Optimization of Binary Interaction Coefficient for

Water- Ammonia Mixture

N. Mehran Bod1, P. Parvasi1,*, A.R. Rahmani1, M. Ranjbaran1, A.R. Sadeghi1

1-Shiraz university, Department of chemical engineering

Abstract:

Water-ammonia system has been used as a major refrigerant in absorption refrigeration

machines for many years. Many studies have been focused on prediction of vapor-liquid
equilibrium and thermodynamic properties of this system. In this study, the vapor-liquid
binary interaction coefficient of the water-ammonia mixture has been determined using two
approaches for PR and SRK equations of state. In the first approach that is commonly used in
the field of applied thermodynamics, one set of coefficients is used for both phases whereas
in the second one, different coefficients have been used for liquid and vapor phases. The
binary interaction coefficients were optimized using experimental phase equilibrium data for
the temperature range of 306 to 618 K and total pressure range of 0.036 to 22.5 MPa.
Comparison of predicted and experimental data showed that a) the average absolute relative
error obtained by the second approach is much smaller than the first one and b) PR equation
of state provide much better predictions compared to SRK.

Keywords: Binary interaction coefficient; Water-ammonia system; Equation of state; Vapor-

liquid equilibrium.

1. Introduction

Design of an industrial process requires reliable knowledge of phase equilibrium data on

components involving in the process. This is usually obtained by means of equations of state that
are trained by experimentally measured Vapor Liquid Equilibrium (VLE) data of the
thermodynamic systems involved in the process. The selection of a suitable well-trained
thermodynamic model for prediction of phase equilibrium is fundamental to process modeling
and simulation. Selection of an inappropriate model will result in convergence problems and
erroneous results.
The water-ammonia system has many applications in industrial processes, geothermal systems
[7], refrigeration, and most recently, electric power generation [7]. Therefore accurate prediction
of thermodynamics properties of this system is a key factor to engineering designs that are
supposed to operate effectively and get acceptance in the highly competitive global economy.
Such property prediction is not easy to achieve because of two property aspects of the water-
ammonia system. The first aspect that is due to toxicity, flammability, corrosiveness, and high
relative volatility of this system that has conspired to limit the quantity and accuracy of
experimental data available on this system. Strong polarity of the pure fluids and their mutual
chemical affinity cause the second aspect that makes it hard to mathematically model behavior of
this system.
This study is a continuation of available sources in open literature on thermodynamic property
prediction of water-ammonia system that aimed to cover broader temperature and pressure ranges

1
and. In this paper, a thorough literature review on thermodynamics property prediction of water-
ammonia system is presented in first section. In the second section the two approaches based on
equation of state used in this research work to model the behavior of this system is outlined.
Comparison between predicted and experimental data using the two approaches is presented in
Section 4 and the last section, Conclusions, provides a brief on methods used and aimed goals
achieved.

2. Equation of state (EOS)

Originally, equations of state were designed to describe mathematically the relation between
pressure, specific volume and temperature (PVT) of homogeneous gas systems. Equations of
state can take different forms from ideal gas law to more complicated forms like that of Lee-
Kesler type. Most commonly used analytical equations are the so-called cubic equations of state.
Cubic nature implies that the expanded form of equation has volume terms raised up to the third
power. This means that the largest positive root corresponds to the molar volume of the vapor and
the smallest positive root to the molar volume of the liquid. Two cubic commonly used equations
of state in the field of applied thermodynamics are PR, [3], and SRK, [5].
Peng and Robinson (1976) proposed the cubic equation of state of the form of Eq. 1, whereas
Soave, Redlich and Kwong (1976) proposed Eq. 2 for correlating PVT behavior of pure
component systems. In some cases, PR EOS is known to give slightly better predications of
liquid densities than SRK EOS [1].

(1)

(1-a)

(2)

(2-a)

where a and b are two parameters that can be calculated using temperature and critical state
properties. To extent the use of these two equations of state, one requires a mixing rule that
allows calculation of equation parameters for the mixture. Literature is rich with verity of mixing
rules that can be applied for PR and SRK equations of state. These rules are ranging from the
simplest, proposed by Van der waals [1] to more complex ones such as extended Twu-Coon [2].

2
In this study the Van der waals mixing rule presented by Eqs. 3 and 4 is used due to the merit of
its simplicity that renders less computational time necessary for complex process simulations and
binary interaction coefficient optimization.

(3)

(4)

where i, j represent components, wi is mole fraction of component in mixture, ai and bi are

equation parameters for pure component and kij is binary interaction coefficient.
The numerical value of binary interaction coefficient at a specific temperature and pressure
can be calculated using experimental VLE data in an optimization algorithm. The optimization
algorithm minimizes discrepancy between experimental and EOS-based calculated data.
Binary interaction coefficient generally has some kind of temperature dependency [1]. Usually
the dependency is linear however polynomials could also be used in some cases [1]. Once such
dependency is put in a mathematical format, one can extend VLE calculation to the outside of the
ranges of experimental data used for optimization algorithm. Worth to note that extrapolation
may be associated with some degree of error. An exponential/logarithmic type correlation for kij
is not advised [1] because it requires more complex mathematical format compared to
polynomials and does not capture the temperature dependency effectively.
The necessary manipulations that should be applied to PR and SRK equations of state to
obtain the equations required for any type of phase equilibrium calculation are well established.
The outcome of such manipulations is the equations required to calculate fugacity coefficient for
each component in different phases. The specific equation for PR and SRK equations of state are
presented in Eq. 5 and 6 respectively.

(5)

(6)

where Z is compressibility factor and the parameter can be defined as:

(7)

The calculated fugacity coefficients for a binary mixture at specific temperature and pressure
are required to perform a phase equilibrium calculation in order to calculate optimized binary
interaction coefficient. The choice of phase equilibrium calculation in this study is discussed in
the following section.

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3. Phase equilibrium calculation

To obtain numerical value of binary interaction coefficient at a specific temperature and

pressure via an optimization algorithm, one may use different types of phase equilibrium
calculations. These phase equilibrium calculations are dew point, bubble point and two-phase
flash calculations. A procedure for obtaining binary interaction coefficient, in which flash
calculation is used provide superior results compared to those obtained from dew and bubble
point calculations. This is due to the fact that in flash calculation the objective function to be
minimized by optimization algorithm includes information for mole fraction of components in
both liquid and vapor phases.
For two-phase flash calculation, pressure, temperature, amount of feed stream, F, and overall
mole fractions, zi, are specified, and amounts of liquid and vapor phases, L and V, and their
compositions at equilibrium, xi and yi, are calculated. The material balance equations can be
expressed as follows:

(8)
(9)

The condition for a two-phase system consisting of vapor and liquid phases at the same P and
T in equilibrium is that the fugacity of each compound is the same in both phases. This condition
is given in Eq. 7.

(10)

where and are liquid and vapor phase fugacity for each component respectively.
There are different types of two-phase flash calculation that are discussed in many textbooks.
The one chosen in this study is based on initial guess of liquid fraction, L/F, because it does not
show convergence problems at high pressures compared to other types of two-phase flash
calculation. A very brief step-by-step procedure is presented here.

a. Provide initial guess for all unknown parameter.

b. Solve the EOS for the phase compressibility factor.
c. Calculate fugacity coefficients of each component in each phase.
d. Calculate the K-values and mole fractions.
e. Check for equilibrium condition against assigned tolerance limits. If the assigned tolerance
limits are met then flash calculation is complete, otherwise perform step f.
f. Provide new value for liquid fraction by a proper method (e.g. Newton’s method) if the
assigned tolerance limits are not met and return back to step b.

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 Figure 1. Flowchart of the flash calculation

4. Optimization procedure

Adjustable binary interaction coefficient in the proposed mixing rules calculated by regression
analysis of experimental phase equilibrium data. The basic idea in the regression analysis usually
employed to determine the optimized binary interaction coefficient is to apply the selected EOS
for calculation of a particular property and then to minimize the difference between predicted and
experimental values of that property according to a specified objective function. The objective
function should be defined based on the application that the trained EOS is supposed to be
applied. In this study, the objective function used to determine optimized binary interaction
coefficient at a specific temperature and pressure is defined by the sum of Absolute Relative
Error (ARE) in mole fractions of both components in two phases.

(11)

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 The reason supporting this choice of objective function is the fact the optimization based on
just one phase or one component may lead to in accurate predictions for the other phase or
component. Figure 2 presents the flowchart of necessary calculations for this optimization.

Figure 2. Flowchart of binary interaction coefficients for vapor and liquid phases.

Correlations have been presented to express temperature dependency of binary interaction

coefficient in compact mathematical format [1]. For example, Nikos and coworkers proposed an
equation [1] that is applicable for multi-component phase equilibrium calculations where the
system under study contains N2, CO2 and CH4. In this study a polynomial function of temperature
of 4th order, shown by Eq. 12, is used to capture temperature dependency of binary interaction
coefficient.

(12)

Where the constants, are considered to be pressure dependent as:

(13)
(14)
(15)
(16)
(17)

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 In Eqs. 12 to 17, T and P are in K and MPa, respectively and these equations collectively show
that Binary interaction coefficients are considered function of both temperature and pressure. An
optimization algorithm based on minimization of the objective function defined by Eq. 18 is used
to find numerical values of the associated constants, in Eqs. 12 to 17.

(18)

where n is number of experimental data points used for optimization.

5. Result and discussion

Optimization of binary interaction coefficient for PR and SRK equations of state is performed
for water-ammonia system for the temperature range of 306 to 618 K and total pressure range of
0.036 to 22.5 MPa.
A flash calculation program based on the calculation sequence of Figure 1 was used to obtain
optimized binary interaction coefficient. Optimization of binary interaction coefficient (kij) was
investigated for a set of data comprises of 300 experimental data [4] for PR and SRK equations of
state. As mentioned earlier in the manuscript, optimization is performed under two different
approaches. In the first approach, one set of coefficients is used for both phases whereas in the
second one, different coefficients have been used for liquid and vapor phases. Optimization
results for these two approaches for a limited subset of experimental data are presented in Tables
1 to 4. Comparison between AREs presented in these four Tables show clearly that considering
different interaction coefficients for liquid and vapor phases improves considerably prediction
accuracy.

Table 1. Optimization result for single binary interaction coefficient for vapor and liquid phases for PR EOS
xExp. yExp. xCalc. yCalc. ARE for PR
T(K) P (Mpa) PR EOS
(NH3) (NH3) (NH3) (NH3) based Eq. 11
451.51 1.106 0.0174 0.1302 0.0174 0.1356 -0.2225 4.7820e-02
451.46 1.416 0.0571 0.3695 0.0571 0.3408 -0.2342 1.2298e-01
451.55 1.709 0.0859 0.4659 0.0859 0.4600 -0.2299 2.3877e-02
451.84 2.364 0.1720 0.6829 0.1720 0.6344 -0.2653 2.2388e-01
451.90 3.353 0.2391 0.7524 0.2391 0.7480 -0.2513 2.3630e-02
452.14 5.172 0.3354 0.8326 0.3354 0.8363 -0.2311 2.6390e-02
452.03 7.072 0.4668 0.8834 0.4495 0.8878 -0.2472 1.1217e-01
451.90 8.851 0.5480 0.9013 0.5099 0.9013 -0.2117 1.5376e-01
451.87 11.677 0.6817 0.9023 0.6111 0.9075 -0.1566 3.8476e-01
451.02 15.114 0.8717 0.8854 0.7691 0.8766 -0.0360 1.0047e+00

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 Table 2. Optimization result for single binary interaction coefficient for vapor and liquid phases for SRK
EOS
xExp. yExp. xCalc. yCalc. ARE for SRK
T(K) P (Mpa) SRK EOS
(NH3) (NH3) (NH3) (NH3) based Eq. 11
451.51 1.106 0.0174 0.1302 0.0174 0.1365 -0.2433 5.5496e-02
451.46 1.416 0.0571 0.3695 0.0571 0.3418 -0.2563 1.1887e-01
451.55 1.709 0.0859 0.4659 0.0859 0.4610 -0.2520 1.9876e-02
451.84 2.364 0.1720 0.6829 0.1720 0.6355 -0.2899 2.1888e-01
451.90 3.353 0.2391 0.7524 0.2391 0.7492 -0.2753 1.7361e-02
452.14 5.172 0.3354 0.8326 0.3354 0.8375 -0.2541 3.5335e-02
452.03 7.072 0.4668 0.8834 0.4500 0.8893 -0.2721 1.2457e-01
451.90 8.851 0.5480 0.9013 0.5065 0.9013 -0.2280 1.6737e-01
451.87 11.677 0.6817 0.9023 0.6128 0.9093 -0.1744 3.9646e-01
451.02 15.114 0.8717 0.8854 0.7652 0.8709 -0.0212 1.0953e+00

Table 3. Optimization result for two binary interaction coefficient for vapor and liquid phases for PR EOS
xExp. yExp. xCalc. yCalc. Optimum Optimum Error based
T(K) P (Mpa)
(NH3) (NH3) (NH3) (NH3) Liquid Vapor Eq. 18
451.51 1.106 0.0174 0.1302 0.0174 0.1346 -0.2302 -0.9544 3.8418e-02
451.46 1.416 0.0571 0.3695 0.0571 0.3695 -0.2049 2.4802 3.3523e-10
451.55 1.709 0.0859 0.4659 0.0859 0.4659 -0.2257 0.1174 1.2248e-10
451.84 2.364 0.1720 0.6829 0.1720 0.6829 -0.2437 1.3340 1.4442e-09
451.90 3.353 0.2391 0.7524 0.2391 0.7524 -0.2493 -0.1444 1.6440e-09
452.14 5.172 0.3354 0.8326 0.3354 0.8326 -0.2330 -0.2993 1.5391e-09
452.03 7.072 0.4668 0.8834 0.4634 0.8834 -0.2755 -0.4487 1.3782e-02
451.90 8.851 0.5480 0.9013 0.5326 0.9013 -0.2568 -0.3914 6.2371e-02
451.87 11.677 0.6817 0.9023 0.6294 0.9023 -0.2209 -0.3532 2.4105e-01
451.02 15.114 0.8717 0.8854 0.0421 0.8737 -0.0600 -0.0500 6.4123e-01

Table 4. Optimization result for two binary interaction coefficient for vapor and liquid phases for SRK EOS
xExp. yExp. xCalc. yCalc. Optimum Optimum Error based
T(K) P (Mpa)
(NH3) (NH3) (NH3) (NH3) Liquid Vapor Eq. 18
451.51 1.106 0.0174 0.1302 0.0174 0.1354 -0.2513 -1.0230 4.7779e-02
451.46 1.416 0.0571 0.3695 0.0571 0.3695 -0.2263 2.5188 4.0775e-10
451.55 1.709 0.0859 0.4659 0.0859 0.4659 -0.2482 0.0537 1.7986e-10
451.84 2.364 0.1720 0.6829 0.1720 0.6829 -0.2676 1.3645 4.8478e-10
451.90 3.353 0.2391 0.7524 0.2391 0.7524 -0.2738 -0.1922 1.0200e-09
452.14 5.172 0.3354 0.8326 0.3354 0.8326 -0.2568 -0.3508 2.8648e-09
452.03 7.072 0.4668 0.8834 0.4621 0.8834 -0.3002 -0.4960 1.8916e-02
451.90 8.851 0.5480 0.9013 0.5315 0.9013 -0.2802 -0.4348 6.6567e-02
451.87 11.677 0.6817 0.9023 0.6292 0.9023 -0.2411 -0.3885 2.4183e-01
451.02 15.114 0.8717 0.8854 0.7513 0.8636 -0.0700 -0.0600 7.7614e-01

The AREs obtained from the optimization for the complete set of experimental data show that
PR EOS provides much accurate predictions compared to SRK EOS.
To avoid including many tables in the manuscript presenting the optimized values of binary
interaction coefficient for the whole set of experimental data, we suffices presenting the
optimized constant of Eqs. 13 to 17 for PR EOS in Tables 5 to 7.

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 Table 5. Optimized constants for single binary interaction coefficient for liquid and vapor phases .
Parameter Value Parameter Value Parameter Value
1.35e-02 -2.36e-02 -1.81e-02
-1.04e-04 3.06e-03 3.03e-03
3.83e-07 -1.68e-05 -2.89e-05
-6.62e-10 3.08e-08 6.98e-08
4.19e-13 -1.88e-11 -5.09e-11

Table 6. Optimized constants of liquid phase binary interaction coefficient .

Parameter Value Parameter Value Parameter Value
2.95e-03 -1.65e-02 2.83e-03
9.04e-05 -5.57e-04 3.27e-03
-4.94e-07 4.29e-06 -3.13e-05
8.70e-10 -1.03e-08 7.50e-08
-5.10e-13 7.82e-12 -5.34e-11

Table 7. Optimized constants of vapor phase binary interaction coefficient .

Parameter Value Parameter Value Parameter Value
-3.36e-02 2.10e-02 8.60e-03
-3.31e-04 1.22e-02 -1.23e-02
-5.34e-07 1.19e-05 -4.00e-04
6.66e-09 -1.83e-07 1.69e-06
-7.94e-12 2.19e-10 -1.68e-09

It is worth to note that the data presented in Table 7 for vapor phase binary interaction
coefficient is valid for the temperature range of 400 to 618 K.

6. Conclusion

The vapor-liquid binary interaction coefficient of the water-ammonia system is determined

using two approaches for PR and SRK equations of state for the temperature range of 306 to 618
K and total pressure range of 0.036 to 22.5 MPa. One set of coefficients is used for both liquid
and vapor phases in the first approach. In the second one, different coefficients are determined for
liquid and vapor phases. The average absolute relative error obtained by the second approach is
much smaller compared to the first one. For the whole set of experimental data used in this study
PR EOS proved to provide more accurate predictions compared to SRK EOS. Negative values of
binary interaction coefficients may be interpreted as an evidence for inadequacy of the
thermodynamic models, PR and SRK equations of state, investigated in this study. However, it is
worth to note that in general these two parameters cubic equations of state provide much better
predictions compared to other two parameters cubic equations of state. Lack of explanation for
negative values of binary interaction coefficients is major set back. In spite of this set back, the
results presented show that the use of PR EOS with two different binary interaction coefficients
for liquid and vapor phases for VLE predictions of water-ammonia system assures high accuracy.

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