Fluid Phase Equilibria 158160 1999.

327335

Molecular solvent design for liquidliquid extraction using the

UNIQUAC model
A.-H. Meniai
a

a, )

, D.M.T. Newsham

Institut de Chimie Industrielle, Uniersite de Constantine, Constantine, Algeria

b
Chemical Engineering Department, UMIST, Manchester, UK
Received 2 April 1998; accepted 17 December 1998

Abstract
In this work molecular solvent design for liquidliquid extraction using a chemical graphics system is
presented. Solvent structures are generated according to specified combinatorial rules and the screening of the
solvent is performed using the UNIQUAC model where the required molecular interaction parameters are
directly obtained from a molecular graphics system. The method is tested with two different industrial examples:
toluenern-heptane and phenolrwater system. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Molecular graphics; Extraction; Solvent design; Activity coefficients

1. Introduction
The great majority of the molecular solvent design methods for liquidliquid extraction processes
described in the literature, are carried out in the following three main steps: a. selection of a number
of groups, according to the nature of the compounds to be separated; b. assembling these groups
according to well-established rules which would prevent any unusual combination to occur, avoiding
violation of the rules of chemistry and ensuring the intramolecular stability of the resulting compound;
c. assessment of the resulting compounds, using thermodynamic and group contribution models,
according to specified criteria like selectivity, capacity, solvent loss, etc. For this step, as an
approximation, these properties can be related to activity coefficients at infinite dilution of the
different compounds present in the extract and raffinate phases and. The UNIFAC model is the most
widely used predictive group contribution method.

Corresponding author. Tel.: q213-4-961386; fax: q213-4-930251

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 0 7 9 - 5

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A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

Generally these group contribution methods present certain advantages like simplicity, low cost in
terms of computer time, etc., but they are limited for two main reasons:
a. They are just an approximation because the contribution of a given group for a particular
property is not necessarily the same in two different molecules. Additivity is also the fundamental
assumption of this theory which considers the contribution made by one group as independent of that
made by another one, ignoring how and where the groups are connected to each other. As an
illustrative example, it is clear that with different combinations of a same set of groups, the resulting
molecular structures would have completely different values and orientations of the dipolar moment,
which is, in most but not all the cases, an important parameter for quantitative andror qualitative
interpretations of many physical properties such as solubility, and therefore, misleading conclusions
may be drawn since a group contribution method would predict a same and unique value for all the
resulting isomers.
b. The second problem is the lack of the necessary group interaction parameters for the property
calculations. For instance, for the UNIFAC model, interaction parameters between certain groups may
not be available, a fact which restricts the number of the groups that can be chosen. As an example,
for the design of solvents for the separation of aromatic and nonaromatic hydrocarbons, the sulphone
SO 2 ., sulphoxide SO. and sultone SO 3 . groups cannot be considered because they are not included
in any existing UNIFAC interaction parameters table although it is known that the organo-sulphur
solvents are among the most selective solvents for this type of separation, as reported by Rawat and
Gulati w1x. Therefore, this is a serious limitation.
Also for the separation of acetic acidwater mixtures considered by Gani et al. w2x, 29 out of 238
solvent candidates had to be discarded because of a nonavailability of certain interaction parameters.
Thus, potentially good solvents may be missed.
To overcome this problem, a molecular solvent design method is presented in this work. It still uses
certain molecular design strategies already elaborated by former workers such as Gani and Brignole
w3x and Brignole et al. w4x, but with the particularity of introducing a molecular graphics system
MGS. as a means of overcoming some of the limitations of group contribution models. The MGS is
operating with a package known as CHEM-X developed and distributed by Chemical Design,
Oxford, England. which is capable of simulating molecular structures, molecular interactions and
hence interaction parameters as reported in a previous work of Meniai and Newsham w5x.

2. Interaction parameter calculation

The calculation of the molecular interaction parameters is still based on the definition of the group
interaction parameter given by Magnussen et al. w6x and hence one can write:
a mn s Umn y Unn . rR

1.

where m and n denote molecules or groups, amn is the corresponding interaction parameter in units of
Kelvin, Umn is the interaction energy between molecules or groups and R is the universal gas
constant.
The calculation of the interaction energy has been thoroughly discussed by Meniai and Newsham
in Ref. w5x. It consists of positioning the two molecules or groups by constructing a simple cube
whose dimensions are calculated according to the experimental density of the system as has been

A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

329

Fig. 1. Simulation box for the phenolrwater system a. before minimisation, b. after minimisation.

done for the simulation of dilute solutions by Meniai and Newsham w7x., one at the centre of the cube
and the other at one of its corners as shown, as an example, in Fig. 1 for the case of the phenolrwater
system.
One molecule or group is kept fixed i.e., having no translational or rotational degrees of freedom.
while the other one is shifted and rotated, until the minimum energy configuration is reached which
corresponds to the most favourable orientation of the two molecules or groups when they are facing
one another. Since only relative motion is important, the fact of moving just one molecule and
keeping the other fixed does not limit the validity of the calculated thermodynamic properties as
stated by Owicki and Scheraga w8x. The determination of the necessary interaction parameters is
straightforward from Eq. 1.. The energy calculation and its minimisation with respect to various
variables like translations or intermolecular orientations and positions, are performed directly by
CHEM-X which incorporates appropriate potential energy functions as already described by Meniai
and Newsham w7x.

3. Description of the design method

Once the groups are combined according to the adopted combination rules extracted from the
literature w24,9x, the combinations retained are transferred to the MGS. A computer program using
CHEM-X commands has been developed to simulate molecular structures by connecting the groups
and optimises them by adjusting bond lengths, torsional angles, angles between bonds, etc., to
minimise the intramolecular energy to find the most stable molecular conformation. As an example
Fig. 2 shows the building of a molecular structure from COOH, CH 3 , as terminal groups with just one
free attachment, and CH 2 COO, the intermediate group with two free attachments. Fig. 2a shows the
structures of the three groups where FA denotes the free attachment. Fig. 2b shows the structure
obtained by just putting the groups together, whereas Fig. 2c shows the final and optimised structure
which will be used for the interaction parameter calculations.
In the next step all required molecular parameters for the use of the UNIFAC model are available
for the calculation of the activity coefficients at infinite dilution of the different compounds and hence

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A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

Fig. 2. Building of a molecular structure from three groups. FA: free attachment.

the required solvent properties. Alternatively, it is proposed to calculate group interaction parameters
by using the MGS, whenever their values are not available from the current UNIFAC table of
Magnussen et al. w6x. The method is best described by the flow diagram shown in Fig. 3.
4. The solvent properties
The selectivity at infinite dilution of a solvent to extract i from an i and j mixture, is generally
calculated as follows:
`
rg i`,s
Sij` s g j,s
2.
`
`
where g i,s
and g j,s
are the activity coefficients at infinite dilution of components i and j, respectively,
in the solvent-rich phase.
Usually the distribution coefficient of the solute between the extract and raffinate phases is a
measure of the solvent capacity as reported by Mukhopadhyay w10x and an estimate of the maximum
value of this property is also calculated at infinite dilution according to the following:
K `ij f 1rg i`,s
3.
`
with g i,s
as defined above.
It should be noted that the solvent capacity has an even greater influence than selectivity when
selecting an optimum extraction process because it determines the flow rate of the circulating solvent
and consequently the design of the extractor. However in most cases Eq. 1. is only a rough estimate
of capacity and the distribution or partition coefficient should be calculated as follows:
m s g i`,rrg i`,s
4.
`
`
with g i,r
and g i,s
the activity coefficients at infinite dilution of components j and i in the raffinate and
extract phases, respectively.
Another important solvent property usually considered in the selection of solvents for separation
processes is the solvent loss or the solvent solubility in the raffinate phase and which can be estimated
from the following expression:
Sl s 1rgs`,r
5.

where gs,r` is the activity coefficient at infinite dilution of the solvent in the raffinate phase.

A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

331

Fig. 3. Flow diagram of the molecular solvent design method.

Clearly, for a liquidliquid extraction, it is desired to have a solvent with a high selectivity and
capacity and a low solvent loss.

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A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

5. Results and discussion

For the sake of simplicity, the method is tested by considering only some groups from the current
UNIFAC tables reported by Magnussen et al. w6x, having one or two free valencies at the most. As
sample calculations, only three group compounds i.e., one intermediate and two terminal groups. are
considered, where 107 compounds which satisfied the combinatorial rules and other criteria, have
been obtained for the separation of toluenern-heptane and phenolrwater and where some of them
may or may not be known to exist as a chemical compound. Tables 1 and 2 show some of the optimal
compounds obtained for the both separation problems as well as the molecular interaction parameters
with n-heptane, toluene, phenol and water, respectively, obtained from CHEM-X, as described
earlier, and hence the values of the solvent properties mentioned above, calculated by means of the
UNIQUAC model. To assess the outcome of the design method we have to rely on comparisons with
existing similar cases reported in the literature, or with results from experimental studies if available.
For instance for the toluenern-heptane separation as shown in Table 1 the CH 2 O, CH 3 O, CHNO 2 ,
SO 3 or SO groups give quite good solvents confirming the results reported by Gani and Brignole w3x
and Rawat and Gulati w1x. However the solvent loss values obtained for this case are quite high by
comparisons with the results obtained by Pretel et al. w9x and this may be explained by the fact that
this latter is just an inverse of an activity coefficients whereas other properties are ratio of these
coefficients.
Table 2 confirms that for the phenolrwater system, compounds having the acetate group esters.
give good selectivities. This is in agreement with experimental results where esters are best indicated
for the phenolrwater separation, as reported by Alvarez Gonzalez et al. w11x. Also for this second
separation problem the values for the distribution coefficient compare very well with the experimental
ones given by Pretel et al. w9x whereas the values obtained for the solvent loss are still quite high.
It has also been attempted to use group interaction parameters calculated according to the method
proposed by Meniai and Newsham w5x. The acetic acidrwater example of Gani et al. w2x presents a
good example in this regard because 29 feasible chemical structures have been discarded because of
nonavailable interaction parameters, particularly between the COOH and certain groups such as
CH 2 CN, CH 2 NH 2 , etc.
The calculations have been performed for a sample combination set for five-group compounds
having C carbon. as the central atom. The results obtained are lower than the ones reported by Gani
et al. w2x, but of the same order of magnitude, as shown by Table 3.

Table 1
A sample set of optimal solvents for the toluener n-heptane separation
Constituting groups of the
solvent candidate

aST r K

aTS r K

aHS r K

aSH r K

Sij`

K `ij

Solvent
loss %.

1. CH 2 COO. CH 3 . CH 3 O.
2. SO 3 . CH 3 . CH 3 .
3. SO. CH 3 . CH 2 CN.
4. CH 2 COO. CH 3 O. CH 2 CN.
5. CHNO 2 . CH 3 . CH 3 .
6. CH 2 O. CH 3 . CH 2 CN.

1800.00
y305.00
y3.50
370.00
625.00
y55.00

y373.50
386.50
506.50
y123.50
y423.50
136.50

y455.00
y480.00
y160.00
y400.00
y210.00
y365.00

889.00
854.00
129.00
949.00
279.00
804.00

58.50
41.66
36.16
34.68
32.71
28.84

1.55
1.19
1.20
0.79
2.17
0.87

2.32
5.54
6.01
1.53
5.46
2.62

6.191
5.965
1.812
3.921
1.370
2.361

S for solvent; T for toluene; H for n-heptane.

A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

333

Table 2
A sample set of optimal solvents for the waterrphenol separation
Constituting groups of the
solvent candidate

a PS r K

aSP r K

a WS r K

aSW r K

Sij`

K `ij

Solvent
loss %.

1. CH 2 COO. CH 3 . CHO.
2. CH 2 . OH. CHCl 2 .
3. CHCl. CH 3 . OH.
4. CH 2 COO. CH 3 . CH 3 .
5. CH 2 . HCOO. CH 2 CN.
CH 2 CO. CH 3 O. CH 2 CN.

y575.00
y510.00
y575.00
y475.00
y510.00
y563.00

1150.00
740.00
1260.00
580.00
855.00
1030.00

305.00
490.00
280.00
705.00
355.00
15.00

255.00
y35.00
340.00
y15.00
55.00
y165.00

477.96
333.91
263.45
227.78
108.67
105.56

194.25
288.98
79.39
155.16
76.31
277.98

555.57
679.03
177.96
640.42
273.60
889.17

0.213
0.244
0.422
0.028
0.431
2.769

S for solvent; P for phenol; W for water.

From this table it can be seen that each group combination from 4 through 7 can lead to two
compounds isomers. depending on whether the two methyl groups present are positioned as adjacent
or separated by a different group such as CH 2 NO 2 , CH 2 CN, etc. and this without violating the rules
described by Gani et al. w2x. Therefore, this offers an opportunity to explore the differences in solvent
properties of the two isomers by the simulation and optimisation of their molecular structures with all
Table 3
Use of calculated group interactions parameters for solvent properties calculation for the acetic acidrwater separation
Constituting groups of the
Solvent candidate
1. C. CH3. 3CH 2 NH 2 .
2. C. CH3. 3CH 3 NH.
3. C. CH3. 3CH 2 CN.
4. C. CH3. 2 CH 2 NH 2 .
CH 2 NO 2 .

5. C. CH3. 2 CH 2 NH 2 .
CH 2 CN.

6. C. CH3. 2 CH 2 CN.
CH 2 NO 2 .

7. C. CH3. 2 CH 3 O.
CH 2 CN.

aCOOH CH2NH2
aCH2NH2 COOH
aCOOH CH3NH
aCH3NH COOH
aCOOH CH2CN
aCH2CN COOH
aCOOH CH2NH2
aCH2NH2 COOH
aCH2NH2 CH2NO2
aCH2NO2 CH2NH2
aCOOH CH2NH2
aCH2NH2 COOH
aCH2NH2 CH2CN
aCH2CN CH2NH2
aCOOH CH2CN
aCH2CN COOH
aCOOH CH2CN
aCH2CN COOH
aCH2CN CH2NO2
aCH2NO2 CH2CN
aCOOH CH2CN
aCH2CN COOH
aCH3O CH2CN
aCH2CN CH3O

Calculated
value from
MGSrK

Sij`

K `ij

y85.00
y581.55
y202.25
y711.80
y315.50
y848.55
y85.00
y581.55
y326.75
97.75
y85.00
y581.55
y59.50
y96.00
y315.50
y848.55
y315.50
y848.55
y614.50
246.50
y315.50
y848.55
y265.75
414.25

415.51

6.85

17.63

0.046

1.37

0.38

0.97

0.004

160.43

47.62

122.57

0.005

31.09

3.82

9.82

0.001

525.44

62.50

160.88

0.092

94.40

20.00

51.48

0.001

131.37

28.57

73.54

0.179

Solvent
loss %.

A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

334

Table 4
Use of calculated molecular interaction parameters for comparison of isomer properties for the acetic acidrwater separation
aSAc r K

a ws r K

asw r K

Sij`

K `ij

Constituting groups of the solvent candidate

aAcS r K

Solvent
loss %.

1a. C. CH3. 2 CH 2 NH 2 . CH 2 CN.

1b. C. CH3. CH 2 NH 2 . CH3. CH 2 CN.
2a. C. CH3. 2 CH 3 O. CH 2 CN.
2b. C. CH3. CH 3 O. CH3. CH 2 CN.
3a. C. CH3. 2 CH 2 NH 2 . CH 2 NO 2 .
3b. C. CH3. CH 2 NH 2 . CH3. CH 2 NO 2 .
4a. C. CH3. 2 CH 2 CN. CH 2 NO 2 .
4b. C. CH3. CH 2 CN. CH3.CH 2 NO 2 .

y340.00
95.00
410.00 y750.00 55.26 34.84 65.50 0.001
y220.00 y105.00 y505.00 1055.00 107.44 17.64 33.16 1.264
y495.00
655.00
360.00 y265.00
2.92 3.51 6.60 0.020
y380.00
350.00
825.00 y220.00
1.53 1.07 2.01 0.231
y540.00 1055.00
95.00
275.00 14.80 2.32 4.36 0.026
y470.00
755.00
505.00 y45.00
4.80 1.51 2.84 0.590
y540.00 1020.00
200.00 y15.00
3.43 1.85 3.48 0.010
y520.00 1115.00
555.00
415.00
9.94 0.46 0.86 0.001

S for solvent; Ac for acetic acid; W for water.

a: The methyl groups are adjacent. b: The methyl groups are not adjacent.

the groups properly interconnected and the calculation of the necessary molecular interactions and
hence the required molecular interaction parameters. Table 4 presents the results for isomers only
where different values have been obtained for each component pair, showing again the need for a
method which relies not only on the type of the groups involved in the system but more on the way
they are interconnected.

6. Conclusion
The obvious solution to the fact that any group contribution method does not distinguish between
the many isomers that may be generated from different combinations of a same set of groups, would
be to consider the molecule as it is structured as a whole. However the original the idea behind a
group contribution method is that with a limited number of groups, a huge number of different
molecules of various compounds can be handled. But with the advent of powerful computing systems
like CHEM-X, which are able to simulate molecular structures as well as interaction energies, an
answer to this problem can be found if reliable molecular interaction parameters can be readily
determined for property calculations, whenever they are required.
From another point of view, the approach proposed in this work can be seen as an attempt to
establish a link between chemical graphics systems and molecular design of solvents. This may be
considered as an important step forward, in the computer-aided molecular-design strategies, which are
based on group contribution methods.

7. List of symbols
a ij
K ij
m
R

interaction parameters between groups i and j

solvent capacity for separation of i and j
distribution coefficient
universal gas constant

A.-H. Meniai, D.M.T. Newshamr Fluid Phase Equilibria 158160 (1999) 327335

Sij
Sl

solvent selectivity for separation of i and j

solvent loss

Greek letters
gi, gj

activity coefficients of components i and j

Subscripts
i,j
m
r
s

component, atom identification

molar, group, number of atoms in a molecule
raffinate phase
solvent phase

Superscripts
`

infinite dilution

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w1x
w2x
w3x
w4x
w5x
w6x
w7x
w8x
w9x
w10x
w11x

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