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J Solution Chem (2008) 37: 203214

DOI 10.1007/s10953-007-9231-5
Estimates of Internal Pressure and Molar Refraction
of Imidazolium Based Ionic Liquids as a Function
of Temperature
Arvind Kumar
Received: 24 May 2007 / Accepted: 29 June 2007 / Published online: 13 December 2007
Springer Science+Business Media, LLC 2007
Abstract Estimates of the internal pressure (U/V)
T
of the ionic liquids (ILs)
1-butyl-3-methylimidazolium tetrauoroborate [BMIM][BF
4
], 1-butyl-3-methylimidazo-
lium hexauorophosphate [BMIM][PF
6
], and 1-methyl-3-octylimidazolium tetrauoro-
borate [OMIM][BF
4
] were made from experimentally determined densities and speeds of
sound in the temperature range 283.15 to 343.15 K. Values (U/V)
T
for all the ILs stud-
ied are higher than those of water and molecular organic liquids. We also measured the
refractive indices n
D
in the temperature range 288.15 to 343.15 K and estimated the mo-
lar refraction R
M
. Refractive indices of ILs were also higher than those of normal organic
liquids but were comparable to those of long hydrocarbon chain organic solvents.
Keywords Ionic liquids Density Speed of sound Refractive index Internal pressure
1 Introduction
Ionic liquids (ILs) [1] are attracting great interest as greener alternatives to conventional
organic solvents because of their wide thermal liquid range and low vapor pressures [2]. ILs
have been used as effective solvent media for catalyzing many organic reactions, with their
better kinetics and selectivity [3]. The catalyzing effect of solvent media can be adjudged by
several parameters, such as hydrogen-bonding, solvent polarity, hydrophobic aggregation,
etc. The internal pressure (U/V)
T
in a liquid, caused by cohesive forces, can be used as
an alternative explanation for describing kinetic rate enhancements in solvent media [47].
To date, the biggest developments in Diels-Alder chemistry have come through reactions
in Li[ClO
4
] + Et
2
O, where the high electrolyte concentrations are cited as being bene-
cial through the high internal pressure of the solvent. It is clear from the cited studies
that extending this concept through to the use of ionic liquid solvents will lead to further
A. Kumar ()
Central Salt and Marine Chemicals Research Institute, Bhavnagar 364002, India
e-mail: arvind@csmcri.org
A. Kumar
e-mail: mailme_arvind@yahoo.com
204 J Solution Chem (2008) 37: 203214
extensions in the scope of various organic reactions and eliminate the need for potentially
explosive reaction media.
A liquid undergoing a small, isothermal volume expansion does work against the cohe-
sive forces causing a change in the internal energy, U. The function (U/V)
T
is known as
the internal pressure, p
i
. Hildebrand [8, 9] showed that U/V =nU
vap
/V , where U
vap
repre-
sents the energy of vaporization of the liquid and V is its molar volume. Due to the very low
vapor pressures of ILs, measurement of the enthalpy of vaporization is not convenient under
ambient conditions and thus direct measurements of (U/V)
T
and the cohesive energy are
difcult. So far, only a few studies [1013] have been done where cohesive energies or vapor
pressure of room temperature ionic liquids were measured directly, or have been estimated
from the experimental results.
The quantity (U/V)
T
can alternatively be obtained by using the so-called thermo-
dynamic equation of state, T (p/T )
V
p. In liquids, the thermal pressure coefcient
(p/T )
V
multiplied by the absolute temperature has values of many thousands of at-
mospheres, so that the contribution from atmospheric pressure, p, becomes negligible by
comparison. Measurement of (U/V)
T
is thereby reduced to the measurement of the ther-
mal pressure coefcient. The thermal pressure coefcient can be equated to /
T
, where
is the coefcient of thermal expansion and
T
is the isothermal compressibility. The quanti-
ties and
T
can be estimated using accurate measurements of density and speed of sound
values at constant temperatures.
In this work we studied the isothermal expansion coefcient , isothermal compression
coefcient
T
, and estimated internal pressure (U/V)
T
of imidazolium based ionic liq-
uids. Besides measuring densities and speeds of sound, we also measured the refractive
index n
D
and estimated the molar refraction R
M
over a temperature range. The natures of
the anion, cation and side-chain length of the cation change the physical properties of ionic
liquids signicantly. Thus, we selected three ILs based on combinations of a common cation
with different anions and a common anion with cations having different alkyl chains.
2 Experimental Section
2.1 Materials
The air- and moisture-stable ILs, 1-butyl-3-methylimidazolium tetrauoroborate [BMIM]
[BF
4
], 1-butyl-3-methylimidazolium hexauorophosphate [BMIM][PF
6
], and 1-methyl-3-
octylimidazolium tetrauoroborate [OMIM][BF
4
], with stated purities >98% mass fraction,
were purchased from Merck. Since the trace amounts of water in ILs can have a dramatic
effect on their physical properties [14, 15], all of the ILs were dried and degassed under
vacuum at 60 C for several days to remove water. Karl-Fisher analysis of the dried samples
indicated that the water content in each liquid was reduced to <0.02%. The chloride content,
measured by Vollhards method [16], was found to be <0.01% in each liquid. The purity of
ILs was also checked by comparing the measured density, speed of sound and refractive
index with literature values [1730] at 298.15 K as shown in Table 1.
2.2 Speed of Sound Measurement
The speed of sound u in ILs was measured at 51,600 Hz using a concentration analyzer
(Model 87, SCM Laboratory Sonic Composition Monitor) based on the sing-around tech-
nique [31], with a single transducer cell that was immersed in a water bath with the tem-
perature controlled to 0.01 K. The analyzer was calibrated by measurements of speeds of
J Solution Chem (2008) 37: 203214 205
Table 1 Comparison of densities (), speeds of sound (u), and refractive indices (n
D
) for different ILs at
298.15 K with literature values
Compound (Ref.) u u (Ref.) n
D
n
D
(Ref.)
(gcm
3
) (gcm
3
) (ms
1
) (ms
1
)
[BMIM][BF
4
] 1.2141 1.204362 [17] 1565.1 1564 8 [22] 1.4197 1.410 [23]
1.21119 [18] (296.85 K)
[BMIM][PF
6
] 1.3679 1.366657 [24] 1442.2 1442.41 [24] 1.4089 1.409 [28]
1.36612 [25] 1441 4 [22]
1.36730 [26] (296.85 K)
1.36543 [18]
[OMIM][BF
4
] 1.1030 1.10368 [29] 1482.2 1491 [30] 1.4319 1.43422 [30]
1.10530 [30]
sound in water as a reference, and the error was estimated to be less than 0.1 ms
1
[31].
Measurements were carried out in a specially designed low-volume sample jar. This sample
jar was provided with an air-tight Teon covering to keep the samples moisture free dur-
ing measurements. Dried and degassed samples kept in desiccators were directly injected
through a syringe into the sample jar, avoiding contact with atmospheric air. To check the
reproducibility of the results, not less than three experiments were performed for each sam-
ple over the whole temperature range. At each temperature the sample was equilibrated for
about 30 minutes.
2.3 Density Measurements
The densities of the liquids were measured with an Anton Paar (Model DMA 4500)
vibrating-tube densimeter with a resolution of 5 10
5
gcm
3
. The temperature of the
apparatus was controlled to within 0.03 K by a built-in Peltier device. The densimeter was
calibrated with doubly distilled and degassed water, with dry air at atmospheric pressure,
and also against the densities of NaCl(aq) [32].
2.4 Refractive Index Measurements
Refractive indices were measured using a Mettler-Toledo (Model RE-40 D) refractometer
with a high-resolution optical sensor. Measurements were made with a resolution and error
limit of 1 10
4
. The temperature of the apparatus was controlled to within 0.1 K by a
built-in Peltier device. Dried and degassed samples kept in desiccators were directly injected
through a syringe into the measuring cell. The reproducibility of the results was determined
by performing at least three experiments for each sample over the whole temperature range.
3 Results and Discussion
3.1 Density and Speed of Sound
Experimental values of the densities, speeds of sound and other derived properties for vari-
ous ILs: ,
s
,
T
and (U/V)
T
as a function of temperature, are reported in Table 2. The
206 J Solution Chem (2008) 37: 203214
Table 2 Experimental densities (), speeds of sound (u), and estimated values of ,
s
,
T
and (U/V )
T
of different ILs in the temperature range 283.15 to 343.15 K
T /K u 10
4
10
12

s
10
12

T
(U/V)
T
(gcm
3
) (ms
1
) (K
1
) (Pa
1
) (Pa
1
) (atm.)
[BMIM][BF
4
]
283.15 1.2252 1604.5 6.04 317.04 371.87 4539
288.15 1.2215 1591.1 6.05 323.38 379.23 4533
293.15 1.2179 1578.0 6.06 329.78 386.84 4532
298.15 1.2141 1565.1 6.05 336.23 394.03 4518
303.15 1.2105 1552.6 6.03 342.73 401.08 4498
308.15 1.2068 1540.3 6.01 349.28 408.15 4478
313.15 1.2032 1528.3 5.98 355.85 415.05 4453
318.15 1.1996 1516.5 5.94 362.46 421.76 4422
323.15 1.1960 1505.1 5.93 369.09 429.08 4408
328.15 1.1925 1493.9 5.91 375.75 436.21 4388
333.15 1.1890 1483.0 5.90 382.42 443.56 4373
338.15 1.1855 1472.0 5.89 389.10 450.90 4359
343.15 1.1820 1462.1 5.87 395.79 458.04 4340
[BMIM][PF
6
]
283.15 1.3807 1479.8 6.13 330.74 386.46 4433
288.15 1.3764 1467.3 6.18 337.45 395.04 4449
293.15 1.3721 1454.8 6.20 344.36 403.29 4448
298.15 1.3679 1442.2 6.22 351.47 411.75 4446
303.15 1.3636 1429.7 6.25 358.78 420.22 4436
308.15 1.3593 1417.2 6.24 366.30 428.92 4424
313.15 1.3551 1404.6 6.22 374.03 437.22 4397
318.15 1.3509 1392.1 6.19 381.99 445.53 4362
323.15 1.3467 1379.6 6.17 390.17 454.25 4332
328.15 1.3425 1367.0 6.16 398.58 463.40 4305
333.15 1.3384 1354.5 6.14 407.25 472.59 4272
338.15 1.3343 1342.0 6.14 416.17 482.45 4247
343.15 1.3302 1329.4 6.15 425.37 492.81 4226
[OMIM][BF
4
]
283.15 1.1134 1522.5
a
6.21 389.51 442.74 3972
288.15 1.1099 1509.5
a
6.22 397.52 451.75 3967
293.15 1.1064 1495.6 6.23 405.77 461.41 3958
298.15 1.1030 1482.2 6.24 414.06 471.01 3944
303.15 1.0995 1468.7 6.26 422.96 481.15 3928
308.15 1.0961 1454.4 6.27 431.94 491.86 3903
313.15 1.0926 1441.3 6.25 441.18 501.50 3880
318.15 1.0892 1428.3 6.24 450.68 511.60 3853
323.15 1.0858 1414.2 6.23 460.47 522.62 3827
328.15 1.0824 1401.2 6.22 470.54 533.28 3797
333.15 1.0791 1388.2 6.20 480.90 544.02 3797
338.15 1.0757 1375.1 6.19 491.61 555.31 3769
343.15 1.0724 1361.1 6.18 502.62 567.62 3736
a
Extrapolated values to linear ts of experimental measurements
J Solution Chem (2008) 37: 203214 207
Table 3 Correlations for the densities (), speeds of sound (u), and refractive indices (n
D
) of different ILs
as a function of temperature between 283.15 and 343.15 K
Compound /gcm
3
s.d.
[BMIM][BF
4
] 1.429 0.0007 (T /K) 0.0002
[BMIM][PF
6
] 1.619 0.0008 (T /K) 0.0001
[OMIM][BF
4
] 1.307 0.0007 (T /K) 0.0001
u/m s
1
[BMIM][BF
4
] 2771.41 5.56 (T /K) +0.005 (T /K)
2
0.18
[BMIM][PF
6
] 2189.52 2.51 (T /K) 0.01
[OMIM][BF
4
] 2283.99 2.69 (T /K) 0.47
n
D
[BMIM][BF
4
] 1.569 0.0007 (T /K) 0.0004
[BMIM][PF
6
] 1.606 0.001 (T /K) 0.0005
[OMIM][BF
4
] 1.654 0.001 (T /K) 0.0003
temperature dependences of density, speed of sound and refractive index were correlated by
means of a polynomial-type equation:
F(Q) =
n

i=1
A
i
T
i1
(1)
where Q represents a measured property (density, speed of sound or refractive index) and
T represents the temperature. Correlation parameters of the density and speed of sound
as a function of temperature, along with their standard deviations, are given in Table 3.
Densities of various ILs as a function of temperature, along with corresponding literature
values, are compared in Fig. 1. Our density measurements are quite compatible with the
available literature data and the maximum deviations are in the range from 1 to 0.5%,
which can be attributed to the presence of different amounts of water and halide impu-
rities in the ILs used by various authors, and also from the different experimental tech-
niques. The densities decrease linearly with increasing temperature for all the liquids inves-
tigated.
Because the temperature dependence of density is linear for the ILs, density val-
ues as a function of temperature were used to calculate the isothermal expansion co-
efcient (reported in Table 2). Estimates of made from experimental densities in-
dicate that the ionic liquids do not expand appreciably between 283.15 and 343.15 K.
All of the investigated ionic liquids show weak temperature dependences for the isother-
mal expansion coefcient, = (5.8 to 6.3 10
4
) K
1
, which are considerably smaller
than those for molecular organic liquids, but are higher than those of high-temperature
molten salts. ILs with a shorter alkyl chain show less expansion when compared with
an IL having the same anion but with a longer alkyl chain on the cation. The ef-
fect from coiling of the chain may be the reason for the larger expansion coef-
cient of the ILs with long alkyl chains. Similarly, the IL with [PF
6
] as the anion
has a larger expansion coefcient when compared with ILs having [BF
4
] as the an-
ion.
Speeds of sound, shown in Fig. 2, decrease linearly with increasing temperature for the
investigated liquids. From the measured speeds of sound, isothermal compressibilities were
208 J Solution Chem (2008) 37: 203214
Fig. 1 Comparison of measured densities with literature values. [BMIM][BF
4
]: Qthis work; [18]; [21];
[19]; [20]. [BMIM][PF
6
]: this work; [18]; [27]; + [26]; [19]. [OMIM][BF
4
]: " this work
Fig. 2 Speeds of sound as a function of temperature: Q [BMIM][BF
4
]; [BMIM][PF
6
]; and
" [OMIM][BF
4
]
J Solution Chem (2008) 37: 203214 209
estimated using the relation,

T
=
s
+(
2
T V
M
)/C
p
(2)
where
s
=1/u
2
is the isentropic compressibility, is the coefcient of thermal expansion,
T is temperature, V
M
is the molar volume and C
p
is the heat capacity (heat capacity values
for various ionic liquids were taken from [21, 33]). The isothermal compressibility increases
linearly with increasing temperature for all of the liquids. ILs studied here are less compress-
ible than organic liquids, as expected due to the strong Coulombic interactions between the
ions. A comparison of
T
values reveals that an ionic liquid with a larger molar volume is
more compressible. Differences between the compressibilities of ILs with a common cation
and different anions are small due to their comparable sizes, whereas an IL with a longer
cation alkyl chain is more compressible compared with an IL having a small alkyl chain and
the same anion. This may be due to a larger free volume resulting from the large cation-
anion volume ratio in the larger IL. Similar observations were made by Tekin et al. [18]
and Brennecke et al. [28], where isothermal compressibilities of ILs were estimated from
density measurements at different pressures.
Estimates of the internal pressure(U/V)
T
were made using the calculated and
T
values, using the relation
(U/V)
T
=T/
T
(3)
where all the symbols have their usual meaning. Although the errors in the individual proper-
ties are compounded when their ratio is calculated, the values obtained are extremely useful
because a direct measurement of (P/T )
V
can not be readily made at or near room tem-
peratures. The overall uncertainties in the derived values are <0.25%. Estimated values of
internal pressure are reported in Table 2 and are shown in Fig. 3. Values of (U/V)
T
of the
Fig. 3 Internal pressure as a function of temperature: Q [BMIM][BF
4
]; [BMIM][PF
6
]; and
" [OMIM][BF
4
]
210 J Solution Chem (2008) 37: 203214
investigated liquids are higher than those of water and molecular organic liquids. This may
be due to the higher contribution from electrostatic interactions in the ILs. However, the ILs
have lower (U/V)
T
values when compared to classical molten salts [34]. This is due to
the fact that in the molten salts, there are purely electrostatic interactions, whereas in the
case of ILs other kinds of molecular interactions such as hydrogen bonding, etc., are also
present. The internal pressure decreases with an increase in temperature for all the ILs. This
decrease in (U/V)
T
is slow at lower temperatures but is more prominent at higher tem-
peratures for all the ILs. Despite the narrow range of structural variation studied, we observe
that (U/V)
T
values are higher in ILs with a smaller alkyl chain at a given temperature.
For ILs with the same cation, higher values of (U/V)
T
were observed for an IL with the
[BF
4
] anion compared to [PF
6
] anion at a certain temperature.
The internal pressure can be equated with the cohesive energy density by the relation
(U/V)
T
= nU
vap
/V . A comparison of our estimated internal pressures and cohesive
energy densities with those estimated by Swiderski and coworkers [10] yields n = 0.459
and 0.494 at 298.15 K for [BMIM][BF
4
] and [BMIM][PF
6
], respectively. Due to the lack of
availability of cohesive energy data, we could not estimate the value of n for [OMIM][BF
4
].
The comparatively lower value of n indicates that the ILs investigated in this paper are
moderately polar.
3.2 Refractive Indices
The experimental temperature dependences of refractive indices n
D
for different ILs are
presented in Table 4 and are shown in Fig. 4. Correlation coefcients of R
1
with temperature
are given in Table 3. The refractive indices of the studied ionic liquids lie in the range 1.41
to 1.44 near room temperature. Such values are comparable to those for typical long-chain
Fig. 4 Refractive index as a function of temperature: Q [BMIM][BF
4
]; [BMIM][PF
6
]; and
" [OMIM][BF
4
]
J Solution Chem (2008) 37: 203214 211
Table 4 Experimental values of the refractive indices (n
D
), and estimated values of molar refraction (R
M
),
of ILs at different temperatures
T /K n
D
R
M
/(g cm
3
)
[BMIM][BF
4
]
288.15 1.4234 47.16
293.15 1.4214 47.11
298.15 1.4197 47.08
303.15 1.4181 47.07
308.15 1.4166 47.06
313.15 1.4155 47.09
318.15 1.4142 47.10
323.15 1.4132 47.14
328.15 1.4120 47.16
333.15 1.4109 47.19
338.15 1.4098 47.22
343.15 1.4087 47.25
[BMIM][PF
6
]
288.15 1.4133 51.52
293.15 1.4110 51.42
298.15 1.4089 51.35
303.15 1.4073 51.34
308.15 1.4057 51.32
313.15 1.4046 51.36
318.15 1.4036 51.40
323.15 1.4025 51.44
328.15 1.4015 51.49
333.15 1.4004 51.52
338.15 1.3994 51.56
343.15 1.3983 51.60
[OMIM][BF
4
]
288.15 1.4357 66.42
293.15 1.4335 66.34
298.15 1.4319 66.33
303.15 1.4302 66.31
308.15 1.4288 66.33
313.15 1.4277 66.39
318.15 1.4266 66.45
323.15 1.4255 66.51
328.15 1.4245 66.58
333.15 1.4234 66.63
338.15 1.4224 66.70
343.15 1.4213 66.76
212 J Solution Chem (2008) 37: 203214
organic solvents such as hexadecane (1.433) and dodecanol (1.441) [35] as a result of the
higher densities of ionic liquids. Values of n
D
decrease in a curvilinear manner with an
increase in temperature for each IL and follow the order [OMIM][BF
4
] >[BMIM][BF
4
] >
[BMIM][PF
6
]. The temperature derivatives of ILs lie in the range (0.2 to 0.4) 10
3
K
1
,
and are somewhat smaller than values found for typical organic solvents. Because molar
properties are more informative, we calculated molar refraction values, R
M
, for these liquids
using the Lorentz-Lorenz relationship
R
M
=

n
2
D
1
n
2
D
+2

(4)
where all the symbols have their usual meaning. Equation 4 is equivalent to
R
M
=N/3
0
(5)
where N is Avogadros number, is mean molecular polarizability ( = 4
0
a
3
, where
a is the spherical radius) and
0
is the permittivity of free space. From Eq. 5, R
M
can be
interpreted as the hard-core volume, i.e., it is an approximate measure of the total volume
(without free space) of one mole of molecules. R
M
values are given in Table 4 and follow
the order [OMIM][BF
4
] >[BMIM][PF
6
] >[BMIM][BF
4
].
4 Conclusions
The density, speed of sound and refractive index of the three ILs [OMIM][BF
4
], [BMIM]
[PF
6
] and [BMIM][BF
4
] were measured as a function of temperature at atmospheric pres-
sure. From the measured properties, estimates were made of the internal pressure and molar
refraction. The internal pressure decreases with increasing temperature for all the ILs. The
internal pressures of the investigated ILs were found to be higher than those of water and
molecular organic liquids. Also, the derived parameters as a function of temperature were
found to vary with the nature of the cation and anion of the ILs.
Acknowledgements The author is thankful to Dr. P.K. Ghosh, Director of the institute, for providing fa-
cilities and interest in this work.
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