Fluid Phase Equilibria 398 (2015) 3645

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Regression of NRTL parameters from ternary liquidliquid equilibria

using particle swarm optimization and discussions
Zheng Li, Kathryn H. Smith, Kathryn A. Mumford, Yong Wang, Geoffrey W. Stevens *
Particulate Fluids Processing Centre, Department of Chemical and Biomolecular Engineering, The University of Melbourne, Melbourne, Victoria 3010, Australia

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 6 November 2014
Received in revised form 2 April 2015
Accepted 7 April 2015
Available online 8 April 2015

The particle swarm optimization (PSO) method was successfully used to regress the nonrandom twoliquid (NRTL) parameters from liquidliquid equilibria (LLE) data and the resulting parameters had
smaller root-mean square deviations (RMSD) compared with literature values. Analysis of the results
reveals that multiple groups of parameters with sufciently small RMSDs can be found for the same set of
LLE data. The activities calculated using these parameters and their corresponding predicted mole
fractions can be far beyond the reasonable range of activity, clearly demonstrating that the NRTL model
does not represent the real activities of components with parameters regressed from LLE. In addition, ve
sets of random data that were normalized to resemble LLE data were correlated by the NRTL model
equally well as correlations of regular LLE data. Therefore, the model does not have any advantage in
correlating LLE data over correlating random data. These limitations of the NRTL model doubt the models
theoretical validity and should be aware of when the model is used.
2015 Elsevier B.V. All rights reserved.

Keywords:
Liquidliquid equilibria
NRTL model
Particle swarm optimization
Activity
Random data

1. Introduction
The nonrandom two-liquid (NRTL) model [1] has been used
widely to correlate and predict vaporliquid equilibria (VLE) [2,3]
and liquidliquid equilibria (LLE) [36] of non-electrolytes, which
have numerous applications including distillation and liquid
liquid extraction, respectively. Extensions to this model for
predicting phase equilibria of systems containing polymers [7,8]
and electrolytes [9,10] have expanded the models versatility.
To predict phase equilibria of multiple component systems, it is
common practice to solve equations of equality of fugacities (for
VLE) [2,3] or activities (for LLE) [3,4,6] under constraints of mass
balance with known binary interaction parameters of the NRTL
model, which can be regressed from experimental data of either
VLE or LLE. As a result, regressing the NRTL parameters is the
precondition for predicting phase equilibria. While regression of
interaction parameters of the NRTL model from VLE is straightforward, regressing parameters from LLE, which minimizes the
difference of experimental and calculated mole fractions, is much
more complicated due to involvement of solving nonlinear
isoactivity equations. Although some researchers have obtained
small root-mean square deviations (RMSD) of mole fractions using
various algorithms [1115], none of these methods can guarantee

obtaining the global minimum. To obtain global minimum of

RMSD, a robust algorithm is essential. The particle swarm
optimization method (PSO) [16] is a powerful optimization
method that has attracted extensive studies in recent years and
has been used across a wide range of applications [17]. Having a
number of entities (particles) interacting with each other and
sharing information in the search space of a function, the swarm as
a whole is more likely to move close to the global minimum of the
function compared with the algorithms that have been used.
Unlike correlation of VLE, which directly deals with the vapor
pressures of components that represent the absolute value of
fugacities, the LLE calculation equates the activities of each
component in two phases without considering the real activity of
each component. As a result, the activities may not be equal to their
real values even if good equalities are obtained. Therefore, a
discussion on correlation of LLE by the NRTL model is warranted.
This study aims to illustrate the utilization of the PSO method to
regress the parameters of the NRTL model from ternary LLE and
discuss the capability of the model in representing the activities of
components in LLE.
2. Parameter regression using the PSO method
2.1. Particle swarm optimization

* Corresponding author. Tel.: +61 3 8344 6621; fax: +61 3 8344 8824.
E-mail address: gstevens@unimelb.edu.au (G.W. Stevens).
http://dx.doi.org/10.1016/j.uid.2015.04.006
0378-3812/ 2015 Elsevier B.V. All rights reserved.

The PSO was rst proposed by Kennedy and Eberhart for

optimization of nonlinear functions by simulating social behaviors

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

such as bird ocks searching for corn [16]. It has since attracted
extensive studies from a wide variety of applications due to its
exibility and ease to utilize and has undergone many variations in
algorithm [17,18]. The PSO optimizes a problem by iteratively
improving the locations of candidate solutions (particles) in the
search space. Each particle updates its location by evaluating the
objective function of its current location and the best known
location (pbest) and the best location of the entire particles (gbest).
The next iteration occurs after all the particles have been moved
and pbest and gbest have been updated. Gradually the particle
swarm is expected to move toward an optimum like a ock of birds
collectively foraging for food. The algorithm applied in this study is
as follows:
vi v  vi c1  R1  pbest  xi c2  R2  gbest  xi

(1)

xi xi k  vi

(2)

Fig. 1. Correlation of LLE data using Fa as objective function.

where vi is the moving velocity of the particle, xi is the current

location, v is inertia weight, c1 and c2 are acceleration factors, R1

Fig. 2. Initial RMSD (a) pre-regressed particles; (b) random initial particles.

Fig. 3. Decrease of RMSD with the number of iterations (a) iteration using pre-regressed particles; (b) iteration using random particles.

37

38

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

Table 1
Comparison of regression by the PSO method with literature values for ternary LLE systems.
System

Method/software

Water(1) + phenol(2) + benzene(3) at 298.15 K

Ethene tetrachloro(1) + 2-propanol(2) + water(3) at 303.15 K
Heptane(1) + ethylbenzene(2) + methanol(3) at 293.15 K
Cyclohexane(1) + enthylbenzene(2) + sulfolane(3) at 303.15 K

RMSD

Literature

This study

Literature

This study

Not given
LevenbergMarquardt
Simplex
ASPEN Plus

PSO
PSO
PSO
PSO

0.0036
0.0078
0.0029
0.023

0.0022
0.0045
0.0026
0.0034

2.2. Optimization method

Fa

(3)

Fx

where xi and g i are the mole fraction and activity coefcient of

component i, respectively, I and II represent the two phases.
Mass balance equations of components are the constraints of
isoactivity equations and can be represented as follows:
nIi nIIi ni

i 1; 2and3

ki k

3 X
2 X
M 
2
X
xjik  ^
x jik

(9)

where i is component, j is phase and k is the number of tie lines, xjik

and ^
x jik are the experimental and calculated mole fraction of
components, respectively.
While minimization of Eq. (8) is straightforward, minimization
of Fx (Eq. (9)) is complex as it involves solving isoactivity equations
under mass balance constraints. Each iteration solves the
equations for each tie line to calculate ^
xik j and then calculates
the value of Fx, which in turn determines the direction of the next
iteration through the algorithm of PSO. The iteration goes on until a
criterion, which is the maximum number of iterations in this study,
is met. The quality of regression is generally evaluated by the
RMSD.

(4)

kj k

k1

(8)

i1 j1 k1

where ni is the total moles of component i. For the prediction of

phase equilibria, a stability test of the solution satisfying Eqs. (3)
and (4) based on the tangent plane criterion [20] or the procedure
proposed by Li et al. [6] is required. This test is not necessary for
regression of parameters.
The activity coefcient equation of the NRTL model is given as
[1]
0
1
N
N
X
X
t ji Gji xj
B
xl t lj Glj C
N
C
X
xj Gij B
j1
B
C

t
 l1
lng i
(5)
B
C
ij
N
N
N
B
C
X
X
X
j1
@
G x
G x
G x A
k1

3 X
M 
X
2
xIik  g Iik  xIIik  g IIik
i1 k1

The isoactivity equations of components in two phases are

applied for calculation of LLE of ternary systems:
i 1; 2and3

[12,p. 292]
[4,p. 148]
[14,p. 62]
[13,p. 1718]

and aji (aji = aij) are the energy parameter and non-randomness
parameter, respectively.
Two types of objective functions [11] are usually used to regress
the parameters:

and R2 are two random numbers distributed in the range of [0, 1], k
is constriction factor. Values of the coefcients used in this study
were selected following Eberhart and Shi [19].

xIi g Ii xIIi g IIi

Reference

2
3
3 X
2 X
M 
2 1=2
X
j
j
^
x

x
6
7
ik
6 i1 j1 k1 ik
7
6
7
RMSD 6
7
6
7
6M
4
5

kj k

k1

(10)

gji gii
RT

(6)

For convenience of evaluating the quality of correlation, Eq. (8)

is modied into Eq. (11).

Gji expaji t ji

(7)

Fa

t ji

3 X
10
X

s ik

(11)

i1 k1

where N is the number of components in the system, gji is the

energy of interaction between a ji pair of molecules; t ji (t ji 6 t ij)

Table 2
Regressed parameters of the NRTL model for ternary LLE systems.
Systems

ij

aij

tij

t ji

Water(1)
Phenol(2)
Benzene(3)
Ethene tetrachloro(1)
2-propanol(2)
Water(3)
Heptane(1)
Ethylbenzene(2)
Methanol(3)
Cyclohexane(1)
Enthylbenzene(2)
Sulfolane(3)

12
13
23
12
13
23
12
13
23
12
13
23

0.24962
0.25426
0.30332
0.2
0.2
0.2
0.4
0.4
0.4
0.3
0.2
0.3

5.5351
5.4491
6.8088
7.2316
5.0656
0.26419
0.94695
2.0569
1.2377
1.0378
4.6788
1.2566

0.96053
3.1784
0.048392
2.9827
5.6934
9.0067
0.5712
2.4497
0.0067217
3.6815
1.6054
2.7125

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

where s ik is dened as
8 I
x  g Iik
>
>
> ik
 1;
<
xIIik  g IIik
s ik
II
II
>
x  g ik
>
>
 1;
: ik
xIik  g Iik

if
if

xIik
xIIik
xIik
xIIik

g
g
g
g

I
ik
II
ik
I
ik
II
ik

1
(12)
<1

used only 30 particles because using more particles is time

consuming due to the involvement of solving nonlinear equations.
The optimization method was further tested by regressing
ternary LLE systems from literature with 30 pre-regressed particles
and 1000 iterations. Comparison of the results with literature is
given in Table 1 and the parameters are given in Table 2. Smaller
RMSDs were obtained using the current method which demonstrates the strength of the PSO method used in this study.

3. Results and discussions

To further illustrate the minimization, we use the ternary
system of Ethene tetrachloro(1) + 2-propanol(2) + water(3)
[4,p. 148] as an example. In this example, all the nonrandomness parameters are xed as 0.2 and the energy
parameters are searched in the range of [15, 15]. Firstly, Fa
was minimized using 200 particles that are generated randomly,
each particle is a group of six energy parameters of the NRTL
model. An example of calculation is given in Fig. 1. It can be seen
that Fa reaches a minimum (either local or global) after
approximately 20 iterations. A few calculations found that
60 iterations are sufcient to reach a local minimum. The
minimization procedure was then repeated for 300 times and
the resulting 300 groups of parameters (called pre-regressed
parameters) were evaluated over RMSD and the results are
presented in Fig. 2a. It is shown that the parameters obtained
from minimization of Fa do not necessarily result in small RMSD,
which is the target of parameter regression. As comparison,
300 groups of randomly generated parameters without any
further manipulation were also evaluated using Eq. (10) with
results presented in Fig. 2b and as shown the RMSD can be very
large.
Following optimization of Fa,Fx was optimized with either
30 pre-regressed particles or 30 randomly generated particles and
each case was repeated 10 times. The results presented in Fig. 3
clearly indicate that the pre-regressed particles are good initial
estimates for the optimization of Fx although initially they may not
have sufciently small RMSDs. Nine out of the 10 calculations using
pre-regressed particles reached very similar RMSD within
1000 iterations, indicating that the RMSD calculated from this
group of parameters is most likely the global minimum. On the
contrary, the optimizations using 30 random particles reached
very different and much larger RMSDs. The comparison demonstrates that the pre-regressed particles are superior over the
random ones. Therefore, it is a good strategy to minimize Fx using
pre-regressed particles obtained from minimization of Fa.
Although selection of the number of particles and iterations
appears arbitrary, there is some rationale behind their selection.
For the optimization of Fa, 200 particles were chosen to ensure a
rapid approach to a local minimum and 60 iterations aim to ensure
the minimum reached is a local one rather than the global
minimum thus to maintain diversity of the pre-regressed particles
that are to be used for optimization of Fx. The optimization of Fx

Table 3
Three groups of parameters for the same LLE data.

Ethene tetrachloro(1)
2-Propanol(2)
Water(3)

Parameters

Group 1

Group 2

Group 3

t12
t21
t13
t31
t23
t32

7.2316
2.9827
5.0656
5.6934
0.26419
9.0067
0.0045
This study

5.8391
2.9387
6.4053
7.7491
0.0256
7.9771
0.0076
This study

483.32/303.15
116.92/303.15
2022.0/303.15
2382.4/303.15
291.60/303.15
259.50/303.15
0.0078
[4,p. 148]

RMSD
Reference

39

Fig. 4. Representation of activities by different groups of parameters.

40

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

3.1. Representation of LLE by the NRTL model

3.1.1. Local and global minimum
Multiple groups of parameters were obtained for the ternary
system of Ethene Tetrachloro(1) + 2 propanol(2) + water(3)
[4,p. 148], two of them from this study and one from literature
are presented in Table 3. Each group corresponds to a local
minimum of RMSD and the smallest RMSD is most likely the global
minimum. In terms of RMSD, all three groups of parameters are
good. However, parameters in different groups show no relevance.
If two pairs of binary interaction parameters in different groups are
exchanged, much larger RMSD will be yielded and the calculated
mole fractions can even be negative which does not make sense.
For example, if the energy parameters t 12 and t 21 in Group 1 are
replaced by the values in Group 3, some of the predicted mole
fractions using the new group of parameters are negative and the
RMSD obtained is 0.5557, which is much larger than both
0.0045 and 0.0078.
3.1.2. Representation of activities of LLE
Equality of fugacity of a component in VLE can be simplied to
be [2]
xi  g i

P  yi
Pi 0

(13)

where yi and xi are the fraction of component i in the vapor and

liquid phase, respectively, P is the total pressure and Pi 0 is the vapor
pressure of the pure component i at the same temperature. It can
be seen that the activity of a component in the liquid is equal to the
ratio of its partial pressure and vapor pressure of the pure
component. The mole fraction xi is within [0, 1], the activity
coefcient can be larger or smaller than unity; thus, mathematically we cannot derive the range of activity. In fact, it is unusual to
nd a component whose activity is larger than unity.
Unlike correlation of VLE which directly correlates partial vapor
pressures of components and composition of liquid phase,
correlation of LLE equates two sides of isoactivity equations
without knowing the real activity of each component. As a result,
representation of activities of LLE system by the NRTL model needs
to be examined. The three groups of parameters in Table 3 and their
corresponding predicted mole fractions are used to calculate
activities and results are shown in Fig. 4. Surprisingly, activities
calculated by the three groups of parameters differ signicantly
and many data points are clearly incorrect as their values are far
beyond the range of [0, 1]. Even the data points within [0, 1] most
likely do not represent the real activities of components as the
values of activities are not considered in the parameter regression.
Consequently, correlation of LLE by the NRTL model is an empirical
tting that may not reect the real activities of components, which
are the properties we aim to correlate. This weakness of the model
limits the models application in predicting phase equilibria using
parameters regressed from LLE. Expansions of the NRTL model
[710] may also suffer from the same weakness as they are
generally obtained by adding additional items to the original
equations of the model while maintaining the models theoretical
concepts and core equations.
4. Correlating normalized random data
The activity coefcient equation of the NRTL model uses a
combination of exponential functions with three adjustable
parameters, providing the model with excellent exibility in
correlating data. However, it has been demonstrated by Li et al. [6]
that the isoactivity equations of ternary LLE using the NRTL model
represent many more data points besides the experimental

equilibrium data due to sensitivity of the exponential functions.

Indeed random data that are normalized to resemble experimental
LLE data have been generated and shown to be able to be tted
equally well as correlations of experimental LLE data, refer to
Appendix A. This reveals the NRTL models empiricism and weak
theoretical basis, which should be considered when using the
model to calculate phase equilibria.
5. Conclusion
The parameters of the NRTL model have been successfully
regressed from LLE data using the particle swarm optimization
(PSO) method and smaller RMSDs were obtained compared with
literature results. Further analysis reveals that multiple groups of
parameters with sufciently small RMSDs can be found for the
same set of LLE data and the activities calculated with these
parameters and their corresponding predicted mole fractions can
be far beyond the reasonable range of activity. This clearly
demonstrates that the NRTL model does not represent the real
activities of components with parameters regressed from LLE.
Moreover, ve sets of normalized random data have been
correlated by the NRTL model equally well as correlations of
regular experimental LLE data. This questions the theoretical
validity of the NRTL model and highlights the need to strengthen
the models theory. The limitations of the NRTL model revealed in
this study should be considered when the model is used for
correlation and prediction of phase equilibria.
Acknowledgements
Support from the Australian Research Council and the Particulate Fluids Processing Centre is acknowledged. Thanks to Prof. Jian
Chen in Tsinghua University for helpful discussions. Zheng Li is
grateful for nancial support from the China Scholarship Council.
Appendix A.

1.1. Generalization of normalized random data

Five arrays of random data in the range of 01 were produced by
the mathematical software MATLAB. Each array comprises ten
rows and six columns of data with every three columns of data
representing a phase. The data in each phase were then normalized
such that the sum of data in a row equals to 1 (Eq. (A1)), thus
resembling an experimental ternary LLE data set, where each data
point represents the mole fraction of a component in one phase.
N
X
xjik 1

i 1; 2; 3; j 1; 2

(A1)

i1

where i is component, j is phase number and k is the number of

rows. The ve sets of normalized data are given in Tables A1A5
and the randomness of these data sets is clearly shown by the
phase diagrams in Fig. A1. To evaluate the correlations, ve regular
ternary LLE systems that also have ten rows of data have been
taken from literatures [2123] and are correlated as comparisons
(refer to Table A6).
1. 2 Correlation and discussions
Fa in Eq. (11) of Section 2.2 was used as the objective function to
correlate all 10 sets of data using the NRTL model with all three
parameters adjustable. Minimization of Fa was performed by the
PSO method as illustrated in Section 2 and the regressed

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

41

Table A1
Normalized random data no. 1.
Phase I

Phase II

x1

x2

x3

x1

x2

x3

0.3868

0.4331

0.1801

0.0359

0.2842

0.6799

0.3971

0.5335

0.0694

0.9403

0.0410

0.0187

0.1333

0.6224

0.2443

0.1416

0.7276

0.1308

0.2848

0.4569

0.2583

0.2618

0.3405

0.3977

0.5170

0.4643

0.0187

0.1253

0.2266

0.6481

0.5626

0.3476

0.0899

0.1399

0.7893

0.0708

0.1501

0.5665

0.2834

0.2327

0.4206

0.3466

0.0332

0.7131

0.2537

0.1050

0.3462

0.5488

0.1277

0.3931

0.4791

0.4940

0.1841

0.3219

0.3246

0.3900

0.2854

0.0997

0.0985

0.8017

x1

x2

x3

x1

x2

x3

0.5004

0.0968

0.4028

0.4969

0.3088

0.1943

0.4737

0.5076

0.0187

0.0291

0.3491

0.6218

0.0657

0.4951

0.4392

0.1631

0.4510

0.3859

0.3915

0.2081

0.4004

0.0460

0.7920

0.1620

0.2995

0.3790

0.3215

0.2410

0.4637

0.2953

0.0978

0.1423

0.7599

0.4546

0.2704

0.2751

0.1929

0.2922

0.5149

0.3308

0.2122

0.4570

0.2948

0.4937

0.2115

0.2432

0.4957

0.2611

0.3981

0.3294

0.2725

0.4233

0.3160

0.2607

0.4604

0.4579

0.0817

0.0340

0.7450

0.2210

Table A2
Normalized random data no. 2.
Phase I

Phase II

Table A3
Normalized random data no. 3.
Phase I

Phase II

x1

x2

x3

x1

x2

x3

0.8003

0.0408

0.1589

0.5117

0.3860

0.1023

0.1278

0.6101

0.2621

0.5316

0.3167

0.1516

0.3530

0.4001

0.2470

0.3143

0.3176

0.3682

42

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

Table A3 (Continued)
Phase I

Phase II

x1

x2

x3

x1

x2

x3

0.2882

0.1622

0.5496

0.1676

0.2852

0.5471

0.2411

0.7363

0.0226

0.3701

0.2939

0.3360

0.3294

0.5819

0.0887

0.4285

0.3980

0.1735

0.3969

0.1515

0.4516

0.0653

0.3949

0.5398

0.0476

0.8646

0.0878

0.0693

0.1473

0.7834

0.5765

0.0672

0.3563

0.3271

0.3695

0.3034

0.8353

0.0075

0.1572

0.1579

0.4580

0.3840

Table A4
Normalized random data no. 4.
Phase I

Phase II

x1

x2

x3

x1

x2

x3

0.1130

0.4734

0.4136

0.1410

0.4457

0.4133

0.3687

0.3665

0.2648

0.3476

0.3987

0.2537

0.3295

0.3704

0.3001

0.5219

0.3870

0.0911

0.5622

0.2998

0.1379

0.3578

0.4432

0.1990

0.2080

0.6424

0.1496

0.2626

0.6813

0.0561

0.3816

0.3801

0.2383

0.1317

0.5413

0.3270

0.5809

0.1051

0.3141

0.1011

0.2481

0.6509

0.2738

0.0603

0.6658

0.4057

0.4611

0.1333

0.0003

0.7269

0.2727

0.4338

0.1958

0.3704

0.0451

0.7700

0.1849

0.4539

0.0965

0.4497

x1

x2

x3

x1

x2

x3

0.3146

0.2183

0.4671

0.3597

0.3395

0.3008

0.3517

0.2915

0.3568

0.6338

0.0725

0.2937

0.3856

0.1152

0.4992

0.1881

0.2986

0.5133

0.5042

0.0630

0.4328

0.5320

0.2341

0.2339

0.5609

0.4093

0.0297

0.2021

0.3114

0.4865

0.5180

0.3861

0.0959

0.2930

0.0603

0.6467

0.5080

0.2071

0.2849

0.4065

0.0707

0.5228

0.1920

0.3427

0.4653

0.6164

0.2453

0.1383

0.0929

0.4440

0.4631

0.0412

0.3605

0.5983

0.2152

0.3011

0.4837

0.3870

0.5936

0.0194

Table A5
Normalized random data no. 5.
Phase I

Phase II

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

43

parameters
and
results
are
given
in
TableA6
and
results
are
also
prese-

Fig. A1. Phase diagrams of normalized random data.

nted in Fig. A2.

Table A6
Regressed NRTL Parameters for data correlation (literature data and random data).
System

ij

tij

t ji

aij

Fa

Reference

n-Hexane(1)
Benzene(2)
Sulfolane(3)
Benzene isopropyl(1)
2-Propanone(2)
Formic acid amide(3)
Ethene tetrachloro(1)
2-Propanone(2)
Water(3)
Ethene trichloro(1)
Hexanoic acid 6-amino lactam(2)
Water(3)
Water(1)
Phenol(2)
Benzene(3)
Normalized random
Data no. 1

12
13
23
12
13
23
12
13
23
12
13
23
12
13
23
12
13
23
12
13
23
12
13
23
12
13
23
12
13
23

9.1825
7.9969
3.3058
15.617
15.537
5.7609
3.4885
13.538
4.102
4.4067
3.7488
1.0684
4.2195
11.022
2.0239
3.3317
4.4288
2.8774
20.000
10.675
3.029
18.214
2.2269
4.2231
2.8988
3.0419
2.8322
3.011
2.8082
16.338

3.4202
5.6226
0.71576
3.5251
6.2466
14.755
4.5286
10.178
4.3232
0.87823
7.9841
4.888
10.272
5.0282
2.2543
3.4104
3.2477
2.6955
3.4461
3.8366
2.6762
3.1006
2.1058
1.7168
19.844
4.302
2.4435
20.000
2.8503
3.1631

0.44505
0.42441
0.49549
0.41036
0.4048
0.47162
0.26742
0.33408
0.32702
0.25113
0.31627
0.34126
0.19513
0.46432
0.50000
0.42839
0.43793
0.43179
0.34736
0.40511
0.43372
0.23501
0.50000
0.44643
0.23173
0.42781
0.45078
0.30478
0.42566
0.31597

0.594

[21,p. 111]

1.578

[4,p. 64]

1.844

[4,p. 148]

0.907

[4,p. 162]

4.048

[12,p. 292]

1.075

This study

0.683

This study

1.748

This study

1.331

This study

0.736

This study

Normalized random
Data no. 2
Normalized random
Data no. 3
Normalized random
Data no. 4
Normalized random
Data no. 5

44

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

Fig. A2. Correlations of the regular LLE data and normalized random data by the NRTL model.

Interestingly, the values of Fa for the normalized random data

and the regular LLE data from literature are comparable, indicating
that the two types of data are correlated equally well. This means
that the NRTL model does not have any advantage in correlating
regular experimental LLE data over correlating normalized random
data. The normalized random data does not have any physical
meaning in terms of molecular interactions, hence the regressed
NRTL parameters are meaningless. Similarly, the parameters for
the regular LLE systems are somewhat empirical, as can be seen
from derivation of the models equations. The weak theoretical
basis of the model explains the inconsistency of different groups of
parameters. Therefore, the NRTL models weaknesses and limitations should be considered when using it to correlate and predict
phase equilibria and further work is required to strengthen the
models theoretical basis.
References
[1] H. Renon, J.M. Prausnitz, Local compositions in thermodynamic excess
functions for liquid mixtures, AIChE J. 14 (1) (1968) 135144, doi:http://dx.
doi.org/10.1002/aic.690140124.
[2] J. Gmehling, U. Onken, VapourLiquid Equilibrium Data Collection Aqueous
Organic Systems, Vol. 1, DECHEMA, Frankfurt/Main, 1977.
[3] J.M. Prausnitz, F.W. Tavares, Thermodynamics of uid-phase equilibria for
standard chemical engineering operations, AIChE J. 50 (4) (2004) 739761, doi:
http://dx.doi.org/10.1002/aic.10069.
[4] J.M. Srensen, W. Arlt, Liquidliquid equilibrium data collection-ternary
systems, DECHEMA, Frankfurt, 1980.
[5] C.-C. Chen, Molecular thermodynamics for pharmaceutical process modeling
and simulation, Chemical Engineering in the Pharmaceutical Industry, John
Wiley & Sons, Inc., 2010, pp. 505519.

[6] Z. Li, K.A. Mumford, Y. Shang, et al., Analysis of the nonrandom two-liquid
model for prediction of liquidliquid equilibria, J. Chem. Eng. Data 59 (8)
(2014) 24852489, doi:http://dx.doi.org/10.1021/je500204v.
[7] C.-C. Chen, A segment-based local composition model for the gibbs energy of
polymer solutions, Fluid Phase Equilib. 83 (0) (1993) 301312, doi:http://dx.
doi.org/10.1016/0378-3812(93) 87033-W.
[8] C.-C. Chen, Y. Song, Solubility modeling with a nonrandom two-liquid segment
activity coefcient model, Ind. Eng. Chem. Res. 43 (26) (2004) 83548362, doi:
http://dx.doi.org/10.1021/ie049463u.
[9] C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, Local composition model for excess
Gibbs energy of electrolyte systems. Part I: single solvent, single completely
dissociated electrolyte systems, AIChE J. 28 (4) (1982) 588596, doi:http://dx.
doi.org/10.1002/aic.69028041.
[10] Y. Song, C.-C. Chen, Symmetric electrolyte nonrandom two-liquid activity
coefcient model, Ind. Eng. Chem. Res. 48 (16) (2009) 77887797, doi:http://
dx.doi.org/10.1021/ie9004578.
[11] J.M. Srensen, T. Magnussen, P. Rasmussen, A. Fredenslund, Liquidliquid
equilibrium data: their retrieval, correlation and prediction Part II. Correlation,
Fluid Phase Equilib. 3 (1) (1979) 4782, doi:http://dx.doi.org/10.1016/03783812(79)80027-8.
[12] J.R. Alvarez Gonzalez, E.A. Macedo, M.E. Soares, A.G. Medina, Liquidliquid
equilibria for ternary systems of waterphenol and solvents: data and
representation with models, Fluid Phase Equilib. 26 (3) (1986) 289302, doi:
http://dx.doi.org/10.1016/0378-3812(86)80024-3.
[13] I. Ashour, S.I. Abu-Eishah, Liquidliquid equilibria of ternary and sixcomponent systems including cyclohexane, benzene, toluene, ethylbenzene,
cumene, and sulfolane at 303.15 K, J. Chem. Eng. Data 51 (5) (2006) 17171722,
doi:http://dx.doi.org/10.1021/je060153n.
[14] B.E. Garca-Flores, J. guila-Hernndez, F. Garca-Snchez, M.A. Aquino-Olivos,
(Liquidliquid) equilibria for ternary and quaternary systems of representative
compounds of gasoline + methanol at 293.15 K: experimental data and
correlation, Fluid Phase Equilib. 348 (2013) 6069, doi:http://dx.doi.org/
10.1016/j.uid.2013.03.022.
[15] Bochove Gv, Two- and Three-Liquid Phase Equilibria in Industrial MixedSolvent Electrolyte Solutions, Technische Universiteit Delft, Delft, 2003.

Z. Li et al. / Fluid Phase Equilibria 398 (2015) 3645

[16] J. Kennedy, R. Eberhart, Particle swarm optimization, Proceedings, IEEE
International Conference on Nov/Dec 1995 4 (1995) 19421948, doi:http://dx.
doi.org/10.1109/icnn.1995.488968 (paper presented at: Neural Networks).
[17] R. Poli, J. Kennedy, T. Blackwell, Particle swarm optimization, Swarm Intell. 1
(1) (2007) 3357, doi:http://dx.doi.org/10.1007/s11721-007-0002-0.
[18] R.C. Eberhart, S. Yuhui, Particle swarm optimization: developments,
applications and resources, Proceedings of the 2001 Congress on 2001 1
(2001)
8186,
doi:http://dx.doi.org/10.1109/cec.2001.934374
(paper
presented at: Evolutionary Computation).
[19] R.C. Eberhart, Y. Shi, Comparing inertia weights and constriction factors in
particle swarm optimization, Proceedings of the 2000 Congress on 2000 1

45

(2000)
8488,
doi:http://dx.doi.org/10.1109/cec.2000.870279
paper
presented at: Evolutionary Computation.
[20] M.L. Michelsen, The isothermal ash problem. Part I. Stability, Fluid Phase
Equilib. 9 (1) (1982) 119, doi:http://dx.doi.org/10.1016/0378-3812(82)850012.
[21] J. Chen, L.-P. Duan, J.-G. Mi, W.-Y. Fei, Z.-C. Li, Liquidliquid equilibria of multicomponent systems including n-hexane, n-octane, benzene, toluene, xylene
and sulfolane at 298.15 K and atmospheric pressure, Fluid Phase Equilib. 173
(1) (2000) 109119, doi:http://dx.doi.org/10.1016/S0378-3812(00)00398-8.