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NotesonStatisticalThermodynamicsPartitionFunctions
Manytimeswedividethestudyofphysicalchemistryintotwobroadclassesofphenomena.Thereisthe
"macroscopicworld,"wherewestudythebulkpropertiesofmatter.Thatis,westudysampleswhichcontain
ontheorderof1023moleculesorparticles.Themaintheoreticalframeworkforthestudyofbulkproperties
inchemistryisthermodynamics(orkineticsformostnonequilibriumphenomena),andthefundamental
equationsarethefirst,second,andthirdlawsofthermodynamics.Ontheotherhand,wealsostudythe
"microscopicworld,"whereweareconcernedwiththepropertiesofindividualmoleculesorparticles.The
usualtheoreticalframeworkofthemicroscopicworldisquantummechanics(orsometimesclassical
mechanics),andthefundamentalequationsareSchrdinger'sequations(orNewton'slaws).Inthe
macroscopicworldwedealwithquantitiessuchasinternalenergy,enthalpy,entropy,heatcapacities,andso
on.Inthemicroscopicworldwedealwithwavefunctions,particlemomenta,kineticandpotentialenergies,
energylevels,andsoon.
Butthepropertiesofbulkmatterobviouslydependonthepropertiesoftheparticlesofwhichitiscomposed.
Howarethemicroscopicpropertiesofindividualmoleculesrelatedtothepropertiesofasamplewhich
contains1023molecules,ormoretothepointhowcanwefindthepropertiesofabulksamplefromthe
propertiesofthemolecules?Thisisthequestionwhichstatisticalthermodynamicsseekstoaddress.Wecan
thinkofstatisticalthermodynamicsasaprocessofmodelbuilding.Weconstructa(theoretical)modelofthe
particles,atoms,molecules,etc.,whichmakeupthesample,andstatisticalthermodynamicswilltelluswhat
thebulkpropertieswillbe.Forexample,ifourmodelisacollectionofmoleculeswhichdonotinteractwith
eachother,wewillgetthebulkpropertiesofanidealgas.Ifwewanttogetthepropertiesofanonidealgas,
wehavetogobacktothemodelandputinthepropertiesofthemoleculeswhichwillmakethegasnonideal.
Inthiscasethatamountstoincludingapotentialenergyofinteractionbetweenthemolecules.
Itwouldbeniceifstatisticalthermodynamicscouldbederivedentirelyfromthefundamentalprincipleswe
alreadyknow,sayquantummechanicsorclassicalmechanics.Unfortunately,thisisnotpossibleatpresent.
Inordertoarriveatatheorywhichworkswemustintroducesomenewpostulates.Thispathisfollowedin
mostbooksonstatisticalthermodynamicsandisquitesuccessfulandlargelysatisfactory.However,inthis
discussionwewilluseaslightlydifferentapproach.HereIamgoingtoaskyoutobelievethatthe
"Boltzmannfactor"whichIwilldescribebelowisacorrectdescriptionofsome"probabilities"relevantto
thesystem,andwewillderiveeverythingelsefromthere.
WewillassumethatwhateversystemweareinterestedinsatisfiestheSchrdingerequation(evenifit
contains1023particles!),andthatweknoworcanfindtheenergiesofthequantumstates.Forconvenience
wewilllabeltheenergystatesinorderofincreasingenergy,E1E2E3E4....Weusethesign
ratherthanthe<signbecausetheremaybedegeneracy,thatis,theremaybegroupsofstateswhichallhave
thesameenergy.Inanycase,eachindividualstatemustbelabeledandaccountedfor.
Now,Iamgoingtoaskyoutobelievethattheprobability,Pi,offindingthesysteminthei'thquantumstate
withenergyEiisproportionaltoaBoltzmannfactor.Namely,
(1)

(TistheKelvintemperatureandkisBoltzmann'sconstant,whichisjustthegasconstantdividedby
Avogadro'snumber.Weassumethatthesystemisatequilibriumsothatthereisawelldefinedtemperature.)
Iwillhavetotrustthatthisformoftheprobabilityisatleastplausibletoyou.Youhaveprobablyseenthis
formbeforeatleasttwice:onceinthekinetictheoryofgases,wheretheprobabilityoffindingagasmolecule
withvelocityvx(inthexdirection)isproportionalto

andagainintheArrheniustheoryofchemicalreactionrates,wheretherateconstantisproportionalto

(or

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onamolarbasis).
Bothexpressionshavetheformoftheexponentialof(energy)/kT.Noticethatmvx2/2isakineticenergy
andthatEaistheArrheniusactivationenergy.Inthelattercasetheassertionisusuallymadethatthe
exponentialfactorisproportionaltothenumberofmoleculeswithsufficientenergytoreact.
Itiscumbersometokeepwriting1/kTallthetime,soitiscustomarytoset1/kT=.Usingthisnotation,the
proportionalitycanbewritten:
(2)

AssumingthatweacceptthattheprobabilityoffindingthesysteminstateiwithenergyEiisproportionalto
,thenextnaturalquestioniswhatistheproportionalityconstant?That'srelativelyeasytoanswer
becauseweknowthattheprobabilitiesmustsumtounitythesystemmustbeinsomestate.Sowecanwrite
(3)
Let'scalltheproportionalityconstantc.Then
(4)
UsingEquation(3)wecansolveforcbywriting

(5)

sothat
(6)

Again,itiscumbersometokeepwriting

allthetimesowesimplifythingsbywriting

(7)
Itturnsoutthatthisquantity,Q,issoimportantinthetheorythatitisevengivenitsownname.Q,so
defined,iscalledapartitionfunction.(Don'tworryaboutwhyitiscalledthat,ithassomethingtodowith
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howenergyispartitionedamongthepossiblestatesofthesystem.Insomebooksthepartitionfunctionis
giventhesymbolzorZ,whichstandsfortheGermanwordzustandssumme,whichmeanssumoverstates.)
ThereasonwhyQissoimportantisthatitconnectsthemechanicalpropertiesofthesystem(throughthe
quantizedenergiesEi)withthermodynamics(throughtheTin=1/kT).Sothisfunctionhasboth
thermodynamicsandmechanicsinit.QisafunctionofTthroughthepartanditisafunctionofthe
mechanicalvariablesinthemodelthroughtheenergiesEi.Forexample,ifthequantizedenergiesofthe
systemdependonthevolume,V,thesystemiscontainedinandonthenumber,N,ofmoleculesinthesystem
andtheygenerallydodependonthesevariablesthenQwillbeafunctionofT,V,andN.
(Qwillalsobeafunctionofotherthings,likethemassoftheindividualmolecules,butwedon'tgenerally
indicatethatexplicitlybecausethemassofamoleculeisnotathermodynamicvariable.)
SoQisusuallyafunctionofT,V,andN,whichwewriteas,
(8)

ItisafunctionofTthroughtheandofVandNthroughthequantizedenergiesEi.(Itisimportantto
rememberthatthesuminEquation7isoverallstatesofthesystemnotjustoverenergylevels.Ifthereis
degeneracysomeofthetermsinEquation7willbeidentical.Forexample,iftherearefourstateswitha
particularenergyE,thentheterm

willoccurinthesummationfourtimes.)

Utilizingthefactthatthenormalizationconstantis1/Q,wecanwritetheprobabilitythatthesystemisin
statei,withenergyEi,as
(9)

Nowthequestionarises,howdoweusethistocalculatequantitiesofinterest?We'llstartwithinternal
energy,U.ThebestworddefinitionofUisthatitisthe(averageofthe)sumofallthepotentialandkinetic
energiesofalltheparticlesinthesystem.Inotherwords,Uisthetotal(average)mechanicalenergyofthe
system.Sinceweknowwhatthepossibleenergystatesofthesystemareandweknowtheprobabilitythat
thesystemisineachstate,wecancalculatetheaverageenergy.WewillsetthisaverageenergyequaltoU
(thisissortofapostulate,butwewon'tworryaboutthatnow),

(10)

SincewehaveanexpressionforPiwecanrewriteEquation10as

(11)

Sofarsogood,butwecansimplifythisbynoticingthat

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(12)

sothat
(13)

and

(14)

Soweseethat
(15)

(Wewillfind,aswegoalong,thatallofthethermodynamicpropertieswilldependonlnQorderivativesof
lnQ.Qitselfusuallyisavery,very,very,largedimensionlessnumber,butitsnaturallogarithmismuch
smallerandwillberelatedtomeasurableproperties.)
ItisfairtoaskwhatisbeingheldconstantintakingthepartialderivativeinEquation15.Ifwerecallthe
definitionofQitwillbeclearthattheonlythingsavailabletobeheldconstantarethemechanicaldefinitions
ofthemodel,suchasV,N,andanyotherpurelymechanicalthingsthattheEimaydependon(butnot
pressure,forexample).
Sometimesitisconvenienttotakederivativeswithrespecttotemperatureinsteadof.Usingelementary
calculuswecanchangevariablesbysetting
(16)

but=1/kT,orT=1/k,sothat
(17)

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then
(18)

Wenowhaveenoughinformationtocalculatetheheatcapacityatconstantvolume.Wecan'tcalculatethe
heatcapacityatconstantpressureyetbecauseQandUarefunctionsofVandnotp.(Wewillcalltheheat
capacityatconstantvolume,CV,butinfactweareholdingallofthemechanicalparametersofthesystem
constant.)ThethermodynamicdefinitionofCVis,
(19)

WhichcanbecalculatedfromourQandUas,
(20)

(Instatisticalthermodynamicsitiscommontoomitthestatementofwhatvariablesarebeingheldconstant
sinceweknowthatQisafunctionofT,V,andN.Thus,itisnotunusualtoseeEquation20written,
(21)

Wehavetwothermodynamicpropertiesofoursystem,UandCV,allcalculatedfromQ.Canweget
anythingelse?Howaboutentropy?Thethirdlawofthermodynamicssaysthattheentropy(ofa"nice"
system)iszeroattheabsolutezerooftemperature.SoallweshouldhavetodoisintegrateCV/Tfrom0K
uptosometemperature,T,
(22)

(IknowthatI'veusedTasbothvariableandlimitofintegration,butyouknowwhatImeansoIwon'tworry
aboutmakingitlookrighttothemathematicians.Ifthisbothersyou,putaprimeontheTanddTinsidethe
integral.)OK,soentropybecomes
(23)

(NoticethatwehavedividedCVbyT,sothatthereisonelessTfactorineachofthetermsintheintegrand
thantherewereinEquation21.)Thisintegralisreallythesumoftwointegrals.Thefirstintegraliseasyand
gives
(24)
Thesecond,
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Introduction to Statistical Thermodynamics, Part I

canbeintegratedbyparts.

Incaseyouhaveforgottenhowtointegratebyparts,recallthat
udv=d(uv)vdu

Here,wearesettingu=Tanddv=2lnQ/T2dT,sothatv=lnQ/T.Theintegrationbypartsthengives
fortheExpression24

(26)

Combiningthetwointegralsweget
(27)

which,uponseparationoftheupperandlowerlimits,becomes
(28)

(WehavenotbotheredtoexplicitlyindicatethatthefirsttwotermsareevaluatedattemperatureT,theyare.)
Thelasttwotermsreferto0Kandarepresumablytheentropyatabsolutezero.Inamoresophisticated
treatmentwewouldshowthattheyareidenticallyzero,buthereweshalljustassumethattheyarezero
becauseofthethirdlaw.Soourexpressionforentropyisjust
(29)

SonowwehavethreethermodynamicfunctionswhichwecancalculatefromlnQ.Wehaveaddedentropyto
thelist.Ifwelookcarefullyatthesecondtermontherightinthelastequation,andcompareittoEquation
(18)wewillseethatthislasttermisjustU/T.So,

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(30)
or
(31)
ButwealreadyknowthatUTSisjusttheHelmholtzfreeenergy,A,so
(32)
ThisEquation32isthefundamentalequationconnectingthepartitionfunctionQtothermodynamics.From
thisequationwecanderivealltheotherequationswhichwehavegivenaboveandmore.Forexample,we
cangetSagainfromtheusualrelationshipsofthermodynamicsas
(33)

KnowingAandSwecangetUas,
(34)
Theheatcapacityatconstantvolumecanbecalculatedtwoways,
(35)

or
(36)

Inaddition,wecangetpressurefrom

(37)
andchemicalpotential,,from

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(38)

CpcanalsobeobtainedfromlnQanditsderivatives.Itisagoodtestofyourthermodynamicskillstoderive
theexpressionforCpintermsoflnQanditsTandVderivatives.
Thefactis,wecangeteverypropertyofoursystemfromlnQthatourmodelcontains.(Anythingthatisnot
inthemodelwillnotshowupinthethermodynamicproperties.Forexample,ifyouwantthepropertiesofa
nonidealgasyouhavetoincludeinteractionsbetweenmoleculesinyourmodel.)Wenowhavethebasic
equations,allthatremainsismakethemodelandwriteQ.Onthenextpagewewillgivesomeadditional
usefulinformationanddevelopsomesimplemodels.

WRS
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ReturntotheTableofContentsfortheDynamicText,or
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