UNIQUAC Interaction Parameters with Closure

for Imidazolium Based Ionic Liquid Systems

Using Genetic Algorithm
Ranjan Kumar Sahoo, Tamal Banerjee and Ashok Khanna*
Department of Chemical Engineering, Indian Institute of Technology, Kanpur, INDIA-208016

Ionic liquids (ILs) are being considered as favourable solvents for liquid-liquid extraction. Ternary phase equilibria containing the ionic liquid
based systems have been reported in the literature for aromatic-aliphatic-IL as well as aliphatic-alcohol-IL ternary systems. In this work global
optimization has been used for the prediction of UNIQUAC interaction parameters for IL based systems. The twin concepts of closure equation
and global optimization via Genetic Algorithm (GA) have been benchmarked and tested on 88 aromatic and 28 hydrogen bonding multi-
component systems. For the aromatic systems the rmsd values obtained with closure equation are ~20 percent better than without closure
equation and ~50 percent better than literature. Similarly for hydrogen bonding systems with closure equation gives ~20 percent better rmsd
values than without closure equations with an overall improvement of ~60 percent. After this rigorous testing we have applied this procedure
on 29 imidazolium based IL ternary systems. Improvements in rmsds with closure have been ~6 percent better than without closure.

Les liquides ioniques (IL) sont considérés comme des solvants favorables pour l’extraction liquide-liquide. Des équilibres de phase ternaire
contenant des systèmes ioniques à base liquide ont été mentionnés dans la littérature scientifique pour des systèmes d’IL aromatiques-alipha-
tiques et des systèmes ternaires aliphatique-alcool-ternaire. Dans ce travail, on a utilisé une optimisation globale pour la prédiction de paramè-
tres d’interaction UNIQUAC pour des systèmes à base d’IL. Les concepts jumeaux d’équation de clôture et d’optimisation globale par
l’algorithme génétique (GA) ont été testés sur 88 systèmes aromatiques et 28 systèmes multicomposants à liaison hydrogène. Pour les systèmes
aromatiques, les valeurs d’écart quadratique moyen rmsd obtenues avec l’équation de clôture sont ~20 pour cent meilleures que sans l’équation
de clôture et ~50 pour cent meilleures que dans la littérature scientifique. De la même manière, pour les systèmes à liaison hydrogène avec
l’équation de clôture les valeurs sont ~20 meilleures que les valeurs rmsd que sans les équations de clôture avec une amélioration globale de
~60 pour cent. Après ces essais rigoureux, nous avons appliqué cette procédure à 29 systèmes ternaires d’IL à base d’imidazolium. Les amélio-
rations dans les rmsd avec clôture sont ~6 pour cent supérieures que sans clôture.

Keywords: ionic liquids, liquid-liquid extraction, UNIQUAC, closure equations, genetic algorithm

INTRODUCTION aromatic-aliphatic as well as aliphatic-alcohol separation using

T
ionic liquid as a solvent.
he separation of aromatic hydrocarbons from C4 to C10
To predict the separation, it is necessary to know the liquid-
aliphatic hydrocarbon mixtures is challenging since these
liquid equilibrium data for a particular system. Various activity
hydrocarbons have boiling points in a close range and
coefficient models such as Universal Quasi Chemical (UNIQUAC)
several combinations form azeotropes. Ionic liquids (ILs) have
and Non-Random Two Liquid (NRTL) can be used to predict the
been an area of interest both in clean industrial processes, such
LLE. Each of these models requires proper binary interaction
as liquid media for separation and extraction. Because of its
parameters that can represent LLE for highly non-ideal liquid
negligible vapour pressure and wide liquidus range, they are
mixtures. These parameters are usually estimated from the known
now used as an alternative to conventional solvents (Brennecke
experimental LLE data via optimization of a suitable objective
and Maginn, 2001; Marsh et al., 2004). The liquid-liquid equilib-
function (Kang and Sandler, 1987). The optimization problem can
rium (LLE) data gives a fair indication of the separation power
be either the least square objective function minimization or
of these novel solvents. Data available till now consists of the
likelihood function maximization. In both cases the objective
infinite dilution activity coefficients (David et al., 2003; Heintz
function is non-linear and non-convex in terms of optimization
et al., 2003) and the liquid-liquid extraction (Letcher and
Deenadayalu, 2003a; Selvan et al., 2000). The LLE data are the
important ones in deciding their suitability of these solvents for * Author to whom correspondence may be addressed.
extraction purpose. Till date ternary tie line data are available for E-mail address: akhanna@iitk.ac.in

Volume 85, December 2007 The Canadian Journal of Chemical Engineering 833
variables; this possesses several local minima/maxima/saddle generated using genetic operators – crossover (arithmetic, heuris-
points within the specified bounds of the variables. Various local tic, and simple) and mutation (boundary, multi-non-uniform,
methods have been proposed to efficiently perform the constrained non-uniform, and uniform). Relationships for selection function
or unconstrained optimization. These use gradient-based and operators are given in Appendix A. GA moves from generation
approaches like Gauss–Newton (Britt and Luecke, 1973; Fabries to generation until a termination criterion is met. The most
and Renon, 1975; Anderson et al., 1978; Schwetlick and Tiller, frequently used stopping criterion is a specified maximum
1985), Gauss–Marquardt (Valkó and Vajda, 1987) or the succes- number of generations (Gmax) (Singh et al., 2005; Houck et al.,
sive quadratic programming SQP methods (Tjoa and Biegler, 1991, 1996). Various input parameters used for selection function and
1992). Alternatively, the possibility of nongradient methods like operators are given in Table 1. Finally GA gives best population of
simplex pattern may be used (Gmehling et al., 1990; Vamos and interaction parameters which is available at the top of the list as
Hass, 1994). Therefore, it is necessary to apply a technique that
results in the global optimization of the variables. Several such
techniques are reported in literature, like Interval methods (Gau
and Stadtherr, 2000a), Branch and Bound methods (Esposito and
Floudas, 1998; Adjiman et al., 1998; Zhu and Inoue, 2001). Moore
et al. (1992) and Ratz and Csendes (1995) have both used
parameter estimation as an example in demonstrating more
general algorithms based on interval methods. Evolutionary
algorithms like genetic algorithm (GA) (Singh et al., 2005;
Papadopoulos and Linke, 2004) and simulated annealing (SA)
(Papadopoulos and Linke, 2004) have been rarely used for the
optimization of LLE processes.
The binary interaction parameters for UNIQUAC and NRTL
models are dependent on each other following a linear relation-
ship called closure equations (Ahmad and Khanna, 2003; Juliá et
al., 2005; Sahoo et al., 2006). For a ternary triplet i-j-k the adjust-
able binary interaction parameters are related as (Hala, 1972):

( t jk − tkj ) = ( tik − tki ) − ( tij − t ji ) (1)

The number of such relationships for a c component system

is 0.5 × c(c – 3) + 1 (Hala, 1972). In the present work, the
closure equation concept has been utilized first on the 116 non-
ionic liquid based systems, and then it has been used on the
ionic liquids along with the closure equations.

THEORY AND CALCULATION

Genetic Algorithm
GA was first proposed by Holland (1975) and has been widely
used recently. It is a method that searches for the global optima of
an objective function through the use of simulated evolution; the
survival of the fittest strategy. Unlike most of the optimization
methods, GA does not require any initial guess but only the upper
and lower bounds of the variables – in our case the interaction
parameters, which is a characteristic of interval methods as well
(Gau et al., 2000).
GA explores all regions of the solution space and exponentially
exploits promising areas through selection, crossover and mutation
operations applied to interaction parameters in the population.
Float genetic algorithm (FGA) is better than both binary genetic
algorithm (BGA) and SA in terms of computational efficiency and
solution quality (Houck et al., 1995). FGA has been used for the
estimation of interaction parameters. Flow diagram for FGA is
given in Figure 1. FGA starts with initial populations of fixed size.
Interaction parameters in the initial populations are generated
randomly. Normalized geometric ranking, a probabilistic selection
method, is used for the selection of populations. This method
selects populations for next generation based on their fitness to
the objective function. This is the role played by the probability of
selecting the best individual (q). Remainder populations are
randomly generated. Size of the population remains the same in
each generation. In each generation, new populations are
Figure 1. Flow diagram for float genetic algorithm (FGA)
Table 1. Values of the parameters used in GA Toolbox of MatLab
(Houck et al., 1995, 1996)
Name Value
Population size, P 100
Maximum number of generations, Gmax 200
Normalized geometric selection
Probability of selecting the best individual, q 0.08
Uniform mutation, number of times 4
Non-uniform mutation, number of times 4
Shape parameter 3
Multi-non-uniform mutation, number of times 6
Shape parameter 3
Boundary mutation, number of times 4
Simple crossover, number of times 4
Arithmetic crossover, number of times 4
Heuristic crossover, number of times 2
Feasibility check, number of times 3
refer to Appendix A

834 The Canadian Journal of Chemical Engineering Volume 85, December 2007
organized by the ranking method from final generation as the
required solution. All types of crossover and mutation operators
have been used for our estimation. However, one can omit any of
the crossover and/or mutation operators.
Closure Equations
The number of closure equation is one for ternary, three for
quaternary and six for quinary system.
Ternary Systems
A ternary system has the following six binary interaction
parameters A12, A21; A13, A31; and A23, A32. Closure equation
which describes the relationship between these six binary
interaction parameters is (Ahmad and Khanna, 2003):
A12 − A21 + A23 − A32 + A31 − A13 = 0 (2)
That is only five out of six binary interaction parameters are
independent.
Quaternary Systems
For a quaternary system, the twelve binary interaction parame-
ters A12, A21; A13, A31; A14, A41; A23, A32; A24, A42; and A34, A43.
Three closure equations for the quaternary systems are (Ahmad
and Khanna, 2003):
A12 − A21 + A23 − A32 + A31 − A13 = 0 (3)
A12 − A21 + A24 − A42 + A41 − A14 = 0 (4)
A23 − A32 + A34 − A43 + A42 − A24 = 0 (5)
That is only nine out of twelve binary interaction parameters
are independent.
Quinary Systems
A quinary system has the following twenty binary interaction
parameters: A12, A21; A13, A31; A14, A41; A15, A51; A23, A32; A24,
A42; A25, A52; A34, A43; A35, A53; and A45, A54. Six closure
equations for quinary systems are (Ahmad and Khanna, 2003):
A12 − A21 + A23 − A32 + A31 − A13 = 0 (6)
A12 − A21 + A24 − A42 + A41 − A14 = 0 (7)
A12 − A21 + A25 − A52 + A51 − A15 = 0 (8)
A23 − A32 + A34 − A43 + A42 − A24 = 0 (9)
A23 − A32 + A35 − A53 + A52 − A25 = 0 (10)
A24 − A42 + A45 − A54 + A52 − A25 = 0 (11)
That is only fourteen out of twenty binary interaction parame-
ters are independent.
Parameter Estimation Procedure
The calculations of LLE were carried using the UNIQUAC model
as given in Appendix B. Binary interaction parameters are
usually obtained from experimental LLE data by minimizing a
suitable objective function.
Volume 85, December 2007 The Canadian Journal of Chemical Engineering 835
Objective Function
The most common objective function is the sum of the square of
the error between the experimental and calculated composition
of all the components over the entire set of tie lines. As GA is
only for maximization, for minimizing the errors between
experimental and calculated mole fractions, the objective function
can be defined as:
m 2 c 2
Max. F=− ∑∑∑ wtli ( xtli − xˆ tli )
t =1 l =1 i =1
w.r.t. Aij ; i, j = 1, 2.....c and j ≠ i (12)
This objective function, with unit weights i.e. wtli = 1, has
been used in this work. The goodness of fit is usually measured
by root mean square deviation (rmsd) defined as:
1/2
 −F 
rmsd =   (13)
 2mc 
Modified Rachford Rice Algorithm (Seader and Henley, 1998)
is used for the calculation of tie lines.
Parameter Elimination
The closure equations have been implemented by the elimina-
tion of the parameters, Aij’s equal to the number of closure
equations. These eliminated parameters can be obtained by the
simultaneous solution of closure equations. There exist several
possibilities of parameter elimination. The number of such
possibilities for ternary system is 6, for quaternary system is 220,
and for quinary system is 38 760. However, all such possibilities
are not feasible. A feasible set is such that the rank of the coeffi-
cient matrix of the eliminated parameters in the closure
equations is equal to the number of independent closure
equations. A general expression for the number of feasible sets
of parameter elimination for a c component system with n
number of closure equation is given as (Ahmad and Khanna,
2003; Hala, 1972):
c c −2 × 2n where n = 0.5 × c( c − 3) + 1 (14)
The following two rules of thumb must be satisfied to obtain
the feasible sets of eliminated parameters (Ahmad and Khanna,
2003),
1. Mirror images (i.e., Aij and Aji) cannot be eliminated
simultaneously.
2. Same component cannot appear as subscript in all the
eliminated parameters.
Thus, number of feasible sets of parameter elimination of
ternary system is 6, for quaternary system is 128 and for quinary
system is 8000. Summary of parameter elimination scheme is
given in Table 2.
RESULTS AND DISCUSSION
Benchmarking
The benchmarking system involves the predictions of LLE for
cyclohexane (1) + xylene (2) + sulpholane (3) ternary system
at 35°C.
 Table 2. Parameter elimination scheme
Parameter elimination procedure System
Ternary Quaternary Quinary
number of components
c 3 4 5
number of binary interaction parameters
a = 2 x c C2 6 12 20
number of closure equations
n = 0.5 x c (c – 3) +1 1 3 6
number of parameter elimination possibilities
aC 6 220 38 760
n

number of feasible sets of parameter elimination

c c–2 x 2n 6 128 8000
number of likely feasible sets of parameter elimination 3 8 21*
* non-aromatic-non-aromatic-aromatic-aromatic-solvent system

Table 3. Effect of bounds on UNIQUAC interaction parameters and rmsd values for the system cyclohexane (1)-xylene (2)-sulpholane (3) at 35°C

Aij /K, woce

Bounds A12 A13 A23 rmsd,
Hitting bound
woce
A21 A31 A32
-105.67 200.00 200.00
±200 0.017 Yes
84.29 200.00 31.12
-20.93 500.00 229.16
±500 0.007 Yes
7.78 92.78 14.92
-233.41 662.70 269.03
±1000 0.006 No
422.52 67.80 9.20
237.05 356.13 910.79
±1500 0.006 No
-229.09 127.34 -137.64
-355.88 668.98 562.32
±2000 0.006 No
840.04 35.41 -98.37

Table 4. Comparison of tielines for cyclohexane (1)-xylene (2)- sulpholane (3) at 35°C (Rappel et al., 2002)

Experimental Predicted
solvent rich phase non-aromatic rich phase solvent rich phase non-aromatic rich phase
x1 x2 x3 x1 x2 x3 x̂1 x̂2 x̂3 x̂1 x̂2 x̂3
0.0241 0.0394 0.9365 0.7230 0.2710 0.0060 0.0276 0.0418 0.9305 0.7250 0.2704 0.0046
0.0225 0.0568 0.9206 0.6456 0.3457 0.0087 0.0266 0.0572 0.9162 0.6456 0.3472 0.0072
0.0312 0.1050 0.8639 0.4303 0.5520 0.0178 0.0238 0.1104 0.8658 0.4352 0.5440 0.0208
0.0316 0.1694 0.8000 0.3154 0.6658 0.0188 0.0237 0.1614 0.8149 0.3128 0.6558 0.0314
0.0259 0.1018 0.8723 0.4540 0.5276 0.0185 0.0240 0.1028 0.8732 0.4551 0.5257 0.0192
rmsd [lit]=0.011 rmsd (woce)=0.006

Lower and Upper Bounds, (ai and bi) Population Size, P

The effect of the value of bounds on the interaction parameters
and rmsd values are given in Table 3. The rmsd value remains
constant after the bound of -1000 and +1000. The lower
values of these, estimate some of the interaction parameters at
the edge of the boundary. Keeping these in mind we have
chosen -1000 and +1000 as the lower and upper bounds for
our estimation.
836 The Canadian Journal of Chemical Engineering Volume 85, December 2007
Effect of population size on absolute objective function value is
shown in Figure 2. It is observed that population size of 100 is
sufficient to give good set of parameters.
Maximum Number of Generation, Gmax
Variation of absolute objective function value against generation
number is shown in Figure 3. It is observed that 200th generation is
sufficient to give a very good set of parameters; further generations­
only seem to improve marginally upon the solution obtained.
Therefore, value of 200 for Gmax has been used for our estimation.
 Table 5. Ternary, quaternary and quinary systems used for parameter estimation

System no. System name Temp., °C Reference

(a) Ternary aromatic extraction systems
1 Pentane(1)-Benzene(2)-Sulpholane(3) 17.0, 25.0, 50.0 (Cassell et al., 1989a)
2 Pentane(1)-Toluene(2)-Sulpholane(3) 17.0, 25.0, 50.0 (Cassell et al., 1989a)
3 Hexane(1)-Benzene(2)-Sulpholane(3) 25.0, 30.0, 50.0, 75.0, 100.0 (Fré and Verhoeye, 1976, Hassan and Fahim, 1988)

Volume 85, December 2007

4 Hexane(1)-Toluene(2)-Sulpholane(3) 25.0, 35.0, 50.0 (Chen et al., 2000a, Rappel et al., 2002)
5 Hexane(1)-Xylene(2)-Sulpholane(3) 25.0, 35.0, 50.0 (Chen et al., 2000a, Rappel et al., 2002)
6 Heptane(1)-Benzene(2)-Sulpholane(3) 25.0, 110.0 (Rawat and Gulati, 1976, Rawat and Prasad, 1980)
7 Heptane(1)-Toluene(2)-Sulpholane(3) 25.0, 30.0, 50.0, 75.0, 100.0 (Fré and Verhoeye, 1976, Hassan and Fahim, 1988)
8 Heptane(1) + xylene(2) + Sulpholane(3) 25.0 (Cassell et al., 1989c)
9 Octane(1)-Benzene(2)-Sulpholane(3) 25.0, 35.0, 45.0, 100.0 (Lee and Kim, 1995, Lin and Kao, 2002)
10 Octane(1)-Toluene(2)-Sulpholane(3) 25.0, 50.0, 75.0 (Lee and Kim, 1995, Lin and Kao, 2002)
11 Octane(1)-Xylene(2)-Sulpholane(3) 25.0, 30.0, 45.0, 50.0 (Hassan and Fahim, 1988, Lee and Kim, 1995, Lin and Kao, 2002)
12 Cyclohexane(1)-Benzene(2)-Sulpholane(3) 25.0, 75.0, 100.0 (Fré and Verhoeye, 1976)
13 Cyclohexane(1) + toluene(2) + sulpholane(3) 25.0 (Mondragón-Garduño et al., 1991)
14 Cyclohexane(1)-Xylene(2)-Sulpholane(3) 35.0, 50.0 (Rappel et al., 2002)
15 Hexene(1)-Benzene(2)-Sulpholane(3) 25.0, 50.0, 100.0 (Fré and Verhoeye, 1976)
16 Hexene(1) + toluene(2) + sulpholane(3) 25.0 (Mondragón-Garduño et al., 1991)
17 Heptene(1) + benzene(2) + sulpholane(3) 25.0 (Chen et al., 2000b)
18 Heptene(1) + toluene(2) + sulpholane(3) 25.0 (Chen et al., 2000b)
19 2-Methylpentane(1) + toluene(2) + sulpholane(3) 25.0 (Mondragón-Garduño et al., 1991)
20 Hexane(1)-Benzene(2)-Dimethyl Sulphoxide(3) 10.0, 25.0, 50.0 (Cassell et al., 1989b)
21 Heptane(1) + benzene(2) + dimethyl sulphoxide(3) 20.5 (Sørenson and Arlt, 1980)
22 Heptane(1) + toluene(2) + dimethyl sulphoxide(3) 25.0 (Sørenson and Arlt, 1980)
23 Cyclohexane(1) + toluene(2) + dimethyl sulphoxide(3) 20.0 (Sørenson and Arlt, 1980)
24 Heptane(1)-Ethylbenzene(2)-Ethylene Glycol(3) 20.0, 30.0, 50.0 (Radwan et al., 1997a)
25 Heptane(1) + benzene(2) + diethylene glycol(3) 50.0 (Sørenson and Arlt, 1980)
26 Heptane(1) + toluene(2) + diethylene glycol(3) 25.0 (Sørenson and Arlt, 1980)
27 Hexane(1) + benzene(2) + triethylene glycol(3) 20.0 (Sørenson and Arlt, 1980)
28 Heptane(1) + benzene(2) + triethylene glycol(3) 20.0 (Sørenson and Arlt, 1980)
29 Heptane(1) + toluene(2) + triethylene glycol(3) 25.0 (Hughes and Haoran, 1990)

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30 Cyclohexane(1) + benzene(2) + triethylene glycol(3) 20.0 (Sørenson and Arlt, 1980)
31 Decane(1) + benzene(2) + tetraethylene glycol(3) 29.0 (Al-Qattan et al., 1994)

837
 32 Decane(1)-Ethylbenzene(2)-Tetraethylene Glycol(3) 25.5, 39.0, 50.0 (Al-Qattan et al., 1994)

838
33 Hexane(1) + benzene(2) + n-methyl pyrrolidone(3) 25.0 (Ahmad, 2003)
34 Heptane(1) + benzene(2) + n-methyl pyrrolidone(3) 25.0 (Sørenson and Arlt, 1980)
35 Heptane(1)-Toluene(2)-N-Methyl Pyrrolidone(3) 15.0, 25.0, 40.0 (Ferreira et al., 1984)
36 Hexane(1)-Benzene(2)-N-Methylformamide(3) 20.0, 25.0 (Ahmad, 2003, Sørenson and Arlt, 1980)
37 Heptane(1) + benzene(2) + n-methyl formamide(3) 20.0 (Sørenson and Arlt, 1980)
38 Hexane(1) + benzene(2) + dimethyl formamide(3) 25.0 (Ahmad, 2003)
39 Heptane(1) + benzene(2) + dimethyl formamide(3) 20.0 (Sørenson and Arlt, 1980)
40 Dodecane(1)-Benzene(2)-Dimethylformamide(3) 20.0, 30.0, 40.0 (Radwan et al., 1997a)
41 Dodecane(1)-Ethylbenzene(2)-Dimethylformamide(3) 20.0, 30.0, 50.0 (Radwan et al., 1997a)
42 Heptane(1) + toluene(2) + propylene carbonate(3) 25.0 (Salem, 1993)
43 Heptane(1) + xylene(2) + propylene carbonate(3) 25.0 (Salem, 1993)
44 Hexane(1) + benzene(2) + furfural(3) 25.0 (Letcher et al., 2003a)
45 Hexane(1) + toluene(2) + furfural(3) 25.0 (Letcher et al., 2003a)

The Canadian Journal of Chemical Engineering

46 Hexane(1) + xylene(2) + furfural(3) 25.0 (Letcher et al., 2003a)
47 Cyclohexane(1) + benzene(2) + furfural(3) 25.0 (Sørenson and Arlt, 1980)
48 Hexane(1) + chlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
49 Hexane(1) + 1,2-dichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
50 Hexane(1) + 1,3-dichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
51 Hexane(1) + 1,2,4-trichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
52 Dodecane(1) + chlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
53 Hexadecane(1) + chlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
54 Hexadecane(1) + 1,2-dichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
55 Hexadecane(1) + 1,3-dichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
56 Hexadecane(1) + 1,2,4-trichlorobenzene(2) + furfural(3) 25.0 (Morawski et al., 2003)
57 Hexane(1) + benzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
58 Hexane(1) + methylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
59 Hexane(1) + 1,2-dimethylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
60 Dodecane(1) + benzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
61 Dodecane(1) + methylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
62 Dodecane(1) + 1,2-dimethylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
63 Hexadecane(1) + benzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
64 Hexadecane(1) + methylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
65 Hexadecane(1) + 1,2-dimethylbenzene(2) + furfuryl alcohol(3) 25.0 (Morawski et al., 2002)
66 Hexadecane(1) + benzene(2) + 1,3-dimethyl-2-imidazolidinone(3) 25.0 (Letcher and Deenadayalu, 2001)

Volume 85, December 2007

 67 Hexadecane(1) + toluene(2) + 1,3-dimethyl-2-imidazolidinone(3) 25.0 (Letcher and Deenadayalu, 2001)
68 Hexadecane(1) + xylene(2) + 1,3-dimethyl-2-imidazolidinone(3) 25.0 (Letcher and Deenadayalu, 2001)
69 Hexadecane(1) + mesitylene(1) + 1,3-dimethyl-2-imidazolidinone(3) 25.0 (Letcher and Deenadayalu, 2001)
70 Hexadecane(1) + ethylbenzene(2) + 1,3-dimethyl-2-imidazolidinone(3) 25.0 (Letcher and Deenadayalu, 2001)
71 Heptane(1) + benzene(2) + thiodiglycol(3) 50.0 (Rawat and Gulati, 1976)
72 Heptane(1) + toluene(2) + thiodiglycol(3) 50.0 (Rawat and Gulati, 1976)
73 Heptane(1) + ethylbenzene(2) + ethylene carbonate(3) 40.0 (Radwan et al., 1997b)

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74 Heptane(1) + toluene(2) + benzyl alcohol(3) 25.0 (Hughes and Haoran, 1990)
75 Heptane(1) + toluene(2) + 3-methyl sulpholane(3) 25.0 (Rawat and Gulati, 1976)
76 Heptane(1) + toluene(2) + mercaptoethanol(3) 25.0 (Rawat and Gulati, 1976)
(b) Quaternary aromatic extraction systems
77 Hexane(1) + benzene(2) + xylene(3) + sulpholane(4) 25.0 (Chen et al., 2000a)
78 Heptane(1) + benzene(2) + toluene(3) + sulpholane(4) 25.0 (Chen et al., 2001)
79 Octane(1) + toluene(2) + xylene(3) + sulpholane(4) 25.0 (Chen et al., 2000a)
80 Hexane(1) + heptane(2) + toluene(3) + sulpholane(4) 25.0 (Chen et al., 2001)
81 Hexane(1) + octane(2) + benzene(3) + sulpholane(4) 25.0 (Chen et al., 2000a)
82 Heptane(1) + octane(2) + xylene(3) + sulpholane(4) 25.0 (Chen et al., 2001)
83 Cyclohexane(1) + heptene(2) + benzene(3) + sulpholane(4) 25.0 (Chen et al., 2000b)
84 Cyclohexane(1) + heptene(2) + toluene(3) + sulpholane(4) 25.0 (Chen et al., 2000b)
85 Heptane(1) + toluene(2) + triethylene glycol(3) + benzyl alcohol(4) 25.0, 40.0 (Hughes and Haoran, 1990)
(c) Quinary aromatic extraction systems
86 Hexane(1) + heptane(2) + toluene(3) + xylene(4) + sulpholane(5) 25.0 (Chen et al., 2001)
87 Hexane(1) + octane(2) + benzene(3) + toluene(4) + sulpholane(5) 25.0 (Chen et al., 2000a)
88 Heptane(1) + octane(2) + benzene(3) + xylene(4) + sulpholane(5) 25.0 (Chen et al., 2001)
(d) Ternary hydrogen bonding systems
89 2-Propanone(1) + glycerol(2) + methanol(3) 20.0 (Katayama et al., 1998)
90 2-Butanone(1) + glycerol(2) + ethanol(3) 20.0 (Katayama et al., 1998)
91 2-Butanone(1) + glycerol(2) + 2-propanone(3) 20.0 (Katayama et al., 1998)
92 Methyl tert-butyl ether(1) + ethanol(2) + water(3) 25.0 (Ashour, 2005)
93 Methyl tert-butyl ether(1) + 1-hexanol(2) + water(3) 25.0 (Ashour, 2005)
94 Epichlorohydrin(1) + water(2) + methanol(3) 0.0 (Vaidya and Naik, 2003)
95 Allyl chloride(1) + water(2) + methanol(3) 0.0 (Vaidya and Naik, 2003)
96 Water(1) + methanol(2) + methylal(3) 20.0 (Albert et al., 2001)

The Canadian Journal of Chemical Engineering

97 Water(1) + methanol(2) + 1,4-dicyanobutane(3) 25.0 (Letcher and Naicker, 2001)
98 Water(1) + ethanol(2) + 1,4-dicyanobutane(3) 25.0 (Letcher and Naicker, 2001)

839
 99 Water(1) + 1-propanol(2) + 1,4-dicyanobutane(3) 25.0 (Letcher and Naicker, 2001)

840
100 Water(1) + methanol(2) + butanenitrile(3) 25.0 (Letcher and Naicker, 2001)
101 Water(1) + ethanol(2) + butanenitrile(3) 25.0 (Letcher and Naicker, 2001)
102 Water(1) + 1-propanol(2) + butanenitrile(3) 25.0 (Letcher and Naicker, 2001)
103 Water(1) + methanol(2) + benzonitrile(3) 25.0 (Letcher and Naicker, 2001)
104 Water(1) + ethanol(2) + benzonitrile(3) 25.0 (Letcher and Naicker, 2001)
105 Water(1) + 1-propanol(2) + benzonitrile(3) 25.0 (Letcher and Naicker, 2001)
106 2-Methoxy-2-methylpropane(1) + ethanol(2) + water(3) 25.0 (Arce et al., 1998)
107 2-Methoxy-2-methylpropane(1) + 1-octanol(2) + water(3) 25.0 (Arce et al., 1998)
108 1-Octanol(1) + ethanol(2) + water(3) 25.0 (Arce et al., 1998)
(e) Quaternary hydrogen bonding systems
109 Water(1) + methanol(2) + xylene(3) + dodecane(4) 25.0 (Mohsen-Nia et al., 2006)
110 Water(1) + ethanol(2) + xylene(3) + dodecane(4) 25.0 (Mohsen-Nia et al., 2006)
111 Methanol(1) + ethanol(2) + xylene(3) + dodecane(4) 25.0 (Mohsen-Nia et al., 2006)

The Canadian Journal of Chemical Engineering

112 Water(1) + methanol(2) + toluene(3) + dodecane(4) 25.0 (Doulabi et al., 2005)
113 Water(1) + ethanol(2) + toluene(3) + dodecane(4) 25.0 (Doulabi et al., 2005)
114 Methanol(1) + ethanol(2) + toluene(3) + dodecane(4) 25.0 (Doulabi et al., 2005)
115 1-Octanol(1) + 2-methoxy-2-methylpropane(2) + water(3) + ethanol(4) 25.0 (Arce et al., 1998)
116 1-Octanol(1) + 2-methoxy-2-methylbutane(2) + water(3) + methanol(4) 25.0 (Arce et al., 1999)
(f) Ternary ionic liquid based systems
117 [Hmim][PF6] (1) + Benzene(2) + Heptane(3) 25.0 (Letcher and Reddy, 2005)
118 [Hmim][BF4](1) + Benzene(2) + Heptane(3) 25.0 (Letcher and Reddy, 2005)
119 [Hmim][BF4](1) + Benzene(2) + Dodecane(3) 25.0 (Letcher and Reddy, 2005)
120 [Hmim][BF4](1) + Benzene(2) + Hexadecane(3) 25.0 (Letcher and Reddy, 2005)
121 [Hmim][PF6] (1) + Benzene(2) + Dodecane(3) 25.0 (Letcher and Reddy, 2005)
122 [Hmim][PF6] (1) + Benzene(2) + Hexadecane(3) 25.0 (Letcher and Reddy, 2005)
123 [Omim][Cl](1) + Ethanol(2) + Hexadecane(3) 25.0 (Letcher et al., 2003c)
124 [Omim][Cl](1) + Ethanol(2) + tert-Amyl ethyl ether (3) 25.0 (Arce et al., 2004a)
125 [Hmim][BF4](1) + Ethanol(2) +Heptene(3) 25.0 (Letcher and Reddy, 2004)
126 [Hmim][BF4] (1) + Ethanol(2) + Hexene(3) 25.0 (Letcher and Reddy, 2004)
127 [Hmim][PF6] (1) + Ethanol(2) + Hexene(3) 25.0 (Letcher and Reddy, 2004)
128 [Hmim][PF6] (1) + Ethanol(2) + Heptene(3) 25.0 (Letcher and Reddy, 2004)
129 [Bmim][CF3SO3](1) + Ethanol(2) + tert-Amyl ethyl ether (3) 25.0 (Arce et al., 2004b)
130 [Bmim][(CF3SO3](1) +Ethanol(2)+ Ethyl-tert-Butyl Ether(3) 25.0 (Arce et al., 2006)
131 [Omim][Cl](1) +Methanol(2) + Hexadecane(3) 25.0 (Letcher et al., 2003b)

Volume 85, December 2007

 132 [Omim][Cl] (1) + Benzene(2) + Heptane(3) 25.0 (Letcher and Deenadayalu, 2003)
133 [Omim][Cl] (1) + Benzene(2) + Dodecane(3) 25.0 (Letcher and Deenadayalu, 2003)
134 [Omim][Cl] (1) + Benzene(2) + Hexadecane(3) 25.0 (Letcher and Deenadayalu, 2003)
135 [Emim][OcSO4] (1) + Benzene (2) + Heptane(3) 25.0 (Deenadayalu et al., 2006)
136 [Emim][OcSO4] (1) + Benzene(2) + Hexadecane(3) 25.0 (Deenadayalu et al., 2006)
137 [Omim][MDeg] (1) + Benzene (2) + Heptane(3) 25.0 (Deenadayalu et al., 2006)
138 [Omim][MDeg] (1) + Benzene (2) + Hexadecane(3) 25.0 (Deenadayalu et al., 2006)

Volume 85, December 2007

139 [Mmim][MeSO4] (1) + Toluene (2) + Heptane(3) 25.0 (Meindersma et al., 2006)
140 [Emim][EthSO4] (1) + Toluene (2) + Heptane(3) 25.0 (Meindersma et al., 2006)
141 [Bmim][[EthSO4] (1) + Toulene (2) + Heptane(3) 25.0 (Meindersma et al., 2006)
142 [Emim][EthSO4] (1) + Ethanol(2) + Hexene(3) 40.15 (Banerjee, 2006)
143 [Emim][EthSO4] (1) + Ethanol(2) + Heptene(3) 40.15 (Banerjee, 2006)
144 [1,2-Emim][EthSO4] (1) + Ethanol(2) + Hexene(3) 40.15 (Banerjee, 2006)
145 [1,2-Emim][EthSO4] (1) + Ethanol(2) + Heptene(3) 40.15 (Banerjee, 2006)

Table 6. Binary interaction parameters for ternary aromatic extraction systems

rmsd rmsd rmsd woce wce wce
System Temp., Binary interaction parameters with closure equations, °K gainlit gainw oce gainlit
no. °C A12 A21 A13 A31 A23 A32 (wce)c (woce) [lit]d (%) (%) (%)
1 17.0 319.87 -16.19 311.90 285.91 5.29 315.36 0.007 0.009 30.11
25.0 272.41 -133.51 571.79 273.82 -0.11 107.83 0.005 0.006 16.67
50.0 -14.37 -22.37 456.24 146.03 187.82 -114.39 0.005 0.005 11.11
2 17.0 309.35 -174.20 618.56 123.38 75.36 63.73 0.006 0.007 18.57
25.0 105.54 -101.67 515.34 86.98 187.13 -34.02 0.004 0.004 0.00
50.0 406.48 -214.90 670.58 198.82 21.72 171.34 0.009 0.007 -25.00
3 25.0 299.75 -81.21 367.10 182.57 16.75 213.18 0.006 0.006 0.00
30.0 905.56 -50.68 367.13 99.55 13.16 701.82 0.007 0.009 22.22
50.0 463.66 -268.49 690.30 112.75 -36.17 118.43 0.004 0.005 20.00
75.0 288.04 -243.42 661.99 13.07 95.27 -22.19 0.007 0.008 12.50
100.0 362.39 -101.39 393.99 113.41 49.70 232.90 0.008 0.006 -33.33
4 25.0 241.62 -151.67 637.25 73.91 152.60 -17.45 0.003 0.005 40.00
35.0 301.77 -210.31 697.68 60.41 165.66 40.47 0.010 0.010 0.020 50.00 0.00 50.00
50.0 -328.17 153.53 517.67 61.70 697.79 -239.88 0.005 0.005 0.011 54.55 0.00 54.55
5 25.0 140.31 -187.94 803.23 36.84 377.60 -60.54 0.004 0.004 0.012 66.67 0.00 66.67

The Canadian Journal of Chemical Engineering

35.0 -191.48 158.71 353.69 98.75 530.05 -75.08 0.004 0.004 0.012 66.67 0.00 66.67
50.0 -10.72 -74.13 531.68 76.47 360.05 -31.75 0.002 0.004 0.018 77.78 50.00 88.89

841
 6 25.0 414.62 -240.71 744.69 170.01 -7.01 73.64 0.005 0.005 0.00

842
110.0 421.53 -146.68 405.71 78.50 14.89 255.89 0.005 0.008 37.50
7 25.0 223.47 -109.66 473.44 174.80 62.87 97.36 0.006 0.009 33.33
30.0 702.28 -152.71 311.33 117.66 -155.37 505.95 0.002 0.002 0.00
50.0 111.49 -106.09 479.87 51.00 182.02 -29.27 0.003 0.004 25.00
75.0 308.47 -233.72 650.05 11.46 113.05 16.65 0.002 0.003 33.33
100.0 426.60 -264.65 570.18 40.27 -5.56 155.78 0.004 0.004 0.00
8 25.0 -46.23 23.47 359.16 119.76 253.67 -55.42 0.007 0.008 12.50
9 25.0 522.15 -49.81 415.12 114.80 91.31 362.95 0.003 0.004 0.004 0.00 25.00 25.00
35.0 386.10 -12.71 336.19 200.29 69.69 332.60 0.005 0.007 0.009 22.22 28.57 44.44
45.0 203.31 -112.49 528.51 61.14 144.60 -6.97 0.004 0.006 0.006 0.00 33.33 33.33
100.0 441.07 -228.79 529.93 110.82 -29.69 221.06 0.006 0.006 0.008 25.00 0.00 25.00
10 25.0 -136.24 523.44 250.90 169.34 671.31 -69.92 0.005 0.007 0.002 -250.00 28.57 -150.00
50.0 300.64 -237.15 706.43 135.17 79.52 46.05 0.006 0.007 0.007 0.00 14.29 14.29

The Canadian Journal of Chemical Engineering

75.0 -65.16 1.26 461.96 48.13 336.30 -143.95 0.004 0.004 0.005 20.00 0.00 20.00
11 25.0 -189.22 206.87 374.46 89.48 533.62 -147.45 0.005 0.006 0.006 0.00 16.67 16.67
30.0 127.64 317.93 197.47 223.97 334.58 170.79 0.008 0.009 11.11
45.0 -34.69 -29.11 412.92 46.23 258.94 -113.33 0.004 0.004 0.005 20.00 0.00 20.00
50.0 -189.22 206.87 374.46 89.48 533.62 -147.45 0.005 0.006 0.006 0.00 16.67 16.67
12 25.0 51.34 -35.42 359.73 105.84 131.85 -35.28 0.005 0.006 16.67
75.0 730.89 -333.79 670.77 49.95 -145.16 298.70 0.006 0.007 14.29
100.0 293.99 -313.01 551.58 21.09 -43.00 33.51 0.003 0.004 25.00
13 25.0 940.22 143.73 468.68 157.30 29.74 514.85 0.007 0.008 12.50
14 25.0 105.59 -125.36 666.94 65.81 311.64 -58.53 0.005 0.006 0.011 45.45 16.67 54.55
50.0 380.39 -257.82 935.42 12.56 270.38 -14.27 0.005 0.006 0.016 62.50 16.67 68.75
15 25.0 225.42 -191.02 508.71 35.69 58.87 2.29 0.003 0.005 40.00
50.0 401.38 -196.08 439.29 58.82 -24.46 192.53 0.005 0.007 28.57
100.0 379.82 -203.92 441.44 18.19 7.26 167.75 0.004 0.005 20.00
16 25.0 270.71 -165.62 542.49 127.67 56.15 77.66 0.006 0.007 14.29
17 25.0 629.93 -318.68 706.53 48.77 -104.00 186.85 0.006 0.009 33.33
18 25.0 569.50 -296.72 856.38 -6.35 55.43 58.92 0.005 0.009 44.44
19 25.0 28.17 -63.35 443.10 103.67 174.73 -73.18 0.006 0.009 33.33
20 10.0 127.64 -13.75 507.34 119.00 238.97 -7.98 0.006 0.009 40.43
25.0 122.15 -86.79 642.98 91.70 240.94 -101.40 0.003 0.004 25.00
50.0 356.98 -164.27 578.78 90.10 63.93 96.50 0.004 0.003 -46.67

Volume 85, December 2007

 21 25.0 242.95 -136.94 584.98 85.95 130.90 11.76 0.006 0.008 25.00
22 25.0 5.89 9.21 498.89 57.27 361.11 -83.83 0.004 0.005 20.00
23 25.0 400.90 -234.81 834.54 58.86 147.19 7.21 0.003 0.004 25.00
24 25.0 76.34 167.60 491.68 131.78 564.01 112.84 0.005 0.005 0.00
30.0 -118.39 222.34 364.45 225.71 560.90 81.43 0.005 0.005 0.00
40.0 -167.55 308.37 372.49 129.29 794.16 75.04 0.003 0.004 8.33
25 25.0 -74.13 146.31 221.93 294.97 190.58 43.18 0.006 0.007 14.29

Volume 85, December 2007

26 25.0 -29.54 47.86 429.12 77.34 411.74 -17.43 0.002 0.002 0.00
27 25.0 23.42 18.77 364.02 93.20 239.52 -26.65 0.003 0.007 57.14
28 25.0 165.80 -95.55 493.93 60.19 179.18 6.79 0.002 0.003 33.33
29 25.0 40.44 35.17 331.53 107.76 224.21 5.72 0.002 0.006 66.67
30 25.0 172.11 -77.95 363.34 115.95 91.23 93.90 0.007 0.008 12.50
31 25.0 -188.46 537.50 -166.45 637.33 61.85 139.67 0.007 0.009 22.22
32 25.0 -14.87 322.58 -95.56 600.55 -27.97 330.69 0.004 0.006 33.33
39.0 -50.64 -90.25 14.25 302.79 -90.00 238.15 0.009 0.009 -1.14
50.0 88.16 -35.18 -16.26 381.14 -141.00 379.74 0.01 0.011 9.26
33 25.0 402.53 12.81 229.64 19.17 121.81 301.06 0.003 0.004 0.006 33.33 25.00 50.00
34 25.0 163.31 -137.62 264.26 6.44 -58.41 -15.28 0.004 0.007 42.86
35 15.0 676.91 -170.08 255.68 13.27 -83.86 520.72 0.002 0.003 0.004 25.00 33.33 50.00
25.0 577.84 -162.56 223.40 19.77 -84.55 452.22 0.002 0.004 0.004 0.00 50.00 50.00
40.0 -323.12 -37.84 206.78 9.41 46.04 -436.61 0.002 0.003 0.014 78.57 33.33 85.71
36 25.0 179.48 -138.68 819.03 19.96 387.11 -93.80 0.003 0.004 0.012 66.67 25.00 75.00
37 25.0 29.39 -76.27 932.09 -30.03 673.43 -183.03 0.005 0.005 0.00
38 25.0 111.00 -81.27 535.74 28.44 267.67 -47.36 0.003 0.006 0.007 14.29 50.00 57.14
39 25.0 -202.71 -107.39 346.87 19.52 54.62 -368.05 0.001 0.004 75.00
40 25.0 682.61 233.79 402.59 -10.42 575.06 610.87 0.003 0.007 57.14
30.0 -149.33 349.98 399.61 -20.11 694.54 -224.49 0.003 0.006 46.77
40.0 922.88 -502.29 419.53 -4.45 -445.78 555.41 0.007 0.009 22.83
41 25.0 480.52 -119.93 520.76 -107.57 193.06 165.18 0.010 0.008 -25.00
30.0 145.27 -354.74 739.53 -36.37 7.74 -268.15 0.008 0.009 20.21
50.0 343.47 -85.80 379.22 -6.50 114.93 158.48 0.005 0.008 36.25
42 25.0 220.33 -164.20 748.88 9.36 279.74 -75.25 0.001 0.004 75.00
43 25.0 -144.30 100.68 630.33 19.42 662.12 -193.77 0.003 0.003 0.00

The Canadian Journal of Chemical Engineering

44 25.0 555.74 108.02 278.05 58.98 211.31 439.96 0.005 0.007 0.008 12.50 28.57 37.50
45 25.0 423.57 -181.82 403.81 53.77 -37.06 218.29 0.003 0.007 0.008 12.50 57.14 62.50

843
 46 25.0 282.98 -174.89 399.36 40.64 14.80 113.96 0.003 0.004 0.007 42.86 25.00 57.14

844
47 25.0 45.95 -119.47 331.96 31.78 47.92 -86.85 0.001 0.004 75.00
48 25.0 533.91 -263.76 529.15 25.66 -93.56 200.61 0.005 0.007 0.011 36.36 28.57 54.55
49 25.0 -163.95 -128.17 343.67 48.23 34.23 -296.99 0.006 0.007 0.010 30.00 14.29 40.00
50 25.0 820.60 -77.85 361.25 53.99 -24.93 566.27 0.006 0.006 0.012 50.00 0.00 50.00
51 25.0 166.60 -97.50 327.77 62.71 41.97 41.01 0.004 0.007 0.016 56.25 42.86 75.00
52 25.0 853.98 -96.47 505.19 -107.38 190.23 528.12 0.008 0.008 0.011 27.27 0.00 27.27
53 25.0 255.73 -152.94 466.55 -46.51 99.45 -4.93 0.003 0.006 0.012 50.00 50.00 75.00
54 25.0 96.01 -309.60 403.24 109.33 -210.76 -99.06 0.007 0.007 0.013 46.15 0.00 46.15
55 25.0 129.65 -131.96 556.58 -98.39 262.33 -131.04 0.010 0.011 0.013 15.38 9.09 23.08
56 25.0 192.09 -45.66 361.49 13.54 150.91 40.71 0.007 0.007 0.011 36.36 0.00 36.36
57 25.0 839.73 -304.08 618.19 21.29 -176.27 370.64 0.005 0.008 0.020 60.00 37.50 75.00
58 25.0 713.05 -274.33 591.81 14.32 -122.13 287.75 0.007 0.012 0.020 40.00 41.67 65.00
59 25.0 426.32 -239.76 547.60 -0.65 4.12 121.95 0.004 0.007 0.020 65.00 42.86 80.00

The Canadian Journal of Chemical Engineering

60 25.0 430.67 -204.02 466.52 -39.78 10.52 138.91 0.011 0.011 0.030 63.33 0.00 63.33
61 25.0 513.07 -251.34 773.08 -114.64 131.58 8.28 0.008 0.010 0.020 50.00 20.00 60.00
62 25.0 28.36 45.02 454.05 -101.08 468.64 -103.15 0.015 0.016 0.030 46.67 6.25 50.00
63 25.0 421.97 -191.39 593.66 -33.25 64.47 50.91 0.003 0.011 0.030 63.33 72.73 90.00
64 25.0 465.79 -251.04 825.71 -69.58 145.27 -33.19 0.005 0.009 0.030 70.00 44.44 83.33
65 25.0 -20.47 78.39 516.96 -108.03 534.30 -189.55 0.008 0.008 0.030 73.33 0.00 73.33
66 25.0 660.48 -404.78 364.90 84.56 -336.29 448.63 0.005 0.007 0.012 41.67 28.57 58.33
67 25.0 779.16 -322.69 440.07 -57.93 -180.64 423.21 0.008 0.008 0.016 50.00 0.00 50.00
68 25.0 77.59 -118.98 333.00 -35.17 102.47 -69.13 0.007 0.008 0.016 50.00 12.50 56.25
69 25.0 485.92 -255.70 420.06 -24.11 -98.38 199.07 0.005 0.008 0.014 42.86 37.50 64.29
70 25.0 868.87 -359.30 477.34 -37.46 -243.16 470.21 0.007 0.007 0.007 0.00 0.00 0.00
71 25.0 -201.27 518.31 201.50 195.73 719.29 -6.06 0.004 0.004 0.00
72 25.0 67.62 -63.50 508.68 92.56 325.53 40.53 0.002 0.002 0.00
73 25.0 -218.39 133.92 564.53 762.06 174.42 19.64 0.002 0.002 0.00
74 25.0 -104.72 -278.86 297.15 -37.97 -126.45 -287.43 0.004 0.006 33.33
75 25.0 -128.37 725.69 215.30 45.63 925.42 -98.31 0.009 0.010 10.00
76 25.0 203.37 -117.48 510.09 28.21 192.62 31.59 0.004 0.008 50.00
average 0.005 0.006 0.013 32.87 20.97 47.69

Volume 85, December 2007

Table 7. Binary interaction parameters for quaternary aromatic extraction systems
Binary interaction parameters with closure equations, °K
System Temp., wce
A12 A13 A14 A23 A24 A34 rmsd rmsd gain woce
no. °C
A21 A31 A41 A32 A42 A43 (woce) (wce) (%)
372.37 -951.30 358.44 -871.18 -44.35 547.78
77 25.0 0.008 0.011 27.27
-122.67 601.11 173.98 726.92 266.23 -739.73
135.00 146.11 664.41 -218.29 225.75 729.77
78 25.0 0.009 0.007 -28.57
-126.09 -121.47 43.42 354.11 -134.16 -202.54
-145.41 90.89 353.15 969.22 526.89 -40.16
79 25.0 0.008 0.008 0.00
384 .02 236.51 275.59 -108.39 -80.09 430.47
-275.32 812.38 419.48 3.00 399.09 260.87
80 25.0 0.006 0.009 33.33
-148.72 -326.96 114.38 -108.18 -32.62 -59.66
182.18 342.63 434.16 423.31 245.71 173.05
81 25.0 0.005 0.009 44.44
-85.23 259.29 88.59 130.75 167.54 387.44
229.39 -86.89 156.53 10.88 156.53 81.61
82 25.0 0.005 0.007 28.57
-503.81 983.40 170.25 569.13 903.45 270.27
-109.07 367.92 683.13 248.22 419.32 -7.99
83 25.0 0.003 0.008 62.50
-769.98 -854.59 -470.84 -313.38 -73.74 60.55
-209.67 288.51 586.64 226.83 441.32 57.27
84 25.0 0.004 0.008 50.00
-834.01 -880.05 -546.81 -293.96 -67.79 68.95
330.10 800.34 331.17 363.21 297.55 249.91
85 25.0 0.005 0.006 16.67
10.77 225.77 -57.83 107.97 227.88 435.48
836.96 812.09 -409.48 -341.99 269.19 -177.86
40.0 0.006 0.006 0.00
-145.33 320.97 -912.76 149.18 748.20 -190.02
average 0.006 0.008 23.42

Table 8. Binary interaction parameters for quinary aromatic extraction systems

Binary interaction parameters with closure equations, °K

A12 A21 A31 A41 A51 wce
rmsd rmsd gain woce
System no. A13 A23 A32 A42 A52 (woce) (wce) (%)
A14 A24 A34 A43 A53
A15 A25 A35 A45 A54

-951.56 -118.86 949.22 949.54 367.70

-174.61 -145.73 145.39 60.06 -296.56

86 0.013 0.019 31.58
-82.30 -139.07 181.79 89.80 -33.60
6.25 174.70 728.78 650.93 -19.46
542.64 50.25 660.14 468.56 330.50
348.79 120.82 924.56 870.17 720.51
87 0.012 0.011 -9.09
13.05 -77.73 142.55 286.71 312.30
151.71 49.33 444.86 356.02 79.30
-91.60 -803.49 -629.77 -731.26 -246.86
854.41 646.35 -125.94 -173.97 76.81
88 0.007 0.010 30.00
262.38 107.78 186.11 676.65 605.54
662.87 274.65 31.09 51.18 135.09
average 0.011 0.013 17.50

Volume 85, December 2007 The Canadian Journal of Chemical Engineering 845
 Table 9. Binary interaction parameters for ternary hydrogen bonding systems
System Binary interaction parameters with closure equations, °K rmsd rmsd rmsd woce gain wce
gain lit
wce
woce gain lit
no. A12 A21 A13 A31 A23 A32 (wce) (woce) [lit] (%) (%) (%)

89 254.09 155.76 -756.29 -371.79 -808.44 -325.61 0.006 0.005 -20.00

90 413.12 114.95 486.30 -304.56 294.57 -198.11 0.004 0.006 33.33
91 284.50 172.68 982.83 -148.46 825.43 -194.04 0.006 0.008 25.00
92 369.81 -149.79 920.24 308.91 218.74 127.01 0.003 0.007 57.14
93 361.54 -89.57 911.75 333.40 456.86 329.62 0.002 0.003 33.33
94 939.42 493.37 624.79 -123.43 297.74 -4.43 0.006 0.008 0.014 42.86 25.00 57.14
95 990.55 539.77 579.74 -25.05 248.06 94.06 0.008 0.007 0.034 79.41 -14.29 76.47
96 -127.00 939.97 183.33 466.18 910.39 126.27 0.001 0.002 50.00
97 519.77 -21.51 203.82 581.14 -137.35 781.26 0.002 0.003 0.011 72.73 33.33 81.82
98 95.08 27.36 192.89 602.94 -162.50 315.27 0.002 0.004 0.007 42.86 50.00 71.43
99 174.49 72.13 192.23 601.88 -208.20 303.81 0.001 0.002 0.013 84.62 50.00 92.31
100 566.71 -58.58 441.00 766.97 -158.62 792.64 0.002 0.003 0.014 78.57 33.33 85.71
101 201.03 48.10 389.24 808.77 -194.05 378.42 0.004 0.006 0.014 57.14 33.33 71.43
102 253.58 212.04 311.04 836.89 -152.48 414.91 0.002 0.003 0.008 62.50 33.33 75.00
103 135.60 39.44 525.06 921.89 -37.81 455.18 0.004 0.006 0.010 40.00 33.33 60.00
104 392.37 189.13 496.44 957.41 -84.48 579.73 0.003 0.003 0.014 78.57 0.00 78.57
105 243.18 237.55 559.95 932.06 -92.04 285.72 0.002 0.003 0.007 57.14 33.33 71.43
106 555.97 -219.24 866.61 398.97 -3.02 304.56 0.004 0.003 0.005 40.00 -33.33 20.00
107 382.60 38.66 905.92 319.60 560.56 318.18 0.004 0.005 0.005 0.00 20.00 20.00
108 255.72 -58.36 553.09 355.38 140.24 256.61 0.002 0.003 0.021 85.71 33.33 90.48
average 0.003 0.005 0.013 58.72 25.47 67.99

Table 10. Binary interaction parameters for quaternary hydrogen bonding systems
Binary interaction parameters with closure equations, °K
woce gain wce wce
System rmsd rmsd rmsd gain lit woce gain lit
A12 A13 A14 A23 A24 A34
no. (wce) (woce) [lit] (%) (%) (%)
A21 A31 A41 A32 A42 A43
-618.19 878.71 805.27 -474.38 -161.15 -687.71
109 0.016 0.018 0.022 18.18 11.11 27.27
-913.69 699.99 904.18 -357.61 233.26 -410.08
-722.43 358.82 604.64 390.77 623.24 560.36
110 0.009 0.020 0.026 23.08 55.00 65.38
419.59 986.45 842.39 -123.63 -281.03 170.49
557.96 336.32 329.52 -29.76 -8.53 -114.30
111 0.014 0.016 0.021 23.81 12.50 33.33
335.10 347.72 598.95 204.50 483.76 143.74
-800.21 -518.21 602.46 -438.48 254.74 188.71
112 0.015 0.019 0.022 13.64 21.05 31.82
5.25 756.00 968.50 30.27 -184.69 -719.47
-372.85 388.63 697.55 676.61 865.53 432.57
113 0.012 0.024 0.030 20.00 50.00 60.00
781.83 922.79 982.67 56.08 -4.04 183.53
-145.52 -320.28 -107.67 -48.06 -32.56 -187.40
114 0.010 0.017 0.033 48.48 41.18 69.70
383.53 474.27 888.41 217.44 434.47 14.14
-60.10 601.45 356.54 812.39 494.83 358.44
115 0.006 0.005 0.018 72.22 -20.00 66.67
162.75 216.53 65.02 204.62 -19.53 451.85
202.54 601.44 198.02 751.89 239.31 14.01
116 0.006 0.005 0.011 54.55 -20.00 45.45
223.59 353.95 -2.70 483.35 17.54 60.79
average 0.011 0.016 0.023 34.25 18.86 49.95

846 The Canadian Journal of Chemical Engineering Volume 85, December 2007
 Table 11. UNIQUAC volume and area parameters (Banerjee et al.,
2005, 2006)
Ionic liquid r q
[C1mim][Cl] 6.337 4.271
[C2mim][Cl] 7.190 4.876
[C3mim][Cl] 7.997 5.403
[C4mim][Cl] 8.739 5.759
[C5mim][Cl] 9.600 6.419
[C6mim][Cl] 10.425 6.871
[C7mim][Cl] 11.200 7.407
[C8mim][Cl] 11.993 7.886 Figure 2. Absolute value of objective function versus population size

[C1mim][BF4] 7.468 4.853
[C2mim][BF4] 8.382 5.331
[C3mim][BF4] 9.247 5.954
[C4mim][BF4] 10.057 6.368
[C5mim][BF4] 10.843 7.035
[C6mim][BF4] 11.658 7.388
[C7mim][BF4] 12.618 8.101
[C8mim][BF4] 13.187 8.357

[C1mim][PF6] 8.592 5.541
[C2mim][PF6] 9.427 5.959 Figure 3. Absolute value of objective function versus generation number

[C3mim][PF6] 10.188 6.532

[C4mim][PF6] 11.034 6.958
[C5mim][PF6] 11.891 7.589
[C6mim][PF6] 12.869 8.166
[C7mim][PF6] 13.903 8.794
[C8mim][PF6] 14.230 8.935
[C4mim][CF3SO3] 12.460 7.518
[C1mim][CH3SO4] 8.768 5.745
[C4mim][CH3SO4] 11.161 7.132
[C2mim][C2H5SO4] 10.381 6.763
[C2mim][C8H17SO4] 14.890 9.490
[C2dmim][C2H5SO4] 11.550 6.84
[C8mim][DEG*] 19.280 11.83
[BmPy][BF4] 10.693 6.864
*diethyleneglycolmonomethylethylsulphate
Comparison of tie line compositions are given in Table 4. The
rmsd value thus obtained is 0.006 as compared to 0.011 in the
literature. After benchmarking with the above system, GA has
been applied and verified on 88 aromatic and 28 hydrogen
bonding multi-component systems. The rmsd values obtained
using GA have been compared with the rmsd values reported in
literature in terms of percentage gain:
woce  rmsdlit − rmsdwoce  systems, it is observed that most of the cases elimination of
gainlit =   × 100 (15)
 rmsdlit  parameters with only i=non-aromatic-j=aromatic, i=non-
wce  rmsdwoce − rmsdwce 
gainwoce =   × 100 (16)
 rmsdwoce 
wce  rmsdlit − rmsdwce 
gainlit =   × 100 (17)
 rmsdlit 
Aromatic Extraction Systems
Application of GA has been studied on 88 aromatic extraction
systems as listed in Table 5a to 5c along with their references.
UNIQUAC volume r and area q parameters have been taken from
Aspen Plus (1998).
The results of parameter estimation along with the correspond-
ing percentage gain values for the ternary systems are given in
Table 6. It is seen that the rmsd value corresponding to the
parameters with the closure equation taken into account is less
than that without closure equations; approximately 21 percent
better than without implementation of closure equation and
48 percent better than literature. This clearly means that parame-
ters obtained with the closure equation will predict the LLE more
accurately than those obtained without closure equation. While
implementing the closure equation for ternary systems all the six
possibilities of parameter elimination have been tried. It was
observed that the rmsd values change slightly with the eliminated
parameters. This is due to the different search path adopted by the
optimization procedure for different eliminated parameter to
reach the final optimum point. The interaction parameters with
closure equation given in Table 6 correspond to the lowest rmsd
for the six possibilities. From parameter elimination for ternary
aromatic-j=solvent and i=solvent-j=aromatic combination gives

Volume 85, December 2007 The Canadian Journal of Chemical Engineering 847
 Table 12. Binary interaction parameters for ternary ionic liquid systems
Binary interaction parameters with closure equations, °K rmsd rmsd rmsd# wce
gain w
System no. oce
A12 A21 A13 A31 A23 A32 (wce) (woce) [lit] (%)

117 -35.70 132.74 140.59 112.05 162.70 -34.28 0.010 0.012 0.015 16.67
118 9.20 137.23 8.96 235.74 26.11 124.86 0.014 0.018 0.018 22.22
119 290.82 -131.54 336.36 -87.12 62.63 61.52 0.013 0.014 0.006 7.14
120 184.35 59.69 206.44 701.84 -93.85 526.20 0.012 0.014 0.016 14.29
121 355.48 -72.68 221.03 415.54 -101.58 521.09 0.016 0.017 0.004 5.88
122 -86.64 223.55 84.25 408.67 67.77 82.00 0.008 0.009 0.004 11.11
123 779.67 99.70 562.86 -135.49 39.15 20.78 0.008 0.007 0.004 -14.29
124 878.39 -300.67 452.04 -75.05 -345.52 306.45 0.008 0.006 0.007 -33.33
125 559.07 -39.59 405.73 -45.17 54.39 202.15 0.007 0.009 0.009 22.22
126 660.55 -10.29 259.87 13.31 15.00 439.27 0.006 0.006 0.005 0.00
127 206.18 -30.19 88.68 142.30 -46.10 243.89 0.009 0.014 0.022 35.71
128 222.56 -22.06 182.49 48.02 28.22 138.37 0.009 0.012 0.037 25.00
129 585.08 -191.93 249.86 23.19 -192.88 357.46 0.004 0.004 0.003 0.00
130 25.30 64.04 42.62 69.88 464.83 453.33 0.013 0.006 0.005 13.33
131 -24.22 57.69 258.50 456.68 124.76 241.03 0.002 0.003 0.000 -33.33
132 284.83 50.51 406.98 65.61 136.48 29.44 0.017 0.015 0.004 -13.33
133 48.45 139.62 459.10 497.98 110.90 58.60 0.009 0.015 0.002 40.00
134 327.08 438.13 322.45 482.35 102.99 151.84 0.007 0.016 0.000 56.25
135 499.98 0.45 151.28 293.43 147.61 789.28 0.015 0.009 -66.67
136 442.20 32.11 490.05 403.30 363.65 686.99 0.007 0.006 -16.67
137 391.50 437.10 351.60 183.13 143.84 -70.23 0.009 0.006 -50.00
138 125.43 29.29 354.78 232.74 246.81 220.92 0.009 0.005 -80.00
139 479.63 486.10 144.23 109.11 158.72 117.13 0.005 0.007 0.0084 28.57
140 491.98 285.45 102.17 21.62 98.15 224.13 0.006 0.008 0.0091 25.00
141 474.70 74.14 277.55 4.08 128.57 255.66 0.004 0.009 0.0148 55.56
142 586.36 38.75 72.88 126.34 114.71 715.78 0.017 0.008 -41.67
143 22.72 44.16 -28.55 71.36 259.61 338.08 0.004 0.013 69.23
144 -23.46 751.48 72.14 789.48 204.95 147.36 0.004 0.005 20.00
145 593.04 743.24 -83.62 695.96 179.17 808.55 0.012 0.016 25.00
average 0.009 0.010 0.008 6.41
# Corresponding NRTL rmsd value from literature

Table 13. Effect of local minimization on rmsd values

System no. Temp., °C rmsd rmsd Difference
(wce) (after local minimization)
1 25.0 0.0053 0.0051 0.0002
80 25.0 0.0059 0.0058 0.0001
103 25.0 0.0040 0.0039 0.0001
117 25.0 0.0097 0.0096 0.0001

better rmsd values than elimination of other binary pairs.
Therefore, for quaternary and quinary systems feasible sets
involving parameters with only these pairings, termed as ‘likely
feasible sets’ have been considered. The number of such likely
feasible sets of parameter elimination is 3 for ternary, 8 for quater-
nary and 21 for quinary systems.
The results of parameter estimation along with the correspond-
ing percentage gain values for the quaternary and quinary systems
are given in Table 7 and Table 8, respectively. It is seen, for quater-
nary and quinary systems too, the rmsd value corresponding to
the parameters with the closure equations taken into account is
less than that without closure equations; 23 percent better for

848 The Canadian Journal of Chemical Engineering Volume 85, December 2007
quaternary and 18 percent better for quinary systems. This would genetic operators and their parametric values has not been
mean, for quaternary and quinary systems also the parameters studied. Genetic algorithm can be applied to predict binary
that satisfy the closure equations predict the LLE more accurately interaction parameters for vapour-liquid systems.
than those do not satisfy the closure equations.
The choice of the parameters to be eliminated to implement ACKNOWLEDGEMENT
the closure equations plays a very important role in decreasing
the rmsd values for quaternary and quinary systems. All likely The authors gratefully acknowledge use of the Genetic
feasible combinations of parameter elimination have been tried. Algorithm Optimization Toolbox (GAOT) of MatLab, developed
The rmsd values varied slightly with the eliminated parameters. by Houck, Joines and Kay of North Carolina State University
Reasons explained for the ternary systems apply here also for (Houck et al., 1995).
this variation. Additionally, the larger deviation is due to the
higher dimension of optimization problem encountered. The NOMENCLATURE
interaction parameters with closure equations given in Table 7 A binary interaction parameters (°K)
and Table 8 correspond to the lowest rmsd of all likely feasible a number of binary interaction parameters
combination of parameter elimination. ai lower bound
bi upper bound
Hydrogen Bonding Systems
c total number of components
Application of GA has also been verified with 28 hydrogen bonding f number of retries
systems as listed in Table 5d and Table 5e along with their F objective function
references. UNIQUAC volume r and area q parameters have been gain percentage gain in rmsd
taken from Aspen Plus (1998). The results of parameter estimation Gmax maximum number of generation
along with the corresponding percentage gain values for the Gn number of generation
ternary and quaternary systems are given in Table 9 and Table 10, Gn+1 next generation
respectively. It has been observed that for these systems also, the lit from literature
rmsd value corresponding to the parameters with the closure m total number of tie lines
equations taken into account is less than that without closure P population size
equations; 25 percent better for ternary and 19 percent better for q area parameter
quaternary systems. The overall percentage gain is now 68 percent r volume parameter
for ternary and 50 percent for quaternary systems than literature. rmsd root mean square deviation
T absolute temperature (°K)
Ionic Liquid Based Systems
x experimental composition (mole fraction)
The ionic liquid based systems considered for parameter estima- x̂ predicted composition (mole fraction)
tion are given in Table 5f along with their references. UNIQUAC wce with closure equations
structural parameters for ILs as estimated from Polarizable woce without closure equations
Continuum Model (PCM) have been used and are reported in z lattice coordination number
Table 11. From Table 12 it can be said that the prediction with the
closure equations is 6 percent better than without closure Greek Symbols
equations. Thus, it can be concluded that the implementation of γ activity coefficient
closure equations for IL based systems gives a better prediction. t adjustable binary parameters
It has been observed that for some cases, rmsd values reported
in the literature are better than GA. It has also been observed that Subscripts
for some cases, without implementation of closure equations
1, 2, 3, 4, 5 components
exhibit better rmsd values than with closure equations. The reason
i, j, k components
is that GA gives solution near to global optima, so it should be
lit from literature
followed by local minimization method to get exact global optima.
t tie line
Inbuilt MatLab routine, fminsearch has been used for local minimi-
woce without closure equations
zation. Table 13 shows the effect of local minimization on rmsd
value. However, only marginal improvement in fourth decimal Superscripts
place has been achieved for the four systems considered. It means
I, II phases
GA gives solution very close to global optima. This extra analysis
l phase
is not needed since this improvement in fourth decimal place is not
wce with closure equations
significant with respect to measurement errors.
woce without closure equations

CONCLUSIONS
A genetic algorithm, which is a structured search-based
optimization­ method, has been applied without and with closure
equations­ to estimate UNIQUAC binary interaction parameters
for liquid-liquid extraction systems. Average root mean square
deviation value with implementation of closure equations is
55 percent better than literature as compared to 40 percent better
for without implementation of closure equations, which is
viewed as a potentially useful improvement for the prediction of
liquid-liquid equilibria. The effect of using different sequences of
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Volume 85, December 2007 The Canadian Journal of Chemical Engineering 849
Appendix
Appendix A
GA selection function and operators (Houck et al., 1995, 1996)
Functions/Operators Type Relationship Notations
Selection Function Normalized q Pi = probability of selection the ith individual,
P = q′(1 − q )r −1; q′ =
geometric i 1 − (1 − q )P q = probability of selecting the best individual,
ranking r = rank of the individual, where 1 is the best,

P = population size

Genetic Operators ai and bi = lower and upper bound, respectively, for each variable i
– –
X and Y = two m-dimensional row vectors denoting individuals (parents) from the population
Mutation

Uniform
xi′ = { U(ax,,b ), ifotherwise
i
i
i i=j

Boundary  ai , if i = j, r < 0.5 r = U(0,1)

xi′ =  bi , if i = j, r ≥ 0.5
 xi , otherwise

Non-uniform  xi + (bi − xi )f (G ) if r1 < 0.5, r1, r2 = U(0,1)

xi′ =  xi − ( xi + ai )f (G ) if r1 ≥ 0.5, G = current generation,
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Gmax

Multi-non- Applies the non-uniform operator _

uniform to all of the variables in the parent X .
Crossover

Simple

{
x , if i < r ,
{
y , if i < r ,
xi′ = yi , otherwise ; yi′ = xi , otherw
i i wise
r = U(1, m)

Arithmetic X ′ = rX + (1 − r )Y ; Y ′ = (1 − r )X + rY r = U(0, 1)
Heuristic X ′ = X + r( X − Y ); Y ′ = X r = U(0, 1)

feasibility = {
1, if xi′ ≥ ai , xi′ ≤ bi ∀i
0, otherw wise

Appendix B
UNIQUAC activity coefficient model (Prausnitz et al., 1999)

 
 
c c c θ j tij 
φi z θi φi 
ln γ i = ln
xi 2
+ qi ln + li −
φi ∑
xi j =1
x j l j + qi  1 − ln

∑ ∑
θ j t ji − c 

where 
j =1
∑
j =1 θ t
k kj 
 k =1 
φi = c
ri xi
; θi = c
qi xi z
; li = (ri − qi ) + 1 − ri ; tij = exp
2
( )
p − Aij / T ; and z = 10
∑ rj x j ∑ qjxj
j =1 j =1

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Manuscript received May 12, 2006; revised manuscript received

February 25, 2007; accepted for publication March 21, 2007.

Volume 85, December 2007 The Canadian Journal of Chemical Engineering 853