Beruflich Dokumente
Kultur Dokumente
pubs.acs.org/jced
Bijan Das*,
Department of Chemistry & Biochemistry, Presidency University, 86/1 College Street, Kolkata 700 073, India
ABSTRACT: Two ionic liquids (ILs), 1-butyl-3-propyl imidazolium bromide ([BPim][Br]) and 1-butyl-3-propyl benzimidazolium
bromide ([BPbim][Br]), have been synthesized from their appropriate imidazole and benzimidazole precursors and were characterized by NMR spectroscopic technique. Their electrical
conductances have been measured as a function of their concentrations in water, methanol, and acetonitrile at three dierent temperatures. The limiting molar conductances (0), the association
constants (KA), and the values of the association diameters (R)
of these ILs have been obtained by analysis of the conductance
data using the Fuoss conductance equation. These ILs have been
found to remain unassociated in water and methanol, whereas
these exhibit slight ionic association in acetonitrile within the
investigated temperature range. The temperature elevation causes an increase in their limiting molar conductances in the three
solvents under investigation. The IL cations [BPim]+ and [BPbim]+ exist as unsolvated species in aqueous solutions, whereas
substantial solvation was noticed for the [BPim]+ ion in methanol and acetonitrile solutions.
INTRODUCTION
EXPERIMENTAL SECTION
Chemicals. Acetonitrile (purity: 99 %) was purchased from
E. Merck, India; it was puried by distillation with P2O5 followed
by redistillation over CaH2. Methanol (purity: 99.9 %) was
procured from Acros Organics and was distilled three times.
Deionized triply distilled water was used for the preparation of
solutions; its specic conductivity was of the order of 0.1 mSm1
at 308 K. The densities (0) and the viscosity coecients (0) of
the solvents thus puried are shown in Table 1, and these
properties agree well with those reported in the literature.2024
The relative permittivities () of these solvents were obtained
from the literature,2023 and these are also listed in Table 1.
The relative permittivity of methanol at 313 K is not available
in the literature, and this was obtained from an interpolation
of the available experimental relative permittivity values in the
temperature range (278 to 328) K.21 1-Bromopropane (purity:
98.5 %), 1-bromobutane (purity: 98 %), and benzimidazole
(purity: 99.5 %) were purchased from Loba Chemie, India, and
imidazole (purity: 99 %) was purchased from SRL, India; these
were used without further purication.
Ionic liquids (ILs) constitute a group of molten organic electrolytes whose chemical and physical properties could be conveniently
engineered by judicious choice of their anions, cations, and the
substituents. They possess specic properties, for example, negligible
vapor pressures, noninammability, good thermal stability under
ordinary conditions, and outstanding catalytic properties, and
above all they oer excellent solubility for inorganic and organic
compounds.14 Recent years have, therefore, witnessed an upsurge
of interest in ILs in the eld of scientic research opened up by the
possibility of their applications in novel eco-friendly and benign
industrial processes.511 Plenty of physicochemical investigations
have, so far, been performed on pure ILs as well as on their
mixtures with molecular solvents.1215 However, only in a limited
number of cases, the innite dilution molar properties1619 were
obtained despite their importance in understanding the ionion
and ionsolvent interactions and the possibility of prediction of
ILs in specic applications such as IL-based chemical reactions.
This article reports the electrical conductances measured for
1-butyl-3-propyl imidazolium bromide ([BPim][Br]) and 1-butyl3-propyl benzimidazolium bromide ([BPbim][Br]) dissolved in
water, methanol, and acetonitrile at (308, 313, and 318) K at
0.1 MPa as a function of concentration of these ILs with a view
to unravel their association and solvation behavior.
2012 American Chemical Society
Article
this work
308
313
318
0.99407
0.99221
0.99024
308
313
318
0.77718
0.77250
0.76770
308
0.76564
313
318
0.75970
0.75501
0/mPas
lit.
this work
Water
0.9940622
0.7194
0.9922422
0.6533
0.9902422
0.5966
Methanol
0.7772023
0.4747
0.4440
0.7677023
0.4185
Acetonitrile
0.7658124
0.3125
0.766225
0.7656026
0.3042
0.7527124
0.2903
0.755925
lit.
0.719422
0.653122
0.596322
74.8222
73.1522
71.5122
0.474223
30.7423
29.81b
28.9223
0.417423
0.31424
24
0.293
0.28925
34.124
34.5425
33.8525
33.1225
a
The uncertainty u is u(T) = 0.05 K. Combined expanded
uncertainties are Uc(0) = 0.00003 gcm3 and Uc(0) = 0.005
mPas (level of condence = 0.95). bObtained from interpolation of
the literature values from ref 21 (please see text).
(1)
p = 1 (1 )
(2)
KA = (1 )/c 2f 2
(3)
ln f =
Figure 1. Structures of the ionic liquids -1-butyl-3-propylbenzimidazolium bromide (1) and 1-butyl-3-propylimidazolium bromide (2).
k
2(1 + kR )
e2
kBT
(4)
(5)
KA = KR (1 + KS)
(6)
26
Article
Table 2. Molalilty Dependence of the Molar Conductances of 1-Butyl-3-propylimidazolium Bromide and 1-Butyl-3propylbenzimidazolium Bromide in Water, Methanol, and Acetonitrile at (308, 313, and 318) K at 0.1 MPaa
104m/molkg1
T = 308 K
T = 313 K
T = 318 K
/Scm2mol1
/Scm2mol1
/Scm2mol1
104m/molkg1
T = 313 K
T = 318 K
/Scm2mol1
/Scm2mol1
1000.40
898.74
762.10
569.63
426.16
319.02
238.91
178.98
134.14
100.54
75.36
56.51
T = 308 K
/Scm2mol1
Standard uncertainties u are u(T) = 0.05 K and u(m) = 0.00002 molkg1, and the combined expanded uncertainty Uc is Uc() = 0.03 Scm2mol1 (level
of condence 0.95).
(7)
Article
T/K
0/Scm2mol1
KA/dm3mol1
R/
2.87
2.57
1.73
0.74
1.16
1.50
0.01
0.02
0.01
0.01
0.01
0.01
8.1
8.0
7.7
12.6
11.4
10.1
0.05
0.06
0.03
0.04
0.02
0.03
2.31
3.06
3.09
0.93
0.58
0.18
0.02
0.05
0.06
0.05
0.04
0.06
4.6
4.8
4.9
5.8
5.8
5.6
0.02
0.04
0.05
0.04
0.04
0.06
32.83
37.61
42.97
49.25
54.76
60.33
0.09
0.12
0.08
0.09
0.09
0.01
7.7
7.2
7.2
10.0
9.7
10.0
0.02
0.02
0.02
0.02
0.02
0.01
Water
[BPim][Br]
[BPbim][Br]
[BPim][Br]
[BPbim][Br]
[BPim][Br]
[BPbim][Br]
308
313
318
308
313
318
130.22
139.89
147.50
108.83
118.87
129.03
308
313
318
308
313
318
79.35
84.75
90.61
79.21
85.09
92.03
308
313
318
308
313
318
128.10
136.41
145.89
166.92
177.04
190.64
0.03
0.05
0.02
0.03
0.02
0.03
Methanol
0.01
0.03
0.04
0.02
0.02
0.04
Acetonitrile
0.04
0.08
0.05
0.05
0.05
0.01
Figure 3. Variation of molar conductivity of 1-butyl-3-propylimidazolium bromide as a function of molality in methanol at dierent
temperatures at 0.1 MPa. The symbols represent the experimental
points, whereas the lines represent the calculations according to eqs 1
through 6. , 318 K; , 313 K; , 308 K.
Figure 2. Variation of molar conductivity of 1-butyl-3-propylimidazolium bromide as a function of molality in water at dierent
temperatures at 0.1 MPa. The symbols represent the experimental
points, whereas the lines represent the calculations according to eqs 1
through 6. , 318 K; , 313 K; , 308 K.
also change in the same order as the limiting equivalent conductivities of the ILs as a whole. It is now well-established33
that some ions exist as bare species (unsolvated) in solution
with sizes being equal to their crystallographic sizes, whereas
others are solvated with a concomitant increase in their actual
sizes in solution. The order of variation of the limiting ionic
equivalent conductivities should, thus, point out the relative
ionic solvodynamic dimensions and hence provide information
on their solvation behavior in solutions.
The ionic mobilities of the IL cations in water decrease in the
order: [BPim]+ > [BPbim]+. This indicates that the larger IL
cation is less mobile than the smaller one in aqueous solution.
This is possible only if the ions remain unsolvated in water; had
these IL cations been hydrated, the smaller ion [BPim]+ with a
higher charge density on its surface would have been more
hydrated compared to the bigger [BPbim]+ ion (with smaller
surface charge density), and hence their ionic mobilities should
(8)
Article
Figure 4. Variation of molar conductivity of 1-butyl-3-propylbenzimidazolium bromide as a function of molality in acetonitrile at dierent
temperatures at 0.1 MPa. The symbols represent the experimental
points, whereas the lines represent the calculations according to eqs 1
through 6. , 318 K; , 313 K; , 308 K.
a0
Water
130.56
108.81
Methanol
79.27
79.03
Acetonitrile
127.91
166.34
a1
r2
1.7280
2.0200
0.9953
0.9996
1.1260
1.2820
0.9994
0.9977
1.7790
2.3720
0.9986
0.9929
CONCLUSIONS
Two ionic liquids, 1-butyl-3-propyl imidazolium bromide
([BPim][Br]) and 1-butyl-3-propyl benzimidazolium bromide
([BPbim][Br]), have been synthesized respectively from their
appropriate imidazole and benzimidazole precursors and characterized by NMR spectroscopic technique. The electrical conductances of these two ionic liquids were measured as functions
of their concentrations in water, methanol, and acetonitrile at
dierent temperatures. Analyses of the conductance data on the
basis of the Fuoss conductance equation provided important
insight into the ion association and solvation behavior on the
investigated ionic liquid solutions.
AUTHOR INFORMATION
Corresponding Author
*E-mail: bijan_dasus@yahoo.com.
Notes
REFERENCES
Article