Accepted Manuscript

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

gases
Saeid Valiollahi, Babak Kavianpour, Sona Raeissi, Mahmood Moshfeghian
PII:

S1875-5100(16)30521-2

DOI:

10.1016/j.jngse.2016.07.049

Reference:

JNGSE 1671

To appear in:

Journal of Natural Gas Science and Engineering

Received Date: 6 April 2016

Revised Date:

19 July 2016

Accepted Date: 22 July 2016

Please cite this article as: Valiollahi, S., Kavianpour, B., Raeissi, S., Moshfeghian, M., A new PengRobinson modification to enhance dew point estimations of natural gases, Journal of Natural Gas
Science & Engineering (2016), doi: 10.1016/j.jngse.2016.07.049.
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A new Peng-Robinson modification to enhance dew point estimations of

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natural gases

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Saeid Valiollahia, Babak Kavianpoura, Sona Raeissia,*, Mahmood Moshfeghianb

School of Chemical and Petroleum Engineering, Shiraz University, Mollasadra Ave., Shiraz 71345, Iran

John M Campbell & Co., 1215 Crossroads Boulevard, Norman, OK 73072, USA

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Intended for publication in: Journal of Natural Gas Science and Engineering.

*Corresponding author
Tel: +987136133707

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Abstract
Equations of state (EOSs) are widely used in calculations such as those involving reservoir simulation,

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process simulation, gas processing and transportation of natural gas. Predicting the phase envelope,
specifically the dew points of natural gas, is among the important roles of EOSs. In this study, a
modification is proposed to improve the predictions of dew point properties by the Peng-Robinson (PR)
EOS, where the attraction parameter has been modified by a new empirical-based coefficient which is a

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function of reduced pressure, reduced temperature and critical density. In order to validate the
modification, results are presented for four major properties of dew points consisting of the

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cricondentherm, cricondenbar, dew point temperature and dew point pressure. Furthermore, the
performances of the original PR, Soave-Redlich-Kwong (SRK), Schmidt-Wenzel (SW) and GERG-2008
EOSs, have been compared to predict the above four properties with respect to the experimental data.
Having similar qualitative trends for the four properties, the results show that the modification of this
study gives better predictions of the dew point curves, followed by the GERG EOS, which was developed

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particularly for processed natural gases. The SRK and SW EOSs have comparatively similar results and

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the PR EOS has the largest deviations.

state.

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Keywords: Hydrocarbon; Phase envelope; Phase equilibria; Cricondentherm; Cricondenbar; Equation of

1. Introduction

Precise predictions of natural gas phase behavior are essential for the design of its production, processing
and transportation facilities. For example, in the design of natural gas pipelines, one favorable alternative
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is to transport the gas as a dense phase or a supercritical fluid [1,2]. 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

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higher temperatures and pressures than the critical point.

Equations of state (EOSs) are extensively used to predict thermodynamic properties and phase behavior.
Cubic EOSs, such as the Soave-Redlich-Kwong (SRK) [3] and the Peng-Robinson (PR) [4], are more

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commonly used due to their reliability, the simplicity of their Pressure-Volume-Temperature (PVT)
relationships, and the relative ease in specifying their thermodynamic functions such as enthalpy, entropy,

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heat capacity and speed of sound, which require algebraic calculations and differentiations [5]. Although
a number of modifications of the PR and SRK EOSs have been proposed to improve their predictions of
vapor pressure and liquid density [6-10] and vapor-liquid equilibria (VLE), EOS modifications
specifically aimed at the improvement of natural gas phase envelope predictions are limited.

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In 1998, Feyzi et al. [6] 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 predictions for a limited number of binary systems. In 2006,
Nasrifar and Bolland [11] demonstrated that SRK-type EOSs and the Schmidt-Wenzel (SW) EOS [12]

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give better agreement with experimental values of two natural gas mixtures, as compared to the PR EOS.
Mrch et al. [13] improved dew point predictions of the Redlich-Kwong (RK) EOS [14] by modifying the

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function for the EOS attractive term [15]. 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
hypothetical heavy fraction because the coefficients of the function (the Mathias and Copeman
coefficients) [16,17] were not proposed to relate the properties of heavy fractions.
Nasrifar et al. [18] studied dew point predictions of a number of EOSs, including the SRK EOS with two
modifications [7,8], the PR EOS with four modifications [19-22], five three-parameter EOSs including
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the SW EOS [12,23-26] and one four-parameter EOS [27]. The calculations were compared with data
from five lean synthetic natural gas mixtures and twelve rich natural gases with heavy ends. Since the
modifications investigated [7,8,19-22] were proposed to enhance properties other than dew points, they

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were not clearly superior with respect to the corresponding original EOS for dew point calculations.
However, the study of Nasrifar et al. [18] 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

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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

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dominant component of natural gas is methane, a more precise prediction of this components fugacity
does not assure better dew point predictions because the dew curve is very sensitive to the composition of
the intermediate and heavy components [2].

In 2010, Tabrizi and Nasrifar [28] slightly improved the accuracy of dew curve calculations of nine
hydrocarbon mixtures, as compared to the PR EOS, using a two-parameter EOS [11] incorporating a

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binary interaction correlation [29]. Rusten et al. [2] evaluated the accuracy of the PR, SRK, PC-SAFT
[30] and GERG-2004 [31] 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 mixtures with

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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

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the cricondenbar on the phase envelope. Their study showed that the phase envelope prediction errors of
an EOScan be higher for the region between the cricondenbar and cricondentherm, 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 mixtures. The modification is validated by experimental data from literature and
its performance is compared to the PR, SRK, SW and GERG-2008 [32] EOS.
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2. Theory and Method

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2.1 Model

In this study, VLE calculations [33] for dew point pressures were performed using the procedure
proposed by Pedersen and Christensen [34], starting from an intermediate pressure and progressively

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going to higher pressures in order to eliminate convergence problems at high pressures [35]. The
calculations for dew point temperatures were accomplished by the suggested procedure of Maddox and

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Erbar [36]. 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 calculations was considered as the cricondenbar.
The prediction of dew points can be improved by using binary interaction parameters. Jaubert and Mutelet

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[37] proposed an approach to calculate binary interaction parameter for the modification of the PR EOS
[29]. In this study the binary interaction parameters are obtained from the study of Knapp and Doring.
These have been summarized by Danesh [38]. However, for the mixtures containing highly polar and

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asymmetric compounds, only optimizing on interaction parameters may sometimes be insufficient for
proper modeling accuracy [39], thus several mixing rules have been proposed for this purpose. In 2004,

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Voutsas et al. [40] 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 [41]. 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

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mixtures of reservoir fluids [38]. 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

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term empirically. To do this, we consider that the PR EOS most often underestimates the corresponding
experimental dew curve data [2,11,13,18], 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

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region between the cricondentherm and cricondenbar.

By multiplying the attraction term of the PR EOS by a suitable coefficient, it might be possible to

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constructively change the shape of the resulting dew curve. However, to get the best results, the
coefficient should not be constant, but rather, mixture-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.

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The following form is considered to introduce an enhancing coefficient, , which is considered to be a

function of temperature and pressure.

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dew
aPR
= aPR

= 1 + F (T ) F ( P )

(1)

(2)

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Where F(T) , F(P), and

are the temperature-dependent function, pressure-dependent function,

the attraction parameter of the original PR EOS [4], and the newly modified attraction parameter,
respectively. The temperature-dependent function has been determined as follows:

F (T ) = (Tr ,mix 0.5 1)

0.5

(3)

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Where Tr,mix denotes the reduced temperature of the mixture. Including this temperature-dependent
function makes the modification specifically suitable for dew point calculations where Tr,mix is greater
than one.

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The function F(P) is obtained by optimizing to experimental data at various temperatures and pressures,
in a way to minimize the following objective function using the Levenberg-Marquardt method.
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.
= exp. F(calc

P
)
F (T )
exp.

(4)

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The parameter exp is the numerical correction coefficient which makes the calculated dew point of the PR
EOS overlap the corresponding experimental dew point. It is unique for each single experimental dew
point. The subtraction term in Eq. 4 denotes the difference of experimental value of the pressuredependent function at the pressure and temperature of the experimental dew point and the corresponding

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calculated pressure-dependent function.

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2.2 Data collection and division of datasets

To propose and verify the model for predicting the cricondentherm, cricondenbar, dew point temperatures

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and dew point pressures of natural gas, a dataset consisting of a total of 36 experimental hydrocarbon gas
mixtures is obtained from literature (Tables 1 and 2). Of these 36 mixtures, 15 (Table 1) were used for the
development of the model, while the remaining 21 mixtures (Table 2) provide purely predictive results to
verify the model.

Not only are the compositions of the mixtures presented in Table 1, but also the different composition
accuracies among the various literature references are given in this table. The reason for the selection of
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these particular data sets is due to their synthetic nature, providing for more accurate compositions as
compared to real natural gas mixtures. In addition, they have an appropriate quantity and distribution of

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experimental data points throughout the phase envelope.

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Table 1 Code names, references and compositions of mixtures utilized to develop the modification

The data used to verify the model (Table 2) also include real natural gas mixtures. The advantage of this

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approach, in addition to validation with mixtures which were not used for its development, is that in
contrast to the synthetic mixtures of Table 1, the real natural gas mixtures (with the code names of Gas 16
to Gas 36) used for validation provide for a wider range of components.

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Table 2 Code names, references and compositions of the natural gas mixtures used only for validation

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In this study, the critical properties of the mixtures were obtained from the proposed method by

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Heidemann and Khalil [42].

3. Results and discussion

Following the method explained above and optimizing to the training dataset given in Table 1, the
following pressure-dependent function is obtained in this study:

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F ( P ) = f1 ( f 2 + f 3 Pr , m ix + f 4 Pr , m ix 2 )

(5)

f1 = 1.030 exp exp(9.3890 0.8524 c , m ix )

f 2 = 3744.556 c , mix 4.2525

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f 3 = 568313.250 c ,mix 5.9531

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Where

(7)

(8)

(9)

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f 4 = 1166215.400 c , mix 6.2409

(6)

in which Pr,mix and c,mix are the reduced pressure and the critical molar density of the natural gas mixture,
respectively.

The pressure-dependent function takes into account the important role of pressure to improve dew point

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predictions. This function, at high pressures, results in the increases of . However, at the near-critical
region, the temperature-dependent function neutralizes the increase of , and at higher temperatures it
makes the enhancing coefficient larger. As a result, the proposed temperature and pressure dependent

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functions can mathematically compensate the underestimations of dew point curves by the PR EOS,
specifically in the supercritical region where larger deviations are observed. The coefficients presented

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through Eq. 5 to 9 have conformity 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 predicting 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, it provides for a purely predictive investigation
of accuracies. In addition, in contrast to the synthetic mixtures of Table 1, real natural gas mixtures (code
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names Gas 16-36) 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

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concern (cricondentherm, cricondenbar, dew point temperature and dew point pressure). Consequently,
the error results presented are limited to the available experimental values for each studied property. The
following relations define the reported deviations.

1
N

ARD % =

calc. exp.
calc . exp .
exp .

100 calc . exp.

exp.
N

(10)

(11)

(12)

(13)

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AARD % =

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AAD =

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AD = calc . exp.

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

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percentage absolute relative deviation, percentage average absolute relative deviation and the number of
data points, respectively.

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The values of experimental and calculated cricondentherms for 28 mixtures of gases and the absolute
deviations (AD) of the cricondentherm predictions with respect to the corresponding experimental values
are presented in Table 3.

Table 3 Experimental and calculated cricondentherms and absolute deviations (AD) of the
cricondentherm calculations for the various models
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Since the GERG EOS has been developed for only limited components, considering the behavior of
natural gas mixtures that contain naphthenic, aromatic and some branched alkanes was not intended for

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this EOS. Subsequently, the average deviations are presented in two groups; one for those which are
compatible with the GERG EOS and one including all of the data. Figure 1summarizes the results of

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cricondentherm prediction accuracies, in the case of only those systems for which GERG is suitable.

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Figure 1 Cricondentherm calculation deviations for the GERG-compatible mixtures

Considering Table 3 and Figure 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

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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 corresponding values for the GERG EOS-compatible

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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

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mixtures and the percentage absolute relative deviations (ARD %) of these cricondenbar calculations.

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

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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

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EOS has insignificantly larger deviations than the SW EOS. The original PR EOS presents the largest
deviations. Figure 2 illustrates the cricondenbar deviations for those mixtures for which the GERG EOS
is applicable.

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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-

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compatible mixtures of Table 2 for calculation of the cricondenbars are equal to 1.18, 1.35, 1.46 and 1.15
respectively.

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Figure 2 Cricondenbar calculation deviations for the GERG-applicable mixtures.

Table 5 shows the average absolute deviations of hydrocarbon dew point temperatures, calculated for 34

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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

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and SW EOSs are identical and the GERG EOS calculates better dew point temperatures than the SRK
and SW. Figure 3illustrates 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.

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

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Figure 3 Dew point temperature calculation deviations for the GERG-applicable mixtures

Table 6 exhibits the percentage average absolute relative deviations (AARD %) for the calculated dew

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point pressures by the various methods for 14 natural gas mixtures, consisting of 106 data points and
Figure 4 illustrates the deviations of the dew point pressure calculations for those mixtures where the

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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 pressures are equal to 1.26, 1.58,

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1.85 and 1.44, respectively.

Table 6 Percentage average absolute relative deviations (AARD %) of dew point pressure calculations for

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14 mixtures of natural gases

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Figure 4 Dew point pressure calculation deviations for the GERG-applicable mixtures
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. Figure 5 shows the predicted hydrocarbon
gas dew points for a number of mixtures, alongside their corresponding experimental data.

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Figure 5 Hydrocarbon gas dew curves for (a) Gas 16 (exp. from [46]); (b) Gas 17 (exp. from [46]); (c)
Gas 18 (exp. from [46]); (d) Gas 19 (exp. from [46]); (e) Gas 20 (exp. from [44]); (f) Gas 29 (exp. from

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[2])

4. Conclusions

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A new modification to the PR EOS [4] 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

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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,

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consisting of thecricondentherm, 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
[3], SW [12] and GERG [32] EOSs for the four properties mentioned above.

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The results indicate that the proposed modification is advantageous in predicting natural gas dew point
properties with respect to the investigated equations of state, followed by the GERG EOS. The SRK and

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SW EOSs have similar accuracies and the PR EOS has the largest deviations. This conclusion is similar
for all of the four 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, 1.69, 4.87 and 1.97, respectively for cricondentherm
predictions and 1.10, 1.12, 1.40 and 1.07, respectively, for cricondenbar predictions. The corresponding
ratios for dew point temperature predictions are 2.30, 1.88, 4.28 and 23.4, respectively and these ratios are
equal to 1.41, 1.32, 1.86 and 1.38, respectively, to predict dew point pressures.

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The considered experimental mixtures used to develop the model were all representative synthetic
mixtures with no heavy fractions. However, the method was even validated with respect to various types
of components within mixtures, including branched alkanes, aromatics, naphthenes and heavy

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components up to n-C12.
Considering all of the results presented for the cricondentherms, cricondenbars, dew point temperatures
and dew point pressures for all of the synthetic and natural gas mixtures, no ascribable relation could be

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nor the relative amounts of aromatic or naphthenic components.

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found between the accuracies of the various models with respect to lightness or heaviness of the mixtures,

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List of Symbols
AD: absolute deviation

ARD%: percentageabsolute of relative deviation

AARD %: percentage average absolute of relative deviations
F(T): temperature-dependent enhancing function

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F(P): pressure-dependent enhancing function

f1, f2, f3, f4: parameters of F(P)

P: pressure (MPa)
Pc: critical pressure (MPa)
Pr: reduced pressure
T: temperature (K, in equations)
Tc: critical temperature (K)

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Tr: reduced temperature

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N: number of data

Greek Symbols

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AAD: average of absolute deviations

: parameter in attraction term of PR EOS

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: enhancing parameter of attraction term of PR EOS

: molar volume (m3 mol-1)

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c: critical mass density (kg.m-3)

: objective function

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[25] J. Valderrama, eacute, O, A Generalized Patel-Teja Equation of State for Polar and Nonpolar Fluids
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consistency revisited, Fluid Phase Equilib., 65 (1991) 59-71.
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Modified PC-SAFT Equation of State for Highly Asymmetric and Associating Mixtures, Ind. Eng. Chem.
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model to multicomponent systems: Prediction of the phase behavior of synthetic natural gas and oil
systems, Fluid Phase Equilib., 261 (2007) 351-358.
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Measurement and Correlation, Energy Fuels, 16 (2002) 928-934.

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[46] S. Avila, S.T. Blanco, I. Velasco, E. Rauzy, S. Otn, 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 (2002) 3714-3721.

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Thermodyn., 38 (2006) 1489-1494.
[49] A.S. Brown, M.J.T. Milton, G.M. Vargha, R. Mounce, C.J. Cowper, A.M.V. Stokes, A.J. Benton,
D.F. Lander, A. Ridge, A.P. Laughton, Measurement of the Hydrocarbon Dew Point of Real and
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TE
D

[50] D.L. George, A.M. Barajas, E. Kelner, M. Nored, Metering research facility program, natural gas
sample collection and handling phaseIV, GRI Topical Report GRI-03/0049, Gas Research Institute, Des
Plaines, Illinois, USA, 2005.
[51] D.L. George, R.C. Burkey, T.B. Morrow, Metering research facility program, natural gas sample
collection and handling phase V., GRI Topical Report GRI-05/0134, Gas Research Institute, Des
Plaines, Illinois, USA, 2005.

AC
C

EP

[52] D.L. George, R.C. Burkey, Measurements of hydrocarbon dew points of rich natural gases, Final
Report to U.S. Department of Energy, DOE Contract No. DE-AP26-04NI41001, 2005.

20

ACCEPTED MANUSCRIPT

Table 1 Code names, references and compositions of mixtures utilized to develop the model

Gas 1
(mol %)
[43]

Gas 2
(mol %)
[43]

Gas 3
(mol %)
[43]

Gas 4
(mol %)
[43]

Gas 5
(mol %)
[44]

Gas 6
(mol %)
[13]

Gas 7
(mol %)
[13]

Gas 8
(mol %)
[13]

Gas 9
(mol %)
[13]

Gas 10
(mol %)
[13]

Gas 11
(mol %)
[45]

Gas 12
(mol %)
[45]

Gas 13
(mol %)
[45]

Gas 14
(mol %)
[45]

Gas 15
(mol %)
[45]

93.505
2.972
1.008
1.050
1.465

84.280
10.067
4.028
0.597
1.028

92.2325

98.6879

97.3065

6.8677

7.7122

6.3712

0.7059

1.6081

1.7107

2.2104

1.0492

0.4597

0.8781

0.8480

0.5428

0.1582

0.07821

0.09047

93.600
2.630
0
1.490
1.490
0
0.795

89.3411

94.085
4.468
0
0
0
0
1.447

90.2309

96.611
0
0
1.527
1.475
0
0.385

0.2653

0.1326

0.09463

0.03582

0.05339

0.05142

0.03196

0.04404

0.009911

0.02949

0
0
0

0
0
0

0
0
0

0.009383
0.001217
0.000003

0.01197
0.001361
0.001018

0.01575
0.003220
0.001585

0.005923
0.003486
0.002175

0.007274
0.002490
0.001763

0
0
0

0
0
0

0
0
0

0.000001
0.004523
0.006103

0.000003
0.005579
0.00419

0.000005
0.005919
0.01398

0.000984
0.003160
0.003536

0.001175
0.005010
0.009786

0.002463

0.003225

0.008588

0.003005

0.005853

0.862

0.410

C1

n-C5

89.9584
8.22
0.9
0.11
0.13
0.0084
0.0032

88.7634
8.54
1.68
0.22
0.29
0.0182
0.0084

86.4838
9.832
2.388
0.183
0.231
0.0139
0.0063

n-C6

96.4654
2.510
0.213
0.184
0.197
0.0096
0.0100
0.0010

0.772
1.700
84.446
8.683
3.297
0.293
0.589
0.084
0.086
0.050

n-C7
n-C8
n-C9

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

n-C10
Cyclohexane
Benzene

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

Toluene

i-C4
n-C4
i-C5

EP

C3

AC
C

C2

SC

0.48

M
AN
U

0.67

TE
D

N2
CO2

RI
PT

Component

21

ACCEPTED MANUSCRIPT

Table 2 Code names, references and compositions of the natural gas mixtures used only for validation
Gas17
(mol %)
[46]
0
0

Gas18
(mol %)
[46]
0
0

Gas19
(mol %)
[46]
0
0

Gas20
(mol %)
[44]
0
0

Gas 21
(mol %)
[47]
0
0

Gas22
(mol %)
[47]
0
0

Gas23
(mol %)
[48]
0
0

Gas24
(mol %)
[49]
0.0319
0.0078

Gas25
(mol %)
[49]
0.0470
0.00070

Gas26
(mol %)
[49]
0.0420
0.00080

Gas27
(mol %)
[49]
0.0329
0.0100

Gas28
(mol %)
[49]
0.0030
0.0062

Gas29
(mol %)
[2]
0
0

Gas30
(mol %)
[2]
0
0

N2
O2
CO2

0.618
0
0.187

2.80
0
0.20

6.90
0
0.51

5.651
0
0.284

1.559
0
25.908

0
0
1.542

0.391
0
1.111

2.031
0
0.403

6.1120
0.0269
0.0569

4.1880
0.0040
1.0020

2.4600
0.0060
0.4775

7.1560
0.0160
0.4713

0.4450
0.0030
1.7290

0.5108
0
1.8922

1.6298
0
0.3207

CO
C1
C2

0
98.943
0.082

0
96.6159
0.18

0
88.1882
2.72

0
83.3482
7.526

0
69.114
2.620

0.095
84.084
7.223

0
83.687
7.595

0
90.991
2.949

0
83.5100
5.7600

0
89.2900
3.9110

0
93.3100
2.8140

0
85.9500
4.3580

0
88.3200
7.3150

0
86.6295
6.1903

0
93.2144
3.7328

C3
i-C4
n-C4

0.065
0.05
0

0.1029
0.0499
0.0095

0.85
0.17
0.32

2.009
0.305
0.520

0.423
0.105
0.104

4.441
1.042
0

4.748
0.231
1.450

1.513
0.755
0.755

2.3990
0.4863
0.8909

0.9790
0.1597
0.2048

0.5024
0.0874
0.1113

1.0650
0.2253
0.3273

1.7830
0.1625
0.1968

2.7941
0.4635
0.7524

0.5654
0.2906
0.0653

i-C5
n-C5
n-C6

0.017
0
0.032

0.0166
0
0.0160

0.0850
0.0940
0.119

0.120
0.144
0.068

0.034
0.023
0.110

0.423
0.493
0.658

0.316
0.331
0.037

0.299
0.304
0

0.2816
0.2314
0.0327

0.0565
0.0528
0.0161

0.0356
0.0331
0.0144

0.1240
0.1040
0.0399

0.0216
0.0143
0.0010

0.2109
0.1837
0.0503

0.0483
0.0167
0.0038

n-C7
n-C8
n-C9

0.0027
0.0033
0

0.0054
0.0038
0

0.0258
0.0180
0

0.0138
0.011
0

0
0
0

0
0
0

0.045
0.058
0

0
0
0

0.0339a
0.0022a
0.00026a

0.0148a
0.0035a
0.0012a

0.0200a
0.0088a
0.0042a

0.0304a
0.0040a
0.00059a

0.00049a
0.000017a
0.000003a

0.0297a
0.0039a
0.0006a

0.0067a
0.0007a
0

n-C10
n-C11
n-C12

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0.000003a
0
0

0.00012a
0.000008a
0

0.00048a
0.000031a
0.0000002a

0.000035a
0.000002a
0

0
0
0

0
0
0

0
0
0

2,2-dimethylpropane
2,2-dimethylbutane
2,3-dimethylbutane

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0.0094
0.0085
0.0121

0.0049
0.0042
0.0034

0.0031
0.0039
0.0029

0.0101
0.0105
0.0066

0
0.00015
0.00055

0.0160
0.0055
0.0094

0.0042
0.0042
0.0065

2-methylpentane
3-methylpentane
Cyclopentane

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0.0546
0.0309
0

0.0124
0.0063
0

0.0100
0.0057
0

0.0307
0.0173
0

0.0011
0.00053
0

0.0402
0.0221
0.0164

0.0165
0.0089
0.0092

Methylcyclopentane
Cyclohexane
Methylcyclohexane

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0.0171
0.0056

0
0.0072
0.0056

0
0.0075
0.0077

0
0.0077
0.0046

0
0.00019
0.000061

0
0.0866a
0

0
0.0408a
0

Cycloheptane
Cyclooctane
Benzene

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0

0
0
0.00025

0
0
0.0250

0
0
0.0226

0
0
0.00039

0
0
0.00034

0.0317a
0.0008a
0.0362a

0.0136a
0.0004a
0.0002a

Toluene
m-Xylene

0
0

0
0

0
0

0
0

0
0

0
0

0
0

0
0

0.000031
0

0.0032
0

0.0053
0

0.00008
0

0.000051
0

0.0209a
0.0023a

0.0004a
0

SC

M
AN
U

TE
D

EP

AC
C

RI
PT

He
H2

Gas 16
(mol %)
[46]
0
0

Component

22

ACCEPTED MANUSCRIPT

Table 2 (cont.)

0
0

N2
O2
CO2

0.993
0
0.501

2.432
0
0.984

5.060
0
1.520

CO
C1
C2

0
94.737
2.022

0
85.500
4.896

0
69.818
9.093

C3
i-C4
n-C4

0.746
0.299
0.302

2.959
0.985
0.986

i-C5
n-C5
n-C6

0.151
0.150
0.032

0.481
0.494
0.079

0.030
0.009
0.001

Gas 34
(mol %)
[51]

Gas 35
(mol %)
[51]

Gas 36
(mol %)
[52]

0
0

0
0

0
0

2.506
0.011
1.006

5.121
0
1.556

2.005
0
1.200

0
85.224
4.995

0
69.410
9.222

0
65.529
10.228

2.997
1.005
1.001

6.117
3.028
3.022

7.907
2.101
6.207

1.003
1.005
0.130

0.503
0.502
0.08096

1.008
1.016
0.13082

1.810
2.212
0.382

0.074
0.022
0.003

0.121
0.036
0.005

0.07542
0.02217
0.00333

0.12187
0.03582
0.00538

0.136
0.060
0.015

0.001
0
0

0.003
0
0

0.004
0
0

0.00256
0
0

0.00414
0
0

0.006
0
0

0
0.001
0.002

0
0.002
0.005

0
0.002
0.008

0
0.00155
0.00523

0
0.0025
0.00846

0
0
0

2-methylpentane
3-methylpentane
Cyclopentane

0.016
0.006
0

0.039
0.015
0

0.064
0.025
0

0.03965
0.01548
0

0.06408
0.02502
0

0
0
0

Methylcyclopentane
Cyclohexane
Methylcyclohexane

0.001
0
0

0.003
0
0

0.005
0
0

0.00337
0
0.00029

0.00545
0
0.00046

0
0
0

Cycloheptane
Cyclooctane
Benzene

0
0
0

0
0
0

0
0
0.049

0
0
0

0
0
0.049

0
0
0.102

Toluene
m-Xylene

0
0

0
0

0.050
0

0
0

0.047
0

0.100
0

n-C10
n-C11
n-C12

AC
C

EP

TE
D

2,2-dimethylpropane
2,2-dimethylbutane
2,3-dimethylbutane

M
AN
U

6.003
2.998
2.999

n-C7
n-C8
n-C9

Gas 33
(mol
%)
[50]
0
0

RI
PT

He
H2

Gas 32
(mol
%)
[50]
0
0

SC

Component

Gas 31
(mol %)
[50]

The model component has been characterized in literature

23

ACCEPTED MANUSCRIPT

Table 3 Experimental and calculated cricondentherms and absolute deviations (AD) of the cricondentherm calculations
for the various models
EOS cricondentherm ( C) ,(AD) ( C)
Gas no.

Exp. ( C)
SRK

PR

GERG

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)

Gas 9

3.65

2.97 , (0.68)

0.97 , (2.68)

3.51 , (1.73)

1.83 , (3.42)

-6.08

-6.59 , (0.51)

-8.71 , (2.63)

Gas 12

-8.94

-8.17 , (0.77)

Gas 13

-6.71

-4.85 , (1.86)

Gas 14

-6.60

-3.86 , (2.75)

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5.25

Gas 11

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-4.48 , (0.37)

-6.14 , (1.29)

-4.30 , (0.55)

2.87 , (0.78)

2.14 , (1.51)

4.00 , (0.35)

5.47 , (0.22)

3.84 , (1.41)

5.30 , (0.05)

NA

-6.70 , (0.62)

-6.40 , (0.32)

-10.82 , (1.88)

NA

-8.13 , (0.81)

-9.11 , (0.17)

-7.69 , (0.98)

NA

-5.03 , (1.68)

-6.20 , (0.51)

-7.26 , (0.66)

NA

-3.05 , (3.55)

-6.41 , (0.19)

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-3.95

-1.64 , (2.32)

Gas 16

-27.65

-26.49 , (1.16)

Gas 17

-27.65

-25.76 , (1.89)

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

Gas 26

2.30

Gas 27

-1.77

Gas 29

-0.86 , (3.09)

-3.80 , (0.15)

-26.78 , (0.87)

-28.50 , (0.85)

-28.35 , (0.70)

-25.71 , (1.94)

-26.06 , (1.59)

-27.70 , (0.05)

9.71 , (1.26)

7.08 , (1.37)

NA

9.13 , (0.68)

9.63 , (1.18)

2.09 , (0.20)

NA

5.08 , (2.78)

3.97 , (1.67)

-0.03 , (1.74)

-2.62 , (0.85)

NA

-0.55 , (1.22)

-0.20 , (1.57)

-37.78

-37.18 , (0.60)

-38.79 , (1.01)

NA

-37.10 , (0.68)

-37.50 , (0.28)

19.97

20.40 , (0.43)

17.85 , (2.12)

NA

19.65 , (0.32)

20.10 , (0.13)

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

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NA

-26.57 , (1.08)

5.12 , (2.81)

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Gas 28

-4.99 , (1.04)

-29.09 , (1.44)

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75.62 , (3.98)

72.41 , (7.19)

NA

75.04 , (4.56)

74.30 , (5.30)

Overall average AD ( C)
(GERG compatible)

0.96

2.39

0.83

1.11

0.49

Overall average AD ( C)

1.38

2.14

NA

1.46

0.81

* NA: Not available

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

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EOS cricondenbar (MPa) ,(ARD %)

Gas no.

Exp. (MPa)

SRK

PR

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Gas 2

7.12

6.94, (2.49)

6.84 , (3.93)

6.96 , (2.25)

Gas 3

7.77

7.20 , (7.34)

6.99 , (10.04)

7.19 , (7.46)

Gas 4

5.84

5.58 , (4.37)

5.51 , (5.79)

5.64 , (3.39)

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6.92 , (2.78)

6.96 , (2.25)

7.13 , (8.27)

7.14 , (8.11)

5.60 , (4.16)

5.60 , (4.11)

8.18 , (0.00)

8.24 , (0.73)

Gas 5

8.18

8.20 , (0.24)

8.07 , (1.34)

8.21 , (0.37)

Gas 16

6.39

6.49 , (1.51)

6.22 , (2.75)

6.64 , (3.85)

Gas 17

6.39

6.55 , (2.58)

6.30 , (1.39)

6.72 , (5.23)

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)

9.07 , (2.53)

10.74

10.27 , (4.37)
3.72

Overall average

3.78

6.42 , (0.47)

8.88 , (0.37)

8.98 , (1.55)

9.03 , (2.12)

9.13 , (3.25)

10.00 , (6.89)

NA

10.22 , (4.90)

10.27 , (4.39)

4.86

3.88

3.81

3.45

5.07

NA

3.92

3.54

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6.31 , (1.25)

6.60 , (3.33)

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Gas 29

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6.50 , (1.66)

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Table 5 AAD of dew point temperature calculations for 34 natural gas mixtures
EOS dew point temperature calculation deviation (AAD)
PR

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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

Gas 12

1.1

Gas 13

1.7

Gas 14

2.5

Gas 15

1.9

Gas 16

1.3

Gas 17

1.9

Gas 18

5.0

Gas 19

0.8

Gas 20

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1.6

NA

0.6

0.7

1.6

NA

1.2

0.7

1.3

NA

1.4

0.6

3.3

NA

2.8

0.7

1.8

NA

2.5

0.4

2.2

2.2

0.8

1.0

1.5

2.9

1.7

0.3

1.9

1.0

2.5

0.6

3.8

0.7

1.1

0.7

1.5

0.6

0.6

1.4

0.5

2.2

6.0

2.7

3.0

1.6

1.0

1.3

NA

0.5

1.1

1.8

2.0

NA

2.0

1.4

2.3

1.1

NA

2.2

1.6

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

(GERG compatible)

1.464

2.679

1.178

1.442

0.626

Overall average AAD

1.836

2.782

NA

1.873

1.221

Gas 23
Gas 24
Gas 25
Gas 26

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

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mixtures of natural gases

EOS dew point pressure calculation deviation (AARD%)

Gas no.

SRK

PR

GERG

Gas 2

4.61

5.3

5.13

Gas 3

9.51

14.11

10.37

Gas 4

6.60

13.24

7.80

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5.17

3.28

10.38

8.50

6.26

7.73

0.72

1.26

0.60

3.13

0.69

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

Gas 19

8.61

Gas 21

4.22

Gas 22

3.67

Gas 23

2.27

Gas 29

3.59

Overall average AARD%

(GERG compatible)

6.42

Overall average AARD%

5.87

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Gas 5

14.13

5.86

10.70

4.93

4.01

2.30

4.60

3.46

4.22

NA

1.66

4.81

5.97

NA

3.30

4.01

1.83

1.80

3.11

NA

4.92

2.85

8.64

6.14

6.54

4.64

8.23

NA

5.85

4.48

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1.50

10.06

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Figure 1 Cricondentherm calculation deviations for the GERG-compatible mixtures

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

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Figure 3 Dew point temperature calculation deviations for the GERG-compatible mixtures

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Figure 4 Dew point pressure calculations deviations for the GERG-compatible mixtures

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Figure 5(a)

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Figure 5(b)

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Figure 5(c)

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Figure 5(d)

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Figure 5(e)

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Figure 5(f)

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Figure 5 Hydrocarbon gas dew curves for (a) Gas 16 (exp. from [46]); (b) Gas 17 (exp. from [46]); (c) Gas 18 (exp.
from [46]); (d) Gas 19 (exp. from [46]); (e) Gas 20 (exp. from [44]); (f) Gas 29 (exp. from [2])

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Highlights:

The Peng-Robinson (PR) EOS, is modified for better natural gas dew point prediction
The modification is applied to the attraction parameter of the equation

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Results are compared with the common methods of natural gas dew point prediction

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The proposed model gives more accurate predictions of natural gas dew point curves