A three-variable model for the explanation of the "supercatalytic" effect of hydrogen ion in the chlorite-tetrathionate reaction.

It has been shown that not only the slow direct but also the indirect (HOCl-catalyzed) reaction between chlorite and tetrathionate ions is second order with respect to hydrogen ion. Since the direct reaction was found to be orders of magnitude slower than the parallel HOCl-catalyzed pathway, a three-variable model is derived from the previously published five-step model taking into account the experimentally determined H+ concentration dependence of its rate coefficients by neglecting the direct reaction. The new three-variable model indicates that the "supercatalytic" effect of the hydrogen ion in the HOCl-catalyzed pathway arises from the pH dependence of the individual reactions of the five-step model. The new three-variable model also accounts for the continuous change of the stoichiometric ratio of the reactants and provides a simple kinetic law for involving it in the partial differential equation systems widely used in the study of spatiotemporal behavior of the chlorite-tetrathionate reaction.