Chapter1

Water:ANaturalWonder

Chapter1AnswerstoEndofChapterProblems
Section1.1.
PhasesofMatter
1.1.

Identifythefollowingasbeingeitherachemicalpropertyoraphysicalproperty.Placea
PbyallthephysicalpropertiesandaCbyallthechemicalproperties.
(a) _____ waterisclearandcolorless
(b) _____ somemetalsreactwithwatertoproducehydrogengas
(c) _____ waterhasadensityof1.000g/cm3at4C
(d) _____ waterboilsat100C
(e) _____ wateristheproductofareactionbetweenanacidandabase
(f) _____ waterisapolarmolecule
Answer:(a)P(b)C(c)P(d)P(e)C(f)C

1.2.

Comparesolids,liquids,andgasesineachgivencategory.
Solids

Liquids

Gases

Definitevolume?
Definiteshape?
Fixedorchangingposition
ofmolecules?
Averagedistancebetween
moleculessmallorlarge?
Answer:
Solids

Liquids

Gases

Definitevolume?

Yes

Yes

No

Definiteshape?

Yes

No

No

Relative
arrangementof
molecules?

Orderly,fixed
positions

Moleculesfreeto
move

Moleculesmove
almostindependently

Relativeaverage
distancebetween
molecules?

Closestofthethree
phases

Close,butnotas
closeasinsolids

Notclose,but
relativelyfarapart

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1.3.

Water:ANaturalWonder

Whichphasesofmatterarereferredtoascondensedphases?Whatisthejustification
fortheuseofthisterm?
Answer:Solidsandliquidsarecalledcondensedphases.Inbothofthesephases,
moleculesarerelativelyclosetogetherandthereforearelikelytohavesomeinteractions.
Themoleculesinthegasphase,bycontrast,arespreadapartwithsignificantlyless
chanceforinteraction.Whiletheprocessofcondensationusuallyreferstotheproduction
ofliquidfromthegas(vapor)phase,bothliquidandsolidphasesaretermedcondensed
phases.

1.4.

(a) Namethephasechangesbetweeneachofthestatesofmatterindicatedbythearrows
inthisdiagram.

(b) Labeleachofthefourarrowsonthediagramtoindicatewhetherenergyisreleased
orabsorbedintheprocess.
Answer:(a)

(b)Energyisreleasedincondensationandfreezing.Energyisabsorbedinvaporization
andmelting.
1.5.

NameasubstanceotherthanwaterthatcommonlyexistsasaliquidatSTP.
Answer:Therearemanypossibleanswers,includinggasoline,rubbingalcohol,and
cookingoil.

1.6.

NameasubstancethatcommonlyexistsasagasatSTP.

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Answer:Therearemanypossibleanswers,includingnitrogen(N2),oxygen(O2),argon
(Ar)andcarbondioxide(CO2),allfoundintheEarthsatmosphere.
1.7.

Whathappensifaclosedglassbottlefullofwateriskeptoutsidewhilethetemperature
fallsbelow0C?
Answer:Whenwaterfreezes,theclosedglassbottlewillbreakbecausethegiven
volumeoficeisgreaterthanthesamevolumeofwater.

1.8.

OnemethodforseparatingaNaCl(aq),sodiumchloridesolution,intoitscomponentsisto
boilthesolutionofsaltwater.Inthiscase,waterwillevaporateandNaCl(s)willbeleft
behind.
(a) WhichpropertyofNaCl(s)andwateraccountsforthisseparation?
(b) Designanapparatusthatcouldchangethewatervaporbackintoaliquidaswellas
recoverNaCl(s).Nameallphasechangesthatoccur.
Answer:IfoneboilsasolutionofNaCl(aq)andwater,thewaterwillevaporate
andthesaltwillbeleftbehindduetothefactthatwaterhasamuchlowerboiling
pointthanatablesalt.Thesimpleapparatusfortheseparationofasodium
chloridesolutionispresentedbelow.Boilingthesolutionevaporatesthewater,
whichiscondensedandcollectedinthereceivingflask.Afterallthewaterhas
boiledaway,NaCl(s)remainsintheboilingflask.Thefigurebelowshowsthe
distillationapparatusthatisusedtoseparatethismixture.

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Chapter1
1.9.

Water:ANaturalWonder

Giventwoliquidsthatdonotdissolveinoneanother(likeoilandwater),designan
experimentthatwouldallowyoutodeterminewhichismoredense.
Answer:Averydirectexperimentistopourafewdropsofeitheroneintotheother.If
theaddedliquidsinks,thenitismoredense.Iftheaddedliquidremainsonthesurface,
thenitislessdense.

1.10.

Howcouldyoudetermine(experimentally)ifthesolidphaseofaparticularsubstanceis
moredenseorlessdensethantheliquidphaseofthesamesubstance?
Answer:Mixingsamplesofthesolidandliquidwillquicklyallowforthe
determinationofrelativedensity.Ifthesolidismoredense,thenitwillsinkintheliquid.
Ifthesolidislessdense,thenitwillfloatintheliquid(asisthecaseforsolidwater(ice)
inliquidwater).

1.11.

ConsiderFigure1.3comparingthedensitiesofsolidandliquidphasesoftbutanolwith
thoseofwater.Whatadditionalinformationdoyouneedtobeabletopredictwhatwill
happenifasampleofsolidtbutanolweredroppedintoliquidwater?Howwouldyou
findthatinformation?
Answer:Thefigureshowsthatthedensityofthesolidalcoholisgreaterthanthatofits
liquidphasebutthatthedensityoftheliquidwaterisgreaterthanthatofitssolidphase.
Whatisnotknownishowthedensityofsolidtbutanolcompareswiththatofliquid
water,anessentialpieceofinformationtopredictifthesolidtbutanolwillsink,float,or
remainjustbuoyantlysuspendedwhendroppedintoliquidwater.Therelativedensity
valuescouldbedeterminedexperimentallyorbylookingupthedensitiesinan
appropriatereferencebook.

1.12.

Ablockoficehasfollowingdimensions:height=20cm,width=20cm,andlength=
20cm.Thedensityofliquidwateris1.000gmL1at0C,andthedensityoficeatthe
sametemperatureis0.917gmL1.Calculatethevolumeofthepuddleofwater,at0C,
thatisleftbehindwhentheblockoficemelts.
Answer:Thevolumeofblockofice:

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V=20cmx20cmx20cm=8000cm3=8000mL

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Themassofice(andwater):d=m/V;m=dxV:m=8000mLx0.917g/mL=
7336g
Thevolumeofpuddle:V=m/d;V=7320g/1.000g/mL=7320mL

1.13.

Ifanironbarweighing100.0gisheatedtoatemperatureaboveitsmeltingpoint
(>1535C),itwillliquefy.Whatisthemassofthemolten(liquid)iron?Isany
additionalinformationneededinordertoanswerthisquestion?
Answer:Noadditionalinformationisnecessary.Aphasechangefromsolidtoliquid
(orfromliquidtogas)doesnotchangetheamountofmatterinvolvedinthephase
change.Massisconservedinallphasechanges,sothemassofthemoltenironmustbe
100.0g.

Section1.2.
AtomicModels
1.14.

Whichofthefollowingarechemicalelements?Howdoyoudecide?
(a) water

(d) ironoxide

(b) saltwater

(e) nitrogen

(c) iron

(f) diamond

Answer:Waterandironoxidearecompounds.Saltwaterisasolutionofone
compound(salt)inanother(water).Nitrogenanddiamondareelements;diamondispure
carbon.
1.15.

Whatisthedifferencebetweencoreelectronsandvalenceelectrons?
Answer:Sincecoreelectronsarestronglyattractedtothenucleus,theyareclosesttothe
nucleusandthuscannotinteractwithotherelectrons.Valenceelectronsarefurthestfrom
thenucleusandinteractwithotheratoms.

1.16.

Howmanyvalenceelectronsandcoreelectronsdothefollowingelementspossess?
(a) sodium

(d) phosphorus

(b) bromine

(e) sulfur

(c) barium

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Answer:(a)1valenceelectron,10coreelectrons;(b)7valenceelectrons,28core
electrons;(c)2valenceelectrons,54coreelectrons;(d)5valenceelectrons,10core
electrons;(e)6valenceelectrons,10coreelectrons.
1.17.

Manyorganismsusetheseionsintheirmetabolism:Na+,K+,Mg2+,Ca2+,Cl,Br.
(a) Completethefollowingtableconcerningtheseions.
Ion

#of
protons

#of
electrons

#ofvalence
electrons

Core
charge

#ofcore
electrons

Na+
K+
Mg2+
Ca2+
Cl
Br
(b) Whatpatternsdoyouobserve?
Answer:
(a)
Ion

#of
protons

#of
electrons

#of
valenceelectrons

Core
atomic
charge

#of
core
electrons

Na+
K+
Mg2+
Ca2+
Cl
Br

11
19
12
20
17
35

10
18
18
18
18
36

0
0
0
0
0
0

+1
+1
+2
+2
1
1

10
18
18
18
18
36

(b)Na+,K+,Mg2+,andCa2+havezerovalenceelectrons.ClandBrhaveeightvalence
electrons(acompleteoctet).Toformions,metalsloseelectronswhilenonmetalsgain
valenceelectrons.
1.18.

Intermsofelectronicstructure,whatisitthatelementsinthesameperiod(row)ofthe
periodictableshareincommon?

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Answer:Elementsinthesameperiodoftheperiodictableallhavethesamenumberof
coreelectrons.
1.19.

Intermsofelectronicstructure,whatisitthatelementsinthesamegroup(column)ofthe
periodictableshareincommon?
Answer:Elementsinthesamegroupoftheperiodictableallhavethesamenumberof
valenceelectrons.

1.20.

Ingeneral,doelementsfromthesameperiodorelementsfromthesamegroupofthe
periodictablehavesimilarchemicalproperties?Justifyyouranswer.
Answer:Recallthatchemicalreactionsandinteractionsdirectlyinvolveonlythe
valenceelectrons.Therefore,elementsinthesamegroup(column)havesimilarchemical
properties,sincetheyhaveidenticalnumbersofvalenceelectrons.

1.21.

Thesemetalions,Mn2+,Fe2+,Fe3+,Cu2+,andZn2+,areavailableforuptakebyliving
organisms.Howmanyprotonsandelectronsdoeseachionhave?
Answer:Mn2+has25protonsand23electrons;Fe2+has26protonsand24electrons;
Fe3+has26protonsand23electrons;Cu2+has29protonsand27electrons;Zn2+has30
protonsand28electrons.

Section1.3.
MolecularModels
1.22.

UsingequationsmodeledafterFigure1.9(c),showhowtoformeachofthefollowing
moleculesfromtheirconstituentatoms.Ineachcase,countelectronsintheproductsto
demonstratethattheoctetruleisfollowedforallsecondrowatoms.
(a) HF(hydrogenfluoride)

(c) CH3OH(methanol)

(b) NH3(ammonia)

(d) H2O2(hydrogenperoxide)

Answer:Theoctetsofelectronshavebeencircledforeachoftheproducts.Notethat
eachcovalentbondiscomposedoftwoelectrons,oneformallycontributedbytheatoms
ateachendofthebond.
(a)

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(b)

NH3(ammonia)

CH3OH(methanol)
H

H
O

1.23.

H
(c)

(d)

H2O2(hydrogenperoxide)

Whichofthesearemacroscopicproperties?Whicharemicroscopicproperties?
(a) theboilingpointofwater
(b) theHOHbondangleinwater
(c) theOHbondlengthinwater
(d) theabilityofwatertodissolvesalt
(e) thedensityofwater
(f) thefactthattheoxygenatomofwaterhastwopairsofnonbondingelectrons
Answer:Thebondangle,bondlength,andnumberofnonbondingpairsofelectronson
oxygenarenotdirectlyobservableandarethereforemicroscopicpropertiescharacteristic
ofindividualwatermolecules.Theboilingpointanddensityofwateranditsabilityto
dissolvesaltaredirectlymeasurableorobservablewithbulksamplesofwaterandare

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thereforemacroscopicproperties.Thesemacroscopicpropertiesofarenotpropertiesof
individualwatermolecules,onlylarge(macroscopicallyobservable)collectionsofwater
molecules.Ofcourse,themicroscopicstructureandmacroscopicpropertiesarerelated
andmuchofthechemistrywewillstudyisconcernedwiththeserelationships.
1.24.

Considerthesefourdifferentmodelsfortheammoniamolecule,NH3:
Model1
NH3

Model2

Model3

Model4

H N H
H

(a) Whatisthenamegiventoeachtypeofmodelshown?
(b) Whatinformationcanbeobtainedfromeachtypeofmodel?
(c) Whatothertypesofmodelscanbeusedtorepresenttheammoniamolecule?
Answer:(a)Model1isamolecularformula,sometimescalledalineformula
andModel2isanelectrondotmodel.Model3isaballandstickrepresentation
andModel4isacomputergeneratedmodelofanammoniamolecule.
(b)Themolecularformulaorlineformulatellsyouthereare3atomsof
hydrogencombinedwithoneatomofnitrogen,formingonemoleculeof
ammonia.Theelectrondotmodelalsoshowstheconnectivitywithinthe
ammoniamoleculeandlocatesthevalenceelectrons.Theballandstickmodel
showsconnectivitybutalsogivessomeinformationaboutthebondangleswithin
themolecule.Notethatthismodeldoesnotshowthepairofnonbondedelectrons.
Thecomputergeneratedmodelshowstheatoms,theirconnectivityandbond
angles,andiscolorcodedtoshownetelectricalchargeonvariouspartsofthe
molecule.
(c)Thepaddlemodelcanbeusedtoshowthelocationofnonbondedelectronpairs.
Spacefillingmodelsshowconnectivity,bondanglesandgiveapproximate
representationsofthespace(volume)occupiedbyelectronsaroundeachatomiccorein
theammoniamolecule.
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Chapter1
1.25.

Water:ANaturalWonder

Writethemolecularformulas(lineformulas)ofthecompoundsrepresentedhere:

(a)

(c)

(b)

(d)

Answer:(a)SF4(b)PCl3(c)CH4(d)CH3COOH
1.26.

Writethemolecularformulasforthefollowingcompounds.(Ifnecessary,useareference
handbookand/orotherbookstofindoutthestructures.)
(a) glucose,asubstanceknownas"bloodsugar"
(b) nitrousoxide,asubstanceusedasananestheticandasanaerosolpropellant.Itis
commonlycalled"laughinggas."
(c) methanol,anorganicsolventandantifreeze
(d) acetylene,agasthatisusedinweldingtorches
Answer:(a)C6H12O6(b)N2O(c)CH4O(However,thestuandwayofwritingthe
molecularformulaformethanolisCH3OH,becauseitshowshowtheatomsarejoinedin
themolecule.)(d)C2H2

Section1.4.
ValenceElectronsinMolecularModels:LewisStructures
1.27.

(a) WhatinformationcanbeobtainedfromaLewisstructure?
(b) WhatinformationcannotbeobtainedfromaLewisstructure?
Answer:(a)FromaLewisstructure,youcandeterminetheshapeofthemolecule.
Fromtheshapeofthemoleculeandrelativeelectronegativities,youcandeterminethe

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polarityofthemolecule.Fromthepolarityofthemolecule,youcandeducemostofthe
chemicalandphysicalpropertiessuchasdeterminingifithasahighboilingpoint,
meltingpoint,and/orheatofvaporization.
(b)Anypropertiesrelatedtogeometryordistributionofelectronsarenotconveyedby
Lewisstructures.Theseincludebondlengths,bondangles,bonddipoles,andmolecular
dipoles.
1.28.

Considerthiselectrondotmodelfortheammoniumion,NH4+:
H

H N H
H

(a) Whatinformationcanbeobtainedfromthismodel?
(b) Whatinformationcannotbeobtainedfromthismodel?
(c) Rewritetheammoniumionusingadashtorepresenteachbondedpairofelectrons.
Doesthischangetheinformationfoundinthemodel?
(d) Howdoesthiselectrondotmodelfortheammoniumioncomparewiththatfor
methane,CH4,giveninWorkedExample1.10?
Answer:(a)Therearefouratomsofhydrogencombinedwithoneatomof
nitrogen,formingtheammoniumion.Thereisapositivechargeontheoverall
ion.Theconnectivitywithinthemoleculeisclearlyshownbythismodel.
(b)Thereisnoinformationaboutbondangles,bondlengths,ordistributionof
chargewithintheammoniumion.
(c)Whenrewrittenusingdashes,themodelis:
H
H N H
H

Thisdoesnotinanywaychangetheinformationfoundinthemodel.Itisjusta
conveniencetoreplaceeachpairofbondedelectronswithadash.
(d)Thestructureformethaneisverysimilarelectronically.Bothshowfourpairs
ofelectronsaroundthecentralatom.Thecentralatomnitrogenhasonemore

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valenceelectronthanthecentralatomcarbonandthereforeoneelectronislostin
formingtheammoniumion,leavingtheionwithapositivecharge.
H
H N H

Ammoniumion:

1.29.

Methane: H C H
H

ExamineTable1.1.Silicontypicallymakesfourcovalentbondsandsulfurtypically
makestwocovalentbonds.Howmanycovalentbondsdoyouexpectforeachofthe
followingelements?Explainyourreasoningineachcase.
(a) phosphorus

(c) selenium

(b) chlorine

(d) bromine

Answer:(a)3(b)1(c)2(d)1
1.30.

Neon(Ne)istheelementtotherightoffluorine(F)intheperiodictable.
(a) ExamineTable1.1.Howmanycovalentbondsandnonbondingpairswouldbe
expectedforneon?Explainthereasoningforyouranswer.
(b) Ne(alongwithHe,Ar,Kr,Xe,andRninthesamegroupoftheperiodictable)were
onceknownastheinertgases.Whyweretheygiventhisname?

Answer:(a)Neonformsno(0)covalentbondsandhasfournonbondingpairsof
electrons.
(b) Inchemistry,inertmeansincapableofreacting.Chemicalreactionsaredefinedby
themakingandbreakingofchemicalbonds.Sinceneoncannotformcovalentbonds,it
canbecharacterizedasinert.
1.31.

DrawtheLewisstructureofethanol,C2H6O.TheformulamayalsobewrittenC2H5OHor
CH3CH2OHtomaketheconnectivitymoreapparent.
Answer:Eachcarbonhas4valenceelectrons,eachhydrogenhas1valence
electron,andoxygenhas6valenceelectrons.Thetotalnumberofvalence
electronsinC2H6Ois:
2(4)+6(1)+1(6)=20valenceelectrons.

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Chapter1

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Theonlypossiblewaytoconstructethanolistoconnectcarbontocarbon,and
thencarbontooxygenatomiccores.Thenthehydrogenatomiccoresareplaced
aroundthecarbonandoxygencoressothateachcarbonhas4covalentbondsand
eachoxygenhas2covalentbonds.Thestructureis:
H H
H C C O
H H H

1.32.

H H
or H C C O
H H H

DrawtheLewisstructuresforozone,O3,sulfurdioxide,SO2,andnitriteion,NO2.What
doallthreeofthesestructureshaveincommon?Hint:SisthecentralatominSO2andN
isthecentralatominNO2.

Answer:

Allthreeareisoelectronic.Thismeansthatthearrangementoftheirvalenceelectronsis
identical.Thefundamentaldifferenceamongstthemisthenumberofbalancebetween
thecorechargesofthethreeatomiccentersandeighteenvalenceelectrons.Whenthe
corecharge(positive)isequaltothechargeduetothevalenceelectrons(negative),then
themoleculeisneutral(ozoneandsulfurdioxide).Iftheyareunequal,thenanionresults
(nitriteanion).
1.33.

EachofthefollowingLewisstructuresforNCCNhasthecorrectnumberofelectrons.
WhichisthebestLewisstructureforNCCN?Explainyourreasoningforrejectingthe
structuresyoudidnotchoose.Hint:Multiplebondsbetweenatomswillbediscussedin
Chapter5.Forthepurposesofthisproblem,simplycounteachstroke(bond)astwo
electronssharedbetweentheatomsitconnects.
(a)

N C C N

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(d)

N C C N

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Chapter1

Water:ANaturalWonder

(b)

N C C N

(e)

(c)

N C C N

(f)

N C C N

N C C N

Answer:
(d)isthecorrectLewisstructureandcontainsanoctetforeachatom.Allotheroptions
lackoctetsononeormoreatoms.
1.34.

WhichofthefollowingLewisstructuresareincorrect?Ineachcase,explainwhythe
structureisincorrect.Rewriteeachoftheincorrectstructuressoitiscorrect.Hint:See
thehintinProblem1.33.
O

(a) HOCl

(b) CS2
(c) NH3

(d) (HO)2CO

H O Cl

(e) H2Se

H O

O H

H Se H

H N H
H

Answer:
Theincorrectstructuresare(d)and(e).Inordertofollowtheoctetrulethey
shouldbedrawnasfollow:

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Section1.5.
ArrangingElectronPairsinThreeDimensions
1.35.

Whichofthefollowingmoleculesorionshasatetrahedral(orclosetotetrahedral)
orientationofbondingandnonbondingelectronpairs?
(a) H2S

(d) NH2

(b) NH4+

(e) CH4

(c) NH3
Answer:Withrespecttothecentralatom,tetrahedralorientationrequiresatotaloffour
pairsofbondingandnonbondingelectrons.Forthisproblem,allhavetetrahedral
orientations.
1.36.

WhatistheshapeofeachofthemoleculesinProblem1.35?Recallthattheshapeofa
moleculedescribesthepositionoftheatomiccoreswithrespecttooneanother.
Answer:
(a) H2S(bent)

(d) NH2(linear)

(b) NH4+(tetrahedral)

(e) CH4(tetrahedral)

(c) NH3(trigonalpyramidal)
1.37.

Figure1.12showedonewaytostackfourballssothat
theyareequidistantfromacentralpoint.Anotherwayis

to

arrangetheminasquareaboutthepoint,asshowninthis
picture.Linesdrawnbetweenthecentersofadjacentballs
formasquareofside2r,whereristheradiusofaball.
Thecenterpointofthediagonalofthesquareisthecenter

of

thesquare.UsethePythagoreantheoremtofindthelengthofthediagonalandthe
distancefromthecenterofanyoftheballstothecenterofthesquare.
Answer:Letc=lengthofdiagonal.
4r2 + 4r2 = c2 ;c = 2r 2;
c
distancefromcenter = = r 2
2

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Chapter1
1.38.

Water:ANaturalWonder

(a) Acubecanbecircumscribedaboutaregulartetrahedron,
asshowninthisfigure.Thefourdotsrepresentthecentersof
thefourballsinFigure1.12,.Thediagonalofoneofthecube
faceshasalength2r,whereristheradiusofaball.Thecenter
pointofanyoneofthecubediagonals(oneisshownbythe
dashedline)isthecenterofthetetrahedron.Usethe
Pythagoreantheoremtofindthelengthofthecubeedgeand
thenagaintofindthelengthofthecubediagonal.Thus,showthatanycornerofthecube,

thatis,thecenterofanyoftheballs,is 6 2 rfromthecenterofthetetrahedron.

(b) Howdoesthedistanceyoucalculatedinpart(a)comparetothedistanceofthe
centerofeachballfromthecenterofthesquareinProblem1.37?Doyourresultshelp
justifythestatementinthetextthatthetetrahedralarrangementputsalltheballsasclose
aspossibletothecentralpoint?Explainwhyorwhynot.
Answer:(a)Callthelengthofthecubeedgese.ApplythePythagoreantheoremtothe
rightisoscelestrianglewithhypotenuse2r:(2r)2=2e2;2r=(2)e;e=

2r
.Callthe
2

lengthofthecubediagonal,d,andapplythePythagoreantheoremtotherighttriangle
2

withsides2randeandhypotenused:d2=(2r)2+

2r
=4r2+4r2/2=6r2;d=(6)r.
2

Therefore,(1/2)d= 6 2 r.

(b)Thedistancecalculatedinpart(a)islessthanthedistancecalculatedinProblem
1.37.Yes,theresultshelpjustifythestatementthat"thetetrahedralarrangementputsall
theballsascloseaspossibletothecentralpoint"becauseitsdistanceisshorterthan
Problem1.37,indicatingthattheballsarecloser.

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Chapter1
1.39.

Water:ANaturalWonder

SiCl4,silicontetrachloride,isusedfortheproductionoftheverypuresiliconrequiredin
manyelectronicdevicessuchastransistors.
(a) DrawtheLewisstructureforSiCl4.
(b) HowdoesthisLewisstructurecomparetothatofmethane,CH4?
(c) PredicttheshapeoftheSiCl4molecule.
Answer:(a) Eachsiliconhas4valenceelectronsandeachchlorinehas7
valenceelectrons.ThetotalnumberofvalenceelectronsinSiCl4is:
1(4)+4(7)=32valenceelectrons.
Thewaytoconnecttheseatomcoresistoconnecteachchlorineatomcoretothecentral
siliconatomcore.Siliconhas4covalentbondsandeachchlorinewillhaveonecovalent
bond.Eachchlorinehas3pairsofnonbondedelectrons.Thestructureis:
Cl
Cl Si Cl
Cl

or

Cl

Cl
Si
Cl

Cl

(b)ThisLewisstructureissimilartothatformethane,CH4inthatthecentral
atomineachcasehasfourcovalentbonds.Siliconisinthesamefamilyonthe
PeriodicTableascarbon,soalsobrings4valenceelectronstothestructure.Each
hydrogenatomcoresinmethanecanonlyhave1bondedpairofelectrons,but
eachchlorineatominsilicontetrachloridehas1bondedpairofelectronsand3
nonbondedpairsofelectrons.
H

Cl

Methane: H C H
Silicontetrachloride: Cl Si Cl
H

Cl

(c)TheshapeofSiCl4,likethatofCH4,willbetetrahedral.
1.40.

(a) DrawtheLewisstructureforborane,BH3.Compoundslikeboranearesometimes
calledelectrondeficient.Howdoyouthinkelectrondeficiencyisdefined?

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(b) Whatshapedoyoupredictforborane?Youmightfinditusefultotryamodified
versionofInvestigateThis1.14tohelpmakeyourprediction.AlsoseetheWebmedia,
Chapter1,Section1.6.
Answer:(a)Boranehasonlysixvalenceelectrons.Becauseitdoesnothavea
fulloctet(eightelectrons),itiscalledelectrondeficient.

(b)Asshowninthedrawing,boraneistrigonalplanarwiththeHBHbondanglesall
equalto120.
Section1.6.
PolarityoftheWaterMolecule
1.41.

Whatiselectronegativity?
Answer:Theforceofattractionanatomhasforasharedpairofelectrons.

1.42.

Answerthefollowingquestionsonelectronegativity.
(a) Whichelementhasthehighestelectronegativityvalue?
(b) Whereontheperiodictabledoyoufindtheelementswiththelowest
electronegativities?
(c) Whereontheperiodictabledoyoufindtheelementswiththehighest
electronegativities?
(d) Whatisthegeneraltrendforelectronegativityasyougofromthetoptothebottom
withinagroup?
(e) Whatisthegeneraltrendforelectronegativityasyougofromthelefttorightacross
aperiod?
(f) Howdotheelectronegativitytrendscomparetotheatomicsizetrends?Referto
Figure1.7forinformationaboutatomicsize.
Answer:(a)Fluorine(b)Bottomlowerleft(c)Topright(excludingnoblegases)(d)
decreases(e)increases(f)Electronegativityincreasesparallelsatomicsizedecreases
(asthesizegoesdowntheelectronegativitygoesup).

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Chapter1
1.43.

Water:ANaturalWonder

Withoutreferringtoatableofelectronegativities,predictwhichmemberofeachpairhas
thegreaterelectronegativity.Explainthebasisforyourpredictionineachcase.
(a) ForS

(c) HorO

(b) CorH

(d) OorC

Answer:(a)F(b)C(c)O(d)O
1.44.

Youcanusetheelectronegativitydifferencebetweentwoatomstopredictthepolarityof
thebondstheymake.Choosethepairofatomsineachcasethatyoupredicttomakethe
morepolarbondandexplainhowyoumakethisprediction.
(a) HForHCl

(c) KSorNaS

(b) CHorNH

(d) OOorNO

Answer:Thehighertheelectronegativitydifferencebetweenthetwoatoms,themore
polarthebondwillbe.
(a)HF(b)NH(c)KS(d)NO
1.45.

Whatwouldbetheconsequencesforlifeifwaterwerealinearmolecule?Considerthe
effectonthepolarityandpropertiesofwaterifitwerelinear.Youmightfinditusefulto
drawpicturesofhowthelinearmoleculesmightinteractwithoneanotherandcompare
whatyougetwiththevariousinteractionspicturedinthischapter.
Answer:Thereisnosingleanswertothisproblem,butyouransweroughtto
involveanunderstandingthatalinearwatermoleculewillhavenopermanent
dipolemoment,sincethebondmomentswillbepointinginoppositedirections
andcanceloneanotherout.Ifthehydrogenatomsareonoppositesidesofthe
oxygenatom,thenonbondingelectronpairsarealsolikelytobeonoppositesides
(forsymmetry),sothearrayofbondingandnonbondingpairsislikelytobe
squareplanar.Hydrogenbondswouldstillbepossibleandcouldeasilyform
planarsheetsofmolecules,eachhydrogenbondedtofourothers,asintheleft
handpicturebelow.Suchlayerscouldstackononeanotherorsmallarraysof
themcouldjumbletogetherlikepotatochipsinabagintheliquidphase.Three
dimensionalstructuresarealsopossible,asintherighthandpicture,alsowith

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Chapter1

Water:ANaturalWonder

fourhydrogenbondstoeachmolecule.Thisthreedimensionalstructureisquite
open.
Withoutapermanentdipolemoment,theattractionsamonglinearwater
moleculeswouldnotbeasstrongandwaterwouldprobablymeltandboilat
lowertemperatures.TheliquidmightexistonEarthatthepresenttemperature
andstillbecompatiblewiththedevelopmentandevolutionoflife.Thethree
dimensionalstructureshownhaslargespacesbetweenmolecules,soasolidwith
thisstructurecouldcollapsetoamoredenseliquid,justasthebentwater
moleculesdo.Thatis,solidlinearwaterwouldprobablyfloatontheliquid,which
isanotherrequirementforlife,asweknowit.Theextensivehydrogenbonding
possibleforlinearwater,wouldleadtoahigherenergyofvaporizationand
specificheatthanifhydrogenbondingwasnotpossible,butthelackofa
permanentdipolewouldprobablymeanlowervaluesthanforthebentmolecule.

1.46.

ConsiderthetwomoleculesH2OandH2S.
(a) ComparetheLewisstructuresofthesetwomolecules.
(b) Comparethemolecularshapeofthesetwomolecules.
(c) Comparethebonddipoleswithineachmolecule.Hint:UsethedatainFigure1.20.
(d) Comparetheoverallelectricdipoleofeachmolecule.
Answer:(a) LewisstructureofH2Ois: H O LewisstructureofH2Sis:
H

H S
H

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Chapter1
(b)

Water:ANaturalWonder
BothH2OandH2Shavebentorangularshapes.Note:Recallthat

thenonbondingelectronsarenotconsideredwhendescribingtheshapeof
molecules.
(c)ThebonddipolesaredifferentinH2OandH2S.Theelectronegativity(EN)of
oxygenis3.44,whilethatofhydrogenis2.20.ThedifferenceinENistherefore
1.24,makingeachhydrogentooxygenbondverypolar.Thevalenceelectronsare
notsharedequallybetweenoxygenandeachhydrogenatom,withoxygenhaving
amuchgreaterattractionforthesharedelectrons.ThisisrepresentedinFigure
1.19.TheENofsulfuris2.58andthatofhydrogenis2.20.ThedifferenceinEN
isthereforeonly0.38.Theruleofthumbisthatasignificantbonddipoleonly
existsforacovalentbondbetweentheatomsoftwoelementsthatdifferby0.5or
moreENunits,sothesebondsareessentiallynonpolar.
(d)H2Ohasasignificantelectricdipole,asrepresentedinfigure1.18.H2S,ontheother
hand,hasessentiallynonpolarbonds,andthereforeeventhoughitisangularinshape,it
cannotexhibitasignificantelectricdipole.
1.47.

DrawtheLewisstructuresforcarbontetrachloride,CCl4,chloroform,CHCl3,and
dichloromethane,CH2Cl2.Clearlylabelthebonddipolesforeachmolecule.Which
moleculesarepolarandwhicharenonpolar?Explainyouranswer.
Answer:Whentheindividualbonddipolescancelout,thenthereisnonetdipole
andthemoleculeisnonpolar.Iftheindividualbonddipolesdonotcancelout,
thenthereisanetdipole.

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Chapter1
1.48.

Water:ANaturalWonder

Eachofthefollowingmoleculeshasadipolemoment=0.Ineachcase,explainwhy
thereisnonet(molecular)dipolemoment.Ifthemoleculehasbonddipoles,drawthem
andexplainhowtheycancelout.
(a) N2(molecularnitrogen)
(b) BH3(borane)Hint:Bdoesnotsatisfytheoctetrule.SeeProblem1.40.
(c) SiCl4(silicontetrachloride)
(d) BeH2(berylliumhydride)Hint:Bedoesnotsatisfytheoctetrule.Whatshapemust
themoleculehave,inordernottohaveanetdipolemoment?Youmightfinditusefulto
tryamodifiedversionofInvestigateThis1.14tohelpdeterminethisshape.

Answer:Given:molecularformulas.
Askedfor:anexplanationwhyallthemoleculeshavedipolemoments=0
Recallthatthedipolemomentofanymoleculeissimplythesumofalltheindividual
bonddipoles.Inordertohavenonet(molecular)dipolemoment,thebonddipolesmust
eitherallequalzeroorbesymmetricallyorientedtoexactlycancelout.[Ifyouhave
studiedvectorsinmath,wecanrestatethismoresimply:themoleculardipoleisthe
vectorsumofthebonddipoles.]
Plan&Analysis:Beforeattemptingananalysisofdipolemoments,thethree
dimensionalshapeofthemoleculemustbeknown.FirsttheLewisstructuremustbe
written,thenthegeometricorientationofthebondsmustbedetermined.Ifthereisany
specialsymmetry,itshouldbenoted.
(a)

N2(molecularnitrogen)hasatriplebondbetweenthetwonitrogenatoms.Since

thetwonitrogenatomsobviouslyhavethesameEN(electronegativity)value,thebond
dipolemustbezero.Asistrueforalldiatomicmoleculesthebonddipoleisequaltothe
moleculardipolemoment.
N

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Chapter1
(b)

Water:ANaturalWonder
BH3(borane)hasatrigonalplanargeometrywithalltheHBHbondangles=

120.Hydrogenismoreelectronegativethanboron,asillustrated.Thecancellationof
thebonddipolesisduetothethreefoldsymmetryofthemolecule.
H
B

(c)

SiCl4(silicontetrachloride)hasitsfourequivalentSiClbondspointingtothe

fourcornersofatetrahedron.Chlorineismoreelectronegativethansilicon.The
cancellationofthebonddipolesisduetothetetrahedralsymmetryofthemolecule.
Cl
Cl

(d)

Cl
Si

Cl

BeH2(berylliumhydride)isalinearmolecule,withthetwoBeHbond
moments180apartopposingoneanother.

Recap:Inordertofigurethenetdipoleforanymolecule,thereareanumberofsteps
required.Eachstepisessentialinordertoarriveatthecorrectanswer.First,drawa
Lewisstructure.Withonlyrareexceptions(suchasBH3andBeH2above),allsecond
rowelementsshouldsatisfytheoctetrule.Next,figurethethreedimensionalshapeof
themoleculethatwillminimizetheseparationofthenegativelychargedvalencepairsof
electronsfromthepositivelychargedatomiccore.Finally,theelectronegativitiesofthe
atomsallowsfortherelativemagnitudesofindividualbondmomentstobeestimated;
fromtheirgeometricsumamoleculardipoledirectionandmagnitudecanbequalitatively
predicted.
1.49.

Whichmolecule,ammonia,NH3,orphosphine,PH3,hasthelargermoleculardipole
moment?Explain.

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Chapter1

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Answer:Sincenitrogenismoreelectronegativethanphosphorus,ammoniawillhave
thegreatermoleculardipole.
Section1.7.
WhyIsWaterLiquidatRoomTemperature?
1.50.

Describeeachofthefollowingtypesofintermolecularattractions:
(a) induceddipoleattractions
(b) dipoledipoleattractions
(c) hydrogenbond
Answer:(a)Themotionofelectronsinanonpolarmoleculecancreatpartial
polarregionsinmolecules.Polarityinonemoleculeinducespolarityina
neighboringmoleculesandtwopolarizedmoleculesattractoneanother.These
attractionsarecalledinduceddipoleattractions.
(b)Adipoledipoleattractsexistbetweenneutralpolarmolecules.Polar
moleculesattracteachotherwhenthepositiveendofonemoleculeisnearthe
negativeendofanother.
(c)Hydrogenbondingisapsecialtrypeofintermolecularattractionsthatexistbetween
thehydrogenatominapolarbond(particularlyaHF,HO,orHNbond)andan
unsharedelectronpaironanearbyelectronegativeatom(usuallyaF,NorOatom)on
anothermolecule.

1.51.

Howareanintramolecularcovalentbondandanintermolecularhydrogenbondsimilar?
Howaretheydifferent?
Answer:Experimentsshowthatthestrengthofahydrogenbondisapproximatelyfive
totenpercentthestrengthofacovalentbond.Therelativeweaknessofhydrogenbonds
meansthattheycanbreakandformrapidlyinsolution.Also,hydrogenbondsarelonger
thancovalentbonds.

1.52.

Whattype(s)ofintermolecularattractionsaretherebetween
(a) allmolecules?
(b) polarmolecules?

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Chapter1

Water:ANaturalWonder

(c) ahydrogenatominawatermoleculeandanitrogenatominammonia(inamixture
ofammoniaandwater)?
Answer:a)dispersionforces(b)dipoledipoleattractions(c)hydrogen
bonding
1.53.

Astatine,At,element85,isradioactiveandhasahalflifeofonly8.3hours(seeChapter
3).OnlyminutetracesofAthavebeenstudied.Thehydride,HAt,hasbeendetectedbut
itsphysicalpropertiesareunknown.BasedonthedatainFigure1.24,whatwouldyou
predictfortheboilingpointofHAt?Explainhowyoumakeyourprediction.
Answer:WiththeincreasingboilingpointsfromHClthroughHI,wewouldpredictthat
theboilingpointforHAtwouldbeapproximately4050C.

1.54.

Methane,CH4,andhydrogensulfide,H2S,donotformhydrogenbonds.Explain.
Answer:Carbonandsulfuratomsdonothavehighelectronegativityvaluesrequiredfor
forminghydrogenbonds.Forhydrogenbondstoform,Hatomsmustbebondedtoa
veryelectronegativeatomsuchasfluorine,nitrogenoroxygen.

1.55.

Listatleastthreepropertiesofwaterthatcanbeattributedtotheexistenceofthe
hydrogenbond.Brieflydescribehoweachpropertywouldbeaffectedifwaterdidnot
formhydrogenbonds.
Answer:1.Waterisinitsliquidstateatroomtemperature.Atroomtemperature,
thehydrogenbondsinwaterarestrongenoughtoholdmoleculestogether.Ifthe
hydrogenbondsarenotpresent,thesmallmoleculeslikewaterwouldoccurinthe
gasstateatroomtemperature.
2.Thelowerdensityofsolidicecomparedtoliquidwater.Theextended
hydrogenbondedstructureiniceproducesmoreopenspacebetweenwater
moleculesthaninliquidwater.Thisstructure,whichextendsinalldirectionsin
space,permitsthemaximumnumberofhydrogenbondinginteractionsbetween
theH2Omolecules.Becausethestructurehaslargehexagonalholes,iceismore
openandlessdensethantheliquid.Ifthehydrogenbondsarenotpresent,ice
wouldbemoredensethantheliquidasitisthecaseformostsubstances.

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Chapter1

Water:ANaturalWonder

3.Theboilingpointofwaterismuchhigherthanitwouldbeexpectedonthe
basisofitsmolecularweight.Becauseofthehydrogenbonds,moreenergyis
neededtodisrupttheintermolecularattractionsbetweenthemoleculesinthe
liquidphase.
Otherconsequencesofthepresenceofhydrogenbondsamongwater
moleculesinclude:highmeltingpointandhighheatcapacity.

1.56.

(a) Howmanyhydrogenbondsarepossibleforonewatermoleculeinasampleof
water?Illustrateyouranswerwithadrawingofthestructureofwaterindicatingwhere
thehydrogenbondsarepossible.

Answer:
1.57.

(a) Howmanyhydrogenbondsarepossibleforoneammoniamoleculeinasampleof
ammonia?Illustrateyouranswerwithadrawingofthestructureofammoniaindicating
wherethehydrogenbondsarepossible.

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Chapter1

Water:ANaturalWonder

(b) Canalltheammoniamoleculesinasampleofliquidammoniahavethemaximum
numberofhydrogenbondsyouillustratedinpart(a)?Ifnot,whatlimitsthenumberand
howmanyhydrogenbonds,onaverage,caneachammoniamoleculehave?
Answer:CompareFigure1.26(a),showinghydrogenbondingforwater,withthedrawing
(below)showinghydrogenbondingforanammoniamolecule.Everywatermoleculein
acollectionofwatermoleculesiscapableofformingfourhydrogenbondsbecauseit
donatesasmanynonbondingpairs(2)ashydrogens(2).Thesituationforammoniais
quitedifferent.Whileanindividualammoniamoleculeiscapableofformingfour
hydrogenbonds,notallmoleculesinasampleofliquidammoniacandothis.The
imbalanceofhydrogenatoms(3)tononbondingpairsofelectrons(1)meansthat,on
average,eachammoniamoleculewillformamaximumofonlyonehydrogenbond.
Theresimplyarentenoughnonbondingpairsofelectronsforeveryavailablehydrogen.

1.58.

RefertothegraphinConsiderThis1.23thatrelatestheboilingpointsofaseriesof
hydrocarbonstothenumberofelectronspermolecule.Whatisthesmallesthydrocarbon
intheseriesthatexistsasaliquidatroomtemperature?
Answer:Inordertoexistasaliquidatroomtemperature,asubstancemusthavea
boilingpointaboveroomtemperature.Thesmallestlinearhydrocarbontofitthis
descriptionispentane(CH3CH2CH2CH2CH3).

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Chapter1
1.59.

Water:ANaturalWonder

Theboilingpointsofthenoblegasesare:
element

He

Ne

Ar

Kr

Xe

Rn

bp,C

269

246

186

152

107

62

(a) PlotthesedataonagraphliketheoneinFigure1.24.Howarethesedatasimilarto
thoseforthehydridesplottedinFigure1.24?Howaretheydifferent?
(b) NoblegasatomsaresphericalandFigure1.22showsthattetrahedralhydrideslike
methanearequitesymmetricandalmostspherical.Whatislikelytobethelargestfactor
responsibleforthedifferenceinboilingpointsbetweenanoblegasandthe
correspondinggroupIVhydride?
Answer:TheplotinFigure1.24withthenoblegasesaddedlookslikethis:
100

IV

50

VI
VII

50

VIII

100
150
200
250
300

10 20 30 40 50 60 70 80 90
NumberofElectrons/Molecule

(a)Theperiods2through5groupVIIInoblegasesfollowatrendthatisremarkably
similartothegroupIVhydridesexcept5080Clowerinboilingpoint.Thetrend
continuestoperiod6,buttherearenohydridesforcomparison.(Theperiod6,groupIV
elementisbismuth,whichismetallicanddoesnotformatetrahydride.)Thereis,of
course,noperiod1,groupIVelement,sonocomparisonwithheliumispossibleeither.
(b)Thesymmetry(sphericalornearspherical)ofthegroupVIIInoblegasesandthe
groupIVhydridesgivesthemsmallsurfaceareasandchargesymmetry,whichmakesthe
induceddipoleattractionsamongtheatomsormoleculesrelativelyweakandaccounts
fortheirlowboilingpoints.Thenuclearchargeonthenoblegasesisfourunitshigher
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Chapter1

Water:ANaturalWonder

thanthecentralatominthecorrespondingperiodhydride,whichholdstheelectrons
closertothenucleus,reducesthesurfaceareaoftheatomrelativetothehydrideand
resultsinevenweakerinduceddipoleattractions,sotheboilingpointsaresubstantially
lower.ThisisthetrendweseealsointhegroupVIIhydrides,whichmighthavebeen
expectedtohavehigherboilingpointsthaneitherthegroupVorVI(ifthetrendfromIV
toVtoVIwasfollowed),buthavelowerboilingpoints(atleastforperiods4and5)than
thegroupVhydrides.
1.60.

Thereareoftendifferentcompoundshavingthesameformula.Asyouwilllearnin
Chapter5,theseareknownasisomers.ForC5H12,therearethreeisomers.Thecommon
names,lineformulas,structures,andboilingpointsoftheisomersaregivenbelow.All
threehavethesamemolecularmass.Whyarenttheirboilingpointsclosertogether?
Hint:Themorecompactamolecule,thelesssurfaceareaithasforitselectronsto
interactwithothermolecules.Buildmodelsofthesemoleculestohelpvisualizethe
surfaceareasofthesemolecules.
pentane

isopentane

neopentane

CH3CH2CH2CH2CH3

(CH3)2CHCH2CH3

C(CH3)4

bp=36C

bp=28C

bp=10C

H HH H
H
C
C
C
C H
H C
H H H H

H H
C HH H
H
C
C
C
H
H C
H
H
H

H H
H
H
C
C H
H
C
C H
H C
H
H
H

Answer:Althoughthemolecularmasses(andmolecularvolumes)arethesameforall
threeisomers,theirsurfaceareasarenot.Asthedegreeofbranchingofthecarbon
skeletonincreases,thesurfaceareadecreases.Asthesurfaceareadecreases,thecontact
withneighboringmoleculesdecreases,thusreducingthedispersionforcesbetween
molecules.Boilingpointsofhydrocarbonsareaconsequenceofdispersionforcesand
thoseforcesexistacrosstheentiresurfaceofamolecule(page34).Youmayrecall
fromgeometrythatasphereisthegeometricsolidwiththelowestsurfaceareatovolume
ratio.Examineyourmolecularmodelsofthethreeisomersandyouwillfindthat

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Chapter1

Water:ANaturalWonder

neopentanemostnearlyresemblesasphere.nPentanehasnoskeletalbranchesandhas
thegreatestsurfaceareaandthegreatestboilingpointofthethree.
Section1.8.
FurtherStructuralEffectsofHydrogenBondinginWater
1.61.

Ifanicecubeisdroppedintoliquidwaterat85C,willitfloatorsink(beforeitmelts)?
Justifyyouranswer.
Answer:Figure1.29showsthatthedensityofliquidwaterat85Cisabout968
gL1(=0.968gcm3).Thedensityoficeis0.917gcm3.Iceismuchlessdense
eventhanhotwaterandwillfloat(untilitmelts)inhotwater.Trythe
experiment.

1.62.

InInvestigateThis1.30,youfoundthatthetemperatureatthebottomofthecontainer
risestoabout4Candremainsalmostconstantaslongasthereisiceleftatthetopofthe
container.Thermalenergy(heat)mustbeenteringthecontainerfromthewarmerroom
air(theicedoesmelt).Youwouldexpectthewateratthebottomtocontinuetowarmup,
butthetemperatureatthebottomstaysconstant.Theseseemtobecontradictory
observations.
(a) Whatisthespecialpropertyofwaterat4C?
(b) Ifthewateratthebottomwarmedabitabove4C,howwouldthisproperty
change?Whatwouldthewaterbelikelytodo?Drawpicturestoillustratewhatyouthink
wouldhappen.
(c) Wouldtheactionofthewatershowninyourdrawingsresolvethecontradiction
suggestedabove?Howcouldyoutestyourmodelexperimentally?
Answer:(a)Thisisthetemperaturerangeinwhichliquidwateratnormal
atmosphericpressurehasitsmaximumdensity,Figure1.29,whichexplainswhy
itisattheverybottomofthecontainer.
(b)Warmingthewaterwillreduceitsdensity,andthewarmerwaterwouldbe
buoyedupandrise.Sincethethermalenergyisenteringthewateratthewallsof
thecontainer,itisthewaternexttothewallsthatincreasesintemperatureand
rises.Whenwaternearthetopofthecontainer,whichiscloseto0C,iswarmed,

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Chapter1

Water:ANaturalWonder

itsdensityincreasesanditsinksinthecontainer.Theneteffectoftheseactionsis
tocreatecurrentsofsinkingwaterinthetemperaturerange04or5Cand
risingwaterwithatemperatureaboveabout5C.Therisingwarmerwateris
cooledasitmixeswithwaternearthetopofthecontainerand,whenits
temperaturefallsbelow4C,itbeginstosink.Theneteffectisacirculationof
thewaterinthecontainerwithrisingwarmerwaternearthewallsofthecontainer
andsinkingcolderwaternearthemiddleofthecontainer.Thecirculationis
drivenbythethermalenergyfromthewarmersurroundingsoftheroomentering
theicewatermixture.
(c)Iftheexplanationaboveiscorrect,theconstanttemperaturemeasuredatthe
bottomofthecontainerisnotthetemperatureofthesamebatchofwater
molecules,butofaconstantlychangingbatchofwatermoleculesasthewarmed
waterisbuoyedupandthecoolerwatersinks.Ifthetemperaturesatthewallsand
inthecenterofthecontaineraremeasuredatthesameheightinthecontainer,
theremightbeadetectabledifference,withthewallwaterattemperatureabove
5Candthecenterbelow5C.Ifadropofdyecouldbeaddedtothewater
withoutdisturbingwhatevercirculationhasbeensetup,themovementofthedye
couldtracethecirculationovertime.Moreelaboratesetupshavebeendevisedto
checkwhetherthiscirculationoccurs.Asearchofthewebcouldturnupsomeof
themforyou.
1.63.

Thestructureofthewatermoleculeisthemolecularbasisforthesurvivalofplantand
animallifeinatemperateclimatelake.Theseasonalturnoverofsuchalakeis
describedinthisfigure.

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Chapter1

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Theseverticaltemperaturechangesaretypicalofalakethatfreezesinwinter.Turnovers,
representedbythecirclingarrows,occurinthespringandfallandmixnutrientsand
oxygenintothedeeperwaters.Theturnoversaretriggeredbywindsatthesurfaceofthe
water.HowwouldyourelateyourobservationsinInvestigateThis1.30tothechanges
describedinthisfigure?Explaintheconnectionsclearly.
Answer:InInvestigateThis1.30,thedenserwaterwasatthebottomofthebeaker.In
thesummer,thesunlightwarmsthewatersothelessdensewater(temperaturegreater
than4C)isonthesurfaceofthewater.Asthetemperaturedecreasesinthefall,the
nutrientsinthelakemix.Now,inthewinter,thelessdensewater(temperaturelessthan
4C)freezesoverthesurfaceofthelake.Asitmeltsinthespring,themixingof
nutrientsoccursagainasthecoldwaterdescendstothebottomofthelake.
1.64.

Considerthisrepresentationofcovalentbondsand
hydrogenbondsinwater:
(a) Whichbondlengthisassociatedwithhydrogenbonds
andwhichwithcovalentbonds?
(b) Offerareasonableexplanationforwhythereisa
differenceinbondlengthbetweenthesetwobonds.
Answer:(a)Theshorterbondlength,100pm,isassociatedwiththecovalent
bondswithinthewatermolecule.Thelongerbondlength,180pm,isassociated

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Chapter1

Water:ANaturalWonder

withthehydrogenbondsbetweenelectropositiveandelectronegativeregionsof
differentmolecules.
(b)Covalentbondsarestrongerthanhydrogenbonds.Thestrongercovalentbondshold
hydrogentooxygenwithinthewatermoleculemorecloselythanmoleculesareheld
togetherwithintermolecularhydrogenbonds.
1.65.

Themeltingpointsformethane,ammonia,water,andhydrogenfluorideareshowninthe
tableattheright.Youcantakethemeltingpointsasan

Compound
CH4
NH3
H2O
HF

indicationoftherelativeamountofenergyrequiredto
disrupttheattractionsbetweenmoleculesinthesolids,so
theyarefreetomoveaboutasaliquid.Developan
explanationforthesedatathattakesintoaccountthekinds

mp,C
182
77.7
0
83.1

ofintermolecularattractionsamongmoleculesofeachcompound.Iswateroutofline
withtherestofthecompounds?Whyorwhynot?Giveamolecularlevelinterpretation
ofyouranswer.
Answer:Essentiallythesameexplanationispossibleforthemeltingpointsasfor
theboilingpoints.Thestructureofsolidwater,Figure1.28(b),showsthateach
watermoleculeishydrogenbondedtofourothers.Methaneformsnohydrogen
bondsandisonlyheldtogetherbyweakinduceddipoleattractionsinthesolid
(andliquid),soitmeltsatquitealowtemperature.Ammoniaandhydrogen
fluorideformhydrogenbonds,butcantformasmany(permolecule)aswater.
Anyindividualmoleculecouldformfourhydrogenbonds,butanextended
structureisnotpossible.Aplotofthemeltingpointdatalooklikethis:
Melting point as function of molar mass
Melting point as function of molar mass
0
15

16

17

18

19

20

-20

-40

melting point

-60

-80

-100

-120

-140

-160

-180

-200
molar mass

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Chapter1

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OnecouldarguethatH2OisinlinewithCH4andNH3.Themeltingpoints
increaseasthemolarmassand,moreimportantly,theamountofhydrogen
bondingincreases.HFmightbeseenasoutofline,butonlyiftheextentof
hydrogenbondingisneglected.Ontheotherhand,thesimilarmeltingpointsof
NH3andHFcanbeexplainedasaresultofaboutthesameamountofhydrogen
bondingattractioninthetwosubstances.Inthiscase,H2Oisoutoflinebecause
ithasahighermeltingpoint,but,sinceithasmorehydrogenbonding,itwouldbe
expectedtohavemoreattractionsandahighermeltingpoint.Argumentsabout
whatvalueisoutoflineareallbasedonpredictionsortrendsthatlookatonly
onecausativeparameter(molarmass,numberofHbonds,etc.).Sinceobservable
propertiesaretheresultofmanymolecularlevelinteractionsandphenomena,it
isntsurprisingtofindthatanyoneofthemcantexplaineverything.

Section1.9.
HydrogenBondsinBiomolecules
1.66.

TheDNAdoublehelix,heldtogetherbythehydrogenbondsshowninFigure1.33,is
quitestiffandresistanttomovementthrougha
solution.Asshowninthisfigure,whenasolution
ofDNAisheated,theabsorptionofultraviolet
lightat260nmrisessharplyoverasmall
temperaturerange.Atthesametimethesolution
suddenlybeginstoflowmoreeasily(morelike
waterthanlikesyrup).ThemiddleofthisrangeisusuallylabeledTm(melting
temperature).WhatishappeningtotheDNAtocausethesechangesinthesolution
properties?Explainyourresponse.

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Chapter1

Water:ANaturalWonder

Answer:AttheTm,manyofthehydrogenbondsholdingtogetherthetwostrands
oftheDNAhelix,Figure1.34,breakandthestrandsbegintocomeaparttoform
moreflexiblechainsthatcancurluponthemselvestoformstructuresthatare
moreglobularandlessresistanttoflow.Thus,theviscosityofthesolution
decreases.Thespectroscopicproperties(lightabsorption)bybasepairsstacked
oneupontheotherinthedoublehelixarequitedifferentthanthefreebases.
Theabsorptionoflight(intheultraviolet)changesmarkedlyasthedoublehelix
comesapartandthebasesarenolongerstacked.

1.67.

Thisfigurshowsmeltingtemperature,Tm(seeProblem1.66),dataforanumberof
differentdoublehelicalDNAsplottedagainstthefractionofATpairsintheDNAs.
WhyarethemeltingtemperaturesafunctionofthefractionofATpairs?Doesthe
directionofthedependencemakesense?Clearlyexplainyourreasoning.Hint:Review
ConsiderThis1.34.
Answer:InSection1.9,youlearnthattherearethreehydrogenbondsbetweenGC
basepairsandtwobetweenATbasepairs.Therefore,moreenergyisrequiredtobreaka
GCpairingthananATpairing.Highertemperatures(greaterthermalenergyinthe
solution)arerequiredtomeltDNAwithhigherproportionsofGC(orlower
proportionsofAT)pairs.ThustheTmdecreasesastheproportionofATincreases,as
showninthefigure.

1.68.

InProblem1.66,themeltingtemperatureofDNAinsolutionwasdefinedasthe
temperatureatwhichsharpchangesinultravioletlightabsorptionandsolutionflow
occur.Whydoyouthinkthisiscalledameltingtemperature?Is(are)thereany
analogy(ies)betweenwhathappenstoDNAinthesesolutionsandwhathappenswhen
icemelts?Explainyourreasoningclearly.
Answer:Whenasolidmelts,thetemperatureofthesolidliquidmixtureremains
constantuntilallthesolidhasmelted.Thechangefromthedoublehelixtoseparate
strandsoccursoverarathershorttemperaturerangewhenthehydrogenbondsinDNA

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breakatthemeltingtemperature.Thus,therelativelysharpchangeinpropertieswithin
afewdegreetemperaturechangeistheDNAanalogytomelting.
1.69.

Theproteinsinmostorganismsaredenaturedattemperaturesaboveabout60C.
Microorganismsthatliveinhotspringsandorganismsthatliveneardeepoceanthermal
ventssurviveattemperaturesnearorabovetheboilingpointofwater,100C.Their
proteinsaremadeofthesameaminoacidsasallotherorganisms.Whatroledoyouthink
hydrogenbondsmightplayinhelpingtheseorganismssurviv?
Answer:Thelargerthenumberofinteractionsamongtheaminoacidsalongtheprotein
chain,themoreenergywillberequiredtodisruptthefoldedstructureoftheprotein.
Theseinteractionscouldbehydrogenbonds,ionicattractionsbetweenchargedgroups
(Chapter2),and/orhydrophobicinteractionsthatstabilizethefoldedstructurebykeeping
hydrophobicgroupsinsidethestructureawayfromwater(Chapters2and6).Themore
suchinteractions,thehigherthetemperaturerequiredtoprovideenoughthermalenergy
todisrupttheproteinstructure.

1.70.

ThestructureoftheDNAofthethermophilic(therme=heat+philos=loving)
organismsdiscussedinProblem1.69alsohastobemaintainedinthehightemperature
environmentswheretheylive.WhatkindofATversusGCcompositionwouldyou
expecttofindfortheDNAintheseorganisms?Presentyourreasoningclearly.Hint:See
Problem1.67.
Answer:ThesamekindofreasoningasinProblem1.49appliestothermophilic
DNA.Themoreattractionbetweenstrands,themorethermallystabletheDNA
(asinProblem1.47).Thus,youexpectthethermophilestohaveahighproportion
ofGC(withthreeHbonds).Thisisobserved.

1.71.

Celluloseisalongchainmoleculemadeupofglucosemoleculesbondedtogetheras
showninthisillustration.Youwilllearn
moreaboutcelluloselater.Manychains
likethesearehydrogenbondedto
neighboringchainstoformthefibersthatareusedtomakepaperandcottonandlinen

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cloth.Thehydrogenbondsmakecottonclothsoftandflexiblebecausetheyareeasily
brokenandremade,whichallowsthefiberstochangeshape.
(a) Howdoyouaccountforthefactthatcottonclothingiseasilywrinkled?Explain
yourreasoningclearly.
(b) Howdoesironingwrinkledcottonclothingrestoreitspress?Usediagramsto
illustrateyouranswer.
(c) Howmightyoumakepermanentpresscottoncloth?Indicatewhatyouwouldtry
toaccomplish;dontbeconcernedaboutthedetailedchemicalprocessesthatmightbe
required.
(d) Permanentpresscottonclothingisnotassoftasregularcottonclothing.Isthisthe
resultyoumightexpectfromyourresponsetopart(c)?Explainwhyorwhynot.
Answer:(a)Cottonclothinggetswrinkledbybeingwornandforcedtoconform
totheshapeofitswearerandotherforceslikechairseats.Theseforcesonthe
fiberscausethemtobebentandpushedandpulledintoshapesthatbreakssome
Hbondsandmakesothers.Whentheforcesarenolongeracting,saywhenthe
clothingisremoved,thenewHbondsholdthefibersinthepositionstheyhad
takenduringthetimetheclothingwasworn.Sincemanyoftheseinvolvethe
foldingandcreasingthatgoeswithoutmovements,thefabricisnowfoldedand
creasedonasmallscale,thatis,wrinkled.
(b)Ironinghastwoeffects.TheheatoftheironhelpstomaketheHbondsbreak
morereadily.ThemassoftheironforcesthefabricflatsothatHbondsthatare
remadearenowholdingthefabricflat.Thusthewrinklesareremovedandthe
pressrestored.
(c)Tomakethefabricpermanentpress,youwanttokeepthecellulosechains
inthepositionstheyhaveinthefiberintheunwrinkledfabric.SincetheHbonds
aretooweaktoaccomplishthis,youneedtofindawaytobondthechainstoone
another.YoumightdothiswithreagentsthatreactwithOHgroupsthatare
closetooneanothertoformapermanentbondholdingthemtogether.

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(d)Sincethesoftnessofcottoncomesfromtheabilityofthecellulosechainsand
fibermadefromthemtochangeshapeeasily,preventingtheseeasychangeswill
makethefabriclesssoft.Thus,bondingthechainstogether,assuggestedinpart
(c)wouldprobablymakethefabriclesssoft.
Section1.10.PhaseChanges:LiquidtoGas
1.72.

Howisenergyinvolvedforasubstancetochangefromonestatetoanother?Explain.
Answer:Energyisrequiredtoloosenintermolecularforcesthatholdsmoleculesinclose
proximitieswhenasubstancechangesfromasolidtoaliquidorfromaliquidtoagas.
Energyisreleasedtocondensemolecules,strengtheningintermolecularforces,whena
substancechangesfromaliquidtoasolidorfromagastoaliquid.

1.73.

Makethefollowingconversions:
(a) 4550J=___________kJ
(b) 250.J=___________calories
(c) 500.Cal=___________J

[1NutritionalCalorie(Cal)=1000calories]

Answer:(a)4.55kJ(b)59.8calories(c)2.09X106J
1.74.

Aphasediagramsuchasthisoneforwater,isa
commonwayofrepresentingphasechanges.Phase
diagramsarepressurevs.temperatureplotsthatshow
thepressuresatwhichthephasechangesofasubstance
occurasafunctionoftemperature.
(a) Whatinformationdoesthisphasediagramgiveyouaboutthephasesofwaterat
standardatmosphericpressureof760mmHg(=1atm)?Explainyourreasoningbriefly.
Hint:Considerstartingatthepressureaxis,movingacrosstheplot(increasing
temperature)ataconstant760mmHg,andnotingwhenphasechangesoccur.
(b) Forachangefromgaseouswatertoliquidwaterat100Cand760mmHg,willthe
signof E bepositiveornegative?Explainyourreasoning.

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(c) Forachangefromliquidwatertosolidwaterat0Cand760mmHg,willthesign
of E bepositiveornegative?Explainyourreasoning.
Answer:(a)Lookingatthenormalatmosphericpressureof760mmHg,one
canobserveasexpectedthatwaterwillbeinthesolidphasebelow0C,inthe
liquidphaseuptoatemperatureof100C,andtheninthegaseousphase.The
phasediagramrepresentsagreatdealmoreinformationaboutthephaseofwater
atdifferenttemperaturesandpressures.
(b)Aswaterchangesfromthegaseousphasetotheliquidphase,itsenergy
decreases.Thismeansthat E willbelessthanzero,anditssignisnegative.
(c)Aswaterchangesfromtheliquidphasetothegaseousphase,itsenergy
increases.Thismeansthat E willbegreaterthanzero,anditssignispositive.
1.75.

Sketchtheenergydiagramsthatdescribethefollowingprocesses.Makesurethatyou
drawanarrowthatrepresentsthedirectionofthechangeandthatyouindicatethesignof
Efortheseprocesses.
(a) Asampleoficemelting,H2O(s)H2O(l),at0C.E>0forthesample.
(b) Thecombustionofhydrogengasinoxygengasisoneofmanychemicalreactions
thatreleaseconsiderablequantitiesofenergy.Thisprocessisdescribedbytheequation:
2H2(g)+O2(g)2H2O(l)+energy
(c) Thedecompositionofmercuryoxide(HgO)occursathightemperatures.Forthis
processtooccur,energyhastobesupplied.Theprocessisdescribedbytheequation:
energy+2HgO(s)2Hg(l)+O2(g)
(d) Theburning(oroxidation)ofmercuryisthereverseofthedecompositionprocessin
part(c)andisdescribedbytheequation:
2Hg(l)+O2(g)2HgO(s)+energy
(e) Burningasampleofmethaneinoxygengas,forwhichE<0.Thisreactionis
describedbytheequation:
CH4(g)+2O2(g)CO2(g)+2H2O(l)

Answer:
(a)
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E>0
H2Osolid

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Chapter1

(b)

Water:ANaturalWonder

2H2(gas) + O2

E<0

2H2O (liquid)

(c)
2 Hg(liquid) + O 2

E<0

2 HgO (solid)
(d)reverseof(c)
2 Hg(liquid) + O 2

E>0

2 HgO (solid)

CH4(gas) +
2O2(gas)

(e)

E<0

CO2 (gas) + 2H2O

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Chapter1

1.76.

Water:ANaturalWonder

Theamountofenergyrequiredtovaporizemethanolis1.22kJg1.Howmanykcalare
requiredtovaporizeonegramofmethanol?

Answer:SeeWorkedExample1.38andCheckThis1.39inwhichsimilarcalculationswere
doneforwaterandhexane.Theonlyadditionalinformationyouneedisthat1kJ=103J
and1kcal=103cal.
energyofvaporization=1.22kJg1=(1.22kJg1)(1kcal/4.184kJ)=0.292kcalg1
Section1.11.CountingMolecules:TheMole
1.77.

Calculatethemolarmassofaformulaunitofthefollowingsubstances:
(a) dimethylether,CH3OCH3
(b) ethanol,CH3CH2OH
Answer:(a)46.08amu(b)46.08amu

1.78.

Howmanymoleculesofwaterareinexactlyonemoleofwater?Howmanygramsof
waterareinexactlyonemoleofwater?
Answer:(a)6.02X1023molecules(b)18.02grams

1.79.

Howmanymolesinthefollowing?
(a) 100.0gofacetone
(b) 100.0gofmethanol
(c) 100.0gofdimethylether
(d) 100.0gofsucrose
Answer:(a)100.0gacetone

1molacetone
1.721molacetone
58.09gacetone

(b)3.120molmethanol
(c)2.170moldimethylether
(d)0.292molsucrose

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Chapter1
1.80.

Water:ANaturalWonder

Howmanymoleculesaretherein1gramofwater,methanol,acetone,ethanol,and
dimethylether?
Answer:Water:

1molH 2 O 6.022 1023 molecules

22
1gH2 O

3.3 10 molecules ofwater

18gH 2 O
1molH 2 O
Methanol:1.9X1022moleculesofmethanol
Acetone:1.0X1022moleculesofacetone
Ethanol:1.3X1022moleculesofethanol
Dimethylether:1.3X1022moleculesofdimethylether
1.81.

Argonatomshaveadiameterofapproximately100pm.Ifamoleofargonatomswere
lineduponeafteranother,howlong,inmeters,wouldthelinebe?Thedistancefromthe
EarthtotheSunis1.51010m.Howmanyroundtripswillthislineofargonatoms
make?
Answer:100pm/atom)(6.021023atoms/mol)(m/1012pm)=6.021013m
Togivesomeconcretemeaningtothisdistance,itcanbecomparedwiththedistance
toourSun,93millionmiles(=1.51010m).Ourlineofargonatomswouldbeableto
makeapproximately2,000roundtripstotheSun!

1.82.

(a) Howmanymolesofhydrogenbondsarethereinamoleofice?Explainhowyouget
youranswer.Hint:IfeachHstoppedhydrogenbonding,allthehydrogenbondswouldbe
gone.
(b) Theenergyrequiredtomelticeis6.02kJmol1.Ifthemodelforicemelting
presentedinthetextiscorrect,howmanymolesofhydrogenbondsarebrokenwhena
moleoficemelts?Whatpercentageofthetotalhydrogenbondsisthis?Clearlyexplain
howyougetyouranswers.Recallthattheenergyrequiredtobreakahydrogenbond
betweentwowatermoleculesis2025kJmol1.
Answer:Given:1moleofice.Theenergyrequiredtomeltonemoleoficeis
6.02kJmol1.
(a)Askedfor:HowmanymolesofHbondsarethereinamoleofice?

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Recall:IfeachHstoppedHbonding,alltheHbondswouldbegone.Anything
thatistrueofrelativenumbersofmoleculesisalsotrueofrelativenumbersof
molesofthosemolecules.
Plan:Usethemolecule>molerelationshiptofindthenumberofmolesofH
bonds.
Calculations:EachhydrogenatomrepresentsoneHbond;eachmoleof
hydrogenatomsreprsentsonemoleofHbonds.Eachmoleculeofwaterhastwo
hydrogenatoms;eachmoleofwaterhastwomolesofhydrogenatoms.
Therefore,therearetwomolesofHbondsinonemoleofwater.
(b)Askedfor:HowmanymolesofHbondsarebrokenwhenamoleofice
meltsandwhatpercentofthetotalmolesofHbondsisthis?
Recall:TheenergyrequiredtobreakamoleofHbondsisapproximately21kJ
mol1,
1molHbonds=21kJ

1=

1molH bonds
21kJ

Frompart(a),therearetwomolesofHbondsinamoleofice.
Plan:Ifweknowtheenergyrequiredtomelticeandtheenergyrequiredto
breakamoleofHbondswecancalculatethenumberofmolesofHbonds
brokenwhenamoleoficemelts.Weassumethattheenergyrequiredtomeltice
isallusedtobreakHbonds.ConvertthisenergytomolesofHbondsbroken
withtheunitaryconversionfactorabove.ThepercentageoftotalHbondsbroken
iscalculatedfromthisresultandthetotalnumberofmolesofHbonds,two
moles.
Calculations:
1molH bonds
6.02kJ(melts1molice)=(6.02kJ)

21kJ
=0.28mol(Hbondsbrokenpermoleicemelted)
%Hbondsbroken=

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molH bondsbroken
0.28mol
100 =
100
molH bondstotal
2mol

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=14%Hbondsbroken

Recap:Ourapproachwastoassumethattheratiooftheenergyrequiredtomelticeto
theenergyrequiredtobreakalltheHbondsintheicewouldgivethefractionofHbonds
brokeninthemeltingprocess.Ourresultindicatesthatonly14%ofthetotalnumberof
hydrogenbondsarebrokenwhenicemelts.ThatmeansmostoftheHbondsarestill
presenteventhoughthewaterhaschangedfromasolidtoaliquid.Thisisoneofthe
resultsthatleadstotheiceclustermodelofliquidwater.
1.83.

Inwhichofthesecompoundscanthemoleculeshydrogenbondtothemselves?Drawa
diagramofthemoleculesofeachcompoundhydrogenbondingamongthemselves.
(a) water

(d) ethanol

(b) methanol

(e) dimethylether

(c) acetone
Answer:Selfhydrogenbondingrequiresthatthemoleculehasboth(1)a
nonbondingpairofelectronsonanoxygenoranitrogenand(2)anOHorNH.
Water,methanol,andethanolcanselfhydrogenbondsinceallthreehaveboth
theessentialfeaturesforhydrogenbondingwithineachindividualmolecule.
AcetoneanddiethylethermoleculeslackOHbonds.(Theyarecapableof
hydrogenbondingwithwaterbutnotwiththemselves.)TheanswertoProblem
1.41showsthehydrogenbondedstructureofwater.Thoseofmethanoland
ethanolareshownbelow.

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(Ethanolwouldlooksimilartomethanol)
1.84.

Theboilingpointsofdimethylether(CH3OCH3)anddiethylether(CH3CH2OCH2CH3)
are25Cand35C,respectively.Whatinteractionismainlyresponsibleforthe
observeddifference?
Answer:Sincethesecompoundscannothydrogenbondwiththemselves,intermolecular
interactionsarelimitedtodipoleattractionsanddispersionforces.Onamolarbasis,both
ethershaveanequalnumberofpolarCObonds.Therefore,dipolarinteractionsare
notresponsibleforthe60Cdifferenceinboilingpoints.Byprocessofelimination,we
areleftwithdispersionforces(induceddipoleinteractions)asthefactorlargely
responsibleforthehigherboilingpointofthelargerether.

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Chapter1
1.85.

Water:ANaturalWonder

Acetone,likedimethylether,hasnoselfhydrogenbondingcapacity,butitsdipole
momentismorethandoublethatoftheether.Canthishighdipolemomentexplainthe
propertiesofacetonecomparedtotheothercompoundsinTable1.2?Clearlyexplainthe
reasoningforyourresponseandincludeasmanycomparisonsaspossible.

acetone

LineFormula

Molar
Mass,
g

Energyof
Vaporization,
kJmol1

Boiling
Point,
C

Dipole
Moment,
Debye

CH3C(O)CH3

58

32

56

2.88

Answer:Dipoledipoleattractionsarethemajorcontributortotheforcesholding
acetonemoleculestogetherintheliquid.Becausetheacetonedipolemoment
(2.88D)issomuchlargerthanthatoftheether(1.30D),theattractionsaremuch
strongerbetweenacetonemoleculesanditsboilingpointis81degreeshigher.
Theenergyofvaporizationforacetoneisintermediatebetweendimethylether
andethanol.Theethanoldipolemomentissmallerthanthatofacetone,butthe
hydrogenbondinginethanolraisesitsboilingpointandenergyofvaporization
abovethoseofacetone.Althoughacetonehasamolarmassthatislowerthanthat
ofhexane,itsenergyofvaporizationandboilingpointarecomparabletohexane,
becausethedipoledipoleattractionsinacetonearestrongerthanthelarger
numberofinduceddipoleattractionsamonghexanemolecules.
Section1.12.SpecificHeatofWater:KeepingtheEarth'sTemperatureStable
1.86.

Definespecificheat.
Answer:Theenergyrequiredtoraisethetemperatureof1gramofasubstance
1C.

1.87.

Whatisthedifferencebetweenanintensiveandanextensiveproperty?
Answer:Anintensivepropertyisindependentoftheamountofthesubstancepresent,
(example:temperature)whileanextensivepropertydependsontheamountofsubstance
present(example:thermalenergy).

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Chapter1
1.88.

Water:ANaturalWonder

Arethefollowingpropertiesintensiveorextensive?
(a) theboilingpointofwater
(b) thedensityofwater
(c) thespecificheatofwater
(d) theratioofhydrogentooxygenatomsinasampleofwater
(e) the(maximum)solubilityofsaltinwater
Answer:Recallthatintensivepropertiesareindependentoftheamountofmaterialand
invariantfromonesampletoanother.Extensivepropertiesdependontheamountof
materialandmayvaryfromonesampletoanother.Allfivepropertiesthelistedinthis
problemareintensiveproperties.Oftentimes,anintensivepropertycanbetheratioof
twoextensiveproperties.Forexampledensity(intensive)istheratioofmassandvolume
(bothextensiveproperties).Solubilityistypicallyexpressedasaratioofmasstovolume
(seeChapter2).

1.89.

Convert37.0Ctokelvin.
Answer:37.0C+273.15=310.15K

1.90.

Howmuchthermalenergyisrequiredtoraisethetemperatureof1.0gramofwaterby
(a) 10.0C?

(c) 25.0K

(b) 25.0C?
Answer:(a)41.8J(b)and(c)104.5J
1.91.

Howmuchthermalenergyisrequiredtoraisethetemperatureofthefollowingby
10.0C?
(a) 10.0gramsofwater

(b) 25.0gramsofwater

Answer:(a)418J(b)1045J
1.92.

Howmuchthermalenergyisrequiredtoraisethetemperatureof20.0gramsofacetone
by15.0C?
Answer:651J

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Chapter1
1.93.

Water:ANaturalWonder

Indrypartsoftheworld,airconditioningisprovidedbyblowingthehotoutsideair
throughmatssoakedinwaterbeforeitentersthebuilding.Onwhatscientificprincipleis
thissystembased?Howdoesitwork?Whatadvantagesanddisadvantagescanyousee
forthepeopleandthingsinthebuilding?
Answer:Thesystemisbasedontheprincipleofevaporativecooling.Asthehot
airflowsoverthemats,heatistransferredfromtheairmoleculestothewater,the
airlosesheatenergy,andthetemperatureoftheairfalls.Theheatenergy
transferredtothewatercausessomeofthewatertoevaporateintotheair.The
heatrequiredtovaporizethewaterisquitesubstantial(recallthehighenergyof
vaporizationofwater)soarelativelysmallamountofevaporationcanremovea
lotofheatfromtheair.Inareasoflowhumiditythissystemwouldhavethe
addedadvantageofincreasingthehumidityintheairinthebuilding.Conversely
inregionsofhighhumiditythismethodofairconditioningmightnotbeas
advantageoussinceincreasingthehumiditycouldresultinincreasedlevelsof
moldandmildewandmightcausedamagetosensitiveinstrumentationfromthe
damp.Italsowouldntworkaswellinhighhumidity;

1.94.

Wouldyouexpectevaporativecoolingofyourskintobemoreeffectiveondrydaysor
humiddays?Clearlyexplainthereasoningforyouranswer.
Answer:Evaporativecoolingshouldbemoreimportantondrydaysthanhumid
dayssincetheamountofwaterthatcanevaporateintotheatmospheredepends
upontheamountofwateralreadyintheatmosphere.Iftheresalotofwater
therealready,onahumiddayforexample,thentheamountofsweatthatcan
evaporatewillberelativelylow.Thisisbecauseatagiventemperaturethe
atmospherecanonlyholdacertainamountofwater,onhumiddaysthe
atmosphereisnearthatlimit.(Ifthelimitisexceeded,watercondensesor
precipitatesoutoftheair.TherelativehumiditythatyourTVweatherperson
talksaboutisthepercentofwatertheaircontainsrelativetothemaximum
amountitcancontainatthattemperature.)Littlewaterwillevaporateand
thereforenotmuchevaporativecoolingwilloccur.

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Chapter1
1.95.

Water:ANaturalWonder

Table1.3givestheheatcapacityofliquidwateras75Jmol1C1(18calmol1C1).
Theheatcapacityofsolidwater(ice)is38Jmol1C1(9.0calmol1C1).Whydoyou
thinktheheatcapacityofthesolidislessthanthatoftheliquid?Areourmodelsofliquid
andsolidwaterconsistentwithyourexplanation?
Answer:Ourmodelofliquidwatersaysthatheatenergyaddedtothewater
makesthemoleculesmovefaster(increasesthetemperature)andcausessomeH
bondstobebroken.Thetemperatureriseisnotaslargeasitwouldbeinthe
absenceoftheHbondbreakingandthespecificheat(orheatcapacity)ishigh
becauseittakesmoreheattomakeagivenchangeintemperature.Heatenergy
addedtoiceattemperaturesbelow0C(sothesoliddoesnotmelt),breaksnoH
bonds;theenergyonlycausesthemoleculestomovefasterastheyvibrateand
jiggleinthepositiontheyareheldbytheirfourHbonds.Alltheenergyadded
goestoraisingthetemperature(increasingmolecularmotion);ittakeslessheat
tomakeagivenchangeintemperatureandtheheatcapacityislowerthanfor
liquidwater.

1.96.

Theheatcapacityofgaseouswater(steam)atoneatmospherepressureis36.7Jmol1C
(8.8calmol1C1).Whatsortofmodeldoyouthinkwoulddescribegaseouswater?

Whydoyouthinktheheatcapacityofthegasislessthanthatoftheliquid(SeeTable1.3
orProblem1.95)?Isyourmodelofthegasandthemodeloftheliquidwehavediscussed
inthischapterconsistentwithyourexplanation?
Answer:Thehighheatcapacityofliquidwaterisreviewedinthesolutionto
Problem1.95.Gasesoccupysomuchmorespacethanthesameamountofliquid,
thatweeitherhavetoassumethatthemoleculesgetalotbiggerorthattheyare
farapartandprobablynotinteractingwitheachotherverymuch.Gasesareall
completelymisciblewithoneanother,sothemodelthathasalotofemptyspace
betweenmoleculesseemstofitthispropertybetter.Ifthismodeliscorrect,then
wewouldexpectessentiallynoHbondsbetweenwatermoleculesinthegas
phase.IftherearenoHbondsalltheheatenergyweputintothegasgoesinto
increasingthespeedofmolecularmotion(temperature).Ittakeslessheatenergy

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tomakeagivenchangeintemperatureandtheheatcapacityofthegasislessthan
thatoftheliquid.Notethattheheatcapacitiesofsolidandgaseouswaterare
similar(abouthalfthatofliquidwater).Thissimilarityisfortuitous;the
molecularmotionsinvolvedinthetemperaturechangesinthesolidandthegas
aredifferent.Inthesolid,themolecularmotionismainlyvibrationandrocking
inplaceinthecrystal.Inthegas,themotionsaremainlytranslation(movement
fromoneplacetoanother)androtation.
1.97.

Table1.2showsthat44kJmol1(10.5kcalmol1)
arerequiredtochangeonemoleofliquidwaterto
watervapor.Thisvalueisforwaternear25C.
Theenergyofvaporizationdependsonthe
temperatureofthewater,asshowninthisfigure.
Whydoestheenergyrequiredtovaporizewater
varywithtemperaturethisway?Clearlyexplain
yourreasoning.
Answer:Athighertemperatures,thewatermoleculeshavegreaterenergyof
motionandfewerHbonds.Ittakeslessenergytovaporizewateratahigher
temperaturebecausetherearefewerHbondstobreak.Forwatermoleculesto
vaporizetheymustescapefromtheliquid.Themorehydrogenbondsholding
themintheliquidphase,themoreenergythisprocesswilltake.Inadditionto
understandingthedirectionofthisphenomenon,youshouldalsonoteits
magnitude.Theheatofvaporizationdecreasesfromabout10.7kcalmol1at0C
toabout9.7kcalmol1at100C.Thisisonlya10%changeovertheentireliquid
range.Theplotmightgivetheimpressionthatthechangeismuchlarger.What
choiceofscalewouldyouusetoshowthatthechangeisactuallyarelatively
smallpercentageofthetotal?

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Section1.13.EXTENSIONLiquidViscosity
1.98.

TowhichphysicalpropertyofliquidsdoestheexpressionslowasmolassesinJanuary
oweitstruth?WouldmolassesbefasterinJune?Why?
Answer:Theexpressionowesitstruthtoviscosity.Viscositymeasurestheresistanceof
fluidstoflow.Thegreatertheviscosity,themoreslowlytheliquidflows.Theviscosity
ofaliquidusuallydecreasesastemperatureincreases.Therefore,molasseswouldflow
muchfasterinJunethanitdoesinJanuary.

1.99.

Theviscosityofnheptane,CH3(CH2)5CH3,asa
functionoftemperatureisplottedhereonthesame
scaleasFigure1.41,whichgivesthecorresponding
datafortheviscosityofwater.Tomaketheplots
comparable,thevaluesherearerelativetothe
viscosityofheptaneat20C.Whatsimilaritiesdo
youobservebetweenthesedataandthosefor
water?Whatdifferencesdoyouobserve?What
explanationcanyouprovideforthesimilaritiesanddifferences?
Answer:

Thedataforheptaneareonthelefthandplotandthoseforwaterareontheright.
(TherighthandplotisFigure1.39;thecaptionispresentbutthegraphicis
missingfromthefieldtestdraftofthetext.)Theaxesonbothplotsareidentical

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asisthereferencepoint(viscosityat20C)fortherelativeviscosity.Therefore,
theshapeandplacementofthetwolinescanbedirectlycompared.Theviscosity
ofbothsubstancesdecreaseswithtemperature.Highertemperaturemeansmore
averageenergypermolecule;itiseasierforthemoleculestoovercomethe
attractionsbetweenthemandthereforemovepastoneanothermorereadily.The
lowtemperaturerelativeviscosityofheptaneislowcomparedtowaterandits
decreasewithtemperatureislesspronouncedthanforwater.Theattractions
amongheptanemoleculesareinduceddipoleinteractions(dispersionforces),
whicharerelativelyweaktobeginwithandremainaboutthesameasthe
temperatureincreasesthemotionsofthemolecules,sothereisarelatively
gradualdecreaseinviscosity.Therelativeviscosityofwaterundergoesamuch
steeperdecreasewithtemperature.Thestronger,moredirectedhydrogenbonds,
thatareresponsibleformuchofthehighviscosityatlowtemperaturesare
disruptedathighertemperaturesandtheincreasedmotionofthewatermolecules
makesthesedirectedbondslesslikelytoformathighertemperatures.Thus,the
dropinrelativeviscosityforwaterismorethantwicewhatisobservedfor
heptane.

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1.100. Natureexploitsthepropertiesofthe
hydrogenbondinmanyways.Scientists
alsoworktofindwaystousethisweak
bondwithitsstrengthinnumbersto

R
O

creatematerialswithinterestingand

O
O

usefulproperties.Onegroupofresearcher

hasmadeacompoundwhosemoleculeshavestickyends;eachendofonemolecule
formsfourhydrogenbondstoanothertoproducelongchains,asrepresentedinthe
figure.
(a) Forsolutionsofthiscompound(inanonhydrogenbondingsolvent)thatvaryin
concentrationfromabout8to80g/L,the
viscosityvariesasshowninthislogarithmicplot.
Astheconcentrationchangesbyafactorof10,
bywhatfactordoestheviscositychange?Clearly

1000

100

10

explainhowyoumightinterpretthisresult.Hint:

0.1

Recallthatlargemoleculescantmoverapidlyin

0.01

10

100

concentration,g/L

solution,sotheirsolutionsresistflow.

(b) Theviscosityofthesesolutionsistemperaturedependent.Doyoupredictan
increaseordecreaseinviscosityasthetemperatureofasolutionisincreased?Explainthe
reasoningforyourprediction.
(c) Theresearchersalsomadeacompoundwhosemoleculesareessentiallyhalfofone
ofthemoleculesshownabove.Thesenewmolecules

12

haveonlyonestickyend.Theviscositiesof

10

mixturesof32g/Loftheoriginalcompoundwith
smallamountsofthenewcompoundareshownin
thisplot.Thehorizontalaxisshowsthedecimal
fractionofthemixturethatisthenewcompound;
0.01,forexample,meansthat1in100ofthe

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6
4
2
0

0.01

0.02

0.03

0.04

0.05

fractionnewcompound

0.06

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Chapter1

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moleculesinthesolutionarethenewmolecules.Clearlyexplainhowyoumightinterpret
whatisgoingoninthesolutiontoproducetheseresults.
Answer:(a)Thescaleonbothaxesislogarithmic.Theconcentrationaxiscovers
afactorof10inconcentration,whiletheviscosityaxiscoversafactorof104
(from0.1to1000).Theviscosityincreasesfromabout.08toabout800onthis
scale,whichisafactorof104.Asmoreandmoreofthestickyendedmolecules
aredissolved,longerandlongerchainsofthemareformed.Thechainsattractone
anotherbydipoleandinduceddipoleinteractionsandalsocanbecomeentangled
withoneanother.Alltheseattractionsmakesitharderforthechainstomovepast
oneanother,sotheviscosityincreases.
(b)Forthesamereasonsthattheviscosityofwaterdecreaseswithincreasing
temperature,thesesolutionsshouldshowdecreasingviscositywithtemperature.
Thehydrogenbondingisdisruptedasthemoleculesbecomemoreenergeticand
movefaster.
(c)Asthefractionofmoleculeswithonlyonestickyendincreases,theviscosity
decreases.Thereisacompetitionamongthestickyendsforoneanother.If
moleculeswithtwostickyendshydrogenbondtooneanother,alongerchainis
formedthathasahigherviscosityandcouldaddmoredoubleendedmoleculesto
makeevenlongerchains.But,ifamoleculewithonestickyendhydrogenbonds
toamoleculewithtwostickyends,thechaincannolongercontinuetogrowat
theendwherethebondingoccurs.Asmoreandmoreofthemoleculespresent
haveonlyonestickyend,theprobabilitythatchaingrowthwillbestuntedgrows
andthechainsaresmaller.Thesmallerchainsgivethesolutionalowerviscosity.
Therapiddecreaseintheviscosityforrathersmallamountsofthesingleended
moleculeadded,showthatitdoesnttakemuchstuntingofthegrowthofthe
chainstohavealargeeffectontheviscosity.
GeneralProblems
1.101. Brieflyexplainwhy:

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(a) Youexperienceacoolingeffectafterwalkingoutoftheoceanontoawarm,sandy
beach,especiallyonabreezyday.
(b) Liquidscanbedefinedas"disordered"solids.Arethereproblemswiththis
definition?
(c) Liquidscanbedefinedas"dense"gases.Arethereproblemswiththisdefinition?
(d) Solidwater(ice)floatsonliquidwater.
(e) Steamcanbadlyburnyou,ifitcondensestowateronyourskin.
(f) Lakesfreezefromthetoptothebottom.
(g) Waterpipesbreak,ifwaterfreezesinthem.
Answer:
(a)Waterneedsheatfromyourskintoevaporate.Whilesupplyingtheheatfor
watertochangefromaliquidtoagas,youfeelacoolingeffectonyourskin.
(b)Themoleculesinliquidsareattractedtooneanotherandstayclosetogether,
similartosolids.However,themoleculesinliquidsaremuchmoredisordered
becausetheycanmovearound,whilestillstayingclosetogether.
(c)Thefactthatthemoleculesinliquidcanmovearoundmakesthemsimilarto
gases.Themoleculesingasesareveryfarapart,movingessentially
independentlyofoneanother.Sincetheraremanymoremoleculesinagiven
volumeofaliquidcomparedtothesamevolumeofagas,liquidsaresometimes
definedas"densegases".
(d)Icefloatsonliquidwaterbecausethedensityofliquidwaterislowerthanthe
densityofice.
(e)Duringcondensation,energyisreleasedtothesurroundings.Thisiswhyyou
canbebadlyburnedbysteam,ifitcondensestowateronyourskin.
(f)Whenlakesfreezeduringthewinter,icecoversthetopoftheliquidwater,
insulatingthewaterbelow.Sinceiceislessdensethanliquidwater,icefloats
anddoesnotfalltothebottomofthelake.
(g)Whenwaterfreezesinpipes,theiceexpandsduetothelargervolumeofice
comparedtoliquidwater.Thiscausesthepipestobreak.
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1.102. Chemistryiseverywhere.Afriendhasaskedyouiftheclaimsarescientificallyaccurate:
Keepabottleofwateratyourdeskandtakefrequentsipsfromit.Onethirdofwateris
oxygen,sodrinkingitwillhelpkeepyoualert.Writearesponsethatwillhelpyour
friendsortoutwhatistrueandwhatmightnotbe.
Answer:Thisisnotaprofoundproblem,butisdesignedtosuggestbeingonthe
lookoutforextraordinaryclaimslikethisone.Onanatombasis,onethirdofthe
atomsinwaterareoxygen,sothetextiscorrectinoneway.Itseemsthatthe
claimissomethingaboutthealertnessenhancingqualitiesofoxygen.Youdo
needoxygenmoleculesfromtheairtokeepyourmetabolismgoingandyouget
tiredmoreeasily,iftheoxygenleveldropssomewhat.(Thatswhyyoufeelstress
whenexertingyourselfathighaltitude,beforeyourbodyacclimatestothelower
pressureofairand,hence,ofoxygenintheair.)Theoxygenatomsinwaterare,
however,totallyunavailableforyoutouseinmetabolism.Theyareboundinvery
stablemolecules.Thebestonecansayaboutthisclaimisthatitcanthurtto
drinksomewateranditisfree,thatis,nothingisbeingsoldhere.

1.103. Onemodelofliquidwater(anicebergmodel)isamixtureofmolecularscale,icelike
structuresamongotherlessordered,lesshydrogenbondedmoleculeswiththemolecules
continuallyexchangingbetweenthetwoforms.Inasampleofliquidwater,itispossible
togiveextraenergyofmotiononlytothosemoleculesthatarepointing(oriented)inthe
samedirection.Thenaturalrockingandjigglingofthesemoleculessoonchangestheir
orientation(theybecomemorerandom).Scientistshavemeasurethetimerequiredforthe
changeandfindthatsomeofthewatermoleculesmakethechangeinanaverageofabout
0.71012s(0.7ps).Theresttakeanaverageofabout131012s(13ps).Thescientists
concludedthatliquidwateractslikeitismadeupoftwospecies.
(a) Isthisconclusionconsistentwiththeicebergmodelofliquidwater?Whatmight
thetwospeciesbe?Clearlystatethereasoningforyouranswers.
(b) Whichofthetwospecieschangesorientationrapidlyandwhichmoreslowly?
Explainyourreasoning.Usedrawings,iftheyarehelpful.

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(c) Iftherearetwospecies,whyarenttheyapparenttooursensesinoureveryday
contactswithwater?
Answer:
(a)Theicebergmodelforliquidwaterhassomeofthewatermoleculeshydrogen
bondedinmolecularscaleicelikestructuresandothersthatarelessorderlyandmore
mobile.Itmakessensethatorderlyandadisorderlywaterstructureswouldbehave
differentlyintermsoftheirabilitytorandomizetheorientationtheyhavebeengivenby
theexperimenters.
(b)Sincethewatermoleculeslockedinanicelikestructurecannotmoveabout
independently,theirmotionsareprobablymoreinhibitedandtakelongertoregaina
morerandomorientation.Thus,wewouldexpecttheshorterrandomizationtimetobe
characteristicofthelessorderly,moremobilemoleculesandthelongertime
characteristicofthemoleculesintheicelikestructures.
(c)Notethatthetimescalesofthechangesobservedherearepicoseconds.The
moleculescanundergoreorientations,whichmeansbreakingsomehydrogenbondsand
makingothersinaveryshorttime.Averagedoverobservationtimesontheorderof
seconds(oureverydaycontactswithwater),suchrapidchangesmakeitimpossibleforus
todetectanydifferencesamongthemoleculesorpossiblerapidlyinterchanging
structuresintheliquid.Onlycleverexperiments(andcalculations)willenableustoget
betterpicturesofthenatureofliquidwater.
1.104. Gasesbehavemuchlikeliquidsintermsofthingsfloatingandsinkinginthem.Whatcan
bededucedfromeachofthesefacts:
(a) Aheliumfilledballoonwillriseinair.
(b) Ahotairballoonwillrisein(colder)air.
(c) Aballoonfilledwithcarbondioxidewillsinkinair.
Answer:(a)Heliumislessdensethanair(unstatedassumption:whenbothareatthe
sametemperatureandpressure).
(b)Hotairislessdensethancoldair(unstatedassumption:whenbothareatthesame
pressure).
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(c)Carbondioxideismoredensethanair(unstatedassumption:whenbothareatthe
sametemperatureandpressure).
1.105. WhatwouldhappenifanastronautstandingontheMoonletgoofaheliumfilled
balloonshewasholding.RecallthattheMoon,unliketheEarth,hasnoatmosphere.
Hint:SeeProblem1.104(a).
Answer:ItwouldbepulledbygravitytothesurfaceoftheMoon.Aheliumballoonon
EarthrisesbecauseitfloatsonthemoredensegasesoftheEarthsatmosphere.Since
thereisnoatmosphereontheMoon,thereisnothingfortheheliumballoontofloatupon.
1.106. Potassiumacidfluorideisasaltcomposedoftheions,K+and(FHF).Thenegativeion,
(FHF),canbethoughtofastwofluorideionshydrogenbondedbyaprotonwiththe
Lewisstructure:

F H F

.TheHFbondlengthinhydrogenfluoride,HF,is93pm.

EachoftheHFbondlengthsin(FHF)is113pm.Formationof(FHF)fromHFandF
releasesabout155kJmol1,makingitbyfarthestrongesthydrogenbondknown,
althoughmuchweakerthanthetwosharedelectroncovalentbondinHFwhichreleases
about565kJmol1whenitforms.
(a) What,ifanything,ispeculiarabouttheLewisstructureshownfor(FHF)?
(b) Discussthesimilaritiesanddifferencesbetweenthishydrogenbondandthe
hydrogenbondbetweentwowatermolecules.Alsodiscusswhetherthe(FHF)example
blursthedistinctionbetweencovalentbondsandhydrogenbonds.
Answer:
(a)TheLewisstructureshowsfourelectronsaroundtheHatom.
(b)Thedifferencesarethatthishydrogenbondisformedwithinanionandwiththe
mostelectronegativeatombeingontheendsoftheion.Inwater,theoxygenatomisthe
centralatom.Italsolookslikethisionwouldbelinearwiththetwofluorineatomstrying
tokeepasfarapartfromeachotherispossible,thusexplainingthebondlength
differencefromHF.Thesimilarityisthatbothformhydrogenbonds.Yes,thisiondoes
blurthedistinctionbetweenahydrogenbondandacovalentbond.

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1.107. (a) About70%(bymass)ofyourbodyiswater.Howmanymolesofwaterdoesyour

bodycontain?Howmanymoleculesofwater?
(b) Theboxedtableonpage127givestheelementalcompositionofyourbody.
Assumethatthesamenumberofatomsofoxygenandnitrogenarecombinedin
moleculesotherthanwater.Howmanyoxygenatoms(per100,000atoms)arecombined
withhydrogenatomstomakethewaterinyourbody?
(c) Useyourresultsfromparts(a)and(b)tocalculatethetotalnumberofatomsinyour
body.Howmanyoftheseatomsarenitrogen?carbon?Howmanymolesofnitrogendoes
yourbodycontain?carbon?
Answer:
(a)Assumea70kg(approximately150pound)person.Themolesandmoleculesof
waterinthisperson(70%water)are:
molH2O=(0.7)(70103g)/(18gmol1)=2.72103mol
molecH2O=(2.72103mol)(6.021023molecmol1)=1.641027molec
(b)If2440Oatomsareincompoundsotherthanwater,then23230(=256702440)O
atoms(outofevery100000atoms)arepresentinwater.
(c)Frompart(b)weknowthat23230moleculesofOarepresentasH2Oforevery
100000atomsinthebody.Frompart(a)weknowthenumberofmoleculesofH2Ointhe
body,sowecangetthetotalnumberofatomsinthebodyas:
total#atoms=[(100000atoms)/(23230moleculesH2O)](1.641027molec)
=7.061027atoms
TogetthenumberofatomsofNandC,wetakethefractionofatomsthatareNandC
timesthetotalnumberofatoms:
atomN=[(2440atomC)/(100000atom)](7.061027atom)=1.721026atom
molN=(1.721026atom)/(6.021023atommol1)=2.86102mol
atomN=[(10680atomC)/(100000atom)](7.061027atom)=7.541026atom
molN=(7.541026atom)/(6.021023atommol1)=1.25103mol

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1.108. Thistablegivesthenames,structures,andenergiesofvaporizationformostofthe
hydrocarbons(moleculescontainingonlycarbonandhydrogenatoms)whoseboiling
pointsaregiveninthefigureinConsiderThis1.23.
hydrocarbon

formula

energyofvaporization
kJmol1

ethane
propane
butane
pentane
hexane
heptane
octane
nonane

CH3CH3
CH3CH2CH3
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)6CH3
CH3(CH2)7CH3

15.65
20.13
24.27
27.61
31.92
35.19
38.58
43.76

(a) Plottheseenergiesofvaporizationasafunctionofthenumberofelectronsineach
molecule.Drawthebestpossiblestraightlinethroughthepoint.(Ifyouuseagraphing
calculatororcomputergraphingprogram,itcanconstructthelineforyou.)Predictthe
energyofvaporizationfordecane,CH3(CH2)8CH3.
(b) WhyisthereanincreaseinenergyrequiredtovaporizethesemoleculesasCH2
groupsareadded?Usetheslopeofyourlinefrompart(a)todeterminehowmuchthe
energyofvaporizationincreasesforeachCH2groupadded.
(c) Assumethatinduceddipoleattractions(dispersionforces)aredirectlyproportional
tothenumberofelectronsinmoleculeswithsecondrowelementsconnectedinachain,
likethoseinthistable.Whatdoyoupredictfortheenergyofvaporizationofdimethyl
ether?HowdoesyourpredictioncomparetothevaluegiveninTable1.2?Howdoyou
explainanydifference?
(d) Theenergiesofvaporizationofdiethylether,CH3CH2OCH2CH3,andbutanol,
CH3CH2CH2CH2OH,are29.1and45.9kJmol1,respectively.Usewhatyouhavelearned
inthepreviouspartsofthisproblem,plusthedatainTable1.2,topredicttheseenergies
andcomparethemwiththeexperimentalvalues.Whatattractionsamongthemolecules
mustyouaccountforineachcase?

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Answer:
(a)Theplotofthedatalookslikethis(afinestraightlineaslongasmethaneisnot
included):
45
40
35
30
25
20
15
10

Energy=0.49(#ofelectrons)+7.3

5
0

10

20

30 40 50 60
electrons/molecule

70

80

Sincedecanehas82electrons,theequationofthelinegivesitsenergyofvaporizationas
47.5kJmol1.
(b)EachCH2groupaddseightelectronsandlengthensthehydrocarbonchainsothat
moreelectronsandmoresurfaceareaareavailablefordispersionforce(induceddipole)
attractions.Theincreaseofeightelectronsaddsabout4kJmol1(=80.5kJmol1
fromtheslopeoftheline).
(c)Dimethyletherhas26electronsandissimilarinthisregardtopropanewithan
energyofvaporizationof20kJmol1.Wecanattributetheextra3kJmol1energyof
vaporizationoftheether(23kJmol1)todipolarattractionduetothepermanentelectric
dipoleofthemolecule.
(d)Diethyletherhas42electronsandissimilartopentanewithanenergyof
vaporizationof28kJmol1.Wefoundinpart(c)thatanethermighthaveanextra3
kJmol1energyofvaporizationattributabletodipolarattraction,sowewouldpredictan
energyofvaporizationof31kJmol1.Itappearsthatthisisanovercorrectionforthe
etherwithlargeralkylgroups,whichmightinterferewiththemoleculesabilitytoorient
asreadily.Thebutanolalsohas42electronsandwewouldagainexpectacontributionof
28kJmol1totheenergyofvaporizationfromdispersionforces.Inaddition,thealcohol
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canformhydrogenbondsandthese,accordingtoourtextualanalysisofthedatainTable
1.2mightcontributeanadditional22kJmol1totheenergyofvaporization,foratotalof
50kJmol1.Again,ourpredictionisoffbyabout8%,butthisisquitegoodagreement
consideringthesimplicityofourassumptionsandthemodels.

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