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TheFirstLawofThermodynamicsChapter8Chapter8TheFirstLawofThermodynamics
8-1ChangesinThermodynamicSystems8-2HeatandWorkDonebyThermodynamicSystems8-3TheFirstLawofThermodynamics8-4SomeSpecialCasesoftheFirstlawofThermodynamics8-5TheMolarSpecificHeatsofanIdealGas8-6TheAdiabaticExpansionofanIdealGas8-7HeatTransferMechanisms8-1ChangesinThermodynamicSystemsThermodynamicsystemsinequilibrium,suchasabottleofhotsteam,aredescribedbyonlyafewthermodynamicvariables.Foragasthesevariablesare
p,V,T,
(orN).Foranidealgas,pV=
RT=
NkT.Assumethat
isfixed,thenitisenoughtodescribethe(equilibrium)stateonatwo-dimensionalplot,suchasap
Vdiagram,ap
Tdiagram,oraV
Tdiagram.ThermodynamicprocessWhenthesurroundingischanged,asystemwilldeviatefromequilibrium.Afteratime
,thesystemwillreachanewequilibriumstate(ifexists).Wesaythatthesystemundergoesathermodynamicprocess.Thetime
iscalledrelaxationtime.
Quasi-staticprocess
Tomaintainthermalequilibriumateachstepinathermalprocess,changesmustbemadesuchslowlythatthetimetakenbythethermalprocessismuchlongerthanrelaxationtime.Suchaprocessiscalled
quasi-staticprocess,whichcanberepresentedasacurveonap
Vdiagram,ap
Tdiagram,oraV
Tdiagram.Unlesswestateotherwise,weconsideronlyquasi-staticprocess.Thermodynamicsisbasedonourabilitytotreatquasi-staticprocess.Therearesituations(suchasfreeexpansion)inwhichprocessesoccurtoofastforequilibriumthermodynamicstoapply.Somequasi-staticprocessesiVp(a)(b)(d)(c)pconstantpressure(isobaric)process;isothermalprocess;isentropic(adiabatic)process;constantvolume(isochoric)process.8-2HeatandWorkDonebyThermodynamicSystemsTESystemTSQEnvironmentTS>TE
Q<0
TESystemTSEnvironmentTS=TE
Q=0
TESystemTSQEnvironmentTS<TE
Q>0
HeatHeatistheenergythatistransferredbetweenasystemanditsenvironmentbecauseofatemperaturedifferencethatexistsbetweenthem.HeatislostbythesystemtotheenvironmentQ<0.HeatisabsorbedbythesystemfromtheenvironmentQ>0.HeatisneitherreleasednorabsorbedQ=0.WorkDonebyThermodynamicSystemsdsApConsiderapistonofareaApushedoutbythepressurepofthegascontainedinthecylinder.TheinfinitesimalworkdonebythegasinmovingthepistondsisThevolumechangesfromVi
toVf:Duringthechangeinvolume,thepressureandtemperaturemayalsochange.Thereareactuallymanywaystotakethegasfromstateitostatef.0pW>0Vifahp0VifcgWnet
>00VpifThermodynamiccycleW<00VpifcompressedW>0Process0VpifexpandedDiscussionW>00VpifcAsystemcanbetakenfromagiveninitialstatetoagivenfinalstatebyaninfinitenumberofprocesses.Heatmayormaynotbeinvolved,andingeneral,theworkWandtheheatQwillhavedifferentvaluesfordifferentprocess.Wesaythatheatandworkarepath-dependentquantitiesCheckpoint18-3TheFirstLawofThermodynamicsIfanamountofheatQentersathermodynamicsystem,itcouldmanifestitselfaseitheranincreaseininternalenergyoraresultingquantityofworkperformedbythesystemonthesurroundings,orabitofboth.Then
Q
=
Eint
W,where
Eintisthechangeinthesystem’sinternalenergy,Wisthenetworkdonebythesystem.Notethatbeforethischapter,thetermwork
meantthattheworkdoneonasystemandissymbolizedW.However,inthischapterandthenext,wedefinethe
workandthesymbolWastheworkdonebyasystem.Ifthethermodynamicsystemundergoesonlyadifferentialprocess,dQ
=
dEint
dW.Checkpoint28-4SomeSpecialCasesoftheFirstlawofThermodynamics1.Constant-volumeprocessesiVpfpfpiOVIfV=constant,W=0.Suchaprocessiscalledanisochoricprocess,
Q
=
Eint
W
Eint
=
Q
Because
Eint=Q
=,ThenNotethat
Eintisafunctionofstateonly,and
Eintisindependentofprocesses,butQdependsonthepath.Therefore,thisequationholdsonlyforconstant-volumeprocess.2.Constant-pressureprocessesW>0ifOpVpVi
Vf
Anisobaricprocessisoneinwhichthepressureiskeptconstant.IfthevolumechangesfromVi
toVf
whilethepressureofthegasisheldconstantp,theworkdonebythegasisgivenby=
p(Vf
Vi)
Eintisindependentofprocesses,foranyprocessQ=
Eint
W=p(Vf
Vi)Fromthefirstlawofthermodynamics,heattransferinanisobaricprocessisgivenby3.Isothermalprocesses.
W>0TOVpifpipfViVfSupposethatweallowanidealgastoexpandfromaninitialvolumeVitoafinalvolumeVf
whilewekeepthetemperatureTofthegasconstant.isothermalexpansion:Vi<Vf
isothermalcompression:Vi>VfForanidealgas,theinternalenergyisthefunctionoftemperature,thusforanisothermalprocess
Eint=0Q=W
Fromthefirstlawofthermodynamics,workdonebyanidealgasduringanisothermalexpansion8-5TheMolarSpecificHeatsofanIdealGasHeatcapacityproportionalityconstantbetweentheheatdQthattheobjectabsorbsorlosesandtheresultingtemperaturechangedToftheobjectTheheatcapacityCofanobjectistheBecauseheatisapath-dependentquantity,theheatcapacityforagivenbodywillhavedifferentvaluesfordifferentprocesses.Forconstantvolume:Forconstantpressure:
MolarSpecificHeatatConstantVolumeSupposethat
molesofanidealgasundergoaninfinitesimalprocess,absorbasmallamountofheat
dQ,andthegastemperaturerisesasmallamountof
dT,F(xiàn)oranidealgasForaconstantvolumeprocess,dV=
0,(holdsforanyprocess)FromthedefinitionforheatcapacityatconstantvolumeThemolarspecificheatatconstantvolumeofanidealgasMolarSpecificHeatatConstantPressureForaconstantpressureprocess,dW=
pdV=
RdT
FromthedefinitionforheatcapacitySubstitutingdWanddEintintoForanyprocess,ThemolarspecificheatatconstantvolumeofanidealgasorSummary(anyidealgas).(idealgas,anyprocess).AchangeintheinternalenergyEintofaconfinedidealgasdependsonthechangeinthegastemperatureonly;itdoesnotdependonwhattypeofprocessproducesthechangeinthetemperature.IntermsofCV,m,EintcanberewrittenasCheckpoint3Example8-2Abubbleof5.00molofheliumatacertaindepthinliquidwaterwhenthewater(andthusthehelium)undergoesatemperatureincrease
Tof20.0C
atconstantpressure.Asaresult,thebubbleexpands.Theheliumismonatomicandideal.(a)Howmuchenergyisaddedaheattotheheliumduringtheincreaseandexpansion?Solution:BecausethepressurepisheldconstantduringtheadditionofenergyBecause=(5.00)(2.5)(8.31)(20)=2077.5J
2078J.(b)Whatisthechange
Eintintheinternalenergyoftheheliumduringthetemperatureincrease?Solution:Foranyprocessofanyidealgas,
Eintdependsonlyonthechangeintemperatu
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