Fluid Phase Equilibria 297 (2010) 107–112

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Fluid Phase Equilibria

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

Mass connectivity index, a new molecular parameter for

the estimation of ionic liquid properties
José O. Valderrama a,b,∗ , Roberto E. Rojas c
a
Univ. of La Serena, Fac. of Engineering, Dept. of Mech. Eng., Casilla 554, La Serena, Chile
b
Center for Technological Information (CIT), Casilla 724, La Serena, Chile
c
Univ. of La Serena, Fac. of Sciences, Dept. of Chemistry, Casilla 554, La Serena, Chile

a r t i c l e i n f o a b s t r a c t

Article history: A new concept named mass connectivity index (MCI) to encode bond contributions and to allow quanti-
Received 26 May 2010 fying the extent of branching in a molecule, especially of ionic liquids, is proposed. The concept is based
Received in revised form 24 June 2010 on the molecular connectivity concept first introduced by Randic in 1975 and modified in different forms
Accepted 25 June 2010
by several authors. The proposed concept is much easier to calculate than any of the connectivity indexes
Available online 3 July 2010
available in the literature. Thus the only data required for determining the MCI are the groups forming the
molecule and the mass of the groups. The groups forming the molecule are defined as commonly done
Keywords:
in group contribution methods. The index is used as a variable in generalized correlations to accurately
Ionic liquids
Connectivity index
estimate the density and the heat capacity of ionic liquids.
Molecular structure © 2010 Elsevier B.V. All rights reserved.
Molecular parameters
General correlations

1. Introduction organic fluids, such as group contributions, and generalized corre-

The estimation of physical and physico-chemical properties of
fluids, and in particular of ionic liquids (ILs), requires the knowledge
of some basic properties not always available. For instance, general-
ized equations to predict the density and the heat capacity of fluids,
among others, require the critical properties, the normal boiling
temperature or the acentric factor, properties not readily available
in many cases [1,2]. Equations of state applications for pure com-
pounds and mixtures also require critical properties, besides other
properties [3,4].
Few years ago Rooney and Seddon [5] stated that because of
the lack of critical properties for ionic liquids, traditional empiri-
cal and semi empirical methods, such as generalized correlations
that make use of these properties could not be used. They also
argued that other techniques for predicting physical properties
such as group contribution methods could not be used because
they failed to account for organic salts. Such a view probably pre-
vented the progress in the area of property estimation of ILs. This
because the statement meant that to estimate those properties a
totally new formalism should be developed, considering the special
characteristics of ILs. However it has been demonstrated in sev-
eral applications that classical methods developed for molecular
∗ Corresponding author at: Univ. of La Serena, Fac. of Engineering, Dept. of Mech.
Eng., Casilla 554, La Serena, Chile. Tel.: +56 51 204205; fax: +56 51 551158.
E-mail address: jvalderr@userena.cl (J.O. Valderrama).
lations can be extended and adapted for estimating some properties
of ILs.
Valderrama and Robles [6] determined critical properties of
ILs using a group contribution method and determined the con-
tributions of new groups that appeared in ionic liquids. In other
communications the authors increased the number of ILs for which
the critical properties were determined, so at present, the crit-
ical properties are available for 294 ionic liquids [7,8]. Gardas
and Coutinho [9–11] have extensively applied group contribu-
tion methods to estimate the density and the heat capacity of ILs.
Jacquemin et al. [12] also presented a group contribution method
to estimate the density of ILs in a wide range of temperature. Ye and
Shreeve [13] proposed a method to estimate the density of ILs based
on group additivity and calculated volume parameters of groups
and fragments for such estimations. Valderrama and Zarricueta
[14], proposed a generalized correlation for estimating the den-
sity of ILs using critical properties and normal boiling temperature
determined by group contributions. Models and correlations for
the heat capacity of ILs have also been proposed for some limited
cases. Strechan et al. [15] correlated the heat capacity of two ILs in
terms of the temperature and the molecular mass of the ILs. Wal-
iszewski et al. [16], used a group contribution method to estimate
the heat capacity of four ILs. Gardas and Coutinho [9], proposed a
group contribution method for heat capacity estimation of ILs based
on experimental liquid heat capacity data collected from the liter-
ature. Also neural networks have been used to estimate properties
of ionic liquids [2,17,18].

0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.06.015
108 J.O. Valderrama, R.E. Rojas / Fluid Phase Equilibria 297 (2010) 107–112
Fig. 1. Dependency of the density and the heat capacity of selected ionic liquids
on temperature. Data are from NIST28 . For density the symbols are: o [bmim][dca],
 [bdmim][PF6], [bmim][PF6] and [emim][bti]. For heat capacity the symbols
are: [emim][BF4], [bmim][ta], [hmim][bti] and 䊉 [emim][bti].
What is common in all these proposals is the use of some sort
of parameters related to the structure of the molecule. This is a
reasonable approach for ILs since the values of the properties are
highly dependent not only on the type of anion and cation forming
the ILs but also on the structure and the branching of the molecule
[19–21]. In this work a molecular parameter that better involves
some characteristics of the molecular structure of the ionic liquid
is proposed as a discriminating parameter for generalized correla-
tions or neural network models. For hydrocarbons, for instance the
acentric factor is a good parameter for correlating several proper-
ties and has been widely employed in many applications [1]. This
is not the case for ILs and acentric factors can be roughly estimated
with the properties available at present, so a new easy-to-calculate
parameter seems to be needed.
2. Property correlations
In the ranges for which density and heat capacity data for ILs
are available, the behavior of these properties with temperature
is relatively simple and well known: the dependency of density
() on temperature is approximately lineal and the heat capacity
(CP ) follows a quadratic dependency (second order polynomial).
Fig. 1 shows data from the literature of these properties for some
selected ILs. Some authors have proposed to generalize the slopes
of these linear or quadratic expressions in terms of some specific
structural parameters or specific properties (group contributions,
critical properties, normal boiling temperature, acentric factor)
[12–14,23].
Several correlations for liquid density of ILs were evaluated by
Valderrama and Zarricueta [14] and a new general linear model was
proposed. In a simple form the model can be written as:
 = ˛o + ˛1 (T − Tb ) (1)
In Eq. (1), the terms ˛0 and ˛1 are evaluated using the critical prop-
erties and the normal boiling temperature, which are determined
by group contributions. Thus, ˛0 and ˛1 are parameters related to
structural properties. If a reference density o at a temperature To
is used, the model can be expressed as:
 = o + ˛1 (T − To ) (2)
In the model by Valderrama and Zarricueta [14] ˛1 is a parameter
related to structural properties, since it is determined using critical
properties and normal boiling temperature, all calculated by group
contribution.
For the heat capacity Gardas and Coutinho [9] developed a group
contribution method in which the classical quadratic temperature
dependency of CP on temperature was used:
CP = A + BT + CT 2 (3)
In this equation, the parameters A, B and C are determined by group
contribution, and the groups are divide into three anion groups, six
cation groups and three neutral groups. Heat capacity data for 19
ILs were used in determining the values of the contributions for
calculating the parameters A, B and C.
If a value for the heat capacity is known at a given reference
temperature (CPo at To ), the above equation can be simplified and
rewritten as:
CP = CPo + B(T − To ) + C(T 2 − To2 ) (4)
In this equation, the parameters B and C are related to structural
properties and determined by group contribution.
These models (linear in T for the density and quadratic in T for
the heat capacity), will be employed to develop generalized corre-
lations with the inclusion of a new molecular parameter based on
the concept of molecular connectivity.
3. Connectivity index
The molecular connectivity concept was first introduced by
Randic [24] and later developed and expanded by Kier and Hall
[25,26]. Randic proposed an algorithm to encode bond contri-
butions to a molecular branching index that is known today as
molecular connectivity. This concept has allows in some way to
at least partially quantify the extent of branching in a molecule, an
aspect of especial importance in group contribution methods, espe-
cially when the method is applied to ILs. The essence of molecular
connectivity is the encoding of the structure in a non-empirical
way. It is not a measured property nor does it derive from or
directly translate into a particular physical property. According to
Hall and Kier [27], this has not been understood by some investi-
gators employing structure–activity models. The authors examined
the Randic algorithm, proposed an alternate structure concept, and
offer an interpretation of the information encoded by molecular
connectivity.
The molecular connectivity index  is calculated by drawing out
a chemical compound in a hydrogen-suppressed molecular struc-
ture and designating a value for each atom. The value of an atom
equals the number of adjacent non-hydrogen atoms. The values of
each atom forming a bond pair designate a bond value, and the bond
values are then summed over all the bonds in the chemical struc-
ture to calculate . In a similar way a valence connectivity index
 J.O. Valderrama, R.E. Rojas / Fluid Phase Equilibria 297 (2010) 107–112 109

Table 1 Table 2
Groups considered in this study for defining the mass connectivity index. Groups connections for [S111] [BF4 ] for the calculation of the MCI.

No Groups without rings Mi –CH3 –S– –B –F

1 –CH3 15.04 –CH3 – 3 – –

2 –CH2 – 14.03 –S– 3 – 1 –
3 >CH– 13.02 –B – 1 – 4
4 >C< 12.01 –F – – 4 –
5 CH2 14.03
6 CH– 13.02
7 C< 12.01 Following the concepts developed by Randic [24], the mass con-
8 –OH 17.01
nectivity index is defined as the sum of the inverse of the mass
9 –O– 16.00
10 >C O 28.01
connectivity interactions, calculated as the square root of the prod-
11 –COO– 44.01 uct of the mass of groups immediately connected in a molecule:
12 –NH2 16.02  
13 –NH– 15.02  1
14 >N– 14.01 =  (7)
15 N– 14.01
mi mj
ij
16 –CN 26.02
17 –NO2 46.01 In this equation, mi and mj are the mass of neighboring groups i and
18 –F 19.00 j in a molecule. In summing up the connections, mi mj is different
19 –Cl 35.45
from mj mi .
20 –Br 79.90
21 –I 126.90 As an example, let’s consider a molecule of the ionic liquid
22 –P 30.97 trimethylsulfonium tetrafluoroborate [S111] [BF4 ]. This ionic liq-
23 –B 10.81 uid has the following global formula C3 H9 SBF4 , so four groups are
24 –S– 32.07 involved. In this case –CH3 is group 1, –S– is group 2, –B is group
25 –SO2 64.07
26 –Al 26.98
3, and –F is group 4. The mass groups are m1 = 15.035, m2 = 32.066,
27 –Sb 121.75 m3 = 10.811 and m4 = 18.998, respectively. The number of connec-
tions between the groups in a molecule of [S111] [BF4 ] are shown
No Groups with rings Mi in Table 2.
28 –CH2 – 14.03 According to the definition given by Eq. (7), the MCI () for
29 CH– 13.02 trimethylsulfonium tetrafluoroborate, is:
30 >C< 12.01  
31 C< 12.01  1 3 3 1 1
32 –OH 17.01 =  = √ +√ +√ +√
33 –NH– 15.02 mi mj m1 m2 m2 m1 m2 m3 m3 m2
ij
34 >N– 14.01
35 N– 14.01 4 4
+√ +√ (8)
m3 m4 m4 m3

v has been defined and used in some applications [24,28]. The
expressions for the molecular connectivity index  and the valence
connectivity index v are:
 
 1
=  (5)
ıi ıj
⎛ ⎞
 1
v = ⎝ ⎠ (6)
ıiv ıvj
Here ıi is the number of non-hydrogen atoms to which the non-
hydrogen atom i is bonded while ıvi incorporates multiple bonding,
heteroatoms and valence states.
These indexes are neither simple nor straightforward to be
determined although the concept behind them is of especial impor-
tance to account for the structure and branching of a molecule in a
quantitative way. What it seem to be a deficiency of these indexes is
that they do not consider de size of the groups forming the molecule
but only their connections with other groups.
A simple mass connectivity index, designated by , which con-
siders both the type of connections between groups and the mass of
such groups is defined in this work. The index is based on the mass
of defined functional groups forming the molecules and is much
simpler to calculate than similar indexes proposed in the literature.
Table 1 shows the groups considered in this method, which are the
same used by the authors in a method to estimate critical prop-
erties and in predicting densities using artificial neural networks
[7,8].
Replacing the values of m1 , m2 , m3 and m4 for the groups forming
the molecule, the value of  for trimethylsulfonium tetrafluorobo-
rate is 0.9389. Values of  for some selected ionic liquids are shown
in Table 3. The supplementary material provides values of  for
476 ILs and an excel file to easily evaluate the connectivity index
for other ionic liquids.
The advantage of the defined mass connectivity index, besides
the simplicity of its calculation, is that not only it encodes the
degree of skeletal branching but also the mass of the groups being
connected. In addition to that, the new mass connectivity index is
simple to calculate and it is directly related to the indexes defined
by Randic  and other indexes such as that modified by Kier and
Hall v . Fig. 2 shows the relation between the mass connectivity
index and other molecular indexes for several organic compounds.
The values of  and v were taken from Li and Li28 , while  was
determined from Eq. (2).
Despite these advantages, the simplicity of the defined MCI
implies certain limitations. Since the calculation of the MCI is simi-
lar to a group contribution method based on the mass of each group
and the way they connect with their neighboring groups, the def-
inition does not reflect other possible factors. Among these, the
electrostatic interaction or hydrogen-bonding effects that may be
of importance to correlate other physical properties which are more
dependent on these complex interactions, that are unique to ionic
liquids. Further analysis on these aspects is needed.
In this work the mass connectivity index  is used as an effective
parameter to discriminate between different ILs so the substance
dependent parameters in the models for determining the temper-
ature dependency of density and heat capacity on temperature are
defined in terms of . Since an experimental reference value of the
110 J.O. Valderrama, R.E. Rojas / Fluid Phase Equilibria 297 (2010) 107–112

Table 3
Values of mass connectivity index  for some selected ionic liquids. A complete table including  for 476 ionic liquids is given as a l.

No Ionic liquid Global formula IUPAC name M 

1 [Ohea] [f] C3 H9 NO3 2-Hidroxyethylammonium formate 107 0.474

2 [mim] [Cl] C4 H7 N2 Cl 1-Methylimidazolium chloride 119 0.963
3 [emim] [Br] C6 H11 N2 Br 1-Ethyl-3-methylimidazolium bromide 191 1.224
4 [dmprim] [Cl] C8 H15 N2 Cl 1,2-Dimethyl-3-propylimidazolium chloride 175 1.558
5 [mbpy] [Br] C10 H16 NBr 1-Butyl-4-methylpyridimiun bromide 230 1.698
6 [deim] [TfO] C8 H13 N2 F3 SO3 1,3-Diethylimidazolium trifluoromethanesulfonate 274 1.972
7 [mhpyr] [dca] C13 H24 N4 n-Methyl-n-hexylpyrrolidinium dicyanamide 236 2.054
8 [tba] [Cl] C16 H36 NCl Tetrabutylammonium chloride 278 2.352
9 [moim] [PF6] C12 H23 N2 PF6 1-Methyl-3-octylimidazolium hexafluorophosphate 340 2.611
10 [N6222] [tos] C19 H35 NSO3 Triethylhexylammonium tosylate 358 3.056
11 [tba] [bti] C18 H36 N2 F6 S2 O4 Tetrabutylammonium bis[(trifluoromethyl)sulfonyl]imide 523 3.477
12 [C16mim] [TfO] C21 H39 N2 F3 SO3 1-Hexadecyl-3-methylimidazolium trifluoromethanesulfonate 457 3.826
12 [top] [Br] C32 H68 PBr Tetraoctylphosphonium bromide 564 4.398
13 [N4444] [doc] C36 H73 NSO7 Tetrabutylammonium docusate 664 5.347
14 [C9(mpy)2] [bti] C25 H34 N4 F12 S4 O8 1,9-Di(methylpyridinium)nonane di-bis[(trifluoromethyl)sulfonyl]imide 875 5.953
15 [C12(benzim)2] [PF6] C32 H44 N4 P2 F12 1,12-Di(3-benzylimidazolium)dodecane bis(hexafluorophosphate) 775 6.99

properties at a reference temperature To are used (o and CPo ), the
influence of molecular structure, represented by the connectivity
index on density and heat capacity is included in the temperature
functionality for each of the properties. For simplicity the depen-
dency on  is considered to be linear for the properties studied:
density and heat capacity. Therefore, the final equations for  and
CP are:
 = o + a(T − To ) (9)
CP = C Po + [c(T − To ) + d(T 2 − To2 )] (10)
The constant “a” for the density and “c” and “d” for the heat capacity
are determined from experimental data taken from the literature.
Once the equation parameters are calculated the constants become
universal parameters to be used for any ionic liquid and the mass
connectivity index  is the parameter that discriminates between
different ionic liquids, providing the temperature dependency of
density and heat capacity.
Fig. 2. Randic connectivity indexes and the mass connectivity index proposed in this
work for selected substances. In the figure:  Randic connectivity  and 䊉 Randic
valence connectivity v .
4. Results and discussion
The parameters in Eqs. (9) and (10) were determined by regres-
sion analysis of available experimental data obtained from the
literature. All data were taken from the NIST Database [22]. For
both the density and the heat capacity part of the data were used
for determining the model parameters and part of the data (around
10%), were used to check the predictive capabilities of the proposed
models. For the density, 479 data points for 106 ILs were used for
determining the parameter “a” in Eq. (9) while 50 values of  were
predicted. For the heat capacity, 461 data points for 31 ILs were
used for determining the parameters “c” and “d” in Eq. (10) while
65 values of CP were predicted. The final general models for the
density and the heat capacity are:
 = o − 3.119 × 10−3 (T − To ) (11)
−4 2
CP = C Po + [0.4579(T − To ) − 3.533 × 10 (T − To2 )] (12)
In these equations o and CPo are the density and the heat capacity
at T0 = 298 K and  is the mass connectivity index (listed in Table 3).
Table 4 summarizes the results, showing the values of the
parameters for each property and some parameters that describe
the accuracy of the proposed models, for both correlation and
prediction. It should be emphasized that the cases considered
for prediction were not used for determining the parameters
of the models. Therefore this type of calculation represents a
good test to check the predictive capabilities of the models. Not
only that but also for some ionic liquids not a single value of
the properties were used for determining the model parameters,
so the calculated temperature dependency is totally predictive
using the mass connectivity index as the parameter that identi-
fies the ionic liquid. Table 5 shows that deviations in predicting
the density for four ILs not included in determining the model
parameters ([tibmp][pTSO3], [bmim][TPES], [bmim][TMEM] and
[C10mim][bti]), are within the limits of the correlation itself.
Similar results are found for heat capacity predictions for other
four ionic liquids ([hdmapy][bti], [bmim][PF6], [emim][SO4] and
[bpy][BF4]).
Tables 6 and 7 present some statistical parameters for the val-
ues calculated by the proposed method and other approaches
reported in the literature. For density there are some general meth-
ods but less information has been published for the heat capacity.
Table 5 shows overall deviations in calculated densities using
the proposed correlation compared with predictions by COSMO-
RS, a model based on quantum chemistry calculations reported
by Palomar et al. [29], with a group contribution method pro-
posed by Jacquemin et al. [12], and with a generalized correlation
previously proposed by the authors [14]. Table 6 shows overall
 J.O. Valderrama, R.E. Rojas / Fluid Phase Equilibria 297 (2010) 107–112 111

Table 4
Results for the density (Eq. (7)) and the heat capacity (Eq. (8)) using the general model including the mass connectivity index.

Density (Eq. (7)) Heat capacity (Eq. (8))

−3
Constants a = −3.119 × 10 c = 0.4579 d = −3.533 × 10−4
Range of temperature (K) 278–358 250–425
Range of property 0.881–1.608 g/cm3 304–1413 J/K mol
Range of connectivity 0.474–6.900 1.509–5.525

Results for data used in correlation

Number of data 479 461
% Av. deviation 0.02 <0.1
% Av. absolute deviation 0.3 0.8
% Max. av. absolute deviation 3.8 5.6

Results for other temperatures and other ionic liquids

Number of data 50 65
% Av. deviation 0.6 −0.2
% Av. absolute deviation 0.7 0.9
% Max. av. absolute deviation 2.6 3.1

Table 5
Density and heat capacity deviations for ionic liquids and temperatures not considered in the calculation of the model parameters.

Cation Anion MCI,  Temp. range (K) % Abs. deviation

Density prediction
[tibmp] [pTSO3] 3.003 298–355 0.8
[bmim] [TPES] 3.381 283–348 1.2
[bmim] [TMEM] 3.229 298–333 0.7
[C10mim] [bti] 3.520 293–298 0.3

Heat capacity prediction

[hdmapy] [bti] 3.419 343–383 2.0
[bmim] [PF6] 2.201 298–323 0.3
[emim] [SO4] 1.694 271–281 0.9
[bpy] [BF4] 2.197 305–329 0.2

Table 6
Overall deviations in calculated densities using the proposed correlation and other methods from the literature.

This work Palomar et al. [29] Jacquemin et al. [12] Valderrama and Zarricueta [14]

Number of data 479 40 961 602

% Av. deviation 0.02 −1.3 −0.8 −0.1
% Av. absolute deviation 0.3 2.1 2.9 2.6
% Max. Av. absolute deviation 3.8 6.3 19.2 12.0

Table 7
Overall deviations in calculated heat capacity using the proposed correlation and other methods from the literature.

This work Waliszewski et al. [16] Ge et al. [30] Gardas and Coutinho [9]

Number of data 541 64 961 2396

% Av. deviation −0.1 – −0.8 0.4
% Av. absolute deviation 0.9 2.5 2.9 2.4
% Max. av. absolute deviation 5.6 12.0 19.3 9.0

deviations in calculated heat capacities using the proposed corre-
lation compared with predictions by group contribution methods
of Waliszewski et al. [16], of Ge et al. [30], and of Gardas and
Coutinho [9].
However, care must be taken when comparing one method to
another. For instance the values of Palomar et al. [29] for the den-
sity were given for only five 1-alkyl-3-methylimidazolium type
ionic liquids. Also, the values reported by Jacquemin et al. [12]
are correlating values only and no predictions were reported. Sim-
ilarly for heat capacity, Waliszewski et al. [16] estimated values
for four ionic liquids using a group contribution method developed
for organic liquids. Ge et al. [30] determined the contributions of
17 groups using literature heat capacity data and correlated values
for 53 ionic liquids. Gardas and Coutinho [9] presented correlated
values only and no predictions were reported. Furthermore, only
imidazolium-, pyridinium-, and pyrrolidinium-based ionic liquids
were considered in the correlations and of the 2396 data points,
1528 values correspond to just one ionic liquid [bmim][PF6]. Addi-
tionally, Cadena and Maginn [31] presented calculated values of
heat capacity for 12 ionic liquids. The value calculated by these
authors for [bmim][NO3] is 248 (J/mol K) while an experimental
values are of the order of 350 (J/mol K), as reported by Strechan et
al. [32].
As seen in the Table 4, average absolute deviations for the den-
sity are 0.3% in correlation and 0.7% in prediction. For the heat
capacity, average absolute deviations are 0.8% in correlation and
0.9% in prediction. Maximum deviations are lower than 4% for the
density and lower than 6% for the heat capacity for both correla-
tion and prediction. Considering the predictive capabilities of the
correlations this deviations are acceptable for engineering calcula-
tions and are below the deviations given by other methods available
in the literature [9–14]. All these results guarantee the robustness
of the proposed models and the appropriateness of the new mass
connectivity index defined in this work.
112 J.O. Valderrama, R.E. Rojas / Fluid Phase Equilibria 297 (2010) 107–112

5. Conclusions logical Research (CONICYT), through the research grant FONDECYT

1070025.
The defined mass connectivity index shows to be a good parame-
ter for generalizing empirical and semi-empirical correlations used Appendix A. Supplementary data
to estimate the density and the heat capacity of ionic liquids at
several temperatures. The mass connectivity index is simple to cal- Supplementary data associated with this article can be found, in
culate and no additional data other than a value of the property at the online version, at doi:10.1016/j.fluid.2010.06.015.
a reference temperature and the mass of the groups forming the
molecules (as described in Table 1), are needed. The method can be References
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