Fluid Phase Equilibria, 6’7(1991) 173-195 173

Elsevier Science Publishers B.V., Amsterdam

Liquid volumetric behavior and phase equilibrium

calculations by a hard-sphere three-parameter equation
of state

Ping Li, Xi-Yin Zheng ’ and Ji-Fang Lin

Department of Chemical Engineering, Dalian University of Technology,
Dalian 116012 (Peoplek Republic of China)
(Received March 16, 1990; accepted in final form June 4, 1991)

ABSTRACT

Li, P., Zheng, X.-Y. and Lin, J.-F., 1991. Liquid volumetric behavior and phase equilibrium
calculations by a hard-sphere three-parameter equation of state. Fluid Phase Equilibria,
67: 173-195.

The repulsive term of the original Patel-Teja equation of state was replaced by the
C&m&an-Starling expression. The proposed modification was found to produce increased
correlation flexibility. It allows for significant improvements in liquid volumetric predictions
of 54 pure non-polar and polar compounds as well as their vapor-liquid equilibrium (VLE)
liquid-liquid equilibrium (LLE) and vapor-liquid-liquid equilibrium (VLLE) calculations.

INTRODUCTION

Equations of state describing thermodynamic properties of substances

may be classified into the virial and van der Waal types. By attributing fluid
non-idealities to the effect of intermolecular attraction and repulsion, van
der Waal (1873) proposed a two-parameter cubic equation of state, which
provided a rather clear physical picture of molecular interactions in real
fluids. It was modified by Clausius (1880), Redlich and Kwong (1949),
Soave (1972), Peng and Robinson (1976) and generalized by Martin (1979)
to achieve a great contribution to the development of separation processes.

Author to whom correspondence should be addressed.

0378-3812/91/$03.50 0 1991 Elsevier Science Publishers B.V. All rights reserved

174

However, due to the inherent limitation of the cubic equations of state,

they are usually not capable of describing the liquid volumetric behavior as
well as phase equilibria in the vicinity of the critical region. Many re-
searchers found that the conventional Soave-Redlich-Kwong equation failed
to fit the saturated liquid density data (such as Peng and Robinson (1976),
Pate1 and Teja (1982), Sato et al. (1987), Suzuki et al. (1989)). Yu et al.
(1986) indicated that a three-parameter equation of state should be used for
simultaneous correlations of phase equilibria and saturated vapor or liquid
densities.
Pate1 and Teja (1982) have proposed a three-parameter equation of state
by introducing a substance-dependent parameter [,, but the critical volume
of the pure substance is poorly predicted. This discrepancy cannot be
remedied by simply setting {c equal to the experimental value, because other
thermodynamic properties would then probably be predicted less accurately.
On the other hand, Ada&i and Lu (1985) have pointed out that the
attractive parameter in the conventional cubic equation of state is the
controlling factor for phase equilibrium calculations. However, the repulsive
term seems to play an important role in the liquid volumetric behavior of
highly asymmetric mixtures.
In fact, most modifications emphasize the effect of the attractive term;
however, relatively less attention has been paid to the repulsive contribu-
tions (de Santis et al., 1976; Ishikawa et al., 1980; Kato et al., 1989). It is
known that the van der Waal free volume is correct only at low pressures
but is a poor approximation in the high pressure region. Wilczek-Vera and
Vera (1987) have asserted that the repulsive term used in the cubic equations
of state to represent free volume contributions failed to account for the
possible overlap of molecules.
Carnahan and Starling (1969, 1972) proposed a semi-empirical expression
for the compressibility factor based on the hard sphere fluid theory, which
has proved to be in good agreement with the Monte Carlo and molecular
dynamics simulation data. Its accuracy was also proved to be higher than
the PadC approximation by Stell et al. (1974). More sophisticated expres-
sions are available such as the hard convex body of Boublik (1981). How-
ever, Sadus et al. (1988) found no significant improvement for its prediction
of critical properties.
In this investigation, a hard-sphere three-parameter equation of state was
proposed by applying the Carnahan-Starling (CS) equation as the repulsive
term in combination with the attractive term of the Patel-Teja (PT) equa-
tion. It combines the advantages of the Virial and van der Waal types to
provide accurate descriptions ‘of saturated pressure and liquid volumetric
behavior of more than 50 pure substances as well as phase equilibria of their
mixtures, including several strongly polar and associating substances.
 175

FUNDAMENTAL EQUATIONS

CS-PT equation of state

By combining the Camahan-Starling hard-sphere equation as the repul-

sive term with the attractive term of the Patel-Teja equation, the expression
for the pressure becomes:

v(v+b) Ic(v-b) (1)

where n = b/4v is the reduced volume,

Soave’s correction factor for the temperature-dependence of the attractive

parameter was used:

a(q) = [l + F(1 - TroyI (2)

Equation (1) rigorously satisfies the following critical criteria:

(3)

(4)

where {c is the pseudo-critical compressibility factor and is substance-depen-

dent.

Analytic solutions for 52,,, L?, and L?,

Q2,, Q2, and Q2,are functions of the pseudo-critical compressibility factor,

tc, and may be derived from eqns. (3)-(5).
Let y = a/RTv and /I = c/4v, which at the critical condition become
y, = a,/RT,vc and /!I,= c/4v,. Then the reduced volume, q,, and pseudo-
176

critical compressibility factor, l,., can be written as follows:

b
71c= 4u,

From the first critical criterion (eqn. (3); see Appendix A), we obtain

(1+ 411,+ 4rl: - 417%

+ $)0 + 4% + 4& - 16%PJ2
Y, = (7)
20 - nJ4(l f 2% + 2&)
Equations (6) and (7) can be simult~eously solved for &:
(1 - 47jc - 20712- l&I: + 972) - 23,(1+ 2%X1 - %I4
P, =
4[lG(1 - nJ4 - 4r/; + 16~: - 1877:- 12n:] (8)
By substituting eqns. (7) and (8) into the second derivative at the critical
condition (see Appendix A), we obtain its root 71,.
Since the value of the reduced volume n should be physically between
zero and unity, eqn. (A2) in Appendix A was solved for the smallest positive
root of qc, which was then substituted into eqns. (7) and (8) to obtain,
respectively, the values of y, and &. Then we obtain the values of at,,, 5;2,
and Q2,by the following equations:
Q2,,= YJ, Q2,= 47Ilcsc Q2,= 4&k (9)

CALCULATIONMETHOD

Pure substances

The temperature-correction coefficient F in eqn. (2) and the pseudo-criti-

cal compressibility factor, {,, are substance-dependent and can be obtained
from PVT data of pure substances.

Calczdation of characteristics 5, and F for each substance

We first assume the initial value of [,, so values of Q,, Q,, and In, are
acquired from the equations in the preceding section. Then from the
equilibrium condition of equal fugacity between vapor and liquid phases

f,’ =fi”
where f denotes the fugacity of the pure component (see Appendix B), the
 177

correction factor a of the attractive parameter a can be obtained for each

temperature. By applying the Golden Section Method, the temperature-cor-
rection coefficient F in eqn. (2) can be estimated. The saturated liquid
density and saturated vapor pressure of pure substances are evaluated for
each datum point and compared with the literature value (Hall, 1981). The
iteration procedure continues until the following objective function satisfies
the convergence criterion:

OF= E( IPexp- pcal>/pexp

j=l
Ij + 1)
I(dxp- dd)/dxp
Values of 5, and F thus obtained for 54 pure substances including several
strongly polar compounds are presented in Table 1. It can be seen that
values of the pseudo-critical compressibility factor SC are quite different
from those of the Patel-Teja equation. For small spherical molecules such as
argon, methane, oxygen and nitrogen, CCis close to the van der Waal value
of 0.375, while for n-alkanes and alkenes, it decreases with increasing carbon
number and is close to the Redlich-Kwong value of 0.333. For most polar
substances, 5, is also close to 0.333. However, for alcohols it increases with
increasing carbon number and is close to the value of the homologous
alkane.

Correlation of & and F with the acentric factor o

In order to extend the applicability of the proposed equation to other
substances not included in Table 1, values of SC and F listed in that table
were correlated with the acentric factor w of the corresponding substances,
which could be divided into two groups: non-polar and polar.
(1) Non-polar substance

F*IPXl-pOl~
= 0.49237 + 1.351590 - 0.27522~~ (11)
= 0.36511 - 0.03461~ - 0.004940’
SC$0l?-pCAa* 02)
(2) Polar substance

F*
po,ar= 0.95453 - 2.21204~ + 4.44139~~ (13)

s*c,polar = 0.36956 - 0.235080 + 0.344840~ (14)

where F”&_polar,F,*,,,,,, S&,n_polarand lC&,iarare designated as the generalized
temperature-correction coefficient and the generalized pseudo-critical com-
pressibility factor respectively.
Values of the acentric factor w for all substances were obtained from Reid
et al. (1977).
178

TABLE 1
Parameters of the CS-PT equation of state 5, and F, and comparisons of saturated liquid
density and vapor pressure

No. Substance {, F Reduced No. of AADV ’ (W) AADP = (56)

temp. rmge ;t;x cs-FT FT cs-FT

1 Methane 0.365 0.5102872 0.593-1.000 11 1.63 3.03 0.39

2 Ethane 0.361 0.6241653 0.567-1.000 18 1.57 3.63 0.28
3 Propane 0.359 0.7062301 0.576-1.000 20 1.33 2.86 0.40
4 n-Butane 0.358 0.7360680 0.572-1.000 22 0.98 3.39 0.44
5 i-Butane 0.359 0.7351618 0.571-1.000 21 1.58 2.61 0.34
6 n-Pentane 0.359 0.8351017 0.560-1.000 25 1.30 3.11 0.61
7 i-Pentane 0.360 0.8037654 0.572-1.000 24 0.72 2.24 0.48
8 n-Hexane 0.355 0.8788605 0.558-1.000 26 0.53 2.24 0.44
9 n-Heptane 0.353 0.9410798 0.552-1.000 28 0.60 2.04 0.84
10 n-Octane 0.353 0.9999135 0.551-1.000 29 1.04 1.34 0.65
11 n-Nonane 0.351 1.0602130 0.544-1.000 22 0.61 0.53 0.57
12 n-Decane 0.347 1.0795800 0.555-0.850 19 1.18 0.62 0.11
13 n-Undecane 0.348 1.1515700 0.553-0.772 15 0.62 0.63 0.10
14 n-Dodecane 0.346 1.1829540 0.567-0.780 15 0.50 0.70 0.08
15 n-Tridecane 0.345 1.2529160 0.567-0.789 16 0.79 0.70 0.08
16 n-Tetra-
decane 0.344 1.2637680 0.583-0.800 16 0.90 0.78 0.08
17 n-Penta-
decane 0.345 1.3256980 0.580-0.768 14 0.26 - 0.09
18 n-Hexa-
decane 0.342 1.3438790 0.580-0.767 14 0.18 - 0.21
19 n-Hepta-
decane 0.338 1.3266780 0.604-0.822 17 0.31 0.94 0.07
20 n-Octa-
decane 0.329 1.2747150 0.608-0.769 13 0.10 1.07 0.17
21 n-Nona-
decane 0.322 1.4219008 0.604-0.747 12 0.44 - 0.14
22 n-Biwsane 0.334 1.4441680 0.617-0.747 11 0.74 1.04 0.12
23 Acetylene 0.356 0.7230005 0.626-0.983 12 0.57 1.83 0.82
24 Ethylene 0.362 0.6108499 0.578-0.967 12 0.63 2.72 0.45
25 Propylene 0.361 0.6941381 0.557-0.996 17 0.64 2.27 0.46
26 1-Butene 0.359 0.7572677 0.556-0.985 19 1.08 1.45 0.52
27 l-Hexene 0.356 0.8606799 0.562-0.979 22 0.45 - 0.66
28 2-Methyl-l-
pentene 0.348 0.7135956 0.554-0.984 22 0.99 - 0.62
29 l-Heptene 0.350 0.8891904 0.564-0.974 23 1.80 _ 0.41
30 Benzene 0.357 0.7669511 0.557-1.000 28 0.51 1.69 0.50
31 Toluene 0.354 0.7928092 0.563-1.000 29 0.63 - 0.59
32 Ethyl-
benzene 0.353 0.8690904 0.556-1.000 31 0.52 - 0.52
33 m-Xylene 0.350 0.8784074 0.556-0.990 31 0.68 - 0.59
 179

TABLE 1 (continued)

No. Substance lc F Reduced No. of AAD?’ a (a) AADP a (%)

temp. range ;r$t; CS_pT pT CS-pT

34 n-Propyl-
benzene 0.351 0.9128492 0.553-0.992 29 0.72 - 0.68
35 n-Butyl-
benzene 0.352 0.9767079 0.565-0.989 29 0.87 - 1.08
36 Ethyl ether 0.356 0.8609599 0.564-0.992 21 0.84 _ 0.70
37 Propylene
oxide 0.333 0.6808226 0.566-0.981 21 1.28 - 1.03
38 Acetone 0.332 0.7332811 0.557-0.990 23 1.06 - 1.31
39 Methyl
acetate 0.347 0.8588353 0.559-0.973 22 0.87 _ 0.81
40 Methanol 0.331 1.0231190 0.552-0.982 23 1.28 0.51 0.88
41 Ethanol 0.349 1.2778210 0.570-0.885 13 0.48 0.51 0.43
42 n-Propanol 0.357 1.3273380 0.565-0.900 11 0.88 0.66 0.52
43 n-Butanol 0.359 1.3166920 0.568-0.853 10 0.67 0.28 0.31
44 n-Pentanol 0.362 1.3194620 0.578-0.816 9 0.48 0.53 0.38
45 n-Hexanol 0.354 1.2537090 0.562-0.841 18 0.65 - 0.51
46 Argon 0.367 0.4857915 0.597-0.962 34 1.25 - 0.95
47 Oxygen 0.365 0.4764945 0.603-0.991 36 1.46 2.37 0.26
48 Nitrogen 0.367 0.5708072 0.580-0.976 32 1.56 2.32 0.26
49 Carbon
monoxide 0.369 0.6123253 0.551-0.927 6 1.73 2.10 0.44
50 Carbon
dioxide 0.360 0.7392856 0.717-1.000 19 0.73 1.78 0.67
51 Hydrogen
sulfide 0.364 0.6345299 0.571-0.973 16 1.31 1.57 0.42
52 Sulfur
dioxide 0.354 0.8107099 0.564-0.982 19 0.42 1.71 0.61
53 Ammonia 0.334 0.6689825 0.575-0.994 18 1.24 2.44 0.65
54 Water 0.321 0.6920028 0.561-0.978 28 1.69 1.57 1.42

Data are from Hall (1981).

; i
J=l
1u,? - VI”’ /v,“”
’ 1
x100.

AADP = ; ;
J=l
IP,“” - p,=l I/p,e”

1
x100.

Temperature dependence of SC
Since the pseudo-critical compressibility factors SCobtained by the pro-
posed equation as listed in Table 1 are substance-dependent and far above
the experimental value Z,, calculations are still not quite satisfactory in the
vicinity of the critical region.
180

In this investigation, the pseudo-critical compressibility factors 5, were

also correlated with temperatures from the PVT data of all substances
investigated.

St
c
= zc+ 1.72% - z,)(l - T,)‘.’ T,I 1
05)
zc T, > 1
From the above equation, it is evident that when q --+1, then 1: + Z,,
equal to the experimental value of each substance. Thus the proposed
equation is expected to accurately predict the critical volumetric behavior
and phase equilibria in the critical region.
If the temperature-dependent [L is substituted in eqn. (9) instead of SC,
the characteristic values of a:,, a; and a;26should also be temperature
dependent. However, as shown in Fig. 1 for some typical compounds,
although CJi, and Qb increase with increasing reduced temperatures, S2: =
P,b/RT, is almost independent of temperature since the volume of hard
sphere can be considered as temperature independent.

Mixtures

When the proposed equation is applied to calculate phase equilibria of

mixtures, the following conventional mixing rules are adopted:

a, = i i XiXj(l - k,j)(a;a,)“2 k,, = kji

r=l j=l

b,,, = i x,b, 06)

I=1

c,= i x;c,
i=l

CALCULATED RESULTS

Saturated liquid volumes and vapor pressures of pure substances

By applying the proposed equation with temperature-dependent pseudo-

critical compressibility factor {,‘, saturated liquid volumes and vapor pres-
sures of 54 substances were calculated and compared with experimental
values. Average absolute deviations of saturated liquid volumes and vapor
pressures are listed in Table 1 in comparison with those of saturated liquid
volumes for 37 substances as calculated by the original Patel-Teja equation
 181

.tJ a5 _-M’
--- ___.--- ,;
--
Ii----
04 - -.---

n-Cl6H34
-
a-
CWH 02,.

05 -
- Tr
Fig. 1. Temperature dependence of Q:,, 0; and Qs.

with SC temperature-modification. However, deviations of vapor pressure

were not reported (Pate1 and Teja, 1982).
Deviations of saturated liquid volumes for both ammonia and n-eicosane
calculated by the proposed equation with S,’ are shown in Figs. 2 and 3 in
comparison with those obtained by the Patel-Teja equation with tempera-
ture-dependent {, .

Vapor-liquid equilibrium correlations

Vapor-liquid equilibrium data of 21 binary systems containing alkanes,

aromatics and polar substances, in all 62 isotherms with 431 datum points,

Fig. 2. Predicted deviations of saturated liquid volume for ammonia.

182

- Ir
Fig. 3. Predicted deviations of saturated liquid volume for n-eicosane.

were correlated with the proposed equation and with the Patel-Teja equa-
tion of state. The flash method was applied to calculate the deviations of
both vapor and liquid phase compositions.
Typical results were summarized in Table 2. For all datum points, the
total average standard deviations AX of vapor and liquid compositions were
0.95 for the proposed equation, compared with 1.72 for the Patel-Teja
equation.

AX= ;(Ax + Ay)

Liquid-liquid equilibrium correlations

High-pressure liquid-liquid equilibrium data of 25 binary systems con-

taining alkanes, aromatics and polar substances with ethane and carbon
dioxide as a common component, in all 610 datum points, were also
correlated by the CS-PT and PT equations of state.
Results obtained are shown in Table 3. The present model is especially
good in comparison with the original Patel-Teja equation, the SRK equa-
tion (Soave, 1972) and the DDLC-EOS model as proposed in our previous
work (Zheng et al., 1988). Several typical results are shown in Figs. 4 and 5.
 183

TABLE 2
Fitting accuracies and binary interaction parameters for high pressure vapor-liquid equilibria
of binary systems

No. System Temp. Pressure No. of CS-PT PT Ref.

range range datum k,,
AX k,, AX
(R) (MPa) points

Ethane + ethyl 298.15 0.92- 6 0.045 0.80 0.032 0.85 1

ether 3.86

Ethane + 298.15 0.48- 7 0.138 0.67 0.155 3.50 1

acetone 3.62

Ethane + methyl 298.15 0.48- 10 0.145 0.99 0.143 2.30 1

ethanoate 3.85

Ethane + 298.15 1.09- 4 0.047 0.49 0.024 0.61 1

methanol 3.86

Ethene + 298.15 1.02- 10 0.037 1.21 0.004 3.76 2

methanol 0.97
313.15 3.08- 12 0.033 1.37 0.003 3.95
10.88

Acetone + water 523.15 4.66- 10 0.131 2.87 0.111 4.33 3

6.76

Propane + ethanol 325.00 0.57- 4 0.026 1.26 0.027 4.32 4

1.44
350.00 0.84- 4 0.024 1.33 0.026 2.44
2.06
375.00 1.13- 4 0.037 1.06 0.030 1.53
3.09
400.00 1.66- 4 0.020 1.55 0.026 1.39
4.69
425.00 2.49- 3 0.021 2.55 0.016 3.53
5.62

Carbon dioxide + 316.65 5.86- 3 0.144 0.60 0.117 1.08 5

2-propanol 7.93
334.85 1.3% 8 0.123 1.33 0.107 1.80
9.31
354.45 5.86- 5 0.098 1.38 0.097 2.50
11.38
394.55 6.90- 5 0.024 1.47 0.066 1.81
12.41

Hydrogen sulfide + 310.93 0.20- 6 0.008 0.36 0.0002 0.48 6

toluene 2.55
352.59 0.41- 7 0.007 0.72 -0.005 0.89
5.64
184

TABLE 2 (continued)

No. System Temp. Pressure No. of CS-PT PT Ref.

range range datum k
12 AX k,, AX
(R) (MPa) points

9 Hydrogen sulfide + 394.26 0.38- 8 0.020 1.51 0.003 1.75

toluene 9.74
447.59 1.38- 6 0.009 0.72 0.020 0.94
11.57

10 Carbon dioxide + 345.40 4.71- 5 0.157 1.13 0.144 2.77 7

trans-decalin 14.95
399.70 4.51- 5 0.118 1.02 0.134 1.96
21.51
523.60 5.10- 4 0.053 0.98 0.115 2.18
22.14

11 Carbon dioxide + 345.90 4.66- 7 0.160 0.80 0.140 2.25 7

tetralin 15.93
415.30 4.07- 6 0.113 0.98 0.135 1.58
22.24
521.20 4.56- 7 0.063 1.16 0.130 1.67
22.73

12 Carbon dioxide + 343.20 4.46- 5 0.080 0.39 0.053 0.83 7

quinoline 13.43
433.40 4.56- 4 0.013 0.47 0.021 0.50
16.37
460.90 7.94- 4 - 0.023 0.70 -0.001 0.70
22.54
541.00 4.95- 7 - 0.085 0.82 - 0.030 1.01
19.90

13 Benzene + 569.20 1.08- 5 0.054 1.39 0.034 1.66 7

tetralin 4.31
609.20 1.57- 14 0.022 0.83 0.026 1.32
5.29
659.00 2.74- 8 0.010 0.95 0.018 1.46
4.90

14 Benzene + 568.50 1.08- 11 0.016 0.46 -0.0004 0.66 7

quinoline 4.51
638.40 1.57- 11 -0.043 1.88 -0.040 2.72
6.08
709.90 3.33- 9 -0.104 1.95 - 0.084 2.51
5.81

15 Nitrogen + 462.20 2.03- 7 -0.178 0.12 0.185 0.06 8

1-methylnapthalene 25.40
542.80 2.08- 7 - 0.434 0.24 0.133 0.21
25.23
 185

TABLE 2 (continued)

No. System Temp. Pressure No. of CS-PT PT Ref.

range range datum k AX kr2 AX
12
(R) (MPa) points

15 Nitrogen + 624.00 3.09- 6 - 0.868 0.62 0.096 0.67

I-methylnapthalene 25.29
703.30 4.08- 7 - 1.976 0.50 -0.144 2.17
25.24

16 Carbon dioxide + 277.65 0.23- 10 0.128 0.76 0.108 1.05 9

n-Pentane 3.75
311.04 0.46- 14 0.155 0.35 0.131 0.69
7.38

17 Carbon dioxide + 303.15 l.OO- 0.122 1.18 0.100 1.52 10

l-hexene 5.91
323.15 0.96- 0.125 0.86 0.105 1.34
6.53
343.15 1.03- 0.123 1.39 0.116 1.59
6.20

18 Carbon dioxide + 303.15 1.02- 0.118 0.78 0.103 1.03 10

l-heptene 5.59
323.15 l.Ol- 0.126 0.74 0.100 1.20
6.28
343.15- 1.01 0.112 1.50 0.103 2.50
7.32

19 Carbon dioxide + 342.15 5.15- 0.113 0.47 0.095 1.87 7

n-decane 12.59
411.20 4.81- 0.057 0.48 0.088 1.11
17.99
520.40 3.09- - 0.020 0.56 0.112 1.59
13.97
594.20 3.95- -0.85 0.26 0.122 1.78
5.49

20 Carbon dioxide + 308.15 0.69- 0.119 1.26 0.088 0.72 11

n-hexadecane 7.97
463.05 2.01- - 0.054 0.11 0.0004 0.09
5.08
542.85 2.01- - 0.122 0.41 - 0.030 0.50
5.09
623.55 2.02- -0.390 0.42 0.015 1.38
5.09
663.75 2.09- - 0.494 0.70 0.010 2.17
5.09
186

TABLE 2 (continued)

No. System Temp. Pressure No. of cs-PT PT Ref.

range range datum k
AX k,, AX
(K) (MPa) points l2
21 Nitrogen+ 310.93 1.72- 11 0.014 0.83 0.114 0.86 12
n-hexane 34.47
344.26 1.72- 11 -0.012 0.83 0.121 0.97
34.47
377.55 1.72- 11 -0.105 1.36 0.057 2.22
34.47
410.95 1.76- 11 -0.231 1.07 -0.066 3.58
29.09
444.25 3.45- 8 - 0.242 0.82 - 0.156 3.59
20.19
Refs.: 1. Ohgaki, K., et al, J. Chem. Eng. Data, 21 (1976) 55; 2. Ohgaki, K., et al., J. Chem.
Eng. Jpn., 16 (1983) 263; 3. Griswold, J., et rd., J. Chem. Eng. Progr. Symp. Ser., 48 (1952) 18;
4. Gomez-Nieto, M., et al., AIChE J., 24 (1978) 672; 5. Maciej, R., et al., J. Chem. Eng. Data,
31 (1986) 43; 6. Ng, H.-J., et al., J. Chem. Eng. Data, 25 (1980) 51. 7. Inomata, H., et al., J.
Chem. Eng. Jpn., 19 (1986) 386; 8. Lin, H.-M., et al., Fluid Phase Equilibria, 10 (1983) 73; 9.
Besserer, G.J., et al., J. Chem. Eng. Data, 18 (1973) 416; 10. Juan, N.V., et al., J. Chem. Eng.
Data, 29 (1984) 269; 11. Sebastian, H.M., et al., J. Chem. Eng. Data, 25 (1980) 138; 12.
Poston, R.S., et al., J. Chem. Eng. Data, 11 (1966) 364.

06 c%m 0.94 1.0

Mole Fraction of CO2
Fig. 4. Comparison of calculated results of LLE for the carbon dioxide(l)- n-Tridecane(2)
system.
 187

Mole Fraction of WIG

Fig. 5. Comparison of calculated results of LLE for the ethane(l)-ethanol(2) system.

Vapor-liquid-liquid equilibrium correlations

Vapor-liquid and vapor-liquid-liquid equilibrium data for the methane

and n-hexane system were correlated by the CS-FT and FT equations of

CH - n-CsHr

273lGK .
24G14K m
22315K +
20150K o
19805K m
19G91K ’
193.1GK A
19050K b
lGG23K .
lG2.46 K
CSPT L

, I .. ,

00 04 QG 0’9 10
Mole Fradlon of CH

Fig. 6. Correlation of VLE and VLLE for the methane(l) -n-hexane(2) system.
TABLE 3
Fitting accuracies and binary interaction parameters for high pressure liquid-liquid equilibria of binary systems

No. System Temp. Pressure No. of CS-PT PT SRK DDLC-EOS Ref.

range range datum k
AX k,, AX k,, AX k,z k,, AX
(K) WPa) points l2

Carbon dioxide + 215.99 0.51 9 0.115 0.84 0.093 4.94 0.107 4.89 0.199 0.290 3.25 1
n-octane -231.49 -0.92

Carbon dioxide + 235.45 1.06 9 0.096 0.22 0.089 1.21 0.107 3.59 0.202 0.309 2.20 2
n-decane -248.74 -1.64

Carbon dioxide + 254.28 2.01 8 0.102 0.18 0.078 1.93 0.105 2.56 0.193 0.278 1.67 3
n-dodecane -267.31 -2.78

Carbon dioxide + 255.16 2.08 14 0.115 0.69 0.078 2.37 0.108 2.69 0.207 0.324 2.11 3
n-tridecane -278.95 -3.93
311.21 8.19 12 0.165 0.07 0.090 0.02 0.100 0.79 0.160 0.061 0.40 4
-313.91 -8.65

Carbon dioxide + 270.40 3.08 10 0.113 2.17 0.080 2.24 0.099 1.94 0.167 0.110 2.06 3
n-tetradecane -305.00 -8.06

Carbon dioxide + 308.15 7.98 10 0.142 0.62 0.081 0.93 0.116 1.81 0.155 0.171 1.32 5
n-hexadecane -14.39

Carbon dioxide + 300.40 6.75 17 0.121 0.64 0.076 0.12 0.118 0.26 0.235 0.074 0.36 6
n-eiwsane -305.03 -1.55
300.40 6.75 20 0.127 0.72 0.073 0.17 0.116 0.12 0.195 0.123 0.11 7
-304.60 -7.43

Carbon dioxide + 301.78 6.98 10 0.116 0.72 0.079 0.16 0.120 0.07 0.189 0.177 0.08 7
n-heneiwsane -303.87 -7.32

Carbon dioxide + 215.89 0.51 9 0.097 0.33 0.085 3.60 - 8

n-butylbenzene -231.00 -0.92
10 Carbon dioxide + 227.89 0.68 7 0.084 0.58 0.080 2.82 0.096 2.62 0.180 0.240 2.24 9
n-hexylbenzene -251.40 -1.82

11 Carbon dioxide + 227.67 0.82 10 0.090 1.13 0.075 3.75 0.097 3.34 0.175 0.243 3.47 9
n-heptylbenzene -270.15 -3.12
302.89 6.87 10 0.149 0.15 0.090 0.47 0.083 0.69 0.114 0.126 1.19 9
-311.72 -8.32

12 Carbon dioxide + 234.11 1.05 18 0.140 2.05 0.085 2.32 10

n-non ylbenzene -303.88 -7.17

13 Carbon dioxide f 275.62 3.71 21 0.117 1.48 0.066 1.40 - - 10

n-pentadecyl- -302.35 -7.06
benzene

14 Carbon dioxide + 234.45 1.05 15 0.152 1.22 0.139 3.12 - 8

trans-decalin -313.15 -8.28

15 Carbon dioxide + 282.25 4.29 10 0.145 1.31 0.128 1.43 0.121 11

Zmethylnaph- -300.15 -6.51
thalene

16 Methane + 182.73 3.45 7 0.096 0.52 0.037 2.08 0.018 1.93 0.039 - 0.04 1.93 12
n-hexane -195.72 -5.20

17 Ethane -k 309.75 5.25 9 0.085 0.05 0.020 0.02 0.028 0.41 0.260 -0.090 0.62 13
n-nonadecane -310.93 -5.39

18 Ethane -f- 306.89 4.95 9 0.124 0.09 0.010 0.04 0.040 0.31 0.215 -0.069 0.67 13
n-eicosane -309.78 -5.29

19 Ethane -k 302.76 4.56 6 0.110 0.10 0.010 0.20 0.022 0.42 0.228 -0.070 0.44 14
n-docosane -307.11 -5.01
300.72 4.39 16 O*llO 0.13 0.011 0.12 0.026 0.39 0.224 -0.067 0.54 15
-307.98 -5.15
Table 3 (continued)

No. System Temp. Pressure No. of CS-PT PT SRK DDLC-EOS Ref. g

range range datum k AX
AX k,, AX k, AX k,, k,,
(K) (MPa) points I2

20 Ethane + 298.94 4.21 11 0.110 0.14 0.012 0.32 0.031 0.38 0.140 -0.045 0.55 14
n-tricosane -305.52 -4.85

21 Ethane + 302.29 4.54 8 0.104 0.12 0.010 0.21 0.035 0.20 0.167 -0.048 0.30 14
n-tetracosane -306.33 -4.95

22 Ethane + 267.50 2.03 5 0.039 5.68 0.021 11.36 - - - _ - 16

methanol -309.57 -5.18

23 Ethane + 307.00 4.90 7 0.075 0.38 0.048 2.59 - - - - - 17

ethanol -314.00 -5.58

24 Carbon dioxide + 298.20 6.42 4 -0.046 0.88 - 0.098 1.42 - _ _ _ - 18

water -10.99

25 Water + 323.2 1.19 4 0.155 0.32 a * - - - - - 18

1,1-difluoroethane -10.13

Refs.: 1. Hotlovy, J.D., et al., J. Chem. Eng. Data, 27 (1982) 298; 2. Kulkami, A.A., et al., J. Chem. Eng. Data, 19 (1974) 92; 3. Hotlovy,
J.D., et al., J. Chem. Eng. Data, 26 (1981) 256; 4. Fall, D.J., et al., J. Chem. Eng. Data, 30 (1985) 276; 5. Charoensombut-Amon, T., et al.,
Fluid Phase Equilibria, 31 (1986) 89; 6. Huie, N.C., et al., J. Chem. Eng. Data, 18 (1973) 311; 7. Fall, D.J., et al., J. Chem. Eng. Data, 30
(1985) 82; 8. Tiffin, D.L., et al., J. Chem. Eng. Data, 23 (1978) 45; 9. Fall, J.L., et al., Fluid Phase Equilibria, 28 (1986) 87; 10. Fall, D.J., et
al., Fluid Phase Equilibria, 23 (1985) 259; 11. Kulkami, A.A., et al., J. Chem. Eng. Data, 19 (1974) 349; 12. Merrill, R.C., et al., J. Chem.
Eng. Data, 28 (1983) 215; 13. Kohn, J.P., et al., J. Chem. Eng. Data, 11 (1966) 333. 14. Estrera, S.S., et al., J. Chem. Eng. Data, 32 (1987)
201; 15. Rodrigues, A.B., et al., J. Chem. Eng. Data, 12 (1967) 191; 16. Ma, Y.-H., et al., J. Chem. Eng. Data, 9 (1964) 3; 17. Paulaitis, M.E.,
et al., Chemical Engineering at Supercritical Fluid Conditions, AM Arbor Science Publishers, 1983, p. 120; 18. Takashi, N., et al., Fluid
Phase Equilibria, 38 (1987) 109.
a No convergence.
 191

TABLE 4
Fitting accuracies and the binary interaction parameters for VLE, LLE and VLLE of the
methane(l)- n-hexane(2) system

No. Temp. Pressure No. of cs-PT PT

range range datum k AX
12 ** k,2
(W (MPa) points

1 182.46 0.14- 13 0.077 0.41 0.045 1.73

3.52
2 186.23 0.3% 17 0.088 0.37 0.034 2.51
4.30
3 190.50 0.14- 19 0.105 0.60 0.041 2.55
5.31
4 193.15 0.14- 19 0.104 0.33 0.040 2.78
6.09
5 195.91 0.14- 18 0.100 0.27 0.038 2.81
6.72
6 198.05 0.14- 14 0.096 0.24 0.052 1.85
6.89
7 210.15 0.14- 13 0.093 0.39 0.046 1.62
9.65
8 223.15 0.14- 16 0.083 0.64 0.040 1.46
11.72
9 248.14 0.14- 19 0.056 1.15 0.029 1.59
15.86
10 273.16 0.17- 20 0.036 1.61 0.018 1.95
18.27

Data from Lin, Y.-N., et al., J. Chem. Eng. Data, 22 (1977) 402.

state. Results obtained were compared in Table 4 and Fig. 6, which

indicated that the Patel-Teja equation could be significantly improved by
introducing the Carnahan-Starling equation in place of the van der Waals
repulsive term.
All phase equilibrium correlations were performed with the temperature-
dependent pseudo-critical compressibility factor l,’ for both CS-PT and
original PT equations.

CONCLUSION

The proposed equation was found to offer an increased correlation

flexibility by using only PC, T, and w. It allows for significant improvement
in PVT predictions and phase equilibrium correlations for polar and non-
polar mixtures without additional parameters. The extension to multicompo-
nent systems is straightforward.
192

ACKNOWLEDGMENT

This work was supported by the National Natural Science Funds of

China.

NOMENCLATURE

attractive parameter (J m2 mole2)

repulsive parameter (m3 mol-‘)
third parameter (m3 mol-‘)
fugacity
temperature-correction coefficient
binary interaction parameter
number of components
number of datum points
pressure (MPa)
gas constant (J mol-’ K-‘)
temperature (K)
reduced temperature
molar volume (m3 mol-‘)
mole fraction
compressibility factor
experimental critical compressibility factor

Greek letters

SC pseudo-critical compressibility factor

11 reduced volume
acentric factor
i.,, G2,, 9, characteristic values defined by eqn. (9)

Subscripts

C critical
Cd calculated
exp experimental
4 j, k component
m mixture
 193

Superscripts

I, II I and II liquid phases

1 liquid phase
V vapor phase
* generalized value
I
temperature-dependent

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APPENDIX A

The first derivative at the critical condition:

(g),=Jf$[- 1 + 4Q + 4T?:- 44: + Y:

(1 - qJ4

+ (I+
2Y,(l + 2% + 2&)

47, + 4& - 1617$J* 1 = ’

(Al)

The second derivative at the critical condition:

1
y,(3 + 127, + 133, + 1671:+ W3: + 4fhc&) =.
-
(1 + 4s, + 4& - 1671,&)~
(A21

APPENDIX B

Fugacity of a pure component by the CS-FT equation

f B(16Z - 3B) _ AF
In p=Z-1-ln Z+
(42-B)* ”
(Bl)
 195

1 2z+II+c+ (B+C)2+4BC
hl
(B+C)2+4BC 2Z+B+C-/(B+C)2+4BC

I (B+C)2< -4BC

where
bP CP
B=m C=m

Compressibility factor by the CS-PT equation

z6 + &{ [16B + 64(C - I)] Zs + [64A - C(112B + 64) - B(36B + SO)]Z4
+ [ B2(60C + 11B - 20) + 48B( C - A)] Z3
+ [12B2( A + c) - B3(13C f B f 3)] z2
+ [B4(C + 1)B3(5C - A)] Z - CB”} = 0 W)
The smallest positive root of the above equation is the liquid-phase
compressibility factor, the largest positive root is the vapor-phase com-
pressibility factor.
Fugacity coefficient of component i in the mixtures
In ~ = B(16Z - 3B) + SZB,@Z - B)
I
(42 - B)2 (42 - B)3 - In z

-( A (I B i( B+3C)+C,(C+3B)](2Z+B+C)

-(Bi+ci)[(B+C)2+4BC]))

x(2[22+ (B-t C)Z-IK][@+ C)2+4BC])-’

xkaki
B,(B+ 3c) + c,(c+ 38)
- 033)
m (B+C)2+4BC

where
aP bP CP biP C,P
A=L B=j& C’j& Bi = RT C, = RT
uw2
I;, is defined above.