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PengRobinsonequation

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PengRobinsonequation
PureFluid
General
EquationwaspresentedinPengandRobinson(1976)withsomecorrectionsmadebythesameauthorsin(1978).Inwhat
followswearetryingtosticktooriginalnotations,someofthemaredescribedhere.
PengRobinsonequationitselfisthespecialversionofthegeneralcubicequationofstatewith

and

= 1

a(T )

RT
P =

= 2

V b

+ 2bV b

where
2

a(T ) = [1 + (1 T r )] a c
2

R T

a c = [a = 0.45724]
b = [b = 0.07780]

kgm

s mol

2
c

Pc

kgm
2

s mol

RT c

Pc

mol

and isadimensionlessparametersuchthat
2

0.49 :

= 0.37464 + 1.54226 0.26992

> 0.49 :

= 0.379642 + 1.48503 0.164423

WithnewvariablesA

= a(T )P /R T

andB

+ (B 1)Z

= bP /RT

+ 0.016666

itcouldberewrittenintermsofcompressibilityfactor
2

+ (A 2B 3B )Z + (B

+ B

AB) = 0

PlotExample
Cubicpolynomialexamplesformethane(CH4)forcriticalpressureatcriticaltemperatureandfornearlycriticalpressureat

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PengRobinsonequation

criticaltemperature:
Itcouldbe
seenthatatsubcriticalpressuretherearetwopossibilitiesforaroot.Itmeansthatthevalueofcompressibilityfactorhastwo
values:liquidandvapor.

Fugacity
Formulaforfugacitycoefficientofsimplefluid,calculatedviaPRequation,hasexpression
f
log = log

Z + (2 + 1)B

A
ln {

= (Z 1) ln {Z B}
P

2 2 B

}
Z (2 1)B

HeatCapacity
Departurefunctionofheatcapacity,calculatedviaPRequation,hasexpression
2

Z + (2 + 1)B

ln {

Cp Cp = a (T )
2 2 b

R(M N )
} +
M

Z (2 1)B

R
2A(Z + B)

Differencebetweencapacities,calculatedviaPRequation,hasexpression
2

R(M N )
Cv Cp =

2A(Z + B) M

where
M =

+2BZB

N = a (T )

ZB

B
bR

Inthecaseofsimplefluidfollowingformulasforderivativeofparametera(T ) couldbeapplied

a (T ) = a c [

Tc

1+
T Tc

a (T ) =

ac (1+)
2 T

Tc

SonicSpeed
Accordingtothesectionaboutsonicspeed,incaseofPRequation,sonicspeedcouldbeexpressedinanalyticformas

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2/19/2015

PengRobinsonequation
us

Cp
2a(T )(V + b)
RT
(
)
= V

2
2 2
2
Cv M w
(V
+ 2bV b )
(V b)

whereMw osthemolarweight.

Mixtures
MixingRules
ParametersofPRequationforthemixtureofN simplefluidswheremolarpercentofthei thcomponentiszi aredefinedby
mixingrules
N

a = z i z j a ij
i=1

b = z i bi

j=1

i=1

Hereaij isexpressedthroughempiricallydeterminedbinaryinteractioncoefficientij characterizingthebinaryformedby

componenti andcomponentjas
aij = (1 ij )

a a
i j

Someij aretabulated(e.g.table4.2inPedersenandChristensen(2006)).Forthoseonewhicharenottabulatedformulaof
ChuehandPrausnitz(1967)couldbeused:

2V

1/6

c,i

1 ij =
V

1/3

c,i

1/6

1/3

+ V

c,j

c,j

Fugacity
Formulaforfugacitycoefficientofthemixture,calculatedviaPRequationandstandardmixingrules,hasexpression(seePeng
andRobinson(1976)orequation4.65inPedersenandChristensen(2006)formoredetail)

log i = log

fi

= ln(Z B) + (Z 1)

zi P

bi

2 2 B

1
[

bi

(2 zj aij )

Z + (2 + 1)B
] ln {

j=1

}
Z (2 1)B

HeatCapacity
Formulasforheatcapacitydeparturefunctionanddifferenceofcapacitiesforthemixtureofsimplefluidsarethesameasfor
thesimplefluid.Correspondingchangesfortheexpressionsofderivativesofa(T ) shouldbedone.
Sincea isthelinearcombinationofparametersaij ,derivativesofa areexpressedthroughderivativesofaij straightforward
N

= zi zj a
i=1

ij

j=1

= zi zj a
i=1

ij

j=1

Derivativesofaij inthecaseoftimeindependentinteractioncoefficientsaregivenbyformulas

ij

http://kshmakov.org/fluid/note/3/

a aj + a ai

1 ij
=

ai aj

ij

[
4

2a i a j (a a j + 2a a

1 ij
=

+ a i a ) (a a j + a a i )
3/2

(a i a j )

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PengRobinsonequation

1. WikionPengRobinsonEquation
2. Peng,D.Y.,andRobinson,D.B.(1976).ANewTwoConstantEquationofStateIndustrialandEngineeringChemistry:Fundamentals15:5964
DOI:10.1021/i160057a011
3. Peng,D.Y.,andRobinson,D.B.(1978).TheCharacterizationoftheHeptanesandHeavierFractionsfortheGPAPeng&ndashRobinsonPrograms
GasProcessorsAssociationDOI:no
4. MethoddocumentationforPVTsim16
5. Poling,B.E.,Prausnitz,J.M.andO'Conell,J.P.(2001).ThePropertiesofGasesandLiquids.McGrawHillProfMed/TechISBN:0070116822,
9780070116825
6. Leland,Th.W.Jr.,andChapellear,P.S.(1968).TheCorrespondingStatesPrincipleAReviewofCurrentTheoryandPracticeIndustrialand
EngineeringChemistry60(7):1543DOI:10.1021/ie50703a005
7. Pedersen,K.S.andChristensen,P.L.(2006).PhaseBehaviorofPetroleumReservoirFluids.CRCPressISBN:9780824706944
8. Chueh,P.L.,andPrausnitz,J.M.(1967).VaporLiquidEquilibriaatHighPressures.CalculationofPartialMolarVolumesinNonpolarLiquid
Mixtures.AIChEJournal13(6):10991107DOI:10.1002/aic.690130612
9. Huron,M.J.,andVidal,J.(1979).NewMixingRulesinSimpleEquationsofStateforRepresentingVaporliquidEquilibriaofStronglyNonIdeal
Mixtures.FluidPhaseEquilibria3(4):255271DOI:10.1016/03783812(79)800011

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