Kinetics and Mechanism of the Oxidation of Formic Acid by Methyltributylammonium Permanganate in Methylene Chloride Solutions

Article abstract of DOI:10.1021/jo00259a022

The oxidation of formic acid by methyltributylammonium permanganate in methylene chloride solutions is strongly autocatalyzed by one of the reaction products, colloidal manganese dioxide.The rate law for the catalytic reaction is first-order with respect to the catalyst and follows the Langmuir isotherm for the adsorption of both the oxidizing and the reducing agents on its surface.The noncatalytic reaction is also first order with respect to permanganate.Both mechanism are dramatically inhibited by the presence of water, and both also exhibit a primary kinetic isotope effect for the oxidation of DCOOH.Possible mechanism, consistent with the experimental information, are discussed.