Diffusion of Transient Radicals in Alcohols and Cyclohexane from Ambient to Supercritical Conditions Studied by the Transient Grating Method

DOI Web Site 被引用文献5件
  • T. Ohmori
    Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502 Japan, and Division of Research Initiatives, International Innovation Center, Kyoto University, Kyoto, 606-8501 Japan
  • Y. Kimura
    Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502 Japan, and Division of Research Initiatives, International Innovation Center, Kyoto University, Kyoto, 606-8501 Japan
  • N. Hirota
    Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502 Japan, and Division of Research Initiatives, International Innovation Center, Kyoto University, Kyoto, 606-8501 Japan
  • M. Terazima
    Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto, 606-8502 Japan, and Division of Research Initiatives, International Innovation Center, Kyoto University, Kyoto, 606-8501 Japan

書誌事項

公開日
2003-05-24
DOI
  • 10.1021/jp034305m
公開者
American Chemical Society (ACS)

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説明

The translational diffusion coefficients of ketyl radicals produced by a hydrogen abstraction reaction in ethanol, methanol, and cyclohexane are investigated by the transient grating (TG) method, from liquid phase to the medium-density region in wide temperature ranges. It is found that the diffusion coefficient of the radical (Dr) is smaller than that of a stable molecule with a similar size (Ds) even under supercritical conditions. In the medium-density region, the values of Dr in alcohols are differently dependent on temperature over viscosity from those in cyclohexane. The activation energy of Dr was determined and compared with that of solvent viscosity. We found that Dr/Ds decreases with decreasing density in the medium-density region for cyclohexane. This tendency is explained in terms of the local density enhancement in the medium-density region. In alcohols, the density dependence of Dr/Ds is not significant.

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