Neural Computing and Applications

https://doi.org/10.1007/s00521-019-04356-w (0123456789().,-volV)(0123456789().,-volV)

ORIGINAL ARTICLE

Modeling the activity coefficient at infinite dilution of water in ionic

liquids using artificial neural networks and support vector machines
Hania Benimam1 • Cherif Si-Moussa1 • Maamar Laidi1 • Salah Hanini1

Received: 23 May 2018 / Accepted: 18 July 2019

 Springer-Verlag London Ltd., part of Springer Nature 2019

Abstract
The activity coefficient at infinite dilution of water in ionic liquids is a thermodynamic property of a paramount importance
in separation processes. However, accurate modeling of this parameter remains a challenging task due to the highly
nonlinear behavior of the water/ionic liquid systems. Also, available models consider a large number of inputs that are
usually difficult to access and require complicated use techniques. Therefore, the main objective of this paper is to use
artificial intelligence techniques to propose models (based on a reduced number of inputs that are easily accessible, and to
improve the accuracy of the correlative performance for activity coefficient at infinite dilution of water in ILs). The present
work features the application of artificial neural networks, support vector machine and least square support vector machine,
among data-driven methods, for modeling the activity coefficient at infinite dilution of water in 53 ionic liquids. Overall,
the models proposed are able to accurately correlate 318 experimental data points gathered from the literature. According
to the results, the ANN is more powerful and effective computational learning machine than the two remaining ones. The
correlation coefficients R2 and deviations expressed as an average absolute relative deviation for the neural network model
are estimated to be 0.99997 and 0.56%, respectively. Furthermore, the neural network model’s interpolation and extrap-
olation capabilities are demonstrated, and its accuracy is compared to other proposed models in the literature based on
multi-linear regression, least squares support vector machine and another feedforward neural network. This work also
includes a graphical user interface for the proposed model, as well as an inputs’ sensitivity analysis.

Keywords Activity coefficient  Ionic liquids  Artificial neural networks  Support vector machine  Least square support
vector machine  Infinite dilution

1 Introduction processes with no negative impact on the atmosphere in

Ionic liquids (ILs) are a new class of organic-based salts
that present numerous advantageous physicochemical
properties compared to volatile organic solvents. They
have attracted a considerable interest during the last two
decades within the academic and industrial fields due to
their growing potential applications. Literature stated that
ILs may help in improving the capability of chemical
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s00521-019-04356-w) con-
tains supplementary material, which is available to autho-
rized users.
& Maamar Laidi
laidi.maamar@univ-medea.dz
1
Biomaterials and Transport Phenomena Laboratory
(LBMPT), University Yahia Fares of Médéa, Médéa, Algeria
contrast to volatile organic solvents. They are normally
composed of a large organic cations and organic or inor-
ganic anions. When the melting point is at room temper-
ature, the ILs are referred to as room-temperature ionic
liquids (RTILs) [1–4].
The remarkable physicochemical properties of ILs such
as low vapor pressure, non-flammability, high solvating
power [5] for organic, inorganic and organometallic com-
pounds and high thermal stability [6] have made them the
subject of exploration in numerous applications. Further-
more, non-aqueous high polarity, viscosity, high thermal
conductivity and solubility of ILs can be finely tuned by
selecting the combination of cations or anions among a
huge diversity, allowing the design of an appropriate IL for
a particular application [7–9], such as reaction media
[10–12], active pharmaceutical ingredients [13], solvents
of poorly soluble drugs, their precursors, and even as drug

123

delivery vehicles [14, 15], catalysts [12] and separation
media [16]. Hence, the subsequent numbers of commer-
cially or not available ILs are annually and exponentially
increasing [17, 18]. The knowledge of their physical and
chemical properties and phase equilibrium is fundamental
for their applications.
It has been roughly estimated that about 106 possible
ionic liquids could be theoretically produced by the com-
bination of cations and anions from the current chemical
database. In addition, the binary and ternary mixture of
ionic liquids could produce 1012 and 1018 ionic liquid
possibilities, respectively [19]. This makes the experi-
mental characterization of all possible ionic liquids for the
selection of an optimum ionic liquid for specific purpose
unfeasible. Therefore, predictive models that enable a
priori estimation of the properties of ionic liquids are
necessary [20].
In order to use ILs as solvents in industry, namely
selection of solvents for liquid–liquid extraction, extractive
distillation, separation of the azeotropic mixtures and
separation processes, or design new ones, the knowledge of
interactions of ILs with different compounds is needed.
The solute–solvent complex and dynamic interactions in
solution are controlled by the nature and interplay of the
cation–anion pair containing the IL. Thus, these interac-
tions are the outcome of various energetic and geometric
factors leading to uniquely organized, hydrogen-bonded
and self-segregated solvent nanostructures [21]. Conse-
quently, a profound study linking the chemical structure of
the ILs with their physicochemical and thermodynamic
properties is indispensable in order to embrace these
compounds as new promising solvents.
For instance, in extraction and separation processes, the
choice of a solvent is interrelated to two fundamental
properties which are its selectivity and capacity. These two
can be calculated using the activity coefficient at infinite-
dilution values by simple expressions: selectivity Sij =
c! ! ! !
i /cj and capacity kj = 1/cj [22].
The most broadly used methods for probing the inter-
action between an ionic liquid and water use either
experimental techniques, such as infrared (IR) and nuclear
magnetic resonance (NMR) spectroscopy [23–28] or the-
oretical calculations [27, 29–31].
Given the importance of the activity coefficient at infi-
nite dilution of organic or inorganic solutes in ILs, in the
selection and design of separation processes, a lot of
researches have been focused in this area. One of the
earliest researches was carried out by Domańska and
Marciniak in 2007 [32] where they measured the activity
coefficients at infinite dilution c!, for 29 solutes, alkanes,
alkenes, alkynes, cycloalkanes, aromatic hydrocarbons,
alcohols and water in the ionic liquid 1-ethyl-3-
methylimidazolium trifluoroacetate ([EMIM] [TFA]) using
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Neural Computing and Applications
gas liquid chromatography (GLC). Their study was fol-
lowed by a succession of works established by the same
authors based on the same principle but different ionic
liquids [33–35]. Other collaborations aiming the estimation
of activity coefficient at infinite dilution of organic and
inorganic solutes and water in different ionic liquids often
by GLC were conducted using almost the same protocol
[36–40]. However, due to the massive number of possible
ILs, conducting time-consuming and expensive experi-
ments for the estimation of infinite-dilution activity coef-
ficient (IDAC) in ILs has became impractical, the reason
why a lot of researches have been devoted to develop
theoretical and computational modeling of this property.
Detailed review of the previous works on modeling the
infinite-dilution activity coefficient of different solutes in
ILs is given in Sect. 2. Paduszynski [41] whose work will
be discussed in detail in the following section summarized
the main research achievements in modeling activity
coefficient at infinite dilution. The author argues that
despite the fact that conductor-like screening model for real
solvents (COSMO-RS) computation method allows a
deeper insight into interactions between ILs and solutes, it
necessitates a commercial package and it is quite compli-
cated in use and requires user’s quantum chemical exper-
tise and experience which makes its implementation in
research quite a difficult and challenging task. Hence,
quantitative structure–property relationship (QSPR) mod-
els seem capable of overcoming these problems; therefore,
the author proposed three QSPR models based on three
machine learning algorithms for activity coefficient esti-
mation [41]. However, the models suffered from a large
number of input variables that needed methods and tech-
niques to reduce their number, and in many cases, the
inputs retained are not easily accessible. Nonetheless, the
quite high deviations that the models capitulate (average
absolute relative deviation AARD of more than 20%) is a
major reason to look for other models with improved
performance and accuracy, and also preferably using
fewer, simply calculated and significant input variables.
In this present work, an attempt will be made to estimate
activity coefficient at infinite dilution of water in ionic
liquids using three methods, a single artificial neural net-
work (ANN) predictive model, a support vector machine
and a least square support vector machine. The same set of
inputs is considered for the three types of models which
includes the temperature of the water/ionic liquid system T,
the molecular weight of the ionic liquid M and four pure
component properties of the ionic liquid: critical temper-
ature Tc, critical pressure Pc, critical volume Vc and
acentric factor x. The properties of the ILs are chosen as
inputs in the purpose of differentiating between the diverse
solvents (ILs) and describing all the systems water/ionic
liquid in one system. To the best of our knowledge, this
Neural Computing and Applications
will be the first attempt to model the IDAC of water in ILs
based on physical properties of ILs using three powerful
machine learning techniques. The number of inputs con-
sidered in this work is the least among other models pre-
viously proposed in the literature. An input sensitivity
analysis will play a double role, that of classification of
inputs parameters in terms of effect on the output and
confirmation of the appropriate choice of inputs. In sum-
mary, the aim of the study is to evaluate the capability of
the different machine learning techniques for modeling the
IDAC in the purpose of correlation and/or prediction, and
to compare the proposed models with three literature
models: a multi-linear regression (MLR) model based on
the COSMO-RS sigma profiles, least squares support
vector machine (LSSVM) model and feedforward artificial
neural network (FFANN) model.
2 Modeling the activity coefficient
at infinite dilution of water in ILs
IDAC can be defined as when the concentration of the
solute tends to zero or in the range from 10-7 to 10-4. The
importance of this parameter resides in describing the
behavior of liquid mixtures, fitting Gibbs free energy
model parameters (like Margules, Wilson, van Laar, non-
random two-liquid (NRTL), universal quasichemical
(UNIQUAC)), and development of predictive methods
such as the universal quasichemical functional group
activity coefficient (Dortmund) (UNIFAC (Do)) model
[42].
The experimental methods used for the measurement of
the infinite-dilution activity coefficients are GLC [43],
dilutor technique [44] and vapor–liquid equilibria VLE
measurements [45, 46]. However, due to the unlimited
possible combinations of cations and anions, the experi-
mental determination of activity coefficient at infinite
dilution of water in ILs is time-consuming and costly. The
opportunity to select new ILs may also be missed [47].
Hence, the use of predictive models is very helpful. Shiflett
and Maginn [48] gave an in-depth elucidation of the fluid
phase equilibrium of gas/IL systems and highlighted the
potential use of predictive computational modeling. A
review of an example application of computational intel-
ligence in hydrology field is presented by Ardabili et al.
[49], and another application in agricultural science is
provided by Zhang et al. [50].
The first type of predictive computational modeling is a
hybrid quantum/statistical thermodynamics method, and
the most commonly used approach in this kind of modeling
is the COSMO-RS. In this method, quantum mechanical
calculations are carried out on a solute in a conducting
continuum without a precise modeling of the solvent
molecules. The interactions between the solutes (in this
case water) and the solvent (IL) are obtained in the form of
pairwise interacting surface segments based on the geom-
etry and surface charge density of the solvent molecules.
Statistical thermodynamics model is subsequently applied
in order to calculate a thermodynamic property of fluids
and liquid mixtures, namely activity coefficient [48]. In-
depth description of the COSMO-RS theory and the
activity coefficient term is described in the literature
[51–55]. The first COSMO-RS model investigating the
activity coefficient at infinite dilution of solutes in ILs was
proposed by Diedenhofen et al. [56]. The study included 38
solutes in three different ionic liquids. The results had
proven the accuracy and capability of COSMO-RS method
in predicting the infinite-dilution activity coefficients in
various ionic liquids. Other researchers like Freire et al.
[57] used COSMO-RS method based on quantum chem-
istry calculations to predict binary liquid–liquid equilibria
LLE and VLE measurements in several alcohols–ILs sys-
tems. Their model predictions were reasonably in good
agreement with experimental data. Banerjee and Khanna
[58], Kurnia et al. [59], Gonfa et al. [60], Gonfa et al. [61]
and Matheswaran et al. [42] all employed COSMO-RS for
the prediction of activity coefficients at infinite dilution in
ILs. The results had proven the capability of the method in
predicting qualitatively the IDAC in ionic liquids, but had
often failed in providing accurate quantitative predictions.
Recently, Paduszynski [62] gave an overview of the
COSMO-RS performance in predicting the IDAC of dif-
ferent solutes in ILs. The approach was able to provide
quantitative and/or qualitative predictions of the largest
data set available yet with 41868 data points related to 150
molecular solutes and 233 ILs. However, the IDAC cal-
culation by this approach yielded an overall AARD of
approximately 30% which is still far from adequate.
Although the COSMO-RS models have become very
popular due to their logarithmic simplicity, numerical sta-
bility and their accuracy despite the outlying charge errors,
their major limitation results from the fact that the quantum
chemical calculations are performed only in the reference
state of a conductor, and not for real solvent polarity [63].
To overcome some of the limitations of COSMO-RS
which treats molecules in an implicit manner, atomistic
force field methods are a reliable alternative for estimation
of not just infinite-dilution activity coefficient in ILs but
also to obtain full isotherms. Based on atomistic simula-
tions and taking into account the energetics, also known as
force fields, this method uses molecular dynamics or Monte
Carlo methods to propose a statistical modeling of all
molecular aspects [48]. However, in the particular case of
water (as a solute), this method has failed to represent
experimental absorption isotherms. This is expected since
123

the current force fields lack polarizability treatment of the
solute and solvent [64].
Correlative methods, usually referred to as QSPR
models, are another computational modeling approach that
has shown high accuracy and robustness, especially when
applying advanced neural networks and other machine
learning techniques. The first QSPR models devoted to the
estimation of infinite-dilution activity coefficients in ILs
were proposed by Eike et al. [65]. Briefly, the study
involved 38 solutes in three ionic liquids and correlated
experimental IDAC with four descriptors for each IL at
four temperatures. However, for each solute/IL system, the
estimation of each descriptor had to be repeated at each
temperature. In addition, the models needed to be validated
both internally and externally to appraise the stability and
predictive ability of the model [66, 67]. The complexity
and inconvenience of the calculation process affected the
implementation of the QSPR models despite the satisfac-
tory results.
ANNs are a computational model inspired in the
behavior of natural neurons intended for modeling complex
nonlinear relationships [68]. Their most important advan-
tages are: (i) their ability to find traceability of the entrees
and (ii) their flexibility to test the interpolation, extrapo-
lation and prediction of the model [69]. The quantity and
placement of neurons in different layers is referred to as its
architecture. The neurons receive data related to a given
property, solubility, for instance, and some independent
variables related to the dependent main variable (temper-
ature at equilibrium, for instance). The input and output
variables are weighed by weights and shifted by a bias
factor specific to each neuron. Through a process of opti-
mization using traditional backpropagation algorithms or
evolutionary algorithms such as particle swarm optimiza-
tion (PSO) [70, 71], firefly algorithm [72], ant colony
optimization, artificial bee colony optimization, intelligent
water drop (IWD) approach [71], sequential genetic-based
negative correlation learning algorithm (SGNCL) [73] and
genetic algorithms, the network learns the relationship
between the variables and stores the values of the weights
and biases that give the lowest error between calculated
and experimental data of the dependent variable (activity
coefficient in this work) [68, 69, 74, 75]. A recent research
paper on swarm intelligence optimization approaches for
ANN optimization is proposed by Kaur et al. [71] and
reviews all the optimizations techniques listed above. Some
of the earliest applications of artificial neural networks-
based QSPR models for the prediction of IDAC in mixtures
were proposed by Ajmani et al. [76], and the constructed
models were satisfactory. Another attempt at predicting the
IDAC for organic solutes in ionic liquids by artificial
neural network was published in 2011 [74]. The authors
investigated 24 structurally different organic compounds
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Neural Computing and Applications
(alkanes, alkenes, alkynes, cycloalkanes, aromatics, and
alcohols) in 16 common imidazolium-based ionic liquids,
at different temperatures. The predicted and experimental
c!
i were in good agreement, and the root mean square error
(RMSE) was equal to 0.128 for test data [74].
Another excellent methodology which has recently
attracted extensive attention is support vector machines
(SVM). This method was developed by Vapnik in 1990s
and is based on statistical learning theory (SLT) imple-
ments structure risk minimization (SRM) theory [77, 78]. It
was primarily employed for nonlinear classification and
regression analysis [79, 80]. In this approach, consider a
training data set of N points (Xi, Yi), with i = 1,…,N. X
represents the model inputs and Y its output. An SVM
model takes the form:
y ð x Þ ¼ x T ;ð x Þ þ b ð1Þ
where ;ðÞ: Rn ! Rm a nonlinear function that maps input
finite-dimensional space into a higher-dimensional space
which is implicitly created, x is a weight vector and b is
the bias [81, 82].
The SVM problems are solved using quadratic pro-
gramming techniques, but these are known for their fol-
lowing disadvantages [83]:
• They are practically difficult to employ.
• They are time-consuming.
• They require a large memory and a considerable central
processing unit time (CPU time).
The least squares support vector machine (LSSVM), a
modified adaptation of the SVM was later developed. It
replaces the convex quadratic programming and inequality
constraints of the original SVM by solving a linear set of
equations and using equality constraints instead. In the
LSSVM method, a kernel function maps the finite input
space into a higher-dimensional attribute space [82, 83].
The LSSVM model can be expressed in Eq. (2) as:
X
N
yð xÞ ¼ ak K ðx; xk Þ þ b ð2Þ
k¼1
where a and b are the solutions of the following equation:
    
a o IT 0
¼ T ð3Þ
b I X þ c1 I y
where a ¼ ½a1 ; . . .; aN T are Lagrange multipliers and b is
the bias that are the solutions of Eq. (3);
I ¼ ½1; . . .; 1T ;
y ¼ ½y1 ; y2 ; . . .; yn T ;
X is a square matrix; the element of the i row and j column
is described as
Neural Computing and Applications
   
Xij ¼ ;ðxi ÞT ; xj ¼ K xi ; xj ð4Þ
where K is the kernel function and c is the regularization
parameter.
The LSSVM adapts as a lost function the square of the
error n2k between calculated and experimental data, while
the SVM chooses simply the error nk between the two
[82, 83].
Accordingly, the characteristics of the two analogous
methods make the LSSVM a better computational learning
machine because it reduces significantly the complexity of
the optimization algorithm, and this decreases the compu-
tational burden and accelerates the computation time [84].
The advantages of the two methods reside in: (i) the
regularization parameter, which results in avoiding over-
fitting; (ii) the use of kernel trick and kernel engineering
that allow an explicit knowledge about the problem; (iii) in
SVM, the problem is solved by a convex optimization,
which circumvents the local minima problem often
encountered with other computational learning machines
[85].
Lately, in silico calculation of infinite-dilution activity
coefficients of molecular solutes including water in ionic
liquids was the subject of a more recent research project
elaborated by Paduszynski [41]. The author gave a critical
review of existing QSPR models and proposed new QSPR
models based on three machine learning algorithms.
Stepwise multiple linear regression (SWMLR)-based,
FFANN-based and LSSVM-based models were compared
in terms of RMSE and AARD between calculated and
experimental c1 . Significant large amount of data were
employed in the work, namely 188 ILs and 128 solutes for
a total data points exceeding 34,000. The FFANN and
LSSVM gave considerably lower errors than the SWMLR,
while it was demonstrated that LSSVM generated slightly
better results compared to FFANN [41].
In the aim of improving the modeling of the activity
coefficient at infinite dilution of water in ionic liquids, our
present work employs FFANN, SVM and LSSVM to
develop correlative/predictive models for IDAC calcula-
tion based on properties of ionic liquids. For this purpose,
the independent variables selected as inputs for the mod-
eling are operating conditions which are the temperature
and the molecular weight and four pure component prop-
erties of the ILs which are Tc, Pc, Vc and x. These lasts
parameters were the subject of numerous researches using
ANN, and the results of those researches were promising
[68].
3 Results and discussion
3.1 ANN modeling
The data used in the ANN modeling are gathered from the
literature expressing the activity coefficient at infinite
dilution of water in 53 ILs at six different temperatures
with a total of 318 data points. The data set can be accessed
in Supporting Information 1. The selection of appropriate
inputs is preliminary step in modeling. The inputs have to
be significant, which means they have a theoretical effect
on the target (output). In this study, the temperature is
considered as an input given the fact that the activity
coefficient is a thermodynamic property, so by definition it
is dependent on temperature. Also, since at infinite dilution,
the molecule of solute is considered fully encircled by
molecules of solvent (in our case IL) and only molecular-
level interactions between the solute and solvent are taking
place, the 3D structure of the IL is a crucial factor to
activity coefficient at infinite dilution [86]; therefore, the
critical volume of the IL and its molecular weight are
considered as inputs in the neural network. On the other
hand, since phase equilibrium between solute/solvent can
be expressed by the iso-fugacity criterion which can be
approximated by the modified Raoult’s law for vapor liquid
equilibrium:
yi P ¼ xi ci Psat
i ð5Þ
where yi and xi are the molar fraction of component i in
vapor and liquid phase, respectively. P is the pressure, ci is
the activity coefficient, and Psat
i is the saturated pressure of
component i at temperature T.
Equation (5) can be written as:
yi P yi P
ci ¼ ¼ : ð6Þ
xi Psat
i xi Psat
i
Since Psat
i is a function of temperature, Eq. 6 shows that ci
is a function of temperature and pressure.
On the other hand, the relationship between the tem-
perature, pressure, volume and compressibility factor can
be expressed by the following equation of state:
PV  ZRT ¼ 0 ð7Þ
where Z is compressibility factor and is a function of
reduced temperature Tr, reduced pressure Pr and acentric
factor x.
Z ¼ f ðPr ; Tr ; xÞ ð8Þ
where Pr ¼ PPc and Tr ¼ TTc
where Tc and Pc are the critical temperature and critical
pressure of the component, respectively.
From the combination of Eqs. (7), (6) and (8), it can be
seen that activity coefficient ci is theoretically dependent
123

on critical properties (Tc, Pc, Vc) and acentric factor (x) of
the component; which justifies the choice of Tc, Pc and x
as additional inputs in the model.
Some of the properties of ionic liquids are calculated by
Valderrama et al. [87] using group contribution method
based on the effect of functional groups present in the IL.
Similarly, for ILs with a molecular weight exceeding
500 g/mol, the extension of a group contribution method
proposed by Valderrama et al. [88] is used to determine the
properties of ionic liquids with high molecular mass,
whereas for the ionic liquids whose properties were not
calculated before, the same group contribution method is
applied to determine the properties. The experimental data
are divided into a training set, a test set and a validation set.
Each data set should be well distributed throughout the
model space. Accordingly, two-thirds of the whole data are
for training set (total 212 data points), and the remaining
one-third of the whole data are equally divided into test
data set (53 data points) and validation (53 data points).
The validation and test data are referred to as a validation
data (106 data points), and the neural network statistical
parameters for validation set include the validation and test
sets combined. The ranges of variables used are given in
Table 1.
The ANN modeling is performed using MATLAB
(version 7.5). Before training, it is often useful to scale
inputs and targets, so that they will fall within a specified
range as this may help avoiding numerical overflows and
accelerates the convergence of the algorithm. Thus, the
present input and output parameters are normalized
between - 1 and 1 using Eq. (5) which can be expressed in
Matlab as ‘‘mapminmax’’ and normalizes each parameter
(xi) of inputs and output into (xin) under the following
expression:
2fxi  minðxi Þg
xin ¼ 1 ð9Þ
fmaxðxi Þ  minðxi Þg
where xin is the normalized variable. The normalization of
inputs and output is made between - 1 and 1.
After selection of T, M, Tc, Pc, Vc and x as appropriate
inputs and the activity coefficient in the form of ‘‘lnc!
i ’’ as
the output, the optimal ANN is selected through a trial-and-
error procedure; screening different types of neural net-
works, numbers of layers, numbers of neurons in each
hidden layer, and using different training algorithms and
Table 1 The variables ranges of the ANN used in this work
Variable T (K) Tc (K) Pc (Mpa)
Ranges of variable (min– 318.15–368.15 767.19–1410.89 1.38–7.10
max)
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Neural Computing and Applications
activation functions in each layer, results in identifying a
final optimized network with a given type and architecture.
It is worth mentioning that in the case of using a nonlinear
function and considering a sufficient number of neurons,
adopting more hidden layers is not recommended as this
may result in over-fitting [89], the reason why a one hidden
layer is considered for our neural network. Accordingly,
the general structure of the ANN used in our modeling of
the activity coefficient at infinite dilution of water in ionic
liquids is depicted in Fig. 1, while its more detailed type
and architecture are illustrated in Table 2.
Levenberg–Marquardt backpropagation algorithm
locates the minimum of a multivariate function which
represents the sum of squares of nonlinear real-valued
functions. The performance function is reduced in an
iterative way during the algorithm. To avoid the conver-
gence of the backpropagation training algorithm to a local
minima instead of a global minima, optimization using
‘‘trainlm’’ function is repeated 50 times, with different sets
of initial weights and bias, and the best results in terms of
error are saved.
A Matlab code documenting the connection weights and
biases of the optimal network Logsig (6,16) and Linear
(16,1) is provided in Supporting Information 4.
In order to assess the predictive ability of the optimized
ANN model, the validation agreement vector and the val-
idation agreement plot of the predicted versus experimental
dependent variable from the validation data set only are
analyzed. Using the Matlab function ‘‘postreg,’’ the plot of
the predicted versus experimental validation data set and
the parameters of the linear regression are directly
obtained.
The total data agreement scheme is shown in Fig. 2a
which illustrates the ANN model’s calculated outputs
versus the experimental data with an agreement vector, [a
(slope), b (y intercept), R (correlation coeffi-
cient)] = [1.0004, 0.0011, 0.99997]. This reveals an ideal
modeling of the whole data by the optimized network.
However, Fig. 2b points up the validation agreement plot
which shows the predicted output values following exactly
the trend of the experimental data values with an agreement
vector approaching the ideal, [a (slope), b (y intercept),
R (correlation coefficient)] = [1.0013,0.0034,0.99992]
which demonstrates the predictive ability and accuracy of
our model.
Vc (cm3/mol) M (g/mol) x c!
i
568.8–1476.7 169.3–605.2 0.1603–2.9211 17 9 10-3–
9.36
Neural Computing and Applications

The statistical parameters of the NN model for the

training set, validation set and total data (training, valida-
T tion and test) are the correlation coefficient R2 and the root
mean square error RMSE (square root of the average sum
Tc
of squares), calculated for the predicted activity coefficient
Pc at infinite dilution of water in ionic liquids by Eq. (10), and
ln i
the average absolute relative deviation AARD is expressed
Vc in Eq. (11):
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
M u N  2
u 1 X 1Exp
RMSE ¼ t ci  c1cali ð10Þ
N i¼1

Fig. 1 Schematic illustration of the optimized ANN model

Table 2 Structure of the optimized ANN model

Type of Training algorithm Input Hidden layer Output layer
network layer
No. of No. of Activation function No. of Activation function
neurons neurons neurons

FFBP NN Levenberg–Marquardt 6 16 Logarithmic sigmoid transfer 1 Linear transfer function.

Matlab backpropagation function. Matlab function ‘‘logsig’’ Matlab function ‘‘purelin’’
function Matlab function
‘‘newff’’ ‘‘trainlm’’

Linear Fit: ln cal=(1)ln exp+(0.0011), R=0.99997 Linear Fit: ln cal=(1)ln exp+(0.0034), R=0.99992
3 3

Data Points Data Points

2 Best Linear Fit Best Linear Fit
2
ln cal = ln exp ln cal = ln exp

1
1

0
ln cal

cal

-1
ln

-1

-2

-2
-3

-3
-4

-5 -4
-5 -4 -3 -2 -1 0 1 2 3 -4 -3 -2 -1 0 1 2 3

ln exp ln
exp

(a) (b)

Fig. 2 Predicted versus experimental data agreement plot: a for the total data, b for the validation data

123

100 X
N
c1Exp  c1cal
i i
AARDð%Þ ¼ ð11Þ
N i¼1 c1Exp
i previously implicated in the study.
Table 3 summarizes the model statistical parameters for
the data sets concerning the training, validation and test.
The correlation coefficient R2 for the training set is 1,
which indicates that the variation in the training data and
the correlation are in ideal agreement. The test data cor-
relation coefficient represents a comparison between the
experimental data and NN predicted results inside the
range of experimental data in order to show the interpo-
lating ability of the ANN model. For the validation data set,
the regression coefficient R2 is 0.99992, which shows
excellent agreement between experimental literature data
and the NN predicted results within the ranges of inde-
pendent variables for which the model has been designed.
For visual representation of the relative deviation
between NN calculated and experimental IDAC, the reader
is referred to Fig. 3. As can be seen, the majority of the
calculated points are aligned near zero relative deviation,
except for few points. Overall, more than 99% of the data
points relative deviations fall within the range ± 10%, and
the couple points outside this range are most likely
explained by the fact that c!i is equal to 1 which makes ln
c!i zero and results in a high RD when dividing the dif-
ference between calculated and experimental ln c! i by
zero. The high correlating performance of ANN in mod-
eling the activity coefficient at infinite dilution and the fact
that the ANN model allows obtaining IDAC directly
through operating temperature T, critical temperature Tc,
critical pressure Pc, critical volume Vc, acentric factor x
and molecular weight M of the ionic liquid, without getting
involved in complicated molecular-level interactions,
reveal the proficiency of ANN in modeling activity coef-
ficient at infinite dilution and call for testing its perfor-
mance for expanded ranges of input variables.
In order to widen the spectrum of use/application of the
ANN model, the ability of the model for interpolation and
extrapolation is studied. The NN’s model interpolation
ability is tested, not only using the test data, but using 15
new data points at temperatures situated inside the ranges
of the variable but were not included in elaboration or
validation of the ANN model, whereas the extrapolation
ability of the ANN model is assessed by withdrawing the
temperature outside the ranges of the variable in a new two
Table 3 Statistical parameters
Data set
of ANN model developed in this
work Number of points
R2
RMSE
AARD(%)
123
Neural Computing and Applications
data points for each ionic liquid. The new data points used
for interpolation and extrapolation test belong to three ILs
The results depicted in Fig. 4 show that the interpolated
and extrapolated data fit perfectly in the trend of IDAC as a
function of temperature and reveal a good agreement
between the IDAC calculated using the NN model and the
new data points; therefore, our model is also capable of
effectively estimating IDAC of water in 53 ILs at any given
temperature within the range [318.15 K–368.15 K] as this
represents the interval of temperature where the model
fitting capability is actually tested.
3.2 SVM modeling
In this paper, the SVM and LSSVM are employed for
nonlinear modeling of the IDAC of water in ionic liquids
using the same literature data used to develop the ANN
model. The SVM and LSSVM models generate a nonlinear
relationship between the inputs, which are T, Tc ; Pc ; Vc ; x
and M, and the output ln c1 . For that reason, a kernel
function is required for implicit mapping of training pat-
terns into feature space. A kernel can be any mathematical
function that satisfies Mercer theorem. The choice of the
kernel and kernel/regularization parameters can be auto-
mated by optimization of model selection criterion [89];
however, this can be a tricky task and may result in severe
over-fitting the model selection criterion (typically cross-
validation based) when more than few hyper-parameter are
to be tuned [85]. Different kernel functions are reported in
the literature [90–94], and since there is no guarantee for a
kernel to work better than the others on a specific data
(other than measuring similarity), it is more practical to test
the performance of different kernels in our modeling.
Therefore, in the present SVM modeling, the kernel func-
tions existing in the tool box R 2018a of Matlab are radial
basis function (RBF), polynomial, linear and Gaussian that
are tested, and the function that gave the best results in
terms of deviation and correlation coefficient is the kernel
used in our SVM modeling.
The data previously used to develop the ANN model are
exploited using the SVM method, partitioned equally
between training and testing using the SVM method. The
inputs and output of the SVM model are normalized to a
scale of - 1 to 1 by the mean of ‘‘premnmx’’ function, and
Training Validation (including test) Total
212 106 318
1 0.99992 0.99997
4.8614 9 10-6 0.0314 0.0181
0.2983 1.0719 0.5562
Neural Computing and Applications

Fig. 3 Relative deviation 30

scatter plot for the NN model
20

Relative Deviation (%)

10

-10

-20

-30
50 100 150 200 250 300

N (data points)

11
[C4C1im][SCN] EXP
10 [C4C1im][SCN] CAL
[C2C1im][SCN] EXP
9
[C2C1im][SCN] CAL
[C4C1pip][SCN] EXP
8
[C4C1pip][SCN] CAL

6
IDAC

1
310 320 330 340 350 360 370 380
Temperature (K)

Fig. 4 Interpolation and extrapolation test results

later unnormalized using ‘‘postmnmx’’ function. The regularization parameter c are obtained through a trial-and-
mathematical expressions of the kernel functions used are error test [93]. Other methods of optimization of parame-
as follows: ters based on optimal design are discussed in depth by
  n o Stehlik et al. [95] and could be used as well. To perform
RBF : k Xi ; Xj ¼ exp Xi  Xj2 =2r2 the SVM and LSSVM modeling, the same software
   d MATLAB (version 7.5) used for ANN modeling is used.
Poly ðpolynomialÞ : k Xi ; Xj ¼ axT þ c The correlation coefficient R2 and AARD are the chosen
 
Linear : k Xi ; Xj ¼ xT y þ c statistical parameters of the models for performance
n o evaluation.
  1
Gaussian : k Xi ; Xj ¼ pffiffiffiffiffiffi exp Xi  Xj2 =2r2 Different permutations of meta-parameters, i.e., penalty
r 2p parameter C and loss function e, and different combina-
where d and r2 are user-defined kernel parameters, r2 is the tions of kernel parameters d and r2 are adopted on a trial-
width of RBF function and d is the degree of polynomial and-error basis. The combinations of parameters with dif-
function. In SVM and LSSVM modeling, the constant e in ferent kernel functions that gave the best performance were
the loss function and penalty parameter C must be defined recorded and set as optimal kernel parameters. An
by the user. In the work, optimal values of d and r2 and

123
 Neural Computing and Applications

illustration of the hyper-parameters optimization results is coefficient R2, AARD and RMSE are 0.9950, 6.70% and
given in Fig. 5. 0.31, respectively.
Optimal values of kernel, penalty and loss function In the SVM model based on Gaussian kernel, optimal
parameter defining the best performance of the SVM values of hyper-parameters r2, e and C correspond to
model, along with the model’s statistical parameters used values of 2.44, 0.0020 and 195, respectively. The number
to assess the performance of the models, are summarized in of support vectors value of 195 is the same for all kernel
Table 4. functions employed in this study, except for the polynomial
Based on the tests’ results presented in Table 4, it can be of degree 3 in which it was found to be 158. This indicates
seen that the linear and the polynomial of degree 2, 2.5, 3 that all the training patterns were used by each kernel to
performed poorly in SVM modeling using our data. The build the optimal regression function that is later used to
fair correlation coefficient and high error that these func- make predictions of test data. Even though a model’s large
tions yield suggest their inaccuracy in SVM modeling the number of support vectors may be a sign of over-fitting of
activity coefficient using the present data set. Nonetheless, test data, the generalization performance of the optimal
despite the improved modeling results achieved with the model is demonstrated by the small difference in correla-
RBF kernel, the polynomial of degree 3.2 and Gaussian tion coefficients and errors between training and testing
kernel, the last function outperformed the two remaining indicating the good generalization performance of the
functions and is found to be the more capable of modeling model. Thus, the results confirm the proper setting of
our data by means of SVM technique; therefore, the hyper-parameters in this work
Gaussian kernel is implemented in the present SVM
modeling. 3.3 LSSVM modeling
As shown in Fig. 6, the SVM model exhibited accept-
able efficiency in correlating the global data, confirmed by In order to develop a third model for activity coefficient at
a correlation coefficient value of 0.9976 and a significant infinite dilution of water in ILs, the LSSVM learning
low average absolute relative deviation AARD of 3.44%. technique is employed. The data splitting is the same for
Also, the predictive ability of the SVM model is demon- LSSVM and SVM modeling (see previous section). The
strated by testing 159 data points which follow closely the inputs and output are normalized to a scale of - 1 to 1
trend of the experimental IDAC, except for few points for using Matlab function ‘‘mapminmax.’’‘ As mentioned
which the deviations between experimental and model previously in this article, the choice of the kernel function
predicted values are noteworthy. The correlation is crucial for model performance. Thus, many functions

AARD
228,0

205,5

183,0
200
160,5

4,4 138,0
150
4,2 115,5

4,0 93,00
AARD

3,8 100 70,50

AARD

3,6 48,00
3,4 50 25,50
3,2
4,000
138
,00
185 0
190 0 0
195
200
,0
2

205 50
2
2,

0
5
si
4

gm

210
2,

sigm
C
a

a
6
2,

215
8

10
2,

220
00
10
0
3,

Fig. 5 3-D optimization of kernel parameter r2 and C as a function of the error AARD (zoom of the optimal combination presented to the left of
the figure)

123
Neural Computing and Applications

Table 4 Models performance using optimal values of kernel, penalty and loss function parameters
Kernel function C e d r2 (Sigma) Quantity of support vectors Cross-validation error R2 (global) AARD (%) (global)

Linear 11 0.5914 – – 159 0.5672 0.8620 97.405

Gaussian 195 0.0020 – 2.44 159 9.9724 9 10-04 0.9976 3.44
Polynomial 76 0.211 2 – 159 0.1856 0.9547 35.81
Polynomial 1 0.241 2.5 – 159 0.1795 0.9614 37.13
Polynomial 26 0.6036 3 – 158 0.6811 0.8258 58.10
Polynomial 6 0.0151 3.2 – 159 0.0163 0.9961 8.14
RBF 500 0.0010 – 2.7 159 5.1677 9 10-04 0.9959 3.76
C Penalty parameter, e loss function, d kernel parameters, r2 width of RBF function, R2 correlation coefficients, AARD (%) average absolute
relative deviation, RBF Radial Basic Function

ln vs. ln , R=0.99761 ln vs. ln , R=0.99501

CalGlobal ExpGlobal CalTest ExpTest
3 3

Data Points Data Points

Best Linear Fit Best Linear Fit
2 2
ln CalGlobal = ln ExpGlobal ln CalTest = ln ExpTest

1
1

0
0
CalGlobal

CalTest

-1
ln

-1
ln

-2

-2
-3

-3
-4

-5 -4
-5 -4 -3 -2 -1 0 1 2 3 -4 -3 -2 -1 0 1 2 3
ln ln
ExpGlobal ExpTest

(a) (b)

Fig. 6 SVM predicted versus experimental data agreement plot: a for the global data, b for the test data

existing in the toolbox of LSSVM [96, 97] are tested in The criteria adopted as a measure of models performance
addition to exponential RBF and Cauchy kernel. The are correlation coefficient R2 and AARD for both global
mathematical expressions of the these lasts are as follows: and test data. The optimal values correspond to the best
   x  y performance of the LSSVM model. The results of testing
Exponential RBF : k Xi ; Xj ¼ exp  different kernels and kernel parameters are given in
2r2
  1 Table 5.
Cauchy : k Xi ; Xj ¼ 2 The two parameters r2 and c are optimized through the
1 þ xy
r2 first part of the training phase (tuning), and the optimal
The function that gives the best results in terms of values of the parameters are then used to perform the rest
correlation performance and least deviation is set as the of the computational calculations.
optimal function for the LSSVM modeling. The assessment Based on the results obtained using the trial-and-error
of the optimal kernel parameters d, r2 and regularization test, it may be observed that all kernel functions have
parameter c, along with the penalty parameter C and loss demonstrated a good degree of accuracy in predicting the
function’s constant e, is performed by a trial-and-error test. activity coefficient at infinite dilution of water in ILs,
except for linear kernel which yielded the highest error in

123
 Neural Computing and Applications

Table 5 Evaluation of different LSSVM models using different kernels and optimal values of hyper-parameters
RBF Linear Polynomial (degree 4) Cauchy ERBF

R2 (total data) 0.9995 0.89336 0.99903 0.9995 0.99956

R2 (test data) 0.9991 0.89605 0.99825 0.99907 0.99919
AARD (global) (%) 2.36 62.9297 3.4199 2.0999 2.0388
AARD (test) (%) 3.94% 60.9036 6.5406 3.7905 3.6279
Kernel function’s parameters c = 3.07 9 107 c = 3.2367 c = 383.6916 c = 1.0221 9 107 c = 1.2833 9 107
2 2 2
r = 26.80 r = 165.5983 r = 11.5885 r2 = 12.7718

terms of AARD value of 62.93% and 60.90% between
global and test, respectively. Overall, the ERBF predicted
values are much less scattered compared to other kernel
functions with a high correlation coefficient value of
0.99956 for training and test (global) and 0.99919 for
testing. Also, the marginal loss between the R2 for training
and testing in the case of ERBF is insignificant suggesting
the high generalization performance of the model in terms
of R2. Nevertheless, the AARD value of 2.04% for global
and 3.63% for testing demonstrates the high accuracy of
the LSSVM model using the ERBF as a kernel function
compared to the other models based on different kernels.
From Fig. 7a, b, it can be seen that the LSSVM predictions
of the ln c1 are in good agreement with the experimental
data.
3.4 Comparison between literature and this
work proposed models
The performance of the models developed in this work is
compared to the performance of other literature models
based on three types of learning algorithms which are
LSSVM, ANN and MLR. For this purpose, a LSSVM
model that was previously proposed by Paduszynski [41]
aiming the prediction of IDAC of various solvents,
including water, in any ionic liquid, along with a FFANN
model developed in the same paper [41], is evaluated in
terms of correlating and predicting accuracy. Both models
are tested for the same set of 53 ILs considered in this
work, but the inputs considered in both models are different
from the inputs selected in this work. Both LSSVM and
FFANN consider 72 inputs, which summarize group

ln vs. ln , R=0.99954 ln vs. ln , R=0.99911

CalGlobal ExpGlobal CalTest ExpTest
3 3

Data Points Datta Poin

nts
Best Linear Fit Best Linear Fit
2
ln CalGlobal =ln
n ExpGlobal 2 ln CalTest = ln ExpTestt

1
1

0
CalGlobal

0
CalTest

-1
ln
ln

-1

-2

-2
-3

-3
-4

-5 -4
-5 -4 -3 -2 -1 0 1 2 3 -4 -3 -2 -1 0 1 2 3
ln ln
ExpGlobal ExpTest

(a) (b)

Fig. 7 LSSVM predicted versus experimental data agreement plot: a for the global data, b for the test data

123
Neural Computing and Applications
contribution parameters and temperature, one output,
which is the IDAC, and one hidden layer with 19 neurons
for the FFANN model. Also, a previous MLR model pro-
posed by Gonfa et al. [61] based on the same experimental
data, but using eight sigma profile molecular descriptors
along with temperature as independent variables, was
brought to comparison.
The applicable input data for the 53 ILs allowing the use
of the final models and the reproduction of the results are
provided in the Supporting Information 2.
As illustrated in Table 6, the ANN model proposed in
the present work is capable of correlating far more accu-
rately the IDAC of water in the 53 ILs, while the proposed
LSSVM model generates a lower average absolute relative
deviation compared to the literature FFANN, literature
MLR, literature LSSVM and this work SVM models; the
NN model proposed in this work predominates all models
with an AARD of 0.56%, more than forty times smaller
than this work’s LSSVM one.
Accordingly, the parity plots demonstrated in Fig. 8
show the scatter of calculated versus experimental c1 i for
three models chosen as example for comparison, namely
this work ANN model (Fig. 8a), literature LSSVM
(Fig. 7b) and literature FFANN (Fig. 8c). As seen, the data
points land exactly along the diagonal in the case of the
present NN model, which proves the accuracy of the pre-
sent modeling. However, the large scatters observed for the
two remaining techniques LSSVM and FFANN reveal a
much lower fitting capability of the two models.
Nonetheless, the fact that the literature FFANN model
considers a large number of inputs, namely functional
groups (66) and Abraham solvation parameters (5), in
addition to temperature leads to more computing com-
plexity and a high-dimensional weights’ matrix (19
rows 9 72 columns) and bias column vector (19 rows),
and that for the hidden layer only. However, the ANN
proposed in this study outperforms the other models and
accurately predicts infinite-dilution activity coefficient
through operating temperature (T), IL’s critical temperature
(Tc), critical pressure (Pc), critical volume (Vc), acentric
factor (x) and molecular weight (M), without getting
Table 6 This work and
Model type
literature models’ statistical
parameters comparison ANN (this work)
LSSVM (this work)
SVM (this work)
LSSVM [41]
FFANN [41]
MLR [61]
R2 Correlation coefficients, AARD (%) average absolute relative deviation, RBF Radial Basic Function
involved in complicated thermodynamic computations.
The results show that the NN model developed in this work
is more accurate in predicting the IDAC of water in 53 ILs
than the LSSVM and FFANN techniques recently proposed
in the literature.
The literature MLR displayed clearly a weaker perfor-
mance in terms of accuracy compared to the NN proposed
in this paper. The RMSE of the proposed NN model is
more than ten times smaller than the MLR one which
demonstrates the stability of the neural network model. The
comparative study carried out illuminated the effect that
the input variables have over model’s performance.
3.5 Graphical user interface of the ANN model
In order to simplify the complexity of the work and pro-
gramming performed in this paper, a graphical interface
(also called user interface) is developed to improve the
usability of the developed ANN model. It is a tool that
allows a direct effortless utilization of the NN model to
calculate the IDAC of water in 53 ionic liquids. The user
graphical interface created in this work is depicted in
Fig. 9.
3.6 Input variables’ sensitivity study
One of the main objectives of the sensitivity analysis is
revealing the input parameters that hold the biggest effect
on the output variable. Nevertheless, this study allows
identifying the inputs that have a weak influence on the
output and permits discarding these parameters that add
unnecessary encumber in the modeling and focus instead
on the more significant parameters [98]. In this context,
regression techniques are the most widely used, and in this
work, standardized regression coefficients method is used
to carry out the sensitivity analysis. During this process,
experimental data of inputs and output are fed into the
regression algorithm which builds a linear model between
each input and the output, whereby the resulting regression
coefficients for each factor describe the sensitivity measure
of that factor on the output [98].
Total data points R2 AARD (%) RMSE
318 0.99997 0.56 0.0181
318 0.9995 2.36 0.0110
318 0.99761 3.44 0.2214
318 0.9015 22.69 0.6971
318 0.9207 40.61 0.6214
318 0.9618 – 0.2806
123
 Neural Computing and Applications

vs. , R=0.99965 vs. , R=0.90148

Cal Exp cal Exp
10 10
Data Points
Data Points
Best Linear Fit
9 9 Best Linear Fit
=
Cal Exp
Cal
= Exp
8 8

7 7

6 6
Cal

cal
5 5

4 4

3 3

2 2

1 1

0 0
0 2 4 6 8 10 0 2 4 6 8 10

Exp Exp

(a) (b)

vs. , R=0.92073
Cal Exp
10
Data Points
Best Linear Fit
9
cal
= Exp

6
Cal

0
0 2 4 6 8 10

Exp

(c)

Fig. 8 Parity plots of the calculated versus experimental c1

i for the same data set. a NN in this work; b LSSVM technique [41]; c FFANN model
[41]

Our models have six inputs: T, Tc, Pc, Vc, x and M, and c1 = f ðT; Tc ; Pc ; Vc ; x; M Þ: The Monte Carlo sample in
one output ln c1 . The models describe ln this case can be represented as:

123
Neural Computing and Applications

1ðiÞ
Matlab function postreg ðln cCal ; ln c1ðiÞ Þ has to exceed
0.7, confirming that the regression model is able to corre-
late the given data. Figure 10 shows the regression model
performance for our case of study where Rlnc1 was calcu-
lated and found to be 0.8398, which ascertains the feasi-
bility of this method for the present sensitivity analysis. In
this case, the effect or sensitivity of each input on the
output is simply quantified and may be prearranged by the
absolute value of its bj .
The pie chart in Fig. 11 is a representation of the relative
importance of the six input variables on the output variable
calculated using the standardized regression coefficients
method. The results demonstrate that all the input variables
have a variable effect on the activity coefficient. The
molecular weight of the ionic liquid holds the highest
contribution with a relative importance of 57.69%, while
the rest of the inputs have less significant contributions,
Fig. 9 The user graphical interface elaborated in this work specifically 11.93%, 9.57%, 8.46%, 7.94% and 4.42%
8 9 corresponding to T, Pc ; x, Vc and Tc , respectively.
> ð1Þ ð1Þ ð1 Þ
>
> T ð1 Þ Tc Pc Vc xð1Þ M ð1 Þ > >
>
>
> >
ð2 Þ >
< T ð2 Þ Tc
ð2Þ
Pc
ð2Þ
Vc
ð2 Þ
xð2Þ M =
M¼ .. >; while
>
>
.. .. .. .. ..
. >
4 Conclusion
>
> . . . . . >
>
>
: ð318Þ ð318Þ ð318Þ ð318Þ >
;
T Tc Pc Vc xð318Þ M ð318Þ
In this work, three machine learning techniques are applied
lnc1ð1Þ to activity coefficient at infinite dilution of water in ionic
lnc1ð2Þ liquids-related literature data to develop and validate models
ln c1 ¼ ..
. capable of predicting this property. Three models based on
lnc 1ð318Þ ANNs, SVM and LSSVM are developed with the aim of
quantifying numerically the relationship that connects the
For example, in order to measure the sensitivity of the input variables to the output. For that reason, six indepen-
input T, the mean and standard deviation MT and STDT , dent variables are chosen, namely the temperature of the
respectively, of the factor T are calculated. Similarly, Mlnc1
and STDlnc1 are the corresponding quantities for the output Outputs vs. Targets, R=0.83981
10
ði Þ
ðiÞ xj Mxj
ln c1 : We consider the two entities x~j = STD and Y ¼
xj
1ð i Þ
lnc lnc M 1 8
STDlnc1 for i = 1,2,…,318 and j = 1,2,…,6 and look for
the regression model in Eq. (12)
1ðiÞ 6
lncCal  Mlnc1 X 6
ðiÞ
¼ bj x~j ð12Þ
STDlnc1
Exp

j¼1
4
ln

where bjs are the standardized regression coefficients and

are determined by least square error eðiÞ , with
2
1ðiÞ
eðiÞ ¼ lncCal  lnc1ðiÞ ð13Þ
Accordingly, bj values obtained in the present work are, 0

respectively, -0.1855, 0.0687, -0.1487, -0.1234, 0.1315

and 0.8968 corresponding to T, Tc ; Pc ; Vc ; x and M: How-
-2
ever, to be able to use those results as a measure of the 0 2 4 6 8 10

sensitivity of the inputs on the output, the regression ln

Cal
1ðiÞ
coefficient Rlnc1 of the fit lncCal ¼ f ðlnc1ðiÞ Þ using the
Fig. 10 Regression model performance plot

123

Fig. 11 Relative importance of input variables on the estimation of
IDAC of water in ionic liquids
system water/ionic liquid, the critical temperature, critical
pressure, critical volume, acentric factor and molecular
weight of the ionic liquid, whereas the activity coefficient at
infinite dilution of water in ionic liquids in the form of ln c1
i
is set as the output dependent variable. Among the models
proposed in this work, the feedforward backpropagation
neural network model has shown the best performance. The
optimal neural network consists of an input layer with 6
neurons, one hidden layer with 16 neurons and an output
layer with one neuron. This model exhibits excellent cor-
relating/predicting ability elucidated by an overall average
absolute relative deviation of 0.56% and a correlation
coefficient of 0.99997, while the SVM and LSSVM models
yielded a higher deviation between experimental and model
calculated results. Moreover, the ANN model demonstrates
an excellent interpolation and extrapolation capability of the
IDAC of water in 53 ionic liquids at any temperature within
the range [313.15 K–373.15 K]. To illustrate the superiority
of the proposed ANN model, the correlative performance of
the proposed models is compared to three literature models
based on three methods: MLR, LSSVM and FFNN. The
comparison reveals that the proposed models have more
accurate correlation ability than the three literature models,
which demonstrates that the choice of input variables is a
crucial step in a modeling process. In addition, including a
relatively high number of unnecessary inputs not only
complicates the calculation process, but also it may add a
factor of inaccuracy to it.
A graphical user interface related to the best proposed
model (ANN) has been elaborated in order to provide a
prediction of the IDAC of water in 53 ILs at any given
temperature within the range studied. Finally, the input
sensitivity analysis is elaborated using standardized
regression coefficients method, appropriately. The results
represent a quantification of the contribution of each input
parameter on the output and reveal the molecular weight as
123
Neural Computing and Applications
the most pertinent parameter on the IDAC, followed by the
temperature, the critical pressure, the acentric factor and
critical volume of the IL, whereas the critical temperature
of the IL is found to be the least influential input, given its
relative importance is less than 5%. Despite the high
accuracy of the models developed in this work, in partic-
ular the ANN model, the modeling techniques used are all
correlative which require large sets of data and usually do
not expand well outside the range of data used to establish
models. Therefore, suggested improvements of this work
consist of broadening the research data, testing a larger
number of ILs and different solutes, and using other
learning methods such as evolutionary and hybrid algo-
rithms in order to develop other models and correlations
capable of prediction. Also, in light of the good results
obtained using the input parameters in this work, it is
hoped, in the future, that researchers and engineers who
apply AI methods for modeling will consider parameters
that are significant and translucently elected to represent
the phenomenon studied.
Acknowledgements The authors gratefully acknowledge the Algerian
Ministry of Higher Education and Scientific Research (CNEPRU
Projects: Nos. J0102620110007 and J0102620140015) and the
University Yahia Fares of Medea.
Compliance with ethical standards
Conflict of interest Authors declare that there is no conflict of interest
to declare.
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