A Generalized Correlation for the Prediction of Phase Behaviour

in Supercritical Systems
M. A . TREBBLE and P. M . SIGMUND
Department of Chemical and Petroleum Engineering, The University of Calgary, 2500 University Dr. N. W., Calgary,
Alberta, Canada. T2N IN4
A generalized two parameter model is presented which uses molecular properties of pure fluids to predict interaction
parameters in the attractive term of the Peng-Robinson equation of state. The predictive method is based on a consideration of London (dispersive) forces and includes attractive forces between polar and non-polar molecules that result
from induction. Polar-polar effects and quantum forces are omitted. A large body of experimental vapor-liquid equilibrium
data measured at near and supercritical conditions (that excludes quantum components and polar-polar systems) was
used to calibrate the generalized model. Overall bubble point pressure deviations calculated using the proposed generalization were 5.66% for 3240 data points which compares to average deviations of 3.27%obtained by using regressed
binary interaction parameters. Average vapor mole fraction deviations were just under 0.0 1 using both the generalized
and the regressed interaction parameters. The sensitivity of predicted phase envelopes to dispersive and inductive term
in the generalized correlation is shown graphically for several systems. Comparisons are also made to another recent
interaction parameter generalization presented by Nishiumi et al. (1988).

On prksente un modele gCnCralise a deux parametres qui utilise les propriCtCs molCculaires de fluides purs pour predire les parametres dinteraction dans le terme dattraction de ICquation dCtat de Peng-Robinson. La mkthode prCdictive est basee sur une considkration des forces (dispersives) de London et inclut les forces attractives entre les molecules
polaires et non polaires qui rksultent de Iinduction. Les effets polaires-polaires et les forces quantiques sont omis.
On a utilise un vaste ensemble de donnCes expkrimentales dCquilibre liquide-vapeur mesurees pres des conditions supercritiques et aux conditions supercritiques (excluant les composantes quantiques et les systemes polaires-polaires) pour
calibrer le modkle gknCralisC. Les Ccarts globaux de pression du point de bullL calcules a Iaide de la generalisation
proposee, sont de 5,66% pour 3243 points de donnees, ce qui se compare aux Ccarts moyens de 3,27%obtenus par
regression de paramktres dinteraction binaires. Les ecarts moyens de la fraction molaire de la vapeur sont juste en-dessous
de 0,Ol a la fois avec les parametres dinteraction ginkralises et les parametres obtenus par regression. La sensibilit6
des enveloppes de la phase dispersCe aux termes de dispersion et dinduction dans la correlation gknkralisee est decrite
sous forme graphique pour plusieurs systemes. Des comparaisons sont tgalement Ctablies avec une genCralisation des
parametres dinteraction presentee rCcemment par Nishiumi et al. (1 988).
Keywords: supercritical systems, phase behaviour, binary interaction parameters, dispersive forces, induction.

he need for binary interaction parameters in equation

of state modelling is well documented (Soave, 1979;
Katz and Firoozabadi, 1978). However, perhaps because of
the desirability of individual calibration of binary pairs (that
unquestionably gives better fits of the data), generalized
methods of estimation are still in the early stages of development. Generalized approaches to the estimation of interaction coefficients have been proposed for the Redlich-Kwong
equation of state by Chueh and Prausnitz as early as 1967.
Their correlation was stated to apply to n-alkane mixtures
and was expressed in terms of a ratio of critical volumes.
Later, Katz and Firoozabadi (1978) developed a generalized
correlation for the prediction of methane-n-alkane interaction coefficients applicable to the Peng-Robinson equation
of state. The correlation variable was the density of the heavy
component at 15.5C. Kato et al. (1981) presented a correlation specifically for carbon dioxide-n-alkane binaries as a
function of temperature and the n-alkane acentric factor. A
new procedure for predicting binary interaction parameters
for the Peng-Robinson equation of state (EOS) has recently
been presented by Nishiumi et al. (1988). Their procedure
utilizes critical volume ratios and acentric factor differences.
The model contains five adjustable constants which are used
in a variety of combinations to fit specific pairs of compound
families,
In this work we are interested in developing an extrapolative model with ties to intermolecular forces. Since equations of state are a convenient means of representing
observable P-V-T behaviour, it is of interest to examine the
relationship between the parameters used in these equations

and those used in describing intermolecular forces. The study

is limited to the practical problem of considering these forces
of attraction in terms of deviations from classical EOS mixing
rules which presume pairwise additivity of molecular interactions. We begin with the Peng-Robinson equation of state
and the usual mixing prescriptions:

p = - - RT
(V

b)

V(V

+ b) + b ( v - b)

. . . . . . . . . (1)

ccx; xj a;j

.............................

(2)

EX;b; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(3)

ajj = ( a ; a j p 5 (1 - 6,) . . . . . . . . . . . . . . . . . . .

(4)

As summarized by Kwak and Mansoori (1989, the work

of Leland and others (1968a, b, 1969) gives a statistical
mechanical argumentation for the relationship between a
and b in the van der Waals EOS, and to both the depth
of the minimum in an intermolecular potential (c), and the
separation distance (u) at which the potential is zero, as
follows:

...................................

(5)

....................................

(6)

(x ( T 3

bcx

( T ~

For the Redlich-Kwong (1949) EOS, Kwak and Mansoori

show the variation of a with E and (T as:
a

0: ~

..........................
.. .~. . .0. . ~

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 68, DECEMBER, 1990

(7)
1033

In order to relate the intermolecular potential functions to

the equation of state parameters, we refer to the work of
Hudson and McCoubrey (1 959) who derived an expression
that related the well depth (E) to a sixth power potential of
attraction via the London theory of dispersive forces given
by :

Introducing a geometric mean mixing rule on E and an arithmetic mean mixing rule on 1.7, they suggested the following
relationships:

'Ti]

u,

+ 'TL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2

(10)

;:

Now if we take aij 0: E

a ; , a' 0: Vci , and u t cc VCij,
then Equations (4), (7), and (9) can be combined to give:

where:

The relationship between the interaction parameter 6, and

the critical volumes of the molecules is therefore seen to be
analogous to that described by Chueh and Prausnitz (1967)
for representing interactions in a binary mixture:

Figure 1 - Polarizibility versus critical volume (cc denotes cm').

Support for the proportionality between the polarizability
and the critical volume is shown by Figure 1 which is a plot
of polarizability versus critical volume for some normal
hydrocarbons up to dodecane.
The resulting generalization is therefore a two constant
(0, 7) description of a binary interaction parameter limited
to pairs of non-polar - non-polar and non-polar - polar
molecules. Potential functions describing forces between
polar molecules are also summarized by Prausnitz et al.
(1986) but were not included in this work. It is likely that
a single binary interaction parameter will prove insufficient
to match phase behaviour in polar-polar systems in any case.

Determination of model parameters

where I9 represents an adjustable parameter to account for
variability in the exponent of the attractive potential.
To include forces of induction between non-polar and polar
molecules we include additional potentials as described by
Prausnitz et al. (1986):
= --3

I'

4)"'
(Il + 4 )

aJ

r;

(aIpJ

+
r;

3(a,QJ2 + Q~Q,') . . . . . . . . . . . . . . . . . . . . .
2r t

(14)

where the first term is the London potential and the last two
terms describe attractive potentials resulting from induction.
Assuming superposition of the potential terms and a proportionality between polarizability (a)and critical volume (Vc),
a semi-empirical expression for the interaction parameter is
given by:

In order to calibrate values of I9 and 7 in Equation (15),

it was necessary to obtain and screen a large vapor-liquid
equilibrium data base. The Gas Processor's Association data
base developed by Daubert (1986) was selected for use in
this application and some minor screening was performed
as described by Trebble (1990). Most of the data contained
in the data base are at conditions which correspond to a supercritical regime for the lighter constituent. Regressed values
for binary interaction parameters for three cubic EOS,
including the Peng-Robinson equation, were also given by
Trebble (1990). Excluding quantum components and binaries
in which both molecules had dipole or quadrupole moments,
reduced the number of binary systems to 72 and the number
of pure component constituents to 28. The 28 pure components are listed with their associated physical properties in
Table 1. Critical properties and dipole moments were
obtained from Reid et al. (1987) while quadrupole moments
were obtained from Prausnitz et al. (1986).
Optimum values of I9 and 9 were determined by minimizing
and deviations in vapor
bubble point pressure deviations (00
phase composition (Or)resulting from fixed T, x bubble point
calculations. More specifically the objective function ( E l )
was defined by the following equations:
Bubble Point at Fixed T, x ;
i = n

El =

......................................
1034

(15)

[of" + DY;] . . . . . . . . . . . . . . . . . . (16)

i = l

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 68, DECEMBER. 1990

TABLE1

Pure Component Properties

Coniponent
nitrogen
hydrogen sulfide

N2
H2S
c02
c1
c2
c3
C4ENE
NC4
IC4
NC5
IC5
NEOC5
CYC6
C6
TOL
ClCYC6
c7
MXYL

carbon dioxide
methane
ethane
propane

1-butene
n-butane
isobutane
n-pentane
2-methyl butane
neo-pen tane

cyclohexane
n-hrxane

toluene
methylcyclohexane
n-heptane
m-xylene
p-x ylene

PXYL

ethy lbenzene
ethy lcyclohexane

C2BEN
C2CYC6
C8
C3BEN
MESI
C3CYC6
c9
c10
C16

n-octane

n-propy lbenzene

meutylene
propy lcyclohexane
n-nonane
n-decane

hexadecane

126.2
373.2
304.1
190.4
305.4
369.8
419.6
425.2
408.2
469.7
460.4
433.8
553.5
507.5
591.8
572.2
540.3
617.1
616.2
617.2
609.0
568.8
638.2
637.3
639.0
594.6
617.7
722.0

3.39
8.94
7.38
4.60
4.88
4.25
4.02
3.80
3.65
3.37
3.39
3.20
4.07
3.01
4.10
3.47
2.74
3.54
3.51
3.60
3.00
2.49
3.20
3.13
2.80
2.29
2.12
1.41

89.8
98.6
93.9
99.2
148.3
203.0
240.0
255 .O
263.0
304.0
306.0
303 .O
308.0
370.0
316.0
368.0
432.0
376.0
379.0
374.0
450.0
492.0
440.0
429.0
450.0
548.0
603.0
960.0

0.0372
0.0971
0.2390
0.0109
0.0979
0.1518
0.1905
0.1994
0.1847
0.2522
0.2286
0.1956
0.2089
0.2990
0.2641
0.2359
0.3494
0.3261
0.3222
0.3027
0.2401
0.3977
0.3454
0.3999
0.2615
0.4488
0.4902
0.7338

-0.474
0.285
- 1.360

-0.206
0.095
0.032
0.032
0.095
0.126
0.095
0.032
0.126

0.032

Discussion of results
Table 2 presents a summary of the regression analysis for
all of the binary systems evaluated. Values of pressure and
composition deviations were evaluated with both zero
(ZERO) interaction parameters and with the regressed (REG)
interaction parameters presented by Trebble (1990). Table
3 includes corresponding results comparing the generalization of Nishiumi, Arai and Takeuchi (NAI) with Equation
(15), hereafter referred to as the TS generalization. Tables
2 and 3 have been filed with the Depository for Unpublished
Data, CISTI, National Research Council of Canada, Ottawa,
Ontario, K1A OS2, and can be obtained from the depository
or from the authors upon request. A summary of these tables
shows average errors in bubble point pressures (DP) and
vapor mole fractions (DY) for the entire data base as follows:

0 = 0.20
regressed 6..

vci vcj

/ vcij

Figure 2 - Generalization for non-polar pairs.

where:

DP

100.0. I P ,

DY

100.0 * I yrxp - yculc1 . . . . . . . . . . . . . . . . . . (18)

Pculc/l P ,

. . . . . . . . . . . . . (17)

An optimum 19value of 0.2 is shown in Figure 2 along with

independently regressed binary interaction parameters for all
of the non-polar pairs contained in the data base. The value
of 7 determined from the minimization was 9OpJ- mol-
where di ole and quadrupole values are expressed as
10iRpJiPcm32and 1026pJ12cm5I2respectively.

ZERO 6,
REG 6ij
NAT 6ij
TS 6 ,

DP = 10.70 DY = 1.57 PTS

DP = 3.27 DY = 0.89 PTS
DP = 4.43 DY = 0.96 PTS
DP = 5.66 DY = 0.99 PTS

= 3199
= 3270
= 3269
= 3240

It is evident from the overall deviations that the NATgeneralization yields lower errors than the TS generalization, but
that both represent most systems very well. The NATgeneralization requires some 30 constants, however, in order to
fit nine families of compounds, some of which include only
one member.
Table 4 compares the results of the Katz and Firoozabadi
correlation for interaction parameters between methane and
n-alkanes to the results of the NAT and TS generalizations.
The graphical correlation of Katz and Firoozabadi was
linearized with the following expression:

THE (ANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 68, DECEMBER, 1990

1035

TABLE4

48.0,

Comparisons of Correlations for Methane-Alkane Binaries

Katz
Alkane

c2
C3
NC4
IC4
NC5
IC5

NEOC5
NC6
NC7
NC8
NClO

1,

0.0000
0.0059
0.0159
0.0131
0.0220
0.0211
0.0175
0.0262
0.0294
0.0318
0.0354

Average

NAT

TS

6i, = 0.052
40.0.-

DP

DY

DP

DY

DP

DY

1.13
3.64
3.98
3.35
4.12
6.64
2.85
8.62
2.58
4.53
3.64

0.27
0.46
0.84
1.64
0.64
3.27
3.42
0.94
0.75
0.53
0.20

1.80
2.25
6.36
1.67
4.08
6.99
2.87
6.63
3.70
2.01
2.54

0.38
0.42
0.84
1.03
0.61
3.14
2.89
1.03
0.69
0.48
0.20

1.30
3.04
3.84
3.03
4.26
6.64
2.66
8.07
2.81
2.21
2.89

0.32
0.45
0.84
1.54
0.65
3.27
3.35
0.95
0.72
0.50
0.19

4.20

0.74

3.72

1.06

3.70

1.16

52.0-

24.0-

16.0-

0.0

TABLE5

Alkane

NAT

8000.0

DY

DP

DY

DP

DY

0.66
0.69
0.96

C2CYC6
NC16

1.95
1.22
2.93
2.74
5.57
2.63
16.98
16.89
13.07

0.81
0.47
1.76
1.75
1.31

3.77
3.93
5.79
4.09
3.58
4.39
4.29
5.54
10.87

0.70
1.25
1.65
1.64
0.74
0.60
1.33
0.98
1.51

6.23
5.43
8.16
6.09
2.85
4.10
3.76
6.38
14.30

1.13
1.54
2.04
1.82
0.71
0.60
1.29
0.90
0.37

Average

5.83

0.98

5.14

1.08

6.94

1.16

c3
NC4
NC5
NC7
NClO

ClCYC6

1.32

6,J = 0.13p(kg/dm3 at 15.5"C) - 0.06 . . . . . . . . (19)

Table 5 gives a similar comparison to the generalization of
Kato et al. (1981) for systems of carbon dioxide with
hydrocarbons.
Figures 3 through 8 show calculated and experimental
phase equilibrium isotherms in a pressure-concentration
format. The figures indicate the sensitivity of the calculated
phase envelopes to interaction coefficients over a range of
conditions that represent the effects of variations in molecular
size, molecular type and temperature in the equation of state.
Table 6 gives the contribution of each of the terms in Equation (15) (disperse and inductive) for the binary pairs used
in the example systems.
The sensitivity of calculated phase behaviour to interaction parameters as a function of dispersive effects of
molecular size difference is illustrated for two n-alkane combinations. In this work the effect of molecular size difference is expressed as a critical volume ratio. The results are
shown in Figures 3 and 4 by way of comparison calculations for the species pairs, methane-n-decane and ethane-ndecane. The negligible quadruple and dipole effects between
these pairs facilitates a comparison of how the critical volume
ratio of a binary pair changes both computed and observed
phase behavior. As shown in Figure 3, the simple quadratic
mixing rule (zero aij) expressed in Equation (4) results in
underestimation of saturation pressures for the methanedecane system, while hij (0.052) predicted from Equation
( I 5) yields excellent agreement with experiment. Examination
1036

0.6

0.8

1.0

6il =o.ooo ....................

0.2

0.4

1.2

Figure 3 - P-z Diagram for methane and decane at 37.7"C.

TS

DP

CI

Mole Fraction Methane

Comparisons of Correlations for C0,-Alkane Binaries

Kato

Figure 4 - P-z Diagram for ethane and decane at 71.0"C.

Mob Fraction Carbon Dioxide

Figure 5 - P-z Diagram for CO, and decane at 104.4"C.

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 68, DECEMBER, 1990

TABLE
6

Interaction Parameter Contributions for Example Systems

~

vc,

vc,

Binary

cm3/mol

cm'/mol

V' ,'
cm3/mol

c1-CIO

99.2
148.3
93.9
93.9

603.O
603.0
603.0
960.0

279.6
324.3
274.2
374.0

c2-c 10

c o 2 - c 10
CO2-Cl6

Dipsenive Term

10 0

6,, = 0.103

Inductive Term

= 1.0 -

h,, = Dispersive Term

Q,

. cm",

Dispersive

Inductive

term

term

0.0521
0.0319
0.0552
0.0842

o.Ooo0

p~",

-0.206
-1.360
-1.360

'I

O.OOO3

0.0474
0.0330

0.0521
0.0322
0.1026
0.1172

. mol-'

= 90 p J - '

+ Inductive Term

18.C

15.c

12.c
n

6.. =

B
I

6.. 0.055 .__.__._.____.......

5

0.c

VI

6 =
li

B
6.a

3.0

0.0
0.0

0.2

0.4

0.6

0.8

0.0

VE

1.0

0.78

0.80

0.82

0.84

Mole Froction Carbon Dioxide

Mole Fraction Carbon Dioxide

Figure 6 - P-z Diagram for CO, and decane at 238.0"C.

Figure 7 - P-y Diagram for CO, and decane at 238.0"C.

12.0

of Figure 4, calculated for the system ethane-n-decane, shows

that as the critical volume ratio more close!y approaches
unity, the dispersive term in the correlation overcorrects the
6, (0.032). For some binary systems, including methaneethane, ethane-propane and propane-decane, slightly negative 6; regressed from the individual n-alkane binary studies
have been reported as the critical volume ratios approach
unity. Since the proposed generalization considers only
attractive forces, the predicted values of 6, are always positive and will necessarily overpredict the interaction parameter
in the above systems.
A sample system illustrating the additional effects of
molecular moments and temperature on the sensitivity of calculated phase behavior to generalized interaction parameters
is shown for carbon dioxide in combination with n-decane
in Figures 5 through 7. Carbon dioxide was chosen for the
illustration not only because of its significance as an extraction agent, but also to show the effect of a large quadrupole
on computed and observed phase behavior. As shown in the
figures it is necessary to consider both the dispersive (0.055)
and inductive (0.048) contributions in the generalized interaction correlation in order to adequately match the observed
phase behaviour data (6i,= 0.103). It is interesting to note
that the temperature independent correlation appears to apply
over a wide range of phase behavior observation. Other than
an apparent overestimation of decane solubility in the vapor
phase (that increases with temperature), no other significant
systematic deviation in computed behaviour with temperature is noticeable.

0.86

10.0.-

blj = 0.m

6..= 0.004

....................

6. = 0.000

-__-------

11

8.0.n

2
z

"

!i

6.0-1

Lf

4.0-

0.0

0.2

0.4

0.6

0.8

1.0

M& Froction Carbon Dioxide

Figure 8 - P-z Diagram for CO, and hexadecane at 35.0"C.

Figure 8 illustrates a comparison of experimental data and
predictions for a binary system of carbon dioxide and hexadecane. The overestimation of the binary interaction may
be attributed to the initial assumption, used in developing
Equation (9), that the ionization potential ratio is close to
unity. Using ionization totentiah from Prausnitz et al.
4 ) is as follows for pairs
(1986), the ratio of 2 (Zi4) 5/(Zi

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 68, DECEMBER, 1990

1037

of hydrocarbons with carbon dioxide:

C 0 2 - methane
0.9997
C02 - propane
0.9949
C 0 2 - heptdne
0.9906
C02 - mesitylene 0.9708
As the ionization potential of the heavy molecule continues
to decrease, the effect may become much larger and the contribution to (,] from the dispersive term would tend to zero.
The correlation also gives larger deviations for the systems
nonane-hydrogen sulphide, ethylcyclohexane-hydrogen sulphide, and propylcyclohexane-hydrogen sulphide. Again this
may be a function of large ionization potential differences
since the 6, values for these systems are also overpredicted.
The carbon dioxide-hexadecane system may therefore
represent an upper limit for the safe application of this generalization. The introduction of a second binary interaction
parameter, to account for correction in the b term, is an
obvious next step and is currently being evaluated for
extending the correlation to larger molecules.
It is also interesting to note that a liquid-liquid phase transition in the carbon dioxide-hexadecane system is evident
at pressures above 8 MPa. The liquid-liquid split is calculated at almost the same pressure regardless of the interaction parameter used even though the phase envelope is
extremely sensitive to the magnitude of the interaction
parameter.
The TS generalization does appear to underpredict the
interaction parameter for most of the binaries containing
nitrogen. One possible explanation for this is that the value
of the quadrupole for nitrogen is inaccurate. If the value for
Q for nitro en were decreased from -0.474 to -0.791
(p5112~ r n ~ ~ x l O
then
~ ~ the
) overall deviations in DP and
DY would drop to 5.37% and 0.99 respectively for 3242
converged bubble point calculations.
For dispersive forces only, a better empirical fit of the data
base was obtained by substituting 44.0/(Vcj VCj)O.for 8 in
Equation 15 (where V,. is given in cm/mol). The average
pressure deviations for this function were 5.5% for 3263 converged points which is slightly better than the results for a
constant 8 value of 0.20. The other advantage of the
44.0/ (VcjVcj). exponent is that it produces a damped
exponent for pairs with large size differences which appears
to fit the data in these systems better (ie. methane-eicosane
regressed 6, is negative) and may in fact correct for the
effect of the ionization potential ratio. A constant 8 value
will give an ever increasing 6.. as the molecular size
differential increases. A constant $was retained at this point
since it is more theoretically satisfying and since a b interaction is envisioned to account more properly for molecular
size differences.

Conclusions
A generalized two parameter model for representing binary
interactions in the attractive term of the Peng-Robinson equation of state has been developed and evaluated. The model
includes both dispersive and inductive force terms and
requires molecular information including critical volume,
dipole moment, and quadrupole moment.
Results of phase behaviour predictions for 72 binary
systems indicate that errors arising from the generalized
model are only slightly higher than those exhibited by the
component dependent models presented by others (Nishiumi
et al., Katz and Firoozabadi, Kato et al.).
1038

This work is seen as a step towards developing a predictive model for describing phase behaviour in a wide range
of systems including those with large molecular size differences and those with strongly polar constituents, typical of
supercritical extraction processes. Although the generalized
model has been used with reasonably large molecules (hexadecane), further development of the model will be necessary in order to include much larger molecules, polar-polar
intermolecular forces, and hydrogen bonding effects.

Acknowledgements
Financial support received from the Natural Sciences and
Engineering Research Council of Canada and from Amoco Canada
Petroleum Co. Ltd. is greatly appreciated.

Nomenclature
equation of state parameter (Pa . ( ~ m ~ / m o l ) ~ )
equation of state parameter (cm3/ moi)
deviation in bubble point pressure
= deviation in vapor mole fraction
E l = objective function defined by Equation (16)
EOS = equation of state
I
= ionization potential (ev)
= binary interaction parameter in TCv
= absolute pressure (Pa)
PTS = number of experimental data points
Q
= quadrupole (pJ c,~~)
r
= intermolecular separation distance (cm)
R
= universal gas constant (Jlmol . K )
REG = regressed value
T
= temperature (K)
v
= molar volume (cmirnol)
v = total volume (cm3)
x
= liquid mole fraction
y
= vapor mole fraction
z
= overall mole fraction

b
DP
DY

=
=
=

kp.

Greek
polarizability (cm3)
binary interaction parameter in a
= intermolecular potential ( p J )
= parameter in Equation (15) ( p J - * mol-)
= parameter in Equation (15)
= dipole moment ( p J * . cm3)
= intermolecular separation (cm)
= attractive potential term
= acentric factor

cy

A,,

77

0
p

u
d,
w

Subscripts
c

critical

calc = calculated
exp = experimental value
i
= component index
j
= component index

References
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Manuscript received October 12, 1989; revised manuscript

received January 26, 1990;accepted for publication February 28,

1990.

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