Accepted Manuscript

Title: Modeling of vapor-liquid-liquid equilibria in binary mixtures

Author: N. Tzabar, H.J.M. ter Brake
PII:
DOI:
Reference:

S0140-7007(16)30005-6
http://dx.doi.org/doi: 10.1016/j.ijrefrig.2016.02.023
JIJR 3278

To appear in:

International Journal of Refrigeration

Received date:
Revised date:
Accepted date:

21-12-2015
23-2-2016
25-2-2016

Please cite this article as: N. Tzabar, H.J.M. ter Brake, Modeling of vapor-liquid-liquid equilibria
in binary mixtures, International Journal of Refrigeration (2016), http://dx.doi.org/doi:
10.1016/j.ijrefrig.2016.02.023.
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Modeling of vapor-liquid-liquid equilibria in binary mixtures

N. Tzabar* and H.J.M. ter Brake

Corresponding author: email: nirtzabar8@gmail.com, phone: +31-6-16167336

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Energy, Materials and Systems, Faculty of Science and Technology, University of

Twente, 7500 AE Enschede, The Netherlands

Highlights

The numerical model determines the temperatures where VLLE occur in

binary mixtures

Only readily available parameters are used

The activity coefficients are determined by the regular solution theory

The excess Gibbs energy is determined by using the two-constant Margules

expression

The numerical method has been successfully verified against experimental

data

Abstract
Vapor compression and Joule-Thomson (JT) cycles provide cooling power at the
boiling temperatures of the refrigerants. Maintaining a fixed pressure in the
evaporator allows for a stable cooling temperature at the boiling point of a pure
refrigerant. In these coolers enhanced cooling power can be achieved by using mixed
refrigerants. However, gas mixtures usually do not change their phase at a constant
temperature, therefore, the cooling temperature has to be actively controlled. An
exception to this rule holds for binary mixtures that can form a vapor-liquid-liquid
equilibrium (VLLE).
Phase equilibria in binary mixtures are usually modeled based on experimental results
only. In the present study only the vapor pressures of the pure mixture components
are required. The calculated results of nitrogen-ethane, nitrogen-ethylene, and

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nitrogen-propane mixtures are compared with experimental data presented in

literature showing deviations of less than 1 %.

Keywords
Binary mixture; Phase equilibrium; Regular solution theory; Margules expansion;
refrigerant

Nomenclature
G

molar Gibbs energy, J mol-1

molar enthalpy, J mol-1

pressure, MPa

universal gas constant, 8.314 J mole-1 K-1

temperature, K

molar energy, J mol-1

molar volume, m3 mol-1

mole fraction in a liquid phase

mole fraction in a vapor phase

Subscripts
calc

calculated

exp

experimental

component i

mix

mixture

Superscripts

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mix

mixing

excess

vap

vaporization

L1

liquid phase 1

L2

liquid phase 2

Greek symbols

activity coefficient

solubility parameter

volume fraction

Abbreviations and Acronyms

EOS

Equation of State

LLE

Liquid-Liquid Equilibrium

RK

Redlich-Kister

PR

Peng-Robinson

RST

Regular Solution Theory

SRK

Soave-Redlich-Kwong

VLE

Vapor-Liquid Equilibrium

VLLE

Vapor-Liquid-Liquid Equilibrium

1. Introduction
Mixed refrigerants are widely investigated for refrigeration cycles, mostly to provide
enhanced cooling power (Nayak and Venkatarathnam, 2009, Tzabar and Lapp, 2010,
Walimbe et al., 2010, Tzabar and Grossman, 2012). The main drawback of the

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mixtures, relative to pure refrigerants, is the dependency of the cooling temperature

on the warm-end temperature of the refrigerator and the heat load. This drawback is a
consequence of the phase transition that occurs over a relatively wide temperature
range rather than at a constant temperature as is the case for pure gases. According to
the Gibbs phase rule, binary mixtures with an equilibrium of three phases behave like
a pure gas in the sense that at a fixed pressure a constant temperature phase transition
is obtained. In a previous study (Tzabar, 2014), the temperatures of the phase
transition for several binary mixtures were estimated by Vapor-Liquid Equilibria
(VLE) calculations, which were experimentally validated.

The objective of the

current research is to establish a method for calculating the Vapor-Liquid-Liquid

Equilibria (VLLE) of binary mixtures to improve the prediction of the cooling
temperature and to allow extensive search for new refrigerants.
Phase equilibria in binary mixed refrigerants have been widely investigated for CO2hydrocarbon refrigeration systems (Garcia et al., 2004, Coquelet and Richon, 2009),
and CO2-hydrofluoro-olefins refrigeration systems (Juntarachat et al., 2014).
Nitrogen-hydrocarbon mixtures are important for the testing and extension of fluid
mixture theories but also for many engineering processes like the separation and
refinement of natural gas. Most researches are dedicated to VLE; however, VLLE are
also considered and published data on nitrogen-ethane (Raabe and Kohler, 2004,
Guedes et al., 2002, Llave et al., 1985, Romig and Hanley, 1986), nitrogen-ethylene
(Gasem et al., 1981), and nitrogen-propane (Llave et al., 1985, Houssin-Agbomson et
al., 2010) mixtures is also available.
VLE can be calculated by different equations of states (EOS) with various mixing
rules. Classical mixing rules are inferior relative to excess Gibbs energy (GE) mixing
rules, as was also shown by Raabe and Kohler (2004) that have tested both Peng-

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Robinson (PR) and Soave-Redlich-Kwong (SRK) EOSs with different mixing rules
and found that for reproducing the complex phase behavior of mixtures the GEmixing rules with temperature-dependent parameters in the activity coefficient model
are needed. Many GE- mixing rules are suggested in literature; however, they all
require the activity coefficient values which often are derived from experimental
results. Holderbaum and Gmahling (1991) have suggested the Predictive SoaveRedlich-Kwong (PSRK) method that is based on the SRK EOS and the UNIFAC
model. Fisher and Gmehling (1996) extended the number of components that may be
used by the PSRK method. Houssin-Agbomson et al. (2010) have adjusted their
experimental results to the PR EOS with the Mathias-Copeman alpha function and the
Huron-Vidal mixing rule involving the Non-Random Two-Liquid (NRTL) activity
coefficient model. A similar method using the Wong-Sandler mixing rules has been
published by Fedali et al. (2014). Staudt and Soares (2012) suggested the SelfConsistent Mixing Rule (SCMR) that is also suitable for elevated pressure and
temperature cases. Other models like Wilson and UNIQAUC are in use and provide
similar results like the above mentioned models.
Molecular- based EOSs are also in use, for example, the Perturbed-Chain Statistical
Associated Fluid Theory (PC-SAFT) that is suggested by Gross and Sadowski (2001)
and used by Garcia-Sanchez et al. (2004) for calculating the VLE of nitrogenhydrocarbon systems.
The motivation of the present study is to evaluate the temperature-pressure relation of
binary mixtures where VLLE exist, for refrigeration applications. In order to scan
multiple components as candidates for mixed-refrigerants and at a wide range of
temperatures and pressures, a model is desired that does not require experimental data
as input. This requirement led us to use the regular solution theory (RST) for

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evaluating the activity coefficient, and the two-constant Margules expansion to

determine the excess Gibbs energy. Satisfactory agreement with experimental results
from the literature is obtained for nitrogen-ethane, nitrogen-ethylene, and nitrogenpropane systems.

2. Method

2.1. Gibbs energy of the liquid phase

The Gibbs energy of a mixture of N components is given by:
N

x i G i RT

x i ln x i G

(1)

Here, G is the total molar Gibbs energy of the mixture, xi is the molar fraction of
component i, Gi is the Gibbs energy of the pure component i, R is the universal gas
constant, and T is the temperature. The first term at the right side of Eq. (1) is a linear
summation of the pure component properties, whereas the other two terms represent
the Gibbs energy of mixing. The former of these two represents the mixing Gibbs
energy for an ideal mixture whereas the latter term is the excess Gibbs energy that
represents the deviation of a real mixture from an ideal one. Different methods are
proposed for evaluating this excess Gibbs energy (GE), and they all rely on the
activity coefficient of the components. In the current research we use the two-constant
Margules expansion (Sandler, 2006):
G

x 1 x 2 A B x 1 x 2

(2)

In this expansion, the parameters A and B can be found by solving the following linear
system:

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 x2
2
x1
2

3 x2 4 x2 A
RT ln 1

3
2
4 x1 3 x1 B
RT ln 2
2

(3)

Here, 1 and 2 are the activity coefficients of components 1 and 2, respectively. In

most cases, either the GE or the activity coefficients are derived from experimental
results. As mentioned above, we instead theoretically evaluated the activity
coefficients according to the RST:
RT ln 1 V 1 2 1 2
2

RT ln 2 V 2 1 1 2
2

(4)

(5)

Where i and Vi are the solubility parameter and the liquid phase molar volume of
component i, respectively. i is the volume fraction of component i defined as:

xiV
V

(6)

mix

We calculate the molar volume of the mixture liquid phase, Vmix, by the SRK EOS,
which in this case was found to be more accurate than the PR EOS. We used the
classical van der Waals mixing rules for both EOSs with the same binary interaction
parameters, which are originally for the PR EOS and are listed in Table 1. The
solubility parameter of component i, i, is determined according to its definition:

vap

(7)

Where vapUi is the molar energy of vaporization of component i, which is calculated

as follows:

vap

Ui

vap

H i RT

(8)

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The heat of vaporization of component i, vapHi, is evaluated by the ClausiusClapeyron equation:

d ln p

vap

dT

vap

(9)

RT

Where pvap is the vaporization pressure of a pure component, which is available data.
2.2. LLE
In a binary mixture two liquid phases will be separated if
G
2

x1

Incorporating Eq. (1) and (2), applying

x 2 1 x1

(10)

and differentiating the result twice

yields:
G
RT

6 B 2 A 12 Bx

2
x 1 1 x 1
x1 T , p
2

(11)

Incorporating Eq. (10) and (11) yields the criteria for the separation of the liquid
phase and the existence of LLE
T

x 1 1 x 1

12

Bx 1 2 A 6 B

(12)

Eq. (12) provides an upper limit for the temperature in searching for VLLE.
2.3. VLLE
The temperature where VLLE exists is determined by additional requirements, which
at low pressures are:
x1 1 p 1
L1

L1

vap

x1 1 p 1
L2

L2

vap

y1 p

(13)

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x2 2 p2
L1

L1

vap

x2 2 p2
L2

L2

vap

y2 p

(14)

Where the superscript L1 and L2 denote the two liquid phases and yi represents the
molar fraction of component i in the vapour phase.

3. Results and discussion

The temperatures in which VLLE occur as a function of the pressure are presented for
nitrogen-ethane, nitrogen-ethylene, and nitrogen-propane in Figures 1, 2, and 3,
respectively. The calculated results are shown in solid lines and experimental results
from literature are shown in symbols. The calculated results are in a good agreement
with the published experimental results along the entire pressure ranges. Both Figure
1 and Figure 3, for nitrogen-ethane and nitrogen-propane mixtures, respectively, show
a horizontal part at the low pressure range, which is associated with the lowest
temperature where VLLE exists. Figure 4 shows the relative errors between the
calculated results in this research and the experimental results from the literature for
all three mixtures. The calculated results in Figure 1 3 are presented up to the
critical temperatures which are obtained by Eq. (12).

Although the objective of this study was to evaluate the temperature-pressure relation
of the VLLE, the presented model can also be used for indicating the composition of
the two liquid phases in the VLLE. The compositions of the two liquid phases, xL1 and
xL2, are shown in Figures 5 and 6 for nitrogen-ethane and nitrogen-propane mixtures,
respectively. The x axis is the nitrogen molar fraction in the liquid and the y axis is
the temperature of the VLLE state. The calculated results from this research are

10

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compared with the experimental results from the literature. Calculated and
experimental results correspond in the sense that the compositions only weakly
depend on the VLLE temperature. However, differences occur in the composition of
the two liquid phases. Deviations of about 60 % and 17 % are obtained for xL1 and xL2,
respectively, for nitrogen-ethane mixtures, and deviations of about 40 % and 9 % are
obtained for xL1 and xL2, respectively, for nitrogen-propane mixtures. These relative
large deviations are a consequence of the numerical algorithm. We aim for a high
accuracy of the VLLE temperature rather than the accuracy of the phase
compositions; therefore, iterative procedures and convergence restrictions yield this
lower accuracy for the compositions. The method has to be further improved to
decrease the inaccuracy of the calculated compositions and shall be used mainly for
estimating the temperatures where VLLE occur. The values of xL1 and xL2 provide the
limits for the mixture composition to be used as a refrigerant in order to obtain the
VLLE.

4. Conclusions
In the current paper we present a method for calculating the temperature where LLE
and VLLE occur in binary mixtures. The strength of the current method is that only
the vapor pressures of the pure components and their binary interaction parameters of
PR EOS for the classical van der Waals mixing rules are required, which usually are
readily available. This is in contrast to other methods proposed in literature that
require mixture data that need to be experimentally determined.
The method proposed in this paper uses the regular solution theory to determine the
activity coefficients and the two-constant Margules expression for calculating the

11

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excess Gibbs energy. The volume of the mixture is calculated with the SRK EOS
applying the classical Van der Waals mixing rules. The method has been verified
against published experimental data for nitrogen-ethane, nitrogen-ethylene, and
nitrogen-propane mixtures. A good agreement between our calculated results and the
published experimental results is obtained for VLLE temperature. The agreement of
the liquid phase compositions is less impressive; however, the main objective of the
current research is to determine the temperature of VLLE mainly for refrigeration
applications.
This method enables a convenient and efficient analytical study on VLLE for a wide
range of binary mixtures at various temperatures and pressures. We intend to use this
method to explore a wide range of mixtures for refrigeration cycles.

Acknowledgments
This work is supported by NanoNextNL, a micro and nanotechnology consortium of
the government of the Netherlands and 130 partners. The authors thank prof. Louis
van der Ham for his comments on the manuscript.

References
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Garcia-Sanchez F., Eliosa-Jimenez G., Silva-Oliver G., and Vazquez-Roman R.,
Fluid Phase Equilibria 217 (2004), pp 241-253.

12

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(2010), pp 248-256.
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13

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Walimbe N.S., Narayankhedkar K.G., and Atrey M.D., Cryogenics 50 (2010), pp

653-659.

Figure 1 VLLE temperature versus pressure for nitrogen-ethane mixtures.

Calculated results (solid line) in comparison with experimental data from literature
(symbols).

14

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Figure 2 VLLE temperature versus pressure for nitrogen-ethylene mixtures.

Calculated results (solid line) in comparison with experimental data from literature
(symbols).

Figure 3 VLLE temperature versus pressure for nitrogen-propane mixtures.

Calculated results (solid line) in comparison with experimental data from literature
(symbols).

15

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Figure 4 Errors of the VLLE temperatures between the calculated results from this
research and the experimental results from the literature for nitrogen-ethane, nitrogenethylene, and nitrogen-propane mixtures.

Figure 5 Liquid phase concentrations for nitrogen-ethane mixture at VLLE state. A

comparison between calculated results and experimental data.

16

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Figure 6 Liquid phase concentrations for nitrogen-propane mixture at VLLE state.

A comparison among this research calculated results and the experimental results
from the literature.

Table 1. Binary interaction parameters used for the SRK EOS (Sandler, 2006)

N2

17

C2H4

C2H6

C3H8

0.086

0.044

0.078

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