Solutions ch08

Chapter8
EntropyandMolecularOrganization
SolutionstoChapter8Problems
Section8.1.
MixingandOsmosis
8.1.
Whichprocessesinvolveanincreaseinorganizationforthesystemspecified?
Whichinvolveadecreaseinorganization?Explainyourreasoningbriefly.
(a) icecreammelting
(b) studentstakingtheirplacesinaclassroomwithfixedseating
(c) ashrubformingspringflowers
(d) obtainingpurewaterfromseawater
(e) openingandshufflinganewdeckofcards
(f) rakingleavesintoasinglepile
Answerto8.1:
(a)Icecreammeltingwilldecreasetheorganizationofthesystem.Rather
thanbeinginidentifiablescoopsoficecreamperchedsecurelyonacone,
therenowwillbeliquidicecreamdrippingontheoutsideofthecone,
ontoyourhands,andpossiblyontoyourclothesaswell.
(b)Studentsenteringaclassroomwithfixedseatingareabouttoundergo
anincreaseinorganization.Thechairsarepermanentlyarrangedsothata
specifiedorderwillbemaintained.
(c)Ashrubformingspringflowerswillbeincreasingtheorganizationof
thesystem.Complexmoleculesarebeingarrangedintoevenmore
complexcells,whichinturnareorganizedintolargerandlargerunitsof
thetree.
(d)Obtainingpurewaterfromseawaterrequiresanincreaseinthe
organizationofthesystem.Startingwiththesaltsolution,watermolecules
areevaporatedthroughadistillationprocess,leavingthepreviously
dissolvedsaltsbehind.
(f)Rakingleavesintoasinglepiledefinitelyrepresentsanincreasein
organization,atleastuntilthenextpuffofwindcomesalong.
8.2.
Explainwhyawatersolubledyespreadsoutwhenitismixedwithwaterresulting
inauniformlycoloredsolution.Willthereverseprocesseverhappen?
Answerto8.2:
RevisionDate:21jan03
ACSGeneralChemistryTrialVersion
Chapter8
Thedyespreadsoutbecausethemixedstateinmoreprobable(seesection8.3for
whyitismoreprobable).Weknowfromeverydaylifethatthereverseprocess
neverhappens,(becausethefinalstateinlessprobable).
8.3.
Afewdropsofgreengoodcoloringareaddedtosomecookiedough.
(a) Arethesedropsoffoodcoloringlikelytodisperseontheirownthroughout
thecookiedough?Explainyourreasoning.
(b) Comparedtoyouranswerinpart(a),aredropsofgreenfoodcoloringmore
orlesslikelytodispersethroughoutaglassfilledwithwater?Explainyour
reasoning.
Answerto8.3:
(a)Itisunlikelythattheliquidfoodcoloringwillspontaneouslydisperse
throughthesemisolidcookiedoughinafiniteamountoftime.Ifenough
mixingisdone,itwillbepossibletoturntheentiresampleofdoughthe
desiredgreencolor.
(b)Dropsofgreenfoodcoloringaremoreeasilymixedwithaliquidthanwith
cookiedough.Themixingstartsasthedropsareaddedtotheliquid,and
molecularmotionintheliquidwillenabletheprocesstocontinue.
8.4.
Themembranesofredbloodcellsaresemipermeable.Movingwateroutofthe
bloodcellcausesthecelltoshrivel,aprocessknownascrenation.Movingwater
intothebloodcellcausesthecelltoswellandrupture,aprocessknownas
hemolysis.Peopleneedingbodyfluidsornutrientsandwhocannotbefedorally
aregivensolutionsbyintravenous(orIV)infusion.AnIVfeedsnutrientsdirectly
intoveins.ExplainwhatwouldhappenifanIVhavingahigherconcentration
thanthesolutionwithintheredbloodcellwasgiven.
Answerto8.4:
Waterfromthebloodcellwouldmoveoutofthebloodcellcausingcrenationof
thecells.
8.5.
Explaintheroleofosmosisineachofthefollowingprocesses.
(a) Swimminginafreshwaterlakemakesyourbodywaterloggedandincreases
yourneedtourinate.
(b) Cucumberswrinkle,losewaterandshrinkwhenplacedinbrine
(concentratedsaltwatersolution).
(c) Prunesandraisinsswellinwater.
Chapter8
(d Yougetthirstyandyourskinwrinkleswhenyouswimintheocean.
(e) Saltandsugarareusedtopreservemanyfoods.
(f) Manysaltwaterfishdiewhenplacedinfreshwaterandviceversa.
Answerto8.5:
(a)Yourmoreconcentratedbodysolutionsdrawsinwaterfromfresh
water.
(b)Thewaterfromthejuiceinsidethecucumbermovesintothehigher
concentratedbrinesolution.
(c)Waterpassesthroughthepruneskinintothemoreconcentrated
solutionwithintheprune.
(d)Thesaltyoceanwaterismoreconcentratedthanyourbodyfluidsand
waterpassesthroughyourskinintotheocean.
(e)Bacteria,whichcausesfoodtospoil,diewhenwaterisdrawnout
throughtheircellmembranes.
(f)Osmosiscausesthesoluteconcentrationsofthefishbodytissuetoincreaseor
decrease.
Section8.2.
ProbabilityandChange
8.6.
Choosethebestanswer(s)andexplainyourchoice(s).
Whenadyesolutionmixeswithwaterinanunstirredcontainer,themixing
occursbecause:
(i) Themixedstatehasahighernumberofdistinguishablearrangementsthan
theunmixedstate.
(ii) Themixedstatehasalowerheatcontentthantheunmixedstate.
(iii) Themixedstateismoreprobablethantheunmixedstate.
Answerto8.6:
(i)and(iii)
8.7.
Whatnumericalvalue(0,1,orsomewhereinbetween)wouldyouassigntothe
chanceofeachofthesechangesbeingobserved?Brieflydiscussyourreasoning,
givinganyconditionsunderwhichtheprobabilitycouldchange.
(a) Abrokeneggshellreformingintoanunbrokeneggshell.
Chapter8
(b) Adropoffoodcoloringdispersingthroughoutacupofwateratroom
temperature.
(c) Drawingtheaceofspadesfromashuffleddeckofcards.
(d) Findingallofthepepperonislicesononehalfofapizzasurface.
(e) Alargeoaktreefallingtothegroundandthenreturningtotheupright
position.
(f) Recoveringsixpairsofcleansocksfromthedryerafterwashingsixpairsof
dirtysocks.
Answerto8.7:
(a)Probability=0.Abrokeneggshellhasneverbeenobservedreforming
itselfintoanunbrokenegg.Itmightbepossibletopainstakinglyglueall
ofthepiecesbackintoawholeshape,butthiswouldrequireconsiderable
work(andskill)onyourpart.
(b)Probability=1.Adropoffoodcoloring,givenenoughtime,can
dispersethroughoutacupofwateratroomtemperature.Themoleculesof
waterandofdyeareconstantlyinmotion,helpingtoachievethecomplete
mixture.
(c)Probability=1/52or0.02.Thereisonlyoneaceofspadesinadeckof
52cards.
(d)Probabilityshouldbecloseto0.Unlessapizzahasspecificallybeen
orderedsothatonlyhalfofitcontainsanypepperonislices,theconsumer
expectsthatapepperonipizzawillhavetheslicesevendistributedover
theentirepizza.Thereisthepossibilityofhumanerrorinplacingthe
pepperoni,butsuchaninitialerrorwouldlikelybedetectedbytheworker
orthesupervisorincharge.
(e)Probability=0.Thelargeoaktreefelltothegroundbecauseof
disease,severeweather,orintentionalcutting.Alarge,heavytree,
respondingtogravitationalforce,hasneverbeenobservedto
spontaneouslyrightitself.Itistruethatsmallertrees,respondingto
circularwindsassociatedwithhurricanesortyphoons,maybendfirstone
wayandthenbacktheotherway.Theprobabilityofsuchtrees
successfullyrightingthemselvesandremaininghealthyisverylow.
(f)Probabilityshouldequal1,giventhatthepersondoingthewashingiscareful
andlooksforallthesocksthatmaybehiddeninotherclothesorthosethatare
Chapter8
droppedsomewhereintheprocess.However,intheexperienceofthisauthor,the
probabilityhoversmysteriouslyaround0.
8.8.
Thinkabouttheexamplesfromyourdailyexperiencesthatwouldillustratethe
statement:Ifasystemcanexistinmorethanoneobservablestate,anychanges
willbeindirectiontowardthestatethatismostprobable.Whichstatewillbethe
mostprobablefor:
(a) waterat5C.
(b) waterat130C.
(c) sugarcrystalsinaglassofhotwater.
(d) adropofperfumeinaroom.
(e) ironfilingsinamagneticfield.(SeeChapter4,Section4.3,Figure4.11.)
Answerto8.8:
Examplesfromdailylifemayinclude,wateratroomtemperaturewhich
existsinaliquidstateratherthansolid(ice)orgaseous(steam).Therefore
thesteamevolvedduringboilingwatercondensesinroomtemperature,
andacubeoficemeltstakenoutfromfreezermeltswhileleftatroom
temperature.
Themostprobablestatesare:
(a)Forwaterat5oCwillbeice.
(b)Forwaterat130oCwillbesteam.
(c)Sugarcrystalswilldissolveinglassofhotwater.
(d)Dropofperfumewillevaporateandspreadthroughthe
room.
(e)Ironfilingswilllineupinthedirectionofmagneticfield.
Section8.3.
CountingMolecularArrangementsinMixtures
8.9.
(a) Findthenumberofpossibledistinguishablearrangementsfortwoidentical
objectsinthefivelabeledboxes(oneobjectperbox)inInvestigateThis8.4.
(b) Howdoesthenumberofarrangementsyoufoundinpart(a)comparewith
thenumberofpossibilitiesfoundinInvestigateThis8.4?Isthistheresultyou
expected?Whyorwhynot?Explainwhytheresultscomeoutastheydo.
Answerto8.9:
(a)Therearetenpossiblearrangements,asshowninthistable.
Chapter8
Arrangement
FirstBox
1.
2.
3.
4.
SecondBox
ThirdBox
FourthBox
FifthBox
X
X
X
X
5.
6.
7.
X
X
X
8.
9.
10.
X
X
X
(b)Thisisthesamenumberofarrangementsthatwerefoundforplacingthree
identicalobjectsinfiveboxes.Toseewhythisisso,comparethearrangements
youtabulatedin8.4Activitywiththissetofarrangements.Foreveryarrangement
inwhichtherearethreeobjects,thereisacorrespondingarrangementherehaving
twoobjectsinpreviouslyunoccupiedboxes.Therefore,threeoccupiedboxesand
twounoccupiedboxeshavethesamenumberofarrangementspossiblefortwo
occupiedboxesandthreeunoccupiedboxes.
8.10.
(a) RefertoFigure8.5.Howmanydistinguishablearrangementsarethereiftwo,
ratherthanthree,solubledyemoleculesareallowedtomixinthetoptwolayers
(6boxes)ofthesystem?Showyoursetofarrangementspictorially.
(b) Compareyourresultfortwodyemoleculesmixingintosixboxeswiththat
showninthefigureforthreedyemoleculesmixingintosixboxes.Explainthe
relationship.
(c) Givenyourcomparisoninpart(b),whatconclusioncanyoudrawaboutthe
affectofnumberofparticlesonthenumberofdistinguishablearrangementsfor
mixingintoafixedvolume(numberofboxes)?Doesthisresultmakesense?
Explain.
Answerto8.10:
(a)Thereare15differentarrangementsfortwodyemoleculesmixing
intosixcells.Thesearethepossibilities.
Chapter8
1.
2.
3.
4.
X
5.
X
6.
X
7.
X
X
8.
X
9.
X
X
10.
X
X
11.
X
X
12.
X
X
13.
X
X
14.
X
Chapter8
15.
X
X
(b)Twodyemoleculemixingintothetoptwolayersofthreecellsproduced15
differentarrangements.InFigure8.5,threedyemoleculesweremixedintothetop
twolayers,producing20differentrelationships.Therearenotthesamenumbersof
possiblearrangements.NotethisresultisdifferentfromtherelationshipofProblem
8.9toInvestigateThis8.4.Here,thetwodyemoleculesinthiscasedonotoccupy
allofthespacesunoccupiedbydyemoleculesinFigure8.5.
(c)Theseresultssuggestthatthemoreparticlesthatmixintoagivenvolume,the
greaterthenumberofarrangements.Thisistruetoapoint.Inthesecountable
systems,whenthenumberofsolutemoleculesexceedsthenumberofsolvent
molecules,thenumberofarrangementsbeginstodecrease.Whenthishappens,you
canthinkofthesoluteandsolventmoleculesexchangingroles,sincethesolventis
usuallytakenasthespeciesinexcess.Inrealsystems,suchasaqueoussolutions,
thisrolereversalcanusuallyonlyoccurforsolutesthataremisciblewiththewater,
solutionsofmethanolorethanol,forexample.
8.11.
InFigure8.6,asthenumberofboxespermoleculeincreasestenfoldfrom2to20,does
thenumberofpossiblearrangementsforthreesolutemoleculesinthecellsalsoincrease
tenfold?Ifitdoesnot,bywhatfactordoesthenumberofarrangementsincrease?
Explainyourreasoning,usinginformationfromFigure8.6.
Answerto8.11:
Asthenumberofcellsincreasesfrom2to20,thenumberofpossiblearrangementsfor
threesolutemoleculesinthecellsincreasesfarmorethantenfold.Figure8.6showsthat
for20cells,thevalueofWisapproximately35,000.Fortwocells,thevalueofWis0.
8.12.
ForsystemslikethoseinSection8.3,thenumberofdistinguishablearrangements,W,of
nidenticalobjectsamongNlabeledboxesis:
W=
N!
(N
Theexclamationpoint,!,denotesafactorial.N!,pronouncedenfactorial,isthe
productofalltheintegersfromNto1.Forexample,5!(5factorial)=54321=120.
(Manyscientificcalculatorshaveafactorialfunctionkeythatgivesyoufactorialsof
numbersupto69limitedbythemaximumvaluethecalculatorcandisplay.)
Chapter8
(a) Usetheformulatocalculatethenumberofdistinguishablearrangementsof3objects
in6boxes.IsyourresultthesameasthenumberofarrangementsshowninFigure8.5?
Explainwhyorwhynot.
(b) Calculatethenumberofdistinguishablearrangementsfortheothermixtures
representedinFigure8.6andcompareyourresultswiththefigure.
(c) Calculatethenumberofdistinguishablearrangementsforamixtureof5objectsin
20boxesandforamixtureof10objectsin20boxes.Doyourresultsreinforcethe
conclusionyoudrewinProblem8.10(c)?Explainwhyorwhynot.
Answerto8.12:
(a)TheformulawithN=6andn=3,is:
W=
6!
6
6
6
=
=
=
=54=20
(6

ThisresultisthesameasthenumberofarrangementsshowninFigure8.5.
(b)IncaseswhereNbecomesquiteabitlargerthann,thefirststepincalculatingthe
ratiooffactorialsistocancel(Nn)!fromthenumeratoranddenominator.Thencancel
n!inthedenominatorwithappropriatetermsinthenumeratorbeforedoingthe
multiplications.ComparetheseresultswiththosegiveninFigure8.6andaccompanying
text.(Theyarethesame.)
N=3,n=3: W=
3!
1
1
= = =1(because0!1)
(3 0! 1
N=6,n=3: W=20(Seepart(a).)
N=9,n=3: W=
9!
9
9
=
=
=347=84
(9
N=12,n=3: W=
12!
12
=
=21110=220
(12

N=15,n=3: W=
15!
15
=
=5713=455
(15

N=30,n=3: W=
30!
30
=
=52928=4060
(30

N=45,n=3: W=
45!
45
=
=152243=14190
(45

N=60,n=3: W=
60!
60
=
=105958=34220
(60

(c)N=20,n=5: W=
20!
20
=
=11931716=15504
(20

Chapter8
N=20,n=10:
W=
20!
20!
=
=184756(usedcalculator)
(20 10!10!
TheconclusioninProblem8.10(c)isreinforcedbytheseresults:themoresolute
moleculesinagivenvolume,thegreaterthenumberofarrangements.Thesame
restrictionapplieshere.ToseetheaffectonWwhenn>N/2,calculateWforN=20and
n=9and11.Istheresultatallsurprising?Why?Canyouexplainwhyyougetthis
result?Whatotherchoicesofnwouldgivesimilarresults?
Section8.4.
ImplicationsforMixingandOsmosisinMacroscopicSystems
8.13.
Imaginealivingplantcellsurroundedbyasemipermeablemembranethroughwhich
watercanpassbutsucrosecannot.Theconcentrationofsucroseinthiscellis0.5%.By
whichoftheseprocessescanyouincreasetheconcentrationofsucroseinthecell?
Explainthereasoningforyourchoiceandthereason(s)yourejecttheothers.
(i) Placethecellinpurewater.
(ii) Placethecellinasucrosesolutionwithaconcentrationgreaterthan0.5%.
(iii) Placethecellinasucrosesolutionwithaconcentrationlessthan0.5%.
(iv) Anyoftheabovewillwork.
Answerto8.13:
(ii)Byplacingthecellinthecontainerwithhigherconcentrationofsucrose,someofthe
waterinsidethecellwilldiffuseintothecontainer.Thereforetheconcentrationofthe
sucroseinthecellwouldincrease.(i)willcausewaterfromthecontainertopassintothe
cell,thusdilutingtheconcentrationofsucroseinthecell.(iii)willcausewaterfromthe
containertopassintothecelldilutingthesugarconcentrationinanefforttocreatethe
sameconcentrationofsugarinsideandoutsidethecell.
8.14.
(a) StartingwiththeinitialarrangementofsoluteandsolventmoleculesshowninFigure
8.7(a),willthenumberofmoleculararrangementsincreaseordecreaseafterosmosis
takesplace?Explain.
(b) DrawadiagrammodeledafterFigure8.7(b)toshowwhatwillhappenifsixofthe
ninesolventmoleculespassfromthesolventintothesolution.Howmanydistinguishable
arrangementsofthesolution,thesolvent,andthetotalsystemarepossibleafterthis
changehasoccurred?Isthechangelikelytooccur?Explainwhyorwhynot.
(c) Istheprocessinpart(b)osmosisorreverseosmosis?Explain.
Answerto8.14:
Chapter8
(a)Thenumberofpossiblemoleculararrangementswillincreaseafterosmosis
takesplace.Themaximumnumberofmoleculararrangementsresultsfrom
spreadingthesolutethroughoutthelargestvolumeofsolution,andthevolumeof
solutionisincreasingbecauseoftheosmosisofsolventmoleculesintothe
H
O
H
O
H
O
2
2
2
H
O
H
O
H
O
H
O
H
O
H
O
H
O
2
2
2
2
2
2
2
H
O
H
O
2
2
H
H
O
H
H
H
O
H
2O
2InitialCon
2O
2O H
2O
2Fina
2OH
2O
solution.
(b)Note:Thesoliddotindicatessolutemolecules.
(c)Thisprocessthatistakingplaceisosmosis,notreverseosmosis.In(forward)
osmosis,thetendencyisforsolventmoleculestomovethroughasemipermeable
membrane,dilutingthesolution.Thisincreasesthenumberofmoleculararrangements
forthesolution,providingthedrivingforceforthechange.
8.15.
Theconcentrationofsoluteparticlesinaredbloodcellisabout2%.Problem8.4states
thatredbloodcellsaresusceptibletocrenationorhemolysis.Redbloodcellswould
probablyshrivelthemostwhenimmersedinwhichofthefollowingsolutions?Explain
thereasoningforyourchoiceandthereason(s)yourejecttheothers.(Sucrosecannot
passthroughthemembraneofbloodcells.)
(i) 1%sucrosesolution
(ii) 2%sucrosesolution
(iii) 3%sucrosesolution
(iv) distilledwater
Answerto8.15:
(iii)Whenredbloodcellsareplacedinthissolution,waterwillmoveoutofthered
bloodcells,causingthecellstoshrivel.
Chapter8
Section8.5.
EnergyArrangementsAmongMolecules
8.16.
(a) Ifenergyistransferredfromawarmerobjectincontactwithanidentical,butcooler,
object,howdoesthenumberofenergyarrangementsafterthetransfercomparetothe
numberbeforethetransfer?Explain.
(b) Whennetenergytransferstops,howwillthefinaltemperaturesoftheobjects
comparewiththeoriginaltwotemperatures?Explain.
Answerto8.16:
(a)Initially,thenumberofpossiblearrangementsofenergyquantainthewarmer
objectisgreaterthanthenumberinthecoolerobject.Asheatenergyis
transferred,thenumberofarrangementsinthewarmerobjectwilldecreaseand
thenumberofarrangementsinthecoolerobjectwillincreaseuntilthetwoobjects
reachthesamefinaltemperature.
(b)Thetwoobjectsarespecifiedasbeingidenticalsotheirmassesmustbethesameand
theymustbemadeofthesamematerial.Thefinaltemperaturewillbehalfwaybetween
thewarmerandthecoolertemperatures.
8.17.
Considertwoidenticalfouratomsolids,onehavingfourquantaofenergyandtheother
havingten.
(a) Whatobservablepropertydiffersbetweenthesetwosolids?
(b) Allowthreequantaofenergytobetransferredfromthesolidwithtenquantatothe
solidwithfourquantaofenergy.UsethedatafromFigure8.9todeterminewhetherthis
energytransferislikely,explainingyourreasoning.
(c) Comparetheresultfrompart(b)totheresultobtainedinWorkedExample8.8.In
bothcases,quantaweretransferredfromawarmerfouratomsolidtoacoolerfouratom
solid.Arebothtransferslikelytotakeplace?Explainthereasoningforyourresponse.
Answerto8.17:
(a)Temperaturedifferenceisthebulkpropertythatdistinguishesthefouratom
solidwitheightenergyquanta(whichhasthehighertemperature)fromthefour
atomsolidwithfourenergyquanta(whichhasthelowertemperature).
(b)ThesevaluesaretakenfromthegraphinFigure8.8.
EnergyContent,
lnW
3.6
37
fouratomsolid
4quanta
Chapter8
7quanta
4.8
120
10quanta
5.6
285
Thenumberofarrangementsinasystemistheproductofthenumberof
arrangementspossibleineachcomponentofthesystem.
Fortheinitialstate,Wtot=W10quantaW4quanta
=28537=10,545
Forthefinalstate,afterthetransferoftwoquanta,
Wtot=W7quantaW7quanta
=120120=14,400
Thereareabout1.4timesasmanywaystoarrangetheenergyquanta
whenbothsolidshavesevenquantacomparedtowhenonesolidhasfour
andtheotherhasten.Thelargerthenumberofpossiblearrangements,the
morelikelyitisthatagivenconditionwillexist.
(c)Inthisexample,thenewnumberofwaystoarrangetheenergyquantawhenthe
transferhasoccurredisabout1.4timesasmanyastheoriginalnumberofpossible
arrangements.InWorkedExample8.8,inwhichtwoquantaweretransferredfroma
fouratomsolidinitiallyhavingonlysixquanta,theratiowasabout1.2timesas
many.Thisillustratesthegeneralprinciplethatthetransferoftwoquantaofenergy
fromanobjecthavingalargerinitialnumberofquantahaslesseffectonthenumber
ofdistinguishablearrangementsthandoesthetransferoftwoquantafromanobject
initiallyhavingfewerquanta.
8.18.
Choosethebestanswer.Explainthereasoningforyourchoiceandthereason(s)you
rejecttheothers.Whichstatementdescribeswhythermal(heat)energymovesfromahot
bodytoacoldbody?
(i) Thereismorethermalenergyinthefinalstate.
(ii) Thereismorethermalenergyintheinitialstate.
(iii) Thenumberofdistinguishablearrangementsfortheenergyquantaishigherinthe
finalstate.
(iv) Thenumberofdistinguishablearrangementsfortheenergyquantaishigherinthe
initialstate.
Answerto8.18:(iii)
Chapter8
Thebestansweris(iii).Energyisconservedinthisprocessandnoworkisdone,sothe
amountofthermalenergyisconstant.Thus,statements(i)and(ii)areincorrect.Ifthe
numberofarrangementswerehigherintheinitialstate,asstatement(iv)says,thenno
transferofenergywouldoccur,sincespontaneouschangesalwaysoccurinadirection
thatincreasesthenumberofdistinguishablearrangements.
8.19.
ForsystemslikethoseinSection8.5,thenumberofdistinguishablearrangements,W,of
nidenticalquantaamongNatomsinasolidis:
W=
(N

SeeProblem8.12forinformationaboutfactorials.
(a) Usetheformulatocalculatethenumberofdistinguishablearrangementsof2quanta
among4atoms.Isyourresultthesameasthenumberofarrangementsyoufoundfortwo
toothpicksinfourcandiesinInvestigateThis8.7?Explainwhyorwhynot.
(b) Calculatethenumberofdistinguishablearrangementsforthecasesrepresentedin
Figure8.9andcompareyourresultswiththefigure.
(c) Considerthetransferoffourquantaofenergyfroman8atomsolidwithaninitial16
quantatoanidentical8atomsolidthatinitiallyhas10quanta.Isthistransferlikelyto
occur?Whyorwhynot?Isthereanothertransferthatismorelikelytooccur?Ifsowhat
isitandwhyisitmorelikely?
Answerto8.19:
(4
5!
5
=
=
=10

3!2!

ThisisthesamenumberofarrangementsyoufoundinInvestigateThis8.7.Sincethe
toothpicksincandiessystemmodelsthequantainatomssystem,weexpecttheresultsto
bethesame.
(b)ComparethefollowingresultswiththoseshowninFigure8.9.(Theyarethesame.)
(a)
N=4,n=2: W=
N=4,n=0: W=
(4
=1(because0!1)

N=4,n=1: W=
(4
4!
=
=4

3!1!
N=4,n=2: W=10(Seepart(a).)
N=4,n=3: W=
(4
6!
=
=20

3!3!
N=4,n=4: W=
(4
7!
=
=35

3!4!
Chapter8
N=4,n=5: W=
(4
8!
=
=56

3!5!
N=4,n=6: W=
(4
9!
9
=
=
347=84

3!6!
N=4,n=7: W=
(4
10!
10
=
=
=1034=120

3!7!

N=4,n=8: W=
(4
11! 11
=
=
=1153=165

3!8!

N=4,n=9: W=
(4
12!
12
=
=
=21110=220

3!9!

N=4,n=10: W=
(4
13!
13
=
=
=13211=286

3!10!

(c)Theinitialstateofthesystemdescribedinthispartistwo8atomsolidswith10and
16quanta,respectively.Thenumberofdistinguishablearrangementsofeachsolidis:
(8 17
W10=
=
=1741213111=19448

W16=
(8
23
=
=23111119317=245157

TheoverallnumberofdistinguishablearrangementsisWtotal=W10W16=4.7678109.
Aftertheproposedenergytransfer,thetwosolidshave14and12quanta,respectively.
Thenumberofdistinguishablearrangementsofeachsolidis:
W14=
(8
21
=
=1119317815=116280

(8 19
=
=1911723213=50388

TheoverallnumberofdistinguishablearrangementsisWtotal=W14W12=5.8591109.It
looksasthoughthetotalnumberofarrangementshasincreasedslightlyinthischange,
buttheenergytransferendsupwiththesolidsatdifferenttemperaturesandtheoriginally
cooleroneisnowwarmer.Weknowthatthisisnotalikelyprocess.Whatweneedto
findisthenumberofarrangementsavailablewhenjustenoughquantahavebeen
transferredtobringbothsolidstothesametemperature(thatis,withthesamenumberof
quanta,13).Inthiscase,thenumberofdistinguishablearrangementsofeachsolidis:
W12=
W13=
(8 21
=
=111931781514=1627920

W13=1627920
TheoverallnumberofdistinguishablearrangementsisWtotal=W13W13=2.65011012.
Asyousee,thissystemoftwoidenticalsolidswiththe26quantadividedequally
Chapter8
betweenthemhasabout450timesasmanyarrangementsastheonewherequantumis
transferredfromonesolidtotheother(the14and12casejustabove).Thisequal
distributionisbyfarthemostprobableforthissystemandexplainswhytheproposed
transferoffourquantaisnotobserved.
Section8.6.
Entropy
8.20.
Statethesecondlawofthermodynamicsinwordsandasanequation.
Answerto8.20:
Thetotalentropyofanisolatedsystemwillalwaysincreaseforanychange.Or
ObservedChangesalwaystakeplaceinadirectionthatincreasesnetentropy.S=klnW.
8.21.
Whatisthedifferencebetweenpositionalentropyandthermalentropy?
Answerto8.21:
Positionalentropydependsonthenumberofdifferentdistinguishablearrangementsina
system.Thermalentropyreferstoenergyquantabeingexchangedamongmoleculesto
producethedistinguishablearrangements.
8.22.
Thesecondlawofthermodynamicsstatesthatobservedchangesalwaystakeplaceina
directionthatincreasesnetentropy.Isthisstatementtrueifonlythermalentropyis
considered?Ifonlypositionalentropyisconsidered?Givethereasonsforyouranswers.
Answerto8.22:
Thestatementmayormaynotbetrueforthermalentropyorpositionalentropyif
consideredasseparatefactors.Thestatementistrueifchangestakeplacethatincrease
thetotalnetentropy.Whetherthenetchangeisdominatedbythethermalentropychange
orbythepositionalenergychangedependsonthesystembeinginvestigated.See,for
example,Figures8.10and8.11.
8.23.
Whyisitpossibletotabulateabsoluteentropies,butnotabsoluteenthalpies?Thatis,why
doesAppendixXXlistSo(notSo)andHfo,(notHo)?
Answerto8.23:
Wecandetermineabsoluteentropiesforcompoundsandelementsbecausethereisa
referencepointforentropiesabsolutezero.Weknowthatthisisthetemperatureat
whichthereisnodisorderandallparticlesareintheirlowestenergystate.Thereforethe
entropyatthistemperatureiszero,entropiesatothertemperaturescanbecalculated
relativetoSat0K.Thereisnosuchreferencepointforenthalpyandsowecanonly
calculatechangesinenthalpyfromonestatetoanother.
Chapter8
8.24.
Answereachofthefollowingstatementseithertrueorfalse.Ifyoudecidethatthe
statementisfalse,writethecorrectstatement.
(a) Theentropyofamoleofsolidmercuryishigherthanamoleofmercuryvapor.
(b) Ifthenetentropyincreasesduringaprocess,theprocessisspontaneous.
(c) Theentropyofasystemdependsonthepathwayittooktoitspresentstate.
(d) Themorepositiveitsnetentropychange,thefastertheprocess.
(e) Theentropyofoneliterofa0.1MaqueoussolutionofNaClislowerthanthe
entropyoftheundissolved0.1moleofNaClandoneliterofwater.
(f) Theentropyislargerforasystemoftwoidenticalblocksofcopperinwhichthe
temperatureofeachblockis60Cthanforthesameblocksofcopperifonehasa
temperatureof20Candtheotherisat120C.
(g) Thereisnoreferencepointformeasuringentropy.
Answerto8.24:
(a)False.Gasphaseshavehigherpositionalentropybecausetheyaremuchless
ordered.
(b)True.Spontaneouschangesalwaystakeplaceinthedirectionthatincreases
netentropy.
(c)False.Entropyisastatefunctionthatisindependentofpathway.
(d)False.Positivechangeofentropyindicatesthatthechangeisfavorable,butit
doesnotindicatetherateoftheprocess.
(e)False.Theentropyofthemixtureisgreaterthantheentropyfortheseparated
componentsbecausemoremoleculararrangementsexistforsystemswithmixed
components.
(f)True.Therearemoreenergyarrangementandgreaterentropyforsystemsin
whichtwoobjectshavethesametemperaturethanwhenoneobjectiswarmer
thantheother.
(g)False.Thereferencepointformeasuringentropyisabsolutezero,atwhich
temperaturetheentropyofperfectlyorderedsubstanceiszero.Absolutezerohasnever
beenexperimentallyachievedthough.
8.25.
Predictwhetherthepositionalentropychangeineachoftheseprocesseswillbepositive
ornegative.Explainyourreasoningineachcase.
(a) precipitationofBaSO4uponmixingBa(NO3)2(aq)andH2SO4(aq)
Chapter8
(b) coolingoftheammoniagasfromroomtemperatureto50C,whichresultsin:
NH3(g)NH3(l)
(c) formationofammoniainthereaction:N2(g)+3H2(g)2NH3(g)
(d) decompositionofCaCO3inthereaction:CaCO3(s)CaO(s)+CO2(g)
(e) formationofNOinthereaction:N2(g)+O2(g)2NO(g)
Answerto8.25:
(a)Theentropychangeofthesystemwillbenegativebecausedissolvedionsof
Ba2+andSO42havehigherpositionalentropythanthesameionsconfinedinthe
crystallattice.
(b)Theentropychangewillbenegativebecauseammoniumgashashigher
positionalentropythanammoniumgasinthecondensedphase.
(c)Theentropychangewillbenegativebecausetherearefewermolesofgasin
theproductthaninthereactants.Thismeansthatsomepositionalentropywas
lostinthisprocess.
(d)Theentropychangewillbepositivebecauseasolidisconvertedintoasolid
andgas.Somepositionalentropyisgainedinthisprocess.
(e)Thechangeinentropyishardtopredictinthiscase,becauseofthesamenumberof
molesofgasisinvolvedinthereactantsandinproduct.
8.26.
Occasionallyonehearsthatevolutionviolatesthesecondlawofthermodynamics.The
claimisthattheincredibleprecisionwithwhichthehumanbodyisarrangedcouldnot
haveevolvedfromlesscomplexorganismswithoutviolatingthesecondlawof
thermodynamics.Whatistheproblemwiththisargument?
Answerto8.26:
[ThisproblemwouldbebetterplacedinSection8.14.]
Thesecondlawofthermodynamicsstatesthatthenetentropychange(accountingforthe
systemandsurroundings)foraspontaneousprocessispositive.Ifachangeinasystem,
suchasevolvingmorecomplexorganismsfromsimplerones,reducesthenumberof
possibledistinguishablearrangementsofthecomponents,thenthechangeinthesystem
canonlybespontaneousifitisaccompaniedbyanincreaseinthenumberof
arrangementsofitssurroundings.Inthecaseofevolution(oreventheformationofthe
firstmostprimitivecell),energyisrequiredtobringthecomponentstogetherinjustthe
rightway(toformthecorrectbondingarrangements,forexample).Inalmostallcases,
thisenergyissuppliedbyelectromagneticradiationfromthesunthatiscapturedin
variouswaysonearthandusedtobringabouttheevolutionarychanges.Thenuclear
Chapter8
processesinthesuntransferaprodigiousamountofenergytoitssurroundings,sothere
areenormousincreasesintheirentropy.Thus,theentropyincreaseofthesunandits
surroundingsaremuchmorethanenoughtodrivetherelativelysmallevolutionary
changesthatreducetheentropyoftheevolvingsystem.
8.27.
Doyouthinkitisscientificallyrighttoblamethesecondlawofthermodynamicsfor
clutterinafriendsworkspace?
Answerto8.27:
Directlyapplyingtheprinciplesofthermodynamicstoworkspaceobjectsisnotagood
idea.Inthermodynamics,weassumethattheenergyofthesystemissufficientthatall
possiblearrangementscanbereachedfromoneanother.Forexample,gasmoleculesare
inconstantmotion,sothesystemcaneasilymovefromonearrangementtoanother.On
theotherhand,ifbooksarearrangedonashelf,weknowthat(barringsomekindofhigh
energyintervention)theyaregoingtostayarrangedontheshelf.Theylackthekinetic
energy(motion)tomakeatransitiontootherarrangements.So,thermodynamicsisnot
responsibleforclutterinafriend'sworkspace.
8.28.
Foreachoftheseisomericpairsofmolecules,predictwhichoneofthepairwillhavethe
higherentropyunderthesamepressureandtemperatureconditions.Explainthebasisof
eachprediction.
(a) butanoicacid,
(b) pentane,
H 3C
H2
C
(c) cyclopropane,
H 3C
C
H2
H2
C
H2
C
C
H2
O
C
OH
or
dioxane,
H2C CH 2
O
O
H2C CH 2
CH 3
CH 3
H2C CH 2
C
H2
or
2,2dimethylpropane,
or
propene, H3C
H
C
H 3C C
CH3
H 3C
CH 2
Answerto8.28:
(a)butanoicacid.Therearemorepositionalarrangementsforbutanoicacidduetobond
rotationsthantheconstrainedringofdioxane.
(b)pentane.Asabove,therearemorepositionalarrangementsforpentaneduetobond
rotations.Thesymmetryin2,2dimethylpropaneoffersfewerpositionalarrangements
thaninpentane.
(c)propene.Therearemorepositionalarrangementsforpropenethanforthe
constrainedringofcyclopropane.
Chapter8
Section8.7.
PhaseChangesandNetEntropy
8.29.
Considerthisstatement:Observedphasechangesalwaystakeplaceinadirectionthat
increasesentropy.Isthisstatementtrue?Criticallyanalyzethisstatementforscientific
accuracy,explainingyourreasoning.
Answerto8.29:
No,thisstatementisnottrueforallcases.Thischapterstartedwiththeobservationthat
complex,highlyorderedsnowflakescanformfromliquidwater.Thisapparently
spontaneousorderingdoesnotincreaseentropyforthewatermoleculesinvolvedinthe
change.Thedifficultyisthatnetentropychange,whichdoesincreaseinassnowflakes
form,hasnotbeenspecifiedinthegivenstatement.Netentropychangereferstothesum
ofalltheentropychangesforboththesurroundingsandthesystem.Asthesnowflakes
form,thereisadecreaseinpositionalentropyofthesystem.Thischangedoesnotfavor
thephasechange.However,thereisanincreaseinthermalenergyofthesurroundings
thatdoesfavorthephasechange.Apositivevaluefornetentropychange,whichmust
considerbothsystemandsurroundings,doesfavorobservedphasechanges.
8.30.
Whichmemberofeachpairhasthehigherentropy?Ineachcase,explainyourreasoning.
(a) H2O(s)
or
H2O(l)
(b) CaCl2(aq)
or
CaCl2(s)
(c) 5.0gH2O(l)at1C
or
5.0gH2O(l)at60C
(d) H2O(g)
or
H2O(l)
(e) CO2(g)
or
CO2(s),dryice
Answerto8.30:
(a)H2O(s)
(b)CaCl2(aq)
(c)5.0gH2O(l)at60.oC
(d)H2O(g)
(e)CO2(g)
8.31.
Thepositionalentropychangeforwaterfreezingisnegative.Explainhowitispossible
forwatertofreeze.
Answerto8.31:
Whenwaterfreezes,theentropychangeofthesystemisnegative,Swater<0.The
thermalenergychangewhenthewaterfreezes(andmanyhydrogenbondsform)is
Chapter8
negative,Hwater<0,andthethermalenergychangeinthesurroundingsispositive,
Hsurround=Hwater.Hsurround/T=Ssurround,whereTisthekelvintemperatureofthe
surroundings.Ifthethermalsurroundingsareatatemperaturelessthan273K,Ssurround+
Swater=Snet>0andtheprocessisspontaneous.Thus,waterfreezes,ifthetemperature
ofsurroundingsisbelow273K.
8.32.
Foreachofthesechanges,explainifthepositionalentropyofthesystemincreases,
decreases,orstaysthesame.
(a) SolidCO2(dryice)changestocarbondioxidegas.
(b) Liquidethanol(C2H5OH)freezes.
(c) Mothballsmadeofnaphthalene(C10H8)sublime.
(d) Plantmaterialsburntoformcarbondioxideandwater.
Answerto8.32:
(a)Thepositionalentropyincreases.Therearemanymorepossiblearrangements
ofCO2moleculesinthegasphasethaninthesolid.
(b)Thepositionalentropydecreases.Therearefewerpossiblearrangementsof
ethanolmoleculeswheninthesolidstatethanwhenintheliquidstate.
(c)Thepositionalentropyincreases.Therearemanymorepossiblearrangements
ofmoleculesofnapthaleneinthegasphasethaninthesolidstate.
(d)Thepositionalentropyincreases.Therearemanymorepossiblearrangementsof
moleculesinthegasesthatresultfromcombustionoftheplantmaterial.
8.33.
Consideranisolatedsystemwhereaballooncontainingsteam,H2O(g),isimmersedintoa
thermallyisolatedcontainerofliquidwaterat10.0C.
(a) Whatwillhappentothesteamintheballoon?
(b) Doestheentropyofthewaterintheballoonincreaseordecrease?Explain.
(c) Doestheentropyofthewateroutsidetheballoonincreaseordecrease?Explain.
(d) Isthenetentropychangeforthisisolatedsystempositiveornegative?Explain.
Answerto8.33:
(a)Itwillcondense.
(b)Itwilldecreaseasthewatercoolsandchangesfromagastoaliquid.Both
thepositionalandthermalentropyofthewaterwilldecrease.
(c)Itwillincrease.Thewateroutsidetheballoonabsorbsheatsoitsthermal
entropywilincrease.
(d)Thetotalentropychangewillbepositive.Otherwise,thechangewouldnotoccur.
Chapter8
8.34.
(a) ThemeltingpointforH2Sis187K(86C).UseadiagramsimilartoFigure8.11to
explaintheentropychangesforthesystem,thesurroundings,andthenetentropychange
formeltingH2Sattemperaturesabove187K.
(b) HowwilltheentropydiagramdifferifliquidH2SchangestosolidH2Sat187K?
(c) Thephasechangeforwaterchangingfromsolidtoliquidtakesplaceat0C
(273K).Explainwhythetwosubstanceshavesuchdifferentmeltingpoints.Hint:H2S
formsonlyweakhydrogenbonds.
Answerto8.34:
(a)Meltingincreasespositionalentropy.
Entro
Entropy
the
surr
ound
the
system
forso
forsolid
toliq
toliqu
is<0
Fina
is>0
the
syst
and
surr
oun
Initialen
the
system
andNetE
surr
ounding
Cha
(b)Freezingdecreasespositionalentropy.
NetEnt
Chang
Fina
the
syste
and
surr
oun
Initialen
the
system
and
surr
ounding
Entro
Entropy
the
surr
oundi
the
system
forliq
forliqui
tosol
tosolid
is<0
is>0
Chapter8
(c)Thedifferencecanbeexplainedbyhydrogenbonding.Thistypeofintermolecular
forceisamajorfactorinwater,butdoesnottakeplaceinH2S.
8.35.
Arrangethecompoundsammonia,methane,andwaterinorderofincreasingentropyof
vaporization,Slg.Explainthereasoningforyourordering.Hint:ReviewChapter1,
Section1.7.
Answerto8.35:
Inorderofincreasingentropyofvaporization:methane>ammonia>water.Water
formsthestrongesthydrogenbondswithotherwatermolecules,followedbyammonia.
Thus,withhydrogenbondedmoleculesinthegasphase,therewillbelessentropythan
comparedtononhydrogenbondedmoleculessuchasmethane.
8.36.
Thecompletecombustionofethanol,C2H5OH(l),isrepresentedbythisequation:
C2H5OH(l)+3O2(g)2CO2(g)+3H2O(l)
Forthecombustionofonemoleofethanolunderstandardconditions,thestandard
entropyandstandardenthalpychangesare139J.K1and1367kJ.mol1,respectively.
(a) Commentonthesevaluesintermsofpositionalentropies.
(b) Commentonthesevaluesintermsofbondformation.
(c) Consideringpositionalentropy,isthisreactionfavoredtoproducecarbondioxide
andwaterunderstandardconditionsoftemperatureandpressure?Whyorwhynot?
Answerto8.36:
Chapter8
(a)Thisreactionchanges3molesofgas(and1moleofthecondensedliquid
phase)into2molesofgas(and3molesofcondensedliquidphase).Thismeans
thatthereisadecreaseinpositionalentropy.Consideringthat4molesofreactants
havechangedto5molesofproducts,thismightbeexpectedtoincreasepositional
entropy.Thefactthattheactualvalueisnegaiveimpliesthatthefirsteffectof
reducingthenumberofmolesofgasmustbethecontrollingfactorintheoverall
entropyincrease.
(b)Theoverallreactionishighlyexothermic,releasing1367kJ.mol1.Thebond
enthalpiesoftheproductswherebondsareformingmustbegreaterthanthoseof
thereactants,whereenergyisrequiredtobreakbonds.
DHsystem
o
o
(c) Snet = DSsystem
andthismeans
T
o
Snet
= 138J mol 1 K 1
1367kJ mol 1 10 3 J
298K
1kJ
o
DSnet
= +4449J
Thelargepositivevaluemeansthatthecombustionishighlyprobablebasedon
positionalentropyconsiderations.Rememberthatitalsoisanexothermicreaction.For
bothreasons,ethanolisusedinmanytypesofautomotivefuelsasanoctaneboosternow
thatleadhasbeeneliminatedfromgasolineintheUS.
8.37.
Considertheprocess:Br2(l)Br2(g)
(a) CalculateHoandSoforthisphasetransition.UsethedatainAppendixXX.
(b) CalculateSonetforthisphasetransitionat:
(i)0.0C(ii)40C(iii)70C.
(c) Atwhattemperaturedoesthebrominebegintoboil?Explainthereasoningyouuse
todeterminetheboilingpoint.
Answerto8.37:
(a)Ho=HofBr2(g)HofBr2(l)=30.90=30.9kJ.mol1
So=SofBr2(g)SofBr2(l)=245.46152.2=93.3J/K.mol
(b)Sonet=SoHo/TremembertoconverttoK(add273)
(i)0C:Sonet=30.9kJ/mol30.9x103J/mol/273K=19.8J/K
(ii)40C:5.42J/K
(iii)70C=3.21J/K
Notethattheprocessbecomesspontaneousbetween40Cand70C.
(c)WhenSo=Ho/TsubstitutingingivesTbp=58.2C.
Chapter8
8.38.
UsetheHoandSoforH2O(l)H2O(g)toshowhowtemperatureinfluenceswhether
theincreaseintheentropyofthesystemwillfavorthephasechange.
Answerto8.38:
Hforwaterboilingis+(heatenergymustbeputintothesystem)sothiswillcontribute
toanegativenetentropychange,sinceSonet=SoHo/T,butSis+(gashasahigher
entropythanliquid)soatthetemperaturerises(whichmakestheHo/Ttermsmaller)
thenetentropychangewillbecomedominatedbytheSsystemterm.
8.39.
(a) Usethestandardentropiesandstandardenthalpiesofformationforliquidand
gaseousethanal,CH3CHO,fromAppendixXXtofinditsstandardentropyof
vaporization,Solg,andstandardenthalpyofvaporization,Holg.
(b) Whatistheboilingpointofethanal?Explainthereasoningyouusetogetyour
result,includinganyassumptionsyoumake.
Answerto8.39:
(a)Holg=HofCH3CHO(g)HofCH3CHO(l)=166.36kJ.mol1(192.30kJ.mol1)
=25.94kJ.mol1
Solg=SofCH3CHO(g)SofCH3CHO(l)=264.22J.K1.mol1160.2J.K1.mol1=
104.02J.K1.mol1;Snet=0.
(b)Sincethereisaphasechange,Snet=0.Therefore,Solg=Holg/T;T=25.94
kJ.mol1/0.104J.K1.mol1;T=249K.
Note:AccordingtotheMerckIndex,theactualboilingpointforethanalis294K.The
thermodynamicvaluesarecorrectaswell.Thediscrepancymaybeduetothe
observationthatthethermodynamicdataforthisreactionmayneedtoberemeasured
thisisoutsidethescopeofthisproject.Studentsshouldnotethatnotalldataintablesare
necessarilycorrect.
(a) Usethestandardenthalpiesofformationforliquidandgaseousmethanol,CH3OH,
fromAppendixXXtofinditsstandardenthalpyofvaporization,Holg.
(b) Theboilingpointofmethanolis65.0C.Whatisthestandardentropyof
vaporization,Solg,formethanol?Explainthereasoningyouusetogetyourresult,
includinganyassumptionsyoumake.
(c) UsethedatainAppendixXXtocalculateSolgformethanol?Howdoesyourvalue
fromthesedatacomparetoyourresultinpart(a)?Howwouldyouexplainany
difference?
Answerto8.40:
Chapter8
(a)Holg=HofCH3OH(g)HofCH3OH(l)=200.66(238.86)=38.20kJ.mol1
(b)Weassumethatthesystemisatconstantpressureandtemperature.The
temperaturesofthesystemandthethermalsurroundingsarethesame.Sinceitisaphase
changeSnetisequalto0.Therefore,Solg=Holg/T;Solg=38.20103J.mol1/338
K;Solg=113.02J.K1.mol1.
(c)FromthedatainAppendixXX,Solg=239.81J.K1.mol1126.8J.K1.mol1=
113.01J.K1.mol1.Thereisgoodagreementbetweenthisvalueandthecalculatedresult
frompart(b).
GibbsFreeEnergy
Considerthecompletecombustionofethanol,C2H5OH(l),giveninProblem8.36.Forthe
combustionofonemoleofethanolatstandardconditions,thestandardchangeinGibbs
freeenergyis1325kJ.mol1at298K.
(a) DoesthevalueoftheGibbsfreeenergychangepredictthisreactionwilltakeplace
at298K?Explain.
(b) Atwhattemperaturewillthisreactionbeatequilibrium?Justifyyourresponse.
(c) Discusswhythenumericalvalueyoucalculatedinpart(b)islikelytobeinerror.
Answerto8.41:
(a)Yes,thevalueoftheGibbsFreeEnergydoespredictthatthisreactionwilltakeplace.
Thevalueis<0,sothechangeispossibleatthistemperatureandpressure.
(b) G = DH system TDSsystem Ifthesystemisatequilibrium,G=0.
0 andT=+9905K
(c) Both H and S areassumedtobeconstantoverthetemperaturerangefrom273

Kto9905K.Thisisdefinitelynotavalidassumptionforsuchalargetemperaturerange.
8.40.
Considerthereaction:2H2O2(g)2H2O(g)+O2(g).Forthisreactionat298K,H=
106kJandS=58JK1.WouldyouexpectH2O2(g)tobestableorlikelytodecompose
at298K?Explainyourreasoning.
Answerto8.42:
G=106Jx103J(298Kx58J/K)=123x103J.ThedecompositionofH2O2(g)is
highlyspontaneous,soatthistemperatureH2O2(g)isnotstable.
8.41.
Acertainreactionisnonspontaneousat300K.Theentropychangeforthereactionis
130JK1.
(a) Isthereactionendothermicorexothermic?Explainyourresponse.
Chapter8
(b) WhatistheminimumvalueofHforthisreaction?Explainthereasoningforyour
answer.
Answerto8.43:
(a)ThisreactionisendothermicsinceHispositive.
(b)Forthisreactiontobenonspontaneous,Hmustbelargerthan39kJ.
8.42.
Thestandardenthalpyofformation(Hof)andthestandardfreeenergyofformation
(Gof)ofelementsarezero.Butthestandardabsoluteentropy(So)isnotzero.Explain
why.
Answerto8.44:
BothH0fandGofarethereferencevalueswhichbydefinitionforelementsintheir
moststableformsareequalzero.Thesevaluesarearbitrarydefined,becausetheycannot
bemeasured.Ontheotherhand,theabsolutestandardentropyvaluescanbedetermined.
8.43.
ChangescanbecharacterizedbythesignsofHandS,for
thesystem,asillustratedinthisdiagram.Forexample,
processeswithpositivevaluesforbothHandSfallinthe
quadrantofthediagramlabeled,B.
(a) Whichquadrant(s),A,B,C,or,D,representschanges
orprocessesthatarealwaysspontaneous?Explainyour
choice(s).
(b) Whichquadrant(s)representschangesorprocessesthatareneverspontaneous?
Explainyourchoice(s).
(c) Twoofthequadrantsrepresentprocessesthatcouldpossiblybespontaneous,
dependinguponthetemperatureatwhichtheprocessesarecarriedout.Whichquadrants
arethese?Whichquadrantrepresentsprocessesthatcouldpossiblybespontaneousat
hightemperatures?Whichquadrantrepresentsprocessesthatcouldpossiblybe
spontaneousatlowtemperatures?Clearlyexplainthereasoningforyourchoices.
(d) Whichquadrantrepresentsthefreezingofaliquid?Explain.
(e) Whichquadrantrepresentsthemeltingofasolid?Explain.
Answerto8.45:
TheanswerstothisproblemarebasedontherelationshipG=HTSandthe
criterionforspontaneity,G<0.
(a)ProcessesthatfallinquadrantAarealwaysspontaneous.AnegativeHandpositive
SalwayscombinetogiveanegativeG.
Chapter8
(b)ProcessesthatfallinquadrantDareneverspontaneous.ApositiveHandnegative
SalwayscombinetogiveapositiveG.
(c)QuadrantCrepresentsthefreezingofaliquid.Inthisprocess,bothSandHare
negative,sothesignofGdependsonthevalueofT.AtalowenoughvalueofT,|H|>
|TS|andGisnegativetheliquidfreezes.
(d)QuadrantBrepresentsthemeltingofasolid.Inthisprocess,bothSandHare
positive,sothesignofGdependsonthevalueofT.AtahighenoughvalueofT,|H|<
|TS|andGisnegativethesolidmelts.
8.44.
Atacertaintemperature, G forthereactionCO2(g) C(s)+O2(g),isfoundtobe

42kJ.Whichofthesestatementsiscorrect?Explainthereasoningforyourchoiceand
thereason(s)yourejecttheothers.
(i) Thesystemisatequilibrium.
(ii) Theprocessisnotpossible.
(iii) CO2willbeformedspontaneously.
(iv) CO2willdecomposespontaneously.
Answerto8.46:Thecorrectstatementis(ii)becausea+Gvalueindicatesthatthe
reactionisnotfavoredinthedirectionthatitiswritten.Statement(i)isrejectedbecause
ifthesystemisatequilibrium,Gwouldbeequalto0.Statement(iii)isrejected
becauseCO2willformspontaneouslyonlyinthereversereaction.Statement(iv)is
incorrectbecauseCO2willdecomposespontaneouslywitha+Gvalue.
8.45.
Considertheoxidationofmethane:CH4(g)+2O2(g)CO2(g)+2H2O(g).
(a) Byinspection,predictthechangeofentropy.Explainthebasisofyourprediction.
(b) UsethevaluesofHofandGoffromAppendixXXtocalculatethechangein
standardenthalpy,freeenergy,andentropyforthisreactionat25Cand1bar.Explain
theproceduresyouuse.
(c) Wasyourpredictioninpart(a)closetothecalculatedvalueinpart(b)?Explainwhy
orwhynot.
Answerto8.47:
(a)Bylookingatthereaction,wecanpredictthatthechangeinentropywillbe
smallbecause3moleculesofgaseousreactantswouldproduce3moleculesof
products.However,acloserlookatthenatureofthereactantsandproductsmay
leadtothinkingthatbecausewaterisbeingformed,eveninthegasphase,water
Chapter8
moleculesmightundergosomeorganizationviahydrogenbonds.Wemaypredict
aslightdecreaseinentropyinthisreaction.
(b)First,determineHforthereaction.
H=H0f(C02)+2H0f(H2O)H0f(CH4)
H=393.5kJ+2(241.8kJ)(74.85kJ)=802.25kJ
ThendetermineGforthereaction:
G=G0f(C02)+2G0f(H2O)G0f(CH4)
G=394.38kJ+2(228.61kJ)(50.79kJ)=800.81kJ
Finally,calculateSforthereaction:
S=(HG)/T
S=[802.25kJ(800.81kJ)]/298K=4.83J/K
(c)Thechangeinentropyissmallandentropydecreasesduringthisreactionsothe
predictionwasright.
8.46.
Thisreaction,2H2(g)+O2(g)2H2O(l),isknowntohavealargenegativefreeenergy
changeatroomtemperature.Doesthismeanthatifyoumixhydrogenandoxygenat
roomtemperatureyoushouldbeabletoseethereactionoccur?Explain.
Answerto8.48:
AlargenegativeGindicatesthatthereactionisspontaneous,butitdoesnotindicateat
whichratethereactionoccurs.Althoughthereactionisspontaneous,thereactionisvery
slow,sowewillnotbeabletoobservethewaterformedafterreactingoxygenand
hydrogenatroomtemperature.
8.47.
Forthisreaction,C(graphite)+2H2(g)CH4(g),Ho=74.8kJandSo=80.8JK1.
(a) Plot,aswasdoneinFigure8.13,H,TS,andGasafunctionoftemperaturefor
thereactionunderstandardconditions.Whatassumptionsmustyoumaketoconstruct
yourplot?
(b) Useyourplottoestimatethetemperatureatwhichthisreactionisinequilibrium
understandardconditions.Explainhowyoufindthetemperature.
(c) Isthetemperatureyoufoundinpart(b)likelytobeanaccurateprediction?Explain
whyorwhynot.
Answerto8.49:
(a)WhenyoudrawthegraphyouwillseethatGbecomespositiveasthe
temperatureincreases
Chapter8
H(kJ/mol)
S(kJ/mol)
74.8
74.8
74.8
74.8
74.8
74.8
74.8
74.8
74.8
74.8
74.8
74.8
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
8.08E02
TdetaS
(kJ/mol)
1.62E+01
2.42E+01
3.23E+01
4.04E+01
4.85E+01
5.66E+01
6.46E+01
7.27E+01
8.08E+01
8.89E+01
9.70E+01
1.05E+02
G(kJ/mol)
T(K)
5.86E+01
5.06E+01
4.25E+01
3.44E+01
2.63E+01
1.82E+01
1.02E+01
2.08E+00
6.00E+00
1.41E+01
2.22E+01
3.02E+01
200
300
400
500
600
700
800
900
1000
1100
1200
1300
plot of delta G delta H and TdeltaS

4.00E+01
2.00E+01
0.00E+00
-2.00E+01
500
1000
1500
Delta G
TdeltaS
-4.00E+01
Delta H
-6.00E+01
-8.00E+01
-1.00E+02
-1.20E+02
Temperature K
Chapter8
TomakeasimpleplotliketheoneinFigure8.13,youmustassumethatSandHare
notfunctionsofT,thatis,thattheydonotvaryasTchanges.
(b)UseyourplottofindtheintersectionoftheHandTSlines,thatis,whereG=
HTS=0.Thisisatabout925KandcorrespondstoT=H/S.
(c)Sincethetemperaturerangerequiredtoestimatetheequilibriumtemperatureismore
than600degrees(298Ktoover900K),theassumptionsthatSandHareindependent
ofTalmostcertainlybreakdown,sothetemperatureestimatedinpart(b)islikelytobe
offsomewhatfromtheexperimentalvalue.
8.48.
Whatisthefreeenergychange,G,whenonemoleofwaterat100Cand100kPa
pressure(standardpressure)isconvertedtogaseouswaterat100Cand100kPa
pressure?Thestandardenthalpychangeforthisprocessis40.6kJ.Explainyouranswer.
Answerto8.50:
FromAppendixXX,thestandardentropychangeis118.9J.K1.mol1.Then,usingthe
equation,G=HTS,G=40.6kJ.mol1(373K)(0.1189kJ.K1.mol1)=4.0
kJ.mol1.
8.49.
Wehaveshownthatobservedchangesoccurinthedirectionthatincreasesthenet
entropyoftheuniverse(oratleastourtinycornerofit),Snet,thesumofpositionaland
thermalentropychangesfortheprocess.Youwillfindotherwriterswhosaythat
observedchangesoccurinthedirectionthatminimizestheenergyofthesystem
undergoingchangeandmaximizesitsentropy.Explainclearlyhowthesetwoviewpoints
areactuallythesame.(Wehaveusedthefirstbecauseitmakestheconnectionbetween
higherprobabilityanddirectionofchangemoreexplicit.)
Answerto8.51:
Thethermalentropychangeforaprocessisameasureoftheentropychangeinthe
thermalsurroundings,Sthermal=H/T,whereHistheenthalpychangeinthesystem
undergoingchange.IfHisnegative(anexothemicprocess),thenSthermalispositiveand
actstoincreasethenetentropyoftheworld,Snet.Thepositionalentropychange,
Spositional,istheentropychangeinthesystem.Fromthepointofviewofthesystemalone,
maximizingitsentropymeansmaximizingSpositional,whichisinthedirectiontomake
Snetlargeandpositive.Minimizingtheenergyofthesystemmeanslosingasmuch
energyaspossibletothesurroundings,anexothermicprocess.Thisexothermicitymakes
Sthermalpositiveandlarge,which,again,isinthedirectiontomakeSnetlargeand
positive.Thus,thetwoviewpointscomedowntothesamething.Theproblemwiththe
Chapter8
energyentropyviewpointisthatitobscurestheunderlyingbasisforthechange,the
increaseinnetentropy,andmakesitseemthatentropyandenergyeffectsaresomehow
incompetition,whichisnotthecase.
Section8.8.
ThermodynamicCalculationsforChemicalReactions
8.50.
Forthiscombustionreaction,CH3COCH3(g)+4O2(g)3CO2(g))+3H2O(l),at298K,
G=1784kJandH=1854kJ.
(a) WillthevalueofTSforthisreactionbeaboutthesamemagnitudeasforGand
H?Makeaqualitativeestimateofthisvalue.
(b) CommentonwhatyourestimatedrelativevalueforTStellsyouaboutthefactor
thatcontributesmosttothenetentropychange,Snet,forthisreaction.
(c) CalculatethevalueofSforthisreaction,reportingyouranswerinJK1.
Answerto8.52:
(a)TheGibbsequationgivestherelationshipamongthesefunctions.
G=HsystemTSsystem.
1784kJ=1854kJ(298K)Ssystem.
Thereareonly70kJofdifferencebetweentheG=Hsystemterms,sothe
valueofSsystem.,whichmustbemultipliedby298KintheTSsystem.term,
mustbequitesmallrelativetothevaluesofGandH.ThesignofSsystem
mustbenegativeforthetwosidesoftheequationtobeequalinvalue.
(b)Theheatenergyreleasedprovidesthedrivingforceinthisandmost
combustionreactions.
(c)G=HsystemTSsystem
1784kJ=1854kJ(298K)Ssystem
Ssystem=0.235kJK1or235JK1
8.51.
Forthisreaction,4Ag(s)+O2(g)2Ag2O(s),at298K,Ho=61.1kJandSo=
0.132kJ.K1.
(a) Assumingthatthereactiontakesplaceatconstantpressure,isitspontaneousat
25C?Explain.
(b) Isitgoingtobespontaneousat273C?Explainthereasoningforyourresponseand
clearlystateanyassumptionsyoumake.
Answerto8.53:
Chapter8
(a)FortheprocesstobespontaneousG<0.Atroomtemperature(293K),G=
61kJ/mole[293Kx(0.132kJ/molK)]=22kJ/moleAtroomtemperaturethis
processisspontaneous.
(b)At273C(546K),G=61kJ/mole[546Kx(0.132kJ/molK)]=11kJ/mole.
Thereforethereactionisnotspontaneous.
8.52.
Thethermodynamicdatainthistablehave
beenobtainedforthegasphasedimerization
reactionofmethanoicacid(dottedlines
HC(O)OH(g)
[HC(O)OH]2(g)
Hof
kJmol1
So
JK1mol1
362.63
785.34
251.0
347.7
representhydrogenbonds):
2
O
H C
O H
O
H O
H C
C H
O H
O
(a) CalculateHo,So,andGoforthegasphasedimerizationat298K.Isthe
formationofthedimerfromthemonomersspontaneousundertheseconditions?Explain.
(b) Calculatetheenthalpychangeperhydrogenbondformedinthegasphase.Show
yourreasoningclearly.
(c) Whyisitnotusefultoestimatethefreeenergyorentropyofhydrogenbond
formationinthesamewayyoudidtheenthalpyinpart(b)?
Answerto8.54:
(a)Usingthedatainthetable,Ho=Hof(dimer)(2)Hof(methanoicacid)=785.34
kJmol1[(2)(362.63kJmol1)]=60.08kJmol1.
So=Sof(dimer)(2)Sof(methanoicacid)=347.7JK1mol1[(2)(251.0JK1mol1)]
=154.3JK1mol1.
Go=HoTSo;Go=60.08kJmol1(298K)(0.1543kJK1mol1)=14.2kJmol
.Yes,theformationofthedimerisspontaneousundertheseconditions.Thecalculated
negativevalueofGoindicatesaspontaneousreaction.
(b)TheHocalculatedvalueof60.08kJmol1isessentiallytheenergyreleasedwhen
twohydrogenbondsareformedduringthedimerization.Therefore,theenthalpychange
perhydrogenbondwouldbehalfofthisvalueor30.04kJmol1.
(c)Unlikeenthalpyvalues,entropyvaluescannotbeaveraged.Alargerentropychange
existsfortwomoleculesofmethanoicacidfindingeachothertoformthefirsthydrogen
bond.Theentropyvalueofformingthesecondhydrogenbondwillbeless.Sincethe
valueoffreeenergydependsonthevalueofentropy,wecannotaccuratelyestimatethe
freeenergyvalueeitherinthesamewaywedidfortheenthalpy.
Chapter8
8.53.
UsedatafromAppendixXXtocalculateHo,So,andGoforeachofthesedissolution
reactions:
KCl(s)K+(aq)+Cl(aq)
AgCl(s)Ag+(aq)+Cl(aq)
(a) DoyourresultssupportthesolubilitieswediscussedinChapter2,Section2.7?
Explainwhyorwhynot.
(b) DoyoupredictthatthesolubilityofKCl(s)shouldincrease,decrease,orstaythe
sameasthetemperatureisincreased?Justifyyouranswerthermodynamically.
(c) DoyoupredictthatthesolubilityofAgCl(s)shouldincrease,decrease,orstaythe
sameasthetemperatureisincreased?Justifyyouranswerthermodynamically.
Answerto8.55:
UsingAppendixXX,HoforKCl(s)K+(aq)+Cl(aq)is:
Ho=[Hof(K+(aq))+Hof(Cl(aq))][Hof(KCl(s)]=17.21kJmol1.
Inthesameway,Socanbecalculated.Forthisreaction,So=76.4JK1mol1.
Go=HoTSo;Go=17.21kJmol1(298K)(0.0764JK1mol1)=
5.55kJmol1.
UsingAppendixXX,HoforAgCl(s)Ag+(aq)+Cl(aq)is:
Ho=[Hof(Ag+(aq))+Hof(Cl(aq))][Hof(AgCl(s)]=65.49kJmol1.
Inthesameway,Socanbecalculated.Forthisreaction,So=32.98JK1mol1.
Go=HoTSo;Go=65.49kJmol1(298K)(0.03298JK1mol1)=
+55.66kJmol1.
(a)Yes,thecalculatedresultssupportthesolubilitiesdiscussedinChapter2.The
negativeGofordissolvingKCl(s)indicatesthatitwilldissolveinwater.Infact,we
observedthatpotassiumsaltsarequitesolubleinwater.However,thepositiveGofor
dissolvingAgCl(s)indicatesthatitwillnotspontaneous.WeobservedthatAgCl(s)wasa
insolublesaltinChapter2.
(b)ThesolubilityofKCl(s)willincreaseasthetemperatureisincreased.With
increasingtemperatures,thevalueofTSowillgrowlargerwhichwillmakeGomore
negative.
(c)ThesolubilityofAgCl(s)willstayaboutthesameasthetemperatureisincreased.
Forexample,doublingthetemperatureto596Konlyresultsinapproximatelya10
kJmol1decreaseinGotoapproximately46kJmol1.
Chapter8
8.54.
(a) For3C2H2(g)C6H6(l),usedatafromAppendixXXtofindGoat298Kforthe
conversionofethynetobenzene.Inwhichdirectionisthereactionspontaneousunder
standardconditions?Explain.
(b)Shoulditbepossibletofindatemperaturewherethisdirectionisreversed?Givea
thermodynamicanswerbasedonthereactantsandcheckitwithdatafromAppendixXX.
Answerto8.56:
(a)Go=[Gof(C6H6(l))](3)[Gof(C2H3(g))];Go=(124.3kJmol1)(3)(209.20
kJmol1)=503.30kJmol1.Understandardconditions,thereactionisspontaneous
underforwardconditions.
(b)Yes,itispossibletofindatemperaturewherethisdirectioncanbereversed.
LetGo=0;thenHo=TSo;UsingAppendixXX,youcancalculateHo=631.19
kJmol1andSo=429.52JK1mol1;SolveforT=1470K.Thus,atanytemperature
above1470K,thedirectionofthisreactionwouldbereversed.
8.55.
(a) Hydrazine,N2H4(l),anditsderivativesareusedasrocketfuels.Severaldifferent
oxidizerscanbeusedwithhydrazine.UsedatafromAppendixXXtocalculateHo,So,
andGoat298KforthereactionwithH2O2(l):N2H4(l)+H2O2(l)N2(g)+2H2O(l).
(b) Isthereactionspontaneous?Explain.
(c) Inarocketengine,thereactantswillgethot.Arehighertemperaturesmorefavorable
orlessfavorableforthereaction?Justifyyouranswerthermodynamically.
Answerto8.57:
(a)Therelevantthermodynamicquantitiesare:
compound
Hof,kJmol1
So,JK1mol1
N2H4(l)
H2O2(l)
N2(g)
H2O(l)
50.63
187.78
0
285.83
121.21
109.6
191.61
69.91
Gof,kJmol1
149.34
120.35
0
237.13
Forthereactionwritten,weget:
Ho=(1mol)Hof[N2(g)]+(2mol)Hof[H2O(l)]
(1mol)Hof[N2H4(l)](1mol)Hof[H2O2(l)]
Ho=(0kJ)+2(285.83kJ)(50.63kJ)(187.78kJ)=434.51kJ
So=(1mol)So[N2(g)]+(2mol)So[H2O(l)](1mol)So[N2H4(l)](1mol)So[H2O2(l)]
So=(191.61JK1)+2(69.91JK1)(121.21JK1)(109.6JK1)=100.62JK1
Go=(1mol)Gof[N2(g)]+(2mol)Gof[H2O(l)]
Chapter8
(1mol)Gof[N2H4(l)](1mol)Gof[H2O2(l)]
Go=(0kJ)+2(237.13kJ)(149.34kJ)(120.35kJ)=743.95kJ
(b)ThestandardGibbsfreeenergychangeforthisreactionislargeandnegative.Under
standardconditionsthereactionisspontaneouswithalargedrivingforce.Sincethe
enthalpychangeforthereactionislargeandnegativeandtheentropychangeislargeand
positive,thereactionshouldbespontaneousunderessentiallyallconditions(seeProblem
8.45),unlesseithertheenthalpyorentropyishighlydependentonchangesinconditions,
whichisnotlikely.
(c)Asthetemperatureincreases,theTStermwillgetlargerandmorenegative,
makingGlargerandmorenegative.Increasingthetemperaturemakesthereactioneven
morefavorable.Athighertemperatures,thehydrazine,hydrogenperoxide,andwaterwill
vaporizeandthiswillrequiresomethermalenergy,butthereisagreatdealreleasedin
thereaction,sothiswillnotchangethesignofG.
8.56.
Considerthereactionthatconvertspyruvicacidtoethanalandcarbondioxide:
CH3COC(O)OH(l)CH3CHO(l)+CO2(g)
(a) UsethedatafromAppendixXtocalculateHo,So,andGoforthisreactionat298
K.Areyourresultsconsistentwithequation(8.19)?Explainwhyorwhynot.
(b) Isthisreactionspontaneousunderstandardconditions?Explain.
(c) Ifthepressureofcarbondioxideisraisedto100atm(about10,000kPa),howwill
theentropyofcarbondioxidebeaffected?Givethereasoningforyourresponse.Hint:
Recallwhattheidealgasequation,Chapter7,Section7.13,equation(7.56),tellsyou
abouttherelationshipofthepressuretothevolumeofagasandhowtheentropyofa
systemvarieswiththevolumeavailabletothemolecules.
(d) Howwillthechangeinpressureofcarbondioxideaffectthefreeenergychangefor
thereaction?Willthereactionbemoreorlesslikelytoproceedaswritten?Explain.
(e) Assumingthatthereactionisinequilibriumbeforethecarbondioxidepressureis
increased,whatdoesLeChateliersprinciplepredictabouttheeffectontheequilibrium
ofincreasingthepressure?Isthispredictionconsistentwithyourresponseinpart(d)?
Explainwhyorwhynot.
Answerto8.58:
8.57.
Whenwatervaporispassedoverhotcarbon,thisreactionoccurs:
C(s)+H2O(g)CO(g)+H2(g)
Chapter8
Theproductmixtureiscalledwatergasorsynthesisgas,sinceitcanbeusedasa
startingmaterialtosynthesizemanycarboncontainingmolecules.
(a) UsedatafromAppendixXXtocalculateHo,So,andGoforthisreactionat
298K.Isthereactionspontaneousunderstandardconditions?Explain.
(b) Willincreasingthetemperaturemakethereactionmorefavorableorlessfavorable
inthedirectionwritten?Justifyyouranswerthermodynamically.
(c) Willthereactionbefavoredinthedirectionwrittenbyincreasingordecreasingthe
pressureofgasesinthesystem?Justifyyouranswerthermodynamically.
(d) Givenyouranswersinparts(b)and(c),whatconditionswouldyourecommendto
optimizetheformationofproducts.
(i)
lowtemperatureandlowpressure
(ii)
lowtemperatureandhighpressure
(iii) hightemperatureandlowpressure
(iv) hightemperatureandhighpressure
Answerto8.59:
(a)Therelevantthermodynamicquantitiesare:
compound
Hof,kJmol1
So,JK1mol1
C(s)
H2O(g)
CO(g)
H2(g)
0
241.82
110.53
0
5.740
188.83
197.67
130.68
Gof,kJmol1
0
228.57
137.17
0
Forthewatergasreaction,weget:
Ho=(1mol)Hof[CO(g)]+(1mol)Hof[H2(g)]
(1mol)Hof[C(s)](1mol)Hof[H2O(g))]
Ho=(110.53kJ)+(0kJ)(0kJ)(241.82kJ)=131.29kJ
So=(1mol)So[CO(g)]+(1mol)So[H2(g)](1mol)So[C(s)](1mol)So[H2O(g)]
So=(197.67JK1)+(130.68JK1)(5.740JK1)(188.83JK1)=133.78JK1
Go=(1mol)Gof[CO(g)]+(1mol)Gof[H2(g)]
(1mol)Gof[C(s)](1mol)Gof[H2O(g)]
Go=(137.17kJ)+(0kJ)(0kJ)(228.57kJ)=91.40kJ
Understandardconditionsat298K,thereactionisnotspontaneous:G=Go>0.
(b)Sincetheentropychangeforthereactionislargeandpositive.increasingthe
temperaturewillmakeTSalargernegativevalue,which,athighenoughtemperature,
shouldmakeG<0andmakethereactionspontaneous.
Chapter8
(c)Thereisanincreaseinnumberofmolesofgasinthewatergasreaction.Ifwestress
thesystembyincreasingthegaspressure,LeChateliersprinciplepredictsthatthe
systemwillrespondbyusingupsomeofthegas,thatis,bygoinginreversetoward
reactants.Thisistheunfavorabledirectionforthereaction,soweshoulddecreasethegas
pressuretofavorproducts.Wealsoknowthattheentropyofgasesincreasesasthe
volumeavailablepermoleculeincreases,sodecreasingthepressure(byeitherincreasing
thevolumeordecreasingthenumberofmolesofgas)willincreasetheentropyofthe
gases.Sincetherearemoreproductthanreactantgases,thenetchangeinentropyforthis
changewillbepositive,sothisthermodynamicargumentalsosuggestsloweringthe
pressuretofavorthereactionaswritten.
(d)Parts(b)and(c)suggestraisingthetemperatureandloweringthepressuretofavor
thereaction.Thisischoice(iii).
Section8.9.
WhyOilandWaterDontMix
8.58.
Thecellulosemolecules(polymersofglucose)thatmakeuppaperarepolarand
hydrophilic.Howdoesthestructureoffatexplainhowwaterbeadsupanddoesnotget
absorbedbywaxedpaper(paperimpregnatedwithfattysubstances)?
O
O
O
O
CH2
CH
H 2C O
Answerto8.60:
[Notethetypo:fatexplainshouldbefatexplain.Also,thestructureshouldprobably
belabeledasatypicalfatmolecule.]
Thepolarendsofthefatmolecules(therighthandendsinthestructureshown)will
interactwiththepolarcellulosemoleculesandcoverthemwithahydrophobiclayerof
thenonpolarendsofthefatmoleculesstickingoutfromthecellulosepolymericchains.
Watermoleculeswillcontactthishydrophobiclayerandnotbeabletointeractwiththe
polarcellulose.Thestronginteractionofwatermoleculeswithoneanother(Hbonding)
willholdthewatertogetherinbeads(droplets)onthehydrophobicsurface.
8.59.
(a) Doyouthinkthepositionalentropychangefortheformationofthemethanewater
clathratefromthepurecompoundsispositiveornegative?Clearlyexplainthereasoning
foryouranswer.
Chapter8
(b) Whatreason(s)canyouthinkoffortheclathrateformationbeingmorefavorableat
lowertemperatures?Clearlyexplainthereasoningforyouranswer.
(c) Whatreason(s)canyouthinkoffortheclathrateformationbeingmorefavorableat
higherpressuresofmethane?Clearlyexplainthereasoningforyouranswer.Hint:The
molarentropyofagasdecreasesasitspressureincreasesatconstanttemperature.(Does
thismakesensetoyou?SeeProblems8.58(c)and8.93(e).)
Answerto8.61:
(a)Thepositionalentropychangeforclathrateformationinvolvesacombination
offactors.Formingamixtureincreasesthepositionalentropy.However,
restrictingagas,methane,fromitsusualfreedomofmotiondecreasesthe
positionalentropy.Furthermore,formationoftheorderedcagesofwater
moleculesaroundthemethanesdecreasesthepositionalentropyofthewater.The
neteffectisadecreaseinpositionalentropy,whichiswhythesolubilityof
methaneinwaterislow.
(b)Atlowertemperatures,themovementofwatermoleculesislessvigorousand
itiseasierforthemtoformtheicelikecagesrequiredforclathrateformation.
Also,thesolutionofmethaneiswaterisslightlyexothermic.Atlower
temperaturesthepositivethermalentropychangeinthesurroundingswillbe
greaterthanathighertemperatures,thusfavoringthesolutionofmethaneand
formationoftheclathrate.
(c)Athigherpressures,theentropyofthegasdecreasesbecausethevolumedecreases
andthereislessroomformoleculestomovearound.Thedifferenceinentropybetween
thegasandthegasmoleculesdissolvedinwaterbecomesless,sothedecreaseinentropy
formethanedissolvingbecomessmaller.Overall,thismeansthatthepositionalentropy
changefordissolvingandclathrateformationbecomesabitmorefavorableandclathrate
formationmorefavored.
8.60.
BenjaminFranklinwasalwaysinterestedintheworldaroundhim.Henoted,for
example,thatateaspoonofoil(about5mL)pouredonthesurfaceofacalmpondspread
outtoformanoilpatchabout1/2acre(about4000m2)inarea.Whatdothesedatatell
youaboutthesize,innm,ofanoilparticle(molecule)?Carefullynoteandexplainany
assumptionsyoumakeinansweringthisquestion.
Answerto8.62:
Chapter8
IfFranklinsoilpatchisacontinuousfilmofoilonemoleculethick,thenwecanequate
thevolumeofoneteaspoonofoilwiththevolumeoftheonemoleculethicklayer.Ifwe
furtherassumethatoilmoleculesareasimpleshape,likecubes,thatstacktogetheras
tightlyaspossibleinboththethreedimensionalandtwodimensionalcase,wecanfigure
outthesizeofthemolecule(cube).Ateaspoonholdsabout5mLofliquidorabout5
106m3.Anacreisabout4047m2;ahalfacreisabout2103m2.Ifthesideofthecubic
oilmoleculeisdmeterslong,thevolumeoftheoilfilmis(2103m2)(dm)=2d103
m3.Settingthetwovolumesequalandsolvingford,givesd=2.5109m=2.5nm=
2500pm.Carboncarbonbondlengthsareabout150pmandoilorfatmoleculescontain
atleast50carbons,soamoleculesimilarinshapetoaphospholipidcouldbefolded
aboutinsuchawayastohaveadiameterofabout2500pm.Franklinsobservationmore
than200yearsagoisinaccordwithwhatwenowknowaboutmolecularstructure.
Section8.10.AmbiphilicMolecules:MicellesandBilayerMembranes
8.61.
Supposeyouhaveseveralambiphiliccompoundswiththesamepolarheadbutnonpolar
tailsofdifferentlengths.Howwillthelengthsofthetailsaffecttheabilityofthe
compoundstoformmicellesinwater?Usedrawingstohelpmakeyourexplanation
clear.
Answerto8.63:
Micellescanformwhenthesizeofthepolarheadsislargeenoughtocoverthe
roughlysphericalvolumeoccupiedbythehydrophobictailstuckedinsidethe
shellofpolarheads,asshowninFigure8.22andreproducedhere:
Ifthenonpolartailsaretoolong,thepolarheadsarenotlargeenoughtoforma
shellthatcancompletelyenclosethem,asshowninthisdrawing:
Chapter8
Asthetailsgetlonger,micellesarehardertoformandtheambiphilesbecomeless
solubleorperhapsformother,moreextendedstructuresmorelikebilayers.
8.62.
Thediagramhereshowsliquidwaterwithalessdensenonpolarliquidfloatingonit(oil
onwater).
nonpolarliquid
water
(a) Supposeyouhaveanambiphiliccompoundthatcantformmicellesinwater
becauseitsnonpolartailistoolong.Ifyouaddjustalittlebitofthisambiphilic
compoundtothesystemabove,wheredoyouthinkthemoleculesofthecompoundwill
beinthesystem?Aspartofyouranswerdrawadiagramtoshowwheretheambiphilic
moleculesareandhowtheyareinteractingwiththewaterandnonpolarliquid.
(b)Ifyouaddmoreoftheambiphiliccompoundtothesystem,wherewillthemolecules
ofthecompoundbeinthesystem?Aspartofyouranswerdrawadiagramtoshowwhere
theambiphilicmoleculesareandhowtheyareinteractingwiththewaterandnonpolar
liquid.Hint:Considerareversedmicelle.Whatisreversed?Howdoesthishelpsolve
theproblem?
Answerto8.64:
(a)Themoleculesoftheambiphilewillcollectattheinterfacebetweenthetwo
phaseswiththeirnonpolartailsintheuppernonpolarliquidandtheirpolarheads
inthewater:
Chapter8
(b)Sincetheambiphilecannotformamicelleinwater,itwillpreferentially
dissolveinthenonpolarsolventandformareversedmicellewiththenonpolar
tailsontheoutsideandthepolarheadsinside:
8.63.
Supposeyouhaveanambiphiliccompoundthatwillformreversedmicellesinthenon
polarliquidinProblem8.64.Doyouthink
itwouldbepossibletoremovesolutes
fromthewaterbygettingthemtodissolve
inthereversedmicellinthenonpolar
Experimentsarebeingdonewithreversed
micellesandliquidCO2asthenonpolarliquidto
seeifsuchextractionsfromwatercanbedone
withoutgeneratingalotofwastesolventsthat
couldpollutetheenvironment.
liquid?(Thiswouldbesortofliketheactionofadetergentinwater.)Whatkindof
propertieswouldthepolarheadoftheambiphiliccompoundneed,inordertogetasolute
outofthewater?
Answerto8.65:
Experimentstotestthefeasibilityofthissortofextractionarebeingcarriedoutinseveral
laboratories.Thepolarheadwouldprobablyhavetohavesomehydrogenbonding
properties,inordertocompetewithwaterforsolutesthatarehydrogenbondedwith
water.Ionsthatarehydratedbutdonothydrogenbondtowatermightbeextractedby
polarheadsthatcanchelatetheions,inordertocompetewithhydrationbythewater
molecules.
8.64.
Hepatocytes,thepredominantcellsinyourliver,areroughlycubicalwithedgelengthsof
about15106m(15m).
(a) Abouthowmanyphospholipidmolecules,Figure8.22,arerequiredtoformthecell
membrane?Statealltheassumptionsyoumaketosolvethisproblemandexplainyour
solutionmethodclearly.
Chapter8
(b)Howmanymolesofphospholipidarerequiredtoformthemembraneandwhatisthe
massofthephospholipidinthemembrane?Stateanyfurtherassumptionsyoumaketo
solvethisproblemandexplainyoursolutionmethodclearly.
Answerto8.66:
(a)Inordertodothisproblem,wehavetomakeanassumptionabouttheareaof
thesurfaceofthecellmembraneoccupiedbyaphopholipidmolecule.Youcould
makeamodelofthegycerolmoleculeandthenextfewatomsbondedtoitinthe
phospholipidshowninFigure8.24andthenmeasurethesizewiththescalethat
comeswiththemodelset.Themeasurementisprobablydifferentindifferent
dimensions,butwewillassumethattheshouldersofeachmoleculeoccupya
squarethatisabout500pm(5001012m)onaside.Theareaofthissquareis
2.51019m2.Theareaofonesurfaceofthecellis(15106m)2=2.31010m2
andtherearesixsides,sotheoutsideareaofthecellsurfaceis1.4109m2.The
membraneisabilayerandwewillassumethattheareaofboththeinnerandouter
surfacesisthesame,sothetotalareathatmustbecoveredis2.8109m2.The
numberofphospholipidmoleculesrequiredtocoverthisareaisabout(2.8109
m2)/(2.51019m2)=11010.
(b)Thenumberofmolesrepresentedby11010phospholipidmoleculesis
(11010molecules)/(61023moleculesmol1)=21014mol.Todeterminethemassof
thismanymoles,weneedthemolarmassofaphospholipid.Thereareagreatvarietyof
phospholipidswithdifferentmolarmasses.UsethemodelshowninFigure8.17togetan
ideaofthemolarmass.Themoleculeshownhastheformula,C44H86O8NP,withamolar
massof8102g.Thus,themassofphospholipidinthehepatocytemembraneisabout
(8102gmol1)(21014mol)=21011g=20pg(picogram).Forcomparison
purposes,themassofthecell,assumingadensityof1gmL1=1106gm3,is(1106
gm3)(15106m)3=3109g=3000pg.Thiscalculationsuggeststhatthemembrane
phospholipidsmakeupalittlelessthan1%ofthemassofthecell.
8.65.
Mayonnaisehasfourmainingredients:oil,vinegar(mostlywater),lemonjuice(mostly
water),andeggyolk.Aneggyolkcontainsalotofphospholipids,proteins,andfatsto
nourishthechickembryoinafertilizedegg.Whatisthepurposeoftheeggyolkinthe
mayonnaise?Clearlyexplainyourreasoning.
Answerto8.67:
Chapter8
Mayonnaiseisbasicallyamixtureofoilandwaterthatdoesnotseparate(atleast,itisnot
supposedtoseparate).Thissortofmixtureiscalledanemulsion.Inordertoprevent
separation,eggyolkisaddedtothemixture.Thephospholipidsintheaddedyolkform
micellesthatholdtheoilintheirinteriors(likeadetergentmicelle)andkeepthemixture
fromseparating.
8.66.
Tocarryouttheirfunctions,membranesneedtostayfluid,sothattheyretaintheir
permeabilityandtheproteinsembeddedinthemcanmoveaboutasnecessary.Oneway
thatcoldbloodedorganismsusetokeeptheirmembranesfluidatdifferenttemperatures
istochangetheproportionofsaturatedandunsaturatedfattyacids,Figure8.22,inthe
phospholipidmembranemolecules.Comparedtoafishthatlivesinthetropics,would
youexpectafishthatlivesincoldArcticwaterstohaveahigherorlowerproportionof
unsaturatedfattyacidsinitsmembranes?Clearlyexplainthereasoningforyour
response,includingmolecularleveldrawings,ifthathelpsyourexplanation.
Answerto8.68:
Themoreuniformlythephospholipidmoleculescanstacktogether,sidebyside,inthe
membrane,thelessfreedomeachhastomoveabout.Thegoodstackingleadstoa
stiffermembraneinwhichmoleculesarelimitedintheirmotion.Tomakethe
membranemoreflexibleorfluid,theorganismneedstodisrupttheuniformstacking.
Notefromthefigurethatdoublebonds(unsaturation)inthefattyacidchainmakesthe
chainkinked,soitcannotpackasuniformlywithitsneighbors.Thus,acoldwaterfish
wouldprobablyhavemoreunsaturatedfattyacidsinitsphospholipids,inorderto
increasethefluidityofitsmembranesevenasthetemperaturetendstostiffenthem.The
propertiesoffatsandoilsprovideafamiliaranalogy.Fatsandoilsareestersofglycerol
withthreefattyacidsbondedtothealcoholgroups.Thedifferencebetweenafatandan
oilisthatafatisasolidatroomtemperatureandanoilisliquid.Thecauseofthis
differenceisamuchhigherproportionofunsaturatedfattyacidchainsinoils.The
moleculesofoilcantstacktogetheraseasilyandmustbetakentoalowertemperature
beforetheycansolidify.
Section8.11.ColligativePropertiesofSolutions
8.67.
OilrichcountriesintheMiddleEastonceconsideredtowingicebergsfromtheArctic
Oceantohelpsolvetheirwatershortages.Wouldnttheicebergsbemadeofsaltwater
liketheoceanwater?Explain.
Chapter8
Answerto8.69:
No,puresolidcrystallizesfromthesolution,notasolidcontainingsodiumions,chloride
ions,andwatermolecules.
8.68.
ExplainwhySsolution>Ssolvent>Ssolid.
Answerto8.70:
Thenumberofdistinguishablearrangementsincreasesasweconsidertheentropyofthe
solute,followedbytheentropyofthesolventtotheentropyofsolution.
8.69.
Whydoesacolligativepropertydependonlyonthenumberofsoluteparticlesandnot
theirchemicalproperties?
Answerto8.71:
Colligativepropertiesdependontheentropythatis,thenumberofarrangmentsofthe
particlesandnottheinteractionsbetweenparticles.
8.70.
Whichsolutionwillhavethelowestfreezingpoint?Explainyouranswer.
(i) 1MNaCl
(ii) 1MCaBr2
(iii) 1MAl(NO3)3
Answerto8.72:
Freezingpointloweringisacolligativeproperty,soitsmagnitudedependsonthenumber
ofparticles(ionsormolecules)inagivenvolumeofthesolution.Assumingthattheseare
aqueoussolutionsandthateachoftheseionicsaltsdissociatescompletelyinsolution,we
get2,3,and4ions,respectively,fromthecompoundsin(i),(ii),and(iii).Thealuminum
nitratesolutionwillhavethelowestfreezingpoint.(Thevolumeofsolutiontestedis
irrelevant.)
8.71.
Explainwhyamixtureofantifreezeandwater,insteadofpurewater,istypicallyplaced
inanautomobile'sradiator.
Answerto8.73:
Mostantifreezeproductsavailabletodaycontainethyleneglycol,HOCH2CH2OH(1,2
ethanediol),whichisarelativelynonvolatileliquidthatismisciblewithwater.
Dissolvingantifreezeinwaterlowersthefreezingpointofthesolution,sotheliquidis
protectedfromfreezingincoldweather.Ifthecoolantsolutionfreezesinyourradiatoror
engine,itcancauseagreatdealofdamage,becauseitexpandsuponfreezingandcan
breakanengineblock.Asecondgreatadvantageofethyleneglycolisthatitincreasesthe
Chapter8
boilingpointofitsaqueoussolutions,soyourengineislesslikelytoboiloverinthe
summer.Thus,thisantifreezemightalsobecalledantiboil.
8.72.
WhichaqueoussolutionhasthelargestTfp?Explainyourreasoning.
(i) 1.5msolutionofglucose,C6H12O6
(ii) 1.5msolutionofsodiumchloride
(iii) 1.5msolutionofmagnesiumchloride
Answerto8.74:
Eachsolutionhasthesamemolalitybutnotthesame#ofparticles,soMgCl2hasmore
particlesthanNaClwhichhasmorethanglucose(whichdoesnotionize).Therefore,
MgCl2wouldgivethegreatestfreezingpointdepression.
8.73.
Whatisthefreezingpointofasolutionmadebydissolving5.00gofsucrose,C12H22O11,
in100.0gofwater?
Answerto8.75:
(Kf=1.86C/m)molalityofsolution=0.146m
Tfp,=0.272C
fp=0.272C
8.74.
Asolutionismadebymixing10.00gofndecane,CH3(CH2)8CH3,with100.00gof
benzene.
(a) Whatisthemolalityofthissolution?
(b) Calculatethefreezingpointdepression,Tfp,forthissolution.
(c) Whatisthefreezingpointofthismixture?
Answerto8.76:
(a)Molality=molsolute/kgsolvent
m=(10g/134g/mol)/100gx1000g/1kg
m=0.746m
(b)Tfp,=Kfxm(Kf=5.12C/m)
Tfp,=5.12C/mx0.746m
Tfp,=3.82C
(c)5.5C3.82C=1.68C
Chapter8
8.75.
Solutionsofanonvolatile,nonionizingsolutearepreparedinbenzeneandin
cyclohexane.Determinewhichsolutionwillfreezeatalowertemperature.Explainyour
procedure.
(i) 0.30msolutioninbenzene
(ii) 0.10msolutionincyclohexane
Answerto8.77:
(a)Usingbenzeneasthesolvent,thechangeinfreezingpointiscalculatedto
be:Tfp=(5.12Cm1)(0.10m)=0.51C
Thefinalfreezingpointwillbe:(5.5C)+(0.51C)=5.0C
(b)Usingcyclohexaneasthesolvent,thechangeinfreezingpointis
calculatedtobe:
Tfp=(3.90Cm1)(0.30m)=1.2C
Thefinalfreezingpointwillbe:(6.6C)+(1.2C)=5.4C
Thesecalculationsshowthatthefirstsolutionfreezesatalowertemperature.
8.76.
(a) Anaqueoussolutionof1.0msodiumchlorideispredictedtohaveafreezingpoint
of3.72C.Explainwhy.
(b) However,theactualfreezingpointis3.53C.Whyistheexperimentalfreezing
pointloweringlessthanthepredictedvalue?
Answerto8.78:
(a)Ionsinwatercauseitsfreezingpointtodecrease.
(b)Becausetheionstendtoassociate(sticktogether)insolutionsotheactualmolaityis
bitlowerthantwicetheinitialmolality.
8.77.
Whatisthefreezingpointofasolutionmadebydissolving5.00gofsodiumsulfate,
Na2SO4in100.0gofwater?
Answerto8.79:
Thereare3.52102molofSO42(aq)and7.04102molofNa+(aq)dissolvedinwater.
Thus,thetotalnumberofmolesindissolvedwateris1.06101mol.Themolality,m,is
1.06101mol/0.100kgH2O=1.06m.
Tfp = 1.86 Cm1 1.06 m = 1.97 C
Thenewfreezingpointis0.0C1.97C,or1.97C.
8.78.
Sorbitolisasweettastingsubstancethatissometimesusedasasubstituteforsucrose.Its
formulaisC6H14O6.Whatwillbethefreezingpointofanaqueoussolutioncontaining
1.00gsorbitolin100.0gofwater?
Chapter8
Answerto8.80:
Molesofsorbitol

Molalityofsolution
Tfp = 1.86 Cm 5.49 102 m = 0.102 C

1
Thenewfreezingpointis0.0C0.102C,or0.102C.
8.79.
Calculatethechangeinthefreezingpointofwaterwhen3.5milligramsofhemoglobin
(molarmass=64,000g)isdissolvedin5.0mLofwater.Wouldthismethodbeaccurate
indeterminingmolarmassesofbiomoleculesofthissize?
Answerto8.81:
Thechange(lowering)ofthefreezingpointofasolventbyasoluteisgivenbyequation
(8.31).Inordertoapplythisrelationship,weneedtofindthemolalityofthissolution.
Wewillassumethat5.0mLofwateris5.0gofwater.Thenumberofmolesof
hemoglobindissolvedis5.5108[=(3.5103g)/(64000gmol1)].Themolalityofthe
solution,m,is(5.5108mol)/(5.0103kg)=1.09105molal.Thefreezingpoint
depressionconstantforwateris1.86Cm1.Theloweringofthefreezingpointis(1.86
Cm1)(1.09105m)=2.0105C.Thisisanunmeasurablysmallchange,so
freezingpointdepressionisnotagoodmethodfordeterminingmolecularweightsof
biomolecules,suchasproteins.
Section8.12.OsmoticPressureCalculations
8.80.
Bothglucosesolutionsandphysiologicalsalinesolutions(NaCl(aq))aregiventopatients
throughintravenousinjections.Theaverageosmoticpressureofbloodserumis7.7atm
at25C.Topreventosmosisthroughthesemipermeablemembraneofaredbloodcell,
theglucosesolutionorphysiologicalsalinesolutiongivenmusthavethesameosmotic
pressureasbloodserum.(Wesaythatthesesolutionsareisotonicwithbloodserum).
Calculatetheconcentrationofglucosesolutionandsalinesolutionthatareisotonicwith
bloodserum.
Answerto8.82:
Therelationshipbetweenosmoticpressureandthemolarity,M,ofmoleculesor
ionsinasolutionis:
=MRTtherefore
Chapter8
ThemolarityofthesolutionisM=/RT.
TheosmoticpressureisgiveninatmospheressowewilluseR=0.0821L
atm/Kmol.
M=7.7atm/(0.0821Latm/Kmolx298K)=0.31M
Theconcentrationofglucosesolutionwhichisisotonicwithbloodserumis0.31M.The
concentrationofNaClwhichisisotonicwithbloodis0.16Mhowever,becauseNaCl
ionizestoformtwoparticlesNa+andClparticles.
8.81.
Supposeyoudissolve0.150gofanewlyisolatedproteinin25.0mLofwater.The
solutionhasanosmoticpressureof0.00342atmat277K.Whatisthemolarmassofthis
protein?
Answerto8.83:

Molarmass

8.82.
Supposeyouhaveasolutionseparatedfrompurewaterbyamembranethatisonly
permeabletowater,asshowninthisdiagram.
solution
water
membranepermeabletowater
Thesolutionwillhaveacertainosmoticpressure,,determinedbythesolutesit
contains.Whatwouldhappenifapressure,P,greaterthanthisosmoticpressureis
appliedtothesolutionbyapiston,asshowninthediagram?Usedrawingstoillustrate
whatishappeningatthemolecularlevel.
Answerto8.84:
Theosmoticpressure,,isthepressurerequiredtodecreasetheentropyofthesolution
tomatchthatofthepurewater,sothereisnonetflowofwaterthroughthemembrane.If
Chapter8
apressuregreaterthanisappliedtothesolution,theentropyofthesolutionwill
decreasestillfurtherandbelessthantheentropyofthepurewater.Underthese
circumstances,thenetentropywillincrease,ifwatermoleculespassfromsolutioninto
thepureliquid.Thus,waterwillflowfromthesolutionintothepurewater.Molecular
levelpicturescanshowthevolumeavailabletothewatermoleculesdecreasingasthe
pressureisincreasedandthesolutioniscompressedatinybit.Ifthepressureishigh
enoughthecompressionislargeenoughtomaketheentropyevenlowerthanforpure
water.
8.83.
TheprocesssuggestedinProblem8.84iscalledreverseosmosis.Whatisitthatis
reversed?Whatpracticalusescanyouthinkofforreverseosmosis?
Answerto8.85:
Inreverseosmosis,theflowofwaterisreversedfromthedirectionweassociatewith
regularosmosis.Theflowisfromsolutiontopureliquid,ratherthantheotherway
around.Purificationofsalt(ocean)watertoproducefresh,waterforirrigationand
drinkingisonepracticaluseofreverseosmosisthatisbeingusedinaridpartsofthe
worldnearoceans,suchastheArabianpeninsula.
8.84.
Freshwatercanbepreparedfromseawaterbytheprocessofreverseosmosis.(See
Problem8.84.)Thismethodinvolvesapplyingapressuregreaterthantheosmotic
pressuretotheseawatertoforcetheflowofpurewaterfromtheseawaterthroughthe
semipermeablemembranetothepurewater.Calculatetheminimumpressurethatmust
beappliedtoaseawatersampletoproducereverseosmosis.Assumethatthe
concentrationsofseawater'ssolutesareasfollows:[Cl]=18,000ppm;[Na+]=
10,500ppm;[Mg2+]=1200ppm;[SO42]=870ppm;[K+]=379ppm.Theabbreviation
ppmstandsforpartspermillion.Oneppmisonemilligramofthesolutein1000gof
solvent.
Answerto8.86:
Reverseosmosiswillbeginwhentheappliedpressureonthesolutionjustexceeds
theosmoticpressureofthesolution.Thus,tosolvethisproblem,weneedtofind
theosmoticpressure,,oftheseawatersolution.Theconcentrationsaregivenin
ppminsteadofmolarity,sowehavetoconvertthemtomolesperliter.Wewill
assumethattheppmarepartspermillionbymass.Forexample,18,000ppmof
Clis18,000gofchlorideioninonemilliongramsofsolution.Wewillfurther
Chapter8
assumethatonemilliongramsofsolutionisonemillionmL(or1000L)of
solution.Thenumberofmolesofeachionin1000Lis:
ion
Cl
Na+
Mg2+
SO42
K+
concentration,ppm
18000
10500
1200
870
379
TOTAL
mol/1000L
510
460
50
9
10
1039
Thetableshowsthatthetotalnumberofmolesofionsin1000Lofthe
seawateris1039.Thus,thetotalionicmolarityoftheseawateris1.04M.This
isthevalueweneedtouseintheosmoticpressureequation,equation8.33,to
get:
=(1.04M)(8.314103PaLmol1K1)(298K)=2.58106Pa26atm
Apressureofabove26atmhastobeexertedontheseawatertogetreverseosmosisto
occur.Thisisahighpressure,butnotextraordinarilyhigh,sotheprocessisquite
feasible.Themajortechnicalproblemisdesignofmembranesthatcanwithstandsuch
pressures,butthisispartlysolvedbyconstructingthemascylinderswiththeseawater
andhighpressureontheoutsideandfreshwaterflowingoutontheinside.Acylindercan
withstandagreatdealmorepressure(uniformlyapplied)thanaflatsurface.
8.85.
ThereisabrandoftimereleaseplantfertilizercalledOsmocote .Thepackagesays,
Theuniqueresincoatedgranulesareeasytouse.Withinoneweekafterapplication
thesoilmoisturecausesthegranulestoswellintoplumpcapsulesofliquefiedplantfood,
whichcontinuouslyreleasenutrientsforapproximately9months.Whatsortof
propertiesdoestheresincoatinghavetohave?Whydoyouthinkthecompanythat
makesthisproductdecidedonthename,Osmocote?
Answerto8.87:
Theresincoatingneedstobesemipermeabletowater.Thereislittlewaterinsidethe
granulestobeginwith,sowaterfromthesurroundingsentersthegranulesbyosmosis
andbeginstodissolvethefertilizercompoundstoformahighlyconcentratedsolution.
Osmosiscontinuestoaddwatertothegranulesandtheirsizeincreases(theyswellinto
plumpcapsules).Asthegranulesswell,itislikelythattheresincoatingfinallybeginsto
developtinyporesthroughwhichthecontentscanoozeandcontinuouslyrelease
Chapter8
nutrientsforapproximately9months.Theproductnameseemstocombinetheideasof
acoating(cote)thathasosmotic(osmo)properties.
Section8.13.TheCostofMolecularOrganization
8.86.
Wecanconsideragrowingplant(thesystem)tobeanexampleofdecreasingentropy.
Smallmolecules,likeCO2andH2O,arebuiltintocomplex,butorderlyarrangementsof
macromolecules.Whichofthesestatementsappliestothisexample?Explainthe
reasoningforyourchoiceandthereason(s)yourejecttheothers.
(i) Thesecondlawofthermodynamicsthatnetentropyalwaysincreasesinobserved
processesisbeingviolated.
(ii) Thesecondlawofthermodynamicsisnotbeingviolatedbecauseoftheentropyof
thesurroundingsisincreasing.
(iii) Thesecondlawofthermodynamicsisnotbeingviolatedbecauseoftheentropyof
thesurroundingsisdecreasing.
(iv) Plantgrowthissocomplexthatthelawsofthermodynamicscannotbeapplied.
(v) Noneofthesestatementsappliestothisexample.
Answerto8.88:
Theonlystatementthatappliescorrectlytothegrowingplantis(ii).Thenetentropyof
thesystem(plantanditsprecursormoleculessuchascarbondioxideandwater)and
surroundings(everythingelse,especiallyenergyfromthesunaswellastheenormous
entropyincreasethesunundergoesinproducingandspreadingtheenergyintothesolar
system)increases.Forexample,photosynthesisoccurstoproducemorecomplex
moleculesfromsimpleonesandusestheenergyofelectromagneticradiationfromthe
suntodrivethereaction.Aswehavejustshown,statement(i)isincorrect.Statement(iii)
isincorrect,becauseitwouldnotprovideamechanismforapositivenetentropychange
forthesystemplussurroundings.Statement(iv)suggeststhatthereissomethingabout
thecomplexityofbiologicalsystemsthatmakesthesecondlawnotapplicable.No
system,simpleorcomplexhasyetbeenfoundtowhichthesecondlawdoesnotapply.
Thatiswhyitiscalledalaw.Noexceptionshavebeenfound.
8.87.
Considerafertilizedchickenegginanincubator,aconstanttemperatureandpressure
environment.Theeggshellanditsmembranearepermeabletoatmosphericgases.In
aboutthreeweekstheeggwillhatchintoachick.
Chapter8
(a) Taketheeggasthesystem.Isthisanopen,closed,orisolatedsystem?Explain.
Hint:Review,Chapter7,Section7.5,ifnecessary.
(b) Inthefertilizedegg,proteinsfromthehenareformedintoahighlyorderedchick.
Doestheentropyofthesystemincreaseordecrease?Brieflyexplainwhythe
developmentofthechickisorisnotconsistentwiththesecondlawofthermodynamics.
(c) Whathappenstotheenergyofthesystemasthechickdevelops?Whatformsof
energycontributetothechangeinenergy(ifany)ofthesystem?
(d) Doesthefreeenergyofthesystemincrease,decrease,orremainthesameduring
development?Howdoyouknow?
Answerto8.89:
(a)Theeggisanopensystem.Sinceatmosphericgasesfromtheatmospherecanenter
theegg,theycanactasreactantsforreactionswithintheegg.
(b)Thesamemolecules,suchasATP,thatarecoupledtosyntheticreactionsinother
livingthingsareatworkintheegg.Theyareproducedinthesamewayasinother
organismsbyoxidationoffoodmolecules(mostlythefatintheyolk)byatmospheric
oxygen.Theoxidationsallhavehighnetpositiveentropychangesandthehydrolysisof
theATPformedintheseprocessesalsohasanetpositiveentropywhichcanbe
harnessedbycouplingthehydrolysistothesyntheticreactions.
(c)Asthemetabolismoccurs,energynotcapturedintheformofpotentialenergyof
chemicalbonds(inATP,forexample)islostfromtheeggtothesurroundingsasthermal
energy.(Ifaneggwereinsulated,soitdidnotlosethermalenergytoitssurroundings,it
wouldgetwarmer.)
(d)Freeenergymustdecreaseduringthedevelopmentprocess.Theprocessis
spontaneous,soG<0.
Section8.15.EXTENSIONThermodynamicsofRubber
8.88.
Supposeyouareinvestigatingabiologicalpolymerthatundergoesareactiontogivea
product,polymerproduct,andfindthat,atagiventemperature,thereactionis
spontaneousandendothermic.
(a) WhatcanyoutellaboutthesignsofH,S,andGforthisreaction?Explainyour
reasoning.
(b) Whatdoyourresultstellyouaboutthestructureoftheproductrelativetothe
polymer?Explainyourreasoning.
Answerto8.90:
(a)Sincethereactionisendothermic,weknowthatH>0forthesystem.Also,since
thereactionisspontaneous,G<0forthesystem.InorderforGtobenegative,ifH
ispositive,S>0,sothatTS<0.
Chapter8
(b)Theproductmusthaveahigherentropythanthereactant,sinceS>0.One
possibilityisforthepolymertobebreakingdowntosmallerpieces,thusgivingmore
freedomofmotiontothepartsthatmadeupthepolymer.Thisprocesswouldrequirethe
netbreakingofbonds,whichwouldrequireenergy,whichisconsistentwiththeobserved
endothermicreaction.Thus,mostlikelyreactionissomesortofbreakdownofthe
polymer.
GeneralProblems
8.89.
Thequestionsinthisproblemarebasedonthedatainthistableofvaluesforthe
enthalpiesofformationandentropiesofseveralhydrocarbonsinthegasphase.(Manyof
thesecompoundsareliquidsat298C,sothegasphasevaluesherearecalculatedin
standardwaysfromotherexperimentaldata.)
Enthalpiesofformationandentropiesforselectedgasphasehydrocarbons.
name
ethene
propene
cyclopropane
1butene
cyclobutane
1pentene
2methyl1butene
3methyl1butene
2methyl2butene
trans2pentene
cyclopentane
1hexene
cyclohexane
1heptene
1octene
1nonene
1decene
1undecene
1dodecene
molecular
formula
C2H4
C3H6
C3H6
C4H8
C4H8
C5H10
C5H10
C5H10
C5H10
C5H10
C5H10
C6H12
C6H12
C7H14
C8H16
C9H18
C10H20
C11H22
C12H24
condensedstructuralformula
H2C=CH2
H2C=CHCH3
Csbondedinanequilateraltriangle
H2C=CHCH2CH3
Csbondedinanonplanarsquare
H2C=CHCH2CH2CH3
H2C=C(CH3)CH2CH3
H2C=CHCH(CH3)2
H3CCH=C(CH3)2
H3CCH=CHCH2CH3
Csbondedinanonplanarpentagon
H2C=CH(CH2)3CH3
Csbondedinanonplanarhexagon
H2C=CH(CH2)4CH3
H2C=CH(CH2)5CH3
H2C=CH(CH2)6CH3
H2C=CH(CH2)7CH3
H2C=CH(CH2)8CH3
H2C=CH(CH2)9CH3
Hfo
kJmol1
So
JK mol1
52.28
20.41
53.30
1.17
26.65
20.92
36.62
28.95
42.55
31.76
77.24
41.7
123.1
62.16
82.93
103.5
124.1
144.8
165.4
219.8
266.9
237.4
307.4
265.4
347.6
342.0
333.5
338.5
342.3
292.9
386.0
298.2
424.4
462.8
501.2
539.6
578.1
616.5
Chapter8
(a) UseaveragebondenthalpiesfromChapter7,Section7.7,Table7.3tocalculatethe
differenceyouwouldexpectbetweentheenthalpiesofformationoftheC3,C4,C5,andC6
cyliccompoundsandtheirlinearalkeneisomers.Doyoupredictthecyclicorlinear
isomerstobemorestable?Howdoesyourcalculateddifferencecomparewiththe
experimentalvaluesfromthetablehere?Isyourpredictioncorrect?Explainyour
reasoning.Useyourmolecularmodelstoconstructmodelsofthecyclicandlinear
isomers.How,ifatall,dothemodelsaffectyourexplanationandreasoning?
(b) ComparetheentropiesoftheC3,C4,C5,andC6cycliccompoundsandtheirlinear
alkeneisomers.Arethedifferencesinthedirectionyouwouldhavepredicted?Explain
thebasisforyourprediction.Usethemolecularmodelsyouconstructedinpart(a)to
developarationalefortherelativemagnitudesaswellasdirectionoftheentropy
differences.Clearlyexplainthebasisforyourreasoning.
(c) Aretheretrendsinthedataforthelinearalkeneisomers?Canyouillustratethese
graphicallyanddrawmorequantitativeconclusions?PredictHfoandSofor
1tetradecene,C14H28.(Whatdoesamodelofthiscompoundlooklike?)Explainhowyou
arriveatyourpredictions.Howconfidentareyouofthesepredictions?
(d) Canyouuseananalysissimilartothatinpart(c)topredictHfoandSofor
cyclooctane,C8H16?(Whatdoesamodelofthiscompoundlooklike?)Explainhowyou
arriveatyourpredictions.Howconfidentareyouofthesepredictions?
(e) WriteadiscussionofthetrendsandcorrelationsinthedataforalltheC5H10alkene
isomersinthetable.Usemodelsasabasisforrationalizingandexplainingwhatyoufind.
Answerto8.91:
(a)Thedifferenceinbondingbetweenanalkeneandthecycloalkanewith
thesamenumberofcarbonsisthebondingbetweencarbons.(Therearethe
samenumberofCHbondsinbothmolecules.)Thecycloalkanehasasmany
CCsinglebondsastherearecarbonsinthering.ThealkenehasaCC
doublebondthatreplacestwooftheCCsinglebonds.Thedifferencein
enthalpybetweenthetwoisomersisjustthedifferencebetweenaCC
doublebondenthalpyandtwoCCsinglebondenthalpies.Figure6.5inthe
lastchaptershowedthisdifferencegraphically.TwoCCsinglebondsare
strongerby74kJmol1thanoneCCdoublebond.Strongerbondingshould
leadtoamorenegativeenthalpyofformationforthecyclicisomers.This
predictionisborneoutbythedataforthefiveandsixcarbonisomers.The
Chapter8
enthalpyofformationofcyclopentaneisabout56kJmol1morenegative
thantheenthalpyofformationof1pentene.Forcyclohexaneand1hexene,
thedifferenceisabout81kJmol1.Justtheoppositeisthecasefor
cyclobutaneandcyclopropane,whichhavemorepositiveenthapiesof
formationthanbuteneandpropene,respectively.Whenyoumakemolecular
modelsoftheseeightmolecules,youfindthatitishardtoforcetheballand
stickmodelstomaketriangularandalmostsquarecarbonstructures,but
thereisnoproblemmakingthefiveandsixcarbonrings.Thedoublebond
inthealkenesisalittledifficulttoform,buttherestofthebondingiseasyto
model.Thesmallerringsarestrainedinthemodelsandtheyarestrainedin
therealmolecules.Thestrainweakensthebondingbetweenthecarbonsand
makesthemweakerthantheaveragebondenergiesweusedinthe
calculation.Thus,thestrainmakescyclopropaneandcyclobutanelessstable,
relativetotheirelements,thanthecorrespondingalkenes.
(b)Thistablecomparesthestandardentropiesforthelinearandcyclic
isomerswith3,4,5,and6carbons,withthedifferencebetweentheentropies
ofthelinearandcyclicisomersgiveninthefourthcolumn:
numberofcarbons
Solinearisomer
JK1mol1
Socyclicisomer
JK1mol1
So(linearcyclic)
JK1mol1
266.9
237.4
32.5
307.4
265.4
42.0
347.6
292.9
54.7
386.0
298.2
87.8
Wewouldexpectthelinearisomerstohavehigherentropies,astheydo,
becausethechainsarefreetoflopaboutintomanydifferentforms.The
endsofthechainarebondedtogetherinthecyclicisomers:thefreedomof
bondrotation(floppiness)islostandtheentropyofthecyclicformsis
lower.Thelongerthechain,themorefloppyitisandthemorefreedomof
motionislostgoingtothecyclicisomer.Aswesee,theentropylossforthe
6carbonchainisalmostthreetimesasgreatasforthethreecarbonchain.
Chapter8
(c)Theenthalpiesofformationgetmorenegativeandtheentropiesmore
positiveasthechainlengthsincrease.Thedataareshowninthesetwoplots:
100
700
50
600
0
500
50
Entropy
400
100
300
150
200
10
12
14
200
Numberofcarbons
10
12
14
Numberofcarbons
Thereisalineardecreaseinenthalpyofformation,tobecomemorenegative
by20kJmol1foreachaddedcarbon,afterbutene.Similarly,thereisa
linearincreaseintheentropyofabout38JK1mol1foreachcarbonadded
afterbutene.EachadditionofaCH2unittothechainseemstohavethe
sameeffect,oncethechainhasgrowntoatleastfourcarbons.Alinear
extrapolationoftheseplotsgives205kJmol1and692JK1mol1forHfo
andSo,respectively,for1tetradecene,C14H28.Theplotslookquitelinear,so
wecanprobablybeconfidentthatthesevaluesfor1tetradecenearewithin
oneunitofitsexperimentalvalues.
Fortheenthalpies,wecanusebondenthalpiesandtheenthalpyofformation
ofC(g)(fromAppendixXX)toestimatethechangeinenthalpyofformation
foraddingaCH2tothechain.
reaction
H,kJmol1
netchange
C(s)C(g)
717
vaporizecarbon
H2(g)2H(g)
436
breakHHbond
C(g)+2H(g)CH2(g)
828
maketwoCHbonds
Cnalkene(g)+CH2(g)C(n+1)alkene(g)
347
makeCCbond
Cnalkene(g)+C(s)+H2(g)C(n+1)alkene(g)
22
summation
Ourresultisveryclosetotheexperimentalvalueof20kJmol1.
(d)Ananalysisforthecyclicisomerssimilartothatforthelinearisomersis
veryshaky.Wedonthaveenoughdataandthesmallerringsarestrained
(aswesaidinpart(a)),sotheirvalueshavetobedisregarded.Thedecrease
Chapter8
inenthalpyofformationgoingfromcyclopentanetocyclohexaneisabout
46kJmol1.Thisisaboutdoublewhatwewouldexpectonthebasisofbond
enthalpies,sincetheanalysisinpart(c)isapplicablehereandpredictsonly
about22kJmol1decreaseinenthalpyofformation.Ifweextrapolatethe
experimentalincrementfortwomorecarbons,wewouldpredictadecrease
of92kJmol1ingoingtocyclooctane;theenthalpyofformationof
cyclooctanewouldbeabout215kJmol1.Ifweextrapolatethebond
enthalpyincrement,wewouldpredictadecreaseof44kJmol1andan
enthalpyofformationof167kJmol1.Thediscrepancybetweenthesetwo
methodsisquitelargeandleavesuswithlittleconfidenceintheresult.A
similarargumentappliestotheentropyextrapolation.
(e)Onewaytoapproachthisanalysisistolisttheisomersinorderof
decreasingentropiestoseeifanytrendsinthestructuresand/orenthalpies
offormationarediscernable.Wechoosetoorderonthebasisofentropy,
becauseentropyismoreobviouslyrelatedtostructure.
isomer
So,JK1mol1 Hfo,kJmol1
1pentene
347.6
20.92
trans2pentene
342.3
31.76
structure
H2 C CHCH2 CH2 CH3
H3 C
2methyl1butene
2methyl2butene
342.0
338.5
36.62
42.55
CH 3
H2 C
H3 C
H3 C
3methyl1butene
333.5
28.95
CH
CH 2CH 3
CH 2CH 3
C
CH 3
H
CH 3
H2 C
CHCH
CH 3
Thetableshowsthatthemorecompactthestructure,theloweritsentropy.Themost
floppystructureis1pentene.Youcantwistitsmodelintomanydifferentconformations
andithasahigherentropythananyoftheothers.Atthebottomofthelist,2methyl2
buteneand3methyl1butenehavelittleflexibility,excepttherotationoftheirmethyl
groups.Theabsolutevaluesoftheentropyarehighbecausethemoleculesaregasesand
theyhavemanyatoms.Ingeneral,themoreatoms,thehighertheentropy.Yousawthis
Chapter8
complexityeffectinthegraphfortheentropyasafunctionofnumberofcarbonsin
part(c).Patternsintheenthalpiesofformationarehardertosee,butitdoesseemthatthe
enthalpyofformation(stability)increasesasthenumberofcarbonsbondedtothe
doublebondedcarbonsincreases.Thelowestvaluesarefor1penteneand3methyl1
butene,theisomerswithonlyonecarbonbondedtothedoublebond.2methyl2butene,
withthreecarbonsbondedtothedoublebondhasthehighestenthalpyofformation.A
deeperknowledgeofbondingisrequiredtofigureoutwhythestabilityincreasesinthis
way.
8.90.
Aninventorclaimstohavediscoveredacatalystthatwillbreakwaterdowntohydrogen
andoxygengasesatroomtemperaturewithoutaninputofenergy.Usedatafrom
AppendixXXandthermodynamicargumentstocounselpossibleinvestorswhetheror
nottoinvesttheirmoneytocommercializethiscatalyst.
Answerto8.92:
Thereactionofbreakingwaterdowntoitselementsisthereverseofthereactionforming
waterfromitselements.Theenthalpychangeforthebreakdownhasthesamemagnitude,
butisoppositeinsigntotheenthalpyofformationofwater.ThedatainAppendixXX
givetheenthalpyofformationofwater(gas)as241.82kJmol1,fromwhichweget
+241.82kJmol1fortheenthalpychangeofthebreakdown.Thisisthenetenthalpy
associatedwithbreakingfourHObondsinwaterandformingtwoHHbondsandone
O=Obond.Althoughthevaluewillvarysomewhatundernonstandardconditions,itwill
alwaysbepositive,thatis,energywillalwaysberequiredtocausethebreakdown.Thus,
investorsshouldbewaryofaninventorwhoclaimsthatthisprocesscanbemadeto
occurwithoutaninputofenergy.Catalystscannotchangetheoverallthermodynamicsof
areaction.
8.91.
Liquidsevaporate,moleculesleavetheliquidandenterthegasphase.Thepressureofthe
gasmoleculesinequilibriumwiththeliquidisthevaporpressureoftheliquidatthat
temperature.Solutionsofnonvolatilesoluteshavelowervaporpressuresthanthepure
solvent;vaporpressureloweringisanothercolligativeproperty.
(a) Whichentropyishigher,thatforpuresolvent,Ssolvent,orthatforasolution,Ssolution?
Explainyourresponse.
(b) Thesameinputofenthalpy,Hvap,isrequiredtovaporizeagivenamountofliquid
solventfromthepuresolventandfromasolution.Atagiventemperature,howdothe
Chapter8
thermalentropychangesforvaporizationofthesameamountofliquid,Hvap/T,compare
forpuresolventandasolution?Explain.
(c) Atequilibrium,thenetentropychange,Snet,mustbezeroforbothvaporizationofa
puresolventandvaporizationofasolution.Givenyouranswerinpart(b),howmustthe
positionalentropychangesfor(solventgas)and(solutiongas)compare?Explain.
(d) Giventherelativevaluesinpart(a)andyouranwerinpart(c),whichgasmusthave
thehigherentropy,theoneinequilibriumwithpuresolventortheoneinequilibrium
withthesolution?Explainyourreasoning.Hint:AdiagramsimilartoFigure8.26might
beuseful.
(e) Theentropyofagasisinverselyrelatedtoitspressure;higherpressure,more
compressedgashasalowerentropythanthesamegasatalowerpressure.Whichgasin
part(d)hasthelowerpressure?Isthisresultconsistentwithvaporpressureloweringbya
nonvolatilesolute.Explainthereasoningforyouranswers.
(f) Abeakerofwaterandabeakerofa1Maqueousglucosesolutionareplacedside
bysideinsideasealed,transparentcontainerheldatconstanttemperature.Ifyouobserve
thissystemformanydays,whatdoyoupredictyouwillobserveabouttheliquidlevelsin
thetwobeakers?Explainthereasoningforyouranswer.
Answerto8.93:
(a)Asolution,amixtureofcomponents,hasahigherentropythanpuresolvent:Ssolution>
Ssolvent.
(b)Sincetheenthalpyofvaporization,Hvap,forthesameamountofsolventfrompure
solventorfromasolutionarethesame,Hvap/Twillbethesame,atthesame
temperature,forbothpuresolventandasolution.
(c)Theentropychangeofthesurroundings,Ssurr,forthevaporizationprocessis
Hvap/T,sinceenergyleavesthesurroundingstobringaboutthevaporization.Hvapisthe
sameforbothpuresolventandasolution,soSsurr<0andhasthesamenumericalvalue
forvaporizationofpuresolventandasolution.Thus,inorderforSnettobezero,the
positionalentropychangesfor(solventgas)and(solutiongas)mustbeequalto
Ssurr,thatis,bepositiveandofthesamenumericalvalueasSsurr.
(d)WeneedtohaveS(solventgas)=S(solutiongas).SinceSsolution>Ssolvent,we
needtohaveSgasoversolution>Sgasoversolvent,inordertohavetheentropydifferencesbethe
same.Therelationshipsareshowninthisdiagram:
Chapter8
(e)Sincethegasinequilibriumwiththesolutionhasthehigherentropy,itmusthavethe
lowerpressure(whichismorevolumepermoleculeforagivenamountofgas).Thus,the
equilibriumpressureofgaseoussolventoverasolutionislowerthanoverpuresolvent.
Thisisconsistentwithandexplainstheloweringofthevaporpressurebyanonvolatile
solute.
(f)Theequilibriumvaporpressureofwaterinthesystemcanbenohigherthanthevapor
pressureinequilibriumwiththeliquidoflowervaporpressure,thatis,thesolutionof
(nonvolatile)glucose.However,atthislowerpressure,morewatermoleculeswillbeable
toenterthevaporphasefromthepurewater.Thisprocesswouldincreasethepressureof
waterinthesystemandplaceastressontheequilibriumbetweentheglucosesolution
andthegas.LeChateliersprinciplesaysthatthesystemwillrespondbytryingtouseup
someoftheextragaseouswater,thatis,somewatervaporwillcondenseintheglucose
solution.Ifthisprocesscontinuesforalongtime(diffusionofgasesisaslowprocess)all
ofthewaterfromthebeakerofpurewaterwillendupinthebeakerofglucosesolution,
whichwillbedilutedbytheprocess.
8.92.
Thetopdiagramisaschematicrepresentationofthebindingofasubstratemolecule(the
squiggle)intheactivesiteonanenzyme(thefattiltedC).Inordertobind,the
substratehastofoldintoashapethatfitsthesite,asshownontherightofthediagram.
Thebottomdiagramshowstheinteractionofthesubstratewithametalion(thelittle
lozengeshape)insolution.Bindingtothemetalioncausesthesubstratetofoldasshown.
+
+
(a) Ifyouconsideronlythechangesrepresentedbythetopdiagram,whatdoyou
predictabouttheentropychangeforthisprocess?Clearlyexplainyourreasoning.
Chapter8
(b) Howwillthepresenceofthemetalioninthesolutionaffecttheentropyofbinding
ofthesubstratewiththeenzyme?Whatassumptionsdoyoumake?Explainyour
reasoning.
Answerto8.94:
(a)Thefreesquigglemoleculecanmoveaboutandtwistintowhatevershapeis
allowedbyitsbonding.Inordertobindtotheenzyme,oneendofthesquiggle
hastofoldintoaparticularshape.Therearefewerwaystodothisthantotwist
aboutrandomly,sothepositionalentropyofthemoleculewilldecreaseasitfolds
intothisparticularshape.Also,whentwomolecules,theenzymeandthe
squiggle,thatarefreetomoveaboutindependentlyofoneanothercometogether
theylosesomefreedomofmovement.Thisisafurthercontributiontoadecrease
inpositionalentropy.Forthebindingprocessshown,thepositionalentropywill
decrease.
(b)Thecomplexformedbetweenthesquigglemoleculeandthemetalionholdsthe
squigglemoleculeinthefoldedformthatbindswellwiththeenzyme.Thesquiggle
moleculeinthemetalboundformisnotfreetotwistaboutrandomly,sotherewillnotbe
agreatlossofpositionalentropywhenitbindswiththeenzyme.Thefreedomof
movementthroughthesolutionislost,sothepositionalentropywillstilldecreaseupon
binding,butnotasmuchasintheabsenceofthemetalion.Weareassumingthatthe
presenceofthemetalinthefoldedsquiggledoesnotinterferewiththebindingbetween
thesquiggleandtheenzyme.Anexampleofasituationliketheonepicturedhereisthe
bindingofATPtomanyoftheproteinswithwhichitinteracts.Manyofthese
interactionsdonottakeplaceunlessmagnesiumion,Mg2+(aq),ispresentinthesolution
tocomplexwiththeATPandholditinthepropershapefortheinteraction.

Solutions ch08

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Solutions ch08

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Chapter8

(c) Both H and S areassumedtobeconstantoverthetemperaturerangefrom273

Atacertaintemperature, G forthereactionCO2(g) C(s)+O2(g),isfoundtobe

plot of delta G delta H and TdeltaS

Tfp = 1.86 Cm 5.49 102 m = 0.102 C

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