ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2008, Vol. 82, No. 7, pp. 1098–1103. © Pleiades Publishing, Ltd.

, 2008.
Original Russian Text © L.M. Ramenskaya, E.P. Grishina, A.M. Pimenova, M.S. Gruzdev, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 7, pp. 1246–1251.

PHYSICAL CHEMISTRY
OF SOLUTIONS

The Influence of Water on the Physicochemical Characteristics

of 1-Butyl-3-methylimidazolium Bromide Ionic Liquid
L. M. Ramenskaya, E. P. Grishina, A. M. Pimenova, and M. S. Gruzdev
Institute of the Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
e-mail: LMR@isc-ras.ru
Received December 20, 2006

Abstract—A modified synthesis of 1-butyl-3-methylimidazolium bromide (BMImBr) was suggested and per-
formed, and some physicochemical properties of the product containing 0.64–13.6 wt % water were deter-
mined. Water increased the electrical conductivity and decreased the viscosity and melting point of the sub-
stance but weakly influenced its density. Water in amounts of 5–8 wt % (45–50 mol %) caused structural
changes. The BMImBr · 0.5H2O crystal hydrate was found to be stable thermodynamically.
DOI: 10.1134/S003602440807008X

INTRODUCTION BMImBr and studies of the influence of water on them

Salts-ionic liquids (ILs) molten at room temperature
as a rule consist of N- or P-containing organic cations
and bulky organic or inorganic anions [1]. Thanks to
their unique properties (high electrical conductivity, a
broad temperature range of the liquid state, thermal sta-
bility, and low volatility), they are treated as new prom-
ising green (environmentally friendly) solvents in
organic synthesis and chemical analysis and electro-
lytes in electrochemical energy accumulators [1, 2].
Successful use of ILs requires thorough studies of
their properties. The purpose of this work was the prep-
aration and determination of some physicochemical
characteristics of 1-butyl-3-methylimidazole bromide
(BMImBr) with various water contents,
– acetonitrile and ethyl acetate. The product was dried in
H3C N N C H Br .
4 9
Although 1,3-substituted imidazolium halides are
extensively used for the preparation of other more com-
plex ILs with complex anions, their physicochemical
properties have been studied incompletely. According
to the Catalog of Ionic Liquids (Merck Darmshtad,
Germany [3]), the melting point of BMImBr (99.9%
major component) is 76°ë. The density (1.77 g/cm3,
20°ë), melting point (65°ë), and decomposition tem-
perature (275°ë) of crystalline BMImBr containing
1.09–1.62 wt % water were reported in [4]. According
to [5], the density obtained from the X-ray diffraction
data on BMImBr crystals is 1.44 g/cm3.
As is well known, water is an inevitable ionic liquid
impurity [1], and the properties of ionic liquids, espe-
cially those of hydrophilic 1-butyl-3-methylimidazo-
lium halides, depend strongly on its content. The deter-
mination of the physicochemical characteristics of
are therefore problems of current interest.
EXPERIMENTAL
We used N-methylimidazole (Acros organics, 99%)
and freshly distilled 1-bromobutane of ch. (pure) grade
as reagents. Acetonitrile and ethyl acetate of kh. ch.
(chemically pure) grade were dehydrated following
standard procedures [6].
The quartenization reaction was performed using a
modified procedure with the direct interaction of the
reagents in a small excess of alkyl halide [7, 8]. We sug-
gested the procedure with adding butyl bromide drop-
wise to N-methylimidazole under intense stirring
strictly at 70°ë. The reaction mixture was treated with
activated carbon and recrystallized from a mixture of
a rotary vacuum evaporator at a pressure of 0.66 kPa
until its weight ceased to change and stored in a desic-
cator at a residual humidity of 5 × 10–3 mg/l. This pro-
cedure gave 1-butyl-3-imidazolium bromide in the
form of a white crystalline mass. The purity and struc-
ture of the product were controlled by melting point
measurements and using thin-layer chromatography,
chromato-mass spectrometry, and NMR and IR spec-
troscopy.
The yield was ~97.5%, Tm = 76.4°ë, water content
0.64 wt %. The 1ç NMR spectrum (D2O, ppm): δ = 0.8
(triplet, J = 7.1 Hz, 3H, –CH3), 1.21 (sextet, J = 7.6 Hz,
2H, CH3–ëH2–(ëH2)N), 1.73 (quintet, J = 7.6 Hz, 2H,
N–ëH2–ëH2–), 3.81 (singlet, J = 7.01 Hz, 3H, N–ëH3),
4.07 (triplet, J = 9.1 Hz, 2H, N–ëH2–), 7.31 (doublet,
J = 5.01 Hz, 2H, N–ëH–ëH–N), and 8.6 (singlet, J =
5.01 Hz, 1H, N–ë(H)–N). The 13ë NMR spectrum
(D2O, ppm, external reference cyclohexanol): δ =
15.72, 34.21, 36.04, 38.69, 54.14, 124.16, 126.39, and

1098
 THE INFLUENCE OF WATER ON THE PHYSICOCHEMICAL CHARACTERISTICS
(a)
4.5 4.0
δ, ppm
Fig. 1. Fragments of 1H NMR spectra of 1-butyl-3-methylimidazole (a) before and (b) after purification.
141.16. Mass spectrum, m/z: 219 [M]+, 125 [M–Me]+,
97 [å–ëH2–CH2–åÂ]+, and 82 [å–C(H)NC(H)–
ëH2–CH2–CH2–åÂ]+.
The chromatograms and mass spectra were obtained
on a Saturn 2000R chromato-mass spectrometer, car-
rier gas helium. The 1H and 13C NMR spectra were
recorded on a Bruker AC-200 (200.13 MHz) instrument
for solutions in D2O. The IR transmission spectra were
studied for samples placed between two KRS-5 win-
dows (transmission range 4000–200 cm–1) on an Avatar
360 FT-IR ESP spectrophotometer. The content of
water (x) in wt % was determined by amperometric
titration according to Fischer [9]. We also synthesized
BMImBr samples with residual water contents of 0.75,
1.78, and 2.6 wt %. BMImBr samples enriched in water
(4–13 wt % ç2é) were prepared by diluting the initial
IL. Water content was controlled according to Fischer.
The phase state and thermal stability of the samples
were studied by thermogravimetry and differential
scanning calorimetry. Thermogravimetric (TG) mea-
surements were taken on a NETZCH TG 209 F1 ana-
lyzer in an argon flow (20 ml/min). The differential
scanning calorimetry (DSC) data were obtained on a
NETZCH DSC 204 F1 instrument, cell material Al,
sample weight ≈20 mg, heating in N2 from –110 to
100°ë, heating rate 10 K/min. The cell was prepared
following the standard procedure directly before each
measurement.
The density of solid and molten BMImBr was deter-
mined at a constant temperature (20, 40, 60, and 80°ë)
with respect to ethyl acetate and water by the volumet-
ric and pycnometric methods [10]. Pycnometer vol-
umes were 1, 2, and 5 cm3. The dynamic viscosity of
molten BMImBr at x = 2.6–10.2 (x is wt % H2O) was
determined on a BROOKFIELD DV-II+Pro viscometer
at 20°ë in a special small-volume cell, plate radius
7.5 mm, gap between plates 1 mm, interval of angular
rotation rates from 10 to 100 rpm. The viscometer was
calibrated against glycerol [11], and a correction coef-
ficient taking into account the special features of the
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1099
(b)
3.5 4.5 4.0 3.5
δ, ppm
design of the cell was determined. After measurements,
the content of water was determined as specified above.
Changes in the content of water did not exceed 0.3–
0.5 wt %.
The conductivity of the solid salt and supercooled
and moistened molten BMImBr was determined using
an R5021 ac bridge in a hermetically sealed tempera-
ture-controlled conductometric cell with smooth plati-
num electrodes. Measurements were taken over the
alternating current frequency range f = 1–20 kHz at
20°ë following the procedure described in [12]. The
conductivities G were then extrapolated to an infinitely
high frequency in the G – 1/f coordinates. The cell con-
stant was determined similarly with the use of a 0.01 N
solution of KCl, because the electrical conductivity of
this solution was comparable with that of molten
BMImBr.
RESULTS AND DISCUSSION
Spectral characteristics.Fragments of the 1H NMR
spectra of BMImBr (0.64 wt % ç2é) (a) before and
(b) after purification are shown in Fig. 1. The absence
of the δ = 3.6 ppm singlet responsible for methyl group
protons in the spectrum of initial N-methylimidazole
was evidence that the product synthesized was a pure
individual compound without initial reagent impurities.
The chromato-mass spectrometry and NMR spectros-
copy data and the melting point (76.4°ë) allow the
product obtained to be identified as 1-butyl-3-meth-
ylimidazolium bromide.
The IR transmission spectra of BMImBr containing
2.6 (and 6.5, parenthesized values) wt % water over the
frequency ν range 4000–500 cm–1 are presented in
Table 1. The spectra contain the characteristic vibration
frequencies of all the structural elements of the BMIm+
cation [13]. Anion–cation interactions in IL based on
imidazole change C–H ring proton binding (3000–
3200 cm–1) [14]. Along with a strong aromatic ring C–H
hydrogen bond at 3082 cm–1, the spectrum of BMImBr
Vol. 82 No. 7 2008
1100 RAMENSKAYA et al.

Table 1. Characteristics of vibrational-rotational transmission spectrum of 1-butyl-3-methylimidazole bromide (2.6 wt % H2O)

This work [13]
ν, cm–1 I, % group bond ν, cm–1
νs 3442 11.04 (28.10) H2O O–H 3500–3200
δas 652 41.88 (50.11) 600–200
δs 622 32.72 (45.75)
νas 2960 15.74 (32.86) –CH3 C–H 2975–2950
νs 2873 23.14 (38.04) 2885–2860
δas 1465 29.29 (43.21) 1470–1435
δs 1382 41.31 (50.97) 1385–1370
νas 2929 weak –CH2– C–H 2940–2915
νs 2973 23.14 (38.04) 2870–2845
2733 weak N–CH3 C–H 2820–2730
ν 3143 (3144) 20.27 (35.46) –CHarom C–H 3095–3010
ν 3082 (3085) 18.19 (36.8) 3000–3100
ν 841 (844) 46.08 (53.59) 900–700
ν 1628 34.79 (45.55) C–Cnonconj C–C 1680–1620
ν 1571 21.59 (38.44) C–Carom C–C 1600–1500
ν 1520 45.04 C–Ncycl C–N 1600–1480
1429 39.48 (49.67) C–C, C–N C–C, C–N 1400–900
950 53.29 (58.87) C–C C–C 1100–900
δ 1337 42.63 (51.88) –(CH2)n– C–H 1350–1180
ν 1279 weak C–N C–N 1360–1000
δ 1169 15.74 (33.02) CHarom C–H 1175–1125
δ 1113 44.78 (53.16) C–H 1110–1070
δ 1022 50.75 (57.09) (1,3-substitution) 1070–1000
δ 754 38.82 (48.98) 810–750
Note: ν and δ are the stretching and bending vibrations, respectively; νs (δs) and νas (δas) are the symmetrical and asymmetric vibrations,
respectively; values for BMImBr with 6.5 wt % H2O are given in parentheses; I is the intensity.

contains a weaker band at 3143 cm–1 corresponding to
ring proton binding with the bromide ion. Water weak-
ens C–H interactions and causes hypsochromic shifts
of maxima by 1–3 cm–1 and an increase in the intensity
of transmission, especially at high frequencies, because
of the superposition of natural O–H bond vibrations
(3500–2500 cm–1) on the characteristic vibrations of
atomic groups in this spectral region.
Crystallization and hygroscopicity. At room temper-
ature, BMImBr (less than 1 wt % ç2é) is a solid salt,
and BMImBr containing more than 1 wt % and less
than 6.5 wt % water can exist in both solid and liquid
states (as a supercooled melt). BMImBr enriched in
water (7 wt % ç2é) stratifies into two phases, transpar-
ent crystals of the composition BMImBr · 0.5ç2é
(3.5 wt % ç2é) and liquid BMImBr (8 wt % ç2é).
BMImBr with more than 7–8 wt % ç2é is a homoge-
neous liquid system that does not form crystals. A
supercooled melt is in a metastable state. At room tem-
perature, it can remain a viscous liquid indefinitely or
experience spontaneous solidification during several
minutes. Crystallization can be initiated by the intro-
duction of crystallization centers or mechanical or tem-
perature actions.
1-Butyl-3-imidazole bromide is infinitely miscible
with water and intensely absorbs it from air. Its hygro-
scopicity decreases as the amount of absorbed water
grows. At 20°ë and a humidity of 78%, BMImBr with
various initial contents of water reaches maximum sat-
uration of 10–11 wt % ç2é (Fig. 2). The influence of
water on physicochemical characteristics was studied
for systems containing more than 2.6 wt % water,
which are stabler toward the action of atmospheric
moisture.
Thermal data. The thermodynamic parameters
obtained from DSC (Fig. 3) and TG (Fig. 4) heating
cycles for the initial solid BMImBr salt samples at x =

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 82 No. 7 2008

 THE INFLUENCE OF WATER ON THE PHYSICOCHEMICAL CHARACTERISTICS 1101

∆m, % exe

12
1
2 1, 1'
3
8

2'
2
4
4
3'
3
0 4 8 12 –60 –20 20 60 100
τ, days t, °C

Fig. 2. Increase in the weight (∆m) of 1-butyl-3-methylimi- Fig. 3. DSC curves of 1-butyl-3-methylimidazole bromide
dazole bromide depending on the content of water at 20°C, with water contents x = (1, 1') 0.64, (2, 2') 1.78, and (3, 3')
x = (1) 0.64, (2) 1.78, (3) 2.6, and (4) 7 wt % water; humid- 2.6 wt %; (1–3) the first heating and (1'–3') the second heat-
ity 78%. ing.

0.64–2.6% are listed in Table 2. Vitrification is observed the ρ(T) straight line is maximum at x = 5.5%. Presum-
for virtually all the salt compositions at temperatures ably, water-containing BMImBr experiences structural
from –60 to −70°C. It is accompanied by a heat capac- changes at x = 5–6 wt % (~45 mol % water).
ity change ∆Cp of 0.3–0.4 J/(g K). The glass transition Densimetric measurements (20°ë) were used to cal-
Tg and melting Tm temperatures decrease as the content culate the molar volume of solid BMImBr with x =
of water increases. The Tg(x) dependence has an extre- 2.6% (153.1 cm3) and its supercooled melt (168.4 cm3).
mum related to polymorphism. During cooling in the It follows that the solid liquid phase transition is
presence of solvent particles (ç2é), not only the ther- accompanied by a ~10% increase in the molar volume,
modynamically stable rhombic polymorph characteris- which closely agrees with the data on melts of other
tic of anhydrous BMImBr, but also the less stable mon- organic salts [16].
oclinic polymorph is likely formed [5]. A decrease in Viscosity. The dynamic viscosities η of BMImBr
Tm is caused by the formation of BMImBr · nç2é crys- melts with x = 2.6–13.6% determined at 20°C are listed
tal hydrates characterized by lower melting points com- in Table 3. The η values were calculated as slopes of the
pared with the anhydrous salt [4, 7, 15]. Water destabi-
lizes the crystal lattice of 1-butyl-3-methylimidazo-
lium bromide. For this reason, glass crystal and ∆m, %
crystal melt phase transitions are not reproduced 120
during heating of BMImBr containing more than 1 wt
% water (Fig. 3). These transitions are, however, 1
observed for the anhydrous salt (x < 1%).
The decomposition of BMImBr (Fig. 4) occurs with 80
the loss of virtually the whole mass. It follows from
Table 2 that water decreases the temperature at which
decomposition begins and increases weight loss (∆m) 1
before the beginning of thermal destruction. 2, 3
40
Density. The densities ρ of BMImBr samples with
x = 2.6–13.6% at various temperatures are listed in
Table 3. The densities of solid BMImBr with x = 0.64,
1.78, and 2.6% (1.42, 1.40, and 1.43 g/cm3, respec- 0
tively) are in satisfactory agreement with the data from 300 600 900
[5]. The density of molten BMImBr, like the densities t, °C
of other ILs [1, 7, 15], decreases insignificantly as the
content of water and temperature increase. The temper- Fig. 4. TG curves of 1-butyl-3-methylimidazole bromide
ature expansion coefficient KT calculated as the slope of with water contents x = (1) 0.64, (2) 1.78, and (3) 2.6 wt %.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 82 No. 7 2008

1102 RAMENSKAYA et al.

Table 2. Thermochemical parameters of 1-butyl-3-methylimidazolium bromide (x is the content of H2O, wt %)

Vitrification Crystallization Melting Decomposition

x
–tg , °C ∆Cp , J/(g K) tc , °C ∆Hc , J/g tm , °C –∆Hm , J/g tinit , °C –∆m, %

0.64 60.5 0.40 30.4 69.2 77.4 66.2 230 0.7

0.75 73.9 0.34 37.0 56.0 69.8 45.8 224 1.75
1.78 76.6 0.28 None None 50.7 54.4 219 2.03
2.60 – – – – 55.2 30.8 117 3.48
2.85 72.6 0.38 None None 2.4 0.12 110 3.75
7.0 1.60
Note: The data on melting at x = 2.6 wt % were obtained from the first heating cycle without preliminary cooling.

Table 3. Density (ρ, g/cm3), temperature expansion coefficient (KT , g cm–3 K–1), specific conductivity (χ, S m–1), and dy-
namic viscosity (η, cP) of molten BMImBr

ρ
x –KT × 104 χ20 η20
20°C 40°C 60°C 80°C

2.6 1.30 1.29 1.28 1.26 6.5 0.027 830

2.6* 1.43 – – – – 0.016 –
4.2 1.29 1.28 1.26 1.25 7.3 0.076 320
5.5 1.28 1.26 1.25 1.23 8.2 0.229 185
6.8 1.28 1.27 1.24 1.24 6.2 0.453 130
8.1 1.29 1.28 1.26 1.25 6.6 0.645 105
10.2 1.27 1.26 1.24 1.23 7.3 0.551 99
13.6 1.27 1.25 1.24 1.23 6.1 – –
* Solid salt.

dependences of shear stress τ on the rate of shear D tak-
ing into account the correction coefficient [17]. The
results obtained show that, unlike ρ, η strongly depends
on the concentration of water. BMImBr melt is a vis-
cous liquid at room temperature even at x = 2.6%. High
η values distinguish imidazolium halides from the
majority of ILs [1]. For instance, η = 1110 cP (25°ë)
for BMImI at x = 0.19% [15].
The dependences of η on D for BMImBr melts
with various water contents are shown in Fig. 5.
Water-containing BMImBr behaves similarly to
other ILs (as a Newton liquid), whose dynamic vis-
cosity is independent of the rate of shear [1]. More
viscous BMImBr (x = 1.78%) is, however, not a
Newton liquid and exhibits properties of a highly
structured crystal-like liquid [18].
Electrical conductivity. There are no literature data
on the electrical conductivity of 1-butyl-3-methylimi-
dazolium bromide, because this salt is usually in the
solid state at 20°ë. In this work, we measured the con-
ductivity of a supercooled melt and solid BMImBr with
x = 2.6%. The supercooled melt was placed into a cell
and crystallized, after which conductivity was mea-
sured. A change in the state of aggregation of the salt
(liquid solid) decreases its conductivity almost
twofold (Table 3). The specific conductivity of the solid
salt is commensurate with the χ value of the melt, likely
because of strong structure imperfection of BMImBr
crystals and mobility of ions caused by the presence of
water. The influence of water on χ of molten BMImBr
is shown in Table 3. The dependence of χ(BåImBr)
on the content of water has a maximum at x = 7–8%
(~50 mol % H2O). After correcting χ for viscosity (χη),
the maximum remains, as is characteristic of systems
with pronounced intercomponent interactions (mole-
cules, salt dissociation products, and water mole-
cules) [19].

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 82 No. 7 2008

 THE INFLUENCE OF WATER ON THE PHYSICOCHEMICAL CHARACTERISTICS
η, ÒP
1 J. Appl. Electrochem. 31, 1089 (2001).
1400
1200
~
~ (4–6), 353 (2001)].
600
400
200
0 20 40 60 80
D, rad/s
Fig. 5. Dependences of dynamic viscosity (η) on the rate of
shear (D) for supercooled melts of 1-butyl-3-methylimida-
zolium bromide with water contents x = (1) 1.78, (2) 3.0,
(3) 4.0, (4) 7.0, and (5) 8.6 wt % at 20°C.
To summarize, water substantially influences the
state of aggregation and physicochemical properties of
1-butyl-3-methylimidazolium bromide. An increase in
the content of water damages salt crystallinity,
increases electrical conductivity, and decreases viscos-
ity and melting point, but weakly influences density.
Water in amounts of 5–8 wt % (45–50 mol %) causes
structural changes. The thermodynamically stable sub-
stance is the BMImBr · 0.5ç2é hydrate. BMImBr mol-
ten at room temperature and containing less than 2 wt
% water exhibits the properties of highly structured
non-Newton liquids.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research, project no. 06-03-
96345-p-tsentr-a.
REFERENCES
1. P. Wassersheid and T. Welton, Ionic Liquids in Synthesis
(Wiley–VCH, Weinheim, 2003).
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1103
2. K. Murase, K. Nitta, T. N. Hirato, and Y. Awakura,
3. http://www.ionicliquids-merck.de.
4. Ya. S. Vygodskii, E. I. Lozinskaya, and A. S. Shaplov,
Dokl. Akad. Nauk 381 (5), 634 (2001) [Dokl. Chem. 381
2 5. J. D. Holbrey, W. M. Reichert, M. Nieuwenhuyren, et al.,
Chem. Commun., p. 1636 (2003).
3 6. D. D. Perrin and W. L. F. Armarego, Purification of Lab-
oratory Chemical (Pergamon, Oxford, 1980).
7. P. Bonhôte, P.-A. Dias, N. Papageorgiou, et al., Inorg.
4 Chem. 35, 1168 (1996).
5
8. S. Carda-Broch, A. Berthod, and D. W. Armstrong, Anal.
Bioanal. Chem. 375, 191 (2003).
9. A. J. Gordon and R. A. Ford, The Chemist’s Companion:
A Handbook of Practical Data, Techniques and Refer-
ences (Wiley, New York, 1972; Mir, Moscow, 1976).
10. P. I. Voskresenskii, Laboratory Procedures (Mir, Mos-
cow, 1973) [in Russian].
11. H. Sedek, A. M. Habez, and F. X. Khalil, Electrochim.
Acta 14, 1089 (1969).
12. B. A. Lopatin, Theoretical Fundamentals of Electro-
chemical Methods for Analysis (Vysshaya Shkola, Mos-
cow, 1975) [in Russian].
13. K. Nakanishi, Infrared Absorption Spectroscopy
(Holden-Day, San Francisco, 1962; Mir, Moscow,
1965).
14. K. Matsumoto, R. Hagiwara, R. Yoshida, et al., Dalton
Trans., p. 144 (2004).
15. J. Q. Huddleston, A. E. Visser, W. M. Reichert, et al.,
Green Chem. 3, 156 (2001).
16. J. Gordon, The Organic Chemistry of Electrolyte Solu-
tion (Wiley, New York, 1975; Mir, Moscow, 1979).
17. V. K. Abrosimov, V. V. Korolev, V. N. Afanas’ev, et al., in
Experimental Methods of Solution Chemistry: Densime-
try, Viscometry, Conductometry, and Other Methods
(Nauka, Moscow, 1997) [in Russian].
18. Practical Manual on Colloid Chemistry, Ed. by
I. S. Lavrov (Vysshaya Shkola, Moscow, 1983) [in Rus-
sian].
19. M. M. Usanovich, Investigations in the Theory of Solu-
tions and Theory of Acids and Bases (Nauka, Alma-Ata,
1970) [in Russian].
Vol. 82 No. 7 2008