereisaninverserelationshipbetweenwavelength()
andenergy(E),givenbytheequation:

whereh=6.62610 34Js(Planck'sconstant)andc=2.99810 8ms1(thespeedoflight).Wecannowfindthe

energycorrespondingtoaphotonofwavelength514nmbyusingtheequation:

Thisvaluetellsusthatthet2gandegorbitalsareseparatedby3.8610 19Jinasingle[Ti(OH2)6]3+ion.Itisusualto
reportthevalueofoforacomplexonamolarbasis,ratherthanforanindividualion,andwedothisbymultiplying
EbytheAvogadroconstant(6.02210 23mol1).Therefore:

Therefore,ofor[Ti(OH2)6]3+=232kJmol1.Itshouldbenotedthattheexactvalueoftocanbedeterminedinthis
wayonlyforasmallnumberofmetalcomplexes.Electronelectronrepulsionsincomplexeswithmorethanoned
electronmeanthattheexactdeterminationofoforsuchcomplexesisdifficult,and,indeed,beyondthescopeofthis
book.However,theprevioustreatmentdoesgiveafairapproximationofointhesecasesandwewillcontinuetouse
itthroughoutthischapter.

WehavealreadyseeninaseriesofCo(III)complexesthatthenatureoftheligandsiscriticalindeterminingthe
colouroftransitionmetalcomplexes(figure13.25)andmustthereforeinfluencethevalueofo.Thegreaterthevalue
ofo,thefurtherapartinenergyarethet2gandegorbitalsand,therefore,theshorterthewavelengthoflightrequired
topromoteanelectronfromthet2gsettotheegsetoforbitals.ThiscanbeillustratedbylookingattheTi(III)
complexes[TiF6]3and[Ti(NCS)6]3,whichhavemaximumabsorbancewavelengths(max)at526nmand543nm,
respectively.Theseareatalongerwavelengththanthatof[Ti(OH2)6]3+,whichhasamaximumabsorbance
wavelengthof514nm.

Theovaluescorrespondingtotheseabsorptionmaximaare232kJmol1for[Ti(OH2)6]3+,227kJmol1for[TiF6]3
and220kJmol1for[Ti(NCS)6]3,meaningthattheseparationofthet2gandegorbitalsvariessignificantlywiththe
identitiesoftheligandsforthesamemetalinthesameoxidationstate(figure13.39).

FIGURE13.39Energyseparationsbetweentheirt2g andeg orbitalsfor[Ti(OH2 )6 ]3+,[TiF6 ]3and[Ti(NCS)6 ]3+

Aligandthatproducesalargecrystalfieldsplittingwithonemetalionalsoproducesalargevalueofoincomplexes
withothermetals.Forexample,CNnearlyalwaysgivesaverylargevalueoforegardlessofthemetaltowhichitis
bound.ComplexescontainingNH3havelowervaluesofothancomplexescontainingCN,whileovaluesfor
complexescontainingH2Oaresmallerstill.Thus,ligandscanbearrangedinorderofthemagnitudeoftheircrystal
fieldsplittingenergies.Thissequenceiscalledthespectrochemicalseries.Suchaseriescontainingsomecommon
ligandsarrangedinorderofdecreasingovaluesis:
Foragivenmetalion,thecarbonylligandproducesthelargestvalueofo,andiodideproducesthesmallest.Ligands
suchasCO,CNandNO2,whichgivelargevaluesofo,arecalledstrongfieldligands,whilethehalideionsand
othersthatinducesmalldorbitalsplittingsarecalledweakfieldligands.Thedorbitalsplittingsinducedbystrong
fieldligandsareoftensolargethattheenergygapbetweenthet2gandegsetsoforbitalsisgreaterthantheenergyof
visiblephotons.Therefore,electronictransitionsbetweenthet2gandegorbitalsinoctahedralcomplexescontaining
onlyCOorCNligandsareoftencausedonlybyUVphotons,sosuchcomplexesareusuallyverypaleyellowor
colourless.

OctahedralcomplexesofZn(II)andhighspinMn(II)arealsooftencolourless,ornearlyso,butforaverydifferent
reasonZn(II)isad10metalion,meaningthatthet2gandegsetsoforbitalsarefull(figure13.40).

FIGURE13.40ThedelectronconfigurationsforcomplexesofZn(II)(left)andhighspinMn(II)(right).
Noelectronictransitionbetweenthet2gandegorbitalsispossible,astheegorbitalsareunabletoaccommodatean
extraelectron.HighspinMn(II)hasad5electronconfigurationasshowninfigure13.40topromoteanelectron
fromat2gorbitaltoanegorbital,wewouldrequiretheelectroninvolvedtochangeitsspinduringthetransition,
otherwiseasituationwouldresultinwhichtwoelectronswiththesamespinoccupyasingleorbital,inviolationofthe
Pauliexclusionprinciple.Wesay,therefore,thatthet2gegelectronictransitioninsuchcomplexesisspinforbidden
theprobabilityofsuchatransitionoccurringisverylow,sothesecomplexesareusuallyverypaleincolour.

Wemightexpectcomplexescontainingtransitionmetalionswithad0electronconfigurationtobecolourless,as
obviouslytherearenopossibleddtransitionsbetweenthet2gandegorbitals,andthisisborneoutinmanycases.
However,ionssuchas[MnO4](purple)and[Cr2O7]2(orange)areveryintenselycoloured,despitethemetalion
havingad0configurationineachcase.Thecolourinsuchcompoundsisduetoligandtometalchargetransfer
(LMCT)transitions,whichinvolvetheformaltransferofanelectronontheligandtoanorbitalonthemetalion.
Whilesuchtransitionsusuallyoccurintheultravioletpartofthespectrumandare,therefore,invisibletotheeye,
somelowenergyLMCTtransitionsareobserved,suchasthosein[MnO4]and[Cr2O7]2.LMCTtransitionshavea
muchhigherprobabilityofoccurringthantransitionsbetweent2gandegorbitals,andthisexplainstheextremely
intensecolourof,forexample,the[MnO4]ion.Insomecomplexeswherethemetalioncontainsoccupieddorbitals,
anelectroncanbeformallytransferredintheoppositedirection,i.e.fromthemetaltotheligand.Suchprocessesare
calledmetaltoligandchargetransfer(MLCT)transitionsandoftenoccurincomplexeshavingaromatic,pyridine
basedligands.Thesetransitionsalsohavehighprobabilitiesandleadtoveryintenselycolouredcomplexes.Oneof
thebestknownexamplesofacomplexthatdisplaysanMLCTtransitionis[Ru(bipy)3]2+,whichcontainsthree
bidentate2,2'bipyridineligands.

Itshouldbenotedthatitisnotthenatureoftheligandsalonethatultimatelydeterminesthecolourofatransition
metalcomplex.Forexample,theisomericcomplexescis[CoCl2(en)2]+andtrans[CoCl2(en)2]+,whichcontain
identicalligandscoordinatedtoaCo(III)centre,arevioletandgreen,respectively.Otherfactorssuchasthe
arrangementoftheligandsandthemetalligandbondlengthscanalsobeimportant.

WORKEDEXAMPLE13.8

ColoursofTransitionMetalComplexes
AstudentpreparedfiveCo(III)complexesinanundergraduatechemistrylaboratoryandstoredthemin
sampletubes.However,thestudentforgottolabelthetubesand,atthestartofthenextlaboratorysession,
couldnotrememberwhichcomplexwaswhich.Toidentifythem,thestudentrecordedtheUV/visible
 spectraofthecomplexesandfoundthatthefivecomplexesexhibitedmaximumabsorbancevaluesinthe
visibleregionat506nm,490nm,534nm,441nmand471nm.Thefivecomplexespreparedbythe
studentwere[CoCl(NH3)5]2+,[Co(NH3)6]3+,[Co(NH3)5OH]2+,[CoCN(NH3)5]2+and[Co(NH3)5OH2]3+.
MatchtheUV/visibledatatothecomplexes.

Analysis

Wehavefiveverysimilarcomplexes,allofwhichcontaina[Co(NH3)5]3+moietyanddifferonlyinthe
natureofthesixthligand.Therefore,weshouldbeabletousethespectrochemicalseriestodecidethe
orderoftheUV/visibleabsorptionmaximaacrossthefivecomplexesthestrongestfieldligandshould
havethelargestenergygapbetweenthet2gandegorbitals,andshouldthereforehavetheshortest
wavelengthabsorptionmaximum.

Solution

Webeginbyorderingthefiveligandsaccordingtotheirpositionsinthespectrochemicalseries,from
strongestfieldtoweakestfield.Theorderistherefore:

WewouldexpectthecomplexcontainingCNtohavethelargestenergygapbetweenthet2gandegsetsof
orbitals,asCNisthestrongestfieldligand,andthereforethiscomplexwillexhibittheshortestwavelength
(highestenergy)absorptionmaximum.ThecomplexcontainingClshouldhavethesmallestenergygap
betweenthet2gandegsetsoforbitals,asClistheweakestfieldligand,andthereforethiscomplexwill
exhibitthelongestwavelength(lowestenergy)absorptionmaximum.Theremainingthreecomplexeswill
beorderedaccordingtothepositionsoftheligandsinthespectrochemicalseriesabove.Therefore,the
identitiesofthecomplexesare:

PRACTICEEXERCISE13.8

Theoctahedralcomplex[CoCl6]4andthe
tetrahedralcomplex[CoCl4]2bothcontainCo(II).
Whichislarger:ofor[CoCl6]4ortfor
[CoCl4]2?Explainyouranswer.

Theabsorbanceofasolutionofatransitionmetalcomplex(andindeed,ofanysolution)isrelatedtotheconcentration
oftheabsorbingspeciesbytheBeerLambertlaw(alsooftencalledBeer'slaw),whichstatesthat:

whereA=absorbance(dimensionless), =molarabsorptioncoefficient(mol1Lcm1),c=concentrationofabsorbing
species(molL1)andl=pathlengthofcell(cm).Thesomewhatunusualunitsof arisefromthefactthatUV/visible
spectraaregenerallymeasuredusingcellsofdimensions1cm1cm.

The valuesfortransitionmetalcomplexesdependonboththegeometryofthemetalionandthetypeofelectronic
transitionoccurringand,assuch,canbeusefulincharacterisingthesespecies.Forexample,ddtransitionsfor
octahedralcomplexesgenerallyhave values<100mol1Lcm1and,asaresult,suchcomplexesareusuallyweakly
coloured.Tetrahedralcomplexesareoftenmoreintenselycoloured,with valuesforddtransitionsintheselyingdin
therange200250mol1Lcm1.Moreintensestill,asdiscussedonthepreviouspage,areLMCTandMLCT
transitions,whichcanhave valuesupto10 4mol1Lcm1.

YouwillnoticethattheUV/visiblespectraarisingfromddtransitionsintransitionmetalcomplexeslookvery
differentfromtheatomicspectrawesawinchapter4(p.120).Whilethelatterdisplaysharplines,indicativeof
electronictransitionsbetweenwelldefined,quantisedenergylevels,theformershowbroadbands,anobservation
seeminglyatoddswiththedefiniteenergiesofthet2gandegsetsoforbitalsbetweenwhichtheseelectronictransitions
occur.Thebroadbandscanberationalisedbyconsideringvibrationsofthecomplexes.Considerforexamplethe
octahedral[Ti(OH2)6]3+ion,theUV/visiblespectrumofwhichisgiveninfigure13.38ifallthe[Ti(OH2)6]3+ionsin
thesampleexhibitedidenticaloctahedralgeometrywithallTiObonddistancesthesame,thentheddabsorbance
bandwouldindeedbemuchnarrowerthanthatobserved.However,vibrationswithinthecationsatroomtemperature
ensurethatthereisavarietyofTiObonddistancesand,therefore,geometriesatanygiventime.Astheenergiesof
thet2gandegsetsoforbitalsdependontheTiObonddistances,thisthereforeleadstoarangeofenergydifferences
betweenthet2gandegsets,whichinturnresultsinbroadabsorptionbands.Singleatomscannotundergovibrationsin
thesamewayasmoleculesorpolyatomicions,andsotheirspectraconsistofsharplines.Thisisillustratedinfigure
13.41.

FIGURE13.41 (a)Intheabsenceofvibrations,theenergiesofthet2g andeg setsoforbitalsarepreciselydefined,and

anelectronictransitionbetweenthesethereforeresultinanarrowspectralline.
(b)Whenvibrationsoccur,theyresultinarangeofenergiesforeachofthet2g andeg setsoforbitals.
ElectronictransitionsbetweenthesethereforespantherangeofenergiesbetweenE1 andE2 ,
therebyleadingtobroadbands.

Themagneticpropertiesoftransitionmetalcomplexes
Aswehaveseenbothinchapter4andearlierinthischapter,aparamagneticsubstanceisonethatisattractedintoa
magneticfield.Forasubstancetobeparamagnetic,itmustcontainunpairedelectrons,thenumberofwhich
determinesthemagnitudeofitsresponsetoamagneticfield.Thisresponsecanbemeasuredbyusingaveryaccurate
balancetodeterminethemassdifferenceofasampleofthecomplexinthepresenceandabsenceofamagneticfield.
Thisallowsustocalculatethemagneticmoment()ofthecomplexand,hence,todeterminethenumberofunpaired
electronsitcontains.ThemagneticmomentofacomplexismeasuredinBohrmagnetons(B)andisdefinedas:

wherenisthenumberofunpairedelectronsinthecomplex.Therefore,acomplexcontainingoneunpairedelectron
shouldhave whilethevalueofforacomplexcontainingthreeunpairedelectronswouldbe
.Notethatthisequationappliesexactlyonlytocomplexesinwhichtheorbitalmotionofthe
unpairedelectronsbetweendegeneratedorbitalsisnegligible.Wewillassumethatthisisthecaseintheexamples
presented.

Havingintroducedtheconceptofhighspinandlowspinelectronconfigurations,wecannowexplaintheunusual
magneticbehaviourofthe[Fe(OH2)6]2+and[Fe(CN)6]4ionsdiscussedonp.566.Bothcomplexescontaind6Fe(II)
metalions,but[Fe(OH2)6]2+isparamagnetic(4.9B)while[Fe(CN)6]4isdiamagnetic(0B).Weknowfrom
thespectrochemicalseriesthatH2OinducesamuchsmallervalueofothandoesCN,meaningthat[Fe(OH2)6]2+is
highspinwhile[Fe(CN)6]4islowspin,asshowninfigure13.42.
 FIGURE13.42Thedistributionofdelectronsin[Fe(OH2 )6 ]2+and[Fe(CN)6 ]4.Themagnitudeofo forthecyanidecomplexis
muchlargerthanthatforthecomplexcontainingwater.Thisproducesamaximumpairingofelectronsinthe
t2g orbitalsin[Fe(CN)6 ]4,andacorrespondinglowspinconfigurationforthiscomplex.

Therefore,[Fe(OH2)6]2+containsfourunpairedelectronsandisparamagnetic,while[Fe(CN)6]4hasnounpaired
electronsandisdiamagnetic.

Magneticmeasurementsallowustodistinguishbetweenhighspinandlowspinpossibilitiesintransitionmetal
complexes.Forexample,themagneticmomentsofthed4Cr(II)complexes[Cr(OH2)6]2+and[Cr(CN)6]4are4.9B
and2.8B,respectively.Thevalueof4.9Bfor[Cr(OH2)6]2+isconsistentwiththepresenceoffourunpaired
electronsand,therefore,ahighspin(t2g)3(eg)1configuration.Thevalueof2.8Bfor[Cr(CN)6]4arisesfromtwo
unpairedelectrons,whichsuggestsalowspin(t2g)4(eg)0configuration.

WORKEDEXAMPLE13.9

ThemagneticBehaviourofOctahedralTransitionMetalComplexes
Predictwhetherthefollowingoctahedraltransitionmetalcomplexionsareparamagneticordiamagnetic:
[Co(CN)6]3,[TiCl6]3,[V(OH2)6]3+,[CoF6]3.Iftheyareparamagnetic,estimatetheirmagneticmoments.

Analysis

Wecancalculatethedelectronconfigurationsofthecomplexesbyfirstdeterminingtheoxidationstates
andthennumbersofdelectronsforeachmetalion.Wherehighspinandlowspinpossibilitiesoccur,we
usethepositionoftheligandinthespectrochemicalseriestodecidebetweenthetwoconfigurations.

Solution

TheoxidationstatesareCo(III),Ti(III),V(III)andCo(III),whichcorrespondtod6,d1,d2andd6electron
configurations,respectively.Highspinandlowspinpossibilitiesexistforboth[Co(CN)6]3and[CoF6]3.
Weknowfromthespectrochemicalseriesonp.572thatCNisastrongfieldligand,whileFisaweak
fieldligand.Wethereforepredictthat[Co(CN)6]3isd6lowspinanddiamagnetic,while[CoF6]3isd6
highspin,withfourunpairedelectrons,andparamagnetic.[TiCl6]3mustbeparamagnetic,asitcontainsan
oddnumberofdelectrons,while[V(OH2)6]3+isalsoparamagnetic,asthetwodelectronsoccupytwoof
thet2gorbitalswithparallelspins.Therefore,theelectronconfigurationsandmagneticmomentsareas
shownontheright.
 Isouranswerreasonable?

Providedwehavecountedthedelectronscorrectlyandfilledtheorbitalsintheappropriatefashion,our
answersshouldbecorrect.

PRACTICEEXERCISE13.9
Determinehowmanyunpairedelectronsare
containedinthefollowingoctahedralcomplexions:
[NiCl6]2,[CuCl6]4,[ZnCl6]4.Estimatethe
magneticmomentsofthesecomplexes.

Itisimportanttorealisethatthesimpleparamagneticcomplexeswehavediscussed,whileattractedintoamagnetic
field,donotthemselvesactaspermanentmagnets.Thepresenceofunpairedelectronsisnotsufficientinitselffora
substancetoactasapermanentmagnetforthis,asubstancemusthaveanonzeromagneticfieldthatpersistsover
time.Intheabsenceofanexternalmagneticfield,theunpairedelectronspinsinaparamagneticmaterialarealigned
randomlytherefore,thetinymagneticfieldsresultingfromeachelectronspincanceleachotherandthenetmagnetic
momentiszero.Applicationofanexternalmagneticfieldresultsintheelectronspinsaligning,andthisorderingof
thespinsresultsinanetmagneticmomentwithinthematerial.However,whentheexternalmagneticfieldisremoved,
theelectronspinsagainalignrandomlyandtheindividualmagneticfieldsagaincanceleachother.Inordertoactasa
permanentmagnet,theseunpairedspinsmustbehavecooperativelytogiveanonzeromagneticmomentinthe
absenceofanexternalmagneticfield.Ofallthemetalsintheperiodictable,onlyfive,iron,cobalt,nickel,dysprosium
andgadolinium,havethisabilityandcanthereforeactaspermanentmagnets.Theydisplayapropertycalled
ferromagnetism,whichmeansthatalloftheelectronspinsareorientedinthesamedirectionintheabsenceofa
magneticfield.

Figure13.43showsthedifferencebetweenparamagneticandferromagneticmaterials.Ferromagneticmaterials
displaythealignmentofelectronspinswithinsmallareascalleddomainsintheabsenceofamagneticfield.Again,
becausetheorderingofthedomainsisrandomised,theindividualmagneticfieldsduetoeachdomaincanceloutand
thereisnonetmagneticmoment.Whenanexternalmagneticfieldisapplied,eachdomainalignswithalltheothers,
andthisalignmentremainswhenthemagneticfieldisswitchedoff,resultinginthematerialhavinganonzero
magneticmomentandbehavingasapermanentmagnet.Manyofyouwillhaveobservedthisbehaviourwhenyou
havemagnetisedaneedlestrokinganeedlewithapermanentmagnetcausestheindividualdomainswithintheneedle
(madeofsteel,aferromagneticmaterial)toalign,andthisalignmentremainswhenthepermanentmagnetisremoved.

FIGURE13.43 Thedifferingbehavioursofparamagneticandferromagneticmaterials.Eacharrowrepresentsasingle
electronspin.Inaparamagneticmaterial:
(a)intheabsenceofanexternalmagneticfield,thedirectionsoftheelectronspinsarerandomised
(b)applyinganexternalmagneticfieldcausestheelectronspinstoalign
(c)whentheexternalmagneticfieldisswitchedoff,theelectronspinsagainrandomise.Ina
ferromagneticmaterial
(d)intheabsenceofanexternalmagneticfield,thereisshortrangeorderingoftheelectronspinsin
individualdomainswithinthematerial
(e)applyinganexternalmagneticfieldcausesalltheelectronspinswithinallthedomainstoalign
(f) whentheexternalmagneticfieldisswitchedoff,theelectronspinsremainalignedtogiveapermanent
magnet.

Whilemagneticmaterialsarewidelyusedindatastorage(themagneticstripsonthebackofyourATMandcredit
cards,forinstance),nanoscalemagneticmaterialsofferpotentiallyenormouspossibilitiesasreplacementsforcurrent
siliconbasedtechnologyincomputers(seep.577).Centraltothisisthedevelopmentofbothmagneticnanoparticles,
whicharewelldefinedmagneticparticleswithadiameteroflessthan100nmandgenerallycomprisingcollectionsof
metalatomsormetaloxides,andsinglemoleculemagnets,inwhichindividualmoleculescontainingunpaired
electronswithalignedspinsactasmagnets.Bothareasarecurrentlythefocusofextensiveworldwideresearch.

ChemistryResearch

Lowspinversushighspinelectronicstatesspincrossover

ProfessorSallyBrooker,UniversityofOtago,Dunedin

Thedevelopmentofnanoscaledevicesthatcouldbeusedasmolecularcomputersiscurrentlyofintense
interest.Thesewillbefarsmallerandmorepowerfulthantoday'scomputersbasedonsiliconchipsthey
willlikelyresultfromabottomupapproachratherthanthecurrenttopdownapproachusedtoetch
smallerandsmallercircuitsontosiliconchipstoimproveperformance.Thelatterapproachcannotcontinue
indefinitelyasultimatelythelimitoftheperformanceofsiliconwillbereachedandshortcircuitswill
result.Chemistryresearchersareparticularlywellplacedtocontributestronglytothebottomupapproach
aswearegoodatmakingmolecules.Moleculeswitharangeoffunctionswillberequiredandwefocus
hereonthoseabletoactasswitches.

Asyouhavelearnedinthischapter,octahedralcoordinationcomplexeswithd4d7electron
configurationscanpotentiallyexistineitherthelowspin(LS)state(o>P)orthehighspin(HS)state(o
<P).However,forsomecomplexes,thevaluesofoandParesimilar,leadingtotheobservedspinstate
beingdependentontheconditions.Suchcomplexesarecalledspincrossovercomplexes.Mostcommonly,
thespinstateofsuchcomplexesisdeterminedbyvaryingthetemperatureandmonitoringthenumberof
unpairedelectrons.Atlowtemperature,themetalioninamonometallicspincrossovercomplexisintheLS
statebutswitchestotheHSstateathightemperature.Thisswitchingbehaviour(usuallyreversible)between
LSandHSstatescanbeconsideredakintoanon/offswitchorabinarycode,0/1.

Mostspincrossovercomplexescontainasinglemetalion,butattheUniversityofOtagoourfocusison
complexescontainingtwo,threeorfourmetalions.Forexample,wehaveobservedunprecedentedspin
crossoverbehaviourinadicobaltcomplex(figure13.44),andmorerecentlywehavedeterminedthecrystal
structureofanunusualmixedspinstatediironcomplex(figure13.45).

FIGURE13.44Thecrystalstructureof[Co2 L(NCS)2 (SCN)2 ],whereLisaneutralmacrocyclicligand.The

cobalt(II)ionsaregreen,nitrogenatomsareblue,carbonatomsareblackandsulfuratomsare
yellow.
 FIGURE13.45Thecrystalstructureof[Fe2 (PMAT)2 ](BF4 )4 DMF,wherePMATisaneutralpolydentateligand.
Theiron(II)ionsarepink,nitrogenatomsareblueandcarbonatomsareblack.

Foracomplexcontainingtwometalions,therearethreepossiblespinstates([LSLS],[LSHS]and[HS
HS])and,therefore,3stateswitchingispossible.However,atambientpressures[Fe2(PMAT)2](BF4)4exists
inonlytwodifferentstatesatroomtemperatureitispaleyellow[HSHS](figure13.46a),whereasatlow
temperatureitispurple[LSHS](figure13.46b).Interestingly,evenwhenthiscomplexisplacedunder
pressureatverylowtemperatures,wecannotforceittoadoptthethirdpossiblestate,[LSLS].

FIGURE13.46 Crystalsof
(a)HSHS[Fe2 (PMAT)2 ](BF4 )4 (yellow)and
(b)LSHS[Fe2 (PMAT)2 ](BF4 )4 (purple).

Clearly,foracomplexcontainingfourmetalions,5stateswitching,fromthefullyLSform[LSLSLSLS]
throughallofthemixedspinstatestothefullyHSform[HSHSHSHS],ispossibleinprinciple,althoughit
hasyettoberealised.

Wegrowcrystalsofthenewspincrossovercomplexeswemakeinordertoworkoutthethreedimensional
arrangementsofatomswithinthemoleculesthatthesecrystalscontain.Knowingthestructureofthesenew
moleculesisvitaltounderstanding,andsubsequentlyfinetuning,thepropertiesexhibitedbyourmolecules.
Studiesinthisareaaimtodevelopbetterunderstandingandcontrolofspincrossover.Improved
understandingoftheeffectoftheexactnatureoftheligandsonthecrystalfieldsplittingenergy(o)
experiencedbythemetalion(s),andhenceonthespincrossoverbehaviourofsuchsystems,may
ultimatelyleadtoapplicationsinmolecularcomputers.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.5TransitionMetalIonsinBiologicalSystems
Almost90%oftheatomsthatmakeupthehumanbodyareeitherhydrogenoroxygen.Mostoftheseareinwater,
whichconstitutesaround70%ofourbodies.Theorganicmoleculesthatmakeupthebody,aswellasthemolecules
involvedinbiosynthesisandenergyproduction,consistalmostentirelyofC,H,NandO.Thesefourelementsaccount
for99%ofalltheatomspresentinahuman.AnothersevenelementsNa,K,Ca,Mg,P,SandClarealso
essentialforallknownlifeforms.Thesesevenaddanother0.9%tothetotalatomcountofahumanbeing.The
remaining0.1%,thesocalledtraceelements,arerequiredbymostorganisms.

Althoughtraceelementsarepresentinonlyminuteamounts,theyareessentialforhealthyfunction.Ofthesetrace
elements,ninearetransitionmetals,namelytheelementsV,Cr,Mn,Fe,Co,Ni,CuandZnfromthefirstrowofthe
transitionmetalsandMo(molybdenum)fromthesecondrow.Manyofthesearenaturalconstituentsofproteins,
biologicalmacromoleculesmadeoflongchainsofaminoacidsthataredescribedinchapter24.Thesemetalloproteins
playthreeessentialrolesinbiochemistry.Someactastransportandstorageagents,movingsmallmoleculesfrom
placetoplacewithinanorganism.Othersareenzymes,catalystsforadiversegroupofbiochemicalreactions.Both
transportandcatalysisdependontheabilityoftransitionmetalstobindandreleaseligands.Thethirdroleof
metalloproteinsistoserveasredoxreagents,addingorremovingelectronsinmanydifferentreactions.Transition
metalsareidealforthispurposebecauseoftheirabilitytocyclebetweentwoormoreoxidationstates.

Transportandstoragemetalloproteins
Organismsextractenergyfromfoodbyusingmolecularoxygentooxidisefatsandcarbohydrates.Formostanimals,
themovementandstorageofO2isaccomplishedbytheironcontainingproteinshaemoglobinandmyoglobin.The
ironatominhaemoglobinbindsO2andtransportsthisvitalmoleculefromthelungstovariouspartsofthebodywhere
oxidationtakesplace.HaemoglobinmakesO2about70timesmoresolubleinbloodthaninwater.Whereas
haemoglobintransportsO2,myoglobinstoresO2intissues,suchasmuscle,thatrequirelargeamountsofoxygen.
Haemoglobinandmyoglobinhavecloselyrelatedstructuresandcontainone(myoglobin)orfour(haemoglobin)haem
groups(figure13.47).Theseareessentiallyironporphyrincomplexes,asshowninfigure13.48onthenextpage.

FIGURE13.47Thehaemgroup,asfoundinhaemoglobinandmyoglobin.
 FIGURE13.48Aribbondepictionofthestructureofmyoglobin,determinedbyXraycrystallography,showingthehaemunit
embeddedinapocketcreatedbythefoldingoftheproteinchain.(FeisshownaspinkandOasred.)

Inmyoglobin,thehaemgroupisboundtoapolypeptidechainof153aminoacidsarrangedinhelicalarrays,andthe
ribbonstructureofmyoglobinisshowninfigure13.48.Thepolypeptidechainfoldstocreateapocketintheprotein
forahaemgroup.

Haemoglobinismadeupoffourpolypeptidechains,eachofwhichissimilarinshapeandstructuretoamyoglobin
molecule.EachhaemunitinbothmyoglobinandhaemoglobincontainsoneFe2+ionboundtofournitrogendonor
atomsinasquareplanararrangement.Thisleavesthemetalwithtwoaxialcoordinationsitestobindotherligands.
OneofthesesitesisoccupiedbyanNdonorligandfromaproteinsidechainthatholdsthehaeminthepocketofthe
protein,whilethesixthcoordinationsiteiswherereversiblebindingofO2takesplace.Ordinarily,interactionofan
Fe(II)ionwithmolecularO2wouldresultinirreversibleoxidationtoFe(III) atpH=7,

but,remarkably,asaresultoftheproteinsurroundingthehaem,bothhaemoglobinand
myoglobinareabletobindO2withoutbeingirreversiblyoxidised(oxidationofhaemoglobingivesacompoundcalled
methaemoglobin,whichcannotbindO2).

Inthelungs,haemoglobinloadsfouroxygenmoleculesandthenmovesthroughthebloodstream.Intissues,the
concentrationofO2isverylow,butthereisplentyofCO2,theendproductofmetabolism.TheconcentrationofCO2
hasanimportanteffectonhaemoglobinoxygenbinding.Likeoxygen,CO2canbindtohaemoglobin.However,CO2
bindstospecificaminoacidsidechainsoftheprotein,ratherthantothehaemgroup.BindingCO2totheprotein
causestheshapeofthehaemoglobinmoleculetochangeinwaysthatreducetheequilibriumconstantforO2binding.
ThereducedbindingconstantallowshaemoglobintoreleaseitsO2moleculesinoxygendeficient,CO2richtissue.
Thebloodstreamcarriesthisdeoxygenatedhaemoglobinbacktothelungs,whereitreleasesCO2andbindsfourmore
moleculesofO2.ThisCO2effectdoesnotoperateinmyoglobin,whichbindsandstorestheoxygenreleasedby
haemoglobin.

CarbonmonoxideseriouslyimpedestransportofO2.ThedeadlyeffectofinhaledCOresultsfromitsreactionwith
haemoglobin.ACOmoleculeisalmostthesamesizeandshapeasO2,soitfitsintothebindingpocketofthe
haemoglobinmolecule.Inaddition,thecarbonatomofCOformsastrongerbondwithFe(II)thandoesO2.Under
typicalconditionsinthelungs,haemoglobinbindsCOover200timesmorestronglythanitbindsO2.Haemoglobin
complexedtoCOcannottransportoxygenso,whenasignificantfractionofhaemoglobincontainsCO,oxygen
starvationoccursatthecellularlevel,leadingtolossofconsciousnessanddeath.

Anadulthumancontainsonlyabout4gofiron,mostofitintheformofhaemcontainingproteins.Yetthedaily
requirementofironinthedietisonlyabout718mg,indicatingthatthebodyrecyclesiron.Therecyclingofiron
requiresatransportsystemandastoragemechanism.Ironistransportedbyaproteincalledtransferrin,whichcollects
ironinthespleenandliver,wherehaemoglobinisdegraded,andcarriesittothebonemarrowwherefreshredblood
cellsaresynthesised.Theproteinferritinstoresironinthebody.Aferritinmoleculeconsistsofaproteincoatandan
ironcontainingcore.Theoutercoatismadeupof24polypeptidechains,eachcomprisingabout175aminoacids,
whichpacktogethertoformasphere.Thesphereishollow,andchannelsthroughtheproteincoatallowmovementof
ironinandoutofthemolecule.Thecoreoftheproteincontainshydratediron(III)oxide,Fe2O3H2O.Theprotein
retainsitsshapewhetherornotironisstoredontheinside.Whenfilledtocapacity,oneferritinmoleculeholdsas
manyas4500ironatoms,butthecoreisonlypartiallyfilledundernormalconditions.Inthisway,theproteincan
provideironasneededforhaemoglobinsynthesisortostoreironifanexcessisabsorbedbythebody.

Metalloenzymes

Aswehaveseeninthissection,molecularoxygenisessentialtolife.However,thesuperoxideion,O2,whichisthe
productofoneelectronreductionofO2,candamagecellsandisthoughttoplayaroleintheageingprocess.The
enzymesuperoxidedismutase(SOD)isabundantinvirtuallyeverytypeofaerobicorganismitsroleincellsisto
destroysuperoxideions.TheactivesiteoftheSODenzyme,theregionoftheenzymewherethecatalyticreaction
occurs,containsonecopperionandonezincion,eachofwhichdisplaysatetrahedralgeometry.Asfigure13.53
shows,thetwometalsareheldclosetogetherbyahistidineligand(histidineisanaminoacid,chapter24)thatformsa
bridgebetweentheCu(II)andZn(II)ions.

ChemistryResearch

ChelatingligandstotreatFeoverload

ProfessorPaulVBernhardt,UniversityofQueensland

ProfessorPaulBernhardtattheUniversityofQueenslandandProfessorDesRichardsonattheUniversityof
Sydneycarryoutresearchintonewligandsthatcancoordinateironinthequestfornewdrugstotreatiron
overload.

Ironisanessentialelementtohumans(andallotherlifeforms)asitisinvolvedinvitalbiologicalprocesses
suchasrespiration,DNAsynthesisandenergyproduction.Inexcess,however,Feispotentiallyhighlytoxic.
ThisconditionisreferredtoasFeoverload.ThetoxicityofexcessFeislinkedtooxidativestresscausedby
socalledFentonchemistrywhereFe(II)catalysesthebreakdownofhydrogenperoxidetotoxichydroxyl
radicals:

causingDNAdamageandaffectingnormalcellfunction.

Feoverloadcanariseinseveralways,butifuntreateditmayleadtoirreversibledamagetotheheartandliver.
CoordinationchemistryoffersasolutiontotheproblemofFeoverloadbytheadministrationofligands(Fe
chelators)asdrugsthatformstablecomplexeswithFeandenableitsremoval(figure13.49)humanshaveno
wayofactivelyexcretingexcessFefromtheirbodies.Thefirstandmostsuccessfuldrughasbeen
desferrioxamine(DFO),ahexadentateligandthatformsanexceptionallystableFe(III)complex(figure
13.51).Thiscompoundhasbeenusedformorethan40yearsasadrugtotreatFeoverload.

FIGURE13.49Thestructureofthemetalcontainingsiteofsuperoxidedismutase,asdeterminedbyXray
crystallography.TheZn2+andCu2+cationslieincloseproximity,withahistidinesidechain(inthe
box)actingasabridgebetweenthemetals.
 FIGURE13.50FeoverloadcanbesuccessfullytreatedbytheadministrationofFechelatorsthatformstable
complexeswithFe.

ThemaindrawbackofDFOtherapyisthatthecompoundcannotbetakenorallybutinsteadisadministered
byslowinjectionsoverperiodsofhoursseveraldaysperweekinevitablymanypatientsfailtocomplywith
thisstrictroutine.ThishasdrivenresearchaimedatfindingalternativeFechelatorsthatcanbetakenorally
butatthesametimeareactiveinchelatingFeandarenontoxic.Arecentbreakthroughistheappearanceof
thedrugdeferasirox(figure13.51),inthiscaseatridentateFechelator,whichistakenorallyoncedailyto
controlsevereFeoverload.

FIGURE13.51Chemicalstructureofdesferrioxamine(DFO,deferoxamine)anditsFe(III)complex.

TheBernhardtandRichardsonresearchgroupsarealsodevelopingalternative,potentiallyorallyactive,Fe
chelatingdrugs.Thetwoligandsinfigure13.52(PCBBHandBBPH)appearsimilarbuttheirFecoordination
chemistryisverydifferent.PCBBHbindsonlyFe(II)(andnotFe(III))whileBBPHbindsonlyFe(III)(andnot
Fe(II)).BothligandsareveryeffectiveinremovingexcessFefromlivingcells,andcompoundsfromthis
familymayeventuallyproveeffectivealternativestoexistingpharmaceuticals.
FIGURE13.52ChemicalstructureofdeferasiroxandthecrystalstructureofanFe(III)complexofacloselyrelated
ligand.
 FIGURE13.53MolecularstructuresofnewbiologicallyactiveFechelatorsandtheirFecomplexes.

ItisthoughtthatO2initiallybindstotheCucentre,whicheventuallyleadstodisproportionation(alsocalled
dismutation)ofO2andformationofO2andH2O2.TheroleoftheZn(II)ionisthoughttobepurely
structural.Interestinsuperoxidedismutasehasincreasedinrecentyearswiththediscoverythatamutationin
thegenecodingforSODislinkedtocertaintypesoftheneurodegenerativediseaseamyotrophiclateral
sclerosis(ALS),andthisiscurrentlyanareaofintenseresearch.

Electrontransferproteins
Themanyredoxreactionsthattakeplacewithinananimaloraplantcellmakeuseofmetalloproteinswithawide
rangeofelectrontransferpotentials.Someoftheseproteinsplaykeyrolesinrespiration,photosynthesisandnitrogen
fixation,whileotherssimplyshuttleelectronstoorfromenzymesthatrequireelectrontransferaspartoftheircatalytic
activity.Inmanyothercases,acomplexenzymemayincorporateitsownelectrontransfercentres.Therearethree
generalcategoriesoftransitionmetalredoxcentres:cytochromes,bluecopperproteinsandironsulfurproteins.
Cytochromesareironcontainingproteinsthatincorporatehaemgroupsandthatfacilitateelectrontransferbycycling
theironbetweenthe(II)and(III)states.Atypicalbluecopperredoxproteincontainsasinglecopperatomina
distortedtetrahedralenvironment.ThecoppercentrecancyclebetweentheCu(I)andCu(II)oxidationstates,thereby
aidingelectrontransfer.Ironsulfurproteinsdisplayavarietyofnuclearities(one,twoorfourironcentres)and
geometriesthetwoavailableoxidationstatesofiron,Fe(II)andFe(III),allowelectrontransfertotakeplace.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
13.6IsolationandPurificationofTransitionMetals
Theproductionandpurificationofmetalsfromtheiroresiscalledmetallurgy.Thistechnologyhasan
ancienthistoryandmayrepresentoneoftheearliestusefulapplicationsofchemistry.Metallurgical
advanceshavehadprofoundinfluencesonthecourseofhumancivilisation,somuchsothathistorians
speakoftheBronzeAge(about3000to5000yearsago)andtheIronAge(startingabout3000yearsago).
MetallurgyhasalsohadanenormousimpactonthehistoriesofbothNewZealandandAustralia,withgold
rushesinthenineteenthcenturycontributingsignificantlytotheeconomyandsocialfabricofboth
countries.Australiaisoneofthemostimportantmineralproducersintheworld,andtheminingindustryisa
majorsourceofoverseasearnings.Inthissection,wediscusssomeofthetechniquesofmetallurgyas
appliedtotransitionmetals,andwealsolookatsomeoftheareasinwhichtransitionmetalsareused.

Nearlyalltransitionmetalsarereadilyoxidised,somostoresarecompoundsinwhichthetransitionmetal
hasapositiveoxidationstate.Examplesincludeoxides(TiO2,rutileFe2O3,haematiteCu 2O,cuprite),
sulfides(ZnS,sphaleriteMoS2,molybdenite)andcarbonates(FeCO3,siderite).Othermineralscontain
oxoanions(MnWO4,wolframite)andthosewithevenmorecomplexstructuressuchascarnotite,
K2(UO2)2(VO4)23H2O.Figure13.54showsinschematicfashionsomeofthealternativepathsleadingfrom
orestopuremetals,allofwhichinvolvereductionastheessentialchemicalprocess.

FIGURE13.54Metallurgyincludesseparation,conversion,reductionandrefiningsteps.Thestartingmaterialis
animpureore,andtheendproductispuremetal.

Thefourmainstepsintheconversionofanoretoapuremetalareseparation,conversion,reductionand
refining.Separationinvolvestheremovalofaparticularcompoundofsomedesiredmetalfromother
contaminants.Theconversionstepentailschemicaltreatmentoftheseparatedmaterialtoconvertitintoa
formthatcanbeeasilyreduced.Chemicalorelectrolyticreductionthengivestheimpuremetal,whichis
finallyrefinedtothepuremetal.

Separation
Oreobtainedfromaminingoperationcontainsadesiredmineralcontaminatedwithothercomponents,
whichmayincludesand,clayandorganicmatter.Thiseconomicallyvaluelessportionoftheore,whichis
calledgangue(pronouncedgang),mustberemovedbeforethemetalcanbeextractedandrefined.Ores
canbeseparatedintocomponentsbyphysicalorchemicalmethods.

Flotation,acommonphysicalseparationprocess,wasdiscoveredanddevelopedinAustralia,andwasfirst
usedonalargescaleatBrokenHillintheearlyyearsofthetwentiethcentury.Duringflotation,theoreis
crushedandmixedwithwatertoformathickslurry.Asshowninfigure13.55,theslurryistransferredtoa
flotationvesselandmixedwithoilandasurfactant(inthiscase,adetergent).

FIGURE13.55Intheflotationprocess,detergentcoatedmineralparticlesfloattothesurfaceofthemixture,where
theybecometrappedinthefroth.Theganguesettlestothebottom.

Thepolarheadgroupsofthedetergentcoatthesurfaceofthemineralparticles,butthenonpolartailspoint
outwards,makingthedetergentcoatedmineralparticleshydrophobic.Airisblownvigorouslythroughthe
mixture,carryingtheoilandthecoatedmineraltothesurface,wheretheybecometrappedinthefroth.
Becausetheganguehasamuchloweraffinityforthedetergent,itabsorbswaterandsinkstothebottomof
theflotationvessel.Thefrothisremovedatthetop,andthegangueisremovedatthebottom.

Leachingisachemicalseparationtechniquethatusessolubilitypropertiestoseparatethecomponentsofan
ore.Forexample,moderngoldproductiondependsontheextractionoftinyparticlesofgoldfromgold
bearingrockdeposits.Aftertherockiscrushed,itistreatedwithanaeratedaqueousbasicsolutionof
sodiumcyanide,resultingintheformationofthesolublecoordinationcomplex[Au(CN)2],aswesawin
workedexample13.7:
Conversion
Sulfideoresmaybetreatedchemicallytoconvertthemtooxidesbeforeextractioncanoccur.Theprocessof
oxidisinganorebyheatingtoahightemperatureinthepresenceofairisknownasroasting.Whensulfide
oreisroasted,sulfideanionsareoxidisedandmolecularoxygenisreduced.Theconversionofsphalerite,
ZnS,(figure13.56)isatypicalexample:

FIGURE13.56Sphalerite.

Unfortunately,roastingproducescopiousamountsofhighlypollutingSO2gasthat,inthepast,seriously
damagedtheenvironmentaroundsulfideoresmelters.Today,zincandothermetalscanbeextractedfrom
sulfidesbyreactionwithaqueousacidtogeneratefreesulfurorsulfateionsratherthanSO2.Herearetwo
examples:

TakingintoaccountthecostofSO2pollutionoftheatmosphere,thesemoreelaborateaqueousseparation
proceduresareeconomicallycompetitivewithconversionbyroasting.Also,inthecaseofCuS,theliberated
SO42(aq)canbeconvertedtoH2SO4foruseinthemanufactureoffertiliser(seechapter14,p.622).

Reduction
Onceanoreisinsuitablypureform,itcanbereducedtothefreemetal.Thisisaccomplishedeither
chemicallyorelectrolytically.Electrolysisiscostlybecauseitrequireshugeamountsofelectricalenergy.
Forthisreason,chemicalreductionisusedunlessthemetalistooreactiveforchemicalreducingagentsto
beeffective.Mercuryisreducedeasilyenoughthatroastingthesulfideorefreesthemetal.Thesulfideionis
thereducingagent,andbothO2andthemetaliongainelectrons:

However,thisreductionproducesSO2,whichmustberemovedfromtheexhaustgases.Oneofthemost
commonchemicalreducingagentsformetallurgyiscoke,aformofcarbonmadebyheatingcoalathigh
temperatureintheabsenceofO2untilallofthevolatileimpuritieshavebeenremoved.MetalssuchasCo,
Ni,FeandZnthathavecationswithamoderatelynegativereductionpotentialcanbereducedbycoke.For
example,directreactionwithcokeinafurnacefreesnickelfromitsoxide:

Refining
Chemicalreductionofanoreusuallygivesmetalthatisnotpureenoughforitsintendeduse.Further
refiningofthemetalremovesundesirableimpurities.Severalimportantmetals,includingCu,Ni,ZnandCr,
arerefinedbyelectrolysis,eitherfromanaqueoussolutionofthemetalsaltorfromanodespreparedfrom
theimpuremetal.Togiveoneexample,Zn(II)ions,obtainedbydissolvingZnSorZnOinacidicsolution,
canbereducedwhilewaterisoxidised:

Table13.4onthenextpageprovidesasummaryofthechemicalspeciesandprocessesinvolvedinthe
metallurgyofmanytransitionmetals.Thefollowingsurveyofseveralmetalsprovidesfurtherexamplesof
thefourphasesofmetallurgy.
TABLE13.4 Metallurgyoftransitionmetals
Metal Ore Separationmethod Intermediate Reducingagent
Ti TiO2 chlorination TiCl4 Mg

Cr FeCr2O4 roasting Cr2O3 Al

Mn MnO2 Mn 2O3 Al
Fe Fe3O4 slagformation (a) C
Co CoAsS roasting CoO C
Ni Ni9S8 complexation Ni(CO)4 H2
Cu CuFeS2 leaching Cu 2+(b)

Zn ZnS roasting ZnO C

Mo MoS2 roasting MoO3 H2
W CaWO4 leaching WO42,WO3 H2

Au Au leaching [Au(CN2)] Zn

Hg HgS roasting (c) S2

(a)CaSiO3isformedasanimpurity.
(b)SO 2isformedasanimpurity.
4
(c)SO2isformedasanimpurity.

Ironandsteel
Ironhasbeenthedominantstructuralmaterialofmoderntimesand,despitethegrowthinimportanceof
aluminiumandplastics,itstillranksfirstintotaluse.Worldwideproductionofsteel(ironstrengthenedby
additives)isintheorderof900milliontonnesperyear.Australiaproducesabout18%oftheworld'siron
ore,thirdbehindChinaandBrazil,withmostcomingfromminesinWesternAustralia(figure13.57).
SignificantdepositsofironsandsarefoundonthewestcoastoftheNorthIslandofNewZealand.
 FIGURE13.57IronorestockpilesinthePilbararegionofWesternAustralia.

Themostimportantironoresaretwooxides,haematite,Fe2O3,andmagnetite,Fe3O4.Theproductionof
ironfromitsoresinvolvesseveralchemicalprocessesthattakeplaceinablastfurnace.Asshowninfigure
13.58,thisisanenormouschemicalreactorinwhichheating,reductionandpurificationoccurtogether.
 FIGURE13.58Adiagrammaticviewshowingthechemicalreactionsoccurringwithinthepicturedblastfurnace.

Therawmaterialsplacedinablastfurnaceincludetheore(usuallyhaematite)andcoke,whichservesasthe
reducingagent.Theoresalwayscontainvariousamountsofsilicondioxide,SiO2,whichisremoved
chemicallybyreactionwithlimestone,CaCO3.Tobegintheconversionprocess,pelletsofore,cokeand
limestonearemixedandfedintothetopofthefurnace,andablastofhotairisblowninatthebottom.As
thestartingmaterialsfallthroughthefurnace,theburningcokegeneratesintenseheat:

Theresultisatemperaturegradientrangingfromabout800Catthetopofthefurnaceto1900Catthe
bottom.

Thereductionofironoxidetakesplaceinseveralstagesindifferenttemperaturezoneswithinthefurnace.
ThereducingagentisCOproducedfromburningcoke.Thekeyreactionsare:

Onceliberatedfromitsoxides,theironmeltswhenthetemperaturereaches1500Candcollectsinapoolat
thebottomofthefurnace.

Whileheatingandreductionoccur,limestonedecomposesintocalciumoxideandCO2.TheCaOthenreacts
withSiO2impuritiesintheoretogeneratecalciumsilicate:

Atblastfurnacetemperatures,calciumsilicateisaliquid,calledslag.Beinglessdensethaniron,slagpools
onthesurfaceofthemoltenmetal.Bothproductsaredrainedperiodicallythroughopeningsinthebottomof
thefurnace.Althoughthischemistryiscomplex,thebasicprocessisreductionofironoxidebycarboninan
atmospheredepletedofoxygen.ArchaeologistshavefoundancientsmeltersinTanzaniathatexploitedthis
chemistrytoproduceironaround2000yearsago.EarlyAfricanpeoplesusedaholelinedwithtermite
residueasafuelbeforeaddingironore.Charredreedsandcharcoalprovidedthereducingsubstance.
Finally,achimneyofmudwasadded.Whenthisfurnacewasfired,apoolofironcollectedinthebottom.

Theironformedinablastfurnace,calledpigiron,containsimpuritiesthatmakethemetalbrittle.These
includephosphorusandsiliconfromsilicateandphosphatemineralsthatcontaminatetheoriginalore,as
wellascarbonandsulfurfromthecoke.Thisironisrefinedinaconverterfurnace.Here,astreamofO2gas
blowsthroughmoltenimpureiron.Oxygenreactswiththenonmetalimpurities,convertingthemtooxides.
Asintheblastfurnace,CaOisaddedtoconvertSiO2intoliquidcalciumsilicate,inwhichtheotheroxides
dissolve.Themoltenironisanalysedatintervalsuntilitsimpuritieshavebeenreducedtosatisfactorylevels.
Thentheliquidmetal,nowinaformcalledsteel,ispouredfromtheconverterandallowedtosolidify.Most
steelscontainvariousamountsofotherelementsthatareaddeddeliberatelytogivethemetalparticular
properties.Theseadditivesmaybeintroducedduringtheconverterprocessorwhenthemoltenmetalis
pouredoff.Oneofthemostimportantadditivesismanganese,whichaddsstrengthandhardnesstosteel.
Manganeseisaddedtonearlyeveryformofsteelinamountsrangingfromlessthan1%tomorethan10%
infact,morethan80%ofallthemanganeseproducedisincorporatedintosteel.

Titanium
Themetallurgyoftitaniumillustratesthepurificationofonemetalbyanother.Themajortitaniumoresare
rutile,TiO2,andilmenite,FeTiO3,andAustraliaprovidesasignificantproportionoftheworld'ssupplyof
these(about30%ofilmeniteand55%ofrutile).Theseoresareconvertedtotitanium(IV)chloridebya
redoxreactionwithchlorinegasandcoke.Forrutile:

Inthisreaction,carbonisoxidisedandchlorineisreduced.Whenthehotgascools,titaniumtetrachloride
(bp=140C)condensestoaliquidthatispurifiedbydistillation.Titaniummetalisobtainedbyreductionof
TiCl4withmoltenmagnesiummetalathightemperature.Thereactiongivessolidtitaniummetal(mp=1660
C)andliquidmagnesiumchloride(mp=714C):

Copper
Copperisfoundmainlyinthesulfideorechalcopyrite,FeCuS2(figure13.59),butchalcocite,Cu 2S,cuprite,
Cu 2O,andmalachite,Cu 2CO3(OH)2,arealsoimportant,whileelementalcoppernuggetscanalsobefound
inpartsoftheworld.Copperoresoftenhaveconcentrationsofcopperlessthan1%bymass,soachieving
economicviabilityrequiresminingoperationsonahugescale.Theextractionandpurificationofcopper
fromchalcopyriteiscomplicatedbytheneedtoremovetheiron.Thefirststepintheprocessisflotation,
whichconcentratestheoretoaround15%Cubymass.Inthenextstep,theconcentratedoreisroastedto
convertFeCuS2toCuSandFeO:

FIGURE13.59Chalcopyrite.

Copper(II)sulfideisunaffectedifthetemperatureiskeptbelow800C.HeatingthemixtureofCuSand
FeOto1400Cinthepresenceofsilica,SiO2,causesthematerialtomeltandseparateintotwolayers.The
toplayerismoltenFeSiO3formedfromthereactionofSiO2withFeO.Asthistakesplace,thecopperinthe
bottomlayerisreducedfromCuStoCu 2S.ThisbottomlayerconsistsofmoltenCu 2Scontaminatedwith
FeS.ReductionoftheCu 2Stakesplaceinaconverterfurnacefollowingthesameprinciplethatconverts
impureironintosteel.Silicaisadded,andoxygengasisblownthroughthemoltenmixture.Ironimpurities
areconvertedfirsttoFeOandthentoFeSiO3,whichisaliquidthatfloatstothesurface.Atthesametime,
Cu 2SisconvertedtoCu 2O,whichreactswithmoreCu 2StogivecoppermetalandSO2:

Coppermetalobtainedfromtheconverterfurnacemustberefinedtobetterthan99.95%puritybeforeitcan
beusedtomakeelectricalwiring.Thisisaccomplishedbyelectrolysis,asillustratedinfigure13.60.

FIGURE13.60Diagramofanelectrolyticcellforthepurificationofcopper.
Theimpurecopperisformedintoslabsthatserveasanodesinelectrolyticcells.Thecathodesare
constructedfromthinsheetsofverypurecopper.TheseelectrodesareimmersedinasolutionofCuSO4
dissolvedindilutesulfuricacid.Applicationofacontrolledvoltagecausesoxidationinwhichcopper,along
withironandnickelimpurities,isoxidisedtoitscations.Lessreactivemetalcontaminants,includingsilver,
goldandplatinum,arenotoxidised.Astheelectrolysisproceedsandtheanodedissolves,theseandother
insolubleimpuritiesfalltothebottomofthecell.Themetalcationsreleasedfromtheanodemigratethrough
thesolutiontothecathode.BecauseCu(II)iseasiertoreducethanFe(II)andNi(II),carefulcontrolofthe
appliedvoltagemakesitpossibletoreduceCu(II)toCumetal,leavingFe(II)andNi(II)dissolvedin
solution.

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13.7ApplicationsofTransitionMetals
Acompletediscussionofallthetransitionmetalsisbeyondthescopeofafirstyearchemistrycourse.
Instead,weprovideabriefsurveyofseveralmetalsthathighlightsthediversityandutilityofthisgroup
ofelements.

Titanium
Titanium,theninthmostabundantelementintheEarth'scrust,ischaracterisedbyitshighstrength,its
lowdensity(57%thatofsteel)anditsstabilityatveryhightemperatures.Whenalloyedwithsmall
amountsofaluminiumortin,titaniumhasthehigheststrengthtoweightratioofalltheengineering
metals.Itsmajoruseisintheconstructionofaircraftframesandjetengines.Becausetitaniumisalso
highlyresistanttocorrosion,itisusedintheconstructionofpipes,pumpsandvesselsforthechemical
industryandforsurgicalimplants(figure13.61).Becauseitisdifficulttopurifyandfabricate,titanium
isanexpensivemetal.Forexample,althoughtitaniumbicyclesarehighlyprizedbyavidcyclists,they
arequiteexpensive,frequentlycostingwellover$1000forjusttheframe.Themostimportant
compoundoftitaniumistitanium(IV)oxide,TiO2.Morethan2milliontonnesofTiO2areproduced
worldwideeveryyear,themajoritybythecontrolledcombustionofTiCl4:

FIGURE13.61Titaniumplatesandpinsareusedtoholdthisbrokenlegtogether.

TheCl2producedinthecombustionreactionisrecycledtoproducemoreTiCl4fromrutileore.
Titaniumdioxideisbrilliantwhite,owingtothed0electronconfigurationoftheTi(IV)ions,highly
opaque,chemicallyinertandnontoxic.Consequently,itfindswideuseasapigmentinpaintsandother
coatings,paper,sunscreens,cosmeticsandtoothpaste.TiO2isalsofindingincreasinguseinsolarcells
andselfcleaningwindowsbecauseofitselectrochemicalproperties.
Chromium
Chromiummakesupjust0.012%oftheEarth'scrust,yetitisanimportantindustrialmetal.Themain
useofchromiumisinmetalalloys.Stainlesssteel,forexample,containsasmuchas20%chromium.
Nichrome,a60:40alloyofnickelandchromium,isusedtomakeheatradiatingwiresinelectrical
devicessuchastoastersandhairdryers.Anotherimportantapplicationofchromiummetalisasa
protectiveanddecorativecoatingforthesurfaceofmetalobjects.Theonlyimportantoreofchromium
ischromite,FeCr2O4.Reductionofchromitewithcokegivesferrochrome,anironchromium
compound:

Ferrochromeismixeddirectlywithmoltenirontoformchromiumcontainingstainlesssteel.

Chromiumcompoundsofhighpuritycanbeproducedfromchromiteorewithoutreductiontothefree
metal.Thefirststepistheroastingofchromiteoreinthepresenceofsodiumcarbonate:

Theproductisconvertedtosodiumdichromatebyreactionwithsulfuricacid:

Whentheresultingsolutionisconcentratedbyevaporation,Na2Cr2O72H2Oprecipitatesfromthe
solution.Thiscompoundisthemostimportantsourceofchromiumcompoundsforthechemical
industry.Itisthestartingmaterialformostotherchromiumcontainingcompoundsofcommercial
importance,including(NH4)2Cr2O7(ammoniumdichromate),Cr2O3(chromium(III)oxide)andCrO3
(chromium(VI)oxide).

Purechromiummetalismadebyatwostepreductionsequence.First,sodiumdichromateisreducedto
chromium(III)oxidebyheatinginthepresenceofcharcoal:

DissolvingCr2O3insulfuricacidgivesanaqueoussolutionofCr(III)cations:

ElectrolysisofthissolutionreducesthecationstopureCrmetal,whichformsahard,durablefilmonthe
surfaceoftheobjectservingasthecathode.ThenamechromiumisderivedfromtheGreekchroma
meaningcolour,becausecompoundsofthismetaldisplayawidevarietyofcolours(figure13.62)

FIGURE13.62Chromiumcompoundsdisplayastrikingrangeofcolours.ShownhereareNa2 CrO4 (yellow),

K2 Cr2 O7 (orange),CrCl3 (green)andCrO3 (darkpurple).
.

Chromiumcompoundshavebeenusedformanyyearsaspigmentsinpaintsandothercoatingsfor
example,Na2Cr2O7isbrightorange,Cr2O3isgreenandthesaltsofCrO42arebrightyellow.However,
inrecentyears,theuseofchromiumpigmentshasdiminishedbecausechromiumintheVIoxidation
stateiscarcinogenic.

Chromiumisalsoimportantinconvertinganimalhidesintoleather.Inthetanningprocess,hidesare
treatedwithbasicsolutionsofCr(III)salts,whichcausecrosslinkingofcollagenproteins.Thehides
toughenandbecomepliableandresistanttobiologicaldecay.

Copper,silverandgold
Thefirstthreepuremetalsknowntohumanitywereprobablycopper,silverandgold(figure13.63),
collectivelyknownasthecoinagemetalsbecausetheyfoundearlyuseascoins.Allthreecanbefound
innatureintheirpureelementalform,andallhavebeenhighlyvaluedthroughoutcivilisation.The
oldestknowngoldcoinswereusedinEgyptaround5400yearsago.Ataboutthesametime,copper
wasobtainedintheMiddleEastfromcharcoalreductionofitsores.Thefirstmetallurgyofsilverwas
developedinAsiaMinor(Turkey)about500yearslater.Allthreeofthesemetalsareexcellentelectrical
conductorsandarehighlyresistanttocorrosion.Theseproperties,coupledwithitsrelativelylowcost,
makecopperoneofthemostusefulmetalsinmodernsociety.Abouthalfofallcopperproducedisfor
electricalwiring,andthemetalisalsowidelyusedforplumbingpipes.

FIGURE13.63Gold,silverandbronzehavebeenwidelyusedinmedalsandcoinsbecausetheydonot
corrode.

Copperisusedtomakeseveralimportantalloys,themostimportantofwhicharebronzeandbrass.
Bothalloyscontaincoppermixedwithsmalleramountsoftinandzincinvariousproportions.The
amountoftininbronzeexceedsthatofzinc,whereastheoppositeistrueforbrass.Thediscoveryof
bronzearound5000yearsagolaunchedtheadvanceofcivilisationknowntodayastheBronzeAge.
Becausebronzeisharderandstrongerthanothermetalsknowninantiquity,itbecameamainstayofthe
civilisationsofIndiaandtheMediterranean,beingusedfortools,cookware,weapons,coinsandobjects
ofart.Today,theprincipaluseofbronzeisforbearings,fittingsandmachineparts.

Copperisresistanttooxidation,butovertimethemetalacquiresacoatingofgreencorrosioncalled
patina(figure13.64).ThegreencompoundisamixedsaltofCu(II),hydroxide,sulfateandcarbonate
ionsthatisformedbyairoxidationinthepresenceofcarbondioxideandsmallamountsofsulfur
dioxide:

FIGURE13.64Overtime,coppermetaldevelopsagreencoatingcalledpatina.

Althoughtraceamountsofcopperareessentialforallformsoflife,themetalistoxicinlargeamounts.
Thus,copper(II)salts,particularlyCuSO45H2O,areusedaspesticidesandwoodpreservatives.Wood
soakedinsolutionsofCu(II)orcoatedwithpaintscontainingCu(II)resistdegradationbybacteria,algae
andfungi.

Silverisusuallyfoundasaminorcomponentoforesofmoreabundantmetalssuchascopperandzinc.
Mostcommercialsilverisproducedasabyproductoftheproductionofthesecommonmetals.For
example,electrolyticrefiningofcoppergeneratesasolidanodicresiduethatisrichinsilverandother
preciousmetals.Thesilverfromthisresiduecanbeisolatedbyoxidisingthemetalintonitrate
containingsolutions,silvernitratebeingoneofthefewsolublesilversalts.Thepuremetalisthen
depositedelectrolytically.Silverisusedfortablewareintheformofsterlingsilver,analloycontaining
smallamountsofcoppertomakethemetalharder.Silverisalsousedinjewellery,mirrorsandbatteries,
and,priortotheadventofdigitalcameras,oneofitsmainuseswasinphotography.Silverdoesnot
formasimpleoxidebydirectoxidationinair,butthemetaldoesformablacktarnishwithoxygenand
traceamountsofhydrogensulfideintheatmosphere:

Theextractionofgoldbyleachinghasbeendescribedonp.584.Goldisusedextensivelyinthe
manufactureofjewellery.Interestingly,Au(I)compoundsareveryeffectiveinthetreatmentof
rheumatoidarthritis,andthereisrecentevidencethatcertaingoldcontainingcompoundshave
anticancerproperties.

Zincandmercury
ZincandmercuryarefoundintheEarth'scrustassulfideores,themostcommonofwhichare
sphalerite,ZnS,andcinnabar,HgStheisolationandpurificationofthemetalsfromtheseisdescribed
onpp.5834.Mostoftheworld'szincoutputisusedtopreventthecorrosionofsteel.Zinciseasierto
oxidisethaniron,asshownbythemorenegativereductionpotentialofZn(II):

Consequently,azinccoatingoxidisespreferentiallyandprotectssteelfromcorrosion.Zinccoatingsare
appliedinseveralways:byimmersioninmoltenzinc,bypaintcontainingpowderedzincandby
electroplating.Zincisalsocombinedwithcopperandtintomakebrassandbronze,andlargeamounts
ofzincareusedtomakeseveraltypesofbatteries.Zincoxideisthemostimportantzinccompound.Its
principalindustrialuseisasacatalysttoshortenthetimeofvulcanisationintheproductionofrubber.
Thecompoundisalsousedasawhitepigmentinpaints,cosmeticsandphotocopypaper.Ineveryday
life,ZnOisusedasacommonsunscreen(figure13.65).

FIGURE13.65ZnOisacommonsunscreen.

Theuseofmercuryforextractingsilverandgoldfromtheiroreshasbeenknownformanycenturies.
Goldandsilverformamalgamswithliquidmercury,whichcanthenberemovedbydistillationtoleave
thepurepreciousmetal.TheRomansminedthemineralcinnabar,HgS,fromdepositsinSpain2000
yearsago,andinthesixteenthcenturytheSpanishshippedmercuryobtainedfromthesameore
depositstotheAmericasfortheextractionofsilver.Mercuryisanimportantcomponentofstreetlamps
andfluorescentlights.Itisusedinthermometersandbarometersandingaspressureregulators,
electricalswitchesandelectrodes.

Theplatinummetals
SixofthetransitionmetalsRu,Os,Rh,Ir,PdandPtareknowncollectivelyastheplatinum
metals.Thegroupisnamedforthemostfamiliarandmostabundantofthesix.Theseelementsare
usuallyfoundmingledtogetherinoredeposits,andtheysharemanycommonfeatures.Althoughthey
arerare(totalannualproductionisonlyabout200tonnes),theplatinummetalsplayimportantrolesin
modernsociety.Theyarevaluablebyproductsoftheextractionofcommonmetalssuchascopperand
nickel,andtheanodicresiduethatresultsfromcopperrefiningisaparticularlyimportantsource.The
chemistryinvolvedintheirpurificationistoocomplicatedtodescribehere,excepttonotethatthefinal
reductionstepinvolvesreactionofmolecularhydrogenwithmetalhalidecomplexes.

Byfarthemostimportantuseoftheplatinummetalsisforcatalysis.Thelargestsingleuseisincatalytic
convertersintheexhaustsystemsofcars.Platinumistheprincipalcatalyst,butcatalyticconvertersalso
containrhodiumandpalladium.Theseelementscatalyseawidevarietyofreactionsinthechemicaland
petroleumindustries.Forexample,platinummetalisthecatalystforammoniaoxidationinthe
productionofnitricacid:

Palladiumisusedasacatalystforhydrogenationreactionsinthefoodindustry,andarhodiumcatalyst
isusedintheproductionofaceticacid:

Osmiumandiridiumholdthedistinctionofbeingthetwomostdenseelementsintheperiodictable,
withatennisballsizedsphereofeithermetalweighingaquiteastonishing3.4kg.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Metalsintheperiodictable
Themajorityofknownelementsaremetals,andtheyoccurindistinctsectionsoftheperiodictable.
Metalsingroups1,2and1316arecalledmaingroupmetals,whilethoseingroups312arecalled
transitionmetals.Compoundsoftheformerareusuallydiamagneticandcolourlesswhilethoseofthe
latterareoftenparamagneticandcoloured.Transitionmetalionsformcomplexesinwhichthemetalion
iscoordinatedtooneormoreligands.Complexescanbepositivelyornegativelychargedorneutral.

Transitionmetals
Transitionmetalsarecharacterisedbydvalenceorbitals,andcanexistinmorethanoneoxidationstate.
Thendorbitalsintransitionmetalionsarealwaysoflowerenergythanthe(n+1)sorbitalssoarefilled
withelectronsfirst.TransitionmetalionsareLewisacids.

Ligands
LigandsareLewisbasesthatcontainoneormoreelectronpairsandcanbenegativelycharged,neutral
or,veryrarely,positivelycharged.Theatomonwhichalonepairislocatediscalledadonoratom
commondonoratomsareF,Cl,Br,I,O,S,NandP,althoughorganiccompoundswithCdonoratoms
arealsoknown.Ligandsthatbindtoametalionusingonlyonedonoratomarecalledmonodentate,
thoseusingtwoarecalledbidentateandthoseusingtwoormorearecollectivelycalledpolydentate.
Whenpolydentateligandsbindtoasingletransitionmetalion,theyformoneormorechelaterings,and
complexescontainingthesearecalledchelates.

Transitionmetalcomplexes
Thestudyoftransitionmetalcomplexesiscalledcoordinationchemistry.Transitionmetalcomplexes
formasaresultofaLewisacidLewisbaseinteractionbetweenatransitionmetalionandaligand.The
bondsbetweenthemetalionandtheligandaresometimescalledcoordinate,donorcovalentordative
bonds,whilethecomplexesareoftencalledcoordinationcompounds.Complexesarewrittenenclosed
insquarebrackets,whilethecounterions(ifany)thatbalancethechargearewrittenoutsidethesquare
brackets.

Themostcommoncoordinationnumberofthecentralmetalionintransitionmetalcomplexesis6,
followedby4and5.Most6coordinatecomplexesdisplayanoctahedralgeometry.The4coordinate
complexesadopteitherasquareplanarortetrahedralgeometry,while5coordinatecomplexesare
usuallytrigonalbipyramidalorsquarepyramidal.

Therearenumerousisomericpossibilitiesintransitionmetalcomplexes.Structuralisomershavethe
samemolecularformula,butdifferentordersofattachmentsoftheconstituentatoms.Fourimportant
typesincoordinationchemistryareionisationisomers,coordinationisomers,linkageisomersand
hydrateisomers.Linkageisomersareformedwithambidentateligands,ligandswithtwoormore
differenttypesofdonoratom.Stereoisomershavethesameconnectionsbetweentheconstituentatoms,
butdifferentarrangementsoftheatomsinspace.Anexampleofsuchisomerismarecistransisomersa
cisisomerhastwogroupsonthesamesideofsomereferenceplaneandatransisomerhasthegroups
ondifferentsides.Meridional(mer)andfacial(fac)isomersarealsopossibleincomplexesoftheform
[ML3X3].TransitionmetalcomplexesarenamedaccordingtoIUPACrules.

Theformationoftransitionmetalcomplexescanbequantifiedbythecumulativeformationconstant
(n),whichistheequilibriumconstantfortheprocess:
where

nvaluesformosttransitionmetalcomplexesareextremelylarge,withthoseforcomplexescontaining
bidentateorpolydentateligandsbeingsignificantlygreaterthanthoseforthecorrespondingmono
dentateligands,amanifestationofthechelateeffect.Complexesthatreadilyexchangetheirligandsare
saidtobelabile,whilethosewithslowratesofligandexchangearecalledinert.

Crystalfieldtheorycanbeusedtodescribethebondingintransitionmetalcomplexes,anditpredicts
thatthedorbitals,whicharedegenerateinafreetransitionmetalion,aresplitbyinteractionswiththe
ligandelectrons.Inanoctahedralcomplex,theyaresplitintoalowerenergyt2gsetofthreeorbitalsand
ahigherenergyegsetoftwoorbitals.Theenergydifferencebetweenthesesetsoforbitalsiscalledthe
crystalfieldsplittingenergy(CFSE),whichisgiventhesymbolo.Thewayinwhichtheseorbitalsare
filledwithelectronsdependsonthecomparativemagnitudesofoandthepairingenergy,P.IfP>o,
ahighspinconfigurationresultsifP<o,alowspinconfigurationresults.Inoctahedralcomplexes,
thesepossibilitiesariseonlyford4,d5,d6andd7configurations.Differentdorbitalsplittingdiagrams
areobtainedforthe4coordinatesquareplanarandtetrahedralgeometries.

Transitionmetalcomplexesareoftencolouredbecauseofelectronictransitionsbetweenthe
nondegeneratedorbitalsthecolourofthecomplexiscomplementarytothatabsorbed.Wequantifythe
absorbedlightbymeasuringtheabsorbancewithaspectrophotometer,andwecancalculatethevalue
ofofromthewavelengthoftheabsorbancepeakintheUV/visiblespectrum.Thepositionofthispeak
isfoundtodependonthenatureoftheligands,andwecanarrangetheligandsinorderofthe
magnitudeoftheircrystalfieldsplittingenergiestogivethespectrochemicalseries.Ligandsgivinga
largeoarecalledstrongfieldwhilethosethatinducesmallsplittingsarecalledweakfield.Inaddition
toelectronictransitionsbetweenthedorbitals,veryintenseligandtometalchargetransfertransitions
canalsooccurintransitionmetalcomplexes.

Transitionmetalionsinbiologicalsystems
ThetransitionmetalsV,Cr,Mn,Fe,Co,Ni,Cu,ZnandMoareessentialforhealthybiological
function.Transitionmetalionsareimportantconstituentsofproteinsandenzymesinvolvedintransport
andstorage(Feinhaemoglobinandferritin),catalysis(CuandZninsuperoxidedismutase)andelectron
transfer(FeincytochromesandironsulfurproteinsandCuinbluecopperproteins).Theabilityofthe
transitionmetaliontoadoptmorethanoneoxidationstateandcoordinationnumberiscrucialtothe
operationofthesebiologicalsystems.

Isolationandpurificationoftransitionmetals
Metallurgyisthestudyoftheproductionandpurificationofmetalsfromtheirores.Asorescontain
metalsinpositiveoxidationstates,reductionisrequiredtoliberatethefreemetals.Thefoursteps
involvedinisolatingapuremetalfromitsoreareseparation,conversion,reductionandrefinement.The
reductionstepiscarriedouteitherchemicallyorelectrolytically,dependingontheore.Ironisthemost
importantmetalandisobtainedfromitsoreusingablastfurnace,withcokeasthereductant.Titanium
isisolatedfromTiO2byconversiontoTiCl4andreductionwithmoltenMg,whilecopperisobtained
fromitssulfideandoxideoresandpurifiedbyelectrolysis.

Applicationsoftransitionmetals
Transitionmetalshaveavastnumberofuses.Titaniumhashighstrengthandlowdensity,makingit
usefulforaircraftandbikeframesandjetengines.Mostchromiumisusedtomakesteelandother
alloys.Copper,silverandgold,thecoinagemetals,arequiteresistanttodirectoxidationcopperis
mainlyusedinelectricalwiring,whilesomegoldcomplexesareusefulfortreatingarthritis.Zincisused
togalvaniseiron,whilemercuryisusedinthermometersandfluorescentlights.Ru,Os,Rh,Ir,Pdand
Ptconstitutetheplatinummetalsandarechemicallyimportantassolidcatalystsinindustrialprocesses
aswellascatalyticconvertersincars.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Determiningdelectronconfigurations(section13.2)
Thisallowsustocalculatethenumberofdelectronsinanytransitionmetalion.Neutralatomshave
valenceelectronconfigurationsof(n+1)s2ndx2,wherexisthegroupnumberofthemetalinthe
periodictableandnistheprincipalquantumnumber.Thendorbitalsarefilledbeforethe(n+1)s
orbitalsintransitionmetalions.

Cumulativeformationconstant(n)(section13.4)
Thisquantifiestheextenttowhichtheformationreactionofatransitionmetalcomplexoccurs.Forthe
equilibrium:

Namingtransitionmetalcomplexes(section13.4)
TheIUPACrulesallowustodeterminethecorrectnameofanytransitionmetalcomplex.
1.Cationicspeciesarenamedbeforeanionicspecies.
2.Thenamesofanionicligandsalwaysendinthesuffixo.Ligandswithnamesendinginide,ite
andatehavethissuffixchangedtoido,itoandato,respectively.
3.Aneutralligandisusuallygiventhesamenameastheneutralmolecule,exceptaquaforH2O,
ammineforNH3andcarbonylforCO.
4.Thenumberofaparticularligandisspecifiedbytheprefixesdi=2,tri=3,tetra=4,penta=
5,hexa=6etc.
5.Ligandsarenamedfirst,inalphabeticalorderwithoutregardtocharge,followedbythenameof
themetal.
6.Negative(anionic)complexionsalwaysendinthesuffixate.Forneutralorpositivelycharged
complexes,themetalisalwaysspecifiedwiththeEnglishnamefortheelement,withoutany
suffix.
7.TheoxidationstateofthemetalinthecomplexiswritteninRomannumeralswithinparentheses
followingthenameofthemetal.
8.Thenumberofcounterionsneednotbespecified.
9.Includeanystereochemicaldescriptors(e.g.cis,trans,mer,fac)atthestartofthename,italicised
andhyphenated.

Crystalfieldtheory(section13.4)
Thisallowsustodeterminethedorbitalsplittingdiagramsfortransitionmetalcomplexesofany
geometry,andhencethedelectronconfigurationinthesecomplexes.Itisbasedonthecrystalfield
splittingenergy,whichistheenergydifference(o)betweenthed xy ,d xzandd yzorbitalsetandthe
andd z2orbitalset.

Thespectrochemicalseries(section13.4)
Thepositionofaligandinthespectrochemicalseriestellsusthemagnitudeofthedorbitalsplittingit
caninduce.Inorderofdecreasingovalues,theseriesis:
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS

METALSINTHEPERIODICTABLEANDTRANSITIONMETALS
13.1Thefollowingcompoundscanbepurchasedfromchemicalsupplycompanies.Determinethe
oxidationstateofthetransitionmetalineach:
(a)MnCO3,
(b)MoCl5,
(c)Na3VO4,
(d)Au 2O3,
(e)Fe2(SO4)35H2O,
(f) NiSO4,
(g)KMnO4,
(h)(NH4)2WO4,
(i) PbCrO4,
(j) ZrOCl28H2O.
13.2Givethenamesandsymbolsfortheelementsthathavethefollowingvalenceconfigurations:
(a) 4s13d5,
(b)5s24d10,
(c) 4s13d10,
(d)5s14d8,
(e) 4s23d2,
(f) 5s14d4.
13.3Writevalenceelectronconfigurationsforthefollowingtransitionmetalcations:
(a) Mn 2+,
(b)Ir3+,
(c) Ni2+,
(d)Mo 2+,
(e) Ti2+,
(f) Fe3+,
(g)Pt2+,
(h)Nb 3+.

LIGANDS
13.4Tobealigand,asubstanceshouldalsogenerallybeaLewisbase.Explain.
13.5Givethenamesoftwomoleculesthatareelectricallyneutral,monodentateligands.
13.6Givetheformulaeoffourionsthathave1chargesandaremonatomic,monodentateligands.
13.7Whatmustbetrueaboutaligandclassifiedasbidentate?
13.8Whatisachelate?UseLewisstructurestoillustratehowtheoxalateion,C O 2,functionsasa
2 4
chelatingligand.
13.9HowmanypotentialdonoratomsdoesEDTA4have?

TRANSITIONMETALCOMPLEXES
13.10Theformationofthecomplexion[Cu(OH ) ]2+isdescribedasaLewisacidbasereaction.
25
(a)Explainthisstatement.
(b)WhataretheformulaeoftheLewisacidandtheLewisbaseinthisreaction?
(c)Whatistheformulaoftheligand?
(d)Whatisthenameofthespeciesthatprovidesthedonoratom?
(e)Whatatomisthedonoratom,andwhyisitsodesignated?
(f) Whatisthenameofthespeciesthatistheacceptor?
13.11Whyaresubstancesthatcontaincomplexionsoftencalledcoordinationcompounds?
13.12UseLewisstructurestoillustratetheformationof[Cu(NH ) ]2+and[CuCl ]2ionsfromtheir
34 4
respective
13.13HowdoesasaltofEDTA4inshampoomaketheshampooworkbetterinhardwater?(Hard
watergenerallycontainshighconcentrationsofmetalionssuchasCa2+andMg 2+.)
13.14Thecobalt(III)ion,Co 3+,formsa1:1complexwithEDTA4.Whatisthenetcharge,ifany,on
thiscomplex,andwhatwouldbeasuitableformulaforit(usingthesymbolEDTA)?
13.15Whichcomplexhasahigher value,[Cr(NH ) ]3+or[Cr(en) ]3+?Why?
n 36 3
13.16Whatisacoordinationnumber?Whatstructuresaregenerallyobservedforcomplexesinwhich
thecentralmetalionhasacoordinationnumberof4?
13.17Whatisthemostcommonstructureobservedforcoordinationnumber6?
13.18Sketchthestructureofanoctahedralcomplexthatcontainsonlyidenticalmonodentateligands.
13.19Whatareisomers?
13.20Definestereoisomerism.
13.21Whatarecisandtransisomers?
13.22Whatiscisplatin?Drawitsstructure.
13.23Onappropriatecoordinateaxes,sketchandlabelthefivedorbitals.
13.24Whichdorbitalspointbetweenthex,yandzaxesandwhichpointalongtheaxes?
13.25Explainwhyanelectronina or orbitalinanoctahedralcomplexexperiencesgreater
repulsionbytheligandsthananelectroninad xy ,d xzord yzorbital.
13.26Sketchthedorbitalenergyleveldiagramforatypicaloctahedralcomplex.
13.27Explainhowthesamemetalinthesameoxidationstatecanformcomplexesofdifferentcolours.
13.28Ifacomplexappearsred,whatcolourlightdoesitabsorb?Whatcolourlightisabsorbedifthe
complexappearsyellow?
13.29Whatdoesthetermspectrochemicalseriesmean?Howcantheorderoftheligandsintheseries
bedetermined?
13.30Whatdothetermslowspincomplexandhighspincomplexmean?
13.31Forwhichdorbitalelectronconfigurationsarebothhighspinandlowspincomplexespossible
inoctahedralcomplexes?
13.32Sketchwhathappenstothedorbitalelectronconfigurationofthe[Fe(CN) ]4ionwhenit
6
absorbsaphotonofvisiblelight.
13.33Thecomplex[Co(O C O ) ]3isdiamagnetic.Sketchthedorbitalenergyleveldiagramforthis
2 2 23
complexandindicatetheelectronoccupancyoftheorbitals.
13.34Considerthecomplex[MCl (OH ) ]illustratedinthecentrebelow.Supposethestructureofthis
4 22
complexisdistortedtogivethestructureontheright,wherethewatermoleculesalongthezaxis
havemovedawayfromthemetalsomewhatandthefourchlorideionsalongthexandyaxes
havemovedcloser.Whateffectwillthisdistortionhaveonthesplittingpatternofthedorbitals?
Useasketchofthesplittingpatterntoillustrateyouranswer.

TRANSITIONMETALIONSINBIOLOGICALSYSTEMS
13.35Summarisethedifferencesbetweenhaemoglobinandmyoglobin.
13.36Whatfeaturesdomyoglobinandthecytochromeshaveincommon?

ISOLATIONANDPURIFICATIONOFTRANSITIONMETALS
13.37Useyourownwordstodefinemetallurgy.
13.38Whatisgangue?
13.39Whycangoldbeseparatedfromimpuritiesofrockandsandbypanning?
13.40Describetheflotationprocess.
13.41WritechemicalequationsforthereactionsthatoccurwhenCu 2SandPbSareroastedinair.Write
achemicalequationtoshowhowSO2evolvedfromtheroastingcanbepreventedfrombeing
releasedtotheenvironment.Whymightasulfuricacidplantbelocatednearaplantthatroasts
sulfideores?
13.42Whyisreduction,ratherthanoxidation,necessarytoextractmetalsfromtheircompounds?
13.43Whatiscoke?Howisitmade?
13.44DescribethechemicalreactionsinvolvedinthereductionofFe2O3thattakeplaceinablast
furnace.Whatistheactivereducingagentintheblastfurnace?
13.45Whatdoesrefiningmeaninmetallurgy?
13.46Whatisthedifferencebetweenpigironandsteel?

APPLICATIONSOFTRANSITIONMETALS
13.47Identifythecoinagemetalsanddescribesomeoftheirapplications.
13.48Identifytheplatinummetalsanddescribesomeoftheirapplications.
13.49Whatfeaturesoftitaniumaccountforitsuseasanengineeringmetal?
13.50Explainwhytitanium(IV)oxideisusedextensivelyasawhitepigment.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
13.51Theiron(III)ionformsacomplexwithsixcyanideions,calledtheferricyanideion.Whatisthe
netchargeonthiscomplexion,andwhatisitsformula?
13.52Writetheformula,includingthecorrectcharge,foracomplexthatcontainsCo(III),twoCl
ligandsandtwoethylenediamineligands.
13.53Writetheformula,includingthecorrectcharge,foracomplexthatcontainsCo(III),twoNH3
ligandsandfourNO2ligands.
13.54Howwouldthefollowingmoleculesorionsbenamedasligandswhenwritingthenameofa
complexion?
(a) C O 2
2 4
(b)S2
(c) Cl
(d)(CH3)2NH(dimethylamine)
(e)NH3
(f) N3
(g)SO 2
4
(h)CH COO
3
13.55GiveIUPACnamesforeachofthefollowing.
(a) [Ni(NH ) ]2+
36
(b)[CrCl3(NH3)3]
(c) [Co(NO ) ]3
26
(d)[Mn(CN) (NH ) ]2
4 32
(e) [Fe(O C O ) ]3
2 2 23
(f) [AgI ]
2
(g)[Co(en)2(OH2)2]2(SO4)3
(h)[CrCl(NH3)5]SO4
(i) K3[Co(O2C2O2)3]
13.56Writechemicalformulaeforeachofthefollowing.
(a)tetraaquadicyanidoiron(III)ion
(b)tetraammineoxalatonickel(II)
(c)diaquatetracyanidoferrate(III)ion
(d)potassiumhexathiocyanatomanganate(III)
(e)tetrachloridocuprate(II)ion
(f) tetrachloridoaurate(III)ion
(g)bis(ethylenediamine)dinitroiron(III)ion
(h)tetraamminedicarbonatocobalt(III)nitrate
(i) ethylenediaminetetraacetatoferrate(II)ion
 (j) diamminedichloridoplatinum(II)
13.57In[FeCl2(en)(OH2)2],whatisthecoordinationnumberofiron?Whatisitsoxidationnumberin
thiscomplex?
13.58Whatisthecoordinationnumberofnickelin[Ni(NO ) (O C O ) ]4?
22 2 2 22
13.59Thecompoundshownbelowiscommonlycalleddiethylenetriamine(notitsIUPACname)andis
abbreviateddien.

Itusesthreedonoratomswhenitbondstoatransitionmetalion.
(a)Identifythedonoratoms.
(b)Whatisthecoordinationnumberofcobaltinthecomplex[Co(dien) ]3+?
2
(c) Sketchthestructureofthecomplex[Co(dien) ]3+.
2
(d)Whichcomplexwouldbeexpectedtohavethelarger value,[Co(dien) ]3+or
n 2
3+
[Co(NH3)6] ?
(e)Drawthestructureoftriethylenetetraamine.
13.60Thefollowingaretwostructuresforacomplex.Aretheydifferentisomers,oraretheyidentical?
Explainyouranswer.

13.61Sketchandlabeltheisomersofthesquareplanarcomplex[PtBrCl(NH3)2].
13.62Thecomplex[CoCl3(NH3)3]canexistintwoisomericforms.Sketchthem.
13.63Foreachofthefollowingpairs,inwhichcomplexdoweexpecttofindthelargero?
(a) [Cr(OH ) ]2+or[Cr(OH ) ]3+
26 26
(b)[Cr(en) ]3+or[CrCl ]3
3 6
13.64Arrangethefollowingcomplexesaccordingtothewavelengthsoftheirabsorptionmaxima,from
lowesttohighest:[Cr(OH2)6]3+,[CrCl6]3,[Cr(en)3]3+,[Cr(CN)6]3,[Cr(NO2)6]3,[CrF6]3,
[Cr(NH3)6]3+.
13.65Whichcomplexisexpectedtoabsorblightofthehighestfrequency:[Cr(OH ) ]3+,[Cr(en) ]3+or
26 3
3
[Cr(CN)6] ?
13.66Ineachofthefollowingpairs,whichcomplexshouldabsorblightofthelongerwavelength?
(a) [Fe(OH ) ]2+or[Fe(CN) ]4
26 6
(b)[Mn(CN) ]3or[Mn(CN) ]4
6 6
13.67Ineachofthefollowingpairs,whichcomplexisexpectedtoabsorbtheshorterwavelengthof
light?Justifyyouranswers.
(a) [RuCl(NH ) ]2+or[FeCl(NH ) ]2+
35 35
 (b)[Ru(NH ) ]2+or[Ru(NH ) ]3+
36 36
13.68Anoctahedralcomplex[CoAo6]3+isred.Thecomplex[CoB ]3+isgreen.Whichligand,AorB,
6
producesthelargercrystalfieldsplittingenergy,o?Explainyouranswer.
13.69Referringtothetwoligands,AandB,describedinquestion13.68,whichcomplexisexpectedto
bemoreeasilyoxidised,[CoA6]2+or[CoB6]2+?Explainyouranswer.
13.70Referringtothecomplexesinquestions13.68and13.69,isthecolourof[CoAo6]2+more
likelytoberedorblue?
13.71Isthecomplex[CoF ]4morelikelytobelowspinorhighspin?Coulditbediamagnetic?
6
13.72Sketchthedorbitalenergylevelsfor[Fe(OH ) ]3+and[Fe(CN) ]3andpredictthenumberof
26 6
unpairedelectronsineach.
13.73Determinetheoxidationstateandnumberofdelectronsforthemetalionineachofthe
followingcoordinationcomplexes.
(a)[Ru(NH3)6]Cl2
(b)trans[Cr(en)2I2]I
(c)cis[PdCl2(P(CH3)3)2]
(d)fac[IrCl3(NH3)3]
(e)[Ni(CO)4]
(f) [Rh(en)3]Cl3
(g)cis[MoBr2(CO)4]
(h)Na3[IrCl6]
(i) mer[IrCl3(NH3)3]
(j) [Mn(CO)5Cl]
13.74Namethecompoundsinquestion13.73.
13.75Drawstructuresofthemetalcomplexesinquestion13.73.
13.76Writetheformulaeofthefollowingcomplexes.
(a)cistetraamminechloridonitrocobalt(III)
(b)amminetrichloridoplatinate(II)
(c)transdiaquabis(ethylenediamine)copper(II)
(d)tetrachloridoferrate(III).
(e)potassiumtetrachloridoplatinate(II)
(f) pentaammineaquachromium(III)iodide
(g)tris(ethylenediamine)manganese(II)chloride
(h)pentaammineiodidocobalt(III)nitrate.
13.77Drawthestructureofeachcomplexioninquestion13.76.
13.78Foranoctahedralcomplexofeachofthefollowingmetalions,drawacrystalfieldenergy
diagramthatshowstheelectronoccupancyofthevariousdorbitals:
(a)Ti(II),
(b)Cr(III),
(c)Mn(II),
 (d)Fe(III),
(e)Zn(II),
(f) Cr(II),
(g)Co(II),
(h)Rh(III).
Whereappropriate,showboththehighspinandlowspinconfigurations.
13.79Predictwhethereachofthefollowingcomplexesisdiamagneticorparamagnetic.Ifthecomplex
isparamagnetic,statethenumberofunpairedelectronsithasandestimateitsmagneticmoment.
(a) [Ir(NH ) ]3+
36
(b)[Cr(OH ) ]2+
26
(c) [PtCl ]2(squareplanar)
4
(d)[Pd(P(CH3)3)4](squareplanar)
(e) [Ru(CN) ]4
6
(f) [Co(NH ) ]3+
36
(g)[CoBr ]2(tetrahedral)
4
(h)[PtCl2(en)](squareplanar)
13.80CompoundsofZr(II)aredarkpurple,butmostZr(IV)compoundsarecolourless.Explain.
13.81Oneofthecoordinationcomplexes[Cr(OH ) ]3+and[Cr(NH ) ]3+isvioletandtheotheris
26 36
orange.Decidewhichiswhichandexplainyourreasoning.
13.82Thecomplex[Fe(en)3]Cl3islowspin.State:
(a)thecoordinationnumberofthemetal
(b)theoxidationnumberandnumberofdelectronsofthemetal
(c)thegeometryofthecomplex
(d)whetherthecomplexisdiamagneticorparamagnetic
(e)thenumberofunpairedelectronsinthecomplex
(f) themagneticmomentofthecomplex.
13.83Thecomplex[Mn(OH2)6]SO4ishighspin.State:
(a)thecoordinationnumberofthemetal
(b)theoxidationnumberandnumberofdelectronsofthemetal
(c)thegeometryofthecomplex
(d)whetherthecomplexisdiamagneticorparamagnetic
(e)thenumberofunpairedelectronsinthecomplex
(f) themagneticmomentofthecomplex.
13.84AsolutioncontainingFe(II)(aq)isparamagnetic.Additionofsodiumcyanidemakesthesolution
diamagnetic.Usecrystalfieldenergydiagramstoexplainwhythemagneticpropertiesofthe
solutionsaredifferent.
13.85Thecomplex[Cr(NH ) ]3+hasitsmaximumabsorbanceat465nm.Calculatethecrystalfield
36
splittingenergyforthecompoundandpredictitscolour.
13.86Thecomplex[Fe(OH ) ]3+hasitsmaximumabsorbanceat724nm.Calculatethecrystalfield
26
splittingenergyforthecompoundandpredictitscolour.
13.87Drawallpossibleisomersofthefollowingcompounds:
(a)[IrCl3(NH3)3],
(b)[PdCl2(PMe3)2],
(c)[CrBr2(CO)4],
(d)[Cr(en)I2(NH3)2].
13.88Drawthestructuresofallpossibleisomersofeachofthefollowingcoordinationcompounds.
(a)tetraamminedibromidocobalt(III)bromide
(b)triamminetrichloridochromium(III)
(c)dicarbonylbis(trimethylphosphane)platinum(0)
13.89Thecarbonateioncanbeeitheramonodentateorabidentateligand.Makesketchesthatshow
theligandbindingtoametalcationinbothmodes.
13.90Writeelectronconfigurationsforthefollowing:
(a)Cr,Cr(II)andCr(III),
(b)V,V(II),V(III),V(IV)andV(V),
(c)Ti,Ti(II)andTi(IV),
(d)Au,Au(I)andAu(II),
(e)Ni,Ni(II)andNi(III),
(f) Mn,Mn(II),Mn(IV)andMn(VII).
13.91Namethefollowingcoordinationcompounds.
(a)

(b)

(c)

(d)

(e)
 (f)

13.92TheCu(II)ionformstetrahedralcomplexeswithsomeanionicligands.WhenCuSO45H2O
dissolvesinwater,abluesolutionresults.TheadditionofaqueousKFsolutionresultsinagreen
precipitate,buttheadditionofaqueousKClresultsinabrightgreensolution.Identifyeachgreen
speciesandwritechemicalreactionsfortheseprocesses.
13.93TheCu(II)ionformstetrahedralcomplexeswithsomeanionicligands.WhenCuSO45H2O
dissolvesinwater,abluesolutionresults.TheadditionofaqueousKCNsolutionresultsina
whiteprecipitateatfirst,buttheadditionofmoreKCNcausestheprecipitatetodissolve.Identify
theprecipitateandthedissolvedspeciesandwritechemicalreactionsfortheseprocesses.
13.94Drawaballandstickmodelofthemerisomerofr[NiCl F ]4,orientedsothatthefluorideions
3 3
areinthetop,bottomandleftforwardpositions.
13.95Drawaballandstickmodelofthefacisomerof[NiCl F ]4,orientedsothatthefluorideionsare
3 3
inthetopandtworearpositions.
13.96Asligands,chlorideandcyanideareatoppositeendsofthespectrochemicalseries.Nevertheless,
experimentsshowthat[CrCl6]3and[Cr(CN)6]3displaysimilarmagneticbehaviour.Explain
howthiscanbeso.
13.97Inoctahedralgeometry,themagnetismind4d7coordinationcompoundsofthe3dtransition
metalsdependsontheligandsandtheoxidationstateofthemetal.Ontheotherhand,d1d3
andd8d9compoundsalwaysdisplaysimilarmagneticbehaviour.Explain.
13.98The andd z2orbitalsaredegenerateinanoctahedralcomplex.However,inasquare
planarcomplex,the orbitalisofhigherenergythanthed z2orbital.Useorbitalsketches
toexplainthedifference.
13.99Useorbitalsketchestoexplainwhythed xzand orbitalshavedifferentenergiesin
octahedralcoordinationcomplexes.
13.100DeterminetheLewisstructureofthedichromateanion,[Cr O ]2,whichcontainsonebridging
2 7
oxygenatom,anddrawamodelshowingitsgeometry.
13.101Writeabalancedequationforthereactioncatalysedbytheenzymesuperoxidedismutase.
Makeasketchofthecoordinationenvironmentaroundthetwometalatoms.
13.102Someresearchersusethetermthebrassenzymetodescribesuperoxidedismutase.Canyou
suggestareasonforthisnickname?
13.103BluecopperproteinsarebluewhentheycontainCu(II)butcolourlessasCu(I)compounds.The
colourcomesfromaninteractioninwhichaphotoncausesanelectrontotransferfromasulfur
lonepaironacysteineligandtothecoppercentre.Whydoesthischargetransferinteraction
 occurforCu(II)butnotCu(I)?
13.104SolutionscontainingCu 2+(aq)ionsareblue,whereassolutionscontainingZn 2+(aq)ionsare
colourless.Explainthisobservation.
13.105Oneofthemostcommonapproachestotheinvestigationofmetalloproteinsistoreplacethe
naturallyoccurringmetalionwithadifferentonethathasapropertyadvantageousforchemical
studies.Forexample,zincproteinsareoftenstudiedbyvisiblespectroscopyafterCo(II)has
beensubstitutedforZn(II).Explain,usingcrystalfieldenergydiagrams,whyCo(II)isabetter
metalthanZn(II)forvisiblespectroscopy.
13.106Explainhowliquidmercurycanbeusedtopurifymetalssuchasgoldandsilver.
13.107Writebalancedchemicalequationsforeachofthefollowingmetallurgicalprocesses:
(a)roastingofCuFeS2,
(b)removalofsiliconfromsteelinaconverter,
(c)reductionoftitaniumtetrachlorideusingsodiummetal.
13.108Acopperorecontains2.37%Cu Sbymass.If5.6010 4kgofthisoreisheatedinair,
2
calculatethemassofcoppermetalthatisobtainedandthevolumeofSO2gasproducedin
ambientconditions(9.9310 4Paand23.5C).
13.109Whatmassoflimestone,inkilograms,shouldbeaddedtoeverykilogramofironoreprocessed
inablastfurnaceifthelimestoneis95.5%CaCO3andtheironorecontains9.75%SiO2?
13.110Bothvanadiumandsilverarelustroussilverymetals.Suggestwhysilveriswidelyusedfor
jewellerybutvanadiumisnot.
13.111Titaniumisnearly100timesmoreabundantintheEarth'scrustthancopper.However,copper
wasexploitedasametalinantiquity,buttitaniumhasfoundapplicationsonlyinrecenttimes.
Explain.
13.112Whatisthechemicalnameandtheformulaoftheblacktarnishthataccumulatesonobjects
madeofsilver?Writeabalancedequationtoshowhowthisblacktarnishforms.
13.113Whatisthechemicalnameandthecompositionofthegreentarnishthataccumulatesonobjects
madeofcopper?Writebalancedequationstoshowhowthisgreentarnishforms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
13.114Thecomplex[PtCl2(NH3)2]canbeobtainedastwodistinctisomericforms.Showthatthis
meansthecomplexcannotbetetrahedral.
13.115Asolutionwaspreparedbydissolving0.500gofCrCl36H2Oin100mLofwater.Excesssilver
nitratesolutionwasadded.ThisproducedaprecipitateofAgCl,whichwasfilteredfromthe
mixture,washed,driedandweighed.TheAgClhadamassof0.538g.
(a)Whatistheformulaofthecomplexionofchromiuminthiscompound?
(b)Whatisthecorrectformulaforthecompound?
(c)Sketchthestructureofthecomplexioninthiscompound.
(d)Howmanydifferentisomersofthecomplexcanbedrawn?
13.116Theoctahedralchromiumcomplexes[Cr(NH ) L]n+,whereLisCl,H OorNH ,have
35 2 3
absorptionmaximaat515nm,480nmand465nm,respectively.
(a)Whatisthevalueofnforeachofthecomplexes?
(b)Predictthecoloursofthethreecomplexes.
(c) CalculatethecrystalfieldsplittingenergyinkJmol1foreachofthecomplexesand
explainthetrendinvalues.
13.117Thecomplexion[Ag(NH ) ]+hasalineargeometry.Predictthecrystalfieldsplittingdiagram
32
forthiscomplex,placingtheligandsalongthezaxis.
13.118Tetracarbonylnickel(0)is[Ni(CO) ],andtetracyanidozinc(II)is[Zn(CN) ]2.Predictthe
4 4
geometryandcolourofeachcomplex.
13.119Carbonmonoxideandtungstenformacolourlessoctahedralcomplex.Sketchthedorbital
splittingfielddiagramforhexacarbonyltungsten(0),andsuggestwhythecomplexiscolourless.
13.120Thecomplex[Ni(CN) ]2isdiamagnetic,but[NiCl ]2isparamagnetic.Proposestructuresfor
4 4
thetwocomplexesandexplainwhytheyhavedifferentmagneticproperties.
13.121Predictwhethereachofthefollowingcomplexesishighspinorlowspin:
(a) [Fe(CN) ]4,
6
(b)[MnCl ]2,
4
(c) [Rh(NH ) ]3+,
36
(d)[Co(OH ) ]2+.
26
Estimatetheirmagneticmoments.
13.122Aportionoftheabsorptionspectrumoftheoctahedralcomplexion[CrCl (OH ) ]+isshown
2 24
aboveright.
 (a) Estimatethecrystalfieldsplittingenergy, ,inkJmol1.
o
(b)Whatcolouristhecomplex?
(c)Namethecomplexcation.
(d)Drawallpossibleisomersofthecomplex.
(e)Drawthedorbitalsplittingdiagramandshowtheelectronictransitionthatgivesthe
complexitscolour.
13.123Inthe1890s,theSwisschemistAlfredWernerpreparedseveralplatinumcomplexesthat
containedbothammoniaandchlorine.Hedeterminedtheformulaeofthesespeciesby
precipitatingthechlorideionswithAg +.Thefollowingtableshowstheempiricalformulaeand
numberofchlorideionsthatprecipitateperformulaunit.

Empiricalformula NumberofClions
PtCl42NH3 0
PtCl43NH3 1
PtCl44NH3 2
PtCl45NH3 3
PtCl46NH3 4

Determinethemolecularformulaeoftheseplatinumcomplexes,namethemanddrawtheir
structures.
13.124SilverplatingprocessesoftenuseAg(CN)2asthesourceofAg +insolution.Tomakeasolution
ofthision,achemistused4.0Lof3.00mNaCNand50Lof0.2mAgNO3.Whatisthe
concentrationoffreeAg +ionsinthissolution?WhyisAgClnotusedinthisprocess?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
absorbance(A) ddtransitions meridional(mer)
ambidentate dativebonds metaltoligandchargetransfer
axial degenerate (MLCT)transitions
Beer'slaw diamagnetic metallurgy
BeerLambertlaw disproportionation monodentate
bidentate donoratom octahedral
chelatecomplexes donorcovalentbonds organometalliccompounds
chelateeffect electronictransition pairingenergy(P)
chelaterings equatorial paramagnetic
cisisomer facial(fac) polydentate
cistransisomers ferromagnetism spectrochemicalseries
complementarycolour highspin squareplanar
complexes hydrateisomers squarepyramidal
coordinatebonds inert Stereoisomers
coordinationchemistry ionisationisomers strongfield
coordinationcompounds labile Structuralisomers
Coordinationisomers ligandtometalchargetransfer tetrahedral
coordinationnumber (LMCT)transitions transisomer
counterions ligands transitionmetals
crystalfieldsplittingenergy linkageisomers trigonalbipyramidal
crystalfieldtheory lowspin weakfield
cumulativeformationconstant magneticmoment()
(n) maingroupmetals

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

14 ThepblockElements
Youmightthinkthateverythinghadlongsincebeenlearnedaboutamoleculeassimpleas
nitricoxide(nitrogenmonoxide),NO,firstpreparedbyJosephPriestleyover200yearsago.
Yet,itisonlyrecentlythatwehaverecognisedtheimportanceofNOinanumberof
biochemicalprocesses.ManyanimalssynthesiseNO,asitplaysrolesinnervefunction,
regulationofbloodpressure,bloodclotting,andimmunesystemresponses.Inmanyofthese
processes,NOisproducedinonepartofanorganismandmovestoanotherpart,whereits
chemicalpropertiestriggerabiochemicalreaction.NOhelpstoadjusttheinteractions
betweenbloodandbloodvessels.Oneexampleisbloodclotting,showninthe
accompanyingphoto.Whenthewallofabloodvesseliscut,anenzymeinthecellwall
sendschemicalsignalsthatinteractwithbloodplatelets,causingclotting.NOinhibitsthis
processaneffectexploitedbymosquitoesthesalivaofmosquitoescontainsNO
generatingchemicalsthatpreventtheirvictim'sbloodfromclottingwhilethemosquitofeeds.

Anotherexampleisthedilationofbloodvessels.Nitroglycerine,C3H5N3O9,hasbeen
prescribedformorethanacenturyasatreatmentofangina(chestpain)becauseitdilates
bloodvessels,therebydecreasingbloodpressureandincreasingbloodflow.Onlyrecently
wasitdiscoveredthatNOisinvolvedinthemechanismofthisprocess.Biochemists
speculatethatNObindstoironintheenzymethatcausesdilation,butdetailedknowledgeis
stilllacking.Thereisevidencethattheneuralprocessesleadingtomemoryincludethe
productionanddiffusionofNO.AnenzymeinthebrainproducesNOfromanaminoacid.
HowdoesNOinteractwithmorecomplexmoleculesasthebrainfunctions?Onepossibility
 isthat,onceaneuraltriggerfires,anadjacentneuronproducesNO,whichdiffusesbackto
theoriginalneuronandstimulatesfurtheractivity.Thiscouldbehowlongtermmemory
develops.

ThecomponentsoftheNOmolecule,nitrogenandoxygen,arepblockelements,aname
giventoelementsbelongingtogroups13to18oftheperiodictable.Theseelementsare
characterisedbythegradualfillingoftheporbitals.Inthischapter,wedescribeselected
featuresofthediversechemistryofthepblockelements.

KEYTOPICS

14.1Thepblockelements
14.2Chemistryofthepblockelements
14.3Thebiogeochemicalcyclesofnature

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14.1ThepblockElements
Inchapter1(figure1.16,p.15),weshowedthatallelementsintheperiodictablecouldbeclassifiedas
oneofthreetypes:metals,nonmetalsandmetalloids.Wealsoshowedthatthedifferentgroupsofthe
periodictable(1to18)aredefinedbythevalenceelectronconfigurationforexample,groups1and2
arecalledsblockelements,owingtotheirns1orns2configurations,whilegroups3to12arecalledd
blockelements,withvalenceelectronconfigurationsof(n+1)s2nd 1to(n+1)s2nd 10.Whilethe
elementsofgroups1to12,andthelanthanoidandactinoidelementsare,withtheexceptionof
hydrogen,exclusivelymetals,groups13to18containelementswhicharepredominantlynonmetalsor
metalloids.Theelementsofgroups13to18arecollectivelycalledpblockelementsandtheyare
characterisedbythegradualfillingoftheporbitalsacrosseachperiod.Ascanbeseeninfigure14.1,
thevalenceshellelectronconfigurationoftheseelementsrangesfromns2np 1(group13)tons2np 6
(group18).

FIGURE14.1Thepblockelements.

Thechemistryexhibitedbytheseelementsisextraordinarilywideandvaried,andadetaileddescription
ofallthepblockelementsisbeyondthescopeofthistext.Wewillthereforeprovideabrief
introductiontoeachofthepblockelementsbeforeconcentratingonrepresentativeelementswhich
illustrateimportantconceptsofstructure,bondingandreactivitywithinthepblock.Wewillalsodetail
theimportanceoftheseelementsinthebiogeochemicalcyclesofnature.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
14.2ChemistryofthepblockElements

Group13

Theelementsingroup13,withtheexceptionofboron,aremetals,andthereforedisplaytheexpectedcharacteristics
outlinedonp.15inchapter1.Theelementshavethevalenceelectronconfigurationns2np 1,andtendtoexhibita
formaloxidationnumberof+3intheircompounds.However,bothindiumandthalliumhaveasignificantchemistry
inthe+1oxidationstateowingtothefactthatthevalencens2electronsexperiencearelativelyhighZeff,andare
thereforeheldrelativelytightly,duetothepoorshieldingcharacteristicsoftheinnerdandfelectrons.

Boronisametalloidand,asbefitsitssmallsizeandconsequenthardLewisacidity,isfoundincombinationwith
oxygeninnature,inavarietyofborateminerals.Theelementitselfisashinyblacksolid,withaveryhighmelting
point(infact,amongthepblockelementsthemeltingpointofboronisexceededonlybythatofcarbon)whichis
attributabletoitsunusualsolidstatestructure.Thevalenceelectronconfigurationofboron,2s22p 1,meansthatitis
unabletocompleteanoctet(p.172)throughtheformationofthreesinglebonds,andelementalborontherefore
adoptsarathercomplexmolecularstructurethatcannotbedescribedbysimpleLewisstructures.Boronexistsin
severaldifferentcrystallineforms(allotropes),eachofwhichischaracterisedbyclustersof12boronatomslocatedat
theverticesofanicosahedron(a20sidedgeometricfigure),asshowninfigure14.2.
 FIGURE14.2 Thestructureofanallotropeofelementalboron.
(a)Thearrangementof12boronatomsinaB12 cluster.
(b)TheelementboronconsistsofaninterconnectingnetworkofB12 clustersthatproducesaveryhardand
highmeltingsolid.

Eachboronatomwithinagivenclusterisequidistantfromfiveothersand,inthesolid,eachoftheseisalsojoinedto
yetanotherboronatomoutsidethecluster(figure14.2b).Theelectronsavailableforbondingarethereforedelocalised
toalargeextentovermanyboronatoms,andthesimpleLewisideaofpairsofelectronsinacovalentbonddoesnot
applyinthiscase.ThelinkingtogetherofB12unitsproducesalarge,threedimensionalcovalentsolidthatisvery
difficulttobreakdown.Asaresult,boronisveryhard(itisthesecondhardestelement)andhasaveryhighmelting
point(about2200C).Boronatomssharewithcarbonatomstheabilitytoundergocatenation(p.38),bondingto
themselvestoformmoderatelysizedmolecules.However,incontrasttocarbon,suchmoleculesgenerallyadoptthree
dimensionalpolyhedralstructures,ratherthanchainsorrings.

Aluminiumistheonlyoneofthefourgroup13metalsnottocontainfilleddorbitalsitthereforehasasmallatomic
radiuswhichrendersit,likeboron,ahardLewisacid.Itisfoundinnatureasbauxite,Al(O)OH,acompoundofwhich
Australiaistheworld'slargestproducer,andinavarietyofcompoundscalledaluminosilicateswhicharecomposedof
aluminium,siliconandoxygeninallthesecompounds,aluminiumexistsasthe3+cation.Reductionofbauxite,or
indeedanyaluminiumcompound,tometallicaluminiumisdifficultand,asaresult,thepureelementwasfirstisolated
onlyin1825fromthereductionofAlCl3withpotassium.Itsrarityforatimefollowingthismeantthataluminiumwas
moreexpensivethangoldorplatinum,andEmperorNapoleonIIIofFrancereputedlyhadaluminiumdinnerware
whichwasusedforimportantguests.Nowadays,aluminiumisproducedfrompurifiedAl2O3byelectrolysis,usingthe
HallHroultprocesswhichwasdevelopedinthe1880s(seeChemicalConnectionsonp.601).Bauxiteisfirst
purifiedofinsolubleimpuritiesthroughconversiontothesolublecomplexion[Al(OH)4]bydissolutioninstrong
base:

DilutionofthissolutionwithwatercausestheprecipitationofAl(OH)3:

anddehydrationofthisgivespureAl2O3:
ThemeltingpointofAl2O3istoohigh(2015C)anditselectricalconductivitytoolowtomakedirectelectrolysis
commerciallyviable.Instead,Al2O3ismixedwithcryolite,Na3AlF6,containingabout10%CaF2.Thismixturehasa
meltingpointof1000C,stillahightemperaturebutnotprohibitivelyso.Aluminiumformsseveralcomplexions
withfluorideandoxide,sothemoltenmixturecontainsavarietyofspecies,includingAlF4,AlF63andAlOF32.
Theseandotherionsmovefreelythroughthemoltenmixtureaselectrolysisoccurs.Figure14.3showsaschematic
representationofanelectrolysiscellforaluminiumproduction.

FIGURE14.3Aluminiummetalisproducedbyelectrolysisofaluminiumoxidedissolvedinmoltencryolite.Al3+isreducedto
Alatthecathode,andCisoxidisedtoCO2 attheanode.

Anexternalelectricalpotentialdriveselectronsintoagraphitecathode,whereAl3+ionsarereducedtoAlmetal:

Theanode,whichisalsomadeofgraphite,isoxidisedduringelectrolysis.Carbonfromtheanodecombineswith
oxideionstoformCO2gas:

Becauseofthevarietyofionicspeciespresentinthemelt,thereactionsthattakeplaceattheelectrodesare
considerablymorecomplexthanthesimplerepresentationsgivenhere.Nevertheless,theoverallreactionistheone
givenbythesumofthesesimplifiedreactions.

Theelectrolysisapparatusoperateswellabovethemeltingpointofaluminium(660C)and,asliquidaluminiumhasa
higherdensitythanthemoltensaltmixture,pureliquidmetalsettlestothebottomofthereactor.Thepuremetalis
drainedthroughaplugandcastintoingots(figure14.4).Aluminiumrefiningconsumeshugeamountsofelectricity.
Infact,thealuminiumsmelteratTiwaiPointinNewZealandconsumes15%ofthecountry'sentireenergyoutput.

FIGURE14.4Aluminiumrefiningusesverylargeamountsofelectricity.
Chemical

ConnectionsHallHroultprocess

Apartfromitsobvioususesincans(figure14.5),foil,andwindowsanddoors,aluminium'sstrength,
lightness,highelectricalandthermalconductivity,andresistancetocorrosionmakeitusefulinkitchen
utensils,car,aircraftandrocketconstruction,electricaltransmissionlinesandincoatingsforhighprecision
mirrorssuchasthoseintelescopes.

FIGURE14.5Australiausesmorethan3millionaluminiumcanseachyearjustoverhalfoftheseareforsoft
drinksjustoveronethirdareforbeer.

AluminiumisthethirdmostabundantelementintheEarth'scrustandthemostabundantmetal.
Nevertheless,aluminiumwasnotisolateduntil1825andwasstillapreciousrarity60yearslater.The
reasonforthiselusivenessisthehighstabilityofAl3+.Thereductionofaluminiumcompoundstothefree
metalrequiresstrongerreducingpowerthancommonchemicalreducingagentscanprovide.Theextraction
ofaluminiumhadtoawaitthebirthofelectrochemistryandthedevelopmentofelectrolysis(seechapter
12).

Two22yearoldscientists,theAmericanchemistCharlesHallandtheFrenchmetallurgistPaulHroult,
developedthesameprocessindependentlyin1886,bothbecomingfamousasfoundersofthealuminium
industry,HallintheUnitedStatesandHeroultinEurope.

Hallwasinspiredbyhischemistryprofessor,whoobservedthatwhoeverperfectedaninexpensivewayof
producingaluminiumwouldbecomerichandfamous.Afterhisgraduation,Hallsettoworkinhishome
laboratorytryingtoelectrolysevariouscompoundsofaluminium.WorkingwithhissisterJulia,whohad
alsostudiedchemistry,Hallsuccessfullyproducedglobulesofthemetalwithin8months.Meanwhile,
HeroultwasdevelopingtheidenticalprocessinFrance.Hallfoundedacompanyforthemanufactureof
aluminium.Thatcompanybecameimmenselysuccessful,eventuallygrowingintoAlcoa.

Successfulelectrolysisofaluminiumrequiresaliquidmediumotherthanwaterthatcanconductelectricity.
ThekeytotheHallHeroultprocessistheuseofmoltencryolite,Na3AlF6,asasolvent.Cryolitemeltsatan
accessibletemperature,itdissolvesAl2O3,anditisavailableinthenecessarypurity.Asecondimportant
featureisthechoiceofgraphitetoserveastheanode.Graphiteprovidesaneasyoxidationprocess,the
oxidationofcarbontoCO2.
 ThereasoningthatledHallandHeroulttotheidenticalprocesswasprobablysimilar.Electrolysiswas
recognisedasapowerfulreducingmethod.Allattemptstoreduceaqueousaluminiumcationsfailed,
makingitclearthatsomemoltensaltwouldhavetobeused.Experimentingwithvarioussalts,nodoubt
guidedbytheprinciplethatlikedissolveslike,thetwoyoungmeneventuallytriedNa3AlF6,amineral
whoseconstituentelementsshouldnotinterferewiththereductionofaluminium.Graphiteelectrodeswere
alreadyinuse,soexperimentingwiththemwouldhavebeenanaturalchoice.Alltheingredientsforthis
inventionmayhavebeeninplace,butthatdoesnotdetractfromitsbrilliance.

Inmorethan100yearsofgrowthinthealuminiumindustry,theonlysignificantchangetotheHallHeroult
processhasbeentheadditionofCaF2tothemelttolowertheoperatingtemperature.

Galliumisasilverywhitemetalthatisobtainedprimarilyasabyproductofthepurificationofbauxite,discussedon
p.600.RemovalofAl(OH)3leadstoconcentrationofgalliumcompoundsintheremainingalkalinesolutionand
electrolysiseventuallyyieldsthepuremetal.GalliumwasoneofthemissingelementspredictedbyMendeleevinhis
originalperiodictable(seefigure1.15,p.14).Galliumisofinterest,amongotherthings,foritsverylowmeltingpoint
(around30C)andtheextremelylargetemperaturerangeoverwhichitexistsasaliquid(itboilsaround2200C).
Compoundsofgalliumfindextensiveuseinlightemittingdiodes(LEDs).

Indiumisnotfoundinnatureinitselementalstate.ItsrelativelylargesizemeansitbehavesasasoftLewisacid,and
thisisreflectedinthefactthatitisgenerallyfoundinsulfideoredepositsalongwithzinc,copperandtin.Thepure
metalisobtainedasabyproductoftheelectrolyticrefiningofzincandisknownforthefactthatitemitsahigh
pitchedcrywhenitisbent.Themajoruseofindiumisinthinfilmsofindiumtinoxide(ITO)whichareusedin
liquidcrystaldisplays.

Thalliumisasoftmetalwhichexhibitsametalliclustrewhenfreshlycut.However,itquicklydevelopsagreyoxide
layeronexposuretoairandgenerallyresemblesleadinappearance.Itisfoundinsulfideandseleniumoredeposits,
reflectingitssoftLewisacidicnature.Thalliumanditscompoundsarehighlytoxicandwereoncepoisonsofchoice
forserialkillers.Infact,SydneywomanCarolineGrillswassentencedtodeathin1953(latercommutedtolifein
prison)fortheattemptedmurderoftwoofherinlawsusingthallium,andoverthepreviousyearthereweresome46
reportedcasesofthalliumpoisoning,with10deaths,inSydney.Thetoxicityoftheelement,whichlimitsits
usefulness,isthoughttoarisefrombothitssimilarityinsizetopotassiumanditsaffinityforsulfurcontainingamino
acids.However,therehasbeensomeinterestinthalliumcontainingmaterialsashightemperaturesuperconductors.

Group14

Group14comprisesanonmetal,twometalloidsandtwometals.Theelementshavevalenceelectronconfigurations
ns2np 2andthepredominantoxidationnumberofgroup14elementsintheircompoundsis+4.However,aswealso
sawingroup13,theheavierelementscandisplayanoxidationstatetwolowerthanthatusuallyfoundinthegroup.
Thusbothtinandleadhavesignificantchemistryinthe+2oxidationstate,withcompoundsofthelatterinthe+4
oxidationstateoftenbeingunstablewithrespecttoreduction.
Wehavealreadybrieflydiscussedthedifferentallotropesofelementalcarbon,andchapter16isdevotedtothe
chemistryofcarbon,sowewillnotconcernourselvesfurtherwiththiselementhere.

SiliconbehavesasahardLewisacid,andoccursinnatureasSiO2(silica)andvarioussilicateanions.Theelement
maybeobtainedbythehightemperaturereductionofsilicausingcokeinanelectricarcfurnace,accordingtothe
equation:

butthisgivessiliconwithapurityofonly98%nothighenoughforitsmostimportantuseinsiliconchips.High
puritysiliconisobtainedbyreductionofSiCl4,itselfpreparedbyreactionofSiO2andcokeinthepresenceofCl2at
hightemperature:

TheSiCl4isdistilledandthenreducedwithmagnesiumtogivesiliconandMgCl2,whichisremovedbywashingwith
water:

Thesiliconispurifiedfurtherbyzonerefining,aprocessdepictedinfigure14.6.Arodofimpuresiliconismeltedand
resolidifiedmanytimesbyaheatingcoilthatpassesbackandforthalongtherod.Duringthisprocess,impurities
remainpreferentiallyintheliquidphase,whichfloatstothetop,yieldingsolidsiliconinthelowerpartoftherod
containinglessthan1partperbillionofimpurities.

FIGURE14.6Inzonerefining,arodofimpuresiliconpassesalongaheatingcoil.Theimpuritiesconcentrateinthemolten
zone,leavingbehindsolidmaterialthatisofhigherpurity.Repeatedpassagethroughthecoilmovesthe
impuritiestotheendoftherod.

Germaniumisfoundinsomesulfidemineralsandzincores,andincoal.Likesilicon,germaniumfindsextensiveuse
insemiconductors,andtheultrapureelementisalsopreparedbyzonerefining.Germaniumcrystallisesasgreywhite
crystalswiththesamestructureasdiamond,butthesearebrittleandnowherenearashard.Themainusesof
germaniumanditscompoundsareinfibreoptics,infraredopticsandsolarcells.Onreductionbysodiuminliquid
ammonia,germanium,likebothtinandleadbelowitintheperiodictable,formsinterestingpolyatomicanions
examplesoftheseincludeGe42,Ge94andGe92.

TinisfoundinnatureasSnO2inthemineralcassiteriteandthiscanbereducedtothemetalusingcharcoalathigh
temperature.Historically,tinwasusedwidelyasaconstituentofmetalalloys,ofwhichbronze,solderandpewterare
commonexamples.Bronze(figure14.7)isanalloyofcoppercontainingapproximately20%tinandsmalleramounts
ofzinc.Pewter(figure14.8)isanotherCuSnalloythatcontainstinasthemajorcomponent(=85%),withroughly
equalportionsofcopper,bismuthandantimony.Solderconsistsof67%leadand33%tin.

FIGURE14.7Bronze.

FIGURE14.8Pewter.

Becauseofitsrelativelylowmeltingpoint(232C)andgoodresistancetooxidation,tinisusedtoprovideprotective
coatingsonmetalssuchasironthatoxidisemorereadily.Tincansareactuallyironcansdippedinmoltentinto
provideathinsurfacefilmoftin.MetalsthataresoftLewisacids,suchascadmium,mercuryandlead,areextremely
hazardoustolivingorganisms.Tin,incontrast,isnot.Onereasonisthattinoxideishighlyinsoluble,sotinisseldom
foundatmeasurablelevelsinaqueoussolution.Perhapsmoreimportantly,thetoxicmetalsgenerallyactbybindingto
sulfurinessentialenzymes.TinisaharderLewisacidthantheotherheavymetals,soithasaloweraffinityforsulfur,
arelativelysoftLewisbase.

Tinholdstherecordforthegreatestnumberofstableisotopesofanyelement(10),andthisisprobablynotunrelated
tothefactthatthetinnucleuscontains50protonsaswewillseeinchapter27(p.1163),50isamagicnumber.

LeadisoneoftheoldestknownmetalsandwasusedextensivelyinpipesintheRomanEmpireinfact,ourmodern
wordplumbingderivesfromtheLatinwordforlead,plumbum.ItisfoundinnatureprimarilyasPbSinthemineral
galena,andthisisconvertedtotheelementfirstbyroastinginairtoformPbO,andsubsequentreductionwith
charcoal:

Leadisasoftbluegreymetal,andbothitanditscompoundsareappreciablytoxictohumans.Indeed,theextensive
useofleadbytheRomansincookinganddrinkingvesselshasledsometospeculatethatleadpoisoningwasafactor
inthedeclineoftheRomanEmpire.Leadcompoundswereusedinhugequantitiesinthetwentiethcenturyas
additivesinbothpetrolandpaintthankfully,theincrediblefollyofthishasfinallybeenappreciatedandsuch
applicationsarenowrare.Themajoruseofleadcurrentlyisinbatteries.

Group15

Group15comprisestwononmetals,twometalloidsandametal.Elementalnitrogenmakesup78%(byvolume)ofthe
airaroundus.ItexistsasthediatomicmoleculeN2,inwhichthetwonitrogenatomsareheldtogetherbyatriplebond
ofconsiderablestrength(942kJmol1,seeworkedexample5.10,p.204).Thismakesthemoleculeunreactiveunder
ambientconditions,afactforwhichhumankindcanbeextraordinarilygrateful,giventhatthismeansitdoesnot
instantlyreactwiththe21%byvolumeofoxygenintheatmosphere.However,itslackofreactivityalsomeansthat,
inorderforittobeconvertedintocompoundsthatcanbeutilisedbylivingsystems,naturehashadtodevelopan
extremelycomplexenzymecallednitrogenase,generallyfoundinlegumes,tocatalysetheconversionofN2to
ammonia.Despitethebesteffortsofsomeofthefinestscientistsovermanyyears,wehaveyettobeabletoreplicate
thisprocessusefullyinthelaboratory,andinordertopreparenitrogenbasedfertilisers,weusetheratherlesselegant
HaberBoschprocess,inwhichN2andH2areheatedtogetherathighpressureoveranironcatalyst.Theimportance
ofthisprocessisshownbythefactthatitconsumesanestimated12%oftheworld'senergysupplyeachyear.
Elementalnitrogenfindsextensiveuseinitsliquidformasacoolantliquidnitrogen(figure14.9)boilsat196Cat
atmosphericpressure.
 FIGURE14.9Liquidnitrogenboilsat196C.

PhosphoruswasisolatedfromthedistillationofurinebyHennigBrandin1669,makingittheelementhavingthe
earliestauthenticateddateofdiscovery.Itexistsasanumberofdifferentcolouredallotropes,themostcommonbeing
white,redandblack.Itis,likenitrogen,essentialtolife,beingaconstituentofthebiologicallyimportantmolecules
DNA,RNA,andadenosinemono,diandtriphosphate.Perhapssurprisinglythen,purewhitephosphorusishighly
toxic,withadoseofonly50mgconsideredlethal.Modernproductionofelementalphosphorususesatechnique
similartothemetallurgicalprocessesdescribedinchapter13.Apatiteismixedwithsilicaandcokeandthenheated
stronglyintheabsenceofoxygen.Undertheseconditions,cokereducesphosphatetoelementalphosphorus,thesilica
formsliquidcalciumsilicate,andthefluorideionsinapatitedissolveintheliquidcalciumsilicate.Thereactionsare
notfullyunderstood,butthestoichiometryforthecalciumphosphatepartofapatiteisasfollows:

Elementalphosphorusisagasatthetemperatureofthereaction,sotheproductdistilsoffalongwithcarbon
monoxide.Whencooledtoroomtemperature,P4condensesasawaxywhitesolid.

WhitephosphorusconsistsofindividualP4moleculeswiththefouratomsatthecornersofatetrahedron.Eachatom
bondstothreeothersandhasonelonepairofelectrons,givingatotaloffourelectronpairsaroundeachPatom
(chapter5).However,thetriangulargeometryofthefacesofthetetrahedronconstrainsthebondanglesintheP4
tetrahedronto60,farfromtheoptimal4coordinategeometryof109.5.Asaresult,P4ishighlyreactive.Samplesof
whitephosphorusarestoredunderwaterbecauseP4burnsspontaneouslyinthepresenceofoxygen(figure14.10).
TheglowthatemanatesfromP4asitburnsinthedarkledtoitsname(fromtheGreekphos,meaninglight,and
phoros,meaningbringing).
 FIGURE14.10Thestrained60bondanglesintetrahedralP4 makewhitephosphorushighlyreactive.Thisformofthe
elementmustbekeptoutofcontactwithair,inwhichitburnsspontaneously.

HeatingwhitephosphorusintheabsenceofoxygencausesthediscreteP4unitstolinktogether,givingachemically
distinctelementalform,redphosphorus.Asfigure14.11shows,onePPbondofeachtetrahedronbreakstoallow
formationofthebondsthatlinktheP4fragments.Thebondanglesthatinvolvethelinksaremuchcloserto109.5,
makingredphosphoruslessstrainedandlessreactivethanwhitephosphorus.Redphosphorusundergoesthesame
chemicalreactionsasthewhiteform,buthighertemperaturesarerequired.Inaddition,redphosphorusisessentially
nontoxic,soitiseasierandsafertohandle.
 FIGURE14.11RedphosphorusconsistsofchainsofP4 tetrahedralinkedthroughPPbonds.

Anotherstableformoftheelementisblackphosphorus,whichcanbepreparedbyheatingredphosphorusunderhigh
pressure.TheblackformcontainschainsofP4unitscrosslinkedbyPPbonds,makingthisformevenmore
polymerisedandlessstrainedthanredphosphorus.Workedexample14.1exploresanotherdifferencebetweenthe
elementalformsofphosphorus.

WORKEDEXAMPLE14.1

Meltingpointsofphosphorus
Themeltingpointofwhitephosphorusis44.1C.Incontrast,redphosphorusremainsasolidupto400C.
Accountforthislargedifferenceinmeltingpoint.

Analysis

Asdescribedinchapter7,meltingpointsofsolidsmaydependonbothcovalentbondsandintermolecular
forces,sowemustexplainthemeltingpointdifferencewithreferencetothebondingdifferencesbetween
thetwoforms.

Solution

WhitephosphorusconsistsofindividualP4molecules.Becausetherearenopolarbonds,themoleculesare
heldinthesolidstatebydispersionforcesonly,anditwouldbeexpectedthatwhitephosphoruswould
havearelativelylowmeltingpoint.RedphosphorusismadeoflongchainsofP4groups,eachofwhichis
heldtogetherbycovalentPPbonds,asshowninfigure14.11onthepreviouspage.Thus,red
phosphorusconsistsofmacromoleculesheldtogetherbydispersionforces.Tomelt,redphosphorusmust
breaksomechemicalbonds.Bondbreakingrequiresmuchmoreenergythantheenergyneededto
overcomedispersionforces,givingredphosphorusthehighermeltingtemperature.

Isouranswerreasonable?

Themolecularmodelsinfigures14.10and14.11showthatwhitephosphorusisamolecularsolid,whereas
redphosphorusisintermediatebetweenmolecularandnetwork.Thiscorrelateswellwiththemelting
points.

PRACTICEEXERCISE14.1
Predictwhetherblackphosphorusmeltsatahigher
orlowertemperaturethanthewhiteandredforms,
andrankthethreeformsofelementalphosphorus
inorderofincreasingdensity,givingareasonfor
yourranking.

Arsenicispossiblybestknownamongthegeneralpublicforbeingapoison.Inadditiontoitsmanyhumanvictims,it
alsohasbeenrecentlyfoundtohaveaccountedfortheearlydemiseofPharLap,thefamousNewZealandbornand
AustraliaraisedracehorseanalysisofhairsfromPharLap'smaneusingsophisticatedXraybasedspectroscopic
techniquesshowedtheingestionofarsenicwhilethehorsewasstillalive.Elementalarsenicexistsasthegrey
allotropicformatroomtemperatureandpressure,whileatleasttwootherallotropesareknown.Itisoftenfoundin
combinationwithsulfurinavarietyofminerals,withFeSAs(arsenopyrite)beingthemostcommonheatingthisinthe
absenceofairgivesthepureelement.Arguablythemostimportantuseofarsenicisinthesemiconductorgallium
arsenide(GaAs),whichshowspropertiessimilar,andinsomecasessuperior,tosiliconindiodesandsolarcells.

Antimonycompoundshavebeenknownforover2000years,withSb 2S3(stibnite)beingusedasbothamedicineand
ablackeyemakeupinancientEgypt.Theelementisagreymetallicsolidatambienttemperaturesandatleastfour
otherallotropesareknown.Stibniteisthemostimportantoreofantimony,andthepureelementisobtainedfrom
eitherroastinginairandsubsequentreductionoftheresultingSb 2O3withcoke,ordirectreductionbyFe.Antimonyis
usedprimarilytohardentheleadusedincarbatteries,whilesomeantimonycompoundshavebeenfoundtobe
effectiveagainstparasitebornetropicaldiseases.

Bismuthisprimarilyobtainedasabyproductofthesmeltingofleadandcopper.Theelementisasoftgreymetal
havingarelativelylowmeltingpoint(271C)andahighboilingpoint(1564C).Theseproperties,coupledwiththe
lowneutronabsorptioncrosssectionoftheelement,makeitusefulasacoolantinnuclearreactors.Bismuthisoneof
thefewsubstances(waterbeingthebestknown)thatexpandsonfreezing.Theelementisfindingincreasinguseasa
nontoxicsubstituteforlead,mostnotablyinshotgunpelletsandleadfreesolders.Thebiologicalimportanceof
bismuthcompoundshaslongbeenknown,particularlyinthetreatmentofgastrointestinalproblemsPeptoBismol
containsthebismuthcompoundbismuthsubsalicylate(figure14.12)asitsactiveingredient.

FIGURE14.12 (a)Thestructureofbismuthsubsalicylate,theactiveingredientin
(b)PeptoBismol.

Group16

Theabilityofphotosyntheticbacteriaovertwobillionyearsagotoproduceelementaloxygenisresponsibleforlifeon
Earthevolvingaswenowknowit.OxygenanditscompoundsareubiquitousthroughouttheEarth'satmosphere,crust
andbiosphere,anditisthethirdmostabundantelementintheuniverse,afterhydrogenandhelium.Itformsstable
compoundswiththemajorityofelementsintheperiodictable,theonlyexceptionsbeingsomeoftheelementsin
group18.Thepuregaseouselementiscolourless,odourlessandtasteless,whiletheliquidformexhibitsapaleblue
colour.ThefirstpersontoisolateandstudyoxygengaswastheSwedishpharmacistCarlWilhelmScheeleoverthe
period177173,buttheEnglishparttimescientistJosephPriestley,whoisolatedoxygenin1774,isusuallycredited
asthediscovererofoxygen.ThisisbecauseScheeledidnotpublishhisworkuntil1777andwasthusbeateninto
printbyPriestleybysometwoyears.AntoineLavoisier(chapter1,p.3)wasalsoinstrumentalinearlyworkon
oxygen,especiallyinrecognisingitsimportanceincombustionreactions.Ozone,O3,isanallotropeofoxygenit
occursintheatmosphere,andalayerinthestratosphereactsasashieldforpotentiallydamagingultravioletradiation
fromtheSun(pp.6667).Itisalsoanexcellentoxidisingagentandisincreasinglybeingusedinplaceofchlorine
basedoxidantsinthepulpandpaperindustry,aswellasforthetreatmentofdrinkingwater.

Sulfurisencounteredmostofteninsulfidemineralssuchaspyrite,FeS2,molybdenite,MoS2,chalcocite,Cu 2S,
cinnabar,HgS,andgalena,PbS.ItisalsopresentinhugeamountsasH2Sinnaturalgasandinsulfurcontaining
organiccompoundsincrudeoilandcoal.Inaddition,sulfurisfoundinabundanceasthepureelement,particularly
aroundhotspringsandvolcanoesandincappinglayersovernaturalsaltdeposits.Referencestosulfuroccur
throughoutrecordedhistory,datingbackmorethan3500years.Underambientconditionselementalsulfurisayellow
crystallinesolidthatconsistsofindividualS8molecules.Asshowninfigure14.13,theeightatomsineachmolecule
formaringthatpuckersinsuchawaythatfouratomslieinoneplaneandtheotherfouratomslieinasecondplane.
Therearealargenumberofsulfurallotropeshavingcyclicstructures,rangingfromS6toS20,whilesomecatenated
formsarealsoknown.

FIGURE14.13Undernormalconditions,sulfurformsyellowcrystals.ThecrystalsconsistofindividualS8 molecules,withthe
eightsulfuratomsofeachmoleculearrangedinapuckeredring.

Themajorpresentdaysourceoftheelementisfromhydrogensulfideproducedasabyproductofoilandgas
refining.Manypetroleumandnaturalgassuppliescontainsomesulfurupto25%insomecases.Besidesbeing
undesirableinthefinalproducts,sulfurpoisonsmanyofthecatalystsusedinoilrefininghence,itmustberemoved
fromcrudepetroleumasafirststepintherefiningprocess.About90%ofworldoutputofsulfurisconvertedto
sulfuricacid,themostproducedindustrialchemicalworldwide,andmorethan60%ofthatsulfuricacidisusedto
extractphosphoricacidfromphosphatemineralstopreparefertilisers.Thismajoruseexploitsthefactthatsulfuric
acidistheleastexpensivestrongBrnstedLowryacid.Inadditiontoprotonatingthephosphateanions,sulfuricacid
sequestersCa2+asCaSO4,awastebyproductoftheprocess.

Seleniumisarareelement,andminingitdirectlyisnoteconomic.Itisthereforeobtainedasabyproductfromthe
electrolyticpurificationofcopper(pp.5878).Atleastsixallotropesareknown,fourofwhicharered,onemetallic
grey(thestableformunderambientconditions),andoneblack.ThreeoftheredallotropesconsistofSe8rings,thus
mirroringthestructureofelementalsulfur.Seleniumisatraceelementbutistoxicinhighdoses.Itisincorporatedinto
proteinsviaselenocysteine(figure14.14),amodifiedaminoacidinwhichthesulfuratomofcysteine(p.1057)has
beenreplacedbyaseleniumatom.Theresultingproteinsact,amongotherthings,toreducereactiveoxygenspecies
andtoregulatethyroidhormones.Theglassindustryisthemajoruserofseleniumitisusedtoremovethegreentint
inglass,causedbyiron,andalsotoabsorbsolarradiationinplateglass.Seleniumalsofindsusesinphotocopiers
beingasemiconductor,itcanbeusedasaphotoreceptortoobtainthelatentimage,whichisthendevelopedbythe
toner.
 FIGURE14.14Structureoftheaminoacidselenocysteine.

Tellurium,likeselenium,isobtainedpredominantlyfromtheelectrolyticpurificationofcopper.Thepureelementis
silverwhitewithametalliclustreandisratherbrittle.Incontrasttothetwoelementsdirectlyaboveitintheperiodic
table,thestableformunderambientconditionsdoesnotconsistofeightatomringsrather,itcompriseshelicalchains.
Themajoruseoftelluriumisasanadditivetoanumberofmetalstoimprovetheirmachiningcharacteristics.Itisalso
startingtofindextensiveuseinCdTe(cadmiumtelluride)solarcells,andalsoinhighspeedrewriteablephasechange
memory(PCM)chips.Compoundsoftelluriumareconsideredmoderatelytoxic,andingestionofeventinyamounts
leadstogarlicsmellingtelluriumbreathfromtheformationofdimethyltellurium(Me2Te)inthebody.Theelement
formsaremarkablevarietyofpolyatomiccationsandanionsexamplesincludeTen2(=25,7,8),Te63,Te42+,
Te62+,Te64+,Te84+andTe102+.

PoloniumwasdiscoveredbytheCuriesin1898andwasnamedafterMarie'shomecountryofPoland.Allisotopesof
poloniumareradioactiveandthis,coupledwithitsverylowabundance(estimatedat0.1mgpertonneofpitchblende,
anoreofuranium),thereforelimitstheusefulnessoftheelement.Inadditiontoitsradioactivity,poloniumistoxicin
thesamewaythatotherheavymetalssuchasleadandmercuryaretoxic.In2006,theRussianjournalistAlexander
Litvinenkowasmurderedusingwhatwasthoughttobeaslittleas1mgoftheisotope210Po.Theintenseenergyofthe
radiationemittedbypoloniumcanbeappreciatedbytheobservationthatasampleofaround0.5gofthepuremetal
willheatitselftoover500C.

Group17

Elementalfluorine,F2,isapalegreengasofextraordinaryreactivity.ItreactsdirectlywithallelementsexceptO2,N2,
He,Ne,KrandAr.CompoundsoffluorinewithallelementsexceptHeandNeareknown.Itdoesnotexistinnature
asthegaseouselement,butasthefluorideion,predominantlyinmineralssuchasfluorspar,CaF2,andcryolite,
Na3AlF6.BecauseF2isanextremelypowerfuloxidisingagent( ,table12.1,p.510),theelement
cannotbepreparedbychemicaloxidationofFandisthereforeobtainedbyelectrolysisofKF2HF,asdepictedin
figure14.15here,KFactsasanelectrolyte.
 FIGURE14.15Schematicviewofanelectrolyticcellusedfortheproductionofmolecularfluorine,showingthemolecular
speciesinvolvedintheredoxreactions.

OverhalfoftheF2producedannuallyisusedtoprepareuraniumhexafluoride(UF6),acompoundusedinthe
separationofthefissileisotope235U(p.1176)fromthepredominant238Uisotopeforuseinnuclearpowerstations.As
wewillseeonpp.7989,theintroductionoffluorineatomsintoorganicmoleculesgivestheminterestingandunusual
properties,themostnotableexampleofthisbeingTeflon,thenonstickpolymerderivedfromtetrafluoroethene,and
suchmoleculesrepresentanimportantuseoffluorine.

Thestableformofchlorinethatexistsunderambientconditionsisthediatomic,palegreengasCl2,but,liketheother
membersofgroup17,itisfoundinnaturepredominantlyasthehalideion,inthiscaseCl.Chlorineisanimportant
industrialchemical,andsomeindustrialapplicationsofchlorinederivativesareoutlinedintable14.1.
TABLE14.1 Majorusesofchlorine
Reactant Intermediate Finalproducts
Organicreagents
benzene chlorobenzenes plastics,dyestuffs
butadiene chloroprene neoprene(chlorinatedrubber)
ethene chloroethenes plastics(PVC),solvents
methane chloromethanes silicones
Inorganicreagents
CO COCl2 plastics(polycarbonate)
NaOH NaOCl bleaches,disinfectants
phosphorus PCl3,POCl3 pesticides,flameretardants
rutile(TiO2ore) TiCl4 paintpigment(pureTiO2)

Thestartingmaterialforallindustrialchlorinechemistryissodiumchloride,obtainedprimarilybyevaporationofsea
water.Likefluorine,chemicaloxidationofthisisnotfeasiblebecauseofthestronglyoxidisingnatureoftheparent
halogen,andsochloridemustbeoxidisedelectrolyticallytoproducechlorinegas.Thisiscarriedoutonanindustrial
scaleusingthechloralkaliprocess,whichisshownschematicallyinfigure14.16.Aswithallelectrolyticprocesses,
theenergycostsareveryhigh,buttheprocessiseconomicallyfeasiblebecauseitgeneratesthreecommercially
valuableproducts:H2gas,aqueousNaOHandCl2gas.

FIGURE14.16Schematicviewoftheelectrolyticchloralkaliprocessshowingthemolecularspeciesinvolvedintheredox
reactions.

Themajoruseofchlorineisintheproductionofchlorinecontainingorganiccompoundssuchas1,2dichloroethane
andchloroethene(vinylchloride)fortheproductionofPVC(polyvinylchloride).Itisalsowidelyusedinthepaper
industry,asanoxidisingagenttobleachbothpulpandpaper,andalsoasableachingagentfortextiles.Molecular
chlorineisusedextensivelyasapurifyingagentforwatersuppliesbecauseitdestroysharmfulbacteria,producingCl
intheprocess.DissolutionofCl2inwaterresultsinformationofhypochlorousacid,HOCl,accordingtotheequation:

Thehypochloriteion,OCl,theconjugatebaseofhypochlorousacid,istheactiveingredientinmostbleaches.This
ionoxidisesmanyorganicmaterialsthatarecoloured,breakingthemintosmaller,colourlesssubstancesthatareeasily
removedbydetergents.Likealltheotherhalogens,molecularchlorineistoxic,anditholdsthedubiousdistinctionof
beingthefirstchemicalwarfareagenttobeusedonalargescale.DuringWorldWarI,nearly6000cylindersof
chlorinewereusedattheSecondBattleofYpres,on22April1915.

WORKEDEXAMPLE14.2

Disproportionation
Show,byassigningoxidationnumberstoallchlorinecontainingspeciesintheequation:

thatthisisanexampleofadisproportionationreaction.Useelectrochemicaldatafromchapter12to
determine forthisprocess,andcommentonitsspontaneityunderstandardconditionsinbothacidic
([H+]=1.0M)andbasic([OH]=1.0M)solution.

Analysis

Aswesawinchapter13,disproportionationisthesimultaneousoxidationandreductionofasinglechemical
species.Inthiscase,molecularchlorine,Cl2,isthespeciesundergoingdisproportionation.Assignoxidation
 numbersusingtherulesfromchapter12(p.491),andcalculate using ,asoutlinedin
chapter12.

Solution

TheoxidationnumberofchlorineinCl2is0,asisthecaseforanyfreeelement.

TheoxidationnumberofchlorineinHOClis+1.Thecompoundisneutral,Hhasanoxidationnumberof+1,
andOhasanoxidationnumberof2.Therefore,Clmusthaveanoxidationnumberof+1sothatthesumof
alloxidationnumbersinthemoleculeiszero.

TheoxidationnumberofchlorineinClis1,thesameasthechargeontheion.

ThuswecanseethatCl2,inwhichtheoxidationnumberofchlorineiszero,isbeingconvertedtospecies
withalower(Cl)andhigher(HOCl)oxidationnumberforchlorinethis,therefore,isanexampleof
disproportionation.

Ifweassumethatreductionoccursattherighthandelectrodeofagalvaniccell,thenwecalculate as
follows(datafromtable12.1,p.510):

Dividingthisby2gives:

Thus,understandardconditionsinacidicsolution,thisreactionisnotspontaneous.

Inbasicsolution,thereactionsareasfollows:

Dividingthisby2gives:

Knowingthat ,wecanthencalculate as:

Thusunderstandardconditionsinbasicsolution,thisreactionisspontaneous.

Recallfromourdiscussiononpp.35960thatapositivevalueof (whichcorrespondstoanegative
valueof )doesnotmeantheforwardreactiondoesnotoccuratallitmerelymeansthatitneverproceeds
tosuchanextentthatallproductswillbepresentat .Thus,dissolutionofCl2in1.0MH3O+willresultin
theformationofsmallamountsofHOClandCl.However,theforwardreactionismuchmorefavouredin
basicsolution,asevidencedbyitslargepositivevalueof .

Bromineisadensedeepredliquid,oneofonlytwoelementsontheperiodictablewhichexistasaliquidunder
ambientconditions(theotherismercury).AsBr2isaweakeroxidisingagentthanCl2,chemicaloxidationofBris
feasibleand,indeed,Br2ispreparedonanindustrialscalebytheoxidationofBrwithCl2.Brisfoundprimarilyin
seawater,saltlakesandbrinedeposits.ThemostwellknownsourceisprobablytheDeadSea,ontheborderofIsrael
andJordan.Brominefindsitsmajoruseinflameretardants,accountingforover50%oftheworld'sannual
production.Likechlorine,itisalsousedinwaterpurification.Beforetheadventofdigitalcameras,silverbromidewas
usedextensivelyasthelightsensitivematerialinphotographicfilm.Bromomethane(methylbromide)isusedinlarge
quantitiesasapesticidehowever,itsuseisdecreasingasitisrecognisedtobeanozonedepletingchemical.

Iodine,likebromine,ispreparedbyoxidationofthehalideionbyCl2.Itisadeeppurplesolidwithasignificant
vapourpressure,andasampleofI2inaclosedcontainerwillbeseentohaveapurplevapouraboveit(seefigure
14.17).Therearenomajorindustrialusesofiodine,butitisincreasinglybeingusedasanalternativetochlorinein
watertreatment,especiallyinAustralia.Iodineisatraceelement,beingaconstituentofthyroxine(p.1058),a
hormonewhichregulatestherateofcellularuseofoxygen.Iodinedeficiencywashistoricallymanifestedbyagoitre,
aswollenthyroidgland,butthecompulsoryadditionofsmallamountsofNaItotablesalt(in1924,NewZealandwas
oneofthefirstcountriesintheworldtodothis)hasallbuteliminatedthisindevelopedcountries.However,itisalso
nowknownthatiodinedeficiencycanleadtodevelopmentaldisabilitiesandironicallythecurrentfadforusing
naturalsaltcontainingnoiodineappearstohavecontributedtoiodinedeficiencyagainbeingaprobleminboth
AustraliaandNewZealand.Forthisreason,bakersinbothcountrieshavebeenrequiredtouseiodisedsaltintheir
productssince2009.

FIGURE14.17Iodinesublimesatatmosphericpressure,andpurpleiodinevapourcanbeseenaboveasampleofsolid
iodine.

AstatineoccursintinyamountsonEarthowingtoitspresenceinthreeradioactivedisintegrationseries(p.1170)and
theextremelyshortlifetime(8.3h)ofitslongestlivedisotope.Allofitsisotopesareradioactive.Itcompeteswith
franciumforthedistinctionofbeingtherarestelementintheEarth'scrust.
Group18

TherewasnoplaceinMendeleev'soriginalperiodictable(chapter1,p.14)fortheelementsofgroup18,simply
becausenoneofthemhadbeendiscoveredatthattime.Theywereoriginallycalledthenoblegases,astheywere
thoughttobechemicallynonreactive,buttheisolationofthefirstnoblegascompoundin1962showedthemtohave
significantreactivityunderthecorrectconditions.Theyallexistasmonatomicgasesunderambientconditions.

Althoughheliumisthesecondmostabundantelementintheuniverse,itispresentonEarthinverylow
concentrations,owingtothefactthatitislightenoughtoescapetheEarth'sgravitationalpull.Heliumisobtained
primarilyfromnaturalgasdeposits,havingbeenformedasaresultofradioactivedecayof238U(p.1170),andisused
extensivelyincryogenic(verylowtemperature)applications.Heliumhasthelowestboilingpointofanyelementit
condensestoaliquidat4.2K.Severalmaterialsbecomesuperconductingatverylowtemperaturesandliquidhelium
isusedtoobtaintheseconditions.Ofparticularinteresttochemistsistheuseofliquidheliumtocoolthe
superconductingmagnetsusedinNMRspectrometers(p.885).Heliumisunusualinthatitcannotbesolidifiedat
atmosphericpressure.Italsoexhibitsaphenomenoncalledsuperfluiditywhenitiscooledbelow2.17Kthismeans
theliquidhaszeroviscosityandwillcoattheentiresurfaceofanycontainerinwhichitisplaced.Thesuperfluidalso
showsextraordinarilyhighthermalconductivity,greaterthanthatofcopper.

Neonisfoundintheatmosphereatconcentrationsof1partin65000,anditisusuallyobtainedfromthefractional
distillationofliquidair.Thepassageofanelectricdischargethroughthegascausesabeautifulorangeredglow
(figure14.18),duetoalargenumberofelectronictransitionsthatgiverisetomanyatomicemissionlinesaround600
nm(figure4.20,p.120).ThiseffectwasusedbyGeorgesClaudeintheconstructionofthefirstneonlightin1910.
Theemissionpropertiesofneonarealsousedinheliumneon(HeNe)laserstheseemitredlightofwavelength632.8
nm.
 FIGURE14.18Emissionofphotonsfromexcitedneonatomsgivesabrilliantredlight.

Argonisthemostabundantofthegroup18elements.Itisthethirdmostabundantcomponentofair(0.934%by
volume)afternitrogenandoxygen,andisobtainedfromthissource.Itsrelativeprofusionandlackofchemical
reactivitymakeittheinertgasofchoiceinapplicationswhichrequireexclusionofoxygenthatarecarriedoutunder
conditionswherenitrogenmightreact.Aswewillseeinchapter27(p.1172),theargonisotope40Arisimportantin
thedatingofrocks.Althoughitisconsideredchemicallyinert,thecompoundHArFhasbeenrecentlyreported
however,itisstableonlyinamatrixoffrozenargonbelow27K.

chemicalConnections

ChemicalConnectionsCompoundsofgroup18elements

Priorto1962,mostchemiststhoughtthatthegroup18elementswerechemicallynonreactiveandwouldnot
formcompoundswithanyelementontheperiodictable.However,theworkofNeilBartlett,ayoung
BritishchemistworkingattheUniversityofBritishColumbiainVancouverintheearly1960s,changedthis
misconceptionforever.

Bartlett'soriginalinterestwasnotinthegroup18elementsbut,rather,incompoundsformedbetween
fluorineandplatinum.AsagraduatestudentinEngland,hehadisolatedanunusualredsolidwiththe
formulaPtF6O2whilestudyingthereactionsofbothmetallicplatinumandsomeplatinumcompoundswith
elementalfluorineinthepresenceofsmallamountsofoxygen.WhenhemovedtoVancouverhesetabout
tryingtocharacterisethisfurther.Heeventuallyshowed,usingavarietyoftechniques,thatthecorrect
formulaofthissolidwasO2+PtF6.ThiswasthefirstexampleofacompoundcontaininganoxidisedO2
moleculeweusuallythinkofO2asbeinganexcellentoxidisingagent,andthereforeitiseasilyreduced.
OxidisingO2shouldbeextremelydifficultandwouldrequireanoxidisingagentofenormousstrength.As
oneofthewaysinwhichhehadpreparedthesolidinvolvedthereactionofthegasPtF6withO2,Bartlett
realisedthatPtF6mustbeanexceptionallygoodoxidisingagent.IsolationofO2+PtF6fromthisreactionwas
anachievementinitself,butevenmoreremarkableresultslayinstore.

Whilepreparingforanundergraduatelecture,Bartletthappenedtolookatatableofionisationpotentials
andfoundthattheenergyrequiredtoremoveanelectronfromXe(g)(1170kJmol1)wasessentiallyequal
tothatrequiredforO2(g)(1177kJmol1).Toputthesenumbersinperspective,recallfromchapter5that
theN Ntriplebond,oneofthestrongestknowncovalentbonds,hasabondenergyof942kJmol1
removinganelectronfromeitherO2orXeisreallydifficult!BartlettthereforereasonedthatifPtF6wasa
strongenoughoxidisingagenttooxidiseO2,itshouldalsobeabletooxidiseXeandpossiblyforma
compoundwiththisgroup18element.Suchreasoningwentagainstallperceivedchemicalwisdomofthe
 timebut,nevertheless,BartlettsetupasimpleapparatusinwhichdeepredgaseousPtF6andcolourlessXe
atroomtemperaturewereseparatedbyasealwhenthesealwasbroken,ayellowsolidformed
immediately,andchemicalhistorywasmade(figure14.19).

FIGURE14.19When
(a)platinumhexafluoride,aredgas,isallowedtomixwithalargemolarexcessofxenon,the
immediatelyformedproductis
(b)ayellowsolidwiththecompositionXePtF6 ,thefirstrecognisedcompoundofanoblegas

Eventoday,theexactidentityoftheyellowsolidisnotcertain.Originally,itwasthoughttobeXe+PtF6,by
analogywiththeO2+compound.However,itnowappearsthatthecompoundisbetterdescribedas
[XeF]+[PtF5].Regardless,Bartlett'sexperimentinspiredchemistsaroundtheworldtostudythereactivityof
thegroup18elementswithstrongoxidisingagents.Thefirstkryptoncompoundwasreportedin1963,
whilethefirstxenonoxide,XeO3,wasalsopreparedthatyear.Bartlettwaspossiblythefirstpersonto
experiencethehighlyunstablenatureofxenonoxideswhenwhatwasthoughttobeasampleofXeO2
explodedinaquartztubewhilehewasnotwearingeyeprotection27yearslater,apieceofglasswas
removedfromhiseye.

Therearenowseveralhundredknowncompoundscontaininggroup18elements,andresearchintotheir
synthesisandpropertiescontinuestothisday.Bartlett'sextraordinarydiscoverychangedchemistry
overnightandforcedchemiststofundamentallyaltertheirideasconcerningreactivitywenownolonger
thinkofgroup18elementsasbeingchemicallyinert.Surprisingly,Bartlett,whodiedin2008,wasnot
awardedtheNobelPrizeforhisachievementhowever,hisnameisimmortalisedineveryinorganic
chemistrytextbookasthemanwhoshowedthatthenoblegasesarenotquitesonoble.

Kryptonhasanabundanceinairaroundonefifththatofhelium.Itsemissionpropertiesmakeitidealforuseinhigh
speedphotographicflashbulbs,asitgivesahighintensitywhitelight,whileitalsofindsuseinkryptonfluoride
(KrF)lasers,whichgiveultravioletlightofwavelength248nm.Kryptonisthefirstofthegroup18elementsthat
showappreciablechemicalreactivitythecompoundKrF2waspreparedin1963bylowtemperature(20K)photolysis
ofamixtureofkryptonandfluorine,anditisstableupto250K.Sincethistime,over30Krcompounds,all
containingKrinthe+2oxidationstateandallofwhichhavekryptonbondedtofluorine,havebeenprepared.

Xenonistheleastabundantofthegroup18elementsfoundintheatmosphere(around0.09partspermillion)butthe
mostchemicallyinteresting.Thefirstxenoncompoundswerepreparedin1962,therebydemonstratingthepotential
reactivityofthesocallednoblegases.ThefluoridesXeF2,XeF4andXeF6areallknown,asaretheoxidesXeO3and
XeO4thelasttwoarebothexcellentoxidisingagentsasevidencedbythefollowingreductionpotentials:
butbotharedangerouslyexplosive.Severalmixedoxofluorideshavebeenprepared,whilecompoundscontainingXe
bondedtoC,N,Clandsometransitionmetalsarealsoknown.Theelementitselfisusedinxenonlamps,lasersandas
ananaesthetic.

Radonisformedfromtheradioactivedecayofradium,whichisinturnformedfrombothuraniumandthorium.All
isotopesofradonareradioactive,andthelongestlivedhasahalflifeoflessthanfourdays.Thismeansthatradon
occursinminisculeamountsonEarth.However,housesconstructedofstone,orbuiltinareascontaininghighlevels
ofuraniumorthoriumminerals,canaccumulatepotentiallydangerousconcentrationsofradonintheirbasements
owingtoitsweightitisaroundeighttimesthedensityofairandkitswhichtestradonconcentrationsinairare
commerciallyavailable.Althoughsomecontroversyexists,recentresearchhasproposedErnestRutherfordasthe
originaldiscovererofradon.

WORKEDEXAMPLE14.3

Lewisstructureofagroup18compound
DrawtheLewisstructureofXeO3,anddeducethemostprobablegeometryofthismolecule.

Analysis

WeobtaintheLewisstructureofthemoleculesusingtherulesinchapter5,andwethenusethese,in
conjunctionwithVSEPRtheory(chapter5)toproposethegeometryofthemolecules.

Solution

Step1:CountthevalenceelectronsXehas8valenceelectronsandeachOatomhas6.
Therefore,thereisatotalof26valenceelectrons.
Step2:Drawthebondingframeworkusingsinglebonds.

Electronsused=6.Therefore,thereare20electronsstilltobeallocated.
Step3:Placethreenonbondingpairsoneachouteratom.

Electronsused=18.Therefore,thereare2electronsstilltobeallocated.
Step4:Assigntheremainingelectronstotheinneratom.

Electronsused=2.Allelectronsarenowassigned.
Step5:Minimiseformalchargesonallatoms.
Theformalchargesoneachatomareasshownbelow.MovingelectronpairstomakethreeXe O
doublebondswillresultineachatomhavingaformalchargeofzero.
 TherearefoursetsofelectronpairsaroundthecentralXeatom,sothestructureofXeO3willbebased
onatetrahedron.Asonlythreeofthesetsareequivalent,themoleculewilladoptatrigonalpyramidal
geometry.

PRACTICEEXERCISE14.2
DrawtheLewisstructuresofXeO4andKrF2,and
determinetheirmostprobablegeometries.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
14.3TheBiogeochemicalCyclesofNature
Havingintroducedthepblockelements,wewillnowconcentrateonwhatarearguablythemostimportantofthese:oxygen,sulfur,
nitrogen,phosphorusandcarbon,whichalllieinthesecondandthirdperiodsoftheperiodictable.Wechoosetheseelements
becauseoftheirimportanceintheEarth'sbiochemicalandgeochemicalsystems.

BondinginthepblockElements
Aswehavealreadyseen,theelementsofthepblockadoptawidevarietyofstructures,andthesecanberelatedtothevalence
electronconfigurationofeachelementandthebondingwhichresultsasaconsequenceofthis.Wefirstintroducedtheconceptofan
octetinchapter5(p.172).Fromwhatwehavelearnedaboutthelackofreactivityofthegroup18elementsinthischapterandtheir
valenceelectronconfigurations(ns2np 6),wecanseethatthepresenceofeightelectronsinthevalenceshellappearstoconfersome
stabilitytoanatom.Thegroup18elementsarereluctanttoundergoreactionwithanybutthemostreactivechemicalreagentsand
existasmonatomicgases.Wealsooftenfindthatanoctetofelectronsaboutanatominamoleculeappearstobeaparticularlystable
energeticsituation,particularlyforelementsinthesecondperiod,andthatthestructuresadoptedbyelementscanberationalisedon
thebasisofthis.Forexample,ifwestartatNe(group18)andgoacrosstheperiodictabletoC(group14),wefindthenumberof
valenceelectronsdecreasesbyoneforeachgroupwetraverse.Therefore,inordertoobtainanoctet,atomsmustshareoneormore
electrons.Thisisillustratedintable14.2.
TABLE14.2 Singleandmultiplecovalentbondinginsecondperiodpblockelements
Element Valenceelectronconfiguration Electronsrequiredforoctet Structure
neon 2s22p 6 0

fluorine 2s22p 5 1

oxygen 2s22p 4 2

nitrogen 2s22p 3 3

carbon 2s22p 2 4

Afluorineatomcanobtainthesingleelectronrequiredforanoctetbysharingasingleelectronwithanotherfluorineatomthisgives
bothatomsashareofanoctet,andsoelementalfluorineexistsasF2,withasingletwoelectronbondbetweentheatoms.Anoxygen
atomrequirestwoelectronsforanoctetandwillthereforesharetwoelectronswithanotheroxygenatom.ThisresultsinO2
molecules,whichcontainadoublebondbetweentheatoms.Thetriplebondinelementalnitrogenresultsfromeachatomsharing
threeelectronswiththeother,togiveN2.Ifthistrendweretobecontinued,wemightexpectcarbontoexistasC2moleculeswitha
quadruplebondbetweentheatoms.However,thisisnotenergeticallyfavourable,andacarbonatominsteadobtainsanoctetby
sharingfourelectronswithfour,threeortwoneighbouringatomstogivealkanes,alkenesandalkynes,respectively.Inspectionof
thefinalcolumnoftable14.2infactshowstherelationshipbetweenthestructuresofF2,O2andN2,andC2H6,C2H4andC2H2,
respectively.WesaythatF2andC2H6areisoelectronic(theycontainthesamenumberofelectrons),asareO2andC2H4,andN2and
C2H2.Themultiplebondsthatholdthelattermoleculestogetherareformedfromoverlapofporbitalsinatypefashion(chapter5,
p.196)thisisfavourableforelementsfromthesecondperiodowingtotheirrelativelysmallsizes,whichallowcloseapproachof
theatomsandcorrespondinglyefficientorbitaloverlap.However,thisisnotthecaseforelementsfromthethirdperiodastheir
atomicradiiarelarger,andbondingbetweentheseisthereforesignificantlyweaker.Therefore,theseelementstendtoadopt
structuresbasedonbondingonlybetweenneighbouringatoms.Thusthestructureofelementalsiliconisthesameasthatof
diamond(pp.2589),witheachSiatomconnectedtofourotherSiatomsphosphorusexistsasbondedP4tetrahedrawitheachP
atombondedtothreeothers(p.605),andsulfuriscomposedofS8ringswithsingleSSbonds(p.607).

Whiletherearesignificantdifferencesbetweenthestructuresofthesecondandthirdperiodelements,thecompoundsthatthese
elementsformwithhydrogenunanimouslyreflectthegrouptowhichtheybelong.Ascanbeseenbelow,thenumberofHatomsin
eachcompoundcorrespondstothenumberofelectronsrequiredbythepblockelementtoobtainanoctet.

Group14 Group15 Group16 Group17 Group18

CH4 NH3 OH2(H2O) FH(HF) Ne

SiH4 PH3 SH2(H2S) ClH(HCl) Ar

Allofthesecompoundscontain4setsofelectronpairsandtherefore,accordingtoVSEPRtheory(p.176),theirstructuresarebased
onthetetrahedron,with0,1,2or3lonepairs.

TheGroup16Cycles

TheOxygenCycle
Wehaveseenearlierinthischapterthattherearetwoallotropesofelementaloxygen:theO2moleculeandtheO3(ozone)molecule.
BotharevitaltolifeonEarth.Therearealsothreereducedformsofoxygen,O2(superoxide),O22(peroxide)andO2(oxide),allof
whichareimportantinlivingsystems.Thesespeciesarerelatedasshownintheoxygencyclebelow:

Theozonemoleculecanbewrittenastworesonanceforms(p.174):

withthetruestructurebeingtheaverageofthese.ThisisreflectedbythefactthattheoxygenoxygenbondlengthsinO3are
identical(128pm)andliebetweenthelengthsoftheOOsinglebondinH2O2(148pm)andtheO OdoublebondinO2(121
pm),therebyattestingtotheirpartialdoublebondcharacter.ThepresenceofalonepaironthecentralOatomresultsinthemolecule
adoptingabentgeometry,withanOOOangleof117.Ozoneispreparedinthelaboratorybythepassageofanelectric
dischargethroughO2,andthepungentodourofozonecanoftenbedetectedinthevicinityofhighvoltageelectricalequipment.In
nature,itisformedintheupperatmospherebytheactionofultravioletradiationfromtheSunonO2.Itisalsoformedatlower
altitudesinphotochemicalsmog,owingtothepresenceofnitrogenoxides(NOx)originatingfromvehicleandindustrialemissions.
TheseareconvertedtoNO2,whichreleasesanoxygenatomonphotolysis,andthisthenreactswithO2togiveO3.Theozone
moleculeishighlyreactive,asmightbeexpectedfromitspositiveGibbsenergyofformation:

anditslargepositivestandardreductionpotential:

Oxygen,O2,isinvolvedinwhatarearguablythetwomostimportantchemicalreactionsinthebiosphere:photosynthesisand
respiration.Inphotosynthesis(p.494),greenplantsusetheSun'senergytoconvertCO2andH2OtocarbohydratesandO2.The
oxidationhalfequationinthisredoxprocessinvolvestheoxidationofH2OtoO2:

andtheelectronsreleasedarethenusedtoreduceCO2to(inthiscase)glucose:

Theoverallreactionthenbecomes:

Giventhat forC6H12O6(s)is911kJmol1,wecanusethedataintable8.6(p.329)toshowthat,fortheoverallreaction,
.ThiscorrespondstoK=210 505at298Kand,intheabsenceofenergyfromsunlight,wewouldexpectthis
reactionnottoproceedatall.

Respirationisessentiallytheoppositeofphotosynthesis.Inthis,glucosereactswithO2togiveCO2andH2O,plusalargeamountof
energywhichcanbeusedbytheorganism.TheoverallreactioninvolvesthefourelectronreductionofO2toH2O,whichdoesnot
occurasasingleprocessbutinaseriesofstepsinvolvingstepwisereductiontoO2andO22.Ofthese,superoxide,O2,istoxicto
cells,andnatureusestheenzymesuperoxidedismutase(pp.57980)tocontroltheamountofthispotentiallydangerousionwithin
anorganism.

WORKEDEXAMPLE14.4
 Electronicstructuresofreducedoxygenspecies

Whatarethebondordersinthesuperoxide,O2,andperoxide,O22,anions?OrderthethreespeciesO2,O22andO2in
orderofdecreasingOObondlength.

Analysis

WewillusetheMOdiagramwederivedfortheO2moleculeinchapter5(figure5.49),addtheappropriatenumberof
electrons,anddeterminethebondorderusingtheequation:

introducedonp.199.

Solution

Usingfigure5.49(p.202),wefindthattheelectronicconfigurationoftheformallydoublebondedO2moleculeis(s)2

(p)2(x)2(y)2 .OneelectronreductiontogiveO2requirestheaddedelectrontobeplacedineither

ofthedegenerateantibonding or orbitals.Thisgivestheelectronicconfiguration(s)2 (p)2(x)2(y)2

.ThebondorderinO2istherefore .

AdditionofafurtherelectrontogiveO22resultsintheelectronicconfiguration(s)2 (p)2(x)2(y)2 ,

inwhichthe*orbitalsarefull.ThebondorderofO22istherefore .

Onthebasisofbondorders,wewouldpredictO22tohavethelongestOObond,followedbyO2andO2.Therespective
OObondlengthsof149pm,128pmand121pmareconsistentwiththismolecularorbitalelectronicdescription.

TheSulfurCycle
Sulfurisanutrientthatisessentialforlife.Itisfoundintheaminoacidscysteine(Cys)andmethionine(Met)(table24.1,p.1057)in
whichthesulfurcontainingfunctionalgroupisathiolandthioether,respectively.Inthesecompounds,sulfurexhibitsitslowest
possibleformaloxidationnumberof2.SulfurasS2isalsofoundcoordinatedtometalionsinavarietyofmetalloproteinsand
metalloenzymes.However,thepresenceofO2inEarth'satmosphereanditsthermodynamicallyfavourablereactionswithmany
sulfurcontainingspeciesmeanthatoxidationisgenerallyafacileprocess,resultingultimatelyincompoundssuchasSO2,SO3and
H2SO4.Thethermodynamicstabilityofthesemoleculesisreflectedintheirvaluesof theseare300.4kJmol1,370.4kJ
mol1and689.9kJmol1forSO2(g),SO3(g)andH2SO4(l),respectively,at25C(appendixA).InvestigationoftheLewisstructures
ofthesemoleculesshowsthatanoctetofelectronsaboutthecentralsulfuratomisnotnecessarilythemostenergeticallyfavourable
arrangement,asisoftenfoundwithelementsfromthethirdperiod.TheSO2moleculeadoptsabentgeometry,withtwoS O
doublebondsandalonepaironthesulfuratom.

TheS Odoublebondsarisefromthenecessitytominimisetheformalchargesontheoxygenandsulfuratoms,anddoingthis
thereforeresultsin10,ratherthan8,electronssurroundingthecentralsulfuratom.AsimilarsituationarisesforSO3,wherethe
Lewisstructureinwhichtheformalchargesareminimisedhas12electronssurroundingtheSatom:
whiletheoptimalLewisstructureforH2SO4alsoplaces12electronsaroundthesulfuratom:

Theabilityofthirdperiodelementsandbelowtobesurroundedbymorethaneightelectrons(sometimescalledexpandingtheoctet)
isattributedbysometoparticipationofdorbitalsonthecentralatominbonding.However,itshouldbenotedthatthisinterpretation
iscontroversialandotherexplanationshavebeenadvanced.

Thebiologicalsulfurcycleisshownbelow.Ascanbeseen,thosesulfurcompoundsimportanttolifetendtocontaintheelementin
thethermodynamicallydisfavourable(inthepresenceofO2)2oxidationstate,andnaturethereforerequiresamethodbywhich
bothsulfurandsulfuroxygencompoundscanbereduced.Thisisachievedbyavarietyofmicroorganismsunderanaerobic
(absenceofoxygen)conditions.Whenmammalsdie,theirreducedsulfurspeciesareoxidisedtosulfatebybiologicaloxidants,and
thisiseitherincorporatedinsulfatemineralsordissolvedinaqueoussolution.Thesameresultcanbeachievedchemicallythrough
theoxidationofsulfurspeciesintheatmospherethedecompositionofplanktonresultsintheformationofvolatiledimethylsulfide,
Me2S,whichescapesintotheatmosphereandisphotochemicallyoxidisedtoSO2.ThisthenreactsfurtherwithO2togiveSO3,and
reactionofthiswithwatergivessulfuricacid,H2SO4,themostimportantcomponentofacidrain.Whilethisprocessoccursnaturally
intheatmosphere,industrialproductionofSO2overthelastcenturyhasincreasedtheamountofH2SO4intheatmospheretothe
pointwhereacidrainhasledtosignificantenvironmentaldamage,mainlyintheNorthernHemisphere.Thesulfurimpuritiesinboth
coalandfossilfuelsinitiallyformSO2oncombustion,andthisisthenconvertedintoH2SO4intheatmosphereviatheaboveroute.
Thereductionofsulfatetosulfiteandeventuallysulfidetakesplaceinplantsandbacteria,whichuseanumberofenzymestoeffect
thisconversion.Theresultingsulfideisthenincorporatedintocysteineandmethionine,andthecyclestartsagain.Itshouldalsobe
notedthatsulfideitselfoccursasaligandintheMS(M=ametalion)centresofanumberofmetalloproteins,mostimportantly
ironsulfurproteins,andappearstoderivefrombreakdownoforganicsulfurspecies,ratherthanbeingdirectlyincorporatedasS2.

TheGroup15Cycles

TheNitrogenCycle
Earlierinthischapter,wediscussedtheextraordinarystabilityoftheN2molecule,aconsequenceofthestrongN Ntriplebond,
andhownatureusesthenitrogenaseenzymetoallowconversionofN2toNH3.Aswithsulfur,thereducedstatesoftheelementare
importantinlivingsystems,andincorporationofnitrogenintobiologicalmoleculessuchasaminoacidsandthenucleicacidbases
(p.1088)generallyoccursthroughNH3.
DecompositionoflivingmatterultimatelyresultsinoxidationofNcontainingmoleculestoNO3inwhichNdisplaysitshighest
oxidationstateof+5.RememberingthatNisasecondperiodelement,itpreferstobesurroundedbyanoctetofelectrons,andthisis
showninthethreepossibleresonancestructuresoftheNO3ioninwhichtheformalchargesontheatomsareminimised.

Nitratecanbereducedbyanaerobicbacteriatovariousnitrogenoxides,andultimatelytomolecularN2.Suchbacteriaessentially
respireusingtheseNcontainingspeciesandareactuallypoisonedbyO2!Theinitialreductionstepinvolvesformationofnitrite
ion,NO2thisisoftenusedasapreservativeinbacon,hamandcornedbeef,althoughtherehavebeensomerecenthealthconcerns
regardingitsuse.Theionadoptsabentgeometry,andtworesonancestructurescanbedrawn.

Subsequentreductiongivesnitricoxide,NO(g),amoleculeofconsiderablebiologicalimportanceasdiscussedintheintroductionto
thischapter.ThisisoneofeightknownneutralcompoundscontainingonlyNandO(theothersareN2O,NO2,NO3,N2O2,N2O3,
N2O4andN2O5).TheLewisstructureofNOisinteresting,as,owingtotheoddnumberofelectronsinanitrogenatom(1s22s22p 3)
andtheevennumberofelectronsinanoxygenatom(1s22s22p 4),themoleculecontainsanoddnumberofelectrons.Thestructure
canbedrawnsuchthatthereisaformaldoublebondbetweenthenitrogenandoxygenatoms,andanunpairedelectronontheN
atom:

althoughitappearsthat,inreality,theunpairedelectronisinvolvedinNObondingtogiveanNObondorderof2.5.Reduction
ofNOyieldsnitrousoxide,N2O,commonlyreferredtoaslaughinggas.Thisnamecameaboutasaresultofanexperimentin1799
bytheEnglishchemistHumphryDavy,whowishedtoshowthattherecentlyprepared(1793)moleculewas,infact,nottoxic.Ina
procedurethatwouldbefrownedupontoday,hesimplyinhaledsmallamountsofthegasmixedwithairandreportednoilleffects.
Whenheeventuallybreathedthepuregas,hereportedahighlypleasurablethrilling,particularlyinthechestandextremitiesand
statedthattrainsofvividvisibleimagesrapidlypassedthroughmymindandwereconnectedwithwordsinsuchamannerasto
produceperceptionsperfectlynovelhehadindirectlydiscoveredtheanaestheticpropertiesofnitrousoxide,althoughitwasnot
usedassuchuntil1844.Themoleculeislinearand,aswesawonpp.1756,threeresonancestructurescanbedrawn,twoofwhich
arethemajorcontributorstotheactualstructure:

Figure14.20showstheelectrondistributionsinNO3,NO2,NOandN2O.
 FIGURE14.20Theelectrondensitydistributionsfor
(a)NO3 ,

(b)NO2 ,

(c)NOand
(d)N2 O.
Redindicatesthehighestelectrondensityandblueindicatesthelowest.

ReductionofN2OgivesN2(g),whichisthenusedasafeedstockinN2fixingbacteriatoformammonia.Theoverallreactionforthis
processis:

wherePiisinorganicphosphate,andMgATPandMgADParethemagnesiumsaltsofadenosinetriphosphate(p.623)andadenosine
diphosphate,respectively.Thisreactioniscatalysedbyavarietyofnitrogenaseenzymes,whicharemetalloenzymescontainingFe,
FeandMo,orFeandV,attheactivesites,andwhichgenerallyoperateunderanaerobicconditions.Althoughtheexactmechanism
ofthereductionprocesshasyettobedetermined,itappearsplausiblethatthereactionproceedsviatwointermediatecompoundsof
nitrogenandhydrogen,diazene,N2H2,andhydrazine,N2H4.

Diazeneisunstable,withalifetimeofonlyminutesatroomtemperature,andcanexistascisandtransisomersowingtotherelative
orientationsofthehydrogenatoms.Purehydrazine,althoughmuchmorestablethandiazeneatroomtemperature,canundergo
violentdecompositionathighertemperaturesandthispropertyhasledtoitsuseasarocketfuel.Inthechemicallaboratory(whereit
isusuallyhandledasanaqueoussolution!),itisanexcellentreducingagent,especiallyinbasicaqueoussolution:

Table14.3showshowtheNOandNNbondlengthsinthenitrogencompoundsdiscussedthusfarcorrelatewiththestructures
wehavedrawn.BothNO3andNO2haveNObondordersgreaterthan1andlessthan2,andthisisreflectedintheirNObond
lengthsof124pm,significantlyshorterthantheNOsinglebondingaseousHNO3(141pm).TheneutralN2Omoleculehasa
slightlyshorterNObondlength(119pm),againconsistentwithabondorderbetween1and2,whereasthe115pmNObond
lengthinNOreflectsabondorderofatleast2.
TABLE14.3 NOandNNbondlengthsinselectednitrogencompounds
Compound NOlength(pm) NNlength(pm)

NO3 124

NO2 124

NO 115
N2O 119 113

N2 110

N2H2 125

N2H4 145

SimilartrendsareseenintheNNbondlengthsofthecompoundsintable14.3.N2H4,withaformalNNsinglebond,displays
thelongestNNdistance(145pm),whichshortensto125pmindoublebondeddiazene.TheresonancestructuresofN2Opredict
anNNbondorderbetween2and3,whichisconsistentwiththestillshorterbondlength(113pm),whiletriplebondedN2
displaystheshortestNNdistance(110pm).

Nitrogenoxides(NOx)resultingfromthecombinationofnitrogenandoxygenathightemperatureininternalcombustionengines
havebeenimplicatedinatmosphericpollution.Ofthesespecies,bothcolourlessNOanddarkbrownNO2causeparticularproblems
involvingozoneNOdestroysO3moleculeswhileNO2,somewhatironically,catalysesformationofO3molecules.Inthelower
atmosphere,NO2canundergophotochemicaldissociationtogivereactiveoxygenatomsandNOtheformercancombinewithO2
moleculestoformO3whilethelatterreactwithoxygentoregenerateNO2.Theoverallprocessisasfollows:

NO2isacatalystinthisprocess,andhenceasinglemoleculeofNO2canpotentiallygenerateanenormousnumberofO3molecules.
WhileO3intheupperatmosphereisbeneficialinthatitabsorbsdamagingultravioletradiationfromtheSun,atloweraltitudesO3
reactswithhydrocarbonsintheatmospheretoformtoxicperoxyacids,inhalationofwhichcanleadtorespiratoryproblems.

Thiscombinationofatmosphericpollutantsiscalledphotochemicalsmog.

Intheupperatmosphere,theNOformedfromphotolysisofNO2reactswithO3,causingitsdepletion.Again,thisisacatalytic
process,asNOisregeneratedfromthereactionofNO2withanoxygenatom.

Catalyticconvertersintheexhaustsystemsofcarshavebeenusedsincethemid1970stominimisetheamountofNOxspecies
emittedthesegenerallyusecatalystscontainingpreciousmetalssuchasplatinumandrhodiumtoconvertNOxspeciestoN2andO2.

ThePhosphorusCycle
Thephosphoruscyclediffersfromthosewehaveinvestigatedsofar,inthatthereisessentiallynoredoxchemistryinvolved.In
contrasttobothsulfurandnitrogen,wherenatureusesthereducedstatesoftheelements,phosphorusinnatureexistsnearly
exclusivelyinthe+5oxidationstateasphosphate,oraphosphatederivative.(Itshouldbenotedthatthetermphosphate
technicallyrefersonlytothePO43ion,butitisoftenusedtodenoteanyphosphoruscontainingspeciesinwhichtherearefour
phosphorusoxygenbonds.InordertodistinguishPO43,andanyofitsprotonatedderivatives,fromotherphosphates,itisoften
referredtoasinorganicphosphate,abbreviatedPi.)Beingathirdperiodelement,phosphorusisabletoaccommodatemorethan
eightelectronsarounditand,aswesawonp.175,therearefourresonancestructuresthatcanbedrawnforthePO43ion.

ThePO43ioncanbethoughtofasderivingfromcompletedeprotonationofphosphoricacid,H3PO4.Thisisarareexampleofa
triproticacid,withpKavaluesof2.15,7.20and12.38correspondingtothethreedeprotonations.
ThefirstpKa of2.15showsphosphoricacidtobeofsignificantstrength,butitisfarfrombeingastrongacid,asisoftenincorrectly
stated.

Phosphoricacidconsistentlyranksamongthetop10industrialchemicalsproduced,owingtoitssubsequentconversiontofertilisers.
Almostallphosphoricacidisproduceddirectlyfromfluoroapatite.Theoreispartiallypurified,crushedandthenslurriedwith
aqueoussulfuricacid.

Thedilutephosphoricacidobtainedfromthisprocessisconcentratedbyevaporationandisoftenhighlycolouredbecauseofthe
presenceofmanymetalionimpuritiesinthephosphaterock.However,thisimpureacidissuitableforthemanufactureofphosphate
fertilisers,whichaccountsforalmost90%ofphosphoricacidproduction.HighpurityH3PO4isobtainedusingamoreexpensive
redoxprocessthatstartsfromthepureelement.Controlledcombustionofwhitephosphorusgivesphosphorus(V)oxide,P4O10
(figure14.21)andadditionofwatertothisgenerateshighpurityphosphoricacid:

FIGURE14.21Phosphorus(V)oxide,P4 O10 ,containsthesametetrahedralarrangementofphosphorusatomsasinP4 (seefigure14.11),but

anoxygenatomisinsertedintoeachPPbond.AnadditionalterminalOatomisdoublebondedtoeachPatom.

Thishighlypureproduct,whichconstitutesabout10%ofthetotalindustrialoutputofphosphoricacid,isthestartingmaterialfor
makingfoodadditives,pharmaceuticalsanddetergents.

Plantstypicallycontainabout0.2%phosphorusbyweight,buttheelementiseasilydepletedfromsoils.Forthisreason,themajor
commercialapplicationofphosphorusisinfertilisers.Thereareseveralcommonphosphorusfertilisers,butthemostimportantone
isammoniumhydrogenphosphate,(NH4)2HPO4.Thisphosphatecompoundisparticularlyvaluablebecauseitishighlysolubleand
providesbothphosphorusandnitrogen.Thecompoundcanbemadebytreatingphosphoricacidwithammonia:

Thisisthepredominantindustrialrouteto(NH4)2HPO4,accountingforthesinglelargestuseofphosphoricacid.
Animportantreactionofphosphoricacid(anditsderivatives)isphosphatecondensation,aprocessthatissimilartothe
condensationreactionsofotherspeciesthatcontainOHbonds.

Theproduct,H4P2O7,ispyrophosphoricacid,atetraproticacid.Asecondcondensationleadstotriphosphoricacid,whichcanlose
fiveprotons.

Thesodiumsaltsoftheseacids,sodiumpyrophosphate,Na4P2O7,andsodiumtriphosphate,Na5P3O10,havebeenusedwidelyin
detergents.Thepolyphosphateanionsaregoodadditivesforcleaningagentsbecausetheyformcomplexeswithmetalions,
includingthosethatmakewaterhard(Ca2+,Mg 2+)andthosethatcancausecolourstains(Fe3+,Mn 2+).Moreover,polyphosphates
arenontoxic,nonflammableandnoncorrosivetheydonotattackdyesorfabrics,andtheyarereadilydecomposedduring
wastewatertreatment.Theseadvantagesappeartomakepolyphosphatesidealforuseincleaningagents.Unfortunately,adding
phosphatestowaterleadstoanimbalanceinaquaticbiosystems,particularlyinlakes.Inorganicphosphateisrapidlyincorporatedas
anutrientbyalgae,leadingtoexcessalgalgrowth,whichcanoverwhelmalakewithdecayingorganicmatter.Organicdecay
consumesoxygen,depletingthelakeofthislifesustainingsubstanceandleadingtothedeathoffishandotheraquaticlifeforms.
Thiscontributesmoreorganicdecaywithacorrespondingincreaseinoxygendepletion,untileventuallythelakesupportsnoanimal
life.

Phosphatecondensationreactionsplayanessentialroleinmetabolism.Theconversionofadenosinediphosphate(ADP)to
adenosinetriphosphate(ATP)requiresaninputofGibbsenergy.

ATPservesasamajorbiochemicalenergysource,releasingenergyinthereverse,hydrolysis,reaction.TheeaseofinterchangingO
HandOPbondsprobablyaccountsforthefactthatnaturechoseaphosphatecondensationhydrolysisreactionforenergy
storageandtransport.

InADPandATP,oneendofthepolyphosphatechainlinkstoadenosinethroughanOCbond.Thesebondsformincondensation
reactionsbetweenhydrogenphosphateandalcohols.OtherbiochemicalsubstancescontainPOClinkages,andtheseare
generallyreferredtoasphosphateesters,byanalogywithorganicesters(chapter23).However,whileitispossibletoreplaceonly
asingleprotoninacarboxylicacidwithanalkylgroup,replacementofone,twoorthreeprotonsinphosphoricacidbyanalkyl
groupgivesphosphatemono,diandtriesters,respectively.

BothADPandATParephosphatemonoesters,whilethemostimportantbiologicalphosphatediestersareDNAandRNA(seefigure
25.5,p.1090).

ThemajorrepositoryforphosphorusonEarthisinphosphateminerals,themostimportantofwhichareapatites.Thesehavethe
generalformulaCa5(PO4)3X,whereX=F(fluoroapatite),Cl(chloroapatite)andOH(hydroxyapatite),allofwhicharesparingly
solubleunderneutralconditions.Toothenamelisessentiallypurehydroxyapatite,andthisisalsoanimportantcomponentofbones.
Useoffluoridatedtoothpasteisthoughttoresultinconversionofhydroxyapatitetothelesssolublefluoroapatite,therebyslowing
therateoftoothdecay.Importantphosphatedepositsarefoundacrosstheworld,perhapsmostinterestinglyonthetiny(21km2)
PacificislandofNauru.Atonetimeinthetwentiethcentury,Nauruhadoneofthehighestpercapitaincomesintheworldsolely
becauseofitsphosphateexports.Today,however,extensivestripmininghasexhaustedthephosphatedepositsand,withthese
providingtheonlysourceofforeignincome,theisland'sfutureisuncertain.
Thephosphoruscycle(figure14.22)essentiallyinvolvestheinterconversionbetweeninorganicandorganicphosphate(here,
organicphosphatereferstobiologicalmoleculessuchasDNA,RNA,ADPandATP).Inorganicphosphate,fromtheweatheringof
rocks,isassimilatedbyplantsandconvertedtoorganicphosphate.Theplantsareconsumedbyanimalsand,whenbothdie,
bacterialactionconvertstheorganicphosphatebacktoinorganicphosphate.

FIGURE14.22Thephosphoruscycle.

TheCarbonCycle
Carbonaccountsforonly0.08%ofthemassofEarthyetalllifeonthisplanetisbasedoncarbon.Whilewewilldiscusstheorganic
chemistryofcarbonindetailoverthesecondhalfofthisbook,wehaveasyetonlytouchedupontheinorganicchemistryofcarbon
indetailinghowCO2canactasagreenhousegas.Carbonappearsinnatureinoxidationstatesrangingfrom4to+4,anditscycling
betweencompoundsexhibitingtheseoxidationstatesisextremelycomplex.Wewillthereforerestrictourselvestothewayinwhich
CO2travelsbetweentheatmosphere,aquaticsystemsandtheEarth'scrust.Thissimplifiedcycle(figure14.23)doesnottherefore
involveanyredoxchemistry.
 FIGURE14.23Thesimplifiedcarboncycle.

Carbondioxideistheultimateproductofthecombustionofanycarboncontainingcompound.Itisalinearmolecule,withformal
doublebondsbetweentheCandOatoms.

CO2currentlycomprisesover380partspermillionoftheEarth'satmosphereandthisamountissteadilyincreasingowingtoburning
offossilfuels.Itisslightlysolubleinwater,withasolubilityof0.145gL1at25C.Theresultingsolutionismeasurablyacidicand
thisisascribedtotheformationofcarbonicacid,H2CO3.

Giventheimportanceofthismolecule,itissurprisingthatconclusiveevidenceforitsexistencewasobtainedonlyin1987,onthe
basisofmassspectrometricmeasurements.

H2CO3isadiproticacidwhichcanundergotwodissociations:

However,thefirstoftheseequilibriaiscomplicatedbythefactthatonlyasmallfractionofdissolvedCO2actuallyexistsasH2CO3
themajorityispresentsimplyashydratedcarbondioxide,CO2(aq).Whenthisistakenintoaccount,thefirstpKadropstoaround
3.7.ItisthepresenceofdissolvedCO2,whichmakesnaturalfreshwaterslightlyacidic,andthiscaneasilybeshown(onasmall
scale)bymeasuringthepHoftapwater,bottledwaterorwaterinthelaboratoryprovideditisnotfreshlydistilled,itwillhavea
pHcloseto5.

Inspectionofthetwoequilibriaaboveshowsthattheyprovideamechanismfortheformationofbothhydrogencarbonate(HCO3,
alsocalledbicarbonate)andcarbonate(CO32)ionswhichcanthenbeincorporatedintomineralsintheEarth'scrustbyprecipitation
asmetalsalts.ThetwomostimportantcarbonatesaltsinthisrespectareMgCO3andCaCO3,bothofwhichareonlyslightlysoluble
(Kspvaluesof210 5and3.310 9,respectively)andprecipitatereadily.

Naturehasprovidedamethodbywhichcarbondioxidecanbeusedasachemicalfeedstockbyplants.Theprocessof
photosynthesistakescarbondioxideandwaterasreactantsandturnsthemintocarbohydratesandoxygen,asweoutlinedinthe
oxygencycleearlier.Therefore,carbonintheatmosphereisfoundprimarilyasCO2inthebiosphereitisfoundmainlyas
carbohydrates,andinthelithosphereitisfoundascarbonatemineralsandsediments.Untilrecently,thedistributionofcarbon
betweentheseterrestrialsphereswasstable.However,withtheadventoftheindustrialrevolutionandburningoffossilfuels,the
atmosphericconcentrationofCO2hassteadilyincreasedoverthelastcentury.IncreasingCO2intheatmospheremaycontributeto
globalwarmingthatcouldhavecatastrophicconsequences.Inawarmerclimate,forexample,muchofthepolaricecapswould
melt,andtheoceanswouldexpandastheirtemperaturesincreased.Sealevelscouldrisebyseveralmetresandinundatemanyofthe
world'smostpopulousregions,suchasBangladesh,theNetherlands,andtheEastandGulfCoastsoftheUnitedStates.Inaddition,
evensmalltemperaturefluctuationsmayalterglobalweatherpatternsandperhapsleadtoseriousdroughts.

Ourplanetissuchacomplicated,dynamicsetofinterconnectedsystemsthatscientistsdonotknowwithcertaintytheresultof
increasingtheconcentrationofatmosphericCO2.Theyarestudyingthecarboncycleinhopesoflearningwhatliesaheadforthe
planet.Thereissomeurgencytosuchstudiesbecauserecentglobalweatherpatternsshowsomeofthecharacteristicspredictedfrom
computermodelsofglobalwarming:averagetemperatureshigherthanthoseinpreviousyearsandanincreasedincidenceof
extremeweathersuchascyclonesandheavyrainfall.

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 SUMMARY
ThePblockElements
Groups13to18oftheperiodictablecontainelementswhicharepredominantlynonmetalsor
metalloids.Theelementsofgroups13to18arecollectivelycalledpblockelementsandare
characterisedbythegradualfillingoftheporbitalsacrosseachperiod.Thevalenceshellelectron
configurationoftheseelementsrangesfromns2np 1(group13)tons2np 6(group18).

ChemistryofthePblockElements
Group13:boron(B),aluminium(Al),gallium(Ga),indium(In),thallium(Tl)

Group14:carbon(C),silicon(Si),germanium(Ge),tin(Sn),lead(Pb)

Group15:nitrogen(N),phosphorus(P),arsenic(As),antimony(Sb),bismuth(Bi)

Group16:oxygen(O),sulfur(S),selenium(Se),tellurium(Te),polonium(Po)

Group17:fluorine(F),chlorine(Cl),bromine(Br),iodine(I),astatine(At)

Group18:helium(He),neon(Ne),argon(Ar),krypton(Kr),xenon(Xe),radon(Rn)

TheBiogeochemicalCyclesofNature
TheoxygencycleinvolvesO2,O3,O2,O22andH2O,whichinterconvertthroughredoxprocesses.
PhotosynthesisinvolvestheformationofO2fromH2O,whilerespirationisessentiallythereverse
reaction,theformationofH2OfromO2viareactionwithglucose.Ozoneisformedintheupper
atmospherethroughtheactionofultravioletlightonoxygen,whileintheloweratmosphereitis
producedfromphotochemicalsmog.

ThesulfurcycleinvolvesS2,Me2S,SO2,SO3,H2SO4,SO42,SO32andsulfurcontainingaminoacids
andMScentres.Formationofcompoundscontainingsulfurinahighoxidationstate(+4or+6)is
thermodynamicallyfavourable.Tobeusefultolivingorganisms,thesearereducedbymicroorganisms
underanaerobicconditions.Acidrainresultsfromtheburningoffossilfuelscontainingsulfur
impurities.

ThenitrogencycleinvolvesN2,NH3,NO3,NO2,NO,N2Oandaminoandnucleicacids.TheN2
molecule,whileusuallychemicallynonreactive,isconvertedtoammoniabythenitrogenaseenzyme,
andthisthenactsasthesourceofnitrogeninaminoacidsandnucleicacids.NO3isformedastheend
resultofdecompositionoflivingmatter,andthisisreducedtotheothernitrogenoxidesbyanaerobic
bacteria.Variousnitrogenoxidesareinvolvedinatmosphericpollution.

Thephosphoruscycleinvolvestheinterconversionoforganicandinorganicphosphate,anddiffers
fromtheothercyclesofimportanceinthatnoredoxchemistryisinvolved.Inorganicphosphate
includesvariousmetalsaltsofphosphateinvaryingstatesofprotonation,alongwithphosphate
mineralssuchasapatites.MoleculessuchasATP,ADP,DNAandRNAconstituteorganicphosphate
thesemoleculesareimportantinenergystorageandthetransferofgeneticinformation.

CO2travelsbetweentheEarth'satmosphere,oceansandcrust.DissolutionofCO2inwatergivessmall
amountsofcarbonicacid,H2CO3,withthemajorityofCO2existingsimplyashydratedCO2.
DeprotonationreactionsgivebothHCO3(hydrogencarbonate)andCO32(carbonate)whichare
incorporatedintotheEarth'scrustbyprecipitationasslightlysolublemetalsaltssuchasMgCO3and
CaCO3.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
TheBiogeochemicalCyclesofNature(section14.3)
Thepblockelementsoxygen,sulfur,nitrogen,phosphorusandcarbonareimportantinnatureand,with
theexceptionofphosphorus,formcompoundscontainingtheelementsinavarietyofoxidationstates.
Thesecompoundsareinvolvedinchemicalcyclesinnature.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Thebiogeochemicalcyclesofnature
14.1Figure14.21highlightsthetriangulararrangementofphosphorusatomsinP4O10.Asevery
phosphorusatombondstofouroxygenatoms,however,thegeometryaroundeachphosphorus
atomistetrahedral,justasinthephosphateanion.Redrawfigure14.21inawaythathighlights
oneofthetetrahedralPO4units.
14.2Shownbelowisaballandstickmodeloftheactiveingredient(glyphosate)inRoundup ,a
commercialherbicide.DrawtheLewisstructureofRoundupanddescribeitsfunctionalgroups.

14.3Determinethechangesinoxidationstatesforthesulfuratomsinthefollowingreactionsthat
convertH2SintoS8.

14.4DeterminetheLewisstructuresanddescribethebondingandgeometryofthefollowing
compounds:
(a)SF4,
(b)BrF5and
(c)F2C CF2.
14.5Whichofthefollowingstatementsaboutspeciesinvolvedinthebiogeochemicalsulfurcycleand
thechemicaltransformationsinthiscycleisincorrect?
A.Thetransformationof(CH3)2StoSO2isanoxidationreaction.
B.SO2isbestdescribedasbeingVshaped.
C.H2SO4isastrongeracidthanH2SO3.
D.Thesulfiteionistrigonalplanarinshape.
E. ThereactionofSO3withwatertoformH2SO4isanonredoxprocess.
14.6Whichoneofthefollowingstatementsaboutspeciespresentinthebiogeochemicalcarboncycle
andthechemicaltransformationsinthiscycleisincorrect?
A.ThetransformationofcoalintoCO2isanoxidationreaction.
B. TheshapeoftheCO 2ionisbestdescribedastrigonalplanar.
3
C. HCO isaweakeracidthanH CO .
3 2 3
D.CO2reactscompletelywithwatertoformH2CO3.
 E. ThereactionofCO2withwaterisanonredoxprocess.
14.7Whichoneofthefollowingstatementsaboutspeciesinvolvedinthebiogeochemicaloxygen
cycleiscorrect?
A.Photosynthesisleadstoproductionofcarbondioxide.
B.Anaerobicorganismsusedioxygentoeliminateelectronsproducedbyoxidationoffood
molecules.
C.O2isevolvedasabyproductofrespiration.
D.H2O2istheneutralformoftheperoxideanion.
E. Twoelectronsarerequiredtoreducedioxygentothesuperoxideanion.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
14.8WriteLewisstructuresforthefollowingthreespeciesfoundinthesolutionthatiselectrolysedto
formaluminiummetal:[AlF4],[AlF6]3and[AlOF3]2.
14.9AlthoughCl2canbemanufacturedbyelectrolysisofaqueousbrine,theanalogousreactioncannot
beusedtomakeF2.ExplainwhyanhydrousHFmustbeusedforproductionofF2.
14.10Pyrophosphate,P O 4,andtriphosphate,P O 5,arethetwosmallestpolyphosphateanions.
2 7 3 10
Whatisthechemicalformulaofthenextlargestpolyphosphateanion?Drawaballandstick
modelofthisanion.
14.11ThreephosphateanionscancondensetoformaringwiththechemicalformulaP O 3.
3 9
DeterminetheLewisstructureanddrawaballandstickmodelofthisanion.
14.12Describethereactionsthatconvertfluoroapatitetophosphoricacid.IdentifyBrnstedLowry
acidbasereactionsandredoxreactions,ifany.
14.13Describethereactionsthatconvertcalciumphosphatetophosphoricacid.IdentifyBrnsted
Lowryacidbasereactionsandredoxreactions,ifany.
14.14Writestructuralformulaeshowingtheconversionofwhitephosphorusintoredphosphorus.Use
curvedarrowstoshowhowelectronsmoveduringthisconversion.
14.15WritestructuralformulaeshowingthereactionofATPwithwatertoformADP.Whatistheother
product?
14.16Identifytheoxidisingagent,reducingagentandchangesofoxidationstatethatoccurinthe
reactionformingSiCl4fromSiO2.
14.17Eachofthefollowingmoleculesorionsplaysacrucialroleinthebiogeochemicalcyclefor
sulfur.ForeachofthesespeciesdrawaLewisstructure,andpredicttheelectronpairgeometry,
molecularshapeandbondangles.Showformalchargeswhererequired.
(a)S8
(b)SO 2
3
(c) SO 2
4
(d)Me2S

Whichofthesespecieshasanonzerodipolemoment?
14.18Denitrifyingbacteriarespireonthedifferentoxidesofnitrogenandcarryout(reductive)
chemicalchangessuchas:

Writebalancedhalfequationsforeachofthesestepsinacidicsolution.

Ontheotherhand,nitrogenfixingbacteriacarryout(oxidative)changessuchas:

Writebalancedhalfequationsforeachofthesestepsinacidicsolution.
14.19 (a)CarbonatebuffersareimportantinregulatingthepHofbloodat7.40.Whatisthe
concentrationratioofCO2(aq)(usuallywrittenH2CO3)toHCO3(aq)inbloodatpH=
7.40?
 (b)PhosphatebuffersareimportantinregulatingthepHofintracellularfluidsatpHvalues
generallybetween7.1and7.2.WhatistheconcentrationratioofH2PO4toHPO42in
intracellularfluidatpH=7.15?

(c) WhyisabuffercomposedofH PO andH PO ineffectiveinbufferingthepHof

3 4 2 4
intracellularfluid?

14.20 (a)Drawthebiologicalnitrogencycle,givingtheformulaofeachofthemoleculesandions
presentinthecycle.
(b)Writeequationstodemonstratethatthepresenceofnitrogendioxideinthelower
atmosphereleadstotheproductionofozoneintheloweratmosphere.
(c)Writeequationstodemonstratethatdiffusionofnitrogendioxidetotheupperatmosphere
leadstothelossofozoneintheupperatmosphere.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
14.21WaterinthermalhotspringsisoftenunpalatableduetodissolvedH2S.TreatmentwithCl2
oxidisesthesulfurtoS8,whichprecipitates(theotherproductisHCl).Balancethisreactionand
calculatethemassofCl2requiredtopurify6.010 3Lofwatercontaining25partspermillion
(bymass)ofdissolvedH2S.
14.22Calciumdihydrogenphosphateisacommonphosphorusfertiliserthatismadebytreating
fluoroapatitewithphosphoricacid.Hydrogenfluorideisabyproductofthesynthesis.Writea
balancedequationfortheproductionofthisfertiliserandcalculatethemasspercentageof
phosphorusinthefertiliser.
14.23TheblacktarnishthatformsonpuresilvermetalisthesulfideAg 2S,whichisformedbyreaction
withH2Sintheatmosphere.

ThesulfideformsinpreferencetoAg 2O,eventhoughtheatmosphereis20%O2withjustatrace
ofH2S.UseLewisacidbaseargumentstoexplainthisbehaviour.
14.24Thionylchloride,SOCl2,isusedtoremovewaterofhydrationfrommetalhalidehydrates.
Besidestheanhydrousmetalhalide,theproductsareSO2andHCl.
(a)DrawtheLewisstructureofSOCl2.
(b)Writethebalancedequationforthereactionofiron(III)chloridehexahydratewithSOCl2.
14.25Ammoniumdihydrogenphosphateandammoniumhydrogenphosphatearecommonfertilisers
thatprovidebothnitrogenandphosphorustogrowingplants.Incontrast,ammoniumphosphate
israrelyusedasafertiliserbecausethiscompoundhasahighvapourpressureoftoxicammonia
gas.Writebalancedequationsshowinghoweachofthesesolidphosphatescouldgenerate
ammoniagas.WhydoesammoniumphosphatehavethehighestvapourpressureofNH3ofthese
threecompounds?
14.26Borontrichlorideisagas,borontribromideisaliquid,andborontriiodideisasolid.Explainthis
trendintermsofintermolecularforcesandpolarisability.
14.27Aluminiumrefiningrequireslargeamountsofelectricity.CalculatethemassesofAlandNathat
areproducedpermoleofchargebyelectrolyticrefiningofAl2O3andNaCl.
14.28Trisodiumphosphateformsstronglybasicsolutionsthatareusedascleaningagents.Write
balancedequationsthatshowwhyNa3PO4solutionsarestronglybasic.IncludepKavaluesto
supportyourequations.
14.29Thefirstcommerciallysuccessfulmethodfortheproductionofaluminiummetalwasdeveloped
in1854byHenriDeville.TheprocessreliedonearlierworkbytheDanishscientistHans
Oersted,whodiscoveredthataluminiumchlorideisproducedwhenchlorinegasispassedover
hotaluminiumoxide.Devillefoundthataluminiumchloridereactswithsodiummetaltogive
aluminiummetal.Writebalancedequationsforthesetworeactions.
14.30Metaloxidesandsulfideoresareusuallycontaminatedwithsilica,SiO2.Thisimpuritymustbe
removedwhentheoreisreducedtothepureelement.Silicacanberemovedbyaddingcalcium
oxidetothereactor.SilicareactswithCaOtogiveCaSiO3.Writeabalancedequationforthis
reaction,anddescribethereactionintermsofLewisacidsandbases.
14.31Phosphorus(V)oxidehasaverystrongaffinityforwaterhence,itisoftenusedasadryingagent
inlaboratorydesiccators.OnemoleofP4O10reactswith6molesofwater.Basedonthis
stoichiometry,identifytheproductofthereactionandbalancetheequation.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERM
pblockelements

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

15 ReactionKinetics
Chemicalreactionsoccuratmanydifferentspeeds.Reactionsliketherustingofiron,
ripeningoffruit,weatheringofstone,spoilingofmilkandbreakdownofplasticstakeplace
veryslowly.Otherreactions,likethecombustionofpetrolandexplosionofgunpowder,
occurveryquickly.Understandingthemechanismofchemicalreactionsandwhysome
reactionsarefastandothersarenotisanimportantfieldinchemicalresearch.Indeed,the
1999NobelPrizeinchemistrywasawardedtoAhmedHZewailfordevelopingultrafast
lasertechniquesthatcanrecordthemotionofatomsinamoleculeduringachemical
reaction.Thisenablesthestudyofreactionmechanisms,includingthedetailedsteps
involvedintransformingreactantsintoproducts.

MarieSchmitt

Theareaofchemistrythatdealswithreactionratesandmechanismsiscalledchemical
kinetics.Reactionspeedsareinfluencedbymanyvariables,suchastemperature,pressure
andconcentration.
Theimagesonthispageshowcrosssectionalviewsofcoronaryarterieswithatherosclerotic
plaque.Arterosclerosisisaconditioninwhichanarterywallthickensastheresultofabuild
upoffattymaterialssuchascholesterol.Inrecentyearsithasbecomeclearthatthestrong
oxidanthypochlorite(HOCl),whichismadebywhitebloodcellsinourbodyinareaction
thatinvolvestheenzymemyeloperoxidase,candamagethebody'sowncellsandstructures.
Myeloperoxidaseispresentandactivewithinthearterywallandmaycontributetothe
developmentofatheroscleroticlesionsandheartdiseaseplaques.Understandingthe
chemicalmechanismbywhichthisenzymegeneratesdamagetothearterywall,andmore
importantlyhowthismightbeprevented,isoffundamentalimportancetohumanhealth.

SPL/Zephyr

KEYTOPICS

15.1Reactionrates
15.2Factorsthataffectreactionrates
15.3Overviewofratelaws
15.4Typesofratelaws:differentialandintegrated
15.5Theoryofchemicalkinetics
15.6Reactionmechanisms
15.7Catalysts
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.1ReactionRates
Inchapter8welearnedaboutthedefinitionofaspontaneousreaction.WhilethevalueandsignofG
indicatethespontaneityofachemicalreaction,theydonottellusanythingabouthowfastthereaction
mightbe.Forexample,thethermodynamicdatafortheconversionofdiamondtographite(figure15.1)tell
usthatthisisaspontaneousprocessunderstandardconditions ,buteverybody
notjustthoseluckyenoughtoownpreciousdiamondjewelleryknowsthatthisreactionisvery,very
slow!Theformationofammoniafromgaseoushydrogenandnitrogenthroughtheprocess:

alsohasathermodynamictendencytooccur,butnoproductsareobservedtoformatroomtemperature
andatmosphericpressure.Therearemanyotherexamplesofspontaneousreactionsthatoccursoslowly
thatwecannotobserveanychangeoverlongperiodsoftime(insomecases,years).

FIGURE15.1 (a)Diamondand
(b)graphitearetwodifferentallotropesofcarbon.Although fortheconversionofdiamond
intocarbonisnegative,adiamondwillnotrevertintographiteatameasurablerateunder
normalconditions.
TylerBoyes

Chemicalkineticscanhelpusunderstandwhyreactionsproceedinaparticularway.Itisthestudyofthe
ratesofchangeoftheconcentrationsofreactantsandproductsinachemicalreaction.Figure12.9onp.
501showsacopperwirebeingdippedintoasolutionofsilvernitrate.Withincreasingreactiontime,the
bluecolouroftheaqueoussolutionintensifies,indicatingformationofCu 2+ions,whereaselementalsilver
continuouslydepositsonthewire.Theratesofchemicalreactionsarestudiedbymonitoringthe
concentrationsofreactantsand/orproductsovertime.Therearemanydifferentwaystoobserve
concentrationchangesasthereactionproceeds.Figure15.2showsaconcentrationtimeprofileforthe
hypotheticalreactionA2B.
 FIGURE15.2Theprogress(concentrationtimeprofile)ofthereactionA2B,showingtheconcentrationsofA
andBovertime.

Figure15.2showsthattheconcentrationofthereactant,A,decreaseswithtime,whiletheconcentrationof
theproduct,B,increaseswithtime,andweusuallytalkoftherateofconsumptionofareactantandtherate
offormationofaproduct.WecandeterminetherateofconsumptionofAandtherateofformationofBby
measuringtheconcentrationsofAandBattwodifferenttimes,t1(earlyinthereaction)andt2(laterinthe
reaction).

ThesquarebracketsindicateconcentrationinmolL1,andthesymbolindicatesachangeinagiven
quantity(finalvolumeinitialvolume).Similarly,therateofformationofBis:

Byconvention,ratesofformationandconsumptionarealwaysreportedasapositivevalue,irrespectiveof
whethersomethingincreasesordecreasesinconcentration.(Thiscanbecomparedwiththespeedofacar
itmaydrivetoorawayfromaparticularspot,butthespeedisalwaysapositivenumber.)

Thesecondandthirdcolumnsoftable15.1showmeasurementsoftheconcentrationsofAandB,
respectively,overtimeasourhypotheticalreactionproceeds.
TABLE15.1 ConcentrationofAandBandaverageratesasafunctionoftimeforthereactionA2B,as
showninfigure15.1

Time(s) [A](molL1) [B](molL1) Timeperiod(s)

0 0.0750 0.0
50 0.0629 0.0242 050 2.410 4
100 0.0529 0.0442 50100 2.010 4
 150 0.0444 0.0612 100150 1.810 4
200 0.0372 0.0756 150200 1.410 4
250 0.0313 0.0874 200250 1.210 4
300 0.0262 0.0976 250300 1.010 4
350 0.0220 0.106 300350 8.010 5
400 0.0185 0.113 350400 7.010 5

Wecanusethedataintable15.1tocalculatetheaveragerateofconsumptionofAinthefirst50seconds
ofthereaction.

Asyoucansee,[A]isanegativequantity,becausetheconcentrationofAdecreaseswithtime.Sincerates
ofchangeofconcentrationarealwayspositivenumbers,therateofconsumptionofareactantisdefinedas:

TheaveragerateofconsumptionofAinthefirst50secondsofthereactionistherefore:

Thelastcolumnoftable15.1givesaverageratesofconsumptionofAforthisreactionduringsomeother
50secondtimeintervals.ThedatashowthataverageratesofconsumptionofAdecreasewithtimeasAis
usedup.ThisisbecausetheseratesusuallydependontheconcentrationofA,whichchangesasthe
reactionproceeds.Therefore,tominimiseerrorsitisbettertodeterminereactionratesovershortperiodsof
time.

Therateofchangeofconcentrationataparticulartimeiscalledtheinstantaneousrateofchangeof
concentration.Lookingbacktofigure15.2,weseethattheinstantaneousrateofconsumptionofAor
formationofBcanbedeterminedfromtheslopeofthetangenttothecurve.Forexample,infigure15.2a
tangentisdrawnatt=50secondsontheAcurve.Theslopeofthisline,ascalculatedfromthevaluesof
[A]andtgiveninfigure15.2,givestheinstantaneousrateofconsumptionofAatt=50seconds
(rememberthatwearelookingattheconsumptionofareactionandthattheslopewill,therefore,be
negative).
Inthisequation,dindicatesaninfinitesimallysmallchange.Rememberthattherateofareactionhasthe
unitconcentrationperunittimeor(concentration)(time)1andthisisusuallymolL1s1.

Now,lookattherateofformationoftheproduct,B.Forthis,thecoefficientsinthebalancedequationfor
thereactionhavetobetakenintoaccount,becausethestoichiometrydeterminestherelativeratesatwhich
reactantsareconsumedandproductsformed.Inthecaseofourhypotheticalreaction,A2B,Bis
producedtwiceasfastasAisconsumed,whichcanbeverifiedfromfigure15.2.Theslopeofthetangent
totheBcurveatt=50secondsgivestheinstantaneousrateofformationofBat50seconds,whichis:

ThisshowsthattherateofformationofBisindeedtwicethatofconsumptionofA.Notethattheslopeof
thetangentispositive.

Asyoucansee,theratesofconsumptionofreactantsandratesofformationofproductsinaparticular
reactionarenotnecessarilythesame.Itismuchmoremeaningfulforustodefinetherateofreaction
whosevalueisthesameregardlessofwhetherwearemonitoringratesofconsumptionofreactantsorrates
offormationofproducts.Forthegeneralreaction:

whereatodarethestoichiometriccoefficientsofthereactantsAandBandtheproductsCandD
respectively,wedefinetherateofreactionas:

Therefore,forourreactionA2B,wewouldwrite:

Therateofareactionhasunitsof(concentration)(time)1.Itisimportantthatyouappreciatethedifference
betweentherateofreactionandtheratesofconsumptionofreactantsandratesofformationofproducts.
Therateofreactionhasonlyonevalueforanyparticularreactionandisindependentofthereaction
stoichiometry,whereastheratesofreactantconsumptionandproductformationaredifferentifthe
stoichiometriccoefficientsdiffer.

WORKEDEXAMPLE15.1

EstimatingtheInitialRateofaReaction
Thefollowingdatahavebeenmeasuredat508Cforthereaction2HI(g)H2(g)+I2(g).

Time(s) [HI](molL1)
0 0.100
50 0.0716
100 0.0558
150 0.0457
 200 0.0387
250 0.0336
300 0.0296
350 0.0265

WhatistheinitialrateofconsumptionofHI,andwhatistheinitialrateofreactionatthis
temperature?

Analysis

TheinitialrateofconsumptionofHIistheinstantaneousrateofconsumptionofHIattimezero.
Onceweplotthedata,wecandrawatangenttothecurveshowing[HI]asafunctionoftimeat
timezero.TheinstantaneousrateofconsumptionofHIistheslopeofthetangent.Theslopeof
thelinecanbecalculatedfromthecoordinatesofanytwopoints(x1,y1)and(x2,y2)usingthe
equation:

Theinitialrateofreactioncanbecalculatedusingthestoichiometryofthereaction.

Solution

Becausewewanttostudytheratesatwhichconcentrationschange,wehavetousedifferential
calculus.Thus,sinceatangenttoacurvetouchesthecurveatonlyonepoint,wecandrawthe
lineasshowninthediagrambelow.

Todeterminetheslopeofthetangentprecisely,weshouldchoosetwopointsthatareasfarapart
aspossible.Wecoulduse,forexample,thepointonthecurve(0s,0.10molL1)andthe
intersectionofthetangentwiththetimeaxis(150s,0molL1),whicharewidelyseparated.

(Thereisnorequirementtorestricttheextrapolationtoconcentration=0tofindtheslope.)
TheslopeisnegativebecausetheconcentrationofHIisdecreasingastimeincreases.Reaction
ratesarepositivequantities,sowereporttheinitialrateofconsumptionofHIas6.710 4mol
L1s1.Todothiscalculation,werelyonaccuratelydrawingbyhandatangenttothecurveatt
=0.Becauseofthis,thereisadegreeofuncertaintyintheaccuracyofouranswer.Theinitial
rateofreactionisdefinedbytheequation:

Wehavealreadycalculatedtheinitial attimezeroasbeing6.710 4molL1s1,so

theinitialrateofreactionis:

Isouranswerreasonable?

Asnotedpreviously,drawingatangenttoacurvebyeyeisnotprecise.Theremaybe
considerablevariationinthedeterminedtimedifference,whichaffectstheaccuracyofour
calculatedrate.Onewayofcheckingouransweristorealisebyinspectionofthegraphthatthe
instantaneousrateofconsumptionofHIattimezeroshouldbecloseto,butslightlygreaterthan,
theaveragerateofconsumptionofHIbetween0sand50s.
 WecancalculatetheaveragerateofconsumptionofHIdirectlyfromthedatainthetableonp.
632,whichhavebeenaccuratelymeasured.

SotheaveragerateofconsumptionofHIfrom0sto50sis5.710 4molL1s1.Asexpected,
thisisclosetobutslightlylessthantheinstantaneousrateofconsumptionofHIattimezero,6.7
10 4molL1s1.

Aconceptrelatedtoreactionrateisthehalflife ofareaction.Thisisthetimetakenforthe

concentrationofaspecifiedreactanttofalltohalfofitsinitialconcentration.Wewilllearnmoreabouthalf
liveslaterinthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.2FactorsthatAffectReactionRates
Fiveprincipalfactorsinfluencereactionrates:thechemicalnatureofthereactants,thephysicalnatureof
thereactants,theconcentrationsofthereactants,thetemperature,andtheavailabilityofrate
acceleratingagentscalledcatalysts.

ChemicalNatureoftheReactants
Duringreactions,bondsbreakandnewbondsform.Themostfundamentaldifferencesbetweenreaction
rates,therefore,lieinthereactantsthemselves,intheinherenttendenciesoftheiratoms,moleculesor
ionstoundergobondbreakingand/orbondmakingprocesses.Somereactionsarefastbynatureand
othersareslow.Asyouhaveseeninchapter4(figure4.50),alkalimetalscanbeeasilyionised,which
leadstoahighreactivityofthesecompoundstowardsoxidation.Thus,afreshlyexposedsurfaceof
metallicsodiumtarnishesalmostinstantlywhenexposedtoairandmoisture.Underidenticalconditions,
potassiumalsoreactswithairandmoisture,butthereactionismuchfasterbecausetheionisationenergy
ofpotassiumisevenlowerthanthatofsodium(figure15.3).Comparedwiththesefastreactions,the
reactionofsilverwithwaterisveryslow,whichyoucancheckbyputtingasilverringintoaglassof
waterandobservingthatnothinghappens.

FIGURE15.3 Thechemicalnatureofthereactantsaffectsreactionrates.
(a)Sodiumiseasilyoxidised,soitreactsquicklywithwater.
(b)Potassiumisevenmoreeasilyoxidisedthansodium,soitsreactionwithwateris
explosivelyfast.

PhysicalNatureoftheReactants
Mostreactionsinvolvetwoormorereactantswhoseconstituentatoms,ionsormoleculesmustcollide
forthereactiontooccur.Thisiswhyreactionsarerarelycarriedoutinthesolidstate,butoftenoccurin
liquidsolutionsorinthegasphasewherethereactantsareabletointermingleandtheirconstituent
atoms,moleculesorionscancollidewitheachothereasily.

Consider,forexample,that,althoughliquidpetrolburnsrapidly,petrolvapourexplodeswhenmixed
withairintherightproportionsandignited.(Anexplosionisanextremelyrapidreactionthatgenerates
hotexpandinggases.)Thecombustionofvaporisedpetrolillustratesahomogeneousreaction,because
allofthereactantsareinthesamephase.

Whenthereactantsarepresentindifferentphases,forexample,ifoneisagasandtheotherisaliquid
orasolid,thereactioniscalledaheterogeneousreaction.Inaheterogeneousreaction,thereactantsare
abletomeetonlyattheinterfacebetweenthephases,sotheareaofcontactbetweenthephasesaffects
thereactionrate.Thisareaiscontrolledbythesizesoftheparticlesofthereactantconstituents.By
pulverisingasolid,thetotalsurfaceareacanbesignificantlyincreased(figure15.4).Thismaximises
contactbetweentheatoms,ionsormoleculesinthesolidstatewiththoseinadifferentphase.

FIGURE15.4Effectofcrushingasolid.Whenasinglesolidissubdividedintomuchsmallerpieces,thetotal
surfaceareaofallofthepiecesbecomesverylarge.

Althoughheterogeneousreactionsareobviouslyimportant,theyareverycomplexanddifficultto
analyse.Inthischapter,therefore,wewillfocusmostlyonhomogeneoussystems.

ConcentrationsoftheReactants
Theratesofbothhomogeneousandheterogeneousreactionsareaffectedbytheconcentrationsofthe
reactants.Forexample,woodburnsrelativelyquicklyinairbutextremelyrapidlyinpureoxygen.Even
redhotsteelwool,whichonlysputtersandglowsinair,burstsintoflamewhenthrustintopureoxygen.
StudieshaveshownthattheEarth'satmospherehashadanoxygencontentashighas35%inthepast
(nowadays,itisonly21%).Thishigheroxygenconcentrationhadsomenegativeconsequences,suchas
firesburninghotterandfaster.
TemperatureoftheSystem
Almostallchemicalreactionsoccurfasterathighertemperatures.Milkdoesn'tspoilasquicklywhenit
iscold.Ittakeslongertocookaneggat80Cthanat100C.Youmayalsohavenoticedthatinsects
movemoreslowlywhentheairiscool.Insectsarecoldbloodedcreatures,whichmeansthattheirbody
temperatureisdeterminedbythetemperatureoftheirsurroundings.Astheaircools,insectscool,andso
theratesoftheirchemicalmetabolismslowdown,makingthemsluggish.

PresenceofCatalysts
Catalystsaresubstancesthatincreasetherateofchemicalreactionswithoutbeingusedup.Catalysts
affecteverymomentofourlivesbecausetheenzymesthatdirectourbodychemistryareallcatalysts.
Manyofthesubstancesusedbythechemicalindustrytomakepetrol,plastics,fertilisersandother
everydayproductsarealsocatalysts.Wewilldiscusshowcatalystsaffectreactionratesinsection15.7.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.3OverviewofRateLaws
Inworkedexample15.1,wediscussedthedecompositionofhydrogeniodide.

Wehaveseeninchapter9thatchemicalreactionsarereversible.Asthedecompositionproceeds,H2andI2areformedandcanthemselves
reacttoformHI(seefigure15.5).

Whenhydrogeniodidegasisfirstplacedinanemptycontainer,theforwardreactionisdominantandtherateofchangeofconcentrationof
HIdependsonlyontherateoftheforwardreaction.Whensufficientproductshaveformed,therateofthereversereactionbecomes
importanttoo,andtherateofchangeofconcentrationofHIthendependsonthedifferenceintheratesoftheforwardandreversereactions.

FIGURE15.5Concentrationtimeprofileforthedecompositionofhydrogeniodide.

Generally,wewanttodeterminetherateofreactionunderconditionsinwhichthereversereactioncanbeignored,thatis,whentherateof
thereactiondependsonlyontheconcentrationofthereactants.

Thiscanbedoneifwedeterminetherateofreactionimmediatelyafterplacingthereactantsintothereactionvessel,whenthereactiontime
hasbeentooshorttobuildupsignificantamountsofproducts.Thisiscalledtheinitialrateofareaction.

Suchanequationinwhichtherateofreactionisgivenasafunctionofreactantconcentrations(inthiscase[HI])iscalledaratelaw.Note
that,becausethereactionhasbeenstudiedunderconditionsinwhichthereversereactiondoesnotcontributetotheoverallrate,theproducts
donotappearintheratelaw.Theratelawcontainsaproportionalityconstantk,whichiscalledtherateconstantorratecoefficientforthe
reaction,andanexponentn,calledtheorderwithrespecttothereactant.Thetermsrateconstantandratecoefficientareoftenused
interchangeably.Inthisbookwewillusethetermrateconstant.Thevalueoftherateconstantdependsontheparticularreactionbeing
studied,aswellasontheconditions,suchastemperatureandpressure,underwhichthereactionoccurs.Itisnotdependentonthe
concentrationsofreactants.Theordercanbepositive,negativeorzero,anintegerorafraction,butcannotbededucedfromthebalanced
equationexceptinveryspecialcircumstances.Thisisaveryimportantpoint,whichwewillexaminesoon.

Aswesawearlier,therateofareactiondoesnotdependonwhetherwemonitortheconsumptionofreactantsortheformationofproducts.
Infact,whichreactantorproductconcentrationwechoosetomonitoroftendependsonwhichdataaretheeasiesttoobtain.Forexample,to
studythedecompositionofhydrogeniodideintoH2andI2,itiseasiesttomonitortheI2concentration,becauseitistheonlycoloured
substanceinthereaction.Asthereactionproceeds,purpleiodinevapourforms,whichcanbemeasuredwithinstrumentsthatrelatethe
intensityofthecolourtotheiodineconcentration.

Thus,ifwedefinetherateofreactionintermsofformationofI2,weget:

Aswehavediscussedbefore,inthisequation,dstandsforanextremelysmallchange.Wecouldalsodefinethereactionrateintermsof
consumptionofHI:

TherateofconsumptionofHIistwicetherateofformationofI2.Onceweknowtherateofformationofiodine,wealsoknowtherateof
formationofhydrogen,becausethestoichiometriccoefficientsofI2andH2arethesame.

WORKEDEXAMPLE15.2

RelationshipsofratesWithinaReaction
Butane,C4H10,burnsinoxygentogiveCO2andH2Oaccordingtotheequation:

Ifthebutaneconcentrationisdecreasingatarateof0.20molL1s1,whatistherateatwhichtheoxygenconcentrationis
decreasing,andwhataretheratesatwhichtheproductconcentrationsareincreasing?

Analysis

Weneedtorelatetherateofconsumptionofoxygenandtheratesofformationoftheproductstothegivenrateofconsumptionof
butane.Thechemicalequationlinksamountsofthesesubstancestotheamountofbutane.Themagnitudesoftheratesrelativeto
eachotherareinthesamerelationshipasthecoefficientsinthebalancedequation.

Solution

Fromourdefinitionofrateofreaction,wecanwrite:

Wearetoldthat:

andwecanthereforeusethis,togetherwithourexpressionfortherateofreaction,todetermine :

Thus:

WecancarryoutsimilarcalculationsforbothH2OandCO2.ForCO2:

Therefore:

ForH2O:

Therefore:

Isouranswerreasonable?

Ifwhatwehavecalculatediscorrect,thentheratioofthenumericalvaluesoftheratesofformationofCO2andH2O,namely0.80
to1.00,shouldbethesameastheratioofthecorrespondingcoefficientsinthechemicalequation,namely8to10(thesameas0.80
to1.00).Theratiosmatch,sowecanbeconfidentinouranswers.

PRACTICEEXERCISE15.1
Hydrogensulfideburnsinoxygentoformsulfurdioxideand
water:
 Ifsulfurdioxideisbeingformedatarateof0.30molL1s1,
whataretheratesofconsumptionofhydrogensulfideand
oxygen?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.4TypesofRateLaws:DifferentialandIntegrated
Inourdiscussion,wedefinedtheratelawforthedecompositionofHIas:

Thisexpressestherateofreactionasafunctionofconcentrationandisknownasadifferentialratelaw
(oftenabbreviatedtoratelaw).Oncetheorder,n,isknown,wecandetermineexactlyhowtherateof
reactiondependsontheconcentrationofHI.Asecondimportanttypeofratelawexpressesthe
concentrationasafunctionoftime.Thisiscalledanintegratedratelaw.

Wecandeterminethedifferentialratelawbymeasuringratechangeswhentheconcentrationsarechanged.
Wecandeterminetheintegratedratelawbymeasuringchangesinconcentrationsovertime.Thetwotypes
ofratelawarerelatedand,ifweknowoneratelawforareaction,wecan,inmostcases,determinethe
other.

Ratelawshelpustoidentifythestepsbywhichachemicalreactionoccursandthusunderstandthe
reaction.Mostreactionsinvolveaseriesofsequentialsteps.Thesumoftheindividualreactionstepsis
calledthereactionmechanism.Theformationofammoniafromnitrogenandhydrogen,whichwe
encounteredatthebeginningofthechapter,isextremelyslowatroomtemperatureunderatmospheric
pressure.ThisisbecausethestrongHHsinglebondandtheN Ntriplebondmustbebroken.Tospeed
thisreactionupandmakeitsyntheticallyusefulbyusingcatalysts,thestepsthatareinvolvedinthe
reactionmustbeknown.

TheDifferentialRateLaw
Tounderstandthemechanismofachemicalreaction,wemustfirstdeterminetheformoftheratelaw.Let
uslookatanotherhypotheticalreaction:

Table15.2andfigure15.6presentthedataforthisreaction.Inthisreactionweassumethatthereverse
reaction2DCismuchslowerthantheforwardreaction,sowearenotconcernedabouttheeffectofthe
reversereactionontherateofreactionatanytime.
TABLE15.2 ConcentrationandtimedataforthereactionC2D

Time(s) [C](molL1)
0 0.70
0.25 0.58
0.50 0.48
0.75 0.40
1.00 0.33
1.25 0.27
1.50 0.23
1.75 0.19
2.00 0.16
 FIGURE15.6DeterminationoftheorderofthereactionC2D.

Fromfigure15.6,wecanseethattheslopesofthetangentstothecurveat[C]=0.60Mand0.30Mgive
theratesofreaction,0.42molL1s1and0.21molL1s1,respectively.

WhentheconcentrationofCishalved,therateofreactionisalsohalved.Thedifferentialratelawforthis
reactionistherefore:

Thatis,therateofreactiondependsontheconcentrationofCtothefirstpowerandwesaythatthe
reactionisfirstorderinC.(Rememberthattheordercannotbedeterminedfromthestoichiometric
coefficientofCinthisexampleitisjustcoincidencethattheyarethesame.Theordercanbe
determinedonlyfromexperiments.)

WORKEDEXAMPLE15.3

CalculatingaRateConstantfromtheRateData
Usethedatainfigure15.6tocalculatetherateconstantforthereactionC2D.

Analysis

WeknowthattheratelawforthereactionC2Dis:

Therefore:

Wesubstitutedatafromfigure15.6intothisequationandsolvefork.

Solution
 For[C]=0.60molL1,wehavefoundthatrateofreaction=0.42molL1s1.Insertingthisinto
theequationgives:

Isouranswerreasonable?

Wecancheckwhetherourcalculationiscorrectbyalsocalculatingtherateconstantforthe
othervalueofthereactionrateshowninfigure15.6.Itshouldbethesameasthatcalculated
above,astherateconstantforareactionisconstantatconstanttemperature.

For[C]=0.30molL1,rateofreaction=0.21mol1L1s1therefore:

Astherateconstantisthesameunderbothconcentrationconditions,wecanbeconfidentthat
ouransweriscorrect.

Let'sgoastepfurther.Considerthefollowinghypotheticalreaction:

Supposethatthedataintable15.3onthenextpagehavebeenobtainedinaseriesoffiveexperimentsat
thesametemperature.Theformoftheratelawforthereactionis:

Thevaluesofnandmarefoundmathematically,andcansometimesbesolvedbylookingforpatternsin
theratedata.Oneoftheeasiestwaystorevealpatternsindataistoformratiosofresultsusingdifferentsets
ofconditions.Thisprocedureisalsocalledthemethodofinitialrates.Becausethistechniqueisquite
generallyuseful,let'slookinsomedetailathowitisappliedtotheproblemoffindingtheratelaw
exponents.
TABLE15.3 ConcentrationandratedataforthehypotheticalreactionA+BCdeterminedatthesame
temperature

Initialconcentrations
Experiment A(molL1) B(molL1) InitialrateofformationofC(molL1s1)
1 0.10 0.10 0.20
2 0.20 0.10 0.40
3 0.30 0.10 0.60
4 0.30 0.20 2.40
5 0.30 0.30 5.40

Forexperiments1,2and3intable15.3,theconcentrationofBwasheldconstantat0.10M.Anychangein
therateofreactionforthesefirstthreeexperimentsmustbeduetothechangein[A].Theratelawtellsus
that,when[B]isheldconstant,therateofreactionmustbeproportionalto[A]nso,ifwetaketheratioof
ratelawsforexperiments1and2,(since[B]mcancelsout)weobtain:

Let'slookatthelefthandsideofthisequationfirst.
Andfortherighthandsideoftheequationwehave:

Sodoubling[A]fromexperiment1toexperiment2doublestherateofreaction.Ifwenowcombinethe
leftandrighthandsidesoftheequation,wecanwrite:

forexperiments1and2.

Fortheotherpossiblecombinationsofexperiments,wehave:

Theonlyvalueofnthatmakesalloftheseequationstrueisn=1.Thereactionmustbefirstorderwith
respecttoA.

Inthefinalthreeexperiments,theconcentrationofBchangeswhiletheconcentrationofAisheldconstant.
Thistimeitis[B]thataffectstherate.Takingtheratioofratelawsforexperiments3and4,wehave:

Foreachuniquecombinationofexperiments3,4and5,wehave:

Theonlyvalueofmthatmakesalloftheseequationstrueism=2.Thereactionmustbesecondorderwith
respecttoB.

Havingdeterminedtheexponentsfortheconcentrationterms,wenowknowthattheratelawforthe
reactionis:

ThereactionisfirstorderwithrespecttoAandsecondorderwithrespecttoB.Theoverallorderofa
reactionisdefinedasthesumoftheordersforeachreactantintheratelaw.Thus,ourhypothetical
reactionA+BChasanoverallorderof3.

WORKEDEXAMPLE15.4

DeterminingtheExponentsofaRateLaw
Sulfurylchloride,SO2Cl2,isadenseliquidwithapungentodourandiscorrosivetotheskinand
lungs.Itisusedtomanufacturetheantisepticchlorophenol.Thefollowingdatawerecollected
onthedecompositionofSO2Cl2atacertaintemperature.
 InitialconcentrationofSO2Cl2(molL1) InitialrateofformationofSO2(molL1s1)

0.100 2.210 6
0.200 4.410 6
0.300 6.610 6

Determinetheratelawandthevalueoftherateconstantforthisreaction.

Analysis

Thefirststepistowritethegeneralformoftheexpectedratelawsowecanseewhich
exponentshavetobedetermined.Thenwestudythedatatoseehowtherateofreaction
changeswhentheconcentrationischangedbyacertainfactor.

Solution

Weexpecttheratelawtohavetheform:

Let'sexaminethedatafromthefirsttwoexperiments.Noticethat,whentheconcentration
doublesfrom0.100molL1to0.200molL1,theinitialrateofreactionalsodoubles(from2.2
10 6molL1s1to4.410 6molL1s1).Ifwelookatthefirstandthirdexperiments,wesee
that,whentheconcentrationtriples(from0.100Mto0.300M),therateofreactionalsotriples
(from2.210 6molL1s1to6.610 6molL1s1).Thisbehaviourtellsusthatthereaction
mustbefirstorderintheSO2Cl2concentration.Theratelawistherefore:

Toevaluatek,wecanuseanyofthethreesetsofdata.Choosingthefirstset:

Isouranswerreasonable?

Weshouldobtainthesamevalueofkbypickinganyotherpairofvalues.Withthelastpairof
data,ataninitial[SO2Cl2]of0.300molL1andaninitialrateofreactionof6.610 6molL1
s1,wecalculatekagaintobe2.210 5s1.Keepinmindthattheunitofafirstorderrate
constantis(time)1(inthisexample,s1).

Notethatwecouldalsouseexperiments2and3todeterminetheorderofthereaction.Fromthe
secondtothethirdexperiment,therateofreactionincreasesbythesamefactor(1.5)asthe
concentration,so,usingthesedatatoo,thereactionmustbefirstorder.

TocalculatethevalueofkfortheA+Bproductsreaction,weneedonlysubstituterateand
concentrationdataintotheratelaw.
Usingthedatafromexperiment1intable15.3:

Aftercancellingunits,thevalueofkwiththenetunitsis:

Notethattheunitofathirdorderrateconstantis(concentration)2(time)1.

Therateofareactionalwayshastheunit(concentration)(time)1.However,itisimportanttounderstand
thattheunitsoftherateconstantdependontheorderofthereaction.

Forexample,forafirstorderreaction,theunitis(time)1,andforasecondorderreactiontheunitis
(concentration)1(time)1.Thiscanalsoberationalisedfrom

Ifn=1,theunitfor[A]nisconcentration,sotheunitforkis(time)1.
Ifn=2,theunitfor[A]nis(concentration)2,sotheunitforkis(concentration)1(time)1.

PRACTICEEXERCISE15.2
Usethedatafromtheotherfourexperiments
(table15.3)tocalculatekforthisreaction.
Whatdoyounoticeaboutthevaluesofk?

Table15.4summarisesthereasoningusedtodeterminetheorderforeachreactantfromexperimentaldata.
TABLE15.4 Relationshipbetweentheorderofareactionandchangesinconcentrationandrate
Factorbywhichthe Factorbywhichtherateof Exponentoftheconcentration
concentrationischanged reactionchanges termintheratelaw

rateofreactionisunchanged

2 2=2 1 1

3 3=3 1 1

4 4=4 1 1

2 4=2 2 2

3 9=3 2 2

4 16=4 2 2
2 8=2 3 3

3 27=3 3 3

4 64=4 3 3

PRACTICEEXERCISE15.3
Thefollowingdataweremeasuredatthesame
temperatureforthereductionofnitricoxide
withhydrogen.

Initial
concentration

[NO] [H2] Initialrateof

(mol (mol formationofH2O
L1) L1) (molL1s1)
0.10 0.10 1.2310 3
0.10 0.20 2.4610 3
0.20 0.10 4.9210 3

Whatistheratelawforthereaction?

WORKEDEXAMPLE15.5

CalculatingReactionRatesfromtheRateLaw
Inthestratosphere,molecularoxygen,O2,canbebrokendownintotwooxygenatomsby
ultravioletradiationfromthesun.Whenoneoftheseoxygenatomsstrikesanozonemolecule,
O3,inthestratosphere,theozonemoleculeisdestroyedandtwooxygenmoleculesareformed.

Thisreactionispartofthenaturalcycleofozonedestructionandformationinthestratosphere.
Theexperimentallydeterminedratelawforthereactionis:

witharateconstantofk=4.1510 5mol1Ls1atthetemperatureoftheexperiment.The
reactantconcentrationsatanaltitudeof25kmare:[O3]=1.210 8molL1and[O]=1.7
10 14molL1.Whatistherateofozonedestructionforthisreactionatanaltitudeof25km?.

Analysis

Becausewealreadyknowtheratelawandthatthereactionisfirstorderforboth[O]and[O3],
theanswertothisquestionisobtainedbysubstitutingthegivenmolarconcentrationsintothe
 ratelaw.

Solution

Substitutingthegivenvaluesintotheratelawgives:

NotethattheunitsofrateofreactionaremolL1s1,whichis(concentration)(time)1,consistent
withwhatwelearnedearlier(seep.632).

Isouranswerreasonable?

Thereisobviouslynosimplecheck.Multiplyingthepowersof10fortherateconstantandthe
concentrationstogetherreassuresusthattherateofreactionisofthecorrectorderofmagnitude,
andwecanseethattheanswerhasthecorrectunits.Itisimportanttorealisethattheunitsofthe
rateconstantkarealwayssuchthatthecalculatedrateofreactionhastheunits(concentration)
(time)1,molL1s1inthisexample.Thismeansthattheunitofarateconstantisdifferentfora
reactionofoverallzero,first,secondorthirdorderetc.Weshowthisinotherexampleslaterin
thischapter.

PRACTICEEXERCISE15.4
Thefollowingreaction:

hastheratelaw:

Whatistheorderofthereactionwithrespect
toeachreactant?Whatistheoverallorderof
thereaction?

TheIntegratedRateLaw
Sofar,wehavelookedatdifferentialratelaws,thatis,ratelawsthatexpresstherateofreactionasa
functionofconcentration.Integratedratelawsarealsouseful.Recallthatintegratedratelawsexpress
concentrationasafunctionoftime.Considerthehypotheticalreaction:

Thedifferentialratelawhastheform:

Theintegratedratelawsforfirstorder(n=1),secondorder(n=2)andzeroorder(n=0)reactionsare
developedindividually.
FirstorderRateLaws
Let'sassumethatourhypotheticalreactionAproductsisfirstorderinA.Thedifferentialratelawisthen:

Rearrangementgives:

Wenowwanttolookatthedevelopmentoftheconcentrationfromthebeginningofthereaction(att=0)
untilacertainreactiontimet.Thismeanswehavetointegratethisrateequation.

Since (ignoringtheconstantofintegration),weobtain:

inwhich[A]tistheconcentrationattimetand[A]0istheinitialconcentration.Theintegratedfirstorderrate
lawisln[A]t=kt+ln[A]0,whichshowshowtheconcentrationofAchangeswithtime.Thus,iftheinitial
concentrationandtherateconstantareknown,[A]atanytimecanbecalculated.Theintegratedfirstorder
ratelawcanalsobeexpressedintermsoftheratioof[A]tand[A]0:

Thelastequationshowsthat,forfirstorderreactions,theconcentrationofAdecaysexponentiallywith
time.

WORKEDEXAMPLE15.6

ConcentrationtimeCalculationsforFirstorderReactions
Dinitrogenpentoxide,N2O5,isnotverystable.Inthegasphaseordissolvedinanonpolar
solvent,suchastetrachloromethane,itdecomposesbyafirstorderreactionintoN2O4andO2.

Theexperimentallydeterminedratelawis:

At45C,therateconstantforthereactionintetrachloromethaneis6.2210 4s1.Iftheinitial
concentrationofN2O5inthesolutionis0.100M,howlongwillittakefortheconcentrationto
dropto0.0100M?

Analysis
 Tosolvetheproblem,wesubstitutequantitiesinto:

andsolvefort.

Solution

First,weassemblethedata.

Substitutingthisintotheequation:

Sincetheunitforconcentration(M)cancelsout,wehave:

Aswehaveseeninearlierchapters,whentakingalogarithmofaquantity,thenumberofdigits
writtenafterthedecimalpointequalsthenumberofsignificantfiguresinthequantity.Here,
10.0hasthreesignificantfigures,sothenaturallogarithmof10.0,whichis2.303,hasthree
digitsafterthedecimal.

Solvingfort:

Thisisthetimeinseconds.

Isouranswerreasonable?

Wecansubstitutethetimeweobtained,alongwiththegiveninitialconcentration,intoour
equationandseewhetherwegetbackthegivenconcentrationattimet.

whichisexactlywhatwestartedwith.

PRACTICEEXERCISE15.5
IftheinitialconcentrationofN2O5ina
tetrachloromethanesolutionat45Cis0.500
M(seeworkedexample15.6),whatwillits
concentrationbeafterexactly1hour?

Theequationln[A]t=kt+ln[A]0isoftheformy=mx+c,whereaplotofyversusxgivesastraightline
withtheslopemandtheinterceptc.
Forfirstorderreactionsaplotofthenaturallogarithmofconcentrationversusreactiontimealwaysgivesa
straightline.Thisfactisoftenusedtodeterminetheorderofareaction.ForthereactionAproducts,the
plotofln[A]tversustisastraightline,ifthereactionisfirstorder.Conversely,iftheplotdoesnotgivea
straightline,thenthereactionisnotfirstorder.Workedexample15.7illustratestheprocedure.

WORKEDEXAMPLE15.7

DeterminingtheOrderofaReaction

Thefollowingdataareforthereaction .

Time(s) [N2O5](molL1)

0 2.00010 1
50 1.41410 1
100 1.00010 1

200 5.00010 2
300 2.50010 2
400 1.25010 2

(a)Showthattheratelawisfirstorderin[N2O5].
(b)Calculatethevalueoftherateconstant.

Analysis

(a)Ifaplotofln[N2O5]versustime,accordingtoln[N2O5]=kt+ln[N2O5]0,givesastraight
line,thereactionmustbefirstorderin[N2O5].
(b)Theslopeoftheplotin(a),ifitisastraightline,isequivalenttothenegativeoftherate
constant.

Solution

Firstwecalculatethenaturallogarithmsofthe[N2O5]values,whichgivesthefollowingdata:

Time(s) ln[N2O5]

0 1.609
50 1.956
100 2.303
 200 2.996
300 3.689
400 4.382

Wethenplotln[N2O5]versustime.

Theplotisastraightline,whichconfirmsthatthereactionisfirstorderin[N2O5](wecouldalso
useacalculatortodothisanalysis).Inthiscase,theslopeofthelineequalsk.Thisgivesus:

Isouranswerreasonable?

Wecansubstitutethisvaluebackintotheoriginalequationln[N2O5]=kt+ln[N2O5]0and
ensureweobtainthesame[N2O5]giveninthetableofdata.Doingthisshowsthatouransweris
correct.

PRACTICEEXERCISE15.6
Usingthedatagiveninworkedexample15.7,
calculate[N2O5]att=150s.

HalflifeofFirstorderReactions
Forafirstorderreaction,thehalflifeofthereactantcanbeobtainedfrom:

bysetting[A]tequaltohalfoftheinitialconcentration[A]0.
Substituting for[A]tand fortintheoriginalequationgives:

Notethatthelefthandsideoftheequationsimplifiestoln2,andso,tosolvetheequationfor wehave:

Notethatthehalflifeofafirstorderreactiondoesnotdependontheinitialconcentrationofthereactant.
Thiscanbeillustratedbyoneofthemostcommonfirstordereventsinnature,thechangethatradioactive
isotopesundergoduringradioactivedecay.Infact,youhaveprobablyheardthetermhalflifeusedin
referencetothelifespansofradioactivesubstances.

131I,anunstable,radioactiveisotopeofiodine,isusedinnuclearmedicineinbothdiagnosisandtherapyof
thyroiddisorders,suchasthyroidcancerandthyrotoxicosis.Thethyroidglandisasmallorganlocatedjust
belowtheAdam'sappleandastridethewindpipe.Itusesiodideionstomakeahormone,so,whena
patientisgivenadoseof131ImixedwithnonradioactiveI,bothionsaretakenupbythethyroidgland
(seefigure15.7).Thetemporarychangeinradioactivityoftheglandisameasureofthyroidactivity.131I
undergoesanuclearreactionwhereitemitsbetaradiation(seechapter27)andchangesintoastable
isotopeofxenon.Theintensityoftheradiationdecreases,ordecays,withtime(seefigure15.8).Notice
thatthetimeittakesforthefirsthalfofthe131Itodisappearis8days.Then,duringthenext8days,halfof
theremaining131Idisappears,andsoon.Regardlessoftheinitialamount,ittakes8daysforhalfofthat
amountof131Itodisappear,whichmeansthatthehalflifeof131Iisaconstant.

FIGURE15.7Scintigramofthyroidglandsafterthepatientwasinjectedwithradioactiveiodine.Thisshowsthe
activityoftheglandfromblue(mostactive)toyellow(leastactive).PasiekaPasieka

FIGURE15.8Firstorderradioactivedecayof131 I.Theinitialconcentrationoftheisotopeisrepresentedby[I]0 .
131Iisalsooneofthemostdangerousradioisotopesreleasedinnuclearexplosionsoraccidents.Ifitis
presentinhighlevelsintheenvironment,suchasafterradioactivefallout,itisabsorbedbythebodyafter
eatingcontaminatedfoodandconcentratesinthethyroidgland.When131Idecays,itcandamagethe
thyroidglandandmayleadtothyroidcancer.Onepossibletreatmentisaniodinesupplement,which
increasesthetotalamountofiodineinthebody.This,therefore,reducestherelativeproportionof131Iand
alsolowerstheuptakeandretentionofthisradioactiveisotopeinthebody.Suchsupplementswere
distributedtopeoplelivingneartheFukushimanuclearpowerplantinJapanafteritexplodedin2011.

WORKEDEXAMPLE15.8

HalflifeCalculations

Thehalflifeofradioactive131Iis8.0days.Whatfractionoftheinitial131Iwouldbepresentina
patientafter32.0daysifnoneofitwereeliminatedthroughnaturalbodyprocesses?

Analysis

Havinglearnedthat131Iisaradioactiveisotopeandsodecaysbyafirstorderprocess,weknow
thatthehalflifeisconstantanddoesnotdependonthe131Iconcentration.

Solution

Wecansolvetheproblemusingtheintegratedfirstorderratelaw.We'llneedthefirstorderrate
constantk,whichwecanobtainfromthehalflifebyrearranging:

Thenwecanuse tocalculatethefraction :

Takingtheantilogarithmofbothsides,wehave:

Isouranswerreasonable?

Aperiodof32.0daysisexactlyfourhalflives.Ifwetakethefractioninitiallypresenttobe1,
wecansetupatable.

Halflife 0 1 2 3 4
 Fraction 1

Halfofthe131Iislostinthefirsthalflife,halfofthatdisappearsinthesecondhalflife,andso
on.Therefore,thefractionremainingafterfourhalflivesis .

Theinitialconcentration,[131I]0,is16.0timesaslargeastheconcentrationafter32.0days.The
fractionremainingafter32.0daysis ,whichisexactlywhatweobtainedusingthe
mathematicalapproach.

SecondorderRateLaws
Forageneralreactioninvolvingonereactant,whichissecondorderin[A]

thesecondorderdifferentialratelawis:

Again,tolookathowtheconcentrationofBchangesovertime,wehavetorearrangethisequationtogive
,andthenintegratethisbetweenthestartofthereaction(t=0)andacertainreactiontime
(t).

As ,andignoringtheconstantofintegration,weobtain:

Thisequationistheintegratedsecondorderratelaw.Itshowsthatforsecondorderreactionsthe
reciprocaloftheconcentrationisrelatedlinearlytotime.

WORKEDEXAMPLE15.9

ConcentrationtimeCalculationsforSecondorderReactions
Nitrosylchloride,NOCl,decomposesslowlytoNOandCl2.

Theratelawshowsthattherateofreactionissecondorderin[NOCl].

Therateconstantkequals0.020mol1Ls1atacertaintemperature.Iftheinitialconcentration
ofNOClinaclosedreactionvesselis0.050M,whatistheconcentrationafter30minutes?

Analysis

Wearegivenaratelawandcanseethatitisforasecondorderreaction.Wemustcalculate
[NOCl]t,themolarconcentrationofNOCl,after30min(1800s)using
.

Solution

Weknowthat:

Thegeneralintegratedsecondorderratelawis:

Makingthesubstitutiongives:

Solvingfor gives:

Takingthereciprocalsofbothsidesgivesusthevalueof[NOCl]:

ThemolarconcentrationofNOClhasdecreasedfrom0.050Mto0.018Mafter30minutes.

Isouranswerreasonable?

TheconcentrationofNOClhasdecreased,asitmust.Wecancheckthecalculationby
substitutingthisvalueintotheoriginalequation.

PRACTICEEXERCISE15.7
 Forthereactioninworkedexample15.9,
determinehowlongitwouldtakeforthe
NOClconcentrationtodropfrom0.040Mto
0.010M.

Therateconstantforasecondorderreactionwitharatelawfollowing canbe
determinedgraphicallybyamethodsimilartothatusedforafirstorderreaction.Theequationcorresponds
toanequationforastraightline:

Whenareactionissecondorder,aplotof versustshouldyieldastraightlinewithaslopek.Thisis
illustratedinfigure15.9bforthedecompositionofHI,accordingto2HI(g)H2(g)+I2(g),usingdata
fromworkedexample15.1.Figure15.9ashowsaplotofln[HI]versustimethefactthatthisisacurve
confirmsthereactionisnotfirstorderin[HI].

FIGURE15.9 Secondorderkinetics:
(a)agraphofln[HI]versustimeand
(b)
agraphof versustimeforthedatainworkedexample15.1.

HalflifeofSecondorderReactions
Afteronehalflifeofasecondorderreactionhaselapsed,wehave:
Insertingthisinto gives:

Thus,incontrasttofirstorderreactions,thehalflifeofasecondorderreactionisinverselyproportionalto
theinitialconcentrationofthereactant.

WORKEDEXAMPLE15.10

HalflifeCalculations

Thereaction2HI(g)H2(g)+I2(g)hastheratelaw,rate=k[HI]2,withk=0.079mol1Ls1at
508C.WhatisthehalflifeforthisreactionatthistemperaturewhentheinitialHIconcentration
is0.050M?

Analysis

Theratelawtellsusthatthereactionissecondorder.Tocalculatethehalflife,weneedtouse

Solution

Theinitialconcentrationis0.050molL1andk=0.079mol1Ls1.Substitutingthesevalues
into gives:

Isouranswerreasonable?

Substitutingthisvaluebackintotheequationaboveshowsthatthisansweriscorrect.

PRACTICEEXERCISE15.8

Supposethatthevalueof foracertain
 reactionwasfoundtobeindependentofthe
initialconcentrationofthereactants.What
couldyousayabouttheorderofthereaction?

ZeroorderRateLaws
Whilemostreactionsthatinvolveonlyonereactantarefirstorsecondorderreactions,therearereactions
forwhichtherateofthereactionisconstantthatis,itdoesnotvarywithconcentration.Anexampleisthe
thermaldecompositionofbromoethaneonazincsurface,whichactsasacatalyst.

Thereactionoccursatthesurfaceofthezincmetal,whichissaturatedwithbromoethane.Therefore,the
reactionrateisnotdependentontheconcentrationofbromoethane.Suchreactionsarecalledzeroorder
reactions.ForthegeneralzeroorderreactionAproducts,wecanwritetheratelawas:

HowdoestheconcentrationofAchangeovertime?Asbefore,wearrangetheratelawtogived[A]=kdt
and,byintegrationbetweenthebeginningofthereaction(t=0)andacertainreactiontime(t),the
integratedratelawforazeroorderreactioncanbeobtained.

Thisequationcorrespondstoanequationforastraightline.

Aplotof[A]versustimegivesastraightlineofslopek,asshowninfigure15.10.

FIGURE15.10Forazeroorderreaction,[A]versustisastraightlinewithslopek.
Thehalflifeofazeroorderreactionis when .Insertingthisintotheequation[A]t=
kt+[A]0gives:

Forazeroorderreaction,thehalflifeisproportionaltotheconcentrationofthereactant.

Manyreactionswhichrequiresurfacesofmetalsshowzeroorderkinetics.Theexampleshowninfigure
15.11isthedecompositionofdinitrogenoxideintonitrogenandoxygenonahotplatinumsurface:

WhentheplatinumsurfaceiscompletelycoveredwithN2Omolecules,anincreasein[N2O]doesnot
changetherateofthereaction.

FIGURE15.11Thedecompositionreaction2N2 O(g)2N2 (g)+O2 (g)takesplaceonaplatinumsurface.The

rateofdecompositionofN2 Oisthesamein(a)and(b),regardlessoftheconcentrationofN2 O,
becausetheplatinumsurfacecanaccommodateonlyacertainnumberofmolecules.Asaresult,
thisreactioniszeroorderin[N2 O].

Also,manythermaldecompositionreactionsfollowzeroorderkinetics,wherethereactionrateis
independentoftheconcentrationofthereactant.Ethanolmetabolisminthebodyiscatalysedbythe
enzymealcoholdehydrogenase.Becauseonlyalimitedamountofethanolcanberemovedinthisway,if
thereisahighconcentrationofethanolintheblood,metabolismcanfollowzeroorderkinetics(seealso
pp.6723).

Beforemovingontolookatthetheoryofchemicalkinetics,studytable15.5,whichsummarisesthe
kineticsforreactionsofdifferentorders.
TABLE15.5 SummaryofthekineticsforreactionsofthetypeAproductsthatarezero,firstorsecondorder
in[A]

Zeroorder Firstorder Secondorder

Ratelaw rate=k rate=k[A] rate=k[A]2
 Integratedratelaw [A]=kt+[A]0 ln[A]=kt+ln[A]0

Lineargraph [A]versust ln[A]versust

Slopeoflineargraph k k k
Unitsofrateconstant molL1s1 s1 mol1Ls1

Halflife

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.5TheoryofChemicalKinetics
Insection15.2wementionedthatnearlyallreactionsproceedfasterathighertemperatures.Generally,the
rateofreactionincreasesbyafactorofabouttwoorthreeforeach10Cincreaseintemperature,although
theexactamountofincreasediffersfromonereactiontoanother.Temperatureevidentlyhasasignificant
effectonreactionrate.Tounderstandwhy,weneedtodevelopsometheoreticalmodelsthatexplainour
observations.Oneofthesimplestmodelsiscalledcollisiontheory.

CollisionTheory
Thebasicprincipleofcollisiontheoryisthattherateofareactionisproportionaltothenumberofeffective
collisionspersecondamongthereactantmolecules.Aneffectivecollisionisonethatactuallyresultsinthe
formationofproductmolecules.Anythingthatcanincreasethefrequencyofeffectivecollisionsshould,
therefore,increasetherate.

Oneoftheseveralfactorsthatinfluencethenumberofeffectivecollisionspersecondisconcentration.As
reactantconcentrationsincrease,thenumberofcollisionspersecondofalltypes,includingeffective
collisions,alsoincreases.

Noteverycollisionbetweenreactantmoleculesactuallyresultsinachemicalchange.Weknowthisbecause
thereactantatomsormoleculesinagasoraliquidundergoanenormousnumberofcollisionspersecond
witheachother.Ifeverycollisionwereeffective,allreactionswouldbeoverinaninstant.Onlyaverysmall
fractionofallthecollisionscanreallyleadtoanetchange.Whyisthisso?

MolecularOrientation
Inmostreactions,whentworeactantmoleculescollidetheymustbeorientedcorrectlyforareactionto
occur.Forexample,thereactionrepresentedbythefollowingequation:

appearstoproceedbyatwostepmechanism,whichwewilldiscussinsection15.6.Atthispoint,itis
sufficienttoknowthatonestepinvolvesthecollisionofanNO2Clmoleculewithachlorineatom,Cl.

TheorientationoftheNO2ClmoleculewhenhitbytheClatomisimportant(seefigure15.12).The
orientationshowninfigure15.12acannotresultintheformationofCl2becausethetwoClatomsarenot
beingbroughtcloseenoughtogetherforanewClClbondtoformasanNClbondbreaks.Figure
15.12bshowsthenecessaryorientationofNO2ClandClthatleadstosuccessfulproductformation.
 FIGURE15.12 Theimportanceofmolecularorientationduringacollisioninareaction.Thekeystepinthe
decompositionofNO2 CltoNO2 andCl2 isthecollisionofClwithaNO2 Clmolecule.
(a)Anineffectivelyorientedcollision
(b)Aneffectivelyorientedcollision.

ActivationEnergy
Notallcollisions,eventhosecorrectlyoriented,areenergeticenoughtoresultintheformationofproducts
thisisthemajorreasonwhyonlyasmallpercentageofallcollisionsactuallyleadtoachemicalchange.

Whyisthisso?ThisquestionwasfirstaddressedbySvanteArrhenius(NobelPrizeinchemistry,1903)in
the1880s(figure15.13).Heproposedtheexistenceofathresholdenergy,theactivationenergy(Ea),
whichmustbeovercomeforareactiontooccur.Thiscanberationalisedbyconsideringtheprevious
reactionofNO2ClwithCl.Inthisreaction,anNClbondmustbreakandaClClbondmustform.
BreakinganNClbondrequiresaconsiderableenergyof188kJmol1,whichmustcomefrom
somewhere.Thecollisiontheorypostulatesthattheenergyrequiredtobreakthebondcomesfromthe
kineticenergy(KE)ofthemoleculesbeforethecollision.Thiskineticenergyisconvertedintopotential
energy(PE)asthemoleculesaredistortedduringacollisionoldbondsinthereactantmoleculesarebroken,
andnewbondsareformedintheproductmolecules.Formostchemicalreactions,theactivationenergyis
quitelarge,andonlyasmallfractionofallwelloriented,collidingmoleculeshaveit.
 FIGURE15.13SvanteArrhenius(18591927)isoneofthefoundersofphysicalchemistry.Hewasawardedthe
NobelPrizeinchemistryin1903forhisworkonthetheoryofionicdissociation.NYPL/Science
Source

Thereactionprogresscanbeplottedasshowninfigure15.14,whichiscalledapotentialenergydiagram.

FIGURE15.14PotentialenergydiagramforthereactionNO2 Cl+ClNO2 +Cl2 .Theactivationenergy,Ea ,is

thecombinedkineticenergythatthecollidingparticlesmusthaveforthereactiontooccur.His
theenthalpydifferencebetweenproductsandreactants.Inanexothermicreaction,whichisshown
here,Hisnegative(H<0).

Theverticalaxisrepresentspotentialenergy,whichchangesduringareactionasthekineticenergyofthe
collidingparticlesisconvertedintopotentialenergy.Thehorizontalaxisiscalledthereactioncoordinate,
anditrepresentstheextenttowhichthereactantshavechangedtotheproducts.Thearrangementfoundon
thetopofthepotentialenergyhill(orbarrier)iscalledthetransitionstate.Atthetransitionstate,
sufficientenergyisconcentratedtoallowthebondsinthereactantstobreak.Astheybreak,energyis
redistributedandnewbondsform,givingproducts.Oncethetransitionstateisreached,thereactioncan
eitherproceedtogiveproductsor,inthereversedirection,togivereactants.Atransitionstatehasadefinite
geometry,adefinitearrangementofbondingandnonbondingelectrons,andadefinitedistributionof
electrondensityandchargetheoldbondsarenotcompletelybrokenandthenewbondshavenotyetbeen
formed.Becauseatransitionstateisatanenergymaximumonanenergydiagram,wecannotisolateitand
cannotdetermineitsstructureexperimentally.Itslifetimeisoftheorderofapicosecond(thedurationofa
singlebondvibration).However,eventhoughwecannotobserveatransitionstatedirectlybyexperimental
means,wecanofteninferagreatdealaboutitsprobablestructurefromotherexperimentalobservations.

Thedifferenceinenergybetweenthereactantsandthetransitionstateiscalledtheactivationenergy,Ea .
Theactivationenergyistheminimumenergyrequiredforareactiontooccuritcanbeconsideredan
energybarrierforthereaction.Iftheactivationenergyislarge,veryfewmolecularcollisionsoccurwith
sufficientenergytoreachthetransitionstate,andthereactionisslow.Iftheactivationenergyissmall,many
collisionsgeneratesufficientenergytoreachthetransitionstate,andthereactionisfast.

Inareactionthatoccursintwoormoresteps,eachstephasitsowntransitionstateandactivationenergy.
Figure15.15showsanenergydiagramforahypotheticalreactionA+BC+D,whichproceedsintwo
steps.Areactionintermediatecorrespondstoanenergyminimumbetweentwotransitionstates,inthis
casetransitionstates1and2.Notethat,becausetheenergiesofthereactionintermediatesarehigherthan
theenergiesofeitherthereactantsortheproducts,theseintermediatesarehighlyreactiveandcanonly
rarelybeisolated.However,becauseintermediateshaveacertainlifetime(incontrasttotransitionstates),
searchingforthepresenceofareactionintermediatewithopticalorotherfastrecordingmethodsmay
provideexperimentalsupportforareactionmechanism.Itisadvisablethatyoubecomefamiliarwiththe
definitionofreactionintermediatesandtransitionstatesinordertoavoidmixingthemup.

FIGURE15.15Energydiagramforatwostepreactioninvolvingtheformationofanintermediate.Theenthalpyof
thereactantsishigherthanthatoftheproducts,andHfortheconversionofA+BtoC+Dis
thereforenegative.

BoththereactionofNO2ClwithCltogiveNO2andCl2showninfigure15.14andourhypotheticalreaction
A+BC+Dinfigure15.15areexothermic,asindicatedbythefactthattheproductshavealower
potentialenergythanthereactants(energydifference,orenthalpyofreactionH<0).Apotentialenergy
diagramforanendothermicreaction,wherethepotentialenergyoftheproductsishigherthanthatofthe
reactants(H>0),isshowninfigure15.16.
 FIGURE15.16Apotentialenergydiagramforanendothermicreaction.

ItisimportanttounderstandthatHhasnoinfluenceontherateofthereaction.Therateofareactionis
solelydeterminedbytheheightoftheactivationbarrier,Ea.

Let'scomebacktoourreactionofNO2ClwithClatomsinfigure15.14.Acertainminimumenergy,Ea ,is
requiredforanNO2ClandaClatomspeciestogetoverthehillandformproducts.Thisisenergyprovided
bythecollisionbetweenthesespecies.AcollisionbetweenanNO2ClmoleculeandaClatomwithsmall
kineticenergiesdoesnotprovideenoughenergytogetoverthebarrier,andnoreactionoccursevenif
theirorientationisideal.Atagiventemperature,onlyacertainfractionofthecollisionspossessenough
energytobeeffectiveandformproducts.

Theconceptthatareactioninvolvingtwomoleculescanoccuronlyaftersuccessfulacollisionbetween
thesespeciesseemsquitelogical.However,manyreactionsinvolveonlyonemolecule:forexample,the
decompositionofN2O5toN2O4andO2showninworkedexample15.7.Howdomoleculesinsuch
reactionsacquiretheenergyrequiredtosurmounttheenergybarrierassociatedwithbreakingthebonds?
ThisquestionwasaddressedforreactionsinthegasphasebytheEnglishscientistsSirCyrilHinshelwood
(NobelPrizeinchemistryin1956)andFredrickAlexanderLindemann(figure15.17)whosuggestedthat
therequiredactivationenergyisaccumulatedthroughcollisionsbetweenthesemolecules,whichproduce
energised(activated)molecules.Qualitatively,therateoftheunimolecularreactionistherefore
proportionaltotheconcentrationofactivatedmolecules,whichinturnisproportionaltotheconcentration
ofunenergisedmolecules.
 FIGURE15.17 (a)SirCyrilHinshelwood(NobelPrizeinchemistryin1956)and
(b)FrederickLindemann,ChiefScientificAdvisortoWinstonChurchillduringWorldWarII.
RayNelson

TemperatureEffects:TheArrheniusEquation
Withtheconceptofactivationenergy,wecanexplainwhytherateofareactionincreasessomuchwith
increasingtemperature.Thetwoplotsinfigure15.18correspondtodifferenttemperaturesforthesame
mixtureofreactants.Eachcurveisaplotofthedifferentfractionsofallcollisions(verticalaxis)thathave
particularvaluesofkineticenergyofcollision(horizontalaxis).Thetotalareaunderacurvethenrepresents
thetotalnumberofcollisions,becauseallofthefractionsmustadduptothistotal.Noticewhathappensto
theplotswhenthetemperatureisincreasedthemaximumpointshiftstotherightandthecurveflattens
somewhat.

FIGURE15.18KineticenergydistributionsforareactionmixtureattwodifferenttemperaturesT1 andT2 .

Theshadedareasunderthecurvesinfigure15.18representthesumofallthefractionsofthetotalcollisions
thatequalorexceedtheactivationenergy.Thissumwecouldcallitthereactingfractionismuch
greateratthehighertemperaturethanatthelowertemperaturebecauseasignificantfractionofthecurve
shiftsbeyondtheactivationenergywithevenamodestincreaseintemperature.Inotherwords,atthehigher
temperature,amuchgreaterfractionofthecollisionsresultinachemicalchange,sothereactantsreact
fasteratthehighertemperature.

Infact,thefractionsofeffectivecollisionsincreaseexponentiallywithtemperature.Arrheniuspostulated
thatthenumberofcollisionshavinganequalorgreaterenergythantheactivationenergyisgivenbythe
expression:

Theterm istheprobabilitythatanygivencollisionwillresultinareaction.

Theshapesofthecurvesinfigure15.18aregivenbythesocalledMaxwellBoltzmanndistributions.All
moleculesofaparticularchemicalspecieshavethesamemasssotheirkineticenergiesdependonlyonthe
velocitiesoftheparticles .Inanymixtureofmovingparticles,someparticleshave
alowspeed(lowenergy),somehaveahighspeed(highenergy),butmosthaveaspeedveryclosetothe
average.TheMaxwellBoltzmanndistributionshowshowthespeeds(energies)ofmovingparticlesina
mixturechangewithtemperature.Asyoucanseeinfigure15.18,therearenomoleculesatzeroenergyand
fewmoleculesathighenergy.Mostimportantly,thereisnomaximumenergyvalue(thecurvedoesnot
touchthexaxis).

Thus,summarisingourdiscussionsofar,tworequirementsmustbesatisfiedforasuccessfulreaction:
1.Thecollisionenergymustequalorexceedtheactivationenergy.
2.Therelativeorientationofthereactantsmustallowformationofanynewbondsthatarenecessaryto
producetheproductsofthereaction.
Withthesetworequirements,therateconstantkcannowbeexpressedas:

Inthisequation,zrepresentsthecollisionfrequency(thetotalnumberofcollisionspersecond).Thefactorp
iscalledthestericfactor,andrepresentsthefractionofcollisionswithcorrectorientationssothattheactual
chemicalreactioncanoccur.Thefactor reflectsthefractionofcollisionswithsufficientenergyto
surmounttheactivationbarrier.Thisequationismostcommonlywrittenas:

ThisiscalledtheArrheniusequation.ThefactorszparereplacedbyA,whichiscalledthepreexponential
orfrequencyfactorforthisreaction.Ahasthesameunitsastherateconstantandthisdependsontheorder
ofthereaction.Inprinciple,Aisdependentonthetemperature,sincethefrequencyofcollisionsincreases
withincreasingtemperature.However,thistemperaturedependenceismuchsmallerthantheexponential
term.Asanapproximation,Aisthereforeusuallyconsideredasaconstant.

Howcantheactivationenergybedeterminedexperimentally?Takingthenaturallogarithmofeachsideof
theArrheniusequationgives:

Thisisalinearequationofthetypey=mx+c,
Thus,bymeasuringtherateconstantatdifferenttemperaturesforareaction,aplotoflnkversus givesa
straightline(ifthereactionobeystheArrheniusequation).Fromtheslopeandtheintercept,Ea andthepre
exponentialfactorAcanbedetermined.Indeed,mostreactionsobeytheArrheniusequationtoagood
approximation,whichindicatesthatthecollisiontheoryisaphysicallyreasonablemodel.

WORKEDEXAMPLE15.11

DeterminationofEaandthepreexponentialfactorA

ConsiderthesecondorderdecompositionofNO2intoNOandO2.Theequationis:

Thefollowingdatawerecollectedforthereaction.

k(mol1Ls1) Temperature(C)
7.8 400
10 410
14 420
18 430
24 440
DeterminetheactivationenergyinkilojoulespermoleandthepreexponentialfactorAforthis
reaction.

Analysis

TheArrheniusequation, ,applies,buttheuseofratedatatodeterminethe
activationenergygraphicallyrequiresthatweplotlnk,notk,versusthereciprocalofthe
temperatureinkelvin,sowehavetoconvertthegivendataintolnkand beforewecanplotthe
graph.Fromtheslopeofthestraightline,Ea canbeobtained.ThefactorAcanbedetermined
eithergraphically,fromtheintercept,oralgebraically,bysubstitutionofthedataintothe
Arrheniusequation.NotethatAmusthavethesameunitsastherateconstantk.

Solution

Toillustrate,usingthefirstsetofdata,theconversionsare:

Wearecarryingextrasignificantfiguresforthepurposeofgraphingthedata.Theremaining
conversionsgivethefollowingtable.

lnk
2.05 1.48610 3
2.30 1.46410 3
2.64 1.44310 3

2.89 1.42210 3
3.18 1.40310 3

Thenweplotlnkversus asshowninthefigurebelow.

Alternatively,youcanuseacomputerorscientificcalculatortocalculatetheslopeofthestraight
linethatbestfitsthedata(linearregression).Thiswillindicatethequalityofthelinearfit.
(a)TodetermineEa ,calculatetheslopeofthestraightlineasfollows:

AfterchangingsignsandsolvingforEa wehave:

(b)TodetermineA,wemustfindtheyinterceptofthegraph.(Ifyouusedacomputeror
 calculatortodeterminetheslope,thelinearregressionalsogivesyoutheintercept.)We
dothisbyusingtheequationy=mx+c,theslopecalculatedinpart(a),andthelnk
versus datagivenonp.656.Puttingthedataintotheequationgivesfivedifferent
valuesforc(22.82,22.80,22.85,22.84and22.80),theaverageofwhichis22.82.This
correspondstolnAn,sotakingtheexponentialofthisgivesA=8.110 9mol1Ls1.The
unitsofAarethoseforasecondorderreaction.

Isouranswerreasonable?

Theactivationenergyandpreexponentialfactorarepositive.Youcancheckthesevaluesby
substitutingthembackintotheoriginalequation.

Theactivationenergycanalsobeobtainedfromtworateconstantsmeasuredatdifferenttemperatures.At
temperatureT1,therateconstantk1isexpressedas:

AttemperatureT2,wethenhave:

SincethepreexponentialfactorAisapproximatelyindependentofthetemperature,subtractionofthefirst
equationfromthesecondgives:

Workedexample15.12illustratestheuseofthisequation.

WORKEDEXAMPLE15.12

CalculatingtheActivationEnergyfromTwoRateConstants

Thedecompositionofhydrogeniodide,HI,hasrateconstantsk=0.079mol1Ls1at508Cand
k=0.24mol1Ls1at540C.WhatistheactivationenergyofthisreactioninkJmol1?

Analysis

Whenthereareonlytwodatasets,thesimplestwaytoestimateEa istosolvetheequation:

Solution

Let'sbeginbyorganisingthedataasmalltableishelpful.Chooseoneoftherateconstantsask1
(itdoesn'tmatterwhichone)andthenfillinthetable.

k(mol1Ls1) T(K)
0.079 508+273=781
 0.24 540+273=813

WealsohaveR=8.314Jmol1K1.Substitutingintotheinitialequationyields:

Multiplyingbothsidesby8.314Jmol1K1gives:

SolvingforEa ,wehave:

Notethatthisisofthesameorderofmagnitudeastheenergyofasinglebond.

PRACTICEEXERCISE15.9
Thereaction2NO22NO+O2hasan
activationenergyof111kJmol1.At400C,
k=7.8mol1Ls1.Whatisthevalueofkat
430C?

Recallfromthestartofthechapterthattheconversionofdiamondintographiteisveryslow,eventhough
graphiteisthermodynamicallystableunderstandardconditionsatroomtemperature.Thereasonforthisis
thattheactivationenergyfortheprocess,whichinvolvesbreakingstrongcarboncarbonbonds,ishigh(it
requirestemperatureshigherthan1500Cunderexclusionofoxygen).Justbecauseaproductisthermo
dynamicallystabledoesnotmeanthatitsformationwillberapid.Athermodynamicallyunstableproduct
canexistunderstandardconditionsifalargeactivationenergyisrequiredforitsreaction.Becauseofthis,
diamondiscalledmetastableatatmosphericpressureandroomtemperature.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.6ReactionMechanisms
Atthebeginningofthischapterwementionedthatmostreactionsdonotoccurinasinglestep.Instead,the
netoverallreactionistheresultofaseriesofsimplereactions,eachofwhichiscalledanelementary
reaction.Anelementaryreactionisareactioninwhichoneormoreofthechemicalspeciesreactsdirectly
toformproductsinasinglereactionstepandwithasingletransitionstate.Inthesecases,theratelawcanbe
writtenfromitschemicalequation,usingitscoefficientsasexponentsfortheconcentrationtermswithout
requiringexperimentstodeterminetheexponents.Theentireseriesofelementaryreactionsiscalledthe
reactionmechanism.Formostreactions,theindividualelementaryreactionscannotactuallybeobserved
instead,weseeonlythenetreaction.Therefore,themechanismachemistwritesisreallyatheoryabout
whatoccursstepbystepasthereactantsarechangedtotheproducts.

Whatmakesanelementaryreactionelementary?Rememberthattheexponentsoftheconcentrationterms
fortheratelawofanoverallreaction(theorder)bearnonecessaryrelationshiptothecoefficientsinthe
overallbalancedequation.Aswekeepemphasising,theexponentsintheoverallratelawmustbe
determinedexperimentally.Sowhatmakesanelementaryreactionelementaryisthatasimplerelationship
betweencoefficientsandexponentsdoesexist.

Becausetheindividualstepsinamechanismsometimescannotbeobserveddirectly,devisingamechanism
forareactionrequiressomeingenuity.However,wecanimmediatelytellwhetheraproposedmechanismis
feasible.Theoverallratelawderivedfromthemechanismmustagreewiththeobservedratelawforthe
overallreaction.

Let'sseehowtheexponentsoftheconcentrationtermsinaratelawforanelementaryreactioncanbe
devised.Considerthefollowingexampleofanelementaryreactionthatinvolvescollisionsbetweentwo
identicalmoleculesleadingdirectlytotheproducts.

Howcanwepredictthevalueoftheexponentn?IftheNO2concentrationwasdoubled,therewouldbe
twiceasmanyindividualNO2moleculesandeachwouldhavetwiceasmanyneighbourswithwhichto
collide.ThenumberofNO2toNO2collisionspersecondthereforewouldincreasebyafactorof4,resulting
inanincreaseintheratebyafactorof4,whichis2 2.Earlierwesawthat,whendoublingaconcentration
leadstoafourfoldincreaseintherate,theconcentrationofthatreactantisraisedtothesecondpowerinthe
ratelaw.Thus,if2NO2NO3+NOrepresentsanelementaryreaction,itsratelawshouldbe:

Bydefinition,theexponentintheratelawforanelementaryreactionisthesameasthecoefficientinthe
chemicalequation.Ifwefound,experimentally,thattheexponentinthisratelawwasnotequalto2,the
reactionisnotreallyanelementaryreaction.Anotherwaytodefineanelementaryreactionisbyits
molecularity.Molecularityisthenumberofspeciesthatmustcollidetoproducethereactioninan
elementaryreaction.Theorderofanelementaryreactionisthesameasthemolecularityofthatreaction:
Anelementaryreactioninvolvingonemoleculeisunimolecularandhasafirstorderratelaw.
Anelementaryreactioninvolvingtwospeciesisbimolecularandhasasecondorderratelaw.
Anelementaryreactioninvolvingthreespeciesistermolecularandhasathirdorderratelaw.(Thereis
lowprobabilitythatthreemoleculeswillcollidewiththecorrectorientationandsufficientenergyto
surmounttheactivationbarrier,sotermolecularreactionsareextremelyrare.)

Rememberthatthisruleappliesonlytoelementaryreactions.Ifallweknowisthebalancedequationforthe
overallreaction,theonlywaywecanfindtheexponentsoftherateequationisbydoingexperiments.
TheRatedeterminingStep
Theratelawofanelementaryreactionhelpschemiststodeterminepossiblereactionmechanisms.Howdoes
thiswork?Letusconsiderthegaseousreaction:

Experimentally,therateisfirstorderinNO2Cl,sotheratelawis:

Thefirstquestionwemightaskis:Couldtheoverallreaction(2NO2Cl2NO2+Cl2)occurinasinglestep
bythecollisionoftwoNO2Clmolecules?Theanswerisno,becausethenitwouldbeanelementaryreaction
andthepredictedratelawwouldincludeasquaredterm,[NO2Cl]2.Buttheexperimentalratelawisfirst
orderinNO2Cl.Sothepredictedandexperimentalratelawsdon'tagree,andwemustlookfurthertofindthe
mechanismofthereaction.

Onthebasisofchemicalintuitionandotherinformation,chemistsbelievetheactualmechanismofthe
reactionisthefollowingtwostepsequenceofelementaryreactions.

TheClatomformedhereinthefirststepisanintermediate.Inthisreaction,weneveractuallyobservetheCl
atombecause,onceitisformed,itquicklyreactsinthesecondstep.Recallfromsection15.5thatan
intermediateishigherinenergyandhasamorelimitedlifetimethanthereactantsandproducts.

Noticethatwhenthetworeactionsareadded,theintermediate,Cl,dropsoutandweobtainthenetoverall
reaction2NO2Cl2NO2+Cl2.Beingabletoaddtheelementaryreactionsandobtaintheoverallreaction
isanothermajortestofamechanism.

Inanymultistepmechanism,onestepisusuallymuchslowerthantheothers.Inthismechanism,for
example,itisbelievedthatthefirststepisslow,andthat,onceaClatomforms,itreactsveryrapidlywith
anotherNO2Clmoleculetogivethefinalproducts.

Thefinalproductsofamultistepreactioncannotappearmorerapidlythandotheproductsoftheslowstep,
sotheslowstepinamechanismiscalledtheratedeterminingsteporratelimitingstep.Inthetwostep
mechanismforthisparticularreaction,then,thefirstreactionistheratedeterminingstepbecausethefinal
productscannotbeformedfasterthantherateatwhichClatomsform.

Theratedeterminingstepissimilartoaslowworkeronanassemblyline.Theproductionratedependson
howquicklytheslowworkerworks,regardlessofhowfasttheotherworkersare.Thefactorsthatcontrolthe
speedoftheratedeterminingstepthereforealsocontroltheoverallrateofthereaction.Thismeansthatthe
ratelawfortheratedeterminingstepisdirectlyrelatedtotheratelawfortheoverallreaction.Notethatthe
ratedeterminingstepcanbeanyofthestepsinasequenceofelementaryreactions(andnotnecessarilyonly
thefirststep,asinourexample).

Becausetheratedeterminingstepisanelementaryreaction,wecanpredictitsratelawfromthecoefficients
ofitsreactants.ThecoefficientofNO2ClinitsrelativelyslowbreakdowntoNO2andClis1.Therefore,the
ratelawpredictedforthefirststepis:

Noticethatthepredictedratelawderivedforthetwostepmechanismagreeswiththeexperimentally
measuredratelaw.Althoughscientistsmayneveractuallyprovethecorrectnessofaproposedmechanism,
atleastconsiderablesupportforitcanbeprovided.Fromthestandpointofkinetics,therefore,the
mechanismisreasonable.

WORKEDEXAMPLE15.13

DrawinganEnergyDiagram
Drawanenergydiagramforatwostepexothermicreactioninwhichthesecondstepisrate
determining.

Analysis

Atwostepreactioninvolvestheformationofanintermediate.Ifthereactionisexothermic,the
productsmustbelowerinenergythanthereactants.Inorderforthesecondsteptoberate
determining,itmusthaveahigherenergybarrier.

Solution

Inthediagram,theintermediateisofrelativelyhighenergyandisformedinareversible
equilibrium(theactivationenergyrequiredtoreformthereactantsisEa1).Theeffectiveenergy
requiredforthereactionisthedifferencebetweentheenergiesofthesecondtransitionstateand
thereactants.Theintermediatecouldalsobeofrelativelylowenergy,buttheactivationenergy
forthesecondtransitionstatewillbecorrespondinglyhigher.

PRACTICEEXERCISE15.10
Inwhatwaywouldtheenergydiagramdrawn
inworkedexample15.13changeifthe
reactionwereendothermic?
MechanismswithFast,ReversibleSteps
Wewillnowstudythefollowinggasphasereaction:

Theexperimentallydeterminedratelawis:

Wecanquicklytellfromthisratelawthat2NO+2H2N2+2H2Oisnotitselfanelementaryreaction.Ifit
were,theexponentfor[H2]wouldbe2.Obviously,amechanisminvolvingtwoormorestepsmustbe
involved.

Achemicallyreasonablemechanismthatyieldsthecorrectformfortheratelawconsistsofthefollowing
twosteps.

Onetestofthemechanism,aswesaid,isthatthetwoequationsmustaddtogivethecorrectoverall
equation,andtheydo.Further,thechemistryofthesecondstephasactuallybeenobservedinseparate
experiments.N2Oisknownaslaughinggasandisusedasananaestheticinmedicineanddentistry.Itdoes
reactwithH2togiveN2andH2O.AnothertestofthemechanisminvolvesthecoefficientsofNOandH2in
thepredictedratelawforthefirststep,thesupposedratedeterminingstep.

ChemistryResearch

ReactionsofCO2inWater:aSimpleKineticSystem?

AssociateProfessorMarcelMaeder,UniversityofNewcastle

IntheChemistryResearchfeatureinchapter9,wesummarisedourstudiesoftheequilibrium
processesinvolvedinthedissolutionofCO2inwater.Here,wenowpresenttheresultsofour
investigationsintothekineticsofthereactionsofCO2inwater.

IthasbeenknownformanyyearsthattherearetwoimportantreactionsinvolvedinCO2
dissolvinginwater.Thefirstisthereversiblereactionwithwatertoformcarbonicacid:

DissolvedCO2canalsoreactwithhydroxideionstogivebicarbonateions:

WhilethereactionofCO2withthehydroxideionismuchfasterthanthatwithwater,atneutralor
acidicpHthereactionwithwaterdominatesastheconcentrationofOHissmall.AtaroundpH
8.5,thehydroxideionconcentrationishighenoughforthehydroxidepathtocatchup,andat
higherpHthehydroxidepathpredominates.

Measuringtheforwardandreverserateconstantsfortheabovereactionsisnotnecessarilya
straightforwardprocess.OneapproachhasbeentorapidlymixasaturatedsolutionofCO2,to
whichanappropriateindicatorhasbeenadded,withasolutionofNaOHofsimilarconcentration,
andmeasuretheresultingabsorbancechangesasafunctionoftime.Thisisdoneusingastopped
flowspectrometer,anapparatusthatmixestwosolutionsextremelyrapidly(inmilliseconds)and
monitorstheabsorbanceoftheresultingsolutionoverarangeofwavelengths.Asampleseriesof
ourresultsisshowninfigure15.19.

FIGURE15.19Absorbancechangesover4secondsfollowingmixingCO2 andNaOH.

Figure15.19displaystheabsorbancechangesat25.0Cofasolutionthatis0.030MinCO2and
0.020MinNaOH,inthepresenceof10 4Mthymolblueindicatorover4seconds.Theindicator
essentiallytellsusthe[H3O+]concentrationasafunctionoftimeandthisknowledge,alongwith
equilibriumdata,allowsthedeterminationoftherateconstantsthroughsophisticatedcomputer
analysisofthedata.

Suchanalysisgivestheconcentrationsofthemajorspeciesovertime,asshowninfigure15.20a.
ThereisaveryfastinitialreactionofCO2withOHthatresultsinafastdecreasein[CO2](black
trace)andincreasein[CO32](redtrace).Thereactionthenslowsdownastheslowerreactionof
CO2withwaterbeginstodominate.Inaparallelprocess,carbonateionsareprotonatedto
bicarbonateions,creatingabufferedsolution.
 FIGURE15.20Changesin
(a)speciesconcentrationsand
(b)pHover4secondsfollowingmixingCO2 withNaOH.

ThegraphofpHasafunctionoftime(figure15.20b)showsasharpdecreaseinpHduetothe
reactionofOHsubsequentlythepHdropsmuchmoreslowly,whichismainlyduetothebuffer
action.Afterabout2.5secondsthecarbonateisexhausted,thereisnobufferactionandthepH
dropsfasteragaintothereachtheequilibriumpHofjustbelow7.

Althoughthisisanapparentlyrelativelysimplesystem,extensivedataarerequiredtoobtaina
completekineticdescriptionofthesystem,anditisnecessarytocollectkineticdataunderawide
varietyofinitial[CO2]and[OH]conditions.Resultsfromthisfundamentalresearchcanthenbe
usedtohelpunderstandanyprocessthatinvolvesCO2inthesecondtominutetimescale,e.g.
respiration,eveniftheseprocessesareenzymaticallycatalysedandthusmuchfasteragain.

Thisrateequationdoesmatchtheexperimentalratelaw,butthereisstillaseriousflawintheproposed
mechanism.Ifthepostulatedslowstepactuallydescribesanelementaryreaction,itwouldinvolvethe
simultaneouscollisionbetweenthreemolecules,twoNOmoleculesandoneH2molecule.Asmentioned
previously,termolecularprocessesareveryrare.Thus,chemistsbelievethereactionproceedsbythe
followingthreestepsequenceofbimolecularelementaryreactions.
Inthismechanismthefirststepisproposedtobearapidlyestablishedequilibriuminwhichtheunstable
intermediateN2O2formsbydimerisationofNOintheforwardreactionandthenquicklydecomposesinto
NObythereversereaction.TheratedeterminingstepisthereactionofN2O2withH2togiveN2Oanda
watermolecule.Thethirdstepisthereactionshownlast.Onceagain,noticethatthethreestepsaddtogive
thecorrectnetoverallchange.

Sincethesecondstepisratedetermining,theratelawforthereactionshouldmatchtheratelawforthisstep.
Wepredictthistobe:

However,theexperimentalratelawdoesnotcontainthespeciesN2O2.Therefore,wemustfindawayto
expresstheconcentrationofN2O2intermsofthereactantsintheoverallreaction.Todothis,let'slook
closelyatthefirststepofthemechanism,whichweviewasareversiblereaction.

Therateofreactionintheforwarddirection,inwhichNOisthereactant,is:

Therateofthereversereaction,inwhichN2O2isthereactant,is:

Ifweviewthisasadynamicequilibrium,thentheratesoftheforwardandreversereactionsareequal,which
meansthat:

Sincewewouldliketoeliminate[N2O2]fromtheratelaw(rate=k[N2O2][H2]),let'srearrangetheabove
equation.

Substitutingintotheratelaw:

yields:

Combiningalltheconstantsintoone(k')gives:

Nowtheratelawderivedfromthemechanismmatchestheratelawobtainedexperimentally.Thethreestep
mechanismdoesappeartobereasonableonthebasisofkinetics.

Theprocedurewehaveworkedthroughhereappliestomanyreactionsthatproceedbymechanisms
involvingsequentialsteps.Stepsthatprecedetheratedeterminingstepareconsideredtoberapidly
establishedequilibriainvolvingunstableintermediates.

PRACTICEEXERCISE15.11
 Ozone,O3,reactswithnitricoxide,NO,to
formnitrogendioxideandoxygen.

Thisisoneofthereactionsinvolvedinthe
formationofphotochemicalsmog.Ifthis
reactionoccursinasinglestep,whatisthe
expectedratelawforthereaction?

TheSteadystateApproximation
Often,insimplecasesofreactionmechanisms,onestepistheratedeterminingstep.However,itisnot
unusualthat,incomplexreactionmechanisms,theratedeterminingstepmayvarywhenthereaction
conditionsarechanged.Insuchcases,wheretheratedeterminingstepcannoteasilybechosen,thesteady
stateapproximationcanbeusedtoanalysethereaction.Thebasicideaofthismethodistheassumption
thattheconcentrationofanyintermediateremainsconstantasthereactionproceeds.(Rememberthatan
intermediateisneitherareactantnoraproduct,butitisproducedandconsumedduringthereaction.)This
willgenerallybethecaseonlywhentheconcentrationoftheintermediateremainslowoverthedurationof
thereaction.

Let'sconsiderthefollowinghypotheticalreaction.

Thisreactionmayproceedviathefollowingmechanism.

TheintermediateinthismechanismisA2B2.IftheconcentrationofA2B2remainsconstantthroughoutthe
reaction,orisassumedtoremainconstant,i.e.:

thesteadystateapproximationcanbeapplied.

Next,allstepsthatareproducingandconsumingintermediateA2B2needtobeidentified,andtheratelaw
foreachhastobewritten.Thenthesteadystateapproximationisappliedbysettingthetotalrateof
formationofA2B2equaltoitstotalrateofconsumption.

Thegeneralprocedureisdemonstratedinthefollowing:
1.RateofformationofA2B2
Inthismechanism,A2B2isproducedonlyintheforwardreactionofthefirstelementarystep.Therate
lawforthisstepis:

2.RateofconsumptionofA2B2
A2B2isconsumedinthereversereactionofthefirststepandinthesecondstep.Theratelawsfor
thesestepsare:
 and

3.Applicationofthesteadystatecondition
UndersteadystateconditionsfortheintermediateA2B2:

Ifwesolvefortheconcentrationofourintermediate[A2B2],weget:

4.Theratelawfortheoverallreaction
Now,theratelawfortheoverallreaction2AB+C2A2B+C2Biswritten.Thiscanbedonein
variousways,dependingonwhetherwechoseareactantoraproducttorepresenttherateofreaction.
InthisexampleweusethedecompositionofC2todefinetherateofreaction.

C2isconsumedonlyinthesecondstepofthemechanism,therefore:

Theequation providesuswithanexpressionfortheconcentrationofour

intermediateA2B2.Substitutionofthisexpressionintotheratelawgives:

Thisistheoverallratelawfortheproposedmechanismbasedonthesteadystateapproximation.Thisrate
lawisquitecomplicated(thisiscommonforratelawsdeterminedusingthesteadystateanalysis).Theusual
waytotestthevalidityoftheratelawinvolveschoosingconcentrationconditionsthatresultina
simplificationoftheratelaw.

Forexample,ifthereactionbetweenABandC2isstudiedunderconditionswheretheconcentrationofC2is
large,thereversereactionofstep1canbeneglected,sinceallA2B2formedinthefirstreactionrapidlyreacts
withC2toproduceA2B+C2B.Thenwehave:

Thisreducesthefullratelawto:

Thus,ifthesuggestedmechanismisvalid,atsufficientlyhighconcentrationsofC2,thereactionshould
showasecondorderdependenceontheconcentrationofAB.

Ontheotherhand,ifthereactionisperformedunderconditionsoflowC2concentrations,theintermediate
A2B2willpreferentiallydecomposeintoABthroughthereversereactionofstep1ratherthanreactingwith
C2.Then,wehave:

Thisleadstoaratelawof:

Studiesundertheseconditionsshouldshowfirstorderdependenceon[C2]andsecondorderdependenceon
[AB],iftheassumedmechanismiscorrect.

WORKEDEXAMPLE15.14

UsingtheSteadystateApproximationforConstructingaRate
Law
Theexperimentallydeterminedratelawforthedecompositionofozone(2O33O2)is:

Thefollowingmechanismhasbeenproposedtoaccountfortheratelaw.

Derivetheratelawforthedecompositionofozonebyapplyingthesteadystateapproximationto
theconcentrationofatomicoxygen.

Analysis

Theproceduretosolvesuchaproblemconsistsofseveralsteps.
(a)Constructtheratelawintermsofconsumptionofozone.
(b)ConstructthesteadystateexpressionfortheintermediateObyapplyingthecriterion
,whichmeansthatrateofformationofO=rateofconsumptionofO.Wehave
toidentifyeachstepthatproducesorconsumesOandwritetheappropriateratelawfor
each.ThesumoftheratelawsthatproduceOarethensetequaltothesumoftherate
lawsthatconsumeO.
(c)Theresultingsteadystateapproximationisthensolvedfor[O].
(d)Theexpressionfromstep(b)for[O]isusedtosubstitutefortheconcentrationofthe
intermediatefoundintheratelawofstep(a).Bydoingthisweobtainanoverallratelaw
thatcontainsonlyreactantand/orproductconcentrations.

Solution

(a)Theoverallreactionisthesumofthetworeactionsteps.Ozoneisconsumedinthe
forwardreactionofstep1andstep2,andisproducedinthereversereactionofstep1.
Theratelawfortheconsumptionofozonecanthenbewrittenas:

(equation1)
 (b)Oisproducedonlyintheforwardreactionofstep1.Thus,rateofformationofO=
k1[O3].Oisconsumedinthereversereactionofstep1andinstep2.Therefore,therateof
consumptionofO=k1[O2][O]+k2[O3][O].
Applyingthesteadystateconditiongives:

(c)SolvingfortheconcentrationofO:

(d)Substitutefor[O]inequation1:

Multiplythefirsttermontherighthandsideby:

toobtain:

k 1k 1[O2][O3]cancelsoutgiving:

(equation2)

Nowwhen[O2]islarge(k1[O2]>>k2[O3])thedenominatorreducestok1[O2],which
meansthatequation2reducesto:

whichiseffectively:

thesameastheexperimentallydeterminedratelaw.

Isouranswerreasonable?

Theratelawobtainedusingthesteadystateapproximationisthesameastheobservedratelaw.
Thisiswhatwewanted.

PRACTICEEXERCISE15.12
Apossiblemechanismforthedecomposition
 ofNO2Clis:

Whatwouldthepredictedratelawbeifthe
secondstepinthemechanismweretherate
determiningstep?

ChemicalConnections

TheAntarcticOzoneHole

Theozonelayerinthestratosphere(>12kmhigh)shieldstheEarthfromdamagingUVradiation
fromtheSun.Overthepast30years,evidencehasbeenbuildingthathumanactivitieshavecaused
adangerousreductioninthestratosphericozonelayer.Whentheozoneholewasdetectedover
Antarctica,itscreationwassoonlinkedtoanincreaseinhalogencontainingcompoundsproduced
fromchlorofluorocarbons(CFCs),chlorinatedsolvents,halons(brominecontainingcompounds)
andbromomethanereleasedintotheatmosphere.Thesechemicalswereoncewidelyusedas
refrigerants,aerosols,cleaningsolvents,firefightingchemicalsandfumigants.Figure15.21shows
thedevelopmentoftheozoneholeintheAntarcticspringfrom1979to2010.Theamountofozone
ismeasuredinDobsonunits(DU),where1DUisdefinedastheamountofozonethatwould
constitutealayer0.01mmthickat0Cand1.01310 5Pa.
 FIGURE15.21Averageozonelevel(Dobsonunits)forOctoberovertheSouthernHemispherein1979,
1984,1989,1994,1999,2001,2006,2008and2010.NASAOzoneHoleWatch,
http://ozonewatch.gsfc.nasa.gov

Howdoestheozonelossoccur?Themostcommonlyfoundbreakdownproducts(oftencalled
reservoirs)ofCFCsarehydrochloricacid,HCl,andchlorinenitrate,ClONO2.Inaddition,
dinitrogenpentoxide,N2O5,isareservoirofnitrogenoxidesandplaysanimportantroleinthe
chemistryofozonedepletion.HClandClONO2(andtheirbrominecounterparts)areconvertedinto
moreactiveformsofchlorine(orbromine)onthesurfaceofpolarstratosphericclouds(PSCs).
ThesePSCsareformedduringwinterpolarnights,whensunlightdoesnotreachtheSouthPole.A
strongcircumpolarwind(polarvortex)developsinthemiddleofthestratospherethisisolatesthe
airoverthepolarregionfromtheremainingatmosphere.Becauseofthelackofsunlight,airwithin
thevortexcangetverycoldPSCsformwhenthetemperaturefallsbelow80C.Theseclouds
consistofnitricacidtrihydrate,HNO33H2O,but,asthetemperaturedecreasesevenfurther,larger
dropletsofwatericecanformwithnitricaciddissolvedinthem.ThesePSCsarethekeytoozone
lossoverAntarctica.

ThemostimportantreactionsleadingeventuallytothedestructionofozoneonPSCsarethosethat
formHNO3,H2OandCl2fromClONO2,HClandN2O5throughtheintermediateHOCl.
 OncesunlightreturnstothepolarregionintheSouthernHemispherespring,theCl2formedinthe
reactionsaboveisphotolysedintochlorineatoms.

Chlorineatomshaveanunpairedelectron.Suchspeciesarecalledfreeradicals.Radicalsarehighly
reactivebecauseofthetendencyofelectronstobecomepairedbyformingionsorcovalentbonds.

AlthoughtherearehighconcentrationsofactiveformsofchlorineabovetheSouthPole,thereare
manymoreozonemoleculesthanchlorinespecies.So,howcantheactivechlorinedestroynearly
alloftheozone?Theanswerliesinwhatisknownasacatalyticcycle.Here,onemolecule
significantlychangesorenablesareactioncyclewithoutitselfbeingalteredbythecycle.The
followingcatalyticcycleisbelievedtoberesponsiblefor70%oftheozonelossoverAntarctica.

Intheseequations,Mstandsforacollisionpartner,whichassistsinprovidingtheenergyrequired
tosurmounttheactivationbarrierforthereaction,butwhichisnotinvolvedinthereactionitself.In
thiscycle,twochlorineatomscatalysethedestructionoftwoozonemoleculestogivethreeoxygen
molecules.

Asaconsequenceoftheozonehole,AustraliansandNewZealanderssufferthehighestratesof
skincancerintheworld(around1400Australiansandmorethan300NewZealandersdiefrom
skincancereachyear).AninternationalagreementcalledtheMontrealProtocol,originallysigned
in1987,limitstheproductionanduseofozonedepletingsubstances.Sincethattime,areductionin
therateofozonelosshasbeenmeasured,andtheconcentrationofCFCsintheatmosphereis
levellingoff.Infact,inthelastfewyears,itappearsthattheozoneholeshavebeenlesssevere.Itis
estimatedthat,ifallcountriesachievethetargetssetbytheMontrealProtocol,theozoneinthe
stratosphereshouldeventuallyrecover.However,becauseofalonglagtimeinchemicalsreaching
thestratosphere,thatrecoveryislikelytotake50years.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
15.7Catalysts
Acatalystisasubstancethatchangestherateofachemicalreactionwithoutbeingusedup.Inotherwords,allof
thecatalystaddedatthestartofareactionispresentchemicallyunchangedafterthereactionhasgonetocompletion.
Theactioncausedbyacatalystiscalledcatalysis.Broadlyspeaking,therearetwokindsofcatalystspositive
catalystsspeedupreactions,andnegativecatalysts,usuallycalledinhibitors,slowreactionsdown.Infuture,when
weusethetermcatalystwemeanpositivecatalyst.

Althoughthecatalystisnotpartoftheoverallreaction,itdoesparticipatebychangingthemechanismofthe
reaction.Thecatalystprovidesapathtotheproductsthathasaratedeterminingstepwithaloweractivationenergy
thanthatoftheuncatalysedreaction(seefigure15.22).Becausetheactivationenergyalongthisnewrouteislower,
agreaterfractionofthecollisionsofthereactantmoleculeshavetheminimumenergyneededtoreact,sothe
reactionproceedsfaster.NotethatacatalystcannotchangeHforareaction.Anendothermicreactioncannot
becomeexothermicbyusingacatalyst.

FIGURE15.22 Effectofacatalystonareaction:
(a)Thecatalystprovidesanalternative,lowerenergypathfromthereactantstotheproducts,which
proceedsthroughadifferentpathwayinvolvingdifferentintermediates.
(b)Alargerfractionofmoleculeshavesufficientenergytoreactwhenthecatalysedpathisavailable.
Althoughnotshown,thepurpleshadingcontinuestotheendofthegraph.

Catalystscanbedividedintotwogroupshomogeneouscatalysts,whichexistinthesamephaseasthereactants,
andheterogeneouscatalysts,whichexistinaseparatephase.

HomogeneousCatalysts
Homogeneouscatalystsareinthesamephaseasthereactants.Anexampleofhomogeneouscatalysisisfoundinthe
leadchamberprocessformanufacturingsulfuricacid.Sulfuricacidisoneofthemostimportantchemicalsin
industry.Itisalsotheacidusedinleadcarbatteries(seesection12.6).Tomakesulfuricacidbythisprocess,sulfur
isburnedtogiveSO2,whichisthenoxidisedtoSO3.TheSO3isdissolvedinwatertogiveH2SO4.

Unassisted,thesecondreaction,oxidationofSO2toSO3,occursslowly.Intheleadchamberprocess,theSO2is
combinedwithamixtureofNO,NO2,airandsteaminlargeleadlinedreactionchambers.TheNO2readilyoxidises
theSO2togiveNOandSO3.TheNOisthenreoxidisedtoNO2byoxygen.

TheNO2servesasacatalystbybeinganoxygencarrierandbyprovidingalowerenergypathfortheoxidationof
SO2toSO3.Notice,asmustbetrueforanycatalyst,theNO2isregeneratedithasnotbeenpermanentlychanged.

HeterogeneousCatalysts
Heterogeneouscatalystsareinaseparatephasefromthereactants.Aheterogeneouscatalystiscommonlyasolid
andusuallyfunctionsbypromotingareactiononitssurface.Oneormoreofthereactantmoleculesareadsorbed
ontothesurfaceofthecatalyst,whereaninteractionwiththesurfaceincreasestheirreactivity.Anexampleisthe
industrialsynthesisofammoniafromhydrogenandnitrogenbytheHaberBoschprocess.

TheHaberBoschprocess(figure15.23)isoneofthemostimportantprocessesinindustry,asitharnessesthe
abundanceofnitrogenintheatmospheretogenerateammonia(nitrogenfixation).Ammoniaistheprecursorto
nitratefertilisersandotherproducts.

FIGURE15.23 (a)FritzHaber(NobelPrizeinchemistry,1918)and
(b)CarlBosch(NobelPrizeinchemistry,1931),whodevelopedtheHaberBoschprocessofammonia
synthesis.
SPL

Aswehavementionedearlier,withoutacatalyst,thisreactionisextremelyslow.IntheHaberBoschprocess,the
reactiontakesplaceonthesurfaceofanironcatalystthatcontainstracesofaluminiumandpotassiumoxides.Itis
thoughtthathydrogenandnitrogenmoleculesdissociateintoatomswhilebeingheldonthecatalyticsurface.The
hydrogenatomsthencombinewiththenitrogenatomstoformammonia.Finally,thecompletedammoniamolecule
breaksaway,freeingthesurfaceofthecatalystforfurtherreaction.Thissequenceofstepsisillustratedinfigure
15.24.
 FIGURE15.24TheHaberBoschprocess.Catalyticformationofammoniamoleculesfromhydrogenandnitrogenonthe
surfaceofacatalyst.MaryEvansPictureLibrary

Heterogeneouscatalystsareusedinmanyimportantcommercialprocesses.Thepetroleumindustryuses
heterogeneouscatalyststocrackhydrocarbonsintosmallerfragmentsandthenreformthemintotheuseful
componentsofpetrol.Theavailabilityofsuchcatalystsallowsrefineriestoproducepetrol,jetfuelandheatingoil
fromcrudeoilinanyrationecessarytomeetthedemandsofthemarketplace.

Avehiclethatusesunleadedpetrolisequippedwithacatalyticconverter(figure15.25)designedtolowerthe
concentrationsofexhaustpollutants,suchascarbonmonoxide,unburnedhydrocarbonsandnitrogenoxides.Airis
introducedintotheexhauststreamthatthenpassesoveracatalystthatadsorbsCO,NOandO2.TheNOdissociates
intoNandOatoms,andtheO2alsodissociatesintoatoms.PairingofnitrogenatomsthenproducesN2,and
oxidationofCObyoxygenatomsproducesCO2.UnburnedhydrocarbonsarealsooxidisedtoCO2andH2O.The
catalystsincatalyticconvertersaredeactivatedorpoisonedbyleadbasedoctaneboosterssuchastetraethyllead,
Pb(C2H5)4,andleadedpetrolcannotbelegallyusedinvehiclesanymore.

FIGURE15.25Amodernthreewaycatalyticconverterofthetypeusedinmostnewcars.CharlesDWinters

EnzymeKinetics
Someofthemostpowerfulhomogeneouscatalystsareenzymes.Enzymes(oftencalledbiocatalysts)consistof
proteinsandcontainaspeciallyshapedareacalledanactivesitethatlowerstheenergyofthetransitionstateofthe
reactionbeingcatalysed.Theyareveryspecificandusuallyhaveadramaticeffectonthereactiontheycontrol.For
example,theactivationenergyfortheacidichydrolysisofsucroseintoglucoseandfructoseis107kJmol1.The
enzymesaccharase(enzymenameshavethesuffixase)reducestheactivationbarrierofthisreactionto36kJmol1,
whichacceleratestheratebyafactorof10 12atbloodtemperature(310K).Enzymecatalysiscanberepresentedby
aseriesofelementaryreactions(seep.658).Qualitatively,thestartingmaterials,orsubstrates,S,arereversibly
boundintheactivesitesoftheenzyme,wheretheyformanenzymesubstratecomplex,ES.Theenzymeenablesthe
conversionofthesubstrateintotheproduct,P,whichisthenreleasedfromtheenzymecomplex.Likeallcatalysts,
theenzymeremainsunchangedafterthereaction.

ChemistryResearch

AbinitioKineticModelling

ProfessorMichelleCoote,AustralianNationalUniversity

Kineticmodelsareequationsforpredictingtheoveralloutcomeofachemicalprocessbasedonatotal
pictureofthereactionconditions.Toachieveaworkingkineticmodelofareaction,therateexpressions
andrateconstantsforeverykineticallydistinctreactionintheprocess,includinganypossiblesidereactions,
needtobedetermined.Theresultingequationsaresolvedsimultaneouslytogivetimedependentvaluesfor
theyieldsofthevariousproducts,asafunctionofthestartingconcentrationsofthereagents.Ofcourse,
obtainingaccuratevaluesoftherateconstantscanbeamajorchallenge,astheyaregenerallynotdirectly
measurable.Instead,parametersarenormallymeasuredbyfittingtheassumedkineticmodeltothedata
thatareactuallymeasured:thetimedependentreactantandproductconcentrations.However,thispresumes
thatthekineticmodeliscorrect.Ifaninvalidmodelisused,thekineticparametersmaycontainhidden
systematicerrorsthatcouldmakethemlessrelevant.Suchdatamaybeusefultoregenerateresultsrelevant
tothesystemtowhichtheywerefittedbut,beyondthat,theirpredictivevaluemaybequitelimited.Theuse
ofmodelfittingcanalsomakeitdifficulttogainapreciseunderstandingofthefundamentalprocess
involved.Thisisbecausedifferentmodelscanbemadetofitthesamedataregardlessoftheirphysical
validitybytreatingthevariouskineticparametervaluesasfudgefactors.Theseproblemsbecome
particularlysignificantforcomplicatedrealworldchemicalreactionssuchasthemultistepprocesses
involvedinradicalpolymerisation(seesection26.3).Forradicalpolymerisationtheremaybehundredsor
eventhousandsofkineticallydifferentreactionstakingplace.Insuchcases,acompletekineticmodelhas
toomanyunknownkineticparameterstobefittedtotheavailabledata,andmajorsimplificationsare
requiredtoreducethenumberofparameterstoamanageablesize(typicallyfewerthanfive).

Toaddresstheseproblems,researchersattheAustralianNationalUniversityhavedevelopedanew
approachtokineticmodellingbasedonquantumchemistry.Insteadofmeasuringrateconstantsviamodel
fitting,ProfessorMichelleCoote,wholeadsthegroup,makespredictionsusingwellestablishedlawsof
quantummechanicsandstatisticalthermodynamics.Inthisway,theabinitio(fromtheLatintermmeaning
fromthebeginning)kineticparametersaretotallyindependentofanyassumedkineticmodelormeasured
experimentaldata.Thismeansthat,whentheyareusedasinputstoakineticmodel,thekineticmodel
predictionsarealsototallyindependentofthemeasuredexperimentaldata,andtheirvaliditycanbe
properlytested(seefigure15.26).Thisisinstarkcontrasttotheconventionalapproach,wherethemodel
predictionsaretestedagainstthesameorsimilardatatowhichthemodelwasoriginallyfitted.Clearlyitis
muchharderforanincorrectmodeltomakeaccuratepredictionswhentherearenofudgefactorstohelp!
 FIGURE15.26Therelationshipbetweenconventionalandabinitiokineticmethods.

Theabinitioapproachalsomakesiteasiertodesignbettermodelsinthefirstplace.Quantumchemical
calculationscanbeusedtoidentifyreactionmechanismsandtestwhethermodelassumptionsarecorrect.
Forexample,wecanusetheorytodetermineifagivensidereactionoccurs,orifarateconstantis
dependentonchainlength.Moreover,becauseeachkineticparameteriscalculatedindependently,thereare
fewerpracticalrestrictionsonthemaximumnumberofparametersamodelcancontain,andtheneedfor
simplifyingassumptionsisthusgreatlyreduced.

Sowhyareallreactionsnotanalysedthisway?Untilrecently,theabinitiopredictionofaccuratekinetic
parametersformosttypesofchemicalreactionshasnotbeenpossible.Theproblemisthatthereareno
simpleanalyticalsolutionstoamanyelectronSchrdingerequation,andthenumericalsolutionsare
thereforeincrediblycomplex.Althoughveryaccuratemethodsexist,theytendtorequirelargeamountsof
computerpower,withthecomputationalcostincreasingexponentiallywiththesizeofthechemicalsystem.
Asaresult,itisusuallynecessarytointroducemajornumericalapproximationsand/ortosimplifythe
chemicalsystem(forexample,byreplacingremotesubstituentswithhydrogenatoms)bothstrategiesarea
potentialsourceoferror.However,rapidadvancesincomputerpower,coupledwiththedevelopmentof
new,moreefficientalgorithms,arehelpingProfessorCoote'sgrouptoovercometheseproblems,andthe
predictionsoftheoryarenowstartingtorivalorevenbetterthoseofexperiment.Evenforcomplex
polymericreactions,researchersattheAustralianNationalUniversityhavedevelopedchemicallyaccurate
techniquesforpredictingrateconstantsandhaveusedthemtosuccessfullypredicttheoutcomesofmulti
componentpolymerisationprocesses(seefigure15.27).Chemistryisnowenteringaneweraofcomputer
ledresearchwherebyquantumchemistrycanbeusedtounderstandchemicalreactionsatthemolecular
levelandtopredictthemacroscopicoutcomeofanoverallchemicalprocess.Thiswillallowchemiststo
design,testandoptimisenewreagentsandcatalystsinsilico,priortoexperimentaltesting.
 FIGURE15.27Measuredlevelsofstartingmaterial(IRAFT),firstreactionproduct(IMRAFT)andsecondreaction
product(IMMRAFT)forthecyanoisopropyldithiobenzoatemediatedpolymerisationofstyrene.

Therearetwodifferenthypothesesforhowthesubstrateisboundintotheenzyme,whichweverybrieflydiscuss
here.Thelockandkeyhypothesisassumesthatthesubstratesimplyfitsintotheactivesitetoformtheenzyme
substratecomplex.Thisisschematicallyshowninfigure15.28.

FIGURE15.28Schematicpresentationofthelockandkeymodelinsubstratebindingbyanenzyme.

Theinducedfithypothesisassumesthattheenzymemoleculechangesshapeasthesubstratemoleculecomesclose
theincomingsubstrateinducesthestructuralchange.Thismoresophisticatedmodelisbasedonthefactthatthe
freerotationalongsinglebondsmakesmoleculesflexible.

UnprotectedexposuretointensesunlightcanleadtotheformationofgenotoxicproductsinDNA.Theimportanceof
efficientmechanismsfortherepairofsuchUVlesionsisdemonstratedbyhereditarydiseasessuchasxeroderma
pigmentosumpatientssufferingthisdiseaselackenzymesthatrepairUVinducedDNAdamage,whichleadsto
carcinomasandotherskinmalignanciesatayoungage.Figure15.29showsthestructureofanenzymesubstrate
complexofDNAphotolyaseandaDNAduplexcontainingadamagedsite,whichwascausedbyUVirradiation.In
prokaryotes,plantsandmanyanimals(suchasmarsupials),DNAphotolyasesaremainlyresponsibleforrepairing
UVlightinducedlesionsinDNA.Intheenzymesubstratecomplex,thelesionisflippedoutoftheduplexDNA
intotheactivesiteoftheenzymeandflippedbackintotheDNAhelixaftertherepairprocessiscomplete.
 FIGURE15.29IllustrationofanenzymesubstratecomplexofDNAphotolyaseandaDNAduplexcontainingasite
damagedbyexposuretoUVradiation.ThesurfaceoftheenzymeisrepresentedbyvanderWaalsradii,
whereasthestructureoftheDNAduplexisshownasatubemodel.

TheactionofanenzymecanbedescribedbytheMichaelisMentenmechanism.Therateofanenzymecatalysed
reactioninwhichthesubstrateSisconvertedintotheproductPisfoundtobedependentontheconcentrationofthe
enzymeE,eventhoughtheenzymedoesnotundergoanetchange.Thus,themechanismofthereactioncanbe
writtenas:

SincetheproductPisformedonlyinthesecondreactionandnotinthefirstreaction,theratelawforformationofP
is:

ESisthereactiveintermediate,anditsconcentrationcanbedescribedusingthesteadystateapproximation,where
rateofformationequalsrateofconsumption,i.e. .

Therefore,wehave:

Thisgives:

[E]and[S]aretheconcentrationsofthefreeenzymeandfreesubstrate,respectively.Ifweconsider[E]0asthetotal
concentrationoftheenzyme,wehave:

(becauseEisacatalyst,whichdoesnotundergonetchange)orafterrearrangement:

SincetheconcentrationofSismuchlargerthanthatoftheenzyme,thefreesubstrateconcentrationisalmostthe
sameasthetotalsubstrateconcentration[S]total.Asanapproximation,wecanthereforeassumethat[S]=[S]total.We
nowhave:
Withthisexpressionfor[ES],wecannowrewritetheratelawfortheformationofPasshownbelow.

(equation1)

iscalledtheMichaelisMentenequationwiththeMichaelisconstant:

Accordingtoequationequation1,therateofenzymecatalysis(enzymolysis)dependslinearlyontheenzyme
concentration[E]0,butinamorecomplicatedwayonthesubstrateconcentration[S].When[S]>>KM,theratelaw
inequationequation1reducesto:

showingthattherateiszeroorderinS.Undertheseconditionstheenzymeissaturated,therateoftheenzyme
reactionisconstantandatitsmaximum,ratemax(seep.650).Undertheseconditions,theMichaelisMenten
equationcanthenbewrittenas:

(equation2)

Ontheotherhand,whenthesubstrateconcentrationissmalland[S]<<KM,theratelawinequationequation1
reducesto:

whichshowsthattherateofproductformationdependsbothontheconcentrationofenzymeandsubstrate.This
behaviourisshowninfigure15.30.

FIGURE15.30Saturationcurveforanenzymereactionshowingtherelationshipbetweenthesubstrateconcentrationand
reactionrate.
TheMichaelisMentenequationisthebasicequationofenzymekinetics,inwhichKMhasasimpleoperational
definition.Atthesubstrateconcentrationwhere[S]=KM,equationequation2becomes:

Here,KMisthesubstrateconcentrationatwhichtherateofreactionishalfofthemaximum.Thus,ifanenzymehas
asmallKM(KMvarieswidelywiththeidentityoftheenzymeandthenatureofthesubstrate),itachievesmaximal
catalyticefficiencyatlowsubstrateconcentrations.

Theactivityofenzymescanbereducedoreveneliminatedbyenzymeinhibitors,whichcanbindtotheenzymeor
theenzymesubstratecomplex(reversibleinhibitors).Irreversibleinhibitorsinactivateenzymesbyformingcovalent
bondswhichmodifytheactivesiteoftheenzyme.

Enzymesarenotusedonlyinbiologicalsystems.Theiruniquepropertiesashighlyspecificcatalystshaveinspired
scientiststousetheminthechemicalindustryandotherapplications.Becauseofthelimitednumberofavailable
enzymesandtheirlackofstabilityinorganicsolventsandathighertemperatures,proteinengineeringisahighly
activeresearchfield,wherenewenzymeswithnovelpropertiesaredesigned.Examplesofenzymesinourdailylife
include:contactlenscleaners,whichcontainenzymescalledproteasesthatremoveproteinsoncontactlensesto
preventinfectionsbiologicaldetergentssuchaslaundrysoap,whichcontainproteasestoassistintheremovalof
proteinstainsfromclothesmachinedishwashingdetergents,whichcontainamylasestoremoveresistantstarch
residues,andlipasestohelpintheremovaloffattyandoilystainsandcellulasesusedinbiologicalfabric
conditioners.

Inthischapter,wehavelearnedthefundamentalsofchemicalkinetics.Wewillapplysomeoftheconceptswehave
learnedhereinchapter18whenwelookatthereactionsofhaloalkanes.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
ReactionRates
Chemicalkineticsisthestudyoftherateofachemicalreactionbydeterminingthechangesin
concentrationsofreactantsandproducts.Therateofchangeinconcentration(forreactionsinsolution)
orpressure(forgasphasereactions)ataparticulartimeiscalledtheinstantaneousrateofchangeof
concentration.

Thetimerequiredforhalfofareactanttodisappearisthehalflife, .

FactorsthatAffectReactionRates
Reactionratesarecontrolledbyfivefactors:(1)thechemicalnatureofthereactants,(2)thephysical
natureofthereactants,(3)theconcentrationsofthereactants,(4)thetemperatureand(5)thepresence
ofcatalysts.Theratesofheterogeneousreactionsaredeterminedlargelybytheareaofcontactbetween
thephasestheratesofhomogeneousreactionsaredeterminedbytheconcentrationsofthereactants.
Therateofareactionismeasuredbymonitoringthechangeinreactantorproductconcentrationswith
timeand,forthegeneralreactionaA+bBcC+dD,isdefinedas:

OverviewofRateLaws
Theratelawforareactionrelatestherateofthereactiontothemolarconcentrationsofthereactants.
Therateofareactionisproportionaltotheproductofthemolarconcentrationsofthereactants,each
raisedtoanappropriatepower(orderofthereactant).Theseexponentsmustbedeterminedby
experimentsinwhichtheconcentrationsarevariedandtheeffectsontherateofthereactionare
measured.Theproportionalityconstant,k,iscalledtherateconstant.Itsvaluedependsontemperature
butnotontheconcentrationsofthereactants.Thesumoftheexponentsintheratelawisdefinedasthe
order(oroverallorder)ofthereaction.

TypesofRateLaws:DifferentialandIntegrated
Thedifferentialratelawshowshowtherateofareactioninsolutionorinthegasphasedependson
concentrations.Theintegratedratelawshowshowtheconcentrationsdependontime.

Equationsexistthatrelatetheconcentrationofareactantatagiventimettotheinitialconcentrationand
therateconstant.Forafirstorderreaction,thehalflifeisaconstantthatdependsonlyontherate
constantforthereactionitisindependentoftheinitialconcentration.Thehalflifeofasecondorder
reactionisinverselyproportionaltoboththeinitialconcentrationofthereactantandtotherate
constant.Thehalflifeofazeroorderreactionisproportionaltotheinitialconcentrationofthereactant
butisinverselyproportionaltotherateconstant.

TheoryofChemicalKinetics
Accordingtothecollisiontheory,therateofareactiondependsonthenumberofeffectivecollisions
persecondbetweenthereactantparticles,whichisanextremelysmallfractionofthetotalnumberof
collisionspersecond.Thisfractionissmallpartlybecausecollisionsusuallydonotresultinproducts
unlessthereactantmoleculesaresuitablyoriented.Themajorreason,however,isthatthecolliding
moleculesmustjointlypossessaminimummolecularkineticenergy,calledtheactivationenergy,Ea .
Asthetemperatureincreases,alargerfractionofthecollisionshasthisnecessaryenergy,makingmore
collisionseffectiveeachsecondandthereactionfaster.

Theenthalpyofareactionisthenetpotentialenergydifferencebetweenthereactantsandtheproducts.
Inreversiblereactions,thevaluesofEa forboththeforwardandreversereactionscanbeidentifiedona
potentialenergydiagram.Thespeciesatthemaximumonanenergydiagramiscalledthetransition
state.Inamultistepreaction,areactionintermediateischaracterisedasanenergyminimumbetween
twotransitionstates.Intermediateshavehigherenergiesthanreactantsandproducts.

TheArrheniusequationshowshowchangesintemperatureaffectarateconstant.TheArrhenius
equationalsoenablesustodetermineEa ,eithergraphicallyorbyacalculationusingtheappropriate
formoftheArrheniusequation.Thecalculationrequirestworateconstantsdeterminedattwodifferent
temperatures.Theactivationenergyandtherateconstantatonetemperaturecanbeusedtocalculatethe
rateconstantatanothertemperature.

ReactionMechanisms
Thedetailedsequenceofelementaryreactionsthatleadtothenetchemicalchangeisthemechanismof
thereaction.Supportforamechanismcomesfrommatchingthepredictedratelawforthemechanism
withtheratelawobtainedfromexperimentaldata.Fortheratedeterminingstep,orforanyelementary
reaction,thecorrespondingratelawhasexponentsequaltothecoefficientsinthebalancedequation.In
morecomplicatedreactionmechanisms,wheretheratedeterminingstepcannotbeeasilyidentified,the
steadystateapproximationcanbeusedtoderivetheratelaw.

Catalysts
Catalystsaresubstancesthatchangeareactionratebutarenotconsumedbythereaction.Negative
catalystsinhibitreactions.Positivecatalystsprovidealternativepathsforreactionsforwhichatleastone
stephasasmalleractivationenergythantheuncatalysedreaction.Homogeneouscatalystsareinthe
samephaseasthereactants.Heterogeneouscatalystsprovideapathofloweractivationenergyby
havingasurfaceonwhichthereactantsareadsorbedandreact.Catalystsinlivingsystemsarecalled
enzymes.EnzymekineticscanbedescribedbytheMichaelisMentenequation,whichcontainsthe
MichaelisconstantKMthisrepresentstheratiooftherateconstantsforformationoftheenzyme
substratecomplexandtheenzymereactiontoformproducts.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Ratelawofareaction(section15.4)
Thisshowsthedependenceoftherateofreactionontheconcentrationofoneormorereactants(and
occasionallyproducts),eachofwhichisraisedtoaparticularexponent.Theoverallorderofareaction
isgivenbythesumoftheseexponents.Therateconstantforareactioncanbecalculatedfromthis,
giventheappropriateratedata.

Integratedfirstorderratelaw(section15.4)
Forafirstorderreactionwithknownk,thisequationisusedtocalculatetheconcentrationofareactant
atsomespecifiedtimeafterthestartofthereaction,ortocalculatethetimerequiredforthe
concentrationtodroptoaspecifiedvalue.

Integratedsecondorderratelaw(section15.4)
Forasecondorderreactionwithknownk,thisequationisusedtocalculatetheconcentrationofa
reactantataspecifiedtimeafterthestartofthereaction,ortocalculatethetimerequiredforthe
concentrationtodroptoaspecifiedvalue.

Integratedzeroorderratelaw(section15.4)
Forazeroorderreactionwithknownk,thisequationisusedtocalculatetheconcentrationofareactant
atsomespecifiedtimeafterthestartofthereaction,ortocalculatethetimerequiredforthe
concentrationtodroptoaspecifiedvalue.

Halflife(section15.4)

Zeroorder:

Firstorder:

Secondorder:

Arrheniusequation(section15.5)
Theseequationsareusedtocalculateahalflifefromexperimentaldataandreactionorder,orto
calculatetherateofdisappearanceofareactant.

MichaelisMentenequation(section15.7)
Thisequationallowsgraphicaldeterminationofanactivationenergyandrelatesrateconstants,
activationenergyandtemperature.
Thisisthebasicequationofenzymekinetics.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
ReactionRates
15.1Whatdoesrateofreactionmeaninqualitativeterms?
15.2Giveanexamplefromeverydayexperienceof:(a)averyfastreaction,(b)amoderatelyfast
reactionand(c)aslowreaction.
15.3Intermsofratesofreaction,whatisanexplosion?
15.4Whatismeantbythetermhalflife?
FactorsthatAffectReactionRates
15.5Fromaneconomicpointofview,whywouldindustrialcorporationswanttoknowaboutthe
factorsthataffecttherateofareaction?
15.6Supposewecomparedtworeactions,onerequiringthesimultaneouscollisionofthreemolecules
andtheotherrequiringacollisionbetweentwomolecules.Fromthestandpointofstatistics,andall
otherfactorsbeingequal,whichreactionshouldbefaster?Explainyouranswer.
15.7Listthefivefactorsthataffecttheratesofchemicalreactions.
15.8Howdoesaninstantaneousrateofreactiondifferfromanaveragerateofreaction?
15.9Explainhowtheinitialinstantaneousrateofreactioncanbedeterminedfromexperimental
concentrationversustimedata.
15.10Whatisahomogeneousreaction?Giveanexample.
15.11Whatisaheterogeneousreaction?Giveanexample.
15.12Whyarechemicalreactionsusuallycarriedoutinsolution?
15.13Whatisthemajorfactorthataffectstherateofaheterogeneousreaction?
15.14Howdoesparticlesizeaffecttherateofaheterogeneousreaction?Why?
15.15Therateofhardeningofepoxygluedependsontheamountofhardenerthatismixedintothe
glue.Whatfactoraffectingratesofreactiondoesthisillustrate?
15.16Whatisacatalyst?
15.17Incoolweather,thenumberofchirpsperminutefromcricketsdiminishes.Howcanthisbe
explained?
15.18Onthebasisofwhatyoulearnedinchapters6and7,whydofoodscookfasterinapressure
cookerthaninanopenpotofboilingwater?
15.19Peoplewhohavebeensubmergedinverycoldwaterandwhoarebelievedtohavedrownedcan
sometimesberevived.Ontheotherhand,peoplewhohavebeensubmergedinwarmerwaterfor
thesamelengthoftimehavedied.Explainthisintermsoffactorsthataffecttheratesofchemical
reactions.
OverviewofRateLaws
15.20Whataretheunitsofrateofreaction?
15.21Whatisaratelaw?Whatistheproportionalityconstantcalled?
15.22Whatismeantbytheorderofareaction?
15.23Whataretheunitsoftherateconstantfor:(a)afirstorderreaction,(b)asecondorderreaction
and(c)azeroorderreaction?
15.24Howmusttheexponentsinaratelawbedetermined?
TypesofRateLaws:DifferentialandIntegrated
15.25Howdoesthedependenceofrateofreactiononconcentrationdifferbetweenazeroorderanda
 firstorderreaction?
15.26Isthereanywaytousethecoefficientsinthebalancedoverallequationforareactiontopredict
withcertaintywhattheexponentsareintheratelaw?
15.27Iftheconcentrationofareactantisdoubledandtherateofreactionisunchanged,whatisthe
orderofthereactionwithrespecttothatreactant?
15.28Iftheconcentrationofareactantisdoubledandtherateofreactiondoubles,whatistheorderof
thereactionwithrespecttothatreactant?
15.29Iftheconcentrationofareactantisdoubled,bywhatfactorwilltherateofreactionincreaseifthe
reactionissecondorderwithrespecttothatreactant?
15.30Inanexperiment,theconcentrationofareactantwastripled.Therateofreactionincreasedbya
factorof27.Whatistheorderofthereactionwithrespecttothatreactant?
15.31Biologicalreactionsusuallyinvolvetheinteractionofanenzymewithasubstrate,thesubstance
thatactuallyundergoesthechemicalchange.Inmanycases,therateofreactiondependsonthe
concentrationoftheenzyme,butisindependentofthesubstrateconcentration.Whatistheorder
ofthereactionwithrespecttothesubstrateinsuchinstances?
15.32Areactionhasthefollowingratelaw:

Whataretheunitsoftherateconstant,k?
15.33Givetheequationsthatrelateconcentrationtotimefor:(a)afirstorderreactionand(b)asecond
orderreaction.
15.34Howisthehalflifeofafirstorderreactionaffectedbytheinitialconcentrationofthereactant?
15.35Howisthehalflifeofasecondorderreactionaffectedbytheinitialreactantconcentration?
15.36Derivetheequationsfor forfirstandsecondorderreactions.
15.37Theintegratedratelawforazeroorderreactionis:

Deriveanequationforthehalflifeofazeroorderreaction.
15.38Theratelawforacertainenzymaticreactioniszeroorderwithrespecttothesubstrate.Therate
constantforthereactionis6.410 2molL1s1.Iftheinitialconcentrationofthesubstrateis
0.275molL1,whatistheinitialrateofthereaction?
TheoryofChemicalKinetics
15.39Whatisthebasicpostulateofthecollisiontheory?
15.40Whattwofactorsinfluencetheeffectivenessofmolecularcollisionsinproducingchemical
change?
15.41Intermsofthekinetictheory,whydoesanincreaseintemperatureincreasetherateofreaction?
15.42Drawthepotentialenergydiagramforanendothermicreaction.Indicateonthediagramthe
activationenergyforboththeforwardandreversereactions.Alsoindicatetheenthalpyof
reaction.
15.43Explain,intermsofthelawofconservationofenergy,whyanendothermicreactionleadstoa
coolingofthereactionmixture(providedheatcannotenterfromoutsidethesystem).
15.44Definethetermtransitionstate.
15.45Drawapotentialenergydiagramforanexothermicreactionandindicateonthediagramthe
locationofthetransitionstate.
15.46Supposeacertainslowreactionisfoundtohaveaverysmallactivationenergy.Whatdoesthis
 suggestabouttheimportanceofmolecularorientationintheformationofthetransitionstate?
15.47Thedecompositionofcarbondioxide:

hasaverylargeactivationenergyofapproximately460kJmol1.Explainwhythisisconsistent
withamechanismthatinvolvesbreakingaC Obond.
15.48StatetheArrheniusequation(whichrelatestherateconstanttotemperatureandactivation
energy),anddefinethesymbols.
ReactionMechanisms
15.49Whatisthedefinitionofanelementaryreaction?Howareelementaryreactionsrelatedtothe
mechanismofareaction?
15.50Whatisaratedeterminingstep?
15.51Inwhatwayistheratelawforareactionrelatedtotheratedeterminingstep?
15.52Thefollowingmechanismhasbeenproposedforaparticularreaction:

Whatisthenetoverallchangethatoccursinthisreaction?
15.53Iftheexperimentalratelawforthemechanisminquestion15.52issecondorderin[NO]and
firstorderin[H2],whichofthereactionstepsistheratedeterminingstep?
15.54IfthereactionNO2+CONO+CO2occursbyaonestepcollisionprocess,whatwouldbethe
expectedratelawforthereaction?Theactualratelawisrate=k[NO2]2.Couldthereaction
actuallyoccurbyaonestepcollisionbetweenNO2andCO?Explain.
15.55OxidationofNOtoNO2,oneofthereactionsintheproductionofsmog,appearstoinvolve
carbonmonoxide.Apossiblemechanismis:

Writethenetchemicalequationforthereaction.
15.56Showthatthefollowingtwomechanismsgivethesamenetoverallreaction.

Mechanism1:

Mechanism2:

15.57TheexperimentalratelawforthereactionNO2+COCO2+NOis:

Ifthemechanismis:
 showthatthepredictedratelawisthesameastheexperimentalratelaw.
15.58ThefollowingmechanismhasbeenproposedforthereductionofNO byMoCl 2.
3 6

Whatistheintermediate?

Deriveanexpressionfortheratelaw,where:

fortheoverallreaction,usingthesteadystateapproximation.
15.59Considerthehypotheticalreaction:

whichisassumedtooccurbythefollowingmechanism:

(Y*representsanactivatedmolecule,whichhasenoughenergytosurmounttheactivation
barrier).
(a)DerivearatelawfortheproductionofAusingthesteadystateapproximation.
(b)Assumingthatthisreactionisknowntobefirstorder,underwhatconditionsdoesyour
derivedratelawagreewiththisobservation?
(c)Explainhowachemicalreactioncanbefirstorderwhen,eveninasimplecase(for
examplethepresentreaction),moleculesmustcollidetobuildupenoughenergytoget
overtheenergybarrier?Whyaren'tallreactionsatleastsecondorder?
15.60Enzymesarebiologicalcatalysts.Oneproposedmechanismforenzymecatalysisofthereaction
ABis:

whereEistheenzyme.Whatistheoverallratelawforthisreactionifstep1istheslowerstep?
Whatistheoverallratelawifstep2istheslowerstep?
Catalysts
15.61Howdoesacatalystincreasetherateofachemicalreaction?
15.62Whatisahomogeneouscatalyst?Howdoesitfunction?
15.63Whatisaheterogeneouscatalyst?Howdoesitfunction?
15.64Whatisthedifferenceinmeaningbetweenadsorptionandabsorption?Whichoneappliesto
heterogeneouscatalysts?
15.65Whatisthefunctionofthecatalyticconverterintheexhaustsystemofacar?Whyshouldleaded
petrolnotbeusedincarsequippedwithcatalyticconverters?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
15.66Thefollowingdatawerecollectedatacertaintemperatureforthedecompositionofsulfuryl
chloride,SO2Cl2,achemicalusedinavarietyoforganicsyntheses.

Time(min) [SO2Cl2](molL1)

0 0.1000
100 0.0876
200 0.0768
300 0.0673
400 0.0590
500 0.0517
600 0.0453
700 0.0397
800 0.0348
900 0.0305
1000 0.0267
1100 0.0234
DrawagraphofconcentrationversustimeanddeterminetherateofformationofSO2att=200
minandt=600min.
15.67Thefollowingdatawerecollectedforthedecompositionofacetaldehyde,CH3CHO(usedinthe
manufactureofavarietyofchemicalsincludingperfumes,dyesandplastics),intomethaneand
carbonmonoxide.Thedatawerecollectedatatemperatureof530C.

Time(s) [CH3CHO](molL1)

0 0.200
20 0.153
40 0.124
60 0.104
80 0.090
100 0.079
120 0.070
140 0.063
160 0.058
180 0.053
200 0.049
 Drawagraphofconcentrationversustimeanddeterminetherateofreactionafter60sandafter
120s.
15.68Inthecatalysedformationofammoniaaccordingtothereaction3H2+N22NH3,howdoes
therateofconsumptionofhydrogencomparewiththerateofconsumptionofnitrogen?How
doestherateofformationofNH3comparewiththerateofconsumptionofnitrogen?
15.69Forthereaction2A2+B3C,itwasfoundthattherateofconsumptionofBwas0.30molL1
s1.WhatweretherateofconsumptionofAandtherateofformationofC?
15.70Inthecombustionofhexane(alowboilingcomponentofpetrol):

itwasfoundthattherateofconsumptionofC6H14was1.20molL1s1.
(a)WhatwastherateofconsumptionofO2?
(b)WhatwastherateofformationofCO2?
(c)WhatwastherateofformationofH2O?
15.71Atacertainmomentinthereaction:

N2O5wasfoundtobedecomposingatarateof2.510 6molL1s1.Whatweretheratesof
formationofNO2andO2?
15.72Calculatetherateofthereaction:

giventhattheratelawforthereaction(at0C)is:

andthereactantconcentrationsare[H2SeO3]=2.010 2M,[I]=2.010 3M,and[H+]=1.0

10 3M.
15.73Calculatetherateofthereaction:

giventhattheratelawforthereactionis:

forneutralwaterwhere[H3O+]=1.010 7Mand[OH]=1.010 7M.

15.74TheoxidationofNO(releasedinsmallamountsintheexhaustofcars)producesthebrownish
redgasNO2,whichisacomponentofurbanairpollution.

Theratelawforthereactionisrateofreaction=k[NO]2[O2].At25C,k=7.110 9L2mol2s1.
Whatwouldtherateofthereactionbeif[NO]=0.0010molL1and[O2]=0.034molL1?
15.75TheratelawforthedecompositionofN2O5is:

Ifk=1.010 5s1,whatistherateofreactionwhentheN2O5concentrationis0.0010molL1?
15.76Forthereaction:

theratelawis:

(a)Whatistheorderofthereactionwithrespecttoeachreactant?
(b)Whatistheoverallorderofthereaction?
15.77Akeyelementaryreactioninthedestructionofstratosphericozonefromnitrogenoxidesinjet
exhaustofhighflyingaircraftisthereaction:

Theratelawis:

(a)Whatistheorderwithrespecttoeachreactant?
(b)Whatistheoverallorderofthereaction?
15.78Thefollowingdatarefertothehypotheticalreaction:

Initialconcentration
[M](molL1) [N](molL1) Initialofreaction(molL1s1)
0.010 0.010 2.510 3
0.020 0.010 5.010 3
0.020 0.030 4.510 2

Whatistheratelawforthereaction?Whatisthevalueoftherateconstant(withcorrectunits)?
15.79Cyclopropane,C3H6,isagasusedasageneralanaesthetic.Itundergoesaslowrearrangementto
propene.

Atacertaintemperature,thefollowingratedatawereobtained.

InitialconcentrationofC3H6(molL1) Rateofformationofpropene(molL1s1)
0.050 2.9510 5
0.100 5.9010 5
0.150 8.8510 5

Whatistheratelawforthereaction?Whatisthevalueoftherateconstant?Includethecorrect
 units.
15.80Thereactionofiodideionswithhypochloriteions,OCl(theactiveingredientinchlorine
bleach),followstheequationOCl+IOI+Cl.Itisarapidreactionthatgivesthefollowing
ratedata.

Initialconcentration

[OCl](molL1) [I](molL1) RateofformationofCl(molL1s1)

1.710 3 1.710 3 1.7510 4

3.410 3 1.710 3 3.5010 4

1.710 3 3.410 3 3.5010 4

Whatistheratelawforthereaction?Determinethevalueoftherateconstantwithitscorrect
units.
15.81Theformationofsmallamountsofnitricoxide,NO,incarenginesisthefirststepinthe
formationofsmog.Nitricoxideisreadilyoxidisedtonitrogendioxidebythereaction:

Thefollowingdatawerecollectedinastudyoftherateofthisreaction.

Initialconcentration

[O2](molL1) [NO](molL1) RateofformationofNO2(molL1s1)

0.0010 0.0010 7.10
0.0040 0.0010 28.4
0.0040 0.0030 255.6

Whatistheratelawforthereaction?Whatistherateconstantwithitscorrectunits?
15.82Atacertaintemperaturethefollowingdatawerecollectedforthereaction2ICl+H2I2+
2HCl.

Initialconcentration

[ICl](molL1) [H2](molL1) RateofformationofI2(molL1s1)

0.10 0.10 0.0015

0.20 0.10 0.0030
0.10 0.0500 0.00075

Determinetheratelawandtherateconstant(withcorrectunits)forthereaction.
15.83Thefollowingdatawereobtainedforthereactionof(CH3)3CBrwithhydroxideionsat55C.

Initialconcentration
 [(CH3)3CBr](molL1) [OH](molL1) Rateofformationof(CH3)3COH(molL1s1)

0.10 0.10 1.010 3

0.20 0.10 2.010 3
0.30 0.10 3.010 3
0.10 0.20 1.010 3
0.10 0.30 1.010 3

Whatistheratelawforthereaction?Whatisthevalueoftherateconstant(withcorrectunits)at
thistemperature?
15.84DataforthedecompositionofSO2Cl2accordingtotheequationSO2Cl2(g)SO2(g)+Cl2(g)
weregiveninquestion15.66.Showgraphicallythatthesedatafitafirstorderratelaw.
Graphicallydeterminetherateconstantforthereaction.
15.85Forthedatainquestion15.67,decidegraphicallywhetherthereactionisfirstorsecondorder.
Determinetherateconstantforthereactiondescribedinthatquestion.
15.86ThedecompositionofSO2Cl2describedinquestion15.66hasafirstorderrateconstantk=2.2
10 5s1at320C.IftheinitialSO2Cl2concentrationinacontaineris0.0040M,whatisits
concentration:(a)after1.00hourand(b)after1.00day?
15.87Ifittakes75.0minfortheconcentrationofareactanttodropto20%ofitsinitialvalueinafirst
orderreaction,whatistherateconstantforthereactionintheunitsmin 1?
15.88Theconcentrationofadruginthebodyisoftenexpressedinunitsofmilligramsperkilogramof
bodyweight.Theinitialdoseofadruginananimalwas25.0mg/kgbodyweight.After2.00
hours,thisconcentrationhaddroppedto15.0mg/kgbodyweight.Ifthedrugiseliminated
metabolicallybyafirstorderprocess,whatistherateconstantfortheprocessinunitsofmin 1?
15.89Inquestion15.88,whatmusttheinitialdoseofthedrugbeinorderforthedrugconcentration
3.00hafterwardtobe5.0mg/kgbodyweight?
15.90Thedecompositionofhydrogeniodidefollowstheequation2HI(g)H2(g)+I2(g).The
reactionissecondorderandhasarateconstantof1.610 3mol1Ls1at700C.Iftheinitial
concentrationofHIinacontaineris3.410 2M,howlongwillittakefortheconcentrationto
bereducedto8.010 4M?
15.91ThesecondorderrateconstantforthedecompositionofHIat700Cwasgiveninquestion
15.90.At2.510 3minafteraparticularexperimenthadbegun,theHIconcentrationwasequal
to4.510 4molL1.WhatwastheinitialmolarconcentrationofHIinthereactionvessel?
15.92Thehalflifeofacertainfirstorderreactionis15min.Whatfractionoftheoriginalreactant
concentrationremainsafter2.0h?
15.93Strontium90hasahalflifeof28years.Howlongwillittakeforallofthestrontium90
presentlyonEarthtobereducedto ofitspresentamount?

15.94Usingthegraphfromquestion15.66,determinethetimerequiredfortheSO2Cl2concentration
todropfrom0.100molL1to0.050molL1.Howlongdoesittakefortheconcentrationtodrop
from0.050molL1to0.025molL1?Whatistheorderofthisreaction?(Hint:Howisthehalf
liferelatedtoconcentration?)
15.95Usingthegraphfromquestion15.67,determinehowlongittakesfortheCH3CHOconcentration
 todecreasefrom0.200molL1to0.100molL1.Howlongdoesittaketheconcentrationtodrop
from0.100molL1to0.050molL1?Whatistheorderofthisreaction?(Hint:Howisthehalf
liferelatedtoconcentration?)
15.96Acertainfirstorderreactionhasarateconstantk=1.610 3s1.Whatisthehalflifeforthis
reaction?
15.97ThedecompositionofNOCl,thecompoundthatgivesayelloworangecolourtoaquaregia(a
mixtureofconcentratedHClandHNO3thatisabletodissolvegoldandplatinum)followsthe
reaction2NOCl2NO+Cl2.Itisasecondorderreactionwithk=6.710 4mol1Ls1at400
K.WhatisthehalflifeofthisreactioniftheinitialconcentrationofNOClis0.20molL1?
15.98Thefollowingdatawerecollectedforareaction.

Rateconstant(mol1Ls1) Temperature(C)

2.8810 4 320

4.8710 4 340

7.9610 4 360

1.2610 3 380

1.9410 3 400

DeterminetheactivationenergyforthereactioninkJmol1bothgraphicallyandbycalculation
using .ForthecalculationofEa ,usethefirstandlastrowsofdatain
thetableinthisquestion.
15.99Rateconstantsweremeasuredatvarioustemperaturesforthereaction:

Thefollowingdatawereobtained.

Rateconstant(mol1Ls1) Temperature(C)

1.9110 2 205

2.7410 2 210

3.9010 2 215

5.5110 2 220

7.7310 2 225

1.0810 1 230

DeterminetheactivationenergyinkJmol1bothgraphicallyandbycalculationusing
.ForthecalculationofEa ,usethefirstandlastrowsofdatainthe
tableabove.
15.100Thereaction2NOCl2NO+Cl hask=9.310 5mol1Ls1at100Candk=1.010 3
2
mol1Ls1at130C.WhatisEa forthisreactioninkJmol1?Usethedataat100Cto
calculatethepreexponentialfactorA.(Hint:Ahasthesameunitastherateconstant.)
15.101Theconversionofcyclopropane,ananaesthetic,topropene(seequestion15.79)hasarate
constantk=1.310 6s1at400Candk=1.110 5s1at430C.
(a) WhatistheactivationenergyinkJmol1?
(b)Whatisthevalueofthepreexponentialfactor,A,forthisreaction?
(c)Whatistherateconstantforthereactionat350C?
15.102ThereactionofCO2withwatertoformcarbonicacid,CO2(aq)+H2O(l)H2CO3(aq),hask=
3.7510 2s1at25Candk=2.110 3s1at0C.Whatistheactivationenergyforthis
reactioninkJmol1?
15.103Ifareactionhask=3.010 4s1at25Candanactivationenergyof100.0kJmol1,whatis
thevalueofkat50C?
15.104ThedecompositionofN O hasanactivationenergyof103kJmol1andapreexponential
2 5
13 1
factorof4.310 s .Whatistherateconstantforthisdecompositionat:(a)20Cand(b)
100C?
15.105At35C,therateconstantforthereaction:

isk=6.210 5s1.Theactivationenergyforthereactionis108kJmol1.Whatistherate
constantforthereactionat45C?
15.106Asucraseenzymebreaksdown0.15Mlactoseevery37minutes.Whatisthereactionratein:
(a) Mmin 1?
(b)mMmin 1?
(c) molmin 1ina500mLflask?
15.107ThefollowingmechanismhasbeensuggestedforthereactionH2(g)+I2(g)2HI(g):

Derivetheratelawusingthesteadystateapproximation.
15.108Apossiblemechanismforthereaction2N2O54NO2+O2is:

Whatistheratelawderivedusingthesteadystateapproximation?
15.109Thedecompositionofmanysubstancesonthesurfaceofaheterogeneouscatalystshowsthe
 followingrelationshipbetweenreactionrateandsubstrateconcentration.

Whydoestheratelawchangefromfirstordertozeroorderintheconcentrationofthe
substrate?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
15.110Forthereactionanddatagiveninquestion15.67,makeagraphofconcentrationversustime
fortheformationofCH4.WhataretheratesofformationofCH4att=40sandt=100s?
15.111Theageofwinecanbedeterminedbymeasuringthetraceamountofradioactivetritium,3H,
presentinasample.Tritiumisformedfromhydrogeninwatervapourintheupperatmosphere
bycosmicbombardment,soallnaturallyoccurringwatercontainsasmallamountofthis
isotope.Oncethewaterisinabottleofwine,however,theformationofadditionaltritiumfrom
thewaterisnegligible,sothetritiuminitiallypresentgraduallydiminishesbyafirstorder
radioactivedecaywithahalflifeof12.5years.Ifabottleofwineisfoundtohaveatritium
concentrationthatis0.100thatoffreshlybottledwine(i.e.[3H]t=0.100[3H]0),whatistheage
ofthewine?
15.11214Cdatingcanbeusedtoestimatetheageofformerlylivingmaterialsbecausetheuptakeof
14Cfromcarbondioxideintheatmospherestopsoncetheorganismdies.Iftissuesamplesfrom

amummycontainabout81.0%ofthe14Cexpectedinlivingtissue,howoldisthemummy?
Thehalflifefordecayof14Cis5730years.
15.113Oneofthereactionsthatoccursinpollutedairinurbanareasis2NO2(g)+O3(g)N2O5(g)+
O2(g).ItisbelievedthataspecieswiththeformulaNO3isinvolvedinthemechanism,andthe
observedratelawfortheoverallreactionis:

ProposeamechanismforthisreactionthatincludesthespeciesNO3andisconsistentwiththe
observedratelaw.
15.114Supposeareactionoccurswiththemechanism:

inwhichstep1isaveryrapidreversiblereactionthatcanbeconsideredtobeessentiallyan
equilibrium(forwardandreversereactionsoccurringatthesamerate)andstep2isslow.
(a)Writetheratelawfortheforwardreactioninstep1.
(b)Writetheratelawforthereversereactioninstep1.
(c)Writetheratelawfortheratedeterminingstep.
(d)Whatisthechemicalequationforthenetreactionthatoccursinthischemicalchange?
(e)Usetheresultsfromparts(a)and(b)torewritetheratelawoftheratedeterminingstep
intermsoftheconcentrationsofthereactantsintheoverallbalancedequationforthe
reaction.
15.115Areactionthathasthestoichiometry:

wasfoundtoyieldthefollowingdata.

Initialconcentration(molL1)
[A] [B] InitialrateofreactionofA(molL1s1)
0.020 0.030 0.0150
0.025 0.030 0.0188

0.025 0.040 0.0334

 (a)Whatistheratelawforthereaction?
(b)Whatistherateconstantforthereaction?Givethecorrectunits.
15.116Thedecompositionofurea,(NH2)2CO,in0.10MHClfollowstheequation:

At60C,k=5.8410 6min 1and,at70C,k=2.2510 5min 1.Ifthisreactionisrunat80

Cstartingwithaureaconcentrationof0.0020M,howlongwillittakefortheurea
concentrationtodropto0.0012M?
15.117Showthatforareactionthatobeysthegeneralratelaw:

agraphoflog(rate)versuslog[A]shouldyieldastraightlinewithaslopeequaltotheorderof
thereaction.Forthereactioninquestion15.66,measuretherateofthereactionatt=150,300,
450and600s.Thengraphlog(rate)versuslog[SO2Cl2]anddeterminetheorderofthereaction
withrespecttoSO2Cl2.
15.118ThebondinginO2wasdiscussedinsection5.7aswasthebondinginN2.Molecularnitrogenis
veryunreactive,whereasmolecularoxygenisveryreactive.Onthebasisofwhatyouhave
learnedinthischapter,whatfactaboutO2isresponsible,atleastinpart,foritsreactivity?What
mightaccountforthelowdegreeofreactivityofmolecularnitrogen?
15.119Itwasmentionedthattheratesofmanyreactionsapproximatelydoubleforeach10Crisein
temperature.Assumingastartingtemperatureof25C,whatwouldtheactivationenergybe,in
kJmol1,iftherateofareactionweretobetwiceaslargeat35C?
15.120Therateatwhichcricketschirpdependsontheambienttemperature,becausecricketsarecold
bloodedinsectswhosebodytemperaturefollowsthetemperatureoftheirenvironment.Ithas
beenfoundthatthetemperatureinCcanbeestimatedbycountingthenumberofchirpsin8
secondsandthenadding4.Inotherwords,tC=(numberofchirpsin8seconds)+4.
(a)Calculatethenumberofchirpsin8secondsfortemperaturesof20,25,30and35C.
(b)Thenumberofchirpsperunitoftimeisdirectlyproportionaltotherateconstantfora
biochemicalreactioninvolvedinthecricket'schirp.Onthebasisofthisassumption,
makeagraphofln(chirpsin8s)versus .Calculatetheactivationenergyforthe
biochemicalreactioninvolved.
(c)Howmanychirpswouldacricketmakein8secondsatatemperatureof40C?
15.121Thecookingofanegginvolvesthedenaturationofaproteincalledalbumen.Thetimerequired
toachieveaparticulardegreeofdenaturationisinverselyproportionaltotherateconstantfor
theprocess.Thisreactionhasahighactivationenergy,Ea =418kJmol1.Calculatehowlongit
wouldtaketocookatraditional3minuteeggontopofacoldmountainonadaywhenthe
atmosphericpressurethereis47kPa.
15.122Whichofthefollowingcannotbeaunitforreactionrate.Explainyouranswers.
(a) molL1s1
(b)gL1s1
(c) %s1
(d)gs1
 (e) mols1
(f) molL1
15.123TheenthalpiesofformationofAl O andB O are1676and1274kJmol1,respectively.Do
2 3 2 3
thesedataindicatetherateofoxidationofaluminiumandboron?Explainyouranswer.
15.124Whichoneofthefollowingreactionsisthemostrapidatroomtemperature.Whichreactionis
theslowest?Explainyouranswers.
(a)2H2+O22H2O
(b)H++OHH O
2
(c)C12H22O1112C+11H2O
(d)H+OHH2O
15.125Whichoneofthefollowingburnseasilyandwhy?
(a)steelbar
(b)steelwool
(c)steelsheet
(d)steelpipe
15.126Therateconstantforareactionis2.9010 9s1at454Kwithanactivationenergyof178.5kJ
mol1.Whatisthevalueoftherateconstantat395K?
15.127Therateconstantforareactionis1.7210 4s1at298Kand2.7510 1s1at301K.Whatis
theactivationenergyinkJmol1?
15.128Theactivationenergyofaunimolecularreactionis190.2kJmol1at295K.Whatisthevalue
oftherateconstant?
15.129ThefollowingratedatahavebeenmeasuredforthereactionA+B+CD.

Initialconcentration(molL1)
[A] [B] [C] Rate(molL1s1)
0.20 0.75 0.25 1.110 1
0.10 0.25 0.25 6.110 1
0.20 0.25 0.25 1.210 0
0.20 0.75 0.75 3.310 1

Whatistheratelawforthereaction?Whatistheoverallorderofthereaction?Determinethe
valueoftherateconstant(withthecorrectunits).
15.130ThefollowingratedatahavebeenmeasuredforthereactionE+F+GH.

Initialconcentration(molL1)
[E] [F] [G] Rate(molL1s1)
0.10 0.050 0.050 1.110 6
0.050 0.050 0.050 2.610 7
 0.10 0.15 0.10 1.910 5
0.10 0.15 0.050 9.510 6

Whatistheratelawforthereaction?Whatistheoverallorderofthereaction?Determinethe
valueoftherateconstant(withthecorrectunits).
15.131 (a) Whatisthehalflifeofafirstorderreactionwherek=2.010 1s1.
(b)Afterwhattimedoesonly1%ofreactantremain?
(c)Whyisitnotpossibletocalculatethehalflifeofasecondorderreactioniftherate
constantistheonlykineticinformationyouhave?
15.132CalculatetheactivationenergyforthereactionClO +H OClO +H fromthefollowing
3 2 4 2
data.

k(s1) Temperature(C)

2.010 3 25

4.010 3 35

8.010 3 45

1.610 3 55

15.133Calculatetheactivationenergyforasecondorderreactionusingthefollowingkineticdata:k=
4Lmol1s1at37Candk=8.0Lmol1s1at87C.
15.134 (a)CalculatetheaveragerateofachemicalreactioniftheconcentrationofreactantAis
0.45Mafter3.0minand0.20Mafter8.0min.
(b)Whydowerefertotheaverageratewhenwearecalculatingareactiontimeinterval?
15.135Whyisthefollowingreactionnotlikelytotakeplaceinonestep.

15.136Thereactioninquestion15.135isbelievedtotakeplaceinthefollowingthreesteps.

(a)Addthethreestepstoshowthatitgivesthecorrectoverallreaction:

(b)Identifyanyreactionintermediatesorcatalysts.
(c)Whichstepistheratedeterminingstep?Explain.
15.137ThehypotheticalreactionA+B2C+Dhasanactivationenergyof130kJandH=40kJ.
(a)Drawandlabelapotentialenergydiagramforthisreaction.
(b)Calculatetheactivationenergyforthereversereaction.
(c)WhatisHforthereversereaction?
15.138 (a)Whyisthereconcernoverexplosionstakingplaceatsawmillsorgrainstorage
buildings?
 (b)Whichofthefivefactorsthataffecttherateofareactionincreasestheratebyincreasing
thefractionofcollisionsthataresuccessful?
15.139 (a)Nametwoadvantagesofusingacatalysttospeedupachemicalreactionratherthan
usingheat.
(b)Nametwothingsthatacatalystdoesnotchangeinachemicalreaction.
15.140Whichofthefivefactorsthataffecttherateofareactionisillustratedineachofthefollowing:
(a)Foodissometimesfrozenbeforeitisused.
(b)Smallsticksofwoodareoftenusedtostartafire.
(c)Inhospitals,thespeedofthehealingprocessisoftenincreasedinanoxygentent.
15.141Whywouldyouexpecttherateofthereaction:

atroomtemperaturetobemuchfasterthantherateofthereaction:

atroomtemperature?
15.142ConsiderthereactionZn(s)+2HCl(aq)ZnCl2(aq)+H2(g).Whatwouldbetheeffectonthe
rateofreactionif:
(a)powderedzincwasusedinsteadofasolidpieceofzincmetal?
(b)theconcentrationofHCl(aq)wasdoubled?
(c)thetemperaturewasincreased?
15.143SketchapotentialenergydiagramforthegeneralreactionA+BC+D,whereHreverse =
10kJmol1andEaforward=+40kJmol1.
15.144Inthedecompositionreaction2N2O54NO2+O2,oxygengasisproducedatanaveragerate
of9.110 1molL1s1.Overthesameperiod,whatistheaveragerateofthefollowing?
(a)productionofnitrogendioxide
(b)lossofdinitrogenpentoxide
15.145ConsidertheformationofammoniaaccordingtoN2(g)+3H2(g)2NH3(g).Iftherateofloss
ofhydrogengasis0.03molL1s1,whatistherateofproductionofammonia?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERM
activationenergy(Ea ) heterogeneousreaction ratecoefficient
Arrheniusequation homogeneouscatalyst rateconstant
averagerate homogeneousreaction ratelaw
catalysis initialrate rateofreaction
catalyst instantaneousrateofchange ratedeterminingstep
chemicalkinetics ofconcentration reactioncoordinate
collisiontheory integratedratelaw reactionintermediate
differentialratelaw Michaelisconstant reactionmechanism
elementaryreaction MichaelisMentenequation steadystateapproximation
frequencyfactor MichaelisMentenmechanism stericfactor
halflife molecularity transitionstate
order
preexponentialfactor
heterogeneouscatalyst

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

16 TheChemistryof
Carbon
Scientistshaveestimatedthat,deepintheworld'soceansandpermafrost,morethan500
gigatonnesofcarbonliestrappedintheformofmethanelockedwithincagesmadefrom
moleculesofH2O.Thesefrozencagesarecalledclathratehydrates(shownburninginthe
photograph)andtheirdiscoverymayhaveimportantimplicationsfortheenvironment.
Methaneisknownasnaturalgasasitisfoundnaturallyinmanyplaces.Methanehasthe
formulaCH4(seeballandstickmodel),whichmakesitoneofthesimplestformsof
molecularcarbon,anditrepresentsanimportantenergysource.Ourcurrentnaturalgas
reservoirs,suchasthoseintheTimorSeatothenorthwestofAustraliaandthosepresentin
thecoalseamsincentralQueenslandandNewSouthWales,vastlyoutweightheestimated
amountofmethanethatistrappedwithinthewaterycagesintheoceansandicecaps.
However,asglobalwarmingraisestheEarth'stemperature,moreandmoreofthissimple
moleculemaybereleasedintotheatmosphereanditsimpactasagreenhousegascould
provetobeverysignificant.Carbondioxide,CO2,isanothersimplegaseousmoleculethat
containscarbonandisalsoinvolvedinglobalwarming.Thesetwosimpleformsofcarbon
mayholdthekeytocontrollingtheclimateofourentireplanet.

Methaneandcarbondioxideareexamplesofmoleculesthatinvolveonlyoneatomof
carbon.Carbonatomscanactuallycombinecovalentlywitheachotherandwithother
elementstoformanenormousvarietyofmoleculesotherthanCO2andCH4.Atthe
molecularleveloflife,natureusescompoundsofcarbon,andtheamazingvarietyofliving
systemsarisesfromthepropertiesofthiselement.Therearemanymillionsofcompounds
thatcontaincarbonincludingcolourfuldyes,drugs,perfumes,syntheticandnaturalfibres,
plastics,flavourings,foodsandfuels.Thelistcoversalmosteverythingweencounterinour
normallivesandalsoincludesthecarbohydrates,proteins,vitamins,fats,cellmembranes
andenzymesthatmakeupourownbodies.
 NationalEnergyTechnologyLaboratory

Organicchemistryisthestudyoftheproperties,preparation,identificationandmodification
ofcompoundsinvolvingcarbon.Themyriadformsofcarboncontainingmoleculeswould
beoverwhelmingbutforthefactthatwecanclassifythemaccordingtothepresenceof
similarlyreactingfunctionalgroups,thenaturesofwhichwewillintroduceoverthenext
severalchapters.However,beforedealingwiththesesystems,wewillfirstlookat
hydrocarbons,organicmoleculescontainingonlycarbonandhydrogen.Hydrocarbonsmake
uptheframeworksupportingthefunctionalgroupsthatarepresentinmostimportant
molecules.Inthischapter,webeginourstudyoforganiccompoundswithalkanes,the
simplesttypeoforganiccompounds.Thenwewillprogresstothefirstfunctionalgroups,
unsaturatedsystemscontainingdoubleandtriplebondsand,finally,wewilllookatcyclic
unsaturatedsystemscalledaromatics.

KEYTOPICS
 16.1Introductiontohydrocarbons
16.2Alkanes
16.3Alkenesandalkynes
16.4Reactionsofalkanes
16.5Reactionsofalkenes
16.6Reactionsofalkynes
16.7Aromaticcompounds
16.8Reactionsofaromaticcompounds:electrophilicaromaticsubstitution

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.1IntroductiontoHydrocarbons
Ahydrocarbonisacompoundcomposedofonlycarbonandhydrogen.Figure16.1showsthefour
classesofhydrocarbons,alongwiththecharacteristictypeofbondingbetweencarbonatomsineach.

FIGURE16.1Thefourclassesofhydrocarbons.

Alkanesarehydrocarbonsthatcontainonlycarboncarbonsinglebonds.Suchhydrocarbonsaresaidto
besaturatedhydrocarbons,meaningthateachcarbonatomhasthemaximumpossiblenumberof
atoms(four)bondedtoit.Weoftenrefertoalkanesasaliphatichydrocarbons,becausethephysical
propertiesofthehighermolecularweightmembersofthisclassresemblethoseofthelongcarbonchain
moleculeswefindinanimalfatsandplantoils(aliphaticisderivedfromtheGreekwordaleiphar
meaningfatoroil).

Alkenesarehydrocarbonsthatcontainoneormorecarboncarbondoublebonds.Alkynesare
hydrocarbonsthatcontainoneormorecarboncarbontriplebonds.Arenesarecyclicstructures
containingcarboncarbonbondsthatimpartspecialstability.Alkenes,alkynesandarenesaresaidtobe
unsaturatedhydrocarbons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.2Alkanes
Recallthatalkanesaresaturatedhydrocarbonstheycontainonlysinglebondsandeachcarbonhasthemaximumnumber
ofatoms(four)bondedtoit.Methane,CH4,andethane,C2H6,arethefirsttwomembersofthealkanefamily.Figure16.2
showsLewisstructuresandballandstickmodelsforthesemolecules.TheLewisstructuresshowtheatomconnectivitybut
donotreflectthethreedimensionalshapesofthemolecules.Welearnedinsection5.4thatmethaneistetrahedral,andall
HCHbondanglesare109.5.Eachcarbonatominethaneisalsotetrahedral,andallbondanglesareabout109.5.
Althoughthethreedimensionalshapesoflargeralkanesaremorecomplexthanthoseofmethaneandethane,thefour
bondsaroundeachcarbonatomarestillarrangedinatetrahedralmanner,andallbondanglesarestillapproximately
109.5.

FIGURE16.2Structuresofmethaneandethane.

Inchapter2welearnedvariouswaystodepictchemicalstructures.Infigure16.3,thenextmembersofthealkanefamily
propane,butaneandpentanearedrawn,firstascondensedstructuralformulaethatshowallcarbonsandhydrogens,
thenaslinestructures,andthenasballandstickmodels.Recallthat,inthistypeofrepresentation,alinerepresentsa
carboncarbonbondandananglerepresentsacarbonatom.AlineendingrepresentsaCH3group.Althoughhydrogen
atomsarenotshowninlinestructures,theyareassumedtobethereinsufficientnumberstogiveeachcarbonatomfour
bonds.

FIGURE16.3Structuresofpropane,butaneandpentane.

Wecanwritecondensedstructuralformulaeforalkanesinstillanotherabbreviatedform.Forexample,thecondensed
structuralformulaofpentane,CH3CH2CH2CH2CH3,containsthreeCH2(methylene)groupsinthemiddleofthechain.We
cancollectthesegroupstogetherandwritethecondensedstructuralformulaasCH3(CH2)3CH3.Table16.1givesthe
IUPACnamesandmolecularformulaeofthefirst10alkanes.Notethatthenamesofallalkanesendinane.
TABLE16.1 Names,molecularformulaeandcondensedstructuralformulaeforthefirst10straightchainalkanes.

Molecular Condensedstructural Meltingpoint Boilingpoint Densityofliquid(gmL1at0

 Name formula formula (C) (C) C)(a)
methane CH4 CH4 182 164 (agas)

ethane C2H6 CH3CH3 183 88 (agas)

propane C3H8 CH3CH2CH3 190 42 (agas)

butane C4H10 CH3(CH2)2CH3 138 0 (agas)

pentane C5H12 CH3(CH2)3CH3 130 36 0.626

hexane C6H14 CH3(CH2)4CH3 95 69 0.659

heptane C7H16 CH3(CH2)5CH3 90 98 0.684

octane C8H18 CH3(CH2)6CH3 57 126 0.703

nonane C9H20 CH3(CH2)7CH3 51 151 0.718

decane C10H22 CH3(CH2)8CH3 30 174 0.730

(a)Forcomparison,thedensityofH Ois1gmL1at4C.
2

AlkaneshavethegeneralmolecularformulaCnH2n+2(withtheexceptionofcycloalkanes,whichwewilldealwithlaterin
thechapter).Thus,giventhenumberofcarbonatomsinanalkane,itiseasytodeterminethenumberofhydrogenatomsin
themoleculeandalsoitsmolecularformula.Forexample,decane,with10carbonatoms,musthave(210)+2=22
hydrogenatomsandamolecularformulaofC10H22.

ConformationofAlkanes
Eventhoughstructuralandcondensedstructuralformulaeareusefulforshowingtheorderofattachmentofatoms,theydo
notshowthreedimensionalshapes.Torecognisetherelationshipsbetweenthestructureandpropertiesofmolecules,itis
crucialtounderstandthethreedimensionalshapesofmolecules.Moleculesarethreedimensionalobjects,anditisessential
thatyoubecomecomfortableindealingwiththemassuch.

Alkanesoftwoormorecarbonatomscanbetwistedintoanumberofdifferentthreedimensionalarrangementsbyrotating
aroundoneormorecarboncarbonbonds.Anythreedimensionalarrangementofatomsthatresultsfromrotationarounda
singlebondiscalledaconformertherepresentationofthepositionoftheatomsinthemoleculeiscalledits
conformation.Figure16.4ashowsaballandstickmodelofastaggeredconformationofethane.Inthisconformation,the
threeCHbondsononecarbonatomareasfarawayaspossiblefromthethreeCHbondsontheadjacentcarbonatom.
Figure16.4bshowsaNewmanprojection,whichisashorthandwayofrepresentingthestaggeredconformationofethane.
InaNewmanprojection,weviewamoleculealongtheaxisofaCCbond.Thethreeatomsorgroupsofatomsnearer
youreyeappearonlinesextendingfromthecentreofthecircleatanglesof120.Thethreeatomsorgroupsofatomson
thecarbonatomfurtherfromyoureyeappearonlinesextendingfromthecircumferenceofthecircleatanglesof120.
Rememberthatbondanglesaroundeachcarbonatominethaneareapproximately109.5andnot120,asthisNewman
projectionmightsuggest.

FIGURE16.4 Astaggeredconformationofethane:
(a)ballandstickmodelsand
(b)Newmanprojection.

Figure16.5showsaballandstickmodelandaNewmanprojectionofaneclipsedconformationofethane.Inthis
conformation,thethreeCHbondsononecarbonatomareascloseaspossibletothethreeCHbondsontheadjacent
carbonatom.Inotherwords,hydrogenatomsonthebackcarbonatomareeclipsedbythehydrogenatomsonthefront
carbonatom.(NotethatintheNewmanprojectionthebondshavebeenoffsetalittleforclarity.)

FIGURE16.5 Aneclipsedconformationofethane:
(a)ballandstickmodelsand
(b)Newmanprojection,withthebondsoffsetslightlyforclarity.

Thedifferenceinpotentialenergybetweenthesetwoconformationsisapproximately12.6kJmol1(seefigure16.6),which
meansthat,atroomtemperature,theratioofethanemoleculesinastaggeredconformationtothoseinaneclipsed
conformationisapproximately100to1.

FIGURE16.6Anenergydiagramshowingtheconformationalanalysisofethane.

Itisimportanttorealisethatmoleculesarenotstaticlikethepicturesyouseeonthispageandinfigure16.7onthenext
page.Atroomtemperaturethebondscanbestretching,shaking,bendingandvibratingupto10 13timespersecond!The
groupsrotatemoreslowly,buttypicalCCbondrotationisstillmorethanabillionrevolutionspersecond.Youwilllearn
moreabouthowchemistsdetectsomeoftheseatommovementswhenwedealwithinfraredspectroscopyinsection20.3.
Thekeypointhereisthat,atroomtemperature,movementbetweenthevariousconformersisconstantandoccurs
extremelyrapidly,evenwiththeenergybarriersthatarisefromeclipsinginteractions.Thus,whileyoumaybeabletodraw
manyconformationalformsforamolecule,inpracticalterms,foratypicalnoncyclicalkane,theydonotexistlongenough
todisplaythedifferentpropertiesthatconstitutionalisomerspossess.
 FIGURE16.7 (a)Noneofthesestructuresrepresentdifferentisomers.Theyareall4ethyl3,6dimethyloctanedrawnindifferent
orientationsorconformations.
(b)Thesephotosdonotrepresentdifferentpiecesofjewellery.Theyareallofthesamecharmbraceletshownin
differentorientationsorconformations.
JohnWiley&SonsAustralia

WORKEDEXAMPLE16.1

DrawingNewmanProjections
DrawNewmanprojectionsforonestaggeredconformationandoneeclipsedconformationofpropane.

Solution

ThefollowingareNewmanprojectionsandballandstickmodelsoftheseconformations.

Viewedendonalongthecentralcarboncarbonbond,wecanseetheatomsalignintheeclipsedconformation
whereas,inthestaggeredconformation,theyaredistributedasfarapartaspossible.

PRACTICEEXERCISE16.1
DrawNewmanprojectionsfortwostaggeredandtwo
eclipsedconformationsofbutaneasvieweddownthe
centralCCbond.

Cycloalkanes
Ahydrocarbonthatcontainscarbonatomsjoinedtoformaringiscalledacyclichydrocarbon.Whenallcarbonatomsof
theringaresaturated,wecallthehydrocarbonacycloalkane.Cycloalkaneswithringsizesofthreetoover30aboundin
nature,but,inprinciple,thereisnolimittoringsize.Fivemembered(cyclopentane)andsixmembered(cyclohexane)
ringsareespeciallyabundantinnature.

Cycloalkanescontaintwofewerhydrogenatomsthananalkanewiththesamenumberofcarbonatoms.Forinstance,
comparethemolecularformulaofcyclohexane,C6H12,withthatofhexane,C6H14.Thegeneralformulaofacycloalkaneis
CnH2n.Notethatcycloalkaneshavethesamemolecularformulaeaslinearalkenes.However,theyhaveessentiallythe
samechemicalreactivityaslinearalkanes,sothisdegreeofunsaturationdoesnotprovideanychemicalfunctionality.

Figure16.8showsthestructuralformulaeofcyclobutane,cyclopentaneandcyclohexane.Whenwritingstructuralformulae
forcycloalkanes,chemistsrarelyshowallcarbonandhydrogenatoms.Rather,theyuselinestructurestorepresent
cycloalkanerings.Eachringisrepresentedbyaregularpolygonhavingthesamenumberofsidesastherearecarbon
atomsinthering.Forexample,chemistsrepresentcyclobutanebyasquare,cyclopentanebyapentagonandcyclohexane
byahexagon.

FIGURE16.8Examplesofcycloalkanes:cyclobutane,cyclopentaneandcyclohexane.

Tonameacycloalkane,prefixthenameofthecorrespondingopenchainhydrocarbonwithcyclo,andnameeach
substituentonthering.Ifthereisonlyonesubstituent,thereisnoneedtogiveitanumber.Iftherearetwosubstituents,
numbertheringbeginningwiththesubstituentofloweralphabeticalorder.Iftherearethreeormoresubstituents,number
theringtogivethemthelowestsetofnumbers,andthenlistthesubstituentsinalphabeticalorder.

WORKEDEXAMPLE16.2

NamingCycloalkanes
WritethemolecularformulaandIUPACnameforeachofthefollowingcycloalkanes.
(a)

(b)

Analysisandsolution
(a)ThemolecularformulaofthiscycloalkaneisC8H16.Becausethereisonlyonesubstituentonthering,
thereisnoneedtonumbertheatomsofthering.IUPACacceptstwonamesforthiscompound:
isopropylcyclopentaneand1methylethylcyclopentane.
(b)Numbertheatomsofthecyclohexaneringbeginningwithtertbutyl,thesubstituentofloweralphabetical
order.Thecompound'snameis1tertbutyl4methylcyclohexaneanditsmolecularformulaisC11H22.
IUPACalsoaccepts1(1,1dimethylethyl)4methylcyclohexane.

PRACTICEEXERCISE16.2
WritethemolecularformulaandIUPACnamefor
 eachofthefollowingcycloalkanes.
(a)

(b)

(c)

Conformationsofcycloalkanes
Whenusinglinestructurepolygonstorepresentcycloalkanerings,itisimportanttorealisethatcycloalkanesarenotflat
structures.Apentagonpossessesanglesof108,whichisclosetotheidealtetrahedralangleof109.5foundinmethane
(seesection5.4).Thisimpliesthattheanglestraininaflatpentagonwouldbesmall.Anglestrainresultswhenabond
angleinamoleculediffersfromtheoptimaltetrahedralangle.Yetcyclopentaneisnotflatbutinfactformsanopen
envelopestructure.

Thisstructurearisestoreducetheeclipsinginteractionsthatwouldoccurifthemoleculewasaflatstructure.Recallfrom
thediscussionsontheconformationofalkanes(p.688)thatthelowestenergyforamoleculeariseswhenbondsare
staggeredandarenoteclipsedintheNewmanprojection(figure16.4).Aflatpentagonstructureforpentanewouldgive
riseto10eclipsedCHbonds.Thisunfavouredinteractionproducestorsionalstrain.Alsocalledeclipsedinteraction
strain,torsionalstrainariseswhennonbondedatomsseparatedbythreebondsareforcedfromastaggeredconformationto
aneclipsedconformation.Foraflatpentagonstructurethistorsionalstrainwouldequatetoabout42kJmol1.Torelieve
someofthisstrain,theatomstwistintotheenvelopeconformation(figure16.9)wherefourcarbonatomsareinaplane
andthefifthcarbonliesabovetheplane,somewhatlikeanenvelopewiththeflapfoldedoutward.

FIGURE16.9Envelopeconformation.

Inthisenvelopeconformationthenumberofeclipsinginteractionsisreduced,buttoattainthisshapetheCCCbond
anglesarealsoreducedto105,thusindicatinganincreaseinanglestrain.Thetotalstrainenergyincyclopentaneinthe
envelopeconformationisabout23.4kJmol1,whichissubstantiallylessthanifthemoleculewascompletelyflat.Itis
importanttoremember,however,thatmoleculesexistinadynamicsituationandthesecyclopentanemoleculesarenot
rigidandunmoving.Althoughtheenvelopeconformationrepresentsapreferredlowerenergystate,atnormaltemperatures
thesemoleculesvibrateandwiggleasbondsstretchandcontract.Theoutofplanecarbonatomcanmovetotheotherside
oftheplane,andindeedothercarbonatomsintheringcanassumetheoutofplaneposition.Thispropertyisparticularly
importantwithotherrings,especiallycyclohexane.

Cyclohexanecanreadilyadoptanumberofpuckeredconformations,themoststableofwhichiscalledthechair
conformation.Inthechairconformation,fourcarbonatomslieinaplanewithonecarbonatomabovetheplaneand
anothercarbonatomontheoppositesideoftheringtakingapositionbelowtheplane.Theshapeofthechairconformation
issomewhatlikethelowrecliningchairsthatyoumightfindbesideaswimmingpool(figure16.10).Thechair
conformationforcyclohexane(figure16.11)isthemoststablearrangementbecausetheCCCbondanglesareallvery
closetotheideal109.5(minimisinganglestrain)andtheCHbondscanallformalowenergystaggeredorientation
(minimisingtorsionalstrain).TheconsequenceofthisisthatinthechairconformationtherearetwosetsofCHbonds,
dependingontheirorientationinspace.SixCHbondsareorientedessentiallyinthesameplaneasthefourcarbonatoms
thatmakeuptheseatofthechair.TheothersixCHbondspointeitherupordownintheapproximatedirectionofthe
chairbackorlegs.Arrangingthebondsinthisconformationminimisesangleandtorsionalstrain,andsocyclohexanein
thechairconformationhasalmostnostrainenergythisexplainswhythesesixmemberedringsofcarbonarefoundso
commonlyinnature.

FIGURE16.10Chairconformation.

FIGURE16.11 Cyclohexane.Themoststableconformationisthechairconformation:
(a)ballandstickmodelviewedfromabove,
 (b)ballandstickmodelviewedfromtheside,
(c)skeletalmodel,
(d)skeletalmodelviewedfromthefrontofthechairand
(e)Newmanprojection.

Equatorialbondsarethosethatareorientedmoreorlessintheplaneoftheseatofthechair(figure16.12b)andthe
hydrogenatomsthereforearecalledequatorialhydrogenatoms.Theotherbondsarecalledaxialbonds(figure16.12c)and
thehydrogenatomsinthisorientationarecalledaxialhydrogenatoms.Threeaxialbondsaredirectedupwardsandthree
downwards.Equatorialbondsarealignedapproximatelyintheplaneoftheseatoftheimaginarychair,butcloseinspection
showsthatthesealsoinvolvethreebondsthatpointslightlyupandthreethatpointslightlydown.Noticealsothatthe
orientationofeithertheaxialortheequatorialbondsalternates,firstupandthendown,asyoumovefromonecarbonatom
intheringtothenext.Iftheaxialbondononecarbonatompointsupthentheequatorialbondonthatcarbonatompoints
slightlydownwards.Conversely,iftheaxialbondonaparticularcarbonatompointsdownwards,thentheequatorialbond
onthatatompointsslightlyupwards.

FIGURE16.12 ChairconformationofcyclohexaneshowingaxialandequatorialCHbonds:
(a)ballandstickmodelshowingall12hydrogenatoms,
(b)thesixequatorialCHbondsand
(c)thesixaxialCHbonds.

Rememberthat,likecyclopentane,cyclohexaneexistsinadynamicstateandtherearemanyothernonplanar
conformationsthattheringeasilyattains.Apartfromotherchairconformations,thereisalsoaboatconformation.The
boatconformationoccurswhenbothoftheoutofplanecarbonatomsareonthesamesideoftheplanemadefromthe
otherfourcarbonatoms.Thisconformationisreadilyformedfromthechairconformationbybendingtheringand
swingingthecarbonatomonthechairlegupsothatitreachesthesamepositionasthecarbonatomonthechairback
(figure16.13).

FIGURE16.13 Conversionof
 (a)achairconformationto
(b)aboatconformation.Intheboatconformation,thereisbothtorsionalstrain,duetothefoursetsofeclipsed
hydrogeninteractions,andstericstrain.Achairconformationismorestablethanaboatconformation.

Theboatconformationislessstablethanthechairconformation.Torsionalstrainispresentintheboatconformationasfour
setsofhydrogenatomsbecomeeclipsed.Anothertypeofstrain,calledstericstrain,isalsogenerated.Stericstrainisalso
callednonbondedinteractionstrain,anditinvolvesstrainwhicharisesinthemoleculewhentwopartstrytooccupythe
samespace.Inthecaseoftheboatconformationofcyclohexane,thetwoaxialhydrogenatomsandtheirattendantelectron
cloudsinteractacrossthering,andthisunfavourableactionleadstostraininthemolecule.Thedifferenceinenergy
betweenthechairandtheboatconformationsisabout27kJmol1.Thismeansthat,atroomtemperature,fewerthan
0.001%ofthemoleculesmightbefoundintheboatconformationatanytime.Infact,tolowertheenergyslightly,theboat
conformationtwistsintoastructurecalledthetwistboat,whichisafewkJmol1lowerinenergy.Nevertheless,theboat
conformationisimportant,asitisthroughthishigherenergyorientationthatonechairconformationisconvertedinto
another.Twoequivalentenergychairconformationsinterconvertrapidlyatroomtemperaturebyfirsttwistingintothe
higherenergyboatconformation(figure16.13)andthenrelaxingintothelowerenergychairconformation.Whenone
chairisconvertedintoanother,achangeoccursinrelativeorientationsinspaceofthehydrogenatomsboundtothecarbon
atomsofthering.Allequatorialhydrogenatomsinonechairbecomeaxialhydrogenatomsintheotherandviceversa
(figure16.14).

FIGURE16.14Interconversionofchaircyclohexanesviaaboatconformation.AllCHbondsthatareequatorialinonechairare
axialintheotherchair,andviceversa.

Thisprocessbecomesmuchmoresignificantwhenoneofthehydrogenatomsisreplacedbyanothergroupsuchasa
methylorotheralkylgroup.Interconversionofonechairtoanothernowhastheconsequenceofconvertingthesubstituted
groupfromanequatorialtoanaxialorientation(orviceversa)andthisnowhasenergyimplications.Alargegroupcan
imposeconsiderablestericstrainacrosstheringwhenitisinanaxialorientation.Thistypeofstrainiscalledanaxialaxial
(ordiaxial)interaction.Thepresenceofsuchagroupontheringfavoursthechairconformationwherethegroupisinthe
equatorialorientation.Foramethylgroup,thismakestheaxialorientationabout7.28kJmol1higherinenergyandso,at
roomtemperatureandatequilibrium,about95%ofthesemoleculeswouldhavethemethylgroupintheequatorial
orientation(figure16.15).Likethehigherenergyboatconformation,however,thisdoesnotmeanthatsuchaconformation
isnotreadilyachievableatroomtemperaturebutratherthatsuchmoleculespreferoneconformationovertheother.
However,thiseffectcanbecomeverysignificantwhenalargegroupispresentonthecyclohexanering.Largegroupscan
essentiallylocktheringintotheconformationwherethegroupisequatorial.Foratertbutylgroup(table2.9,p.55),
whichisconsiderablylargerthanamethylgroup,thispreferencemeansthattheequatorialconformeris4000timesmore
abundantthantheconformerwherethetertbutylgroupisintheaxialorientation.Ineffect,theringislockedintoone
conformation,andchemistsactuallycallsuchmoleculesconformationallylockedisomers.

FIGURE16.151,3diaxialinteractionleadstostericstrain.

WORKEDEXAMPLE16.3

CycloalkaneConformationalIsomers
Isitpossibletodrawalowerenergyconformationforthefollowingmolecule?

Analysis

Inalowerenergyconformation,thelargetbutylgroupwouldnotbeinanaxialpositionasitinteractswiththe
axialhydrogenatomsoncarbons3and5.Weknowthatcyclohexanescaneasilyfliptheirorientationfromone
chairconformertotheother,soweshouldseewhatthestructurelookslikeaftersuchatransformation.

Solution

Bringingthelefthandsideoftheringdownwardsandliftingtherighthandsideupwardsswapsthepositionsof
thecurrentaxialgroupswiththeequatorialposition.
Isouranswerreasonable?

ThespeedatwhichCCbondsrotatemeansthatthetbutylgroupcanbethoughtofasahighspeedfanwith
themethylgroupblades,strikingtheaxialhydrogenatomsoncarbons3and5.Thelargetbutylgroupisnow
placedfurtherawayfromtheotherpartsofthecyclohexane,withwhichitwaspreviouslyinteracting.

PRACTICEEXERCISE16.3
Foreachofthefollowingpairs,whichisthelower
energyconformation?Explainyouranswers.
(a) i.

ii.

(b) i.

ii.

(c) i.

ii.
CistransIsomerisminCycloalkanes
Cycloalkaneswithsubstituentsontwoormorecarbonatomsoftheringarecalledcistransisomers.Allcistransisomers
have(1)thesamemolecularformula,(2)thesameorderofattachmentofatomsand(3)anarrangementofatomsthat
cannotbeinterchangedbyrotationaroundbondsunderordinaryconditions(seechapter5).Incisisomers,thegroupsare
onthesamesideintransisomers,thegroupsareacrossfromeachother.

Inchapter2,weillustratedcistransisomerismincycloalkanesusing1,2dimethylcyclopentane.

Forsimplicity,samehydrogenatomshavebeenomittedand,toaddclarity,thecyclopentaneringhasbeendrawnasa
planarpentagonviewededgeon.(Weknowthatcyclopentaneexistsprimarilyinanenvelopeconformationshowninthe
ballandstickmodelsabove.However,toanalysethestructuralrelationshipbetweenthesubstituents,wecanrepresentthis
asapentagonallinedrawing.)Carboncarbonbondsoftheringthatprojectforwardsareshownaboveasheavylines.
Whenviewedfromthisperspective,substituentsbondedtothecyclopentaneringprojectaboveandbelowtheplaneofthe
ring.Intheisomerof1,2dimethylcyclopentaneshownaboveleft,themethylgroupsareonthesamesideofthering
(eitherbothaboveorbothbelowtheplaneofthering)andwecallthisarrangementcisintheisomershownontheright,
themethylgroupsareonoppositesidesofthering(oneaboveandonebelowtheplaneofthering)andwecallthis
arrangementtrans.

Alternatively,thecyclopentaneringcanbeviewedfromabove,withtheringintheplaneofthepaper.Substituentsonthe
ringtheneitherprojecttowardsyou(thatis,theyprojectabovetheplaneofthepage)andareshownbysolidwedges,or
projectawayfromyou(theyprojectbelowtheplaneofthepage)andareshownbyhashedwedges.Inthefollowing
structuralformulae,onlythetwomethylgroupsareshown(hydrogenatomsoftheringarenotshown).

WORKEDEXAMPLE16.4

DrawingCistransIsomers
Whichofthefollowingcycloalkanesshowcistransisomerism?Foreachthatdoes,drawbothforms.
(a)methylcyclopentane
(b)1,1dimethylcyclobutane
(c)1,3dimethylcyclobutane
 Analysisandsolution
(a)Methylcyclopentanedoesnotshowcistransisomerism.Ithasonlyonesubstituentonthering.
(b)Onlyonearrangementispossibleforthetwomethylgroupsonthering,whichmustbetrans,so1,1
dimethylcyclobutanedoesnotshowcistransisomerism.

(c)Thefollowingdiagramshowsthecistransisomerismof1,3dimethylcyclobutane.Notethat,inthese
structuralformulae,weshowonlythehydrogenatomsoncarbonatomsbearingthemethylgroups.

PRACTICEEXERCISE16.4
Whichofthefollowingcycloalkanesshowcistrans
isomerism?Foreachthatdoes,drawbothisomers.
(a)1,3dimethylcyclopentane
(b)ethylcyclopentane
(c)1ethyl2methylcyclobutane

PhysicalPropertiesofAlkanes
Themostimportantpropertyofalkanesistheiralmostcompletelackofpolarity.Thisisillustratedinfigure16.16,which
showstheuniformdistributionoftheouterbondingelectronsinpentane.Aswesawinchapter5,thedifferencein
electronegativitybetweencarbonandhydrogenis2.52.1=0.4onthePaulingscaleand,giventhissmalldifference,we
classifyaCHbondasanonpolarcovalentbond.Therefore,alkanesarenonpolarcompounds,andthereareonlyweak
interactionsbetweenmolecules.

FIGURE16.16Theelectrondensitymodelofpentane(likeallalkanes)showsnoevidenceofpolarity.

BoilingPoints
Aswesawinchapter6(pp.2412),interactionsbetweenalkanemoleculesconsistofonlyweakdispersionforces.
Becauseofthis,theboilingpointsofalkanesarelowerthanthoseofalmostanyothertypeofcompoundofthesamemolar
mass.Asthenumberofatomsandelectronsand,therefore,themolarmassofanalkaneincrease,thenumber,andhence
totalstrength,ofdispersionforcesbetweenalkanemoleculesincreases,therebyincreasingtheboilingpoint(seefigure
6.34).

Alkanescontainingonetofourcarbonatomsaregasesatroomtemperatureandatmosphericpressure,andthosecontaining
fiveto17carbonatomsarecolourlessliquids.Highmolarmassalkanes(thosewith18ormorecarbonatoms)arewhite,
waxysolids.Severalplantwaxesarehighmolarmassalkanes.Thewaxfoundnaturallyinappleskins,forexample,isan
unbranchedalkanewiththemolecularformulaC27H56.Paraffinwax,amixtureofhighmolarmassalkanes,isusedfor
waxcandles,inlubricantsandtosealhomemadejamsandotherpreserves.Petrolatum,sonamedbecauseitisderived
frompetroleumrefining,isaliquidmixtureofhighmolarmassalkanes.SoldasmineraloilandVaseline,petrolatumis
usedasanointmentbaseinpharmaceuticalsandcosmeticsandasalubricantandrustpreventative.

MeltingPointandDensity
Themeltingpointsofalkanesincreasewithincreasingmolarmass.Theincrease,however,isnotasregularasthat
observedforboilingpoints,becausetheabilityofmoleculestopackintoorderedpatternsofsolidschangesasthe
molecularsizeandshapechange.

Theaveragedensityofthealkaneslistedintable16.1isabout0.7gmL1whereasthatofhighermolarmassalkanesis
about0.8gmL1.Allliquidandsolidalkanesarelessdensethanwater(1.0gmL1)andsofloatonwater.

IsomericAlkanes
Recallthatisomersaremoleculeswiththesamemolecularformulabutdifferentstructures,andconstitutionalisomersare
compoundswiththesamemolecularformulabutdifferentstructuresbecauseofdifferentsequencesofatomconnectivity.
Alkanesexhibitconstitutionalisomerismarisingfromsidechainsinthecarbonsequence.Aswelearnedinchapter2(pp.
556),eachisomerhasauniquenameaccordingtoasetofrulesinwhichnumbersareusedtoindicatethepositionsofthe
sidechains.

Theabilityofcarbonatomstoformstrongstablebondswithothercarbonatomsresultsinastaggeringnumberof
constitutionalisomers.Astable16.2shows,therearethreeconstitutionalisomerswiththemolecularformulaC5H12,75
constitutionalisomerswiththemolecularformulaC10H22andmorethan36millionconstitutionalisomerswiththe
molecularformulaC25H52.

TABLE16.2 ConstitutionalisomersofvariousCn H2n+2 hydrocarbons.

Molecularformula No.ofconstitutionalisomers
CH4 0
C5H12 3
C10H22 75

C15H32 4347
C25H52 36797588

Thus,forevenasmallnumberofcarbonandhydrogenatoms,averylargenumberofconstitutionalisomersispossible.In
fact,thepotentialforstructuralandfunctionalgroupindividualityamongorganicmoleculesmadefromjustthebasic
buildingblocksofcarbon,hydrogen,nitrogenandoxygenispracticallylimitless.

WORKEDEXAMPLE16.5

HydrocarbonIsomers
HowmanytypesofdifferenthydrocarbonmoleculesaretherewiththeformulaeC4H10,C5H12,C6H14,C11H24
 andC30H62?

Analysis

Thequestionseemsstraightforwardand,atleastinitially,itis.Thecompoundslistedareordinaryhydrocarbons.
Therearenootherelementspresentsoallstructuralvarietyarisesfromthedifferentsequencesbywhichcarbon
atomsandhydrogenatomscanbeassembled.Thereisnosimpleshortcuttotheanswertothisquestionand,in
fact,wearebetterservedbydrawingoutthepossiblestructurestobetterunderstandthenatureofthemolecules
involved.

Solution

Startingwiththesimplest,C4H10,therearetwopossiblestructures.Themostobviousanswerisasimplechainof
carbonatoms.Thereisanotherpossiblesequence,however,involvingabranch.

WithC5H12,threedifferentmoleculesarepossible:

ForC6H14,therearefivedifferentwaystoassemblethecarbonandhydrogenatoms:

Hereyouwillnoticethat,forclarity,wehavenotusedlinestructures.However,evenifwedid,spaceprecludes
drawingallthepossiblestructuresforC11H24thereare159!

YouwillnotbesurprisedtoknowthattherearealotofisomersofC30H62,butyouwillstillnodoubtbe
shockedtoknowjusthowmany.Therearemorethan4billionwaysofassemblingthese92atoms.Most
organiccompoundscontainmanymorethanthisnumberofatomsandalmostallinvolveotherelementsand
morecomplicatedbondingthanispresentinsimplehydrocarbons.Thisiswhyorganicchemistryissucha
challengingfieldofscienceandwhyweneedtofindgroupingsofsimilarpropertiesandcategoriestosimplify
thetopic.

Isouranswerreasonable?

Toconfirmthatthestructuralformulaedrawnrepresentconstitutionalisomers,writethemolecularformulaof
eachandcheckthattheyarethesame,andcheckeachstructuretoensurethatsimplerotationaroundanybond
doesnotreproduceoneoftheotherstructures.

Aswelearnedinchapter2,constitutionalisomershavedifferentphysicalproperties.Table16.3liststheboilingpoints,
meltingpointsanddensitiesofthefivecompoundswiththemolecularformulaC6H14.Theboilingpointofeachofthe
branchedchainmoleculesislowerthanthatofhexaneitself,andthemorebranchingthereisthelowertheboilingpointis.
Thesedifferencesinboilingpointsarerelatedtomolecularshape.Theonlyforcesofattractionbetweenalkanemolecules
aredispersionforces.Asbranchingincreases,theshapeofanalkanemoleculebecomesmorecompact,anditssurfacearea
decreases.Asthesurfaceareadecreases,sotoodoestheareaofcontactbetweenmolecules.Thisdecreaseleadstoweaker
dispersionforces,soboilingpointsalsodecrease(seefigure16.17).Thus,foranygroupofconstitutionalisomers,itis
usuallyobservedthattheleastbranchedisomerhasthehighestboilingpointandthemostbranchedisomerhasthelowest
boilingpoint.Thetrendinmeltingpointsislessobvious,but,aspreviouslymentioned,itcorrelateswithamolecule's
abilitytopackintoorderedarraysofsolids.
TABLE16.3 PhysicalpropertiesoftheisomericalkaneswiththemolecularformulaC6 H14 .

Name Boilingpoint(C) Meltingpoint(C) Density(gmL1at0C)

hexane 69 95 0.659
3methylpentane 63 118 0.664
2methylpentane 60 153 0.653
2,3dimethylbutane 58 128 0.662
2,2dimethylbutane 50 100 0.649

FIGURE16.17Asbranchingincreases,theshapeofanalkanemoleculebecomesmorecompact,anditssurfaceareadecreases.
Asthesurfaceareadecreases,thestrengthofthedispersionforcesdecreases,andtheboilingpointalso
decreases.

WORKEDEXAMPLE16.6

PhysicalPropertiesofAlkanes
Arrangethealkanesineachofthefollowingsetsinorderofincreasingboilingpoint.
(a)butane,decaneandhexane
(b)2methylheptane,octaneand2,2,4trimethylpentane

Analysisandsolution
(a)Allofthecompoundsareunbranchedalkanes.Asthenumberofcarbonatomsinthechainincreases,the
dispersionforcesbetweenmoleculesincrease,andtheboilingpointincreases.Decanehasthehighest
boilingpointandbutanethelowest.

(b)ThesethreealkanesareconstitutionalisomerswiththemolecularformulaC8H18.Theirrelativeboiling
pointsdependonthedegreeofbranching.Themosthighlybranchedisomer,2,2,4trimethylpentane,has
thesmallestsurfaceareaandthelowestboilingpoint.Octane,theunbranchedisomer,hasthelargest
surfaceareaandthehighestboilingpoint.

PRACTICEEXERCISE16.5
 Arrangethealkanesineachofthefollowingsetsin
orderofincreasingboilingpoint.
(a)2methylbutane,2,2dimethylpropaneand
pentane
(b)3,3dimethylheptane,2,2,4trimethylhexane
andnonane

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.3AlkenesandAlkynes
Somehydrocarbonshavedoublebondsortriplebondsbetweencarbonatomsand,hence,fewerhydrogenatomsthan
thecorrespondingalkanes.Thesearecalledunsaturatedhydrocarbons.Therearethreeclassesofunsaturated
hydrocarbons:alkenes,alkynesandarenes.Alkenescontainoneormorecarboncarbondoublebonds,andalkynes
containoneormorecarboncarbontriplebonds.AlkeneshavethegeneralformulaCnH2n.Alkyneshavethegeneral
formulaCnH2n2.Etheneisthesimplestalkene,andethyneisthesimplestalkyne:

Arenesarethethirdclassofunsaturatedhydrocarbons.Thesimplestareneisbenzene:

Arenesarecompoundsthatcontainoneormorebenzenerings.Thechemistryofbenzeneanditsderivativesisquite
differentfromthatofalkenesandalkynesandwillbedescribedlaterinthechapter.Allweneedtorememberatthis
pointisthatabenzeneringisnotchemicallyreactiveunderanyoftheconditionswedescribeforsimplealkenesand
alkynes.

Compoundscontainingcarboncarbondoublebondsareespeciallywidespreadinnature.Manyorganiccompounds
foundinnaturearederivedfromanalkenecalledisoprene.Isopreneisamajorcontributortothehazeandscentthat
arecharacteristicofAustralianeucalyptusforests(figure16.18).Furthermore,severallowmolarmassalkenes,
includingetheneandpropene,haveenormouscommercialimportanceinourmodern,industrialisedsociety.The
organicchemicalindustryproducesmoreetheneworldwidethananyotherchemical.
 FIGURE16.18ThebluehazethatgivestheBlueMountainstheirnamearisesfromisopreneandotherhydrocarbonsreleased
fromeucalyptustreesonexposuretosunlightandhightemperatures.

Etheneisunusualamongthealkenesinthatitoccursonlyintraceamountsinnature(whereitplaysanessentialrolein
theprocessbywhichfruitripens).Theenormousamountsofitrequiredtomeettheneedsofthechemicalindustryare
generatedfromtherefiningofcrudeoilintopetrolortheconversionofethaneextractedfromnaturalgasasshown
below.

Thecrucialpointtorecogniseisthatetheneandallofthecommercialandindustrialproductsmadefromit(suchas
plasticshoppingbags)arederivedfromeithernaturalgasorcrudeoilbothnonrenewablenaturalresources!

ShapesofAlkenesandAlkynes
Usingthevalenceshellelectronpairrepulsion(VSEPR)model(seechapter5),wepredictavalueof120forthebond
anglesaroundeachcarbonatominadoublebond.TheobservedHCCbondangleinetheneis121.7,avalue
closetothatpredictedbythismodel.Inotheralkenes,deviationsfromthepredictedangleof120maybesomewhat
largerasaresultofstrainbetweengroupsbondedtooneorbothcarbonatomsofthedoublebond.TheCCC
bondangleinpropene,forexample,is124.7.

UsingtheVSEPRmodelagain,wepredictallofthebondanglesaroundeachcarbonatominthetriplebondtobe
180.Thesimplestalkyneisethyne,C2H2.Ethyneisindeedalinearmoleculeallofitsbondanglesare180.(Note:
Allorbitals,exceptpinkorbitals,arethesamephase.Coloursareusedforclarityonly.)

Aswesawinchapter5,aC Ctriplebondisdescribedintermsoftheoverlapofsphybridorbitalsofadjacent
carbonatomstoformabond,theoverlapofparallel2p y orbitalstoformonebond,andtheoverlapofparallel2p z
orbitalstoformasecondbond.Inethyne,eachcarbonatombondstoahydrogenatombytheoverlapofansp
hybridorbitalofcarbonwitha1satomicorbitalofhydrogen.
CistransIsomerisminAlkenes
Inchapter5,wedescribedtheformationofacarboncarbondoublebondintermsoftheoverlapofatomicorbitals.A
carboncarbondoublebondconsistsofonebondandonebond.Eachcarbonatomofthedoublebondusesits
threesp 2hybridorbitalstoformbondswiththreeatoms.Theunhybridised2patomicorbitals,whichlie
perpendiculartotheplanecreatedbytheaxesofthethreesp 2hybridorbitals,combinetoformthebondofthe
carboncarbondoublebond.

Whereasrotationaroundasinglebondisrelativelyfree(theenergybarrierinethaneisapproximately12.5kJmol1),it
takesconsiderablymoreenergytorotateadoublebond.Tobreakthebondinethene(i.e.torotateonecarbonatom
by90withrespecttotheothersothatnooverlapoccursbetween2porbitalsonadjacentcarbonatoms)requires
approximately264kJmol1(figure16.19).Thisenergyisconsiderablygreaterthanthethermalenergyavailableat
roomtemperature,sorotationaroundacarboncarbondoublebondisseverelyrestricted.

FIGURE16.19 Restrictedrotationaroundthecarboncarbondoublebondinethene:
(a)Orbitaloverlapmodelshowingthebond
(b)ThebondisbrokenbyrotatingtheplaneofoneHCHgroupby90withrespecttotheplaneof
theotherHCHgroup.
Becauseofrestrictedrotationaroundacarboncarbondoublebond,analkeneinwhicheachcarbonatomofthe
doublebondhastwodifferentgroupsbondedtoitshowscistransisomerism.Consider,forexample,but2ene.In
cisbut2ene,thetwomethylgroupsareonthesamesideofthedoublebondintransbut2ene,thetwomethyl
groupsareonoppositesidesofthedoublebond.

Thesetwocompoundscannotbeconvertedintooneanotheratroomtemperaturebecauseoftherestrictedrotation
aroundthedoublebondtheyaredifferentcompoundswithdifferentphysicalandchemicalpropertiesandarecalled
configurationalisomers.

Becauseofrepulsionbetweenalkylsubstituentsonthesamesideofthedoublebondinthecisisomer,cisalkenesare
lessstablethantheirtransisomers.Thiscanbeseenfromtheforcingtogetherofthemethylhydrogenatomsinthe
spacefillingmodelofcisbut2enemodelabove.

ChemicalConnections

TheChemistryofVision:FromMantoMollusc

Remarkably,allvertebrates,arthropodsand,indeed,somemolluscsshareaspectsoftheamazingchemistry
thatdrivestheprocessofvision.Tosomeextent,allofthesecreaturesrelyonthesamemolecule,11cis
retinal,anunsaturatedalkenethatstronglyabsorbsbluegreenlight(between450and550nmwithapeak
absorptionat498nm).Thismolecule,whenboundtotheproteinopsininhumaneyes,formsrhodopsina
purplecolouredmaterialthatisthebasisofhowwesenselightandconvertthistoabiologicalresponse.

Oureyesaresophisticatedorganswithtwoformsoflightsensingcellsthat,becauseoftheirshape,arecalled
rodsandcones.About100millionrodcellsarelocatedprimarilyontheperipheryoftheretina,andthese
allowvisioninlowlight.However,thissensitivitydoesnotextendtocolourrecognition,sotheviewis
monochromatic.Todetectcolour,therearethreetypesofconecells,eachofwhichusesretinalboundto
proteins,slightlydifferentfromopsin,callediodopsins.Variationinafewkeyaminoacidsintheiodopsin
chaindistortsretinal'sbondsystemtochangethepositionofthepeakofmaximumlightabsorption.

Inthehumaneye,thereareonlyabout3millionconecells,andthephotoreceptorsinthesecellsaresensitive
tothreedifferentportionsofthevisiblespectrumcoveringfromabout380nmto750nm.Agreenappleis
perceivedbyustobegreenonlybecauseoureyeisabletodistinguishbetweendifferentwavelengths.A
greenappledoesnotemitgreenlight.Rather,itsimplyabsorbsallthewavelengthsoflightshiningonit
exceptthewavelengthswecallgreen,whicharereflected,enteroureyeandaredetectedbyourbrainas
green(figure16.20).
 FIGURE16.20Agreenappleabsorbsallwavelengthsoflightexceptgreen,whichitreflects.Thereflectedlight
entersoureyesandthebraindetectsitasgreen.

Thesignalsgeneratedbytherodandconecellsintheretinaareconvertedbyourbraintoavisualimageof
thecolourandbrightnessofanobject.Thisprocessreliesonaremarkablefusionofphysics,chemistryand
biology:thephysicsoflightinteractingwithmatter,thechemistryofhowamolecule'sshapeiscontrolledby
thenatureofitsbondsandthebiologyofthewayamolecule'sshapegovernsacellularmembranetocreatea
flowofionsandanerveresponse.Tointeractwithlight,amoleculemusthavebondsthatallowabsorptionof
thepreciseenergyofthelightweseeasvisible.Mostorganicmoleculesdonotabsorbanylightinthis
regionandso,naturally,cannotformthebasisofachemicallightdetector.However,when11cisretinalis
boundtoopsin,itabsorbstheenergyofphotonsofwavelengtharound500nmrightinthemiddleofour
visibleregion.Thisisonlythefirststepinacomplicatedprocess,however(seefigure16.21).Absorptionof
lightallows11cisretinaltorelaxfromabentshape(arisingfromthecisdoublebond)toalowerenergy,
alltransarrangement.Thestraighteralltransretinalcannolongerfitinthereceptordesignedfor11cis
retinalandisejected.Thischangeleadstodifferencesincellmembranepotentialand,asionsarepumped
intothecell,thisresponseturnsintoanerveimpulsethattravelstothebrain.Thatisnottheendofthematter
thealltransretinalgeneratedbythisprocessisreconvertedto11cisretinalbyspecificenzymes,whichcan
rebindintothereceptor,readytointeractwithanotherphotonoflight.
 FIGURE16.21Thechemistryofcolourdetectionintheeyefollowingabsorptionofaparticularwavelengthoflight
byrhodopsin.

NomenclatureofAlkenesandAlkynes
Likealkanes,alkenesarenamedusingtheIUPACsystem,but,asweshallsee,somearestillreferredtobytheir
commonnames.

WeformIUPACnamesofalkenesbychangingtheancomponentofthenameoftheparentalkanetoen.Hence,
CH2 CH2isnamedethene,andCH3CH CH2isnamedpropene.Inhigheralkeneswherethelocationofthe
doublebonddiffersbetweenisomers,weuseanumberingsystem.Weidentifythelongestcarbonchainthatcontains
thedoublebondandnumberitinthedirectionthatgivesthecarbonatomsofthedoublebondthelowersetof
numbers.Wethenusethenumberofthefirstcarbonatomofthedoublebondtoshowitslocation.Asseenbelow,
hex1enehasthedoublebondattheendofthechain,thedoublebondinhex2eneinvolvesthe2ndand3rdcarbon
atoms,andthedoublebondinhex3eneisinthemiddleofthechain.Wenamebranchedorsubstitutedalkenesina
mannersimilartothewaywenamealkanes.Wenumberthecarbonatoms,locatethedoublebond,locateandname
substituentgroups,andnamethemainchain.

Notethatthereisasixcarbonchainin2ethyl3methylpent1ene.However,becausethelongestchainthatcontains
thedoublebondhasonlyfivecarbonatoms,theparenthydrocarbonispentane,andwenamethemoleculeasa
disubstitutedpent1ene.

WeformIUPACnamesofalkynesbychangingtheancomponentofthenameoftheparentalkanetoyn.Thus,HC
CHisnamedethyne,andCH3C CHisnamedpropyne.(TheIUPACsystemretainsthenameacetylene,sothere
aretwoacceptablenamesforethyne:ethyneandacetylene.Ofthesetwonames,acetyleneisusedmuchmore
frequently(figure16.22).)Forlargermolecules,suchasthoseshownbelow,wenumberthelongestcarbonchainthat
containsthetriplebondfromtheendthatgivesthetriplebondedcarbonatomsthelowersetofnumbers.Weindicate
thelocationofthetriplebondbythenumberofthefirstcarbonatomofthetriplebond.

FIGURE16.22Thecombustionofethyne(commonlycalledacetylene)inanoxyacetylenetorchyieldsenergythatproduces
veryhightemperatures.
WORKEDEXAMPLE16.7

NamingAlkenesandAlkynes
WritetheIUPACnameofeachofthefollowingunsaturatedhydrocarbons.
(a)CH2 CH(CH2)5CH3
(b)

(c)CH3(CH2)2C CCH3

Analysisandsolution
(a)Aswithallnomenclature,thefirsttaskistofindthelongestchaininvolvingthefunctionalgroup:in
thiscase,adoublebond.Thenamegiventohydrocarbonswithdoublebondsisalkene.Theeight
carbonatomsinthischaingivetheparentname,octene.Wethennumberthechaintogivethe
carbonatomsinvolvedinthedoublebondthesmallestnumbers:inthiscase,1and2.Hencethe
nameisoct1ene.
(b)Usethesameprocessasfor(a).Inthiscase,thefunctionalgroupisagainadoublebondandthe
longestchainisfourcarbonatoms,sotheparentnameisbutene.Thedoublebondisbetween
carbonatoms2and3,sowehavebut2ene.Thereisamethylsubstituent,alsooncarbonatom2.
Hencethenameis2methylbut2ene.
(c)Inthiscase,thefunctionalgroupisatriplebond,whichmakesthehydrocarbonanalkyne,andthe
longestchainissixcarbonatoms.Thetriplebondisbetweencarbonatoms2and3,sothenameis
hex2yne.

PRACTICEEXERCISE16.6
WritetheIUPACnameofeachofthefollowing
unsaturatedhydrocarbons.
(a)

(b)

(c)
DespitetheprecisionanduniversalacceptanceofIUPACnomenclature,somealkenesandalkynesparticularly
thoseoflowmolarmassareknownalmostexclusivelybytheircommonnames,asillustratedbelow.

DesignatingConfigurationinAlkenes
Aswesawpreviously(p.701),thephysicalpropertiesofbut2enedependontheorientationofthesubstituents(or
bondstothesubstituents)inrelationtothedoublebond.Thesedifferentorientationsrepresentdifferentmolecules
(cistransisomers).Weneedaprecisewayofdescribingthedifferentisomersthatcanarisewhenadoublebondis
presentinahydrocarbon.Therearecurrentlytwowaysofdesignatingtheorientationofgroupsattachedtocarbon
atomsinadoublebond:cistransisomersandE,Zisomers.

TheCistransSystem

Themostcommonmethodforspecifyingtheconfigurationofadisubstitutedalkeneusestheprefixescisandtrans.In
thissystem,theorientationoftheatomsoftheparentchaindetermineswhetherthealkeneiscisortrans.The
followingisthestructuralformulaforthecisisomerof4methylpent2ene.

Inthisexample,carbonatomsofthemainchain(carbons1and4)areonthesamesideofthedoublebondsothe
configurationofthisalkeneiscis.

WORKEDEXAMPLE16.8

DescribingCistransIsomersinAlkenes
Nameeachofthefollowingalkenes,and,usingthecistranssystem,specifytheconfigurationaroundeach
doublebond.
(a)

(b)

Analysisandsolution
(a)Thechaincontainssevencarbonatomsandisnumberedfromtheendthatgivesthelowernumber
tothefirstcarbonatomofthedoublebond.Thecarbonatomsoftheparentchainareonopposite
sidesofthedoublebond.Thecompound'snameistranshept3ene.
(b)Thelongestchaincontainssevencarbonatomsandisnumberedfromtheright,sothatthefirst
 carbonatomofthedoublebondisC(3)ofthechain.Thecarbonatomsoftheparentchainareon
thesamesideofthedoublebond.Thecompound'snameiscis6methylhept3ene.

PRACTICEEXERCISE16.7
Nameeachofthefollowingalkenes,and,usingthe
cistranssystem,specifyitsconfiguration.
(a)

(b)

TheE,ZSystem

Considerthetwopossiblestructuresofthemolecule1bromo2chloro1fluoroethene.

Thecistransconventionfailswhentryingtogiveadefinitivenametoeachoftheseisomers.TheE,Zsystemmustbe
usedfortriandtetrasubstitutedalkenes.Thissystemusesasetofrulestoassignprioritiestothesubstituentsoneach
carbonatomofadoublebond.Ifthegroupsofhigherpriorityareonthesamesideofthedoublebond,the
configurationofthealkeneisZ(fromtheGermanwordzusammenmeaningtogether).Ifthegroupsofhigherpriority
areonoppositesidesofthedoublebond,theconfigurationisE(fromtheGermanwordentgegenmeaningopposite).

ThemostimportantstepindetermininganEoraZconfigurationistocorrectlyassignaprioritytoeachofthegroups
bondedtoeachcarbonatom.Thepriorityrulesareshowninfigure16.23.(Thepriorityrulesareoftencalledthe
CahnIngoldPrelog(CIP)rulesafterthechemistswhodevelopedthesystem.)

1.Priorityisbasedonatomicnumber.Thehighertheatomicnumber,thehigherthepriority.Thefollowingare
severalsubstituentsarrangedinorderofincreasingpriority(theatomicnumberoftheatomdeterminingpriorityis
showninparentheses):

2.Ifprioritycannotbeassignedonthebasisoftheatomsbondeddirectlytothedoublebond,lookatthenextsetof
atoms,andcontinueuntilaprioritycanbeassigned.Priorityisassignedatthefirstpointofdifference.The
followingisaseriesofgroups,arrangedinorderofincreasingpriority(again,numbersinparenthesesgivethe
atomicnumberoftheatomonwhichtheassignmentofpriorityisbased):
 3.Wetreatatomsparticipatinginadoubleortriplebondasiftheywerebondedtoanequivalentnumberofsimilar
atomsbysinglebondsthatis,atomsofadoublebondarereplicated.Accordingly:

FIGURE16.23PriorityrulesfortheE,Zsystem.

WORKEDEXAMPLE16.9

AssigningPrioritiesintheE,ZSystem
Assignprioritiestothegroupsineachofthefollowingsets.
(a)

(b)CH2NH2andCH2OH

Analysisandsolution

(a)ThefirstpointofdifferenceistheOoftheOHinthecarboxylgroup,comparedwiththeHin
thealdehydegroup.Thecarboxylgrouphashigherpriority.

(b)Oxygenhashigherpriority(higheratomicnumber)thannitrogen.Therefore,thecarboxylgrouphas
higherprioritythantheprimaryaminogroup.

WORKEDEXAMPLE16.10

SpecifyingConfigurationsofAlkenesUsingtheE,ZSystem
NameeachofthefollowingalkenesandspecifyitsconfigurationusingtheE,Zsystem.
(a)
 (b)

Analysisandsolution
(a)ThegroupofhigherpriorityonC(2)ismethylthatofhigherpriorityonC(3)isisopropyl.Because
thegroupsofhigherpriorityareonthesamesideofthecarboncarbondoublebond,thealkenehas
theZconfiguration.Itsnameis(Z)3,4dimethylpent2ene.
(b)ThegroupsofhigherpriorityonC(2)andC(3)areClandCH2CH3.Becausethesegroupsare
onoppositesidesofthedoublebond,theconfigurationofthisalkeneisE,anditsnameis(E)2
chloropent2ene.

PRACTICEEXERCISE16.8
Nameeachofthefollowingalkenesandspecifyits
configurationusingtheE,Zsystem.
(a)

(b)

(c)

Cycloalkenes
Doublebondscanbepresentincyclichydrocarbonsandthesemoleculesarecalledcycloalkenes.Therulesfor
namingcycloalkenesfollowthesamelogicwehaveseenpreviously.Innamingcycloalkenes,wenumberthecarbon
atomsoftheringdoublebond1and2inthedirectionthatgivesthesubstituentsthesmallestpossiblenumbers.We
nameandlocatesubstituentsandlisttheminalphabeticalorder,asinthefollowingcompounds.
ChemistryResearch

HerbalRemedies:aChemicalBasis

ProfessorJamesDeVoss,UniversityofQueensland

Herbalmedicinesrepresentamultibilliondollarindustry.TheDeVossresearchgroupattheUniversityof
Queenslandisinvolvedinidentifyingandsynthesisingtheconstituentsofvariouspopularherbalmedicines
inconjunctionwithacompanycalledIntegriaHealthcare.Integria,throughitsbrandMediherb,specialises
indevelopingmedicinalproductsfromnaturalsources(figure16.24).Thechemicalmakeupofherbsand
othernaturalremediesisremarkablycomplicatedanditisimportanttoassessaccuratelythelevelsofactive
ingredients,someofwhichmayvaryfromseasontoseasonandevenfromplanttoplant.Surprisingly,
detailedchemicalprofilesformanyherbalextractsareunavailable,makingproductionofuniformquality
herbalextractsachallengeforcompaniessuchasIntegria.

FIGURE16.24MedicinalechinaceaisproducedintabletandliquidformsfromextractsofEchinaceapurpurea
andE.angustifolia.AmandaMurfitt

TheDeVossresearchgroupistacklingthisproblembysynthesisingthecomplicatedactiveingredientsof
herbalremediesusingsmallermoleculesavailableinthelaboratory.Thisprovidesaccuratestandardsagainst
whichtomeasurethequalityoftheextracts.Forinstance,theactiveingredientsinechinaceaextractsare
thoughttobemixturesofpolyunsaturatedcompoundssuchas(a)(c)(shownbelow),butdetermining
exactlywhichofthesecompoundsispresentisachallengingtask.Recently,theDeVossgrouphas
synthesisedallfouroftheE,ZisomerspossiblefortheC(8)C(9)andC(10)C(11)doublebondspresentin
compounds(a)(d),thusprovidingthepurematerialsrequiredtocomparewiththeactualisomerspresentin
speciesofEchinacea(figure16.25).ThearrangementofthegroupsaroundtheC Cbondscanhave
profoundeffectsonthephysicalandbiologicalpropertiesofthesemolecules.Thekeystepinthesynthesis
wasthecontrolledintroductionofthedoublebonds,i.e.eitherEorZ.Forinstance,theZdoublebondsof
compound(a)wereintroducedbyreductionofacompoundthathadalkynesatthecarbonatoms
correspondingtotheZalkenesinthefinalproduct.AlthoughthegroupexploredtheuseofLindlarcatalysts
(p.722),theyfinallyusedadifferentreagenttoreducethesensitivediynesystememployed.
(a)

(b)
 (c)

(d)

FIGURE16.25FlowersofEchinaceapurpurea.Currently,thespeciesmostcommonlyusedformedicinal
purposesareE.purpurea,E.angustifoliaandE.pallida.

Withallfourisomersshownabovesynthesisedandcharacterised,theDeVossgroupwasableto
demonstratethat(a)and(b)arethemajorproductspresentinextractsofspeciesofEchinacea,butthattheir
levelsvariedconsiderably.TheyshowedforthefirsttimethattheE,Zisomer(c)isalsopresentinechinacea
extracts.ThisspecificisomerhadbeenreportedinanAfricanplant,Spilanthesmauritiana,andwasthought
tohavepotentialasanaturalagenttocontrolmosquitolarvae.However,theworkoftheDeVossgroup
showedthattheoriginalreportwaswrongandthattheisolatedcompoundwasactuallyisomer(a).

Onepostulatetoexplainthebiologicalactionofechinaceaextractsisthattheyinteractwithproteinsinthe
bodycalledcannabinoidtype2(CB2)receptors.Thesearebelievedtoplayaroleinmanyprocesses
includingthoseofthecellularimmunesystem.TheDeVossgroupsubsequentlyinvestigatedhowwelleach
ofthefourisomers(a)(d)bindstoCB2receptors.Itwasdeterminedthat,while(a)bindstightly,theaffinity
of(d)isapproximately1500timeslower,withisomers(b)and(c)havingintermediateaffinity.The
arrangementofthegroupsaroundacarboncarbondoublebondisimportantindeterminingboththe
reactivityandtheshapeofsuchmolecules.Itisthislatterpropertythatinfluenceshowthesemolecules
interactwithbiologicalreceptorsandthusgovernstheirbiologicalactivity.

Althoughthesynthesisofsuchcompoundsisadifficulttask,itisonlywhenthefullycharacterised
compoundsareinhandthatresearcherssuchasthoseintheDeVossgroupcantrulyunderstandthenature
oftheactionofherbalremedies.
WORKEDEXAMPLE16.11

NamingCycloalkenes
WritetheIUPACnamesforthefollowingcycloalkenes.
(a)

(b)

(c)

Analysis

Wenumberthecarbonatomsofthedoublebond1and2inthedirectionthatgivesthesubstituentsthe
smallestpossiblenumbers.Wenameandlocatesubstituentsandlisttheminalphabeticalorder.

Solution
(a)3,3dimethylcyclohexene
(b)1,2dimethylcyclopentene
(c)4isopropyl1methylcyclohexene

PRACTICEEXERCISE16.9
WritetheIUPACnamesforthefollowing
cycloalkenes.
(a)

(b)

(c)
CistransIsomerisminCycloalkenes

Thefollowingarestructuralformulaeforfourcycloalkenes.

Intheserepresentations,theconfigurationaroundeachdoublebondiscis.Becauseofanglestrain,itisnotpossibleto
haveatransconfigurationincycloalkenesofsevenorfewercarbonatoms.Todate,transcyclooctene(shownbelow)
isthesmallesttranscycloalkenethathasbeenpreparedinpureformandthatisstableatroomtemperature.Yet,even
inthistranscycloalkene,thereisconsiderableintramolecularstrain.Theisomerciscycloocteneismorestablethanits
transisomerby38kJmol1.

Dienes,Trienes,andPolyenes

Wenamealkenesthatcontainmorethanonedoublebondasalkadienes(twodoublebonds),alkatrienes(threedouble
bonds)andsoon.Werefertothosethatcontainseveraldoublebondsmoregenerallyaspolyenes(fromtheGreek
wordpolymeaningmany).Threeexamplesofdienesareshownonthenextpage.

Thusfar,wehaveconsideredcistransisomerisminalkenescontainingonlyonecarboncarbondoublebond.Foran
alkenewithonecarboncarbondoublebondthatcanshowcistransisomerism,therearetwoisomers:onecisand
onetrans.Foranalkenewithncarboncarbondoublebonds,eachofwhichcanshowcistransisomerism,a
maximumof2 ncistransisomersarepossible.

WORKEDEXAMPLE16.12

CistransIsomerisminPolyenes
 (a)Howmanycistransisomersarepossibleforhepta2,4diene?
(b)NametheseisomersusingtheE,Znomenclature.

Analysisandsolution

(a)Thismoleculehastwocarboncarbondoublebonds,eachofwhichexhibitscistransisomerism.
Asthefollowingtableshows,2 2=4cistransisomersarepossible(totherightofthetableareline
structuresfortwooftheseisomers).

Doublebond
C2 C3 C4 C5
trans trans
trans cis
cis trans
cis cis

(b)AlloftheseisomersaredisubstitutedalkenesandthereforeciscanbereplacedwithZandtranscan
bereplacedwithE.So,forinstance,thenamesofthetwoisomersshownbecome(E,E)hepta2,4
dieneand(E,Z)hepta2,4diene,respectively.

PRACTICEEXERCISE16.10
Drawstructuralformulaeforthetwocistrans
isomersofhepta2,4dienenotshowninworked
example16.12.

WORKEDEXAMPLE16.13

DrawingCistransIsomersofPolyenes
Drawallpossiblecistransisomersforthefollowingunsaturatedalcohol.

Analysisandsolution

ItispossibletohavecistransisomerismonlyaroundthedoublebondbetweenC(2)andC(3)ofthechain.
Itisnotpossiblefortheotherdoublebond,becauseC(7)hastwoidenticalgroupsonit.Thus,2 1=2
cistransisomersarepossible.Thetransisomerofthisalcohol,namedgeraniol,isamajorcomponentof
theoilsofrose,citronellaandlemongrass(figure16.26).
 FIGURE16.26Geraniolisamajorcomponentoftheoilsofcitronella,roseandlemongrass.KariAnnTapp

PRACTICEEXERCISE16.11
Howmanycistransisomersarepossibleforthefollowing
unsaturatedalcohol?

VitaminAisanexampleofabiologicallyimportantcompoundforwhichanumberofcistransisomersarepossible.
Therearefourcarboncarbondoublebonds(highlightedinblue)inthechainofcarbonatomsbondedtothe
substitutedcyclohexenering,andeachhasthepotentialforcistransisomerism.Thus,2 4=16cistransisomersare
possibleforamoleculewiththisstructuralformula.VitaminAisthealltransisomer.Theenzymecatalysedoxidation
ofvitaminAconvertstheprimaryhydroxylgroup(highlightedinred)toanaldehydegroup(red)togiveretinal,the
biologicallyactiveformofthevitamin.

PhysicalPropertiesofAlkenesandAlkynes
Alkenesandalkynesarenonpolarcompounds,andtheonlyattractiveforcesbetweentheirmoleculesaredispersion
forces.Therefore,theirphysicalpropertiesaresimilartothoseofalkaneswiththesamecarbonskeletons.Alkenesand
alkynesthatareliquidatroomtemperaturehavedensitieslessthan1.0gmL1,sotheyarelessdensethanwater.Like
alkanes,alkenesandalkynesaresolubleineachother.Becauseoftheircontrastingpolaritywithwater,theydonot
dissolve.Instead,theyformaseparatelayerwhenmixedwithwateroranotherpolarorganicliquidsuchasmethanol.

WORKEDEXAMPLE16.14

PhysicalPropertiesofAlkenesandAlkynes
Describewhathappenswhennon1eneismixedeachofwiththefollowingcompounds.
(a)water
(b)8methylnon1yne

Analysisandsolution
(a)Becausenon1eneisanalkene,itisnonpolar.Itwillnotdissolveinapolarsolventsuchaswater.
Waterandnon1enewillformtwolayerswaterhasthehigherdensityandsowillbethelower
layer,andnon1enewillbetheupperlayer.
(b)Becausealkenesandalkynesarebothnonpolar,theywilldissolveinoneanother.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.4ReactionsofAlkanes
Forcompleteness,weshouldstartwiththereactionsofalkanes,yetalkanesactuallyhaveverylittle
reactivity.Itisforthisreasonthatchemistsdescribealkanesasunfunctionalised.Theyarequite
unreactivewithmostreagents,abehaviourconsistentwiththefactthattheyarenonpolarcompounds
containingonlystrongbonds.

Undercertainconditions,however,alkanesandcycloalkanesreactwithoxygen,O2.Byfartheirmost
importantreactionwithoxygenisoxidation(combustion)toformcarbondioxideandwater.The
oxidationofsaturatedhydrocarbonsisthebasisfortheiruseasenergysourcesforheat(naturalgas,
liquefiedpetroleumgas(LPG)andfueloil)andpower(petrol,dieselfuelandaviationfuel).The
followingarebalancedequationsforthecompletecombustionofmethane,themajorcomponentof
naturalgas,andforpropane,themajorcomponentofLPG.

Anotherreactionofalkanesinvolvesasubstitutionreactionwherehalogensreplacehydrogenatoms,
andthiswillbediscussedinchapter18.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.5ReactionsofAlkenes
Themostcharacteristicreactionofalkenesisadditiontothecarboncarbondoublebondsothatthebondisbrokenand,inits
place,bondsareformedtotwonewatomsorgroupsofatoms.Severalexamplesofreactionsatthecarboncarbondoublebond
areshownintable16.4,alongwiththedescriptivename(s)associatedwitheach.
TABLE16.4 Characteristicadditionreactionsofalkenes.

Fromtheperspectiveofthechemicalindustry,themostimportantreactionoflowmolarmassalkenesistheproductionofpolymers
(e.g.polyethyleneandpolystyrene).Polymersarisefromthesequentialadditionofmanylowmolarmassmoleculestocreatevery
largemoleculesofhighmolarmass,asillustratedherebytheformationofpolyethylenefromethene(ethylene):

Toachievesuchanaddition,alkenesfirstreactwithaspecificreagentcalledaninitiatorandthenwitheachothertoformasteadily
growingchain.Inalkenederivedpolymersofindustrialandcommercialimportance,nisalargenumber,typicallyseveral
thousand.Wediscusstheformationofpolymersfromalkenesinmoredetailinchapter26.

Anotherreactionofalkenesisreductiontoalkanes,whichisessentiallytheadditionofH2acrossthedoublebond.Wewilldiscuss
thisafterwelookattheadditionreactions.

ElectrophilicAdditionReactions
Thebasisofreactivityistheattractionbetweenpositiveandnegativespecies.Thedoublebondinalkenesisanelectronrich(i.e.
negative)targetforpositivespecies.Thesepositivespeciesarecalledelectrophiles(whichliterallymeansattractedtoelectrons).
Alkenesundergoadditionreactionswithelectrophilestoproducesaturatedcompounds.

Inthissectionweexaminethethreemostimportanttypesofelectrophilicadditionreactions:theadditionofhydrogenhalides(HCl,
HBr,andHI),water(H2O)andhalogens(Br2,Cl2).Wefirststudysomeoftheexperimentalobservationsabouteachaddition
reactionandthenitsmechanism.Byexaminingtheseparticularreactions,wedevelopageneralunderstandingofhowalkenes
undergoadditionreactions.

AdditionofHydrogenHalides
ThehydrogenhalidesHCl,HBrandHI(commonlyabbreviatedHX)addtoalkenestogivehaloalkanes(alkylhalides).These
additionsmaybecarriedouteitherwiththepurereagentsorinthepresenceofapolarsolventsuchasaceticacid.Theadditionof
HCltoethenegiveschloroethane:
TheadditionofHCltopropenegives2chloropropanehydrogenaddstoC(1)ofpropene,andchlorineaddstoC(2).Ifthe
orientationofadditionwerereversed,1chloropropanewouldbeformed.

Theobservedresultisthat2chloropropaneisformedtothevirtualexclusionof1chloropropane:

WesaythattheadditionofHCltopropeneishighlyregioselectiveandthat2chloropropaneisthemajor(indeedalmostexclusive)
productofthereaction.Aregioselectivereactionisoneinwhichonedirectionofbondformingorbreakingoccursinpreferenceto
allotherdirections.

NineteenthcenturyRussianchemistVladimirMarkovnikovobservedthisregioselectivityandmadethegeneralisation,knownas
Markovnikov'srule,that,intheadditionofHXtoanalkene,hydrogenaddstothedoublebondedcarbonatomwiththegreater
numberofhydrogenatomsalreadybondedtoit.

WORKEDEXAMPLE16.15

AlkeneAdditionReactions
Nameanddrawastructuralformulaforthemajorproductofeachofthefollowingalkeneadditionreactions.
(a)

(b)

Analysisandsolution

UsingMarkovnikov'srule,wepredictthat2iodo2methylpropaneistheproductin(a)and1chloro1
methylcyclopentaneistheproductin(b).
(a)

(b)

PRACTICEEXERCISE16.12
Nameanddrawthestructuralformulaofthemajor
productofeachofthefollowingalkeneadditionreactions.
(a)CH3CH CH2+HI
(b)
AlthoughMarkovnikov'sruleprovidesawaytopredicttheproductofmanyalkeneadditionreactions,itdoesnotexplainwhyone
productpredominatesoverotherpossibleproducts.Todothis,weneedtounderstandthemechanismoftheprocess.Aswesawin
chapter15,mechanismsprovideacompletedescriptionofthebondbreakingandbondformingprocessesthatoccurinthe
transformationofstartingmaterialstointermediatespeciesand,then,toproducts.Werepresentthemovementofthetwoelectrons
involvedinthesebondbreakingandbondformingstepswithacurvedarrow.Forexample,wecanrepresentthebreakingofthe
singlebondinthehypotheticalABmoleculebyusingcurvedarrows:

Notethatthearrowbeginsatthebondthatisbeingbrokenandtheheadofthearrowshowsthedestinationofthepairofelectrons.
Weusearrowstoshowthemovementofelectronsineachbondformingandbondbreakingstepinamechanism.Oncewehavea
completemechanisticdescriptionforaparticularreaction,itispossibletomakegeneralisationsandthenpredicthowothersimilar
reactionsmightoccur.

ChemistsaccountfortheadditionofHXtoanalkenebyatwostepmechanism,whichweillustratebythereactionofbut2ene
withhydrogenchloridetogive2chlorobutane.Letusfirstlookatthistwostepmechanismingeneralandthengobackandstudy
eachstepindetail.
Step1:ThereactionbeginswiththetransferofaprotonfromHCltobut2ene,asshownbythetwocurvedarrowsontheleft
sideofthefollowingequation:

Thefirstcurvedarrowshowsthebreakingofthebondofthealkeneanditselectronpairnowforminganewcovalentbond
withthehydrogenatomofHCl.ThesecondcurvedarrowshowsthebreakingofthepolarcovalentbondinHClandthis
electronpairbeinggivenentirelytochlorine,formingachlorideion.Step1inthismechanismresultsintheformationofan
organiccationandachlorideion.Itisimportanttorememberthat,eventhoughwedescribedthisprocessasaprotontransfer,a
mechanisticarrowalwaysshowsthemovementofelectrons,notprotons.Amechanisticarrowshouldneverstartfroma
hydrogenatominanorganicmolecule.
Step2:Thereactionofthecation(aLewisacid)withachlorideion(aLewisbase)completesthevalenceshellofcarbonand
gives2chlorobutane:

Nowletuslookattheindividualstepsinmoredetail.Thereisagreatdealofimportantorganicchemistryembeddedinthesetwo
steps,anditiscrucialthatyouunderstanditnow.

Step1resultsintheformationofanorganiccation.Onecarbonatominthiscationhasonlysixelectronsinitsvalenceshelland
carriesachargeof+1.Aspeciescontainingapositivelychargedcarbonatomiscalledacarbocation(carbon+cation).
Carbocationsareclassifiedasprimary(1),secondary(2)ortertiary(3),dependingonthenumberofcarbonatomsbondedtothe
carbonatombearingthepositivecharge.Thecationinthereactiongivenaboveisa2carbocation.AllcarbocationsareLewis
acids(chapter11).Theyarealsoelectrophiles.

Inacarbocation,thecarbonatombearingthepositivechargeisbondedtothreeotheratoms,and,aspredictedbythevalenceshell
electronpairrepulsion(VSEPR)model,thethreebondsaroundthatcarbonatomarecoplanarandformbondanglesof
approximately120.Accordingtothevalencebondtheory,theelectrondeficientcarbonatomofacarbocationusesitssp 2hybrid
orbitalstoformbondstothethreeattachedgroups.Theunhybridised2porbitalliesperpendiculartothebondframeworkand
containsnoelectrons.ALewisstructureandanorbitaloverlapdiagramforacommontertiarycarbocation(C4H9+)areshownin
figure16.27.Thiscarbocationisgiventhecommonnametertiarybutylcationortertbutylcation.
 FIGURE16.27 Representationsofthestructureofatertiary(3)carbocation:
(a)Lewisstructureand
(b)anorbitalpicture.

Recallfromchapter15thattheprocessofareactioncanalsobedepictedbytheenergychangesfromstartingmaterialto
intermediatespeciesthroughtoproducts.Figure16.28showssuchanenergydiagramforthetwostepreactionofbut2enewith
HCl.Theslower,ratedeterminingstep(thathastopassoverthehigherenergybarrier)isstep1(i.e.Ea1isgreaterthanEa2),which
leadstotheformationofthe2carbocationintermediate.Thisintermediateliesinanenergyminimumbetweenthetransitionstates
forsteps1and2.Assoonasthecarbocationintermediate(aLewisacid)forms,itreactswithachlorideion(aLewisbase)ina
Lewisacidbasereactiontogive2chlorobutane.Notethattheenergyof2chlorobutane(theproduct)islessthantheenergyofbut
2eneandHCl(thereactants).Thus,inthisalkeneadditionreaction,heatisreleasedsothereactionisexothermic.

FIGURE16.28EnergydiagramforthetwostepadditionofHCltobut2ene.Thereactionisexothermic.

Giventhattheratedeterminingstepofthereactioninfigure16.28involvesbothbut2eneandHClasreactants,wewouldexpect
theratelawforthisreactiontohavetheform:

andthereactionshoulddisplaysecondorderkinetics(seechapter15).

RelativeStabilitiesofCarbocations:RegioselectivityandMarkovnikov'sRule

ThereactionofHXwithanasymmetricalalkenecan,atleastinprinciple,givetwodifferentcarbocationintermediates,depending
onwhichofthedoublebondedcarbonatomshasH+addedtoit,asillustratedbythereactionofHClwithpropene.

Themajorproductformedis2chloropropane,and1chloropropaneisformedinonlytraceamounts.Becausecarbocationsreact
veryquicklywithchlorideions,thevirtualabsenceof1chloropropaneasaproducttellsusthatthe2carbocationisformedin
preferencetothe1carbocation.
Similarly,inthereactionofHClwith2methylpropene,thetransferofaprotontothecarboncarbondoublebondmightform
eithera1carbocation(isobutylcation)ora3carbocation(tertbutylcation).

Inthisreaction,theobservedproductis2chloro2methylpropane,indicatingthatthe3carbocationformsinpreferencetothe1
carbocation.

Fromsuchexperimentsandagreatamountofotherexperimentalevidence,welearnthata3carbocationismorestableandhasa
loweractivationenergyforitsformationthana2carbocation.A2carbocation,inturn,ismorestableandhasaloweractivation
energyforitsformationthana1carbocation.Itfollowsthatamorestablecarbocationintermediateformsmorerapidlythanaless
stablecarbocationintermediate.Figure16.29showstheorderofstabilityoffourtypesofalkylcarbocations.

FIGURE16.29Theorderofstabilityoffourtypesofalkylcarbocations.

AlthoughtheconceptoftherelativestabilitiesofcarbocationshadnotbeendevelopedinMarkovnikov'stime,itistheunderlying
basisforhisrulethatis,theprotonofHXaddstothelesssubstitutedcarbonatomofadoublebond,becausethismodeof
additionproducesthemorestablecarbocationintermediate.

Nowthatweknowtheorderofstabilityofcarbocations,howdoweaccountforit?Theprinciplesofphysicsteachusthatasystem
bearingacharge(eitherpositiveornegative)ismorestableifthechargeisdistributedoverthesystemratherthanlocalisedata
particularpointwithinthesystem.Ifweassumethatalkylgroupsbondedtoapositivelychargedcarbonatomreleaseelectrons
towardsthecationiccarbonatom,therebydistributingthechargeofthecationoverthestructure,thisexplainstheorderofstability
ofcarbocations.Theelectronreleasingabilityofalkylgroupsbondedtoacationiccarbonatomisaccountedforbytheinductive
effect.

Theinductiveeffectoperatesinthefollowingway:theelectrondeficiencyofthecarbonatombearingapositivechargeexertsan
electronwithdrawinginductiveeffectthatpolariseselectronsfromadjacentbondstowardsit.Thus,thepositivechargeofthe
cationisnotlocalisedonthetrivalentcarbonatom,butratherispartiallydistributedovernearbyatoms.Asthenumberofalkyl
groupsbondedtothecationiccarbonatomincreases,thepositivechargecanbedistributedovermoreatomsandthestabilityofthe
cationincreases.

Theinductiveeffectisnottheonlyfactorthatinfluencesthestabilityofcarbocations.Infuturestudiesinchemistry,youmaylearn
abouttheprincipleofhyperconjugation,whichalsoaffectscarbocationstability.Hyperconjugationinvolvesthatinteractionof
adjacentporbitalsofalkylgroups,helpingtostabilisethecarbocation.Again,aswiththeinductiveeffect,themorealkylgroups
boundtothecarbocation,thegreaterisitsstability.

WORKEDEXAMPLE16.16

RelativeStabilitiesofCarbocations
Arrangethefollowingcarbocationsinorderofincreasingstability.
(a)

(b)

(c)

Solution

Carbocation(a)issecondary,(b)istertiaryand(c)isprimary.Inorderofincreasingstability,theyare(c),(a)and(b).

PRACTICEEXERCISE16.13
Arrangethefollowingcarbocationsinorderofincreasing
stability.
(a)

(b)

(c)

WORKEDEXAMPLE16.17

TheMechanismofAddition
ProposeamechanismfortheadditionofHItomethylenecyclohexane,whichgives1iodo1methylcyclohexane.
 Whichstepinyourmechanismisratedetermining?

Analysisandsolution

ProposeatwostepmechanismsimilartothatproposedfortheadditionofHCltopropene.
Step1:AratedeterminingprotontransferfromHItothecarboncarbondoublebondgivesa3carbocation
intermediate.

Step2:Reactionofthe3carbocationintermediate(aLewisacid)withaniodideion(aLewisbase)completesthe
valenceshellofcarbonandgivestheproduct.

PRACTICEEXERCISE16.14
ProposeamechanismfortheadditionofHIto1
methylcyclohexene,whichgives1iodo1
methylcyclohexane.Whichstepinyourmechanismisrate
determining?

AdditionofWater:AcidcatalysedHydration
Inthepresenceofanacidcatalystmostcommonly,sulfuricacidwateraddstothecarboncarbondoublebondofanalkene
togiveanalcohol.Theadditionofwateriscalledhydration.Theprecisemechanismofthishydrationisgivenbelowbut,ineffect,
forsimplealkenes,Hisaddedtothecarbonatomofthedoublebondwiththegreaternumberofhydrogenatoms,andOHisadded
tothecarbonatomwiththelowernumberofhydrogenatoms.Thus,HOHaddstoalkenesinaccordancewithMarkovnikov's
rule:
 WORKEDEXAMPLE16.18

AcidcatalysedHydration
Drawthestructuralformulaoftheproductoftheacidcatalysedhydrationof1methylcyclohexene.

Analysis

Weknowthatahydrogenatomfromwaterwilladdtothecarbonatomofthedoublebondbearingmoreattached
hydrogenatoms.ThisthenmeansthattheOHwilladdtothecarbonatombearingthemethylgroup.Wecantherefore
writethestructuralformulaoftheproduct.

Solution

PRACTICEEXERCISE16.15
Drawstructuralformulaeoftheproductsofthefollowing
alkenehydrationreactions.
(a)

(b)

ThemechanismoftheacidcatalysedhydrationofalkenesissimilartothemechanismwehavedescribedfortheadditionofHCl,
HBrandHItoalkenesandisillustratedbythehydrationofpropenetopropan2ol.Thismechanismisconsistentwiththefactthat
acidisacatalyst.ForeveryH3O+consumedinstep1,anotherisgeneratedinstep3.
Step1:Protontransferfromtheacidcatalysttopropenegivesa2carbocationintermediate(aLewisacid):

Step2:Reactionofthecarbocationintermediate(aLewisacid)withwater(aLewisbase)completesthevalenceshellofcarbon
andgivesanoxoniumion:

Step3:Protontransferfromtheoxoniumiontowatergivesthealcoholandgeneratesanewmoleculeofthecatalyst:
 WORKEDEXAMPLE16.19

TheMechanismofAcidcatalysedHydration
Proposeamechanismfortheacidcatalysedhydrationofmethylenecyclohexanetogive1methylcyclohexanol.Which
stepinyourmechanismisratedetermining?

Solution

Themechanisminvolvesthreesteps,similartothosefortheacidcatalysedhydrationofpropene.Theformationofthe3
carbocationintermediateinstep1isratedetermining.
Step1:Protontransferfromtheacidcatalysttothealkenegivesa3carbocationintermediate(aLewisacid):

Step2:Reactionofthecarbocationintermediate(aLewisacid)withwater(aLewisbase)completesthevalenceshell
ofcarbonandgivesanoxoniumion:

Step3:Protontransferfromtheoxoniumiontowatergivesthealcoholandgeneratesanewmoleculeofthe
catalyst:

PRACTICEEXERCISE16.16
Proposeamechanismfortheacidcatalysedhydrationof
1methylcyclohexenetogive1methylcyclohexanol.
Whichstepinyourmechanismisratedetermining?

AdditionofBromineandChlorine
Chlorine,Cl2,andbromine,Br2,reactwithalkenesatroomtemperaturebytheadditionofhalogenatomstothetwocarbonatoms
ofthedoublebond,formingtwonewcarbonhalogenbonds:

Fluorine,F2,alsoaddstoalkenes,but,becauseitsreactionsareveryfastanddifficulttocontrol,additionoffluorineisnotauseful
laboratoryreaction.Iodine,I2,alsoaddstoalkenes,buttheproductsofthereactioncaninsomecasesbeunstableandsubsequently
degrade,generatingotherproducts.

Theadditionofbromineandchlorinetoacycloalkenegivesatransdihalocycloalkane.Forexample,theadditionofbromineto
cyclohexenegivestrans1,2dibromocyclohexanethecisisomerisnotformed.Thus,theadditionofahalogentoacycloalkeneis
stereospecific.Astereospecificreactionisareactioninwhichonestereoisomerisformedordestroyedinpreferencetoallothers
thatmightbeformedordestroyed.Additionofbrominetoacycloalkeneishighlystereospecificthehalogenatomsalwaysadd
transtoeachother.

Thereactionofbrominewithanalkeneisaparticularlyusefulqualitativetestforthepresenceofacarboncarbondoublebond.If
wedissolvebromineindichloromethane,CH2Cl2,thesolutionbecomesredduetothepresenceoftheredcolouredbromine(figure
16.30).Bothalkenesanddibromoalkanesarecolourless.Ifwenowmixafewdropsofthebrominesolutionwithanalkene,the
bromineisconsumed,adibromoalkaneisformedand,withtheremovalofthebromine,thesolutionbecomescolourless.

FIGURE16.30Asolutionofbromineindichloromethane,CH2 Cl2 ,isred(left).Addafewdropsofanalkeneandtheredcolourdisappears

(right).CharlesDWinters

WORKEDEXAMPLE16.20

AdditionofBromineandChlorine
Completethefollowingreactions,showingtherelativeorientationsofthesubstituentsintheproducts.
(a)

(b)
 Solution

Thehalogenatomsaretranstoeachotherineachproduct.
(a)

(b)

PRACTICEEXERCISE16.17
Completethefollowingreactions.
(a)

(b)

BridgedHaloniumIonIntermediatesandAntiSelectivity

Weexplaintheadditionofbromineandchlorinetocycloalkenes,aswellastheirselectivity(theyalwaysaddtranstoeachother),
byatwostepmechanismthatinvolvesahalogenbearingapositivecharge,calledahaloniumion.Thecyclicstructureofwhich
thisionisapartiscalledabridgedhaloniumion.Thebridgedbromoniumionshowninstep1ofthemechanismbelowmaylook
oddtoyou,butitisanacceptableLewisstructure.Acalculationofformalchargeplacesapositivechargeonbromine.Then,instep
2,abromideionreactswiththebridgedintermediatefromthesideoppositethatoccupiedbythebromineatom,givingthe
dibromoalkane.Thus,bromineatomsaddfromoppositefacesofthecarboncarbondoublebond.Wesaythatthisadditionoccurs
withantiselectivity.Alternatively,wesaythattheadditionofhalogensisstereospecificinvolvingantiadditionofthehalogen
atoms.
Step1:Reactionoftheelectronsofthecarboncarbondoublebondwithbromineformsabridgedbromoniumion
intermediateinwhichbrominebearsapositiveformalcharge:

Step2:Abromideion(aLewisbase)attacksacarbonatomofthethreememberedring(aLewisacid)fromthesideopposite
thebridgedbromoniumion,openingthethreememberedring:
AswecanseefromtheNewmanprojectionabove,thesebromineatomsaretranstoeachotherbut,inopenchainalkanes,this
relativepositionisrapidlyscrambledbynormalbondrotationaroundthecarboncarbonbonds.Ontheotherhand,suchrotationis
notpossibleinacycloalkenesothebromineatomsremainonoppositesidesofthering.

ReductionofAlkenes:FormationofAlkanes
Mostalkenesreactquantitativelywithmolecularhydrogen,H2,inthepresenceofatransitionmetalcatalysttogivealkanes.
Commonlyusedtransitionmetalcatalystsincludeplatinum,palladium,rutheniumandnickel.Yieldsareusuallyquantitativeor
nearlyso.Becausetheconversionofanalkenetoanalkaneinvolvesreductionbyhydrogeninthepresenceofacatalyst,the
processiscalledcatalyticreductionorcatalytichydrogenation.

Themetalcatalystisusedasafinelypowderedsolid,whichmaybesupportedonsomeinertmaterialsuchaspowderedcharcoalor
alumina.Thereactioniscarriedoutbydissolvingthealkeneinethanoloranothernonreactingorganicsolvent,addingthesolid
catalyst,andexposingthemixturetohydrogengasatpressuresrangingfrom110 5to10010 5Pa(i.e.upto100timesnormal
atmosphericpressure).Alternatively,themetalmaybeboundtocertainorganicmoleculesandusedintheformofasoluble
complex.

Catalyticreductionisstereospecific,themostcommonpatternbeingthesynadditionofhydrogenatomstothecarboncarbon
doublebond(meaningthehydrogenatomsareaddedtothesamesideofthecarboncarbondoublebond).Thecatalyticreduction
of1,2dimethylcyclohexene,forexample,yieldscis1,2dimethylcyclohexane:

Thetransitionmetalsusedincatalyticreductioncanadsorblargequantitiesofhydrogenontotheirsurfaces,probablybyforming
metalhydrogenbonds.Similarly,thesetransitionmetalsadsorbalkenesontheirsurfaces,formingcarbonmetalbonds(figure
16.31).Hydrogenatomsareaddedtothealkeneinmorethanonestep.

FIGURE16.31 synadditionofhydrogentoanalkeneinvolvingatransitionmetalcatalyst.
 (a)Hydrogenandthealkeneareadsorbedonthemetalsurface,and
(b)onehydrogenatomistransferredtothealkene,forminganewCHbond.Theothercarbonatomremainsadsorbedon
themetalsurface.
(c)AsecondCHbondformsandthealkaneisdesorbed.

EnthalpiesofHydrogenationandtheRelativeStabilitiesofAlkenes

Theenthalpyofhydrogenationofanalkeneisdefinedasitsenthalpyofreaction, ,withhydrogentoformanalkane.Table
16.5liststheenthalpiesofhydrogenationofseveralalkenes.
TABLE16.5 Enthalpiesofhydrogenationofseveralalkenes.

Name Structuralformula
ethene CH2 CH2 137

propene CH3CH CH2 126

but1ene CH3CH2CH CH2 127

cisbut2ene 120

transbut2ene 116

2methylbut2ene 113

2,3dimethylbut2ene 111

Threeimportantpointsfollowfromtheinformationintable16.5.
1.Thereductionofanalkenetoanalkaneisanexothermicprocess.Thisobservationisconsistentwiththefactthat,during
hydrogenation,thereisnetconversionfromweakerbondingtostrongerbondingthatis,onebond(HH)andone
bond(C C)arebroken,andtwonewbonds(CH)areformed.
2.Theenthalpiesofhydrogenationdependonthedegreeofsubstitutionofthecarboncarbondoublebond:thegreaterthe
substitution,thelowertheenthalpyofhydrogenation.Compare,forexample,theenthalpiesofhydrogenationofethene(no
substituents),propene(onesubstituent),but1ene(onesubstituent)andthecisandtransisomersofbut2ene(two
substituentseach).
3.Theenthalpyofhydrogenationofatransalkeneislessthanthatoftheisomericcisalkene.Compare,forexample,the
enthalpiesofhydrogenationofcisbut2eneandtransbut2ene.Becausethereductionofbothalkenesgivesbutane,any
differenceintheirenthalpiesofhydrogenationmustbeduetoadifferenceinrelativeenergybetweenthetwoalkenes(figure
16.32).Thealkenewiththelower(lessnegative)valueof isthemorestablealkene.Weexplainthegreaterstabilityof
transalkenesrelativetocisalkenesintermsofnonbondedinteractionstrain.Incisbut2ene,thetwoCH3groupsare
sufficientlyclosetoeachotherthatthereisrepulsionbetweentheirelectronclouds.Thisrepulsionisreflectedinthelarger
enthalpyofhydrogenation(decreasedstability)ofcisbut2enecomparedwiththatoftransbut2ene.
 FIGURE16.32Enthalpiesofhydrogenationofcisbut2eneandtransbut2enetransbut2eneismorestablethancisbut2eneby
4kJmol1 .

Wehavelookedatmoleculeswithonedoublebond.Moleculeswithmorethanonecarboncarbondoublebondundergothesame
additionreactions.However,thereisaclassofunsaturatedmoleculesthatdonotundergoanyoftheseadditionreactions.These
moleculesarecalledaromaticcompoundsandarecoveredinsection16.7.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.6ReactionsofAlkynes
Muchofthechemistryofalkynesmirrorsthechemistryofalkenestheyundergothesamereduction
reactions,aswellashydrogenhalideadditionandhalogenadditionreactions.Alkynesalsoundergo
hydration,butunlikealkenesthesyntheticoutcomeisaketoneandthisiscoveredinchapter21.

Reductionofalkynesisparticularlyimportantinthesynthesisofcomplicatedmoleculesusedinmaking
pharmaceuticals.Alkynesareeasilyreducedtoalkanesbyadditionofhydrogengasusingametal
catalyst.Thesignificantdifferencesfromthereductionofalkenesarethatthisreductionoccursinstages
andthechoiceofcatalystcancontrolthesyntheticoutcome.Completereductionofthealkyneoccurs
whenpalladiumcoatedontocarbonisusedasthecatalyst.Anothercatalystinvolvingdeactivated
palladium,calledLindlarcatalyst,producesthecisalkenefromthetriplebond.Thetransalkenecanbe
generatedusingsodiumorlithiumdissolvedinliquidammonia.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.7AromaticCompounds
Thesimplestexampleofanaromaticcompoundisbenzene,C6H6.Benzene,acolourlessliquid,wasfirst
isolatedbyMichaelFaradayin1825fromtheoilyresiduethatcollectedinthegaspipesofLondon.
Benzene'smolecularformula,C6H6,suggestsahighdegreeofunsaturation.Remember,CnH2n+2isthe
formulaforalkanes,soanalkanewithsixcarbonatomshasamolecularformulaofC6H14anda
cycloalkanewithsixcarbonatomshasamolecularformulaofC6H12.Consideringbenzene'shighdegree
ofunsaturation,itmightbeexpectedtoshowmanyofthereactionscharacteristicofalkenes.Yet,benzene
isremarkablyunreactive!Itdoesnotundergotheaddition,oxidationandreductionreactionscharacteristic
ofalkenes.Forexample,benzenedoesnotundergoadditionreactionswithbromine,hydrogenchlorideor
otherreagentsthatusuallyaddtocarboncarbondoublebonds.Whenbenzenereacts,itdoessoby
substitution(seechapter18)inwhichahydrogenatomisreplacedbyanotheratomoragroupofatoms.

Thetermaromaticwasoriginallyusedtoclassifybenzeneanditsderivativesbecausemanyofthemhave
distinctiveodours.Itbecameclear,however,thatabetterclassificationforthesecompoundswouldbeone
basedonstructureandchemicalreactivity,ratherthanaroma.Asitisnowused,thetermaromaticrefers
insteadtothefactthatbenzeneanditsderivativesarehighlyunsaturatedcompoundsthatarestabletowards
reagentsthatreactwithalkenes.

Weusethetermarenetodescribearomatichydrocarbons,byanalogywithalkaneandalkene.Benzeneis
theparentarene.JustaswecallagroupderivedbytheremovalofanHfromanalkaneanalkylgroupand
giveitthesymbolR(chapter2),wecallagroupderivedbytheremovalofanHfromanareneanaryl
groupandgiveitthesymbolAr.

TheStructureofBenzene
Letusimagineourselvesinthemidnineteenthcenturyandexaminetheevidenceonwhichchemists
attemptedtobuildamodelforthestructureofbenzene.First,becausethemolecularformulaofbenzeneis
C6H6,itseemedclearthatthemoleculemustbehighlyunsaturated.Yetbenzenedoesnotshowthe
chemicalpropertiesofalkenes,theonlyunsaturatedhydrocarbonsknownatthattime.Benzenedoes
undergochemicalreactions,butitscharacteristicreactionissubstitutionratherthanaddition.Whenbenzene
istreatedwithbromineinthepresenceofiron(III)chlorideasacatalyst,forexample,onlyonecompound,
withmolecularformulaC6H5Br,forms:

Chemistsconcluded,therefore,thatallsixcarbonatomsandallsixhydrogenatomsofbenzenemustbe
equivalent.Whenbromobenzeneistreatedwithbromineinthepresenceofiron(III)chloride,threeisomeric
dibromobenzenesareformed:

Forchemistsinthemidnineteenthcentury,theproblemwastoincorporatetheseobservations,alongwith
theacceptedtetravalenceofcarbon,intoastructuralformulaforbenzene.Beforeweexaminetheir
proposals,weshouldnotethattheproblemofthestructureofbenzeneandotheraromatichydrocarbons
occupiedtheeffortsofchemistsforoveracentury.Itwasnotuntilthe1930sthatchemistsdevelopeda
generalunderstandingoftheuniquechemicalpropertiesofbenzeneanditsderivatives.
Kekul'sModelofBenzene
ThestructureforbenzeneproposedbyAugustKekulin1872consistedofasixmemberedringwith
alternatingsingleanddoublebondsandwithonehydrogenatombondedtoeachcarbonatom.Kekul
furtherproposedthattheringcontainsthreedoublebondsthatshiftbackandforthsorapidlythatthetwo
formscannotbeseparated.EachstructurehasbecomeknownasaKekulstructure.

BecauseallofthecarbonatomsandhydrogenatomsofKekul'sstructureareequivalent,substituting
bromineforanyoneofthehydrogenatomsgivesthesamecompound.Thus,Kekul'sproposedstructure
wasconsistentwiththefactthattreatingbenzenewithbromineinthepresenceofiron(III)chloridegives
onlyonecompound,withmolecularformulaC6H5Br.

Hisproposalalsoaccountedforthefactthatthebrominationofbromobenzenegivesthree(andonlythree)
isomericdibromobenzenes:

AlthoughKekul'sproposalwasconsistentwithmanyexperimentalobservations,itwascontestedforyears.
Themajorobjectionwasthatitdidnotaccountfortheunusualchemicalbehaviourofbenzene.Ifbenzene
containsthreedoublebonds,why,hiscriticsasked,doesn'titshowthereactionstypicalofalkenes?Why
doesn'titadd3molesofbrominetoform1,2,3,4,5,6hexabromocyclohexane?Why,instead,doesbenzene
reactbysubstitutionratherthanaddition?

TheValenceBondModelofBenzene
Theconceptsofthehybridisationofatomicorbitalsandthetheoryofresonance,bothcomponentsof
valencebondtheory(seechapter5)developedbyLinusPaulinginthe1930s,providedthefirstadequate
descriptionofthestructureofbenzene.ThecarbonskeletonofbenzeneformsaregularhexagonwithCC
CandHCCbondanglesof120.Forthistypeofbonding,carbonusessp 2hybridorbitals.Each
carbonatomformsbondstotwoadjacentcarbonatomsbytheoverlapofsp 2sp 2hybridorbitalsandone
bondtohydrogenbytheoverlapofsp 21sorbitals.Asdeterminedexperimentally,allcarboncarbon
bondsinbenzenearethesamelength,1.39,avaluebetweenthelengthofasinglebondbetweensp 3
hybridisedcarbons(1.54)andthatofadoublebondbetweensp 2hybridisedcarbons(1.33):

Eachcarbonatomalsohasasingleunhybridised2porbitalthatcontainsoneelectron.Thesesix2porbitals
lieperpendiculartotheplaneoftheringandoverlaptoformacontinuouscloudencompassingallsix
carbonatoms.Theelectrondensityofthesystemofabenzeneringliesinonetorus(adoughnutshaped
region)abovetheplaneoftheringandinasecondtorusbelowtheplane(figure16.33).

FIGURE16.33 Orbitaloverlapmodelofbondinginbenzene:
(a)Thecarbonhydrogenframework.Thesix2porbitals,eachwithoneelectron,areshown
uncombined.
(b)Theoverlapofparallel2porbitalsformsacontinuouscloud,shownbyonetorusabove
theplaneoftheringandasecondbelowtheplaneofthering.

TheResonanceModelofBenzene
Theconceptofresonanceintroducedinchapter5tellsusthat,ifwecanrepresentamoleculeorionbytwo
ormorecontributingstructures,thatmoleculecannotbeadequatelyrepresentedbyanysinglecontributing
structure.Werepresentbenzeneasahybridoftwoequivalentcontributingstructures,oftenreferredtoas
Kekulstructuresandweindicatetherelationshipbetweenthetwobytheuseofadoubleheadedarrow:

EachKekulstructuremakesanequalcontributiontothehybridthus,theCCbondsareneithersingle
nordoublebonds,butsomethingintermediate.Werecognisethatneitherofthesecontributingstructures
exists(theyaremerelyalternativewaystopair2porbitals,withnoreasontopreferoneovertheother)and
thattheactualstructureissomethinginbetween.Analternativemeansofrepresentingthebenzeneringthat
highlightsthespecialnatureofthearomaticstructureistoshowacirclewithinthesixmemberedringof
carbonatoms:

Nevertheless,wecontinuetouseasinglecontributingstructure,alsocalledaresonancestructure,to
representthismoleculebecauseitservestoremindusofthetetravalenceofthecarbonatomsinvolvedand
allowsustomoreeasilyrepresentthemovementofelectronsinreactionmechanisms.

TheResonanceEnergyofBenzene
Resonanceenergyisthedifferenceinenergybetweenaresonancehybridanditsmoststablehypothetical
contributingstructure.Onewaytoestimatetheresonanceenergyofbenzeneistocomparetheenthalpiesof
hydrogenationofcyclohexeneandbenzene.Inthepresenceofatransitionmetalcatalyst,hydrogenreadily
reducescyclohexenetocyclohexane(p.721):

Bycontrast,benzeneisreducedonlyveryslowlytocyclohexaneundertheseconditions.Itisreducedmore
rapidlywhenheatedandunderveryhighpressuresofhydrogen:

Thecatalyticreductionofanalkeneisanexothermicreaction(p.304).Theenthalpyofhydrogenationper
doublebondvariessomewhatwiththedegreeofsubstitutionofthedoublebondforcyclohexene,
.Ifweconsiderbenzenetobe1,3,5cyclohexatriene,ahypotheticalcompound
withalternatingsingleanddoublebonds,wemightexpectitsenthalpyofhydrogenationtobe3120=
360kJmol1.Instead,theenthalpyofhydrogenationofbenzeneisonly208kJmol1.Thedifferenceof
152kJmol1betweentheexpectedvalueandtheexperimentallyobservedvalueistheresonanceenergyof
benzene.Figure16.34showstheseexperimentalresultsintheformofagraph.
 FIGURE16.34Theresonanceenergyofbenzene,asdeterminedbyacomparisonoftheenthalpiesof
hydrogenationofcyclohexene,benzeneandthehypothetical1,3,5cyclohexatriene.

Forcomparison,thestrengthofacarboncarbonsinglebondisabout333418kJmol1,andthatof
hydrogenbondinginwaterandlowmolarmassalcoholsisabout8.421kJmol1.Thus,althoughthe
resonanceenergyofbenzeneislessthanthestrengthofacarboncarbonsinglebond,itisconsiderably
greaterthanthestrengthofhydrogenbondinginwaterandalcohols.Insection19.1,wewillseethat
hydrogenbondinghasagreatereffectonthephysicalpropertiesofalcoholsandlittleimpactonthoseof
alkanes.Figure16.34showsthattheresonanceenergyofbenzeneandotheraromatichydrocarbonshasa
dramaticeffectontheirchemicalreactivity.

Thefollowingdiagramshowsresonanceenergiesforbenzeneandseveralotheraromatichydrocarbons.

TheConceptofAromaticity
Manytypesofmoleculesotherthanbenzeneanditsderivativesshowaromaticcharacterthatis,they
containhighdegreesofunsaturation,yetfailtoundergocharacteristicalkeneadditionandoxidation
reductionreactions.Whatchemistshadlongsoughttounderstandweretheprinciplesunderlyingaromatic
character.GermanchemicalphysicistErichHckelsolvedthisprobleminthe1930s.

Hckel'scriteriaaresummarisedasfollows.Tobearomatic,aringmust:
 1.haveone2porbitaloneachofitsatoms
2.beplanarornearlyplanar,sothatthereiscontinuousoverlapornearlycontinuousoverlapofall2p
orbitalsofthering
3.have2,6,10,14,18,andsoon,electronsinthecyclicarrangementof2porbitals.(Notethatthese
numbersaresolutionstotheequation4n+2,wherenisequalto0,1,2,3,4andsoon.)

Benzenemeetsthesecriteria.Itiscyclic,planar,hasone2porbitaloneachcarbonatomofthering,andhas
sixelectrons(anaromaticsextet)inthecyclicarrangementofits2porbitals.Ifstructureswithmorethan
oneringmeetthesecriteria,theyarealsoaromaticandsomeexamplesoftheseappearabove.

Theunsaturatedringsmayalsocontainatomsotherthancarbon,andthesemoleculesarecalled
heterocycliccompounds.Forexample,pyridineandpyrimidineareanaloguesofbenzene.Inpyridine,one
CHgroupofbenzeneisreplacedbyanitrogenatomand,inpyrimidine,twoCHgroupsarereplacedby
nitrogenatoms.

BoththepyridineandpyrimidinemoleculesmeettheHckelcriteriaforaromaticity.Theyarebothcyclic
andplanar,haveone2porbitaloneachatomofthering,andhavesixelectronsinthesystem.Inpyridine,
nitrogenissp 2hybridiseditsunsharedpairofelectronsoccupiesansp 2orbitalperpendiculartothe2p
orbitalsofthesystemandsoisnotapartofthesystem.Inpyrimidine,neitherunsharedpairofelectrons
ofnitrogenispartofthesystem.Theresonanceenergyofpyridineis134kJmol1,slightlylessthanthat
ofbenzene.Theresonanceenergyofpyrimidineis109kJmol1.

Thefivememberedringcompoundsfuran,pyrroleandimidazolearealsoaromatic:
Intheseplanarcompounds,eachheteroatom(noncarbonatom)issp 2hybridised,anditsunhybridised2p
orbitalispartofacontinuouscycleoffive2porbitals.Infuran,oneunsharedpairofelectronsofthe
heteroatomliesintheunhybridised2porbitalandisapartofthesystem(figure16.35).Theother
unsharedpairofelectronsliesinansp 2hybridorbital,perpendiculartothe2porbitals,andisnotapartof
thesystem.Inpyrrole,theunsharedpairofelectronsonnitrogenispartofthearomaticsextet.In
imidazole,theunsharedpairofelectronsononenitrogenispartofthearomaticsextettheunsharedpairon
theothernitrogenisnot.

FIGURE16.35Originofthesixelectrons(thearomaticsextet)infuranandpyrrole.Theresonanceenergyof
furanis67kJmol1 andthatofpyrroleis88kJmol1 .

Natureaboundswithcompoundshavingaheterocyclicringfusedtooneormoreotherrings.Twosuch
compoundsespeciallyimportantinthebiologicalworldareindoleandpurine.

Indolecontainsapyrroleringfusedtoabenzenering.Compoundsderivedfromindoleincludetheamino
acidltryptophan(section24.1)andtheneurotransmitterserotonin.Purinecontainsasixmembered
pyrimidineringfusedtoafivememberedimidazolering.Adenineisoneofthebuildingblocksof
deoxyribonucleicacid(DNA)andribonucleicacid(RNA),asdescribedinchapter25.Itisalsoa
componentofthebiologicaloxidisingagentnicotinamideadeninedinucleotide,abbreviatedNAD+.

Nomenclature
Thesimplestaromatichydrocarbonisbenzene,whichcontainsonlyhydrogenatomsboundtothearomatic
ring.Ofcourse,therearemanyaromatichydrocarbonswithnumerousdifferentsubstituentsinvarious
positionsaroundthering.Asalways,weneedtohaveaclearmeanstodescribeeachoftheseindividual
molecules.

MonosubstitutedBenzenes
Monosubstitutedalkylbenzenesarenamedasderivativesofbenzeneanexampleisethylbenzene.The
IUPACsystemretainscertaincommonnamesforseveralofthesimplermonosubstitutedalkylbenzenes.
Examplesaretoluene(ratherthanmethylbenzene)andstyrene(ratherthanphenylethene):

Thecommonnamesphenol,aniline,benzaldehyde,benzoicacidandanisolearealsoretainedbythe
IUPACsystem:

ThesubstituentgroupderivedbythelossofanHfrombenzeneisaphenylgroup(Ph)thatderivedbythe
lossofanHfromthemethylgroupoftolueneisabenzylgroup(Bn):

Inmoleculescontainingotherfunctionalgroups,phenylgroupsandbenzylgroupsareoftennamedas
substituents:

DisubstitutedBenzenes
Whentwosubstituentsoccuronabenzenering,threeconstitutionalisomersarepossible.Welocate
substituentseitherbynumberingtheatomsoftheringorbyusingthelocatorsortho,metaandpara,which
areabbreviatedtoo,mandprespectively.Thenumbers1,2areequivalenttoortho(Greekwordmeaning
straight),1,3tometa(Greekwordmeaningafter)and1,4topara(Greekwordmeaningbeyond).

Whenoneofthetwosubstituentsontheringimpartsaspecialnametothecompound,suchastoluene,
phenolandaniline,wenamethecompoundasaderivativeofthatparentmolecule.Inthiscase,thespecial
substituentoccupiesringpositionnumber1.TheIUPACsystemretainsthecommonnamexyleneforthe
threeisomericdimethylbenzenes.Whenneithergroupimpartsaspecialname,welocatethetwosubstituents
andlisttheminalphabeticalorderbeforethewordbenzene.Thecarbonatomofthebenzeneringwiththe
substituentthatcomesfirstinalphabeticalorderisnumberedC(1).

PolysubstitutedBenzenes
Whenthreeormoresubstituentsarepresentonaring,wespecifytheirlocationsbynumbers.Ifoneofthe
substituentsimpartsaspecialname,themoleculeisnamedasaderivativeofthatparentmolecule.Ifnone
ofthesubstituentsimpartsaspecialname,wenumberthemtogivethesmallestsetofnumbersandlistthem
inalphabeticalorderbeforethewordbenzene.Inthefollowingexamples,thefirstcompoundisa
derivativeoftoluene,andthesecondisaderivativeofphenol.Becausethereisnospecialnameforthethird
compound,wenumberthecarbonatomsusingthesmallestpossiblesetofnumbers,thenlistitsthree
substituentsinalphabeticalorder,followedbythewordbenzene:

WORKEDEXAMPLE16.21

NomenclatureofSubstitutedBenzenes
Writenamesforthefollowingcompounds.
(a)
 (b)

(c)

(d)

Analysis

Welookfortheimportantfunctionalgroupsthatmaygoverntheparentname.Forexample,the
presenceofamethylgroupboundtobenzenegeneratestheparentnametolueneacarboxyl
group,benzoicacid.Whenthesubstituentbecomescomplicatedwenamethebenzeneringasthe
substituentphenyl.

Solution
(a)3iodotolueneormiodotoluene
(b)3,5dibromobenzoicacid
(c)1chloro2,4dinitrobenzene
(d)3phenylpropene

PRACTICEEXERCISE16.18
Writenamesforthefollowingcompounds.
(a)

(b)
 (c)

Polycyclicaromatichydrocarbons(PAHs)containtwoormorearomaticrings,andeachpairofrings
sharestwocarbonatoms.Naphthalene,anthraceneandphenanthrene,themostcommonPAHs,and
substancesderivedfromthemarefoundincoaltarandhighboilingpointpetroleumresidues.Atonetime,
naphthalenewasusedasamothrepellentandinsecticideinpreservingwoollens,butitsusehasdecreased
duetotheintroductionofchlorinatedhydrocarbonssuchaspdichlorobenzene.Alsofoundincoaltarare
lesseramountsofacompoundcalledbenzo[a]pyrene.Thiscompoundisalsofoundintheexhaustsof
petrolpoweredinternalcombustionengines(suchascarengines)andincigarettesmoke.Benzo[a]pyreneis
averypotentcarcinogenandmutagen.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
16.8ReactionsofAromaticCompounds:Electrophilic
AromaticSubstitution
Byfarthemostcharacteristicreactionofaromaticcompoundsissubstitutionataringcarbonatom.Somegroupsthat
canbeintroduceddirectlyontotheringarethehalogens(X),thenitro(NO2)group,thesulfonicacid(SO3H)
group,alkyl(R)groupsandacyl(RCO)groups.

Halogenation:

Nitration:

Sulfonation:

Alkylation:

Acylation:

Thereareseveraltypesofelectrophilicaromaticsubstitutionreactionsthatis,reactionsinwhichahydrogenofan
aromaticringisreplacedbyanelectrophile,E+.Themechanismsofthesereactionsareactuallyverysimilar.Infact,
theycanbebrokendownintothreecommonsteps.
Step1:Formationoftheelectrophile:

Step2:Reactionoftheelectrophilewiththearomaticringtogivearesonancestabilisedcationintermediate:
 Step3:Protontransfertoabasetoregeneratethearomaticring:

Thereactionsweareabouttostudydifferonlyinthewaytheelectrophileisgeneratedandinthebasethatremoves
theprotontoreformthearomaticring.Youshouldkeepthisprincipleinmindasweexplorethedetailsofeach
reaction.

ChlorinationandBromination
Chlorinealonedoesnotreactwithbenzene,incontrasttoitsinstantaneousadditiontocyclohexene(section16.5).
However,inthepresenceofaLewisacidcatalyst,suchasiron(III)chlorideoraluminiumchloride,chlorinereactsto
givechlorobenzeneandHCl.Chemistsaccountforthistypeofelectrophilicaromaticsubstitutionbythefollowing
threestepmechanism.
Step1:Formationoftheelectrophilebyreactionbetweenchlorine(aLewisbase)andFeCl3(aLewisacid),
givinganionpaircontainingachloroniumion(anelectrophile):

Step2:ReactionoftheCl2FeCl3ionpairwiththeelectroncloudofthearomaticring,formingaresonance
stabilisedcationintermediate,representedhereasahybridofthreecontributingstructures:

Step3:ProtontransferfromthecationintermediatetoFeCl4,formingHCl,regeneratingtheLewisacidcatalyst
andgivingchlorobenzene:

TreatmentofbenzenewithbromineinthepresenceofaLewisacidgivesbromobenzeneandHBr.Themechanism
forthisreactionisthesameasthatforthechlorinationofbenzene.

Themajordifferencebetweentheadditionofahalogentoanalkeneandsubstitutionbyahalogenonanaromatic
ringisthefateofthecationintermediateformedinthefirststepofeachreaction(figure16.36).Recallthatthe
additionofchlorine(orbromine)toanalkeneisatwostepprocessthefirstandslowerstepistheformationofa
bridgedchloroniumionintermediate.Thisintermediatethenreactswithachlorideiontocompletetheaddition.With
aromaticcompounds,thecationintermediatelosesH+toregeneratethearomaticringandregainitslargeresonance
stabilisation.Thereisnosuchresonancestabilisationtoberegainedinthecaseofanalkene.

FIGURE16.36Thepositivechargeontheresonancestabilisedintermediateisdistributedapproximatelyequallyoncarbon
atoms2,4and6oftheringrelativetothepointofsubstitution.

NitrationandSulfonation
Thesequenceofstepsforthenitrationandsulfonationofbenzeneissimilartothatforchlorinationandbromination.
Fornitration,theelectrophileisthenitroniumion,NO2+,generatedbythereactionofnitricacidwithsulfuricacid.
InthefollowingequationsnitricacidiswrittenHONO2toshowmoreclearlytheoriginofthenitroniumion.
Step1:Formationoftheelectrophileby(a)protontransferfromsulfuricacidtotheOHgroupofnitricacid,
givingtheconjugateacidofnitricacid:

and(b)lossofwaterfromthisconjugateacid,givingthenitroniumion,NO2+:

Steps2and3ofthenitrationaregiveninworkedexample16.22.

Thesulfonationofbenzeneiscarriedoutusinghot,concentratedsulfuricacid.Theelectrophileunderthese
conditionsiseitherSO3orHSO3+,dependingontheexperimentalconditions.TheHSO3+electrophileisformedfrom
sulfuricacidinthefollowingway.
Step1:Formationoftheelectrophilebyacidcatalyseddehydration:

Steps2and3ofsulfonationfollowthesamemechanismasfornitration.

WORKEDEXAMPLE16.22
 ElectrophilicAromaticSubstitutionofBenzene
Writeastepwisemechanismforthenitrationofbenzene.

Analysisandsolution
Step1:Formationoftheelectrophile,asgivenabove
Step2:Reactionofthenitroniumion(anelectrophile)withthebenzenering(anucleophile),givinga
resonancestabilisedcationintermediate:

Step3:ProtontransferfromthisintermediatetoH2Oregeneratingthearomaticringandgiving
nitrobenzene:

PRACTICEEXERCISE16.19
Writeastepwisemechanismforthesulfonationof
benzene.UseHSO3+astheelectrophile.

Alkylation
Alkylationisaveryimportantsyntheticoutcomeasthenewcarboncarbonbondbetweenbenzeneandanalkyl
groupbuildsupthecomplexityofthemolecule.Thisisillustratedbythereactionofbenzenewith2chloropropane
inthepresenceofaluminiumchloride:

Thisformofalkylation,oftencalledFriedelCraftsalkylationafterthetwochemistswhodiscovereditin1877,is
amongthemostimportantmethodsforaddingnewcarboncarbonbondstoaromaticrings.Thereactioninvolvesthe
followingsteps.
Step1:Formationoftheelectrophilebyreactionofahaloalkane(aLewisbase)withaluminiumchloride(a
Lewisacid),givingamolecularcomplexinwhichaluminiumhasanegativeformalchargeandthehalogenofthe
haloalkanehasapositiveformalcharge.Redistributionofelectronsinthiscomplexthengivesanalkyl
carbocationaspartofanionpair:
 Step2:Reactionofthealkylcarbocationwiththeelectronsofthearomaticring,givingaresonancestabilised
cationintermediate:

Step3:ProtontransferregeneratingthearomaticcharacteroftheringandtheLewisacidcatalyst:

TherearetwomajorlimitationsonFriedelCraftsalkylations.Thefirstisthatitispracticalonlywithstable
carbocations,suchas3and2carbocations.Youmightexplorethereasonsforthisinsubsequentchemistry
o

ThesecondlimitationonFriedelCraftsalkylationisthatitfailsaltogetheronbenzeneringsbearingoneormore
stronglyelectronwithdrawinggroups(indicatedbytheletterY):

Whenanyofthefollowinggroupsispresentonthearomaticring,thebenzeneringdoesnotundergoFriedelCrafts
alkylation.

Acommoncharacteristicofthesegroupsisthateachhaseitherafullorpartialpositivechargeontheatombondedto
thebenzenering(seeexamplesonthenextpage).Forcarbonylcontainingcompounds,thispartialpositivecharge
arisesbecauseofthedifferenceinelectronegativitybetweenthecarbonyloxygenandcarbonatoms.FortheCF3
andCCl3groups,thepartialpositivechargeoncarbonarisesbecauseofthedifferenceinelectronegativitybetween
thecarbonatomandthehalogensbondedtoit.Inboththenitrogroup,NO2,andthetrialkylammoniumgroup,
suchasN(CH3)3+below,thereisapositivechargeonnitrogen:
Acylation
Treatinganaromatichydrocarbonwithanacylhalideinthepresenceofaluminiumchlorideformsacarboncarbon
bondandgivesaketoneinaprocessknownasacylation.Anacylhalideisaderivativeofacarboxylicacidinwhich
theOHofthecarboxylgroupisreplacedbyahalogen,mostcommonlychlorine(seechapter23).Acylhalidesare
alsoreferredtoasacidhalides.AnRCOgroupisknownasanacylgroup.Thereactionofanacylhalidewithan
aromatichydrocarbonisillustratedbelowbythereactionofbenzeneandacetylchlorideinthepresenceof
aluminiumchloridetogiveacetophenone.

ThisreactionisrelatedtotheFriedelCraftsalkylationinthataluminiumchlorideisusedtogeneratetheelectrophile,
whichinthiscaseiscalledanacyliumion.ThisreactionwasalsodiscoveredbyFriedelandCraftssoisoftencalled
theFriedelCraftsacylation.Themechanismisshownbelow.

WORKEDEXAMPLE16.23

FormingCarboncarbonBondstoAromaticRings
WriteastructuralformulafortheproductformedbyFriedelCraftsalkylationoracylationofbenzenewith
eachofthefollowing.

(a)

(b)
 Analysisandsolution

Benzeneisunsubstitutedsocanundergobothalkylationsandacylations.
(a)Treatmentofbenzylchloridewithaluminiumchloridegivestheresonancestabilisedbenzylcation.
Reactionofthiscationwithbenzene,followedbylossofH+,givesdiphenylmethane:

(b)Treatmentofbenzoylchloridewithaluminiumchloridegivesanacylcation.Reactionofthiscation
withbenzene,followedbylossofH+,givesbenzophenone:

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
IntroductiontoHydrocarbons
Ahydrocarbonisacompoundthatcontainsonlycarbonandhydrogenatoms.Thefourclassesof
hydrocarbonsarealkanes,alkenes,alkynesandarenes.

Alkanes
Asaturatedhydrocarboncontainsonlysinglebonds.AlkaneshavethegeneralformulaCnH2n+2.
Constitutionalisomershavethesamemolecularformulabutadifferentconnectivity(adifferentorderof
attachmentoftheiratoms).AlkanesarenamedaccordingtoasetofrulesdevelopedbyIUPAC.

Analkanethatcontainscarbonatomsbondedtoformaringiscalledacycloalkane.Tonamea
cycloalkane,prefixthenameoftheopenchainhydrocarbonwithcyclo.Compoundswiththesame
molecularformulaandthesameorderofattachmentofatoms,butarrangementsofatomsinspacethat
cannotbeinterconvertedbyrotationaroundsinglebonds,arecalledcistransisomers.Thetermcis
meansthatsubstituentsareonthesamesideoftheringtransmeansthattheyareonoppositesidesof
thering.Mostcycloalkaneswithsubstituentsontwoormorecarbonatomsoftheringshowcistrans
isomerism.

Alkanesarenonpolarcompounds,andtheonlyforcesofattractionbetweentheirmoleculesare
dispersionforces,whichareweakelectrostaticinteractionsbetweentemporarypartialpositiveand
negativechargesonatomsormolecules.

AlkenesandAlkynes
Analkeneisanunsaturatedhydrocarbonthatcontainsacarboncarbondoublebond.Alkeneshavethe
generalformulaCnH2n.Analkyneisanunsaturatedhydrocarbonthatcontainsacarboncarbontriple
bond.AlkyneshavethegeneralformulaCnH2n2.Weshowthepresenceofacarboncarbondouble
bondbychangingthenamingcomponentoftheparenthydrocarbonfromantoen.Weshowthe
presenceofacarboncarbontriplebondbychangingthenamingcomponentoftheparentalkanefrom
antoyn.

Thestructuralfeaturethatmakescistransisomerismpossibleinalkenesisrestrictedrotationaroundthe
twocarbonatomsofthedoublebond.Ifatomsoftheparentchainareonthesamesideofthedouble
bond,theconfigurationofthealkeneiscisiftheyareonoppositesides,theconfigurationistrans.
Usingasetofpriorityrules,wecanalsospecifytheconfigurationofacarboncarbondoublebondby
theE,Zsystem.Ifthetwogroupsofhigherpriorityareonthesamesideofthedoublebond,the
configurationofthealkeneisZiftheyareonoppositesides,itisE.

ReactionsofAlkanes
Alkaneshaveverylimitedreactivity.Themostimportantreactionofalkanesiscombustionwith
oxygen,whichisthebasisoftheiruseasenergysources.

ReactionsofAlkenes
Acharacteristicreactionofalkenesisaddition,duringwhichabondisbrokenandbondstotwo
newatomsorgroupsofatomsareformed.Thisprocessisdescribedassynadditionorantiaddition
dependingonwhethertheatomsappearonthesameoroppositesidesoftheoriginalcarboncarbon
bond.

Anelectrophileisanymoleculeorionthatcanacceptapairofelectronstoformanewcovalentbond.
AllelectrophilesareLewisacids.Theratedeterminingstepinelectrophilicadditiontoanalkeneisthe
reactionofanelectrophilewithacarboncarbondoublebondtoformacarbocationanionthat
containsacarbonatomwithonlysixelectronsinitsvalenceshellandthathasapositivecharge.
Carbocationsareplanar,withbondanglesof120aroundthepositivecarbonatom.Theorderof
stabilityofcarbocationsis3>2>1>methyl.

ReactionsofAlkynes
Alkynescanundergosimilarreactionstoalkenes:addition,reductionandoxidation.Ofparticular
importanceisreductionusinghydrogengaswherethechoiceofcatalystdetermineswhetheranalkene
oranalkaneisproduced.

AromaticCompounds
Benzeneanditsalkylderivativesareclassifiedasaromatichydrocarbons,orarenes.Theconceptsof
hybridisationofatomicorbitalsandthetheoryofresonanceareusedtodescribethestructureof
benzene.Theresonanceenergyofbenzeneisabout152kJmol1.

AccordingtotheHckelcriteriaforaromaticity,aringisaromaticifit(1)hasoneporbitaloneach
atomofthering,(2)isplanar,sothatoverlapofallporbitalsoftheringiscontinuousornearlyso,and
(3)has2,6,10,14,18,andsoon(i.e.4n+2),electronsintheoverlappingsystemofporbitals.A
heterocyclicaromaticcompoundcontainsoneormoreatomsotherthancarboninanaromaticring.

AromaticcompoundsarenamedbytheIUPACsystem.Thecommonnamestoluene,xylene,styrene,
phenol,aniline,benzoicacidandbenzaldehydeareretained.TheC6H5groupisnamedphenyl,and
theC6H5CH2groupisnamedbenzyl.Tolocatetwosubstituentsonabenzenering,eithernumberthe
atomsoftheringorusethelocatorsortho(o),meta(m)andpara(p).

Polycyclicaromatichydrocarbonscontaintwoormorefusedbenzenerings.Particularlyabundantare
naphthalene,anthraceneandphenanthrene,andtheirderivatives.

ReactionsofAromaticCompounds:ElectrophilicAromaticSubstitution
Aromaticcompoundsreactwithmanyformsofpositivelychargedelectrophilestogivesubstituted
aromaticsystems.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Oxidationofalkanes(section16.4)
Alkanesdisplayvirtuallynoreactivity,exceptunderharshconditionswheretheymaybecompletely
oxidisedtocarbondioxideandwater.Thisprocessliberatesenergyandprovidesthebasisfortheiruse
assourcesofheatandpower:

AdditionofHXtoalkenes(section16.5)
AdditionofHXisregioselectiveandfollowsMarkovnikov'srule.Reactionoccursintwostepsand
involvestheformationofacarbocationintermediate:

Acidcatalysedhydrationofalkenes(section16.5)
HydrationisregioselectiveandfollowsMarkovnikov'srule.Reactioninvolvestwostepsandformsa
carbocationintermediate:

Additionofbromineandchlorinetoalkenes(section16.5)
Additionoccursintwostepsandinvolvesantiadditionbywayofabridgedbromoniumorchloronium
ionintermediate:

Reductionofalkenes:formationofalkanes(section16.5)
Catalyticreductioninvolves,predominantly,thesynadditionofhydrogen:

Reductionofalkynestoalkenesoralkanes(section16.6)
Thechoiceofcatalystcontrolsthesyntheticoutcomeofthereductionofalkynes:
Chlorinationandbrominationofaromaticcompounds(section16.8)
Theelectrophileisahaloniumion,Cl+orBr+,formedbytreatingCl2orBr2withAlCl3orFeCl3:

Nitrationofaromaticcompounds(section16.8)
Theelectrophileisthenitroniumion,NO2+,formedbytreatingnitricacidwithsulfuricacid:

Sulfonationofaromaticcompounds(section16.8)
TheelectrophileisHSO3+:

Alkylationofaromaticcompounds(section16.8)
TheelectrophileisanalkylcarbocationformedbytreatinganalkylhalidewithaLewisacid:

Acylationofaromaticcompounds(section16.8)
TheelectrophileisanacylcationformedbytreatinganacylhalidewithaLewisacid:
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
IntroductiontoHydrocarbons
16.1Definethetermhydrocarbon.
16.2Whatdefineseachofthefollowing?
(a)alkane
(b)alkene
(c)alkyne
(d)arene
16.3Explainthedifferencebetweensaturatedandunsaturatedhydrocarbons.
Alkanes
16.4Whichofthesestatementsaretrueaboutconstitutionalisomers?
(a)Theyhavethesamemolecularformula.
(b)Theyhavethesamemolarmass.
(c)Theyhavethesameorderofattachmentofatoms.
(d)Theyhavethesamephysicalproperties.
16.5Writealinestructureforeachofthesecondensedstructuralformulae.
(a)

(b)

(c)(CH3)2CHCH(CH3)2
(d)

(e)(CH3)3CH
(f) CH3(CH2)3CH(CH3)2
16.6Writeacondensedstructuralformulaandthemolecularformulaforeachofthefollowingalkanes.
(a)

(b)
 (c)

16.7Foreachofthefollowingcondensedstructuralformulae,provideanevenmoreabbreviated
formula,usingparenthesesandsubscripts.
(a)

(b)

(c)

16.8Nameanddrawlinestructuresforthenineconstitutionalisomerswiththemolecularformula
C7H16.
16.9Foreachofthefollowing,statewhetherthetwostructuralformulaeshownrepresentconstitutional
isomers.
(a)

(b)

(c)

(d)

(e)
 (f)

16.10Ineachofthefollowing,arethetwocompoundsconstitutionalisomers?
(a)

(b)

(c)

(d)

(e)

(f)

16.11WriteIUPACnamesforeachofthefollowingalkanesandcycloalkanes.
(a)

(b)

(c)

(d)
 (e)

(f)

16.12Writelinestructuresforthesealkanes.
(a)2,2,4trimethylhexane
(b)2,2dimethylpropane
(c)3ethyl2,4,5trimethyloctane
(d)5butyl2,2dimethylnonane
(e)4isopropyloctane
(f) 3,3dimethylpentane
(g)trans1,3dimethylcyclopentane
(h)cis1,2diethylcyclobutane
16.13ExplainwhyeachofthefollowingnamesisanincorrectIUPACname,andwritethecorrect
IUPACnamefortheintendedcompound.
(a)1,3dimethylbutane
(b)4methylpentane
(c)2,2diethylbutane
(d)2ethyl3methylpentane
(e)2propylpentane
(f) 2,2diethylheptane
(g)2,2dimethylcyclopropane
(h)1ethyl5methylcyclohexane
16.14Whatstructuralfeatureofcycloalkanesmakesitpossibleforthemtoexhibitcistrans
isomerism?
16.15Iscistransisomerismpossibleinalkanes?
16.16Nameanddrawstructuralformulaeforthecisandtransisomersof1,2dimethylcyclopropane.
16.17NameanddrawstructuralformulaeforallcycloalkaneswiththemolecularformulaC5H10.Be
certaintoincludecistransisomers,aswellasconstitutionalisomers.
16.18Usingaplanarpentagonrepresentationforthecyclopentanering,drawstructuralformulaefor
thecisandtransisomersofthefollowing.
(a)1,2dimethylcyclopentane
(b)1,3dimethylcyclopentane
AlkenesandAlkynes
16.19Drawastructuralformulaforeachofthesecompounds.
(a)trans2methylhex3ene
 (b)2methylhex3yne
(c)2methylbut1ene
(d)3ethyl3methylpent1yne
(e)2,3dimethylbut2ene
(f) cispent2ene
(g)(Z)1chloropropene
(h)3methylcyclohexene
16.20Drawastructuralformulaforeachofthesecompounds.
(a)1isopropyl4methylcyclohexene
(b)(6E)2,6dimethylocta2,6diene
(c)trans1,2diisopropylcyclopropane
(d)2methylhex3yne
(e)2chloropropene
(f) tetrachloroethene
16.21WritetheIUPACnameforeachofthesecompounds.
(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)
16.22WritethestructuralformulaeandgivetheIUPACnamesforallpossiblealkyneswitheachofthe
followingmolecularformulae.
(a)C5H8
(b)C6H10
(c)C8H12
16.23GivetheIUPACnamesforthefollowing.
(a)

(b)CH3C CCH2C CCH2CH3

(c)

(d)HC CCH2HC CCH2CH3

16.24Explainwhythefollowingnamesareincorrect.Givethecorrectnameanddrawthestructural
formula.
(a)but3yne
(b)pent3yne1ene
(c)but3en1yne
16.25Explainwhythesenamesareincorrect,andwriteacorrectnamefortheintendedcompound.
(a)1methylpropene
(b)pent3ene
(c)2methylcyclohexene
(d)3,3dimethylpentene
(e)hex4yne
(f) 2isopropylbut2ene
16.26Explainwhythesenamesareincorrect,andwriteacorrectnamefortheintendedcompound.
(a)2ethylprop1ene
(b)5isopropylcyclohexene
(c)4methylhex4ene
(d)2secbutylbut1ene
(e)6,6dimethylcyclohexene
(f) 2ethylhex2ene
16.27Whichofthesealkenesshowcistransisomerism?Foreachthatdoes,drawstructuralformulae
forbothisomers.
(a)hex1ene
 (b)hex2ene
(c)hex3ene
(d)2methylhex2ene
(e)3methylhex2ene
(f) 2,3dimethylhex2ene
16.28Whichofthesealkenesshowcistransisomerism?Foreachthatdoes,drawstructuralformulae
forbothisomers.
(a)pent1ene
(b)pent2ene
(c)3ethylpent2ene
(d)2,3dimethylpent2ene
(e)2methylpent2ene
(f) 2,4dimethylpent2ene
16.29Whichofthesealkenescanexistaspairsofcistransisomers?Foreachalkenethatcan,drawthe
transisomer.
(a)CH2 CHBr
(b)CH3CH CHBr
(c)(CH3)2C CHCH3
(d)(CH3)2CHCH CHCH3
16.30Arrangethegroupsineachofthesesetsinorderofincreasingpriority.
(a)CH3,Br,CH2CH3
(b)OCH3,CH(CH3)2,CH2CH2NH2
(c)CH2OH,COOH,OH
(d)CH CH2,CH O,CH(CH3)2
16.31Foreachofthesemoleculesthatshowscistransisomerism,drawthecisisomer.
(a)

(b)

(c)

(d)
16.32Explainwhyeachofthesenamesisincorrectorincomplete,andthenwriteacorrectname.
(a)(Z)2methylpent1ene
(b)(E)3,4diethylhex3ene
(c)trans2,3dimethylhex2ene
(d)(1Z,3Z)2,3dimethylbuta1,3diene
16.33DrawstructuralformulaeforallcompoundswiththemolecularformulaC5H10thatare:
(a)alkenesthatdonotshowcistransisomerism
(b)alkenesthatdoshowcistransisomerism
(c)cycloalkanesthatdonotshowcistransisomerism
(d)cycloalkanesthatdoshowcistransisomerism.
Reactionsofalkanes
16.34Writebalancedequationsforthecombustionofeachofthefollowinghydrocarbons.Assumethat
eachisconvertedcompletelytocarbondioxideandwater.
(a)hexane
(b)cyclohexane
(c)2methylpentane
Reactionsofalkenes
16.35Selectthemorestablecarbocationfromeachofthesepairs.
(a)

(b)

16.36Selectthemorestablecarbocationfromeachofthesepairs.
(a)

(b)

16.37Writeabalancedequationforthecombustionof2methylpropeneinairtogivecarbondioxide
andwater.TheoxidisingagentisO2,whichmakesupapproximately20%ofair.
16.38DrawtheproductformedbytreatingeachofthesealkeneswithH2/Ni.
(a)

(b)
 (c)

(d)

16.39Showhowtoconvertetheneintothesecompounds.
(a)ethane
(b)ethanol
(c)bromoethane
(d)1,2dibromoethane
(e)chloroethane
ReactionsofAlkynes
16.40Usinganyalkyneandtherequiredcatalyst,describehowyouwouldpreparethefollowing
alkenes.
(a)cisoct2ene
(b)transhept2ene
(c)3methylhex1ene
16.41Predicttheproductsofthereactionofhex2ynewiththefollowing.
(a)H2andPd/C
(b)H2andNa/NH3
(c)H2usingLindlarcatalyst
(d)H2usingLindlarcatalystfollowedbytheadditionofBr2
16.42Writeequationsforthefollowingreactionsofalkynes.
(a)pent2yne(1mole)+H2(1mole)+Lindlarcatalyst
(b)hex3yne(1mole)+Br2(2moles)
(c)but2yne(1mole)+Li(1mole)inNH3(l)
(d)but1yne(1mole)+H2(2moles)+Pd/Ccatalyst
16.43Whatistheproductofthefollowingreaction?

Aromaticcompounds
16.44Namethesecompounds.
(a)
 (b)

(c)

(d)

(e)

(f)

(g)

(h)

16.45Drawstructuralformulaeforthesecompounds.
 (a)1bromo2chloro4ethylbenzene
(b)4iodo1,2dimethylbenzene
(c)2,4,6trinitrotoluene
(d)4phenylpentan2ol
(e)pcresol(pmethylphenol)
(f) 2,4dichlorophenol
(g)1phenylcyclopropanol
(h)styrene(phenylethene)
(i) mbromophenol
(j) 2,4dibromoaniline
(k)isobutylbenzene
(l) mxylene
ReactionsofAromaticCompounds:ElectrophilicAromaticSubstitution
16.46Drawastructuralformulaforthecompoundformedbytreatingbenzenewitheachofthe
followingcombinationsofreagents.
(a)CH3CH2Cl/AlCl3
(b)CH2 CH2/H2SO4
(c)CH3CH2OH/H2SO4
16.47Showthreedifferentcombinationsofreagentsyoumightusetoconvertbenzeneto
isopropylbenzene.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
16.48Inquestion16.8,youdrewstructuralformulaeforallconstitutionalisomerswithmolecular
formulaC7H16.Predictwhichofthoseisomershasthelowestboilingpointandwhichhasthe
highest.
16.49Whatgeneralisationscanyoumakeaboutthedensitiesofalkanesrelativetothatofwater?
16.50Whichunbranchedalkanehasaboutthesameboilingpointaswater(seetable16.1)?Calculate
themolarmassofthisalkane,andcompareitwiththatofwater.
16.51Table16.1showsthateachCH2groupaddedtothecarbonchainofanalkaneincreasesthe
boilingpointofthealkane.TheincreaseisgreatergoingfromCH4toC2H6andfromC2H6to
C3H8thanitisfromC8H18toC9H20orfromC9H20toC10H22.Whatdoyouthinkisthereason
forthistrend?
16.52Asstatedinsection16.2,thewaxfoundnaturallyinappleskinsisanunbranchedalkanewith
themolecularformulaC27H56.Explainhowthepresenceofthisalkanepreventsthelossof
moisturefromwithinanapple.
16.53Predictanswerstothefollowingquestionsaboutdodecane,C12H26,anunbranchedalkane.
(a)Willitdissolveinwater?
(b)Willitdissolveinhexane?
(c)Willitburnwhenignited?
(d)Isitaliquid,solidorgasatroomtemperatureandatmosphericpressure?
(e)Isitmoreorlessdensethanwater?
16.54Thefollowingtableshowsenthalpiesofcombustionformethaneandpropane.

Hydrocarbon Componentof
CH4 naturalgas 886
CH3CH2CH3 LPG 2220

Onagramforgrambasis,whichofthesehydrocarbonsisthebettersourceofheatenergy?
16.55TherearethreecompoundswiththemolecularformulaC2H2Br2.Twoofthesecompoundshave
adipolemomentgreaterthanzero,andonehasnodipolemoment(seechapter5,p.183).Draw
structuralformulaeforthethreecompounds,andexplainwhytwohavedipolemomentsbutthe
thirdonedoesnot.
16.56NameanddrawstructuralformulaeforallalkeneswiththemolecularformulaC5H10.Asyou
drawthesealkenes,rememberthatcisandtransisomersaredifferentcompoundsandmustbe
countedseparately.
16.57NameanddrawstructuralformulaeforallalkeneswiththemolecularformulaC6H12thathave
thefollowingcarbonskeletons(countcisandtransisomersseparately).
(a)

(b)
 (c)

16.58DrawthestructuralformulaforatleastonebromoalkenewiththemolecularformulaC5H9Br
that:
(a)showsE,Zisomerism
(b)doesnotshowE,Zisomerism.
16.59AtrienefoundinthefragranceofcottonblossomsandseveralessentialoilshastheIUPACname
(3Z)3,7dimethylocta1,3,6trieneandthecommonnameocimene.Drawitsstructural
formula.
16.60Determinewhetherthestructuresineachofthefollowingsetsrepresentthesamemolecule,
cistransisomersorconstitutionalisomers.Iftheyarethesamemolecule,determinewhether
theyareinthesameordifferentconformations.

(a)

(b)

(c)

(d)

16.61Whichalkyneandwhichreagentcouldbeusedtogiveeachofthefollowing.
(a)2,2dichlorobutane
(b)butan2ol
(c)2,2,3,3tetrabromobutane
16.62Howwouldyoucarryoutthefollowingtransformations?
(a)

(b)

(c)
 (d)

16.63Drawstructuralformulaefortheisomericcarbocationintermediatesformedbythereactionof
eachofthefollowingalkeneswithHCl.Labeleachcarbocationasprimary,secondaryortertiary,
andstatewhich,ifeither,oftheisomericcarbocationsisformedmorereadily.
(a)

(b)

(c)

(d)

16.64Fromeachofthesepairsofcompounds,selecttheonethatreactsmorerapidlywithHI,drawthe
structuralformulaofthemajorproductformedineachcase,andexplainthebasisforyour
ranking.
(a)

(b)

16.65Completetheseequationsbypredictingthemajorproductformedineachreaction.
(a)

(b)

(c)

(d)
 (e)

(f)

16.66Thereactionof2methylpent2enewitheachofthefollowingreagentsisregioselective.Draw
thestructuralformulafortheproductofeachreaction,andaccountfortheobserved
regioselectivity.
(a)HI
(b)H2OinthepresenceofH2SO4
16.67Theadditionofbromineandchlorinetocycloalkenesisstereospecific.Predictthe
stereochemistryoftheproductformedineachofthesereactions.
(a)1methylcyclohexene+Br2
(b)1,2dimethylcyclopentene+Cl2
16.68Ineachofthefollowingreactions,drawthestructuralformulaofanalkenewiththeindicated
molecularformulathatgivesthecompoundshownasthemajorproduct.Notethatmorethanone
alkenemaygivethesamecompoundasthemajorproduct.
(a)

(b)

(c)

16.69DrawthestructuralformulaofanalkenewiththemolecularformulaC5H10thatreactswithBr2to
giveeachoftheseproducts.
(a)

(b)
 (c)

16.70DrawthestructuralformulaofacycloalkenewiththemolecularformulaC6H10thatreactswith
Cl2togiveeachofthesecompounds.
(a)

(b)

(c)

(d)

16.71DrawthestructuralformulaofanalkenewiththemolecularformulaC5H10thatreactswithHCl
togiveeachofthefollowingchloroalkanesasthemajorproduct.
(a)

(b)

(c)

16.72Thecompoundscishex3eneandtranshex3enearedifferentandhavedifferentphysicaland
chemicalproperties.Yet,whentreatedwithH2O/H2SO4,eachgivesthesamealcohol.Whatis
thealcohol,andhowdoyouaccountforthefactthateachalkenegivesthesameone?
16.73Drawthestructuralformulaofanalkenethatundergoesacidcatalysedhydrationtogiveeachof
thefollowingalcoholsasthemajorproduct.Notethatmorethanonealkenemaygivethesame
compoundasthemajorproduct.
(a)hexan3ol
 (b)1methylcyclobutanol
(c)2methylbutan2ol
(d)propan2ol
16.74Drawthestructuralformulaofanalkenethatundergoesacidcatalysedhydrationtogiveeachof
thefollowingalcoholsasthemajorproduct.Notethatmorethanonealkenemaygivethesame
compoundasthemajorproduct.
(a)cyclohexanol
(b)1,2dimethylcyclopentanol
(c)1methylcyclohexanol
(d)1isopropyl4methylcyclohexanol
16.75Terpinispreparedcommerciallybytheacidcatalysedhydrationoflimonene:

(a)Proposeastructuralformulaforterpinandamechanismforitsformation.
(b)Howmanycistransisomersarepossibleforthestructuralformulayouproposedin(a)?
16.76Thetreatmentof2methylpropenewithmethanolinthepresenceofasulfuricacidcatalystgives
tertbutylmethylether:

Proposeathermodynamicallysoundmechanismfortheformationofthisether.
16.77Thetreatmentof1methylcyclohexenewithmethanolinthepresenceofasulfuricacidcatalyst
givesacompoundwiththemolecularformulaC8H16O:

Proposeastructuralformulaforthiscompoundandamechanismforitsformation.
16.78HydrocarbonA,C5H8,reactswith2molesofBr2togive1,2,3,4tetrabromo2methylbutane.
WhatisthestructureofhydrocarbonA?
16.79AlkenesAandBbothhavetheformulaC5H10.BothreactwithH2/PtandwithHBrtogive
identicalproducts.WhatarethestructuresofAandB?
16.80Showhowtoconvertcyclopenteneintothesecompounds.
(a)
 (b)

(c)

(d)

16.81Showhowtoconvertbut1eneintothesecompounds.
(a)butane
(b)2bromobutane
(c)butan2ol
(d)1,2dibromobutane
16.82Showhowthefollowingcompoundscanbesynthesisedingoodyieldsfromanalkene.
(a)

(b)

(c)

16.83Showthatpyridinecanberepresentedasahybridoftwoequivalentcontributingstructures.
16.84Showthatnaphthalene(pp.7278)canberepresentedasahybridofthreecontributing
structures.Showalso,bytheuseofcurvedarrows,howonecontributingstructureisrelatedto
thenext.
16.85Drawfourcontributingstructuresforanthracene(p.728).
16.86Whichofthefollowingcompoundsarearomatic?
 (a)

(b)

(c)

(d)

(e)

(f)

16.87Explainwhycyclopentadiene(pKa =16)ismanyordersofmagnitudemoreacidicthan
cyclopentane(pKa >50)(Hint:Drawthestructuralformulaoftheanionformedbyremovingone
oftheprotonsontheCH2group,andthenapplytheHckelcriteriaforaromaticity.)

16.88HowmanymonochlorinationproductsarepossiblewhennaphthaleneistreatedwithCl2/AlCl3?
16.89Writeastepwisemechanismforthefollowingreaction,usingcurvedarrowstoshowtheflowof
electronsineachstep.
16.90Writeastepwisemechanismforthepreparationofdiphenylmethanebytreatingbenzenewith
dichloromethaneinthepresenceofanaluminiumchloridecatalyst.
16.91Usingstyrene,C6H5CH CH2,astheonlyaromaticstartingmaterial,showhowtosynthesise
thefollowingcompounds.Inadditiontostyrene,useanyothernecessaryorganicorinorganic
chemicals.Anycompoundsynthesisedinonepartofyouranswermaybeusedtomakeany
othercompoundintheanswer.
(a)

(b)

(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
16.92Explainwhy1,2dimethylcyclohexanecanexistascistransisomers,while1,2
dimethylcyclododecanecannot.
16.93Eachcarbonatominethaneandinetheneissurroundedbyeightvalenceelectronsandhasfour
bondstoit.Explainhowthevalenceshellelectronpairrepulsion(VSEPR)model(section5.4)
predictsabondangleof109.5aroundeachcarbonatominethane,butanangleof120around
eachcarbonatominethene.
16.94Usethevalenceshellelectronpairrepulsion(VSEPR)modeltopredictallbondanglesaround
eachofthefollowinghighlightedcarbonatoms.
(a)

(b)

(c)

(d)

16.95Foreachhighlightedcarbonatominquestion16.94,identifywhichorbitalsareusedtoform
eachbondandwhichareusedtoformeachbond.
16.96Predictallbondanglesaroundeachofthefollowinghighlightedcarbonatoms.
(a)

(b)

(c)

(d)
16.97Foreachhighlightedcarbonatominquestion16.96,identifywhichorbitalsareusedtoform
eachbondandwhichareusedtoformeachbond.
16.98Thestructureofpropa1,2diene(allene)isshownbelow.TheplanecreatedbyHCHofC(1)
isperpendiculartothatcreatedbyHCHofC(3).

(a)Statetheorbitalhybridisationofeachcarbonatominallene.
(b)Accountforthemoleculargeometryofalleneintermsoftheorbitaloverlapmodel.
Specifically,explainwhyallfourhydrogenatomsarenotinthesameplane.
16.99Eachofthefollowingsecondarycarbocationsismorestablethanthetertiarycarbocationshown.

(a)

(b)

(c)

Explainwhyeachofthecarbocationsmightbemorestablethanthetertiarycarbocation.
16.100Oleicacidandelaidicacidare,respectively,thecisandtransisomersofoctadec9enoicacid.
Oneofthesefattyacids,acolourlessliquidthatsolidifiesat4C,isamajorcomponentof
butterfat.Theother,awhitesolidwithameltingpointof4445C,isamajorcomponentof
partiallyhydrogenatedvegetableoils.Whichofthesetwofattyacidsisthecisisomerandwhich
isthetransisomer?
16.101RecallthatanalkenepossessesacloudofelectronsaboveandbelowtheplaneoftheC C
bond.Anyreagentcan,therefore,reactwitheitherfaceofthedoublebond.Determinewhether
thereactionofeachofthefollowingreagentswiththetopfaceofcisbut2enewillproducethe
sameproductasthereactionofthesamereagentwiththebottomface.(Hint:Buildmolecular
modelsoftheproductsandcomparethem.)
 (a)H2/Pt
(b)Br2/CH2Cl2
16.102Thebombardierbeetlegeneratespquinone,anirritatingchemical,bytheenzymecatalysed
oxidationofhydroquinone,usinghydrogenperoxideastheoxidisingagent.Heatgeneratedin
thisoxidationproducessuperheatedsteam,whichisejected,alongwithpquinone,with
explosiveforce.

(a)Balancetheequation.
(b)Isthisanoxidationreaction(seechapter12)?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
acylation catalyticreduction meta
additiontothecarboncarbon chairconformation Newmanprojection
doublebond cistransisomers nitroniumion
aliphatichydrocarbon configurationalisomers ortho
alkane conformation oxoniumion
alkene conformer para
alkylation cycloalkane phenol
alkyne cycloalkene phenylgroup
anglestrain E,Zsystem polycyclicaromatic
aniline electrophile hydrocarbon(PAH)
anisole electrophilicaromatic regioselectivereaction
antiaddition substitution resonanceenergy
antiselectivity enthalpyofhydrogenation saturatedhydrocarbon
arene equatorialbonds stereospecificreaction
aromatic FriedelCraftsacylation stericstrain
arylgroup FriedelCraftsalkylation styrene
axialbonds haloniumion synaddition
benzaldehyde heterocycliccompound theoryofresonance
benzoicacid hybridisationofatomic toluene
benzylgroup orbitals torsionalstrain
boatconformation hydration unsaturatedhydrocarbon
bridgedhaloniumion hydrocarbon xylene
carbocation inductiveeffect
catalytichydrogenation Kekulstructure
Markovnikov'srule

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

17 Chirality
Thedrugthalidomidewasdevelopedinthelate1950stotreatmorningsicknesssufferedby
somewomenduringpregnancy.Unfortunately,thalidomidecanexistintwomolecular
forms.Oneformisindeedaneffectivetreatmentformorningsickness,buttheotherform
causesterriblebirthdefectsinchildrenwhosemotherstakethedrugduringtheearlystages
ofpregnancy.TheAustralianobstetricianDrWilliamMcBridefirstalertedtheworldtothis
linkthroughalettertothemedicaljournalTheLancetinDecember1961.Ittookuntil2010,
however,beforescientistsfromJapanwereabletodiscoverthatoneformofthalidomide
inhibitsproductionofacrucialproteincalledcereblon,whichcreatesthekeyenzymes
neededforlimbdevelopment.Eachofthetwoformsofthalidomidehasexactlythesame
atomconnectivitythesameatomsconnectedinthesamesequencebuttherelative
positionsoftheatomsinspace,whenviewedinthreedimensions,aresubtlydifferent.Inthe
caseofthalidomide,thetwomolecularformsaremirrorimagesofeachother.Today,
pharmaceuticalcompaniesarerequiredtoprovethatbothformsofanysuchdrugsaresafe
fortheirintendeduse.Thalidomide,nowsoldasThalomidbyCelgenePtyLtd,remainsin
usetoday,butnowitspotenteffectoncellularbiochemistryisexploitedasalastlineof
defenceagainstsomecancersandasatreatmentforleprosyandcertainskindiseases.

Inearlierchapters,welearnedaboutconstitutionalisomersandhowthesequenceof
connectionsoftheatomsinamoleculeinfluencesthepropertiesofthesubstance.Inthis
chapter,wewilllearnaboutmoleculesthatcontainthesameatomsandthesamesequenceof
connections(atomconnectivity)butinwhichtheatomshavedifferentrelativepositionsin
space.

Thesemoleculesareknownasstereoisomers.Asweknowfromthalidomide,thesedifferent
threedimensionalarrangementscanleadtosubstantialdifferencesinproperties.

Asoundunderstandingofstereoisomersisfundamentaltoourunderstandingoforganic
chemistryandbiochemistry.
KEYTOPICS

17.1Stereoisomers
17.2Enantiomerism
17.3Namingstereocentres:theR,Ssystem
17.4Moleculeswithmorethanonestereocentre
17.5Opticalactivity:detectingchiralityinthelaboratory
17.6Chiralityinthebiologicalworld
17.7Synthesisingchiraldrugs
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.1Stereoisomers
Inchapter2welearnedthatisomersaremoleculeswiththesamemolecularformula(thesamenumbersofeachtypeof
atom)butdifferentstructures.Wedescribedhowdifferentsequencesofatomconnectivityleadtomoleculeswithdifferent
propertiesandwecalltheseconstitutionalisomers.Forexample,butaneand2methylpropane(isobutane)havethesame
numbersofcarbonatoms(four)andhydrogenatoms(ten),buttheircarbonatomsareconnectedinadifferentsequence.
Butanehasalinearchainandisobutanehasabranch,asshowninfigure17.1.Thesedifferentsequencescangiveriseto
differencesinproperties,suchasboilingpoint.

FIGURE17.1Butaneandisobutaneareconstitutionalisomers.Theirdifferentatomconnectivitygivesthemdifferentproperties.

Othermoleculescancontainthesamenumbersandkindsofatoms,allbondedtoeachotherinthesameorder,withthe
onlydifferencebetweenthemoleculesbeingthatsomebondsand,therefore,atomsarearrangeddifferentlyinspace.This
canalsogivethemdifferentproperties.Suchisomersarecalledstereoisomers.Therearetwotypesofstereoisomers:
enantiomersanddiastereomers.Let'sdescribeenantiomersfirst.

Oneoftheeasiestwaystograsptheconceptofenantiomersisbylookingatourhands.Figure17.2showsalefthand,its
reflectioninamirror,andarighthand.Noticethatthelefthand'sreflectionlooksjustliketherighthand.Thatis,ourleft
andrighthandsaremirrorimagesofeachother.

FIGURE17.2Theleftandrighthandsarenonsuperimposablemirrorimagesofeachother.Stereoisomersthatare
nonsuperimposablemirrorimagesofeachotherarecalledenantiomers.

Nowlookatyourownhands.Thelefthandhasfourdifferentfingersandathumbinaparticularorder,therighthandhas
fourdifferentfingersandathumbinthesameorder,butitisquiteobviousthatyourleftandrighthandsarenotthesame.
Superimposabilityistheabilityoftwoobjectstofitonewithintheotherwithnomismatchofparts.Nomatterhowyou
moveyourhands,theyarenotsuperimposable.Justtryputtingalefthandedgloveonyourrighthand(seefigure17.3).
Objectsthatarenonsuperimposableontheirmirrorimages,suchastheshellsinfigure17.5,aresaidtobechiral
(pronouncedkiraltorhymewithspiral,fromtheGreekwordcheirmeaninghand)thatis,theyshowhandedness.
 FIGURE17.3Alefthandedglovedoesnotfitthatis,itisnotsuperimposableontherighthand.

Chiralityisencounteredinthreedimensionalobjectsofallsorts.Aspiralbindingonanotebookischiral.Aclockfaceis
alsochiral.Asyouexaminetheworldaroundyou,youwillseethatmanyobjectsarechiral(e.g.aceilingfan,thethreadof
ascrew,acomputerkeyboard).Chiralityevenunderpinstheworkingsofthingsthatyoucannotsee.Modernliquidcrystal
displaysthatarefoundinHDtelevisions,smartphones(figure17.4)andcomputerscreensworkbecausethestructuresof
thematerialsthatarepresentinthesedisplaysarearrangedinchiralorientations.Evenindividualmoleculescanbechiral.
Suchmolecules,stereoisomersthatcannotbesuperimposedontheirmirrorimages,arecalledcalledenantiomers.
 FIGURE17.4LCDscreensrelyonmaterialsthatarearrangedinchiralorientations.

FIGURE17.5Thenexttimeyouareatthebeach,keepaneyeoutforacoiledshell.Youwillseethatthecoilingformsaspiral.
(a)Mostcoiledshellsspiralinthesamedirectionwiththeshellapexpointingupwards,theshell'sopeningistothe
right,asintheseAustralianandNewZealandexamples.Whilethisisthecaseformostcoiledshells,itisnottrue
forallspecies
(b)someoccurinbothlefthandedandrighthandedforms.
(c)Interestingly,forsomespeciesinwhichonechiralformpredominates,veryinfrequentlyexamplesoftheopposite
chiralityarefoundforexample,1in10000shellsfromthespeciesCymbiolavespertilioislefthanded.

Thetwotypesofmoleculespresentinthedrugthalidomideareenantiomers.Asimplerexampleofenantiomersisglucose
(Dglucopyranose)anditsmirrorimage,ascanbeseeninfigure17.6.

FIGURE17.6Apairofenantiomers:Dglucopyranoseanditsnonsuperimposablemirrorimage.

Ifourhandsweresuperimposable,wewouldhavetwolefthandsortworighthands.Ifthemirrorimagesofmoleculeswere
superimposable,theywouldbethesamemolecule.Objectsthathavesuperimposablemirrorimagesaresaidtobeachiral.
Thatis,theydonotexhibithandedness.
Imagineforamomentthatyoucanmakethelittlefingerofyourrighthandstandat90totheotherfingersonyourright
hand(perhapsyoucan).Holditnexttoyourlefthand.Therearestillfourfingersandathumboneachhand,connectedin
thesamesequence,but,asshowninfigure17.7,thehandsnolongerlooklikemirrorimages.Thatis,ifyouheldyourleft
handtoamirror,itsreflectionwouldnotlookliketherighthandinthisposition.

FIGURE17.7Providedthatyoudon'tmovethelittlefingeronyourrighthandfromthisposition,theleftandrighthandsarenolonger
mirrorimagesofeachother.Stereoisomersthatarenotmirrorimagesofeachotherarecalleddiastereomers.

Stereoisomersthatarenotmirrorimagesofeachotherarecalleddiastereomers.Anexampleofdiastereomersthatwehave
alreadyencountered(p.695)isshowninfigure17.8:cistransisomersincycloalkanes.(Rememberthatthesolidwedge
representsabondpointingabovetheplaneofthepageandahashedwedgerepresentsabondpointingbelowtheplaneof
thepage.)Incis1,2dimethylcyclopentane,bothCH3groupsareabovetheplaneofthepage.Intrans1,2
dimethylcyclopentane,oneCH3groupisbelowtheplaneofthepageandoneisabovetheplaneofthepage.

FIGURE17.8Thecistransisomersof1,2dimethylcyclopentaneareapairofdiastereomers.Theyarestereoisomers,buttheyare
notmirrorimagesandsotheyarenotenantiomers.

Thedifferenttypesofisomersaresummarisedinfigure17.9.Thischapterwillfocusonenantiomersand,toalesserextent,
ondiastereomers.Thesignificanceofdiastereomerswillbecomeclearwhencarbohydratesarediscussedinchapter22.
 FIGURE17.9Relationshipsamongisomers.(Note:Thisdescriptionexcludesconformers(seep.688),whichcaninterconvert
withoutbreakingbonds.)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.2Enantiomerism
Aswehavelearnedabove,enantiomersarestereoisomersthatarenonsuperimposablemirrorimagesofeach
other.Exceptforinorganiccompoundsandafewsimpleorganiccompounds,thevastmajorityofmolecules
inthebiologicalworldshowenantiomerism,includingcarbohydrates(chapter22),lipids(chapter23),
aminoacidsandproteins(chapter24),andnucleicacids(chapter25).Further,approximatelyhalfofall
pharmaceuticalsshowenantiomerism.

Tounderstandthesignificanceofenantiomerism,recallthatenantiomershavesomedifferentproperties.
Whiletheyhavethesameboilingpoints,meltingpointsandsolubilities,eachofapairofenantiomersreacts
differentlytowardsotherchiralmolecules.Thisisespeciallyimportantinbiology.Forexample,oneformof
thalidomideactsinthebodytoproduceasedative/hypnoticeffectthatcontrolsthesymptomsofmorning
sickness,whereastheotherformactstoproducebirthdefects.

Asthestructureofthalidomideiscomplicated,wewillstartbylookingatasimplerexample.Infigure
17.10,differentatomsarepresentedasdifferentshapesandcolourstohelpusvisualiseandmentally
manipulatethemoleculesinthreedimensions.Infigure17.10,(a)isanatomwithfourdifferentgroups
attachedtoit.Wecanuseamirrortoproduce(b),itsmirrorimage.Imaginethatwecanlift(b)outofthe
mirror.Nomatterhowwetrytomove(b),wecannotsuperimposethetwomolecules.Becausetheyare
mirrorimagesandnonsuperimposable,theyareenantiomers.

FIGURE17.10Enantiomersaremirrorimagesofeachotherthatcannotbesuperimposed,nomatterhowwerotate
theoriginalmoleculeanditsmirrorimage.

Nowlet'slookatarealexample.Themoleculebutan2ol,anaturalbyproductoffermentationusedasa
flavouringagentandasasolventforpaints,hasfourdifferentgroupsbondedtoacentralcarbonatom.

Thestructuralformulaabovedoesnotshowtheshapeofbutan2olortheorientationofitsatomsinspace.
Let'slookatthemoleculeinthreedimensions:
Ontheleftisaballandstickmodelandontherightishowwedrawthethreedimensionallinestructure.

Nowlet'slookatthemirrorimageofthisstructure.Imagineifyoucouldsomehowlookintoboththemirror
worldandtherealworld.Thenyoucouldseeboththeoriginalmoleculeanditsmirrorimageasthree
dimensionalmolecules:

Ontheleftatthebottomofthepreviouspageiswhatwewillcalltheoriginalmolecule.Ontherightisthe
mirrorimage.Atfirstglance,theymaylookthesame:TheOHandCH3groupsonC(2)areintheplane
ofthepaper,theHisbehindtheplaneandtheCH2CH3groupisinfrontofit.

Thequestionis:Aretheythesame?

Imaginethatyoucanpickupthemirrorimageandmoveitinspaceinanywayyouwish.Ifyouholdthe
mirrorimagebytheCOHbondandrotatethebottompartofthemoleculeby180aroundthisbondas
shownbelow,theOHgroupretainsitspositioninspace,buttheCH3group,theCH2CH3groupand
theHatomarenowindifferentorientations.

Nomatterhowyoumovethemirrorimageinspace,youcannotfit(superimpose)itontheoriginalsothat
allbondsandatomsmatch.
Nomatterwhichwayyouorientthemolecule,aslongasnobondsarebrokenorrearranged,onlytwoofthe
fourgroupsbondedtothecentralcarbonatomofthemirrorimagecanbemadetocoincidewiththoseon
theoriginal.Themoleculesaremirrorimagesandnonsuperimposable.Recallthatwedescribesuchobjects
aschiralandsuchmoleculesasenantiomers.Likegloves,eachenantiomeralwayshasapartner
enantiomersoccurinpairswithonebeingthereflectionoftheother.

Notallmirrorimagesofmoleculesaredifferent.Ifwecanmovethemirrorimageinspaceandfindthatit
fitsovertheoriginalsothateverybond,atomanddetailofthemirrorimageexactlymatchesthebonds,
atomsanddetailsoftheoriginal,thenthetwoaresuperimposable.Thisisshowninfigure17.11:(a)isan
atomwithfourgroupsattachedtoit,andwecanuseamirrortoproduce(b),itsmirrorimage.Imaginethat
wecanlift(b)outofthemirror.Wecanseethatwecanindeedsuperimposethetwomolecules.Inthiscase,
themirrorimageandtheoriginalrepresentthesamemolecule.
 FIGURE17.11Superimposablemirrorimagesareexactlythesamemolecule.

Let'sconsideramoleculesuchaspropan2ol,whichhasacentralcarbonatombondedtofourgroups,two
ofwhicharethesame,aCH3group:

Thefollowingdiagramshowsathreedimensionalrepresentationofpropan2olontheleftanditsmirror
imageontheright:

Aswecanseebelow,themirrorimageofthismoleculeissuperimposableontheoriginal.

Ifamoleculeanditsmirrorimagearesuperimposable,thenthemoleculeanditsmirrorimageareidentical,
andthereisnopossibilityofenantiomerism.Recallthatwedescribesuchamoleculeasachiral(without
chirality).Itdoesnothavelefthandandrighthandversions.

Anyachiralobjectgenerallyhasatleastoneplaneofsymmetry.Aplaneofsymmetry(alsocalledamirror
plane)isanimaginaryplanepassingthroughanobjectanddividingitsothatonehalfoftheobjectisthe
reflectionoftheotherhalf.Thebeakershowninfigure17.12hasasingleplaneofsymmetry,whereasa
cube(figure17.12b)hasseveralplanesofsymmetry.Anexampleofamoleculewithasingleplaneof
symmetryispropan2ol(figure17.12c).

FIGURE17.12Planesofsymmetryin
(a)abeaker,
(b)acubeand
(c)propan2ol.Thebeakerandpropan2oleachhasoneplaneofsymmetrythecubehas
severalplanesofsymmetry,onlythreeofwhichareshowninthefigure(thediagonalsform
theotherplanesofsymmetry).

Stereocentres
Themostcommonbasisforenantiomerisminorganicmoleculesisthepresenceofacarbonatombondedto
fourdifferentgroups.Suchacarbonatomisanexampleofastereocentre.Astereocentreisthepartofa
moleculethatcanbeassembledintwodifferentwaystoformstereoisomers.

Inorganicmoleculescanalsoexhibitenantiomerism.Whereasthemajorityofexamplesofenantiomersin
organicchemistryarebasedonacarbonatombondedtofourdifferentgroups,ametalatomisoftenthe
stereocentreininorganicenantiomers.Inorganicenantiomersexhibitawidevarietyofgeometries.Aclassic
exampleofacoordinationcomplex(seechapter13)thatcanexistasenantiomersisthegoldenyellow
[Co(en)3]3+ion(figure17.13).
 FIGURE17.13Thestructuresof[Co(en)3 ]3+andethylenediamine,orethane1,2diamine(en).

[Co(en)3]3+comprisesacentral6coordinateCo 3+ionboundtothreebidentateethylenediamineligands.
Ethylenediamine,whichisalsoknownmorecorrectlyasethane1,2diamine,isgiventheabbreviationen.
Herethestereocentreisthecentralcobaltatom,withtheenantiomersarisingfromthetwodifferentwaysin
whichthethreeligandsarearrangedaroundit(figure17.14).(Noticethatthebidentateethylenediamine
liganditselfisachiral.)

FIGURE17.14Thetwoenantiomersof[Co(en)3 ]3+.Enantiomer2isconstructedasthemirrorimageofenantiomer
1.Nomatterhowenantiomer2isturned,itisnotsuperimposableonenantiomer1.

Similarly,enantiomerscanexistforcomplexesthatcontainonlytwoenligands,suchascis[Co(en)2Cl2]+
(figure17.15).

FIGURE17.15Isomersofthe[Co(en)Cl2 ]+ion.Themirrorimageofthetransisomer(notshown)canbe
superimposedexactlyontheoriginal,sothetransisomerisnotchiral.However,thecisisomer
(enantiomer1)ischiralbecauseitsmirrorimage(enantiomer2)cannotbesuperimposedonthe
original.

Enantiomerscanalsoexistforcomplexescontainingoneenligandanexampleofthisiscis[Co(en)
(NH3)2Cl2]+.

RepresentingEnantiomersofComplicatedOrganicMolecules
Itisimportantthatwecanclearlyrepresentthethreedimensionalstructuresofenantiomersonatwo
dimensionalpage.Thisisrelativelystraightforwardforsimplemoleculessuchasthosewehavealready
encounteredinthischapter,butitbecomesmorechallengingforcomplicatedmolecules.

Inourinitialdiscussionsofbutan2ol,weusedtherepresentationinfigure17.16atoshowthetetrahedral
geometryofthecentralcarbonatom(thestereocentre)init,twogroups(CH3andOH)areintheplane
ofthepaper,one(CH2CH3)iscomingoutoftheplanetowardsus,andone(H)isbehindtheplane,
awayfromus.

FIGURE17.16Fourrepresentationsofoneenantiomerofbutan2ol.

Infigure17.16,wecanturn(a)slightlyinspaceandtipitabittoplacethecarbonframeworkintheplane
ofthepaper.Doingsogivesusrepresentation(b),inwhichwestillhavetwogroupsintheplaneofthe
paper(CH3andCH2CH3),onecomingtowardsus(OH)andonegoingawayfromus(H).Foran
evenmoreabbreviatedrepresentationofthisenantiomerofbutan2ol,wecanturn(b)intothelinestructure
(c).Althoughwedon'tnormallyshowhydrogenatomsinalinestructure,wedoin(c)justtoremind
ourselvesthatthefourthgrouponthisstereocentreisreallythereandthatitisH.Finally,wecancarrythe
abbreviationastepfurtherandwritebutan2olas(d).Here,weomittheHonthestereocentre,butwe
knowthatitmustbethere(carbonneedsfourbonds),andweknowthatitmustbebehindtheplaneofthe
paper.Clearly,theabbreviatedrepresentations(c)and(d)aretheeasiesttodraw,especiallyforvery
complicatedstructures,andwewilltendtorelyontheseabbreviatedrepresentationsthroughoutthe
remainderofthetext.

Whenyouhavetowritethreedimensionalrepresentationsofstereocentres,trytokeepthecarbon
frameworkintheplaneofthepaperandtheothertwoatomsorgroupsofatomsonthestereocentretowards
andawayfromyou,respectively.Usingrepresentation(d)asamodel,wegetthefollowingtwodifferent
representationsofitsenantiomer:

Noticethattherighthandstructureisthemiddlestructurerotatedhorizontallyby180.

Whendrawingtheenantiomericpairsofmorecomplicatedstructures,youmayfinditusefultomapa
molecule'simageacrossanimaginarymirror,whichwecanrepresentbyaverticalline.Ifthemirror
reflectionisnotsuperimposable,itisadifferentmolecule(anenantiomer).Figure17.17showsthis
techniquefor4methylcyclopent2enone.
 FIGURE17.17Animaginarymirrorcanbeusedtomapamolecule'smirrorimage:inthiscase,4methylcyclopent
2enone.

Rotatingthemirrorimageby180bringsthedoublebondintheringintoalignmentwiththemoleculeon
theleft.However,noticethat,inthemoleculeontheleftofthemirror,themethylgroupsitsabovetheplane
ofthepagewhereasitliesbeneathintherotatedmoleculeontherightofthemirror.Similarly,thehydrogen
atom,whichisbelowtheplaneofthepageinthemoleculeontheleftofthemirrorisabovetheplaneinthe
rotatedmirrorimage.

Thereasonweneedasimplifiedwayofdrawingthreedimensionalstructuresbecomesapparentwhenwe
havetorepresentverycomplicatedorganicmoleculessuchasTaxol(figure17.18).

FIGURE17.18StructureoftheimportantanticancerdrugTaxolshowingthemanystereocentrespresentinthis
complicatedmolecule.

WORKEDEXAMPLE17.1

DrawingStereoisomers
Eachofthefollowingmoleculeshasonestereocentre.
(a)

(b)
Drawthreedimensionalrepresentationsoftheenantiomersofeachofthesemolecules.

Analysis

Youwillfindithelpfultostudythemodelsofeachpairofenantiomersandtoviewthemfrom
differentperspectives.Asyouworkwiththesemodels,noticethateachenantiomerhasacarbon
atombondedtofourdifferentgroups,whichmakesthemoleculechiral.

Youmayfindithelpfultousethemappingprocesstorepresenttheenantiomersinvolved.For
(b),thisprocessgives:

Solution

Thehydrogenatomatthestereocentreisshownin(a),butnotin(b).
(a)

(b)

PRACTICEEXERCISE17.1
Eachofthefollowingmoleculeshasone
stereocentre.
(a)
 (b)

Drawthreedimensionalrepresentationsofthe
enantiomersofeachofthesemolecules.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.3NamingStereocentres:TheR,SSystem
Becauseenantiomersaredifferentcompounds,eachmusthaveadifferentname.Theoverthecounter
drugibuprofen(ananalgesicsoldundervariousnamesincludingNurofen ,figure17.19),forexample,
showsenantiomerismandcanexistasthefollowingpairofenantiomers:

FIGURE17.19Ibuprofenisacommonlyusedanalgesic.

Onlyoneenantiomerofibuprofenhasatherapeuticeffect.Thisenantiomerreacheseffective
concentrationsinthehumanbodyinapproximately12minutes.However,inthiscase,theinactive
enantiomerisnotwasted.Thebodyslowlyconvertsittotheactiveenantiomer.

Weneedtobeabletoassignauniquenametoeachenantiomerofibuprofen(oranyotherpairof
enantiomers,forthatmatter).Todothis,chemistshavedevelopedtheR,Ssystemfororganicmolecules.
TheR,Ssystemisasetofrulesforspecifyingtheconfigurationaroundastereocentre.ThiscanbeanR
configurationoranSconfiguration.ThefirststepinassigninganRorSconfigurationistoarrangethe
groupsbondedtothestereocentreinorderofpriority.Forthis,weusethesamesetofpriorityruleswe
usedinsection16.3toassignanE,Zconfigurationtoanalkene.

ToassignanRorSconfiguration:
1.Locatethestereocentre,identifyitsfoursubstituents,andassignapriorityfrom1(highest)to4
(lowest)toeachsubstituent(asdescribedinsection16.3).
2.Orientthemoleculeinspacesothatthegroupoflowestpriority(4)isdirectedawayfromyou,as
thesteeringcolumnofacarwouldbe.Thethreegroupsofhigherpriority(13)thenproject
towardsyou,asthespokesofasteeringwheelwould.
3.Readthethreegroupsprojectingtowardsyouinorder,fromhighestpriority(1)tolowestpriority
(3).
 4.Ifreadingthegroupsproceedsinaclockwisedirection,theconfigurationisdesignatedR(from
theLatinwordrectusmeaningstraightorcorrect)ifreadingproceedsinananticlockwise
direction,theconfigurationisS(fromtheLatinwordsinistermeaningleft).Youcanalso
visualisethissituationasfollows:TurningthesteeringwheeltotherightequalsR,andturningit
totheleftequalsS.

NowletusassignRandSconfigurationstoourthreedimensionaldrawingsoftheenantiomersof
ibuprofen.Inorderofdecreasingpriority,thegroupsbondedtothestereocentreareCOOH>C6H4
>CH3>H.Intheenantiomerbelowontheleft,thesequenceofgroupsonthestereocentreinorder
ofpriorityoccursclockwise.Therefore,thisenantiomeris(R)ibuprofen,anditsmirrorimageis(S)
ibuprofen:

WORKEDEXAMPLE17.2

UsingtheR,SSystem
AssignanRorSconfigurationtothestereocentresinthefollowingmolecules.
(a)

(b)
Analysisandsolution

Vieweachmoleculethroughthestereocentreandalongthebondfromthestereocentre
towardsthegroupoflowestpriority.
(a)TheorderofpriorityisCl>CH2CH3>CH3>H.Thegroupoflowest
priority,H,pointsawayfromyou.Readingthegroupsintheorder1,2,3occursin
ananticlockwisedirection,sotheconfigurationisS.

(b)TheorderofpriorityisOH>CH CH>CH2CH2>H.Withhydrogen,
thegroupoflowestpriority,pointingawayfromyou,readingthegroupsintheorder
1,2,3occursinaclockwisedirection,sotheconfigurationisR.

PRACTICEEXERCISE17.2
AssignanRorSconfigurationtoeachofthe
followingstereocentres.
(a)
 (b)

(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.4MoleculeswithMoreThanOneStereocentre
Wehavenowseenseveralexamplesofmoleculeswithonestereocentreandverifiedthat,foreach,two
stereoisomers(onepairofenantiomers)arepossible.Nowletusconsidermoleculeswithmultiplestereo
centres.Togeneralise,foramoleculewithnstereocentres,themaximumpossiblenumberofstereoisomers
is2 n.Weknowthat,foramoleculewithonestereocentre,2 1=2stereoisomersarepossible.Foramolecule
withtwostereocentres,2 2=4stereoisomersarepossibleforamoleculewiththreestereocentres,2 3=8
stereoisomersarepossible,andsoon.However,itshouldbenotedthatsometimesthemaximumnumberof
stereoisomersisnotpossible,aswewillseeonp.758formesocompounds.

AcyclicMoleculeswithTwoStereocentres
Webeginourstudyofacyclicmoleculeswithtwostereocentresbyconsidering2,3,4trihydroxybutanal.
Thisaldehydecomprisesalinearsequenceoffourcarbonatomsandhastwostereocentres:thatis,two
carbonatomswithfourdifferentgroupsattached.Thetwostereocentres,atC(2)andC(3),aremarkedwith
asterisks:

Themaximumnumberofstereoisomerspossibleforthismoleculeis2 n=2 2=4,eachofwhichisdrawnin

figure17.20.Eachofthesemoleculeshasauniquename,andweusetheR,Ssystemtoassigna
configurationaroundeachofthestereocentres,C(2)andC(3).Weuseaspecialnotationtodescribethese
configurations.Forexample,2R(seefigure17.20).

FIGURE17.20Thefourstereoisomersof2,3,4trihydroxybutanal,acompoundwithtwostereocentres.

Stereoisomers(a)and(b)arenonsuperimposablemirrorimagesandare,therefore,apairofenantiomers.
Stereoisomers(c)and(d)arealsononsuperimposablemirrorimagesandrepresentasecondpairof
enantiomers.Wedescribethefourstereoisomersof2,3,4trihydroxybutanalbysayingthattheyconsistof
twopairsofenantiomers.Enantiomers(a)and(b)arenamederythrose,whichissynthesisedinerythrocytes
(redbloodcells)hencethename.Enantiomers(c)and(d)arenamedthreose.Erythroseandthreose
belongtotheclassofcompoundscalledcarbohydrates.

Wealsoneedtodefinetherelationshipbetween(a)and(c).Theyarestereoisomersbutarenotmirror
imagesofeachother.Asyouwillrecallfromp.747,wecallstereoisomersofthistypediastereomers.
Similarly,(a)and(d),(b)and(c),and(b)and(d)arepairsofdiastereomers.Diastereomersare
stereoisomersthatarenotenantiomersthatis,theyarestereoisomersthatarenotmirrorimagesofeach
other.Likeenantiomers,diastereomershavethesamesequenceofconnection.However,whileenantiomers
havemostlythesamephysicalproperties(meltingpoint,boilingpoint,densityetc.),diastereomerscanhave
completelydifferentproperties.Thisisveryevidentwithcarbohydrates,whichwewilltalkaboutinchapter
22.

WORKEDEXAMPLE17.3

EnantiomersandDiastereomers
Thefollowingarestereorepresentationsofthefourstereoisomersofbutane1,2,3triol.
i.

ii.

iii.

iv.

Configurationsaregivenforthestereocentresin(i)and(iv).
(a)Whichpairsofcompoundsareenantiomers?
(b)Whichpairsofcompoundsarediastereomers?

Analysisandsolution

(a)Enantiomersarestereoisomersthatarenonsuperimposablemirrorimages.Compounds(i)
and(iv)areonepairofenantiomers,andcompounds(ii)and(iii)areasecondpairof
enantiomers.Notethattheconfigurationsofthestereocentresin(i)aretheoppositeof
 thosein(iv),itsenantiomer.
(b)Diastereomersarestereoisomersthatarenotmirrorimages.Compounds(i)and(ii),(i)and
(iii),(ii)and(iv),and(iii)and(iv)arediastereomers.

PRACTICEEXERCISE17.3
Thefollowingarestereorepresentationsofthe
fourstereoisomersof3chlorobutan2ol.
i.

ii.

iii.

iv.

(a)Whichpairsofcompoundsare
enantiomers?
(b)Whichpairsofcompoundsare
diastereomers?

MesoCompounds
Certainmoleculeswithtwoormorestereocentresdonothaveasmanystereoisomersasyoumightexpect
fromthe2 nrule.Onesuchmoleculeis2,3dihydroxybutanedioicacid,morecommonlynamedtartaricacid.
Tartaricacidisacolourless,crystallinecompoundoccurringlargelyinplants,especiallyingrapes.The
structureoftartaricacidis:

C(2)andC(3)oftartaricacidarestereocentres,and,fromthe2 nrule,themaximumnumberofstereoisomers
youmightexpectis2 2=4.Figure17.21showsthetwopairsofmirrorimagesofthiscompound.Structures
(a)and(b)arenonsuperimposablemirrorimagesand,therefore,theyareapairofenantiomers.Structures
(c)and(d)arealsomirrorimages,buttheyaresuperimposableiftheyarerotatedtotheappropriate
orientation.Therefore,(c)and(d)arenotdifferentmoleculestheyarethesamemolecule,justoriented
differently.Because(c)anditsmirrorimage(d)aresuperimposable,theyarethesamemoleculeandachiral.
Thismeansthattheyareopticallyinactiveanddonotinteractwithplanepolarisedlight(seesection17.5for
moredetails).

FIGURE17.21Stereoisomersoftartaricacid,onepairofenantiomersandonemesocompound.Thepresenceof
aninternalplaneofsymmetryindicatesthatthemoleculeisachiral.

Recallfromp.751thatanymoleculewithaninternalplaneofsymmetrysuchthatonehalfisthereflection
oftheotherhalfisachiralanddoesnothaveenantiomers.Thus,eventhough(c)hastwostereocentres,itis
achiral.Itsplaneofsymmetryisshowninfigure17.21.Thestereoisomeroftartaricacidrepresentedby(c)
or(d)iscalledamesocompound,definedasanachiralcompoundwithtwoormorestereocentres.

Wecannowreturntotheoriginalquestion:Howmanystereoisomersarethereoftartaricacid?Theanswer
isthree:onemesocompoundandonepairofenantiomers.Notethatthemesocompoundisadiastereomer
ofeachoftheotherstereoisomers.

WORKEDEXAMPLE17.4

EnantiomersandmesoCompounds
Thefollowingarestereorepresentationsofthethreestereoisomersofbutane2,3diol.
i.
 ii.

iii.

(a)Whichpairofmoleculesareenantiomers?
(b)Whichisthemesocompound?

Solution
(a)Compounds(i)and(iii)areenantiomers.
(b)Compound(ii)isamesocompound.

PRACTICEEXERCISE17.4
ThefollowingarefourNewmanprojection
formulae(seesection16.2)oftartaricacid.
i.

ii.
 iii.

iv.

(a)Whichformulaerepresentthesame
compound?
(b)Whichformulaerepresentenantiomers?
(c)Whichformula(e)represent(s)meso
tartaricacid?

CyclicMoleculeswithTwoStereocentres
Inthissection,weconcentrateonderivativesofcyclopentaneandcyclohexanecontainingtwostereo
centres.Wecananalysechiralityinthesecycliccompoundsinthesamewaywedidforacycliccompounds.

DisubstitutedDerivativesofCyclopentane

Letusstartwith2methylcyclopentanol,acompoundwithtwostereocentres.Usingthe2 nrule,wepredicta
maximumof2 2=4stereoisomers.Boththecisisomerandthetransisomer(section16.2)arechiral,with
thecisisomerexistingasonepairofenantiomersandthetransisomerexistingasasecondpair:

Because1,2cyclopentanediolalsohastwostereocentres,the2 nrulepredictsamaximumof2 2=4

stereoisomers.However,asseeninthefollowingdiagram,onlythreestereoisomersexistforthiscompound:
Thecisisomerisachiral(meso)becauseitissuperimposableonitsmirrorimage.Toputitanotherway,the
cisisomerisachiralbecauseitpossessesaplaneofsymmetrythatbisectsthemoleculeintotwomirror
imagehalves.Thetransisomerischiralandexistsasapairofenantiomers.

WORKEDEXAMPLE17.5

Stereoisomersfor3methylcyclopentanol
Howmanystereoisomersarepossiblefor3methylcyclopentanol?

Analysisandsolution

Therearefourstereoisomersof3methylcyclopentanol,withthecisisomerexistingasonepairof
enantiomersandthetransisomerasasecondpair:

PRACTICEEXERCISE17.5
Howmanystereoisomersarepossiblefor1,3
cyclopentanediol?

DisubstitutedDerivativesofCyclohexane
Asanexampleofadisubstitutedcyclohexane,letusconsiderthemethylcyclohexanols.Firstly,4
methylcyclohexanolcanexistastwostereoisomersapairofcistransisomers.Boththecisandtrans
isomersaremesocompoundsandareachiral.Ineach,aplaneofsymmetryrunsthroughtheCH3and
OHgroupsandthetwoattachedcarbonatoms.

Similarly,3methylcyclohexanolcontainstwostereocentresandexistsas2 2=4stereoisomers,withthecis
isomerasonepairofenantiomersandthetransisomerasasecondpair:

Again,2methylcyclohexanolhastwostereocentresandexistsas2 2=4stereoisomers,withthecisisomeras
onepairofenantiomersandthetransisomerasasecondpair:

WORKEDEXAMPLE17.6

StereoisomersforCyclohexane1,3diol
Howmanystereoisomersexistforcyclohexane1,3diol?

Analysisandsolution

Accordingtothe2 nrule,cyclohexane1,3diolhastwostereocentres,soithasamaximumof2 2
=4stereoisomers.Thetransisomerofthiscompoundexistsasapairofenantiomers.Thecis
isomerhasaplaneofsymmetrysoisamesocompound.
 Therefore,althoughthe2 nrulepredictsamaximumoffourstereoisomersforcyclohexane1,3
diol,onlythreeexistonepairofenantiomersandonemesocompound.

PRACTICEEXERCISE17.6
Howmanystereoisomersexistfor
cyclohexane1,4diol?

MoleculeswithThreeorMoreStereocentres

The2 nruleappliesequallytomoleculeswiththreeormorestereocentres.Hereisadisubstituted
cyclohexanolwiththreestereocentres,eachmarkedwithanasterisk:
Thereisamaximumof2 3=8stereoisomerspossibleforthismolecule.Menthol,oneoftheeight,hasthe
configurationshownaboveontheright.Theconfigurationateachstereocentreisindicated.Mentholisthe
majorcomponentpresentinpeppermintandothermintoilsthatgivesthesetheircharacteristictaste.

Cholesterol,amorecomplicatedmolecule,haseightstereocentres:

Toidentifythestereocentres,remembertoaddanappropriatenumberofhydrogenatomstocompletethe
tetravalenceofeachcarbonatomyouthinkmightbeastereocentre.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.5OpticalActivity:DetectingChiralityinthe
Laboratory
Weindicatedintheprevioussectionthatonediastereomer(menthol)of2isopropyl5
methylcyclohexanolisprimarilyresponsiblefortheflavourofpeppermint.Diastereomershave
markedlydifferentproperties.Enantiomersalsohavedifferentproperties,butthedifferencesaremore
subtle.Ingeneral,enantiomershaveidenticalphysicalandchemicalproperties.Forinstance,theyhave
thesamemeltingpoint,thesameboilingpointandthesamesolubilitiesinwaterandothercommon
solvents.Theydodiffer,however,intheiropticalactivity(theabilitytorotateaplaneofpolarised
light).Thispropertyisparticularlyusefultochemistsasitallowsustodetectenantiomersinthe
laboratory.

Eachmemberofapairofenantiomersrotatesaplaneofpolarisedlightintheoppositedirection.To
understandhowopticalactivityisdetectedinthelaboratory,wemustfirstunderstandplanepolarised
lightandapolarimeter,theinstrumentusedtodetectopticalactivity.

PlanepolarisedLight
Ordinarylightconsistsofwavesoscillatinginallplanesperpendiculartoitsdirectionofpropagation
(shownontheleftsideoffigure17.22).Certainmaterials,suchascalciteandPolaroidsheet(aplastic
filmwithorientedcrystalsofanorganicsubstanceembeddedinit),selectivelytransmitlightwaves
vibratinginparallelplanes(shownontherightsideoffigure17.22).Electromagneticradiation
vibratingonlyinparallelplanesissaidtobeplanepolarised.

FIGURE17.22Theeffectofapolarisingfilteronlight.

Polarimeters
Apolarimeterconsistsofalightsource,apolarisingfilterandananalysingfilter(eachmadeofcalcite
orPolaroidfilm),andasampletube(figures17.23and17.24).Ifthesampletubeisempty,theintensity
oflightreachingthedetector(inthiscase,youreye)isatitsmaximumwhenthepolarisingaxesofthe
twofiltersareparallel.Iftheanalysingfilteristurnedeitherclockwiseoranticlockwise,lesslightis
transmitted.Whentheaxisoftheanalysingfilterisatrightanglestotheaxisofthepolarisingfilter,the
fieldofviewisdark.Thispositionoftheanalysingfilteristakentobe0ontheopticalscale.

FIGURE17.23Alightpolarimeter.

FIGURE17.24Polarisingfiltersareusedinliquidcrystaldisplays(LCD).

ThissameprincipleformsthebasisforhowimagesareproducedontheLCDscreensofsmartphones
andlaptops(seefigure17.24).

MeasuringtheRotationofPlanepolarisedLight
Theabilityofmoleculestorotateaplaneofpolarisedlightcanbeobservedwiththeuseofapolarimeter
inthefollowingway(seefigure17.25).First,asampletubefilledwithsolventisplacedinthe
polarimeter,andtheanalysingfilterisadjustedsothatnolightpassesthroughtotheobserverthatis,
thefilterissetto0.Thenweplaceasolutionofanopticallyactivecompoundinthesampletube.
Whenwedoso,wefindthatacertainamountoflightnowpassesthroughtheanalysingfilter.Wealso
findthattheplaneofpolarisedlightfromthepolarisingfilterhasbeenrotatedsothatitisnolongerat
anangleof90totheanalysingfilter.Wethenrotatetheanalysingfiltertorestoredarknessinthefield
ofview.Thenumberofdegrees,,throughwhichwemustrotatetheanalysingfiltertorestoredarkness
tothefieldofviewiscalledtheobservedrotation.Ifwemustturntheanalysingfiltertotheright
(clockwise)torestorethedarkfield,wesaythatthecompoundisdextrorotatory(fromtheLatinword
dextermeaningontherightside)ifwemustturnittotheleft(anticlockwise),wesaythatthe
compoundislevorotatory(fromtheLatinwordlaevusmeaningontheleftside).

FIGURE17.25Schematicdiagramofapolarimeterwithitssampletubecontainingasolutionofanoptically
activecompound.Theanalysingfilterwouldneedtobeturnedclockwisebydegreesto
restorethedarkfield.

Themagnitudeoftheobservedrotationforaparticularcompounddependsonitsconcentration,the
lengthofthesampletube,thetemperature,thesolventandthewavelengthofthelightused.The
specificrotation([])isdefinedastheobservedrotationataspecificcelllengthandsample
concentration:

Thestandardcelllengthis1decimetre(1dm=0.1m,seefigure17.26),althoughcellsofdifferent
lengthscanbeused.Theconcentrationofasampledissolvedinasolventisexpressedasgramsper
millilitreofsolution.Thetemperature(T,indegreesCelsius)andwavelength(,innanometres)oflight
aredesignated,respectively,assuperscriptandsubscript.Thelightsourcemostcommonlyusedin
polarimetryisthesocalledsodiumDline(=589nm),firstnamedbyGermanphysicistJosephvon
FraunhoferwhenheobservedthedarkbandsintheopticalspectrumoftheSun.Thesamelineis
responsiblefortheyellowcolourofsodiumvapourlampsseeninmanystreetlights(seeworked
example4.3onpp.11617).

FIGURE17.26A1dmpolarimetercell.
Inreportingeitherobservedorspecificrotation,itiscommontoindicateadextrorotatorycompound
withaplussigninparentheses,(+),andalevorotatorycompoundwithaminussigninparentheses,().
Foranypairofenantiomers,oneenantiomerisdextrorotatoryandtheotherislevorotatory.Foreach
pair,thevaluesofthespecificrotationareexactlythesame,butthesignsareopposite.Thefollowing
arethespecificrotationsoftheenantiomersofbutan2olat25C,observedwiththeDlineofsodium:

Youwillnoticeinthespecificrotationsforbutan2olthatSisthedextrorotatoryenantiomerandRis
thelevorotatoryenantiomer.TheRandSdesignationisnotrelatedtotheopticalactivitythatis,S
enantiomersmaybeeitherlevorotatoryordextrorotatory,andviceversa.

WORKEDEXAMPLE17.7

CalculatingSpecificRotation
Asolutionispreparedbydissolving4.00goftestosterone,amalesexhormone,in100mL
ofethanolandplacingitinasampletube1.00dminlength.Theobservedrotationofthis
sampleat25C,usingtheDlineofsodium,is+4.36.Calculatethespecificrotationof
testosterone.

Analysisandsolution

Theconcentrationoftestosteroneis4.00g/100mL=0.0400g/mL.Thelengthofthesample
tubeis1.00dm.Insertingthesevaluesintotheequationforcalculatingspecificrotation
gives:

PRACTICEEXERCISE17.7
Thespecificrotationofprogesterone,a
femalesexhormone,is+172,measuredat
20C.Calculatetheobservedrotationfora
solutionpreparedbydissolving4.00gof
progesteronein100mLofdioxaneand
placingitinasampletube1.00dmlong.

RacemicMixtures
Anequimolarmixtureoftwoenantiomersiscalledaracemicmixture,atermderivedfromthename
racemicacid(fromtheLatinwordracemusmeaningclusterofgrapes),originallygiventoan
equimolarmixtureoftheenantiomersoftartaricacid.Becausearacemicmixturecontainsequal
numbersofthedextrorotatoryandthelevorotatorymolecules,itsspecificrotationis0.Alternatively,we
saythataracemicmixtureisopticallyinactive.Aracemicmixtureisindicatedbyaddingtheprefix()
tothenameofthecompound.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.6ChiralityintheBiologicalWorld
Almostallthemoleculesinlivingsystems,bothplantandanimal,arechiral.Althoughthesechiral
moleculescanexistasanumberofstereoisomers,almostinvariablyonlyonestereoisomerisfoundin
nature.Ofcourse,instancesdooccurinwhichmorethanonestereoisomerisfound,buttheserarelyexist
togetherinthesamebiologicalsystem.

Perhapsthemostconspicuousexamplesofchiralityamongbiologicalmoleculesaretheenzymes,allof
whichhavemanystereocentres.Anexampleischymotrypsin,anenzymefoundintheintestinesofanimals
thatcatalysesthedigestionofproteins.Chymotrypsinhas251stereocentres.Themaximumpossible
numberofstereoisomersisthusstaggeringlylarge,almostbeyondcomprehension.Fortunately,naturedoes
notsquanderitspreciousenergyandresourcesunnecessarilyonlyoneofthesestereoisomersisproduced
andusedbyanygivenorganism.Becauseenzymesarechiralsubstances,mostproduceorreactonlywith
substancesthatmatchtheirstereochemicalrequirements.

HowanEnzymeDistinguishesBetweenEnantiomers
Foranenzymetocatalyseabiologicalreaction,themoleculeinvolvedmustfirstattachtoachiralbinding
siteontheenzyme'ssurface.Anenzymewithbindingsitesspecificforthreeofthefourgroupsona
stereocentrecandistinguishbetweenamoleculeanditsenantiomeroroneofitsdiastereomers.Let'slookat
figure17.27,whichisarepresentationofanenzymethatcatalysesareactionofglyceraldehyde.The
enzymehasthreesitesarrangedonitssurface:abindingsitespecificforH,asecondspecificsitefor
OHandathirdspecificsiteforCHO.Theenzymecandistinguish(R)(+)glyceraldehyde(thenatural,or
biologicallyactive,form)fromitsenantiomerbecausethenaturalenantiomercanbebound,withthree
groupsinteractingwiththeirappropriatebindingsitesfortheSenantiomer,onlytwogroupsatmostcan
interactwiththesebindingsites.

FIGURE17.27Aschematicdiagramofanenzymesurfacecapableofinteractingwith(R)(+)glyceraldehydeat
threebindingsites,butwith(S)()glyceraldehydeatonlytwoofthesesites.

Becauseinteractionsbetweenmoleculesinlivingsystemstakeplaceinachiralenvironment,weshould
expectthatamoleculeanditsenantiomeroroneofitsdiastereomerselicitdifferentphysiological
responses.Aswehavealreadyseen,(S)ibuprofenisactiveasapainandfeverreliever,whereasitsR
enantiomerisinactive.TheSenantiomerofthecloselyrelatedanalgesicnaproxenisalsotheactivepain
relievingformofthiscompound,butitsRenantiomerisalivertoxin!
ChemicalConnections

ChemistryandForensics

SomeofthemostpopularshowsonTVtodayinvolvescientistssolvingcrimesusingchemistry
skills.Crimestorieshavealwaysbeenpopularhowever,today'sforensicscientistshaveaccessto
toolsandtechniquesthatallowmodernscriptwriterstodevelopcomplexandwiderangingstory
linesfortheseshows,eveniftheyareoftenviewedasunrealisticbyactualforensicscientists.
However,even80yearsago,crimewriterswereusingtheirknowledgeofchemistrytoproduce
originalstories.Onesuchexampleisthe1930crimestoryTheDocumentsintheCasecowritten
byDorothyLSayersandRobertEuston.

Inpossiblythefirstexampleoftheinvolvementofrealisticforensicsciencetosolveawhodunit,a
murdererwasbroughttojusticethroughanunderstandingofchiralityinorganicchemistry.The
1930storybySayersandEustonconcernedGeorgeHarrison,founddeadinthekitchenofhis
smallcottageinthewoodscalledTheShack.BesideHarrison'sbodyweresomewildmushrooms,
whichitwasknownhewasfondofcollectingfromthewoods.Inthesubsequentinquest,the
HomeAnalyst,SirJamesLubbock,testifiedthatthecauseofdeathwaspoisoningbymuscarine,
theactiveprinciplefromthemushroomAmanitamuscaria(figure17.28),alargeamountofwhich
wasfoundinthestomachandvomitusofthevictim.SirJameshadnohesitationindeclaringtothe
coronerthatthedeatharosethroughaccidentalingestionofthepoisonduringthepreparationofa
mealinvolvingthemushrooms.ThejuryagreedandbroughtinaverdictofAccidentalDeathdue
topoisoningbyAmanitamuscaria.

FIGURE17.28Amanitamuscaria.

AndtherethematterwouldhaveendedexceptfortheeffortsofJohnBunting,afriendofthe
 AndtherethematterwouldhaveendedexceptfortheeffortsofJohnBunting,afriendofthe
deceased,whocouldnotbelievethatHarrisonwouldhavemistakenthemushroomforanedible
variety.Bunting'sinitialinvestigationswereallfruitlessuntilhetalkedtoanorganicchemist.In
doingso,hediscoveredthatlifehasakindofbiasalopsidednesssotospeak,anditis
sometimespossibletodistinguishbetweensyntheticsubstancesandthosederivedfromliving
organisms.Synthesisgenerallyproducestheracemate,thecombinedchiralformsofamolecule,
whereasthenaturalproductsareusuallyofoneformonly,singleenantiomers.Theorganic
chemisttoldBuntingthatasimplepolarimetermeasurementwouldconfirmthatthepoisoncame
fromthemushroomand,aftersomeeffort,BuntingwasabletoconvincetheHomeAnalystto
undertaketheanalysis.WhenLubbock'smeasurementshowednoopticalactivity,itwasclearthat
themuscarine(figure17.29)wasaracemicmixtureandthereforeofsyntheticorigin.Harrison's
deathmusthavebeenduetofoulplay.Subsequently,thesourceoftheracemicmixtureof
muscarinewastracedtoMrsHarrison'sloverwhopaidthefullpenaltyunderthelawdeathby
hanging.

FIGURE17.29 (a)Muscarineactivatesthenervoussystembymimickingacetylcholine.
(b)Acetylcholinethemessengermoleculeinvolvedinnerveimpulse
transmission.

Chiralityismuchmoreinvolvedwithsavinglivesthanendingthem,asmanymodernmedicines
aresoldasasingleenantiomer.Thechiraldrugindustrynowrepresentsclosetoonethirdofall
drugsalesworldwide.Singleenantiomerdrugsandintermediatesrepresentmorethan150billion
dollarsinsaleseachyear.AstraZenecaforinstancesoldover5.7billiondollarsworthofonedrug
alone(esomeprazole,usedtotreatulcers)inoneyear,makingitthethirdbiggestselling
pharmaceuticaldrugthatyear.Theindustry'sgrowthisrooted,inpart,inthechemistrybywhich
moleculesinteractwithbiologicalsystems.Biologicalmessengermoleculesandcellsurface
receptorsthatmedicinalchemiststrytoaffectormimicarechiral,sodrugmoleculesmustmatch
thisasymmetry.Thechiraldrugssynthesisedbythepharmaceuticalindustrytodayaregenerated
bysyntheticreactionsthatleadpredominantlytooneenantiomer,orbyspecialseparation
techniquesusedtoisolatetheenantiomers.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
17.7SynthesisingChiralDrugs
Manyoftoday'smedicinesinvolvechiralcompounds.Someofthese,suchasibuprofen(seep.754),aresoldas
amixtureofbothenantiomers.Others,however,mustbeenantiomericallypurebecauseonlyoneenantiomer
hasthedesiredtherapeuticeffect.Pharmaceuticalcompaniesapproachtheproductionofenantiomericallypure
medicinesintwowaystheycansynthesisearacemicmixtureofthedrugandthenseparatethetwoenantiomers
(resolution)ortheycancontrolthesyntheticconditionssothatonlyoneenantiomerisformed(asymmetric
synthesis).

Resolution
Resolutionistheseparationofamixtureintoitsindividualcomponents.Resolutionofenantiomersis,in
general,difficult,butseverallaboratorymethodscanbeused.Inthissection,weillustratejustone:theuseof
enzymesaschiralcatalysts.Theprincipleinvolvedinthismethodisthataparticularenzymewillcatalysea
reactionofachiralmolecule,butnotofitsenantiomer(seefigure17.27onp.764).

Theesteraseshavereceivedparticularattentioninthisregard.Thisclassofenzymecatalysesthehydrolysisof
esterstogiveanalcoholandacarboxylicacid.Figure17.30illustratestheresolutionof(R,S)naproxen.The
ethylestersofboth(R)and(S)naproxenaresolidswithverylowsolubilitiesinwater.Chemistsuseanesterase
inalkalinesolutiontoselectivelyhydrolysethe(S)ester,whichgoesintoaqueoussolutionasthesodiumsaltof
the(S)carboxylicacid.The(R)esterisunaffectedbytheseconditions.Filteringthealkalinesolutionrecovers
thecrystalsofthe(R)ester.Afterthecrystalsareremoved,thealkalinesolutionisacidifiedtoprecipitatepure
(S)naproxen.Therecovered(R)estercanberacemised(convertedtoanR,Smixture)andtreatedagainwiththe
esterase.Byrecyclingthe(R)ester,theracemicesterisconvertedto(S)naproxen.
 FIGURE17.30Theresolutionof(R,S)naproxen.

Thesodiumsaltof(S)naproxenistheactiveingredientinmanyoverthecounternonsteroidalanti
inflammatorydrugs(NSAIDs).The(S)enantiomerismuchmoreeffectivethanthe(R)enantiomer,andmore
importantlythe(R)enantiomerhassignificantlivertoxicitysomustnotbepresentinthedrug.

Removingthe(R)enantiomerofnaproxentoprovideenantiomericallypure(S)naproxenmakesthisauseful
andeffectivedrug,butthisisnotthecaseforallsingleenantiomers.Forexample,resolutionoftheenantiomers
ofthalidomidewouldstillresultinadrugwithunwantedsideeffectsbecausethebodyisabletoconvertone
enantiomertotheother.

AsymmetricSynthesis
Inorganicstereoisomersareessentialfortheindustrialsynthesisofsomeimportantchiraldrugs.In2001the
NobelPrizeinchemistrywasawardedtochemistsWilliamKnowles,RyojiNoyoriandBarrySharplesswho
developedchiralinorganiccatalyststhat,forthefirsttime,enabledthepracticalsynthesisofchirallypure
compoundsusedtomakemedicines,suchasLDOPA,fortreatmentofParkinson'sdisease,andnaproxen,the
structuresofwhichareshownbelow.

Asymmetricsynthesisisthenamechemistsgivetoproceduresthatgiverisetopredominantlyoneenantiomer.
Efficientasymmetricsynthesisiscrucial,particularlyforcompaniesthatmakepharmaceuticals.Thefirst
commercialisedcatalyticasymmetricsynthesisusingachiraltransitionmetalcomplexasthecatalystwasthe
productionofLDOPAfromanonchiralaromaticalkene.Thisreactionhasbeenincommercialusesince1974
andisnowknownastheMonsantoprocess(figure17.31)afterthenameofthecompanythatdevelopedit.The
commercialsuccessofthesynthesisofLDOPAstimulatedthesubsequentdevelopmentandapplicationofother
catalyticasymmetricreactions.
 FIGURE17.31TheMonsantoprocessfortheproductionofL DOPA,whichisusedtotreatParkinson'sdisease.

Aswellasbeingproducedbyresolutionasdiscussedpreviously,(S)naproxencanalsobesynthesised
industriallyusingspecialcatalystswithchiralligands.Thisasymmetricsynthesis(figure17.32)usesthechiral
BINAPcomplex.Thisclean,simpleandeconomicalapproachmaybeappliedonanyscalefrom<100mgto
>100kg.BINAPcatalysedasymmetricsynthesesareappliedtotheindustrialproductionofmedicinal
compoundsinquantitiesofwellover100tonnesayear.Thisapproachhasbeenusedtodeveloparangeof
pharmaceuticals,agrochemicals,flavoursandfragrances.

FIGURE17.32Thecommercialasymmetricsynthesisoftheantiinflammatorydrugnaproxen(soldasNaprogesicin
AustraliaandNewZealand).

Becauseasymmetricsynthesisisdifficult,evenforrelativelysmallmolecules,thecompletesynthesisofcomplex
organicmoleculessuchastheimportantcancerfightingdrugTaxol(seep.753)providesatremendous
challenge.ChemistsproduceTaxolbystartingwithasimplercompoundfoundinnatureandthenmakingafew,
lessdemanding,asymmetrictransformationstoachievethedesiredmaterial.

Asymmetricsynthesisallowsustocreatenewmedicinesandcompoundswithspecificbiologicaleffects.
Achievingstereochemicalcontroloversyntheticreactions,however,isoneofthegreatestchallengesfacing
chemiststoday.Tomastersuchchallengingmethodology,wemustfirstlearnaboutthekeyfunctionalgroups,
theirpropertiesandhowtheyreactthiswillbecoveredinthefollowingchapters.

ChemistryResearch

WheredidChiralityComeFrom?

TheBigBangisthecurrentlyacceptedscientificexplanationfortheformationoftheuniverse.Thebest
estimatesputtheageoftheuniverseatbetween13and14billionyears,whiletheEarthisthoughttobe
about4.5billionyearsold.ThesimplemoleculespresentonEarthinitsinfancyhavegraduallyevolved
overthistimetogiveextraordinarilycomplexmolecules,suchasDNA,whicharethebasisoflifeaswe
 knowit.

OneintriguingunansweredquestionisWhydomanymoleculesinbiologicalsystemsexistasonlyone
oftwopossibleenantiomers?Forexample,aswewillseeinchapter24,the19chiralaminoacids,the
buildingblocksofproteins,existnearlyexclusivelyasasingleenantiomerinbiologicalsystems.This
mustmeanthat,somewhereoverthepast4.5billionyears,naturedevelopedapreferenceforoneofthe
twoenantiomers.Oneofthemanyhypothesesforthisbiomolecularhomochiralityisthattheremight
beatinyenergydifferencebetweenthem.Thisrunssomewhatcountertooureverydayexperiencewith
chiralmolecules,as,whentwoenantiomersofthesamemoleculeareplacedinanachiralenvironment,
theyappeartobehavechemicallyandphysicallyidentically.Therefore,ifanysuchenergydifference
doesexist,itmustbeabsolutelytiny.

ProfessorPeterSchwerdtfegerofMasseyUniversity(NewZealand)iscurrentlysearchingforchiral
moleculesthatexhibitenergydifferencesbetweentheirenantiomers(figure17.33),andheisusing
highlevelcomputationalchemistryashisprimarytechnique.Calculationshaveshownthatveryheavy
moleculesaremuchmorelikelytoexhibitsuchbehaviour.Therefore,hisresearchconcentrateson
calculatingtheenergiesofthetwoenantiomersofchiralmoleculescontainingveryheavyatomssuch
asthirdrowtransitionmetalsandactinideelements.Thisintroducessignificantdifficultiesintothe
calculations,asthetimerequiredisproportionaltoatleastn 3,wherenisthenumberofelectronsinthe
system,andthereforesupercomputersarerequiredtocompletetheseinareasonabletime.

FIGURE17.33Sophisticatedcalculationsonthechiralmolecule[(C5 H5 )Re(CO)(NO)I]suggestthatthere
maybeasmallenergydifferenceof300Hz(=1010 kJmol1 )betweenthetwoenantiomers.
Suchadifferenceshouldbedetectablewiththecorrectinstruments.

Oncethecalculationsarecomplete,thecandidatemoleculesmustbepreparedandtechniquesfoundto
determinethesmallenergydifferencesexpected.ProfessorSchwerdtfegeriscollaboratingwithagroup
inFrancetousevibrationalspectroscopyasapossibleenergyprobe,whileothergroupsaroundthe
worldareproposingtouseNMRspectroscopy.Regardlessofthetechniqueused,theobservationofan
energydifferencebetweenenantiomerswillbeamassivescientificachievementandwillforceusto
changethewaywethinkaboutchirality.Thecalculationsdosuggestthatsuchanenergydifference
exists,sotheraceison!

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Stereoisomers
Isomersaremoleculeswiththesamemolecularformulabutdifferentstructures.Constitutionalisomers
areisomerswithdifferentsequencesofatomconnectivity.Stereoisomershavethesameorderof
attachmentofatoms,butadifferentthreedimensionalorientationoftheiratomsinspace.Achiral
objectisonethatisnotsuperimposableonitsmirrorimage.Enantiomersarestereoisomersthatare
chiral.Anachiralobjectisthesameasitsmirrorimage.Diastereomersarestereoisomersthatarenot
superimposableandarenotmirrorimages.

Enantiomerism
Mostbiologicalmoleculesareenantiomeric.Enantiomershavethesamephysicalandchemical
propertiesbuteachofapairreactsdifferentlywithotherchiralmolecules.Aplaneofsymmetryisan
imaginaryplanepassingthroughanobject,dividingitsuchthatonehalfisthereflectionoftheother
half.Objectswithplanesofsymmetryareachiral.Astereocentreisthepartofamoleculethatcanbe
assembledintwodifferentwaystogeneratestereoisomers.Themostcommontypeofstereocentre
amongorganiccompoundsisatetrahedralcarbonatomwithfourdifferentgroupsbondedtoit.
Inorganicmoleculescanalsohavestereocentresand,therefore,enantiomersanddiastereomers.

Namingstereocentres:TheR,SSystem
TheconfigurationatastereocentrecanbespecifiedbytheR,Ssystem.Toapplythisnamingsystem,(1)
eachatomorgroupofatomsbondedtothestereocentreisassignedapriorityandisnumberedfrom
highestprioritytolowestpriority,(2)themoleculeisorientedinspacesothatthegroupoflowest
priorityisdirectedawayfromtheobserver,(3)theremainingthreegroupsarereadinorder,from
highestprioritytolowestpriority,and(4)ifthesequenceofthegroupsisclockwise,theconfigurationis
R,ifanticlockwise,theconfigurationisS.

MoleculeswithMoreThanOneStereocentre
Foramoleculewithnstereocentres,themaximumpossiblenumberofstereoisomersis2 n.Aplaneof
symmetryinamoleculereducesthenumberofstereoisomerstofewerthanthatpredictedbythe2 nrule.
Amesocompoundcontainstwoormorestereocentresassembledsothatitsmoleculesareachiral.

OpticalActivity:DetectingChiralityintheLaboratory
Enantiomersdifferintheiropticalactivitythatis,theirabilitytorotateaplaneofpolarisedlight.
Planepolarisedlightoscillatesonlyinparallelplanes.Apolarimeterisaninstrumentusedtodetectand
measurethemagnitudeofopticalactivity.Observedrotationisthenumberofdegreesaplaneof
polarisedlightisrotated.Specificrotationistheobservedrotationmeasuredwithacell1dmlong.
Levorotatorycompoundsrotateaplaneofpolarisedlightanticlockwise.Dextrorotatorycompounds
rotateaplaneofpolarisedlightclockwise.Aracemicmixtureisamixtureofequalamountsoftwo
enantiomersandhasaspecificrotationof0.

ChiralityintheBiologicalWorld
Chiralityisveryimportantinbiology.Almostallthemoleculesinlivingsystems,bothplantandanimal,
arechiral.Enzymescatalysebiologicalreactionsforonespecificenantiomer.Eachenantiomerofadrug
canhavedifferentbiologicalactivity.

SynthesisingChiralDrugs
Enantiomericallypuredrugscanbeproducedviatwoapproaches:aracemicmixtureofthedrugcanbe
separatedinaprocesscalledresolution,orthesyntheticconditionscanbecontrolledsothatonlyone
enantiomerisformed.Onemeansofresolutionistotreattheracemicmixturewithanenzymethat
catalysesaspecificreactionofoneenantiomerbutnottheother.Chiralinorganiccatalystscanbeuseful
toolsinasymmetricsynthesistocontrolreactionssothatonlyoneenantiomerisformed.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
TheR,Ssystem(section17.3)
Orientingmoleculeswiththelowestprioritybondawayfromthepointofviewandprioritisingthethree
remaininggroupsgivesaclockwise(R)orananticlockwise(S)sequence.

The2nrule(section17.4)
Foramoleculewithnstereocentres,therewillbeatmost2nstereoisomers.

Specificrotationformulaforenantiomers(section17.5)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Stereoisomers
17.1Definethetermstereoisomer.
17.2Howareconstitutionalisomersdifferentfromstereoisomers?Howaretheythesame?
17.3Whichoftheseobjectsarechiral?(Assumethatthereisnolabelorotheridentifyingmark.)
(a)pairofscissors

(b)tennisball

(c)paperclip

(d)bulldogclip

(e)beaker

(f) screw
17.4Considerthehelicalcoilofatelephonecordorthespiralbindingonanotebook.Ifyouviewthe
spiralfromoneendandfindthatithasalefthanded(anticlockwise)twist,doesthespiralhavea
righthanded(clockwise)oralefthandedtwistwhenviewedfromtheotherend?
17.5Nexttimeyouhavetheopportunitytoviewacollectionofconeshellsorotherseashellswitha
helicaltwist,studythechiralityoftheirtwists.Doyoufindanequalnumberoflefthandedand
righthandedshellsor,forexample,dotheyallhavethesamehandedness?

Mediancrosssectionthroughtheshellofachamberednautilusfoundinthedeepwatersofthe
PacificOcean.Theshellshowshandednessthiscrosssectionisarighthandedspiral.
17.6Whenyounexthaveanopportunitytoexamineanyoftheseeminglyendlessvarietiesofspiral
pasta,lookhowtheyaretwistedtoformaspiral.Dopiecesofanyonekindofpastaalltwistinthe
samedirection?(Thatis,dotheyallhavearighthandedtwistoralefthandedtwist,oraretheya
mixture,possiblyevenaracemicmixture?)
Enantiomerism
17.7Statewhethereachofthefollowingstatementsistrue.
(a)Allenantiomersarechiral.
(b)Adiastereomerofachiralmoleculemustalsobechiral.
(c)Amoleculewithaninternalplaneofsymmetrycanneverbechiral.
(d)Allachiralmoleculeshaveenantiomers.
(e)Allachiralmoleculeshavediastereomers.
(f) Allchiralmoleculeshaveenantiomers.
(g)Allchiralmoleculeshavediastereomers.
17.8Whichofthefollowingcompoundscontainstereocentres?
(a)2chloropentane
(b)3chloropentane
(c)3chloropent1ene
(d)1,2dichloropropane
17.9Drawtheenantiomerofeachofthefollowingmolecules.
(a)
(b)

(c)

(d)

(e)

(f)

(g)

(h)

(i)

(j)

(k)
 (l)

17.10Closelyexaminethefollowingfourmetalcomplexes.Whichofthesecomplexesarechiral
thatis,hasanenantiomer?Drawtheseenantiomers.
(a)

(b)

(c)

(d)
17.11Drawthetwoenantiomersofthecomplex[Co(C O ) ]3,whichhasthreebidentateoxalate
2 43
ligands(seechapter13,p.547).
17.12Markeachstereocentreinthefollowingmoleculeswithanasterisk.(Note:Notallcontain
stereocentres.)
(a)

(b)

(c)

(d)

17.13Markeachstereocentreinthefollowingmoleculeswithanasterisk.(Note:Notallcontain
stereocentres.)
(a)

(b)
 (c)

(d)

NamingStereocentres:theR,SSystem
17.14WhichofthefollowingmoleculeshaveanRconfiguration?
(a)

(b)

(c)

(d)

17.15Assignprioritiestothegroupsineachofthefollowingsets.
(a)H,CH3,OH,CH2OH
(b)CH2CH CH2,CH CH2CH3,CH2COOH
(c) CH ,H,COO,+NH
3 3
(d)CH ,CH SH,+NH ,COO
3 2 3
MoleculeswithMoreThanOneStereocentre
17.16WritethestructuralformulaofanalcoholwithamolecularformulaC6H14Othatcontainstwo
stereocentres.
17.17Forcenturies,ChineseherbalmedicinehasusedextractsofEphedrasinicatotreatasthma.
Investigationofthisplantresultedintheisolationofephedrine,apotentdilatoroftheair
passagesofthelungs.Thenaturallyoccurringstereoisomerislevorotatoryandhasthefollowing
structure:
 AssignanRorSconfigurationtoeachstereocentre.
17.18AtorvastatinissoldunderthetradenameLipitorandisusedforloweringcholesterol.Annual
globalsalesofthiscompoundexceed$13billion.Assignaconfigurationtoeachchiralitycentre
inatorvastatin.

17.19Labeleachstereocentreinthefollowingmoleculeswithanasterisk.
(a)

(b)

(c)

(d)

(e)
 (f)

(g)

(h)

Howmanystereoisomersarepossibleforeachmolecule?
17.20Identifythenumberofstereoisomersexpectedforeachofthefollowing.
(a)

(b)

(c)

(d)
 (e)

(f)

17.21Labelwithasterisksthefourstereocentresinamoxicillin,whichbelongstothefamilyof
semisyntheticpenicillins.

17.22Inthemorestablechairconformationofglucose,allgroupsonthe6memberedringare
equatorial:

(a)Identifyallstereocentresinthismolecule.
(b)Howmanystereoisomersarepossible?
(c)Howmanypairsofenantiomersarepossible?
(d)Whatistheconfiguration(RorS)atC(1)andC(5)inthestereoisomershown?
OpticalActivity:DetectingChiralityintheLaboratory
17.23Whatisaracemicmixture?Isaracemicmixtureopticallyactive(i.e.willitrotateaplaneof
polarisedlight)?
17.24Thespecificrotationofnaturallyoccurringephedrine,showninquestion17.17,is41.Whatis
thespecificrotationofitsenantiomer?
ChiralityintheBiologicalWorld
17.25Insectsuseparticularorganicmoleculescalledpheromonesassignalstoattractmates.Asan
example,thepinesawflyspeciesNeodiprionandDiprionuseanesterderivativeof3,7
 dimethylpentadecan2olasasexpheromone:

(a)Howmanydifferentstereoisomersexistforthismolecule?
(b)Thestereoisomershownproducesmuchofthepheromoneactivityofthismolecule.
UsingtheR,Snamingsystem,givethecorrectnameforthismolecule.
(c)(c)Interestingly,thestereoisomershownmustbemixedwithprecisely0.1%ofthe
(2S,3R,7S)diastereomerformaximumactivity.Drawthestructureofthiskey(2S,3R,7S)
isomer.
SynthesisingChiralDrugs
17.26Whatarethetwoapproachestoachievingenantiomericallypurecompounds?
17.27Whyisitnecessaryforsomedrugstoberesolvedintotheirseparateenantiomers?
17.28Ibuprofenissoldasa()racemicmixture.Whyisitnotnecessarytoresolvethismixtureintothe
pureenantiomers?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
17.29Onereasonwecanbesurethatsp 3hybridisedcarbonatomsaretetrahedralisthenumberof
stereoisomersthatcanexistfordifferentorganiccompounds.
(a)HowmanystereoisomersarepossibleforCHCl3,CH2Cl2andCHBrClFifthefouratoms
bondedtothecarbonatomhaveatetrahedralarrangement?
(b)Howmanystereoisomersarepossibleforeachofthecompoundsifthefouratoms
bondedtothecarbonatomhaveasquareplanararrangement?
17.30UsingonlyC,HandO,writestructuralformulaeforthelowestmolarmasschiralmoleculeof
eachofthefollowingclassesofcompounds.
(a)alkane
(b)alcohol
(c)aldehyde
(d)ketone
(e)carboxylicacid
17.31WhichalcoholswiththemolecularformulaC5H12Oarechiral?
17.32WhichcarboxylicacidswiththemolecularformulaC6H12O2arechiral?
17.33Markeachstereocentreinthefollowingmoleculeswithanasterisk.(Note:Notallcontain
stereocentres.)
(a)

(b)

(c)

(d)

(e)

(f)
 (g)

17.34Thefollowingareeightstereorepresentationsoflacticacid.
(a)

(b)

(c)

(d)

(e)

(f)

(g)
 (h)

Take(a)asthereferencestructure.Whichstereorepresentationsareidenticalto(a)andwhichare
mirrorimagesof(a)?
17.35Thefollowingarestructuralformulaefortheenantiomersofcarvone.

Eachenantiomerhasadistinctiveodourcharacteristicofitssource.AssignanRorS
configurationtothestereocentreineach.Howcantheyhavesuchdifferentpropertieswhenthey
aresosimilarinstructure?
17.36Thefollowingisastaggeredconformationofoneofthestereoisomersofbutan2ol.

(a)Isthis(R)butan2olor(S)butan2ol?
(b)DrawaNewmanprojectionforthisstaggeredconformation,viewedalongthebond
betweenC(2)andC(3).
(c)DrawaNewmanprojectionforonemorestaggeredconformationofthismolecule.Which
ofyourconformationsisthemorestable?AssumethattheOHandCH3groupsare
comparableinsize.
17.37Labelallstereocentresinloratadine(Claritin inNewZealandorClaratyneinAustralia)and
fexofenadine(Telfast),nowthetopsellingantihistaminesinAustraliaandNewZealand.
(a)

(b)
 Howmanystereoisomersarepossibleforeachcompound?
17.38Thefollowingarestructuralformulaeforthreeofthemostwidelyprescribeddrugsusedtotreat
depression.
(a)

(b)

(c)
 Labelallstereocentresineachcompound,andstatethenumberofstereoisomerspossiblefor
each.
17.39Triamcinoloneacetonide,theactiveingredientinAzmacortinhalers,isasteroidusedtotreat
bronchialasthma.

(a)Labeltheeightstereocentresinthismolecule.
(b)Howmanystereoisomersarepossibleforthemolecule?(Onlyonestereoisomeristhe
activeingredientinAzmacort.)
17.40Howmanystereoisomersarepossiblefor1,2cyclobutanediol?
17.41Howmanystereoisomersarepossiblefor1,3cyclobutanediol?
17.42Howmanystereoisomersarepossiblefor1,2cyclopentanediol?
17.43Howmanystereoisomersarepossiblefor1ethyl2methylcyclobutane?
17.44Howmanystereoisomersarepossiblefor1ethyl3methylcyclobutane?
17.45Howmanystereoisomersarepossibleforeachofthefollowingcompounds?
(a)

(b)
 (c)

(d)

17.46Whichofthefollowingstructuralformulaerepresentmesocompounds?
(a)

(b)

(c)

(d)
 (e)

(f)

17.47DrawaNewmanprojection,viewedalongthebondbetweenC(2)andC(3),forboththemost
stableandtheleaststableconformationsofmesotartaricacid:

17.48Howmanystereoisomersarepossiblefor1,3dimethylcyclopentane?Whicharepairsof
enantiomers?Whicharemesocompounds?
17.49Asdescribedinquestion17.24,ephedrineisopticallyactiveandrotatesaplaneofpolarisedlight
41anticlockwise.Whichofthefollowingcompoundswouldrotateplanepolarisedlight41ina
clockwisedirection?

(a)

(b)

(c)
 (d)

(e)

17.50Thenaturalproduct(R)glyceraldehydeshownbelowhasaspecificrotation,[]Dat25C,of
+13.5whenmeasuredinaqueoussolution.Whenasamplefromthelaboratorywasmeasured,
theobservedrotationwas+9.4.
(a)Usetheformulaforcalculatingtheopticalactivityofenantiomerstodeterminethe
concentrationof(R)glyceraldehydeusedinthismeasurement.
(b)Whatwouldbetheobservedopticalactivityofthiscompoundiftheconcentrationusedin
themeasurementwashalved?
(c)Whatwouldbethevaluemeasuredifthemixturecontainedhalftheoriginal
concentrationof(R)glyceraldehydeandthesameamountof(S)glyceraldehyde?

17.51The(S)enantiomerofthefollowingmoleculeis(+)carvone,whichisextractedfromtheoilof
carawayseeds:

The(R)enantiomeris()carvone,anditisisolatedfromtheoilofspearmint.Drawthecorrect
molecularstructuresforthesemolecules.Ifthespecificrotationofapuresampleofcarvonewas
 measuredas+62.5at20C,whichenantiomerofcarvonewasmeasuredinthepolarimeter?
17.52Atropine,extractedfromtheplantAtropabelladonna,hasbeenusedinthetreatmentof
bradycardia(lowheartrate)andcardiacarrest.Drawtheenantiomerofatropine.

17.53(R)limoneneisfoundinmanycitrusfruits,includingorangesandlemons.

Foreachofthefollowingcompounds,identifywhetheritis(R)limoneneoritsenantiomer,(S)
limonene.
(a)

(b)

(c)
 (d)

17.54Drawallpossiblestereoisomersofhex4en2ol.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
17.55Statewhethereachofthefollowingstatementsistrueformolecules(i)and(ii).
i.

ii.

(a)Molecules(i)and(ii)arethesame.
(b)Molecules(i)and(ii)arediastereomersofeachother.
(c)Gentleheatingofmolecule(i)convertsittomolecule(ii),sothesecompoundsare
thermalisomers.
(d)Bothmolecules(i)and(ii)havecyclicimidefunctionalgroupssocannothave
enantiomericisomers.
(e)Molecule(i)wouldrotateaplaneofpolarisedlightintheoppositedirectiontomolecule
(ii).
17.56Predicttheproduct(s)ofthefollowingreactions(wheremorethanonestereoisomerispossible,
showeachstereoisomer).
(a)

(b)

17.57Whichalkene,(a)or(b),whentreatedwithH2/Pdwillensureahighyieldofthefollowing
stereoisomer,cisdecalin.
 (a)

(b)

17.58Whichofthefollowingreactionswillyieldaracemicmixtureofproducts?
(a)

(b)

(c)

(d)

17.59Drawallthestereoisomersthatcanbeformedinthefollowingreaction.Commentonhowuseful
thisparticularreactionwouldbeasasyntheticmethod.

17.60Explainwhytheproductofthefollowingreactiondoesnotrotateplanepolarisedlight.
17.61Usingonlyethylenediamine(en=H2NCH2CH2NH2)andbromideanionsasligands,constructa
cationicoctahedralcomplexofcobalt(III)yourcomplexcationshouldhaveachargeof+1and
itshouldbechiral.Drawathreedimensionalstructureforthiscoordinationcomplex.Thendraw
thestructureofadiastereomerofthiscomplex.
17.62Drawallpossiblestereoisomersof[CoCl (en)(NH ) ]+.Whichofthesestereoisomersarechiral?
2 32
(en=H2NCH2CH2NH2)
17.63Itispossibleforacompoundtobechiraleventhoughitlacksacarbonatomwithfourdifferent
groups.Forexample,considerthestructureofthefollowingcompound,whichbelongstothe
classofcompoundscalledallenes.Thisalleneischiral.Drawitsenantiomer,andexplainwhy
thiscompoundischiral.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
achiral levorotatory R,Ssystem
asymmetricsynthesis mesocompound racemicmixture
chiral observedrotation resolution
constitutionalisomers opticalactivity S
dextrorotatory planeofsymmetry specificrotation[]
diastereomers planepolarised stereocentre
enantiomers polarimeter stereoisomers
isomers R

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

18 Haloalkanes
Haloalkanesarecompoundsthatcontainahalogenatomcovalentlybondedtoansp 3
hybridisedcarbonatom.Thecarbonhalogenbondcanbeverystrong,especiallyfor
fluorine,andthepropertiesthathalogenatomsimpartonthemoleculecanbeveryuseful.As
anindicationofthis,almostonefifthofalldrugscontainfluorine,andhaloalkanesarealso
usedasflameretardants,infireextinguishersandasrefrigerantsandsolvents.Whilethese
applicationsarisefromthelowreactivityofhaloalkanes,undertherightchemicalconditions
haloalkanescanbeconvertedtoalcohols,ethers,thiols,aminesandalkenes,andsotheyare
veryversatilemolecules.Indeed,haloalkanesareoftenusedasstartingmaterialsforthe
synthesisofmanyusefulcompoundsfoundinallwalksoflife,includingmedicine,food
chemistryandagriculture.Forexample,startingwiththehaloalkane1,2dichloroethane,we
canproducepolyvinylchloride(thediagrambelowisarepresentationofonemoleculeof
vinylchloride,orchloroethene).Polyvinylchlorideisoneofthemainsubstancesthatmake
uptheCDsandDVDsinyourmusic,softwareorvideogamecollection.

Understandinghowhaloalkanesaretransformedallowsgreatcontroloverthetransformation
ofsimplemoleculesintomorevaluableproducts.Inthischapter,westudytwocharacteristic
reactionsofhaloalkanes:nucleophilicsubstitutionandelimination.
 KEYTOPICS

18.1Haloalkanes
18.2Nucleophilicsubstitution
18.3elimination
18.4Substitutionversuselimination

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18.1Haloalkanes
Haloalkanesarecompoundscontainingahalogenatomcovalentlybondedtoansp 3hybridisedcarbonatom.The
generalsymbolforahaloalkaneisRX,whereXmaybeF,Cl,BrorI:

Ofallthehaloalkanes,thechlorofluorocarbons(CFCs)manufacturedunderthetradenameFreon arethemostwidely
known.CFCsarenontoxic,nonflammable,noncorrosiveandodourless.Originally,theyseemedtobeideal
replacementsforthehazardouscompounds,suchasammoniaandsulfurdioxide,formerlyusedinrefrigeration
systems.AmongtheCFCsmostwidelyusedforthispurposeweretrichlorofluoromethane(CCl3F,Freon11)and
dichlorodifluoromethane(CCl2F2,Freon12).TheCFCsalsofoundwideuseasindustrialcleaningsolvents.In
addition,theywereemployedaspropellantsinaerosolsprayssuchassprayondeodorantsandspraypaint(figure
18.1).However,itwastheorisedasearlyas1974thatCFCswereresponsiblefordamagingthestratosphericozone
layer.TheozonelayershieldstheEarthfromshortwavelengthultravioletradiationfromtheSun.Itwasthoughtthat
anincreaseinthisradiationwouldincreasetheincidenceofskincancer,aswellashavingahostofpotentially
catastrophicenvironmentaleffects.By1987,themembersoftheUnitedNationshadagreedtophaseouttheuseof
CFCs.Hydrochlorofluorocarbons(HFCs)arenowusedasareplacementforCFCsinmanyapplications,including
airconditioners,refrigeratorsandportablefireextinguishers.HFCshavemuchlesspotentialtodepletetheozonelayer,
buttheiruseisalsobeingphasedout.

FIGURE18.1In1989,AustraliabannedtheuseofCFCsinaerosolcans.NewZealandstoppedtheirusein1990.

Nomenclature
IUPACnamesforhaloalkanesarederivedbynamingtheparentalkaneaccordingtotherulesgiveninsection2.3.
Locateandnumbertheparentchainfromthedirectionthatgivesthesubstituentencounteredfirstthelower
number.
Showhalogensubstituentsbytheprefixesfluoro,chloro,bromoandiodo,andlisttheminalphabeticalorder,
alongwithothersubstituents.
Useanumberprecedingthenameofthehalogentolocateeachhalogenontheparentchain.
Inmoleculescontainingfunctionalgroupsdesignatedbyasuffix(suchasolforalcohols,alforaldehydes,onefor
ketonesandoicacidforcarboxylicacids),thefunctionalgroupstakeprecedenceinthenomenclature.Thelocationof
thefunctionalgroupindicatedbythesuffixthendeterminesthenumbering,andthehalogenissimplyclassedasa
substituentakintoanalkylsidechain.

Inhaloalkenes,thelocationofthedoublebonddeterminesthenumberingoftheparenthydrocarbonagain,the
halogenisclassedasasubstituent.

Commonnamesofhaloalkanesconsistofthecommonnameofthealkylgroup,followedbythenameofthehalideas
aseparateword.Hence,thetermalkylhalideisacommonnameforthisclassofcompounds.Inthefollowing
examples,theIUPACnameofthecompoundisgivenfirst,followedbyitscommonnameinparentheses.

Methanemayhaveoneormorehydrogenatomsreplacedbyhalogenatoms.Halogenatedmethanescontainingmore
thanonehalogenatomareusefulsolventsandaregenerallyreferredtobytheircommonnames.Dichloromethane
(methylenechloride)isthemostwidelyusedhaloalkanesolvent(seefigure18.2).CompoundsofthetypeCHX3are
calledhaloforms.ThecommonnameforCHCl3,forexample,ischloroform.ThecommonnameforCH3CCl3is
methylchloroform.
 FIGURE18.2Methylchloroformandtrichloroethenearesolventsusedforcommercialdrycleaning.

WORKEDEXAMPLE18.1

NamingHaloalkanes
WritetheIUPACnameforeachofthefollowingcompounds.
(a)

(b)

(c)

Analysisandsolution
(a)Thelongestcontinuouscarbonchainhasthreecarbonatoms.Therearenofunctionalgroupsapart
fromthehalogen,sothecorrectsolutioninvolvesnumberingthesethreecarbonatomstogivethe
carbonatombondedtothebromineatomthelowestnumber:inthiscase,1.Consequently,the
methylsubstituentisonthesecondcarbonatomofthechain.TheIUPACnameis1bromo2
methylpropane.Itscommonnameisisobutylbromide.
(b)Thereisanalkenefunctionalgrouppresent,andthisisindicatedbyusingthesuffixene.Thefirst
stepinvolvesfindingthelongestcarbonchainthatincludesthedoublebond.Thenwenumberthis
chainsothatthefirstcarbonatomofthedoublebondhasthelowestpossiblenumber.
 Wethenprioritisethegroupspresentonthealkene.OfthegroupsboundtoC(3),bromoethylhas
priorityovermethyl(seetheCIPrulesinchapter16onp.706).OnC(2),themethylgrouphas
priorityoverthehydrogenatom,whichispresentbutnotshown.Thetwoprioritygroupsareon
oppositesidesofthedoublebond,andthisisdesignatedE.Therefore,theIUPACnameis(E)4
bromo3methylpent2ene.NotethatC(4)isastereocentrebut,astheconfigurationisnotshown,
wecannotdesignateitaseitherRorS.
(c)Therearenofunctionalgroupsapartfromthehalogenwenumberthesixcarbonatomspresentso
thatthebromineatomisonC(2).Inthiscase,C(2)isastereocentreandtherearetwopossiblethree
dimensionalstructures.Recallfromchapter17thatwehavetoprioritisethegroupspresentonthis
chiralcarbonatom.Thebromineatom,whichhasthehighestatomicnumber,hasthehighest
priority,followedbyC(3),C(1)andthehydrogenatom.Viewedwiththishydrogenatomdirected
awayfromtheeye,theprioritygroupsarearrangedinananticlockwisesequenceandthemolecule
isgiventhedesignationS.Therefore,theIUPACnameis(S)2bromohexane.

Isouranswerreasonable?

Rememberthat,whenanalkeneispresent,therecanbetwowaysofconstructingamolecule,sothename
mustincludeadescriptortospecifywhichisomerisinvolved.Therearetwowaysofrepresentingthe
groupsonastereocentreandthenamemustdescribethespecificisomerpresent.

PRACTICEEXERCISE18.1
WritetheIUPACnameforeachofthefollowing
compounds.
(a)

(b)

(c)

(d)

SynthesisofHaloalkanes
Welearnedinchapter16thatalkanesaredescribedasbeingunfunctionalisedbecauseoftheirveryunreactivenature.
Alkanespossessonlystrongbonds.Furthermore,astheelectronegativitiesofcarbonandhydrogenaresosimilar,
theelectronsthataresharedinthesebondsareevenlydistributed.Thismeansthattherearenoregionsofincreased
partialchargeinalkaneswithoutsuchdipoles,neithernucleophilesnorelectrophilesareattracted.Thislackof
reactivityledearlychemiststoclassifyalkanesasparaffinsaftertheLatintermparumaffinis,whichmeanslittle
affinity.Alkanescanreactunderextremeconditionsinchapter16wedescribedhowcompleteoxidationofalkanes
generatesheat,CO2andwater.Inthischapterwewilllearnhow,againunderextremereactionconditions,alkanescan
bepushedtoundergoareactioncalledhalogenation.Halogenationdescribesareactionwheresomeofthehydrogen
atomsinalkanesaresubstitutedbyhalogenatoms,mostcommonlychlorineorbromine.

ChlorinationandBromination
Ifchlorine,Cl2,andmethanegas,CH4,aremixedtogetheratroomtemperatureintheabsenceofstronglight,no
reactionoccurs.However,ifthetwogasesareheatedtoahightemperature,oriftheyareexposedtoanintenselight
source,areactionbeginsandheatisliberated.Aswellasunreactedchlorineandmethanegas,twonewsubstancescan
bedetected:chloromethaneandhydrogenchloride.Ifthereactionisallowedtoprogressfurtherwithmorechlorine
gasbeingadded,chloromethaneitselfbeginstoreactandamixtureofdichloromethane,CH2Cl2,trichloromethane,
CHCl3(alsoknownaschloroform),andtetrachloromethane,CCl4(alsoknownascarbontetrachloride),isgenerated.

Thestrongconditionsrequiredforthereactionmakeitdifficulttocontrol,andonlybyusingaverylargeexcessof
alkaneorhalogencanthereactionbelimitedtoasinglesubstitutionproduct.

Themechanismbywhichthesubstitutionreactionoccursiswellunderstoodanditoccursinthreestages:initiation,
propagationandtermination.Wewillillustratethisprocessforthemonochlorinationofmethanementionedabove:

Initiation
Thefirststageinvolvesbreakingabondinachlorinemoleculeasaresultofhightemperatureorabsorptionoflight.
Thisbondcleavageoccursevenly(homolytically)togivetwochlorineatoms,2Cl,eachwithanunpairedelectronin
itsoutershell.

Suchoddnumberedelectronspeciesarecalledradicals(orfreeradicals)andtheoverallreactiontogivethe
chlorinatedalkaneisdefinedasaradicalsubstitutionreaction.

Propagation
Thesecondstageinvolvesformationoftheproductandregenerationoftheradical.Theinitiallyformedchlorine
radicalsareextraordinarilyreactiveandcanremove(orabstract)hydrogenatomsfromothermoleculestoreacquire
thestable,filled,outerelectronshell.Inthiscase,thechlorineatomradicalreactswithmethanetogiverisetoHCl.
(Weusesingleheadedarrowsratherthandoubleheadedarrowstoindicatethatthemovementofonlyoneelectronis
involved.)Theotherproductofthereactionisalsoaradical,inthiscase,amethylradical,CH3,anditisreactive
enoughtoabstractachlorineatomfromCl2.This,inturn,producesanotherradical,andsoon.Wecallthissequence
ofevents,wheretheproductofonestepisthereactantinthenextstep,achainreaction.

Inthismanner,thegenerationofonlyafewradicalsintheinitialhomolyticstagegivesrisetoasubstantialnumberof
reactionswiththealkane,CH4,and,consequently,conversiontothehaloalkane,CH3Cl.

Termination
Thereactionisstoppedwhentworadicalsencountereachothertoproducenonradicalspecies.Notethat,becausethe
concentrationofradicalsgeneratedatanyonetimeissolow,thechancesoftworadicalsencounteringeachotherare
muchlowerthanthatofaradicalencounteringanalkanemolecule.

Brominecanalsoundergothisradicalsubstitutionreaction.Forexample,brominecanreactwithethanetogenerate
bromoethaneand,ifthereactionisnotcontrolled,dibromoethaneandtribromoethane.

Whilethissubstitutionreactioncanoccurfortheotherhalogensaswell,itisgenerallyusedonlywithchlorineor
bromineforanumberofpurelypracticalreasons.Fluorine,F2,reactswithalkanesundertheseconditions,butthe
reactionsarehighlyexothermic(reflectingthestrengthoftheCFbond)andsoareverydifficulttocontrol.Iodine,
I2,ontheotherhandisseldomusedbecausethereactionisendothermicandtoomuchenergyisrequiredtoinitiatethe
reaction,makingitdifficulttocontrol.

WhenanalkanewithdifferenttypesofCHbondsisreactedwithahalogenundertheseconditions,allofthe
possiblesubstitutionproductsmaybedetected.Forinstance,reacting2methylbutanewithchlorineat300Cgivesthe
followingmixtureoffourproducts:

Thisisnotastatisticaldistribution.AstherearenineCHbondsthatarepartofCH3groups,twoCHbondsfrom
CH2groupsandonlyoneCHbondonthetertiarycarbonatom,thestatisticaldistributionwouldbe75%,
16.7%and8.3%.ClearlysometypesofCHbondsaremoresusceptibletoreactionthanothers.Theproductsofthe
reactionaredeterminedbothbythenumbersofCHbondsandbythestabilityoftheradicalsthatwouldbeformed
bytheabstraction.Forthischlorinationreaction,a3hydrogenatomisabout4timesmorelikelytobesubstitutedthan
a1CH,anda2CHisabout2.5timesmorelikelytobesubstitutedthana1CH.Thisarisesfromthe
differentstabilityoftheradicalsgeneratedbytheabstraction.ThehalogenatomradicalsClandBrhavedifferent
reactivities,butthedifferentstabilitiesofthecarboncentredradicalsthatmaybeformedalsoinfluencethereaction
outcome.Themorestabletheradical,themoreeasilyitisformed.Thisisbecausethestabilityoftheradicalis
reflectedinthestabilityofthetransitionstateleadingtoitsformation.Therefore,itiseasiertoremoveahydrogenatom
froma2carbonatomtogeneratea2radicalthanitistoremoveahydrogenatomfroma1carbonatomtoproduce
a1radical.Tertiaryradicalsaremorestablethan2radicals.Otherradicals,especiallysomethatinvolveheteroatoms
suchasthosederivedfromphenols,areevenmorestableandareimportantantioxidantsusedtointerruptthedamage
thatmorereactiveradicalscangenerate.

WORKEDEXAMPLE18.2

DeterminingtheProductsofRadicalSubstitutionReactions
GivethestructuresandIUPACnamesoftheproductsofthefollowingradicalsubstitutionreactions
(ignoringstereochemistryandassumingmonosubstitution).
(a)

(b)

(c)

Analysisandsolution
(a)Thecompoundtobereactedwithbromineiscalled2methylpropane.ThereareonlytwotypesofC
Hbondspresentinthiscompound.Thereisasingle3CHpresent,andtherestofthehydrogen
atomsarepartofmethylgroups.Thismeansthatonlytwopossiblemonosubstitutedhaloalkanescan
arise.

(b)Thecompoundtobereactedwithchlorineiscalledcyclohexane.Asthemoleculeisflexible(only
onemonosubstitutionproductispossible,andnostereochemistryissuesareinvolved),weconsider
thatthereisonlyonetypeofCHbondpresent,sotheproductofmonosubstitutionwithchlorine
wouldbecalledchlorocyclohexane.
(c)Thecompoundtobereactedwithbromineiscalled2,2dimethylbutane,andtherearethreepositions
wherehydrogencanbesubstitutedbybromine.
 Isouranswerreasonable?

Rememberthatsinglebondsareallfreelyrotatable,soallthreeCH3groupsboundtoasinglecarbonatom
areequivalent.Underthestrongconditionsusedforhalogenationofalkanes,allpossiblehydrogenatoms
canbesubstituted.Thepresenceofhalogensinanalkaneisindicatedbyaddingtheprefixchloroor
bromototheparentalkanename.Thepositionnumbersshouldbechosentogivethesmallesttotal.

PRACTICEEXERCISE18.2
GivethestructuresandwritetheIUPACnamesforallofthe
possibleproductsofthefollowingsubstitutionreactions(ignoring
stereochemistryandassumingmonosubstitution).
(a)

(b)

(c)

(d)

PrincipalReactionsofHaloalkanes
Haloalkanesareusefulinthesynthesisofmorecomplicatedorganicmolecules.Thisisbecausethepolarisedcarbon
halogenbondisreadilyattackedbyspecieswithanegativecharacter.Suchspeciesarecallednucleophiles(which
literallymeansattractedtothenucleus).Anucleophileis,infact,anyreagentwithanunsharedpairofelectronsthat
canbedonatedtoanotheratomoriontoformanewcovalentbondnucleophileisanothernameforaLewisbase.
Nucleophilicsubstitutionisanyreactioninwhichonenucleophileissubstitutedforanother.Inthefollowinggeneral
equation, isthenucleophile,Xistheleavinggroup,andsubstitutiontakesplaceonansp 3hybridisedcarbon
atom.

Halideions,withafilledouterelectronshellequivalenttothenoblegases,makeexcellentleavinggroups,which
explainsthevalueofhaloalkanesforthesynthesisofothermolecules.

Theprocessofnucleophilicsubstitutionisevidentfromthenameanatomorgroupisreplaced(substituted)by
another.Thisisnotsoclearwithelimination,whereatomsorgroupsareremovedfromtwoadjacentcarbonatoms.
Forexample,HandXcouldberemovedfromahaloalkane,orHandOHfromanalcohol,togiveacarboncarbon
doublebondinbothcases.

Becauseallnucleophilesarealsobases,nucleophilicsubstitutionandbasecatalysedeliminationarecompeting
reactions.(Thedegreetowhicheachoccursisgovernedbysubtlevariationsinstructureandreactionconditionsyou
mayencountermoreonthistopicinlatercourses.)Theethoxideion,CH3CH2O,forexample,isbothanucleophile
andabase.Withbromocyclohexane,itreactsasanucleophile(pathwayshowninred)togiveethoxycyclohexane
(cyclohexylethylether)andasabase(pathwayshowninblue)togivecyclohexeneandethanol.

Inthischapter,westudybothoftheseorganicreactions.Usingthem,wecanconverthaloalkanestocompoundswith
otherfunctionalgroupsincludingalcohols,ethers,thiols,sulfides,amines,nitriles,alkenesandalkynes.Molecules
withthesefunctionalgroupsareimportantasmedicines,industrialchemicalsandmodernmaterials.Anunderstanding
ofthenucleophilicsubstitutionandeliminationreactionsofhaloalkanesenableschemiststocreatesomeofthe
complexorganicmoleculesweuseinourmodernsociety.

ChemicalConnections

FightingFireAntswithHaloalkanes

Untilrecently,organochlorinecompoundswereusedworldwideasinsecticides.Theyarepartofagroupof
substancesreferredtoaspersistentorganicpollutants(orPOPs),andmanypeoplehaveconcernsabouttheir
environmentalimpact.Althoughthesecompoundsaregenerallyharmlesstohumans,thisconcernlargely
arisesfromtheirpersistencetheyremainunchangedintheenvironmentsolongthattheyhavebeen
detectedinthebreastmilkofwomenlivinginthearctictundrathousandsofkilometresawayfromany
applicationtocontrolinsects.Apartfromtheirinsecticidalaction,organochlorineshavelittlechemical
reactivitysotheyarenoteasilydegradedandcanbedetectedinsoildecadesafterapplication.

OrganochlorineswereusedwidelyinAustralia,especiallyasinsecticides(mostcommonlyDDT,heptachlor
(figure18.3),chlordane(figure18.4),dieldrin,aldrinandlindane(figure18.5).Dieldrinwasusedfortreating
cropstocontrolrootflylarvae,locusts,cricketsandgrasshoppersinbuildingandindustrytocontroltermites
andtocontroldiseasevectorssuchascockroaches,fleasandmosquitolarvae.Theuseofdieldrinwasbanned
in1994.Heptachlorwasusedasasoiltreatmenttocontrolantsandgrubsinsugarcane,bananaweevilborer
(Cosmopolitessordidus)inbananaplantationsandtermitesinbuildingsandotherstructures.Agriculturaluse
ofheptachlorceasedin1987,butitwasstillusedfortermitecontrolinQueenslanduntil1995.Lindanehas
similarapplicationstodieldrinandheptachlorand,althoughitsusewasquicklybannedinallotherstatesof
Australia,itwasstillusedinQueenslandtocontrolwhitegrubsandsymphylidsonpineapplesuntil2010.

FIGURE18.3Heptachlor(bannedinmostcountries,includingAustraliaandNewZealand).

FIGURE18.4Chlordane.

FIGURE18.5Lindane.

Althoughthereismountingevidenceontheenvironmentalimpactoforganochlorines,itisimportantto
understandthat,onbalance,theseinsecticideshaveplayedverybeneficialrolesforhumanity.Reductionin
malariadeathsduetomosquitocontrolisjustonemajorimpactofthesecompounds.Althoughchemistsare
nowdevelopingotherinsecticidestoreplacethebannedorganochlorines,thesecompoundsstillrepresentour
mostpowerfulweaponsforcontrollinginsects.Thisisevidentfromtheirrecentlimitedapprovalforusein
NorthernTerritoryandQueenslandinattemptstoeradicatetheimportedredfireant(figure18.6),whichwas
discoveredinBrisbaneinearly2001andsubsequentlyinVictoriaandotherplacesincludingAuckland.
 FIGURE18.6Aredfireant.

Queensland'sDepartmentofPrimaryIndustriesandFisheriesdescribedfireants(Solenopsisinvicta)asthe
greatestecologicalthreattoAustralia'senvironmentsincetheintroductionoftherabbit.Fireantsarea
recognisedproblemintheUSAwheretheyhaveamultibilliondollarimpactontheeconomy.Fireantsinflict
apainfulstingthatoftencausestheskintoblister(figure18.7).Theblisteringiscausedbytheantsusingtheir
jawstogripthefleshwhileinjectingatoxincalledsolenopsinA(figure18.8).

FIGURE18.7Fireantbites.
 FIGURE18.8 ThestructureofsolenopsinA,thevenomoftheimportedredfireantrepresentedas
(a)aballandstickmodeland
(b)asacondensedlinestructure.

Despitesomepeople'sconcernsabouttheirenvironmentalpersistence,governmentshavejudgedthat
applicationofthesepowerfulhaloalkaneinsecticidesiswarrantedtoprotectAustralianandNewZealandflora
andfaunafromsuchimportedpests.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
18.2NucleophilicSubstitution
Nucleophilicsubstitutionisoneofthemostimportantreactionsofhaloalkanesandcanleadtoawidevarietyof
newfunctionalgroups,severalofwhichareillustratedintable18.1.
TABLE18.1 Somenucleophilicsubstitutionreactions

Nucleophile Product Classofcompoundformed

alcohol

ether

thiol(mercaptan)

sulfide(thioether)

alkyliodide

CH3NH3+ alkylammoniumion

alcohol(afterprotontransfer)

ether(afterprotontransfer)

Notethefollowingpointsfromtable18.1.
1.Whilethesymbol isusedtorepresentanynucleophile,notallnucleophilesarenegativelycharged.
2.Ifthenucleophileisnegativelycharged,asforOHandRS,theatomdonatingthepairofelectronsinthe
substitutionreactionbecomesneutralintheproduct.
3.Ifthenucleophileisuncharged,asforNH3andCH3OH,theatomdonatingthepairofelectronsinthe
substitutionreactionbecomespositivelychargedintheproduct.Often,theproductthenundergoesasecond
stepinvolvingprotontransfertoyieldaneutralsubstitutionproduct.

WORKEDEXAMPLE18.3

Determiningtheproductsofnucleophilicsubstitution
Completethefollowingnucleophilicsubstitutionreactions.
(a)

(b)

Analysisandsolution

Thenucleophileattacksthehaloalkaneandahalideion,X,isejected.(a)Hydroxideionisthe
nucleophileandbromineistheleavinggroup:
 (a)

(b)Ammoniaisthenucleophileandchlorineistheleavinggroup:

Isouranswerreasonable?

Checkthestructurestobesureeachatomhasthecorrectvalencythatis,theyareboundtothe
appropriatenumberofgroupsandhavechargesasrequired.

PRACTICEEXERCISE18.3
Completethefollowingnucleophilicsubstitution
reactions.
(a)

(b)

MechanismsofNucleophilicSubstitution
Onthebasisofdecadesofexperimentalobservations,chemistshaveproposedtwocontrollingmechanismsfor
nucleophilicsubstitutions.Afundamentaldifferencebetweenthemisthetimingofbondbreakingbetweencarbon
andtheleavinggroupandofbondformingbetweencarbonandthenucleophile.

SN2Mechanism

Atoneextreme,bondbreakingandbondformingoccursimultaneously.Thus,thedepartureoftheleavinggroup
isassistedbytheincomingnucleophile.ThismechanismisdesignatedSN2,whereSstandsforsubstitution,Nfor
nucleophilicand2forabimolecularreaction.Abimolecularreactionisoneinwhichtwospeciesareinvolvedin
thetransitionstateoftheratedeterminingstep.Thistypeofsubstitutionreactionisclassifiedasbimolecular
becauseboththehaloalkaneandthenucleophileareinvolvedintheratedeterminingstepandcontributetothe
ratelawofthereaction:

Figure18.9showstheSN2mechanismforthereactionofahydroxideionandbromomethanetoformmethanol
andabromideion.Thenucleophileattacksthereactivecentrefromthesideoppositetheleavinggroup,asshown
inthefigurebelow.Youcanseethat,forachiralcompound,anSN2reactionatastereocentregivesrisetoachiral
product.Thisoccurswithinversionoftheconfigurationaroundthestereocentre.

FIGURE18.9TheSN2reactionisdrivenbytheattractionbetweenthenegativechargeofthenucleophile(inthiscase,the
negativelychargedoxygenatomofthehydroxideion)andthecentreofpositivechargeoftheelectrophile
(inthiscase,thepartialpositivechargeonthecarbonatombearingthebromineleavinggroup).

Figure18.10showsanenergydiagramforanSN2reaction.Thereisasingletransitionstateandnoreactive
intermediate.
 FIGURE18.10AnenergydiagramforanSN2reaction.Thereisonetransitionstateandnoreactiveintermediate.

SN1Mechanism

Intheotherlimitingmechanism,calledSN1,bondbreakingbetweencarbonandtheleavinggroupiscompleted
beforebondformingwiththenucleophilebegins.InthedesignationSN1,Sstandsforsubstitution,Nfor
nucleophilicand1foraunimolecularreaction.Aunimolecularreactionisoneinwhichonlyonespeciesis
involvedinthetransitionstateoftheratedeterminingstep.Thistypeofsubstitutionisunimolecularbecauseonly
thehaloalkaneisinvolvedintheratedeterminingstepandcontributestotheratelaw:

TheSN1mechanismisillustratedbythereactionof2bromo2methylpropane(tertbutylbromide)inmethanol,
CH3OH,toform2methoxy2methylpropane(tertbutylmethylether).Thisisanexampleofasolvolysisreaction
areactioninwhichthesolventplaystheroleofthenucleophileinthesubstitutionreaction.
Step1:TheionisationofaCXbondformsa3carbocationintermediate:

Step2:Reactionofmethanolateitherfaceoftheplanarcarbocationintermediategivesanoxoniumion:

Step3:Protontransferfromtheoxoniumiontomethanol(thesolvent)completesthereactionandgivestert
butylmethylether:

Figure18.11showsanenergydiagramfortheSN1reactionof2bromo2methylpropaneandmethanol.Thereis
onetransitionstateleadingtoformationofthecarbocationintermediateinstep1andasecondtransitionstatefor
thereactionofthecarbocationintermediatewithmethanolinstep2togivetheoxoniumion.Thereactionleading
toformationofthecarbocationintermediatehasthehigherenergybarrier(Ea1),soitistheratedeterminingstep.
Recallthatyouhavepreviouslyencounteredthistypeofenergydiagraminchapter15(p.653).
 FIGURE18.11AnenergydiagramfortheSN1reactionof2bromo2methylpropaneandmethanol.Thereisone
transitionstateleadingtoformationofthecarbocationintermediateinstep1andasecondtransitionstate
forthereactionofthecarbocationintermediatewithmethanolinstep2.Step1crossesthehigherenergy
barrierandsoisratedetermining.

IfanSN1reactioniscarriedoutatatetrahedralstereocentre,theproductisaracemicmixture(seechapter17).We
canillustratethisresultwiththefollowingexample.Uponionisation,theRenantiomerformsanachiral
carbocationintermediate.AttackbythenucleophilefromtheleftfaceofthecarbocationintermediategivestheS
enantiomerattackfromtherightfacegivestheRenantiomer.Becauseattackbythenucleophileoccurswithequal
probabilityfromeitherfaceoftheplanarcarbocationintermediate,theRandSenantiomersareformedinequal
amounts,andtheproductisaracemicmixture.

ExperimentalEvidenceforSN1andSN2Mechanisms

Letusnowexaminesomeoftheexperimentalevidenceonwhichthesetwocontrastingmechanismsarebased.As
wedo,weconsiderthefollowingquestions:
1.Whateffectdoesthenatureofthenucleophilehaveontherateofreaction?
2.Whateffectdoesthestructureofthehaloalkanehaveontherateofreaction?
3.Whateffectdoesthestructureoftheleavinggrouphaveontherateofreaction?
4.Whatistheroleofthesolvent?
NatureoftheNucleophile
Nucleophilicityisakineticproperty,whichwemeasurebyrelativeratesofreaction.Wecanestablishtherelative
nucleophilicitiesforaseriesofnucleophilesbymeasuringtherateatwhicheachdisplacesaleavinggroupfroma
haloalkaneunderdefinedconditions.Forexample,wecouldmeasuretherateatwhichvariousnucleophiles
displacebromidefrombromoethaneinethanolat25C.Thefollowingequationshowsthisreactionwith
ammonia,NH3,asthenucleophile:

Comparingtherateofreactionofbromoethaneunderthesedefinedconditionswiththenucleophileslistedintable
18.2allowsustodefinetheirrelativenucleophilicity.Themoreeffectivenucleophilesarethosethatreactmore
rapidly.Thenucleophilesintable18.2arethosewedealwithmostcommonlyinthistext.
TABLE18.2 Examplesofcommonnucleophilesandtheirrelativeeffectiveness

BecausethenucleophileparticipatesintheratedeterminingstepinanSN2reaction,thebetterthenucleophile,the
morelikelyitisthatthereactionwilloccurbythatmechanism.Thenucleophiledoesnotparticipateintherate
determiningstepinanSN1reaction.Thus,anSN1reactioncan,inprinciple,occuratapproximatelythesamerate
withanyofthecommonnucleophiles,regardlessoftheirrelativenucleophilicities.

StructureoftheHaloalkane
SN1reactionsaregovernedmainlybytherelativestabilitiesofcarbocationintermediates.SN2reactions,by
contrast,aregovernedmainlybyfactorsinvolvingthesizeandbulkinessofthemoleculesinvolved.Wedescribe
thesefactorsassterichindrance,whichreferstotheabilityofgroups,becauseoftheirsizeandshape,tohinder
accesstoareactionsitewithinamolecule.SN2transitionstatesareparticularlysensitivetocrowdingaroundthe
siteofreaction.Thedistinctionisasfollows:
1.Relativestabilitiesofcarbocations:Aswelearnedinsection16.5(figure16.29),3carbocationsarethe
moststablecarbocations,requiringthelowestactivationenergyfortheirformation1carbocationsarethe
leaststable,requiringthehighestactivationenergyfortheirformation.Infact,1carbocationsareso
unstablethattheyhaveneverbeenobservedinsolution.Therefore,3haloalkanesarethemostlikelyto
reactbycarbocationformation2haloalkanesarelesslikelytoreactinthismannerandmethyland1
haloalkanesneverreactinthismanner.
2.Sterichindrance:InanSN2reaction,thenucleophilebeginstoformanewcovalentbondtothesubstitution
centrebyapproachingat180totheleavinggroup.Ifwecomparetheeaseofapproachbythenucleophile
tothesubstitutioncentreofa1haloalkanewiththatofa3haloalkane,weseethatthisapproachis
considerablyeasierinthecaseofthe1haloalkane.Twohydrogenatomsandonealkylgroupshieldthe
substitutioncentreofa1haloalkane.Incontrast,threealkylgroupsshieldthesubstitutioncentreofa3
haloalkane.Thiscentreinbromoethaneiseasilyaccessedbyanucleophile,whilethereisextremecrowding
arounditin2bromo2methylpropane:

Giventhecompetitionbetweenelectronicandstericfactors,wefindthat3haloalkanesreactbytheSN1
mechanismbecause3carbocationintermediatesareparticularlystableandbecausetheapproachofanucleophile
tothesubstitutioncentreina3haloalkaneishinderedbythethreegroupssurroundingit3haloalkanesnever
reactbytheSN2mechanism.Halomethanesand1haloalkaneshavelittlecrowdingaroundthesubstitutioncentre
andreactbytheSN2mechanismtheyneverreactbytheSN1mechanism,becausemethyland1carbocationsare
sounstable.SecondaryhaloalkanesmayreactbyeithertheSN1ortheSN2mechanism,dependingonthe
nucleophileandsolvent.Thecompetitionbetweenelectronicandstericfactorsandtheireffectsonrelativeratesof
nucleophilicsubstitutionreactionsofhaloalkanesaresummarisedinfigure18.12.

FIGURE18.12EffectofelectronicandstericfactorsincompetitionbetweenSN1andSN2reactionsofhaloalkanes.

TheLeavingGroup
Inthetransitionstatefornucleophilicsubstitutiononahaloalkane,theleavinggroupdevelopsapartialnegative
chargeinbothSN1andSN2reactionstherefore,theabilityofagrouptofunctionasaleavinggroupisrelatedto
howstableitisasananion.Themoststableanionsandthebestleavinggroupsaretheconjugatebasesofstrong
acids.Thus,wecanuseinformationontherelativestrengthsoforganicandinorganicacidsinappendixEto
determinewhichanionsarethebestleavinggroups:

ThebestleavinggroupsinthisseriesarethehalideionsI,BrandCl.Hydroxideions,OH,methoxideions,
CH3O,andamideions,NH2,aresuchpoorleavinggroupsthattheyrarely,ifever,aredisplacedinnucleophilic
substitutionreactions.

TheSolvent
Solventsprovidethemediuminwhichreactantsaredissolvedandinwhichnucleophilicsubstitutionreactionstake
place.Commonsolventsforthesereactionsaredividedintotwogroups:proticandaprotic.

ProticsolventscontainOHgroupsandarehydrogenbonddonors.Commonproticsolventsfornucleophilic
substitutionreactionsarewater,lowmolarmassalcoholsandlowmolarmasscarboxylicacids(table18.3).Each
cansolvate(seechapter10,p.396)boththeanionicandcationiccomponentsofioniccompoundsbyelectrostatic
interactionbetweenitspartiallynegativelychargedoxygenatom(s)andthecationandbetweenitspartially
positivelychargedhydrogenatomandtheanion.ThesesamepropertiesaidintheionisationofCXbondsto
giveanXanionandacarbocationthus,proticsolventsaregoodsolventsinwhichtocarryoutSN1reactions.

TABLE18.3 Commonproticsolvents

AproticsolventsdonotcontainOHgroupsandcannotfunctionashydrogenbonddonors.Table18.4liststhe
aproticsolventsmostcommonlyusedfornucleophilicsubstitutionreactions.Dimethylsulfoxideandacetoneare
polaraproticsolventsdichloromethaneanddiethyletherarerelativelynonpolaraproticsolvents.Theaprotic
solventslistedintable18.4areparticularlygoodforSN2reactions.Polaraproticsolventscansolvatecationsonly
theycannotsolvateanions(i.e.theanionsarenotcloselysurroundedbysolventmolecules),soanionsinaprotic
solventsaremuchmorereactiveasnucleophiles.
 TABLE18.4 Commonaproticsolvents

Table18.5summarisesthefactorsfavouringSN1andSN2reactionsitalsoshowsthechangeinconfiguration
whennucleophilicsubstitutiontakesplaceatastereocentre.
TABLE18.5 ComparisonbetweenSN1andSN2reactionsofhaloalkanes
Typeof
haloalkane SN2 SN1
methyl, SN2isfavoured. SN1doesnotoccur.Themethylcationisso
CH3X unstablethatitisneverobservedinsolution.
primary, SN2isfavoured. SN1doesnotoccur.Primarycarbocationsareso
RCH2X unstablethattheyareneverobservedinsolution.
secondary, SN2isfavouredinaproticsolventswith SN1isfavouredinproticsolventswithpoor
R2CHX goodnucleophiles. nucleophiles.
tertiary, SN2doesnotoccurbecauseofsteric SN1isfavouredbecauseoftheeaseofformation
R3CX hindrancearoundthesubstitutioncentre. of3carbocations.
substitution Inversionofconfigurationthe Racemisationthecarbocationintermediateis
ata nucleophileattacksthestereocentre planar,andanattackbythenucleophileoccurs
stereocentre fromthesideoppositetheleaving withequalprobabilityfromeitherside.
group.

AnalysisofSeveralNucleophilicSubstitutionReactions
Predictionsaboutthemechanismofaparticularnucleophilicsubstitutionreactionmustbebasedonconsiderations
ofthestructureofthehaloalkane,thenucleophile,theleavinggroupandthesolvent.Thefollowingareanalysesof
threesuchreactions.

Example1

Methanolisapolarproticsolventandagoodoneinwhichtoformcarbocations.Forexample,2chlorobutane
ionisesinmethanoltoforma2carbocationintermediate.Methanolisaweaknucleophile.Fromthisanalysis,we
predictthatreactionoccursbytheSN1mechanism.The2carbocationintermediate(anelectrophile)thenreacts
withmethanol(anucleophile)followedbyprotontransfertogivetheobservedproduct.Theproductisformedasa
50:50mixtureofRandSconfigurationsthatis,itisformedasaracemicmixture.
Example2

Theequationbelowshowsa1bromoalkaneinthepresenceofaniodideion,agoodnucleophile.Because1
carbocationsaresounstable,theyneverforminsolution,andanSN1reactionisnotpossible.Dimethylsulfoxide
(DMSO),apolaraproticsolvent,isagoodsolventinwhichtocarryoutSN2reactions.Fromthisanalysis,we
predictthatreactionoccursbytheSN2mechanism.

Example3

Bromideisagoodleavinggroupona2carbonatom.Themethylsulfideionisagoodnucleophile.Acetone,a
polaraproticsolvent,isagoodmediuminwhichtocarryoutSN2reactions,butapoormediuminwhichtocarry
outSN1reactions.Therefore,wepredictthatthereactionbelowoccursbytheSN2mechanism,andthatthe
productformedhastheRconfiguration.

WORKEDEXAMPLE18.4

PredictingReactionProductsandMechanisms
Writetheexpectedproductofeachofthefollowingnucleophilicsubstitutionreactionsandpredictthe
mechanismbywhichtheproductisformed.
(a)

(b)

Analysisandsolution

Withourknowledgeofthefactorsthatcontrolthereactionmechanismsofhaloalkanes,wecanpredict
theproductsandthemannerinwhichtheyareformed.
(a)Methanolisapoornucleophile.Itisalsoapolarproticsolventthatcansolvatecarbocations.
Ionisationofthecarboniodinebondformsa2carbocationintermediate.Wepredictthatthe
reactionoccursbytheSN1mechanism:

(b)Bromideisagoodleavinggroupona2carbonatom.Theacetateionisamoderate
nucleophile.DMSOisaparticularlygoodsolventforSN2reactions.Wepredictsubstitutionby
theSN2mechanismwithinversionofconfigurationatthestereocentre:
Isouranswerreasonable?

Checkyouranswerbyansweringthesetwoquestions:Aretheproductssensibleintermsofthegroups
andbonding?Dotheproductshavepoorerleavinggroupsthanthestartingmaterials?

PRACTICEEXERCISE18.4
Writetheexpectedproductofeachofthefollowingnucleophilicsubstitutionreactions
andpredictthemechanismbywhichtheproductisformed.
(a)

(b)

ChemistryResearch

GreenSolvents

DrJasonHarper,UniversityofNewSouthWales

Solventsclearlyaffecttheoutcomeofreactions,particularlybychangingthe
freeenergiesofstartingmaterialsandtransitionstatecomplexes.Thisis
usefulsyntheticallyastherate,andoftentheutilityofaprocess,canbe
modifiedbychangingthesolvent.Ourgroupisinvestigatingwaysof
affectingreactionprogressusingnovelsolventsystems.

Recently,therehasbeenagreatpushtowardsenvironmentallyfriendlyor
greenchemistry.Oneareahasbeenreducingtheuseofvolatileorganic
solventsandreplacingthemwithionicliquids(seefigure18.13).Ionic
liquidsaresaltsthat,unlikethosesimplesaltsmadeupofametalcationand
anonmetalanion,aremadeupofcomplexioniccomponentstheresultis
thattheyareliquidatroomtemperature.Whiletheyareliquid,theforces
betweenthecomponentsareelectrostaticandverystrong,sothattheydonot
evaporate.Theseuniquepropertiesmeanthattheyarenotlosttothe
environmentandarehenceconsideredasgreenalternativestoconventional
solvents.
 FIGURE18.13 Anexampleofanionicliquidboththe
(a)cationand
(b)anionarelargeandthechargeisdiffuse.

Theelectrostaticinteractionsarenotjustbetweentheanionandcation
componentsofanionicliquidbutalsobetweenthesolutesdissolvedinthem
thissolvation(seesection10.3)istypicallymoresignificantthanin
molecularsolvents.Wehaveshownthatthiscandramaticallyaffect
substitutionreactions,suchasthoseshowninfigure18.14,notonlyby
stabilisingthedevelopingchargesinthetransitionstatebutalsothrough
orderingofthesolventaroundthecomponentsofthereactionmixture.By
changingtherelativecontributionsofthesetwofactors,whichcanbedone
bychangingtheproportionofionicliquidinthesolvent,therateofreaction
canbeoptimised.Theultimategoalistodevelopsystemsinwhichtherateof
reactionismaximisedusingonlytheseenvironmentallyfriendlysolvents.
 FIGURE18.14 (a)SN1and
(b)SN2processesthatarechangeddramaticallyby
movingtoanionicliquidsolvent.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
18.3elimination
Earlierinthischapter(p.783),wedescribedoneofthereactionsofhaloalkanesaseliminationtoproduce
alkenes.Thesearecalledeliminationsand,inthissection,westudyatypeofeliminationcalled
dehydrohalogenation.Inthisprocess,inthepresenceofastrongbasesuchashydroxideionsorethoxide
ions,hydrogencanberemovedfromacarbonatomadjacenttothehalogen,followedbyremovalofthe
halogen,toformacarboncarbondoublebond:

Astheequationshows,wecallthecarbonatombearingthehalogenthecarbonatomandtheadjacent
carbonatomthecarbonatom.

Becausemostnucleophilescanalsoactasbasesandviceversa,itisimportanttokeepinmindthat
eliminationandnucleophilicsubstitutionarecompetingreactions.Atthislevel,itisnotnecessarytoexplore
whichismorefavoured,althoughwewilldealwithsomeoftheprinciplesthatgoverntheoutcomein
section18.4.Atthisstage,notethatbothprocessesmayoccurinthereactionofsomemolecules.

CommonstrongbasesusedforeliminationareOH,ORandNH2.Thefollowingarethreeexamplesof
basepromotedreactions:

Inthefirstexample,thebaseisshownasareactantonthelefthandsideofthearrowandthereaction
equationisbalanced.Inthesecondandthirdexamples,althoughthebaseisstillareactant,itisshownover
thereactionarrowandtheequationisnotbalanced.Inorganicchemistry,wefocusprimarilyonchangesto
theorganicstructureandwedonotnecessarilyshowthepresenceofreactantsandspectatorions.The
secondandthirdexamplesaremorecomplicatedthanthefirsttherearenonequivalentcarbonatoms,
eachbearingahydrogenatom.Therefore,twoalkenesarepossiblefromeacheliminationreaction.In
eachcase,themajorproductoftheseandmostothereliminationreactionsisthemoresubstitutedalkene
(itisalsothemorestablealkene).ThisisknownasZaitsev'srule(orZaitsevelimination)inhonourofthe
chemistwhofirstmadethisgeneralisation.
WORKEDEXAMPLE18.5

PredictingeliminationProducts
Predicttheeliminationproduct(s)formedwheneachofthefollowingbromoalkanesistreated
withsodiumethoxideinethanol(iftwoproductsmightbeformed,predictthemajorproduct).
(a)

(b)

Analysisandsolution

Whenstrongbasescanremoveahydrogenatomtoformarelativelystablecarbocation,
eliminationbecomespossible.
(a)Therearetwononequivalentcarbonatomsinthisbromoalkane,sotwoalkenesare
possible.Themajorproductis2methylbut2ene,themoresubstitutedalkene.

(b)Thereisonlyonecarbonatominthisbromoalkane,soonlyonealkeneispossible.

Isouranswerreasonable?

Youshouldcheckyouranswertoensurethatthenewlyformeddoublebondinvolvesthecarbon
atomthatwasbondedtothehalogen.Also,ensurethatthevalenciesofalltheatomsinthe
productsarecorrect.Rememberthataneutralcarbonatommustalwayshavefourbonds.

PRACTICEEXERCISE18.5
 Predicttheeliminationproductsformed
wheneachofthefollowingchloroalkanesis
treatedwithsodiumethoxideinethanol(iftwo
productsmightbeformed,predictwhichisthe
majorproduct).
(a)

(b)

(c)

Mechanismsofelimination
Therearetwotypesofmechanismsforeliminationreactions.Afundamentaldifferencebetweenthemis
thetimingofthebondbreakingandbondformingsteps.Recallthatwemadethissamestatementaboutthe
twolimitingmechanismsfornucleophilicsubstitutionreactionsinsection18.2.

E1Mechanism
Whenthecarbonhalogenbondiscompletelybrokenbeforethebaseremovesahydrogenatomtogivethe
carboncarbondoublebond,themechanismisdesignatedE1.Estandsforeliminationand1fora
unimolecularreactiononlyonespecies,inthiscasethehaloalkane,isinvolvedintheratedeterminingstep.
TheratelawforanE1reactionhasthesameformasthatforanSN1reaction:

ThemechanismforanE1reactionisillustratedbythereactionof2bromo2methylpropanetoform2
methylpropene.Inthistwostepmechanism,theratedeterminingstepisthebreakingofthecarbonhalogen
bondtoformacarbocationintermediate(justasitisintheSN1mechanism).
Step1:RatedeterminingbreakingoftheCBrbondgivesacarbocationintermediate:
 Step2:Protontransferfromthecarbocationintermediatetomethanol(whichinthisinstanceisboththe
solventandareactant)givesthealkene:

E2Mechanism
Whenthebaseremovesahydrogenatomatthesametimeasthecarbonhalogenbondisbroken,itis
designatedanE2reaction.Estandsforeliminationand2forabimolecularreaction.Theratelawforthe
ratedeterminingstepdependsonboththehaloalkaneandthebase:

Thestrongerthebase,themorelikelyitisthattheE2mechanismwilldominate.WeillustratetheE2
mechanismbythereactionof1bromopropanewithsodiumethoxide.Inthismechanism,protontransferto
thebase,formationofthecarboncarbondoublebondandejectionofthebromideionoccur
simultaneouslythatis,allbondformingandbondbreakingstepsoccuratthesametime.

ForbothE1andE2reactions,themajorproductisthatformedinaccordancewithZaitsev'sruleas
illustratedbythisE2reaction:

Table18.6summarisesthegeneralisationsmadeonthisandthepreviouspagesaboutreactionsof
haloalkanes.

TABLE18.6 ComparisonbetweenE1andE2reactionsofhaloalkanes
Haloalkane E1 E2
primary, E1doesnotoccur.Primarycarbocationsareso E2isfavoured.
RCH2X unstablethattheyareneverobservedinsolution.

secondary, E1isthemainreactionwithweakbasessuchas E2isthemainreactionwith

R2CHX H2OandROH. strongbasessuchasOHand
OR.
tertiary, E1isthemainreactionwithweakbasessuchas E2isthemainreactionwith
R3CX H2OandROH. strongbasessuchasOHand
OR.
WORKEDEXAMPLE18.6

PredictingeliminationReactionMechanisms
PredictwhethereachofthefollowingeliminationreactionsproceedspredominantlybytheE1
orE2mechanism,andwriteastructuralformulaforthemajororganicproduct.
(a)

(b)

Analysisandsolution

Basedonthestructureofthehaloalkaneandthestrengthoftheacid,thelikelyreactionmech
anismcanbedetermined.
(a)A3chloroalkaneisheatedwithastrongbase.EliminationbyanE2reaction
predominates,giving2methylbut2eneasthemajorproduct:

(b)A3chloroalkaneisdissolvedinaceticacid,asolventthatpromotestheformationof
carbocations,toforma3carbocationthatthenlosesaprotontogive2methylbut2ene
asthemajoreliminationproduct.ThereactionoccursbytheE1mechanism:

Isouranswerreasonable?

Checkyouranswerbyaskingthesetwoquestions:Dothestructuresmakesense?Arethe
conditionsandbasestrengthsufficientforthereactiondescribed?
 PRACTICEEXERCISE18.6
Predictwhethereachofthefollowingelimination
reactionsproceedspredominantlybytheE1orE2
mechanism,andwriteastructuralformulaforthemajor
organicproduct:
(a)

(b)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
18.4SubstitutionVersusElimination
Thusfar,wehaveconsideredtwotypesofreactionsofhaloalkanes:nucleophilicsubstitutionandelimination.Many
ofthenucleophileswehaveexamined,suchashydroxideionsandalkoxideions,arealsostrongbases.Accordingly,
nucleophilicsubstitutionandeliminationoftencompetewitheachother,andtheratioofproductsformedbythese
reactionsdependsontherelativeratesofthetworeactions:

SN1VersusE1Reactions

Reactionsof2and3haloalkanesinpolarproticsolventsgivemixturesofsubstitutionandeliminationproducts.In
bothreactions,step1istheformationofacarbocationintermediate.Thisstepisthenfollowedbyeither(1)thelossof
ahydrogenatomtogiveanalkene(E1),or(2)reactionwiththesolventtogiveasubstitutionproduct(SN1).Inpolar
proticsolvents,theproductsformeddependonlyonthestructureoftheparticularcarbocation.Forexample,tertbutyl
chlorideandtertbutyliodidein80%aqueousethanolbothreactwiththesolvent,givingthesamemixtureof
substitutionandeliminationproducts:

Becausetheiodideionisabetterleavinggroupthanthechlorideion,tertbutyliodidereactsover100timesfasterthan
tertbutylchloride.However,theratioofproductsisthesame.

ChemistryResearch

HaloalkaneChemistry

AssociateProfessorRogerRead,MolecularDesignandSynthesisGroup,UniversityofNewSouthWales

Halogenatomsaregenerallymonovalentand,inthisrespect,canparticipateinbondinginasimilarwayto
hydrogenatoms.Haloalkanesresemblehydrocarbonsandarefoundassmallandlargemolecules,straight
chainedandbranched,saturatedandunsaturated.Theycanalsoexistassinglysubstitutedspeciesorin
multisubstitutedsituations.Thepresenceofahalogenimpartsreactivitytothehydrocarbons,but,becausethe
carbonhalogenbondisrelativelystrong,haloalkanesarerelativelystable.Forexample,wellknown
chlorinatedhydrocarbons,suchasdichloromethane,CH2Cl2,chloroform,CHCl3,andtrichloroethane,
CH3CCl3,areextremelyusefulsolvents.Theyundergoreactionundersometimesmildconditions,buttheease
ofreactiondependsonthetypeofhalogen(iodoalkanesarethemostreactivewhilefluoroalkanesaretheleast
reactive)andthedegreeofsubstitutionatthepointofattachment.

Fullyfluorinatedmolecules,suchasperfluorohexane(tetradecafluorohexane,figure18.15),havetwo
extremelyinterestingproperties.Firstly,theydissolveverylargequantitiesofoxygen,comparedwithother
solvents.Secondly,theperfluorocarbonsdonotmixwellwithwaterorregular(organic)solventssuchas
toluene,ethylacetate,ethanoloracetonitrile.Thesefeatureshavemadethemsuitableasshorttermblood
replacements.Polymersofperfluoroalkaneshavealsobeendevelopedandthosederivedfrom
poly(tetrafluoroethylene)arewellknownunderthetradenameofTeflon .Thesematerialsrepelwaterand
greasesandarerelativelyheatstable.Thisallowsthepolymericmaterialtobeappliedtosurfacestogivethem
nonstickproperties.Thesamematerialscanalsobeincorporatedintopaintsandclothtomakethemnonstick,
waterresistantanddirtresistant.

FIGURE18.15Perfluorohexane(seefigure18.19formoredetail).

Thereisalsogrowinguseforperfluorocarbons,suchasperfluorohexane,C6F14,asspecialistsolventsin
liquidliquidseparationtechnologies,andhybridsolvents,suchasbenzotrifluoride(trifluoromethylbenzene,
C6H5CF3),forreactionmedia.Conventionalsystemsallowseparationofsolutesintowaterororganic
solvents.Forexample,theseparationofsugarfrompetroliseasilyachievedbyshakingthemixturewith
waterthesugardissolvesinthewaterandcanberemovedbyseparatingthetwolayersofwaterandpetrol.
Becauseperfluorocarbonsdonotmixwithaqueousorwithorganicsolvents,theyformathreephasesystem:
organic,aqueousandfluorous(figure18.16),allowinganadditionalopportunityforseparation.
 FIGURE18.16 Comparisonof
(a)2phaseand
(b)3phaseliquidsystemsforseparationofreactionmixtures.

Aspartofthiseffort,theMolecularDesignandSynthesisGroupattheUniversityofNewSouthWaleshas
beendesigningtaggingagentsthatwilltemporarilyintroducehighlyfluorinatedalkylgroupstomoleculesto
aidinorganicsynthesis(forexample,seefigure18.17).IfaTeflonlikecoatingisappliedseparatelytoan
adsorbant,thiscanallowseparationoffluoroustaggedsubstancesbysimplefiltrationthroughthemodified
adsorbant.Thisoperationtakesadvantageofconventionalsolidphaseextraction(SPE)andintroduces
fluoroussolidphaseextraction(FSPE).Afterseparation,thefluoroustagscanberemovedandthemolecules
returnedtotheirnormalstateandbehaviour.Thistypeofchemistryisverynewandtherearemanynew
taggingagentsandreagentsthatcouldbedeveloped.
 FIGURE18.17Atypicalsynthesisinwhichafluoroustag(inthiscase,adiolwithpolyfluoroalkylgroups,shownin
red)isintroducedtoassistinseparationeventsduringintermediatestagesofthesyntheticprocess.
Removalatthefinalstepreleasesthedesirednonfluorousproductandagainprovideseasy
separationfromthefluorousmaterial.Notethatinthissynthesisthetaggantalsoservestoprotect
onealdehydegroup(asanacetal)thetaggingagentcanberecoveredandrecycled.

Thestrongdislikeofnonfluorousentitiesforfluorinecauseshighlyfluorinatedalkylgroupstobeshunned
andactuallyaggregatetogetheroutofdefencetheyaggregateevenmoreefficientlythancomparable
hydrocarbonsystems.Thishasopenedupfurtheropportunitiestodesignwelldefinedbuttotallyartificialand
stablemultilayer,micelleandvesiclestructures.Weareinvestigatingthisapproachinthedesignoffunctional
fluoroussurfactantsbasedonsmallheterocycliccompounds(figure18.18).Aggregatesofthemolecules
couldformmolecularcontainersandspecialsurfaceactivematerials,whilesubstituentsattachedtothe
moleculeswillbedesignedtoprovideaddedfunctionality.

FIGURE18.18Fluorousmoleculessuchasthesehaveshownusefulsurfaceactivity,buttheirapplicationwill
dependonhowtheyassociate(forexample,inopposition,asinthebilayerstructure,orinconcert,
asinthemicellarstructure).

Therearemanyopportunitiesandexcitingdiscoveriesyettobemadeinhaloalkanechemistry.
 Aconformationalcuriosity

Unlikenormalalkylchains,whicharemoststableinlinearzigzagconformations,equivalentpolyfluoroalkyl
groupsadoptarelativelyrigid,helixlikeconformation(followthecarbonframeworkinfigure18.19).Thisis
duetothecombinedeffectsoftheshort,buthighlypolarised,CFbond,andtherelativelylargersizeofthe
fluorineatomsoverhydrogenatoms.

FIGURE18.19 Stereoviewsof
(a)perfluorodecaneshowingahelicaltwistinthecarbonframework(blackballs)comparedwith
(b)thenormalzigzagarrangementintheequivalenthydrocarbon,ndecane.Notetherelative
atomsizesoffluorine(green)atomsandhydrogen(pink)atomsinthetwomolecules.This
andthestrongdipoleoftheCFbondcomparedwiththeCHbondarethedrivingforces
behindthedifferentpreferredconformations.Bothdiagramscanbeviewedin3Dwithalittle
practice.

SN2VersusE2Reactions

Itisconsiderablyeasiertopredicttheratioofsubstitutiontoeliminationproductsforreactionsofhaloalkaneswith
reagentsthatactasbothnucleophilesandbases.Theguidingprinciplesareasfollows:
1.Branchingatthecarbonorcarbon(s)increasessterichindrancearoundthecarbonandsignificantlyretards
SN2reactions.Bycontrast,branchingatthecarbonorcarbon(s)increasestherateofE2reactionsbecause
oftheincreasedstabilityofthealkeneproduct.
2.Thegreaterthenucleophilicityoftheattackingreagent,thegreateristheSN2:E2ratio.Conversely,thegreater
thebasicityoftheattackingreagent,theloweristheSN2:E2ratio.

Primaryhaloalkanesreactwithbases/nucleophilestogivepredominantlysubstitutionproducts.Withstrongbases,such
ashydroxideionsandethoxideions,apercentageoftheproductisformedbyanE2reaction,butitisgenerallysmall
comparedwiththatformedbyanSN2reaction.Withstrong,bulkybases,suchasthetertbutoxideion,theE2product
becomesthemajorproduct.Tertiaryhaloalkanesreactwithallstrongbases/goodnucleophilestogiveonlyelimination
products.
Secondaryhaloalkanesareborderline,andsubstitutionoreliminationmaybefavoured,dependingontheparticular
base/nucleophile,solventandtemperatureatwhichthereactioniscarriedout.Eliminationisfavouredwithstrong
bases/goodnucleophiles,suchashydroxideionsandethoxideions.Substitutionisfavouredwithweakbases/poor
nucleophiles,suchasacetateions.Table18.7summarisesthisinformationaboutsubstitutionversuselimination
reactionsofhaloalkanes.
TABLE18.7 Summaryofsubstitutionversuseliminationreactionsofhaloalkanes
Haloalkane Mechanism Comments
methyl, SN2 SN2istheonlysubstitutionreactionobserved.
CH3X
SN1reactionsofmethylhalidesareneverobserved.Themethylcationisso
unstablethatitisneverformedinsolution.
primary, SN2 SN2isthemainreactionwithstrongbases,suchasOHandEtO,andwithgood
RCH2X
nucleophiles/weakbases,suchasIandCH3COO.
E2 E2isthemainreactionwithstrong,bulkybases,suchaspotassiumtertbutoxide.
PrimarycarbocationsareneverformedinsolutionsoSN1andE1reactionsof1
haloalkanesareneverobserved.
secondary, SN2 SN2isthemainreactionwithweakbases/goodnucleophiles,suchasIand
R2CHX
CH3COO.
E2 E2isthemainreactionwithstrongbases/goodnucleophiles,suchasOHand
CH3CH2O.
SN1/E1 SN1andE1arecommoninreactionswithweaknucleophilesinpolarprotic
solvents,suchaswater,methanolandethanol.
tertiary, SN2reactionsof3haloalkanesareneverobservedbecauseoftheextreme
R3CX crowdingaroundthe3carbonatom.
E2 E2isthemainreactionwithstrongbases,suchasHOandRO.
SN1/E1 SN1andE1arethemainreactionswithpoornucleophiles/weakbases.

WORKEDEXAMPLE18.7

SubstitutionVersusElimination
Predictwhethereachofthefollowingreactionsproceedspredominantlybysubstitution(SN1orSN2)or
elimination(E1orE2)orwhetherthetwocompete.Writestructuralformulaeforthemajororganic
product(s).
(a)

(b)

Analysisandsolution
(a)A3chloroalkaneisheatedwithastrongbase/goodnucleophile.EliminationbyanE2reaction
predominatestogive2methylbut2eneasthemajorproduct:
 (b)Reactionofa1bromoalkanewithtriethylamine,amoderatenucleophile/weakbase,gives
substitutionbyanSN2reaction:

PRACTICEEXERCISE18.7
Predictwhethereachofthefollowingreactionsproceeds
predominantlybysubstitution(SN1orSN2)orelimination
(E1orE2)orwhetherthetwocompete.Writestructural
formulaeforthemajororganicproduct(s).
(a)

(b)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Haloalkanes
Haloalkanescontainahalogenatomcovalentlybondedtoansp 3hybridisedcarbonatom.IntheIUPAC
system,halogenatomsarenamedasfluoro,chloro,bromooriodosubstituentsandarelistedwith
othersubstituentsinalphabeticalorder.Haloalkanesareoftencalledalkylhalides.Commonnamesare
derivedbynamingthealkylgroup,followedbythenameofthehalideasaseparateword.Compounds
ofthetypeCHX3arecalledhaloforms.

Haloalkanescanbegeneratedinseveralwaysbutoneofthemostimportantisdirecthalogenationofan
alkaneviaafreeradicalsubstitutionreaction.Thereactionisnotveryselectiveandgenerallyall
possiblemonosubstitutionproductsareformed.Ifthereactionisnotcontrolledandanexcessofalkane
isnotpresent,multiplesubstitutioncanoccur.

Anucleophileisanyreagentwithanunsharedpairofelectronsthatcanbedonatedtoanotheratomor
iontoformanewcovalentbond.Nucleophilicsubstitutionisanyreactioninwhichonenucleophileis
substitutedforanother.eliminationisanyreactioninwhichatomsorgroupsareremovedfromtwo
adjacentcarbonatoms.Becauseallnucleophilesarealsobases,nucleophilicsubstitutionandbase
promotedeliminationarecompetingreactions.

NucleophilicSubstitution
Inanucleophilicsubstitutionreaction,negativelychargednucleophilesbecomeneutralafterthe
reaction.Unchargednucleophilesbecomepositivelychargedandmustundergoasecondsteptolose
theproton.

AnSN2reactionoccursinonestep.Thelossofonegroupisassistedbytheincomingnucleophile,and
bothareinvolvedinthetransitionstateoftheratedeterminingstep.Astwospeciesareinvolved,itis
calledabimolecularreaction.

AnSN1reactionoccursintwosteps.Thefirststepinvolveslossofahalogentoformacarbocation
intermediatethisisslowsoitgovernstherateofthereaction.Thesecondstepisarapidreactionwitha
nucleophiletocompletethesubstitution.AnSN1reactionisaunimolecularreactiononlyonespeciesis
involvedinthereactionleadingtothetransitionstateoftheratedeterminingstep.

Solvolysisdescribesareactionwherethesolventplaystheroleofthenucleophileinthesubstitution
reaction.ForSN1reactionstakingplaceatastereocentre,thereactionoccurswithracemisation.

Thenucleophilicityofareagentismeasuredbytherateofitsreactioninareferencenucleophilic
substitution.SN1reactionsaregovernedbyelectronicfactors,namely,therelativestabilitiesof
carbocationintermediates.SN2reactionsaregovernedbysterichindrance,theabilityoflargergroupsto
hinderaccesstothesiteofsubstitution.Theabilityofagrouptofunctionasaleavinggroupisrelatedto
itsstabilityasananion.Themoststableanionsandthebestleavinggroupsaretheconjugatebasesof
strongacids.ProticsolventscontainOHgroups.Theyinteractstronglywithpolarmoleculesandions
andaregoodsolventsinwhichtoformcarbocations.ProticsolventsfavourSN1reactions.Aprotic
solventsdonotcontainOHgroups.Theydonotinteractasstronglywithpolarmoleculesandions,
andcarbocationsarelesslikelytoforminthem.AproticsolventsfavourSN2reactions.

elimination
Dehydrohalogenation,atypeofeliminationreaction,istheremovalofHandXfromadjacentcarbon
atoms.Aeliminationthatgivesthemosthighlysubstituted,andthereforemoststable,alkeneissaidto
followZaitsev'srule.

AnE1reactionoccursintwosteps:breakingtheCXbondtoformacarbocationintermediate,
followedbythelossofH+toformanalkene.AnE2reactionoccursinonestep:reactionwithabaseto
removeH+,formationofthealkeneanddepartureoftheleavinggroup,alloccurringsimultaneously.

SubstitutionVersusElimination
Whenanucleophileisalsoastrongbase,nucleophilicsubstitutionandeliminationoftencompetewith
eachother.Reactionsof2and3haloalkanesinpolarproticsolventsgivemixturesofsubstitutionand
eliminationproducts.Aftertheformationofthecarbocationintermediate,either(1)H+islosttogivean
alkene(E1),or(2)solventaddstogiveasubstitutionproduct(SN1).Inpolarproticsolvents,the
productsformeddependonlyonthestructureoftheparticularcarbocation.Forreactionsofhaloalkanes
withreagentsthatactasbothnucleophilesandbases,sterichindrancesignificantlyretardsSN2
reactions,whilebranchingatthecarbonorcarbon(s)increasestherateofE2reactionstogivethe
alkeneproduct.Thegreaterthenucleophilicityoftheattackingreagent,thegreateristheSN2:E2ratio.
Conversely,thegreaterthebasicityoftheattackingreagent,thesmalleristheSN2:E2ratio.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Halogenation:aradicalsubstitutionreaction(section18.1)
Substitutionofhydrogensatomsonanalkanecanbeachievedusinghightemperaturesorintenselight
toinducearadicalchainreaction.Onlybromineandchlorinearepracticalforthishalogenation
reaction.

Nucleophilicsubstitution:SN2(section18.2)
SN2reactionsoccurinonestep,andboththenucleophileandtheleavinggroupareinvolvedinthe
transitionstateoftheratedeterminingstep.Thenucleophilemaybenegativelychargedorneutral.SN2
reactionsresultinaninversionofconfigurationatthereactioncentre.Theyareacceleratedinpolar
aproticsolventscomparedwithpolarproticsolvents.SN2reactionsaregovernedbystericfactors,
namely,thedegreeofcrowdingaroundthesiteofreaction.

Nucleophilicsubstitution:SN1(section18.2)
AnSN1reactionoccursintwosteps.Step1istheslow,ratedeterminingcleavageoftheCXbondto
formacarbocationintermediate,followedinstep2bytheintermediate'srapidreactionwitha
nucleophiletocompletethesubstitution.Reactionatastereocentregivesaracemicproduct.SN1
reactionsaregovernedbyelectronicfactors,namely,therelativestabilitiesofcarbocationintermediates.
elimination:E1(section18.3)
E1reactionsinvolvetheeliminationofatomsorgroupsofatomsfromadjacentcarbonatoms.Reactions
occurintwostepsandinvolvetheformationofacarbocationintermediate.

elimination:E2(section18.3)
AnE2reactionoccursinonestep:reactionwithbasetoremoveahydrogenatom,formationofthe
alkeneanddepartureoftheleavinggroup,alloccurringsimultaneously.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Haloalkanes
18.1WritetheIUPACnameofeachofthefollowingcompounds.
(a)CH2 CF2
(b)

(c)Cl(CH2)6Cl
(d)

(e)CF2Cl2
(f)

18.2WritetheIUPACnameofeachofthefollowingcompounds(becertaintoincludeadesignationof
configuration,whereappropriate,inyouranswer).
(a)

(b)

(c)

(d)

(e)
 (f)

18.3DrawastructuralformulaforeachofthefollowingcompoundswiththeIUPACnamegiven.
(a)3bromopropene
(b)(R)2chloropentane
(c)meso3,4dibromohexane
(d)trans1bromo3isopropylcyclohexane
(e)1,2dichloroethane
(f) bromocyclobutane
18.4Drawastructuralformulaforeachofthefollowingcompoundswiththecommonnamegiven.
(a)isopropylchloride
(b)secbutylbromide
(c)allyliodide
(d)methylenechloride
(e)chloroform
(f) tertbutylchloride
(g)isobutylchloride
18.5Whichofthefollowingcompoundsare2haloalkanes?
(a)isobutylchloride
(b)2iodooctane
(c)trans1chloro4methylcyclohexane
18.6Ignoringstereochemistry,writethestructuralformulaeandgivetheIUPACnamesfortheproducts
ofthefollowinghalogenationreactions.
(a)

(b)

(c)

(d)
NucleophilicSubstitution
18.7Writestructuralformulaeforthefollowingcommonorganicsolvents.
(a)dichloromethane
(b)acetone
(c)ethanol
(d)diethylether
(e)dimethylsulfoxide
18.8Arrangetheseproticsolventsinorderofincreasingpolarity:H2O,CH3CH2OH,CH3OH.
18.9Arrangetheseaproticsolventsinorderofincreasingpolarity:acetone,pentane,diethylether.
18.10Fromeachofthefollowingpairs,selectthebetternucleophile.
(a) H OorOH
2
(b)CH COOorOH
3
(c) CH SHorCH S
3 3
18.11WhichstatementsaretrueforSN2reactionsofhaloalkanes?
(a)Boththehaloalkaneandthenucleophileareinvolvedinthetransitionstateoftherate
determiningstep.
(b)Thereactionproceedswithinversionofconfigurationatthesubstitutioncentre.
(c)Thereactionproceedswithretentionofopticalactivity.
(d)Theorderofreactivityis3>2>1>methyl.
(e)Thenucleophilemusthaveanunsharedpairofelectronsandbearanegativecharge.
(f) Thegreaterthenucleophilicityofthenucleophile,thegreateristherateofreaction.
elimination
18.12Drawstructuralformulaeforthealkene(s)formedbytreatingeachofthefollowinghaloalkanes
withsodiumethoxideinethanol.AssumethateliminationoccursbytheE2mechanism.Where
twoalkenesarepossible,useZaitsev'sruletopredictwhichalkeneisthemajorproduct.
(a)

(b)

(c)

(d)
18.13Whichofthefollowinghaloalkanesundergodehydrohalogenationtogivealkenesthatdonot
showcistransisomerism?
(a)2chloropentane
(b)2chlorobutane
(c)chlorocyclohexane
(d)isobutylchloride
18.14Whathaloalkanemightyouuseasstartingmaterialtoproduceeachofthefollowingalkenesin
highyieldanduncontaminatedbyisomericalkenes?
(a)

(b)

SubstitutionVersusElimination
18.15ThereactionofmethyliodidewithsodiumhydroxidetogivemethanolalwaysinvolvestheSN2
mechanism.WhyisitthatSN1cannotplayaroleinthisconversion?
18.16Whatistheproductofthereactionof2bromoethanewithpotassiumtertbutoxide?Whyisitthat
littlesubstitutionoccursinthisreaction?
18.17Whatisthemajorproductofthereactionof2iodopropanewithsodiumethoxide?
18.18Thereactionof2bromo2methylpropaneandsodiumhydroxideoccursprimarilybywhich
mechanism,SN1,SN2,E1orE2?
18.19Considerthefollowingsubstitutionreaction.

(a)DeterminewhetherthisreactionproceedsviaanSN1orSN2process.
(b)Drawthemechanismforthisreaction.
(c)Whatistherateequationforthisreaction?
(d)Wouldthereactionoccuratafasterrateifsodiumbromidewereaddedtothereaction
mixture?
(e)Drawanenergydiagramforthisreaction.
18.20Considerthefollowingsubstitutionreaction.

(a)DeterminewhetherthisreactionproceedsviaanSN1orSN2process.
 (b)Drawthemechanismforthisreaction.
(c)Whatistherateequationforthisreaction?
(d)Wouldthereactionoccuratafasterrateiftheconcentrationofcyanideweredoubled?
(e)Drawanenergydiagramforthisreaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
18.21Ignoringstereochemistry,writethestructuralformulaeandgivetheIUPACnamesforthe
productsofthefollowinghalogenationreactions.
(a)
(b)

(c)
(d)

18.22CompletethefollowingSN2reactions.
(a)

(b)

(c)

18.23CompletethefollowingSN2reactions.
(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)
18.24Youweretoldthateachreactioninquestion18.23proceedsbytheSN2mechanism.Suppose
youwerenottoldthemechanism.Describehowyoucouldconclude,fromthestructuresofthe
haloalkane,thenucleophileandthesolvent,thateachreactionisinfactanSN2reaction.
18.25Inthefollowingreactions,ahaloalkaneistreatedwithacompoundthathastwonucleophilic
sites.Selectthemorenucleophilicsiteineachpart,andshowtheproductofeachSN2reaction.
(a)
(b)

(c)
18.26WhichstatementsaretrueforSN1reactionsofhaloalkanes?
(a)Boththehaloalkaneandthenucleophileareinvolvedinthetransitionstateoftherate
determiningstep.
(b)Thereactionatastereocentreproceedswithretentionofconfiguration.
(c)Thereactionatastereocentreproceedswithlossofopticalactivity.
(d)Theorderofreactivityis3>2>1>methyl.
(e)Thegreaterthestericcrowdingaroundthereactivecentre,theloweristherateof
reaction.
(f) Therateofreactionisgreaterwithgoodnucleophilesthanwithpoornucleophiles.
18.27DrawastructuralformulafortheproductofeachofthefollowingSN1reactions.
(a)

(b)

(c)

(d)
18.28Youweretoldthateachsubstitutionreactioninquestion18.27proceedsbytheSN1mechanism.
Supposethatyouwerenottoldthemechanism.Describehowyoucouldconclude,fromthe
structuresofthehaloalkane,thenucleophileandthesolvent,thateachreactionisinfactanSN1
reaction.
18.29Selectthememberofeachofthefollowingpairsthatundergoesnucleophilicsubstitutionin
aqueousethanolmorerapidly.
(a)

(b)

(c)

18.30Identifythereagentyouwouldusetoaccomplisheachofthefollowingtransformations.
(a)cyclobutanolbromocyclobutane
(b)tertbutanoltertbutylchloride
(c)ethylchloride
18.31Proposeamechanismfortheformationoftheproducts(butnottheirrelativepercentages)inthis
reaction.

18.32Therateofreactioninquestion18.31increasesby140timeswhencarriedoutin80%water/
20%ethanolcomparedwith40%water/60%ethanol.Accountforthisdifference.
18.33WhathybridisationbestdescribesthereactingcarbonatomintheSN2transitionstate?
18.34Haloalkenessuchasvinylbromide,CH2 CHBr,undergoneitherSN1norSN2reactions.What
factorsaccountforthislackofreactivity?
18.35Showhowyoumightsynthesisethefollowingcompoundsfromahaloalkaneandanucleophile.
(a)
 (b)

(c)

(d)

(e)

(f)

(g)

18.36Showhowyoumightsynthesisethefollowingcompoundsfromahaloalkaneandanucleophile.
(a)

(b)

(c)

(d)

(e)

(f) (CH3CH2CH2CH2)2O
18.37Foreachofthefollowingalkenes,drawstructuralformulaeofallchloroalkanesthatundergo
 dehydrohalogenationwhentreatedwithKOHtogivethatalkeneasthemajorproduct(forsome
alkenes,onlyonechloroalkanegivesthedesiredalkeneasthemajorproductforotheralkenes,
twochloroalkanesmaywork).
(a)

(b)

(c)

(d)

(e)

18.38Whencis4chlorocyclohexanolistreatedwithsodiumhydroxideinethanol,itgivesonlyone
substitutionproduct,trans1,4cyclohexanediol(1).Underthesameexperimentalconditions,
trans4chlorocyclohexanolgivescyclohex3enol(2)andthebicyclicether(3).
 (a)Proposeamechanismfortheformationofproduct(1),andaccountforitsconfiguration.
(b)Proposeamechanismfortheformationofproduct(2).
(c)Accountforthefactthatthebicyclicether(3)isformedfromthetransisomer,butnot
fromthecisisomer.
18.39Ineachofthefollowingreactions,showhowtoconvertthegivenstartingmaterialintothe
desiredproduct(notethatsomesynthesesrequireonlyonestep,whereasothersrequiretwoor
moresteps).
(a)

(b)

(c)

(d)

(e)
 (f)

18.40Howmanyisomers,includingcistransisomers,arepossibleforthemajorproductof
dehydrohalogenationofeachofthefollowinghaloalkanes?
(a)3chloro3methylhexane
(b)3bromohexane
18.41Givetheproductsofthereactionof1iodopropanewitheachofthefollowing.
(a)NaOH
(b)NaNH2
(c)NaCN
(d)NaOOCCH3
(e)NaI
(f) NaOC(CH3)3
18.42Belowaretwopotentialmethodsforpreparingthesameether,butonlyoneofthemis
successful.Identifythesuccessfulapproachandexplainyourchoice.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
18.43TheWilliamsonethersynthesisinvolvestreatingahaloalkanewithametalalkoxide.The
followingtworeactionsareintendedtogivebenzyltertbutylether.Onereactiongivestheether
ingoodyield,buttheotherdoesnot.Whichreactiongivestheether?Whatistheproductofthe
otherreaction,andhowdoyouaccountforitsformation?
(a)

(b)

18.44Thefollowingetherscan,inprinciple,besynthesisedbytwodifferentcombinationsofa
haloalkaneorhalocycloalkanewithametalalkoxide.Showonecombinationthatformsether
bond1andanotherthatformsetherbond2.Whichcombinationgivesthehigheryieldofether?
(a)

(b)

(c)

18.45Proposeamechanismforthefollowingreaction.
18.46AnOHgroupisapoorleavinggroup,yetsubstitutionoccursreadilyinthefollowingreaction.
ProposeamechanismforthisreactionthatshowshowOHovercomesitslimitationofbeinga
poorleavinggroup.

18.47Explainwhy(S)2bromobutanebecomesopticallyinactivewhentreatedwithsodiumbromidein
DMSO.

18.48Explainwhyphenoxideisamuchpoorernucleophilethancyclohexoxide.

18.49Inethers,eachsideoftheoxygenisessentiallyanORgroupandsoisapoorleavinggroup.
Epoxidesarethreememberedringethers(oxiraneinquestion18.45isanexampleofan
epoxide).Explainwhyanepoxidereactsreadilywithanucleophiledespitebeinganether.

18.50Whatalkene(s)andreactionconditionsgiveeachofthefollowinghaloalkanesingoodyield?
(Hint:Reviewchapter8.)
(a)

(b)

(c)
18.51Showreagentsandconditionsthatbringaboutthefollowingconversions.
(a)

(b)

(c)

(d)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
elimination haloform radical
aproticsolvents halogenation SN1
bimolecularreaction nucleophile SN2
dehydrohalogenation nucleophilicsubstitution solvolysis
E1 nucleophilicity sterichindrance
E2 aproticsolvents unimolecularreaction
haloalkanes radicalsubstitution Zaitsev'srule

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

19 Alcohols,AminesandRelated
Compounds
Onapercapitabasis,AustraliaandNewZealandhavethehighestincidenceofasthmaintheworld.The
inhalerinthepicturedeliverspuffsofsalbutamol(alsoknownasalbuterolor,morecommonly,asVentolin
),whichisapotentsyntheticbronchodilatorusedinthetreatmentofasthma.Thestructureofsalbutamol
(shownbelow)ispatternedafterthatofepinephrine(adrenaline)and,likemanydrugs,salbutamolisa
polyfunctionalcompound(itcontainsmorethanonetypeoffunctionalgroup).Thefunctionalgroupspresent
insalbutamolincludeaprimaryandsecondaryalcohol,aphenolandasecondaryamine.Thesefunctional
groupsareimportantinthebindingofsalbutamoltothereceptors(activesite)inthelungswhichcauses
smoothmusclerelaxation.Thebindingoccursthroughhydrogenbondingbetweenthehydroxylgroups,and
ionionattractionsbetweentheprotonatedamineandacarboxylategroupintheactivesite.Thebulkytertiary
butylgrouphelpstoreducesideeffectsbypreventingbindingatsimilarshapedreceptorsthatcausesmooth
musclecontraction.

Alcohols,phenols,ethersandaminesareextremelycommoninnatureandthesefunctionalgroupsplay
importantrolesinmanybiological,pharmaceuticalandindustrialapplications.Thiols,sulfurcontaining
analoguesofalcohols,playimportantrolesinbiologicalsystemsincludingflavourandodourchemistry.In
thischapter,westudythephysicalandchemicalpropertiesofthesefunctionalgroups.Wewilllearnhowthey
canbepreparedfrom,andtransformedinto,otherfunctionalgroups.

KEYTOPICS

19.1Alcohols
19.2Reactionsofalcohols
19.3Phenols
19.4Ethers
19.5Thiols
19.6Amines
19.7Reactionsofamines
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.1Alcohols
Alcohols,phenolsandetherscanbethoughtofasthreeclassesofcompoundsthatarerelatedtowater,
whilethiolsaresulfurcontaininganaloguesofalcohols.

Alcoholsareparticularlyimportantinbothlaboratoryreactionsandbiochemicaltransformationsof
organiccompounds.Theycanbeconvertedintoothertypesofcompounds,suchasalkenes,
haloalkanes,aldehydes,ketones,carboxylicacidsandesters.Alcoholscanbeconvertedtothese
compounds,andtheycanalsobepreparedfromthem.Thus,alcoholsplayacentralroleinthe
interconversionoforganicfunctionalgroups.

ThealcoholfunctionalgroupisanOH(hydroxyl)groupbondedtoansp 3hybridisedcarbonatom.
Theoxygenatomofanalcoholisalsosp 3hybridised.Twosp 3hybridorbitalsofoxygenformbonds
toatomsofcarbonandhydrogen.Theothertwosp 3hybridorbitalsofoxygeneachcontainsan
unsharedpairofelectrons.Figure19.1showsaLewisstructureandaballandstickmodelofmethanol,
CH3OH,thesimplestalcohol.

FIGURE19.1 Methanol,CH3 OH:

(a)Lewisstructureand
(b)ballandstickmodel.Thebondanglesinmethanolareveryclosetothetetrahedral
angle.

WeexplainedthebasicrulesofIUPACnomenclatureinchapter2.Here,wewillbrieflydescribethe
processfornamingalcoholstorefreshyourmemory.Alcoholsarenamedinthesamemanneras
alkanes,withthefollowingdifferences:
 1.Select,astheparentalkane,thelongestchainofcarbonatomsthatcontainstheOHgroup,and
numberthatchainfromtheendclosesttotheOHgroup.Innumberingtheparentchain,the
locationoftheOHgrouptakesprecedenceoveralkylgroupsandhalogens.
2.Changethesuffixoftheparentalkanefrometool(section2.3),anduseanumbertoshowthe
locationoftheOHgroup.Theendingoltellsusthatthecompoundisanalcohol.Forcyclic
alcohols,numberingbeginsatthecarbonatombearingtheOHgroup.
3.Nameandnumbersubstituentsandlisttheminalphabeticalorder.

Toderivecommonnamesforalcohols,wenamethealkylgroupbondedtotheOHgroupandaddthe
wordalcohol.ThefollowingdiagramshowstheIUPACnamesand,inparentheses,thecommonnames
ofeightlowmolarmassalcohols.

WORKEDEXAMPLE19.1

NamingAlcohols
WritetheIUPACnameforeachofthefollowingalcohols.
(a)CH3(CH2)6CH2OH
(b)

(c)

Analysis

Ageneralstrategyfornomenclaturequestionsistodrawthestructure(ifitisnotalreadyina
suitableform),identifythekeyfunctionalgroup(inthiscasetheOHgroup),andthen
numberthecarbonchainstartingfromtheendclosesttothefunctionalgroup.Finally,
identifyallothersubstituents.Asthecompoundsinthisexamplearealcohols,thenameswill
allendinol.Compound(a)isderivedfromanunbranchedalkanesoweneedtoidentify
 onlythealkaneandthepositionoftheOHgroup.Compound(b)includesabranchonthe
secondlastcarbonatom,andtheOHgroupisonthesecondcarbonatom.Compound(c)
isalittlemorecomplex.Itisacyclicalcohol,sowestartnumberingfromtheOHgroup.
ThereisalsoamethylgrouponthesecondcarbonatomwhichistranstotheOHgroup.
Thus,ataminimum,weneedtoindicatetherelativestereochemistry,thepositionofthe
substituentandthatitisacyclicalcohol.Tobemoreprecise,weshouldindicatetheabsolute
stereochemistryofthetwostereocentresusingthe(R,S)systemfromsection17.3.

Solution
(a)octan1ol
(b)4methylpentan2ol
(c)trans2methylcyclohexanolor(1R,2R)2methylcyclohexanol

Isouranswerreasonable?

Thebestwaytocheckifyouranswerisreasonableistodrawastructurefromyouranswer
anddetermineifthestructurerepresentsthesamemoleculeasthequestion.

PRACTICEEXERCISE19.1
WritetheIUPACnameforeachofthe
followingalcohols.
(a)

(b)

(c)

IntheIUPACsystem,acompoundcontainingtwohydroxylgroupsisnamedasadiol,onecontaining
threehydroxylgroupsisnamedasatriolandsoon.InIUPACnamesfordiols,triolsandsoon,the
finaleoftheparentalkanenameisretained,forexample,ethane1,2diol.

Aswithmanyorganiccompounds,commonnamesforcertaindiolsandtriolshavepersisted.
Compoundscontainingtwohydroxylgroupsonadjacentcarbonsareoftenreferredtoasglycols.
Ethyleneglycol(seefigure19.2)andpropyleneglycolaresynthesisedfromethylene(ethene)and
propylene(propene)respectively,hencetheircommonnamesasshownbelow.
 FIGURE19.2Ethyleneglycolisapolarmoleculeanddissolvesreadilyinwater,apolarsolvent.(Note:
Ethyleneglycolitselfiscolourless.)

Weclassifyalcoholsasprimary(1),secondary(2)ortertiary(3),dependingonwhethertheOH
groupisonaprimary,secondaryortertiarycarbonatom.

WORKEDEXAMPLE19.2
Primary,SecondaryandTertiaryAlcohols
Classifyeachofthefollowingalcoholsasprimary,secondaryortertiary.
(a)

(b)

(c)

Analysis

Todeterminewhetheranalcoholisprimary,secondaryortertiary,identifythecarbonatom
bondedtotheOHgroup.Nowcountthenumberofalkylgroupsbondedtothiscarbon
atom.Ifthereisone,thealcoholisprimary,iftwo,secondary,andifthree,tertiary.
Alternatively,youmaywishtoconsiderthenumberofhydrogenatomsonthecarbonatom
withtheOHgrouptwohydrogenatoms=primary,onehydrogenatom=secondary,and
nohydrogenatoms=tertiary.

Solution
(a)secondary(2)
(b)tertiary(3)
(c)primary(1)

Isouranswerreasonable?

Astherearetwocountingmethods(numberofalkylgroupsornumberofhydrogenatoms),
youshoulddoublecheckyouranswerbyusingthealternativemethod.

PRACTICEEXERCISE19.2
Classifyeachofthefollowingalcoholsas
primary,secondaryortertiary.
(a)

(b)
 (c)CH2 CHCH2OH
(d)

PhysicalProperties
ThemostimportantphysicalpropertyofalcoholsisthepolarityoftheirOHgroups.Thelarge
differenceinelectronegativity(figure5.5,p.168)betweenoxygenandcarbon(3.52.5=1.0)and
betweenoxygenandhydrogen(3.52.1=1.4),meansboththeCOandOHbondsarepolar
covalent,andalcoholsarepolarmolecules,asshownformethanolinfigure19.3.

FIGURE19.3 PolarityoftheCOHbondinmethanol:
(a)Therearepartialpositivechargesoncarbonandhydrogenandapartialnegative
chargeonoxygen.
(b)Anelectrondensitymapshowingthepartialnegativecharge(inred)aroundoxygen
andapartialpositivecharge(inblue)aroundhydrogenoftheOHgroup.

Table19.1liststheboilingpointsandwatersolubilityforfivegroupsofalcoholsandalkaneswiththe
samenumberofelectronsandsimilarmolarmass.Noticethat,ofthecompoundscomparedineach
group,thealcoholhasthehigherboilingpointandismoresolubleinwater.
TABLE19.1 Boilingpointsandsolubilitiesinwateroffivegroupsofalcoholsandalkaneswiththesame
numberofelectronsandsimilarmolarmass

Molar Total Boilingpoint Solubilityin

Structuralformula Name mass electrons (C) water
CH3OH methanol 32 18 65 infinite
CH3CH3 ethane 30 18 89 insoluble

CH3CH2OH ethanol 46 26 78 infinite

CH3CH2CH3 propane 44 26 42 insoluble
 CH3CH2CH2OH propan1ol 60 34 97 infinite
CH3CH2CH2CH3 butane 58 34 0 insoluble

CH3CH2CH2CH2OH butan1ol 74 42 117 8g/100g

CH3CH2CH2CH2CH3 pentane 72 42 36 insoluble

CH3CH2CH2CH2CH2OH pentan1ol 88 50 138 2.3g/100g

HOCH2CH2CH2CH2OH butane1,4 90 50 230 infinite
diol
CH3CH2CH2CH2CH2CH3 hexane 86 50 69 insoluble

Theboilingpointsofalltypesofcompounds,includingalcohols,increasewithincreasingnumberof
electronsbecauseofincreaseddispersionforcesbetweenlargermolecules(seechapter6,pp.2412).
Compare,forexample,theboilingpointsofethanol,propan1ol,butan1olandpentan1olintable
19.1.

Alcoholshavehigherboilingpointsthanalkaneswiththesameorasimilarnumberofelectrons,
becausealcoholsarepolarandcanassociateintheliquidstatebyhydrogenbondingasdepictedfor
ethanolinfigure19.4.Wefirstencounteredthistypeofintermolecularattractioninsection6.8.

FIGURE19.4Theassociationofethanolmoleculesintheliquidstate.EachOHgroupcanparticipateinup
tothreehydrogenbonds(onethroughhydrogenandtwothroughoxygen).Onlytwoofthese
threepossiblehydrogenbondspermoleculeareshowninthefigure.

Extraenergyisrequiredtoseparateeachalcoholmoleculefromitsneighboursbecauseofhydrogen
bondingbetweenalcoholmoleculesintheliquidstate.Thisresultsintherelativelyhighboilingpoints
ofalcoholscomparedwithalkanes.Additionalhydroxylgroupsinamoleculefurtherincreasetheextent
ofhydrogenbonding,ascanbeseenbycomparingtheboilingpointsofpentan1ol(138C)and
butane1,4diol(230C),whichhavethesamenumberofelectrons(andhencethesamedispersion
forces).
Alcoholsaremuchmoresolubleinwaterthanalkanes,alkenesandalkyneswithacomparablenumber
ofelectrons.Thehydroxylgroupinalcoholsreadilyformshydrogenbondswithwatermolecules,
resultinginthehighersolubilityofalcoholsinwater.Methanol,ethanolandpropan1olaresolublein
waterinallproportions.Asthenumberofelectrons(andsize)increases,thephysicalpropertiesof
alcoholsbecomemorelikethoseofhydrocarbonswithasimilarnumberofelectrons.Alcoholsof
highermolarmassaremuchlesssolubleinwaterbecauseoftheincreasedsizeofthehydrocarbonparts
ofthemolecules.

PreparationofAlcohols
Alcoholscanbepreparedfrommanyfunctionalgroupsusingmanydifferentreactions.Someofthese
reactionsarediscussedbrieflyhereandinmoredetailelsewhereinthistext.Asethanolisarguablythe
mostimportantalcohol,wewilldiscussitsmanufactureseparatelybeforegoingontothegeneral
syntheticmethodsavailableforthepreparationofalcohols.

InAustralia,ethanolisproducedbythefermentationofsugars.Therearetwomainsourcesofthese
sugars:sugarcane(figure19.5)andgrains.Sugarsfromcaneandmolasses(abyproductofthesugar
industry)canbeconverteddirectlyintoethanol.Grains,however,producestarches,whichmustfirstbe
hydrolysed(brokendown)tofermentablesugars,beforebeingusedtoproduceethanol.

FIGURE19.5Sugarcanecanbeusedforethanolproduction.

Ethanolisalsoproducedindustriallybythevapourphasehydrationofethylene(ethene)inthepresence
ofanacidcatalyst.

PreparationfromAlkenes
Alcoholscanbepreparedbytheacidcatalysedhydrationofalkenes(seesection16.5).Whenthe
alkeneisasymmetricallysubstituted,theadditionobeysMarkovnikov'srule(thehydrogenatomaddsto
thecarbonatomofthedoublebondwithmorehydrogenatoms,thusproducingthemorestable
carbocationintermediate).
PreparationfromHaloalkanes
Alcoholscanbepreparedfromhaloalkanesbynucleophilicsubstitutionwithahydroxideionorwater
(seesection18.2).Tertiaryhaloalkanesarereadilyconvertedtoalcoholsbywater.

Secondaryandprimaryalcoholsarebetterpreparedbyreactionwithhydroxideions.
ReductionofCarbonylCompounds
Alcoholscanbepreparedbythereductionofcarbonylcompounds.Aldehydesarereducedtoprimary
alcohols,andketonesarereducedtosecondaryalcohols(discussedfurtherinsection21.5).Thisismost
commonlycarriedoutusingmetalhydridereducingagentssuchassodiumborohydride,NaBH4,or
lithiumaluminiumhydride,LiAlH4.

Carboxylicacidsandesterscanbereducedtoformprimaryalcohols(discussedfurtherinsection23.5).
Thisreductionrequirestheuseofthemorepowerfulreducingagent,LiAlH4.

AdditionofGrignardReagentstoCarbonylCompounds
AlcoholscanbepreparedbytheadditionofGrignardreagentstocarbonylcompounds.Aldehydesreact
withGrignardreagentstogivesecondaryalcohols(exceptformaldehyde(methanal),whichgives
primaryalcohols),whileketonesgivetertiaryalcohols(discussedingreaterdetailinsection21.5).
EsterscanalsobeconvertedintotertiaryalcoholsbyreactionwithGrignardreagents(discussedfurther
insection21.5).Inthiscase,2equivalentsofGrignardreagentaddtotheestertogivethetertiary
alcohol.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.2ReactionsofAlcohols
Inthissection,westudytheacidityandbasicityofalcohols,theirdehydrationtoalkenes,theirconversionto
haloalkanes,andtheiroxidationtoaldehydes,ketonesorcarboxylicacids.

AcidityofAlcohols
Alcoholshavesimilaracidionisationconstants(pKa )towater(15.7),whichmeansthataqueoussolutionsof
alcoholshaveapHclosetothatofpurewater.ThepKa ofethanol,forexample,is15.9.Thereactionbelowisa
simpleacidbasereactioninwhichethanolisactingasanacidandwaterisactingasabase.

Table19.2givestheacidionisationconstantsforseverallowmolarmassalcohols.Methanolandethanolareabout
asacidicaswater.Highermolarmass,watersolublealcoholsareslightlyweakeracidsthanwater(pHofaqueous
solutions=7).(Atthispoint,itwouldbeworthwhiletoreviewthepositionofequilibriuminacidbasereactions
discussedinchapter11).Notethat,althoughaceticacidisaweakacidcomparedwithacidssuchasHCl,itsKa is
still10 10timesgreaterthanthatofalcohols.
TABLE19.2 pKa valuesforselectedalcoholsindiluteaqueoussolution(a).

(a)AlsogivenforcomparisonarepKa valuesforwater,aceticacidandhydrogenchloride.

BasicityofAlcohols
Inthepresenceofastrongacid,theoxygenatomofanalcoholisaweakbaseandreactswiththeacidbyproton
transfertoformanoxoniumion.Thereactionbelowisasimpleacidbasereactioninwhichethanolisactingasa
baseandthehydroniumionisactingasanacid.
Thus,dependingonconditions,alcoholscanfunctionasbothweakacidsandweakbases.

ReactionwithActiveMetals
Likewater,alcoholsreactwithLi,Na,K,Mgandotheractivemetalstoliberatehydrogengas,although,inthe
caseofalcohols,metalalkoxidesratherthanhydroxidesareformed.Inthefollowingoxidationreductionreaction,
NaisoxidisedtoNa+andH+isreducedtoH2(figure19.6).

FIGURE19.6Methanolreactswithsodiummetaltoproducehydrogengas.

Tonameametalalkoxide,writethenameofthecationfollowedbythenameoftheanion.Thenameofan
alkoxideionisderivedfromaprefixshowingthenumberofcarbonatomsandtheirarrangement(e.g.meth,eth,
isoprop,tertbut)followedbythesuffixoxide.Alkoxidescanalsobenamedasalkanolatesbyaddingthesuffix
atetothealcoholname(e.g.methanolate,ethanolate).

Alkoxideionsaregenerallystrongerbasesthanthehydroxideion.Inadditiontosodiummethoxide,thefollowing
metalsaltsofalcoholsarecommonlyusedinorganicreactionsthatrequireastrongbaseinanonaqueoussolvent:
sodiumethoxideinethanol,andpotassiumtertbutoxidein2methylpropan2ol(tertbutylalcohol).

Aswesawinchapter18,alkoxideionscanalsobeusedasnucleophilesinsubstitutionreactions.

ConversiontoHaloalkanes
TheconversionofanalcoholtoahaloalkaneinvolvessubstitutingahalogenfortheOHgroupatasaturated
carbonatom.Themostcommonreagentsforthisconversionarethehydrohalicacids(halogenacids),thionyl
chlorideandphosphorushalides.

ReactionwithHydrohalicAcids(HCl,HBrandHI)
WatersolubletertiaryalcoholsreactveryrapidlywithHCl,HBrandHI.Mixingatertiaryalcoholwith
concentratedhydrochloricacidforafewminutesatroomtemperatureconvertsthealcoholtoawaterinsoluble
chloroalkanethatseparatesfromtheaqueouslayer.

Lowmolarmass,watersolubleprimaryandsecondaryalcoholsdonotreactundertheseconditions.

WaterinsolubletertiaryalcoholsareconvertedtotertiaryhalidesbybubblinggaseousHXthroughasolutionof
thealcoholdissolvedindiethyletherortetrahydrofuran(THF).

Waterinsolubleprimaryandsecondaryalcoholsreactonlyslowlyundertheseconditions.

Primaryandsecondaryalcoholsareconvertedtobromoalkanesandiodoalkanesbytreatmentwithconcentrated
hydrobromicandhydroiodicacids.Theconditionsrequiredtoconvertaprimarlyalcoholtoabromoalkaneare
veryharshandcannotbeusedinthepresenceofmostotherfunctionalgroups.Forexample,boilingbutan1ol
withconcentratedHBrgives1bromobutane.

FromobservationsoftherelativeeaseofreactionofalcoholswithHX(3>2>1),itwasproposedthatthe
conversionoftertiaryandsecondaryalcoholstohaloalkanesbyconcentratedHXoccursbyanSNlmechanism
(seesection18.2forfurtherdiscussionofnucleophilicsubstitutionmechanisms)andinvolvestheformationofa
carbocationintermediate.Thiswaslaterconfirmedbyappropriatekineticsexperiments.Thereactionisbelievedto
occurthroughthethreestepsshownbelow.
Step1:RapidandreversibleprotontransferfromtheacidtotheOHgroupgivesanoxoniumion(asimple
acidbasereaction).ThisprotontransferconvertstheleavinggroupfromOH,apoorleavinggroup,toH O,a
2
betterleavinggroup.
 Step2:Lossofwaterfromtheoxoniumiongivesa3carbocationintermediate(ora2carbocation
intermediateifwestartedwitha2alcohol).

Whenwesaythatareactionisslow,wearenotsuggestingthatindividualbondsarebroken/formedslowly.
Thenumberofmoleculesthatundergothedescribedtransformationinagivenperiodoftimedeterminesthe
rateofthereaction(seesection15.1formoredetails).
Step3:Reactionofthe3carbocationintermediate(anelectrophile)withachlorideion(anucleophile)gives
thehaloalkaneproduct.

PrimaryalcoholsreactwithHXbyanSN2mechanism.Intheratedeterminingstep,thehalideiondisplacesH2O
fromthecarbonatombearingtheoxoniumion.ThedisplacementofH2OandtheformationoftheCXbondare
simultaneous.
Step1:RapidandreversibleprotontransfertotheOHgroup(asimpleacidbasereaction)convertsthe
leavinggroupfromOHtoH O,whichisabetterleavinggroup.
2

Step2:ThenucleophilicdisplacementofH2ObyBrthengivesthebromoalkane.

(Theoreticallythisstepisreversible,butinpracticethereversereactionissoslowthatwegenerallyconsiderit
asnonreversible.)

WhydotertiaryalcoholsreactwithHXbyformationofcarbocationintermediates(SN1),whereasprimaryalcohols
reactbydirectdisplacementoftheOH2+group(theprotonatedOHgroup)(SN2)?Theanswerisa
combinationofthesametwofactorsinvolvedinnucleophilicsubstitutionreactionsofhaloalkanes(section18.2):
1.Electronicfactors:Tertiarycarbocationsarethemoststableandmostreadilyformed,whereasprimary
carbocationsaretheleaststableandhardesttoform.Therefore,tertiaryalcoholsaremostlikelytoreactby
carbocationformation,secondaryalcoholsareintermediateandprimaryalcoholsrarely,ifever,reactby
 carbocationformation.
2.Stericfactors:ToformanewcarbonhalogenbondbyanSN2mechanism,thehalideionmustapproachthe
carbonatombearingtheleavinggroupfromthesidedirectlyoppositethatgroupandbegintoformanew
covalentbond.Ifwecomparethecarbonatomattachedtotheoxygenatomofanoxoniumiongenerated
fromaprimaryalcoholwithonegeneratedfromatertiaryalcohol,weseethattheapproachisconsiderably
easierinthecaseoftheprimaryalcohol.Foraprimaryalcohol,theapproachfromthesideoppositethe
carbonatombearingtheoxoniumionisscreenedbytwohydrogenatomsandonealkylgroup,whereas,in
tertiaryalcohols,thistypeofapproachisscreenedbythreealkylgroups.
ReactionwithThionylChloride,SOCl2

Themostwidelyusedreagentfortheconversionofprimaryandsecondaryalcoholstoalkylchloridesisthionyl
chloride,SOCl2.ThebyproductsofthisnucleophilicsubstitutionreactionareHClandSO2,bothgivenoffas
gases.Often,anorganicbasesuchaspyridineisaddedtoneutralisetheHClbyproduct.

ReactionwithPhosphorusHalides
Alcoholscanalsobeconvertedintohaloalkanesbyreactionwithphosphorushalides(PX3orPX5,whereX=Clor
Br).Theseareparticularlyusefulfortheformationofalkylbromides.Thereactionbyproductsarewatersoluble
sotheyareeasilyseparatedfromthehaloalkaneashaloalkanesarenotnormallysolubleinwater.Notethat3
equivalentsofalcoholcanreactwith1equivalentofphosphorustribromide.

AcidcatalysedDehydrationtoAlkenes
Analcoholcanbeconvertedtoanalkenebydehydration,thatis,bytheeliminationofamoleculeofwaterfrom
adjacentcarbonatoms.Insection16.5,wediscussedtheacidcatalysedhydrationofalkenestogivealcohols.In
thissection,wewilldiscusstheacidcatalyseddehydrationofalcoholstogivealkenes.Infact,hydration
dehydrationreactionsarereversible.Alkenehydrationandalcoholdehydrationarecompetingreactions,andthe
followingequilibriumexists:

How,then,dowecontrolwhichproductwillpredominate?RecallthatLeChtelier'sprinciple(section9.4,p.364)
statesthatasysteminequilibriumwillrespondtoastressintheequilibriumbycounteractingthatstress.This
responseallowsustocontrolthesetworeactionstogivethedesiredproduct.Largeamountsofwater(achieved
withtheuseofdiluteaqueousacid)favouralcoholformation,whereasascarcityofwater(achievedusing
concentratedacid)orexperimentalconditionsthatremovewater(forexample,heatingthereactionmixtureabove
100C)favouralkeneformation.Thus,dependingontheexperimentalconditions,itispossibletousethe
hydrationdehydrationequilibriumtoselectivelyprepareeitheralcoholsoralkenesinhighyields.

Inthelaboratory,thedehydrationofanalcoholismostoftencarriedoutbyheatingitwitheither85%phosphoric
acidorconcentratedsulfuricacid(typically98%).Primaryalcoholsarethemostdifficulttodehydrateand
generallyrequireheatinginconcentratedsulfuricacidattemperaturesashighas180C.Secondaryalcohols
undergoacidcatalyseddehydrationatsomewhatlowertemperatures.Theacidcatalyseddehydrationoftertiary
alcoholsoftenrequirestemperaturesonlyslightlyaboveroomtemperature.

Thus,theeaseofacidcatalyseddehydrationofalcoholsoccursintheorder:

Whenisomericalkenesareobtainedintheacidcatalyseddehydrationofanalcohol,themorestablealkene(the
onewiththegreaternumberofsubstituentsonthedoublebondgenerallypredominatesthatis,theacidcatalysed
dehydrationofalcoholsfollowsZaitsev'srule(section18.3).

WORKEDEXAMPLE19.3

AcidcatalysedDehydration
Drawstructuralformulaeforthealkenesthatformuponacidcatalyseddehydrationofthealcoholon
theright,andpredictwhichalkeneisthemajorproduct.

Analysis

IdentifythecarbonatombearingtheOHgroup,whichisC(2)inthisexample.Inadehydration
reaction,ahydrogenionisremovedfromoneofthecarbonatomsneighbouringthiscarbonatom,C(1)
orC(3)inthiscase.ThedoublebondisformedbetweenthecarbonatomwiththeOHgroupandthe
carbonatomthatlosesthehydrogenion,inthisexample,betweenC(2)andC(3),orC(2)andC(1).To
predictthemajorproduct,useZaitsev'srule.

Solution

Withthreealkylgroups(threemethylgroups)onthedoublebond,2methylbut2eneisthemajor
productandisformedbyeliminationbetweenC(2)andC(3).Withonlyonealkylgroup(anisopropyl
group)onthedoublebond,3methylbut1eneistheminorproductandisformedbyelimination
betweenC(2)andC(1).

Isouranswerreasonable?

Youshouldcheckthat,ineachofthealkenes,thecarbonatomthatwasbondedtotheOHgroupis
nowoneofthecarbonatomsinthedoublebond.

PRACTICEEXERCISE19.3
Drawstructuralformulaeforthealkenesthatform
uponacidcatalyseddehydrationofthefollowing
alcohols,andpredictwhichalkeneisthemajor
product.
(a)

(b)
Fromtherelativeeaseofdehydrationofalcohols(3>2>1),chemistsproposedathreestepmechanismforthe
acidcatalyseddehydrationofsecondaryandtertiaryalcohols.Thismechanisminvolvestheformationofa
carbocationintermediateintheratedeterminingstepandisthereforeanE1mechanism.
Step1:ProtontransferfromH3O+totheOHgroupofthealcoholgivesanoxoniumion(asimpleacidbase
reaction).ThisconvertsOH,apoorleavinggroup,intoH O,abetterleavinggroup.
2

Step2:BreakingoftheCObondgivesa2carbocationintermediate(ora3carbocationintermediateifwe
startedwitha3alcohol)andH2O.

Youshouldnotethatthetwostepsabovearethesameasthosefortheacidcatalysedconversionofsecondary
andtertiaryalcoholsintohaloalkanes(p.817).
Step3:ProtontransfertoH2Ofromthecarbonatomadjacenttothepositivelychargedcarbonatomgivesthe
alkeneandregeneratesthecatalyst.TheelectronsofaCHbondbecometheelectronsofthecarbon
carbondoublebond.

Notethatbut2ene,themajorproductaspredictedbyZaitsev'srule,isobtainedasamixtureofcisandtrans
isomers.Removalofaprotonfromthemethylgroupadjacenttothepositivelychargedcarbonatomwillproduce
but1ene.

Becausetheratedeterminingstepintheacidcatalyseddehydrationofsecondaryandtertiaryalcoholsisthe
formationofacarbocationintermediate,therelativeeaseofdehydrationofthesealcoholsparallelstheeaseof
formationofcarbocations.

Primaryalcoholsdonotreadilydehydrate,but,whentheydo,itisbelievedthattheyreactbythefollowingtwo
stepE2mechanism,inwhichstep2istheratedeterminingstep.
Step1:ProtontransferfromH3O+totheOHgroupofthealcoholgivesanoxoniumion(asimpleacidbase
reaction).
 Step2:SimultaneousprotontransfertothesolventandlossofH2Ogivesthealkene.

Oxidationofprimaryandsecondaryalcohols
Theoxidationofalcoholsisanotherexampleofoxidationreduction(redox)chemistry,asdiscussedinchapter12
(seesections12.1and12.2).Oxidationofaprimaryalcoholgivesanaldehydeoracarboxylicacid,dependingon
theexperimentalconditions.Secondaryalcoholsareoxidisedtoketones.Tertiaryalcoholsarenoteasilyoxidised.
Thefollowingisaseriesoftransformationsinwhichaprimaryalcoholisoxidisedfirsttoanaldehydeandthento
acarboxylicacid.Thefactthateachtransformationinvolvesoxidationisindicatedbythesymbol[O]overthe
reactionarrow.

Therearemanyoxidisingagentsavailablefortheoxidationofalcohols.Asmallselectionofthesereagents
includespotassiumpermanganate,sodiumhypochlorite(bleach)andnitricacid.However,thereagentmost
commonlyusedinthelaboratoryfortheoxidationofaprimaryalcoholtoacarboxylicacid,andasecondary
alcoholtoaketone,ischromicacid,H2CrO4.Chromicacidispreparedbydissolvingeitherchromium(VI)oxide
orpotassiumdichromateinaqueoussulfuricacid.

Theoxidationofoctan1olbychromicacidinaqueoussulfuricacidgivesoctanoicacidinhighyield.These
experimentalconditionsaremorethansufficienttooxidisetheintermediatealdehydetoacarboxylicacid.

Letusconsiderthetwohalfequationsforthereactionabove(forrevision,seesection12.2)andthebalanced
equation.Thisallowsustodeterminethenumberofequivalentsofoxidisingagentrequired.Forconvenience,we
willusethemolecularformulaeforoctan1olandoctanoicacid:

Topreparealdehydesbyoxidisingprimaryalcohols,themildoxidisingagent,pyridiniumchlorochromate
(PCC),iscommonlyused.ThisispreparedbydissolvingCrO3inaqueousHClandaddingpyridinetoprecipitate
thePCCasanorangesolidasshownbelow.(Note:Theoxidationstateofchromiumisstill+6.)PCCoxidationsare
carriedoutinaproticsolvents,mostcommonlydichloromethane,CH2Cl2.

Thisreagentisselectivefortheoxidationofprimaryalcoholstoaldehydesandalsohaslittleeffectoncarbon
carbondoublebondsorothereasilyoxidisedfunctionalgroups.Inthefollowingexample,geraniol,amolecule
producedbyhoneybees,isoxidisedtogeranial,alemonscentedmoleculeusedinperfumes,withoutaffecting
eithercarboncarbondoublebond.

SecondaryalcoholsareoxidisedtoketonesbybothchromicacidandPCC.

TertiaryalcoholsareresistanttooxidationbecausethecarbonatombearingtheOHgroupisbondedtothree
carbonatomsandthereforecannotformacarbonoxygendoublebond.
Notethattheessentialfeatureoftheoxidationofanalcoholisthepresenceofatleastonehydrogenatomonthe
carbonatombearingtheOHgroup.Tertiaryalcoholslacksuchahydrogen,sotheyarenotoxidised.

WORKEDEXAMPLE19.4

PCCOxidations
DrawtheproductofthetreatmentofeachofthefollowingalcoholswithPCC.
(a)

(b)

(c)

Analysis

AstheoxidisingagentisPCC,primaryalcoholswillbeoxidisedtoaldehydesandsecondaryalcoholsto
ketones.IdentifythecarbonatombearingtheOHgroupthecarbonylgroupisformedatthis
position.

Solution

Theprimaryalcoholhexan1olisoxidisedtohexanal.Thesecondaryalcoholhexan2olisoxidisedto
hexan2one.Cyclohexanol,asecondaryalcohol,isoxidisedtocyclohexanone.
(a)

(b)
 (c)

Isouranswerreasonable?

Checkthatanaldehydehasbeenformedfromaprimaryalcohol,andaketonehasbeenformedfroma
secondaryalcohol.Checkalsothatthepositionofthecarbonylgroupiscorrect(particularlyimportant
forketones).

PRACTICEEXERCISE19.4
Whatistheproductobtainedontreatingeachof
thealcoholsinworkedexample19.4with
chromicacid?

EsterFormation
Animportantreactionofalcoholsistheformationofestersbycondensationwithcarboxylicacids,acidchlorides
oranhydrides.Thechemistrywillbeintroducedbrieflyhereanddiscussedingreaterdetailinchapter23.

Alcoholscanalsoformesterswithinorganicacidssuchasnitricacid,phosphoricacid,sulfuricandsulfonicacids
(RSO3H).Nitroglycerinisanexampleofanesterformedbetweenglycerolandthreemoleequivalentsofnitric
acid.DNAandRNA(seechapter25)arepolymersinwhichthebackboneconsistsofalternatingunitsof
phosphoricacidandamonosaccharidebondedtogetherthroughesterlinkagesbetweenthealcoholgroupsofthe
monosaccharideandthephosphoricacidmolecules.Figure19.7showssomeexamplesofestersformedbetween
alcoholsandinorganicacids.
 FIGURE19.7 Examplesofestersofinorganicacids:
(a)pentaerythritoltetranitrate(anexplosive),
(b)dimethylsulfate(anindustrialmethylatingagent)and(c)afragmentofRNA.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.3Phenols
Phenolsarecompoundswithoneormorehydroxylgroupsbondeddirectlytoanaromaticring.Inthe
previoussectionwediscussedthechemistryofalcohols(ROH)andherewewillintroducethechemistryof
phenols(ArOH).Althoughthesefunctionalgroupsaresimilar(theybothformestersandethers),theyhave
someimportantdifferences,particularlytheiracidity.

Wenamesubstitutedphenolseitherasderivativesofphenolorbycommonnamesasshownbelow.

Notethatbenzylalcohol(phenylmethanol)isnotaphenolbecausethehydroxylgroupisnotconnected
directlytothearomaticring.Itisthedirectconnectionofthehydroxylgrouptoanaromaticringthatgives
risetothedifferentchemicalpropertiesofphenolsthesewillbediscussedbelow.

Phenolsarewidelydistributedinnature.Phenolitselfandtheisomericcresols(o,mandpcresol)are
foundincoaltar(theliquiddistilledfromcoalintheproductionofcoke).Thephenolderivativesthymol
andvanillinareimportantconstituentsofthymeandvanillabeans(figure19.8),respectively.
 FIGURE19.8Vanillinisaconstituentofvanillabeans.

Phenol,orcarbolicacid,asitwasoncecalled,isasolidwithalowmeltingpointandisonlyslightlysoluble
inwater.Insufficientlyhighconcentrations,itiscorrosivetoallkindsofcells,becauseithasahigh
permeabilityacrossthecellmembraneanddisruptsbiochemicalprocesseswithinthecell.Indilutesolutions,
phenolhassomeantisepticpropertiesandwasintroducedintothepracticeofsurgerybyJosephLister,who
demonstratedhistechniqueofasepticsurgeryattheUniversityofGlasgowSchoolofMedicinein1865.
Nowadays,phenolhasbeenreplacedbyantisepticsthataremorepowerfulandhavefewerundesirableside
effects.Amongtheseishexylresorcinol,whichiswidelyusedinnonprescriptionpreparationsasamild
antisepticanddisinfectant.Eugenol,whichcanbeisolatedfromtheflowerbudsofEugeniaaromatica
(clove),isusedasadentalantisepticandanalgesic.Capsaicinisthepungentcomponentofvariouschillies
andisalsotheactiveingredientinoleoresincapsicumspray(commonlyknownaspepperspray,figure
19.9).

FIGURE19.9Capsicumspraycontainsthephenolderivativecapsaicin.

Acidityofphenols
PhenolsandalcoholsbothcontainanOHgroup.Wegroupphenolsasaseparateclassofcompounds,
however,becausetheirchemicalpropertiesarequitedifferentfromthoseofalcohols.Oneofthemost
importantdifferencesisthatphenolsaresignificantlymoreacidicthanalcohols.Indeed,theacidityconstant
forphenolis10 6timeslargerthanthatofethanol.

Anotherwaytocomparetherelativeacidstrengthsofethanolandphenolistolookatthehydroniumion
concentrationandpHofa0.1maqueoussolutionofeach(table19.3).Forcomparison,the[H3O+]andpH
of0.1mHClarealsoincluded.
TABLE19.3 Relativeaciditiesof0.1Msolutionsofethanol,phenolandHCl

Acidionisationequation [H3O+] pH
CH3CH2OH+H2O CH3CH2O+H3O+ 1.010 7 7.0

C6H5OH+H2O C6H5O+H3O+ 3.310 6 5.4

HCl+H2O Cl+H3O+ 0.1 1.0

Inaqueoussolution,alcoholsareneutralsubstances,andthehydroniumionconcentrationof0.1Methanol
isthesameasthatofpurewater.A0.1MsolutionofphenolisslightlyacidicandhasapHof5.4.By
contrast,0.1MHCl,astrongacid(completelyionisedinaqueoussolution),hasapHof1.0.

Thegreateracidityofphenolscomparedwithalcoholsresultsfromthegreaterstabilityofthephenoxideion
comparedwithanalkoxideion.Thenegativechargeonthephenoxideionisdelocalisedbyresonance.The
twocontributingstructuresbelowleftforthephenoxideionplacethenegativechargeonoxygen,whilethe
threeontherightplacethenegativechargeontheorthoandparapositionsofthering.Thus,inthe
resonancehybrid,thenegativechargeofthephenoxideionisdelocalisedoverfouratoms,whichstabilises
thephenoxideionrelativetoanalkoxideion,forwhichnodelocalisationispossible.

Notethat,althoughtheresonancemodelhelpsusunderstandwhyphenolisastrongeracidthanethanol,it
doesnotprovideanyquantitativemeansofpredictingjusthowmuchstrongeranaciditmightbe.Tofind
outhowmuchstrongeroneacidisthananother,wemustdeterminetheirpKa valuesexperimentallyand
comparethem.

Ringsubstituentshavemarkedeffectsontheaciditiesofphenolsthroughacombinationofinductiveand
resonanceeffects.Electronwithdrawinggroupssuchaschloro,cyanoandnitrowithdrawelectrondensity
fromthearomaticring,weakentheOHbondandstabilisethephenoxideion.Thediagramatthetopof
thenextpageshowstheresonanceformsforthe4nitrophenoxideion.Youwillnoticethatthereisanextra
resonanceform(onlyoneoftheKekulformshasbeenshown)forthisionwherethechargehasbeen
delocalisedonanoxygenatomofthenitrogroup.Thisdelocalisationontheoxygenatomincreasesthe
stabilityofthephenoxideionandmakes4nitrophenolastrongeracidthanphenol.

Conversely,electrondonatinggroupslikeamino,alkoxyandalkylgroupsincreasetheelectrondensityof
thearomaticringanddestabilisethephenoxideion.Table19.4liststhepKa valuesforsomephenols.

TABLE19.4 ThepKa valuesforsomephenols.ThepKa1 valueforaceticacidisgivenforcomparison

 WORKEDEXAMPLE19.5

Acidity
Arrangethesecompoundsinorderofincreasingacidity:2,4dinitrophenol,phenolandbenzyl
alcohol.

Analysis

Asalcoholsaresignificantlylessacidicthanphenols,theseshouldbelistedfirst.Ofthephenols,
determinewhetherthesubstituentsareelectronwithdrawingorelectrondonating.Electron
withdrawinggroupsincreasetheacidityofthephenol,whileelectrondonatinggroupsdecrease
theacidity.

Solution

Benzylalcohol,aprimaryalcohol,hasapKa ofapproximately16.ThepKa ofphenolis9.99.

NitrogroupsareelectronwithdrawingandincreasetheacidityofthephenolicOHgroup.In
orderofincreasingacidity,thesecompoundsare:

Isouranswerreasonable?

Checkthatyouranswerhasthecompoundsintheorderof:alcohols<phenolswithelectron
donatinggroups<phenol<phenolswithelectronwithdrawinggroups.

PRACTICEEXERCISE19.5
Arrangethesecompoundsinorderof
increasingacidity:2,4dichlorophenol,phenol
andcyclohexanol.

AcidbaseReactionsofPhenols
Phenolsareweakacidsandreactwithstrongbases,suchasNaOH,toformwatersolublesalts.
Mostphenolsdonotreactwithweakerbases,suchassodiumbicarbonate,anddonotdissolveinaqueous
sodiumbicarbonate.Carbonicacidisastrongeracidthanmostphenolsand,consequently,theequilibrium
forthereactionofphenolswithbicarbonateionsliesfartotheleft(seechapter11).

Thefactthatphenolsareweaklyacidic,whereasalcoholsareneutral,providesaconvenientwaytoseparate
phenolsfromwaterinsolublealcohols.Supposethatwewanttoseparate4methylphenolfrom
cyclohexanol.Eachisonlyslightlysolubleinwatertherefore,theycannotbeseparatedonthebasisoftheir
watersolubility.Theycanbeseparated,however,onthebasisoftheirdifferenceinacidity.First,themixture
ofthetwoisdissolvedindiethyletherorsomeotherwaterimmisciblesolvent.Next,theethersolutionis
placedinaseparatingfunnelandshakenwithdiluteaqueousNaOH.Undertheseconditions,4
methylphenolreactswithNaOHtogivesodium4methylphenoxide,awatersolublesalt.Theupperlayerin
theseparatingfunnel,diethylether(density=0.74gmL1),nowcontainsonlydissolvedcyclohexanol.The
loweraqueouslayercontainsdissolvedsodium4methylphenoxide.Thelayersareseparated,anddistillation
oftheether(bp=35C)leavespurecyclohexanol(bp=161C).Acidificationoftheaqueousphasewith
0.1MHCloranotherstrongacidconvertssodium4methylphenoxideto4methylphenol,whichissparingly
solubleinwaterandcanbeextractedwithetherandrecoveredinpureform.Theflowchartontheright
summarisestheseexperimentalsteps.
OxidationofPhenols
Phenolsarereadilyoxidisedtogivequinones.Quinonesareintenselycolouredcompoundsrangingfrom
redthroughtoviolet.Thepinktingefoundinoldbottlesofphenolisduetotraceamountsofquinones.The
pHindicatoralizarinisaquinone.Ithastwoacidichydrogens,soitcanbeusedfortwodifferentpH
regions.ItisyellowatpH<5.5,redatpH6.811andpurpleatpH>12.
Theoxidationofphenolsisquitedifferentfromtheoxidationofalcohols(seesection19.2)becausetheydo
nothaveahydrogenatomonthecarbonatombearingthehydroxylgroup.Theparentcompound,phenol,is
easilyoxidisedandgivesrisetocyclohexa2,5dien1,4dione(pbenzoquinone).

Theoxidationof1,2and1,4dihydroxybenzenealsooccursreadilyandgivesthecorrespondingoandp
benzoquinone.Thebenzoquinonecanalsobeeasilyreducedtotheoriginaldihydroxybenzenebytreatment
withamildreducingagent.

EsterandEtherFormation
Phenolscanformestersbyreactionwithacidchloridesoracidanhydrides.However,unlikethealcohols
(seesection19.2),esterscannotbepreparedbytreatmentofphenolswithcarboxylicacidsasphenolsare
generallytoounreactive.Thislackofreactivityisdueinparttothedelocalisationoftheelectronsonthe
oxygenatomofthephenol,makingitlessnucleophilic.
Sincephenolsarequiteacidic,theyarereadilydeprotonatedtogivephenoxideions.Theseionsaregood
nucleophilesandwilldisplacehalogensfromhaloalkanes(seesection18.2)toproduceethers.

Youmayhavenoticedthatmanyofthereactionsofphenolsaresimilartothoseofalcohols.Careful
inspectionwillrevealthatphenolsandalcoholsreactinthesamewaywhenthereactioninvolvesbreaking
theOHbond(reactionswithbases,oxidation,andetherandesterformation).Phenolsdonotreadily
undergoreactionsthatrequirebreakingtheCObond(reactionwithHXtoformarylhalidesor
dehydration).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.4Ethers
Intheprevioussectionswestudiedcompoundsrelatedtowaterinwhichahydrogenatomwasreplaced
byanalkylgroup(alcohols)oranarylgroup(phenols).Inthissectionwewillinvestigaterelativesof
waterwherebothhydrogenatomshavebeenreplacedbyeitheralkylorarylgroupsethers.The
functionalgroupofanetherisanatomofoxygenbondedtotwocarbonatomsthatarenotbondedto
heteroatoms(e.g.O,N,S,halogen).Figure19.10showsaLewisstructureandballandstickmodelof
dimethylether,CH3OCH3,thesimplestether.Indimethylether,twosp 3hybridorbitalsofoxygenform
bondstocarbonatoms.Theothertwosp 3hybridorbitalsofoxygeneachcontainanunsharedpairof
electrons.

FIGURE19.10 Dimethylether,CH3 OCH3 :

(a)Lewisstructureand
(b)ballandstickmodel.

Inethylvinylether,theetheroxygenatomisbondedtoonesp 3hybridisedcarbonatomandonesp 2
hybridisedcarbonatom.

EthersarenamedintheIUPACsystembyselectingthelongestcarbonchainastheparentalkaneand
namingtheORgroupbondedtoitasanalkoxy(alkyl+oxygen)group.Commonnamesarederived
bylistingthealkylgroupsbondedtooxygeninalphabeticalorderandaddingthewordether.

Chemistsalmostinvariablyusecommonnamesforlowmolarmassethers.Forexample,although
ethoxyethaneistheIUPACnameforCH3CH2OCH2CH3,itisrarelycalledthat,butinsteadiscalled
diethylether,ethylether,or,evenmorecommonly,simplyether.

Cyclicethersareheterocycliccompoundsinwhichtheetheroxygenatomisoneoftheatomsinaring.
Theseethersaregenerallyknownbytheircommonnames.

WORKEDEXAMPLE19.6

NamingEthers
WritetheIUPACandcommonnamesforeachofthefollowingethers.
(a)

(b)

Analysis

Tonameethers,youshouldfirstidentifytheetheroxygenatomandthenidentifythetwo
alkylgroupsattachedtothisoxygenatom.IntheIUPACsystem,thelargerofthetwogroups
(iftheyaredifferent)istheparentalkaneandtheotheristhealkoxygroup.Usingthe
commonnomenclature,thealkylgroupsarelistedalphabeticallyfollowedbytheword
ether.

Solution
(a)2ethoxy2methylpropane.Itscommonnameistertbutylethylether.
(b)cyclohexoxycyclohexane.Itscommonnameisdicyclohexylether.

Isouranswerreasonable?

Tocheckthatyournamesaresensible,drawstructuresthatcorrespondtoyouranswersand
comparethesewiththestructuresprovidedinthequestion.

PRACTICEEXERCISE19.6
WritetheIUPACandcommonnamesfor
eachofthefollowingethers.
 (a)

(b)

PhysicalProperties
Ethersaremoderatelypolarcompoundsinwhichtheoxygenatomhasapartialnegativecharge,and
eachcarbonatombondedtoithasapartialpositivecharge(figure19.11).Becauseofsterichindrance,
however,onlyweakforcesofattractionexistbetweenethermoleculesinthepureliquid.Consequently,
boilingpointsofethersaremuchlowerthanthoseofalcoholswithasimilarnumberofelectrons(table
19.5)andareclosertohydrocarbonsofcomparablenumberofelectrons(table19.1).

FIGURE19.11Ethersarepolarmolecules,but,becauseofsterichindrance,onlyweakattractiveinteractions
existbetweentheirmoleculesinthepureliquid.

TABLE19.5 Boilingpointsandsolubilitiesinwaterofsomealcoholsandethersofcomparablenumberof
electrons

Total Boilingpoint Solubilityin

Structuralformula Name electrons (C) water
CH3CH2OH ethanol 26 78 infinite
CH3OCH3 dimethylether 26 24 7.8g/100g

CH3CH2CH2CH2OH butan1ol 42 117 7.4g/100g

CH3CH2OCH2CH3 diethylether 42 35 8g/100g
CH3CH2CH2CH2CH2OH pentan1ol 50 138 2.3g/100g
CH3CH2CH2CH2OCH3 butylmethylether 50 71 slight
CH3OCH2CH2OCH3 1,2 50 84 infinite
dimethoxyethane
Becausetheoxygenatomofanethercarriesapartialnegativecharge,ethersformhydrogenbondswith
water(figure19.12)andaremoresolubleinwaterthanhydrocarbonswithasimilarnumberofelectrons
andshape(comparedataintables19.1and19.5).

FIGURE19.12Dimethyletherinwater.Thepartiallynegativeoxygenatomoftheetheristhehydrogenbond
acceptor,andapartiallypositivehydrogenatomofawatermoleculeisthehydrogenbond
donor.Ethersarehydrogenbondacceptorsonlytheyarenothydrogenbonddonors.

Theeffectofhydrogenbondingisillustrateddramaticallybycomparingtheboilingpointsofethanol
(78C)anditsconstitutionalisomerdimethylether(24C).Thedifferenceinboilingpointsbetween
thesetwocompoundsisduetothepolarOHgroupinthealcohol,whichiscapableofforming
intermolecularhydrogenbonds.Thishydrogenbondingincreasestheattractiveforcebetween
moleculesofethanolthus,ethanolhasahigherboilingpoint(andwatersolubility)thandimethylether.

WORKEDEXAMPLE19.7

Solubility
Arrangethefollowingcompoundsinorderofincreasingsolubilityinwater.

Analysis

Aswaterisapolarsolventweexpectpolarcompoundstohaveagreatersolubilityinwater
thannonpolarcompounds.Bothdiethyletherand1,2dimethoxyethanearepolarcompounds
duetothepresenceofpolarCOCgroups,andeachinteractswithwaterasahydrogen
bondacceptor.Hexaneisanonpolarhydrocarbonand,therefore,weexpectittohavethe
lowestsolubilityinwater.Generally,compoundswithmorepolargroupsaremoresolublein
 water.

Solution

Isouranswerreasonable?

Checkthenumberofpolargroupsineachcompound.Areyourcompoundslistedinorderof
lowestnumberofpolargroupstohighestnumberofpolargroups?

PRACTICEEXERCISE19.7
Arrangethefollowingcompoundsinorderofincreasing
boilingpoint.

ReactionsofEthers
Ethers,ROR,resemblehydrocarbonsintheirresistancetochemicalreactions.Theydonotreact
readilywithoxidisingagents(e.g.potassiumdichromateorpotassiumpermanganate)orreducing
agents(e.g.sodiumborohydrideorlithiumaluminiumhydride).Theyarenotaffectedbymostacidsor
basesatmoderatetemperatures.However,theycanbecleavedwithconcentratedhydrobromicor
hydroiodicacidtogivethecorrespondinghaloalkaneandalcohol.IfanexcessofHXisused,the
alcoholcanreactfurthertogiveahaloalkaneandwater(seesection19.2).

Thisreactionisanotherexampleofanucleophilicsubstitutionandissimilartothereactionofalcohols
withHX.Thefirststepinvolvestheprotonationoftheetheroxygentoformanoxoniumion(R2OH+).

Becauseoftheirgoodsolventpropertiesandgeneralinertnesstochemicalreaction,ethersareexcellent
solventsinwhichtocarryoutmanyorganicreactions.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.5Thiols
Thesulfuranalogueofanalcoholiscalledathiol(thifromtheGreek:theion,sulfur)or,intheolder
literature,amercaptan,whichliterallymeansmercurycapturing.Sincesulfurandoxygenbelongto
thesamegroupoftheperiodictable,theysharesimilarchemicalproperties.Thiolsformthioesters,
thioethersandthioacetalsinthesamewayalcoholsformesters,ethersandacetals(seechapter21).The
functionalgroupofathiolisanSH(sulfhydryl)group.

Figure19.13showsaLewisstructureandaballandstickmodelofmethanethiol,CH3SH,thesimplest
thiol.Theelectronegativitiesofcarbonandsulfurinmethanethiolarevirtuallyidentical(2.55and2.58
respectively),whilesulfurisslightlymoreelectronegativethanhydrogen(2.58versus2.20).The
electrondensitymodelshowssomeslightpartialpositivechargeonhydrogenatomoftheSHgroup
andsomeslightpartialnegativechargeonthesulfuratom.

FIGURE19.13 Methanethiol,CH3 SH:

(a)Lewisstructure,
(b)ballandstickmodeland
(c)electrondensitymodel.

IntheIUPACsystem,thiolsarenamedinthesamewayasalcohols,exceptthattheendingthiolis
addedtothenameoftheparentalkane.Commonnamesforsimplethiolsarederivedbynamingthe
alkylgroupbondedtotheSHgroupandaddingthewordmercaptan.Incompoundscontainingother
functionalgroups,thepresenceofanSHgroupisindicatedbytheprefixmercapto.

SulfuranaloguesofethersarenamedbyusingthewordsulfidetoshowthepresenceoftheS
group.Thefollowingarecommonnamesoftwosulfides.

Themostoutstandingpropertyoflowmolarmassthiolsistheirstrong,oftenunpleasantodour,suchas
thosefromrotteneggsandsewage.However,notallthiolshaveanunpleasantodourforexample,
grapefruits,mushrooms,onions,garlicandcoffee(figure19.14)allcontainsulfurcompounds.
 FIGURE19.14Allofthesefoodscontainsulfurcompounds.

Thearomaofgrapefruitisprimarilyduetoathiol,commonlyknownasgrapefruitmercaptan.The
structuralformulaandaballandstickmodelofgrapefruitmercaptanareshownbelow.OnlytheR
enantiomerhasthecharacteristicodour.

PhysicalProperties
Becauseofthesmalldifferenceinelectronegativitybetweensulfurandhydrogen(2.52.1=0.4),we
classifytheSHbondasnonpolarcovalent.Becauseofthislackofpolarity,thiolsshowlittle
intermolecularassociationbyhydrogenbonding.Consequently,theyhavelowerboilingpointsandare
lesssolubleinwaterandotherpolarsolventsthanalcoholsofsimilarmolarmass.Table19.6givesthe
boilingpointsofthreelowmolarmassthiols.Forcomparison,thetablealsogivestheboilingpointsof
alcoholswiththesamenumberofcarbonatoms.
TABLE19.6 Boilingpointsofthreethiolsandthreealcoholswiththesamenumberofcarbonatoms
Thiol Boilingpoint(C) Alcohol Boilingpoint(C)
methanethiol 6 methanol 65
ethanethiol 35 ethanol 78
butane1thiol 98 butan1ol 117
Earlier,weillustratedtheimportanceofhydrogenbondinginalcoholsbycomparingtheboilingpoints
ofethanol(78C)anditsconstitutionalisomerdimethylether(24C).Bycomparison,theboiling
pointofethanethiolis35C,andthatofitsconstitutionalisomerdimethylsulfideis37C.

Thefactthattheboilingpointsoftheseconstitutionalisomersarealmostidenticalindicatesthatlittleor
nohydrogenbondingoccursbetweenthiolmolecules.

ReactionsofThiols
Inthissection,wediscusstheacidityofthiols,andtheirreactionwithstrongbasesandwithmolecular
oxygen.

Acidity
Hydrogensulfideisastrongeracidthanwater.

Similarly,thiolsarestrongeracidsthanalcohols.Compare,forexample,thepKa ofethanolandthepKa
ofethanethiolindiluteaqueoussolution.

Thiolsaresufficientlystrongacidsthat,whendissolvedinaqueoussodiumhydroxide,theyare
convertedcompletelytoalkylsulfidesalts.

OxidationtoDisulfides
Manyofthechemicalpropertiesofthiolsoccurbecausethesulfuratomofathioliseasilyoxidisedto
severalhigheroxidationstates.Themostcommonreactionofthiolsinbiologicalsystemsistheir
oxidationtodisulfides,thefunctionalgroupofwhichisadisulfide(SS)bond.Thiolsarereadily
oxidisedtodisulfidesbymolecularoxygen.Infact,theyaresosusceptibletooxidationthattheymust
beprotectedfromcontactwithairduringstorage.Disulfides,inturn,areeasilyreducedtothiolsby
severalreagents.Thiseasyinterconversionbetweenthiolsanddisulfidesisveryimportantinprotein
chemistry,aswewillseeinchapter24.
Wederivecommonnamesofsimpledisulfidesbylistingthenamesofthegroupsbondedtosulfurand
addingtheworddisulfide,forexample,CH3SSCH3isnameddimethyldisulfide.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.6Amines
Aminesarederivativesofammoniainwhichoneormorehydrogenatomsarereplacedbyalkyloraryl
groups.Aminesareclassifiedasprimary(1),secondary(2)ortertiary(3),dependingonthenumber
ofhydrogenatomsofammoniathatarereplaced.Notethat1,2and3refertothedegreeof
substitutiononthenitrogenatom,notthecarbonatombearingthenitrogenatom(unlikehaloalkanes
andalcoholsseesection19.1).

Aminesarefurtherdividedintoaliphaticaminesandaromaticamines.Inanaliphaticamine,allthe
carbonatomsbondeddirectlytothenitrogenatomarederivedfromalkylgroupsinanaromatic
amine,oneormoreofthegroupsbondeddirectlytothenitrogenatomarearylgroups.Notethatthe
thirdexamplebelow(benzyldimethylamine)isnotclassedasanaromaticaminebecausethenitrogen
atomisnotbondeddirectlyontothearomaticring.

Anamineinwhichthenitrogenatomispartofaringisclassifiedasaheterocyclicamine.Whenthe
nitrogenatomispartofanaromaticring(section16.7,p.726),theamineisclassifiedasaheterocyclic
aromaticamine.Thefollowingarestructuralformulaefortwoheterocyclicaliphaticaminesandtwo
heterocyclicaromaticamines.

WORKEDEXAMPLE19.8

ClassifyingAmines
Alkaloidsarebasicnitrogencontainingcompoundsfoundinplants.Manyalkaloidshave
physiologicalactivitywhenadministeredtohumans.
Examplesofalkaloidsthatarephysiologicallyactiveinhumansincludescopolamine,
nicotineandcocaine.Scopolamine(alsoknownashyoscine)isobtainedfromtheleavesof
theAustralianDuboisiatreeandisclassifiedasananticholinergic(itblockstheactionof
acetylcholine).Thehydrobromidesaltisusedinthepreventionofmotionsickness.Insmall
doses,nicotineisanaddictivestimulant.Inlargerdoses,itcausesdepression,nauseaand
vomiting.Instilllargerdoses,itisadeadlypoison.Solutionsofnicotineinwaterareusedas
insecticides.Cocaineisacentralnervoussystemstimulantobtainedfromtheleavesofthe
cocaplant.

Classifyeachaminogroupinthefollowingalkaloidsaccordingtotype(primary,secondary,
tertiary,heterocyclic,aliphaticoraromatic).
(a)

(b)

(c)

Analysis

Firstidentifythenitrogenatominthecompound.Now,checkthefollowing.
i. Ensurethatthenitrogenatomispartofanamine.(Thereareotherfunctionalgroups
wherethenitrogenatomisnotboundtoalkylorarylgroups.Thesearecalledamide,
nitrileandnitrogroups.)
ii. Ifthenitrogenatomispartofaring,thecompoundisheterocyclic.
 iii.Ifthenitrogenatomisbondeddirectlytoanaromaticring,orpartofanaromaticring,
thenthecompoundisanaromaticamine.
Thencountthenumberofgroupsbondedtothenitrogenatomtodetermineifitisprimary,
secondaryortertiary.

Solution
(a)atertiaryheterocyclicaliphaticamine
(b)onetertiaryheterocyclicaliphaticamineandoneheterocyclicaromaticamine
(c)atertiaryheterocyclicaliphaticamine

PRACTICEEXERCISE19.8
Identifyallcarbonstereocentresin
scopolamine,nicotineandcocaine.

Systematicnamesforaliphaticaminesarederivedjustastheyareforalcohols.Thesuffixeofthe
parentalkaneisdroppedandisreplacedbyaminethatis,theyarenamedalkanamines.

Commonnamesformostaliphaticaminesarederivedbylistingthealkylgroupsbondedtonitrogenin
alphabeticalorderinonewordendinginthesuffixaminethatis,theyarenamedasalkylamines.

WORKEDEXAMPLE19.9

NamingAmines
WritetheIUPACnameforeachofthefollowingamines.

(a)

(b)
 (c)

Analysis

First,youneedtoidentifythelongestchainasthiswillbetheparentamine.Thesuffixeof
theparentalkaneisthendroppedandreplacedbyaminetogiveanalkanamine.Ifthereis
morethanoneaminogroup,thenusediamine,triamineetc.rememberingtoindicatethe
positionoftheaminogroups.Nextyoushouldidentifyanysubstituents.Thesearelistedin
alphabeticalorder,withnumbersindicatingthepositionofthesubstituent.

Solution
(a)hexan1amine
(b)butane1,4diamine(Thisisalsocommonlyknownasputrescinebecauseitsmells
putrid.)
(c)Thesystematicnameofthiscompoundis(R)1phenylpropan2amine.Itscommon
nameisamphetamine.Thedextrorotatoryisomerofamphetamine(shownhere)isa
centralnervoussystemstimulantandismanufacturedandsoldunderseveraltrade
names.ThesaltwithsulfuricacidismarketedasDexedrinesulfate.

Isouranswerreasonable?

Tocheckthatyournamesarecorrect,drawstructuresthatcorrespondtoyouranswersand
comparethesewiththestructuresprovidedinthequestion.

PRACTICEEXERCISE19.9
Writeastructuralformulaforeachofthe
followingamines.
(a)2methylpropan1amine
(b)cyclohexanamine
(c)(R)butan2amine

IUPACnomenclatureretainsthecommonnameanilineforC6H5NH2,thesimplestaromaticamine.Its
simplederivativesarenamedwiththeprefixeso,mandp,ornumberstolocatesubstituents.Several
derivativesofanilinehavecommonnamesthatarestillwidelyused.Amongthesearetoluidine,fora
methylsubstitutedaniline,andanisidine,foramethoxysubstitutedaniline.
SecondaryandtertiaryaminesarecommonlynamedasNsubstitutedprimaryamines.Forasymmetrical
amines,thelargestgroupistakenastheparentamine,thenthesmallergrouporgroupsbondedto
nitrogenarenamed,andtheirlocationisindicatedbytheprefixN(specifyingthattheyareattachedto
nitrogen).

Amongthevariousfunctionalgroupsdiscussedinthistext,theNH2grouphasoneofthelowest
nomenclaturepriorities(theprioritylistisprovidedintable20.1).Thefollowingcompoundseach
containsafunctionalgroupofhigherprecedencethantheaminogroup,and,accordingly,theNH2
groupisindicatedbytheprefixamino.

PhysicalProperties
Aminesarepolarcompounds,andbothprimaryandsecondaryaminesformintermolecularhydrogen
bonds(figure19.15).

FIGURE19.15Intermolecularassociationof1and2aminesbyhydrogenbonding.Nitrogenis
approximatelytetrahedralinshape,withtheaxisofthehydrogenbondalongthefourthaxisof
thetetrahedron.
AnNHNhydrogenbondisweakerthananOHOhydrogenbond,becausethedifferencein
electronegativitybetweennitrogenandhydrogen(3.02.1=0.9)islessthanthatbetweenoxygenand
hydrogen(3.52.1=1.4).Wecanillustratetheeffectofintermolecularhydrogenbondingby
comparingtheboilingpointsofmethylamineandmethanolasshowninthetablebelow.

CH3NH2 CH3OH
numberofelectrons 18 18
boilingpoint(C) 6.3 65.0

Bothcompoundsarepolarmoleculesandinteractinthepureliquidbyhydrogenbonding.Methanolhas
thehigherboilingpointbecausehydrogenbondingbetweenitsmoleculesisstrongerthanthatbetween
moleculesofmethylamine.

Allclassesofaminesformhydrogenbondswithwaterandaremoresolubleinwaterthanhydrocarbons
ofacomparablenumberofelectrons.Mostlowmolarmassaminesarecompletelysolubleinwater
(table19.7).Highermolarmassaminesareonlymoderatelysolubleorinsoluble.
TABLE19.7 Physicalpropertiesofselectedamines
Name Structuralformula Meltingpoint(C) Boilingpoint(C) Solubilityinwater
ammonia NH3 78 33 verysoluble

Primaryamines
methylamine CH3NH2 95 6 verysoluble
ethylamine CH3CH2NH2 81 17 verysoluble
propylamine CH3CH2CH2NH2 83 48 verysoluble
cyclohexylamine C6H11NH2 17 135 slightlysoluble

Secondaryamines
diethylamine (CH3CH2)2NH 48 56 verysoluble

Tertiaryamines
triethylamine (CH3CH2)3N 114 89 slightlysoluble

Aromaticamines
aniline C6H5NH2 6 184 slightlysoluble

Heterocyclicaromaticamines
pyridine C5H5N 42 116 verysoluble

PreparationofAmines
Aminescanbepreparedbyavarietyofmethods,fromarangeofstartingmaterials.Someofthemore
commonmethodswillbediscussedhere.
PreparationfromHaloalkanes
Aminescanbepreparedfromhaloalkanesbynucleophilicsubstitutionreactions(seesection18.2).
Giventhatammoniaisagoodnucleophile,itcanbeusedtoprepareaminesfromhaloalkanes.

Notethatthechargeisbalanced(bothsideshavezeronetcharge).Thealkylammoniumsaltisreadily
convertedtotheaminebyreactionwithastrongerbasethantheamine(e.g.NaOH).

Aproblemwithusingammoniatoprepareprimaryaminesisthattheseaminesarealsonucleophilic
speciesandcanreactinthesamewayasammoniatoproducesecondaryamines.Similarly,secondary
aminescanreacttogivetertiaryamines.Consequently,mixturesof1,2and3aminesareusually
obtained.

Primaryaminescanbeprepared,inatwostepprocess,byusingtheazideion(N3)orphthalimideion
(useofthelatterisknownastheGabrielsynthesis)asnucleophiles.Usingtheseprocesses,secondary
andtertiaryaminesarenotproduced.

SynthesisofArylamines:ReductionoftheNO2Group
Aswehavealreadyseen(section16.8),thenitrationofanaromaticringintroducesaNO2group.A
particularvalueofnitrationisthefactthattheresultingnitrogroupcanbereducedtoaprimaryamino
group,NH2,byhydrogenationinthepresenceofatransitionmetalcatalystsuchasnickel,palladium
orplatinum.

Chemistry

ChemistryResearch
Synthesisingpolyhydroxyalkaloids

Thedevelopmentofnewstrategiesandreactionsforthesynthesisofcompoundsisan
importantfieldofchemistryresearch.Thisresearchprovidesuswithaccesstoawiderange
ofcompoundsthatcanbeusedinavarietyofapplications,includingmedicine,agriculture,
industryandtheenvironment.Naturalproducts(compoundsobtainedfromplantsoranimals)
areoftenchosenassynthetictargetstodemonstratetheutilityofthenewstrategiesor
reactions.Thesenewstrategiesoftenallowthesynthesisofanaloguesorisomersof
compoundswithonlyminormodificationtothesyntheticprocess,thusprovidingscientists
witharangeofsimilarcompoundsthatcanbeusedtobetterunderstandtheeffectofstructure
onreactivityingivenprocesses(usuallybiologicalprocesses).

TheresearchteamledbyProfessorStephenPyneattheUniversityofWollongonghas
developednewstrategiesforthesynthesisofpolyhydroxyalkaloids.Ofparticularinterestare
swainsonineandaustraline,whichhavebeenisolatedfromAustralianplantsandhave
significantbiologicalactivity(i.e.theyaffectbiologicalprocessesinlivingthings).

AsaresultofinvestigationstoidentifythetoxiccomponentresponsibleforSwainsona
poisoning,MurdochUniversityresearchersisolatedswainsoninefromtheAustralianDarling
pea(Swainsonacanescens,figure19.16).Itisthefirstinhibitorofglycoproteinprocessing
enzymes(glycoproteinsarecompoundscontainingcarbohydratesbondedtoproteinsandare
involvedinmanycellularprocesses)tobeselectedforclinicaltestingasananticancerdrug
however,clinicaltrialshavebeenhamperedbyitshighcost.Australinewasisolatedfromthe
seedsoftheAustraliantreeCastanospermumaustrale(figure19.17)andisalsoaninhibitor
ofglycoprocessingenzymes.
 FIGURE19.16AustralianDarlingpea(Swainsonacanescens).

FIGURE19.17Castanospermumaustrale.

ThestrategiesusedbyPyne'sgroupinthesynthesisofthesealkaloidscanbesummarised
intothreekeysteps:
1.reactionofaprimaryaminewithanepoxide(Epoxidesarehighlystrainedcyclicethers
inwhichtheoxygenatomispartofathreememberedring.)
2.theformationofacycloalkene
3.theoxidationofthealkenegrouptoformavicinaldiol.(TheOHgroupsareon
adjacentcarbonatoms.)
Thesereactionsareillustratedbelowusingtheparticularstepsinthesynthesisofswainsonine.

Thefirstkeystepinvolvesthecleavageofanether.Althoughethersaregenerallyfairlyunre
active,epoxidesareanexceptionduetothehighringstrainassociatedwiththethree
 memberedring.Consequentlytheopeningoftheepoxidebyreactionwithanamineoccurs
quitereadily.

Inthesecondkeystep,knownasaringclosingmetathesis,twoalkenegroupsreactto
produceacyclicalkene(withlossofethene).Thedeveloperofthisreaction,RobertGrubbs,
wasawardedthe2005NobelPrizeinchemistryforhiscontributionstometathesisreactions.

Thefinalkeystepistheconversionofanalkenetoadiolwithcontrolofthestereochemistry
(knownasasymmetricdihydroxylation).Thedeveloperofthischemistry,BarrySharpless,
wasawardedaNobelPrizein2001forthedevelopmentofasymmetricoxidationreactions.

Thismethodhasthepotentialdisadvantagethatothersusceptiblegroups,suchasacarboncarbon
doublebond,andthecarbonylgroupofanaldehydeorketone,mayalsobereduced.Notethatneither
theCOOHnorthearomaticringisreducedundertheseconditions.

Alternatively,anitrogroupcanbereducedtoaprimaryaminogroupbyametalinacid.

Themostcommonlyusedmetalreducingagentsareiron,zincortinindiluteHCl.Whenreducedby
thismethod,theamineisobtainedasasalt,whichisthentreatedwithastrongbasetoliberatethefree
amine.

OtherMethodsforthePreparationofAmines
Therearemanyothermethodsavailableforthepreparationofamines.Someofthese,discussedinmore
detaillater,includethereductiveaminationofaldehydesandketones(section21.5),andthereduction
orhydrolysisofamides(section23.5).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
19.7ReactionsofAmines
Thereactionsofaminesaregovernedbytheunsharedpairofelectronsonthenitrogenatom.Becauseofthese
unsharedelectrons,aminesarebothbasicandnucleophilic.Consequently,aminesreactreadilywithacidstoform
saltsandalsoreactwithelectrophilicspecieslikehaloalkanes,acylhalidesandmanyothers.

BasicityofAmines
Likeammonia,allaminesareweakbases,andaqueoussolutionsofaminesarebasic.Thefollowingacidbase
reactionbetweenanamineandwateriswrittenusingcurvedarrowstoemphasisethat,inthisprotontransfer
reaction,theunsharedpairofelectronsonnitrogenformsanewcovalentbondwithhydrogenanddisplacesthe
hydroxideion.

ThevalueofKb,thebaseionisationconstant,formethylamineis4.3710 4(pKb=3.36).

Itisalsocommontodiscussthebasicityofaminesbyreferringtotheacidityconstantofthecorresponding
conjugateacid,asillustratedfortheionisationofthemethylammoniumionbelow.

ValuesofpKa andpKbforanyacidconjugatebasepairarerelatedbytheequation:

ValuesofpKa andpKbforselectedaminesaregivenintable19.8onthenextpage.Youmaywishtoreview
chapter11forfurtherdiscussionofacidbaseequilibria.
TABLE19.8 Basestrengths(pKb )ofselectedaminesandacidstrengths(pKa )oftheirconjugateacidsat25C(a)

Amine Structure pKb pKa

ammonia NH3 4.74 9.26
Primaryamines
ethylamine CH3CH2NH2 3.19 10.81
cyclohexylamine C6H11NH2 3.34 10.66

Secondaryamines
diethylamine (CH3CH2)2NH 3.02 10.98
Tertiaryamines
triethylamine (CH3CH2)3N 3.25 10.75
Aromaticamines
 aniline 9.36 4.64

4methylaniline 8.92 5.08

4nitroaniline 13.0 1.0

Heterocyclicaromaticamines
pyridine 8.82 5.18

(a)Foreachamine,pKa +pKb=14.00at25C.

WORKEDEXAMPLE19.10

PredictingEquilibrium
Predictthepositionofequilibriumfortheacidbasereactionbelow.

Analysis

Usetheapproachwedevelopedearliertopredictthepositionofequilibriuminacidbasereactions.
Equilibriumfavoursthereactionbetweenthestrongeracidandstrongerbasetoformtheweakeracid
andweakerbase.

Solution

Equilibriumfavourstheformationofmethylammoniumionsandacetateions.

PRACTICEEXERCISE19.10
Predictthepositionofequilibriumforthe
followingacidbasereaction.

Fromtheinformationintable19.8,wecanmakethefollowinggeneralisationsabouttheacidbasepropertiesof
thevariousclassesofamines:
1.Allaliphaticamineshaveaboutthesamebasestrength,withpKbvaluesfrom3.0to4.0,andareslightly
 strongerbasesthanammonia.
2.Aromaticaminesareconsiderablyweakerbasesthanaliphaticamines.Compare,forexample,thevaluesof
pKbforanilineandcyclohexylamineshownbelow.

Thebasicityconstantforanilineissmaller(thelargerthevalueofpKb,theweakeristhebase)thanthatfor
cyclohexylaminebyafactorof10 6.
Aromaticaminesareweakerbasesthanaliphaticaminesbecauseoftheresonanceinteractionoftheunshared
pairofelectronsonnitrogenwiththeelectronsystemofthearomaticring.Thisresonanceinteractionisalso
thereasonthatphenolsaremoreacidicthanalcohols(comparetheresonancediagrambelowwiththatfor
phenoxideiononp.826).Thisresonancereducestheelectrondensityonthenitrogenatom(oroxygenatom
inthecaseofphenols)makingitapoorerprotonacceptor(orabetterprotondonorinthecaseofphenols)
thanthenonaromaticanalogues.Becausenoresonanceinteractionispossibleforanalkylamine,theelectron
paironitsnitrogenatomismoreavailableforreactionwithanacid.

3.Electronwithdrawinggroupssuchashalogens,andnitroandcarbonylgroupsdecreasethebasicityof
substitutedaromaticaminesbyfurtherdecreasingtheavailabilityoftheelectronpaironnitrogen.The
diagrambelowshowstheresonanceformsfor4nitroanilineshowinghowthenitrogroupreducesthe
basicity.Youwillnoticethattherearefourresonanceformsinwhichthenitrogenatomoftheaminogroup
doesnothaveanonbondingpairofelectrons(inthecaseaboveforanilinetherearethree).Thiselectron
withdrawingeffectofthenitrogrouphasbeendiscussedpreviouslywithrespecttoincreasingtheacidityof
phenols(seesection19.3).Inbothcases,thenitrogroupiswithdrawingelectronsfromtheheteroatom
(nitrogeninanilines,oroxygeninphenols).
WORKEDEXAMPLE19.11

StrengthofBases
Selectthestrongerbaseineachofthefollowingpairsofamines.
(a)

(b)

Analysis

Inworkedexample19.8,weclassifiedaminesasprimary,secondary,tertiary,heterocyclic,aliphaticor
aromatic.Fromtable19.8wededucethataliphaticaminesarestrongerbasesthanaromaticamines.
Therefore,onceyouhaveclassifiedtheaminesyoushouldbeabletodeterminewhichisthestronger
base.

Solution
(a)Morpholine(B)isthestrongerbase(pKb=5.79).Ithasabasicitycomparabletothatof
secondaryaliphaticamines.Pyridine(A),aheterocyclicaromaticamine(pKb=8.82),is
considerablylessbasicthanaliphaticamines.
(b)Benzylamine(D),aprimaryaliphaticamine,isthestrongerbase(pKb=34).Thearomatic
amine,otoluidine(C),istheweakerbase(pKb=910).

PRACTICEEXERCISE19.11
Selectthestrongeracidfromeachofthefollowingpairsofions.
(a)

(b)
Guanidine,withapKbvalueof0.4,isoneofthestrongestbasesamongneutralcompounds.

Theremarkablebasicityofguanidineisattributedtothefactthatthepositivechargeontheguanidiniumionis
delocalisedequallyoverthethreenitrogenatoms,asshownbythethreeequivalentcontributingstructuresbelow.

Hence,theguanidiniumionisahighlystablecation.Thepresenceofaguanidinegroupintheaminoacidarginine
accountsforthebasicityofitssidechain(section24.2).

ReactionwithAcids
Amines,whethersolubleorinsolubleinwater,reactquantitativelywithstrongacidstoformwatersolublesalts,as
illustratedbelowbythereactionof(R)norepinephrine(noradrenaline)withaqueousHCltoformahydrochloride
salt.

chemicalConnections

BasicityandDrugActivity

Alkaloidsarenitrogencontainingcompoundsofplantoranimaloriginwithsignificantpharmacological
properties.Manydrugsalsocontainatleastonenitrogenatom.Whyisthenitrogenatomimportantfor
pharmacologicalactivity?Youwillnoticethatthenitrogenatomsinthecompoundsmentionedhere,
alongwithsomeothersmentionedpreviously(forexamplesulbutamolandthoseinworkedexample
19.8)areallpresentasaminogroups.BecauseaminesareweakbasesatphysiologicalpH(7.4),they
arepresentasanequilibriummixtureoftheprotonated(ionic)andnonprotonated(neutral)formsatthis
pH,theionicformpredominates.TheequilibriumconcentrationsofthetwoformsdependonthepKa
valueoftheionicformandthepHoftheenvironment.Itistheionicformthatbindstotheactivesite
thepositivelychargedammoniumionbindstoanegativelychargedcarboxylateion.Althoughtheionic
formisrequiredtobindtotheactivesite,itisincapableofcrossingthenonpolarenvironmentofthecell
membranes.Sohowdoesthedrugreachthetarget?
Theanswerliesintheequilibriumbetweentheionicandneutralformsofthedrug.Theneutralform
crossesthemembraneand,onceontheotherside,reestablishesequilibrium,producingsomeofthe
ionicformthatbindstothereceptor.Ontheothersideofthemembrane,theionicformthatcouldnot
crossthemembranealsoreestablishesequilibriumbyformingmoreoftheneutralformthatcancross
themembrane.Inthisway,thedrugcancrossthemembraneintheneutralformandinteractwiththe
activesiteastheionicform.Therateatwhichthisprocessoccursdependsontheequilibrium
concentrationsofthetwoforms.

Morphineandcodeine(amonomethyletherofmorphine)areopioidanalgesicsobtainedfromunripe
seedpodsoftheopiumpoppy,Papaversomniferum(figure19.18),andhavebeenknownforcenturies.
Heroinisnotnaturallyoccurringbutissynthesisedbytreatingmorphinewith2moleequivalentsof
aceticanhydride.

FIGURE19.18Theopiumpoppy,Papaversomniferum,isthesourceofmorphineandcodeine.
Eventhoughmorphineisoneofmodernmedicine'smosteffectivepainkillers,ithastwoseriousside
effectsitisaddictive,anditdepressestherespiratorycontrolcentreofthecentralnervoussystem.Large
dosesofmorphine(orheroin)canleadtodeathbyrespiratoryfailure.Forthesereasons,chemistshave
soughttoproducepainkillerswithouttheseseriousdisadvantages.Onestrategyinthisongoingresearch
hasbeentosynthesisecompoundsrelatedinstructuretomorphineinthehopethattheywouldbe
equallyeffectiveanalgesics,butwithdiminishedsideeffects.Thefollowingarestructuralformulaefor
twosuchcompoundsthathaveprovenclinicallyuseful.

Levomethorphanisapotentanalgesic.Interestingly,itsdextrorotatoryenantiomer,dextromethorphan,
hasnoanalgesicactivity.Itdoes,however,showapproximatelythesamecoughsuppressingactivityas
morphineandisusedextensivelyincoughremedies.Althoughnaltrexonehasasimilarstructuretothat
ofmorphine,itcountersmorphine's(andheroin's)effectandhasbeenusedtocombatheroinaddiction.

Ithasbeendiscoveredthattherecanbeevenfurthersimplificationinthestructureofmorphinelike
analgesicsthemorphineruledescribestheminimumrequirementsforopiatelikeeffects.Therule
statesthat,foracompoundtoexhibitopiatelikeeffects,itshouldcontain(1)anaromaticring,(2)a
quaternarycarbonatomattachedtotheringand(3)atertiaryaminetwocarbonatomsfromthe
quaternarycarbonatom,and(4)oneofthegroupsonthetertiaryaminemustbesmall(e.g.amethyl
group).Onesuchsimplificationisrepresentedbymeperidine,thehydrochloridesaltofwhichisthe
widelyusedanalgesicDemerol.Itwashopedthatmeperidineandrelatedsyntheticdrugswouldbefree
ofmanyofthemorphinelikeundesirablesideeffects.Itisnowclear,however,thattheyarenot.

In1992,thealkaloidepibatidinewasisolatedfromtheskinoftheEcuadorianpoisonfrog,Epipedobates
 tricolor(figure19.19).

FIGURE19.19Epipedobatestricolor,theEcuadorianpoisonfrog.

Epibatidinehasseveraltimestheanalgesicpotencyofmorphineandisthefirstchlorinecontaining,
nonopioid(nonmorphinelikeinstructure)analgesiceverisolatedfromanaturalsource.Itishopedthat
thissimplealkaloidwillbealeadcompoundinthedevelopmentofanewfamilyofpainkillers.Itis
currentlymarketedasitstartratesaltforuseinbiomedicalresearch.

Norepinephrineisaneurotransmitterandastresshormonesecretedbythemedullaoftheadrenalgland.Itplaysan
importantpartinattentionandfocus.PeoplewithADD/ADHD(attentiondeficithyperactivitydisorder)are
prescribeddrugsthathelpincreasethelevelsofnorepinephrineinthebrain.

Drugcompanieshavetakenadvantageofthereactionofamineswithstrongacidstoimprovethesolubilityof
manydrugs,includingcodeineandsalbutamol.Inthetreatmentofasthma,salbutamolissoldasthesulfatesaltfor
increasedwatersolubilityinthelungs.
Thebasicityofaminesandthesolubilityofaminesaltsinwatercanbeusedtoseparateaminesfromwater
insoluble,nonbasiccompounds.Figure19.20isaflowchartfortheseparationofanilinefromanisole.Notethat
anilineisrecoveredfromitssaltbytreatmentwithNaOH.

FIGURE19.20Separationandpurificationofanamineandaneutralcompound.

WORKEDEXAMPLE19.12

AminoAcidAlanine
Thefollowingaretwostructuralformulaeforalanine,2aminopropanoicacid,oneofthebuilding
blocksofproteins(chapter24).
 IsalaninebetterrepresentedbystructuralformulaAorB?

Analysis

Thisquestionissimilartoworkedexample19.10exceptthattheamineandthecarboxylicacidareon
thesamemolecule.StructuralformulaAcontainsbothanaminogroup(abase)andacarboxylgroup
(anacid),whilestructureBcontainstheammoniumgroup(theconjugateacid)andthecarboxylate
group(theconjugatebase).

Solution

Protontransferfromthestrongeracid(COOH)tothestrongerbase(NH2)givesaninternalsalt
therefore,Bisthebetterrepresentationofalanine.Withinthefieldofaminoacidchemistry,theinternal
saltrepresentedbyBiscalledazwitterion(chapter24).

PRACTICEEXERCISE19.12
Asshowninworkedexample19.12,alanineis
betterrepresentedasazwitterion.Supposethat
thezwitterionisdissolvedinwater.
(a)Inwhatwaywouldyouexpectthe
structureofalanineinaqueoussolutionto
changeifconcentratedHClwereaddedto
adjustthepHofthesolutionto2.0?
(b)Inwhatwaywouldyouexpectthe
structureofalanineinaqueoussolutionto
changeifconcentratedNaOHwereadded
tobringthepHofthesolutionto12.0?

ReactionofPrimaryAromaticAmineswithNitrousAcid
Nitrousacid,HNO2,isanunstablecompoundthatispreparedbyaddingsulfuricorhydrochloricacidtoan
aqueoussolutionofsodiumnitrite,NaNO2.Nitrousacidisaweakacidandionisesaccordingtothefollowing
equation.

Nitrousacidreactswithaminesindifferentways,dependingonwhethertheamineisprimary,secondaryor
tertiary,andwhetheritisaliphaticoraromatic.Weconcentrateonthereactionofnitrousacidwithprimary
aromaticamines,becausethisreactionisusefulinorganicsynthesis.

Treatmentofaprimaryaromaticamine,forexampleaniline,withnitrousacidgivesarelativelystablediazonium
salt.
Wecanalsowritetheequationforthisreactioninthefollowingmoreabbreviatedform.

Primaryaliphaticaminesalsogivediazoniumsalts,buttheseareunstableanddecomposeimmediatelytogivea
complexmixtureofproducts.Whenwewarmanaqueoussolutionofanaromaticdiazoniumsalt,theN2+group
isreplacedbyanOHgroup.Thisreactionisoneofthefewmethodswehaveforthesynthesisofphenols.It
enablesustoconvertanaromaticaminetoaphenolbyfirstformingthearomaticdiazoniumsaltandthenheating
thesolution.Inthismanner,wecanconvert2bromo4methylanilineto2bromo4methylphenol.

WORKEDEXAMPLE19.13

ConversionofTolueneto4hydroxybenzoicAcid
Showthereagentsthatwillbringabouteachstepinthisconversionoftolueneto4hydroxybenzoic
acid.

Analysis

Inthisquestionyouneedtoidentify,ineachstep,thechangeingoingfromthestartingmaterialtothe
product.
Step1:Thisisanelectrophilicaromaticsubstitutionreaction(section16.8),specificallyanitration
 reaction.
Step2:Thisisanoxidationofthebenzyliccarbonatom(section23.4).
Step3:Thisisareductionofthenitrogroup(section19.6 ).
Step4:Thisisaconversionofaprimaryaromaticaminetoaphenol(section19.7 ).

Solution
Step1:Treatmentwithnitricacid/sulfuricacid,followedbyseparationoftheorthoandpara
isomers.
Step2:Treatmentwithchromicacidorpotassiumpermanganate.
Step3:TreatmentwithH2inthepresenceofatransitionmetalcatalystorusingFe,SnorZninthe
presenceofaqueousHCl,followedbyneutralisationofthehydrochloridesalt.
Step4:TreatmentwithNaNO2/HCltoformthediazoniumionsaltandthenwarmingthesolution.

PRACTICEEXERCISE19.13
Showhowyoucanusethesetofstepsfrom
workedexample19.13,butinadifferentorder,to
converttolueneto3hydroxybenzoicacid.

Diazoniumsaltscanalsoundergocouplingreactionswithphenolsandanilinestogiveazocompounds(ArN
NAr).Thesecompoundsarebrightlycolouredandarecommonlyusedasdyes.Thiscouplingisanother
exampleofanelectrophilicaromaticsubstitutionreaction(seesection16.8),wheretheelectrophileisthe
diazoniumsalt.Theadditionofthediazoniumsaltderivedfrom4nitroanilinetoabasicsolutionofphenol
instantlygivesabrilliantreddye(figure19.21).

FIGURE19.21Azodyesproducedbytheadditionof4nitrobenzenediazoniumchloridetophenol(red),1naphthol(blue)
and2naphthol(purple).
ThereactionofsecondaryamineswithnitrousacidproducesNnitrosamines.

Nitrosaminesareimportantbecausemanyareknowntobecarcinogensinanimals,andtheyhavebeenfoundin
cookedfoodsthathavebeenpreservedwithsodiumnitrite.Sodiumnitriteisaddedtomeatstoinhibitthegrowth
ofClostridiumbotulinum,whichcausesbotulism,adeadlyformoffoodpoisoning.

Amideformation
Animportantreactionofaminesistheformationofamidesbycondensationwithacidchloridesorcarboxylic
anhydrides.Thechemistrywillbediscussedingreaterdetailinchapter23(carboxylicacids)andchapter24
(aminoacidsandproteins).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
Alcohols
ThealcoholfunctionalgroupisanOH(hydroxyl)groupbondedtoansp 3hybridisedcarbonatom.
Alcoholsareclassifiedasprimary,secondaryortertiary,dependingonwhethertheOHgroupis
bondedtoaprimary,secondaryortertiarycarbonatom.IUPACnamesforalcoholsareformedby
changingthesuffixoftheparentalkanefrometool.Commonnamesforalcoholsarederivedby
namingthealkylgroupbondedtotheOHgroupandaddingthewordalcohol.

Alcoholsarepolarcompoundswiththeoxygenatombearingapartialnegativechargeandboththe
carbonatomandhydrogenatombondedtoitbearingpartialpositivecharges.Becauseofinter
molecularhydrogenbonding,theboilingpointsofalcoholsarehigherthanthoseofhydrocarbonswith
asimilarnumberofelectrons.Becauseofincreaseddispersionforces,theboilingpointsofalcohols
increasewithincreasingnumberofelectrons(molarmass).Alcoholsinteractwithwaterbyhydrogen
bondingandthereforearemoresolubleinwaterthanhydrocarbonswithasimilarnumberofelectrons.

Reactionsofalcohols
Sincealcoholshaveareactivitysimilartowater,theycanbereadilydeprotonatedtoformalkoxides,or
protonatedtoformoxoniumions.Theyarereadilyconvertedintoalkenes,haloalkanes,aldehydes,
ketones,carboxylicacidsandesters.Theycanalsobepreparedfromthesefunctionalgroups.

Phenols
ThephenolfunctionalgroupisanOHgroupbondeddirectlytoabenzenering.Phenolandits
derivativesareweakacids,withpKa valuesofapproximately10.0,butareconsiderablystrongeracids
thanalcohols,whichhavepKa valuesof1618.Theyreactquantitativelywithstrongbasestogive
watersolublephenoxidesalts.

Ethers
Theetherfunctionalgroupisanoxygenatombondedtotwocarbonatomsthatarenotalsobondedtoa
heteroatom.IntheIUPACnameofanether,theparentalkaneisnamed,andthentheORgroupis
namedasanalkoxysubstituent.Commonnamesarederivedbynamingthetwogroupsbondedto
oxygen,followedbythewordether.Ethersaremoderatelypolarcompounds.Theirboilingpointsare
closetothoseofhydrocarbonswithasimilarnumberofelectrons.Becauseethersarehydrogenbond
acceptors,theyaremoresolubleinwaterthanarehydrocarbonswithasimilarnumberofelectrons.

Thiols
AthiolisthesulfuranalogueofanalcoholitcontainsanSH(sulfhydryl)groupinplaceofanOH
group.Thiolsarenamedinthesamemannerasalcohols,butthesuffixeisreplacedbythiol.Common
namesforthiolsarederivedbynamingthealkylgroupbondedtoSHandaddingtheword
mercaptan.Incompoundscontainingfunctionalgroupsofhigherprecedence,thepresenceofathiolis
indicatedbytheprefixmercapto.Forthioethers,namethetwogroupsbondedtosulfur,followedby
thewordsulfide.TheSHbondisnonpolar,andthephysicalpropertiesofthiolsaresimilartothose
ofhydrocarbonswithasimilarnumberofelectrons.

Amines
Aminesareclassifiedasprimary,secondaryortertiary,dependingonthenumberofhydrogenatomsof
ammoniareplacedbyalkylorarylgroups.Inanaliphaticamine,allcarbonatomsbondedtonitrogen
arederivedfromalkylgroups.Inanaromaticamine,oneormoreofthegroupsbondedtonitrogenare
arylgroups.Aheterocyclicamineisanamineinwhichthenitrogenatomispartofaring.A
heterocyclicaromaticamineisanamineinwhichthenitrogenatomispartofanaromaticring.

InIUPACnomenclature,aliphaticaminesarenamedalkanamines.Inthecommonsystemof
nomenclature,aliphaticaminesarenamedalkylamines,withthealkylgroupslistedinalphabeticalorder
inonewordendinginthesuffixamine.

Aminesarepolarcompounds,andprimaryandsecondaryaminesassociatebyintermolecularhydrogen
bonding.BecauseanNHNhydrogenbondisweakerthananOHOhydrogenbond,amines
havelowerboilingpointsthanalcoholswithasimilarnumberofelectronsandstructure.Allclassesof
aminesformhydrogenbondswithwaterandaremoresolubleinwaterthanhydrocarbonswithasimilar
numberofelectrons.

Reactionsofamines
Aminesareweakbases,andaqueoussolutionsofaminesarebasic.Thebasicityconstantforanamine
inwaterisgiventhesymbolKb.Itisalsocommontodiscusstheacidbasepropertiesofaminesby
referencetotheacidityconstant,Ka ,fortheconjugateacidoftheamine.Acidityandbasicityconstants
foranamineinwaterarerelatedbytheequationpKa +pKb=14.00at25C.

Aminesreactwithstrongacidstoproducewatersolublesalts,astrategyusedbydrugcompaniesto
enhancethesolubilityofdrugs.Aminescanalsoreactasnucleophilesinsubstitutionreactions.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Preparationofalcoholsfromalkenes(section19.1)
Alcoholscanbepreparedbytheacidcatalysedhydrationofalkenes.

Preparationofalcoholsfromhaloalkanes(section19.1)
AlcoholscanbepreparedfromhaloalkanesbythenucleophilicsubstitutionofOHorwater.

Preparationofalcoholsbyreductionofcarbonylcompounds(section19.1)
Alcoholscanbepreparedbythereductionofcarbonylcompounds.Aldehydes,acidsandestersare
reducedtoprimaryalcohols,andketonesarereducedtosecondaryalcohols.

PreparationofalcoholsfromGrignardreagents(section19.1)
AlcoholscanbepreparedbytheadditionofGrignardreagentstocarbonylcompounds.Aldehydesgive
secondaryalcohols,whileketonesandestersgivetertiaryalcohols.

Acidityofalcohols(section19.2)
Indiluteaqueoussolution,methanolandethanolarecomparableinaciditytowater.Secondaryand
tertiaryalcoholsareweakeracidsthanwater.

Reactionofalcoholswithactivemetals(section19.2)
AlcoholsreactwithLi,Na,Kandotheractivemetalstoformmetalalkoxides,whicharegenerally
strongerbasesthanNaOHandKOH.

ReactionofalcoholswithHCl,HBrandHI(section19.2)
PrimaryalcoholsreactwithHBrandHIbyanSN2mechanism.

TertiaryalcoholsreactwithHCl,HBrandHIbyanSN1mechanism,withtheformationofacarbocation
intermediate.

SecondaryalcoholsmayreactwithHCl,HBrandHIbyanSN2oranSN1mechanism,dependingonthe
alcoholandexperimentalconditions.

ReactionofalcoholswithSOCl2(section19.2)
Thereactionofalcoholswiththionylchlorideisoftenthemethodofchoiceforconvertinganalcohol
intoanalkylchloride.

Reactionofalcoholswithphosphorushalides(section19.2)
Thereactionofalcoholswithphosphorushalidesisoftenusedforthepreparationofalkylbromides.

Acidcatalyseddehydrationofalcohols(section19.2)
Whenisomericalkenesarepossible,themajorproductofacidcatalyseddehydrationofalcoholsis
generallythemoresubstitutedalkene(Zaitsev'srule).

Oxidationofaprimaryalcoholtoanaldehyde(section19.2)
Theoxidationofaprimaryalcoholtoanaldehydeismostconvenientlycarriedoutusingpyridinium
chlorochromate(PCC).

Oxidationofaprimaryalcoholtoacarboxylicacid(section19.2)
Aprimaryalcoholisoxidisedtoacarboxylicacidbychromicacid.

Oxidationofasecondaryalcoholtoaketone(section19.2)
AsecondaryalcoholisoxidisedtoaketonebychromicacidandbyPCC.

Esterformation(section19.2)
Alcoholsreactreadilywithcarboxylicacidsunderacidcatalysistoproduceesters(thisreactionwillbe
discussedinmoredetailinchapter23).

Acidityofphenols(section19.3)

Substitutionbyelectronwithdrawinggroups,suchashalogensorthenitrogroup,increasestheacidity
ofphenols.

Reactionofphenolswithstrongbases(section19.3)
Waterinsolublephenolsreactquantitativelywithstrongbasestoformwatersolublesalts.

Oxidationofphenols(section19.3)

Esterformation(section19.3)
Estersofphenolscanbepreparedbyreactionwithacidchloridesoranhydrides.

ThisreactionisoftencarriedoutinthepresenceofabasetoneutralisetheHClasitisformed.
Etherformation(section19.3)
Duetotheacidityofphenols,theyreactwithhaloalkanestoproduceethersundermildlybasic
conditions.

Acidityofthiols(section19.5)
Thiolsareweakacids,pKa =89,butareconsiderablystrongeracidsthanalcohols,pKa =1618.

Oxidationtodisulfides(section19.5)
OxidationofathiolbyO2givesadisulfide.

Preparationofaminesfromhaloalkanes(section19.6)
Aminescanbepreparedfromhaloalkanesbynucleophilicsubstitutionwithanappropriatenucleophile.

ReductionofanaromaticNO2group(section19.6)
AnNO2grouponanaromaticringcanbereducedtoanaminogroupbycatalytichydrogenation,orby
treatmentwithametalandhydrochloricacid,followedbyastrongbasetoliberatethefreeamine.

Basicityofaliphaticamines(section19.7)
Mostaliphaticamineshavecomparablebasicities(pKb=3.04.0)andareslightlystrongerbasesthan
ammonia.
Basicityofaromaticamines(section19.7)
Aromaticamines(pKb=9.010.0)areconsiderablyweakerbasesthanaliphaticamines.Resonance
stabilisationfrominteractionoftheunsharedelectronpaironnitrogenwiththesystemofthearomatic
ringdecreasestheavailabilityofthatelectronpairforreactionwithanacid.Substitutionontheringby
electronwithdrawinggroupsfurtherdecreasesthebasicityoftheNH2group.

Reactionofamineswithstrongacids(section19.7)
Allaminesreactquantitativelywithstrongacidstoformwatersolublesalts.

Conversionofaprimaryaromaticaminetoaphenol(section19.7)
Treatmentofaprimaryaromaticaminewithnitrousacidgivesanarenediazoniumsalt.Heatingthe
aqueoussolutionofthissaltproducesN2gasandaphenol.

Formationofazodyes(section19.7)
Arenediazoniumsaltsalsocouplewithphenolsandanilinestogiveazodyes.

FormationofNnitrosamines(section19.7)
SecondaryaminesreactwithnitritesunderacidicconditionstoproduceNnitrosamines.

Formationofamides(section19.7)
Aminescanreactwithacidchloridesandanhydridestoproduceamides(thisreactionwillbediscussed
inmoredetailinchapter23).
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Alcohols
19.1Classifythefollowingalcoholsasprimary,secondaryortertiary.
(a)

(b)

19.2Classifythefollowingalcoholsasprimary,secondaryortertiary.
(a)(CH3)3COH
(b)

19.3Namethefollowingcompounds.
(a)
(b)
(c)

(d)

19.4Namethefollowingcompounds.
(a)

(b)

(c)

(d)

19.53butanolisnotapropername,butastructurecouldstillbewrittenforit.Whatisthisstructure,
andwhatIUPACnameshouldbeused?
19.61chloropentan4olisnotapropername,butastructurecouldstillbewrittenforit.Whatisthis
structure,andwhatIUPACnameshouldbeused?
19.7ExplainwhyCH3CH2CH2OHismoresolubleinwaterthanCH3CH2CH2CH3.
19.8Examinethestructuresofthefollowingcompounds.

(a)Whichhasthehighestsolubilityinwater?Explain.
(b)Whichhasthelowestsolubilityinwater?Explain.
19.9Arrangethecompoundsinquestion19.8inorderofincreasingboilingpoint.
19.10Arrangethesecompoundsinorderofincreasingboilingpoint(valuesinCare42,78,117and
198).
(a)CH3CH2CH2CH2OH
(b)CH3CH2OH
(c)HOCH2CH2OH
(d)CH3CH2CH3
19.11Givethestructuralformulaofanalkeneoralkenesfromwhicheachofthefollowingalcohols
canbeprepared.
(a)butan2ol
(b)1methylcyclohexanol
(c)2methylpentan2ol
19.12Givethestructuralformulaofanalkeneoralkenesfromwhicheachofthefollowingalcohols
canbeprepared.
(a)hexan3ol
(b)cyclopentanol
(c)4methyloctan2ol
19.13Givethestructuralformulaofthealcohol(s)formedonthereductionofthefollowingcarbonyl
compounds.
(a)

(b)

19.14Givethestructuralformulaofthealcohol(s)formedonthereductionofthefollowingcarbonyl
compounds.
(a)
 (b)

Reactionsofalcohols
19.15Showhowtodistinguishbetweencyclohexanolandcyclohexeneusingasimplechemicaltest.
19.16Showhowtodistinguishbetweenpentan2oland2methylpentan2olusingasimplechemical
test.
19.17Writeequationsforthereactionofbutan1ol,aprimaryalcohol,withthefollowingreagents.
(a)Nametal
(b)HBr,heat
(c)K2Cr2O7,H2SO4,heat
(d)SOCl2
(e)pyridiniumchlorochromate(PCC)
(f) PBr3
19.18Writeequationsforthereactionof(i)butan2ol,asecondaryalcohol,and(ii)1
methylcyclohexanol,atertiaryalcohol,withthefollowingreagents.
(a)Nametal
(b)H2SO4,heat
(c)HBr,heat
(d)K2Cr2O7,H2SO4,heat
(e)SOCl2
(f) pyridiniumchlorochromate(PCC)
19.19Writetheequationfortheequilibriumthatispresentinasolutionofpropanoicacidand
methanolwithatraceofstrongacid.
19.20Whenthereactiondescribedin19.19iscarriedoutinthelaboratory,methanolisusedinvast
excess,usuallyasthesolvent,eventhoughonlyonemoleequivalentisrequired.Whatisthe
advantageofusingsuchanexcessofmethanol?
Phenols
19.21Amonofunctionalorganicoxygencompounddissolvesinaqueousbasebutnotinaqueousacid.
Towhichfamilyoforganiccompoundsthatwestudiedinthischapterdoesthiscompound
belong?Explain.
19.22Whydowaterinsolublecarboxylicacids(pKa =45)dissolvein10%sodiumbicarbonatewith
theevolutionofagas,butwaterinsolublephenols(pKa =9.510.5)donotshowthischemical
behaviour?
19.23Useresonancetheorytoexplainwhyphenol(pKa =9.99)isastrongeracidthancyclohexanol
(pKa =18).
19.24Arrangethecompoundsineachofthefollowingsetsinorderofincreasingacidity(fromleast
acidictomostacidic).
(a)
 (b)

(c)

19.25Givethestructureoftheexpectedproductformedwhen2bromophenolreactswitheachofthe
followingreagents.
(a)sodiumhydroxide
(b)chromicacid
(c)acetylchloride
(d)sodiumhydroxidefollowedbymethyliodide
(e)benzenediazoniumchloride(section19.7 )
19.26Givethestructureoftheexpectedproductformedwhen4methoxyphenolreactswitheachofthe
followingreagents.
(a)Nametal
(b)K2Cr2O7,H2SO4
(c)sodiumhydroxidefollowedby2bromopropane
(d)benzoylchloride
Ethers
19.27Writenamesforthefollowingethers.
(a)

(b)

(c)

19.28Drawastructuralformulaforeachofthefollowingethers.
(a)diisopropylether
(b)1,4dimethoxybenzene
(c)3chloro1ethoxybutane
19.29Whichofthefollowingcompoundsismoresolubleinwater?Explain.
19.30Arrangethefollowingcompoundsinorderofincreasingboilingpoint(valuesinCare42,24,
78and118).
A.CH3CH2OH
B.CH3OCH3
C.CH3CH2CH3
D.CH3COOH
19.31Eachofthefollowingcompoundsisacommonorganicsolvent.Fromeachpairofcompounds,
selectthesolventwiththegreatersolubilityinwater.
(a)CH3CH2OCH2CH3orCH2Cl2
(b)CH3CH2OCH2CH3orCH3CH2OH
19.32Eachofthefollowingcompoundsisacommonorganicsolvent.Fromeachpairofcompounds,
selectthesolventwiththegreatersolubilityinwater.
(a)CH3CH2OCH2CH3orCH3(CH2)3CH3
(b)CH3CH2OCH2CH3orCH3OCH2CH2OCH3
(c)CH3CH2OCH2CH3or(CH3)2CHOCH(CH3)2
Thiols
19.33DrawstructurescorrespondingtothefollowingIUPACnames.
(a)3methylbutane1thiol
(b)dipropylsulfide
(c)2mercaptoethanol
19.34Namethefollowingcompounds.
(a)

(b)

(c)

(d)

19.35Thefollowingarestructuralformulaeforbutan1olandbutane1thiol.Oneofthesecompounds
hasaboilingpointof98.5C,theotherhasaboilingpointof117C.Whichcompoundhas
whichboilingpoint?
19.36Whichofthetwocompoundsinquestion19.35wouldyouexpecttohavegreatersolubilityin
water?Whichwouldbemoresolubleindilutesodiumhydroxidesolution?Explain.
19.37Fromeachofthefollowingpairs,selectthestrongeracid,andwriteastructuralformulaforits
conjugatebase.
(a)H2OorH2S
(b)CH3OHorCH3SH
(c)CH3COOHorCH3CH2SH
19.38Fromeachofthefollowingpairs,selectthestrongerbase,andwritethestructuralformulaofits
conjugateacid.
(a) OHorCH CH O
3 2
(b)CH CH SorCH CH O
3 2 3 2
Amines
19.39Classifyeachaminogroupinthefollowingcompoundsasprimary,secondaryortertiary,andas
aliphaticoraromatic.
(a)

(b)

19.40Drawexamplesof1,2and3aminesthatcontainatleastfoursp 3hybridisedcarbonatoms.
Usingthesamecriterion,provideexamplesof1,2and3alcohols.Howdoestheclassification
systemdifferbetweenthetwofunctionalgroups?
19.41Drawastructuralformulaforeachofthefollowingamines.
(a)(R)butan2amine
(b)octan1amine
(c)2,2dimethylpropan1amine
 (d)2bromoaniline
19.42Drawastructuralformulaforeachofthefollowingamines.
(a)pentane1,5diamine
(b)tributylamine
(c)N,Ndimethylaniline
(d)benzylamine
19.43Whydoesbutan1aminehavealowerboilingpointthanbutan1ol?

19.44Propylamine,ethylmethylamine,andtrimethylamineareconstitutionalisomerswithmolecular
formulaC3H9N.

Explainwhytrimethylaminehasthelowestboilingpointofthethree,andpropylaminehasthe
highest.
Reactionsofamines
19.45Amonofunctionalorganicnitrogencompounddissolvesinaqueoushydrochloricacidbutnotin
aqueoussodiumhydroxide.Whatkindoforganiccompoundisit?
19.46Acrystallinemonofunctionalorganicnitrogencompoundreadilydissolvesinwater,but
producesaprecipitatewhenthissolutionismadealkalinewithsodiumhydroxide.Whatkindof
organiccompoundisit?
19.47Useresonancetheorytoexplainwhyaniline(pKb=9.36)isaweakerbasethancyclohexylamine
(pKb=3.34).
19.48Whydoessubstitutionofanitrogroupmakeanaromaticamineaweakerbase,butitmakesa
phenolastrongeracid?Forexample,4nitroanilineisaweakerbasethananiline,but4
nitrophenolisastrongeracidthanphenol.
19.49Fromeachofthefollowingpairsofcompounds,selectthestrongerbase.
(a)

(b)

19.50Fromeachofthefollowingpairsofcompounds,selectthestrongerbase.
(a)
 (b)

19.51Thefollowingisastructuralformulaofpyridoxamine,oneformofvitaminB6.

(a)Whichnitrogenatomofpyridoxamineisthestrongerbase?
(b)Drawthestructuralformulaofthehydrochloridesaltformedwhenpyridoxamineis
treatedwith1moleofHCl.
19.52Procainewasoneofthefirstlocalanaestheticsusedforinfiltrationandregionalanaesthesia.

ThehydrochloridesaltofprocaineismarketedasNovocaine.
(a)Whichnitrogenatomofprocaineisthestrongerbase?
(b)Drawtheformulaofthesaltformedbytreatingprocainewith1moleofHCl.
(c)Isprocainechiral?WouldasolutionofNovocaineinwaterbeopticallyactiveoroptically
inactive?
19.53Givethestructureoftheexpectedproductformedwhenbenzylaminereactswitheachofthe
followingreagents.
(a)HBr
(b)iodomethane
(c)acetylchloride
(d)aceticacid
(e)1bromobutane
19.54Givethestructureoftheexpectedproductformedwhenanilinereactswitheachofthefollowing
reagents.
(a)benzoylchloride
(b)2bromopropane
(c)dilutehydrochloricacidsolution
(d)nitrousacid
(e)propanoicacid

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
19.55Drawastructuralformulaforeachofthefollowingcompounds.
(a)isopropylalcohol
(b)propyleneglycol
(c)(R)5methyl2hexanol
(d)4aminobutanoicacid
(e)2aminoethanol(ethanolamine)
(f) 2aminobenzoicacid
19.56Drawastructuralformulaforeachofthefollowingcompounds.
(a)2methyl2propyl1,3propanediol
(b)2,2dimethyl1propanol
(c)2hydroxybutanoicacid
(d)(S)2aminopropanoicacid(alanine)
(e)4aminobutanal
(f) 4amino2butanone
19.57Nameanddrawstructuralformulaefortheeightisomericalcoholswithmolecularformula
C5H12O.Whichofthesearechiral?
19.58ThereareeightconstitutionalisomerswithmolecularformulaC4H11N.Nameanddrawa
structuralformulaforeach.Classifyeachamineasprimary,secondaryortertiary.
19.59Drawastructuralformulaforeachofthefollowingcompoundswiththegivenmolecular
formula.
(a)2arylamine,C7H9N
(b)3arylamine,C8H11N
(c)1aliphaticamine,C7H9N
19.60Drawastructuralformulaforeachofthefollowingcompoundswiththegivenmolecular
formula.
(a)chiral1amine,C4H11N
(b)3heterocyclicamine,C5H11N
(c)trisubstituted1arylamine,C9H13N
19.61Epinephrineisahormonesecretedbytheadrenalmedulla.Oneofepinephrine'sactionsisasa
bronchodilator.Albuterol,soldunderseveraltradenamesincludingVentolin andSalbutamol,
isoneofthemosteffectiveandwidelyprescribedantiasthmadrugs.TheRenantiomerof
albuterolis68timesmoreeffectiveinthetreatmentofasthmathantheSenantiomer.
 (a)Labelandnameeachfunctionalgrouppresent.
(b)Classifyeachalcoholandaminogroupasprimary,secondaryortertiary.
(c)Listthesimilaritiesanddifferencesbetweenthestructuralformulaeofthesecompounds.
19.62Naltrexoneisusedtohelprecoveringnarcoticaddictsstaydrugfree.

(a)Labelandnameallthefunctionalgroups.Whererelevant,indicatewhetherthegroupis
primary,secondaryortertiary.
(b)Uponadditionofdilutehydrochloricacidsolution,naltrexoneformsawatersolublesalt.
Drawthestructureofthissalt.
19.63MacromerinehasbeenisolatedfromthecactusCoryphanthamacromerisandcauses
hallucinogenicreactionsinanimals.
 (a)Labelandnameallthefunctionalgroups.Whererelevant,indicatewhetherthegroupis
primary,secondaryortertiary.
(b)Uponadditionofdilutehydrochloricacidsolution,macromerineformsawatersoluble
salt.Drawthestructureofthissalt.
19.64Explainwhyputrescine,afoulsmellingcompoundproducedbyrottingflesh,ceasestosmell
upontreatmentwithtwoequivalentsofHCl.

19.65Drawallpossiblestaggeredconformationsofethane1,2diol,HOCH2CH2OH.Explainwhythe
synconformationismorestablethantheanticonformationbyapproximately4kJmol1?
19.66Describeaprocedureforseparatingamixtureofhexan1oland2methylphenol(ocresol)and
recoveringeachinpureform.Bothareinsolubleinwaterbutaresolubleindiethylether.
19.67Anilineispreparedbythecatalyticreductionofnitrobenzene.

Deviseachemicalprocedurebasedonthebasicityofanilinetoseparateitfromanyunreacted
nitrobenzene.
19.68Supposethatyouhaveamixtureofthefollowingthreecompounds.

Deviseachemicalprocedurebasedontheirrelativeacidityorbasicitytoseparateandisolate
eachinpureform.
19.69Fromeachofthefollowingpairs,selectthestrongerbase.
(a)

(b)

(c)
 (d)

19.70Predictthepositionofequilibriumforeachofthefollowingacidbasereactionsthatis,does
eachlieconsiderablytotheleft,doeseachlieconsiderablytotheright,oraretheconcentrations
evenlybalanced?
(a) CH CH OH+Na+OH CH3CH2ONa++H2O
3 2
(b)CH CH SH+Na+OH CH3CH2SNa++H2O
3 2
(c) CH CH OH+CH CH SNa+ CH3CH2ONa++CH3CH2SH
3 2 2 2
(d)

19.71ThepKa valueofthemorpholiniumionis8.33.

(a)CalculatetheratioofmorpholinetomorpholiniumioninaqueoussolutionatpH7.0.
(b)AtwhatpHaretheconcentrationsofmorpholineandmorpholiniumionequal?
19.72ThepKbofamphetamineisapproximately3.2.Calculatetheratioofamphetaminetoits
conjugateacidatpH7.4,thepHofbloodplasma.
19.73CalculatetheratioofamphetaminetoitsconjugateacidatpH1.0,suchasmightbepresentin
stomachacid.
19.74Arrangethecompoundsineachofthefollowingsetsinorderofdecreasingsolubilityinwater.
(a)ethanol,butane,diethylether
(b)hexan1ol,hexane1,2diol,hexane
19.75Writethestructuresoftheproductsoftheacidcatalyseddehydrationsofthefollowing
compounds.
(a)

(b)
 (c)

19.76Writethestructuresoftheproductsoftheacidcatalyseddehydrationsofthefollowing
compounds.Ifmorethanonealkeneispossibleshowthemall,andindicatewhichisomerwould
predominate.
(a)

(b)

(c)

19.77Writethestructuresofthesubstitutionproductsthatformwhenthealcoholsinquestion19.75are
heatedwithconcentratedhydroiodicacid.
19.78Writethestructuresofthesubstitutionproductsthatformwhenthealcoholsinquestion19.76are
heatedwiththionylchloride(SOCl2).
19.79Writethestructuresoftheproductsthatcanbepreparedbytheoxidationofthecompoundsin
question19.75usingpyridiniumchlorochromate(PCC).
19.80Writethestructuresoftheproductsthatcanbepreparedbytheoxidationofthecompoundsin
question19.76usingchromicacid(H2CrO4).
19.81Writethestructureoftheproductoftheacidcatalyseddehydrationofpropan2ol.Writethe
mechanismofthereaction.
19.82When(R)butan2olisleftinaqueousacid,itslowlylosesitsopticalactivity.Whentheorganic
materialisrecoveredfromtheaqueoussolution,onlybutan2olisfound.Accountforthe
observedlossofopticalactivity.
19.83Whatisthemostlikelymechanismofthefollowingreaction?

Drawastructuralformulafortheintermediate(s)formedduringthereaction.
19.84Inthecommercialsynthesisofmethyltertbutylether(MTBE),onceusedasanantiknock,
octaneimprovingpetroladditive,2methylpropeneandmethanolarepassedoveranacid
catalysttogivetheetherasshownbelow.
 Proposeamechanismforthisreaction.
19.85Completetheequationsforthefollowingreactions.
(a)

(b)

(c)

19.86Completetheequationsforthefollowingreactions.
(a)

(b)

19.87Writeequationsshowingthereactionbetweenthefollowingpairsofsubstances.
(a)

(b)

(c)

(d)
19.88Writeequationsshowingthereactionbetweenthefollowingpairsofsubstances.
(a)

(b)

(c)CH3CH2CH2OH+SOCl2
(d)

(e)

19.89Explainhowyoucouldusesimplechemicalteststodistinguishbetweenthefollowingsetsof
compounds.Explainyourobservationsandgiveequationswherenecessary.
(a)

(b)

19.90Explainhowyoucouldusesimplechemicalteststodistinguishbetweenthefollowingsetof
compounds.Explainyourobservationsandgiveequationswherenecessary.

19.91Showhowtoconvertcyclohexanoltothefollowingcompounds.
(a)cyclohexene
(b)cyclohexane
 (c)cyclohexanone
19.92Showhowtoconvert:
(a)propan1oltopropan2olintwosteps
(b)cyclohexenetocyclohexanoneintwosteps
(c)propenetoacetone(propanone)intwosteps.
19.93Showhowtoprepareeachofthefollowingcompoundsfrom2methylpropan1ol.
(a)

(b)

(c)

Foranypreparationinvolvingmorethanonestep,showeachintermediatecompoundformed.
19.94Showhowtoprepareeachofthefollowingcompoundsfrom2methylcyclohexanol.
(a)

(b)

(c)

Foranypreparationinvolvingmorethanonestep,showeachintermediatecompoundformed.
19.95Showhowtoconvertthealcoholonthelefttocompounds(a),(b)and(c).

(a)
 (b)

(c)

19.96Showreagentsandexperimentalconditionsthatcanbeusedtosynthesisethefollowing
compoundsfrompropan1ol(anyderivativeofpropan1olpreparedinanearlierpartofthis
questionmaybeusedforalatersynthesis).
(a)propanal
(b)propanoicacid
(c)propene
(d)propan2ol
(e)2bromopropane
(f) 1chloropropane
(g)acetone
19.97Thecompound4aminophenolisabuildingblockinthesynthesisoftheanalgesic
acetaminophen.Showhowthisbuildingblockcanbeusedinthesynthesisofacetaminophenin
threestepsfromphenol.

19.98Thetopicalanaestheticbenzocainecanbesynthesisedinfourstepsfromtoluene.Showhowthis
canbeachieved.
19.99Theoverthecounteranalgesicphenacetinissynthesisedinfourstepsfromphenol.

Showreagentsforeachstepofthesynthesisofphenacetin.
19.100Theintravenousanaestheticpropofolissynthesisedfromphenolinfoursteps.Showthe
reagentsrequiredforsteps(1)to(3).
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
19.101Whichofthefollowingcompoundsisabetternucleophile?Givereasonsforyouranswer.

19.102Radiopaqueimagingagentsaresubstances,administeredeitherorallyorintravenously,that
absorbXraysmorestronglythanbodymaterialdoes.Oneofthebestknownoftheseagentsis
bariumsulfate,thekeyingredientinthebariumcocktailusedforimagingthegastrointestinal
tract.AmongotherXrayimagingagentsarethetriiodoaromatics.Youcangetsomeideaofthe
kindsofimagingtheyareusedforfromthefollowingselectionoftradenames:Angiografin ,
Gastrografin,Cardiografin,Cholografin,Renografin,andUrografin .Themostcommonofthe
triiodoaromaticsarederivativesofthefollowingthreetriiodobenzenecarboxylicacids.

Thecompound3amino2,4,6triiodobenzoicacidissynthesisedfrombenzoicacidinthree
steps.
 (a)Showthereagentsrequiredforsteps(1)and(2).
(b)Iodinemonochloride,ICl,ablackcrystallinesolidwithameltingpointof27.2Canda
boilingpointof97C,ispreparedbymixingequimolaramountsofI2andCl2.Propose
amechanismfortheiodinationof3aminobenzoicacidusingthisreagent.
(c)Showhowtoprepare3,5diamino2,4,6triiodobenzoicacidfrombenzoicacid.
(d)Showhowtoprepare5amino2,4,6triiodoisophthalicacidfrombenzene1,3
dicarboxylicacid.
19.103Rankthemembersineachofthefollowingsetsofreagentsfrommosttoleastnucleophilic.
(a)

(b)

19.104Inchapter23wewillseethatthereactivityofthefollowingcarbonylcompoundsisdirectly
proportionaltothestabilityoftheleavinggroup.Usingthis,ranktheorderofreactivityofthe
carbonylcompoundsfrommostreactivetoleastreactive.

19.105Predicttheproductofthefollowingacidbasereaction.

19.106Aminescanactasnucleophiles.Foreachofthefollowingmolecules,circletheatomthatwould
 mostlikelybeattackedbythenitrogenatomofanamine.
(a)

(b)

(c)

19.107Howcanthefollowingtransformationbeaccomplished?(Hint:Thisisatwostepprocess
involvinganalcoholintermediate.)

19.108Giveatleasttwochemicallyreasonablesynthesesofethyl2methylpropylether(ethylisobutyl
ether)usingethanolandmethylpropan1olasyourstartingmaterials.

19.109Apureliquid,X,reactswithsodiumtoproducehydrogen.Italsoreactswithphosphorus
pentachloridetoyieldcompoundY,whichontreatmentwithalcoholicpotassiumhydroxide
solutiongivespent1eneonly.WhatarethestructuresofXandYandthereactionsinvolved?
19.110Whenneopentylalcohol(2,2dimethylpropan1ol),(CH3)3CCH2OH,isheatedwithacid,itis
slowlyconvertedintoan85:15mixtureoftwoalkeneswiththeformulaC5H10.Whatarethese
alkenesandhowaretheyformed?Whatdoyouthinkisthemajorproductandwhy?
19.111CompoundA,C5H10O,absorbs1moleofhydrogenoncatalytichydrogenationtogiveB.Both
AandBreactwithsodiummetaltoproducehydrogengas.B,whentreatedwithphosphorus
tribromide,givesC,C5H11Br,whichwhentreatedwithlithiumaluminiumhydridegivesD,
C5H12.CompoundAcontainsnomethylgroups.DrawacyclicandanacyclicstructureforA,
andexplainallreactionsinvolved.
19.112AnunknowncompoundX,C7H9N,isonlysparinglysolubleinwater,butdissolvesreadilyin
dilutehydrochloricacid.Theresultingsolution,ontreatmentwithsodiumnitrite,doesnotform
anazodyewhenaddedtoanalkalinesolutionof2naphthol.However,Xgivesapositivetest
foraprimaryamine.DeducethestructureofX.
19.113Acidcatalysedhydrationof1methylcyclohexeneyieldstwoalcohols.Themajorproductdoes
notundergooxidation,whiletheminorproductdoesundergooxidation.Explain.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
hydroxylgroup cyclicether heterocyclicaromaticamine
alcohol dehydration hydrogenbonding
aliphaticamine diol mercaptan
alkoxy disulfide phenol
alkylamines ether pyridiniumchlorochromate
aniline glycol (PCC)
aromaticamine heteroatom thiol
azocompounds heterocyclicamine triol
zwitterion

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

20 Spectroscopy
Wehaveencounterednumerousreactionsandcompoundsintheearlierchaptersofthisbook.Haveyou
everwonderedhowchemistsknowthestructureofthecompoundsusedorproducedinthevarious
reactions?Rememberthatchemistryisanexperimentalscienceandevidencemustbeprovidedtosupport
anyclaimedresults.Untilthemidtwentiethcentury,thedeterminationofthestructureofacompoundwas
adifficultandtimeconsumingexercise.Withtheadventofmoderninstrumentaltechniques,thisprocess
hasbeengreatlysimplified(butitisnotaseasyasdepictedonforensicscienceTVshows).Inthischapter
wewilldiscussthethreemostcommonlyusedtools:massspectrometry(MS),infrared(IR)spectroscopy
andnuclearmagneticresonance(NMR)spectroscopy.Thesetechniqueshavetheadvantagesthatonlya
smallamountofmaterialisrequired,complexstructurescanbereadilyanalysed,andtheprocessis
relativelyquick.Wewillintroducesomeofthefeaturesandapplicationsofthesetechniquesthataidinthe
determinationofthestructureofmolecules.

Oneofthemostpowerfuldiagnostictoolsinmodernmedicineismagneticresonanceimaging(MRI),a
techniquefoundedontheprinciplesofNMRspectroscopy.MRIdifferentiatesthedifferenttissuesinthe
bodybydetectingthehydrogennucleiofwatermoleculesinthedifferingenvironmentswithinthose
tissues.Analogously,thedifferentenvironmentsthatnucleisuchashydrogen,carbonorphosphorusreside
ingiverisetodifferentNMRsignals.AsatestamenttotheimportanceofMRIinmodernmedicine,the
2003NobelPrizeinphysiologyormedicinewasawardedtoPaulLauterburandSirPeterMansfieldfor
developingthistechnique.

KEYTOPICS
 20.1Toolsfordeterminingstructure
20.2Massspectrometry
20.3Infraredspectroscopy
20.4Interpretinginfraredspectra
20.5Nuclearmagneticresonancespectroscopy
20.6InterpretingNMRspectra
20.7Othertoolsfordeterminingstructure

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.1ToolsforDeterminingStructure
Letusconsidertworeactionswehavestudiedpreviously:thehydrationof3methylbut1eneandthe
dehydrationof3methylbutan2ol.

Howdochemistsdeterminethattheproductformedisanalcoholinthefirstreactionandanalkenein
thesecond?Furthermore,theyneedtodeterminethepositionoftheOHgroupandthealkenegroup.
Howcanthisbedone?Answeringthefirstquestionbyclassicalmethods(thosemethodsavailableto
theearlychemists)isnotsohardtherearenumeroustesttubetestsavailabletoidentifyanalcoholor
alkenegroup.Thesecondquestioncanalsobeansweredbyclassicaltechniques,butthisisnotso
simple.Today,chemistsrelyalmostexclusivelyoninstrumentalmethodsofanalysisforstructure
determination.Althoughinthischapterwewillfocusonmassspectrometry(MS),infrared(IR)
spectroscopyandnuclearmagneticresonance(NMR)spectroscopy,thesearebynomeanstheonly
toolschemistsuse.SomeothertoolsusedbychemistsincludeXraycrystallography,UV/visible
spectroscopyandelectronspinresonance.Thegeneralapplicationoftheseothertechniqueswillbe
describedbrieflyinsection20.7.

TheIndexofHydrogenDeficiency
Wecanobtainvaluableinformationaboutthestructuralformulaofanunknowncompoundby
inspectingitsmolecularformula.Inadditiontolearningthenumberofeachtypeofatominamolecule
ofthecompound,wecandetermineitsindexofhydrogendeficiency(IHD)(alsoknownasdouble
bondequivalentsordegreesofunsaturation),whichisthesumofthenumberofringsandbondsina
molecule.Forahydrocarbon,wecandeterminethisquantitybycomparingthenumberofhydrogen
atomsinthemolecularformulaofacompoundofunknownstructurewiththenumberofhydrogen
atomsinareferencecompoundwiththesamenumberofcarbonatomsandwithnoringsorbonds.
ThemolecularformulaofthereferencehydrocarbonisCnH2n+2.

Letusconsider,forexample,thealkanes(CnH2n+2),cycloalkanes(CnH2n),alkenes(CnH2n)and
alkynes(CnH2n2)(seechapter16).ThesehaveanIHDof0,1,1and2respectively.TheIHD
(sometimescalledtheunsaturationindexorthedoublebondequivalents)canbeveryusefulin
determiningthestructureofamolecule.IfanunknowncompoundhasanIHDof0,weknow
immediatelyitdoesnotcontainanyringsorbonds,whileanIHDof1wouldindicatethepresenceof
eitheraringorabond.SincebenzenehasanIHDof4(oneringandtheequivalentofthreedouble
bonds),compoundscontainingabenzeneringmusthaveanIHD4anIHD<4indicatesthatsucha
ringisnotpresentinthemolecule.
 WORKEDEXAMPLE20.1

CalculatingtheIHDofHydrocarbons
Calculatetheindexofhydrogendeficiencyforisopropylbenzene(cumene)withthe
molecularformulaC9H12andaccountforthisdeficiencybyreferencetothestructural
formulaofthecompound.

Analysis

ThemolecularformulaofthereferencehydrocarbonwithninecarbonatomsisC9H20.

Solution

Theindexofhydrogendeficiencyofcumeneis(2012)/2=4andisaccountedforbythe
threedoublebondsandoneringincumene.

Isouranswerreasonable?

Drawthestructureofthecompoundandcountthenumberofdoublebondsandrings.
Benzenoidcompounds(compoundsbasedonbenzene)musthaveanIHDofatleast4.

PRACTICEEXERCISE20.1
Calculatetheindexofhydrogendeficiency
ofcyclohexene,C6H10,andaccountforthis
deficiencybyreferencetothestructural
formulaofthecompound.

Todeterminethemolecularformulaofareferencecompoundcontainingelementsotherthancarbon
andhydrogen,writetheformulaofthereferencehydrocarbon,addtoitotherelementscontainedinthe
unknowncompound,andmakethefollowingadjustmentstothenumberofhydrogenatoms:
1.Foreachatomofamonovalentgroup17element(F,Cl,Br,I)addedtothereference
hydrocarbon,subtractonehydrogenatomhalogensubstitutesforhydrogenandreducesthe
numberofhydrogenatomsbyoneperhalogenatom.Thegeneralformulaofanacyclic
monochloroalkane,forexample,isCnH2n+1Cl.
2.Nocorrectionisnecessaryfortheadditionofatomsofgroup16elements(O,S,Se)tothe
referencehydrocarbon.Insertingadivalentgroup16elementintoareferencehydrocarbondoes
notchangethenumberofhydrogenatoms.
3.Foreachatomofatrivalentgroup15element(NandP)addedtotheformulaofthereference
hydrocarbon,addonehydrogenatom.Insertingatrivalentgroup15elementaddsonehydrogen
atomtothemolecularformulaofthereferencecompound.Thegeneralmolecularformulaforan
acyclicalkylamine,forexample,isCnH2n+3N.
WORKEDEXAMPLE20.2

CalculatingtheIHD
Isopentylacetate(3methylbutylacetate),acompoundwithabananalikeodour,isa
componentofthealarmpheromoneofhoneybees.ItsmolecularformulaisC7H14O2.
Calculatetheindexofhydrogendeficiencyofthiscompound.

Analysis

ThemolecularformulaofthereferencehydrocarbonwithsevencarbonatomsisC7H16.
Addingoxygenatomstothisformuladoesnotchangethenumberofhydrogenatoms.

Solution

ThemolecularformulaofthereferencecompoundisC7H16O2,andtheindexofhydrogen
deficiencyis(1614)/2=1,indicatingeitheroneringoronebond.Ascanbeseenfrom
thestructuralformulaofisopentylacetate,itcontainsonebond,thecarbonoxygendouble
bond.

Isouranswerreasonable?

Drawthestructureofthecompoundandcountthenumberofdoublebondsandrings.

PRACTICEEXERCISE20.2
Theindexofhydrogendeficiencyof
nicotinamideis5.Accountforthisvalueby
referencetothestructuralformulaof
nicotinamide:
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.2MassSpectrometry
Inchapter10youlearnedthatthecolligativepropertiesofsolutionscanbeusedtodeterminethemolar
massofthedissolvedsolutes.Analternativeandmorewidelyusedmethodismassspectrometry.This
techniqueallowsustodeterminethemassofmoleculesandfragmentsofmolecules.Thethreekeysteps
inmassspectrometryare(1)ionisationofthesample,(2)separationoftheresultingionsand(3)
detectionoftheions.Thefundamentalprincipleisthat,whenamoleculeisionised,itcanbeaccelerated
throughanelectricormagneticfieldwhereionsofdifferentmassaredeflectedtodifferentextents.The
ionsarethencountedbythedetectorandtheirabundanceisplottedonagraphagainsttheirmassto
chargeratios(m/z).Aschematicrepresentationofamassspectrometerisgiveninfigure20.1.

FIGURE20.1Schematicrepresentationofonetypeofmassspectrometer.Inthesamplesource,anelectron
beamionisesgasmoleculesintopositivelychargedions.Theionsareacceleratedandthen
deflectedbyamagnet.Eachfragmentfollowsatrajectorythatdependsonitsmasstocharge
ratio(m/z).CameronKepert

Whenasampleisintroducedintoamassspectrometer,itisbombardedwithastreamofhighenergy
electrons,whichcausessomeofthemoleculestobeionisedbytheejectionofanelectron.This
producesionsthatareradicalcations(radicalbecausethereisanunpairedelectronandcation
becauseofthepositivecharge).Theseionsaretermedmolecularions(orparentions)andhave
essentiallythesamemassastheoriginalmoleculesbecausethemassofthelostelectronisnegligible.

Thepeakduetothemolecularioncanbeusedtoquicklydifferentiatebetweenmoleculesofsimilar
mass(usuallytheonewiththehighestm/zvalue).Consider,forexample,theproblemofdifferentiating
betweensamplesofhexaneandcyclohexane.Massspectrometrywillallowidentificationbecausethey
havedifferentmolecularmasses(86and84,respectively)asshowninfigure20.2.Inchapter1,we
definedatomicmassasthemassofoneatom,measuredinamu.Wecandothesameforasingle
molecule.Thus,molecularmassisthemassofonemolecule,measuredinamu.
FIGURE20.2 Themassspectraofhexaneandcyclohexane:
(a)Themolecularionsignalatm/z86indicatesthatthisspectrumisofhexane,
(b)whilem/z84indicatescyclohexane.Theotherpeaksinthespectraaredueto
fragmentationproducts(seep.868).CameronKepert

chemistryResearch

IdentificationandStructuralAnalysisofBiomolecules

ProfessorMarkABuntine,CurtinUniversity

Massspectrometryisanextremelypowerfultoolfordeterminingthemassofmoleculesand
thesequenceinwhichvariousfunctionalgroupsarejoinedtogetherwithinamolecule.Laser
spectroscopy,throughtheexcitationofelectrons(electronicspectroscopy)orthepromotion
ofvibrations(vibrationalspectroscopy),isaneffectivewayoflearningabouttheshapeof
moleculesandthestrengthofthevariousbondsthatholdtheatomstogetherwithina
molecule.Whenthetwotechniquesarecombined,chemistscanstudymolecularshapeand
functionwithgreatsensitivityandaccuracy.

However,massspectrometryandthehighestresolutionlaserspectroscopyrequiremolecules
tobeinthegasphase.Theionscreatedinamassspectrometerwouldreactveryquicklyif
theywerenotisolatedinthecollisionfreeconditionsofavacuumchamber.Insolution,
solutesolventandotherintermolecularinteractionsblurmuchofthedetailprovidedbylaser
spectroscopyofgaseousmolecules.Onecommonwaythatchemistshaveintroduced
moleculesintothegasphaseforstudybythesetechniqueshasbeentoheatthemtoobtainthe
samplevapour.However,heatinglargermolecules,suchasthoseofbiologicalinterest,
usuallycausesthemtodecompose.

Itisamajorchallengeformassspectrometrytodevelopmethodstointroducenonvolatile
moleculesintothegasphase.Twoofthebestapproachestodateareelectrosprayionisation
(ESI)andmatrixassistedlaserdesorptionandionisation(MALDI).Thedevelopersofthese
techniques,JohnFenn(forESI)andKoichiTanaka(forMALDI)sharedtheNobelPrizein
chemistryin2002fortheircontributionstothefield.

ESIandMALDIdosufferfromsomelimitations,however.Oftensaltsorsugarsneedtobe
mixedwiththebiologicalmoleculesofinteresttohelpgetthemintothegasphase.These
additivescansignificantlyalterthenormalintermolecularbondingenvironments,thereby
changingtheirmolecularshape.

ChemistsatCurtinUniversityareresearchingtheuseofliquidmicrojetsasanalternative
largemoleculeintroductiontechnologythatdoesnotrequireanyadditivesthatmightaffect
molecularshape.Averythinstreamofliquid(10micrometresindiameterapproximately
thethicknessofahumanhair)isinjecteddirectlyintoavacuumchamber.Apulsedinfrared
laserspecificallytunedtoanabsorptionbandofthewatersolventrapidlyheatstheliquid
sampleandtherebyejectsmoleculesintothegasphase.Followingthis,apulsedultraviolet
laserremovesanelectronfromthemolecule,creatinganiondetectablebymassspectrometric
analysis.Aschematicofthistechniqueisshownbelow.Measuringtheefficiencywithwhich
abiomoleculeisionisedasafunctionoftheUVlaserphotonenergygivesdetailsofits
molecularshape.Unambiguousmassidentificationisobtainedbythemassspectrometric
detectionoftheions.
 OnesignificantapplicationoftheliquidmicrojettechniquebeingstudiedbythePerth
researchersisaninvestigationoftheshapeofbiomolecules,whichoftencontrolstheir
biologicalactivityandfunction.Itisknownthatthebondsthatformbetweenbiomolecules
andthewatersolventcontrolthisshape.However,verylittleisknownaboutthestrengthand
structureofthesebondsatdifferentsitesaroundthebiomolecule.Someexperimentshave
informedusaboutthestrengthofthebondsothershavetolduswherethebondsoccur.The
WesternAustralianteamisgatheringbothpiecesofinformationinasingleexperiment,
allowingabetterunderstandingofbiochemicalinteractions.

WORKEDEXAMPLE20.3

DeterminingMolecularFormulaefromMassSpectra
Themassspectrumofanunknownalkaneshowedamolecularionpeakatm/z128.Whatis
themolecularformulaofthiscompound?

Analysis

AsthisisanalkaneweknowitcontainsonlyCandHandithasthegeneralformulaCnH2n+
2.

Solution

SubstitutingourknownvaluesintoCnH2n+2givestheequation12n+[1(2n+2)]=
128.Solvingforngivesn=9.Therefore,themolecularformulaofthecompoundisC9H20.

Isouranswerreasonable?

YoushouldcheckthatthemolecularmassofC9H20is128.

PRACTICEEXERCISE20.3

(a)Themassspectrumofanunknown
alkaneshowedamolecularionpeak
atm/z198.Whatisthemolecular
formulaofthiscompound?
(b)Themassspectrumofanunknown
cycloalkaneshowedamolecularion
peakatm/z140.Whatisthe
molecularformulaofthis
compound?

Whenionisingthesampleinamassspectrometer,manyoftheresultingmolecularionsfragmenttogive
cationsoflowermass(sometimescalleddaughterions)andneutralradicals(whicharenotdetectedas
theyarenotcharged).Thesefragmentcationsaresortedaccordingtotheirmasstochargeratios(m/z).
Asthechargeisalmostalways+1whenmoleculesareionisedinthisway,m/zisequivalenttothemass
oftheion.Analysisofthesefragmentationpatternscanbeusedtohelpdeterminethestructureofa
compoundhowever,detailsofthisprocesswillnotbecoveredhere.Instead,wewillfocusontheuse
ofmassspectrometrytodeterminemolarmassesandmolecularformulae.

IsotopesinMassSpectrometry
Uponinspectionofthespectrainfigure20.2,youwillnoticethatthem/zvaluesforallthepeaksare
givenaswholenumbers.Thisissufficientformostpurposes.However,itdoesnotallowusto
differentiatebetweenmoleculeswiththesamemass(whenquotedinwholenumbers)butdifferent
formulae.Theaccuratemassofthemolecularion,andconsequentlythemolecularformula,ofa
compoundcanbedeterminedbyusingatechniquecalledhighresolutionmassspectrometry.Inthis
process,themasstochargeratioofions(includingthemolecularion)ismeasuredwithahighdegreeof
precision(usuallytofourdecimalplaces).Forexample,considerthefourcompoundslistedintable
20.1,allofwhichhavedifferentmolecularformulaebutthesamenominalmolecularmass.Youwill
alsonoticethatthemolecularmassandtheaccuratemassarenotthesame.Thisisbecause,in
determiningtheaccuratemass,weusetheaccuratemassofthemostabundantisotopeofeachelement,
ratherthantheatomicmassoftheelement.Table20.2listssomeaccuratemassesfortheelements
commonlyencounteredinorganicchemistry,alongwiththeirnaturalabundances.
TABLE20.1 Comparisonofthemassesoffourcompoundswithmolecularmassof88
Molecular Molecularmass Accuratemass
Name Structure formula (amu) (amu)
butanoicacid C4H8O2 88.11 88.0524

butane2,3 C4H12N2 88.15 88.1001

diamine

pentan3ol C5H12O 88.15 88.0888

N,N C3H8N2O 88.11 88.0637

dimethylurea

TABLE20.2 Isotopeabundanceandaccuratemassofselectedelementsthatarecommonlyencountered
inorganicchemistry

Element Atomicmass(amu) Isotope %Naturalabundance Accuratemass(amu)

hydrogen 1.0079 1H 99.985 1.0078

2H 0.015 2.0140

carbon 12.011 12C 98.89 12.0000

13C 1.11 13.0034

nitrogen 14.0067 14N 99.64 14.0031

 nitrogen 14.0067 14N 99.64 14.0031
15N 0.36 15.0001

oxygen 15.9994 16O 99.76 15.9949

17O 0.04 16.9991

18O 0.20 17.9992

phosphorus 30.9738 31P 100.00 30.9738

sulfur 32.064 32S 95.00 31.9721

33S 0.76 32.9715

34S 4.22 33.9679

36S 0.02 35.9671

fluorine 18.9984 19F 100.00 18.9984

chlorine 35.453 35Cl 75.77 34.9688

37Cl 24.23 36.9659

bromine 79.904 79Br 50.69 78.9183

81Br 49.31 80.9163

iodine 126.9044 127I 100.00 126.9044

WORKEDEXAMPLE20.4

DeterminingMolecularFormulaefromHighResolutionMass
Spectra
WhichofthemolecularformulaeC7H16,C6H14N,C5H12N2,C6H12OandC5H8O2
correspondstoanaccuratemassofm/z100.0888?

Analysis

Asastartingpoint,youwillnoticeallofthesemolecularformulaehaveanominalmolecular
massof100.Tosolvethisproblem,simplydeterminetheaccuratemasscorrespondingto
eachformulausingtheaccuratemassvalueforthemostabundantisotopeofeachelement.

Solution

C6H12O

Isouranswerreasonable?

Doublecheckyourcalculationsfortheaccuratemass.Itispossibletoworkbackwardsfrom
anaccuratemasstodeterminethemolecularformula,butthisrequiresacomputerprogram
(orextensivetrialanderror).
 PRACTICEEXERCISE20.4
WhichofthemolecularformulaeC8H18,
C7H14O,C7H16N,C6H14N2,C6H12NOand
C6H10O2correspondstoanaccuratemassof
114.1158?

Youmayhavenoticedthat,oftheelementslistedintable20.2,manyhadoneisotopewithanatural
abundanceofmorethan99%.Intheothercases,wecanusetheisotopeabundancetohelpdetermine
thepresenceofparticularelements.Bromineisparticularlyeasytorecognisebythepresenceoftwo
signalsofequalintensityandamassdifferenceof2,duetothe79Br(M+ion)and 81Br[(M+2)+ion]
isotopes,whicharenearlyequallyabundant.Thepresenceofachlorineatominamoleculewillgive
risetoan(M+2)+signalonethirdtheheightoftheM+signal(theratioof35Clto37Clis3:1).Isotope
distributionhasalsobeenusedtohelpidentifymanymetallicandorganometallicmaterialsinthe
environment.Forexample,thepollutantslead,mercuryandtinhavefour,sevenandtennatural
isotopesrespectively.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.3InfraredSpectroscopy
Spectroscopictechniques,includinginfrared(IR)spectroscopyandnuclearmagneticresonance(NMR)spectroscopy,
involvetheinteractionofmoleculeswithelectromagneticradiation.Thus,tounderstandthefundamentalsof
spectroscopy,wemustfirstreviewsomeofthefundamentalsofelectromagneticradiation.

ElectromagneticRadiation
Insection4.2,westudiedthecharacteristicsoflight,aformofelectromagneticradiation,andwewillprovideonlya
summaryhere.Gammarays,Xrays,ultravioletlight,visiblelight,infraredradiation,microwavesandradiowavesare
allexamplesofelectromagneticradiationandpartoftheelectromagneticspectrum.Becauseelectromagneticradiation
behavesasawavetravellingatthespeedoflight,itisdescribedintermsofitswavelengthandfrequency.Figure20.3
summarisesthewavelengthsandfrequenciesofsomeregionsoftheelectromagneticspectrum.

FIGURE20.3Wavelengthandfrequencyofsomeregionsoftheelectromagneticspectrum.

Wavelengthisthedistancebetweenanytwoconsecutiveequivalentpointsonthewave(forexample,cresttocrest).
Wavelengthisgiventhesymbol(Greeklowercaselambda)andisusuallyexpressedintheSIbaseunitofmetres.
Otherderivedunitscommonlyusedtoexpresswavelengtharegivenintable20.3.
TABLE20.3 Commonunitsusedtoexpresswavelength()

Thefrequencyofawaveisthenumberoffullcyclesofthewavethatpassagivenpointinasecond.Frequencyisgiven
thesymbol(Greeklowercasenu)andisreportedins1,alsocalledhertz(Hz).Wavelengthandfrequencyare
inverselyproportional,andwecancalculateonefromtheotherusingtherelationship:

whereisfrequencyins1,cisthevelocityoflight(2.99810 8ms1),andisthewavelengthinmetres.

Analternativewaytodescribeelectromagneticradiationisintermsofparticles.Wecalltheseparticlesphotons.The
energyofaphotonandthefrequencyofradiationarerelatedbytheequation:

whereEistheenergyinkJandhisPlanck'sconstant,6.62610 34Js.Thisequationtellsusthathighenergyradiation
correspondstoshortwavelengths,andviceversa.Thus,ultravioletlight(higherenergy)hasashorterwavelength
(approximately10 7m)thaninfraredradiation(lowerenergy),whichhasawavelengthofapproximately10 5m.

TheVibrationalInfraredSpectrum
Aswediscussedinchapter5,moleculesareflexiblestructureswithatomsandgroupsofatomsabletorotatearound
covalentsinglebonds.Covalentbondsstretchandbendjustasiftheatomswerejoinedbyflexiblesprings.Weknow
fromexperimentalobservationsandfromtheoriesofmolecularstructurethatallenergychangeswithinamoleculeare
quantisedthatis,theyaresubdividedintosmall,butwelldefined,increments.Forexample,vibrationsofbondswithin
moleculescanundergotransitionsonlybetweenallowedvibrationalenergylevels.

WecancauseatomsormoleculestoundergoatransitionfromenergystateE1toahigherenergystateE2byirradiating
themwithelectromagneticradiationcorrespondingtotheenergydifferencebetweenstatesE1andE2asillustrated
schematicallyinfigure20.4.Whentheseatomsormoleculesreturntothegroundstate,anequivalentamountofenergy
isemitted.Whenasampleisirradiatedwithelectromagneticradiationofvariouswavelengths,itabsorbsenergyof
particularwavelengths,whilethewavelengthsnotabsorbedsimplypassthroughorarereflectedfromthesample
unchanged.Ininfrared(IR)spectroscopy(figure20.5),whenweirradiateasamplewithinfraredradiation,thisradiation
isabsorbedwhenitsenergy(frequency)isexactlyequaltotheenergyrequiredtoexcitethemoleculestoahigher
energystate.Becausedifferentfunctionalgroupshavedifferentbondstrengths,theenergyrequiredtobringaboutthese
transitionsvariesfromonefunctionalgrouptoanother.Thus,ininfraredspectroscopy,wedetectfunctionalgroupsby
thevibrationsoftheirbonds.

FIGURE20.4AbsorptionofenergyintheformofelectromagneticradiationexcitesatomsormoleculesinenergystateE1 toa
higherenergystateE2 .
 FIGURE20.5Aninfraredspectrophotometer.Spectraareshownonthemonitor.

Theinfraredregionoftheelectromagneticspectrum(figure20.3)coverstherangeofwavelengthsfrom7.810 7m(
justlongerthanthevisibleregion)to2.010 3m(justshorterthanthemicrowaveregion).Inchemistry,however,we
routinelyuseonlytheportionthatextendsfrom2.510 6to2.510 5m.Thisregionisoftencalledthevibrational
infraredregionandwecommonlyrefertoradiationinthisregionbyitswavenumber ,thenumberofwavesper
centimetre.Toconvertwavelengthtowavenumber,simplycalculatethereciprocalofthewavelength(incm).Expressed
inwavenumbers,thevibrationalregionoftheinfraredspectrumextendsfrom4000to400cm1(theunitcm1isread
reciprocalcentimetre).Anadvantageofusingwavenumbersisthattheyaredirectlyproportionaltoenergythehigher
thewavenumber,thehighertheenergyofradiation.

Figure20.6showsaninfraredspectrumofaspirin.Thehorizontalaxisiscalibratedinwavenumbers(cm1).The
wavenumberscaleisoftendividedintotwoormorelinearregions.Forallspectrareproducedinthistext,itisdivided
intothreelinearregions:40002200cm1,22001000cm1and1000450cm1.Theverticalaxismeasures
transmittance,with100%transmittanceatthetopand0%transmittanceatthebottom.Thus,thebaselineforaninfrared
spectrum(100%transmittanceofradiationthroughthesample=0%absorption)isatthetopofthechart,andthe
absorptionofradiationcorrespondstoatroughorvalley.Strangeasitmayseem,wecommonlyrefertoinfrared
absorptionsaspeaks,eventhoughtheyareactuallytroughs.Theyarealsocalledbandsorsignals.Ifabsorptionof
lightisusedontheverticalaxisinsteadoftransmittance,thesignalsareactuallypeaks.

FIGURE20.6Infraredspectrumofaspirin.

MolecularVibrations
Atomsjoinedbycovalentbondsarenotpermanentlyfixedinonepositionbut,instead,undergocontinuousvibrations
relativetoeachother.Theenergiesassociatedwithtransitionsbetweenvibrationalenergylevelsinmostcovalent
moleculesrangefrom8to40kJmol1.Suchtransitionscanbeinducedbytheabsorptionofradiationintheinfrared
regionoftheelectromagneticspectrum.
Formoleculestoabsorbinfraredradiation,thebondsundergoingvibrationmustbepolar,andtheirvibrationmustcause
aperiodicchangeinthebonddipolethegreaterthepolarityofthebonds,themoreintenseistheabsorption.Any
vibrationthatmeetsthesecriteriaissaidtobeinfraredactive.Covalentbondsinhomonucleardiatomicmolecules,such
asH2andBr2,andsomecarboncarbondoubleortriplebondsinsymmetricalalkenesandalkynesdonotabsorb
infraredradiationbecausetheyarenotpolarbonds.Themultiplebondsinthefollowingtwocompounds,forexample,
donothaveadipolemomentsoarenotinfraredactive.

Fornonlinearmoleculescontainingnatoms,3n6allowedfundamentalvibrationsexist.Foracompoundassimpleas
ethanol,CH3CH2OH,thereare21fundamentalvibrations,andforhexanoicacid,CH3(CH2)4COOH,thereare54.Thus,
evenforrelativelysimplemolecules,alargenumberofvibrationalenergylevelsexist,andthepatternsofenergy
absorptionfortheseandlargermoleculesarequitecomplex.

Thesimplestvibrationalmotionsinmoleculesgivingrisetotheabsorptionofinfraredradiationarestretchingand
bendingmotions.Thefundamentalstretchingandbendingvibrationsforamethylenegroupareillustratedinfigure20.7.

FIGURE20.7Fundamentalmodesofvibrationforamethylenegroup.

Tosomeoneskilledintheinterpretationofinfraredspectra,absorptionpatternscanyieldanenormousamountof
informationaboutchemicalstructure.Thevalueofinfraredspectraforus,however,isthatwecanusethemtodetermine
thepresenceorabsenceofparticularfunctionalgroups.Carbonylgroups,forexample,typicallyshowstrongabsorption
atapproximately16301800cm1m.Thepositionofabsorptionforaparticularcarbonylgroupdependsprincipallyon
thefunctionalgrouptowhichitbelongs(aldehyde,ketone,carboxylicacid,anhydride,acidchloride,esteroramide).
Otherfactorsinfluencingthefrequencyofabsorptionincluderingstrain(ifthecarbonylgroupispartofaring)and
conjugation(havinganalkeneoraromaticringimmediatelyadjacenttothecarbonylgroup).

CorrelationTables
DataonabsorptionpatternsofselectedfunctionalgroupsarecollectedintablescalledcorrelationtablesTable20.4
givesthecharacteristicinfraredvibrationalfrequenciesforthetypesofbondsandfunctionalgroupswedealwithmost
often.AppendixHcontainsacumulativecorrelationtable.Inthesetables,werefertotheintensityofaparticular
absorptionasstrong(s),medium(m)orweak(w).
TABLE20.4 CharacteristicIRvibrationalfrequenciesofselectedfunctionalgroups

Bond Frequency(cm1) Intensity

OH 32003500 strongandbroad
NH 31003500 medium
 CH 28503100 mediumtostrong
C C 21002260 weak
C O 16301800 strong
C C 16001680 weak
CO 10501250 strong

Ingeneral,wewillpaymostattentiontotheregionfrom3650to1500cm1,wherethecharacteristicstretching
vibrationsformostfunctionalgroupsarefound.Vibrationsintheregionfrom1500to400cm1canarisefrom
phenomenasuchascombinationsoftwoormorebandsorharmonicsoffundamentalabsorptionbands.Suchvibrations
aremuchmorecomplexandfarmoredifficulttoanalyse.Becauseevenslightvariationsinmolecularstructureleadto
differencesinabsorptionpatternsinthisregion,itisoftencalledthefingerprintregion.Iftwocompoundshaveeven
slightlydifferentstructures,thedifferencesintheirinfraredspectraaremostclearlydiscernibleinthefingerprintregion.

WORKEDEXAMPLE20.5

IdentifyingFunctionalGroupsUsingIRSpectroscopy
DeterminethefunctionalgroupthatismostlikelypresentifacompoundgivesanIRsignalat:
(a) 1705cm1
(b)2150cm1.

Analysis

Checkthecorrelationtablesforsignalsintherequiredregions.Inthisexample,table20.4providessufficient
information.

Solution
(a) AcarbonylC Ogroup(signalsbetween1630and1800cm1)
(b)AnalkyneC Cgroup(signalsbetween2100and2260cm1)

Isouranswerreasonable?

Checkthatthesignalfallswithintherequiredrange.Checkalsoifthereismorethanonepossibility.

PRACTICEEXERCISE20.5
Acompoundgivesastrong,verybroadIRsignalin
theregionfrom3200to3500cm1andastrong
signalat1715cm1.Whichfunctionalgroup
accountsforbothofthesesignals?

WORKEDEXAMPLE20.6

DistinguishingBetweenIsomersUsingIRSpectroscopy
Acetone(propanone)andallylalcohol(prop2en1ol)areconstitutionalisomers.Showhowthesemaybe
distinguishedbyIRspectroscopy.

Analysis

Firstly,youneedtoidentifythekeyfunctionalgroupdifferences:inthiscase,aketone(C O)inacetone
andanalcohol(OH)andalkene(C C)inallylalcohol.Nowconsulttable20.4.

Solution

OnlyacetonegivesastrongsignalintheC Ostretchingregion,16301800cm1.Alternatively,onlyallyl
alcoholgivesastrongsignalintheOHstretchingregion,32003500cm1.

Isouranswerreasonable?

Checkthatyouhavechosentheappropriatestrongsignals(alkenesoftendisplayweaksignalsandare,
therefore,notalwaysagoodchoice).

PRACTICEEXERCISE20.6
Propanoicacidandmethylacetateareconstitutionalisomers.ShowhowthesemaybedistinguishedbyIR
spectroscopy.

chemistryResearch

Thespectroscopyoffingerprints

AssociateProfessorSimonWLewis,CurtinUniversity

Fingermarksarethemostwidelyusedmethodofpersonalidentificationinlawenforcement.Their
presenceatacrimesceneoronanobjectisinstrumentalinconnectingindividualstoacasetheyare
aprimeexampleofLocard'sexchangeprinciplethateverycontactleavesatrace.Themost
commonformofthesearelatent(hidden)fingermarks,andsuccessfulrecoveryfromasceneoran
objectreliesupontheirdetection.Ondeposition,thefingermarkcanbeconsideredasamixtureof
thenaturalsecretionspresentontheskin,anemulsionofwaxes,oilsandaqueouscomponents,and
whateversurfacecontaminantsmaybepresent.Detectionmethodstargetdifferencesbetweenthe
latentfingermarkandthesurfaceuponwhichitislaidandarebasedeitheronphysicalattractionora
chemicalreaction.Forexample,latentfingermarksonpapercanbedetectedbytreatingwiththe
chemical1,2indanedione,whichreactswiththeaminoacidspresentinthelatentfingermarktogive
pinkimpressions,whichareluminescentwhenilluminatedwithbluegreenlight(505nm)and
viewedthroughorangegoggles(seefigure20.8).
 FIGURE20.8A1,2indanedionetreatedfingermarkviewedinphotoluminescencemode.SimonLewis

Thesuccessfuldevelopmentoflatentfingermarksreliesheavilyuponthechemistryofthelatent
fingermarkresidue.Withtime,thechemicalnatureofthelatentdepositwillchangedueto
evaporationofvolatilecomponents,bacterialactionandoxidation.Therateofchangewilldepend
ontheinitialchemicalcompositionoftheresidueandtheenvironmentalconditions.Thisageing
processcanhaveasignificanteffectonthesuccessfuldevelopmentofalatentfingermark.Despite
theseissues,mostfingermarkdetectiontechniqueshavebeendevelopedonthebasisofknowledge
ofthecomponentsofhumanskinsecretions,withoutregardforthepotentialforageingoftheprint.
Inaddition,thereiscurrentlynoreliabletechniqueforestimatingtheageofalatentfingermark.

Theabilitytomakefutureimprovementstocurrentfingermarkdetectionmethodsandthe
developmentofnewapproachestothevisualisationoflatentfingermarksdependscriticallyupona
greaterunderstandingofthechemistryofthefingermarkresidue.Themajorityofstudiesonthe
compositionofskinsecretionshavebeenformedicalpurposesandhavefocusedonthecollectionof
thesecretionsfromthebodyratherthanfromthelatentfingermarkdeposit.Suchstudiestherefore
produceresultsthatarenotrepresentativeofatruelatentfingermark.Morerecentstudieshave
lookedattheforensicaspectsoffingermarkchemistry.However,theseapproachesoftenrequirethe
removalofthelatentfingermarkdepositfromitssubstrate,thusdestroyingitscontextandalso
preventingageingstudiesonthelatentmark.
 FIGURE20.9 (a)TypicalsynchrotronIRspectrumofalatentfingermark
(b)latentfingermarkongoldplatedglass.SimonLewis

ResearchersatCurtinUniversity,incollaborationwithscientistsattheinfrared(IR)beamlineatthe
AustralianSynchrotron,havebeenusingsynchrotronIRmicroscopytoinvestigatethechemistryof
latentfingermarksandhowthischangeswithtime.Fingermarksfromdonorsofdifferentageand
genderweredepositedongoldplatedglassandsubjectedtoIRanalysisatregularintervalsovera
periodof12months.ThesynchrotronsourceismuchbrighterthanconventionalIRspectrometers,
andthissignificantlyenhancesthesignaltonoiseratiosandtherebyreducesthetimerequiredto
producethespectra.Inaddition,thesynchrotronalsoprovidesmuchhigherspatialresolutionthis
enablesskincelldebristobeavoidedbyselectingverysmallareasforanalysis.Thisapproachhas
beenveryusefulformonitoringthevariationinlipidcontentofdepositedlatentfingermarks.

Futureresearchwillincludeinvestigationofthepotentialofmassspectralimagingincombination
withIRdatatoobtainabetterunderstandingofthefundamentalchemistryoflatentfingermark
chemistry.Thiswillprovideaplatformforthedevelopmentofthenextgenerationoflatent
fingermarkdetectionmethods.Observedchangesinchemicalcompositionovertimeandunder
differentenvironmentalconditionswillalsoprovideavaluableinsightintothefingermarkageing
process.Inaddition,theknowledgegainedwillprovideasteptowardsthedevelopmentofa
standardlatentfingermark,vitalforestablishingtheeffectivenessofnewdetectionmethodsandfor
qualityassuranceandqualitycontrolinfingermarkdetection.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.4InterpretingInfraredSpectra
Interpretingspectroscopicdataisaskillthatiseasytoacquirethroughpracticeandexposuretoexamples.AnIR
spectrumwillrevealnotonlythefunctionalgroupsthatarepresentinasample,butalsothosethatcanbeexcluded
fromconsideration.Often,wecandeterminethestructureofacompoundsolelyfromthedatainthespectrumofthe
compound.Atothertimes,wemayneedadditionalinformation,suchasthemolecularformulaofthecompoundor
knowledgeofthereactionsusedtosynthesisethemolecule.Inthissection,wewillseespecificexamplesofIRspectra
forcharacteristicfunctionalgroups.Familiarisingyourselfwiththemwillhelpyoutomasterthetechniqueofspectral
interpretation.

GeneralRulesforInterpretationofIRSpectra
BelowisasetofgeneralrulesandguidelinesfortheanalysisandinterpretationofIRspectra.
Thestrongerthebond,thehigheristhevibrationalfrequency.

TheCYstretchingfrequencydecreaseswithanincreaseinmassofY.

Bendingusuallyoccursatalowerfrequencythanstretching.

Hybridisationeffectscausethestretchingfrequencytoincreaseaswemovefromsp 3tosp

Alkanes
Infraredspectraofalkanesareusuallysimple,withfewsignals,themostcommonofwhicharegivenintable20.5.
TABLE20.5 CharacteristicIRsignalsofalkanes,alkenesandalkynes
Hydrocarbon Vibration Frequency(cm1) Intensity
Alkane
CH stretching 28503000 strong
CH2 bending 1450 medium
CH3 bending 1375and1450 weaktomedium
Alkene

CH stretching 30003100 weaktomedium

C C stretching 16001680 weaktomedium
Alkyne
CH stretching 3300 mediumtostrong
C C stretching 21002260 weaktomedium
Figure20.10showsaninfraredspectrumofdecane.Thestrongsignalwithmultiplesplittingsbetween2850and3000
cm1ischaracteristicofalkaneCHstretching.TheCHsignalisstronginthisspectrumbecausetherearesomany
CHbondsandnootherfunctionalgroups.Theotherprominentsignalsinthespectrumarethoseduetomethylene
bendingat1465cm1andmethylbendingat1380cm1.BecausealkaneCH,CH2andCH3groupsarepresentin
manyorganiccompounds,thesepeaksareamongthemostcommonlyencounteredininfraredspectroscopy,and
consequentlytheyareusuallynotveryusefulasadiagnostictool.

FIGURE20.10Infraredspectrumofdecane.

Alkenes
AneasilyrecognisedalkenesignalisthestretchingbandforthevinylicCHinC CHataslightlyhigher
frequency(at30003100cm1)thanthealkaneCHfrequency(vinylichydrogenatomsarethoseonacarbonatom
ofacarboncarbondoublebond).AlsocharacteristicofalkenesistheC Cstretchingbandat16001680cm1.This
vibration,however,isoftenweakanddifficulttoobserve.SignalsforbothCHstretchinginvinylicC CHand
C Cstretchingcanbeseenintheinfraredspectrumofcyclopentene(figure20.11).Alsovisiblearethesignalsfor
aliphaticCHstretchingnear2900cm1andthemethylenebendingnear1440cm1.

FIGURE20.11Infraredspectrumofcyclopentene.

Alkynes
TheIRspectraofterminalalkynesexhibitastrongsignalat3300cm1duetoCHstretchinginC CH.This
absorptionbandisabsentininternalalkynesbecausethetriplebondisnotbondedtoaproton(terminalalkyneshave
theC Cgroupattheendofthechainininternalalkynes,theC Cgroupisnotattheendofthechain).Alkynes
giveaweaksignalbetween21002260cm1,duetoC Cstretching.Thesignalforthisstretchingisshownclearly
inthespectrumofoct1yne(figure20.12)butisabsentinoct4yne.

FIGURE20.12Infraredspectrumofoct1yne.

Alcohols
AlcoholsareeasilyrecognisedbytheircharacteristicOHstretchingsignalintheirIRspectra(table20.6).Boththe
positionofthissignalanditsintensitydependontheextentofhydrogenbonding(section6.8).Undernormal
conditions,wherethereisextensivehydrogenbondingbetweenalcoholmolecules,OHstretchingoccursasabroad
signalat32003500cm1.ThesignalduetotheCOstretchingvibrationofalcoholsappearsintherange1050
1250cm1.
TABLE20.6 CharacteristicIRsignalsofalcohols
Bond Frequency(cm1) Intensity
OH(hydrogenbonded) 32003500 mediumandbroad
CO 10501250 medium

Figure20.13showsaninfraredspectrumofpentan1ol.ThehydrogenbondedOHstretchingappearsasastrong,
broadsignalcentredat3340cm1.ThesignalforCOstretchingappearsnear1050cm1,avaluecharacteristicof
primaryalcohols.

FIGURE20.13Infraredspectrumofpentan1ol.

Ethers
TheCOstretchingfrequenciesofethersaresimilartothoseobservedinalcoholsandesters.Dialkyletherstypically
showasinglesignalinthisregionbetween1070and1150cm1.ThepresenceorabsenceofasignalforOH
stretchingat32003500cm1forahydrogenbondedOHcanbeusedtodistinguishbetweenanetherandan
alcohol.TheCOstretchingvibrationisalsopresentinesters.Inthiscase,wecanusethepresenceorabsenceofa
signalforC Ostretching(1735to1750cm1)todistinguishbetweenanetherandanester.Figure20.14showsan
infraredspectrumofdiethylether.NoticetheabsenceofasignalforOHstretching.

FIGURE20.14Infraredspectrumofdiethylether.

BenzeneandItsDerivatives
TheIRspectraofaromaticringsshowamediumtoweaksignalintheCHstretchingregionatapproximately3030
cm1,characteristicofCHbondsonsp 2carbonatoms.TheyalsoshowseveralsignalsduetoC Cstretching
between1450and1600cm1.Inaddition,theyshowstrongsignalsintheregionfrom690to900cm1duetoCH
bendingofthearomaticrings(table20.7).Finally,thepresenceofweak,broadbandsbetween1700and2000cm1
canbeanindicatorofabenzenering(oftenthesearesoweakthattheyarenotobserved).
TABLE20.7 CharacteristicIRsignalsofaromatichydrocarbons
Bond Vibration Frequency(cm1) Intensity
CH stretching 3030 mediumtoweak
CH bending 690900 strong
C C stretching 1475and1600 strongtomedium

TheCHandC Csignalpatternscharacteristicofaromaticringscanbeseenintheinfraredspectrumoftoluene
(figure20.15).

FIGURE20.15Infraredspectrumoftoluene.

Amines
ThemostimportantandreadilyobservedinfraredsignalsofprimaryandsecondaryaminesareduetoNHstretching
vibrations,whichappearintheregionfrom3100to3500cm1.Primaryamineshavetwosignalsinthisregion,one
causedbysymmetricstretchingvibrationandtheotherbyasymmetricstretching.ThetwoNHstretchingbands
characteristicofaprimaryaminecanbeseenintheIRspectrumofbutylamine(figure20.16).Secondaryaminesgive
onlyonebandinthisregion.TertiaryamineshavenoNHandsoaretransparentinthisregionoftheinfrared
spectrum.

FIGURE20.16Infraredspectrumofbutylamine,aprimaryamine.

AldehydesandKetones

Aldehydesandketonesshowcharacteristicstronginfraredsignalsbetween1705and1780cm1associatedwiththe
stretchingvibrationofthecarbonoxygendoublebond.Thestretchingvibrationforthecarbonylgroupofmenthone
occursat1705cm1(figure20.17).

FIGURE20.17Infraredspectrumofmenthone.

Becauseseveraldifferentfunctionalgroupscontainacarbonylgroup,itisoftennotpossibletotellfromsignalsinthis
regionalonewhetherthecarbonylcontainingcompoundisanaldehyde,aketone,acarboxylicacidoranester.

CarboxylicAcidsandTheirDerivatives
ThemostimportantinfraredsignalsofcarboxylicacidsandtheirfunctionalderivativesareduetotheC Ostretching
vibrationthesesignalsaresummarisedintable20.8.
TABLE20.8 CharacteristicIRsignalsofcarboxylicacids,estersandamides
C Ovibrational
Compound frequency(cm1) Additionalsignals(cm1)
16301680 NHstretchingat3200and3400(1amideshavetwoNHpeaks)
(2amideshaveoneNHpeak)

17001725 OHverybroadstretchingat24003400COstretchingat1210
1320
 17351750 COstretchingat10001100and12001250

Thecarboxylgroupofacarboxylicacidgivesrisetotwocharacteristicsignalsintheinfraredspectrum.Oneofthese
occursintheregionfrom1700to1725cm1andisassociatedwiththestretchingvibrationofthecarbonylgroup.This
regionisessentiallythesameasthatobservedforthecarbonylgroupsofaldehydesandketones.Theotherinfrared
signalcharacteristicofacarboxylgroupisabandbetween2400and3400cm1duetothestretchingvibrationoftheO
Hgroup.Thissignal,whichoftenoverlapstheCHstretchingband,isgenerallyverybroadduetohydrogen
bondingbetweenmoleculesofthecarboxylicacid.BothC OandOHstretchingscanbeseenintheinfrared
spectrumofbutanoicacid,showninfigure20.18.

FIGURE20.18Infraredspectrumofbutanoicacid.

TheIRspectraofestersdisplaystrongsignalsforC Ostretchingintheregionbetween1735and1750cm1m.In
addition,theydisplaystrongsignalsforCOstretchingintheregionfrom1000to1250cm1(figure20.19).

FIGURE20.19Infraredspectrumofethylbutanoate.

Thesignalduetocarbonylstretchingofamidesoccursatlowerwavenumbers(16301680cm1)thanothercarbonyl
compounds.Liketheamines,primaryandsecondaryamidesshowNHstretchingintheregionfrom3200to3400
cm1mprimaryamides(RCONH2)showtwoNHsignals,whereassecondaryamides(RCONHR)showonlya
singleNHsignals.Tertiaryamides,ofcourse,donotshowNHstretchingabsorptions.Comparethethreespectra
infigure20.20.
 FIGURE20.20 Infraredspectraof
(a)N,Ndiethyldodecanamide,atertiaryamide,
(b)Nmethylbenzamide,asecondaryamide,and
(c)butanamide,aprimaryamide.

WORKEDEXAMPLE20.7

DeterminingaCompoundFromanIRSpectrumandMolecularFormula
AnunknowncompoundwiththemolecularformulaC3H6O2yieldsthefollowingIRspectrum.Drawpossible
structuresforthecompound.
Analysis

Therearemanywaystosolvethissortofproblem.Weshouldstartbydeterminingtheindexofhydrogen
deficiency(IHD).BasedonthereferenceformulaofC3H8,theIHD=1.Thismeanswehaveeitheronering
oronedoublebond.Nowwecaninspectthespectrumforkeyfunctionalgroupsignals(seetable20.4)and
thendrawpossibleisomersthatwouldmatchthedata.Donotforgettoalsoconsidermissingsignals.For
example,inthiscase,thereisnosignalforanOHstretchat~3300cm1,whichautomaticallyexcludes
carboxylicacidsandalcohols.

Solution

TheIRspectrumshowsastrongsignalatapproximately1750cm1,whichisindicativeofaC Ogroupand,
therefore,wecannothaveanalkeneoraring(IHD=1).ThespectrumalsoshowsstrongCOsignalspeaks
at1250and1050cm1.Furthermore,therearenosignalsabove3000cm1,whicheliminatesthepossibilityof
anOHgroup.Now,let'sputtheinformationtogethersowecanproposesomestructures.Sincewecannot
haveanacidoralcohol(noOHsignal),thetwooxygenatomsmustbepartofanester,oranetherandan
aldehyde(wedonothaveenoughcarbonatomsforanetherandaketone).Onthebasisofthisdata,three
structuresarepossibleforthegivenmolecularformula:

Thegivenspectrumcannowbeannotatedasfollows:

Isouranswerreasonable?

Checkthatthecompoundssuggestedwouldgivetheappropriatesignals.Checkalsothatthecompoundshave
thecorrectmolecularformula.

PRACTICEEXERCISE20.7
Whatdoesthevalueofthewavenumberofthe
stretchingfrequencyforaparticularfunctional
groupindicateabouttherelativestrengthofthe
bondinthatfunctionalgroup?
WORKEDEXAMPLE20.8

InterpretingIRSpectra
DeterminepossiblestructuresforacompoundthatyieldsthefollowingIRspectrumandhasamolecular
formulaofC7H8O.

Analysis

GiventhemolecularformulaofC7H8O,youshoulddeterminetheindexofhydrogendeficiencytobe4,
basedonthereferenceformulaofC7H16.Whileaccountingforthisvaluemayseemdauntingatfirst(consider
thepossiblecombinationsoffourringsorbonds),recallthatthebenzeneringhasanindexofhydrogen
deficiencyof4.LookforcharacteristicbandsforaromaticcompoundsintheIRspectrumiftheyarepresent,
youknowthattherearenootherdoublebondsorringsinthemolecule.Theoxygenatommaybepresentas
analcohol/phenol,ether,aldehydeorketone(thelasttwowouldnotbepossibleiftherewasanaromaticring
present).

Solution

Aquickinspectionofthespectrumindicatesastrong,broadsignalatapproximately3310cm1duetoOH
stretchingandtheabsenceofasignalduetoacarbonylgroupbetween1700and1800cm1.Becausewe
musthaveanOHgroup,wecannotproposeanystructureswithanethergroup(oranaldehydeora
ketone).CloserinspectionofthespectrumshowsthecharacteristicaromaticCHbendingbandsat690and
740cm1andtheweak,broadbandsbetween1700and2000cm1,whichsupporttheexistenceofabenzene
ring.Also,asignalforsp 2CHstretchingispresentjustabove3000cm1.AromaticC Cstretching
absorptionbandsat1450and1490cm1alsoindicateabenzenering.Now,giventhatthemolecularformula
isC7H8OandwehaveabenzeneringandanOHgroup,wehavetoaccountforonlyonemorecarbon
atom.Thislastcarbonatommustbebondedtothebenzenering.Thereareonlyfourpossibleplaceswecan
attachanOHgrouptotoluene(methylbenzene)andthesestructuresaregivenbelow.

Thegivenspectrumcannowbeannotatedasfollows:
 Isouranswerreasonable?

YoushouldcheckthatalloftheproposedcompoundshavethecorrectIHDandthatthekeysignalsforeach
compoundarepresentinthespectrum.

TheprecedingexamplesillustratethepowerandlimitationsofIRspectroscopy.Thepowerliesinitsabilitytoprovide
uswithinformationaboutthefunctionalgroupsinamolecule.IRspectroscopydoesnot,however,provideuswith
informationonhowthosefunctionalgroupsareconnected.Fortunately,anothertypeofspectroscopynuclear
magneticresonance(NMR)spectroscopydoesprovideuswithconnectivityinformation.NMRspectroscopyisthe
nexttopicofthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.5NuclearMagneticResonanceSpectroscopy
Webeganthischapterwithanintroductiontomassspectrometryandwesawhowitcouldbeusedtodetermine
molecularmassesandmolecularformulae.Wethendiscussedinfraredspectroscopyandsawhowinfraredlightcould
beusedtodeterminethetypesoffunctionalgroupspresentinanunknowncompound.Nowwewillconcentrateonthe
techniqueknownasnuclearmagneticresonance(NMR)spectroscopy.Thephenomenonofnuclearmagnetic
resonancewasfirstdetectedin1946byFelixBlochandEdwardPurcell,whosharedthe1952NobelPrizeinphysics
fortheirdiscoveries.NMRspectroscopyhasbecomethemostimportanttoolinthedeterminationoforganicstructures.
Theparticularvalueofnuclearmagneticresonance(NMR)spectroscopyisthatitgivesusinformationaboutthe
numberandtypesofatomsinamoleculeandcanalsoprovideinformationonhowtheyareconnected.1HNMR
spectroscopygivesinformationaboutthenumberandtypesofhydrogenatomswithinamoleculewhile13CNMR
spectroscopytellsusaboutthenumberandtypesofcarbonatoms.Althoughwewillconsideronlyhydrogenand
carbonNMR,itisalsopossibletoobtainNMRspectraofmanyotherelements.

TheOriginofNuclearMagneticResonance
Fromourstudyinchapter4,wearealreadyfamiliarwiththeconceptthatanelectronhasaspinandthataspinning
chargecreatesanassociatedmagneticfield.Ineffect,anelectronbehavesasifitisatinybarmagnet.Anatomic
nucleusthathasanoddmassoranoddatomicnumberalsohasaspin(anuclearspin)andalsobehavesasifitisatiny
barmagnet.Recallthat,whendesignatingisotopes,asuperscriptrepresentsthemassoftheelement.Thus,thenucleiof
1Hand13C,isotopesofthetwoelementsmostcommoninorganiccompounds,alsohaveanuclearspin,whereasthe

nucleiof12Cand16Odonothaveanuclearspin.Accordingly,inthissense,nucleiof1Hand 13Carequitedifferent
fromnucleiof12Cand16O.

WORKEDEXAMPLE20.9

DeterminingWhetheranAtomicNucleusHasaSpin
Whichofthefollowingnucleihasaspin?
(a)
(b)

Analysis

Recallthattohaveanuclearspinanisotopemusthaveeitheranoddatomicnumberoranoddmass.

Solution
(a) 14C,aradioactiveisotopeofcarbon,hasneitheranoddmassnumbernoranoddatomicnumberand,
therefore,doesnothaveaspin.
(b)14N,themostcommonnaturallyoccurringisotopeofnitrogen(99.63%ofallnitrogenatoms),hasan
oddatomicnumberand,therefore,hasaspin.

Isouranswerreasonable?

Checkthateitherthemassnumberortheatomicnumberisodd.

PRACTICEEXERCISE20.8
Whichofthefollowingnucleihasaspin?
 (a)
(b)

Withinacollectionof1Hand13Catoms,thespinsoftheirnucleiarecompletelyrandominorientation.Whenweplace
theminapowerfulmagneticfield,however,interactionsbetweentheirnuclearspinsandtheappliedmagneticfieldare
quantised,andonlytwoorientationsareallowed(figure20.21).

FIGURE20.21 1 Hand13 Cnuclei

(a)intheabsenceofanappliedmagneticfieldand
(b)
inthepresenceofanappliedfield.1 Hand13 Cnucleiwithspin+ arealignedwiththeapplied

magneticfieldandareinthelowerspinenergystatethosewithspin arealignedagainstthe
appliedmagneticfieldandareinthehigherspinenergystate.

Whenhydrogennucleiareplacedinanappliedmagneticfield,asmallmajorityoftheirnuclearspinsalignwiththe
appliedfieldinthelowerenergystate.Irradiationofnucleiwithradiofrequencyradiationoftheappropriateenergy
causessomeofthoseinthelowerenergyspinstatetoabsorbenergyandresultsintheirnuclearspinsflippingfromthe
lowerenergystatetothehigherenergystate,asillustratedinfigure20.22.Inthiscontext,resonanceisdefinedasthe
absorption(oremissionwhenthenucleireturntoequilibrium)ofelectromagneticradiationbyaspinningnucleusand
theresultingflipofitsnuclearspinstate.(Note:(Resonanceusedinthiscontextiscompletelydifferentfromthe
resonancetheoryofchemicalstructuresdiscussedearlier.)

FIGURE20.22Anexampleofresonancefornucleiofspin+ and .

Ifastrongenoughmagneticfieldisused,thentheenergyrequiredtocausethisflippingcorrespondstothatof
radiowaves.Forexample,anappliedfieldstrengthof7.05tesla(T)isreadilyavailablewithpresentday
superconductingelectromagnets(forcomparison,themagnitudeoftheEarth'smagneticfieldisapproximately3060
microtesla).Insuchfields,thedifferenceinenergybetweennuclearspinstatesfor1His0.120Jmol1,which
correspondstoelectromagneticradiationofapproximately300MHz(300000000Hz).Atthesamemagneticfield
strength,thedifferenceinenergybetweennuclearspinstatesfor13Cis0.035Jmol1,whichcorrespondsto
electromagneticradiationof75MHz.Thus,wecanuseelectromagneticradiationintheradiofrequencyrangetodetect
changesinnuclearspinstatesfor1Hand13C.Inthenextseveralsections,wedescribehowthesemeasurementsare
madefornuclearspinstatesofthesetwoisotopesandthenhowthisinformationcanbecorrelatedwithmolecular
structure.

Shielding

Ifweweredealingwith1Hnucleiisolatedfromallotheratomsandelectrons,anycombinationofappliedfieldand
electromagneticradiationthatproducesaresonancesignalforonehydrogennucleuswouldproducethesame
resonancesignalforallotherhydrogennuclei.Inotherwords,thesameamountofenergywouldcauseallhydrogen
atomstoresonate,andthehydrogenatomswouldbeindistinguishablefromoneanother.NMRwouldthenbean
ineffectivetechniquefordeterminingthestructureofamoleculebecauseallthehydrogenatomsinacompoundwould
resonateatthesamefrequency,givingrisetooneandonlyoneNMRsignal.

Fortunately,hydrogenatomsinorganicmoleculesaresurroundedbyelectronsandbyotheratoms.Theelectronsthat
surroundanucleusalsohavespinsotheycreatelocalmagneticfieldsthatopposetheappliedfield.Consequently,the
magneticfieldexperiencedbyahydrogenatominamoleculeisslightlylessthanthatoftheappliedmagneticfieldof
theinstrument.Althoughtheselocalmagneticfieldscreatedbyelectronsareordersofmagnitudeweakerthanthe
appliedmagneticfieldsusedinNMRspectroscopy,theyarenonethelesssignificantatthemolecularlevel.Theresultof
theselocalmagneticfieldsisthathydrogenatomsareshieldedfromtheappliedfield.Thegreatertheshieldingofa
particularhydrogenatombylocalmagneticfields,thegreateristheenergy(frequencyofradiowaves)requiredtobring
thathydrogenatomintoresonance.

Aswelearnedinpreviouschapters,theelectrondensityaroundanucleuscanbeinfluencedbytheatomsthatsurround
thenucleus.Forexample,theelectrondensityaroundthehydrogenatomsinfluoromethane(figure20.23)islessthan
thataroundthehydrogenatomsinchloromethane(figure20.24),duetothegreaterelectronegativityoffluorinerelative
tochlorine.Thus,wecansaythatthehydrogenatomsinchloromethanearemoreshieldedthanthehydrogendatoms
influoromethane.Conversely,wecansaythehydrogenatomsinfluoromethanearemoredeshielded(reducedelectron
densityaroundeachhydrogenatom)thanthoseinchloromethane.

Thedifferencesinresonancefrequenciesbetweenthevarious1Hnucleiwithinamoleculecausedbyshieldingare
generallyverysmall.Thedifferencebetweentheresonancefrequenciesofhydrogenatomsinchloromethane
comparedwiththoseinfluoromethane,forexample,isonly360Hzunderanappliedfieldof7.05tesla.Considering
thattheradiofrequencyradiationusedatthisappliedfieldisapproximately300MHz,thedifferenceinresonance
frequenciesbetweenthesetwosetsofhydrogenatomsisonlyslightlygreaterthan1partpermillion(1ppm)compared
withtheirradiatingfrequency.

FIGURE20.23Fluorine'sgreaterelectronegativityproducesalargerinductiveeffectand,therefore,reducestheelectron
densityaroundeachhydrogenatom.Wesaythatthesehydrogenatomsaredeshielded.

FIGURE20.24Chlorineislesselectronegativethanfluorine,resultinginasmallerinductiveeffectand,therefore,agreater
electrondensityaroundeachhydrogenatom.Wesaythatthehydrogenatomsinchloromethanearemore
shielded(bytheirlocalenvironment)thanthoseinfluoromethane.

Theimportanceofshieldingforelucidatingthestructureofamoleculewillbediscussedlaterinthissection.
AnNMRSpectrometer
ModernNMRspectrometers(figure20.25)workbyirradiatingasamplewithashortpulseofradiationthatcoversthe
entirerangeofrelevantradiowavefrequencies.Allhydrogenatomsaresimultaneouslyexcitedandthenbegintoreturn
(ordecay)totheiroriginalspinstate.Aseachatomdecays,itreleasesenergyofaparticularfrequencythatisdetected
asanelectricalimpulseinthereceivercoils.Theresultingcombinationofelectricalimpulsesgeneratedfromalldecay
frequenciesiscalledafreeinductiondecay(FID).TypicallyanFIDcanberecordedevery12seconds,andmanyare
collectedandthenaveragedtogenerateaspectrumusingamathematicaltechniquecalledFouriertransformation.This
signalaveragingallowsustoeasilymeasuretheNMRspectrumofverysmallamountsofsample(aslittleas1mg).

FIGURE20.25Schematicdiagramofanuclearmagneticresonancespectrometer.

Torecordaspectrum,thesampleisdissolvedinasolventhavingno1Hhydrogenatoms,mostcommonlydeutero
chloroform,CDCl3,ordeuteriumoxide,D2O(deuterium,D,isthe2Hisotopeofhydrogen).Thesamplecellisasmall
glasstubesuspendedinthehollowboreatthecentreofthemagnetandsetspinningonitslongaxistoensurethatall
partsofthesampleexperienceahomogeneousappliedfield(figure20.26).
 FIGURE20.26AnNMRsampletubeinitsspinningassembly.

Itiscustomarytomeasuretheresonancefrequenciesofindividualnucleirelativetotheresonancefrequencyofthe
samenucleiinareferencecompound.Thereferencecompoundnowuniversallyacceptedfor1HNMRand13CNMR
spectroscopyinorganicsolventsistetramethylsilane(TMS):

Whenwedeterminea1HNMRspectrumofacompound,wereporthowfartheresonancesignalsofitshydrogen
atomsareshiftedfromtheresonancesignalofthehydrogenatomsinTMS.Whenwedeterminea13CNMRspectrum,
wereporthowfartheresonancesignalsofitscarbonatomsareshiftedfromtheresonancesignalofthefourcarbon
atomsinTMS.

TostandardisereportingofNMRdata,scientistshaveadoptedaquantitycalledthechemicalshift()expressedin
partspermillion:

Inatypical1HNMRspectrum,thehorizontalaxisrepresentsthe(delta)scale,withvaluesfrom0ontherightto10
ontheleft,butvaluescanfalloutsidethisrange(forexample,seefigures20.31and20.47andtable20.9).Thevertical
axisrepresentstheintensityoftheresonancesignal.Figure20.27showsa1HNMRspectrumofmethylacetate,a
compoundusedinthemanufactureofartificialleather.Thesmallsignalat0inthisspectrumrepresentsthehydrogen
atomsofthereferencecompound,TMS.Theremainderofthespectrumconsistsoftwosignals:oneforthehydrogen
atomsoftheOCH3groupandoneforthehydrogenatomsofthemethylattachedtothecarbonylgroup.Itisnotour
purposeatthemomenttodeterminewhichhydrogenatomsgiverisetowhichsignalbutonlytorecognisetheformin
whichwerecordanNMRspectrumandtounderstandthemeaningofthecalibrationmarks.
 FIGURE20.271 HNMRspectrumofmethylacetate.

Anoteonterminology:Ifasignalisshiftedtowardstheleftofthespectrum,wesaythatthenucleigivingrisetothat
signalaredeshielded(alsooftenreferredtoasshifteddownfield).Conversely,ifasignalisshiftedtowardstherightof
thespectrum,wesaythatthenucleigivingrisetothatsignalareshielded(alsooftenreferredtoasshiftedupfield).
Figure20.28summarisessomeofthecommonNMRterms.

FIGURE20.28AsummaryofsomecommonNMRterms.

EquivalentHydrogenAtoms
Giventhestructuralformulaofacompound,howdoweknowhowmanysignalstoexpect?Theansweristhat
equivalenthydrogenatomsgivethesame1HNMRsignalconversely,nonequivalenthydrogenatomsgivedifferent
1HNMRsignals.Adirectwaytodeterminewhichhydrogenatomsinamoleculeareequivalentistoreplaceeachin
turnbyatestatom,suchasahalogenatom.Ifreplacementoftwohydrogenatomsinturngivesthesamecompound,
thetwohydrogenatomsareequivalent.Ifreplacementgivesdifferentcompounds,thetwohydrogenatomsare
nonequivalent.

Usingthissubstitutiontest,wecanshowthatpropanecontainstwosetsofequivalenthydrogenatoms:asetofsix
equivalent1hydrogenatoms(hydrogenatomsattachedtoa1carbonatom)andasetoftwoequivalent2hydrogen
atoms(hydrogenatomsattachedtoa2carbonatom).Thuswewouldexpecttoseetwosignals:oneforthesix
equivalentmethylhydrogenatomsandoneforthetwoequivalentmethylene(CH2)hydrogenatoms.

Replacementofanyoftheredhydrogenatomsbyachlorineatomgives1chloropropanethus,alloftheredhydrogenatomsin
propaneareequivalent.
Replacementofeitherofthebluehydrogenatomsbyachlorineatomgives2chloropropanethus,bothofthebluehydrogen
atomsinpropaneareequivalent.

WORKEDEXAMPLE20.10

EQuivalentHydrogenAtoms
Determinethenumberofsetsofequivalenthydrogenatomsineachofthefollowingcompoundsandthe
numberofhydrogenatomsineachset.
(a)

(b)

Analysis

Youshouldstartbyidentifyingallthehydrogenatomsinthemolecules.Compound(a)has10and
compound(b)has12.Nowapplythesubstitutionprocessdescribedpreviouslytoidentifyequivalent
hydrogenatoms.

Solution
(a)Therearetwosetsofequivalenthydrogenatomsin2methylpropaneasetofnineequivalent1
hydrogenatomsandone3hydrogenatom.

Replacinganyoneoftheredhydrogenatomswithachlorineatomyields1chloro2methylpropane.
Replacingthebluehydrogenatomwithachlorineatomyields2chloro2methylpropane.

(b)Therearefoursetsofequivalenthydrogenatomsin2methylbutanetwodifferentsetsof1
hydrogenatoms,onesetof2hydrogenatomsandone3hydrogenatom.

Replacinganyoftheredhydrogenatomswithachlorineatomyields1chloro2methylbutane.Replacingthe
bluehydrogenatomwithachlorineatomyields2chloro2methylbutane.Replacingapurplehydrogenatom
withachlorineatomyields2chloro3methylbutane.Replacingagreenhydrogenatomwithachlorineatom
yields1chloro3methylbutane.

Isouranswerreasonable?

Checkthatyouhaveidentifiedallhydrogenatomsandthatthedifferentgroupsareactuallydifferent.

PRACTICEEXERCISE20.9
 Determinethenumberofsetsofequivalent
hydrogenatomsineachofthefollowing
compoundsandthenumberofhydrogenatomsin
eachset.
(a)

(b)

Herearefourorganiccompounds,eachofwhichhasonesetofequivalenthydrogenatomsandgivesonesignalinits
1HNMRspectrum:

Thestructuresbelowshowthatmoleculeswithtwoormoresetsofequivalenthydrogenatomsgiverisetoadifferent
resonancesignalforeachset.Forexample,1,1dichloroethanehas(a)threeequivalent1hydrogenatomsand(b)one
3hydrogenatom,sotherearetworesonancesignalsinits1HNMRspectrum.

Youshouldseeimmediatelythatvaluableinformationaboutacompound'smolecularstructurecanbeobtainedsimply
bycountingthenumberofsignalsina1HNMRspectrumofthatcompound.Consider,forexample,thetwo
constitutionalisomerswithmolecularformulaC2H4Cl2.Thecompound1,2dichloroethanehasfourequivalent2
hydrogenatomsandshowsonesignalinits1HNMRspectrum.Itsconstitutionalisomer1,1dichloroethanehasthree
equivalent1hydrogenatomsandone3hydrogenatomthisisomershowstwosignalsinits1HNMRspectrum.
Thus,simplycountingsignalscanallowyoutodistinguishbetweentheseconstitutionalisomers.Forexample,in
workedexample20.7wenarroweddownthreepossiblecandidateswithamolecularformulaofC3H6O2thatcould
haveproducedtheIRspectrum.Now,ifweconsiderthenumberofsignalsinthe1HNMRspectrumofthese
compounds,weseethattheygiverisetotwo,threeandthreesignalsrespectively.

Laterwewillseehowwecandistinguishbetweenethylformateandmethoxyacetaldehyde.
WORKEDEXAMPLE20.11

StructuralFormulaeFromNumberofSignalsin1HNMRSpectra

Eachofthefollowingcompoundsgivesonlyonesignalinits1HNMRspectrum.Proposeastructural
formulaforeach.
(a)C2H6O
(b)C3H6Cl2
(c)C6H12

Analysis

WeshouldstartbydeterminingtheIHDasthiswilltellyouifyouneedtoconsiderringsordoublebonds.
Withthisinformation,youthenneedtoconsiderhowyoucanputtheatomsintheformulaetogethersothat
allhydrogenatomsareequivalent(drawingpossibleisomersandcheckingthenumberofdifferenthydrogen
atomsisprobablytheeasiestway).

Solution

GiventhattheIHDforthethreecompoundsare0,0and1,respectively,weknowthatweneedtoconsider
aringoralkeneonlyfor(c).Thefollowingarestructuralformulaeforeachofthegivencompounds.Notice
that,foreachstructure,thereplacementofanyhydrogenatomwithachlorineatomwillyieldthesame
compoundregardlessofthehydrogenbeingreplaced.
(a)CH3OCH3
(b)

(c)

Isouranswerreasonable?

Checkthat,foreachstructure,thereplacementofanyhydrogenatomwithachlorineatomwillyieldthe
samecompoundregardlessofthehydrogenatombeingreplaced.

PRACTICEEXERCISE20.10
Eachofthefollowingcompoundsgivesonlyone
signalinits1HNMRspectrum.Proposeastructural
formulaforeachcompound.
(a)C3H6O
(b)C5H10
(c)C5H12
(d)C4H6Cl4
SignalAreas

Wehavejustseenthatthenumberofsignalsina1HNMRspectrumgivesusinformationaboutthenumberofsetsof
equivalenthydrogenatoms.Signalareasina1HNMRspectrumcanbemeasuredbyamathematicaltechniquecalled
integration.Inmostofthespectrashowninthistext,thisinformationisdisplayedintheformofalineofintegration
superimposedontheoriginalspectrum.Theverticalriseofthelineofintegrationovereachsignalisproportionaltothe
areaunderthatsignal,which,inturn,isproportionaltothenumberofhydrogenatomsgivingrisetothesignal.

Figure20.29showsanintegrated1HNMRspectrumofthepetroladditivetertbutylacetate,C6H12O2.Thespectrum
showssignalsat1.4and2.0.Theintegratedareaofthemoreshieldedsignal(totheright:67chartdivisions)isnearly
threetimesthatofthelessshieldedsignal(totheleft:23chartdivisions).Wehaveusedthehorizontallinesonthechart
asaunitofmeasure(10chartdivisionsareequivalenttothedistancebetweentwoconsecutivesolidhorizontallines)
alternatively,wecouldmeasurethelineseparationwitharuler).Thisrelationshipcorrespondstoaratioof3:1.We
knowfromthemolecularformulathatthereisatotalof12hydrogenatomsinthemolecule.Theratiosobtainedfrom
theintegrationlinesareconsistentwiththepresenceofonesetofnineequivalenthydrogenatomsandonesetofthree
equivalenthydrogenatoms.WewilloftenmakeuseofshorthandnotationinreferringtoanNMRspectrumofa
molecule.Thenotationliststhechemicalshiftofeachsignal,beginningwiththemostdeshieldedsignalandfollowed
bythenumberofhydrogenatomsthatgiverisetoeachsignal(basedontheintegration).Theshorthandnotation
describingthespectrumoftertbutylacetate(figure20.29)wouldbe2.0(3H)and1.4(9H).

FIGURE20.291 HNMRspectrumoftertbutylacetate,C6 H12 O2 ,showingalineofintegration.Theratioofsignalareasforthe

twopeaksis3:1,which,foramoleculepossessing12hydrogenatoms,correspondstonineequivalent
hydrogenatomsofonesetandthreeequivalenthydrogenatomsofanotherset.

Analternativewayofrepresentingintegrationvaluesistohavetheintegrationvaluesprintedbelowthehorizontalscale
axis.Itisquitenormalforthenumericalvaluesprovidednottoexactlymatchtheratio,butthisisnotaproblemaswe
knowwemusthaveintegervaluesforthenumberofhydrogenatoms.Asanexample,thespectrumofbenzylalcohol
isgiveninfigure20.30.
FIGURE20.301 HNMRspectrumofbenzylalcohol,C7 H8 O,showingtheintegrationvalues.Theratioofsignalareaforthe
threepeaksis5:2:1(fromlefttoright).Althoughthenumericalvaluesprovideddonotexactlymatchtheratio,
thisisnotaproblemasthenumberofhydrogenatomsmustbeintegers.

WORKEDEXAMPLE20.12

DeterminingIntegrationValues

Thefollowingisa1HNMRspectrumofacompoundwiththemolecularformulaC9H10O2.Fromananalysis
oftheintegrationdata,calculatethenumberofhydrogenatomsgivingrisetoeachsignal.

Analysis

Determinetherelativeratioofthethreesignals,bearinginmindthatthereisatotalof10hydrogenatomsin
themolecule.Rememberalsothateachsignalmustrepresentawholenumberofhydrogenatoms(e.g.you
cannothave0.2hydrogenatoms).

Solution

Theratiooftherelativesignalheights(obtainedfromthenumberofhorizontalchartdivisions)is5:2:3.The
molecularformulaindicatesthattherearetenhydrogenatoms.Thus,thesignalat7.3representsfive
hydrogenatoms,thesignalat5.1representstwohydrogenatoms,andthesignalat2.1representsthree
hydrogenatoms.Consequently,thesignalsandthenumberofhydrogenatomseachsignalrepresentsare
7.3(5H),5.1(2H)and2.1(3H).

Isouranswerreasonable?
 Checkthatthesumofthenumberofhydrogenatomsforeachsignalequalsthetotalnumberofhydrogen
atomsinthemolecule.

PRACTICEEXERCISE20.11

Theintegrationvaluesofthetwosignalsinthe1H
NMRspectrumofaketonewithmolecularformula
C7H14Oaregivenasaratioof6.2to1.0.Calculate
thenumberofhydrogenatomsgivingrisetoeach
signal,andproposeastructuralformulaforthis
ketone.

ChemicalShift
ThepositionofasignalalongthexaxisofanNMRspectrumisknownasthechemicalshiftofthatsignal.The
chemicalshiftofasignalina1HNMRspectrumcangiveusvaluableinformationaboutthetypeofhydrogenatoms
givingrisetothatabsorption.Hydrogenatomsonmethylgroupsbondedtosp 3hybridisedcarbons,forexample,
typicallygiveasignalnear0.81.0(seefigure20.33foranexample).Hydrogenatomsonmethylgroupsbondedto
acarbonylcarbongivesignalsnear2.02.3(seefigures20.27and20.29),andhydrogenatomsonmethylgroups
bondedtooxygengivesignalsnear3.73.9(seefigure20.27).Table20.9liststheaveragechemicalshiftformostof
thetypesofhydrogenatomswedealwithinthistext.Noticethatmostofthevaluesshownfallwithinarathernarrow
rangefrom0to12units(ppm).Infact,althoughthetableshowsavarietyoffunctionalgroupsandhydrogenatoms
bondedtothem,wecanusetherulesofthumbinfigure20.31torememberthechemicalshiftsofmosttypesof
hydrogenatom.

FIGURE20.31Asimplecorrelationchartfor1 HNMRchemicalshifts.WheretherangeislabelledRCH2 Y(Y=halogen,Nor

O),shiftsformethylandmethinehydrogenatoms,R2 CHY,alsofallwithinthisrange(withthemethylbeingat
slightlylowerchemicalshiftandthemethineatslightlyhigherchemicalshift).

TABLE20.9 Averagevaluesofchemicalshiftsofrepresentativetypesofhydrogenatoms

Typeofhydrogen(a) Chemicalshift()(b)

(CH3)4Si (bydefinition)

RCH3 0.81.0

RCH2R 1.21.4

R3CH 1.41.7

R2C CRCHR2 1.62.6

 RC CH 2.03.0
ArCH3 2.22.5

ArCMH2R 2.32.8

ROH 0.56.0
RCH2OH 3.44.0

R2NH 0.55.0

R2NH 0.55.0

2.02.3

2.22.6

3.73.9

4.14.7

RCH2I 3.13.3

RCH2Br 3.43.6

RCH2Cl 3.63.8

RCH2F 4.44.5

ArOH 4.510

R2C CH2 4.65.0

R2C CHR 5.05.7

ArH 6.58.5
9.510.1

1012

(a)R=alkylgroup,Ar=arylgroup.
(b)Valuesareapproximate.Otheratomswithinthemoleculemaycausethesignaltoappearoutsidethese
ranges.

WORKEDEXAMPLE20.13

IdentifyingIsomersUsingChemicalShiftData
ThefollowingaretwoconstitutionalisomerswiththemolecularformulaC6H12O2.
 (a) Predictthenumberofsignalsinthe1HNMRspectrumofeachisomer.
(b)Predicttheratioofareasofthesignalsineachspectrum.
(c)Showhowtheseisomersmaybedistinguishedonthebasisofchemicalshift.

Analysis

Firstidentifythetypesofdifferenthydrogenatomsandthenthenumbersofeachtype.Nowcarefully
examinethetwostructuresandidentifythekeydifferences.Ifthereareanyhydrogenatomsinvery
differentenvironments,thenthesignalsduetothesehydrogenatomswillbemostimportantin
distinguishingbetweenthetwostructures.

Solution
(a)Eachcompoundcontainsasetofnineequivalentmethylhydrogenatomsandasetofthree
equivalentmethylhydrogenatoms.
(b)The1HNMRspectrumofeachconsistsoftwosignalsintheratio9:3or3:1.
(c)ThetwoconstitutionalisomerscanbedistinguishedbythechemicalshiftofthesingleCH3group
(showninblueforeachcompound).Usingourrulesofthumbinfigure20.31,wefindthatthe
hydrogenatomsofCH3Oarelessshielded(appearfurtherdownfield)thanthehydrogenatomsof
CH3C O.Table20.9givesapproximatevaluesforeachchemicalshift.Experimentalvaluesareas
follows:

Isouranswerreasonable?

Checkthecorrelationtablestoensurethatthechemicalshiftsarecorrect.

PRACTICEEXERCISE20.12

(a)Thefollowingaretwoconstitutionalisomerswithmolecularformula
C4H8O2.

i.Predictthenumberofsignalsinthe1HNMRspectrumofeach
isomer.
ii.Predicttheratioofareasofthesignalsineachspectrum.
iii.Showhowtheseisomersmaybedistinguishedonthebasisof
chemicalshift.
(b)Considerthecompoundsinworkedexample20.7.Wehavealready
determinedthenumberofsignalsasshownbelow.
 i.Predicttheratioofareasofthesignalsineachspectrum.
ii.Showhowtheseisomersmaybedistinguishedonthebasisof
chemicalshift.

SignalSplittingandthe(n+1)Rule

Wehavenowseenthreekindsofinformationthatcanbederivedfromanexaminationofa1HNMRspectrum:
1.Fromthenumberofsignals,wecandeterminetheminimumnumberofsetsofequivalenthydrogenatoms.
2.Byintegratingoversignalareas,wecandeterminetherelativenumbersofhydrogenatomsgivingrisetoeach
signal.
3.Fromthechemicalshiftofeachsignal,wecanderiveinformationaboutthetypesofhydrogenatomsineachset.

Wecanderiveafourthkindofinformationfromthesplittingpatternofeachsignal.Considerthe1HNMRspectrum
of1,1,2trichloroethane(figure20.32),asolventforwaxesandnaturalresins.Thismoleculecontainstwo2hydrogen
atomsandone3hydrogenatom,and,accordingtowhatwehavelearnedsofar,wepredicttwosignalswithrelative
areas2:1,correspondingtothetwohydrogenatomsoftheCH2Clgroupandtheonehydrogenatomofthe
CHCl2group.Youseefromthespectrum,however,thatthereareinfactfivepeaks.Howcanthisbewhenwepredict
onlytwosignals?Theansweristhatahydrogenatom'sresonancefrequencycanbeaffectedbythetinymagneticfields
ofotherhydrogenatomscloseby.Thosefieldscausethesignaltobesplitintonumerouspeaks.Asignalmaybesplit
intotwopeaks(calledadoublet,d),threepeaks(atriplet,t),fourpeaks(aquartet,q)andsoon.Asignalthathasnot
beensplitisreferredtoasasinglet(s)andthosewithcomplexsplittingpatternsaretermedmultiplets(m).Ingeneral,
signalsaresplitiftherearehydrogenatomsonadjacentcarbonatoms.Signalsplittingwhentherearemorethanthree
bondsbetweenthehydrogenatoms,asinHCCCH,areuncommon,exceptwhenbondsareinvolved(for
example,inaromaticrings).

FIGURE20.321 HNMRspectrumof1,1,2trichloroethane.

Thesignalat4.0inthe1HNMRspectrumof1,1,2trichloroethaneisduetothehydrogenatomsoftheCH2Cl
group,andthesignalat5.8isduetothesinglehydrogenoftheCHCl2group.

WesaythattheCH2signalat4.0issplitintoadoubletandthattheCHsignalat5.8issplitintoatriplet.Inthis
phenomenon,calledsignalsplitting,the1HNMRsignalfromonesetofhydrogenatomsissplitbytheinfluenceof
neighbouringhydrogenatomsthatareequivalenttoeachotherbutnotequivalenttothehydrogenatom(s)givingrise
tothesignal.Thedegreeofsignalsplittingcanbepredictedonthebasisofthe(n+1)rule,wherenisthenumberof
hydrogenatomsequivalenttoeachotheronadjacentcarbonatoms.Notethat,ifthesignalduetoHaissplitbyHbon
anadjacentcarbonatom,thenthesignalduetoHbisalsosplitbyHa.Nosignalsplittingisobservedbetween
equivalentneighbouringhydrogenatoms.Forexample,thespectrumof1,2dichloroethanehasonlyonesignal(a
singlet)at3.7.

Pascal'strianglecanbeusedtodescribethesplittingpattern(alsocalledthemultiplicity)andthepeakintensitieswithin
splitsignals,asshownintable20.10.
TABLE20.10 Multiplicityandrelativeintensitiesofpeaksinsplitsignals
Numberofequivalenthydrogenatomscausingsplitting Multiplicity Relativepeakintensities
1 doublet 1:1
2 triplet 1:2:1
3 quartet 1:3:3:1
4 quintet 1:4:6:4:1
5 sextet 1:5:10:10:5:1
6 septet 1:6:15:20:15:6:1

Letusapplythe(n+1)ruletotheanalysisofthespectrumof1,1,2trichloroethane(figure20.32).Thetwohydrogen
atomsoftheCH2Clgrouphaveoneneighbouringhydrogen(n=1),sotheirsignalissplitintoadoublet(1+1=2).
ThesinglehydrogenatomoftheCHCl2grouphasasetoftwoequivalentneighbouringhydrogenatoms(n=2),so
itssignalissplitintoatriplet(2+1=3).

Letusnowconsiderthesplittingpatternin1chloropropane(figure20.33).ThetwohydrogenatomsonC(1)havetwo
neighbouringequivalenthydrogenatomsontheadjacentcarbonatomandsothesignal(3.5)forthesehydrogen
atomsissplitintoatriplet(2+1).Similarly,thesignalduetothethreehydrogenatomsonC(3)(1.1)issplitintoa
triplet.ThetwohydrogenatomsonC(2)areflankedononesidebyasetoftwohydrogenatomsonC(1),andonthe
othersidebyasetofthreehydrogenatomsonC(3).BecausethesetsofhydrogenatomsonC(1)andC(3)arenot
equivalenttoeachother,theycancausethesignalfortheCH2grouponC(2)tobesplitintoacomplexpattern,which
wewillrefertosimplyasamultiplet.IfthemagnitudeofthesplittingbetweenthehydrogenatomsofC(1)andC(2)is
equaltothatbetweenC(2)andC(3),thenwecandescribethesignalasasextet.The(n+1)rulecanbeusedincases
wherethecouplingbetweentheobservedhydrogenatom(s)andadjacentnonequivalenthydrogenatomsisequal.

FIGURE20.331 HNMRspectrumof1chloropropane.

WORKEDEXAMPLE20.14

SplittingPatterns
Predictthenumberofsignalsandthesplittingpatternofeachsignalinthe1HNMRspectrumofeachofthe
followingcompounds.
(a)

(b)

(c)

Analysis

Firstidentifythedifferenttypesofhydrogenatoms.Nowconsiderthenumberofhydrogenatomsonthe
neighbouringcarbonatom.Applyingthe(n+1)rulewillgivethesplittingpattern.

Solution

Thesetsofequivalenthydrogenatomsineachmoleculearecolourcodedbelow.Inmolecule(a),thesignal
fortheredmethylgroupisunsplit(asinglet)becausethegroupistoofar(>3bonds)fromanyother
hydrogenatoms.TheblueCH2grouphasthreeequivalentneighbouringhydrogenatoms(n=3)soit
showsasignalsplitintoaquartet(3+1=4).Thegreenmethylgrouphastwoequivalentneighbouring
hydrogenatoms(n=2)soitssignalissplitintoatriplet.Theintegrationratiosforthesesignalswouldbe3:
2:3.

Molecules(b)and(c)canbeanalysedinthesameway.Thus,molecule(b)showsatripletandaquartetina
3:2ratio(rememberthatthetwoCH2groupsareequivalent,asarethetwoCH3groups).Molecule(c)
showsasinglet,aseptet(6+1=7)andadoubletintheratio3:1:6.
(a)

(b)

(c)

Isouranswerreasonable?

Checkthatyouhaveconsideredonlythehydrogenatomsonneighbouringatoms.

PRACTICEEXERCISE20.13

(a)Thefollowingarepairsofconstitutionalisomers.Predictthenumberof
signalsandthesplittingpatternofeachsignalinthe1HNMRspectrum
ofeachisomer.
i.

ii.
 (b)Determinethemultiplicitiesforeachtypeofhydrogenatomintheesters
fromworkedexample20.7(p.881).Althoughthesecompoundscanbe
distinguishedwithoutconsideringmultiplicity,itisausefulcheckthat
yourinitialanalysisiscorrect.

Splittingpatternsgivevaluableinformationaboutthenumberofhydrogenatomsonneighbouringcarbonatoms.For
example,atripletindicatesthattherearetwoequivalenthydrogenatomsonneighbouringcarbonatomsandaquartet
thattherearethreeequivalentneighbouringhydrogenatoms.

Awordofcaution:Studentsoftenconfuseinformationobtainedfromintegrationwiththatfrommultiplicity.
Integrationvaluesindicatethenumberofhydrogenatomsgivingrisetoasignal.Multiplicityindicatesthenumberof
equivalenthydrogenatomsonadjacentcarbonatoms.Table20.11showssomecommonsplittingpatternsandthe
correspondingstructuralunits.
TABLE20.11 Characteristicsplittingpatternsforcommonorganicgroups
Group Splittingpatterns

ethylgroup

isopropylgroup
 XisdifferentfromY.Itisassumedthatthehydrogenatomsinthegroupsshownarenotcoupledtoother
hydrogenatoms.

13CNMRSpectroscopy

Nucleiof12C,themostabundant(98.89%)naturalisotopeofcarbon,donothaveanuclearspinandsoarenot
detectedbyNMRspectroscopy.Nucleiof13C(naturalabundance1.11%),however,dohavenuclearspinandsoare
detectedbyNMRspectroscopyinthesamemannerashydrogenatomsaredetected.

Inthemostcommonmodeforrecordinga13Cspectrum,aprotondecoupledspectrum,all13Csignalsappearas
singlets.The13CNMRspectrumofcitricacid(figure20.34),acompoundusedtoincreasethesolubilityinwaterof
manypharmaceuticaldrugs,consistsoffoursinglets.Noticethat,asin1HNMR,equivalentcarbonatomsgenerate
onlyonesignal.

FIGURE20.34The13 CNMRspectrumofcitricacid.

Figure20.35isasimplecorrelationchartforrememberingthe13CNMRchemicalshiftsofvariouscarbonatoms.If
youcomparethiswithfigure20.31,acorrelationchartfor1HNMRchemicalshifts,youwillnoticethatsignalsforthe
CatomsfallinapproximatelythesamerelativeregionofthespectrumastheircorrespondingHatomsinthevarious
functionalgroups.Table20.12showsapproximatechemicalshiftsin13CNMRspectroscopy.
 FIGURE20.35Carbonchemicalshiftsforcommonfunctionalgroups.

Noticehowmuchbroadertherangeofchemicalshiftsisfor13CNMRspectroscopythanfor1HNMRspectroscopy.
Whereasmostchemicalshiftsfor1HNMRspectroscopyfallwithinarathernarrowrangeof012ppm,thosefor13C
NMRspectroscopycover0210ppm.Becauseofthisexpandedscale,itisveryunusualtofindanytwononequivalent
carbonatomsinthesamemoleculewithidenticalchemicalshifts.Mostcommonly,eachdifferenttypeofcarbonatom
withinamoleculehasadistinctsignalthatisclearlyresolvedfromallothersignals.Noticefurtherthatthechemical
shiftofcarbonylcarbonatomsisquitedistinctfromthechemicalshiftsofsp 3hybridisedcarbonatomsandothertypes
ofsp 2hybridisedcarbonatoms.Thepresenceorabsenceofacarbonylcarbonatomisquiteeasytorecogniseina13C
NMRspectrum.

Agreatadvantageof13CNMRspectroscopyisthatitisgenerallypossibletocountthenumberofdifferenttypesof
carbonatomsinamolecule.However,becauseoftheparticularmannerinwhich13CNMRspectraareobtained,
integratingsignalareasisoftenunreliable,anditisgenerallynotpossibletodeterminethenumberofcarbonatomsof
eachtypeonthebasisofthesignalareas.

WORKEDEXAMPLE20.15

13CNMRspectra

Predictthenumberofsignalsinthe13CNMRspectrumofeachofthefollowingcompounds.
(a)

(b)

(c)

Analysis

Checkforsymmetry.Ifthereisnosymmetry,thenumberofsignalswillequalthenumberofcarbonatoms.
Ifthereissymmetry,thenumberofsignalswillbelessthanthenumberofcarbonatoms.Countthenumber
ofnonequivalentcarbonatoms.

Solution

Thediagrambelowshowsthenumberofsignalsineachspectrum,alongwiththechemicalshiftofeach,
colourcodedtothecarbonatomresponsibleforthatsignal.Thechemicalshiftsofthecarbonylcarbon
atomsarequitedistinctive(table20.12)andare171.4,208.9,and212.0intheseexamples.
TABLE20.12 13 CNMRchemicalshifts

Typeofcarbon Chemicalshift()(a)
040
 RCH3

RCH2R 1555

R3CH 2060

RCH2I 040
RCH2Br 2565

RCH2Cl 3580

R3COH 4080

R3COR 4080

RC CR 6585

R2C CR2 100150

110160

160180

165180

175185

180210

(a)Valuesareapproximate.Otheratomswithinthemoleculemaycausethesignaltoappearoutside
theseranges.
(a)

(b)

(c)

Isouranswerreasonable?

Haveyouidentifiedeverycarbonatom(thisisparticularlyimportantwhencondensedstructuresorline
structuresareused)?Checkalsothatyouhavenotoverlookedanysymmetry.
 PRACTICEEXERCISE20.14
Explainhowtodistinguishbetweenthemembersofeach
ofthefollowingpairsofconstitutionalisomersonthebasis
ofthenumberofsignalsinthe13CNMRspectrumofeach
isomer.
(a)

(b)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.6InterpretingNMRSpectra
InterpretingNMRspectroscopicdataisaskillthatisbestacquiredthroughpracticeandexposureto
examples.Inthissection,wewillseespecificexamplesofNMRspectraforcharacteristicfunctionalgroups.
Familiarisingyourselfwiththemwillhelpyoutomasterthetechniqueofspectralinterpretation.

Alkanes

Becauseallhydrogenatomsinalkanesareinsimilarchemicalenvironments,1HNMRchemicalshiftsof
theirhydrogenatomsfallwithinanarrowrangeof0.81.7,sosignalsoftenoverlap.Chemicalshiftsfor
alkanecarbonatomsin13CNMRspectroscopyfallwithinthewiderrangeof060.Noticehowitis
relativelyeasytodistinguishallthesignalsinthe13CNMRspectrumof2,2,4trimethylpentane(common
nameisooctane,figure20.36),amajorcomponentinpetrol,comparedwiththesignalsinthe1HNMR
spectrumof2,2,4trimethylpentane(figure20.37).Inthe13CNMRspectrum,wecanseeallfivesignalsin
the1HNMRspectrum,weexpecttoseefoursignalsbut,infact,weseeonlythree.Thereasonisthat
nonequivalenthydrogenatomsoftenhavesimilarchemicalshifts,whichleadtoanoverlapofsignals.Note
that,inthe13CNMRspectrumbelow,thethreecloselyspacedpeaksat77areduetothesolventCDCl3.
Infact,asignalduetothesolventisobservedinall13CNMRspectra,exceptthoseruninD2O.

FIGURE20.3613 CNMRspectrumof2,2,4trimethylpentane,showingallfivesignals.

FIGURE20.371 HNMRspectrumof2,2,4trimethylpentane,showingonlythreesignals.Twosetsofnonequivalent
hydrogenatomsproducesignalsat0.9,givinganintegrationratioof1:2:15forthepeaksat
1.7,1.1and0.9,respectively.

Alkenes

The1HNMRchemicalshiftsofvinylichydrogenatoms(hydrogenatomsonacarbonatomofacarbon
carbondoublebond)arelargerthanthoseofalkanehydrogenatomsandtypicallyfallintotherange4.6
5.7.Figure20.38showsa1HNMRspectrumof1methylcyclohexene.Thesignalfortheonevinylic
hydrogenatomappearsat5.4splitintoatripletbythetwohydrogenatomsoftheneighbouringCH2
groupofthering.

FIGURE20.381HNMRspectrumof1methylcyclohexene.

Thesp 2hybridisedcarbonsofalkenescomeintoresonancein13CNMRspectroscopyintherange100
150(table20.12),whichisconsiderablydownfieldfromresonancesofsp 3hybridisedcarbons.

Alcohols

Thechemicalshiftofahydroxylhydrogenatomina1HNMRspectrumisvariableanddependsonthe
purityofthesample,thesolvent,theconcentrationandthetemperature.Normally,theshiftappearsinthe
range3.04.5,but,dependingonexperimentalconditions,itmayhaveachemicalshiftaslowas0.5.
HydrogenatomsonthecarbonatombearingtheOHgrouparedeshieldedbytheelectronwithdrawing
inductiveeffectoftheoxygenatom,andtheirabsorptionstypicallyappearintherange3.44.0.Figure
20.39showsa1HNMRspectrumof2,2dimethylpropan1ol.Thespectrumconsistsofthreesignals.The
hydroxylhydrogenatomappearsat2.2asaslightlybroadsinglet.Thesignalofthehydrogenatomson
thecarbonatombearingthehydroxylgroupin2,2dimethylpropan1olappearsasasingletat3.3.

FIGURE20.391 HNMRspectrumof2,2dimethylpropan1ol.

SignalsplittingbetweenthehydrogenatomontheOHgroupanditsneighboursontheadjacentCH2
groupisnotseeninthe1HNMRspectrumof2,2dimethylpropan1ol.Thereasonisthattracesofacid,
baseorotherimpuritiesintheNMRsolventorthesamplecatalysethetransferofthehydroxylprotonfrom
theoxygenatomofonealcoholmoleculetothatofanotheralcoholmolecule.
Signalsfromalcoholhydrogenatomstypicallyappearasbroadsinglets,asshowninthe1HNMRspectrum
of3,3dimethylbutan1ol(figure20.40).

FIGURE20.401 HNMRspectrumof3,3dimethylbutan1ol,showingthebroadhydroxylsignalat2.1.

BenzeneanditsDerivatives

Allsixhydrogenatomsofbenzeneareequivalent,andtheirsignalappearsinits1HNMRspectrumasa
sharpsingletat7.3.Hydrogenatomsbondedtoasubstitutedbenzeneringappearintheregion6.58.5.
Fewothertypesofhydrogenatomsgivesignalsinthisregionthus,aromatichydrogenatomsarequite
easilyidentifiablebytheirdistinctivechemicalshifts.

Recallthatvinylichydrogenatomsappearat4.65.7.Hence,aromatichydrogenatomsabsorbradiationof
evenhigherfrequencythanvinylichydrogenatoms.

The1HNMRspectrumoftoluene(figure20.41)showsasingletat2.3forthethreehydrogenatomsofthe
methylgroupandacloselyspacedmultipletat7.3forthefivehydrogenatomsofthearomaticring.The
hydrogenatomsofanaromaticringcanproducequitecomplexsignalsasseeninthespectrumofethyl
benzoate(figure20.42)withamultipletat8.1(integratingfortwohydrogenatoms)andamultipletat7.5
(integratingforthreehydrogenatoms).Thespectrumalsoshowsthetypicaltriplet(1.4)andquartet(4.4)
pairofsignalscharacteristicofanethoxygroup.
 FIGURE20.411 HNMRspectrumoftoluene.

FIGURE20.421 HNMRspectrumofethylbenzoate.

In13CNMRspectroscopy,carbonatomsofaromaticringsappearintherange110160.Benzene,for
example,showsasinglesignalat128.Because13Csignalsforalkenecarbonatomsappearinthesame
range,itisgenerallynotpossibletoestablishthepresenceofanaromaticringby13CNMRspectroscopy
alone.However,13CNMRspectroscopyisparticularlyusefulinestablishingsubstitutionpatternsof
aromaticrings.The13CNMRspectrumof2chlorotoluene(figure20.43)showssixsignalsinthearomatic
regionthecompound'smoresymmetricisomer4chlorotoluene(figure20.44)showsonlyfoursignalsin
thearomaticregion.Thus,todistinguishbetweentheseconstitutionalisomers,justcountthesignals.Notice
inthe13CNMRspectrabelowthatthesignalintensitiesarenotproportionaltothenumberofequivalent
carbonatomsgivingrisetothatsignal,sointegratingsignalareasisoftenunreliable.Thisisaconsequence
ofthewayinwhich13Cnucleireturntotheirlowerenergystates.Typically,quaternary(4)carbonatoms
(thosenotbondedtoahydrogenatom)givesignalsoflowintensity.

FIGURE20.4313 CNMRspectrumof2chlorotoluene.
 FIGURE20.4413 CNMRspectrumof4chlorotoluene.

Amines
Thechemicalshiftsofaminehydrogenatoms,likethoseofhydroxylhydrogenatoms,arevariableandmay
befoundintheregion0.55.0,dependingonthesolvent,theconcentrationandthetemperature.
Furthermore,signalsplittingisnotgenerallyobservedbetweenaminehydrogenatomsandhydrogenatoms
onanadjacentcarbonatomduetorapidintermolecularexchangeoftheNHhydrogenatoms.

Thus,aminehydrogenatomsgenerallyappearassinglets.TheNH2hydrogenatomsinbenzylamine,
C6H5CH2NH2,forexample,appearasasingletat1.4(figure20.45).

FIGURE20.451 HNMRspectrumofbenzylamine.
AldehydesandKetones
1HNMRspectroscopyisanimportanttoolforidentifyingaldehydesandfordistinguishingbetween
aldehydesandothercarbonylcontainingcompounds.Justasthesignalofavinylichydrogenatomhasa
higherchemicalshift(relativetooneonansp 3hybridisedcarbonatom),thesignalofanaldehydehydrogen
atomalsohasahigherchemicalshift(relativetooneonansp 3hybridisedcarbonatom),typicallyto9.5
10.1.Signalsplittingbetweenthishydrogenatomandthoseontheadjacentcarbonatomisslight
consequently,thealdehydehydrogensignaloftenappearsasacloselyspaceddoubletortriplet.Inthe
spectrumofbutanal,forexample,thetripletsignalforthealdehydehydrogenatomat9.8issoclosely
spacedthatitlooksalmostlikeasinglet(figure20.46).

FIGURE20.461 HNMRspectrumofbutanal.

Justasthesignalforanaldehydehydrogenatomisonlyweaklysplitbytheadjacentnonequivalent
hydrogenatoms,thehydrogenatomsareweaklysplitbythealdehydehydrogenatom.Hydrogenatoms
onancarbonatomofanaldehydeorketonetypicallyappeararound2.12.6.Thecarbonylcarbon
atomsofaldehydesandketonesarereadilyidentifiablein13CNMRspectroscopybythepositionoftheir
signalbetween180and210.

CarboxylicAcids
Thehydrogenatomofthecarboxylgroupgivesasignalintherange1012.Thechemicalshiftofa
carboxylhydrogenatomissolargeevenlargerthanthechemicalshiftofanaldehydehydrogenatom(
9.510.1)thatitservestodistinguishcarboxylhydrogenatomsfrommostothertypesofhydrogenatoms.
Thesignalofthecarboxylhydrogenof2methylpropanoicacid,labelledconthe1HNMRspectrumin
figure20.47,hasbeenoffsetby2.4.(Add2.4tothepositionatwhichthesignalappearsonthespectrum.)
Thechemicalshiftofthishydrogenis12.0.
 FIGURE20.471 HNMRspectrumof2methylpropanoicacid(isobutyricacid).

Esters
Hydrogenatomsonthecarbonatomofthecarbonylgroupofanesterareslightlydeshieldedandgive
signalsat2.12.6.Hydrogenatomsonthecarbonatombondedtotheesteroxygenatomaremore
stronglydeshieldedandgivesignalsat3.74.7.Itisthuspossibletodistinguishbetweenethylacetateand
itsconstitutionalisomer,methylpropanoate,bythechemicalshiftsofeitherthesinglet(s)CH3absorption
(compare2.0with3.7)orthequartet(q)CH2absorption(compare4.1with2.3):

SolvingNMRProblems
Oneofthefirststepsindeterminingthemolecularstructureofacompoundistoestablishthecompound's
molecularformula.Inthepast,thiswasmostcommonlydonebyelementalanalysis,asdescribedinchapter
3.Morecommonlytoday,wedeterminemolecularmassandmolecularformulabymassspectrometry.In
theexamplesthatfollow,weassumethatthemolecularformulaofanyunknowncompoundhasalready
beendeterminedandweproceedfromthere,usingspectralanalysistodetermineastructuralformula.

Thefollowingstepsmayprovehelpfulasasystematicapproachtosolving1HNMRspectralproblems:
Step1:Molecularformulaandindexofhydrogendeficiency.Examinethemolecularformula,calculate
theindexofhydrogendeficiency(section20.1),anddeduceanyinformationyoucanaboutthepresence
orabsenceofringsorbonds.
Step2:Numberofsignals.Countthenumberofsignalstodeterminetheminimumnumberofsetsof
equivalenthydrogenatomsinthecompound.
Step3:Integration.Usesignalintegrationandthemolecularformulatodeterminethenumberof
hydrogenatomsineachset.
Step4:Patternofchemicalshifts.ExaminetheNMRspectrumforsignalscharacteristicofthemost
commontypesofequivalenthydrogenatoms.(Seethegeneralrulesofthumbfor1HNMRchemical
shiftsinsection20.5,p.891.)Keepinmindthattherangesarebroadandthathydrogenatomsofeach
typemaybeshiftedoutsidetherange,dependingondetailsofthemolecularstructureinquestion.
 Step5:Splittingpattern.Examinesplittingpatternsforinformationaboutthenumberofnonequivalent
neighbouringhydrogenatoms.
Step6:Structuralformula.Writeastructuralformulaconsistentwiththeinformationlearnedinsteps1
5.

Spectralproblem1:ThecompoundisacolourlessliquidwithmolecularformulaC5H10O.

Analysisofspectralproblem1:
Step1:Molecularformulaandindexofhydrogendeficiency.ThereferencecompoundisC5H12Oso
theindexofhydrogendeficiencyis1andthemoleculecontainseitheroneringoronebond.
Step2:Numberofsignals.Therearetwosignals(atripletandaquartet)sotherearetwosetsof
equivalenthydrogenatoms.
Step3:Integration.Bysignalintegration,wecalculatethatthenumberofhydrogenatomsgivingriseto
eachsignalisintheratio3:2.Becausethereare10hydrogenatoms,weconcludethatthesignal
assignmentsare1.1(6H)and2.4(4H).
Step4:Patternofchemicalshifts.Thesignalat1.1isinthealkylregionand,basedonitschemical
shift,mostprobablyrepresentsamethylgroup(twomethylgroupsbasedonintegrationdataonthe
previouspage).Nosignaloccursat4.6to5.7,sotherearenovinylichydrogenatoms.(Ifthereisa
carboncarbondoublebondinthemolecule,therearenohydrogenatomsonitthatis,itis
tetrasubstituted.)Thesignalat2.4isintheregionforhydrogenatomsonthecarbonatomofthe
carbonylgroup(2.12.6).
Step5:Splittingpattern.Themethylsignalat1.1issplitintoatriplet(t),soitmusthavetwo
equivalentneighbouringhydrogenatoms,indicatingCH2CH3.Thesignalat2.4issplitintoaquartet
(q),soitmusthavethreeequivalentneighbouringhydrogenatoms,whichisalsoconsistentwith
CH2CH3.Consequently,anethylgroupaccountsforthesetwosignals.Noothersignalsoccurinthe
spectrumtherefore,therearenoothertypesofhydrogenatomsinthemolecule.
Step6:Structuralformula.Sofarwehavelearnedthattherearetwosignalswithanintegrationof6H
and4H(steps2and3)andthatthesebelongtotwoequivalentethylgroups(steps4and5).This
accountsforallthehydrogenatomsintheformulaandfourofthecarbonatomsthisleavesonecarbon
atomandoneoxygenatom.Step1gaveIHD=1,sotheremainingcarbonandoxygenatomsmustbea
carbonylgroup.Puttingthisinformationtogetherwearriveatthefollowingstructuralformula.Notethat
thechemicalshiftofthemethylenegroup(CH2)at2.4isconsistentwithanalkylgroupadjacentto
acarbonylgroup.
Spectralproblem2:ThecompoundisacolourlessliquidwithmolecularformulaC7H14O.

Analysisofspectralproblem2:
Step1:Molecularformulaandindexofhydrogendeficiency.Theindexofhydrogendeficiencyis1,so
thecompoundcontainsoneringoronebond.
Step1:Numberofsignals.Therearethreesignalsandthereforethreesetsofequivalenthydrogen
atoms.
Step1:Integration.Bysignalintegration,wecalculatethatthenumberofhydrogenatomsgivingriseto
eachsignalisintheratio2:3:9,readingfromlefttoright.
Step1:Patternofchemicalshifts.Thesingletat1.0ischaracteristicofamethylgroupadjacenttoan
sp 3hybridisedcarbonatom(threemethylgroupsbasedontheintegration).Thesingletsat2.1and2.3
arecharacteristicofalkylgroupsadjacenttoacarbonylgroup.
Step1:Splittingpattern.Allsignalsaresinglets(s),whichmeansthatnoneofthehydrogenatomsare
withinthreebondsofeachother.
Step1:Structuralformula.Summarisingthedataabove,wehavethreeequivalentmethylgroups(
1.0):anothermethylgroup(2.1)adjacenttoacarbonylgroup,andamethylenegroup(2.3)also
adjacenttoacarbonylgroup.WealsohaveacarbonylgroupasdeducedfromtheIHD,molecular
formulaandthechemicalshiftofthemethylandmethylenegroups.Thisaccountsforsixcarbonatoms,
14hydrogenatomsandoneoxygenatom.Bycomparisonwiththemolecularformula,weknowthatwe
mustalsohaveacarbonatomnotbondedtoanyhydrogenatoms.Now,toputthisinformationtogether,
let'sstartbyconsideringthecarbonylgroupandthetwoattachedgroups,givingusCH2C(O)CH3.The
onlypossiblearrangementfortheremainingquaternarycarbonatomandthreemethylgroupsis
C(CH3)3.Therefore,wegetthecompound4,4dimethylpentan2one.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
20.7OtherToolsforDeterminingStructure
Thischapterhasfocusedonthetoolsmostcommonlyusedbychemists.However,thereareotheruseful
techniquesincludingUV/visiblespectroscopy,Xraycrystallographyandelectronspinresonance.

UV/visiblespectroscopyisusedinthestudyofcompoundsthatabsorblightintheultravioletvisible
regionofthespectrum(=200800nmseesection4.2,p.112).Thetechniqueisapplicabletoorganic
compoundswithconjugatedbonds(asequenceoffourormoresp 2hybridisedatoms)andtocoordination
compoundsoftransitionmetalswithpartiallyfilleddorbitals.UV/visiblespectroscopyisausefultoolfor
studyingthecoordinationchemistryofmetals,aschangesincoordinationgeometryandliganddonoratom
canhavemarkedeffectsonthespectrum.ThecoloursandthetheoryofUV/visiblespectroscopyof
coordinationcompoundshavebeendescribedindetailinsection13.4.Asageneralrule,fororganic
substances,thewavelengthofmaximumabsorption(max)increaseswithanincreaseintheextentof
conjugation(seetable20.13forsomeexamples).
TABLE20.13 Wavelengthofmaximumultravioletabsorptionofselectedconjugatedmolecules
Molecule Structure max(nm)
2methylbuta1,3diene 220

but3en2one 219

octa2,4,6triene 263
benzene 254

Thespectraobtainedhavefewabsorptionbandsandgenerallylackfinedetail.Consequentlythistechnique
isnowrarelyusedtodeterminethestructureoforganiccompounds.However,UV/visiblespectroscopyis
usedwidelyindetectorsfortheanalysisofliquidandgassamplesasitcandetectverylowconcentrations
ofanalyteandprovidesquantitativedata.ThequantificationispossiblebyapplyingtheBeerLambertlaw
(commonlyknownasBeer'slaw),whichrelatestheabsorbancetotheconcentrationoftheanalyteandthe
samplecellpathlength:

where isthemolarabsorptivity(Lmol1cm1),bisthepathlengthofthecell(cm),andcisthe
concentrationofthesample(molL1).

WORKEDEXAMPLE20.16

ApplicationoftheBeerLambertLaw

Themolarabsorptivityofvanillinatawavelengthof231nmis14200Lmol1cm1.Asample
ofvanillinwasfoundtohaveanabsorbanceof0.764Lmol1cm1atawavelengthof231nm
whenpassingthroughacellwithapathlengthof1.00cm.Whatistheconcentrationofvanillinin
thissample?
 Analysisandsolution

Beforewestart,itisgoodtocheckthedatayouareprovidedwithandwhetheritisallrequiredto
solvetheproblem.NotethatthewavelengthoflightisnotpartoftheBeerLambertlaw,sothis
isnotrequiredtodeterminetheconcentration.Itisprovidedbecausethevalueofthemolar
absorptivityisdependentonthewavelengthoflightabsorbed.Astheconcentrationisrequired,
theBeerLambertlawcanberewrittenintermsofconcentration:

Nowsubstitutingintotheequationweget:

Isyouranswerreasonable?

Asimplewaytocheckyouransweristodeterminetheabsorbanceusingthevalueofthe
concentrationyouhavedetermined.

PRACTICEEXERCISE20.15
Colchicineisanaturalproductusedinthe
treatmentofgout.Ithasamolarabsorptivity
of29200Lmol1cm1atawavelengthof
231nm.Whatistheconcentrationofa
colchicinesamplethathasanabsorbanceof
0.845Lmol1cm1atawavelengthof231
nmandcellpathlengthof5.00cm?

AnimportantapplicationofUVabsorbingcompoundsisinsunscreenstoprotectagainstskincancer(figure
20.48).Octylmethoxycinnamateand4methylbenzylidinecamphor,whichbothabsorbUVBradiation(290
320nm),aretheUVabsorbersmostcommonlyusedinsunscreens.
 FIGURE20.48UVabsorbingcompoundsareusedinsunscreens.

XraycrystallographyisthestudyofcrystalstructuresthroughXraydiffractiontechniquesandisa
powerfulwayofobtainingdetailedinformationonstructureandbondingwithinacrystal.Whenabeamof
Xrayspassesthroughacrystal,thebeamisdiffractedinamannerthatisdependentonthesizeandposition
oftheatomswithinthecrystal(seechapter7,p.278).Analysisofthediffractionpatternallowsthe
determinationofthethreedimensionalstructureofthecompound,includingbondlengthsandbondangles.
Eachyear,Xraycrystallographyisusedtodeterminethestructureofthousandsofinorganic,organic,
organometallicandbiologicalcompounds.Itisthemostimportanttechniqueavailableforthedetermination
ofthe3Dstructureofproteinsandotherlargebiomolecules.However,thistechniqueislimitedto
crystallinesamplesofsuitablequalityandsize.Growingappropriatecrystals,particularlyofbiomolecules,
canbeasignificantchallengeinitself.

Electronspinresonance(ESR)alsoknownaselectronparamagneticresonance(EPR)isatypeof
magneticresonancethatisusefulforthestudyoffreeradicals,paramagneticspecies(seesection13.1,p.
544)andothersubstancescontainingunpairedelectrons.Itisarguablythemostimportanttechniquefor
studyingstructureinfreeradicalsandplaysanimportantpartinunderstandingreactionmechanisms.

chemistryResearch

LookingforMoleculesinSpace

TimSchmidtandScottKable,UniversityofSydney

InthelaserspectroscopylaboratoriesattheUniversityofSydney,researchersTimSchmidtand
ScottKablearelookingformoleculesinspace.Becauseinterstellarmoleculesaresoveryfaraway,
theonlywaytoidentifythemisbyanalysingthelightthattheyemitandabsorb.

TimandScottcollaboratewithRobSharpfromtheAngloAustralianObservatorytoacquire
spectraofastrophysicalobjectssuchasdustcloudsandnebulae(figure20.49).Byusinga
backgroundstarasalightsource,theyareabletomeasureabsorptionspectraofdiffuseinterstellar
cloudsusingaspectrometerattachedtothetelescope.Mostoftheabsorptionspectraobservedin
thevisiblerangeareduetounidentifiedmolecules.Theresearchershopethat,byrecreatingthe
samespectrainalaboratorysetting,theycanidentifythesemolecules,whichareabsorbinglight
manylightyearsaway.
 FIGURE20.49TheRedRectangleisasourceofunidentifiedmolecularemissionbands.Someofthese
bandsareclosetotheunidentifieddiffuseinterstellarbands.TimSchmidtandRob
SharparestudyingthecarbonclusterC2 intheRedRectangletolearnmoreaboutits
photophysicalenvironment.

ThecarbonclustersC2andC3arereadilyobservedininterstellarspectra.Byrecreatinginterstellar
conditionsoflowtemperatureandhighvacuuminthelaboratory,TimandScottcanmakethese
interstellarmoleculesinahydrocarbondischargeandstudythemusingatechniqueknownas
laserinducedfluorescence.Inthistechnique,thesampleisirradiatedwithlaserlightwhichis
variedoverarangeofwavelengths.Fluorescenceisobservedatthewavelengthwherethesample
absorbslight.Absorptionspectraaredifficulttoacquireforthesemolecules,butsuchfluorescence
givessimilarinformationasafunctionoflaserwavelength.Usingspectroscopictechniques
developedbyastronomerssuchasRobSharp,theSydneyresearcherscanalsoanalysetheemitted
light.Theresultisatwodimensionalfluorescencemap(figure20.50).BylookingbetweentheC2
andC3features,theyhavebeenabletolocatespectraofhithertounobservedspecies.Onenew
discoveryofgreatchemicalinterestwasthephenylpropargylradical,C9H9.Thisisthemost
conspicuouslyfluorescentspeciesinanelectricaldischargecontainingbenzene,hintingatits
importanceinthechemistryofplanetaryatmospheres,combustionandtheinterstellarmedium.
 FIGURE20.50AtwodimensionalfluorescencespectrumofabenzenedischargeshowingC2 ,C3 and
therecentlyidentifiedphenylpropargylradical.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
ToolsforDeterminingStructure
Theindexofhydrogendeficiencyisthesumofthenumberofringsandbondsinamolecule.Itcan
bedeterminedbycomparingthenumberofhydrogenatomsinthemolecularformulaofacompoundof
unknownstructurewiththenumberofhydrogenatomsinareferencecompoundwiththesamenumber
ofcarbonatomsandwithnoringsorbonds.

MassSpectrometry
Massspectrometryisatechniquethatallowsustodeterminethemassofmoleculesandfragmentsof
molecules.Inmassspectrometry,asampleisionisedbybombardmentwithastreamofhighenergy
electronstoproduceamolecularion(aniongeneratedbyremovalofanelectronfromthemolecule)
andfragmentions.Themolecularionisaradicalcation,becauseithasoneunpairedelectronandis
positivelycharged,andhasthesamemassastheparentmolecule.Highresolutionmassspectrometryis
aprocessthatmeasuresthemasstochargeratioofions(includingthemolecularion)withahighdegree
ofprecision(usuallytofourdecimalplaces),allowingthedeterminationofamolecularformula.
Relativeabundancesofisotopesmaybeusedtoidentifyelementspresentinamolecule.

InfraredSpectroscopy
Electromagneticradiationcanbedescribedintermsofitswavelength()andfrequency().Frequency
isreportedins1.Analternativewaytodescribeelectromagneticradiationisintermsofitsenergy,
whereE=h.Molecularspectroscopyistheexperimentalprocessofmeasuringthefrequenciesof
radiationthatareabsorbedoremittedbyasubstanceandcorrelatingthesepatternswithdetailsof
molecularstructure.Interactionsofmoleculeswithinfraredradiationexcitecovalentbondstohigher
vibrationalenergylevels.

Thevibrationalinfraredspectrumextendsfrom4000to400cm1.Radiationinthisregionisreferredto
byitswavenumber inreciprocalcentimetres(cm1).Tobeinfraredactive,abondmustbepolarthe
morepolaritis,thestrongerisitsabsorptionofIRradiation.Thereare3n6fundamentalvibrationsfor
anonlinearmoleculecontainingnatoms.Thesimplestvibrationsthatgiverisetotheabsorptionof
infraredradiationarestretchingandbendingvibrations.Stretchingmaybesymmetricalorasymmetrical.

InterpretingInfraredSpectra
Functionalgroupswithinmoleculeshavecharacteristicvibrationalfrequencies,andtheseareoftenlisted
oncorrelationtables.Theintensityofasignalisreferredtoasstrong(s),medium(m)orweak(w).
Stretchingvibrationsformostfunctionalgroupsappearintheregionfrom3650to1000cm1.The
regionfrom1000to450cm1iscalledthefingerprintregion.

NuclearMagneticResonanceSpectroscopy
Theinteractionofmoleculeswithradiofrequencyradiationgivesusinformationaboutnuclearspin
energylevels.Nucleiof1Hand13C,isotopesofthetwoelementsmostcommontoorganiccompounds,
haveaspinandbehaveliketinybarmagnets.Whenplacedinapowerfulmagneticfield,thenuclear
spinsoftheseelementsbecomealignedeitherwiththeappliedfieldoragainstit.Nuclearspinsaligned
withtheappliedfieldareinthelowerenergystatethosealignedagainsttheappliedfieldareinthe
higherenergystate.Resonanceistheabsorptionofelectromagneticradiationbyanucleusandthe
resultingflipofitsnuclearspinfromalowerenergyspinstatetoahigherenergyspinstate.AnNMR
spectrometerrecordssucharesonanceasasignal.

InterpretingNMRSpectra
Ina1HNMRspectrum,aresonancesignalisreportedbyhowfaritisshiftedfromtheresonancesignal
ofthe12equivalenthydrogenatomsintetramethylsilane(TMS).Aresonancesignalina13CNMR
spectrumisreportedbyhowfaritisshiftedfromtheresonancesignalofthefourequivalentcarbon
atomsinTMS.Achemicalshift()isthefrequencyshiftfromTMS,dividedbytheoperatingfrequency
ofthespectrometer.

Equivalenthydrogenatomswithinamoleculehaveidenticalchemicalshifts.Theareaofa1HNMR
signalisproportionaltothenumberofequivalenthydrogenatomsgivingrisetothatsignal.Insignal
splitting,the1HNMRsignalfromonehydrogenatomorsetofequivalenthydrogenatomsissplitby
theinfluenceofhydrogenatomsonadjacentcarbonatomsthatareequivalenttoeachotherbutnotto
theatomsgivingrisetothesignal.Accordingtothe(n+1)rule,ifahydrogenatomhasnhydrogen
atomsthatarenotequivalenttoit,butareequivalenttoeachother,onadjacentcarbonatom(s),its1H
NMRsignalissplitinto(n+1)peaks.Complexsplittingpatternsoccurwhenahydrogenatomis
flankedbytwoormoresetsofhydrogenatomsandthosesetsarenonequivalent.Splittingpatternsare
commonlyreferredtoassinglets(s),doublets(d),triplets(t),quartets(q),quintetsandmultiplets(m).

In13CNMRspectra,allthe13Csignalsappearassinglets.Thenumberofsingletsalmostalways
correspondstothenumberofnonequivalentcarbonatomswithinamolecule.Theareaofa13CNMR
signalisnotproportionaltothenumberofequivalenttcarbonatomsgivingrisetothatsignal.

OtherToolsforDeterminingStructure
UV/visiblespectroscopyisusedinthestudyofcompoundsthatabsorblightintheultravioletvisible
regionofthespectrum(=200800nm).Xraycrystallographyisthestudyofcrystalstructures
throughXraydiffractiontechniques.Electronspinresonance(ESR),alsoknownaselectron
paramagneticresonance(EPR),isatypeofmagneticresonancethatisusefulforthestudyoffree
radicals,paramagneticspeciesandothersubstancescontainingunpairedelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Indexofhydrogendeficiency(section20.1)
Thesumofthenumberofringsandbondsinamolecule.

(n+1)rule(section20.5)
AccordingtothisrulefordeterminingsplittingpatternsinNMRspectroscopy,ifahydrogenatomhasn
hydrogenatomsthatarenotequivalenttoit,butequivalenttoeachother,onthesameoradjacent
atom(s),thenthe1HNMRsignalofthehydrogenatomissplitinto(n+1)peaks.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
ToolsforDeterminingStructure
20.1Completethefollowingtable.

Classof Molecular Indexofhydrogen Reasonforhydrogen

compound formula deficiency deficiency
alkane CnH2n+2 0 (referencehydrocarbon)
alkene CnH2n 1 onebond
alkyne
alkadiene
cycloalkane
cycloalkene

20.2Calculatetheindexofhydrogendeficiencyofeachofthefollowingcompounds.
(a)aspirin,C9H8O4
(b)urea,CH4N2O
(c)ascorbicacid(vitaminC),C6H8O6
(d)cholesterol,C27H46O
(e)pyridine,C5H5N
(f) trichloroaceticacid,C2HCl3O
MassSpectrometry
20.3Whatinformationcanwegainfrommassspectrometry?
20.4Whatisamolecularion?
20.5Whatdoesm/zstandfor?
20.6Inthemassspectrumofdecane,thepeakduetothemolecularion(M)+isatm/z=142.This,however,isnot
thepeakwiththehighestm/zvalue.Thereisapeakatm/z=143withanintensityofapproximately10%thatof
the(M)+peak.Thispeakisreferredtoasthe(M+1)+peak.Whatisthesourceofthispeak?
20.7Inthemassspectrumofchlorobenzene,thereisapeakatm/z=112(M)+andanotheratm/z=114(M+2)+.
Explaintheoccurrenceofthesetwopeaks.
20.8Youareprovidedwiththemassspectrumofacompoundthatcontainsoneofthefollowinghalogens:fluorine,
chlorineorbromine.Usingyourknowledgeofisotopes,explainhowyoucouldidentifythehalogenpresentin
thecompound.
20.9Whatmassspectrometrytechniquecanbeusedtodeterminethemolecularformulaofacompound?
20.10Determinetheaccuratemassofeachofthefollowingcompounds.
(a)hexan3ol
(b)4aminobutanal
(c)bromobenzene
(d)chloroaceticacid
(e)phenol

(f) bromobenzene
(g)cholesterol,C27H46O
20.11Matcheachofthefollowingcompoundswiththeappropriatespectrum.
(a)
(b)

(c)

(d)
InfraredSpectroscopy
20.12Whatinformationcanwegainfrominfraredspectroscopy?
20.13Whichregionoftheelectromagneticspectrum,IRorUV,containsphotonsofhigherenergy?
20.14Whichregionoftheelectromagneticspectrum,radioorvisible,ischaracterisedbywavesofshorter
wavelength?
20.15Arrangethefollowingregionsoftheelectromagneticspectruminorderofdecreasingwavelength:
microwaves,visiblelight,ultravioletlight,infraredradiation,Xrays.
20.16Whichhasalowercharacteristicstretchingfrequency,aCCoraCObond?Explainbriefly.
20.17Whichhasalowercharacteristicstretchingfrequency,aC ObondoraCObond?Explainbriefly.
20.18HowcouldIRspectroscopybeusedtodistinguishbetweenthecompounds(CH3)3NandCH3NHCH2CH3?
20.19PredictthepositionoftheC Ostretchingabsorptioninacetateion,CH3CO2,relativetothatinaceticacid,
CH3CO2H.
InterpretingInfraredSpectra
20.20ThefollowingistheIRspectrumofLtryptophan,anaturallyoccurringaminoacidthatisabundantinfoods
suchasturkey.
 Formanyyears,theLtryptophaninturkeywasbelievedtomakepeopledrowsyafterChristmasdinner.
ScientistsnowknowthatconsumingLtryptophanmakesyoudrowsyonlyifthecompoundistakenonan
emptystomach.Therefore,itisunlikelythatyourChristmasturkeyisthecauseofdrowsiness.NoticethatL
tryptophancontainsonestereocentre.Itsenantiomer,Dtryptophan,doesnotoccurinnature,butcanbe
synthesisedinthelaboratory.WhatwouldtheIRspectrumofDtryptophanlooklike?
20.21ThesexattractantofthecodlingmothhasthemolecularformulaC13H24O.ItgivesanIRspectrumwitha
broadsignalbetween3200and3600cm1andtwosignalsbetween1600and1700cm1.
(a)Determinetheindexofhydrogendeficiencyforthiscompound.
(b)Whatfunctionalgroupsarepresentinthiscompound?
NuclearMagneticResonanceSpectroscopy
20.22WhatisusedasthereferenceinNMRspectroscopyitssignalisassigned=0in1Hand13CNMR
spectroscopy?
20.23WhatformofelectromagneticradiationisusedinNMRspectroscopy?
20.24Predictthenumberofsignalsexpected,theirsplittingandtheirrelativeareasinthe1HNMRspectrumof
1,2dichloroethane,ClCH2CH2Cl.
20.25Howmanydistinctcarbonsignalsareexpectedinthe13CNMRspectrumof5methylhexan3ol?
20.26Determinethenumberofsignalsyouwouldexpecttoseeinthe1HNMRspectrumofeachofthefollowing
compounds.
a

g
 h

20.27Determinethenumberofsignalsyouwouldexpecttoseeinthe13CNMRspectrumofeachofthe
compoundsinquestion20.26.
InterpretingNMRSpectra
20.28Thefollowingarestructuralformulaefortheconstitutionalisomersofdimethylbenzene(oxylene,pxylene
andmxylene)andthreesetsof13CNMRspectra.Assigneachconstitutionalisomertoitscorrectspectrum.

(a)

(b)

(c)
OtherToolsforDeterminingStructure
20.29Whatisthemostimportantanalyticaltechniquefordeterminingthethreedimensionalstructureofproteins?
20.30WhatstructuralfeatureisrequiredfororganicmoleculestoabsorbUVlight?
20.31Determinethemolarabsorptivityofacompoundthathasanabsorbanceof0.845Lmol1cm1(pathlength
=2cm)forasolutionwithaconcentrationof5.610 5m.
20.32Codeinephosphatehasamolarabsorptivityof1570Lmol1cm1inwaterat284nm.Determinethe
concentrationofasolutionofcodeinephosphatethathasanabsorbanceof0.82.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
20.33Themassspectrumbelowisthatofanunbranchedalkane.Whichalkaneproducedthisspectrum?

20.34Themassspectrumbelowisthatofanoncyclicalkene.Whatisthemolecularformulaforthealkenethatproduced
thisspectrum?

20.35CompoundA,withthemolecularformulaC6H10,reactswithH2/NitogivecompoundB,withthemolecularformula
C6H12.TheIRspectrumofcompoundAisprovided.FromthisinformationaboutcompoundA,determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundA
(c)thestructuralfeature(s)thatwouldaccountfortheindexofhydrogendeficiencyofcompoundA.

20.36ThefollowingareinfraredspectraofcompoundsCandD.Onespectrumisofhexan1ol,theotherofnonane.

Assigneachcompoundtoitscorrectspectrum.
20.37CompoundE,withthemolecularformulaC6H12,reactswithH2/NitogivecompoundF,withthemolecularformula
C6H14.TheIRspectrumofcompoundEisprovided.FromthisinformationaboutcompoundE,determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundE
(c)thestructuralfeature(s)thatwouldaccountfortheindexofhydrogendeficiencyofcompoundE.

20.38Theconstitutionalisomers2methylbutan1olandtertbutylmethyletherhavethemolecularformulaC5H12O.
Assigneachcompoundtoitscorrectinfraredspectrum,GorH.
20.39ExaminethefollowingIRspectrumandthemolecularformulaofcompoundI,C9H12O,anddetermine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundI
(c)whichstructuralfeaturewouldaccountforitsindexofhydrogendeficiency
(d)whichoxygencontainingfunctionalgroupcompoundIcontains.

20.40ExaminethefollowingIRspectrumandthemolecularformulaofcompoundJ,C5H13N.Determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundJ
(c)thenitrogencontainingfunctionalgroup(s)compoundJmightcontain.

20.41ExaminethefollowingIRspectrumandthemolecularformulaofcompoundK,C6H12O.Determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundK
(c)whichstructuralfeatureswouldaccountforitsindexofhydrogendeficiency.
20.42ExaminethefollowingIRspectrumandthemolecularformulaofcompoundL,C6H12O2.Determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundL
(c)theoxygencontainingfunctionalgroup(s)compoundLmightcontain.

20.43ExaminethefollowingIRspectrumandthemolecularformulaofcompoundM,C3H7NO.Determine:
(a)itsindexofhydrogendeficiency
(b)thenumberofringsorbonds(orboth)incompoundM
(c)theoxygenandnitrogencontainingfunctionalgroup(s)incompoundM.

20.44ShowhowIRspectroscopycanbeusedtodistinguishbetweenthefollowingcompounds.
(a)butan1olanddiethylether
(b)butanoicacidandbutan1ol
(c)butanoicacidandbutanone
(d)butanalandbut1ene
(e)butanoneandbutan2ol
(f) butaneand(Z)but2ene
20.45Thefollowingareaninfraredspectrumandastructuralformulaformethylsalicylate,thefragrantcomponentofoil
ofwintergreen.Onthisspectrum,locatetheabsorptionpeak(s)dueto:
(a)OHstretchingofthehydrogenbondedOHgroup(verybroadandofmediumintensity)
(b)CHstretchingofthearomaticring(sharpandofweakintensity)
(c)C Ostretchingoftheestergroup(moderatelysharpandofstrongintensity)
(d)C Cstretchingofthearomaticring(sharpandofmediumintensity).
20.46Foreachofthefollowingpairsofcompounds,listonemajorfeaturethatappearsintheIRspectrumofone
compoundbutnottheother.Inyouranswer,statewhattypeofbondvibrationisresponsibleforthespectralfeature
youlist,andgiveitsapproximatepositionintheIRspectrum.
(a)

(b)

(c)

(d)

20.47Thefollowingisa1HNMRspectrumforcompoundA,withthemolecularformulaC H .CompoundAdecolourises
7 14
asolutionofbromineindichloromethane,CH2Cl2.ProposeastructuralformulaforcompoundA.

20.48Thefollowingisa1HNMRspectrumforcompoundB,withthemolecularformulaC H .CompoundBdecolourises
8 16
asolutionofBr2inCH2Cl2.ProposeastructuralformulaforcompoundB.

20.49Thefollowingarethe1HNMRspectraofcompoundsCandD,bothwiththemolecularformulaC H Cl.Each
4 7
compounddecolourisesasolutionofBr2inCH2Cl2.ProposestructuralformulaeforcompoundsCandD.
 compounddecolourisesasolutionofBr2inCH2Cl2.ProposestructuralformulaeforcompoundsCandD.

20.50ThefollowingarethestructuralformulaeofthreealcoholswiththemolecularformulaC H Oandthreesetsof13C
7 16
NMRspectraldata.Assigneachconstitutionalisomertoitscorrectspectraldata.
(a)CH3CH2CH2CH2CH2CH2CH2OH
(b)

(c)

Spectrum1 Spectrum2 Spectrum3

=74.7 =71.0 =62.9
30.5 43.7 32.8
7.7 29.2 31.9
26.6 29.1
23.3 25.8
14.1 22.6
14.1

20.51AlcoholE,withthemolecularformulaC6H14O,undergoesacidcatalyseddehydrationwhenitiswarmedwith
phosphoricacid,givingcompoundF,withthemolecularformulaC6H12,asthemajorproduct.A1HNMRspectrum

ofcompoundEshowspeaksat0.9(t,6H),1.1(s,3H),1.4(s,1H)and1.5(q,4H).The13CNMRspectrumof
compoundEshowspeaksat73.0,33.7,25.9and8.2.ProposestructuralformulaeforcompoundsEandF.
 compoundEshowspeaksat73.0,33.7,25.9and8.2.ProposestructuralformulaeforcompoundsEandF.
20.52CompoundG,C H O,doesnotreactwithsodiummetalanddoesnotdischargethecolourofBr inCCl .The1H
6 14 2 4
NMRspectrumofcompoundGconsistsofonlytwosignals:a12Hdoubletat1.1anda2Hseptetat3.6.Propose
astructuralformulaforcompoundG.
20.53Proposeastructuralformulaforeachofthefollowinghaloalkanes.
(a)C2H4Br22.5(d,3H)and5.9(q,1H)
(b)C4H8Cl21.7(d,6H)and2.2(q,4H)
(c)C5H8Br43.6(s,8H)
(d)C4H9Br1.1(d,6H),1.9(m,1H),and3.4(d,2H)
(e)C5H11Br1.1(s,9H)and3.2(s,2H)
(f) C7H15Cl1.1(s,9H)and1.6(s,6H)
20.54Thefollowingarestructuralformulaeforesters(a),(b)and(c)andthree1HNMRspectra.Assigneachcompoundto
itscorrectspectrumandassignallsignalstotheircorrespondinghydrogenatoms.
(a)

(b)

(c)
20.55CompoundK,C H O ,isnotsolubleinwater,10%NaOHor10%HCl.A1HNMRspectrumofcompoundK
10 10 2
showssignalsat2.6(s,6H)and8.0(s,4H).A13CNMRspectrumofcompoundKshowsfoursignals.Fromthis
information,proposeastructuralformulaforK.
20.56CompoundL,C15H24O,isusedasanantioxidantinmanycommercialfoodproducts,syntheticrubbersand
petroleumproducts.ProposeastructuralformulaforcompoundLbasedonthefollowing1HNMRand13CNMR
spectra.
20.57AcompoundwithmolecularformulaC H exhibitsa1HNMRspectrumwithonlyonesignalanda13CNMR
8 18
spectrumwithtwosignals.Proposeastructureforthiscompound.
20.58AcompoundwithmolecularformulaC H exhibitsa1HNMRspectrumwithonlyonesignalanda13CNMR
9 18
spectrumwithtwosignals.Deducethestructureofthiscompound.
20.59AcompoundwithmolecularformulaC H Oproducessixsignalsinits13CNMRspectrumandexhibitsthe
8 10
1
following HNMRspectrum.Deducethestructureofthecompound.

20.60DeducethestructureofacompoundwithmolecularformulaC9H12thatproducesthefollowing

20.61Proposeastructuralformulaforeachofthefollowingcompounds,whichallcontainanaromaticring.
(a)C9H10O1.2(t,3H),3.0(q,2H)and7.48.0(m,5H)
(b)C10H12O22.2(s,3H),2.9(t,2H),4.3(t,2H)and7.3(s,5H)
(c)C10H141.2(d,6H),2.3(s,3H),2.9(septet,1H)and7.0(s,4H)
(d)C8H9Br1.8(d,3H),5.0(q,1H)and7.3(s,5H)
20.62CompoundM,withthemolecularformulaC9H12O,readilyundergoesacidcatalyseddehydrationtogivecompound
N,withthemolecularformulaC9H10.A1HNMRspectrumofcompoundMshowssignalsat0.9(t,3H),1.8(m,
2H),2.3(s,1H),4.6(t,1H)and7.5(m,5H).Fromthisinformation,proposestructuralformulaeforcompoundsM
andN.
20.63Proposeastructuralformulaforeachofthefollowingketones.
(a)C4H8O1.0(t,3H),2.1(s3H)and2.4(q,2H)
(b)C7H14O0.9(t,6H),1.6(sextet,4H)and2.4(t,4H)
20.64ProposeastructuralformulaforcompoundO,aketonewiththemolecularformulaC H Oandthe1HNMR
10 12
 ProposeastructuralformulaforcompoundO,aketonewiththemolecularformulaC10H12Oandthe1HNMR
spectrumshownbelow.

20.65Thefollowingisa1HNMRspectrumofcompoundP,withthemolecularformulaC H O .CompoundPundergoes
6 12 2
acidcatalyseddehydrationtogivecompoundQ,C6H10O.ProposestructuralformulaeforcompoundsPandQ.

20.66ProposeastructuralformulaforcompoundR,withthemolecularformulaC H O.Thefollowingareits1HNMR
12 16
and13CNMRspectra.

20.67ProposeastructuralformulaforeachofthefollowingcarboxylicacidswiththeNMRsignalsgiveninthetables.
(a)C5H10O2
 (a)C5H10O2

1HNMR 13CNMR

0.9(t,3H) 180.7
1.4(m,2H) 33.9
1.6(m,2H) 26.8
2.4(t,2H) 22.2
12.0(s,1H) 13.7

(b)C6H12O2

1HNMR 13CNMR

1.1(s,9H) 179.3
2.2(s,2H) 46.8
12.1(s,1H) 30.6
29.6

(c)C5H8O4

1HNMR 13CNMR

0.9(t,3H) 170.9
1.8(m,2H) 53.3
3.1(t,1H) 21.9
12.7(s,2H) 11.8

20.68Thefollowingare1HNMRand13CNMRspectraofcompoundS,withthemolecularformulaC H O .Proposea
7 14 2
structuralformulaforcompoundS.

20.69Thefollowingare1HNMRand13CNMRspectraofcompoundT,withthemolecularformulaC H NO.Proposea
10 15
structuralformulaforthiscompound.
20.70ProposeastructuralformulaforamideU,withthemolecularformulaC H NOandthe1HNMRspectrumshown
6 13
below.

20.71Proposeastructuralformulafortheanalgesicphenacetin,withthemolecularformulaC H NO ,basedonits1H
10 13 2
NMRspectrum.

20.72Thefollowingisa1HNMRspectrumandastructuralformulaforanethole,C H O,anaturalfragrantproduct
10 12

obtainedfromanise.Usingthelinesofintegration,determinethenumberofprotonsgivingrisetoeachsignal.Show
thatthisspectrumisconsistentwiththestructureofanethole.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
20.73Limoneneisahydrocarbonfoundinthepeelsoflemonsthatcontributessignificantlytothesmelloflemons.
Limonenehasamolecularionpeakatm/z=136initsmassspectrum,andithastwodoublebondsandoneringinits
structure.Whatisthemolecularformulaoflimonene?
20.74FollowingaretheIRspectrumandmassspectrumofanunknowncompound.Proposeatleasttwopossiblestructures
fortheunknowncompound.

20.75FollowingaretheIRspectrumandmassspectrumofanunknowncompound.Proposeatleasttwopossiblestructures
fortheunknowncompound.
20.76ProposeastructuralformulaforeachofthefollowingesterswiththeNMRsignalsgiven.
(a)C6H12O2

1HNMR 13CNMR

1.2(d,6H) 177.2
1.3(t,3H) 60.2
2.5(m,1H) 34.0
4.1(q,2H) 20.0
14.3

(b)C7H12O4

1HNMR 13CNMR

1.3(t,6H) 166.5
3.4(s,2H) 61.4
4.2(q,4H) 41.7
14.1

(c)C7H14O2

1HNMR 13CNMR

0.9(d,6H) 171.2
1.5(m,2H) 63.1
1.7(m,1H) 37.3
2.1(s,3H) 25.1
4.1(t,2H) 22.5
21.1

20.77CompoundVisanoilyliquidwiththemolecularformulaC8H9NO2.ItisinsolubleinwaterandaqueousNaOH,butit
dissolvesin10%HCl.WhenitssolutioninHClisneutralisedwithNaOH,compoundVisrecoveredunchanged.A1H
NMRspectrumofcompoundVshowssignalsat3.8(s,3H),4.2(s,2H),7.6(d,2H)and8.7(d,2H).Proposea
structuralformulaforcompoundV.
20.78ProposeastructuralformulaforcompoundW,C H O,basedonthefollowingIRand1HNMRspectra.
4 6
20.79ProposeastructuralformulaforcompoundX,C H O ,basedonthefollowingIRand1HNMRspectra.
5 10 2

20.80ProposeastructuralformulaforcompoundY,C5H9ClO2,basedonthefollowingIRandspectra.
20.81ProposeastructuralformulaforcompoundZ,C H O,basedonthefollowingIRand1HNMRspectra.
6 14

20.82Determinethestructureoftheunknowncompoundwiththespectroscopicdatagivenonthisandthenextpages.Note:
DEPTspectraareaspecialtypeof13CNMRspectroscopyinwhichwecandeterminethenumberofhydrogenatoms
oneachcarbonatom.IntheDEPTcomponentofthe13CNMRspectrum,thesignalspointingupwardsaredueto
eitherCHorCH3groups,whilethosepointingdownwardsareduetoCH2groups.Quaternarycarbons(those
withoutanyhydrogenatoms)arenotobservedinDEPTspectra.
20.83Determinethestructureoftheunknowncompoundwiththespectroscopicdataonthisandthenextpages.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
(n+1)rule frequency referencecompound
13CNMRspectroscopy Hertz(Hz) resonance
1HNMRspectroscopy highresolutionmass shielded
spectrometry signalsplitting
BeerLambertlaw
indexofhydrogendeficiency singlet
bending
(IHD) splittingpattern
chemicalshift()
infraredactive stretching
complexsplittingpatterns
infraredradiation tetramethylsilane(TMS)
correlationtables
integration triplet
deshielded
lineofintegration upfield
doublebondequivalents
localmagneticfields UV/visiblespectroscopy
doublet
massspectrometry vibrationalinfrared
downfield
molecularions Wavelength
electromagneticradiation
multiplets wavenumber
electronparamagnetic
multiplicity Xraycrystallography
resonance(EPR)
nuclearmagneticresonance
Electronspinresonance(ESR)
(NMR)spectroscopy
equivalenthydrogenatoms
quartet
fingerprintregion
radicalcations
radiofrequencyradiation

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

21 AldehydesandKetones
EveningbarbecuesandpoolpartiesarecommonsummerleisureactivitiesinAustraliaandNew
Zealand.However,alsocommonarethedreadedmosquitoesandsandflies.Citronellacandlesarean
increasinglypopularweaponinthebattletopreventmosquitobites.Citronella(structureshownbelow)
isaprincipalcomponentofcitronellaoilandbelongstothefamilyofnaturalproductsknownas
terpenes.Ithasapleasantlemonyscentandiswidelyusedasafragranceinsoaps.Ofthetwo
functionalgroupsincitronellal,analkeneandanaldehyde,itisthealdehydegroupthatisofmost
interesthere.

Inthisandseveralofthefollowingchapters,westudythephysicalandchemicalpropertiesof
compoundscontainingthecarbonylgroup,C O.Sincethecarbonylgroupispresentinaldehydes,
ketones,andcarboxylicacidsandtheirderivatives,itisoneofthemostimportantfunctionalgroupsin
organicchemistry.Thechemicalpropertiesofthecarbonylgrouparestraightforward,andan
understandingofitscharacteristicreactionsleadstoanunderstandingofawidevarietyoforganic
reactions.
 KEYTOPICS

21.1Structureandbonding
21.2Nomenclature
21.3Physicalproperties
21.4Preparationofaldehydesandketones
21.5Reactions
21.6Ketoenoltautomerism

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.1StructureandBonding
Whenacarbonylgroupisbondedtoahydrogenatomandahydrocarbongroup(orasecondhydrogen
atom),thecompoundisanaldehyde.Thesimplestaldehyde,formaldehyde(methanal),hasthecarbonyl
groupbondedtotwohydrogenatoms.Inallotheraldehydes,thecarbonylgroupisbondedtoonehydrogen
atomandonecarbonatom.WhenthecarbonatomoftheC Ogroupisbondedtotwohydrocarbon
groups,thecompoundisaketone.ThefollowingareLewisstructuresforthealdehydesformaldehyde
(methanal)andacetaldehyde(ethanal),andforthesimplestketones,acetone(propanone)andmethylethyl
ketone(butanone).TheIUPACnameofeachcompoundisinparentheses.

ThealdehydegroupisoftenwrittenCHO,thedoublebondofthecarbonylgroupbeingimplied.The
abbreviationCOHisnotappropriatebecauseitsuggestsanalcoholfunctionalgroup.Theketonegroupis
sometimescondensedtoCO.

Thecarbonylgroupisaplanargroupcomprisingacarbonatombondedtoanoxygenatomandtwoother
atoms.Thebondanglesaroundthecarbonylcarbonatomareapproximately120.Accordingtothevalence
bondtheory(seesection5.6),acarbonoxygendoublebondconsistsofonebondformedbytheoverlap
ofthesp 2hybridorbitalsofcarbonandoxygen,andonebondformedbytheoverlapoftwoparallel2p
orbitals.Thetwononbondingpairsofelectronsontheoxygenatomlieinthetworemainingsp 2hybrid
orbitals(figure21.1).

FIGURE21.1 Representationsofacarbonoxygendoublebond:
(a)Lewisstructureofformaldehyde,CH2 O,
 (a)Lewisstructureofformaldehyde,CH2 O,
(b)thebondframeworkandnonoverlappingparallel2patomicorbitals,
(c)overlapofparallel2patomicorbitalstoformabondand
(d)anelectrondensitymodelshowingtheunevendistributionofelectronsinthecarbonylgroup.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.2Nomenclature
TheIUPACsystemofnomenclatureforaldehydesandketonesfollowsthepatternoffirstselectingthelongestchainof
carbonatomsthatcontainsthefunctionalgroupastheparentalkane.Weshowthepresenceofthealdehydegroupby
changingthesuffixeoftheparentalkanetoal,asinmethanal(section2.3).Asthecarbonylgroupofanaldehyde
canappearonlyattheendofaparentchain,itspositionisunambiguousthereisnoneedtouseanumbertolocate
it.

ForcyclicmoleculesinwhichtheCHOgroupisbondeddirectlytothering,wenamethemoleculebyaddingthe
suffixcarbaldehydetothenameofthering.Wenumbertheatomoftheringbearingthealdehydegroupas1.

Thecommonnameforanaldehydeisderivedfromthecommonnameofthecorrespondingcarboxylicacidby
droppingthewordacidandchangingthesuffixicoroictoaldehyde.Wecanillustratethisusingtwocommon
namesofcarboxylicacidswithwhichyouarefamiliar.Thenameformaldehydeisderivedfromformicacid,andthe
nameacetaldehydefromaceticacid.

AmongthealdehydesforwhichtheIUPACsystemretainscommonnamesare:formaldehyde,acetaldehyde,
benzaldehydeandcinnamaldehyde.

Noteherethealternativewaysofwritingthephenylgroup(C6H5).Inbenzaldehyde,itiswrittenasalinestructure,
whileincinnamaldehydeitisabbreviatedtoPh.

IntheIUPACsystem,wenameketonesbyselectingthelongestchainthatcontainsthecarbonylgroupandmakingit
theparentalkane.Thepresenceoftheketoneisindicatedbychangingthesuffixfrometoone(section2.3).We
numbertheparentchainsothatthecarbonylcarbonatomhasthesmallestnumber.TheIUPACsystemretainsthe
commonnamesacetone,acetophenoneandbenzophenone.
Commonnamesforketonesarederivedbynamingeachalkylorarylgroupbondedtothecarbonylgroupasa
separateword,followedbythewordketone.Groupsaregenerallylistedinorderofincreasingatomicweight.For
example,methylethylketone,MEK,isacommonsolventforvarnishesandlacquers.

WORKEDEXAMPLE21.1

NamingAldehydesandKetones

(a)

(b)

(c)

Analysis
(a)Identifythelongestchaincontainingthealdehydegroup.Thiswillbetheparentchain.Numberthe
chainstartingfromthealdehydegroup.
(b)Numberthesixmemberedringbeginningwiththecarbonylcarbonatom.
(c)Thismoleculeisderivedfrombenzaldehyde,soitshouldbenamedasasubstitutedbenzaldehyde.
 Solution
(a)TheIUPACnameofthiscompoundis2ethyl3methylpentanal.
(b)TheIUPACnameofthiscompoundis3methylcyclohex2enone.
(c)TheIUPACnameofthiscompoundis2ethylbenzaldehyde.

Isouranswerreasonable?

Checkthattheanswerleadsunambiguouslytothegivenstructure.Checkthatthestructureisnumbered
fromthecorrectendandthatthesubstituentsarenumberedappropriately.

PRACTICEEXERCISE21.1
WritetheIUPACnameforeachofthefollowing
compounds,andspecifytheconfigurationof(c).
(a)

(b)

(c)

WORKEDEXAMPLE21.2

DrawingStructuralFormulaeforKetones
WritestructuralformulaeforallketoneswiththemolecularformulaC6H12O,andgiveeachitsIUPAC
name.Whichoftheseketonesarechiral?

Analysis

Firstly,identifythepossibleskeletalarrangementswithsixcarbonatomsthatcouldgiveaketone.The
possibleketonesarederivedfromhexane,2and3methylpentane,and2,2dimethylbutane.Achiral
ketonehasatleastonestereocentre(bondedtofourdifferentgroups).

Solution

ThefollowingarelinestructuresandIUPACnamesforthesixketoneswiththemolecularformulaC6H12O.
 Only3methylpentan2onehasastereocentreandischiral.

Isouranswerreasonable?

Themostcommonerroristoduplicateormisssomestructures.Checkthateachstructureisdifferent(to
avoidduplication).Thebestwaytoensurethatyouhaveincludedallthepossiblestructuresistocheckthat
thebasicskeletalframeworksarecovered(asgivenintheanalysis)andthensystematicallymovethe
carbonylgrouptoeachpossibleposition.

PRACTICEEXERCISE21.2
Writestructuralformulaeforallaldehydeswiththe
molecularformulaC6H12O,andgiveeachits
IUPACname.Whichofthesealdehydesarechiral?

IUPACNamesforCompoundswithMorethanOneFunctionalGroup
Innamingcompoundsthatcontainmorethanonefunctionalgroup,IUPAChasestablishedanorderofprecedenceof
functionalgroups.Thatis,asystemforprioritisingfunctionalgroupsforthepurposesofIUPACnomenclature.Table
21.1givestheorderofprecedenceforsixfunctionalgroups.
TABLE21.1 Decreasingorderofprecedenceofsixfunctionalgroups.
Functional Exampleofwhenthefunctionalgroupisnothighestpriorityandisused
group Suffx Prefix asaprefix
carboxyl oic
group acid
aldehyde al oxo 3oxopropanoicacid
group

ketonegroup one oxo 3oxobutanoicacid

alcoholgroup ol hydroxy 4hydroxybutanal

aminogroup amine amino 3aminobutanal

sulfhydryl thiol mercapto 2mercaptoethanol

WORKEDEXAMPLE21.3

NamingComplexAldehydesandKetones
WritetheIUPACnameforeachofthefollowingcompounds.

(a)

(b)

(c)

Analysis
(a)Analdehydehashigherprecedencethanaketone,soweindicatethepresenceofthecarbonylgroup
oftheketonebytheprefixoxo.
(b)Thecarboxylgrouphashigherprecedencethantheaminogroup,soweindicatethepresenceofthe
aminogroupbytheprefixamino.
(c)Thecarbonylgrouphashigherprecedencethanthehydroxylgroup,soweindicatethehydroxyl
groupbytheprefixhydroxy.TodeterminetheR,Sconfiguration,followtheprocedureinsection
17.3.

Solution
(a)TheIUPACnameofthiscompoundis3oxobutanal.
(b)TheIUPACnameis4aminobenzoicacid.Alternatively,thecompoundmaybenamedp
aminobenzoicacid,abbreviatedPABA.PABA,agrowthfactorofmicroorganisms,isrequiredfor
thesynthesisoffolicacid.
(c)TheIUPACnameofthiscompoundis(R)6hydroxyheptan2one.

Isouranswerreasonable?

Tocheckeachanswer,drawastructurefromthenamethathasbeendetermined.Itshouldbethesameas
thecompoundfromthequestion.

PRACTICEEXERCISE21.3
WriteIUPACnamesforthefollowingcompounds,
eachofwhichisimportantinmetabolicprocesses.
(a)

(b)
 (c)

Thenameshownisthecompound'scommonname
asusedinthebiologicalsciences.

ChemistryResearch

PlantProtection

AssociateProfessorEmilioGhisalberti,UniversityofWesternAustralia

Aldehydesandketonesoccurverywidelyinnature.Manysubstancesrequiredby,andproducedby,living
organismscontainthesefunctionalgroups.Inthechemicalindustry,simplealdehydesandketonesare
producedinlargequantitiesassolventsandforuseinthepreparationofothercompounds.Manyhave
pleasantodoursandflavoursandareusedinperfumes,soapsandinfoodtechnology.

Inrecentyears,scientistshavediscoveredthatsomealdehydesandketonesareusedbylivingorganismsto
communicatewithmembersofthesamespeciesandtodefendthemselvesfrompredators.Plantshave
developedmethodsthatusealdehydesandketonestodefendthemselvesfromherbivores,particularlyinsects.

Theproductionofdefencecompoundsbyplantswhentheyareinjuredcanbeeasilydemonstrated.Ifafew
bladesofgrass,oraplantleaf,arecrushedbetweenthefingers,adistinctivesmellcanbedetectedafterafew
seconds.Thissmell,oftenreferredtoasthesmelloffreshlycutgrassorgreenodour,isduetoeight
differentcompoundsincludingthefouraldehydesshownbelow.

Theredleggedearthmiteisasignificantpestofpastures,cropsandvegetablesinSouthAfrica,Australiaand
NewZealand.InAustralia,itisapestofsubterraneanclover(figure21.2)andisresponsibleforlossesin
pasturecropsofanestimated$100million.
 FIGURE21.2TrifoliumsubterraneumatypeofsubterraneancloverthatgrowsinAustralia.
SPL/Maria&BrunoPetriglia

Fortunately,somevarietiesofsubterraneanclovershowresistancetothemiteanddeterthemitefromfeeding
onthem.Itwassuggestedthatwhenthemiteprobedtheleafsurfacewithitsmouthparts,theresistant
varietiesproducedacompoundunpalatabletothemite.Afteraconsiderableamountofwork,theGhisalberti
researchgroup,workingincollaborationwiththeentomologysectionofCSIRO,showedthistobethecase.
Infact,thecompoundthatdetersthemitesfromfeedingwasshowntobetheketoneoct1en3one(shown
below).Thisnontoxiccompoundcanbeusedinsteadofpesticidestoprotectthecrop.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.3PhysicalProperties
Oxygenismoreelectronegative(seechapter5,p.168)thancarbon(=3.5comparedwith2.5)
therefore,acarbonoxygendoublebondispolar,withtheoxygenatombearingapartialnegative
chargeandthecarbonatombearingapartialpositivecharge.Resonanceeffectsalsocontributetothe
polarityofthecarbonylgroups.

Theelectrondensitymodel(above)showsthatthepartialchargeonanacetonemoleculeisdistributed
bothonthecarbonylcarbonatomandonthetwoattachedgroups.Becauseofthepolarityofthe
carbonylgroup,aldehydesandketonesarepolarcompoundsandinteractintheliquidstatethrough
dipoledipoleinteractions.Asaresult,aldehydesandketoneshavehigherboilingpointsthannonpolar
compoundswithacomparablenumberofelectrons.Table21.2liststheboilingpointsofsixcompounds
withasimilarnumberofelectrons.
TABLE21.2 Boilingpointsofsixcompoundsofcomparablemolarmassandsimilarnumbersofelectrons.
Name Structuralformula Numberofelectrons Boilingpoint(C)
diethylether CH3CH2OCH2CH3 42 34
pentane CH3CH2CH2CH2CH3 42 36

butanal CH3CH2CH2CHO 40 76
butanone CH3CH2COCH3 40 80

butan1ol CH3CH2CH2CH2OH 42 117

propanoicacid CH3CH2COOH 40 141

Pentaneanddiethyletherhavethelowestboilingpointsofthesesixcompounds.Bothbutanaland
butanonearepolarcompounds,andhavehigherboilingpointsbecauseoftheintermolecularattraction
betweencarbonylgroups.Alcohols(section19.1)andcarboxylicacids(section23.1)arealsopolar
compounds,andbecausetheirmoleculesassociatebyhydrogenbondingtheirboilingpointsarehigher
thanthoseofbutanalandbutanonecompoundsthatcannotformintermolecularhydrogenbonds
betweenlikemolecules.

Lowmolarmassaldehydesandketonesaremoresolubleinwaterthannonpolarcompoundsofsimilar
molarmassbecausecarbonylgroupsinteractwithwatermoleculesbyhydrogenbonding.Thecarbonyl
groupisahydrogenbondacceptor(theoxygenatomprovidestheelectronstoformthehydrogenbond
withwater),asshownontheright.
Table21.3liststheboilingpointsandsolubilitiesinwaterofseverallowmolarmassaldehydesand
ketones.
TABLE21.3 Physicalpropertiesofselectedaldehydesandketones.
IUPAC Boilingpoint Solubility(g/100g
name Commonname Structuralformula (C) water)
methanal formaldehyde HCHO 21 infinite
ethanal acetaldehyde CH3CHO 20 infinite

propanal propionaldehyde CH3CH2CHO 49 16

butanal butyraldehyde CH3CH2CH2CHO 76 7

hexanal caproaldehyde CH3(CH2)4CHO 129 slight

propanone acetone CH3COCH3 56 infinite

butanone methylethyl CH3COCH2CH3 80 26
ketone
pentan3 diethylketone CH3CH2COCH2CH3 101 5
one

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.4PreparationofAldehydesandKetones
Aldehydesandketonescanbepreparedfrommanyfunctionalgroupsusingvariousreactions.Someof
thesewillbediscussedbrieflyhereandinmoredetailelsewhereinthistext.However,beforedescribing
specificexamplesofthesynthesisofaldehydesandketones,wewilllookbrieflyatsomeofthemore
industriallyimportantcompoundsinthisclass.

IndustriallyImportantAldehydesandKetones
Formaldehydeisprobablythemostimportantaldehydeproducedonanindustrialscale,withover17
milliontonnesproducedannually,principallybytheoxidationofmethanol.Itisusedmainlyinthe
manufactureofresinsfortheconstructionindustry,particularlyintheproductionofwoodbased
products.Thenextmostabundantlyproducedaldehydesarethebutanals(butanalandmethylpropanal).
Theseareproducedbythehydroformylation(additionofcarbonmonoxideandhydrogen)ofpropene
byaprocessknownastheoxoprocess(seetheequationbelow).Approximately6milliontonnesof
butanalsareproducedannually,mainlyforthemanufactureofplasticisers.Thealiphaticaldehydeswith
6to13carbonatomsareusedextensivelyinthefragranceindustry.

Industriallyimportantaromaticaldehydesincludephenylacetaldehyde(usedintheflavourand
fragranceindustry)andsalicylaldehyde(2hydroxybenzaldehyde),whichisusedinthesynthesisof
coumarinfortheelectroplatingindustryandalsoforthesynthesisofagrochemicals,pharmaceuticals
andfragrances.

Acetoneisthesimplestandmostimportantketoneandfindsubiquitoususeasasolvent.Higher
membersofthealiphaticmethylketoneseries(suchasmethylethylketone,methylisobutylketone,
methylamylketone)arealsoindustriallysignificantsolvents.Acetonehasbeenproducedindustrially
foroveracenturybyavarietyofmethods.However,today,mostoftheworld'ssupplyisobtainedasa
coproductinthepreparationofphenolbythehydroperoxidationofcumene.Acetoneisusedasa
solventinthepreparationofmethylmethacrylateandbisphenolA(bothusedintheproductionof
polymers).Theothermethylketones,includingmethylethylketone(MEK,butanone)andmethyl
isobutylketone(MIBK,4methylpentanone)arealsoimportantindustrialsolvents,particularlyfor
coatingsandinks.
Importantaromaticketonesinclude,acetophenone,propiophenone(ethylphenylketone)(usedinthe
manufactureofephedrineandasafragranceenhancer)andbenzophenone(usedasaphotoinitiatorin
UVcurableinksandcoatings).

FriedelcraftsAcylation
KetonescanbepreparedbyFriedelCraftsacylationofaromaticcompounds(seesection16.8)as
illustratedbythereactionofbenzeneandacetylchlorideinthepresenceofaluminiumchloridetogive
acetophenone.

Acetophenoneisproducedindustriallybythisprocessandisusedinthepreparationofpaintsand
resins,andinpharmaceuticals,perfumesandpesticides.

OxidationofAlcohols
Wehavealreadyseeninchapter19thatprimaryalcoholscanbeoxidisedundermildconditionstogive
aldehydes(formoreexamplesofthisreactionseesection19.2).

PCC(pyridiniumchlorochromate)isamildoxidisingagentthatwilloxidiseprimaryalcoholsto
aldehydesbutwillnotfurtheroxidisealdehydestocarboxylicacids.Ketonescanbeobtainedbythe
oxidationofsecondaryalcohols(formoreexamplesofthisreactionseesection19.2).
OzonolysisofAlkenes
Alkenesarereadilycleavedbyreactionwithozonefollowedbyreductivehydrolysistogivealdehydes
and/orketones.Ozoneisbubbledthroughasolutionofthealkeneinaninertsolventtoproducean
unstableozonide.Thisozonideisnotisolatedbuttreatedwithamildreducingagent(typically
zinc/water/acidordimethylsulfide)togivecarbonylcompoundsasshownbelow(alongwithinorganic
products,whicharenotshown).

Althoughthereactionmaylookcomplex,thefinaloutcomeissimplythecleavageofaC Cbondand
itsreplacementwithtwoC Ogroups.Whenthealkeneispartofaring,asinglecompoundwithtwo
carbonylgroupsisformed.

HydrationofAlkynes
Insection16.5,theelectrophilicadditionofwatertoalkenes(hydration)togivealcoholswasdiscussed.
Watercanalsobeaddedtoalkynesunderacidicconditionsinthepresenceofamercuricsulfate
catalyst.Theinitialproductofthisreactionisanenol(analkenewithan OHgroup)whichundergoes
tautomerism(seesection21.6)togiveaketone.TheadditionobeysMarkovnikov'srule(section16.5),
andterminalalkynes(thosewiththealkynegroupattheendofthechain)givemethylketones.
Internalalkynesgiveamixtureoftwoketones(theintermediateenolisnotshown).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.5Reactions
Aldehydesandketonesareveryreactiveduetothepolarityandstructureofthecarbonylgroup(figure21.3).They
areelectronrichgroupsduetothebondandthetwononbondingpairsofelectronsontheoxygenatom.The
polarityoftheC bondenhancestheattractionofnucleophiles(tothe+carbonatom)andelectrophiles(tothe
oxygenatom),whiletheflatstructureallowseasyaccesstothesereactivecentres.Aldehydesareusuallymore
reactivethanketonesbecauseaccesstothecarbonylcarbonatomiseasierastheyhaveonlyonealkylgroup(which
isbulkierthanahydrogenatom)attached.

FIGURE21.3Anelectrondensitymodelhighlightingthepolarityofthecarbonylgroup.

Themostcommonreactionthemeofthecarbonylgroupistheadditionofnucleophilestoformtetrahedral
carbonyladditionintermediates.Inthefollowinggeneralreaction,thenucleophilicreagentiswrittenasNu:to
emphasisethepresenceofanunsharedpairofelectrons.

AdditionofGrignardReagents
Theadditionofcarbonnucleophilesisamongthemostimportanttypesofnucleophilicadditiontocarbonylgroups,
becausethesereactionsformnewcarboncarbonbonds.Inthissection,wedescribethepreparationandreactionsof
Grignardreagents,andtheirreactionwithaldehydesandketones.

FormationandStructureofOrganomagnesiumCompounds
Alkyl,arylandvinylichalidesreactwithgroup1,group2andcertainothermetalstoformorganometallic
compounds.Anorganometalliccompoundisacompoundcontainingacarbonmetalbond.Organomagnesium
compoundsareamongthemostreadilyavailable,easilypreparedandeasilyhandledorganometalliccompounds.
OrganomagnesiumcompoundsofthetypeRMgXorArMgXarecommonlynamedGrignardreagents,afterVictor
Grignard,whowasawardedthe1912NobelPrizeinchemistryfortheirdiscoveryandtheirapplicationtoorganic
synthesis.

Grignardreagentsaretypicallypreparedbytheslowadditionofalkyl,arylorvinylhalidestoastirredsuspensionof
magnesiummetalinanethersolvent,mostcommonlydiethyletherortetrahydrofuran(THF).Organoiodidesand
bromidesgenerallyreactrapidlyundertheseconditions,whereaschloridesreactmoreslowly.Butylmagnesium
bromide,forexample,ispreparedbyadding1bromobutanetoanethersuspensionofmagnesiummetal.Aryl
Grignards,suchasphenylmagnesiumbromide,arepreparedinasimilarmanner.

Giventhatthedifferenceinelectronegativitybetweencarbonandmagnesiumis1.3(2.51.2),thecarbon
magnesiumbondisbestdescribedaspolarcovalent,withthecarbonatombearingapartialnegativechargeandthe
magnesiumatombearingapartialpositivecharge.Inthestructuralformulabelowright,thecarbonmagnesium
bondisshownasionictoemphasiseitsnucleophiliccharacter.Notethat,althoughwecanwriteaGrignardreagent
asacarbanion(ananioninwhichthecarbonatomhasanunsharedpairofelectronsandbearsanegativecharge),a
moreaccuraterepresentationshowsitasapolarcovalentcompound(belowleft)and,infact,eachofthese
representsaresonanceformoftheactualCMgbond.

Inchapter18,youlearnedthatthecarbonatomsbondedtohalogensareelectrophilic(theyare+andundergo
reactionswithnucleophiles).ThefeaturethatmakesGrignardreagentssovaluableinorganicsynthesisisthatthe
carbonatombearingthehalogenistransformedfromanelectrophile(+)intoanucleophile(),asshowninthe
equationbelow.

ReactionWithProticAcids
Grignardreagentsareverystrongbasesandreactreadilywithawidevarietyofacids(protondonors)toform
alkanes.Ethylmagnesiumbromide,forexample,reactsinstantlywithwatertogiveethaneandmagnesiumsalts.This
reactionisanexampleofaverystrongbasecompletelydeprotonatingwater.

AnycompoundcontaininganOH,NHorSHbondwillreactwithaGrignardreagentbyprotontransfer.The
followingareexamplesofcompoundscontainingthosefunctionalgroups.

BecauseGrignardreagentsreactsorapidlywiththeseproticacids,theycannotbemadefromanyhalogen
containingcompoundsthatalsocontainproticacids.

WORKEDEXAMPLE21.4
 ReactionsofGrignardReagents
Writeanequationfortheacidbasereactionbetweenethylmagnesiumiodideandanalcohol.Usecurved
arrowstoshowthebondbreakingandbondformingprocessesinthisreaction.Inaddition,showthatthe
reactionisanexampleofaBrnstedLowryacidbasereaction.

Analysis

First,identifythepolarityofthespecies(+/).Theelectronswillcomefromtheportiontoforma
bondwiththe+portion.Inthisacidbasereactionthealcoholgroupprovidestheproton.

Solution

Thealcoholisaweakacidandtheethylcarbanionisaverystrongbase.

Isouranswerreasonable?

Checkthatthecurvedarrowsstartatanelectronrichregion(atomorbond)andendatanelectronpoor
atom.Checkthatthe+atomsarepairedwiththeatoms.

PRACTICEEXERCISE21.4
ExplainwhyGrignardreagentscannotbeformedfromthefollowing
organohalides.Whatwouldbeproducedwhenmagnesiummetalis
treatedwith(a)4bromophenoland(b)4bromobutanoicacid?

AdditionofGrignardReagentstoAldehydesandKetones
ThespecialvalueofGrignardreagentsisthattheyprovideexcellentwaystoformnewcarboncarbonbonds.In
theirreactions,Grignardreagentsbehaveasthoughtheywerecarbanions.Acarbanionisagoodnucleophileand
addstothecarbonylgroupofanaldehydeorketonetoformatetrahedralcarbonyladditioncompound(seeequation
below).Thereasonforthesereactionsoccurringsoreadilyistheattractionbetweenthepartialnegativechargeon
thecarbonatomoftheorganometalliccompoundandthepartialpositivechargeofthecarbonylcarbonatom.Inthe
examplesthatfollow,themagnesiumoxygenbondiswrittenasO[MgBr]+toemphasiseitsioniccharacter.The
alkoxideionsformedinGrignardreactionsarestrongbasesandformalcoholswhentreatedwithanaqueousacid
suchasHCloraqueousNH4Clduringseparationofthereactionproducts,byproductsandunreactedstarting
material.AgeneralschemeforthereactionofGrignardreagentswithcarbonylcompoundsshowingthepolarityof
thereactingspeciesisgivenbelow.Aneasywaytodeterminetheproductistoidentifythepolarityofthespecies(
+/).TheproductistheresultofthepartoftheGrignardreagentformingabondwiththe+carbonatomofthe
carbonylgroup(andbetweenthe+partoftheGrignardreagentandtheoxygenatomofthecarbonylgroup).

AdditiontoFormaldehyde(Methanal)Givesa1Alcohol
TreatmentofaGrignardreagentwithformaldehyde(methanal),followedbyhydrolysisinaqueousacid,givesa
primaryalcohol.

AdditiontoanAldehyde(ExceptFormaldehyde)Givesa2Alcohol
ThetreatmentofaGrignardreagentwithanyaldehydeotherthanformaldehyde,followedbyhydrolysisinaqueous
acid,givesasecondaryalcohol.Thestepsrequiredforthisreactionareshownbelow.

AdditiontoaKetoneGivesa3Alcohol
TreatmentofaGrignardreagentwithaketone,followedbyhydrolysisinaqueousacid,givesatertiaryalcohol.

AdditiontoCarbonDioxideGivesaCarboxylicAcid
Grignardreagentsreactwithcarbondioxidetogiveamagnesiumcarboxylate,whichisconvertedintoacarboxylic
acidbyacidification.Thisreactionisapplicabletoalkylandarylhalides,andproducescarboxylicacidswithone
carbonatommorethantheoriginalorganohalide,asshownintheschemebelow.
WORKEDEXAMPLE21.5

Synthesisof3AlcoholsUsingGrignardReagents
Thetertiaryalcohol2phenylbutan2olcanbesynthesisedbythreedifferentcombinationsofaGrignard
reagentandacarbonylcompound.Showeachcombination.

Analysis

First,drawthestructureof2phenylbutan2ol.Asatertiaryalcohol,itcanbeproducedbythereactionof
aketonewithaGrignardreagent.Todeterminewhichketonesaresuitable,identifythecarbonatom
bondedtotheOHgroupthiswasthecarbonylcarbonatom.Twoofthegroupsbondedtothiscarbon
atomformtheketoneandthethirdformstheGrignardreagent.Astherearethreedifferentgroupswecan
havethreedifferentGrignardreagentsand,byaprocessofelimination,threedifferentketones.

Solution

Curvedarrowsineachsolutionshowtheformationofthenewcarboncarbonbondandthealkoxideion,
andlabelsonthefinalproductshowwhichsetofreagentsformseachbond.

Isouranswerreasonable?

Asimplewaytocheckifyouranswersmakesenseistocountthecarbonatomsinthestartingmaterials
andcomparethisnumberwiththeproduct(10carbonatoms).Iftheseagree,thencheckthateachcase
hasamethyl,anethylandaphenylgroup.

PRACTICEEXERCISE21.5
Showhowthefollowingthreecompoundscanbe
 synthesisedfromthesameGrignardreagent.
(a)

(b)

(c)

AdditionofOtherCarbonNucleophiles
Treatmentofaldehydesandsomeketoneswithsodiumcyanideanddiluteacidproducescyanohydrins,compounds
withanOHandaCNgroupbondedtothesamecarbonatom.Ketoneswithbulkygroupsdonotundergothis
reaction.Inthisreaction,thenegativelychargedcarbonatomofthecyanideionaddstothe+carbonylcarbon
atom,andthentheprotonfromtheacidaddstotheresultingnegativeoxygenatom.

Cyanohydrinsareusefulcompoundsinorganicchemistrybecausetheycanbeconvertedtohydroxycarboxylic
acidsor,unsaturatedacids(dependingonconditionsused),oraminoalcohols(seesection23.5).

Notethatwehavenowseenthreeconvenientmethodsofaddingonecarbonatomtoacarbonchain:theadditionof
cyanideionstocarbonylcompounds,andreactionsofGrignardreagentswithformaldehydeandwithcarbon
dioxide.
AdditionofAlcohols
Treatmentofaldehydesandketoneswithalcoholsinthepresenceofanacidcatalystproducesacetals.The
intermediatehemiacetals(halfacetals)aregenerallyunstableandareonlyminorcomponentsofanequilibrium
mixture,exceptinoneimportanttypeofmolecule(asdiscussedbelow).

ThehemiacetalgroupisacarbonatombondedtoanOHgroupandanORorOArgroup.Ahemiacetal
derivedfromaketoneissometimesreferredtoasahemiketal.

TheacetalfunctionalgroupisacarbonatombondedtotwoORorOArgroups.Acetalsderivedfromketonesare
sometimesreferredtoasketals.

Hemiacetalsarestablewhenahydroxylgroupispartofthesamemoleculethatcontainsthecarbonylgroup,and
fiveorsixmemberedringscanform.Inthesecases,thecompoundexistsalmostentirelyinacyclichemiacetal
form.

Weexaminecyclichemiacetalsinmoredetailwhenweconsiderthechemistryofcarbohydratesinchapter22.

Forclarity,wewillstudythereactionofalcoholswithaldehydesandketonesintwostages:(i)theformationof
hemiacetalsand(ii)thesubsequenttransformationofhemiacetalsintoacetals.

Thereactionofalcoholswithaldehydesandketonesisanacidcatalysedexampleofadditiontoacarbonyl
compoundtoproduceatetrahedralcarbonyladditionintermediate(inthiscase,thehemiacetal).Inthisprocess,H+
addstothecarbonyloxygenatom,andtheoxygenatomofthealcoholaddstothe+carbonylcarbonatom.
Thisisanotherexampleofgoeswith+.

Amechanismfortheformationofhemiacetalscanbedividedintothreesteps.NotethattheacidHAisatrue
catalystinthisreactionitisusedinstep1andisregeneratedinstep3.
Step1:Protontransferfromtheacid,HA,tothecarbonyloxygenatomgivesaresonancestabilisedcation.

Step2:Reactionoftheresonancestabilisedcation(anelectrophile)withmethanol(anucleophile)givesthe
conjugateacidofahemiacetal.

Step3:ProtontransferfromtheprotonatedhemiacetaltoAgivesthehemiacetalandregeneratestheacid
catalyst,HA.

Hemiacetalscanreactfurtherwithalcoholstoformacetalsplusamoleequivalentofwater.

Amechanismfortheacidcatalysedconversionofhemiacetalstoacetalscanbedividedintofoursteps.Notethatthe
acid,HA,isalsoacatalystinthisreactionitisusedinstep1andisregeneratedinstep4.
Step1:Protontransferfromtheacid,HA,tothehemiacetalOHgroupgivesanoxoniumion.
 Step2:Lossofwaterfromtheoxoniumiongivesaresonancestabilisedcation.

Step3:Reactionoftheresonancestabilisedcation(anelectrophile)withmethanol(anucleophile)givesthe
conjugateacidoftheacetal.

Step4:ProtontransferfromtheprotonatedacetaltoAgivestheacetalandgeneratesanewmoleculeofHA.

FormationofacetalsisoftencarriedoutusingthealcoholasasolventanddissolvingdryHCl(hydrogenchloride),
concentratedH2SO4orarenesulfonicacid(ArSO3H)inthealcohol.Becausethealcoholisbothareactantandthe
solvent,itispresentinalargemolarexcess,whichdrivesthereactiontotherightandfavoursacetalformation.
Alternatively,thereactionmaybedriventotherightbytheremovalofwaterasitisformed.
Notethat,aswaterisaproductinthisreaction,thereagents(thecarbonylcompoundandthealcohol)mustbe
anhydrous.Anyexcesswaterinthereactionmixturelimitstheamountofproductformed.

WORKEDEXAMPLE21.6

FormationofAcetals
Showthereactionofthecarbonylgroupofeachofthefollowingketoneswithonemoleequivalentof
alcoholtoformahemiacetal.Thenshowthereactionwithasecondmoleequivalentofalcoholtoforman
acetal(notethat,inpart(b),ethane1,2diol(ethyleneglycol)isadiolandprovidesbothOHgroups).
(a)

(b)

Analysis

Thecarbonylcarbonatomwillbecomethehemiacetal,andthentheacetal,sohighlightthisatom.The
hemiacetalisformedbyfirstforminganOHbondbetweenthecarbonyloxygenatomandtheacid
catalyst,andthenaCORbondbetweenthecarbonylcarbonatomandthealcoholoxygenatom.The
acetalisformedbyreplacingtheOHgroupwithanORgroup.

Solution

Herearestructuralformulaeofthehemiacetalandthentheacetal.
(a)

(b)

Isouranswerreasonable?

Asimplewaytocheckifyourstructuresmakesenseistocheckthatthenumberofcarbonatomsonthe
lefthandsideofthereactionisthesameastherighthandside.Iftheseagree,thencheckthateach
hemiacetalhasacarbonatomwithanOHandanORgroupand,fortheacetal,thiscarbonatomnow
hastwoORgroups.

PRACTICEEXERCISE21.6
 Thehydrolysisofanacetalformsanaldehydeora
ketoneandtwoequivalentsofalcohol.The
followingarestructuralformulaeforthreeacetals.
(a)

(b)

(c)

Drawthestructuralformulaefortheproductsof
thehydrolysisofeachacetalinaqueousacid.

Likeethers,acetalsareunreactivetobases,reducingagents,Grignardreagentsandoxidisingagents(except,of
course,thosewhichinvolveaqueousacid).Becauseoftheirlackofreactivitywiththesereagents,acetalsareoften
usedtoprotectthecarbonylgroupsofaldehydesandketoneswhilereactionsarecarriedoutonfunctionalgroupsin
otherpartsofthemolecule.Theacetalgroupcanthenbereadilyremovedinhighyieldbymildacidhydrolysis.

AcetalsasCarbonylprotectingGroups
Theuseofacetalsascarbonylprotectinggroupsisillustratedbythesynthesisof5hydroxy5phenylpentanalfrom
benzaldehydeand4bromobutanal.

Oneobviouswaytoformanewcarboncarbonbondbetweenthesetwomoleculesistotreatbenzaldehydewiththe
Grignardreagentformedfrom4bromobutanal.ThisGrignardreagent,however,wouldreactimmediatelywiththe
carbonylgroupwithinthesamemoleculeorinanothermoleculeof4bromobutanal,causingittoselfdestruct
duringpreparation.Awaytoavoidthisproblemistoprotectthecarbonylgroupof4bromobutanalbyconvertingit
toanacetal.Cyclicacetalsareoftenusedbecausetheyareparticularlyeasytoprepareandaremorestableto
hydrolysis.Thisissimilartothechelateeffectobservedinthecoordinationofbidentateligandstometalions(see
section13.4).
Treatmentoftheprotectedbromoaldehydewithmagnesiumindiethylether,followedbytheadditionof
benzaldehyde,givesamagnesiumalkoxide.

Treatmentofthemagnesiumalkoxidewithaqueousacidaccomplishestwothings.First,protonationofthealkoxide
aniongivesthedesiredhydroxylgroup,andthen,hydrolysisofthecyclicacetalregeneratesthealdehydegroup.

AdditionofAmmonia,AminesandRelatedCompounds
ThechemistryinthissectioncanbesummarisedbythegeneralreactionshownatthetopofthenextpagewhereG
canbearangeofgroupsincludingH,R,Ar,NH2,NHArandOHbutnotanacylgroup,C( O)R.
Ultimatelythecarbonyloxygenatomisreplacedbyasubstitutednitrogenatom(NG)withtheformationofwater
asabyproduct.

FormationofImines
Ammonia,primaryaliphaticamines,RNH2,andprimaryaromaticamine,ArNH2,reactwiththecarbonylgroupof
aldehydesandketonesinthepresenceofanacidcatalysttogiveimines(compoundsthatcontainacarbonnitrogen
doublebond).
Amechanismisdescribedinthefollowingsteps:
Step1:Additionofthenitrogenatomofammoniaoraprimaryaminetothecarbonylcarbonatom,followedby
protonationoftheoxygenatomanddeprotonationofthenitrogenatom,givesatetrahedralcarbonyladdition
intermediate.

Thisstepisanalogoustotheformationofhemiacetals,asbothareexamplesofcarbonyladditionreactions.The
intermediateformedinstep1isunstable,andstep2occursspontaneously.
Step2:ProtonationoftheOHgroup,followedbylossofwaterandprotontransfertothesolventgivesthe
imine.NoticethatthelossofwaterandtheprotontransferhavethecharacteristicsofanE2reaction(seesection
18.3).Twothingshappensimultaneouslyinthisdehydration:thecarbonnitrogendoublebondforms,andthe
leavinggroup(inthiscase,awatermolecule)departs.

Step3:Deprotonationofthenitrogenatomintheresonancestabilisedcationgivestheimine.

OneexampleoftheimportanceofiminesinbiologicalsystemsistheactiveformofvitaminAaldehyde(retinal),
whichisboundtotheproteinopsininthehumanretinaintheformofaniminecalledrhodopsinorvisualpurple(see
chapter16,pp.7023).Theaminoacidlysine(table21.1,p.1057)providestheprimaryaminogroupforthis
reaction.
WORKEDEXAMPLE21.7

StructuralFormulaeforImines
Writeastructuralformulafortheimineformedineachofthefollowingreactions.
(a)

(b)

Analysis

ThecarbonylcarbonatomwillbebondedtothenitrogenatombyaC Ndoublebond.Theoxygen
atomofthecarbonylgroupandthetwohydrogenatomsoftheNH2groupcombinetoformwater.

Solution

Belowisastructuralformulaforeachimine.
(a)

(b)

Isouranswerreasonable?

CheckthatyougetthestartingmaterialsifyoucleavetheC Ndoublebondandaddanoxygenatomto
thecarbonatomandtwohydrogenatomstothenitrogenatom.

PRACTICEEXERCISE21.7
Acidcatalysedhydrolysisofaniminegivesanamineandan
aldehydeoraketone.Whenoneequivalentofacidisused,the
amineisconvertedtoitsammoniumsalt.Foreachofthe
followingimines,writeastructuralformulafortheproductsof
 hydrolysis,usingoneequivalentofHCl.
(a)

(b)

FormationofOximesandHydrazones
Whenaldehydesandketonesreactwithhydroxylamine,H2NOH,theyformoximes(compoundscontainingaC
NOHgroup).

TheLIXreagentsareexamplesofoximesandareproducedindustriallyforthesolventextractionofcopperand
nickelfromleachsolutions.ThesereagentscanbemadetocoordinateselectivelytoCu 2+andNi2+ionsbycareful
manipulationofthepH.Thelargealkylgroupparatothephenolensuresthereagentshavelowsolubilityinaqueous
solutionsandremainintheorganicsolvent(usuallykerosene).

Aconvenientspottestforaldehydesandketonesinvolvestheadditionofasolutionof2,4dinitrophenylhydrazine
(Brady'sreagent),alsoknownasthe2,4DNPtest.Inthepresenceofaldehydesorketonesthisreagentformsbright
orange/redhydrazones.

ReductiveAminationofAldehydesandKetones
Oneofthechiefvaluesofiminesisthatthecarbonnitrogendoublebondcanbereducedtoacarbonnitrogen
singlebondbyhydrogeninthepresenceofacatalyst(typicallynickel,palladiumorplatinum).Bythistwostep
reaction,calledreductiveamination,aprimaryamineisconvertedintoasecondaryaminethroughanimine
intermediate,asillustratedbelowbytheconversionofcyclohexylaminetodicyclohexylamine.

Conversionofanaldehydeoraketonetoanamineisgenerallycarriedoutinonelaboratoryoperationbymixing
togetherthecarbonylcontainingcompound,theamineorammonia,hydrogen,andthetransitionmetalcatalyst.The
imineintermediateisnotisolated.

ChemicalConnections

DrugDeliverybyHydrolysis

Methenamineasaprodrugofformaldehyde

Formaldehydehasantisepticpropertiesandcanbeusedtotreaturinarytractinfectionsduetoitsabilityto
reactwithnucleophilespresentinurine.However,formaldehydecanbetoxicwhenexposedtoother
regionsofthebody.Therefore,theuseofformaldehydeasanantisepticagentrequiresamethodfor
selectivedeliverytotheurinarytract.Thiscanbeaccomplishedbyusingaprodrugcalledmethenamine.

Thiscompoundisanitrogenanalogueofanacetal.Thatis,eachcarbonatomisconnectedtotwonitrogen
atoms,verymuchlikeanacetalinwhichacarbonatomisconnectedtotwooxygenatoms.Acarbonatom
thatisconnectedtotwoheteroatoms(OorN)canundergoacidcatalysedhydrolysis.
Eachofthecarbonatomsinmethenaminecanbehydrolysed,releasingformaldehyde.

Methenamineisplacedinspecialtabletsthatdonotdissolveastheytravelthroughtheacidicenvironment
ofthestomach,butdodissolveoncetheyreachthebasicenvironmentoftheintestinaltract.Methenamineis
therebyreleasedintotheintestinaltract,whereitisstableunderbasicconditions.Onceitreachestheacidic
environmentoftheurinarytract,methenamineishydrolysed,releasingformaldehyde,asshownabove.In
thisway,methenamineisusedasaprodrugthatenablesdeliveryofformaldehydespecificallytotheurinary
tract.Thismethodpreventsthesystemicreleaseofformaldehydetootherorgansofthebodywhereitwould
betoxic.

FIGURE21.4 Methenamineisstableunderbasicbutnotacidicconditions.Therefore,itisadministeredin
tabletsthatdonotdissolvein
(a)theacidicenvironmentofthestomach
(b)thetabletsdissolvewhentheyreachthebasicenvironmentoftheintestinaltract.
SPL/Gastrolab

Iminesasprodrugs

Theiminemoietyisusedinthedevelopmentofmanyprodrugs.Herewewillexploreoneexample.The
compoundbelow,aminobutyricacid,isanimportantneurotransmitter.

Adeficiencyofthiscompoundisthatitcancauseconvulsions.Administeringaminobutyricaciddirectly
toapatientisnotaneffectivetreatmentbecausethecompounddoesnotreadilycrossthebloodbrain
barrier.Thisisbecause,atphysiologicalpH,theaminogroupisprotonatedandthecarboxylicacidmoiety
isdeprotonated.
Thecompoundexistsprimarilyinthisionicform,whichcannotcrossthenonpolarenvironmentofthe
bloodbrainbarrier.Progabideisaprodrugderivativeusedtotreatpatientswhoexhibitthesymptomsofa
deficiencyofaminobutyricacid.

Thecarboxylicacidhasbeenconvertedtoanamide,andtheaminogrouphasbeenconvertedintoanimine
(highlightedinblueabove).AtphysiologicalpH,thiscompoundexistsprimarilyasaneutralcompound
(uncharged),anditcanthereforecrossthebloodbrainbarrier.Onceinthebrain,itisconvertedto
aminobutyricacidviahydrolysisoftheimineandamidemoieties.

Progabideisjustoneexampleinwhichtheiminemoietyhasbeenusedinthedevelopmentofaprodrug.

WORKEDEXAMPLE21.8

SynthesisofAmines
Showhowtosynthesiseeachofthefollowingaminesbyreductiveamination.
(a)
 (b)

Analysis

Inreductiveamination,animineisreducedtoanaminebyadditionofhydrogenacrosstheC Ndouble
bond.Workingbackwardstodeterminethestructureoftheimine,simplydrawinadoublebond
betweentheCandNatoms(andremoveahydrogenatomfromthenitrogenatom).In(a)thereisonly
oneCNbond,sothechoiceiseasyin(b)therearetwo,butthegroupsarethesame,soagainthe
choiceiseasy.Todeterminethestructureofthecarbonylcompound,replacetheC NRgroupwithaC
Ogroup.Theidentityoftheamineisdeterminedbyaddingtwohydrogenatomstothenitrogenatom
ofthe NRgroup.

Solution

ThecarbonylcompoundistreatedwithammoniaoranamineinthepresenceofH2/Ni.
(a)

(b)

Isouranswerreasonable?

Checkthattheskeletalstructuresofthecarbonylcompoundsandtheaminesareconsistentwiththoseof
theimineintermediateandthetargetamines.

PRACTICEEXERCISE21.8
Showhowtoprepareeachofthefollowingamines
bythereductiveaminationofanappropriate
aldehydeorketone.
(a)

(b)
Reduction
Aldehydesarereducedtoprimaryalcohols,andketonesarereducedtosecondaryalcohols.

CatalyticReduction
Thecarbonylgroupofanaldehydeoraketoneisreducedtoahydroxylgroupbyhydrogeninthepresenceofa
transitionmetalcatalyst,mostcommonlyfinelydividedpalladium,platinum,nickelorrhodium.Reductionsare
generallycarriedoutattemperaturesfrom25Cto100Candatpressuresofhydrogenfrom100to500kPa(15
timesatmosphericpressure).Undersuchconditions,cyclohexanoneisreducedtocyclohexanolasshownbelow.

Thecatalyticreductionofaldehydesandketonesproceedswithgenerallyveryhighyields,andisolationofthefinal
productisveryeasy.However,adisadvantageisthatsomeotherfunctionalgroupsaremorereactivethanaldehydes
andketonestowardscatalyticreduction(forexample,carboncarbondoublebonds)andthereforearealsoreduced
undertheseconditions.

MetalHydrideReductions
Byfarthemostcommonlaboratoryreagentsusedtoreducethecarbonylgroupofanaldehydeorketonetoa
hydroxylgrouparesodiumborohydrideandlithiumaluminiumhydride.Eachofthesecompoundsbehavesasa
sourceofthehydrideion,H,whichisaverystrongnucleophile.Ahydrideionisahydrogenatomwithtwo
electronsinitsvalenceshell, .Thestructuralformulaedrawnbelowshowformalnegativechargesonboronand
aluminium.

Infact,hydrogenismoreelectronegativethaneitherboronoraluminium(H=2.2,Al=1.6andB=2.0)andthe
formalnegativechargeinthetworeagentsresidesmoreonhydrogenatomsthanonthemetal.
Lithiumaluminiumhydrideisaverypowerfulreducingagentitrapidlyreducesnotonlythecarbonylgroupsof
aldehydesandketones,butalsothoseofcarboxylicacidsandtheirfunctionalderivatives(section23.5).Sodium
borohydrideisamuchmoreselectivereagent,reducingonlyaldehydesandketonesrapidly.

Reductionsusingsodiumborohydridearemostcommonlycarriedoutinaqueousmethanol,puremethanolor
ethanol.Theinitialproductofreductionisatetraalkylborate,whichisconvertedtoanalcoholandsodiumborate
saltsupontreatmentwithwater.Onemoleofsodiumborohydridereduces4molesofaldehydeorketone.

Thekeystepinthemetalhydridereductionofanaldehydeorketoneisthetransferofahydrideionfromthe
reducingagenttothecarbonylcarbonatomtoformatetrahedralcarbonyladditioncompound.Inthisreaction,only
thehydrogenatomattachedtothecarbonatomcomesfromthehydridereducingagentthehydrogenatombonded
totheoxygenatomcomesfromthewateraddedtohydrolysethemetalalkoxidesalt.

Thenexttwoequationsillustratetheselectivereductionofacarbonylgroupinthepresenceofacarboncarbon
doublebondand,alternatively,theselectivereductionofacarboncarbondoublebondinthepresenceofacarbonyl
group.

Selectivereductionofacarbonylgroupcanbecarriedoutusingsodiumborohydride.

Selectivereductionofacarboncarbondoublebondcanbeachievedusinghydrogeninthepresenceofatransition
metalcatalyst.Notethatthisreactionispossiblebecausealkenesareeasiertoreducebycatalyticreductionthan
ketones.Bycarefullymonitoringthereactionandstoppingitafteronemoleequivalentofhydrogenhasbeen
consumed,wecanreadilyobtainthecarbonylcompound.

WORKEDEXAMPLE21.9

ReductionofAldehydesandKetones
Completethefollowingreductions.
(a)
 (b)

Analysis

Thekeyhereistorecognisethatthecarbonatomofthecarbonylgroupwillbecomethealcoholcarbon
atom.Todeterminethestructureofthereductionproduct,simplyaddahydrogenatomtoboththecarbon
andtheoxygenatoms.

Solution

Thecarbonylgroupofthealdehydein(a)isreducedtoaprimaryalcohol,andthatoftheketonein(b)is
reducedtoasecondaryalcohol.
(a)

(b)

Isouranswerreasonable?

Thereductionofaldehydesgivesprimaryalcohols,andreductionofketonesgivessecondaryalcohols.
Checkthatyourproposedstructuresagreewiththisrule.

PRACTICEEXERCISE21.9
Whataldehydeorketonegiveseachofthe
followingalcoholsuponreductionbyNaBH4?
(a)

(b)

(c)
OxidationofAldehydestoCarboxylicAcids
Aldehydesareoxidisedtocarboxylicacidsbyavarietyofcommonoxidisingagents,includingchromicacidand
molecularoxygen.Infact,aldehydesareoneofthemosteasilyoxidisedfunctionalgroups.Oxidationbychromic
acidisillustratedbelowbytheconversionofhexanaltohexanoicacid.

Aldehydesarealsooxidisedtocarboxylicacidsbysilver(I)ions.Onelaboratoryprocedureistoshakeasolutionof
thealdehydedissolvedinaqueousethanolortetrahydrofuran(THF)withaslurryofAg 2O.

Tollensreagent,anotherformofsilver(I)ion,ispreparedbydissolvingAgNO3inaqueousammoniatogivethe
silverammoniacomplexiondiamminesilver(I)nitrate.

WhenTollens'reagentisaddedtoanaldehyde,thealdehydeisoxidisedtoacarboxylateanion,andsilverionsare
reducedtometallicsilver.Ifthisreactioniscarriedoutproperly,silverprecipitatesasasmooth,mirrorlikedeposit,
hencethenamesilvermirrortest(figure21.5).
 FIGURE21.5AsilvermirrorhasbeendepositedontheinsideofthisflaskbythereactionofanaldehydewithTollens
reagent.
CharlesDWinters

Nowadays,silverionsarerarelyusedfortheoxidationofaldehydesbecauseofthehighcostofsilverandbecause
other,moreconvenientoxidationmethodsexist.Thereaction,however,isstillcommonlyusedforsilveringmirrors.
Inthisprocess,formaldehydeorglucoseisusedasthealdehydetoreducethesilver(I)ions.

Aldehydesarealsooxidisedtocarboxylicacidsbymolecularoxygenandbyhydrogenperoxide.

Molecularoxygenistheleastexpensiveandmostreadilyavailableofalloxidisingagents,and,onanindustrial
scale,airoxidationoforganicmolecules,includingaldehydes,iscommon.Airoxidationofaldehydescanalsobea
problemaldehydesthatareliquidatroomtemperaturearesosensitivetooxidationbymolecularoxygenthatthey
mustbeprotectedfromcontactwithairduringstorage.Often,thisisdonebysealingthealdehydeinacontainer
underanatmosphereofnitrogen.

WORKEDEXAMPLE21.10

OxidationofAldehydes
Drawastructuralformulaoftheproductformedbytreatingeachofthefollowingcompoundswith
Tollens'reagent,followedbyacidificationwithaqueousHCl.
(a)pentanal
(b)cyclopentanecarbaldehyde

Analysis

Onlythealdehydegroupineachcaseisoxidised.Thisoxidationgivesacarboxylicacidgroup.

Solution
(a)

(b)

Isouranswerreasonable?
Checkthattheproductsarecarboxylicacidsandthatthenumberofcarbonatomsinthestartingmaterial
isthesameastheproduct.

PRACTICEEXERCISE21.10
Completethefollowingoxidations.
(a)3oxobutanal+O2
(b)3phenylpropanal+Tollensreagent

ChemistryResearch

MakingMoleculesforMedicines

ProfessorMargaretBrimble,TheUniversityofAuckland

Maturalproductshavelongbeenregardedasnature'smedicinechestbecausetheyofferarich
sourceofcompoundswithcomplexandnovelstructuresthatinspirethedevelopmentofnew
drugs.Thesynthesisofthesechallenging,naturallyoccurringcompoundsinthelaboratoryisa
scientificendeavourthatformsthebackboneofthepharmaceuticalindustry.Bysynthesising
naturalcompoundsandcloselyrelatedsyntheticanalogues,scientistsgleanvaluable
informationabouthowthenaturalcompoundswork,ultimatelyproducingevenbetter
compoundsasdrugcandidates.

ProfessorMargaretBrimble'sresearchgroupfocusesonmakingandmodifyingcomplex,rare,
bioactivecompoundsderivedfromplants,animaltissues,microbes,ormarineandsoil
organismsthatexhibitantimicrobial,anticancerorantiviralactivity.Thesynthesesofthe
bioactivetargetssheandherteamprepareofteninvolve30ormorestepsand,aseachstep
posesauniquechallenge,theprojectcantakeyearstocomplete.

Oneareaofextensiveresearchisthesynthesisofshellfishtoxins,whichareassociatedwiththe
algalblooms(figure21.7)thatoccurincoastalwaters(redtidephenomena).Suchblooms
mayhaveadevastatingeffectonfishandmarinespecies,oftenresultingintheclosureof
shellfishfarms.Inhumans,thetoxinscausesymptomsrangingfromdiarrhoeatoextreme
cardiovascularandneurotoxiceffects.Sinceshellfishtoxinstargetionchannelstocausethese
biologicaleffects,moleculesthatcanmodulatethefunctionofionchannelsareusefulstarting
pointsfortherationaldesignanddevelopmentofdrugs.Thesemoleculesmayimpacton
clinicalconditionsrangingfrompain,epilepsyandhypertensionthroughtomajordiseasessuch
asstrokeandcancer.Shellfishtoxinsalsorepresentsomeofthemostcomplexmolecular
structuresknown,thusprovidingsyntheticchemistssignificantchallengestoachievetheir
synthesis.

Onefamilyofshellfishtoxinsunderinvestigationisafamilycalledthespirolides(seefigure
21.6),whichwereisolatedfromthedigestiveglandsofcertainmusselsandscallopsduring
algalbloomsinCanada.Theprefixspiroreferstostructuresthatinvolvetworingsjoinedat
onecommonatom.Thespirolidescontainanunusualspiroacetalring,wherethetwooxygen
atomsoftheacetalformthespirostructure,aswellasararespiroiminering.IminesinvolveaC
Ndoublebondandusuallyarereadilyhydrolysed.Asimilarspiroimineringsystemisfound
ingymnodimine,whichhasbeenisolatedfromshellfishcollectedafteroutbreaksofalgal
bloomsinNewZealand.
FIGURE21.6Structureofthespirolides.
 FIGURE21.7AnalgalbloomnearCapeRodney,NewZealand.

Thesynthesisofthespirolidesprovidescompoundsforthedevelopmentofpharmacological
probesfortheactivationofLtypecalciumchannels,whichareresponsibleforthecontraction
ofmyocardialandvascularsmoothmuscles.CompoundsthatblockLtypecalciumchannels
provideatherapeuticapproachtotreatcardiovascularconditionssuchashypertension.The
synthesisofspirolidesrequiresanunderstandingthatthesemoleculesarechiral(seechapter17)
andknowledgeofhowthefunctionalgroupscontainedinthesemoleculesreact.Tocheck
whetherthereactionsusedtoconstructthespirolideshaveinfactworked,NMRspectraare
recordedforallofthesyntheticintermediates(seechapter20).

Inotherwork,theBrimblegrouprecentlyaccomplishedmoreefficientsynthesisof
gammarubromycin(figure21.8),apotentinhibitorofhumantelomerase.Telomeresarethe
protectiveendsofchromosomesconsistingofarepetitivesequencethatshortenswitheachcell
division.Theyserveasamitoticclockthatcontrolsthenumberofdivisionsthatacellcan
undergobeforeenteringsenescence.Thelengthofatelomereismaintainedbytelomerase,a
uniqueenzymethataddsthetelomericrepeatsontotheendsofthechromosome.Telomerase
helpspreventthefrayingofchromosomesthatunderliesmanyageingandcancerprocesses.
The2009NobelPrizeinmedicinewasawardedforthediscoveryoftelomeresandthe
telomeraseenzyme.
 FIGURE21.8Aconceptualdepictionofgammarubromycinanditsinteractionwithtelomerase.

Thenewsynthesisofgammarubromycinismoreefficientthanthepreviouslyreported
approachandproducesthisimportanttelomeraseinhibitorinmuchbetteroverallyield.
However,morethan16stepsarestillrequiredtopreparegammarubromycin,andthetactics
andsyntheticmanoeuveringrequiredinasynthesislikethishavebeencomparedtothelogic
andrationalebehindagameofchess.But,inthisgame,youfirsthavetolearnhowthepieces
movebyunderstandingthereactionsoffunctionalgroups.

OxidationofKetonestoCarboxylicAcids
Ketonesaremuchmoreresistanttooxidationthanaldehydes.Forexample,ketonesarenotnormallyoxidisedby
chromicacidorpotassiumpermanganateatroomtemperature.Infact,thesereagentsareusedroutinelytooxidise
secondaryalcoholstoketonesingoodyield(section19.2).

Ketonesundergooxidativecleavage,viatheirenolform(seebelow),usingpotassiumdichromateandpotassium
permanganateathighertemperatures,aswellasbyhigherconcentrationsofnitricacid,HNO3.Thecarboncarbon
doublebondoftheenoliscleavedtoformtwocarboxylorketonegroups,dependingonthesubstitutionpatternof
theoriginalketone.Animportantindustrialapplicationofthisreactionistheoxidationofcyclohexanoneto
hexanedioicacid(adipicacid),oneofthetwomonomersrequiredforthesynthesisofthepolymernylon6,6(section
26.3).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
21.6KetoenolTautomerism
Acarbonatomadjacenttoacarbonylgroupiscalledancarbon,andanyhydrogenatomsbondedtoitare
calledhydrogens.

Analdehydeorketonethathasatleastonehydrogenatomisinequilibriumwithaconstitutionalisomer
calledanenol.ThenameenolisderivedfromtheIUPACdesignationofitasbothanalkene(en)andan
alcohol(ol).

Ketoandenolformsareexamplesoftautomers,whichareconstitutionalisomersinequilibriumwitheach
other.Tautomersdifferinthelocationofahydrogenatomandadoublebondrelativetoaheteroatom,most
commonlyO,SorN.Thistypeofisomerismiscalledtautomerism.

Formostsimplealdehydesandketones,thepositionoftheequilibriuminketoenoltautomerismliesfaronthe
sideoftheketoform(table21.4),becauseacarbonoxygendoublebondisstrongerthanacarboncarbon
doublebond.
TABLE21.4 Thepositionofketoenolequilibriumforfouraldehydesandketones.
Ketoform Enolform %Enolatequilibrium

610 5

610 7

110 6

110 5

Theequilibrationofketoandenolformsiscatalysedbyacid,asshowninthefollowingtwostepmechanism
(notethatamoleculeofHAisconsumedinstep1,butanotherisgeneratedinstep2):
Step1:Protontransferfromtheacidcatalyst,HA,tothecarbonyloxygenatomformstheconjugateacid
ofthealdehydeorketone.
Step2:Protontransferfromthecarbonatomtothebase,A,givestheenolandgeneratesanew
moleculeoftheacidcatalyst,HA.

Thistautomerismcanalsobebasecatalysed.Theprocessisthereverseoftheacidcatalysedprocessinthat
thebaseremovesaprotonfromthecarbonatomfirst.Theresultingalkoxidethenremovesaprotonfrom
theconjugateacid(formedwhenthebaseremovesthehydrogenatom).

WORKEDEXAMPLE21.11

EnolForms
Writetwoenolformsforeachofthefollowingcompounds,andstatewhichenolpredominatesat
equilibrium.
(a)

(b)

Analysis

Thecarbonatomofthecarbonylgroupwillremainsp 2hybridised(itwillbepartofthealkeneinthe
enol).Thetwopossibleenolsareobtainedbyremovalofanhydrogenatomfromthetwocarbon
atoms.Zaitsev'srule(section18.3)willhelppredictthemajorenolform.

SolutionIneachcase,themajorenolformhasthemoresubstituted(themorestable)carboncarbon
doublebond.
(a)
 (a)

(b)

Isouranswerreasonable?

Checkthatoneoftheatomsinthealkenegroupwasthecarbonylcarbonatom.

PRACTICEEXERCISE21.11
Drawthestructuralformulafortheketoformof
eachofthefollowingenols.
(a)

(b)

(c)

RacemisationatancarbonAtom
Whenenantiomericallypure(eitherRorS)3phenylbutanoneisdissolvedinethanol,nochangeoccursinthe
opticalactivityofthesolutionovertime.If,however,atraceofacidisadded,theopticalactivityofthesolution
beginstodecreaseandgraduallydropstozero.When3phenylbutanoneisisolatedfromthissolution,itis
foundtobearacemicmixture(section17.5).Thisobservationcanbeexplainedbytheacidcatalysedformation
ofanachiralenolintermediate.Inthetautomerismoftheachiralenoltothechiralketoform,thehydrogenion
canaddtocarbon3oftheenoletherfromaboveorbelowtogeneratetheRandSenantiomerswithequal
probability.
Racemisationbythismechanismoccursonlyatcarbonstereocentreswithatleastonehydrogenatom.

Halogenation
Aldehydesandketoneswithatleastonehydrogenatomreactwithbromineandchlorineatthecarbonatom
togiveanhaloaldehydeorhaloketone.Acetophenone,forexample,reactswithbromineinaceticacidto
givebromoacetophenone,anbromoketone.

Acidicandbasicconditionsbothcatalysehalogenation.Foracidcatalysedhalogenation,theHBrorHCl
generatedcatalysesfurtherreaction.
Step1:Acidcatalysedketoenoltautomerismgivestheenol.

Step2:Nucleophilicattackoftheenolonthehalogenmoleculegivesthehaloketone.

Thevalueofhalogenationisthatitconvertsancarbonatomintoacentrethathasagoodleavinggroupand
isthereforesusceptibletosubstitutionbyavarietyofgoodnucleophiles.Inthefollowingexample,
diethylamine(anucleophile)reactswiththebromoketonetogiveandiethylaminoketone.
Inpractice,thistypeofnucleophilicsubstitutionisgenerallycarriedoutinthepresenceofaweakbase,suchas
potassiumcarbonate,toneutralisetheHXasitisformed.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
StructureandBonding
Analdehydecontainsacarbonylgroupbondedtoahydrogenatomandacarbonatom.Aketone
containsacarbonylgroupbondedtotwocarbonatoms.

Nomenclature
Analdehydeisnamedbychangingtheesuffixoftheparentalkanetoal.ACHOgroupbondedtoa
ringisindicatedbythesuffixcarbaldehyde.Aketoneisnamedbychangingtheesuffixoftheparent
alkanetooneandusinganumbertolocatethecarbonylgroup.Innamingcompoundsthatcontain
morethanonefunctionalgroup,theIUPACsystemhasestablishedanorderofprecedenceoffunctional
groups.Ifthecarbonylgroupofanaldehydeoraketoneislowerinprecedencethanotherfunctional
groupsinthemolecule,itisindicatedbytheinfixoxo.

PhysicalProperties
Aldehydesandketonesarepolarcompoundsandinteractinthepurestatebydipoledipoleinteractions
theyhavehigherboilingpointsandaremoresolubleinwaterthannonpolarcompoundsofsimilar
molarmassandsimilarnumberofelectrons.

PreparationofAldehydesandKetones
Aldehydesandketonescanbepreparedfromvariousfunctionalgroupsusingmanydifferentreactions.
FriedelCraftsacylationofaromaticcompoundsyieldsketones(aldehydescannotbeobtainedbythis
method).Aldehydesandketonescanbepreparedbytheoxidationofalcoholsprimaryalcoholsgive
aldehydes,andsecondaryalcoholsgiveketones.Ozonolysisofalkenescleavesthecarboncarbon
doublebondtoproducetwocarbonylgroups.Ketonescanalsobepreparedbythehydrationof
alkynes.Thisprocessproceedsviaanenol,whichundergoestautomerismtogivetheketone.

Reactions
Aldehydesandketonesareveryreactivegroupsduetothepolarityandstructureofthecarbonylgroup.
Aldehydesareusuallymorereactivethanketonesbecauseaccesstothecarbonylgroupiseasier.The
mostcommonreactionofthecarbonylgroupistheadditionofanucleophiletoformatetrahedral
carbonyladditionintermediate.

Alkyl,arylandvinylichalidesreactwithcertainmetalstoformorganometalliccompounds.
OrganomagnesiumcompoundsarecommonlycalledGrignardreagents.Thecarbonmetalbondin
Grignardreagentshasapartialioniccharacter.Grignardreagentsbehaveascarbanionsandareboth
strongbasesandgoodnucleophiles.

Treatmentofaldehydesandsomeketoneswithsodiumcyanideanddiluteacidproducescyanohydrins,
compoundswithanOHandaCNbondedtothesamecarbonatom.

Theadditionofanalcoholmoleculetothecarbonylgroupofanaldehydeorketoneformsahemiacetal.
ThehemiacetalfunctionalgroupisacarbonatombondedtoanOHgroupandanORorOAr
group.Hemiacetalscanreactfurtherwithalcoholstoformacetalsplusamoleculeofwater.Theacetal
functionalgroupisacarbonatombondedtotwoORorOArgroups.

Ammonia,primaryaliphaticamines,RNH2,andprimaryaromaticamines,ArNH2,reactwiththe
carbonylgroupofaldehydesandketonesinthepresenceofanacidcatalysttogiveimines(compounds
thatcontainacarbonnitrogendoublebond).Whenaldehydesandketonesreactwithhydroxylamine,
H2NOH,theyformoximes(compoundscontainingaC NOHgroup).Aprimaryamineisconverted
toasecondaryaminebywayofanimineinatwostepreactioncalledreductiveamination.

Aldehydesarereducedtoprimaryalcohols.Ketonesarereducedtosecondaryalcohols.Sodium
borohydrideandlithiumaluminiumhydridearethemostcommonlaboratoryreagentsusedtoreduce
thecarbonylgroupofanaldehydeorketone.Eachactsasasourceofahydrideion,whichisavery
strongnucleophile.

Aldehydesareoneofthemosteasilyoxidisedofallfunctionalgroups.Theyoxidisetocarboxylicacids.
TheadditionofTollens'reagentoxidisesanaldehydetoacarboxylateanionandsilverionsarereduced
tometallicsilver.Silverfromthisreactionprecipitatesasasmooth,mirrorlikedeposit,andthereaction
isknownasthesilvermirrortest.

KetoenolTautomerism
Acarbonatomadjacenttoacarbonylgroupiscalledancarbon,andahydrogenattachedtoitis
calledanhydrogen.Analdehydeorketonethathasatleastonehydrogenatomisinequilibrium
withaconstitutionalisomercalledanenol.Constitutionalisomersinequilibriumwitheachotherthat
differinthelocationofahydrogenatomandadoublebondrelativetoaheteroatomarecalled
tautomers,andthistypeofisomerismiscalledtautomerism.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
PreparationofketonesbyFreidelCraftsacylation(section21.4)
KetonescanbepreparedbyFriedelCraftsacylationofaromaticcompounds.

Preparationofaldehydesandketonesbyoxidationofalcohols(section21.4)
Primaryalcoholscanbeoxidisedundermildconditionstogivealdehydes,andsecondaryalcoholscan
beoxidisedtogiveketones.

Preparationofaldehydesandketonesbyozonolysisofalkenes(section21.4)
Alkenesarereadilycleavedbyozone,whichwhenfollowedbyreductivehydrolysisgivesaldehydes
and/orketones.

Preparationofketonesbyhydrationofalkynes(section21.4)
Hydrationofalkynesyieldsketones.

ReactionwithGrignardreagents(section21.5)
TreatmentofformaldehydewithaGrignardreagent,followedbyhydrolysisinaqueousacid,givesa
primaryalcohol.Similartreatmentofanyotheraldehydegivesasecondaryalcohol.

Additionofothercarbonnucleophiles(section21.5)
TreatmentofaketonewithaGrignardreagentgivesatertiaryalcohol.
Aldehydesandketoneswillreactwithcyanideionstoformcyanohydrins.

Additionofalcoholstoformhemiacetals(section21.5)
Hemiacetalsareonlyminorcomponentsofanequilibriummixtureofanaldehydeoraketone,andan
alcohol,exceptwheretheOHandC Ogroupsarepartsofthesamemoleculeandafiveorsix
memberedringcanform.

Additionofalcoholstoformacetals(section21.5)
Theformationofacetalsiscatalysedbyacid.

Additionofammoniaandamines(section21.5)
Theadditionofammoniaoraprimaryaminetothecarbonylgroupofanaldehydeoraketoneformsa
tetrahedralcarbonyladditionintermediate.Lossofwaterfromthisintermediategivesanimine.

Formationofoximes(section21.5)
Thecondensationofaldehydesandketoneswithhydroxylaminegivesoximes.

Reductiveaminationtoamines(section21.5)
Thecarbonnitrogendoublebondofaniminecanbereducedbyhydrogeninthepresenceofa
transitionmetalcatalysttoacarbonnitrogensinglebond.
Catalyticreduction(section21.5)
Catalyticreductionofthecarbonylgroupofanaldehydeoraketonetoahydroxylgroupcanbe
achievedinhighyields.However,thisoccursmuchmoreslowlythanthereactionofalkenesand
requiresmorevigorousconditions.

Metalhydridereduction(section21.5)
BothLiAlH4andNaBH4reducethecarbonylgroupofanaldehydeoraketonetoahydroxylgroup.
Theyareselectiveinthatneitherreducesisolatedcarboncarbondoublebonds.

Oxidationofanaldehydetoacarboxylicacid(section21.5)
Thealdehydegroupisamongthemosteasilyoxidisedfunctionalgroups.Oxidisingagentsinclude
H2CrO4,silver(I)ionsincludingTollens'reagent,andO2.

Ketoenoltautomerism(section21.6)
Theketoformofanaldehydeoraketonegenerallypredominatesovertheenolformatequilibrium.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Structureandbonding
21.1Drawstructuralformulaefortheoneketoneandtwoaldehydeswiththemolecularformula
C4H8O.
21.2DrawstructuralformulaeforthefouraldehydeswiththemolecularformulaC5H10O.Whichof
thesealdehydesarechiral?
21.3Usethe+andnotationtoshowthepolarityofthefollowingcarbonylcompounds.
(a)

(b)

21.4Compareandcontrastthebondinginacarbonylgroup(C O)andanalkenegroup(C C).

Whatarethesimilaritiesandwhatarethedifferences?
Nomenclature
21.5Drawstructuralformulaecorrespondingtothefollowingcompoundnames.
(a)bromoacetone
(b)methylbutanone
(c)3,5dinitrobenzaldehyde
(d)3,5dimethylcyclohexanone
(e)tetramethylpentan3one
(f) butandial
(g)3hydroxybutanone
(h)3phenylpropenal
21.6Drawstructuralformulaecorrespondingtothefollowingcompoundnames.
(a)chloropropanone
(b)3hydroxybutanal
(c)4hydroxy4methylpentan2one
(d)3methyl3phenylbutanal
(e)(S)3bromocyclohexanone
(f) 3methylbut3enone
(g)5oxohexanal
 (h)2,2dimethylcyclohexanecarbaldehyde
(i) 3oxobutanoicacid
21.7NamethefollowingcompoundsusingtheIUPACsystemofnomenclature.
(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

21.8NamethefollowingcompoundsusingtheIUPACsystemofnomenclature.
(a)

(b)

(c)
 (d)

(e)

(f)

(g)

(h)

21.9Provideasystematic(IUPAC)nameforeachofthefollowingcompounds.
(a)

(b)

(c)
 (d)

21.10Namethefamilytowhicheachofthefollowingcompoundsbelongs.
(a)CH3CH CH2
(b)CH3CH2OH
(c)

(d)

(e)CH3CH2CH2NH2
(f) HOCH2CH2CH3
21.11Towhichorganicfamilydoeseachofthefollowingcompoundsbelong?
(a)CH3C CH
(b)

(c)

(d)CH3OCH2CH3
(e)CH3CH2NH2
(f)

PhysicalProperties
21.12Whydoaldehydesandketoneshaveboilingpointsthatarelowerthanthoseoftheir
correspondingalcohols?
21.13Explainwhyaldehydesandketoneshavehigherboilingpointsthanalkanesofsimilarmolar
massandsimilarnumberofelectrons.
21.14Whichwouldyouexpecttobemoresolubleinwater,acetaldehyde(ethanal)orhexanal?Explain
youranswer.
21.15Whichwouldyouexpecttobemoresolubleinwater,acetone(propanone)orhexan3one?
 Explainyouranswer.
21.16Withtheaidofasketch,showthehydrogenbondingbetweenwaterandpropanal.
21.17Useasketchtoshowthehydrogenbondingbetweenmethanolandbutanone.
PreparationofAldehydesandKetones
21.18Completethefollowingreactions.
(a)

(b)

(c)

(d)

21.19GivethestructuralformulaeofthealdehydeorketoneobtainedbythePCCoxidationofthe
followingalcohols.
(a)1phenylethanol
(b)2phenylethanol
21.20Givethestructuralformulaeoftheketone(s)obtainedbythehydrationofthefollowingalkynes.
(a)hex1yne
(b)hex2yne
(c)hex3yne
21.21Givethestructuralformulaeofthecarbonylcompoundsobtainedbyozonolysisandreductive
hydrolysisofthefollowingalkenes.
(a)

(b)

(c)

(d)
Reactions
21.22WritethestructuresoftheisomericalcoholswiththeformulaC4H10Othatcouldbeoxidisedto
aldehydes.Writethestructureoftheisomerthatcouldbeoxidisedtoaketone.
21.23Whichisomerofbutan1olcannotbeoxidisedbydichromateions?Writeitsstructureand
IUPACname.
21.24Writethestructureoftheprincipalorganicproductofeachofthefollowingreactions:
(a)magnesiumwith2iodopropaneindiethylether
(b)theproductof(a)withformaldehydeinether,followedbydiluteacid
(c)theproductof(a)withcyclopentanoneinether,followedbydiluteacid
(d)theproductof(a)withbenzaldehydeinether,followedbydiluteacid.
21.25Writeanequationfortheacidbasereactionbetweenphenylmagnesiumiodideandacarboxylic
acid.Usecurvedarrowstoshowthebondbreakingandbondformingstepsinthisreaction.In
addition,showthatthereactionisanexampleofastrongeracidandstrongerbasereactingto
formaweakeracidandweakerbase.
21.26Drawstructuralformulaefortheproductformedbytreatingeachofthefollowingcompounds
withpropylmagnesiumbromide,followedbyhydrolysisinaqueousacid.
(a)CH2O
(b)

(c)

21.27Drawstructuralformulaefortheproductformedbytreatingeachofthefollowingcompounds
withpropylmagnesiumbromide,followedbyhydrolysisinaqueousacid.
(a)

(b)

21.28Predicttheproductofthereactionofpropanalwitheachofthefollowingreagents.
(a)lithiumaluminiumhydride,followedbytreatmentwithwater
(b)sodiumborohydrideinmethanol
(c)hydrogenwithanickelcatalyst
 (d)methylmagnesiumiodide,followedbydiluteacid
(e)aniline(PhNH2)
(f) 4nitrophenylhydrazine
(g)sodiumcyanidewithadditionofsulfuricacid
(h)silverammoniacomplex(Tollens'reagent)
(i) acidifiedpotassiumdichromatesolution
21.29Repeatquestion21.28withcyclopentanoneasthereactant.
KetoenolTautomerism
21.30Writethestructuralformulaeforallpossibleenolsof:
(a)pentanal
(b)pentan2one
(c)pentan3one.
21.31Writethestructuralformulaeofallpossibleproductsresultingfromthebrominationofthe
followingketones:
(a)pentan2one
(b)pentan3one
(c)cyclopentanone.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
21.32Completethefollowingreactions.
(a)

(b)

(c)

(d)

21.33Foreachofthefollowingpairs,identifywhichcompoundwouldbeexpectedtoreactmore
rapidlywithanucleophile.
(a)

(b)

21.34Howcanthefollowingconversionsbecarriedout?
(a)pentan1oltopentanal
(b)pentan1oltopentanoicacid
(c)pentan2oltopentan2one
(d)pent1enetopentan2one
(e)benzenetoacetophenone
(f) styrenetoacetophenone
(g)cyclohexanoltocyclohexanone
(h)cyclohexenetocyclohexanone
21.35Suggestasynthesisforeachofthefollowingalcohols,startingfromanaldehydeorketoneand
anappropriateGrignardreagent.(ThenumberofcombinationsofGrignardreagentandaldehyde
orketonethatmightbeusedisshowninparenthesesbeloweachtargetmolecule.)
(a)
 (b)

(c)

21.36ChooseaGrignardreagentandaketonethatcanbeusedtoproduceeachofthefollowing
compounds.
(a)3methyl3pentanol
(b)1ethylcyclohexanol
(c)triphenylmethanol
(d)5phenyl5nonanol
21.37Completethefollowingreactionstoshowthemajororganicproduct.
(a)

(b)

(c)

(d)

21.38Drawstructuralformulaeforthehemiacetalandthentheacetalformedfromeachofthe
followingpairsofreactantsinthepresenceofanacidcatalyst.
(a)
 (b)

(c)

21.39Drawstructuralformulaefortheproductsofhydrolysisofeachofthefollowingacetalsand
ketalsinaqueousacid.
(a)

(b)

(c)

21.40Thefollowingcompoundisacomponentofthefragranceofjasmine.Fromwhatcarbonyl
containingcompoundandalcoholisitderived?

21.41Proposeamechanismfortheformationofthefollowingcyclicacetalbytreatingacetonewith
ethyleneglycolinthepresenceofanacidcatalyst.Makesurethatyourmechanismisconsistent
withthefactthattheoxygenatomofthewatermoleculeisderivedfromthecarbonyloxygen
atomofacetone.
21.42Proposeamechanismfortheformationofacyclicacetalfrom4hydroxypentanalandone
equivalentofmethanol.Ifthecarbonyloxygenatomof4hydroxypentanalisenrichedwith
oxygen18,doesyourmechanismpredictthattheoxygenlabelappearsinthecyclicacetalorin
thewater?Explain.

21.435hydroxyhexanalformsasixmemberedcyclichemiacetalthatpredominatesatequilibriumin
acidicaqueoussolution.

(a)Drawastructuralformulaforthiscyclichemiacetal.
(b)Howmanystereoisomersarepossiblefor5hydroxyhexanal?
(c)Howmanystereoisomersarepossibleforthecyclichemiacetal?
21.44Showhowthesecondaryaminebelowcanbepreparedbytwosuccessivereductiveaminations.

21.45Showhowtoconvertcyclohexanonetoeachofthefollowingamines.
(a)

(b)

(c)

21.46RimantadineiseffectiveinpreventinginfectionscausedbytheinfluenzaAvirusandintreating
theestablishedillness.Thedrugisthoughttoexertitsantiviraleffectbyblockingalatestagein
theassemblyofthevirus.Thefollowingisthefinalstepinthesynthesisofrimantadine.
 (a)Describetheexperimentalconditionswhichbringaboutthisconversion.
(b)Isrimantadinechiral?
21.47Methenamine,aproductofthereactionofformaldehydeandammonia,isaprodruga
compoundthatisinactivebyitselfbutisconvertedtoanactivedruginthebodybya
biochemicaltransformation.Thestrategybehindtheuseofmethenamineasaprodrugisthat
nearlyallbacteriaaresensitivetoformaldehydeatconcentrationsof20mgmL1orhigher.
Formaldehydecannotbeuseddirectlyinmedicinebecauseaneffectiveconcentrationinplasma
cannotbeachievedwithsafedoses.MethenamineisstableatpH7.4(thepHofbloodplasma)
butundergoesacidcatalysedhydrolysistoformaldehydeandammoniumionsundertheacidic
conditionsofthekidneysandtheurinarytract.
 Thus,methenaminecanbeusedasasitespecificdrugtotreaturinaryinfections.
(a)Balancetheequationforthehydrolysisofmethenaminetoformaldehydeandammonium
ions.
(b)DoesthepHofanaqueoussolutionofmethenamineincrease,remainthesameor
decreaseasaresultofthehydrolysisofthecompound?Explain.
(c)Explainthemeaningofthefollowingstatement:Thefunctionalgroupinmethenamineis
thenitrogenanalogueofanacetal.
(d)Accountfortheobservationthatmethenamineisstableinbloodplasmabutundergoes
hydrolysisintheurinarytract.
21.48Drawastructuralformulafortheproductformedbytreatingbutanalwitheachofthefollowing
setsofreagents.
(a)LiAlH4followedbyH2O
(b)NaBH4inCH3OH/H2O
(c)H2/Pt
(d)[Ag(NH ) ]+inNH /H OandthenHCl/H O
32 3 2 2
(e)H2CrO4
(f) C6H5NH2inthepresenceofH2/Ni
21.49Drawastructuralformulafortheproductofthereactionofpbromoacetophenonewitheachset
ofreagentsinquestion21.48.
21.50Showhowyouwouldchemicallydistinguishbetweenthecompoundsinthefollowingsets.
Describeanyobservationsandgiveequationswhereapplicable.
(a)
 (b)

21.51Showhowyouwouldchemicallydistinguishbetweenthefollowingcompounds.Describeany
observationsandgiveequationswhereapplicable.

21.52Thefollowingmoleculebelongstoaclassofcompoundscalledenediols.Eachcarbonatomof
thedoublebondinanenediolcarriesanOHgroup.

Drawstructuralformulaeforthehydroxyketoneandthehydroxyaldehydewithwhichthis
enediolisinequilibrium.
21.53Indiluteaqueousacid,(R)glyceraldehydeisconvertedintoanequilibriummixtureof(R,S)
glyceraldehydeanddihydroxyacetone.

Proposeamechanismforthisisomerisation.
21.54Showthereagentsandconditionsthatwillcausetheconversionofcyclohexanolto
cyclohexanecarbaldehyde.

21.55Startingwithcyclohexanone,showhowtopreparethefollowingcompounds(inadditiontothe
givenstartingmaterial,useanyotherorganicorinorganicreagents,asnecessary).
(a)cyclohexanol
 (b)cyclohexene
(c)1methylcyclohexanol
21.56Startingwithcyclohexanone,showhowtopreparethefollowingcompounds(inadditiontothe
givenstartingmaterial,useanyotherorganicorinorganicreagents,asnecessary).
(a)1methylcyclohexene
(b)1phenylcyclohexanol
(c)1phenylcyclohexene
21.57Glutaraldehydeisagermicidalagentthatissometimesusedtosterilisemedicalequipmentthatis
toosensitivetobeheatedinanautoclave.Inmidlyacidicconditions,glutaraldehydeexistsina
cyclicform(belowright).Drawaplausiblemechanismforthistransformation.

21.58Showhowtobringaboutthefollowingconversions(inadditiontothegivenstartingmaterial,
useanyotherorganicorinorganicreagents,asnecessary).
(a)

(b)

(c)

21.59UsingaGrignardreaction,showhowyoucouldprepareeachofthefollowingalcohols.
(a)

(b)

(c)
 (d)

21.60Whatreagentswouldyouusetoperformeachofthefollowingtransformations?
(a)

(b)

21.61Manytumoursofthebreastareoestrogendependent.Drugsthatinterferewithoestrogenbinding
haveantitumouractivityandmayevenhelppreventtheoccurrenceoftumours.Awidelyused
antioestrogendrugistamoxifen.

(a)Howmanystereoisomersarepossiblefortamoxifen?
(b)Specifytheconfigurationofthestereoisomershownhere.
(c)ShowhowtamoxifencanbesynthesisedfromthegivenketoneusingaGrignardreaction,
 followedbydehydration.
21.62Thefollowingisapossiblesynthesisoftheantidepressantbupropion(Wellbutrin ).

Showthereagentsthatwillbringabouteachstepinthissynthesis.
21.63AnunknowncompoundAgaveapositivesilvermirrortest.ReactionofAwithethylmagnesium
bromidefollowedbytreatmentwithadiluteacidgavecompoundB,C6H14O.CompoundB,
upontreatmentwithconcentratedsulfuricacid,gavecompoundC,C6H12.ReactionofCwith
ozonefollowedbyzincinwatergavetwoproducts,propanalandacetone.Identifyeachofthe
compoundsA,BandC,basedonthechemicalinformationgiven.Writeanequationforeach
reactiondescribedinthequestion.
21.64CompoundA,C5H10O,isusedasaflavouringagentformanyfoodsthatpossessachocolateor
peachflavour.Itscommonnameisisovaleraldehydeanditgives13CNMRpeaksat202.7,
52.7,23.6and22.6.ProvideastructuralformulaforisovaleraldehydeandgiveitsIUPACname.
21.65Thefollowingisasynthesisfordiphenhydramine.
 Thehydrochloridesaltofthiscompound,bestknownbyitstradename,Benadryl,isan
antihistamine.
(a)Proposereagentsforsteps1and2.
(b)Proposereagentsforsteps3and4.
(c)Showthatstep5isanexampleofnucleophilicaliphaticsubstitution.Whattypeof
mechanism,SN1orSN2,ismorelikelyforthisreaction?Explain.
21.66Thefollowingisasynthesisfortheantidepressantvenlafaxine.
 (a)Proposeareagentforstep1,andnamethetypeofreactionthattakesplace.
(b)Proposereagentsforsteps2and3.
(c)Proposereagentsforsteps4and5.
(d)Proposeareagentforstep6,andnamethetypeofreactionthattakesplace.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
21.67Diethyletherispreparedonanindustrialscalebytheacidcatalyseddehydrationofethanol.

ExplainwhydiethyletherusedinthepreparationofGrignardreagentsmustbecarefullypurifiedtoremove
alltracesofethanolandwater.
21.68IdentifythestructuresofcompoundsAtoEbelow.

21.69ReactionofaGrignardreagentwithcarbondioxide,followedbytreatmentwithaqueousHCl,givesa
carboxylicacid.Proposeastructuralformulaforthebracketedintermediateformedbythereactionof
phenylmagnesiumbromidewithCO2,andproposeamechanismfortheformationofthisintermediate.

21.70Providetheenolformoftheketonebelowandpredictthepositionofequilibrium.

21.71Howwouldyouprepare6hydroxyhexan2onefrommethyl5oxohexanoate?Estersarereadilyreducedto
primaryalcoholswithlithiumaluminiumhydride.Morethanonestepisrequired.

21.72DrawthecyclichemiacetalformedbyreactionofthehighlightedOHgroupwiththealdehydegroup.
(a)
 (b)

21.73Showhowthefollowingtransformationscanbecarriedout.Givethereagentsrequiredandthestructureof
anyintermediatecompounds.Morethanonestepisrequiredinallcasesandmorethanonemethodmaybe
possible.
(a)

(b)

(c)

(d)

21.74Proposeamechanismfortheacidcatalysedreactionofthefollowinghemiacetal,withanamineactingasa
nucleophile.

21.75IdentifythestructuresofcompoundsAtoCbelow,andthenidentifythereagentsthatcanbeusedtoconvert
cyclohexeneintocompoundCinjustonestep.
21.76AnaldehydewiththemolecularformulaC H OexhibitsanIRsignalat1715cm1.
4 6
(a)Proposetwopossiblestructuresthatareconsistentwiththisinformation.
(b)Describehowyoucoulduse13CNMRspectroscopytodeterminewhichofthetwopossiblestructures
iscorrect.
21.77Thefollowingare1HNMRandIRspectra(seechapter20)ofcompoundB,C H O .Proposeastructural
6 12 2
formulaforcompoundB.

21.78AcompoundwiththemolecularformulaC H Oexhibitsastrongsignalat1687cm1initsIRspectrum.The
9 10
1Hand13CNMRspectraofthecompoundareshownbelow.Identifythestructureofthiscompound.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
carbon Grignardreagent oximes
hydrogens hemiacetal reductiveamination
acetal hydrideion silvermirrortest
aldehyde ketal tautomerism
carbanion ketone tautomers
cyanohydrins orderofprecedenceof tetrahedralcarbonyladdition
enol functionalgroups intermediate
organometalliccompounds Tollensreagent

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

22 Carbohydrates
Carbohydratesisachemicaltermthatalmosteverybodyknowsanduses,perhapswithoutafull
understandingofitsmeaning.Carbohydratesrepresentamajorclassoforganicmoleculesthatareimportant
inareasrangingfromfoodtomaterialsandmedications.Theyaresomeofthemostabundantandimportant
compoundsintheplantandanimalworld.Carbohydratesgiveplantcellwallsthestrengthandrigiditythey
need,andtheyaccountforapproximatelythreequartersofthedryweightoftheplant.Animalcellsare
coveredinadensearrayofcarbohydratechainsthatarecriticalforacell'ssurvivalandhealthyfunction.
Carbohydratesactasstorehousesofchemicalenergy(glucose,starch,glycogen)andarecomponentsof
supportivestructuresinplants(cellulose),crustaceanshells(chitin)andconnectivetissuesinanimals
(polysaccharides).Animals(includinghumans)gettheircarbohydratesfromeatingplants,buttheydonot
storemuchofwhattheyconsume,withlessthanonepercentofthebodyweightofananimalbeingmadeof
carbohydrates.However,theircrucialroleinbiologicalchemistryisfargreaterthanthisimplies.Theyare
essentialcomponentsinthenucleicacidsRNA(Dribose)andDNA(2deoxyDribose),andtheyplaycrucial
rolesincellsurfaceandmembranerecognitionnecessaryforcellfunction.Smallcarbohydratemolecules,
suchasglucose,arereadilysolubleinwaterandsocanbetransportedthroughthevascularsystemtomeeta
plant'soranimal'senergyneeds.

Oursocietyisalsointegrallylinkedtocarbohydrates,notonlyforfoodbutalsoaskeydriversinour
economy.ForexampleAustralia'swheat(starch)andsugarcane(sucrose)industriesaloneareworthmore
than$7.5billionperyear.EquallyimportantinNewZealand,agriculturerepresentsthreequartersofthe
economy,withNewZealandexportingmorethan$1billionoffruiteachyear,includingsupplyingone
quarteroftheworld'skiwifruit.
 KEYTOPICS

22.1Introductiontocarbohydrates
22.2Monosaccharides
22.3Thecyclicstructureofmonosaccharides
22.4Reactionsofmonosaccharides
22.5Disaccharidesandoligosaccharides
22.6Polysaccharides

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22.1IntroductiontoCarbohydrates
Carbohydratespossessmanyfunctionalgroups,whichleadstosomeinterestingproperties.Theyare
alsooffundamentalimportanceasbiochemicals.Inchapters19and21wedealtwiththeindividual
functionalgroupsfoundincarbohydrates(alcohols,aldehydesandketones),somanyoftheproperties,
reactivitiesandconceptswillbefamiliar.Therangeandvarietyofcarbohydratechemistryareimmense
andwewillcoveronlythesimplestforms.However,itiscrucialtorememberthatallcarbohydrates,no
matterhowcomplex,aregovernedbythepropertiesoftheindividualchemicalgroupsfromwhichthey
areconstructed.

ThewordcarbohydratemeanshydrateofcarbonandderivesfromtheformulaCn(H2O)m.Two
examplesofcarbohydrateswithmolecularformulaethatcanbewrittenashydratesofcarbonare:
glucose(bloodsugar),C6H12O6,whichcanbewrittenasC6(H2O)6
sucrose(tablesugar),C12H22O11,whichcanbewrittenasC12(H2O)11.

However,notallcarbohydrateshavethisgeneralformula.Somecontaintoofewoxygenatoms,and
somecontaintoomany.Somealsocontainnitrogen.Butthetermcarbohydratehasbecomefirmly
rootedinchemicalnomenclatureand,althoughnotcompletelyaccurate,itpersistsasthenameforthis
classofcompounds.

Atthemolecularlevel,mostcarbohydratesarepolyhydroxyaldehydes,polyhydroxyketonesor
compoundsthatyieldthemafterhydrolysis.Therefore,thechemistryofcarbohydratesisessentiallythe
chemistryofhydroxylandcarbonylgroups,andoftheacetalbonds(section21.5)formedbetween
thesetwofunctionalgroups.

Almostallcarbohydratesarechiral.Thismeansthattheyinteractwithplanepolarisedlight(seechapter
17).Chiralityissignificantfortheirbiologicalactivityasmanycellularinteractionsarecontrolledby
specificcarbohydratestereoisomers.Thisisalsowhybloodtransfusionsrequirespecificmatchingblood
types,thedifferentbloodtypesarisefromdifferentcarbohydratespresentonthesurfaceofcells.
Anotherimportantfactorgovernedbythedifferentstructuresofcarbohydratesistheirperceived
sweetness.Onecarbohydratemaybeverysweetwhileanotherwithonlyaminorstructuraldifference
mayhavelittleapparentsweetness.Notably,allofthevariouscarbohydratesfromthesimplest
throughtothemostcomplexstereoisomersimportantinbiologicalactivityhaveultimatelyarisen
fromthesimplenonchiralCO2moleculeviaplantphotosynthesis.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
22.2Monosaccharides
ThewordsaccharidecomesfromtheancientLatinwordforsweetandmonosaccharidesarethesimplest
formsofcarbohydrate,unabletobehydrolysedtoanythingsmaller.

MonosaccharideshavethegeneralformulaCnH2nOn,withoneofthecarbonatomsbeingpartofacarbonyl
groupofeitheranaldehydeoraketone.Themostcommonmonosaccharidescontainfromthreetonine
carbonatoms.Thereisacommonnamingsystemwherethesuffixoseindicatesthatamoleculeisa
carbohydrate,andtheprefixestri,tetr,pent,andsoon,indicatethenumberofcarbonatomsinthechain.
Monosaccharidescontaininganaldehydegroupareclassifiedasaldosesthosecontainingaketonegroup
areclassifiedasketoses.

Thereareonlytwotriosesglyceraldehyde,whichisanaldotriose,anddihydroxyacetone,whichisa
ketotriose.

Oftenthedesignationsaldoandketoareomitted,andthesemoleculesarereferredtosimplyastrioses,
tetrosesetc.Althoughthesenamesdonotdescribethenatureofthecarbonylgroup,theydoindicatethatthe
monosaccharidecontainsthreeandfourcarbonatoms,respectively.

RememberthatthesemoleculescanalsobenamedusingtheIUPACnomenclaturesystem(seechapter2).
Forexample,thecorrectIUPACnameforglyceraldehydeis2,3dihydroxypropanal,anddihydroxyacetone
ismorecorrectlycalled1,3dihydroxypropanone.

Stereoisomerism
Glyceraldehydecontainsonestereocentreandexistsasapairofenantiomers(seechapter17).The
stereoisomershownatthetopleftonthenextpagehastheRconfigurationandisnamed(R)
glyceraldehyde,whileitsenantiomer,shownatthetoprightonthenextpage,isnamed(S)glyceraldehyde.
FischerProjections
ChemistscommonlyusetwodimensionalrepresentationscalledFischerprojectionstoshowthethree
dimensionalconfigurationofcarbohydrates.TodrawaFischerprojection,drawathreedimensional
representationwiththemostoxidisedcarbonatomtowardsthetopandthemoleculeorientedsothatthe
verticalbondsfromeachstereocentrearedirectedawayfromyouandthehorizontalbondsaredirected
towardsyou.Thenwritethemoleculeasatwodimensionalfigurewitheachstereocentreindicatedbythe
pointatwhichthebondscross.YounowhaveaFischerprojection.

ThetwohorizontalsegmentsofthisFischerprojectionrepresentbondsdirectedtowardsyou,andthetwo
verticalsegmentsrepresentbondsdirectedawayfromyou.Theonlyatomintheplaneofthepaperisthe
stereocentre.NotethatyoucannottreataFischerprojectionasa3Dobjectasyoucanwiththestructureon
theleft.ThehorizontalandverticallinesinaFischerprojectionhavestructuralimplications.Ifyourotatea
Fischerprojectionby90thenyoucreateanew3Dstructure.

DandLmonosaccharides

EventhoughtheR,Ssystemiswidelyacceptedasastandardfordesignatingtheconfigurationof
stereocentres,westillcommonlyindicatetheconfigurationofcarbohydratesusingtheD,Lsystemproposed
byEmilFischerin1891.Heassignedthedextrorotatoryandlevorotaryenantiomersofglyceraldehydethe
followingconfigurationsandnamedthemDglyceraldehydeandLglyceraldehyde,respectively.
ThemonosaccharidesDglyceraldehydeandLglyceraldehydeserveasreferencepointsfortheassignment
ofrelativeconfigurationsforallotheraldosesandketoses.Thereferencepointisthestereocentrefurthest
fromthecarbonylgroup.Becausethisstereocentreisthenexttothelastcarbonatomonthechain,itis
calledthepenultimatecarbon.ADmonosaccharideisamonosaccharidethathasthesameconfiguration
atitspenultimatecarbonatomasDglyceraldehyde(itsOHisontherightinaFischerprojection).(Note
thattheDusedin referstothesodiumDline(seechapter17)andisunrelatedtotheDinD
glyceraldehyde.)AnLmonosaccharidehasthesameconfigurationatitspenultimatecarbonatomasL
glyceraldehyde(itsOHisontheleftinaFischerprojection).Almostallmonosaccharidesinthebiological
worldbelongtotheDseries,andthemajorityofthemareeitherhexosesorpentoses.

Figure22.1showsthenamesandFischerprojectionsforallDaldotrioses,tetroses,pentosesandhexoses.
Eachnameconsistsofthreeparts.Theletterdspecifiestheconfigurationatthestereocentrefurthestfrom
thecarbonylgroup.Prefixes,suchasrib,arabinandgluc,specifytheconfigurationsofallother
stereocentresrelativetooneanother.Thesuffixoseshowsthatthecompoundisacarbohydrate.

FIGURE22.1ConfigurationalrelationshipsamongtheisomericDaldotetroses,DaldopentosesandDaldohexoses.
TheconfigurationofthereferenceOHonthepenultimatecarbonatomisshowninblue.

ThethreemostabundanthexosesinthebiologicalworldareDglucose,DgalactoseandDfructose.Thefirst
twoareDaldohexoseswhilethethird,fructose,isaD2ketohexose.Glucose,byfarthemostabundantof
thethree,isalsoknownasdextrosebecauseitisdextrorotatory.Othernamesforthismonosaccharide
includegrapesugarandbloodsugar.Humanbloodnormallycontains65110mgofglucose/100mLof
blood.Dfructoseisoneofthetwomonosaccharidebuildingblocksofsucrose(tablesugar,section22.5).

WORKEDEXAMPLE22.1

NamingandDrawingSimpleCarbohydrates

(a)DrawFischerprojectionsforthefouraldotetroses.
(b)WhichofthefouraldotetrosesareDmonosaccharides,whichareLmonosaccharidesand
whichareenantiomers?
(c)RefertoFigure22.1,andnameeachaldotetroseyouhavedrawn.

Analysis

Onewayofapproachingthisquestionistobuildchemicalmodelsofthealdotetrosesand
comparetherelationshipsoftheatomsandbondsinthreedimensionalspace.However,ifyoudo
nothaveachemicalmodelkit,youcandrawandnamethestructuresinordertoproperly
visualisetherelationshipsbetweentheatomsandbondsinvolvedinthesemolecules.

Solution

TheFischerprojectionsforthefouraldotetrosesare:

NotethatintheFischerprojectionofaDaldotetrosetheOHonC(3)isontherightandinanL
aldotetroseitisontheleft.

Isouranswerreasonable?

ThemostcommonmistakewithFischerprojectionsisincorrectlycountingthenumberofcarbon
atomsinthechain.Remembertoputthemostoxidisedcarbonatomatthetopofthechainand
putthe(nonchiral)terminalCH2OHatthebottom.Everyintersectionofverticalandhorizontal
 linesrepresentsacarbonatom.

PRACTICEEXERCISE22.1

(a)DrawFischerprojectionsforall2
ketopentoses.
(b)Whichofthe2ketopentosesareD
ketopentoses,whichareL
ketopentoses,andwhichare
enantiomers?

AminoSugars
AminosugarscontainanNH2groupinplaceofanOHgroup.Onlythreeaminosugarsarecommonin
nature:Dglucosamine,DmannosamineandDgalactosamine.NacetylDglucosamine,aderivativeofD
glucosamine,isacomponentofmanypolysaccharides,includingconnectivetissuesuchascartilage.Itis
alsoacomponentofchitin,thehardshelllikeexoskeletonoflobsters,crabs,prawnsandothershellfish.
Severalotheraminosugarsarecomponentsofnaturallyoccurringantibiotics.

PhysicalProperties
Monosaccharidesarecolourless,crystallinesolids.Becausehydrogenbondingispossiblebetweentheir
polarOHgroupsandwater,allmonosaccharidesareverysolubleinwater.Theyareonlyslightlysoluble
inethanolandareinsolubleinnonpolarsolventssuchasdiethylether,dichloromethaneandbenzene.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
22.3TheCyclicStructureofMonosaccharides
Insection21.5,wesawthataldehydesandketonesreactwithalcoholstoformhemiacetals,sometimes
referredtoashemiketalswhenderivedfromaketone.Wealsosawthatcyclichemiacetalsformreadily
whenhydroxylandcarbonylgroupsarepartsofthesamemoleculeandtheirinteractioncanforma
fiveorsixmemberedring.Forexample,4hydroxypentanalformsafivememberedcyclichemiacetal
asshownonthenextpage.Notethat4hydroxypentanalcontainsonestereocentreandthatasecond
stereocentreisgeneratedatC(1)byhemiacetalformation.

Monosaccharidescontainhydroxylandcarbonylgroupsinthesamemolecule,andtheyexistalmost
exclusivelyasfiveandsixmemberedcyclichemiacetals.

HaworthProjections
AcommonwayofrepresentingthecyclicstructureofmonosaccharidesistheHaworthprojection,
whichisnamedaftertheEnglishchemistSirWalterNormanHaworth(NobelPrizeinchemistry,1937).
InaHaworthprojection,afiveorsixmemberedcyclichemiacetalisrepresentedasaplanarpentagon
orhexagonlyingroughlyperpendiculartotheplaneofthepaper.Groupsbondedtothecarbonatoms
oftheringthenlieeitheraboveorbelowtheplaneofthering.Thenewstereocentrecreatedinforming
thecyclicstructureiscalledtheanomericcarbon.Stereoisomersthatdifferinconfigurationonlyatthe
anomericcarbonatomarecalledanomers.TheanomericcarbonatomofanaldoseisC(1)inD
fructose,themostcommonketose,itisC(2).

Typically,Haworthprojectionsarewrittenwiththeanomericcarbonatomattherightandthe
hemiacetaloxygenatomatthebackright(figure22.2).
 FIGURE22.2HaworthprojectionsforDglucopyranoseandDglucopyranose.

AsyoustudytheopenchainandcyclichemiacetalformsofDglucose,notethatinconvertingfroma
FischerprojectiontoaHaworthstructure:
groupsontherightintheFischerprojectionpointdownintheHaworthprojection
groupsontheleftintheFischerprojectionpointupintheHaworthprojection
foraDmonosaccharide,theterminalCH2OHpointsupintheHaworthprojection
theconfigurationoftheanomericOHgroupisrelativetotheterminalCH2OHgroup:ifthe
anomericOHgroupisonthesamesideastheterminalCH2OH,itsconfigurationisifthe
anomericOHgroupisontheoppositeside,itis.

Asixmemberedhemiacetalringisnamedwiththecomponentpyran,andafivemembered
hemiacetalringisnamedwiththecomponentfuran.Thetermsfuranoseandpyranoseareused
becausemonosaccharidefiveandsixmemberedringscorrespondtotheheterocycliccompounds
pyranandfuran.

Afuranoseisafivememberedcyclichemiacetalformofamonosaccharide.Apyranoseisasix
memberedcyclichemiacetalformofamonosaccharide.

Becausetheandformsofglucosearesixmemberedcyclichemiacetals,theyarenamedD
glucopyranoseandDglucopyranose,respectively.However,thedesignationsfuranandpyranare
notalwaysusedinthenamesofmonosaccharides.Thus,theglucopyranosesareoftennamedsimply
DglucoseandDglucose.

Aldopentosesalsoformcyclichemiacetals.ThemostprevalentformsofDriboseandotherpentosesin
thebiologicalworldarefuranoses.HaworthprojectionsforDribofuranose(Dribose)and2
deoxyDribofuranose(2deoxyDribose)areshownonthenextpage.

Theprefix2deoxyindicatestheabsenceofoxygenatC(2).UnitsofDriboseand2deoxyDribosein
nucleicacidsandmostotherbiologicalmoleculesarefoundalmostexclusivelyintheconfiguration.

Fructosealsoformsfivememberedcyclichemiacetals.Dfructofuranose,forexample,isfoundinthe
carbohydratesucrose(section22.5).

ConformationRepresentations
AfivememberedringissoclosetobeingplanarthatHaworthprojectionsareadequatetorepresent
furanoses.Forpyranoses,however,thesixmemberedringismoreaccuratelyrepresentedbywhatis
knownasachairconformation,socalledbecausethemoleculelookslikeachair.Thechair
conformationallowsallofthecarbonatomstohavebondanglesthatareveryclosetotheoptimal
tetrahedralbondangleandthestraininthemoleculeisthereforeminimal.Figure22.3showsstructural
formulaeforDglucopyranoseandDglucopyranose,bothdrawnaschairconformations.Thefigure
alsoshowstheopenchain,orfree,aldehydeformwithwhichthecyclichemiacetalformsarein
equilibriuminaqueoussolution.Noticethateachgroup,includingtheanomericOH,inthechair
conformationofDglucopyranoseisequatorial.NoticealsothattheOHgroupontheanomeric
carbonatominDglucopyranoseisaxial.BecauseoftheequatorialorientationoftheOHonits
anomericcarbonatom,Dglucopyranoseismorestableandpredominatesinaqueoussolution.
 FIGURE22.3ChairconformationsofDglucopyranoseandDglucopyranose.BecauseDglucoseand
Dglucosearedifferentcompounds(theyareanomers),theyhavedifferentspecificrotations.

Atthispoint,youshouldcomparetherelativeorientationsofgroupsontheDglucopyranoseringinthe
Haworthprojectionandchairconformation.

NoticethattheorientationsofthegroupsonC(1)toC(5)intheHaworthprojectionofD
glucopyranoseareup,down,up,downandup,respectively.Thesameisthecaseinthechair
conformation,whichhasbeendrawnwithoutshowingthehydrogenatoms,forclarity.

WORKEDEXAMPLE22.2

RepresentingCarbohydratesintheChairConformation
DrawchairconformationsforDgalactopyranoseandDgalactopyranose.Labelthe
anomericcarbonatomineachcyclichemiacetal.

Analysisandsolution
 DgalactosediffersinconfigurationfromDglucoseonlyatC(4).Therefore,torepresentD
galactose,simplydrawtheandformsofDglucopyranoseandtheninterchangethe
positionsoftheOHandHgroupsonC(4).Thespecificrotationsofeachanomerare
shownandyouwillnotetheimpactontheopticalrotationoftheinversionofone
stereocentre.

Isouranswerreasonable?

Rememberthattheandanomersdifferonlyintheorientationofthegroupsonthecarbon
atomofthehemiacetalgroup.Therefore,thestructuresoftheandformsofthemolecule
shouldbethesameinallaspectsexceptforthestereochemistryofthiscarbonatom.

PRACTICEEXERCISE22.2
DrawchairconformationsforD
mannopyranoseandDmannopyranose.
Labeltheanomericcarbonatomineach.

Mutarotation
Mutarotationisthechangeinspecificrotationthataccompaniestheinterconversionofand
anomersinaqueoussolution.Asanexample,asolutionpreparedbydissolvingcrystallineD
glucopyranoseinwatershowsaninitialrotationof+112(figure22.3),whichgraduallydecreasestoan
equilibriumvalueof+52.7asDglucopyranosereachesanequilibriumwithDglucopyranose.A
solutionofDglucopyranosealsoundergoesmutarotation,duringwhichthespecificrotationchanges
fromaninitialvalueof+18.7tothesameequilibriumvalueof+52.7.Theequilibriummixture
consistsof64%Dglucopyranoseand36%Dglucopyranoseandonlytraces(0.003%)oftheopen
chainform.Mutarotationoccursinallcarbohydratesthatexistinhemiacetalforms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
22.4ReactionsofMonosaccharides
Inthissection,wediscussthereactionsofmonosaccharideswithalcohols,reducingagentsandoxidising
agents.Wealsoexaminehowthesereactionsareusefulinoureverydaylives.

FormationofGlycosides(Acetals)
Aswesawinsection21.5,treatinganaldehydeorketonewithonemoleculeofanalcoholyieldsa
hemiacetal,andtreatingthehemiacetalwithamoleculeofanalcoholyieldsanacetal.Treatinga
monosaccharide,allofwhichexistascyclichemiacetals,withanalcoholgivesanacetal,asillustratedby
thereactionofmethanolwithDglucopyranose(Dglucose)drawnintheHaworthprojectionto
emphasisethedifferencesinthestructuresofthetwoproducts.

Acyclicacetalderivedfromamonosaccharideiscalledaglycoside,andthebondfromtheanomeric
carbontotheORgroupiscalledaglycosidicbond.Unlikeahemiacetal,anacetalisnolongerin
equilibriumwiththeopenchaincarbonylcontainingcompoundinneutraloralkalinesolutions.Likeother
acetals(section21.5),glycosidesarestableinwaterandaqueousbase,butundergohydrolysisinaqueous
acidtoformanalcoholandamonosaccharide.

Wenameglycosidesbylistingthealkylorarylgroupbondedtooxygen,followedbythenameofthe
carbohydratewiththeendingereplacedwithide.Forexample,glycosidesderivedfromD
glucopyranosearenamedDglucopyranosidesthosederivedfromDribofuranosearenamedD
ribofuranosides.

WORKEDEXAMPLE22.3

UnderstandingtheStructuresofGlycosides
DrawastructuralformulaformethylDribofuranoside(methylDriboside).Labelthe
anomericcarbonatomandtheglycosidicbond.

AnalysisBydrawingapreciserepresentationofthestructureofaglycosidefromitsnameyou
willgainanappreciationofhowtheatomsarearrangedtogiverisetothisfunctionalgroup.

Solution
 Isouranswerreasonable?

Glycosidesareacetals,so,unlikehemiacetals,theyarealwayslockedintoacyclicform.
Consequently,youcannotuseaFischerprojectiononlyaHaworthprojectionorperhapsafull
structuralrepresentation.Forsimpleglycosides,aHaworthprojectionclearlyshowstherelative
arrangementoftheOHgroups,whichiscrucialfordeterminingwhichofthemanymono
saccharidesisinvolved(figure22.1).

PRACTICEEXERCISE22.3
Drawastructuralformulaforthechair
conformationofmethylDmannopyranoside
(methylDmannoside).Labeltheanomeric
carbonatomandtheglycosidicbond.

JustastheanomericcarbonatomofacyclichemiacetalreactswiththeOHgroupofanalcoholtoforma
glycoside,itcanalsoreactwiththeNHgroupofanaminetoformanNglycoside.Especiallyimportant
inthebiologicalworldaretheNglycosidesformedbetweenDriboseand2deoxyDribose(eachasa
furanose),andtheheterocyclicaromaticaminesuracil,cytosine,thymine,adenineandguanine(figure
22.4).Nglycosidesofthesecompoundsarethestructuralunitsofnucleicacids(chapter25).

FIGURE22.4StructuralformulaeofthefivemostimportantpurineandpyrimidinebasesfoundinDNAandRNA.
ThehydrogenatomshownincolourislostintheformationofanNglycoside.

WORKEDEXAMPLE22.4

UnderstandingtheStructuresofMoreComplicated,
 BiologicallyRelevantGlycosides
DrawastructuralformulafortheNglycosideformedbetweenDribofuranoseandcytosine.
LabeltheanomericcarbonatomandtheNglycosidicbond.

AnalysisPuttingtogetherthestructuralrepresentationswehavemadeforsimplefunctional
groupsallowsustobegintobuilduprepresentationsofeventhemostcomplicatedbiological
molecules,suchasDNA.AnNglycosidecontainsanNatombondedtotheanomericcarbon
atomofthecarbohydrate.ThedesignationmeansthattheNatomwilllieonthesamesideof
theringastheCH2OHgroup.

Solution

Isouranswerreasonable?

ThebasistothestructurehastobetheHaworthprojection,sofirstchecktoensurethatitis
correctlydrawn.Theacetaloxygenthatformstheringshouldbeattherearofthestructureand
theterminalCH2OHshouldalsobetotherear,pointingup.Thencheckthatthebondbetween
Dribofuranoseandcytosineiscorrect.Thebondisdrawnupwardsfromtheanomericcarbon
atomtothenitrogenatomofcytosineandisthereforeaNglycosidicbond.

PRACTICEEXERCISE22.4
DrawastructuralformulafortheN
glycosideformedbetweenDribofuranose
andadenine.

ReductiontoAlditols
Thecarbonylgroupofamonosaccharidecanbereducedtoahydroxylgroupbyavarietyofreducing
agents,includingNaBH4(section21.5,p.957).Thereductionproductsareknownasalditols.Reductionof
DglucosegivesDglucitol,morecommonlyknownasDsorbitol.Dglucoseisshownbelowintheopen
chainform,onlyasmallamountofwhichispresentinsolution.However,asitisreduced,theequilibrium
betweenthecyclichemiacetalformandtheopenchainformshiftstoreplacetheDglucose.NotethatD
glucosehasalsobeenrepresentedinachairconformation,whichmorerealisticallyrepresentstherealityof
itsshape.
ChemistryResearch

CombattingFluwithGlycomics

ProfessorMarkvonItzstein,InstituteforGlycomics,GriffithUniversity

Theimportantandsometimesessentialrolesofcarbohydratesinbiologicalprocesses,particularly
inanumberofdiseaserelatedprocesses,havebecomebetterdefined.Understandinghow
carbohydrates,andproteinsthatrecognisethem,areinvolvedindiseaseprovidesexciting
opportunitiesfordrugdiscovery.Forexample,influenzavirususesitsmembraneassociated
carbohydraterecognisingprotein,haemagglutinin(HA),totargetspecifichostcellbound
carbohydratesintherespiratorytractandinitiateinfection.Thevirusalsohasamembrane
associated,carbohydraterecognisingenzymeknownassialidase(neuraminidase,NA)thatacts
asapairofbiologicalscissorsitclipscarbohydratesawayfromtheinfectedcellsurfaceand
enablesthevirionprogenytomoveonandinfectnewcells.Clearlybothoftheseinfluenzavirus
surfaceproteinsarepossibledrugdesigntargetsastheyarebothessentialinthelifecycleofthe
virus.

In1993,theAustralianbasedvonItzsteingroupreportedthefirstdesignerantiinfluenzadrug
nowknownasRelenza(figure22.5).Thiscarbohydratebaseddrugblockstheactionofthe
enzymesialidase,leavingthevirionprogenyclumpedattheinfectedcellsurface.Theclumped
virionprogenyarethenreadilycleanedupbytheimmunesystemandthespreadofinfectionis
halted.Relenzaissynthesisedfromanaturallyoccurringandwidelydistributed,negatively
chargedcarbohydrateknownasNacetylneuraminicacid.

FIGURE22.5StructureofRelenza.
 Importantly,thedrugisactiveagainstallstrainsofinfluenzavirus.vonItzsteinandhisgroup
continuetheireffortstowardsthedevelopmentofnextgenerationantiinfluenzadrugsthatare
basedonrelativelyinexpensivesimplecarbohydratessuchasNacetylDglucosamine(shown
below).SuchcompoundsmimicthedrugRelenzaandshowpotentactivityininvitroenzyme
andcellculturebasedassays.InarecentpublicationinNatureCommunications,thevonItzstein
groupandresearchersfromInstitutPasteurinParisandtheUniversityofStAndrewsinScotland
describedthedevelopmentofaseriesofinhibitorsforthedesignofnextgenerationanti
influenzadrugs.

Glycomics,thestudyofthechemistryandbiologyofcarbohydrates,promisestoprovidenew
opportunitiesforthediscoveryofclinicallyusefulmedicines.GriffithUniversity'sInstitutefor
Glycomics,oneofonlysixdedicatedglycomicsresearchfacilitiesintheworld,isaleaderinthe
fieldofcarbohydratescienceandhasmadesignificantbreakthroughsintherolethat
carbohydratesplayindiseaseandtheageingprocess.

Alditolsarenamedbyreplacingtheoseinthenameofthemonosaccharidewithitol.Sorbitolisfoundin
theplantworldinmanyberriesandincherries,plums,pears,apples,seaweedandalgae.Itisabout60per
centassweetassucrose(tablesugar)andisusedinthemanufactureoflolliesandasasugarsubstitutefor
diabetics.Amongotheralditolscommoninthebiologicalworldareerythritol,Dmannitolandxylitol,the
lastofwhichisusedasasweeteningagentinsugarlessgum,confectioneryandsweetcereals(figure
22.6).
 FIGURE22.6Manysugarfreeproductscontainsugaralcohols,suchasDsorbitolandxylitol.

WORKEDEXAMPLE22.5

DeterminingtheStructureofMonosaccharideReaction
Products
Sodiumborohydride,NaBH4,reducesDglucosetoDglucitol.Doyouexpectthealditolformed
undertheseconditionstobeopticallyactiveoropticallyinactive?Explain.

Analysis

Understandinghowafunctionalgrouptransformationcancontrolamolecule'spropertiesisbest
achievedbydrawingtheprecisestructureoftheproduct.

Solution

Opticalactivityrequiresachiralmolecule,andDglucitolischiral.ReductionbyNaBH4doesnot
affectanyofthefourstereocentresinDglucose,andtheproductdoesnothaveaninternalplane
ofsymmetry,soitisnotamesoisomer.Therefore,wecanpredictthattheproductisoptically
active.

Isouranswerreasonable?

ReductionusingNaBH4removesthealdehydefunctionalgroupandthereforeprevents
hemiacetalformation.Thegenerationofahemiacetalcreatesanewchiralcarbonatom,sothis
possibilityisprevented.However,theotherchiralcarbonatomsareunaffected,sotheproduct
moleculestillretainsopticalactivity.
 PRACTICEEXERCISE22.5
Sodiumborohydride,NaBH4,reducesD
erythrosetoerythritol.Doyouexpectthe
alditolformedundertheseconditionstobe
opticallyactiveoropticallyinactive?Explain.

OxidationtoAldonicAcids(ReducingSugars)
Wesawinsection21.5thatseveralagents,includingO2,oxidisealdehydes(RCHO)tocarboxylicacids
(RCOOH).Theeaseofoxidationofaldehydesleadstoaspecifictestforthisfunctionalgroupcalledthe
Tollens'test(chapter21,p.959),whichisalsorelevantformonosaccharides.Similarly,underbasic
conditions,thealdehydegroupofanaldosecanbeoxidisedtoacarboxylategroup.Undertheseconditions,
thecyclicformofthealdoseisinequilibriumwiththeopenchainform,whichisthenoxidisedbyamild
oxidisingagent.Dglucose,forexample,isoxidisedtoDgluconate(theanionofDgluconicacid).

Anycarbohydratethatreactswithanoxidisingagenttoformanaldonicacidisclassifiedasareducing
sugar.(Itreducestheoxidisingagent.)

OxidationtoUronicAcids
EnzymecatalysedoxidationoftheprimaryalcoholatC(6)ofahexoseyieldsauronicacid.Enzyme
catalysedoxidationofDglucose,forexample,yieldsDglucuronicacid,shownhereinbothitsopenchain
andcyclichemiacetalforms(onlytheformisshown).
Dglucuronicacidiswidelydistributedinboththeplantandanimalworlds.Inhumans,itisanimportant
componentoftheacidicpolysaccharidesofconnectivetissues.Thebodyalsousesittodetoxifyforeign
phenolsandalcohols.Intheliver,thesecompoundsareconvertedtoglycosidesofglucuronicacid
(glucuronides),tobeexcretedinurine.Theintravenousanaestheticpropofol,forexample,isconvertedto
thefollowingwatersolubleglucuronideandthenexcretedinurine.

LascorbicAcid(VitaminC)

OneofthemostimportantreactionsofglucoseisitsconversiontoLascorbicacid(vitaminC).Thisvitamin
issynthesisedbiochemicallybyplantsandsomeanimalsfromDglucose.Humans,however,donothave
theenzymesystemsrequiredforthissynthesisandsoforusLascorbicacidisavitamin,i.e.anessential
componentofourdiet.CaptainCookinsistedthathiscrewconsumesauerkrautandlimejuiceonthelong
voyagesfromEnglandwhenhemappedtheeastcoastofAustraliaandcircumnavigatedNewZealand.
LimesarerichinvitaminCandsohiscrewdidnotsufferfromscurvy,avitaminCdeficiencythatwas
commonamongsailorsofthetime.Today,vitaminCisoneofthemostcommonlyuseddietary
supplementsasthereisaperceptionthatitisanimportantantioxidantwhichcontrolsfreeradicalsand
ageing(figure22.7).

FIGURE22.7VitaminCinanorangeisidenticaltoitssynthetictabletform.

ThestructuralformulaofvitaminC(Lascorbicacid)resemblesthatofamonosaccharide.Lascorbicacidis
veryeasilyoxidisedtoLdehydroascorbicacid,adiketone.
ItisthiseaseofoxidationthatmakesvitaminCacrucialantioxidantinthebody'sbiologicaldefence
mechanisms.BothLascorbicacidandLdehydroascorbicacidarephysiologicallyactiveandarefound
togetherinmostbodyfluids.

ChemicalConnections

MeasuringBloodSugar(Glucose)toManageDiabetes

AlmosttwomillionpeopleinAustraliaandNewZealandsufferfromdiabetes,andmorethan100
000arediagnosedeachyear.Thesepeopleneedtocloselymonitortheirbloodsugarlevelsand
administermedicationtomanagetheircondition.Accuratelydeterminingthelevelofglucosein
blood,urineandotherbiologicalfluidsisoneofthemostcommonanalyticalprocedures
performedinclinicalchemistrylaboratories.

Diabeticpeopleandanimalsproduceinsufficientlevelsofthepolypeptidehormoneinsulin
(section24.4).Ifthebloodconcentrationofinsulinistoolow,muscleandlivercellsdonot
absorbglucosethiscanquicklyleadtoincreasedlevelsofbloodglucose(hyperglycaemia),
impairedmetabolismoffatsandproteins,ketosisand,possibly,diabeticcoma.Therefore,
diabeticsneedtomeasuretheirownbloodsugarlevelsregularly.Arapidprocedurefor
determiningbloodglucoselevelsiscriticalforearlydiagnosisandeffectivemanagementofthis
disease.Inadditiontobeingrapid,atestmustgiveanaccuratemeasureofDglucosethatis,it
mustbespecificforDglucoseandnotbeaffectedbyothersubstancespresentinblood.Modern
glucosemonitorsusetechnologybasedontheenzymeglucoseoxidase.Thisenzymecatalyses
theoxidationofDglucosetoDgluconicacid.

GlucoseoxidaseisspecificforDglucose.Therefore,completeoxidationofanysample
containingbothDglucoseandDglucoserequiresconversionoftheformtotheform.

Intheearlierformsofbloodglucosemonitors,molecularoxygen,O2,wasusedastheoxidising
agent,producinghydrogenperoxide,H2O2,theconcentrationofwhichcanbedetected
spectrophotometrically.Forexample,hydrogenperoxideconvertscolourlessotoluidinetoa
colouredproductinareactioncatalysedbytheenzymeperoxidise.
Theoriginalteststripsusedtomeasurebloodsugarlevels(seefigure22.8)reliedonacolour
intensitycharttodeterminetheextentofthereactionandhencetheconcentrationofglucosein
thetestsolution.Thefirstelectronictestersusedaspectrophotometricapproachtodeterminethe
concentrationofthecolouredoxidationproduct.

FIGURE22.8Abloodteststrip,whichusesacolourintensitycharttomeasureglucoseconcentration.

Newerdevicesthatdonotrelyoncolourhavecomeontothemarket.Instead,anenzymelinked
electrodecontainingglucoseoxidaseisexposedtoapreciseamountofblood.Theextentof
oxidationofDglucoseisdetectedbytheelectrodeandaglucosereadingisgivenbasedonthe
currentgenerated(figure22.9).
 FIGURE22.9Ahomebloodsugarmonitor.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
22.5DisaccharidesandOligosaccharides
Mostcarbohydratesinnaturecontainmorethanonemonosaccharideunit.Thosewhichcontaintwounits
arecalleddisaccharidesthosewhichcontainthreeunitsarecalledtrisaccharides,andsoon.Themore
generalterm,oligosaccharide,isoftenusedforcarbohydratesthatcontainfromsixtotenmonosaccharide
units.Carbohydratescontaininglargernumbersofmonosaccharideunitsarecalledpolysaccharides.

Inadisaccharide,twomonosaccharideunitsarejoinedbyaglycosidicbondbetweentheanomericcarbon
atomofoneunitandanOHoftheother.Sucrose,lactoseandmaltoseareimportantdisaccharides.

Sucrose
Sucrose(tablesugar)isthemostabundantdisaccharideinthebiologicalworld.Itisobtainedprincipally
fromthejuiceofsugarcaneandsugarbeets.Insucrose,C(1)ofDglucopyranosebondstoC(2)ofD
fructofuranosethroughan1,2glycosidicbond.

Becausetheanomericcarbonatomsofboththeglucopyranoseandfructofuranoseunitsareinvolvedin
formationoftheglycosidicbond,neithermonosaccharideunitisinequilibriumwithitsopenchainform.
Thus,sucroseisanonreducingsugar.

Lactose
Lactose,theprincipalsugarinmilk,accountsfor5to8percentofhumanmilkand4to6percentofcow's
milk.ThisdisaccharideconsistsofDgalactopyranose,bondedbya1,4glycosidicbondtoC(4)ofD
glucopyranose.
Lactoseisareducingsugar,becausethecyclichemiacetaloftheDglucopyranoseunitisinequilibriumwith
itsopenchainformandcanbeoxidisedtoacarboxylgroup.

Ithasbeenestimatedthat1in10AustraliansandNewZealandersexperiencesomedegreeoflactose
intolerance.LactoseintoleranceisanespeciallyimportanthealthissueforIndigenousAustraliansandMaori
amongwhomtheincidenceismuchhigher.Peoplewithlactoseintolerancemaysufferfromcalcium
deficienciesunlesstheirdietincludesnondairysourcesofcalcium.

ChemicalConnections

LactoseIntolerance

Inourbodies,anenzymecalledlactase(galactosidase)catalysesthehydrolysisoflactoseto
formglucoseandgalactose.

Thegalactoseproducedinthisprocessissubsequentlyconvertedbytheliverintoadditional
glucose,whichisthenfurthermetabolisedtoproduceenergy.Manypeopledonotproducea
sufficientamountoflactaseandareincapableofhydrolysinglargequantitiesoflactose.Instead,
lactoseaccumulatesandisultimatelybrokendownintoCO2andH2bybacteriapresentinthe
intestines.Bacterialdegradationoflactoseproducesseveralbyproducts,includinglacticacid.
 Thebuildupoflacticacidandotheracidicbyproductscausescramps,nauseaanddiarrhoea.
Thisconditioniscalledlactoseintolerance,anditisestimatedthatover10%ofthepopulationis
lactoseintolerantandsoareunabletoenjoyevenaglassofmilk(figure22.10).Differentethnic
andracialgroupsareaffectedtodifferentextents,wihthehighestincidenceoflactoseintolerance
occurringamongAsiansandthelowestincidenceoccurringamongEuropeans.

FIGURE22.10Somepeoplelacktheenzymesneededtometabolisedairyproducts.

Lactoseintolerancedevelopswithtime.Lactoseproductionbeginstodeclineformostchildrenat
aboutagetwo,althoughmanypeopledonotexperiencesymptomsoflactoseintoleranceuntil
laterinlife.Itisestimatedthat75%oftheadultpopulationworldwidewilldeveloplactose
intoleranceatsomestageintheirlife.Thisconditionalsoaffectsotherspecies,includingdogs
andcats,bothofwhichareparticularlysusceptibletodevelopinglactoseintolerance.

Lactoseintoleranceiseasilytreatedthroughacontrolleddietthatminimisestheintakeoffood
productscontaininglactose.Severaldairyproductsareproducedviaprocessesthatremovethe
lactose,andtheseproductsaremarketedasbeinglactosefree.Inaddition,theenzymelactaseis
availableintabletorliquidandcanbetakenpriortoeatingproductscontaininglactose.

Maltose
Maltosederivesitsnamefromitspresenceinmalt,thejuicefromsproutedbarleyandothercerealgrains.
MaltoseconsistsoftwounitsofDglucopyranose,joinedbyaglycosidicbondbetweenC(1)(theanomeric
carbonatom)ofoneunitandC(4)oftheotherunit.Becausetheoxygenatomontheanomericcarbonatom
ofthefirstglucopyranoseunitis,thebondjoiningthetwounitsiscalledan1,4glycosidicbond.

Youmightliketoconsiderhowyoucouldbestrepresentthestructureofthecarbohydrateringsandthe
disaccharidelinkagethatispresentinmaltose.ShownbelowareHaworthprojectionsandachair
conformationformaltose,sonamedbecausetheOHgroupontheanomericcarbonatomoftheglucose
unitontherightis.RememberthattheprotocolforHaworthprojectionsisthatthebondscomingfromthe
ringsaredrawnverticallytotheplaneofthering.ThiswouldmeanthattwoHaworthprojectionslinked
togetherwouldrequirethattheringsareorientedatanangletoeachother.Perhapsabetterrepresentation
keepstheringsinthehorizontalplaneorientationbutshowstheglycosidebondasnotbeingvertical.

Inrealitythestructureofdisaccharidesisbestrepresentedbytheactualchairconformation,whichmore
clearlyshowstherealbondanglesanddistances,asdiscussedinchapter17(p.691).Insometextsyou
mightseetheglycosidelinkagedrawnasaUshapedconnection.Thisisnotaverygoodrepresentation,as
themethodfordrawingstructuresoutlinedinchapter17(p.687)suggeststhattwolinesmeetingatanangle
indicatethepresenceofacarbonatom,andthisisclearlynotthecasewithaglycosidicbond.

WORKEDEXAMPLE22.6

Understandingthe3DStructureofDisaccharides
DrawachairconformationfortheanomerofadisaccharideinwhichtwounitsofD
glucopyranosearejoinedbyan1,6glycosidicbond.

AnalysisandsolutionFirstdrawachairconformationofDglucopyranose.Thenconnect
theanomericcarbonatomofthismonosaccharidetoC(6)ofasecondDglucopyranoseunitby
anglycosidicbond.Theresultingmoleculeiseitherordependingontheorientationofthe
OHgrouponthereducingendofthedisaccharide.Thedisaccharideshownhereis.
 Isouranswerreasonable?

Lookcloselyatthedrawingofthemolecule.Fora1,6connection,thefirstcarbonatomofone
ring,C(1),connectstothelastcarbonatomofthesecondring,C(6).Anconnectionisoriented
downwardsfromthefirstring.

PRACTICEEXERCISE22.6
DrawaHaworthprojectionandachair
conformationfortheformofadisaccharide
inwhichtwounitsofDglucopyranoseare
joinedbya1,3glycosidicbond.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
22.6Polysaccharides
Polysaccharidesconsistofalargenumberofmonosaccharideunitsjoinedtogetherbyglycosidicbonds.
Threeimportantpolysaccharides,allmadeupofglucoseunits,arestarch,glycogenandcellulose.

Starch:AmyloseandAmylopectin
Starchisfoundinallplantseedsandtubers,anditistheforminwhichglucoseisstoredforlateruse.Starch
canbeseparatedintotwoprincipalpolysaccharides:amyloseandamylopectin.Althoughthestarchfrom
eachplantisunique,moststarchescontain20to25percentamyloseand75to80percentamylopectin.

CompletehydrolysisofbothamyloseandamylopectinyieldsonlyDglucose.Amyloseiscomposedof
continuous,unbranchedchainsofasmanyas4000Dglucoseunitsjoinedby1,4glycosidicbonds.
Amylopectincontainschainsofupto10000Dglucoseunits,alsojoinedby1,4glycosidicbonds.In
addition,amylopectinhasconsiderablebranchingfromthislinearnetwork.Atbranchpoints,newchainsof
24to30unitsstartby1,6glycosidicbonds(figure22.11).

FIGURE22.11AmylopectinisahighlybranchedpolymerofDglucose.Chainsconsistof24to30unitsofD
glucose,joinedby1,4glycosidicbonds,andbranchescreatedby1,6glycosidicbonds.

Whyarecarbohydratesstoredinplantsaspolysaccharidesratherthanmonosaccharides,amoredirectly
usablesourceofenergy?Theanswerhastodowithosmoticpressure,whichisproportionaltothemolar
concentration,notthemolarmass,ofasolute.If1000moleculesofglucoseareassembledintoonestarch
macromolecule,asolutioncontaining1gofstarchper10mLwillhaveonlyonethousandththeosmotic
pressurerelativetoasolutionof1gofglucoseinthesamevolume.Thisfeatofpackagingisatremendous
advantagebecauseitreducesthestrainonvariousmembranesenclosingsolutionsofsuchmacromolecules.

Glycogen
Glycogenisthereservecarbohydrateforanimals.Likeamylopectin,glycogenisabranchedpolymerofD
glucose.Eachbranchcontainsapproximately1214glucoseunits,joinedby1,4and1,6glycosidic
bonds.Thetotalamountofglycogeninthebodyofawellnourishedadulthumanisabout350g,divided
almostequallybetweenliverandmuscle.

Cellulose
Cellulose,themostwidelydistributedplantskeletalpolysaccharide,constitutesalmosthalfofthecellwall
materialofwood.Cotton(figure22.13)isalmostpurecellulose.

FIGURE22.13Cottonreadytobeharvested.

Cellulose,alinearpolymerofDglucoseunitsjoinedby1,4glycosidicbonds(figure22.12),hasan
averagemolarmassof400000gmol1,correspondingtoapproximately2800glucoseunitspermolecule.

FIGURE22.12CelluloseisalinearpolymerofDglucose,joinedby1,4glycosidicbonds.

Cellulosemoleculesactlikestiffrodsbyaligningthemselvessidebysideintowellorganised,water
insolublefibresinwhichtheOHgroupsformnumerousintermolecularhydrogenbonds.This
arrangementofbundlesofparallelchainsgivescellulosefibrestheirhighmechanicalstrengthandexplains
whycelluloseisinsolubleinwater.Whenapieceofcellulosecontainingmaterialisplacedinwater,there
arenotenoughOHgroupsonthesurfaceofthefibretopullindividualcellulosemoleculesawayfromthe
stronglyhydrogenbondedfibre.Atthemolecularlevel,thechainsofcarbohydratesbindtogetherthrough
hydrogenbondingtoformbundles(figure22.14).Thesebundlesoffibresarecalledmicrofibrils.Theyare
gluedtogetherbysmallerpolysaccharidechains,calledhemicelluloses,andactasthestructuralunitsthat
giveplantwallstheirstrengthandrigidity.
 FIGURE22.14 (a)Principalstructuresofplantcellwalls,whicharecomposedofcrosslinkedcellulose
microfibrilsconstructedfromlinkedglucosechains
(b)electronmicrographofcellwallshowingcrosslinkedmicrofibrils.

Humanscannotusecelluloseasfoodbecauseourdigestivesystemsdonotcontainglucosidases,enzymes
thatcatalysethehydrolysisofglycosidicbonds.Instead,wehaveonlyglucosidaseshence,the
polysaccharidesweuseassourcesofglucosearestarchandglycogen.Bycontrast,manybacteriaand
microorganismsdocontainglucosidasesandcandigestcellulose.Termitesarefortunate(muchtoour
regret)tohavesuchbacteriaintheirintestinesandcanusewoodastheirprincipalfood.Ruminants(cud
chewinganimals)andhorsescanalsodigestgrassesandhay,becauseglucosidasecontainingmicro
organismsarepresentwithintheiralimentarysystems.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
IntroductiontoCarbohydrates
Carbohydratesarepolyhydroxyaldehydes,polyhydroxyketonesorsubstancesthatyieldthese
compoundsafterhydrolysis.Carbohydrates,nomatterhowcomplex,aregovernedbythepropertiesof
theindividualchemicalgroupsfromwhichtheyareconstructed.

Monosaccharides
Monosaccharidesarepolyhydroxyaldehydesorpolyhydroxyketones.Themostcommonhavethe
generalformulaCnH2nOn,wherenvariesfrom3to9.Theirnamescontainthesuffixose.Theprefixes
tri,tetr,pentandsoonshowthenumberofcarbonatomsinthechain.Theprefixaldoindicatesan
aldehyde,theprefixketodesignatesaketone.Monosaccharidescontaininganaldehydegroupare
classifiedasaldoses,andthosecontainingaketonegroupareketoses.

InaFischerprojectionofacarbohydrate,thecarbonchainiswrittenvertically,withthemosthighly
oxidisedcarbonatomtowardsthetop.Horizontallinesshowgroupsprojectingabovetheplaneofthe
page,verticallinesshowgroupsprojectingbehindtheplaneofthepage.Amonosaccharidethathasthe
sameconfigurationatthepenultimatecarbonatomasDglyceraldehydeiscalledaDmonosaccharide
onethathasthesameconfigurationatthepenultimatecarbonatomasLglyceraldehydeiscalledanL
monosaccharide.

AnaminosugarcontainsanNH2groupinplaceofanOHgroup.

TheCyclicStructureofMonosaccharides
Monosaccharidesexistprimarilyascyclichemiacetalsinachairconformation.Thenewstereocentre
resultingfromhemiacetalformationisreferredtoasananomericcarbonatom.Thestereoisomers
formedthiswayarecalledanomers.Whenananomerofoneformisaddedtoanaqueoussolution,it
formsanequilibriumwiththeotheranomerinaprocesscalledmutarotation,whichisdetectedbythe
changeintheopticalrotationoftheinitialsolution.

Asixmemberedcyclichemiacetaliscalledapyranose,afivememberedcyclichemiacetalisa
furanose.ThesymbolindicatesthattheOHontheanomericcarbonatomisonthesamesideofthe
ringastheterminalCH2OH.ThesymbolindicatesthatOHontheanomericcarbonatomisonthe
oppositesideoftheringfromtheterminalCH2OH.Furanosesandpyranosescanbedrawnas
Haworthprojections.

ReactionsofMonosaccharides
Aglycosideisanacetalderivedfromamonosaccharide.Thebondfromtheanomericcarbonatomto
theORgroupiscalledaglycosidicbond.Thenameoftheglycosideiscomposedofthenameofthe
alkylorarylgroupbondedtotheacetaloxygenatom,followedbythenameofthemonosaccharidein
whichtheterminalehasbeenreplacedbyide.

Analditolisapolyhydroxycompoundformedbythereductionofthecarbonylgroupofa
monosaccharide.Analdonicacidisacarboxylicacidformedbyoxidationofthealdehydegroupofan
aldose.Thealdosereducestheoxidisingagentandisthereforecalledareducingsugar.Enzyme
catalysedoxidationoftheterminalCH2OHtoaCOOHgivesauronicacid.

Thedeterminationofbloodglucoselevelsisanimportantclinicaltestforthediagnosisandmanagement
ofdiabetes.Thetestusestheenzymeglucoseoxidase,whichcatalysestheoxidationofDglucoseto
Dgluconicacid.
Lascorbicacid(vitaminC)issynthesisedinnaturefromDglucosebyaseriesofenzymecatalysed
steps.

DisaccharidesandOligosaccharides
Adisaccharidecontainstwomonosaccharideunitsjoinedbyaglycosidicbond.Termsappliedto
carbohydratescontaininglargernumbersofmonosaccharidesare:trisaccharide,tetrasaccharide,
oligosaccharideandpolysaccharide.

SucroseisadisaccharideconsistingofDglucosejoinedtoDfructosebyan1,2glycosidicbond.
LactoseisadisaccharideconsistingofDgalactosejoinedtoDglucosebya1,4glycosidicbond.
MaltoseisadisaccharideoftwomoleculesofDglucosejoinedbyan1,4glycosidicbond.

Polysaccharides
Starchcanbeseparatedintotwofractionscalledamyloseandamylopectin.Amyloseisalinearpolymer
ofupto4000unitsofDglucopyranosejoinedby1,4glycosidicbonds.Amylopectinisahighly
branchedpolymerofDglucosejoinedby1,4glycosidicbondsand,atbranchpoints,by1,6
glycosidicbonds.Glycogen,thereservecarbohydrateofanimals,isahighlybranchedpolymerofD
glucopyranosejoinedby1,4glycosidicbondsand,atbranchpoints,by1,6glycosidicbonds.
Cellulose,theskeletalpolysaccharideofplants,isalinearpolymerofDglucopyranosejoinedby1,4
glycosidicbonds.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Formationofcyclichemiacetals(section22.3)
Amonosaccharideexistingasafivememberedringisafuranoseoneexistingasasixmemberedring
isapyranose.ApyranoseismostcommonlydrawnasaHaworthprojectionorachairconformation.

Formationofglycosides(section22.4)
Treatmentofamonosaccharidewithanalcoholinthepresenceofanacidcatalystformsacyclicacetal
calledaglycoside.ThebondtothenewOCH3groupiscalledaglycosidicbond.

Reductiontoalditols(section22.4)
Reductionofthecarbonylgroupofanaldoseoraketosetoahydroxylgroupyieldsapolyhydroxy
compoundcalledanalditol.

Oxidationtoanaldonicacid(section22.4)
Amildoxidisingagentoxidisesthealdehydegroupofanaldosetoacarboxylgrouptogivea
polyhydroxycarboxylicacidcalledanaldonicacid.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
Monosaccharides
22.1Whatisthedifferenceinstructurebetween:
(a)analdoseandaketoseand
(b)analdopentoseandaketopentose?
22.2Whichhexoseisalsoknownasdextrose?
22.3DandLglyceraldehydeareenantiomers.Explainwhatthismeans.
22.4Explainthemeaningofthedesignationsdandlasusedtospecifytheconfigurationof
carbohydrates.
22.5HowmanystereocentresarepresentinDglucose?HowmanystereocentresarepresentinD
ribose?Howmanystereoisomersarepossibleforeachmonosaccharide?
22.6WhichofthefollowingcompoundsareDmonosaccharidesandwhichareLmonosaccharides?
(a)

(b)

(c)

22.7Explainwhyallmonoanddisaccharidesaresolubleinwater.
22.8Whatisanaminosugar?Namethethreeaminosugarsmostcommonlyfoundinnature.
TheCyclicStructureofMonosaccharides
22.9Definethetermanomericcarbon.
22.10Explaintheconventionsforusingandtodesignatetheconfigurationsofcyclicformsof
monosaccharides.
22.11AreDglucoseandDglucoseanomers?Explain.Aretheyenantiomers?Explain.
22.12AreDguloseandlguloseanomers?Explain.
22.13Hexopyranosesaresometimesrepresentedinthechairform.Inwhatwayarechair
conformationsamoreaccuraterepresentationofmolecularshapeofhexopyranosesthan
Haworthprojections?
22.14Explainthephenomenonofmutarotationincarbohydrates.Bywhatmeansismutarotation
detected?
22.15Dgalactopyranosehasan[]D=+150.7.Whenitisdissolvedinwater,however,thespecific
rotationofthesolutionaftersometimeismeasuredas+80.2.Whatwouldbethespecific
rotationofasolutionofDgalactopyranosemeasuredunderthesameconditions?
22.16ThespecificrotationofDglucoseis+112.2.Whatisthespecificrotationoflglucose?
22.17WhenDglucoseisdissolvedinwater,thespecificrotationofthesolutionchangesfrom
+112.2to+52.7.Doesthespecificrotationoflglucosealsochangewhenitisdissolvedin
water?Ifso,towhatvaluedoesitchange?
ReactionsofMonosaccharides
22.18TherearefourDaldopentoses(figure22.1).IfeachisreducedwithNaBH4,whichyieldoptically
activealditols?Whichyieldopticallyinactivealditols?
22.19AccountfortheobservationthatthereductionofDglucosewithNaBH4givesanopticallyactive
alditol,whereasthereductionofDgalactosewithNaBH4givesanopticallyinactivealditol.
22.20WhichtwoDaldohexosesgiveopticallyinactive(meso)alditolsonreductionwithNaBH4?
(Hint:Seechapter17.)
22.21NamethetwoalditolsformedbyNaBH4reductionofDfructose.
22.22Isascorbicacidabiologicaloxidisingagentorabiologicalreducingagent?Explain.
DisaccharidesandOligosaccharides
22.23Definethetermglycosidicbond.
22.24Whatisthedifferenceinmeaningbetweenthetermsglycosidicbondandglucosidicbond?
22.25Doglycosidesundergomutarotation?
22.26Inmakinglolliesorsyrupfromsugar,sucroseisboiledinwaterwithalittleacid,suchaslemon
juice.Whydoestheproductmixturetastesweeterthanthestartingsucrosesolution?
22.27WhichofthefollowingdisaccharidesarereducedbyNaBH4?
(a)sucrose
(b)lactose
(c)maltose
Polysaccharides
22.28Whatisthedifferenceinstructurebetweenoligosaccharidesandpolysaccharides?
22.29NamethreepolysaccharidesthatarecomposedofunitsofDglucose.Inwhichofthethree
polysaccharidesaretheglucoseunitsjoinedbyglycosidicbonds?Inwhicharetheyjoinedby
glycosidicbonds?
22.30Starchcanbeseparatedintotwoprincipalpolysaccharides:amyloseandamylopectin.Whatis
themajordifferenceinstructurebetweenthetwo?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
22.312,6dideoxyDaltrose,knownalternativelyasDdigitoxose,isamonosaccharideobtainedfrom
thehydrolysisofdigitoxin,anaturalproductextractedfrompurplefoxglove(Digitalis
purpurea).Digitoxinhasfoundwideuseincardiologybecauseitreducesthepulserate,
regularisesheartrhythmandstrengthenstheheartbeat.Drawthestructuralformulaof2,6
dideoxyDaltrose.

Thefoxgloveplantproducestheimportantcardiacmedicationdigitalis.

22.32DrawFischerprojectionsforthemonosaccharidesLriboseandLarabinose.
22.33DrawDglucopyranose(Dglucose)asaHaworthprojection.Now,usingonlythefollowing
information,drawHaworthprojectionsforthefollowingmonosaccharides.
(a)Dmannopyranose(Dmannose).TheconfigurationofDmannosediffersfromthatof
DglucoseonlyatC(2).
(b)Dgulopyranose(Dgulose).TheconfigurationofDgulosediffersfromthatofD
glucoseatC(3)andC(4).
22.34ConverteachofthefollowingHaworthprojectionstoanopenchainformandthentoaFischer
projection.
(a)

(b)

Namethemonosaccharidesyouhavedrawn.
22.35ConverteachofthefollowingchairconformationstoanopenchainformandthentoaFischer
projection.
(a)

(b)

Namethemonosaccharidesyouhavedrawn.
22.36TheconfigurationofDarabinosediffersfromtheconfigurationofDriboseonlyatC(2).Using
thisinformation,drawaHaworthprojectionforDarabinofuranose(Darabinose).
22.37DrawFischerprojectionsfortheproduct(s)formedbythereactionofDgalactosewiththe
followingcompounds,andstatewhethereachproductisopticallyactiveoropticallyinactive.
(a)NaBH4inH2O
(b)AgNO3inNH3,H2O
22.38Repeatquestion22.37,butuseDriboseinplaceofDgalactose.
22.39ThereductionofDfructosebyNaBH4givestwoalditols,oneofwhichisDsorbitol.Nameand
drawastructuralformulafortheotheralditol.
22.40Lfucose,oneofseveralmonosaccharidescommonlyfoundinthesurfacepolysaccharidesof
animalcells,issynthesisedbiochemicallyfromDmannoseinthefollowingeightsteps.
 (a)Describethetypeofreaction(oxidation,reduction,hydration,dehydrationetc.)involved
ineachstep.
(b)Explainwhythismonosaccharide,whichisderivedfromDmannose,nowbelongstothe
Lseries.
22.41Ascorbicacidisadiproticacidwiththefollowingacidionisationconstants:pKa1=4.17and
pKa2=11.57.Thetwoacidichydrogenatomsarethoseconnectedwiththeenediolpartofthe
molecule.Whichhydrogenatomhaswhichionisationconstant?(Hint:Drawseparatelytheanion
derivedbythelossofoneofthesehydrogenatomsandthatformedbythelossoftheother
hydrogenatom.Whichanionhasthegreaterdegreeofresonancestabilisation?)
22.42Trehaloseisfoundinyoungmushroomsandisthechiefcarbohydrateinthebloodofcertain
insects.TrehaloseisadisaccharideconsistingoftwoDmonosaccharideunits,joinedbyan
1,1glycosidicbond.
 (a)Istrehaloseareducingsugar?
(b)Doestrehaloseundergomutarotation?
(c)Namethetwomonosaccharideunitsofwhichtrehaloseiscomposed.
22.43Hotwaterextractsofgroundwillowbarkareaneffectivepainreliever.Unfortunately,theliquid
issobitterthatmostpeoplerefuseit.Thepainrelieverintheseinfusionsissalicin.

Namethemonosaccharideunitinsalicin.
22.44AFischerprojectionofNacetylDglucosamineisgivenonp.981.
(a)DrawaHaworthprojectionandachairconformationfortheandpyranoseformsof
thismonosaccharide.
(b)DrawaHaworthprojectionandachairconformationforthedisaccharideformedby
joiningtwounitsofthepyranoseformofNacetylDglucosaminebya1,4glucosidic
bond.Ifyourdrawingiscorrect,youhavethestructuralformulafortherepeatingdimer
ofchitin,thestructuralpolysaccharidecomponentoftheshelloflobstersandother
crustaceans.
22.45Proposestructuralformulaefortherepeatingdisaccharideunitinthefollowingpolysaccharides.
(a)Alginicacid,isolatedfromseaweed,isusedasathickeningagentinicecreamandother
foods.AlginicacidisapolymerofDmannuronicacidinthepyranoseform,joinedby
1,4glycosidicbonds.
(b)Pecticacidisthemaincomponentofpectin,whichisresponsiblefortheformationof
jelliesfromfruitsandberries.PecticacidisapolymerofDgalacturonicacidinthe
pyranoseformjoinedby1,4glycosidicbonds.
22.46ThefollowingareaHaworthprojectionandachairconformationfortherepeatingdisaccharide
unitinchondroitin6sulfate.

Thisbiopolymeractsasaflexibleconnectingmatrixbetweenthetoughproteinfilamentsin
cartilageandisavailableasadietarysupplement,oftencombinedwithDglucosaminesulfate.
Somebelievethatthecombinationcanstrengthenandimprovejointflexibility.
(a)Fromwhattwomonosaccharideunitsistherepeatingdisaccharideunitofchondroitin6
sulfatederived?
(b)Describetheorientationoftheglycosidicbondbetweenthetwounits.
(c)Whichisthebetterrepresentationofthestructureofchondroitin6sulfate?
22.47Trehaloseisanaturallyoccurringdisaccharidefoundinbacteria,insectsandmanyplants.It
protectscellsfromdryconditionsbecauseofitsabilitytoretainwater,therebypreventing
cellulardamagefromdehydration.Thispropertyoftrehalosehasalsobeenexploitedinthe
preparationoffoodandcosmetics.Trehaloseisnotareducingsugar,itishydrolysedtoyield
twoequivalentsofDglucose,anditdoesnothaveanyglycosidelinkages.Drawthestructure
oftrehalose.
22.48Salicinisanaturalanalgesicpresentinthebarkofwillowtrees,andithasbeenusedfor
thousandsofyearstotreatpainandreducefevers.
 (a)Issalicinareducingsugar?
(b)Identifytheproductsobtainedwhensalicinishydrolysedinthepresenceofanacid.
(c)Issalicinanglycosideoraglycoside?
(d)Drawthemajorproductexpectedwhensalicinistreatedwithexcessaceticanhydridein
thepresenceofpyridine.
(e)Wouldyouexpectsalicintoexhibitmutarotationwhendissolvedinneutralwater?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
22.1Onestepinglycolysis,thepathwaythatconvertsglucosetopyruvate,involvesanenzyme
catalysedconversionofdihydroxyacetonephosphatetoDglyceraldehyde3phosphate.

Showthatthistransformationcanberegardedastwoenzymecatalysedketoenoltautomerisations
(section21.5).
22.2Onepathwayforthemetabolismofglucose6phosphateisitsenzymecatalysedconversionto
fructose6phosphate.

Showthatthistransformationcanberegardedastwoenzymecatalysedketoenol
tautomerisations.
22.3Epimersarecarbohydratesthatdifferinconfigurationatonlyonestereocentre.
(a)Whichofthealdohexosesareepimersofeachother?
(b)Areallanomerpairsalsoepimersofeachother?Explain.Areallepimersalsoanomers?
Explain.
22.4Oligosaccharidesareveryvaluabletherapeutically,butareespeciallydifficulttosynthesise,even
thoughthestartingmaterialsarereadilyavailable.Thestructureofglobotrioseisshownbelow.
ThismoleculeisareceptorforaseriesoftoxinssynthesisedbysomestrainsofE.coli.

Fromlefttoright,globotrioseconsistsofan1,4linkageofgalactosetoagalactosethatispartof
a1,4linkagetoglucose.Thesquigglylineindicatesthattheconfigurationatthatcarbonatom
canbeor.Suggestwhyitwouldbedifficulttosynthesisethistrisaccharide,forexample,by
firstformingthegalactosegalactoseglycosidicbondandthenformingtheglycosidicbondto
 glucose.

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 KEYTERMS
alditols Fischerprojections Monosaccharides
aldoses furanose Mutarotation
anomericcarbon glycoside oligosaccharide
anomers glycosidicbond penultimatecarbon
carbohydrates Haworthprojection polysaccharides
chairconformation hemiacetals pyranose
Dmonosaccharide ketoses reducingsugar
disaccharides Lmonosaccharide trisaccharides

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CHAPTER

23 CarboxylicAcidsandtheir
Derivatives
Carboxylicacidsandtheirderivativesareimportantcompoundsinourlivesbecausetheyplayasignificantrole
infoodsandmanybiologicalprocesses.Theyalsofindindustrialapplicationsintheformofpolyesters,
polyamidesandmorerecentlyasbiodieselfuel.Carboxylicacidsareweakacidsandareresponsibleforthe
sourtasteinmanyfoods.

Carboxylicacidsandtheirestersareimportantflavourcomponentsoffruits.Citricacid(belowleft)isabundant
inoranges,lemons,limes,grapefruitsandmandarins.Malicacidwassonamedbecauseitwasisolatedfrom
apples(appletreesbelongtothegenusMalus).Whiletartaricacidisfoundinmanyfruits,itisanimportant
acidingrapesandabyproductofthewineindustry.Carboxylicacidsalsoinhibitorretardmicrobialgrowth.
Thisaccountsfortheuseofvinegar(whichcontainsabout5%aceticacid)topickle(preserve)meatsand
vegetables.Benzoicacid(additive210211213areitssodium,potassiumandcalciumsalts)iscommonly
usedasafoodpreservative,andcitricacid(foodacid330331isitssodiumsalt)isacommonadditiveinsoft
drinks.Theodourandflavouroffruitsareduetoacomplexmixtureofcompounds,notjustindividualesters.
However,individualesterscanbeimportantcontributorstotheodourandflavour.Forexample,theestersof
aceticacidareimportantcontributorstotheodoursofbanana(isopentylacetate,belowright,andbutyl
acetate),pear(pentylacetate)andorange(octylacetate).Similarly,theestersofbutanoicacid(avery
unpleasantsmellingacid)arecommoninapplesandpineapples(methylandethylbutanoate),pears(pentyl
butanoate),andstrawberriesandapricots(isopentylbutanoate).

Inthischapterwewillstudythechemistryofcarboxylicacidsandfourclassesoforganiccompoundsderived
fromthecarboxylgroup:acidhalides,acidanhydrides,estersandamides.
 KEYTOPICS

23.1Structureandbonding
23.2Nomenclature
23.3Physicalproperties
23.4Preparationofcarboxylicacids
23.5Reactionsofcarboxylicacidsandderivatives
23.6Triglycerides

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23.1StructureandBonding
Carboxylicacidsandtheirderivativeshavesimilarstructuralandbondingfeaturesthatresultinsimilar
reactions.However,theirsubtlestructuraldifferencesalsoleadtoquitedifferentreactivities.

CarboxylicAcids
Thecarboxylicacidgroupcomprisesthecarboxylgroup,sonamedbecauseitismadeupofacarbonyl
groupandahydroxylgroup.ThefollowingisaLewisstructureofthecarboxylgroup,aswellastwo
alternativerepresentationsofit:

ThegeneralformulaofanaliphaticcarboxylicacidisRCOOHthatofanaromaticcarboxylicacidis
ArCOOH(Ar=aromaticring).Thegeneralformulaforeachofthefourcarboxylicacidderived
functionalgroupsisgivenbelow,alongwithadrawingtohelpyouseehowthegroupisformallyrelated
toacarboxylgroup.Inallofthesegroups,thecarbonylcarbonatomisbondedtoaheteroatom(anatom
otherthancarbonorhydrogen).

AcidHalides
Theacidhalide(acylhalide)functionalgroupcomprisesanacylgroup(RCO)bondedtoahalogen
atom.ThesearesometimeswritteninabbreviatedformasRCOXorArCOX(whereX=halogen).The
mostcommonacidhalidesaretheacidchlorides.
AcidAnhydrides
Theacidanhydridefunctionalgroup(commonlyreferredtosimplyasananhydride)istwoacylgroups
bondedtoanoxygenatom.Theanhydridemaybesymmetrical(withtwoidenticalacylgroups),orit
maybemixed(withtwodifferentacylgroups).

EstersofCarboxylicAcids
TheesterfunctionalgroupisanacylgroupbondedtoanORoranOArgroup.

Whenestersareformedbetweenanalcoholandacarboxylicacidgroupfromwithinthesamemolecule,
theyarecyclicandaretermedlactones.

AmidesofCarboxylicAcids
Theamidefunctionalgroupisanacylgroupbondedtoatrivalentnitrogenatom.Amidescanbe
classifiedasprimary(Nbondedtoonecarbonatom),secondary(Nbondedtotwocarbonatoms)or
tertiary(Nbondedtothreecarbonatoms).
Whenamidesareformedbetweenanaminogroupandacarboxylicacidgroupfromwithinthesame
molecule,theyarecyclicandaretermedlactams.Amidebondsarethekeystructuralfeaturethatjoins
aminoacidstogethertoformpolypeptidesandproteins(chapter24).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
23.2Nomenclature
WeexplainedthebasicrulesofIUPACnomenclatureinchapter2.Here,wewillbrieflydescribethe
processforcarboxylicacidsandtheirderivatives.Wewillcommencewiththecarboxylicacidsand
workprogressivelythroughtheacidhalides,anhydrides,estersandfinallytheamides.

CarboxylicAcids
WederivetheIUPACnameofacarboxylicacidfromthatofthelongestcarbonchainthatcontainsthe
carboxylgroupbydroppingthefinalefromthenameoftheparentalkaneandreplacingitwithoic
acid.Wenumberthechainbeginningwiththecarbonatomofthecarboxylgroupsinceitisunderstood
tobeC(1),thereisnoneedtogiveitanumber.Inthefollowingexamples,thecommonnameofeach
acidisgiveninparentheses.

Manyaliphaticcarboxylicacidswereknownlongbeforethedevelopmentofstructuraltheoryand
IUPACnomenclatureandwerenamedaccordingtotheirsourceorforsomecharacteristicproperty.
Table23.1listsseveraloftheunbranchedaliphaticcarboxylicacidsfoundinthebiologicalworld(e.g.
figure23.1),alongwiththecommonnameofeach.Thosewith16,18and20carbonatomsare
particularlyabundantinfatsandoils(section23.6).
TABLE23.1 Severalaliphaticcarboxylicacidsandtheircommonnames.
Structure IUPACname Commonname Derivation
HCOOH methanoicacid formicacid Latin:formica,ant
CH3COOH ethanoicacid aceticacid Latin:acetum,vinegar
CH3CH2COOH propanoicacid propionicacid Greek:propion,firstfat

CH3(CH2)2COOH butanoicacid butyricacid Latin:butyrum,butter

CH3(CH2)3COOH pentanoicacid valericacid Latin:valere,tobestrong

 CH3(CH2)4COOH hexanoicacid caproicacid Latin:caper,goat

CH3(CH2)6COOH octanoicacid caprylicacid Latin:caper,goat

CH3(CH2)8COOH decanoicacid capricacid Latin:caper,goat

CH3(CH2)10COOH dodecanoicacid lauricacid Latin:laurus,laurel

CH3(CH2)12COOH tetradecanoicacid myristicacid Greek:myristikos,fragrant

CH3(CH2)14COOH hexadecanoicacid palmiticacid Latin:palma,palmtree

CH3(CH2)16COOH octadecanoicacid stearicacid Greek:stear,solidfat

CH3(CH2)18COOH eicosanoicacid arachidicacid Greek:arachis,peanut

FIGURE23.1Formicacidwasfirstobtainedin1670fromthedestructivedistillationofantsbelongingtothe
genusFormica.Itisoneofthecomponentsoftheirvenom.

IntheIUPACsystem,acarboxylgrouptakesprecedenceovermostotherfunctionalgroups(table23.1,
p.937),includinghydroxylandaminogroups,aswellasthecarbonylgroupsofaldehydesand
ketones.Asillustratedinthefollowingexamples,anOHgroupofanalcoholisindicatedbythe
prefixhydroxy,anNH2groupofanaminebyamino,andan Ogroupofanaldehydeorketone
byoxo.

Dicarboxylicacidsarenamedbyaddingthesuffixdioic,followedbythewordacid,tothenameofthe
carbonchainthatcontainsbothcarboxylgroups.Becausethetwocarboxylgroupscanbeonlyatthe
endsoftheparentchain,thereisnoneedtonumberthem.ThefollowingareIUPACnamesand
commonnamesforseveralimportantaliphaticdicarboxylicacids.
Thenameoxalicacidisderivedfromoneofitssourcesinthebiologicalworld,namely,plantsofthe
genusOxalis,oneofwhichisthesoursob(sourgrass)plant,O.pescaprae(figure23.2).Oxalicacid
alsooccursinhumanandanimalurine,andcalciumoxalate(thecalciumsaltofoxalicacid)isamajor
componentofkidneystones.Adipicacidisoneofthetwomonomersrequiredforthesynthesisofthe
polymernylon6,6.

FIGURE23.2ThesoursobplantisanintroducedplantandisclassifiedasaweedinmanypartsofAustralia.
Itmaycauseoxalatepoisoningifeatenbylivestock.

Acarboxylicacidcontainingacarboxylgroupbondedtoacycloalkaneringisnamedbygivingthe
nameoftheringandaddingthesuffixcarboxylicacid.Theatomsoftheringarenumberedbeginning
withthecarbonatombearingtheCOOHgroup.

Thesimplestaromaticcarboxylicacidisbenzoicacid.Derivativesarenamedbyusingnumbersand
prefixestoshowthepresenceandlocationofsubstituentsrelativetothecarboxylgroup.Certain
aromaticcarboxylicacidshavecommonnamesbywhichtheyaremoreusuallyknown.Forexample,2
hydroxybenzoicacidismoreoftencalledsalicylicacid,namedbecauseitwasfirstobtainedfromthe
barkofthewillow,atreeofthegenusSalix.Aromaticdicarboxylicacidsarenamedbyaddingthe
wordsdicarboxylicacidtobenzene.Examplesarebenzene1,2dicarboxylicacidandbenzene1,4
dicarboxylicacidthesearemoreusuallyknownbytheircommonnames,phthalicacidandterephthalic
acid,respectively.Terephthalicacidisoneofthetwoorganiccomponentsrequiredforthesynthesisof
PET(polyethyleneterephthalate)plasticbottles.

WORKEDEXAMPLE23.1
NamingCarboxylicAcids
WritetheIUPACnameforeachofthefollowingcarboxylicacids.
(a)

(b)

(c)

Analysis
(a)Firstdeterminethenumberofcarbonatomsinthelongestchainandthentheposition
ofanysubstituentoralkene(startnumberingfromtheacidgroup).Wherenecessary,
indicatethestereochemistry.
(b)Thisshouldbenamedasacycloalkanecarboxylicacid.
(c)Determinethestereochemistryofthechiralcentre(seesection17.3).

Solution

Commonnamesaregiveninparentheses.
(a)Zoctadec9enoicacid(oleicacid,cisoctadec9enoicacid)
(b)(R,R)2hydroxycyclohexanecarboxylicacid
(c)(R2hydroxypropanoicacid((R)lacticacidorDlacticacid)

Isouranswerreasonable?

Tocheckyouranswer,drawastructurefromthenameandseeifitmatchesthestructure
given.Isthistheonlystructurepossiblefromyouranswer?

PRACTICEEXERCISE23.1
Eachofthefollowingcompoundshasa
wellrecognisedcommonname.Aderivative
ofglycericacidisanintermediatein
glycolysis.Maleicacidisanintermediatein
thetricarboxylicacid(TCA)cycle(also
knownasthecitricacidorKrebscycle).
Mevalonicacidisanintermediateinthe
 biosynthesisofsteroids.
(a)

(b)

(c)

WritetheIUPACnameforeachofthese
compounds.Becertaintoshowthe
configurationofeach.

AcidHalides
Acidhalidesarenamedbychangingthesuffixicacidinthenameoftheparentcarboxylicacidtoyl
halide.

AcidAnhydrides
Acidanhydridesarenamedbyreplacingthewordacidwithanhydride.Whentheanhydrideisnot
symmetrical,bothacidgroupsarenamed.
EstersandLactones
BothIUPACandcommonnamesofestersarederivedfromthenamesoftheparentcarboxylicacids.
Thealkylorarylgroupbondedtotheoxygenatomisnamedfirst.Thisisfollowed,asaseparateword,
bythenameoftheacid,inwhichthesuffixicacidisreplacedbythesuffixate.

TheIUPACnameofalactoneisformedbydroppingthesuffixoicacidfromthenameoftheparent
carboxylicacidandaddingthesuffixolactone.Thecommonnameisderivedsimilarly.Thelocationof
theoxygenatomintheringisindicatedbyanumberiftheIUPACnameoftheacidisusedandbya
Greekletter(,,,, etc.)ifthecommonnameoftheacidisused.

AmidesandLactams
AmidesarenamedbydroppingthesuffixoicacidfromtheIUPACnameoftheparentacid,oricacid
fromitscommonname,andaddingamide.Ifthenitrogenatomofanamideisbondedtoanalkylor
arylgroup,thegroupisnamedanditslocationonthenitrogenatomisindicatedbyN.Twoalkylor
arylgroupsonthenitrogenatomareindicatedbyN,NdiifthegroupsareidenticalorbyNalkylN
alkyliftheyaredifferent.

Cyclicamidesaregiventhespecialnamelactam.Theircommonnamesarederivedinthesamewayas
lactonesexceptthatthesuffixisolactam.
Thecompound6hexanolactam(caprolactam)isakeyintermediateinthesynthesisofnylon6(section
26.3,p.1125).Note:Thehexinhexanolactamreferstothenumberofcarbonatoms,ratherthanthe
ringsize.

WORKEDEXAMPLE23.2

NomenclatureofCarboxylicAcidDerivatives
WritetheIUPACnameforeachofthefollowingcompounds.
(a)

(b)

(c)

(d)

Analysis

Firstidentifythefunctionalgrouppresentandthentheacidfromwhichitisderived.The
ketonegroupin(b)mustbenamedwiththeprefixoxo.Compound(d)hasbeenderived
fromasubstitutedaceticacid.

Solution

Commonnamesandderivationsaregiveninparentheses.
(a)methyl3methylbutanoate(methylisovalerate,fromisovalericacid)
(b)ethyl3oxobutanoate(ethylacetoacetate,fromacetoaceticacidethylketobutyrate
 fromketobutyricacid)
(c)hexanediamide(adipamide,fromadipicacid)
(d)phenylethanoicanhydride(phenylaceticanhydride,fromphenylaceticacid)

Isouranswerreasonable?

Tocheckyouranswer,drawastructurefromthenameandseeifitmatchesthestructure
given.

PRACTICEEXERCISE23.2
Drawastructuralformulaforeachofthe
followingcompounds.
(a)Ncyclohexylacetamide
(b)butylacetate
(c)cyclobutylbutanoate
(d)N(2octyl)benzamide
(e)diethyladipate
(f) propanoicanhydride

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
23.3PhysicalProperties
Intheliquidandsolidstates,carboxylicacidsareassociatedbyintermolecularhydrogenbondingintodimers,as
shownbelowforaceticacid.

ChemicalConnections

CarboxylicAcidsandDerivativesinMedicine

Fromtreebarktoantiinflammatoryagents

Thefirstdrugdevelopedforwidespreadusewasaspirin,today'smostcommonpainreliever.Thestoryofthe
developmentofthismodernpainrelievergoesbackmorethan2000yearswhentheGreekphysician
Hippocratesrecommendedchewingthebarkofthewillowtreetoalleviatethepainofchildbirthandtotreat
eyeinfections.

Theactivecomponentofwillowbarkwasfoundtobesalicin,acompoundcomposedofsalicylalcohol
joinedtoaunitofDglucose(chapter22).Hydrolysisofsalicininaqueousacidgivessalicylalcohol,which
canthenbeoxidisedtosalicylicacid,anevenmoreeffectiverelieverofpain,feverandinflammationthan
salicin,andwithoutanextremelybittertaste.

In1883,chemistsatBayerinGermanypreparedacetylsalicylicacid(aspirin)andfoundittobeeffectivein
relievingthepainandinflammationofrheumatoidarthritis.Italsodidnothavesalicylicacid'sunpleasant
sideeffectofcausingsevereirritationofthemucousmembraneliningthestomach.Bayerbeganlargescale
productionofaspirinin1899.
Inthe1960s,inasearchformoreeffectiveandlessirritatinganalgesicsandantiinflammatorydrugs,the
BootsPureDrugCompanyinEnglanddiscoveredanevenmorepotentcompound,ibuprofen,andsoon
thereafterSyntexCorporationintheUnitedStatesdevelopednaproxen.

Intheearly1970s,scientistsdiscoveredthataspirinactsbyinhibitingcyclooxygenase(COX),akeyenzyme
intheconversionofarachidonicacidtoprostaglandins.Prostaglandinsarebiochemicalregulatorswithmany
importantfunctionsincludingstimulatinginflammationandinducingfever.Ibuprofenandnaproxenare
believedtoactbyinhibitingtheCOXenzyme.

ThediscoverythatthesedrugsowetheireffectivenesstotheinhibitionofCOXopenedanentirelynew
avenuefordrugresearch.Ifweknowmoreaboutthestructureandfunctionofthiskeyenzyme,itmightbe
possibletodesignanddiscoverevenmoreeffectivenonsteroidalantiinflammatorydrugsforthetreatmentof
rheumatoidarthritisandotherinflammatorydiseases.

Frommouldtoantibiotics

Thepenicillinswerediscoveredin1928bytheScottishbacteriologistSirAlexanderFleming.Asaresultof
thebrilliantexperimentalworkofSirHowardFlorey,anAustralianpathologist,andErnstChain,aGerman
chemistwhofledNaziGermany,penicillinGwasintroducedintothepracticeofmedicinein1943.Fortheir
pioneeringworkindevelopingoneofthemosteffectiveantibioticsofalltime,Fleming,FloreyandChain
wereawardedtheNobelPrizeinphysiologyormedicinein1945.Thepenicillinsowetheirantibacterial
activitytoacommonmechanismthatinhibitsthebiosynthesisofavitalpartofbacterialcellwalls.The
structuralfeaturecommontoallpenicillinsisalactamringfusedtoafivememberedringcontainingone
sulfuratomandonenitrogenatom.

Soonafterthepenicillinswereintroducedintomedicalpractice,penicillinresistantstrainsofbacteriabegan
toappearandhavesinceproliferated.Oneapproachtocombatingresistantstrainsistosynthesisenewer,
moreeffectivepenicillins.Anotherapproachistosearchfornewer,moreeffectivelactamantibiotics.The
mosteffectiveofthesediscoveredsofararethecephalosporins,thefirstofwhichwasisolatedfromthe
fungusCephalosporiumacremonium.Thisclassoflactamantibioticshasanevenbroaderspectrumof
antibacterialactivitythanthepenicillinsandiseffectiveagainstmanypenicillinresistantbacterialstrains.

Frommouldyclovertoanticoagulants

In1933,adisgruntledfarmerdeliveredapailofunclottedbloodtothelaboratoryofDrKarlLinkatthe
UniversityofWisconsinandtoldtalesofcowsbleedingtodeathfromminorcuts.Overthenextcoupleof
years,Linkandhiscollaboratorsdiscoveredthat,whencowsarefedmouldyclover,theirbloodclottingis
inhibited.Fromthemouldyclover,Linkisolatedtheanticoagulantdicoumarol,asubstancethatdelaysor
preventsbloodfromclottingbyinterferingwithvitaminKactivity.Withinafewyearsafteritsdiscovery,
dicoumarolbecamewidelyusedtotreatvictimsofheartattackandothersatriskofdevelopingbloodclots.
 dicoumarolbecamewidelyusedtotreatvictimsofheartattackandothersatriskofdevelopingbloodclots.

Coumarinisalactone(cyclicester)thatgivescloveitspleasantsmell.Itdoesnotinterferewithbloodclotting
andhasbeenusedasaflavouringagentinthefoodindustry.Coumarinisconvertedtodicoumarolassweet
cloverbecomesmouldy.

Inasearchforevenmorepotentanticoagulants,Linkdevelopedwarfarin,nowusedprimarilyasaratpoison:
Whenratsconsumewarfarin,theirbloodfailstoclot,andtheybleedtodeath.Soldunderthebrandname
Coumadin ,warfarinisalsousedasabloodthinnerinhumans.Thecommercialproductisaracemic
mixture,buttheSenantiomerismoreactivethantheRenantiomer.

Carboxylicacidshavesignificantlyhigherboilingpointsthanothertypesoforganiccompoundswithsimilarnumbers
ofelectrons(and,therefore,comparablemolarmass),suchasalcohols,aldehydesandketones.Forexample,butanoic
acid(table23.2)hasahigherboilingpointthaneitherpentan1olorpentanal.Thisisbecausecarboxylicacidsare
polarandformverystrongintermolecularhydrogenbonds.
 TABLE23.2 Boilingpointsandsolubilitiesinwaterofselectedcarboxylicacids,alcoholsandaldehydesofcomparable
molarmass.

Molar Numberof Boilingpoint Solubility(g/100mL

Structure Name mass electrons (C) H2O)
CH3COOH aceticacid 60.1 32 118 infinite
CH3CH2CH2OH propan1ol 60.1 34 97 infinite
CH3CH2CHO propanal 58.1 32 48 16

CH3(CH2)2COOH butanoic 88.1 48 163 infinite

acid
CH3(CH2)3CH2OH pentan1ol 88.1 50 137 2.7
CH3(CH2)3CHO pentanal 86.1 48 103 slight

CH3(CH2)4COOH hexanoic 116.2 64 205 1.0

acid
CH3(CH2)5CH2OH heptan1ol 116.2 66 176 0.2
CH3(CH2)5CHO heptanal 114.1 64 153 0.1

Carboxylicacidsalsointeractwithwatermoleculesbyhydrogenbondingthroughboththeircarbonylandhydroxyl
groups.Becauseofthesehydrogenbonds,carboxylicacidsaremoresolubleinwaterthanarealcohols,ethers,
aldehydesandketonesofcomparablemolarmass.Thesolubilityofacarboxylicacidinwatergenerallydecreasesas
itsmolarmassincreases(table23.2).Weaccountforthistrendinthefollowingway.Acarboxylicacidhastwo
regionsofdifferentpolarityapolarhydrophiliccarboxylgroupand,exceptforformicacid,anonpolar
hydrophobichydrocarbonchain.Thehydrophilic(waterloving)carboxylgroupincreaseswatersolubilitythe
hydrophobic(waterhating)hydrocarbonchaindecreaseswatersolubility.

Thefirstfouraliphaticcarboxylicacids(formic,acetic,propanoicandbutanoicacids)areinfinitelysolubleinwater
becausethehydrophiliccharacterofthecarboxylgroupmorethancompensatesforthehydrophobiccharacterofthe
hydrocarbonchain.Asthesizeofthehydrocarbonchainincreasesrelativetothesizeofthecarboxylgroup,water
solubilitydecreases.Thesolubilityofhexanoicacidinwateris1.0g/100gwaterthatofdecanoicacidisonly0.2
g/100gwater.

Oneotherphysicalpropertyofcarboxylicacidsmustbementioned.Theliquidcarboxylicacids,frompropanoicacid
todecanoicacid,havefoulodours,althoughnotasbadasthoseofthiols.Butanoicacidisfoundinrancidbutter,stale
parmesancheese,staleperspirationandvomit.Pentanoicacidsmellsevenworseandgoats,whichsecreteC6,C8
andC10acids,arenotfamousfortheirpleasantodours.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
23.4PreparationofCarboxylicAcids
Therearemanymethodsavailableforthepreparationofcarboxylicacids.Someofthesewillbediscussed
brieflyhereandinmoredetailelsewhereinthistext.

OxidationofPrimaryAlcoholsandAldehydes
Primaryalcoholsandaldehydesarereadilyoxidisedtocarboxylicacidsbyavarietyofcommonoxidising
agents(discussedingreaterdetailinsections19.2and21.5).

OxidationofAlkylbenzenes
Althoughbenzeneisunaffectedbystrongoxidisingagents,suchasKMnO4andH2CrO4,alkylbenzenes
areoxidisedatthebenzyliccarbon(thecarbonatomattachedtothebenzenering)togivecarboxylic
acids.Whenwetreattoluenewiththeseoxidisingagentsundervigorousconditions,thesidechainmethyl
groupisoxidisedtoacarboxylgrouptogivebenzoicacid.

Ethylbenzeneandisopropylbenzenearealsooxidisedtobenzoicacidundertheseconditions.Theside
chainoftertbutylbenzene,whichhasnobenzylichydrogen(ahydrogenatombondedtoabenzylic
carbonatom),isnotaffectedbytheseoxidisingconditions.Fromtheseobservations,wecangeneralise
that:
ifabenzylichydrogenatomexists,thebenzyliccarbonatomisoxidisedtoacarboxylgroupandall
othercarbonatomsofthesidechainareremoved
ifnobenzylichydrogenatomexists,asintertbutylbenzene,thesidechainisnotoxidised
ifmorethanonealkylsidechainexists,eachisoxidisedtoacarboxylicacidgroup.
Oxidationof1,3diethylbenzenegivesbenzene1,3dicarboxylicacid,morecommonlynamedisophthalic
acid.
CarbonationofGrignardReagents
Grignardreagents(section21.5)reactwithcarbondioxidetogiveamagnesiumcarboxylatethatis
convertedintothecarboxylicacidbyacidification.Thisreactionisapplicabletoalkylandarylhalidesand
producescarboxylicacidswithonecarbonatommorethantheoriginalorganohalide.Ageneralreactionis
givenonthenextpage,followedbytwospecificexamples.

ThisreactionfollowsthesameprocessasthatinthereactionofGrignardreagentswithaldehydesand
ketones(section21.5).

FormationandHydrolysisofNitriles
Anothermethodofpreparingcarboxylicacidsfromhaloalkanesisbytheformationandsubsequent
hydrolysisofnitriles(compoundscontainingacyanogroup,C N).Likethecarbonationreaction
describedabove,thisprocessproducescarboxylicacidswithonecarbonatommorethantheoriginal
haloalkane.Thenitrileisformedbyanucleophilicsubstitutionreaction(section18.2)bycyanideionson
ahaloalkane.Theresultingnitrilecanthenbehydrolysedbyreactionwitheitherhotaqueousacidor
base.
HydrolysisofCarboxylicAcidDerivatives
Carboxylicacidscanalsobeobtainedbythehydrolysisofcarboxylicacidderivatives,particularlyesters
andamidesforexample:

Thechemistryofthisreactionwillbediscussedindetailinsection23.5.

WORKEDEXAMPLE23.3

FormationofCarboxylicAcids
Showhoweachofthefollowingcompoundscanbeconvertedinto3methylbutanoicacid.
(a)3methylbutanal
(b)1bromo2methylpropane

Analysis

First,drawthestructuresoftheproductandthestartingmaterial.Now,comparethetwo
compoundsanddeterminewhatchangesarerequiredtogofromthestartingmaterialtothe
product.Theproducthasonemoreoxygenatomthan(a),suggestingthatoxidationisrequired.
Theproducthasonemorecarbonatomthan(b),whichmeansthatweneedtointroduce
anothercarbonatomthismightbedoneviaaGrignardreactionorbythehydrolysisofa
nitrile.

Solution
(a)

Arangeofoxidisingagentscanbeused,includingKMnO4solutionorchromicacid,
H2CrO4.PCC(pyridiniumchlorochromate)isnotsuitable.
(b)

or
 Isouranswerreasonable?

Ineachcase,checkthatthecarbonskeletonisconsistentwiththenumberofcarbonatoms.
Youshouldalsocheckthatthereagentschosenareappropriatefortheproposed
transformations.

PRACTICEEXERCISE23.3
Showhoweachofthefollowingcompounds
canbeconvertedintobenzoicacid.
(a)benzylalcohol(phenylmethanol)
(b)iodobenzene

WORKEDEXAMPLE23.4

OxidationatBenzylicCarbonAtoms
DrawthestructuralformulafortheproductofvigorousoxidationbyH2CrO4ofeachofthe
followingcompounds.
(a)1,4dimethylbenzene(pxylene)
(b)1tertbutyl4ethylbenzene

AnalysisStartbycheckingwhetherthealkylgroupshaveatleastonebenzylichydrogen
atom.Iftheydo,thenchromicacidoxidisesthemtocarboxylicacidgroups,COOH.Ifnot,
thenitisnotoxidised.

Solution
(a)

(b)

Isouranswerreasonable?
 Checkthatthecarbonskeletonisconsistentwiththenumberofcarbonatoms.Checkalsothat
theoxidationhasoccurredatthebenzyliccarbonatom.

PRACTICEEXERCISE23.4
Predicttheproductsresultingfromvigorous
oxidationofeachofthefollowing
compoundsbyH2CrO4.
(a)

(b)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
23.5ReactionsofCarboxylicAcidsandDerivatives
Thereactionsofcarboxylicacidscanbeclassifiedintotwogeneraltypes:(a)acidbaseand(b)nucleophilic
acylsubstitution:

Wewillcommencethissectionwiththeacidbasechemistryofcarboxylicacids.Wewillthenstudythe
nucleophilicacylsubstitutionofthecarboxylicacidsandtheirderivatives.

Acidity
Althoughcarboxylicacidsareweakacids,relativetothemineralacids,theyaresignificantlymoreacidic
thanalcoholsandphenols(sections19.2and19.3).Atthispoint,itmaybeworthwhiletoreviewchapter11
andthediscussionofthepositionofequilibriuminacidbasereactions.

AcidIonisationConstants

ValuesofKaformostunsubstitutedaliphaticandaromaticcarboxylicacidsarebetween10 4and10 5.The

valueofKaforaceticacid,forexample,is1.810 5,sothepKaofaceticacidis4.74.

Carboxylicacids(pKa=45)arestrongeracidsthanalcohols(pKa=1618)becauseresonancestabilisesthe
carboxylateanionbydelocalisingitsnegativecharge.Nocomparableresonancestabilisationexistsin
alkoxideions.
Substitutionatthecarbonwithanatomoragroupofatomsofhigherelectronegativitythancarbon
increasestheacidityofcarboxylicacids,oftenbyseveralordersofmagnitude.Compare,forexample,the
aciditiesofaceticacid(pKa=4.74)andchloroaceticacid(pKa=2.85).Asinglechlorinesubstituentonthe
carbonatomincreasestheacidityconstantbynearly100times!Bothdichloroaceticacidand
trichloroaceticacidarestrongeracidsthanphosphoricacid(pKa=2.1).

Theacidstrengtheningeffectofhalogensubstitutionfallsoffratherrapidlywithincreasingdistancefrom
thecarboxylgroup.Althoughtheacidityconstantof2chlorobutanoicacid(pKa=2.83)is100timesthatof
butanoicacid,theacidityconstantof4chlorobutanoicacid(pKa=4.52)isonlyabouttwicethatofbutanoic
acid.

Ringsubstituentshavemarkedeffectsontheaciditiesofaromaticcarboxylicacidsthroughacombinationof
inductiveandresonanceeffects(asimilareffectwasdescribedforphenolsinsection19.3).Electron
withdrawinggroups,suchaschloro,cyanoandnitro,withdrawelectrondensityfromthearomaticring,
weakentheOHbondandstabilisethecarboxylateion.Conversely,electrondonatinggroups,suchas
amino,alkoxyandalkyl,increasetheelectrondensityofthearomaticringanddestabilisethecarboxylate
ion.Table23.3liststhepKavaluesofsomearomaticacids.

TABLE23.3 ThepKa valuesofsomearomaticacids.

WORKEDEXAMPLE23.5

Acidity
Whichacidineachofthefollowingsetsisthestronger?
(a)

(b)

Analysis

Firstidentifythedifferencebetweenthetwoacids.Inbothcasesitisthesubstituentonthe
carbonatom.Thecompoundwiththebetterelectronwithdrawinggroupwillbethestrongeracid.

Solution
(a)Thestrongeracidis2hydroxypropanoicacidbecauseoftheelectronwithdrawing
inductiveeffectofthehydroxyloxygenatom.
(b)Thestrongeracidis2oxopropanoicacidbecausetheelectronwithdrawinginductive
effectofthecarbonyloxygenatomisgreaterthanthatofthehydroxyloxygenatom.

Isouranswerreasonable?

CheckthepKavaluesoftheacidsalowerpKavaluemeansastrongeracidpropanoicacid
 (pKa=4.89),2hydroxypropanoicacid(pKa=3.85)and2oxopropanoicacid(pKa=2.39).

PRACTICEEXERCISE23.5
Matcheachofthefollowingcompoundswith
itsappropriatepKavalue:5.03,3.85or0.22.
(a)

(b)

(c)

ReactionwithBases
Allcarboxylicacids,whethersolubleorinsolubleinwater,reactwithNaOH,KOHandotherstrongbasesto
formwatersolublesalts.

Sodiumbenzoate,afungalgrowthinhibitor,isoftenaddedtobakedgoodstoretardspoilage.Calcium
propanoateisusedforthesamepurpose.
Carboxylicacidsalsoformwatersolublesaltswithammoniaandamines.

Carboxylicacidsreactwithsodiumhydrogencarbonateandsodiumcarbonatetoformwatersolublesodium
saltsandcarbonicacid(arelativelyweakacid).Carbonicacid,inturn,decomposestogivewaterandcarbon
dioxide,whichevolvesasagas.

Saltsofcarboxylicacidsarenamedinthesamewayassaltsofinorganicacids:Namethecationfirstand
thentheanion.Derivethenameoftheanionfromthenameofthecarboxylicacidbydroppingthesuffixic
acidandaddingthesuffixate.Forexample,thenameofCH3CH2COONa+issodiumpropanoate,andthat
ofCH3(CH2)14COONa+issodiumhexadecanoate(sodiumpalmitate).

Becausecarboxylicacidsaltsarewatersoluble,wecanconvertwaterinsolublecarboxylicacidstowater
solublealkalimetalorammoniumsaltsandthenextractthemintoaqueoussolution.Inturn,wecan
transformthesaltintothefreecarboxylicacidbyaddingastrongacid,suchasHClorH2SO4.These
reactionsallowustoseparatewaterinsolublecarboxylicacidsfromwaterinsolubleneutralcompounds.

Figure23.3showsaflowchartfortheseparationofbenzoicacid,awaterinsolublecarboxylicacid,from
benzylalcohol,awaterinsolublenonacidiccompound.First,wedissolvethemixtureofbenzoicacidand
benzylalcoholindiethylether.Next,weshaketheethersolutionwithaqueousNaOHtoconvertbenzoic
acidtoitswatersolublesodiumsalt.Thenweseparatetheetherfromtheaqueousphase.Distillationofthe
ethersolutionyieldsfirstdiethylether(bp=35C)andthenbenzylalcohol(bp=205C).Whenweacidify
theaqueoussolutionwithHCl,benzoicacidprecipitatesasawaterinsolublesolid(mp=122C)andis
recoveredbyfiltration.Similarseparationschemesweredescribedpreviouslyforphenols(section19.3)and
amines(section19.7).
 FIGURE23.3Flowchartforseparatingbenzoicacidfrombenzylalcohol.

NucleophilicAcylSubstitution
Themostcommonreactionofthecarboxylicacidfamily(carboxylicacids,acidhalides,anhydrides,esters
andamides)isnucleophilicacylsubstitution.Thekeystepinthisreactionistheadditionofanucleophileto
thecarbonylcarbontoformatetrahedralcarbonyladditionintermediate.Inthisrespect,thereactionsof
thesefunctionalgroupsaresimilartonucleophilicadditiontothecarbonylgroupsinaldehydesandketones
(section21.5).Inthereactionsofaldehydesandketones,thetetrahedralcarbonyladditionintermediate
formedisthenprotonated.Theresultofthisreactionisnucleophilicadditiontoacarbonylgroupofan
aldehydeoraketone.
Forfunctionalderivativesofcarboxylicacids,thefateofthetetrahedralcarbonyladditionintermediateis
quitedifferentfromthatofaldehydesandketones.Thisintermediatecollapsestoexpeltheleavinggroup
andregeneratethecarbonylgroup.Theresultofthisadditioneliminationsequenceisnucleophilicacyl
substitution.

Themajordifferencebetweenthesetwotypesofcarbonyladditionreactionsisthataldehydesandketones
donothaveagroup,Y,thatcanleaveasastableanion.Theyundergoonlynucleophilicacyladdition.The
carboxylicacidderivativeswestudyinthischapterdohaveagroup,Y,thatcanleaveasastableanion,so
theycanundergonucleophilicacylsubstitution.

Inthegeneralreactiononthepreviouspage,weshowthenucleophileandtheleavinggroupasanions.That
neednotbethecase,however.Neutralmolecules,suchaswater,alcohols,ammoniaandamines,mayalso
serveasnucleophilesintheacidcatalysedversionofthereaction.Ontheright,weshowtheleavinggroups
asanionstoillustrateanimportantpoint:theweakerthebase,thebetteristheleavinggroup(section18.2).

Theweakestbasesintheseriesontheright,andhencethebestleavinggroups,arethehalideionsCl,Br
andI,andthereforeacidhalidesarethemostreactivetowardsnucleophilicacylsubstitution.Thestrongest
base,andhencethepoorestleavinggroup,istheamideion,andthereforeamidesaretheleastreactive
towardsnucleophilicacylsubstitution.Acidhalidesandacidanhydridesaresoreactivethattheyarenot
foundinnature.Estersandamides,however,areextremelycommon.
Thefigurebelowgivesasummaryofkeyexamplesofnucleophilicacylsubstitutionreactionsthatthe
carboxylicacidfamilycanundergo.Theamides(Y=NH2),however,followthisgeneralschemeonlyfor
thehydrolysisreaction(additionofwater).Allthesewillbediscussedinmoredetaillaterinthischapter.

AcidHalideFormation
Amongtheacidhalides,acidchloridesarethemostfrequentlyusedinthelaboratoryandinindustrial
organicchemistry.Recallfromsection19.2thatalcoholscanbeconvertedintochloroalkanesbytreatment
withthionylchloride,SOCl2,orwithphosphoruschlorides,PCl3orPCl5.Thesereagentsalsoconvertthe
OHgroupofacarboxylicacidintoachloride,anexampleofanucleophilicacylsubstitutionreaction.The
mostcommonwaytoprepareanacidchlorideistotreatacarboxylicacidwiththionylchloride.
WORKEDEXAMPLE23.6

FormationofAcidChlorides
Completeeachofthefollowingequations.
(a)

(b)

Analysis

Inthistypeofquestion,youshouldtrytoclassifythereagentaccordingtoitspurpose.Inthese
examples,thereagentsconvertOHgroupstochlorides.

Solution
(a)

(b)

Isouranswerreasonable?

ThetwoprincipalreactionsofcarboxylicacidsarebreakingtheOHbond(aciddissociation)
andbreakingtheCOHbond(nucleophilicacylsubstitution).Inthiscase,itisthelatter,sothe
productsshouldshowthisi.e.hastheOHgroupbeenreplacedwithCl?

PRACTICEEXERCISE23.6
Completeeachofthefollowingequations.
(a)

(b)
ReactionswithAlcohols
Thereactionofcarboxylicacidsandtheirderivativeswithalcoholsisimportantforthepreparationofesters.
Inthefollowingpages,wewilldiscusstheesterificationreactionstartingwiththereactionofcarboxylic
acidswithalcohols.Wewilltheninvestigatethereactionsofacidchlorides,acidanhydrides,estersand
amideswithalcohols.

CarboxylicAcidstheFischerEsterification
Treatmentofacarboxylicacidwithanalcoholinthepresenceofanacidcatalyst(mostcommonly,
concentratedsulfuricacid)givesanester.ThismethodofforminganesterisgiventhespecialnameFischer
esterificationaftertheGermanchemistEmilFischer(18521919,NobelPrizeinchemistry,1902).Asan
exampleofaFischeresterification,treatingaceticacidwithethanolinthepresenceofconcentratedsulfuric
acidgivesethylacetate,acommonsolvent(figure23.4),andwater:

FIGURE23.4Theseproductscontainethylacetateasasolvent.KariAnnTapp

Acidcatalysedesterificationisreversible,andgenerally,atequilibrium,significantquantitiesofcarboxylic
acidandalcoholremain.Bycontrollingtheexperimentalconditions,however,wecanuseFischer
esterificationtoprepareestersinhighyields.Ifthealcoholischeaperthanthecarboxylicacid,wecanusea
largeexcessofthealcoholtodrivethereactiontotherightandachieveahighconversionofcarboxylicacid
toitsester.

WORKEDEXAMPLE23.7
FischerEsterification
CompletethefollowingFischeresterificationreactions.
(a)

(b)

Analysis

Sincetheseareexamplesofnucleophilicacylsubstitution,wesimplyneedtoidentifythenucleo
phileandthegrouptobesubstituted.Thenucleophileistheoxygenatomofthealcohol.

Solution
(a)

(b)

Isouranswerreasonable?

CheckthatyouhavesubstitutedalltheOHgroupsoftheacidswithORgroups.

PRACTICEEXERCISE23.7
CompletethefollowingFischeresterificationreactions.
(a)
 (b)

Notethat,althoughweshowtheacidcatalystasH2SO4whenwewriteFischeresterificationreactions,the
actualprotontransferacidthatinitiatesthereactionistheoxoniumionformedbythetransferofaproton
fromH2SO4(thestrongeracid)tothealcohol(thestrongerbase)usedintheesterificationreaction.

Thereactionaboveissimilartothefamiliarreactionofwaterwithsulfuricacid.

AmechanismfortheFischeresterificationreactionisshownbelowandweurgeyoutostudyitcarefully.Do
notbeoverwhelmedbythenumberofstepsitisstillbasicallyonlyanucleophilicacylsubstitution.

Step Protontransferfromtheacidcatalysttothecarbonyl
1: oxygenatomincreasestheelectrophilicityofthe
carbonylcarbonatom.
Step Thenucleophilicoxygenatomofanalcoholaddstothe
2: electrophiliccarbonylcarbonatomtoformanoxonium
ion.
Step Protontransferfromtheoxoniumiontoasecond
3: moleculeofalcoholgivesatetrahedralcarbonyladdition
intermediate(TCAI).
Step ProtontransfertooneoftheOHgroupsoftheTCAI
4: givesanewoxoniumion.
Step Waterislostfromthisoxoniumion.
5:
Step Protontransfertoamoleculeofalcoholgivestheester
6: andwaterandregeneratestheacidcatalyst.
Notethat,inthemechanismonthepreviouspage,steps1,3,4and6aresimplyprotontransferprocesses.
Step2istheformationofaCObond(theadditionpartofnucleophilicacylsubstitution)andstep5isthe
breakingofaCObond(theeliminationpartofnucleophilicacylsubstitution).Notealsothattheoxygen
atomofthealcoholisretainedintheester,whiletheOHgroupofthecarboxylicacidislost(aswater).
Thishasbeenconfirmedexperimentallybyusinganalcohollabelledwithaheavyisotopeofoxygen(18O).
Uponseparationofthecomponents,itwasfoundthattheestercontained18O,whilethewaterdidnot.

AcidChlorides
AcidchloridesreactwithalcoholsviaanucleophilicacylsubstitutionreactiontogiveanesterandHCl.
Becauseacidchloridesaresoreactivetowardsevenweaknucleophilessuchasalcohols,nocatalystis
necessaryforthesereactions.Phenolandsubstitutedphenolsalsoreactwithacidchloridestogiveesters.

AcidAnhydrides
Acidanhydridesreactwithalcoholstogive1moleequivalentofesterand1moleequivalentofacarboxylic
acid:

Aspirinissynthesisedonanindustrialscalebyreactingaceticanhydridewithsalicylicacid:

Notethat,intheuseofanhydridesforthepreparationofesters(andamides),1moleofcarboxylicacidis
producedasabyproduct.Thisisaninefficientuseofthecarboxylicacidand,consequently,anhydridesare
usedonlywhentheyareparticularlycheap(e.g.aceticandphthalicanhydrides).

Esters
Whentreatedwithanalcoholinthepresenceofanacidorbasecatalyst,estersundergoanexchange
reactioncalledtransesterification.Inthisreaction,theoriginalORgroupoftheesterisexchangedfora
newORgroup.Inthefollowingexample,thetransesterificationcanbedriventocompletionbyheating
thereactionatatemperatureabovetheboilingpointofmethanol(65C)sothatmethanoldistillsfromthe
reactionmixture:
Amides
Amidesdonotreactwithalcoholsunderanyexperimentalconditions.Alcoholsarenotstrongenough
nucleophilestoattackthecarbonylgroupofanamide.

Thereactionsofcarboxylicacids,acidchlorides,anhydrides,estersandamideswithalcoholsare
summarisedbelow.Notethattherearelargedifferencesintheratesandexperimentalconditionsunder
whichthesefunctionalgroupsundergoreactionswithalcohols.Atoneextremeareacidchloridesand
anhydrides,whichreactrapidlyattheotherextremeareamides,whichdonotreactatall.

Summaryofthereactionsofcarboxylicacids,acidchlorides,anhydrides,estersandamideswith
alcohols

ReactionwithWater:Hydrolysis
Thehydrolysisofcarboxylicacidderivativesisyetanotherexampleofanucleophilicacylsubstitution
reaction.Essentially,thecarboxylicacidderivativereactswithwatertogiveacarboxylicacidandHY.
AcidChlorides
LowmolarmassacidchloridesreactveryrapidlywithwatertoformcarboxylicacidsandHCl.

Highmolarmassacidchloridesarelesswatersolubleandsoreactlessrapidlywithwater.

AcidAnhydrides
Acidanhydridesaregenerallylessreactivethanacidchlorides.Lowmolarmassanhydrides,however,react
readilywithwatertoformtwomoleequivalentsofcarboxylicacid.

Esters
Estersarehydrolysedonlyveryslowly,eveninboilingwater.Hydrolysisbecomesconsiderablymorerapid,
however,whenestersareheatedinaqueousacidorbase.Whenwediscussedacidcatalysed(Fischer)
esterificationearlier(p.1019),wepointedoutthatesterificationisanequilibriumreaction.Hydrolysisof
estersinaqueousacidisalsoanequilibriumreactionandproceedsbythesamemechanismasesterification,
exceptinreverse.Theroleoftheacidcatalystistoprotonatethecarbonyloxygenatom,therebyincreasing
theelectrophiliccharacterofthecarbonylcarbonatomandsofacilitatingadditionbywatertoforma
tetrahedralcarbonyladditionintermediate.Collapseofthisintermediategivesthecarboxylicacidandan
alcohol.

Inthisreaction,theacidisacatalystasitisconsumedinthefirststepandisregeneratedattheendofthe
reaction.
Hydrolysisofesterscanalsobecarriedoutwithhotaqueousbase,suchasaqueousNaOH.Hydrolysisof
estersinaqueousbaseisoftencalledsaponification,areferencetotheuseofthisreactioninthe
manufactureofsoaps(section23.6).Eachmoleofesterhydrolysedrequires1moleofbase,asshowninthe
followingbalancedequation:

Thefollowingshowsamechanismforhydrolysisofanesterinaqueousbase.
Step1:Additionofahydroxideiontothecarbonylcarbonatomsoftheestergivesatetrahedral
carbonyladditionintermediate.

Step2:Collapseofthisintermediategivesacarboxylicacidandanalkoxideion.

Step3:Protontransferfromthecarboxylgroup(anacid)tothealkoxideion(abase)givesthe
carboxylateanion.Thisstepisirreversiblebecausethealcoholisnotastrongenoughnucleophileto
reactwithcarboxylateanion.

Notethatsteps1and2describeatypicalnucleophilicacylsubstitutionreactionstep3issimplyanacid
basereaction.

Therearetwomajordifferencesbetweenthehydrolysisofestersinaqueousacidandthatinaqueousbase.
1.Forhydrolysisinaqueousacid,acidisrequiredinonlycatalyticamounts.Forhydrolysisinaqueous
base,baseisrequiredinequimolaramountsbecauseitisareactant,notjustacatalyst.
2.Hydrolysisofanesterinaqueousacidisreversible.Hydrolysisinaqueousbaseisirreversible,
becausecarboxylateanionsdonotreactwithalcohols.

WORKEDEXAMPLE23.8

HydrolysisofEsters
Completeandbalancethefollowingequationsforthehydrolysisofeachesterinaqueoussodium
hydroxide,showingallproductsastheyareionisedinaqueousNaOH.
(a)
 (b)

Analysis

Firstidentifythecarbonylcarbonatom(s)oftheestersandtheleavinggroups.Substitutionofthe
ORgroup(theleavinggroup)byanOHgroupoccursatthesecarbonatoms.Finally,the
acidreactswiththestronglybasicalkoxideion(RO).

Solution
(a)

(b)

Isouranswerreasonable?

Theproductsofhydrolysisareacarboxylicacidandanalcohol.InaqueousNaOH,the
carboxylicacidisconvertedtoitssodiumsalt.Therefore,1moleofNaOHisrequiredforthe
hydrolysisof1moleofester.Compound(b)isadiester,so2molesofNaOHarerequired.

PRACTICEEXERCISE23.8
Completeandbalancethefollowingequationsforthehydrolysisof
eachesterinaqueoussolution,showingeachproductasitisionised
underthegivenexperimentalconditions.
(a)
 (b)

Amides
Amidesrequireconsiderablymorevigorousconditionsforhydrolysisinbothacidandbasethandoesters.
Amidesundergohydrolysisinhotaqueousacidtogiveacarboxylicacidandammonia(oramines).
Hydrolysisisdriventocompletionbytheacidbasereactionbetweenammoniaortheamineandacidto
formanammoniumsalt.Onemoleofacidisrequiredpermoleofamide.

Inaqueousbase,theproductsofamidehydrolysisareacarboxylicacidandammoniaoranamine.Base
catalysedhydrolysisisdriventocompletionbytheacidbasereactionbetweenthecarboxylicacidandbase
toformasalt.Onemoleofbaseisrequiredpermoleofamide.

Thereactionsofacidchlorides,anhydrides,estersandamideswithwateraresummarisedbelow.Remember
that,althoughallfourfunctionalgroupsreactwithwater,therearelargedifferencesintheratesand
experimentalconditionsunderwhichtheyarehydrolysed.

Summaryofthereactionsofacidchlorides,anhydrides,estersandamideswithwater
WORKEDEXAMPLE23.9

HydrolysisofAmides
Writeanequationforthehydrolysisofeachofthefollowingamidesinconcentratedaqueous
HCl,showingallproductsastheyexistinaqueousHClandshowingtheamountofHClrequired
forthehydrolysisofeachamide.
(a)

(b)

Analysis

Firstidentifythecarbonylcarbonatomoftheamide.SubstitutionoftheNR2orNHRgroup
byanOHgroupwilloccuratthiscarbonatom.Rememberthatthehydrolysisofanamide
givesacarboxylicacidandanamine(orammonia).In(b),thecarboxylicacidandtheamineare
partofthesamemolecule,soonlyoneproductwillbeformed.Finallyconsidertheconditionsof
thereactiontodeterminetheionisedformoftheproduct(s).
 Solution
(a)HydrolysisofN,Ndimethylacetamidegivesaceticacidanddimethylamine.
Dimethylamine,abase,isprotonatedbyHCltoformadimethylammoniumionandis
showninthebalancedequationasdimethylammoniumchloride.Completehydrolysisof
thisamiderequires1moleofHClforeachmoleoftheamide.

(b)Hydrolysisofthislactamgivestheprotonatedformof5aminopentanoicacid.Onemole
ofacidisrequiredpermoleoflactam.

Isouranswerreasonable?

CheckthatthecarbonylcarbonatomisnowpartofacarboxylicacidgroupandthattheNpartof
theamideisnowanaminogroup.Nowcheckthatthestateofionisationiscorrectforthereaction
conditionsused(acidconditionsgiveammoniumionsbasicconditionsgivecarboxylateions).
Sincethereactioniscarriedoutunderacidicconditions,theamineproductwillreactfurtherto
produceanammoniumion.

PRACTICEEXERCISE23.9
Completeequationsforthehydrolysisofthe
amidesinworkedexample23.9in
concentratedaqueousNaOH.Showall
productsastheyexistinaqueousNaOH,and
showtheamountofNaOHrequiredforthe
hydrolysisofeachamide.

ReactionswithAmmoniaandAmines
Carboxylicacidsreactwithammoniaandaminesinanacidbaseneutralisationreactiontogiveammonium
carboxylates.

AcidChlorides
Acidchloridesreactreadilywithammoniaandwith1and2aminestoformamides.Completeconversion
ofanacidchloridetoanamiderequires2moleequivalentsofammoniaoramine,1moleequivalenttoform
theamideand1moleequivalenttoneutralisethehydrogenchlorideformed.
AcidAnhydrides
Acidanhydridesreactwithammoniaandwith1and2aminestoformamides.Aswithacidchlorides,2
moleequivalentsofammoniaoraminearerequired,1moleequivalenttoformtheamideand1mole
equivalenttoneutralisethecarboxylicacidbyproduct.Tohelpyouseewhathappens,thisreaction
equationisbrokenintotwosteps,which,whenaddedtogether,givethenetreactionforthereactionofan
anhydridewithammonia.

Esters
Estersreactwithammoniaandwith1and2aminestoformamides:

Becauseanalkoxideanionisapoorerleavinggroupthanahalideorcarboxylateion,estersarelessreactive
towardsammonia,1aminesand2aminesthanareacidchloridesoracidanhydrides.

Amides
Amidesdonotreactwithammoniaoramines.

Thereactionsofcarboxylicacids,acidchlorides,anhydrides,estersandamideswithammoniaandamines
aresummarisedbelow.

Summaryofthereactionsofacidchlorides,anhydrides,estersandamideswithammoniaand
amines
WORKEDEXAMPLE23.10

FormationofAmidesfromEsters
Completethefollowingequations(thestoichiometryofeachisgivenintheequation).
(a)

(b)

Analysis

Firstidentifythecarbonylcarbonatomoftheester.Nucleophilicsubstitutionoccursatthis
carbonatom.SubstitutetheORgroupwiththenucleophileandthendotheappropriateproton
transferreaction.In(b),theprocessoccurstwice.

Solution
(a)
 (b)

Isouranswerreasonable?

Checkthatthesubstitutionhasoccurredatthecarbonatomofthecarbonylgroup.Checkalso
thatthealcoholformedcorrespondstotheORgroupofthestartingesters.

PRACTICEEXERCISE23.10
Completethefollowingequations(thestoichiometryofeachis
givenintheequation).
(a)

(b)

Reduction
Thecarboxylgroupisoneoftheorganicfunctionalgroupsthatismostresistanttoreduction.Itisnot
affectedbycatalyticreductionunderconditionsthateasilyreducealdehydesandketonestoalcohols,or
alkenestoalkanes.

Mostreductionsofcarbonylcompounds,includingaldehydesandketones,arenowaccomplishedby
transferringhydrideionsfromboronoraluminiumhydrides.Wehavealreadyseentheuseofsodium
borohydrideandlithiumaluminiumhydridetoreducethecarbonylgroupsofaldehydesandketonesto
hydroxylgroups(section21.5).Themostcommonreagentforthereductionofacarboxylicacidtoa
primaryalcoholistheverypowerfulreducingagentlithiumaluminiumhydridesodiumborohydrideisnota
sufficientlypowerfulreducingagenttoreducethecarboxylicacidderivatives.

CarboxylicAcids
Lithiumaluminiumhydride,LiAlH4,reducesacarboxylgrouptoaprimaryalcoholinexcellentyield.
Reductionismostcommonlycarriedoutindiethyletherortetrahydrofuran(THF).Analuminiumalkoxide
isproducedinitiallyandisthentreatedwithwatertogivetheprimaryalcohol,andlithiumandaluminium
hydroxides.ThesehydroxidesareinsolubleindiethyletherandTHFsocanberemovedbyfiltration.Evap
orationofthesolventyieldstheprimaryalcohol.

Alkenesaregenerallynotaffectedbymetalhydridereducingreagents.Thesereagentsfunctionashydride
iondonors(nucleophiles)andalkenesarenotnormallyattackedbynucleophiles.

Esters
Anesterisreducedbylithiumaluminiumhydridetotwoalcohols.Thealcoholderivedfromtheacylgroup
isprimary.

Sodiumborohydrideisnotnormallyusedtoreduceesters,becausethereactionisveryslow.Therefore,itis
possibletousesodiumborohydridetoreducethecarbonylgroupofanaldehydeoraketonetoahydroxyl
groupwithoutreducinganesterorcarboxylgroupinthesamemolecule.

Althoughitmaynotbeimmediatelyobvious,thereductionofestersinvolvesanucleophilicacyl
substitutionmechanismfollowedbyreductionoftheresultingaldehydetogive,ultimately,theprimary
alcohol.Themetalhydridereductionofaldehydeshasbeendiscussedinsection21.5.

Amides
Thereductionofamidesbylithiumaluminiumhydridecanbeusedtoprepare1,2or3amines,
dependingonthedegreeofsubstitutionoftheamide.
WORKEDEXAMPLE23.11

SynthesisofAminesfromCarboxylicAcids
Showhowtobringabouteachofthefollowingconversions.
(a)

(b)

Analysis

Thekeystepistoconvertacarboxylicacidintoanamidethatcanthenbereducedwithlithium
aluminiumhydridetogivetherequiredamine.Wehavediscussedacoupleoftwostepmethods
ofconvertingcarboxylicacidstoamides:viatheacidchlorideandviatheester.

Solution

TheamidecanbepreparedbytreatingthecarboxylicacidwithSOCl2toformtheacidchloride
andthentreatingtheacidchloridewithanamine.Alternatively,thecarboxylicacidcanbe
convertedtoanesterbyFischeresterificationandtheestertreatedwithanaminetogivethe
amide.Toillustratebothmethods,wehaveshowntheacidchloriderouteforconversion(a)and
theesterrouteforconversion(b).
(a)
 (b)

Isouranswerreasonable?

Checkthattheproductsofeachreactionstephavetheappropriatenumberofcarbonand
hydrogenatoms.

PRACTICEEXERCISE23.11
Showhowtoconverthexanoicacidtoeachof
thefollowingaminesingoodyield.
(a)

(b)

SelectiveReductionofotherFunctionalGroups
Catalytichydrogenationdoesnotreducecarboxylgroups,butdoesreducealkenestoalkanes.Therefore,we
canuseH2andametalcatalysttoreducethisfunctionalgroupselectivelyinthepresenceofacarboxyl
group.
Wesawinsection21.5thataldehydesandketonesarereducedtoalcoholsbybothLiAlH4andNaBH4.
OnlyLiAlH4,however,reducescarboxylgroups.Thus,itispossibletoreduceanaldehydeoraketone
carbonylgroupselectivelyinthepresenceofacarboxylgroupbyusingthelessreactiveNaBH4asthe
reducingagent.

EsterswithGrignardReagents
Treatinganesterofformicacidwith2moleequivalentsofaGrignardreagent,followedbyhydrolysisofthe
magnesiumalkoxidesaltinaqueousacid,givesa2alcoholtreatinganesterofanyothercarboxylicacid
withaGrignardreagentgivesa3alcoholinwhichtwoofthegroupsbondedtothecarbonatombearing
theOHgrouparethesame.

ReactionofanesterwithaGrignardreagent(shownabove)involvestheformationoftwosuccessive
tetrahedralcarbonyladditionintermediates.Thefirstcollapsestogiveanewcarbonylcompoundan
aldehydefromaformateester,aketonefromallotheresters.Thesecondintermediateisstableand,when
protonated,givesthefinalalcohol.ItisimportanttorealisethatitisnotpossibletouseRMgXandanester
toprepareanaldehydeoraketonetheintermediatealdehydeorketoneismorereactivethantheesterand
reactsimmediatelywiththeGrignardreagenttogiveanalcohol.
Steps1and2:Thesetwostepsdescribethenucleophilicacylsubstitutionreaction.Thereactionbegins
instep1withtheadditionof1moleequivalentofGrignardreagenttothecarbonylcarbontoforma
tetrahedralcarbonyladditionintermediate.Thisintermediatethencollapsesinstep2togiveanew
carbonylcontainingcompoundandamagnesiumalkoxidesalt.
 Steps3and4:Thesetwostepsdescribethetypicalcarbonyladditionreactionofaldehydesandketones
(seesection21.5).Thenewcarbonylcontainingcompoundreactsinstep3withasecondmoleequivalent
ofGrignardreagenttoformasecondtetrahedralcarbonyladditioncompound,which,afterhydrolysisin
aqueousacid(step4),givesa3alcohol(ora2alcoholifthestartingesterwasaformate).

AlthoughitmaynotbeobviousfromtheproductsobtainedinthereactionofesterswithGrignardreagents
orreducingagents,thereactionproceedsviaanucleophilicacylsubstitution.However,inbothcases,the
productsofthisinitialreactionreactreadilywiththereagentspresenttoultimatelyproducealcohols.

WORKEDEXAMPLE23.12

ReactionofEsterswithGrignardReagents
CompleteeachofthefollowingGrignardequations.
(a)

(b)

Analysis

Inbothcases,identifythecarbonylcarbonatomthiswillbethecarbonatombearingtheOH
groupintheproduct.ThefirstmoleequivalentofGrignardreagentwillsubstitutethealkoxy
group(inthesecases,theOCH3group)togiveanaldehydeorketone.Thesethenreactfurther,
intheusualfashion(seesection21.5),toproducealcohols.

Solution
(a)
 (b)

Isouranswerreasonable?

Since(a)isanesterofformicacid,thefinalproductshouldbea2alcohol.Ester(b)should
producea3alcohol.BothproductsshouldalsohavetwoequivalentRgroups.

PRACTICEEXERCISE23.12
Showhowtoprepareeachofthefollowing
alcoholsbytreatinganesterwithaGrignard
reagent.
(a)

(b)

InterconversionofFunctionalDerivatives
Onthelastfewpages,wehaveseenthatacidchloridesarethemostreactivecarboxylderivativestowards
nucleophilicacylsubstitutionandthatamidesaretheleastreactive.
Anotherusefulwaytothinkabouttherelativereactivitiesofthesefourfunctionalderivativesofcarboxylic
acidsissummarisedinfigure23.5.Anyfunctionalgroupinthisfigurecanbepreparedfromanyfunctional
groupaboveitbytreatmentwithanappropriateoxygenornitrogennucleophile.Anacidchloride,for
example,canbeconvertedtoanacidanhydride,anester,anamideoracarboxylicacid.However,acid
anhydrides,estersandamidesdonotreactwithchlorideionstogiveacidchlorides.

FIGURE23.5Relativereactivitiesofcarboxylicacidderivativestowardsnucleophilicacylsubstitution.
Amorereactivederivativemaybeconvertedtoalessreactivederivativebytreatmentwithan
appropriatereagent.Treatmentofacarboxylicacidwiththionylchlorideconvertsittothemore
reactiveacidchloride.Carboxylicacidsareaboutasreactiveasestersunderacidicconditionsbut
areconvertedtotheunreactivecarboxylateanionsunderbasicconditions.

Noticethatallcarboxylicacidderivativescanbeconvertedtocarboxylicacids,whichinturncanbe
convertedtoacidchlorides.Thus,anyacidderivativecanbeusedtosynthesiseanother,eitherdirectlyor
viaacarboxylicacid.

WORKEDEXAMPLE23.13

InterconversionofFunctionalGroups
Showhowtoconvertphenylaceticacidintoeachofthefollowingcompounds.
(a)

(b)

(c)
 (d)

Analysis

First,drawthestructureofphenylaceticacidandthencomparethisstructure(thestarting
material)withthoseoftheproducts.Compounds(a)and(b)arecarboxylicacidderivatives,
whichcanbeobtainedfromphenylaceticacidbynucleophilicacylsubstitutionreactions(more
thanonestepmayberequired).Compounds(c)and(d),however,areproductsobtainedfromthe
reductionofcarboxylicacidderivatives.

Solution

Preparethemethylester(a)byFischeresterification(pp.101922)ofphenylaceticacidwith
methanol.Thentreatthisesterwithammoniatopreparetheamide(b).Alternatively,treat
phenylaceticacidwiththionylchloride(table23.5)togiveanacidchloride,andthentreatthe
acidchloridewithtwoequivalentsofammoniatogiveamide(b).Reductionofamide(b)by
LiAlH4givesthe1amine(c).Similarreductionofeitherphenylaceticacidorester(a)givesthe
1alcohol(d).

Isouranswerreasonable?

Checkthatthecarbonskeletonofphenylaceticacidisretainedineachstepthatis,thePhCH2
Cshouldbeconsistentthroughout.In(a)and(b),theCispartofacarbonylgroupwhilein(c)
and(d)itisaCH2group.

PRACTICEEXERCISE23.13
Showhowtoconvert(R)2phenylpropanoic
acidtoeachofthefollowingcompounds.
(a)
 (b)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
23.6Triglycerides
Thetriglyceridesbelongtoagroupofnaturallyoccurringorganiccompoundscalledlipidsthatareclassifiedtogetheronthebasisoftheir
commonsolubilityproperties.Lipidsareinsolubleinwaterbutsolubleinrelativelynonpolar,aproticorganicsolvents,includingdiethylether
anddichloromethane.(Note:Thisclassificationisbasedonaphysicalproperty,notastructuralfeature.)

Triglyceridesortriacylglycerolsaretriestersofglycerolandlongchaincarboxylicacidsandtheyplayamajorroleinhumanandanimal
biology.Theyarestoragedepotsofchemicalenergyintheformoffatshumansstoreenergyintheformoffatglobulesinadiposetissue.

Animalfatsandvegetableoils,themostabundantnaturallyoccurringlipids,arealsocalledtriglyceridesortriacylglycerols.Hydrolysisofa
triglycerideinaqueousbase,followedbyacidification,givesglycerolandthreefattyacids(acidswithlongcarbonchains).

ChemistryResearch

MolecularMachines

ProfessorChrisEaston,ResearchSchoolofChemistry,AustralianNationalUniversity

Nanotechnologyisahottopicinchemistryresearch.Itallowsthecontrolofmatterandthefabricationofdevicesonthenanometre
scale.Thisprimarilyinvolvesmoleculesinteractingwithothermoleculestherebygivingrisetouniquepropertiesorfunctionsdifferent
fromthoseoftheseparatespecies.Chemistshavenamedthisspecialfieldofresearchsupramolecularchemistry.

ProfessorChrisEaston'sgroupattheResearchSchoolofChemistryattheAustralianNationalUniversity(ANU)isveryactiveinthe
areaofsupramolecularchemistryandhasrecentlycreatedanextraordinarilysmallnanotechnologicaldevice:amolecularmachine.A
machineisanapparatusconsistingofinterrelatedpartswithseparatefunctionsthatcanbeusedtodosomeformofwork.Research
chemistsinProfessorEaston'sgrouphavedevelopedsyntheticskillsandtechniquesthatallowthemtoassemblenovelmolecular
structuresthatcanessentiallyperformtheactionsofamachine,butonananoscale(representedconceptuallyinfigure23.6).Professor
Easton'smolecularmachine(amolecularpump)usesanamidebondconstrainedatanoddanglethroughbindingforceswithina
truncatedconeshapedmoleculecalledacyclodextrin(figure23.7).RecallthatamidesarederivativesofcarboxylicacidswheretheC
Nbondhasdoublebondcharacterandsoisnotfreetorotate.

FIGURE23.6Conceptualrepresentationof(top)amechanicalmachineand(bottom)itsmolecularcounterpartdevelopedbyresearchersatANU.
 FIGURE23.7Cyclodextrinsareformedfromsacchariderings.TheEastongroup'sworkisbasedoncyclodextrin,inwhichn=2.

Withthismolecularpump,theworkdonebythesystemcontrolsmolecularmotionsandoccursinresponsetoexternalstimulithatmay
bechemical,thermalorphotochemical.Thebasisforthemachine'sfunctionisthatanexternalstimulusisusedtopushthesystemout
ofequilibriumandworkisdonewhenthesystemrespondstorestoreequilibrium,ProfessorEaston'sgrouphasmeasuredthework
outputresultingfromthismolecularinteractiontobeoftheorderof5.9kJmol1.

Thesimplestformofthemachine(figure23.8)comprisesanaromaticsubstituentattachedtoacyclodextrin.Cyclodextrinsareunusual
truncatedconeshapedmoleculesgeneratedwhenapolysaccharidechainisjoinedtoformalargecyclicstructure.Thecyclodextrin
anditssidechainbehaveasthecylinderandpiston,respectively,ofamolecularpump.Thepumpisfuelledby1adamantanol.

FIGURE23.8Graphicalrepresentationofthesimplestformofthemolecularmachine(structure1)comprisingcyclodextrin(cylinder)andits
aromaticsidechain(piston).EandZrefertothe(E)and(Z)typeisomers.

Duringthecompressionstrokeofthepiston,thearomaticsidechainsubstituentisinsertedwithinthecyclodextrincavityand1
adamantanolisremovedbyanexternalstimulus.Thisinsertionprocesstakesenergybutisdrivenbythenonpolarbindingbetweenthe
innersurfaceofthecyclodextrinandthehydrocarbonsofthesidechain.Thisintramolecularinsertiondistortsthesidechainfromthe
preferred(E)typeisomerforthepartialdoublebondcharacteroftheamidegrouplinkingthecyclodextrintothephenylsubstituent.As
thegroupisdrawnintothecyclodextrincavity,thedistortioncreatesstrainenergyintheamidebondsothisfunctionalgroupthen
servesasatorsionbarholdingenergyinthesystemreadyforrelease.

Duringthedecompressionstrokeofthepiston,1adamantanolisaddedagain.The1adamantanolismorepreferentiallyboundwithin
thecyclodextrinthanisthesidechainandso,asitreentersthesystem,thesidechainisreleased,thusreleasingenergy.
 Asthismolecularmachineisfartoosmalltobeseenbyanymicroscopytechnique,theconformationsofthedeviceweredetermined
by1HNMRspectroscopy.Theequilibriumlevelsofthevariousisomerswereusedtocalculatetheenergydifferencesbetweenthe
isomerspresent.

Thegrouphasalsoproducedamoreadvancedformofthemachine,whichusestwoisomersthatcanbeinterconverted
photochemically.Onlyoneoftheisomerscanbeforcedtofitintothecyclodextrinandperformthework,sothephotoisomerisation
turnsthemachineonandoff.Inthismoreadvancedversionofthemachine(figure23.9),theCH2CH2linkingthephenylring
tothecyclodextrinwasconvertedtoanalkene,andthisservesasaphotochemicalon/offswitch.Irradiationat300nmconvertsthe
transcinnamidesidechainofstructure2tothecisisomerofstructure3,whilethereverseprocessoccursat254nm.Theworkoutput
oftheswitcheDonmachineisoftheorderof8.8kJmol1.

FIGURE23.9Graphicalrepresentationofamoreadvancedformofthemolecularmachine(structures2and3)usingtwoisomersthatcanbe
interconvertedphotochemicallytocreateanon/offswitch.EandZrefertothe(E)and(Z)typeisomers.

Theratiosoftheamideisomersofstructures2and3(infigure23.9)weredeterminedasforstructure1(infigure23.8).Inthiscase,
however,theorientationofthecisdoublebondpreventsthesidechaininsertingintothecavityandsointhatmodethemachineis
turnedoff.Bycontrast,thetransalkenemoietydoesallowinsertion,andsointhismodethemachineisturnedon.

TheapparatusdevelopedbytheEastonresearchgroupconstitutesarguablythesmallestmachineeverbuilt.Thisnanotechnological
deviceisamachinewheretheoutputenergyofmolecularbindingisharnessedtodoworkandconstrainthegeometryofanamide
bond.Thephotoisomerisationofthetranscinnamidesidechainofstructure2andthecisisomerofstructure3providesthemachine
withanon/offswitch.Theapparentworkperformedontheamidebondhasamaximumof8.8kJmol1.Thisdemonstrationbythe
Eastongroupthatworkoutputcanbeharnessedandquantifiedinsuchmolecularmachinestakesresearchersonestepclosertothe
practicalapplicationofnanotechnology.

FattyAcids
Morethan500differentfattyacidshavebeenisolatedfromvariouscellsandtissues.Table23.4givescommonnamesandstructuralformulae
forthemostabundantfattyacids.Thenumberofcarbonsinafattyacidandthenumberofcarboncarbondoublebondsinitshydrocarbon
chainareshownbytwonumbersseparatedbyacolon.Inthisnotation,linoleicacid,forexample,isdesignatedasan18:2fattyacidits18
carbonchaincontainstwocarboncarbondoublebonds.Thethreemostabundantfattyacidsinnaturearepalmiticacid(16:0),stearicacid
(18:0)andoleicacid(18:1).
TABLE23.4 TheMostAbundantFattyAcidsinAnimalFats,VegetableOils(figure23.10)andBiologicalMembranes
Carbonatoms:doublebonds Structure Commonname Meltingpoint(C)
Saturatedfattyacids
12:0 (a) CH3(CH2)10COOH lauricacid 44
14:0 CH3(CH2)12COOH myristicacid 58
16:0 CH3(CH2)14COOH palmiticacid 63
18:0 CH3(CH2)16COOH stearicacid 70
20:0 CH3(CH2)18COOH arachidicacid 77
Unsaturatedfattyacids
16:1 CH3(CH2)5CH CH(CH2)7COOH palmitoleicacid 1
18:1 CH3(CH2)7CH CH(CH2)7COOH oleicacid 16
18:2 CH3(CH2)4(CH CHCH2)2(CH2)6COOH linoleicacid 5
18:3 CH3CH2(CH CHCH2)3(CH2)6COOH linolenicacid 11
20:4 CH3(CH2)4(CH CHCH2)4(CH2)2COOH arachidonicacid 49

(a)Thefirstnumberisthenumberofcarbonatomsinthefattyacidthesecondisthenumberofcarboncarbondoublebondsinits
hydrocarbonchain.

FIGURE23.10Somevegetableoilsusedincooking.KariAnnTapp

Themostabundantfattyacidsfoundinhigherplantsandanimalshaveseveralimportantcharacteristics:
1.Nearlyallfattyacidshaveanevennumberofcarbonatoms,mostbetween12and20,inanunbranchedchain.
2.Inmostunsaturatedfattyacids,thecisisomerpredominatesthetransisomerisrare.
3.Unsaturatedfattyacidshavelowermeltingpointsthantheirsaturatedcounterparts.Thegreaterthedegreeofunsaturation,thelowerthe
meltingpoint.Compare,forexample,themeltingpointsofthesefour18carbonfattyacids.

stearicacid(18:0)

(mp=70C)
oleicacid(18:1)

(mp=16C)

linoleicacid(18:2)

(mp=5C)

linolenicacid(18:3)

(mp=11C)

WORKEDEXAMPLE23.14
 TriglycerideStructure
Drawthestructuralformulaofatriglyceridederivedfromonemoleculeeachofpalmiticacid,oleicacidandstearicacid,thethree
mostabundantfattyacidsinthebiologicalworld.

Analysis

Thetriglycerideisatriesterofglycerol(atriol)soeachofthethreecarboxylicacidswillformanesterwithanOHgroupof
glycerol.Thereismorethanonepossibletriglycerideusingthreedifferentfattyacids.

Solution

Inthisstructure,palmiticacidisesterifiedatC(1)ofglycerol,oleicacidatC(2),andstearicacidatC(3).

Isouranswerreasonable?

Checkthattheestergroupisdrawnthecorrectwayaround.Thatis,isthealkoxygroup(OR)derivedfromglycerol?Checkalso
thatthenumberofcarbonatomsiscorrect.

PRACTICEEXERCISE23.14

(a)Howmanyconstitutionalisomersarepossiblefora
triglyceridecontainingonemoleculeeachofpalmitic
acid,oleicacidandstearicacid?
(b)Whichoftheconstitutionalisomersthatyoufoundin(a)
arechiral?

PhysicalProperties
Thephysicalpropertiesofatriglyceridedependonitsfattyacidcomponents.Ingeneral,themeltingpointofatriglycerideincreasesasthe
numberofcarbonatomsinitshydrocarbonchainsincreasesandasthenumberofcarboncarbondoublebondsdecreases.Triglyceridesrichin
oleicacid,linoleicacidandotherunsaturatedfattyacidsaregenerallyliquidsatroomtemperatureandarecalledoils(e.g.cornoilandolive
oil).Triglyceridesrichinpalmitic,stearicandothersaturatedfattyacidsaregenerallysemisolidsorsolidsatroomtemperatureandarecalled
fats(e.g.humanfatandbutterfat).Fatsoflandanimalstypicallycontainapproximately40%to50%saturatedfattyacidsbyweight(table
23.5).Mostplantoils,ontheotherhand,contain20%orlesssaturatedfattyacidsand80%ormoreunsaturatedfattyacids.Thenotable
exceptiontothisgeneralisationaboutplantoilsarethetropicaloils(e.g.coconutandpalmoils),whichareconsiderablyricherinlowmolar
masssaturatedfattyacids.
TABLE23.5 GramsofFattyAcidPer100gofTriglycerideofSeveralFatsandOils
Saturatedfattyacids Unsaturatedfattyacids
Fatoroil Lauric(12:0) Palmitic(16:0) Stearic(18:0) Oleic(18:1) Linoleic(18:2)
humanfat 24.0 8.4 46.9 10.2
beeffat 27.4 14.1 49.6 2.5
butterfat 2.5 29.0 9.2 26.7 3.6
canolaoil 3.9 1.9 64.1 18.7

coconutoil 45.4 10.5 2.3 7.5 trace

cornoil 10.2 3.0 49.6 34.3
oliveoil 6.9 2.3 84.4 4.6
palmoil 40.1 5.5 42.7 10.3
 peanutoil 8.3 3.1 56.0 26.0
soybeanoil 0.2 9.8 2.4 28.9 50.7
sunfloweroil 0.5 6.8 4.7 18.6 68.7
Note:Onlythemostabundantfattyacidsaregivenotherfattyacidsarepresentinlesseramounts.

Thelowermeltingpointsoftriglyceridesthatarerichinunsaturatedfattyacidsarerelatedtodifferencesinthreedimensionalshapebetweenthe
hydrocarbonchainsoftheirunsaturatedandsaturatedfattyacidcomponents.Inasaturatedtriglyceride,thehydrocarbonchainslieparallelto
eachother,givingthemoleculeanordered,compactshape.Becauseofthiscompactthreedimensionalshapeandtheresultingstrengthofthe
dispersionforces(section6.8)betweenhydrocarbonchainsofadjacentmolecules,triglyceridesthatarerichinsaturatedfattyacidshave
meltingpointsaboveroomtemperature.

Thethreedimensionalshapeofanunsaturatedfattyacid,particularlythosecontainingcis(Z)alkenes,isquitedifferentfromthatofasaturated
fattyacid.Recallthatunsaturatedfattyacidsofhigherorganismsarepredominantlyofthecis(Z)configurationtrans(E)configurationsare
rare.

Polyunsaturatedtriglycerides(triglycerideswithseveralcarboncarbondoublebonds)havealessorderedstructureanddonotpacktogetheras
closelyorascompactlyassaturatedtriglycerides.Therefore,intramolecularandintermoleculardispersionforcesareweaker,sopolyunsaturated
triglycerideshavelowermeltingpointsthantheirsaturatedcounterparts.

ReductionofFattyacidChains
Foravarietyofreasons,inpartconvenienceandinpartdietarypreference,theconversionofoilstofatshasbecomeamajorindustry.The
processiscalledhardeningofoilsandinvolvesthecatalyticreductionofsomeorallofanoil'scarboncarbondoublebonds.Inpractice,the
degreeofhardeningiscarefullycontrolledtoproducefatsofadesiredconsistency.Theresultingfatsaresoldforkitchenuse.Margarineand
otherbuttersubstitutesareproducedbypartialhydrogenationofpolyunsaturatedoilsderivedfromcanola,sunflower,oliveandsoybeanoils
(seefigure23.11).Tothehardenedoilareaddedcarotene(togiveitayellowcolourandmakeitlooklikebutter),saltandabout15%milkby
volumetoformthefinalemulsion.VitaminsAandDmaybeaddedaswell.Finally,becausetheproductatthisstageistasteless,acetoinand
diacetyl,twocompoundsthatmimicthecharacteristicflavourofbutter,areoftenadded:

FIGURE23.11Somecommonproductscontaininghydrogenatedvegetableoils.KariAnnTapp

Anunintendedconsequenceofpartialhydrogenationofthealkenegroupsinpolyunsaturatedoilsistheisomerisationofasmallproportionof
thecisalkenestotransalkenes.Theseareknownastransfatsandareofconcernastheyarebelievedtoincreasetheriskofcoronaryheart
disease.Thesetransfatsdooccurnaturally,althoughonlytoasmallextent.Canolaoilnaturallyhasarelativelyhighleveloftransfats,but
mostothernaturaloilshaveverylittletransfat.Lambandmuttonalsonaturallycontainmoderatelevelsoftransfats.

RancidificationofFatsandOils
Unsaturatedfatsandoils,whenexposedtoair,canundergoaprocessofrancidification.Inthisprocessthealkeneunitsareoxidativelycleaved
togivelowmolarmassaldehydesandcarboxylicacids.Thesecompoundshaveunpleasantodoursandflavours,thusmakingthefood
unpalatable.
Oftenantioxidantsareaddedtounsaturatedfatsandoilstoretardthisoxidationprocess.

SoapsandDetergents
Naturalsoapsarepreparedmostcommonlyfromablendoftallowandcoconutoil.Inthepreparationoftallow,thesolidfatsofcattleare
meltedwithsteam,andthetallowlayerthatformsonthetopisremoved.Thepreparationofsoapsbeginsbyboilingthesetriglycerideswith
sodiumhydroxide.Thereactionthattakesplaceiscalledsaponification(fromtheLatinsaponemmeaningsoap).

Atthemolecularlevel,saponificationcorrespondstobasepromotedhydrolysisoftheestergroupsintriglycerides(section23.5).Theresulting
soapscontainmainlythesodiumsaltsofpalmitic,stearicandoleicacidsfromtallowandthesodiumsaltsoflauricandmyristicacidsfrom
coconutoil.

Afterhydrolysisiscomplete,sodiumchlorideisaddedtoprecipitatethesoapasthickcurds.Thewaterlayeristhendrawnoff,andglycerolis
recoveredbyvacuumdistillation.Thecrudesoapcontainssodiumchloride,sodiumhydroxideandotherimpuritiesthatareremovedbyboiling
thecurdinwaterandprecipitatingagainwithmoresodiumchloride.Afterseveralpurifications,thesoapcanbeusedasaninexpensive
industrialsoapwithoutfurtherprocessing.OthertreatmentstransformthecrudesoapintopHcontrolledcosmeticsoaps,medicatedsoapsand
thelike.

HowSoapCleans
Soapowesitsremarkablecleaningpropertiestoitsabilitytoactasanemulsifyingagent.Becausethelonghydrocarbonchainsofnaturalsoaps
areinsolubleinwater,theytendtoclustertominimisetheircontactwithsurroundingwatermolecules.Thepolarcarboxylategroups,by
contrast,tendtoremainincontactwiththesurroundingwatermolecules.Thus,inwater,soapmoleculesspontaneouslyclusterintomicelles
(figure23.12).Amicelleisasphericalarrangementoforganicmoleculesinwatersolutionclusteredsothattheirhydrophobicpartsareburied
insidethesphereandtheirhydrophilicpartsareonthesurfaceofthesphereandincontactwithwater.

FIGURE23.12Soapmicelles.Nonpolar(hydrophobic)hydrocarbonchainsareclusteredintheinteriorofthemicelle,andpolar(hydrophilic)carboxylate
groupsareonthesurfaceofthemicelle.Soapmicellesrepeleachotherbecauseoftheirnegativesurfacecharges.

Mostofthethingswecommonlythinkofasdirt(suchasgrease,oilandfatstains)arenonpolarandinsolubleinwater.Whensoapandthis
typeofdirtaremixedtogether,asinawashingmachine,thenonpolarhydrocarboninnerpartsofthesoapmicellesdissolvethenonpolardirt
molecules.Ineffect,newsoapmicellesareformed,thistimewithnonpolardirtmoleculesinthecentre(figure23.13).Inthisway,nonpolar
organicgrease,oilandfataredissolvedandwashedawayinthepolarwashwater.
 FIGURE23.13Asoapmicellewithadissolvedoilorgreasedroplet.

Soaps,however,havetheirdisadvantages,themainonebeingthattheyformwaterinsolublesaltswhenusedinhardwater,whichcontains
Ca(II),Mg(II)orFe(III)ions.

Thesecalcium,magnesiumandironsaltsoffattyacidscreateproblems,includingringsaroundthebathtub,filmsthatspoilthelustreofhair,
andgreynessandroughnessthatbuildupontextilesafterrepeatedwashings.

SyntheticDetergents
Afterthecleaningactionofsoapswasunderstood,chemistswereinapositiontodesignasyntheticdetergent.Moleculesofagooddetergent,
theyreasoned,musthavealonghydrocarbonchainpreferably12to20carbonatomslongandapolargroupatoneendofthemolecule
thatdoesnotforminsolublesaltswiththeCa(II),Mg(II)orFe(III)ionsinhardwater.Theseessentialcharacteristicsofasoap,theyrecognised,
couldbeproducedinamoleculecontainingasulfonate(SO3)groupinsteadofacarboxylate(COO)group.Calcium,magnesiumandiron
saltsofmonoalkylsulfuricandsulfonicacidsaremuchmoresolubleinwaterthancomparablesaltsoffattyacids.

Themostwidelyusedsyntheticdetergentstodayarethelinearalkylbenzenesulfonates(LAS).Oneofthemostcommonoftheseissodium4
dodecylbenzenesulfonate.Topreparethistypeofdetergent,alinearalkylbenzeneistreatedwithsulfuricacidtoformanalkylbenzenesulfonic
acid,followedbyneutralisationofsulfonicacidwithNaOH:

Theproductismixedwithbuildingagentsandspraydriedtogiveasmooth,flowingpowder.Themostcommonbuilderissodiumsilicate.
Alkylbenzenesulfonatedetergentswereintroducedinthelate1950s,andtodaytheycommandcloseto90%ofthemarketonceheldbynatural
soaps.

Amongthemostcommonadditivestodetergentpreparationsarefoamstabilisers(toencouragelongerlastingbubbles),bleachesandoptical
brighteners.Theamidepreparedfromdodecanoicacid(lauricacid)and2aminoethanol(ethanolamine)isacommonfoamstabiliseraddedto
liquidsoaps,butnotlaundrydetergentsforobviousreasonsimagineatoploadingwashingmachinewithfoamspewingoutofthelid!The
mostcommonbleachusedinwashingpowdersissodiumperborate,whichdecomposesattemperaturesabove50Ctogivehydrogen
peroxide,theactualbleachingagent.

Alsoaddedtolaundrydetergentsareopticalbrighteners(opticalbleaches).Thesesubstancesareabsorbedintofabricsand,afterabsorbing
ambientlight,fluorescewithabluecolour,offsettingtheyellowcolouracquiredbyfabricasitages.Opticalbrightenersproduceawhiterthan
whiteappearance(seefigure23.14).YoumostcertainlyhaveobservedtheireffectsifyouhaveseentheglowofwhiteTshirtsorblouses
whentheyareexposedtoblacklight(UVradiation).
 FIGURE23.14OpticalbrightenersconvertUVlighttobrighterfluorescentcolours.Stone/JaymeThornton

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
StructureandBonding
Thecarboxylicacidfunctionalgroupisthecarboxylgroup,COOH.Theacidhalidefunctionalgroup
isanacylgroupbondedtoahalogenatom.Themostcommonandwidelyusedoftheacidhalidesare
theacidchlorides.Thecarboxylicanhydridefunctionalgroupistwoacylgroupsbondedtoanoxygen
atom.TheesterfunctionalgroupisanacylgroupbondedtoanORorOArgroup.Acyclicesteris
giventhenamelactone.Theamidefunctionalgroupisanacylgroupbondedtoatrivalentnitrogen
atom.Acyclicamideisgiventhenamelactam.

Nomenclature
IUPACnamesofcarboxylicacidsarederivedfromtheparentalkanebydroppingthesuffixeand
addingoicacid.Dicarboxylicacidsarenamedasdioicacids.Acidhalidesarenamedbychanging
thesuffixicacidinthenameoftheparentcarboxylicacidtoylhalide.Acidanhydridesarenamedby
replacingthewordacidwithanhydride.Whentheanhydrideisnotsymmetrical,bothacidgroupsare
named.Inesters,thealkylorarylgroupbondedtooxygenisnamedfirst,followedasaseparateword
bythenameoftheacidinwhichthesuffixicacidisreplacedbythesuffixate.Amidesarenamedby
droppingthesuffixoicacidfromtheIUPACnameoftheparentacid,oricacidfromitscommon
name,andaddingamide.

PhysicalProperties
Carboxylicacidsarepolarcompoundsthatassociatebyhydrogenbondingintodimersintheliquidand
solidstates.Carboxylicacidshavehigherboilingpointsandaremoresolubleinwaterthanalcohols,
aldehydes,ketonesandethersofcomparablemolarmass.Acarboxylicacidconsistsoftworegionsof
differentpolarity:apolar,hydrophiliccarboxylgroup,whichincreasessolubilityinwater,anda
nonpolar,hydrophobichydrocarbonchain,whichdecreasessolubilityinwater.Thefirstfouraliphatic
carboxylicacidsareinfinitelysolubleinwater,becausethehydrophiliccarboxylgroupmorethan
offsetsthehydrophobichydrocarbonchain.Asthesizeofthecarbonchainincreases,however,the
hydrophobicgroupbecomesdominantandsolubilityinwaterdecreases.

PreparationofCarboxylicAcids
Carboxylicacidscanbepreparedbytheoxidationofprimaryalcohols,aldehydesandalkylbenzene
derivatives.TheycanbepreparedbythereactionofGrignardreagentswithcarbondioxideandbythe
hydrolysisofnitrilesandcarboxylicacidderivatives.

ReactionsofCarboxylicAcidsandDerivatives
ValuesofpKaforaliphaticcarboxylicacidsrangefrom4.0to5.0.Electronwithdrawingsubstituents
nearthecarboxylgroupincreaseacidityinbothaliphaticandaromaticcarboxylicacids.

Acommonreactionthemeoffunctionalderivativesofcarboxylicacidsisnucleophilicacyladditionto
thecarbonylcarbonatomtoformatetrahedralcarbonyladditionintermediate,whichthencollapsesto
regeneratethecarbonylgroup.Theresultisnucleophilicacylsubstitution.Listedinorderofincreasing
reactivitytowardsnucleophilicacylsubstitution,thesefunctionalderivativesare:
Anymorereactivefunctionalderivativecanbedirectlyconvertedtoanylessreactivefunctional
derivativebyreactionwithanappropriateoxygenornitrogennucleophile.

Triglycerides
Lipidsareaheterogeneousclassofcompoundsgroupedtogetheronthebasisoftheirsolubility
propertiestheyareinsolubleinwaterbutsolubleindiethyletheranddichloromethane.Carbohydrates,
aminoacidsandproteinsarelargelyinsolubleintheseorganicsolvents.

Triglycerides(triacylglycerols),themostabundantlipids,aretriestersofglycerolandfattyacids.Fatty
acidsarelongchaincarboxylicacidsderivedfromthehydrolysisoffats,oilsandthephospholipidsof
biologicalmembranes.Themeltingpointofatriglycerideincreasesas(1)thelengthofitshydrocarbon
chainsincreasesand(2)itsdegreeofsaturationincreases.Triglyceridesrichinsaturatedfattyacidsare
generallysolidsatroomtemperaturethoserichinunsaturatedfattyacidsaregenerallyoilsatroom
temperature.

Soapsaresodiumorpotassiumsaltsoffattyacids.Inwater,soapsformmicelles,whichdissolve
nonpolarorganicgreaseandoil.NaturalsoapsprecipitateaswaterinsolublesaltswithMg 2+,Ca2+and
Fe3+ionsinhardwater.Themostcommonandmostwidelyusedsyntheticdetergentsarelinear
alkylbenzenesulfonates.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Preparationofcarboxylicacidsbyoxidationofprimaryalcoholsandaldehydes(section23.4)
Primaryalcoholsandaldehydesarereadilyoxidisedtocarboxylicacidswithavarietyofoxidising
agents.

Preparationofcarboxylicacidsbyoxidationofalkylbenzenes(section23.4)
Alkylbenzenesareoxidisedtobenzoicacidsundervigorousoxidisingconditions.

PreparationofcarboxylicacidsbycarbonationofGrignardreagents(section23.4)
CarboxylicacidscanbepreparedbytreatmentofGrignardreagentswithCO2.

Preparationofcarboxylicacidsbyformationandhydrolysisofnitriles(section23.4)
Carboxylicacidscanbepreparedfromalkylhalidesbyformationandsubsequenthydrolysisofnitriles.

Acidityofcarboxylicacids(section23.5)
ValuesofpKaformostunsubstitutedaliphaticandaromaticcarboxylicacidsrangefrom4to5.

SubstitutionbyelectronwithdrawinggroupsdecreasesthepKavalue(increasesacidity).

Reactionofcarboxylicacidswithbases(section23.5)
Carboxylicacidsformwatersolublesaltswithalkalimetalhydroxides,carbonatesandbicarbonates,as
wellaswithammoniaandamines.

Conversiontoacidhalides(section23.5)
Acidchlorides,themostcommonandwidelyusedoftheacidhalides,arepreparedbytreating
carboxylicacidswiththionylchloride.

Fischeresterification(section23.5)
Fischeresterificationisreversible.

Toforcethereactiontotheright,useexcessalcohol.

Reactionofanacidchloridewithanalcohol(section23.5)
TreatmentofanacidchloridewithanalcoholgivesanesterandHCl.

Reactionofanacidanhydridewithanalcohol(section23.5)
Treatmentofanacidanhydridewithanalcoholgivesanesterandacarboxylicacid.

Reactionofanesterwithanalcohol(section23.5)
Treatmentofanesterwithanalcoholinthepresenceofanacidcatalystresultsintransesterification:that
is,thereplacementofoneORgroupbyadifferentORgroup.

Hydrolysisofanacidchloride(section23.5)
Lowmolarmassacidchloridesreactvigorouslywithwaterhighmolarmassacidchloridesreactless
rapidly.
Hydrolysisofanacidanhydride(section23.5)
Lowmolarmassacidanhydridesreactreadilywithwaterhighmolarmassacidanhydridesreactless
rapidly.

Hydrolysisofanester(section23.5)
Estersarehydrolysedonlyinthepresenceofbaseoracidbaseisrequiredinanequimolaramountacid
isacatalyst.

Hydrolysisofanamide(section23.5)
Eitheracidorbaseisrequiredinanamountequivalenttothatoftheamide.

Reactionofanacidchloridewithammoniaoranamine(section23.5)
Thisreactionrequires2moleequivalentsofammoniaoramine1moleequivalenttoformtheamide
and1moleequivalenttoneutralisetheHClbyproduct.

Reactionofanacidanhydridewithammoniaoranamine(section23.5)
Thisreactionrequires2moleequivalentsofammoniaoramine1moleequivalenttoformtheamide
and1moleequivalenttoneutralisethecarboxylicacidbyproduct.
Reactionofanesterwithammoniaoranamine(section23.5)
Treatmentofanesterwithammonia,a1amineora2aminegivesanamide.

Reductionbylithiumaluminiumhydride(section23.5)
Lithiumaluminiumhydridereducesacarboxylgrouptoaprimaryalcohol.

Reductionofanester(section23.5)
Reductionofestersbylithiumaluminiumhydridegivestwoalcohols.

Reductionofanamide(section23.5)
Reductionofanamidebylithiumaluminiumhydridegivesanamine.

ReactionofanesterwithaGrignardreagent(section23.5)
TreatingaformateesterwithaGrignardreagent,followedbyhydrolysis,givesa2alcohol,whereas
treatinganyotheresterwithaGrignardreagentgivesa3alcohol.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
StructureandBonding
23.1DrawstructuralformulaeforthefourcarboxylicacidswiththemolecularformulaC5H10O2.
Whichofthesecarboxylicacidsischiral?
23.2DrawthestructuralformulaeforthesevencarboxylicacidswiththemolecularformulaC6H12O2.
Whichoftheseischiral?.
23.3Drawstructuralformulaefor(a)anester,(b)anacidchloride,(c)ananhydrideand(d)anamide.
23.4Onthestructuresyouhavedrawninquestion23.3,showthepolarityoftheatomsinthe
functionalgroupsusingthe+/notation.
23.5Identifythefunctionalgroupsineachofthefollowingcompounds.
(a)

(b)

(c)

23.6Identifythefunctionalgroupsineachofthefollowingcompounds.
(a)

(b)

Nomenclature
23.7WritetheIUPACnameforeachofthefollowingcompounds.
(a)
 (b)

(c)

(d)

(e)

(f) CH2(COOCH2CH3)2
23.8WritetheIUPACnameforeachofthefollowingcompounds.
(a)

(b)

(c)

(d)

(e)

(f)
23.9Drawthestructuralformulaforeachofthefollowingcarboxylicacids.
(a)4nitrophenylaceticacid
(b)4aminopentanoicacid
(c)3chloro4phenylbutanoicacid
(d)cishex3enedioicacid
23.10Drawthestructuralformulaforeachofthefollowingcarboxylicacids.
(a)2,3dihydroxypropanoicacid
(b)3oxohexanoicacid
(c)2oxocyclohexanecarboxylicacid
(d)2,2dimethylpropanoicacid
23.11Drawthestructuralformulaforeachofthefollowingcompounds.
(a)dimethylcarbonate
(b)pnitrobenzamide
(c)octanoylchloride
(d)diethyloxalate(diethylethanedioate)
23.12Drawthestructuralformulaforeachofthefollowingcompounds.
(a)ethylcispent2enoate
(b)butanoicanhydride
(c)dodecanamide
(d)ethyl3hydroxybutanoate
23.13Drawthestructuralformulaformethyllinoleate.Becertaintoshowthecorrectconfigurationof
groupsaroundeachcarboncarbondoublebond.
23.14Drawstructuralformulaeforeachofthefollowingsalts.
(a)sodiumbenzoate
(b)lithiumacetate
(c)ammoniumacetate
(d)disodiumadipate(disodiumhexanedioate)
(e)sodiumsalicylate(sodium2hydroxybenzoate)
(f) calciumbutanoate
PhysicalProperties
23.15Aceticacidandmethylformateareconstitutionalisomers.Bothareliquidsatroomtemperature,
onewithaboilingpointof32C,theotherwithaboilingpointof118C.Whichofthetwohas
thehigherboilingpoint?
23.16Aceticacidhasaboilingpointof118C,whereasitsmethylesterhasaboilingpointof57C.
Accountforthefactthattheboilingpointofaceticacidishigherthanthatofitsmethylester,
eventhoughaceticacidhasalowermolarmass.
23.17Arrangethecompoundsineachofthefollowingsetsinorderofincreasingboilingpoint.
(a)CH3(CH2)5COOH,CH3(CH2)6CHO,CH3(CH2)6CH2OH
(b)CH3CH2COOH,CH3CH2CH2CH2OH,CH3CH2OCH2CH3
23.18Arrangethecompoundsineachofthefollowingsetsinorderofincreasingsolubilityinwater.
(a)CH3(CH2)5COOH,CH3(CH2)6CHO,CH3(CH2)6CH2OH
(b)CH3CH2COOH,CH3CH2CH2CH2OH,CH3CH2OCH2CH3
23.19Decanoicacidisnotverysolubleinwater.Woulditbemoresolubleunderacidicorbasic
conditions?Explainyouranswer.
23.20Characterisethestructuralfeaturesnecessarytomakeagoodsyntheticdetergent.
PreparationofCarboxylicAcids
23.21Drawastructuralformulafortheproductformedbytreatingeachofthefollowingcompounds
withwarmchromicacid,H2CrO4.
(a)CH3(CH2)4CH2OH
(b)

(c)

23.22Givethestructureofthecarboxylicacidsformedineachofthefollowingreactions.
(a)

(b)

ReactionsofCarboxylicAcidsandDerivatives
23.23Whichisthestrongeracidineachofthefollowingpairs?
(a)phenol(pKa=9.89)orbenzoicacid(pKa=4.20)
(b)lacticacid(K =1.410 4)orascorbicacid(K =7.910 5)
a a
23.24Arrangethesecompoundsinorderofincreasingacidity:benzoicacid,benzylalcohol,phenol.
23.25AssigntheappropriatepKatoeachoftheacidsinthefollowingsets.
(a)

(b)
23.26AssigntheappropriatepKatoeachoftheacidsinthefollowingsets.
(a)

(b)

23.27Rankthefollowinginorderofincreasingacidity:butanoicacid,2chlorobutanoicacid,3
chlorobutanoicacid,4chlorobutanoicacid.
23.28Rankthefollowinginorderofincreasingacidity:2bromobutanoicacid,2chlorobutanoicacid,
2fluorobutanoicacid,2iodobutanoicacid.
23.29Atroomtemperature,nicotinicacidhasamoderatesolubilityinwaterofapproximately1gram
per60mL.HowwoulditssolubilitychangeifthepHofthewaterwas(a)decreasedtopH=2
and(b)increasedtopH=10?Useequationstoexplainyouranswer.

23.30Hippuricacidisonlyslightlysoluble(4g/L)inwateratroomtemperature.Howwouldits
solubilitychangeifthepHofthewaterwas(a)decreasedtopH=2and(b)increasedtopH=
10?Useequationstoexplainyouranswer.

23.31Givetheexpectedorganicproductsformed(ifany)whenphenylaceticacid,PhCH2COOH,is
treatedwitheachofthefollowingreagents.
(a)SOCl2
(b)NaHCO3,H2O
(c)NH3,H2O
(d)LiAlH4thenH2O
 (e)CH3OH,H2SO4(catalyst)
(f) H2/Niat25Cand300kPapressure
23.32Givetheexpectedorganicproductsformed(ifany)when4chlorobenzoicacidistreatedwith
eachofthefollowingreagents.
(a)PCl5
(b)NaOH,H2O
(c)CH3CH2NH2
(d)NaBH4thenH2O
(e)(CH3)2CHOH,H2SO4(catalyst)
23.33Arrangethefollowingcompoundsinorderofincreasingreactivitytowardsnucleophilicacyl
substitution.

23.34CompletethefollowingFischeresterificationequations.(Assumeexcessalcohol.)
(a)

(b)

(c)

23.35Identifythecarboxylicacidandthealcoholthatarenecessaryinordertomakeeachofthe
followingcompoundsviaaFischeresterification.
(a)

(b)
 (c)CH3CH2CO2C(CH3)3
23.36Writetheproduct(s)ofthetreatmentofpropanoylchloridewitheachofthefollowingreagents.
(a)ethanol(1equivalent)
(b)ammonia(2equivalents)
23.37Writetheproduct(s)ofthetreatmentofbenzoicanhydridewitheachofthefollowingreagents.
(a)ethanol(1equivalent)
(b)ammonia(2equivalents)
23.38Whatproduct(s)is(are)formedwhenethylbenzoateistreatedwiththefollowingreagents?
(a)H2O,NaOH,heat
(b)LiAlH4thenH2O
(c)H2O,H2SO4,heat
(d)CH3CH2CH2CH2NH2
(e)C6H5MgBr(2moles)thenH2O,HCl
23.39Whatproduct(s)is(are)formedwhenbenzamideistreatedwiththefollowingreagents?
(a)H2O,HCl,heat
(b)NaOH,H2O,heat
(c)LiAlH4thenH2O
23.40Showhowtoconvertbutanoicacidintoeachofthefollowingcompounds(morethanonestep
mayberequired).
(a)methylbutanoate
(b)Nmethylbutanamide
(c)butanoylchloride
(d)2methylpentan2ol
(e)ammoniumbutanoate
23.41Showhowtoconvertethylbenzoateintoeachofthefollowingcompounds(morethanonestep
mayberequired).
(a)benzylalcohol
(b)benzoicacid
(c)benzoylchloride
(d)benzamide
(e)3phenylpentan3ol
Triglycerides
23.42Definethetermhydrophobic.
23.43Whatismeantbythetermhardeningasappliedtovegetableoils?
23.44Explainwhythemeltingpointsofunsaturatedfattyacidsarelowerthanthoseofsaturatedfatty
acids.
23.45Whichwouldyouexpecttohavethehighermeltingpoint,glyceryltrioleateorglyceryl
trilinoleate?
23.46WhatamountofH2isusedinthecatalytichydrogenationof1moleofatriglyceridederived
fromglycerol,stearicacid,linoleicacidandoleicacid?
23.47Whatamountofhydrogenisusedinthecatalytichydrogenationof1moleofatriglyceride
derivedfromglycerol,stearicacid,linoleicacidandarachidonicacid?
23.48Drawthestructureofatriglyceridederivedfromglycerol,palmiticacid,andtwoequivalentsof
oleicacidthatisnotchiral.Onthisstructureidentifythehydrophobicandhydrophylicregions.
23.49Drawthestructureofatriglyceridederivedfromglycerol,stearicacid,andtwoequivalentsof
oleicacidthatischiral.Ifthiswashydrogenated,wouldtheproductbechiral?Explain.
23.50Showhowtoconvertpalmiticacid(hexadecanoicacid)intoeachofthefollowing.
(a)ethylpalmitate
(b)palmitoylchloride
(c)hexadecan1ol(cetylalcohol)
(d)hexadecan1amine
(e)N,Ndimethylhexadecanamide
23.51Palmiticacid(hexadecanoicacid,16:0)isthesourceofthehexadecyl(cetyl)groupinthe
followingcompounds.

Eachcompoundisamild,surfaceactinggermicideandfungicideandisusedasatopical
antisepticanddisinfectant.
(a)Cetylpyridiniumchlorideispreparedbytreatingpyridinewith1chlorohexadecane(cetyl
chloride).Showhowtoconvertpalmiticacidtocetylchloride.
(b)BenzylcetyldimethylammoniumchlorideispreparedbytreatingbenzylchloridewithN,
Ndimethylhexadecan1amine.Showhowthistertiaryaminecanbepreparedfrom
palmiticacid.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
23.52Megatomoicacid,thesexattractantofthefemaleblackcarpetbeetle,hasthestructure:

(a)WhatistheIUPACnameformegatomoicacid?
(b)Howmanystereoisomersarepossibleforthiscompound?
23.53TheIUPACnameforibuprofenis2[4(2methylpropyl)phenyl]propanoicacid.Drawthe
structuralformulaforibuprofen.Onthestructure,identifythe2methylpropylandthepropanoic
acidcomponents.
23.54Themonopotassiumsaltofoxalicacidispresentincertainleafyvegetables,includingrhubarb.
Bothoxalicacidanditssaltsarepoisonousinhighconcentrations.Drawthestructuralformula
formonopotassiumoxalate.
23.55Potassiumsorbateisaddedasapreservativetocertainfoodstopreventspoilagebybacteriaand
mouldsandtoextendtheshelflife.TheIUPACnameforpotassiumsorbateispotassium
(2E,4E)hexa2,4dienoate.Drawthestructuralformulaforpotassiumsorbate.
23.56Drawthestructuralformulaofacompoundwitheachofthefollowingmolecularformulaethat,
onoxidationbychromicacid,givesthecarboxylicacidordicarboxylicacidshown.
(a)

(b)

(c)

23.57Completethefollowingacidbasereactions.
(a)

(b)CH3CH CHCH2COOH+NaHCO3
(c)

(d)

(e) CH CH CHCH2COONa++HCI
3
23.58ThenormalpHrangeforbloodplasmais7.357.45.Undertheseconditions,wouldyouexpect
thecarboxylgroupoflacticacid(pKa=3.85)toexistprimarilyasacarboxylgrouporasa
carboxylateanion?Explain.
23.59ThepKaofascorbicacidis4.10.Wouldyouexpectascorbicaciddissolvedinbloodplasma(pH
=7.357.45)toexistprimarilyasascorbicacidorasascorbateanions?Explain.
23.60Excessascorbicacid(pKa=4.10)isexcretedintheurine,thepHofwhichisnormally4.88.4.
Whatformofascorbicacidascorbicaciditselforascorbateanionswouldyouexpecttobe
presentinurinewithpH=8.4?
23.61ThepHofhumangastricjuiceisnormally1.03.0.Whatformoflacticacid(pKa=3.85)
lacticaciditselforitsanionwouldyouexpecttobepresentinthestomach?
23.62Inchapter24,wediscussaclassofcompoundscalledaminoacids,sonamedbecausethey
containbothanaminogroupandacarboxylgroup.Thefollowingaretwostructuralformulaefor
theaminoacidalanine.

IsalaninebetterrepresentedbystructuralformulaAorB?Explain.
23.63Thefollowingisthestructuralformulafortheaminoacidphenyalanineintheformofa
zwitterion.

Whatwouldyouexpecttobethemajorformofphenylalaninepresentinaqueoussolutionat(a)
pH=2.0,(b)pH=56and(c)pH=11.0?Explain.
23.64Explainwhyaminoacids,thebuildingblocksofproteins(chapter24),havepKavaluesnearly
athousandtimeshigherthanaliphaticcarboxylicacids.

23.65Formicacidisoneofthecomponentsresponsibleforthestingofbitingantsandisinjectedunder
theskinbybeesandwasps.Awaytorelievethepainistorubtheareaofthestingwithapaste
ofbakingsodaandwater,whichneutralisestheacid.Writeanequationforthisreaction.
23.66Showhowtoconverttrans3phenylpropenoicacid(cinnamicacid)toeachofthefollowing
compounds.
(a)

(b)
 (c)

23.67Showhowtoconvert3oxobutanoicacid(acetoaceticacid)toeachofthefollowingcompounds.
(a)

(b)

(c)CH3CH CHCOOH
23.68Methyl2hydroxybenzoate(methylsalicylate)hastheodourofoilofwintergreen(Dencorub ).
ThisesterispreparedbyFischeresterificationof2hydroxybenzoicacid(salicylicacid)with
methanol.Drawthestructuralformulaformethyl2hydroxybenzoate.
23.69Benzocaine,atopicalanaesthetic,ispreparedbytreating4aminobenzoicacidwithethanolin
thepresenceofanacidcatalyst,followedbyneutralisation.Drawthestructuralformulafor
benzocaine.
23.70Fromwhichcarboxylicacidandalcoholiseachofthefollowingestersderived?
(a)

(b)

23.71Fromwhichcarboxylicacidandalcoholiseachofthefollowingestersderived?
(a)

(b)

23.72Whentreatedwithanacidcatalyst,4hydroxybutanoicacidformsacyclicester(alactone).Draw
thestructuralformulaofthislactone.
23.73Theanalgesicphenacetinissynthesisedbytreating4ethoxyanilinewithaceticanhydride.Write
anequationfortheformationofphenacetin.
23.74AcarboxylicacidcanbeconvertedtoanesterbyFischeresterification.Showhowtosynthesise
eachofthefollowingestersfromacarboxylicacidandanalcoholbyFischeresterification.
(a)
 (b)

23.75Acarboxylicacidcanbeconvertedtoanesterintworeactionsbyfirstconvertingthecarboxylic
acidtoitsacidchlorideandthentreatingtheacidchloridewithanalcohol.Showhowtoprepare
eachesterinquestion23.74fromacarboxylicacidandanalcoholbythistwostepscheme.
23.76Writeamechanismforthereactionofbutanoylchlorideandammoniatogivebutanamideand
ammoniumchloride.
23.77Showhowtoprepareeachofthefollowingamidesbyreactionofanacidchloridewithammonia
oranamine.
(a)

(b)

(c)

23.78Whatproductisformedwhenbenzoylchlorideistreatedwitheachofthefollowingreagents?
(a)C6H6,AlCl3
(b)CH3CH2CH2CH2OH
(c)CH3CH2CH2CH2SH
(d)CH3CH2CH2CH2NH2(2equivalents)
(e)H2O
(f)

23.79Nicotinicacid,morecommonlynamedniacin,isoneoftheBvitamins.Showhownicotinicacid
canbeconvertedtoethylnicotinateandthentonicotinamide.
23.80Completethefollowingreactions.
(a)

(b)

(c)

(d)

23.81Showhowtoconvert2hydroxybenzoicacid(salicylicacid)toeachofthefollowing
compounds.
(a)

(b)

23.82Showtheproductoftreatingbutyrolactonewitheachofthefollowingreagents.
 (a)NH3
(b)LiAlH4thenH2O
(c)NaOH,H2O,heat
23.83ShowtheproductoftreatingNmethylbutyrolactamwitheachofthefollowingreagents.
(a)HCl,heat
(b)NaOH,heat
(c)LiAlH4thenH2O
23.84Treatingbutyrolactonewith2equivalentsofmethylmagnesiumbromide,followedby
hydrolysisinaqueousacid,givesacompoundwiththemolecularformulaC6H14O2.

Proposeastructuralformulaforthiscompound.
23.85Completethefollowingreactions.
(a)

(b)

(c)

23.86Procaine(itshydrochlorideismarketedasNovocaine)wasoneofthefirstlocalanaesthetics
developedforinfiltrationandregionalanaesthesia.ItissynthesisedbythefollowingFischer
esterification.
 Drawthestructuralformulaofprocaine.
23.87TheactiveingredientN,Ndiethylmtoluamide(DEET)inseveralcommoninsectrepellentsis
synthesisedfrom3methylbenzoicacid(mtoluicacid)anddiethylamine.

Showhowthissynthesiscanbeaccomplished.
23.88ShowhowanestercanreactwithH+/H Otogiveacarboxylicacidandanalcohol.
2

(Hint:ThisisthereverseofFischeresterification.)
23.89Insection23.5,itwassuggestedthatthemechanismfortheFischeresterificationofcarboxylic
acidswouldbeamodelformanyofthereactionsofthefunctionalderivativesofcarboxylic
acids.Thereactionofanacidhalidewithwater,isonesuchreaction.

Suggestamechanismforthisreaction.
23.90WhatcombinationofesterandGrignardreagentcanbeusedtoprepareeachofthefollowing
alcohols?
(a)2methylbutan2ol
(b)3phenylpentan3ol
(c)1,1diphenylethanol
23.91Showhowtoconvertethylpent2enoateintoeachofthefollowingcompounds.
(a)
 (b)

23.92PhosgeneishighlytoxicandwasusedasachemicalweaponinWorldWarI.Itisalsoa
syntheticprecursorusedintheproductionofmanyplastics.

(a)Whenvapoursofphosgeneareinhaled,thecompoundrapidlyreactswithany
nucleophilicsitespresent(OHgroups,NH2groupsetc.),producingHClgas.Drawa
mechanismforthisprocess.
(b)Whenphosgeneistreatedwithethyleneglycol(HOCH2CH2OH),acompoundwith
molecularformulaC3H4O3isobtained.Drawthestructureofthisproduct.
23.93Theanalgesicacetaminophen(paracetamol)issynthesisedbytreating4aminophenolwith1
equivalentofaceticanhydride.Writeanequationfortheformationofacetaminophen.(Hint:
RememberthatanNH2groupisabetternucleophilethananOHgroup.)
23.94Thereactionsofacidhalides,acidanhydridesandesterswithammoniaandaminesareexamples
ofthenucleophilicacylsubstitutionreaction.Writeanequationforthereactionofeachofthe
following.
(a)anacidhalidewithammonia
(b)anacidanhydridewithaprimaryamine
(c)anesterwithasecondaryamine
Ineachcase,identifythenucleophile,theleavinggroupanddrawthestructureofthetetrahedral
carbonyladditionintermediate.
23.95WhencompoundX,C7H7O2N,wasboiledwithconcentratedNaOH,itdissolvedreadily,
evolvingammonia.Theresultingsolutiononacidificationgaveawhiteprecipitatethat,on
refluxingwithmethanolandatraceofsulfuricacid,gavethecharacteristicsmellofmethyl
salicylate.

IdentifyXandtracethereactionsequenceinvolved.
23.96Devisechemicalteststodistinguishbetweenthefollowingcompounds,allofwhicharewhite
solids.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
23.97Fluphenazineisanantipsychoticdrugthatisadministeredasanesterprodrugviaintramuscular
injection.

Thehydrophobictailoftheesterisdeliberatelydesignedtoenableaslowreleaseoftheprodrug
intothebloodstream,wheretheprodrugisrapidlyhydrolysedtoproducetheactivedrug.
(a)Drawthestructureoftheactivedrug.
(b)Drawthestructureofandassignasystematicnameforthecarboxylicacidthatis
producedasabyproductofthehydrolysisstep.
23.98Benzylacetateisapleasantsmellingesterfoundintheessentialoilofjasmineflowersandis
usedinmanyperfumeformulations.Startingwithbenzeneandusinganyotherreagentsofyour
choice,designanefficientsynthesisforbenzylacetate.

23.99Doesanucleophilicacylsubstitutionoccurbetweentheesterandthenucleophileshown?

Proposeanexperimentthatwouldverifyyouranswer.
23.100Reactionofa1or2aminewithdiethylcarbonateundercontrolledconditionsgivesa
carbamicester.
 Proposeamechanismforthisreaction.
23.101Methyl2aminobenzoate,aflavouringagentwiththetasteofgrapes,canbepreparedfrom
toluenebythefollowingseriesofsteps.

Showhowyoumightbringabouteachstepinthissynthesis.
23.102Methyl4aminobenzoateandpropyl4aminobenzoateareusedaspreservativesinfoods,
beveragesandcosmetics.

Showhowthesyntheticschemeinquestion23.101canbemodifiedtogiveeachofthese
compounds.
23.103Startingmaterialsforthesynthesisoftheherbicidepropanil,usedtokillweedsinricepaddies,
arebenzeneandpropanoicacid.Showthereagents(1)to(5)requiredforthissynthesis.
23.104Whenchemistsfollowareactionscheme,theyneedtoverifythattheproductobtainedineach
stepisactuallywhattheywereexpecting.Forthereactionschemebelow,whatevidencecould
beusedtoconfirmthatnicotinicacidhassuccessfullybeenconvertedintoethylnicotinate,and
thenthatethylnicotinatehasbeenconvertedintonicotinamide?Youshouldprovideboth
spectroscopicevidence(chapter20)andsimplechemicaltests.

23.105Thefollowingarestructuralformulaeoftwolocalanaesthetics.
 Lidocainewasintroducedin1948andisnowthemostwidelyusedlocalanaestheticfor
infiltrationandregionalanaesthesia.ItshydrochlorideismarketedunderthenameXylocaine.
Mepivacaine(itshydrochlorideismarketedasCarbocaine)actsfasterthanlidocaineandits
effectslastsomewhatlonger.
(a)Proposeasynthesisoflidocainefrom2,6dimethylaniline,chloroacetylchloride
(ClCH2COCl)anddiethylamine.
(b)Whichamineandacidchloridecanbereactedtogivemepivacaine?
23.106Byconsideringtherelativeacidityofthefollowingcompounds,brieflydescribehowyou
wouldseparatethem.Useequationstoexplainthechemistryinvolved.

23.107Chemistshavedevelopedseveralsynthesesfortheantiasthmaticdrugsalbutamol(alsoknown
asalbuterolor,morecommonly,Ventolin ).Oneofthesesynthesesstartswithsalicylicacid,
thesameacidthatisthestartingmaterialforthesynthesisofaspirin.
 (a)Proposeareagentandacatalystforstep1.Whatnameisgiventothistypeofreaction?
(b)Proposeareagentforstep2.
(c)Nametheamineusedtobringaboutstep3.
(d)Step4isareductionoftwofunctionalgroups.Namethefunctionalgroupsreducedand
namethereagentthatwillaccomplishthereduction.
23.108Considerthefollowinghydrolysisreaction.Neitheroftheproductsisappreciablysolublein
water.Byconsideringtherelativeacidityoftheproducts,brieflydescribehowyouwould
separatethetwo.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
acidanhydride fattyacids nucleophilicacylsubstitution
acidhalide Fischeresterification oil
acylgroup hardening saponification
amide hydrophilic soap
benzyliccarbon hydrophobic transesterification
benzylichydrogen lactam triacylglycerol
carboxylgroup lactone Triglyceride
carboxylicacidgroup lipid tropicaloil
ester micelle
fat nitrile

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

24 AminoAcidsand
Proteins
Thepropertiesofaminoacidsarisefromacombinationofthechemistryofamines(chapter
19)andthatofcarboxylicacids(chapter23).Aminoacidsareimportantintheirownright,
buttheyalsoprovidethebuildingblocksofproteins.Inthischapterwewilllookattheacid
basepropertiesofaminoacidsasthesecontrolmuchofthenatureofproteins,including
manyofthecatalyticfunctionsofenzymes.Understandingthechemistryofaminoacids
allowsusinturntounderstandthemuchmorecomplexstructureandpropertiesofproteins.
Proteinsareamongthemostimportantofallbiologicalcompoundsastheyperformthevital
functionsof:
structure:Structuralproteinssuchascollagenandkeratinarethechiefconstituentsof
skin,bones,hairandfingernails.
catalysis:Virtuallyallreactionsthattakeplaceinlivingsystemsarecatalysedbya
specialgroupofproteinscalledenzymes.
movement:Musclefibresaremadeofproteinscalledmyosinandactin.
transport:Theproteinhaemoglobinisresponsibleforthetransportofoxygenfromthe
lungstotissues,whileotherproteinstransportmoleculesacrosscellmembranes.
protection:Agroupofproteinscalledantibodiesisoneofthebody'smajordefences
againstdisease.
 KEYTOPICS

24.1Aminoacids
24.2Acidbasepropertiesofaminoacids
24.3Peptides,polypeptidesandproteins
24.4Primarystructureofpolypeptidesandproteins
24.5Threedimensionalshapesofpolypeptidesandproteins
24.6Denaturingproteins

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.1AminoAcids
Anaminoacidisacompoundthatcontainsbothacarboxylgroupandanaminogroup.Althoughmany
typesofaminoacidsareknown,theaminoacidsarebythefarthemostsignificantinthebiologicalworld
becausetheyarethebuildingblocksfromwhichthemuchlargerproteinmoleculesareconstructed.Proteins,
likethenucleicacidsyouwilllearnaboutinchapter25,areexamplesofnaturalpolymers.Polymers,which
wewilldiscussinchapter26,areverylargemoleculescomposedofmanysmallermoleculesrepeatedly
linkedtogether.Themillionsofdifferenttypesofproteinsarisefromcombinationsofonly20typesof
aminoacid.Thegeneralstructuralformulaofanaminoacidisshowninfigure24.1.

FIGURE24.1 Representationsofanaminoacid:
(a)the(unrealistic)nonchargedformand
(b)theactualinternalsalt(zwitterion)form.

Althoughfigure24.1seemstobeatypicalwayofwritingstructuralformulaeforaminoacids,itisnot
accuratebecauseitshowsanacid(COOH)andabase(NH2)withinthesamemolecule.Theseacidic
andbasicgroupsreactwitheachothertoformaninternalsalt(adipolarion)(figure24.1),whichisgiventhe
specialnamezwitterion.Notethatazwitterionhasnonetchargeitcontainsonepositivechargeandone
negativecharge.

Becausetheyexistaszwitterions,aminoacidshavemanyofthepropertiesassociatedwithsalts.Theyare
crystallinesolidswithhighmeltingpointstheyarefairlysolubleinwaterbutinsolubleinnonpolarorganic
solventssuchasetherandhydrocarbonsolvents.

Chirality

Withtheexceptionofglycine, ,allproteinderivedaminoacidshaveatleastone
stereocentreandare,therefore,chiral(seechapter17).Figure24.2showsFischerprojectionformulaeforthe
enantiomersofalanine.ThevastmajorityofcarbohydratesinthebiologicalworldareoftheDseries(section
22.2),whereasthevastmajorityofaminoacidsinthebiologicalworldareoftheLseries.Fromtherules
wedevelopedinchapter17,ListheSstereoisomer.(Note,however,thatLcysteineistheRstereoisomer
becauseofthehigherpriorityofthesulfuratom.)
 FIGURE24.2Theenantiomersofalanine.ThevastmajorityofaminoacidsinthebiologicalworldhavetheL
configurationatthecarbonatom.

ProteinderivedAminoAcids
Table24.1givescommonnames,structuralformulaeandstandardthreeletterandoneletterabbreviations
forthe20commonLaminoacidsfoundinproteins.Theaminoacidsshownaredividedintofourcategories:
thosewithnonpolarsidechainsthosewithpolar,butunionised,sidechainsthosewithacidicsidechains
andthosewithbasicsidechains.Asyoustudytheinformationinthistable,notethefollowingpoints:
1.All20oftheseproteinderivedaminoacidsareaminoacids,meaningthattheaminogroupis
locatedonthecarbonatomadjacenttothecarboxylgroup.
2.For19ofthe20aminoacids,theaminoatomgroupisprimary.Prolineisdifferentitsamino
groupissecondary.
3.Withtheexceptionofglycine,thecarbonatomofeachaminoacidisastereocentre.Althoughnot
showninthetable,all19chiralaminoacidshavethesamerelativeconfigurationatthecarbonatom.
IntheD,Lconvention,allareLaminoacids.
4.Isoleucineandthreoninecontainasecondstereocentre.Fourstereoisomersarepossibleforeachof
theseaminoacids,butonlyoneofthefourisfoundinproteins.
5.Thesulfhydrylgroupofcysteine,theimidazolegroupofhistidineandthephenolichydroxylof
tyrosinearepartiallyionisedatpH=7.0,buttheionicformisnotthemajorformpresentatthatpH.
TABLE24.1 The20CommonAminoAcidsFoundinProteins
NonpolarSideChains
alanine phenylalanine

(Ala,A) (Phe,F)

glycine proline

(Gly,G) (Pro,P)

isoleucine tryptophan

(Ile,I) (Trp,W)

leucine
 (Leu,L)

methionine valine

(Met,M) (Val,V)

Polarsidechains
asparagine serine

(Asn,N) (Ser,S)

glutamine threonine

(Gln,Q) (Thr,T)

Acidicsidechains Basicsidechains
aspartic arginine
acid
(Arg,R)
(Asp,D)

glutamic histidine
acid
(His,H)
(Glu,E)

cysteine

(Cys,C)
tyrosine lysine

(Tyr,Y) (Lys,K)

Note:Eachionisablegroupisshownintheformpresentinhighestconcentrationinaqueoussolutionat
pH=7.0.

WORKEDEXAMPLE24.1

AssessingtheStructuralVariationsoftheCommonAmino
Acids
Ofthe20proteinderivedaminoacidsshownintable24.1,howmanycontain(a)aromaticrings,
(b)sidechainOHgroups,(c)phenolicOHgroups,(d)sulfurand(e)basicgroups?

Analysis
 Aminoacidscanlookstructurallycomplex,butitisimportanttounderstandtheirsimilaritiesas
wellastheirdifferences.Thetypeofsidechainpresenthasasubstantialimpactontheproperties
oftheaminoacid,andsoyouwillneedtorecognisethefunctionalgroupspresentintheside
chain.Lookfortheamineandthecarboxylicacidlinkedbyasinglecarbonatomasthecommon
structuralunit,andthenassessthenatureofthefunctionalgroupspresentinthesidechain.

Solution
(a)Phenylalanine,tryptophan,tyrosineandhistidinecontainaromaticrings.
(b)Serineandthreoninecontainsidechainhydroxylgroups.
(c)TyrosinecontainsaphenolicOHgroup.
(d)Methionineandcysteinecontainsulfur.
(e)Arginine,histidineandlysinecontainbasicgroups.

Isouranswerreasonable?

Table24.1showsthestructuresofthegroupspresentontheaminoacids.Aromaticringsrequirea
continuouscycleofsp 2hybridisedatomssuchthatthetotalnumbersofelectronsinthesystem
equals6(or10,14,18etc.).Consequently,histidinecontainsanaromaticringasdotryptophan
andtyrosine.NotethatanOHgroupboundtoanaromaticringimpartsconsiderablydifferent
propertiesfromoneboundtoanalkylchain,whichiswhywedefinealcoholhydroxylgroups
(serineandthreonine)asdifferentfromphenolichydroxylgroups(tyrosine).

Asparagineandglutaminepossessamidesidechains,sothesegroupsarenotbasicsincethe
carbonylorbitalsinteractwiththeloneelectronpaironthenitrogenatom,makingitunavailableto
bondtohydrogenions,H+.

PRACTICEEXERCISE24.1
Ofthe20proteinderivedaminoacidsshown
intable24.1,whichcontain(a)nostereocentre
and(b)twostereocentres?

SomeOtherCommonAminoAcids
Althoughthevastmajorityofplantandanimalproteinsareconstructedfromjustthese20aminoacids,
manyexamplesofotherkindsofaminoacidcanalsobefoundinnature.Ornithineandcitrulline,for
example,arefoundpredominantlyintheliverandareanintegralpartoftheureacycle,themetabolic
pathwaythatconvertsammoniatourea:
Thyroxineandtriiodothyronine,twoofseveralhormonesderivedfromtheaminoacidtyrosine,arefoundin
thyroidtissue.

Theprincipalfunctionofthesetwohormonesistostimulatemetabolisminothercellsandtissues.

Theaminoacid4aminobutanoicacid(aminobutyricacid,orGABA)isfoundinhighconcentration(0.8
10 3M)inthebrain,butinnosignificantamountsinanyothermammaliantissue.GABAissynthesisedin
neuraltissuebydecarboxylationofthecarboxylgroupofglutamicacidandisaneurotransmitterinthe
centralnervoussystemofinvertebratesandpossiblyinhumansaswell.

OnlyLaminoacidsarefoundinproteins,andonlyrarelyareDaminoacidsapartofthemetabolismof
higherorganisms.SeveralDaminoacids,however,alongwiththeirLenantiomers,arefoundinlowerforms
oflife.Forexample,DalanineandDglutamicacidarestructuralcomponentsofthecellwallsofcertain
bacteria.SeveralDaminoacidsarealsopresentinsyntheticantibioticsmadefromaminoacids.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.2AcidbasePropertiesofAminoAcids
Aminoacidsareunusualmoleculesinthattheypossessbothanacidicfunctionalgroupandabasic
functionalgroupinthesamemolecule.Thismeansthatinthebiologicalenvironmenttheycanplaytherole
ofproton(H+)donorsorproton(H+)acceptors.

AcidicandBasicGroupsofAminoAcids
Amongthemostimportantchemicalpropertiesofaminoacidsaretheiracidbasepropertiesallcanbe
weakpolyproticacidsbecauseoftheirCOOHandNH3+groups.Theexactabilityofthesegroupsto
acceptordonateH+isindicatedbytheirpKavalues.(Recallfromchapter11thatthesmallerthepKathe
moreacidicisthegroup.AtlowerpH,carboxylicacidsarefoundintheRCOOHformandaminesarefound
intheRNH3+form.AthigherpH,theoppositeistruecarboxylicacidsarepresentasthesaltRCOOand
aminesarepresentasunchargedRNH2.Figure24.3onp.1061showshowthislooksatdifferentpH).Table
24.2givespKavaluesforeachionisablegroupofthe20proteinderivedaminoacids.

TABLE24.2 ValuesofpKa forIonisableGroupsofAminoAcids

Aminoacid pKaofCOOH pKaofNH3+ pKaofsidechain Isoelectricpoint(pI)(a)

alanine 2.35 9.87 (b) 6.11

arginine 2.01 9.04 12.48 10.76

asparagine 2.02 8.80 5.41
asparticacid 2.10 9.82 3.86 2.98
cysteine 2.05 10.25 8.00 5.02
glutamicacid 2.10 9.47 4.07 3.08
glutamine 2.17 9.13 5.65
glycine 2.35 9.78 6.06
histidine 1.77 9.18 6.10 7.64
isoleucine 2.32 9.76 6.04
leucine 2.33 9.74 6.04
lysine 2.18 8.95 10.53 9.74
methionine 2.28 9.21 5.74
phenylalanine 2.58 9.24 5.91
proline 2.00 10.60 6.30
serine 2.21 9.15 5.68
threonine 2.09 9.10 5.60
tryptophan 2.38 9.39 5.88
tyrosine 2.20 9.11 10.07 5.63
valine 2.29 9.72 6.00

(a)Seep.1063.
(b)Noionisablesidechain.
AcidityofcarboxylGroups
TheaveragevalueofpKaforancarboxylgroupofaprotonatedaminoacidis2.19.Thus,thecarboxyl
groupisaconsiderablystrongeracidthanaceticacid(pKa=4.74)andotherlowmolarmassaliphatic
carboxylicacids.Thisgreateracidityisaccountedforbytheelectronwithdrawinginductiveeffectofthe
adjacentNH3+group(recallthatweusedsimilarreasoninginsection23.5toaccountfortherelative
aciditiesofaceticacidanditsmono,di,andtrichloroderivatives).

AcidityofSidechainCarboxylGroups

DuetotheelectronwithdrawinginductiveeffectoftheNH3+group,thesidechaincarboxylgroupsof
protonatedasparticacidandglutamicacidarealsostrongeracidsthanaceticacid(pKa=4.74).Noticethat
thisacidstrengtheninginductiveeffectdecreaseswithincreasingdistanceoftheCOOHgroupfromthe
NH3+group.ComparetheaciditiesoftheCOOHgroupofalanine(pKa=2.35),theCOOHgroupof
asparticacid(pKa=3.86)andtheCOOHgroupofglutamicacid(pKa=4.07).

AcidityofammoniumGroups

TheaveragevalueofpKaforanammoniumgroup,NH3+,is9.47,comparedwithanaveragevalueof
10.76forprimaryaliphaticammoniumions(section19.7).

Thus,theammoniumgroupofanaminoacidisaslightlystrongeracidthanaprimaryaliphatic
ammoniumionand,conversely,anaminogroupisaslightlyweakerbasethanaprimaryaliphaticamine.

BasicityoftheGuanidineGroupofArginine
Thesidechainguanidinegroupofarginine(N C(NH2)2)isaconsiderablystrongerbasethanan
aliphaticamine.Guanidineisthestrongestbaseofanyneutralcompound.Theremarkablebasicityofthe
guanidinegroupofarginineisattributedtothelargeresonancestabilisationoftheprotonatedformrelative
totheneutralform.
BasicityoftheImidazoleGroupofHistidine
Becausetheimidazolegrouponthesidechainofhistidinecontainssixelectronsinaplanar,fully
conjugatedring,imidazoleisclassifiedasaheterocyclicaromaticamine(section19.6).Theunsharedpairof
electronsononenitrogenatomisapartofthearomaticsextet,whereasthatontheothernitrogenatomis
not.Itisthepairofelectronsthatisnotpartofthearomaticsextetthatisresponsibleforthebasicproperties
oftheimidazolering.Protonationofthisnitrogenatomproducesaresonancestabilisedcation:
TitrationofAminoAcids
ValuesofpKafortheionisablegroupsofaminoacidsaremostcommonlyobtainedbyacidbasetitration
(section11.7)andbymeasuringthepHofthesolutionasafunctionofaddedbase(oraddedacid,
dependingonhowthetitrationisdone).Toillustratethisexperimentalprocedure,considerasolution
containing1.00moleofglycinetowhichhasbeenaddedenoughstrongacidsothatboththeaminoand
carboxylgroupsarefullyprotonated.Next,thesolutionistitratedwith1.00mNaOHthevolumeofbase
addedandthepHoftheresultingsolutionarerecordedandthenplottedasshowninfigure24.3.

Themoreacidicgroup,andtheonetoreactfirstwithaddedsodiumhydroxide,isthecarboxylgroup.When
exactly0.50moleofNaOHhasbeenadded,thecarboxylgroupishalfneutralised.Atthispoint,the
concentrationofthezwitterionequalsthatofthepositivelychargedion,andthepHof2.35equalsthepKa
valueofthecarboxylgroup(pKa1):
 FIGURE24.3Titrationofglycinewithsodiumhydroxide.
Theendpointofthefirstpartofthetitrationisreachedwhen1.00moleofNaOHhasbeenadded.Atthis
point,thepredominantspeciespresentisthezwitterion,andtheobservedpHofthesolutionis6.06.The
nextsectionofthecurverepresentstitrationoftheNH3+group.Whenanother0.50moleofNaOHhas
beenadded(bringingthetotalto1.50moles),halfoftheNH3+groupsareneutralisedandconvertedto
NH2.Atthispoint,theconcentrationsofthezwitterionandnegativelychargedionareequal,andthe
observedpHis9.78,whichequalsthepKavalueoftheammoniumgroupofglycine(pKa2):

Thesecondendpointofthetitrationisreachedwhenatotalof2.00molesofNaOHhavebeenaddedand
glycineisconvertedentirelytoananion.

AminoAcidChargeatPhysiologicalpH
KnowingthepKaofthefunctionalgroupsallowsustounderstandthenatureoftheaminoacidina
physiologicalcontext.Recallfromchapter11thatpKareferstotherelationshipbetweentheequilibrium
concentrationsoftheundissociatedacid(HA)andtheconjugatebase(A).Itisimportanttounderstandthe
implicationsofthisforaminoacidsatthepHconditionsfoundinbiologicalenvironments.Forinstance,if
anaminoacidhasapKaof2,thenKa=10 2.TheratioofHAtoAisderivedfromtheHenderson
Hasselbalchequation:

PhysiologicalsystemsarebufferedandremainatacontrolledpHcloseto7,so[H3O+]=10 7inthese
environments.Substitutingintothisequationgives:

andrearranginggives:

Consequently,theratioofdissociatedRCOOtoundissociatedRCOOHis100000:1(i.e.thereisverylittle
RCOOHpresent),andwecansaythatalloftheaminoacidiseffectivelypresentinthechargedRCOO
form.IfthepKavalueoftheaminoacidisequaltothepH,thereisa50:50mixtureofthetwocomponents:
andrearranginggives:

WhenthepKavalueis1logunitbelowphysiologicalpH(pH=7),theratiois90:10ifitis2logunits
belowthepH,theratiois99:1.Wecanusethisrelationshiptocontrolthechargeoftheaminoacidby
controllingthepH.IfwemakethepHofthesolutioncontainingtheaminoacid2logunitsaboveitspKa
value,weknowthattheaminoacidisessentiallypresent(99%)initsdissociatedform.Toaidyour
understanding,table24.3showstheratiosofundissociatedacids,HA,comparedwiththeconjugatebase,
A,atphysiologicalpHforvariouspKavalues.

TABLE24.3 RatiosofUndissociatedAminoAcids,HA,ComparedwiththeConjugateBase,A,at
PhysiologicalpHforVariouspKa Values

pKa 4 5 6 7 8 9 10
A 99.9 99 90 50 10 1 0.1

HA 0.1 1 10 50 90 99 99.1

Usingthisanalysis,itisclearwhy,atphysiologicalpH,allaminoacidandsidechaincarboxylicacid
groupsareionisedandfoundintheRCOOform.Furthermore,atphysiologicalpH,allamino,sidechain
aminoandguanidinogroupsareprotonated.However,tyrosine'sphenolgroupisnotionised,cysteine's
thiolgroupislargely(butnotcompletely)unionised,andhistidine'ssidechainislargely(butnot
completely)protonated.

IsoelectricPoint
Titrationcurves,suchasthatforglycine(figure24.3),enableustodeterminepKavaluesfortheionisable
groupsofanaminoacid.ThepKavaluesinturnallowustodeterminetheratioofchargedtouncharged
groupsinamolecule.Titrationcurvesalsoenableustodetermineanotherimportantproperty:theisoelectric
point(pI)thepHatwhichmostofthemoleculesoftheaminoacidinsolutionhaveanetchargeof0.The
isoelectricpointsforcommonaminoacidsaregivenintable24.2.Byexaminingthetitrationcurve(figure
24.3),youcanseethattheisoelectricpointforglycinefallshalfwaybetweenthepKavaluesforthecarboxyl
groupsandtheammoniumion:

AtpH=6.06,thepredominantformofglycinemoleculesisthezwitterionfurthermore,atthispH,the
concentrationofpositivelychargedglycinemoleculesequalstheconcentrationofnegativelycharged
glycinemolecules.

Givenavaluefortheisoelectricpointofanaminoacid,itispossibletoestimatethechargeonthatamino
acidatanypH.Forexample,thechargeontyrosineatpH=5.63(theisoelectricpointoftyrosine)is0.A
smallfractionoftyrosinemoleculesispositivelychargedatpH=5.00(0.63ofalogunitlessthanitspI),
andvirtuallyallarepositivelychargedatpH=3.63(2.00logunitslessthanitspI).Asanotherexample,the
netchargeonlysineis0atpH=9.74.AtpHvaluessmallerthan9.74,anincreasingfractionoflysine
moleculesispositivelycharged.
Electrophoresis
Electrophoresis,theprocessofseparatingcompoundsonthebasisoftheirelectriccharges,isusedto
isolateandidentifythecomponentspresentinmixturesofaminoacidsandproteins.Electrophoretic
separationsmostcommonlyusepolyacrylamidegelsandthetechniqueisreferredtoasPAGE,for
polyacrylamidegelelectrophoresis.Atypicalelectrophoresisseparationsetupisshowninfigure24.4a,b.
 FIGURE24.4 Electrophoresisofamixtureof:
(a)and
(b)proteinsbySDSPAGEand
(c)aminoacidsbypaperelectrophoresis.DuringSDSPAGE,proteinswiththehighestmolecular
weightcarrythemostchargeandmovetowardsthepositiveelectrodemostquickly.During
paperelectrophoresis,dependingonthepHofthesolution,aminoacidswithanegative
chargemovetowardsthepositiveelectrode,andthosewithapositivechargemovetowards
thenegativeelectrodethoseattheirisoelectricpointdonotmove.

Theaminoacidsarecolourless,butabluedye,bromophenolblue,isaddedtoaidinloadingthemixture
andtoindicatewhentheprocesshasbeencompleted.Whenanelectricalpotentialisappliedtothegel,
aminoacidsmigratetowardstheelectrodemoleculeswithahighchargedensitymovemorerapidlythan
thosewithalowerchargedensity.Anymoleculealreadyatitsisoelectricpointremainsattheorigin.PAGE
canbedoneonunmodifiedmixtures(nativePAGE),whereseparationisbasedonchargeandmolecular
mass,ortheproteinscanbedenatured(section24.6)usingsodiumdodecylsulphate,astrongdetergent
(SDSPAGE).Thedetergentleavestheproteinwithasimilarlinearstructureandanoverallnegativecharge.
Separationthendependsonlyonmolecularweight.Aftertheseparationiscomplete,thegelmaybetreated
withadyesuchasCoomassieBrilliantBluethattransformseachcomponentintoacolouredband,making
theseparationvisible.OneadvantageofnativePAGEoverSDSPAGEisthatproteinsarenotalteredinthe
separationprocessandmaylaterbedetectedonthebasisofspecificenzymeinteractionsorsubjectedto
furtheranalyticaltechniquessuchasmassspectrometry(section20.2).
Electrophoresiscanalsobeperformedusingotherpolymers,starch,agarandevenpaper.Withpaper
electrophoresisapaperstripsaturatedwithanaqueousbufferofpredeterminedpHservesasabridge
betweentwoelectrodevessels(figure24.4c).Whenanelectricalpotentialisappliedtotheelectrodevessels,
theaminoacidsmigratetowardstheelectrodecarryingthechargeoppositetotheirown.Aspreviously,
moleculeswithahighchargedensitymovemorerapidlythanthosewithalowerchargedensity,andany
moleculealreadyatitsisoelectricpointremainsattheorigin.

Aftertheelectrophoresisprocessiscomplete,theseparatedcomponentsneedtobedetected,orvisualised.
Oftenthisinvolvestreatmentwithadyethattransformseachaminoacidorproteinintoacoloured
compound.Otherapproachesinvolveblotting,whichtransferstheseparatedcompoundstoanothersurface
whichmaycontainreactivedyesorenzymelinkedcolouredresponses.Formixturesofaminoacids,
treatmentwithninhydrin(1,2,3indanetrionemonohydrate)isoftenused.Ninhydrinreactswithamino
acidstoproduceanaldehyde,carbondioxideandapurplecolouredanion:
Thisreactioniscommonlyusedinbothqualitativeandquantitativeanalysesofaminoacids.Ofthe20
proteinderivedaminoacids,19haveprimaryaminogroupsandgivethesamepurplecolouredninhydrin
derivedanion.Proline,asecondaryamine,givesadifferent,orangecoloured,compound.

WORKEDEXAMPLE24.2

AnalysingAminoAcidsBasedontheirCharge
Theisoelectricpointoftyrosineis5.63.Towardswhichelectrodedoestyrosinemigrateduring
paperelectrophoresisatpH=7.0?

Analysis

Negativelychargedmaterialsmovetowardsthepositiveelectrodeandpositivelychargedspecies
movetowardsthenegativeelectrode.Youcandeterminethedirectionofmovementduring
electrophoresisifyouknowthechargeontheaminoacid.

Solution

DuringpaperelectrophoresisatpH=7.0(morebasicthanitsisoelectricpoint),tyrosinehasanet
negativechargesomigratestowardsthepositiveelectrode.

Isouranswerreasonable?

IfthepHofasolutionisequaltothepKavalueofanionisablegroup,thegroupispresentasa50
:50mixtureofchargedandunchargedspecies.Thesituationbecomesmorecomplicatedwhen
thereareseveralionisablegroupspresent,buttheisoelectricpointgivesameasureofthepH
requiredformostofthemoleculestobeuncharged.Here,thepHofthesolutionat7.0ismore
basicthantheisoelectricpoint,sothemoleculeshouldbenegativelycharged.

PRACTICEEXERCISE24.2
 Theisoelectricpointofhistidineis7.64.
Towardswhichelectrodedoeshistidine
migrateduringpaperelectrophoresisatpH=
7.0?

WORKEDEXAMPLE24.1

SeparationofaMixtureofAminoAcidsBasedontheirCharge
Theelectrophoresisofamixtureoflysine,histidineandcysteineiscarriedoutatpH=7.64.
Describethebehaviourofeachaminoacidundertheseconditions.

Analysis

Negativelychargedmaterialsmovetowardsthepositiveelectrodeandpositivelychargedspecies
movetowardsthenegativeelectrode.IfyouknowthepHofthesolutionandthevaluesofthe
isoelectricpointfortheaminoacidsinvolved,youcandeterminethechargespresentandthe
directioninwhichthespecieswillmove.

Solution

Theisoelectricpointofhistidineis7.64.AtthispH,histidinehasanetchargeof0andsoitdoes
notmovefromtheorigin.ThepIofcysteineis5.02atpH=7.64(morebasicthanitsisoelectric
point),cysteinehasanetnegativechargeandsoitmovestowardsthepositiveelectrode.ThepI
oflysineis9.74atpH=7.64(moreacidicthanitsisoelectricpoint),lysinehasanetpositive
chargeandsoitmovestowardsthenegativeelectrode.

Isouranswerreasonable?

Thisseparationcanworkonlyifthemoleculespresenthavedifferentisoelectricpoints.Herethe
isoelectricpointsare5.02,7.64and9.74so,atpH=7.64,wehaveanunchargedmolecule,a
negativelychargedmoleculeandapositivelychargedmolecule.

PRACTICEEXERCISE24.3
Describethebehaviourofamixtureof
glutamicacid,arginineandvalineduring
paperelectrophoresisatpH=6.0.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.3Peptides,PolypeptidesandProteins
In1902,EmilFischerproposedthatproteinswerelongchainsofaminoacidsjoinedtogetherbyamide
bondsbetweenthecarboxylgroupofoneaminoacidandtheaminogroupofanother.Fortheseamide
bonds,Fischerproposedthespecialnamepeptidebond.Figure24.5showsthepeptidebondformed
betweenserineandalanineinthemoleculeserylalanine.

FIGURE24.5Thepeptidebondinserylalanine.

Peptideisthenamegiventoashortpolymerofaminoacids.Weclassifypeptidesbythenumberofamino
acidunitsintheirchains.Amoleculecontainingtwoaminoacidsjoinedbyanamidebondiscalleda
dipeptide.Thosecontainingthreetotenaminoacidsarecalledtripeptides,tetrapeptides,pentapeptides
andsoon.Moleculescontainingmorethantenbutfewerthan20aminoacidsarecalledoligopeptides.
Thosecontaining20ormoreaminoacidsarecalledpolypeptides.Proteinsarebiologicalmacromolecules
withamolarmassof5000u(morethanabout40aminoacids)orgreaterandconsistingofoneormore
polypeptidechains.Thedistinctionsinthisterminologyarenotatallprecise.

Byconvention,polypeptidesarewrittenfromlefttoright,beginningwiththeaminoacidwiththefree
NH3+groupandproceedingtowardstheaminoacidwiththefreeCOOgroup.Theaminoacidwiththe
freeNH3+groupiscalledtheNterminalaminoacid,andthatwiththefreeCOOgroupiscalledthe
Cterminalaminoacid:

WORKEDEXAMPLE24.4
RepresentingtheStructuresofPeptides
DrawthestructuralformulaforCysArgMetAsn.LabeltheNterminalaminoacidandtheC
terminalaminoacid.WhatisthenetchargeonthistetrapeptideatpH=6.0?

Analysis

Aspeptidestructurescanbequitecomplicated,itisimportanttorepresenttheminassimpleand
commonaformaspossible.StartwithCysatthelefthandendthiswillbetheNterminal
aminoacid.Formapeptidebondbetweenthecarboxylcarbonatomofthisandtheaminogroup
ofthenextaminoacid,Arg.Continuealongthechaininthisfashionuntilyoucometotheend
aminoacid,Asn.ThiswillbetheCterminalaminoacid.Thenetchargecanbecalculatedby
analysisofthepKadataforalloftheacidicandbasicgroupspresentinthepeptide.

Solution

ThebackboneofCysArgMetAsn,atetrapeptide,isarepeatingsequenceofnitrogen
carboncarbonyl.Thefollowingisitsstructuralformula:

AtpH=6.0,thebasicgroupspresentarestrongenoughbases(pKaoftheirconjugateacids=
10.2and12.5)tobeprotonated,andtheacidicgroupisastrongenoughacid(pKa=4.1)to
dissociatetogivetheconjugatebase.Thethiolisnotacidicenough(pKa=8.0)todissociate.The
netchargeonthistetrapeptideatpH=6.0istherefore+1.

Isouranswerreasonable?

Linkingaminoacidstomakeapeptideremovestheeffectofmanyofthecarboxylicacidand
aminegroupsonthechargeataparticularpH.Youshouldnotethatapeptide(oramide)linkage
isnotbasic,sothenitrogenatominthispartofthemoleculewillnotbeabletobeprotonatedand
becomecharged.Onlytheterminalamineandcarboxylicacid,aswellastheirsidechaingroups,
governtheoverallchargeonapeptide.

PRACTICEEXERCISE24.4
DrawthestructuralformulaforLysPheAla.
 LabeltheNterminalaminoacidandtheC
terminalaminoacid.Whatisthenetchargeon
thistripeptideatpH=6.0?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.4PrimaryStructureofPolypeptidesand
Proteins
Theprimary(1)structureofapolypeptideorproteinisthesequenceofaminoacidsinitspolypeptide
chain.Inthissense,theprimarystructureisacompletedescriptionofallcovalentbondingina
polypeptideorprotein.

In1953,FrederickSanger(figure24.6)ofCambridgeUniversity,England,reportedtheprimary
structureofthetwopolypeptidechainsofthehormoneinsulin.Thiswasaremarkableachievementin
analyticalchemistryitalsoclearlyestablishedthatallthemoleculesofagivenproteinhavethesame
aminoacidcompositionandthesameaminoacidsequence.Today,theaminoacidsequencesofover
20000differentproteinsareknown,andthenumberisgrowingrapidly.

FIGURE24.6FrederickSangerwasawardedtheNobelPrizeinchemistryin1958forhisworkoninsulin.He
wasawardedasecondNobelPrizeinchemistryin1980forhisworkondeterminingthebase
sequencesinDNA.

AminoAcidAnalysis
Thefirststepindeterminingtheprimarystructureofapolypeptideishydrolysisandquantitative
analysisofitsaminoacidcomposition.Recallfromsection23.5(p.1025)thatamidebondsareresistant
tohydrolysis.Typically,samplesofproteinarehydrolysedin6mHClinsealedglassvialsat110Cfor
24to72hours.(Thishydrolysiscanbedoneinamicrowaveoveninashortertime.)Afterthe
polypeptideishydrolysed,theresultingmixtureofaminoacidsisanalysedbyionexchange
chromatography.Inthisprocess,themixtureofaminoacidsispassedthroughaspeciallypacked
column.Eachofthe20aminoacidsrequiresadifferenttimetopassthroughthecolumn.Aminoacids
aredetectedbyreactionwithninhydrinastheyemergefromthecolumn(section24.2),followedby
absorptionspectroscopy.Currentproceduresforthehydrolysisofpolypeptidesandtheanalysisof
aminoacidmixtureshavebeenrefinedtothepointwhereitispossibletodeterminetheaminoacid
compositionfromaslittleas50nanomoles(5010 9mole)ofapolypeptide.Figure24.7showsthe
analysisofapolypeptidehydrolysatebyionexchangechromatography.Notethat,duringhydrolysis,
thesidechainamidegroupsofasparagineandglutaminearehydrolysed,andtheseaminoacidsare
detectedasasparticacidandglutamicacid.Foreachglutamineorasparaginehydrolysed,anequivalent
amountofammoniumchlorideisformed.

FIGURE24.7AnalysisofamixtureofaminoacidsbyionexchangechromatographyusingAmberliteIR120,
asulfonatedpolystyreneresin.TheresincontainsphenylSO3 Na+groups.Theaminoacid
mixtureisappliedtothecolumnatlowpH(3.25),conditionsunderwhichtheacidicamino
acids(Asp,Glu)areweaklyboundtotheresinandthebasicaminoacids(Lys,His,Arg)are
tightlybound.Sodiumcitratebuffersoftwodifferentconcentrationsandthreedifferentvaluesof
pHareusedtoelutetheaminoacidsfromthecolumn.Cysteineisdeterminedascystine,Cys
SSCys,thedisulfideofcysteine.

SequenceAnalysis
Oncetheaminoacidcompositionofapolypeptidehasbeendetermined,thenextstepistodetermine
theorderinwhichtheaminoacidsarejoinedinthepolypeptidechain.Themostcommonsequencing
strategyistocleavethepolypeptideatspecificpeptidebonds,determinethesequenceofeachfragment,
andthenmatchoverlappingfragmentstoarriveatthesequenceofthepolypeptide.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.5ThreedimensionalShapesofPolypeptidesand
Proteins
Manyofthepropertiesofpolypeptidesandproteinsaregovernedbytheprecisethreedimensionalshapeofthese
complexmolecules.Thecomplexityoftheshapearisesfromthenatureofthepeptidebond.

GeometryofaPeptideBond
Inthelate1930s,LinusPauling(NobelPrizeinchemistry,1954)beganaseriesofstudiesaimedatdeterminingthe
geometryofapeptidebond.Oneofhisfirstdiscoverieswasthatapeptidebondisplanar.Asshowninfigure24.8,the
fouratomsofapeptidebondandthetwocarbonatomsjoinedtoitalllieinthesameplane.

FIGURE24.8Planarityofapeptidebond.Bondanglesaroundthecarbonylcarbonatomandtheamidenitrogenatomare
approximately120.

Hadyoubeenaskedinchapter5todescribethegeometryofapeptidebond,youprobablywouldhavepredictedbond
anglesof120aroundthecarbonylcarbonatomand109.5aroundtheamidenitrogenatom.Thispredictionagrees
withtheobservedbondanglesofapproximately120aroundthecarbonylcarbonatom.Itdoesnotagree,however,
withtheobservedbondanglesof120aroundtheamidenitrogen.Toaccountforthisgeometry,Paulingproposedthat
apeptidebondismoreaccuratelyrepresentedasaresonancehybridofthesetwocontributingstructures.

Contributingstructure1showsacarbonoxygendoublebond,andstructure2showsacarbonnitrogendoublebond.
Thehybrid,ofcourse,isneitheroftheseintherealstructure,thecarbonnitrogenbondhasconsiderabledoublebond
character.Accordingly,inthehybrid,thesixatomgroupshowninthetworesonancestructuresisplanar.

Becauseofthepartialdoublebondcharacter,twoconfigurationsarepossiblefortheatomsofaplanarpeptidebond.
Inone,thetwocarbonatomsarecistoeachotherintheother,theyaretranstoeachother.Thetransconfiguration
ismorefavourablebecause,inthetransconfiguration,thecarbonatomswiththebulkygroupsbondedtothemare
furtherfromeachotherthantheyareinthecisconfiguration.Virtuallyallpeptidebondsinnaturallyoccurringproteins
studiedtodatehavethetransconfiguration.
SecondaryStructure
Secondary(2)structureistheorderedarrangement(conformation)ofaminoacidsinlocalisedregionsofa
polypeptideorproteinmolecule.ThefirststudiesofpolypeptideconformationswerecarriedoutbyLinusPaulingand
RobertCorey,beginningin1939.Theyassumedthat,inconformationsofgreateststability,allatomsinapeptidebond
lieinthesameplaneandthereishydrogenbondingbetweentheNHofonepeptidebondandtheC Oofanother,
asshowninfigure24.9.

FIGURE24.9Hydrogenbondingbetweenamidegroups.

Onthebasisofmodelbuilding,Paulingproposedthattwotypesofsecondarystructureshouldbeparticularlystable:
thehelixandtheantiparallelpleatedsheet.

Thehelix
Inanhelixpattern,showninfigure24.10,apolypeptidechainiscoiledinaspiral.Asyoustudythissectionofthe
helix,notethefollowing:
1.Thehelixiscoiledinaclockwise,orrighthanded,manner.Righthandedmeansthatifyoudturnthehelix
clockwise,ittwistsawayfromyou.Inthissense,arighthandedhelixisanalogoustotherighthandedthreadof
acommonwoodormachinescrew.
2.Thereare3.6aminoacidsperturnofthehelix.
3.Eachpeptidebondistransandplanar.
4.TheNHgroupofeachpeptidebondpointsroughlydownwards,paralleltotheaxisofthehelix,andtheC
Oofeachpeptidebondpointsroughlyupwards,alsoparalleltotheaxisofthehelix.
5.ThecarbonylgroupofeachpeptidebondishydrogenbondedtotheNHgroupofthepeptidebondfour
aminoacidunitsawayfromit.Hydrogenbondsareshownasdashedlines.
6.AllRgroupspointoutwardsfromthehelix.
 FIGURE24.10Anhelix.ThepolypeptidechainisrepeatingunitsofL alanine.(Dashedlinesindicatehydrogenbonding.)

AlmostimmediatelyafterPaulingproposedthehelixconformation,otherresearchersprovedthepresenceofhelix
conformationsinkeratin,theproteinofhairandwool.Itsoonbecameobviousthatthehelixisoneofthe
fundamentalfoldingpatternsofpolypeptidechains.

ChemistryResearch

AntimicrobialPeptides

ProfessorFrancesSeparovic,UniversityofMelbourne

Someantibioticsliterallydeliverakillerblowwhentheyfightdisease,accordingtoresearchbybiophysical
chemistsattheUniversityofMelbourne.Theseantibioticsdestroybacteriabyeffectivelypunchingholes
intheircellmembranes.Thiscanupsettheosmoticbalancesothatwaterflowsin,andthebacteriaswelland
eventuallyburst.AUniversityofMelbourne,SchoolofChemistryresearchteamdiscoveredthiswhile
studyingthestructureofantibioticpeptidesandhowtheykillcells.

Peptidesaresmallproteinsthatplayakeyroleinbiochemistry.Forexample,amphibiansandbacteria
produceantimicrobialpeptidesasprotectionagainstdisease,someofwhichcanactasantibiotics.Manyof
thesepeptidesdestroycellmembranesbutthemechanismisnotwellunderstood.
AccordingtoresearchteamleaderProfessorFrancesSeparovic,moststudieshavelookedatpeptide
antibioticsinsolutioninsteadofobservingtheiractiondirectlyincellmembranes.Togetherwith
collaboratorsattheUniversityofAdelaide,ProfessorSeparovichasbeenstudyingantimicrobialpeptidesin
membranesandinlivebacteriausingNMRspectroscopy,atechniquefordeterminingmolecularstructure.
Theseantibioticpeptidesactasthoughtheypunchholesincellmembranes.

ProfessorSeparovicsaysearlystudiesoftheantibioticpeptidegramicidinAinsolutionshowedittobe
composedoftwotightlyintertwinedstrands.However,herstudiesofthepeptideinsituwithinamodelcell
membranerevealedadifferentpicture.Ratherthanthedoublehelixfoundinsolution,twomoleculesofthe
peptideformasinglehelicalstrandontopofoneanotherwithinthemembrane,formingaholethatserves
asanionchannel.Ionsandwaterflowinoroutofthecellsothatthecellswellsandfinallybursts.This
researchwasthefirsttodeterminethemolecularstructureofapeptidewithinamembranebilayer.

Otherscientistsarenowusingthegramicidinionchannel(figure24.11)aspartofabiosensor(figure
24.12).ProfessorSeparovicsaysthetechniqueinvolveslinkingreceptorsforparticularchemicals,suchas
drugs,tothepeptide.Ifthedrugispresent,itbindstothereceptor,preventstheformationofanionchannel
andreducestheioncurrentthroughthemembrane,whichthesensorcandetect.
 FIGURE24.11GramicidinAionchannelwithbiotinylatedlinkerattached.

FIGURE24.12Graphicalrepresentationofanionchannelswitchbiosensor.Thepinkbarrelwithredlinker
attachedisonehalfofabiotinylatedgramicidinAchannelinalipidbilayermembraneattachedto
agoldelectrode.Whenananalytemolecule(green)bindstothereceptor(red),theioncurrentis
reducedandtheelectrodesensesitspresence.

ThepleatedSheet
Anantiparallelpleatedsheetconsistsofanextendedpolypeptidechainwithneighbouringsectionsofthechain
runninginopposite(antiparallel)directions.Inaparallelpleatedsheet,theneighbouringsectionsruninthesame
direction.Incontrasttothehelixarrangement,NHandC Ogroupslieintheplaneofthesheetandareroughly
perpendiculartothelongaxisofthesheet.TheC OgroupofeachpeptidebondishydrogenbondedtotheNH
groupofapeptidebondofaneighbouringsectionofthechain(figure24.13).
 FIGURE24.13Threepolypeptidechainsrunninginopposite(antiparallel)directionsinapleatedsheetconformation
(dashedlinesindicatehydrogenbondingyellowshapesrepresentsidechains).

Asyoustudythissectionofpleatedsheet,notethefollowing:
1.Thethreesectionsofthepolypeptidechainlieadjacenttoeachotherandruninopposite(antiparallel)
directions.
2.Eachpeptidebondisplanar,andthecarbonatomsaretranstoeachother.
3.TheC OandNHgroupsofpeptidebondsfromadjacentsectionspointateachotherandareinthesame
plane,sothathydrogenbondingispossiblebetweenadjacentsections.
4.TheRgroupsonanyonechainalternate,firstabove,thenbelow,theplaneofthesheet,andsoon.

ThepleatedsheetconformationisstabilisedbyhydrogenbondingbetweenNHgroupsofonesectionofthechain
andC Ogroupsofanadjacentsection.Bycomparison,thehelixisstabilisedbyhydrogenbondingbetweenN
HandC Ogroupswithinthesamepolypeptidechain.

TertiaryStructure
Tertiary(3)structureistheoverallfoldingpatternandarrangementinspaceofallatomsinasinglepolypeptide
chain.Nosharpdividinglineexistsbetweensecondaryandtertiarystructures.Secondarystructurereferstothespatial
arrangementofaminoacidsclosetooneanotheronapolypeptidechain,whereastertiarystructurereferstothethree
dimensionalarrangementofallatomsinapolypeptidechain.Amongthemostimportantfactorsinmaintaining3
structurearedisulfidebonds,hydrophobicinteractions,hydrogenbondingandsaltlinkages.

Disulfidebondsplayanimportantroleinmaintainingtertiarystructure.Disulfidebondsareformedbetweenside
chainsoftwocysteineunitsbyoxidationoftheirthiolgroups(SH)toformadisulfidebond(section19.5).
Treatmentofadisulfidebondwithareducingagentregeneratesthethiolgroups:
Figure24.14showstheaminoacidsequenceofhumaninsulin.Thisproteinconsistsoftwopolypeptidechains:anA
chainof21aminoacidsandaBchainof30aminoacids.TheAchainisbondedtotheBchainbytwointerchain
disulfidebonds.Anintrachaindisulfidebondalsoconnectsthecysteineunitsatpositions6and11oftheAchain.

FIGURE24.14Humaninsulin.TheAchainof21aminoacidsandBchainof30aminoacidsareconnectedbyinterchain
disulfidebondsbetweenA7andB7andbetweenA20andB19.Inaddition,asingleintrachaindisulfidebond
occursbetweenA6andA11.

Asanexampleof2and3structure,letuslookatthethreedimensionalstructureofmyoglobin,aproteinfoundin
skeletalmuscleandparticularlyabundantindivingmammals,suchaswhales(figure24.15),dolphinsandseals.
Myoglobinanditsstructuralrelative,haemoglobin,aretheoxygentransportandstoragemoleculesofvertebrates.
Haemoglobinbindsmolecularoxygeninthelungsandtransportsittomyoglobininmuscles.Myoglobinstores
molecularoxygenuntilitisrequiredformetabolicoxidation.
 FIGURE24.15Likeallhumpbackwhales,Migalooreliesonmyoglobinasastorageformofoxygen.

Myoglobinconsistsofasinglepolypeptidechainof153aminoacids.Myoglobinalsocontainsasinglehaemunit.
HaemconsistsofoneFe2+ion,coordinatedinasquareplanararraywiththefournitrogenatomsofamoleculeof
porphyrin(figure24.16).

FIGURE24.16Representationsofthestructureofhaemfoundinmyoglobinandhaemoglobin.

Determinationofthethreedimensionalstructureofmyoglobinrepresentedamilestoneinthestudyofmolecular
architecture.Fortheircontributiontothisresearch,JohnCKendrewandMaxFPerutz,bothofBritain,sharedthe
1962NobelPrizeinchemistry.Thesecondaryandtertiarystructuresofmyoglobinareshowninfigure24.17.The
singlepolypeptidechainisfoldedintoacomplex,almostboxlikeshape.

FIGURE24.17Ribbonmodelofmyoglobin.Thepolypeptidechainisshowninyellow,thehaemligandinredandtheFeatom
asawhitesphere.

Thereareseveralimportantstructuralfeaturesofthethreedimensionalshapeofmyoglobin:
1.Thebackboneconsistsofeightrelativelystraightsectionsofhelix,eachseparatedbyabendinthe
polypeptidechain.Thelongestsectionofhelixhas24aminoacids,theshortesthasseven.Some75%ofthe
 aminoacidsarefoundintheseeightregionsofhelix.
2.Hydrophobicsidechainsofphenylalanine,alanine,valine,leucine,isoleucineandmethionineareclusteredin
theinteriorofthemolecule,wheretheyareshieldedfromcontactwithwater.Hydrophobicinteractionsarea
majorfactorindirectingthefoldingofthepolypeptidechainofmyoglobinintothiscompact,threedimensional
shape.
3.Theoutersurfaceofmyoglobiniscoatedwithhydrophilicsidechains,suchasthoseoflysine,arginine,serine,
glutamicacid,histidineandglutamine,whichinteractwiththeaqueousenvironmentbyhydrogenbonding.The
onlypolarsidechainsthatpointtotheinteriorofthemyoglobinmoleculearethoseoftwohistidineunits,which
pointinwardstowardsthehaemgroup.
4.Oppositelychargedaminoacidsidechainsclosetoeachotherinthethreedimensionalstructureinteractby
electrostaticattractionscalledsaltlinkages.Anexampleofasaltlinkageistheattractionofthesidechainsof
lysine(NH3+)andglutamicacid(COO).

Thetertiarystructuresofhundredsofproteinshavealsobeendetermined.Itisclearthatproteinscontainhelixand
pleatedsheetstructures,butthatwidevariationsexistintherelativeamountsofeach.Lysozyme,with129aminoacids
inasinglepolypeptidechain,hasonly25%ofitsaminoacidsinhelixregions.Cytochrome,with104aminoacidsin
asinglepolypeptidechain,hasnohelixstructure,butdoescontainseveralregionsofpleatedsheet.Yet,whatever
theproportionsofhelix,pleatedsheetorotherperiodicstructure,virtuallyallnonpolarsidechainsofwatersoluble
proteinsaredirectedtowardstheinteriorofthemolecule,whereaspolarsidechainsareonthesurfaceofthemolecule,
incontactwiththeaqueousenvironment.

WORKEDEXAMPLE24.1

RecognisingPeptideSideChainsthatInfluenceTertiaryStructure
Thesidechainsofwhichofthefollowingaminoacidscanformhydrogenbondswiththesidechainof
threonine?
(a)valine
(b)asparagine
(c)phenylalanine
(d)histidine
(e)tyrosine
(f) alanine

Analysis

Hydrogenbondsoccurbetweenheteroatomsthatpossesslonepairsofnonbondingelectronsandpolarised
NHorOHbonds.ThreoninehasanOHgrouponthesidechain,whichisastronghydrogen
bondinggroup.ItshouldbeabletoformhydrogenbondswithanygroupcontaininglonepairsofNHor
OHbonds.

Solution

Thesidechainofthreoninecontainsahydroxylgroupthatcanparticipateinhydrogenbondingintwo
ways:
1.Itsoxygenatomhasapartialnegativechargeandcanfunctionasahydrogenbondacceptor.
2.Itshydrogenatomhasapartialpositivechargeandcanfunctionasahydrogenbonddonor.

Therefore,thesidechainofthreoninecanformhydrogenbondswiththesidechainsoftyrosine,asparagine
andhistidine.
 PRACTICEEXERCISE24.5
Thesidechainsofwhichaminoacidscanformsalt
linkageswiththesidechainoflysineatpH=7.4?

QuaternaryStructure
Mostproteinswithmolarmassgreaterthan50000uconsistoftwoormorenoncovalentlylinkedpolypeptidechains.
Thearrangementofproteinmonomersintoanaggregationisknownasquaternary(4)structure.Agoodexampleis
haemoglobin(figure24.18),aproteinthatconsistsoffourseparatepolypeptidechains:twochainsof141amino
acidseachandtwochainsof146aminoacidseach.

FIGURE24.18Ribbonmodelofhaemoglobin.Thechainsareshowninpurple,thechainsinyellow,thehaemligandsin
redandtheFeatomsaswhitespheres.

Theseparatepolypeptidespacktogetherandareheldinthisarrangementbythesametypeofinteractionsseenwithin
thetertiarystructures:hydrogenbonds,saltbridgesandhydrophobicinteractions.Forproteinsinaqueous
environments,aggregationsinquaternarystructuresarestabilisedmainlybyhydrophobicinteractions.Thus,separate
polypeptidechainsfoldintocompactthreedimensionalshapestoexposepolarsidechainstotheaqueous
environmentinmostcases,however,thisstillleavessomehydrophobicsectionsoftheproteinsincontactwithwater.
Byaggregatingtoformquaternarystructures,theyareprotectedfromexposure.

ChemistryResearch

ProteinFolding,UnfoldingandMolecularChaperones
ProfessorJohnCarver,UniversityofAdelaide

Proteinsaresynthesisedasunfoldedlinearchainsofaminoacids(U)thatfoldviathefoldingpathway(figure
24.19)intothecorrect(native(N))threedimensionalstructure.Alongthispathway,theproteinadoptsa
varietyofpartiallyfolded,intermediatestates(I)withsomeelementsofsecondarystructureinplace.Under
conditionsofcellularstress,suchaselevatedtemperature,infectionandoxidation,thereverseprocess,protein
unfolding(fromthenativefoldedstate),occursviatheseintermediatestates.Theseintermediateshavetheir
hydrophobiccoreexposedtosolutionand,ifpresentforlongenough,mayaggregateviatheofffolding
pathwaysshown.Muchresearchactivityhasbeengeneratedlatelybecausetheunfoldingofspecificproteins
isassociatedwithmanydiseases,particularlythoseofageingsuchasAlzheimer's,Parkinson'sandcataract.In
thecaseofAlzheimer'sdisease,theunfolding,aggregationandprecipitationofasmallprotein,theamyloid
peptide(A),arebelievedtoberesponsibleforthedisease.Aformshighlyorderedstructuresknownas
amyloidfibrilsandistheprincipalcomponentoftheproteindeposits(plaques)foundinAlzheimer'sdisease.
Thus,understandingtheunfoldingandaggregationofA,andotherdiseaserelatedproteinsthatformsimilar
aggregates,willhelpdeterminethefundamentalprocessesandchemistryassociatedwiththesediseasesand
developmentoftherapeuticsfortheirtreatmentandprevention.

FIGURE24.19Proteinfoldingandunfolding.Offfoldingpathwaysgiveriseeithertodisorderedaggregatesthat
mayprecipitateortohighlyorderedamyloidfibrils,whicharethemajorcomponentsoftheprotein
deposits(plaques)foundindiseasessuchasAlzheimer'sandParkinson's.Smallheatshock
proteins(sHsps)preventbothtypesofproteinaggregationbyinteractingwithintermediatestates(I)
earlyalongtheirofffoldingpathways.NandUindicatethenativeandunfoldedstatesoftheprotein,
respectively.

Invivo,thefoldingandunfoldingofproteinsisregulatedbyadiversegroupofproteinsknownasmolecular
chaperones.Whenreferringtoproteinfolding,thetermchaperoneismostappropriateas,byanalogywitha
humanchaperone,thefunctionofamolecularchaperoneistofacilitatecorrectintimateassociationofa
polypeptidechainbutnottoremainpartofthefinalfunctional,foldedformoftheprotein.Thewellstudied
bacterialchaperone,GroEL,formsaverylargecylindricalaggregatewithacentralcavityintowhichthe
foldingtargetproteinissequestered.Inthisisolatedenvironment,theproteincanfoldwithoutthepossibility
ofillicitinteractionswithothercellularcomponentsthatmayleadtoanincorrectlyfoldedstate.Whenthe
proteinisfolded,itisreleasedfromtheGroELcavity.

Ourstudieshaveconcentratedmainlyonsmallheatshockproteins(sHsps),aubiquitousclassofmolecular
chaperonesthatarespecificallyinvolvedinpreventingtheunfoldingandaggregationoftargetproteins.
Underconditionsofcellularstress,theirsynthesisisenhancedgreatlyandtheythereforeactasoneofthe
primarycellulardefencemechanisms.Becauseoftheirinherentabilitytopreventtargetproteinaggregation,
theseheatshockproteinsarepotentialtherapeuticsinthetreatmentofproteinaggregationdiseasessuchas
Alzheimer'sdisease.Indeed,sHspsarecommonlyfoundassociatedwiththeinvivoproteindepositsthat
characterisethesediseases.Themicrographsinfigure24.20showthatonesHsp,Bcrystallin,preventsin
vitroamyloidfibrilformationbytheproteinsynuclein,themajorcomponentofLewybodydepositsin
Parkinson'sdisease.
 FIGURE24.20Transmissionelectronmicrographsoftheinhibitionofsynucleinamyloidfibrilformationbythe
smallheatshockproteinBcrystallin.
(a)AtneutralpH,synucleinspontaneouslyformsfibrils.
(b)However,inthepresenceofBcrystallin,fibrilformationispreventeddisordered
aggregatesareformedinstead.

Ourworkadoptsahighlyinterdisciplinaryapproachbyusingavarietyofcomplementarybiophysical,protein
chemical,cellbiologicalandspectroscopictechniquestoinvestigatethestructure,functionandinteractionsof
sHsps.Forexample,ourNMRspectroscopicstudieshaveshownthattheyhaveahighlyflexibleand
unstructuredregionattheirextremeCterminus,whichiscrucialinchaperonefunctionandinmaintainingthe
protein'sstructuralintegrity.

Iftwoormoreproteinsassemblesothatthehydrophobicsectionsmatchup,thesecomponentsarethenshieldedfrom
theaqueousenvironment.Thenumbersofsubunitsforseveralproteinsthatareknowntoformquaternarystructures
areshownintable24.4.
TABLE24.4 QuaternaryStructureofSelectedProteins
Protein Numberofsubunits
alcoholdehydrogenase 2
aldolase 4
haemoglobin 4
lactatedehydrogenase 4
insulin 6
glutaminesynthetase 12
tobaccomosaicvirusproteindisc 17

Ontheotherhand,aboutonethirdofallproteinsareactuallypresentinthenonaqueousenvironmentofcell
membranes.Proteinsthatareincorporatedincellmembranesarecalledintegralmembraneproteinsbecausethey
traverseamembranebilayerpartiallyorcompletely.Tokeeptheproteinstableinthenonpolarenvironmentofalipid
bilayer,theseproteinsformquaternarystructuresinwhichtheoutersurfaceislargelynonpolarandcaninteract
favourablywiththelipidenvironment.Theintegralmembraneproteinsaggregatebecausemostofthepolargroups
turninwardsawayfromthenonpolarenvironment,thusformingthequaternarystructuresandshieldingthesegroups
fromthelipids.Figure24.21representsthefourlevelsoforganisationalstructurefoundinproteins.

FIGURE24.21Primary,secondary,tertiaryandquaternarystructuresofaprotein.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
24.6DenaturingProteins
Thefunctionsandpropertiesofproteinsarisefromacombinationofthesecondary,tertiaryandquaternarystructures
thatgiveaproteinitsparticularshapeandconformation.Anyphysicalorchemicalagentthatinterfereswiththese
stabilisingstructureschangestheconformationoftheproteinandoftenremovestheprotein'sfunctionality.Wecallthis
processdenaturation.

Heat,forexample,breaksaparthydrogenbonds,soboilingaproteindestroysitshelicalandpleatedsheet
structures.Thepolypeptidechainsofglobularproteinsunfoldwhenheatedtheunravelledproteinscanthenbind
stronglytoeachotherandprecipitateorcoagulate.Thisiswhathappenswhenaneggisboiledandtheliquidwhiteis
turnedintoasolid.

Similartransformationscanbeachievedbytheadditionofdenaturingchemicals.Forexample,aqueousurea,H2N
CONH2,formsstronghydrogenbonds,soitcandisruptotherhydrogenbondsandcauseglobularproteinsto
unfold.Ethanoldenaturesproteinsbycoagulation.Detergentschangeproteinconformationbydisturbingthe
hydrophobicinteractions,whereasacids,basesandsaltsinterferewithionicsaltbridgesinthetertiaryandquaternary
structures.Otherchemicalagentssuchasreducingagentscanbreakthekeydisulfidebonds(SS)holding
tertiarystructurestogether.Additionally,heavymetalions(Pb 2+,Hg 2+,Cd 2+etc.)attackthiolgroups(SH)toform
newsaltbridgesanddisruptothersaltbridges.Table24.5outlinessomecommondenaturingfactorsandtheregionsof
theproteinthatareaffected.
TABLE24.5 ProteinDenaturingAgentsandtheirModesofAction
Denaturingagent Affectedregion
heat Hbonds
6murea Hbonds
detergents hydrophobicregions
acids/bases saltbridgesandHbonds
salts saltbridges
reducingagents disulfidebonds
heavymetals disulfidebonds/thiols/saltbridges
alcohol hydrationlayers

ChemistryResearch

PuttingtheHeatonPoisonousProteins

In2006,AustraliaandNewZealandweredeclaredbytheWorldOrganisationforAnimalHealthtobetwoof
onlyfourcountriesintheworldthatarefreeofmadcowdisease.Socalledmadcowdiseaseisthename
giventobovinespongiformencephalopathy(BSE),adebilitatingdiseasethatcausesstrangebehaviourin
cattleandeventuallydeath.ConsumingmeatfromanimalsaffectedbyBSEisalsoharmfultohumans.Ithas
beenshownthateatingcontaminatedmeatcanleadtoavariantofthedisease,calledCreutzfeldtJakob
disease(CJD).BSEandCJDarisefromthepresenceofaspecifictypeofmisfoldedproteincalledaprion.Itis
believedthatthesesmall,robustproteinscansurvivethedigestionprocessandbecomeincorporatedintothe
brain,wheretheyleadtosimilarmisfoldingofthebrain'sproteins.Theydothisbyactingasatemplate
aroundwhichthelargerbrainproteinswrap,possiblybecominglockedintheseincorrectstructuresbyafree
radicalorsomeothernonreversiblechemicalreaction.

AustraliaandNewZealandowetheirBSEfreestatustothefactthattheydidnotfollowtheUSandUK'slead
infeedingcattlewithproteinsupplementssourcedfromsheepandchickens.Asimilardiseasecalledscrapie
hasbeenknowninsheepforover200years.However,BSEandCJDhaveonlyrecentlybecomeaproblem
duetoachangeintheregulationscontrollingthewayproteinsupplementsfromsheepweretreated.Ina
terribleexampleofthedangersthatarisewheneconomicsoverrulesscience,lawswerechangedinthe1980s
toallowsheepproteintobetreatedatalowertemperaturethanpreviously.Youhavelearnedinthischapter
thatheatdenaturesproteins,anditisthoughtthattreatmentatthelowertemperature,whilecheaper,allowed
prionproteinsfromscrapietobetransferredtocattle.Fromthere,theprionsweretransferredintothehuman
population,possiblyviapoorlycookedmincecontainingoffal.

Interestingly,AustraliaandNewZealandarefreeofscrapie,notbecauseofhigherstandards,butmorelikely
becauseofthefreerangepracticesusedforraisingcattle.AustraliaandNewZealandcanbethankfulforthis
asCJDhasalreadykilledmorethan150peopleworldwide.Unfortunately,manymoresufferersareexpected
toemerge,asithasbeenestimatedthatmorethan400000cattleinfectedwithBSEenteredthehumanfood
chaininthe1980s.

Australiahasareputationofharbouringthedeadliestcreatures,includingsharks,snakesandcrocodiles.Even
thetimidplatypus(figure24.22)candeliverapowerfulstingthroughaclawonitshindfoot.NewZealand
doesnothaveasmanydangerouscreaturesbutitdoeshavethekatipoorredkatipo(Latrodectuskatipo),
whichisavenomousspiderfoundinmanypartsofNewZealand.Itisawidowspiderandisrelatedto
Australia'sredbackspider(figure24.23)andtheUSA'sblackwidowspiders.

FIGURE24.22Platypus.
 FIGURE24.23Redbackspider.

Interestingly,manyofthevenomsinjectedbyspiders,suchastheredbacksandkatipos,areacocktailof
proteinsthatinterferewithnervetransmissionandcellularfunction.Platypusvenoms(figure24.24),snake
venomsandeventhestingingagentsfromtheboxjellyfish(figure24.25)foundinnorthernAustralianwaters
areallsimilarinthattheycontainpotentmixesofpoisonousproteins,enzymesandpolypeptides.While
antivenomsexistforkatipo,redbackspiderandmanysnakevenoms,nosuchtreatmentisavailablefor
jellyfishstings.Thesestingscausetremendouspain,leavesignificantscarsandhaveledtoanumberof
deaths.Overtheyears,therehavebeenseveralrecommendedinitialtreatmentsforsuchstings,includingsalt
bridgedisruptingsolutionsofinorganicions,includingStingoseandmildacid(vinegar).Currently,the
recommendedfirstaidtreatmentforjellyfishstingsishotwaterashotasthevictimcanstand.Proteins,
enzymesandpolypeptidesmustretainspecificstructurestomaintainactivity,soanyactionthatdisruptstheir
structurewilllowerorpreventtheireffects.Liketheheattreatmentneededtodenaturescrapieprions,hot
waterdenaturesjellyfishtoxinstosomeextentandtheheatmayalsopenetrateintotheaffectedarea,helping
toalleviatetheeffectsofthispainfulsting.
 FIGURE24.24Stereoviewoftheactiveconformationsofoneoftheproteinspresentinplatypusvenom(seepp.44
5forhelpinviewingthisthreedimensionalimage).ReproducedwithpermissionfromAllanMTorres
etal.,JournalofBiochemistry,vol.341,1999,78594.TheBiochemistrySociety

FIGURE24.25Boxjellyfish.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
AminoAcids
Anaminoacidisacompoundwithanaminogroupadjacenttoacarboxylgroup.Aminoacidsexist
aszwitterions,orinternalsalts,atphysiologicalpH.Withtheexceptionofglycine,allproteinderived
aminoacidsarechiral.IntheD,Lconvention,allareLaminoacids.Isoleucineandthreoninecontain
twostereocentres.The20proteinderivedaminoacidscanbedividedintofourcategories:ninewith
nonpolarsidechainsfourwithpolar,butunionised,sidechainsfourwithacidicsidechainsandthree
withbasicsidechains.

AcidbasePropertiesofAminoAcids
Theisoelectricpoint,pI,ofanaminoacid,polypeptideorproteinisthepHatwhichithasnonet
charge.Electrophoresisistheprocessofseparatingcompoundsonthebasisoftheirelectriccharge.
Compoundswithahighchargedensitymovemorerapidlythanthosewithalowerchargedensity.Any
aminoacidorproteininasolutionwithapHthatequalsthepIofthecompoundremainsattheorigin.

Peptides,PolypeptidesandProteins
Apeptidebondisthespecialnamegiventotheamidebondformedbetweenaminoacids.A
polypeptideisabiologicalmacromoleculecontaining20ormoreaminoacidsjoinedbypeptidebonds.
Byconvention,thesequenceofaminoacidsinapolypeptideiswrittenfromtheNterminalaminoacid
totheCterminalaminoacid.

PrimaryStructureofPolypeptidesandProteins
Theprimary(1)structureofapolypeptideisthesequenceofaminoacidsinitspolypeptidechain.

ThreedimensionalShapesofPolypeptidesandProteins
Apeptidebondisplanarthatis,thefouratomsoftheamidebondandthetwocarbonatomsofa
peptidebondlieinthesameplane.Bondanglesaroundtheamidenitrogenatomandthecarbonyl
carbonatomareapproximately120.Secondary(2)structureistheorderedarrangement
(conformation)ofaminoacidsinlocalisedregionsofapolypeptideorprotein.Twotypesofsecondary
structurearethehelixandthepleatedsheet.Tertiary(3)structureistheoverallfoldingpatternand
arrangementinspaceofallatomsinasinglepolypeptidechain.Quaternary(4)structureisthe
arrangementofindividualpolypeptidechainsintoanoncovalentlybondedaggregate.

DenaturingProteins
Denaturationisthelossofaprotein'spropertiesduetotheapplicationofchemicalsorphysical
conditionsthatinterferewithits2,3and4structures.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Acidityofcarboxylgroups(section24.2)
AnCOOH(pKa 2.19)ofaprotonatedaminoacidisaconsiderablystrongeracidthanaceticacid(pKa =
4.74)orotherlowmolarmassaliphaticcarboxylicacids,duetotheelectronwithdrawinginductiveeffectof
theNH3+group.

Acidityofammoniumgroups(section24.2)
AnNH3+group(pKa 9.47)isaslightlystrongeracidthanaprimaryaliphaticammoniumion(pKa
10.76):

Basicityoftheguanidinegroupofarginine(section24.2)
Theprotonatedformoftheargininesidechainformsreadilybecauseofsubstantialresonancestabilisation.

Basicityoftheimidazolegroupofhistidine(section24.2)
Protonationofthenitrogenatomofimidazoleproducesaresonancestabilisedcation.

Reactionofanaminoacidwithninhydrin(section24.2)
Treatinganaminoacidwithninhydringivesapurplecolouredsolution.

Treatingprolinewithninhydringivesanorangecolouredsolution.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
AminoAcids
24.1Whichaminoaciddoeseachofthefollowingabbreviationsstandfor?
(a)Phe
(b)Ser
(c)Asp
(d)Gln
(e)His
(f) Gly
(g)Tyr
24.2Definethetermzwitterion.
24.3Drawzwitterionformsofthefollowingaminoacids.
(a)valine
(b)phenylalanine
(c)glutamine
24.4WhyareGluandAspoftencalledacidicaminoacids?
24.5WhyisArgoftencalledabasicaminoacid?Whichtwootheraminoacidsarealsobasicamino
acids?
24.6Whatisthemeaningofthealphaasitisusedinaminoacid?
24.7Severalaminoacidsexist.Aunitofalanine,forexample,iscontainedwithinthestructureof
coenzymeA.Writethestructuralformulaofalanine.
24.8Whatisthedifferenceinstructurebetweentyrosineandphenylalanine?
24.9Classifythefollowingaminoacidsasnonpolar,polar,neutral,acidicorbasic.
(a)arginine
(b)leucine
(c)glutamicacid
(d)asparagine
(e)tyrosine
(f) phenylalanine
(g)glycine
24.10Whydoesglycinehavenodorlform?
AcidbasePropertiesofAminoAcids
24.11Drawthestructuralformulafortheformofeachofthefollowingaminoacidsthatismost
prevalentatpH=1.0.
(a)threonine
(b)arginine
(c)methionine
(d)tyrosine
24.12Drawthestructuralformulafortheformofeachofthefollowingaminoacidsthatismost
prevalentatpH=10.0.
(a)leucine
 (b)valine
(c)proline
(d)asparticacid
24.13Writethezwitterionformofalanineandshowthereactionof1moleofalaninewitheachofthe
following.
(a)1.0molNaOH
(b)1.0molHCl
24.14WritetheformoflysinemostprevalentatpH=1.0,andthenshowtheproductofthereactionof
1moleoflysinewitheachofthefollowing.(Seetable24.2forpKa valuesoftheionisable
groupsinlysine.)
(a)1.0molNaOH
(b)2.0molNaOH
(c)3.0molNaOH
24.15WritetheformofasparticacidmostprevalentatpH=1.0,andthenshowthereactionof1mole
ofasparticacidwiththefollowing.(Seetable24.2forpKa valuesoftheionisablegroupsin
asparticacid.)
(a)1.0molNaOH
(b)2.0molNaOH
(c)3.0molNaOH
24.16GivenpKa valuesforionisablegroupsfromtable24.2,sketchcurvesforthetitrationof
(a)glutamicacidwithNaOHand
(b)histidinewithNaOH.
24.17Drawastructuralformulafortheproductformedwhenalanineistreatedwitheachofthe
followingreagents.
(a)aqueousNaOH
(b)aqueousHCl
(c)CH3CH2OH,H2SO4
(d)(CH3CO)2O,NaOOCCH3
24.18Dothefollowingcompoundsmigratetothecathodeortheanodeonelectrophoresisatthe
specifiedpH?
(a)histidineatpH=6.8
(b)lysineatpH=6.8
(c)glutamicacidatpH=4.0
(d)glutamineatpH=4.0
(e)GluIleValatpH=6.0
(f) LysGlnTyratpH=6.0
24.19AtwhatpHwouldyoucarryoutanelectrophoresistoseparatetheaminoacidsineachofthe
followingmixtures?
(a)Ala,His,Lys
(b)Glu,Gln,Asp
(c)Lys,Leu,Tyr
Peptides,PolypeptidesandProteins
24.20Whatisthenameofthebondthatlinksaminoacidsinapolypeptideorprotein?
24.21Howmanycarbonatomsalwaysseparatethenitrogenatomsinaproteinorpolypeptide?
24.22Drawallofthestructurespossibleforatripeptidemadefromthreonine,arginineandmethionine.
24.23Considerthefollowingtripeptide.

(a)Usethethreeletterabbreviationsforaminoacidstorepresentthetripeptide.
(b)WhichaminoacidistheCterminalendandwhichistheNterminalend?
PrimaryStructureofPolypeptidesandProteins
24.24Basedonyourknowledgeofthechemicalpropertiesofaminoacidsidechains,suggesta
substitutionforleucineintheprimarystructureofaproteinthatwouldprobablynotchangethe
characteroftheproteinverymuch.
24.25IfaproteincontainsfourSHgroups,howmanydifferentdisulfidesarepossibleifonlyasingle
disulfidebondisformed?Howmanyarrangementsofdifferentdisulfidebondsarepossibleif
twodisulfidebondsareformed?
24.26Howmanydifferenttetrapeptidescanbemadeineachofthefollowingcases.
(a)ThetetrapeptidecontainsoneuniteachofAsp,Glu,ProandPhe.
(b)All20aminoacidscanbeused,buteachonlyonce.
24.27Drawastructuralformulaofeachofthefollowingtripeptides.Markeachpeptidebond,theN
terminalaminoacidandtheCterminalaminoacid.
(a)PheValAsn
(b)LeuValGln
24.28EstimatethepIofeachtripeptideinquestion24.27.
24.29Considerthefollowingtripeptide.

Whichaminoacidswouldbeformeduponhydrolysis(digestion)?
ThreedimensionalShapesofPolypeptidesandProteins
24.30Examinethehelixconformation(p.1070).Areaminoacidsidechainsarrangedallinsidethe
helix,alloutsidethehelixorrandomly?
24.31Distinguishbetweenintermolecularandintramolecularhydrogenbondingbetweenthebackbone
groupsonpolypeptidechains.Inwhichtypeofsecondarystructuredoyoufindintermolecular
hydrogenbonds?Inwhichtypedoyoufindintramolecularhydrogenbonding?
DenaturingProteins
24.32Enzymesareexamplesofproteins.Whydoenzymeslosesomeoftheiractivityathigherthan
physiologicaltemperatures?
24.33Whenaneggisboiled,theyolkchangescolourandconsistencybut,whenitiscooledtoits
originaltemperature,itdoesnotregainitsoriginalnature.Explain.
24.34Itisessentialtowearsafetyglassesinthelaboratory.Explainwhytheeyemustbeprotected
fromevenminoramountsofacidorbase.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
24.35Methionineenkephalinisapentapeptidethatisproducedbythebodytocontrolpain.Fromthe
sequenceofitsaminoacidresidues,drawalinestructureofmethionineenkephalin.

24.36TheconfigurationofthestereocentreinaminoacidsismostcommonlyspecifiedusingtheD,L
convention.TheconfigurationcanalsobeidentifiedusingtheR,Sconvention.Doesthe
stereocentreinLserinehavetheRortheSconfiguration?
24.37AssignanRorSconfigurationtothestereocentreineachofthefollowingaminoacids.
(a) Lphenylalanine
(b)Lglutamicacid
(c) Lmethionine
24.38Theaminoacidthreoninehastwostereocentres.Thestereoisomerfoundinproteinshasthe
configuration(2S,3R)aroundthetwostereocentres.DrawaFischerprojectionofthis
stereoisomerandathreedimensionalrepresentation.
24.39Apartfromthreonine,whichaminoacid(oracids)containmorethanonestereocentre?
24.40AlthoughonlyLaminoacidsoccurinproteins,Daminoacidsareoftenapartofthemetabolism
oflowerorganisms.TheantibioticactinomycinD,forexample,containsaunitofDvaline,and
theantibioticbacitracinAcontainsunitsofDasparagineandDglutamicacid.DrawFischer
projectionsandthreedimensionalrepresentationsforthesethreeDaminoacids.
24.41Bothnorepinephrineandepinephrinearesynthesisedfromthesameproteinderivedaminoacid.
(a)

(b)

Fromwhichaminoacidarethetwocompoundssynthesised,andwhattypesofreactionsare
involvedintheirbiosynthesis?
24.42Histamineissynthesisedfromoneofthe20proteinderivedaminoacids.Suggestwhichamino
acidisthebiochemicalprecursorofhistamine,andnamethetypeoforganicreaction(s)(e.g.
oxidation,reduction,decarboxylation,nucleophilicsubstitution)involvedinitsconversionto
histamine.
24.43Fromwhichaminoacidareserotoninandmelatoninsynthesisedandwhattypesofreactionsare
involvedintheirbiosynthesis?
(a)

(b)

24.44Enzymesareusuallyproteinsandcatalysecommonorganicreactions.Whyareaminoacidssuch
ashistidine,asparticacidandserinemorecommonlyfoundnearthecatalyticsiteoftheenzyme
butaminoacidssuchasleucineandvalineappearlessoftenintheselocations?
24.45WhyishistidineconsideredabasicaminoacidwhenthepKa valueoftheprotonatedformofits
sidechainis6.1?
24.46Accountforthefactthattheisoelectricpointofglutamine(pI=5.65)ishigherthanthe
isoelectricpointofglutamicacid(pI=3.08).
24.47Enzymecatalyseddecarboxylationofglutamicacidgives4aminobutanoicacid.EstimatethepI
of4aminobutanoicacid.
24.48Guanidineandtheguanidinogrouppresentinargininearetwoofthestrongestbiochemical
basesknown.Accountfortheirbasicity.
24.49AtpH=7.4,thepHofbloodplasma,dothemajorityofproteinderivedaminoacidsbearanet
negativechargeoranetpositivecharge?
24.50Examinetheaminoacidsequenceofhumaninsulin(figure24.14)andnotehowmanyAsp,Glu,
His,LysandArgaminoacidsoccurinthismolecule.Doyouexpecthumaninsulintohavean
isoelectricpointnearerthatoftheacidicaminoacids(pI=2.03.0),theneutralaminoacids(pI
=5.56.5)orthebasicaminoacids(pI=9.511.0)?
24.51Glutathione(GSH),oneofthemostcommontripeptidesinanimals,plantsandbacteria,isa
scavengerofoxidisingagents.
 Inreactingwithoxidisingagents,glutathioneisconvertedtoGSSG.
(a)Nametheaminoacidsinthistripeptide.
(b)WhatisunusualaboutthepeptidebondformedbytheNterminalaminoacid?
(c)Isglutathioneabiologicaloxidisingagentorabiologicalreducingagent?
(d)Writeabalancedequationforthereactionofglutathionewithmolecularoxygen,O2,to
formGSSGandH2O.Ismolecularoxygenoxidisedorreducedinthisreaction?
24.52Thefollowingisthestructuralformulafortheartificialsweeteneraspartame.

(a)Namethetwoaminoacidsinthismolecule.
(b)Estimatetheisoelectricpointofaspartame.
(c)Drawstructuralformulaefortheproductsofthehydrolysisofaspartamein1mHCl.
24.53Prolineisoftendescribedasanhelixterminatorthatis,itisusuallyintherandomcoil
secondarystructurefollowinganhelicalportionofaproteinchain.Whydoesprolinenotfit
easilyintoanhelixstructure?
24.54Manyplasmaproteinsfoundinanaqueousenvironmentareglobularinshape.Whichofthe
followingaminoacidsidechainswouldyouexpecttofindonthesurfaceofaglobularprotein,
incontactwiththeaqueousenvironment,andwhichwouldyouexpecttofindinside,shielded
fromtheaqueousenvironment?Explainyouranswers.
(a)Leu
(b)Arg
(c)Ser
(d)Lys
(e)Phe

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
24.55Heatingcandisruptthe3structureofaprotein.Explainthechemicalprocessesthatoccurupon
heatingaprotein.
24.56Someaminoacidscannotbeincorporatedintoproteinsbecausetheyareselfdestructive.As
shownontheright,homoserine,forexample,canuseitssidechainOHgroupinan
intramolecular,nucleophilicacylsubstitutiontocleavethepeptidebondandformacyclic
structureononeendofthechain.

Drawthecyclicstructureformedandexplainwhyserinedoesnotsufferthesamefate,asshown
ontheright.

24.57Wouldyouexpectadecapeptideofonlyisoleucineresiduestoformanhelix?Explain.
24.58Whichtypeofproteinwouldyouexpecttohavethefollowingeffect?
24.59Greenfluorescentprotein(GFP),firstisolatedfrombioluminescentjellyfish,isaprotein
containing238aminoacidresidues.ThediscoveryofGFPhasrevolutionisedthefieldof
fluorescencemicroscopy,whichenablesbiochemiststomonitorthebiosynthesisofproteins.The
2008NobelPrizeinchemistrywasawardedtoMartinChalfie,OsamuShimomuraandRoger
TsienforthediscoveryanddevelopmentofGFP.ThestructuralsubunitofGFPresponsiblefor
fluorescence,calledthefluorophore,resultswhenthreeaminoacidresiduesundergocyclisation.
Identifythethreeaminoacidsthatgointothebiosynthesisofthisfluorophore.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
aminoacids Hydrophobicinteractions primary(1)structure
helix integralmembraneproteins Proteins
pleatedsheet isoelectricpoint(pI) quaternary(4)structure
aminoacid Nterminalaminoacid saltlinkages
Cterminalaminoacid oligopeptides Secondary(2)structure
denaturation pentapeptides Tertiary(3)structure
dipeptide Peptide tetrapeptides
Disulfidebonds peptidebond tripeptides
Electrophoresis polymers zwitterion
hydrogenbonding polypeptides

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

25 TheChemistryofDNA
Deoxyribonucleicacid(DNA)isanenormousmoleculethatstoresourgeneticinformation.
Thisinformationmakesuswhoweareandhelpstodeterminemanyofouroutward
characteristics,suchaseye,hairandskincolour,heightandweight,tonamebutafew.
NaturehaschosenDNAasourgeneticmaterialasitisarelativelyrobustmoleculeanddoes
notreadilyundergoundesirablechemicalreactions.However,damagetotheDNAmolecule
canoccurundersomecircumstances,andthiscanleadtocancer.Skincanceristhemost
commonformofcancerinAustraliaandNewZealand.Itismostoftencausedbythe
damagingeffectofultravioletlightinsunlightonDNAintheskin,whichleadstomutations
andcancerouscellgrowth(shownatright).Thedarkpigmentmelaninhelpstoprotect
humanskinbyabsorbingultravioletlight.Fairskinnedpeople,suchasthoseofAngloCeltic
originwhomakeupthelargestfractionoftheAustralianandNewZealandpopulations,do
notdevelopmuchmelaninintheirskinandsoaremoreatriskofsundamage.Infact,the
incidenceofskincancerinNewZealandandAustraliaisthehighestintheworldtwoin
threeNewZealandersandoneintwoAustralianswilldevelopaskincanceratsometimein
theirlives.

Inthischapter,wewilllookattheDNAmolecule(modelshownatright)indetailtogainan
understandingofitsstructureandfunction.Westartbyexaminingthestructureofthe
buildingblocksofDNAandhowthesearecovalentlybondedtogethertoformthemolecule.
ThenweexplorehowgeneticinformationisencodedbymoleculesofDNA,thefunctionof
thethreetypesofribonucleicacidsand,finally,howtheprimarystructureofaDNA
moleculeisdetermined.

JamesStevenson/SPL
KEYTOPICS

25.1Nucleosidesandnucleotides
25.2Thestructureofdeoxyribonucleicacid(DNA)
25.3Ribonucleicacid(RNA)
25.4Thegeneticcode
25.1NucleosidesandNucleotides
Geneticinformationisstoredinmoleculesofnucleicacid:deoxyribonucleicacid(DNA)andribonucleic
acid(RNA).Acell'sDNAencodestheinformationthatdeterminesthenatureofthecellandcontrolsits
growthanddivisionitalsocontainsinstructionsforthebiosynthesisofenzymesandotherproteinsthatare
essentialforthefunctioningofthecell.RNAisinvolvedinthesynthesisofproteins.Nucleicacidsconsistof
threetypesofsimplerbuildingblockmolecules:
1.aromaticmolecules,consistingofoneortwofusedringswheresomecarbonatomsarereplacedby
nitrogen(suchcompoundsarealsocalledheterocyclic),whichcanactasbases(sections19.6and
19.7)
2.monosaccharides(pentoses),whicharefivememberedcarbohydrates(section22.2)
3.phosphate,asphosphateestersofthepentoses.
Figure25.1showsthefiveheterocyclicaromaticaminebasesmostcommoninnucleicacids.Uracil,
cytosineandthyminearecalledpyrimidinebasesaftertheparentbase.Guanineandadeninearecalled
purinebases.Thebases,exceptforadenine,existasanequilibriumofenolandamidetautomers(seesection
21.6).Oftheseforms,themoststableisthecyclicamide.Suchcyclicamidesarecalledlactams.However,
theenoltautomer(calledalactim)mostclearlydemonstratesthearomaticnatureofthebase.Pyrimidineand
purinebasesarearomaticinnaturebecausetheycontainsixandtenelectrons,respectively(seep.726),
whichsatisfiesthe(4n+2)electronHckelrule.

FIGURE25.1NamesandoneletterabbreviationsfortheheterocyclicaromaticaminebasesmostcommoninDNA
andRNA.Basesarenumberedaccordingtothepatternsofpyrimidineandpurine,theparent
compounds.Thetautomeric(lactim)enolformsofuracilandguaninearegiventoshowtheirstructural
resemblancetothepyrimidineandpurineparents,respectively.

Anucleosideisacompoundcontainingapentose,suchasDriboseand2deoxyDribose,bondedtoa
purineorpyrimidinebasebyaNglycosidicbond(section22.4).ThemonosaccharidecomponentofDNA
is2deoxyDribose(the2deoxyreferstotheabsenceofahydroxylgroupatthe2position),andthatof
RNAisDribose.TheglycosidicbondisbetweenC(1)(theanomericcarbonatom)ofriboseor2
deoxyriboseandN(1)ofapyrimidinebaseorN(9)ofapurinebase.Figure25.2a,bshowsthestructural
formulaofuridine,anucleosidederivedfromriboseanduracil.Atomnumbersonthemonosacchariderings
areprimedtodistinguishthemfromatomnumbersontheheterocyclicbase.Figure25.2cshowsthymidine,
whichcontains2deoxyriboseasthemonosaccharidecomponent.
 FIGURE25.2 Uridine,anucleoside
(a)drawnshowingallhydrogenatoms.
(b)Forconvenience,thehydrogenatomsofCHbondsareusuallyomitted.Atomnumberson
themonosaccharideringsareprimedtodistinguishthemfromatomnumbersonthe
heterocyclicbase.
(c)Thymidinepossesses2deoxyriboseasthemonosaccharidecomponent.

Thenamesofthenucleosides,whichcorrespondtoeachofthebases,arecompiledintable25.1.
TABLE25.1 Nomenclatureofnucleosidesq
Base Nameofnucleoside
uracil uridine
thymine thymidine
cytosine cytidine
guanine guanosine
adenine adenosine

Anucleotideisanucleosideinwhichamoleculeofphosphoricacidisesterifiedwithafreehydroxylgroup
ofthemonosaccharideatthe3orthe5hydroxylgroup.Anucleotideisnamedbygivingthenameofthe
parentnucleoside,followedbythewordmonophosphate.Thepositionofthephosphoricesterisspecified
bythenumberofthecarbonatomtowhichitisbonded.Figure25.3showsthestructuralformulaeof
adenosine5monophosphate,2deoxyadenosine5monophosphateand2deoxyadenosine3
monophosphate.MonophosphoricestersarediproticacidswithpKa valuesofapproximately1and6(see
section11.4).Therefore,atapHof7,thephosphoricmonoesterisionised,givingthenucleotideachargeof
2.
 FIGURE25.3 Thenucleotides
(a)adenosine5monophosphate,
(b)2deoxyadenosine5monophosphateand
(c)2deoxyadenosine3monophosphate.ThephosphategroupisionisedatpH7.0,givingthese
nucleotidesachargeof2.

Nucleosidemonophosphatescanbefurtherphosphorylatedtoformnucleosidediphosphatesandnucleoside
triphosphates.Figure25.4showsthestructuralformulaofadenosine5triphosphate(ATP).ATPisa
phosphorylatingagent(thatis,itdonatesphosphatetoothermolecules)inmanybiochemicalprocesses,
whereitactsasanenergysource.

FIGURE25.4Adenosinetriphosphate(ATP3).

NucleosidediphosphatesandtriphosphatesarealsopolyproticacidsandareextensivelyionisedatpH7.0.
ThevaluesofpKa forthefirstthreeionisationstepsforadenosinetriphosphatearelessthan5.0.Thevalue
ofpKa4isapproximately7.0.Therefore,atpH7.0,approximately50%ofadenosinetriphosphateispresent
asATP4and50%ispresentasATP3.

WORKEDEXAMPLE25.1

DrawingStructuralFormulaeforNucleotides
Drawthestructuralformulafor2deoxycytidine5diphosphateinitstrianionicform(charge=
3).

Analysis

CytidineisformedbyaNglycosidicbondbetweenN(1)ofcytosineandC(1)ofthecyclic
hemiacetalformof2deoxyDribose.The5hydroxylofthepentoseisbondedtoaphosphate
groupbyanesterbond,andthisphosphateisinturnbondedtoasecondphosphategroupbyan
anhydridebond.

Solution
 PRACTICEEXERCISE25.1
Drawthestructuralformulaof2
deoxythymidine3monophosphateinitsdi
anionicform.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
25.2TheStructureofDeoxyribonucleicAcid(DNA)
Inchapter24,wesawthatthefourlevelsofstructuralcomplexityinpolypeptidesandproteinsareprimary,secondary,
tertiaryandquaternary.Therearethreelevelsofstructuralcomplexityinnucleicacids,and,althoughtheselevelsare
somewhatcomparabletothoseinpolypeptidesandproteins,theyalsodifferinsignificantways.

PrimaryStructure:theCovalentBackbone
Deoxyribonucleicacidsconsistofabackboneofalternatingunitsof2deoxyriboseandphosphateinwhichthe3
hydroxylofonedeoxyriboseunitisjoinedbyaphosphodiesterbondtothe5hydroxylofanotherdeoxyriboseunit
(figure25.5).Apurineorpyrimidinebaseadenine,guanine,thymineorcytosineisbondedtoeach2
deoxyriboseunitbyaNglycosidicbond.TheprimarystructureofaDNAmoleculeistheorderofheterocyclic
basesalongthe2deoxyribosephosphodiesterbackbone.The5endistheendofapolynucleotideatwhichthe5
OHgroupoftheterminal2deoxyriboseisfree.The3endofthepolynucleotideistheendatwhichthe3OH
groupoftheterminal2deoxyriboseisfree.Byconvention,thesequenceofbasesisreadfromthe5endtothe3end.
Forexample,infigure25.5,thesequenceis,therefore,TCAG.

FIGURE25.5Atetranucleotidesection,TCAG,ofasinglestrandedDNAshowingthephosphatebackbone(red),deoxyribose
units(black)andnucleobases(blue).TheendofthepolynucleotidehasariboseunitwithafreeOHgroupat
eitherthe3or5position.Thisexampleshowsasectionwithafree3end.

WORKEDEXAMPLE25.2

DrawingStructuralFormulaeforSectionsofDNA
DrawthestructuralformulaoftheDNAdinucleotideTGthatisphosphorylatedatthe5endonly.
 Analysis

Sincethesequenceofbasesisalwaysreadfromthe5endtothe3end,athymidineisconnectedviaa
phosphodiesterbondtoguanosineatthe5endofthelatter.The3endoftheguanosinehasafreeOH
group.

Solution

PRACTICEEXERCISE25.2
DrawthestructuralformulaforasectionofDNA
thatcontainsthebasesequenceCTGandis
phosphorylatedatthe3endonly.

SecondaryStructure:theDoubleHelix
Bytheearly1950s,itwasclearthatDNAmoleculesconsistofchainsofalternatingunitsofdeoxyriboseand
phosphatejoinedby3,5phosphodiesterbonds,withabaseattachedtoeach2deoxyriboseunitbyaNglycosidic
bond.In1953,theAmericanbiologistJamesDWatsonandtheBritishphysicistFrancisHCCrickproposedadouble
helixmodelforthesecondarystructureofDNA.

TheWatsonCrickmodel(seefigure25.6)wasbasedonmolecularmodellingandtwolinesofexperimental
observations:chemicalanalysesofDNAbasecompositionsandmathematicalanalysesofXraydiffractionpatternsof
crystalsofDNA.Watson,CrickandtheNewZealandbornMauriceWilkinssharedthe1962NobelPrizein
physiologyormedicinefortheirdiscoveriesconcerningthemolecularstructureofnucleicacids,anditssignificance
forinformationtransferinlivingmaterial.AlthoughRosalindFranklin(figure25.7)alsotookpartinthisresearch,her
namewasomittedfromtheNobellistbecauseofherdeathin1958attheageof37.TheNobelFoundationdoesnot
makeawardsposthumously.
FIGURE25.6JamesWatsonandFrancisCrickwiththeirDNAmodel.
SPL/ABarrington
 FIGURE25.7RosalindFranklin(19201958):In1951,shejoinedtheBiophysicalLaboratoryatKing'sCollege,London,
whereshebeganherworkontheapplicationofXraydiffractionmethodstothestudyofDNA.Sheiscredited
withdiscoveriesthatestablishedthedensityofDNA,itshelicalconformationandothersignificantaspects.Her
workwasthusimportanttothemodelofDNAdevelopedbyWatsonandCrick.Shediedofovariancancerin
1958attheageof37and,becauseaNobelPrizeisneverawardedposthumously,shedidnotsharethe1962
NobelPrizeinphysiologyormedicinewithWatson,CrickandWilkins.AlthoughtherelationbetweenWatson,
CrickandFranklinwasinitiallystrained,Watsonlatersaidthatwelatercametoappreciatethestrugglesthe
intelligentwomanfacestobeacceptedbythescientificworldwhichoftenregardswomenasmerediversions
fromseriousthinking.PhotoResearchers/IncPhoto

BaseComposition
Atonetime,itwasthoughtthatthefourprincipalbasesoccurredinthesameratiosinallorganismsandwasrepeated
inaregularpatternalongthe2deoxyribosephosphodiesterbackboneofDNA.However,moreprecisedeterminations
oftheircompositionbyErwinChargaffrevealedthatthebasesdonotoccurinthesameratios(table25.2).
TABLE25.2 ComparisonofDNAfromseveralorganismsbasecomposition,inmolepercent
Purines Pyrimidines
Organism A G C T A/T (a) G/C(b) Purines/pyrimidines(c)
human 30.9 19.8 19.9 29.4 1.05 0.99 1.03
sheep 29.3 21.4 21.0 28.3 1.04 1.02 1.03
yeast 31.3 17.1 18.7 32.9 0.95 0.91 0.94
E.coli 24.7 25.7 26.0 23.6 1.05 0.99 1.02

(a)Ratioofmolepercentagesofadenineandthiamine
(b)Ratioofmolepercentagesofguanineandcytosine
(c)Ratioofmolepercentagesofpurinesandpyrimidines

Researchersusedthedataintable25.2andrelateddatatoconclude(Chargaff'srules)that,withinexperimentalerror:
1.ThemolepercentbasecompositionofDNAinanyorganismisthesameinallcellsoftheorganismandis
characteristicoftheorganism.
2.Themolepercentagesofadenine(apurinebase)andthymine(apyrimidinebase)areequal.Themole
percentagesofguanine(apurinebase)andcytosine(apyrimidinebase)arealsoequal.
3.Themolepercentagesofpurinebases(A+G)andpyrimidinebases(C+T)areequalandhavea1:1ratio.

AnalysesofXrayDiffractionPatterns
FundamentalinformationaboutthestructureofDNAemergedwhenXraydiffractionphotographs(seesection7.5)
takenbyRosalindFranklinwereanalysed.Thediffractionpatternsrevealedthat,eventhoughthebasecompositionof
DNAisolatedfromdifferentorganismsvaries,DNAmoleculesthemselvesareremarkablyuniforminthickness.They
arelongandfairlystraight,withanoutsidediameterofapproximately2.0nmandnotmorethan12atomsthick.
Furthermore,thecrystallographicpatternrepeatsevery3.4nm.Thispresentedoneofthechiefproblemstobesolved:
HowcouldthemoleculardimensionsofDNAbesoregular,eventhoughtherelativepercentagesofthevariousbases
differsowidely?Withthisaccumulatedinformation,thestagewassetforthedevelopmentofahypothesisaboutDNA
structure.

TheWatsonCrickDoubleHelix
TheheartoftheWatsonCrickmodelisthepostulatethatamoleculeofDNAisacomplementarydoublehelix
consistingoftwoantiparallelpolynucleotidestrandscoiledinarighthandedmanneraroundthesameaxis.As
illustratedintheribbonmodelsinfigure25.8,chiralityisassociatedwithadoublehelixlikeenantiomers(seechapter
17)lefthandedandrighthandeddoublehelicesarerelatedbyreflection.
 FIGURE25.8ADNAdoublehelixhasanassociatedchirality.Righthandedandlefthandeddoublehelicesofotherwise
identicalDNAchainsarenonsuperimposablemirrorimages.

ToaccountfortheobservedbaseratiosanduniformthicknessofDNA,WatsonandCrickpostulatedthatpurineand
pyrimidinebasesprojectinwardstotheaxisofthehelixandalwayspairinaspecificmanner.Accordingtoscale
models,thedimensionsofanadeninethyminebasepairarealmostidenticaltothedimensionsofaguaninecytosine
basepair,andthelengthofeachpairisconsistentwiththecorethicknessofaDNAstrand(figure25.9).Thus,ifthe
purinebaseinonestrandisadenine,itscomplementintheantiparallelstrandmustbethymine.Similarly,ifthepurine
inonestrandisguanine,itscomplementintheantiparallelstrandmustbecytosine.Inotherwords,ifthesequenceof
onestrandisknown,thesequenceoftheotherstrandcanbeinferred.Thebasepairsareheldtogetherbyhydrogen
bonds(seesection6.8)betweenalonepairofelectronsonacarbonyloxygenatomoraniminenitrogenatominone
baseandaprotonofanaminogroupintheotherbase.
 FIGURE25.9Basepairingbetweenthecomplementarybasesadenineandthymine(AT)andbetweenthecomplementary
basesguanineandcytosine(GC).AnATbasepairisheldbytwohydrogenbonds,whereasaGCbasepair
isheldbythreehydrogenbonds.

AsignificantfeatureofWatsonandCrick'smodelisthatnootherbasepairingisconsistentwiththeobserved
thicknessofaDNAmolecule.Apairofpyrimidinebasesistoosmalltoaccountfortheobservedthickness,whereasa
pairofpurinebasesistoolarge.Thus,accordingtotheWatsonCrickmodel,therepeatingunitsinadoublestranded
DNAmoleculearenotsinglebasesofdifferingdimensions,butratherbasepairsofalmostidenticaldimensions.

ToaccountfortheperiodicityobservedfromXraydata,WatsonandCrickpostulatedthatbasepairsarestackedone
ontopoftheother,withadistanceof0.34nmbetweenbasepairsandwith10basepairsinonecompleteturnofthe
helix.Thus,thereisonecompleteturnofthehelixevery3.4nm.Figure25.10showsaribbonmodelofdouble
strandedBDNA,thepredominantformofDNAindiluteaqueoussolutionandthoughttobethemostcommonform
innature.

FIGURE25.10RibbonmodelofdoublestrandedBDNA.Eachribbonshowsthe2deoxyribosephosphodiesterbackboneof
asinglestrandedDNAmolecule.Thestrandsareantiparallel,onerunningtotheleftfromthe5endtothe3
end,theotherrunningtotherightfromthe5endtothe3end.Hydrogenbondsareshownbythreedotted
linesbetweeneachGCbasepairandtwodottedlinesbetweeneachATbasepair.

Inthedoublehelix,thebasesineachbasepairarenotdirectlyoppositeeachotheracrossthediameterofthehelix,but
ratherareslightlydisplaced.Thisdisplacementandtherelativeorientationoftheglycosidicbondslinkingeachbaseto
thesugarphosphatebackboneleadtotwodifferentsizedgrooves:amajorgrooveandaminorgroove(figure25.10).
Eachgrooverunsalongthelengthofthecylindricalcolumnofthedoublehelix.Themajorgrooveisapproximately
1.2nmwideandtheminorgrooveapproximately0.6nmwidewithbothhavingintermediatedepth.

Figure25.11bshowsmoredetailofaBDNAdoublehelix,especiallythemajorandminorgrooves.
 FIGURE25.11 Computergeneratedmodelsof
(a)ADNA,
(b)BDNAand
(c)ZDNA.Allhydrogenatomshavebeenomittedforclarity.
KennethEward

Otherformsofsecondarystructureareknownthatdifferinthedistancebetweenstackedbasepairsandinthenumber
ofbasepairsperturnofthehelix.

WORKEDEXAMPLE25.3

ComplementaryDNABaseSequence
OnestrandofaDNAmoleculecontainsthebasesequence5ACTTGCCA3.Writeitscomplementarybase
sequence.

Analysis

Rememberthatabasesequenceisalwayswrittenfromthe5endofthestrandtothe3end,thatApairs
withT,andthatGpairswithC.

Solution

IndoublestrandedDNA,thetwostrandsruninopposite(antiparallel)directions,sothatthe5endofone
strandisassociatedwiththe3endoftheotherstrand:
 Writtenfromthe5end,thecomplementarystrandis5TGGCAAGT3.

PRACTICEEXERCISE25.3
WritethecomplementaryDNAbasesequencefor
5CCGTACGA3.

AnotherofthemostcommonsecondarystructuresofDNAisADNA(figure25.11a),whichformsunderconditions
ofhighsaltconcentrationandminimalwaterandisalsoarighthandedhelix.ADNAhasalargerdiameterthanB
DNA(2.6nm)andhas11basepairsperturn,whichis2.5nmlong.Thebasepairsaredisplacedaroundthehelixaxis,
unlikeBDNAwherethebasepairsarecentredaroundthehelixaxis.ThemajorgrooveinADNAisextremely
narrowandverydeep,whereastheminorgrooveisshallowandwide.

ZDNA(figure25.11c)isaconformationvariation,whichhasalefthandeddoublehelix.ComparedwithBDNA,Z
DNAissmallerindiameter(1.8nm)andlonger(4.6nmperturnandeachturnhas12basepairs).Themajorgrooveis
flattenedoutonthehelixsurface,andtheminorgrooveisverydeepandnarrow.ZDNAhasnodefinitebiological
significance.However,itisassumedthattemporaryformationofZDNAduringDNAtranscriptioncouldprovide
torsionalstrainrelief.

TertiaryStructure:SupercoiledDNA
ThelengthofaDNAmoleculeisconsiderablygreaterthanitsdiameter,andtheextendedmoleculeisquiteflexible.A
DNAmoleculeissaidtoberelaxedifithasnotwistsotherthanthoseimposedbyitssecondarystructure.Putanother
way,relaxedDNAdoesnothaveaclearlydefinedtertiarystructure.However,DNAcanexhibittwotypesoftertiary
structure:oneinducedbyperturbationsincircularDNA,theotherintroducedbythecoordinationoflinearDNAwith
nuclearproteinscalledhistones.Theformationoftertiarystructureofnucleicacids,whateverthetype,iscalled
supercoiling.

SupercoilingofCircularDNA
CircularDNAisatypeofdoublestrandedDNAinwhichthe5and3endsofeachstrandarejoinedby
phosphodiesterbonds(figure25.12a).ThistypeofDNA,whichisthemostprominentforminbacteriaandviruses,is
alsoreferredtoascircularduplex(becauseitisdoublestranded)xDNA.OnestrandofcircularDNAmaybeopened,
partiallyunwoundandthenrejoined.Theunwoundsectionintroducesastrainintothemoleculebecausethe
nonhelicalgapislessstablethanhydrogenbonded,basepairedhelicalsections.Thestraincanbelocalisedinthe
nonhelicalgap.Alternatively,thestrainmaybespreaduniformlyovertheentirecircularDNAbytheintroductionof
superhelicaltwists,onetwistforeachturnofahelixunwound(supercoiledcircularDNA).ThecircularDNAshown
infigure25.12bhasbeenunwoundbyfourcompleteturnsofthehelix.Thestrainintroducedbythisunwindingis
spreaduniformlyovertheentiremoleculebytheintroductionoffoursuperhelicaltwists(figure25.12c).
InterconversionofrelaxedandsupercoiledDNAiscatalysedbygroupsofenzymescalledtopoisomerasesand
gyrases.
 FIGURE25.12 RelaxedandsupercoiledDNA:
(a)CircularDNAisrelaxed.
(b)Onestrandisbroken,unwoundbyfourturnsandtheendsthenrejoined.Thestrainofunwindingis
localisedinthenonhelicalgap.
(c)Supercoilingbyfourtwistsdistributesthestrainofunwindinguniformlyovertheentiremoleculeof
circularDNA.

SupercoilingofLinearDNA
ChromatinisacombinationofDNAandproteinsthatmakeupchromosomes.ChromatincontainsalloftheDNAof
thenucleusinanimalorplantcellsandrepresentsatypeofsupercoilingoflinearDNA.Thefundamentalstructural
unitofchromatinisthenucleosome,anassemblyconsistingofagroupofcertainproteins,calledhistones(designated
H1,H2A,H2B,H3andH4,seefigure25.13a),wrappedinDNA(figure25.13b).Histonesareparticularlyrichinthe
basicaminoacidslysineandarginine,and,atphysiologicalpH,haveanabundanceofpositivelychargedsitesalong
theirlength.Inanucleosome,BDNAiswoundaroundthehistoneunitbyabout1.8coils(figure25.13b,25.13c).This
arrangementisheldtogetherthroughelectrostaticforcesbetweenthenegativelychargedphosphatebackboneofthe
DNAandthepositivechargesinthehistoneproteins.Thenucleosomesarefurtherfoldedtoformafilament,witha
diameterof~30nm,whichhasbeenproposedtohavethestructureshowninfigure25.13d.
 FIGURE25.13 Chromatinfibresconsistof
(a)histones
(b)wrappedinDNAtoform
(c)nucleosomes,whichare
(d)groupedtoresemblebeadsonathread(C=CterminalandN=NterminalendoftheproteinH=
histone).

DNAsupercoilingisimportantforpackagingDNAwithincells.DNAisaverylongmolecule,andsupercoiling
reducesspace.

DNAReplication
ReplicationofDNAoccurswhencellsdivide.ThereplicationiscatalysedbyenzymescalledDNApolymerase,which
usesinglestrandedDNAastemplatesforthesynthesisofthecomplementarystrandfromtheappropriate2
deoxyribonucleosidetriphosphate.NearlyallknownDNApolymerasescanaddanucleotideonlyatthefree3
hydroxylgroup,soDNAchainsareextendedinthe53direction.
DNAreplicatesbytheprogressiveseparationoftheduplexstrands,whichisaccompaniedbysynthesisofthe
respectivecomplimentarystrands.Helicasesareenzymesthatbreakthehydrogenbondstoformastructureknownas
thereplicationfork.Thetwoprongsarecalledtheleadingstrandandthelaggingstrand.Theleadingstrandisthe
templatewherethereplicationforkmovesalonginthe35directionsothatthecomplementarystrandcanbe
continuouslysynthesisedbyDNApolymeraseinthe53direction.

Incontrasttothis,thelaggingstrandisorientedinthe53direction.Sincethisisoppositetotheorientationof
DNApolymerase,replicationofthelaggingstrandismorecomplicated.Itwasfoundthatthecomplementarystrandis
alsosynthesisedinthe53direction,butdiscontinuouslyinsmallfractions(thesocalledOkazakifragments),
whicharesubsequentlycovalentlyjoinedbytheenzymeDNAligase.Thissynthesisisinitiatedbytheenzyme
primase,whichreadstheDNAandaddsRNAinshortsegments.DNApolymeraseusesthisprimertosynthesisethe
Okazakifragments,fromwhichtheRNAmoietiesaresubsequentlyremovedandreplacedbyDNAnucleotidesbefore
ligationfusesthefragmentstogether.

ChemistryResearch

ProteinRecognition

AssociateProfessorJacquelineAnneWilce,MonashUniversity

Proteinsareemployedtocarryoutanenormousrangeoftasksinourcells.Theseincludeproteinsonthe
surfaceofcellstoreceiveextracellularsignals,structuralproteinsthatgiveourcellsshape,enzymesthat
catalysereactionsandproteinsthatregulatetheactivitiesofoligonucleotides.Aswesawinchapter24,these
proteinscarryouttheirindividualrolesduetotheiruniquethreedimensionalstructure.Theirsurfaceshape
anditschemistryallowthemtorecogniseabindingpartnerandbindthroughnoncovalentinteractions.

Inordertounderstandhowaproteinstructurerecognisesitsbindingpartner,wecanuseanumberof
spectroscopictools,includingXraycrystallography(seechapter7)andnuclearmagneticresonance(NMR)
spectroscopy(seechapter20).AssociateProfessorJacquelineWilceisinterestedinthemolecularbasisof
proteininteractionswithbindingpartners.SheisanNMRspectroscopistandProfessorMatthewWilce,with
whomsherunsherlaboratory,isanexpertinXraycrystallography.Thesetechniquescomplementone
anothertogivehighlydetailedinformationaboutthechemistryofmolecularrecognition.

Thereplicationterminatorprotein(RTP)ofBacillussubtilisplaysanimportantroleincoordinatingthe
replicationofthebacterialchromosome.Itisadimericproteinthatbindswithexceptionallyhighaffinityto
duplexDNAatspecificnucleotidesequencesformingaterminationcomplexthatpreventsfurtherDNA
replication.ExactlyhowRTPrecognisestheDNAtoformaterminationcomplexhasbeenstudiedusinga
combinationofXraycrystallographyandNMRspectroscopy.AftergrowingcrystalsofhighlypurifiedRTP
combinedwithashortstretchofduplexDNA,theXraydiffractionpatterncanbeusedtoobtainadetailed
pictureoftheatomsinvolvedintheRTP/DNAcomplex(figure25.14).

FIGURE25.14Structureofthereplicationterminatorprotein(RTP)boundtoduplexDNAdeterminedusingXray
crystallography.TheRTPdimerisshownasacartoonwithonemonomercolouredpurpleandthe
othermonomercolouredorange.ReprintedfromBiochemicalandBiophysicalResearch
Communications,Vol.335(2),HastingsAF,OttingG,FolmerRH,DugginIG,WakeRG,WilceMC,
WilceJA

NMRspectroscopyisanalternativetechniqueforderivingstructuralinformationforproteins.Itusesthe
radiofrequencysignalsemittedfrommagneticallysusceptiblenucleiwithintheprotein.Thesignalsfrom1H
areusedtodeterminetheirdistancesfromother1Hnuclei.Amodeloftheproteincanbederivedwhen
enoughofsuchdistanceconstraintsaredetermined.Thismethodofstructuredeterminationisreadilyapplied
tosmallerproteinsbutnottohighmolecularmassmoleculesfromwhichsignalsarelessreadilymeasured.

However,NMRisalsoahighlysensitivetechniqueforprobingtheinteractionbetweenaproteinandits
bindingpartner.Eveninteractionsofquitelargeproteins,suchasthe29kDaRTPdimer,canbeprobedusing
NMRspectroscopy.AcommonNMRexperimentistheheteronuclearsinglequantumcoherence(HSQC)
experimentthatdetectssignalsarisingfrom1Hnucleithatarecovalentlyboundto15Nnuclei.Sincenearly
everyaminoacidhasanNHgroup(exceptforproline),asignalcanbeobtainedthatrepresentstheNH
ofeachaminoacid.AtwodimensionalHSQCNMRspectrum,whichshowssignalsattheintersectionof1H
and15Nfrequencyaxes,actsasaveryusefulmolecularfingerprintforaprotein(figure25.15).
 FIGURE25.15 TheHSQCNMRexperiment.
(a)OverlayedHSQCspectrashowingthesignalsarisingfromtheNHgroupsofeachamino
acidinRTPbeforeDNAisadded(blackspots)andafterDNAisadded(redspots).Many
signalsstayinthesameplace,showingthattheelectronicenvironmentofthatNHgroupis
notperturbedbyDNAbinding.However,spotsthatmoveindicatethataparticularNH
grouphasbeenperturbedbyDNAbinding.

(b)DepictionofuncomplexedRTP(black)andRTPincomplexwithDNA(red)correspondingto
thetwostatesobservedintheHSQCexperiment.
ReprintedfromBiochemicalandBiophysicalResearchCommunications,Vol.335(2),HastingsAF,
OttingG,FolmerRH,DugginIG,WakeRG,WilceMC,WilceJA

Sincetheradiofrequencysignalsofthefingerprintarehighlysusceptibletotheirsurroundingelectronic
environment,evenaslightchangetotheirlocalsurroundingscanbedetectedbyachangeinthefrequencyof
thesignal.Thus,ifduplexDNAisaddedtotheRTPprotein,theHSQCspectrumthatisobtainedisvisibly
changed,revealingwhichindividualaminoacidsarenowexperiencingadifferentelectronicenvironment.
TogetherwithXraycrystallography,NMRcanbeusedtogetadetailedunderstandingofhowtwomolecular
speciesinteract.

ChemistryResearch

Nanotechnology
ProfessorMaxLuandDrZhiPingXu,UniversityofQueensland

Cleanenergy,environmentandhealthcareareallcriticaltoourcontinuedsustainabledevelopment.This
posesagreatchallengeforscienceandtechnology,butnanostructuredmaterialswillmakesignificant
contributionstomeetthesechallenges.Nanoscalescienceandengineeringrepresentnewparadigmsin
scienceandtechnologyandarelogicalconvergencesofthebasicsciencesofchemistry,biologyand
physics.Nanotechnologyofferstremendouspotentialtorevolutionisematerialsanddevices,thewaythey
aremadeandperform,andindeedthewaywelive.

Nanotechnologywillmakethingsbetter,faster,smallerandcheaper,andwillalsocreatenewclassesof
productsandservices,andconsequentlynewmarkets.Nanoscienceisahugeinterdisciplinaryfield,but,
withmanychallengesahead,itishardtopredictwhereitwilllead.Chemists,biologists,physicistsand
engineerswillneedtoworktogethertomeetthesechallenges.

Comparedwithbulkmaterials,nanomaterialsprobablypossessimprovedphysicalandchemicalproperties.
Thesepropertieschangewithparticlesizeandcanbecontrolledbymanipulatingthebuildingblocks.In
nanomaterialresearch,weoftenrefertofunctionalnanomaterialsthesehaveessentialfunctionalproperties
thatareusefulinprocessessuchasadsorption,ionconduction,separation,catalysis,biosensingand
biomoleculardelivery.

Oneexampleoffunctionalnanoparticlesisnanometresizedlayereddoublehydroxides(LDHs),whichhave
beensuccessfullyexploredascellulardeliveryvehiclesforvariousdrugsandbioactivemoleculessuchas
genesegments.Recentwork,ledbyProfessorMaxLuattheUniversityofQueensland,revealsthatthe
hexagonalLDHnanoparticles(figure25.16)candeliversmallmolecularweightheparin(HP,agoodblood
anticoagulant)tovascularsmoothmusclecells(SMCs)moreefficientlythanheparinitself(figure25.17).
ThisefficientdeliveryofHPtoSMCs,togetherwithitssustainablereleasefromLDHHPnanohybrids
(figure25.18),enhancestheprohibitioneffectofHPonSMCmigrationandproliferation,whichisactively
pursuedinsearchofeffectiveantirestenosistreatment.Nonetheless,LDHnanoparticleshavebeenproven
tobelesstoxicthananycommercialdeliveryagentandsafeevenindosesupto100gmL1.Ongoing
researchinProfessorLu'slaboratoryincludesthetreatmentofratswithanartificiallyinjuredarterybyusing
LDHHPnanohybridsthataremodifiedwithanantibodythatcanfindtheinjuredarteryregions.
Investigationsareongoingtoevaluatetheefficiencyofthissystemicdelivery.

FIGURE25.16SEMofplateletlayereddoublehydroxideheparinnanohybrids(LDHHP).
 FIGURE25.17Confocalimagesofsmoothmusclecells(blue)internalising(AE)FITClabelledheparin(HP,
green)or(AE)FITClabelledLDHHP(green)atdifferenttimes.

FIGURE25.18InvitroheparinreleaseprofilefromLDHHPinPBSsolutionat37C.ReprintedfromBiochemical
andBiophysicalResearchCommunications,Vol.335(2).HastingsAF,OttingG,FolmerRH,
DugginIG,WakeRG,WilceMC,WilceJA,Interactionofthereplicationterminatorproteinof
BacillussubtiliswithDNAprobedbyNMRspectroscopy,3616,September23,2005,with
permissionfromElsevier

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
25.3RibonucleicAcid(RNA)
Ribonucleicacid(RNA)isinvolvedinproteinsynthesis.ThestructureofRNAisprincipallysimilarto
deoxyribonucleicacid(DNA)inthatit,too,consistsoflong,unbranchedchainsofnucleotidesjoinedby
phosphodiestergroupsbetweenthe3hydroxylofonepentoseandthe5hydroxylofthenext.Thereare,
however,threemajordifferencesinstructurebetweenRNAandDNA:
1.ThepentoseunitinRNAisDriboseratherthan2deoxyDribose(seefigure25.2).
2.ThepyrimidinebasesinRNAareuracilandcytosineratherthanthymineandcytosine(seefigure
25.1).
3.RNAissinglestrandedratherthandoublestranded.

CellscontainuptoeighttimesasmuchRNAasDNA,and,incontrasttoDNA,RNAoccursindifferent
formsandinmultiplecopiesofeachform.RNAmoleculesareclassifiedaccordingtotheirstructureand
functionduringproteinsynthesisintothreemajortypes:ribosomalRNA,transferRNAandmessenger
RNA.Table25.3summarisesthemolarmass,numberofnucleotidesandpercentageofcellularabundance
ofthethreetypesofRNAincellsofEscherichiacoli.Thisorganismisoneofthebeststudiedbacteriaanda
workhorseforcellularstudies.Itisoneofthemainspeciesofbacterialivinginthelowerintestinesof
mammals,anditspresenceinsurfacewaterisanindicatoroffaecalcontamination.E.colicancauseseveral
intestinalandextraintestinalinfections,suchasurinarytractinfections,meningitisandgramnegative
pneumonia.
TABLE25.3 TypesofRNAfoundincellsofEscherichiacoli.
Type Molarmassrange(u) Numberofnucleotides PercentageofcellRNA
mRNA 250001000000 753000 2
tRNA 2300030000 7394 16
rRNA 350001100000 1202904 82

RibosomalRNA
ThebulkofribosomalRNA(rRNA)isfoundinthecytoplasminsubcellularparticlescalledribosomes,
whichcontainabout60%RNAand40%protein.Ribosomesarethesitesincellsatwhichproteinsynthesis
takesplace.

Ribosomesaremajortargetsforthedevelopmentofnewantibioticsagainstvariousdiseases.Antibioticscan
blockthefunctionofbacterialribosomes,killingthebacteria.Becauseoftheimportanceoftheribosome's
innermostworkingsinthedevelopmentofnewdrugs,the2009NobelPrizeinchemistrywasawardedto
VenkatramanRamakrishnan,ThomasASteitzandAdaEYonathfortheirworkonunderstandingthe
bindinginteractionsbetweenantibioticsandribosomes.

TransferRNA
TransferRNA(tRNA)moleculeshavethelowestmolarmassofallnucleicacids.Theyconsistof73to94
nucleotidesinasinglestrand.tRNAhastheroughshapeofacloverleaf,whichisformedbypairingof
complementarybaseswithinthestrand(figure25.19).ThefunctionoftRNAistocarryaminoacidstothe
sitesofproteinsynthesisontheribosomes.EachaminoacidhasatleastonetRNAdedicatedspecificallyto
thispurposeseveralaminoacidshavemorethanone.
 FIGURE25.19SecondarystructureofayeasttRNAthatcodesforphenylalanine.

EachaminoacidiscodedbyasocalledanticodontripletononeleafofthetRNA(seefigure25.19).Inthe
transferprocess,theaminoacidisjoinedtoitsspecifictRNAbyanesterbondbetweenthecarboxyl
groupoftheaminoacidandthe3hydroxylgroupoftheriboseunitatthe3endofthetRNA(acceptor
stem).Theexampleinfigure25.19isayeasttRNAthatcodesforphenylalanine.

MessengerRNA
MessengerRNA(mRNA)ispresentincellsinrelativelysmallamountsandisveryshortlived.Messenger
RNAmoleculesaresinglestranded,andtheirsynthesisisdirectedbyinformationencodedonDNA
molecules.Asillustratedatthebottomofthenextpage,doublestrandedDNAisunwound,anda
complementarystrandofmRNAissynthesisedalongonestrandoftheDNAtemplate,beginningatthe3
end.ThesynthesisofmRNAfromaDNAtemplateiscalledtranscriptionbecausegeneticinformationina
sequenceofbasesofDNAistranscribedintoacomplementarysequenceofbasesonmRNA.

ThenamemessengerisderivedfromthefunctionofthistypeofRNA,whichistocarrycodedgenetic
information(theblueprintsforaspecialpolypeptide)fromDNAtotheribosomesforthesynthesisof
proteins.
WithrespecttothesynthesisofmRNAfromaDNAtemplate,itisimportanttounderstandthatonlyoneof
thetwoDNAstrandsistranscribedintomRNA.Thestrandcontainingthegeneiscalledthecodingstrand
(orsensestrand),andthestrandthatistranscribedintomRNAisthetemplatestrand(orantisensestrand).
Sincethetemplateandthecodingstrandsarecomplementary,andthetemplatestrandandthemRNA
moleculearealsocomplementary,themRNAmoleculeproducedduringtranscriptionisacopyofthe
codingstrand.TheonlydifferencebetweenthecodingstrandandmRNA(apartfromthefactthatRNA
containsriboseandDNAcontains2deoxyribose)isthattheRNAmoleculehasUineveryplacethatthe
DNAcodingstrandhasaT.

WORKEDEXAMPLE25.4

SequenceofBasesofmRNA1
ThefollowingisabasesequencefromaportionofDNA:

WritethesequenceofbasesofthemRNAsynthesisedwiththissectionofDNAasatemplate.

Solution

RNAsynthesisbeginsatthe3endoftheDNAtemplateandproceedstowardsthe5end.The
complementarymRNAstrandisformedusingthebasesC,G,AandU.Uracil(U)isthe
complementofadenine(A)ontheDNAtemplate.
 Readingfromthe5end,weseethatthesequenceofmRNAis5UCGGUACACUGG3.

PRACTICEEXERCISE25.4
Hereisaportionofthenucleotidesequencein
phenylalaninetRNA:

WritethenucleotidesequenceoftheDNA
complementofthissequence.

WORKEDEXAMPLE25.5

SequenceofBasesofmRNA2
WritethemRNAproducedfromthefollowingsegmentofaDNAcodingstrand.

Solution

ThemRNAproducedduringtranscriptionisacopyoftheDNAcodingstrandwitheachT
replacedbyaU.Therefore,themRNAstrandhasthefollowingsequence.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
25.4TheGeneticCode
Itwasclearbytheearly1950sthatthesequenceofbasesinDNAmoleculesconstitutesthestoreofgenetic
informationanddirectsthesynthesisofmessengerRNA,which,inturn,directsthesynthesisofproteinsby
ribosomalRNAwiththeassistanceoftransferRNA.Thiscorrespondencebetweennucleicacidsequencesand
polypeptidesequencesiscalledthegeneticcode.

TripletNatureoftheCode
TheideathatthesequenceofbasesinDNAdirectsthesynthesisofproteinspresentsthefollowingproblem:
Howcanamoleculecontainingonlyfourvariableunits(adenine,cytosine,guanineandthymine)directthe
synthesisofmoleculescontainingupto20variableunits(theproteinderivedaminoacids)?Howcanan
alphabetofonlyfourletterscodefortheorderoflettersinthe20letteralphabetthatoccursinproteins?

Anobviousansweristhatacombinationofbases,ratherthanasinglebase,codesforeachaminoacid.Ifthe
codeconsistsofnucleotidepairs,thereare4 2=16combinationsthisisamoreextensivecode,butitisstillnot
extensiveenoughtocodefor20aminoacids.Ifthecodeconsistsofnucleotidesingroupsofthree,thereare4 3
=64combinations,morethanenoughtocodefortheprimarystructureofaprotein.Thisappearstobeavery
simplesolutiontotheproblemforasystemthatmusthavetakeneonsofevolutionarytrialanderrorto
develop.Yetproofnowexists,fromcomparisonsofgene(nucleicacid)andprotein(aminoacid)sequences,
thatnaturedoesindeeduseasimplethreeletterortripletcodetostoregeneticinformation.Suchatripletof
nucleotidesiscalledacodon.

DecipheringtheGeneticCode
Thenextquestionis:Whichofthe64tripletscodesforwhichaminoacid?In1961,MarshallNirenberg
providedasimpleexperimentalapproachtotheproblem,basedontheobservationthatsynthetic
polynucleotidesdirectpolypeptidesynthesisinmuchthesamemannerasdonaturalmRNAs.Nirenbergfound
that,whenribosomes,aminoacids,tRNAsandappropriateproteinsynthesisingenzymeswereincubatedin
vitro,nopolypeptidesynthesisoccurred.However,whenheaddedsyntheticpolyuridylicacid(polyU),a
polypeptideofhighmolarmasswassynthesised.Moreimportantly,thesyntheticpolypeptidecontainedonly
phenylalanine.Withthisdiscovery,thefirstelementofthegeneticcodewasdeciphered:ThetripletUUU
codesforphenylalanine.

Similarexperimentswerecarriedoutwithdifferentsyntheticpolyribonucleotides.Itwasfound,forexample,
thatpolyadenylicacid(polyA)leadstothesynthesisofpolylysine,andthatpolycytidylicacid(polyC)leads
tothesynthesisofproline.By1964,all64codonshadbeendeciphered(table25.4).Nirenberg,RobertHolley
andHarGobindKhoranasharedthe1968NobelPrizeinphysiologyormedicinefortheirgroundbreaking
work.
TABLE25.4 Thegeneticcode:mRNAcodonsandtheaminoacidthateachcodondirects
Firstposition(5end) Secondposition Thirdposition3end)
U C A G
UUU Phe UCU Ser UAU Tyr UGU Cys U
UUC Phe UCC Ser UAC Tyr UGC Cys C
U
UUA Leu UCA Ser UAA Stop UGA Stop A
UUG Leu UCG Ser UAG Stop UGG Trp G
CUU Leu CCU Pro CAU His CGU Arg U

CUC Leu CCC Pro CAC His CGC Arg C

C
 CUC Leu CCC Pro CAC His CGC Arg C
C
CUA Leu CCA Pro CAA Gln CGA Arg A
CUG Leu CCG Pro CAG Gln CGG Arg G
AUU Ile ACU Thr AAU Asn AGU Ser U
AUC Ile ACC Thr AAC Asn AGC Ser C
A
AUA Ile ACA Thr AAA Lys AGA Arg A

AUG(a) Met ACG Thr AAG Lys AGG Arg G

GUU Val GCU Ala GAU Asp GGU Gly U

GUC Val GCC Ala GAC Asp GGC Gly C
G
GUA Val GCA Ala GAA Glu GGA Gly A
GUG Val GCG Ala GAG Glu GGG Gly G

(a)AUGalsoservesastheprincipalinitiationcodon.

PropertiesoftheGeneticCode
Severalfeaturesofthegeneticcodeareevidentfromastudyoftable25.4.
1.Only61tripletscodeforaminoacids.Theremainingthree(UAA,UAGandUGA)aresignalsforchain
terminationtheysignaltotheproteinsynthesisingmachineryofthecellthattheprimarysequenceofthe
proteiniscomplete.ThethreechainterminationtripletsareindicatedinthetablebyStop.
2.Thecodeisdegenerate,whichmeansthatseveralaminoacidsarecodedforbymorethanonetriplet.
Onlymethionineandtryptophanarecodedforbyjustonetriplet.Leucine,serineandargininearecoded
forbysixtriplets,andtheremainingaminoacidsarecodedforbytwo,threeorfourtriplets.
3.Forthe15aminoacidscodedforbytwo,threeorfourtriplets,itisonlythethirdletterofthecodethat
varies.Forexample,glycineiscodedforbythetripletsGGA,GGG,GGCandGGU.
4.Thereisnoambiguityinthecode,meaningthateachtripletcodesforonlyoneaminoacid.
5.AUGistheinitiationsignal,anditisalsothecodonfortheaminoacidmethionine.Inallprotein
sysnthesis,thefirstaminoacidplacedisalwaysmethionine.

WORKEDEXAMPLE25.6

Transcription
Duringtranscription,aportionofmRNAissynthesisedwiththefollowingbasesequence:

(a)WritethenucleotidesequenceoftheDNAtemplatestrandfromwhichthisportionofmRNA
wassynthesised.

(b)WritetheprimarystructureofthepolypeptidecodedforbythissectionofmRNA.

Solution
(a)Duringtranscription,mRNAissynthesisedfromaDNAstrand,beginningfromthe3endof
theDNAtemplate.TheDNAstrandmustbethecomplementofthenewlysynthesisedmRNA
strand:
 NotethatthecodonUGAcodesforterminationofthegrowingpolypeptidechaintherefore,
thesequencegiveninthisproblemcodesforapentapeptide.
(b)ThesequenceofaminoacidsisshowninthefollowingmRNAstrand:

PRACTICEEXERCISE25.5
ThefollowingsectionofaDNAtemplatestrandcodesforoxytocin,apolypeptide
mammalianhormonethatisreleasedduringlabour:

(a)WritethebasesequenceofthemRNAsynthesisedfromthissectionofDNA.
(b)Useyoursequenceofbasesin(a)towritetheprimarystructureofoxytocin.

PolypeptideSynthesis
Aswehavejustseen,eachtripletofbasesasitoccursonmRNAiscalledacodon,andeachcodon
correspondstoaspecificaminoacid.Thetranslationofcodonstoaminoacidsconstitutesthegeneticcode.
Oneofthemostremarkablefeaturesofthecodeisthatitisessentiallyuniversal.Thecodonspecifyingalanine
inhumans,forexample,alsospecifiesalanineinthegeneticmachineryofallknownspeciesofbacteria,
aardvarks,camels,rabbitsandstinkbugs.Ourchemicalkinshipwiththeentirelivingworldisprofound(even
humbling).

AtripletofbasescomplementarytoacodonoccursontRNAandiscalledananticodon(seefigure25.19).A
tRNAmolecule,bearingtheaminoacidcorrespondingtoitsanticodon,canlineupatapositiononastrandof
mRNAonlywheretheanticodonfitsbyhydrogenbondingtothematchingcodon.Forexample,ifthe
anticodonisACC,theAontheanticodonmustfindaUonthemRNAatthesametimethatitsneighbouring
twoCbasesfindneighbouringGbasesonthemRNAstrand.Thustheanticodonandcodonlineupasshown
below,wherethedottedlinesindicatehydrogenbonds.
CodonsonmRNAdeterminethesequenceinwhichtRNAunitslineup,andthissetsthesequenceinwhich
aminoacidunitsbecomejoinedinapolypeptide.Figure25.20carriesthisdescriptionfurther,whereweenter
theprocesssoonafterspecialsteps(notshown)havelaunchedit.

FIGURE25.20PolypeptidesynthesisatanmRNAstrand.

Infigure25.20a,atRNAglycineunitarrivesatmRNAwhereitfindstwosituations,namely,adipeptide
alreadystartedandacodontowhichthetRNAglycinecanfit.Infigure25.20b,thetRNAglycineunitisin
place.Itistheonlysuchunitthatcouldfitherebasepairingbetweenthetwotripletscodontoanticodon
ensuresthis.ItisimportanttounderstandthatthebindingoftRNAcarryingacertainaminoacidtothecodons
onmRNAisanequilibriumreaction.ThereasonthatoneandnotanotheraminoacidonatRNAmolecule
bindsisrelatedtotherelativemagnitudeofthehydrogenbondsthatarecreatedduringthisbindingprocess.

Infigure25.20c,thewholedipeptideunitmovesoverandisjoinedtotheglycineunitbyanewlyformed
peptidebond.ThisleavesatripeptideattachedviaatRNAunittothemRNA.

Becausethenextcodoninfigure25.20d,GCU,codesfortheaminoacidalanine,onlyatRNAalanineunit
canfitthenextsite.Soalanine,withitsmethylgroupasthesidechain,istheonlyaminoacidthatcanenterthe
polypeptidechainatthispoint.Theseelongationstepsrepeatuntilaspecialcodonisreachedthatisdesigned
tostoptheprocess.Thepolypeptideisnowcomplete.Ithasauniquesequenceofsidechainsthathasbeen
initiallyspecifiedbythemolecularstructureofagene.

Asshowninfigure25.21,synthesisofthepeptidetakesplaceinribosomes,whicharemadefromcomplexes
ofRNAandproteins.Ribosomesconsistoftwosubunitsofdifferentsizes.Thesmallersubunitbindsto
mRNA,whilethelargersubunitbindstotRNAandtheaminoacids.Oncetheribosomehasfinishedreadinga
sequenceofmRNA,thesubunitsseparate.

FIGURE25.21RepresentationofthetranslationofanmRNAsequenceandsynthesisofapeptidechainata
ribosome.AnincomingtRNAmoleculeisshownreadytobindtothenextcodonandaddaleucine
aminoacidtothegrowingchain.

GeneticDefects
About2000diseasesareattributedtovariouskindsofdefectsinthegeneticmachineryofcells.Withsomany
stepsfromgenetopolypeptide,weshouldexpectmanyopportunitiesforthingstogowrong.Suppose,for
example,thatjustonebaseinagenewasmissing.ThismeansthatonebaseonanmRNAstrandwouldbe
wrong(withrespecttogettingthepolypeptidewewant).Thiswouldchangeeveryremainingcodon.For
example,ifthenextcodonsonastrandofmRNAwereUCUGGUGCUU,andthefirstGwasdeleted,the
sequencewouldbecomeUCUGUGCUU.Allremainingtripletschange!Youcanimaginehowthiscould
leadtoanentirelydifferentpolypeptidefromtheonewewant.

Suppose,instead,thatthesecondGwasreplacedbyaC.ThiswouldmeanthattheGGUcodonbecomesa
GCUcodonsothatUCUGGUGCUbecomesUCUGCUGCU.Oneaminoacidintheresulting
polypeptidewouldbeincorrect.Suchamutationmakesthedifference,forexample,betweenthenormal
haemoglobinproteinandthesicklecellhaemoglobinproteinorcancausesomeformsofcysticfibrosis.

Viruses
Virusesaremicroscopicparticlesusuallyconsistingofnucleicacidsandproteinsthatcaninfectcellsof
biologicalorganisms.Theycannotreproduceontheirown,butreplicatethroughinfectionofahostcell.Thus,
thenucleicacidsofvirusescantakeoverthegeneticmachineryofthecellsofparticularhosttissues,
manufacturemorevirusparticlesandmultiplyenoughtoburstthehostcell.Becausecancercellsdivide
irregularly,andusuallymorerapidlythannormalcells,somevirusesarethoughttobeamongtheagentsthat
cancausecancer.

Thereareextensivediscussionsaboutwhethervirusesarelivingorganisms.Sincetheydonotpossessacell
membraneormetaboliseontheirown(thegenerallyaccepteddefinitionoflife),theyareoftenconsidered
nonlivingspecies.Figure25.22onthispageshowsanelectronmicrographoftheEbolavirus.Thisviruscauses
Ebolahaemorrhagicfever,adiseasewithnovaccineortreatmentandthathasamortalityrateofbetween50
and90%.ThesymptomsofEbolaincludevomiting,diarrhoea,internalandexternalbleedingandfever.

FIGURE25.22AnelectronmicrographoftheEbolavirusat19000timesmagnification.SPL/BarryDowsett

ReverseTranscriptase
Aswehaveseen,normaltranscriptioninvolvesthesynthesisofmRNAfromDNA.In1970,itwasdiscovered
thatthereverseprocessisalsopossible,wheresinglestrandedRNAisultimatelytranscribedintodouble
strandedDNA(seefigure25.23).TheRNAdependentDNApolymeraseenzyme(alsocalledreverse
transcriptase),whichisresponsibleforthisprocess,iscentraltotheinfectiousnatureofreversetranscribing
viruses(retroviruses),severalofwhichcausediseaseinhumans.
 FIGURE25.23ReplicationofviralDNArequiresthetranscriptionofsinglestrandedRNAintodoublestrandedDNA.
ThisprocessisthereverseofnormaltranscriptionofmRNAfromDNA,anditrequirestheenzyme
reversetranscriptase.

Aprominentexampleisthehumanimmunodeficiencyvirustype1(HIV1).Onceinsideacell,retroviruses
reversetranscribetheirRNAgenomeintoDNA,whichisthenintegratedintothehostgenomeandreplicated
alongwiththehost'sDNA.Withoutreversetranscriptase,theviralgenomecannotbeincorporatedintothehost
cell,andthisisessentialforthevirustoreproduce.

Sinceerrorscanoccurduringreversetranscriptase,notallvirusesproducedinasingleinfectedcellare
identical.Thisresultsinviruseswithavarietyofsubtlemoleculardifferencesintheirsurfaceproteincoats.
Vaccines,whichinducetheproductionofantibodiesthatrecogniseandbindtoveryspecificsurfacemolecules
onavirus,areanunlikelysolutiontofightingHIVinfectionthisisbecause,throughouttheinfection,HIV
surfacemoleculesarecontinuallychanging.

ThefirstdrugsthatweresuccessfulinslowingdownHIVinfectionsactbyblockingtherecodingofviralRNA
intoDNA.OneexampleofsuchareversetranscriptaseinhibitoristhecompoundAZT(seefigure25.22),
whichdelaystheprogressionfromHIVinfectiontoAIDS(acquiredimmunedeficiencysyndrome).

ChemicalConnections
TheSearchforAntiviralDrugs

Thesearchforantiviraldrugshasbeenmoredifficultthanthesearchforantibacterialdrugs,
primarilybecauseviralreplicationdependsonthemetabolicprocessesoftheinvadedcell.Thus,
antiviraldrugsarealsolikelytocauseharmtothecellsthatharbourthevirus.Thechallengein
developingantiviraldrugsistounderstandthebiochemistryofvirusesandtodevelopdrugsthat
targetprocessesspecifictothem.Comparedwiththelargenumberofantibacterialdrugsavailable,
thereisonlyahandfulofantiviraldrugs,andtheyhavenowhereneartheeffectivenessthat
antibioticshaveagainstbacterialinfections.

Acyclovirwasoneofthefirstofanewfamilyofdrugsforthetreatmentofinfectiousdiseases
causedbyDNAvirusescalledherpesvirus.Herpesinfectionsinhumansareoftwokinds:herpes
simplextype1,whichgivesrisetomouthandeyesores,andherpessimplextype2,whichgivesrise
toseriousgenitalinfections.Acyclovirishighlyeffectiveagainstherpesviruscausedgenital
infections.Thestructuralformulaofacyclovirinfigure25.24showsitsstructuralrelationshipto2
deoxyguanosine.ThedrugisactivatedinvivobytheconversionoftheprimaryOH(which
correspondstothe5OHofaribosideoradeoxyriboside)toatriphosphate.Becauseofitsclose
resemblancetodeoxyguanosinetriphosphate,anessentialprecursorofDNAsynthesis,acyclovir
triphosphateistakenupbyviralDNApolymerasetoformanenzymesubstratecomplexonwhich
no3OHexistsforreplicationtocontinue.Thus,theenzymesubstratecomplexisnolongeractive
(itisadeadendcomplex),viralreplicationisdisrupted,andthevirusisdestroyed.

FIGURE25.24Acyclovirisananalogueof2deoxyguanosine,whichdoesnotcontainacarbohydrate
moiety.
PerhapsthebestknownoftheHIVfightingviralantimetabolitesiszidovudine(AZT),ananalogue
ofdeoxythymidineinwhichthe3OHhasbeenreplacedbyanazidogroup,N3(figure25.25).AZT
iseffectiveagainstHIV1,aretrovirusthatisthecausativeagentofAIDS.AZTisconvertedinvivo
bycellularenzymestothe5triphosphate,isthenrecognisedasdeoxythymidine5triphosphateby
viralRNAdependentDNApolymerase(reversetranscriptase),andisaddedtoagrowingDNA
chain.There,itstopschainelongationbecausethereisno3OHonwhichtoaddthenext
deoxynucleotide.AZTowesitseffectivenesstothefactthatitbindsmorestronglytoviralreverse
transcriptasethanitdoestohumanDNApolymerase.

FIGURE25.25Zidovudineisananalogueof2deoxythymidineinwhichthe3OHgrouphasbeen
replacedbyanazidogroup,N3 .

ChemicalConnections

DNAProfiling

Ifthemanycrimedramasontelevisionaretobetakenasaguide,DNAholdsthekeytosolving
otherwiseunsolvablecrimes.Inadditiontohelpingconvictcriminals,ithasalsoexoneratedsuspects
(andpeoplewronglyconvicted),helpedintheidentificationofdisastervictimsandestablishedthe
paternityofchildren.ComparingDNAsamplesisknownasDNAprofilingorDNAfingerprinting.

Eachhumanbeinghasageneticmakeupconsistingofapproximately3billionpairsofnucleotides.
AlmostalloftheDNAsequenceisidenticalbetweendifferentindividuals.However,partsofDNA
moleculesdifferfrompersontopersonoranimaltoanimal(withtheexceptionofidenticaltwinsand
clones)highlyvariablerepeatedsequencesofsidechainbasescalledshorttandemrepeatsor
minisatellitesgiveeachpersonauniqueDNAfingerprintthatcanbeusedquitereliablytoidentify
anindividual.HumanDNAsamplescanbeobtainedfromhair,blood,semen,salivaorskinleftata
crimescene.Infact,everycell,exceptthesexcells(spermandova)andhairshafts,containsthe
entiresetofDNAuniquetotheindividual.

ToproduceaDNAfingerprint,asampleofDNAfromatraceofblood,skinorothertissueistreated
withspecificenzymesthatbreaktheDNAintosmallfragments,whichcanbevisualisedbyspecial
techniques.ThefinalresultofDNAprofilinglooksmuchlikeabarcode:aseriesofparallellinesthat
differfrompersontopersoninnumber,thicknessandseparation.

IntheDNAfingerprintinfigure25.26,lanes1,5and9representinternalstandards,orcontrollanes.
Lanes2,3and4wereusedinapaternitysuit.TheDNAfingerprintofthemotherinlane4contains
fivebandsthatmatchfiveofthesixbandsintheDNAfingerprintofthechildinlane3.TheDNA
fingerprintoftheallegedfatherinlane2containssixbands,threeofwhichmatchbandsintheDNA
fingerprintofthechild.Becausethechildinheritsonlyhalfofitsgenesfromthefather,onlyabout
halfofthechild'sandfather'sbandsintheDNAfingerprintsareexpectedtomatch.Inthisinstance,
wecansay,onthebasisoftheDNAfingerprintmatching,thattheallegedfatheris,indeed,the
child'sfather.Theprobabilitythatheisnotthefatherisextremelysmallabout1in100000.

FIGURE25.26DNAfingerprint.DrLawrenceKobilinsky

Lanes6,7and8containDNAfingerprintpatternsusedasevidenceinacriminalcase.Lanes6and
7areDNAfingerprintsobtainedfromacrimescene.Lane8istheDNAfingerprintpatternofthe
 suspect.Ascanbeseen,theDNAfingerprintpatternsinlanes7and8areidentical.Thepatternin
lane6mustarisefromapersonotherthanthesuspect.Incaseswherethesequenceprofilesfroma
knownindividualmatchtheDNAobtainedatthecrimescene,theprobabilitythattheDNAisnot
fromthesameperson(i.e.thatanotherpersoncommittedthecrime)isapproximately1in82billion
extraordinarilylow.

ThefiercedebateovertheuseofDNAevidenceincriminalcasesisnotrelatedtothereliabilityof
DNAmatchingratheritisrelatedtothevagariesofthevariouslawsandtothecareorlackofcare
showningatheringthesamplesfromthecrimescene.Identificationcanbecomplicatedifacrime
sceneiscontaminatedwithDNAfromseveralpeople,whomayincludetheperpetrator,victim,
investigatorsandanyoneelsewhohadvisitedthelocation.Investigatorseliminatethevictim'sDNA
andthatofothersknowntobeinnocent,leavingthemwiththeDNAofpotentialsuspects.

NewZealandwasthesecondcountryintheworldtocreateanationalDNAdatabase,usingDNA
fromvolunteersandconvictedoffenders.Australialaggedbehind,withdifferentstatelaws
preventingtheestablishmentofanationalDNAdatabase.Attheendof2006,theDNAforensic
laboratoriesinthelargeststatesinAustraliahadabacklogofseveralthousandcases.In2007,the
statesagreedtoaligntheirlegislationandsoallowsharingofDNAprofilesviathefederal
government'sCrimTracagency.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
NucleosidesandNucleotides
Nucleicacidsarecomposedofthreetypesofmonomerunits:heterocyclicaromaticaminebasesderived
frompyrimidineandpurine,themonosaccharideDriboseor2deoxyDribose,andphosphateions.A
nucleosideisacompoundcontainingDriboseor2deoxyDribosebondedtoaheterocyclicaromatic
aminebasebyaNglycosidicbond.Anucleotideisanucleosideinwhichamoleculeofphosphoric
acidisesterifiedwithanOHgroupofthemonosaccharide,mostcommonlythe3orthe5OH
group.Nucleosidemono,diandtriphosphatesarestrongpolyproticacidsandareextensivelyionised
atpH7.0.AtthatpH,adenosinetriphosphate,forexample,isa50:50mixtureofATP3andATP4.

TheStructureofDeoxyribonucleicAcid(DNA)
Theprimarystructureofdeoxyribonucleicacid(DNA)consistsofnucleosides(possessing2
deoxyribose)linkedby3,5phosphodiesterbonds.Thesequenceofnucleotidesisreadfromthe5end
ofthepolynucleotidestrandtothe3end.

TheheartoftheWatsonCrickmodelofthestructureofDNAisthepostulatethatamoleculeofDNA
consistsoftwoantiparallelpolynucleotidestrandscoiledinarighthandedmanneraroundthesameaxis
toformadoublehelix.Purineandpyrimidinebasespointinwardstotheaxisofthehelixandarealways
pairedGCandAT.InBDNA,basepairsarestackedoneontopofanother,withaspacingof0.34nm
and10basepairsper3.4nmhelicalrepeat.InADNA,basesarearrangedwith11basepairsper2.5
nmhelicalrepeat.ZDNAisalefthandeddoublehelix,whichisthinnerandlongerthanBDNA.

TheformationofthetertiarystructureofDNAiscommonlycalledsupercoiling.BacterialcircularDNA
isatypeofdoublestrandedDNAinwhichthe5and3endsofthestrandsarejoinedby
phosphodiestergroups.Theopeningofonestrandfollowedbythepartialunwindingandrejoiningof
theendsintroducesstraininthenonhelicalgap.Thestraincanbespreadovertheentiremoleculeof
circularDNAbytheintroductionofsuperhelicaltwists.

Histonesareparticularlyrichinlysineandarginineandsohaveanabundanceofpositivecharges.The
associationofDNAwithhistonesproducesacomplexcalledchromatin.

RibonucleicAcid(RNA)
Therearetwoimportantdifferencesbetweentheprimarystructuresofribonucleicacid(RNA)and
DNA:
(a)ThemonosaccharideunitinRNAisDribose.
(b)BothRNAandDNAcontainthepurinebasesadenine(A)andguanine(G)andthepyrimidine
basecytosine(C).Asthefourthbase,however,RNAcontainsuracil(U),whereasDNAcontains
thymine(T).

TheGeneticCode
Thegeneticcodeconsistsofnucleosidesingroupsofthreethatis,itisatripletcode.Only61triplets
codeforaminoacidstheremainingthreecodefortheterminationofpolypeptidesynthesis.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Nucleicacids(section25.1)
Theseconsistofpyrimidineandpurinebases,riboseor2deoxyribose,andphosphate.

Basepairing(section25.2)
InDNAandRNA,G(guanine)pairswithC(cytosine).

InDNA,A(adenine)pairswithT(thymine)inRNA,ApairswithU(uracil).

Thegeneticcode(section25.4)
Thisdescribesthecorrespondencebetweennucleicacidsequencesandtheresultantpolypeptide
sequences.DNAistranscribedtomRNA,whichisthentranslatedtoproteinviatRNA,whichmatches
codonstoaminoacids.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
NucleosidesandNucleotides
25.1Writethenamesandstructuralformulaeofthefivenitrogenbasesfoundinnucleosides.
25.2Writethenamesandstructuralformulaeofthetwosugarsfoundinnucleosides.
25.3Explainthedifferenceinstructurebetweenanucleosideandanucleotide.
TheStructureofDeoxyribonucleicAcid(DNA)
25.4WhataretheprincipalstructuraldifferencesbetweenDNAandRNA?
25.5Listthecompositions,abbreviationsandstructuresofthevariousnucleotidesinDNA.
25.6Writeastructuralformulaforasegmentofapolynucleotidewithfournucleotides.
25.7ListthepostulatesoftheWatsonCrickmodelofDNAsecondarystructure.
25.8Whatismeantbythetermcomplementarybases?
25.9DescribethedifferencesbetweenADNA,BDNAandZDNA.
RibonucleicAcid(RNA)
25.10DescribethedifferencesbetweenmRNA,tRNAandrRNA.
25.11Listthecompositions,abbreviationsandstructuresofthevariousnucleotidesinRNA.
25.12ExplainthedifferencebetweenthecodingstrandandthetemplatestrandduringmRNA
synthesis.
TheGeneticCode
25.13Whatisthegeneticcode?
25.14DescribeandillustratethereplicationprocessofDNA.
25.15Whyareatleastthreenucleotidesneededforoneunitofthegeneticcode?
25.16Brieflyoutlinethebiosynthesisofproteins,startingfromDNA.
25.17Inproteinsynthesis,howdoesterminationdifferfromelongation?
25.18Howdoesacodondifferfromananticodon?
25.19Whatisreversetranscription?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
25.20Twodrugsusedinthetreatmentofacuteleukaemiaare6mercaptopurineand6thioguanine.

Notethat,ineachofthesedrugs,theoxygenatomatC(6)oftheparentmoleculeisreplacedby
divalentsulfur.Drawstructuralformulaefortheenethiol(thesulfurequivalentofanenol)forms
of6mercaptopurineand6thioguanine.Showthattheycanform10electronaromaticsystems.
25.21Thefollowingarestructuralformulaeforcytosineandthymine.

Drawtwoadditionaltautomericenolformsforcytosineandthreeforthymine.Showthe6
electronaromaticsystem.
25.22Indicatewhethereachfunctionalgroupofthefivebasesinnucleicacidscanfunctionasa
hydrogenbondacceptor(A),hydrogenbonddonor(D)orboth(A/D).
25.23UsingtheA,DandA/Ddesignationfromquestion25.22,indicatehowbasepairingwouldbe
affectedifthebasesexistedintheenolforms.
25.24Drawstructuralformulaefornucleosidescomposedof:
(a)Driboseandadenine
(b)2deoxyDriboseandcytosine.
25.25Nucleosidesarestableinwaterandindilutebase.Indiluteacid,however,theglycosidicbondof
anucleosideundergoeshydrolysistogiveapentoseandaheterocyclicaromaticaminebase.
Proposeamechanismforthisacidcatalysedhydrolysis.
25.26DrawastructuralformulaforeachofthefollowingnucleotidesandestimateitsnetchargeatpH
7.4,thepHofbloodplasma.
(a)2deoxyadenosine5triphosphate(dATP)
(b)guanosine3monophosphate(GMP)
(c)2deoxyguanosine5diphosphate(dGDP)
25.27Cyclicadenosinemonophosphate(AMP),firstisolatedin1959,isinvolvedinmanydiverse
biologicalprocessesasaregulatorofmetabolicandphysiologicalactivity.Inthiscompound,a
singlephosphategroupisesterifiedwithboththe3and5hydroxylsofadenosine.Drawthe
structuralformulaofcyclicAMP.
25.28Whyaredeoxyribonucleicacidscalledacids?Whataretheacidicgroupsintheirstructure?
25.29Whyarethepyrimidineandpurinebasesinnucleosidescalledbases?Whatarethebasicgroups
intheirstructure?
25.30HumanDNAisapproximately30.4%A.EstimatethepercentagesofG,CandTandcompare
themwiththevaluespresentedintable25.2.
25.31ExplainwhytheratioofthyminetoadenineinDNAis1:1,buttheratioofadeninetocytidine
isnotnecessarily1:1.
25.32WhichofthefollowingpairsofnucleotidesarepresentinDNAinequalamounts?
(a)TAandAT
(b)GTandCA
(c)ATandCG
(d)CAandTG
(e)GGandCC
(f) CGandGT
(g)AAandGG
(h)ACandTG
25.33DrawastructuralformulafortheDNAtetranucleotide5AGCT3.Estimatethenetchargeon
thistetranucleotideatpH7.0.Whatisthecomplementarytetranucleotideofthissequence?
25.34DrawindetailthestructureofasectionofRNAfourresidueslongthathasthesequence5
GCUA3.Labelthe5and3ends.
25.35TheWatsonCrickmodelisbasedoncertainexperimentalobservationsofbasecompositionand
moleculardimensions.Describetheseobservationsandshowhowthemodelaccountsforeach.
25.36ComparethehelixofproteinsandthedoublehelixofDNAintermsof:
(a)theunitsthatrepeatinthebackboneofthepolymerchain
(b)theprojectioninspaceofsubstituentsalongthebackbone(theRgroupsinthecaseof
aminoacidspurineandpyrimidinebasesinthecaseofdoublestrandedDNA)relativeto
theaxisofthehelix.
25.37DiscusstheroleofhydrophobicinteractionsinstabilisingdoublestrandedDNA.
25.38Namethetypeofcovalentbond(s)joiningmonomersineachofthefollowingbiopolymers.
(a)polysaccharides
(b)polypeptides
(c)nucleicacids
25.39Atelevatedtemperatures,nucleicacidsbecomedenaturedthatis,theyunwindintosingle
strandedDNA.AccountfortheobservationthatshorterDNAstrandsgenerallyundergo
denaturationatlowertemperaturethanlongerstrands.
25.40ThestabilityofaDNAdoublehelixcanbedeterminedbyitsmeltingtemperature,Tm,whichis
definedasthetemperatureatwhich50%ofthedoublehelixisdissociatedintoindividual
strands.
(a)Whydoesthedoublehelixformedbetweenpolydeoxyadenylicacid(polyA)and
polydeoxythymidylicacid(polyT)haveaTmofonly68C,butthedoublehelixformed
betweenpolydeoxyguanylicacid(polyG)andpolydeoxycytidylicacid(polyC)hasaTm
of91C?
(b)WhichofhumanadenovirusI(Tm=58.5C)andfowlpoxvirus(Tm=35C)hasthe
higherratioof(G+C)to(A+T)?Explain.
25.41WritetheDNAcomplementof5ACCGTTAAT3.Labelthe5and3endsofthecomplement
 strand.
25.42WritetheDNAcomplementof5TCAACGAT3.Labelthe5and3endsofthecomplement
strand.
25.43ComparethedegreeofhydrogenbondinginthebasepairATfoundinDNAwiththatinthe
basepairAUfoundinRNA.
25.44CompareDNAandRNAintermsofeachofthefollowing.
(a)monosaccharideunits
(b)principalpurineandpyrimidinebases
(c)primarystructure
(d)locationinthecell
(e)functioninthecell
25.45WhichtypeofRNAhastheshortestlifetimeincells?
25.46WritethemRNAcomplementof5ACCGTTAAT3.Labelthe5and3endsofthecomplement
strand.
25.47WritethemRNAcomplementof5TCAACGAT3.Labelthe5and3endsofthecomplement
strand.
25.48Thegeneticcodeisdegenerate.Whatdoesthismean?
25.49Asparticacidandglutamicacidhavecarboxylgroupsontheirsidechainsandarecalledacidic
aminoacids.Comparethecodonsforthesetwoaminoacids.
25.50Comparethestructuralformulaeofthearomaticaminoacidsphenylalanineandtyrosine.
Comparetheircodons.
25.51Glycine,alanineandvalineareclassifiedasnonpolaraminoacids.Comparetheircodons.What
similaritiesanddifferencesdoyoufind?
25.52ThecodonsCUU,CUC,CUAandCUGallcodefortheaminoacidleucine.Inthisset,thefirst
andsecondbasesareidentical,andtheidentityofthethirdbaseisirrelevant.Forwhichother
setsofcodonsisthethirdbaseirrelevant,andforwhichaminoacid(s)doeseachsetcode?
25.53Comparetheaminoacidscodedforbythecodonswithapyrimidine,eitherUorC,asthe
secondbase.Dothemajorityoftheaminoacidsspecifiedbythesecodonshavehydrophobicor
hydrophilicsidechains?
25.54Comparetheaminoacidscodedforbythecodonswithapurine,eitherAorG,asthesecond
base.Dothemajorityoftheaminoacidsspecifiedbythesecodonshavehydrophilicor
hydrophobicsidechains?
25.55WhatpolypeptideiscodedforbythismRNAsequence?

25.56Thealphachainofhumanhaemoglobinhas141aminoacidsinasinglepolypeptidechain.
CalculatetheminimumnumberofbasesonDNAnecessarytocodeforthealphachain.Include
inyourcalculationthebasesnecessaryforspecifyingtheterminationofpolypeptidesynthesis.
25.57Thereisevidencethatalkylationoftheoxygenatomatposition4inthymineisamutagenic
eventleadingtocancer.
(a)DrawthestructureofthymineafterO4methylation.
(b)ExplainwhyO4alkylationatthyminewoulddisruptWatsonCrickbasepairing.
25.58Spontaneousmutationscanoccurduringtheprocessofreplicationbyimproperbasepairing,as
showninquestion25.57.Iftautomerisationofguanine(seep.1088)occursataparticular
momentofreplication,thymineinsteadofcytosinecouldbeintroducedtothecomplementary
DNAstrand.WhaterrorwouldthisnewDNAstrandintroduceintoitscomplementarystrand
 duringreplication?
25.59Geneticmutationscanbecausedbychemicals.Nitrousacid,HNO2,isoneofthemostpotent
mutagensitreactswithandultimatelyremovesaminogroupsincytosine,adenineandguanine.
TreatmentofadeninewithHNO2leadstothefollowingmodifiedbase:

Thismodifiedbasehasbeenshowntopairwithcytosine.Writeastructuralformulashowingthe
hydrogenbondsinthisbasepair.
25.60Sicklecellanaemiaiscausedbyreplacementoftheaminoacidglutamicacidbyvalineinthe6
positionofthechaininthehumanhaemoglobinHbS.
(a)Listthetwocodonsforglutamicacidandthefourcodonsforvaline.
(b)Refertoquestions25.57to25.59toexplainhowanerrorofasinglebaseineachstrand
ofDNAcouldbringaboutthisaminoaciderror.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
25.61ThelossofthreeconsecutiveunitsofTfromthegenethatcodesforCFTR,atransmembrane
conductanceregulatorprotein,resultsinthediseaseknownascysticfibrosis.Whichaminoacid
ismissingfromCFTRtocausethisdisease?
25.62Thefollowingcompoundshavebeenstudiedaspotentialantiviralagents:
(a)

(b)

(c)

SuggesthoweachofthesecompoundsmightblockthesynthesisofRNAorDNA.
25.63Onesynthesisofzidovudine(AZT)involvesthefollowingreaction(DMFisthesolventN,
Ndimethylformamide):
 Whattypeofreactionisthis?
25.64Manymethodshavebeendevelopedforthelaboratorysynthesisofnucleosidesfromthe
constituentsugarsandbasesortheirrespectiveprecursors.Onetechniqueinvolvesformationof
theheterocyclicbasethroughcondensationonaribosylaminederivative(inwhichthehydroxyl
groupsareprotectedwithacetylgroups).Proposethemechanismforthefirststepintheuridine
synthesisshownbelow.

25.65BesidesthenormalWatsonCrickbasepairing,whichleadstothepairsCGandAT,several
nonWatsonCrickpairs,suchasUGandUA,arealsopossible.Writestructuralformulae
showingthehydrogenbondsinthesocalledwobblepairs,UGandUA.
25.66Asshowninsection25.1(p.1088),themoststableformofguanineisthelactamform.If
guaninetautomerisestotheabnormallactimform,itpairswiththymineratherthancytosine.
Writestructuralformulaeshowingthehydrogenbondsinthisabnormalbasepair.
25.67Showtheerrorsthattheconversionofadenineintothemodifiedbaseshowninquestion25.59
wouldgenerateinDNAthroughtworeplications.
25.68Considerthefollowinghexapeptide:

(a)Usingthefirstcodongivenforeachaminoacidintable25.4,writethebasesequenceof
mRNAthatwouldtranslateintothishexapeptide.
(b)WhatbasesequenceinDNAwouldtranscribeasynthesisofthemRNAin(a)?
(c)WhatanticodonswouldappearinthetRNAsinvolvedinthesynthesisofthis
hexapeptide?
25.69ThefollowingbasesequencesarefoundinsegmentsofDNA.
(a)5AUGCCCAGAACAAGC3
(b)5CTAAGCACTTCGGGGCCG3
(c)5TTTTATGGCGCTTAC3
i.WhichbaseswouldappearinthemRNAtranscribedfromthesesegments?
ii.Ifthefirstbaseisthebeginningofacodon,writetheprimarystructureofthe
polypeptidessynthesisedalongthesesegments.
25.70ConsideranmRNAstrandwiththefollowingsequence:

(a)WhatistheaminoacidsequenceofapeptidecodedbythismRNAstrand.
(b)WritethesequenceoftheDNAfromwhichthemRNAistranscribed.
(c)WhatwouldbethetranslationproductresultingfromasinglemutationthatchangesUto
Aatposition15fromthe5end?
25.71MutationsinDNAcanoccurwhenonebaseissubstitutedbyanotherorwhenanextrabaseis
insertedintotheDNAstrand.Whyisaninsertionmechanismpotentiallymoreharmfulthana
substitutionmutation?
25.72Inproteinbiosynthesis,aminoacidsarecoupledtotRNAstoformaminoacyltRNAcomplexes
usingATP.Thisisusuallyatwostepprocessinthefirststep,anaminoacyladenylateisformed.

Forthiscompound,identifytheribosesugar,thenucleicacidbase,theaminoacidandthe
phosphategroup.Bywhichfunctionalgroupistheaminoacidlinkedtotherestofthemolecule?
25.73Ifapeptideissynthesisedfromthefollowingcodons,howmanycarboxylategroupswouldbe
present?
25.74Thehighlymutageniccompound5bromouracilisusedincancerchemotherapy.After
administration,itisultimatelyincorporatedintoDNAinplaceofthymine.Whydoesitcause
mutations?(Hint:Thebromosubstituentincreasesthestabilityofthelactimtautomer.)

25.75HydrolysisofRNAgivesthe2,3cyclicphosphodiestershownbelow.Whenthiscyclic
phosphodiesterreactswithwater,amixtureof2and3phosphatesisobtained.Proposea
mechanismforthisreaction.

25.76Usingthesingleletterabbreviationsfortheaminoacidsintable24.1onp.1057,writethe
sequenceofaminoacidsinapentapeptiderepresentedbythefirstfivedifferentletters(whichare
assignedtoaminoacids)inyournameortown.Don'tuseanylettermorethanonce.Writea
sequenceofbasesinmRNAthatwouldresultinthesynthesisofthatpolypeptide.Writethebase
sequenceonthesensestrandofDNAthatwouldresultinformationofthatfragmentofmRNA.
25.77ConsiderthefollowingpieceofmRNA:

(a)Whatoctapeptideiscodedforbythispiece?
(b)WhatwouldtheNterminalaminoacidbeifthecodonatthe5endunderwentthe
followingmutations:(i)thefirstbaseischangedtoA,(ii)thesecondbaseischangedto
A,(iii)thethirdbaseischangedtoA,(iv)thethirdbaseischangedtoC?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
3end doublehelix reversetranscriptaseinhibitor
5end geneticcode ribosomalRNA(rRNA)
ADNA histone ribosome
acceptorstem messengerRNA(mRNA) RNA
anticodon nucleicacid secondary(2)structure
antisensestrand nucleoside sensestrand
BDNA nucleosome supercoiling
chromatin nucleotide superhelicaltwist
circularDNA Okazakifragments templatestrand
codingstrand primary(1)structure tertiary(3)structure
codon primase transcription
DNA replicationfork transferRNA(tRNA)
DNAligase retrovirus ZDNA
DNApolymerase reversetranscriptase

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

26 Polymers
Australiahasoneoftheharshestclimatesintheworld.Insummer,thetemperatureontheroofsofhouses
canreach95C,whichputsalotofstressontheroofingmaterial,especiallythecoatingspresentona
metalroof.Thischallengesscientiststodeveloppaintmaterialsthatcanwithstandhightemperaturesand
intenseUVradiationwithoutanymeasurabledegradationordiscolourationovermanydecades.

Aspartofthesearchfornewmaterials,scientistshavemadeincreasinguseoforganicchemistryto
preparesyntheticmaterialsknownaspolymers.Theversatilityaffordedbythesepolymersallowsthe
creationandfabricationofmaterialswithrangesofpropertiesunattainableinmaterialssuchaswood,
metalsandceramics.Deceptivelysimplechangesinthechemicalstructureofapolymercanchangeits
mechanicalproperties,forexample,fromthoseofsomethingtowrapyourlunchintothoseofa
bulletproofvest.Furthermore,structuralchangescanintroducepropertiesneverbeforeimagined.For
example,usingwelldefinedorganicreactions,chemistscanturnonetypeofpolymerintoaninsulator,
suchasthatusedtomakethesheaththatsurroundselectricalcordsiftreateddifferently,thesame
polymerbecomesanelectricalconductorwithconductivitynearlyequaltothatofmetalliccopper.

Polymertechnologyhascreatedthewaterbased(latex)paintsthathaverevolutionisedthecoatings
industry,andplasticfilmsandfoamshavedonethesameforthepackagingindustry.Thelistcouldgoon
andonaswethinkofthemanufactureditemseverywherearoundusinourdailylives.
 Corbis

KEYTOPICS

26.1Thearchitectureofpolymers
26.2Polymernotationandnomenclature
26.3Formationofpolymers
26.4Siliconpolymers
26.5Recyclingplastics

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26.1TheArchitectureofPolymers
Nearlyallofthecompoundsthatwehaveencounteredsofarhaverelativelylowmolarmasses.However,
manymoleculesinnatureandinthesyntheticworldaremadefromhundredsoreventhousandsofatoms.
Moleculeswithsuchalargemolarmass(over1000gmol1)arecalledmacromolecules.Inprevious
chapters,wehaveseenexamplesofthethreemajorclassesofbiologicalmacromoleculesDNA(which
storesgeneticinformation,seechapter25),RNAandproteins(whichinducebiochemicaltransformations,
seechapter24),andpolysaccharides(whichstoreenergyandareusedasstructuralmaterials,seechapter
22)arecalledbiopolymer,sincetheyaresynthesisedbyorganisms.Thestructureandpropertiesofthese
biopolymershavebeendiscussedinpreviouschapters.Inthischapter,wewillfocusonsynthetic
macromolecules.

Syntheticcompoundsmadeofmacromoleculesareexamplesofthechemicalconversionofordinary
feedstocks,suchascoal,oil,waterandair,intonewmaterialswithnewpropertiesandusefulapplications.
Forexample,surfboards,parachutes,backpackinggearandallsortsofotherrecreationalequipmentderive
theirstrengthfrommacromolecules.Manymaterialsmadeintothreadandclothconsistofmacromolecules,
asdocontactandartificiallenses,andfillingsforteeth.

Somemacromolecularsubstanceshavemorestructuralorderthanothers.Apolymerisamacromolecular
substanceconsistingoflargeamountsofsmallidenticalunits,calledmonomers,whicharelinked.The
processoflinkingmonomerstoformapolymeriscalledpolymerisation(figure26.1).Polymerisationofthe
smallestalkene,ethene(commonnameethylene),givesthepolymerpolyethylene.Itshouldbenotedthat,
althoughthecommonnameethyleneisnolongerusedforethene,thecommonnameisretainedinthe
polymername.Thesameisthecaseforpropeneandbutene(commonnamespropyleneandbutylene)and
theirpolymerspolypropyleneandpolybutylene,respectively.

FIGURE26.1Polymerisationlinksmonomerstoformapolymer.

Becauseoftheirlargesize,theadditionorremovalofafewatomsoratomgroupsdoesnotaffectthe
propertiesofmacromolecules.Polymersgenerallyconsistofmanyindividualchains(seefigure26.5)of
differentlengths,andthereforedifferentmolecularmasses,andsoitisdifficulttospecifythemolarmassof
apolymer.Withtheexceptionofsomebiologicalmolecules,macromoleculesofaparticularsubstance
containadistributionofmolecularmasses,usuallyformingabellcurve(figure26.2).Thismeansthatsome
ofthepolymerchainsarelarge,withhighmolecularmasses,andappearontherighthandsideofthecurve.
Otherpolymerchainsaremuchsmallerwithlowermolecularmasses,andarefoundonthelefthandsideof
thecurve.Usually,mostchainlengthsareclumpedaroundacentralpoint,thehighestpointonthecurve.
Thismassdistribution,andhencethemolarmass,dependsonhowthemacromoleculesaremanufactured.
 FIGURE26.2Comparisonofthebellcurvesfortwopolymerswithdifferentmolecularmassdistributions.Thered
curveshowsapolymerwithawidemolecularmassdistribution.Thebluecurveshowsapolymer
withanarrowmolecularmassdistribution.

Itisquiteremarkablethattheexistenceofmacromoleculeswasnotdemonstrateduntilthe1920s.Hermann
Staudinger(18811965,figure26.3),aGermanchemistwhowasawardedtheNobelPrizeinchemistryin
1953,insistedthatmacromoleculesareheldtogetherbycovalentbonds,whicharefoundinsmall
molecules.Itmightsoundstrangetodaybut,atthattime,scientiststhoughtthatmacromoleculescouldnot
beformedthroughnormalchemicalbondsbutmustbeheldtogetherbyotherforces.Wewillcomebackto
thisinsection26.3.

FIGURE26.3HermannStaudinger.
SPL

Themolarmassesofpolymersaregenerallyhigherthanthoseofcommonorganiccompoundsandtypically
rangefrom10000gmol1tomorethan1000000gmol1.Thearchitecturesofthesemacromoleculescan
bequitediversemoleculescanbelinearorbranchedorhaveacomb,ladderorstarstructure(figure26.4).
Additionalstructuralvariationscanbeachievedbyintroducingcovalentcrosslinksbetweenindividual
polymerchains.
 FIGURE26.4Variouspolymerarchitectures.

FIGURE26.5 (a)Achainisagoodmodelofapolymer,suchas
(b)polyacetylene,whichresultsfromthepolymerisationofethyne(acetylene)monomers.

Linearandbranchedpolymersmadefromhydrophobicmonomersareoftensolubleinsolventssuchas
chloroform,benzene,toluene,dimethylsulfoxide(DMSO)andtetrahydrofuran(THF).Inaddition,many
linearandbranchedpolymerscanbemeltedtoformhighlyviscousliquids.Inpolymerchemistry,the
generaltermplasticdescribesanypolymerthatcanbemoulded,extrudedorcastintovariousshapes.
Plasticscanbesubdividedintothermoplasticsandthermosettingplastics.Thermoplasticsarepolymersthat,
whenmelted,becomesufficientlyfluidthattheycanbemouldedintoshapesthatareretainedwhentheyare
cooled.Mostthermoplasticmaterialsarehighmolarmasspolymerswithchainsthatareassociatedbyweak
vanderWaalsforces(e.g.polyethylene),strongerdipoledipoleinteractionsandhydrogenbonding(e.g.
nylons),orstackingofaromaticrings(socalledstacking,e.g.polystyrene).

Thermosettingplastics(orthermosets)arepolymersthatcurebytheadditionofenergy(asprovidedby
heat,lightorachemicalreaction)toastrongerform.Thismeansthatthesematerialscanbemouldedwhen
theyarefirstpreparedbut,oncecooled,hardenirreversiblyandcannotberemelted.Examplesofthermosets
areepoxyresins(usedasadhesives)andbakelite,aphenolformaldehyderesin,thefirstplasticmadefrom
syntheticcomponents,whichisanonconductiveandheatresistantmaterialusedinearlytelephonecasings,
electricalinsulators,kitchenware,costumejewelleryandtoys.Becauseoftheirverydifferentphysical
characteristics,thermoplasticsandthermosetsmustbeprocesseddifferentlyandareusedinverydifferent
applications.

Themostimportantpropertiesofpolymersatthemolecularlevelarethesizeandshapeoftheirchains.A
goodexampleoftheimportanceofsizeisacomparisonbetweenparaffinwax,anaturalpolymer,and
polyethylene,asyntheticpolymer,bothmadefromethene(figure26.1).Thesetwodistinctmaterialshave
identicalrepeatingunits,namelyCH2,butdiffergreatlyinthesizeoftheirchains.Paraffinwaxhas
between25and50carbonatomsperchain,whereaspolyethylenehasbetween1000and3000carbon
atomsperchain.Paraffinwax,suchasthatusedinbirthdaycandles,issoftandbrittle,butpolyethylene,
usedtomakeplasticbeveragebottles,forexample,isstrong,flexibleandtough.Thesevastlydifferent
propertiesarisedirectlyfromthedifferenceinsizeoftheindividualpolymerchains.

Polymers,likesmallorganicmolecules,tendtocrystalliseuponprecipitationorastheyarecooledfroma
moltenstate.However,theirlargesizeoftenhampersdiffusion,andtheirsometimescomplicatedorirregular
structurescanpreventefficientpackingofthechains.Theresultisthatpolymersinthesolidstatetendtobe
composedofbothorderedcrystallinedomains(crystallites)anddisorderedamorphousdomain(seefigure
26.6).Therelativeamountsofcrystallineandamorphousdomainsdifferfrompolymertopolymerand
frequentlydependonhowthematerialisprocessed.Weoftenfindhighdegreesofcrystallinityinpolymers
withregular,compactstructuresandstrongintermolecularforces,suchashydrogenbonding.The
temperatureatwhichcrystallitesmeltisthemelttransitiontemperature(Tm)ofthepolymer.Asthedegree
ofcrystallinityofapolymerincreases,itsTmincreases.Withanincreaseincrystallinitycomesa
correspondingincreaseinstrengthandstiffness.Examplesofthesepolymerswillbegivenlaterinthis
chapter.

FIGURE26.6Representationofamorphous(irregular)andcrystalline(regular)domainsinapolymer.

Rubbermaterials,suchasthatusedinrubberballs,areelasticandbounceatroomtemperature.Such
polymersarecalledelastomers(elasticpolymers).Ifsucharubberballiscooledbyplacingitintoliquid
nitrogen(bp=196C),thematerialisconvertedtoarigid,brittle(glassy)solidandallelastomeric
propertiesarelost(figure26.7).Apoorunderstandingofthisbehaviourofelastomerscontributedtothe
Challengerspaceshuttledisasterin1986.TheelasrtomericOringsusedtosealthesolidboosterrockets
becamebrittleataround0C.Whenthetemperaturedroppedtoanunanticipatedlowonthemorningofthe
launchofthecraft,theOringsealschangedfromelastomerstorigidglass,losinganysealingcapabilities.
Therestistragichistory.ThephysicistRichardFeynmandemonstratedthisdramaticallyinafamous
televisedhearinginwhichheputaChallengertypeOringinicewaterandshowedthatitselasticitywas
lost.
 FIGURE26.7 (a)Arubberballiselasticatroomtemperature,asdemonstratedbythedeformationwhentheball
isstruckwithahammer.
(b)Iftherubberballiscooledbyplacingitintoliquidnitrogen,thematerialisconvertedtoarigid
brittle(glassy)solidand
(c)allelastomericpropertiesarelost.
AllanBlackman

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
26.2PolymerNotationandNomenclature
Wetypicallyshowthestructureofapolymerbyplacingparenthesesaroundtherepeatingunit,whichis
thesmallestmolecularfragmentthatcontainsallthestructuralfeaturesofthemonomer.Asubscriptn
placedoutsidetheparenthesesindicatesthattheunitrepeatsntimes.Thus,wecanreproducethe
structureofanentirepolymerchainbyrepeatingtheenclosedstructureinbothdirections.Anexampleis
polypropylene,whichisderivedbythepolymerisationofpropene.Polypropyleneisapolymerwith
manyuses,includingdishwashersafefoodcontainers,indooroutdoorcarpetingandartificialturf.

ChemistryResearch

MultifunctionalMaterials

ProfessorCraigHawker,Director,MaterialsResearchLaboratory,UniversityofCalifornia,
SantaBarbara

Whilenaturehasusedmolecularengineeringonthenanoscaleforbillionsofyears,only
recentlyhavechemistsbeenabletocrudelymimicnature'sperfection.Evenwiththese
tentativesteps,significantprogressandnewdiscoverieshavehadanimpactonourdaily
lives.Byvaryingthethreedimensionalstructuresandpositionsoffunctionalgroups,
syntheticchemistshavedevelopedtheabilitytoaccuratelycontrolthephysicalpropertiesof
bothsmallmoleculesandmacromolecules,aswellastocontroltheirinteractionswith
biologicalsystems.Classicalexamplesoftheuseofnanotechnologyincludethedesignof
volatileestersinthefragranceindustry,witharomasdirectlyrelatedtomolecularshape/size,
andthediscoveryofnumeroussyntheticdrugs.Thisgeneralthemeofpropertycontrol
throughmoleculardesignhasfoundincreasingattentionandapplicationinpolymersciencein
recentyearsandistheprimefocusoftheresearchgroupledbyCraigHawker,aUniversityof
Queenslandgraduate.

Traditionally,smallchangesinstructurehavebeenshowntohavedramaticeffectsonthe
propertiesofpolymersandoneneedstolooknofurtherthanpoly(ethylene)and
poly(propylene)toobservetheseeffects,withpoly(propylene)havingalowerimpactstrength
butsuperiorworkingtemperatureandtensilestrengththanpoly(ethylene).Thisallows
polyethyleneandpolypropylenetobeusedindramaticallydifferentapplications.Amajor
drivingforcebehindthisworkistherealisationthatmanyofthepromisingapplicationsof
nanotechnologyrelyonextendingsyntheticorganicchemistryintothenanometrelength
scale,especiallyasnanodevicesaredesignedwithincreasingsophistication.Therefore,the
principleofcontrollingstructureandfunctionalityonthenanometrescaleisapplicableto
theseverydifferentfields.Asaresult,creativeapproachesusingsyntheticchemistryare
requiredtocontroleveryfacetofmacromolecularstructureandtoenablefunctionalgroupsto
beintroducedatdefinedlocations.

TheHawkerresearchgroupdesignsmultifunctionalnanoscalematerialsforapplicationsas
diverseasthesynthesisofnanoparticlesfordiseasediagnosisandtherapeutictreatmentand
thedevelopmentofnovelstrategiesforpatterningsiliconwafersatsub20nmdimensionsfor
advancedmicroelectronicdevices.Thethreedimensionalnanoparticlesusedfordiagnostics
andtherapeuticshaveveryspecificandcontrolledsurfaces,internallayersandcores(see
figure26.8).Thesurfaceofaca.50nmnanoparticleisadornedwithpeptideligandsfor
specificallytargetingthenanoparticlestothetissueofchoice.Thesurfaceofthenanoparticles
isalsocomposedofpoly(ethyleneglycol)unitstoallowlongcirculationandresidencetimes
inthebodywithouttoxicorimmunogenicresponses.Theinternallayershavediagnosticunits
forimagingagents,suchasGdionsformagneticresonanceimaging(MRI)and64Cufor
positronemissiontomography(PET)imaging,whiledrugmoleculescanbeattachedor
adsorbedtotheinternallayersorcore.Bypreciselycontrollingallofthesenanoscopic
features,highperformancematerialscanbeconstructedthatmimicmanyoftheunique
featuresofnaturalsystems.

FIGURE26.8Aschematicviewofafunctionalnanoparticle.Thecore(grey),internallayers
(yellow)andsurface(blue)eachperformsaspecificfunctionwithinthenanosized
molecularassembly.Forexample,theblueouterlayerscouldbepeptidetargeting
groups,directingthenanostructuretospecificcellswheretheinternal(yellow)
layersdeliveratherapeuticdrug.
Themostcommonmethodofnamingapolymeristoaddtheprefixpolytothenameofthemonomer
fromwhichthepolymerissynthesised.Examplesarepolyethyleneandpolystyrene.Formorecomplex
monomersorwhenthenameofthemonomerismorethanoneword(e.g.vinylchloride),parentheses
areusedtoenclosethenameofthemonomer:

Table26.1givessomeexamplesofpolymersformedfromcompoundsrelatedtoethene,alongwiththeir
commonnamesandmostimportantuses.Notethat,whileIUPACgenerallyencouragestheuseof
systematicnames,itretainssomecommonnamesinpolymerchemistrybecauseoftheirestablishment
byusage.Itishoped,however,thatcommonnamesforpolymersarekepttoaminimumforscientific
communication.
TABLE26.1 Polymersderivedfrometheneandsubstitutedethenes
Commonname
Monomerformula (IUPACname) Polymername(s)typecommonuses
CH2 CH2 ethylene(ethene) polyethylene,polythene(PE)thermoplastic
polymerbreakresistantcontainersandpackaging
materials
CH2 CHCH3 propylene polypropylene,Herculon(PP)thermoplastic
(propene) polymertextileandcarpetfibres
CH2 CHCl vinylchloride poly(vinylchloride),PVCthermoplasticpolymer
(chloroethene) constructionandhealthcaresector
CH2 CCl2 1,1 poly(1,1dichloroethylene)thermoplasticpolymer
dichloroethylene clingfilmisacopolymerwithvinylchloride
(1,1
dichloroethene)
CH2 CHCN acrylonitrile polyacrylonitrile,Orolon acrylicsandacrylates
(propenenitrile)
nitrilerubber(Nipol,KrynacandEuroprene)is
acopolymerwithbutan1,3diene
CH2 CF2 1,1 poly(1,1difluoroethylene)thermoplasticpolymer
difluoroethylene piezoelectricmaterial,headphonemembranes
(1,1
difluoroethene)
CF2 CF2 tetrafluoroethylene poly(tetrafluoroethylene),PTFEthermoplastic
(tetrafluoroethene) polymerTeflon ,nonstickcoatings

CH2 CHC6H5 styrene polystyrene,Styrofoamthermoplasticpolymer

insulatingmaterials
ethylacrylate poly(ethylacrylate)moderatelythermoplastic
 (ethylpropenoate) polymerlatexpaints

methyl poly(methylmethacrylate),Lucite,Plexiglas
methacrylate thermoplasticpolymerglasssubstituent
(methyl2
methylpropenoate)

Polymerscanbederivedbypolymerisationofonlyonemonomer(theseareoftencalledhomopolymers)
orbypolymerisationoftwoormoredifferentmonomers(copolymers).Forexample,acopolymer
consistingofthemonomerunitsAandBcanhaveanalternatingarrangement(ABABAB
)orastatisticalarrangement(AAABABBABAA).blockcopolymers
consistsoftwoormorehomopolymersubunits(AAABBBBAAABBB
).

WORKEDEXAMPLE26.1

WritingtheFormulaforaPolymer
Giventhefollowingstructure,determinethepolymer'srepeatingunit:

Redrawthestructureusingthesimplifiedparentheticalnotationandnamethepolymer.

Analysisandsolution

Therepeatingunitis(CH2CF2)andthepolymeriswritten(CH2CF2)n.Therepeating
unitisderivedfrom1,1difluoroethyleneandthepolymerisnamedpoly(1,1
difluoroethylene).

PRACTICEEXERCISE26.1
Giventhefollowingstructure,determinethe
polymer'srepeatingunit:

Redrawthestructureusingthesimplified
parentheticalnotationandnamethepolymer.

ThediscoveryofTeflon(PTFE)canbedatedbackto6April1938.DuPontchemistDrRoyJPlunkett,
asDuPont'sJacksonLaboratoryinNewJersey,wascheckingafrozen,compressedsampleof
tetrafluoroethylene,whenheandhisassociatesdiscoveredthatthesamplehadpolymerised
spontaneouslyintoawhite,waxysolid,whichwaspolytetrafluoroethylene(PTFE).

Thisdiscoverywasanexampleofserendipityandisconsideredasoneofscience'stop10accidental
inventions.PTFEhasrevolutionisedtheplasticsindustry.IndustrialcoatingsofPTFEcanbeusedon
carbonsteel,aluminium,stainlesssteel,steelalloys,brassandmagnesium,aswellasnonmetalssuchas
glass,fibreglassandsomerubberandplastics.Theversatilityofthesecoatingsallowsapplicationtoan
almostunlimitedvarietyofsizesandconfigurations.Oneofthemostwidespreadexamplesofthisis
possiblythenonstickfrypan.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
26.3FormationofPolymers
Therearetwomainwaysthatmonomersarejoinedtoformpolymers.Oneprocessiscalledcondensationorstep
growthpolymerisation,inwhichasmallmoleculeisusuallyeliminatedwhenthetwomonomerunitsarejoined.The
otherprocessiscalledadditionorchaingrowthpolymerisation,inwhichmonomerunitsarejoinedwithouttheloss
ofatoms.

CondensationorStepgrowthPolymers
Stepgrowthpolymersareformedbythereactionbetweendifunctionalmolecules(whichhavetwofunctionalgroups
ofthesameordifferenttypes)witheachnewbondcreatedinaseparatestep.Duringpolymerisation,monomersreact
toformdimers,dimersreactwithmonomerstoformtrimers,dimersreactwithdimerstoformtetramers,andsoon.
Althoughasmallmoleculeisusuallyeliminatedwhenthevariousunitsarejoinedtogether,thisdoesnothappeninall
polymerisationsofthistype.However,becauseoftheirusuallysimilarmechanism,theyareallcalledcondensations.

Therearetwocommontypesofstepgrowthprocesses:(1)reactionbetweenAMAandBNBtypemonomers
togive(AMABNB)npolymersand(2)theselfcondensationofAMBmonomerstogive(A
MB)npolymers.Inthisnotation,MandNindicatethemonomer,andAandBthereactivefunctional
groupsonthemonomer.Ineachtypeofstepgrowthpolymerisation,anAfunctionalgroupreactsexclusivelywithaB
functionalgroup,andaBfunctionalgroupreactsexclusivelywithanAfunctionalgroup.Newcovalentbondsinstep
growthpolymerisationsaregenerallyformedbyreactionsbetweenAandBfunctionalgroups:forexample,
nucleophilicsubstitutionatanacylgroup(seechapter23).Afterpolymensation,theendsofthechainremainactive.In
thissection,wediscussfivetypesofstepgrowthpolymers:polyamides,polyesters,polycarbonates,polyurethanesand
epoxyresins.Themolecularmassofthepolymerisusuallycontrolledbythereactiontime,i.e.thelongerthereaction,
thehigheristhemolecularmass.

Polyamides
Intheearly1930s,WallaceHCarothers(figure26.9)andhiscoworkersatE.I.DuPontdeNemours&Companyin
theUSAbeganfundamentalresearchintothereactionsbetweendicarboxylicacidsanddiaminestoformpolyamides.
Toputtheirresearchintohistoricalcontext,asmentionedearlier,atthattimethechemicalreactionsusedtosynthesise
polymerssuchaspolystyreneandpoly(vinylchloride)werenotwellunderstoodbyorganicchemists.Therewasan
ongoingscientificargumentaboutthequestion:Whichforcesholdthemonomerunitstogetherinthepolymer?Itwas
believeduntilthefirstfewdecadesofthetwentiethcenturythatlargemoleculescouldnotbeboundbynormal
chemicalbondsasinsmallmolecules.Therefore,researchersatDuPontwantedtosynthesisepolymersusingwidely
understoodchemicalreactions,suchasthosebetweenacidsandaminestogiveamides,orbetweenacidsandalcohols
togiveesters.Thus,in1934,theysynthesisedthefirstfullysyntheticcommercialfibre,nylon6,6,apolyamide,so
namedbecauseitisproducedfromtwodifferentmonomers,eachcontainingsixcarbonatoms.
 FIGURE26.9WallaceHCarothers.
PhotoResearchers

Inthesynthesisofnylon6,6,adipicacid(1,6hexanedioicacid)andhexane1,6diaminearedissolvedinaqueous
ethanol,inwhichtheyreactinanacidbasereactiontoformaonetoonesaltcallednylonsalt(figure26.10).Thissalt
isthenheatedinanautoclaveto250Candaninternalpressureof1510 5Pa.Undertheseconditions,COO
groupsfromthediacidandNH3+groupsfromthediaminereactwiththelossofH2Otoformanamidebond.
Becausewaterisreleased,thistypeofreactioniscalledacondensation.Asyoucansee,theamidebondthatholdsthe
monomerunitstogetheristhesamebondthatholdstheaminoacidstogetherinsimpleamidesandpeptides(see
section24.3).Nylon6,6formedundertheseconditionsmeltsat250to260Candhasamolarmassrangingfrom10
000to20000gmol1.Thedifferencebetweenpeptidesandpolyamidesisthattheamidebondsinpeptidesare
separatedbyonlyonecarbonatom,whereas,inpolyamides,theamidebondsareseparatedbymorethanonecarbon
atom.
 FIGURE26.10Theformationofnylon6,6.

Inthefirststageoffibreproduction,crudenylon6,6ismelted,spunintofibresandcooled.Next,themeltspunfibres
arecolddrawn(drawnatroomtemperature)toaboutfourtimestheiroriginallengthtoincreasetheirdegreeof
crystallinity.Howdoesthiswork?Inthemoltenstage,thenylon6,6moleculesareindisarray,tangledwithoneother.
Whenthenylonisdrawn,theindividualpolymermoleculesarelinedupandbecomeorientedinthedirectionofthe
fibreaxis,enablinghydrogenbondstoformbetweencarbonyloxygenatomsofonechainandamidehydrogenatoms
ofanotherchain(seesection6.8):

Theregulararrangementofthechainsenforcedbyhydrogenbondingbetweenthemanyamidegroupsalongthe
alignedchains(whicharesimilartothehydrogenbondsinpeptides)encouragescrystallisationtotakeplace.This
givesstrengthandstiffnesstothenylonfibreandmakesitanexceptionallystrongmaterial.Attemptstopullthefibres
apart,eitherparallelorperpendiculartothestretchdirection,mustovercomethehydrogenbondsandthe
crystallisationforces,whichbotharisefromthecolddrawingprocessofthemeltedpolymer.Colddrawinghas
becomeanessentialstepintheproductionofmostsyntheticfibres.

Thenylonsareafamilyofpolymers,themembersofwhichhavesubtlydifferentpropertiesthatmakethemsuitedto
oneuseoranother(figure26.11).Thetwomostwidelyusedmembersofthefamilyarenylon6,6andnylon6.Nylon
6issonamedbecauseitissynthesisedfrom caprolactam(azepan2one),asixcarbonmonomer.Inthesynthesisof
nylon6, caprolactamispartiallyhydrolysedto6aminohexanoicacidandthenheatedto250Ctobringabout
polymerisation:
Nylon6isfabricatedintofibres,bristles,rope,highimpactmouldingsandtyrecords.

FIGURE26.11Thefirstnylonproduct(atoothbrushwithnylonbristles)wasmadein1938.Women'spreferenceforshorter
skirtsanddressesinthe1920sresultedinanincreasingdemandforstockings.Silkwasthefibreofchoiceat
thattime,butitwasexpensiveandhadtobeimportedfromeastAsia.Nylonturnedouttobetheperfect
syntheticreplacement,andnylonstockingsfirstbecameavailablein1939.
KariAnnTapp

Basedonextensiveresearchintotherelationshipsbetweenmolecularstructureandbulkphysicalproperties,scientists
atDuPontreasonedthatapolyamidecontainingaromaticringswouldbestifferandstrongerthaneithernylon6,6or
nylon6.Inearly1960,DuPontintroducedKevlar,apolyaromaticamide(aramid)fibresynthesisedfromterephthalic
acid(benzene1,4dicarboxylicacid)andbenzene1,4diamine.

WhatmakesKevlarfibressomuchstrongerthannylon,eventhoughthelinkingunitisthesameinboth?The
structuralflexibilityinnylonmeansthattheamidelinkageinanylonfibrecanassumetwodifferentconformations,
whichareinequilibrium(asshownontheleft):themorestabletransarrangementandthelessstablecisarrangement
(thisissimilartotheconformationinpeptides,whichwasdescribedinchapter24,p.1069).

Thefibrewithtransconformationattheamidebondhasalinearshape,whichcaneasilylineupintomoreordered
structuresleadingtocrystallisation.However,increasingconcentrationsofcisamidebondsinthepolymerbreakup
thisorder,preventingahigherdegreeofcrystallisation.

InKevlar,becauseoftheparaarrangement(seesection16.7)oftheamidebondsatthearomaticrings,thepolymer
chainisinflexibleandstiffandcannotinterloop.Incontrasttonylons,aramidscannotassumethecisconformationat
theamidebondbecausethiswouldcausesignificantsterichindrancebetweentheprotonsintheorthopositionatthe
aromaticrings:
Therefore,Kevlarpolymerstrandscanlineupalongsideeachothertoproduceahighdegreeoforderandtherefore
crystallinity.TheextraordinarystrengthofKevlarfibresisduenotonlytothehydrogenbondsbetweentwoamide
moietiesbutalsotostackingofthearomaticringsthisiscalledstackingorinteractions.

OneoftheremarkablefeaturesofKevlarisitslightweightcomparedwiththatofothermaterialsofsimilarstrength.
Forexample,a7.6cmcablewovenofKevlarhasastrengthequaltothatofasimilarlywoven7.6cmsteelcable.
However,whereasthesteelcableweighsabout30kgm1,theKevlarcableweighsonly6kgm1.Kevlarnowfinds
useinsucharticlesasanchorcablesforoffshoredrillingrigs,reinforcingfibresforcartyres,asbestosreplacement,
flameresistantclothingandsailcloth.Kevlarisalsowovenintoafabricthatissotoughthatitcanbeusedfor
bulletproofvests(figure26.12).
 FIGURE26.12BulletproofvestshaveathicklayerofKevlar.
AFPPhoto/CandidoAlves

WORKEDEXAMPLE26.2

SynthesisinganAramid
Howdoesthechemicalstructureofanaramidchangeifametasubstitutedaromaticdicarboxylicacidis
usedinsteadoftheparasubstitutedaromaticdicarboxylicacidinKevlar?Drawapolymerchainconsisting
offourmonomerunits.

Analysisandsolution

Themetasubstitutedaromaticdicarboxylicacidisisophthalicacid(1,3benzenedicarboxylicacid)andthe
diaminocompoundisbenzene1,4diamine.Reactionofanaminogroupwithacarboxylicacidgivesan
amidebond.Thepolymerconsistingoffourmonomershasafreeaminogroupononeendandafree
carboxylicacidmoietyontheotherend.
 PRACTICEEXERCISE26.2
Drawachainoffourmonomerunitsofapolymer
madefromphthalicacid(1,2benzenedicarboxylic
acid)andbenzene1,3diamine.

Polyesters
Polyestersarepolymersinwhicheachmonomerunitisjoinedtothenextbyanesterbond.Thefirstpolyester,
developedinthe1940s,wasformedbypolymerisationofterephthalicacid(benzene1,4dicarboxylicacid)with
ethyleneglycol(1,2ethanediol)togivepoly(ethyleneterephthalate),abbreviatedPET.VirtuallyallPETisnowmade
fromthedimethylesterofterephthalicacidbythefollowingtransesterificationreaction(p.1022):
Thecrudepolyestercanbemelted,extrudedandthencolddrawntoformthetextilefibreDacron polyester,the
outstandingfeaturesofwhichareitsstiffness(aboutfourtimesthatofnylon6,6),veryhighstrengthandremarkable
resistancetocreasingandwrinkling.EarlyDacronpolyesterfibreswereharshtotouch,duetotheirstiffness,sothey
wereusuallyblendedwithcottonorwooltomakeacceptabletextilefibres.Newlydevelopedfabricationtechniques
nowproducesofterDacronpolyestertextilefibres.PETisalsofabricatedintoMylarfilmsandrecyclableplastic
beveragecontainers(figure26.13).

FIGURE26.13PETsoftdrinkbottles.

PolymersinMedicine
Polymersareimportantmaterialsforheavydutyindustrialandhouseholdpurposes,andtheyhavealsofoundarolein
medicalapplications.Asthetechnologicalcapabilitiesofmedicinehavegrown,sohasthedemandforsynthetic
materialsthatcanbeusedinsidethebody.Polymershavemanyofthecharacteristicsofanidealbiomaterialtheyare
lightweightandstrong,areinertorbiodegradable(dependingontheirchemicalstructure)andhavephysicalproperties
(softness,rigidityandelasticity)thatareeasilytailoredtomatchthoseofnaturaltissues.Carboncarbonbackbone
polymersareresistanttodegradationandareusedwidelyinpermanentorganandtissuereplacements.

Artificialhearts,heartlungmachinesandartificialkidneysareexamplesofartificialorgansthatconsist,toamajor
extent,ofsyntheticpolymers.Also,modernartificialjointsaremadefromsyntheticpolymersforexample,artificial
hipsoftencontainapolymericacetabularcup(figure26.14).

FIGURE26.14Xrayimageofanartificialhipshowingthepolymercupsocketforthemetallicballjoint.
SPL/GustoImages

Polymericdrugsandpolymerdeliverysystemshavebeendevelopedwiththeaimofalteringthepharmokineticsand
pharmodynamicsoftherapeuticagents.Thesesystemscanbeusedtointroducenewandefficientmethodsofdrug
administrationandtodecreasedrugtoxicityandensuresafety.Forexample,polymerboundchemotherapeuticdrugs
forthetreatmentofcancerareconstructswherethedrugiscovalentlyboundtoapolymer.Thisensuresmoreefficient
deliveryofthedrugtotheaffectedorganinthebody,anditalsoreducesthetoxicityofthedrugitself.

Eventhoughmostmedicalusesofpolymericmaterialsrequirebiostability,applicationshavebeendevelopedthatuse
thebiodegradablenatureofsomemacromolecules.Anexampleistheuseofglycolicacid(2hydroxyethanoicacid)
andlacticacid(2hydroxypropanoicacid)toproducecopolymersthatactasabsorbablesutures(dissolvingstitches):

Traditionalsuturematerialssuchascatgutmustberemovedbyahealthcarespecialistaftertheyhaveservedtheir
purpose.Stitchesofthesehydroxyesterpolymers,however,areslowlyhydrolysedatphysiologicalpHover23
weeksbythetimethetissueshavehealed,thestitchesarefullydegradedandneednotberemoved.Thesuture
materialdegradesbynucleophilicattackofwateratthecarbonatomofoneoftheestergroups,whichcleavestheester
intoanacidandanalcohol.Intheexampleabove,thisrupturesthepolymerstrand.Furtherstepbystephydrolysisof
theremainingestergroupsleadsultimatelytothecompletebreakdownofthepolymertothemonomers,glycolicand
lacticacid,whichareexcretedbyexistingbiochemicalpathways.

WORKEDEXAMPLE26.3

SynthesisingaPolyester
Describethestructureofthepolymerthatwouldbeformedfrompropan1,3diolandadipicacid.Drawthe
repeatingunit.

Analysisandsolution

Thesetwocompoundsreacttoformanesterbond:
 PRACTICEEXERCISE26.3
Describethestructureofapolyesterformedfrom
adipicacidandglycerol(propane1,2,3triol).Draw
therepeatingunit.

Polycarbonates
Polycarbonatesarepolyestersinwhichthecarboxylgroupsarederivedfromcarbonicacid.Themostfamiliaris
Lexan ,acommerciallyimportantclassofengineeringpolyesters.Lexanformsbythereactionbetweenphosgene
(carbonyldichloride)andthedisodiumsaltofbisphenolA(4[2(4hydroxyphenyl)propan2yl]phenol):

Notethatphosgeneisthedichlorideofcarbonicacid,whichisunstablehydrolysisofphosgenegivescarbonicacid,
H2CO3,and2HCl.

Lexanisatough,transparentpolymerwithhighimpactandtensilestrengthsthatretainsitspropertiesoverawide
temperaturerange.Itisusedinsportingequipment(suchashelmetsandfacemasks,figure26.15),tomakelight,
impactresistanthousingsforhouseholdappliancesandinthemanufactureofsafetyglassandunbreakablewindows.
 FIGURE26.15Manymodernhelmetsincorporatealightweight,impactresistant,polycarbonateshell.
AFP/PunitParanjpe/Stringer

Polyurethanes
Aurethane,orcarbamate,isanesterofcarbamicacid,H2NCOOHthus,aurethaneorcarbamatefunctionalgroup
consistsofbothanesterandanamidelinkage.Carbamatesaremostcommonlypreparedbytreatinganisocyanate
withanalcohol.Inthisreaction,theHandORofthealcoholaddtotheC Nbondinareactioncomparabletothe
additionofanalcoholtoaC Obond:

Polyurethanesconsistofflexiblelowmolarmasspolyesterorpolyetherunits(blocks)alternatingwithrigidurethane
blocksderivedfromadiisocyanate,commonlyamixtureoftoluene2,4diisocyanateandtoluene2,6diisocyanate
(2,4diisocyanato1methylbenzeneand1,3diisocyanato2methylbenzene):

Notethatformationofpolyurethaneistheonlyexampleofstepgrowthpolymerisationthatdoesnotgenerateasmall
moleculeasabyproduct.

Ifthepolymerisationoftoluene2,6diisocyanateisperformedwithamoleculecontainingmorethantwohydroxyl
groups,suchasglycerol,crosslinkingbetweenthepolymerchainsoccurstoformathreedimensionalnetwork.
Generally,polymerswithcrosslinkedchainslosetheabilityoftheindividualpolymerchainstomoveindependently.
Themorecrosslinkingthereis,thelessflexibleistheresultingpolymerthisisusuallyaccompaniedbyahigher
meltingpointofthepolymer.Thermosetpolymershavearigidthreedimensionalstructureandusuallycannotbe
heatedtotheirmeltingpointwithoutdecomposition.

Wecanobtainsofter,moreelasticandmoreflexiblepolyurethanesbyusinglineardifunctionalpolyethyleneglycol
segments(oftencalledpolyetherpolyols)tocreatetheurethanelinks.SuchfibreshavefounduseasSpandex and
Lycra(figure26.16),thestretchfabricsusedinbathingsuits,leotards,sportscompressionclothingand
undergarments.Morerigidproductsresultifpolyfunctionalpolyolsareused,whichcreateathreedimensionalcross
linkedstructure.

FIGURE26.16ManystretchfabricsincorporateflexiblepolyurethanessuchasSpandexandLycra.
HamishBlair

Polyurethanefoamsforupholsteryandinsulatingmaterials(figure26.17)aremadebyaddingsmallamountsofwater
duringpolymerisation.Waterreactswithisocyanategroupstoformacarbamicacid.Carbamicacidsareunstable
compoundsthatundergospontaneousdecarboxylationtoproducegaseouscarbondioxide,whichthenactsasa
foamingagent:

FIGURE26.17Polyurethanefoamisoftenusedforcushioninginfurniture,insulationpanels,carpetpaddingandpackaging
materials.
PhotoResearchers/CharlesDWinters

EpoxyResins
Incontrasttothepreviouslydiscussedhighlyorderedsyntheticfibres,suchaspolyamidesandpolyesters,aresinisan
amorphous,viscousorsolid,mostlytransparentpolymerofnaturalorsyntheticoriginwithahighmolarmassandno
definitemeltingpoint.Epoxyresinsaresyntheticmaterialspreparedbypolymerisationinwhichonemonomer
containsatleasttwoepoxygroups(orethyleneoxidegroups,seesection19.4).Withinthisrange,alargenumberof
polymericmaterialsarepossible,andepoxyresinsareproducedinformsrangingfromlowviscosityliquidstohigh
meltingsolids.Themostwidelyusedepoxidemonomerisadiepoxidepreparedbytreating1moleofbisphenolA
with2molesofepichlorohydrin(2chloromethyloxirane):
Topreparethefollowingepoxyresin,thediepoxidemonomeristreatedwithethylenediamine(ethane1,2diamine):

Theprecedingreactioncorrespondstonucleophilicopeningofthehighlystrainedthreememberedepoxideringatthe
lesssubstitutedcarbonatom.

WORKEDEXAMPLE26.4

MechanismofDiepoxideFormation
Bywhattypeofmechanismdoesthereactiononthepreviouspagebetweenthedisodiumsaltofbisphenol
Aandepichlorohydrintakeplace?

Solution

ThereactionoccursbytheSN2mechanism.ThephenoxideionofbisphenolAisagoodnucleophile,and
chlorineontheprimarycarbonatomofepichlorohydrinistheleavinggroup.

PRACTICEEXERCISE26.4
Drawtherepeatingunitoftheepoxyresinformedfromthefollowingreaction.
(Hint:Drawthemechanismoftheepoxideringopeningreaction.)

Ethylenediamineisusuallyonecomponentinthetwocomponentepoxyresinkits(figure26.18)thatyoucanbuyin
hardwareorcraftstores(itisoftenwronglycalledcatalystonthepackaging)itisalsothereagentwiththeacrid
smell.

FIGURE26.18Anepoxyresinkit.
KariAnnTapp

Epoxyresinsarewidelyusedasadhesivesandinsulatingsurfacecoatings.Theyhavegoodelectricalinsulating
propertiesandsoareusedtoencapsulateelectricalcomponentsrangingfromintegratedcircuitboardstoswitchcoils,
andinsulatorsforpowertransmissionsystems.Epoxyresinsarealsousedascompositeswithothermaterials,suchas
glassfibre,paper,metalfoilsandothersyntheticfibres,tocreatestructuralcomponentsforjetaircraft,rocketmotor
casingsandsoon.

AdditionorChaingrowthPolymers
Additionorchaingrowthpolymerisationisatypeofpolymerisationthatinvolvessequentialadditionreactions,either
tounsaturatedmonomersortomonomerswithotherreactivefunctionalgroups.Incontrasttocondensation
polymerisation,allatomsofthemonomerarefoundinpolymersformedbyadditionpolymerisationnoatomislostor
gainedintheconversionofthemonomertothepolymer.Additionpolymerisationisfundamentaltothechemical
industry.Anexampleistheformationofpolyethylenefromethene:

Themechanismofchaingrowthpolymerisationdiffersgreatlyfromthemechanismofstepgrowthpolymerisation.In
thelatter,allmonomersplusthepolymerendgroupspossessequallyreactivefunctionalgroups,allowingforall
possiblecombinationsofreactionstooccur,includingmonomerwithmonomer,dimerwithdimer,monomerwith
tetramerandsoon.Incontrast,chaingrowthpolymerisationsinvolveendgroupswithreactivecentresthatreactonly
withamonomer.Theoverallprocessinvolvesconversionofbondsinthemonomerintobondsthatholdthe
repeatingunitsinthepolymertogether.Sincebondsarestrongerthanthebondsofthemonomerunits,much
energyisreleasedduringpolymerisation.Thereactiveintermediatesusedinchaingrowthpolymerisationinclude
radicals,carbanions,carbocationsandcertainmetalcompoundsknownasorganometalliccomplexes.

Manymonomersundergochaingrowthpolymerisation,includingalkenes,alkynes,allenes,isocyanatesandcyclic
compoundssuchaslactones,lactams,ethersandepoxides.Wewillconcentrateonthechaingrowthpolymerisationof
etheneandsubstitutedethenesandshowhowthesecompoundscanbepolymerisedbyradical,cationicand
organometalmediatedmechanisms.

RadicalChaingrowthPolymerisation
Thefirstcommercialpolymerisationsofethenewereinitiatedbyradicalsformedbythermaldecompositionoforganic
peroxides.Aradicalisanymoleculethatcontainsoneormoreunpairedelectrons,andwehaveseensomeexamples
oftheseinchapter15.Theycanbeformedbythecleavageofabondinsuchawaythateachatomorfragment
participatinginthebondretainsoneelectron(homolyticcleavage).Forexample,whendiacylperoxidesareheated(the
mostprominentarebenzoylperoxideandacetylperoxide),theperoxidicOObondiscleavedtogivetwoacyloxyl
radicals,whichbothhaveanunpairedelectronontheoxygen.Acyloxylradicalscanundergofurtherhomolyticbond
breakage,bywhicharadicalRisformedandcarbondioxideisreleased.

Asaconvention,fishhook(singleheaded)arrowsareusedtoshowthechangeinpositionofsingleelectrons.

radicalchaingrowthpolymerisationofetheneandsubstitutedethenesinvolvesthreesteps:(1)chaininitiation,(2)
chainpropagationand(3)chaintermination.Althoughradicalpolymerisationscanbeperformedwithalltypesof
systems(doublebondsortriplebonds),wewilldiscussonlypolymerisationsofalkenessincetheyarethemost
importantadditionpolymerisations.
Step1:chaininitiationformationofradicalsfromamoleculethathasonlypairedelectronsandthatpossesses
aweakbond:

Inthegeneralequationabove,InInrepresentsaninitiator,whichcleavestogivetworadicals(In).Theenergy
requiredtobreakthisbondhomolyticallycanbeprovidedbyheatorbylightofasuitablewavelength.Thereare
manymethodsofproducingradicalsfrommanydifferenttypesofinitiatorsInIn.Oneclassofradicalinitiators
arediacylperoxides,whichhaveaverylabile(reactive)OObond.Inthereactionatthetopofthispage,boththe
acyloxylradicalsandtheradicals,R,thatresultthroughlossofCO2areactuallyactingasinitiatorradicals.Other
commonradicalchaininitiatormoleculesaretheazoalkanes,suchasazobisisobutyronitrile(AIBN),whichwhen
heatedorirradiatedgivetwoinitiatorradicalswiththereleaseofonemoleculeofN2:

TheinitiatorradicalInundergoesadditiontothebondinanalkene.Oneoftheelectronsofthebondformsa
 newelectronpairwiththeincomingradical,whiletheremainingelectronoftheformerbondremainsunpaired:

Step2:chainpropagationTheresultingradicalsubsequentlyaddstoanotheralkaneinaselfperpetuating
reactionthatbuildsagrowingpolymerchain.

Step3:chainterminationcombinationofradicals.Evenifnotallreactantmoleculesareconsumed,reactions
canoccurthatterminatethespeciescarryingtheradicalchain.Oneterminationprocessisthesimplecombination
oftwochainsbyformingabondbetweenfreeendsoftheradicalchain.Anotherpathwayisadisproportionation
betweentworadicalchains,bywhichoneradicalspeciesisoxidisedtoanalkene(throughlossofahydrogen
atom)andtheotherisreducedtoanalkane(throughuptakeofahydrogenatom).Inbothcases,theradicalsare
transformedintononradicalspecies.
a.Coupling

b.Disproportionation

Youmayaskwhythechainterminationprocessesaboveoccuratall,orwhytheydonotoccurallthetime.The
answerliesinthekineticsofradicalchainreactions(seechapter15).Thereasonforthesuccessofradicalchain
processesistheverylowconcentrationofreactiveradicalspecies.Onlyveryfewradicalsareproducedintheinitiation
process,andtheyreactextremelyfastwiththeexcessalkenetoproducenewradicals,againinverylowconcentration,
andsoon.Becauseofthelargeconcentrationofalkene,thereisonlyaverylowprobabilityoftworadicalsmeetingto
terminatethechainhowever,thisdoeshappenandisthereasonwhychainpropagationcanstopbeforeallstarting
materialsareconsumed.

Thecharacteristicfeatureofthechainpropagationstepisthereactionofaradicalandamoleculetogiveanew
radical.Propagationstepsrepeatoverandover,withtheradicalformedinonestepreactingwithamonomerto
produceanewradicalandsoon.Thenumberoftimesacycleofchainpropagationstepsrepeatsiscalledthechain
lengthandisgiventhesymboln.Inthepolymerisationofethene,chainlengtheningreactionsoccurataveryhigh
rate,oftenasfastasthousandsofadditionspersecond,dependingontheexperimentalconditions.

Therelativestabilitiesofalkylradicalsaresimilartothoseofalkylcarbocations:
Thus,radicalpolymerisationsofsubstitutedethenesalmostalwaysgivethemorestable(moresubstituted)radical.
Becauseadditionsarebiasedinthisfashion,polymerisationsofsubstitutedethenemonomerstendtoyieldpolymers
withmonomerunitsjoinedbythehead,C(1),ofoneunittothetail,C(2),ofthenextunit:

Themolecularmassofanadditionofchaingrowthpolymerisusuallycontrolledbytheratioofinitiatorandmonomer.
Ifmoreinitiatorisused,morepolymerchainswillgrowsimultaneously,whichwillconsumemonomers,resultingin
polymerswithalowmolarmass.Ontheotherhand,ifveryfewinitiatormoleculesarepresent,eachpolymerchain
willgrowlongersothatthemolarmassincreases.

WORKEDEXAMPLE26.5

SynthesisingaChaingrowthPolymer
Showthemechanismfortheformationofaradicalsegmentofpoly(vinylchloride)containingthreeunitsof
vinylchloride,initiatedbyAIBN.

Analysisandsolution

AIBNisaradicalinitiator,sowearedealingwithachaingrowth(addition)polymerisation.Inthefirststep,
radicalsaregeneratedfromAIBNbyheatorlight.Theresultingalkylradicalsattackvinylchloridesothat
themorestablesecondaryradicalisformed.Thelatterattacksanothervinylchloridemonomerandsoon.
Inthegrowingpolymerchain,eachthirdcarbonatombearsasidechainwithachlorinesubstituent.

(b)Radicalchainpropagation
 PRACTICEEXERCISE26.5
Showthemechanismfortheformationofaradical
segmentofpolystyrenecontainingthreeunitsof
styrene,initiatedbydiacetylperoxide.

Thefirstcommercialprocessforethenepolymerisationusedperoxidecatalystsattemperaturesof500Cand
pressuresof100010 5Patoproduceasoft,toughpolymerknownaslowdensitypolyethylene(LDPEorPELD)
withadensityofbetween0.91and0.94gcm3andamelttransitiontemperature,Tm,ofabout115C.Because
LDPE'smeltingpointisonlyslightlyabove100C,itcannotbeusedforproductsthatwillbeexposedtoboiling
water.Atthemolecularlevel,chainsofLDPEarehighlybranched.

Thebranchingonchainsoflowdensitypolyethyleneresultsfromabackbitingreactioninwhichtheradicalend
grouptakesahydrogenatomfromthefourthcarbonatomback,C(5)thisconvertsthelessstable1radicaltoamore
stable2radical.Asidereactionsuchasthisiscalledachaintransferreactionbecausetheactivityoftheendgroup
istransferredfromonechaintoanother.Continuedpolymerisationofmonomersfromthisnewradicalcentreleadsto
abranchfourcarbonatomslong.
Approximately65%ofallLDPEisusedforthemanufactureoffilms.LDPEfilmisinexpensiveandcanbemoulded
whenheatedthismakesitidealforpackagingconsumeritemssuchasbakedgoods,vegetablesandotherproduce,for
garbagebagsandforinsulatingelectricalequipmentandcables.

ZieglernattaChaingrowthPolymerisation
Thebackbitingmechanismthatcausesbranchinginpolymerchainsisanunavoidablesidereactioninradical
polymerisations.Thisbranchinggreatlyaffectsthepropertiesofpolyethylene.Forexample,whereaslinearregionsof
thepolyethylenechaincanpackclosetogethertoformhighlyordered,crystallineregionsinthepolymer,thebranched
regionswiththeirstructuralirregularitiescannotparticipateinthiscrystallisation.Sincecloserpackingand
crystallisationgivethismaterialitshighdensityandstrength,chainbranchingmeanslowerdensityandmore
flexibility.Sincebothdensityandcrystallisationpropertiesofpolymersarecloselyconnectedtotheircommercialuse,
thedevelopmentofapolymerisationprocessthatcontrolsbranchingandchainlengthwasofgreatinteresttochemists
inthefirsthalfofthetwentiethcentury.Thisledtothedevelopmentoftransitionmetalcatalysts,whichallowthe
polymerisationofetheneandsubstitutedetheneswithoutradicals.

Polyethylene

Inthe1950s,KarlZieglerfromGermanyandGiulioNattafromItalydevelopedanalternativemethodforthe
polymerisationofalkenes,forwhichtheysharedtheNobelPrizeinchemistryin1963.TheearlyZieglerNatta
catalystswerehighlyactive,heterogeneousmaterialscomposedofaMgCl2support,agroup4transitionmetalhalide
suchasTiCl4andanalkylaluminiumcompound,Al(CH2CH3)2Cl.ThereactionbetweenAl(CH2CH3)2ClandTiCl4
belowresultsinanalkyltitaniumspecies(step1).Onceformed,etheneunitsarerepeatedlyinsertedintothetitanium
carbonbondofthealkyltitaniumcompoundtoyieldpolyethylene(steps2and3).Thesecatalystsbringaboutthe
polymerisationofetheneandpropeneat1410 5Paandattemperaturesaslowas60C.
Step1:Formationofatitaniumcarbonbond:

Step2:Insertionofetheneintothetitaniumcarbonbond:

Step3:Repeatedinsertionofetheneintothetitaniumcarbonbond:
Over27billionkilogramsofpolyethyleneareproducedworldwideeveryyearwithZieglerNattacatalysts.
PolyethylenefromZieglerNattasystems,termedhighdensitypolyethylene(HDPEorPEHD),hasahigherdensity
(0.96gcm3)andmelttransitiontemperature(133C)thanlowdensitypolyethylene,isthreetotentimesstronger,
andisopaqueratherthantransparent.Theaddedstrengthisduetomuchlesschainbranchingand,therefore,ahigher
degreeofcrystallinityinHDPEthanLDPE.Asaresultofthehighercrystallinity,thescatteringoflightisincreased
leadingtohigheropacityofthepolymer.

EvengreaterimprovementsinpropertiesofHDPEcanberealisedthroughspecialprocessingtechniques.Inthemelt
state,HDPEchainshaverandomlycoiledconformationssimilartothoseofcookedspaghetti.Engineershave
developedextrusiontechniquesthatforcetheindividualpolymerchainsofHDPEtouncoilintolinearconformations.
Theselinearchainsthenalignwithoneanothertoformhighlycrystallinematerials.HDPEprocessedinthisfashionis
stifferthansteelandhasapproximatelyfourtimesitstensilestrength!Becausethedensityofpolyethylene(~1.0g
cm3)isconsiderablylessthanthatofsteel(8.0gcm3),thesecomparisonsofstrengthandstiffnessareevenmore
favourableiftheyaremadeonamassbasis.

Polyethyleneofultrahighmolarmass,alsoknownashighperformancepolyethylene(HPPE)containsextremelylong
polymerchainswithamolarmassof26million.PolyethylenechainsareheldtogetherbyvanderWaalsforces,
whicharenotverystrong.However,becauseoftheextremelylongchainsinHPPE,thevanderWaalsinteractions
becomeverystrong.HPPEishighlyresistanttochemicalsandisusedinfibrematerialsandmedicalapplicationssuch
asartificialjoints(seepp.11289).

Polypropylene

Whentheasymmetricalalkenepropene(seesection26.2)ispolymerised,thepolypropylenechainhasamethyl
branchoneverysecondcarbonatomthismeansthatthiscarbonatomischiral.Thepropertiesofpolypropyleneare
stronglyinfluencedbythethreedimensionalarrangementofthesemethylbranches:thatis,whetherallmethylgroups
areonthesamesideofthechain(isotacticpolypropylene),alternating(syndiotacticpolypropylene)ortaking
positionsrandomlyalongthechain(atacticpolypropylene).

Whenpropeneispolymerisedthroughradicalpolymerisation,mostlyatacticpolypropyleneisobtained.Itwas,
therefore,abigscientificchallengetodevelopamethodthatallowedthepolymerisationofpropene(andother
monosubstitutedalkenes)insuchawaythatthechainconfigurationconsistsofsmallregularlyorientedunitsina
singlesequentialarrangement(calledstereoregular).In1956,NattadevelopedamodifiedZieglerNattacatalyst
consistingoftriethylaluminium,Al(C2H5)3,andtitanium(III)chloride,TiCl3,whichyieldsover90%ofisotactic
polypropylene.

Isotactic,syndiotacticandatacticpolypropylenearenotmirrorimagesofeachother.Therefore,theyare
diastereomers(seesection17.1),andthesethreevariationsofpolypropylenehavedifferentphysicalandchemical
properties.Thehighlyorderedcarbonchainsinisotacticpolypropyleneresultinamaterialofhighstrengthand
stiffness,whichiswidelyusedcommercially.Atacticpolypropylenewithpolymersoflowmolarmass(oligomers)is
stickyandsoisusefulinadhesives.Syndiotacticpolypropyleneissomewhatsofterthanisotacticpolypropylene,but
alsotoughandclear.Itbecamesynthetically(andcommercially)availableonlyafterthedevelopmentofcertainchiral
organometalliccatalyststhatcandistinguishbetweenthetwomirrorrelatedfacesofpropene,asshownbelow.

Wewillnotgointomoredetailhereaboutasymmetricsynthesisbutyoumayencountermethodstosynthesiseonly
oneenantiomerofachiralcompound(seesection17.7)inyourfuturestudiesinchemistry.

CationicPolymerisation
Anothertypeofadditionpolymerisationiscationicpolymerisation,whichisinitiatedbyanelectrophile,generallya
proton.TheprotonisderivedfromareactionbetweenaLewisacid,suchasAlCl3,SnCl4,BF3orTiCl4,andaproton
donatingLewisbase,suchaswater.Cationicpolymerisationsareusedtopolymeriseelectronrichalkenes,suchas
styrene,vinylethersandisobutene(isobutylene),thelastofwhichwewilldiscusshere.
Step1:ChaininitiationReactionofborontrifluoridewithwaterreleasesaproton,whichaddstothesp 2carbon
atominisobutene,formingthemorestable3carbocation(seesection16.5).

Step2:ChainpropagationThecationformedintheinitiationstepreactswithanothermoleculeofisobuteneto
formanewcationthat,inturn,reactswithathirdmonomerandsoon.Witheverynewmonomerunitaddingtothe
poly(isobutylene)chain,thepositivechargemovestotheendofthemostrecentlyaddedmonomerunit.

Step3:ChainterminationCationicpolymerisationcanbeterminatedeitherbylossofaproton,whichleadsto
 formationofanalkene,orbyreactionwithanucleophile.

Poly(isobutylene)isalsoknownasbutylrubber.Itisanelastomerthatisimpermeabletoairandsohasmany
applicationswhereairtightrubberisrequired.Thefirstmajorapplicationofbutylrubberwastyreinnertubes,whichis
stillanimportantsegmentofthemarkettoday.Inaddition,butylrubberisusedtomakeadhesivesandclingfilm,and
isusedasanadditiveinpetrolanddieselandeveninchewinggum.

WORKEDEXAMPLE26.6

SynthesisingaPolymerThroughCationicPolymerisation
Showthemechanismfortheprotoncatalysedformationofacationicsegmentofpoly(methylvinylether)
containingthreeunitsofmethylvinylether.

Analysisandsolution

Methylvinyletherisanunsymmetricallysubstitutedalkene.Thepolymerisationisinitiatedbyadditionofa
protontothedoublebondformingthemorestable(morehighlysubstituted)carbocation.Thisisattacked
byanothermoleculeofmethylvinyletherinastepwisemannertoproducethepolymer.Eachthirdcarbon
atomofthepolymerbackboneissubstitutedbyamethoxygroup.

PRACTICEEXERCISE26.6
Showthemechanismforthecationic,proton
catalysedpolymerisationofstyrenebydevelopinga
segmentofpolystyrenecontainingthreeunitsof
styrene.
AnionicPolymerisation
Additionpolymerisationcanalsobeperformedwithanionicspeciesbeingthechaincarrier.Thistypeof
polymerisationusesalkeneswithelectronwithdrawinggroups,whichcanstabilisenegativechargesverywell,suchas
throughresonance(seesection19.3).Examplesinclude1,3butadiene,styrene,acroleinandmethylacrylonitrile.

Anionicpolymerisationsareinitiatedbytheadditionofnucleophilestothealkene.Thesenucleophilescouldbemetal
amides,hydroxidesandalkoxides,aswellasorganometallicspecies,suchasGrignardreagents(seesection21.5)and
alkyllithiumcompounds,inwhichthealkylresiduehasanegativepolarity.

WewilldiscussheretheanionicpolymerisationofstyreneinitiatedbyadditionofanalkyllithiumRLitothealkene
doublebond.
Step1:ChaininitiationoccursbyadditionofthealkylresidueR,leadingtoformationofacarbanion,whichis
stabilisedbyresonance.

Step2:Chainpropagationinvolvesadditionoftheaniontoanothermoleculeofstyrenetoformanewanion,
whichinturnreactswithafurtherstyrenemonomer.Thenegativechargemovestotheendofthemostrecently
addedmonomerunit.

Step3:Chaintermination.Anionicpolymerisationhasnoformalterminationpathway.Usually,terminationoccurs
throughthepresenceofimpurities,suchaswaterorotherelectrophiles.Terminationthroughreactionwitha
BrnstedLowryacid(seesection11.1)isshownbelow.
ReversibledeactivationRadicalPolymerisation
Radicalpolymerisationisamaturetechnologythatiswidelyusedinindustry.Forexample,vinylpolymersare
producedonascaleofmillionsoftonnesperyear.However,amajordisadvantageisthatthehighreactivityofthe
radicalchaincarrierspreventstheindustrialproductionofpolymerswithcontrolledarchitecture(e.g.block
copolymersandstarpolymers,seep.1118)andlowpolydispersity(e.g.ahighlyuniformmolecularmassdistribution).
Inthelatetwentiethcentury,anewconceptwasdevelopedwhichisbasedontheprincipleofreversibledeactivation
ofthepolymerchaingrowthduringradicalpolymerisation.Thesemethodsrelyonadynamicequilibriumbetweenlow
concentrationsofpropagatingradicalsandvarioustypesofdormantspeciesproducedthroughrapiddeactivationof
growingradicals.

Figure26.19illustratestheuseofnitroxidesasmediatorsinsuchreversibledeactivationradicalpolymerisation.
NitroxidesareradicalspeciespossessinganunpairedelectronattheoxygenatomofanNOgroup(thenitroxide).
TEMPO(theIUPACnameis2,2,5,5tetramethylpiperidineNoxyl)isthemostwellknownofthesenitroxidesitisa
stableorangesolidandiscommerciallyavailable.ReversiblerecombinationofTEMPOwithastyrylradicalleadstoa
dormantnonradicalspecies.HeatingbreakstheCObondbetweenthestyrylandTEMPOmoietiesandtransforms
thedormantcompoundintotheactivestyrylradical,whichcanthenundergoradicalpolymerisation.Thegrowing
polymerchaincanbereversiblytrappedbyreactionwithTEMPOtoyieldanotherdormantspecies.Theoverallrateof
theradicalpolymerisationisdeterminedbytheratioofactivation,deactivationandtheactualpolymerisationstep.
ManyanaloguesofTEMPOhavebeendesignedforthesynthesisofspecialpolymerarchitecturesthroughthis
reversibledeactivationradicalpolymerisationmethod.
 FIGURE26.19Theconceptofcontrolledradicalpolymerisationusingnitroxidemediatedpolymerisation.

ChemicalConnections

CSIRO'sRAFTTechnology

Polymersaremacromoleculeswhicharecomposedofdiscretechemicalunitscalledmonomers.Polymersare
importantbecausesomuchofwhatweareandwhatweuseinoureverydaylivesismadeupofpolymers:
fromnaturalpolymers,suchasproteinsandourownDNA,throughtosyntheticpolymers,suchasplastics,
therapeutics,electronics,paints,oilsandcosmetics.Polymersynthesisisacomplexprocessthatcanbe
classifiedintotwobroadcategories:additionpolymerisationandcondensationpolymerisation.

Inadditionpolymerisation,polymersaremadebyaddingmonomersonebyonetoanactivesiteonthe
growingchain.Themostcommontypeofadditionpolymerisationisfreeradicalpolymerisation.Polymeric
materialsmadebyconventionalfreeradicalpolymerisationarecharacterisedbyabroadmixtureofpolymer
chainlengths,eachwithadifferentmolecularmass,resultinginabroadmolecularmassdistribution(figure
26.20).

FIGURE26.20Aschematicshowingtheprocessofadditionpolymerisation,resultinginpolymerchainswithawide
rangeofmolecularmasses.

Polymersmadebyconventionalfreeradicalpolymerisationaresatisfactoryforgeneralpurposeapplications,
suchasgeneralpaintsandplastics,astheirpropertiesdonothavetobeprecise.Ourmodernworld,however,
ishungryfornew,highlyfunctionalisedpolymerstoaddressthemanynewandexistingchallengesthatwe
face,includingtheneedfornewtherapeuticsanddrugdeliverysystems,multifunctionalpolymersfor
personalcareuses,andnewcontrolledreleaseagentstohelpoptimiseagriculturalyields.Toaddressthislevel
offunctionandsophistication,polymersofwelldefinedsize,compositionandarchitectureareneeded.

CSIRO'sRAFT(reversibleadditionfragmentationchaintransfer)technologyprovidesarevolutionarylevelof
controlsuitableforhighlyfunctionalisedpolymers.RAFTisatypeofadditionpolymerisationinwhich
terminationreactionsarelargelysuppressed,andpolymergrowthcancontinueuntilthemonomersupplyhas
beenexhausted.Thepolymerisationwillresumeifmoremonomers(andinitiators)areaddedtothesolution.

ThisfeatureofRAFTgivesthemanufacturerveryspecificcontroloverthesize,compositionandarchitecture
ofthepolymerbeingformed.Itenablesthecreationofpolymerchainsthataremoreuniforminmolecular
mass(i.e.lowpolydispersity,seefigure26.21),whichmeansthatsuchpolymersexhibitmorerefined
properties.

FIGURE26.21Aschematicshowingtheprocessofadditionpolymerisationusingreversibleadditionfragmentation
chaintransfer(RAFT)technology,resultinginpolymerchainswithanarrowrangeofmolecular
masses.

RAFTiscompatiblewithawiderangeofmonomersandmonomermixturesandcanbeusedinallmodesof
freeradicalpolymerisation,includingsolution,emulsionandsuspensionpolymerisations.Importantly,
polymermanufactureusingtheRAFTprocessiscompatiblewithexistingindustrialplantsandprocesses,
whichmakesitsimplementationinindustrystraightforwardwithouttheneedfornewsignificantcapital
investment.

RAFTderivedpolymersarealsocharacterisedbydefinedendgroupswhichcanbespecificallymanipulated
(seebelowforexamplesoftherangeofpossibleendgroups).Thisallowsuserstodeploysuchpolymersas
syntheticintermediatesintheirownrightformyriadapplications,includingtheattachmenttoothermolecules,
materialsandsurfaces.Thisisplainlynotpossiblewithconventionallyderivedadditionpolymers.RAFT
providestheopportunitytodesignandsynthesisehighlyfunctionalisedmoleculesandmaterialswithnew
propertiesandfeatures.
Insummary,RAFTisarevolutionarytechniqueinthefieldofpolymerdesignandsynthesis.Itsabilityto
controlmolecularmass,compositionandarchitecture,andtoproducepolymersthatcanbeattachedtoother
molecules,materials,andsurfaces,istrulyenabling.

TheapplicationsofRAFTaremanifoldanddiverse,andincludepersonalcareproducts,genesilencingforthe
treatmentofhumandiseases,highperformancepaints,circuitboardsandelectronics,industriallubricants,
flexibleelectronicsandnewmaterialstoimprovetheefficiencyandlowertheenvironmentalimpactof
agrichemicals.
Thisisaveryexcitingareaofchemistryandweareseeingahugeamountofglobalinterestinthis
technology.Thereareover450newinventionsthatuseRAFTthathavebeenpatented,morethan3000
scientificpapersthatciteourRAFTworkandwehavelicensedthetechnologyto15companiestoexploit
thetechnologyinadiverserangeoffields.WearenowseeingthefirstnewproductsmadeusingRAFT
enterthemarket.(DrEzioRizzardo,CSIRO,leadinventorofRAFT)

CSIRO'sRAFTscientistsarecontinuingtheresearchandcommercialisationofmultifunctionalpolymers,
particularlyintheareasofagriculture,drugdelivery,biomedicalmaterials,personalcareandcosmeticsand
flexibleelectronics(figure26.22).TolearnmoreaboutRAFTanditsapplications,goto
www.csiro.au/products/RAFT.

FIGURE26.22 CSIROisusingRAFTtechnologytodeveloppolymersforusein
(a)personalcareproducts,
(b)spraypaintsand
(c)drugdelivery.

ChemistryResearch

IntelligentMaterials

ProfessorGordonWallace,UniversityofWollongong

Traditionalpolymershavebeenengineeredtoprovidematerialsthatarelowdensity,mechanicallystrong
andenvironmentallystable.Theyhavebeenmadetobenonresponsivetheyare,infact,lightweight,
dumbmaterials!

Intelligentpolymersareengineeredfromthemolecularleveltorespondtoenvironmentalstimuliinaway
thatenhancestheirperformance.Imagine,forexample,apolymerthatchangescolourinsunlighttostop
transmissionoflight,orthatbecomesstrongerinresponsetostress.Considerapolymercoatingthatreleases
acorrosioninhibitorinresponsetotheonsetofcorrosionorevenamedicaldevicethatreleasesanti
inflammatorydrugsinresponsetotheonsetofinfection.

Polymerssuchaspolypyrroleconductelectricityandcanbereversiblyoxidisedandreducedaccordingto
theprocessesshowninfigure26.23.Unliketraditionalpolymers,theyarenotelectronicinsulatorsthey
conductelectricity.Also,unliketraditionalpolymers,theyarenotinerttheyaredynamic(electroactive)
structures.
 FIGURE26.23Polypyrroledynamic(electroactive)polymerstructure(A=anion).

Thechemical,biological,electricalandmechanicalpropertiesoftheseconductingpolymersarecritically
dependentontheoxidationstateofthestructureandhenceontheirworkingenvironment.Ifthisdynamic
behaviourcanbedeterminedbyappropriatemolecularengineering,trulyintelligentpolymerstructureswill
emerge.

Thesedynamicpropertiesofpolymerscanalsobefinetunedintheworkingenvironmentbytheapplication
ofanexternalelectricalpotential.Forexample,electricalstimulationhasbeenusedtoinitiateanionflux
acrossaconductingpolymermembrane.SimplesaltssuchasNaClcanbepumpedacrossthesedynamic
membranesusinganappliedpotential,andtheionfluxcanbeswitchedoffatanytimebyremovingthe
electricalstimulus.

Usingasimilarbutnowtrilayermembranestructure,electricalstimulationcanbeusedtoinducemovement
inconductingpolymerscreatingsocalledartificialmuscles(seefigure26.24).Electricalstimulationcauses
anionstomoveintotheoxidisedsideofthemembranestructure,causingexpansion,andexpelsanionsfrom
theotherside,causingcontraction,resultinginmovement(seefigure26.24b).Theabilitytoinducesuch
chemicalandmechanicalchangesinsitupresentssomeexcitingopportunitiesfortheuseoftheseintelligent
polymersinbiomedicaldevices.

FIGURE26.24 Electricalstimulationcausesdramaticmovement(curling)inthepolymer.Schematicstructure
oftheconductingpolymeractuatorin
(a)theneutralpositionand
(b)theelectricallystimulatedstate.
Recently,researchersattheIntelligentPolymerResearchInstitute,incollaborationwithscientistsatthe
BionicEarInstituteandStVincent'sHospital,showedthatthesepolymerscanbedesignedsothattheyare
compatiblewithnervecells.Throughelectricalstimulation,theycanreleasenervegrowthfactorsand
facilitatetheoutgrowthofneuritesfromthesecells(figure26.25).Suchpolymersmaywellfindusein
improvingtheelectrodecellinterfaceinmedicalbionicdevicessuchasthecochlearimplant(abionicear
pioneeredbyProfessorGraemeClarkinAustralia).

FIGURE26.25Electricalstimulationbyaconductingpolymercausesdramaticimprovementsinneuriteoutgrowth
fromnervecells.
GordonWallace

Alsoonthemedicalfront,intelligentpolymershavebeendevelopedthatrespondtoelectricalstimuliby
producingaforceormovement.Suchpolymersmayassistsurgeonsduringimplantationofmedicaldevices
suchasthebionicear,whichisasteerableimplant.

Asthemechanicalstrengthofintelligentpolymersisimproved,theymayevenbeusedaswearable
prostheticstoassistwithlimbmovement.Recently,usingnanotechnology,smallamountsofcarbon
nanotubeshavebeenaddedtoaconductingpolymertoproducethestrongestartificialmusclefibrestodate.
Somemovementisstillpossibleevenunderstressesof100MPainexcessofwhathumanmusclecan
withstand.
 Theabilityofconductingpolymerstosensetheenvironmentisbeingcoupledwithanabilitytorespond,
producingtrulyintelligentsystems.Asimpleexampleisthedevelopmentofaconductingpolymertrilayer
systemthatrespondstooxygenlevelstoopenavalvetomonitortheoptimumenvironmentalconditionsfor
foodpackagingduringtransport.

Aswedevelopourabilitytomolecularlyengineerthesesystems,somefascinatingsystemswillemerge.

Acontrolledradicalpolymerisationprocessbasedonreversibleadditionfragmentationchaintransfer(RAFT)hasbeen
developedbyCSIROinAustraliaandRhodiainFrance.Theconceptisbasedonthereversibleadditionofradicalsto
carbonsulfurdoublebondsinthiocarbonylthiotransferreagents(RS(C S)Z(figure26.26).Verypotentreagents
arexanthates,whichareestersderivedfromcarbonicacid,wheretwooxygenatomsarereplacedbysulfur,i.e.Zis
OR.TheadditionofagrowingpolymerchainradicaltotheC SbondisfollowedbyfragmentationofanS
polymerchainbond.Thisreleasesapolymerradical,whichcanundergofurtherchaingrowth,untilitisagaintrapped
byreversibleadditiontoaCSbond.Today,theRAFTtechnologyisaverypowerfultoolfordesigningfunctional
polymerarchitecturesforapplicationsinmedicine,electronicsandphotovoltaics,aswellascoatingsandpaints.

FIGURE26.26TheRAFTpolymerisationprocess.

NaturalRubberandTheVulcanisationProcess
NaturalrubberisanimportantproductderivedfromthelatexoftherubbertreeHeveabrasiliensis.Itisapolymerof
isoprene(2methylbutan1,3diene,seesection16.3)thatfeaturesaZgeometryatthedoublebondineachunit.On
average,anaturalrubbermoleculecontainsupto5000unitsofisoprene.Thebiologicalfunctionofrubberlatexisto
protectthetreeafterinjurybyformingabandagethatcoversthewound.
GuttaperchaisanisomerofrubberthatisfoundintropicaltreesinsoutheasternAsiaandnorthernAustralasia.Itis
alsoapolyisoprene,butwithEconfigurationatthedoublebond.Guttaperchaisharderandmorebrittlethanrubber.
In1848,thefirstgolfballmadefromguttaperchawasproduceditreplacedthefeatherballswithinafewyearsand
revolutionisedthegame.Becauseitdoesnotreadilyreactwithinthehumanbody,guttaperchaisalsousedfora
varietyofsurgicalapplicationsandisthefillingmaterialthatdentistsuseduringrootcanaltherapy.

Whennaturalrubberlatexwasfirstdiscovered,itwasnotparticularlyuseful.Inhotweatheritbecamesticky,andin
thecolditbecamebrittleandhard.Aftermanyexperimentstoimprovethepropertiesofnaturalrubber,theAmerican
CharlesGoodyeardiscoveredin1839that,byaddingsulfurtotherubberlatexandheating,thepropertiesofrubber
couldbedrasticallyimproved.Henamedhisnewproductvulcanisedrubberandtheprocessiscalledvulcanisation.

Whenrubberlatexistreatedwithsulfur,groupsofsulfuratomsformbridges,socalledcrosslinks,betweenthe
variousstrandsofpolyisoprene.(Undertheconditionsusedtotreatrubber,sulfurexistssubstantiallyaseight
memberedrings,S8.)Themechanismofcrosslinkingiscomplicatedandwillnotbediscussedhere.

Whenthestrandsarelinked,theycannoteasilysliponeachotherwhenitishotsotherubberdoesnotmelt.The
increasedstrengthalsopreventsthepolymerfrombecomingbrittleandeasilybrokenwhencold.Crosslinkingalso
givesthepolymeramemory,whichenablesittosnapbackintoitsoriginalshapewhenreleasedafterbeing
stretchedyouhaveexperiencedthispropertywhenusingrubberbandsorthrowingrubberballs.Theamountof
sulfurusedtovulcanisetherubberlatexalsoaffectsthepropertiesofthefinishedproduct.Ifonlyasmallamountof
sulfur(13%)isused,thepolymerissoftandelastic.Astheextentofcrosslinkingincreases,theproductbecomes
harderandlessresilient.Rubbermadewith310%sulfurisusedinthemanufactureoftyres.Vulcanisedrubberis,
likethediscoveryofTeflon,consideredasoneofthetop10accidentalinventions.

DegradationofPolymers
Polymersareexposedtoconsiderableenvironmentalstress.Forexample,gardenfurniturestartstoloseitsappealing
lookwhenitisleftoutsidethroughouttheyeartheseandother,formerlywhite,plasticsstarttodiscolourafterawhile,
changingtoadirtyyellowcolour,whichnolongerlooksattractive.Otherpolymersbecomebrittleandbreakinto
smallpieces.Obviously,theenvironmentwherecommercialpolymersareusedhasasignificanteffectontheir
lifespan.Inpractice,anychangeinpropertiesofapolymerrelativetotheirinitialdesiredproperties,iscalled
degradation.

Exposureofplasticstosunlightandsomeartificiallightsources(especiallytheUVcomponentofthelight)canrupture
chemicalbondsinthepolymer.Thisprocessiscalledphotodegradationandcanultimatelyleadtocracking,chalking,
discolourationandthelossofotherphysicalproperties,suchaselasticity.Onceachemicalbondinthemoleculeis
broken,freeradicalsareproduced,whichleadtooxidativedegradationofthepolymerinaradicalchainprocessthat
involvesreactionwithoxygeninambientair.Inasimilarway,chemicaldegradationbyatmosphericradicals,suchas
hydroxylradicals(HO),leadstodestructionofthepolymermaterial.

Stabilisersareoftenaddedtopolymerstopreventsuchdegradationreactionsfromoccurring.Phenolicstabilisersare
frequentlyusedbecausetheycanintercepttheradicalchaindegradationprocessthroughdonationofhydrogenatoms
totheintermediateperoxylradicals.Thephenoxylradical,whichisformedduringthisprocess,isunreactive.Thus,the
antioxidanteffectofphenolstabilisers(radicalscavengers)cantransformhighlyreactiveradicalspeciesinto
unreactivecompoundswhichdonotpropagatefurtherradicalchaindegradation.

Socalledhinderedaminelightstabilisers(HALS)areextremelyefficientatstabilisingmostpolymersagainstlight
induceddegradation.Themechanismofthisprocessishighlycomplexandnotyetfullyunderstood.Theadvantages
ofaHALS,comparedwithaphenolicstabiliser,isthatitisconstantlyregeneratedandisnotconsumed,and,therefore,
itprovidesextremelylongtermthermalandlightstabilisationtothepolymer.
Besidesradicalscavengingprocesses,whichdeactivateradicalsthathavealreadyformed,UVlightcanalsobe
absorbedbeforeanydamagetothepolymerchainoccurs.Theconceptusedtoprotectpolymersisthesameasthat
usedtoprotectourskinfromsunburn.SuchUVabsorberscanbeinorganicpigments(suchasTiO2andZnO
ingredientsinsunscreens)ororganiccompoundswhichtransformharmfulUVradiationintothermalenergythrough
photophysicalprocessesthedetailsofthesearebeyondthescopeofthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
26.4SiliconPolymers
Eachpolymerdiscussedsofarisclassifiedasanorganicpolymerbecausethepolymer'sbackbone(the
mainpolymerchain)iscomposedpredominantlyofcarbonatoms,inadditiontosmalleramountsof
nitrogenandoxygenatoms(e.g.polyestersandpolyamides).Themanyapplicationsofthevarious
syntheticorganicpolymersgiveninthischaptermakeitclearthatourliveswouldbeverydifferent
withoutthem.However,organicpolymershavesomegeneraldisadvantages.Forexample,they
typicallybecomebrittlewhencoldanddeterioratewhenveryhot.Theyalsotendtobeflammable,swell
inorganicsolventsandareusuallynotcompatiblewithlivingtissue(forexample,whenusedasa
medicalimplant).Becauseofthis,otherpolymersthatare,forexample,flexibleatlowtemperaturesand
abletowithstandhightemperatureshavebeendeveloped.

Siliconpolymers(silicones)haveabackboneofalternatingsiliconandoxygenatoms,withorganic
groupsattachedtoeachsiliconatom:

Becausethereisnocarboninthebackbone,siliconesareknownasinorganicpolymers.

Siliconpolymersareformedbycondensationpolymerisation,beginningwiththehydrolysisofsilicon
compoundssuchas(CH3)2SiCl2.ThisgivesSiOHbondsthatsubsequentlyundergocondensationto
produceSiOSilinkages:

Dependingonthechainlengthandthedegreetowhichchainsarecrosslinked,siliconescanbeoils,
greasesorrubberysolids.

Siliconeoilrepelswaterandwaterbasedproducts.Forthisreason,ithasbeenusedinfurnitureandcar
polishes,aswaterproofingtreatmentsforfabricsandleather,andforgasketsandsealingringsinjet
engines.Siliconegreasesareusedaspermanentlubricantsinclocksandballbearings.Siliconerubber
hasexcellentelectricalinsulatingpropertiesandsoisusedinelectricmotorsandtocoatelectricalwire.
Theserubberymaterialsalsoretaintheirflexibilityoverwidetemperaturerangesandcanbeusedin
placeofnaturalrubberforbothhighandlowtemperatureapplications.Siliconerubbersmaintaintheir
flexibilityatlowtemperatures,whereotherelastomerssuchasnaturalrubberbecomehardandstiff,
becauseoftheconformationalmotionofthesiliconoxygenbondsinthebackboneofthepolymer.

Siliconpolymershavebecomeimportantmaterialsformedicalimplants,suchasbreastimplants(figure
26.27)usedaftersurgeryorforaugmentation.Therearedifferenttypesofimplantsincludingsaline
implants,whichhaveasiliconeelastomershellandarefilledwithsterilesalineliquid,andsiliconegel
implants,whichhaveasiliconeshellfilledwithaviscoussiliconegel.Inthe1980s,concernswere
raisedthatsiliconeleakingfrombreastimplantscouldincreasetheriskofarangeofconditions,suchas
autoimmunedisordersandevencancer.Despitethecontroversy,thereisnounambiguousevidenceof
anassociationbetweensiliconegelimplantsandincreasedriskofanydiseasescertainvarietiesofboth
siliconeandsalinefilledimplantsareapprovedforuseinAustraliaandNewZealand.

FIGURE26.27Siliconpolymershavemanymedicalapplications,includingtheiruseinbreastimplants.
BridgemanArtLibrary/GabrielCloquemin

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
26.5RecyclingPlastics
Oursocietyisverydependentonpolymersintheformofplastics.Durableandlightweight,plasticsareprobablythe
mostversatilesyntheticmaterialsinexistence.Thereareabout40differentplasticsorpolymersincommonusetoday
Australiaproducesabout1.2milliontonnesayear,andNewZealandabout242000tonnes.Plasticshavecomeunder
criticism,however,fortheircontributiontorubbishthatendsupaslandfill.

Ifthedurabilityandchemicalinertnessofmostplasticsmakethemidealforreuse,whyaremoreplasticsnotbeing
recycled?Theanswertothisquestionhasmoretodowitheconomicsandconsumerhabitsthanwithtechnological
obstacles.InAustraliaandNewZealand,unlikeEuropeandNorthAmerica,recyclingbinsanddropoffstationsfor
recyclableshaveonlyrecentlybecomewidelyestablished(figure26.28)andsotheamountofusedmaterialavailable
forreprocessinghastraditionallybeensmall.Thislimitation,combinedwiththeneedforanadditionalsortingand
separationstep,renderedtheuseofrecycledplasticsinmanufacturingmoreexpensivethanvirginmaterials.
However,increasedrecyclinghasledtogreaterefficienciesofscale,whichbringdowncosts.Inaddition,theincrease
inenvironmentalawarenessoverthelastdecadehasresultedingreaterdemandforrecycledproducts.

FIGURE26.28RecyclingplasticshasbecomeroutineinmosthouseholdsinAustraliaandNewZealand.

Tohelpidentifydifferentplastics,manufacturersstampaplasticsidentificationcodeontheirproducts(figure26.29).
Thecodeisanumberinsideatriangleformedbythreearrows.Themostcommonplasticshavethecodes17andare
shownintable26.2.

FIGURE26.29Aselectionofproductpackagingmanufacturedfromrecycledplastics.
KariAnnTapp

TABLE26.2 IdentificationcodesforplasticsinAustraliaandNewZealand
Plastic
identification
code
New
Australia Zealand Polymer Commonuses Usesofrecycledpolymer
polyethyleneterephthalate
 softdrink softdrinkbottles
bottles (multilayer)detergentbottles
fillingfor clearfilmforpackaging
sleepingbags
carpetfibres
textilefibres
fleecyjackets
highdensitypolyethylene crinkly compostbins
shopping crates
bags
agriculturalpipes
freezerbags
pallets
milkand
rubbishbins
creambottles
furniture
shampoo
bottles cargoliners
milkcrates rulers
packagingmaterials
unplasticisedpoly(vinyl clearcordial detergentbottles
chloride) andjuice tiles
bottles
plumbingpipefittings
blisterpacks
plumbing
pipesand
fittings
plasticisedpoly(vinyl gardenhose hoseinnercore
chloride)
shoesoles industrialflooring
bloodbags
lowdensitypolyethylene lidsofice filmforbuilders,industry,
cream packagingandplant
containers nurseries
garbagebags bags
rubbishbins
blackplastic
sheeting
polypropylene icecream compostbins
containers kerbsiderecyclingcrates
potatochip wormfactories
bags
drinking
straws
hingedlunch
boxes
polystyrene yoghurt clothespegs
containers coathangers
plastic officeaccessories
cutlery
rulers
imitation
CDcases
crystal
glassware
expandedpolystyrene hotdrink synthetictimber
cups
 takeaway
food
containers
meattrays
packaging

includesallotherplastics, carparts concreteaggregate

suchasacrylicandnylon
packaging outdoorfurniture
computers agriculturalpipes
PlasticsandChemicalsIndustriesAssociation

Mostplasticscanberecycled,but,duetothedifficultyincollecting,sorting,cleaningandreprocessing(figure
26.30),itiseconomicallyviabletorecycleonlythreetypesofplasticsfromdomesticsources:PET,HDPE(PEHDin
NewZealand)andPVC(alsoVforvinylinAustralia).Ofthese,HDPEisthemostoftenrecycledplastic.

FIGURE26.30Workersortingrubbishatarecyclingdepot.
ToddMartynJones

Theprocessofrecyclingmostplasticsissimple,withseparationofthedesiredplasticsfromothercontaminantsbeing
themostlabourintensivestep.Forexample,PETsoftdrinkbottles(p.1128)usuallyhaveapaperlabelandadhesive
thatmustberemovedbeforethePETcanbereused.Therecyclingprocessbeginswithhandormachinesorting,after
whichthebottlesareshreddedintosmallchips.Anaircyclonethenremovespaperandotherlightweightmaterials.
Anyremaininglabelsandadhesivesareeliminatedwithadetergentwash,andthePETchipsarethendried.PET
producedbythismethodis99.9%freeofcontaminantsandsellsforabouthalfthepriceofthevirginmaterial.PET
chipscanbemeltedandspunintofibres.Unfortunately,plasticswithsimilardensitiescannotbeseparatedwiththis
technology,andplasticscomposedofseveralpolymerscannotbebrokendownintopurecomponents.However,
recycledmixedplasticscanbemouldedintoplastictimberthatisstrong,durableandresistanttograffiti.

Besidesthesemechanicalmethodsofpolymerrecyclingandpurification,chemicalrecycling(monomerrecycling)
canbeusedtoessentiallyreversethecondensationpolymerisationreactionthatwasusedtocreatethepolymer.This
yieldsthesamemixofchemicalsthatformedtheoriginalpolymer,whichcanbepurifiedandusedtosynthesisenew
polymerchainsofthesametype.Forexample,EastmanKodaksalvageslargeamountsofitsPETfilmscrapbya
transesterificationreaction.Thescrapistreatedwithmethanol(methanolysis)inthepresenceofanacidcatalystto
giveethyleneglycolanddimethylterephthalate,monomersthatarepurifiedbydistillationorrecrystallisationand
usedasfeedstocksfortheproductionofmorePETfilm:

Anotherpotentialoptionforchemicalrecyclingofplasticsistheconversionofassortedpolymersintopetroleum
hydrocarbonsbyasocalledthermaldepolymerisationprocess.Longchainpolymerscontainingcarbon,hydrogen
andoxygenaredecomposedunderpressureandheatintopetroleumhydrocarbonswithchainlengthsofaround18
carbonatoms.Thermaldepolymerisationmimicsthenaturalgeologicalprocessesthatproducedfossilfuels.Thus,like
naturalpetroleum,therecycledchemicalsproducedcanbemadeintofuelsaswellaspolymers.Suchaprocesscould
acceptalmostanypolymerormixofpolymers.

Theproblemsassociatedwithplasticrecyclingcanprincipallybecircumventedbyusingbiodegradablepolymer,
whichcanbebrokendownbyenzymesproducedbymicroorganisms.Thecarboncarbonbondsinchaingrowth
polymersareinerttoenzymecatalyseddegradation,sotheyarenotbiodegradable.However,ifthepolymercontains
smallunitswithbondsthatcanbebrokenbyenzymes,thepolymerisdegradedbymicroorganismsonceitisburied
aswaste.ThepolyesterPET,forexample,canbemadedegradablebyincorporatingaliphaticesterunitsintoits
structurethiscreatesweakspotsinthepolymericchainsandmakesthemsusceptibletodegradationbyhydrolysis.

ChemicalConnections

PolymerBanknotes

Australiaistheworldleaderinthetechnologythatisusedtomakeplasticbanknotes.Aftera21year
researcheffort,Australiareleasedtheworld'sfirstpolymerbanknotein1988(figure26.31).Thetechnology
wasfurtherimprovedinthefollowingyearsandby1996allnotesinAustraliawereplastic.Todaytheyare
usedinmorethan22countriesfromNewZealand(figure26.32)toMexico,andmanymore,includingthe
UnitedStates,areconsideringtheirintroduction.
 FIGURE26.31Theworld'sfirstpolymerbanknote.

FIGURE26.32NewZealandpolymerbanknotes.
AllanBlackman

ThepolymerbanknotetechnologywasdevelopedbytheCSIRODivisionofChemicalsandPolymersand
NotePrintingAustralia(whichisapartoftheReserveBankofAustralia).Theresearchscientistwho
inventedtheplasticnotetechnologywasCSIRO'sDavidSolomon,nowaprofessorialfellowinthePolymer
 ScienceGroupattheUniversityofMelbourne.(Solomoniscurrentlyworkingonapolymerfilmtocover
largewaterstoragestopreventevaporation.)

Traditionalpaperbanknoteswearoutquickly,andtendtodisintegrateiftheygetwet.Theyarealsoeasily
counterfeited.Infact,itwasthewidespreadcounterfeitingofthe$10noteshortlyafterAustraliaconvertedto
decimalcurrencyin1966thatpromptedtheresearchthatledtothedevelopmentofthepolymernote.The
counterfeitingproblembecameworsewiththedevelopmentofhighqualitycolourscannersand
photocopiersthatmadeiteasytoproduceconvincingcounterfeitpapermoney.

Polymernotesaremuchmoredurablethanpaperforexample,theplastic$5notesurvivesalmost3.5years
incirculation,whereastheoldpapernoteslastedonlyabout6months.Interestingly,oncepolymernotesare
takenoutofcirculation,theyareshreddedandthenrecycledintoproductssuchascompostbins.

Polymernoteshaveprovenmuchmoredifficulttocounterfeitthanpapernotes.Thepolymersubstratestarts
asabiaxiallyorientedpolypropylenefilmofatypethatisnotavailablecommercially.Itissuppliedtothe
ReserveBank(RBA)andothercurrencyproducersbyajointventurebetweentheRBAandtheBelgium
basedchemicalfirmUnionChemieBelge.Multiplecoatingsarethenappliedtotheclearfilmtomakeit
opaqueandtoembedsecurityfeaturessuchasdiffractiveopticallyvariabledevices(includingtheimagein
theholographicwindowthatchangesappearancedependingontheviewingangleandthelight).The
polymeralsoallowsmostoftheusualpapernoteprintingtechniquesandfeatures,suchasintricatepatterns
anddetails,seethroughregistration(similartoawatermark),fluorescentfeatures,andtheuseofdifferent
inks.Infact,acombinationofseveraldifferentprintingtechniquesisusedtofurthercomplicateany
counterfeitingattempts.Thenotesarethenfinishedwithaspecialprotectivecoatingtokeepthemcleanand
resistanttomoisture.

Workiscontinuingtodevelopbetterpolymersubstratesandwaystomakecounterfeitingevenmore
difficult.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
TheArchitectureofPolymers
Polymerisationistheprocessofjoiningmanysmallmonomersintohighmolarmasspolymers.The
propertiesofpolymericmaterialsdependonthestructureoftherepeatingunit,aswellasonthechain
architectureandmorphologyofthematerial.

Polymershavedifferentarchitecturesandcanbeclassifiedaslinearorbranched,orhavingacomb,
ladderorstarstructure.Theintroductionofcovalentcrosslinksbetweenindividualpolymerchains
leadstoadditionalstructuralvariations.Thermoplasticsarepolymersthat,whenmelted,become
sufficientlyfluidthattheycanbemouldedintoshapesthatareretainedwhentheyarecooled.
Thermosettingplastics(orthermosets)arepolymersthatcureirreversiblythroughtheadditionofenergy
(asprovidedbyheat,lightorachemicalreaction)toastrongerform.Polymersmaybecomposedof
bothorderedcrystallinedomains(crystallites)anddisorderedamorphousdomains.Therelativeamounts
ofcrystallineandamorphousdomainsdifferfrompolymertopolymerandfrequentlydependonhow
thematerialisprocessed.

PolymerNotationandNomenclature
Whendrawn,thestructureofapolymerisusuallyshownbyplacingparenthesesaroundtherepeating
unit,whichisthesmallestmolecularfragmentthatcontainsallthenonrepeatingstructuralfeaturesofthe
chain.Themostcommonmethodofnamingapolymeristoaddtheprefixpolytothenameofthe
monomerfromwhichthepolymerissynthesised.

FormationofPolymers
Polymersareformedbyvarioustechniques.Stepgrowthpolymerisationsinvolvethestepwisereaction
ofdifunctionalmonomers.Importantcommercialpolymerssynthesisedthroughstepgrowthprocesses
includepolyamides,polyesters,polycarbonates,polyurethanesandepoxyresins.

Chaingrowthpolymerisationproceedsbythesequentialadditionofmonomerunitstoanactiveend
grouponthechain.Radicalchaingrowthpolymerisationconsistsofthreestages:chaininitiation,chain
propagationandchaintermination.Inchaininitiation,radicalsareformedfromnonradicalmolecules.In
chainpropagation,aradicalandamonomerreacttogiveanewradical.Thechainlengthisthenumber
oftimesacycleofchainpropagationstepsrepeats.Inchaintermination,radicalsaredestroyed.New
conceptsenablecontrolledradicalpolymerisation,whichproducespolymerswithdefinedarchitecture
andlowpolydispersity.ZieglerNattachaingrowthpolymerisationsformanalkyltransitionmetal
compoundthenalkenemonomersarerepeatedlyinsertedintothetransitionmetalcarbonbondtoyield
asaturatedpolymerchain.

ModifiedZieglerNattacatalystsallowthestereoregularpolymerisationofunsymmetricalalkenes,such
aspropene.Thisleadstoisotactic,atacticandsyndiotacticpolypropylenes,whichhavedifferent
arrangementsofthemethylgrouponthecarbonpolymerchainand,therefore,differentchemicaland
physicalproperties.

Cationicpolymerisations,usuallyofelectronrichalkenes,areinitiatedbycationicreagentsthatgive
carbocations,whichactaspolymerisationchaincarriers.Thechainisterminatedbyreactionwitha
nucleophile,usuallyananion.

Anionicpolymerisationreactionsusuallyuseelectrondeficientalkenes,whichcanstabilisenegatively
chargedintermediates(throughresonance,forexample).Thesepolymerisationsareinitiatedbyaddition
ofanucleophile(suchasametallorganiccompound)togivecarbanions,whichactaschaincarriers.
Anionicpolymerisationreactionshavenoformalterminationpathway,butreactionswithelectrophilic
specieswhichmaybepresentasimpuritiesusuallyleadtotermination.

Naturalrubberisapolymerofisoprene,whichisstickyathightemperaturebutbrittleandhardwhenit
iscold.Itspropertiescanbeimprovedbyvulcanisation,aprocessbywhichthepolyisoprenechains
becomecrosslinkedwithsulfurchains.Theamountofsulfurinvulcanisedrubberdeterminesits
propertiessmallamountsmakethepolymerelasticmoreincreasesthenumberofcrosslinks,
makingtherubberhardandlessresilient.

SiliconPolymers
Siliconpolymershaveanoncarbonbackbonethatconsistsofsiliconandoxygenatoms.Theymaintain
theirflexibilityevenatverylowandveryhightemperatures.Becauseoftheirchemicalresistance,they
areusedinmedicalapplicationssuchasimplantmaterials.

RecyclingPlastics
Recyclingincreasesthelifeofplastics,eitherbymechanicaldegradationandmeltingintoanewshape
orbychemicalrecyclingthroughdepolymerisationtechniques.Aplasticsidentificationcodeisusedto
helpidentifydifferentplastics.Biodegradablepolymersaremodifiedpolymersthatcontainlabileunits
thatcanbeenzymaticallydegradedbymicroorganisms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Polymerisationreactionsformingcondensationorstepgrowthpolymers(section26.3)
Inthispolymerisationtechnique,asmallmoleculeisusuallyeliminatedwhenthetwomonomerunits
arejoined.Thestructureofthepolymercanbepredictedfromthestructureofthemonomers.

Polymerisationreactionsformingadditionorchaingrowthpolymers(section26.3)
Inthispolymerisationtechnique,twomonomerunitsarejoinedwithoutthelossofatoms.Thestructure
ofthepolymercanbepredictedfromthestructureofthemonomers.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
TheArchitectureofPolymers
26.1Whyarebranchedpolymersmoreflexiblethanlinearpolymers?
26.2Giveoneexampleeachofpolymerswithchainsthatareassociatedbyeachofthefollowing.
(a)vanderWaalsforces
(b)hydrogenbonding
(c)stackingofaromaticrings
26.3Listthedifferencesbetweenthermosettingandthermoplasticpolymers.
26.4Whatareelastomers?
Polymernotationandnomenclature
26.5Thefollowingarestructuralformulaeforsectionsoftwopolymers:
(a)

(b)

Fromwhatalkenemonomeriseachpolymerderived?
26.6Drawachainofthreesegmentsofeachofthefollowingpolymers.
(a)Teflon
(b)poly(vinylfluoride)
(c)polyacrylonitrile
26.7Whatistherepeatingunitinthepolymersinquestion26.6?
FormationofPolymers
26.8Explainthegeneraldifferencebetweenstepgrowthandchaingrowthpolymers.
26.9Whyisaninitiatorrequiredinchaingrowthpolymerisations?
26.10Whyarecationicpolymerisationsgenerallyperformedwithelectronrichalkenes?
26.11Whyareanionicpolymerisationsusuallyperformedwithelectronpooralkenes?
26.12Explainthestructuraldifferencebetweenatactic,isotacticandsyndiotacticpolypropylene.
26.13Explainthebackbitingmechanismthatleadstobranchinginthepolymerisationofethene.
SiliconPolymers
26.14Outlinethegeneralstructureofasiliconpolymer.
26.15Whyaresiliconpolymersmoreflexiblethancarbonbasedpolymersatlowtemperature?
RecyclingPlastics
26.16Explainthedifferencebetweenmechanicalandchemicalrecyclingofpolymers.
26.17Whatisthedifferencebetweenbiodegradableandnonbiodegradablepolymers?1
26.18Whatisthemainwayofmakingapolymerbiodegradable?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
26.19Considerthefollowingpolymer.

(a)Identifywhatmonomersyouwouldusetomakethispolymer.
(b)Whichtypeofbondlinksthemonomerunitstogether?
(c)Wouldyouuseacidicconditionsorbasicconditionsforthispolymerisationprocess?
26.20Identifythemonomersrequiredforthesynthesisofeachofthefollowingstepgrowthpolymers.
(a)

(b)

(c)

(d)

26.21Drawthestructureofthealkenemonomerusedtomakeeachofthefollowingchaingrowth
polymers.
(a)
 (b)

(c)

(d)

26.22Poly(ethyleneterephthalate)(PET)canbepreparedbythefollowingreaction.Proposea
mechanismforthestepgrowthreactioninthispolymerisation.

26.23Polyethylenecanbeusedfortheproductionofsolidfoodcontainersaswellasflexiblecling
film.Whichofthesetwoitemsismadefrommorehighlybranchedpolyethylene?Explain.
26.24Nomex isanaromaticpolyamide(aramid)preparedbythepolymerisationof1,3
benzenediamineandtheacidchlorideof1,3benzenedicarboxylicacid:

Thephysicalpropertiesofthepolymermakeitsuitableforhighstrength,hightemperature
applicationssuchasparachutecordsandjetaircrafttyres.Drawthestructuralformulaforthe
repeatingunitofNomex.
26.25Nylon6,10(seequestion26.20d)canbepreparedbyreactingadiamineandadiacidchloride.
Drawthestructuralformulaofeachreactant.
26.26Thefollowingisthestructuralformulaofasectionofpolypropylenecorrespondingtothreeunits
ofthepropenemonomer:
 Drawthestructuralformulaforacomparablesectionof:
(a)poly(vinylchloride)
(b)polytetrafluoroethylene(PTFE)
(c)poly(methylmethacrylate).
26.27Currently,about30%ofPETsoftdrinkbottlesarebeingrecycled.Inonerecyclingprocess,
scrapPETisheatedwithmethanolinthepresenceofanacidcatalyst.Themethanolreactswith
thepolymer,liberatingethyleneglycolanddimethylterephthalate.Thesemonomersarethen
usedasfeedstockfortheproductionofnewPETproducts.Writeanequationforthereactionof
PETwithmethanoltogiveethyleneglycolanddimethylterephthalate.
26.28LDPE(PELD)hasahigherdegreeofchainbranchingthanHDPE(PEHD).Explainthe
relationshipbetweenchainbranchinganddensity.
26.29Polymerisationofvinylacetategivespoly(vinylacetate).Hydrolysisofthispolymerinaqueous
sodiumhydroxidegivespoly(vinylalcohol).Drawtherepeatingunitsofbothpoly(vinylacetate)
andpoly(vinylalcohol).

26.30Poly(vinylalcohol)ismadebythepolymerisationofvinylacetate,followedbyhydrolysisin
aqueoussodiumhydroxide(seequestion26.29).Whyispoly(vinylalcohol)madebythis
processandnotbythepolymerisationofvinylalcohol,CH2 CHOH?
26.31Considerthefollowingthreepolymers.

(a)Whichdoyouexpecttobethemostrigid?
(b)Whichdoyouexpecttobethemosttransparent?(Assumeequalmolarmasses.)
26.32Thestructureofvinylacetateisshowninquestion26.29.Thiscompoundformsanaddition
polymerinthesamewayasetheneandpropene.Drawasegmentofthepoly(vinylacetate)
polymerthatcontainsthreeoftherepeatingunits.
26.33IfthefollowingtwocompoundspolymerisedinthesamewaythatPETforms,whatwouldbethe
repeatingunitoftheirpolymer?
26.34Ifthefollowingtwocompoundspolymerisedinthesamewaythatnylonforms,whatwouldbe
therepeatingunitinthepolymer?

26.35Listthecompoundsineachofthefollowinggroupsofmonomersinorderofincreasingabilityto
undergocationicpolymerisation.
(a)

(b)

Now,listeachgroupofcompoundsinorderofdecreasingabilitytoundergoanionic
polymerisation.
26.36Drawasegmentof(a)poly(vinylchloride)and(b)polystyrenethatcontainsheadtoheadand
tailtotaillinkages,ratherthanthenormalheadtotaillinkages.
26.37Whichpolymerwouldbemorelikelytoformsegmentswithheadtoheadlinkages:polystyrene
orpoly(vinylchloride)?
26.38Whichmonomersarerequiredtoformeachofthefollowingpolymers.Caneachofthese
polymersbemadefromonesingletypeofmonomer?
(a)

(b)

(c)
 (d)

26.39Drawashortsegmentofnylon5.
26.40Drawashortsegmentofnylon5,5.
26.41WhathappenstoaTshirtmadeofpolyesterifaqueousNaOHisspilledonit?
26.42Drawtherepeatingunitofthepolymersderivedfromeachofthefollowingmonomers.
(a)

(b)

(c)

(d)

(e)

(f)

26.43Explainwhypoly(isobutylene)isnotisotactic,syndiotacticoratactic.
26.44Quianaisasyntheticpolymerthatcanbeusedtomakefabricthatmimicsthetextureofsilk.It
canbepreparedfromthefollowingmonomers.
 (a)DrawthestructureofQuiana.
(b)IsQuianaapolyester,apolyamide,apolycarbonateorapolyurethane?
(c)IsQuianaastepgrowthpolymerorachaingrowthpolymer?
(d)IsQuianaanadditionpolymeroracondensationpolymer?
26.45Drawthestructureofthemonomerormonomersusedtosynthesisethepolymerswitheachof
thefollowingrepeatingunits.Indicatewhethereachpolymerisachaingrowthorastepgrowth
polymer.
(a)

(b)

(c)

(d)

(e)
 (f)

26.46Polystyreneisformedbyaddingasmallamountofaperoxidetostyrene.Ifasmallamountof
1,4divinylbenzeneisaddedtothereactionmixture,astrongerandmorerigidpolymeris
formed.Explainthereasonforthis.Drawasmallsegmentofthismorerigidpolymer.

26.47Astudenthasstartedtwopolymerisationreactions.Achaingrowthpolymerisationisoccurring
inoneflaskandastepgrowthpolymerisationinanotherflask.Bothreactionsareterminated
earlyinthepolymerisationprocessandthecontentsoftheflasksareanalysed.FlaskAcontainsa
highmolecularmasspolymerandverylittlematerialofintermediatemassflaskBcontains
mainlymaterialwithintermediatemassandverylittlehighmolecularmasspolymer.Whichtype
ofpolymerisfoundineachflask?Explainyouranswer.
26.48Polyformaldehyde,soldunderthetradenameDelrin,isastrongpolymerusedinthe
manufactureofmanyguitarpicks.Itispreparedviatheacidcatalysedpolymerisationof
formaldehyde.
(a)Drawthestructureofpolyformaldehyde.
(b)Wouldyoudescribepolyformaldehydeasapolyetherorapolyester?
(c)Ispolyformaldehydeastepgrowthpolymerorachaingrowthpolymer?
26.49Whenasolutionofaqueoussodiumhydroxideisspilledonpolyesterclothing,aholedevelops
inthefabric.Describehowthepolyesterisdestroyed.
26.50Aclingwrapissynthesisedthroughchaingrowthcopolymerisationof1,1dichloroetheneand
vinylchloride(chloroethene).Drawashortsegmentofthepolymerchain.
26.51Plexiglasisatransparentplasticwithexcellentopticalproperties.Itispolymerisedfrommethyl
methacrylateusingfreeradicalinitiation.Writethemechanismfortheradicalpolymerisationof
methylmethacrylatetogivethreesegmentsofpoly(methylmethacrylate).

26.52Considerthestructureofpolystyreneonp.1122.
(a)Drawstructuralformulaeforsegmentsofthechainsofisotactic,syndiotacticandatactic
 polystyrene.
(b)Ifsolutionsofeachoftheseformsofpolystyrenearemade,whichwouldyouexpectto
showopticalactivity?
26.53Whenethyleneoxideistreatedwithastrongnucleophile,theepoxideringisopenedtoforman
alkoxideionthatcanfunctionasanucleophiletoattackanothermoleculeofethyleneoxide.This
processrepeatsitself,andapolymerisformed.

Theresultingpolymeriscalledpoly(ethyleneoxide)orpoly(ethyleneglycol).Itissoldunderthe
tradenameCarbowaxandisusedasanadhesiveandathickeningagent.
(a)Drawamechanismshowingtheformationofasegmentofpoly(ethyleneoxide).
(b)Ethyleneoxidecanalsobepolymerisedwhentreatedwithanacid.Drawthemechanism
offormationofasegmentofpoly(ethyleneoxide)underacidicconditions.
(c)Identifythemonomeryouwouldusetopreparethefollowingpolymer.

(d)Determinewhetheryouwouldusebasicconditionsoracidicconditionstopreparethe
followingpolymer.Explainyourchoice.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
26.54Isarepeatingunitrequiredforacompoundtobecalledapolymer?
26.55Additionofasmallamountofglycerol(propane1,2,3triol)tothereactionmixtureoftoluene
2,6diisocyanateandethyleneglycolduringthesynthesisofapolyurethanefoamproducesa
muchstifferpolymer.Explainthisfinding.

26.56Unsaturatedestersandacrylonitrilearesuccessfullypolymerisedusingfreeradicaloranionic
initiation.However,polymerisationdoesnotoccurwhencationicinitiatorsareused.Explain.

26.57Whichpolymershouldbemoreresistanttostrongbase:nylon6,6orthepolyesterinquestion
26.45a?Explain.
26.58Guttaperchaisnotveryelastic,evenafteritisvulcanised.Explain.
26.59Glyptalisaparticularlystrongpolymerusedtomakeelectronicparts.Itismanufacturedfrom
phthalicacid(1,2benzenedicarboxylicacid)andglycerol.Drawasmallsegmentofthepolymer
andexplainwhyitissostrong.
26.60Poly(vinylpyrrolidone)wasonceusedasanextenderforbloodplasma.

(a)Whichmonomerisusedforthesynthesisofthispolymer?
(b)Wouldyousynthesisethispolymerusingfreeradicalinitiationorcationicinitiation?
Explain.
(c)Proposeamechanismforthepolymerisationofasegmentconsistingofthreerepeating
units.
(d)Poly(vinylpyrrolidone)clearlycontainsamidelinkages.Isthis,therefore,apolyamide?
Explain.
26.61Atypicalpolyurethanecanbemadebypolymerisingadipicacidwithexcessethyleneglycol.
Theresultingpolyesteristhentreatedwithtoluene2,6diisocyanate(seequestion26.55).
(a)Drawasegmentofthepolyester.
(b)Drawasegmentofthepolyurethane.
(c)Whyisexcessethyleneglycolusedinmakingthepolyester?
26.62Nitroethene,CH2 CHNO2,isaverylabilecompoundthatmustbepreparedwithcare.If
purificationofnitroetheneisattempted,generallyonlysmallamountsarerecovered,butthe
innerwallsofthedistillationapparatusarecoveredwithawhitefilm.Explain.
26.63Drawthestructureoftherepeatingunitofapolyurethanepreparedbyreactionofglycerolwith
methanediphenyldiisocyanate(MDI).

26.64Poly(vinylchloride),PVC,isusedforrigidstructuressuchaswindowframes.IfPVCisusedfor
moreflexibleproductssuchasplasticbags,about2030%dialkylphthalates,suchasthe
compoundshownbelow,areincorporatedduringpolymerisation.Explain.

26.65Neoprene(shownbelow)isachemicallyinertpolymerofchloroprene.Itisusedinmany
applications,suchaswetsuits.
(a)Drawthestructureofthemonomerofneoprene.
(b)NamethemonomerchloropreneaccordingtotheIUPACrules.

26.66 (a)Describethetypeofisomericpossibilitiesinthefreeradicalpolymerisationofstyrene?
 Drawstructuresofanypossibleisomers.
(b)Wouldthefreeradicalpolymerisationofstyrenedistinguishbetweentheisomer
possibilitiestofavourone?
26.67Drawthestructure(repeatingunit)ofthepolymerthatwouldbeformedfrom1,5pentanedioic
acidandethyleneglycol.Whatfunctionalgroupslinktheunitsofthechain?
26.68Whatwouldhappeninthepolymerisationofnylon6,6ifadipicacid(1,6hexanedioicacid)
containedaceticacidasanimpurity?
26.69 (a)Drawseveralsegmentsofthestructureofneoprene(polychloroprene).Notethatthe
doublebondhasEconfiguration.

(b)DrawseveralsegmentsofthestructureofthepolymerchainwithZconfigurationatthe
doublebond.Suggesthowthischangeinstereochemistryatthedoublebondmightaffect
thepropertiesofthispolymer.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
additionpolymerisation crosslinks Polyesters
alternating crystallinedomains polymer
amorphousdomains degradation additionpolymerisation
antioxidant elastomers Polyurethanes
aramid epoxyresins Radicalchaingrowth
atacticpolypropylene fishhook(singleheaded) polymerisation
biodegradablepolymers arrows radicals
biopolymers highdensitypolyethylene repeatingunit
block (HDPEorPEHD) Siliconpolymers
cationicpolymerisation isotacticpolypropylene silicone
Chaininitiation lowdensitypolyethylene statistical
chainlength (LDPEorPELD) stepgrowthpolymerisation
Chainpropagation macromolecules syndiotacticpolypropylene
Chaintermination melttransitiontemperature thermoplastic
chaingrowthpolymerisation (Tm) thermosettingplastic
chaintransferreaction monomers vulcanisation
condensationpolymerisation Naturalrubber vulcanisedrubber
photodegradation ZieglerNattacatalysts
plastic
polyamides
Polycarbonates

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

27 NuclearChemistry
LifeonEarthispredominantlysolarpowered.Aswesawinchapter12,greenplantsusesolarphotonswith
wavelengthsinthevisibleregionasanenergysourcetoconvertcarbondioxideandwatertocarbohydrates,
whichultimatelyprovidethebasisforessentiallyalllife.Butfromwheredothesolarphotonsobtaintheir
energy?Theanswertothisquestionisfoundintheatomicnucleus.OurSunispoweredbynuclearreactions
(asshowninthephotobelow)whichinvolvethefusingofhydrogennucleitogiveheliumnucleiunder
conditionsofextremelyhightemperatureandpressure.Thisnuclearprocessconsumesaquiteastonishing
600milliontonnesofhydrogenpersecondandemitsanenormousamountofenergy.Anotherpossible
energysourceinvolvingtheatomicnucleusarisesfromthefactthatsomeheavyatomicnucleiarealso
inherentlyunstableandbreakaparttogivelighternuclei,againwiththeemissionofsignificantamountsof
energyavariationofthisprocessisusedintheproductionofnuclearpower.Inthischapter,wewilldiscuss
someoftheprocesseswhichoccurinatomicnuclei.Wewillinvestigatewhysomenucleiarestableandsome
areradioactive,andwewilldetailsomeoftheusesofradioactivematerials.

KEYTOPICS

27.1Nuclearstability
27.2Unstablenuclei
27.3Synthesisofnewelements
27.4Radioactivedatingmethods
 27.4Radioactivedatingmethods
27.5Applicationsofnuclearprocesses

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
27.1NuclearStability
Asdescribedinchapter1,atomicnucleicanbedividedintotwotypes:stableandradioactive.Radio
activenucleiundergospontaneousdecay,andthereforewesaythattheyareunstable.However,before
webeginourdiscussionofnuclearstability,wemustfirstdefineexactlywhatwemeanbytheword
stableinthecontextofanatomicnucleus.Thisismosteasilydonebydefiningitsopposite,unstable.
Asanexample,considertheradioactiveneodymiumnucleus144Nd.Thishasahalflifeof2.2910 15
years.Aswelearnedinchapter15,thismeansthatanysampleofthisisotopedecaysbyhalfoverthis
period,andittakes2.2910 16yearstodecaycompletely.Theselengthsoftime,byoureveryday
standards,arealmostincomprehensible(indeedtheyareaboutamilliontimestheageoftheuniverse!).
Tous,asampleof144Ndwouldshownoobviouschangeandappeartobestableovertheperiodofour
lifetime.Despitethis,westillsaythatthe144Ndnucleusisunstable,eventhoughitsrateofdecayis
extremelyslow.Thereareradioactivenucleiwithhalflivesoffractionsofasecondandotherswith
halflivesof10 19years,buttheyareallunstableastheyallundergoanuclearprocessthatresultsin
theirradioactivedecay.Therefore,astablenucleusisoneinwhichsuchnuclearprocessesdonotoccur.

Oneoftheimportantfactorsthatdetermineswhetherornotaparticularnucleusisstableistheratioof
protonstoneutronsinthenucleus.Thisisevidentwhenweconsiderfigure27.1,whichshowsallthe
stablenucleionaplotofthenumberofneutrons(N)versusthenumberofprotons(Z).Thesedatahave
adefinitepatternthatshowsthatallstablenucleifallwithinabandofstability(theshadedregionin
figure27.1).Anynucleuswitharatioofneutronstoprotonsthatfallsoutsidethebandofstabilityis
unstableanddecomposesspontaneously.LighternucleilieonorclosetotheN=Zline,but,asthe
atomicnumberincreases,theN:Zratioofstablenucleirisesslowlyuntilitreaches1.54.Thetrendis
illustratedbytheN:Zratios(inparentheses)ofthefollowingstablenuclei:
.
 FIGURE27.1PlotofnumberofneutronsversusnumberofprotonsforalltheelementsfromH(Z=1)toPb(Z
=82).Thenumbersinsquareboxesindicatemagicnumbers(seep.1163).

Theattractiveforcethatholdsthenucleustogetheriscalledthestrongnuclearforceitactsbetween
protonsandneutronsandoperatesthroughtheexchangeofsubatomicparticlescalledmesons.The
strongnuclearforceoperatesonlyatverysmalldistancestoholdprotonsandneutronstogetherwithin
thenucleus,and,atthesedistances,itisabout100timesstrongerthanprotonprotonrepulsion.AsZ
increases,theeffectofelectricalrepulsionincreases,and,therefore,moreneutronsarerequiredto
generateenoughnuclearforcetostabilisethenucleus.Thisaccountsforthegradualincreaseinthe
slopeoftheplotinfigure27.1.However,whenZincreasesbeyondacertainpoint,addedneutronscan
nolongerstabilisethenucleus,andthisissuggestedinfigure27.1bythefactthattherearenostable
nucleibeyondlead,Z=82(the nucleuswas,formanyyears,thoughttobestable,butwasshown
in2003toundergoalphadecay,withahalflifeof1.910 19years).SomeelementswithhigherZare
foundonEarth,notablyradium(Z=88),thorium(Z=90)anduranium(Z=92),butallsuchelements
areunstable(alltheirisotopesareradioactive)andeventuallydisintegrateintonucleiwithZ<83.
Consequently,thesetofstablenuclei,thosethatmakeuptheworldofnormalchemistryandprovide
thematerialforallterrestrialchemicalreactions,isasmallsubsetofallpossiblenuclei.Careful
inspectionoffigure27.1showsthattherearenostablenucleihavingZ=43orZ=61.These
correspondtotheelementstechnetium(Tc)andpromethium(Pm),neitherofwhichoccursnaturallyon
Earth.The(relatively)shorthalflivesofallknownisotopesoftheseelementsmeansthatanyoriginally
presentonEarthhavedecayedovertheintervening4billionyears.

Althoughstablenucleidonotundergospontaneousradioactivedecay,notallstablenucleiareequally
stableinotherwords,theydonotallhavethesameenergy.Wecaninfactcalculatethenuclear
bindingenergy,theenergythatholdsthenucleustogether.Wedothisusingthemostwellknown
equationinallofscience,Einstein'sequationE=mc2,whichquantifiestheequivalenceofmassand
energy.Thekeytothiscalculationistheaccuratemeasurementofthemassofanatomicnucleus,and
alsothemassesofthecomponentsoftheatomicnucleus,theprotonandtheneutron.Ifweaddthe
massesoftheindividualprotonsandneutronsinanatomicnucleus,wefindthatitalwaysaddsupto
slightlymorethantheactualmassofthenucleusitself.Themassdifference(sometimescalledthemass
defect)isduetomassthatisconvertedtoenergyonformationoftheatomicnucleusfromits
components,andwecancalculatethisliberatedenergyusingEinstein'sequation.Ifwewishedtobreak
thenucleusapartintoitsconstituentnucleons,i.e.protonsandneutrons(seep.8),wewouldneedto
supplyanamountofenergyequaltothenuclearbindingenergytherefore,thegreaterthenuclear
bindingenergy,themorestablethenucleus.Thecalculationisillustratedinworkedexample27.1.

WORKEDEXAMPLE27.1

CalculatingtheNuclearBindingEnergy

The nucleusconsistsoftwoprotonsandtwoneutrons.Usethefollowingdatato
calculatethenuclearbindingenergyofthe nucleus.

Analysis

Wearegiventhemassofthe nucleus,aswellasthoseofaprotonandaneutron.We
startbycalculatingthemassoftwoprotonsandtwoneutrons,andcomparingthiswiththe
actualmassofthe nucleustodeterminethemassdefect.WethenuseEinstein'sequation
toconvertthemassdefecttotheequivalentenergy,whichisthenuclearbindingenergy.

Solution

Wecancalculatethemassdefectasfollows:

BeforewecanuseEinstein'sequation,wemustconvert0.030377uintokg.Weusethe
conversionfactor1u=1.6605410 27kgtocalculatethat0.030377u=5.044210 29
 kg.Knowingthatthespeedoflight,c,=2.99810 8ms1,wecannowcalculatetheenergy
equivalentof5.044210 29kgusingEinstein'sequation:

Thisisthenuclearbindingenergyofasingle nucleus.Inotherwords,formationofone
nucleusfromtwoisolatedprotonsandtwoisolatedneutronsreleases4.53410 12J,
whichappearstobeanegligibleamountofenergy.However,whenweconvertthistothe
amountofenergyreleasedonformationof1mole(4g)of nucleifromitsconstituent
nucleons,weobtainavalueof2.7310 12J,equivalenttotheenergycontainedin650
tonnesofthehighlyexplosiveTNT.

Isouranswerreasonable?

Inpredominantlyarithmeticalproblemslikethis,wecanonlycheckthatwehavesubstituted
thecorrectnumbersintotheequationsandcarriedoutthearithmeticcorrectly.Whilethe
amountofenergyliberateddoesseemextraordinary,wehavedoneallmanipulations
correctlyandwecanthereforebeconfidentoftheanswer.

PRACTICEEXERCISE27.1
Themassofthe nucleusis3.014932u.
Calculatethenuclearbindingenergyof1
moleofthisnucleus.

Youcanseefromworkedexample27.1thattheenergiesinvolvedintheatomicnucleusaresubstantial.
Shouldweeverbeabletoharnessthoseenergiesinacontrollableway,wewouldhaveavirtually
limitlesssourceofenergy.Therearetwopossiblenuclearprocessesthatwecanexploitassourcesof
energy.Nuclearfusionisthejoiningtogetheroflightnucleitoformheaviernuclei,whilenuclear
fissionisthesplittingofheavynucleiintonucleioflowermassnumber.Bothprocessesproduce
significantamountsofenergy.

Calculationsshowthat,asthemassnumberincreases,sodoesthenuclearbindingenergyofthe
nucleus.However,thebindingenergypernucleonismoreimportantfortheoverallstabilityofthe
nucleus.Thisquantityisthenuclearbindingenergydividedbythemassnumber,A,anditmeasures
howtightlyeachnucleonisboundtothenucleus.Asthebindingenergypernucleonbecomesmore
positive,nucleibecomeenergeticallymorestable.Figure27.2showsthebindingenergypernucleon
plottedversusmassnumber.
 FIGURE27.2Bindingenergiespernucleon.TheenergyunithereisthemegaelectronvoltorMeV(1MeV=
1.6021013 J).

Thecurveinfigure27.2reachesamaximumat ,whichmeansthatthesenucleiarethemost
energeticallystableofall.However,theplotdoesnothaveasharpmaximum,soelementswithmass
numbersintherange50to80containthemostenergeticallystableisotopesinnature.Lighternuclei
are,therefore,moreunstablethantheseandwewouldexpectsuchnucleitoundergofusionreactionsto
approachtheregionofgreateststability.Fusionreactionsdoinfactoccurinstarsandithasbeen
proposedthatalltheelementsonEarthuptoandincluding areproductsofsuchreactions.Aswe
continuetofollowtheplotoffigure27.2tothehighestmassnumbers,thenucleidecreaseinstabilityas
thebindingenergiespernucleondecrease.Amongtheheaviestatoms,therefore,wewouldexpectto
findisotopesthatchangetomorestableformsbybreakingupinfissionreactions.

Carefulinspectionoffigure27.1showsthat,whenthenumbersofneutronsandprotonsinanucleusare
botheven,theisotopeisfarmorelikelytobestablethanwhenbothnumbersareodd.Ofthe263stable
isotopes,onlyfivehaveoddnumbersofbothprotonsandneutrons,whereas157haveevennumbersof
both.Theresthaveanoddnumberofonenucleonandanevennumberoftheother.Toseethis,notice
how,infigure27.1,thehorizontallineswiththelargestnumbersofdarksquares(stableisotopes)most
commonlycorrespondtoevennumbersofneutrons.Similarly,theverticallineswiththemostdark
squaresmostoftencorrespondtoevennumbersofprotons.Thisisrelatedtothespinsofnucleons,a
conceptanalogoustoelectronspin,whichwefirstencounteredinchapter1.Protonsandneutronsalso
behaveasthoughtheyhavespin,and,whentwoprotonsortwoneutronshaveoppositespins(paired),
theircombinedenergyislowerthanwhenthespinsarethesame(unpaired).Onlywhenthereareeven
numbersofbothprotonsandneutronscanallspinsbepaired,therebyresultinginalowerenergy
nucleus.Therefore,theleaststablenucleitendtobethoseinwhichthenumberofprotonsandneutrons
areodd.

Anotherruleofthumbfornuclearstabilityisbasedonmagicnumbersofnucleons.Isotopeswith
specificnumbersofprotonsorneutrons,themagicnumbers,aremorestablethantherest.Themagic
numbersofnucleonsare2,8,20,28,50,82and126,andfigure27.1shows,withtheexceptionof
number126,wheretheyfall.Whenthenumbersofbothprotonsandneutronsarethesamemagic
number,astheyarein ,theisotopeisverystable.Theheaviestknownstableisotope,
,involvestwodifferentmagicnumbers,82protonsand126neutrons.Theexistenceofmagic
numberssupportsthehypothesisthatanucleushasashellstructurewithenergylevelsanalogousto
electronenergylevels.Electronlevels,aswehaveseen,areassociatedwiththeirownspecialnumbers,
thosethatequalthemaximumnumberofelectronsallowedinaprincipalenergylevel:2,8,18,32,50,
72and98(forprincipalquantumnumbersn=1,2,3,4,5,6and7,respectively).Thetotalnumbersof
electronsintheatomsofthemostchemicallystableelementsthenoblegasesalsomakeupa
specialset:2,10,18,36,54and86electrons.Thus,specialsetsofnumbersarenotuniquetonuclei.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
27.2UnstableNuclei
Wehaveseeninfigure27.1thattherearerelativelyfewcombinationsofprotonsandneutronsthatgiverise
tostablenuclei.AnyotherN:Zratiosgiveunstablenucleiinwhicheitherthenumberofneutronsorthe
numberofprotonsistoogreat.Theseunstablenucleispontaneouslyundergoradioactivedecaytogive
nucleiwithmorefavourableN:Zratios.Thereareanumberofpossibleradioactivedecaypathsavailableto
anunstableatomicnucleusandwesummarisetheseonthenextfewpages.

AlphaDecay
Wefirstmentionedalphaparticlesinchapter1whenwediscussedRutherford'sgoldfoilexperiment.An
alphaparticleisaheliumnucleus,comprisingtwoprotonsandtwoneutrons,andissymbolisedas .It
hasa2+charge,althoughthisisusuallynotincludedinthesymbol.Alphaparticlesarethemostmassiveof
anycommonlyemittedbyradionuclides.Whenejectedfromthenucleus,alphaparticlesmovethroughthe
atom'selectroncloud,reachingemergingspeedsofuptoonetenththespeedoflight.Theirsize,however,
preventsthemfromgoingfar.Bythetimetheyhavetravelledatmostonlyafewcentimetresinair,alpha
particleshavecollidedwithmoleculesintheair,lostkineticenergy,pickedupelectronsandbecomeneutral
heliumatoms.Alphaparticlescannotpenetratetheskin,althoughenoughexposurecausesasevereskin
burn.However,ifaradioactivesubstancethatemitsalphaparticlesisinhaledoringested,itcanendupin
thesofttissuesofthelungsortheintestinaltractandcancauseseriousharm.Thiswasgraphicallyillustrated
bythedeathoftheRussianexpatriateAlexanderLitvinenko,whowaspoisonedbythealphaemitter210Po
inLondoninlate2006.

Whenanucleusemitsanalphaparticle,Zdecreasesby2,andtheatomisconvertedtoanotherelement.
AlphadecayisthepreferreddecaymethodofmostnucleihavingZ>82.Wecanillustratethisdecay
processusinganuclearequation,which,incontrasttoabalancedchemicalequation,requiresonlythat
bothAandZarebalancedoneithersideofthearrow.Thus,wecanshowthealphadecayoftheuranium
isotope as:

Noticethattheproductofalphadecayisadifferentchemicalelement,withanatomicnumber2lessthan
thatoftheparentnucleus.Ageneraldiagramofalphadecayisgiveninfigure27.3.

FIGURE27.3Emissionofanalphaparticlefromanatomicnucleus.

BetaDecay
Abetaparticleissimplyanelectron.Innuclearchemistry,itissymbolisedas .Itmayseemsomewhat
counterintuitivetosaythatanatomicnucleuscandecaybyemissionofanelectron,butthisonlyservesto
showtheextraordinaryworkingsofthenucleus.And,infact,betadecayinvolvesmorethanjustthe
emissionofabetaparticleaparticlecalledanantineutrinoisalsoejected.Incontrasttoalphaparticles,
whichareallemittedwiththesamediscreteenergyfromagivenradionuclide,betaparticlesemergefroma
givenbetaemitterwithacontinuousrangeofenergiesfromzerotoacharacteristicfixedupperlimitforeach
radionuclide.Thisfactoncegavenuclearphysicistsconsiderabletrouble,partlybecauseitwasanapparent
violationofenergyconservation.Tosolvethisproblem,WolfgangPauli(19001958,NobelPrizein
physics,1945)proposedin1927thatbetaemissionisaccompaniedbyyetanotherdecayparticle,thisone
electricallyneutralandalmostmassless.EnricoFermi(19011954,NobelPrizeinphysics,1938)suggested
thenameneutrino(littleneutralone),buteventuallyitwasnamedtheantineutrino,symbolisedas .

Wewillillustratebetadecaywithreferencetotritium,theradioactiveisotopeofhydrogen:

Theemittedbetaparticleandantineutrino (figure27.4)actuallyariseasaresultoftheconversionofa
neutrontoaprotoninthedecayprocessasfollows:

Theentiredecayprocessisdepictedinfigure27.4.

FIGURE27.4Emissionofabetaparticlechangesaneutronintoaproton.Thisresultsinapositivelychargedion,
whichpicksupanelectrontobecomeaneutralatom.

Again,wefindthatbetadecayresultsintheconversionofonechemicalelementtoanother.

Asanelectronisextremelysmall,abetaparticleislesslikelythananalphaparticletocollidewiththe
moleculesofanythingthroughwhichittravels.Dependingonitsinitialkineticenergy,abetaparticlecan
travelupto3mindryair.However,onlythehighestenergybetaparticlescanpenetratetheskin.Nuclei
lyingabovethebandofstability(figure27.1)tendtoundergoradioactivedecayviabetaemission,asthis
increasesZwithoutchangingA,therebydecreasingtheneutrontoprotonratioandmovingthenucleus
closertothebandofstability.Forexample,bybetadecay, decreasesitsneutrontoprotonratiofrom11
:9to10:10.

Thesurviving nucleusisclosertothecentreofthebandofstability.Figure27.5,anenlargementofthe
relevantpartoffigure27.1,explainsthischangefurther.Figure27.5alsoshowshowthebetadecayof
to lowerstheneutrontoprotonratio.
 FIGURE27.5Anenlargedsectionofthebandofstability.Betadecayfrom and reducestheirneutronto
protonratioandmovesthemclosertothebandofstability.Positronemission(seebelow)from
and alsoincreasesthisratioandmovesthesenucleiclosertothebandofstability.

GammaDecay
Gammaradiation,whichoftenaccompanieseitheralphaorbetaradiation,consistsofhighenergyphotons.
Agammarayphotonisgiventhesymbol or,often,simply.Gammaradiationisextremelypenetrating
andiseffectivelyblockedonlybyverydensematerialssuchaslead.Theemissionofgammaradiation
involvestransitionsbetweenenergylevelswithinthenucleuswhenanucleusemitsanalphaorbeta
particle,itissometimesleftinanexcitedenergystate,andsubsequentemissionofagammarayphoton
allowsthenucleustorelaxtoalowerenergystate.

PositronEmission
Thisisarelativelyrareformofradioactivedecayandinvolvesemissionofapositron,apositivelycharged
electron,symbolisedas .Apositronformsinthenucleusbytheconversionofaprotontoaneutron,as
showninfigure27.6.
 FIGURE27.6Theemissionofapositronandneutrinoresultsintheconversionofaprotontoaneutroninthe
nucleus.

Positronemission,likebetaemission,isaccompaniedbyachargelessandvirtuallymasslessparticle,a
neutrino(v e ).Forexample, isapositronemitteranddecaystoastableisotopeofiron:

Theejectedpositroneventuallycollideswithanelectron,andthetwoparticlesannihilateeachotherwith
productionoftwogammarayphotons,calledannihilationradiationphotons,accordingtothenuclear
equation:

Becauseapositrondestroysaparticleofordinarymatter(anelectron),itiscalledaparticleofantimatter.
Tobeclassifiedasantimatter,aparticlemusthaveacounterpartofordinarymatter,andthetwomust
annihilateeachotherwhentheycollide.Forexample,theantiprotonandtheantineutronaretheantimatter
equivalentsoftheprotonandtheneutron.Similarly,theantineutrinoejectedduringbetadecayisthe
antimattercounterpartoftheneutrinoejectedinpositronemission.Positronemissionismostoftenfoundin
nucleilyingbelowthebandofstability(figure27.1),asthisincreasestheneutrontoprotonratio,sothe
resultingnucleusliesclosertothebandofstability.A nucleus,forexample,increasesitsneutronto
protonratiobyemissionofapositronandaneutrinotogive asshowninfigure27.5:

Figure27.5alsoshowsthatpositrondecayby togive producesasimilarshifttowardsthecentre

ofthebandofstability.

NeutronEmission
Thisissimpleemissionofaneutron,whichdoesnotchangeZ.Theextremelyunstable nucleus(half
life310 21s)decaysvianeutronemission:
ElectronCapture
Asthenamesuggests,electroncaptureinvolvesthenucleuscapturinganelectronfromthesurrounding
innershellsofelectrons.Itisveryrareamongnaturalisotopesbutcommonamongsyntheticradionuclides.
Forexample, nucleicancaptureelectrons,therebyconvertingtotitaniumnuclei,withtheemissionof
Xraysandneutrinos:

Theneteffectofelectroncaptureisconversionofaprotoninthenucleustoaneutron,asshownforthe
nucleusinfigure27.7:

ElectroncapturechangesZbutnotA.Itleavesaholeintheinnerelectronshells,andtheatomemitsXray
photonsasotherorbitalelectronsdropdowntofillthehole.Moreover,thenucleusthathasjustcapturedan
orbitalelectronmaybeinanexcitedenergystateandsocanemitagammarayphoton.

FIGURE27.7Electroncaptureoccurswhenanorbitalelectroncollapsesintothenucleus,therebyconvertinga
protonintoaneutron.

WORKEDEXAMPLE27.2

WritingaBalancedNuclearEquation

,oneoftheradioactiveproductsfromanuclearpowerplant,emitsbetaandgammaradi
ation.Writethenuclearequationforitsdecay.

Analysis

Westartwithanincompleteequationusingthegiveninformationandthendetermineanyother
dataneededtocompletetheequation,rememberingthatbothZandAmustbalanceonbothsides
oftheequation.

Solution
Theincompletenuclearequationis:

Theelementsymbolcanbeobtainedfromtheperiodictableafterwehavedeterminedtheatomic
numberoftheproduct.Thismaybefoundusingthefactthattheatomicnumber(55)ontheleft
handsideoftheequationmustequalthesumoftheatomicnumbersontherighthandside.

HenceZ=56,andfromtheperiodictablewecandeterminethattheproductisBa(barium).To
determinewhichisotopeofbariumforms,werecallthatthesumsofthemassnumbersoneither
sideoftheequationmustalsobeequal.LettingAbethemassnumberofthebariumisotope:

HenceA=137.Thebalancednuclearequationistherefore:

Isouranswerreasonable?

Besidesdoublecheckingthatelement56isbarium,theanswersatisfiestherequirementsofa
nuclearequationthatis,thesumsofboththemassandatomicnumbers,onbothsidesofthe
equation,arethesame.

PRACTICEEXERCISE27.2
MarieCurie(figure27.8)wasawardedthe
NobelPrizeforchemistryin1911forthe
discoveryoftheelementspoloniumand
radium,andforthestudyofradiumandits
compounds.Sheisoneofonlyfourwomento
beawardedtheNobelPrizeforchemistry.She
hadearlierbeenawardedthe1903NobelPrize
forphysics,jointlywithherhusbandPierre
andHenriBecquerel(seep.5).MarieCurieis
oneofonlyfourpeopletobeawardedtwo
NobelPrizes.
 FIGURE27.8MarieCurie(18671934),
oneofonlyfourpeopletobe
awardedtwoNobelPrizes
(physicsin1903and
chemistryin1911).

Radiumwasoriginallyusedinthetreatmentof
cancer. isanalphaandgammaemitter.
Writeabalancednuclearequationforits
decay.

PRACTICEEXERCISE27.3
Writethebalancednuclearequationforthe
decayof ,abetaemitter.( isoneof
themanyradionuclidespresentinthewastes
ofoperatingnuclearpowerplants,andis
particularlydangerousasitcansubstitutefor
itsfellowgroup2elementcalciuminhuman
bones,therebyleadingtoirradiationof
neighbouringtissue.)

RatesofRadioactiveDecay
Themethodsofradioactivedecayoutlinedinthissectionallinvolveejectionofaparticleoraphoton.Ifwe
canmeasurethenumbersofthesethatareemittedoveraperiodoftime,wecanmeasuretherateof
radioactivedecay.Thisispossibleusingthefollowingdevices.
Geigercounter:TheGeigerMllertube,onepartofaGeigercounter(figure27.9),detectsbetaand
gammaradiationwithenergyhighenoughtopenetratethetube'swindow.Insidethetubeisagas
underlowpressureinwhichionsformwhenradiationenters.Theionspermitapulseofelectricityto
flow,whichactivatesacurrentamplifier,apulsecounterandanaudibleclick.
 FIGURE27.9AGeigercounterisoftenusedtoensuresafetyinlaboratoriesthatuseradioactivereagents.
Thiscountermeasuresradiationinunitsofmicrosievertsperhour.Thesievert(Sv)isanSI
derivedunit,with1Svequivalentto1Jkg1 .AFP/GenyaSavilov

Scintillationcounters:Ascintillationcounter(figure27.10)hasasurfacecoatedwitha
phosphorescentchemicalthatemitsatinyflashoflightwhenstruckbyaparticleofradiation.These
flashescanbemagnifiedelectronicallyandautomaticallycounted.

FIGURE27.10Ascintillationcounterbeingusedtotestradiationlevelsoutsideanuclearfacility.DarrinGray
Dosimeters:Peoplewhoworknearradiationsourcesweardosimeterstomeasuretheirtotalexposure.
Ifexposureexceedsapredeterminedlimit,theyarereassignedtoanunexposedworkplaceforaperiod
oftime.Initially,filmdosimeterswereused.Thedarkeningofaphotographicfilmexposedtoradiation
 overaperiodoftimeisproportionaltothetotalquantityofradiationreceived.Filmdosimetershave
largelybeenreplacedbymoremoderntechnologies(figure27.11):thermoluminescentdosimeters
(TLDs)andopticallystimulatedluminescence(OSL)dosimeters.

FIGURE27.11Thermoluminescentdosimeterscontainacrystaloflithiumfluorideorcalciumfluoridethat
absorbsradiation.Thecrystalisheatedinaspecialisedmachinethatcandeterminethe
radiationdose.Opticallystimulatedluminescencedosimetersmeasureexposuretodifferent
typesofradiationusingvariousfiltersandathinlayerofaluminiumoxide.Toreadthedose,
abluelaserisusedtostimulatethealuminiumoxide,causingittobecomeluminescent.The
luminescenceisproportionaltothequantityofradiationreceived.LynseyAddario

Wedefinetheactivityofaradioactivesubstanceasthenumberofdisintegrationsitundergoespersecond.
TheSIunitofactivityisthebecquerel(Bq),namedappropriatelyafterHenriBecquerel,(18521908,Nobel
Prizeinphysics,1903)whodiscoveredradioactivity1becquerelis1disintegrationpersecond.Asaguide,
1litreofairhasanactivityofabout0.04Bq,dueto14Cinitscarbondioxide,while1gramofnatural
uraniumhasanactivityofabout2.610 4Bq.Ourbodiesthemselvesarealsoradioactiveowingtothe
presenceofnaturallyoccurringisotopessuchas40Kthankfully,thelownaturalabundance(0.01%)and
longhalflife(10 9years)ofthisisotopemeansthatwearenotveryradioactive.

Forasufficientlylargesampleofaradioactivematerial,theactivityisexperimentallyfoundtobe
proportionaltothenumberofradioactivenuclei,N:

wheretheproportionalityconstant,k,iscalledthedecayconstantk.Thedecayconstantischaracteristicof
theparticularradioactivenuclide,anditgivestheactivitypernuclideinthesample.Sinceactivityisthe
numberofnucleithatdisintegratepersecond,wecanwrite:

whichiscalledthelawofradioactivedecay.Nisthechangeinthenumberofradioactivenucleioverthe
timeintervaltandisdefinedasNfinalNinitial.AsNisthereforenegative,anegativesignisintroducedto
makeactivityapositivenumber.Theaboveequationisanexampleofafirstorderkineticprocess(chapter
15)allradioactivedecayprocessesare,infact,firstorder,meaningthattheactivityofaradionuclideis
directlyproportionaltothenumberofnucleipresent.Themostimportantfacetofafirstorderprocesswith
respecttoradioactivityisthatthehalflife ofaradioactivematerial,thetimetakenforexactlyhalfof
thesampletodecay,isindependentoftheamountofthematerialpresent.Theconceptofhalflifeis
depictedinfigure27.12(seealsop.634),whichshowsthetypicalamountversustimedecaycurvefora
radioactivenucleus,inthiscase32P,anuclidewidelyusedinlabellingbiologicalsamples.
 FIGURE27.12Decayof32 P,aradioactivenuclidewithahalflifeof14.3days.Theamountofthenuclidepresent
halvesevery14.3days.

Thisnuclidehasahalflifeof14.3days,anddecaysviabetaemissiontogive32S.Therefore,afterthefirst
14.3dayperiod,exactlyhalfofthesamplehasdecayed,sowehavea50:50mixtureof32Pand32S.After
afurther14.3dayperiod,exactlyhalfoftheremaining32Phasdecayed,meaningthatthesampleisnow
75%32Sand25%32P.After10halflives(143days),thereis0.098%oftheoriginal32Psampleremaining.
Table27.1givesthehalflivesofsomenaturallyoccurringandsyntheticradioactivenucleiandtheirmodes
ofdecay.
TABLE27.1 Halflivesanddecaymodesofsomeradioactivenuclei.
Element Isotope Halflife Modeofdecay
Naturallyoccurringradionuclides
potassium 1.2510 9years beta,electroncapture,gamma

tellurium 9.210 16years electroncapture

neodymium 2.2910 15years alpha

rhenium 4.1210 10years beta
radon 3.82days alpha
radium 1.610 3years alpha,gamma

thorium 7.5410 4years alpha

uranium 4.47109years alpha

Syntheticradionuclides
tritium 12.32years beta
oxygen 122seconds positron
 phosphorus 14.3days beta
technetium 6.01hours gamma

iodine 8.03days beta

caesium 30.08years beta

strontium 28.9years beta

plutonium 87.7years alpha

americium 7.3710 3years alpha

Youcanseefromthesedatathatthehalflivesrangefromsecondstoquadrillionsofyears,andobviously,
therefore,nucleardecayreactionscanoccuratvastlydifferentrates.

Sometimesoneradionuclidedoesnotdecaytoastableisotopebutdecaysinsteadtoanotherunstable
radionuclide.Thedecayofoneradionuclideafteranothercontinuesuntilastableisotopeforms.The
sequenceofsuchsuccessivenuclearreactionsiscalledaradioactivedisintegrationseries.Fourseries
occurnaturally,and238Uisattheheadoftheoneshowninfigure27.13.

FIGURE27.13The radioactivedisintegrationseries.Thetimegivenbeneatheacharrowisthehalflifeofthe
precedingisotope.

WORKEDEXAMPLE27.3

DecaySequences

isanunstablenuclidethathasbeendetectedintheairofsomestonehouses,owingtothe
decayofnaturallyoccurringuraniuminthestone.Itspresenceisaconcernbecauseofhigh
healthhazardsassociatedwithexposuretoitsradioactivity.Gaseousradoneasilyentersthe
lungs,and,onceitdecays,itssolidproductsremainembeddedinlungtissue. changestoa
stablenuclidebyemittingandparticles.Thefirstfourstepsare,,and.Writethis
sequenceofnuclearreactionsandidentifyeachproduct.

Analysis

Chargenumberandmassnumbermustbeconservedineachreaction.Thus,eachparticle
decreasesthenuclearchargeby2unitsandthemassnumberby4units.Similarly,each
emissionincreasesthenuclearchargeby1unitbutleavesthemassnumberunchanged.Consulta
periodictabletoidentifytheelementsymbolofeachproductnuclide.

Solution
 Thestartingnuclideis222Rn,which,accordingtothedecaysequence,emitsanparticle:

TheproducthasA=2224=218andZ=862=84.Element84isPo,so222Rndecomposesto
giveanparticleand218Po:

Thepoloniumnucleusisunstable,andthesequenceindicatesthatitdecaysviaemission:

Thedecaysequenceindicatesthat isunstableaswell.Thisnuclideconvertsaneutrontoa
protonbyemission:

Forthisproduct,A=2140=214andZ=82(1)=83.Theproductnucleusisbismuth,
element83:

Thefourthdecayinthesequenceisalsoemission,whichproduces214Po,anotherisotopeof
element84:

Isouranswerreasonable?

YoucanconfirmthatbothAandZareconservedintheseprocesses.Extraheavynuclideslike
222Rnfrequentlydecaythroughsequencesofanddecays,becausetoreachthebandof
stabilitytheymustnotonlyshedmass(decay)butalsodecreasetheirN:Zratios(decay).

PRACTICEEXERCISE27.4
Thedecaysequenceinworkedexample27.3
continueswithfourmoresteps:,,,and.
Determinethecorrectequationsforthese
reactions.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
27.3SynthesisofNewElements
Chemistryasatruescientificdisciplinehaditsbeginningsonlyinthelateseventeenthandearlyeighteenth
centuries.Priortothis,man'smajorchemicalambitionwastobeabletoturnmetalelementssuchaslead
andmercuryintogold,anonsciencecalledalchemy.Notsurprisingly,despitethecenturiesofeffort
expendedinthisexercise,allattemptsendedinfailure.However,thischangedintheearlyyearsofthe
twentiethcenturywhenErnestRutherford,inturningnitrogenintooxygenbybombardingitwithalpha
particles,becamethefirstsuccessfulalchemist.Changingoneelementintoanotheriscalled
transmutation,and,aswehaveseen,isaresultofthenaturalalphaandbetadecayofradioactive
elements.Transmutationcanalsobeinduced,asRutherforddid,bythebombardmentofnucleiwithhigh
energyparticles,suchasalphaparticlesfromnaturalemitters,neutronsfromnuclearreactors,orprotons
madebystrippingelectronsfromhydrogen.Theparticlesusedtoeffecttransmutationsmustusuallybe
acceleratedtohighspeedstopenetratetheelectroncloudandthenucleusofanatomthiscanbeachieved
usingelectricfieldsinlinearandcircularaccelerators(figure27.14).

FIGURE27.14Inthislinearaccelerator(theLargeHadronCollideratCERNinSwitzerland),protonscanbe
acceleratedtojustunderthespeedoflightandgivenupto33GeVofenergybeforetheystrike
theirtarget(1GeV=109 eV=1.6x1010 J).JohannesSimon

Alinearacceleratorgivesparticlesgreaterenergyandenablesthemtosweepthroughthetargetatom's
electroncloudandbecomeburiedinitsnucleus(althoughbetaparticlescanbeaccelerated,theyare
repelledbyatargetatom'sownelectrons).Boththeenergyandthemassofabombardingparticleenterthe
targetnucleusatthemomentofcapture.Theenergyofthenewnucleus,calledacompoundnucleus,
quicklybecomesdistributedamongallofthenucleons,butthenucleusisneverthelessrenderedsomewhat
unstable.Togetridoftheexcessenergy,acompoundnucleusgenerallyejectssomethinganeutron,
protonorelectronandoftenemitsgammaradiationaswell.Thisleavesthenewnucleusofanisotope
differentfromtheoriginaltarget,soanoveralltransmutationhasoccurred.

In1917,ErnestRutherfordobservedthefirstexampleofartificialtransmutation.Whenheletalpha
particlespassthroughachambercontainingnitrogenatoms,anentirelynewradiationwasgenerated,one
muchmorepenetratingthanalpharadiation.Itwasfoundtoconsistofprotons.Rutherfordwasableto
showthattheprotonscamefromthedecayofthecompoundnucleus producedwhena nucleus
capturedabombardingalphaparticle:
wheretheasteriskin denotesacompoundnucleus.Thisprocessisillustratedinfigure27.15andalso
ontheNewZealandpostagestamppicturedinfigure27.16.

FIGURE27.15Transmutationofnitrogenintooxygen.Whenthenucleusof capturesanalphaparticle,it

becomesacompoundnucleusof .Thisthenexpelsaprotonandbecomesthenucleusof

FIGURE27.16OneoftwoNewZealandpostagestampsreleasedin1971tohonourthecentenaryof
Rutherford'sbirth.NewZealandPostLimited

Morethan1000isotopeshavebeenmadebytransmutations.Mostdonotoccurnaturally,andtheseappear
inthebandofstability(figure27.1)assmallopensquares,nearly900innumber.Thenaturallyoccurring
isotopesaboveatomicnumber82allhaveverylonghalflives.Othersmighthaveexisted,buttheirhalf
livesprobablyweretooshorttopermitthemtolastintoourera.Alloftheelementsfromneptunium
(atomicnumber93)upwards,thetransuraniumelements,aresynthetic.Elementsfromatomicnumbers
93to103completetheactinoidseriesoftheperiodictable,whichstartswithelement90,thorium.Beyond
thisseries,theelementsupto118havebeenmadesynthetically.Bombardingparticleslargerthan
neutrons,suchasalphaparticlesorthenucleiofheavieratoms,areusedtomaketheheaviestelements.
Forexample,darmstadtium(Ds,element110)wasmadewhenaneutronwasejectedfromthecompound
nucleusformedbythefusionof and :

Someatomsofthemostrecentlynamedelement,copernicium(element112),wereformedwhenaneutron
waslostfromthecompoundnucleusmadebybombarding with inareactionverysimilarto
thatabove.Thenewestelementontheperiodictable,Uus(element117),wasreportedin2010.Fiveatoms
of andoneof werepreparedfromthebombardmentof with ,andandthesehad
halflivesoftensofmilliseconds.Thenameofelement117,ununseptium,aswellasthoseforelements
113to116and118,aretemporary,andtheseelementswillnotbeassignedpropernamesuntiltheir
syntheseshavebeenindependentlyverified.

Thesynthesisofartificialisotopesisnotmerelyanacademicexercise,andmanyartificialisotopeshave
importantuses.Forexample,thetechnetiumisotope99mTcfindsextensiveuseasanimagingagentin
medicine.The239Puisotopeisfissionable,andcanthereforebeusedasafuelinnuclearpowerstations.
ThesmokedetectorsinmosthousesinAustraliaandNewZealandcontaintinyamountsofelement95,
americium(Am).60Coisagammaemitterandisusedtoirradiatefoodstuffstoincreasetheirshelflives.In
addition,thesynthesisofnewelementshelpsustounderstandthestructureofthenucleusGlennSeaborg
(19121999,NobelPrizeinchemistry,1951)predictedthatthereshouldbeanislandofstabilityamong
thenormallyshortlivedtransuraniumelements,andthat,likethe nucleus,theasyetunknown
element shouldshowunusualstabilitybecauseofthepresenceofmagicnumbersofbothprotons
andneutrons.Withthisinmind,muchtimeandmoneyisbeingexpendedinthesynthesisofnewheavy
elements.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
27.4RadioactiveDatingMethods
Thedeterminationoftheageofageologicaldepositoranarchaeologicalfindbytheuseof
radionuclidesthatarenaturallypresentiscalledradiologicaldating.Itisbasedpartlyonthepremise
thatthehalflivesofradionuclideshavebeenconstantthroughouttheentiregeologicalperiod.This
premiseissupportedbythefindingthathalflivesareinsensitivetoallenvironmentalforcessuchas
heat,pressure,magnetismandelectricalstresses.Ingeologicaldating,apairofisotopesissoughtthat
arerelatedasaparenttoadaughterinaradioactivedisintegrationseries,suchasthe series
(figure27.13). (asparent)and (asdaughter)havebeenusedasaradiologicaldatingpair
ofisotopes.Thelonghalflifeof (510 9years)isanecessarycriterionforgeologicaldating.
Aftertheconcentrationsof and aredeterminedinarockspecimen,theratioofthe
concentrationstogetherwiththehalflifeof isusedtocalculatetheageoftherock.Probablythe
mostwidelyusedisotopesfordatingrockarethe pair. isanaturallyoccurring
radionuclidewithahalflifenearlyaslongasthatof .Oneofitsmodesofdecayiselectron
capture,whichresultsintheproductionof :

Theargonproducedbythisreactionremainstrappedwithinthecrystallatticesoftherockandisfreed
onlywhentherocksampleismelted.Theamountofargoncanbemeasuredwithamassspectrometer
(chapter20)theageofthespecimenisthenestimatedusingtheobservedratioof to ,together
withthehalflifeoftheparent.Becausethehalflivesof and aresolong,sampleshavetobeat
least300000yearsoldforeitherofthesetwoparentdaughterisotopepairstowork.

14CDating

14Cdatingisusedtoestimatetheageoforganicremains,suchaswoodenorboneobjectsfromancient

tombs.Theratioof14C(abetaemitter)tostablecarbon,12C,inanancientsampleismeasuredand
comparedwiththeratioinrecentorganicremains.Thedatacanthenbeusedtocalculatetheageofthe
sample.

ChemistryResearch

SequencingtheEarlySolarSystem

DrClaudineStirling,UniversityofOtago,Dunedin

Oursolarsystemevolvedfromagiantmolecularcloudofdustandgasthatcollapsed
gravitationallymorethan4.5billionyearsago.Whattriggeredthiscollapseisthesubjectof
debate,butoneleadingtheoryinvokesshockwavesfromanearbymassiveexplodingstar
asupernova.OurresearchattheUniversityofOtagoaimstoinvestigatetheroleofa
supernovaintriggeringthebirthofoursolarsystemandreconciletheprecisetimescaleof
eventsleadingtoitsformation.Thisisachievedusingmultiplecollectorinductivelycoupled
plasmamassspectrometry(MCICPMS,figure27.17)tosearchforminute(onepartin10
000)variationsintheuraniumisotopiccompositionofmeteoritesderivedfromasteroidal
sizedobjectsthatwereformedatthestartofthesolarsystemthesevariationswerepreviously
toosmalltodetect.
 FIGURE27.17TheMCICPMSinstrumentusedtomeasureuraniumisotopes.DavidAHardy,
www.astroart.org

Thesupernovahypothesis:Didamassiveexplodingstartriggerthebirthofoursolar
system?

Byfarthemostlikelyastrophysicalsitefortheformationofuraniumandtheotherradioactive
actinoidsisasupernova,asthehighfluenceoftheneutronsreleasedfromtheexplosion
allowssynthesisoftheveryheavyelements.Thiscontrastswithlighterelements,whichcan
beproducedinarangeofdifferentastrophysicalenvironments.Therefore,thedetectionof
specificactinoidsincondensatesofthefirstsolarsystemthatarepreservedinmeteorites
providesauniquefingerprintofsupernovaeventsthatoccurredclosetotheprotosolar
molecularcloud,theregionofspacethatevolvedtobecomeoursolarsystem.Acritically
importantactinoidistheshortlivedisotope247Cm,whichdecaysto235Uwithahalflifeof
16millionyears.Givenitsshorthalflife,247Cmispresentlyextinct,butitsformerexistence
canbedetectedbysearchingforsmallexcessesinits235Udaughterisotope.Ifanomaliesin
theabundanceof235U(measuredrelativeto238Uas238U/235U)arefoundthatcanberelated
to247Cmdecay,thenitbecomespossibletousethe247Cm 235Uradioactivedecaysystemto
datethetimingofthelastsupernovaeventandevaluateitsroleintriggeringthebirthofour
solarsystem.

Solarsystemevolutionandtheuraniumleaddatingmethod

Theuraniumleadgeologicaldatingmethodhasbeenwidelyusedtodefinethetimescaleand
sequenceofeventsacrosstheEarthandsolarsystem.Theuraniumleaddatingmethodis
basedonacombinationofthe238Uand235Uradioactivedisintegrationseriesandtheslow
decayoftheradioactive238Uand235Uparentisotopes(withhalflivesof4.510 9years
and710 8years,respectively)totheirstabledaughterisotopesof206Pband207Pb,
respectively.Likemostradioactivedatingtechniques,theaccuracyandprecisionofthe
uraniumleadmethodhasexperiencedongoingimprovementsinrecentyearsas
instrumentationhasadvanced.Infact,themodernuraniumleadmethoddefinesthemost
preciseageofthesolarsystemat4.56720.0006billionyearsandprovidescompellingnew
evidencethatthedebrisintheearlysolarsystemevolvedrapidlyfromdustsizedparticlesto
largeplanetesimalsexceeding100kmacrossinonly2to3millionyears.Untilveryrecently,
theuraniumleaddatingmethodassumedaconstantratiobetweenthe238Uand235Uparent
 isotopesuraniumwasnotexpectedtofractionateisotopicallyduetoitsveryheavymass.
However,newtechniquesinmassspectrometry,allowingthe238U/235/Uratiotobemeasured
upto100timesmorepreciselythanpreviously,haveshownsignificantvariabilityinthe
238U/235Uratioofsometerrestrialrocks,andthefundamentaltimescaleoftheearlysolar
systemwillneedtobedrasticallyrevisedifuraniumisotopicvariationsarealsofoundin
meteorites.

FIGURE27.18Planetstakeshapeinthedustydiskaroundayoungstarinanartist'sconception.
ThesceneisanexampleofwhatthingsmightbelikearoundMWC419,ablue
starabout2100lightyearsfromEarth.

Therearetwoapproachesto14Cdating.Theoldermethod,whichwasintroducedbyitsdiscoverer
WillardFLibby(19081980,NobelPrizeinchemistry,1960),measurestheradioactivityofasample
takenfromthespecimen.Theradioactivityisproportionaltotheconcentrationof14C.However,the
newerandcurrentmethodof14Cdating,acceleratormassspectrometry,cancountsingle14Cnucleiin
thepresenceof10 15stableatoms.Thisapproachpermitstheuseofsmallersamples(0.55mgversus
120gfortheLibbymethod),itworksatmuchhigherefficiencies,anditgivesmoreprecisedates.The
halflifeofthe14Cnucleus(5730years)meansthatobjectsupto60000yearsoldcanbedated,but
estimationismoreaccurateforobjectslessthan7000yearsold.

14Chasbeenproducedintheatmosphereformanythousandsofyearsbytheactionofcosmicrayson
atmosphericnitrogen.PrimarycosmicraysarestreamsofparticlesfromtheSun,mostlyprotonsbutalso
thenucleiofmanyelementsashighasatomicnumber26.Theircollisionswithatmosphericatomsand
moleculesgeneratesecondarycosmicrays,whichincludeallsubatomicparticles.Secondarycosmic
rayscontributetoourbackgroundradiation,andpeoplelivingathighaltitudesreceivemoreofthis
radiationthanothers.

Neutronsoftheproperenergyinsecondarycosmicrayscantransmutenitrogenatomsinto14Catoms
accordingtotheequation:

Thenewlyformed14Cdiffusesintotheloweratmosphere,whereitisabsorbedas14CO2bygreenplants
duringphotosynthesis.Thus,14Cbecomesincorporatedintoplantsubstancesandintotheanimalsthat
eatplants.The14Cdecaysbutmoreisingestedbythelivingorganism.Theneteffectisanoverall
equilibriuminvolving14Cintheglobalsystem.Aslongastheplantoranimalisalive,itsratioof14C
atomsto12Catomsisconstant.Atdeath,theamountof14Cinanorganism'sremainsisatitsmaximum,
anditslowlylosesthis14Cbydecay.Thedecayisafirstorderprocesswitharateindependentofthe
numberoforiginalcarbonatoms.Theratioof14Cto12C,therefore,canberelatedtothetimethathas
elapsedbetweenthedeathoftheorganismandthetimeofthemeasurement.Thecriticalassumptionin
14Cdatingisthatthesteadystateavailabilityof14Cfromtheatmospherehasremainedlargely
unchangedovertheperiodforwhichmeasurementsarevalid.Incontemporarybiologicalsamples,the
ratio14C:12Cisabout1.310 12.Thus,eachfresh1.0gsampleofbiologicalcarboninequilibrium
withthe14CO2oftheatmospherehasaratioof5.810 10atomsof14Cto4.810 22atomsof12C.The
ratiodecreasesbyafactorof2every5730years,thehalflifeof14C.Knowingthe14C:12Cratiointhe
sampleallowsustocalculateitsageusingthefirstorderkinetictreatmentthatwesawinchapter15.If
weletr0standforthe14C:12Cratioatthetimeofdeathofthecarboncontainingspeciesandrtstand
forthe14C:12Crationow,itcanbeshownthat:

wheretistheageofthesampleinyears.Radiocarbondatinghasbeenusedwithgreatsuccesstodefuse
anumberofcontroversies,asshowninworkedexample27.4.

WORKEDEXAMPLE27.4

RadiocarbonDating
In1996,theJinmiumAboriginalrockshelterintheKimberleyregionoftheNorthern
Territorywasdatedataround120000yearsoldusingatechniquecalled
thermoluminescence,meaningthathumanhabitationofAustraliawouldhaveoccurredat
least60000yearsearlierthanpreviouslythought.However,themethodusedwaslatercalled
intoquestion,and14Cdatingofcharcoalfragmentswasusedtorevealthetrueageofthe
site.The14C:12Cratioinacharcoalsamplewas1.0810 12,whilethesameratioinliving
objectsis1.3310 12.Howoldisthesample?

Analysis

Weknowthe14C:12Cratioinboththecharcoalsampleandinlivingobjects.Therefore,we
simplyusethesevaluesintheequationgivenabovetofindt.

Solution

Usingtheequation:

andsubstitutingthevaluesabovegives:
 Hence:

Thetrueageoftheupperlevelsindepositsatthesitewasoftheorderof10003000years,
whilelowerlevelsweredatedatnoolderthan10000years.Theearliestknowndateof
humanhabitationofAustralia,therefore,remainsataround5000060000yearsago.

Isouranswerreasonable?

Inproblemslikethis,involvingthesubstitutionofdataintoanequation,alwaysgobackand
checkthatyouhaveputthecorrectnumbersinthecorrectplaces.Weappeartohavedone
this,andtheanswerweobtainedisplausible,sowecanbeconfidentwearecorrect.

PRACTICEEXERCISE27.5
In1988,theShroudofTurin(figure27.19),
claimedbysometohavebeenusedtobury
Christ,wasdatedbyisotopicanalysisofits
carboncontent.The14C:12Cratioofa
samplefromtheshroudwas1.2210 12,
whilethesameratioinlivingobjectsis1.33
10 12.Howoldistheshroud?

FIGURE27.19TheshroudofTurin.

Calculationsofages,asillustratedinworkedexample27.4,assumethatthelevelof14Cinthe
atmosphereatthetimeofdeathwasthesameasitistoday.Tocheckthevalidityof14Cdating,itsage
estimateshavebeencomparedwiththoseobtainedbytreeringdating,whichinvolvesfewer
assumptionsthanradiocarbondating.Alargenumberofsuchcomparisonsshowsmallbutconsistent
differences,indicatingthatthefractionalamountof14Cintheatmospherehaschangedslowlybut
steadilywithtime.Archaeologistsuseasmallmultiplyingfactortocorrectforthissmalldriftwhenthey
useradiocarbondatingonobjectsthatdonotretaintreerings,suchascharcoalandcloth.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
27.5ApplicationsofNuclearProcesses
TherearefewmoreemotivewordsintheEnglishlanguagethannuclear.Ontheonehand,nuclearpower
canpotentiallyprovideenergyfortheplanetfortheforeseeablefuture.Ontheotherhand,Hiroshimaand
NagasakiservetoremindusthatnuclearprocessescanpotentiallydestroylifeonEarth.Thenucleardebate
hasragedforover60yearsandwilldoubtlesscontinueformanymore.Itisimportantthatallparticipantsin
thisdebatearewellinformed,so,inthissection,weaimtoexplaintheprocessesthatallowusaccesstothe
hugeenergiesofthenucleusthroughnuclearfissionandnuclearfusion.Wealsotakeabrieflookatnuclear
medicine,inwhichradioactivematerialsareusedinacontrolledfashionfordiagnosisandtreatmentof
disease.

NuclearFission
Wehavealreadyseenthatnucleartransmutationreactionscanbeinducedbybombardmentofparticular
nucleiwithalphaparticles.Becauseoftheirelectricalneutrality,neutronspenetrateanatom'selectroncloud
easily,sotheycanenterthenucleus.EnricoFermidiscoveredintheearly1930sthatslowmovingthermal
neutrons,thosewithanaveragekineticenergythatputstheminthermalequilibriumwiththeirsurroundings
atroomtemperature,canbecapturedbynuclei.WhenFermidirectedthermalneutronsatauraniumtarget,
severaldifferentspeciesofnucleiwereproduced,aresultthatFermicouldnotexplain.Nonehadanatomic
numberabove82.HeandotherphysicistsdidnotfollowuponasuggestionbychemistIdaNoddackTacke
thatnucleiofmuchloweratomicnumberprobablyformedatthattime,theforcesholdinganucleus
togetherwereconsideredtoostrongtopermitsucharesult.

In1939,OttoHahn(18791968,NobelPrizeinchemistry,1944)andFritzStrassmanfinallyverifiedthat
theprocessaboveproducesseveralisotopesmuchlighterthanuranium,suchas .Shortlythereafter,
LiseMeitner(afterwhomelement109,meitnerium,isnamed)andOttoFrischshowedthatanucleusofone
oftherareisotopesinnaturaluranium, ,splitsintoroughlytwoequalpartsafteritcapturesaslow
neutron.Theynamedthisbreakupnuclearfission.Anisotopethatcanundergofissionafterneutroncapture
iscalledafissileisotope. isthenaturallyoccurringfissileisotopeofuraniumusedinnuclearreactors
andhasanabundanceof0.72%.Twootherfissileisotopes, and ,canbemadeinnuclear
reactors.Thegeneralfissionreactionof canberepresentedas:

XandYcanbealargevarietyofnuclei,withmorethan30havingbeenidentified.Thecoefficientbhasan
averagevalueof2.47,theaveragenumberofneutronsproducedbyfissionevents.Atypicalspecificfission
is:

Thecompoundnucleus istheonethatactuallyundergoesnuclearfission.Ithas144neutronsand92
protonsforaneutron:protonratioofroughly1.6.Initially,theemergingkryptonandbariumisotopeshave
thesameratio,andthisismuchtoohighforthem.Theneutron:protonratioforstableisotopeswith36to
56protonsisnearer1.2to1.3(figure27.1).Therefore,theinitiallyformed,neutronrichkryptonandbarium
nuclidespromptlyejectneutrons,calledsecondaryneutrons,thatgenerallyhavemuchhigherenergiesthan
thermalneutrons.Thesesecondaryneutronsbecomethermalneutronsastheyareslowedbycollisionswith
surroundingmaterials.Theycannowbecapturedbyunchanged atomsandtheprocessisrepeated.
Becauseeachfissioneventproduces,onaverage,morethantwonewneutrons,thepotentialexistsfora
nuclearchainreaction(figure27.20).
 FIGURE27.20Anuclearchainreaction.Whenevertheconcentrationofafissileisotopeishighenough(ator
abovethecriticalmass),theneutronsreleasedbyonefissioncanbecapturedbyenough
unchangednucleitocausemorethanoneadditionalfissionevent.Inciviliannuclearreactors,the
fissileisotopeistoodiluteforthistogetoutofcontrol.Inaddition,controlrodsofnonfissile
materialsthatareabletocaptureexcessneutronscanbeinsertedorwithdrawnfromthereactor
coretoensurethattheheatgeneratedcanberemovedasfastasitdevelops.

Achainreactionisaselfsustainingprocesswhereproductsfromoneeventcauseoneormorerepetitionsof
theprocess.Ifthesampleof issmallenough,thelossofneutronstothesurroundingsissufficiently
rapidtopreventachainreaction.However,atacertaincriticalmassof ,afewkilograms,thislossof
neutronsisinsufficienttopreventasustainedreaction.Avirtuallyinstantaneousfissionofthesampleensues
resultinginanexplosionthatreleasesanenormousamountofenergy.Theenergyproducedbythefission
of1kgof (aboutthesizeofagolfball)isroughly810 13J,thesameenergyasiscontainedin19
000tonnesofTNT.

Virtuallyallciviliannuclearpowerplantsthroughouttheworldoperateonthesamegeneralprinciples.The
heatoffissionisusedeitherdirectlyorindirectlytoincreasethepressureofsomegasthatthendrivesan
electricgenerator.Theheartofanuclearpowerplantisthereactor,wherefissiontakesplaceinthefuel
core.Thenuclearfuelisgenerallyuraniumoxide,enrichedto24% andformedintoglasslikepellets.
Thesearehousedinlong,sealedmetaltubescalledcladding.Bunchesoftubesareassembledinspacersthat
permitacoolanttocirculatearoundthetubes.Areactorhasseveralsuchassembliesinitsfuelcore.The
coolantcarriesawaytheheatoffission.

Thereisnodangerofanuclearpowerplantundergoinganuclearexplosionastheconcentrationoffissile
isotopesinareactor(2to4%)istoolow.However,ifthecoolantfailstocarryawaytheheatoffission,the
reactorcorecanmeltdown,andthemoltenmassmightevengothroughthethickwalledcontainmentvessel
inwhichthereactoriskept.Itisalsopossiblethattheheatcansplitmoleculesofcoolantwaterinto
hydrogenandoxygen,which,onrecombining,couldproduceanimmenseexplosion.Thisiswhat
happenedwhenthereactorattheUkrainianenergyparkatChernobylfailedin1986andwhenthe
FukushimareactorinJapanwasdamagedbyanearthquakein2011.

Toconvertsecondaryneutronstothermalneutrons,thefuelcorehasamoderator,whichisthecoolantwater
itselfinnearlyallcivilianreactors.Collisionsbetweensecondaryneutronsandmoderatormoleculesheatup
themoderator.Thisheatenergyeventuallygeneratessteamthatenablesanelectricturbinetorun.Ordinary
waterisagoodmoderator,andsoareheavywater(deuteriumoxide,D2O,aformofwaterinwhichallthe
protonshavebeenreplacedbydeuteriumatoms)andgraphite.Twomaintypesofreactorsdominatecivilian
nuclearpower,theboilingwaterreactorandthepressurisedwaterreactor.Bothuseordinarywaterasthe
moderator,andsoaresometimescalledlightwaterreactors.Apressurisedwaterreactor,suchasthat
depictedinfigure27.21,hastwoloops,andwatercirculatesinboth.

FIGURE27.21Pressurisedwaterreactor.Waterintheprimarycoolantloopispumpedaroundandthroughthefuel
elementsinthecore,anditcarriesawayheatproducedbythenuclearchainreactions.Thehot
waterdeliversitsheattothecoolerwaterinthesecondarycoolantloop,wheresteamisgeneratedto
drivetheturbines.(DrawingfromWASH1261,U.S.AtomicEnergyCommission,1973)

Theprimarycoolantloopmoveswaterthroughthereactorcore,whereitpicksupthermalenergyfrom
fission.Thewateriskeptintheliquidstatebybeingunderhighpressure(hencethenamepressurisedwater
reactor).Thehotwaterintheprimarylooptransfersthermalenergytothesecondaryloopatthesteam
generator.Thismakessteamathightemperatureandpressure,whichispipedtotheturbine.Asthesteam
drivestheturbine,thesteampressuredrops.Thecondenserattheendoftheturbine,cooledbywater
circulatingfromariverorlakeorfromhugecoolingtowers,forcesalargepressuredropwithintheturbine
bycondensingthesteamtoliquidwater.Thereturnedwateristhenrecycledtohighpressuresteam.(Inthe
boilingwaterreactor,thereisonlyonecoolantloop.Thewaterheatedinthereactoritselfischangedto
steamthatdrivestheturbine.)

Currently,neitherAustralianorNewZealandhasacommercialfissionreactorforelectricitygeneration.
However,AustraliahastheOPALresearchreactoratLucasHeights(figure27.22),justoutsideSydney.This
isusedfor,amongotherthings,theproductionofradioisotopesforbothindustrialandmedicaluses,and
processingsiliconchips.OPALreplacedtheHIFARreactor,whichcommencedoperationin1960and
begandecommissioningin2007,aprocessthatwillbecompletedin2016.
 FIGURE27.22TheLucasHeightsResearchReactor,ontheoutskirtsofSydney.IanWaldie

Themajorproblemwithfission,andonethatappearsinsurmountable,isthatsignificantamountsof
radioactivenuclearwasteareproduced.Suchwastemustbesafelycontainedforatleast10halflives
(0.098%oftheoriginalsampleremainsafterthistime)andthispresentsenormouspracticaldifficulties.
Radioactivewastesfromnuclearpowerplantsoccurasgases,liquidsandsolids.Thegasesaremostly
radionuclidesofkryptonandxenonbut,withtheexceptionof ,thegaseshaveshort
halflivesanddecayquickly.Duringdecay,theymustbecontained,andthisisonefunctionofthecladding.
Otherdangerousradionuclidesproducedbyfissioninclude , and . mustbecontained
becausethehumanthyroidglandconcentratesiodideionstomakethehormonethyroxine.Oncetheisotope
isinthegland,betaradiationfrom couldcauseharm,possiblythyroidcancerorimpairedthyroid
function.Aneffectivecountermeasureto poisoningistotakedosesofordinaryiodine(assodium
iodide).Statistically,thisincreasesthelikelihoodthatthethyroidwilltakeupthestableiodideionrather
thantheradioactiveanionof . and alsoposeproblemstohumans.Caesiumisingroup1
togetherwithsodium,soradiating cationscantraveltosomeofthesameplacesinthebodywhere
sodiumionsareconcentrated.Strontiumisingroup2withcalcium,so cationscanreplacecalciumions
inbonetissue,sendingradiationintobonemarrowandpossiblycausingleukaemia.Thehalflivesof
and ,however,arerelativelyshort.Someradionuclidesinwastesaresolonglivedthatsolidreactor
wastesmustbekeptawayfromallhumancontactfortensofcenturies,longerthananynationhaseveryet
endured.Probablythemostintensivelystudiedprocedureformakingsolidradioactivewastessecureisto
convertthemtoglasslikeorrocklikesolidsandburythemdeepwithinarockstratumorinamountain
believedtobegeologicallystablewithrespecttoearthquakesandvolcanoes.Thereisnoknownwayof
makingnuclearwastesafewesimplyhavetowaituntilithasundergonecompletedecay.
NuclearFusion
Fusionisamoreattractiveenergysourcethanfission.Whereasfissionoccursforonlyafewrare,extremely
heavynuclides,fusionispossibleforabundantlightnuclidessuchas1H.Moreover,somefusionreactions
releasemoreenergyperunitmassthandofissionreactions.Forexample,thefusionoftwohydrogen
isotopes,deuteriumandtritium,releases3.410 8kJg 1,comparedwith810 7kJg 1releasedinthe
fissionof235U.Anotherattractivefeatureoffusionreactionsisthattheproductnuclidesareusuallystable,
sosmalleramountsofradioactivebyproductsresultfromfusionthanfromfission.

Themajorimpedimenttofusionreactionsisthatthereactingnucleimusthaveveryhighkineticenergiesto
overcometheelectricalrepulsionbetweenpositiveparticles.Thefusionoftwohydrogennucleihasthe
lowestpossiblerepulsionbarrierbecauseitinvolvestwoZ=1nuclei.Evenso,thisreactionrequireskinetic
energiesequivalenttotemperaturesof10 7K(thetemperatureatthecoreoftheSun)orgreater.AsZ
increases,sodoesthisenergyrequirement,andthefusionoftwo12Cnuclei,forexample,requireskinetic
energiesequivalenttoatemperatureof10 9K.Thereareseveralwaystoproducenucleiwithenoughkinetic
energytofuse.Onemethodusesparticleacceleratorstogeneratesmallquantitiesoffastmovingnuclei.The
characteristicsoffusionreactionsarestudiedwithsuchaccelerators,butthescaleoffusioneventsinthese
experimentsistoosmalltoreleaseusefulamountsofenergy.Asecondwaytoinducefusionusestheenergy
releasedingravitationalattractiontogenerateatemperaturehighenoughtostartthereaction.TheSunand
otherstarsoperateinthisway.Athirdwayisthefusionbomb,whichusesafissionbombtogeneratea
temperaturehighenoughforfusion.Noneoftheseprovidesamethodforharnessingfusionasapractical
sourceofpoweronEarth.However,mucheffortiscurrentlybeingexpendedininitiatingausefulfusion
reactionbyheatingaplasmaconfinedinamagneticfield.Ifsuccessful,thismethodmayharnessfusionasa
sourceofpower.Thetechnologicalproblemsareimmense,however,becausethefusingmaterialmustbe
confinedtoavolumesmallenoughtogeneratehighnucleardensitiesandmanynuclearcollisions.Because
allmaterialsvaporiseattemperatureswellbelowthatrequiredtosustainfusionreactions,containersthat
wouldwithstandsustainedfusioncannotbebuilt.Theapproachmostoftentakentoaddresstheseproblems
istouseahot,ionisedplasmathatcontainscationsof2H,3Hand6Li,alongwithenoughelectronsto
maintainchargeneutrality.Thisplasmaisheatedintensely,usuallybypowerfullaserbeams.Tokeepthe
plasmafromflyingapart,itisconfinedbyadoughnutshapedmagneticfieldinanapparatuscalleda
tokamak.Figure27.23showsadiagramofsuchamagneticfieldandaphotoofaprototypethatisin
operationintheUSA.
 FIGURE27.23Thetokamakisaversionofafusionreactorthathasbeenthesubjectofintensedevelopmentefforts.
Thedesignandanexperimentalprototypeofthetokamakareshownhere.USDepartmentofEnergy

Fusioncannotbecomeapracticalsourceofenergyunlesstheenergyreleasedexceedstheenergyusedto
heatandconfinetheplasma.Unfortunately,theenergyinputrequirementisenormous,eveninsmallscale
experimentalstudies.Thebestexperimentsconductedsofarhavemanagedtoachievefusionbutnotsustain
itlongenoughtoachieveanynetproductionofenergy.Assumingthatasustainedfusionreactionis
achieved,somewaymustbefoundtoharnessitsenergyoutput.Becausethefieldconfiningtheplasma
preventstheescapeofchargedparticles,mostoftheenergyoutputofthereactorisexpectedtobephotons,
ranginginenergyfrominfraredraystorays.Thesephotonswillhavetobeabsorbedbyasuitablematerial
thatconvertstheirenergy,directlyorindirectly,intoelectricity.Currently,afullscaleexperimentalfusion
reactorcalledITER(InternationalThermonuclearExperimentalReactor)isunderconstructioninCadarache,
France,withcompletionexpectedin2017andthefirstplasmatobegeneratedin2019.Thiswilluse
tokamaktechnologyandwillattempttodemonstratetheviabilityofcommercialelectricityproductionfrom
fusion.Thereareenormouspracticaldifficultiestobeovercomebeforefusioncanbeusedasanenergy
source,and,evenifthisexperimentalreactorprovestobesuccessful,itisestimatedthatcommercialfusion
reactorswouldnotbecomeoperationaluntilatleasttheyear2050.

NuclearMedicine
Aswehaveseen,manyradioisotopesareextremelyhazardoustohumanhealth.Despitethis,radioisotopes
arenowwidelyusedinmedicine,bothasdiagnosticaidsandastreatments.Asadiagnostictool,nuclear
decompositionallowsdoctorstoexamineinternalorgansbynoninvasiveprocedures.AlthoughXraysare
goodforformingimagesofbonesandteeth,mostsofttissueorgansaretransparenttoXrays.Forthese
organs,raysresultingfromnucleardecaycanbeusedtoproduceimages.LikeanXrayfilm,aray
imagerevealsabnormalities,allowingphysicianstodiagnoseailmentsoftheheart,spleen,liver,brainand
othervitalorgans.

Radioactivetracersformedicalimagingaredesignedtoconcentrateinspecificorgans.Forexample,glucose
canbelabelledwith11C,apositronemitter,foruseinpositronemissiontomography(PET),averyuseful
techniqueformonitoringbrainfunction.APETscandetectssituationswhereglucoseisnottakenup
normally,e.g.inbipolardisorder,schizophreniaandAlzheimer'sdisease.Afterthe11Clabelledglucoseis
ingested,radiationdetectorsoutsidethebodypickuptheannihilationradiationofpositronemission
specificallyfromthosebrainsitesthatuseglucose.PETscantechnology,forexample,hasshownthatthe
uptakeofglucosebyabraincontainingnicotineislessthanthatofanormalbrain,suggestingthatsmokers
cannotgetasmuchglucoseintothebrainasnonsmokers(figure27.24).
 FIGURE27.24Positronemissiontomography(PET)inthestudyofbrainactivity:(left)nonsmoker,(right)smoker.
Thecoloursarerelatedtothedegreeofuptakeofglucose,withredbeingthehighestandbluethe
lowest.ThePETscanrevealswidespreadreductionintherateofglucosemetabolismwhen
nicotineispresent.(PhotoscourtesyofE.D.London,NationalInstituteofDrugAbuse)EDLondon,
NationalInstituteofDrugAbuse

Otherexamplesofradionuclidesthatareusefulfortargetingspecificorgansinclude52Feforbonemarrow
scans,133Xeforstudyinglungfunctionsand131Iforthethyroidgland.Probablythemostimportant
diagnosticradioisotopeinusetodayisthetechnetiumisotope99mTc.Thisisametastableisotope,meaning
thatthenucleusisinahighenergystateanddecaysbyemissionofaraytogivethegroundstate99Tc
nuclidewithahalflifeofabout6hours.99mTchasnearperfectpropertiesformedicalimaging.First,it
emitsraysofmoderateenergythatareeasytodetectbutarenothighlydamagingtolivingtissue.Second,
althoughtechnetiumisnotnormallyfoundinthebody,theelementcanbeboundtomanychemicalspecies
calledtracersthatthebodyrecognisesandprocesses,therebyallowingtargetingofspecificorgans.Third,
theisotopedecomposesataratethatisslowenoughtodelivertracerscontaining99mTctothebodyand
generateanimage,butfastenoughtominimiselongtermeffectsofradiation.About95%ofthe99mTc
administeredforamedicalscandecomposeswithinthefirst24hoursafterintroductionintothebody.

Becauseexposuretoradiationisahealthrisk,theadministrationofradioactiveisotopesmustbemonitored
andcontrolledcarefully.Isotopesthatemitalphaorbetaparticlesarenotusedforimagingbecausethese
radiationscausesubstantialtissuedamage.Specificityforatargetorganisessentialsothattheamountof
radioactivematerialcanbekeptaslowaspossible.Inaddition,anisotopeformedicalimagingmusthavea
decayratethatisslowenoughtoallowtimetomakeandadministerthetracercompoundyetfastenoughto
ridthebodyofradioactivityinasshortatimeaspossible.

Radioactivityisalsousedtotreatcertaincancersthatrespondparticularlywelltoradiationtherapy.Thekey
toradiationtherapyisthatcancercellsreproducemorerapidlythannormalcells,andrapidlyreproducing
cellsaremoresensitivetoradiation.Ifconcentrateddosesofradiationarefocusedonthemalignantcells,a
cancermaybedestroyedwithminimaldamagetohealthytissue.Thyroidcancersareoftentreatedwith
radioactiveiodinebecausethethyroidglandpreferentiallyabsorbsiodine.Ifapatientistreatedwith131I,the
emissionsfromthisisotopeareconcentratedinthegland,destroyingcancerouscellsmorerapidlythan
normalcells.Atthecorrectdosage,thecancermaybeeliminatedwithoutdestroyingthehealthypartofthe
thyroidgland.Inanalternativeapproach,ametalwireofradioactive197Irisimplantedwithinthetargetarea
throughacatheter.Thewireimplantisremovedafterthecorrectdoseofradiationhasbeenadministered.
Theradioactivesourceneednotalwaysbeintroducedintothebody.Inoperablebraintumourscanbe
treatedwithraysfromanexternalsource,usuallyasampleof60Co,whichcanbefocusedonthetumour,
therebyminimisingdamagetosurroundinghealthytissue.

ChemicalConnections

Radiopharmaceuticals

Althoughweusuallythinkofradioactivesubstancesasbeingharmfultohealth,anumberof
radioactiveisotopeshavefoundextensiveuseinboththetreatmentanddiagnosisofavarietyof
medicalconditions.Intherapeuticnuclearmedicine,radiopharmaceuticalsareintroducedtothe
bodytotargettumourcells.Theradiopharmaceuticalsusedusuallyemitbetaparticles,whichcan
killcancercells.

Indiagnosticnuclearmedicine,thepatientisinjectedwithasmallquantityofaradioisotope,and
thepatternofradiation(gammarays)emittedfromwithintheirbodyisthenrecordedbyagamma
camera.Tocreatethedesiredimage,theinjectedisotopemustbetargetedtotheorganofinterest.
Thisisoftendonebyincorporatingtheisotopeintoamoleculethatistakenuppreferentiallyby
thatorgan.Forexample,glucose,whichisusedbynervecellsforenergy,istaggedwitha
radioisotopeforstudiesofthebrain.Twoisotopesofiodine,123Iand131I,canbeincorporatedby
thethyroidglandsimplyasiodideions,andsoallowbothimagingandtreatmentofthyroid
disorders.

Nuclearmedicineimagingcreatesanimageoftheactivityoftheorganofinterest,ratherthanjust
theanatomy.Becauseofthis,anyunusualactivity,suchasthatproducedbythepresenceof
cancercells,canbedetectedbythepresenceofahotspotorcoldspotontheimageproduced
(seefigure27.25).Infact,nuclearmedicineimagingcandetectcancer,heartdiseaseandother
medicalconditionsmuchearlierthansomeotherimagingtechniquessuchasCTscans.Mostof
theradioisotopesusedindiagnosticimaginginAustraliaareproducedbytheLucasHeights
reactor.Itisexpectedthat,onaverage,mostAustralianswillneedatleastonenuclearmedicine
procedureintheirlifetime.
 FIGURE27.25Colouredpositronemissiontomography(PET)scanofahealthybrain(left)andone
affectedbyatumour(right).Thecerebralhemispheresofthehealthybrainshowa
regularyellowband.Thetumourappearsblue(coldspot)withintheyellowband.It
showslowbloodsupplybecauseoftissuedamageortissuedeathatthe
tumour.SPL/NationalCancerInstitute

Themostwidelyusedradioisotopeisthemetastabletechnetiumisotope99mTc,whichcanbeused
toimagethelungs,brain,kidneys,heart,lymphnodesandbones,oncoordinationtosuitable
ligands.Itisalsousedincombinationwithanantimonysulfurcolloidinsentinelnodeimaging,a
processthatcanidentifythefirstlymphnodethatreceiveslymphaticflowfromthebreast,thereby
reducingtheneedfortheextensiveremovaloflymphnodesincasesofbreastcancer.

The13Nand18Fisotopesarebeingusedincreasinglyinpositronemissiontomographyand18Fis
particularlyusefulincancerdiagnosis.Cancercellsrelyonaprocesscalledglycolysisfortheir
energy,ratherthantheKrebscycleusedbynormalcells.18Flabelleddeoxyglucoseis
incorporatedintotheKrebscycleandcanthereforebeusedasanindexofcanceractivity.

Whilemanydiagnosticproceduresinvolvingradioactiveisotopesinvolvesometypeofimaging,
AustralianphysicianBarryMarshalldevelopedasimplebreathtestforthepresenceof
Helicobacterpylori(thebacteriumthatcausespepticulcers)whichuses14Clabelledurea.Asthe
bacteriumrapidlyconvertsureatocarbondioxideandammonia,thecarbondioxideislabelled
withradioactive14C.Thepatientisadministeredwiththelabelledureaand,shortlyafterwards,
blowsupaballoon.Thepresenceof14Cintheexhaledairconfirmsinfectionbythebacterium.
ForthisandotherworkwithHelicobacterpylori,DrMarshallwasawardedtheNobelPrizein
physiologyormedicinein2005,alongwithhisAustraliancoworkerRobinWarren.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 SUMMARY
NuclearStability
Thestabilityofaparticularnucleusisdeterminedbyitsneutrontoprotonratio.Onaplotofnumberof
neutronsversusnumberofprotons,thestablenucleilieinabandofstabilityinwhichtheratioincreases
from (1.00)to (1.54).Thenucleusisheldtogetherbythestrongnuclearforce,whichacts
betweenprotonsandneutronsatextremelyshortdistances.However,protonprotonrepulsionincreases
asZincreases,andtherearenostablenucleibeyondlead(Z=82).

Thesumofthemassesoftheconstituentnucleonsinanucleusisalwaysgreaterthantheactualmassof
thenucleus,assomemassisconvertedtoenergyonformationofthenucleusinaprocesscallednuclear
fusion.Thismassdifference,themassdefect,allowsthenuclearbindingenergytobecalculated,which
showsthesubstantialenergiesinvolvedintheatomicnucleus.Thenuclearbindingenergydividedby
themassnumberAgivesthebindingenergypernucleon,whichmeasureshowtightlyeachnucleonis
boundtothenucleus.Usingthiscriterion,itcanbeshownthatthe nucleusisthemoststableofall
nuclei.NucleiofgreaterZwouldbeexpectedtoundergonuclearfission,abreakupofthenucleusinto
smallerparts,tobecomemorestable.

Nucleihavingevennumbersofbothprotonsandneutronsaremorelikelytobestablethanthosehaving
bothoddnumbers.Magicnumbersof2,8,20,28,50,82and126protonsand/orneutronsalsoimpart
stabilitytothenucleus.

UnstableNuclei
Unstablenucleiundergoradioactivedecaytogivenucleiwithmorefavourableneutrontoprotonratios.
Theprocessesavailableforsuchdecayarealphadecay,betadecay,gammadecay,positronemission,
neutronemissionandelectroncapture,andtheseprocessescanbedepictedbyuseofnuclearequations.
Betadecayinvolvesemissionofabetaparticlefromthenucleus,gammadecaygivesrisetogamma
radiation,andpositronemissionresultsfromejectionofapositron,theantimattercounterpartofthe
electron.Neutronemissionandelectroncaptureinvolveejectionofaneutronandcaptureofanorbital
electron,respectively.Decayprocessesoccuratdifferentrates,whichwecanquantifybymeasuringthe
changeinactivity(measuredinbecquerels)overtime.Thelawofradioactivedecaystatesthat:

wherekisthedecayconstantandNisthechangeinthenumberofradioactivenuclei(NfinalNinitial)
overthetimeintervalt.Radioactivedecayisafirstorderprocess,meaningthatthehalflifeofa
radioactivenucleusisindependentoftheamountofthenucleuspresent.Whentheproductnucleusof
radioactivedecayisitselfradioactive,aradioactivedisintegrationseriescanbeformed,andfourof
theseoccurnaturally.

SynthesisofNewElements
Transmutationoccurswhenoneelementisconvertedtoanother.Thiscanoccurthroughnaturaldecay
processesorcanbeinducedbybombardmentofnucleiwithhighenergyparticles.Suchbombardment
cangiverisetoacompoundnucleusthatisshortlivedanddecaystogivetheproductnucleus.Allthe
transuraniumelements(elements93118)havebeenpreparedusingthesetechniques.

RadioactiveDatingMethods
Naturallyoccurringradionuclidescanbeusedinradiologicaldating,andthe pairin
particularhavebeenusedtodatetheEarth.14Cdatingiswidelyusedtodateorganicremainsandrelies
oncomparisonofthe14C:12Cratiointheobjectofinterestwiththeratioinlivingobjects.The
equation:

isusedtodeterminetheageofthesample,wherer0isthe14C:12Cratioatthetimeofdeathandrtis
thecurrentratio.

ApplicationsofNuclearProcesses
Nuclearfissionwasdiscoveredinthe1930s.Inthiscase,afissileisotopeundergoesdecayfollowing
captureofaneutrontogivesmallernucleiandthereleaseofsignificantamountsofenergy.Useofa
criticalmassofafissilenucleusresultsinachainreactionthateventuallyleadstoanexplosion.Nuclear
powerplantsoperateusingtheheatderivedfromnuclearfissionreactionstoproducesteamthatspins
turbinesandgenerateselectricity.Nuclearfusionisacleanerprocessthannuclearfissionandinvolves
thefusionofsmallnucleitogivelargernuclei.Incontrasttofission,fusioncannotbeeasilyinduced
andcurrentlyrequiresveryhightemperaturestobeinitiated.Radioactiveisotopesareusefulinnuclear
medicineandcanbeusedasboththerapeuticanddiagnosticreagents.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYCONCEPTSANDEQUATIONS
Bandofstability(section27.1)
Thebandascertainsthestabilityofnuclei,andidentifiesthelikelydecaytypefromtheratioofneutrons
toprotons.

Magnitudeofthenuclearbindingenergy(section27.1)
Thispropertyallowscomparisonofthestabilityofnuclei.

Nuclearequations(section27.2)
Thesereactionsquantitativelydescribenuclearreactionsandrelateamountsofnuclearreactantsand
products.

Lawofradioactivedecay(section27.2)
Theequation:

relatesactivities,decayconstantsandthenumberofdisintegratingatomsinasample.

Halflife(section27.2)
Thispropertyquantitativelymeasuresthestabilityofanynucleus.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWQUESTIONS
NuclearStability
27.1Whyisn'tthesumofthemassesofallnucleonsinonenucleusequaltothemassoftheactual
nucleus?
27.2Whatdataareplottedandwhatcriterionisusedtoidentifytheactualbandinthebandofstability?
27.3Both123Baand140Baareradioactive,butwhichismorelikelytohavethelongerhalflife?
Explainyouranswer.
27.4112Snisastablenuclidebut112Inisradioactiveandhasaveryshorthalflife .What

does112Snhavethat112Indoesnottoaccountforthisdifferenceinstability?
27.5139Laisastablenuclidebut140Laisunstable .Whatruleofthumbconcerningnuclear
stabilityexplainsthis?
27.6Astheatomicnumberincreases,theneutron:protonratioincreases.Whatdoesthissuggestisa
factorinnuclearstability?
27.7Although164Pbhastwomagicnumbers,82protonsand82neutrons,itisunknown.208Pb,
however,isknownandstable.Whatproblemaccountsforthenonexistenceof164Pb?
UnstableNuclei
27.8Threekindsofradiationmakeupnearlyalloftheradiationobservedfromnaturallyoccurring
radionuclides.Whatarethey?
27.9Givethecompositionofeachofthefollowing.
(a)alphaparticle
(b)betaparticle
(c)positron
27.10Whyisthepenetratingabilityofalpharadiationlessthanthatofbetaorgammaradiation?
27.11Whatdecayparticleisemittedfromanucleusoflowtointermediateatomicnumberbuta
relativelyhighneutron:protonratio?Howdoestheemissionofthisparticlebenefitthenucleus?
27.12Whatdecayparticleisemittedfromanucleusoflowtointermediateatomicnumberbuta
relativelylowneutron:protonratio?Howdoestheemissionofthisparticlebenefitthenucleus?
27.13Whatdoeselectroncapturedototheneutron:protonratioinanucleus:increaseit,decreaseitor
leaveitunchanged?Whichkindsofradionuclidesaremorelikelytoundergoelectroncapture:
thoseaboveorthosebelowthebandofstability?
27.14Whatisthemostprobabledecayprocessforsilicon32?Writethebalancednuclearequation.
SynthesisofNewElements
27.15Compoundnucleiformanddecayalmostatonce.Whataccountsfortheinstabilityofa
compoundnucleus?
27.16Rutherfordtheorisedthatacompoundnucleusformswhenheliumnucleihit14Nnuclei.Ifthis
compoundnucleusdecayedbythelossofaneutroninsteadofaproton,whatwouldtheother
productbe?
27.17Whyisiteasiertouseneutronstoformcompoundnucleiratherthanalphaparticlesorother
nuclei?
RadioactiveDatingMethods
27.18
 Ifasampleusedfor14Cdatingiscontaminatedbyair,thereisapotentiallyseriousproblemwith
themethod.Whatisit?
27.19Anarchaeologistdiscoversanewsitewheresmallpiecesofcharcoalaremixedwithhuman
remains.BurningasmallsampleofthischarcoalgivesgaseousCO2that,whenplacedina
counter,registers1.75decayspersecond.WhenanequalmassofCO2fromfreshcharcoalis
placedinthiscounter,thecountrateis3.85decayspersecond.Howoldisthearchaeological
site?
ApplicationsofNuclearProcesses
27.20Whyshouldaradionuclideusedinmedicaldiagnosticworkhaveashorthalflife?Ifthehalflife
istooshort,whatproblemarises?
27.21Analphaemitterisnotusedinmedicaldiagnosticwork.Why?
27.22Whyisiteasierforanucleustocaptureaneutronthanaproton?
27.23Whatdoeseachofthefollowingtermsmean?
(a)thermalneutron
(b)nuclearfission
(c)fissileisotope
27.24Whichfissileisotopeoccursinnature?
27.25Whatfactaboutthefissionof235Umakesitpossibleforachainreactiontooccur?
27.26Explainingeneraltermswhyfissiongeneratesmoreneutronsthanneededtoinitiateit.
27.27Whywouldtherebeasubcriticalmassofafissileisotope?(Whyisn'tanymassof235Ucritical?)
27.28Whatpurposeisservedbyamoderatorinanuclearreactor?
27.29Whyistherenopossibilityofanatomicbomblikeexplosionfromanuclearpowerplant?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 REVIEWPROBLEMS
27.30CalculatethebindingenergyinJofthefollowingnuclei.
(a)deuteriumnucleus(mass=2.0135u)
(b)tritiumnucleus(mass=3.01550u)
27.31Completethefollowingnuclearequationsbywritingthesymbolsofthemissingparticles.
(a)
(b)

(c)
(d)
(e)
(f)
(g)
(h)

27.32Writeabalancednuclearequationforeachofthefollowingchanges.
(a) alphaemissionby242Pu
(b)betaemissionby28Mg
(c) positronemissionby26Si
(d)electroncaptureby37Ar
(e) electroncaptureby55Fe
(f) betaemissionby42K
(g)positronemissionby93Ru
(h)alphaemissionby251Cf
27.33Writethesymbols,includingtheatomicandmassnumbers,fortheradionuclidesthatwouldgive
eachofthefollowingproducts.
(a) 257Fmbyalphaemission
(b)211Bibybetaemission
(c) 141Ndbypositronemission
(d)179Tabyelectroncapture
27.34Eachofthefollowingnuclidesformsbythedecaymodedescribed.Writethesymbolsofthe
parents,givingbothatomicandmassnumbers.
(a) 80Rbformedbyelectroncapture
(b)121Sbformedbybetaemission
(c) 50Crformedbypositronemission
(d)253Cfformedbyalphaemission
27.3587Krdecaysto86Kr.Whatotherparticleforms?
27.36Writethesymbolofthenuclidethatformsfrom58Cowhenitdecaysbyelectroncapture.
27.37Ifanatomof38Khadtheoptionofdecayingbypositronemissionorbetaemission,whichroute
woulditmorelikelytake,andwhy?Writethenuclearequation.
27.38Supposethatanatomof37Arcoulddecaybyeitherbetaemissionorelectroncapture.Which
routewoulditmorelikelytake,andwhy?Writethenuclearequation.
27.39Ifwebeginwith3.00mgof131I ,howmuchremainsaftersixhalflifeperiods?

27.40Smokedetectorscontainasmallamountof241Am,whichhasahalflifeof432.6years.Ifthe
detectorcontains0.20mgof241Am,whatistheactivity,inbecquerels?
27.4190Srisadangerousradioisotopepresentinfalloutproducedbynuclearweapons.Ithasahalflife
of28.9years.Whatistheactivityof1.00gof90Sr,inbecquerels?
27.42131Iisaradioisotopepresentinradioactivefalloutthattargetsthethyroidgland.If1.00mgof
131Ihasanactivityof4.610 12Bq,whatisthedecayconstantfor131I?Whatisthehalflife,in
seconds?
27.43A10.0mgsampleof201Tlhasanactivityof7.910 13Bq.Whatisthedecayconstantfor201Tl?
Whatisthehalflifeof201Tl,inseconds?
27.44When51Vcapturesadeuteron, whatcompoundnucleusforms?(Writeitssymbol.)This
particleexpelsaproton, .Writethenuclearequationfortheoverallchangefrom51V.
27.45Thealphaparticlebombardmentof19Fgenerates22Naandneutrons.Writethenuclearequation,
includingtheintermediatecompoundnucleus.
27.46Gammaraybombardmentof81Brcausesatransmutationinwhichneutronsareoneproduct.
Writethesymboloftheotherproduct.
27.47Neutronbombardmentof115Cdresultsinneutroncaptureandthereleaseofgammaradiation.
Writethenuclearequation.
27.48When55Mnisbombardedbyprotons,neutronsarereleased.Whatelseforms?Writethenuclear
equation.
27.49Whichnuclideformswhen23Naisbombardedbyalphaparticlesandthecompoundnucleus
emitsagammarayphoton?
27.50Thenucleiofwhichisotopeofzincwouldbeneededasbombardmentparticlestomakenucleiof
element112from208Pbiftheintermediatecompoundnucleuslosesaneutron?
27.51Atreekilledbybeingburiedundervolcanicashwasfoundtohavearatioof14Catomsto12C
atomsof4.810 14.Howlongagodidtheeruptionoccur?
27.52Awoodendoorlintelfromanarchaeologicalexcavationwouldbeexpectedtohavewhatratioof
14Cto12Catomsifthelintelis9.010 3yearsold?

27.53Completethefollowingnuclearequationbysupplyingthesymbolfortheotherproductofthe
fission.

27.54Bothproductsofthefissioninquestion27.53areunstable.Accordingtofigures27.1and27.5,
whatisthemostlikelywayforeachofthemtodecay:byalphaemission,betaemissionor
positronemission?Explain.Whataresomeofthepossiblefatesoftheextraneutronsproduced
bythefissionshowninquestion27.53?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 ADDITIONALEXERCISES
27.55Whatisthenuclearequationforeachofthefollowingchanges?
(a) betaemissionby30Al
(b)alphaemissionby252Es
(c) electroncaptureby93Mo
(d)positronemissionby28P
27.56Calculatethebindingenergy(Jpernucleon)ofthenucleusofanatomof56Fe.Theobserved
massofoneatomis55.9349u.
27.57Calculatethebindingenergy(Jpernucleon)of235U.Theobservedmassofoneatomis
235.0439u.
27.58Givethenuclearequationforeachofthefollowingchanges.
(a) positronemissionby10C
(b)alphaemissionby243Cm
(c) electroncaptureby49V
(d)betaemissionby20O
27.59Ifapositronistobeemittedspontaneously,howmuchmoremass(asaminimum)mustanatom
oftheparenthavethananatomofthedaughternuclide?Explain.
27.60Thereisagaininbindingenergypernucleonwhenlightnucleifusetoformheaviernuclei.Yet,
atritiumatomandadeuteriumatom,inamixtureoftheseisotopes,donotspontaneouslyfuseto
givehelium(andenergy).Explainwhynot.
27.61The14Ccontentofanancientpieceofwoodwasfoundtobeoneeighthofthatinlivingtrees.

Howmanyyearsoldisthispieceofwood ?

27.62Dinitrogentrioxide,N2O3,islargelydissociatedintoNOandNO2inthegasphase,wherethe
followingequilibriumexists:

TodeterminethestructureofN2O3,amixtureofNOand*NO2wasprepared,containing
isotopicallylabelled*NintheNO2.Afteraperiodoftime,themixturewasanalysedandfound
tocontainsubstantialamountsofboth*NOand*NO2.Explainhowthisisconsistentwiththe
structureforN2O3beingONONO.
27.63Whichelementhasthelargestbindingenergypernucleon?Whathappenstothenucleiwhenthe
bindingenergyistoosmall?
27.64Whichismoredangerous:ingestingaradioactivecompoundwithashorthalflifeora
radioactivecompoundwithalonghalflifeifthecompoundcanbeeliminatedfromthebody
withinaday?
27.65Theageofyounggroundwatercanbedeterminedbymeasuringtheratiooftritiumto3Hein
water.Ifyounggroundwaterisnomorethan40yearsold,whatpercentoftritiumremainsin
waterafter40years?Theamountof3Heinthewaterismeasuredatthesametimeastheamount
oftritium.Whatwouldthesumoftheamountsoftritiumand3Herepresent?
27.66Thereaction(CH3)2Hg+HgI22CH3HgIisbelievedtooccurthroughatransitionstatewith
thestructure:
 Ifthisisso,whatshouldbeobservedifCH3HgIand*HgI2aremixed,wheretheasteriskdenotes
aradioactiveisotopeofHg?Explainyouranswer.
27.67Alarge,complexpieceofapparatushasacoolingsystembuiltintoitcontaininganunknown
volumeofcoolingliquid.Itisdesiredtomeasurethevolumeofthecoolantwithoutdrainingthe
lines.Tothecoolantwasadded10.0mLof14Clabelledmethanol.Itsspecificactivitywas580
countsperminutepergram(cpmg 1),asdeterminedusingaGeigercounter.Thecoolantwas
permittedtocirculatetoensurecompletemixing.Asamplewasthenwithdrawnandfoundto
haveaspecificactivityof29cpmg 1.Calculatethevolumeofcoolantinthesysteminmillilitres.
Thedensityofmethanolis0.792gmL1,andthedensityofthecoolantis0.884gmL1.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 EPILOGUE
Wehavereachedtheendofourchemistryjourney.Webeganthisbookbylookingattheconstituents
oftheatomandshowinghowwecouldorderall118differenttypesofatomsonthebasisoftheir
atomicnumbertogivetheperiodictable.Wehavelookedindepthatthestructureoftheatom,andhow
andwhyatomscometogethertoformmolecules.Wehaveshownthatallmatterexistsasasolid,liquid
orgasunderdefinedconditions,andwehavediscussedthefactorsthatdeterminewhichofthesethree
phasesasubstancewilladopt.Thepowerofthermodynamicstopredictthepreferreddirectionof
chemicalchangewasdiscussedandwealsolookedatchemicalequilibriumandthespeedofchemical
change.Wethenturnedourattentiontodifferentareasoftheperiodictable,withparticularemphasison
thetransitionmetalsandthepblockelements.Welookedextensivelyatthechemistryofcarbon,and
organicchemistryingeneral,focusingonthereactivityoforganicmolecules,andsomeofthewaysin
whichwecoulddeterminethestructuresofsuchmolecules.Aftersomediscussionofimportant
biologicalmolecules,weeventuallyfoundourselvesbackwherewestarted,attheatom,and
particularlyitsnucleus.

Itisappropriatethatthelastsectionofthebookconcentratedontheapplicationsofchemistrytohuman
life.Ourwayoflifeowesanenormousamounttochemistryandtheadvancesmadeinthissciencein
thefuturewill,toasignificantextent,determinethenatureofourworldinyearstocome.Giventhe
importanceofchemistry,itis,inourview,vitalthatasmanypeopleaspossiblehaveatleastaworking
knowledgeofthesubject,andwehaveaimedtoimpartjustsuchaworkingknowledgetoyouoverthe
past27chapters.Ofcourse,whatiscontainedwithinthistextbookisbynomeansallofchemistry
thoseofyouwhowillcontinueoninthesubjectwillfindawealthofmaterialthatwehavebarely
touchedon,ifatall.Butwehavepresentedyouwiththebasicswhichunderpinboththisscience,and
manyothers.

Allwecandowithinthecontextofatextbookisprovideyouwiththematerialandexplainitin(what
wehopeis)acomprehensibleway.It'suptoyoutolearnandunderstandit.Inthis,wewishyouallthe
best.

Goodluck!

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
 KEYTERMS
activity electroncapture nuclearfission
alphaparticle fissileisotope Nuclearfusion
antimatter gammaradiation positron
bandofstability halflife radioactivedecay
becquerel(Bq) radioactivedisintegration
betaparticle lawofradioactivedecay series
bindingenergypernucleon magicnumbers radiologicaldating
compoundnucleus massdefect strongnuclearforce
criticalmass neutronemission transmutation
decayconstantk nuclearbindingenergy transuraniumelements
nuclearequation

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixA
ThermodynamicDataforSelectedElements,CompoundsandIons(25C)

Substance
Aluminium
Al(s) 0 28.3 0
Al3+(aq) 524.7 481.2

AlCl3(s) 704 110.7 629

Al2O3(s) 1669.8 51.0 1576.4
Al2(SO4)3(s) 3441 239 3100
Arsenic
As(s) 0 35.1 0
AsH3(g) +66.4 223 +68.9
As4O6(s) 1314 214 1153
As2O5(s) 925 105 782
H3AsO3(aq) 742.2
H3AsO4(aq) 902.5
Barium
Ba(s) 0 66.9 0
Ba2+(aq) 537.6 9.6 560.8
BaCO3(s) 1219 112 1139
BaCrO4(s) 1428.0 159 1345
BaCl2(s) 860.2 125 810.8
BaO(s) 553.5 70.4 525.1
Ba(OH)2(s) 998.22 8 875.3
Ba(NO3)2(s) 992 214 795
BaSO4(s) 1465 132 1353
Beryllium
Be(s) 0 9.50 0
BeCl2(s) 468.6 89.9 426.3
BeO(s) 611 14 582
Bismuth
Bi(s) 0 56.9 0
BiCl3(s) 379 177 315
Bi2O3(s) 576 151 497
Boron
B(s) 0 5.87 0
BCl3(g) 404 290 389
B2H6(g) +36 232 +87
B2O3(s) 1273 53.8 1194
B(OH)3(s) 1094 88.8 969
Bromine
Br2(l) 0 152.2 0
Br2(g) +30.9 245.4 3.11
HBr(g) 36 198.5 53.1

Br(aq) 121.55 82.4 103.96

Cadmium
Cd(s) 0 51.8 0

Cd 2+(aq) 75.90 73.2 77.61

CdCl2(s) 392 115 344

CdO(s) 258.2 54.8 228.4
CdS(s) 162 64.9 156
CdSO4(s) 933.5 123 822.6
Calcium
Ca(s) 0 41.4 0

Ca2+(aq) 542.83 53.1 553.58

CaCO3(s) 1207 92.9 1128.8

CaF2(s) 741 80.3 1166
CaCl2(s) 795.0 114 750.2
CaBr2(s) 682.8 130 663.6
Cal2(s) 535.9 143 529
CaO(s) 635.5 40 604.2
Ca(OH)2(s) 986.59 76.1 896.76
Ca3(PO4)2(s) 4119 241 3852
CaSO3(s) 1156
CaSO4(s) 1432.7 107 1320.3
1575.2 131 1435.2

2021.1 194.0 1795.7

CaSO42H2O(s)
Carbon
C(s,graphite) 0 5.69 0
C(s,diamond) +1.88 2.4 +2.9
CCl4(l) 134 214.4 65.3
CHCl3(g) 82.0 234.2 58.6
CO(g) 110.5 197.9 137.3
CO2(g) 394 213.6 394.4
CO2(aq) 413.8 117.6 385.98
H2CO3(aq) 699.65 187.4 623.08

HCO3(aq) 691.99 91.2 586.77

CO32(aq) 677.14 56.9 527.81

CS2(l) +89.5 151.3 +65.3

CS2(g) +115.3 237.7 +67.2
HCN(g) +135.1 201.7 +124.7
CN(aq) +150.6 94.1 +172.4
CH4(g) 74.848 186.2 50.79
C2H4(g) +226.75 200.8 +209
C2H4(g) +51.9 219.8 +68.12
C2H6(g) 84.667 229.5 32.9
C2H8(g) 104 269.9 23
C4H10(g) 126 310.2 17.0
C6H6(l) +49.0 173.3 +124.3
CH3OH(l) 238.6 126.8 166.2
C2H5OH(l) 277.63 161 174.8
HCOOH(g) 363 251 +335
CH3COOH(l) 487.0 160 392.5
HCHO(g) 108.6 218.8 102.5
CH3CHO(g) 167 250 129
(CH3)2CO(l) 248.1 200.4 155.4
C6H5CO2H(s) 385.1 167.6 245.3
CO(NH2)2(s) 333.19 104.6 197.2
CO(NH2)2(aq) 319.2 173.8 203.8
532.9 103.5 373.4
CH2(NH2)CO2H(s)
Chlorine

Cl2(g) 0 223.0 0

Cl(aq) 167.2 56.5 131.2

HCl(g) 92.30 186.7 95.27
HCl(aq) 167.2 56.5 131.2
HClO(aq) 131.3 106.8 80.21
Chromium
Cr(s) 0 23.8 0
Cr3+(aq) 232

CrCl2(s) 326 115 282

CrCl3(s) 563.2 126 493.7
Cr2O3(s) 1141 81.2 1059
CrO3(s) 585.8 72.0 506.2
(NH4)2Cr2O7(s) 1807
K2Cr2O7(s) 2033.01 291 1882
Cobalt
Co(s) 0 30.0 0

Co 2+(aq) 59.4 110 53.6

CoCl2(s) 325.5 106 282.4

Co(NO3)2(s) 422.2 192 230.5
CoO(s) 237.9 53.0 214.2
CoS(s) 80.8 67.4 82.8
Copper
Cu(s) 0 33.15 0

Cu 2+(aq) +64.77 99.6 +65.49

CuCl(s) 137.2 86.2 119.87

CuCl2(s) 172 119 131
Cu 2O(s) 168.6 93.1 146.0
CuO(s) 155.25 42.6 127
Cu 2S(s) 79.5 121 86.2
CuS(s) 53.1 66.5 53.6
CuSO4(s) 771.4 109 661.8
CuSO45H2O(s) 2279.7 300.4 1879.7
Fluorine
F2(g) 0 202.7 0

F(aq) 332.6 13.8 278.8

HF(g) 271 173.5 273

Gold
Au(s) 0 47.7 0
Au 2O3(s) +80.8 125 +163
AuCl3(s) 118 148 48.5
Hydrogen
H2(g) 0 130.6 0
H2O(l) 285.9 69.96 237.2
H2O(g) 241.8 188.7 228.6
H2O2(l) 187.6 109.6 120.3
H2Se(g) +76 219 +62.3
H2Te(g) +154 234 +138
Iodine
I2(s) 0 116.1 0
I2(g) +62.4 260.7 +19.3
HI(g) +26.6 206 +1.30
Iron
Fe(s) 0 27 0

Fe2+(aq) 89.1 137.7 78.9

Fe3+(aq) 48.5 315.9 4.7

Fe2O3(s) 822.3 90.0 741.0

Fe3O4(s) 1118.4 146.4 1015.4
FeS(s) 100.0 60.3 100.4
FeS2(s) 178.2 52.9 166.9
Lead
Pb(s) 0 64.8 0

Pb 2+(aq) 1.7 10.5 24.4

PbCl2(s) 359.4 136 314.1

PbO(s) 219.2 67.8 189.3
PbO2(s) 277 68.6 219
Pb(OH)2(s) 515.9 88 420.9
PbS(s) 100 91.2 98.7
PbSO4(s) 920.1 149 811.3
Lithium
Li(s) 0 28.4 0

Li+(aq) 278.6 10.3

LiF(s) 611.7 35.7 583.3

LiCl(s) 407.5 59.29 383.7
LiBr(s) 350.3 66.9 338.87
Li2O(s) 596.5 37.9 560.5
Li3N(s) 199 37.7 155.4
Magnesium
Mg(s) 0 32.5 0

Mg 2+(aq) 466.9 138.1 454.8

MgCO3(s) 1113 65.7 1029

MgF2(s) 1124 79.9 1056
MgCl2(s) 641.8 89.5 592.5
MgCl22H2O(s) 1280 180 1118
Mg 3N2(s) 463.2 87.9 411
MgO(s) 601.7 26.9 569.4
Mg(OH)2(s) 924.7 63.1 833.9
Manganese
Mn(s) 0 32.0 0

Mn 2+(aq) 223 74.9 228

MnO4(aq) 542.7 191 449.4

KMnO4(s) 813.4 171.71 713.8

MnO(s) 385 60.2 363
Mn 2O3(s) 959.8 110 882.0
MnO2(s) 520.9 53.1 466.1
Mn 3O4(s) 1387 149 1280
MnSO4(s) 1064 112 956
Mercury
Hg(l) 0 76.1 0
Hg(g) +60.84 175 +31.8
Hg 2Cl2(s) 265.2 192.5 210.8
HgCl2(s) 224.3 146.0 178.6
HgO(s) 90.83 70.3 58.54
HgS(s,red) 58.2 82.4 50.6
Nickel

Ni(s) 0 30 0
NiCl2(s) 305 97.5 259
NiO(s) 244 38 216
NiO2(s) 199
NiSO4(s) 891.2 77.8 773.6
NiCO3(s) 664.0 91.6 615.0
Ni(CO)4(g) 220 399 567.4
Nitrogen
N2(g) 0 191.5 0
NH3(g) 46.0 192.5 16.7

NH4+(aq) 132.5 113 79.37

N2H4(g) +95.40 238.4 +159.3

N2H4(l) +50.6 121.2 +149.4
NH4Cl(s) 315.4 94.6 203.9
NO(g) +90.37 210.6 +86.69
NO2(g) +33.8 240.5 +51.84
N2O(g) +81.57 220.0 +103.6
N2O4(g) +9.67 304 +98.28
N2O5(g) +11 356 +115
HNO3(l) 173.2 155.6 79.91

NO3(aq) 205.0 146.4 108.74

Oxygen
O2(g) 0 205.0 0
O3(g) +143 238.8 +163

OH(aq) 230.0 10.75 157.24

Phosphorus
P(s,white) 0 41.09 0
P4(g) +314.6 163.2 +278.3
PCl3(g) 287.0 311.8 267.8
374.9 364.6 305.0
PCl5(g)
PH3(g) +5.4 210.2 +12.9
P4O6(s) 1640
POCl3(g) 1109.7 646.5 1019
POCl3(l) 1186 26.36 1035

P4O10(s) 3062 228.9 2698

H3PO4(s) 1279 110.5 1119
Potassium
K(s) 0 64.18 0

K+(aq) 252.4 102.5 283.3

KF(s) 567.3 66.6 537.8

KCl(s) 435.89 82.59 408.3
KBr(s) 393.8 95.9 380.7
KI(s) 327.9 106.3 324.9
KOH(s) 424.8 78.9 379.1
K2O(s) 361 98.3 322
K2SO4(s) 1433.7 176 1316.4
Silicon
Si(s) 0 19 0
SiH4(g) +33 205 +52.3
SiO2(s,alpha) 910.0 41.8 856
Silver
Ag(s) 0 42.55 0

Ag +(aq) +105.58 72.68 +77.11

AgCl(s) 127.1 96.2 109.7

AgBr(s) 100.4 107.1 96.9
AgNO3(s) 124 141 32
Ag 2O(s) 31.1 121.3 11.2
Sodium
Na(s) 0 51.0 0

Na+(aq) 240.12 59.0 261.91

NaF(s) 571 51.5 545
NaCl(s) 411.0 72.38 384.0
NaBr(s) 360 83.7 349
NaI(s) 288 91.2 286
 NaHCO3(s) 947.7 102 851.9
Na2CO3(s) 1131 136 1048
Na2O2(s) 510.9 94.6 447.7
Na2O2(s) 510 72.8 376
NaOH(s) 426.8 64.18 382

Na2SO4(s) 1384.5 149.4 1266.83

Sulfur
S(s,rhombic) 0 31.9 0
SO2(g) 296.9 248.5 300.4
SO3(g) 395.2 256.2 370.4
H2S(g) 20.15 206 33.6
H2SO4(l) 811.32 157 689.9
H2SO4(aq) 909.3 20.1 744.5
SF6(g) 1209 292 1105
Tin
Sn(s,white) 0 51.6 0

Sn 2+(aq) 8.8 17 27.2

SnCl4(l) 511.3 258.6 440.2

SnO(s) 285.8 56.5 256.9
SnO2(s) 580.7 52.3 519.6
Zinc
Zn(s) 0 41.6 0

Zn 2+(aq) 153.9 112.1 147.06

ZnCl2(s) 415.1 111 369.4

ZnO(s) 348.3 43.6 318.3
ZnS(s) 205.6 57.7 201.3
ZnSO4(s) 982.8 120 874.5

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixB
AverageBondEnthalpies(25C)

Bond Bondenthalpy(kJmol1)
CC 348
C C 612
CC 960
CH 412
CN 305
C N 613
CN 890
CO 360
C O 743
CF 484
CCl 338
CBr 276
CI 238
HH 436
HF 565
HCl 431
HBr 366
HI 299
HN 388
HO 463
HS 338
HSi 376

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixC
SolubilityProducts(25C)

Salt Solubilityequilibrium Ksp

Fluorides
MgF2 MgF2(s) Mg 2+(aq)+2F(aq) 6.610 9
CaF2 CaF2(s) Ca2+(aq)+2F(aq) 3.910 11
SrF2 SrF2(s) Sr2+(aq)+2F(aq) 2.910 9
BaF2 BaF2(s) Ba2+(aq)+2F(aq) 1.710 6
LiF LiF(s) Li+(aq)+F(aq) 1.710 3
PbF2 PbF2(s) Pb 2+(aq)+2F(aq) 3.610 8
Chlorides
CuCl CuCl(s) Cu +(aq)+Cl(aq) 1.910 7
AgCl AgCl(s) Ag +(aq)+Cl(aq) 1.810 10
Hg 2Cl2 Hg 2Cl2(s) Hg 22+(aq)+2Cl(aq) 1.210 18
TlCl TlCl(s) Tl+(aq)+Cl(aq) 1.810 4
PbCl2 PbCl2(s) Pb 2+(aq)+2Cl(aq) 1.710 5

AuCl3 AuCl3(s) Au 3+(aq)+3Cl(aq) 3.210 25

Bromides
CuBr CuBr(s) Cu +(aq)+Br(aq) 510 9
AgBr AgBr(s) Ag +(aq)+Br(aq) 5.010 13
Hg 2Br2 Hg 2Br2(s) Hg 22+(aq)+2Br(aq) 5.610 23
HgBr2 HgBr2(s) Hg 2+(aq)+2Br(aq) 1.310 19
PbBr2 PbBr2(s) Pb 2+(aq)+2Br(aq) 2.110 6

Iodides
CuI CuI(s) Cu +(aq)+I(aq) 110 12
AgI AgI(s) Ag +(aq)+I(aq) 8.310 17
Hg 2I2 Hg 2I2(s) Hg 22+(aq)+2I(aq) 4.710 29
HgI2 HgI2(s) Hg 2+(aq)+2I(aq) 1.110 28
PbI2 PbI2(s) Pb 2+(aq)+2I(aq) 7.910 9
Hydroxides
Mg(OH)2 Mg(OH)2(s) Mg 2+(aq)+2OH(aq) 7.110 12
Ca(OH)2 Ca(OH)2(s) Ca2+(aq)+2OH(aq) 6.510 6
Mn(OH)2 Mn(OH)2(s) Mn 2+(aq)+2OH(aq) 1.610 13
Fe(OH)2 Fe(OH)2(s) Fe2+(aq)+2OH(aq) 7.910 16
Fe(OH)3 Fe(OH)3(s) Fe3+(aq)+3OH(aq) 1.610 39
Co(OH)2 Co(OH)2(s) Co 2+(aq)+2OH(aq) 110 15
Co(OH)3 Co(OH)3(s) Co 3+(aq)+3OH(aq) 310 45
Ni(OH)2 Ni(OH)2(s) Ni2+(aq)+2OH(aq) 610 16
Cu(OH)2 Cu(OH)2(s) Cu 2+(aq)+2OH(aq) 4.810 20
V(OH)3 V(OH)3(s) V3+(aq)+3OH(aq) 410 35
Cr(OH)3 Cr(OH)3(s) Cr3+(aq)+3OH(aq) 210 30
Zn(OH)2 Zn(OH)2(s) Zn 2+(aq)+2OH(aq) 3.010 16
Cd(OH)2 Cd(OH)2(s) Cd 2+(aq)+2OH(aq) 5.010 15
Al(OH)3(alphaform) Al(OH) (s) Al3+(aq)+3OH(aq) 310 34
3

Cyanides
AgCN AgCN(s) Ag +(aq)+CN(aq) 2.210 16
Zn(CN)2 Zn(CN)2(s) Zn 2+(aq)+2CN(aq) 310 16
Sulfites
CaSO3 CaSO3(s) Ca2+(aq)+SO32(aq) 310 7
Ag 2SO3 Ag 2SO3(s) 2Ag +(aq)+SO32(aq) 1.510 14
BaSO3 BaSO3(s) Ba2+(aq)+SO32(aq) 810 7
Sulfates
CaSO4 CaSO4(s) Ca2+(aq)+SO42(aq) 2.410 5
SrSO4 SrSO4(s) Sr2+(aq)+SO42(aq) 3.210 7
BaSO4 BaSO4(s) Ba2+(aq)+SO42(aq) 1.110 10
RaSO4 RaSO4(s) Ra2+(aq)+SO42(aq) 4.310 11
Ag 2SO4 Ag 2SO4(s) 2Ag +(aq)+SO42(aq) 1.510 5
Hg 2SO4 Hg 2SO4(s) Hg 22+(aq)+SO42(aq) 7.410 7
PbSO4 PbSO4(s) Pb 2+(aq)+SO42(aq) 6.310 7
Chromates
BaCrO4 BaCrO4(s) Ba2+(aq)+CrO42(aq) 2.110 10
CuCrO4 CuCrO4(s) Cu 2+(aq)+CrO42(aq) 3.610 6
Ag 2CrO4 Ag 2CrO4(s) 2Ag +(aq)+CrO42(aq) 1.210 12
Hg 2CrO4 Hg 2CrO4(s) Hg 22+(aq)+CrO42(aq) 2.010 9
CaCrO4 CaCrO4(s) Ca2+(aq)+CrO42(aq) 7.110 4
PbCrO4 PbCrO4(s) Pb 2+(aq)+CrO42(aq) 1.810 14
Carbonates
MgCO3 MgCO3(s) Mg 2+(aq)+CO32(aq) 3.510 8
CaCO3 CaCO3(s) Ca2+(aq)+CO32(aq) 4.510 9
SrCO3 SrCO3(s) Sr2+(aq)+CO32(aq) 9.310 10
BaCO3 BaCO3(s) Ba2+(aq)+CO32(aq) 5.010 9
MnCO3 MnCO3(s) Mn 2+(aq)+CO32(aq) 5.010 10
FeCO3 FeCO3(s) Fe2+(aq)+CO32(aq) 2.110 11
CoCO3 CoCO3(s) Co 2+(aq)+CO32(aq) 1.010 10
NiCO3 NiCO3(s) Ni2+(aq)+CO32(aq) 1.310 7
CuCO3 CuCO3(s) Cu 2+(aq)+CO32(aq) 2.310 10
Ag 2CO3 Ag 2CO3(s) 2Ag +(aq)+CO32(aq) 8.110 12
Hg 2CO3 Hg 2CO3(s) Hg 22+(aq)+CO32(aq) 8.910 17
ZnCO3 ZnCO3(s) Zn 2+(aq)+CO32(aq) 1.010 10
CdCO3 CdCO3(s) Cd 2+(aq)+CO32(aq) 1.810 14
PbCO3 PbCO3(s) Pb 2+(aq)+CO32(aq) 7.410 14
Phosphates
Ca3(PO4)2 Ca3(PO4)2(s) 3Ca2+(aq)+2PO43(aq) 2.010 29
Mg 3(PO4)2 Mg 3(PO4)2(s) 3Mg 2+(aq)+2PO43(aq) 6.310 26
SrHPO4 SrHPO4(s) Sr2+(aq)+HPO42(aq) 1.210 7
BaHPO4 BaHPO4(s) Ba2+(aq)+HPO42(aq) 4.010 8
LaPO4 LaPO4(s) La3+(aq)+PO43(aq) 3.710 23
Fe3(PO4)2 Fe3(PO4)2(s) 3Fe2+(aq)+2PO43(aq) 110 36
Ag 3PO4 Ag 3PO4(s) 3Ag +(aq)+PO43(aq) 2.810 18
FePO4 4.010 27
 FePO4(s) Fe3+(aq)+PO43(aq)
Zn 3(PO4)2 Zn 3(PO4)2(s) 3Zn 2+(aq)+2PO43(aq) 510 36
Pb 3(PO4)2 Pb 3(PO4)2(s) 3Pb 2+(aq)+2PO43(aq) 3.010 44
Ba3(PO4)2 Ba3(PO4)2(s) 3Ba2+(aq)+2PO43(aq) 5.810 38
Ferrocyanides
Zn 2[Fe(CN)6] Zn 2[Fe(CN)6](s) 2Zn 2+(aq)+[Fe(CN)6]4(aq) 2.110 16
Cd 2[Fe(CN)6] Cd 2[Fe(CN)6](s) 2Cd 2+(aq)+[Fe(CN)6]4(aq) 4.210 18
Pb 2[Fe(CN)6] Pb 2[Fe(CN)6](s) 2Pb 2+(aq)+[Fe(CN)6]4(aq) 9.510 19

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixD
CumulativeFormationConstantsofComplexes(25C)

Equilibrium n n
Halidecomplexes
Al3++6F [AlF6]3 2.510 4 6

Al3++4F [AlF4] 2.010 8 4

Be2++4F [BeF4]2 1.310 13 4

Sn 4++6F [SnF6]2 110 25 6

Cu ++2Cl [CuCl2] 310 5 2

Ag ++2Cl [AgCl2] 1.810 5 2

Pb 2++4Cl [PbCl4]2 2.510 15 4

Zn 2++4Cl [ZnCl4]2 1.6 4

Hg 2++4Cl [HgCl4]2 5.010 15 4

Cu ++2Br [CuBr2] 810 5 2

Ag ++2Br [AgBr2] 1.710 7 2

Hg 2++4Br [HgBr4]2 110 21 4

Cu ++2I [CuI2] 810 8 2

Ag ++2I [AgI2] 110 11 2

Pb 2++4I [PbI4]2 310 4 4

Hg 2++4I [HgI4]2 1.910 30 4

Ammoniacomplexes
Ag ++2NH3 [Ag(NH3)2]+ 1.610 7 2

Zn 2++4NH3 [Zn(NH3)4]2+ 7.810 8 4

Cu 2++4NH3 [Cu(NH3)4]2+ 1.110 13 4

Hg 2++4NH3 [Hg(NH3)4]2+ 1.810 19 4

Co 2++6NH3 [Co(NH3)6]2+ 5.010 4 6

Co 3++6NH3 [Co(NH3)6]3+ 4.610 33 6

Cd 2++6NH3 [Cd(NH3)6]2+ 2.610 5 6

2.010 8 6
Ni2++6NH3 [Ni(NH3)6]2+
Cyanidecomplexes

Fe2++6CN [Fe(CN)6]4 1.010 24 6

Fe3++6CN [Fe(CN)6]3 1.010 31 6

Ag ++2CN [Ag(CN)2] 5.310 18 2

Cu ++2CN [Cu(CN)2] 1.010 16 2

Cd 2++4CN [Cd(CN)4]2 7.710 16 4

Au ++2CN [Au(CN)2] 210 38 2

Complexeswithothermonodentateligands
methylamine(CH3NH2)

Ag ++2CH3NH2 [Ag(CH3NH2)2]+thiocyanateion(SCN) 7.810 6 2

Cd 2++4SCN [Cd(SCN)4]2 110 3 4

Cu 2++2SCN [Cu(SCN)2] 5.610 3 2

Fe3++3SCN [Fe(SCN)3] 210 6 3

Hg 2++4SCN [Hg(SCN)4]2hydroxideion(OH) 5.010 21 4

Cu 2++4OH [Cu(OH)4]2 1.310 16 4

Zn 2++4OH [Zn(OH)4]2 210 20 4

Complexeswithbidentateligands(a)

Mn 2++3en [Mn(en)3]2+ 6.510 5 3

Fe2++3en [Fe(en)3]2+ 5.210 9 3

Co 2++3en [Co(en)3]2+ 1.010 14 3

Co 3++3en [Co(en)3]3+ 5.010 48 3

Ni2++3en [Ni(en)3]2+ 4.110 17 3

Cu 2++2en [Cu(en)2]2+ 4.010 19 2

Mn 2++3bipy [Mn(bipy)3]2+ 110 6 3

Fe2++3bipy [Fe(bipy)3]2+ 1.610 17 3

Ni2++3bipy [Ni(bipy)3]2+ 3.010 20 3

Co 2++3bipy [Co(bipy)3]2+ 810 15 3

Mn 2++3phen [Mn(phen)3]2+ 210 10 3

Fe2++3phen [Fe(phen)3]2+ 110 21 3

 Co 2++3phen [Co(phen)3]2+ 610 19 3

Ni2++3phen [Ni(phen)3]2+ 210 24 3

Co 2++3C2O42 [Co(C2O4)3]4 4.510 6 3

Fe3++3C2O42 [Fe(C2O4)3]3 3.310 20 3

Complexesofotherligands

Zn 2++EDTA4 [Zn(EDTA)]2 3.810 16 1

Mg 2++2NTA3 [Mg(NTA)2]4 1.610 10 2

Ca2++2NTA3 [Ca(NTA)2]4 3.210 11 2

(a)en=ethylenediamine

bipy=bipyridine

phen=1,10phenanthroline

EDTA4=ethylenediaminetetraacetateion

NTA3=nitrilotriacetateion

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixE
AcidityandBasicityConstantsforWeakAcidsandBases(25C)

Monoproticacids Name Ka
Cl3CCOOH trichloroaceticacid 2.210 1
HIO3 iodicacid 1.710 1
Cl2CHCOOH dichloroaceticacid 5.010 2
ClCH2COOH chloroaceticacid 1.410 3
HNO2 nitrousacid 7.110 4
HF hydrofluoricacid 6.810 4
HOCN cyanicacid 3.510 4
HCOOH formicacid 1.810 4
CH3CH(OH)COOH lacticacid 1.410 4
C4H4N2O3 barbituricacid 9.810 5
C6H5COOH benzoicacid 6.310 5
CH3CH2CH2COOH butanoicacid 1.510 5
HN3 hydrazoicacid 1.810 5
CH3COOH aceticacid 1.810 5
CH3CH2COOH propanoicacid 1.410 5
HOCl hypochlorousacid 3.010 8
HOBr hypobromousacid 2.110 9
HCN hydrocyanicacid 6.210 10
C6H5OH phenol 1.310 10
HOI hypoiodousacid 2.310 11
H2O2 hydrogenperoxide 1.810 12
Polyproticacids Name Ka1 Ka2 Ka3

H2SO4 sulfuricacid large 1.010 2

H2CrO4 chromicacid 5.0 1.510 6

H2C2O4 oxalicacid 5.610 2 5.410 5

H3PO3 phosphorousacid 310 2 1.610 7

H2SO3[SO2(aq)] sulfurousacid 1.210 2 6.610 8

H2SeO3 selenousacid 4.510 3 1.110 8
 H2TeO3 tellurousacid 3.310 3 2.010 8

HOOCCH2COOH malonicacid 1.410 3 2.010 6

C6H4(COOH)2 phthalicacid 1.110 3 3.910 6

HOOCCH(OH)CH(OH)COOH tartaricacid 9.210 4 4.310 5

C6H8O6 ascorbicacid 6.810 5 2.710 12

H2CO3 carbonicacid 4.510 7 4.710 11
H3PO4 phosphoricacid 7.110 3 6.310 8 4.510 13
H3AsO4 arsenicacid 5.610 3 1.710 7 4.010 12
C6H8O7 citricacid 7.110 4 1.710 5 6.310 6
Weakbases Name Kb

(CH3)2NH dimethylamine 9.610 4

CH3NH2 methylamine 4.410 4
CH3CH2NH2 ethylamine 4.310 4
(CH3)3N trimethylamine 7.410 5
NH3 ammonia 1.810 5
N2H4 hydrazine 1.710 6
NH2OH hydroxylamine 6.610 9
C5H5N pyridine 1.710 9
C6H5NH2 aniline 4.110 10

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixF
StandardReductionPotentials(25C)

Halfreaction

F2(g)+2e 2F(aq) +2.87

O3(g)+2H+(aq)+2e O2(g)+H2O(l) +2.08

S2O82(aq)+2e 2SO42(aq) +2.01

Co 3+(aq)+e Co 2+(aq) +1.82

H2O2(aq)+2H+(aq)+2e 2H2O(l) +1.77

PbO2(s)+HSO4(aq)+3H+(aq)+2e PbSO4(s)+2H2O(l) +1.69

2HOCl(aq)+2H+(aq)+2e Cl2(g)+2H2O(l) +1.63

Mn 3+(aq)+e Mn 2+(aq) +1.51

MnO4(aq)+4H+(aq)+3e MnO2(s)+2H2O(l) +1.51

MnO4(aq)+8H+(aq)+5e Mn 2+(aq)+4H2O(l) +1.49

PbO2(s)+4H+(aq)+2e Pb 2+(aq)+2H2O(l) +1.47

BrO3(aq)+6H+(aq)+6e Br(aq)+3H2O(l) +1.46

Au 3+(aq)+3e Au(s) +1.42

Cl2(g)+2e 2Cl(aq) +1.36

Cr2O72(aq)+14H+(aq)+6e 2Cr3+(aq)+7H2O(l) +1.33

O3(g)+H2O(l)+2e O2(g)+2OH(aq) +1.24

MnO2(s)+4H+(aq)+2e Mn 2+(aq)+2H2O(l) +1.23

O2(g)+4H+(aq)+4e 2H2O(l) +1.23

Pt2+(aq)+2e Pt(s) +1.20

Br2(aq)+2e 2Br(aq) +1.07

NO3(aq)+4H+(aq)+3e NO(g)+2H2O(l) +0.96

NO3(aq)+3H+(aq)+2e HNO2(aq)+H2O(l) +0.94

2Hg 2+(aq)+2e Hg 22+(aq) +0.91

HO2(aq)+H2O(l)+2e 3OH(aq) +0.87

NO3(aq)+4H+(aq)+2e 2NO2(g)+2H2O(l) +0.80

Ag +(aq)+e Ag(s) +0.80

Fe3+(aq)+e Fe2+(aq) +0.77

O2(g)+2H+(aq)+2e H2O2(aq) +0.69

I2(s)+2e 2I(aq) +0.54

NiO2(s)+2H2O(l)+2e Ni(OH)2(s)+2OH(aq) +0.49

SO2(aq)+4H+(aq)+4e S(s)+2H2O(l) +0.45

O2(g)+2H2O(l)+4e 4OH(aq) +0.401

Cu 2+(aq)+2e Cu(s) +0.34

Hg 2Cl2(s)+2e 2Hg(l)+2Cl(aq) +0.27

PbO2(s)+H2O(l)+2e PbO(s)+2OH(aq) +0.25

AgCl(s)+e Ag(s)+Cl(aq) +0.23

SO42(aq)+4H+(aq)+2e H2SO3(aq)+H2O(l) +0.17

S4O62(aq)+2e 2S2O32(aq) +0.169

Cu 2+(aq)+e Cu +(aq) +0.16

Sn 4+(aq)+2e Sn 2+(aq) +0.15

S(s)+2H+(aq)+2e H2S(g) +0.14

AgBr(s)+e Ag(s)+Br(aq) +0.07

2H+(aq)+2e H2(g) 0.00

Pb 2+(aq)+2e Pb(s) 0.13

Sn 2+(aq)+2e Sn(s) 0.14

AgI(s)+e Ag(s)+I(aq) 0.15

Ni2+(aq)+2e Ni(s) 0.25

Co 2+(aq)+2e Co(s) 0.28

In 3+(aq)+3e In(s) 0.34

Tl+(aq)+e Tl(s) 0.34

PbSO4(s)+H+(aq)+2e Pb(s)+HSO4(aq) 0.36

Cd 2+(aq)+2e Cd(s) 0.40

Fe2+(aq)+2e Fe(s) 0.44

Ga3+(aq)+3e Ga(s) 0.56

PbO(s)+H2O(l)+2e Pb(s)+2OH(aq) 0.58

Cr3+(aq)+3e Cr(s) 0.74

Zn 2+(aq)+2e Zn(s) 0.76

 Cd(OH)2(s)+2e Cd(s)+2OH(aq) 0.81

2H2O(l)+2e H2(g)+2OH(aq) 0.83

Fe(OH)2(s)+2e Fe(s)+2OH(aq) 0.88

Cr2+(aq)+2e Cr(s) 0.91

N2(g)+4H2O(l)+4e N2O4(aq)+4OH(aq) 1.16

V2+(aq)+2e V(s) 1.18

ZnO22(aq)+2H2O(l)+2e Zn(s)+4OH(aq) 1.216

Ti2+(aq)+2e Ti(s) 1.63

Al3+(aq)+3e Al(s) 1.66

U3+(aq)+3e U(s) 1.79

Sc3+(aq)+3e Sc(s) 2.02

La3+(aq)+3e La(s) 2.36

Y3+(aq)+3e Y(s) 2.37

Mg 2+(aq)+2e Mg(s) 2.37

Na+(aq)+e Na(s) 2.71

Ca2+(aq)+2e Ca(s) 2.76

Sr2+(aq)+2e Sr(s) 2.89

Ba2+(aq)+2e Ba(s) 2.90

Cs+(aq)+e Cs(s) 2.92

K+(aq)+e K(s) 2.92

Rb +(aq)+e Rb(s) 2.93

Li+(aq)+e Li(s) 3.05

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixG
IonisationEnergiesandElectronAffinitiesoftheFirst36Elementsat25C

Z Symbol EA IE1 IE2 IE3

1 H 72.8 1312
2 He >0 2372 5250
3 Li 59.7 520.2 7298 11815
4 Be >0 899.4 1757 14848
5 B 26.8 800.6 2427 3660
6 C 121.9 1086 2353 4620
7 N >0 1402 2856 4578
8 0 141.1 1314 3388 5300
9 F 322.0 1681 3374 6050
10 Ne >0 2080 3952 6122
11 Na 52.9 495.6 4560 6912
12 Mg >0 737.7 1450 7730
13 Al 42.7 577 1817 2745
14 Si 133.6 786.4 1577 3232
15 P 72.0 1012 1908 2912
16 S 200.4 999.6 2251 3357
17 Cl 348.8 1256 2297 3822
18 Ar >0 1520 2666 3931
19 K 48.4 418.8 3051 4420
20 Ca 2.4 589.8 1145 4912
21 Sc 18.2 633 1235 2389
22 Ti 7.7 658 1310 2653
23 V 50.8 650 1414 2828
24 Cr 64.4 652.8 1591 2987
25 Mn >0 717.4 1509 3248
26 Fe 14.6 763 1561 2957
27 Co 63.9 758 1646 3232
28 Ni 111.6 736.7 1753 3396
29 Cu 119.2 745.4 1958 3554
30 Zn >0 906.4 1733 3833
31 Ga 28.9 578.8 1979 2963
32 Ge 119 761 1537 3302
 33 As 78 947 1798 2736
34 Se 195.0 940.9 2045 2974
35 Br 324.6 1143 2103 3500
36 Kr >0 1351 2350 3565

AllvaluesareinkJmol1.Avalueof>0meansthattheanionisunstable,soitselectronaffinity
cannotbedeterminedexperimentally.Colourshadingindicatestheprincipalquantumnumber,n,
oftheelectronwhoseionisationenergyislisted:blue,n=1green,n=2orange,n=3purple,n
=4yellow,n=5.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
AppendixH
CharacteristicInfraredAbsorptionFrequencies

Bonding Frequency(cm1) Intensity(a)

CH alkane 28503000 s
CH3 1375and1450 wm
CH2 1450 m
alkene 30003100 wm
6501000 s
alkyne 3300 ms
16001680 wm
aromatic 30003100 s
690900 s
aldehyde 27002800 w
28002900 w
C C alkene 16001680 wm
aromatic 1450and1600 wm
CO 10501100(sp 3CO) s
s
12001250(sp 2CO) s
C O amide 16301680 s
carboxylicacid 17001725 s
ketone 17051780 s
aldehyde 17051740 s
ester 17351750 s
anhydride 1760and1800 s
OH alcohol,phenol
free 36003650 m
Hbonded 32003500 m
carboxylicacid 24003400 m
NH amineandamide 31003500 ms
(a)m=medium,s=strong,w=weak

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.


GLOSSARYOFEQUATIONS
acidityconstantforthe
acidbasereaction:HA(aq)
+H2O(l) H3O+(aq)+
A(aq)
Arrheniusequation

Avogadro'sLaw

basicityconstantforthe
acidbasereaction:B(aq)+
H2O(l) BH+(aq)+
OH(aq)
boilingpointelevation

bondorder bondorder (numberofelectronsinbondingmolecularorbitals

numberofelectronsinantibondingmolecularorbitals)
Boyle'sLaw

Braggequation
cellpotential

Charles'Law

concentrationmolality

molarity

cumulativeformation
constantfortheformation
reaction:Mx+(aq)+nL(aq)
[MLn]x+(aq)
Dalton'slawofpartial
pressures
deBroglieequation
electrostaticpotential
energy
energyofaphoton

enthalpy

entropyofreaction,
standardforthegeneral
reaction:aA+bBcC+
dD
entropyandenthalpy,
relationship

equilibriumconstant
expressionforthesolution
phasereaction:aA+bB
cC+dD

equilibriumconstantforthe
gasphasereaction:aA+bB
cC+dD

Faraday'slaw

firstlawofthermodynamics

freezingpointdepression

gasdensity

Gibbsfreeenergy

changeinstandardGibbs
freeenergy
halflifeforafirstorder
reaction

halflifeforasecondorder
reaction

halflifeforazeroorder
reaction

heat

heatofreaction

HendersonHasselbalch
equation

Henry'slaw

Hess'slawequationforthe
generalreaction:aA+bB
cC+dD
hydrogenatomemission
energies

hydrogenatomemission
frequencies

idealgasequation

indexofhydrogendeficiency
(IHD)

integratedratelawfora
firstorderreaction

integratedratelawfora
secondorderreaction

integratedratelawfora
zeroorderreaction
isoelectricpointofanamino
acid

kineticenergy

KpabdKc,relationship

lawofradioactivedecay

magneticmomentofa
transitionmetalcomplex
MichaelisMentenequation

molarmass

molefraction

momentumofaparticle

Nernstequation

NMRchemicalshift

partialpressureofa
componentofagasmixture
percentagebymass

percentageyield

pH

pKaandpKb,relationship

radiocarbondating

Raoult'slaw
Raoult'slawforatwo
componentsystem:
ratelawsfororganic
reactions

rateofreactionforthe
generalreaction:aA+bB
cC+dD
reactionquotientforthe
solutionphasereaction:aA
+bB cC+dD
rootmeansquarespeedof
gasatoms/molecules

Schrdingerequation

solubilityproductofasalt
for:MaXb(s) aMb+(aq)
+bXa(aq)
specificheat

specificrotation

speedofalightwave
vanderWaalsequation

van'tHoffequation
van'tHoffequationfor
osmoticpressure
van'tHofffactor

workdoneinthe
expansion/compressionofa
gas

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.


GLOSSARY
A
absolute Anuncertaintywhichhasthesameunitsasthequantitybeingmeasured.(p.31)
uncertainty
absorbance Ameasureofthelightabsorbedbyasolutionofacompounddefinedbythe
(A) equation .(p.571)
absorption Thedistributionofwavelengthsoflightabsorbedbyaspecies.(p.117)
spectrum
acidanhydride Acompoundinwhichtwoacylgroupsarebondedtothesameoxygenatom.(p.
1002)
acceptorstem ThepartofthetRNAmoleculethatcarriestheaminoacidandinwhichnucleotide
sequencesfromthe5and3endsarepairedtoformduplexRNA.(p.1101)
accuracy Ameasurementisofhighaccuracyifitisclosetothecorrectvalue.(p.34)
acetal AmoleculecontainingtwoORorOArgroupsbondedtothesamecarbonatom.
(p.946)
achiral Describesanobjectthatlackschirality,thatis,itissuperimposableonitsmirror
image.(p.747)
acid ArrheniustheoryasubstancethatproducesH+ionsinwater(p.428)Brnsted
Lowrytheoryaprotondonor(p.428)Lewistheoryanelectronpairacceptor.
(p.476)
acidbase Adyehavingonecolourinacidandanothercolourinbase.(p.467)
indicator
acidbase Areactionthatinvolvesthetransferofasingleprotonfromonespeciestoanother.
reaction (NotethatthisistheBrnstedLowrydefinition.)(p.428)
acidbase Ananalyticalprocedureinvolvingthegradualadditionofasolutionofanacidor
titration baseofknownconcentrationtoaspecifiedvolumeofasolutionofabaseoracidof
unknownconcentration.(p.467)
acidhalide AderivativeofacarboxylicacidinwhichtheOHofthecarboxylgroupis
replacedbyahalogen,mostcommonlychlorine.(p.1002)
acidic Describesanaqueoussolutioninwhich[H O+]>[OH].(p.433)
3
acidity Theequilibriumconstantforthedissociationofanacidinaqueoussolution.Forthe
constant(Ka) generalequilibrium:

(p.443)
actinoids Elements89to103oftheperiodictable.(p.14)
activation Theminimumkineticenergythatmustbepossessedbythereactantsinordertogive
energy(Ea) aneffectivecollisionleadingtoproducts.(p.652)
activities Effectiveconcentrationsthatgiverisetothermodynamicequilibriumconstantswhen
substitutedintoanequilibriumconstantexpression.(p.353)
activity Thenumberofdisintegrationspersecondofaradioactivesubstance.(p.1168)
actualyield Themassofaproductobtainedfromareaction.(p.88)
acyclicalkanes Alkanemoleculesthatconsistsolelyofchainsofcarbonatoms.(p.54)
acylation Theprocessofintroducinganacylgroupintoacompound.(p.734)
acylgroup Acarbonylgroupbondedtoanalkylorarylgroup.(p.1002)
addition Seechaingrowthpolymerisation.(p.1123)
polymerisation
additiontothe Acharacteristicreactionofalkenesinwhichthebondisbrokenand,initsplace,
carbon bondsareformedtotwonewatomsorgroupsofatoms.(p.712)
carbondouble
bond
adduct TheproductofareactionbetweenaLewisacidandaLewisbase.(p.476)
ADNA AthickerformofDNAthanBDNA.Thebasepairsare0.25nmapart,and11base
pairsformonecompleteturnofthehelix.(p.1095)
alcohol AcompoundcontaininganOH(hydroxyl)groupbondedtoansp 3hybridised
carbonatom.(p.810)
aldehyde Acompoundinwhichacarbonylgroupisbondedtoahydrogenatomplusa
hydrocarbongroup(orasecondhydrogenatom).(p.934)
alditol TheproductformedwhentheC Ogroupofamonosaccharideisreducedtoa
CHOHgroup.(p.986)
aldoses Monosaccharidescontaininganaldehydegroup.(p.978)
aliphatic Anamineinwhichthenitrogenatomisbondedonlytoalkylgroups.(p.834)
amine
aliphatic Seealkane.(p.686)
hydrocarbon
alkalimetals Theelementsingroup1(excepthydrogen)oftheperiodictable.(p.15)
alkaline Atypeofpowercelldependentonthereactionbetweenzincandmanganesedioxide
battery (Zn/MnO2).(p.530)
alkalinedry Seealkalinebattery.(p.530)
cell
alkaline Analternativewordforbasic.(p.433)
alkalineearth Theelementsingroup2oftheperiodictable.(p.15)
metals
alkane Amoleculecomposedonlyofcarbonandhydrogenatomsinwhichallcarbon
carbonbondsaresingle.(pp.54,686)
alkene Anunsaturatedhydrocarbonwithacarboncarbondoublebond.(p.686)
alkoxy AnORgroup,whereRisanalkylgroup.(p.829)
alkylamines Aminesinwhichthenitrogenatomisbondedonlytoalkylgroups.(p.835)
alkylation Thetransferofanalkylgroupfromonecompoundtoanother.(p.733)
alkylgroup Agroupderivedfromanalkanebytheremovalofahydrogenatom,commonly
representedbythesymbolR.(p.55)
alkyne Anunsaturatedhydrocarbonwithacarboncarbontriplebond.(p.686)
aminoacid Anaminoacidinwhichtheaminogroupisattachedtothecarbonatomadjacentto
thecarboxylgroup.(p.1056)
carbon Acarbonatomadjacenttoafunctionalgroup.(p.962)
helix Atypeofsecondarystructureinwhichasectionofpolypeptidechaincoilsintoa
 spiral,mostcommonlyarighthandedspiral(p.1070)
hydrogen Ahydrogenatombondedtoancarbonatom.(p.962)
alphaparticle Thenucleusofaheliumatom .(pp.7,1163)
alternating DescribesapolymerwithregularlyalternatingAandBunits.(p.1122)
ambidentate Describesligandswithtwoormoredifferentpotentialdonoratoms.(p.555)
amide Anacylgroupbondedtoatrivalentnitrogenatom.(p.1003)
aminoacid Acompoundthatcontainsbothacarboxylgroupandanaminogroup.(p.1056)
amorphous Withoutanyorganisedregularrepeatingpattern.(p.281)
amorphous Adisordered,noncrystallineregioninthesolidstateofapolymer.(p.1119)
domain
amountof AbasequantityintheSIsystem,withtheunitofmole.(p.75)
substance
ampere(A) TheSIunitofelectriccurrent1A=1Cs1.(pp.25,527)
amphiprotic Asolventthatcanacteitherasaprotondonororaprotonacceptor.(p.430)
amplitude Themaximumdisplacementofawavefromitscentre.(p.110)
anglestrain Thestraininducedinamoleculeasaresultofbondanglesthataredistortedfromthe
idealvalues.(p.691)
anhydrous Describesachemicalsubstancethatcontainsnowater.(p.37)
aniline ThecommonnameforthemonosubstitutedbenzeneC6H5NH2.(pp.728,836)
anion Anegativelychargedion(p.2)
anisole ThecommonnameforthemonosubstitutedbenzeneC6H5OCH3.(p.728)
anode Thepositiveelectrodeinagasdischargetubetheelectrodeatwhichoxidation
occursduringanelectrochemicalchange.(p.503)
anomeric Thehemiacetalcarbonatomofthecyclicformofamonosaccharide.(p.982)
carbon
anomers Monosaccharidesthatdifferinconfigurationonlyattheiranomericcarbonatoms.(p.
982)
antiaddition Theadditionofatomsorgroupsofatomsfromoppositesidesorfacesofacarbon
carbondoublebond.(p.720)
antibonding Amolecularorbitalthathaselectrondensityconcentratedoutsidethebonding
molecular region,makingitlessstablethantheatomicorbitalsfromwhichitforms.(p.199)
orbital
anticodon AtripletofbasesontRNAthatpairstoamatchingtriplet(acodon)onanmRNA
moleculeduringmRNAdirectedpolypeptidesynthesis.(p.1101)
antimatter Anyparticleannihilatedbyaparticleofordinarymatter.(p.1166)
antioxidant Usuallyanaddedsubstanceorcompoundwhichhasaloweroxidationpotentialthan
itssurroundingssothatitispreferentiallyoxidisedinsteadofthematerialitis
protecting.(p.1148)
antiselectivity Thecharacteristicthatbromineandchlorinealwaysaddtranstoeachotherin
cycloalkenes.(p.720)
antisense ThestrandofDNAthatistranscribedintomRNAduringtranscription.Theresulting
strand RNAtranscriptisthesameasthesensestrandexceptthatthenucleotidesareRNA
andthebasethymineissubstitutedbyuracil.(p.1102)
aprotic SolventsthatdonotcontainOHgroupsand,therefore,cannotfunctionas
solvents hydrogenbonddonors.(p.791)
aramid Apolymerinwhichthemonomerunitsareanaromaticdiamineandanaromatic
dicarboxylicacid.(p.1125)
arene Acompoundcontainingoneormorebenzenerings.(p.686)
aromatic Describesacompoundcontainingoneormorebenzenerings.(p.723)
aromatic Anamineinwhichthenitrogenatomisbondedtoatleastonearomaticring.(p.834)
amine
Arrhenius Anequationthatrelatestherateconstantofareactiontothereaction'sactivation
equation energy.(p.655)
arylgroup Agroupderivedfromanaromaticcompoundbytheremovalofahydrogenatom.
(p.723)
association Theclusteringofmolecularspeciesinsolution.(p.421)
asymmetric Asyntheticprocedurethatgivesrisetopredominantlyoneenantiomer.(p.767)
synthesis
atactic Onediastereomericformofpolypropyleneinwhichthemethylgroupstakerandom
polypropylene positionsinthefrontandbackofthecarbonchain.(p.1138)
atom Aneutralparticlehavingonenucleusthesmallestrepresentativesampleofan
element.(p.2)
atomicmass Theaveragemass(inu)oftheatomsoftheisotopesofagivenelementastheyoccur
naturally.(p.10)
atomicmass Themass(1.6605410 27kg)equalto ofthemassofoneatomof12C.(p.10)
unit(u)

atomic Thenumberofprotonsinanucleus.(p.9)
number(Z)
atomicradius Thedistancefromthenucleusofanatomatwhichelectronelectronrepulsion
preventscloserapproachofanotheratom.(p.148)
atomisation Theenthalpychangeonrupturingallofthebondsin1moleofasubstanceinthe
enthalpy gasphasetoproduceitsatoms,alsointhegasphase.(p.314)
(atH)
Aufbau Thestatementthatthemoststablearrangementofelectronsinanatomresultsfrom
principle placingeachsuccessiveelectroninthemoststable(lowestenergy)availableatomic
orbital.(p.138)
autoprotolysis Aprocessinvolvingthetransferofaprotonbetweentwoidenticalmolecules.(p.
432)
autoprotolysis Theequilibriumconstantforthereaction:
constantof
water(Kw)
IthastheformKw=[H3O+][OH,whereKw=1.010 14at25.0C.(p.433)
averagerate Therateofareactionoveraparticulartimeperiod.(p.631)
Avogadro 6.02210 23thenumberofspecifiedentitiesin1mole.(p.75)
constant(NA)
axial Describesthetwoligandsinanoctahedralortrigonalbipyramidalcomplexthat,by
convention,pointaboveandbelowtheplanedefinedbytheequatorialligandsalso
describestheorientationofthegroupsboundtoacycloalkanethatareaboveor
belowtheplaneofthering(p.553)
axialbonds Thebondsconnectingaxialgroups.Forinstance,inanoctahedralortrigonal
bipyramidalcomplex,axialbondspointaboveandbelowtheplanedefinedbythe
equatorialligands.Fororganicconformers,theaxialbondsarethosethatare
 orientedperpendiculartotheplaneofthechair,boatorenvelope.(p.692)
azimuthal Thequantumnumber,restrictedtointegersfrom0to(n1),thatindexesthe
quantum electrondistributionofanatomicorbital.(p.128)
number(l)
azo CompoundsoftheformArN NAr,commonlyusedasdyes.(p.848)
compounds

B
balanced Achemicalequationthathasthesamenumberofeachtypeofatomandthesamenet
chemical chargeonoppositesidesofthearrow.(p.72)
equation
ballandstick Athreedimensionalrepresentationofamoleculeinwhichatomsareshownasballs
model andbondsbetweenatomsassticks.(p.43)
bandof Theenvelopethatenclosesjustthestablenuclidesinaplotofallnuclidesconstructed
stability accordingtotheirnumbersofneutronsversustheirnumbersofprotons.(p.1161)
barometer Aninstrumentformeasuringatmosphericpressure.(p.214)
base ArrheniustheoryasubstancethatreleasesOHionsinwater(p.410)Brnsted
Lowrytheoryaprotonacceptor(p.428)Lewistheoryanelectronpairdonor.
(p.476)
basic Describesanaqueoussolutioninwhich[H O+]<[OH].(p.433)
3
basicity Theequilibriumconstantforthereactionofabasewithwater.Forthegeneral
constant(Kb) equilibrium:

(p.443)
battery Agroupofgalvaniccellsusuallyconnectedinseries.(p.528)
BDNA ThepredominantformofDNAindiluteaqueoussolutionandthemostcommonform
innature.Thebasepairsarestackedontopofeachother,withadistanceof0.34nm
betweenthebasepairsandwith10basepairsinonecompleteturnofthehelix.(p.
1093)
becquerel TheSIunitfortheactivityofaradioactivesource1Bq=1disintegrations1.(p.
(Bq) 1168)
Beer Thisrelatestheabsorbance(A)ofasolutiontothemolarabsorptioncoefficient( )of
Lambertlaw theabsorbingspecies,theconcentration(c)oftheabsorbingspecies,andthe
pathlengthofthecell(l),viatheequationA= cl.(pp.574,905)
Beer'slaw SeeBeerLambertlaw.(p.574)
elimination Aneliminationreactionwhereatomsorgroupsareremovedfromtwoadjacent
carbonatoms.(p.783)
bending Atypeofvibrationthatchangesbondangles.(p.872)

benzaldehyde ThecommonnameforthemonosubstitutedbenzeneC6H5CHO.(p.728)
benzoicacid ThecommonnameforthemonosubstitutedbenzeneC6H5COOH.(p.728)
benzylgroup
 TheC6H5CH2group.(p.728)
benzylic Ansp 3carbonatombondedtoabenzenering.(p.1011)
carbon
benzylic Ahydrogenatombondedtoabenzyliccarbonatom.(p.1011)
hydrogen
betaparticle Anelectronemittedbyradioactivedecay.(p.1164)
pleated Atypeofsecondarystructureinwhichtwosectionsofpolypeptidechainarealigned
sheet parallelorantiparalleltooneanother.(p.1072)
bidentate Describesligandswithtwodonoratomsthatcanbesimultaneouslyattachedtothe
samemetalion.(p.547)
bimolecular Areactioninwhichtwospeciesareinvolvedinthetransitionstateoftherate
reaction determiningstep.(p.786)
binary Acompoundthatcontainsonlytwoelements.(p.36)
compound
binding Thenuclearbindingenergydividedbythemassnumber,Aameasureofhowtightly
energyper eachnucleonisboundtothenucleus.(p.1162)
nucleon
biodegradable Apolymerdesignedtodegradeasaresultofenzymecatalysedhydrolysisofthe
polymer polymerchainintosmaller,biologicallyacceptableunits.(p.1151)
biopolymer Apolymerfoundinnature,suchasstarch,proteinsandpeptides,DNAandRNA.(p.
1118)
block Describesapolymerwithtwoormorehomopolymersubunitsjoinedtogetherby
covalentbonds.(p.1123)
boat Theconformationofcyclohexanethatroughlyresemblesaboat.(p.692)
conformation
bodycentred Thecrystalstructurewhoseunitcellisacubewithlatticepointsatitscornersandits
cubiclattice centre.(p.273)
(bcc)
boilingpoint Acolligativepropertyofasolutionbywhichthesolution'sboilingpointishigher
elevation thanthatofthepuresolvent.(p.412)
(Tb)
bomb Apparatususedinthedeterminationoftheheatofareactionunderconstantvolume
calorimeter conditions.(p.302)
bondenergy Theenergydifferencebetweentwoatomsattheirbonddistanceandtheinfinitely
separatedatoms.(p.167)
bondenthalpy Theenthalpychangeonbreaking1moleofaparticularbondtogiveelectrically
neutralfragments.(p.313)
bonding Anorbitalformedfromatomicorbitalsinwhichelectrondensityismaximised
molecular betweenthebondedatoms.(p.198)
orbital
bonding Anorbitalwithhighelectrondensitybetweenatoms,formedbyconstructive
orbital interactionbetweenatomicorbitals.(p.189)
bondlength Theseparationdistancebetweentwoatomsthatgivesthemaximumpossible
energeticadvantageoverinfinitelyseparatedatoms.(p.167)
bondorder (numberofelectronsinbondingmolecularorbitalsnumberofelectronsin
antibondingmolecularorbitals).(p.199)
boundary Theinterfacebetweenasystemanditssurroundingsacrosswhichenergyormatter
 mightpass.(p.296)
Bragg n=2dsin.(p.278)
equation
bridged Acyclicstructurecontainingahaloniumion.(p.720)
haloniumion
Brnsted Adefinitionofacidsandbasesinwhichanacidisaprotondonorandabaseisa
Lowry protonacceptor.(p.428)
buffer AmeasureoftheamountofH O+orOHthatcanbeaddedtoabuffersolution
3
capacity withoutsignificantchangeinitspH.(p.467)
buffer Asolutioncontainingappreciableamountsofeitheraweakacidanditsconjugate
solution base,oraweakbaseanditsconjugateacid.(p.462)
burette Adeviceusedfortheadditionofaccuratelymeasuredvolumesofsolutionina
titration.(p.467)
byproduct Substancesformedbysidereactions.(p.88)

C
13CNMR Nuclearmagneticresonancespectroscopyofcarbonatomswithinmolecules.It
spectroscopy providesinformationaboutthecarbonhydrogenframeworkofamolecule.(p.
883)
Cterminal TheaminoacidofapolypeptidewiththefreeCOOgroup.(p.1066)
aminoacid
calorimeter Adeviceformeasuringtheheatevolvedorabsorbedinachemicalreaction.(p.
302)
candela TheSIunitofluminousintensity.(p.25)
capillaryaction Theupwardmovementofaliquidinanarrowtubeagainsttheforceofgravity.(p.
254)
carbanion Ananioninwhichcarbonhasanunsharedpairofelectronsandbearsanegative
charge.(p.943)
carbocation Aspeciescontainingapositivelychargedcarbonatomwithonlythreebondstoit.
(p.714)
carbohydrates Polyhydroxyaldehydes,polyhydroxyketonesorsubstancesthatgiveeitherofthese
compoundsafterhydrolysis.(p.978)
carboxylicacid Seecarboxylgroup.(p.1002)
group
carboxylgroup ACOOHgroup.(p.1002)
catalysis Rateenhancementcausedbyacatalyst.(p.668)
catalyst Asubstancethatinrelativelysmallproportionsacceleratestherateofareaction
withoutbeingchemicallychanged.(p.668)
catalytic Reductionbyhydrogeninthepresenceofacatalyst.(p.720)
hydrogenation
catalytic Reductioninthepresenceofacatalyst.(p.720)
reduction
catenation Thelinkingofatomsofthesameelement(particularlycarbon)toformchains.(p.
38)
cathode Thenegativeelectrodeinagasdischargetubetheelectrodeatwhichreduction
 occursduringanelectrochemicalchange.(p.503)
cathodic Theprocessinwhichastructuralmetal,suchasiron,isprotectedfromcorrosion
protection byconnectingittoametalthathasamorenegativereductionhalfcellpotential.
(p.523)
cation Apositivelychargedion.(p.2)
cationic Ionicpolymerisationinwhichthechaincarriersarecations.(p.1138)
polymerisation
celldiagram Ashorthandwayofdescribingthemakeupofagalvaniccell.(p.505)
cellpotential Themaximumpotentialthatagivencellcangenerate.(p.507)
(Ecell)
cellreaction Theoverallchemicalchangethattakesplaceinanelectrolyticcelloragalvanic
cell.(p.502)
ceramics Materialscomposedofinorganiccomponentsthathavebeenheattreated.(p.282)
chaingrowth Polymerisationthatinvolvessequentialadditionreactions,eithertounsaturated
polymerisation monomersortomonomerswithotherfunctionalgroups.(p.1123)
chaininitiation Inradicalorcationicpolymerisation,theformationofradicalsorcarbocationsfrom
moleculescontainingonlypairedelectrons.(p.1134)
chainlength Inpolymerisation,thenumberoftimesacycleofchainpropagationstepsrepeats.
(p.1135)
chain Inradicalorcationicpolymerisation,thereactionofaradicalorcarbocationwitha
propagation moleculetogiveanewradicalorcarbocation.(p.1134)
chain Inradicalpolymerisation,thereactionbetweentworadicalstoformacovalent
termination bondortoundergodisproportionationintoasaturatedandanunsaturated
compoundincationicpolymerisation,thereactionbetweenacarbocationandan
aniontogiveanunchargedstablecompound.(p.1134)
chaintransfer Inradicalpolymerisation,thetransferofreactivityofanendgroupfromonechain
reaction toanotherduringpolymerisation.(p.1136)
chair Themoststablepuckeredconformationofacyclohexanering.(pp.691,983)
conformation
chalcogens Theelementsingroup16oftheperiodictable.(p.15)
chelatecomplex Acomplexioncontainingoneormorechelaterings.(p.547)
chelateeffect Thelargervalueofthecumulativeformationconstant(n)foundforcomplexes
containingchelateringswhencomparedwithanalogouscomplexescontaining
monodentateligands.(p.562)
chelatering Theringformedwhenapolydentateligandcoordinatestoatransitionmetalion.
(p.547)
chemical Aformofnotationusedtodescribechemicalreactions,inwhichthereactantsand
equation productsofthereactionareseparatedbyadirectionalarrow,withthereactants
appearingonthelefthandside.(pp.4,72)
chemical Asituationinwhichthechemicalcompositionofasystemdoesnotchangewith
equilibrium time.(p.346)
chemical Aformulawrittenusingchemicalsymbolsandsubscriptsthatdescribesthe
formula compositionofachemicalcompoundorelement.(p.36)
chemical Thestudyoftheratesofchemicalreactions.(p.630)
kinetics
chemical Aprocessinvolvingtransformationofchemicalspeciesintodifferentchemical
reaction species,usuallyinvolvingthemakingand/orbreakingofchemicalbonds.(pp.2,
72)
chemicalshift ThequantityusedinNMRspectroscopytoidentifythepositionsofsignals
() producedbythenucleiofasample.Theunitofchemicalshift()ispartsper
million(ppm).(p.885)
chemicalsymbol Theformulaofanelement.(p.9)
chemical Thestudyoftheroleofenergyinchemicalchangeandindeterminingthe
thermodynamics behaviourofmaterials.(p.295)
chiral Describesanobjectthatisnotsuperimposableonitsmirrorimage.(p.746)
chromatin AcomplexformedbetweennegativelychargedDNAmoleculesandpositively
chargedhistones.(p.1096)
circularDNA AtypeofdoublestrandedDNAinwhichthe5andthe3endsofeachstrandare
joinedbyphosphodiestergroups.(p.1095)
cisisomer Astereoisomerinwhichtwogroupslieonthesamesideofareferenceplane.(p.
555)
cistrans Stereoisomersthatdifferinthepositioningoftwogroupswithrespecttoa
isomers referenceplane.(pp.555,695)
closepacked Themostefficientarrangementforpackingatoms,moleculesorionsinaregular
structures crystal.(p.270)
codingstrand TheDNAstrandwhichhasthesamebasesequenceasthemRNAtranscript
producedduringDNAtranscription,exceptthatthethyminebaseisreplacedby
uracil.(p.1102)
codon AtripletofnucleotidesonmRNAthatdirectstheincorporationofaspecificamino
acidintoapolypeptidesequence.(p.1103)
colligative Aproperty,suchasvapourpressurelowering,boilingpointelevation,freezing
property pointdepressionandosmoticpressure,thatdependsonlyontheratioofthe
numbersofmolesofsoluteandsolventparticlesandnotontheirchemical
identities.(p.408)
collisiontheory Atheorythatassumesthatforareactiontooccur,reactantmoleculesmustcollide
withproperorientationandwithanenergylargerthanathresholdvalue.(p.651)
combustion Arapidreactionwithoxygenaccompaniedbyaflameandtheevolutionofheat
andlight.(p.82)
combustion Thereactionofachemicalsubstancewithoxygen.(p.302)
reaction
commonion Anioninamixtureofionicsubstancesthatiscommontotheformulaeofatleast
twoofthosesubstances.(p.404)

commonion Theeffectbywhichthesolubilityofonesaltisreducedbythepresenceofanother
effect havingacommonion.(p.404)
competing Areactionthatreducestheyieldofthemainproductbyformingbyproducts.(p.
reaction 88)
complementary Thecolourofthereflectedortransmittedlightwhenonecomponentofwhitelight
colour isremovedbyabsorption.(p.571)
complex Thecombinationofoneormoreanionsorneutralmolecules(ligands)witha
transitionmetalion.(p.544)
complex Asplittingpatternresultingfrommorethanonesetofequivalenthydrogenatoms.
splittingpattern Signalsofthistypearecalledmultiplets.(p.892)
compound Achemicalsubstancecontainingtwoormoreelementsinadefiniteand
unchangingproportion.(p.2)
compound Anatomicnucleuscarryingexcessenergyfollowingitscaptureofsome
nucleus bombardingparticle.(p.1171)
concentration Theratioofthequantityofsolutetothequantityofsolution(orthequantityof
solvent)seealsomolalconcentrationmolarconcentrationmolefraction.(p.90)
concentration Anelectrolyticcellinwhichthepotentialdifferenceiscausedbyadifferencein
cell concentrationofsomecomponentintheelectrolyte.(p.521)
concentration Atablethatoutlinesthechangesinconcentrationthatoccurasachemicalsystem
table comestoequilibrium.(p.371)
condensation Conversionofavapourintoitsliquid.(p.240)
condensation Seestepgrowthpolymerisation.(p.1123)
polymerisation
condensed Ashorthandmethodofrepresentingmoleculesinwhichbondsbetweenatomsare
structural notdrawnexplicitly.(p.39)
formula
configurational Isomersthatcannotbeinterconvertedbyrotationaroundasinglebond.(p.701)
isomers
conformation Therepresentationofthepositionofatomsinaconformer.(p.688)
conformer Anythreedimensionalarrangementofatomsthatresultsfromrotationarounda
singlebond.(p.688)
conjugateacid Thespeciesinaconjugateacidbasepairthathasthegreaternumberofprotons.
(p.430)
conjugateacid Twospeciesthatdifferonlybyaproton.(p.430)
basepair
conjugatebase Thespeciesinaconjugateacidbasepairthathasthefewernumberofprotons.(p.
430)
constitutional Isomerswithdifferentsequencesofatomconnectivity.(pp.58,746)
isomers
coordinatebond AcovalentbondbetweenaLewisacidicmetalionandaLewisbasicligandin
whichbothelectronsoriginatefromtheligand.(p.552)
coordination Thestudyoftransitionmetalcomplexes.(p.552)
chemistry
coordination Atransitionmetalcomplex.(p.552)
compound
coordination Isomersthatresultwhenligandsareexchangedbetweenacomplexcationanda
isomers complexanionofthesamecoordinationcompound,e.g.[Co(NH3)6][Cr(CN)6]and
[Cr(NH3)6][Co(CN)6].(p.555)
coordination Thenumberofdonoratomscoordinatedtoametalion.(p.553)
number
coreelectrons Theinneratomicelectronswithprincipalquantumnumberlessthanthatofthe
valenceelectrons.(p.140)
correlationtable Atableofdataonspectroscopicabsorptionpatternsofselectedfunctionalgroups.
(p.872)
coulomb(C) TheSIunitofelectriccharge.(p.501)
counterion Anionthatbalancesthechargeonacationicoranioniccomplexion.(p.552)
covalentbond Achemicalbondinwhichtwoatomsshareoneormorepairsofelectrons.(pp.2,
166)
criticalmass Themassofafissileisotopeabovewhichaselfsustainingchainreactionoccurs.
(p.1176)
criticalpoint Thetemperatureandpressureabovewhichthedistinctionbetweentheliquidand
vapourphasesdisappears.(p.263)
criticalpressure Thepressureassociatedwiththecriticalpoint.(p.263)
critical Thetemperatureassociatedwiththecriticalpoint.(p.263)
temperature(Tc)
crosslinks Abridgeformedbetweenpolymerstrands.(p.1147)
crystalfield Thedifferenceinenergybetweenthetwosetsofdorbitalsinanoctahedralor
splittingenergy tetrahedralcomplexion.(p.567)
(o)
crystalfield Atheorythatconsiderstheeffectsofthepolaritiesorthechargesoftheligandsin
theory acomplexionontheenergiesofthedorbitalsofthecentralmetalion.(p.566)
crystallattice Thelatticeofacrystallinesolid.(p.273)
crystalline Imperfectionsinaregularsolid.(p.281)
defects
crystalline Anorderedcrystallineregioninthesolidstateofapolymeralsocalledcrystallites.
domain (p.1119)
crystallinesolid AsolidthathasaregulararrangementofunitcellsanddiffractsXrays.(p.273)
cubicclose ThearrangementinwhichclosepackedlayersarestackedinanABCABC
packed(ccp) pattern.(p.270)
cumulative Theequilibriumconstantfortheprocess:
formation
constant(n)

givenbytheexpression (p.561)

cyanohydrins AcompoundinwhichbothanOHandaCNgrouparebondedtothesame
carbonatom.(p.946)
cyclicether Anetherinwhichtheoxygenatomisoneoftheatomsofaring.(p.829)

cycloalkane Asaturatedhydrocarbonwithcarbonatomsjoinedtogethertoformaring.(pp.54,
690)
cycloalkene Anunsaturatedhydrocarbonwithcarbonatomsjoinedtogethertoformaringthat
containsacarboncarbondoublebond.(p.707)

D
dblockelements Collectivenamefortheelementsingroups3to12oftheperiodictable.(p.
14)
ddtransition Anelectronictransitionbetweenthet2gandegsetsoforbitalsinanoctahedral
complex.(p.570)
Dalton'satomic Matterconsistsoftiny,indestructibleparticlescalledatoms.Allatomsofone
theory elementareidentical.Theatomsofdifferentelementshavedifferentmasses.
Atomscombineindefiniteratiosofatomswhentheyformcompounds.(p.4)
Dalton'slawof Thelawstatingthatinagasmixture,eachgasexertsapressureequaltothe
partialpressures pressurethatitwouldexertifpresentbyitselfunderotherwiseidentical
conditions.(p.227)
dativebond Acoordinatebond.(p.552)
decayconstant(k) Thefirstorderrateconstantforradioactivedecay.(p.1168)
degenerate Describesorbitalswiththesameenergy.(pp.135,566)
degradation Anychangeinpropertiesofapolymerrelativetotheirinitialdesired
properties.(p.1147)
dehydration Eliminationofamoleculeofwaterfromacompound.(p.819)
dehydrohalogenation Aprocessinwhichahalogenisremovedfromonecarbonatomofa
haloalkaneandahydrogenatomisremovedfromtheadjacentcarbonatomto
formacarboncarbondoublebond.(p.794)
delocalisedbond Abondinwhichelectrondensityisdistributedovermorethantwoatoms.(p.
189)
denaturation Interferencewiththesecondary,tertiaryandquaternarystructuresofaprotein,
changingitsconformationandoftenremovingitsfunctionality.(p.1078)
deposition Thephasechangeinwhichavapourconvertsdirectlytoasolidwithout
passingthroughtheliquidphase.(p.261)
deshielded DescribesthesituationinNMRspectroscopyinwhichresonanceorinductive
effectsreducetheelectrondensityaroundanucleus,thusincreasingtheability
ofanappliedmagneticfieldtobringthenucleusintoresonance.(p.885)
dextrorotatory Describestheclockwiserotationofaplaneofpolarisedlightinapolarimeter.
(p.762)
dialysis Thepassageofsolventandsmallmoleculesandionsthroughasemipermeable
membrane.(p.414)
diamagnetic Thequalityofnotbeingattractedtoamagneticfield.Substanceswithno
unpairedelectronsarediamagnetic.(pp.146,544)
diastereomers Apairofstereoisomersthatarenotmirrorimagesofeachother.(p.747)
differentialratelaw Aratelawthatexpressestherateofareactionasafunctionofconcentration.
(p.637)
diffractionpattern ThepatternformedfromXraysdiffractedbyacrystal.(p.278)
diffusion Themovementofonetypeofgasmoleculethroughmoleculesofanother
type.(p.223)
dimensionalanalysis Theuseofunitsofaphysicalquantitytoderivetheequationusedto
determineitsvalue.(p.28)
dimer Acloseassociationoftwosimilarmolecules.(p.421)
diol Acompoundwithtwoalcoholgroups.(p.811)
dipeptide Amoleculecontainingtwoaminoacidunitsjoinedbyapeptidebond.(p.
1066)
dipoledipoleforce Theattractiveforcebetweenpolarmoleculesthatresultsfromthenegativeend
ofonemoleculealigningwiththepositiveendofitsneighbour.(p.241)
dipoleinduceddipole Theforceresultingfromtheinductionofadipoleinamoleculebya
force neighbouringmoleculehavingapermanentdipole.(p.241)
dipolemoment Thenetelectricalcharacterarisingfromanasymmetricchargedistribution.(p.
183)
diproticacid Anacidthatcanpotentiallydonatetwoequivalentsofprotonstowater.(p.
429)
disaccharides Carbohydratescontainingtwomonosaccharideunitsjoinedbyaglycosidic
bond.(p.991)
dispersionforce Theattractionbetweenthenegativelychargedelectroncloudofonemolecule
andthepositivelychargednucleiofneighbouringmolecules.(p.241)
diproticbase Abasewhichisabletoaccepttwoprotons.(p.430)
disproportionation Anelectrochemicalprocessinwhichaspeciesissimultaneouslyoxidisedand
reducedtoformtwodifferentproducts.(pp.529,565)
dissociation Thebreakingapartofamoleculeorionicsolidintoionswhendissolvedina
solvent(usuallywater).(pp.96,418)
dissolution Theprocessofdissolvingasoluteinasolvent.(p.390)
disulfide AcompoundoftheformRSSR,wheretheRgroupsareeitheralkyloraryl
groups.(p.834)
disulfidebond Acovalentbondbetweentwosulfuratoms,i.e.anSSbond.(p.1072)
Dmonosaccharide Amonosaccharidethat,whenwrittenasaFischerprojection,hastheOHon
itspenultimatecarbonatomtotheright.(p.979)
DNA Deoxyribonucleicacid,anucleicacidthathydrolysesto2deoxyribose,
phosphateions,adenine,thymine,guanineandcytosine,andthatcarries
genes.(p.1088)
DNAligase Anenzymethatrepairssinglestrandeddiscontinuitiesindoublestranded
DNA.(p.1097)
DNApolymerase Anenzymethatcatalysesthepolymerisationofdeoxyribonucleotidestoform
DNA.(p.1097)
donoratom Anatomofaligandinacomplexthatisdirectlycoordinatedtothetransition
metalion.(p.547)
donorcovalentbond Acoordinatebond.(p.552)
doublebond Achemicalbondcontainingtwopairsofbondingelectrons.(p.171)
doublebond Seeindexofhydrogendeficiency.(p.864)
equivalent
doublehelix AtypeofsecondarystructureofDNAmoleculesinwhichtwoantiparallel
polynucleotidestrandsarecoiledinarighthandedmanneraroundthesame
axis.(p.1092)
doublet Asignalin1HNMRspectroscopythathasbeensplitintotwopeaksinaratio
of1:1.(p.892)
downfield DescribesasignalinNMRspectroscopythatistowardstheleftofthe
spectrumorofanothersignal.(p.886)
drycellbattery Acellwithanimmobilisedelectrolyte,suchastheLeclanchcell.(p.529)
dynamicequilibrium Anequilibriuminwhichtheratesoftheforwardandreversereactionsare
equal.(p.346)

E
E1 Aprocessinwhichthebondtotheleavinggroupiscompletelybrokenbeforethe
hydrogenatomisremovedandthecarboncarbondoublebondisformed.(p.795)
E2 Aprocessinwhichthehydrogenislostatthesametimeasthebondtothe
leavinggroupisbrokenandthecarboncarbondoublebondisformed.(p.796)
effectivenuclear Thenetpositivecharge,equaltothenuclearchargeminustheeffectsofscreening,
charge(Zeff) thatanelectroninanatomicorbitalexperiences.(p.136)
effusion Theescapeofagasthroughapinholefromacontainerintoavacuum.(p.223)

elastomer Amaterialthat,whenstretchedorotherwisedistorted,returnstoitsoriginalshape
 whenthedistortingforceisreleased.(p.1120)
electrochemical Achemicalchangethatiscausedby,orthatproduces,electricity.(p.503)
changes
electrochemical Thepotentialdifferencebetweentheelectrodesinagalvaniccell.(p.502)
potential
electrochemistry Thestudyofelectrochemicalchanges.(p.503)
electrolysis Theproductionofachemicalchangebythepassageofelectricitythrougha
solutionthatcontainsionsorthroughamoltenioniccompound.(p.524)
electrolysiscell Anapparatusforelectrolysis.(p.524)
electrolyticcell Seeelectrolysiscell.(p.524)
electrolytic Thetransportofelectricchargebyions.(p.524)
conduction
electromagnetic Energypropagatedthroughspaceintheformofoscillatingelectricandmagnetic
radiation fields.(pp.110,870)
electron Asubatomicparticle withachargeof1andmassof5.485810 4u

(9.109410 31kg),thatisoutsideanatomicnucleustheparticlethatmoveswhen
anelectriccurrentflows.(p.2)
electronaffinity Theenergychangeaccompanyingtheattachmentofanelectrontoanatomor
(EEA) anion.(p.151)
electroncapture Thecapturebyanucleusofanorbitalelectronthatchangesaprotonintoaneutron
inthenucleus.(p.1166)
electron Thedistributionofelectronsamongthevariousorbitalsofanatom,moleculeor
configuration ion.(p.141)
electrondensity Atwodimensionaldotdrawingrepresentingthedistributionofelectrondensityin
picture anorbital.(p.131)
electrondensity Aplotofthedistributionofelectronprobabilityinspacearoundanatomor
plot molecule.(p.131)
electronegativity Ameasureoftheabilityofanatominamoleculetoattractthesharedelectronsin
achemicalbond.(p.168)
electronic Theconductionofelectricchargebythemovementofelectrons.(p.504)
conduction
electron Seeelectronspinresonance(ESR).(p.906)
paramagnetic
resonance(EPR)
electronspin Atypeofmagneticresonanceusedtostudyfreeradicals,paramagneticspecies
resonance(ESR) andothersubstancescontainingunpairedelectronsalsoknownaselectron
paramagneticresonance(EPR).(p.906)
electronic Themovementofelectronsbetweenstatesofdifferentenergies.(pp.17,570)
transition
electrophile Anymoleculeorionthatcanacceptapairofelectronstoformanewcovalent
bondaLewisacid.(pp.477,712)
electrophilic Areactioninwhichanelectrophile,E+,substitutesforahydrogenonanaromatic
aromatic ring.(p.730)
substitution
electrophoresis Theprocessofseparatingcompoundsonthebasisoftheirelectriccharge.(p.
1063)
element Achemicalspeciesconsistingofatomsofasingletype.(p.2)
elemental Amethodofchemicalanalysisbywhichagivenamountofacompoundis
analysis decomposedchemicallytofindthemassesofelementswithinit.(p.80)
elementary Oneoftheindividualstepsinthemechanismofareaction.(p.658)
reaction
emission Thedistributionofwavelengthsoflightgivenoffbyaspeciesinanexcitedstate.
spectrum (p.117)
empirical Achemicalformulathatusesthesmallestwholenumbersubscriptstogivethe
formula proportionsofatomsofthedifferentelementspresent.(p.77)
enantiomers Apairofstereoisomersthatarenonsuperimposablemirrorimagesofeachother.
(p.746)
endothermic Describesachangeinwhichenergyentersasystemfromthesurroundings.(p.
304)
endpoint Thepointinatitrationwhentheindicatorchangescolour.(p.467)
energylevel Adiagramofthespecificenergylevelsofaspecies,showingincreasingenergyon
diagram theyaxis.(p.122)
enol AmoleculecontaininganOHgroupbondedtoacarbonatomofacarbon
carbondoublebond.(p.962)
enthalpy(H) Theheatcontentofasystemmeasuredunderconstantpressureconditions.(p.
296)
enthalpyof Theenthalpyofreaction, ,withhydrogen.(p.721)
hydrogenation
enthalpyof Theenthalpychangethataccompaniestheformationofasolutionfromasolute
solution(solH) andasolvent.(p.398)
entropy(S) Athermodynamicquantityrelatedtothenumberofequivalentwaystheenergyof
asystemcanbedistributed.Thegreaterthisnumber,themoreprobableisthestate
andthehigheristheentropy.(p.296)
epoxyresin Materialpreparedbyapolymerisationinwhichonemonomercontainsatleasttwo
epoxygroups.(p.1132)
equatorial Describesacovalentbondlocatedintheplaneperpendiculartotheaxialligandsof
anoctahedralortrigonalbipyramidalmolecule.(p.553)
equatorialbonds Bondsorientedinachairconformationofacyclicstructureinthegeneralplaneof
theseatofthechair.(p.692)
equilibrium Thevalueoftheequilibriumconstantexpressionwhenthesystemisat
constant(K) equilibrium.(p.347)
equilibrium Afractioninwhichthenumeratoristheproductoftheequilibriummolar
constant concentrationsoftheproducts,eachraisedtoapowerequaltoitscoefficientinthe
expression equilibriumequation,andthedenominatoristheproductoftheequilibriummolar
concentrationsofthereactants,eachraisedtoapowerequaltoitscoefficientinthe
equation.(Forgaseousreactions,partialpressurescanbeusedinplaceofmolar
concentrations.)(p.347)
equivalence Thepointinatitrationwhenthestoichiometryofthereactionissatisfied.(p.467)
point
equivalent Hydrogenatomsthatarechemicallyequivalent.(p.886)
hydrogenatoms
ester Afunctionalgroupgeneratedbycombiningacarboxylicacidandanalcoholwith
theeliminationofwatertogiveacarbonylcarbonatomthatisalsofurtherbound
toadifferentsaturatedcarbonatomviaanoxygenatomlinkage.(p.1003)
ether AcompoundoftheformROR,wheretheRgroupsareeitheralkylorarylgroups,
 suchthatanoxygenatomisbondedtotwocarbonatomsthatarenotalsobonded
toaheteroatom.(p.829)
excessreagent Thereagentleftoverwhenthelimitingreagenthasbeenusedup.(p.87)
excitedstate Anystateinwhichachemicalsystemisnotinitslowestpossibleenergystate.(pp.
16,116)
exothermic Describesachangeinwhichenergyleavesasystemandentersthesurroundings.
(p.304)
extensive Apropertyofanobjectthatisdescribedbyaphysicalquantity(suchasmassand
property volume)thatisproportionaltothesizeoramountoftheobject.(p.300)
E,Zsystem Asystemusedtospecifytheconfigurationofgroupsaboutacarboncarbon
doublebond.(p.706)

F
fblockelements Acollectivenameforthelanthanoidandactinoidelements.(p.14)
facecentred Acrystallinestructurewhoseunitcellhaslatticepointsateachcornerofacube
cubicstructure plusoneadditionallatticepointinthecentreofeachfaceofthecube.(p.274)
(fcc)
facial(fac) Anisomerofanoctahedralcomplex[ML X ]n+inwhichthetwosetsofligands
3 3
occupythefaceofanoctahedron.(p.557)
Faraday 1F=96485Cmol1.(p.516)
constant
Faraday'slaw Allowsthecalculationoftheamountofproductformedduringelectrolysis
amountofproduct (p.527)
fat Atriglyceridethatissemisolidorsolidatroomtemperature.(p.1039)
fattyacid Along,unbranchedcarboxylicacid,mostcommonlyof12to20carbonatoms,
derivedfromthehydrolysisofanimalfats,vegetableoilsorthephospholipidsof
biologicalmembranes.(p.1038)
ferromagnetism Apropertyofspeciescontainingunpairedelectronswherealloftheelectronspins
areorientedinthesamedirectionintheabsenceofamagneticfield.(p.576)
fingerprint Ininfraredspectroscopy,theregionofthespectrumfrom1000to400cm1.(p.
region 872)
firstlawof AformalstatementofthelawofconservationofenergyU=q+w.(p.298)
thermodynamics
Fischer Theprocessofforminganesterbyrefluxingacarboxylicacidandanalcoholin
esterification thepresenceofanacidcatalyst,commonlysulfuricacid.(p.1019)
Fischer Twodimensionalrepresentationsthatshowtheconfigurationofastereocentre
projections horizontallinesrepresentbondsprojectingforwardfromthestereocentre,vertical
linesrepresentbondsprojectingtotherear.(p.979)
fishhookarrow Asinglebarbed,curvedarrowusedtoshowthechangeinpositionofasingle
electron.(p.1134)
fissileisotope Anisotopecapableofundergoingfissionfollowingneutroncapture.(p.1176)
5end Theendofapolynucleotideatwhichthe5OHgroupoftheterminal2
deoxyribose/riboseunitisfree.(p.1090)
formalcharge Thechargethatanatominamoleculewouldhaveifeachofitsbondingelectrons
wereequallysharedwithitsbondingpartner(s).(p.173)
freezingpoint Acolligativepropertyofaliquidsolutionbywhichthefreezingpointofthe
depression(Tf) solutionislowerthanthatofthepuresolvent.(p.412)
frequency() Thenumberoffullcyclesofawavethatpassagivenpointinasecond.(pp.110,
870)
frequencyfactor TheproportionalityconstantAintheArrheniusequation.(p.655)
FriedelCrafts Theacylationofaromaticringswithanacylchlorideusinganhydrousaluminium
acylation chlorideasacatalyst.(p.734)
FriedelCrafts Thealkylationofanaromaticringandanalkylhalideusinganhydrousaluminium
alkylation chlorideasacatalyst.(p.733)
fuelcell Anelectrochemicalcellthatconvertsthechemicalenergyofareactionbetween
fuels,suchasliquidhydrogenandliquidoxygen,directlyandcontinuouslyinto
electricalenergy.(p.533)
functionalgroup Agroupofatomswithinanorganicmoleculethatdeterminesthemolecule's
chemicalreactivity.(p.50)
furanose afivememberedcyclichemiacetalformofamonosaccharide.(p.982)

G
galvaniccell Anelectrochemicalcellinwhichaspontaneousredoxreactionproduces
electricity.(p.502)
galvanisation Thecoatingofametal,suchasiron,withanother,suchaszinc,toprotectagainst
corrosion.(p.523)
gammaradiation Electromagneticradiationwithwavelengthsintherangeof110 10morless.(p.
1165)
gasconstant(R) Theproportionalityconstantusedintheidealgasequation.(p.216)
geneticcode Thecorrelationofcodonswithaminoacids.(p.1103)
Gibbsenergy(G) Athermodynamicquantitythatrelatesenthalpy(H),entropy(S)andtemperature
(T)bytheequationG=HTS.(p.296)
Gibbsenergy AplotofthechangesinGibbsenergyforasystemversusitscomposition.(p.
diagram 357)
glass Anamorphoussolidthathascooledtoasolidstatewithoutcrystallising.(p.281)
glycol AdiolinwhichtheOHgroupsareonadjacentcarbonatoms.(p.811)
glycoside AcarbohydrateinwhichtheOHonitsanomericcarbonatomisreplacedby
OR.(p.985)
glycosidicbond ThebondfromtheanomericcarbonatomofaglycosidetoanORgroup.(p.
985)
Grignardreagent AnorganomagnesiumcompoundofthetypeRMgXorArMgX.(p.942)
groundstate Thelowestpossibleenergystateofachemicalsystem.(pp.16,116)
groundstate Themoststableorbitalarrangementofelectronsinanatomormolecule.(p.137)
configuration
group Averticalcolumnofelementsintheperiodictable.(p.14)

H
1HNMR Nuclearmagneticresonancespectroscopyofhydrogenatomswithinmolecules.It
spectroscopy providesinformationaboutthecarbonhydrogenframeworkofamolecule.(p.
883)
halfcell Thatpartofagalvaniccellinwhicheitheroxidationorreductiontakesplace.(p.
502)
halfequation Achemicalequationdescribingeithertheoxidationorreductionprocessinaredox
reaction.(p.496)
Thetimerequiredforareactantconcentrationorthemassofaradionuclidetobe
halflife
reducedbyhalf.(pp.634,1168)
haloalkanes Compoundscontainingahalogenatomcovalentlybondedtoansp 3hybridised
carbonatom.(p.778)
haloform Asubstitutedmethanemoleculecontainingthreehalogenatomsofthesametype.
(p.779)
halogenation Areactioninwhichsomeofthehydrogenatomsaresubstitutedbyhalogenatoms.
(p.780)
halogens Theelementsingroup17oftheperiodictable.(p.15)
haloniumion Anioninwhichahalogenatombearsapositivecharge.(p.720)
hardening Theprocessofconvertingoilstofatsbycatalytichydrogenationofthedouble
bonds.(p.1040)
hardLewisacid ALewisacidcontaininganacceptoratomoflowpolarisibility.(p.479)
hardLewisbase ALewisbasecontainingoneormoreelectronpairsoflowpolarisibility.(p.479)
hashedwedge Ahashedwedgedenotesabondgoingintotheplaneofthepageawayfromthe
observer.(pp.40,43)
Haworth Awayofviewingfuranoseandpyranoseformsofmonosaccharides.Theringis
projection drawnflatandviewedthroughitsedge,withtheanomericcarbonatomontheright
andtheoxygenatomoftheringatthereartotheright.(p.982)
heat(q) Atransferofenergyduetoatemperaturedifference.(p.295)
heatcapacity Thequantityofheatneededtoraisethetemperatureofanobjectby1K.(p.299)
(C)
heatofreaction Theheatofareactioninanopensystem.(p.304)
atconstant
pressure(q p)
heatofreaction Theheatofareactioninasealedvessel,suchasabombcalorimeter.(p.302)
atconstant
volume(q v)
hemiacetal AmoleculecontaininganOHandanORorOArgroupbondedtothesame
carbonatom.(pp.946,981)
Henderson AnequationthatrelatesthepHofabuffersolutiontothepKa oftheweakacidand
Hasselbalch theratiooftheconjugatebasetotheacid
equation

(p.464)
Henry'slaw Theconcentrationofagasdissolvedinaliquidatanygiventemperatureisdirectly
proportionaltothepartialpressureofthegasabovethesolution.(p.394)
Hertz(Hz) TheSIunitoffrequency.Onehertzequalsonewavecyclepersecond.(p.870)
Hess'slaw Foranyreactionthatcanbewritteninsteps,thestandardenthalpyofreactionisthe
sameasthesumofthestandardenthalpiesofreactionforthesteps.(p.308)
heteroatom Anyatominanorganicmoleculeotherthancarbonorhydrogen.(p.829)
heterocyclic Anamineinwhichnitrogenisoneoftheatomsofaring.(p.834)
amine
heterocyclic Anamineinwhichnitrogenisoneoftheatomsofanaromaticring.(p.834)
aromaticamine
heterocyclic Anorganiccompoundwithoneormoreatomsotherthancarboninitsring.(p.
compound 726)
heterogeneous Acatalystthatisinadifferentphasefromthereactants.(p.668)
catalyst
heterogeneous Anequilibriumsysteminvolvingmorethanonephase.(p.356)
equilibrium
heterogeneous Areactioninwhichnotallofthechemicalspeciesareinthesamephase.(pp.356,
reaction 635)
heterolytic Describesabondbreakingprocessinwhichbothelectronsofasinglebondendup
ononeoftheatomsofthebond.(p.45)
heterolytic Seeheterolytic.(p.457)
cleavage
hexagonal Theclosepackingarrangementinwhichclosepackedlayersarestackedinan
closepacked ABABpattern.(p.270)
(hcp)
highdensity Polyethylenewithadensityof0.96gcm3andamelttransitiontemperature(T )of
m
polyethylene 133C.(p.1137)
(HDPEorPE
HD)
highresolution Atechniquethatallowstheprecisemeasurementofthemasstochargeratioofions.
mass (p.868)
spectrometry
highspin Describesacomplexionorcoordinationcompoundwiththemaximumnumberof
unpairedelectrons.(p.568)
histone Aproteinthatisparticularlyrichinthebasicaminoacidslysineandarginineand
thatisfoundassociatedwithDNAmoleculesseealsochromatin.(p.1096)
homogeneous Acatalystthatisinthesamephaseasthereactants.(p.668)
catalyst
homogeneous Anequilibriumsysteminwhichallcomponentsareinthesamephase.(p.356)
equilibrium
homogeneous Achemicalreactioninwhichallparticipatingspeciesareinthesamephase.(pp.
reaction 356,635)
homolytic Describesabondbreakingprocessinwhicheachofthebondedatomsreceivesone
electron.(p.46)

homolytic Seehomolytic.(p.457)
cleavage
Hund'srule Theobservationthatthelowestenergyarrangementofelectronsamongorbitalsof
equalenergyistheonethatmaximisesthenumberofunpairedelectronspins.(p.
144)
hybridisationof Theformationofasetofhybridorbitalswithfavourabledirectionalcharacteristics
atomicorbitals bymixingtogethertwoormorevalenceorbitalsofthesameatom.(pp.190,724)
hybridorbital Anatomicorbitalobtainedbycombiningtwoormorevalenceorbitalsonthesame
atom.(p.190)
hydrate Asolidthatcontainsadefinitenumberofwatersofcrystallisation.(p.37)
hydration Theadditionofwaterthedevelopmentinanaqueoussolutionofacageofwater
moleculesaroundionsorpolarmoleculesofthesolute.(pp.396,717)
hydration Theenthalpychangewhengaseoussoluteparticles(obtainedfrom1moleof
enthalpy solute)aredissolvedinwater.(p.397)
hydrateisomers Isomersofcomplexionsinwhichwateriseithercoordinatedtothetransitionmetal
ionoractsaswaterofcrystallisation.(p.555)
hydrideion AhydrogenatomwithtwoelectronsinitsvalenceshellH:.(p.957)
hydrocarbon Amoleculecomposedonlyofcarbonandhydrogenatoms.(pp.54,686)
hydrogen Amoderatelystrongintermolecularattractioncausedbythepartialsharingof
bonding electronsbetweenahighlyelectronegativeatomofF,OorNandthepolar
hydrogenatominaFH,OHorNHbond.(pp.241,813,1074)
hydrometer Aninstrumentusedformeasuringthedensityofaliquid.(p.529)
hydroniumion Theproductofthereactionofaprotonwithwater.Itcanalsobethoughtofasa
(H3O+) hydratedproton.(p.428)
hydrophilic Describesapolarcompoundthatdissolvesreadilyinwater.(p.1010)
hydrophobic Describesanonpolarcompoundthattendstobeinsolubleinwater.(p.1010)
hydrophobic Theforceofattractionbetweennonpolarpartsofamoleculeormolecules.(p.
interaction 1074)
hydroxideion Theproductofdeprotonationofwater.(p.428)
(OH)
hydroxylgroup AnOHgroup.(p.810)
hypertonic Describesasolutionthathasahigherosmoticpressurethancellularfluids.(p.417)
hypotonic Describesasolutionthathasalowerosmoticpressurethancellularfluids.(p.417)

I
idealgas Agasinwhichmolecularvolumesandintermolecularforcesarebothnegligible.(p.
216)
idealgas Theequationdescribingthebehaviourofanidealgas,pV=nRT.(p.216)
equation
idealsolution AhypotheticalsolutionthatobeysRaoult'slawexactly.(p.410)
immiscible Describesliquidsthatdonotmixseealsoinsoluble.(p.394)
indexof Thesumofthenumberofringsandbondsinamolecule.(p.864)
hydrogen
deficiency
(IHD)
inductive Thepolarisationofelectrondensitytransmittedthroughcovalentbondscausedbya
effect nearbyatomofhigherelectronegativity.(p.716)
inertcomplex Atransitionmetalcomplexinwhichligandexchangeisslow.(p.565)
infraredactive Anyvibrationthatresultsintheabsorptionofinfraredradiation.Foramoleculeto
absorbinfraredradiation,thebondundergoingvibrationmustbepolarandits
vibrationmustcauseaperiodicchangeinthebonddipolethegreaterthepolarityof
thebond,themoreintensetheabsorption.(p.872)
infrared Theportionoftheelectromagneticspectrumwithwavelengthsintherange7.810 7
radiation mto2.010 3m.(p.870)
initialrate Therateofachemicalreactionimmediatelyaftermixingthereactants.(p.636)
insoluble Describesasolutethatdoesnotdissolveinasolvent.(p.397)
instantaneous Therateofchangeofconcentrationofareactantorproductinachemicalreactionat
rateofchange aparticulartime.(p.632)
of
concentration
integral Aproteinincorporatedintoacellmembrane.(p.1078)
membrane
protein
integrated Aratelawthatexpressestherateofareactionasafunctionoftime.(p.637)
ratelaw
integration AmathematicalprocessusedfordeterminingtheareaunderasignalinanNMR
spectrum.(p.888)
intensity Thebrightness(numberofphotons)oflight.(p.110)
intensive Apropertyofanobjectthatisdescribedbyaphysicalquantity(suchasdensityand
property temperature)thatisindependentofthesizeofthesample.(p.300)
intercalation Thereversibleinclusionofamoleculeoratomintothecrystallatticeofanother
compound.(p.532)
intermolecular Forcesthatexistbetweenmolecules.(p.236)
forces
internal Thesumofallofthekineticenergiesandpotentialenergiesoftheparticleswithina
energy(U) system.(p.296)
interstitial Thespacebetweenspheres/atoms.(p.276)
hole
ion Achargedchemicalspecies.(p.2)
ionic Acompoundformedbetweentwoelementswithdifferentelectronegativities.(p.
compound 168)
ionicproduct Analternativenameforthereactionquotient(Qsp).(p.404)
ionicsolid Asolidcontainingcationsandanionsthatareattractedtoeachotherbyelectrical
interactionsratherthancovalentbonds.(p.257)
ionisation Theenergyrequiredtoremoveanelectronfromanisolatedspecies.(p.135)
energy(Ei)
ionisation Isomersinwhichacoordinatedligandisexchangedwithacounterion,e.g.
isomers [Co(NH3)5Br]SO4and[Co(NH3)5SO4]Br.(p.555)
ionpair Amoreorlesslooselyassociatedpairofionsinasolution.(p.419)
isoelectric ThepHatwhichanaminoacid,apolypeptideoraproteinhasnonetcharge.(p.
point(pI) 1063)
isoelectronic Havingthesamenumberofelectrons.(p.146)
isomers Moleculeswiththesamemolecularformulabutdifferentstructures.(pp.39,746)
isotactic Onediastereomericformofpolypropylene,inwhichallmethylgroupsarearranged
polypropylene onthesamesideofthecarbonchain.(p.1138)
isotonic Describesasolutionthathasthesameosmoticpressureascellularfluids.(p.417)
isotopes Atomsofthesameelementhavingdifferentnumbersofneutronsintheirnuclei.(p.
9)
J
joule(J) TheSIunitofenergy1J=1kgm2s2.(pp.296,501)

K
Kekul OneofthetwocontributingstructuresofbenzeneproposedbyAugustKekul.(p.
structure 723)
kelvin TheSIunitoftemperature.(p.25)
ketal Aversionofanacetalformedfromaketoneratherthananaldehyde.(p.947)
ketone AcompoundinwhichthecarbonatomoftheC Ogroupisbondedtotwo
hydrocarbongroups.(p.934)
ketoses Monosaccharidescontainingaketonegroup.(p.978)
kilogram TheSIunitofmass.(p.25)
kilojoule(kJ) 1000J.(p.296)

L
labile Describesatransitionmetalcomplexinwhichligandexchangeisrapid.(p.
564)
lactam Acyclicamide.(p.1003)
lactone Acyclicester.(p.1003)
lanthanoids Elements57to71oftheperiodictable.(p.14)
lattice Asetofpointswithidenticalenvironmentsthatdescribesapattern.(p.271)
latticeenergy Theenergychangeonconverting1moleofanionicsolidintoitsconstituent
gaseousions.(p.170)
latticeenthalpy Theenthalpyrequiredtoseparate1moleofacrystallinecompoundintoits
gaseousconstituentparticles.(p.397)
latticepoint Apointwithinalattice.(p.271)
lawofconservation Nodetectablegainorlossinmassoccursinchemicalreactions.Massis
ofmass conserved.(p.2)
lawofdefinite Inagivenchemicalcompound,theconstituentelementsarealwayscombined
proportions inthesameproportionbymass.(p.2)
lawofmultiple Whenevertwoelementsformmorethanonecompound,thedifferentmasses
proportions ofoneelementthatcombinewiththesamemassoftheotherareinaratioof
smallwholenumbers.(p.5)
lawofradioactive Activity ,whereNisthechangeinthenumberof
decay
radioactivenucleiduringthetimespant,andkisthedecayconstant.(p.
1168)
leadstoragebattery Aleadsulfuricacidstoragebatteryinamotorvehicleusuallya12volt
batteryofsixcells.(p.528)
LeChtelier's Ifanoutsideinfluenceupsetsanequilibrium,thesystemundergoesachange
principle inadirectionthatcounteractsthedisturbinginfluenceand,ifpossible,returns
thesystemtoequilibrium.(p.364)
Leclanchcell Aprimarybatterydependentonthereactionbetweenzincandmanganese
dioxide(Zn/MnO2)seealsodrycellbattery.(p.529)
levorotatory Describestheanticlockwiserotationofaplaneofpolarisedlightina
polarimeter.(p.762)
Lewisacid Anelectronpairacceptor.(p.476)
Lewisbase Anelectronpairdonor.(p.476)
Lewisstructure Arepresentationofcovalentbondingthatusessymbolsfortheelements,dots
fornonbondingvalenceelectrons,andlinesforpairsofbondingvalence
electrons.(p.171)
ligand Amoleculeorananionthatcancoordinatetoatransitionmetaliontoforma
complex.(p.544)
ligandtometal Electronictransitionsthatinvolveformaltransferofanelectronfromaligand
chargetransfer toatransitionmetalion.(p.573)
(LMCT)transitions
light Electromagneticradiationinthevisibleportionofthespectrum,between=
380nmand=780nm.(p.110)
likedissolveslike Stronglypolarandionicsolutestendtodissolveinpolarsolvents,and
rule nonpolarsolutestendtodissolveinnonpolarsolvents.(p.395)
limitingreagent Thereagentthatdetermineshowmuchproductcanformwhennon
stoichiometricamountsofreagentsareused.(p.87)
linear Lyingalongastraightline.(p.177)
lineofintegration Acurvedlineatasignalona1HNMRspectrumthatallowsthedetermination
oftherelativenumberofhydrogenatomsgivingrisetothatsignal.(p.888)
linestructure Ashorthandmethodofdrawingstructuralformulaeinwhicheachvertexand
lineendingrepresentsacarbonatom.(p.39)
linkageisomers Isomersthatresultfromthedifferentwaysinwhichanambidentateligandcan
bindtoametalion.(p.555)
lipid Abiomoleculeisolatedfromplantoranimalsourcesbyextractionwith
nonpolarorganicsolvents,suchasdiethyletherandacetone.(p.1034)
lithiumioncell Rechargeablebatterywithtwicetheenergycapacityofanickelcadmium
(nicad)battery.(p.532)
Lmonosaccharide Amonosaccharidethat,whenwrittenasaFischerprojection,hastheOHon
itspenultimatecarbonatomtotheleft.(p.979)
localmagneticfield Themagneticfieldgeneratedbyelectronssurroundinganucleus.(p.884)
localisedbond Achemicalbondthatinvolvesonlytwoatoms.(p.189)
lonepair Apairofvalenceelectronsthatislocalisedonanatomratherthaninvolvedin
bonding.(p.172)
lowdensity Polyethylenewithadensitybetween0.91and0.94gcm3andamelt
polyethylene(LDPE transitiontemperature(Tm)ofabout115C.(p.1136)
orPELD)

lowspin Describesacomplexionorcoordinationcompoundwiththeminimum
numberofunpairedelectrons.(p.568)

M
macromolecule Amoleculewithaverylargemolecularmass.(p.1118)
magicnumbers Thenumbers2,8,20,28,50,82and126.Thesignificanceofthesenumbersin
nuclearscienceisthatanuclideinwhichthenumberofprotonsorneutronsequals
amagicnumberhasnucleithatarerelativelymorestablethanthoseofother
nuclidesnearbyinthebandofstability.(p.1163)
magnetic Apropertyrelatedtothenumberofunpairedelectronsinatransitionmetal
moment() complexthroughtheequation (p.574)
magnetic Thequantumnumber,restrictedtointegersbetween+landl,thatindexesthe
quantumnumber orientationinspaceofanatomicorbital.(p.129)
(ml)
maingroup Acollectivetermforthemetalsingroups1,2and1316oftheperiodictable.(p.
metals 544)
mainreaction Thedesiredreactionbetweenthereagentsratherthancompetingreactionsthat
givebyproducts.(p.88)
manometer Abenttube,containingaliquidandopenatbothends,usedtomeasure
differencesinpressure.(p.214)
Markovnikov's IntheadditionofHXorH2Otoanalkene,hydrogenaddstothecarbonatomof
rule thedoublebondhavingthegreaternumberofhydrogenatoms.(p.713)
massdefect Foragivenisotope,themassthatchangedintoenergyasthenucleonsgatheredto
formthenucleus,thisenergybeingreleasedfromthesystem.(p.1161)
massnumber(A) Thenumericalsumoftheprotonsandneutronsinanatomofagivenisotope.(p.
9)
masspercentage Alistofthepercentagesbymassoftheelementsinacompound.(p.80)
composition
mass Atechniqueusedtodeterminethemassofmoleculesandfragmentsofmolecules.
spectrometry (p.865)
matter Anythingthathasmassandoccupiesspace.(p.2)
mechanistic Arrowswhichshowthemovementofelectronsinbondbreakingandbondmaking
arrows processes.(p.45)
melttransition Thetemperatureatwhichcrystallineregionsofapolymermelt.(p.1120)
temperature
(Tm)
meniscus Thecurvedsurfaceofaliquidcontainedinanarrowtube.(p.254)
mercaptan Analternativenameforathiol.(p.832)
meridional(mer) Anisomerofanoctahedralcomplex[ML X ]n+inwhichthedonoratomsofeach
3 3
setofidenticalligandsarecoplanar.(p.557)
mesocompound Anachiralcompoundwithtwoormorestereocentres.(p.758)
messengerRNA AribonucleicacidthatcarriescodedgeneticinformationfromDNAtoribosomes
(mRNA) forthesynthesisofproteins.(p.1101)
meta Describesgroupsoccupyingpositions1and3onabenzenering.(p.728)
metallicsolid Anelementalsolidwhoseatomsareheldtogetherbyvalenceelectronsoccupying
delocalisedorbitalsspreadacrosstheentiresolid.(p.257)
metalloids Elementswithpropertiesthatliebetweenthoseofmetalsandnonmetals,andthat
arefoundintheperiodictablearoundthediagonallinerunningfromboron,B,to
astatine,At.(p.15)
metallurgy Thescienceandtechnologyofmetals,theproceduresandreactionsthatseparate
metalsfromtheirores,andtheoperationsthatcreatepracticalusesformetals.(p.
580)
metals Elementsthataregoodconductorsofheatandelectricity,aremalleable(canbe
beatenintoathinsheet)andductile(canbedrawnoutintoawire),andhavethe
usualmetalliclustre.(p.15)
metaltoligand Anelectronictransitioninatransitionmetalcomplexinwhichanelectronis
chargetransfer transferredfromthemetaltotheligand.(p.573)
transition
metre TheSIunitoflength.(p.25)
micelle Asphericalarrangementoforganicmoleculesinaqueoussolution,clusteredso
thattheirhydrophobicpartsareburiedinsidethesphereandtheirhydrophilicparts
areonthesurfaceofthesphereandincontactwithwater.(p.1041)
Michaelis Inenzymereactions,thesubstrateconcentrationathalfofthemaximumreaction
constant rate.(p.673)
Michaelis Anequationthatdescribesthereactionrateofmanyenzymecatalysedreactions.
Mentenequation (p.673)
Michaelis Thereactionmechanism,bywhichmanyenzymecatalysedreactionsproceed.(p.
Menten 672)
mechanism
miscible Describesliquidsthatmixcompletelyseealsosoluble.(p.394)
molalboiling Thenumberofdegrees(C)perunitofthemolalconcentrationboilingpoint
pointelevation elevationofasolutionrelativetothepuresolvent.(p.412)
constant(Kb)
molal Thenumberofmolesofsolutein1000gofsolventalsocalledmolality.(p.408)
concentration(b)
molalfreezing Thenumberofdegrees(C)perunitofthemolalconcentrationfreezingpoint
pointdepression depressionofasolutionrelativetothepuresolvent.(p.412)
constant(Kf)
molality(b) Molalconcentration.(p.408)
molar TheconcentrationofasolutioninunitsofmolL1alsocalledmolarity.(p.408)
concentration(c)
molarenthalpy Theenthalpychangeonmelting1moleofasubstanceatitsnormalmeltingpoint.
offusion(fusH) (p.261)
molarenthalpy Theenthalpychangeonsublimationof1moleofasubstanceatitsnormal
ofsublimation sublimationpoint.(p.261)
(subH)
molarenthalpy Theenthalpychangeonvaporisationof1moleofasubstanceatitsnormalboiling
ofvaporisation point.(p.261)
(vapH)

molarheat Theheatcapacityof1moleofasubstance.(p.301)
capacity
molarity(c) Molarconcentration.(pp.90,408)
molarmass(M) Themassof1moleofthespecifiedsubstance.(p.75)
molarsolubility Thenumberofmolesofsoluterequiredtoprepare1Lofasaturatedsolutionof
(s) thesolute.(p.402)
mole SIunitofamountofsubstance.Onemoleistheamountofsubstancethatcontains
thesamenumberofelementaryentities(6.02210 23)asthereareatomsin
exactly12gof12C.(pp.25,75)
molecular Aformulathatshowstheactualnumbersofdifferenttypesofatomspresentina
formula molecule.(pp.36,81)
molecularion Anionisedmoleculethatproducesapeakinamassspectrum.Thisisusuallythe
peakwiththehighestm/zvalue.(p.866)
molecular Athreedimensionalwavethatencompassesanentiremoleculeanddescribesa
orbital(MO) boundelectron.(p.198)
molecular Anenergyleveldiagramdisplayingthemolecularorbitalsofaparticular
orbitaldiagram molecule.(p.199)
molecular Abondingtheorythatconsidersallpossibleoverlapsbetweenatomicorbitalsina
orbitaltheory molecule.Theoverlapoftwoatomicorbitalsleadstotheformationofone
bondingmolecularorbitalandoneantibondingmolecularorbital.Molecular
orbitalsaregenerallydelocalisedandcanbespreadovertheentiremolecule.(p.
198)
molecularsolid Asolidcontainingdiscretemoleculesthatdonothavechemicalbondsbetween
them.(p.257)
molecularity Thenumberofcollidingmoleculesinvolvedinanelementarystep.(p.659)
molecule Anunchargedcollectionofatomsbondedtogetherinadefinitestructure.(p.2)
molefraction(x) Thenumberofmolesofacomponentinasolutiondividedbythetotalnumberof
molesofmaterialinthesolution.(pp.227,409)
monodentate Describesaligandthatcancoordinatetoametalionusingonlyonedonoratom.
(p.547)
monomer Thesimplestnonredundantunitfromwhichapolymerisformed.(p.1118)
monoproticacid Anacidthatcandonateonlyasingleprotontowater.(p.429)
monosaccharides Carbohydratesthatcannotbehydrolysedtosimplercompounds.(p.978)
multiplet Thesplittingpatternofacomplexsignalin1HNMRspectroscopy.(p.892)
multiplicity Thesplittingpatternofasignalin1HNMRspectroscopy,whichcanbedescribed
as,singlet,doublet,triplet,quartet,multipletetc.(p.893)
mutarotation Thechangeinopticalactivitythatoccurswhenanorformofacarbohydrateis
convertedtoanequilibriummixtureofthetwoforms.(p.984)

N
(n+1)rule ArulefordeterminingsplittingpatternsinNMRspectroscopy.Ifahydrogenatom
hasnotherhydrogenatomsthatarenotequivalenttoit,butareequivalenttoeach
other,onthesameoradjacentatom(s),its1HNMRsignalissplitinto(n+1)peaks.
(p.893)
Nterminal TheaminoacidofapolypeptidewiththefreeNH +group.(p.1066)
3
aminoacid
natural Anelasticmaterialobtainedfromthelatexsapoftrees(especiallytreesofthespecies
rubber Heveabrasiliensis)thatcanbevulcanisedandmadeintoavarietyofproducts.(p.
1146)
Nernst (p.519)
equation
netionic Anionicequationfromwhichspectatorionshavebeenomitted.Itisbalancedwhen
equation bothatomsandelectricalchargebalance.(p.97)
networksolid Asolidcontaininganarrayofcovalentbondslinkingeveryatomtoitsneighbours.
(p.257)
neutral Describesasolutioninwhich[H O+]=[OH].(p.433)
3
neutron Asubatomicparticle(n, ),withachargeof0andamassof1.0086u(1.6749
10 27kg),thatexistsinallatomicnucleiexceptthoseofthe1Hisotope.(p.8)
neutron Anuclearreactioninwhichaneutronisejected.(p.1166)
emission
Newman Awaytoviewamoleculebylookingalongacarboncarbonbond.(p.688)
projection.
nicadbattery Anickelcadmiumbattery,commonlyusedinlaptopcomputers.(p.531)
nickel Seenicadbattery.(p.531)
cadmium
storagecell
nitrile aCNgroup.(p.1012)
nitroniumion NO +.(p.732)
2
noblegas Theportionofthedistributionofelectronsamongtheorbitalsofanatomthat
configuration matchesthatofoneofthenoblegases.(p.143)
noblegases Theelementsingroup18oftheperiodictable.(p.15)
node Apoint,lineorsurfacewheretheelectrondensityofanorbitaliszero.(pp.132,198)
nomenclature Asystemofnaming.(p.46)
nonmetals Nonductile,nonmalleable,nonconductingelements.(p.15)
nonoxidising Anacidinwhichtheanionisapooreroxidisingagentthanthehydrogenion(e.g.
acid HCl,H3PO4).(p.513)
nonvolatile Describesasubstancewithahighboilingpointandalowvapourpressurethat,
consequently,doesnotevaporate.(p.408)
normal Theboilingpointofasubstanceunderoneatmosphere(1.0132510 5Pa)of
boilingpoint pressure.(p.240)
normal Thefreezingpointofasubstanceunder1.0132510 5Papressure.(p.240)
freezingpoint
nuclear Theenergyequivalentofthedifferenceinmassbetweenanatomicnucleusandthe
binding sumofthemassesofitsnucleons.(p.1161)
energy
nuclear Adescriptionofanuclearreactionthatusesthespecialsymbolsofisotopes,that
equation describessomekindofnucleartransformationordisintegrationandthatisbalanced
whenthesumsoftheatomicnumbersoneithersideofthearrowareequalandthe
sumsofthemassnumbersarealsoequal.(p.1163)
nuclearfission Thebreakingapartofatomicnucleiintosmallernucleiaccompaniedbythereleaseof
energythesourceofenergyinnuclearreactors.(p.1162)
nuclearfusion Theformationofatomicnucleibythejoiningtogetherofthenucleioflighteratoms.
(p.1162)
nuclear Aspectroscopictechniquethatmeasurestheabsorptionofenergybynucleiinthe
magnetic presenceofamagneticfield.(p.883)
resonance
(NMR)
spectroscopy
nucleicacid Abiopolymercontainingthreetypesofmonomerunits:heterocyclicaromaticamine
basesderivedfrompurineorpyrimidine,themonosaccaridedriboseor2deoxyd
riboseandphosphate.(p.1088)
nucleon Aprotonoraneutron.(p.8)
nucleophile Anyreagentwithanunsharedpairofelectronsthatcanbedonatedtoanotheratom
oriontoformanewcovalentbondaLewisbase.(pp.477,783)
nucleophilic Areactioninwhichanucleophilebondedtoacarbonylcarbonatomisreplacedby
acyl anothernucleophile.(p.1017)
substitution
nucleophilicity Atermfortherelativerateatwhichareagentundertakesnucleophilicsubstitution.(p.
788)
nucleophilic Anyreactioninwhichonenucleophileissubstitutedforanother.(p.783)
substitution
nucleoside Thebuildingblockofnucleicacids,consistingofdriboseor2deoxydribose
bondedtoaheterocyclicaromaticaminebasebyaNglycosidicbond.(p.1088)
nucleosome ThefundamentalunitofthechromatinstructureconsistingofDNAwrappedaround
histones.(p.1096)
nucleotide AnucleosideinwhichamoleculeofphosphoricacidisesterifiedwithanOH
groupofdriboseor2deoxydribose,mostcommonlythe3or5OHgroup.(p.
1089)
nucleus Thedensecoreofanatomthatcomprisesprotonsandneutrons.(p.7)
nuclide Aparticularatomofspecifiedatomicnumberandmassnumber.(p.9)

O
observedrotation Theanglethroughwhichacompoundrotatesaplaneofpolarisedlight.(p.762)
octahedral Describesamoleculeinwhichacentralatomissurroundedbysixatomslocated
attheverticesofanimaginaryoctahedron.(pp.181,553)
oil Atriglyceridethatisliquidatroomtemperature.(p.1039)
Okazaki ShortmoleculesofsinglestrandedDNAformedduringDNAreplicationonthe
fragments laggingstrand.(p.1097)
oligopeptide Apeptidecontainingmorethan10butfewerthan20aminoacids.(p.1066)
oligosaccharides Carbohydratescontainingfrom4to10monosaccharideunitsjoinedby
glycosidicbonds.(p.991)
opticalactivity Theabilitytorotateaplaneofpolarisedlight.(p.761)
orbital Athreedimensionalwavedescribingaboundelectron.(pp.16,128)
orbitalmixing Interactionsamongsandpatomicorbitalsthatchangetherelativeenergiesofthe
molecularorbitalsresultingfromtheseatomicorbitals.(p.203)
orbitaloverlap Theextenttowhichtwoorbitalsondifferentatomsinteract.(p.189)
order Inareaction,thesumoftheexponentsintheratelawistheoverallorder.Each
exponentgivestheorderwithrespecttotheindividualreactant.(p.636)
orderof Asystemforrankingfunctionalgroupsinorderofpriorityforthepurposesof
precedenceof IUPACnomenclature.(p.937)
functionalgroups

organometallic Acompoundcontainingacarbonmetalbond.(pp.551,942)
compound
ortho Describesgroupsoccupyingpositions1and2onabenzenering.(p.728)
osmosis Thepassageofsolventmolecules,butnotthoseofsolutes,througha
semipermeablemembrane(morelimitingthandialysis).(p.414)
osmotic Amembranethatallowspassageofsolvent,butnotsoluteparticles.(p.414)
membrane
osmoticpressure Thebackpressurethathastobeappliedtopreventosmosisoneofthecolligative
(II) properties.(p.414)
oxidation Achangeinwhichanoxidationnumberincreases(becomesmorepositiveorless
negative)alossofelectrons.(p.490)
oxidationnumber Thechargethatanatominamoleculeorionwouldhaveifalloftheelectronsin
itsbondsbelongedentirelytothemoreelectronegativeatomstheoxidationstate
ofanatom.(p.491)
oxidationstate Seeoxidationnumber.(p.491)
oxidisingacid AnacidinwhichtheanionisastrongeroxidisingagentthanH+(e.g.HClO ,
4
HNO3).(p.514)
oxidisingagent Thesubstancethatcausesoxidationandthatisitselfreduced.(p.490)
oximes CompoundscontainingaC NOHgroup.(p.953)
oxoanion Anegativelychargedioncontainingtwoormoreelements,oneofwhichis
oxygen.(p.50)
oxoniumion Anioninwhichoxygenisbondedtothreeotheratomsandbearsapositive
charge.(p.718)

P
pblockelements Acollectivenamefortheelementsingroups13to18oftheperiodictable.(pp.
14,598)
pairingenergy Theenergyrequiredtoforcetwoelectronstobecomepairedandoccupythesame
(P) orbital.(p.568)
para Describesgroupsoccupyingpositions1and4onabenzenering.(p.728)
paramagnetic Describessubstancesthatareattractedintoamagneticfieldasaresultofthe
presenceofoneormoreunpairedelectrons.(pp.146,544)
parentchain Thelongeststraightcarbonchaininanorganicmolecule.(p.54)
partialpressure Thepressureexertedbyonecomponentofagaseousmixture.(p.226)
partsperbillion Thenumberofentitiesofoneparticularcomponentpresentinonebillionobjects.
(ppb) (p.228)
partspermillion Thenumberofentitiesofoneparticularcomponentpresentinonemillionobjects.
(ppm) (p.228)
pascal(Pa) TheSIunitofpressure,onenewtonpersquaremetre.(p.215)
passivation Thestabilisationofasubstance(usuallyametal)bytheformationofathinoxide
layeronitssurface(p.523)
Pauliexclusion Therequirementthatnotwoelectronsinachemicalspeciescanbedescribedby
principle thesamesetoffourquantumnumbers.(p.130)
pentapeptide Amoleculecontainingfiveaminoacidunitsjoinedbypeptidebonds.(p.1066)
penultimate Thestereocentreofamonosaccharidefurthestfromthecarbonylgroupfor
carbon example,C(5)ofglucose.(p.979)
peptide Ashortpolymerofaminoacids.(p.1066)
peptidebond Thenamegiventotheamidebondformedbetweentheaminogroupofone
aminoacidandthecarboxylgroupofanotheraminoacid.(p.1066)
percentageby Thenumberofgramsofanelementpresentin100gofacompound.(p.80)
mass
percentage Anuncertaintyexpressedasapercentage.(p.31)
uncertainty
percentageyield Theratio,givenasapercentage,betweenthequantityofproductactually
obtainedinareactionandthetheoreticalyield.(p.88)
period Ahorizontalrowofelementsintheperiodictable.(p.14)
periodictableof Atableinwhichsymbolsfortheelementsaredisplayedinorderofincreasing
theelements atomicnumberandarrangedsothatelementswithsimilarpropertieslieinthe
samecolumn.(p.13)
pH log[H O+].(p.434)
3
phase Thestartingpositionofawavewithrespecttoonewavelength.(p.111)
phasechange Thetransitionofasubstancefromonephasetoanother.(p.260)
phasediagram Apressuretemperaturegraphshowingtheconditionsunderwhichasubstance
existsassolid,liquidandgas.(p.263)
phenol AcompoundthatcontainsanOHgroupbondedtoabenzenering.(pp.728,
823)
phenylgroup TheC6H5group.(p.728)
photoelectric Theejectionofelectronsfromametalsurfacebylight.(p.112)
effect
photodegradation Degradationofamaterialorcompoundcausedbyexposuretolight.(p.1147)
photons Particlesoflight,characterisedbyenergyE=hv.(p.113)
pi()bond Achemicalbondformedbysidebysideorbitaloverlapsothatelectrondensityis
concentratedaboveandbelowthebondaxis.(p.196)
pKa logKa .(p.443)
pKb logKb.(p.443)
pKw logKw.(p.435)
Planck'sconstant Thephysicalconstant,6.62610 34Js,thatrelatestheenergyofaphotontoits
(h) frequency.(p.113)
planeof Animaginaryplanepassingthroughanobjectanddividingitsothatonehalfis
symmetry themirrorimageoftheotherhalf.(p.751)
planepolarised Vibratingonlyinparallelplanes.(p.761)
plastic Apolymerthatcanbemouldedwhenhotandretainsitsshapewhencooled.(p.
1119)

pnictogens Theelementsingroup15oftheperiodictable.(p.15)
pOH log[OH].(p.434)
polarcovalent Abondthatpossessesanasymmetricdistributionofelectrons.(p.167)
bond
polarimeter Aninstrumentformeasuringtheabilityofacompoundtorotateaplaneof
polarisedlight.(p.762)
polarisability Theeasewithwhichtheelectrondensityaboutanatomormoleculecanbe
distorted.(p.241)
polyamide Apolymerinwhicheachmonomerunitisjoinedtothenextbyanamidebond.
(p.1124)
polycarbonate Apolyesterinwhichthecarboxylgroupsarederivedfromcarbonicacid.(p.
1130)
polycyclic Ahydrocarbonwithtwoormorefusedaromaticrings.(p.729)
aromatic
hydrocarbon
(PAH)
polydentate Describesaligandcontainingtwoormoreatomsthatcancoordinate
simultaneouslytoametalion.(p.547)
polyester Apolymerinwhicheachmonomerunitisjoinedtothenextbyanesterbond.(p.
1128)
polymer Anylongchainedmoleculesynthesisedbylinkingmanysinglepartscalled
monomers.(pp.1056,1118)
polymerisation Achemicalreactioninwhichtwoormoresmallmolecules(monomers)combine
toformlargermolecules(polymers)thatcontainrepeatingstructuralunitsofthe
monomers.(p.1118)
polypeptide Amacromoleculecontainingmorethan20aminoacidunits,eachjoinedtothe
nextbyapeptidebond.(p.1066)
polyproticacid Anacidwhichcandonatemorethanoneproton.(p.429)
polyproticbase Abasewhichcanacceptmorethanoneproton.(p.430)
polysaccharides Carbohydratescontainingalargenumberofmonosaccharideunitsjoinedtogether
byoneormoreglycosidicbonds.(p.991)
polyurethane ApolymercontainingtheNHC(O)Ogroupastherepeatingunit.(p.1131)
positron Apositivelychargedparticlewiththemassofanelectron.(p.1165)
potential Voltage,whichisameasureoftheamountofenergythatcanbedeliveredasa
difference currentmovesthroughacircuit.(p.501)
precision Agroupofmeasurementsisofhighprecisionifallthevalueslieclosetogether.
(pp.32,34)
preexponential Seefrequencyfactor.(p.655)
factor
pressure Forceperunitarea.(p.214)
primarycarbon Acarbonatomattachedtoonlyoneothercarbonatom.(p.51)
atom
primarycell Anonrechargeablebattery.(p.528)

primary(1) Thesequenceofsmallermolecularcomponentsthatareassembledtomakea
structure biopolymerthusforproteinsandpeptidesitisthespecificaminoacidsina
polypeptidechainreadfromtheNterminalaminoacidtotheCterminalamino
acid(p.1067),andforDNAandRNAitisthesequenceofbasesalongthe2
deoxyribose/ribosephosphodiesterbackboneofaDNAorRNAmoleculeread
fromthe5endtothe3end.(p.1090)
primase AnenzymethatcatalysesthesynthesisofsmallRNAmoleculesusedasprimers
forDNApolymerases.(p.1097)
primitivecubic Thecrystalformwithaunitcellcontainingonelatticepointateachcornerofa
structure cubeonly.(p.273)
principal Thequantumnumber,restrictedtopositiveintegers,thatindexestheenergyand
quantumnumber sizeofanatomicorbital.(p.128)
(n)
product Thechemicalspeciesobtainedastheresultofachemicalreaction.(pp.2,72)
protein Abiologicalmacromoleculewithamolarmassof5000uormoreandconsisting
ofoneormorepolypeptidechains.(p.1066)
proticsolvents SolventsthatcontainOHgroupsandarehydrogenbonddonors.(p.790)
proton Asubatomicparticle ,withachargeof+1andamassof1.0073u(1.6726

10 27kg),thatisfoundinatomicnuclei.(p.8)
pyranose Asixmemberedcyclichemiacetalformofamonosaccharide.(p.982)
pyridinium Amildoxidisingagent,commonlyusedtopreparealdehydesfromprimary
chlorochromate alcohols.(p.822)
(PCC)

Q
qualitative Theuseofexperimentalprocedurestodeterminewhatelementsarepresentina
analysis substance.(p.72)
quantisation Aphenomenonwherebytheenergyofachemicalsystemisnotcontinuousbutis
restrictedtocertaindefinitevalues.(p.17)
quantised Havingdiscreteallowedvalues.(p.121)
quantitative Theuseofexperimentalprocedurestodeterminethepercentagecompositionofa
analysis compoundorthepercentageofacomponentofamixture.(p.72)
quantum Anintegerorhalfintegerdescribingtheallowedvaluesofsomequantisedproperty.
number (p.128)
quartet Asignalin 1HNMRspectroscopythathasbeensplitintofourpeaksinaratioof1:3
:3:1.(p.892)
quaternary Thearrangementofpolypeptidemonomersintoanoncovalentlybonded
(4)structure aggregation.(p.1075)

R
R UsedintheR,Ssystemtoshowthattheorderofpriorityofgroupsonastereocentre
isclockwisefromtheLatinwordrectusmeaningright.(p.755)
racemic Amixtureofequalamountsoftwoenantiomers.(p.764)
mixture
radical Anonmetalspeciescontaininganoddnumberofelectronsinitsouterelectronshell.
(pp.780,1133)
radicalcation Aspecieswithapositivechargeandanunpairedelectron.(p.866)
radicalchain Atypeofpolymerisationinwhichthechaincarrierisaradical.(p.1134)
growth
polymerisation
radical Asubstitutionreactionthatinvolvesaradicalinthemechanismofsubstitution.(p.
substitution 780)
radioactive Abletoemitvariousatomicradiationsorgammarays.(p.9)
radioactive Thechangeofanucleusintoanothernucleus(orintoamorestableformofthesame
decay nucleus)bythelossofasmallparticleoragammarayphoton.(p.1163)
radioactive Asequenceofnuclearreactionsbeginningwithaverylonglivedradionuclideand
disintegration endingwithastableisotopeofloweratomicnumber.(p.1170)
series
radio Theportionoftheelectromagneticspectrumwithwavelengthsgreaterthanametre.
frequency (p.884)
radiation
radiological Atechniqueformeasuringtheageofageologicalformationoranancientartefactby
dating determiningtheratiooftheconcentrationsoftwoisotopes,oneradioactiveandthe
otherastabledecayproduct.(p.1172)
radionuclide Aradioactiveisotope.(p.9)
Raoult'slaw Thevapourpressureofonecomponentaboveamixtureofmolecularcompounds
equalstheproductofitsmolefractionanditsvapourpressurewhenpure.(p.409)
rareearth Analternativenameforthelanthanoidelements.(p.14)
elements
ratecoefficient Analternativenamefortherateconstant,theproportionalityconstantintheratelaw.
(p.636)
rateconstant Theproportionalityconstantintheratelaw.(p.636)
rate Thesloweststepinareactionmechanism.(p.659)
determining
step
ratelaw Anequationthatrelatestherateofareactiontothemolarconcentrationofthe
reactantsraisedtopowers.(p.636)
rateof Theamount(inmolesormassunits)pervolumeperunittimeofproductsformedor
reaction reactantsconsumedinaparticularreaction.(p.632)
reactant Achemicalspeciesthatistransformedinachemicalreaction.(pp.2,72)
reaction Thehorizontalaxisofapotentialenergydiagramforareaction.(p.652)
coordinate
reaction Aspeciesproducedduringareactionthatdoesnotappearinthereactionequation
intermediate becauseitisconsumedinasubsequentstepinthemechanism.(p.653)
reaction Theseriesofindividualsteps(elementaryprocesses)inachemicalreactionthat
mechanism givesthenet,overallchange.(p.638)
reaction Thenumericalvalueoftheequilibriumconstantexpressionunderanyconditions
quotient(Q) seealsoequilibriumconstantexpression.(p.349)
reaction Afractioninwhichthenumeratoristheproductofthemolarconcentrationsofthe
quotient products,eachraisedtoapowerequaltoitscoefficientintheequilibriumequation,
expression andthedenominatoristheproductofthemolarconcentrationsofthereactants,each
raisedtoapowerequaltoitscoefficientintheequation.(Forgaseousreactions,
partialpressurescanbeusedinplaceofmolarconcentrations.)(p.349)
redoxreaction Areactioninvolvingthetransferofoneormoreelectronsbetweenchemicalspecies.
(pp.17,490)
reducingagent Asubstancethatcausesreductionandisitselfoxidised.(p.490)
reducingsugar Acarbohydratethatreactswithanoxidisingagenttoformanaldonicacid.(p.988)

reduction Achangeinwhichanoxidationnumberdecreases(becomeslesspositiveormore
negative)againofelectrons.(p.490)
reduction Seeredoxreaction.(p.490)
oxidation
reaction
reduction Ameasureofthetendencyofagivenhalfreactiontooccurasareduction.(p.507)
potential
(Ered)
reductive Theformationofaniminefromanaldehydeorketone,followedbyitsreductionto
amination anamine.(p.953)
reference AcompoundaddedtoasampletobestudiedbyNMRspectroscopy,usually
compound tetramethylsilane(TMS).Thepositionsofthesignalsinthespectrumarethen
comparedwiththoseofthereferencecompound.(p.864)
refractory Aheatresistantceramicmaterial.(p.282)
regioselective Areactioninwhichonedirectionofbondbreakingorbondformingoccursin
reaction preferencetoallotherdirections.(p.713)
repeatingunit Thesmallestmolecularfragmentthatcontainsallthenonrepeatingstructuralfeatures
ofapolymerchain.(p.1119)
replication AstructurethatformswithinDNAduringreplicationithastwobranchesofsingle
fork strandedDNAsplittingfromasinglepointsuchthatitresemblesafork.(p.1097)
resolution Theseparationofaracemicmixtureintoitsenantiomers.(p.766)
resonance Theabsorptionofelectromagneticradiationbyaspinningnucleusandtheresulting
flipofitsnuclearspinstate.(p.884)
resonance Thedifferenceinenergybetweenaresonancehybridandthemoststableofits
energy hypotheticalcontributingstructures.(p.725)
resonance Theenergeticstabilisationthatoccursondelocalisationofnegativechargeovertwo
stabilisation ormoreatoms.(p.460)
resonance OneoftwoormoreLewisstructuresthatareequivalenttooneanother.(p.174)
structure
retrovirus AnRNAvirusthatpropagatesusingthehostcell'sDNAreplicationchemistryby
usingareversetranscriptaseenzymetoproduceDNAfromitsRNAgenome.(p.
1108)
reverse ADNApolymeraseenzymethattranscribessinglestrandedRNAintosingle
transcriptase strandedDNAthisisthereverseofnormaltranscription,whichinvolvesthe
synthesisofRNAfromDNA.(p.1108)
reverse Aninhibitorofthereversetranscriptaseenzyme.(p.1108)
transcriptase
inhibitor
reversible Areactioncapableofproceedingineithertheforwardorreversedirection.(p.72)
reaction
ribosomal Ribonucleicacidfoundinribosomes,thesitesofproteinsynthesis.(p.1101)
RNA(rRNA)
ribosome Acomponentofabiologicalcellwhichassemblesthespecificaminoacidstoform
proteinsasdeterminedbythenucleotidesequenceofanRNAmolecule.(p.1101)

RNA Ribonucleicacid,anucleicacidthathydrolysestoribose,phosphateions,adenine,
uracil,guanineandcytosine.(p.1088)
rootmean Averagespeedobtainedbytakingthesquarerootofthemeanvalueofthesquares
squarespeed oftheindividualspeeds.(p.223)
R,Ssystem Asetofrulesforspecifyingtheconfigurationofgroupsaroundastereocentre.(p.
754)

S
S UsedintheR,Ssystemtoshowthattheorderofpriorityofgroupsona
 stereocentreisanticlockwisefromtheLatinwordsinistermeaningleft.(p.
755)
sblockelements Acollectivenamefortheelementsingroups1and2oftheperiodictable.(p.
14)
saltbridge Atubecontaininganelectrolyte,thatconnectsthetwohalfcellsofagalvanic
cell.(p.504)
saltlinkage Anionicbondinginteractionbetweenchargedfunctionalgroupsinapeptide.
(p.1074)
saponification ThehydrolysisofanesterinaqueousNaOHorKOHtoanalcoholandthe
sodiumorpotassiumsaltofacarboxylicacid.(p.1024)
saturatedcalomel Areferenceelectrodethatconsistsofelementalmercury,mercury(I)chloride
electrode andHg 2Cl2(calomel)insaturatedKClsolution.(p.511)
saturated AcompoundcomposedsolelyofcarbonandhydrogenatomsinwhichallC
hydrocarbon Cbondsaresingleseealsoalkane.(pp.54,686)
saturatedsolution Asolutioninwhichnomoresolutewilldissolveataspecifiedtemperature.(p.
390)
scientificnotation Amethodofexpressingnumbersintermsofpowersof10.Forexample,the
number3613becomes3.61310 3inscientificnotation.(p.30)
second TheSIunitoftime.(p.25)
secondarycarbon Acarbonatomattachedtotwoothercarbonatoms.(p.51)
atom
secondarycell Abatterythatcanberecharged.(p.528)
secondary(2) Theorderedarrangement(conformation)ofabiopolymerthustheorganised
structure shapeofthechainofaminoacidsinlocalisedregionsofapolypeptideor
protein,seenassheetsorcoils(p.1069),andtheorderedarrangementofDNA
andRNAstrands(p.1091),toformadefinedthreedimensionalshape.
secondlawof Wheneveraspontaneouseventtakesplaceinouruniverse,thetotalentropyof
thermodynamics theuniverseincreases(S total>0).(p.322)
seesawshape Themolecularshapethatresemblesaseesaw.(p.180)
sensestrand Complimentarytotheantisensestrand,thesensestrandhasexactlysamebase
sequenceasthemRNAtranscriptproduced(exceptwiththyminereplacedby
uracil)suchthattheultimatepeptidegeneratedfromtheprocesshasanamino
acidsequencedefinedbythebasespresentonthisstrand.(p.1102)
shielded DescribesthesituationinNMRspectroscopyinwhichlocalmagneticfields
fromelectronssurroundinganucleusdecreasetheabilityofanapplied
magneticfieldtobringthenucleusintoresonance.(p.884)
shielding Thepartialcancellationoftheelectrostaticattractionbetweenthenucleusand
anelectronwithinanatom,causedbyoneormoreelectronsoflowerprincipal
quantumnumber.(p.136)
sigma()bond Abondthatistotallysymmetricwithrespecttorotationabouttheinternuclear
axis.(p.167)
signalsplitting AphenomenoninNMRspectroscopyinwhichthe1HNMRsignalfromone
setofhydrogenatomsissplitbytheinfluenceofneighbouringnonequivalent
hydrogenatoms.(p.893)
significantfigures Thefiguresinaphysicalmeasurementthatareknowntobecertainplusthefirst
figurethatcontainsuncertainty.(p.30)
silicone Seesiliconpolymer.(p.1149)
siliconpolymer Inorganicpolymerwithasiliconoxygenbackbone.(p.1149)
silver/silver AreferenceelectrodewhereanAgrodisdippedintoamixtureofAgCland
chlorideelectrode KClofdifferentconcentrations.(p.511)
silvermirrortest AqualitativetestforanaldehydeusingTollens'reagentthealdehydeis
oxidisedtoacarboxylateanion,andAg +isreducedtometallicsilver.(p.959)
singlebond Achemicalbondformedbyonepairofelectronssharedbetweentwoatoms.
(p.171)
singlet Asignalin 1HNMRspectroscopythathasnotbeensplit.(p.892)
SI(Systme Asystemofunitsbasedonsevenbaseunitsfromwhichallotherscanbe
International)units derived.(p.24)
SN1 Atypeofnucleophilicsubstitutionreactioninwhichonlyonemoleculeis
involvedintheratedeterminingstep.(p.787)
SN2 Atypeofnucleophilicsubstitutionreactioninwhichtwomoleculesorionsare
involvedintheratedeterminingstep.(p.786)
soap Thesodiumorpotassiumsaltofafattyacid.(p.1041)
softLewisacid ALewisacidhavinganacceptoratomofhighpolarisibility.(p.479)
softLewisbase ALewisbasehavingalargedonoratomofhighpolarisabilityandlow
electronegativity.(p.479)
solidwedge Asolidwedgedenotesabondcomingoutofthepagetowardstheobserver.(p.
43)
solubility Themaximumamountofasolutethatdissolvescompletelyinagivenmassor
volumeofsolventataparticulartemperature.(p.390)
solubilityproduct Theequilibriumconstantforthedissolutionofanionicsalt.(p.400)
(Ksp)
soluble Describesasolidoragasthatdissolvesinasolvent.(p.390)
solute Thedissolvedsubstancecontainedinasolution.(pp.90,390)
solution Ahomogeneousmixtureinwhichallparticlesareofthesizeofatoms,small
moleculesorsmallions.(pp.90,390)
solvation Thedevelopmentofacagelikenetworkofasolution'ssolventmolecules
aroundamoleculeorionofthesolute.(p.396)
solvationenthalpy Theenthalpychangeduetotheinteractionofgaseousmoleculesorionsof
solutewithsolventmoleculesduringtheformationofasolution.(p.397)
solvent Theliquidcomponentofasolution.(pp.90,390)
solvolysis Areactioninwhichthesolventplaystheroleofthenucleophileinthe
substitutionreaction.(p.787)
spacefillingmodel Athreedimensionalrepresentationofamoleculethatattemptstoshowthe
actualrelativesizesofatomswithinamolecule.(p.43)
specificheat(c) Seespecificheatcapacity.(p.301)
specificheat Thequantityofheatthatwillraisethetemperatureof1gofasubstanceby1K,
capacity(c) usuallyinunitsof1Jg 1K1alsocalledspecificheat.(p.301)
specificrotation[] Theobservedrotationofaplaneofpolarisedlightwhenasampleisplacedina
tube1.0dmlongandataconcentrationof1.0g/100mLifapuresampleis
used,itsconcentrationisgivening/mL(i.e.itsdensity).(p.763)
spectatorion Anionwhoseformulaisidenticalonbothsidesofanionicequation,thatdoes
notparticipateinthereactionandthatisexcludedfromthenetionicequation.
(p.97)
spectrochemical Alistofligandsorderedintermsoftheirabilitytoproduceacrystalfield
series splitting.(p.572)
sphybridorbitals Twoatomicorbitalsconstructedbytheinteractionbetweenansorbitalandap
orbitalonthesameatom.(p.194)
sp 2hybridorbitals Threeatomicorbitalsconstructedbytheinteractionsbetweenansorbitaland
twoporbitalsonthesameatom.(p.193)
sp 3hybridorbitals Fouratomicorbitalsconstructedbytheinteractionsbetweenansorbitaland
threeporbitalsonthesameatom.(p.190)
spin Theintrinsicangularmomentumofelectronsandprotonsthatgivesthem
magnetism.(pp.17,129)
spinquantum Thequantumnumber,restrictedtoeither ,whichindexesthe
number(ms )
orientationofelectronspin.(p.130)
splittingpattern Thepatternobtainedwhenasignalina1HNMRspectrumissplitbythe
influenceofneighbouringnonequivalenthydrogenatoms.Thesecanbe
describedasmultiplets,singlets,doublets,triplets,quartetsetc.(p.892)
spontaneous Describesachangethatoccursbyitselfwithoutoutsideassistance.(p.294)
squareplanar Ageometryadoptedby4coordinatecomplexesinwhichthefourMLbonds
pointtothecornersofasquare(p.554)
squarepyramidal Ageometryadoptedby5coordinatecomplexes,consistingofapyramidwith
fourtriangularsidesandasquarebase.(p.554)

standardcell Awayofdescribingtheanodeandcathodehalfcellsinagalvaniccell.The
notation anodehalfcellisspecifiedontheleft,withtheelectrodematerialoftheanode
givenfirstandaverticalbarrepresentingthephaseboundarybetweenthe
electrodeandthesolution.Dasheddoublebarsrepresentthesaltbridge
betweenthehalfcells.Thecathodehalfcellisspecifiedontheright,withthe
materialofthecathodegivenlast.Onceagain,asingleverticalbarrepresents
thephaseboundarybetweenthesolutionandtheelectrode.(p.505)
standardcell Thepotentialofagalvaniccellat25C,whenallionicconcentrationsare
potential exactly1mandthepartialpressuresofallgasesare10 5Pa.(p.507)
standardenthalpy Theenthalpychangeforthecombustionof1moleofacompoundunder
ofcombustion standardconditions.(p.313)

standardenthalpy Theenthalpychangewhen1moleofacompoundisformedfromitselements
offormation intheirstandardstates.(p.309)

standardenthalpy Theenthalpychangeofareactionwhendeterminedwithreactantsandproducts
ofreaction at10 5Paandonthescaleofthemolequantitiesgivenbythecoefficientsofthe
balancedequation.(p.306)
standardentropy Theentropyofasubstancemeasuredunderstandardconditions.(p.323)

standardentropyof Theentropychangewhen1moleofasubstanceisformedfromitselementsin
formation theirstandardstates.(p.324)

standardentropyof Theentropychangeofareactionwhendeterminedwithreactantsandproducts
reaction at10 5Paandonthescaleofthemolequantitiesgivenbythecoefficientsofthe
balancedequation.(p.324)
standardGibbs (p.327)
energychange

standardhydrogen
Thestandardofcomparisonforreductionpotentialsandforwhich has
electrode
avalueof0V(25C,10 5Pa)when[H+]=1minthereversiblehalfcell
reaction2H+(aq)+2e H2(g).(p.508)
standardreduction Thereductionpotentialofahalfreactionat25Cwhenallionconcentrations
potential are1mandthepartialpressuresofallgasesare10 5Pa.(p.507)

standardstate Theconditioninwhichasubstanceisinitsmoststableformat10 5Paatthe

specifiedtemperature.(p.306)
statefunction Aquantitythatdependsonlyontheinitialandfinalstatesofthesystemandnot
onthepathtakenbythesystemtogetfromtheinitialtothefinalstatep,V,T,
H,SandGareallstatefunctions.(p.297)
statistical Describesapolymerinwhichthesequenceofmonomersfollowsastatistical
rule.(p.1123)
steadystate Amethodtoderivetheratelawforareaction,usingtheassumptionthatthe
approximation concentrationofanyintermediateremainsconstantasthereactionproceeds.(p.
662)
stepgrowth Apolymerisationinwhichchaingrowthoccursinastepwisemannerbetween
polymerisation difunctionalmonomers,generallywithreleaseofasmallmolecule.(p.1123)
stereocentre Forcarbon,atetrahedralcarbonatomwithfourdifferentgroupsbondedtoitin
generalterms,anyatomwithsufficientatomsorgroupsarrangedaroundit,so
thatstereoisomersmaybeformedonexchangeofanytwoatomsorgroups.(p.
751)
stereoisomers Isomerswiththesamemolecularformulaandthesameconnectivitybut
differentorientationsoftheiratomsinspace.(pp.555,746)
stereospecific Areactioninwhichonestereoisomerisformedordestroyedinpreferencetoall
reaction othersthatmightbeformedordestroyed.(p.719)
stericfactor Afactorthatreflectsthefractionofcollisionswitheffectiveorientations.(p.
655)
sterichindrance Theabilityofgroups,becauseoftheirsizeandshape,tohinderaccesstoa
reactionsitewithinamolecule.(p.789)
stericstrain Thestraininducedinamoleculearisingfromtherepulsionbetweenthe
electronsofthebondsinthemolecule.(p.692)
stoichiometric Numbersinfrontofformulaeinchemicalequations.(p.72)
coefficients
stoichiometry Adescriptionoftherelativequantitiesbymolesofthereactantsandproductsin
areactionasgivenbythestoichiometriccoefficientsinthebalancedequation.
(p.72)
stretching Atypeofvibrationthatchangesbondlengths.(p.872)
strongacid Anacidthatreactscompletelywithwatertogivequantitativeformationof
H3O+.(p.438)
strongbase AbasethatreactscompletelywithwatertogivequantitativeformationofOH.
(p.438)
strongnuclear Theattractiveforcebetweenprotonsandneutronsthatholdsthenucleus
force together.(p.1161)
strongfield Describesligandsthatproducelargecrystalfieldsplittings.(p.572)
structuralformula Adepictionofamoleculeorpolyatomicionthatshowshowtheconstituent
atomsarearranged,towhichotheratomstheyarebonded,andthekindsof
bonds(single,doubleortriple)present.(p.37)
structuralisomers Isomerswiththesamemolecularformula,butdifferentordersofattachmentsof
theconstituentatoms.(p.555)
styrene Thecommonnameforphenylethylene.(p.728)
subatomicparticles Electrons,protonsandneutrons.(p.8)
sublimation Thephasechangebetweensolidandvapour.(p.261)
substituent Agroupattachedtothelongestcarbonchainofanorganicmolecule.(p.54)
supercoiling Thethreedimensionalarrangementofallatomsofanucleicacid.(p.1095)
superconductor Amaterialthatoffersnoresistancetotheflowofelectricity.(p.286)
supercriticalfluid Aphaseinwhichtheliquidvapourtransitionisnolongerpossible.A
supercriticalfluidisabletoexpandtofilltheavailablespace(likeagas),butis
resistanttofurthercompression(likealiquid).(p.263)
superhelicaltwist Achangeofconformationthatresultsincompensationofstrainintroducedinto
circularDNAifthehelicaltwistischanged.(p.1095)
surfacetension Theresistanceofaliquidtoanincreaseinitssurfacearea.(p.254)
surroundings Thatpartoftheuniverseotherthanthesystembeingstudiedandseparated
fromthesystembyarealoranimaginaryboundary.(p.295)
symproportionation Anelectrochemicalprocessinwhichtworeactantsthatcontainthesame
elementindifferentoxidationstatesreacttogiveasingleproducthavingan
oxidationnumberintermediatebetweenthetworeactants.(p.529)
synaddition Theadditionofatomsorgroupsofatomsfromthesamesideorfaceofa
carboncarbondoublebond.(p.721)
syndiotactic Onediastereomericformofpolypropyleneinwhichthemethylgroupsalternate
polypropylene fromfronttobackalongthecarbonchain.(p.1138)
system Thatpartoftheuniverseunderstudyandseparatedfromthesurroundingsbya
realoranimaginaryboundary.Asystemmaybeopen,closedorisolated.(p.
295)

T
tautomerism Aformofisomerisminwhichconstitutionalisomersareinequilibriumwitheach
other.Theisomersdifferinthelocationofahydrogenatomandadoublebond
relativetoaheteroatom,mostcommonlyO,SorN.(p.962)
tautomers Constitutionalisomersthatdifferinthelocationofhydrogenandadoublebond
relativetoO,NorS.(p.962)
templatestrand Analternativenameforantisensestrandseealsocodingstrand,sensestrand.(p.
1102)
terminalcarbon Acarbonatomattheendofachainofcarbonatoms.(p.38)
tertiarycarbon Acarbonatomattachedtothreeothercarbonatoms.(p.51)
atom
tertiary(3) Thethreedimensionalarrangementinspaceofallatomsinasinglepolypeptide
structure chain(p.1072)thethreedimensionalarrangementofallatomsofaDNAor
RNAseealsosupercoiling.(p.1095)
tetrahedral Ageometryadoptedby4coordinatecomplexesinwhichthecentralmetalionis
coordinatedtofourliganddonoratomslocatedatthecornersofanimaginary
tetrahedron.(pp.178,554)
tetrahedral Anintermediateformedfromtheadditionofanucleophiletothecarbonylgroup.
carbonyladdition (p.942)
intermediate
tetramethylsilane ThereferencestandardusedinNMRspectroscopy.Itssignalissetat=0.(p.
(TMS) 885)
tetrapeptide Amoleculecontainingfouraminoacidsunitsjoinedbypeptidebonds.(p.1066)
theoreticalyield Theamountofaproductdeterminedbythestoichiometryofthereaction.(p.88)
theoryof Thetheorythatsomemoleculeshavestructuresthatcannotberepresentedbyany
resonance singlecontributingstructuresomustberepresentedasahybridoftwoormore
equivalentcontributingstructures.(p.724)
thermochemical Abalancedchemicalequationaccompaniedbythevalueof that
equation correspondstothemolequantitiesspecifiedbythecoefficients.(p.306)
thermodynamic Anequilibriumconstantdefinedintermsofactivities.(p.353)
equilibrium
constant
thermodynamic Atemperaturescaleinwhichtemperatureismeasuredinkelvin.(p.295)
temperature
thermoplastic Apolymerthatcanbemeltedandmouldedintoashapethatisretainedwhenitis
cooled.(p.1119)
thermosetting Apolymerthatcanbemouldedwhenitisfirstprepared,but,oncecooled,
plastic hardensirreversiblyandcannotberemelted.(p.1119)
thiol AcompoundcontaininganSH(sulfhydryl)group.(p.832)
thirdlawof Atabsolutezero,theentropyofaperfectlyorderedpurecrystallinesubstanceis
thermodynamics 0.(p.323)
3end Theendofapolynucleotideatwhichthe3OHgroupoftheterminal2
deoxyribose/riboseunitisfree.(p.1090)
titrant Anacidorbaseofknownconcentrationusedinanacidbasetitration.(p.467)
titrationcurve Foranacidbasetitration,agraphofpHversusthevolumeoftitrantadded.(p.
468)
Tollens'reagent Asolutionofsilvernitrateinaqueousammonia.(p.959)
toluene Thecommonnameformethylbenzene.(p.728)
torsionalstrain Atypeofstericstrainwhererepulsionfromtheelectronsinbondsinducesa
twistingforceawayfromaneclipsinginteraction.(p.691)
transcription TheprocessbywhichacomplementaryRNAcopyofasequenceofDNAis
created.(p.1101)
transesterification Thereactionofanesterwithanalcoholtoproduceadifferentester.(p.1022)
transferRNA Ribonucleicacidthatcarriesaspecificaminoacidtothesiteofproteinsynthesis
(tRNA) onribosomes.(p.1101)
transisomer Astereoisomerthatcontainstwogroupsthatprojectonoppositesidesofa
referenceplane.(p.555)
transitionmetals Theelementsingroups3to12oftheperiodictable.(pp.14,544)
transitionstate Theenergymaximumonthepotentialenergysurfaceofareaction.Itisthebrief
momentduringanelementaryprocessinareactionmechanismwhenthespecies
involvedhaveacquiredtheminimumamountofpotentialenergyneededfora
 successfulreaction.(p.653)
transmutation Theconversionofoneisotopeintoanother.(p.1171)
transuranium Elements93andhigher.(p.1172)
elements
triacylglycerol Seetriglyceride.(p.1034)
triglyceride Anesterofglycerolwiththreefattyacids.(p.1034)
trigonal Ageometryadoptedby5coordinatecomplexesinwhichacentralmetalionis
bipyramidal coordinatedtofiveliganddonoratomslocatedatthecornersofatrigonal
bipyramid.(pp.179,554)
trigonalplanar Themolecularshapeinwhichacentralatomisbondedtothreeotheratomslying
inaplaneat120anglestooneanother.(p.177)
triol Acompoundwiththreealcoholgroups.(p.811)
tripeptide Amoleculecontainingthreeaminoacidunitsjoinedbypeptidebonds.(p.1056)
triplebond Abondbetweentwoatomsconsistingofthreepairsofbondingelectrons.(p.
171)
triplepoint Thetemperatureandpressureatwhichsolid,liquidandvapourcancoexistat
equilibrium.(p.264)
triplet Asignalin 1HNMRspectroscopythathasbeensplitintothreepeaksinaratioof
1:2:1.(p.892)
triproticacid Anacidthatcandonatethreeprotons.(p.429)
trisaccharides Carbohydratescontainingthreemonosaccharideunitsjoinedbyglycosidic
bonds.(p.991)
tropicaloil Aplantoil,suchascoconutoilorpalmoil,thatcontainsarelativelyhigh
proportionoflowmolarmasssaturatedfattyacids.(p.1039)

U
uncertainty Theassertionthatpositionandmomentumcannotbothbeexactlyknown.(p.127)
principle
unimolecular Areactioninwhichonlyonespeciesisinvolvedinthetransitionstateoftherate
reaction determiningstep.(p.787)
unit Aspecificstandardquantityofaparticularproperty,againstwhichallother
quantitiesofthatpropertycanbemeasured.(p.24)
unitcell Thesimplestrepeatingunitofaregularpattern,usuallywithinacrystal.(p.271)
universe Asystemanditssurroundingstakentogether.(p.295)
unsaturated Ahydrocarboninwhichatleastonecarbonatomdoesnothavethemaximum
hydrocarbon possiblenumberofatomsbondedtoit.(p.686)
upfield DescribesasignalinNMRspectroscopythatistowardstherightofthespectrumor
ofanothersignal.(p.886)
UV/visible Atechniqueusedtostudycompoundsthatabsorblightintheultravioletvisible
spectroscopy region.(p.905)

V
valenceelectrons Theelectronsofanatomthatoccupyorbitalsofhighestprincipalquantum
 numberandincompletelyfilledorbitals.(p.140)
valenceshell Theprincipleofminimisingelectronelectronrepulsionbyplacingelectron
electronpair pairsasfarapartaspossible.(p.176)
repulsion(VSEPR)
vanderWaals Anequationthatcorrectstheidealgasequationfortheeffectsofmolecular
equation sizeandintermolecularforces.(p.238)
van'tHoffequation
.Thisshowshowthevalueofanequilibriumconstantvaries
withtemperature.(p.368)
van'tHofffactor(i) Theratiooftheobservedfreezingpointdepressiontothevaluecalculated
assumingthatthesolutedissolvesasunionisedmolecules.(p.419)
vaporisation Conversionofaliquidintoitsvapour.(p.240)
vapourpressure Thepartialpressureofavapourinequilibriumwithacondensedphase.(p.
255)
vibrationalinfrared Theportionoftheinfraredregionwithafrequencyrangeof4004000cm1.
(p.871)
viscosity Theresistancetoflowofafluid.(p.255)
volt(V) TheSIunitofelectricpotentialinjoulespercoulomb1V=1JC1.(p.501)
voltmeter Aninstrumentformeasuringpotentialdifference.(p.502)
vulcanisation Achemicalreactioninwhichthephysicalpropertiesofanelastomerare
changedbyreactionwithsulfurtoformcrosslinksbetweenthepolymer
chains.(p.1147)
vulcanisedrubber Naturalrubberthathasbeentreatedwith,forexample,sulfurthatforms
crosslinksbetweenthepolymerchainsandimprovesthepropertiesofthe
rubber.(p.1147)

W
wavelength Thedistancebetweenanytwoconsecutiveidenticalpointsonawave.(pp.110,870)
()
wavenumber Thenumberofwavelengthspercentimetre.Theunitofwavenumberisthereciprocal
centimetre(cm1)andiscommonlyusedininfraredspectroscopy.(p.871)
weakacid Anacidthatreactsincompletelywithwatertoformlessthanstoichiometricamountsof
H3O+.(p.438)
weakbase Abasethatreactsincompletelywithwatertoformlessthanstoichiometricamountsof
OH.(p.438)
weakfield Describesligandsthatproducesmallcrystalfieldsplittings.(p.572)
work(w) Theenergyexpendedinmovinganopposingforcethroughaparticulardistance.Work
hasunitsofforcedistance.(p.298)

X
Xraycrystallography ThestudyofcrystalstructuresbyXraydiffractiontechniques.(p.906)
xylene Thecommonnameforthethreeisomericdimethylbenzenes.(p.728)
Z
Zaitsev's Arulestatingthatthemajorproductofaeliminationreactionisthemoststable
rule alkenethatis,thealkenewiththemostsubstituentsonthecarboncarbondouble
bond.(p.794)
ZDNA OneofthemanypossibleDNAdoublehelicalstructuresitshelixislefthanded.(p.
1095)
Ziegler Acatalyst,typicallybasedontitaniumtetrachlorideandtheorganometalliccompound
Natta triethylaluminium,whichisusedintheproductionofunbranched,stereoregular
catalyst polyalkenepolymers.(p.1137)
zinc SeedrycellbatteryLeclanchcell.(p.529)
manganese
dioxidecell
zwitterion Anionicsaltinwhichbothcationandanionarepartofthesamemolecule.(pp.445,
847,1056)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.


FRONTCOVER
Periodictableoftheelements

Atomicmassesinparenthe
tothelongestlivedisotope
element.

Commonphysicalconstants
Massofelectron me =9.10938215(45)10 31kg(5.4857991010 4u)
Massofproton mp=1.672621637(83)10 27kg(1.007276467u)
Massofneutron mn=1.674927211(84)10 27kg(1.008664916u)
Electroniccharge e=1.602176487(40)10 19C
Atomicmassunit u=1.660538782(83)10 27kg
Gasconstant R=8.314472(15)Jmol1K1
Molarvolumeofanidealgas V =22.710981(40)Lmol1(at0Cand1.0010 5Pa)
m

TheAvogadroconstant
NA=6.02214179(30)10 23mol1
Speedoflightinavacuum c=2.9979245810 8ms1
Planck'sconstant h=6.62606896(33)10 34Js
Faradayconstant F=9.64853399(24)10 4Cmol1

Name Symbol Atomicnumber Molarmass(gmol1)(a)

actinium Ac 89 227.0278 (b)
aluminium Al 13 26.9815386(8)
americium Am 95 243.0614 (b)
antimony Sb 51 121.760(1)
argon Ar 18 39.948(1)
arsenic As 33 74.92160(2)
astatine At 85 209.9871(b)
barium Ba 56 137.327(7)
berkelium Bk 97 247.0703(b)
beryllium Be 4 9.012182(3)
bismuth Bi 83 208.98040(1)
bohrium Bh 107 (d)

boron B 5 [10.80610.821](e)
bromine Br 35 79.904(1)
cadmium Cd 48 112.411(8)
cadmium Cd 48 112.411(8)
caesium Cs 55 132.9054519(2)
calcium Ca 20 40.078(4)
californium Cf 98 251.0796 (b)
carbon C 6 [12.009612.0116](e)
cerium Ce 58 140.116(1)
chlorine Cl 17 [35.44635.457](e)
chromium Cr 24 51.9961(6)
cobalt Co 27 58.933195(5)
copernicium Cn 112 285.174 (b)
copper Cu 29 63.546(3)
curium Cm 96 247.0704 (b)
darmstadtium Ds 110 281.162 (b)
dubnium Db 105 268.125 (b)
dysprosium Dy 66 162.500(1)
einsteinium Es 99 252.0830 (b)
erbium Er 68 167.259(3)
europium Eu 63 151.964(1)
fermium Fm 100 257.0951(b)
fluorine F 9 18.9984032(5)
francium Fr 87 223.0197 (b)
gadolinium Gd 64 157.25(3)
gallium Ga 31 69.723(1)
germanium Ge 32 72.63(1)
gold Au 79 196.966569(4)
hafnium Hf 72 178.49(2)
hassium Hs 108 277.150 (b)
helium He 2 4.002602(2)
holmium Ho 67 164.93032(2)
hydrogen H 1 [1.007841.00811](e)
indium In 49 114.818(3)
iodine I 53 126.90447(3)
iridium Ir 77 192.217(3)
iron Fe 26 55.845(2)
krypton Kr 36 83.798(2)
lanthanum La 57 138.90547(7)
lawrencium Lr 103 262.1096 (b)
lead Pb 82 207.2(1)
lithium Li 3 [6.9386.997](e)
lutetium Lu 71 174.9668(1)
magnesium Mg 12 24.3050(6)
manganese Mn 25 54.938045(5)
meitnerium Mt 109 276.151(b)
mendelevium Md 101 258.0984 (b)
mercury Hg 80 200.59(2)
molybdenum Mo 42 95.96(2)
neodymium Nd 60 144.242(3)
neon Ne 10 20.1797(6)
neptunium Np 93 237.0482 (b)

nickel Ni 28 58.6934(4)
niobium Nb 41 92.90638(2)
nitrogen N 7 [14.0064314.00728](e)
nobelium No 102 259.1010 (b)
osmium Os 76 190.23(3)
oxygen O 8 [15.9990315.99977](e)
palladium Pd 46 106.42(1)
 phosphorus P 15 30.973762(2)
platinum Pt 78 195.084(9)
plutonium Pu 94 244.0642 (b)
polonium Po 84 208.9824 (b)
potassium K 19 39.0983(1)
praseodymium Pr 59 140.90765(2)
promethium Pm 61 144.9127 (b)
protactinium Pa 91 231.03588(2)(b)
radium Ra 88 226.0254 (b)
radon Rn 86 222.0176 (b)
roentgenium Rg 111 280.164 (b)
rhenium Re 75 186.207(1)
rhodium Rh 45 102.90550(2)
rubidium Rb 37 85.4678(3)
ruthenium Ru 44 101.07(2)
rutherfordium Rf 104 265.1167 (b)
samarium Sm 62 150.36(2)
scandium Sc 21 44.955912(6)
seaborgium Sg 106 271.133(b)
selenium Se 34 78.96(3)
silicon Si 14 [28.08428.086](e)
silver Ag 47 107.8682(2)
sodium Na 11 22.98976928(2)
strontium Sr 38 87.62(1)
sulfur S 16 [32.05932.076](e)
tantalum Ta 73 180.94788(2)
technetium Tc 43 97.9072 (b)
tellurium Te 52 127.60(3)
terbium Tb 65 158.92535(2)

thallium Tl 81 [204.382204.385](e)
thorium Th 90 232.03806(2)(b)
thulium Tm 69 168.93421(2)
tin Sn 50 118.710(7)
titanium Ti 22 47.867(1)
tungsten W 74 183.84(1)

ununhexium(c) Uuh 116 (d)

ununoctium(c) Uuo 118 (d)

ununpentium(c) Uup 115 288.192 (b)

ununquadium(c) Uuq 114 289.187 (b)

ununseptium(c) Uus 117 (d)

ununtrium(c) Uut 113 284.178 (b)

uranium U 92 238.02891(3)(b)
vanadium V 23 50.9415(1)
xenon Xe 54 131.293(6)
ytterbium Yb 70 173.054(5)
yttrium Y 39 88.90585(2)
zinc Zn 30 65.38(2)
zirconium Zr 40 91.224(2)
(a)Allknownsignificantfiguresaregiven.Parenthesesindicatethatthefigureisuncertain.
(b)Elementhasnostablenuclides.Themolarmassofthelongestlivedisotopeisgiven.
(c)UnnamedatSeptember2011.
(d)Accuratemolarmasshasnotyetbeendetermined.
(e)Themolarmassintervalreflectsthesetofmolarmassvaluesinnormalmaterials.

Source:Wieser,MEandCoplen,TB,Atomicweightsoftheelements2009PureAppl.Chem.,vol.83,no.2,pp.35996,IUPAC2010
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BACKCOVER

Aselectionofinterconversionspossibleforsomeofthesimplerfunctionalgroups

Someimportantorganicfunctionalgroups
Functionalgroup(a) Example Name

acidanhydride ethanoicanhydride(acetic
anhydride)

acidchloride ethanoylchloride(acetyl
chloride)

alcohol CH3CH2OH ethanol(ethylalcohol)

aldehyde ethanal(acetaldehyde)

alkene CH2 CH2 ethene(ethylene)

alkyne HC CH ethyne(acetylene)
amide ethanamide(acetamide)
 amine,primary CH3CH2NH2 ethylamine

amine, (CH3CH2)2NH diethylamine

secondary
amine,tertiary (CH3CH2)3N triethylamine

arene benzene

carboxylicacid ethanoicacid(aceticacid)

disulfide CH3SSCH3 dimethyldisulfide

ester methylethanoate(methyl
acetate)

haloalkane CH3CH2Cl chloroethane(ethylchloride)

X=F,Cl,Br,I
ketone propanone(acetone)

phenol phenol

sulfide CH3SCH3 dimethylsulfide

thiol CH3CH2SH ethanethiol(ethylmercaptan)

(a)Functionalgroupshowninred.R=hydrogen,alkylorarylgroup,exceptforamines,alcohols,
haloalkanes,ketonesandthiolswhereRcannotbeH.

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