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J. Chem. Thermodynamics 40 (2008) 949956

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Density and refractive index in mixtures of ionic liquids and

organic solvents: Correlations and predictions
Manuel A. Iglesias-Otero, Jacobo Troncoso, Enrique Carballo *, Luis Roman
Departamento de Fsica Aplicada, Universidad de Vigo, Facultad de Ciencias, Campus As Lagoas, 32004 Ourense, Spain

Received 4 December 2007; received in revised form 29 January 2008; accepted 29 January 2008
Available online 5 February 2008

Abstract

Correlations between volumetric properties and refractive index of binary mixtures of room temperature ionic liquids (RTILs) and
organic solvents were examined. To this end, the density and refractive index for a set of these systems were measured at atmospheric
pressure at 298.15 K throughout the composition range. These data were used to calculate excess volumes and refractive index deviations
by using expressions rmly based on the physical signicance of each quantity, fact that allowed the expected relations between the two
quantities to be conrmed. Based on these results, the molar refraction and free or void volume of the mixtures are calculated with a view
to estimating the relative contribution of both quantities to the excess molar volume. Once molar refraction was conrmed to exhibit a
near-ideal behaviour in all mixtures, a method for predicting the density and refractive index of RTIL + organic solvent mixtures was
developed; the results show that this procedure can be a highly useful alternative to the usually complex experimental methods available
for the thermophysical characterization of these systems.
2008 Elsevier Ltd. All rights reserved.

Keywords: LorentzLorenz equation; Molar volume; Molar refraction; Free volume; Ionic liquid

1. Introduction the accurate physicochemical characterization of systems

Room temperature ionic liquids (RTILs) have received
increasing attention in the last decade by virtue of their
ability to successfully replace traditional, organic solvents
in many chemical processes [14]. These compounds pos-
sess unusual properties [5] that may be useful for specic
scientic applications. Thus, RTILs typically have extre-
mely low vapour pressures and most exhibit a broad liquid
range. Also, they are usually chemically stable and non-
corrosive. However, their most salient feature is possibly
that their physicochemical properties can be nely adjusted
via slight structural modications of the cation or anion;
this makes them potentially useful as designer solvents
[6]. Although such appealing properties have been known
for some time and investigated to a substantial extent,
much work remains to be done in order to accomplish
*
Corresponding author. Tel.: +34 988387213; fax: +34 988387227.
E-mail address: gonzalez@uvigo.es (E. Carballo).
containing an RTIL.
Because of its high signicance and experimental acces-
sibility, density has probably been the most widely studied
physical property of RTILs [713]. The earliest attempts at
determining this quantity in RTILs resulted in large dier-
ences between the results obtained by some authors, which
has been ascribed to an unusually strong inuence of impu-
rities on density [14]. Also the most commonly used tech-
nique for determining density, which uses a vibrating-
tube densimeter, is allegedly subject to systematic errors
due to the damping eect arising from the typically high
viscosity of RTILs [15]. By now, impurities in RTILs have
been substantially reduced, their inuence on density at
least partly elucidated and the consequences of the damp-
ing eect avoided by using a variety of techniques most
of which require the knowledge of the sample viscosity
[1618]. However, the most recent and accurate values
for RTILs continue to dier signicantly and to a greater
extent than those reported for usual molecular solvents.

0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.01.023
950 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956
The refractive index of RTILs has received compara-
tively little attention [1922]. Most techniques for deter-
mining refractive indices are very expeditious and highly
accurate; also, they usually employ very small amounts of
sample. Refractive indices are often reported together with
density values for non-electrolytes as proofs of purity of the
samples concerned thanks to the high precision obtained
with these now common, inexpensive techniques [23]. Sur-
prisingly, however, these two quantities have rarely been
studied jointly despite their strong correlation as reected
in the LorentzLorenz equation [24,25]:
 2 
n 1 N Aa
Vm ; 1
n2 2 3e0
where n is the refractive index, Vm the molar volume, NA
Avogadros number, e0 the permittivity of vacuum and a
the mean molecular polarizability. Based on this equation,
the molar refraction, R, can be dened as follows:
 2  from rearrangement at relative positions of the particles
n 1
R V m: 2 forming the mixture [27] (i.e. changes in free volume).
n2 2
Simple calculations reveal that, for a hard-core spheri-
cal model [26], a = 4pe0a3, a being the sphere radius.
Substituting this expression into equation (1) yields R =
NA4pa3/3; therefore, R represents the hard-core molar
volume. Although these equations only hold at the zero
frequency limit, they have proved applicable at optical
frequencies in non-highly conductive, non-magnetic mate-
rials [27]. Also it must be noted that, although this rela-
tion was derived from the hard-core model, it has been
revealed as a quite accurate expression for real liquids
[2527]. The molar refraction and molar volume can be
used to obtain the molar free volume, Vm,f, which repre-
sents the volume not occupied by molecules or ions, sim-
ply as Vm,f = Vm  R. This free volume appears in many
liquid-state models, for instance, in those based on the
famous van der Waals equation-of-state. Therefore, a
joint analysis of density and refractive index can provide
highly useful information about the volumetric behaviour
of a system.
The study of these magnitudes for mixtures presents
some diculties, since their values for an ideal solution
are not as easily dened as those of typical Solution Ther-
modynamics quantities such as the volume, heat capacity,
or enthalpy. This is a result of the refractive index being
by no means an equilibrium property; in fact, it is deter-
mined at frequencies in the region of 1015 Hz, which is very
far from the zero frequency limit (i.e. from the region
where this quantity might possess physical signicance
from the standpoint of equilibrium thermodynamics).
Many denitions of the ideal refractive index and molar
refraction are based on analogies with other quantities and
on wrong, bold surmises [2830]. Such approaches often
lead to useless results that are inconsistent with the values
for other thermodynamic variables such as volume or
enthalpy. Nevertheless, one can use very simple, reasonable
assumptions in order to establish meaningful denitions of
these ideal quantities and obtain results not only consis-
tent with thermodynamic data, but also useful with a view
to interpreting microscopic phenomena related to the mix-
ing process [31].
As regards molar refraction, a single, very reasonable
assumption allows one to obtain an expression for the
ideal value: since R is a volume (the hard-core volume),
one can assume the rule of volume additivity to hold and
hence
Rid xR1 1  xR2 ; 3
where x is the mole fraction of component 1 and subscripts
denote pure-product properties. The deviation from an
ideal mixture, which is equivalent to an excess function
for an equilibrium quantity, is obviously DR = R  Rid.
If R is assumed to be equivalent to a hard-core volume,
then DR should be small relative to the excess volume since
changes in volume upon mixing are known to result mainly
Therefore, one can expect the hard-core volume of the par-
ticles to change very little from the pure liquids to a mix-
ture, and hence the molar refraction of the mixture to be
very similar to Rid. The application of equation (3) to real
mixtures has provided the expected results (i.e. very small
DR values relative to excess volumes)[27,32]; by contrast,
other denitions such as that which establishes Rid by
weighing pure-product molar refractions with volume frac-
tions, can provide DR values that are even higher than
excess volumes [33].
A rigorous denition of the ideal refractive index can
be obtained from those of the ideal volume and ideal
molar refraction, using equation (2), by assuming both
quantities to obey the volume additivity rule in terms of
mole fractions. Based on these assumptions and equation
(3), one obtains
 2 2 1=2
n1 n2 2/n21 21  /n22
nid ; 4
2 /n22 1  /n21
where / xV m;1 =V id
m is the volume fraction and Vm,1 the
molar volume of the rst component. Under the assump-
tion that the dierence between the refractive indices of
the two components is small, equation (4) can be substan-
tially simplied [34] to:
nid /n1 1  /n2 : 5
Obviously, the analogy with excess quantities is, again,
straightforward: the deviation of the refractive index is
dened as Dn = n  nid, nid being given by equations (4)
or (5). This latter denition of nid has frequently been used
and provided good, consistent results [27,31,35]. This is not
the case with other denitions of nid such as that based on
an analogy with the molar volume, nid = xn1+(1  x)n2,
which is also frequently used but has no physical ground
and usually gives meaningless results [2830].
 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956 951

Because the approximation that molar refraction
behaves ideally (equation (3)) has proved highly accurate
with most of the binary systems studied to date in this
respect [27], it can be used to make accurate predictions.
Thus, the density and refractive index of pure compounds,
and the refractive index of their mixture can be used in con-
junction with equation (3) to estimate the density of the
mixture. Obviously, the refractive index of the mixture
can be estimated by using the inverse procedure if the den-
sity and refractive index of the pure components, and the
density of the mixture, are known [33].
The main purpose of this work is to nd to what extent
the previous reasoning applies to systems consisting of an
ionic liquid and an organic solvent. To this end, density
and refractive index measurements were made throughout
the composition range for 10 binary systems at atmospheric
pressure at 298.15 K. The studied RTILs included 1-butyl-
3-methylimidazolium tetrauoroborate ([Bmim][BF4]) and
1-butyl-3-methylimidazolium methylsulfate ([Bmim][-
MeSO4]), and were selected on the grounds that they had
previously exhibited quite dierent behaviour in their solu-
tions with organic solvents [21,3638]. The molecular liq-
uids used were intended to represent various some of the
major families of organic compounds: alcohols, ethers,
nitroalkanes, and chloroalkanes. No non-polar compounds
such as alkanes or aromatic hydrocarbons were studied
owing to their low miscibility with ionic liquids. The results
were analysed under the LorentzLorenz equation with a
view to correlating the target quantities and predicting den-
sity from refractive index values and vice versa.
2. Experimental
the densimeter is assumed to behave as an oscillator with-
out damping. This is true with low-viscosity samples, but
not with high-viscosity ones, where the damping contribu-
tion is signicant and the measured density is higher than
the actual density as a result [15]. Therefore, measurements
for high-viscosity samples with this type of densimeter
necessitate some correction. Almost all available methods
for this purpose require the knowledge of the actual viscos-
ity of the sample and use a simple analytical expression to
correct it [1618]. The main advantage of the DMA5000
densimeter is its ability to apply such a correction automat-
ically without the need for any information about the vis-
cosity of the sample [13,39]. The instrument was
calibrated with ultrapure water and dry air. The tempera-
ture uncertainty was estimated to be 0.01 K. Calibration
was checked by comparing experimental density values for
various high-purity organic compounds with literature
data; consistency between both data sets was quite high
(dierences were in the region of only 1  105 g  cm3).
An uncertainty of 1  104 g  cm3 was assumed in view
of the unusually strong inuence of the water content of
ionic liquids on their density [14], which signicantly
reduces the accuracy of measurements.
Refractive index measurements were made with a Met-
tler Toledo RE 50 refractometer. The measurement princi-
ple is based on Snells law: a light beam at the sodium line
(589.3 nm) is emitted by a photodiode and a sensor is used
to detect the deviation angle [39]. Uncertainty in these mea-
surements was also worsened by the strong eect of water
present in RTILs on their physical properties; therefore,
although it can be as low as 2  105 for some organic sol-
vents, in this work we assumed it to be 2  104.

2.1. Chemicals 3. Results and discussion

The RTILs studied were supplied by Solvent Innovation, 3.1. Excess volumes and refractive index change
both in a certied purity greater than 0.99. They were fur-
ther puried by stirring at a moderate temperature The experimental density and refractive index of the stud-
(333.15 K) in vacuo in order to remove water and other vol- ied RTILs at 298.15 K at atmospheric pressure are shown in
atile impurities, and stored at room temperature under vac- tables 1 to 3. The results were used to calculate excess vol-
uum. The water content of the puried RTILs was estimated umes and refractive index deviations, using the equations:
using the KarlFischer method and it was found to be, in xM 1 1  xM 2 M1 M2
mole fraction, <0.009 for [Bmim][BF4] and <0.016 for V Em V m  V id
m x  1  x ;
q q1 q2
[Bmim][MeSO4]. Ethanol (purity P0.995) was supplied by
Merck; nitromethane (P0.985) by Fluka; and 1,3-dichloro- 6
propane (purity P0.99), diethylene glycol monoethyl ether Dn n  nid ; 7
(DEGEE) (purity P0.99) and ethyleneglycol (purity
P0.998) by Aldrich. Samples were prepared by weighing
TABLE 1
to within 1  105 g on a Mettler AE 240 balance. The uncer- Density and refractive index of pure compounds at 298.15 K
tainty in the mole fraction was estimated to be 1  104.
q/(g  cm3) nD
[Bmim][BF4] 1.20141 1.4219
2.2. Apparatus and procedure
[Bmim][MeSO4] 1.20775 1.4794
Ethanol 0.78518 1.3593
Density was measured with an Anton Paar DMA-5000 Nitromethane 1.13117 1.3796
vibrating-tube densimeter. An appropriate amount of sam- 1,3-Dichloropropane 1.17910 1.4460
ple is used to ll the U-shaped tube and a periodic pertur- DEGEE 0.98368 1.4253
Ethylene glycol 1.11002 1.4304
bation applied by means of an electronic system. Usually,
952 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956

TABLE 2
Experimental densities (q/g  cm3) at 298.15 K for the studied mixtures xIL + (1  x) organic solvent
Ethanol Nitromethane 1,3-Dichloropropane DEGEE Ethylene glycol
x q x q x q x q x q
x[Bmim][BF4]+(1  x) organic solvent
0.0517 0.85045 0.0512 1.14818 0.0536 1.18413 0.0544 1.00336 0.0517 1.12311
0.0918 0.89163 0.0991 1.15864 0.1135 1.18780 0.1016 1.01820 0.1380 1.13878
0.1995 0.97613 0.1392 1.16519 0.1516 1.18978 0.1492 1.03287 0.1928 1.14651
0.2495 1.00741 0.2026 1.17312 0.2101 1.19232 0.1941 1.04510 0.2567 1.15422
0.2518 1.04290 0.2986 1.18143 0.2817 1.19471 0.2686 1.06522 0.3000 1.15872
0.3228 1.08197 0.3565 1.18514 0.3528 1.19653 0.3215 1.07837 0.3324 1.16186
0.4219 1.11711 0.3972 1.18727 0.4042 1.19751 0.3932 1.09493 0.4020 1.16789
0.5356 1.13894 0.4553 1.18989 0.4626 1.19841 0.5108 1.11982 0.4162 1.16898
0.6244 1.15656 0.5231 1.19230 0.5254 1.19914 0.6016 1.13749 0.4997 1.17510
0.7090 1.17774 0.5949 1.19448 0.5466 1.19938 0.6657 1.14916 0.5803 1.18022
0.8295 1.19274 0.6863 1.19669 0.5955 1.19976 0.6998 1.15507 0.6320 1.18329
0.8073 1.19886 0.6786 1.20034 0.8304 1.17650 0.6960 1.18682
0.8634 1.19969 0.7863 1.20089 0.9551 1.19504 0.8045 1.19248
0.9028 1.20120 0.9083 1.19733

x[Bmim][MeSO4]+(1  x) organic solvent

0.0459 0.85062 0.0398 1.14667 0.0429 1.18363 0.0517 1.00336 0.0854 1.11582
0.0987 0.90924 0.1021 1.16166 0.0674 1.18562 0.0891 1.01608 0.1946 1.12361
0.1420 0.94807 0.1433 1.16887 0.1040 1.18824 0.1483 1.03502 0.2999 1.12601
0.1905 0.98434 0.1988 1.17621 0.1376 1.19037 0.2233 1.05710 0.4399 1.13805
0.2357 1.01298 0.2444 1.18095 0.1894 1.19317 0.2901 1.07498 0.6360 1.14398
0.2733 1.03354 0.2998 1.18558 0.2496 1.19576 0.3194 1.08250 0.5061 1.15015
0.3516 1.06963 0.3979 1.19169 0.3166 1.19802 0.3902 1.09982 0.7170 1.15576
0.4381 1.10130 0.4786 1.19547 0.3917 1.20002 0.4732 1.11860 0.3530 1.16456
0.5335 1.12908 0.5652 1.19852 0.4881 1.20198 0.5364 1.13183 0.2446 1.17078
0.5712 1.13845 0.7127 1.20266 0.5686 1.20319 0.6235 1.14855 0.1079 1.17289
0.6742 1.16039 0.8212 1.20474 0.6797 1.20461 0.6960 1.16173 0.8055 1.18208
0.7665 1.17677 0.8546 1.20540 0.7887 1.20573 0.8065 1.17990 0.5299 1.18848
0.8482 1.18891 0.8987 1.20682 0.8947 1.19318 0.0341 1.19509
0.9248 1.19903 0.9070 1.20187

where M denotes molar mass and nid is given by equation only if an appropriate denition of the ideal refractive
(4). We used equation (4) instead of the simpler equation index is used can the experimental results follow this trend.
(5) because the latter was derived under the assumption In fact, it has been shown [27] that, if Dn is calculated
that the dierence n1  n2 is small, which was not true through the approximation given by equation (5), experi-
for some of the studied systems. The data were tted to mental excess volumes are correlated with experimental
the following RedlichKister equation: Dn values; thus, positive values for V Em correspond to neg-
Xn ative Dn values and vice versa.
i
Y x1  x Ai 2x  1 8 Within the framework of the LorentzLorenz approxi-
i1 mation, Dn and V Em can be correlated via the change in
the Ai coecients in which are listed in table 4. reduced free volume, namely:
The experimental V Em and Dn data are shown in gures 1    id
V m;f V m;f V m;f
and 2. As can be seen, there was strong correlation between D  : 9
R R R
both quantities. Thus, negative V Em values corresponded to
positive Dn values; also, the maximum or minimum of both Application of the LorentzLorenz equation allows this
quantities occurred at virtually the same molar fraction expression to be reduced to
(maximum deviation less than 0.1), and, if absolute values  
V m;f 3 3
are considered, high V Em values corresponded to high Dn D 2  : 10
values. As can be easily envisaged, Dn and V Em must be R n  1 nid 2  1
related somehow: if V Em is positive, then there will be more Provided R = Rid, which, as noted earlier, is most often
available free volume than in the ideal solution and pho- a highly accurate approximation, the following expression
tons will be less likely to interact with the molecules or ions can be obtained:
constituting the compound; as a result, light will travel at a  
higher velocity in the medium concerned and its refractive V m;f VE
D m: 11
index will be lower than in an ideal solution. Obviously, R R
 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956 953

TABLE 3
Experimental refractive index values (nD) at 298.15 K for the studied mixtures xIL + (1  x) organic solvent
Ethanol Nitromethane 1,3-Dichloropropane DEGEE Ethylene glycol
x nD x nD x nD x nD x nD
x[Bmim][BF4]+(1  x) organic solvent
0.0517 1.3703 0.0512 1.3889 0.0536 1.4448 0.0544 1.4268 0.0517 1.4287
0.0918 1.3767 0.0991 1.3952 0.1135 1.4430 0.1016 1.4274 0.1380 1.4261
0.1995 1.3898 0.1392 1.3990 0.1516 1.4418 0.1492 1.4277 0.1928 1.4250
0.2495 1.3943 0.2026 1.4038 0.2101 1.4401 0.1941 1.4278 0.2567 1.4240
0.2518 1.3946 0.2986 1.4089 0.2817 1.4381 0.2686 1.4278 0.3000 1.4235
0.3228 1.3998 0.3565 1.4112 0.3528 1.4359 0.3215 1.4277 0.3324 1.4231
0.4219 1.4058 0.3972 1.4125 0.4042 1.4345 0.3932 1.4273 0.4020 1.4226
0.5356 1.4105 0.4553 1.4142 0.4626 1.4330 0.5108 1.4265 0.4162 1.4225
0.6244 1.4137 0.5231 1.4158 0.5254 1.4314 0.6016 1.4257 0.4997 1.4219
0.7090 1.4161 0.5949 1.4172 0.5466 1.4309 0.6657 1.4250 0.5803 1.4216
0.8295 1.4188 0.6863 1.4188 0.5955 1.4296 0.6998 1.4247 0.6320 1.4215
0.8073 1.4202 0.6786 1.4276 0.8304 1.4235 0.6960 1.4215
0.8634 1.4207 0.7863 1.4255 0.9551 1.4223 0.8045 1.4215
0.9028 1.4234 0.9083 1.4217

x[Bmim][MeSO4]+(1  x) organic solvent

0.0459 1.3791 0.0398 1.3953 0.0429 1.4499 0.0517 1.4307 0.0854 1.4373
0.0987 1.3956 0.1021 1.4128 0.0674 1.4518 0.0891 1.4339 0.1946 1.4449
0.1420 1.4067 0.1433 1.4218 0.1040 1.4543 0.1483 1.4388 0.2999 1.4511
0.1905 1.4170 0.1988 1.4316 0.1376 1.4564 0.2233 1.4443 0.4399 1.4582
0.2357 1.4253 0.2444 1.4382 0.1894 1.4596 0.2901 1.4488 0.6360 1.4672
0.2733 1.4314 0.2998 1.4449 0.2496 1.4624 0.3194 1.4507 0.5061 1.4616
0.3516 1.4414 0.3979 1.4541 0.3166 1.4654 0.3902 1.4548 0.7170 1.4703
0.4381 1.4503 0.4786 1.4596 0.3917 1.4677 0.4732 1.4593 0.3530 1.4540
0.5335 1.4581 0.5652 1.4648 0.4881 1.4706 0.5364 1.4626 0.2446 1.4479
0.5712 1.4609 0.7127 1.4714 0.5686 1.4725 0.6235 1.4663 0.1079 1.4390
0.6742 1.4667 0.8212 1.4748 0.6797 1.4747 0.6960 1.4697 0.8055 1.4735
0.7665 1.4715 0.8546 1.4758 0.7887 1.4765 0.8065 1.4735 0.5299 1.4625
0.8482 1.4745 0.8987 1.4784 0.8947 1.4763 0.0341 1.4334
0.9248 1.4772 0.9070 1.4768

Therefore, V Em DV m;f DR: 13

E id
V 3Rn n
m
Dn Dnf R; nid ; n: 12
R 2
n  1nid  1
2 be calculated throughout the composition range. The
It is easy to see that f(R, nid, n) is always positive; there-
fore equation (12) provides the explicit evidence that V Em
and Dn are of opposite sign. Also, it allows V Em to be calcu-
lated from Dn and vice versa if the densities and refractive
indices for the pure products are known. This is consistent
with the correlation found between experimental V Em and
Dn values as the approximation involves the sole assump-
tions that R behaves ideally and the LorentzLorenz equa-
tion holds; also, it conrms that both hypotheses are
accurate for (ionic liquid + molecular liquid) systems.
The usefulness of these approximations for predicting den-
sity and refractive index will be shown at the end of this
section.
3.2. Free volume and molar refraction changes
Equations (3) and (10) can be used to calculate the
molar refraction and free volume changes occurring upon
mixing. These two quantities are related to the excess molar
volume through
Fitting curves provided by equation (8) allowed both to
results are shown in gure 3 together with excess volume
tted values. As can be seen, most excess volume was due
to changes in free volume upon mixing since molar refrac-
tion changes were very small in all cases. This is consistent
with previous results obtained in a number of studies
involving non-electrolyte binary systems [27]. Also, there
is evidence that positive DR is associated to net destruction
of interactions, destruction of the mixture order and inef-
fectual packing upon mixing [40]. V Em is negative for most
studied systems, so mixtures are expected to be well-
packed. However, most of the DR values obtained in this
work were positive; therefore, mixing can be expected to
result in net destruction of interactions and mixture order,
which should reect in positive excess isobaric heat capac-
ities, C Ep;m , and/or excess enthalpies, H Em . Unfortunately, no
such data have been reported for the studied binary sys-
tems. In any case, the above-described diculties in mea-
suring thermodynamic properties of RTILs would result
in scarcely precise thermophysical data, so any predictions
of H Em and C Ep based on the very small values of DR
obtained for these systems would be rather unreliable.
954 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956

TABLE 4
Parameters Ai and standard deviations for equation (8)
Ethanol Nitromethane 1,3-Dichloropropane DEGEE Ethylene glycol
x[Bmim][BF4]+(1  x) organic solvent
V Em
A1/(cm3  mol1) 12.0603 11.2304 9.2100 19.8036 1.5432
A2/(cm3  mol1) 48.2550 28.2497 32.0943 64.5843 20.4184
A3/(cm3  mol1) 104.0755 34.5886 69.0678 122.3853 45.9352
A4/(cm3  mol1) 109.0969 20.7316 73.0184 117.1379 47.6411
A5/(cm3  mol1) 42.6841 4.5122 28.6169 42.7349 18.1204
r 0.012 0.003 0.003 0.018 0.004
Dn
A1 0.0674 0.1115 0.0345 0.0557 0.0087
A2 0.1927 0.2997 0.0581 0.1177 0.0883
A3 0.2240 0.3014 0.0375 0.1129 0.1383
A4 0.0971 0.1087 0.0121 0.0450 0.0648
r 0.00008 0.00005 0.00006 0.00003 0.00018

x[Bmim][MeSO4]+(1  x) organic solvent

V Em
A1/(cm3  mol1) 12.0671 11.8585 6.2480 12.4433 9.9555
A2/(cm3  mol1) 29.3266 33.6983 15.4226 34.2982 2.7646
A3/(cm3  mol1) 30.6232 44.7672 27.7897 49.7253 3.9416
A4/(cm3  mol1) 10.6385 28.7035 29.0426 33.2635 10.8486
A5/(cm3  mol1) 1.2307 6.5268 11.0504 7.9544 5.7313
r 0.006 0.007 0.003 0.011 0.013
Dn
A1 0.1196 0.1055 0.0277 0.0387 0.1098
A2 0.3564 0.2997 0.0287 0.0509 0.1322
A3 0.4186 0.3305 0.0053 0.0038 0.0128
A4 0.1792 0.1349 0.0081 0.0280 0.0253
r 0.00017 0.00010 0.00008 0.00011 0.00007

2
1
Vm
E

0
-1
-2 (a) (b) (c) (d) (e)

7.5
103n

-7.5

0 x 1

FIGURE 1. Excess volumes and refractive index deviations for binary systems consisting of [Bmim][BF4]+ (a) ethanol, (b) nitromethane, (c) 1,3-
dichloropropane, (d) DEGEE, and (e) ethylene glycol.

2
1
V Em

0
-1
-2 (a) (b) (c) (d) (e)

7.5
103n

-7.5

0 x 1

FIGURE 2. Excess volumes and refractive index deviations for binary systems consisting of [Bmim][MeSO4]+ (a) ethanol, (b) nitromethane, (c) 1,3-
dichloropropane, (d) DEGEE, and (e) ethylene glycol.
 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956 955

V Em ; V m, f ; R
-1
(a) (b) (c) (d) (e)
2
-2

-1
(f) (g) (h) (i) (j)
-2
0 x 1

FIGURE 3. Excess volume (-) and deviations of free volume (- -) and molar refraction (3 3) for the studied systems: [Bmim][BF4]+ (a) ethanol, (b)
nitromethane, (c) 1,3-dichloropropane, (d) DEGEE, and (e) ethylene glycol; and [Bmim][MeSO4]+ (f) ethanol, (g) nitromethane, (h) 1,3-dichloropropane,
(i) DEGEE, and (j) ethylene glycol.

3.3. Density and refractive index predictions
If molar refraction is assumed to behave as it does in an
ideal mixture, the following predictive expression for q can
be obtained from equations (2) and (3) within the frame-
work of the LorentzLorenz approximation [24,25]:
 
n2 1
xM 1 1  xM 2
n2 2
q n2 1
 2  : 14
1 M1
1  x
n2 1 M 2
n2 2 q1 n2 2 q2
1 2
Hence, if q and n for the pure products, and n for the
mixture, are known, one can estimate the density of the
mixture. Figure 4 shows the dierence between the experi-
mental and predicted density values. As can be seen, the
dierences were all less than 0.003 g  cm3 and even less
than 0.000 3 g  cm3 for some systems. It must be pointed
out that reported density values from the literature often
exhibit dierences as large as 0.005 g  cm3 and, if no vis-
cosity correction is applied, the resulting density values
depart by up to 0.000 8 g  cm3 from the corrected values.
As stated above, viscosity correction often entails deter-
mining its experimental value, which is labour-intensive
and expensive for systems containing RTILs [11,18]. By
contrast, experimental measurements of the refractive
index are usually very fast and use a very small amount
of sample, which is very important in view on the diculty
of obtaining high-purity RTIL samples. Therefore, the pro-
posed prediction method is an eective choice for the fast,
reliable estimation of density in binary mixtures. Obvi-
ously, determining density with a high precision will
require using a highly precise densimeter with viscosity
correction.
Equation (14) allows one to obtain the inverse predic-
tions (i.e., to calculate n from pure-product density and
refractive index data and from the experimental density
of the mixture). Figure 5 shows the dierences between
the experimental and calculated refractive index values
thus obtained. Again, consistency was quite good for all
studied systems. Thus, dierences were all less than 0.001
and even less than 0.0002 in some cases. These results con-
rm the ability of the proposed method to provide quite
accurate refractive index data for binary systems contain-
ing RTILs.
Finally, we should note that the accuracy of both den-
sity and refractive index predictions increases with increase
in that of the approximation R = Rid (i.e., the smaller is
DR, the better are the results). This also applies to the cor-
relation between V Em and Dn (equation (12)), which relies on
the same approximation. Based on the interpretation of
molar refraction as a hard-core molar volume, the approxi-
mations involved can be assumed accurate, and the above-
described correlations and predictions between n and q
applicable unless dramatic changes causing R to deviate
from its ideal behaviour occur upon mixing.

4
103(exp - pred) / gcm-3

-4 (a) (b) (c) (d) (e)

4

-4 (f) (g) (h) (i) (j)

0 x 1

FIGURE 4. Dierences between experimental and predicted density values for the studied systems: [Bmim][BF4]+ (a) ethanol, (b) nitromethane, (c) 1,3-
dichloropropane, (d) DEGEE, and (e) ethylene glycol; and [Bmim][MeSO4]+ (f) ethanol, (g) nitromethane, (h) 1,3-dichloropropane, (i) DEGEE, and
(j) ethylene glycol.
956 M.A. Iglesias-Otero et al. / J. Chem. Thermodynamics 40 (2008) 949956
1.5
103(nexp -npred)
0
-1.5
1.5
-1.5
0 x
FIGURE 5. Dierences between experimental and predicted refractive index values for the studied systems: [Bmim][BF4]+ (a) ethanol, (b) nitromethane,
(c) 1,3-dichloropropane, (d) diethyleneglycol monoethyl ether, and (e) ethyleneglycol; and [Bmim][MeSO4]+ (f) ethanol, (g) nitromethane, (h) 1,3-
dichloropropane, (i) diethyleneglycol monoethyl ether, and (j) ethyleneglycol.
4. Conclusions
This paper exposes the strong correlation between the
density and refractive index of binary mixtures consisting
of an RTIL and an organic solvent. Based on the results,
assuming molar refraction to behave ideally is an accurate
approximation that enables reliable predictions of density
from refractive index data and vice versa. Unless a very
high precision is required, the proposed method could be
quite useful for predicting density as the procedure
involved for measuring refractive index is much simpler.
Acknowledgements
The authors are grateful to the Consellera de Innova-
cion e Industria, Direccion Xeral de I+D da Xunta de
Galicia (Project PGIDIT-06PXIB3832828-PR) and to the
Ministerio de Educacion y Ciencia, Direccion General de
Investigacion (Projects #BFM2003-09295 and MAT2006-
12984) for nancial support.
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JCT 07-409