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org/jced Article

Dragonfly-Support Vector Machine for Regression Modeling of the

Activity Coefficient at Infinite Dilution of Solutes in Imidazolium
Ionic Liquids Using σ‑Profile Descriptors
Hania Benimam,* Cherif Si Moussa, Mohamed Hentabli, Salah Hanini, and Maamar Laidi
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ABSTRACT: Ionic liquids (ILs) have shown remarkable potential

for applications in separation, such as extractive distillation and
liquid−liquid extraction. Crucial to these applications is the
estimation of a significant property of the ILs which is the infinite
dilution activity coefficient (IDAC) of different solutes in ILs. In
this context, the present paper aims to model IDAC of 17 solutes
in 44 imidazolium ILs using 2666 experimental data points
gathered from the literature and based on support vector machine
for the regression (SVMr) learning algorithm. Two models are
developed, one based on SVMr and the other one based on
dragonfly algorithm (DA) associated with SVMr. Both models
consider the same set of predictive variables which are the
temperature, the molecular weight of solute and solvent, and five conductor-like screening models for real solvents (COSMO-RS) σ-
profile descriptors related to the solute and IL. The DA is applied for optimization of SVMr hyper-parameters. The results show the
superiority of the DA-SVMr model demonstrated by its correlation coefficient (R) and root mean square error values of 0.996 and
0.170, respectively.

1. INTRODUCTION such applications of ILs in factual processes dictate their

As the sustainable development of processes continues to characterization by establishing accurate quantitative structure
receive a great amount of attention, the introduction of cleaner property relationships which give insight into the properties
and behavior of the IL based on its molecular structure.6 In a
technologies has become a high priority, and opting for eco-
separation process that involves the use of an IL as an
friendly solvents to replace harmful solvents has preoccupied
entrainer, the liquid−liquid equilibrium (LLE) and vapor−
researchers both in academia and industry.1 Ionic liquids (ILs)
liquid equilibrium (VLE) data of the ternary system including
are organic salts that consist entirely of ions and have melting
the IL is preliminary in the design and optimization of the
points much lower than those for conventional inorganic ionic
extraction phase; the reason why considerable efforts have
compounds.2 As explained by Paduszyński,3 in ILs, the
been made to report the experimental results of LLE and VLE
Coulomb forces between ions are strong resulting in their
of different systems relating ILs.7 Infinite dilution activity
extremely low volatility, and the reason why they are
coefficient (IDAC) (γ∞) of a solute in an IL is another
considered eco-friendly. The high-solvating power of ILs for
significant thermodynamic property of ILs giving information
a large variety of materials including organic, inorganic, and
about their affinity and basically justifies opting for a particular
organo-metallic compounds enhances their performance as the IL over others in a given separation process. At infinite dilution
solvent, and particularly, their capacity for selective separation of a solute in an IL, the interactions between molecules of IL
of similar compounds.3 Moreover, the properties of ILs can be and those of a solute are predominant compared to the
adjusted and tuned to selectively separate similar compounds interactions between IL and IL, and the difference in values of
by a careful choice of anion and cation combination.3 γ∞ of two solutes reveals the IL’s selectivity in the separation
The numerous pros of ILs, compared to the cons of volatile
organic compounds (VOCs), resulted in many of their
applications in extractive distillation and liquid−liquid Received: February 16, 2020
extraction,4,5 leading thus to more environmentally friendly Accepted: May 14, 2020
processes due to the nonvolatility of ILs compared to that of
VOCs and enhanced separation processes by tuning some key
parameters such as capacity and selectivity through a judicious
choice of anions and cations in designing the ILs. Unarguably,

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jced.0c00168

A J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
process of the ternary mixture of the two solutes and IL. Also,
the estimation of property γ∞ is more economical and easier
than establishing LLE and VLE phase diagrams,3 which makes
studying this parameter more advantageous in the design and
optimization of separation processes. Because of the rise of
research studies aiming for the estimation of γ∞, a large
number of papers have reported values of γ∞ for different
solutes in more than 200 ILs since 2001.3
Clearly, experimental-based characterization is the most
reliable means for estimation of properties of a matter, but with
ample availability of ILs, which are estimated at 250,000 based
on currently available binary anion/cation systems,8 exper-
imental measurements are costly, often difficult, and time-
consuming, and the reason why modeling methods of IDAC
have arisen.
Thermodynamic models based on the activity coefficient are
the most extensive approach to predict IDAC. These models
are classified into predictive models such as group contribution
models UNIFAC,9 Scatchard Hildebrand, Flory−Huggins, and
COSMO, and semi-predictive models which necessitate fitting
the Gibbs free energy model parameters such as Van Laar,
Margules, NRTL, and UNIQUAC.10 In that context, many
correlative models predicting IDAC by simple statistical
regression11−18 based on least squares have been proposed.
In addition, other models based on advanced machine learning
algorithms have been developed and seemed more robust.
However, despite their fast computation ability, these
techniques require a large amount of data and usually do not
broaden well outside the ranges and classes of the systems
from which they were established and the accuracy is
conditional to the availability and validity of experimental
data because they are correlative methods.19 A more advanced
computational technique based on quantum mechanical
calculations and statistical thermodynamics such as con-
ductor-like screening model for real solvents (COSMO-RS)
appear capable of circumventing challenges and limitations
encountered in correlative modeling mainly because they are
more predictive because they do not rely on the experimental
data for calculations. Although they require sophisticated
materials and a user’s expertise and are the most computa-
tionally exhaustive, they are promising in virtually screening
and evaluating different combinations of anions/cations
forming the ILs.19,20 The σ-profile of ions may be alternatively
obtained using nonproprietary software such as COSMO-
SAC.21 An overview of the COSMO-RS technique along with
related research studies and papers are given in the following
section.
So far, computational modeling of IDAC has been proposed
in numerous papers, mainly based on correlative methods such
as neural networks22,23 or quantum mechanical/statistical
thermodynamic methods.3,18,24−27 As correlative models
depend on the availability of accurate experimental data, and
the latter models are complicated in use and require expertise,
it is interesting to explore a hybrid approach where results and
data obtained from quantum mechanical/statistical thermody-
namic calculations are correlated using a robust machine
learning algorithm to develop a model for estimation of IDAC
of different solutes in ILs. To the best of our knowledge, there
has been only one paper18 that combined the two computa-
tional methods for modeling IDAC of water in ILs based on
temperature and sigma profiles of anions and cations using
multilinear regression and there has not been any similar
research that involved different solutes in ILs. Therefore, the
B https://dx.doi.org/10.1021/acs.jced.0c00168
pubs.acs.org/jced Article
present work aims at modeling IDAC of seventeen solutes in
44 imidazolium-based ILs, based exclusively on temperature
and COSMO-RS sigma profiles of both the solutes and
solvents, and using a support vector machine (SVM) technique
associated with the dragon-fly swarm algorithm for better
optimization of hyper-parameters.
2. METHODS AND DATASET
2.1. COSMO-RS. Possibly, COSMO-RS which is based on
quantum calculations combined with a continuum treatment of
the solvent is the most popular approach for modeling
solubility.19 The method was developed and applied for the
first time by Klamt and co-workers.25 The researchers adopted
the conductor-like screening model in a real solvent comport-
ment which mainly consists of carrying out quantum
mechanical calculations on a given individual solute in a
conducting continuum manner, hence modeling explicitly
solvent molecules is unnecessary. The consequential surface
charge densities and geometries are then exploited to compute
the interactions between the solute and solvent by way of pair-
wise interrelating surface segments. Subsequently, a statistical
thermodynamic perspective is used for estimation of activity
coefficients of solutes.19 In depth description of the COSMO-
RS can be found in the literature.28
Numerous papers have reported the prescreening of solutes
in ILs based on COSMO-RS,3,18,29−31 and the method gave
good qualitative and, in many cases, quantitative predictions of
IDAC of solutes in ILs. Also, the ability of the method to
perform virtual screening of different solutes in different ILs in
a fast pace has played a major role in its attractiveness. In the
present contribution, COSMO-RS sigma profiles of seventeen
solutes and different ions forming the ILs are considered as
molecular descriptors of the binary mixture solute/IL and are
subsequently used for modeling the IDAC.
2.2. SVM for Regression. SVM is a correlative computa-
tional technique-like artificial neural network (ANN), however
it is built on structural risk minimization32 instead of empirical
risk minimization-based ANN, the reason being that this
technique is robust and accurate as stated by Yoon et al.33
Therefore, it is a reliable algorithm both for classification and
regression.34 For regression analysis, SVM regression (SVMr)
hypothetically reduces the predictable error in a learning
process and decreases the problem of overfitting often
encountered in machine learning.35 Leading in many cases to
a better performance of the SVMr compared to other learning
methods.33,36−39 As explained by Parveen et al.,40 SVM
regression analysis of a training data set: TD = {(a1,b1),
(a2,b2), ..., (aN,bN)}, where ai is a vector of real independent
variables and bi is the corresponding real dependent variables.
Accordingly, in feature space, the regression equation can be
estimated by:
z(a , w) = (w·⌀(a) + c) (1)
where w represents the weight vector, ⌀(a) corresponds to the
feature function, w·⌀(a) is the dot product, and c is a constant.
Theoretically, SVM reduces the predictable error through
minimization of the following equation
1 1
Q (f ) = C Lε(b , z(a , w) + W 2
N 2 (2)
and
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
l
o
o0
Lε(b , z(a , w) = m
o
o
if |b , z(a , w)| ≤ ε
n|b , z(a , w)| − ε otherwise
Q(f) represents the empirical error and the term C indicates
the measure of optimization between the empirical error and
the model complexity shown in the right term of eq 2; whereas
the loss function is expressed in eq 3 and is labeled insensitive
loss function ε.41 By integrating the Langrangian multiplier β
and β*, the optimization problem is transformed into a dual
problem. The coefficients with a value different than zero and
their corresponding input vectors ai are named the support
vectors. The resulting regression equation is the following
Nsv
z(a , βi , βi*) = ∑ (βi − βi*)(⌀(ai)·⌀(aj)) + c
i=1
By introducing the kernel function k(xi,xj), the above
function takes the following form
Nsv
z(a , βi , βi*) =
∑ (βi − βi*)k(a , ai) + c
i=1
Karush−Kuhn−Tucker provisions are employed to calculate
the value of the entity c. In SVMr modeling, the so-called
hyper-parameters are the cost function C and the radius of the
insensitive tube ε in addition to the kernel function’s parameter
γ, and these parameters are directly associated to the SVMr’s
performance ability for the problem at hand. In the present
work, SVMr modeling is elaborated using MATLAB 2018. The
importance of the values that hyper-parameters take in SVMr
requires the optimization of these parameters. Basically, there
are infinite possible values that hyper-parameters may take, so
testing all values and combinations of values is computationally
and practically impossible. Therefore, for the present study,
dragonfly algorithm (DA), a swarm intelligence (SI) algorithm,
has been used with SVM for the optimization of hyper-
parameters.
2.3. Dragonfly Algorithm. SI is a field of study first
proposed by Beni and Wang in 1993.42 The study aims at
understanding the different interactions between individual
living creatures that may result in social intelligence.
Accordingly, it simulates and implements the collective and
social intelligence behavior of a whole population based on
discovered rules between some of the population.43 Tharwat
and co-workers44 summarized the principles leading any swarm
behavior as:
• Separation principal: represents the constant collision
avoidance between individuals in a population, and this
follows the following equation: Si = −∑ni=1(x − xi);
where x represents the current solution’s and xi is the
position in the neighborhood individual i, while n is the
total number of members in a neighborhood.
• Cohesion principal: this principal is based on the
tendency of individuals for arrangement toward the
mass midpoint of the neighborhood, and it is described
n
∑i = 1 xi
as Ci = n
− x.
• Alignment principal: represents the identical velocity of
dragonflies members existing in the same group, and it is
∑
n
V area, and Aj(σ) the total surface area of all of the segments with
defined as, Ai = i=n1 i , where Vi is the velocity of
neighborhood individual i.
pubs.acs.org/jced Article
Movement of dragonflies in nature toward food can be
expressed as Fi = x+ + x, where x+ represents the food’s
position, and their movement away from the enemy is Ei = x−
(3) + x, given x− is the enemy’s position.45
The localization/coordinate of a dragonfly is the sum of its
position x and its step Δx and can be expressed as, xt+1 = xt +
Δxt+1, where t is the current iteration and Δxt+1 is determined
using the following equation
Δxt + 1 = sSi + aAi + cCi + fFi + eEi + ωΔxi (6)
where Si is the separation for xi and s is its separation weight; Ai
is the alignment of xi and a is its alignment weight; Ci is the
cohesion of xi and c is its weight; Fi is the food attraction of xi
and f is the food parameter; and Ei is the distraction from
enemy and e is its factor; and ω is the inertia weight. The
factors s, a, c, f, and e are determined during optimization and
(4) have a double action that of exploration and of exploitation in
the DA algorithm.45
3. RESULTS AND DISCUSSION
3.1. Data Collection and Analysis. 3.1.1. Sigma Profile.
A brief description of the COSMO-RS sigma profile similar to
(5)
Mullins’s et al.46 is presented here. In theory, COSMO-based
models picture the solute molecule inside a cavity surrounded
by a uniform medium representing the solvent, and based on a
set of explicit rules and atoms’ structural aspects, the model
build the cavity hypothetically within an ideal conductor and a
perfect solvation process. The dipole and higher moments of
the solute molecule induce charge from the adjacent medium
to the surface of the cavity by eliminating the electric field
inside the conductor and lateral to the surface. The resulting
surface charge is defined by the following equation
ϕtot = ϕsol + Dq* = 0 (7)
where φtot is the total potential on the surface of the cavity, φsol
is the potential on the solute molecule because of the charge
distribution, D represents the Coulomb interaction matrix
defining the interactions among surface charges and is a
function of its geometry.47 The surface charge dispersal in a
dielectric solvent is estimated by the fitting of the surface
charge distribution in a conductor (σ*).
The COSMO calculation response (σ*) is then approxi-
mated over a circular surface section to attain a new surface
charge distribution labeled σ, which characterizes the
probability distribution of a molecular surface section that
has a specific electric charge density, and the probability
distribution is referred to as the sigma profile p(σ) of a
molecule,46 and it is defined by Klamt48,49 for a molecule j as
Nj(σ ) A j (σ )
pj (σ ) = =
Nj Aj (8)
Aj
Nj = ∑ Nj(σ ) =
σ
aeff (9)
Aj = ∑ A j (σ )
(10)
σ
wherein Nj(σ) represents the quantity of segments with a
discretized surface charge density σ, Aj the total cavity surface
a particular charge density σ. aeff is known as the effective
surface area and represents the theoretical contact surface
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Table 1. σ-Profile Descriptors and the Margins Limiting Each Section

cation’s molecular descriptors anion’s molecular descriptors solute’s σ-profile descriptor
S1 S2 S3 S4 S5
σ (e/nm2) [−2.5, −1.0] [−1.0, 2.0] [−1.1, 1.5] [1.5, 3.0] [−2.5, 2.5]

Table 2. Most Important Information About the Data Adjusted in This Work
variable category factors unit domain SD variance kurtosis
input M (IL) g/mol [169.247−643.79] 131.327 17,251.967 −0.3689
T K [293.15−413] 21.1643 448.0465 −0.51456
S1 e/nm2 [1.2583−3.86975] 0.4504 0.2030 2.4220
S2 e/nm2 [11.50845−48.7078] 6.2359 38.8849 5.7886
S3 e/nm2 [0−25.8853] 6.523 42.5475 −0.83620
S4 e/nm2 [0−5.281] 1.7947 3.2214 −0.2266
M (Sol) g/mol [18.015−198.394] 30.6218 935.636 1.445
S5 e/nm2 [4.327−31.699] 4.842 23.401476 0.98834
output IDAC [0.013−4222.32] 331.527 109,945.803 51.072

Figure 1. Probability density distribution of variables.

between molecules. In some works,50 the parameter aeff is
adjusted to a value of 7.1 Å2.
Usually, the σ-profile of a solute or a solvent is divided into
four sections, and each section is defined by an interval of σ
(e/nm2). The sections were previously considered as
molecular descriptors by Gonfa.18
In this work, the sigma profile of solutes, anions, and cations
of the IL are partitioned into two sections. Table 1 shows the
σ-profile descriptors considered in the present study and their
ranges.
S1 represents the hydrogen bond donor character of the
cation, S2 correspond to the nonpolar character of the cation
and its hydrogen bond acceptor behavior. Similarly, S3
indicates the hydrogen bond donor character in addition to
nonpolarity of the anion and S4 designates the strong
hydrogen bond acceptor behavior of the anion. Whereas, S5
is the summation of the three characters of the solutes
D https://dx.doi.org/10.1021/acs.jced.0c00168
(hydrogen bond donor character, the nonpolar character, and
the hydrogen bond acceptor behavior). The fusion of the three
σ-profile regions of the solute is justified by the idea that at
infinite dilution, the molecules of solutes are theoretically
entirely surrounded by solvent molecules and in that specific
condition, the electric surface density distribution by region is
not as important as the total value of σ.
3.1.2. Statistical Data Analysis. Table 2 summarizes the
dependent and independent variables, their ranges, unit of
measure, domain studied, their standard deviation, variance
and Kurtosis.
3.1.2.1. Kernel Density Distribution. The probability
density function (pdf) of a random variable can be represented
nonparametrically as a kernel distribution, when a parametric
distribution cannot describe the data and to avoid making
assumptions about the data distribution. A smoothing function
and a bandwidth value control the smoothness of the resultant
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 2. Input variables binary interactions.
density curve and characterize the kernel distribution. For a
given predictive factor x, the estimated pdf of the variable
represent its kernel density estimator and is defined as
i x − xi yz
∑ kjjj zz
n To overcome this problem, regularization techniques such as
nh j = 1 k h {
1
fĥ (x) =
(11)
where x1, x2, ..., xn are random sample values from an
unidentified distribution, n is the data sample size, k represents
the kernel smoothing function, and h is the bandwidth.51
Accordingly, the probability density distribution of pre-
dictive variables considered in this work is represented in
Figure 1.
3.1.2.2. Least Absolute Shrinkage and Selection Operator
(Lasso). To evaluate the accuracy of a trained model using a
machine learning method, an optimization of a loss function is
required. In regression, the value of the predicted output is
continuous and is reliant on the choice and collection of inputs
that best describe the problem in hand. Also, any interferences
that may exist between inputs should be closely identified, and
for that purpose the binary interactions between inputs are
illustrated in Figure 2.
Training a model consists at minimizing the quadratic loss
which is the sum of deviations between the predicted and
actual output value. The multivariable linear regression
problem is represented by eq 12
γj∞ = β1X1j + β2X 2j + β3X3j + ... + βi Xij + β0 (12)
where X1j, X2jX3j, Xij are the i inputs variables corresponding to
the output γ∞j in the line j in the dataset and β1, β2, β3, βi are
their respective coefficients while β0 is the intercept coefficient.
Minimization of the loss function and finding optimal β
coefficients through an iterative process allow the development
of a trained model for regression. However, a problem of
overfitting the data is often encountered in machine learning
algorithms, therefore attention should be given to the optimal
E https://dx.doi.org/10.1021/acs.jced.0c00168
pubs.acs.org/jced Article
number of dependent variables, as an excess of them may lead
to more noisy samples, and subsequently a trained model
memorizing the noise instead of learning the trend of the data.
Lasso and Ridge that lead to simple models that usually do not
overfit. In brief, in a regularized machine learning model, the
loss function includes an additional term, also known as the
regularization term, that has to be minimized as well and is
defined as
L= ∑ (γj∞pred − γj∞real)2 + λ∑ |β| (13)
The regularization term in the Lasso loss function not only
punishes the function for high values of coefficients β, but it
also sets them to zero if they are not relevant. As a result, the
model will include the most pertinent inputs and the least
significant ones will be discarded. The results of Lasso
regularization applied to the problem discussed in this work
and using different types of interaction matrixes can be
accessed in the Supporting Information.
3.1.2.3. Ridge Regularization. Ridge regularization, also
known as Tikhonov Regularization, is the most popular
technique used for shrinking the number of inputs and
improving the predictive accuracy of correlative models prior
to Lasso. The difference between these two regularization
techniques is in the penalty term in the loss function L as
follows
L= ∑ (γj∞pred − γj∞real)2 + λ∑ β 2 (14)
Although Ridge regularization punishes high values of
coefficients β by the sum of squared in the loss function, it
does not eliminate the least significant covariates like Lasso
does, and as a result, it reduces overfitting but does not set the
irrelevant inputs’ coefficients to zero. Outcomes of Ridge
regularization of the present data and a statistical analysis of
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input variables’ distribution are available in the Supporting
Information.
3.2. Modeling IDAC. 3.2.1. SVMr Model. In this paper,
SVMr learning algorithm is used for nonlinear modeling of the
IDAC of 17 solutes in imidazolium-based ILs using the largest
available/accessible literature data. The optimal SVMr model
is obtained through the process illustrated in Figure 3.
Figure 3. Flowchart of the SVMr optimization process.
performed randomly. In the next step, the kernel function that
fits best our data trend and hyper-parameters are optimized
within the following ranges:
C ∈ [10−3,103], ε ∈ [0,10−2], γ ∈ [10−3, 10], and n ∈ [2, 6];
while the different kernel functions tested are linear,
polynomial with different degrees, and Gaussian and radial
basis function (RBF). The optimal SVMr model is achieved
through a repetition of the steps listed above and based on the
best predictive ability of the model, which is measured in this
work by the root mean squared error (RMSE).
Based on the results, the Gaussian function is the kernel
function that fits best the data in this work, and the
hyperparameters C, ε, and γ have the values of 91, 0.0586,
and 2, respectively. The dataset used, Matlab code and model
parameters that allow the reproduction of the results are
available in the Supporting Information.
Different model’s statistical evaluation criteria are adopted in
this work in order to assess the predictive ability of the
developed models, the RMSE, the mean absolute error (MAE),
the mean absolute percentage error (MAPE), the coefficient of
correlation (R), the determination coefficient (R2), and the
intercept coordinate τ. Mathematical equations for these
parameters are
N
1
RMSE = ∑ (γ ∞exp − γi∞cal)2
N i=1 i (15)

First, the data reporting IDAC of 17 solutes in 44 n

imidazolium-based ILs is collected and organized in an excel 1
MAE = ∑ |(γ ∞Exp − γi∞cal)|
folder to be processed by the machine learning algorithm. The n i=1 i (16)
ILs and solutes involved in this study are recapitulated in Table
3. Second, the total dataset is divided into training and test sets
using the holdout function included in the statistical and 100
N
γ ∞Exp − γ ∞cal
machine learning toolbox of Matlab. A quarter of the whole MAPE (%) = ∑ i ∞Expi
N i=1 γi (17)
data is set for the test and the choice of selected points is

Table 3. ILs and Solutes Implicated in the Present Work

ILs solutes
IM-2,1 SCN IM-6,1 BF4 N-PENTANE
IM-2,1 AC IM-2,1 OTF N-HEXANE
IM-4,1 CL IM-4,1 PO2-O1,O1 N-HEPTANE
IM-2,1 DCA IM-6,1 TCB N-OCTANE
IM-2OH,1 DCA IM-2,1 SO3-PH1 N-NONANE
IM-4,1 SCN IM-4,1 OTF N-DECANE
IM-2,1 BF4 IM-10,1 BF4 N-UNDECANE
IM-4,1 AC IM-4,1 SO3-PH1 N-DODECANE
IM-2,1 CCN3 IM-6,1 OTF N-TRIDECANE
IM-6,1 CL IM-10,1 TCB N-TETRADECANE
IM-4,1 DCA IM-1,1 NTF2 CYCLOPENTANE
IM-2,1 SO3-1 IM-2,1 NTF2 METHYLCYCLOPENTANE
IM-2OH,1 BF4 IM-2OH,1 NTF2 CYCLOHEXANE
IM-1,1 PO2-O1,O1 IM-4,1 NTF2 METHYLCYCLOHEXANE
IM-2,1 TFA IM-6,1 NTF2 CYCLOHEPTANE
IM-6,1 SCN IM-6,1,1 NTF2 CYCLOOCTANE
IM-4,1 BF4 IM-1O6,1 NTF2 WATER
IM-2,1 TCB IM-2,1 FAP
IM-4,1 CCN3 IM-2OH,1 FAP
IM-4,1 SO3-1 IM-1O6,1O6 NTF2
IM-2,1 PO2-O1,O1 IM-6,1 FAP
IM-4,1 TFA IM-10,10,1 NTF2

F https://dx.doi.org/10.1021/acs.jced.0c00168
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 ÅÄÅ N ÑÉÑ
Journal of Chemical & Engineering Data pubs.acs.org/jced Article

ÅÅ ∞cal Ñ
Ñ
Å
R = ÅÅ∑ (γi − γ )ÑÑÑ
ÅÅ ÑÑ
learning algorithm, associated to DA algorithm for optimiza-

ÅÇ i = 1 ÑÖ
∞Exp exp ∞cal
− γ ̅ ) × (γi tion of its hyper-parameters. The division proportions of the

ÅÄÅ N ÑÉÑ
ÅÅ ÑÑ
data for training and test, along with the ranges of the hyper-

/ÅÅÅ ∑ (γiÅ − γ ) ÑÑÑÑ

parameters are the same as that for SVMr discussed in the

ÅÅ ÑÑ
ÅÅÇ i = 1 ÑÑÖ
∞ Exp exp 2
− γ ̅ ) × (γi ∞ cal ∞ cal 2 previous section. The steps leading to the development of the
(18)
optimal DA-SVMr hybrid algorithm are illustrated in the
flowchart presented in Figure 5.
n
∑i = 1 (γiexp − γical)2
R2 = 1 − n
∑i = 1 (γiexp − γ ̅ exp)2 (19)
In order to evaluate the predictive ability of the optimized
SVMr model, the validation agreement vector, and the
validation agreement plot of the predicted versus experimental
response variable from the validation dataset only are analyzed.
Using the Matlab function “postreg”, the linear regression of
the calculated versus experimental output is visualized.
The total data agreement scheme is shown in Figure 4,
which illustrates the SVMr model’s calculated outputs versus

Figure 5. Flowchart of the DA-SVM optimization process.

The machine learning algorithm principle remains the same,

Figure 4. Scatter plot of the global data adjusted by the optimal SVMr
model.
the experimental data with an agreement vector [α (slope), τ
(y intercept), R (correlation coefficient)] = [0.9871, 0.0466,
0.9951]. The results reveal an overall accuracy of the
developed model in correlating the total data. Moreover, the
preponderance of the test data which follows exactly the trend
of the SVMr model linear regression except for few points
(<3% of the test data) that yielded higher deviations, elucidates
the prediction precision of the optimized model appraised by
its RMSE, R and R2 of a value of 0.1827, 0.9951, and 0.9899,
respectively.
As mentioned above, in the previous SVMr modeling, the
optimization of the three hyper-parameters, which are the
regularization constant C, the ε-insensitive loss function
parameter, and the kernel function’s parameter γ, is crucial
to the performance of the model and is performed during the
training phase through a grid search within the parameters
intervals listed earlier and based on holdout cross-validation.
However, this optimization technique is quite traditional and
the chance of missing the optimal target is high because of the
unavoidable spans inside each interval. Therefore, it will be
interesting to adopt other types of optimization of the hyper-
parameters, among which a SI based method known as DA.
3.2.2. DA-SVMr Model. Previous papers have coupled SI
optimization algorithms with learning machines and the results
were promising.52−54 The proposed model is based on SVMr
G https://dx.doi.org/10.1021/acs.jced.0c00168
however, the DA algorithm feeds the SVM initially with a
random combination of hyper-parameters within their ranges.
The steps beginning with division of data and up until the
development of SVMr model are repeated and the minimum
value of RMSE obtained is saved as best through five iterations
of a simulation. Then, the DA generates a new population of
hyper-parameters for the SVMr algorithm and the same set of
steps are repeated in order to achieve a new best RMSE and
that is for 100 trials, amongst which the minimum RMSE
corresponds to the resultant optimal DA-SVMr model.
The same process explained above is tested with different
kernel functions, namely, linear, polynomial, RBF and
Gaussian. Results of DA-SVMr modeling of the same data
using different kernel functions are summarized in a Table 4.
Based on the results obtained, the linear kernel function gave
fair modeling results by DA-SVMr and yielded the highest
errors and lowest correlation coefficient among all kernel
functions. The nonlinearity of the system studied and its
complexity thermodynamically and physicochemically are the
main reasons for the poor linear kernel performance. On the
other hand, the polynomial kernel degree is finely tuned to an
optimal fractional order which usually gives better results than
the real values of orders. Although, the polynomial of
optimized degree 3.33 and the Gaussian kernels gave better
results than the linear one, the RBF outperformed all tested
functions and the DA-SVMr RBF-based model capitulated the
most accurate predictions.
The hyper-parameters optimized by DA for hybrid modeling
of IDAC based on SVM for regression (SVMr) using the RBF
kernel function are C, ε, and γ estimated at 176.023, 0.032, and
2.190, respectively.
All the necessary files for reproduction of the results are
available in the Supporting Information.
As shown in Figure 6, the optimal DA-SVMr model using
the RBF exhibited a remarkable efficiency in correlating the
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data pubs.acs.org/jced Article

Table 4. Results of DA-SVMr Modeling Using Different Kernel Functions

DA-optimized hyper-parameters DA-SVMr model statistical parameters
C ε γ n quantity of support vectors R R2 RMSE MAPE (%) MAE
linear 21.368 0.7967 1748 0.8758 0.6891 0.8926 30.608 0.4996
RBF 176.023 0.0319 2.1901 1457 0.9954 0.9906 0.1785 3.7801 0.0979
polynomial 1 0.1321 3.3273 1485 0.9799 0.9588 0.3635 12.6783 0.2716
Gaussian 244.2572 0.0458 1.8723 1421 0.99295 0.9855 0.2141 4.336 0.1203

affect the accuracy of the data points, which influence the

validity of the model.55 The data points distant from the
general trend of the majority of data points are called outliers.
Furthermore, discovering such data points is crucial for
improving the model accuracy by eliminating the suspected
inexact experimental data which weakens the model perform-
ance.56 In the present study, the Leverage mathematical
technique is used to detect outliers, where the residual values
and a Hat matrix are employed. Mohammadi et al.57 gave a
detailed path for creating the Hat values, and the main steps
are the following

H = X(XTX )−1XT (20)

where X designates the input experimental observation matrix

Figure 6. Scatter plot of the global data adjusted by the optimal DA-
SVMr model.
global data, confirmed by a correlation coefficient’s value of
0.99575 and a significant low RMSE of 0.1696. Also, the
predictive ability of the DA-SVM model is demonstrated by
testing 666 data points which follow closely the trend of the
experimental IDAC, except for few points for which the
deviations between experimental and model predicted values
are noteworthy. The predictive correlation coefficient R,
RMSE, and MAPE are 0.9954, 0.1785, and 3.7801%,
respectively. Also, the marginal loss between the R2 for
training and testing of an optimal DA-SVMr model is
insignificant suggesting its high generalization performance in
terms of R2.
3.2.3. Outlier Detection for the DA-SVM Model. As shown
in Figure 6, there are data points relatively distant from the
bisector line. The fact that in this study, a large experimental
dataset is used to develop the regression model, errors, and
uncertainties resulting from laboratorial measurements may
(m × n), m is the number of observations, and n is the number
of model input parameters. The Hat values are deducted
directly from the diagonal of the matrix H created by eq 20.
Hat = diagonale(H ) (21)
In our study, the DA-SVM model presents higher accuracy
than the SVM model, the reason why it is considered for the
outlier search. Consequently, a William’s diagram representing
graphically the normalized residuals according to the Leverage
(Hat) values is established and allows the classification of the
total data points between validated data and outliers
(suspected data). The critical leverage H* in the plot is
defined by the following equation
3(n + 1)
H* =
m (22)
The normalized residuals are calculated using eq 23

Figure 7. William’s Diagram for detection of outliers for the DA-SVM model.

H https://dx.doi.org/10.1021/acs.jced.0c00168
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data pubs.acs.org/jced Article

(γi∞exp − γi∞cal) Table 5. Statistical Evaluation of the Models’ Performance

(R _Norm)i = i = 1, ...m
Var(γi∞exp − γi∞cal) COSMO-RS3 SVM DA-SVM
RMSE 1.1180 0.2421 0.1785
(23)
MAE 0.7822 0.1077 0.0979
Normalized residuals equal ±3 are considered margin limits MAPE 22.7504 3.6446 3.7801
for validated data, whereas residuals outside these ranges MSE 1.2499 0.0586 0.0319
define suspected data. In addition, all data points with Hat MRSE 0.1905 0.0101 0.0116
values > H* are also considered as suspected data. The results RAE 507.9285 6.7443 7.7576
of the outlier analysis is presented in Figure 7. Af 1.2724 1.0382 1.0503
Based on the abovementioned figure, the H* value is 0.0101, Bf 0.9703 0.9975 0.9907
and only the data represented by green circles is the valid data R 0.8412 0.9912 0.9954
and for which the model’s accuracy is confirmed. This set has R2 0.7076 0.9825 0.9908
2573 data points out of the 2666 overall data that was
originally used to develop the DA-SVM model and represents a
ratio of 96.51% of the overall experimental data. The doubtful allow the representation of the nonlinear relationship between
data are designated by blue triangles and encloses 93 outliers the IDAC of solutes in 44 imidazolium-based ILs and the
corresponding to 3.49% of the overall experimental data. The molecular structural charge density of the solute and solvent,
validation of the model is moreover confirmed within the range and that to a large extent.
of the validated data and suspicious data and is clearly Despite the fact that COSMO-RS is an advanced technique
perceived. that is considered predictive insofar as it does not rely on
3.3. Comparison of Models. The SVMr and DA-SVMr experimental data for predicting IDAC, this hybrid quantum
models developed in this work and the COSMO-RS-based mechanical thermodynamic method provides rough estima-
model3 for the estimation of IDAC are compared in terms of tions of the parameter, which can be clearly seen in Figure 8.
certain statistical indices for the determination of models’ Whereas, the σ-profile of molecules delivered by COSMO-RS3
performance. The evaluation criteria listed above which are the seem to be closely relevant and quantitatively representative of
RMSE, the MAE, the MAPE, the coefficient of correlation (R), the molecular level interactions between the solute and the
and the determination coefficient (R2) calculated by eqs solvent without explicit knowledge of these interactions. The
15−19, respectively, are calculated for the evaluation of judicious choice of the COSMO-RS σ-profile descriptors as
performance of each model, hence accentuation of the model inputs for the development of correlative models based on the
that gave the most accurate predictions. In addition, other SVM algorithm resulted in significantly more accurate models
evaluation terms are considered, namely, the mean square error for IDAC estimation, and Table 5 confirms these results in
(MSE), the mean relative squared error (MRSE), the relative terms of the statistical evaluation parameters of the three
absolute error (RAE), the accuracy factor (Af), and bias factor models.
(Bf) are given by eqs 24−28,respectively.58 By associating DA with SVM regression and using COSMO-
RS σ-profile descriptors as input variables, the DA-SVMr
N
1 model promotes approximately zero uncertainties in inputs and
MSE = ∑ (γ ∞Exp − γi∞cal)2 finely selected hyper-parameters of SVMr. In trade off, the
N i=1 i (24) good results obtained by the DA-SVMr model is the absolute
N i ∞Exp
jγ − γi∞cal yzz
MRSE = ∑ jjjj i zz
independency of the validation dataset from the training

zz
2

N i=1 j
1 dataset and from the subset of data which is used in the

k {
γi∞Exp assessment of the DA-SVMr optimization performance. For
(25) this purpose, the function Matlab “holdout” for cross-
validation is used and to ensure that the DA-SVMr optimal
N
γi∞Exp − γi∞cal model is not contingent on the validation data. Consequently,
RAE = ∑ the improved predictive accuracy of the model is the result of
i=1
γi∞Exp (26) the swarm optimization of the learning machine hyper-
γi∞cal
parameters and certainly not the result of overfitting.59,60
N
(∑i + 1 |log |/N)
A f = 10 γi∞exp (27) 4. CONCLUSIONS
N γ ∞cal In this study, two SVMr models were developed for the
(∑i + 1 log i∞exp /N) estimation of IDAC of seventeen solutes in 44 imidazolium-
Bf = 10 γi (28)
based ILs based on temperature, molecular weight of solute
The values of the ten statistical evaluation indices of the and solvent, and five COSMO-RS σ-profile descriptors for
three models discussed in this work for prediction (validation both ILs and solutes. Experimental data is selected from the
data) are summarized in Table 5. literature and is closely analyzed statistically. Two advanced
Based on the models’ statistical parameter RMSE, it can be deep learning regularization techniques, known as Lasso and
seen that the two SVMr-based models surpassed the COSMO- Ridge are applied in this study to illustrate the decisive
RS model.3 The difference between the two models (SVMr selection of input parameters. The two developed models show
and DA-SVMr) is insignificant compared to that of the two a good correlative and predictive accuracy. Statistical the
same models with the COSMO-RS one. Moreover, the values comparison of different models reveals a weak performance of
of R2 (for validation) and ΔR2 in addition to the RMSE imply a COSMO-RS model3 in predicting IDAC in contrast to the
that the DA-SVMr model has more predictive power than the two SVMr models. The results confirm that the COSMO-RS is
SVMr. This means that the two models proposed in this work a good source of structural molecular information about the
I https://dx.doi.org/10.1021/acs.jced.0c00168
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 8. Parity plots of the experimental versus calculated γ∞
i by the three models. (a) COSMO-RS , (b) SVMr model, and (c) DA-SVMr model.
molecules of solutes and solvents (ILs). Furthermore, the DA-
SVMr model outperformed the SVM model with a validation
correlation coefficient of 0.9954 and a RMSE equal to 0.1785.
These results demonstrate the improved performance of SVM
for regression when the hyper-parameters are optimized using
DA. Despite the better results and improved accuracy obtained
with the DA-SVMr model, associating SVMr with other SI
algorithms for optimization of hyper-parameters is highly
recommended as this may lead to even more accurate models.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jced.0c00168.
ZIP file contains ‘data_ss.xlsx’ and ‘data_ss_Info.docx’
providing the data points used for modeling. It also
encloses two folders ‘DA-SVM’ and ‘SVM’ which include
the two models developed in this work using Matlab,
along with a ‘README_File.docx’ that describes each of
the other files and how they are used together (ZIP)
■
AUTHOR INFORMATION
Corresponding Author
Hania Benimam − Biomaterials and Transport Phenomena
Laboratory (LBMPT), University Yahia Fares of Medea,
Medea 26000, Algeria; orcid.org/0000-0002-9786-7166;
Phone: +213 669542184; Email: hbenimam@gmail.com
Authors
Cherif Si Moussa − Biomaterials and Transport Phenomena
Laboratory (LBMPT), University Yahia Fares of Medea,
Medea 26000, Algeria; Department of Process Engineering,
Institute of Technology, University Dr. Yahia Fares of Medea,
Medea 26000, Algeria
Mohamed Hentabli − Biomaterials and Transport Phenomena
Laboratory (LBMPT), University Yahia Fares of Medea,
Medea 26000, Algeria; Department of Process Engineering,
Institute of Technology, University Dr. Yahia Fares of Medea,
Medea 26000, Algeria; Laboratory of Quality Control, Physico-
Chemical Department, SAIDAL of Medea, Medea 26000,
Algeria; orcid.org/0000-0002-6693-0708
Salah Hanini − Biomaterials and Transport Phenomena
Laboratory (LBMPT), University Yahia Fares of Medea,
Medea 26000, Algeria
J https://dx.doi.org/10.1021/acs.jced.0c00168
pubs.acs.org/jced Article
3
Maamar Laidi − Biomaterials and Transport Phenomena
Laboratory (LBMPT), University Yahia Fares of Medea,
Medea 26000, Algeria; Department of Process Engineering,
Institute of Technology, University Dr. Yahia Fares of Medea,
Medea 26000, Algeria
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jced.0c00168
Notes
The authors declare no competing financial interest.
■ REFERENCES
(1) Welton, T. Room-Temperature Ionic Liquids. Solvents for
Synthesis and Catalysis. Chem. Rev. 1999, 99, 2071−2084.
(2) Freemantle, M. An Introduction to Ionic Liquids; Royal Society of
Chemistry, 2010.
(3) Paduszyński, K. An Overview of the Performance of the
COSMO-RS Approach in Predicting the Activity Coefficients of
Molecular Solutes in Ionic Liquids and Derived Properties at Infinite
Dilution. Phys. Chem. Chem. Phys. 2017, 19, 11835−11850.
(4) Lei, Z.; Dai, C.; Zhu, J.; Chen, B. Extractive Distillation with
Ionic Liquids: A Review. AIChE J. 2014, 60, 3312−3329.
(5) Kato, R.; Krummen, M.; Gmehling, J. Measurement and
Correlation of Vapor−liquid Equilibria and Excess Enthalpies of
Binary Systems Containing Ionic Liquids and Hydrocarbons. Fluid
Phase Equilib. 2004, 224, 47−54.
(6) Brennecke, J. F.; Maginn, E. J. Ionic Liquids: Innovative Fluids
for Chemical Processing. AIChE J. 2001, 47, 2384−2389.
(7) Kazakov, A.; Magee, J. W.; Chirico, R. D.; Diky, V.; Muzny, C.
D.; Kroenlein, K.; Frenkel, M. NIST Standard Reference Database 147:
NIST Ionic Liquids Database(ILThermo). Version 2.0; National
Institute of Standards and Technology: Gaithersburg MD. There is no
Corresp. Rec. this Ref, 2013.
(8) Paduszyński, K. In Silico Calculation of Infinite Dilution Activity
Coefficients of Molecular Solutes in Ionic Liquids: Critical Review of
Current Methods and New Models Based on Three Machine
Learning Algorithms. J. Chem. Inf. Model. 2016, 56, 1420−1437.
(9) Weidlich, U.; Gmehling, J. A Modified UNIFAC Model. 1.
Prediction of VLE, HE, and .Gamma..Infin. Ind. Eng. Chem. Res. 1987,
26, 1372−1381.
(10) Simoni, L. D.; Lin, Y.; Brennecke, J. F.; Stadtherr, M. A.
Modeling Liquid− Liquid Equilibrium of Ionic Liquid Systems with
NRTL, Electrolyte-NRTL, and UNIQUAC. Ind. Eng. Chem. Res.
2008, 47, 256−272.
(11) Eike, D. M.; Brennecke, J. F.; Maginn, E. J. Predicting Infinite-
Dilution Activity Coefficients of Organic Solutes in Ionic Liquids. Ind.
Eng. Chem. Res. 2004, 43, 1039−1048.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(12) Tämm, K.; Burk, P. QSPR Analysis for Infinite Dilution
Activity Coefficients of Organic Compounds. J. Mol. Model. 2006, 12,
417−421.
(13) Xi, L.; Sun, H.; Li, J.; Liu, H.; Yao, X.; Gramatica, P. Prediction
of Infinite-Dilution Activity Coefficients of Organic Solutes in Ionic
Liquids Using Temperature-Dependent Quantitative Structure −
Property Relationship Method. Chem. Eng. J. 2010, 163, 195−201.
(14) Grubbs, L. M.; Ye, S.; Saifullah, M.; McMillan-Wiggins, M. C.;
Acree, W. E.; Abraham, M. H.; Twu, P.; Anderson, J. L. Correlations
for Describing Gas-to-Ionic Liquid Partitioning at 323 K Based on
Ion-Specific Equation Coefficient and Group Contribution Versions
of the Abraham Model. Fluid Phase Equilib. 2011, 301, 257−266.
(15) Mutelet, F.; Ortega-Villa, V.; Moïse, J.-C.; Jaubert, J.-N.; Acree,
W. E. Prediction of Partition Coefficients of Organic Compounds in
Ionic Liquids Using a Temperature-Dependent Linear Solvation
Energy Relationship with Parameters Calculated through a Group
Contribution Method. J. Chem. Eng. Data 2011, 56, 3598−3606.
(16) Stephens, T. W.; Chou, V.; Quay, A. N.; Shen, C.; Dabadge, N.;
Tian, A.; Loera, M.; Willis, B.; Wilson, A.; Acree, W. E.; Twu, P.;
Anderson, J. L.; Abraham, M. H. Thermochemical Investigations of
Solute Transfer into Ionic Liquid Solvents: Updated Abraham Model
Equation Coefficients for Solute Activity Coefficient and Partition
Coefficient Predictions. Phys. Chem. Liq. 2014, 52, 488−518.
(17) Gonfa, G.; Bustam, M. A.; Sharif, A. M.; Mohamad, N.; Ullah,
S. Tuning Ionic Liquids for Natural Gas Dehydration Using COSMO-
RS Methodology. J. Nat. Gas Sci. Eng. 2015, 27, 1141−1148.
(18) Gonfa, G.; Bustam, M. A.; Shariff, A. M.; Muhammad, N.;
Ullah, S. Quantitative Structure−activity Relationships (QSARs) for
Estimation of Activity Coefficient at Infinite Dilution of Water in
Ionic Liquids for Natural Gas Dehydration. J. Taiwan Inst. Chem. Eng.
2016, 66, 222−229.
(19) Shiflett, M. B.; Maginn, E. J. The Solubility of Gases in Ionic
Liquids. AIChE J. 2017, 63, 4722−4737.
(20) Matheswaran, P.; Wilfred, C. D.; Kurnia, K. A.; Ramli, A.
Prediction of Activity Coefficient of Sulfones at Infinite Dilution in
Ionic Liquids and Their Modeling Using COSMO-RS. AIP Conference
Proceedings; AIP Publishing, 2016; Vol. 1787, p 020007.
(21) Wang, S.; Sandler, S. I.; Chen, C.-C. Refinement of COSMO−
SAC and the Applications. Ind. Eng. Chem. Res. 2007, 46, 7275−7288.
(22) Ajmani, S.; Rogers, S. C.; Barley, M. H.; Burgess, A. N.;
Livingstone, D. J. Characterization of Mixtures Part 1: Prediction of
Infinite-Dilution Activity Coefficients Using Neural Network-Based
QSPR Models. QSAR Comb. Sci. 2008, 27, 1346−1361.
(23) Nami, F.; Deyhimi, F. Prediction of Activity Coefficients at
Infinite Dilution for Organic Solutes in Ionic Liquids by Artificial
Neural Network. J. Chem. Thermodyn. 2011, 43, 22−27.
(24) Banerjee, T.; Khanna, A. Infinite Dilution Activity Coefficients
for Trihexyltetradecyl Phosphonium Ionic Liquids: Measurements
and COSMO-RS Prediction. J. Chem. Eng. Data 2006, 51, 2170−
2177.
(25) Diedenhofen, M.; Eckert, F.; Klamt, A. Prediction of Infinite
Dilution Activity Coefficients of Organic Compounds in Ionic Liquids
Using COSMO-RS. J. Chem. Eng. Data 2003, 48, 475−479.
(26) Freire, M. G.; Ventura, S. P. M.; Santos, L. M. N. B. F.;
Marrucho, I. M.; Coutinho, J. A. P. Evaluation of COSMO-RS for the
Prediction of LLE and VLE of Water and Ionic Liquids Binary
Systems. Fluid Phase Equilib. 2008, 268, 74−84.
(27) Kurnia, K. A.; Pinho, S. P.; Coutinho, J. A. P. Evaluation of the
Conductor-like Screening Model for Real Solvents for the Prediction
of the Water Activity Coefficient at Infinite Dilution in Ionic Liquids.
Ind. Eng. Chem. Res. 2014, 53, 12466−12475.
(28) Diedenhofen, M.; Klamt, A. COSMO-RS as a Tool for Property
Prediction of IL Mixtures-A Review. Fluid Phase Equilib. 2010, 294,
31−38.
(29) Kumar, A. A. P.; Banerjee, T. Thiophene Separation with Ionic
Liquids for Desulphurization: A Quantum Chemical Approach. Fluid
Phase Equilib. 2009, 278, 1−8.
(30) Kurnia, K. A.; Pinho, S. P.; Coutinho, J. A. P. Evaluation of the
Conductor-like Screening Model for Real Solvents for the Prediction
K https://dx.doi.org/10.1021/acs.jced.0c00168
pubs.acs.org/jced Article
of the Water Activity Coefficient at Infinite Dilution in Ionic Liquids.
Ind. Eng. Chem. Res. 2014, 53, 12466−12475.
(31) Matheswaran, P.; Wilfred, C. D.; Kurnia, K. A.; Ramli, A.
Overview of Activity Coefficient of Thiophene at Infinite Dilution in
Ionic Liquids and Their Modeling Using COSMO-RS. Ind. Eng.
Chem. Res. 2016, 55, 788−797.
(32) Vapnik, A. V. The Nature of Statistical Learning Theory;
Springer-Verlag: New York, 1995.
(33) Yoon, H.; Jun, S.-C.; Hyun, Y.; Bae, G.-O.; Lee, K.-K. A
Comparative Study of Artificial Neural Networks and Support Vector
Machines for Predicting Groundwater Levels in a Coastal Aquifer. J.
Hydrol. 2011, 396, 128−138.
(34) Drucker, H.; Burges, C. J. C.; Kaufman, L.; Smola, A. J.; Vapnik,
V. Support Vector Regression Machines. Advances in Neural
Information Processing Systems; MIT Press, 1997; pp 155−161.
(35) Yu, P.-S.; Chen, S.-T.; Chang, I.-F. Support Vector Regression
for Real-Time Flood Stage Forecasting. J. Hydrol. 2006, 328, 704−
716.
(36) Wu, C.-H.; Ho, J.-M.; Lee, D. T. Travel-Time Prediction with
Support Vector Regression. IEEE Trans. Intell. Transp. Syst. 2004, 5,
276−281.
(37) Wen, Y. F.; Cai, C. Z.; Liu, X. H.; Pei, J. F.; Zhu, X. J.; Xiao, T.
T. Corrosion Rate Prediction of 3C Steel under Different Seawater
Environment by Using Support Vector Regression. Corros. Sci. 2009,
51, 349−355.
(38) Chevalier, R. F.; Hoogenboom, G.; McClendon, R. W.; Paz, J.
A. Support Vector Regression with Reduced Training Sets for Air
Temperature Prediction: A Comparison with Artificial Neural
Networks. Neural Comput. Appl. 2011, 20, 151−159.
(39) He, Z.; Wen, X.; Liu, H.; Du, J. A Comparative Study of
Artificial Neural Network, Adaptive Neuro Fuzzy Inference System
and Support Vector Machine for Forecasting River Flow in the
Semiarid Mountain Region. J. Hydrol. 2014, 509, 379−386.
(40) Parveen, N.; Zaidi, S.; Danish, M. Support Vector Regression
Model for Predicting the Sorption Capacity of Lead (II). Perspect. Sci.
2016, 8, 629−631.
(41) Vapnik, V.; Golowich, S. E.; Smola, A. J. Support Vector
Method for Function Approximation, Regression Estimation and
Signal Processing. In Advances in Neural Information Processing
Systems; MIT Press, 1997; pp 281−287.
(42) Beni, G.; Wang, J. Swarm Intelligence in Cellular Robotic
Systems. Robots and Biological Systems: Towards a New Bionics?;
Springer Berlin Heidelberg: Berlin, Heidelberg, 1993; pp 703−712.
(43) Bonabeau, E.; Dorigo, M.; Theraulaz, G. Swarm Intelligence:
From Natural to Artificial Systems; Oxford University Press: New York,
1999.
(44) Tharwat, A.; Moemen, Y. S.; Hassanien, A. E. Classification of
Toxicity Effects of Biotransformed Hepatic Drugs Using Whale
Optimized Support Vector Machines. J. Biomed. Inf. 2017, 68, 132−
149.
(45) Mirjalili, S. Dragonfly Algorithm: A New Meta-Heuristic
Optimization Technique for Solving Single-Objective, Discrete, and
Multi-Objective Problems. Neural Comput. Appl. 2016, 27, 1053−
1073.
(46) Mullins, E.; Oldland, R.; Liu, Y. A.; Wang, S.; Sandler, S. I.;
Chen, C.-C.; Zwolak, M.; Seavey, K. C. Sigma-Profile Database for
Using COSMO-Based Thermodynamic Methods. Ind. Eng. Chem. Res.
2006, 45, 4389−4415.
(47) Klamt, A. The COSMO and COSMO-RS Solvation Models.
Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2011, 1, 699−709.
(48) Klamt, A. Conductor-like Screening Model for Real Solvents: A
New Approach to the Quantitative Calculation of Solvation
Phenomena. J. Phys. Chem. 1995, 99, 2224−2235.
(49) Eckert, F.; Klamt, A. Fast Solvent Screening via Quantum
Chemistry: COSMO-RS Approach. AIChE J. 2002, 48, 369−385.
(50) Klamt, A.; Jonas, V.; Bürger, T.; Lohrenz, J. C. W. Refinement
and Parametrization of COSMO-RS. J. Phys. Chem. A 1998, 102,
5074−5085.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data pubs.acs.org/jced Article

(51) Peter D, H. Kernel Estimation of a Distribution Function.

Commun. Stat. Theor. Methods 1985, 14, 605−620.
(52) Khaouane, L.; Si-Moussa, C.; Hanini, S.; Benkortbi, O.
Optimization of Culture Conditions for the Production of Pleuro-
mutilin from Pleurotus Mutilus Using a Hybrid Method Based on
Central Composite Design, Neural Network, and Particle Swarm
Optimization. Biotechnol. Bioprocess Eng. 2012, 17, 1048−1054.
(53) Amroune, M.; Bouktir, T.; Musirin. Power System Voltage
Stability Assessment Using a Hybrid Approach Combining Dragonfly
Optimization Algorithm and Support Vector Regression. Arabian J.
Sci. Eng. 2018, 43, 3023−3036.
(54) Keskes, S.; Hanini, S.; Hentabli, M.; Laidi, M. Artificial
Intelligence and Mathematical Modelling of the Drying Kinetics of
Pharmaceutical Powders. Kem. Ind. 2020, 69, 137−152.
(55) Rousseeuw, P. J.; Leroy, A. M. Robust Regression and Outlier
Detection; Wiley: New York, 1987; Vol. 254.
(56) Hosseinzadeh, M.; Hemmati-Sarapardeh, A. Toward a
Predictive Model for Estimating Viscosity of Ternary Mixtures
Containing Ionic Liquids. J. Mol. Liq. 2014, 200, 340−348.
(57) Mohammadi, A. H.; Gharagheizi, F.; Eslamimanesh, A.; Richon,
D. Evaluation of Experimental Data for Wax and Diamondoids
Solubility in Gaseous Systems. Chem. Eng. Sci. 2012, 81, 1−7.
(58) Soleimani, R.; Saeedi Dehaghani, A. H.; Shoushtari, N. A.;
Yaghoubi, P.; Bahadori, A. Toward an Intelligent Approach for
Predicting Surface Tension of Binary Mixtures Containing Ionic
Liquids. Korean J. Chem. Eng. 2018, 35, 1556−1569.
(59) Huang, C.-L.; Wang, C.-J. A GA-Based Feature Selection and
Parameters Optimizationfor Support Vector Machines. Expert Syst.
Appl. 2006, 31, 231−240.
(60) Lin, S.-W.; Ying, K.-C.; Chen, S.-C.; Lee, Z.-J. Particle Swarm
Optimization for Parameter Determination and Feature Selection of
Support Vector Machines. Expert Syst. Appl. 2008, 35, 1817−1824.

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