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Eect of structural variations in cations of ionic liquids on the
coexistence curve of isobutyric acid and waterw
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Awanish Kumar, P. Madhusudhana Reddy and Pannuru Venkatesu*

Received (in Gainesville, FL, USA) 4th June 2012, Accepted 13th August 2012
DOI: 10.1039/c2nj40462a

Interestingly, various behaviors of ionic liquids (ILs) having dierent cation chains with a
common anion is observed in the coexistence curve of isobutyric acidwater (IBW). The critical
region of IBW was found to increase in the presence of aliphatic chain 1-hexyl-3-methyl-
imidazolium tetrauoroborate [C6mim][BF4], (IL-1) whereas the critical region decreased in the
presence of aromatic chain 1-benzyl-3-methylimidazolium tetrauoroborate [Bnmim][BF4], (IL-2).
Adding 0.52.0 mg ml 1 of IL-1 or IL-2 to IBW caused the critical temperature (Tc) to decrease
by 0.5532.898 K (for IL-1) and to increase by 0.5021.664 K (for IL-2). The critical exponent (b)
increases with increasing the IL concentrations, which are fully renormalized critical exponents.
Further, our dynamic light scattering (DLS) results for the binary critical solution of IBW
indicate that there exists a uctuation in the local density that contributes signicantly to the
uctuations in the scattered intensity at Tc. The variations in uctuations are found to be
pronounced in the presence of IL as an impurity. The reason for this behavior may be the
formation of large water clusters with the neighboring molecules of ILs at Tc. This indicates that
the IL entangles with the both coexisting phases, thereby, the IL strongly interacts with the
neighboring solvent molecules. In addition, we report the uorescence spectroscopy data for the
critical mixture of IBW and its mixture with ILs as impurities using Nile Red as a uorescent
probe. Noticeable transitions of the two phases were detected at Tc through uorescence
technique. The observed variations in the uorescence intensities with temperature predict
unambiguously the formation of the solvation structure at Tc for the pure critical mixture
as well as in presence of ILs.

1. Introduction of chemical reactions occurring in binary liquid critical

The mutual miscibility of coexisting liquid phases of isobutyric
acid + water (IBW) is a very promising technology for novel
separation and extraction processes.1 Phase transitions of the
IBW system have been well characterized by a number of
investigators over the years.2,3 The advantage of studying IBW
mixtures is that they are stable and provide information of
universal quantity as the critical exponent (b), which depicts
the shape of the coexistence curve.4 Further, the coexistence
curve of IBW represents a readily accessible way of studying
the mixing of molecules. For coexisting liquid phases, the
critical temperature (Tc) is known to be very sensitive to
impurities.57 Changes in the consolute or critical point (Tc)
and b can be exploited by the eects of criticality on the rates
Department of Chemistry, University of Delhi, Delhi 110 007, India.
E-mail: venkatesup@hotmail.com, pvenkatesu@chemistry.du.ac.in;
Fax: +91-11-2766 6605; Tel: +91-11-27666646-142
w Electronic supplementary information (ESI) available: Schematic
representation of experimental set up to determine the critical
coexistence curve using density measurements (Scheme IS) and repre-
sentative data (Table IS and IIS). See DOI: 10.1039/c2nj40462a
mixtures.8,9
Ionic liquids (ILs), a class of environmentally friendly
solvents, are used in a wide range of industrial processes and
have a large number of applications. ILs as green solvents
have a negligible vapor pressure; therefore, they are considered
suitable for measuring physicochemical properties of pure
substances and their mixtures.1012 They are entirely composed
of ions that have designable properties.1315 The development
of neoteric solvents, i.e., ILs, for chemical synthesis holds
great promise for green chemistry applications.16 The physi-
cochemical properties of ILs are quite sensitive towards the
structure and nature of their cations and anions. ILs are also
chemically diverse owing to the huge number of possible ion
combinations that can be synthesized in laboratories. The
most popular group of room temperature ILs contains a
1-alkyl-3-methylimidazolium cation and the anions Cl ,
BF4 , and PF6 are particularly appealing in various research
activities. Some ILs are known to be insoluble in water, while
others do not mix with non-polar solvents, and such systems
form liquidliquid compositions. Nevertheless, very few
individual liquidliquid phase behaviors of ILs with water

2266 New J. Chem., 2012, 36, 22662279 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012

have been reported.1719 ILs can be recycled and reused after
accomplishing specic tasks due to their immiscibility with a
range of solvents.20 This approach appears to allow the
controlled production of desired products from reactants
due to the tendency of ILs to suppress conventional solva-
tion and solvolysis phenomena. ILs may be suitable, and
indeed favorable, media for the design of novel liquidliquid
extraction systems.20,21 Recently, there has been consider-
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able interest in the use of room temperature ILs as solvents
for industrial purpose liquidliquid extraction systems.21 An
interesting aspect is that ILs are able to inuence the physico-
chemical properties of mixtures and even a slight variation in
their ions can lead to substantial dierences in their properties.
However, very little is known about the appropriate varia-
tion in critical phenomena of binary mixtures upon varying
either the anions or cations of ILs. In this context, a deep
knowledge of the critical phenomena of liquid mixtures
containing ILs is essentially required within the scientic
community.
The critical phenomena of various IL, notably IL-molecular
solvent systems, have been published by several research
groups over the past few decades. However, the inuence of
ILs on critical binary mixtures is entirely absent from the
scientic literature. The critical behavior of binary mixtures
with added ions is an area of active experimental22,23 and
theoretical24,25 research. Moreover, in the case of critical liquid
mixtures, an impurity which dissolves in both the liquids
generally lowers the upper critical solution temperature
(UCST), while an impurity which is soluble in only one of
the liquids raises the UCST.26,27 In this context, much atten-
tion has been focused on the critical behavior of IBW with
ionic salts28,29 and polymers.3,4
In order to address ILs as designer solvents, an under-
standing of the structure of the IL in coexisting liquid phases
is an interesting area of research from a scientic point of view.
Despite this need, the necessary experimental data for many
properties are scarce and often inconsistent between various
sources. However, by using accurate data and an experimental
set up, predictive physical models can be developed which are
highly useful and, as some would consider, essential if ILs are
to realize their full potential. To the best of our knowledge,
however, the details of the IL-induced phase separation
mechanism of water with IB remain unexplored. Moreover,
the solubility data for ILs in a critical mixture of water and IB
are not reported in the literature. This is because of the limited
individual studies that have been conducted with few ILs with
little variation of anion, alkyl chain length, or additional
substituent groups on the IL.
To acquire a clear understanding of the eect of IL structure
on the coexisting liquid phases, we have simultaneously per-
formed precise measurements of the coexistence curve of the
critical IBW mixture near its consolute point in the presence of
various amounts of ILs using a density technique. Additionally,
we have determined the Tc using uorescence spectroscopy, and
the diusion coecients by dynamic light scattering (DLS)
measurements for the mixture of IBW and IL in IBW near its
consolute point. Based on our experimental results, opposing
behaviors of the ILs; 1-hexyl-3-methyl-imidazolium tetrauoro-
borate [C6mim][BF4] (IL-1) and 1-benzyl-3-methylimidazolium
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tetrauoroborate [Bnmim][BF4] (IL-2), were observed in the
critical mixture of IBW. We have detected a dierence in the
Tc when the IL was addedthe shift of Tc decreases in the case
of IL-1 and is increased for IL-2, and is dependent on the
nature of the IL added to the critical mixture.
2. Experimental
2.1 Materials
1-Hexyl-3-methyl-imidazolium tetrauoroborate (r1.0% water
content) and 1-benzyl-3-methyl-imidazolium tetrauoroborate
(r0.2% water content) were purchased from Sigma Aldrich,
USA and were used as obtained. Ultra pure water at 18.3 O cm
resistivity (from Ultra 370 Series) was used for sample pre-
paration. Clear solutions were prepared gravimetrically using
a Mettler Toledo balance with a precision of  0.0001 g.
Special precautions were taken in order to avoid the evapora-
tion of IB or water during the weighing process.
2.2 Density measurements for the coexisting liquid phases of
IBW and IL in IBW
The solubility of the ILs was checked separately with water and
IB. For each of the concentrations of the ILs (0.52.0 mg ml 1)
water was found to be good solvent for both; however, IL-2
was found to be insoluble in IB i.e. a poor solvent for IL-2. As
the cation size on the imidazolium ring increases, the IL (IL-2)
tends to become immiscible with IB. A series of critical
samples of the binary IBW mixture with various IL concen-
trations (C = 0.5, 1.0, 1.5 and 2.0 mg ml 1) were prepared.
The IL was then dissolved with continuous stirring of the
mixture overnight.
For a sample of pure IBW, we prepared from 2.5080 g of
water and 1.5505 g of IB with a UCST of 26.924 1C using an
equal volume criterion, which is in good agreement with the
literature values reported in earlier published articles.1,3,4
The cell containing the solution mixture was immersed in the
isolated water bath where it could be seen through a window
of the water bath. The temperature of the water bath was
controlled up to a third decimal place (for instance 25.003 1C
with an accuracy of  0.002) using a Eurotherm temperature
controller (Eurotherm 3500 Series) attached with a RTD
probe.
Density (r) measurements have been accomplished with a
modied densitometer (Anton Paar, Austria) and the r of
each phase was measured using the procedure as elucidated
elsewhere.4,28,30 A schematic representation of the complete
experimental setup is represented in Scheme IS.w Prior to use,
precautions were taken during sample transfer into the sample
cell to avoid air bubbles. The detailed setup includes a sample
cell on a submersible magnetic stirrer clamped with a
sample holder. The tubing in a sample cell was connected to
a many-way chromatic valve, which was also connected to the
vibrating tube of a densitometer. The sample holder and the
entire experimental setup were placed in a water bath, made of
2 cm thick transparent plexiglass. The temperature of the
water bath was controlled and monitored with an accuracy
of  0.002 1C using a high precession RTD probe thermo-
meter connected to a EUROTHERM temperature controller
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Scheme 1 Schematic representation of the uorescence intensity decrease with change in temperature. The blue, violet and pink colored spheres
represents water, IB, and Nile red molecules.
(3500 series) which was further controlled by a computer
(Scheme ISw). A stirrer was provided to maintain the tem-
perature homogeneity throughout the water bath. The r of
each phase was measured without disturbing the equilibrium
with a modied Anton Parr densitometer having an accuracy
of  0.00005 g cm 3. After each measurement, the densito-
meter was cleaned with water and then with acetone to remove
any contamination. Visual detection of the solution was
employed to determine r data on the temperature-composition
phase diagram corresponding to coexisting equilibrium at
atmospheric pressure. For each measurement, we have
checked carefully that the Tc value of the sample, which gives
the solution, is in the coexisting liquid phase.
In order to quantify the experimental results, in the vicinity
of the critical point, we obtained b from the r measurements of
two coexisting phases with the relative distance from the Tc,
dened by the relation (r1 r2) p (Tc T)b, with r1 and r2
being the individual r values for each coexisting phase. The
detailed analysis for obtaining the b values from experimental
densities of both coexisting phases is depicted in our previous
papers.4 Complete determination of the coexistence curve
is a time-consuming process, and establishing a precise
equilibrium transition temperature can take hours for each
data point.
2.3 Fluorescence measurements for coexisting liquid phases of
IBW and IL in IBW
For uorescent measurements, the choice of the uorescent
probe was caried out with care. Nile Red was chosen as
the uorescent probe since it is soluble in organic solvents.31
Nile Red was dissolved in the bulk solution of IB (10 ml) so
that its absorbance was less than 0.1, and then this solution
was again used for preparing the critical mixture of IBW.
It was possible to measure the uorescence spectra only for
the two samples (IBW and 2.0 mg ml 1 of IL in IBW) with
high accuracy. The lower concentrations of IL were not
considered because of the restriction imposed by the high
viscosity of the IL throughout weighing. Steady-state uores-
cence measurements were conducted with a Cary Eclipse
spectrouorimeter (Varian optical spectroscopy instruments,
2268 New J. Chem., 2012, 36, 22662279 This journal is
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Mulgrave, Victoria, Australia) equipped with thermostated
cell holders, and the temperature was kept constant by
a circulating water bath using a peltier device (accuracy of
 0.01 1C) attached to the sample holder of the uorimeter.
The excitation wavelength was set at 555 nm in order to
calculate the contribution of Nile Red to the overall uores-
cence emission. The experiments were performed in the range
of 2132 1C by using a 1 cm sealed cell and both the excitation
and emission slit widths were set at 5 nm and corrected for
background signal.
The temperature of the uorescence cuvette chamber was
rst raised above the critical temperature to 32 1C, at which a
homogeneous mixture of IBW was formed. The steady-state
scan was taken for the mixture at that temperature. Then the
temperature was lowered by 0.5 1C and the scan was taken
after a time interval of 1 h. Since, in the IBW system, the
diusion of the components was very slow, we allowed a
signicant time interval to achieve complete equilibrium of
the molecules for each of the components in each phase. A
similar procedure was applied to the rest of the samples
containing IL. The schematic representation of the uores-
cence measurements is provided in Scheme 1.
2.4 Dynamic light scattering measurements for coexisting
liquid phases of IBW and IL in IBW
To gain more information about the phenomenal changes of
IL in IBW, we have performed the dynamic light scattering
(DLS) measurements for the same concentration which were
used in the uorescence measurements. The light scattering
measurements were performed on a MALVERN Zetasizer
Nano instrument. The instrument is equipped with a 4 mW
He-Ne laser (633 nm) and tted with an automatic laser
attenuator with a transmission of 100 to 0.0003%. The time-
averaged intensities were measured at a scattering angle of 901.
An advanced avalanche photodiode, Q.E. 4 50% at 633 nm
was used as a detector. The instrument has an in-built auto-
mated correlator for the detection of the scattered intensity
and the necessary auto correlation function calculations were
performed by the instrument using advanced system utilities
and additional analysis algorithms.
c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012

In a DLS experiment, the mutual diusion coecient is
determined from an analysis of the time scale for the decay
of uctuations in the intensity of light scattered by a solu-
tion. The temporal dependence of the scattered intensity is
described quantitatively by the intensity autocorrelation
function. The temperature accuracy of the instrument was
 0.1 1C. The temperature was lowered stepwise from 29 to
22 1C in steps of approximately 0.2 1C and at every level kept
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constant until thermal equilibrium was attained. The measure-
ments for each temperature were performed and recorded
repeatedly for 50 runs to improve the signal-to-noise ratio of
the experiment.
Moreover, for the analysis of the diusion coecient, the
intensity correlation function must be analyzed. The standard
procedure for this is the application of the cumulant method.
By tting a polynomial of third degree to the logarithm of the
intensity correlation function, the decay rate G is obtained
(cumulant). The decay rate is directly related to the diusion
coecient D:
G = q2D
Where q is the wave vector, which is dependent on the
scattering angle. The quality of the result, however, depends
signicantly on the quality of the data and the constraint
settings of the tting procedure. The analysis is actually the t
of a polynomial to the log of the G1 correlation function.
ln[G1] = a + bt + ct2 + dt3 + et4+. . .. . .
The value of b is known as the second order cumulant, or the
z-average diusion coecient.
The Zetasizer software uses algorithms to extract the decay
rates for a number of size classes to produce a size distribution.
3. Results
3.1 Critical behavior of IBW by density measurements
At room temperature, IBW forms a two phase system with
water as the lower and IB as the upper phase.1,3,4 The
coexistence curve of IBW was determined by equilibrating
the binary mixture at a given temperature, followed by the r
measurements of the upper and the lower phases of the
mixture, simultaneously. Upon slowly heating this system of
IB and water, a coexisting phase with an upper critical
consolute point at 26.924  0.002 1C is obtained.1 Cooling
of the one-phase mixture results again in phase separation.
The experimental r values of the pure IBW mixture were
reproducible and are summarized in Fig. 1 as a function
of temperature and provided in Table IS.w On the other
hand, the behavior of the critical mixture in the vicinity
of the critical point was characterized by a set of critical
exponents. We found a b value of 0.326  0.002, for the pure
IBW system which is consistent with the 3D Ising value
of 0.325.
3.2 IL-1 eect on the critical properties of IBW
It is interesting to probe the changes in the Tc due to the
addition of IL-1 in IBW. This assumption can be measured by
observing the equal volume of phase separated coexisting
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phases. The Tc of IL-1 at four dierent concentrations
(0.5, 1.0, 1.5 and 2.0 mg ml 1) in IBW were experimentally
located at 26.371  0.002, 26.192  0.002, 24.309  0.002,
and 24.026  0.002 1C, respectively. The r values of both
coexisting liquid phases of IL-1 in IBW were also displayed in
Fig. 1(a) and included in Table IS.w Looking at the data
in Fig. 1(a), it is observed that as the concentration of IL-1
increases in IBW, the Tc decrease rapidly which indicates that
the ion of the IL-1 favors the mixing of the solvent molecules.
In other words, in the renormalization group theory, the
observed b value for the IBW  IL-1 mixture was plotted
from the dierence in r values (Dr) against temperature (DT)
(Fig. 2a). There is an increase in b from 0.326 for pure (IBW)
to 0.371, 0.409, 0.413, and 0.426 for corresponding IL-1
concentrations of 0.5, 1.0, 1.5 and 2.0 mg ml 1 in IBW,
respectively. Fig. 3(a) depicts the variation in the b values
for IL-1 in IBW.
3.3 IL-2 eect on the critical properties of IBW
(1) The Tc of IL-2 at four dierent concentrations (0.5, 1.0, 1.5
and 2.0 mg ml 1) in IBW were experimentally situated at
27.424  0.002, 27.549  0.002, 28.458  0.002 and 28.591 
0.002 1C, respectively. The temperature dependence of the r
values (i.e., coexistence curves) of the coexisting phases of IL-2
in IBW was reproducible and is summarized in Fig. 1(b) and
also listed in Table IIS.w On close examination of Fig. 1(b), it
(2) is surprising and interesting to note that as the concentration
of IL-2 increases in IBW, not only the shape of the coexistence
curve, but also the Tc values increase simultaneously. This
behavior is quite opposite to IL-1 behavior in IBW. The values
in Fig. 3(b) reveal that an increase in b is observed from 0.327
for pure (IBW) to 0.357, 0.385, 0.468, and 0.469 for IL-2
concentrations of 0.5, 1.0, 1.5, and 2.0 mg ml 1, respectively,
as calculated from Fig. 2(b).
The increase in the b value upon addition of an IL impurity
is quite consistent with the existing literature in which any
another impurity increases the b value of the coexisting liquid
phases.35,24,3234 On the basis of our experimental studies, we
noticed that b is closely related to the behavior of the critical
point and the third component such as an IL modies the
critical exponents of the binary critical mixture. Clearly, b
follows the same trend in the presence of IL-1 and IL-2
(Fig. 3). The increase in the b value with IL concentration
points towards an interaction between the IL and the solvent
molecules.
3.4 Phase transition of IBW and ILs in IBW monitored by
uorescence spectroscopy
The Tc value for IBW was also obtained from uorescence
measurements. Obviously, the uorescence results are in good
agreement with the r measurements. Nile Red is poorly
soluble in water; therefore, an insignicant overall solvation
capacity of pure water exists for Nile Red in aqueous media.35
On the other hand, the probe exhibits high solubility in pure
IB and in IBW mixtures at high temperatures where a single
homogeneous phase is obtained. Therefore, we slowly
decreased the temperature of IBW towards its UCST value
from a higher temperature, so that the changes in the probe
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Fig. 1 Coexistence curves of the temperature dependence of the density measurements of IBW (K) with dierent concentrations of (a) IL-1 or
(b) IL-2 (0.5 ( ), 1.0 ( ), 1.5 ( ) and 2.0 ( ) mg ml 1). The inset represents an enlargement of the data close to the critical point.

Fig. 2 Logarithmic representation of the density dierence (Dr) between the coexisting phases with respect to the distance from the critical
temperature (DT) for () 0.0, ( ) 0.5, ( ) 1.0, ( ) 1.5 and ( ) 2.0 mg ml 1 of IL-1 (a) and IL-2 (b) in IBW. The experimental data were analyzed
with a properly weighted linear least-squares t to the simple scaling relationship Dr = BDTb, where B is the critical amplitude. The error in Dr
was taken as  0.00056, and the error in Dr was  0.0028 1C. For the sake of simplicity and clarity, we did not show the ts and error bars for ILs
in the IBW system.

emission intensities could be monitored with a decrease in
temperature.
Fig. 4(a) represents the inuence on the emission spectra of
Nile Red in various solutions of dierent water concentration
at constant temperature (32 1C) in IB. Clearly, the inuence of
water on the solvation properties of the probe in IB was
observed. In all cases, a blue shift was observed while increasing
composition or water concentration at constant temperature,
which is represented in Fig. 4(a). Obviously, from Fig. 4(b), we
observed the dependence of the wavelength shift (i.e. solvato-
chromism) in uorescence spectra on the change in com-
position of the mixture. Moreover, at a constant critical
composition of IBW, no wavelength shift in the uorescence
spectra of the probe was observed with variations in tempera-
ture (Fig. 5). Additionally, it can be seen from Fig. 5 that the
uorescence maximum (lmax) for Nile Red remained constant
(642.5 nm) throughout the experiment. From Figs. 4 and 5, we
can conclude that the formation of the solvation structure
around the probe molecule is drastically changed with varia-
tions in the composition of each component in the critical
mixture as well as with variations in the temperature itself.
It is well known that the intensity, position, and shape of the
spectral bands of dissolved chromophores are inuenced by
the change in solvents, due to the dierent stabilization of their
electronic ground and exited states. However, in a mixed
solvent, the solvatochromic indicator interacts to a dierent
extent with the solvents of the mixture and hence the composi-
tion of the solvation sphere is dierent from the composition
of the bulk solvent. With increasing solvent polarity, the
emission band undergoes a red shift, the eect being more
prominent for the uorescence of Nile Red. The observations
in the increase of the wavelength with addition of water in IB

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Fig. 3 Inuence of IL-1 (a) and IL-2 (b) on b as a function of IL concentration in IBW. Error bars indicate the standard deviation.

Fig. 4 (a) Emission spectra of Nile Red in various solutions of dierent water concentration (0, 0.0718, 0.1023, 0.4020, 0.7018, 1.002, 1.3025,
1.6022, 1.9019, 2.2018, and 2.5076 g) at constant temperature (32 1C) in 1.5505 g of IB (moving from top to bottom) and (b) variations in
wavelength with increasing water concentration (as provided in Fig. 4. (a)) in IB.

Fig. 5 Fluorescence emission spectra of Nile Red in IBW with
variation in temperature from 3226 1C.
suggest that the solubility of the Nile red molecule in the presence
of water molecules signicantly modies their electronic energies
by interacting with specic sites of the probe. The amino and
carbonyl groups of the solvatochromic dye should also speci-
cally interact strongly with water, and due to the change in
polarity, we observe a solvatochromism eect/shift with the
gradual addition of water in the homogeneous region.
The Tc of the critical mixture of IBW was obtained from the
changes in the Nile Red intensities with changes in tempera-
ture. Therefore, to see the intensity variations of the probe in
IBW, we slightly increased the photomultiplier tube (PMT)
voltage of the uorimeter. Simultaneously, we found that, as
Tc is approached, the intensity of the uorescent probe is
decreased. Fig. 6(a) collects the variations in the intensity of
the probe in IBW at various temperatures. This seems to be the
diminishing eect of the water interactions around the Nile
Red molecule at Tc. There may be very complicated inter-
actions between the critical mixtures in this region and the
chemical physics is unclear.32 At this moment the plausible
explanation based on the experimental results is that the
hydrogen-bond between water and the probe becomes weaker

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Fig. 6 Intensity vs temperature graph for (a) IBW, (b) 2 mg ml 1 of IL-1 in IBW, and (c) 2 mg ml
starting point of the decrease in intensity was taken to be the Tc value for both the mixtures.
as Tc is approached, and that this eect would also reduce the
water concentration around the probe molecule. According to
Gutkowski et al.,35 these dierences in the solvation shell are
promoted by short range interactions between moieties
with dierent electron densities in the probe molecules, and
mixtures of solvent molecules with dierent polarities. Since
the intensity of a uoroprobe depends on its amount; there-
fore, at Tc we can assume that the phase separation has started
and the uoroprobe is separating from the aqueous-rich phase
along with the IB molecules. The intensity decrease is sharp
because of the movement of the molecules of IB and water.
This indicates that the mixing of IB and water is completely
thermally controlled and interactions of any type occurring
between the neighboring IB and water molecules are minimal.
We noticed from uorescence analysis that at temperatures
below Tc, the intensity is at a constant value for the IBW
mixture which suggests that the separation of two phases has
been achieved completely.
For IBW, we observed the Tc to be at 27 1C, which
correlates very well with the r measurements. The uorescence
intensity measurement results obtained for IBW  2.0 mg cm 3
ILs are collected in Fig. 6(b and c), and are also very interesting
and coincide well with the observed Tc value by r measure-
ments. However, the Tc for ILs in IBW as measured by
intensity measurements, are located at 24.0 and 29.5 1C for
IBW  2 mg ml 1 IL-1 and IBW  2 mg ml 1 IL-2,
respectively. The results clearly indicate that ILs strongly
inuence the Tc of the IBW critical mixture.
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1
of IL-2 in IBW mixtures, respectively. The
Moreover, on comparing Fig. 6(ac), we observed that the
emission intensities of the probe increase sharply in the
presence of ILs. This enhancement is observed only when
the local environment around the probe is changed; probably
due to the solvation eects in the critical mixture while
approaching the Tc.35 From the experimental results, it is
obvious that the solvophobic interactions in the neighboring
solvent molecules in the presence of ILs as impurities are
stronger than those in the absence of ILs. Thus, the formation
of a new solvation surface disturbs the environment of the
probe in IBW, thereby enhancing the emission intensities.
3.5 Phase transition of IBW and ILs in IBW monitored by DLS
To address the inuence of ILs on IBW in detail, we examined
IL induced phase transition under various temperatures moni-
tored by DLS experiments. The DLS measurements allow us
to predict the existence of the exponential decay function
in DLS in a near-critical uid mixture.3638 The uid under
investigation is in a state of thermal equilibrium and the infor-
mation on the thermo-physical properties is obtained by investi-
gating the relaxation behavior of macroscopic uctuations.39 For
a binary solution, uctuations in both the local concentration
and the local r contribute to the uctuations in the scattered
intensity.40 In this work, we focus our attention on the
statistical uctuations of the light scattered by a critical liquid
mixture of IBW while approaching its phase transition
temperature (i.e. Tc). The auto correlation function technique
c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012
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Fig. 7 Scattering vs. size distribution graph for (a) IBW (red), (b) 2 mg ml
their respective Tc values.
was employed in the analysis of photon-count data to obtain
the scattering intensity and thermal diusivity of the critical
mixtures. Tc was dened at the maximum scattering intensity
and those at the minimum diusion coecient for the critical
mixture.
The DLS signals for a scattering angle of 901 were analyzed
from 28 to 23 1C for the pure IBW critical mixture. We
observed a large increase in the scattered intensity in the
sample while approaching the Tc. For the sake of clarity and
presentation, variations in the scattering intensity with dia-
meter (size) of IBW or IL in IBW at Tc are represented in
Fig. 7. From Fig. 7, it can be seen that there is a formation of
large clusters of molecules at Tc. The size of IBW increases
upon addition of IL-1 or IL-2. It is clear from Fig. 7 that once
again the dierent roles of the two ILs are emphasized by the
variation of size with the addition of IL. Additionally, Fig. 8
exemplarily depicts the resulting normalized correlation func-
tions at dierent temperatures for the critical mixture of IBW
and IL in IBW. The diusion coecient was calculated from
the best t of Fig. 8 to an exponential decay of the time
correlation function. Fig. 9 illustrates the temperature depen-
dency of the diusion coecients of IBW and IL in IBW. The
Tc was observed where the minimum diusion coecient, D,
was obtained from the diusion-temperature plot of Fig. 9.
The results in Fig. 9 show a diusion coecient of 14.4 m2 s 1
at 28 1C for IBW which gradually decreases to a lower value of
4.42 m2 s 1 at 26.4 1C. Upon moving to a lower temperature,
the value of the diusion coecient again starts increasing
from 26.2 1C towards higher values. The temperature at which
the diusion coecient decreases to the minimum value is
referred to as Tc, which correlates well with the observed Tc
values of 26.924 and 27.0 1C by r and uorescence measure-
ments for the critical mixture of IBW, respectively. In addi-
tion, the variations in the diusion coecient in the presence
of ILs correlate well with the observed experimental values of
r and uorescence measurements. From Fig. 9, we have
This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012
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1 1
of IL-1in IBW (green) and (c) 2 mg ml of IL-2 in IBW (blue), at
minimum diusion coecients of 2.3 m2 s 1 for IL-1 in IBW,
and 2.4 m2 s 1 for IL-2 in IBW at 28.2 1C.
The DLS analysis also supports our ndings that the
presence of an aliphatic IL decreases the Tc while the presence
of an aromatic IL increases the Tc for the IBW. A comparison
between dierences in the Tc values for 2 mg ml 1 of IL
containing IBW critical mixtures is provided in Fig. 10. Our
experimental results for IBW are in good agreement with the
existing literature values, of which, Shresth et al.41 reported a
Tc of 26.250 1C; Greer1 reported a Tc of 26.445 1C; Xia and
Maher42 reported a Tc of 26.40 1C; Seki et al.43 reported a Tc of
27.05 1C; Beysens and Bourgou44 reported a Tc of 26.793 1C;
Morrison and Knobler 45 reported a Tc of 26.963 1C; Bouanz
and Beysens46 reported a Tc of 26.948 1C; and Bouanz23
reported a Tc of 27.140 1C.
3.6 Comparison between eect of IL-1 and IL-2 on IBW
It is very interesting to note that upon comparison, the ILs
show exactly opposite eects on the UCST curve of IBW.
Fig. 11 combines the eect of both the ILs on the UCST of
IBW. We observe a non-linear behavior of the Tc of IBW with
the addition of various concentrations of both the ILs. More-
over, IL-1 decreases the Tc, whereas IL-2 increases the Tc of
the critical mixture of IBW. This discrepancy is mainly due to
the imidazolium cations of IL-1 and IL-2 being constituted of
aliphatic and aromatic chains, respectively. Therefore, the
anomaly in the behavior of both the ILs on the Tc is because
of their structural dissimilarity and the nature of the cations of
IL. As a result, the inuence of an IL on the critical region of
IBW mainly depends on the coordination of its ions.
Considering the case of IL-1, we observed an increase in the
r of the IB-rich phase upon addition of IL, as compared to the
water-rich phase (see Fig. 1(a)). The results indicate that
the solubility of the IL favours the organic phase more than
the water phase. Moreover, there is a large gap in Tc values on
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1 1
Fig. 8 Auto-correlation function (ACF) analysis for the critical mixture of (a) IBW, (b) 2 mg ml of IL-1 in IBW and (c) 2 mg ml of
IL-2 in IBW.

Fig. 9 Diusion coecient vs temperature graph for the critical mixture

of () IBW, ( ) 2 mg ml 1 of IL-1 in IBW and ( ) 2 mg ml 1 of IL-2 Fig. 10 Size vs temperature graph for the critical mixture of () IBW,
in IBW. ( ) 2 mg ml 1 of IL-1 in IBW and ( ) 2 mg ml 1 of IL-2 in IBW.

moving towards a higher concentration of IL (1.5 and alkyl chain means less polarity and more hydrophobicity, the
2.0 mg ml 1) which can be attributed to the fact that the solubility of the IL is thus reduced in water. Therefore, the
interaction of IL with the organic phase increases signicantly interaction of the cation chain is assumed to be more favour-
at higher concentrations of IL. In view of the fact that a longer able for the IB rich phase and the interaction of the anion part

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Fig. 11 Eect of IL-1 (a) and IL-2 (b) on Tc, as a function of IL concentration in IBW.
with the water rich phase, respectively. The weak co-ordinating
ability of the [BF4 ] anion decreases the hydrophobicity of the IL
and, preferentially, the anion part adsorbs the water molecules.
The interaction of IL-1 with the IBW critical mixture is schema-
tically represented in Scheme 2.
On the other hand, the results displayed in Fig. 1(b) indicate
that the solubility of IL-2 favors the water phase more than the
IB phase. Moreover, we observed the solubility of IL-2 in
water only, and found it to be insoluble in IB. The dierence,
as well as the increase, in the Tc values was observed upon
moving towards a higher concentration of IL-2 (1.5 and
2.0 mg ml 1) which can be attributed to the fact that the
interaction of the IL with the water phase increases signicantly
at higher concentrations of IL-2. As a result, the aromatic ring of
the IL tends to be more soluble in polar compounds (i.e. water
(m = 1.82)) than non-polar compounds (i.e. IB (m = 1.08)).
Scheme 2 Schematic representation of the interaction of the IL-1
with IB rich and water rich phase.
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Moreover, in the case of the uorescence measurements;
for IL-1 and IL-2, there is a decrease in the intensity below
the Tc values, while the intensity hardly varies above the Tc
values (Fig. 6(b) and (c)). However, in both the cases, the
intensity does not reach zero as observed in the case of the
pure IBW mixture. This indicates that both the ILs inter-
acted with the Nile Red probe. At this stage we dont have a
suitable explanation for the above phenomenon, which is
being extensively studied in our lab. We may expect that this
might be due to the solubility behavior as well as structural
modications of Nile Red with the ILs. On close examination,
we could observe that the deviations in the intensity increase
after 24.00 and 29.00 1C for 2.0 mg ml 1 of IL-1 and IL-2,
respectively. This can be taken in good agreement with our r
measurements in which the Tc was observed to be located
at 24.026 and 28.591 1C for 2.0 mg ml 1 of IL-1 and IL-2,
respectively.
The decrease or increase in Tc for IL-1 or IL-2 is mainly due
to the interactions between the ILs and the solvent particles.
Fig. 10 reveals the variation in size observed for the IBW and
IBW with ILs at various temperatures. Moreover, upon
comparison of both IL-1 and IL-2 in IBW by DLS measure-
ments, we found a large size dierence between IL-1 and IL-2
in IBW at their individual Tc values. The size gradually
increases from 51.14 nm at 27.2 1C and approaches the highest
value of 115.7 nm at Tc (26.4 1C) and again starts decreasing to
73.03 nm from 26.2 1C onwards for IBW. In presence of IL-1
we observed a size of 199.3 nm at 24.0 1C, and for IL-2, a value
of 210.9 nm at 28.2 1C. Additionally, we observed a large
decay time with an increase in size. Fig. 8 represents the
variations in the decay time with variations in intensity at
various temperatures. Moreover, the dierence in the size was
observed below the Tc values where the two phases are
distinctly separated. For the case of 2 mg ml 1 ILs; in the
presence of IL-1 we observed a value of 26.1 nm at 23 1C;
whereas, a value of 37.67 nm at 26 1C was observed in the
presence of IL-2 for the lower phase (i.e. water rich phase).
The dierence in size and decay time can be accounted for by
the dierences between the sizes of the IL cations, which
provide varying solvation sites for the neighboring solvent
New J. Chem., 2012, 36, 22662279 2275

molecules and, thereby, aect the diusion rate. Moreover, a
sudden and sharp decrease in size in the presence of IL-1 as
compared to IL-2 in Fig. 10 is observed after Tc at lower
temperatures. This reects that, in the presence of IL-1, the
molecules (i.e. the solvation structures) assembled and broke
up randomly below Tc in the sample volume, resulting in
strong density uctuations from the average. Additionally, the
dierence in the size of the cations of both the ILs cannot be
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ruled out. This points toward the slow diusion of IL-2 in
both the phases (Fig. 9). In support, we observed from Fig. 8,
larger decay curves for the IBW mixture in the presence of
IL-2 than in IL-1.
4. Discussion
4.1 The cation eect of ILs on the coexistence curve of IBW
For the removal of organic products from aqueous media,
ILs with low water solubility are required.47 Therefore, the
knowledge of the mutual solubility of water and ILs prior to
their industrial applications is of primary importance.17 The
inuence of cation structure on the miscibility of ILs may be
explained by two factors: (a) the similarity of the polarity
between the IL and the other uid,18 and (b) the free space
between molecules caused by large side chains.18 Since a longer
alkyl chain means less polarity and more hydrophobicity, the
solubility of the IL is thus reduced in polar solvents. For
instance, Dullius et al.19 reported that an alkyl derivative of
methylimidazolium tetrauoroborate IL is miscible with water
at room temperature depending upon their alkyl chain in the
cation. Imidazolium based ILs can act both as hydrogen bond
acceptors (anion) and donors (cation) and would be expected
to interact with solvents with both accepting and donating
sites, such as water. Thus, it can be concluded that the
imidazolium cation presents a higher anity for water. This
suggests that the solubility between water and imidazolium
based ILs is primarily dened by the hydrogen-bonding cap-
ability between the cation and the water oxygen.19
On the other hand, alkanes are known to be hydrophobic
compounds; therefore, an inuence on the ability to absorb
water is expected to be more pronounced for imidazolium-
based ILs bearing shorter alkyl chains. Consequently, in the
case of water-soluble ILs, an increase in the alkyl chain length
of their cations should lead to a lower water uptake. As
expected, ILs with aromatic groups absorb less water than
ILs with alkyl side chains due to the higher hydrophobicity of
the aromatic substituents.48 As a result, the miscibility of the
IL with water is gradually lowered. Since, we have taken very
small amounts of ILs (IL-1 and IL-2), we would expect that
the hydrophobicity of the cation chain is very low and is
overwhelmed by the attractive interactions such as H-bonding
existing between the polar C2 position of the imidazolium
cation and the water molecule, thereby resulting in the solva-
tion of the IL cations. Thus, the IL is moderately soluble in
water at its lower concentrations.
Moreover, the solubility of the IL with IB cannot be
ignored. It is well documented in the literature that the
solubility of ILs in organic solvents is completely dependent
on the alkyl chain length of the cation.49 The solubility of
2276 New J. Chem., 2012, 36, 22662279 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012
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alcohols is observed to increase with an increase in the cation
chain length of the IL. Attempts to nd liquidliquid phase
transitions in non-alcohol solvents have not been successful
because of the crystallization of the solvent from the mixture,
or because the two phase system started boiling below the
temperature at which the two phases might mix.50 However,
Holbrey et al.51 discussed the underlying specic interactions
between the imidazolium cations and the aromatic hydro-
carbon molecules during which the structure reveals that the
imidazolium cations form a weak CH


p hydrogen-bonded
zigzag chain. Further, the lipophilicity of the ILs, and the
solubility of non-polar solutes can be increased by adding an
additional non-polar alkyl functionality to the ILs, thus redu-
cing further Coulombic ion-ion interactions. However, it has
been reported that polar molecules, or those containing a
strong proton donor functionality, interact strongly with
ILs, and the compounds with weak proton donoracceptor
functions appear to interact with the ILs through induced ion-
dipole or weak van der Waals interactions.52 We may assume
that such interactions, predominantly hydrogen bonds,53 are
probably responsible for the solubility of the ILs with organic
solvents. In this regard from Fig. 1(a), we observed a large
increase in r of the IB rich phase in the presence of IL-1.
Therefore, when IL-1, at a small concentration, is added to
IBW, IL-1 preferably adsorbs to molecules of the solvent.
In addition, this phenomenon results in an important change
in the location of the critical region of the binary system
(Scheme 2).
From the above discussions, we could assume that the
IBW mixture is composed of two precursor solvents. The
blue shifts in the uorescence results from Fig. 4 reect that
the less polar solvent component is favored in the solvation
shell around the probe molecule. Moreover, upon addition of
IL, the mixture contains several types of pure as well as
hydrogen bonded species such as, IB, water, IL-IB and IL-water.
The increase in the intensity maximum of the probe with
addition of IL indicates the fact that the probe is preferen-
tially solvated by species like IL-IB and IL-water instead of
IBW at Tc.
The DLS analysis does not show any scattering for the pure
IB or water. Together with the absence of signals for the pure
components, this evidences a direct relation between the
solvation process and Tc which occur only in the mixtures
and depend on their compositions. The situation for IBW is
dierent from the other binary uid mixtures where the
thermal behavior shows only a weakly divergent behavior
when asymptotically approaching the critical point.5456 We
observed signicant scattering for the critical mixture of IBW
at Tc (Fig. 7). The reason for this behavior may be the
existence of water clusters in the mixture around the IB
molecules. Moreover, we found that the behavior of the
mutual diusion coecients for IBW is inuenced by the
nature of the chosen ILs. Eventually, from Fig. 7, a vast
increase in the scattered intensity is observed upon addition
of ILs, which supports the fact that the IL was mutually
solvated by the neighboring molecules. In another view, we
can also guess that the neighboring molecules were induced to
a large solvation extent in the presence of the ILs. The
presence of IL in the IBW increases the size of the water

cluster in the critical mixture, thereby decreasing the diusion
process at Tc (Fig. 9). However, there is a sudden and sharp
decrease in size in the presence of IL-1 as compared to IL-2 in
Fig. 10. This dierence may be a result of the dierence in the
size of the cations of the ILs. As evident from Fig. 8, the decay
curves are larger for IL-2 than IL-1. This may be predicted to
the slow diusion of the IL-2 in both the phases as obtained
from Fig. 9. It can be speculated that this is a result of the
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strong internal hydrogen bonds between the water molecules
and IL, promoting the formation of water clusters. As the
mobility of water clusters in the mixture is lower than that of
molecular water, the diusion of the clusters should be
observable at a large time scale at Tc.
Additionally, apart from all these factors, the solubilization
of a solute in a molecular solvent can be considered to depend
upon the cavity in the solvent, i.e. the size suitable to accom-
modate the solute. We expect that the substitution of a large
group like benzyl eliminates the possibility of interaction
between the IL cation and the IB molecules, causing a decrease
in the mutual solubilities of the IL and IB. As a result, the
benzyl cation is increasingly solvated by the water molecules.
The intermolecular hydrophobic interactions, in the presence
of the benzyl group of the IL cation, are rapidly reduced due
to steric hindrances, which results in less contact for inter-
molecular associations between the IL and IB. Additionally,
this may also be explained by the formation of water clusters
around IL-2 which cannot penetrate the interstitials of IB as
eciently as molecular solvents. In support, Klahn et al.,57
based on a simulation technique, predicted that it is indeed the
cation size that generally determines the interaction strength of
ILs with the neighboring solvents. Nevertheless, the hydro-
phobic mechanism is less clear for tetrauoroborate con-
taining ILs, and more understanding is required. Scheme 3
represents the solvation of the IL-2 cation by the water
molecules in the critical mixture of IBW.
Scheme 3 Schematic representation of the interaction of IL-2 with
the IB-rich and water-rich phases.
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From the analysis of our experimental results, we can
conclude that it is the eect of the IL cation chain that brings
about a varying extent of interactions with the neighboring
solvents molecules in the coexisting liquid mixture of IBW.
Furthermore, the aliphaticity of IL-1 and the aromatic char-
acter of IL-2 can now also be considered to be key factors for
the opposite eects on the Tc values of the IBW. Signicantly,
the solubility of the hydrophobic part (cation) of the IL plays
an important role in determining the UCST values of the IBW
critical mixture.
4.2 The anion eect of IL on the coexistence curve of IBW
The interactions of the anions with the solvent molecules
remain an active research eld.58 Therefore, the role of the
anion cannot be ignored. Various trials have been undertaken
to obtain a fundamental understanding of the interaction
between water and the ILs.5961 Moreover, the mutual solu-
bility of water in ILs is primarily dened by the type of anion
present in the ILs, and the solubility of water in the ILs is less
aected by the presence of the anion than the solubility of ILs
in water. Welton and co-workers59 investigated the state of
water in room temperature ILs based on the 1-alkyl-3-methyl-
imidazolium cation with several anions using Infrared (IR)
spectroscopy and suggested that the water molecules prefer-
entially interact with the anions. Additionally, quantum
chemical calculations60 have been used to investigate the
interaction between water molecules and ILs based on the
imidazolium cation with the anions [Cl] , [Br] , and [BF4] .
The predicted geometries and interaction energies implied that
the water molecules interact with the [Cl] , [Br] , and [BF4]
anions to form X


H2O (X = Cl or Br ), 2X


2H2O,
BF4


H2O, and H2O


BF4


H2O complexes. Wang
et al.60 signicantly found that the strengths of the interactions
between IL-cationwater, IL-anionwater, and ion-pairwater
follow the trend anionwater 4 cationwater 4 ion-pairwater,
respectively. Additionally, the strength of H-bonding between
anion and water increases in the order [PF6] o [SbF6] o
[BF4] o [Tf2N] o [ClO4] o [NO3] o [CF3CO2] .61
Therefore, water uptake is expected to exist for the [BF4]
ion in IL-1 and IL-2. The role of anion interaction with
organic molecules is still not clear. However, the ability of
the IL to create a hydrogen bond with organic molecules
signicantly increases the solubility of the IL. Research analysis
suggests that ILs containing the [BF4] anion show less inter-
actions with organic solvents.62 This could also account for the
minimum insolubility behavior of IL-2 in IB, where steric
repulsions overwhelm the weak interactions in neighboring
species because of the large size of the cation.
That the water structuring nature of the IL results in an
increase in the hydrogen bond network of water has been
conrmed by several research laboratories,59,63,64 and hence
IL-1 forces water molecules to diuse more with the IB
molecules in the mixture. This could also be regarded as a
simple consequence of the water[BF4] attractive interaction
that forces the water to surround the cation. However, the
participation of water[BF4] interactions to the stabilization
of the system cannot be ruled out a priori and the possibility
that cation hydrogen atoms could act as hydrogen bond
New J. Chem., 2012, 36, 22662279 2277

donors toward water might be taken into account as a working
hypothesis.65 The decrease in solubility of IL-2 in IB and its
solubility in water plays a major role in shifting the critical
temperature of the mixture to higher values. Since IL-2 is
conned only to the lower phase (i.e. water), more interactions
take place in the water-rich phase. Thus, we can suggest that
the hydrophobic interactions of the ILs permit solvation of the
cation by water molecules, and the steric interactions of IL-2
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with IB restrict the water molecules to diuse with the IB
phase. Eventually, IL-2 increases the Tc value of IBW at all
studied concentrations of IL-2. Our results point towards the
fact that ILs are much more complex solvents capable of
undergoing many types of interactions. Characterizing them
with a single polarity term fails to describe the type and
magnitude of individual interactions that makes each IL
unique. Despite the fundamental importance of the above
mentioned properties of ILs, their microscopic nature is far
from being well understood. However, the complexity of the
intermolecular (inter-ionic) as well as intra-molecular inter-
actions in ILs makes the prediction of their properties dicult,
and, therefore, the choice and design of the cations and anions
are not always successful.
5. Conclusions
On the basis of our experimental results, we conclude that the
change in the critical properties of the critical mixture of IBW
is totally attributed to the change in IL cation conformations
and their solvating properties. On the other hand, the eect of
the anion cannot be ignored but can be considered to have the
same solvating eects in water, as both the ILs (IL-1 and IL-2)
possess the same tetrauoroborate anion. As mentioned in the
discussion section, the formation of a solvation layer or water
cluster demonstrates that IL systems are complex and that
analyzing interactions on a molecular level tends to be
approximate. Since, there are a nite number of cationanion
combinations that can be examined experimentally, it is
crucial to establish a key parameter to characterise the proper-
ties of ILs. Our results conclude that the coordinating ability
of the ions of ILs, and the size of the cations, are the key
factors in obtaining an IL inuence on the coexistence curve.
Further, a minor change in the structure of the cation of an IL
can have a signicant inuence on the coexistence liquid
phases. The use of ILs as designer solvents in liquidliquid
composition requires detailed knowledge of their thermo-
physical properties. The observations of an approximate
correspondence between the distributions of densities of
individual phases of IBW in the presence of an IL system is
useful in studying molecular interactions. Our results explicitly
support the fact that ILs represent a novel class of solvents and
may now also be considered as a novel medium for studying
phase transitions in critical mixtures. Limited experience with
room temperature ILs based on a [Cnmim]+ cation and a
[BF4] anion suggests that such systems may be easily adapted
to conventional liquidliquid composition practice. These
interesting biphasic systems continue to be actively studied
in our laboratory for the development of novel, clean separa-
tion technologies. For ILs which act as impurities in critical
mixture systems, their partition problems can be much more
2278 New J. Chem., 2012, 36, 22662279 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012
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complicated than what is expected for simple two phase
systems. Currently, we only have a very limited explanation
for this dierent behavior. Our study makes ILs attractive not
only as solvents for chemical processes but also for the
separation and extraction of materials. More information is
needed to identify the eect of ILs on the critical phenomena
i.e. UCST as well as LCST. This is the subject of on-going
work in our laboratory.
Acknowledgements
Financial support from the Department of Science and
Technology (DST) [SR/SI/PC-54/2008] and University Grant
Commission (UGC) [37-404/209 (SR)], New Delhi, is grate-
fully acknowledged. We are very thankful to Mr Amit,
Application lab, Malvern, Aimil Ltd., New Delhi for carrying
out necessary DLS experiments.
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