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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
InCl
4
ZnCl
3
CuCl
2
NbF
6
TaF
6
Fe
2
Cl
7
Zn
2
Cl
5
Zn
3
Cl
7
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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