Physicochemical properties and structures of room-temperature ionic liquids. 3. Variation of cationic structures 10.1021/jpO53396f

被引:562
作者
Tokuda, H
Ishii, K
Susan, MABH
Tsuzuki, S
Hayamizu, K
Watanabe, M
机构
[1] Yokohama Natl Univ, Dept Chem & Biotechnol, Hodogaya Ku, Yokohama, Kanagawa 2408501, Japan
[2] CREST, JST, Yokohama, Kanagawa 2408501, Japan
[3] Natl Inst Adv Ind Sci & Technol, Tsukuba, Ibaraki 3058568, Japan
[4] Natl Inst Adv Ind Sci & Technol, Tsukuba, Ibaraki 3058565, Japan
关键词
D O I
10.1021/jp053396f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A series of room-temperature ionic liquids (RTILs) were prepared with different cationic structures, 1-butyl-3-methylimidazolium ([bmim]), 1-butylpyridinium ([bpy]), N-butyl-N-methylpyrrolidinium, ([bmpro]), and N-butyl-N,N,N-trimethylammonium ([(n-C4H9)(CH3)(3)N]) combined with an anion, bis(trifluoromethane sulfonyl)imide ([(CF3SO2)(2)N]), and the thermal property, density, self-diffusion coefficients of the cation and anion, viscosity, and ionic conductivity were measured over a wide temperature range. The self-diffusion coefficient, viscosity, ionic conductivity, and molar conductivity follow the Vogel-Fulcher-Tamman equation for temperature dependencies, and the best-fit parameters have been estimated. to-ether with the linear fitting parameters for the density. The relative cationic and anionic self-diffusion coefficients for the RTILs, independently determined by the pulsed-field-gradient spin-echo NMR method, appear to be influenced by the shape of the cationic structure. A definite order of the summation of the cationic and anionic diffusion coefficients for the RTILs: [bmim] [(CF3SO2)(2)N] > [bpy] [(CF3SO2)2N] > [bmpro] [(CF3SO2)(2)N] > [(n-C4H9)(CH3)(3)N][(CF3SO2)(2)N], has been observed, which coincides with the reverse order to the viscosity data. The ratio of molar conductivity obtained from the impedance measurements to that calculated by the ionic diffusivity using the Nernst-Einstein equation quantifies the active ions contributing to ionic conduction in the diffusion components and follows the order: [bmpro][(CF3SO2)(2)N] > [(n-C4H9)(CH3)(3)N][(CF3SO2)(2)N] > [bpy][(CF3SO2)(2)N] > [bmim][(CF3SO2)(2)N] at 30 degrees C.
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页码:2833 / 2839
页数:7
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