Autocatalysis and self-inhibition: coupled kinetic phenomena in the chlorite-tetrathionate reaction.

The initial rate of formation of chlorine dioxide in the chlorite-tetrathionate reaction changes in an unusual fashion. The formal kinetic order of both reactants varies over a very wide range. Moreover, chlorite ion behaves not just as a simple reactant, but also as a self-inhibitor. A five-step scheme, derived from an eight-step mechanism, is proposed in which the autocatalytic formation of HOCl plays a central role in accounting for this kinetic behavior.