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A priori prediction of complex liquid–liquid–liquid

equilibria in organic systems using a continuum
Cite this: Phys. Chem. Chem. Phys.,
2020, 22, 22023 solvation model†
Priyotosh Bairagya, ‡a Debashis Kundu ‡bc and Tamal Banerjee*c

Received 16th June 2020,
Accepted 16th September 2020
DOI: 10.1039/d0cp03225e
rsc.li/pccp
Liquid–liquid–liquid equilibria (LLLE) is usually observed in many industrial processes primarily linked to
enhanced oil recovery techniques. However their measurements are complex and so are their computa-
tions. An inherently predictive tool is often useful for elucidating their distribution ratios and phase
compositions. In the present work, the phase behavior of nine ternary and two quaternary LLLE systems
were predicted employing the quantum chemical based COnductor like Screening MOdel-Segment
Activity Coefficient (COSMO-SAC) model. The methodology namely, Rachford–Rice LLLE (RRL3E)
algorithm and Henley–Rosen LLLE (HRL3E) algorithm were used to predict the triphasic compositions in
each system. In the RRL3E approach, the triphasic systems were assumed into two co-existing biphasic
liquid–liquid equilibria systems, whereas in the HRL3E approach, all three phases were considered to be
in equilibrium with each other simultaneously. Apart from predicting the local compositions, the HRL3E
algorithm was also used to predict the individual phase splits and phase fractions of the LLLE region.
Average overall root mean square deviation (rmsd (%)) values considering all 42 datasets and corres-
ponding to 414 data points were recorded as 4.65% and 4.83% using the RRL3E and HRL3E algorithms
respectively. Further, the RRL3E algorithm was extended to correlate the LLLE data for all systems using
the Genetic Algorithm (GA) based NRTL (GA-NRTL) and UNIQUAC (GA-UNIQUAC) models.

1. Introduction
Multicomponent phase equilibria involving more than two
liquids are often encountered in chemical processes and
industries. The knowledge of multicomponent as well as multi-
phase liquid equilibrium is essential to design the extraction
plant as well as to understand the behavior of coexisting
phases. Significant interest in liquid systems with more than
two liquid phases has been observed in recent years. This in
return necessitates the knowledge of multicomponent as well
as multiphase liquid equilibria for designing separation units,
Enhanced Oil Recovery (EOR) operations and phase transfer
catalytic processes. Liquid–liquid–liquid equilibria (LLLE) systems
a
Department of Chemical Engineering, Jadavpur University, Kolkata, West Bengal,
700032, India
b
Department of Chemical Engineering, Institute of Chemical Technology
Marathwada Campus, Jalna, Maharashtra, 431203, India
c
Department of Chemical Engineering, Indian Institute of Technology Guwahati,
Guwahati, Assam, 781039, India. E-mail: tamalb@iitg.ac.in
† Electronic supplementary information (ESI) available: COSMO-SAC (2002)
model, assumptions in COSMO-SAC, RRL3E and HRL3E models, boundary
conditions, structures of ILs, Phase diagram of GA-NRTL, GA-UNIQUAC models,
binary interaction parameters of GA-NRTL and GA-UNIQUAC model, UNIQUAC
parameters from PCM calculation. See DOI: 10.1039/d0cp03225e
‡ Both the authors have equal contribution.
can be classified as either Treybal type III or Winsor type III
systems.1,2 The Treybal type III system corresponds to the
existence of three pairs of binary liquid regions with a single
triphasic LLLE region in between.1 The Winsor type classifica-
tion characterizes the phase behavior of oil/water/surfactant
systems often encountered in EOR operations.2 The Winsor
type-III systems have a large triphasic region flanked by two
minor biphasic regions, with an often undetectable third
biphasic region present adjacent to the triphasic zone.
Separation processes involving LLLE systems are observed in
microextraction of lipids and polymers where the bulk concen-
tration of the polymer/lipid exists as a separate liquid phase in
addition to aqueous and hydrocarbon phases.3 Phase transfer
catalytic operations show LLLE behavior by forming a middle
catalyst rich phase separating the reactant and product
phases.4,5 In wastewater treatment systems, three liquid phases
are observed in the separation of volatile organic solutes, heavy
metals etc.6 A limited number of three phase equilibria or LLLE
systems are being reported in the literature which shall serve as
experimental database of our present work.
In general, the computation of LLLE is challenging due to its
complex phase equilibria. The phase behavior of multiphase
liquid systems depends on the type of components involved as
well as temperature, pressure and presence or absence of salts.

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Hence, the classical LLLE problem needs to be revisited and
the knowledge of phase equilibria of these systems needs to be
expanded for more accurate correlation and modelling of
experimental LLLE data. Presently, there is only a handful
of computational algorithms for solving LLLE systems. Stateva
et al.7 have developed one of the earliest methods of LLLE
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computation based on Gibbs minor common tangent plane
stability analysis. Lucia et al.8 in collaboration with AspenTech
Corp. have developed a multiphase flash algorithm based on
Gibbs energy minimization technique capable of solving LLLE
problems. Their method has been further improved by Denes
et al.9 and is tested on a benchmark LLLE problem consisting
of hexanol–nitromethane–water mixture. Other types of LLLE
computation approaches include an algorithm by Marcilla
et al.10 based on the topology of dimensionless Gibbs mixing
energy (GM/RT).
If the occurrence of LLLE is not validated or checked for
while designing liquid–liquid extraction systems, operational
inconsistencies including the presence of multiple steady states
(MSS) can occur within the equipment. Hence, a generalized
computational framework for a priori LLLE prediction in multi-
component systems would provide a much-needed workaround
for troubleshooting and designing modern extraction processes.
In the present work, we employ the quantum-chemical based
COnductor-like Screening MOdel – Segment Activity Coefficient
(COSMO-SAC) approach for a priori prediction of activity
coefficients of multicomponent systems. The COSMO-SAC
model computes the activity coefficients from molecular inter-
actions arising from quantum chemical solvation calculations
in a hypothetical perfect conductor.11 For LLLE prediction,
COSMO-SAC is incorporated within a suitable equation-
solving flash algorithm to calculate the predicted compositions
of the triphasic zone. Two such algorithms developed in the
present work include the Rachford–Rice LLLE (RRL3E) and the
Henley–Rosen LLLE (HRL3E) methods. The RRL3E algorithm is
based on equilibrium relations of two-phase flash while the
HRL3E algorithm is based on modified Henley–Rosen three
phase adiabatic flash. Kundu and Banerjee used similar
algorithms with COSMO-SAC model for a priori VLLE predic-
tions of eight ternary and two quaternary systems.12 Recently,
Bairagya et al.13 used these algorithms for a priori VLLE predic-
tions of six imidazolium and three pyridinium based ternary
Ionic Liquid (IL) systems.
Ionic liquids are molten salts consisting of organic cations
and organic or inorganic anions. Tunable physio-chemical
properties, nonvolatility, wide liquidus temperature ranges
make ILs a suitable solvent for separation processes.14 Surface
Active Ionic Liquids (SAILs) showing surfactant properties
for EOR applications, form LLLE systems with water and
1-dodecane mixtures.15 In the present work, both non-Ionic-
Liquid (non-IL) and Ionic-Liquid (IL) systems have been studied.
The non-IL based LLLE systems studied include 1-decane/
1-hexadecane + water + triacetin systems reported by Revellame
et al.,16,17 aniline + 1-octane + water system reported by
Grenner et al.,18 1-hexane + aniline + water system reported by
Frolkova et al.,19 and water + 2-butoxyethanol (C4E1) + 1-dodecane
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reported by Lin et al.20 In the present work, IL systems with
trihexyltetradecylphosphonium dicyanamide ([P66614][DCA]), trihexyl-
tetradecylphosphonium bis(trifluoromethylsulfonyl)imide
([P66614][NTf2]), 1-decyl-3-methylimidazolium bis(trifluoromethyl-
sulfonyl)imide ([C10mim][NTf2]), and 1-dodecyl-3-methyl-
imidazolium bis(trifluoromethylsulfonyl)imide ([C12mim][NTf2])
ILs have been studied.21–23 As a first, the phase behavior of
two quaternary LLLE systems have been successfully predicted
i.e. 1-heptane + aniline + 1-hexane + water and 1-heptane +
aniline + water + benzene systems.19
2. Computational methods
2.1. Geometry optimization and COSMO file generation
Activity coefficients are calculated by the COSMO-SAC (2002)
model developed by Lin and Sandler.11 Further, the governing
equations of COSMO-SAC and the values of universal COSMO-
SAC constants are given in Table S1 of the ESI.† Implementing
the COSMO-SAC model is a four-step process which involves:
(1) geometry optimization of individual molecules; (2) COSMO
file generation; (3) generation of s – profile from COSMO file;
and (4) using the s – profile data for the calculation of activity
coefficients. Initially molecular geometries are drawn in Gauss
View 5.0 visualization package and are optimized in Gaussian
09 QC package in accordance with their most stable
conformer.24,25 All molecules are optimized with density func-
tional theory (DFT) using the 6-31+G(d) basis set. Becke’s three-
parameter exact exchange functional coupled with the gradient
correlation function of Lee, Young, and Parr, abbreviated as
B3LYP, has been used as the DFT level of theory.26,27 In the
COSMO solvation calculation step, the molecular geometries
are optimized at the DFT level using BVP86 functional and
DGA1 density fitted SVP basis sets.28–30 The DGA1 density
gradient approximation expands the electron density of atoms
as atom-centred functions which saves computational time by
selectively integrating the coulomb interaction in contrast to all
electron integrals. SCF energies are refined in the COSMO-
solvation step by switching to full integral accuracy. The
combination of B3LYP/6-31+G(d) for geometry optimization
and BVP86/SVP/DGA1 for COSMO-solvation calculation offers
the best trade-off for saving computational time while retaining
the highest possible accuracy for the COSMO-solvation step. In
the next step, the COSMO file (‘.cosmo’ extension) is used in
our in house reimplementation of COSMO-SAC code to gene-
rate the s – profile and to predict the activity coefficients of the
constituents.
COSMO-SAC is an extension of the COSMO solvation theory
where molecules are considered as a collection of surface
segments.31,32 Each segment has a segmental area and screening
charge. The segmental areas are grouped into 71 discrete bins
(0.035 e Å2 to +0.035 e Å2 with an increment of +0.001 e Å2)
and a representative screening charge density profile namely,
s – profile is created. The normalized form of s – profile is the
two-dimensional representation of three dimensional charged
segments grouped in a specified number of bins (usually 71).
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With the help of s – profile, we estimate how segments interact Similarly for the middle-bottom LLE system we have:
with each other, leading to the establishment of intra and LM
intermolecular interactions. The s-profile of IL constituents is cMB ¼
LM þ LB
constructed by linear averaging of cationic and anionic s-profiles
These interactions originate from the non-uniform contact among
segments, leading to misfit energy and non-bonded interactions From the overall mass balance the following relation holds:
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such as hydrogen bonding interactions. The segment activity F = LT + LM + LB (6)

coefficient is calculated self-consistently from a set of statistical-
mechanical equations given in by Lin and Sandler.11 Finally, the Here, cTM is calculated by solving the objective function f (cTM)
sum of all such segmental activity coefficients leads to the activity iteratively given as:
 
coefficient of the compound in the mixture. The excess Gibbs free Xc
zMT
i 1  KiMT
energy is thus divided into restoring solvation free energy and a f ðcTM Þ ¼ ¼0 (7)
i¼1
1 þ cTM ðKiMT  1Þ
combinatorial term that originates due to the size and shape of
the molecule. The in-house COSMO-SAC code is integrated with Similarly where cMB is calculated iteratively from the objec-
the RRL3E and HRL3E subroutines to predict the phase behavior tive function f (cMB) as:
of the LLLE systems. These subroutines are discussed below.  
Xc
zMB
i 1  KiBM
f ðcMB Þ ¼ ¼0 (8)
2.2. Rachford–Rice LLLE (RRL3E) algorithm i¼1
1 þ cMB ðKiBM  1Þ
In this approach, the three phase equilibria is considered to be The phase-wise calculation for the mole-fraction is given by:
composed of two dependent subsystems i.e. top-middle and
middle-bottom phases respectively. Therefore, the feed F splits KiMT zMT
xTi ¼ i
(9)
into three liquid phases having molar holdups of LT, LM, and LB 1 þ cTM ðKiMT  1Þ
with the local compositions xTi , xM B
i and xi for top, middle and
bottom phases respectively. Feed compositions of top-middle zMT
xM
i ¼
i
(10)
and middle-bottom phases are denoted by zTM i and zBM
i respec- 1 þ cTM ðKiMT  1Þ
tively. For COSMO-SAC predictions, feed compositions zTM i and
zBM are obtained by the arithmetic averaging of top-middle and zBM
i xBi ¼ i
(11)
middle-bottom compositions of experimental LLLE data since 1 þ cMB ðKiBM  1Þ
feed composition data for LLLE systems gets rarely reported in
The following relation holds irrespective of the LLE system
literature and any feed guess outside the reported phase
in consideration:
boundary may lead to convergence failure.
At equilibrium the governing equations relating the compo- X
c X
c X
c
xTi ¼ xM
i ¼ xBi ¼ 1 (12)
sitions of each component in different phases are given as: i¼1 i¼1 i¼1

xTi gTi = xM M B B
i gi = xi gi (1) Fig. 1 represents the flowchart for RRL3E algorithm where
Here, gTi , gM gBi COSMO-SAC calculations are invoked for updating the value of
and i , denote the activity coefficients of the ith
component in the top, middle and bottom phases respectively. activity coefficients at every iteration step. Separate subroutines
While considering the top-middle phase LLE system we have: are developed for the top-middle and middle-bottom LLE
systems. Within the iteration loops, the objective functions
xTi gM
¼ iT ¼ KiMT (2)
xM
i gi

Similarly considering the middle-bottom phase LLE system

we have:

xM gBi
i
B
¼ M ¼ KiBM (3)
xi gi

where KMTi denotes the ratio between the activity coefficients

gTi and gM
i whereas Ki
BM
denotes the ratio between the activity
coefficients gi and gBi respectively. For the top-middle LLE
M

system we have:

LT
cTM ¼ (4)
LT þ LM

where cTM is the ratio of the top phase split (LT) to the total split
(LT + LM) for the top-middle LLE system. Fig. 1 Flowchart of Rachford–Rice LLLE (RRL3E) algorithm.

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(eqn (7) and (8)) are minimized using a modified bisection X

c X
c
xM
i  xBi ¼ 0 (20)
method. The choice of modified bisection method ensures that i¼1 i¼1
the function domain always exists within the range corres-
ponding to f (xi = 0) and f (xi = 1).
X
c X
c
2.3. Henley–Rosen LLLE (HRL3E) algorithm xBi  xTi ¼ 0 (21)
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i¼1 i¼1
The original Henley–Rosen formulation for vapor–liquid–liquid
equilibria (VLLE) computation using rigorous three-phase flash
relations was based on coupled non-linear equation solving Additionally, 0 o a o 1 and 0 o b o 1 need to be satisfied
approaches. A simplified version of the Henley–Rosen algo- along with eqn (12) which serves as a check for phase stability.
rithm was presented by Sampath and Leipzeiger for VLLE However, this means that for complex mixtures having unstable
calculations.33 Keeping the structure similar to Sampath and three-phase regions, the algorithm might suffer. For these
Leipzeiger’s original algorithm, we have modified the Henley– cases, the RRL3E algorithm is preferred since it has fewer
Rosen algorithm for LLLE computations. In this approach, we assumptions. The values of a and b are obtained iteratively
consider the flashing of the liquid feed F into three separate and need to be simultaneously solved using separate objective
liquid phases having molar holdups of LT, LM, and LB denoting functions as discussed below. However, simultaneous initializa-
the top, middle and bottom phases respectively. This scheme is tion of both a and b are difficult and often leads to convergence
based on the calculation of local compositions from two failures. Sampath and Leipzeiger33 introduced a convenient way
independent variables a and b. Here, a is defined as the fraction of estimating b from a which is presented below in eqn (22). For
of molar holdup of top liquid phase LT to the total feed F and is the initial guess, a = 0.33 is used in our calculations which is
given by the relation: recommended by Sampath and Leipzeiger.33
 
LT zH2 O gBH2 O  a KHB2 O  1  1
a¼ (13)
F b¼ ! (22)
KHB2 O
While b is given by: ð1  aÞ 1
KHM2 O
LM
b¼ (14)
LM þ LB The rationale behind this approximation is that most tri-
Here, b relates to the fraction of middle phase split L to the M phasic systems encountered in the industry have an aqueous
total split (LM + LB) of the middle-bottom LLE system. The local phase which is largely immiscible with the other two phases.
composition of the middle phase xM Often, the mole-fraction of water in this aqueous phase is close
i is given by:
to unity. This allows to approximate the activity of water in the
zi
xM
i ¼ (15) aqueous phase to be very close to unity at all compositions as:
KiMT
bð1  aÞ þ ð1  aÞð1  bÞ þ aKiMT aw w w
H2 O ¼ gH2 O xH2 O ¼ 1. Choosing pure water as the reference in
KiBT
the aqueous phase, the addition of a hydrocarbon to this phase
where zi denotes the arithmetic average composition of the results in breaking of hydrogen bonds while no new hydrogen
three phases (top, middle and bottom). KMT i is given by eqn (2) bonds are formed thus increasing the entropy of mixing.
þ 
and KBT
i is defined as the ratio of activity coefficients gBi and gTi Hence, gw H2 O ! 1 while xwH2 O ! 1 indicating that their
(bottom phase and top phase respectively) which is given by: product aw w w w
H2 O ¼ gH2 O xH2 O remains close to unity even if gH2 O
and xw
H2 O deviate slightly from unity.
xTi gB
B
¼ iT ¼ KiBT (16) The objective functions that need to be solved iteratively at
xi gi
each step depending on the values of a and b are given below:
Consequently the compositions for the bottom and top  
phases are given by: X
c
1  KiMT zi
fMT ða; bÞ ¼  
K MT
KiMT M i¼1 bð1  aÞ þ ð1  aÞð1  bÞ iBT þ aKiMT
xBi ¼ x (17) Ki
KiBT i ¼0
(23)

xTi = KMT M
i xi (18)
 MT
The solution must satisfy the following three conditions for Ki MT
X
c  K i zi
convergence: KiBT
fBT ða; bÞ ¼  
K MT
X
c X
c i¼1 bð1  aÞ þ ð1  aÞð1  bÞ iBT þ aKiMT
xTi  xM Ki
i ¼0 (19)
i¼1 i¼1 ¼0 (24)

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KiMT LM = b(1 a) (29)
X
c 1 zi
KiBT
fMB ða; bÞ ¼   LB = (1  a)(1  b) (30)
K MT
i¼1 bð1  aÞ þ ð1  aÞð1  bÞ iBT þ aKiMT
Ki
The flowchart for HRL3E algorithm is given in Fig. 2.
¼0
The accuracy of the predictions with respect to the experi-
(25)
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mental values are denoted by root-mean-square-deviation

[rmsd (%)] which is defined as:
Depending on the value of b one can obtain the value of a
from the relation: " #1
X
c X m ðxj
p X j 2 2
calc;i;k  xexpt;i;k Þ
! rmsd ð%Þ ¼ 100  (31)
  KHB2 O i¼1 j¼1 k¼1
mcp
B
zH2 O gH2 O  1  b 1
KHM2 O
a¼ ! (26) where m refers to the number of tie-lines, c refers to the number
  KHB2 O
KHB 2 O  1  b  1 of system components and p denotes the number of phases.
KHM2 O Here, i, j, and k denote indices of components, phases, and
tielines respectively.
Using this method, one can also find the individual splits
(LT, LM, and LB) for the system from a and b provided that a unit
molar feed-rate is assumed: 3. Results and discussions
3.1. Phase equilibria data
LT + LM + LB = 1 (27)
Calculation of experimental and predicted phase-wise compo-
LT = a (28) sition data is executed with mole-fraction basis. The list of LLLE

Fig. 2 Flowchart for Henley–Rosen LLLE (HRL3E) algorithm.

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systems studied can be found in Table 1. For the present work,
nine ternary and two quaternary systems have been considered.
The ternary systems have been grouped based on having
non-Ionic Liquid (non-IL) and Ionic Liquid (IL) constituents.
Experimental data for quaternary LLLE systems is extremely
limited and the two systems studied in the present work are
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model allows for the prediction of phase splits for the top, middle
and bottom phases (LT, LM and LB respectively). The phase split
values along with their corresponding phase fraction data
(a and b) from HRL3E algorithm can be found in Table S2 of
the ESI.† Both the RRL3E and HRL3E approaches to COSMO-SAC
prediction describe the three-phase region with sufficient

classified as having only non-IL components. We have assumed accuracy. A consolidated list of assumptions and boundary
that the cationic and anionic moieties of the IL constituents conditions applicable to the COSMO-SAC, RRL3E and HRL3E
exist separately in solution. It has been established by Bharti models has been provided in Table S3 of the ESI.† The average
et al.14 that this assumption significantly increases the quality overall rmsd (%) values using the RRL3E and HRL3E methods
of COSMO-SAC based LLE predictions while lowering the like- are obtained as 4.648% and 4.831% respectively.
lihood of encountering a no-split (NS) condition. Fractional 3.1.1. COSMO-SAC predictions of ternary non-IL based
dissociation of IL constituents has not been considered due to LLLE systems. Further subclassification of the ternary non-IL
the empirical nature of the IL-dissociation constant (a0) which systems is based on the type of constituents of these systems.
also depends on temperature and IL-concentrations. Existence Broadly, three types of systems have been studied in this section
of long-range electrostatic interactions in the IL-systems has namely, water–oil–triglyceride, water–aliphatic–aromatic and
been neglected since, additional terms in the activity coefficient water–oil–nonionic surfactant systems.
calculation to describe such electrostatic interactions affect the The oil–water–triglyceride systems i.e., 1-decane + water +
thermodynamic consistency.34,35 The phase diagrams of COSMO- triacetin (system1) and 1-hexadecane + water + triacetin (system2)
SAC predictions using the RRL3E and HRL3E approaches for show a large triphasic region containing a hydrocarbon (1-decane/
ternary systems have been provided in Fig. 3. For the quaternary 1-hexadecane) top phase, a middle phase rich in the triglyceride
LLLE systems, the COSMO-SAC predicted phase diagrams using fraction (i.e. triacetin) and an aqueous bottom phase.16,17 The
the RRL3E and HRL3E algorithms have been provided in Fig. 4. COSMO-SAC predictions for system1 using RRL3E and HRL3E
Relative deviations of the predicted data against the experimental algorithms can be found in Fig. 3(a) and (b) respectively. In this
results are gauged in terms of rmsd (%) as given by eqn (31). case, RRL3E algorithm performs better than the HRL3E
Phase-wise (top, middle and bottom phases) and overall rmsd (%) algorithm. We observe overall rmsd (%) values of 0.71% and
values for COSMO-SAC predictions using the RRL3E and HRL3E 6.06% using the RRL3E and HRL3E approaches respectively.
algorithms can be found in Tables 2 and 3 respectively. Using the RRL3E algorithm, the triacetin-rich phase and
In addition to the prediction of the local compositions of the the overall triphasic zone is predicted with marginal loss of
triphasic region, the HRL3E algorithm with the COSMO-SAC accuracy. Results of COSMO-SAC prediction using HRL3E algo-
rithm show a larger triphasic region and greater enrichment of
triacetin in the triacetin-rich phase compared to the experi-
mental phase behavior. This can be attributed to the lower
Table 1 List of LLLE systems studied in the present work
solubility of water in triacetin as predicted by COSMO-SAC.
Number Both approaches predict the compositions of the aqueous and
System of tie-
hydrocarbon rich phases with minor deviations. For system2,
Type of system number Components triangles Ref.
COSMO-SAC predictions using the HRL3E algorithm shows
Ternary systems
lower overall rmsd (%) than RRL3E algorithm at 1.86% and
Non-IL systems 1 1-Decane + water + triacetin 8 16
2 1-Hexadecane + water + 1 17 9.23% respectively. The predicted phase diagram for system2
triacetin using the RRL3E and HRL3E algorithms can be found in
3 Aniline + 1-octane + water 7 18
Fig. 3(c) and (d) respectively.
4 1-Hexane + aniline + water 1 19
5 Water + C4E1 + 1-dodecane 3 20 Two LLLE systems containing water–aliphatic–aromatic
IL systems 6 Water + [C10mim][NTf2] + 2 21 components have been studied in the present work i.e. aniline +
1-dodecane
1-octane + water (system3) and 1-hexane + aniline + water
7 Water + [C12mim][NTf2] + 2 21
1-dodecane (system4). These systems have a hydrocarbon top-phase
8 Water + [P66614][DCA] + 2 22 (1-octane/1-hexane), aromatic middle phase (aniline) and an
1-dodecane
aqueous bottom phase.18,19 Experimental data for system3 has
9 Water + [P66614][NTf2] + 4 23
1-dodecane been obtained within a temperature range of 298.15 K to
Quaternary systems 363.15 K as reported by Grenner et al.18 It has been further
Non-IL systems 10 1-Heptane + aniline + 6 19
reported that at 298.15 K the aqueous phase becomes the
1-hexane + water
11 1-Heptane + aniline + 6 19 middle phase while the aniline-rich phase becomes the bottom
water + benzene phase due to a phase inversion phenomenon. The key reason is
[P66614][DCA]: trihexyltetradecylphosphonium dicyanamide; [P66614]- being the drastic differences in temperature-density relation-
[NTf2]: trihexyltetradecylphosphonium bis(trifluoromethylsulphonyl)- ships of 1-octane and aniline.18
imide; [C10mim][NTf2]: 1-decyl-3-methylimidazolium bis(trifluoromethyl-
sulfonyl)imide; [C12mim][NTf2]: 1-dodecyl-3-methylimidazolium bis(trifluoro- COSMO-SAC predictions using the RRL3E algorithm describes
methylsulfonyl)imide; C4E1: 2-butoxy-ethanol. almost quantitative phase behavior with marginal deviations.

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Fig. 3 Phase diagrams showing COSMO-SAC predictions for ternary LLLE systems using RRL3E and HRL3E approaches. (a) and (b) system1 (c) and
(d) system2, (e) and (f) system3, (g) and (h) system4, (i) and (j) system5, (k) and (l) system6, (m) and (n) system7, (o) and (p) system8, and (q) and (r) system9.

In addition to predict the correct temperature dependencies on
LLLE behavior, well-resolved triphasic regions are obtained using
the RRL3E algorithm. In contrast, COSMO-SAC predictions using
the HRL3E algorithm describe a slightly larger triphasic region
at all temperatures due to a marginal overestimation of the
aniline content in the aniline-rich phase. The phase diagrams
for COSMO-SAC predictions using RRL3E and HRL3E approaches
for system3 has been depicted in Fig. 3(e) and (f) respectively.
Overall rmsd (%) values for system3 using RRL3E and HRL3E
approaches are found to be 1.99% and 4.80% respectively. For
system4, COSMO-SAC predictions using both RRL3E and HRL3E
algorithms show similar phase behavior where the predicted
triphasic region is smaller as compared to the experimental
measurements. For the RRL3E algorithm, an overall rmsd (%)

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Table 3 rmsd (%) values of COSMO-SAC predictions using HRL3E

algorithm

Phase-wise rmsd values (%)

System Overall
Type of system number Top Middle Bottom rmsd (%)
Non-IL systems 1 0.21 10.48 0.45 6.06
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(ternary) 2 0.33 1.23 2.96 1.86

3 2.00 7.97 1.25 4.80
4 3.33 5.76 0.06 3.84
5 1.36 5.22 8.17 7.39
IL systems (ternary) 6 0.84 0.00 3.44 2.04
7 0.90 0.00 7.68 4.46
8 2.30 8.51 0.00 5.09
9 12.05 12.96 0.00 10.21
Non-IL systems 10 1.78 5.42 1.01 3.34
(quaternary) 11 3.66 5.91 0.89 4.05
Average Ternary systems 5.083
Quaternary systems 3.695
Overall 4.831

Fig. 4 Phase diagrams showing COSMO-SAC predictions for quaternary indicates that a sizeable amount of C4E1 is solubilized in this
LLLE systems using RRL3E and HRL3E approaches. (a) and (b) system10,
phase. This occurs due to the surfactant–water interactions,
(c) and (d) system11.
where C4E1 acts both as a hydrogen bond (H-bond) donor (due
to R–O–R groups) and a H-bond acceptor (due to R–O–H
Table 2 rmsd (%) values of COSMO-SAC predictions using RRL3E
groups) promoting cross-H bonding with water. This causes a
algorithm deviation in the activity of the aqueous phase (i.e. aH2O o 1)
because as C4E1 solubilizes in water, mole-fraction of water
Phase-wise rmsd values
(xH2O) decreases while cross H-bonding between C4E1 and water
(%)
System Overall decreases the activity coefficient (gH2O) by decreasing the
Type of system number Top Middle Bottom rmsd (%)
entropy of mixing.18 This causes a deviation in the predicted
Non-IL systems (ternary) 1 0.21 1.13 0.44 0.71 value of b from a (eqn (22)) within the HRL3E algorithm leading
2 0.94 1.01 15.93 9.23
3 3.09 1.46 0.39 1.99
to an overall rmsd (%) value of 7.39%. A similar reasoning can
4 2.32 5.14 0.02 3.25 be applied for RRL3E algorithm which describes an overall
5 1.85 2.86 8.12 5.08 rmsd (%) of 5.08%. This conclusion is based on the observation
IL systems (ternary) 6 0.02 0.00 11.48 6.63
7 0.02 0.00 12.35 7.13
of the qualitative aspects of COSMO-SAC predicted LLLE
8 3.16 8.56 0.00 8.07 regions which are almost similar while using either algorithm.
9 10.27 1.99 0.00 6.04 3.1.2. COSMO-SAC predictions of IL based ternary LLLE
Non-IL systems 10 1.30 1.34 0.85 1.18
(quaternary) 11 2.06 2.16 0.95 1.81
systems. Surface Active Ionic Liquids (SAILs) are a class of ILs
Average Ternary systems 5.348 that have properties useful for the separation of oil–water
Quaternary systems 1.495 mixtures commonly encountered in secondary and tertiary oil
Overall 4.648
recovery operations.15 These ILs induce phase separation
by one of the two processes: (i) by creating a third phase
separating the oil and water-rich phases through bulk aggrega-
value of 3.25% is observed with a decreased enrichment of aniline tion and (ii) by lowering the interfacial tension between
in the aniline-rich phase. While for the HRL3E algorithm, the oil–water two-phase mixtures through micelle formation and
aniline rich phase shows a greater enrichment of 1-hexane creating an intermediate phase consisting of IL microemulsion
compared to the experimental values. An overall rmsd (%) value (also known as micellar flooding).15 All the IL systems studied
of 3.84% is obtained for the HRL3E algorithm. The COSMO-SAC in the present work correspond to Winsor type III systems. ILs
predicted phase diagrams using the RRL3E and HRL3E algo- with substituted alkyl chain in the imidazolium ring [CXmim]+
rithms can be found in Fig. 3(g) and (h) respectively. and tetra-alkyl phosphonium [PXXXX]+ moieties (the subscript
Polyoxy-ethylene alcohols of the series CH3–(CH2)j1– ‘X’ refers to the chain length of the alkyl group) describing LLLE
(OCH2CH2)j–OH (abbreviated at CiEj systems) acts as bulk behavior have been studied in the present work. The structures
non-ionic surfactants in the separation of oil–water mixtures. of these ILs can be found in Table S4 of the ESI.† The nature
In the present study, system5 containing water + 2-butoxy- of ILs in regular solutions has been considered as consisting
ethanol (C4E1) + 1-dodecane has been considered.20 Phase of an equimolar mixture of cations and anions which exists
diagrams of COSMO-SAC predictions for system5 using the separately.14
RRL3E and HRL3E algorithms can be found in Fig. 3(i) and (j) IL systems with substituted imidazolium moieties include
respectively. Both approaches predict that the aqueous phase water + [C10mim][NTf2] + 1-dodecane (system6) and water +
exclusively consists of water although the experimental data [C12mim][NTf2] + 1-dodecane (system7) systems.21 These ILs

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have a charged imidazolium head connected with a ‘long-tail’
alkyl group which promotes aggregate formation with
1-dodecane + water mixtures. However, the method of oil–water
separation (as noted by Rodrı́guez-Palmeiro et al.21) for both ILs
are different i.e. [C10mim][NTf2] causes phase separation
without the aggregate formation, while [C12mim][NTf2] readily
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promotes micellar flooding. The possible reason is that even
if IL aggregates are formed above Critical Aggregate Concen-
tration (CAC), the attractive forces between the alkyl groups
of [C10mim][NTf2] are not strong enough to promote stable
micelle formation.36 The IL-rich phase in these systems is
heavier than the water and 1-dodecane exclusive phases (having
r 4 1.05 g cm3). These systems have a hydrocarbon top phase,
an aqueous middle phase and an IL-rich bottom phase. For
system6, COSMO-SAC predictions using RRL3E and HRL3E
algorithms describe overall rmsd (%) values of 6.63% and
2.04% respectively. Using the RRL3E approach, the correct
trend of temperature dependency for the IL-rich phase is not
observed in general. The predicted phase diagrams with RRL3E
algorithm almost coincide with each other as seen from Fig. 3(k).
For the HRL3E algorithm, better reproduction of the three-phase
region is observed at various temperatures as depicted in Fig. 3(l).
For system7, the COSMO-SAC predicted phase diagrams using
RRL3E and HRL3E algorithms can be found in Fig. 3(m) and (n)
respectively. Overall rmsd (%) values for system7 using RRL3E
and HRL3E algorithm are obtained as 7.13% and 4.46% respec-
tively. The increased deviations using the RRL3E approach results
from the overestimation of IL-component in the IL-rich phase
within the COSMO-SAC model.14
Two ternary systems having ILs with tetra-alkyl phos-
phonium moieties include: water + [P66614][DCA] + 1-dodecane
(system8) and water + [P66614][NTf2] + 1-dodecane (system9)
systems.22,23 The common mechanism of phase separation
for these systems is through the formation of a middle layer
comprising of an IL microemulsion which separates the
1-dodecane top phase and aqueous bottom phase. For system8,
overall deviations to the COSMO-SAC predictions are noted as
8.07% and 5.09% for the RRL3E and the HRL3E algorithms
respectively. The corresponding phase diagrams can be seen
from Fig. 3(o) and (p) respectively. With the RRL3E algorithm,
a larger triphasic region is seen for system8 due to the over-
estimation of the IL component in the IL-excess phase. For the
HRL3E algorithm, the predicted triphasic region is smaller
than the experimental envelop.
COSMO-SAC predictions for system9 shows increased devia-
tions due to the extremely hydrophobic nature of the [P66614]+
moiety.37 Overall rmsd (%) values of 6.04% and 10.21% have
been recorded using the RRL3E and HRL3E algorithms respec-
tively. The predicted phase diagram using the RRL3E algorithm
(Fig. 3(q)) shows accurate compositions for the IL rich phase
while depicting a residual IL fraction in the aqueous phase. For
the HRL3E algorithm, the predicted compositions of the IL-rich
and aqueous phases lie extremely close to each other thus
describing a pseudo two phase behavior which is observed from
Fig. 3(r). The [P66614]+ cation induces greater interaction with
1-dodecane while the anion [NTf2] forms 1 : 2 H-bonded
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complexes in the IL-rich phase having the structure anion–
H2O–anion.36 It has been reported by Zhang et al.36 that
aqueous solubility of an IL depends on its anionic structure,
[NTf2] due to the presence of two sulphonyl groups is a strong
H-bond donor that solubilizes a large quantity of water in the
IL-rich phase. Prediction of activity coefficients using the
COSMO-SAC model is challenging in this case because the IL
[P66614][NTf2] has an affinity for both hydrophobic and hydro-
philic constituents of the system. From the overall results of
COSMO-SAC predictions for the ternary systems having IL
constituents, it can be asserted that the HRL3E algorithm
performs better than the RRL3E algorithm, producing better
tie-line slopes and reasonably accurate three-phase zones when
compared to the RRL3E algorithm.
3.1.3. COSMO-SAC predictions of quaternary LLLE systems.
Two quaternary systems studied in the present work include:
1-heptane + aniline + 1-hexane + water (system10) and
1-heptane + aniline + water + benzene (system11). The experi-
mental data for these systems have been obtained from pre-
vious quaternary LLLE experiments by Frolkova et al.19
To conveniently represent the triphasic region for these
systems, we have used a pseudo-component approximation
where components of similar chemical nature are grouped
together. Using this approach, the LLLE regions are plotted
in terms of varying feed component fractions. For system10,
1-heptane and 1-hexane have been grouped together as pseudo-
components and the corresponding tie-triangles are repre-
sented in terms of the feed heptane fraction (Mheptane) which
ranges from 0.1 to 0.85 and is given by the following expression:
zheptane
Mheptane ¼ (32)
zheptane þ zhexane
Similarly, for system11, benzene and aniline are treated
as pseudo-components and corresponding tie-triangles are
represented in terms of the feed aniline fraction (Maniline) which
ranges from 0.75 to 0.94. COSMO-SAC predictions of the LLLE
behavior of system10 can be seen from Fig. 4(a) and (b) for the
RRL3E and HRL3E approaches respectively. While the same for
system11 can be seen from Fig. 4(c) and (d) respectively.
In general, the predictions using RRL3E algorithm shows lower
overall deviations (rmsd (%)) for both systems which are
recorded as 1.18% and 1.81% for system10 and system11
respectively. The use of HRL3E algorithm with the COSMO-SAC
model results in a substantial increase in qualitative deviations of
the predicted compositions. Overall rmsd (%) values of 3.34% and
4.05% are noted for system10 and system11 respectively using the
HRL3E algorithm.
3.2. Comparison of GA-NRTL and GA-UNIQUAC models with
the COSMO-SAC model and literature
For evaluating the influence of the thermodynamic model on
the proposed LLLE computation algorithms, we have used
the Genetic Algorithm (GA) promoted NRTL (GA-NRTL) and
UNIQUAC (GA-UNIQUAC) models. The RRL3E algorithm is
used as the flash method for GA-NRTL and GA-UNIQUAC
correlations. Stochastic global optimization of a suitable
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objective function is performed by GA to estimate the binary
interaction parameters required within the GA-NRTL and
GA-UNIQUAC models.38 The relevant objective function used
in the present work is given below as:
N X
X II X
m 
minfFðyÞg ¼ Wikj xjcalc;i;k  xjexpt;i;k
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structural parameters (r and q) are predicted a priori from
Polarizable Continuum Model (PCM) calculations.38 GEnerating
POLyhedra (GEPOL) algorithm is used for creating the PCM cavity
based on the concept of solvent excluded surface.39 The relevant
values of the UNIQUAC structural parameters (r and q) have been
2 tabulated in Table S11 of the ESI.† Using the RRL3E algorithm,

(33)
i¼1 j¼1 k¼1
the GA-NRTL and GA-UNIQUAC models reproduce the experi-
mental three-phase zone with very high accuracy. A comparison of
the correlative models used in the present work with the literature
The equation minimizes the square of the differences
approaches has been provided in Table 4. COSMO-SAC predic-
among experimental and calculated compositions denoted by
tions using the RRL3E and HRL3E approaches have been
x jexpt,i,k and x jcalc,i,k respectively. W jik is a weight factor and has
included in this comparison. The results indicate that using the
been set to unity for the present case.38 The phase diagrams for
GA-NRTL and GA-UNIQUAC models with the RRL3E algorithm
GA-NRTL and GA-UNIQUAC correlations for the ternary LLLE
produce more accurate and quantitative representation of the
systems can be found in Fig. S1 of the ESI.† While the same for
LLLE region as compared to the literature.15–20 For the ternary
quaternary LLLE systems can be found in Fig. S2 of the ESI.†
LLLE systems, average overall rsmd (%) values of 0.347% and
The binary interaction parameters of the GA-NRTL and
0.343% are observed for the GA-NRTL and GA-UNIQUAC models
GA-UNIQUAC models for the ternary LLLE systems can be
respectively. For the quaternary LLLE systems, the GA-NRTL and
found in Tables S5 and S6 of the ESI† respectively. For the
GA-UNIQUAC models describe average overall rmsd (%) values of
quaternary LLLE systems, binary interaction parameters of the
0.845% and 0.045% respectively. The GA-UNIQUAC model takes
GA-NRTL and GA-UNIQUAC models have been presented in
into account the entropic contributions to phase equilibria which
Tables S7 and S8 of the ESI.† Since the RRL3E algorithm
is significant for these systems which also explains the lower
describes the overall LLLE behavior based on two simultaneous
overall deviations observed when compared to the GA-NRTL
LLE systems (LTLME and LMLBE, where T, M and B denote the
model. Since, both GA-NRTL and GA-UNIQUAC are correlative
top, middle and bottom phases respectively), two sets of binary
models, they show much lower deviations than the predictive
interaction parameters are obtained corresponding to LTLME
COSMO-SAC model.
and LMLBE systems. In theory, it is possible to use a single set of
parameters for correlating the entire LLLE region, however
such approaches would require a different objective function
with a separate three-phase flash algorithm. It might be possible
4. Conclusions
to adapt the three-phase HRL3E flash algorithm for such a In the present work, the COSMO-SAC model was employed
purpose however, it would require new ways of initializing a from to predict the activity coefficients of nine ternary and two
b and vice-versa (eqn (22) and (26) respectively) since accurate quaternary LLLE systems. The computational approaches
KHB2 O , KHH2 O and gBH2 O values are needed in advance which is not namely the Rachford–Rice LLLE (RRL3E) and Henley–Rosen
possible for a correlative method. Overall deviations for LLLE LLLE (HRL3E) algorithms were adopted in this work. Both
correlations have been recorded in terms of rmsd (%). Their RRL3E and HRL3E algorithms successfully predicted the phase
values can be found in Tables S9 and S10 of the ESI† for behavior of all systems with overall rmsd (%) values of less than
GA-NRTL and GA-UNIQUAC models respectively. The UNIQUAC 5%. The phase behavior predicted using the RRL3E algorithm

Table 4 Comparison of GA-NRTL (RRL3E) and GA-UNIQUAC (RRL3E) models with literature approaches. (COSMO-SAC predicted data using the RRL3E
and HRL3E algorithms also included for comparison)

COSMO-SAC prediction LLLE correlation rmsd (%)

rmsd (%) (present work) (present work)
System Correlative Reported
number System model used rmsd (%) RRL3E HRL3E GA-NRTL GA-UNIQUAC Ref.
a
1 1-Decane + water + triacetin NRTL 0.94 0.71 6.06 0.249 0.014 16
2 1-Hexadecane + water + triacetin NRTL; UNIQUAC 1.96a; 4.46a 6.09 1.86 0.013 0.009 17
3 Aniline + 1-octane + water NRTL; UNIQUAC N.R.; N.R. 1.99 4.80 2.117 2.960 18
4 1-Hexane + aniline + water NRTL 2.44 3.25 3.84 0.087 0.000 19
5 Water + C4E1 + 1-dodecane UNIQUAC 3.34 5.08 7.39 0.245 0.071 20
6 Water + [C10mim][NTf2] + 1-dodecane NRTL 0.24b 0.63 2.04 0.002 0.002 15
7 Water + [C12mim][NTf2] + 1-dodecane NRTL 0.46b 7.13 4.46 0.001 0.001 15
8 Water + [P66614][DCA] + 1-dodecane NRTL 0.71b 8.07 5.09 0.275 0.001 15
9 Water + [P66614][NTf2] + 1-dodecane NRTL 0.25b 6.04 10.21 0.135 0.026 15
10 1-Heptane + aniline + 1-hexane + water N.A. N.A. 1.18 3.34 0.986 0.044 19
11 1-Heptane + aniline + water + benzene N.A. N.A. 1.81 4.05 0.663 0.047 19
Average 4.362 4.831 0.434 0.288 —

N.R.: Not Reported; N.A.: Not Available. a Deviations are reported in terms of Standard Deviations (SD). b
Mean deviations reported in terms of
mole percentages (expression not reported).

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was 3.79% more accurate as compared to the HRL3E algorithm.
However, in addition to predict the local compositions of the
LLLE regions, the HRL3E algorithm was also able to predict the
individual phase splits of the triphasic regions. Additionally,
classical thermodynamic models namely, GA-NRTL and
GA-UNIQUAC models were employed to correlate the LLLE data
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using the RRL3E algorithm. These results were benchmarked
against the available literature approaches and were able to
reproduce the LLLE regions with higher quantitative accuracy.
From a computational efficiency stand-point, the RRL3E algo-
rithm was preferred due to fewer simplifications and slightly
higher overall accuracy as compared to the HRL3E algorithm.
Overall, a priori prediction of the phase behavior of Treybal
type III and Winsor type III systems initiates design aspects of
extraction equipment experiencing three-phase behavior.
To that end, COSMO-SAC based method can be used for the
rapid qualitative screening of multicomponent mixtures for
complex LLLE phenomena prior to detailed experimentation.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
The authors acknowledge the computational resource of the
Param-Ishan Supercomputing facility at the Indian Institute of
Technology Guwahati for the quantum chemical calculations.
One of the authors, Mr. Priyotosh Bairagya gratefully acknowl-
edges the funding of the TEQIP-III vide IITG/CET/TEQIP-III/CR/
2018-19/6.
Notes and references
1 R. E. Treybal, Liquid Extraction, McGraw-Hill, New York,
2nd edn, 1963.
2 P. A. Winsor, Solvent Properties of Amphiphilic Compounds,
Butterworth, London, 1st edn, 1954.
3 X. He, K. Huang, P. Yu, C. Zhang, K. Xie, P. Li, J. Wang, Z. An
and H. Liu, Chin. J. Chem. Eng., 2012, 20, 27–35.
4 J. J. Krueger, M. D. Amiridis and H. J. Ploehn, Ind. Eng.
Chem. Res., 2001, 40, 3158–3163.
5 V. Nardello-Rataj, L. Caron, C. Borde and J.-M. Aubry, J. Am.
Chem. Soc., 2008, 130, 14914–14915.
6 C. Zhang, K. Huang, P. Yu and H. Liu, Sep. Purif. Technol.,
2013, 108, 166–173; C. Sosa, J. Andzelm, B. C. Elkin,
E. Wimmer, K. D. Dobbs and D. A. Dixon, J. Phys. Chem.,
1992, 96, 6630–6636.
7 R. P. Stateva, G. S. Cholakov, A. A. Galushko and W. A.
Wakeham, Chem. Eng. Sci., 2000, 55, 2121–2129.
8 A. Lucia, L. Padmanabhan and S. Venkataraman, Comput.
Chem. Eng., 2000, 24, 2557–2569.
9 P. Lang and M. Lang-Lazi, IChemE Symp. Ser., 2006, 152,
877–890.
This journal is © the Owner Societies 2020
View Article Online
Paper
10 A. Marcilla, M. M. Olaya, M. D. Serrano, R. Velasco and
J. A. Reyes-Labarta, Fluid Phase Equilib., 2009, 281, 87–95.
11 S.-T. Lin and S. I. Sandler, Ind. Eng. Chem. Res., 2002, 41,
899–913.
12 D. Kundu and T. Banerjee, Ind. Eng. Chem. Res., 2011, 50,
14090–14096.
13 P. Bairagya, D. Kundu and T. Banerjee, Asia-Pac. J. Chem.
Eng., 2020, e2513, DOI: 10.1002/apj.2513.
14 A. Bharati, D. Kundu, D. Rabari and T. Banerjee, Phase
Equilibria in Ionic Liquid Facilitated Liquid-Liquid Extractions,
CRC Press, Boca Raton, 1st edn, 2017.
15 I. Rodrı́guez-Escontrela, A. Arce, A. Soto, A. Marcilla,
M. M. Olaya and J. A. Reyes-Labarta, Phys. Chem. Chem.
Phys., 2016, 18, 21610–21617.
16 E. D. Revellame, W. E. Holmes, R. Hernandez, W. T. French,
L. Lerma, A. Forks, T. Ashe and L. A. Estévez, J. Chem.
Thermodyn., 2013, 67, 21–27.
17 E. D. Revellame, W. E. Holmes, R. Hernandez, W. T. French,
A. Forks, T. Ashe and L. A. Estévez, J. Chem. Thermodyn.,
2016, 95, 105–110.
18 A. Grenner, M. Klauck, R. Meinhardt, R. Schumann and
J. Schmelzer, J. Chem. Eng. Data, 2006, 51, 1009–1014.
19 A. V. Frolkova, A. A. Akishina, A. K. Frolkova and E. V.
Illarionova, J. Chem. Eng. Data, 2017, 62, 1348–1354.
20 B.-J. Lin and L.-J. Chen, J. Chem. Eng. Data, 2002, 47,
992–996.
21 I. Rodrı́guez-Palmeiro, O. Rodrı́guez, A. Soto and C. Held,
Phys. Chem. Chem. Phys., 2015, 17, 1800–1810.
22 I. Rodrı́guez-Escontrela, I. Rodrı́guez-Palmeiro, O. Rodrı́guez,
A. Arce and A. Soto, Fluid Phase Equilib., 2015, 405, 124–131.
23 S. Lago, B. Rodrı́guez-Cabo, A. Arce and A. Soto, J. Chem.
Thermodyn., 2014, 75, 63–68.
24 R. Dennington, T. Keith and J. Millam, GaussView (Version 5),
Semichem Inc., Shawnee Mission, KS, 2009.
25 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin,
V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene,
J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,
R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,
K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador,
J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas,
J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox,
Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT,
2013.
26 A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652.
27 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B: Condens. Matter
Mater. Phys., 1988, 37, 785–789.
Phys. Chem. Chem. Phys., 2020, 22, 22023--22034 | 22033

Paper
28 J. P. Perdew, Phys. Rev. B: Condens. Matter Mater. Phys., 1986,
33, 8822–8824.
29 A. Schäfer, H. Horn and R. Ahlrichs, J. Chem. Phys., 1992, 97,
2571–2577.
30 C. Sosa, J. Andzelm, B. C. Elkin, E. Wimmer, K. D. Dobbs
and D. A. Dixon, J. Phys. Chem., 1992, 96, 6630–6636.
Published on 17 September 2020. Downloaded by Auckland University of Technology on 11/6/2020 1:57:34 AM.
31 A. Klamt, J. Phys. Chem., 1995, 99, 2224–2235.
32 A. Klamt and G. Schüürmann, J. Chem. Soc., Perkin Trans. 2,
1993, 799–805.
33 V. R. Sampath and S. Leipziger, Ind. Eng. Chem. Process Des.
Dev., 1985, 24, 652–658.
34 B.-S. Lee and S.-T. Lin, Ind. Eng. Chem. Res., 2015, 54,
9005–9012.
22034 | Phys. Chem. Chem. Phys., 2020, 22, 22023--22034
View Article Online
PCCP
35 C.-K. Chang and S.-T. Lin, J. Chem. Eng. Data, 2020, 65,
1019–1027.
36 K. Dong, G. Garau, B. Han, Y. Hu, H. Li, X. Lu, T. Mu,
X. Peng, R. D. Rogers, H. Wang, H. Wang, J. Wang, Q. Qang,
S. Zhang and Q. Zhou, Structures and Interactions of Ionic
Liquids, Springer-Verlag, Berlin, 1st edn, 2014.
37 M. G. Freire, P. J. Carvalho, R. L. Gardas, L. M. N. B.
F. Santos, I. M. Marrucho and J. A. P. Coutinho, J. Chem.
Eng. Data, 2008, 53, 2378–2382.
38 M. K. Singh, T. Banerjee and A. Khanna, Comput. Chem.
Eng., 2005, 29, 1712–1719.
39 T. Banerjee, M. K. Singh, R. K. Sahoo and A. Khanna, Fluid
Phase Equilib., 2005, 234, 64–76.
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