THE MECHANISMS OF PERMANGANATE OXIDATION VI. THE OXIDATION OF CYANIDE ION

Abstract

Kinetic and oxygen-18 tracer experiments have been used in an attempt to elucidate the mechanism(s) of permanganate oxidation of cyanide. From pH 12 to 14.6 the oxidation is represented by the equation,[Formula: see text]From pH 12 to 6 the reaction was found to be complex and unstoichiometric yielding cyanate, carbon dioxide, cyanide ion, and finally cyanogen at pH 9 to 6.The rate of reduction of permanganate, as followed iodometrically and spectrophotometrically, is found to be markedly dependent on the pH of the medium and reactant concentration. The rate is negligible in acid solution but rapid in basic media.At pH greater than 12 two parallel processes are indicated which have been designated as reaction A and reaction B. Reaction A appears at low reactant concentrations 0.0004 M cyanide and higher hydroxyl ion concentrations pH 13 and is represented by the kinetic expression[Formula: see text]where k2 is independent of hydroxyl ion concentration and is insensitive to the presence of manganate and barium ions. A positive salt effect is observed and labeling experiments using permanganate enriched in oxygen18 showed that the oxygen introduced into the product cyanate comes mainly from the oxidant (70%–80% oxygen-18 transferred).The existence of a second process reaction B was indicated by the changing kinetics at higher reactant concentrations and lower basicities, by the non-linear Arrhenius plots, and by the observation that only 15–25% oxygen-18 transfer from permanganate to substrate had occurred at pH 13. The rate of this latter process is approximately represented by the kinetic expression[Formula: see text]These reactions are discussed in terms of mechanism