Kinetics and mechanism of the osmium-tetroxide-catalysed oxidation of mandelate ion by hexacyanoferrate(III) ion

Abstract

The osmium-tetroxide-catalysed oxidation of mandelate ion by hexacyanoferrate(111) ion has been studied kinetically. The reaction rate has been found to be independent of hexacyanoferrate(111) ion while the order with respect to both osmium tetroxide and mandelate ion comes out to be unity. The reaction rate follows first-order kinetics at low hydroxyl ion concentration and becomes zero order at higher concentrations. The course of the reaction has been considered to proceed through the formation of an activated mandelate-OsO₄, complex which decomposes in alkaline medium giving reduced osmium(V1) followed by a fast oxidation by hexacyanoferrate(111) ion. The probable course of the reactions is also described with the help of its oxidation product, benzoic acid.