Kinetics of disproportionation of chlorous acid

Abstract
A mechanism involving HOCl, Cl—ClO2, and Cl2 as intermediates is proposed for the disproportionation of chlorous acid. In the absence of chloride, the reaction is controlled by two simultaneous processes, 2HClO2 → H+ + HOCl + ClO3 and HClO2 + ClO2 → HOCl + ClO3. Chloride has a catalytic effect and an inhibiting effect as well on the formation of chlorine dioxide. The initial reaction rate passes through a minimum at a certain concentration of chloride at low acidities, which can be interpreted by the postulated mechanism. Under chloride catalysis, the reaction is controlled by the process H+ + Cl + HClO2 → 2HOCl.

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