MATCH MATCH Commun. Math. Comput. Chem.

78 (2017) 529-564
Communications in Mathematical
and in Computer Chemistry ISSN 0340 - 6253

Development of an ANN Based

Additive-Constitutive Method for
Estimating Viscosity ln (T) of Ionic Liquids
Using Particle Swarm Optimization
Juan A. Lazzus
Departamento de Fsica y Astronoma,
Universidad de La Serena, Casilla 554, La Serena, Chile
jlazzus@dfuls.cl

(Received October 30, 2016)

Abstract

An additive-constitutive method was developed using a hybrid algorithm con-

sisting of an artificial neural network and particle swarm optimization for estimating
viscosity of ionic liquid as a function of temperature. Several neural network ar-
chitectures were studied, and the optimum architecture was determined by adding
neurons in systematic form and evaluating the mean square error (MSE) during the
learning process. Input data of 260 ionic liquids (1238 data points) were used for
training the network. In order to discriminate among different substances, molecu-
lar weight and molecular structure (as defined by the concepts of the classical group
contribution methods) were given as input parameters. Capabilities of the designed
network were tested by estimating the viscosity of 119 ionic liquids not consid-
ered during the training phase (413 data points). The effect of cation and anion
structures, molecular weight, and measurement uncertainty on viscosity estimation
were studied. The results showed that the hybrid algorithm was able to estimate
the viscosity of several ionic liquids with an acceptable accuracy (AARD=2% and
R2 =0.994).
 -530-

1. Introduction
An ionic liquid (ILs) can be defined as any liquid composed of ions, whether organic salts
or molten salts. However, the term ionic liquid is currently associated to salts in liquid
state at room temperature (lower than 100 C). An IL consists of a big organic cation
and a smaller inorganic anion [1]. The most suitable combination for a specific IL to
be adapted to a certain application demands can be chosen from the above definition.
Thus, an ionic liquid designed can have a main component, i.e. a cation, determining
chemical behaviour, and another component, i.e. an anion, providing most of physical
properties [2], so the physical and chemical properties of ILs depend on its combination
of ions [3].
ILs offer a new range of technological possibilities, therefore knowledge of ILs physical
and chemical properties is considerably important for its various applications [4]. Cur-
rently, a series of efforts has been made for providing a better access to ionic liquids
property data [5]. However, all of these efforts are still insufficient, so new methods for
property estimation that reduce experimental costs and may be applied to a variety of
ILs, are required [6]. In this context, this study introduces a new method for estimating
ionic liquid viscosity at different temperatures using an artificial neural network opti-
mized by a particle swarm algorithm for updating network synaptic weights, resulting in
an ANN+PSO hybrid algorithm.
In physics, viscosity () is described as a fluids internal resistance to flow, but it
should be described as a friction measurement [7]. For industrial applications, viscosity
is a property affecting solute diffusion and important technical parameters for mixture
operation and agitation as well as for fluid pumping. Due to its ionic nature, ionic fluids
are much more viscous than conventional reaction media, which can bring adverse effects
for some industrial applications such as pumping and mixing; however, viscosity can be
fitted by adequately combining the cation and the anion in a way that the needed viscosity
would be designed [8].
Nowadays there are many methods for the estimation of ionic liquid viscosity, which
can be classified into correlations, additive-constitutive methods (ACM), and quantitative
structure-property relationship methods (QSPR) [9]. Table 1 shows a list of ionic liquid
viscosity estimation methods in the literature. Note that, additive-constitutive method
has been successfully used for estimating the viscosity of various classes of ionic liquids
 -531-

Table 1. Some reported methods for predicting viscosity of ILs.

Method T (K) (cP) NIL Ndata ILclass Deviation %Emax R2 Ref.

ACM 293393 421000 29 500 Diverse 7.7 28 [10]
ACM 293393 41065 25 482 Diverse 7.5 23 [11]
ACM 250433 443 1672 Diverse 6.3 31 0.854 [12]
ACM 293373 44123500 4 20 Magnetics 7.64 0.98 [13]
ACM 253395 620883 326 1445 Diverse 4.5 25 0.94 [14]
QSPR 283353 62 Diverse 0.9464 [15]
QSPR 293363 146 Diverse 10 0.9379 [16]
QSPR 263353 300 Diverse 0.8971 [17]
QSPR 298 16553 76 Imidazolium 24 >0.89 [18]
QSPR 293 435 Diverse 8.77 0.8096 [19]
QSPR 273353 329 Diverse 0.9308 [20]
QSPR 293 33 Diverse <0.87 [21]
QSPR 293343 Imides >0.82 [22]
QSPR 258433 82289 26 304 Diverse 27 >0.9 [23]

[1023]. Based on this success, a simple ACM was applied on the ANN+PSO algorithm
for estimating ln (T ) of ILs. Concerning the ANN aplications to the study of ILs, only
the backpropagation neural network (BPNN) has been used to correlate and predict the
viscosity of ILs [10]. Valderrama et al. [24] proposed the use of BPNN in order to estimate
the viscosity of 31 data points for 26 ILs. Billard et al. [25] used a BPNN for estimating
viscosity of ILs, but only at the fixed temperature of 298K. Also, Dutt et al. [26] proposed
a BPNN in order to predict ln (T ) of 73 ILs at 654 data points. However, to the best of
the authors knowledge, there is no application for ionic liquid viscosity as a function of the
temperature ln (T ), such as the one presented here, and certainly there is no publication
on the estimation of this transport property for several ILs using a hybrid method based
on ACM+ANN+PSO.

2. Proposed Algorithm
2.1. Artificial neural network (ANN)
An artificial neural network (ANN) is a distributed computing scheme inspired by the
human nervous system structure. The most important property of artificial neural network
is its capacity of learning from a set of training patterns, i.e. finding a model that can
adjust the data. Feedforward neural networks (FANN) are the most studied type of ANN
in the scientific field and the most used in several application [27]. This ANN consists of
one input layer with N inputs, one hidden layer with q units and one output layer with
n outputs. A FANN model contain a weight vector W equivalent to synaptic connections
 -532-

in the real neurons, and they are updated during a training process. Calculations of all
connection weight modifications start on the output layer and continue backwards through
all network layers to the input layer [28]:
q N
! !
X X
Yn = f n Wnj fj Wji Xi + Bj + B0 (1)
j=1 i=1
2


where Xi is the input vector Xi = xi xmin
i xmax xmin
1, where xmin
i and xmax
i are the
i i

smallest and largest data values; Wnj are the weights between unit j and unit n of input
and hidden layers and Wji are the weights between hidden layer and an output; Bj and
B0 are the bias of the hidden layer and the output layer, respectively. The activation
functions fn (x) and fj (x) can be linear or nonlinear. We used one hidden layer with fj (x)
as a tangent hyperbolic nonlinear activation functions, and fn (x) as linear function in
output layer, defined as:

eyj eyj
fj (Yj ) = (2)
eyj + eyj
fn (Yn ) = Yn (3)

where Yj is the output of the hidden layer, and Yn is the final output of the ANN. Finally,
the network response yn is obtained denormalized the output vector Yn
During the training the ANN weights and biases are iteratively adjusted to minimize
the mean square error (MSE) between the calculated value (calc) and the real data (real)
for the total data points (N ):

PN
2
i=1 y calc y real i
MSE = (4)
N
FANNs are usually trained by using a descending algorithm for the gradient of the
error function, also known as backpropagation (BP). Thus, the implementation of back-
propagation learning updates the network weights and biases in the direction in which
the performance function decreases most rapidly, the negative of the gradient. Then, one
iteration k of this algorithm can be described as:

k+1 = k k gk (5)

where k is a vector of current weights and biases, gk is the current gradient, and k is
the learning rate. Note that, BPNN is the most commonly ANN used, and for its general
 -533-

description see [29]. Although this algorithm is very efficient, it tends to get stuck on min-
imum locals greatly depending on the search start point. In order to solve this problems
and many others occurred during the training step, a new training techniques combining
metaheuristic algorithms with global-search methods have been recently suggested [30],
allowing metaheuristic algorithms to globally search for the optimum in a more effective
performance and to work with non-differentiable, multimodal-error surfaces. As there is
not any need for information related to the gradient of the error function, these methods
are considerably useful when the information is not available, causing the use of hybrid
neural networks for the resolution of a number of real problems where traditional training
algorithms do not provide an optimum global minimum. For this study, a particle swarm
optimization (PSO) algorithm was used. The PSO algorithm has been proven effective
at solving common problems in the training of artificial neural networks [31, 32].

2.2. Particle swarm optimization (PSO)

PSO was developed by Kennedy and Eberhart [33] and was based on the social behaviour
of animal groups such as bird flocks, swarms, and fish banks. In PSO, particles fly
over a n-dimensional search space trying to find the optimum solution. In order to do so,
each member of the group fits its position according to a linear combination of its inertia,
its own experience and the swarms knowledge. Each swarm particle i knows its current
position Si = [si,1 , si,2 , , si,n ], the velocity Vi = [vi,1 , vi,2 , , vi,n ] at which it arrived to
its position, and the best position Pi = [pi,1 , pi,2 , , pi,n ] it has been in called individual
best. Additionally, all particles know the best positions G = [g1 , g2 , , gn ] found inside
the swarm, called global best. Assuming a use of the information from the global best,
each component j of the velocity and the position of each particle i in the swarm in each
iteration t of the PSO algorithm is updated according to [33]:

Vi (t + 1) = Vi (t) + c1 r1 (Pi (t) Si (t)) + c2 r2 (G(t) Si (t)) (6)

Si (t + 1) = Si (t) + Vi (t + 1) (7)

where is the inertial parameter regulating the impact of the previous velocities on
the new velocity of the particle, c1 is the cognitive parameter indicating the maximum
influence of the best individual experience of the particle on its new velocity, and c2 is the
social parameter indicating the maximum influence of the social information on the new
 -534-

velocity value of the particle. While r1 and r2 are functions returning a random number in
the interval [0, 1] determining the real influence of the individual and social information
on the new velocity for the particle Vi (t + 1) [31].
This way, the swarm randomly initializes in the time t from a homogeneous probability
distribution. In each iteration, Eqs. 6 and 7 are used for updating the velocity and position
of each particle in the swarm. The total number of iterations in the PSO algorithm is
chosen so as to ensure that the algorithm converges, and G is adopted as the solution
obtained from the PSO. More details on the PSO deployment can found in Kennedy and
Eberhart [33].

2.3. ANN+PSO algorithm

The proposed algorithm is combining the best implementation of ANN and PSO. Now,
the net outputs (yn ) are calculated for the hidden neurons coming from the inputs neurons
as shows Eq. 1, and then, PSO is applied in order to obtain the optimal weights for the
FANN. From this point on, all the neurons of the ANN have an associated activation
value for a given input pattern, and the algorithm continues to find the error for each
neuron, except for those in the input layer. After finding the output values, the weights
of all layers of the network are actualized W W 0 by PSO, using Eqs. 6 and 7 [31].
Thus, on each step PSO compares each weight using the data set. The network with the
highest fitness is considered the global best. The other weights are updated based on the
global best network rather than their personal error or fitness [32] (for more details on
the implementation of hybrid ANN+PSO algorithm, please see [31, 32]).

3. Estimating Viscosity ln (T ) of ILs

3.1. Database used
A total of 1651 viscosity data points as a temperature function ln (T ) of 379 ILs was
collected from the literature (Note that, data not determined by experimental methods
were not considered for this study). Then, data was divided into two sets: training
and prediction. Data of 260 ionic liquids (1238 data points in total) was used for the
training set, and 413 data points (of 119 ILs) not used in the training set were used for
the prediction set. For clarity, all data for one IL were assigned to the same set. Table
S1 shows the values of experimental liquid viscosity considered in this study [5] (see,
 -535-

Supporting Information).

3.2. Additive-constitutive method as input parameters

The suggested method considers the following properties as input parameters: tempera-
ture T , molecular weight M , and 52 structural groups forming the molecules (obtained
by an additive-constitutive method). Note that, this method was divided into cation and
anion parts, assuming that cation and anion contributions have a distinct impact on liq-
uid viscosity (as is known, additive-constitutive methods suggest that a physical property
depends on the total contributions made by structural groups [6]). The 20 cation groups
included imidazolium, pyridinium, pyrrolidinium, piperidinium, phosphonium, ammo-
nium, morpholinium, oxazolidinium, sulfonium, and guanidinium. Additionally, other
32 anion groups included structural groups for the following IL-types: halides, pseudo-
halides, sulfates, sulfonates, tosylates, imides, amides, borates, phosphates, carboxylates,
trifluoracetates, and metal complexes. For these entrances (T , M , and 52 structural
groups), a leave-25%-out cross-prediction method was used to estimate the predictive
capabilities of the proposed method (ACM+ANN+PSO). Thus, training and prediction
sets were selected with the consideration that in the structural groups, the molecules
are decomposed into fragments and all fragments are present with adequate frequency
in the training data set. The value associated to the structural group was defined as
following: 0, when the group does not appear in the substance, and k, when the group
appears k-times in the substance [14]. Table 2 shows all 54 input parameters considered
for this study. As shown in this Table, for the total data set (T ) properties cover wide
ranges, such as 253433 K for the temperature, and 226100 cP for the liquid viscosity. In
addition, the ILs included in this study have very different physical and chemical charac-
teristics, e.g. low molecular weight substances such as 2-hydroxyethylammonium formate
M = 106, or high molecular weight substances such as trihexyl(tetradecyl)phosphonium
bis[(trifluoromethyl)sulfonyl]imide, M = 764, and low viscosity value = 2.86 (443K) for
1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [34], and high viscosity
value of = 26100 (293K) for triethylammonium trifluoroacetate [35]. These values are
of special importance in order to verify that an acceptable range of liquid viscosity was
covered in this study.
 -536-

Table 2. Input parameters considered in the proposed method.

No. occurrence
No. Input xmin xmax
Training set Prediction set Total set
1 T 253.15 433.15 1238 413 1651
2 M 106.230 934.92 1238 413 1651

3 0 2 974 269 1243

Imidazolium(+)

4 0 1 41 19 60
Pyridinium(+)

5 0 2 22 27 49
Pyrrolidinium(+)

6 0 1 98 56 154
Ammonium(+)

7 0 2 38 7 45
Phosphonium(+)

8 0 1 43 17 60
Sulfonium(+)

9 0 1 7 7 14
Piperidinium(+)

10 0 1 5 2 7
Morpholinium(+)
Continued on next page
 -537-

Table 2 continued from previous page

No. occurrence
No. Input xmin xmax
Training set Prediction set Total set

11 0 1 4 7 11
Oxazolidinium(+)

12 0 1 6 2 8
Guanidinium(+)
13 H(+) 0 3 958 272 1230
(+)
14 CH3 0 6 1229 410 1639
15 CH2 (+) 0 36 1229 381 1610
16 CH<(+) 0 2 8 13 21
17 OH(+) 0 1 4 6 10
18 O(+) 0 3 29 22 51
(+)
19 =CH2 0 2 12 2 14
20 CH=(+) 0 2 12 2 14
21 CN(+) 0 2 3 4 7
22 Benzyl(+) 0 2 5 2 7
()
23 CH3 0 3 95 25 120
24 CH2 () 0 7 86 3 89
25 >CH() [CH]() 0 1 6 6 12
26 >C<() [>C]() 0 1 7 0 7
27 COO() [COO]() 0 1 19 25 44
28 COOH() 0 1 4 2 6
29 >C=O() 0 2 15 4 19
30 OH() 0 2 6 4 10
31 O() [O]() 0 4 102 47 149
32 =O() 0 1 1 0 1
33 CN() 0 4 73 47 120
34 >N () [N]() 0 2 533 174 707
()
35 NO3 0 1 1 5 6
36 S() 0 1 9 4 13
37 SO2 () 0 4 583 182 765
()
38 CF3 0 4 546 196 742
()
39 CF2 0 3 41 18 59
40 F() 0 7 504 108 612
41 Cl() 0 4 46 36 82
42 I() 0 1 5 7 12
43 Br() 0 2 5 3 8
44 P() 0 1 184 67 251
45 B() 0 1 311 39 350
46 Ni() 0 1 6 3 9
47 Al() 0 1 3 0 3
48 U() 0 1 2 0 2
49 Ta() 0 1 1 0 1
50 Nb() 0 1 1 0 1
51 As() 0 1 1 0 1
52 Sb() 0 1 10 1 11
53 Fe() 0 1 24 20 44
54 W() 0 1 2 0 2

Note that, the minimum and maximum values for each input parameter, and the num-
ber of occurrence, are shown in Table 2. For, the output parameter (ln ) the minimum
and maximum values are 1.0508 and 10.1697, respectively.
 -538-

3.3. ACM+ANN+PSO implementation

Using the above methodology in Section 2, several network architectures were tested to
select the most accurate topology. Note that, the number of layers and the number
of neurons in each layer, forming the so called network topology or architecture. The
topologies which best fit the solution for the problem were determined by a trial-and-
error procedure. In this study, various topologies were analysed until a topology that
best correlated and estimated the viscosity of ionic liquids was found. As a result, the
number of neurons in the hidden layers presented a greater influence on the accuracy
of the results obtained during the training process. Figure 1 shows the MSE found in
correlating ln (T ) as a function of the number of neurons in the hidden layer (NHL). As
observed in this Figure, the optimum number of neurons in the hidden layer is between 8

0.09

0.08

0.07

0.06
MSE

0.05

0.04

0.03

0.02

0.01
2 4 6 8 10 12 14 16 18 20
NHL
Figure 1. Mean squared error (MSE) found in correlating ln (T ) of ILs as a
function of the number of neurons in the hidden layer (NHL) using
ANN+PSO. Training step () and prediction step ().
 -539-

and 11. The network architecture that showed the lowest deviations during the training
was an architecture of one hidden layer of 9 neurons, as well as 54 neurons in the input
layer, and one in the output layer (54-9-1), with a MSE=0.0167 during training and
MSE=0.0218 during prediction step.
Figure 2 shows an overview of the optimum training achieved by the hybrid algorithm
ANN+PSO with architecture 54-9-1. Figure 2 (left panel) shows the correlation between
calculated values and the experimental values for viscosity during the training step. Figure
2 (right panel) shows the calculated values (dashed line) and the experimental values
(circles) for viscosity as a temperature function for all ionic liquids included in the training
set. Figure 2 shows, in general terms, that the neural network can be trained using the
PSO algorithm and that the obtained optimum architecture can estimate ln (T ) with an
acceptable accuracy.

4. Results and Discussion

4.1. Prediction phase
At the end of the training process optimal network weights are obtained. Table 3 shows
the optimum weights determined by the hybrid algorithm PSO+ANN. The weights rep-
resent the network solutions for the studied problem. Once the optimum architecture
for correlating training data was found, the estimation of ln (T ) for ILs not used in the
training, i.e. testing or prediction process, take place.
Figure 3 shows the results for the prediction set using the optimum architecture and
weights obtained in the training step. Figure 3 (left panel) shows the correlation between
calculated values versus the literature values of viscosity obtained for the prediction set.
Figure 3 (right panel) shows the calculated values (dashed line) and the experimental
values (circles) for viscosity data used in the prediction set. These results shown that the
proposed ANN+PSO algorithm is an excellent option for estimating ln (T ) of ILs.
In addition, the accuracy of the suggested method was checked using the average
relative absolute deviation for each IL (%E) and for the total set (AARD). Table 4
summarizes the minimum, maximum, and average deviations obtained for the training
and prediction sets using the suggested ANN+ PSO method with architecture 54-9-1.
The results showed that the suggested method can estimate the viscosity of several ILs
with enough accuracy: AARD less than 2.03% for the 260 ILs (1238 experimental data
 10 10

9 9

8 8

7 7

6 6
ln

ln (calc)
5 5
-540-

4 4

3 3

2 2

1 1
1 2 3 4 5 6 7 8 9 10 250 300 350 400 450
ln (exp) T (K)

Figure 2. (a) Correlation between experimental and calculated values of ln during the training step. (b) Comparison between
experimental and calculated values of ln (T ) for the training set.
 Table 3. Optimum weights obtained by ACM+ANN+PSO for the network model 54-9-1.

Input Wij 1 2 3 4 5 6 7 8 9 RC
T 1 0.05332 0.05075 0.79908 0.09792 0.58577 0.07408 1.13336 0.03014 1.21174 0.226
M 2 0.29199 0.19181 0.50551 0.86181 0.69535 0.42769 0.46490 0.89767 0.28113 0.283
Imidazolium(+) 3 0.25543 0.18903 0.79219 0.10275 0.83994 0.56112 0.05503 0.72528 0.33380 0.221
Pyridinium(+) 4 0.77496 0.04686 0.19180 0.16937 0.91977 0.58713 0.01578 0.16368 0.34447 0.197
Pyrrolidinium(+) 5 0.09482 0.12356 0.46946 0.06335 0.25503 0.14765 0.18212 0.52780 0.89195 0.155
Ammonium(+) 6 0.02958 0.10894 0.40127 0.12696 1.95497 0.25344 0.11611 0.02288 0.09970 0.162
Phosphonium(+) 7 0.99756 0.17009 0.56317 0.00172 0.47561 0.19547 0.19100 0.42134 0.42899 0.199
Sulfonium(+) 8 0.01023 0.39974 0.54625 0.31484 0.02465 0.27268 0.21797 0.25428 0.29266 0.146
Piperidinium(+) 9 0.25113 0.23511 0.03126 0.02032 0.43023 0.05127 0.19079 0.05550 0.11238 0.081
Morpholinium(+) 10 0.30564 0.71664 0.56295 0.19039 0.47902 0.44267 0.65878 0.01009 0.30877 0.230
Oxazolidinium(+) 11 0.10822 0.11022 0.36167 0.03225 0.38646 0.20343 0.73129 0.97666 0.15390 0.177
Guanidinium(+) 12 0.07474 0.65145 0.12458 0.00225 0.05905 0.28702 0.77134 0.49633 0.05428 0.163
H(+) 13 0.55419 0.24213 0.22329 0.49089 0.64953 0.25965 0.20372 0.68128 0.36740 0.223
(+)
CH3 14 0.34846 0.08099 0.42231 0.56429 0.03283 0.18842 0.13065 0.13700 0.50283 0.152
CH2 (+) 15 0.96725 -0.12821 1.93182 0.40183 0.98738 0.46144 0.35367 1.79586 0.27628 0.407
CH<(+) 16 0.25173 0.16695 0.09475 0.47979 0.62905 0.16335 0.67364 0.12881 0.04014 0.164
-541-

OH(+) 17 0.08212 0.01957 0.47751 0.12326 0.08789 0.27079 0.23210 0.04612 0.09009 0.087
O(+) 18 0.14426 0.14322 0.07058 0.70773 0.02814 0.04322 0.27308 0.04750 0.07126 0.106
(+)
=CH2 19 0.03803 0.06707 0.15245 0.26506 0.12862 0.19914 0.41112 0.09810 0.23552 0.102
CH=(+) 20 0.34032 0.27520 0.31270 0.25165 0.19968 0.11524 0.08529 0.01108 0.15397 0.108
CN(+) 21 0.11957 0.17399 0.59940 0.01065 0.57917 0.45726 0.48483 0.15519 0.31972 0.171
Benzyl(+) 22 0.32531 0.50123 0.10538 0.00186 0.19965 0.15006 0.27751 0.16304 0.10732 0.116
()
CH3 23 0.34096 0.21312 0.43701 0.03467 0.49525 0.10717 0.11593 0.19797 0.05537 0.112
CH2 () 24 0.69453 0.55972 0.39722 0.00900 0.66102 0.01345 0.39837 0.48108 0.17583 0.195
>CH() [CH]() 25 0.28341 0.49834 0.05014 0.16777 0.76909 0.26127 0.50900 0.82195 0.47313 0.229
>C<() [>C]() 26 0.11528 0.18835 0.54365 0.09293 0.39049 0.30738 0.05513 0.14306 0.06019 0.111
COO() [COO]() 27 0.56462 0.90164 0.65728 0.09334 0.27373 0.02642 0.21146 1.19187 0.47133 0.255
COOH() 28 0.44771 0.05179 0.08625 0.04834 0.05390 0.15531 0.28858 0.35222 0.35247 0.113
>C=O() 29 0.16019 0.22512 0.58860 0.47567 0.43089 0.07083 0.28789 0.14497 0.07905 0.145
OH() 30 0.63224 0.22715 0.11384 0.32858 1.23080 0.28136 0.36726 0.04968 0.06819 0.197
O() [O]() 31 0.27079 0.63886 0.46379 0.01612 0.92244 0.74441 0.13080 0.03309 0.30396 0.218
=O() 32 0.04682 0.30546 0.05145 0.09250 0.01589 0.03444 -0.03990 0.19916 0.00206 0.051
Continued on next page
 Table 3 continued from previous page
Input Wij 1 2 3 4 5 6 7 8 9 RC
CN() 33 0.10484 0.24076 0.22684 0.30122 0.07821 0.33734 0.17471 0.10225 0.70330 0.146
>N() [N]() 34 0.12185 0.41257 0.79738 0.14941 0.21339 0.50363 0.14593 0.48557 0.97765 0.227
()
NO3 35 0.29095 0.13264 0.13953 0.36123 0.05546 0.07131 0.31214 0.04453 0.45819 0.119
S() 36 0.06874 0.41494 0.30130 0.16059 0.20710 0.04141 0.11857 0.94036 0.68431 0.169
SO2 () 37 0.27081 0.09116 0.67279 0.38435 0.01073 0.26779 0.67541 0.05945 0.25339 0.168
()
CF3 38 0.08264 0.50900 0.76610 0.67533 1.00125 0.19203 0.15503 0.68372 1.00697 0.292
()
CF2 39 0.33961 0.11302 0.26429 0.39315 0.71801 0.05916 0.10286 0.51061 0.15793 0.152
F() 40 0.49822 0.37942 0.33395 0.08797 0.74235 0.01914 0.12160 0.71440 0.10176 0.168
Cl() 41 0.33573 0.04743 1.02807 0.17594 0.16948 0.00955 0.45503 0.07423 1.49338 0.210
I() 42 0.01537 0.11264 0.10473 0.09151 0.03609 0.14350 0.22347 0.20533 0.06938 0.064
Br() 43 0.51943 0.17094 0.62040 0.17438 0.09102 0.09789 0.49283 0.64958 0.90848 0.217
P() 44 0.42251 0.20007 0.35668 0.57255 0.17363 0.16720 0.51978 0.14123 0.15574 0.173
-542-

B() 45 0.11244 0.81993 0.07554 0.01360 0.19435 0.33679 0.22020 0.00365 0.20595 0.133
Ni() 46 0.50291 0.02540 0.95841 0.09906 0.78876 0.04045 0.00078 0.06797 0.21218 0.139
Al() 47 0.30404 0.40271 0.38956 0.68611 0.05178 0.15194 0.39423 0.56337 0.07385 0.193
U() 48 0.10181 0.28102 0.20817 0.12529 0.26314 0.19407 0.00995 0.14813 0.23142 0.095
Ta() 49 0.29388 0.03237 0.18418 0.25283 0.17369 0.14985 0.00281 0.08513 0.03875 0.077
Nb() 50 0.00974 0.00922 0.33491 0.34602 0.04932 0.41757 0.40829 0.17231 0.04640 0.119
As() 51 0.08287 0.12534 0.08670 0.39986 0.19437 0.07195 0.32518 0.35896 0.39192 0.126
Sb() 52 0.26370 0.09445 0.10556 0.47778 0.06026 0.25239 0.03590 0.20786 0.05187 0.106
Fe() 53 0.65379 0.95292 1.23240 0.05714 0.86115 0.16455 0.22266 0.56321 0.64898 0.302
W() 54 0.07273 0.11433 0.30603 0.38191 0.05590 0.06689 0.09289 0.43023 0.12174 0.100
W0j 1.52019 1.04585 0.70297 0.44195 0.22329 0.29451 0.65584 1.04256 1.53730
Wnj 1.75274 1.68261 1.67528 1.75534 0.99910 1.60782 1.36301 0.84786 1.67990
Wn0 0.83219
 10 10

9 9

8 8

7 7

6 6
ln

ln (calc)
5 5
-543-

4 4

3 3

2 2

1 1
1 2 3 4 5 6 7 8 9 10 250 300 350 400
ln (exp) T (K)

Figure 3. (a) Correlation between experimental and calculated values of ln during the prediction step. (b) Comparison between
experimental and calculated values of ln (T ) for the prediction set.
 -544-

Table 4. Summary of deviations in the viscosity estimation (as ln ) using the

ACM+ANN+PSO method.

Statistics Training set Prediction set Total set

Ndata 1238 413 1651
AARD 2.03 2.16 2.06
%Emin 0.00 0.00 0.00
%Emax 17.18 15.48 17.18
%E < 10 1229 403 1632
%E > 10 9 10 19
R2 0.9949 0.9942 0.9947
MRE() 0.09 0.09 0.09

points) used in the training set, and AARD less than 2.16% for the other 119 ILs (413
experimental data points) used in the prediction set. As AARD is a statistical param-
eter that has not much physical meaning as an accuracy metric for prediction of vis-
cosity logarithm, the relative error of prediction was added, as | ln(calc ) ln(exp )| =
| ln(calc /exp )| = | ln(1 + (calc exp )/exp )| |(calc exp )|/exp = MRE(). Then,
the proposed method shows a MRE of 0.09 with a MREmax of 0.22 for the training step,
while it shows a MRE of 0.09 and a MRE of 0.25 during the prediction phase. In general,
the results obtained for the training and prediction phases show that the developed ANN
is very homogeneous, which confirms that it was correctly trained. For interested read-
ers, Table S1 and Table S2 detail the results obtained for training and prediction sets,
respectively (please see Supporting Information).

4.2. Relative contribution of inputs

From optimal weights obtained in the training phase (see Table 3), the relative contri-
bution (RC) of the inputs used (and based on an additive-constitutive method) were
calculated by the Garsons algorithm [36]. This approach provides a quantitative tool for
assisting in the network interpretation [37]. The following protocol was used for testing
the statistical significance of connection weights and input variables: (i) select the neural
network with the best predictive performance, record the optimum weights obtained in
constructing this network; (ii) calculate the input-hidden-output connection weights as
the product of input-hidden and hidden-output connection weights for each input and
hidden neuron; (iii) calculate RC or overall connection weight as the sum of the input-
hidden-output connection weights for each input variable. It is important to note that
Garsons algorithm uses the absolute values of the final connection weights when calculat-
 -545-

ing variable contributions, and therefore does not provide the direction of the relationship
between the input and output variables as illustrated in the following equation:
N
!
X |Wji Wnj |
RC = PM (8)
i=1 j=1 |Wji Wnj |
PM
where RC is the relative contribution of each input X, and j=1 |Wji Wnj | is sum of

product of final weights of the connections from input neurons to hidden neurons with the
connections from hidden neurons to output neurons. Table 3 (final column) shows the RC
obtained for each input of the ACM used. By RC the contributions of molecular structures
for cations were: Morpholinium(+) > Imidazolium(+) > Phosphonium(+) > Pyridinium(+)
> Oxazolidinium(+) > Guanidinium(+) > Ammonium(+) > Pyrrolidinium(+) > Sulfo-
nium(+) > Piperidinium(+) , while the RC for the anion structures were mainly: Fe() >
()
CF3 > COO() [COO]() > >CH() [CH]() > >N() [N]() > O() [O]()
()
> Br > Cl() , where highlight the corresponding structures to metal complexes and
halogens. Note that, the application of this effective model could effectively offer better
understanding of the input parameters govern the ACM. This would be beneficial because
it can provide an insight regarding which structures can contribute more towards viscosity,
and can help in designing ionic liquids with desired viscosity (maximum or minimum).

4.3. Cation & anion effects

Table 5 summarizes the results obtained with the proposed method for different ILs
classes. This Table shows the following MRE ranges during training: Guanidinium <
Piperidinium < Pyridinium < 0.05 < 1,3-Dialkyl-imidazolium < 1-Alkyl-imidazolium <
Oxazolidinium < Sulfonium < 0.10 < Pyrrolidinium < Ammonium < Phosphonium <
Morpholinium < Tri-alkyl-imidazolium < 0.15, however, MRE shows the following ranges
for the prediction set: Guanidinium < Morpholinium < Piperidinium < 0.05 < Oxazoli-
dinium < 1-Alkyl-imidazolium < Pyrrolidinium < Pyridinium < 1,3-Dialkyl-imidazolium
< Phosphonium < Ammonium < 0.10 < Sulfonium < Tri-alkyl-imidazolium < 0.15. This
analysis shows the impact of the cation size effect on neural network performance in both
phases. Recent studies show that viscosity depends greatly on the IL structure [14, 38],
and the viscosity of ILs depends strongly of the cation type. For example, the viscos-
ity of 1-isobutyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (83 cP) is more
than three times the viscosity of 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sul-
 -546-

Table 5. Deviations obtained for the cation classes with the proposed
ACM+ANN+PSO in the viscosity estimation of ILs.

IL class Ndata T (K) (cP) ln M MRE() R2

Training set
1,3-Dialkyl-imidazolium 957 258433 218089 110 158935 0.08 0.9960
1-Alkyl-imidazolium 9 293298 40550 36 183477 0.08 0.9915
Tri-alkyl-imidazolium 7 293298 3690 35 274419 0.14 0.9510
Ammonium 106 289373 626100 110 106859 0.12 0.9900
Guanidinium 6 293333 124335 46 537705 0.04 0.9912
Morpholinium 5 298298 2601035 57 295440 0.14 0.9692
Oxazolidinium 4 298298 90704 47 233424 0.10 0.9860
Phosphonium 38 283373 354145 38 443783 0.13 0.9882
Piperidinium 7 298298 681240 47 245482 0.04 0.9981
Pyridinium 42 283353 9502 26 237857 0.05 0.9977
Pyrrolidinium 22 293301 371680 37 194507 0.11 0.9872
Sulfonium 35 253353 6509 16 171449 0.10 0.9868
Prediction set
1,3-Dialkyl-imidazolium 258 273394 620883 110 170893 0.09 0.9940
1-Alkyl-imidazolium 9 293298 815222 49 199567 0.07 0.9985
Tri-alkyl-imidazolium 2 298373 2634 34 284358 0.14 0.9999
Ammonium 59 293373 31017 17 120629 0.10 0.9912
Guanidinium 2 293318 267415 56 205491 0.01 0.9999
Morpholinium 2 298298 466532 66 345438 0.04 0.9999
Oxazolidinium 7 298303 117731 47 231433 0.07 0.9867
Phosphonium 7 293298 441370 37 405764 0.09 0.9952
Piperidinium 7 298298 88456 46 293482 0.04 0.9954
Pyridinium 19 293353 12134 25 458472 0.09 0.9829
Pyrrolidinium 27 293343 1179 24 208424 0.08 0.9907
Sulfonium 14 253333 7120 25 143185 0.13 0.9799

fonyl]imide (27 cP) [39]. Particularly, ILs viscosity values behave in the following order
for Imidazo-lium(+) structure (the most frequent cation): [dca] < [CF3 BF3 ] < [C2 F5 BF3 ]
< [NTf2 ] < [TfO] < [NfO] < [MeSO4 ] < [BF4 ] < [PF6 ] [19]. Additionally, Table 6 shows
the accuracy of viscosity estimation at 298K of ILs based on different cation types. Note
that, viscosity at 298K is one of the most important physical properties when consider-
ing any scale-up of IL applications [14, 40]. In this case, the results show the obtained
deviations for the most commonly used cations as follows: Ammonium, Phosphonium
< Imidazolium (alkyl, di-alkyl, tri-alkyl), results in an acceptable prediction for the
broad diversity of ILs. Moreover, viscosity comparison among different ILs based on the
Imidazolium(+) structure is produced on the relationship between Van der Waals forces
and alkyl chain length.
Remarkable differences in viscosity are also observed for several anion types [41]. ILs
with larger anions clearly show higher viscosities, e.g. from trifluoroacetates (35 cP)
 -547-

Table 6. Viscosity estimation at 298 K for different cation types using the
ACM+ANN+PSO method.

Training set Prediction set

Cation class
N298K MRE() R2 N298K MRE() R2
1,3-Dialkyl-imidazolium 200 0.09 0.9885 49 0.10 0.9933
1-Alkyl-imidazolium 8 0.08 0.9917 7 0.08 0.9990
Tri-alkyl-imidazolium 4 0.14 0.8919 1 0.14
Ammonium 53 0.10 0.9855 26 0.10 0.9812
Morpholinium 5 0.10 0.9692 2 0.04 1.0000
Oxazolidinium 4 0.10 0.9860 6 0.03 0.9990
Phosphonium 5 0.12 0.9836 6 0.09 0.9952
Piperidinium 7 0.04 0.9981 7 0.04 0.9954
Pyridinium 6 0.06 0.9886 2 0.04 1.0000
Pyrrolidinium 20 0.11 0.9654 7 0.09 0.8981
Sulfonium 5 0.10 0.8985 1 0.00
to heptafluorobutanoates (105 cP) for 1-ethyl-3-methylimidazolium cation [39]. Table 7
shows viscosity estimation using ACM+ANN+PSO method for the most common anion
types. In this Table, the deviation of MRE() during training as follows: 0.15 > [I] ,
[Br] , [TfO] > 0.10 > [SCN] , [dca] , [TA] , [PF6 ] , Metal complexes, [TSAC] , [Ac] ,
[BETI] , [BF4 ] , [NTf2 ] , [Cl] > 0.05 > [nSO4 ] , [f] 0, and shows ranges of: 0.15 >
[SCN] , [BETI] , [PF6 ] > 0.10 > [TA] , [TfO] , [Ac] , [dca] , [NTf2 ] , [BF4 ] > 0.05 >
[f] , [Cl] , [nSO4 ] , [TSAC] , [I] , Metal complexes, [Br] 0, for the prediction set.
For other anion types MRE were lower than 0.05 for both set. Note that, anion effect
shows a similar behaviour for 298K .
On the other hand, dicationic and dianionic ILs were included in this study as well.
In this case, MRE during the training step was 0.04 for 6 ILs, and MRE during the
prediction step was 0.06 for 3 ILs. As discussed above, the anion and cation structures
affect the viscosity of ILs, and in general the main advantage of the proposed method
is the reproduction of the anion/cation effect (governed essentially by van der Waals
volume and H-bonding [42]), but now in terms of the contributions of structural groups
on viscosity.
Figure 4 shows the capability of the proposed method for the reproduction of the effect
(+)
of the n-alkyl chain length ([CH3 ](+) + [CH2 ]n ) on the viscosity of 1-alkyl-3-methyl-
imidazolium cations for the anion type [NTf2 ] at 298K. As this graph illustrates, smaller
(+)
alkyl chain lengths of the Imidazolium(+) structure, such as ethyl ([CH3 ](+) + [CH2 ]1 ),
(+)
present lower viscosity than the decyl ([CH3 ](+) + [CH2 ]9 ) substituted
 -548-

Table 7. Viscosity estimation using the ACM+ANN+PSO method for the most common anion types.

Anion class Acronym Ndata T (K) (cP) ln MRE() R2

Training set
2,2,2-Trifluoro-n-(trifluoromethylsulfonyl)acetamide [TSAC] 14 298298 25391 36 0.08 0.9833
Acetate [Ac] 10 283353 221630 37 0.08 0.9970

Bis(perfluoroethylsulfonyl)imide [BETI] 11 283353 14292 26 0.08 0.9907
Bis(trifluoromethylsulfonyl)imide [NTf2 ] 444 258433 21266 17 0.08 0.9920
Bromide [Br] 4 298298 6631665 68 0.12 0.8007
Chloride [Cl] 12 298394 1518089 210 0.07 0.9994
Dicyanamide [dca] 49 253363 5509 16 0.10 0.9927
Formate [f] 4 298298 70854 47 0.03 0.9994
Hexafluorophosphate [PF6 ] 183 273373 146410 29 0.09 0.9939
Iodide [I] 5 298298 11103125 78 0.14 0.9308
Metal complexes [X] 50 283373 204145 38 0.09 0.9908
Sulfates [nSO4 ] 74 273395 13875 27 0.04 0.9986
Tetrafluoroborate [BF4 ] 263 273373 82291 28 0.08 0.9940
Thiocyanate [SCN] 9 293348 10625 27 0.10 0.9918
Trifluoroacetate [TA] 6 293298 3526100 310 0.09 0.9991
Trifluoromethanesulfonate [TfO] 17 278348 112030 28 0.11 0.9887
Prediction set
2,2,2-Trifluoro-n-(trifluoromethylsulfonyl)acetamide [TSAC] 3 298 298 117 187 46 0.04 0.9988
Acetate [Ac] 3 293298 91701 47 0.09 0.9967
Bis(perfluoroethylsulfonyl)imide [BETI] 2 298298 218552 57 0.12 1.0000
Bis(trifluoromethylsulfonyl)imide [NTf2 ] 124 283373 8606 27 0.09 0.9909
Bromide [Br] 2 298298 827 1370 68 0.01 1.0000
Chloride [Cl] 13 298394 2720883 310 0.05 0.9997
Dicyanamide [dca] 41 253343 7267 26 0.09 0.9799
Formate [f] 2 298298 78229 46 0.05 1.0000
Hexafluorophosphate [PF6 ] 67 273373 323924 38 0.12 0.9823
Iodide [I] 7 293353 491535 38 0.04 0.9998
Metal complexes [X] 24 278373 6144 15 0.02 0.9996
Sulfates [nSO4 ] 18 293343 16289 26 0.04 0.9988
Tetrafluoroborate [BF4 ] 25 283343 53731 47 0.08 0.9887
Thiocyanate [SCN] 4 293298 861017 47 0.14 0.9804
Trifluoroacetate [TA] 18 283353 10192 26 0.10 0.9836
Trifluoromethanesulfonate [TfO] 26 283353 13208 26 0.10 0.9826
 -549-

4.5
ln

3.5
1 2 3 4 5 6 7 8 9
nalkyl chain length

(+)
Figure 4. Reproduction of the n-alkyl chain length effect ([CH3 ](+) + [CH2 ]n )
on the viscosity of 1-alkyl-3-methylimidazolium cations for the anion
type [NTf2 ] at 298K using ACM+ANN+PSO. () Experimental vis-
cosity values, and (+) calculated values.

cation structures, with a correlation coefficient R2 = 0.9954 for the relationship ln 298K =
(+)
0.1595([CH2 ]n )+3.4269. This Figure confirms the discussion presented above and
shows that ACM+ANN+PSO method can reproduce, for this case, the tendency for the
n-alkyl chain length to increase with the viscosity (ln 298K ).

4.4. Molecular weight effect

Molecular weight contribution can be quantified using the RC into the network (see
Table 3). In this context, M has one of the largest RC within the viscosity. Note that,
heavier molecules present a stronger van der Waals force, and this stronger intermolecular
 -550-

force result in higher viscosity value [23]. This shows the importance of M on , and
illustrates why it has been used by other researchers for estimating transport properties of
ILs [23,43]. In addition, molecular weight range (M ) used impose additional difficulties
to the problem that the ACM+ANN+PSO technique has been able to solve (see Table
5).
Figure 5 shows the molecular weight variation effect on 1-alkyl-3-methyli-midazolium
with [BF4 ] anion, where dots represent the experimental viscosity values at 298K (speci-
ficly ethyl, propyl, butyl, hexyl, and octyl), and crosses represent the calculated values
by ACM+ANN+PSO. As it illustrates, the viscosity increases with the molecular weight,
and the proposed method can reproduce this effect on the viscosity (as ln ) with good
accuracy. Note that the point corresponding to 1-propyl-3-methylimidazolium [BF4] is
off in Figure5. This point was not obtained from theoretical methods, correlations or
extrapolations of any kind, and it was taken from experimetal data guaranteed in the
literature. Nevertheless, from the context of analisys of homologous series [44], the cal-
culated values by the proposed method (as +) exhibit physically expected trends within
the homologous series and the temperature dependence (for more examples of analisys of
homologous series of ILs, see [45]).

4.5. Comparative analisys

A number of models has been used for the estimation of liquid viscosity in the litera-
ture [46, 47]. Poling et al. [48] discussed a variety of correlation and prediction methods
for viscosities. Due to the complexity of some non-linear models, a molecule can be de-
scribed in many different ways. Additionally, if model parameters are larger they require a
significant number of computational resources for the estimation of liquid viscosity of pure
compounds. In this case, the suggested ACM for ln (T ) was developed using the hybrid
ANN+PSO algorithm [31]. Note that, the relationship between the molecular stucture
and thermodynamic properties is highly non-linear, and consequently, an artificial neural
network type can be a suitable alternative for modelling the underlying thermodynamic
properties. In this context, a comparison was made between the ANN+PSO algorithm,
and a neural network with standard back-propagation (BPNN) with similars architecture
(54-9-1) and database. This BPNN shows statistical results of an AARD of 9.7%, and a
%Emax larger than 50%. Figure 6 shows the AARD found in the prediction of ln (T )
 -551-

5.5

5
ln

4.5

3.5
180 200 220 240 260 280 300
M

Figure 5. Reproduction of the molecular weight effect on the viscosity of

1-alkyl-3-methylimidazolium [BF4 ] at 298K by ACM+ANN+PSO. ()
Experimental viscosity values, and (+) calculated values. In increasing
order: ethyl, propyl, butyl, hexyl, and octyl.

using BPNN and ANN+PSO. From the physical point of view, BPNN shows a MRE()
greater than 0.3, while low deviations found by the proposed model (an AARD a little
higher than 2%, a %Emax of 17%, and a MRE() lower than 0.09), indicate that it
can estimate ln (T ) of ILs with low deviations can others ANN-types. Regarding ILs
viscosity estimation by ANN-types, Valderrama et al. [24] presented a BPNN to predict
the viscosity of 58 ILs using the molecular mass, the mass connectivity index and the
density at 298K as input parameters. Some considerable disadvantages of Valderramas
neural network model are: (i) the used small database that results in considerably poor
predictions; (ii) the use of density at 298K of ILs. Note that, Coutinho et al. [9] presented
a critical review on predictive methods for the estimation of thermophysical properties of
 -552-

60

50

40
AARD

30

20

10

0
0 2 4 6 8 10 12
ln

Figure 6. Average absolute relative deviations found in the estimation of ln (T )

of ILs using: artificial neural network with particle swarm optimization
(), and artificial neural network with standard back-propagation ().

ILs, with an AARD a slightly higher than 6% for density at 298K. Thus, input data
reliability is never established, making interpretation of deviations between the Valder-
ramas neural network model and experimental data of impossible to be made; (iii) the
larger hidden layers used (two hidden layers). It should be stated that there is no need
to have more than one hidden layer for providing the ability to generalize in a neural
network [31]. This premise is supported by theoretical results and by many simulations
in different science fields [49]. Kurkova [50] gave a direct proof of the universal approxi-
mation capabilities of an ANN with one hidden layer. In addition, ANN weights contain
the most important information related to the problem to be solve by ANN [51], but
Valderrama et al. [24] did not provide the optimal weight obtained by ANN; however,
 -553-

they did provide the program codes and input files to calculate . In contrast, the use of
PSO on ANN provides a reduced number (only one) of hidden layers, and a very good
tool to obtaining the optimal ANN weights [32].
Other comparison was made with a group contribution method (GCM) reported in
the literature in order to estimate ln of ILs. Gharagheizi et al. [12] introduced their
GCM for predicting ln with an AARD higher than 6% and a %Emax higher than 31%.
Gharagheizis GCM employs a total of 46 sub-structures in addition to the temperature
for 1672 viscosity values of 443 ILs. Please note that the data points used in the pro-
posed method and the Gharagheizis GCM are similars, 1651 and 1672 respectively, but,
the supporting material provided by Gharagheizi et al. [12] shows duplicate data points,
and this fact would reduce their data points. Then, it is worth pointing out that both
methods obtained their results from different databases with different correlation and
prediction sets (or training and prediction sets), and based on different methodologies
and the results cannot be compared directly with one another. However, a comparison
can be made for some selected datasets of common ILs for both methods. Table 8 shows
a comparison between the proposed method (ACM+ANN+PSO) and the Gharagheizis
GCM [12] for estimating ln (T ) of ILs. This Table contains 60 datasets of ILs in com-
mon taken from [34,5277]. Note that this comparison is based only on AARD because in
Gharagheizi et al. [12] present their results only with this statistical parameter. Based on
these results, Gharagheizis GCM showed an AARD of 6.5%, while the proposed method
resulted in an AARD of 2.0%. In particular, the proposed method shows a much higher
accuracy than Gharagheizis GCM when applied to ILs composed of anions like halides,
sulfonates and metal complexes. But in general, the suggested ACM+ANN+PSO tech-
nique presented a higher accuracy and more advantages than the other reported methods
for predicting (T ) of ILs (e.g. [12, 14]). Note that, the incorporation of cation groups,
such as imidazolium, pyridinium, pyrrolidinium, piperidinium, phosphonium, ammonium,
morpholinium, oxazolidinium, sulfonium, and guanidinium, have applications for several
ILs used in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis,
and chemical separations [78]. Also, the incorporation of groups for the ionic liquids with
halide-containing cations, and pseudohalides and metal complexes for the anion, trans-
forms this method in the most complete one for esimating ln (T ) of ILs that has been
reported so far (see Table 1).
 Table 8. Comparison between the proposed method and a GCM reported in the literature for estimating ln (T ) of ILs.
Gharagheizi et al. [12] This work
Set Cation Anion Ndata T (K) (cP) ln Ref.
AARD AARD
1 [Bis(aminomethylene)C1(2) ammonium bis(trifluoromethylsulfonyl)imide 5 303333 124335 46 2.0 0.8 [52]
2 1-(2-methoxyethyl)-3-methylimidazolium hexafluorophosphate 3 283303 148608 56 3.1 1.3 [53]
3 1-(2-methoxyethyl)-3-methylimidazolium tetrafluoroborate 3 283303 138374 46 10.6 2.0 [53]
4 1,3-Dimethylimidazolium bis(trifluoromethylsulfonyl)imide 7 298353 838 24 9.7 1.5 [54]
5 1,3-Dimethylimidazolium bis(trifluoromethylsulfonyl)imide 8 283353 877 24 9.0 2.4 [55]
6 1,3-Dimethylimidazolium methylsulfate 7 293343 1693 25 11.2 1.0 [56]
7 1-Butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide 10 283343 22152 35 4.0 2.3 [57]
8 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate 10 283343 66307 46 6.4 2.2 [57]
9 1-Butyl-3-methylimidazolium acetate 8 283343 421630 37 5.6 1.3 [58]
10 1-Butyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide 9 283353 14292 26 1.2 0.8 [54]
11 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 3 295323 2252 34 8.3 2.1 [59]
12 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 6 283333 15107 25 4.1 0.6 [55]
13 1-Butyl-3-methylimidazolium hexafluoroantimony 10 283343 29177 35 17.2 0.6 [57]
14 1-Butyl-3-methylimidazolium hexafluorophosphate 9 283353 23824 37 5.9 1.2 [54]
15 1-Butyl-3-methylimidazolium hexafluorophosphate 24 273353 261717 37 4.7 1.1 [60]
16 1-Butyl-3-methylimidazolium octylsulfate 9 293373 23875 37 4.8 1.1 [61]
17 1-Butyl-3-methylimidazolium thiocyanate 6 298348 1052 24 4.8 3.0 [62]
18 1-Butyl-3-methylimidazolium tetrafluoroborate 9 283353 13256 26 4.2 0.9 [54]
19 1-Butyl-3-methylimidazolium tetrafluoroborate 47 273353 14543 26 2.7 0.7 [63]
20 1-Butyl-3-methylimidazolium methylsulfate 9 293343 30289 36 1.7 0.6 [64]
21 1-Butyl-3-methylimidazolium trifluoromethanesulfonate 9 283353 13208 25 3.1 2.9 [54]
-554-

22 1-Butyl-3-methylimidazolium trifluoromethanesulfonate 10 283343 19131 25 3.9 1.4 [57]

23 1-Butyl-3-methylimidazolium chloride 6 303394 273950 38 12.3 1.1 [65]
24 1-Butyl-3-methylimidazolium trifluoroacetate 9 283353 10192 25 2.9 2.8 [54]
25 1-Butyl-3-methylimidazolium trifluoroacetate 8 283343 13155 25 1.3 1.0 [66]
26 1-Decyl-3-methylimidazolium tetrafluoroborate 3 283303 223846 57 2.9 3.8 [53]
27 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 8 293353 839 24 9.0 2.7 [54]
28 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 7 293353 839 24 9.6 3.2 [55]
29 1-Ethyl-3-methylimidazolium ethylsulfate 10 298343 1998 25 1.1 0.3 [67]
30 1-Ethyl-3-methylimidazolium ethylsulfate 8 273333 25458 36 1.9 0.4 [68]
31 1-Ethyl-3-methylimidazolium tetrafluoroborate 7 293323 1645 24 18.4 5.5 [69]
32 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate 8 278348 1196 25 6.6 2.8 [70]
33 1-Ethyl-3-methylimidazolium dicyanamide 5 273313 1152 24 3.3 3.6 [68]
34 1-Hexyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide 8 283343 22317 36 2.7 2.2 [66]
35 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 5 293373 890 24 7.0 0.4 [34]
36 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 8 283353 11154 25 2.2 1.4 [55]
37 1-Hexyl-3-methylimidazolium chloride 4 298343 34018089 510 20.0 1.3 [67]
38 1-Hexyl-3-methylimidazolium tetrafluoroborate 8 288323 54316 46 1.4 1.4 [71]
39 1-Hexyl-3-methylimidazolium hexafluorophosphate 4 293353 35707 37 4.6 1.8 [66]
40 1-Hexyl-3-methylimidazolium hexafluorophosphate 25 273353 353924 38 5.7 1.9 [72]
41 1-Isobutyl-3-methylimidazolium tetrafluoroborate 10 288313 53214 45 1.6 0.7 [73]
42 1-Methyl-3-allylimidazolium chloride 6 303394 151150 27 10.9 2.1 [65]
Continued on next page
 Table 8 continued from previous page
Gharagheizi et al. [12] This work
Set Cation Anion Ndata T (K) (cP) ln Ref.
AARD AARD
43 1-Octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 9 283353 13200 25 2.3 2.0 [54]
44 1-Octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 8 283353 13218 25 2.2 1.7 [55]
45 1-Octyl-3-methylimidazolium hexafluorophosphate 29 273353 436410 39 5.1 0.8 [74]
46 1-Octyl-3-methylimidazolium hexafluorophosphate 4 293353 421052 37 5.7 0.6 [66]
47 1-Octyl-3-methylimidazolium tetrafluoroborate 27 273353 282291 38 7.6 2.1 [74]
48 1-Octyl-3-methylimidazolium tetrafluoroborate 8 288323 67412 46 1.7 4.8 [71]
49 1-Octyl-3-methylimidazolium chloride 4 298343 38720883 610 21.6 0.9 [67]
50 1-Octyl-3-methylimidazolium tetrachloronickelate(II) 3 301313 50144 35 4.3 1.4 [75]
51 1-Pentyl-3-methylimidazolium tetrachloronickelate(II) 3 298313 33125 35 6.1 0.7 [75]
52 1-Propyl-3-methylimidazolium iodide 7 293353 491535 37 7.5 0.7 [76]
-555-

53 Ethyldibutylsulfonium dicyanamide 6 253353 9494 26 5.4 3.7 [77]

54 Ethyldimethylsulfonium dicyanamide 5 253333 9120 25 10.5 1.7 [77]
55 Ethyldipropylsulfonium dicyanamide 6 253353 7173 15 11.5 4.1 [77]
56 Methyldibutylsulfonium dicyanamide 6 253353 10509 26 4.7 7.5 [77]
57 Methyldiethylsulfonium dicyanamide 5 253333 9102 25 8.9 1.3 [77]
58 Methyldipropylsulfonium dicyanamide 6 253353 7185 15 11.4 2.4 [77]
59 Tri-ethylsulfonium dicyanamide 5 253333 895 25 12.4 5.8 [77]
60 Tri-methylsulfonium dicyanamide 4 273333 1176 24 10.1 3.1 [77]
Overall 6.5 2.0
 -556-

5. Conclusions
In this study, the viscosity of several ILs at different temperatures was correlated and
estimated using an artificial neural network (ANN) optimized with particle swarm opti-
mization (PSO) in order to update the weights of the network. In order to discriminate
among different IL classes, molecular weight and molecular structure, as defined by the
concepts of an additive-constitutive methods, were used as input parameters. Thus, the
complete method was called ACM+ANN+PSO.
Based on the results and discussion presented in this study, the following conclusions
can be drawn:
(i) The proposed method (ACM+ANN+PSO) allows the viscosity estimation of sev-
eral IL classes composed of 20 cation groups and 32 anion groups in a wide range of
temperatures (253433 K), and viscosities (226100 cP). For a database consisting of
1651 data points for 413 ILs, the AARD observed was 2%. The great differences in the
chemical structure, and the physical properties of the ILs considered in the study impose
additional difficulties to the problems that the proposed method has been able to handle
(see, Table 2).
(ii) The accuracy of the model was tested by comparing calculated and experimentally
measured viscosity values from the literature [5], resulting in a correlation coefficient of
R2 =0.994 (see, Figures 2 to 3). Results show that the ACM+ANN+PSO techique can
estimate the viscosity of ILs at different temperatures with low deviations (see, Tables
4 to 8). It is also applicable at a temperature range that is higher than those methods
referenced by other authors and mentioned in this study. Note that the proposed method
should be able to predict the viscosity of a larger range of ILs as data for these to become
available. Thus, the values calculated using the proposed model are considered to be
accurate enough for engineering calculations, for generalized correlations and for equations
of state methods, among other uses.
(iii) An important observation that is worth pointing out is the influential effects of
the structural groups in the correlation and prediction of the viscosity. Note that the main
advantage of the proposed method is to reproduce the cation and anion effects (governed
essentially by van der Waals forces and H-bonding [42]) in terms of the contributions
of structural groups on the viscosity (see, Figure 4). Similar results were also obtained
for reproducing the molecular weight effect on the viscosity with the ACM+ANN+PSO
 -557-

technique (see, Figure 5).

(iv) The incorporation of a PSO for the optimization of the neural network weights
has positive effects on architecture, reducing the number of neurons in the hidden layer
while controlling the selection of network connection weightings in a wide numerical range
(see, Table 3). Traditional optimization techniques such as the back-propagation learning
algorithm can also determine the number of network parameters, such as network connec-
tion weightings; however, traditional optimization techniques are not able to control the
network parameter optimizations. In contrast, the PSO was able to solve this problem.

Acknowledgments: The author thanks the Direction of Research of the University of La

Serena (DIULS), through the research project PEQ16141, and the Department of Physics
of the University of La Serena (DFULS) for the special support that made possible the
preparation of this paper.

Supporting Information
For interested readers, all data of substances and properties used in the ACM+ANN+PSO
model can be provided via the authors e-mail.
Tables S1 and S2 contain the database used for the training and prediction sets,
respectively, Table S3 provides a program code for ln estimation using the trained
ACM+ANN+PSO model. Note that this code is not made for a specific commercial
software, and can be used with any calculation software. Using this code, you may be
able to independently reproduce the results present in this study.

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