Kinetic Role of Reactive Intermediates in Controlling the Formation of Chlorine Dioxide in the Hypochlorous Acid–Chlorite Ion Reaction

[Image: see text] An advanced experimental protocol is reported for studying the kinetics and mechanism of the complex redox reaction between chlorite ion and hypochlorous acid under acidic condition. The formation of ClO(2) is followed directly by the classical two-component stopped-flow method. In sequential stopped-flow experiments, the target reaction is chemically quenched using NaI solution and the concentration of each reactant and product is monitored as a function of time by utilizing the principles of kinetic discrimination. Thus, in contrast to earlier studies, not only the formation of one of the products but the decay of the reactants was also directly followed. This approach provides a firm basis for postulating a detailed mechanism for the interpretation of the experimental results under a variety of conditions. The intimate details of the reaction are explored by simultaneously fitting 78 kinetic traces, i.e., the concentration vs. time profiles of ClO(2)(–), HOCl, and ClO(2), to an 11-step kinetic model. The most important reaction steps were identified, and it was shown that two reactive intermediates have a pivotal role in the mechanism. While chlorate ion predominantly forms via the reaction of Cl(2)O, chlorine dioxide is exclusively produced in reaction steps involving Cl(2)O(2). This study leads to clear conclusions on how to control the stoichiometry of the reaction and achieve optimum conditions to produce chlorine dioxide and to reduce the formation of the toxic chlorate ion in practical applications.