Glass transition behaviour of the quaternary ammonium type ionic liquid,
{[DEME][I] + H2O} mixtures

Yusuke Imai,a Hiroshi Abe,a Hitoshi Matsumoto,a Osamu Shimada,b Tomonori Hanasaki,b Yukihiro Yoshimurac

aDepartment of Materials Science and Engineering, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan
bDepartment of Applied Chemistry, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan
cDepartment of Applied Chemistry, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan

J. Chem. Thermodynamics 43 (2011) 319-322.

Abstract

By a simple DTA system, the glass transition temperatures of the quaternary ammonium type ionic liquid, {N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium iodide, [DEME][I] + H2O} mixtures after quick pre-cooling were measured as a function of water concentration (x mol% H2O). Results were compared with the previous results of {[DEME][BF4] + H2O} mixtures in which double glass transitions were observed in the water concentration region of (16.5 to 30.0) mol% H2O. Remarkably, we observed the double glass transition phenomenon in {[DEME][I] + H2O} mixtures too, but the two-Tgs regions lie towards the water-rich side of (77.5 to 85.0) mol% H2O. These clearly reflect the difference in the anionic effect between BF4- and I- on the water structure. The end of the glass-formation region of {[DEME][I] + H2O} mixtures is around x = 95.0 mol% H2O, and this is comparable to that of {[DEME][BF4] + H2O} mixtures (x = 96.0 mol% H2O).

Fig. 1
Schematic chemical structure of (a) [DEME] cation and (b) iodide anion.


Fig. 2
Schematic DTA warm-up traces of (a) 55.0, (b) 85.0 and (c) 90.1 mol% H2O mixed solutions. At x = 85.0 mol% H2O, an exothermic crystallization-like peak appeared at around T = 168 K just after the first Tg.
Fig. 3.
The re-quenching procedure for detecting the Tg2 at x = 85.0 mol% H2O. The thin solid line corresponds to the first run, and the dotted line represents the requenching process. After the re-quenching, a clear downward Cp shift was observed as the Tg2 in the second run (thick line).
Fig. 4.
Plot of Tg as a function of x mol% H2O, (a) [DEME][BF4]-H2O and (b) [DEME][I]-H2O mixed solutions. Symbols of *, * and * stand for Tg, Tg1 and Tg2, respectively. The Tg data of [DEME][BF4]-H2O mixed solutions [11] are shown for comparison. The dotted vertical lines are only guides for the eye.
Fig. 5.
Comparison of the Raman spectra between [DEME][I]-H2O (thick line) and [DEME][BF4]-H2O (thin line) at the corresponding water concentration (x = 55 mol% H2O) in the liquid state. Peak intensities are normalised by the strongest peak of CH stretching vibrational mode of [DEME] cation. (a) The CH and OH stretching vibrational modes of the solutions and (b) the enlarged OH stretching vibrational region.
Fig. 6.
The Raman spectra of [DEME][I]-H2O solution (x = 80.0 mol% H2O) in (a) the CH and OH and (b) the OH stretching vibrational region at T = 297 K (thin line) and T = 77 K (thick line).
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Last Modified: April 1, 2011