Phasebehaviorofmixtures

Theinteractionofthedifferentmoleculesinamixturecausesbehaviornotobservedinpurefluids(/Phase_behavior_of_pure_fluids).Phasediagrams(/Phase_diagrams)
describethevolumetricbehaviorofmixtures.Thisarticlepresentsthebasicproceduretopredicttheequilibriumphasebehaviorofmixturesbyacubicequationofstate
(/Equations_of_state)(EOS).Moredetailedinformationcanbefoundinmanysources,includingFiroozabadi[1]andWhitsonandBrule.[2]

Contents
1EOSofamixture
2Procedureforequilibriumcalculationsofamixture
3Nomenclature
4References
5NoteworthypapersinOnePetro
6Externallinks
7Seealso

EOSofamixture
ThethermodynamicpropertiesofamixturecanbecalculatedwiththesameEOSforapurefluid,withsomemodifications.Theprimarydifferenceisthatthemixturemolar
volumeforaphaseiscalculatedwithEOSconstantsandtemperaturedependentfunctionsofthephasemolarcomposition,eitherxioryi.Forexample,theSoaveRedlich
KwongEOSwrittenforamixtureis

(/File%3AVol1_page_0364_eq_001.png)

wheresubscriptmindicatesamixtureproperty.Themixturepropertiesarecalculatedwithmixingrulesthatareoftenlinearorquadraticfunctionsofthephasemolefractions.
Forexample,fortheliquidphase,themixingrulefortheproduct,a,isoftenthequadraticequation,

(/File%3AVol1_page_0364_eq_002.png)

where (/File%3AVol1_page_0364_inline_001.png).Theparameterskijarecalledbinaryinteractionparameters.Binaryinteractionparametersare
constantsthataredeterminedbyfittingthecubicEOStoexperimentalPVTdata.ThemixingruleforaistheoreticallyjustifiedfromvirialEOS,whicharediscussedinseveral
sources.[1][3][4][5][6][2]Forbm,thelinearrelationship, (/File%3AVol1_page_0364_inline_002.png),isoftenused.

Forequilibriumcalculations,thefugacityofeverycomponentineachphasemustbecalculated.Eq.1isusedforthispurpose.Forexample,substitutionoftheSoaveRedlich
KwongEOSintoEq.1givesthefugacityofacomponentintheliquidphase,whichiswrittenas

(/File%3AVol1_page_0364_eq_003.png)....................(2)

where (/File%3AVol1_page_0364_inline_003.png).Asimilarequationiswrittenforthevaporphase,wherexiisreplacedbyyi,andsuperscriptLisreplacedbyV.

Procedureforequilibriumcalculationsofamixture
Theprocedureforequilibriumcalculationsofapotentialtwophasemixtureismorecomplexthanthatofapurefluid.Foranequilibriumflashcalculation,thepressureand
temperatureandoverallmolefractionsarespecified(i.e.,pressureandtemperaturearenowindependent,asspecifiedbytheGibbsphaserule).Thegeneralprocedureforaflash
calculationisdiscussednext.

1.MakeaninitialguessoftheKvalues,where (/File%3AVol1_page_0365_inline_001.png).WhentheguessoftheKvaluesisneartheequilibriumsolution,the
procedurewillconvergerapidly.Iftheguessisnotgood,theproceduremightnotconvergeatall.MostEOSprogramsusesomeempiricalcorrelationtoestimatethe

phasemolefractionsbasedonKvalues.TheWilsonequation[7]isoftenused,where (/File%3AVol1_page_0365_inline_002.png).

2.CalculatexiandyiwiththeRachfordRiceprocedure.[8]OncetheKvaluesforeachcomponentarespecified,theRachfordRiceprocedureisusedtoestimatethephase
molefractions.Amaterialbalanceoneachcomponentgiveszi=Lxi+(1L)yi,whereListhemolefractionliquid(seeEq.2).Substitutionofyi=Kixiintothematerial

balanceequationgives,uponrearrangement, (/File%3AVol1_page_0365_inline_003.png)oralternatively

(/File%3AVol1_page_0365_inline_004.png).Substitutionoftheseexpressionsintothefunction (/File%3AVol1_page_0365_inline_005.png)

gives (/File%3AVol1_page_0365_inline_006.png).ThisisanonlinearequationthatcanbestbesolvedbyasimpleNewtonRaphson

iteration,whereforeachiterationthenewvalueoftheliquidmolefractionisfoundfrom (/File%3AVol1_page_0365_inline_007.png).Forthe

firstiteration,chooseL=0.5anditerateuntil (/File%3AVol1_page_0365_inline_008.png).
 (/File%3AVol1_page_0335_eq_001.png)....................(2)

3.CalculatethecubicEOSparameters(e.g.,amandbm).ThisstepisverystraightforwardanddependsontheselectedEOSanditsassociatedmixingrules.Thecritical
temperatures,pressures,andacentricfactorsforeachcomponentareneededtocalculatetheEOSparameters.
4.SolvethecubicEOSforthephasemolarvolumesVmLandVmV.ThissteprequiressolutionofthecubicEOSforthecompressibilityfactor,Z,ofthevaporandliquid(or
alternativelyforVVandVL).Becausethecompositionsofthevaporandliquidaredifferent,twoseparatesolutionsfortherootsofthecubicEOSarerequired.Acubic
equationsolveroriterationmethodshouldbeusedtoobtaintherootsoftheEOS.

TheprocedureforthisstepismorecomplexthanforapurefluidbecausesixrootsofthecubicEOSarecalculated(i.e.,threerootsfortheliquidandthreefor
thevapor).Themiddlerootforthevaporandliquidarediscardedbecausethatsolutionleadstounstablephases,similartopurefluids.Oneoftheremaining
twoliquidrootsispairedwithoneoftheothervaporrootstocalculatecomponentfugacitiesandequilibrium.Ifthewrongrootpairingisselected,thesolution
couldbefalseinthatanunstableormetastablesolutioncouldbeobtained.ThecorrectequilibriumsolutionistheonethatminimizesthetotalGibbsenergy
comparedwiththeotherpossiblerootpairings.Firoozabadi[1]andWhitsonandBrule[2]provideagooddescriptionofhowtoselecttheliquidandvaporrootsso
thatthetotalGibbsenergyofthetwophasemixtureisminimized.Formostcases,thecorrectrootfortheliquidistheonethatgivesthesmallestmolarvolume,
andthecorrectrootforthevaporistheonethatgivesthelargestmolarvolume.
Firoozabadi[1]andWhitsonandBrule[2]alsoexamineusingstabilityanalysestodeterminewhetheramixturewillformthreephasesinsteadofjustoneortwo
phases.PhasediagramsforEORprocesses(/Phase_diagrams_for_EOR_processes)discussestheformationofthreeequilibriumphasesinCO2/crudeoil
systems.

5.Calculatethecomponentfugacitiesofeachcomponentineachphase, (/File%3AVol1_page_0366_inline_001.png)and
(/File%3AVol1_page_0366_inline_002.png).TheselectedcubicEOSisusedtodetermineanexpressionforthefugacityofacomponentinaphase(seeEq.2for
example).
6.Checktoseeifequilibriumhasbeenreached.Agoodcriterionis (/File%3AVol1_page_0366_inline_003.png)forallcomponents.Ifthecriteriaare

satisfied,equilibriumhasbeenobtained.Thecorrectequilibriumsolutionisfoundwhen (/File%3AVol1_page_0366_inline_004.png)foreachcomponent.

Becausethesolutionisneverfoundexactly,weacceptthesolutionif (/File%3AVol1_page_0366_inline_003.png)foreachcomponent.Thetoleranceof

105canbedecreasedifbetteraccuracyisrequired.
7.Ifthecriteriahavenotbeensatisfied,theKvaluesshouldbeupdatedandstepstwothroughsixrepeated.Thisstepisalsoveryimportantitaffectsboththerateof
convergenceandwhethertheiterationconvergesatall.Oneprocedurethatworkswellisthesimplesuccessivesubstitutionschemethatreliesonthefactthat

(/File%3AVol1_page_0366_inline_005.png)and (/File%3AVol1_page_0366_inline_006.png)foreachcomponent.Therefore,

(/File%3AVol1_page_0366_inline_007.png).Atequilibrium,thecomponentfugacitiesareequalsothat (/File%3AVol1_page_0366_inline_008.png).We

canusethisratiotoestimatenewKvaluesfromtheoldones.Thatis, (/File%3AVol1_page_0366_inline_009.png).OncethenewKvaluesare
determined,stepstwothroughsixarerepeateduntilconvergenceinstepsixisachieved.Convergencefromsuccessivesubstitutionscanbeslownearthecriticalregion.
Othermethodsmayberequiredwhenconvergenceisslow.[1]

Nomenclature
(/File%3AVol1_page_0367_inline_001.png) = fugacityofacomponentinamixture,mole2pressure/mole2,Pa
k = binaryinteractionparameter,dimensionless
Ki = Kvalueofithcomponent,yi/xi,dimensionless
L = liquidmolefraction,molesliquid/totalmoles,dimensionless
p = pressure,force/area,Pa
R = gasconstant,pressurevolume/temperature/mole,Pam3/(Kelvinmole)
t = time,seconds
T = temperature,Kelvin
V = vapormolefraction,molesvapor/totalmoles,dimensionlessormolarvolumeoffluid,volume/mole,m3/mole
x = xcoordinate,length,m
xi = molefractionofithcomponentinliquid,molesithcomponentinliquid/totalmolesliquid,dimensionless
(/File%3AVol1_page_0368_inline_001.png) = fugacitycoefficientforacomponentinamixture,mole2pressure/mole2pressure,dimensionless

References
1.1.01.11.21.31.4Firoozabadi,A.1999.ThermodynamicsofHydrocarbonReservoirs.355.NewYorkCity:McGrawHillBookCo.Inc
2.2.02.12.22.3Whitson,C.H.,andBrule,M.R.2000.PhaseBehavior,Vol.20.Richardson,Texas:MonographSeries,SPE.
3.Prausnitz,J.M.,Lichtenthaler,R.N.,anddeAzevedo,E.G.1999.MolecularThermodynamicsofFluidPhaseEquilibria,thirdedition.NewJersey:PrenticeHall.
4.Sandler,S.I.2000.ChemicalandEngineeringThermodynamics,thirdedition.NewYorkCity:JohnWiley&Sons.
5.Smith,J.M.,VanNess,H.C.,andAbbott,M.M.2001.ChemicalEngineeringThermodynamics,sixthedition.787.NewYorkCity:McGrawHillBookCo.Inc.
6.Walas,S.M.1985.PhaseEquilibriainChemicalEngineering.671.Boston,Massachusetts:ButterworthPublishings.
7.Wilson,G.M.1969.AModifiedRedlichKwongEquationofState,ApplicationtoGeneralPhysicalDataCalculations.Paper15cpresentedattheAIChENatl.Meeting,
Cleveland,Ohio,47May.
8.RachfordJr.,H.H.andRice,J.D.1952.ProcedureforUseofElectronicDigitalComputersinCalculatingFlashVaporizationHydrocarbonEquilibrium.JPetTechnol4
(10):19,3.SPE952327.http://dx.doi.org/10.2118/952327G(http://dx.doi.org/10.2118/952327G)

NoteworthypapersinOnePetro
UsethissectiontolistpapersinOnePetrothatareaderwhowantstolearnmoreshoulddefinitelyread

Externallinks
UsethissectiontoprovidelinkstorelevantmaterialonwebsitesotherthanPetroWikiandOnePetro
Seealso
Thermodynamicsandphasebehavior(/Thermodynamics_and_phase_behavior)

Firstlawofthermodynamics(/First_law_of_thermodynamics)

Secondlawofthermodynamics(/Second_law_of_thermodynamics)

Equationsofstate(/Equations_of_state)

Phasebehaviorofpurefluids(/Phase_behavior_of_pure_fluids)

Phasecharacterizationofinsitufluids(/Phase_characterization_of_insitu_fluids)

PEH:Thermodynamics_and_Phase_Behavior(/PEH%3AThermodynamics_and_Phase_Behavior)

Categories(/Special%3ACategories): 5.2.1PhasebehaviorandPVTmeasurements(/Category%3A5.2.1_Phase_behavior_and_PVT_measurements)
5.2.2Fluidmodeling,equationsofstate(/Category%3A5.2.2_Fluid_modeling,_equations_of_state)

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