Premium
Kinetics and mechanism of oxidation of quinols by tris(1,10‐phenanthroline) iron(III) complexes in aqueous acidic perchlorate media
Author(s) -
Mentasti Edoardo,
Pelizzetti Ezio
Publication year - 1977
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550090206
Subject(s) - chemistry , phenanthroline , kinetics , reaction rate constant , perchlorate , semiquinone , photochemistry , tris , aqueous solution , reaction mechanism , computational chemistry , inorganic chemistry , redox , catalysis , organic chemistry , ion , biochemistry , physics , quantum mechanics
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.