Homogeneous redox catalysis of electrochemical reactions: Part III. Rate determining electron transfer. Kinetic characterization of follow-up chemical reactions |
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Authors: | CP Andrieux JM Dumas-Bouchiat JM Saveant |
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Institution: | Laboratoire d''Electrochimie, Université de Paris VII, 2, place Jussieu, 75221 Paris-Cedex 05 (France) |
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Abstract: | Electrochemical systems involving moderately fast charge transfers and very fast irreversible follow-up chemical reactions usually escape from kinetic and mechanistic characterization through the standard use of electrochemical techniques. It is shown that these difficulties can be overcome using an indirect approach which involves the homogeneous redox catalysis of the considered electrochemical reaction. A procedure for determining the rate constant of such fast follow-up reaction is presented. It is illustrated by the determination of the cleavage rate constant of the chlorobenzene anion radical in DMF which reaches a value on the order of 107 s?1. |
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