Correlation

Cite This: Ind. Eng. Chem. Res. 2019, 58, 4341−4353 pubs.acs.org/IECR

Modeling the Water Solubility in Imidazolium-Based Ionic Liquids

Using the Peng−Robinson Equation of State
Jeremías Martínez,†,‡ María A. Zúñiga-Hinojosa,§ and Ricardo Macías-Salinas*,§
†
Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón y Paseo Tollocan S/N, Toluca, Estado de México
C.P. 50120, México
‡
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco, km 14.5, Toluca,
Estado de México C.P. 50200, México
§
Instituto Politécnico Nacional, Departamento de Ingeniería Química, ESIQIE, Ciudad de México, Mexico City C.P. 07738, México
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ABSTRACT: Ionic liquids (ILs), which are also known as liquid salts or ionic
fluids, are organic salts with a low fusion point. They behave as a liquid at low
temperature or ambient temperature. Accordingly, they are prominent solvents
to be used in the green chemical processes, because of their attractive
physicochemical properties such as low vapor pressure, high thermal stability,
an excellent solvation behavior, and high gas solubility. Recently, various
experimental researches have reported the water solubility in different
imidazolium-based ILs at different temperature, pressure, and composition
conditions. In this study, we present the modeling of the vapor−liquid
equilibrium of the H2O−IL system using the Peng−Robinson cubic equation
of state (EoS), coupled with the Wong-Sandler mixing rules; eight binary
systems were studied for this purpose. In addition, improved temperature-
dependent parameters were introduced into the EoS as those proposed by
Stryjek and Vera for water [Can. J. Chem. Eng. 1986, 64, 323] and by Yokozeki
for the IL [Int. J. Thermophys. 2001, 22, 1057]. The studied ILs were [CxMIM][Cl] (x = 2, 4, 6), [C4MIM][PF6],
[C2MIM][BF4], [C4MIM][BF4], [OHC2MIM][BF4], and [OHC2MIM][Cl]. The obtained results showed a satisfactory
agreement between the experimental and the calculated solubility data using the present modeling approach under different
conditions of temperature, pressure, and composition.

■ INTRODUCTION
Ionic liquids (ILs) have recently attracted the attention within
the research and industrial community, since they are
considered as new potential solvents for replacing the
traditional organic solvents. They present an extremely low
vapor pressure, which prevents their evaporation at room
conditions; accordingly, ILs are called “green solvents.”1,2
Other properties include their high thermal stability and their
high capacity for solubilizing several gases; in addition, they
remain in a liquid state over a wide range of temperatures. In
this context, the vapor−liquid equilibrium (VLE) of the H2O−
IL system has potential applications in different separation
process, e.g., the extractive distillation (breaking azeo-
tropes),2−6 and absorption.7 ILs could be also used in
refrigeration and air conditioning industries, in which
refrigerant−absorbent pairs such as H2O−LiBr and H2O−
NH38,9 are commonly used. Traditional refrigerant−absorbent
pairs have some disadvantages such as crystal formation,
toxicity, and flammability.10 Several studies have shown that
ILs can be used in the gas industry to prevent hydrate
formation, since they modify the dissociation equilibrium curve
of gas hydrates. That is, ILs show a dual function: behaving
simultaneously as thermodynamic and kinetic inhibitors.7,11−13
This peculiar characteristic is due to a strong electrostatic
charge and a high tendency to create hydrogen bonds.11
ILs are organic salts formed by large and asymmetric organic
cations, e.g., imidazolium cation, bonded to alkyl groups, and
organic and inorganic anions. Therefore, synthesizing a
significant amount of ILs for fitting some physicochemical
properties is possible.14,15 The physical and chemical proper-
ties of ILs present many advantages over traditional solvents.
Accordingly, it is necessary to have a vast knowledge of ILs
before overtaking in a process at the industrial scale. However,
to create an extensive phase equilibrium database of H2O−IL
systems, it is necessary to perform an extensive experimental
investigation; consequently, this is time- and money-consum-
ing. In this context, modeling is of vital importance, allowing
one to calculate and predict physicochemical properties, and
the phase equilibrium behavior. Despite the complexity in
predicting the water solubility in the ionic liquids, several
thermodynamic models have been used, such as activity
coefficient models, equations of state (EoS), and unimolecular
Received: October 18, 2018
Revised: January 10, 2019
Accepted: February 15, 2019
Published: February 15, 2019

© 2019 American Chemical Society 4341 DOI: 10.1021/acs.iecr.8b05153

Ind. Eng. Chem. Res. 2019, 58, 4341−4353
Industrial & Engineering Chemistry Research Correlation

quantum chemical calculations. Calvar et al.3 and Carvalho et ylimidazolium tetrafluoroborate [OHC2MIM][BF4]; and 1-(2-
al.16 used the Nonrandom Two-Liquid (NRTL) model to hydroxyethyl)-3-methylimidazolium chloride [OHC2MIM]-
correlate the experimental data of the H2O−[CxMIM][Cl] (x [Cl].
= 2, 4, 6) systems, obtaining absolute average deviation (AAD)
values of <1%. Whereas, Yokozeki and Shiflett17,18 used the
Redlich−Kwong EoS19 with the empirical modification in the
■ DESCRIPTION OF THE MODEL
The vapor−liquid phase behavior between water and IL was
temperature-dependent parameter of the pure component, and determined by the PR EoS,31 expressed as
the modified van der Waals-Berthelot mixing rule.20 Vetere21
calculated the critical properties of ILs by using a RT a(T )
P= −
compressibility factor of 0.256. The solubilities of the v−b v(v + b) + b(v − b) (1)
[C2MIM][BF4] and [C4MIM][BF4] ILs in water were
where a and b are the constants for pure components given by
predicted with AAD values of <0.02%.
The Statistical Associating Fluid Theory (SAFT) proposed RTc
a = 0.45723552821 α(T )
by Chapman et al.22 and Huan and Radosz23 in their variations Pc (2)
have also been used for several research groups to model the
H2O−IL solution. Passos et al.24 applied the PC-SAFT and
approach for calculating water solubility in diverse ILs using RTc
the cation [C4MIM+] as a base. In this case, ILs were b = 0.077960739039
Pc (3)
considered as associating species with two association sites.
The model parameters were calculated by simultaneous 35
The Soave correlation is defined as
adjustment to pure ILs densities, water activity coefficients at
T
298.15 K, and VLE experimental data at 0.1 MPa. Their results α(T ) = [1 + κ(1 − Tr 0.5)] , Tr ≡
showed a satisfactory agreement between the experimental and Tc (4)
calculated data obtaining AAD values between 1.01 and 7.85. where κ is only a function of the acentric factor ω. To model
Vega et al.25,26 modeled the water−IL system using the soft- the water, we use the Stryjek and Vera32 expression, in which
SAFT equation, where the IL was considered as a homonuclear the κ parameter was modified:
chain, i.e., cation and anion as one molecule with a specific
association number of sites; independently, the alkyl chain κ = κ0 + κ1(1 + Tr 0.5)(0.7 − Tr) (5)
length in imidazolium cation and the corresponding anion
were modeled. With regard to the equation parameters of the where
model for the system [CxMIM][Cl] (x = 2, 4, 6), the segment κ0 = 0.378893 + 1.4897153ω − 0.17131848ω2 + 0.0196554ω3
diameter parameter was set at an average value, whereas a (6)
variation in the chain length and the dispersive energy
κ1 has a specific value for pure components, i.e., when the
parameters were observed as the alkyl chain length of the
critical properties and the acentric factor of the components
cation increased. In this particular case, the AAD value
were known, the experimental vapor pressures were fitted to
obtained by Vega et al. was 0.1%.25,26 Freire et al.27 modeled
obtain the κ1 value (see Table 1). For water, the κ1 and ω
the H2O−[C4MIM][BF4] and H2O−[C4MIM][PF6] systems values are −0.06635 (ref 32) and 0.3438, (ref 36), respectively.
using the Conductor-like Screening for Real Solvents The following modification in the temperature-dependent a
(COSMO-RS) model; nevertheless, they only showed parameter of the pure component in the PR EoS17,18 was used
qualitative results. This model, based on the statistical for the eight ILs:20
i Tc T yzz
∑ βkjjjjj
thermodynamics, calculates the chemical potential of any

z
Tc zz{
species in any mixture and does not have a concentration ≤3 k

dependency in the excess Gibbs free-energy function
(UNIFAC).28 In contrast, Zhou et al.29 and Khan et al.30
obtained results with a better precision using COSMO-RS.
In the present work, we calculated the water solubility in
imidazolium-based ILs using the Peng−Robinson equation of
state (PR EoS)31 at different temperature, pressure, and
composition conditions. Regarding the proposed modeling
approach for the H2O−IL systems, we incorporated in the PR
EoS the modification in the temperature-dependent parameter
a (cohesive energy) of the pure IL, as suggested by Yokozeki,20
whereas, we included the α expression of Stryjek and Vera for
water.32 Furthermore, we applied the Wong-Sandler (WS)
modern mixing rules33 in combination with the UNIQUAC
model34 for estimating the excess free energy. In this modeling
effort, the studied ILs were 1-ethyl-3-methylimidazolium
chloride, [C2MIM][Cl]; 1-butyl-3-methylimidazolium chlor-
ide, [C4MIM][Cl]; 1-hexyl-3-methylimidazolium chloride,
[C6MIM][Cl]; 1-butyl-3-methylimidazolium hexafluorophos-
phate, [C4MIM][PF6]; 1-ethyl-3-methylimidazolium tetra-
fluoroborate, [C2MIM][BF4]; 1-butyl-3-methylimidazolium
tetrafluoroborate [C4MIM][BF4]; 1-(2-hydroxyethyl)-3-meth-
4342
kT
α (T ) = −
k=0 (7)
The critical properties were taken from Valderrama et al. The 38
authors calculated such properties using a group contribution
method (see Table 1); the βk values presented in this work
were fitted to PTx experimental solubility data of each binary
system. We observed that β0 values approach to one; while, β2
and β3 values did not significantly affect the vapor−liquid
equilibrium calculations. So that, in the temperature dependent
correlation β1 was the only adjustable parameter, which will be
further discussed. Therefore, we applied the equation proposed
by Yokozeki in solubility calculations.20
ij T T yz
α(T ) = 1 + β1jjj c − zzz
jT Tc z{
k
(8)
On the other hand, Wong and Sandler33 proposed a set of
mixing rules to better represent the nonideal behavior of
mixtures such as the water−ILs system. These mixing rules
combine an excess free-energy model with a cubic EoS to
produce the desired EoS behavior at both low and high
DOI: 10.1021/acs.iecr.8b05153
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Table 1. Properties of Pure Components

component Tc [K] Pc [bar] r q q′
H2O 647.286a 220.8975a 0.920b 1.400b 1.000b
[C2MIM]Cl 748.6 34.17 12.089 10.488 7.489
[C4MIM]Cl 789.0 27.85 13.438 11.568 8.256
[C6MIM]Cl 829.2 23.50 14.787 12.648 9.031
[C4MIM][PF6] 719.4 17.28 17.405 11.006 7.858
[C2MIM][BF4] 596.2 23.59 13.808 8.550 6.105
[C4MIM][BF4] 643.2 20.38 15.157 9.630 6.876
[OHC2MIM][BF4] 691.7 24.67 14.582 9.442 6.742
[OHC2MIM]Cl 832.1 36.21 12.862 11.380 8.126
a
Poling et al.36 bPrausnitz et al.37

densities without being density-dependent. These rules allow
extrapolation over a wide range of temperature and pressure.
WS mixing rules are based on two significant observations. The
first states that the van der Waals one-fluid mixing rules (eqs 9
and 10) are sufficient conditions to ensure the proper
composition dependence of the second virial coefficient (eq
11) and that they are not necessary conditions, since they
impose constraints on the a and b parameters to satisfy eq 12.
a= ∑ ∑ xixjaij
i j
where AEEoS represents the excess Helmholtz free energy
derived from an EoS, whereas, the AEγ and GEγ expressions refer
to excess free energies derived from an activity coefficient
model.
In the WS mixing rules context, for the infinite pressure limit
of an EoS, the molecules in the liquid solution are assumed to
be so tightly packed that there is no free volume, i.e., lim v =
P →∞
b.
Finally, from the above set of equations, Wong and
Sandler33 obtained the following expressions for am and bm:
i D yz
am = RT ·Q jjj
(9)

zz
∑ ∑ xixjbij k1 − D {
b= (16)
i j (10)
Q
B(x , T ) = ∑ ∑ xixjBij(T ) bm =
1−D (17)
i j (11)

i a y
∑ xixjjjjb − zzz
where

k RT {ij
a am
bm − m = ∑ Q = bm −
RT i j (12) RT (18)

i ai yz
∑ xijjjjj zz + G
z
z
To apply the combining rule (eq 12), an interaction parameter, E

k bi RT { C RT
kij, is introduced as follows: D=

ij a yz
(19)

jjb − zz =
ai aj
bi − ( ) + (bj − RT ) (1 − k )
k RT {ij
RT
ij
where C is an EoS-specific constant that is dependent on the
2 (13) used EoS; the C value for PR EoS is [ln( 2 − 1)]/ 2 .
To calculate the excess Gibbs free energy for water−IL
Note that the composition dependence of the second virial systems, the UNIQUAC equation34 was used:
coefficient, that is, the limit condition to low density, is
satisfied. Moreover, eq 12 does not provide any relationship to GE GE,combinatorial GE,residual
calculate the a and b parameters separately, but only for the = +
RT RT RT (20)
sum (b − a/RT); thus, an additional equation is needed.
The second observation indicates that the excess of the where the combinatorial term describes the dominant entropic
Helmholtz free energy of a mixture is less pressure dependent contribution (eq 21); which consists of two compositional
than the excess Gibbs free energy, i.e., variables: area fraction θ, and segment fraction ϕ, i.e.,
combinatorial part is determined by the composition, and
GE(T , P = low, xi) = AE(T , P = low, xi) molecular shape and size only. Moreover, z, is the coordination

ÅÄÅ É
= AE(T , P = ∞ , xi) number (equal to 10).
ij θ yzÑÑÑÑ
(14)
ji ϕ zy ji ϕ zy z ÅÅ ij θ yz
= x1 lnjjjj 1 zzzz + x 2 lnjjjj 2 zzzz + ÅÅÅÅx1q1 lnjjjj 1 zzzz + x 2q2 lnjjjj 2 zzzzÑÑÑÑ
k x 2 { 2 ÅÅÅÇ j ϕ1 z j ϕ2 zÑÑ
The first term comes from the fact that GE = AE + PvE, and the GE,combinatorial
PvE expression is negligible at low pressures; whereas, the RT k x1 { k { k {ÑÖ
second one is a result of the essential pressure independence of (21)
AE term at high densities. Accordingly, the second equation for
where the segment fraction, ϕ, and area fractions θ and θ’ are
a and b parameters comes from the condition
given by
E
AEoS (T , P = ∞ , x) = A γE(T , P = ∞ , x) xiqi
θi = i , j = 1, 2
= A γE(T , P = low, x) = GγE(T , P = low, x) (15) xiqi + xjqj (22)

4343 DOI: 10.1021/acs.iecr.8b05153

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Table 2. Experimental H2O Solubilities in Different Ionic Liquids (ILs)

x-H2O
ionic liquids T [K] P [bar] maximum source
[C2MIM]Cl 355.58−409.3, 364.02−421.93, 373.66−435.03 0.5, 0.7, 1.0 0.998 Carvalho et al.16
[C4MIM]Cl 354.92−405.02, 363.49−414.97, 372.66−429.69 0.5, 0.7, 1.0 0.988 Carvalho et al.16
[C6MIM]Cl 354.64−383.26, 363.46−393.61, 373.13−405.3, 0.5, 0.7, 1.0, 1.01 0.998 Carvalho et al.,16
373.3−415.51 Calvar et al.41
[C4MIM][PF6] 283.1, 298.15, 323.15 0.002−0.010, 0.002−0.020, 0.005−0.050 0.151 Anthony et al.42
[C2MIM][BF4] 323.15, 328.15, 333.15 0.057−0.097, 0.073−0.124, 0.094−0.159 0.8 Han et al.43
373.15 0.025−0.756 0.778 Jork et al.5
[C4MIM][BF4] 308.17−443.65, 298.16−433.68, 285.13−433.92, 0.008−0.520, 0.013−1.228, 0.009−2.001, 0.582 Guan et al.44
284.95−433.28 0.011−3.192
[OHC2MIM][BF4] 392.6−464.8, 403.0−427.4, 361.6−402.2, 0.122−0.879, 0.483−1.008, 0.267−1.0, 0.8 Kim et al.45
325.8−383.8 0.092−0.988
[OHC2MIM]Cl 318.57−398.32, 314.82−391.60, 300.73−380.1, 0.033−0.805, 0.041−1.023, 0.028−1.011, 0.988 Nie et al.46
301.40−375.60, 301.87−373.56 0.036−1.008, 0.039−1.008

xiqi′ purposes of the H2O−IL systems. We present in, Table 2, the

θi′ = i , j = 1, 2 corresponding temperature and pressure ranges, the maximum
xiqi′ + xjq′j (23) H2O solubility measured, and the source of the experimental
xiri solubility data for all ILs considered in this study. As shown in
ϕi = i , j = 1, 2 Table 2, the temperature range is moderate (283.15−443.15
xiri + xjrj (24) K), whereas the pressure range is low (0.008−3.192 bar). The
Parameters r, q, and q’ are pure-component molecular maximum H2O solubility is reported for the H2O−IL−Cl−
structural constants, which are dependent on the molecular system at a water molar fraction of 0.998.
size and external surface areas. The UNIQUAC structural The simplex optimization procedure of Nelder and Mead47
parameters of the ionic species were obtained from Lei et al.,39 was used in the computations for searching the minimum of
by correlating the activity coefficients of solutes at infinite the following objective functions, according to the reported
dilution in ILs at different temperatures; whereas the r and q experimental data:
values for water were taken from Prausnitz et al.37 With regard N N
to the q′ values of both ILs and water, these were estimated by min f = ∑ [P jexp − P jcalc]2 + ∑ [1 − yHcalcO,j ]2
following expression: 0.7 × q.37 j=1 j=1
2
(27)
On the other hand, the residual term mainly describes the
intermolecular forces that are responsible for the enthalpy of or
mixing and is given by N N

G E,residual min f = ∑ [T jexp − T jcalc]2 + ∑ [1 − yHcalcO,j ]2

= −q1x1 ln(θ1 + θ2τ2,1) − q2x 2 ln(θ2 + θ1τ1,2)
RT
where τ1,2 and τ2,1 are adjusted parameters, which are expressed
as a function of characteristic energies ΔUi,j:
ΔUi , j
ln τi , j = − i , j = 1, 2
RT
In most of the cases, the above equation gives the primary
effect of temperature on τi,j. This work aims to predict the
water solubility in ILs using the PR EoS coupled with WS
mixing rules. This modeling approach is restricted to β1
parameter first; subsequently, to both UNIQUAC parameters
(ΔU1,2 and ΔU2,1) and finally, to the interaction parameter for
the second virial coefficient k12 = k21. The above-mentioned
parameters were fitted to experimental solubility data. All
vapor−liquid equilibrium calculations were performed using
the phi-phi method. The required expressions for the fugacity
coefficients of each species in the mixture, based on Wong−
Sandler approach, are given elsewhere.33,40
j=1 j=1
2
(28)
(25)
where N is the number of experimental points, Pexp and Pcalc
are experimental and calculated pressures, Texp and Tcalc stand
for experimental and calculated temperatures, and ycalc
H2O is the
equilibrium composition of H2O in the vapor phase. Note that,
in this modeling approach, only water is considered in the
(26)
vapor phase. In a first attempt to obtain the value of the β1,
ΔU 1,2 , ΔU2,1 , and k 12 parameters, we correlated the
experimental solubilities at 298 K, as suggested by Macias- ́
48
Salinas. However, we found that the experimental solubility
data of the H2O−[C4MIM][PF6] system was only reported at
298 K in the literature. Therefore, we decided to use the
solubilities at the lowest temperature, pressure, or H2O molar
fraction, according to the available experimental data. We
found that the β1 value must be our priority, because of its
reasonable representation of the cohesive energy (α) for ILs.
Once optimized, β1 was set constant, and the ΔU1,2, ΔU2,1, and
k12 parameters were fitted using the same initial values in each
isotherm, isobar, or isopleth. Note that the ΔU1,2 and ΔU2,1

■ RESULTS AND DISCUSSION

The ILs considered in this work are based on the imidazolium
cation bonded to the [Cl−], [PF−6 ], and [BF−4 ] anions. In this
context, the anion plays a more significant role than the alkyl
chain length; in addition, the shape and size of the anion
determine its miscibility extent in a solvent.5 For modeling
4344
values showed similar values in each isobar of H2O−
[CxMIM][Cl] (x = 2, 4, 6) systems; therefore, we set either
ΔU1,2 or ΔU2,1 to optimize again the ΔU1,2 or ΔU2,1, and k12
parameters. When we obtained the suitable β1, ΔU1,2, and
ΔU2,1 values, we set them constant, and finally, we fitted the
k12 parameter. For purposes of modeling, we chose the
appropriate values of the adjusted parameters based on a k12
DOI: 10.1021/acs.iecr.8b05153
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value of <1 and the lowest percent absolute average deviation Figure 1 shows the experimental and calculated solubilities
(AAD%) for each water solubility in IL calculation. Table 3 with the present modeling approach for H2O−[CxMIM][Cl]
(x = 2, 4, 6) systems at 0.5, 0.7, and 1 bar. In Figure 1a, a
Table 3. Adjusted Parameters with the PR-WS Model for reasonable agreement is observed between the experimental
H2O−[CxMIM][Cl] (x = 2, 4, 6) Systems and calculated temperatures using the 3-methylimidazolium
cation and the chloride anion, irrespective of the alkyl chain
ionic liquid, IL [C2MIM]Cl [C4MIM]Cl [C6MIM]Cl total
length of the cation and pressure. A characteristic, per se, of the
Na 93 81 123 297 WS approach, consists of reproducing the desired equation of
β1 10.27 0.78 10.07 state behavior at both low and high densities without being
ΔU12 [cal/mol] −1512.82 −842.77 −612.67 density-dependent and allows extrapolation over a wide range
ΔU21 [cal/mol] 1209.13 −422.43 115.16 of temperature and pressure, as shown in Figure 1. Carvalho et
k1,2 0.663 0.876 0.810 al.16 showed in the vapor−liquid equilibrium for H2O−
AAD, T% 0.14 0.22 0.18 [CxMIM][Cl] (x = 2, 4, 6) systems that, as the alkyl chain
a
N = number of experimental points. length increases in the cation, the boiling points decrease,
because of weak solvation of the cations. This phenomenon
can be explained through the UNIQUAC model. As
shows the correlating results of the model parameters β1, mentioned above, the residual term (eq 25) describes the
ΔU1,2, ΔU2,1, and k12, and the AAD% between experimental intermolecular forces that are responsible for the enthalpy of
and calculated temperatures of H2O−[CxMIM][Cl] (x = 2, 4, mixing; whereas, the combinatorial term describes the entropic
6) systems. As can be seen, the β1 value for H2O− contribution, which is determined by the composition,
[C4MIM][Cl] is smaller than the β1 values for H2O− molecular shape, and size. Although the UNIQUAC model
[C2MIM][Cl] and H2O−[C6MIM][Cl] systems. We observed was not developed to describe the behavior of mixtures
an increase in ΔU1,2 values, as the alkyl chain length increases containing electrolyte species, it can be applied in systems of
in the 1-alkyl-3-methylimidazolium cation; whereas ΔU2,1 water with IL solutions, since, in ILs, the ion charge is usually
values do not show any tendency. Table 3 also shows k12 dispersed, and the long-range electrostatic forces are weak,
values, which are >0.5. In addition, the predictive capability of compared with the short-range intermolecular forces, so that
the modeling approach to represent the experimental data of they can be neglected. Figure 2 presents the analysis of the
the water solubility in ILs with the Cl− anion is rather good, enthalpic and entropic contributions for H2O−[CxMIM][Cl]
because of the maximum AAD value of 0.22%. (x = 2, 4, 6) systems using the UNIQUAC model at 1 bar. As

Figure 1. Solubility of the systems with the PR-WS model: (a) H2O−[C2MIM][Cl], (b) H2O−[C4MIM][Cl] at 0.5, 0.7, and 1.0 bar, and (c)
H2O−[C6MIM][Cl] at 0.5, 0.7, 1.0, and 1.01 bar. Symbols represent experimental data, and solid lines represent calculated data.

4345 DOI: 10.1021/acs.iecr.8b05153

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Industrial & Engineering Chemistry Research
Figure 2. Analysis of the entropic and enthalpic contributions for
H2O−[CxMIM][Cl] (x = 2, 4, 6) systems using the UNIQUAC
model at 1 bar.
can be seen in this figure, the water solubility in IL is
dependent on the enthalpic contribution noticeably. Fur-
thermore, all systems show an exothermic behavior,
irrespective of alkyl chain length of the imidazolium cation.
An examination of this figure also shows that, as the alkyl chain
length of cation increases, the enthalpic contribution increases,
while the entropic contribution decreases to a lesser extent. A
possible explanation is that the molecular interactions between
H2O and IL decrease as the size of IL increases, because of an
increase in the alkyl chain length cation, regardless of the Cl−
anion. Freire et al.27,49 showed that the decrease of the water
solubility in IL is due to the increase of hydrophobic character
of the cation, which is caused by the alkyl chain length.
Therefore, such behavior can be related to the decrease in the
polarity of the IL, no matter the type of anion. According to
Zhang et al.,50 a smaller alkyl chain length of the cation results
in a stronger interaction between water and IL. It can be seen
in Figure 2 that, as the molar fraction of the H2O increases, the
enthalpic contributions decrease up to a minimum value, and
subsequently, they approach zero, irrespective of alkyl chain
length of the cation. A maximum interaction exists between
H2O and the ILs: [C 2 MIM][Cl], [C4MIM][Cl], and
[C6MIM][Cl] at 0.69, 0.75, and 0.79 molar fraction of the
H2O, respectively. This behavior suggests that, at the molar
fractions above-mentioned, the interaction between H2O and
IL is 1:1. In addition, as the amount of water increases, the
H2O−H2O interactions are dominant, i.e., the solvation
behavior is predominant. Khan et al.30 predicted the activity
coefficient of water in ILs and the excess enthalpies using the
COSMO-RS approach. This study consisted of setting the
[C4MIM+] cation; whereas the anion was varied, with one of
them being the Cl− anion. The results of this study showed
that the addition of H2O to binary solution reduces the
electrostatic interaction between the [C4MIM+] cation and the
Cl− anion, and both species are attracted to H2O. Moreover,
the hydrogen of water presents a greater preference to bond
with the lone pairs of electrons of the Cl− anion. Accordingly,
as the amount of water increases, the hydrogens of the
molecules of water cluster around Cl− anions up to a saturation
limit. The saturation limit obtained in this work is 0.75, similar
to those reported in the literature. Niazi et al.51 showed that
the maximum saturation limit of the molar fraction of the H2O
4346
Correlation
is 0.75 for H2O−[C4MIM][Cl] system by using molecular
dynamics.
Regarding H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4]
systems, when we obtained the optimized β1 value, we only
observed in the H2O−[C4MIM][PF6] system similar values of
the ΔU2,1 parameter. In a first attempt, we set β1 and ΔU2,1
values and optimized ΔU1,2 and k12 parameters in each
isotherm to know the parameter variation, as a function of
temperature. However, we found that a great deal of scatter
existed among the adjusted ΔU1,2 parameters. This fact
notwithstanding, we correlated the ΔU1,2 and k12 parameters
to a straight-line equation, as a function of temperature. To
reduce the number of fitted parameters, after extensive testing
of solubility calculations, we set the k12 parameter constant at
the highest value (0.645). Figure 3 shows the behavior of the
Figure 3. Fitted ΔU2,1 parameter, as a function of temperature for
H2O−[C4MIM][PF6] system.
ΔU1,2 parameter, as a function of the temperature from the
H2O−[C4MIM][PF6] system at 283.15, 298.15, and 323.15 K.
This figure shows that the ΔU1,2 parameters become less
positive, and even negative as the temperature increases.
Therefore, we correlated them using the following straight-line
equation:
ΔU1,2 = c·T + d (29)
where c and d are the constants of the correlation, and T is the
temperature. The adjusted parameters of the modeling
approach for the H2O−[C2MIM][BF4] system presented a
similar behavior to the H2O−[C4MIM][PF6] system. The
main difference was that the ΔU1,2 values were comparable in
each isotherm and the ΔU2,1 values did not show any
tendency. Thus, we followed the above-mentioned approach
for the fitting of the parameter. First, we fixed the value of the
ΔU1,2 parameter, and then the k12 parameter at the highest
value (0.553). Finally, we adjusted the ΔU2,1 parameter as a
function of temperature. The corresponding results are shown
in Figure 4, where it can be seen that all values are positive and
they become less positive as the temperature increases. This
figure also showed that the values decrease in a scattered
manner as temperature increases. This fact notwithstanding,
we correlated them according to the following straight-line
expression, as a function of temperature:
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Figure 4. Fitted ΔU2,1 parameter, as a function of temperature for

Figure 5. Solubility of the H2O−[C4MIM][PF6] system at 283.1,
H2O−[C2MIM][BF4] system.
298.15, and 323.15 K with the PR-WS model. Symbols represent
experimental data, and solid lines represent the calculated data.
ΔU2,1 = e·T + g (30)
where e and g are the constants of the correlation, and T is the
temperature. Table 4 presents the β1, ΔU1,2, ΔU2,1, and k12

Table 4. Fitted Model Parameters for H2O−[C4MIM][PF6]

and H2O−[C2MIM][BF4] Systems
ionic liquid coefficient [C4MIM][PF6] [C2MIM][BF4] total
Na 33 27 60
β1 4.26 13.79
ΔU12 [cal/mol c −5.10
d 1571.38 −793.89
ΔU21 [cal/mol] e −5.43
g 1439.82 3618.87
k12 0.645 0.554
AAD, P% 2.50 3.90
a
N = number of experimental points.

Figure 6. Solubility of the H2O−[C2MIM][BF4] system at 323.15,

values for H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4]
systems. As seen in Table 4, the predictive capability of the
present approach for calculating the H2O solubility in ILs is
quite good.
Figure 5 shows the H2O solubility in [C4MIM][PF6] at
283.1, 298.15, and 323.15 K; whereas, Figure 6 presents the
H2O solubility in [C2MIM][BF4] at 323.15, 328.15, and
333.15 K. These figures show that the pressure increases as the
molar fraction of the H2O increases. Both figures present a
satisfactory agreement between experimental and calculated
solubilities, even at the dilution region, as demonstrated in
Figure 5.
Figures 7 and 8 depict the analysis of the entropic and
enthalpic contributions with the UNIQUAC model for H2O−
[C4MIM][PF6] and H2O−[C2MIM][BF4] systems, respec-
tively. As shown in both figures, the behavior of the entropic
contributions is the same at any temperature, because neither
the size or shape of the ILs are different. However, the
behavior of the enthalpic contributions exhibits a variation as
the molar fraction of the H2O is increased, as revealed in
Figures 7 and 8. As can be seen in Figure 7, all enthalpic
contributions are positive; this means that the behavior of
these systems is endothermic. Also, it is shown that as
temperature increases, the enthalpic contributions are less
4347
328.15, and 333.15 K with the PR-WS model. Symbols represent
experimental data, and solid lines represent the calculated data.
positive, because of the stronger molecular interactions
between H2O and [C4MIM][PF6]. These molecular inter-
actions increase, in a linear manner, as the molar fraction of the
H2O increases. The behavior of the enthalpic contributions is
entirely different for the H2O−[C2MIM][BF4] system as
shown in Figure 9. This figure presents that all enthalpic
contributions are negative, and they decrease as the temper-
ature increases at a 0.4 molar fraction of the H2O; that is, the
molecular interactions between H2O and [C2MIM][BF4]
increase as the temperature increases. It is important to note
that, as the molar fraction of the H2O increases at 0.5, the
values of enthalpic contributions are similar; meaning that, the
molecular interactions are equal, regardless of the temperature.
At molar fractions of >0.5, the enthalpic contributions begin to
increase with temperature. This variation indicates that the
molecular interactions between H2O and [C2MIM][BF4] are
less favorable at higher temperatures. The latter behavior also
shows that the effect of the composition is stronger than that of
temperature, since the slope of the straight line in the range
from 0.4 to 0.7 molar fraction of the H2O does not change,
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Figure 7. Analysis of the entropic and enthalpic contributions for
H2O−[C4MIM][PF6] system at 283.15, 298.15, and 323.15, K using
the UNIQUAC model. Dotted lines represent data from the entropic
contribution, and solid lines represent data from the enthalpic
contribution.
Figure 8. Analysis of the entropic and enthalpic contributions for
H2O−[C2MIM][BF4] system at 323.15, 328.15, and 333.15 K using
the UNIQUAC model. Dotted lines represent data from the entropic
contribution, and solid lines represent data from the enthalpic
contribution.
regardless of temperature. In Figure 9, it is also shown that
there is little effect on the enthalpic contributions at H2O
molar fractions of >0.7. According to Cammarata et al.,52 who
studied the H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4]
systems with the ATR-IR spectroscopy, the increase of the
H2O solubility in imidazolium-based ILs is dependent on the
formation of the hydrogen bond between H2O and the anion
of IL.
Figure 10 shows the entropic and enthalpic contributions for
H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4] systems at
323.15 K and H2O−[C2MIM][Cl] and H2O−[C4MIM][Cl]
systems at 1 bar. As can be seen, the entropic contributions are
positive for H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4]
systems. Regarding the enthalpic contributions, they are
positive for the H2O−[C4MIM][PF6] system, which indicates
its hydrophobic character in the H2O solubility; whereas the
4348
Correlation
Figure 9. Analysis of the enthalpic contribution for H2O−[C2MIM]-
[BF4] system at 323.15, 328.15, and 333.15 K, using the UNIQUAC
model.
Figure 10. Analysis of the entropic and enthalpic contributions for the
H2O−[C4MIM][PF6] and H2O−[C2MIM][BF4] systems at 323.15 K
and the H2O−[C2MIM][Cl] and H2O−[C4MIM][Cl] systems at 1
bar, using the UNIQUAC model. Dotted lines represent data from
the entropic contribution, and solid lines represent data from the
enthalpic contribution.
enthalpic contributions are negative for the H2O−[C2MIM]-
[BF4] system, leading to more favorable interactions between
H2O and [C2MIM][BF4] molecules. It is important to
highlight that the binary solutions do not present a comparable
range of molar fractions of the H2O, cation or anion, although
both anions are fluorinated. However, when the H2O−
[C2MIM][BF4], and H2O−[C2MIM][Cl] systems are com-
pared (Figure 10), it can be observed that the entropic
contribution for the H2O−[C2MIM][BF4] system is greater
than for the H2O−[C2MIM][Cl] system. Figure 10 also shows
that the entropic contribution for the H2O−[C2MIM][BF4]
system is greater than for the H2O−[C4MIM][Cl] system;
even though the [C4MIM+] cation has a larger alkyl chain
length. The enthalpic contributions are negative for the three
systems, what indicates an exothermic behavior and favorable
molecular interactions. It can also be observed in Figure 10
that the H2O solubility degree in the H2O−[C2MIM][Cl] is
more significant than in the H2O−[C2MIM][BF4] system.
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Figure 11. (a) Fitted ΔU2,1 parameter for the H2O−[C4MIM][BF4] system at H2O molar fractions of 0.112, 0.280, 0.398, and 0.582, and (b) fitted
ΔU2,1 parameter at H2O molar fractions of 0.112, 0.280, and 0.398 for the H2O−[C4MIM][BF4] system.

Figure 12. (a) Fitted ΔU2,1 parameter for the H2O−[OHC2MIM][BF4] system at H2O molar fractions of 0.2, 0.4, 0.6, and 0.8 , and (b) fitted
ΔU2,1 parameter for H2O−[OHC2MIM][BF4] system at H2O molar fractions of 0.2, 0.4, and 0.6.

Figure 13. (a) Fitted ΔU1,2 parameter for the H2O−[OHC2MIM][Cl] system at H2O molar fractions of 0.693, 0.795, 0.9, 0.955, and 0.988, and
(b) fitted ΔU1,2 parameter at H2O molar fractions of 0.693, 0.795, 0.9, and 0.955 for the H2O−[OHC2MIM][Cl].

According to Khan et al.,30 the increase in the size of the
halogenated anions causes a lesser interaction with H2O.
Furthermore, they showed that the fluorinated anions decrease
the interaction force between H2O and the IL. As evidenced in
Figure 10, the UNIQUAC model was able to capture the size
and shape effects of the anion (via entropic contribution), as
well as the force in the molecular interactions between the
H2O and IL, regardless of the type of anion. Jork et al.5 and
4349
Freire et al.49 noted that the size or shape of anion has a more
considerable effect than the alkyl chain length of the
imidazolium cation in the solubility of the above-mentioned
systems.
To obtain the fitted parameters of the modeling approach at
constant composition for the H2O−[C4MIM][BF4], H2O−
[OHC2MIM][BF4], and H2O−[OHC2MIM][Cl] systems, we
followed the above-mentioned methodology. First, we
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Table 5. Fitted Model Parameters for the H2O−[C4MIM][BF4], H2O−[OHC2MIM][BF4], and H2O−[OHC2MIM][Cl]
Systems
ionic liquid coefficient [C4MIM][BF4] [OHC2MIM][BF4] [OHC2MIM][Cl] total
Na 45 35 48 128
β1 11.95 13.71 2.75
ΔU12 [cal/mol] h 2171.10
l 108.48 −757.65 −1778.30
ΔU21 [cal/mol] n 1952.74 265.16
o 432.67 −327.66 −48.05
k12 −0.517 0.748 0.591
AAD, P% 11.65 8.64 1.93
a
N = number of experimental points.

Figure 14. Solubility of the systems with the PR-WS model: (a) H2O−C4MIM][BF4] system at H2O molar fractions of 0.112, 0.280, 0.398, and
0.582 , (b) H2O−[OHC2MIM][BF4] system at H2O molar fractions of 0.2, 0.4, 0.6, and 0.8, and (c) H2O−[OHC2MIM][Cl] system at H2O
molar fractions of 0.693, 0.795, 0.9, 0.955, and 0.988. Symbols represent experimental data, and solid lines represent calculated data.

optimized the β1, ΔU1,2, ΔU2,1, and k12 parameters, and then
we chose the β1 value at the lowest AAD, P%. Subsequently,
we set the β1 value constant, and ΔU1,2, ΔU2,1, and k12
parameters were then again optimized. At this point, we
observed that ΔU1,2 showed similar values for the H2O−
[C4MIM][BF4] and H2O−[OHC2MIM][BF4] systems, so that
it was set constant for both systems. After that, we adjusted
ΔU2,1 and k12, and we observed a great deal of scatter among
them; regardless of it, we correlated ΔU2,1 values to a straight-
line equation as a function of the molar fraction of the H2O,
and then we fitted the k12 parameter. Finally, we chose the
highest k12 value and set it constant to optimize the ΔU2,1
parameter again. Figure 11 shows the fitted ΔU2,1 values, as a
function of the molar fraction of the H2O for the H2O−
[C4MIM][BF4] system. As can be seen, all values are positive,
4350
and they increase as the molar fraction of the H2O increases.
Figure 11a shows that, at a molar fraction of 0.582, there is not
a linear trend of the ΔU2,1 parameters. Figure 12 presents the
ΔU2,1 values as a function of the molar fraction of the H2O for
the H2O−[OHC2MIM][BF4] system. Figure 12a shows that
all values are negative, and they became less negative as the
molar fraction of the H2O increases, except at 0.8. Figures 11a
and 12a show that the H2O−[C4MIM][BF4] and H2O−
[OHC2MIM][BF4] systems show a deviation of the linear
equation at the highest molar fraction of the H2O. This
behavior could be attributed to the solvation effect between
the H2O and the [BF−4 ] anion, which has been evidenced as
the amount of water is increased.30 Since this modeling
approach only takes into account the short-range interactions,
we decide to exclude the obtained ΔU2,1 values at the highest
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Industrial & Engineering Chemistry Research
molar fraction of H2O. A similar procedure for the fitting of
parameters was followed for the H2O−[OHC2MIM][Cl]
system. The main difference is that we set the ΔU2,1 parameter
constant and adjusted the ΔU1,2 parameter, as a function of the
molar fraction of the H2O. Figure 13a shows the fitted ΔU1,2
values as a function of the molar fraction of the H2O. It is
observed that the ΔU1,2 values increase linearly from negative
to positive, when the molar fraction of the H2O is increased,
except at 0.988. We suggested that the presence of the
hydroxyl group in the cation and the high concentration of
H2O, regardless of the size of the anion, produce such
behavior. However, the proposed model was not able to
describe this trend, because it includes only the short-range
interactions. Therefore, we fitted the ΔU1,2 values to a linear
equation without taking into account the last point, as shown
in Figure 13b. The following straight-line equation was used to
correlate ΔU1,2 and ΔU2,1 parameters as a function of the
composition:
ΔU1,2 = h·x + l (31)
ΔU2,1 = n·x + o (32)
where h, l, n, and o are the correlation constants and x is the
molar fraction of the H2O. The correlating results of the β1,
ΔU1,2, ΔU2,1, and k12 parameters and the AAD, P% are listed in
Table 5. This table shows that the AAD, P% values are high for
the H2O−[C4MIM][BF4] and H2O−[OHC2MIM][BF4]
systems: 11.65% and 8.64%, even though the ΔU1,2 parameter
was correlated as a function of the molar fraction of H2O.
Figure 14 shows the experimental and calculated solubilities
with the modeling approach for the H2O−[C4MIM][BF4]
system at H2O molar fractions of 0.112, 0.280, 0.398, and
0.582, the H2O−[OHC2MIM][BF4] system at H2O molar
fractions of 0.2, 0.4, 0.6, and 0.8, and the H2O−[OHC2MIM]-
[Cl] at H2O molar fractions of 0.693, 0.795, 0.900, 0.955, and
0.988. Figures 14a and 14b show that there exist a poor
agreement between experimental and calculated solubilities at
the highest isopleths. A possible explanation of these
discrepancies is that the solvation interactions are not taken
into account in the modeling approach. These solvation forces
are present as the concentration of water increase, especially in
systems with bulky anions, e.g., [PF−6 ] and [BF−4 ]. On the other
hand, Figure 14c shows good agreement between the
experimental and calculated solubilities, probably because the
size of the halide ion, such as Cl−, is smaller than the bulky
anions.
Figure 15 depicts entropic and enthalpic contributions for
the H2O−[C4MIM][BF4], H2O−[OHC2MIM][BF4], and
[OHC2MIM][Cl] systems at H2O molar fractions of 0.582,
0.6, and 0.693, respectively. Although it is not valid to compare
such systems, because they present different compositions, we
only exhibited them to understand the behavior of their
contributions as a function of the molar composition of the
H2O. As can be seen in this figure, the entropic contributions
are represented by a point, because the molar fractions are
constant. The entropic contributions for the binary systems
with the anion [BF−4 ] are positive, whereas the solution with
the Cl− anion is negative. On the other hand, the enthalpic
contributions are described by solid lines. These contributions
are negative for the H2O−[OHC2MIM][BF4] and H2O−
[OHC2MIM][Cl] systems, which indicate that the molecular
interactions between H2O and the IL are favorable. However,
the enthalpic contributions are positive for the H2O−
4351
Correlation
Figure 15. Analysis of the entropic and enthalpic contributions using
the UNIQUAC model for the H2O−[C4MIM][BF4], H2O−
[OHC2MIM][BF4], and [OHC2MIM][Cl] systems at H2O molar
fractions of 0.582, 0.6, and 0.693, respectively. Symbols represent data
from the entropic contribution, and solid lines represent data from the
enthalpic contributions.
[C4MIM][BF4] system; this behavior shows that the molecular
interactions are unfavorable between H2O and [C4MIM]-
[BF4]. An examination of this figure also shows a poor
variation in the values of the enthalpic contributions for all
systems, especially in the H2O−[OHC2MIM][Cl] system.
Thus, the behavior of the entropic and enthalpic contributions
are not well represented by the UNIQUAC model using
experimental solubility data at constant composition.
■
CONCLUSIONS
A formal modeling approach was devised here to calculate and
predict the H2O solubility in imidazolium-based ILs. It made
use of the Peng−Robinson cubic equation of state (EoS) and
the Wong−Sandler mixing rules under different conditions of
temperature, pressure, and composition. The following
conclusions can be drawn from this work:
(1) The agreement between experimental and calculated
solubility data was remarkably good when the anion of
the ILs are small, such as halides. However, the model
requires the use of temperature-dependent ΔU values
for improving H2O−solubility estimations when the ILs
present bulky anions or hydroxyl groups in cations.
(2) Results of the comparison showed a poor agreement
between the experimental data and the calculated values
when the IL exhibits (i) a bulky anion, and (ii) a
hydroxyl group in the cation.
(3) The UNIQUAC model was able to predict the behavior
of the molecular interactions (enthalpic contribution) at
constant temperature and pressure, as well as the effect
of the alkyl chain length in cation and the size of the
anion (entropic contribution).
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: rms@ipn.mx.
ORCID
Ricardo Macías-Salinas: 0000-0002-0372-8190
Notes
The authors declare no competing financial interest.
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■ ACKNOWLEDGMENTS
J.M. and M.A.Z.-H. gratefully acknowledge the National
exp = experimental value
residual = residual property
Council for Science and Technology of Mexico (CONACyT)
for providing financial support for this work. R.M.S. is also
grateful for the financial support provided by the Instituto
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