1. Nuclear magnetic resonance studies on the rotational and translational motions of ionic liquids composed of 1-ethyl-3-methylimidazolium cation and bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide anions and their binary systems including lithium salts
- Author
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Hayamizu, Kikuko, Tsuzuki, Seiji, Seki, Shiro, and Umebayashi, Yasuhiro
- Subjects
NUCLEAR magnetic resonance spectroscopy ,ROTATIONAL motion ,TRANSLATIONAL motion ,IONIC liquids ,IMIDAZOLES ,CATIONS ,AMIDES ,BINARY metallic systems ,MOLECULAR dynamics ,RELAXATION phenomena - Abstract
Room temperature ionic liquids (ILs) are stable liquids composed of anions and cations. 1-ethyl-3-methyl-imidazolium (EMIm, EMI) is a popular and important cation that produces thermally stable ILs with various anions. In this study two amide-type anions, bis(trifluoro-methanesulfonyl)amide [N(SO2CF3)2, TFSA, TFSI, NTf2, or Tf2N] and bis(fluorosulfonyl)amide [(N(SO2F)2, FSA, or FSI] were investigated by multinuclear NMR spectroscopy. In addition to EMIm-TFSA and EMIm-FSA, lithium-salt-doped binary systems were prepared (EMIm-TFSA-Li and EMIm-FSA-Li). The spin-lattice relaxation times (T1) were measured by 1H, 19F, and 7Li NMR spectroscopy and the correlation times of 1H NMR, τc(EMIm) (8 × 10-10 to 3 × 10-11 s) for the librational molecular motion of EMIm and those of 7Li NMR, τc(Li) (5 × 10-9 to 2 × 10-10 s) for a lithium jump were evaluated in the temperature range between 253 and 353 K. We found that the bulk viscosity (η) versus τc(EMIm) and cation diffusion coefficient DEMIm versus the rate 1/τc(EMIm) have good relationships. Similarly, linear relations were obtained for the η versus τc(Li) and the lithium diffusion coefficient DLi versus the rate 1/τc(Li). The mean one-jump distances of Li were calculated from τc(Li) and DLi. The experimental values for the diffusion coefficients, ionic conductivity, viscosity, and density in our previous paper were analyzed by the Stokes-Einstein, Nernst-Einstein, and Stokes-Einstein-Debye equations for the neat and binary ILs to clarify the physicochemical properties and mobility of individual ions. The deviations from the classical equations are discussed. [ABSTRACT FROM AUTHOR]
- Published
- 2011
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