Kinetics and mechanism of oxidation of secondary alcohols by potassium bromate

The oxidation by Br(V) of propan-2-ol follows the rate law (?dBr(V)]/dt) = k₄ alcohol]Br(V)]H⁺]². The initial reaction is complicated by the presence of the product bromide ion. The reaction is composed of two second order reactions—the first, a comparatively slow one and the second stage, a faster reaction which is mainly bromine oxidation. The pure bromate oxidation can be followed by the initial addition of mercuric acetate which prevents the accumulation of bromine in the system under these conditions. The reaction rate does not depend on the nature and structure of the alcohol. A mechanism involving a slow rate-determining formation of an alkyl-bromate ester followed by a fast decomposition to the products is in accord with the observed results.