Fugacity

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Inchemicalthermodynamics,thefugacityofarealgasisaneffectivepartialpressurewhichreplacesthe
mechanicalpartialpressureinanaccuratecomputationofthechemicalequilibriumconstant.Itisequal
tothepressureofanidealgaswhichhasthesamechemicalpotentialastherealgas.Forexample,
nitrogengas(N2)at0CandapressureofP=100atmhasafugacityoff=97.03atm.[1]Thismeans
thatthechemicalpotentialofrealnitrogenatapressureof100atmislessthanifnitrogenwereanideal
gasthevalueofthechemicalpotentialisthatwhichnitrogenasanidealgaswouldhaveatapressureof
97.03atm.
FugacitiesaredeterminedexperimentallyorestimatedfromvariousmodelssuchasaVanderWaalsgas
thatareclosertorealitythananidealgas.Theidealgaspressureandfugacityarerelatedthroughthe
dimensionlessfugacitycoefficient.[2]

Fornitrogenat100atm,thefugacitycoefficientis97.03atm/100atm=0.9703.Foranidealgas,
fugacityandpressureareequalsois1.
ThecontributionofnonidealitytothechemicalpotentialofarealgasisequaltoRTln.Againfor
nitrogenat100atm,thechemicalpotentialis=id+RTln0.9703,whichislessthantheidealvalue
idbecauseofintermolecularattractiveforces.
Thefugacityiscloselyrelatedtothethermodynamicactivity.Foragas,theactivityissimplythe
fugacitydividedbyareferencepressuretogiveadimensionlessquantity.Thisreferencepressureis
calledthestandardstateandnormallychosenas1atmosphereor1bar,Againusingnitrogenat100atm
asanexample,sincethefugacityis97.03atm,theactivityisjust97.03withoutunits.
Accuratecalculationsofchemicalequilibriumforrealgasesshouldusethefugacityratherthanthe
pressure.Thethermodynamicconditionforchemicalequilibriumisthatthetotalchemicalpotentialof
reactantsisequaltothatofproducts.Ifthechemicalpotentialofeachgasisexpressedasafunctionof
fugacity,theequilibriumconditionmaybetransformedintothefamiliarreactionquotientform(orlaw
ofmassaction)exceptthatthepressuresarereplacedbyfugacities.
Foracondensedphase(liquidorsolid)inequilibriumwithitsvaporphase,thechemicalpotentialis
equaltothatofthevapor,andthereforethefugacityisequaltothefugacityofthevapor.Thisfugacityis
approximatelyequaltothevaporpressurewhenthevaporpressureisnottoohigh.
Theword"fugacity"isderivedfromtheLatinfor"fleetness",whichisofteninterpretedas"thetendency
tofleeorescape".TheconceptoffugacitywasintroducedbyAmericanchemistGilbertN.Lewisin
1901.[3]

Contents
1 Definitionintermsofchemicalpotential
2 Evaluationoffugacityforarealgas
3 Fugacityofapureliquid

3
4
5
6

Fugacityofapureliquid
Seealso
References
Externallinks
6.1 Videolectures

Definitionintermsofchemicalpotential
Thefugacityofarealgasisformallydefinedbyanequationanalogoustotherelationbetweenthe
chemicalpotentialandthepressureofanidealgas.
Ingeneral,thechemicalpotentialisdefinedasthepartialmolarGibbsfreeenergy.However,forany
puresubstanceitisequaltothemolarGibbsfreeenergy,anditsvariationwithtemperature(T)and
pressure(P)isgivenby
.
Atconstanttemperature,thisexpressioncanbeintegratedasafunctionofP.Wemustalsoseta
referencestate.Foranidealgasthereferencestatedependsonlyonpressure,andwesetP=1barso
that

Now,foranidealgas:

therefore

Reordering,weget

Thisgivesthechemicalpotentialforanidealgasinanisothermalprocess,withareferencestateis
P=1bar.
Forarealgas,theintegral

cannotbecalculatedbecausethereisnosimpleexpressionforarealgas'smolarvolume.Evenifusing
anapproximateexpressionsuchasthevanderWaalsequation,theRedlichKwongoranyother
equationofstate,itwoulddependonthesubstancebeingstudiedandwouldbethereforeofverylimited
utility.

Additionally,chemicalpotentialisnotmathematicallywellbehaved.Itapproachesnegativeinfinityas
pressureapproacheszeroandthiscreatesproblemsindoingrealcalculations.
Itisdesirablethattheexpressionforarealgas'schemicalpotentialtobesimilartotheoneforanideal
gas.Thereforeonecandefineaquantity,calledfugacity,sothatthechemicalpotentialforarealgas
becomes

withagivenreferencestatetobediscussedlater.Thisistheusualformofthedefinition,butitmaybe
solvedforftoobtaintheequivalentexplicitform

Evaluationoffugacityforarealgas
Fugacityisusedtobetterapproximatethechemicalpotentialofrealgasesthanestimationsmadeusing
theidealgaslaw.Yetfugacityallowstheuseofmanyoftherelationshipsdevelopedforanidealized
system.
Intherealworld,gasesapproachidealgasbehavioratlowpressuresandhightemperaturesundersuch
conditionsthevalueoffugacityapproachesthevalueofpressure.Yetnosubstanceistrulyideal.At
moderatepressuresrealgaseshaveattractiveinteractionsandathighpressuresintermolecularrepulsions
becomeimportant.Bothinteractionsresultinadeviationfrom"ideal"behaviorforwhichinteractions
betweengasatomsormoleculesareignored.
ForagiventemperatureT,thefugacityfsatisfiesthefollowingdifferentialrelation:

whereGistheGibbsfreeenergy,Risthegasconstant,Visthefluid'smolarvolume,andf0isa
referencefugacitywhichisgenerallytakenas1bar.Foranidealgas,whenf=P,thisequationreduces
totheidealgaslaw.
Thus,foranytwophysicalstatesatthesametemperature,representedbysubscripts1and2,theratioof
thetwofugacitiesisasfollows:

Foranidealgas,thisbecomessimply
or
ButforP0,everygasisanidealgas.Therefore,fugacitymustobeythelimitequation

Wedeterminefbydefininganewfunction,whichisthedifferencebetweentheactualmolarvolume
andtheidealgasmolarvolume:

WecanobtainvaluesforexperimentallyeasilybymeasuringV,TandP.
Fromtheexpressionabovewehave

(Itismoreobviousherethatisthe"extra"molarvolumeofanonidealgas.)Wecanthenwrite

Where

Sincetheexpressionforanidealgaswaschosentobe
,
wemusthave

SupposewechooseP0.Since
,
weobtain

Thefugacitycoefficientisdefinedas= Pf (notethatforanidealgas,=1),anditwillthenverify

Theintegralcanbeevaluatedviagraphicalintegrationifweexperimentallymeasurevaluesforwhile
varyingP.
WecanthenfindthefugacitycoefficientofagasatagivenpressurePandcalculate
.
Thereferencestatefortheexpressionofarealgas'schemicalpotentialistakentobe"idealgas,atP=1
barandtemperatureT".Sinceinthereferencestatethegasisconsideredtobeideal(itisanhypothetical
referencestate),wecanwritethatfortherealgas

ForagasobeyingthevanderWaalsequation,theexplicitformula[4]forthefugacityis

Thisformulaisdifficulttouse,sincethepressuredependsonthemolarvolumeV[p]soonemust
chooseavolume,calculatethepressure,andthenusethesetwovaluesontherighthandsideofthe
equation.

Fugacityofapureliquid
Forapurefluidinvaporliquidequilibrium,thevaporphase
fugacityisequaltotheliquidphasefugacity.Atpressuresabove
thesaturationpressure,theliquidphasefugacityis:[5]

wherevliqisthemolarvolumeoftheliquid.
Thefugacitycorrectionfactorforthevapor,sat,shouldbe
evaluatedatthesaturationpressureandisunitywhenPsatislow.
TheexponentialtermrepresentsthePoyntingcorrectionfactor
andisusuallynear1unlesspressuresareveryhigh.Frequently,
thefugacityofthepureliquidisusedasareferencestatewhen
definingandusingmixtureactivitycoefficients.

Fugacityvs.pressureofethaneat
60F(51C).Notethe
"breakpoint"atthesaturationpressure
andthecurvatureathigherpressures
asthePoyntingcorrectionfactor
comesintoplay

Seealso
Activity(chemistry),themeasureofthe"effectiveconcentration"ofaspeciesinamixture
Chemicalequilibrium
Electrochemicalpotential

Excesschemicalpotential
Partialmolarproperty
Thermodynamicequilibrium
Fugacitycapacity
Multimediafugacitymodel

References
1.Atkins,PeterDePaula,Julio(2006).Atkins'PhysicalChemistry(8thed.).W.H.Freeman.p.112.
2.Atkins,PeterLocke,JohnW.(January2002).Atkins'PhysicalChemistry(7thed.).OxfordUniversityPress.
ISBN0198792859.
3.Lewis,GilbertNewton(June1901)."TheLawofPhysicoChemicalChange".ProceedingsoftheAmerican
AcademyofArtsandSciences37(4):4969.doi:10.2307/20021635.
4.David,CarlW.(2015)."FugacityExamples2:Thefugacityofahardspheresemiidealgasandthevander
Waalsgas".ChemistryEducationMaterials91.
5.Prausnitzetal.(1999).MolecularThermodynamicsofFluidPhaseEquilibria(3rded.).PrenticeHall.p.40
43.

Externallinks
Videolectures
Thermodynamics,UniversityofColoradoBoulder,2011
Introductiontofugacity:Wherediditcomefrom?(http://www.youtube.com/watch?v=fkqm
f_QR4Yg)
Whatisfugacity?(http://www.youtube.com/watch?v=AMBoLiQJMFQ)
Whatisfugacityinmixtures?(http://www.youtube.com/watch?v=OZFB48wVtjw)
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Categories: Physicalchemistry Chemicalthermodynamics Thermodynamicproperties
Statefunctions
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