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Kinetics and mechanism of oxidation of quinols by tris(1,10-phenanthroline) iron(III) complexes in aqueous acidic perchlorate media

✍ Scribed by Edoardo Mentasti; Ezio Pelizzetti

Publisher
John Wiley and Sons
Year
1977
Tongue
English
Weight
399 KB
Volume
9
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The kinetics of oxidation of several substituted quinols by a series of Tris(1,10‐phenanthroline)iron(III) complexes has been investigated with a stopped‐flow technique at 6.0 and 20.0°C. The reactions were found to be first order on both reactants and independent of acidity. The second‐order specific rate constants were strongly dependent on free energy of reaction. An interpretation of the mechanism in the light of Marcus theory has been developed. The first electron abstraction with semiquinone radical formation has been suggested as the rate‐determining step, and on this basis, intrinsic parameters of the reactions have been derived. A good agreement was found between experimental and computed data.

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