Fluid Phase Equilibria 143 1998.

7182

Prediction of vaporliquid equilibria for asymmetric systems at low

and high pressures with the PSRK model
Jiding Li b , Kai Fischer c , Jurgen
Gmehling

a, )

Uniersitat
Oldenburg, Technische Chemie, Postfach 2503, D-26111 Oldenburg, Germany
b
Department of Chemical Engineering, Tsinghua Uniersity, Beijing, China
Ecole des Mines de Paris, Centre Reacteurs et Processus, 35 Rue Saint-Honore, F-77305 Fontainebleau, France
Received 11 January 1996; revised 20 May 1997; accepted 5 August 1997

Abstract
The idea of effective R )k , Q k) for the subgroups CH 3 , CH 2 , CH and C of UNIFAC in PSRK is proposed.
Based on this idea, an empirical expression has been developed, allowing the reliable prediction of vaporliquid
equilibria for asymmetric systems at low and high pressures with the help of the PSRK model. Published by
Elsevier Science B.V.
Keywords: Asymmetric systems; Equation of state; Group contribution; Vaporliquid equilibria

1. Introduction
Since Huron and Vidal w1x proposed an approach that allowed to incorporate excess Gibbs energy
models into the mixing rules for cubic equations of state, many group contribution equations of state
have been developed. One of them is the PSRK model proposed by Holderbaum and Gmehling w2x, in
which the PSRK mixing rule combines the UNIFAC model w3x with the SRK equation of state. A
comparison with other group contribution equations of state, such as the MHV2 w4,5x, LCVM w6x,
W-S w7,8x, UNIWAALS w9x, GCEOS w10x, showed w2,11x that the PSRK model has some very
important advantages, as 1. the PSRK mixing rule has a well defined reference state the liquid
mixture at atmospheric pressure., whereby the constant A o s y0.64663 used in the PSRK mixing
rule is basically calculated using quasi liquid volumes of many substances at one atmosphere; 2. the
PSRK model gives reliable results for vaporliquid equilibria and gas solubility in a large temperature
and pressure range; and 3. the parameter matrix of the PSRK model is much larger than for the other
methods, meaning PSRK has a larger range of applicability.
)

Corresponding author.

0378-3812r98r$19.00 Published by Elsevier Science B.V.

PII S 0 3 7 8 - 3 8 1 2 9 8 . 0 0 2 0 6 - 9

72

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

The PSRK model has been successfully used for different applications. However, poor results are
obtained when the model is applied to highly asymmetric systems; for example, asymmetric alkane
systems as also observed by Kalospiros et al. w12x. The same situation occurs in other group
contribution equations of state, such as the MHV2 model. In this work, the idea of effective R )
k and
Q k) for the different subgroups k s CH 3 , CH 2 , CH and C in UNIFAC is presented, overcoming this
weakness, and allows reliable predictions of the PSRK model not only for systems with similar
compounds, but also for those with different sizes.
The suggestion of modifying the R k and Q k values of the different alkane subgroups, depending
on the size of the molecule, is strongly motivated by the request to extend the range of applicability of
the PSRK method to asymmetric systems. The empirical function given below, used as empirically
adjusted, has the advantage not to influence the results on those systems, where excellent results are
already obtained not too asymmetric, limitation: ratio of molecular size lower than about 8. . New
applications, e.g., the prediction of the phase equilibrium behavior exploited for supercritical fluid
extraction, are opened, which means that PSRK with the idea of effective van der Waals properties
extends again the range of applicability.
There had been several attempts to understand and overcome the error that leads to the poor results
of group contribution G E mixing rules LCVM w6,13x.. The proposed modifications of the model
equations do not differ much in the weakness of their theoretical justification. But the problem is
clearly located in the insufficient way of characterizing the molecule dimensions in the sense of
Bondis method w14x, that means the simple addition of the group dimensions. It can be shown that the
term x i ln brbi . used in G 0E mixing rules corresponds almost exactly to the combinatorial part of
the UNIFAC method. But the covolumes b are molecular properties and the van der Waals properties
are summed up by group dimensions, leading to a discrepancy in asymmetric systems. This
understanding leads to two possible ways of improvement.
a. Skipping the combinatorial part of UNIFAC as well as the term x i ln brbi . in the PSRK
mixing rule. This leads to surprisingly good results, e.g., for symmetric and asymmetric alkanealkane systems, where no group interaction parameters are required. But the use of UNIFAC for
non-alkane systems leads generally to poor results. This can be overcome by refitting all the
parameters, which would be extremely time-consuming.
b. An empirical recorrection of the error introduced by the additive way of calculating the group
dimensions: that is the subject of this work. The correction of R k and Q k values given below was
found to be generally, applicable and thus represents a simple way to extend the range of applicability
of PSRK.

2. Corrected R )k and Q k) for the subgroups CH 3 , CH 2 , CH and C

The concept of group contributions is, that the distribution of free groups is homogeneous in the
solution. For small molecules, there is no large difference between the partition of groups, or
molecules in the solution. If the differences between small and large molecules are not considered,
and the R k and Q k values for small molecules are generally used, poor results are obtained when the
group contribution equation of state is applied for asymmetric systems containing components very
different in size. The results listed in Table 1 show that the above explained inference is apparent. In
the examples shown in Table 1, all systems consist only of alkane groups CH 2 . It should be noticed

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

73

Table 1
Results of the PSRK model original R k and Q k used. for ethaneq n-alkanes
System

T K.

P bar.

NDP a

D Pr P b %.

C 2 H 6 C 3 H 8
C 2 H 6 nC 4 H 10
C 2 H 6 nC 5 H 12
C 2 H 6 nC 6 H 14
C 2 H 6 nC 7 H 16
C 2 H 6 nC 8 H 18
C 2 H 6 nC 10 H 22
C 2 H 6 nC 11 H 24
C 2 H 6 nC 12 H 26
C 2 H 6 nC 20 H 42
C 2 H 6 nC 22 H 46
C 2 H 6 nC 28 H 58
C 2 H 6 nC 36 H 74
C 2 H 6 nC 44 H 90

127369
260394
277450
290450
338450
273373
277510
318
273373
323573
360360
348573
373573
423

0.151.8
0.655.7
0.368.3
0.979.1
27.688.2
4.166.0
0.1118.3
12.052.5
3.662.8
3.7167.6
2.792.8
5.651.8
3.747.6
5.329.8

503
119
94
76
78
68
244
10
155
102
7
36
25
6

2.1
3.6
2.7
5.8
3.4
2.2
6.8
7.6
11.0
41.8
46.0
80.8
117.1
168.0

NDPs number of data points.

D Pr P %. s100= < Pexp y Pcalc .r Pexp <.

that in PSRK, C 2 H 6 C 3 H 8 ., for example, are described by 2CH 3 2CH 3 q CH 2 . groups. Since the
interaction parameters between the alkane groups are equal to zero, the real behavior is calculated
only by the combinatorial term, meaning, by the van der Waals properties R k and Q k . Using original
R k and Q k for systems with small alkanes carbon number less than 12. , the results are satisfactory,
but, e.g., for systems containing ethane and large alkanes carbon number more than 12. , the results
become poor, whereby the deviations between experimental and predicted data increase regularly.
To describe these differences between small and large alkanes, the idea of effective van der Waals
volumes and surface areas is proposed, in which the effective values of the van der Waals volumes
and surface areas for the subgroups CH 3 , CH 2 , CH and C depend directly on the number of carbon
atoms in the molecule:
R)
k s f nc . R k

1.

Q k) s f n c . Q k

2.

where R k , Q k are the original and R k) , Q k) are the effective values of the relative van der Waals
volume and the surface area of the subgroup k. The subscript k refers to the different subgroups CH 3 ,
CH 2 , CH and C. n c is the number of alkylcarbon atoms in the molecule, for example, C 10 H 21CN:
n c s 10; C 8 H 17 CH5CH 2 : n c s 8. f n c . is a correction factor for both R k and Q k Fig. 1.. This
term was formulated empirically as follows:
3r4
5r4
3r2
f n c . s 1.0 y 0.36983n1r2
n c - 45 .
c q 1.0287n c y 1.0199n c q 0.41645n c y 0.05536 n c
3.

For the application of this formula, for each component of the given mixture, the number of CH 2
groups must be calculated. Then, for all the subgroups CH 3 , CH 2 , CH and C present in the molecule,
the original subgroup values of R k , Q k must be multiplied with the function f n c .. This corresponds

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

74

Fig. 1. The relationship between the correction factor f n c . and the number of carbon atoms n c in the molecule.
)
quasi to define new subgroups for each different molecule. The new values R )
k , Q k are used in all
calculations required to obtain the activity coefficients combinatorial and residual part. . It should be
)
noticed, that, e.g., the R )
k , Q k values of the subgroup CH 3 in hexane has another value than in
hexadecane. But it still belongs to the same main group.
It is well known that in most cases the alkyl C n H 2 nq1 . chain forms the main portion of large
molecules, while the other functional groups, such as OH, CHO, NH 2 , NO 2 represent a smaller
portion, except for aromatic components. A correction of R k , Q k for aromatic groups is not required,
because the geometry of the aromatic CH groups is independent on the molecular size. Thus, it can be
concluded that the problem occurring for the group contribution models applied to asymmetric
)
systems might be solved only by means of corrected R )
k , Q k of the subgroups CH 3 , CH 2 , CH and C
in a quite empirical, but general way. A similar approach of simply correcting the relative van der
Waals group dimensions might be promising also to improve the problems of group contribution
methods with isomeric effects, which cannot be considered up to now.
The function f n c . plotted in Fig. 1 shows that the correction factor increases very slowly with the
chain length, and remains almost equal to 1.0 when n c is less than 5, increases quite slowly between
5 - n c - 12, and increases faster when n c ) 12. The reliability of Eq. 3. has been tested from n c s 2
to n c s 44 using all experimental vaporliquid equilibrium data found in the Dortmund Data Bank
w15,16x. It is suggested that if Eq. 3. is used for components with more than 45 carbon atoms, the
results should be checked by experimental data. However, efforts to extend the idea explained above
not only for large molecules but also for polymers seems to be promising.

3. Results and discussion

The results for systems with CO 2 q large alkanes, CH 4 q large alkanes, small alkanesq large
alkanes predicted by PSRK model are summarized in Tables 2 and 3. There are about 400 VLE data
sets 2469 data points. for the gases CO 2 , CH 4 with large alkanes, and small alkanes with large
alkanes in the Dortmund Data Bank. The large amount of papers reporting the experimental
information referred to in Tables 13 would extend this article too much for this journal. The
complete bibliographic information can be requested from the authors. The mean deviation between
experimental and predicted results with the PSRK model is less than 5.6% for the pressure, and less
than 0.0085 for the vapor-phase mole fraction Tables 2 and 3. . These results show that the PSRK

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

75

Table 2
Results for CO 2 qlarge alkanes, CH 4 qlarge alkanes
System

T K.

P bar.

NDP D Pr P %.
PSRK

CO 2 nC 10 H 22
CO 2 nC 12 H 26
CO 2 nC 14 H 30
CO 2 nC 15 H 32
CO 2 nC 16 H 34
CO 2 nC 18 H 38
CO 2 nC 19 H 40
CO 2 nC 20 H 42
CO2 nC 22 H 46
CO 2 nC 24 H 50
CO 2 nC 28 H 58
CO 2 nC 32 H 66
CO 2 nC 36 H 74
CH 4 nC 10 H 22
CH 4 nC 12 H 26
CH 4 nC 13 H 28
CH 4 nC 16 H 34
CH 4 nC 20 H 42
CH 4 nC 24 H 50
CH 4 nC 28 H 58
CH 4 nC 32 H 66
CH 4 nC 36 H 74
Total indices

288594
288305
240305
313
297663
396605
313
310573
323373
373573
348573
348573
373573
244583
323373
373423
373623
323573
373573
348573
473623
473573

0.1188.4
9.071.2
8.364.9
17.064.2
4.3257.0
10.161.9
9.479.6
5.176.0
9.671.8
10.150.7
8.196.0
9.572.3
5.286.3
0.1362.0
13.3103.8
9.8456.0
20.3563.9
10.1106.9
10.150.7
9.370.9
10.150.7
10.250.6

197
12
23
8
47
24
35
110
44
15
38
52
33
596
13
25
123
27
25
23
20
29
1519

3.5
6.8
4.9
1.2
6.3
7.5
5.2
3.9
6.6
4.3
7.4
9.8
8.7
4.8
6.7
9.0
5.3
10.5
6.7
9.5
6.1
6.5
5.4

PSRK PSRK
2.7
3.8
4.5
16.5
25.7
33.7
29.3
33.2
45.2
46.8
67.5
85.4
102.1
6.6
18.0
25.5
31.3
48.4
58.0
60.6
85.9
118.6

NDP D Pr P %.

100=D y
)

PSRK

PSRK

100=D y

LCVM PSRK ) LCVM

0.82

0.94

157

2.6

4.4

0.36

0.80

0.33
0.50

1.69
1.05

21

4.3

5.5

0.29

1.00

0.05

0.26

0.06
0.04
0.02

0.02
0.05
0.01

6.3
5.0
4.0
3.4
3.7
5.5
5.8
3.5

0.20
0.00
0.00

0.76

5.2
4.4
6.6
4.3
5.8
8.1
5.4
3.6

0.06
0.04
0.02

0.85

35
70
44
15
30
41
18
126

0.53

0.20

0.20
0.82
0.08
0.05
0.05
0.04

0.27
1.18
0.21
0.02
0.06
0.01

10.5

2.1

9.5

9.5

5
572

6.5
4.4

10.6
4.6

PSRK: original R k and Q k are used.

)
PSRK ) : effective R )
k and Q k are used.
Table 3
Results for small alkanes with large alkanes with zero interaction parameters
System

T K.

P bar.

NDP D Pr P %.
PSRK

C 2 H 6 nC 10 H 22
C 2 H 6 nC 11 H 24
C 2 H 6 nC 12 H 26
C 2 H 6 nC 20 H 42
C 2 H 6 nC 22 H 46
C 2 H 6 nC 28 H 58
C 2 H 6 nC 36 H 74
C 2 H 6 nC 44 H 90
C 3 H 8 nC 10 H 22
C 3 H 8 nC 16 H 34
nC 4 H 10 nC 10 H 22
Total indices

277510 10.1118.3 244

318318 12.052.5
10
273373 3.662.8 155
323573 2.3167.6 194
300360 2.192.8
47
348573 5.651.8
36
373573 3.747.6
25
423423 5.329.8
6
277510 0.170.9
65
293313 0.612.7
30
310510 0.149.2 138
950

PSRK: original R k and Q k are used.

)
PSRK ) : effective R )
k and Q k are used.

4.0
4.1
4.2
10.1
13.9
9.9
7.3
6.1
3.7
1.6
2.1
5.7

100=D y

PSRK PSRK
6.8
7.6
11.0
41.8
46.0
80.8
117.1
168.0
5.0
10.8
2.4

NDP D Pr P %.

PSRK

0.80

0.78

0.20

0.42

0.47

0.43

0.59

0.53

PSRK

100=D y

LCVM PSRK ) LCVM

113
10
50
137
47
28
17
6

3.8
4.1
4.9
8.9
13.9
9.6
8.3
6.1

7.3
4.8
9.1
8.2
13.7
5.6
5.8
5.5

408

7.4

8.3

0.33

0.30

76

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

. PSRK )-model effective R k) , Q k) values

Fig. 2. Prediction of bubble point pressures for gas n-alkane systems.
used., v, B, l. experimental values; a. v CO 2 1.q nC 20 H 42 2., 473.15 K w17x, B CO 2 1.q nC 28 H 58 2., 473.45 K
w18x, l CO 2 1.q nC 36 H 74 2., 473.35 K w19x; b. v CH 4 1.q nC 20 H 42 2., 573.15 K w18x, B CH 4 1.q nC 28 H 58 2.,
573.25 K w18x, l CH 4 1.q nC 36 H 74 2., 573.15 K w19x; c. v C 2 H 6 1.q nC 10 H 22 2., 410.93 K w20x, B C 2 H 6
1.q nC 36 H 74 2., 423.2 K w21x, l C 2 H 6 1.q nC 44 H 90 2., 423.2 K w21x.
)
model with the modified R )
k , Q k values proposed in this work can be used to predict reliably VLE
for the gases CO 2 , CH 4 with large alkanes and small alkanes C 2 H 6 , C 3 H 8 , nC 4 H 10 . with large
alkanes.

Fig. 3. Prediction of vaporliquid equilibria for CO 2 1.q nC 16 H 34 2. and CH 4 1.q nC 16 H 34 2. in a large temperature
. PSRK )-model effective R k) , Q k) values used., - - -. PSRK model original R k , Q k values
and pressure range.
used., v, `. experimental data. a. CO 2 1.q nC 16 H 34 2. w22x; b. and c. CO 2 1.q nC 16 H 34 2. w23x; d., e. and f.,
CH 4 1.q nC 16 H 34 2. w24x.

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

77

78

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

79

Table 4
Results for different binary and ternary asymmetric systems
System

T K.

P bar.

NDP

D Pr P %.
PSRK

CO 2 nC 15 H 32 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 C 6 H 6 nC 16 H 34
H 2 nC 10 H 22 p-CH 3 C 6 H 4OH
H 2 nC 10 H 22 p-CH 3 C 6 H 4OH
H 2 nC 10 H 22 p-CH 3 C 6 H 4OH
H 2 S nC 16 H 34 nC 20 H 42
C 3 H 8 nC 6 H 14 nC 16 H 34
C 3 H 8 nC 6 H 14 nC 16 H 34
C 3 H 8 nC 6 H 14 nC 16 H 34
C 3 H 8 nC 6 H 14 nC 16 H 34
C 3 H 8 nC 6 H 14 nC 16 H 34
CH 4 n 2 nC 10 H 22
CH 4 N2 nC10H 22
CO 2 nC 14 H 29 CH5CH 2
CO 2 nC 14 H 29 CH5CH 2
CO 2 nC 14 H 29 CH5CH 2
N2 nC 10 H 22
N2 nC 12 H 26
N2 nC 16 H 34
CO nC 10 H 22
CO nC 20 H 42
CO nC 28 H 58
CO nC 36 H 74
H 2 nC 10 H 22
H 2 nC 16 H 34
H 2 nC 20 H 42
H 2 nC 28 H 58
H 2 nC 36 H 74
H 2 S nC 13 H 28
H 2 S nC 15 H 32
H 2 S nC 16 H 34
H 2 S nC 20 H 42
H 2 S nC 30 H 62

313
573
473
473
473
573
573
353
393
433
323
273
283
293
303
313
311
344
314
288
531
303
297
423
311
473
573
473
453
573
373
573
573
473
423
423
361
523

1764
200
101
201
301
101
301
20135
20135
25101
1030
14
15
16
28
210
69345
69345
1051
1051
1051
21341
48103
25490
28100
1051
1051
1051
19118
100300
1051
1051
1051
310
11112
674
552
310

8
6
5
5
5
3
3
14
15
12
15
14
20
17
17
17
44
41
5
5
5
26
2
20
6
5
5
5
6
3
5
5
5
5
8
8
6
5

4.32
6.68
17.46
22.35
25.04
11.40
4.44
5.54
5.26
1.74
8.18
1.12
1.77
1.66
1.50
3.47
8.32
6.17
2.25
2.26
3.57
5.20
8.03
6.70
8.54
16.02
16.1
9.55
5.97
15.84
20.64
25.34
21.18
7.59
4.87
7.14
5.20
24.45

References
PSRK
14.02
26.86
32.83
49.58
60.81
34.86
42.02
11.71
11.18
6.19
23.60
4.16
7.88
7.26
6.89
8.68
16.17
13.72
9.68
14.28
12.81
12.58
20.91
32.76
15.98
55.24
96.99
137.58
12.94
54.64
64.10
117.29
179.29
18.01
15.82
25.00
29.08
102.91

w27x
w28x
w23x
w23x
w23x
w23x
w23x
w29x
w29x
w29x
w30x
w31x
w31x
w31x
w31x
w31x
w32x
w32x
w33x
w33x
w33x
w34x
w35x
w24x
w36x
w25x
w25x
w25x
w37x
w28x
w25x
w25x
w25x
w26x
w38x
w39x
w40x
w26x

PSRK: original R k and Q k are used.

)
PSRK ) : effective R )
k and Q k are used.
Fig. 4. Prediction of bubble-point pressures for CO 1.q nC 28 H 58 2., CO 1.q nC 36 H 74 2., H 2 1.q nC 28 H 58 2., H 2
)
1.q nC 36 H 74 2., and H 2 S 1.q nC 30 H 62 2. at different temperatures.
. PSRK ) model effective R )
k , Qk
values used., - - -. PSRK model original R k , Q k values used., v . experimental data. a. CO 1.q nC 28 H 58 2. w25x; b.
CO 1.q nC 36 H 74 2. w25x; c. H 2 1.q nC 28 H 58 2. w25x; d. H 2 1.q nC 36 H 74 2. w25x; e. and f. H 2 S 1.q nC 30 H 62
2. w26x.

80

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

A limited comparison with the results of the LCVM model is also shown in Tables 2 and 3. The
data sets used for the comparison and their results calculated with the LCVM model are equal to those
presented by Boukouvalas et al. Tables 57 in Ref. w6x.. It can be seen that the results of PSRK are
slightly better than those of the LCVM model. In addition, the theoretical basis of the PSRK mixing
rule is better than that of the LCVM model in which no explicit reference state is defined.
)
Furthermore, the idea of effective R )
k , Q k values proposed in this paper is applicable for any group
contribution method.
Some results for CO 2 with large alkanes, CH 4 with large alkanes, small alkanes with large alkanes
are presented in Figs. 2 and 3. Fig. 2 shows the results of the bubble point pressure calculations for
CO 2 1. q nC 20 H 42 2., CO 2 1. q nC 28 H 58 2., CO 2 1. q nC 36 H 74 2., CH 4 1. q nC 20 H 42 2.,
CH 4 1. q nC 28 H 58 2. , CH 4 1. q nC 36 H 74 2., C 2 H 6 1. q nC 10 H 22 2. , C 2 H 6 1. q nC 36 H 74 2. ,
C 2 H 6 1. q nC 44 H 90 2.. Fig. 3 presents the vaporliquid equilibrium behavior for CO 2 1. q nC 16 H 34
2. , and CH 4 1. q nC 16 H 34 2. in a large temperature and pressure range. From Figs. 2 and 3 it can
)
be concluded that the PSRK model with the corrected R )
k , Q k values works reliably for these
systems.
Besides the systems composed of CO 2 with large alkanes, CH 4 with large alkanes and small
alkanes with large alkanes, the PSRK model has been used to predict the vaporliquid equilibria for
CO q large alkanes, H 2 q large alkanes, H 2 S q large alkane. Fig. 4 gives the results for CO
1. q nC 28 H 58 2., CO 1. q nC 36 H 74 2., H 2 1. q nC 28 H 58 2., H 2 1. q nC 36 H 74 2., and H 2 S
1. q nC 30 H 62 2.. It is shown again, that a great improvement is made for the PSRK model with the
)
corrected R )
k , Q k values.
It should be noticed that the interaction parameters published by Holderbaum and Gmehling w2x,
and Fischer and Gmehling w11x for the PSRK model were used without changes or adjustment in this
)
work. Probably the results would be even better, if the corrected R )
Eqs. 1. 3.. were
k , Qk
included in the PSRK model before fitting the model interaction parameters, in spite of the convincing
results obtained by PSRK in this work.
In Table 4 the results for selected data, which are fully referenced in this article, are shown. They
indicate the typical improvement of the PSRK method for binary and ternary systems.

4. Conclusion
)
The idea of effective R )
k , Q k values for the subgroups CH 3 , CH 2 , CH and C of UNIFAC used in
the PSRK model has been proposed. Based on this idea, an empirical expression correcting the van
der Waals properties of the alkane subgroups, depending on the chain length of the molecules, has
been developed. The expression combined with the PSRK model has been used to predict vaporliquid
equilibria for many asymmetric systems. For CO q large alkanes, H 2 q large alkanes, H 2 S q large
alkane, the predictive results are in good agreement with the experimental data. For CO 2 q large
alkanes, CH 4 q large alkanes, small alkanesq large alkanes more than 2400 data points., the total
mean deviation between experimental and predicted is smaller than 5.6% for pressure, and the
maximum deviation less than 0.0085 for vapor phase mole fraction. These results show that the PSRK
)
model using modified R )
k , Q k values as proposed in this work can provide a reliable prediction of
vaporliquid equilibria at low and high pressures for highly asymmetric systems, apart from those
mentioned by Holderbaum and Gmehling w2x, and Fischer and Gmehling w11x.

J. Li et al.r Fluid Phase Equilibria 143 (1998) 7182

81

)
It should be pointed out that the idea of the effective R )
k , Q k values proposed in this paper can be
used for all group contribution methods or group contribution equations of state.

Acknowledgements
The authors thank BMWi, Arbeitsgemeinschaft Industrieller Forschungsvereinigungen AIF. ,
Project No. 10931Nr1, and K.-C. Wong Foundation for financial support.

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