Chemical Engineering Science, Volume 41, No. 5, pp.

1303-1309, 1986

VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS

OF STATE. APPLICATIONS FOR SUPERCRITICAL
FLUID EXTRACTION MODELLING
T. Y. KWAK and G. A. MANSOORI
Department of Chemical Engineering, University of Illinois at Chicago, (M/C 063), Chicago, IL 60607-7052, USA
Abstract - A new concept for the development of mixing rules for cubic equations of state consistent with
statistical-mechanical theory of the van der Waals mixing rules is introduced. Utility of this concept is
illustrated by its application to the Redlich-Kwong (RK) and the Peng-Robinson (PR) equations of state. The resulting
mixing rules for the Redlich-Kwong and the Peng-Robinson equations of state are tested through prediction of
solubility of heavy solids in supercritical fluids. It is shown that the new mixing rules can predict supercritical
solubilities more accurately than the original mixing rules of the Redlich-Kwong and Peng-Robinson equations of
state.

INTRODUCTION Extensive research on equations of state have in­

There has been extensive progress made in recent years dicated that the van der Waals equation of state is not
in research towards the development of analytic accurate enough for the prediction of properties of
statistical-mechanical equations of state applicable for compressed gases and liquids (Rowlinson and
process design calculations (Alem and Mansoori, Swinton, 1982). This deficiency of the van der Waals
1984). However,cubic equations of state are still widely equation of state has initiated a great deal of research
used in chemical engineering practice for the calcu­ on the development of other equations of state,
lation and prediction of properties of fluids and fluid through the use of principles of statistical mechanics or
mixtures (Renon, 1983). These equations of state are by empirical or semi-empirical means. The majority of
generally modifications of the van der Waals equation equations of state used in chemical engineering prac­
of state, tice are of the second category and are mostly cubic in
RT
P=---­2
a the volume, like the van der Waals equation of state
(1)
v- b v itself, but contain other forms of the temperature and
volume dependencies. One such equation of state
which was proposed by van der Waals in 1873. which has a simple form is the Redlich-Kwong
According to van der Waals, the extension of this equation of state (Redlich and Kwong, 1949):
equation of state to mixtures requires replacement of a
and b by the following composition-dependent RT a
P=-------- (6)
expressions: 112
v-b T v(v-b)"
" " This equation of state has found widespread appli­
a = L L x,x1a,1 (2) cations in chemical engineering calculations. We
i J
would also like to mention that there exist a large
(3) number of more sophisticated empirical versions of the
van der Waals and Redlich-Kwong modifications. Of
Equations (2) and (3) are called the van der Waals this category of equations of state, the Peng-Robinson
mixing rules. In these equations, aiJ and biJ (i = j) are equation of state (Peng and Robinson, 1976)
parameters corresponding to pure component(i) while = RT _ a(T)
+
a,j and blJ (i j) are called the unlike-interaction p
v-b v(v+b)+b(v-b)
( 1)
parameters. It is customary to relate the unlike­
a(T) = a(Tc ){l +,c(l -T:12 )}
2
interaction parameters to the pure-component par­ (8)
ameters by the following expression: a(Tc ) = 0.45724 R;T!/Pc (8.1)
=
a,1 (1 -ki1 )(aiiaiJ)112 (4) "= 0.37464+ 1.54226co -0.26992co 2
(9)
=
bi) (b;; + bjj )/2. (5) b = 0.0778 RTc/Pc (10)
In eq. (4), k11 is a fitting parameter which is known as is widely used for thermodynamic property
the coupling parameter. With eq. (5) substituted in eq. calculations.
(3), the expression for b will reduce to the following While there has been extensive activity in the
one-summation form: development of new and more accurate empirical cubic
(3.1) equations of state, there has been little attention to the
fact that the van der Waals mixing rules are used
1303
1304
erroneously in these equations, eqs (2) and (3). In other +
(3) Knowing that uii (for i j), the unlike-interaction
words, for the extension of applicability of a cubic diameter, for spherical molecules, is equal to
equation of state it is not generally correct to use eqs (2)
(16)
and (3.1) as the mixing rules without attention to the
algebraic form of the equation of state. In the present This gives the following expression for b;; of
paper we introduce a new concept for the development spherical molecules:
of mixing rules for cubic equations of state in the spirit
of the van der Waals mixing rules. This concept is (17)
based on statistical-mechanical arguments and the fact Then for non-spherical molecules the expression
that the van der Waals mixing rules are for constants of for b1; will be
an equation of state and not for any thermodynamic
bij = (1-l,;)[ (bf;1 3 +b1/ )] • (18) 3 3

state function which may appear in an equation

of state. The resulting mixing rules for the With the use of these guidelines, we now derive the
Redlich-Kwong equation of state, which is a simple van der Waals mixing rules for the two representative
modification of the van der Waals equation of state, equations of state. A similar procedure can be used for
and for the Peng-Robinson equation of state, which is deriving the van der Waals mixing rules for other
an advanced modification of the van der Waals equations of state.
equation of state, are tested through prediction of
solubility of heavy solids in supercritical fluids. Mixing rules for the Redlich-Kwong equation of state
The Redlich-Kwong equation of state, eq. (6), can
'JHEORY OF THE VAN DER WAALS MIXING RULES be written in the following form:
Leland and co-workers (1968a, b, 1969) were able to
PV v a
re-derive the van der Waals mixing rules with the use of (l9)
z=
=
v-b - RTu (v+ b)"
statistical-mechanical theory of radial distribution
RT

functions. According to these investigators, for a fluid In this equation of state, b has the dimension of a molar
mixture with a pair intermolecular potential energy volume,
function between molecules of the mixture in the form
b = 0.26vc oc N0 u3 •
u1;(r) = BiJ f{r/t7iJ) (11)
Then the mixing rule for b will be the same as that for
the following mixing rules will be derived: the first van der Waals mixing rule, eq. (3). However,
n n the mixing rule for a will be different from the second
u3 = LLX;x;u& (12) van der Waals mixing rule. Parameter a appearing in
i i the Redlich-Kwong equation of state has the dimen­
sions of R- 112 (molecular energy)3 12 (molecular
eu3
" n
=LLX;X1£i;t7fi.
I i
(13) volume), that is,

In these equations, e11 is the interaction energy par­ a = 1.2828RT/· 5v" oc: N0 (e/k) 1 . 5 u3•
ameter between molecules i and j and U;; is the As a result, the second van der Waals mixing rule, eq.
intermolecular interaction distance between the (13), cannot be used directly for the a parameter of the
two molecules. Coefficients a and b of the van der Redlich-Kwong equation of state. However, since
Waals equation of state are proportional to e and q ( R 1 '2ab 1 '2) has the dimensions of (molecular energy)
according to the following expressions: x (molecular volume), the second van der Waals
a = 1.1250 R T" v" oc N0 eu3 (14) mixing rule, eq. (13), can be written for this term.
Finally, the van der Waals mixing rules for the
b = 0.3333v" oc N0 u3 • (15) Redlich-Kwong equation of state will be in the
We can see that eqs (12) and (13) are identical with following form:

t
eqs [2] and [3], respectively. Statistical-mechanical n
arguments used in deriving eqs (12) and (13) dictate the 3 bf/3
}1.5 / (" )1/2
a= X ; X; a r/ X 1 X1 b11
�; �
following guidelines in using the van der Waals mixing { • ,.
rules: (20)

(1) The van der Waals mixing rules are for constants of b = L I;x1x1b iJ
. (3)
an equation of state. i j

(2) Equation (12) is a mixing rule for the molecular These mixing rules, when combined with the
volume, and eq. (13) is a mixing rule for (molecular Redlich-Kwong equation of state, will constitute the
volume) x (molecular energy). It happens that b Redlich-Kwong equation of state for mixtures, con­
and a of the van der Waals equation of state are sistent with the statistical-mechanical basis of the van
proportional to molecular volume and (molecular der Waals mixing rules.
volume) x (molecular energy), respectively, and, as
a result, these mixing rules are used in the form Mixing rules for the Peng-Robinson equation of state
which was originally proposed by van der Waals. In order to separate thermodynamic variables from
___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986
 Van der Waals mixing rules 1305

constants of the Peng-Robinson equation of state, we In order to calculate solubility from eq. (29), we need
will insert eqs (8) and (9) into eq_ (7) and we will write it to choose an expression for the fugacity coefficient.
in the following form: Generally, for calculation of a fugacity coefficient an
equation of state with appropriate mixing rules is used
a/RT+d - 2 ,/(ad/RT)
z=-Y-- (21) in the following expression (Prausnitz, 1969):
u-b (u + 6) + (b/u)@ - 6)

where a = a( T,) (1 + rc)* and d = a( T,)h-*/RT,_

This form of the Peng-Robinson equation of state
.RTln&= m C(dPldni)r.,.,,,~-_(RTIY)ldV
I V
suggests that there exist three independent constants in
- RTln Z (30)
this equation of state: a, b and d. Now, following the
prescribed guidelines for the van der Waals mixing
where 2 = Pu/RT.
rules, the mixing rules for a, b and d of the
Peng-Robinson equation of state will be In the case of the van der Waals equation of state, eq.
(l), with eqs (2) and (3) as the mixing rules, the
following expression for the fugacity coetlicient of a
a = 2 5 xixjaij
1 j solute in a supercritical gas will be derived:
& = RT/(u-b)(l/P)exp {(-b+2Zx,b,)/(u-6)
b = 2 k xixjbij
1 j -22Zxjaii/uRT}. (31)

d = 5 2 x,xjdij For the Redlich-Kwong equation of state, with eqs

(24)
1 i (2) and (3) as its mixing rules (as customary in the
literature), the following expression for the fugacity
with the following interaction parameters:
coefficient is obtained:
aij = (1 - kij)(aiiajj)“’ (25)
In & = In (u/(u - 6)) + (2zxj 6, - b)/(u - 6) - In Z
6, = (1 - lij) { (b:i’3 + bjj3)/2}’ (261
+a((2Zxjbi, - b)/(b*RT’.‘)) (In ((u + 6)/u)
d, = (1 -n~~)((di”~+d~_/~)/2}~. (27)
- b/(u + 6)) - ((2Zx,a,,)/(bRT “‘))
These mixing rules, when joined with the
Peng-Robinson equation of state, eq. (7), will con- x In ((u + 6)/u). (32)
stitute the Peng-Robinson equation of state of a Now with the use of the correct version of the van
mixture, consistent with the statistical-mechanical der Waals mixing rules, eqs (3) and (20), in the
basis of the van der Waals mixing rules. Redlich-Kwong equation of state, the fugacity coef-
ficient will assume the following form:

APPLICATION FOR SUPERCRITICAL FLUID In&i = In (Y/(u - 6)) + (2Xx, 6, - b)/(u - 6) - In Z

EXTRACTION MODELLING + (a(2Exj 6, - b)/(b*RT I.‘)) (In ((u + 6)/u)
A serious test of mixture equations of state is shown
- b/(u + 6)) - ((3~ “2(Zxjaf_,~3b~,~3)/b’f2
to be their application for the prediction of solubility
of heavy solutes in supercritical fluids (Mansoori and - a2j3 (Zxj 6, )/b3/*)/(bRT ‘.5))
Ely, 1985). In the present paper, we apply the van der
x In ((u +6)/u) (33)
Waals, the Redlich-Kwong and the Peng-Robinson
equations of state for supercritical fluid extraction of where
solids and study the effect of choosing different mixing
rules for predicting the solubility of solids in super-
critical fluids.
The solubility of a condensed phase, y,, in a vapour
phase at supercritical conditions can be defined as: The fugacity coefficient based on the Peng-
Robinson equation of state with eqs (2) and (3) as the
mixing rules (as usually derived) has the following
Y2 = (W*/P) (l/+2MY’ exp (@“/RT) dP form (Kurnik et al., 1981):

(28) In& = ((2Zxjbij-b)/b)(Z-1)sln(Z-B)

- (A/2 J2B) (2Xxjaii/a - (2Xx1 6, -6)/b)
where +I’ is the fugacity coefficient of the condensed
phase at the saturation pressure Pi”‘, and C& is the x {ln((Z+2J2B)/(Z-2J2B))] (34)
vapour phase fugacity at pressure P. Provided we
assume that uys* is independent of pressure, the above where A = aP/R’T * and B = bP/RT.
expression is converted to the following form: With the use of the correct version of the van der
Waals mixing rules, eqs (22~(24), in the Peng-
Y, = (PFt/P) (1/4,)exp {@*<P - PF’)/RT}. (29) Robinson equation of state, the following expression
___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986
1306 T. Y. KWAK and G. A. MANSOOR~

for the fugacity coefficient is derived: this figure, predictions by the van der Waals equation
of state will improve when eq. (3), along with the
In 4, = ((2Xx,& - b)/b)(Z- l)-ln(Z-B)
combining rule, eq. (17), is used as the mixing rule for b
- (A/(2 ,/2B)) ((2Xx,4, + 2RTZx, d,, instead of eq. (3.1) as customarily used. This com-
parison, and similar comparisons reported elsewhere
-2,/(RT)(aEc,dij
(Mansoori and Ely, 1985) for other solute-solvent
+ dZxiuii)/J(ad))/~* - (2Z~jb, - b)/b) systems, establish the superiority of the double-
summation mixing rule, eq. (3), for b over the single-
x (ln ((Z + (1 + J2)B)l(Z - (1 - J2)g))) summation expression, eq. (3.1).
(35) In Fig. 2, the same experimental solubility data as in
where Fig. I are compared with predictions using the
a* = a+RTd -2J(adRT) Redlich-Kwong equation of state. According to this
figure, the corrected van der Waals mixing rules for the
A = a*P/(RT)
Red&h-Kwong equation of state, eqs (3) and (20), are
B = bRT/(RT). clearly superior to the mixing rules which are cus-
tomarily used, eqs (2) and (3.1), for this equation of
We now utilize the above expressions for fugacities
state. Similar observations are made for the prediction
in order to predict the solubility of solids in super-
of solubilities of other solids in supercritical fluids,
critical gases at different temperatures and pressures,
which are not reported here.
and compare the results with the experimental data.
The Peng-Robinson equation of state with its
customary mixing rules, eqs (2) and (3), is widely used
RESULTS AND DISCUSSION
for predicting the solubility of heavy solutes in super-
In Fig. 1, the solubility of 2,3-dimethyl naphthalene critical gases and for petroleum reservoir fluid-phase
(DMN) in supercritical carbon dioxide is plotted vs. equilibrium calculations (Firooxabadi et al., 1978;
pressure at 308 K along with predictions obtained Katz and Firoozabadi, 1978; Kurnik et al., 1981). In
from the van der Waals equation of state. According to Fig. 3 the same experimental solubility data as in Figs 1
and 2 are compared with the predictions using the
. I Peng-Robinson equation of state with its original
mixing rules and with its corrected van der Waals
mixing rules. According to this figure, the corrected

k .=-0.3537
“+
==_

kj-0 “‘” 326

l
Co2 - 23

308K k,-
_____
DMN

- 0.095
- 318 K ly = -0.090
l 328K Kt= -O.ceS

> I

0 50 100 150 200 250 2

~~!%?ilJRE (BAR >

Fig. 1. Solubility of 2, 3-dimethyl naphthaleue(DMN) in Fig. 2. Solubility of 2, 3-dimethyl naphthalene (DMN) in

supercriticalcarbon dioxide at 308 K vs. pressure.The solid supercritical carbon dioxide at 308, 318 and 328 K vs.
dots arc the experimental dam (Kurnik et al., 1981). The pressure_ The solid dots are the experimental data (Kumik
dashed lines are the results of the van der Waals equation of et al.. 1981). The dashed lines are the results of
state with eqs (2) and (3.1) as the mixing rules. The solids lines the Redhch-Kwong equation of state with eqs (2) and (3.1) as
are results of the van der Waals equation of state with eqs (2) the mixing rules. The solid lines are the results of the
and (3) as the mixing rules and eqs (4) and (17) as the Redlich-Kwong equation of state with eqs (3) and (20) as
combining rules. the mixing rules and eqs (4) and (17) as the combining rules.
___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986
 Van der Wsals mixing ruks 1307
van der Waals mixing rules of the Peng-Robinson
equation of state apparently do not improve solubility
predictions over the original mixing rules. However,
variation of solubility vs. pressure for the new mixing
rules is more consistent with the experimental data
than the old mixing rules. Also considering the fact that
the new mixing rules for the Peng-Robinson equation
of state contain three adjustable parameters (ku, I, and
m,) whereas the old mixing rules contain only two
adjustable parameters (k, and 1, ) makes the new
mixing rules more attractive. A demonstration of the
superiority of the new mixing rules for the
Peng-Robinson equation of state is shown here in Figs
4-9. According to these figures, when the unlike-
interaction adjustable parameters of the mixing rules
are fitted to the experimental data, the Peng-Robinson
equation of state with the corrected van der Waals
mixing rules can predict solubility of heavy solids in
supercritical fluid more accurately than with the
original mixing rules over different ranges of tempera-
ture and pressure and for different solutes and super- A :318K
critical solvents. -:328 K

jc0 50 loo 150 200 250 3

PRESSURE (BAR)
Fig. 4. Volubility of 2, 3-dimethyl naphthalene (DMN)
in supercritical carbon dioxide as calculated by the
Peng-Robinson equationof state usingeqs (2) and (3) as the
mixing rules and compared with the experimentaldata.

l l
l

-23DMN CC523 DMN

Tm308K

. 2 318K
n : 328 K

0 50 loo 150 200 250 3(

PRESURE (BAR)
3

Fig. 3. Solubihty of 2, 3-dimethyl naphthalene(DMN) in 0 50 loo 150 200 250 3

supercriticalcarbondioxideat 308 K vs. pressure.The dashed PRESSURE t BAR 1
linesare the resultsof the Peng-Robinson equation of state Fig. 5. Solubigty of 2, 3-dimethyl naphthalene(DMN) in
witheqs (2) and (3) as the mixingrules.The solid linesare the carbondioxideas eakukted by the Peng-Robinson equation
resultsof the Peng-Robinson equation of state with eqs (3) of state with eqs (X$-o-(4) as the mixing ruks and compared
and (20) as the mixingrules.Roth sets of linesare for k, = 0. with the experimtntaldata.
___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986
1308 T. Y. KWAK and G. A. MANSOORI

.
328

CO2 2SDMN
9f4 23DMN kS = am 7
= 0-2 I ij x-02420
“ii
Iii =-(X2482 ’ .:308 K
4 -3t8 K
0~308 K -:328 K
~~318 K
I :328 K

l-,sl, CI I

0 50 100 150 200 250 3 0 loo 150 200

50 250 3(
PRESSURE (SARI PRESSURE (BAR)
Fig. 6. Solubihty of 2, 3-dimethyl naphthalene (DMN) in Fig 8. Solubility of 2, 6-dimethyl naphthalene (DMN) in
supercritical ethylene as calculated by the Pcng-Robinson carbon dioxide as calculated by the Peng-Robinson equation
equation of state with eqs (2) and (3) as the mixing rules and of state with eqs (2) and (3) as the mixing rules and compared
compared with the experimental data with the experimental data.

.
c

328 K

328 K

w-23 DMN
k jj=o.l8~
I ijSO.2723 Iii = -0.242
mu=06602 ‘ij = 0.3117
l t3D8K . : 308X
4’3l8K A : 318-K
m:328K
- : 328’K

i
C,
0 50 loo 150 200 250 3 ,0 50 loo 150 200 250 3(
PRESSURE (BAR, PRESSURE BAR)
Fig. 7. Solubihty of 2,3-dimethyl naphthalene in supercritical Fig. 9. Solubility of 2. 6-dimethyl naphthalene (DMN) in
ethylene as calculated by the Peng-Robinson equation of supercritical carbon dioxide as calculated by the
state with eqs (22)-(24) as the mixing rules and compared with Peng-Robinson equation of state with eqs (22)-(24) as the
mixing rules and compared with the experimental data.
the experimental data. ___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986
 Van der Weals mixing rules 1309

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___________________________________________
T. Y. KWAK and G. A. MANSOORI
VAN DER WAALS MIXING RULES FOR CUBIC EQUATIONS OF STATE.
APPLICATIONS FOR SUPERCRITICAL FLUID EXTRACTION MODELLING
Chem. Eng’g Sci. 41(5): 1303-1309, 1986