Fluid Phase Equilibria 388 (2015) 182–187

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

A thermodynamic consistency test for experimental isobaric data of

wax solubility in gaseous systems
Javad Kondori a , Hamed Hashemi b , Saeedeh Babaee b , Jafar Javanmardi a ,
Amir H. Mohammadi b,c, * , Deresh Ramjugernath b, **
a
Department of Chemical Engineering, Shiraz University of Technology, Shiraz, Iran
b
Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V, Avenue, Durban 4041, South
Africa
c
Institut de Recherche en GénieChimiqueetPétrolier (IRGCP), Paris Cedex, France

A R T I C L E I N F O A B S T R A C T

Article history: The ever-increasing demand for natural gas as an energy source has led to a great deal of interest and
Received 3 May 2014 numerous studies being undertaken by researchers in the field. The efficient production of natural gas
Received in revised form 27 December 2014 from deep well reservoirs has always been an area of intense research in the gas production industry,
Accepted 31 December 2014
with immense efforts to understand and mitigate issues which can affect this efficiency. The solubility of
Available online 3 January 2015
the waxy compounds in some natural gases can be regarded as one of these issues that may affect
production efficiency. In order to fully understand the phenomenon of wax solubility in natural gas,
Keywords:
reliable experimental data are required. This study aims to investigate the reliability of such data using a
Thermodynamic consistency test
Wax solubility
thermodynamic model. For this purpose, the wax solubility in supercritical constituents of natural gas,
Isobaric experimental data such as carbon dioxide and ethane, has been estimated using the Peng–Robinson equation of state and
Gibbs–Duhem two-fluid van der Waals (vdW2) mixing rules. The residual enthalpies were evaluated using the results
Supercritical fluids obtained. The Gibbs–Duhem equation at constant pressure was applied for evaluation of the consistency
of the experimental data. From the analysis, the data were classified as thermodynamically consistent
(TC), not fully consistent (NFC), and thermodynamically inconsistent (TI).
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction which are comprised mainly of paraffin hydrocarbons (C18—C36),

Natural gas, until the middle of the 20th century, was dismissed
as an impractical by-product of crude oil production. This has
changed significantly with natural gas now accounting for
approximately 22% of the world’s energy consumption, with the
percentage likely to increase with every larger reserves being
discovered. It has been predicted by the International Energy
Agency that the demand for the natural gas will increase nearly
43% by 2035. Natural gas is regarded as the cleanest and most
economical conventional fuel compared to hydrocarbon fuels such
as oil and coal which produce high levels of greenhouse emissions.
The temperature depression in petroleum pipelines conveying
waxy crudes may result in the formation of solid compounds
* Corresponding author at: Institut de Recherche en GénieChimiqueetPétrolier
(IRGCP), Paris Cedex, France.
** Corresponding author.
E-mail addresses: a.h.m@irgcp.fr, amir_h_mohammadi@yahoo.com
(A.H. Mohammadi), ramjuger@ukzn.ac.za (D. Ramjugernath).
known as paraffin wax and naphthenic hydrocarbons (C30—C60).
The presence of such compounds may be expected in some natural
gas production fields [1,2]. The extraction of these compounds by
supercritical constituents of natural gas, such as carbon dioxide
and ethane, in gas production from deep well or acid gas fields may
have catastrophic repercussions [1,2]. Therefore, the measurement
of solubility of such compounds in supercritical fluids is an
important area of research [2]. Hence, before design of the related
facilities for natural gas production from gas reservoirs, the
solubility of waxes should be taken into account to avoid any
possible failure in the system (lost production, or failure of piping
system) [2]. For this purpose the knowledge of natural gas + wax
phase behavior is inevitable [2]. Accordingly, developing a reliable
model for predicting this phase behavior is necessary [2].
Unfortunately, there are a scarcity of experimental data in the
open literature which have considered this phenomenon [2]. The
reliability of the model depends on the accuracy of the
experimental data which are employed for the fitting of model
parameters. The use of inaccurate or incorrect measured experi-
mental data would result in parameters which produce a model

http://dx.doi.org/10.1016/j.fluid.2014.12.048
0378-3812/ ã 2015 Elsevier B.V. All rights reserved.
 J. Kondori et al. / Fluid Phase Equilibria 388 (2015) 182–187 183

In this study, the consistency of isobaric wax solubility

Nomenclature
experimental data in carbon dioxide and ethane have been
thermodynamically evaluated. The Gibbs–Duhem [3,6,7] equation,
A Area (m2)
in terms of residual molar enthalpy and molar volume, has been
ARD Absolute relative deviation
applied for this purpose. The thermodynamic consistency, partial
d Derivative operator
consistency (not fully consistent), and thermodynamic inconsis-
E Error
tency of data have been determined.
EoS Equation of state
k Binary interaction parameter
2. Thermodynamic consistency test
f Fugacity
G Gibbs energy
The “Gibbs–Duhem” [3,6,7] relation can be written in terms of
H Molar enthalpy
residual molar enthalpy (HR) and residual molar volume (VR) for a
l Binary interaction parameter
homogeneous mixture as follows [6,14]:
NDP Number of experimental data points " #
P Pressure (MPa) GR HR VR
PR Peng–Robinson S yi d i ¼ 2 dT þ dP (1)
i RT RT RT
R Universal gas constant (MPa m3/mol
T Temperature (K) where yi stands for the mole fraction of species i in the mixture, GRi
TC Thermodynamically consistent data is the residual Gibbs energy, R represents the universal gas
V Molar volume (m3/mol) constant, and P and T are the pressure and temperature of the
vdW2 van der Waals 2 fluid mixing rule system, respectively. Residual Gibbs energy “GRi ” can be expressed
y Mole fraction in gas phase by the following equation [5–7]:
Z Compressibility factor
GRi ¼ RTln’i (2)
Greek symbols in which fi represents the fugacity coefficient of component i in
f Fugacity coefficient the mixture. Substitution of Eq. (2) into Eq. (1) gives:
D Difference value
v Acentric factor HR VR
S yi d½ln’i Š ¼ 2
dT þ dP (3)
i RT RT
Subscripts
For the case of study (wax solubility in the gaseous system) only
A Area R
two components are involved and Eq. (3) considering h ¼ HR =RT
c Critical property
can be simplified as follows [3,6,7]:
i ith component in a mixture or ith experimental data set
j jth component in a mixture or jth individual calculated R
" #
h
area dT ¼ y1 dðln’1 Þ þ y2 dðln’2 Þ (4)
T
T Refers to experimental P–T–y data
f Refers to calculated parameters of the model for evalua- where y1 and y2 are the mole fraction of supercritical fluid and
tions of the integrals in Eqs. (8)–(10) solute (wax) in the gas phase, respectively and f1, f2 represent the
1 Refers to supercritical CO2 or ethane fugacity coefficients of the components in the gas phase. The
2 Refers to paraffin wax following equation is used for evaluation of hR:

ZV
Superscripts R @Z dV
h ¼T ð Þ þ ðZ 1Þ (5)
cal Calculated @T V
1
exp Experimental
s Solid where Z indicates the compressibility factor of the gas phase, and T
R Residual property and V are temperature and molar volume of the system,
sat Saturation (sublimation) pressure (MPa) respectively. A mathematical re-arrangement of Eq. (4) in terms
of the wax composition in the gas phase (y2 = 1 y1) gives:
1 1 ð1 y2 Þ
Z Z Z
which is inaccurate or incorrect. Analyzing the reliability of dT ¼ R
d’ 2 þ R
d’1 (6)
Ty2 ð h Þ’2 ð h Þy2 ’1
experimental data has become an area of interest for many
researchers. in which the parameters, hR, f1, f2, and Z can be calculated using an
The “Slope Test”, the “Integral Test”, the “Differential Test” and accurate thermodynamic model for the wax–gas equilibria.
the “Tangent-Intercept Test” are among the well-known Further simplifications can also be made by designating the left
approaches which have been developed so date for evaluating and right hand sides of Eq. (6) by AT and Af, respectively, as follows
the consistency of experimental data [3–8]. Comprehensive [8,14]:
reviews of these methods can be found in literature [4,5]. Z
1
Valderrama can be regarded one as the pioneers of thermody- AT ¼ dT (7)
Ty2
namic consistency testing of experimental data [8–13]. The Gibbs–
Duhem [3,6,7] equation has been adopted by Valderrama for this A’ ¼ A’1 þ A’2 (8)
purpose at constant temperature. In a previous study, a new
where
approach for assessing the water content of methane experimental
data at constant pressures was developed [14]. Hence depending ð1 y2 Þ
Z
A’1 ¼ R
d’1 (9)
on experimental data being considered, and whether the data are ð h Þy2 ’1
at constant pressure or temperature, either the constant pressure
or constant temperature approach can be employed.
184 J. Kondori et al. / Fluid Phase Equilibria 388 (2015) 182–187

No Table 2
Is ARD% within [0-25]%? Change the correlang model
Sublimation pressures of the investigated paraffin waxes at different temperatures
[2].
Yes
Compound T/K Sublimation pressure/MPa
Yes The data are thermodynamically
Are all ∆A% in the range of [0-18]%? n-C25H52 308 1.58  10 11
consistent 11
313 5.39  10
No
13
n-C28H58 308 1.71 10
12
Are the data outside the range of [0- NO 318 2.67  10
The data are Not Fully Consistent 325 1.68  10 11
18]% greater than 25% of the whole
(NFC)
dataset?
14
n-C30H62 308 1.50  10
14
313 6.46  10
Yes
15
The data are Thermodynamically n-C32H66 308 1.02  10
15
Inconsistent (TI) 313 4.74  10
14
318 2.12  10
14
319 2.86  10
Fig. 1. Flowchart diagram of the thermodynamic consistency test used in this study
[8]. n-C33H68 308 1.15  10 15

15
313 5.43  10
14
318 2.44  10

1
Z
A’2 ¼ R
d’2 (10)
ð h Þ’2
and 5% for experimental solubility data of wax in carbon dioxide
and ethane are assumed. It should be noted that these
In this study, the Simpson 3/8 integration method was used for uncertainties are dependent on the experimental measurement
determination of AT and Af. The equivalency of AT and Af within an methods, for example the method which was used by Teja et al.
acceptable deviation will determine the consistency of the dataset was based on dynamic method [2]. The relative average absolute
considered. This deviation is defined using a percent area deviation deviations range between [0–18]% for the solubility data of the
between experimental and calculated values [1,14]: investigated waxes in supercritical carbon dioxide and ethane was

jA AT i j
 obtained applying the central finite difference method [18] in two
DAi ¼ 100 ’ i (11) preceding equations. This range has been considered as the
AT i
maximum acceptable error for areas (DAi) in Eq. (11). A flowchart
where i indicates the number of the dataset. The error propagation for the procedure used for the checking of the thermodynamic
method [15] has been used for the evaluation of the boundaries for consistency of the investigated dataset is shown in Fig. 1.
these deviations at constant pressure. Considering mole fraction of
wax in the gas phase as the independent measured variable and Af 3. Thermodynamic model
as the dependent measured variable, the error in the calculated
areas, EA, and the percent error, %EA can be obtained using In this study, the equality of the fugacities of solutes (wax) in
following equations [16,17]: adjacent phases (pure solid and gas phase) has been used as the

@ A’
 
@A’
 equilibrium criteria [1,2]:
EA ¼ DP þ Dy (12)
@P @y solid gas
fi ¼ fi (14)
where f stands for the fugacity of component i in the mixture. In
EA this study, the following assumptions have been made for the
%EA ¼ 100j j (13)
A’ j modeling of the wax–gas system [1,2]:
where subscript j indicates the jth calculated area. In this study, a
1 The supercritical fluid is not soluble in the solid (solute-
maximum uncertainty of 0.1 MPa for the experimental pressure
containing) phase.
2 The fugacity of the pure solid i represents the fugacity of the
Table 1 solute i in the mixture.
Experimental datasets used for the consistency test in this study. 3 The pressure dependency of the solute molar volume has been
neglected.
System NDPa P range/ T range/K y2  106 range/mole Ref.
MPa fractionb
4 The solid phase is incompressible.
5 The saturated fugacity coefficient of the solute is assumed to be
CO2 + n- 4 10.35–20.5 308–313 215–952 2
C25H52 unity.
CO2 + n- 2 20 308–318 435–689 2
C28H58
CO2 + n- 2 11 308.15–318.15 54.6–76 21
Table 3
C28H58
Solid molar volumes (Vs) of the paraffin waxes [2] investigated.
Ethane + n- 8 6.57–13.64 308.1–313.1 486–1710 2
C30H62 Solute vs  103/m3/mol
Ethane + n- 16 6.57–20.2 308.1–319.1 149–2180 2
C32H66 n-C25H52 0.4513
Ethane + n- 16 6.47–20.2 308.1–318.1 183–2970 2 n-C28H58 0.4894
C33H68 n-C30H62 0.5222
n-C32H66 0.555
a
Number of data points. n-C33H68 0.5714
b
Wax solubility.
 J. Kondori et al. / Fluid Phase Equilibria 388 (2015) 182–187 185

Table 4 Psat s
i exp½vi ðP Psat
i Þ=RTŠ
Acentric factors (v) and critical properties (Tc: critical temperature and Pc: critical
yi ¼ (15)
’i P
pressure) of the pure compounds investigated.

Compound Tc/K Pc/MPa v

Th Peng–Robinson equation of state [19] and the two-fluid van
C2H6 305.32 4.872 0.099 der Waals (vdW2) [20] mixing rules have been used for calculation
CO2 304.19 7.382 0.2276
n-C25H52 818.56 1.0256 1.066
of the solid, solutes, and supercritical fluids fugacity coefficients
n-C28H58 842.11 0.9694 1.163 (fi) in the mixture and also other required parameters. More
n-C30H62 856.17 0.9421 1.226 details in this regard are given elsewhere [1].
n-C32H66 869.12 0.9208 1.287
n-C33H68 875.22 0.9119 1.317
4. Consistency criteria

Considering the preceding assumptions and using Eq. (14), the
following equation will be obtained for calculation of the solid
solubility in the supercritical fluid:
The accuracy of the model used for correlation / representation
of the experimental data is crucial in the thermodynamic
consistency test. In other words, the average absolute deviations
between the model predictions and the experimental data should
be within the acceptable margin of errors. In this study, the range

Table 5
Model predictions for the paraffin waxes (2) solubility in CO2 and ethane (1).

System P/Mpa T/K yexp  106 ycal 6 ARD% kijb lijb

2 2  10

CO2 + n-C25H52 10.35 308.00 215 236.2 9.90 0.194 0.418 [2]
313.00 321 324.0 1.00 [2]
20.50 308.00 602 663.0 10.20 [2]
313.00 952 1043.0 9.60 [2]

CO2 + n-C28H58 20.00 308.00 689 751.1 8.90 0.035 0.32 [2]
318.00 435 439.5 1.00 [2]
11.00 308.15 54.6 82.3 50.73a [21]
318.15 76 69.3 8.82 [21]

Ethane + n-C32H66 6.57 308.10 216 258.4 19.70 0.057 0.19 [2]
313.10 177 208.9 18.00 [2]
319.10 149 196.8 32.10a [2]
10.10 308.10 713 855.6 20.00 [2]
313.10 933 1110.1 19.00 [2]
319.10 1280 1675.1 30.90a [2]
12.02 308.10 801 962.9 20.20 [2]
313.10 1150 1370.8 19.20 [2]
319.10 1440 1889.3 31.20a [2]
13.64 308.10 959 1140.5 18.90 [2]
313.10 1440 1709.7 18.70 [2]
319.10 2140 2818.0 31.70a [2]
16.67 308.10 1260 1527.1 21.20 [2]
313.10 1730 2062.2 19.20 [2]
20.20 308.10 1810 2184.7 20.70 [2]
313.10 2180 2581.1 18.40 [2]

Ethane + n-C33H68 6.47 308.10 371 441.4 18.98 0.35 0.151 [2]
313.10 288 344.4 19.58 [2]
318.10 183 239.2 30.71a [2]
10.20 308.10 963 1155.6 20.00 [2]
313.10 1540 1844.9 19.80 [2]
318.10 1540 2005.1 30.20a [2]
12.12 308.10 1140 1359.7 19.27 [2]
313.10 1470 1754.9 19.38 [2]
318.10 1960 2565.6 30.90a [2]
13.64 308.10 1360 1627.1 19.64 [2]
313.10 1720 2062.1 19.89 [2]
318.10 2970 3890.7 31.00a [2]
16.67 308.10 1640 1966.9 19.93 [2]
313.10 2240 2658.2 18.67 [2]
20.20 308.10 2370 2846.4 20.10 [2]
313.10 2930 3508.4 19.74 [2]

Ethane + n-C30H62 6.57 308.10 549 667.0 21.49 0.06 0.06 [2]
313.10 486 610.8 25.68a [2]
10.10 308.10 1240 1483.7 19.65 [2]
313.10 1450 1801.0 24.21
12.02 308.10 1450 1744.1 20.28 [2]
313.10 1450 1832.8 26.40a [2]
13.64 308.10 1710 2066.4 20.80 [2]
313.10 1710 2171.4 27.00a [2]
a
Data out of model predictions criteria (doutful data).
b
Interaction parameters between the ith and jth compounds in the mixture, which are consistent with those reported in Ref. [2].
186 J. Kondori et al. / Fluid Phase Equilibria 388 (2015) 182–187

of [0–25]% has been chosen as the acceptable range for the absolute
relative deviations (ARD) of the model predictions which is defined
as follows:
jycal
i yexp
i
j
ARD% ¼ 100 
yexp
i Fig. 1 shows the procedure schematically [8].
where superscripts “cal” and “exp” stand for calculated and
experimental values, respectively.
According to what has been discussed so far, the following
procedure has been adopted for determination of thermodynami-
cally consistent (TC), thermodynamically inconsistent (TI), and not
fully consistent (NFC) determination of experimental data:
1 Initially, the ARD% of the model should lie between 0 and 25%,
otherwise the poor prediction should be eliminated and the
correlating model changed. In these cases, the related experi-
mental data are regarded as doubtful data and they are not used
in the test.
2 A dataset is deemed to be thermodynamically consistent (TC) if
the model provides acceptable error ranges (ARD%) and the area
test is met for all data points in the dataset.
3 Thermodynamically inconsistent (TI) experimental datasets are
defined as the datasets in which that the area test is not fulfilled
for most of the data (more than 25% of the areas) even though
the thermodynamic model correlates the experimental data
correctly (with ARD% between 0 and 25%).
4 parameters of the model are reported in Table 5. As can been seen,
Not fully consistent (NFC) experimental datasets are defined as
data which are predicted by the model correctly, however less
than 25% of the data are outside the defined margin of errors, i.e.
[0–18]%.
(16)
5. Experimental data
48 isobaric experimental datasets were considered in this
study, most of which were taken from GPA research report 171 [2],
and are summarized in Table 1. These datasets include solubility of
paraffin waxes (alkanes from n-C24 to n-C33) in CO2 and ethane.
Tables 2 and 3, show the sublimation pressures and solid molar
volumes of the paraffin waxes, respectively. Acentric factors and
critical properties of the investigated compounds are reported in
Table 4.
6. Result and discussion
The consistency check procedure adopted in this study can be
divided in two parts: first obtaining the thermodynamic model
predictions of the wax solubility data, and second evaluating the
experimental data using the obtained results. The results obtained
from the model for the prediction of the paraffin wax solubility in
supercritical CO2 and ethane, as well as adjusted interaction

Table 6
Results of the thermodynamic consistency test for the experimental paraffin waxes (2) solubility data in supercritical fluids (1).

System P/MPa T/K Z f1 f2 HR AT Af DAi% Test result

6
CO2 + n-C25H52 10.35 308 0.264 0.5210 1.210  10 3.465 69.788 62.635 10.2 TC
6
313 0.292 0.5527 3.650  10 3.126
6
20.5 308 0.401 0.3310 1.010  10 4.006 21.873 19.036 14.9 TC
6
313 0.417 0.3493 2.810  10 3.779

6
CO2 + n-C28H58 20 308 0.397 0.3337 0.050  10 3.976 59.707 60.852 1.88 TC
6
318 0.420 0.3770 0.087  10 3.564

6
Ethane + n-C32H66 6.57 308.1 0.254 0.5282 0.037  10 3.496 42.077 46.598 9.70 TC
6
313.1 0.285 0.5610 0.085  10 3.167
6
10.1 308.1 0.326 0.3880 0.029  10 3.883 12.236 14.308 14.47 TC
6
313.1 0.343 0.4165 0.044  10 3.942
6
12.02 308.1 0.378 0.3503 0.032  10 3.907 17.073 17.393 1.83 TC
6
313.1 0.386 0.3728 0.049  10 3.736
6
13.64 308.1 0.415 0.3244 0.040  10 3.959 14.000 14.269 1.84 TC
6
313.1 0.422 0.3456 0.059  10 3.803
6
16.67 308.1 0.484 0.2900 0.094  10 4.0324 11.055 11.336 2.48 TC
6
313.1 0.491 0.3095 0.093  10 3.8809
6
20.2 308.1 0.5652 0.2646 0.040  10 4.0794 8.1457 8.2785 1.61 TC
6
313.1 0.5695 0.2824 0.059  10 3.9376

7
Ethane + n-C30H62 10.1 308.1 0.333 0.3919 0.416  10 3.832 12.05 12.27 1.82 TC
7
313.1 0.343 0.4164 0.631 10 3.644

Ethane + n-C33H68 6.47 308.1 0.251 0.5343 1.56  10 12 3.496 49.596 46.955 5.62 TC
313.1 0.279 0.5630 0.127  10 12 3.139
10.2 308.1 0.328 0.3861 0.244  10 12 3.901 13.611 12.890 5.58 TC
313.1 0.337 0.4101 0.65  10 12 3.728
12.12 308.1 0.372 0.3450 0.196  10 12 3.988 12.550 12.648 0.15 TC
313.1 0.379 0.3670 0.485  10 12 3.823
13.64 308.1 0.407 0.3211 0.186  10 12 4.039 10.609 10.625 4.71 TC
313.1 0.413 0.3418 0.435  10 12 3.883
16.67 308.1 0.475 0.2860 0.206  10 12 4.111 8.512 8.933 4.72 TC
313.1 0.482 0.3057 0.446  10 12 3.960
20.2 308.1 0.555 0.2610 0.283  10 12 4.168 6.149 6.203 0.86 TC
313.1 0.561 0.2784 0.585  10 12 4.022
 J. Kondori et al. / Fluid Phase Equilibria 388 (2015) 182–187
the ability of the model used for prediction of the experimental
data is acceptable and for most of the data, absolute deviation
values lie within the range of [0–25]%. For some cases, the
thermodynamic model criteria was not met (model predictions
were not within the range of [0–25]%); in these cases the poor
predictions were eliminated and the data were not considered in
the consistency test. The results of the thermodynamic consistency
test for the datasets investigated are reported in Table 6. As can be
observed, all the datasets considered (the datasets which are well
correlated by the thermodynamic model) are thermodynamically
consistent. The same result was found in the previous study [1] at
constant temperature which confirms the reliability of the
proposed thermodynamic consistency test in this study. Several
factors should be taken into consideration when evaluating the
reliability or accuracy of an experimental dataset, such as the
procedure or technique used for the measurement of the
experimental dataset; the accuracy of the calibration methods;
the ability of the researcher performing the experiments; the
accuracy of the low solubility measurements; and so on. It can be
inferred from the thermodynamic consistency check of the
datasets analyzed in this study that researchers have taken great
care in the measurement of the experimental data. The results of
this study would confirm the reliability of experimental data which
can then be used with confidence for the tuning of thermodynamic
model parameters. Thermodynamically inconsistent data or not
fully consistent data will result in erroneous predictions of the
model for further applications and the reason of such deviations
may not be identified easily.
It should be note that the proposed thermodynamic consistency
test is only applicable to isobaric experimental data and the
developed equations in this study are based on this assumption. In
a previous study [1] an isothermal procedure was performed for
the evaluation of the thermodynamic consistency of the experi-
mental data. Hence, depending on the way in which the
experimental data has been presented (isothermal or isobaric)
either procedure (temperature constant or pressure constant) can
be applied. Looking for isobaric or isothermal experimental data is
one of the limitations of the proposed consistency tests. One
solution to this problem is generating pseudo experimental data
using statistical software. However, in generating such data
thermodynamically tested data are required.
7. Conclusions
A new thermodynamic consistency test based on calculation of
the residual enthalpies was applied at constant pressure for 48
experimental data of paraffin wax solubilities in supercritical CO2
and ethane. The original Gibbs–Duhem [3,6,7] equation was used
to relate the calculated residual enthalpies to solubility and
fugacity coefficients of the components. The PR EoS [19] coupled
with vdW2 [20] mixing rule was used for the prediction of the
paraffin wax solubilities in supercritical CO2 and ethane. The
results show that all the considered datasets which are within the
model capability seem to be thermodynamically consistent. These
results are in good agreement with the results obtained from a
previous study [1] in which the datasets were tested thermody-
namically at constant temperature. Since all the datasets
187
considered in this study are thermodynamically consistent, the
procedure applied by Teja et al. [2] in their measurements can be
concluded as reliable.
Given the importance of solubility data of paraffin waxes in
supercritical fluids and the fact that these kinds of data are indeed
rare, the results obtained in this study can be used for further
applications in natural gas systems.
Acknowledgements
This work is based upon research supported by the South
African Research Chairs Initiative of the Department of Science and
Technology and National Research Foundation.
References
[1] A.H. Mohammadi, A. Eslamimanesh, D. Richon, Wax solubility in gaseous
system: thermodynamic consistency test of experimental data, Ind. Eng.
Chem. Res. 50 (8) (2011) 4731–4740.
[2] A.S. Teja, V.S. Smith, T.S. Sun, J. Mendez-Santiago, Solids deposition in natural
gas systems, Res. Rep. 171 (2000) 905–993 GPA project.
[3] J.M. Prausnitz, R.N. Lichtenthaler, E.G. de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, Pearson Education, 1998.
[4] J. Raal, A. Mühlbauer, Phase Equilibria: Measurement and Computation, Taylor
& Francis, Washington, 1998.
[5] B. Poling, J. Prausnitz, J. O’Connell, The Properties of Gases and Liquids, fifth ed.,
New York, Mc-Graw Hill, 2001.
[6] J. Smith, H. van Ness, M. Abbott, Introduction to Chemical Engineering
Thermodynamics, sixth ed., McGraw-Hill, New York, 2003.
[7] H. van Ness, M. Abbott, Classical Thermodynamics of Non-Electrolyte
Solutions, McGraw-Hill, New York, 1982.
[8] J.O. Valderrama, V.H. Alvarez, A versatile thermodynamic consistency test for
incomplete phase equilibrium data of high-pressure gas–liquid mixtures,
Fluid Phase Equilib. 226 (1–2) (2004) 149–159.
[9] C.A. Faúndez, J.F. Díaz-Valdés, J.O. Valderrama, Consistency test of solubility
data of ammonia in ionic liquids using the modified Peng–Robinson equation
of Kwak and Mansoori, Fluid Phase Equilib. 348 (2013) 33–38.
[10] J.O. Valderrama, A. Reátegui, W.W. Sanga, Thermodynamic consistency test of
vapor–liquid equilibrium data for mixtures containing ionic liquids, Ind. Eng.
Chem. Res. 47 (21) (2008) 8416–8422.
[11] J.O. Valderrama, P.A. Robles, A. Reátegui, Data analysis, modeling and
thermodynamic consistency of CO2 + b-carotene high pressure mixtures, J.
Supercrit. Fluids 55 (2) (2010) 609–615.
[12] J.O. Valderrama, P.A. Robles, Thermodynamic consistency of high pressure
ternary mixtures containing a compressed gas and solid solutes of different
complexity, Fluid Phase Equilib. 242 (1) (2006) 93–102.
[13] J.O. Valderrama, J. Zavaleta, Thermodynamic consistency test for high pressure
gas–solid solubility data of binary mixtures using genetic algorithms, J.
Supercrit. Fluids 39 (1) (2006) 20–29.
[14] J. Kondori, J. Javanmardi, A. Eslamimanesh, A.H. Mohammadi, Thermodynamic
consistency test for isobaric experimental data of water content of methane,
Fluid Phase Equilib. 347 (2013) 54–61.
[15] H.S. Mickley, T.K. Sherwood, C.E. Reed, Applied Mathematics in Chemical
Engineering, McGraw-Hill, New York, 1957.
[16] A. Eslamimanesh, A.H. Mohammadi, D. Richon, Thermodynamic consistency
test for experimental data of water content of methane, AIChE J. 57 (9) (2011)
2566–2573.
[17] A. Eslamimanesh, A.H. Mohammadi, D. Richon, Thermodynamic consistency
test for experimental data of sulfur content of hydrogen sulfide, Ind. Eng.
Chem. Res. 50 (6) (2011) 3555–3563.
[18] A. Constantinides, N. Mostoufi, Numerical Methods for Chemical Engineers
with MATLAB Applications, Prentice Hall, New Jersey, 1999, pp. 443.
[19] D.-Y. Peng, D.B. Robinson, A new two-constant equation of state, Ind. Eng.
Chem. Fundam. 15 (1) (1976) 59–64.
[20] M. Mukhopadhyay . Natural Extracts Using Supercritical Carbon Dioxide, CRC
Press.
[21] E. Reverchon, P. Russo, A. Stassi, Solubilities of solid octacosane and
triacontane in supercritical carbon dioxide, J. Chem. Eng. Data 38 (1993)
458–460.