ESR studies of solvent and pressure effects on spin exchange of nitroxide radicals in solution.
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概要
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The rate constants of spin exchange for 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxyl (Tanone) in various solvents at high pressures were estimated from the line-broadening in ESR spectra. The rate constants of the spin exchange were in the range of 10<SUP>9</SUP>–10<SUP>10</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP> and were compared with the calculated ones on the basis of the Smoluchowski–Stokes–Einstein equation. A significant disagreement between them was observed as the solvent viscosity decreased. The activation volumes estimated from the pressure dependence of the rate constant for the spin exchange were slightly smaller than those for diffusive processes. These findings suggest that the rate process for the spin exchange is virtually a diffusion-controlled one. An interpretation of activation volumes for diffusive process of spin exchange is given.
- 公益社団法人 日本化学会の論文
著者
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Sueishi Yoshimi
Department Of Chemistry Faculty Of Science Okayama University
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Kuwata Keiji
Department Of Chemistry Faculty Of Science Osaka University
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Nishimura Norio
Department Of Chemistry Faculty Of Science Okayama University
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Hirata Koichi
Department Of Gastrointestinal Surgery And Oncological Surgery Sapporo Medical University School Of
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Hirata Koichi
Department of Chemistry, Faculty of Science, Osaka University
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