B2
Printed in Islamic Republic of Iran, 2001
to Shiraz University
MODIFICATION OF THE VAN LAAR ACTIVITY
Yr
COEFFICIENT MODEL
G. R. VAKILINEZHAAD*1, H. MODARRESS *2AND G. A. MANSOORI
3
IChemical Engineering Department, Faculty of Engineering, University of Kashan, Kaspan, 1 R. of Iran
2 Chemical Engineering Department, Amirlcabir (polytcclmic) University of Technology, Tehran, I. R. of Iran
3 Chemical Engineering Department, University of illinois, 810 S. Clinton Street, Chicago, USA
Abstract  Based on statistical and mechanical arguments, the original van Laar activity
coefficient model has been improved by reasonable assumptions. This modification has been
done by replacing the van der Waals equation of state with the RedlichKwong equation of
state in the formulation of van Laar with consistent mixing rules for the energy and volume
parameters of this equation of state (a",ix, b
mix
). Other equations of state, such as the Soave
modification of the RedlichKwong equation of state, PengRobinson and MohsenNia,
Modarress and Mansoori equations of state, have been introduced in the formulation of van
Laar for the activity coefficients of the components present in the binary liquid mixtures, and
their effects on the accuracy of the resultant activity coefficient models have been examined.
The results of these revised models have been compared with the experimental data and it
was found that the RedlichKwong equation of state with the van der Waals mixing rules for
the volume and energy parameters of this equation, is the best choice among these equations
of state. In addition, it can improve the original van Laar activity coefficient model and,
therefore a better agreement with the experimental data is obtained.
Keywords statistical mechanics, phase equilibria, activity coefficients models, nonideal solutions
1. INTRODUCTION
There are two ways for the estimation of fugacities of the species in liquid mixtures: (i) For the
mixtures involving onfy hydrocarbons and dissolved gases, simple equations of state such as the Peng
Robinson equation of state [1] may be used for the estimation of species fugacities. (ii) However, for
liquid mixtures containing alcohols or electrolytes, in which one or more of the components cannot
presently be described by an equation of state in the liquid phase, another procedure for estimating
species fugacitieS must be used. The most common starting point can be written as follows:
(1)
where r I is the activity coefficient and J/ is the fugacity of the species (i) in the pure state. It is
evident from the above equation that in case (ii) for the purpose of studying the behavior of the liquid
mixture, one must have the activity coefficient of the species present in the liquid mixtures.
Many efforts have been made to present the various activity coefficient models, such as
Margules, van Laar, UNIQUAC, etc. In this work, the van Laar model is improved to increase its
accuracy in activity coefficient calculations for liquid mixtures.
'Received by the editors November I, 1998 and in final revised form Octohec 4, 1999
'Corresponding author
282 G. R. Va/cJIlne:/uuzd / et Q/.
In the van Laai' theory leading to its activity coefficient mo<;iel, which is based on the application
of the van der Waals equation of state, for a two component mixture with mole fractions Xl andx
2
,
two main assumptions are involved, which are: ~ = O and S=O. This means that when mixing two
pure components no volume change occurs, and the entropy change of mixing is equal to its ideal
value.
The van Laar theory comprises of three stages as follows [2]:
a) Expansion of pure liquids isothermally to a very low pressure.
b) Mixing the resultant ideal gases (due to very low pressure).
c) Isothermal compression of the mixture of ideal gases.
Van Laar used these stages for the formulation of the excess Gibbs free energy of mixing and
obtained the following equations for the activity coefficients of components (1) and (2):
In  b
VDw2
[ ( ~ ra;;;;;;)2/(1 b
vDw2
X2 )2]
rVDW2    + 
RT b
VDWI
b
vDw2
b
VDWI
Xl
where, arow and brow are the parameters obtained from van der Waals equation of state. Van der
Waals equation of state is presented as:
P= RT aVDW
vbVDw v
2
(2)
(3)
(4)
where, aroWi and browl can be expressed in terms of critical properties of component (i), Pel and Vel,
in the following form:
(5)
and
(6)
On the other hand, according to statistical mechanical arguments, it hlJS been proved that the
mixing rules for the cubic equations of state must be consistent with their algebraic form [3]. In this
work, we have modified the original formulation of the van Laar activity coefficient model using
these concepts.
2. THEORY AND FORMULATION OF THE REVISED VAN LAAR MODEL
Based on the works of Leland [46], and using the concepts of the statistical mechanics, the theory of
the van der Waals mixing rules bas been proposed by Kwak and Mansoori [3]. They proposed some
guidelines for derivation of the van der Waals mixing rules for the various equation of states, which
for the RedlichKwong equation of state we demonstrate their results as follows [7]:
{
n n 213 1/3}l.S (n n )112
a(RK)mb: = 77 XiX jaij bij / 77 XiX jbij
(7)
Iranilln Journal of Science & Technology, Volume 25, Number B2 Spr/ng2001
ModijiClldon of tire van Laar 283
/1 . /1
and b(RK)mix = L L XjX jbij (S)
j j
Where, a and b are the parameters of the RedlichKwong equation of state. The RedlichKwong
equation is;
P= RT
vb
RK
where, the parameters aRK and b
RK
can be expressed in terms of clitical properties as:
I and
b
_O.OS664RTc
RK
Pc
The combining rules for the aij and b/j parameters are as follows:
a/j = (1 kij )(a1ia.ii )112
and
L 113 1/3 / j
bij = + b ii ) 2
(9)
(10)
(11)
(12)
(13)
Using the RedlichKwong equation of state with the mixing rules presented in Eqs. (7) and (S),
we have reformulated the van Laar theory. Here we demonstrate the steps of the new formulation as
follows:
According to the thermodynamic relation,
(14)
and using Eq. (9), we can write
(15)
Therefore, for the RedlichKwong equation of state, similar to the van Laar form'.llation can be
obtained:
which can be written as,
3aRKI 1 V
xI{Ujdeal U)I = r;;; xI{)ln
2vT b
RKI
v+biUCl I
VI
(16)
(17)
In this stage a reasonable assumption for molar volume vi of each component is applied, that is
Vi bRJ(, therefore,
(IS)
Similarly for component 2,
3aRK2 ln2
x2(uideal uh = r;;; x2
. 2b
RK2
vT
(19)
lranion JourlUll of Science & Techn%gy, Volume 25, Number B2
284 G. It VakJIl..neduuul / et til.
Therefore, the new formulation for internal energy change for the stage (a) as presented by van Laar
theory can be expressed as follows:
A 3ln2 (aRKIXI aRK2X2)
aU   + .....:..:;:===
a  2"fi b
RKI
b
RK2
(20)
On the other hand, the isothermal mixing of ideal gases has no internal energy change, therefore, for
stage (b) we have,
(21)
For stage (c) which, is the isothermal compression of the mixture of ideal gases, the following
equation can be written:
Ilu = _3ln 2 a(RK)mix
c 2"fi b(RK)mix
(22)
and the total internal energy change, which in this theory is taken as equal to the excess Gibbs free
energy, can be written as,
(23)
Using Eq. (23), the activity coefficientsof components 1 and 2 are readily obtained;
In 3ln2 (a
RKI
M 3/2 3 M 1/2 M )
YRKI = 2RT3/2 b
RKI
 I "2 I 2
(24)
and
lny = 3ln2 (a
RK2
M 3/2 1/2 M )
RK2 2RT
3/2
b
RK2
I 2 I 3
(25)
where, M\ , M2 and M3 are given in the appendix.
This procedure is repeated with the other equations of state such as the Soave modification of the
RedlichKwong [9], PengRobinson [1] and MohsenNia, Modarress and Mansoori [10] equations of
state. Here, for the sake of simplicity, we mention only the results of $ese formulations, the details of
which are given in the appendix. The activity coefficients which have been obtained from the Soave
RedlichKwong are as follows:
In 2 aSRKl  MAlT
InYsRKr
RT b
SRK1
2[Xl (aSRKl  MAlT) + x2 (.,JaSRx 1 aSRK 2  MA12T)]
(x1b
SRK1
+ X2 bSRK2)  b
SRK
1 [(aSRK 1  MAIT)xl +
(aSRK2  + 2x
1
X
2 (.Ja SRK 1 aSRK 2  MAI2T)]
(x\b
1
+ X2 b2)2
(26)
Iranian Journal o/Science & Technology, Volume 25, Number B2 Spring ZOOI
In 2 a SRK2  MA2T
lnrSRK2 =
RT b
SRK2
Modijicllllon o/the wzn Latu
2[x2(aSRK2 MA2T) + Xl (,JaSRKlaSRK2 MA12T)J
(x1b
SRKI
+X2bSRK2)bSRK2[(aSRKI MAIT)x; +
(aSRK2 MA2T)xi MA12T)
(x1b
SRKl
+ X2bSRK2)2
285
(27)
If we use the PengRobinson equation of state in the fonnulation of the activity coeffl.cient then the
following equations will be obtained:
In 0.6232 0
1
 MTETl
rPR1=RT b
PRI
and for the component 2
In 0.6232 02  MTET2
rPR2 =RT b
PR2
2[Xl(01 MTETl)+X2(,JOI02 MTETl2)]
. 2
(x1b
pRI
+X2bpR2)bpR1[(Ol MTETl)Xl +
(02 +2XIX2(..j8;ii; MmTl2)]
(x1b
pRI
+X2bpR2)2
2[X2 (0
2
 MTET2) + xI (,JOI02  MTET12)]
(x1b
pRI
+ X2bpR2)  b
pR2
[(01  MTETl)xt +.
(02  MTET2)xi + 2xlx2 (..[if;ii;  MTETl2)]
2
(x1b
pRl
+ x2bpR2)
(28)
(29)
Finally, if we use the MohsenNia,. Modarress and Mansoori equation of state in the modelling of the
activity coefficients, for a binary liquid the resulting equations are,
2(xl a MMMl + Xl..J a MMMI aMMM2 )M  1
1 2 .J
ln r M'(Xl aMMMl +X2
a
.IJMM2 + 2XI X2 aMMMlaMMM2) r
MMMI.  RT 3!2 b
MMMI
M ' J
and for the component 4,
In 0.41 aMMM2
rMMM2 = RT 3/ 2 b
MMM2
2(X2aMMM2 + xl,JaMMMlaMMM2)M 
S(XraMMMl + + 2xIX1,JraMMM,aMM'M2)
M2
(30)
(31)
Spring 2001 Iranian Jourlflll o/Science & Technology, Volume 25, Number B2
286 G.lt
Various parameters which are present iti the above equations, as well as the details for the derivation
of these equations, are given in the
3. RESULTS AND DISCUSSION
. .
In order to compare the accuracy of the various models presented in this work, which are given by
Eqs. (24) to (31) with the original van Laar model given by Eqs. (2) and (3), we have calculated
vapor pressures of some binary mixtures at various temperatures. To calculate the vapor pressure of
the mixtures, the following equation may be used:
(32)
Figure 1 shows the variations of vapor pressure for system of Diethyl Ketone/nHexaJle at 65
0
C
calculated by the new model based on the RedlichKwong equation of state and'those obtained from
the van Laar original model as well as the experimental data. As it is seen from this figure, the vapor
pressures calculated by the new model are closer to the experimental data, which indicates the fact
that when the RedlichKwong eqUation of state, which is the improved form of van der Waals
equation of state, is used along with the appropriate mixing rule.s, the prediction of the van Laar
model is improved. The same trend is obtained '.for the systems of acetone/chloroform,
chloroformll,4dioxane, acetone/methanol, methyl ethyl ketone/toluene, nitrogen/methane, and
nitrogen/ethane which are presented in Figs. 210. It is worth noting that Figs. 610 are for high
pressure calculations which again indicates that the new formulation is ,more effective in vapor
pressure prediction compared to the original van Laar equation.
G,_,
II II
, II
1
II
II
.L__ __ ____ L_ __ J_ __
OJ .. u u
. ,
OJ .. u u
IIoIetactioaal_
Fig. 1. System Diethyl KetonelnHexane at 6SoC
Fig. 2. Acetone/Chloroform at SOC
... ,,
j :
II
, ..
i :
to
II
.L__ L ____ __ ____ __
...
.L__ __ __ ____ __
o u u u u
IIoIeFtll:tlanalllEK
Fig. 3. AcetoneIMethanol at. SSoC
Fig. 4. MEKlfoluene at SOC
lranilm JourlUll of Science & Technology, Volume 25, NUlllber B2
Spring, JOO}
ModijiclltJon of tile v_ lAIzr
287
'"
..
50
6
..
~
J
..
~
f===t=..
I ...
~
J
...
..

II
... ... ... ..
u ... u u
Fig. 5. System Chlorofonnll, 4Dioxane at 50"C Fig. 6. System AcetoneJMethanol at loO"C
 ,..., ,..,
, ...

, ..
, ...
, 
i :
j :
...
!GO
.. .. .. ..
__ 0I,*, __ 01 '*"III"
Fig. 7. System NitrogenlMethane at 99.82 K Fig. 8. System NitrogenlMethane at 110.93 K
,...,

, 
.. , , ...
, ...
... ... . ... .. __ 0 1 ~
Fig. 9. System NitrogenlMethane at 122.04K
",...,
14
I :
, .
i
.. ,
... ... ... __ 01,*,
Fig. 10. System Nitrogen/Ethane at 200 K
Table 1. Average absolute deviation (AAO%) for each system using .
different equations of state
System Average Absolute Deviation (AAI)OIo)
VOW
RI( SRI( PR MMM
    
Diethyl ketone'Hexape 29.12 2.43 2.58 2.65 30.15
AcetoneiChlorofonn 20.01 0.86 0.98 1.03 22.18
AcetonelMetharioi 4.52 1.42 1.58 1.63 4.86
MEKlroluene 5.18 0.46 0.53 0.62 5.88
ChlOrofonn/l,4Dioxane 23.24 2.02 2.31 2.44 25.20
Nitrogen! Methane 7.23 4.22 4.45 4.53 7.87
Nitrogen I Ethane 20.33 6.75 6.88 6.93 20.86
Spring 2001 Iranian JOll17l4l ofScknce & Technology, Volume 25, Nllmber B2
288 G. R. VakIllneduuu/letaL
The same calculations have been performed using PengRobinson, SoaveRedlichK wong, and
MohsenNiaModarressMansoori equations of state. To avoid presenting similar figures as 110, we
have reported the final results as the Absolute Average Deviation (AAO%) from experimental results
for the same systems in Table 1. From Table 1 it can be seen that the RedlichKwong equation of
state provides the van Laar theory with bettet; vapor pressure prediction for binary liquid mixtures.
4. CONCLUSION
It has been shown that the van Laar activity coefficient model, which is based on the van der Waals
equation of state, can be improved by replacing this equation of state with other more accurate
equations such as RedlichKwong, SoaveRedlichKwong, and PengRobinson equations of state.
However, the best results have been obtained using the RedlichKwong equation of state .
. The new formulation presented in this work has two main advantages. The first advantage is
demonstrated by the application of a more accurate equation such as RedlichKwong, instead of the
van der. Waals equation of state, which is used in the original van Laar theory. The second advantage
is shown by application of a mixing rule which has a sound theoretical basis from the statistical
mechanical point of view.
On the other hand, in spite of the more complex nature of three parametric equations of state
such as PengRobinson or SoaveRedlichKwong equations of state, the results obtained were not as
accurate as those of the RedlichKwong equation of state which has only two parameters. This can be
attributed to two reasons. Firstly, the RedlichKwong equation of state is the improved form of the
van der Waals equation of state and the reformulation of the van Laar activity coefficient model is
completely compatible with the original formulation of van Laar; thus, as one would expect using the
RedlichKwong equation of state gives a more accurate result. Secondly, the application of the Soave
RedlichKwong, and PengRobinson equations of state imposes a constraint on the parameters of this
equation which is not compatible with the general assumptions of the van Laar model.
Similar reason can also be put forward for the MohsenNia, Modarress and Mansoori equation of
state, which has a different form of mixing rule which is not compatible with the assumptions of the
van Laar theory. Therefore, these equations of state cannot predict vapor pressure close to
experimental values when combined with the van Laar theory.
Finally, it can be concluded that introducing the RedlichKwong equation of state with the new
mixing rules in van Laar's formulation provides an activity coefficient model, which is more accurate
than the original model, based on the van der Waals equation of state for both low and high vapor
pressure calculations for binary liquid mixtures.
a
a"
M
NOMENCLATURE
constant in the equations of state
a constant of the PengRobinson equation of state which is defined in Eq.(AIS)
volume parameter of the equations of state
fugacity of species i in the pure state
fugacity of species i in the mixture
molar Gibbs free energy
interaction parameter inEq. (12)
a parameter in the SRK equation of state, defined in Eq. (A3)
parameter of Eqs. (30) and (31), defined in Eq. (A28)
parameter ofEq. (31), defined in Eq. ( ~  2 9 )
parameter of Eqs. (24) and (25), defined in Eq. (A31)
IranUtn Journal of Science & Technology, Volume 25, Number B2 Spring 2001
M2
M3
MAlT
MA2T
MAl2T
MTETI
MTE12
MTETI2
P
R
S
T
u
v
Greek letters
r
o
CD
Subscripts
C
1,2,i
mix
MMM
PR
PK
SRK
VDW
Superscripts
E
Sat.
Modijklzdoll oftlu! WIll Lmzr
p a r a m e ! ~ ofEq. (24), defined in Eq. (A32)
parameter ofEq. (25), defined in Eq. (A33)
parameter of Eqs. (26) and (27), defined in Eq. (AIO)
parameter of Eqs. (26) and (27), defined in Eq. (Att)
parameter of Eqs. (26) and (27), defined in Eq. (At2)
parameter of Eqs. (28) and (29), defined in Eq. (A19)
parameter of Eqs. (28) and (29), defined in Eq. (A20)
parameter of Eqs.(28) and (29), defined in Eq. (A2t)
absolute pressure
gas constant
parameter ofEq. (31), defined in Eq. (A30) and entropy
absolute temperature
molar internal energy
molar volume
mole fraction of the ith compOnent in the mixture
compressibility factor
Activity coefficient
A parameter in the PengRobinson equation of state, defined in Eq. (A14)
Eccentric factor
Critical state
Component number
Mixture
MohsenNia  Modarress  Mansoori equation of state
PengRobinson equation of state
RedlichKwong equation of state
Soave modification of the RedlichKwong equation of state
van der Waals equation of state
Excess property
Saturation
REFERENCES
289
1. Peng, D. Y. and Robinson, D. B., A new twoconstant equation of state .. Ind. Eng. Chem. Fundam., 15, p.
59 (1976).
2. Prausnitz, J. M., Lichtenthaler, R. N. and Gomes de Azevedo, E., Molecular Thermodynamics of Fluid
Phase Equilibria, 2nd ed., PrenticeHall, Englewood Cliffs, NJ (1986).
3. Kwak, T .. Y. and Mansoori, G. A., Van der Waals mixing rules for cubic equations of state. Application for
supercritical fluid extraction modelling, Chem. eng. Sci., 41, p. 1303 (1986).
4. Leland, T. W. and Chappelear, P. S., Recent developments in the theory of fluid mixtures, Ind. Eng. Chem.,
60, p. 15 (1968a).
5. Leland, T. W., Rowlinson, J. S., Sather, G. A. and Watson, I. D., Statistical thermodynamics of mixtures of
molecules of different sizes, Trans. Faraday Soc., 64, p. 1447 (1968b).
Spring 2001 Irtl11Uz" JounuU ofSciellce & Technology, Volume 25, Numbet' B2
290
6. Leland, T. W., Rowlinson, J. S., Sather, O. A. and Watson, I. D., Statistical thermodynamics of twofluid
models of mixtures, Trans. Faraday Soc., 65, p. 2034 (1969).
7. Redlich, O. and Kwong, J. N. S., On the thermodynamics of solutions. V. An equation of state: fugacities of"
gaseous solutions, Chern. Rev., 44, p. 233 (1949).
8. Soave, G. S. Equilibrium constants from a modified RedlichKwong equation of state, Chern. Eng. Sci., 27,
p. 1197 (1972).
9. MohsenNia, M., Modarress, H. and Mansoori, G. A., A cubic equation of state based on a simplified hard
core model, Chern. Eng. Cornrn., 131, p. 15 (1995).
APPENDIX A
The detailed derivation ofEqs. (26) to (31) is explained as follows:
Derivation ofEqs. (26) and (27) was based on the SoaveRedlichKwong equation of state which
may be written as:
p= RT
vbSRJ(
where, aSRK and b
SRK
are as follows:
 0.42747R
2
TJ, ~ (1 ji;) J
Q,"'RK  +m  .
0>. P. I n
Ci
where mj is a function of the eccentric factor of the ith component in the mixture,
mi = 0.48508 + 1.55171mj  O. 15613ml
and
(AI)
(A2)
(A3)
b
i
= 0.08664 RTcl
P
CI
(A4) i
Similar to the procedure applied for the RedlichKwong equation of state, the following equations arc
obtained:
GO 8a
( )
_. J
X
l (Q SRKI  T SRK.lj or dv
Xl Uid!Ul1  U 1 
'" v(v+b
SRK1
)
(A5)
Therefore,
(A6)
Which can be written in the following form:
Xlln2( mSRK1)
xl(uideDl U)1 =  QSRKI T=="
bSRKI OJ'
(A+7)
Similarly, for .component 2 we have,
X2ln2( m
SRK2
)
X2(Uideal u h = QSRK2  T    = = ~
b
SRK2
OJ'
(A8)
Using similar assumptions which have been applied in the van Laar formulation we get the following
result for the excess Gibbs free energy of the 'binary mixture,
lranilln JounuU of Science &: TecluuJlogy, VoIUlfle 25, NUlflber B2 Sprlng2001
I
,Jodijktzdon olthe NIl LtIIIr 291
(
ib
SRKI
) xl ( ib
SRK2
) X2 '
aSRKI T + aSRK2 T 
E " iJ]' b
SRKI
iJ]' bSRK2
g =ln2
(
, CU(SRK)mix )
 a(SRK)mix  T iJ]' / b(SRK)mix
(A9)
Now using this equatien and the following definitions for various parameters, Eqs. (26) and (27) may
readily be obtained.
and
MAlT = T cu SRKI
iJ]'
MA2T = T cuSRK2
iJ]'
For derivation ofEqs. (28) and (29) , first we write the PengRobinson equation of state,
wliere,
and
P= RT (}PR
2 2
v  b PR v + 2b PR v . b PR
b
_ O.07780RTc
PR 
Pc
(AIO)
(All)
(A12)
(A13)
(A14)
(AIS)
(A16)
If we repeat the same procedure as applied to the RedichKwong equation of state above, the
following result will be obtained:
E iJ(}PRI xliJ(}PR2 iJtJ
mix
g =O.6232[(}PRIT)+(}PR2 T)(}mix T)] (AI 7)
iJ]' b PRI iJ]' iJ]'
Using this equation as well as the following definitions, Eqs. (28) and (29) are obtained,
(}mix = LLXjX/)PRj(}PRj
. j j 
and
MTETI = T iJ(}PRI
iJ]'
MTET2 = T iJ(}PR2
iJ]'
(AI 8)
(A19)
(A20)
(A21)
The last equation which w e ~ p p l i e d was the MMM equation of state which can be written as follows:
Spring 2001 lnutitul Jolllfflll olScknce & Teclutology, Volume 25, Number.B2
292 Go R. VIlkilHle:JuuuJ/etaL
Z = v+0.62b
MMM
_ aMMMv
v  0.47b
MMM
RT[T
1I2
V(V + 0.47b
MMM
)]
(A22)
where, aMMM and b
MMM
parameters are as follows:
aMMM = 1.46243RTp2
vC
(A23)
and
b
MMM
= 0.41274vc (A24)
This equation of state can be written for the mixtures in the following form:
v + 0.62b(MMM)mbe (L LXix jaij(MMMv I RT
Z m =   :  : : :     : . ~ ~    ' '    
v 0.47b(MMM)mbe [T
1I2
v(v + 0.47Lx
j
b(MMM]
(A25)
where,
(A26)
where the combining rules for the volui;ne and energy parameters of this equation of state have the
same definitions as Eqs. (12 ) and (13 ).
Therefore, if the same procedure as in the above is used, we obtain the following result:
a(MMM)mbe]
b(MMM)mbe
(A27)
Using this equation, as well as the following definitions, Eqs. (30) and (31). can readily be obtained.
(A28)
and
(A29)
(A30)
Finally, the parameters M1,M 2 and M3 which exist in Eqs. (24) and (25) are as follows:
(A31)
M
2
=
(A32)
Iranian Journal o/Science & Technology, Volume 25, Number B2 Spring 2001