Fluid Phase Equilibria 441 (2017) 2e8

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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

Prediction of critical temperature and critical pressure of multi-

component mixtures
Maogang He*, Yang Liu, Xiangyang Liu
Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, Xi'an Jiaotong University, Xi'an, Shaanxi Province, 710049, PR China

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

Article history: A new correlation is presented to predict critical temperature and critical pressure of multi-component
Received 28 October 2016 mixtures, in which binary interaction coefficients tij and kij are used to describe non-ideal contribution of
Received in revised form binary mixtures. The binary interaction coefficients of 515 binary mixtures for critical temperature and
15 November 2016
319 binary mixtures for critical pressure are determined. Compared with the experimental data, the
Accepted 21 November 2016
average absolute relative deviations of the correction for calculating critical temperature and pressure
Available online 22 November 2016
are 1.65% and 5.21%, respectively. In order to predict critical temperature and critical pressure of the
mixtures which did not list in this paper, the Chueh-Prausnitz equation can be used to calculate the
Keywords:
Critical temperature
binary interaction coefficients tij and kij. The specific coefficients in the equations have been given for 9
Critical pressure types of binary mixtures. In order to evaluate the ability of this method to predict the critical temper-
Prediction ature and critical pressure of multi-component mixtures, 348 experimental data were collected and the
Multi-component mixtures corresponding values were calculated by this method. The absolute average relative deviation of the
prediction values is about 1.10% for critical temperature and 6.39% for critical pressure.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction industrial production are often determined experimentally, and the

The prediction of the critical point of a multi-component
mixture is very important both in practice and in theory [1e3].
The vapor and liquid phases near the critical point share the same
properties, so the critical point of the mixture is a key part of the
development of accurate liquid theory. Knowledge of the critical
state can also be used to classify the phase behavior of the mixture
and to determine whether retrograde evaporation is possible [4].
According to Kay [4] and Hicks & Young [1], retrograde behavior
and its relation to critical points are particularly important at high
pressures. The critical properties of pure materials can be obtained
experimentally, but for the mixture, the experimental determina-
tion of critical data have high technical requirements. Since the
critical properties of the mixture is usually not a simple linear
relationship by the different components, and the experimental
measurement of the critical point is usually a time-consuming and
very expensive task. Therefore, the critical properties of some
representative mixtures or mixtures that are closely related to
* Corresponding author.
E-mail address: mghe@mail.xjtu.edu.cn (M. He).
critical properties of other mixtures are frequently calculated by
prediction methods. So that it is very important to find effective
methods for predicting the critical points of different mixture
systems.
Most of the computational models are empirical methods for
estimating the critical properties of mixtures. These methods are
limited in their application, and many of them are specifically
designed to predict a specific mixture system and are difficult to
generalize to other types of mixtures. And some methods can be
used to predict the binary mixtures, but difficult to generalize to the
multi-component mixtures. Wilson [5] first used the renormali-
zation group theory to research the critical phenomena in 1971,
which made a breakthrough in the theoretical research of critical
phenomena. However, due to the strong density fluctuation near
the critical point, it is difficult to apply to the practical application of
engineering.
Actually, the methods to predict the critical properties of mix-
tures can be divided into two types: rigorous method and fast es-
timate method. The rigorous method is based on the
thermodynamic conditions of the critical point of the mixture given
by Gibbs [6]:

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 M. He et al. / Fluid Phase Equilibria 441 (2017) 2e8 3

0 1 several methods, suggested for fast prediction of critical tempera-

v2 G v2 G v2 G ture of multi-component mixtures. The representative methods in
B … C
B vx21 vx1 vx2 vx1 vxn1 C this category have been proposed by Li [13], and Chueh & Prausnitz
B C
B C [14]. Spencer et al. [15] and Elliott & Daubert [16] have assessed the
B v2 G v2 G v2 G C
B … C accuracy of these techniques together with some rigorous methods.
B vx2 vxn1 C
J1 ¼ B vx2 vx1 vx22 C¼0 (1) Through the study of binary mixture critical temperature,
B C
B « « « C Rowlinson [17] found that the critical temperature expression of
B C
B C the mixture tends to be quadratic function of the mole fraction. He
B 2 2 2 C
@ v G v G v G A put forward the following expression:
…
vxn1 vx1 vxn1 vx2 2
vxn1

0 1 Tct ¼ y1 Tc1 þ y2 Tc2 þ 2y1 y2 DT12 (3)

vJ1 vJ1 vJ1
B …
B vx1 vx2 vxn1 C C where yi is the mole fraction of pure component i. Tci is the critical
B C temperature of pure component i. Tct is the true critical tempera-
B v2 G 2
v G v2 G C
B … C ture of mixture. DT12 is a function defined by Rowlinson, calculated
B vx vx vx2 vxn1 C
J2 ¼ B
B 2 1 vx22 C¼0
C (2) by the molecular potential energy and the interaction between two
B C
B « « « C substances on the characteristics of energy. However, this
B C
B C assumption is only applicable to the substances with the molecules
@ v2 G v2 G v2 G A close to spherically symmetric, and of similar size.
…
vxn1 vx1 vxn1 vx2 vx2n1 Instead of using mole fractions directly in the mixing rule, Li
preferred an arbitrary parameter called fj that is expressed as,
where G presents Gibbs energy of the system. All the variables used
in the equations are calculated by the states equation, so that the yv
accuracy of this method will be affected by the selected state fi ¼ Pn i ci (4)
equation. Redlich-Kwong (RK) equation [7], Soave-Redlich-Kwong i¼1 yi vci

(SRK) equation [8], Peng-Robinson (PR) equation [9] and SAFT

where vci is the critical specific volume of pure component i. Then,
equation [10e12] are commonly used.
the true critical temperature can be estimated by,
The fast estimate methods usually consider the critical proper-
ties of the mixture as the sum of the linear part of each pure
component and non-linear part caused by the interaction of X
n
Tct ¼ fi Tci (5)
different molecules. These methods are with simple forms, easy to
i¼1
use. But most of these correlations have been semi-empirical and
therefore they represent limited type of systems. A large number of A similar approach is proposed by Chueh and Prausnitz. They
experimental data were often needed to obtain satisfactory results defined a surface fraction parameter expressed as, qi:
by this method.
In contrast to fast estimate methods, most rigorous methods can 2=3
y vci
predict all mixture types, and can be applied to the calculation of qi ¼ Pn i 2=3
(6)
the phase diagram in addition to the critical point. But these models i¼1 yi vci
are always complex, difficult to implement, and inefficient for
Then, the true critical temperature can be estimated by:
multicomponent mixtures.
From a practical engineering point of view, fast estimate
methods have some advantages can not be ignored. These methods X
n X
n X
n
Tct ¼ qi Tci þ qi qj tij (7)
are easy to implement and are computationally inexpensive and
i¼1 i¼1 j¼1
can be used for multi-component mixtures with complex mixtures.
At the same time, there are large numbers of experimental data
where tij is a dimensionless parameter which consists of a range of
on the critical properties of binary mixtures, which can be gener-
values in (∞, þ∞). In the above model, it is assumed that: tij ¼ tji,
alized for multiple components of liquid mixtures are encountered
tii ¼ 0. tij is calculated by:
in industrial applications according to binary mixtures. These
methods were mainly developed at the end of 1960s and 1970s, the
experimental data used in the methods were measured even jT ¼ A þ BdT þ C d2T þ Dd3T þ Ed4T (8)
earlier. The types of mixture and the data volume are few, which
leads to poor accuracy when calculating other unknown mixtures.
After several decades of experimental research, the experimental 2tij
jT ¼ (9)
data of the critical properties of binary and multi-component Tci þ Tcj
mixtures become great rich, the data volume of the mixture has
been greatly expanded, so it is possible to propose a more accurate  
T  T 
prediction method.  ci cj 
dT ¼   (10)
Tci þ Tcj 

2. Fast prediction methods of critical temperature for multi-
component mixture
Unlike many thermophysical properties of mixtures, critical
temperature of a mixture is usually not a linear mole fraction
average of the critical temperature of pure components. There are
Chueh and Prausnitz have provided tij values for 65 binary
mixtures in their main paper. Those data were obtained from fitting
experimental critical temperatures of binary mixtures with Eq. (7).
The constants of Eq. (8) (i.e., A, B, C, D, E) can also be selected ac-
cording to Table 1. Later, this method had been revised and modi-
fied by many researchers [18e20].
4 M. He et al. / Fluid Phase Equilibria 441 (2017) 2e8

Table 1 symmetric, and of similar size. And Chueh - Prausnitz method is

Constants of Eq. (7) for prediction of tij in modified ChuehePrausnitz (MCP) method: limited to the materials with molecular dipole moment is 0 or close
a selection guide.
to 0, not apply to the polarity fluid and quantum fluid. Also as can
Binary mixtures A B C D E be seen, Chueh e Prausnitz method is very complex, and requires a
Containing aromatics 0.0219 1.227 24.277 147.673 259.433 lot of parameters in the calculation, which could lead to larger error.
Containing H2S 0.0479 5.725 70.974 161.319 0
Containing CO2 0.0953 2.185 33.985 179.068 264.522
Containing C2H2 0.0785 2.152 93.084 722.676 0 4. New method
Containing CO 0.0077 0.095 0.225 3.528 0
Others 0.0076 0.287 1.343 5.443 3.038
4.1. Critical temperature

Among the above temperature prediction methods, Rowlinson

3. Fast prediction methods of critical pressure for multi-
component mixture
The relationship between the critical pressure of the mixture
and the mole fraction is often non-linear strongly, so the extrapo-
lation of critical pressure is often not reliable enough.
Through the study of binary mixture critical pressure, Row-
linson found that the critical pressure expression of the mixture
tends to be quadratic function of the mole fraction. He put forward
the following expression:
pct ¼ y1 pc1 þ y2 pc2 þ 2y1 y2 Dp12
where yi is the mole fraction of pure component i. pci is the critical
temperature of pure component i. pct is the true critical pressure of
mixture. Dp12 is a special pressure parameter between two
components.
Chueh and Prausnitz proposed another method to predict crit-
ical pressure of mixtures, related the pct, Vct and Tct with a modified
Redlich e Kwong equation:
RTct am
pct ¼  0:5
Vct  bm Tct Vct ðVct þ bm Þ
method is not widespread applicable, Li method is not dependent
on binary experimental data, only the calculations in Chuehe-
Prausnitz method can be easily extended to multi-component
mixtures with data obtained from binary mixtures. Li method
and ChuehePrausnitz method need to define a new surface fraction
parameter, which required the critical volume data. But a lot of
materials lack of the critical volume data, and joining in the
calculation of the critical volume data do not have definite physical
meaning, even would cause to new error.
Based on these considerations, a new method to predict the
critical temperature is proposed in this paper, which combined the
(11)
forms of Rowlinson method, Li method and ChuehePrausnitz
method. In this method, the true critical temperature can be esti-
mated by,
X XX
Tct ¼ yi Tci þ yi yj tij Tref (20)
i i j
where Tref is a reference temperature. In this paper, we assume that
Tref ¼ 1 K. For a binary mixture, true critical temperature can be
estimated by simplified form of Eq. (21) as follows:
(12)
Tct ¼ y1 Tc1 þ y2 Tc2 þ 2y1 y2 tij (21)

where Tct and Vct are calculated by their method which mentioned Like the ChuehePrausnitz method, tij is calculated by:
in their paper [14], and the mixture parameters am and bm are
calculated by: jT ¼ A þ BdT þ C d2T þ Dd3T þ Ed4T (22)
XX
am ¼ yi yj aij (13) 2tij
i j jT ¼ (23)
Tci þ Tcj

X X yj Ubj RTcj  
T  T 
bm ¼ y j bj ¼ (14)  ci cj 
pcj dT ¼   (24)
j j Tci þ Tcj 

Prediction of true critical temperature by this method has relied

Ubj ¼ 0:0867  0:0125uj þ 0:011u2j (15) primarily on the availability of fitted binary interaction parameter
(i.e., tij) for each binary set in the mixture, which can be fitted
Uai R2 Tci2:5 accurately from the experimental data sets of vaporeliquid critical
aii ¼ (16) temperature of binary mixtures. It is obvious that a data set with
pci
wider range of data involving components with various chemical
    families and also more experimental data points could lead to
Uai þ Uaj RTcij
1:5 V þ V
ci cij better prediction of tij, and as a result, better prediction of true
aij ¼    (17) critical temperature.
4 0:291  0:04 ui þ uj
In order to extend the range of data points and improve the
prediction capability of this method, a data set containing the
 qffiffiffiffiffiffiffiffiffiffiffi
Tcij ¼ 1  kij Tci Tcj (18) experimental data of vaporeliquid critical temperature for 515
different binary mixtures with 4453 data points has been prepared.
!   These experimental data points were mainly selected from two
RTcj pcj Vcj Vcj þ bj major references: Design Institute for Physical Properties (DIPPR)
Uaj ¼  pcj  2 (19)
Vcj  bj RTcj [21] and Hicks & Young [1]. There were few data sets which were
selected from different references [22e59]. Critical properties of
Similar with the critical temperature, Rowlinson method is only pure components were mainly obtained from DIPPR project 801. In
applicable to the substances with the molecules close to spherically the present study, the binary interaction coefficient (tij) was
 M. He et al. / Fluid Phase Equilibria 441 (2017) 2e8 5

calculated for each binary system by the aid of new provided data Table 3
set and using proper minimization technique. The results are Statistical evaluation of predication capabilities of different methods in prediction of
critical temperatures of 515 binary mixtures of the present data set.
shown in Supplementary information.
The results were analyzed by several statistical criteria sum- Method Li Modified Chueh-Prausnitz This work
marized in Table 2. The prediction capabilities of this method have RAE 0.1117 0.0924 0.0832
been compared with other methods such as Li, and MCP in pre- MAE 10.56 8.736 5.358
dicting true critical temperature of binary mixtures included in the RMSE 26.08 21.93 8.547
MSE 680.2 481.3 283.4
present data set. The comparison results are shown in Table 3. As
AARD/% 2.51 2.058 1.65
can be observed, the average absolute relative deviation (AARD) of R2 0.9522 0.9666 0.9754
the present method, Li method and modified Chueh-Prausnitz
method are 1.65%, 2.51% and 2.06%, respectively. The application
of this method leads to a major improvement in prediction of
of mixtures. The expression is as follows:
critical temperature of binary mixtures in comparison with the
X XX
other methods. pct ¼ yi pci þ yi yj kij pref (25)
The method proposed in this paper has satisfactory results in i i j
the calculation of the critical temperature of the mixture of most
organic compounds and can provide reliable support for the pre- where pref is a reference pressure. In this paper, we assume that
diction of other properties. The results show that the method pref ¼ 1 MPa. For a binary mixture, true critical pressure can be
proposed in this paper achieve a good predictive effect to calculate estimated by simplified form of Eq. (26) as follows:
the critical temperature of binary mixtures of n-alkanes, other
hydrocarbons, containing halogenated compounds, silicon com- pct ¼ y1 pc1 þ y2 pc2 þ 2y1 y2 kij (26)
pounds and oxygen-containing organic compounds. For methane-
containing mixtures, the deviation is larger than that of the kij is calculated by:
mixture of other organics. The critical properties showed irregular
phenomenon which need further research. For the critical tem- jp ¼ A þ Bdp þ C d2p þ Dd3p þ Ed4p (27)
perature of a mixture of common gases and mixtures of common
gas and organic substance, the compatibility of the mixture be-
2kij
comes an important influencing factor of the critical properties. For jp ¼ (28)
pci þ pcj
a well-dissolved system, the critical temperature seems more
regularly, which is similar to the critical properties of the water-  
containing mixture, and needs further research to obtain better p  p 
 ci cj 
classification. dp ¼   (29)
pci þ pcj 
In order to promote the calculation method, and try to predict
mixtures which do not included in the current data, the binary Similar to the critical temperature prediction, prediction of true
mixtures were classified into 9 types as n-alkanes, other hydro- critical pressure by this method has relied primarily on the avail-
carbons, oxygen-containing systems, containing water, containing ability of fitted binary inter-action parameter (i.e., kij) for each bi-
halogen compound system, containing silicon compound system, nary set in the mixture, which can be fitted accurately from the
containing methane, common gases, common gas þ organic com- experimental data sets of vaporeliquid critical pressure of binary
pound. The constants for prediction of tij and the average absolute mixtures. It is obvious that a data set with wider range of data
relative deviation of calculate values of each type are shown in involving components with various chemical families and also
Table 4. The deviation of calculated results according to this kind of more experimental data points could lead to better prediction of kij,
classification method, which the average absolute relative devia- and as a result, better prediction of true critical pressure.
tion is about 2.25%, is slightly larger. But for the mixtures which did In order to extend the range of data points and improve the
not mentioned in this paper, the calculation is more convenient. prediction capability of this method, a data set containing the
experimental data of vaporeliquid critical pressure for 319
4.2. Critical pressure different binary mixtures with 2827 data points has been prepared.
These experimental data points were mainly selected from two
For the critical pressure, on the basis of a lot of experimental major references: Design Institute for Physical Properties (DIPPR)
data, a new method was proposed to predict true critical pressure Project [21] and Hicks & Young [1]. There were few data sets which

Table 2
Statistical criteria employed to evaluate the prediction capabilities of different models.

Statistical parameter Definition

 
Average absolute relative deviation (AARD)  exp pred 
Pn TcT;i TcT;i 

AARDð%Þ ¼ 100  1n i¼1  T exp 
 cT;i 
Mean squared error (MSE) Pn pred exp 2
MSE ¼ n1 i¼1 ðTcT;i  TcT;i Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P ffi
Root mean squared error (RMSE) pred exp
RMSE ¼ n1 ni¼1 ðT cT;i  T cT;i Þ2
Mean absolute error (MAE) P  exp pred 

MAE ¼ n1 ni¼1 TcT;i  TcT;i 
Coefficient of determination (R2) 0 12
B Pn pred exp Pn exp Pn pred C
B n i¼1 ðTcT;i TcT;i Þð i¼1 TcT;i Þð i¼1 TcT;i Þ C
R2 ¼ B
Bqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn exp 2 Pn exp 2 Pn pred 2 Pn pred 2 C
C
@ ðn i¼1 ðT cT;i Þ ð i¼1 T cT;i Þ Þðn i¼1 ðT cT;i Þ ð i¼1 T cT;i Þ ÞA
6 M. He et al. / Fluid Phase Equilibria 441 (2017) 2e8

Table 4
Constants for prediction of tij in the new method of critical temperature.

Binary mixtures A B C D E AARD/%

n-alkanes 0.0009 0.0612 2.4463 7.1177 26.6840 0.49

Other hydrocarbons 0.0064 0.3682 3.1377 26.9332 57.8487 0.62
Oxygen-containing organic compound systems 0.0285 0.1287 2.0091 13.9953 35.9244 1.17
Containing water 0.2023 5.6403 27.6025 43.4468 23.4237 5.23
Containing methane 6.2592 80.8985 378.3160 752.4695 544.2958 5.12
Containing halogen compound 0.0374 1.4696 23.6408 209.6009 550.8955 1.98
Containing silicon compound 0.0052 0.4996 12.8625 31.7026 8.8100 1.24
Common gases 0.0088 0.3185 5.3759 12.9486 9.5197 4.68
Common gas þ organic compound 0.0292 1.0036 7.2712 10.1890 4.6845 4.97

were selected from different references [22e59]. Critical properties not mentioned in this paper, the calculation is more convenient.
of pure components were mainly obtained from DIPPR project 801. The linearity of critical pressure was not so well, so the calculation
In the present study, the binary interaction coefficient (kij) was deviation of the critical pressure is much larger than that of the
calculated for each binary system by the aid of new provided data critical temperature.
set and using proper minimization technique. The results are In order to evaluate the prediction capability of the proposed
shown in Supplementary information. methods to predict critical temperature and critical pressure of
The results show that the prediction effect is best in calculating multi-component mixtures, 348 experimental data on vapor-
the critical pressure of common gases mixtures, and achieved good eliquid critical temperature and critical pressure of some ternary
prediction effect in calculating the critical pressure of alkane sys- mixtures were collected [58e70], including several groups of data
tems, other hydrocarbon systems, containing halogen compound from our previous work [58e60]. The calculated results were
systems, containing methane systems and oxygen-containing compared to the experimental values, and the deviations were
organic systems. Like the critical temperature, for the critical shown in Figs. 1 and 2, where d presents the relative deviations of
pressure of a mixture of common gases and mixtures of common calculation values compared to experimental values. The results
gas and organic substance, the compatibility of the mixture be- show that the data were fitted well. For critical temperature and
comes an important influencing factor of the critical properties. For critical pressure, the relative deviations of most of the points are
a well-dissolved system, the critical pressure seems more regularly, within 3% and 10%, and the absolute average relative deviation
which is similar to the critical properties of the water-containing (AARD) of all the data points are 1.10% and 6.39%, respectively. The
mixture, and needs further research to obtain better classification. deviations of critical pressures are much larger than which in
The absolute average relative deviation of this method in
calculating the critical pressure of binary mixtures is 5.21%. But we
found that the largest source of the general deviation is water
system and a few mixtures of gas and organic system. If we ignore
the influence of water systems and eliminate some deviations
which have clearly wrong, the absolute average relative deviation
of the method to predict the critical pressure can be decreased to
2.71%.
In order to promote the calculation method, and try to predict
mixtures which do not included in the current data, we classified
the mixtures into several kinds, as shown in Table 5. The binary
mixtures were classified as n-alkanes, iso-alkanes, other hydro-
carbons, oxygen-containing systems, containing water systems,
containing halogen compound systems, containing methane sys-
tems, common gases and common gas þ organic compound sys-
tems. The constants for prediction of kij and the average absolute
relative deviation of calculate values of each type are shown in
Table 5. The deviation of calculated results according to this kind of
classification method, which the average absolute relative devia-
tion is about 8.69%, is slightly larger. But for the systems which did Fig. 1. Relative deviations of true critical temperatures and fitted critical temperatures
of multi-components mixtures.

Table 5
Constants for prediction of kij in the new method of critical pressure.

Binary mixtures A B C D E AARD/%

n-alkanes 0.2812 12.5717 163.5609 889.2193 1419.8074 5.19

n-alkane & iso-alkane 6.5095 106.7323 625.3477 1560.8208 1408.2196 3.85
Other hydrocarbons 0.3949 10.3256 87.3034 245.3810 217.1128 4.03
Oxygen-containing organic compound systems 0.3494 3.9663 14.8436 20.8294 7.4822 5.12
Containing water 82.3314 713.3017 2158.4326 2628.8878 1108.0968 34.27
Containing halogen compound 0.0866 2.5230 10.4934 12.0388 57.7108 6.68
Containing methane 3.4837 204.7510 2399.7731 10324.5205 13213.5566 7.04
Common gases 0.2323 26.2257 497.8281 3297.3706 7184.0450 3.25
Common gas þ organic compound 0.7309 8.6185 98.0086 284.3883 238.3237 15.52
 M. He et al. / Fluid Phase Equilibria 441 (2017) 2e8
Fig. 2. Relative deviations of true critical pressures and fitted critical pressures of
multi-components mixtures.
critical temperatures, mainly because of a lot of system containing
carbon dioxide and hydrogen in the multi-component mixture
experiment points. The mechanism that the prediction critical
pressure for these mixtures have the more deviation from the
experimental data is not clear, which need further research.
5. Conclusion
This work aims at predicting the critical temperature and critical
pressure of multi-component mixtures based on the modification
of the traditional method and the newly experimental data. A new
correlation is presented to predict critical temperature and critical
pressure of multi-component mixtures, in which binary interaction
coefficients tij and kij are used to describe non-ideal contribution of
binary mixtures. The binary interaction coefficients of 515 binary
mixtures for critical temperature and 319 binary mixtures for
critical pressure are determined from 4453 critical temperature
values and 2827 critical pressure values of binary mixtures. The
accuracy of the new correlations is superior to the traditional cor-
relations, compared with the experimental data, the average ab-
solute relative deviations of calculating the critical temperatures
and pressures using the new correlations are 1.65% and 5.21%,
respectively.
We also used the related expression of Chueh-Prausnitz equa-
tion to predict the interaction coefficients tij and kij for the different
kinds binary mixtures as n-alkanes, other hydrocarbons, oxygen-
containing systems, containing water, containing halogen com-
pound systems, containing silicon compound systems, containing
methane, common gases, common gas þ organic compound. The
corresponding average absolute relative deviations are 2.25% and
8.69%, respectively.
Finally, we predict the critical temperatures and pressures of
some ternary mixtures, the absolute average relative deviations are
1.10% for critical temperature and 6.39% for critical pressures,
compared with the experimental data.
Acknowledgments
This work was supported by the National Basic Research Pro-
gram of China (No. 2015CB251502), the National Science Fund for
Distinguished Young Scholars of China (No. 51525604) and 111
project B16038.
7
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.fluid.2016.11.017.
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