ISSN:
1572-901X
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary The kinetics of oxidation of α,β-unsaturated alcohols (UA's), such as prop-2-ene-1-ol, but-2-ene-1-ol and 3-phenyl-prop-2-ene-1-ol, by manganese(III) acetate in aqueous H2SO4 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 [MnIII] and fractional order in [UA]. The reaction showed first order dependence in [H+], and the rate decreased on addition of [MnII]. Added salts, such as Na2SO4, had a negligible effect on the rate. The data suggested that disproportionation of the MnIII-UA complex into free radicals was the rate determining step in the presence of [MnII]. A mechanism consistent with the experimental data is proposed. The activation parameters have been evaluated for the temperature range 298–313 K.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00139949
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