ISSN 00360244, Russian Journal of Physical Chemistry A, 2009, Vol. 83, No. 11, pp. 18831886.

Pleiades Publishing, Ltd., 2009.

Original Russian Text E.P. Grishina, L.M. Ramenskaya, A.M. Pimenova, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 11, pp. 20722075.
1883
INTRODUCTION
Room temperature molten salts (RTMS) are a
comparatively new continuously broadening class of
compounds. One of the most extensively studied
groups of lowtemperature melts (ionic liquids, ILs) is
N,N'dialkylimidazolium chlorideAlCl
3
systems [1].
Depending on the ratio between melt components,
these systems behave either as Lewis bases (if the
organic salt is present in excess) or as Lewis acids (in
the presence of excess AlCl
3
). In basic ILs, the Al
3+
cation forms the mononuclear complex ion. In
acid ILs, polynuclear complex particles are
present along with .
When transition metal salts are dissolved in chloro
aluminate ionic liquids, the form in which they exist
depends on the composition of the solvent. For
instance, the silver ion is incorporated into halide
complexes in basic systems and exists as a free cation
in acid media [2]. The formation of complex anions
was observed in the solution of MoCl
5
[3], UCl
5

SOCl
2
[4], and other metal chlorides in chloroalumi
nate ILs. According to [5], transition metal salts
MCl
2
(Me = Ni, Mn, and Co) can form with
complex anions with the composition [Me(AlCl
4
)
3
]

in
acid ILs. Review [2] contains data on the electro
chemical precipitation of In, Sb, Te, Cd, Cu, Ag, Pd,
Au, Zn, and Sn from solutions of the corresponding
metal chlorides forming complex ions in basic and
acid chloroaluminate ionic liquids.
According to [610], there are lowtemperature
ionic liquids with metalcontaining anions which, as
distinct from the well studied haloaluminate liquids,
have higher moisture and air stability and are therefore
AlCl
4

Al
2
Cl
7

AlCl
4

AlCl
4

more simple to use. As with chloroaluminate ILs, the

composition of the anionic part of these melts depends
on the molar ratio between mixture components. If the
content of a metal salt does not exceed 50 mol %,
mononuclear complex anions ( , ,
, , , , etc.) are largely
present, and if the fraction of the salt is higher than
50 mol %, polynuclear complex particles ( ,
, , etc.) are formed.
For several ionic liquids of the N,N'dialkylimida
zolium chloridemetal chloride type, melting points
were measured, phase diagrams constructed [1, 6],
and the structure of melts determined [11, 12]. How
ever, for many systems (except chloroaluminate ILs),
such important physicochemical characteristics as
density, viscosity, and electrical conductivity were not
studied. It was well established for hightemperature
binary salt melts [13, 14] that these characteristics
were very sensitive to the formation of complex com
pounds between IL solvents and dissolved metal salts.
Lowtemperature bromide melts, in particular, those
based on 1butyl3methylimidazolium bromide
(BMImBr), were studied to a still lesser extent. At the
same time, the physicochemical properties mentioned
above are of great importance for creating technolo
gies with the use of lowtemperature ionic melts.
The purpose of this work was to study the influence
of temperature and the ratio between the components
on the physicochemical characteristics (density, glass
transition temperature, viscosity, and electrical con
ductivity) of the BMImBrAgBr lowtemperature
liquid.
FeCl
4

InCl
4

ZnCl
3

CuCl
2

NbF
6

TaF
6

Fe
2
Cl
7

Zn
2
Cl
5

Zn
3
Cl
7

The Physicochemical Properties of the LowTemperature Ionic

Liquid Silver Bromide1Butyl3Methylimidazolium Bromide
E. P. Grishina, L. M. Ramenskaya, and A. M. Pimenova
Institute of the Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
email: epg@iscras.ru
Received July 18, 2008
AbstractThe physicochemical properties of the lowtemperature ionic liquid based on 1butyl3meth
ylimidazolium bromide (BMImBr) and silver bromide were studied. Differential scanning calorimetry, Fou
rier transform IR spectroscopy, densimetry, viscometry, and conductometry measurements were performed
to determine the dependences of the parameters under study on the concentration of AgBr. It was shown that
the temperature and concentration behavior of the physicochemical properties of BMImBrAgBr melts
characterized the interaction between the system components with the formation of complex particles.
DOI: 10.1134/S0036024409110132
PHYSICAL CHEMISTRY
OF SOLUTIONS
1884
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 11 2009
GRISHINA et al.
EXPERIMENTAL
Binary electrolyte systems were prepared by
directly mixing the ionic liquid (BMImBr, water con
tent 2.6 wt %, melting point 55 [15]) and silver bro
mide AgBr of kh. ch. (chemically pure) grade at a
temperature insignificantly higher than the melting
point of the IL (~70) [15]. Studies were performed
for mixtures with silver bromide contents = 0.015
0.220 mole fractions (0.0721.225 mol AgBr/kg
BMImBr).
The IR transmission spectra were recorded for
samples squeezed between two KRS5 plates (trans
mission range 4000200 cm
1
) on an Avatar 360
FTIR ESP spectrophotometer.
The density of melts was determined under isother
mal conditions pycnometrically (pycnometer volumes
1, 2, and 5 cm
3
) with respect to water [16] using an
ME215S Sartorius analytical balance; the accuracy of
weighing was 1 10
5
g.
The dynamic viscosity of BMImBrAgBr ionic
liquids was measured at 20 on a BROOKFIELD
DVII + Pro viscometer in a special smallvolume
cell, plate radius 7.5 mm, gap between plates 1 mm,
range of angular rotation velocities 10100 rpm. The
viscometer was calibrated against glycerol [17] to
determine the correction coefficient taking into
account cell design characteristics.
The vitrification of ionic liquid samples was studied
by differential scanning calorimetry on a NETZCH
DSC 204 F1 instrument using an Al capsule; sample
weight was 20 mg, heating was performed in an N
2
atmosphere from 110 to 100, heating rate was
10 K/min. The capsule was prepared following the
standard procedure immediately before each mea
surement.
The conductivity of lowtemperature BMImBr
AgBr melts was determined at 20 0.1 using an
E720 immitance meter in a hermetically closed tem
peraturecontrolled conductometric cell with smooth
platinum electrodes. Measurements were performed
over the alternating current frequency range f = 1
20 kHz using the procedure described in [18]. Con
ductivity G was extrapolated to an infinite frequency in
the G1/f coordinates. The constant of the conducto
metric cell was determined using a 0.01 N solution of
KCl [19], whose electrical conductivity was compara
ble with that of the ionic liquid studied.
RESULTS AND DISCUSSION
The spectral characteristics. The table contains
data on the IR Fourier transform transmission spectra
of the BMImBrAgBr (x = 0.188) ionic liquid over the
frequency range 40002500 cm
1
(similar transmis
sion spectra were obtained for ILs with other compo
sitions). The bands were assigned to atomic group
vibrations according to [20]. A comparison with the
spectrum of initial BMImBr [15] shows that the intro
duction of AgBr causes a bathochromic shift of the
characteristic minimum at 3143 cm
1
corresponding
to the Hbond between the C2 heteroring atom and Br.
Clearly, the salts interact through the bromide ion with
the formation of the [BMImBr (AgBr)] complex salt.
Density. Our studies showed that the density () of
solutions of AgBr in BMImBr linearly increased as the
concentration of the silver salt grew. The dependence
of on the mole fraction of AgBr at 20 was approx
imated by the linear equation = 1.300 + 1.098x (r =
0.998).
According to the literature data, density is not very
sensitive to weak chemical interactions in melts.
Chemical interactions are usually revealed using den
sity temperature coefficient (/t)composition
dependences [13]. Such a dependence for the AgBr
BMImBr system has an extremum at x ~ 0.13 (Fig. 1).
The densities of solutions of AgBr in BMImBr were
used to calculate molar volumes V (V = (M
1
x
1
+
M
2
x
2
)/, where M
1
and M
2
are the molecular weights
of the binary system components). It is shown in Fig. 2
that the experimental molar volumecomposition
dependence ( = 168.4 134.2x, r = 1) has a
positive deviation from additivity over the whole con
centration range studied ( = 168.3 150.0x, r =
0.999). Additive values were calculated using the
density of crystalline AgBr, whose melting point is
424 [21].
The conclusion can be drawn that the BMImBr
AgBr system exhibits concentration and tempera
tureinduced density variations characteristic of
binary melts with chemical intercomponent interac
tions [13].
Vitrification. According to the differential scanning
calorimetry data, the glass transition temperature of a
supercooled BMImBr melt with water impurity is
lower than 70 [15]. For BMImBrAgBr mixtures,
V
mol
expt
V
mol
dd
Characteristics of the IR transmission spectrum (3500
2500 cm
1
) of BMImBrAgBr and BMImBr ionic liquids
, cm
1
Atomic
group
Bond , cm
1
[20]
BMImBr
AgBr
BMImBr
[15]
3473 (
s
) 3442 H
2
O 35003200
2958 (
as
)
2872 (
s
)
2960
2873
CH
3
CH 29752950
28852860
2933 (
as
)
2871 (
s
)
2929
2873
CH
2
CH 29402915
28702845
2733 2733 NCH
3
CH 28202730
3137 ()
3087 ()
3143
3082
CH

CH 30953010
30003100
Note:
s
denotes symmetrical and
as
asymmetric stretching vibra
tions.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 11 2009
THE PHYSICOCHEMICAL PROPERTIES OF THE LOWTEMPERATURE IONIC LIQUID 1885
this temperature is more positive and increases from
70.2 to 48.8 as the content of AgBr grows
from 0.078 to 0.220 mole fractions. According to
[13], an increase in the freezing temperature of
binary melt is evidence of binding of more than one
halide ion of the meltsolvent by dissolved salt mole
cules with the formation of the corresponding com
plex ions.
Dynamic viscosity and electrical conductivity. The
dynamic viscosity values were calculated taking into
account the correction coefficient [15] as the slope of
the straight line in the shear stress ()rate of shear (D)
coordinates [22]. The dependences of on D for
BMImBrAgBr ionic liquids with various composi
tions are shown in Fig. 3. At x
AgBr
< 0.188, the system
behaves like initial BMImBr and exhibits the proper
6
0
7
8
9
0.05 0.10 0.15 0.20
x
AgBr
, mole fractions
(/t) 10
4
, g/(cm
3
K)
Fig. 1. Dependence of /t on the content of AgBr for
BMImBrAgBr melts.
0
170
150
0.1 0.2
x
AgBr
, mole fractions
V, m
3
2
1
Fig. 2. Dependences of the molar volume of BMImBr
AgBr binary melts on the content of AgBr at 20:
(1) experimental dependence and (2) dependence based
on the additivity rule.
10
4
, P
1.2
0
1.0
0.8
20 60 40 80
D, rad/s
4
3
2
1
Fig. 3. Dependence of dynamic viscosity on the rate of
shear D in the BMImBrAgBr system at AgBr contents
(mole fractions) of (1) 0, (2) 0.120, (3) 0.169, and (4) 0.188.
10
4
, P
1.4
0
1.0
0.6
0.2
0.05 0.10 0.15 0.20
40
30
20
10
0
10
4
, Sm/m
x
AgBr
, mole fractions
Fig. 4. Dependences of specific conductivity and
dynamic viscosity on the ratio between BMImBrAgBr
binary melt components at 20.
1886
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 11 2009
GRISHINA et al.
ties of Bengham liquids. Initially, they are character
ized by an increase in viscosity. When the yield point is
reached, the system behaves as a Newton liquid, and
is independent of D. At x
AgBr
0.188, BMImBrAgBr
binary melts behave like BMImBr (with a 1.78 wt %
water content) [15], that is, like a highly structured
dilatant liquid, and increases as D grows [23].
The influence of the composition (x) on and spe
cific conductivity () of BMImBrAgBr melts is shown
in Fig. 4. We see that the saltsolvent (BMImBr) has a
lower conductivity at 20 than dilute solutions of
AgBr in it. At this temperature, BMImBr is in the
metastable supercooled melt state (melting point
55 [15]) with a sharply decreased ability to experi
ence viscous flow, whereas binary systems are liquids
under these conditions. The viscosity isotherm in the
region of compositions under consideration passes a
minimum. Such a concentration behavior of viscosity
is characteristic of melts of salts in the associated state,
which dissociate when mixed with other salts [13]. The
value sharply decreases as the content of AgBr in
melts increases. This can be related to the formation of
largesized silvercontaining complex ions with low
mobility [14].
To summarize, the experimental propertycom
position dependences for the lowtemperature
BMImBrAgBr ionic liquid have the form character
istic of binary melts with intercomponent interaction
of the complex formation type.
ACKNOWLEDGMENTS
This work was financially supported by Program
no. 9 of the Division of Chemistry and Materials Sci
ence, Russian Academy of Sciences, New
Approaches to Improvement of Corrosion and Radia
tion Resistance of Materials and Radioecological
Safety, project no. 1.
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