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The PredictionofVapour Liquid Equilibrium Behaviourof

Zakari4 Z andTee,S.Y.
GasEngineeringDepartmentFacultyof Chemical& Natmal ResourcesEngineeflng
UniversitiTeknologiMalaysia81310UTM SkudaiJohorDarulTakzim
Tel: 607-5535497
This paperis a contributionto the developmentofmathematicalmodel for the prediction
ofvapour liquid equilibrium behaviourofpropanebutale mixtue at non-idealstate.The
proposedmodel is based on the generalizedvirial equation of state atd GalDma,?hi
formulation.Mathematicalmodeling Mathcadis usedto numerically solve for fugacity,
fugacity coefficient, activity coefficient and vapour-phasecomposition of propane
butanemixtue by taking into considerationthe effects of temperatureand pressure.A
rangeof263.15Kto 313.l5K chosenin this modelingis ofpracticabilityfor
propane butane mixtue in cylindrical storage. The prediction of vapour liquid
equilibrium behaviour for prcpane butane mixtule is illustrated in P*y diagram at
different system temperatures.It is clearly shown that solution fugacity coefficient
steadilyas systemtemperature
increase.It is alsoshownthatthe
solution fugacity increaseswith s)tstemtemperatueandprcssure.Activity coefficientof
butane in mixtue becomes larger as system tempemtule and pressure tncrease.
Meanwhile, there is insignificant decreasein activity coeJTicientof propane with
temperatue and prcssure.As systemtempemtweard pressrre go higher, vapour-phase
compositionof propanedecreases
while for butane,its concentration
in vapourphase


Activity coefficient

Fugacitycofficientofpue species

p"gacity coefficientofspeciesin solution


fugacity ofpue species


Fugacityofspciesin solution

Liquid phasemole fraction




Vapor phasemol fractio[






Satunted condition


The acculateprcdiction ofphase equilibrium offluid mixtures is extremelyimpofiant in
many industdal applications, such as rcservoir modeling, process design, and gas
exampleofphaseequilibdumis thepdmary
processin an oil refinery which involves the sepa.rationof the crude oil into the more
valuablefiactioN i.e.,gasoline,kerosene,
dieselfuel, etc.by distillation.Equilibriumis
a static condition in which no changesoccur in the properfiesof a systemwith time. A
state of equilibrium is a state of rest (Lewis and Rardall, 1961). Phase-equilibrium
thermodlaDmics seeks to establish the relations among the various properties, in
particular, temperature,prcssrre and composition,that ultimately prevail when two or
morephasesreacha stateof equilibrium whereinall tendenciesfor cha.nges
Most of the initial work in vapor liquid equilibrium (VLE) behaviour of hydrocarbon
mixtue was with the systemat low pressweand low temperaturewhere an ideal state
wasusually assumed.Basedon the previousrcsearches,there are no studiescarriedout
olr the hydrocarbon system, especially the light hydrccarbon system, at non-ideal
condition. Ideal model like Raoult's law model is applied to the hydrocaxbonsystemat
ideal state. Situations chaagewhen the said system is not at ideal state since ideal
systemshaxdly exist in real life. The deviations from mixtwe ideality should be
accountedin the predictionofVLE for propanebutanemixtule.


Fugacityand FugacityCoeflicient
The fugacity is a quantity that conespondsto the pressulefor a non-ideal gas.Fugacity
is a pseudoor effective pressrre.It is the pressuleat which the chemicalpotentialofan
ideal gasis the sameasthat ofthe ral gasat the true prcssue. Fugacityofa component
in a gasmixtue is a pseudoor effctivepartial pressue for that component.

Fugacity fi is a propertyof a pwe materialandit dependsupontemperatureand

pressue,which must be uniform tfuoughoutboth phasesat equilibrium. The criterion of
for multicomponenr
systemis asloilowsl



Fugacitycoefficientis anothernew propelty, which is dimensionless.The fugacity

coefficientofpure speciesi,f, is definedas:


Whendealingwith ideal gas,At =l ardlt

= P. On theotherhand,thedefinitionof

thefugacityofa speciesin solutionis parallelto thedefinitionofthe pure-species

fugacity.Fugacitycoefficientofspeciesi in solutionis exprcssed



Activity Coefficient

In contrastto fugacity, activity coefficientis inherentlya multicomponentco[cept that is

useful only for mixtures. It is introducedinto Raoult's law to accountfor liquid-phase
non-idealities.In llon-ideal mixtures, activity coefficients depend stongly on liquidphasecomposition.Ideal solution servesas a standaxdto which real-solutionbehaviour
canbe compared.Activity coeflicient is definedin the following expression:


/ i - ----;


Formulationof VLE
Modified Raoult's law includesthe activity coefficient to accountfor liquid-phasenonidealities, but it is limited by the assumptionof vapour-phaseideality. This can be
overcomeby introducing the vapour-phasefugacity coefficient. For speciesi in vapour
mixture and in liquid solution, tugacity of speciesI in vapourphaseand in liquid phase
caobe rcpresentedby:

i: = y,6,p ard ]i = x,y,f,


The criterion for phaseequilibrium is that thesebe equal:


In order to calculatewith confide[ce the fugacitiesin a gasmixture, it is advantageous
to use a.nequationof statwhere the parametershave physical significance,i.e. where
car be relatedto intermolecular
desirableability is the virial equationof state.The fundamertal advantageof the virial
equation is that it directly rclates fugacities in mixtures to intermolecular forces
1999). Vapour phase non-idealities in the calculation of
thermodynamicspropertisnear atmosphedcpressureand often up to about 1.5MPacan
(Prausnitz et

be representedby the virial equationof state with the inclusion of the secondvirial
coe{ficientonly (Virendra et al., 1995).The gereralizedvirial equationhasbeenwidely
used becauseit only requiresthe substance-dependent
critical paxametenanctacentnc
factor. Generalizedvirial equation is of greater applicability to all gases.The most
importantadvartageofthe vidal equatio[ofstatefor applicationto phaseequilibriumis
et al., 1999).Mixing rulesshouldbe included
its directextensionto mixtues (Prausnitz
when dealing with mixtue. For two-term truncated form, mixture second virial
coefficientis a function oftemperatue only.

This researchproject involves mathernaticalmodeling. Mathcad is used to numerically
solve fugacity, fugacity coefficient and activity coefficient for propanebutanemixtule.
All the required inputs like propertiesofpropa.neand n-butare shouldbe definedin the
early stage.Then suitable equationsare listed in coffect sequencesin order to get the
final results. There are four paxameteNto be solved in this study. They are fugacity,
fugacity coefficients, activity coefficie[ts and vapour phase compositions for each
speciesin propale butanemixhfe. Liquid phasecomposition and systemtempenture
are setbeforc solving the aboveparameters.In order to establisha mathematicalmodel,
appropriateassumptionsare made. The generalizedvirial equation of state method is
suitablefor propanebutanemixtwe. That is, the operatingcondition of propanebutane
mixture at 10 baxs is assumedas moderate presswe while appllng this method.
Limitationofthis methodis its applicabilityto low andmoderate
In this study,
10 bars is consideredhigh pressurefor propanebutane system but in the other way
round it is consideredas moderateprcssue when applying this method. Next, the
rcquiredliquid compositionofpropane butanemixture is referredto the composrhonat
equilibrium statewhich is obtainedthroughthe compositionanalyzer.Besides,butanein
the mixture is actually consisting of n-butanea.ndisobutane.In this project, butaneis
refefied to a mixture of 50% ofn-butane ard 50% of isobutane.In addition,propaneand
butane are chemically similar speciesand both speciesale non-reactivein a mixture.
of fugacitycoefficientin gasphase1f') equalsto thefugacity
Therefore,an assumption
coefficientin liquid phase(fr ) is made. This assumption
is basedon the fact thatthe
pure speciestugacitycoefficientin gasphase(/") equalsto the pwe speciesfugacity
ln LLqurc

This researchstudy focuseson the effect of temperaturealld pressureon the vapour
liquid equilibrium behaviour of propanebutare mixture. Mathematical modeling has
been developedin order to predict the VLE behaviow. The model cuaently proposed
cal be usedfor the predictionofVLE ofpropanebutanemixturein the full composition

Effect ofComposition
A t ?ical Prl diagam for six different tempemturescan be seenin Figure 1. It clearly
shows that when there is an increasein temperatue, there is an i[crcase in system
prcssure.For each temperatue, the upper curv rcprcsentsbubble point line while the
dew point line. A temperatwemngeof 263.15K to 313.15K
lower curyerepresents
chosenin this modeling is of practicability for propanebutare mixtue in cylindrical

Effect ofTemperature
Figure 2 displaysthe effect of temperaturecha[geson the fugacity coefficient. Here, it
is assumedthat mole llactions in liquid phasefor both the propanealld butaneare 0.6
and 0.4, rcspectively.The sameassumptionalso goes to Figures 3, 4 and 6. It can be
seenclearly that fugacity coafficients of solution as well as of individual specresin
mixtwe decrcasessteadilyas the systemtemperatureincreases.That is, the deviationof
fugacity coefficient from unity becomeslarger as the system tempemtue becomes
Figure 3 showsthe effect oftemperaturechangeson fugacity aswell assystempressue.
As shownin Figure 3, solution fugacity increasesasthe systemtemperatureincreases.It
is showedthat the solution fugacity appearsvery closely to the fugacity of propanein

Figure 1: P4r diagramfor several


Figue 2: Fugacitycoefficients
different temperatues



Figwe 3: Fugacityandvaporr pressrre

at differcnt temperatwes

Figwe 4: Activity coefficientsat

different temperatures

This is becausefugacity is known asa parameterrepresentingth effectivepressurein

vapourphase(Prausnitzet a1.,1999).Sincethereis more propanein vapourphass,
thereforeboth the solution fugaciryard fugacityof propanein mixture showthe similar
trend.That is, thereis negligiblegapbetweenthesetwo pammeters.On the otherhand,

Figure 3 showsclearly that the systempressurealwaysgreaterthan the solution fugacity.

A systemis considerdasan ideal systemwhe[ thesetwo parametemshownegligible
difference.As shownin Figure 3, differencebetweensystempressureandsolution
fugacitybecomeslargerwhen systemtemperatuebecomeshigher.That is, deviation
liom ideality for propanebutanemixture is more apparentat higher temperatrre.


Figue 5: Vapourphasecompositionsat
As can be seenfiom Figure 4, it is known that activity coefTicientof butare tncreases
appreciably as temperatwe glows higher. Mearwhile, there are only insignificant
decreasesin activity coefficient of propanewith temperature.As can be seen,activity
coefficient of propane sta) closely to unity while the activity coefficient of butane
deviatesfiom unity. Activity coe{ficientis a pam.rreterusedto accountfor liquid-phase
In general,thereis morcbutanein liquid phase.Therefore,the effectof
temperatureon activity coefficient of propanein liquid solution is quite imignificant
1 while the effect of tempemtulebdngs relatively significant changeson butane.Figue 5
showsthe effect of temperatrrgon yaporr phasecomposition.As temperatuebecomes
higher, more butare vaporizes therefore the vapour phase composition of butare
increaseswhile the vapour phasecompositionof propanedecrcases.Howver,there is
alwaysmore propanein vapour phasedue to its higher vapour pressule.Thesevapour

phasecompositionsare then usedin the study of dischargingFocess of propanebuta.ne

mixtue ftom cylindrical stomge.
Effect ofPressure
Figwe 6 displaysthe effect of pressrueon activity coefficient at different temperatures.
At constanttemperature,as pressuregoes higher deviationsof activity coefficient for
butanebecomemore noticeable.Even though therc is a deviation from unity, the said
deviation can actually be neglectedbecause,as can be seenfrom Figure 6, the highest
value of activity coefEcientis less than 1.02 for these six temperutwes.This value is
actually not far fiom unity. Sometimes,this value can even be approximatedto unity.
Unlessnear the critical region, activity coeJficientis little affected by pressureand is
strongly affected by the natue of pure chemicals comprising the liquid solution
(Alvarado,1993).This statementclearly explainsthat it is reasonable
to neglectthe
deviation of activity coefficient when pressurechaages.Meanwhile, activity coefficient
ofpropane approachesunity at certainpressure.Apart from that paxticularpressure,it is
clearly shown that activity coefficientgoes larger than unity at lower pressureand
smaller than unity at higher pressure. Besides, larger range of value of activity
coefllcientis accounted
Figue 7 depicts the effect of system pressure on solution fugacity at differcnt
temperatus. It is cleaxly shown that as the pressure increases,solution fugacity
inqeases at coNtant temperature.At higher tempemture,solution fugacity becomes
larger and it obviously accountsfor larger range of values. Figwe 7 clearly tells that
solution fugacity is always smaller thar systempressuredue to the non-idealitiesin
t propane butare mixtwe. However, the difference between these tlvo parametersfor
propanebutanemixtue is always small. Judgingfrom the modeling, the ratio between
solutionfugacityand systempressue(?P) alwaysrangesAom 0.73 to 0.87.Figure8
depicts the effect of system pressrueon solution fugacity coefficient at different
temperatures.It is clearly shown that as the prcssurc increases,solution fugacity

coeffrcientdeoeasesat coDstanttemperature.At higher temperature,solution fugacity

coefficientaccountsfor largerrangeofvalues andthe deviationsfrom unity are larger.


Figure 6: Effect ofpresswe on activity

coefficient at differcnt

Figure 7 : Effect ofpressureon

solution tugacity at
different temperatures

Figwe 8 : Effect ofpressureon solution

fugacity coefficientat
diffrent temperatures

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