A MODIFIED PENG–ROBINSON 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 modified Peng–Robinson equation of state, MPR2 EOS, is introduced by incorporating a new alpha function and a temperature dependent
function for covolume, b. The modified cubic EOS has three input per each substance: critical temperature, critical pressure, and acentric factor.
The coefficients 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 fitting 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 modified 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 vapour–liquid equilibria of gas condensates.
The results demonstrate that the new MPR2 EOS can be used for calculation of vapour–liquid equilibrium of pure components and mixtures with
good accuracy.

Une équation de Peng-Robinson modifiée de l’Etat, EOS MPR2, est introduit en intégrant une fonction nouvelle alpha et une fonction dépendant
de la température de covolume, b. L’EOS modification de cube a trois entrées pour chaque substance: la température critique, pression critique
et le facteur acentrique. Les coefficients de dépendance de la température des fonctions alpha et bêta, relatives aux paramètres a et b de l’EOS
nouveaux cubes, sont obtenus par montage simultané de données expérimentales de plusieurs composants purs à saturation. L’écart moyen
absolu pour cent (AAD%) de 1,35, 3,09 et 2,22 sont obtenus à la corrélation de la pression de vapeur saturante, la densité du liquide et le volume
de vapeur, respectivement. Aussi l’ADD de 2,21% est calculé pour la prévision de la saturation et de l’enthalpie de vaporisation des composés
purs. L’EOS modifiée pour le calcul des équilibres entre phases de mélange est utilisé pour la prédiction de la densité de liquides, des mélanges
de GNL. Aussi l’EOS MPR2 nouvelle méthode est appliquée pour la construction de la phase de l’enveloppe de gaz naturel de synthèse, SNG,
des mélanges. Les résultats démontrent que l’EOS MPR2 nouvelle peut être utilisé pour le calcul de l’équilibre liquide-vapeur des corps purs et
mélanges avec une bonne précision.

Keywords: modified Peng–Robinson, cubic equation of state, new alpha function, temperature-dependent covolume, vapour–liquid equilibrium

INTRODUCTION point of natural gas mixtures. Generally, for improvement calcu-

E
quation of state is widely used in phase equilibrium
calculation to design of many processes in chemical, petro-
chemical, and natural gas industries. Peng–Robinson cubic
equation of state (Peng and Robinson, 1976) is one of the most
popular EOSs in calculation of the phase equilibrium for hydrocar-
bon 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 pres-
sure of heavy hydrocarbons and relatively poor estimation of dew
lation of liquid density, there are two paths for modification 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. 89:1376–1387, 2011
© 2011 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20519
Published online 21 April 2011 in Wiley Online Library
(wileyonlinelibrary.com).

| 1376 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, DECEMBER 2011 |
and introducing a temperature dependent function for covolume, MODIFIED PENG–ROBINSON EQUATION OF STATE
b (Orbey and Sandler, 1998). Several cubic EOSs (Péneloux et al., (MPR2)
1982; Magoulas and Tassios, 1990; Tsai and Chen, 1998; Ahlers
and Gmehling, 2001; Lin and Duan, 2005) were incorporated The PR EOS in density form is presented as:
the concept of volume translated and improved the accuracy of RTp ap2
liquid density for pure components; however, this method intro- P= − (1)
duces an additional parameter that leads to an extra mixing rule. 1−bp 1 + 2bp−b2p2
On the other hand, there are many equations of state in which
uses the different temperature functions for covolume parameter where the attractive and repulsive parameters, a and b, for pure
(Fuller, 1976; Heyen,and
1981; Xu and Sandler, components. can beΣ obtained using critical properties as:
et al., 1988; Nasrifar Moshfeghian, 2001;1987; Moshfeghian
Mohsen-Nia et al., R2 T 2
0 45724 ( ) (2)
2003; Dashtizadeh et al., 2006) to calculate the liquid density a=. c
˛T
accurately. Pc
In addition, the empirical correlations are also used in calcu-
. Σ
lation of liquid densities for different saturated components and RTc
b = 0.07780 (3)
compressed hydrocarbon liquids. These methods such as Rack- Pc
ett (1970) and COSTALD (Hankinson and Thomson, 1979), that
are convenient and accurate, have extensive application in the √
˛(T) = (1 + k(1− Tr))2 (4)
petroleum industries.
Introducing Soave’s alpha function in RK EOS significantly
k = 0.37464 + 1.54226ω−0.26992ω2 (5)
improved the capability of cubic EOS in calculation of vapour
pressure of pure components and mixtures. The various alpha
where R, Tc, Pc, and ω stand for gas constant, critical temperature,
functions have been proposed for cubic EOSs that were exten-
critical pressure, and pitzer acentric factor, respectively.
sively reviewed by the others (Twu et al., 1995; Poling et al.,
The various relations have been proposed for the alpha function
2000; Gasem et al., 2001). The recently proposed alpha func-
(Twu et al., 1995; Poling et al., 2000; Gasem et al., 2001). This
tions have been improved the correlation of the vapour pressure
function requires three characteristics as following: its value is
of heavy hydrocarbons and polar components so that no need
equal one at critical point, take finite value when temperature
for switch function and correction of the limiting value at high
tends to infinity, and be positive for any temperature and it is valid
reduced temperatures. However, the poor calculation of liquid
at the whole range of reduced temperature and acentric factor so
density is still unresolved in the recently modified Peng–Robinson
that no needs to use a switch function. For satisfaction of these
EOS.
three conditions, Haghtalab et al. (2010) have proposed a new
On the other hand, a variety of models using cubic equa-
alpha function as following:
tion of state have been proposed to correlation and prediction
of the phase equilibria of hydrocarbon mixtures specially those Σ Σ
containing asymmetric compounds. Jaubert and Mutelet (2004) ˛(T) = exp (k 4+ k T5 )(1−(k
r +6 k ω 7+ k ω2 )8 ln Tr ) (6)

developed the Predictive PR78 EOS, PPR78, that is a combina-

tion of the modified 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 vapour–liquid equilibria of asymmetric systems
with a volume-translated Peng–Robinson equation of state. Using
EOS/GE approach, Haghtalab and Mahmoodi (2010) applied the
UNIFAC-NRF group contribution model and modified 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 imple-
mented in which the input variables to the new EOS only are
critical temperature, critical pressure and acentric factor. The mod-
ified Peng–Robison, 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.
where this alpha function is already used successfully for calcu-
lation the physical properties of pure fluids and for prediction of
vapour–liquid 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 Peng–Robinson equation of state, coupled by covolume tem-
perature dependence parameter as following:
. Σ
RTc
b = 0.07780 ˇ(T) (7)
Pc
where a linear temperature dependence relation for beta function
(Trebble and Bishnoi, 1986; Moshfeghian et al., 1988) is applied
as:
ˇ(T) = (1 + m(1−Tr)) (8)
where the parameter m is a function of acentric factor. In the
alpha function proposed by Haghtalab et al. (2010), for simplifi-
cation, the first term in Equation (6) is neglected so that the new
alpha function is presented as:
˛(T) = exp(1−nln 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 fac-
tor, calculation of vapour–liquid equilibria were performed using

| VOLUME 89, DECEMBER 2011 | | 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 Tc (K) Pc (bar) ω np Tr range Refs.

C1 190.56 45.99 0.0113 19 0.50–0.97 [a]

C2 305.33 48.71 0.1004 15 0.52–0.98 [a]
C3 369.82 42.47 0.1542 17 0.51–0.95 [a]
n-C4 425.16 37.96 0.2004 20 0.54–0.99 [a]
i-C4 408.1 36.48 0.181 17 0.54–0.98 [a]
n-C5 469.7 33.7 0.251 57 0.40–1.00 [b]
n-C6 507.82 30.34 0.304 30 0.41–0.98 [b]
n-C7 540.1 27.35 0.346 11 0.57–0.74 [a]
n-C8 568.8 24.97 0.396 12 0.60–0.98 [a]
n-C9 594.55 22.81 0.446 30 0.50–0.99 [b]
n-C10 618.59 21.3 0.4885 14 0.55–0.94 [a]
n-C12 658.66 18.32 0.5746 28 0.57–0.98 [b]
C2H4 282.3 50.403 0.086 12 0.57–0.96 [a]
C2H2 308.7 62.47 0.188 12 0.65–0.97 [a]
C3H6 365.6 46.65 0.137 19 0.52–0.98 [a]
C6H6 562.2 48.979 0.209 25 0.55–0.98 [a]
C6H5CH3 591.8 41.04 0.262 20 0.51–0.98 [a]
Ar 150.9 48.98 0 13 0.56–0.96 [a]
CHCl3 536.6 54.72 0.228 14 0.52–0.99 [a]
CF4 227.5 37.45 0.174 10 0.57–0.97 [a]
CCL4 556.4 45.6 0.191 27 0.50–0.97 [a]
CO2 304.2 73.83 0.224 14 0.72–0.99 [a]
CL2 417.15 77.1 0.073 19 0.53–0.97 [a]
CO 132.91 34.96 0.048 8 0.72–0.98 [a]
Ne 44.4 26.53 −0.038 9 0.59–0.95 [a]
Xe 289.7 58.21 0 12 0.59–0.97 [a]
Kr 209.39 54.96 0 11 0.55–0.96 [a]
N2 126.25 33.96 0.037 13 0.51–0.95 [a]
SO2 430.75 78.81 0.244 20 0.53–0.98 [a]
F2 144.3 52.15 0.053 15 0.49–0.97 [a]
O2 154.77 50.87 0.02 17 0.48–0.97 [a]
CH3C1 416 69 0.154 35 0.49–0.99 [a]
[–(CF2)4–] 388.5 27.83 0.352 19 0.51–0.98 [a]
CH3CHF2 386.41 45.17 0.274 21 0.49–0.98 [a]
CH3CF3 346.75 38.32 0.253 18 0.52–0.98 [a]
CH3CClF2 410 41.5 0.239 21 0.49–0.98 [a]
CHF2CF3 339.4 35.95 0.293 18 0.51–0.97 [a]
CHClFCF3 395.65 36.34 0.281 17 0.59–0.99 [a]
C2CL3F3 487.5 34.11 0.252 25 0.49–0.98 [a]
CH2F2 351.4 57.927 0.27 15 0.60–0.97 [a]
CHCl2F 440 43.26 0.232 19 0.57–0.98 [a]
CClF3 302 38.7 0.167 17 0.43–0.99 [a]
CCL2F2 385 41.31 0.178 21 0.47–0.99 [a]
CCL3F 471.2 44.09 0.187 17 0.51–0.98 [a]
H2S 373.1 90 0.096 38 0.50–0.93 [a]
H2 O 647.3 221.2 0.343 40 0.49–0.96 [a]
CH4O 512.6 80.95 0.566 18 0.63–0.97 [a]
C2H6O 516.3 63.9 0.643 19 0.60–0.95 [a]
C3H6O 508.2 47.61 0.307 18 0.65–0.98 [a]
Overall 956
[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/fluid).

the saturated vapour pressure experimental data of 53 pure com- (9), with the SRK, PR, modified PR of Gasem et al. (2001); and
ponents and liquid density of the same 49 pure components. Thus, Coquelet et al. (2004) are investigated. In this text, the last two
the following relations are obtained for n and m, respectively, as: EOSs are called GPR and CPR EOSs, respectively. The CPR alpha
function is expressed as:
n = 1.7309 + 1.6571ω + 0.1554ω2 (10)
√ √
m = 0.2476−0.8857ω + 0.1900ω2 (11) ˛(T) = exp(k1(1−Tr))(1 + k2(1− Tr)2 + k3(1− Tr)3)2 Tr < 1
(12)
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 ˛(T) = exp(k1(1−Tr)) Tr > 1 (13)

| 1378 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | 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 Liquid density

Component PR PR78 SRK CPR GPR MPR2 PR PR78 SRK CPR GPR MPR2

C1 0.639 0.639 1.826 2.054 0.976 1.009 8.914 8.914 4.423 9.203 8.997 2.439
C2 0.349 0.349 1.426 1.057 0.373 0.757 6.612 6.612 7.723 6.691 6.611 2.857
C3 0.834 0.834 1.101 0.947 0.481 0.823 5.209 5.209 7.956 5.240 5.190 2.300
n-C4 0.515 0.515 1.241 0.424 0.657 0.653 4.921 4.921 10.427 4.913 4.909 3.390
i-C4 1.079 1.079 0.723 1.068 0.956 1.054 5.136 5.136 9.601 5.148 5.105 3.339
n-C5 2.148 2.148 1.755 0.451 1.269 1.766 3.608 3.608 11.707 3.612 3.629 2.901
n-C6 1.594 1.594 2.996 1.623 0.662 1.741 2.695 2.695 12.757 2.680 2.711 2.754
n-C7 1.652 1.652 0.652 1.996 2.340 0.563 0.687 0.687 12.135 0.712 0.729 0.658
n-C8 1.566 1.566 1.781 1.784 2.024 1.234 5.905 5.905 16.754 5.930 5.983 4.389
n-C9 1.259 1.259 1.868 0.557 0.762 1.086 6.859 6.859 17.517 6.852 6.896 4.159
n-C10 1.749 1.749 2.110 1.046 1.323 1.468 5.930 5.930 16.812 5.915 5.948 3.238
n-C12 12.029 7.577 1.981 2.639 3.294 5.985 8.021 7.954 18.305 7.907 7.941 0.759
C2H4 0.637 0.637 0.799 0.861 0.547 0.351 6.206 6.206 7.209 6.324 6.205 2.288
C2H2 1.482 1.482 2.259 1.366 1.687 1.539 4.194 4.194 11.425 4.175 4.191 3.214
C3H6 1.462 1.462 0.881 0.924 1.555 0.797 6.623 6.623 7.125 6.682 6.601 3.284
C6H6 0.897 0.897 0.667 0.809 1.133 0.777 3.170 3.170 11.211 3.157 3.164 2.061
C6H5CH3 1.318 1.318 1.148 1.040 1.626 0.919 2.446 2.446 13.269 2.438 2.476 2.898
Ar 0.306 0.306 1.640 2.597 1.084 1.050 10.343 10.343 3.618 10.724 10.444 3.633
CHCl3 3.956 3.956 4.293 4.137 3.553 4.445 6.670 6.670 8.101 6.666 6.632 5.330
CF4 1.380 1.380 1.375 1.201 1.756 1.091 6.136 6.136 7.795 6.156 6.100 3.854
CCL4 1.525 1.525 0.935 1.178 1.760 1.148 4.247 4.247 10.489 4.242 4.248 2.555
CO2 0.712 0.712 0.390 0.746 0.184 0.900 3.162 3.162 10.882 3.148 3.122 2.419
CL2 1.411 1.411 0.820 1.145 1.100 0.701 4.086 4.086 9.498 4.170 4.103 2.731
CO 0.161 0.161 0.642 1.157 0.134 0.227 7.232 7.232 6.755 7.426 7.243 4.064
Ne 1.023 1.023 1.534 2.317 0.939 0.977 13.332 13.332 4.193 13.995 13.527 5.501
Xe 1.072 1.072 0.800 1.484 0.297 0.403 7.213 7.213 6.436 7.509 7.292 2.073
Kr 0.579 0.579 1.458 2.297 0.722 0.680 9.254 9.254 3.822 9.577 9.354 2.250
N2 0.667 0.667 1.187 1.632 0.213 0.419 9.789 9.789 3.459 10.037 9.843 3.454
SO2 2.390 2.390 2.084 2.286 2.872 1.943 2.328 2.328 12.978 2.318 2.370 2.724
F2 0.432 0.432 1.897 1.557 0.775 1.006 9.491 9.491 3.879 9.661 9.528 3.682
O2 1.569 1.569 1.540 1.290 0.407 0.455 10.611 10.611 3.369 10.913 10.692 3.603
CH3C1 2.622 2.622 1.871 1.826 2.656 1.781 4.790 4.790 10.500 4.809 4.782 2.683
[–(CF2)4–] 1.447 1.447 1.131 1.461 1.485 1.015 5.619 5.619 8.243 5.599 5.596 6.757
CH3CHF2 0.424 0.424 2.082 0.669 0.877 0.768 8.597 8.597 19.101 8.600 8.669 9.090
CH3CF3 1.386 1.386 1.485 1.293 1.897 0.819 5.556 5.556 16.437 5.554 5.635 6.482
CH3CClF2 3.980 3.980 5.718 4.299 4.434 4.344 3.338 3.338 9.331 3.333 3.312 2.142
CHF2CF3 1.065 1.065 2.070 1.533 1.548 1.066 2.928 2.928 12.036 2.922 2.944 2.868
CHClFCF3 0.833 0.833 1.173 1.032 1.504 0.460 4.346 4.346 12.060 4.323 4.337 4.143
C2CL3F3 1.458 1.458 0.728 1.055 1.494 1.188 4.948 4.948 9.629 4.939 4.932 4.074
CH2F2 1.091 1.091 1.992 1.247 1.768 0.904 17.405 17.405 26.989 17.414 17.486 17.866
CHCl2F 1.714 1.714 0.680 1.719 1.702 1.510 17.075 17.075 26.690 17.066 17.153 18.182
CClF3 2.771 2.771 1.366 1.991 2.587 1.925 6.229 6.229 8.594 6.252 6.209 3.501
CCL2F2 1.758 1.758 0.951 1.202 1.683 1.244 5.529 5.529 8.709 5.547 5.510 3.117
CCL3F 1.031 1.031 0.809 0.785 1.261 0.803 10.576 10.576 12.061 10.602 10.533 8.076
H 2S 2.125 2.125 1.169 1.211 1.831 1.191 7.237 7.237 5.217 7.398 7.229 2.263
H2 O 3.330 3.330 5.913 4.249 3.944 4.198 18.437 18.437 27.788 18.440 18.481 17.502
CH4O 1.876 1.491 2.565 1.721 1.916 2.155 17.606 17.527 27.146 17.554 17.594 13.642
C2H6O 0.725 2.042 1.914 1.872 1.680 1.775 7.715 7.572 18.358 7.583 7.638 4.622
C3H6O 2.118 2.118 1.725 1.922 1.729 2.305 13.647 13.647 23.670 13.672 13.749 13.520
Overall 1.636 1.564 1.656 1.566 1.499 1.376 7.196 7.190 11.718 7.260 7.216 4.803
Σ .P cal −P exp
i i
.
∗ AAD = 100np exp
Pi
.
i

where the 1, 2, and 3 are written in terms of acentric factor. In k3 = −0.01871 + 1.93328ω (16)
this study, it should be pointed out that the adjustable parameters
of the CPR equation were correlated again using the same database
as follows: RESULTS AND DISCUSSION
k1 = 0.41287 + 1.34494ω + 0.00421ω2 (14) To demonstrate the accuracy of the modified PR EOS, calculation
of some thermodynamic properties of pure components and mix-
k2 = 0.03982 + 0.08551ω−1.05521ω2 (15) tures are carried out. Table 2 presents the percent absolute average

| VOLUME 89, DECEMBER 2011 | | 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 significant
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 vapourisa-
tion, respectively. Table 4 shows the results of the vapour pressure
calculation of heavy hydrocarbons using the five cubic EOSs. A
notable improvement has been achieved by new modified 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 Enthalpy of vapourisation

Component PR PR78 SRK CPR GPR MPR2 PR PR78 SRK CPR GPR MPR2

C1 1.004 1.004 2.288 2.402 1.562 1.949 1.442 1.442 2.513 1.447 1.881 2.451
C2 0.959 0.959 1.504 1.660 1.078 1.542 1.739 1.739 2.755 1.728 1.899 1.942
C3 1.278 1.278 1.272 1.389 0.924 1.344 1.014 1.014 1.400 0.863 0.757 0.963
n-C4 1.059 1.059 1.203 1.056 0.890 1.372 2.068 2.068 2.944 1.890 2.153 2.194
i-C4 1.190 1.190 0.641 1.044 1.448 1.178 1.220 1.220 1.336 1.125 1.011 1.156
n-C5 2.231 2.231 2.008 0.620 1.167 2.003 2.191 2.191 2.310 1.520 1.604 2.272
n-C6 2.037 2.037 3.928 2.202 1.021 2.235 1.607 1.607 2.099 1.541 1.252 1.827
n-C7 1.757 1.757 0.503 2.042 2.380 0.899 0.591 0.591 1.199 0.122 0.249 0.544
n-C8 1.971 1.971 2.268 1.730 1.815 2.231 3.258 3.258 4.163 3.203 3.256 3.720
n-C9 1.644 1.644 2.570 0.924 0.890 1.667 1.744 1.744 2.165 1.454 1.481 2.049
n-C10 1.733 1.733 2.883 1.683 1.530 2.471 1.890 1.890 2.761 1.996 1.849 2.591
n-C12 9.108 6.548 2.280 2.974 3.100 5.375 2.556 2.277 1.610 1.423 1.342 2.652
C2H4 1.170 1.170 0.574 1.350 1.084 1.190 1.233 1.233 1.659 1.184 1.065 1.410
C2H2 1.241 1.241 1.400 1.359 0.912 1.487 3.795 3.795 4.425 3.669 3.784 3.911
C3H6 1.452 1.452 0.404 1.173 1.560 1.127 1.678 1.678 1.695 1.572 1.406 1.605
C6H6 1.150 1.150 0.735 1.049 1.145 1.133 1.309 1.309 1.398 1.105 1.289 1.314
C6H5CH3 2.543 2.543 1.870 2.090 2.599 2.322 2.930 2.930 3.266 2.465 2.658 2.976
Ar 1.568 1.568 2.262 3.687 2.394 2.690 1.267 1.267 2.558 1.734 1.759 2.135
CHCl3 4.461 4.461 4.692 4.583 4.457 5.011 4.316 4.316 4.665 4.335 4.709 4.343
CF4 1.666 1.666 0.893 1.624 1.599 1.535 — — — — — —
CCL4 2.244 2.244 0.919 1.922 2.248 2.019 2.074 2.074 1.908 1.805 1.803 2.042
CO2 1.449 1.449 1.383 1.438 0.907 1.573 1.160 1.160 1.738 1.036 1.006 1.271
CL2 3.035 3.035 1.350 1.579 2.751 2.777 3.180 3.180 1.985 2.352 2.880 3.436
CO 6.501 6.501 5.025 6.069 6.494 7.046 1.885 1.885 1.878 1.239 1.761 2.647
Ne 1.513 1.513 1.106 3.038 1.602 2.372 1.343 1.343 2.821 2.580 2.060 2.179
Xe 2.496 2.496 1.023 2.007 1.651 2.653 2.484 2.484 2.511 1.524 1.998 3.171
Kr 1.897 1.897 2.181 2.957 2.151 2.495 1.874 1.874 2.493 1.421 1.808 2.416
N2 1.340 1.340 1.479 2.036 1.178 1.542 1.690 1.690 2.711 1.297 2.035 2.442
SO2 2.572 2.572 1.902 2.479 2.661 2.227 1.116 1.116 1.164 0.886 0.729 1.080
F2 1.276 1.276 2.149 2.256 1.788 2.156 1.841 1.841 1.980 1.569 1.309 1.988
O2 2.168 2.168 1.652 2.004 1.405 1.821 2.116 2.116 2.654 1.482 2.043 2.683
CH3C1 4.978 4.978 3.059 4.175 5.071 4.393 2.453 2.453 2.853 2.253 2.188 2.428
[–(CF2)4–] 1.773 1.773 1.332 1.763 1.790 1.504 — — — — — —
CH3CHF2 1.677 1.677 3.432 1.775 1.097 2.139 2.230 2.230 3.342 2.414 2.355 2.453
CH3CF3 1.563 1.563 2.134 1.297 1.176 1.490 1.891 1.891 2.755 1.807 1.733 2.021
CH3CClF2 5.591 5.591 7.690 6.029 5.300 6.222 — — — — — —
CHF2CF3 1.473 1.473 1.992 1.948 2.194 1.554 2.151 2.151 1.926 2.264 2.440 1.985
CHClFCF3 1.358 1.358 1.805 1.184 1.079 1.488 6.010 6.010 6.891 5.865 5.953 6.239
C2CL3F3 2.247 2.247 1.072 1.792 2.005 2.115 2.347 2.347 2.434 1.904 2.090 2.379
CH2F2 6.712 6.712 7.686 6.561 5.906 7.133 6.502 6.502 7.388 6.545 6.316 6.694
CHCl2F 3.946 3.946 3.034 3.915 4.631 3.638 6.676 6.676 5.950 6.588 6.895 6.603

CClF3 3.125 3.125 1.152 2.556 3.048 2.661 3.588 3.588 3.274 3.222 3.268 3.555
CCL2F2 2.762 2.762 1.540 2.299 2.616 2.519 2.416 2.416 2.463 2.074 2.122 2.415

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 CCL3F 1.242 1.242 0.816 1.001 1.584 1.083 1.470 1.470 1.402 1.203 1.265 1.410
H2S 1.988 1.988 0.283 1.381 1.750 1.484 — — — — — —
H 2O 4.573 4.573 7.427 5.367 4.595 5.692 — — — — — —
CH4O 6.005 7.229 7.521 6.773 6.579 7.275 — — — — — —
C 2 H 6O 17.052 15.867 16.192 16.161 16.402 16.401 — — — — — —
C 3H 6 O 3.253 3.253 3.898 3.056 2.896 3.406 — — — — — —
Overall 2.837 2.786 2.621 2.724 2.615 2.891 2.350 2.343 2.718 2.139 2.231 2.575

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

AAD% in P

Compound np Tr range Refs. Tc (K) Pc (bar) ω PR PR78 SRK CPR GPR MPR2

n-C14 10 0.50–0.76 [a] 692.17 15.92 0.6572 2.207 3.452 6.435 5.085 4.498 5.153
11 0.62–0.76 [b] 692.17 15.92 0.6572 3.202 0.217 1.058 0.299 0.297 0.838
16 0.54–0.85 [c] 692.17 15.92 0.6572 4.151 0.768 1.719 0.321 0.787 1.171
n-C16 10 0.52–0.78 [a] 720.67 13.94 0.7368 8.517 4.179 2.870 3.035 3.486 3.192
26 0.59–0.77 [d] 720.67 13.94 0.7368 12.285 5.038 1.470 3.084 3.349 2.383
20 0.54–0.81 [c] 720.67 13.94 0.7368 6.706 0.630 1.732 0.384 0.458 1.374
16 0.64–0.77 [e] 720.67 13.94 0.7368 4.727 0.199 0.850 0.367 0.275 0.915
n-C18 17 0.55–0.79 [c] 745.25 12.29 0.8137 9.450 0.542 1.909 0.682 0.824 1.836
23 0.50–0.76 [d] 745.25 12.29 0.8137 9.901 3.510 4.887 3.726 3.987 3.879
n-C20 21 0.51–0.75 [d] 766.66 10.91 0.8883 20.823 4.782 4.433 4.741 3.794 5.038
21 0.47–0.61 [f] 766.66 10.91 0.8883 34.731 6.782 3.417 1.303 4.231 3.329
29 0.51–0.82 [g] 766.66 10.91 0.8883 17.563 2.453 1.372 1.229 1.334 2.380
32 0.56–0.76 [c] 766.66 10.91 0.8883 13.662 0.593 1.209 0.767 0.428 1.855
Overall 252 11.379 2.549 2.566 1.925 2.134 2.565
[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 tem-
peratures 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 den-
sity 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) P (bar) pexp (kg/m3) PR SRK MPR2

91 0.52 451.031 12.76 0.21 0.16

100.15 0.56 438.779 12.74 0.06 1.08
108.05 0.95 427.699 12.61 −0.18 1.77
114.94 1.55 417.697 12.37 − 0.49 2.26
150.3 14.757 360 8.17 − 4.50 2.13
151.807 27.698 360 8.32 − 4.25 2.57
153.619 43.24 360 8.49 − 3.97 3.08
155.457 58.309 360 8.58 − 3.76 3.50
168.735 171.383 360 9.45 − 2.31 6.48
180.089 266.271 360 9.91 − 1.52 8.52
188.496 335.421 360 10.14 − 1.09 9.87
159.295 19.589 341 6.12 − 6.26 1.18
172.744 116.019 341 7.56 − 4.07 5.04
176.864 145.434 341 7.87 − 3.61 5.97
181.641 179.513 341 8.19 − 3.13 6.98
189.751 236.731 341 8.60 − 2.50 8.50
168.227 29.564 321 3.78 − 8.11 0.07
170.158 41.084 321 4.13 − 7.61 0.84
172.545 55.272 321 4.50 − 7.08 1.69
178.454 90.637 321 5.31 − 5.97 3.53
186.819 140.828 321 6.19 − 4.78 5.67
175.605 31.599 297 0.24 − 11.02 2.54
178.055 43.229 297 0.90 − 10.14 1.28
182.805 65.97 297 1.95 − 8.79 0.72
182.805 65.943 297 1.94 − 8.80 0.71
188.261 92.321 297 2.91 − 7.61 2.56
Total AAD% 7.07 4.68 3.41
∗ Dev% = pcal −ppexp .
exp

| 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 CH4 12.61 0.89 3.34 10.27 9.23 13.35

N2 C2H6 7.43 4.24 3.75 49.36 42.25 60.34
N2 C3H8 3.29 7.71 5.77 76.20 72.21 80.15
CH4 C2H6 9.65 2.55 1.49 3.69 4.85 4.84
CH4 C3H8 8.48 3.54 1.88 8.11 9.59 7.97
CH4 i-C4H10 5.22 6.17 3.17 22.61 23.06 21.62
CH4 nC4H10 8.67 3.51 1.46 30.97 31.35 30.64
C2H6 C3H8 5.66 5.79 3.96 — — —
C2H6 i-C4H10 5.09 6.23 4.54 — — —
C2H6 n-C4H10 4.44 6.82 4.25 — — —
C3H8 i-C4H10 2.86 8.18 5.08 — — —
C3H8 n-C4H10 2.97 8.08 4.43 — — —
i-C4H10 n-C4H10 2.21 8.70 4.46 — — —
Overall 6.04 5.57 3.66 28.74 27.51 31.27

Without using coupling interaction parameter, the classi-
cal quadratic mixing rules were applied for calculations of
vapour–liquid equilibrium of the binary systems. As one can see
from Table 6, the present EOS predicts the liquid density with bet-
ter 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 x(N2) x(CH4) x(C2H6) x(C3H8) x(i-C4H10) x(n-C4H10)

A1 — 0.34242 0.31372 0.34386 — —

A2 — 0.80284 0.09902 0.09814 — —
B — 0.85443 0.05042 0.04038 0.02577 0.02901
C1 0.338 0.3414 0.3206 — — —
C2 0.1635 0.6704 0.1661 — — —
D 0.099 0.7977 — 0.1028 — —
E 0.0484 0.8526 0.0483 0.0507 — —
F 0.049 0.806 0.0468 0.0482 0.05 —
G 0.0554 0.7909 0.056 0.05 — 0.0477
H 0.0425 0.813 0.0475 0.0487 0.0241 0.0242

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 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 8.31 3.63 2.21 9.72 10.98 9.92

B 10.38 1.98 0.62 3.20 6.20 3.25
C 12.09 0.56 1.79 21.16 17.51 28.58
D 11.57 1.03 0.99 25.09 22.80 30.98
E 11.81 0.84 0.74 19.61 18.50 24.60
F 10.80 1.63 0.55 28.44 26.84 33.25
G 10.69 1.65 0.36 28.06 26.05 33.57
H 10.69 1.72 0.55 35.31 34.05 39.45
Overall 10.79 1.63 0.98 21.32 20.37 25.45

by the new MPR2 are in very good agreement with experimental dence of covolume parameter on temperature in the new modified
data. However, the results of the vapour pressure are not as well PR has significant influence in prediction of liquid density.
as liquid density, although the PR prediction of vapour pressure To demonstrate the capability of the present EOS in construction
is better than the new EOS. This can be explained that the depen- of the phase diagrams, five synthetic natural gases (SNGs) were

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

SNG 1 SNG 2 SNG 3 SNG 4 SNG 5 Gas condensate 1 Gas condensate 2 Gas condensate 3

Nitrogen 0.00000 0.00000 0.000 0.004800 0.006180 0.0075 0.0034 0.0042

Carbon dioxide — — — — 0.001870 0.03912 0.0217 0.0061
Methane 0.84280 0.93600 0.890 0.887634 0.989430 0.70203 0.7064 0.5753
Ethane 0.10067 0.02630 0.070 0.085400 0.000820 0.0922 0.1076 0.1345
Propane 0.04028 — — 0.016800 0.000650 0.02759 0.0494 0.0752
i-Butane 0.00597 0.01490 — 0.002200 0.000500 0.00662 0 0
n-Butane 0.01028 0.01490 0.040 0.002900 — 0.00981 0.0302 0.0415
i-Pentane — — — 0.000182 0.000170 0.00402 0 0
n-Pentane — 0.00795 — 0.000084 — 0.00422 0.0135 0.0233
n-Hexane — — — — 0.000320 0.00816 0.009 0.0179
n-Heptane — — — — 0.000027 — — —
n-Octane — — — — 0.000033 — — —
C7+ — — — — — 0.09873 0.0588 0.1220
Mw of C7+ — — — — — 192.8 153.0 193.0
SG of C7+ — — — — — 0.8030 0.810 0.8115
Reference [a] [a] [b] [c] [d] [e] [f] [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 fluid

Exp %AAD(P)

Mixture T (K) P (bar) PR SRK MPR2 Data type

Gas condensate 1 313.5 450.2 31.963 27.231 17.186 Bubble point

Gas condensate 1 333.2 458.9 28.018 23.063 15.759 Bubble point

Gas condensate 1 352.8 465.3 24.938 19.692 14.655 Bubble point

Gas condensate 1 371.6 466.8 22.211 16.599 13.304 Bubble point

| VOLUME 89, DECEMBER 2011 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 1383 |
 Gas condensate 1 390.5 460.7 19.015 12.912 11.115 Dew point
Gas condensate 1 410.1 453.1 16.222 9.573 9.097 Dew point
Gas condensate 1 429.5 446.6 14.391 7.184 8.173 Dew point
Gas condensate 1 450.3 428.8 11.311 3.119 5.410 Dew point
Gas condensate 2 408.7 334.7 11.703 4.260 5.886 Dew point
Gas condensate 3 360.9 305.3 12.125 15.801 10.748 Bubble point
Overall 19.190 13.944 11.133

| 1384 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, DECEMBER 2011 |
chosen that their compositions are given in Table 9. The first 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 ij=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 flu-
ids. In addition, the compositions of the gas condensates mixtures
Figure 2. Comparison of phase envelope prediction of various SNGs with different EOSs and experimental data.
| VOLUME 89, DECEMBER 2011 |
are given in Table 9. The heavy ends of these mixtures are charac-
terised 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 proper-
ties and finally Kesler–Lee correlation (Kesler and Lee, 1976) is
used for finding the critical properties of the SCN groups. As it is
presented in Table 10, the present model shows better accuracy
in prediction of vapour–liquid 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
| THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 1385 |
 Figure 2. (Continued )

some unphysical results at high pressures and temperatures. Neg- condensate mixtures using the modified PR EOS represented the
ative values of covolume for substances with ω< 0.3 at Tr > 5, better accuracy than SRK and PR EOSs.
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). Notation
Thus, the application of the present EOS at the temperatures and a attraction parameter (Pam6 mol−1)
pressures far from those encountered in chemical industry must b molar co-volume (m3 mol−1)
be carefully notified. H enthalpy (J mol−1)
m,n parameters in the new equation of state
N number of compounds
np number of experimental points
CONCLUSION p pressure (bar)
A modified PR EOS was introduced by considering a new tem- R universal gas constant (8.314 J mol−1 K−1)
perature dependence function for the attractive parameter of a T temperature (K)
and a linear temperature relation for the covolume parameter b. V vapour volume
The results of the new EOS (MPR2) for a large number of pure x liquid phase mole fraction
components were presented for calculation of vapour pressure, y vapour phase mole fraction
liquid density, vapour molar volume and enthalpy of vapourisa-
tion. While the modified PR EOS correlated the liquid density Greek Letters
of pure components with better accuracy, however the results of
vapour pressure (excluding heavy hydrocarbons), vapour molar ˛ alpha function
volume and enthalpy of vapourisation are almost the same using ˇ beta function
both the new PR and the original PR. Also the new EOS demon- p density (kg m−3)
strated more accurate results for the vapour pressure of pure heavy ω Pitzer acentric factor
hydrocarbons than original PR. The results of the new modified
PR EOS for prediction of liquid density of a number of binaries Subscripts
and the LNG mixtures showed a reasonable accuracy and com- c critical
patible with both PR and SRK EOSs. In addition, the prediction i,j indices
of the phase envelope of SNGs and dew and bubble points of gas r reduced

| 1386 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, DECEMBER 2011 |
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.
| VOLUME 89, DECEMBER 2011 |