Chemical Engineering Science 80 (2012) 326333

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Development of a group contribution method for determination

of viscosity of ionic liquids at atmospheric pressure
Farhad Gharagheizi a, Poorandokht Ilani-Kashkouli a, Amir H. Mohammadi b,a,n,
Deresh Ramjugernath a,nn, Dominique Richon c,a
a

Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa
nergetique et Procedes, 35 Rue Saint Honore, 77305 Fontainebleau, France
MINES ParisTech, CEP/TEP-Centre E
c
Technical University of Denmark, Center for Energy Resources Engineering (CERE), Department of Chemical and Biochemical Engineering, DK-2800 Kgs. Lyngby, Denmark
b

H I G H L I G H T S
c
c
c
c
c

A data set consisting of 1672 viscosity values and comprising 443 ILs was collated from the literature.
A reliable group contribution method has been developed using this dataset.
The method employs a total of 46 sub-structures in addition to the temperature to predict the viscosity of ILs.
Twenty four sub-structures related to anions, and 22 sub-structures related cations were implemented.
The model produces very encouraging results.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 4 April 2012
Received in revised form
3 June 2012
Accepted 13 June 2012
Available online 27 June 2012

In this study, a wide literature survey has been carried out to collect an extensive set of liquid viscosity
data for ionic liquids (ILs). A data set consisting of 1672 viscosity values and comprising 443 ILs was
collated from 204 different literature sources. Using this data set, a reliable group contribution method
has been developed. The method employs a total of 46 sub-structures in addition to the temperature to
predict the viscosity of ILs. In order to differentiate the effects of the anion and cation on the viscosity of
ILs, 24 sub-structures related to the chemical structure of anions, and 22 sub-structures related to the
chemical structure of cations were implemented. The proposed model produces a low average relative
deviation (AARD) of less than 6.4% taking into consideration all 1672 experimental data values.
& 2012 Elsevier Ltd. All rights reserved.

Keywords:
Viscosity
Ionic liquids
Group contribution
Model
Database
Estimation

1. Introduction
There has been great interest in ionic liquids (ILs) which has
grown steadily in recent years in both academia and industry.
The interest is due to the potential of the ILs in the majority of
scientic and engineering applications, and particularly owing to
ionic conductive properties and the potential tuneability of ILs to
applications.
Ionic liquids refer to the class of salts composed of ions which
are typically liquids at ambient temperatures with insignicant

n
Corresponding author at: MINES ParisTech, CEP/TEP-Centre Energetique et Procedes, 35 Rue Saint Honore, 77305 Fontainebleau, France. Tel.: 33 1 64 69 49 70;
fax: 33 1 64 69 49 68.
nn
Corresponding author. Tel.: 27 312603128; fax: 27 312601118.
E-mail addresses: amir-hossein.mohammadi@mines-paristech.fr
(A.H. Mohammadi), ramjuger@ukzn.ac.za (D. Ramjugernath).

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.06.045

vapor pressure (Freemantle, 2010; Meindersma et al., 2000). There

are a number of properties which make them promising options for
superseding the conventional hydrocarbon based solvents. Their
physical, chemical and biological characteristics have the potential
to be tuned by the combination of appropriate anions and cations.
However, this is not a simple task owing to the vast possible number
of ILs possible via the permutations of anions and cations (Rogers and
Seddon, 2003). Hence, it is essential to propose predictive computational tools capable of contributing to enable tailoring new ILs with
desired properties.
In this study, the main aim is to develop a reliable model for
the estimation of viscosity of ILs. Viscosity is the internal friction
or resistance to ow caused by intermolecular interactions and is
accordingly very important in all physical processes involving
uid movement or components dissolved in them. For that reason,
any chemical or pharmaceutical unit operations dealing with the
transfer of uids or energy require knowledge of the viscosity of pure

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

compounds and/or their mixtures. Viscosity is the most important

physical property when considering any scale-up of ionic liquid
applications (Reichardt and Welton, 2011; Rooney et al., 2009).
Prediction of viscosity is normally difcult, and exible predictive models will require further experimental data in order to
obtain a better understanding of this property. There are several
models proposed for the prediction of ionic liquid viscosity.
Abbott (2004) proposed a theoretical model for prediction of

viscosity by modifying hole theory, originally proposed by Furth

(1941a,b). In his paper, 11 ILs mainly based on imidazolium at
three temperatures (298, 303 and 364 K) were investigated.
Despite interesting, theoretical interpretation, the model fails to
predict viscosity data with acceptable accuracy and therefore has
no merit for practical applications (average absolute relative
deviation (AARD) 122%).
Matsuda et al. (2007) introduced a quantitative structureproperty relationship (QSPR) method for the prediction of viscosity. For these purposes, a polynomial expansion model was
developed. It contains terms related to temperature, cation, the
side alkyl chain attached to cation and the other side chain except
for the anion and alkyl chain. The model derived was based on
300 experimental viscosity data points belonging to the alkylamine, pyrrole, piperidine, pyridine and imidazole families. Their
data points were within the range of 263353 K. In comparison
with experimental data, their model made inferior predictions for
pyridine cation and ethylsulfate. The correlation between the
model and experimental data had a squared correlation coefcient (R2) of 0.8971. As mentioned earlier, their model is based on
a limited number of anion and cation groups, and therefore the
prediction of viscosity of ionic liquids for which either their anion
or cation groups were not part of the data set should be undertaken with caution. Apart from this, relating the viscosity which
has an intermolecular origin merely to the graph structure of the
molecules is disputable. In addition, for new anion or cation
introduced to the data set, all calculations have to be repeated to
determine the proper correlation coefcients.
Bini et al. (2008) also developed a QSPR method for prediction
of ionic liquid viscosity. They studied viscosity data for 33 ILs
based on imidazolium, pyridinium, piperidinium and morpholinium cations, bearing linear alkyl or oxyalkyl chains at two
temperatures (293 and 353 K). After omitting all data points
pertaining to nitrile-functionalized ILs as outliers, they proposed
a four-parameter model for the prediction of viscosity values
at (293 and 353 K) with the R2 values of 0.8755 and 0.9460,
respectively. According to their results, the model could not
satisfactorily predict low-viscosity data. Besides, the absence of other
ionic liquid families in addition to very limited temperature range,
drastically conne the predictive capability of their derived model.
Gardas and Coutinho (2008) applied an OrrickErbar-type
group contribution method to develop a predictive model for
viscosity. They investigated a large compilation of 498 experimental data points comprising 29 ILs based on imidazolium,
pyridinium and pyrrolidinium with the range of temperature
from 293 to 393 K and viscosity from 4 to 21,000 cP. Their model
predicts the viscosity of ILs with an acceptable AARD of less than
8%. However, their proposed model contains a density term,
which should be estimated prior to the calculation. On the other
hand, merely three classes of ionic liquids were investigated in
their work. As indicated in previous studies, the cation and anion
structures have a profound effect on the viscosity. Thus, the
prediction capability of the model merely limits its application
to the three ILs classes and any extrapolation for ILs belonging to
absent classes may bring about erroneous results. In their later
publication (Gardas and Coutinho, 2009), they proposed a new
correlation based on the VogelTammannFulcher equation without a density term. However, the model still suffers from a lack of

327

extrapolation ability due to the limited number of investigated

ionic liquid classes.
In another study, Ghatee and Zare (2011), Ghatee et al. (2010)
implemented the well-known form of the power law equation of
viscosity and proposed a three-parameter model with two components; temperature dependent and characteristic exponent parameters. They derived the model parameters for 49 ILs based on 403
experimental data values. The major deciency of their model is
that its parameters are solely derived from statistical and regression
calculations. In other words, for ILs not present in their study,
experimental data are needed to calculate the model parameters.
Han et al. (2011) proposed a QSPR method for prediction of the
viscosity of imidazolium based ionic liquids. Initially, they gathered a database of 1731 experimental data values at various
temperatures and pressures for 255 ILs (comprising 79 cations
and 71 anions) from literature. Then, they developed some QSPR
models for viscosity of ILs at 298.15 K and 1 atm. For this purpose,
they employed a sub-data set containing 84 viscosity data values
from the database. They split the data set into 4 subsets and
derived a correlation for each one: [BF4]  , [Tf2N]  , [C4mim] and
[C2mim] . There are several drawbacks associated with their
models. First, the derived models are temperature independent,
which connes its application to predict viscosity merely at
298.15 K. Second, their attention was focused on just a single
class of imidazolium-based ILs; however, they did not propose a
universal correlation for all ILs present in their study.
Very recently, Mirkhani and Gharagheizi (2012b) presented a
QSPR method for prediction of ILs viscosity. Their model shows an
AARD of less than 9% from 435 experimental data values for
293 ILs.
Among various chemical structure-based methods (Poling et al.,
2001), quantitative structure-property relationships (Gharagheizi,
2012a,b; Gharagheizi et al., 2011a, 2011c, 2011f, 2011g, 2011h,
2011i; 2012a, 2012b, 2012c, 2012d; Gharagheizi and Sattari, 2010;
Mirkhani and Gharagheizi, 2012a; Mirkhani et al., 2012a, 2012b;
Mousavisafavi et al., 2012a; Mousavisafavi et al., 2012b), and particularly, the group contribution methods (GC) have gained recognition
in the correlation and prediction of various physical, chemical and
biological properties.(Gharagheizi, 2009a,b,c; Gharagheizi and Abbasi,
2010; Gharagheizi et al., 2010, 2008; Gharagheizi et al., 2011b,d,e,
2011h, 2011j; Gharagheizi and Salehi, 2011; Keshavarz et al., 2011)
A major purpose of the GC is to relate a desired property to the
number of occurrences of some chemical substructures. The favored
feature of these models is their simplicity and capability to give a
rational determination of the properties. Considering this, a comprehensive GC model is presented for estimation of the viscosity of ionic
liquids in the present work.

2. Methodology
2.1. Data preparation
A wide literature survey was performed to collect an extensive
experimental viscosity database for ILs at atmospheric pressure.
Finally, 1672 data for 443 ILs composed of 76 anions and 191
cations were collected from 204 different references. The chemical structures of the anions and cations are presented as supplementary materials (see Tables mmc1 and mmc2).
In case of multiple reported data points, the latest corresponding
data point was considered. The ILs within the data set were classied
into 17 groups containing 1,3-dialkyl imidazolium, 1-alkyl imidazolium, amino acids, ammonium, double imidazolium, guanidinium,
isoquinolinium, morpholinium, oxazolidinium, phosphonium, piperidinium, pyridinium, pyrrolidinium, pyrroline, sulfonium, tetra-alkyl
imidazolium and tri-alkyl imidazolium.

328

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

The information about the names, abbreviations, groups and

the original reference for each data point are presented as
supplementary materials (see table mmc3).
To construct a reliable method, the selected experimental data
are typically divided into the two parts: a training and a test
set. The training set is used to develop the model. The test set
is used to check the capability of the model to predict the desired
property of the compounds absent in model derivation. In this
study, K-means clustering is applied to select training and test
sets. K-means clustering is a method of cluster analysis, which
aims to partition n observations into k clusters in which each
observation belongs to the cluster with the nearest mean. According to the rule of thumb, nearly 20% of the data (336 data points)
were kept out to test the model (Gharagheizi, 2007). The remaining data were implemented for model development.
2.2. Development of new group contributions
In this step, the chemical structures of all the ILs were
analyzed with much attention paid to comparing the chemical
sub-structures to dene the most efcient contributions to the
viscosity. To differentiate the effects of anions and cations on the
viscosity, the contributions of anions and cations were independently investigated. Pursuing the procedure, a compilation of 46
chemical sub-structures (24 for anions and 22 for cations) in
addition to temperature were found to be most efcient for the
estimation of viscosity. The sub-structures used and their number
of occurrences in chemical structures of anions and cations for
each IL were used as the model parameters. They are presented as
supplementary materials (see table mmc3).
2.3. Development of model
The major step in developing a GC method is to search for a
relationship between the chemical sub-structures and the desired
physical property. The simplest method for this purpose is the
assumption of existence of a multi-linear relationship between
the groups and the property (here the viscosity). This technique is
generally used to develop most of the GC methods. As a result, the
provided collection of 46 sub-structures in addition to temperature is employed to develop the model (input parameters).
To calculate the contribution of these functional groups, the
well-known least square method is implemented.

3. Results and discussion

According to the aforementioned procedure, the contributions
of each of 46 parameters were determined. The proposed model
for estimation of viscosity of ILs (The units for Z and T are
respectively cP and K) is found as follows:
logZ

Na
X
i1

Nai Zai

Nc
X
i1

Nci Zci AT

B
D
CT 2 2 Z0
T
T

where Nai , Nci , Zai , Zci ,and Z0 are, respectively, the number of
occurrence of ith sub-structure of anions and cations, the contribution of the ith sub-structure of anions and cations, and the
intercept of Eq.(1). The obtained group contributions, namely Zai ,
Zci , Z0 , as well as the temperature coefcients A, B, C, and D are
presented in Table 1.
The predicted viscosities and their absolute relative deviations
(ARD) from experimental values are presented as supplementary
information (see table mmc3). Moreover, the references for the
viscosity data points are presented as supplementary materials
(see table mmc3). The statistical parameters of the model are
presented in Table 2. The results demonstrate that this GC model

can reliably estimate the viscosity of ILs. The model results,

respectively, show an average absolute relative deviation, standard deviation, and root mean square error of 6.4%, 0.21, and 0.21
from the 1672 experimental data.
The AARD% of the model for each class of ILs used in this study
are presented in Table 3.
The predicted viscosities in comparison with the experimental
values are presented in Fig. 1. In addition, the deviation of the model
in comparison with the experimental data is presented as Fig. 2.
These comparisons clearly show that this model can be used as
a predictive tool for the prediction of the viscosity of various ILs.
A comparison between the model predictions and their corresponding experimental values is depicted in Fig. 3.
Careful analysis of the 39 points for which the model shows
an ARD of more than 25%, indicates that 25 points belong to the
1,3-dialkyl imidazolium group, 5 points to ammonium, 5 point to
phosphonium, one point to guanidinium, one point to pyrrolidinium, one point to sulfonium, and the last point to tri-alkyl
imidazolium. The large number of 1,3-Dialkyl imidazolium-based
ILs which show high deviations is expected as 1382 data values
from 1672 experimental data values used in this study are for
1,3-Dialkyl imidazolium group. It appears that the high model
deviation do not belong to a particular group of ILs and are almost
scattered among various groups of ILs. It seems that they have
distributed over various chemical families according to the total
number of data from those chemical families. Therefore, large
deviation of these points may be due to inaccurate experimental
data rather than other reasons.
The models results for [C2mim][DCA], [C10mim][NTf2], [C1mim]
[NTf2], and [C2mim][C2SO4] as a function of temperature are presented in Fig. 4. As depicted, the model can accurately predict the
viscosity of ILs as a function of temperature.
One of the major causes of error in experimental data that may
bring about large deviations when developing models is the
presence of contaminations (Mirkhani and Gharagheizi, 2012b)
in the ILs or ILs which are not of extremely high purity being used.
They can signicantly affect various properties of ILs particularly
their viscosities. The contaminants are mostly composed of water,
halides, and other organic solvents. For instance existence of traces
of Cl ion in [C4mim][BF4] will result in a signicant deviation in its
viscosity. Moreover, with increasing the concentration of such ions,
the viscosity dramatically increases. For instance when the concentration of Cl increases from 0.01 to 0.5 m, the viscosity of
[C4mim][BF4] increases from 154 to 201 cP (Seddon et al., 2000).
In comparison with the previous models that have been
proposed, this model is more applicable across a wider domain.
It has been developed and evaluated using 443 ILs composed of
76 and 191 unique anions and cations. Additionally, the temperature range of experimental data in this study is 250433 K which
is wider than that of previous models. The model is even superior
to the previous QSPR model proposed by one of the authors
(Mirkhani and Gharagheizi, 2012b) due to its comprehensiveness
(76 and 191 unique anions and cations vs. 36 and 146 unique
anions and cations in the previous study) and accuracy (6.4% vs.
9% AARD in the previous study).

4. Conclusion
In this study, a group contribution method was successfully
developed to estimate the viscosity of ionic liquids. A comprehensive data set of 1672 viscosity data belonging to 443 ILs
composed of 76 anions, and 191 cations was employed to develop
this model. A collection of 46 chemical sub-structures in addition
to temperature was implemented as model inputs from which, 24
were anion-based, and the other 22 were cation-based. Using this

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

329

Table 1
The GCs table.
No.

GC

Chemical structure

2
3
4
5
6
7

]0
A
B
C
D
]a1
]a2
]a3
]a4
]a5
]a6






IBrClU-2
WCCY3

]a7

]a8

10

]a9

11

]a10

12
13

]a11
]a12

14

Comment

Terminal primary C(sp3) Y any terminal atom or

heteroaromatic group (i.e., H, X, OH, NH2, etc.)
number of total quaternary C(sp3)

Sum of all the carbons belonging to any

aromatic and heteroaromatic structure

Value
34.25030
 0.11968
 2665.71676
0.00013
64753.03094
1.61584
1.81349
1.41641
0.62500
0.91580
 0.05754
0.75075

0.03970
0.24272

Number of aliphatic tertiary C(sp2)

0.35111

Ketones (aliphatic)
Number of positive charged N

 0.99321
0.39962

]a13

Sulfones

0.27155

15

]a14

Sulfonates (thio-/dithio-) Y O or S

0.19610

16
17
18
19
20
21
22
23
24
25
26

]a15
]a16
]a17
]a18
]a19
]a20
]a21
]a22
]a23
]a24
]c1

27

]c2

Number of total secondary C(sp3)

YH or any heteroatom

28

]c3

Number of ring secondary C(sp3)

YH or any heteroatom

Al2  C O

CX4
R-C(X)-X or R-C#X or X C X
Ha attached to C0(sp3) no X attached to next C
H attached to alpha-Cb
O
Al O  Al
O
Fa attached to C2(sp2)-C4(sp2) or C1(sp) or C4(sp3) or X
Cla attached to C2(sp2)-C4(sp2) or C1(sp) or C4(sp3) or X
R-SH
Number of terminal primary C(sp3)
Yany terminal atom or heteroaromatic
group (i.e., H, X, OH, NH2, etc.)

-0.71840
0.03673
0.03434
0.20447
0.05793
0.32578
0.42818
0.17232
0.12641
0.29909
0.04208

0.06492

 0.03341

330

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

Table 1 (continued )
No.

GC

29

Chemical structure

Comment

Value

]c4

unsubstituted benzene C(sp2)

0.09674

30

]c5

Number of terminal primary C(sp2)

Yany terminal atom or heteroaromatic
group (i.e., H, X, OH, NH2, etc.)

0.48322

31

]c6

Quaternary N

0.26407

32

]c7

Sulfonates (thio-/dithio-) Y O or S

1.10870

33

]c8

Number of Pyrrolidines

 0.19189

34

]c9

Number of donor atoms

for H-bonds (N and O)

 0.06625

35
36
37
38
39
40
41
42
43
44
45
46
47

]c10
]c11
]c12
]c13
]c14
]c15
]c16
]c17
]c18
]c19
]c20
]c21
]c22

4N o

Sum of the hydrogens linked to all of the Os and

Ns in the molecule
CH2RX
CHR2X
CRX3
CHR
R   CX   X
R  C( X)  X or R-C#X or XC X
X   CR..X
Ha attached to C1(sp3) or C0(sp2)
Ha attached to C3(sp3) or C2(sp2) or C3(sp2) or C3(sp)
H attached to alpha-Cb
Ha attached to C0(sp3) with 1X attached to next C
phenol or enol or carboxyl OH
4Sio

0.10956
0.74750
0.67414
-0.59573
0.92095
0.36601
0.26392
 0.02346
 0.08650
 0.04089
 0.06775
1.09741
0.52255

R represents any group linked through carbon; X represents any electronegative atom (O, N, S, P, Se, halogens); Al and Ar represent aliphatic and aromatic groups,
respectively; represents a double bond; # represents a triple bond;represents an aromatic bond as in benzene or delocalized bonds such as the NO bond in a nitro
group;yrepresents aromatic single bonds as the CN bond in pyrrole.
a
b

The superscript represents the formal oxidation number.

An alpha-C may be dened as a C attached through a single bond with C X, C#X, CX.

Table 2
The statistical parameters of the model.
Statistical Parameter
Training set
R2
Average absolute relative deviationa
Standard deviation errorb
Root mean square errorc
Nd

0.880
6.21
0.20
0.20
1336
Test set

R2
Average absolute relative deviation
Standard deviation error
Root mean square error
N

0.854
6.79
0.22
0.22
336
Total

R2
Average absolute relative deviation
Standard deviation error

0.874
6.32
0.21

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

331

Table 2 (continued )
Statistical Parameter
Root mean square error
N
N
P

R2 1 P
N

%AARD

Calci=Estiexpi2

Calci=Estiaverageexpi2

0.21
1672

100
N

N
P
9Calc i=Est iexp i9
exp i

N q
P
Calc  i=Est  iaverageCalc  i=Est  i2
Std N1
i

0P
N

Calci=Estiexpi2

B
RMSE @i 1

11=2
C
A

Table 3
The AARD% of the model for different classes of ILs. In the table the units for T and Z are, respectively K and cP.
No.

Class

AARD%

T range

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

1,3-Dialkyl imidazolium
1-Alkyl imidazolium
Amino acids
Ammonium
Double imidazolium
Guanidinium
Isoquinolinium
Morpholinium
Oxazolidinium
Phosphonium
Piperidinium
Pyridinium
Pyrrolidinium
Pyrroline
Sulfonium
Tetra-alkyl imidazolium
Tri-alkyl imidazolium

5.86
10.06
9.87
8.01
3.58
5.81
6.69
10.85
8.47
16.00
8.56
3.86
7.51
3.62
9.57
0.00
7.45

258.15
293.15
353.15
289.15
298.15
293.15
329.15
298.15
298.15
293.15
298.15
293.15
293.15
298.15
253.15
333.15
293.15

log(Z


















433.15
298.15
353.15
343.15
358.15
333.15
329.15
303.15
303.15
303.15
298.15
353.15
301.15
298.15
353.15
333.15
373.15

0.53
1.56
1.95
0.55
2.09
2.05
2.56
2.28
2.15
1.53
1.92
1.11
1.55
1.62
0.66
2.99
1.47

exp

log(Z

) range
3.99
2.91
3.71
3.92
3.22
3.36
2.56
2.58
2.63
4.28
2.41
2.30
2.41
1.82
2.68
2.99
2.23



















pred

) range

0.46
1.56
2.01
0.54
2.06
2.09
2.75
2.35
1.95
1.54
1.83
1.13
1.57
1.76
0.81
2.99
1.53

N
5.41
2.74
3.19
3.45
3.05
3.07
2.75
3.01
2.86
3.32
3.09
2.38
3.23
1.76
2.71
2.99
2.99



















1381
26
2
86
19
9
1
9
12
19
14
7
21
3
50
1
12

40

30

5
Relative deviation %

20

log(pred)

10
0
10
20

30
40

0
0

3
log(

exp

log(exp)

Fig. 1. Estimated viscosity values from Eq. (1) versus experimental values.(n) and
(o) denote the training set and the test set, respectively. The unit for Z is cP.

Fig. 2. Relative deviation of predicted viscosity values versus experimental ones.(n)

and (o) denote the training set and the test set, respectively. The unit for Z is cP.

model, a training set composed of 1336 experimental data was

correlated with a low AARD% of about 6.3. A test set consists of
336 data point was used to validate this model. It shows an

AARD% of 6.8 for the test set. To recapitulate; the model proposed
here is reliable and can be used to predict the viscosity of various
ionic liquids.

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F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

60

Table A1
GC

Percent of Data in each Range

50

Number

Values

]a6
]a19
]a20
]a21
Anion
[C2SO4]

1
2
1
1

 0.05754
0.05793
0.32578
0.42818

]c1
]c10
]c17
]c18
]c20

1
1
5
2
3

0.04208
0.10956
 0.02346
 0.08650
 0.06775

Cation
[C2mim]

40

30

20

10

0
0

10
15
20
Relative Deviation Range %

25

Fig. 3. A comparison between the model results and their corresponding experimental values: approximately 54% of the viscosities are predicted within 05%,
26% within 510%, 10% within 1015%, 6% within 1520%, 2% within 2025%, and
the remaining 2% within 2531%.

According to the values presented for A, B, C, D, and Z0 in

Table A1, the viscosity of [C2mim][C2SO4] at 338.15 would be
calculated as follows:

3
exp [C2mim][DCA]
rep/pred[C2mim][DCA]
exp [C10mim][NTf2]
rep/pred[C10mim][NTf2]
exp [C1mim][NTf2]
rep/pred[C1mim][NTf2]
exp [C2mim][C2SO4]
rep/pred[C2mim][C2SO4]

2.5

logZ 0:812260:34191-0:11968  338:15

0:00013  338:152

log()

1.5

Supplementary data associated with this article can be found in

the online version at http://dx.doi.org/10.1016/j.ces.2012.06.045.

280

290

300

310 320
T/K

330

340

350

360

Fig. 4. Logarithm of viscosity as function of temperature. The unit for ] is cP.

Appendix
In order to use the model, the cation and the anion of the desired
IL should be decomposed to identify the substructures of the model
as well as the number of occurrences of each one. In this section the
model is applied for [C2mim][C2SO4] as an example.
Nai Zai 1x0:05754 2  0:05793 1  0:32578

i1

1  0:42818 0:81226
Nc
X

1:2968

Appendix A. Supporting information

Na
X

338:152

It should be noted that the experimental value reported is

1.3222.

0.5
270

64753:03094

2665:71676
338:15

Nci Zci 1  0:04208 1  0:10956 5x0:02346

i1

2x0:08650 3x0:06775 0:34191

References
Abbott, A.P., 2004. Application of hole theory to the viscosity of ionic and
molecular liquids. Chem. Phys. Chem. 5, 12421246.
Bini, R., Malvaldi, M., Pitner, W.R., Chiappe, C., 2008. QSPR correlation for
conductivities and viscosities of low-temperature melting ionic liquids.
J. Phys. Org. Chem. 21, 622629.
Freemantle, M., 2010. An Introduction to Ionic Liquids,Royal Society of Chemistry,
Cambridge.

Furth,
R., 1941a. On the theory of the liquid state. Math. Proc. Cambridge Philos.
Soc. 37, 281290.

Furth,
R., 1941b. On the theory of the liquid state. Math. Proc. Cambridge Philos.
Soc. 37, 252275.
Gardas, R.L., Coutinho, J.A.P., 2008. A group contribution method for viscosity
estimation of ionic liquids. Fluid Phase Equilib. 266, 195201.
Gardas, R.L., Coutinho, J.A.P., 2009. Group contribution methods for the prediction
of thermophysical and transport properties of ionic liquids. AIChE J. 55,
12741290.
Gharagheizi, F., 2007. QSPR analysis for intrinsic viscosity of polymer solutions by
means of GA-MLR and RBFNN. Comput. Mater. Sci. 40, 159167.
Gharagheizi, F., 2009a. A new group contribution-based model for estimation of
lower ammability limit of pure compounds. J. Hazard. Mater. 170, 595604.
Gharagheizi, F., 2009b. New neural network group contribution model for
estimation of lower ammability limit temperature of pure compounds. Ind.
Eng. Chem. Res.. 48, 74067416.
Gharagheizi, F., 2009c. Prediction of upper ammability limit percent of pure
compounds from their molecular structures. J. Hazard. Mater. 167, 507510.

F. Gharagheizi et al. / Chemical Engineering Science 80 (2012) 326333

Gharagheizi, F., 2012a. Determination of diffusion coefcient of organic compounds in water using a simple molecular-based method. Ind. Eng. Chem. Res.
51, 27972803.
Gharagheizi, F., 2012b. Determination of normal boiling vaporization enthalpy
using a new molecular-based model. Fluid Phase Equilib. 317, 4351.
Gharagheizi, F., Abbasi, R., 2010. A new neural network group contribution method
for estimation of upper ash point of pure chemicals. Ind. Eng. Chem. Res. 49,
1268512695.
Gharagheizi, F., Abbasi, R., Tirandazi, B., 2010. Prediction of Henrys law constant of
organic compounds in water from a new group-contribution-based model.
Ind. Eng. Chem. Res. 49, 1014910152.
Gharagheizi, F., Alamdari, R.F., Angaji, M.T., 2008. A new neural network-group
contribution method for estimation of ash point temperature of pure
components. Energy Fuels 22, 16281635.
Gharagheizi, F., Eslamimanesh, A., Farjood, F., Mohammadi, A.H., Richon, D., 2011a.
Solubility parameters of nonelectrolyte organic compounds: determination
using quantitative structure-property relationship strategy. Ind. Eng. Chem.
Res. 50, 1138211395.
Gharagheizi, F., Eslamimanesh, A., Ilani-Kashkouli, P., Mohammadi, A.H., Richon,
D., 2012a. QSPR molecular approach for representation/prediction of very
large vapor pressure dataset. Chem. Eng. Sci. 76, 99107.
Gharagheizi, F., Eslamimanesh, A., Ilani-Kashkouli, P., Mohammadi, A.H., Richon, D.,
2012b. QSPR molecular approach for representation/prediction of very large
vapor pressure dataset. Chem. Eng. Sci. 76, 99107.
Gharagheizi, F., Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011b. Determination of parachor of various compounds using an articial neural networkgroup contribution method. Ind. Eng. Chem. Res. 50, 58155823.
Gharagheizi, F., Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011c. QSPR
approach for determination of parachor of non-electrolyte organic compounds. Chem. Eng. Sci. 66, 29592967.
Gharagheizi, F., Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011d. Representation/prediction of solubilities of pure compounds in water using articial
neural network-group contribution method. J. Chem. Eng. Data 56, 720726.
Gharagheizi, F., Eslamimanesh, A., Mohammadi, A.H., Richon, D., 2011e. Use of
articial neural network-group contribution method to determine surface
tension of pure compounds. J. Chem. Eng. Data 56, 25872601.
Gharagheizi, F., Eslamimanesh, A., Tirandazi, B., Mohammadi, A.H., Richon, D.,
2011f. Handling a very large data set for determination of surface tension of
chemical compounds using quantitative structure-property relationship strategy.
Chem. Eng. Sci. 66, 49915023.
Gharagheizi, F., Eslamimanesh, A., Tirandazi, B., Mohammadi, A.H., Richon, D.,
2011g. Handling a very large data set for determination of surface tension of
chemical compounds using quantitative structure-property relationship strategy.
Chem. Eng. Sci. 66, 49915023.
Gharagheizi, F., Gohar, M.R.S., Vayeghan, M.G., 2011h. A quantitative structureproperty relationship for determination of enthalpy of fusion of pure compounds. J. Therm. Anal. Calorim., 16.
Gharagheizi, F., Ilani-Kashkouli, P., Mirkhani, S.A., Farahani, N., Mohammadi, A.H.,
2012c. QSPR molecular approach for estimating Henrys law constants of pure
compounds in water at ambient conditions. Ind. Eng. Chem. Res. 51, 47644767.
Gharagheizi, F., Ilani-Kashkouli, P., Mirkhani, S.A., Mohammadi, A.H., 2012d.
Computation of upper ash point of chemical compounds using a chemical
structure-based model. Ind. Eng. Chem. Res. 51, 51035107.
Gharagheizi, F., Keshavarz, M.H., Sattari, M., 2011i. A simple accurate model for
prediction of ash point temperature of pure compounds. J. Therm. Anal.
Calorim., 18.

333

Gharagheizi, F., Mirkhani, S.A., Tofangchi Mahyari, A.R., 2011j. Prediction of

standard enthalpy of combustion of pure compounds using a very accurate
group-contribution-based method. Energy Fuels 25, 26512654.
Gharagheizi, F., Salehi, G.R., 2011. Prediction of enthalpy of fusion of pure
compounds using an articial neural network-group contribution method.
Thermochim. Acta 521, 3740.
Gharagheizi, F., Sattari, M., 2010. Prediction of triple-point temperature of pure
components using their chemical structures. Ind. Eng. Chem. Res. 49, 929932.
Ghatee, M.H., Zare, M., 2011. Power-law behavior in the viscosity of ionic liquids:
existing a similarity in the power law and a new proposed viscosity equation.
Fluid Phase Equilib. 311, 7682.
Ghatee, M.H., Zare, M., Zolghadr, A.R., Moosavi, F., 2010. Temperature dependence
of viscosity and relation with the surface tension of ionic liquids. Fluid Phase
Equilib. 291, 188194.
Han, C., Yu, G., Wen, L., Zhao, D., Asumana, C., Chen, X., 2011. Data and QSPR study
for viscosity of imidazolium-based ionic liquids. Fluid Phase Equilib. 300,
95104.
Keshavarz, M.H., Gharagheizi, F., Pouretedal, H.R., 2011. Improved reliable
approach to predict melting points of energetic compounds. Fluid Phase
Equilib. 308, 114128.
Matsuda, H., Yamamoto, H., Kurihara, K., Tochigi, K., 2007. Computer-aided reverse
design for ionic liquids by QSPR using descriptors of group contribution type
for ionic conductivities and viscosities. Fluid Phase Equilib. 261, 434443.
Meindersma, G.W., Maase, M., De Haan, A.B., 2000. Ionic Liquids, Ullmanns
Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA.
Mirkhani, S.A., Gharagheizi, F., 2012a. Predictive quantitative structure-property
relationship model for the estimation of ionic liquid viscosity. Ind. Eng. Chem.
Res. 51, 24702477.
Mirkhani, S.A., Gharagheizi, F., 2012b. Predictive quantitative structureproperty
relationship model for the estimation of ionic liquid viscosity. Ind. Eng. Chem.
Res. 51, 24702477.
Mirkhani, S.A., Gharagheizi, F., Ilani-Kashkouli, P., Farahani, N., 2012a. An accurate
model for the prediction of the glass transition temperature of ammonium
based ionic liquids: a QSPR approach. Fluid Phase Equilib. 324, 5063.
Mirkhani, S.A., Gharagheizi, F., Sattari, M., 2012b. A QSPR model for prediction of
diffusion coefcient of non-electrolyte organic compounds in air at ambient
condition. Chemosphere 86, 959966.
Mousavisafavi, S.M., Gharagheizi, F., Mirkhani, S.A., Akbari, J., 2012a. A predictive
quantitative structure-property relationship for glass transition temperature
of 1,3-dialkyl imidazolium ionic liquidsPart 2. The nonlinear approach.
J. Therm. Anal. Calorim., 110.
Mousavisafavi, S.M., Mirkhani, S.A., Gharagheizi, F., Akbari, J., 2012b. A predictive
quantitative structure-property relationship for glass transition temperature
of 1,3-dialkyl imidazolium ionic liquidsPart 1. The linear approach. J. Therm.
Anal. Calorim., 112.
Poling, B.E., Prausnitz, J.M., OConnell, J.P., 2001. The Properties of Gases and
Liquids, fth ed. McGraw-Hill, New York.
Reichardt, C., Welton, T., 2011. Solvents and Solvent Effects in Organic Chemistry,
4th, updated and enlarged ed. ed. Wiley-VCH, Weinheim.
Rogers, R.D., Seddon, K.R., 2003. Chemistry ionic liquidssolvents of the future.
Science 302, 792793.
Rooney, D., Jacquemin, J., Gardas, R., 2009. Thermophysical Properties of Ionic
Liquids 290, 185212.
Seddon, K.R., Stark, A., Torres, M.-J., 2000. Inuence of chloride, water, and organic
solvents on the physical properties of ionic liquids. Pure Appl. Chem. 72,
22752287.