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Kinetics and mechanism of oxidation ofα,β-unsaturated alcohols by manganese(III) acetate in aqueous sulphuric acid medium

✍ Scribed by S. Pulla Rao; M. Anand Rao

Publisher
Springer
Year
1993
Tongue
English
Weight
329 KB
Volume
18
Category
Article
ISSN
0340-4285

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✦ Synopsis

The kinetics of oxidation of c~,/?-unsaturated alcohols (UA's), such as prop-2-ene-l-ol, but-2-ene-l-ol and 3phenyl-prop-2-ene-l-ol, by manganese(III) acetate in aqueous H2SO 4 at constant ionic strength and different acidities has been studied. The reaction was found to proceed through an outer sphere mechanism. The reactions were first order with respect to [Mn m] and fractional order in [UA]. The reaction showed first order dependence in [H+], and the rate decreased on addition of [Mn~X]. Added salts, such as Na2SO4, had a negligible effect on the rate. The data suggested that disproportionation of the MnH~-UA complex into free radicals was the rate determining step in the presence of [MnH]. A mechanism consistent with the experimental data is proposed. The activation parameters have been evaluated for the temperature range 298-313 K.

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