A MODIFIED PENGROBINSON EQUATION OF STATE FOR

PHASE EQUILIBRIUM CALCULATION OF LIQUEFIED,

SYNTHETIC NATURAL GAS, AND GAS CONDENSATE
MIXTURES
Ali Haghtalab,* Peyman Mahmoodi and Seyed Hossein Mazloumi
Department of Chemical Engineering, Tarbiat Modares University, PO Box 14115-143, Tehran 123, Iran

A modied PengRobinson equation of state, MPR2 EOS, is introduced by incorporating a new alpha function and a temperature dependent
function for covolume, b. The modied cubic EOS has three input per each substance: critical temperature, critical pressure, and acentric factor.
The coefcients of temperature dependence of the alpha and beta functions, relating to the parameters a and b of the new cubic EOS, are
obtained by simultaneous tting of saturated experimental vapour pressure and liquid density data for several pure components. The percent
absolute average deviation (AAD%) of 1.38, 4.80 and 2.89 are obtained to correlation of the saturation vapour pressure, liquid density and vapour
volume, respectively. Also the ADD% of 2.575 is computed for prediction of saturation enthalpy of vapourisation of the pure compounds. For
calculation of phase equilibrium of mixture, the modied PR EOS is used for prediction of liquid density of the LNG mixtures. Also the new EOS is
applied for construction of the phase envelop of synthetic natural gas, SNG, mixtures and calculation vapourliquid equilibria of gas condensates.
The results demonstrate that the new MPR2 EOS can be used for calculation of vapourliquid equilibrium of pure components and mixtures with
good accuracy.
Une e quation de Peng-Robinson modiee de lEtat, EOS MPR2, est introduit en integrant une fonction nouvelle alpha et une fonction dependant
de la temperature de covolume, b. LEOS modication de cube a trois entrees pour chaque substance: la temperature critique, pression critique
et le facteur acentrique. Les coefcients de dependance de la temperature des fonctions alpha et beta, relatives aux param`etres a et b de lEOS
nouveaux cubes, sont obtenus par montage simultane de donnees experimentales de plusieurs composants purs a` saturation. Lecart moyen
absolu pour cent (AAD%) de 1,35, 3,09 et 2,22 sont obtenus a` la correlation de la pression de vapeur saturante, la densite du liquide et le volume
de vapeur, respectivement. Aussi lADD de 2,21% est calcule pour la prevision de la saturation et de lenthalpie de vaporisation des composes
purs. LEOS modiee pour le calcul des e quilibres entre phases de melange est utilise pour la prediction de la densite de liquides, des melanges
de GNL. Aussi lEOS MPR2 nouvelle methode est appliquee pour la construction de la phase de lenveloppe de gaz naturel de synth`ese, SNG,
des melanges. Les resultats demontrent que lEOS MPR2 nouvelle peut e tre utilise pour le calcul de lequilibre liquide-vapeur des corps purs et
melanges avec une bonne precision.
Keywords: modied PengRobinson, cubic equation of state, new alpha function, temperature-dependent covolume, vapourliquid equilibrium

INTRODUCTION

quation of state is widely used in phase equilibrium

calculation to design of many processes in chemical, petrochemical, and natural gas industries. PengRobinson cubic
equation of state (Peng and Robinson, 1976) is one of the most
popular EOSs in calculation of the phase equilibrium for hydrocarbon and non-hydrocarbon systems. However, this EOS has some
known defects, such as poor prediction of liquid density of pure
component and mixtures, low accurate prediction of vapour pressure of heavy hydrocarbons and relatively poor estimation of dew

1376

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

point of natural gas mixtures. Generally, for improvement calculation of liquid density, there are two paths for modication of
cubic equation of state that are using volume translated method

Author to whom correspondence may be addressed.

E-mail address: haghtala@modares.ac.ir
Can. J. Chem. Eng. 89:13761387, 2011
2011 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20519
Published online 21 April 2011 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 89, DECEMBER 2011

and introducing a temperature dependent function for covolume,

b (Orbey and Sandler, 1998). Several cubic EOSs (Peneloux et al.,
1982; Magoulas and Tassios, 1990; Tsai and Chen, 1998; Ahlers
and Gmehling, 2001; Lin and Duan, 2005) were incorporated
the concept of volume translated and improved the accuracy of
liquid density for pure components; however, this method introduces an additional parameter that leads to an extra mixing rule.
On the other hand, there are many equations of state in which
uses the different temperature functions for covolume parameter
(Fuller, 1976; Heyen, 1981; Xu and Sandler, 1987; Moshfeghian
et al., 1988; Nasrifar and Moshfeghian, 2001; Mohsen-Nia et al.,
2003; Dashtizadeh et al., 2006) to calculate the liquid density
accurately.
In addition, the empirical correlations are also used in calculation of liquid densities for different saturated components and
compressed hydrocarbon liquids. These methods such as Rackett (1970) and COSTALD (Hankinson and Thomson, 1979), that
are convenient and accurate, have extensive application in the
petroleum industries.
Introducing Soaves alpha function in RK EOS signicantly
improved the capability of cubic EOS in calculation of vapour
pressure of pure components and mixtures. The various alpha
functions have been proposed for cubic EOSs that were extensively reviewed by the others (Twu et al., 1995; Poling et al.,
2000; Gasem et al., 2001). The recently proposed alpha functions have been improved the correlation of the vapour pressure
of heavy hydrocarbons and polar components so that no need
for switch function and correction of the limiting value at high
reduced temperatures. However, the poor calculation of liquid
density is still unresolved in the recently modied PengRobinson
EOS.
On the other hand, a variety of models using cubic equation of state have been proposed to correlation and prediction
of the phase equilibria of hydrocarbon mixtures specially those
containing asymmetric compounds. Jaubert and Mutelet (2004)
developed the Predictive PR78 EOS, PPR78, that is a combination of the modied group contribution of Abdoul et al. (1991)
and PR78 EOSs (Peng and Robinson, 1978) for estimation of the
temperature-dependent binary interaction parameter. This model
has been already applied for calculation of phase equilibrium
for various hydrocarbon and non-hydrocarbon systems such as
nitrogen, carbon dioxide, hydrogen sulphide (Jaubert et al., 2005,
2010; Mutelet et al., 2005; Vitu et al., 2006, 2008; Privat et al.,
2008a, 2008b, 2008c, 2008d). Louli et al. (2007) have developed
Universal Group Contribution Equation of State, UMR-PRU, for
prediction of the vapourliquid equilibria of asymmetric systems
with a volume-translated PengRobinson equation of state. Using
EOS/GE approach, Haghtalab and Mahmoodi (2010) applied the
UNIFAC-NRF group contribution model and modied PR EOS of
Twu et al. (1995) for accurate correlation and prediction of phase
behaviour of asymmetric and non-asymmetric systems.
In this work, considering the aforementioned advantages for
alpha function, a new alpha function for the parameter a together
with a linear temperature function for parameter b are implemented in which the input variables to the new EOS only are
critical temperature, critical pressure and acentric factor. The modied PengRobison, MPR2, improves accuracy of the correlation
of vapour pressure of heavy hydrocarbons and liquid density of
both pure components and mixtures. Moreover, the calculation of
dew and bubble point of some synthetic natural gas, SNGs, and gas
condensate presents more accurate results using the new MPR2
EOS in comparison to SRK EOS that is widely used in prediction
of the phase diagram for SNG.

VOLUME 89, DECEMBER 2011

MODIFIED PENGROBINSON EQUATION OF STATE

(MPR2)
The PR EOS in density form is presented as:
P=

a
2
RT

1b
1 + 2b
b2
2

(1)

where the attractive and repulsive parameters, a and b, for pure

components can be obtained using critical properties as:

R2 Tc2
a = 0.45724
Pc

RTc
b = 0.07780
Pc
(T) = (1 + k(1


(T)

(2)


(3)

Tr ))2

(4)

k = 0.37464 + 1.542260.269922

(5)

where R, Tc , Pc , and stand for gas constant, critical temperature,

critical pressure, and pitzer acentric factor, respectively.
The various relations have been proposed for the alpha function
(Twu et al., 1995; Poling et al., 2000; Gasem et al., 2001). This
function requires three characteristics as following: its value is
equal one at critical point, take nite value when temperature
tends to innity, and be positive for any temperature and it is valid
at the whole range of reduced temperature and acentric factor so
that no needs to use a switch function. For satisfaction of these
three conditions, Haghtalab et al. (2010) have proposed a new
alpha function as following:

(T) = exp (k4 + k5 Tr )(1(k6 + k7 + k8 2 )ln Tr )

(6)

where this alpha function is already used successfully for calculation the physical properties of pure uids and for prediction of
vapourliquid equilibria of hydrocarbon systems with the cubic
HKM three-parameter cubic equation of state (Haghtalab et al.,
2010). In this study, a shorter form of this alpha function is used
with PengRobinson equation of state, coupled by covolume temperature dependence parameter as following:

RTc
b = 0.07780
Pc


(T)

(7)

where a linear temperature dependence relation for beta function

(Trebble and Bishnoi, 1986; Moshfeghian et al., 1988) is applied
as:
(T) = (1 + m(1Tr ))

(8)

where the parameter m is a function of acentric factor. In the

alpha function proposed by Haghtalab et al. (2010), for simplication, the rst term in Equation (6) is neglected so that the new
alpha function is presented as:
(T) = exp(1nln Tr )

(9)

where the parameter n is a function of acentric factor as similar as

Equation (6). To obtain the functions n and m versus acentric factor, calculation of vapourliquid equilibria were performed using

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

1377

Table 1. The pure compounds, critical constants, the number of experimental data points, the range of reduced temperature used in this work
Component
C1
C2
C3
n-C4
i-C4
n-C5
n-C6
n-C7
n-C8
n-C9
n-C10
n-C12
C2 H4
C2 H2
C3 H6
C6 H6
C6 H5 CH3
Ar
CHCl3
CF4
CCL4
CO2
CL2
CO
Ne
Xe
Kr
N2
SO2
F2
O2
CH3 C1
[(CF2 )4 ]
CH3 CHF2
CH3 CF3
CH3 CClF2
CHF2 CF3
CHClFCF3
C2 CL3 F3
CH2 F2
CHCl2 F
CClF3
CCL2 F2
CCL3 F
H2 S
H2 O
CH4 O
C 2 H6 O
C 3 H6 O
Overall

Tc (K)

Pc (bar)

190.56
305.33
369.82
425.16
408.1
469.7
507.82
540.1
568.8
594.55
618.59
658.66
282.3
308.7
365.6
562.2
591.8
150.9
536.6
227.5
556.4
304.2
417.15
132.91
44.4
289.7
209.39
126.25
430.75
144.3
154.77
416
388.5
386.41
346.75
410
339.4
395.65
487.5
351.4
440
302
385
471.2
373.1
647.3
512.6
516.3
508.2

45.99
48.71
42.47
37.96
36.48
33.7
30.34
27.35
24.97
22.81
21.3
18.32
50.403
62.47
46.65
48.979
41.04
48.98
54.72
37.45
45.6
73.83
77.1
34.96
26.53
58.21
54.96
33.96
78.81
52.15
50.87
69
27.83
45.17
38.32
41.5
35.95
36.34
34.11
57.927
43.26
38.7
41.31
44.09
90
221.2
80.95
63.9
47.61

0.0113
0.1004
0.1542
0.2004
0.181
0.251
0.304
0.346
0.396
0.446
0.4885
0.5746
0.086
0.188
0.137
0.209
0.262
0
0.228
0.174
0.191
0.224
0.073
0.048
0.038
0
0
0.037
0.244
0.053
0.02
0.154
0.352
0.274
0.253
0.239
0.293
0.281
0.252
0.27
0.232
0.167
0.178
0.187
0.096
0.343
0.566
0.643
0.307

np

Tr range

19
15
17
20
17
57
30
11
12
30
14
28
12
12
19
25
20
13
14
10
27
14
19
8
9
12
11
13
20
15
17
35
19
21
18
21
18
17
25
15
19
17
21
17
38
40
18
19
18
956

0.500.97
0.520.98
0.510.95
0.540.99
0.540.98
0.401.00
0.410.98
0.570.74
0.600.98
0.500.99
0.550.94
0.570.98
0.570.96
0.650.97
0.520.98
0.550.98
0.510.98
0.560.96
0.520.99
0.570.97
0.500.97
0.720.99
0.530.97
0.720.98
0.590.95
0.590.97
0.550.96
0.510.95
0.530.98
0.490.97
0.480.97
0.490.99
0.510.98
0.490.98
0.520.98
0.490.98
0.510.97
0.590.99
0.490.98
0.600.97
0.570.98
0.430.99
0.470.99
0.510.98
0.500.93
0.490.96
0.630.97
0.600.95
0.650.98

Refs.
[a]
[a]
[a]
[a]
[a]
[b]
[b]
[a]
[a]
[b]
[a]
[b]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]
[a]

[a] Perry and Green (1988). [b] National institute of standard and technology (NIST). Standard Reference Database Number 69 June (2005), available from
(webbook.nist.gov/chemistry/uid).

the saturated vapour pressure experimental data of 53 pure components and liquid density of the same 49 pure components. Thus,
the following relations are obtained for n and m, respectively, as:
n = 1.7309 + 1.6571 + 0.15542

(10)

m = 0.24760.8857 + 0.19002

(11)

The critical properties and acentric factor of pure compounds

used to optimisation of the adjustable parameter are given in Table
1. In this study for comparison, the new alpha function, Equation

1378

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

(9), with the SRK, PR, modied PR of Gasem et al. (2001); and
Coquelet et al. (2004) are investigated. In this text, the last two
EOSs are called GPR and CPR EOSs, respectively. The CPR alpha
function is expressed as:
(T) = exp(k1 (1Tr ))(1 + k2 (1

Tr )2 + k3 (1

Tr )3 )2

Tr < 1
(12)

(T) = exp(k1 (1Tr ))

Tr > 1

(13)

VOLUME 89, DECEMBER 2011

Table 2. The percent absolute average deviation (AAD% ) in calculation of vapour pressure and liquid density for pure components by different
equations of state
Vapour pressure
Component
C1
C2
C3
n-C4
i-C4
n-C5
n-C6
n-C7
n-C8
n-C9
n-C10
n-C12
C 2 H4
C 2 H2
C 3 H6
C 6 H6
C6 H5 CH3
Ar
CHCl3
CF4
CCL4
CO2
CL2
CO
Ne
Xe
Kr
N2
SO2
F2
O2
CH3 C1
[(CF2 )4 ]
CH3 CHF2
CH3 CF3
CH3 CClF2
CHF2 CF3
CHClFCF3
C2 CL3 F3
CH2 F2
CHCl2 F
CClF3
CCL2 F2
CCL3 F
H2 S
H2 O
CH4 O
C 2 H6 O
C 3 H6 O
Overall

AAD =

100
np

PR


 P
i

0.639
0.349
0.834
0.515
1.079
2.148
1.594
1.652
1.566
1.259
1.749
12.029
0.637
1.482
1.462
0.897
1.318
0.306
3.956
1.380
1.525
0.712
1.411
0.161
1.023
1.072
0.579
0.667
2.390
0.432
1.569
2.622
1.447
0.424
1.386
3.980
1.065
0.833
1.458
1.091
1.714
2.771
1.758
1.031
2.125
3.330
1.876
0.725
2.118
1.636

exp
cal
Pi
i
exp
Pi




Liquid density

PR78

SRK

CPR

GPR

MPR2

0.639
0.349
0.834
0.515
1.079
2.148
1.594
1.652
1.566
1.259
1.749
7.577
0.637
1.482
1.462
0.897
1.318
0.306
3.956
1.380
1.525
0.712
1.411
0.161
1.023
1.072
0.579
0.667
2.390
0.432
1.569
2.622
1.447
0.424
1.386
3.980
1.065
0.833
1.458
1.091
1.714
2.771
1.758
1.031
2.125
3.330
1.491
2.042
2.118
1.564

1.826
1.426
1.101
1.241
0.723
1.755
2.996
0.652
1.781
1.868
2.110
1.981
0.799
2.259
0.881
0.667
1.148
1.640
4.293
1.375
0.935
0.390
0.820
0.642
1.534
0.800
1.458
1.187
2.084
1.897
1.540
1.871
1.131
2.082
1.485
5.718
2.070
1.173
0.728
1.992
0.680
1.366
0.951
0.809
1.169
5.913
2.565
1.914
1.725
1.656

2.054
1.057
0.947
0.424
1.068
0.451
1.623
1.996
1.784
0.557
1.046
2.639
0.861
1.366
0.924
0.809
1.040
2.597
4.137
1.201
1.178
0.746
1.145
1.157
2.317
1.484
2.297
1.632
2.286
1.557
1.290
1.826
1.461
0.669
1.293
4.299
1.533
1.032
1.055
1.247
1.719
1.991
1.202
0.785
1.211
4.249
1.721
1.872
1.922
1.566

0.976
0.373
0.481
0.657
0.956
1.269
0.662
2.340
2.024
0.762
1.323
3.294
0.547
1.687
1.555
1.133
1.626
1.084
3.553
1.756
1.760
0.184
1.100
0.134
0.939
0.297
0.722
0.213
2.872
0.775
0.407
2.656
1.485
0.877
1.897
4.434
1.548
1.504
1.494
1.768
1.702
2.587
1.683
1.261
1.831
3.944
1.916
1.680
1.729
1.499

1.009
0.757
0.823
0.653
1.054
1.766
1.741
0.563
1.234
1.086
1.468
5.985
0.351
1.539
0.797
0.777
0.919
1.050
4.445
1.091
1.148
0.900
0.701
0.227
0.977
0.403
0.680
0.419
1.943
1.006
0.455
1.781
1.015
0.768
0.819
4.344
1.066
0.460
1.188
0.904
1.510
1.925
1.244
0.803
1.191
4.198
2.155
1.775
2.305
1.376

PR78

8.914
6.612
5.209
4.921
5.136
3.608
2.695
0.687
5.905
6.859
5.930
8.021
6.206
4.194
6.623
3.170
2.446
10.343
6.670
6.136
4.247
3.162
4.086
7.232
13.332
7.213
9.254
9.789
2.328
9.491
10.611
4.790
5.619
8.597
5.556
3.338
2.928
4.346
4.948
17.405
17.075
6.229
5.529
10.576
7.237
18.437
17.606
7.715
13.647
7.196

8.914
6.612
5.209
4.921
5.136
3.608
2.695
0.687
5.905
6.859
5.930
7.954
6.206
4.194
6.623
3.170
2.446
10.343
6.670
6.136
4.247
3.162
4.086
7.232
13.332
7.213
9.254
9.789
2.328
9.491
10.611
4.790
5.619
8.597
5.556
3.338
2.928
4.346
4.948
17.405
17.075
6.229
5.529
10.576
7.237
18.437
17.527
7.572
13.647
7.190

SRK
4.423
7.723
7.956
10.427
9.601
11.707
12.757
12.135
16.754
17.517
16.812
18.305
7.209
11.425
7.125
11.211
13.269
3.618
8.101
7.795
10.489
10.882
9.498
6.755
4.193
6.436
3.822
3.459
12.978
3.879
3.369
10.500
8.243
19.101
16.437
9.331
12.036
12.060
9.629
26.989
26.690
8.594
8.709
12.061
5.217
27.788
27.146
18.358
23.670
11.718

CPR
9.203
6.691
5.240
4.913
5.148
3.612
2.680
0.712
5.930
6.852
5.915
7.907
6.324
4.175
6.682
3.157
2.438
10.724
6.666
6.156
4.242
3.148
4.170
7.426
13.995
7.509
9.577
10.037
2.318
9.661
10.913
4.809
5.599
8.600
5.554
3.333
2.922
4.323
4.939
17.414
17.066
6.252
5.547
10.602
7.398
18.440
17.554
7.583
13.672
7.260

GPR
8.997
6.611
5.190
4.909
5.105
3.629
2.711
0.729
5.983
6.896
5.948
7.941
6.205
4.191
6.601
3.164
2.476
10.444
6.632
6.100
4.248
3.122
4.103
7.243
13.527
7.292
9.354
9.843
2.370
9.528
10.692
4.782
5.596
8.669
5.635
3.312
2.944
4.337
4.932
17.486
17.153
6.209
5.510
10.533
7.229
18.481
17.594
7.638
13.749
7.216

MPR2
2.439
2.857
2.300
3.390
3.339
2.901
2.754
0.658
4.389
4.159
3.238
0.759
2.288
3.214
3.284
2.061
2.898
3.633
5.330
3.854
2.555
2.419
2.731
4.064
5.501
2.073
2.250
3.454
2.724
3.682
3.603
2.683
6.757
9.090
6.482
2.142
2.868
4.143
4.074
17.866
18.182
3.501
3.117
8.076
2.263
17.502
13.642
4.622
13.520
4.803

where the k1 , k2 , and k3 are written in terms of acentric factor. In

this study, it should be pointed out that the adjustable parameters
of the CPR equation were correlated again using the same database
as follows:
k1 = 0.41287 + 1.34494 + 0.00421
k2 = 0.03982 + 0.085511.055212

PR

VOLUME 89, DECEMBER 2011

(14)
(15)

k3 = 0.01871 + 1.93328

(16)

RESULTS AND DISCUSSION

To demonstrate the accuracy of the modied PR EOS, calculation
of some thermodynamic properties of pure components and mixtures are carried out. Table 2 presents the percent absolute average

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

1379

deviation, AAD%, to correlation of the vapour pressure and liquid

density of 49 pure components using the new MPR2, original PR,
PR78, CPR, GPR, and SRK equations of state. The results present
that the new MPR2 EOS is more accurate in comparison to original
PR, PR78, CPR, GPR, and SRK EOSs. As one can see a signicant
improvement is achieved in calculation of the liquid density of
pure components.
Table 3 presents the deviation of results with experiment for
calculation of the vapour molar volume and the enthalpy of

vapourisation for the same pure components using the MPR2,

original PR, PR78 CPR, GPR, and SRK EOSs. It can be observed
that the best results are achieved by the original SRK and PR EOSs
in calculating of vapour molar volume and enthalpy of vapourisation, respectively. Table 4 shows the results of the vapour pressure
calculation of heavy hydrocarbons using the ve cubic EOSs. A
notable improvement has been achieved by new modied PR EOS
respect to the original PR EOS, however its results are not as well
as the CPR and GPR EOSs.

Table 3. The percent absolute average deviation (AAD%) in calculation of vapour volume and enthalpy of vapourisation for pure components by
different equations of state
Vapour volume
Component
C1
C2
C3
n-C4
i-C4
n-C5
n-C6
n-C7
n-C8
n-C9
n-C10
n-C12
C 2 H4
C 2 H2
C 3 H6
C 6 H6
C6 H5 CH3
Ar
CHCl3
CF4
CCL4
CO2
CL2
CO
Ne
Xe
Kr
N2
SO2
F2
O2
CH3 C1
[(CF2 )4 ]
CH3 CHF2
CH3 CF3
CH3 CClF2
CHF2 CF3
CHClFCF3
C2 CL3 F3
CH2F2
CHCl2 F
CClF3
CCL2 F2
CCL3 F
H2 S
H2 O
CH4 O
C 2 H6 O
C 3 H6 O
Overall

1380

Enthalpy of vapourisation

PR

PR78

SRK

CPR

GPR

MPR2

PR

PR78

SRK

CPR

GPR

MPR2

1.004
0.959
1.278
1.059
1.190
2.231
2.037
1.757
1.971
1.644
1.733
9.108
1.170
1.241
1.452
1.150
2.543
1.568
4.461
1.666
2.244
1.449
3.035
6.501
1.513
2.496
1.897
1.340
2.572
1.276
2.168
4.978
1.773
1.677
1.563
5.591
1.473
1.358
2.247
6.712
3.946
3.125
2.762
1.242
1.988
4.573
6.005
17.052
3.253
2.837

1.004
0.959
1.278
1.059
1.190
2.231
2.037
1.757
1.971
1.644
1.733
6.548
1.170
1.241
1.452
1.150
2.543
1.568
4.461
1.666
2.244
1.449
3.035
6.501
1.513
2.496
1.897
1.340
2.572
1.276
2.168
4.978
1.773
1.677
1.563
5.591
1.473
1.358
2.247
6.712
3.946
3.125
2.762
1.242
1.988
4.573
7.229
15.867
3.253
2.786

2.288
1.504
1.272
1.203
0.641
2.008
3.928
0.503
2.268
2.570
2.883
2.280
0.574
1.400
0.404
0.735
1.870
2.262
4.692
0.893
0.919
1.383
1.350
5.025
1.106
1.023
2.181
1.479
1.902
2.149
1.652
3.059
1.332
3.432
2.134
7.690
1.992
1.805
1.072
7.686
3.034
1.152
1.540
0.816
0.283
7.427
7.521
16.192
3.898
2.621

2.402
1.660
1.389
1.056
1.044
0.620
2.202
2.042
1.730
0.924
1.683
2.974
1.350
1.359
1.173
1.049
2.090
3.687
4.583
1.624
1.922
1.438
1.579
6.069
3.038
2.007
2.957
2.036
2.479
2.256
2.004
4.175
1.763
1.775
1.297
6.029
1.948
1.184
1.792
6.561
3.915
2.556
2.299
1.001
1.381
5.367
6.773
16.161
3.056
2.724

1.562
1.078
0.924
0.890
1.448
1.167
1.021
2.380
1.815
0.890
1.530
3.100
1.084
0.912
1.560
1.145
2.599
2.394
4.457
1.599
2.248
0.907
2.751
6.494
1.602
1.651
2.151
1.178
2.661
1.788
1.405
5.071
1.790
1.097
1.176
5.300
2.194
1.079
2.005
5.906
4.631
3.048
2.616
1.584
1.750
4.595
6.579
16.402
2.896
2.615

1.949
1.542
1.344
1.372
1.178
2.003
2.235
0.899
2.231
1.667
2.471
5.375
1.190
1.487
1.127
1.133
2.322
2.690
5.011
1.535
2.019
1.573
2.777
7.046
2.372
2.653
2.495
1.542
2.227
2.156
1.821
4.393
1.504
2.139
1.490
6.222
1.554
1.488
2.115
7.133
3.638
2.661
2.519
1.083
1.484
5.692
7.275
16.401
3.406
2.891

1.442
1.739
1.014
2.068
1.220
2.191
1.607
0.591
3.258
1.744
1.890
2.556
1.233
3.795
1.678
1.309
2.930
1.267
4.316

2.074
1.160
3.180
1.885
1.343
2.484
1.874
1.690
1.116
1.841
2.116
2.453

2.230
1.891

2.151
6.010
2.347
6.502
6.676
3.588
2.416
1.470

2.350

1.442
1.739
1.014
2.068
1.220
2.191
1.607
0.591
3.258
1.744
1.890
2.277
1.233
3.795
1.678
1.309
2.930
1.267
4.316

2.074
1.160
3.180
1.885
1.343
2.484
1.874
1.690
1.116
1.841
2.116
2.453

2.230
1.891

2.151
6.010
2.347
6.502
6.676
3.588
2.416
1.470

2.343

2.513
2.755
1.400
2.944
1.336
2.310
2.099
1.199
4.163
2.165
2.761
1.610
1.659
4.425
1.695
1.398
3.266
2.558
4.665

1.908
1.738
1.985
1.878
2.821
2.511
2.493
2.711
1.164
1.980
2.654
2.853

3.342
2.755

1.926
6.891
2.434
7.388
5.950
3.274
2.463
1.402

2.718

1.447
1.728
0.863
1.890
1.125
1.520
1.541
0.122
3.203
1.454
1.996
1.423
1.184
3.669
1.572
1.105
2.465
1.734
4.335

1.805
1.036
2.352
1.239
2.580
1.524
1.421
1.297
0.886
1.569
1.482
2.253

2.414
1.807

2.264
5.865
1.904
6.545
6.588
3.222
2.074
1.203

2.139

1.881
1.899
0.757
2.153
1.011
1.604
1.252
0.249
3.256
1.481
1.849
1.342
1.065
3.784
1.406
1.289
2.658
1.759
4.709

1.803
1.006
2.880
1.761
2.060
1.998
1.808
2.035
0.729
1.309
2.043
2.188

2.355
1.733

2.440
5.953
2.090
6.316
6.895
3.268
2.122
1.265

2.231

2.451
1.942
0.963
2.194
1.156
2.272
1.827
0.544
3.720
2.049
2.591
2.652
1.410
3.911
1.605
1.314
2.976
2.135
4.343

2.042
1.271
3.436
2.647
2.179
3.171
2.416
2.442
1.080
1.988
2.683
2.428

2.453
2.021

1.985
6.239
2.379
6.694
6.603
3.555
2.415
1.410

2.575

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 89, DECEMBER 2011

Table 4. The percent absolute average deviation (AAD%) in vapour pressure calculation of heavy hydrocarbons by different equations of state
AAD% in P
np

Tr range

Refs.

Tc (K)

Pc (bar)

PR

PR78

SRK

CPR

GPR

MPR2

10
11
16
10
26
20
16
17
23
21
21
29
32
252

0.500.76
0.620.76
0.540.85
0.520.78
0.590.77
0.540.81
0.640.77
0.550.79
0.500.76
0.510.75
0.470.61
0.510.82
0.560.76

[a]
[b]
[c]
[a]
[d]
[c]
[e]
[c]
[d]
[d]
[f]
[g]
[c]

692.17
692.17
692.17
720.67
720.67
720.67
720.67
745.25
745.25
766.66
766.66
766.66
766.66

15.92
15.92
15.92
13.94
13.94
13.94
13.94
12.29
12.29
10.91
10.91
10.91
10.91

0.6572
0.6572
0.6572
0.7368
0.7368
0.7368
0.7368
0.8137
0.8137
0.8883
0.8883
0.8883
0.8883

2.207
3.202
4.151
8.517
12.285
6.706
4.727
9.450
9.901
20.823
34.731
17.563
13.662
11.379

3.452
0.217
0.768
4.179
5.038
0.630
0.199
0.542
3.510
4.782
6.782
2.453
0.593
2.549

6.435
1.058
1.719
2.870
1.470
1.732
0.850
1.909
4.887
4.433
3.417
1.372
1.209
2.566

5.085
0.299
0.321
3.035
3.084
0.384
0.367
0.682
3.726
4.741
1.303
1.229
0.767
1.925

4.498
0.297
0.787
3.486
3.349
0.458
0.275
0.824
3.987
3.794
4.231
1.334
0.428
2.134

5.153
0.838
1.171
3.192
2.383
1.374
0.915
1.836
3.879
5.038
3.329
2.380
1.855
2.565

Compound
n-C14

n-C16

n-C18
n-C20

Overall

[a] Stull (1947). [b] Camin and Rossini (1955). [c] Morgan and Kobayashi (1989). [d] Myers and Fenske (1955). [e] Camin et al. (1954). [f] Sasse et al. (1988).
[g] Chirico et al. (1989).

Figure 1 shows the limit of the new alpha function at high temperatures that approaches to an asymptote which is the theoretical
limiting behaviour of alpha function, as mentioned by the others
(Gasem et al., 2001); however, the alpha function of original PR
EOS does not obey this correct feature.

Table 5 shows the predicted liquid density of compressed

methane using the new MPR2, original PR and SRK EOSs. As
one can observe the overall AAD% of the new EOS is less than
SRK and PR EOSs. Table 6 presents the prediction of liquid density for the binary systems by PR, SRK, and the new MPR2 EOSs.

Table 5. The percent absolute average deviation (AAD%) in liquid density prediction of compressed methane by various equations of state,
experimental data (Vennix et al., 1970; Rodosevich and Miller, 1973)
Dev%
Temp (K)
91
100.15
108.05
114.94
150.3
151.807
153.619
155.457
168.735
180.089
188.496
159.295
172.744
176.864
181.641
189.751
168.227
170.158
172.545
178.454
186.819
175.605
178.055
182.805
182.805
188.261
Total AAD%

Dev% =

cal
exp

exp

P (bar)

exp (kg/m3 )

PR

SRK

MPR2

0.52
0.56
0.95
1.55
14.757
27.698
43.24
58.309
171.383
266.271
335.421
19.589
116.019
145.434
179.513
236.731
29.564
41.084
55.272
90.637
140.828
31.599
43.229
65.97
65.943
92.321

451.031
438.779
427.699
417.697
360
360
360
360
360
360
360
341
341
341
341
341
321
321
321
321
321
297
297
297
297
297

12.76
12.74
12.61
12.37
8.17
8.32
8.49
8.58
9.45
9.91
10.14
6.12
7.56
7.87
8.19
8.60
3.78
4.13
4.50
5.31
6.19
0.24
0.90
1.95
1.94
2.91
7.07

0.21
0.06
0.18
0.49
4.50
4.25
3.97
3.76
2.31
1.52
1.09
6.26
4.07
3.61
3.13
2.50
8.11
7.61
7.08
5.97
4.78
11.02
10.14
8.79
8.80
7.61
4.68

0.16
1.08
1.77
2.26
2.13
2.57
3.08
3.50
6.48
8.52
9.87
1.18
5.04
5.97
6.98
8.50
0.07
0.84
1.69
3.53
5.67
2.54
1.28
0.72
0.71
2.56
3.41

VOLUME 89, DECEMBER 2011

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

1381

Figure 1. Comparison of asymptotic behaviour of the new alpha function and the original alpha function of PR EOS for ethane.

Table 6. The percent absolute average deviation (AAD%) in liquid density and vapour pressure prediction of binary systems by different equations
of state, experimental data from Hiza et al. (1977)
AAD%
Liquid density

Vapour pressure

Comp. 1

Comp. 2

PR

SRK

MPR2

PR

SRK

MPR2

N2
N2
N2
CH4
CH4
CH4
CH4
C2 H 6
C2 H 6
C2 H 6
C3 H 8
C3 H 8
i-C4 H10
Overall

CH4
C 2 H6
C 3 H8
C 2 H6
C 3 H8
i-C4 H10
nC4 H10
C 3 H8
i-C4 H10
n-C4 H10
i-C4 H10
n-C4 H10
n-C4 H10

12.61
7.43
3.29
9.65
8.48
5.22
8.67
5.66
5.09
4.44
2.86
2.97
2.21
6.04

0.89
4.24
7.71
2.55
3.54
6.17
3.51
5.79
6.23
6.82
8.18
8.08
8.70
5.57

3.34
3.75
5.77
1.49
1.88
3.17
1.46
3.96
4.54
4.25
5.08
4.43
4.46
3.66

10.27
49.36
76.20
3.69
8.11
22.61
30.97

28.74

9.23
42.25
72.21
4.85
9.59
23.06
31.35

27.51

13.35
60.34
80.15
4.84
7.97
21.62
30.64

31.27

Without using coupling interaction parameter, the classical quadratic mixing rules were applied for calculations of
vapourliquid equilibrium of the binary systems. As one can see
from Table 6, the present EOS predicts the liquid density with better accuracy respect to the other EOSs; however in spite of the

vapour pressure was predicted better by PR but the AAD% of

three EOSs is high. The new MPR2 EOS is applied for the LNG
mixtures that are shown by Table 7. The results of prediction of
the liquid density of LNG mixtures have been presented in Table
8. Thus as one can see from this table, the results of liquid density

Table 7. Composition of LNG mixtures used for liquid density prediction, experimental data from Hiza and Haynes (1980)
Mixture
A1
A2
B
C1
C2
D
E
F
G
H

1382

x(N2 )

x(CH4 )

x(C2 H6 )

x(C3 H8 )

x(i-C4 H10 )

x(n-C4 H10 )

0.338
0.1635
0.099
0.0484
0.049
0.0554
0.0425

0.34242
0.80284
0.85443
0.3414
0.6704
0.7977
0.8526
0.806
0.7909
0.813

0.31372
0.09902
0.05042
0.3206
0.1661

0.0483
0.0468
0.056
0.0475

0.34386
0.09814
0.04038

0.1028
0.0507
0.0482
0.05
0.0487

0.02577

0.05

0.0241

0.02901

0.0477
0.0242

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 89, DECEMBER 2011

Table 8. The percent absolute average deviation (AAD%) in liquid density and vapour pressure prediction of LNG mixtures by various equations of
state, experimental data from Hiza and Haynes (1980)
AAD%
Liquid density

Vapour pressure

Mixture

PR

SRK

MPR2

PR

SRK

MPR2

A
B
C
D
E
F
G
H
Overall

8.31
10.38
12.09
11.57
11.81
10.80
10.69
10.69
10.79

3.63
1.98
0.56
1.03
0.84
1.63
1.65
1.72
1.63

2.21
0.62
1.79
0.99
0.74
0.55
0.36
0.55
0.98

9.72
3.20
21.16
25.09
19.61
28.44
28.06
35.31
21.32

10.98
6.20
17.51
22.80
18.50
26.84
26.05
34.05
20.37

9.92
3.25
28.58
30.98
24.60
33.25
33.57
39.45
25.45

by the new MPR2 are in very good agreement with experimental

data. However, the results of the vapour pressure are not as well
as liquid density, although the PR prediction of vapour pressure
is better than the new EOS. This can be explained that the depen-

dence of covolume parameter on temperature in the new modied

PR has signicant inuence in prediction of liquid density.
To demonstrate the capability of the present EOS in construction
of the phase diagrams, ve synthetic natural gases (SNGs) were

Table 9. Composition of different SNGs and gas condensates used in this work

Nitrogen
Carbon dioxide
Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane
n-Hexane
n-Heptane
n-Octane
C7+
Mw of C7+
SG of C7+
Reference

SNG 1

SNG 2

SNG 3

SNG 4

SNG 5

Gas condensate 1

Gas condensate 2

Gas condensate 3

0.00000

0.84280
0.10067
0.04028
0.00597
0.01028

[a]

0.00000

0.93600
0.02630

0.01490
0.01490

0.00795

[a]

0.000

0.890
0.070

0.040

[b]

0.004800

0.887634
0.085400
0.016800
0.002200
0.002900
0.000182
0.000084

[c]

0.006180
0.001870
0.989430
0.000820
0.000650
0.000500

0.000170

0.000320
0.000027
0.000033

[d]

0.0075
0.03912
0.70203
0.0922
0.02759
0.00662
0.00981
0.00402
0.00422
0.00816

0.09873
192.8
0.8030
[e]

0.0034
0.0217
0.7064
0.1076
0.0494
0
0.0302
0
0.0135
0.009

0.0588
153.0
0.810
[f]

0.0042
0.0061
0.5753
0.1345
0.0752
0
0.0415
0
0.0233
0.0179

0.1220
193.0
0.8115
[f]

[a] Morch et al. (2006). [b] Blanco et al. (2000). [c] Avila et al. (2002a). [d] Avila et al. (2002b). [e] Yang et al. (1997). [f] Coats and Smart (1986).

Table 10. The percent absolute average deviation (AAD%) in bubble and dew point prediction of heavy gas condensate reservoir uid
Exp

%AAD(P)

Mixture

T (K)

P (bar)

PR

SRK

MPR2

Data type

Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 1
Gas condensate 2
Gas condensate 3
Overall

313.5
333.2
352.8
371.6
390.5
410.1
429.5
450.3
408.7
360.9

450.2
458.9
465.3
466.8
460.7
453.1
446.6
428.8
334.7
305.3

31.963
28.018
24.938
22.211
19.015
16.222
14.391
11.311
11.703
12.125
19.190

27.231
23.063
19.692
16.599
12.912
9.573
7.184
3.119
4.260
15.801
13.944

17.186
15.759
14.655
13.304
11.115
9.097
8.173
5.410
5.886
10.748
11.133

Bubble point
Bubble point
Bubble point
Bubble point
Dew point
Dew point
Dew point
Dew point
Dew point
Bubble point

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chosen that their compositions are given in Table 9. The rst 3

SNGs are consisting of only hydrocarbons without CO2 and N2 .
The SNG mixtures of 4 and 5 contain N2 and the last ones (SNG5)
include both CO2 and N2 . Applying the three EOSs for the SNG
mixtures using classical mixing rules with kij = 0, the dew point
calculations are carried out so that the results are shown in Figure
2. In most cases the results of the present MPR2 EOS are in better
agreement with experimental data, particularly, at high pressures.
Table 9 shows the percent absolute average deviation (AAD%)
in bubble and dew point prediction of gas condensate reservoir uids. In addition, the compositions of the gas condensates mixtures

are given in Table 9. The heavy ends of these mixtures are characterised by Pedersen et al. (1992) splitting method. Each fraction
is divided to 14 single carbon number, SCN, the properties of the
SCN are determined by Whitson (1983) SCN generalised properties and nally KeslerLee correlation (Kesler and Lee, 1976) is
used for nding the critical properties of the SCN groups. As it is
presented in Table 10, the present model shows better accuracy
in prediction of vapourliquid equilibria of the gas condensate
mixtures.
Finally, it should be pointed out the use of the MPR2 EOS, that
utilises a linear temperature function for covolume, can generate

Figure 2. Comparison of phase envelope prediction of various SNGs with different EOSs and experimental data.

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VOLUME 89, DECEMBER 2011

Figure 2. (Continued )

some unphysical results at high pressures and temperatures. Negative values of covolume for substances with < 0.3 at Tr > 5,
crossing of isotherms at high temperatures and negative residual
isochoric heat capacity at very high pressures are the pitfalls of
the present EOS (Deiters and de Reuck, 1997; Polishuk, 2009).
Thus, the application of the present EOS at the temperatures and
pressures far from those encountered in chemical industry must
be carefully notied.

CONCLUSION
A modied PR EOS was introduced by considering a new temperature dependence function for the attractive parameter of a
and a linear temperature relation for the covolume parameter b.
The results of the new EOS (MPR2) for a large number of pure
components were presented for calculation of vapour pressure,
liquid density, vapour molar volume and enthalpy of vapourisation. While the modied PR EOS correlated the liquid density
of pure components with better accuracy, however the results of
vapour pressure (excluding heavy hydrocarbons), vapour molar
volume and enthalpy of vapourisation are almost the same using
both the new PR and the original PR. Also the new EOS demonstrated more accurate results for the vapour pressure of pure heavy
hydrocarbons than original PR. The results of the new modied
PR EOS for prediction of liquid density of a number of binaries
and the LNG mixtures showed a reasonable accuracy and compatible with both PR and SRK EOSs. In addition, the prediction
of the phase envelope of SNGs and dew and bubble points of gas

VOLUME 89, DECEMBER 2011

condensate mixtures using the modied PR EOS represented the

better accuracy than SRK and PR EOSs.

Notation
a
b
H
m,n
N
np
p
R
T
V
x
y

attraction parameter (Pam6 mol1 )

molar co-volume (m3 mol1 )
enthalpy (J mol1 )
parameters in the new equation of state
number of compounds
number of experimental points
pressure (bar)
universal gas constant (8.314 J mol1 K1 )
temperature (K)
vapour volume
liquid phase mole fraction
vapour phase mole fraction

Greek Letters

alpha function
beta function
density (kg m3 )
Pitzer acentric factor

Subscripts
c critical
i,j indices
r reduced

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Superscripts
cal calculated
exp experimental

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Manuscript received May 15, 2010; revised manuscript

received July 16, 2010; accepted for publication October 7, 2010.

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