Kinetics and mechanism of oxidation of nitrous acid by chlorite ion

Article abstract of DOI:10.1021/j100312a030

Although the oxidation of nitrite by chlorite both stoichiometrically and kinetically is a fairly simple reaction when nitrite is in excess and the pH is above 4, it becomes exceedingly complex in acidic solution containing chlorite in excess. Cl₂O₂ appears to be a key intermediate, the transitory formation of which explains both the formation of ClO₂ and peculiar three-extrema E versus time curve. Assuming that the electrode process on the bright Pt electrode is HOCl + e^- + H⁺ = Cl₂ + H₂O, the reaction is an oligooscillatory one in which the concentration of HOCl exhibits three extrema at most.