Solutions ch07

SolutionstoChapter7Problems
Section7.1.
EnergyandChange
7.1.
Asliceofcheesepizzatypicallycontains180Caloriesoffoodenergy.Thehuman
heartrequiresabout1Jofenergyforeachbeat.
(a) Assumingthatwhenyoumetabolizethepizza,allofthefoodenergywillbe
usedtokeepyourheartbeating,howmanyheartbeatscanthissliceofpizza
sustain?Abouthowmanyminuteswouldthiskeepyourheartgoing?Hint:1
Calorie=1kcal.
(b)Assumetheefficiencyofuseofthisfoodenergyisaboutthesameasthat
calculatedforcapturingtheenergyfromglucoseoxidation,Section7.9.Whatare
youranswersforpart(a)inthiscase?Explainyourreasoning.
Answerto7.1:
180 Cal
7.2.
Pastaislargelystarchandadeepfriedpotatochipismostlystarchandfat.
(a) WhatdoyourobservationsfromInvestigateThis7.1tellyouaboutthe
energyvalueofthesefoods?Dotheycombineexothermicallywithoxygen?What
istheevidenceandreasoningforyourresponse?
(b) Starchisapolymerofglucose.Isthiscompositionconsistentwithyour
answersinpart(a)andotherdatafromInvestigateThis7.1?Explainyour
reasoning.
Answerto7.2:
(a)Oncetheyhavebeenignitedboththepastaandpotatochipcontinueto
burnontheirown.Theyreleaseenergyintheformoflightandenough
thermalenergytokeeptheirtemperatureshighenoughtocontinue
burning.Youmightfindthatapotatochipburnssomewhatbetterthan
pasta,becausethefatisabetterfuelthanstarch.Thisisreflectedintheir
nutritionalCalorievaluesaswell.Agramofstarchprovidesabout4
Calories(17kJ)andagramoffatabout9Calories(38kJ).
(b)Theoxidationofglucosehasbeenusedasanexamplethroughoutthechapter.
Youknowthattheoxidationisquiteexothermic,whichisshownbytheburning
pasta,potatochip,andmarshmallow(mainlysugarsincludingglucose).Itdoesnt
matterthattheglucoseunitsarestrungtogetherasapolymerinstarchor
Chapter7
ACSChemistryBetaDraft
1
separatedinamarshmalloweachstilloxidizestoproducealargeoutputof
enthalpy.
7.3.
PredicthowtheresultsofInvestigateThis7.1woulddifferifabaked,ratherthan
afried,potatochipwereused.Whatwillhappenifarawpotatosliceisused?
WhatdoyoupredictwillbeobservedifachipusingOlestraisused?Ineach
case,explainthereasonsforyourprediction.
Answerto7.3:
Thebakedchipwillstillburn,butitispredictednottoburnasvigorouslyasthe
friedchipbecausethereislessresidualfatavailableasfuelonthebakedchip.
Therawpotatoslicemaynotburnatallbecauseithasahighwatercontent.The
Olestrachipwillalsoburnquitewell,fortheOlestraisalongchainpolymeric
fattyacid.Itdoesnotproduceheatvalueinthebodybecauseitcannotbe
metabolized.
Section7.2.
ThermalEnergy(Heat)andMechanicalEnergy(Work)
7.4.
Severaldifferenttypesofenergyhavebeendiscussedinthischapter.These
includekineticenergy,mechanicalenergy(work),potentialenergy,andthermal
e
n
r
g
y
potenialenrgm
yechanicalenrkgiyneticenrgytherm
alenrgy
energy(heat).Howarethesetermsrelated?
Answerto7.4:
Potentialenergyandkineticenergyarethetwotypesofenergy.
Mechanicalenergyandthermalenergyarebothexamplesofkinetic
energy.Thisisavisualrepresentationoftherelationship.
7.5.
Figure7.2illustratesamodelforthemovementofcombustiongases.
(a) Drawasimilardiagramforatetheredheliumfilledballoon.Hint:Unlike
Figure7.2,therewillonlybeonetypeofparticle,representingheliumatoms.
(b) Willtheheliumatomsinthetetheredballoonexhibitanydirectedmotion?
Whyorwhynot?Whatwillhappentothemotionoftheheliumatomsinthe
balloonwhenthetetherisreleased?Explainbriefly.
Chapter7
2
Answerto7.5:
(a)
TetheredBalloon
(b)Theheliumatomsintheballoonareinconstant,randommotion.They
donotexhibitanydirectionmotion.Theheliumatomsintheballoonare
stillinconstant,randommotion,keepingtheballoonfullyinflated.The
balloonitselfwilldriftupward,buoyedbytheairmoleculesaroundit.
7.6.
Consideradropofwaterinawaterfall.Attheverytopofthefall,themolecules
inthedroparemovingrandomly.Whileitisfalling(pulleddownbygravity),its
moleculeshaveanoveralldownwardmotion.Whenithitsthepoolatthebottom,
themolecularmotionagainbecomesrandom.
(a) Thewateratthebottomofthewaterfallisalittlewarmerthanthewaterat
thetop.Whatcanyousayaboutthechangeininternalenergyofyourdropof
waterasitgoesfromthetopofthewaterfalltothebottom?
(b) Hasworkbeendoneorhasthermalenergybeentransferredtocausethe
changeintheinternalenergyofthewaterdrop?Explainwheretheworkand/or
thermalenergycomefrom.
Answerto7.6:
(a)Sincethetemperatureofthewaterincreaseswhenitfallsandhitsthe
pool,itsinternalenergymusthaveincreased.
(b)Workhasbeendoneonthewatertoincreaseitsinternalenergy(and,hence,
itstemperature).Theworkisdoneonthewaterwhenitspotentialenergyatthe
topofthefallisconvertedtokinetic(directed)motionasitisfallingandthenthis
directedmotionischangedtorandommotionwhenithitsthepoolatthebottom
andrapidlydeceleratesduetotheforceofthecollision.
Chapter7
3
7.7.
WhenheatisaddedtoH2O to do work, whydoesthevaporformofwater

generatemoreworkthaneithericeorliquidwater?
Answerto7.7:
Watermoleculesinicearetightlyorderedinthecrystallattice.These
moleculesareheldinplacebyhydrogenbondsthatmoveonlyslightly
withinthislattice.Liquidwatermoleculesalsohydrogenbond,butare
capableofbreakingandremakingtheserelativelyweakintermolecular
attractionsasthesewatermoleculesmoverelativetooneanother.Keepin
mindthatthemoleculesofliquidwatermoveslowlycomparedtowater
moleculesinthevaporphase.Thereismorepotentialenergythankinetic
energyassociatedwiththesetwophasesofwater.Inthevaporphase,
wherewatermoleculesareonaverage,quitedistantfromtheirneighbors,
hydrogenbondingisnegligible.Alltheheatenergyaddedtothevapor
phasewateristransformedintokineticenergyandfromthereintouseful
mechanicalwork.Ontheotherhand,heatenergyaddedtoliquidwateris
usedprimarilytobreakhydrogenbondsandonlysecondarilytoincrease
theaveragekineticenergyofthemolecules.
7.8.
Whyisitimportanttoyou,asaconsumer,forautomotiveengineerstodesign
enginesthatconvertthehighestpossiblepercentageofenergytowork?
Answerto7.8:
Economicandenvironmentalfactorsareimportanttoeveryconsumer.Whatever
thepriceofgasoline,consumerswanttoobtainthemaximumnumberofmiles
possiblepergallonofgasoline.Thiscanonlybedoneifthechemicalenergyfrom
thefuelisconvertedefficientlyaspossibletowork,andnotwastedasheat.
Efficientconversionoffuelenergytoworkalsomeansreleaseoflower
concentrationsofcarbonmonoxideandhydrocarbonsintotheatmosphere.
Section7.3.
ThermalEnergy(Heat)Transfer
7.9.
Foreachcasebelow,isthermalenergybeingtransferredbyradiationorbya
contactprocessofconductionand/orconvection?Brieflyjustifyyourchoice.
(a) Asilverspoonatroomtemperature,whenplacedinacupofhotwater,
becomestoowarmtotouch.
(b) Anapplepieisbakedinanelectricoven.
Chapter7
4
(c) Thewaterinanoutdoorswimmingpoolcoolsfrom25Cto20Casthe
summerseasonchangesintoautumn.
(d) Yousunbathewithyourbackexposedtothesun,untilyourbackfeelsvery
warm.
Answerto7.9:
(a)Theprocessofthermalenergytransferisbycontact,usingconduction.
Thewatermoleculesaremovingmorerapidly,ontheaverage,thanthe
silveratomsinthespoon.Thermalenergyistransferredfromthewarmer,
moreenergeticwatermoleculestothecooler,lessenergeticsilveratoms
inthespoon,causingittobecomeuncomfortablywarm.
(b)Thermalenergytransferislikelytakingplacethroughcontact.Both
conductionandconvectionplayaroleinbakingthisapplepie.The
electricheatingunitwilltransferthermalenergytomoleculesofgasesin
theairdirectlyincontactwiththeunit;thisisconduction.Thewarmerair
rises,allowingthedenser,coolerairtocirculateneartheheatingcoil;this
setsupaconvectioncurrent.(Inovensadvertisedasconvectionovens,
thereisatleastonefantohelpdistributetheairevenly.)Themoleculesof
hotgasthatareincontactwiththepiewillconductthermalenergyintothe
pie,eventuallyresultinginbakingthepie.
(c)Thewatertemperatureisgoingdownbecausethermalenergyisbeing
lostbycontactbetweenwarmerwatermoleculesandthecoolerair.
Conductionisinvolveddirectlyatthewater/airinterface,butconvection
currentsinbothwaterandairarelikelythemajorfactorsinthisheat
transferprocess.
(d)Thermalenergyisbeingtransferredfromthesuntoyourbackbymeansofthe
longwavelengthinfraredelectromagneticradiation.Astheradiationisabsorbed
bytheskinonyourback,themoleculesinyourskinaremovingfasterwhich
increasestheirtemperature.Infraredradiationisaccompaniedbythemore
energeticultravioletrays,soremembertousesunscreentoavoidskindamage.
7.10.
Attheendofaskatingseason,anindooricerinkwasclosed.Withoutanyoutside
cooling,howwilltheroofandtheicerinkfloorreachacommontemperature?
Willitbeasloworfastprocess?Explainyouranswer.
Answerto7.10:
Chapter7
5
Sincethecoolerairneartheicerinkfloorhasahigherdensity,itwillstay
stagnantforarelativelylongtime.Theicerinkfloorwillremaincooluntilitis
warmedupbyheatconductionfromtheroofortheoutsidethroughthewalls.
Heatwillbeconductedbytheinteractionsofwarmandcoolairmolecules.This
processisnotgoingtobefast.Convectionisveryinefficientinthissituation.
7.11.
Afterbeingimmersedincoldwater,thecorebodytemperatureofanindividual
maybeabnormallylow.Designthreemethods,oneusingconvection,thesecond
usingconduction,andthethirdusingradiationtotransferheattowarmupan
individualasquicklyandsafelyaspossible.Whichmethodwillbethemost
efficientinthiscase?
Answerto7.11:
Theconvectionmethodmightconsistofasmallchamberwithaheatedfloor.
Theproblemwiththisheatingmethodisthataborderofstagnant,coldairmay
surroundtheindividual.Sincethecoolerairneartheindividualhasahigher
density,itwillstaystagnantforarelativelylongtimeandpreventefficient
warming..Theradiationmethodmayconsistofalargechamberwithsecured,
openflameinside.Inthismethod,thermalenergywillbetransferredtothevictim
fromtheflamebyinfraredelectromagneticradiation,.Itisnotgoingtobesafe
andefficientmethodbecauseoftherisksofburningtheindividual.Also,since
radiationtravelsinstraightlines,notallareasoftheindividualwillbewarmed
equally.Wrappingthevictiminanelectricblanketwillbethemostefficient
processofheating.Inthismethod,heatistransferredbyconduction.The
individualwillbeheatedquicklyanduniformly.
Section7.4.
StateFunctionsandPathFunctions
7.12.
Yourmonthlybankstatementgivestheopeningbalanceforyouraccount,details
thetransactionsthathaveoccurred,andreportstheendingbalance.Whichaspects
ofthisstatementcorrespondtostatefunctionsandwhichtopathdependent
functions?
Answerto7.12:
Thedifferencebetweentheendingandinitialbalancecorrespondstoa
statefunction.
Balance = Balanceend Balancestart
Chapter7
6
Allofthetransactionscorrespondtopathdependentfunctions.Theydescribeall
thedifferentexpendituresanddepositsthatareresponsiblefortheoverallchange
inbalance.
7.13.
Thequarterbackstartsaplayonhisown35yardline,butispushedbackbythe
defensetohisown25yardline.Hethensuccessfullycompletesapasstothe
opponents40yardline.Whatisthenumberofyardsgainedintheplay?Isthe
numberofyardsgainedastatefunctionorapathdependentfunction?
Answerto7.13:
Theplayhasmovedtheteamfromtheirown35yardline,pastmidfield,andto
theopponents40yardline.Theteamhasmovedtheball25yardsclosertothe
endzone,anotherexampleofastatefunction.Thepathtakendoesnotmatter,
onlythefactthatthisisafirstdownplaysuccessfullycompleted.
7.14.
Todaysmostadvancedfossilfuelburningpowerplantsproducingelectricity
operateatanefficiencyofabout42%.Suggestsomereasonswhyahigher
percentageoftheenergyfromburningthefossilfuelsisnotconvertedtowork.
Doyouthinkitistheoreticallypossibletoconvert100%oftheenergyintowork?
Explainyourreasoning.
Answerto7.14:
Asignificantfractionoftheheatenergyistransferredtothewaterusedtocool
theturbines,andtherearemanysourcesoffrictionintheturbinesandgenerator.
Evenwhentheelectricityhasbeengenerated,therewillbelossesoverlong
distancepowerlinesusuallyrequiredtoreachthepowergrid.Moststudentswill
intuitivelyrecognizethatrealizethisseemsunlikelyandtheintroductiontothis
chaptertellsthemitisnotpossible.Heatlossesmustpresentseriouslimitations,
giventhatthebestengineershaveonlyfounda42%efficiencyratepossible.A
morecompleteanswertothisquestionwillbepossibleafterstudyingChapter8,
Entropy,wheretheSecondLawofThermodynamicsisstudiedinmoredetail.
7.15.
Considertwodifferentcasesinwhichafullychargedbatterybecomestotally
discharged.
Case1:Thebatteryisusedtoprovidepowertoaflashlight.
Case2:Thebatteryisusedtoprovidepowerforachildstoycar.
Chapter7
7
(a)Willthechangefromthebatterybeingfullychargedtobeingtotally
dischargedbeastatefunctionorapathdependentfunctionineachcase?Explain
yourreasoning.
(b)Willtherebeanythermalenergytransferbyradiationorbycontactineither
useofthebattery?Explainyourreasoning?
Answerto7.15:
(a)Thechangefromthebatterybeingfullychargedbatterytobeing
totallydischargedbatteryisastatefunctioninbothcases.Thepathis
quitedifferent,buttheendresultisexactlythesame,adeadbattery.State
functionsdonotdependonthepathtakentoachievethepresentstate.
(b)InCase1,muchoftheenergylostbythebatterywillbereleasedasradiant
energy,light.Batteriesdogetwarmastheyarebeingused,alsoindicatingthat
thereissomethermalenergytransfer.InCase2,therewillbesomethermal
energytransferbecauseoffrictionbetweenthetoycarandtheroadbedonwhich
thecarruns.Muchoftheenergylostwillbechangedtomechanicalworkdonein
movingthetoycar.
7.16.
ConsideraC172airplane(smallprivateplane),ahelicopter,aparachutejumper,
andahawk,allpresentlyat1892feetabovetheClemson,SouthCarolinaairport,
whichisatanaltitudeof892feet.Eachplansalandingattheairport.Comment
onthestatefunctionsandpathfunctionsforeachoftheseairborneobjects.
Answerto7.16:
Thestatefunctionswillbeidentical,aseachobjectwillmakeanaltitudechange
of1000feettolandsafelyontheground.Thepathfunctionswillbequite
different,however.Theairplaneandhelicopterareobligedtofollowcertain
trafficpatterns,withdesignatedaltitudesanddescentratesintotheairport.The
parachutejumperwilllikelybefollowingaspiralpatterntolandsafely.Thebird
willtakewhateverpathitwantsto,withlittleregardtotheairplane,helicopter,or
parachutejumper.Interestinglyenough,thebirdalsolandsintothewind,justas
theotherairborneobjectsplantodo!
Chapter7
8
Section7.5.
SystemandSurroundings
7.17.
Whichending(s)forthefollowingsentenceis(are)correct?Explainyour
reasoningineachcase.Theenthalpychangeforasystemopentotheatmosphere
is
(a) dependentontheidentityofthereactantsandproducts
(b) zero
(c) negative
(d) qP
(e) positive
Answerto7.17:(a)and(d)
7.18.
Givereallifeexamplesofthefollowing:
(a) anopensystem
(b) aclosedsystem
(c) anisolatedsystem
(d) anexothermicprocess
(e) anendothermicprocess
Answerto7.18:
(a)Anopensystemreferstopartoftheuniversebeingstudiedthatcan
exchangematterandenergywithitssurroundings.Someopensystem
examplesincludeanopenaquarium,acupofcoffee,andhotsprings.Our
bodyisalsoanopensystemsinceweexchangebothenergy(intheform
ofheat)andmatter(food,O2,CO2,H2O)withthesurroundings.
(b)Inaclosedsystem,onlyenergyisexchanged.Anexampleofsuch
systemisacupwithhotcoffeethatistightlyclosedsonovaporsmay
escapebutthecupisnotisolatedsoheatenergymaybeexchangedwith
surroundings.
(c)Anisolatedsystemdoesnotexchangematterorenergy.Anexampleof
anearlyisolatedsystemmightbeaproperlystopperedThermosbottle.
Astopperpreventswatervaporfromescaping,whilethevacuum
constructionkeepsheatfrombeinglosttothesurroundings.
(d)Anexothermicprocessisaprocessthatreleasesheattoits
surroundings.Reactionsofsodiummetalwithwater,burningofamatch
orsolidificationofmoltenmetalsareexamplesexothermicprocesses.
Chapter7
9
(e)Anendothermicprocessisaprocessthatabsorbsheatintoitssurroundings.
Meltingiceorevaporationofrubbingalcoholareexamplesofendothermic
processes.
7.19.
AproperlystopperedThermos bottlecontainingcoffeeisnearlyanisolated
system.Thestopperpreventswatervaporfromescaping,whilethevacuum
constructionkeepsheatfrombeinglosttothesurroundings.Howwouldyouturn
thisisolatedsystemintoanopensystem?Aclosedsystem?
Answerto7.19:
Anopensystemcanexchangematterandenergybetweensystemand
surroundings.OpeningthestopperwouldchangeThermos bottleintoopen
systeminwhichmatter(vapors)andheatcanbetransferred.Aclosedsystemcan
exchangeenergywithitssurroundings,butnomatter.If,forexample,thestopper
ofThermos bottleispiercedwithapieceofheavygaugecopperwire,heat
wouldleavethesystembyconductionalongthecopperwire.Removingthe
vacuumconstructionwouldalsoconverttheisolatedsystemofThermos bottle
intoanopensysteminwhichheatcanbeexchangedthroughthewallsofthe
bottle.
7.20.
Theearthissometimesdescribedasaclosedsystem,particularlywhen
consideringregionalorglobalenvironmentalproblems.Forexample,acidrain
mayfallatgreatdistancefromtheoriginalsiteofemissionsresponsibleforthe
observedeffect.OzonedepletionneartheSouthPoleislinkedtotheemissionof
fluorocarbonsfromusesinindustrialnations.Whilethisviewdoesconveya
senseofthemanyconnectionsthataffectenvironmentalissues,isitcorrectto
thinkoftheearthasaclosedsystemfromthestandpointofthermodynamics?
Whyorwhynot?
Answerto7.20:
Theearthisanopensystembecausematterandenergyisexchangedonaregular
basiswiththesurroundings.Forexample,moleculesescapetheearthssurface
regularly,placinggasesthatareresponsibleforacidrainintotheatmosphere.
Meteoritesfalltotheearthfromouterspace.Thermalenergyistransferredfrom
theearthtotheatmosphere,andvarioustypesofelectromagneticenergyare
transferredtotheearthssurface.
Chapter7
10
7.21.
Thisdiagramshowsan
experimentinwhichahotsilver
barisaddedtoabeakerofwater
atroomtemperature.
(a) Iftheobjectofthe
experimentistofindthespecific
heatofthesilver,definethe
systemandthesurroundings.
(b) Ifyoualreadyknowthespecificheatofthesilver,thesameexperimentalset
upmightbeusedtodetermineifthereisheatlossthroughthewallsoftheglass
beakerorfromthethermometeritself.Definethesystemandsurroundingsinthat
experiment.
(c) Doesthisexperimentaldiagramillustrateanopen,closed,orisolatedsystem?
Givethereasoningbehindyourchoice.
Answerto7.21:
(a)Thesilverbarandthewaterformthecollectionofatomsand
moleculesunderconsideration,thesystem.Everythingelse,includingthe
beaker,thethermometer,theairabovethewater,andeverythingelsein
theuniversearesurroundings.Therewillbethermalenergytransferfrom
thewarmersilverbartothecoolerwatermoleculesuntilequilibriumis
reached.Atthatpoint,theheatreleasedbythesilverbarequalstheheat
gainedbythewater.Itisnecessarytoknowthemassofthesilverbar,the
massofwaterpresent,andthespecificheatofwater.
(b)Thesilverbar,thewater,thebeaker,andthethermometerareallpart
ofthesysteminthisexperiment.Everythingelseformsthesurroundings.
(c)Thisisanopensystembecausematterandenergycanbeexchangedwiththe
surroundings.Forexample,watermoleculescanevaporatefromorcondenseonto
thesurfaceofthewater.Heatmaybeexchangedbetweenthesystemandthe
surroundings.Therefore,thiscannotbeaclosedsystembecausemattercanbe
exchanged.Itisnotanisolatedsystemasthereisnoattempttocontrolthermal
exchangesbetweenthesystemandthesurroundings.
Chapter7
11
Section7.6.
CalorimetryandIntroductiontoEnthalpy
7.22.
Inacalorimetricmeasurement,whymightitbeimportanttoknowtheheat
capacityofthecalorimeter?Thecalorimeterheatcapacityistheamountof
thermalenergythecalorimeter(container,thermometer,etc.)transfersperdegree
temperaturechange.
Answerto7.22:
Toaccuratelymeasurethethermalenergychangeforreaction,weneedtoaccount
forheatthatgoestoheating(inthecaseofexothermicreaction)orcooling(inthe
caseofendothermicreaction)thecalorimeteritself.Theheatlostorgainedtothe
calorimetermustbeexperimentallydeterminedforeachcalorimetertoassurethe
accuracyofcalorimetricmeasurements.
7.23.
Choosethebestresponsetocompletethefinalsentence.Explainwhyyoumake
thischoiceandwhatiswrongwitheachoftheothers.Theequationfor
decompositionofgaseousammonia,NH3(g),is:
NH3(g)1/2N2(g)+3/2H2(g)
H=45.9kJ
Thisreactionequationandenthalpychangeindicatethattheformationofgaseous
ammonia
(a) evolves45.9kJforeachmoleofammoniaformed.
(b) evolves23kJforeachmoleofnitrogenused.
(c) absorbs45.9kJforeachmoleofammoniaformed.
(d) absorbs23kJforeachmoleofnitrogenused.
(e) isanexothermicprocess.
Answerto7.23:(c)
7.24.
A10.0gsampleofanunknownmetalwasheatedto
100.0Candthenaddedto20.0gofwaterat23.0Cin
aninsulatedcalorimeter.Atthermalequilibrium,the
temperatureofthewaterinthecalorimeterwas25.0C.
Whichofthemetalsinthislistismostlikelytobethe
unknown?
SpecificHeatData
H2O(l) 4.184Jg1C1
Au(s)
0.13Jg1C1
Ag(s)
0.22Jg1C1
Al(s)
0.90Jg1C1
Answerto7.24:
Whenthehotmetalisplacedinthecoolerwater,theheatlostbythemetal
andtheheatgainedbythewatersumtozero.
Chapter7
12
heatlost+heatgained=0
heatlost=heatgained
mmetalsmetal(Tf,metalTi,metal)=mH2OsH2O(Tf,H2OTI,H2O)
4.184J
10gsmetal(25.0C100.0C)=20gwater g (25.0C23.0
C)
specificheatmetal=0.22Jg1C1Themetalislikelytobesilver.
7.25.
Astudentreceived55.0gofunknownmetalfromhislaboratoryinstructor.To
identifythismetal,hedecidedtocalculateitsspecificheat.Heheatedthemetal
sampletoatemperatureof98.6Cinawaterbath.Thenhetransferreditslowly
toacalorimetercontaining100.mLofwaterat24.6C.Themaximum
temperaturereachedbythecalorimetersystemwas25.8C.Hislabinstructor,
whowaswatchingtheexperiment,explainedtothestudentthathehad
introducedalargeamountoferrorandaskedhimtorepeattheexperimentwith
thecorrectprocedure.Inthesecondtrial,thetemperatureofthewaterbathwas
98.4Candtheinitialtemperatureofwaterinthecalorimeterwas24.3C.The
maximumtemperatureafterthesamplewasimmersedinthecalorimeterwas26.5
C.Whaterrorhadthestudentmade?Explainhowyouknow.
Answerto7.25:
Thestudenttransferredthehotmaterialintothecalorimetertooslowly.Theheat
lostfrommetalwastransferredtotheairoutsidethecalorimeteranditwasnot
equaltotheheatgainedbythewaterinthecalorimeter.Therefore,thestudent
measuredalowerfinaltemperatureofthewaterforthefirsttrial.
7.26.
Astudentmixed100.mLof0.5MHCland100.mLof0.5MofNaOHina
Styrofoamcupcalorimeter.Thetemperatureofthesolutionincreasedfrom
19.0Cto22.2C.Isthisprocessexothermicorendothermic?Assumingthatthe
calorimeterabsorbsonlyanegligiblequantityofheat,thatthedensityofthe
solutionis1.0gmL1,andthatitsspecificheatis4.18Jg1C1,calculatethe
molarenthalpychangeforthereaction:
HCl(aq)+NaOH(aq)H2O(l)+NaCl(aq)
Answerto7.26:
Totalvolumeofsolutionis200mL.Themassofthesolutionis:(200
mL)x1g/mL=200g
Thetemperaturechangeis22.2oC19.0oC=3.2oC.
Chapter7
13
Thetemperatureincreased.Thismeansthatthermalenergyisreleased
fromthesystemandthereactionisexothermic.
Theheatgainedbywaterisgivenbytheproductofthemass,specific
heat,andtemperaturechange.
qp=(200g)x(4.18J/goC)x(3.2oC)=2700J=2.7kJ
Theheatgainedbythesystem(reactingchemicals)isq=2.7kJ.
Tofindtheheatevolvedpermoleofreactants(enthalpychange)we
havetocalculatethenumberofmoles.
(0.1L)x(0.5mol/L)=0.050mole
H=2.7kJ/0.05mole=54kJ/mole
7.27.
Instantcoldpacks,suchasthoseusedtotreatathleticinjuries,containammonium
nitrateandaseparatepouchofwater.Whenthepackisactivatedbysqueezingto
breakthewaterpouch,theammoniumnitratedissolvesinwater.Thisisan
endothermicreactionandthechangeinenthalpyis25.7kJmol1ofammonium
nitratedissolved.
(a) Whydoesthisendothermicreactionproduceacoldsensationonyourskin?
(b) Thecoldpackcontains125gofwatertodissolve50.0gofammonium
nitrate.Whatwillbethefinaltemperatureoftheactivatedcoldpack,iftheinitial
roomtemperatureis25C?Assumethatthespecificheatofthesolutionisthe
sameasthatforwater,4.184Jg1C1.
(c)Whatotherassumptionsdoyoumakeincarryingoutthecalculationinpart
(b)?
(d) Thefinaltemperatureisabout7C.Doesthisresultjustifytheassumptions
inparts(b)and(c)?Ifnot,explainwhichassumption(s)mightnotbevalid.
Answerto7.27:
(a)Thesolutionprocessisendothermicandisdrawingheatfromyour
bruisedskintoenabletheammoniumnitratetodissolve.
(b)Ifthecoldpackcontainsamplewatertodissolve50.0gofammonium
nitrate,
50.0gNH 4 NO 3
Chapter7
is

14
theheatabsorbedbythedissolvingammoniumnitrate.Thisisequalto
theheatabsorbedbythewater.
1.61 10 4 J = 175gH 2O
4.184J
(XC 25C)
g C
X
(c)Itisassumedthatthereisnoheatlossorgainbetweentheheatpackandthe
surroundings.
Section7.7.
BondEnthalpies
7.28.
Ethanol,byitselforinblends,isanimportantalternativefuelforgasoline
poweredengines.Themolecularequationforthecompletecombustionofethanol
is:
C2H5OH(l)+3O2(g)2CO2(g)+3H2O(l)
(a) RewritethebalancedequationusingfullLewisstructuresforeachreactant
andproductmolecule.
(b) Useyourmodelsetandbuildamodelofeachreactantandproductmolecule
inthisreaction.
(c) RefertotheLewisstructures,themodels,andTable7.3todeterminethe
totalenthalpyinputthatwillberequiredtobreakallthebondsinthereactants.
(d) RefertotheLewisstructures,themodels,andTable7.3todeterminethe
totalenthalpythatwillbereleasedinformingallbondsintheproducts.
(e) Whatisthenetenthalpychangeinthiscombustionreaction?Isyourresult
likelytobeanoverestimateorunderestimateoftheexperimentalHoreaction?
Explainyourreasoning.
(f) Ethanolisalsoafuelwhenconsumedbyhumans.Willyourresultinpart(e)
alsogiveanestimateforethanolsfuelvalueinourbodies?Whyorwhynot?
Answerto7.28:
(a)
Answer7.1.
H
+3
O
H
Answer7.2. (b)Useyourmodelsetandbuildamodelofeachreactant
andproductmoleculeinthisreaction.
Chapter7
+3
15
Answer7.3. (Couldinsertphotoofmodelshere)
Answer7.4. (c)BHreactants=(5BHCH+1BHCC+1BHCO+1
BHOH)+(3BHO=O)
=[(5mol414kJmol1)+(1mol347kJmol1)+(1mol351
kJmol1)+(1mol460kJmol1)]+[(3mol499kJmol1)=4725kJ
Thisistheenergyrequiredtobreakallbondsinreactants.Thesignis
positiveshowingbondbreakingisanendothermicprocess.
(d)BHproducts=(22BHC=O+32BHOH)
=[(4mol745kJmol1)+(6mol460kJmol1)=5740kJThisis
theenergyreleasedinformingallbondsinproducts.Thesignisnegative
showingthatbondformationisanexothermicprocess.
(e)H=BHreactants+BHproducts=+4725kJ+5740kJ=1015kJThe
combustionofalcoholisanexothermicprocessoverall,justasisexpected
ifthesubstanceisbeingusedasafuel.Theexperimentalreactionenthalpy
willinvolveareactant(ethanol)andproduct(water)intheirliquidstates,
butthecalculationsbasedonbondenthalpiesassumeallspeciesaregases.
Sincethisisanexothermicreaction,theethanolisatahigherenergythan
theproducts.Convertinggaseousethanoltoliquidwillloweritsenergy,
sotheeffectwouldbetoreducetheexperimentalrelativetocalculated
energy.Convertinggaseouswatertoliquidwillloweritsenergyandthe
effectwouldbetowidentheenergygapbetweenthereactantsand
productsandthusincreasetheexperimentalrelativetocalculatedenergy.
Whicheffectwouldpredominate?Threemolesofwaterareliquefied,but
onlyonemoleofethanol.Themolarenthalpyofvaporization(or
condensation)ofethanolandwaterareaboutthesame(Table1.2in
Chapter1),sothewatereffectwouldbelargerandthecalculatedenergy
wouldlikelybeanunderestimate.(Thevaluecalculatedfromstandard
enthalpiesofformationSection7.8isabout1368kJmol1,which,as
predicted,issomewhatlargerthanthevalue,1231kJmol1,frombond
enthalpies.)
Chapter7
16
(f)Thecalculationoftheenthalpyofcombustionwasdoneusingaverage
bondenthalpiesforgaseouscompoundsat25Candthereissomeerrorin
usingsuchvaluesforcompoundsinotherstates.Theresurelywouldalso
besomedifferencesifcombustionthroughmetabolicprocesseswereto
takeplace.Still,valuesforfoodenergyaredeterminedthrough
combustionreactionscarriedoutintypicalcalorimetricexperiments.
7.29.
Ethanol,CH3CH2OH,anddimethylether,CH3OCH3,areisomers.Useaverage
bondenthalpiestodeterminewhichoftheisomersisthemorestable.Byhow
much?Clearlyexplainyourreasoningandthecalculationsyoudotogetyour
result.
Answerto7.29:
Themorestableisomerwillrequiregreaterenergytodissociateitinto
atoms.Wecanusebondenthalpiestocalculatetheenthalpychangefor
atomizationofeachisomerandcomparetheresults.
ethanol
dimethylether
bond #bonds BH,kJ
#bonds BH,kJ
CH 5
2070
6
2484
CC 1
347
OH 1
460
CO 1
351
2
702
Total
3228
Total
3186
7.30.
Ethanolrequiresmoreenthalpytoatomizetothesamecollectionofatoms,soitis
themorestableofthesetwoisomersbyabout42kJ(permoleof
isomer).Considerthisreactioninwhichtwoaminoacidsjointoformapeptide
bond,releasingawatermolecule:
H H
O
N C C
H R
O H
H O
N C C
H
R' O H
H
H O
H
N C C
O
H
N
C C
R
H R' O H
H
H
O
Useaveragebondenthalpiestoestimatetheenthalpychangeforthisreaction.
Answerto7.30:
H=BHreactants+BHproducts=(1BHCO+1BHNH)+(1BHCN+1
BHOH)=[(1molkJmol1)+(1molkJmol1)]+
[(1molkJmol1)+(1molkJmol1)]=740kJ+736
kJ=+4kJ
Chapter7
17
7.31.
Theglucosemoleculecanexistinanumberofdifferentforms,includingthe
openchainandcyclicformsrepresentedbelow.Byconvention,thecarbonsinthe
chainarenumbered1through6beginningatthetop,asshown.Carbon1inthe
cyclicformistheoneatthefarrightofthestructure.Tomakethecyclicform,the
oxygenbondedtocarbon5inthelinearformbecomestheringoxygeninthe
cyclicformwhereitisbondedtobothcarbon1andcarbon5.Whichisthemore
stable,theopenchainorthecyclicstructure?Howmuchmorestable?Showyour
reasoningandcalculationsclearly.
H 1C
H 2C
HO 3C
H 4C
H 5C
H 6C
H
O
OH
H
OH
OH
OH
H
O
H
C
O
HO
C H
H C
O C
O
H
H
H
H
C
CO
H
H
openchain
cyclic
Answerto7.31:
Allthebondsinthetwoformsarethesame,exceptthoseinvolvedin
makingthecyclicformfromtheopenchainform.Thechangeinvolves
breakingaC=Ooncarbon1andmakingtwoCObondsinitsplace.
AnOHbondalsohastobebroken,butanotherismade,sotheycancelout.Thus,
thedifferenceis745kJforC=Ocomparedto702kJfor2CO.Bythis
calculation,theopenchainformwouldbemorestable(requiremoreenergyto
atomize)byabout43kJthanthecyclicform.Innature,almostallglucose
Chapter7
18
moleculesexistincyclicforms.Theremustbeanotherstabilizinginfluence(or
bondenthalpycalculationsforglucose,whichisasolid,arenotaccurateenough
togiveustheactualenthalpydifference).
7.32.
TwoisomerswiththemolecularformulaCH2N2are:
H
C N N
H
diazomethane
H
H
N
N
diazirine
Diazomethaneanddiazirinearebothgases.Underappropriateconditions,each
canreacttogiveetheneandnitrogen:
2CH2N2(g)H2C=CH2(g)+2N2(g)
(a) UseaveragebondenthalpiestocalculateHreactionfordiazomethaneandfor
diazirineundergoingthisreaction.Arethereactionsexothermicorendothermic?
(b) Constructenthalpyleveldiagrams(likeFigure7.11)forthetworeactions.
Whichisomeristhemorestable?Arethereanyfactorsthatmightcomplicateuse
ofbondenthalpiesforthesemolecules?
(c) Doesourmolecularbondingmodelhelpexplaintherelativestability?
Explainwhyorwhynot.
Answerto7.32:
(a)Notethat,forbothreactions,wecanignoretheCHbonds,sincethereare
fourinreactantsandfourintheproducts.Wehavetofocusonthecarbon
nitrogen,andnitrogennitrogenbonds.
Forthereactionoftwomolesofdiazomethane,wehave:
Hrxn=BH(C=C)2BH(NN)+2BH(C=N)+2BH(N=N)
Hrxn=6202(941.4)+2(615)+2(418)=437kJ
Forthereactionoftwomolesofdiazirine,wehave:
Hrxn=BH(C=C)2BH(NN)+4BH(CN)+2BH(N=N)
Hrxn=6202(941.4)+4(276)+2(418)=563kJ
Thesereactionsarehighlyexothermicwiththepredominantcontributioninboth
casescomingfromthegreatstabilityofthetriplebondednitrogenproduct.Note
thatthatonlydifferencebetweenthesetwocalculationsisthebreakingof
differentkindsofcarbonnitrogenbonds.Fordiazomethane,twoC=Nbondsare
brokenand,fordiazirine,fourCNbondsarebroken.Recallthattheenthalpy
changerequiredtobreakoneC=Nbondisgreaterthantwicetheenthalpychange
Chapter7
19
tobreaktwoCNbonds.Thedifference,63kJ.Fortwomolesofdiazomethane
anddiazirine,thedifferenceinreactionenthalpiesis126kJ(=263kJ),reflecting
thedifferenceincarbonnitrogenbondsbroken.
(b)
Diazomethaneisthemorestablemolecule,relativetodiazirine.Complicating
factorscouldbethestrainofmakingthethreememberedring(whichdistortsthe
usualbondinganglesforcarbonandnitrogen)indiazirineand/ortheformal
separationofchargeinthediazomethanemoleculethatcouldmakeitlessstable
thanacomparablemoleculewithoutformalcharge.
(c)Youmightarguethatthestrainenergyindiazirineisresponsibleforitshigher
energy(63kJmol1higher,basedonthesebondenthalpycalculations),butthe
argumentisnotwhollysatisfactory.Tocomplicatematters,wefind
experimentallythatdiazirinecanbekeptasagasinthedarkatroomtemperature
indefinitely,whereassamplesofgaseousdiazomethanereactasshownhereand
onthewallsoftheircontainerswithinafewhours.Basedonexothermicity,the
reactionsshownhereseemveryfavorable,althoughweknowthatexothermicity
isnotagoodcriterionfordecidingthedirectionofareaction.Diazomethanedoes
react,butsomefactorslowsthediazirinereactionsomuchthatitisundetectable.
Chapter7
20
Chapter7
21
7.33.
Thetableattherightgivesthemolecular
Sugar
formulasandenthalpiesofcombustionfor
Formula
Hcombustion
1
kJ mol
fructose C6H12O6
galactose C6H12O6
glucose C6H12O6
threecommonsugarsfoundinliving
organisms.Whatconclusionscanyoudraw
fromthesedataaboutthebondinginthese
2812
2803
2803
molecules?Explainyourresponse.
Answerto7.33:
Asyousee,thesemoleculesareisomers,andtheircompletecombustionwillgive
identicalproductsineachcase:6moleculesofCO2and6moleculesofH2Ofor
eachmoleculeofsugaroxidized.Theidenticalvaluesoftheirenthalpiesof
combustion(towithin0.3%)indicatesthatthebondingmustbeessentially
identicalintheseisomers.Thatis,theremustbethesamenumberofCC,CH,
CO,C=O,andOHbondsinallthreemolecules.Thisistrueifyoucompare
theiropenchainformswithoneanotherortheircyclicformswithoneanother(in
nature,thecyclicformsvastlypredominate).
7.34.
Disaccharidesaresugarsformedbythecombinationoftwosimplersugars.A
maltosemolecule,forexample,isacombinationoftwoglucosemolecules:
H
O
H H
C
O
H O
C H
H C
OC
O
H
H
H
H
C
H
O
H H
C
O
H O
C H
H C
O C
O
C O
H
H
H
H
H
H
C
C O
H
H
H O
H
C
H
O
HCH
O C
H H
C
H
H
C
O
H
H
C
H
O
H
C
O
C H
O
H C
OC
O
C OH
H
H
H
H
H
C
H2 O
(a) EstimateHreaction,usingbondenthalpies.Isitnecessarytodoanynumerical
calculationstomakethisestimate?Explainwhyorwhynot.
(b) Useyourresultfrompart(a)andthedatafromtheProblem7.33toestimate
theenthalpyofcombustionofmaltose.Theexperimentalvalueis5644kJmol1.
Howwelldoesyourestimatecomparetotheexperimentalvalue?Howdoyou
explaintheagreementorlackofagreement?
Answerto7.34:
(a)InthisreactionaCObondisbrokeninonesugarandanOHbondin
theother.Thentomaketheproducts,aCObondismadebetweenthe
twosugarsandanOHbondismadetoproducethewater(fromtheOH
thathadleftasugar).Exactlythesamenumberandkindofbondsare
brokenandmade.Bondenthalpycalculations(whichwedonothaveto
Chapter7
22
do,ifthereisnochangeinthekindandnumberofbonds)givean
estimatedHreaction=0kJforthisreaction.
(b)Onewaytoestimatetheenthalpyofcombustionofmaltoseistobreak
thereactionintotworeactions:hydrolysisofmaltosetogivetwoglucose
andthencombustionoftheglucose:
maltose+H2O2glucose
Hrxn=0kJ
2glucose+12O212CO2+12H2O
Hrxn=5606kJ(from7.17)
Thesumofthesetworeactionsis:
maltose+12O212CO2+11H2O
Hrxn=5606kJ
Thisisthecombustionreactionformaltose;wepredictHrxn=5606kJtobe
comparedwiththeexperimentalvalueof5644kJ.Thedifferenceissmall(only
about0.6%),butthecombustionenthalpiesareexperimentalvaluesthataregood
toatleastfoursignificantfigures.Thismeansthattheestimatedvalueof0kJfor
theformationofmaltose(orthereverse,itshydrolysis)isincorrect.Theactual
valueforthehydrolysisabovemustbeabout36kJ,inordertomakethesumof
thetworeactionenthalpiesaboveequaltothemeasuredenthalpyofcombustion
ofmaltose.Weknowthatbondenthalpiesareaveragesthatcanbeoffbyafew
percentforanyparticularbondinamolecule,soweshouldntbesurprisedthat
thissmalldiscrepancyoccurs.Itisawarning,however,nottotrustbond
enthalpieswhenthequantityofinterestisthedifferencebetweentwolargevalues
smallerrorsinthelargevaluescanleadtolargepercentagediscrepanciesin
theirdifference.
7.35.
Thereactionbetweenhydrazineandhydrogenperoxideinrocketenginescanbe
representedas:
H2NNH2(g)+2HOOH(g)N2(g)+4H2O(g)
(a)Useaveragebondenthalpiestoestimatethestandardenthalpychange(inkJ
permoleofhydrazine)forthereaction.
(b)Comparetheenergyreleasedinthehydrazinereactiontotheenergythat
wouldbeobtainediftwomolesofammoniawereoxidizedbyhydrogenperoxide.
2NH3(g)+3HOOH(g)N2(g)+6H2O(g)
(c) Whichprovidesthemostenergypergramoffuel,hydrazineorammonia?
Answerto7.35:
Chapter7
23
(a)LetscanceltheHObondsbeforegoingthroughallthearithmetic.
Fourarebrokenontheleftandeightaremadeontheright,sowewill
includefourintheproducts,butignoretheminthereactants.TheHrxn
forthisreactionisgivenby:
Hrxn=BH(NN)4BH(HO)+4BH(HN)+BH(NN)+2BH(OO)
Hrxn=9411840+1572+193+284=732kJ
(b)Inthiscase,cancelingtheHObondsleavesanetofsixinthe
products:
Hrxn=BH(NN)6BH(HO)+6BH(HN)+3BH(OO)
Hrxn=9412760+2358+426=917kJ
Twomolesofammoniareactingreleaseabout25%moreenthalpythana
moleofhydrazine.
(c)Amoleofhydrazineis32gofhydrazine,sotheenthalpychangefrom
hydrazineis22.88kJg1((=732kJ)/(32g)).Thecomparablevaluefor
ammoniais26.97kJg1((=917kJ)/(34g)).
Sincemoreenthalpyisreleasedbytheammoniareaction,whyisntammonia
used,insteadofhydrazineasthefuel?Therearequitepracticalreasonsforusing
hydrazine.Probablythemostimportant,fromanengineeringpointofview,isthat
hydrazineisaliquidatroomtemperature,Table7.4,andcanbeeasilystoredand
pumpedaroundintherocket.Ammonia,ontheotherhand,isagasatroom
temperatureandhastoberefrigeratedand/orkeptunderhighpressuretostoreit
asaliquid.Thisjustincreasesthecomplexityoftherocket.Consideralsothe
oxidant,hydrogenperoxide.Aboutoneandonehalftimesasmuchperoxideis
requiredfortheoxidationofammoniaasforanequalmassofhydrazine.
Therefore,theamountoffuelandoxidanttogetherislessforhydrazine.Thesame
sizerocketcancarryasomewhatgreaterpayloadwiththehydrazinefuelbecause
lessmassoffuelandoxidantareneeded.Workoutforyourselftheenthalpy
changeforreactionofonegramofthestoichiometricmixtureoffuelandoxidant
7.36.
foreachfuel.
WEB
WEBChap7,Sect7.7.23.OnWebCompanionpage7.7.2youselectthe
bondsthatarebrokeninthereactantsandmadeintheproducts.
(a) Usethedataonpage7.7.3tocalculatetheenthalpychangeforthisprocess.
Chapter7
24
(b) Howdoesyourresultinpart(a)comparewiththeanalysisonpage7.7.3
whereallreactantbondsarebrokenandallproductbondsformed?
(c) Explainwhythecomparisoninpart(b)comesoutthewayitdoes.
Answerto7.36:
(a)Thetwobondsthathavetobebrokeninthereactantsandthethreethathave
tobemadeintheproductareindicatedhere:
H H
C H
H O H
H H
C H
H O H
BreakingtheHOandC=Cbondsrequires460+620=1080kJmol1.Making
theCH,CO,andCCbondsreleasesenergy,sotheenthalpychangeis
negative,(414+351+347)=1112kJmol1.Thenetchangeinenthalpyisthe
sumofthesetwovalues,1080+(1112)=32kJmol1.
(b)OnWebCompanionpage7.7.3,youfindthatbreakingallthebondsinthe
reacatantsrequires3196kJmol1andmakingallbondsintheproductreleases
3228kJmol1.Thenetchangeforthereactionis32kJmol1.Theresultsforthe
twomethodsareidentical.
(c)Findingthattheresultsofthetwomethodsareidenticalisexpected.Whenall
thebondsinthereactantsarebroken(atomizingthemolecules),wearebreaking
severalkindsofbonds,severalCHbonds,forexample,thatwillsimplybe
remadeintheproduct.Ourassumptioninusingaveragebondenthalpiesisthat
thebondenthalpyforagivenkindofbondisthesameinallmolecules.Thus
whenthebondsareremadeintheproduct,exactlythesameamountofenthalpyis
releasedaswasrequiredtobreakthebondsinthefirstplacethebreakingand
makingsimplycancelout.Theonlybondbreakingandmakingthatcontributeto
anetdifferenceforthereactionarethosethataredifferentinthereactantsand
product,whichiswhatwefocusedoninpart(a).Youcanseethisargument
graphicallyonWebCompanionpage7.7.3,ifyoufirstbreakthetwobonds
selectedonpage7.7.2andthenbreakalltheotherstoatomizethereactants.Now
whenyoumaketheproductbonds,firstmakeallthosethatarethesameinthe
productasinthereactantsandthen,finally,makethethreenewbonds.Compare
thelengthsofthebarsonthegraphforthebreakingandmakingthesamesetof
bonds.
7.37.
Carbonhydrogenbonddissociationenthalpiesareshownfortwodifferent
hydrogensinthereactionsofpropeneand2buteneshownhere.Theenthalpies
forthetwodifferentbonddissociationsarequitedifferent.Thedissociationofa
Chapter7
25
carbonhydrogenbondonacarbonthatisnexttoadoublybondedcarbon,
reactions(1)and(3),requireslessenergy.
(1)
H
H
H C C C
H H H (2)
(3)
H
H H
H C C C C H
H H
H
(4)
dissociationenthalpy
kJmol1
H
H C C C
H H H
361
H
H
H C C C
H
H
430
H H
H C C C C H
H H
H
358
H
H
H C C C C H
H H
H
430
(a) Arethepropylandbutylfreeradicalsformedinreactions(1)and(3),
respectively,morestable(lowerenthalpy)orlessstable(higherenthalpy)than
thoseformedinreactions(2)and(4)?Clearlyexplainthereasoningforyour
response,usingenthalpyleveldiagrams,iftheseaidyourexplanation.
(b) Theunpairedelectroninthethreecarbonandfourcarbonfreeradicals
formedinreactions(1)and(3)isoftenshownasparticipatingindelocalized
bonding(seeChapter5,Section5.7),withthetwoelectronsfromtheadjacent
doublebond.WriteLewisstructuressupportingthismodel.Dothebond
dissociationenthalpiesandyourinterpretationinpart(a)supportthismodel?
Howwoulddelocalizationoftheunpairedelectronorbitalaffecttheenergyofthe
radical?Explainyourreasoningclearly.
Answerto7.37:
(a)Theenthalpyleveldiagramattherightrepresentstheenthalpiesofthe
reactantandthetwosetsofproductsfromreactions(1)and(2).
Chapter7
26
Ittakeslessenthalpytoproducethe
productsfromreaction(1).Thus,thefreeradicalsformedinreaction(1)
{and(3)}aremorestable(by69kJ)thanthoseformedinreaction(2)
{and(4)}.
(b)TheequivalentLewisstructuresforthethreeandfourcarbonfreeradicals
formedinreactions(1)and(3)are:
H
H C C C
H H H
C C C H
H H H
H H
H C C C C H
H H
H
H H
H C C C C H
H H
H
Thestructuresforthethreecarbonradicalareidenticalinenergy,soweknow
fromourdiscussioninChapter5,Section5.7,thattheelectronsinvolvedare
delocalizedandoflowerenergythantheywouldbeifthetwopidoublebond
electronsandsinglefreeradicalelectrondidnotinteract.Thetwofourcarbon
structuresarenotquiteidentical,butthesigmabondingtothecarbonatomswith
thefreeradicalelectronisverysimilarinthetwostructures(totwohydrogen
atomsinthefirstandtoahydrogenatomandcarbonatominthesecond),sowe
cantreatthestructuresasenergyequivalentandagainseethatthereiselectron
delocalizationtolowertheenergyofthisfreeradical
Section7.8.
StandardEnthalpiesofFormation
7.38.
Youusuallyseesulfurintheformofalightyellowpowder,therhombic
crystallineallotropeofsulfur.Ifyoumeltthissolid(m.p.112.8C),pourthe
liquidintoafilterpapercone,andthenunfoldtheconeasthesamplecools,you
findthattheliquidhassolidifiedindarkyellowneedles.Thisisthetriclinic
crystallineallotropeofsulfur.Afterseveraldays,theneedlesbecomecoveredby
Chapter7
27
alightyellowlayer.Whichallotropeofsulfurisprobablyitsmoststableform
understandardconditions?Explainyouranswer.
Answerto7.38:
Therhombicallotrope,thelightyellowpowder,isthemorestableatroom
temperature.Athighertemperatures,nearthemeltingpoint,thetriclinicallotrope
mustbemorestable,sinceitistheformthatcrystallizesfromthemoltensulfur.
Uponstandingatroomtemperature,therhombicallotropeformsslowlyonthe
surfaceofthetriclinicneedles,whichindicatesaslowtransformationtothemore
stableform.Ifwewaitlongenough,alltheneedleschangebacktothelight
yellowpowder.
7.39.
Urea(Latinurina=urine),H2NC(O)NH2,isawatersolublecompoundmadeby
manyorganisms,includinghumans,toeliminatenitrogen.Usestandard
enthalpiesofformationtofindtheenthalpyforthereactionproducingureafrom
ammoniaandcarbondioxide.
2NH3(g)+CO2(g)H2NC(O)NH2(s)+H2O(l)
Showallyourworksoyourprocedureisclear.
Answerto7.39:
Thestandardenthalpiesofformationforammonia,carbondioxide,urea,
andwaterare46.1,393.5,333.0,and285.8kJmol1,respectively.
Thestandardenthalpychangeforthereactionis(wherethestoichiometric
coefficientsunitsofmolarenotshown,iftheyareunity):
Horxn=Hof(H2O(l))+Hof(H2NC(O)NH2(s))2Hof(NH3(g))Hof(CO2(g))
Horxn=(285.8kJ)+(333.0kJ)(92.2kJ)(393.5kJ)=133.1kJ
7.40.
InProblem7.39,youusedenthalpiesofformationtocalculatetheenthalpyfor
makingureafromammoniaandcarbondioxide.Howcouldyouestimatethe
enthalpyofvaporizationofurea?Explaintheprocedureyouwoulduseandthen
carryitout.Hint:Whatotherwaycouldyouestimatetheenthalpyofthereaction
formingurea?Howdothetwowaysdiffer?
Answerto7.40:
Chapter7
28
Recallthatbondenthalpyvaluesare
applicabletogasphasemolecules.We
couldusebondenthalpiestocalculatethe
enthalpychangeforthereactionin7.25
withtheureaandwaterasgasesand
comparetheresultwiththeenthalpy
changecalculatedin7.25fortheureaasa
solidandwaterasaliquid.Thedifference
isanestimateoftheenthalpyof
sublimationofureaplustheenthalpyof
vaporizationofwater.(Theproblemis
misstatedwhenitasksfortheenthalpyof
vaporizationofurea.Youcangetthe
enthalpyofsublimation,buthavenoway
toestimatethechangesfromsolidto
liquidtogas.)Forthegasphasereaction
wehave:
Horxn=2BH(HO)4BH(HN)2BH(CN)BH(C=O)+
6BH(HN)+
2BH(C=OinCO2)
H rxn=9201572552745+2358+1598=+167kJ
o
Enthalpyisrequiredtomakegaseousureaandwaterfromammoniaandcarbon
dioxide.Theenthalpychange(decreaseexothermicchange)goingfromthe
gasestosolidureaandliquidwateris133(167)=300kJ.Theenthalpyof
vaporizationofwateris44kJmol1,sothecondensationofwateraccountsfor
44kJ.Thisleaves256kJastheenthalpyreleasedwhengaseousureacondenses
tosolidurea.Ourestimatefortheenthalpyofsublimationofureaisabout256
kJmol1.
7.41.
Duringfermentationoffruitandgrains,glucoseisconvertedtoethanoland
carbondioxideaccordingtothisreaction:
C6H12O6(s)2C2H5OH(l)+2CO2(g)
(a) UsingthedatainAppendixXX,calculateHreaction.
(b) Isthisreactionexothermicorendothermic?
Chapter7
29
(c) Whichhashigherenthalpy,thereactantortheproducts?
(d) CalculateHfortheformationof5.0gofC2H5OH(l).
(e) Whatquantityofheatisreleasedwhen95.0gofC2H5OH(l)isformedat
constantpressure?
Answerto7.41:(a)Hreaction=68.0kJmol1(b)exothermic(c)reactants
(d)3.7kJ(e)70.2kJ
7.42.
Considerthisgasphasereactioninwhichmethanoic(formic)acidreactswith
ammonia.Theproductformamidecontainsapeptidebondandthereistherelease
ofawatermolecule:
O
H C
N H
O H
H C
N H
H
H
O
(a) Useaveragebondenthalpiestoestimatetheenthalpychangeforthis
reaction.HowdoesthisHcomparetotheHyoucalculatedinproblem7.29?
Wouldyouhaveexpectedthisresult?Whyorwhynot?
(b) Usestandardenthalpiesofformationtocalculatethechangeinenthalpyfor
thisreaction,assumingreactantsandproductsaregasesintheirstandardstates.
Theenthalpiesofformationofgaseousmethanoicacidandformamideare379
and186kJmol1,respectively.
(c) Comparetheresultsofyourcalculationsinparts(a)and(b).Offersome
reasonstohelpexplainyourcomparison.
Answerto7.42:
(a)H=BHreactants+BHproducts=(1BHCO+1BHNH)+(1BHCN+
1BHOH)=[(1molkJmol1)+(1molkJmol1)]+[(1mol
kJmol1)+(1molkJmol1)]=740kJ+736kJ=+4kJ
Notethatthecalculationusingaveragebondenthalpiesisthesameasin
thepreviousproblem,forexactlythesamebondsarebrokenandformed.
(b)Calculationusingstandardenthalpiesofformation.
Hreaction=npH0f(products)nrH0f(reactants)
=[(1mol)254kJmol1)+(1mol)285.8kJmol1)]
[(1mol)363kJmol1)+(1mol)46.3kJmol1)]
=130.5kJ
Chapter7
30
(c)Thetwocalculationsarenotveryclose.Averagebondenthalpiesarebasedon
gaseouscompoundsat25C.Standardenthalpiesofformationarebasedonthe
assumptionthatreactantsandproductsareintheirstandardstatesat25C.
Neithersetofassumptionscanbeexpectedtoholdtrueforthisreaction,which
likelytakesplaceinaqueoussolution.Thebondenthalpieswithinthewater
moleculearegivenforthegaseousstate,butthestandardstateforwaterat25C
isliquid.EvencorrectingfortheEnthalpyofVaporizationforwaterdoesnot
yieldthatclosearesult,becauseitstillwouldbenecessarytocorrectforthe
EnthalpyofSolutionvaluesfortheotherreactantsandproducts.
7.43.
Thecombustionofammoniaisrepresentedbythisequation:
4NH3(g)+5O2(g)4NO(g)+6H2O(g)
Experimentally,wefindHreaction=905kJforthereactionaswritten.
(a) UsethestandardenthalpiesofformationforNO(g)andH2O(g)from
AppendixXXandthestandardenthalpychangeforthereactiontocalculatethe
standardenthalpyofformationforNH3(g).
(b) Howdoesyourresultinpart(a)comparewiththestandardenthalpyof
formationforNH3(g)inAppendixXX?Explainwhytheyarethesame(or
different).
Answerto7.43:
(a)
Hreaction=npH0f(products)nrH0f(reactants)
905kJ=[(4mol90.4kJmol1)+6((1mol241.8kJmol1)]
[4(H0f(NH3)+5(0)]
905kJ=[361.6kJ1450.8kJ]4(H0f(NH3)
H0f(NH3)=46.0kJmol1
(b)Thetablevalueis46.3kJmol1.Thisisexcellentagreementandpointsup
thefactthatthetablevaluesareoftendeterminedbymeansofvaluesfor
combustionreactionswhicharerelativelystraightforwardtorun.
7.44.
Intheprocessknownascoalgasification,coalcanbereactedwithsteamand
oxygentoproduceamixtureofhydrogen,carbonmonoxide,andmethanegases.
Thesegasesaredesirableasfuelsandtheycanalsoserveasthestartingmaterial
forthesynthesisofotherorganicsubstancessuchasmethanol,usedforthe
Chapter7
31
productionofsyntheticfibersandplastics.Considerthesethreereactionsthatcan
takeplaceintheprocessofcoalgasification.
Reaction1:C(s)+H2O(g)H2(g)+CO(g)
Reaction2:C(s)+1/2O2(g)CO(g)
Reaction3:C(s)+2H2O(g)CH4(g)+O2(g)
Usestandardenthalpiesofformationtofindtheenthalpiesofreactionforeachof
thesethreereactions.Ifitispossibletocontrolthereactionconditionstofavor
oneormoreofthesereactions,whichisthemostenergeticallyfavorable?the
leastenergeticallyfavorable?Explainyourreasoning.
Answerto7.44:
(a)
Reaction1:Horxn=+373.1kJ
Reaction2:Horxn=110.5kJ
Reaction3:Horxn=393.5kJ
(b)ThemostexothermicreactionisReaction3.Thisdoesnotimplythatchemists
shouldworktocontrolthereactionconditionstomaximizethisreaction.The
maingoalofcoalgasificationistoproducefuelsandstartingmaterialsfor
synthesis.COandH2arethedesiredproducts,butthereactiontoproducecarbon
dioxidetakesplaceatthesametime.
Section7.9.
HarnessingEnergyinLivingSystems
7.45.
Whatisacoupledreaction?Whatisitsimportanceinbiologicalreactions?
Answerto7.45:
Inacoupledreaction,thereactionprovidingtheenergydoesnotproceedunless
thereactionrequiringtheenergyoccurs.Forexample,theexothermicoxidation
ofglucoseiscoupledwiththeendothermicformationofadenosinediphosphate,
ADP3,fromadenosinetriphosphate,ATP4.Thereversereaction,thehydrolysis
ofATP4toATP3isexothermicandiscoupledtootherenergyrequiring
biologicalfunctionssuchaslocomotion,informationprocessing,andsynthesizing
newbiologicalmolecules.
7.46.
WhatistheroleofATPinbiologicalreactions?
Answerto7.46:
ThefunctionofATPistostoreenergywhenenergyisnotneededforbiological
reactionsandtoreleaseitinstantlywhenbiologicalreactionsrequireit.
Chapter7
32
7.47.
Coupledreactionstakeplaceinlivingsystems,butcoupledprocesseshavemany
applicationsinindustryaswell.Forexample,wasteheatfromapowerplantcan
becapturedandusedtodowork,suchasdesaltingseawater.
(a) Otherthantheavailabilityofseawater,whatdoyouthinkmightlimitthe
usefulnessofthisexampleofacoupledprocess?
(b) Canyouthinkofanyotherexamplesofenergeticallycoupledprocessesfrom
yourpersonalexperienceorothercoursesyouhavetaken?Brieflydescribesucha
process.Youmightfinditusefultoresearchthistopicusingwebbasedresources.
Answerto7.47:
(a)Therearelimitationsontheoverallefficiencyofthiscoupledprocess.
Oneofthemajorlimitingfactorsisusingwasteheatfromapowerplant
fordesaltingseawateristhattheheatcontentofthewasteheatisrelatively
low.Itisnotgreatenoughtoboilwater,soaprocessofflashdistillationis
used.Thiscoupledprocessisnotwidelyusedintheworld,althoughsolar
distillationprocessesaremorecommon.
(b)Answerswillvarydependingonthebackgroundofthestudents.Theymay
presentexamplesfromengineering,otherbiologicalapplications,orfromecology
courses.Note:Thisquestioncouldbeassignedasawebbasedresearchquestion.
7.48.
ManyATP4coupledreactionsrequirethatMg2+bepresentaswell.Whatdoyou
thinkisthefunctionofMg2+inthesereactions?Hint:SeeChapter6,Section6.6.
Answerto7.48:Mg2+cancomplexwiththenegativelychargedATPions,
providingathreedimensionalscaffoldthatallowthesecoupledreactionstooccur.
7.49.
Theaerobicreactionsequenceofglycolysisinvolvesthecompleteoxidationof
pyruvicacid,CH3C(O)C(O)OH(=C3H4O3).Thisreactioniscoupledtothe
formationofATP4,accordingtothisoverallreaction:
2C3H4O3(l)+5O2(g)+30ADP3(aq)+30HOPO32(aq)+30H+(aq)
6CO2(g)+34H2O(l)+30ATP4(aq)
(a) CalculatetheH for the uncoupled oxidation of pyruvic acid to
CO2 and H2O.
(b) Calculate the H for the coupled reaction and determine the
percentage of energy converted to ATP4-.
Answer to 7.49:
(a)Theseparateequationfortheuncoupledoxidationofpyruvicacidis:
Chapter7
33
2C3H4O3(l)+5O2(g)6CO2(g)+4H2O(l)
Hpyruv oxid =
-2332 kJ
Hpyruv oxid is calculated from the heats for formation as shown:
Hpyruv oxid = [6mol(-393.5 kJmol-1) + (4mol)(-285.8 kJmol-1)]
- [2mol(-585.8 kJmol-1)
= -2332 kJ
(b) Recall that Hreaction= 21 kJmol-1 for the formation of
one ATP4fromADP3andHOPO32.Therefore,theenergyrequired
toform30ATP4willbe30timesasgreat.
30ADP3(aq)+30HOPO32(aq)+30H3O+(aq)60H2O(l)+30ATP4(aq)
Hreaction = (30mol)(21 kJmol-1) = 630 kJ
The Hcoupled reaction is: (-2332 kJ) + 630kJ = -1703kJ.
The 27% percent efficiency is calculated as follows:
% efficiency=
630 kJ
100=27%
2332 kJ
Only630kJofthe2332kJreleasedinthisoxidationareusedeffectivelyinthe
productionofATP4.Theremaining1703kJislostasheat.
Section7.10.PressureVolumeWork,InternalEnergy,andEnthalpy
7.50.
Aninventorclaimstohavebuiltadevicethatisabletodoabout0.8kJofwork
forevery1kJofthermalenergyputintoit.Heislookingforinvestorstobuy
sharesinhiscompany,sohecancommercializehisinvention.Wouldyouinvest
inhiscompany?Explainwhyorwhynot.
Answerto7.50:
Chapter7
34
Youshould,byallmeans,investinthisinventor(afteryouhaveseenproofthat
hisdevicecanactuallydowhathesays).Thisdeviceisabout80%efficientin
convertingrandomthermalmotiontothedirectedmotionofwork.Thisisagood
dealbetterthanthebestenginesnowavailable.Thereisnoviolationofthefirst
lawhere,sinceheisnotgettingoutmorethanheputsin.Thelostenergy
presumablyremainsinthedeviceinsomeformorisexpelledasthermalenergy
tosomeotherpartofthesurroundings.Theinventorsyouhavetolookoutforare
thosewhoclaimtogetmoreworkoutofathermalenginethanthethermalenergy
theyputin;thatisaviolationofthefirstlaw.
7.51.
Thevolumeofagasisdecreasedfrom10.Lto1.0Lataconstantpressureof5.0
atmospheres.Calculatetheworkassociatedwiththeprocess.Isworkdoneonthe
gasorbythegas?(1Latm=101.3J)
Answerto7.51:
101.3J
(a)PV=(5atm)(10.0L1.0L)=45Latm;45 1L =4.6103J
(b)Workisbeingdoneonthegas,asthevolumeisdecreasingfrom10.0Lto1.0
L.Apositivesignisassociatedwithworkdoneonthesystem.
7.52.
Ahotairballoonisinflatedbyusingapropaneburnertoheattheairinthe
balloon.Ifduringthisprocess1.5108Jofheatenergycausethevolumeofthe
balloontochangefrom5.0106Lto5.5106L,whatarethevaluesofq,w,and
Eforthisprocess?Assumethattheballoonexpandsagainstaconstantpressure
of1.0atmosphere.(1Latm=101.3J)
Answerto7.52:
Thevalueofqpisgiven,thisis1.5108J.Thisistheheatenergyadded
tothesystematconstantpressure.
Thepressurevolumeworkdonecanbecalculatedinthismanner.
w=PV
w=(1.0atm)(5.5106L5.0106L)
Finally,Ecanbecalculatedfromthevaluesforqpandw;E=qpPV
w = (1.0atm)(5.5
E=(1.5108J)(5107J)=1.0108J
Chapter7
35
7.53.
Photographicflashbulbs,oncemorecommonthantheyarenow,producedlight
fromthereactionofeitherzirconiumormagnesiumwirewithoxygeninthebulb,
forexample:
2Mg(s)+O2(g)2MgO(s)+energy(lightandheat)
Theybecamequitewarmwhenused,butonlyrarelydidtheyactuallyexplode!
DiscussthechangesinE,q,andwforthechemicalreactionthattakesplaceina
flashbulb.
Answerto7.53:
Thechemicalenergyofreactionofthemetalwithoxygenistransformedtolight
energyandheatenergyinthecourseofthereaction.Aslongasthebulbdoesnot
explode,thisisaconstantvolumereaction.Thismeansnopressurevolumework
ispossible,sow=0.ThisalsomeansE=H.
7.54.
Agaseouschemicalreactionoccursinwhichthesystemlosesheatandcontracts
duringtheprocess.Whatarethesigns,"+"or"",forPV,EandH?Explain
yourreasoning.
Answerto7.54:
SinceH=E+PV,weknowthatHisnegativesincethesystemlosesheat.
ThesystemcontractssoVfinal<Vinitial.ThismeansthatPVwillbenegativesince
Pisalwaysapositivenumber.Emaybeeitherpositiveornegativedepending
onthemagnitudeofHandPV.
7.55.
Considertwoexperimentsinwhichagasiscompressedinaclosedsyringeby
pushingtheplungeragainstthetrappedgas.Bothexperimentsusethesamesize
syringe.
ExperimentA
Chapter7
36
ExperimentB
(a) HowdoesthepressurevolumeworkperformedinExperimentAcompareto
thatperformedinExperimentB?Assumetheexternalpressureisthesameinboth
experiments.Explainyourreasoning.
(b) Assumethatathirdexperimentisperformedusingasyringewithawider
diameterthantheoneusedinthefirsttwoexperiments.Howwouldthepressure
volumeworkcomparewiththatinExperimentsAifxisthesame?Assumethe
pressureisthesameinbothexperiments.
Answerto7.55:
(a)ThepressurevolumeworkperformedinExperimentAislessthanthat
performedinExperimentB.Giventhatthecrosssectionalareaisthesame
forbothsyringesandthepressureisconstant,thepressurevolumeworkis
directlyproportionaltothevalueofx,whichissmallerforExperiment
A.Themathematicalrelationshipis:
w=PAx
(b)Althoughxisthesameforbothexperiments,Visnotthesamebecausethe
crosssectionalareaofthesyringeisgreaterinthethirdexperiment.Because
pressurevolumeworkisaproductofthepressure,whichisconstant,andthe
changeinvolume,theworkdoneinthethirdexperimentisgreaterthanthatdone
inExperimentA.
7.56.
Considerthechangesthatoccurinthisreaction:
3H2(g) + N2(g) 2NH3(g)
Isworkdonebythesystem(gaseousreactantsandproduct)oronthesystem?
Explainyouranswer.Assumethatthisreactionoccursatconstanttemperature
andpressure.
Answerto7.56:
WecalculateVbynotingthat3litersofH2(g)reactwith1literofN2(g)to
produce2litersofNH3(g).Inthiscase,V=2litersandworkisgreaterthan
zero,indicatingthatworkmustenterthesystem.
7.57.
Mostofthenitrogenusedtoinflateanautomobileairbagisproducedbythe
reactionofsodiumazide:
2[Na+][N3](s)>2Na(g)+3N2(g)
Adriverssideairbagmighttypicallycontainabout95gofsodiumazide.
Chapter7
37
(a) Amoleofnitrogengasoccupiesabout25Lat25C.Howlargeistheairbag
thisnitrogenwillinflate?
(b) Howmuchworkisdonebythenitrogenasitinflatestheairbag?
(c) Ifthisexothermicreactionisinvestigatedinaconstantvolumecalorimeter,
willthemeasuredthermalenergyreleasebegreaterorlessthanthethermal
energyreleasedatconstantpressure?Howlargewillthedifferencebe?Clearly
explainyourreasoning.
Answerto7.57:
(a)Thestoichiometricequationshowsthat3molesofnitrogengasare
producedforeverytwomolesoftheazidethatreacts.Theazidehasa
molarmassof65g.Therefore:
95gazide
molN2formed=
=2.2molN2
65g
Thevolumeoccupiedby2.2molN2is55L(2.2mol25Lmol1)sothe
airbagisabout55Linvolume,whichisapproximately2cubicfeet(or
youcanimagineabout25empty,twolitersoftdrinkbottlessuddenly
appearinginfrontofyouwhentheairbagdeploys).
(b)Theexternalpressureagainstwhichtheairbagpushestoinflateis
atmosphericpressure,Patm,whichis1.0105Pa(Nm2).Thevolume
change,V,ofthegasis55103m3(sincewegofromnogastoafinal
volumeof55Landaliteris103m3=acubicdecimeter).Thus:
workdonebythegas=PatmV=(1.0105Nm2)(55103m3)=5500J
(c)WeknowthatH=E+PVandthatthepressurevolumeproductisa
positive5500J.Therefore,themeasuredthermalenergyreleaseatconstant
volume,qV=E,willbesmallerby5500Jthanthatmeasuredatconstant
pressure,qP=H.
7.58.
Forthisreaction,aswritten,H=484kJ:
2H2(g)+O2(g)2H2O(g)
When0.5molofH2(g)wasreactedwith0.3molofO2(g),ataconstantpressureof
1.0atm,thechangeinvolumewas6.1liters.Calculatehowmuchworkwas
doneandthevalueofEforthisreaction.Isworkdoneonthesystemorbythe
system?
Answerto7.58:
Chapter7
38
SinceE=HPV,wewillfirstneedtocalculatebothHandPVto
obtainthevalueforE.NotethattheinitialamountsofH2(g)andO2(g)
arenotinthe2:1molarratiodemonstratedbythebalancedequation.In
fact,H2(g)isthelimitingreagentandisconsumedcompletelywhile
0.05molofO2(g)remainsunreacted.Hfortheamountsgivenis:
H =0.5mol H2(g)
-484kJ
= 121kJ
2mol H2(g)
101J 1kJ
3 ) =+0.62kJ
L atm 10 J
Work (-PextV) is determined next:
work = - (1atm)(-6.1
L
Note: Work is done on the system.

Therefore, E = -121kJ + 0.62kJ = 120.4kJ
Section7.11.WhatEnthalpyDoesntTellUs
7.59.
Indicatewhethereachofthefollowingstatementsistrueorfalse.Ifastatementis
false,writethecorrectstatement.
(a) Considera10mLsampleofpurewaterat25Cand1atmpressure(state
A).Thesampleiscooledto1Candthenthepressureisreducedto0.5atm
(stateB).Ittakes5hourstocarryoutthechangefromstateAtostateB.The
sampleisthenheatedandthepressureisraisedto1atm.Inoneminutethewater
isbackat25C(thesampleisbackatstateA).Theinternalenergychangein
goingfromstateAtoBisequalto,butoppositeinsigntotheinternalenergy
changegoingfromstateBtoA.
(b) TheworkdoneinchangingfromstateAtoBandtheworkdoneinchanging
fromstateBtoAinpart(a)arenumericallythesamebutoppositeinsign.
(c) Theenthalpychangeforachangeofstateofasystemisindependentofthe
exactstateofthereactantsorproducts.
(d) Atconstantpressuretheamountofheatabsorbedorevolvedbyasystemis
calledtheenthalpychange,H.
Chapter7
39
(e) Ifvolumedoesnotchange,theamountofheatreleasedduringachangeof
stateofasystemisequaltothedecreaseininternalenergyofthatsystem.
(f) Ifareactionisspontaneous,itisalwaysexothermic.
(g) Iftheenthalpychangeforthisreaction,N2(g)+O2(g)2NO(g),is180.5kJ,
thentheenthalpychangeforthisreaction,1/2N2(g)+1/2O2(g)NO(g),is90.2
kJ.
Answerto7.59:
(a)True.Internalenergyisastatefunction.Thedifferenceintheinternal
energiesoftwostatesisindependentofthepathtakenbetweenthestates.
(b)False.Workdependsonthepath,i.e.,themethodofgoingfromone
statetoanother.
(c)False.Theenthalpyofreactionisdependentontheexactstateofthe
reactantsorproducts.
(d)True.TherelationshipbetweenHandEisH=E+pV.At
constantvolumetheamountofheatabsorbedorevolvedbyasystemis
equaltoeternalenergychange.
(e)True.AtconstantvolumeH=Eandqv=qp
(f)False.Endothermicreactionwhicharespontaneousincludefreezing
waterattemperaturesbelow0oCanddissolvingmanysalts(forexample
NH4NO3).
(g)True.
7.60.
When1molofNH4Cl(s)isdissolvedinwater,formingNH4+(aq)andCl(aq),the
changeinenthalpyis14.8kJmol1.When1molofCaCl2(s)isdissolvedinwater,
formingCa2+(aq)andCl(aq),thechangeinenthalpyis82.9kJmol1.
(a) Which beaker felt cool to touch after the salt dissolved in
water? Which one felt warm?
(b) What would you have to do to maintain the temperature of
each beaker at 25C?
(c) To determine H for dissolution of salts in water, what
factors must you consider?
Answer to 7.60:
(a)TheNH4Clsolutioniscooltotouch,whiletheCaCl2solutioniswarm
totouch.
Chapter7
40
(b)FortheNH4Clsolution,15.1kJofheatmustbeadded.FortheCaCl2
solution,82.9kJmustberemoved.
(c)Theconcentrationofthedissolvedsaltmustbeconsidered.Theabovevalues
fortheenthalpychangesareobtainedbymeasuringenthalpychangesand
extrapolatingtothelimitofinfinitedilution.Also,wenotethatitisimpossibleto
assigntheenthalpychangesassociatedwiththeindividualionsofasaltwithout
givinganarbitraryenthalpyvaluetooneoftheions.
7.61.
GiventhatHfforCl(aq)=167.4kJmol1,usetheenthalpyofreactiondata
fromProblem7.60tocalculateHfforNH4+(aq)andforCa2+(aq).
Answerto7.61:
ForNH4+(aq):
H form[NH4+(aq)] + H form[Cl-(aq)] = H form[NH4Cl(s)] + 15.1
kJmol-1
H form[NH4+(aq)] + (-167.4 kJmol-1) = -315.4 kJmol-1 + 15.1
kJmol-1
H form[NH4+(aq)] = -132.9 kJmol-1
For Ca2+(aq):
H form[Ca2+(aq)] + H form[2Cl-(aq)] = H form[CaCl2(s)] - 82.9
kJmol-1
H form[Ca2+(aq)] - 334.8 kJmol-1 = -795.8 kJmol-1 - 82.9
kJmol-1
H form[Ca2+(aq)] = -543.9 kJmol-1
7.62.
Anineteenthcenturychemist,MarcellinBerthelot,suggestedthatallchemical
processesthatproceedspontaneouslyareexothermic.Isthiscorrect?Givesome
examplesthatjustifyyouranswer.
Answerto7.62:
Chapter7
41
Berthelotssuggestionwasincorrect.Endothermicprocessesthatarespontaneous
includefreezingwaterattemperaturesbelow0oCanddissolvingmanysalts(for
exampleNH4NO3).
Section7.13.EXTENSIONIdealGasesandThermodynamics
7.63.
Considertwosamplesofgasinidenticalsizecontainers.Whichofthese
statementsistrue?Explainyourreasoningforeachchoice.Rewritethefalse
statementstomakethemtrue.
(a) Ifthetemperatureofthetwosamplesisthesame,thenthepressureofgasin
eachcontaineristhesame.
(b) Ifthetemperatureandpressureofthetwosamplesarethesame,thenthe
numberofmolesofgasineachcontaineristhesame.
(c) Ifthegasineachcontaineristhesameandthetemperatureandnumberof
molesofgasineachcontainerarethesame,thenthenumberofcollisionswith
thewallperunittimeisthesameinbothcontainers.
Answerto7.63:
(a)Thestatement,asgiven,isnottrue.Althoughthetemperatureandvolumeof
thegassamplesarethesame,wehavenoinformationaboutthequantityofgas,
thatis,thenumberofmolesofgas,ineachcontainer.Theonewithmoremoles
willhavethehigherpressure,sinceP=n(RT/V)andallthequantitiesinsidethe
parenthesesontherightarethesameforbothsamples.Wecanamendthe
statementintwoways:(1)Ifthetemperatureandnumberofmolesofgasisthe
same,thenthepressureofgasineachcontaineristhesameor(2)Ifthe
temperatureofthetwosamplesisthesame,thenthepressurewillbehigherinthe
containerwiththegreaternumberofmolesofgas.
(b)Thisstatementistrue,sincen=PV/RTandallthequantitiesontherightare
thesameforbothsamples.
(c)Thisstatementistrue.Toseewhythisisso,wenotethatthepressureofthe
gasineachcontaineristhesame,sinceP=nRT/Vandallthequantitiesonthe
rightarethesameforbothsamples.Pressureisaresultofcollisionsofthegas
moleculeswiththewalls.Sincethegasmoleculesandthepressurearethesame
ineachcontainer,thenumberofcollisionsperunittimemustbethesameineach
container.
7.64.
Moleculesofallgasesatthesameabsolute(Kelvin)temperaturehavethesame
averagekineticenergyoftranslation,KE=1/2mu2,wheremisthemassofa
moleculeanduistheaveragespeed.Ifagasisinacontainerthathasoneormore
Chapter7
42
tinyholes,themoleculeswillbeabletoescapethroughtheholes.Fastermoving
moleculesescapemorereadily.
(a) Arubberballoonwasinflatedwithheliumgasandfloatedintheairatthe
endofitsstring.Thenextday,theballoonwassomewhatsmallerandnolonger
floated.Explainwhy.Hint:Whenathinsheetofrubberisstretched,tinyholes
forminthesheet.
(b) Twoidenticalrubberballoonswereblownuptothesamesize,onewith
heliumgasandtheotherwithair.Thenextday,bothballoonsweresomewhat
smaller,butnotthesamesize.Whichgaswasinthelargerballoon?Explainyour
answer.
Answerto7.64:
(a)Theballoondecreasedinsizebecausetheheliumatomsinsidewereableto
escape(slowly)throughthetinyholesinthestretchedrubber.Afterenough
heliumhadescaped,themassoftherubberballoonplustheremaininghelium
wasgreaterthanthemassofairdisplacedbythenowsmallerballoonandthe
balloonnolongerfloated.Thisisadensityphenomenon.Whenthereisalotof
heliuminaballoon,itsvolumeislargeanddisplacesairwithalargermassthan
thecombinedmassoftheheliumplustherubber.Thustheballoonisbuoyedup
(andwillkeepgoingup,asyouknow,ifyouhaveeverletgoofaheliumballoon
outdoors).
(b)Thelargerballooncontainsair.Moleculesofairandatomsofheliumleak
fromtheballoonsthroughthetinyholes,buttheheliumatomshavelowermass,
soaremovingfasterthantheairmolecules,hittheholesmoreoften,andleakout
faster.Airmoleculesfromtheoutsidecanalsoleakintotheballoons,buttherate
isslowerbecausethepressureinsidetheballoonsisslightlyaboveatmospheric
pressureandthenetflowofgasisgenerallyoutward.
7.65.
Achangeinvolvinggasesiscarriedoutatconstantpressureinacylinderwitha
piston,liketheoneillustratedinFigure7.20.Thefinalpositionofthepistonis
higherinthecylinderthanitwasinitially.Whatpossiblechange(s)mightoccurin
thesystemenclosedinthecylindertocausetheobservedchangeinthepositionof
thepiston?Clearlyexplainhowthechange(s)yousuggestwouldaccountforthe
movementofthepiston.
Answerto7.65:
FromtheidealgasequationweknowthatV=nRT/P.Ifthepressureremainsthe
same,butthevolumeofgasinthecylinderincreases(thesortofchange
illustratedinFigure7.20),thechangethatoccursmustinvolveanincreasein
Chapter7
43
numberofmolesofgas,nf>ni,atconstanttemperature,anincreaseinthe
temperatureofthegas,Tf>Ti,withoutachangeinnumberofmoles,orsome
combinationofchangesinthenumberofmolesandtemperature,suchthatthe
productoftheirfinalvalues,nfTfisgreaterthantheproductoftheirinitialvalues,
niTi.Areactionthatproducesmoremolesofgaseousproductsthanwerepresent
initially,suchasthereactioninInvestigateThis7.72isapossibilityforincreasing
thenumberofmoles.Somegasphasecombustionreactionsbeginandendwith
samenumbermolesofgas,butreleaseagreatdealofenergywhichincreasesthe
temperatureoftheproducts.Oneexampleis:
C2H4(g)+3O2(g)2CO2(g)+2H2O(g)
7.66.
Problem7.57(a)saysamoleofnitrogengasoccupiesabout25Lat25C(and1
atmpressure).Showthatthisistrue.Whatisthevolumeforamoleofoxygen?
Explain.
Answerto7.66:
ThevalueofRinappropriateunitsis8.21102Latmmol1K1.Withn=1mol,
P=1atm,andT=298K,weget:
V=nRT/P=(1mol)(8.21102Latmmol1K1)(298K)/(1atm)
V=24.5L25L
7.67.
Asampleofgasisputintoarigid(fixedvolume)containerat3Canda
pressureof38.3kPa.Thecontaineristhenplacedinanovenat267C.
(a) Whatpressurewouldyouexpecttomeasureforthegasinthecontainerat
thishighertemperature?Explain.
(b) Themeasuredpressureofthegasinthecontainerat267Cis137.2kPa.
Howdoesthisexperimentalvaluecomparewiththepressureyoucalculatedin
part(a)?Iftheyaredifferent,whatfactor(s)couldaccountforthedifference?
Clearlyexplainyourreasoning.
Answerto7.67:
(a)AtconstantVandn,weknowthatP/T=nR/V=constant.Thus,wecanwrite:
P1/T1=P2/T2=(38.3kPa)/(270K)=P2/(540K)
P2=76.6kPa
Wecouldalsohaveobservedthattheabsolutetemperaturedoubled,sothe
pressurealsoshouldhavedoubled,asthecalculationsindicate.
(b)Themeasuredpressureinthecontainerat540Kis137.2kPa,whichisalmost
twiceashighaswewouldhavepredictedfromtheidealgasequation.Evidently
thenumberofmolesofgasinthecontainerhasincreased,sincethevolumehas
remainedconstant.Thesimplestexplanationisthatsomeofthegasmoleculeswe
addedtothecontainermighthavedissociatedtogivetwoormoremoleculesfor
Chapter7
44
eachmoleculeinitiallypresent.Anexampleofsuchacaseisthedissociationof
anN2O4moleculetogivetwoNO2molecules(seeSection9.11).
7.68.
Analysisofaliquidhydrocarbonsampleshowsthattheratioofcarbonto
hydrogenatomsinthecompoundisonetoone.A0.237gsampleoftheliquidis
placedina327mLflaskattachedtoapressuresensor.Theairispumpedoutof
theflaskandthentheflaskissealedandheatedto150C,atwhichtemperature
theliquidhasallvaporizedandthepressureintheflaskis33.2kPa.
(a) Howmanymolesofthehydrocarbonsampleareintheflask?Explainhow
yougetyouranswer.
(b) Whatisthemolarmassofthehydrocarbon?Whatisthemolecularformula
ofthehydrocarbon?Explainhowyougetyouranswers.
Answerto7.68:
(a)Weusetheidealgasequationtofind,n,thenumberofmolesofgasinthe
flask:
n=PV/RT=(33.2kPa)(0.327L)/(8.315LkPamol1K1)(423K)
n=3.09103mol
(b)Nowweknowthatan0.237gsampleofthehydrocarbonis3.09103mol,
sowehavethemolarmass=(0.237g)/(3.09103mol)=76.8gmol1.Weknow
thattheratioofcarbontohydrogenatomsinthehydrocarbonisonetoone,soits
molecularformulaisCzHzanditsmolarmassisz(12.0gmol1)+z(1.00gmol1)
=z(13.0gmol1).Weequateourtwovaluesforthemolarmassandsolveforzto
getthemolecularformula:
z(13.0gmol1)=76.8gmol1
z=5.9=6
ThemolecularformulaofthehydrocarbonisC6H6.Themostcommon
hydrocarbonwiththisformulaisbenzene,whichisaliquidatroomtemperature
andagasat150C,soitspropertiesareconsistentwiththecompoundinthis
problem.
7.69.
Amineralsamplecontainsseveraldifferentioniccompounds,includingcalcium
carbonate,CaCO3(s).A1.587gsampleofthemineralwasheatedtodecompose
thecalciumcarbonatetoCaO(s)andCO2(g),Thegaswascollectedandmeasured
andhadapressureof83.35kPaat295.3Kina127.5mLcollectioncontainer.
(a) Howmanymolesofgaswereevolvedbythesample?Explainhowyouget
youranswer.
(b) HowmanymolesofCaCO3(s)werepresentinthemineralsample.Explain.
Chapter7
45
(c) WhatpercentageofthemineralsampleisCaCO3(s).Explainhowyouget
youranswer.
Answerto7.69:
(a)Weusetheidealgasequationtofind,n,thenumberofmolesofgasinthe
container:
n=PV/RT=(83.35kPa)(0.1275L)/(8.315LkPamol1K1)(295.3K)
n=4.328103mol
(b)ThereactionequationforthedecompositionofCaCO3(s)is:
CaCO3(s)CaO(s)+CO2(g)
Thus,onemoleofCaCO3(s)yieldsonemoleofCO2(g);theirare4.328103mol
ofCaCO3(s)intheoriginalsample.
(c)TogetthepercentageofCaCO3(s)intheoriginalsample,weneedthemassof
CaCO3(s)intheoriginalsample,whichwegetbyconvertingtheknownnumber
ofmolestomass:
massCaCO3(s)=(4.328103mol)(100.09gmol1)=0.433g
ThepercentageoftheoriginalsamplethatisCaCO3(s)is:
%CaCO3(s)=[(0.433g)/(1.587g)](100%)=27.3%
7.70.
Thefermentationofglucoseproducesethanolandreleasescarbondioxide.This
equationrepresentsthereaction.
C6H12O6(s)2C2H5OH(l)+2CO2(g)
(a) DoEandHhavethesamevalueforthisreaction?Explainyour
reasoning.
(b) IfEandHdiffer,whichislarger?byhowmuch?Explainclearly.
Answerto7.70:
(a)EoandHoaredifferentforthefermentationprocessbecausethenumberof
molesofgaschangesduringthereactionfromzerototwo.
(b)Theinternalenergychange,Eo,forthisreactionisequalto,qV,thethermal
energytransferredintooroutofthesystemifthereactioniscarriedoutat
constantvolume.Ifthereactioniscarriedoutatconstantpressure,thechangein
internalenergyisstillthesame(itisastatefunction),butnowworkisdoneby
thesysteminpushingbacktheatmosphere.Underthiscondition,thesystemloses
energyaspressurevolumework,soEo=qPPV=HoPV,whereHois
substitutedforqP,theamountofthermalenergytransferredatconstantpressure.
SincePVispositiveforthefermentationreaction(gasisformed,soV>0),the
equationrelatingEoandHoshowsthatEowillbemorenegativethanHo.
Usingtheidealgasequation,weshowedthatPV=(n)RT,equation(7.59).
Thus:
Eo=Ho(n)RT
Chapter7
46
Sincen=2mol,wehave(n)RT=(2mol)(8.315Jmol1K1)(298K)=4.96
103J,assumingreactionat298K.Thus,EowillbemorenegativethanHoby
4.96kJ.
GeneralProblems
7.71.
AconstantpressurecalorimetersimilartotheoneshowninFigure7.7canbe
usedtostudythereactionofmagnesiumwithhydroniumion:
Mg(s)+H3O+(aq)Mg2+(aq)+H2(g)
100.0mLof0.5Mhydrochloricacid,HCl(aq),wasputinthecalorimeter;its
temperaturewas19.32C.Then,0.1372gofMgmetalwasaddedtotheacidand
thetemperatureobserveduntilitreachedamaximumof25.69C.
(a) WhatisHreaction,inkJpermoleofMgreacted?
(b) CalculateEreaction,inkJpermoleofMgreacted.
(c)HowcouldyoumeasureEreactiondirectly?Aredatalikethoseinthisproblem
preciseenoughtomeasureanydifferencebetweenEreactionandHreaction?Explain
whyyouanswerasyoudo.
Answerto7.71:
(a)Thebalancedstoichiometricequationis:
Mg(s)+2H3O+(aq)Mg2+(aq)+H2(g)+2H2O(l)
Assumethatthemagnesiumreactscompletely,sothat(0.1372g)/
(24.31gmol1)=5.644103molofMgreacts.Theoriginalacidic
solutioncontained5102molH3O+(=(0.5M)(0.1L)),whichis
aboutfivetimesasmuchasneededtoreactwithalltheMg.Assume
thatthespecificheatofthesolutionis4.184JK1g1,that100.0mLis
100.0g,andthattheheatcapacityofthecalorimeteriszero.The
energychangeinthecalorimeteris:
qP=(100.0g)(25.6919.32K)(4.184JK1g1)=2.67kJ
Hreaction=(2.67kJ)/(5.644103mol)=472kJmol1
(b)Sinceagasisformed,weneedtocorrectforthepressurevolumeworkdone.
OnemoleofgasisformedforeverymoleofMgreacted,son=1andwehave:
E=HnRT=472kJmol1(1mol)(8.314JK1mol1)(298K)
E=472kJmol12.47kJ(permolMg)470kJmol1
Chapter7
47
(c)YoucouldmeasureEdirectlybycarryingoutthereactioninasealed
container(likeabombcalorimeter)withsomearrangementtodroptheMginthe
acidwhenthecontainerhadbeensealed.Intheory,theprecisionofthedata
aboveisgoodenoughtomeasurethehalfpercentdifferencebetweenEandH.
However,inorderactuallytogetdatathatareaccurateenoughtoobservethis
difference,youwouldhavetotakeaccountoftheactualmassofthecalorimetric
liquid,itstruespecificheat,and(probablymostimportant)theheatcapacityof
thecalorimeter.
7.72.
Severalelegantexperimentshavebeendonetodeterminetheamountofworkthat
molecularmotorsfromlivingcellscando.Themotorintheillustratioconsistsof
sevenproteins,three,three,anda,thatcome
togetherasshown.Themotoristoosmall(about
10108nm)tobeobserved,soalongactin
filamentisattachedtothemotorshaft,theprotein,
andmovementofthefilamentisobservedundera
microscope.Therotationoftheshaftisin120
steps.Eachstepappearstorequirethecoupled
hydrolysisofoneATPmolecule,reaction(7.37).Calculationsbasedonthe
observedmotionindicatethatthemotorisabletoproduceaforceofatleast
1001012N.Inonecompleterevolution,thetopofthemotorshaftmovesabout
1nm.
(a) Howmuchworkdoesthemotordoinonecompleterevolution?(1J=1
Nm).
(b) Howmuchenergy(enthalpy)isprovidedbyATPduringonecomplete
revolution?
(c) Whatistheapproximateefficiencyofthismotor?Explainhowyouarriveat
yourconclusion.
Answerto7.72:
(a)Recallthatworkisequaltoforcetimesthedistancethroughwhichthe
forceacts.Inonerevolutiontheshaftmovesabout1nm=1109mso:
workinarevolution=(1001012N)(1109m)=11019Nm(orJ)
(b)OurestimateinthischapterwasthatthehydrolysisofATPproduces
about21kJmol1.HydrolysisofonemoleculeofATPwouldproduce
Chapter7
48
about3.51020J.SincehydrolysisofthreemoleculesofATPisrequired
foreachrevolutionofthemotor,theenergyprovidedbytheATP
hydrolysisisabout3(3.51020J)=11019J.
(c)TheenthalpysuppliedbytheATPisessentiallythesameastheworkdoneby
themotor.Themotoris100%efficientinconvertingitsenergysourceintowork.
Evenifourestimatesareoffsomewhat,thismolecularmotorappearstobean
extremelyefficientdevice.
7.73.
CalculatetheHreactionforthehydrolysisofamoleculeofglycylglycinetotwo
moleculesofglycineusingtheHcombustiondataforglycylglycineandglycine.
AssumethatthenitrogenatomsinbothmoleculesareoxidizedtoNO2.Explain
yourprocedure.
Hcombustionfor glycine, H2NCH2C(O)OH = 981 kJmol-1
Hcombustionforglycylglycine,H2NCH2C(O)NHCH2C(O)OH=1,996kJmol1
Answerto7.73:
Thebalancedequationforthecombustionofglycylglycine:
C4H8O3N2 + 13/2 O2 2NO2 + 4CO2 + 4H2O
= -1966 kJ
reaction
Thebalancedequationforthecombustionofglycineneedstobe
doubledandusedinthereversedirection:
2NO2 + 4CO2 + 5H2O 2C2H5O2N + 13/2 O2
H reaction= (2mol)(981 kJmol-1) = 1962
kJmol-1
Summingthesetwoequationsgivestheoverallreactionwhichisthe
balancedequationforthehydrolysisofglycylglycine.Summingthe
correspondingheatsofcombustiongivestheHhydrolysisfor1moleof
glycylglycine:
C4H8O3N2 + 4H2O 2C2H5O2N
hydrolysis
7.74.
= -4 kJmol-1
Thediagramshowsaglassdemonstrationversionofafiresyring
(alsocalledafirepiston).Atinyamountofaflammablematerial,
clothorpaper,isplacedattheclosedendofthesyringe.Theplunger
isinsertedandthenthrustquicklyintothepiston,compressingthe
airinsidetoabout1/20thofitsinitialvolume.Thetemperatureofthe
Chapter7
49
airrisesalmostinstantlytoabout1000Kandignitestheflammablematerial,
whichburnswithabrightflash.
(a) Theinternalenergyofagasdependsonitstemperature.Whenthe
temperatureofthegaschanges,itschangeininternalenergydependsonits
constantvolumemolarheatcapacity(CV),thenumberofmolesofgas,andthe
temperaturechange:E=nCVT.CVforairis21kJmol1.WhatisEfor
thegascompressedinafiresyringethatis15cmlongandhasacrosssectional
areaof0.20cm2?Onemoleofgasat300Koccupiesabout25L.
(b) Thecompressioninafiresyringeissorapidthatthegashasnotimeto
transferthermalenergytoitssurroundingsduringthecompression.Howmuch
workisdoneonthegasduringthecompression?Whatpressure(inatm)onthe
plungerisrequiredtoobtainthismuchwork?Explainclearlyhowyouobtain
youranswer.(1Latm=101.3J)
(c) Togetabetterfeelfortheeffortrequiredtooperateafiresyringe,
calculatetheforceinpoundsrequiredtoproducethepressureyoucalculatedin
part(b).Usethefactthatapressureof1atm=15poundin2.Showclearlyhow
youdothenecessaryunitconversions.Istheforcerequiredareasonableamount
forahumantoproduce?
(d) Makeamolecularleveldrawing
showingthemotionofthemoleculesofair
inthesyringebefore,during,and
immediatelyafterthecompression.
Clearlyshowhowtheyobtaintheincrease
Firesyringesmadeofhollowwoodlikebamboo
haveapparentlybeenusedtostartfiresforseveral
centuries.AfirepistonwaspatentedinEngland
in1807.Thedieselengineworksonthissame
principle:theairintheenginecylinderis
compressedquicklyandthefuelisinjectedjust
inenergyyoucalculatedinpart(a).
(e) Whydoestheamountofflammablematerialinthesyringehavetobesmall?
Ifthetemperatureofthegasreaches1000K,couldntitsetfiretoalarger
quantity?Hint:Considertheheatcapacity(orspecificheat)ofapieceofsolid
clothorpaper.
Answerto7.74:
(a)TogetE,weneedthenumberofmolesofgasinthesyringeandthe
temperaturechangeuponcompression.Thetemperaturechangeisfrom
roomtemperature,about300K,toabout1000K:T=700K.Theinitial
volumeofgasinthecylinderis:
volumeofgas=(15cm)(0.20cm2)=3.0cm3(mL)
Chapter7
50
Thisvolumeofgasis1.2104mol(=(3.0mL)/(25000mLmol1),so
theinternalenergychangeis:
E=nCVT=(1.2104mol)(21Jmol1K1)(700K)=1.8J
(b)Ifnothermalenergyisexchangedwiththesurroundingsduringthe
compression,thenqiszeroforthecompressionandtheworkdoneonthe
gasisequaltoitschangeininternalenergy:w=E=1.8J.Thisworkis
theresultofadecreaseinvolumeofthegasto1/20thofitsinitialvolume
(partofthedescriptionatthebeginningoftheproblem).Thechangein
volume,V,isadecreaseof19/20thoftheinitialvolume=19/20(3.0
mL)=2.85mL=2.85103L.Theworkonthegasis:
w=1.8J=1.8102Latm=PV=P(2.85103L)
P=(1.8102Latm)/(2.85103L)=6.2atm
(c)Youhavetomultiplypressureinatmospheresby(15poundin2/1atm)
togetpressureinpoundin2.Theresultisabout93poundin2.Asquare
inch,in2,is(2.54cm)2=6.5cm2.Toconverttheareaofthepistonto
squareinches,wehavetomultiplytheareaincm2by(1in2/6.5cm2).The
resultis3.0102in2.Therefore,itrequiresabout3poundsofforce(=
(93poundin2)(3.0102in2))toproduceapressureof93poundin2on
thetinypiston.Threepoundsofforceiseasyformostteenagersoradults
toexert,sothefirepistonshouldbeeasytouse.
(d)Beforethecompression,themoleculesaremovingrandomlyandrelatively
slowly(shortarrows).Duringthecompression,themoleculeshavealarge
componentofmotioninthedirectionofthecompressionsuperimposedontheir
randommotion.Whenthecompressionstops,thelargecomponentofmotiongets
Chapter7
51
randomizedandthemoleculesareagainmovingrandomlybutatmuchgreater
speed(longerarrows)correspondingtoahighertemperature.
(e)Themaximumtemperatureisnottherelevantvariablehere.Theamountof
energyavailableinthecompressedgasiswhatyouhavetoconsider.The
calculationinpart(a)showsthattheinternalenergychangeofthegasisalittle
lessthan2J.Handbooksshowthatthespecificheatofpaperorcotton(bothmade
ofcellulose,aglucosepolymer)isintheballparkof1Jg1K1.Thekindling
temperatureofpaperis451F(whichisthesourceofthetitle,Fahrenheit451,
ofaRayBradburystoryaboutbookburning)orabout233C.Thus,youhaveto
raisethetemperatureofpaperabout200degreesfromroomtemperaturetogetit
toburn.Onegramofpaperwouldrequireabout200Jofenergytoincreaseits
temperaturethismuch.Sinceyouonlyhaveabout2Jofenergyinthecompressed
airofthefirepiston,youhaveenoughenergytoraisethetemperatureofabout10
mgofpaperorcottontoitskindlingpoint.Thatiswhyyouuseawispofcottonin
thedemonstration.Tostartalargerfire,youusetheglowingtindertoignitesome
furthersmallpiecesofmaterialandfinallybuilduptoarealfire.Thematchwasa
greatinventionandquicklymadefirepistonsobsolete.
7.75.
Giventheseatomizationreactionsandtheircorrespondingenthalpychanges,
calculateHforthecombustionof1molofPH3(g)toyieldH2O(g)andP2O5(g).
Showyourreasoningclearly.
PH3(g) P(g) + 3H(g)
H = 965 kJmol-1
O2(g) 2O(g)
H = 490 kJmol-1
H2O(g) 2H(g) + O(g)
H = 930 kJmol-1
P2O5(g) 2P(g) + 5O(g)
H = 3382 kJmol-1
Answer to 7.75:
Beginthisproblembyfiguringoutthebalancedequation:
2PH3(g) + 4O2(g) --> P2O5(g) + 3H2O(g)
Theatomizationreactionsneedtobecombinedinsuchawaythattheir
sumisequaltothebalancedequation.Asneeded,somereactionswill
needtobeusedmorethanonce.Forexample,theatomizationofPH3(g)is
usedtwiceso2(PH3(g)P(g)+3H(g))becomes2PH3(g)2P(g)+
6H(g)andHforthereactionisalsodoubledasgivenbelow.Other
Chapter7
52
reactionsareneededinthereversedirection,whichchangesthesignof
Hfrom(+)to().
Reactionsfromgivendata:
2PH3(g) --> 2P(g) + 6H(g)
H = 2mol(965 kJmol-1) =
1,930 kJ
H = 4mol(490 kJmol-1) = 1,960
4O2(g) --> 8O(g)

kJ
2P(g) + 5O(g) --> P2O5(g)
H = -3,382 kJ
6H(g) + 3O(g)
H = 3mol(-930 kJmol-1) =
3H2O(g)
-2,790 kJ
Summingthesefourequationsdoes,infact,generatethebalanced
equation:
overallequation:2PH3(g)+4O2(g)P2O5(g)+3H2O(g)
SummingthecorrespondingHvaluesgivesanoverallHwhichequals
2,282kJ.
Note:ThisHvalueisfor2molesofPH3.Therefore,forthecombustionof1
moleofPH3,H=1,141kJ.
Chapter7
53

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SolutionstoChapter7Problems

WhenheatisaddedtoH2O to do work, whydoesthevaporformofwater

Note: Work is done on the system.

H2O(g) 2H(g) + O(g)

P2O5(g) 2P(g) + 5O(g)

4O2(g) --> 8O(g)

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