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A Self-Consistent Gibbs Excess Mixing Rule for Cubic Equations of State:

derivation and fugacity coefficients


Paula B. Staudt, Rafael de P. Soares
Departamento de Engenharia Qumica, Escola de Engenharia, Universidade Federal do Rio Grande do Sul, Rua Engenheiro Luis Englert, s/n,
Bairro Farroupilha, CEP 90040-040, Porto Alegre, RS, Brazil
July 2013

Abstract
The extension of the applicability of cubic equations of state (EoS) with Gibbs excess models to the prediction of highpressure/high-temperature vaporliquid equilibria of polar and/or asymmetric is well known. In a recent work (Fluid
Phase Equilib., vol. 334, 2012, pp 7688) we have proposed the so called SelfConsistent Mixing Rule (SCMR).
The method was derived solely based on the assumption of a zero excess volume liquid-like phase. Tests with substances dissimilar in size, shape and chemical nature have shown that any cubic equation of state coupled with the
proposed mixing rule can reproduce the underlying liquid activity model at low pressures, showing that the method
is self-consistent. Further, the method was extended for high pressures/temperatures by assuming a constant thermal expansion coefficient liquidlike phase as the reference state. Very good results were obtained when the proposed
method was coupled with Wilson, UNIQUAC, UNIFAC and a COSMO-based model in liquidliquid and vaporliquid
equilibrium examples. The present document contains a minimum description of the SCMR method, its derivation
and the equations for the fugacity coefficient.
Key words: cubic equations of state, EoS/GE mixing rules, Gibbs excess models, vapor-liquid equilibrium,
liquid-liquid equilibrium.

1. Introduction
In Staudt and Soares [1] a new G E based mixing rule for cubic equations of state was developed. The main
advantage of the proposed method is that the combined model reproduces very well the GE model it is based on
without any additional empirical correction.
For a detailed description of the method as well as comparison with similar methods and experimental data, please
refer to the fulllength manuscript available at http://dx.doi.org/10.1016/j.fluid.2012.06.029. In this
document only the mixing rule derivation and the fugacity coefficient equations are shown.
2. Mixing rule derivation
Most of the cubic equations of state (EoS) available today are special cases of a general cubic equation [2], which
can be written as:
RT
a (T )
P=
(1)

V b (V + b) (V + b)
where P is the pressure, T is the temperature, V is the molar volume,  and are constants for all substances and
depend on the particular EoS (see Table 1) and a (T ) and b are, respectively, the attractive and co-volume parameters
specific for each substance.
author. Tel.:+55 51 33083528; fax: +55 51 33083277
Email address: rafael@enq.ufrgs.br (Paula B. Staudt, Rafael de P. Soares)

Corresponding

The attractive a (T ) and co-volume b parameters are usually determined using generalized correlations based on
critical properties and acentric factor, according to:
a (T ) =
b=

(T r , ) R2 T c2
Pc

(2)

RT c
Pc

(3)

where T c is the critical temperature, Pc is the critical pressure, is the acentric factor, T r = T/T c the reduced
temperature and the other symbols are shown in Table 1.
Table 1: Specific cubic equation parameters.
EoS
(T r )


van der Waals (vdW)
1
0
0
RedlichKwong (RK)
T r1/2
1
0
SoaveRedlichKwong (SRK)
S RK (T r ; )a
1
0
1 2
Peng-Robinson (PR)
PR (T r ; )b
1+ 2
h

i
a
2) 1 T 2
(T
;
)
=
1
+
(0.48
+
1.574

0.176
S RK r
r
h

i
b (T ; ) = 1 + (0.37464 + 1.54226 0.269922 ) 1 T 2
PR r
r

1/8
0.08664
0.08664
0.07780

27/64
0.42748
0.42748
0.45724

2.1. Mixing rule


When dealing with mixtures, the expressions for the attractive a and co-volume b parameters should be computed
as a function of the pure substances values ai and bi through mixing rules.
The van der Waals (vdW) or classic mixing rule, present in most professional process simulation systems, is given
by:
a=

N
X

xi x j ai a j (1 ki j )

(4)

xi bi

(5)

i=1

b=

N
X
i=1

where xi is the mole fraction of the substance i and ki j is the binary interaction parameter, introduced to improve the
correlation of phase equilibrium of mixtures.
G E based mixing rules, in contrast to the classic mixing rule, obtain the interaction information from excess Gibbs
energy GE models, originally developed for the prediction of liquid activity coefficients i .
One possible expression for computing the Gibbs excess energy from a cubic EoS is [3]:
GE
RT

= ln

xi ln i

(6)

where is the mixture fugacity coefficient and i is the fugacity coefficient of the pure substance i, all in the same
conditions of temperature and pressure.
The fugacity coefficient considered in Equation 6 for any cubic EoS in the generic form (Equation 1) is given by
[4]:
ln = (Z 1) ln(Z ) + qI

(7)

where Z PV/RT is the compressibility factor and the other auxiliary variables are: Pb/RT , q a/bRT ,
V+b
I I0 ln V+b
, and I0 is a constant given by 1/( ).
2

Using Equation 7 one can compute ln as well as ln i by exchanging the mixture properties (Z, , q, and I) by
the pure substance properties (Zi , i , qi , and Ii ). Thus, by combining Equation 6 and Equation 7, the Gibbs excess
energy for a cubic EoS can be computed by:
GE
RT

= (Z 1) ln(Z ) + qI

xi ((Zi 1) ln(Zi i ) + qi Ii )

(8)

P
P
+ ln(V b) one can
Using the definition of excess volume V E V i xi Vi and recalling that ln(Z ) = ln RT
obtain:
!
X
GE
PV E X
Vi bi
=
+
+ qI
xi ln
xi qi Ii
(9)
RT
RT
V b
i
i
The expression given by Equation 9 contains no simplification assumptions and can be used to get a fully consistent
mixing rule if we make GE = GE . Although exact, the practical use of Equation 9 is limited because it is an implicit
mixing rule (the mixture volume V depends on q and viceversa). Now, by assuming that the excess volume is
P
negligible (V E = 0, V = V Id = i xi Vi ) the following expression is obtained:
!
X
GE X
Vi bi
xi ln Id
xi qi Ii
(10)
=
+ qI Id
RT
V b
i
i
where b should be computed with the mixing rule Equation 5, the volume of the pure substances Vi , as well as I Id and
Ii , should be computed using the liquid-like root of the pure fluids at the system temperature and pressure.
However, for cubic equations, the attractive parameter a should depend on temperature and composition only.
Since most GE are developed for nearatmospheric pressure, in this work the liquidlike root required for the determination of Vi is obtained at 1 bar. The results would be essentially the same if a zero pressure is taken as reference.
Finally, by making GE = GE a new explicit mixing rule is obtained by isolating q in Equation 10:
E

! X

1 G X
Vi bi
q = Id
xi qi Ii
(11)
+
xi ln Id

RT
I
V b
i
i
The mixing rule given by Equation 11 will reproduce the GE model as long as the the system pressure is not too
far from 1 bar and the zero excess volume assumption holds. For all tests considered (see the full-length manuscript)
the GE reproduced the GE very well. Thus, the mixing rule given by Equation 11 was referred as the SelfConsistent
Mixing Rule (SCMR). The derivation of fugacity coefficients of substances in mixture according to the SCMR is
given in Section 3.
2.2. Extension for high pressure/temperature
In the mixing rule proposed in the present work, the pure fluid liquidlike volume of each substance in mixture
is necessary. At high temperature conditions, usually above T r T/T c = 0.7, one can have problems with finding a
liquidlike root from the cubic EoS.
To circumvent this problem, an alternative procedure is adopted in this work to compute the pure fluid liquid-like
molar volume to be used in Equation 11. From the definition of the volumetric thermal expansion coefficient of a pure
fluid i :
!
1 Vi
i
(12)
Vi T P
and assuming a constant i , evaluated at a reference temperature T i , the molar volume of a pure substance can be
obtained by the following expression:
ln

Vi
= i (T T i )
Vi

(13)
3

The pure fluid thermal expansion i , according to an EoS, is easily determined by its definition (Equation 12).
In this work, the reference temperature T i chosen was that to correspond to a T i,r = 0.5. This temperature corresponds, approximately, to the normal boiling temperature. This reference temperature assures a valid liquidlike root,
consequently no problems will occur to evaluate Vi .
Then, in the SCMR mixing rule, the pure fluid liquidlike root Vi is always evaluated by Equation 13, allowing its
application to high pressure/temperature and/or supercritical systems.
2.3. Polymer solutions
Specially for polymer components, the required pure component liquid-like volume Vi = bi /ui was computed by
considering a constant and universal value for the inverse packing fraction ui = 1.288. This value, taken from Sanchez
and Cho [5], corresponds to the average value of the ratio of the van der Waals density and the characteristic density
, which is very chose to the Bondi constant 1.3[6]. With this assumption the liquid-like volume value, to be used by
the mixing rule, is constant for pure polymers. The solvent liquid-like volume is still calculated using the volumetric
thermal expansion coefficient, as explained in subsection 2.2.
3. Fugacity coefficients from SCMR
The fugacity coefficient of a substance i in a mixture, for any cubic EoS given by Equation 1, can be obtained by
[4]:
bi
(Z 1) ln(Z ) + qi I
(14)
b
where bi and qi are partial molar properties defined by:
!
nT k

ki
(15)
ni T,P,n j,i
P
with nT = l nl .
For the SCMR mixing rule, the covolume parameter b is given by the linear mixing rule, Equation 5, then bi = bi .
In order to simplify the notation in the derivation of qi , let us introduce the quantity for the SCMR mixing rule
(Equation 11):
! X
GE X
Vi bi
Id
xi ln Id
xi qi Ii
(16)

+
qI =
RT
V b
i
i
ln i =

which leads to:

Id
1
Ii
qi = q + Id i Id
I
I

(17)

and the remaining partial molar properties are:


!
Vi bi
Vi bi
i = ln i ln Id
+ Id
1 + qi Ii
V b
V b
!
Ii Id = I Id + I0 Vi + bi Vi + bi
V Id + b V Id + b

(18)
(19)

where the activity coefficient i should be computed by the chosen Gibbs excess model GE .
References
[1] P. B. Staudt, R. d. P. Soares, A self-consistent Gibbs excess mixing rule for cubic equations of state, Fluid Phase Equilibria 334 (0) (2012) 76
88.
[2] J. O. Valderrama, Ind. Eng. Chem. Res. 42 (8) (2003) 16031618.
[3] K. Fischer, J. Gmehling, Fluid Phase Equilib. 121 (1-2) (1996) 185206.
[4] J. M. Smith, H. C. V. Ness, M. M. Abbott, Introduction to Chemical Engineering Thermodynamics, McGraw-Hill, New York, 2005.
[5] I. C. Sanchez, J. Cho, Polymer 36 (15) (1995) 29292939.
[6] A. Bondi, van der Waals Volumes and Radii, J. Phys. Chem. 68 (3) (1964) 441451.