Korean J. Chem. Eng.

, 23(1), 113-116 (2006)

Surface tension and viscosity of 1-butyl-3-methylimidazolium iodide

and 1-butyl-3-methylimidazolium tetrafluoroborate, and solubility
of lithium bromide+1-butyl-3-methylimidazolium bromide in water
Ki-Sub Kim, Dorjnamjin Demberelnyamba, Bae-Kun Shin, Sun-Hwa Yeon, Sukjeong Choi,
Jong-Ho Cha, Huen Lee , Chul-Soo Lee* and Jae-Jin Shim**
†

Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology,
373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701, Korea
*Department of Chemical and Biological Engineering, Korea University,
5-1 Anam-dong, Songbuk-gu, Seoul 131-071, Korea
**School of Chemical Engineering and Technology, Yeungnam Univ.,
214-1 Tae-dong, Kyongsam City, Gyeongbuk 712-749, Korea
( )
Received 13 May 2005 • accepted 6 July 2005

Abstract−The surface tension and viscosity of 1-butyl-3-methylimidazolium iodide ([bmim][I]) and 1-butyl-3-meth-
ylimidazolium tetrafluoroborate ([bmim][BF4]) were measured over a temperature range of 298. 15 to 323.15 K. It was
found that both the viscosity and surface tension decrease with increasing temperature and that the surface tension and
viscosity values of [bmim][I] were higher than those of [bmim][BF4]. Additionally, the solubility of lithium bromide
(2)+1-butyl-3-methylimidazolium bromide ([bmim][Br]) (3) in water (1) was measured at three different mass ratios
(w2/w3=4 and 7, w3=0) by using a visual polythermal method. The solubility of the suggested systems was better than
that of lithium bromide in water.
Key words: Surface Tension, Viscosity, Solubility, Ionic Liquid, Imidazolium Salt

INTRODUCTION Park et al., 1997]. To suppress the crystallization of the working

fluid solutions, organic compounds such as ethanolamine and 1,3-
As a neoteric solvent, ionic liquids (ILs) have attracted increas- propanediol were added, and the systems were found to have ade-
ing interest over the recent years because they have proven to be quately wide operation ranges without salt crystallization. However,
excellent alternatives to conventional organic solvents. Potentially, because of the volatility of the additives, the absorption heat pump
ILs can be used in various industrial applications, such as in liquid- performed poorly. Therefore, we suggest a new working fluid that
liquid extractions, reaction media, catalysts, and electrolytes [Marsh consists of H2O+LiBr+IL because the addition of the IL can effec-
et al., 2002; Kim et al., 2004a]. Typical ILs are salts that are based tively suppress crystallization without the vaporization in an absorp-
on a substituted heterocyclic cation and an inorganic anion such as tion cycle as its vapor pressure is not detectable.
a halide, [AlCl4], [BF4], or [TFSI]. Accordingly, an IL can be syn- In this work, 1-butyl-3-methylimidazolium bromide ([bmim][Br])
thesized in an enormous number of ways depending on the proper and 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), 1-butyl-3-
combination of ions. There is a limited amount of reliable data related methylimidazolium iodide ([bmim][I]), and 1-butyl-3-methylimida-
to the physical and chemical properties of ILs because even a small zolium tetrafluoroborate ([bmim][BF4]) were synthesized and the
amount of impurity, including that caused by water and halide anions, purity of each IL was checked. The solubility of LiBr (2)+IL (3) in
critically affects the properties of an IL. To rectify this gap in knowl- H2O (1) at three different mass ratios (w2/w3=4 and 7, w3=0) was
edge, our highest research priority should be in performing a severe measured by using a visual polythermal method, and we compared
synthesis of ILs and an exact analysis of their purity. them to the conventional H2O+LiBr system. Furthermore, the sur-
In our recent publication, we suggested some ILs that have po- face tension and viscosity of [bmim][I] and [bmim][BF4] were meas-
tential as working fluids for use in an absorption heat pump [Kim ured. The measured physical properties of the suggested systems
et al., 2004b, c]. A working fluid actually consists of two fluids: are essential in order to design an absorption heat pump.
one acts as a refrigerant and the other acts as an absorbent. For the
refrigerant, a fluid with strong volatility is used, whereas the fluid for EXPERIMENTAL SECTION
the absorbent is characterized by a much smaller volatility, though
it still has a strong affinity to the refrigerant. A system consisting of 1. Synthesis of ILs
water (H2O)+Lithium bromide (LiBr) is a conventional working [bmim][Br], [bmim][Cl], [bmim][I], and [bmim][BF4] were pre-
fluid. However, the H2O+LiBr system is hampered by an opera- pared according to our previous reports [Kim et al., 2004b, c, d].
tional limit caused by salt crystallization [Kim et al., 1996, 2001; The 1H NMR and FAB Mass spectra were recorded on a Bruker
DMX 600 MHz NMR spectrometer and FAB mass JMS-HX110A,
To whom correspondence should be addressed.
†
respectively. The presence of residual Cl− was examined by the ionic
E-mail: h_lee@kaist.ac.kr chromatography (System: Bio-LC DX-300 (Dionex, Sunnyvale,
113
114 K.-S. Kim et al.
CA, USA), Detector: Suppressed Conductivity (PED2), Column: 0.53 mol). After stirring for 24 h, the resulting NaCl precipitate was
ICSep AN300 with ICSep ANSC guard). Water contents were de- then filtered through a plug of celite and the volatiles were removed
termined by 756 Karl Fisher coulometer. by rotary evaporation, leaving a yellowish, opaque liquid. The prod-
1-1. [bmim][Br] uct was dried for 3 more days under a high vacuum at 0.03 mmHg.
In a 1,000 mL three necked round-bottomed flask equipped with The chemical shift for the 1H NMR spectrum (ppm, D2O) is as fol-
a reflux condenser, dropping funnel, and magnetic stirrer, under vig- lows: δ 8.71 [s, 1H, H(2)], 7.49 [s, 1H, H(4)], 7.44 [s, 1H, H(5)],
orous stirring, 305.64 g (390 mL, 2.85 mol) of freshly distilled bro- 4.21 [t, 2H, NCH2], 3.91 [s, 3H, NCH3], 1.87 [m, 2H, NCH2CH2],
mobutane was added dropwise under vigorous stirring over a period 1.35 [m, 2H, NCH2CH2CH2], 0.94 [t, 3H, CH3]. FAB MS: m/z=
of 1 h to a 225.43 mL (232.2 g, 2.83 mol) solution of 1-methylimi- 139. The water and chloride contents were 200 and 13 parts per
dazole in 200 mL of 1,1,1-trichloroethane at ambient temperature. million, respectively.
The mixture was then heated under reflux for 2 h and was decanted 2. Apparatus and Procedure
from the hot solution in a separatory funnel, washed twice with 300 2-1. Viscosity
mL of trichloroethane at 50 oC, and dried under reduced pressure Appropriately, the viscosities of the imidazolium salts were meas-
at 40 oC for 3 days. The 1H NMR spectrum (ppm, D2O) contains ured with two appropriate Ubbelohde viscometers. First, in consid-
peaks: δ 8.91 [s, 1H, H(2)], 7.64 [s, 1H, H(4)], 7.59 [s, 1H, H(5)], eration of the viscosity values, a suitable viscometer was selected.
4.32 [t, 2H, NCH2], 4.02 [s, 3H, NCH3], 1.95 [m, 2H, NCH2CH2], Then, the viscometer was put into a bath in which the temperature
1.42 [m, 2H, NCH2CH2CH2], 1.00 [t, 3H, CH3]. FAB MS: m/z= was controlled with a bath circulator within ±0.05 K. The equilib-
139. The water content was 1300 parts per million. rium time was about 15 min. The efflux time of the liquid solution
1-2. [bmim][Cl] through the capillary was measured manually with a stopwatch. The
A 1,000 mL three-necked round-bottom flask fitted with a water dynamic viscosity values were calculated from the following Eq. (1)
condenser and a gas inlet and provided with a Teflon-coated mag- η=tKρ (1)
netic bar was charged under N2 with 1-methylimidazole (246.3 g,
3 mol). Butyl chloride (390 mL) was added into the reaction vessel where η is the dynamic viscosity, K the instrument constant, t the
under continuous magnetic stirring in batches of 1,000 mL. The reac- efflux time, and ρ the density of the sample.
tion mixture was heated under nitrogen N2 at 80 oC for 72 h with 2-2. Surface Tension
stirring until two phases formed. The top phase, containing the un- The surface tension of each IL was measured by the Plate (Wil-
reacted starting material, was decanted and ethyl acetate (300 ml) helmy) method using a Dynamic Contact Angle analyzer (DCA)
was added through mixing. The ethyl acetate was first decanted and manufactured by Cahn Instruments [Kim and Lee, 2002a]. The plate
then fresh ethyl acetate was added; this step was repeated twice. was made of perfectly clear glass measuring 24×30 mm2 and with
After the third decanting of ethyl acetate, any remaining ethyl acetate uniform surface quality, precisely squared edges, perfect flatness,
was removed by heating the bottom phase to 60 oC and stirring while and exact dimensions. The operation and analysis of the procedure
on a vacuum line. The product was found to be slightly yellow and were automatically controlled by an external computer that was con-
became crystalline at room temperature, depending on the amount nected to the DCA. To control the temperature of the sample within
of water present in that phase. The product was recrystallized from ±0.05 K, a bath circulator was used. The accuracy of the instru-
dry acetonitrile and dried under vacuum at 70 oC for 12 h to yield ment is ±0.01 mN/m.
pure crystalline [bmim][Cl]. The 1H NMR spectrum (ppm, D2O) 2-3. Solubility
contains peaks: δ 8.7 [s, 1H, H(2)], 7.5 [s, 1H, H(4)], 7.4 [s, 1H, Solubilities were measured by a visual polythermal method. A
H(5)], 4.2 [t, 2H, NCH2], 3.9 [s, 3H, NCH3], 1.8 [m, 2H, NCH2CH2], schematic diagram of the apparatus is shown in Fig. 1. The appara-
1.3 [m, 2H, NCH2CH2CH2], 0.9 [t, 3H, CH3]. FAB MS: m/z=139. tus consisted of a glass vessel with an internal volume of 50 cm3, a
1-3. [bmim][I] thermistor thermometer capable of measuring up to 0.01 K, a con-
1-Methylimidazole (50 cm3, 0.63 mol) was dissolved in 500 cm3 stant temperature bath, a circulator for both cooling and heating,
of THF, and 55 cm3 (0.67 mol) of iodobutane was added to the solu- and two stirrers. Each sample solution of a desired water concen-
tion in a 1 L round-bottomed three-necked flask. The mixture was
refluxed for 20 h with vigorous stirring under nitrogen pressure.
Initially, the mixture formed two liquid phases. After the reaction
period was completed and the mixture had been cooled to room
temperature, the two layers were isolated from each other. The brown
liquid was isolated and washed with 300 ml of THF. The salt was
dried in a rotary-evaporator and was placed under a vacuum for
24 h. The 1H NMR spectrum (ppm, D2O) contains peaks: δ 8.75
[s, 1H, H(2)], 7.51 [s, 1H, H(4)], 7.46 [s, 1H, H(5)], 4.21 [t, 2H,
NCH2], 3.92 [s, 3H, NCH3], 1.86 [m, 2H, NCH2CH2], 1.34 [m, 2H,
NCH2CH2CH2], 0.96 [t, 3H, CH3]. FAB MS: m/z=139. The water
content was 220 parts per million. Fig. 1. Experimental apparatus for measuring solubility.
1-4. [bmim][BF4] 1. Sample vessel 5. Thermometer
A solution of [bmim][Cl] (93 g, 0.53 mol) in acetone (500 cm3) 2. Constant temperature bath 6. Circulator for heating
at room temperature was added to sodium tetrafluoroborate (58.3 g, 3,4. Stirrer 6. and cooling
January, 2006
 Physical properties of various systems of imidazolium salts 115
tration at a given mixing ratio was accurately prepared by weigh-
ing each component with a precise balance. Approximately 30 cm3
of the sample solution was placed in the vessel and stirred well. The
solution was first incrementally heated above the crystallization tem-
perature to dissolve all the crystals. The constant temperature bath
and the circulator enabled the solution temperature to be lowered
and then raised at a very slow rate, less than 0.1 K min−1. After a
series of dissolving and nucleation procedures, the temperature at
which the last crystal disappeared was taken as the crystallization
temperature for a given solution in this polythermal run.
RESULTS AND DISCUSSION

Fig. 4. Solubilities of the H2O (1)+LiBr (2)+[bmim][Br] (3) Sys-

tem: w2/w3 =4 (● ); w2/w3 =7 ( □ ); w3=0 ( ▲ ).
The viscosities and surface tensions of [bmim][I] and [bmim][BF4]
were measured over a temperature range of 298.15 to 323.15 K.
The experimental results for the viscosities of [bmim][I] and [bmim]
[BF4] are plotted in Figs. 2 and 3. The viscosity and surface tension
values were found to decrease with increasing temperature in both
samples, but the measured values of [bmim][I] were higher than
those of [bmim][BF4].
The solubility of the LiBr (2)+[bmim][Br] (3) in H2O (1) was
measured at three different mass ratios, w2/w3=4 and 7, and w3=0.
The saturated solubilities at crystallization temperatures were meas-
ured in the 61.5 to 75.0 mass% range of LiBr+IL concentration. The
Fig. 2. Viscosities of [bmim][I] ( ■ ) and [bmim][BF4] ( ▲ ). experimental results are presented in Fig. 4. In Fig. 4, the solubility
curves show a shift to the right, indicating enhanced solubility when
the amount of [bmim][Br] increases. There is little solubility effect
at w2/w3=7. For the specified temperature and concentration ranges of
this study, the maximum solubility was found to be about 75 mass%
of LiBr+[bmim][Br] at 330.15 K with a mass ratio of w2/w3=4. It
should be noted that adding [bmim][Br] as an anticrystallization
additive into the H2O+LiBr solution resulted in increased salt solu-
bility and reduced crystallization temperature. Until now, the use of
organic compounds such as ethylene glycol and 1,3-propanediol
has caused operational difficulties because a rectifier is needed to
ensure the purity of the regenerated refrigerant since a noticeable
amount of the organic additives can exist with refrigerants in the
vapor phase in the generator. In contrast, an absorption cycle that
includes ILs as anticrystallization additives does not require the use
of a rectifier because most ILs do not have a detectable vapor pres-
sure. The solubility result presented in Fig. 4 assists in extending
the operation range of the absorption chiller.
CONCLUSION
We synthesized [bmim][Br], [bmim][Cl], [bmim][I], and [bmim]
Fig. 3. Surface tensions of [bmim][I] (○) and [bmim][BF4] (●). [BF4] and analyzed the purity of each. The viscosities and surface
Korean J. Chem. Eng.(Vol. 23, No. 1)
116 K.-S. Kim et al.
tensions of [bmim][I] and [bmim][BF4] were investigated under the trifluoroethanol+quinoline system,” J. Chem. Eng. Data, 47, 216
various temperature conditions, and the solubility of the LiBr+[bmim] (2002a).
[Br] in H2O was measured. The viscosity and surface tension values Kim, K.-S., Choi, S., Demberelnyamba, D., Lee, H., Oh, J., Lee, B.-B.
of [bmim][I] were higher than those of [bmim][BF4]. The solubil- and Mun, S.-J., “Ionic liquids based on N-alkyl-N-methylmorpho-
ity data indicate that [bmim][Br] extends the solubility area for the linium salts as potential electrolytes,” Chem. Commun., 828 (2004a).
absorption process. Therefore, the IL can be a potential an additive Kim, K.-S., Park, S.-Y., Choi, S. and Lee, H., “Vapor pressures of the 1-
as an alternative to the conventional organic compounds. However, butyl-3-methylimidazolium bromide+water, 1-butyl-3-methylimi-
further tests of other thermodynamic and transport properties are dazolium tetrafluoroborate+water, and 1-(2-hydroxyethyl)-3-meth-
required before this mixture can be used as a working fluid. ylimidazolium tetrafluoroborate+water systems,” J. Chem. Eng. Data,
49, 1550 (2004c).
ACKNOWLEDGMENT Kim, K.-S., Shin, B.-K. and Lee, H., “Physical and electrochemical prop-
erties of 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimi-
This work was supported by Grant No. R01-2003-000-10300-0 dazolium iodide, and 1-butyl-3-methylimidazolium tetrafluoroborate,”
from the Basic Research Program of the Korea Science & Engineer- Korean J. Chem. Eng., 21, 1010 (2004d).
ing Foundation and also partially funded by the Brain Korea 21 Pro- Kim, K.-S., Shin, B.-K., Lee, H. and Ziegler, F., “Refractive index and
ject. The authors would like to thank KBSI (Korea Basic Science heat capacity of 1-butyl-3-methylimidazolium bromide and 1-butyl-
Institute) for assistance with NMR and FAB mass. 3-methylimidazolium tetrafluoroborate, and vapor pressure of binary
systems for 1-butyl-3-methylimidazolium bromide+trifluoroethanol
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January, 2006