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A new Peng-Robinson modification to enhance dew point estimations of

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 Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

A new Peng-Robinson modification to enhance dew point estimations

of natural gases
Saeid Valiollahi a, Babak Kavianpour a, Sona Raeissi a, *, Mahmood Moshfeghian a, b
a
School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave., Shiraz, 71345, Iran
b
PetroSkills - John M. Campbell, 410 W. Grand Pkwy, So., Ste 400, Katy, TX 77494, USA

a r t i c l e i n f o a b s t r a c t

Article history: Equations of state (EOSs) are widely used in calculations such as those involving reservoir simulation,
Received 6 April 2016 process simulation, gas processing and transportation of natural gas. Predicting the phase envelope,
Received in revised form specifically the dew points of natural gas, is among the important roles of EOSs. In this study, a modi-
19 July 2016
fication is proposed to improve the predictions of dew point properties by the Peng-Robinson (PR) EOS,
Accepted 22 July 2016
Available online 25 July 2016
where the attraction parameter has been modified by a new empirical-based coefficient which is a
function of reduced pressure, reduced temperature and critical density. In order to validate the modi-
fication, results are presented for four major properties of dew points consisting of the cricondentherm,
Keywords:
Hydrocarbon
cricondenbar, dew point temperature and dew point pressure. Furthermore, the performances of the
Phase envelope original PR, Soave-Redlich-Kwong (SRK), Schmidt-Wenzel (SW) and GERG-2008 EOSs have been
Phase equilibria compared to predict the above four properties with respect to the experimental data. Having similar
Cricondentherm qualitative trends for the four properties, the results show that the modification of this study gives better
Cricondenbar predictions of the dew point curves, followed by the GERG EOS, which was developed particularly for
Equation of state processed natural gases. The SRK and SW EOSs have comparatively similar results and the PR EOS has the
largest deviations.
© 2016 Published by Elsevier B.V.

1. Introduction specifying their thermodynamic functions such as enthalpy, en-

Precise predictions of natural gas phase behavior are essential
for the design of its production, processing and transportation fa-
cilities. For example, in the design of natural gas pipelines, one
favorable alternative is to transport the gas as a dense phase or a
supercritical fluid (Secord and Clarke, 1966; Rusten et al., 2008).
However, liquid formation is still possible in the pipeline, although
the pressure and temperature are higher than the critical point of
the mixture, because the two-phase region of the phase envelope of
a natural gas usually has regions with higher temperatures and
pressures than the critical point.
Equations of state (EOSs) are extensively used to predict ther-
modynamic properties and phase behavior. Cubic EOSs, such as the
Soave-Redlich-Kwong (SRK) (Soave, 1972) and the Peng-Robinson
(PR) (Peng and Robinson, 1976), are more commonly used due to
their reliability, the simplicity of their Pressure-Volume-
Temperature (PVT) relationships, and the relative ease in
* Corresponding author.
E-mail address: raeissi@yahoo.com (S. Raeissi).
tropy, heat capacity and speed of sound, which require algebraic
calculations and differentiations (Kavianpour et al., 2014). Although
a number of modifications of the PR and SRK EOSs have been
proposed to improve their predictions of vapor pressure and liquid
density (Feyzi et al., 1998; Twu et al., 1995a; Souahi et al., 1998;
Nazarzadeh and Moshfeghian, 2013; Lin and Duan, 2005) and
vapor-liquid equilibria (VLE), EOS modifications specifically aimed
at the improvement of natural gas phase envelope predictions are
limited.
Feyzi et al. (1998) proposed a modified PR EOS, mainly to
improve VLE calculations and liquid density predictions by
considering empirical-based coefficients for the EOS. However their
modification showed enhancements in dew point pressure pre-
dictions for a limited number of binary systems. Nasrifar and
Bolland (2006) demonstrated that SRK-type EOSs and the
Schmidt-Wenzel (SW) EOS (Schmidt and Wenzel, 1980) give better
agreement with experimental values of two natural gas mixtures,
as compared to the PR EOS. Mørch et al. (2006) improved dew point
predictions of the Redlich-Kwong (RK) EOS (Redlich and Kwong,
1949) by modifying the function for the EOS attractive term

http://dx.doi.org/10.1016/j.jngse.2016.07.049
1875-5100/© 2016 Published by Elsevier B.V.
1138 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147
(Mathias and Copeman, 1983). The model was then validated using
the experimental data of five synthetic natural gas mixtures.
However, the method cannot be used for natural gases with a hy-
pothetical heavy fraction because the coefficients of the function
(the Mathias and Copeman coefficients) (Nasrifar and Moshfeghian,
1998; Nasrifar et al., 2000) were not proposed to relate the prop-
erties of heavy fractions.
Nasrifar et al. (2005) studied dew point predictions of a number
of EOSs, including the SRK EOS with two modifications (Twu et al.,
1995a; Souahi et al., 1998), the PR EOS with four modifications
(Danesh et al., 1995; Twu et al., 1995b; Flo € ter et al., 1998; Gasem
et al., 2001), five three-parameter EOSs including the SW EOS
(Schmidt and Wenzel, 1980; Guo and Du, 1989; Patel and Teja, 1982;
Valderrama, 1990; Mohsen-Nia et al., 2003) and one four-
parameter EOS (Salim and Trebble, 1991). The calculations were
compared with data from five lean synthetic natural gas mixtures
and twelve rich natural gases with heavy ends. Since the modifi-
cations investigated (Twu et al., 1995a; Souahi et al., 1998; Danesh
€ter et al., 1998; Gasem et al., 2001)
et al., 1995; Twu et al., 1995b; Flo
were proposed to enhance properties other than dew points, they
were not clearly superior with respect to the corresponding original
EOS for dew point calculations. However, the study of Nasrifar et al.
(2005) showed that the SRK family of EOS gave better predictions
as compared to the PR EOS family. Furthermore, the SW EOS
calculated dew points of lean natural gas mixtures and rich gases
with good accuracy. In this way, the study indicated that EOSs with
a greater number of parameters are not necessarily superior in
predicting natural gas phase envelopes. Although the dominant
component of natural gas is methane, a more precise prediction of
this component's fugacity does not assure better dew point pre-
dictions because the dew curve is very sensitive to the composition
of the intermediate and heavy components (Rusten et al., 2008).
Farshchi Tabrizi and Nasrifar (2010) slightly improved the ac-
curacy of dew curve calculations of nine hydrocarbon mixtures, as
compared to the PR EOS, using a two-parameter EOS (Nasrifar and
Bolland, 2006) incorporating a binary interaction correlation
(Robinson and Peng, 1978). Rusten et al. (2008) evaluated the ac-
curacy of the PR, SRK, PC-SAFT (von Solms et al., 2003) and GERG-
2004 (Kunz et al., 2007) EOSs for eleven synthetic natural gas
mixtures and two real natural gases. Their results showed that the
GERG-2004 EOS predicted the dew points of lean synthetic mix-
tures with high accuracy, the PC-SAFT and SRK EOSs gave similar
results for all cases, the PR EOS was superior for real natural gases,
specifically near the cricondentherm and the SRK EOS indicated
better results near the cricondenbar on the phase envelope. Their
study showed that the phase envelope prediction errors of an EOS
can be higher for the region between the cricondenbar and cri-
condentherm, than for the other parts of the dew curve.
In this study, an empirical-based modification is presented for
the PR EOS to enhance dew point predictions of natural gas mix-
tures. The modification is validated by experimental data from
literature and its performance is compared to the PR, SRK, SW and
GERG-2008 (Kunz and Wagner, 2012) EOS.
2. Theory and method
2.1. Model
In this study, VLE calculations (Prausnitz et al., 1999) for dew
point pressures were performed using the procedure proposed by
Pedersen and Christensen (Pedersen and Christensen, 2007),
starting from an intermediate pressure and progressively going to
higher pressures in order to eliminate convergence problems at
high pressures (Michelsen, 1980). The calculations for dew point
temperatures were accomplished by the suggested procedure of
Maddox and Erbar (1982). After performing the above estimations,
the maximum value of temperature obtained from dew point
temperature calculations was considered as the cricondentherm
and the maximum value of pressure from dew point pressure cal-
culations was considered as the cricondenbar.
The prediction of dew points can be improved by using binary
interaction parameters. Jaubert and Mutelet (2004) proposed an
approach to calculate binary interaction parameters for the modi-
fication of the PR EOS (Robinson and Peng, 1978). In this study the
binary interaction parameters are obtained from the study of
Knapp and Doring. These have been summarized by Danesh (1998).
However, for the mixtures containing highly polar and asymmetric
compounds, only optimizing on interaction parameters may
sometimes be insufficient for proper modeling accuracy (Knudsen
et al., 1993), thus several mixing rules have been proposed for
this purpose. In 2004, Voutsas et al. (2004) proposed a universal
mixing rule (UMR) which can be incorporated into cubic EOSs, such
as the PR EOS. The UMR method showed very satisfactory results
for systems containing polymers or polar components. It also
showed satisfactory VLE predictions for synthetic natural gases
(Louli et al., 2007). In this study, we have chosen to concentrate
only on interaction coefficients, and to consider the van der Waals
mixing rules as the fixed model since, while being quite simple and
readily available in commercial packages, it has been shown to be
adequate to predict the phase behavior properties of hydrocarbon
mixtures of reservoir fluids (Danesh, 1998). However, while the
effects of different mixing rules have not been considered here, it is
suggested to be evaluated for more complex mixtures.
For further improvement of dew point predictions by the PR
EOS, we attempt to modify the attractive term empirically. To do
this, we consider that the PR EOS most often underestimates the
corresponding experimental dew curve data (Rusten et al., 2008;
Nasrifar and Bolland, 2006; Mørch et al., 2006; Nasrifar et al.,
2005), and although the general status of dew point predictions
for the near critical region and the low pressure dew points is fair,
the largest deviations are observed for the region between the
cricondentherm and cricondenbar.
By multiplying the attraction term of the PR EOS by a suitable
coefficient, it might be possible to constructively change the shape
of the resulting dew curve. However, to get the best results, the
coefficient should not be constant, but rather, condition-dependent
so as not to deteriorate the predictions of the bubble curve and the
critical point. This has led us to the idea of considering different
forms for an enhancing coefficient on the attraction term, to
improve natural gas dew point predictions of the PR EOS.
The following form is considered to introduce an enhancing
coefficient, b, which is considered to be a function of temperature
and pressure.
PR ¼ aPR  b
adew (1)
b ¼ 1 þ FðTÞ  FðPÞ (2)
Where F(T), F(P), aPR and adew
are the temperature-dependent
PR
function, pressure-dependent function, the attraction parameter
of the original PR EOS (Peng and Robinson, 1976), and the newly
modified attraction parameter, respectively. The temperature-
dependent function has been determined as follows:

0:5
0:5
FðTÞ ¼ Tr;mix 1 (3)
Where Tr,mix denotes the reduced temperature of the mixture.
Including this temperature-dependent function makes the modi-
fication specifically suitable for dew point calculations where Tr,mix
is greater than one.
 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147 1139

The function F(P) is obtained by optimizing to experimental data

et al., 2003) et al., 2006) et al., 2006) et al., 2006) et al., 2006) et al., 2006) et al., 2009a) et al., 2009a) et al., 2009a) et al., 2009a) et al., 2009a)
at various temperatures and pressures, in a way to minimize the

Gas 5 (mol Gas 6 (mol Gas 7 (mol Gas 8 (mol Gas 9 (mol Gas 10 (mol Gas 11 (mol Gas 12 (mol Gas 13 (mol Gas 14 (mol Gas 15 (mol
%) (Brown

0.007274
0.002490
0.001763
0.001175
0.005010
0.009786
0.005853
following objective function using the Levenberg-Marquardt

97.3065

0.09047

0.05339
0.02949
1.6081
0.8781
method.

0
0

0
!2
X bexp:  1
U¼ calc:
 FðPÞ

%) (Brown
(4)

0.009911
0.005923
0.003486
0.002175
0.000984
0.003160
0.003536
0.003005
FðTexp: Þ

98.6879

0.07821

0.03582
0.7059
0.4597
The parameter bexp is the numerical correction coefficient which

0
0

0
makes the calculated dew point of the PR EOS overlap the corre-

%) (Brown

0.003220
0.001585
0.000005
0.005919

0.008588
sponding experimental dew point. It is unique for each single

92.2325

0.09463
0.04404
0.01575

0.01398
6.3712
1.0492

0.1582
experimental dew point. The subtraction term in Eq. (4) denotes
the difference of experimental value of the pressure-dependent

0
0

0
function at the pressure and temperature of the experimental

%) (Brown
dew point and the corresponding calculated pressure-dependent

0.001361
0.001018
0.000003
0.005579

0.003225
89.3411

0.03196
0.01197

0.00419
7.7122
2.2104

0.5428

0.1326
function.

0
0

0
%) (Brown
2.2. Data collection and division of datasets

0.009383
0.001217
0.000003
0.000001
0.004523
0.006103
0.002463
90.2309

0.05142
6.8677
1.7107

0.8480

0.2653
To propose and verify the model for predicting the criconden-

0
0

0
therm, cricondenbar, dew point temperatures and dew point

%) (Mørch
pressures of natural gas, a dataset consisting of a total of 36

93.600
experimental hydrocarbon gas mixtures is obtained from literature

2.630

1.490
1.490

0.795
(Tables 1 and 2). Of these 36 mixtures, 15 (Table 1) were used for the

0
0

0
0
0
0
0
0
0
0
development of the model, while the remaining 21 mixtures

%) (Mørch
(Table 2) provide purely predictive results to verify the model.

94.085
Not only are the compositions of the mixtures presented in

4.468

1.447
Table 1, but also the different composition accuracies among the

0
0

0
0
0
0

0
0
0
0
0
0
0
0
various literature references are given in this table. The reason for
%) (Mørch

the selection of these particular data sets is due to their synthetic

96.611
nature, providing for more accurate compositions as compared to

1.527
1.475

0.385
real natural gas mixtures. In addition, they have an appropriate
0
0

0
0

0
0
0
0
0
0
0
0
quantity and distribution of experimental data points throughout
%) (Mørch

the phase envelope.

84.280
10.067

The data used to verify the model (Table 2) also include real
4.028
0.597
natural gas mixtures. The advantage of this approach, in addition 1.028
0
0

0
0
0
0
0
0
0
0
0
0
to validation with mixtures which were not used for its devel-
%) (Mørch

opment, is that in contrast to the synthetic mixtures of Table 1,

93.505
2.972
1.008
1.050
1.465

the real natural gas mixtures (with the code names of Gas 16 to
Code names, references and compositions of mixtures utilized to develop the model.

Gas 36) used for validation provide for a wider range of

0
0

0
0
0
0
0
0
0
0
0
0
components.
%) (Jarne

In this study, the critical properties of the mixtures were ob-

84.446
0.772
1.700

8.683
3.297
0.293
0.589
0.084
0.086
0.050

tained from the proposed method by Heidemann and Khalil (1980).

0
0
0
0
0
0
0
Gas 4 (mol
%) (Avila

96.4654

3. Results and discussion

2002a)

0.0096
0.0100
0.0010
0.410

2.510
0.213
0.184
0.197
et al.,

0
0
0
0
0
0
0

Following the method explained above and optimizing to the

Gas 3 (mol

training dataset given in Table 1, the following pressure-dependent

%) (Avila

86.4838
2002a)

0.0139
0.0063

function is obtained in this study:

0.862

9.832
2.388
0.183
0.231
et al.,


0

0
0
0
0
0
0
0
0

2
FðPÞ ¼ f1 f2 þ f3 Pr;mix þ f4 Pr;mix (5)
Gas 2 (mol
%) (Avila

88.7634
2002a)

0.0182
0.0084
et al.,

Where
0.48

8.54
1.68
0.22
0.29
0

0
0
0
0
0
0
0
0

h
i
f1 ¼ 1:030  exp  exp 9:3890  0:8524rc;mix (6)
Component Gas 1 (mol
%) (Avila

89.9584
2002a)

0.0084
0.0032
et al.,

0.67

8.22

0.11
0.13
0.9

f2 ¼ 3744:556  r4:2525 (7)

0

0
0
0
0
0
0
0
0

c;mix
Cyclohexane
Benzene
Toluene

f3 ¼ 568313:250  r5:9531 (8)

Table 1

n-C10

c;mix
n-C4

n-C5
n-C6
n-C7
n-C8
n-C9
CO2

i-C4

i-C5
N2

C1
C2
C3
 1140
Table 2
Code names, references and compositions of the natural gas mixtures used only for validation.

Component Gas 16 Gas17 Gas18 Gas19 Gas20 Gas 21 Gas22 Gas23 Gas24 Gas25 Gas26 (mol Gas27 Gas28 Gas29 Gas30 Gas 31 Gas 32 Gas 33 Gas 34 Gas 35 Gas 36 (mol
(mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) %)
(Avila (Avila (Avila (Avila (Jarne (Beronich (Beronich (Zhou (Brown (Brown (Brown (Brown (Brown (Rusten (Rusten (George (George (George (George (George (George
et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., et al., and Burkey,
2002b) 2002b) 2002b) 2002b) 2003) 2009) 2009) 2006) 2009b) 2009b) 2009b) 2009b) 2009b) 2008) 2008) 2005a) 2005a) 2005a) 2005b) 2005b) 2005)

He 0 0 0 0 0 0 0 0 0.0319 0.0470 0.0420 0.0329 0.0030 0 0 0 0 0 0 0 0

S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147
H2 0 0 0 0 0 0 0 0 0.0078 0.00070 0.00080 0.0100 0.0062 0 0 0 0 0 0 0 0
N2 0.618 2.80 6.90 5.651 1.559 0 0.391 2.031 6.1120 4.1880 2.4600 7.1560 0.4450 0.5108 1.6298 0.993 2.432 5.060 2.506 5.121 2.005
O2 0 0 0 0 0 0 0 0 0.0269 0.0040 0.0060 0.0160 0.0030 0 0 0 0 0 0.011 0 0
CO2 0.187 0.20 0.51 0.284 25.908 1.542 1.111 0.403 0.0569 1.0020 0.4775 0.4713 1.7290 1.8922 0.3207 0.501 0.984 1.520 1.006 1.556 1.200
CO 0 0 0 0 0 0.095 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
C1 98.943 96.6159 88.1882 83.3482 69.114 84.084 83.687 90.991 83.5100 89.2900 93.3100 85.9500 88.3200 86.6295 93.2144 94.737 85.500 69.818 85.224 69.410 65.529
C2 0.082 0.18 2.72 7.526 2.620 7.223 7.595 2.949 5.7600 3.9110 2.8140 4.3580 7.3150 6.1903 3.7328 2.022 4.896 9.093 4.995 9.222 10.228
C3 0.065 0.1029 0.85 2.009 0.423 4.441 4.748 1.513 2.3990 0.9790 0.5024 1.0650 1.7830 2.7941 0.5654 0.746 2.959 6.003 2.997 6.117 7.907
i-C4 0.05 0.0499 0.17 0.305 0.105 1.042 0.231 0.755 0.4863 0.1597 0.0874 0.2253 0.1625 0.4635 0.2906 0.299 0.985 2.998 1.005 3.028 2.101
n-C4 0 0.0095 0.32 0.520 0.104 0 1.450 0.755 0.8909 0.2048 0.1113 0.3273 0.1968 0.7524 0.0653 0.302 0.986 2.999 1.001 3.022 6.207
i-C5 0.017 0.0166 0.0850 0.120 0.034 0.423 0.316 0.299 0.2816 0.0565 0.0356 0.1240 0.0216 0.2109 0.0483 0.151 0.481 1.003 0.503 1.008 1.810
n-C5 0 0 0.0940 0.144 0.023 0.493 0.331 0.304 0.2314 0.0528 0.0331 0.1040 0.0143 0.1837 0.0167 0.150 0.494 1.005 0.502 1.016 2.212
n-C6 0.032 0.0160 0.119 0.068 0.110 0.658 0.037 0 0.0327 0.0161 0.0144 0.0399 0.0010 0.0503 0.0038 0.032 0.079 0.130 0.08096 0.13082 0.382
n-C7 0.0027 0.0054 0.0258 0.0138 0 0 0.045 0 0.0339a 0.0148a 0.0200a 0.0304a 0.00049a 0.0297a 0.0067a 0.030 0.074 0.121 0.07542 0.12187 0.136
n-C8 0.0033 0.0038 0.0180 0.011 0 0 0.058 0 0.0022a 0.0035a 0.0088a 0.0040a 0.000017a 0.0039a 0.0007a 0.009 0.022 0.036 0.02217 0.03582 0.060
n-C9 0 0 0 0 0 0 0 0 0.00026a 0.0012a 0.0042a 0.00059a 0.000003a 0.0006a 0 0.001 0.003 0.005 0.00333 0.00538 0.015
n-C10 0 0 0 0 0 0 0 0 0.000003a 0.00012a 0.00048a 0.000035a 0 0 0 0.001 0.003 0.004 0.00256 0.00414 0.006
n-C11 0 0 0 0 0 0 0 0 0 0.000008a 0.000031a 0.000002a 0 0 0 0 0 0 0 0 0
n-C12 0 0 0 0 0 0 0 0 0 0 0.0000002a 0 0 0 0 0 0 0 0 0 0
2,2- 0 0 0 0 0 0 0 0 0.0094 0.0049 0.0031 0.0101 0 0.0160 0.0042 0 0 0 0 0 0
dimethylpropane
2,2-dimethylbutane 0 0 0 0 0 0 0 0 0.0085 0.0042 0.0039 0.0105 0.00015 0.0055 0.0042 0.001 0.002 0.002 0.00155 0.0025 0
2,3-dimethylbutane 0 0 0 0 0 0 0 0 0.0121 0.0034 0.0029 0.0066 0.00055 0.0094 0.0065 0.002 0.005 0.008 0.00523 0.00846 0
2-methylpentane 0 0 0 0 0 0 0 0 0.0546 0.0124 0.0100 0.0307 0.0011 0.0402 0.0165 0.016 0.039 0.064 0.03965 0.06408 0
3-methylpentane 0 0 0 0 0 0 0 0 0.0309 0.0063 0.0057 0.0173 0.00053 0.0221 0.0089 0.006 0.015 0.025 0.01548 0.02502 0
Cyclopentane 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0164 0.0092 0 0 0 0 0 0
Methylcyclopentane 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.001 0.003 0.005 0.00337 0.00545 0
Cyclohexane 0 0 0 0 0 0 0 0 0.0171 0.0072 0.0075 0.0077 0.00019 0.0866a 0.0408a 0 0 0 0 0 0
Methylcyclohexane 0 0 0 0 0 0 0 0 0.0056 0.0056 0.0077 0.0046 0.000061 0 0 0 0 0 0.00029 0.00046 0
Cycloheptane 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0317a 0.0136a 0 0 0 0 0 0
Cyclooctane 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0008a 0.0004a 0 0 0 0 0 0
Benzene 0 0 0 0 0 0 0 0 0.00025 0.0250 0.0226 0.00039 0.00034 0.0362a 0.0002a 0 0 0.049 0 0.049 0.102
Toluene 0 0 0 0 0 0 0 0 0.000031 0.0032 0.0053 0.00008 0.000051 0.0209a 0.0004a 0 0 0.050 0 0.047 0.100
m-Xylene 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0023a 0 0 0 0 0 0 0
a
The model component has been characterized in literature.
 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147 1141

Table 3
Experimental and calculated cricondentherms and absolute deviations (AD) of the cricondentherm calculations for the various models.

Gas no. Exp. ( C) EOS cricondentherm ( C), (AD) ( C)

SRK PR GERG SW This work

Gas 2 35.75 36.31, (0.56) 37.81, (2.06) 36.61, (0.86) 36.49, (0.74) 36.20, (0.45)
Gas 3 32.35 33.35, (1.00) 34.45, (2.10) 34.02, (1.70) 33.51, (1.16) 33.10, (0.75)
Gas 4 54.25 54.33, (0.08) 56.21, (1.96) 54.69, (0.44) 54.34, (0.09) 55.10, (0.85)
Gas 5 11.75 11.99, (0.24) 14.15, (2.40) 12.21, (0.46) 12.34, (0.59) 12.08, (0.33)
Gas 6 16.75 17.49, (0.74) 19.11, (2.36) 16.68, (0.07) 17.99, (1.24) 16.70, (0.05)
Gas 7 10.95 12.43, (1.48) 14.09, (3.14) 12.27, (1.32) 12.78, (1.83) 12.02, (1.07)
Gas 8 4.85 6.42, (1.57) 8.06, (3.21) 4.48, (0.37) 6.14, (1.29) 4.30, (0.55)
Gas 9 3.65 2.97, (0.68) 0.97, (2.68) 2.87, (0.78) 2.14, (1.51) 4.00, (0.35)
Gas 10 5.25 3.51, (1.73) 1.83, (3.42) 5.47, (0.22) 3.84, (1.41) 5.30, (0.05)
Gas 11 6.08 6.59, (0.51) 8.71, (2.63) NA 6.70, (0.62) 6.40, (0.32)
Gas 12 8.94 8.17, (0.77) 10.82, (1.88) NA 8.13, (0.81) 9.11, (0.17)
Gas 13 6.71 4.85, (1.86) 7.69, (0.98) NA 5.03, (1.68) 6.20, (0.51)
Gas 14 6.60 3.86, (2.75) 7.26, (0.66) NA 3.05, (3.55) 6.41, (0.19)
Gas 15 3.95 1.64, (2.32) 4.99, (1.04) NA 0.86, (3.09) 3.80, (0.15)
Gas 16 27.65 26.49, (1.16) 29.09, (1.44) 26.57, (1.08) 26.78, (0.87) 28.50, (0.85)
Gas 17 27.65 25.76, (1.89) 28.35, (0.70) 25.71, (1.94) 26.06, (1.59) 27.70, (0.05)
Gas 18 4.15 4.52, (0.37) 2.04, (2.11) 4.81, (0.66) 3.70, (0.44) 4.50, (0.35)
Gas 19 0.35 0.20, (0.15) 2.41, (2.76) 0.17, (0.52) 0.28, (0.63) 0.10, (0.45)
Gas 20 20.95 19.37, (1.58) 21.55, (0.60) 20.43, (0.52) 19.64, (1.31) 20.50, (0.45)
Gas 23 6.05 7.27, (1.22) 10.97, (4.92) 7.60, (1.55) 7.97, (1.92) 6.80, (0.75)
Gas 24 8.45 9.71, (1.26) 7.08, (1.37) NA 9.13, (0.68) 9.63, (1.18)
Gas 26 2.30 5.12, (2.81) 2.09, (0.20) NA 5.08, (2.78) 3.97, (1.67)
Gas 27 1.77 0.03, (1.74) 2.62, (0.85) NA 0.55, (1.22) 0.20, (1.57)
Gas 28 37.78 37.18, (0.60) 38.79, (1.01) NA 37.10, (0.68) 37.50, (0.28)
Gas 29 19.97 20.40, (0.43) 17.85, (2.12) NA 19.65, (0.32) 20.10, (0.13)
Gas 32 24.42 29.06, (4.64) 26.06, (1.64) NA 28.43, (4.01) 28.30, (3.88)
Gas 34 28.82 29.30, (0.48) 26.25, (2.57) NA 28.62, (0.20) 28.70, (0.12)
Gas 36 79.60 75.62, (3.98) 72.41, (7.19) NA 75.04, (4.56) 74.30, (5.30)
Overall average AD ( C) 0.96 2.39 0.83 1.11 0.49
(GERG compatible)
Overall average AD ( C) 1.38 2.14 NA 1.46 0.81

*NA: Not available.

molar density of the natural gas mixture, respectively.

f4 ¼ 1166215:400  r6:2409
c;mix (9) The pressure-dependent function takes into account the
important role of pressure to improve dew point predictions. This
in which Pr,mix and rc,mix are the reduced pressure and the critical function, at high pressures, results in the increases of b. However, at

Fig. 1. Cricondentherm calculation deviations for the GERG-compatible mixtures.

1142 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147

Table 4
Experimental and calculated cricondenbars (MPa) and percentage absolute relative deviation (ARD %) of the calculated cricondenbars for the various models.

Gas no. Exp. (MPa) EOS cricondenbar (MPa), (ARD %)

SRK PR GERG SW This work

Gas 2 7.12 6.94, (2.49) 6.84, (3.93) 6.96, (2.25) 6.92, (2.78) 6.96, (2.25)
Gas 3 7.77 7.20, (7.34) 6.99, (10.04) 7.19, (7.46) 7.13, (8.27) 7.14, (8.11)
Gas 4 5.84 5.58, (4.37) 5.51, (5.79) 5.64, (3.39) 5.60, (4.16) 5.60, (4.11)
Gas 5 8.18 8.20, (0.24) 8.07, (1.34) 8.21, (0.37) 8.18, (0.00) 8.24, (0.73)
Gas 16 6.39 6.49, (1.51) 6.22, (2.75) 6.64, (3.85) 6.50, (1.66) 6.31, (1.25)
Gas 17 6.39 6.55, (2.58) 6.30, (1.39) 6.72, (5.23) 6.60, (3.33) 6.42, (0.47)
Gas 18 10.60 9.59, (9.50) 9.25, (12.70) 9.72, (8.29) 9.58, (9.57) 9.71, (8.37)
Gas 19 9.23 8.96, (2.91) 8.73, (5.42) 9.00, (2.50) 9.01, (2.38) 9.00, (2.49)
Gas 23 8.84 9.07, (2.53) 8.88, (0.37) 8.98, (1.55) 9.03, (2.12) 9.13, (3.25)
Gas 29 10.74 10.27, (4.37) 10.00, (6.89) NA 10.22, (4.90) 10.27, (4.39)
Overall average 3.72 4.86 3.88 3.81 3.45
(GERG compatible)
Overall average 3.78 5.07 NA 3.92 3.54

Fig. 2. Cricondenbar calculation deviations for the GERG-compatible mixtures.

the near-critical region, the temperature-dependent function
neutralizes the increase of b, and at higher temperatures it makes
the enhancing coefficient larger. As a result, the proposed tem-
perature and pressure dependent functions can mathematically
compensate the underestimations of dew point curves by the PR
EOS. The coefficients presented through Eqs. (5)e(9) have confor-
mity with the PR EOS fugacity coefficient equation, thus no further
mathematical calculations are required for this modification to
predict dew points of natural gas mixtures.
To investigate the validity of the proposed modification in pre-
dicting the cricondentherm, cricondenbar, dew point temperatures
and dew point pressures of natural gas, the performance of model is
evaluated against a total of the 36 experimental hydrocarbon gas
mixtures of Tables 1 and 2. Since the datasets of Table 2 were not
used for the development of the model, this table provides for a
purely predictive investigation of accuracies. In addition, in
contrast to the synthetic mixtures of Table 1, real natural gas mix-
tures (code names Gas 16e36) are included for validation, thus, a
wider range of components is considered in the validation.
However not all of the literature sources contain experimental
values on all of the four properties of concern (cricondentherm,
cricondenbar, dew point temperature and dew point pressure).
Consequently, the error results presented are limited to the avail-
able experimental values for each studied property. The following
relations define the reported deviations.
AD ¼ jcalc:  exp:j (10)
1X
AAD ¼ jcalc:  exp:j (11)
N
 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147 1143

Table 5
AAD of dew point temperature calculations for 34 natural gas mixtures.

Gas no. EOS dew point temperature calculation deviation (AAD)

SRK PR GERG SW This work

Gas 1 0.6 1.0 0.7 0.6 0.5

Gas 2 0.6 2.0 1.0 0.8 0.5
Gas 3 0.5 1.3 0.7 0.6 0.4
Gas 4 0.5 2.3 0.9 0.5 1.0
Gas 5 0.3 2.3 0.6 0.4 0.3
Gas 6 1.3 3.0 0.8 1.9 0.4
Gas 7 0.8 2.3 0.8 1.2 0.6
Gas 8 1.8 3.6 0.3 1.6 0.7
Gas 9 2.0 4.6 2.5 3.0 0.4
Gas 10 2.3 4.5 0.4 2.0 0.5
Gas 11 0.7 1.6 NA 0.6 0.7
Gas 12 1.1 1.6 NA 1.2 0.7
Gas 13 1.7 1.3 NA 1.4 0.6
Gas 14 2.5 3.3 NA 2.8 0.7
Gas 15 1.9 1.8 NA 2.5 0.4
Gas 16 1.3 2.2 2.2 0.8 1.0
Gas 17 1.9 1.5 2.9 1.7 0.3
Gas 18 5.0 1.9 1.0 2.5 0.6
Gas 19 0.8 3.8 0.7 1.1 0.7
Gas 20 1.5 0.6 0.6 1.4 0.5
Gas 23 2.2 6.0 2.7 3.0 1.6
Gas 24 1.0 1.3 NA 0.5 1.1
Gas 25 1.8 2.0 NA 2.0 1.4
Gas 26 2.3 1.1 NA 2.2 1.6
Gas 27 2.0 0.8 NA 1.5 1.8
Gas 28 0.8 0.8 NA 0.9 0.5
Gas 29 0.8 4.0 NA 1.5 0.4
Gas 30 6.5 9.6 NA 6.9 4.7
Gas 31 1.2 2.1 NA 1.1 1.3
Gas 32 3.9 2.4 NA 3.3 3.6
Gas 33 2.6 5.4 NA 3.1 2.7
Gas 34 1.7 2.6 NA 1.7 1.9
Gas 35 3.6 4.3 NA 3.9 3.5
Gas 36 3.0 5.7 NA 3.4 3.9
Overall average AAD 1.464 2.679 1.178 1.442 0.626
(GERG compatible)
Overall average AAD 1.836 2.782 NA 1.873 1.221

jcalc:  exp:j 100 X jcalc:  exp:j

ARD% ¼ (12) AARD% ¼ (13)
jexp:j N jexp:j

in which AD, AAD, ARD%, AARD% and N are the absolute deviation,

Fig. 3. Dew point temperature calculation deviations for the GERG-applicable mixtures.
1144 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147

Table 6
Percentage of average absolute relative deviations (AARD %) of dew point pressure calculations for 14 mixtures of natural gases.

Gas no. EOS dew point pressure calculation deviation (AARD%)

SRK PR GERG SW This work

Gas 2 4.61 5.3 5.13 5.17 3.28

Gas 3 9.51 14.11 10.37 10.38 8.50
Gas 4 6.60 13.24 7.80 6.26 7.73
Gas 5 0.60 3.13 0.69 0.72 1.26
Gas 6 10.85 16.19 8.83 12.29 6.34
Gas 7 12.83 15.70 12.49 14.46 9.81
Gas 16 2.07 4.56 5.31 1.73 1.89
Gas 17 3.59 3.16 6.91 3.85 0.70
Gas 18 9.10 14.13 5.86 10.70 4.93
Gas 19 8.61 4.01 2.30 4.60 3.46
Gas 21 4.22 4.22 NA 1.66 4.81
Gas 22 3.67 5.97 NA 3.30 4.01
Gas 23 2.27 1.50 1.83 1.80 3.11
Gas 29 3.59 10.06 NA 4.92 2.85
Overall average AARD% 6.42 8.64 6.14 6.54 4.64
(GERG compatible)
Overall average AARD% 5.87 8.23 NA 5.85 4.48

average absolute deviation, percentage absolute relative deviation,
percentage average absolute relative deviation and the number of
data points, respectively.
The values of experimental and calculated cricondentherms for
28 mixtures of gases and the absolute deviations (AD) of the cri-
condentherm predictions with respect to the corresponding
experimental values are presented in Table 3.
Since the GERG EOS has been developed for only limited com-
ponents, considering the behavior of natural gas mixtures that
contain naphthenic, aromatic and some branched alkanes was not
intended for this EOS. Subsequently, the average deviations are
presented in two groups; one for only those which are compatible
with the GERG EOS and one including all of the data. Fig. 1 sum-
marizes the results of cricondentherm prediction accuracies, in the
case of only those systems for which GERG is suitable.
Considering Table 3 and Fig. 1, the proposed modification shows
the best results of all the EOS models investigated in predicting the
cricondentherm; following that, is the GERG EOS which shows
higher accuracies than the SW and SRK. The SRK has slightly better
results than the SW. The ratio of the errors of the SW, GERG, PR and
SRK to the errors of our model for all available cricondentherm
calculations are 2.26, 1.69, 4.87 and 1.97, respectively and the cor-
responding values for the GERG EOS-compatible mixtures of
Table 2 are equal to 1.24, 2.16, 1.73 and 1.31, respectively.
Table 4 presents the experimental and calculated values of the
cricondenbars for ten hydrocarbon gas mixtures and the percent-
age absolute relative deviations (ARD %) of these cricondenbar
calculations.
According to Table 4, the prediction results of SRK, PR, SW, GERG
and our modification are relatively close to one another, however
the model suggested in this work is somewhat more accurate with
respect to the others. The SRK EOS predicts the cricondenbars
slightly better than the SW EOS and the GERG EOS has insignifi-
cantly larger deviations than the SW EOS. The original PR EOS

Fig. 4. Dew point pressure calculations deviations for the GERG-compatible mixtures.
 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147 1145

Fig. 5. Hydrocarbon gas dew curves for (a) Gas 16 (exp. from Avila et al., 2002b); (b) Gas 17 (exp. from Avila et al., 2002b); (c) Gas 18 (exp. from Avila et al., 2002b); (d) Gas 19 (exp.
from Avila et al., 2002b); (e) Gas 20 (exp. from Jarne et al., 2003); (f) Gas 29 (exp. from Rusten et al., 2008).

presents the largest deviations. Fig. 2 illustrates the cricondenbar
deviations for those mixtures for which the GERG EOS is applicable.
Based on Table 4, the ratios of errors of the SW, GERG, PR and
SRK to those of this work to calculate cricondenbars are 1.10, 1.12,
1.40 and 1.07 respectively; the corresponding error ratios for the
GERG-compatible mixtures of Table 2 for calculation of the cri-
condenbars are equal to 1.18, 1.35, 1.46 and 1.15 respectively.
Table 5 shows the average absolute deviations of hydrocarbon
dew point temperatures, calculated for 34 mixtures, consisting of
249 data points. As indicated from this Table, the PR EOS has the
largest deviations and the modification of this study has the least
errors. The prediction accuracies of the SRK and SW EOSs are
similar and the GERG EOS calculates better dew point temperatures
than the SRK and SW. Fig. 3 illustrates the deviations of dew point
calculations where the GERG EOS is applicable. Considering Table 5,
the ratio of errors of SW, GERG, PR and SRK to this work to calculate
dew point temperatures are 2.30, 1.88, 4.28 and 2.34, respectively;
the corresponding error ratios for the available mixtures of Table 2
for calculation of dew point temperatures are equal to 1.29, 2.15,
1.75 and 1.32, respectively.
Table 6 exhibits the percentage average absolute relative de-
viations (AARD %) for the calculated dew point pressures by the
various methods for 14 natural gas mixtures, consisting of 106 data
points and Fig. 4 illustrates the deviations of the dew point pressure
calculations for those mixtures where the GERG EOS is applicable.
The ratios of the errors of the SW, GERG, PR and SRK to this model
to calculate dew point pressures are 1.41, 1.32, 1.86 and 1.38,
respectively, and the corresponding errors for the GERG-
compatible mixtures of Table 2 for calculation of dew point pres-
sures are equal to 1.26, 1.58, 1.85 and 1.44, respectively.
The results of the various EOSs for the studied mixtures
demonstrate a similar qualitative pattern of errors for dew point
temperature and dew point pressure calculations. Fig. 5 shows the
predicted hydrocarbon gas dew points for a number of mixtures,
alongside their corresponding experimental data.
4. Conclusions
A new modification to the PR EOS (Peng and Robinson, 1976) has
been proposed to improve dew point curve predictions of natural
gases. This model presents an enhancing coefficient for the
attraction parameter of the PR EOS which is a function of reduced
temperature, reduced pressure and critical density of the mixture.
Furthermore, since the only required properties to utilize this
method are the critical properties, the method is able to be
extended to include heavy fractions as well. In order to evaluate the
model comprehensively, four major properties of the dew point
curve were compared to experimental data, consisting of the cri-
condentherm, cricondenbar, dew point temperatures and dew
point pressures. In addition to experimental data, the modified PR
was compared to the conventional PR, as well as the SRK (Soave,
1972), SW (Schmidt and Wenzel, 1980) and GERG (Kunz and
1146 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147

Fig. 5. (continued).

Wagner, 2012) EOSs for the four properties mentioned above. ascribable relation could be found between the accuracies of the
The results indicate that the proposed modification is advanta- various models with respect to lightness or heaviness of the mix-
geous in predicting natural gas dew point properties with respect tures, nor the relative amounts of aromatic or naphthenic
to the investigated equations of state, followed by the GERG EOS. components.
The SRK and SW EOSs have similar accuracies and the PR EOS has
the largest deviations. This conclusion is similar for all of the four List of Symbols
properties investigated. The ratios of the errors of the SW, GERG, PR
and SRK EOSs to this new model for the studied mixtures are 2.26, AD absolute deviation
1.69, 4.87 and 1.97, respectively for cricondentherm predictions and AAD average of absolute deviations
1.10, 1.12, 1.40 and 1.07, respectively, for cricondenbar predictions. ARD% percentage absolute of relative deviation
The corresponding ratios for dew point temperature predictions are AARD % percentage average absolute of relative deviations
2.30, 1.88, 4.28 and 23.4, respectively and these ratios are equal to F(T) temperature-dependent enhancing function
1.41, 1.32, 1.86 and 1.38, respectively, to predict dew point pressures. F(P) pressure-dependent enhancing function
The considered experimental mixtures used to develop the f1, f2, f3, f4 parameters of F(P)
model were all representative synthetic mixtures with no heavy N number of data
fractions. However, the method was even validated with respect to P pressure (MPa)
various types of components within mixtures, including branched Pc critical pressure (MPa)
alkanes, aromatics, naphthenes and heavy components up to n-C12. Pr reduced pressure
Considering all of the results presented for the criconden- T temperature (K, in equations)
therms, cricondenbars, dew point temperatures and dew point Tc critical temperature (K)
pressures for all of the synthetic and natural gas mixtures, no Tr reduced temperature
 S. Valiollahi et al. / Journal of Natural Gas Science and Engineering 34 (2016) 1137e1147
Greek Symbols
b enhancing parameter of attraction term of PR EOS
n molar volume (m3 mol1)
rc critical mass density (kg.m3)
U objective function
References
Avila, S., Blanco, S.T., Velasco, I., Rauzy, E., Otín, S., 2002. Thermodynamic properties
of synthetic natural gases. 2. Dew Point curves of synthetic natural gases and
their mixtures with water and methanol. Measurement and correlation. Energy
Fuels 16, 928e934.
Avila, S., Blanco, S.T., Velasco, I., Rauzy, E., Otín, S., 2002. Thermodynamic properties
of synthetic natural gases. 1. Dew-point curves of synthetic natural gases and
their mixtures with water and methanol. Measurement and correlation. Ind.
Eng. Chem. Res. 41, 3714e3721.
Beronich, E.L., Abdi, M.A., Hawboldt, K.A., 2009. Prediction of natural gas behaviour
in loading and unloading operations of marine CNG transportation systems.
J. Nat. Gas. Sci. Eng. 1, 31e38.
Brown, A.S., Milton, M.J.T., Vargha, G.M., Mounce, R., Cowper, C.J., Stokes, A.M.V.,
Benton, A.J., Lander, D.F., Ridge, A., Laughton, A.P., 2009. Measurement of the
hydrocarbon dew point of real and synthetic natural gas mixtures by direct and
indirect methods. Energy Fuels 23, 1640e1650.
Brown, A.S., Milton, M.J.T., Vargha, G.M., Mounce, R., Cowper, C.J., Stokes, A.M.V.,
Benton, A.J., Lander, D.F., Ridge, A., Laughton, A.P., 2009. Measurement of the
hydrocarbon dew point of real and synthetic natural gas mixtures by direct and
indirect methods. Energy Fuels 23, 1640e1650.
Danesh, A., 1998. PVT and Phase Behaviour of Petroleum Reservoir Fluids, first ed.
Elsevier Science B.V, London.
Danesh, A., Xu, D.H., Tehrani, D.H., Todd, A.C., 1995. Improving predictions of
equation of state by modifying its parameters for super critical components of
hydrocarbon reservoir fluids. Fluid Phase Equilib. 112, 45e61.
Farshchi Tabrizi, F., Nasrifar, K., 2010. Application of predictive equations of state in
calculating natural gas phase envelopes and critical points. J. Nat. Gas. Sci. Eng.
2, 21e28.
Feyzi, F., Riazi, M.R., Shaban, H.I., Ghotbi, S., 1998. Improving cubic equations of state
for heavy reservoir fluids and critical region. Chem. Eng. Commun. 167,
147e166.
€
Floter, E., de Loos, T.W., de SwaanArons, J., 1998. Improved modeling of the phase
behavior of asymmetric hydrocarbon mixtures with the PengRobinson
equation of state using a different temperature dependency of the parameter a.
Ind. Eng. Chem. Res. 37, 1651e1662.
Gasem, K.A.M., Gao, W., Pan, Z., Robinson Jr., R.L., 2001. A modified temperature
dependence for the PengeRobinson equation of state,. Fluid Phase Equilib. 181,
113e125.
George, D.L., Burkey, R.C., 2005. Measurements of Hydrocarbon Dew Points of Rich
Natural Gases. Final Report to U.S. Department of Energy, DOE Contract No. DE-
AP26e04NI41001.
George, D.L., Barajas, A.M., Kelner, E., Nored, M., 2005. Metering Research Facility
Program, Natural Gas Sample Collection and Handling e PhaseIV. GRI Topical
Report GRI-03/0049. Gas Research Institute, Des Plaines, Illinois, USA.
George, D.L., Burkey, R.C., Morrow, T.B., 2005. Metering Research Facility Program,
Natural Gas Sample Collection and Handling e Phase V. GRI Topical Report GRI-
05/0134. Gas Research Institute, Des Plaines, Illinois, USA.
Guo, T.-M., Du, L., 1989. A three-parameter cubic equation of state for reservoir
fluids. Fluid Phase Equilib. 52, 47e57.
Heidemann, R.A., Khalil, A.M., 1980. The calculation of critical points. AlChE J. 26,
769e779.
Jarne, C., Avila, S., Blanco, S.T., Rauzy, E., Otín, S., Velasco, I., 2003. Thermodynamic
Properties of synthetic natural gases. 5. Dew point curves of synthetic natural
gases and their mixtures with water and with water and methanol: mea-
surement and correlation. Ind. Eng. Chem. Res. 43, 209e217.
Jaubert, J.N., Mutelet, F., 2004. VLE predictions with the PengeRobinson equation of
state and temperature dependent kij calculated through a group contribution
method. Fluid Phase Equilib. 224, 285e304.
Kavianpour, B., Shariati, A., Moshfeghian, M., 2014. Thermodynamic investigation
and hydrate inhibition of real gas flow through orifice during depressurization.
Process Saf. Environ. Prot. 92, 224e230.
Knudsen, K., Stenby, E.H., Fredenslund, A., 1993. A comprehensive comparison of
mixing rules for calculation of phase equilibria in complex systems,. Fluid Phase
Equilib. 82, 361e368.
Kunz, O., Wagner, W., 2012. The GERG-2008 wide-range equation of state for nat-
ural gases and other mixtures: an expansion of GERG-2004. J. Chem. Eng. Data
57, 3032e3091.
Kunz, O., Klimeck, R., Wagner, W., Jaeschke, M., 2007. The GERG-2004 Wide-range
Equation of State for Natural Gases and Other Mixtures; GERG TM15, 2007;
Fortschr.-Ber. VDI, Reihe 6, Nr. 557, VDI Verlag: Düsseldorf, 2007. Also available
View publication stats
1147
as GERG Technical Monograph 15.
Lin, H., Duan, Y.Y., 2005. Empirical correction to the PengeRobinson equation of
state for the saturated region. Fluid Phase Equilib. 233, 194e203.
Louli, V., Boukouvalas, C., Voutsas, E., Magoulas, K., Tassios, D., 2007. Application of
the UMR-PRU model to multicomponent systems: prediction of the phase
behavior of synthetic natural gas and oil systems. Fluid Phase Equilib. 261,
351e358.
Maddox, R.N., Erbar, J.H., 1982. In: first ed. Gas Conditioning and Processing, Volume
3- Advanced Techniques and Applications. Campbell Petroleum Series by John
M. Campbell, Oklahoma.
Mathias, P.M., Copeman, T.W., 1983. Extension of the Peng-Robinson equation of
state to complex mixtures: evaluation of the various forms of the local
composition concept. Fluid Phase Equilib. 13, 91e108.
Michelsen, M.L., 1980. Calculation of phase envelopes and critical points for
multicomponent mixtures. Fluid Phase Equilib. 4, 1e10.
Mohsen-Nia, M., Modarress, H., Mansoori, G.A., 2003. A cubic hard-core equation of
state,. Fluid Phase Equilib. 206, 27e39.
Mørch, Ø., Nasrifar, K., Bolland, O., Solbraa, E., Fredheim, A.O., Gjertsen, L.H., 2006.
Measurement and modeling of hydrocarbon dew points for five synthetic
natural gas mixtures. Fluid Phase Equilib. 239, 138e145.
Nasrifar, K., Bolland, O., 2006. Prediction of thermodynamic properties of natural
gas mixtures using 10 equations of state including a new cubic two-constant
equation of state. J. Pet. Sci. Eng. 51, 253e266.
Nasrifar, K., Moshfeghian, M., 1998. A saturated liquid density equation in
conjunction with the Predictive-SoaveeRedlicheKwong equation of state for
pure refrigerants and LNG multicomponent systems,. Fluid Phase Equilib. 153,
231e242.
Nasrifar, K., Ayatollahi, S., Moshfeghian, M., 2000. Generalized saturated liquid
density prediction method for pure compounds and multi-component mix-
tures. Fluid Phase Equilib. 168, 71e90.
Nasrifar, K., Bolland, O., Moshfeghian, M., 2005. Predicting natural gas dew points
from 15 equations of state. Energy Fuels 19, 561e572.
Nazarzadeh, M., Moshfeghian, M., 2013. New volume translated PR equation of state
for pure compounds and gas condensate systems. Fluid Phase Equilib. 337,
214e223.
Patel, N.C., Teja, A.S., 1982. A new cubic equation of state for fluids and fluid mix-
tures. Chem. Eng. Sci. 37, 463e473.
Pedersen, K.S., Christensen, P.L., 2007. Phase Behavior of Petroleum Reservoir Fluids.
CRC Press, New York.
Peng, D.Y., Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng.
Chem. Fundam. 15, 59e64.
Prausnitz, J.M., Lichtenthaler, R.N., de Azevedo, E.G., 1999. Molecular Thermody-
namics of Fluid-phase Equilibria, third ed. Prentice-Hall, New Jersey.
Redlich, O., Kwong, J.N.S., 1949. On the thermodynamics of solutions. V. An equation
of state. Fugacities of gaseous solutions. Chem. Rev. 44, 233e244.
Robinson, D.B., Peng, D.Y., 1978. The Characterization of Heptanes and Heavier
Fractions for the GPA Peng-Robinson Program, Research Report PR-28. Gas
Processors Association, Tulsa, OK.
Rusten, R.H., Gjertsen, L.H., Solbraa, E., Kirkerød, T., Haugum, T., Puntervold, S., 2008.
Determination of the phase envelopee crucial for process design and problem
solving. In: 87th Annual GPA Convention, Grapevine.
Salim, P.H., Trebble, M.A., 1991. A modified TrebbledBishnoi equation of state:
thermodynamic consistency revisited,. Fluid Phase Equilib. 65, 59e71.
Schmidt, G., Wenzel, H., 1980. A modified van der Waals type equation of state,.
Chem. Eng. Sci. 35, 1503e1512.
H.J. Secord, B.J. Clarke, Method of Storing Natural Gas for Transport, US Patent
3232725 (1966).
Soave, G., 1972. Equilibrium constants from a modified Redlich-Kwong equation of
state. Chem. Eng. Sci. 27, 1197e1203.
Souahi, F., Sator, S., Albane, S.A., Kies, F.K., Chitour, C.E., 1998. Development of a new
form for the alpha function of the RedlicheKwong cubic equation of state. Fluid
Phase Equilib. 153, 73e80.
Twu, C.H., Coon, J.E., Cunningham, J.R., 1995. A new generalized alpha function for a
cubic equation of state Part 2. Redlich-Kwong equation,. Fluid Phase Equilib.
105, 61e69.
Twu, C.H., Coon, J.E., Cunningham, J.R., 1995. A new generalized alpha function for a
cubic equation of state Part 1. Peng-Robinson equation. Fluid Phase Equilib. 105,
49e59.
Valderrama, J.O., 1990. A generalized patel-teja equation of state for polar and
nonpolar fluids and their mixtures. J. Chem. Eng. Jpn. 23, 87e91.
von Solms, N., Michelsen, M.L., Kontogeorgis, G.M., 2003. Computational and
physical performance of a modified PC-SAFT equation of state for highly
asymmetric and associating mixtures. Ind. Eng. Chem. Res. 42, 1098e1105.
Voutsas, E., Magoulas, K., Tassios, D., 2004. Universal mixing rule for cubic equations
of state applicable to symmetric and asymmetric systems: results with the
PengRobinson equation of state. Indus. Eng. Chem. Res. 43, 6238e6246.
Zhou, J., Patil, P., Ejaz, S., Atilhan, M., Holste, J.C., Hall, K.R., 2006. (p, vm, T) and phase
equilibrium measurements for a natural gas-like mixture using an automated
isochoric apparatus. J. Chem. Thermodyn. 38, 1489e1494.