J. Chem.

Thermodynamics 41 (2009) 334341

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Excess molar properties for binary systems of alkylimidazolium-based ionic

liquids + nitromethane. Experimental results and ERAS-model calculations
Gonzalo Garca-Miaja, Jacobo Troncoso, Luis Roman *
Departamento de Fsica Aplicada, Universidad de Vigo, Facultad de Ciencias, Campus As Lagoas, 32004 Ourense, Spain

a r t i c l e

i n f o

Article history:
Received 18 July 2008
Received in revised form 5 September 2008
Accepted 8 September 2008
Available online 15 September 2008
Keywords:
Excess molar enthalpy
Isobaric molar heat capacity
Ionic liquid
Nitromethane
ERAS

a b s t r a c t
Density, isobaric molar heat capacity, and excess molar enthalpy were experimentally determined at
atmospheric pressure for a set of binary systems ionic liquid + nitromethane. The studied ionic liquids
were: 1-butyl-3-methylimidazolium tetrauoroborate, 1-hexyl-3-methylimidazolium tetrauoroborate,
1-butyl-3-methylpyridinium tetrauoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium triuoromethanesulfonate, and 1butyl-3-methylimidazolium triuoromethanesulfonate. Density and heat capacity were obtained within
the temperature range (293.15 to 318.15) K whereas excess molar enthalpy was measured at 303.15 K;
excess molar volume and excess molar isobaric heat capacity were calculated from experimental data.
The ERAS-model was applied in order to study the microscopic mechanisms involved in the mixing process. Although the studied compounds are not self-associated, ERAS-model describe adequately the
experimental results if cross-association between both compounds is considered.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Study of room temperature ionic liquids (RTILs) as solvents has
received an increasing attention in the last years from fundamental
and applied points of view [115]. As for thermodynamics of RTILs
in solution with other compounds, there are many experimental
and theoretical studies which deal on the behavior of thermodynamic properties of mixtures RTIL + common organic solvent
[1633]; however, due to the enormous number of possible binary
systems, a lot of work remains to be done. Polar compounds present good solubility with ionic liquids; therefore, there are several
works that study the thermodynamic properties of RTILs + polar
compound, being the RTIL + CO2 system extensively studied due
to its importance for supercritical extraction [1618]. On the other
hand, much effort in this eld has been devoted to the study of
RTIL + water and RTIL + alcohol binary systems, mainly motivated
by their solubility with RTILs as well as their low environmental
impact [1927]. The thermodynamic properties of RTILs with other
polar compounds have been studied in some extent [2933], especially volumetric properties, but there are few works that study
their thermodynamic behavior considering thermal properties as
enthalpy or heat capacity.
The present work analyzes the excess molar enthalpy, excess
molar volume, and excess molar isobaric heat capacity of
RTIL + nitromethane systems by means of the ERAS-model. With
* Corresponding author. Tel.: +34 988 387 211; fax: +34 988 387 227.
E-mail address: romani@uvigo.es (L. Roman).
0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.09.002

this purpose, excess enthalpy, density, and heat capacity were

experimentally determined for a set of RTIL + nitromethane binary
systems. The RTILs were selected in order to be able to study the
effect of changing the chemical structure of the cation and/or the
anion on thermodynamic properties. To observe the inuence of
varying the chemical nature of only the cation or the anion, most
of the selected RTILs present a common ion. Considering the
bibliographic data available, the selected RTILs were: 1-butyl-3methylimidazolium tetrauoroborate, [bmim][BF4]; 1-hexyl-3methylimidazolium tetrauoroborate, [hmim][BF4]; 1-butyl-3methylpyridinium tetrauoroborate, [bmpyr][BF4]; 1-ethyl-3methylimidazolium ethylsulfate, [emim][EtSO4]; 1-butyl-3-methylimidazolium methylsulfate, [bmim][MetSO4]; 1-ethyl-3-methylimidazolium triuoromethanesulfonate, [emim][triate]; and
1-butyl-3-methylimidazolium triuoromethanesulfonate, [bmim][triate]. Density and isobaric molar heat capacities were
measured in a temperature interval from (293.15 to 318.15) K at
atmospheric pressure for all systems except for [bmpyr][BF4], since
these data are available in literature [29]; from these, excess molar
volume and excess molar isobaric heat capacity were calculated.
Excess molar enthalpy was measured at 303.15 K and atmospheric
pressure for all systems except for those containing [bmim][BF4]
and [bmim][MetSO4] since there are available data in literature
[31]. The experimental results are analyzed in the frame of the Extended Real Associated Solution theory, ERAS [3436], with the
hypothesis that RTILs and nitromethane cannot self-associate,
but they can cross-associate. The obtained ERAS parameters are
analyzed in order to determine the main microscopic processes

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G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

that explain the values of the studied excess thermodynamic

properties.

TABLE 1
Density and isobaric molar heat capacity for pure components at T = 298.15 K and
comparison with literature data

q/(g  cm3)

2. Experimental section
2.1. Chemicals
Nitromethane was obtained from Fluka with purity greater than
0.985 in mass fraction and was dried in Fluka 0.3 nm molecular
sieves before use. All ionic liquids were purchased from Solvent
Innovation and they were dried in vacuum at 333.15 K for 48 h
prior to use in order to eliminate water and other volatile compounds. It was not observed decomposition of the RTILs at the
experimental conditions. The water mass fraction of the dried
RTILs was determined through Karl Fisher titration, and it was
found to be less than 1.3  103 for all samples.

[bmim][BF4]
[hmim][BF4]
[emim][EtSO4]
[bmim][MetSO4]
[emim][triate]
[bmim][triate]
Nitromethane

Cp/(J  mol1  K1)

This work

Literature

This work

Literature

1.2041
1.1453
1.2372
1.2074
1.3853
1.2976
1.1334

1.2141
1.1481
1.2376
1.2124
1.3836
1.2980
1.1313

363.1
427.8
394.4
416.2
363.2
424.1
106.9

364.8 [32]
416 [13]
377.6 [8]
255.3 [9]
375.6 [10]
417.2 [11]
105.89 [42]

[12]
[28]
[25]
[27]
[22]
[7]
[42]

TABLE 2
Density, q/(g  cm3), as a function of temperature for pure compounds
T/K

2.2. Apparatus and procedure

Mixtures were prepared by weighing on a Mettler AE240 balance. The uncertainty in mole fraction was estimated to be
1  104. Densities, q, were determined by means of an AntonPaar DMA5000 densimeter, which performs automatically the viscosity correction, needed for high viscosity samples, as most of the
studied RTILs. This apparatus was calibrated using MilliQ water
and dry air as standards. The uncertainty of the measurement is
estimated to be 1  104 g  cm3. A more detailed description of
this instrument can be found elsewhere [37,38]. Isobaric molar
heat capacities, Cp, were calculated from experimental density
and isobaric heat capacity per unit volume, CpV1. This last quantity was measured in a Setaram MicroDSCIII differential scanning
calorimeter, n-butanol and toluene were used as standards; their
densities and molar heat capacities were obtained from literature
[3941]. The uncertainty of the measurements is quoted in 0.3%.
A comprehensive description of the apparatus as well as the calibration procedure can be found in literature [43,44]. Excess enthalpy, HE, was measured in a Calvet microcalorimeter; the classical
arrangement was modied in order to stir the sample, a fact
needed due to the high viscosity of the RTILs. The uncertainty of
the measurements was estimated to be less than 4%. Detailed
information about this instrument can be found elsewhere [45].
The speed of sound, u, of some pure compounds was measured because it is needed for the ERAS-model calculations; an Anton-Paar
DSA48 sound analyzer was used to this end. A more detailed
description about the experimental procedure is given in [46].
The temperature uncertainty is estimated to be 0.01 K for density,
heat capacity and speed of sound measurements and 0.05 K for
excess enthalpy.
3. Results
In table 1 the densities and isobaric molar heat capacities of
pure compounds at 298.15 K are presented and compared to the
literature data. As a rule, good agreement was achieved; only the
heat capacity of [emim][EtSO4] differs signicantly from that reported in literature. Taking into account the similar chemical structure of this RTIL and [bmim][MetSO4], the heat capacity of both
compounds must be similar, and therefore, the value reported in
literature seems to be wrong. Tables 2 to 4 show density, isobaric
molar heat capacity, and speed of sound at several temperatures
for pure compounds. The excess molar enthalpies HE for the studied systems are presented in table 5 whereas the experimental values of density and isobaric molar heat capacity are deposited as
Supplementary Material. Excess molar volume and excess molar
isobaric heat capacity were calculated at (298.15, 308.15 and
318.15) K from

[bmim][BF4]
[hmim][BF4]
[emim][EtSO4]
[bmim][MetSO4]
[emim][triate]
[bmim][triate]
Nitromethane

293.15

298.15

303.15

308.15

313.15

318.15

1.2076
1.1488
1.2406
1.2107
1.3895
1.3016
1.1402

1.2041
1.1453
1.2372
1.2074
1.3853
1.2976
1.1334

1.2005
1.1418
1.2338
1.2041
1.3811
1.2937
1.1266

1.1970
1.1384
1.2304
1.2008
1.3769
1.2897
1.1197

1.1934
1.1350
1.2270
1.1975
1.3727
1.2858
1.1129

1.1899
1.1316
1.2237
1.1942
1.3686
1.2819
1.1060

TABLE 3
Isobaric molar heat capacity, Cp/(J  mol1  K1), as a function of temperature for pure
compounds
T/K

[bmim][BF4]
[hmim][BF4]
[emim][EtSO4]
[bmim][MetSO4]
[emim][triate]
[bmim][triate]
Nitromethane

293.15

298.15

303.15

308.15

313.15

318.15

359.8
425.1
392.2
413.7
361.1
421.6
106.6

363.1
427.8
394.4
416.2
363.2
424.1
106.9

366.1
430.4
396.8
418.5
365.3
426.7
107.3

368.7
433.0
399.3
420.9
367.4
429.5
107.7

371.0
435.5
402.0
423.3
369.6
432.4
108.2

372.9
438.1
404.9
425.6
371.8
435.5
108.6

TABLE 4
Speed of sound, u/(m  s1), as a function of temperature for pure compounds
T/K

[bmpyr][BF4]
[bmim][BF4] [30]
[hmim][BF4]
[emim][EtSO4] [25]
[bmim][MetSO4] [14]
[emim][triate] [22]
[bmim][triate]
Nitromethane

YE YM 

2
X

293.15

298.15

303.15

308.15

313.15

318.15

1599.8
1594.9
1532.7
1691.4
1670.9
1447.0
1403.4
1339.6

1587.0
1576.1
1519.5
1679.0
1658.4
1435.6
1392.1
1320.1

1574.8
1555.5
1506.9
1666.6
1646.0
1424.3
1380.9
1300.5

1562.6
1543.9
1494.5
1654.0
1633.5
1413.1
1369.8
1280.7

1550.7
1532.5
1482.3
1641.6
1621.1
1402.1
1358.8
1261.1

1538.9
1521.2
1470.5
1629.2
1608.6
1391.1
1348.1
1241.6

xi Y 0i ;

i1

where xi is the molar fraction of the RTIL and Y can be molar volume
V or isobaric molar heat capacity Cp. The experimental excess properties at each temperature were tted to polynomials of the form

Y E x1  x

n
X

Ai xi=2 :

i0

Fitting coefcients, Ai, are given in tables 6 to 8 for the studied excess properties, as well as the parameter v2, which gives informa-

336

G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

TABLE 5
Excess molar enthalpies at T = 303.15 K for xRTIL + (1  x) nitromethane
[bpyr][BF4]

[hmim][BF4]
E

H /(J  mol

0.0992
0.1547
0.1998
0.3029
0.3978
0.4973
0.6053
0.7038
0.7950
0.8525

252
328
401
443
476
470
396
336
233
162

1

[emim][EtSO4]
E

H /(J  mol

0.1000
0.2074
0.3028
0.4096
0.5095
0.6072
0.7148
0.7891
0.8821

73
124
146
160
159
143
113
94
50

1

[emim][triate]
E

H /(J  mol

0.1001
0.1977
0.3075
0.4001
0.5071
0.6026
0.6953
0.8026
0.8668

288
485
594
644
620
547
451
308
209

1

[bmim][triate]
E

1

H /(J  mol

0.1234
0.2533
0.3774
0.5026
0.6253
0.7438
0.8668

126
191
196
201
167
125
58

HE/(J  mol1)

0.1022
0.1994
0.3029
0.4044
0.5067
0.5931
0.7030
0.7814
0.8933

39
57
62
59
56
45
31
5
9

TABLE 6
Fitting coefcients for VE for xRTIL + (1  x) nitromethane

[bmim][BF4]

[hmim][BF4]

[emim][EtSO4]

[bmim][MetSO4]

[emim][triate]

[bmim][triate]

v2

T/K

A0/
(cm3  mol1)

A1/
(cm3  mol1)

A2/
(cm3  mol1)

A3/
(cm3  mol1)

298.15
308.15
318.15

10.332
11.457
12.735

22.314
25.012
28.053

21.029
23.634
26.545

7.574
8.555
9.612

0.00002

298.15
308.15
318.15

9.149
9.919
11.193

21.780
22.743
26.192

22.128
21.617
25.352

8.368
7.500
9.052

0.00004

298.15
308.15
318.15

9.870
10.932
12.122

17.082
18.899
20.930

8.648
9.548
10.563

0.00011

298.15
308.15
318.15

9.362
10.490
11.637

17.006
19.217
21.244

9.376
10.650
11.656

0.00008

298.15
308.15
318.15

10.780
11.924
13.179

23.434
26.232
29.176

21.919
24.647
27.363

7.853
8.837
9.749

298.15
308.15
318.15

9.651
10.665
11.813

23.283
25.898
28.825

24.664
27.301
30.254

9.960
10.966
12.076

0.00002

2.19E06

TABLE 7
Fitting coefcients for C Ep for xRTIL + (1  x) nitromethane

[bmim][BF4]

[hmim][BF4]

[emim][EtSO4]

[bmim][MetSO4]

[emim][triate]

[bmim][triate]

A0/(J  mol1  K1)

298.15
308.15
318.15

17.66
19.77
21.88

24.26
25.04
25.83

298.15
308.15
318.15

39.64
44.82
51.83

81.21
93.59
115.64

44.39
54.42
73.25

0.00983

298.15
308.15
318.15

22.96
24.04
25.12

66.99
65.66
64.34

44.03
42.23
40.43

0.00946

298.15
308.15
318.15

27.46
31.60
36.79

73.25
82.40
93.49

46.26
52.79
60.17

0.0125

298.15
308.15
318.15

10.79
12.41
13.62

10.20
11.77
12.73

298.15
308.15
318.15

31.75
38.30
44.85

64.29
82.40
100.51

tion about the quality of the t, since it is dened as the sum of the
squares of the deviations of experimental data from the tting
curve divided by the number of experimental points minus the
number of parameters; in fact, the tting process is based on min-

A1/(J  mol1  K1)

A2/(J  mol1  K1)

v2

T/K

0.0876

0.157
36.85
51.21
65.57

0.0998

imizing v2. An F-test was performed in order to obtain the optimum

number of parameters.
Experimental excess molar volumes VE and those of
[bmpyr][BF4] + nitromethane, obtained from literature [29] are

337

G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

for all systems. Small heat capacity values are found for all systems
(within 1 and 2.5 J  mol1  K1). There is a dependence on the
size of the cation: as the cation is smaller, C Ep becomes more positive. The higher C Ep values are found for sulfate-based RTILs. HE are
shown in gure 3 as well as those of the [bmim][BF4] + nitromethane and [bmim][MetSO4] + nitromethane systems [31]. All the obtained HE are small and they are negative except for
[bmim][triate] + nitromethane, which are positive at RTIL at low
molar fraction and around x = 0.85 becomes negative.

TABLE 8
Fitting coefcients for HE for xRTIL + (1  x) nitromethane

[bpyr][BF4]
[hmim][BF4]
[emim][EtSO4]
[emim][triate]
[bmim][triate]

T/K

A0/
(J  mol1)

A1/
(J  mol1)

303.15
303.15
303.15
303.15
303.15

3412.6
961.5
3391.6
1496.3
1486.1

2224.6
467.4
13.8
1002.3
5560.8

A2/
(J  mol1)

A3/
(J  mol1)

1799.9
8957.3

5097.5

v2
134
6
23
47
21

presented in gure 1. VE is negative for all systems over the whole

composition range with a minimum between (0.6 and
0.8) cm3  mol1. The temperature dependence is negative for
all systems. The most negative VE are obtained for [bmim][BF4],
[emim][EtSO4], and [emim][triate]. A clear dependence of VE on
the cation size is observed: the bigger the cation the lower the VE
in absolute value is. Figure 2 shows the experimental excess isobaric molar heat capacities C Ep , the corresponding ts to equation
(2) and those of [bmpyr][BF4] + nitromethane system, obtained
from literature [29]. The behavior of this property is similar for
all systems: there is a region of negative C Ep at low RTIL mole fraction, passing through a minimum and then C Ep increases, becoming
positive and presenting a maximum at high RTIL mole fraction for
some of the systems. The C Ep temperature dependence is negative

4. ERAS-model
The Extended Real Associated Solution Theory, ERAS, [3436]
was applied to the studied RTIL + nitromethane systems. Although
this is a model devoted to describe associated compound properties and neither RTILs nor nitromethane self-associate, previous
works have shown that it is possible cross-association between
an RTIL and polar compound [18,4749], fact which have motivated the use of this model, assuming only cross-association between RTIL and nitromethane. The ERAS parameters related with
this process are KAB, DhAB, and DvAB. KAB represents the equilibrium
constant of the reaction
K AB

A B $ AB;

V E/ (cm3mol-1)

0.0

-0.2

-0.4

-0.6

-0.8

(b)

(a)

(c)

(e)

(d)

(f)

(g)

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

FIGURE 1. Excess molar volume for x RTIL + (1  x) nitromethane at: (j) 298.15 K; () 308.15 K; (N) 318.15 K; () equation (2) at each temperature for: (a) [bmim][BF4]; (b)
[hmim][BF4]; (c) [emim][EtSO4]; (d) [bmim][MetSO4]; (e) [bmim][triate]; (f) [emim][triate]; and (g) [bmpyr][BF4] at () 298.15 K; (- - -) 308.15 K; (  ) 318.15 K from
reference [29].

Cp / (Jmol-1K -1)

1.0

(c)

(b)

(a)

(d)

(e)

(f)

(g)

0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.5

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

FIGURE 2. Excess molar isobaric heat capacity for x RTIL + (1  x) nitromethane at: (j) 298.15 K; () 308.15 K; (N) 318.15 K; () equation (2) at each temperature for: (a)
[bmim][BF4]; (b) [hmim][BF4]; (c) [emim][EtSO4]; (d) [bmim][MetSO4]; (e) [bmim][triate]; (f) [emim][triate]; and (g) [bmpyr][BF4] at () 298.15 K; (- - -) 308.15 K; (  )
318.15 K from reference [29].

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G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

and uA1 denotes the volume fraction of the RTIL which are in the
monomer state. This quantity as well as uB1, dened as the volume
fraction of nitromethane molecules which are not associated with
RTIL, are dened by

UA uA1 1 K AB uB1 ;



V
UB uB1 1 B K AB uA1 :
VA

Excess enthalpy is given by

-200

H / (Jmol )

-1

H xB K AB DhAB

/A1

VA
VB

K AB /A1

pM V EC
e2
V
M

 UA pA UB pB pM

V A xA V B xB


eA
eB
eM
V
V
V

!
8

-400
TABLE 9
ERAS-model parameters for pure compounds
MW/
(g  mol1)

0.4

0.6

0.8

where A and B denote the RTIL and nitromethane, respectively.

DhAB and DvAB represent the enthalpy and volume changes of this
reaction. It is worth to note that this cross-association only reverts
on the creation of dimers RTILnitromethane; the own denition of
the association process do not allow the creation of any more complex structure. This is consistent with previous studies on (RTIL +
polar), concretely on the RTILCO2 binary system in the frame of
the tPC-PSAFT model [47,48], in which only one negative and one
positive association sites are considered for the RTIL and CO2,
respectively.
In order to apply ERAS, it is necessary to know the characteristic
parameters V*, T*, and p* of each compound. They were calculated
from density, q, isobaric thermal expansivity, ap, and isothermal
compressibility, jT, at atmospheric pressure and all the studied
temperatures. Further information on the procedure to obtain
them can be found in literature as well as the mixing rules needed
to calculate V*, T*, and p* for mixtures [52].
Considering that the compounds that form the binary mixtures
only cross-associate, VE is given by

V E xB K AB DvAB

/A1

VA
VB

K AB /A1

e M  UA V
e A  UB V
eB ;
 V


xV A

xV A
1  xV B

S/nm

817.53
820.71
821.34
819.13
814.51
807.04

4750
4752
4764
4785
4815
4852

0.153266b

[bpyr][BF4]

237.045

293.15
298.15
303.15
308.15
313.15
318.15

173.10
173.10
173.26
173.57
174.05
174.69

593.14
598.89
600.62
598.01
590.94
579.16

7326
7328
7365
7440
7555
7713

0.113515b

[bmim][BF4]

226.023

293.15
298.15
303.15
308.15
313.15
318.15

162.05
162.18
162.32
162.45
162.60
162.74

609.88
608.16
604.90
607.34
609.59
611.62

7221
7255
7289
7323
7358
7392

0.104371a

[hmim][BF4]

254.076

293.15
298.15
303.15
308.15
313.15
318.15

190.80
191.08
191.37
191.65
191.94
192.24

561.26
559.93
558.71
557.33
555.83
554.32

7074
7132
7190
7248
7307
7367

0.104445a

[emim][EtSO4]

236.29

293.15
298.15
303.15
308.15
313.15
318.15

166.38
166.50
166.63
166.77
166.91
167.03

648.35
651.01
653.49
655.62
657.71
659.60

7615
7651
7687
7723
7759
7795

0.104045b

[bmim][MetSO4]

250.316

293.15
298.15
303.15
308.15
313.15
318.15

180.36
180.58
180.81
181.04
181.28
181.53

626.28
626.15
625.78
625.06
624.16
622.90

7551
7610
7669
7728
7788
7848

0.105712b

[emim][triate]

260.235

293.15
298.15
303.15
308.15
313.15
318.15

161.62
161.78
161.95
162.12
162.30
162.47

597.79
599.19
600.45
601.56
602.55
603.43

7086
7126
7167
7207
7248
7289

0.100783b

[bmim][triate]

288.288

293.15
298.15
303.15
308.15
313.15
318.15

191.05
191.22
191.38
191.56
191.73
191.91

536.78
538.51
540.14
541.66
543.06
544.51

7068
7102
7136
7171
7205
7240

0.104305a

e V=V  and subscripts M, A, and B denote the properties of

where V
mixture, pure ionic liquid, and nitromethane, respectively. Ui are
the hard core volume fractions, dened as

UA 1  UB

T*/K

41.82
41.83
41.87
41.94
42.04
42.17



V A xA V B xB
4

p*/
MPa

293.15
298.15
303.15
308.15
313.15
318.15

x
FIGURE 3. Excess molar enthalpy for x RTIL + (1  x) nitromethane at 303.15 K; (j)
[bmpyr][BF4]; (h) [hmim][BF4]; () [emim][EtSO4]; () [emim][triate]; (M)
[bmim][triate]; () equation (2) at 303.15 K; (- - -) [bmim][BF4] and (  )
[bmim][MetSO4] from reference [31].

V*/
(cm3  mol1)

61.04

Nitromethane

-600

0.2

T/K

a
b

Reference [50].
Reference [51].

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G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

substance [50,51]. These ratios for the studied systems as well as

their source are given in table 9.
XAB is the physical binary interaction parameter, which is proportional to the difference between the physical interactions between like and unlike molecules that form the mixture. These
physical interactions refer to all interactions that are not involved in the association process, which are called chemical interactions. XAB was supposed to be linearly dependent on
temperature

TABLE 10
ERAS-model parameters for mixtures of RTIL + nitromethane

[bmpyr][BF4]
[bmim][BF4]
[hmim][BF4]
[emim][EtSO4]
[bmim][MetSO4]
[emim][triate]
[bmim][triate]

KAB

DhAB/
(J  mol1)

DvAB/
(cm3  mol1)

X 0AB

dXAB/dT

0.72
0.81
1.26
0.45
0.68
0.99
1.65

12262
12262
12262
12262
12262
12262
12262

11.64
11.64
11.64
11.64
11.64
11.64
11.64

1.3
0.8
26.5
16.5
0.3
21.2
43.4

0.201
0.232
0.329
0.093
0.143
0.302
0.395

X AB X 0AB dX AB =dTT  T 0 ;

12

X 0AB

where
is the value of the parameter at the reference temperature T0 (298.15 K).
Analytic expressions for C Ep can be derived from HE from its
denition

and pM is given by

pM UA pA UB pB  UA HB X AB ;

where HB, the surface fraction of component B can be obtained by

HB 1  HA

SAB UB
UA SAB UB

C Ep

10

SA
;
SB

!
13

;
p

nevertheless, we have found that the results obtained by numerical

differentiation are the same.
Therefore, once pure product parameters are calculated, ve
system-dependent quantities must be determined by tting to
the thermodynamic data of the mixtures: KAB, DhAB, DvAB, XAB,
and dXAB/dT. The presented experimental data for VE, C Ep , and HE
were used to t the system-dependent parameters of ERAS by

and SAB is dened as

SAB

oHE
oT

11

where SA and SB are the surface to volume ratio of each compound,

which can be obtained from the molecular structure of the

1.0

V E/ (cm3mol-1)

0.5
0.0
-0.5
-1.0
-1.5

(b)

(a)

(c)

(d)

(e)

(f)

(g)

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

FIGURE 4. Excess molar volume for x RTIL + (1  x) nitromethane at 298.15 K; () experimental data; () ERAS prediction; (- - -) ERAS physical contribution; (  ) ERAS
chemical contribution for: (a) [bmpyr][BF4]; (b) [bmim][BF4]; (c) [hmim][BF4]; (d) [emim][EtSO4]; (e) [bmim][MetSO4]; (f) [emim][triate]; and (g) [bmim][triate].

800

(b)

(a)

(c)

(d)

(e)

(f)

(g)

-1

H / (Jmol )

400

-400

-800
0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

FIGURE 5. Excess molar isobaric heat capacity for x RTIL + (1  x) nitromethane at 298.15 K; () experimental data; () ERAS prediction; (- - -) ERAS physical contribution;
(  ) ERAS chemical contribution for: (a) [bmpyr][BF4]; (b) [bmim][BF4]; (c) [hmim][BF4]; (d) [emim][EtSO4]; (e) [bmim][MetSO4]; (f) [emim][triate]; and (g)
[bmim][triate].

340

G. Garca-Miaja et al. / J. Chem. Thermodynamics 41 (2009) 334341

(b)

Cp / (Jmol-1K -1)

(a)

(d)

(c)

(f)

(e)

(g)

-4

-8
0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

0.2 0.4 0.6 0.8

FIGURE 6. Excess molar enthalpy for x RTIL + (1  x) nitromethane at 303.15 K; () experimental data; () ERAS prediction; (- - -) ERAS physical contribution; (  ) ERAS
chemical contribution for: (a) [bmpyr][BF4]; (b) [bmim][BF4]; (c) [hmim][BF4]; (d) [emim][EtSO4]; (e) [bmim][MetSO4]; (f) [emim][triate]; and (g) [bmim][triate].

using the Marquardt algorithm. This was done in two stages: Initially, all ve parameters were allowed to be varied. Since DhAB
and DvAB acquired similar values for all systems, we decided to
x them to the mean value and t the other parameters, i.e. KAB,
XAB, and dXAB/dT. The nal values for all system-dependent parameters are listed in table 10.
The results at 298.15 K for VE and C Ep , and at 303.15 K for HE are
presented together with experimental data in gures 46. The
physical and chemical contributions are also shown. It is observed
that the results are good; all data are properly reproduced by the
model. Small values for the equilibrium constant KAB where found,
indicating that even though cross-association is present it is weak,
fact corroborated by the DhAB value of 12262 J  mol1. It was obtained a highly negative DvAB value (11.64 cm3  mol1), which is
responsible for the quite negative data of VE. It is worth noting that
the xed values of DhAB and DvAB were enough for describing all
studied properties for all studied systems and KAB is very similar
for all the binary systems, which indicates that cross association
RTILnitromethane there must be akin for all the mixtures. As for
the physical interaction parameter XAB, it was found quite different
values; in fact, since cross-association is very similar for all systems, this parameter produces the most important differences between the studied systems; as can be seen in gures 4 and 5, XAB
mainly indicates the magnitude of the physical contribution to VE
and HE. The temperature dependence of the physical contribution
parameter dXAB/dT presents in all cases a small negative dependence, which causes the negative sign of the C Ep physical contribution (see gure 6). At last it must be noted that chemical
contribution to C Ep is positive, fact which comes from the strong
dependence of association against temperature: as temperature
is increased, cross-association is destroyed, reverting in an increment of entropy against temperature higher than in an ideal mixture, and, therefore, in a positive contribution to C Ep .
5. Conclusions
Excess molar volume, heat capacity, and enthalpy were measured for a set of binary systems of RTIL + nitromethane, showing
all the systems a quite similar behavior, which does not highly
deviate from that of the ideal mixture. In order to get information
about the microscopic processes involved in the mixing process,
the ERAS-model was applied to experimental data under the
assumption that both compounds do not self-associate but they
cross-associate, obtaining good results for the studied excess properties. The analysis of the ERAS parameters revealed that crossassociation is very similar for all the systems and the observed

differences mainly comes from the physical contribution, i.e., from

differences in non-specic interactions between the RTILs and
nitromethane.
Acknowledgements
The authors are grateful to the Direccin Xeral de I + D da Xunta
de Galicia (Project # PGIDIT-03-DPI-38301-PR) and to the
Ministerio de Educacin y Ciencia, Secretara de Estado de Poltica
Cientca y Tecnolgica del Gobierno Espaol (Projects #
BFM2003-09295 and # MAT2006-12984) for nancial support. G.
Garca-Miaja is supported by the Programme Alban, the European
Union Programme of High Level Scholarships for Latin America,
Scholarship No. E05D056044MX.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jct.2008.09.002.
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JCT 08-258