Disproportionation of chlorous acid. II. Kinetics

Article abstract of DOI:10.1021/ic50060a014

Kinetic data are presented for the disproportionation of chlorous acid at an ionic strength of 2.0 M under a variety of hydrogen ion conditions from 1.2 × 10^-3 to 2.0 M and with up to 0.1 M added chloride ion concentration. At 1.2 and 2.0 M hydrogen ion concentrations and at 25°, the rate law is -d[HClO₂] / dt = k₁ [HClO₂]² + k₂[HClO₂][Cl^-]² / K + [Cl^-] The parameters k₁ and K are independent of the hydrogen ion concentration and correspond to 1.17 × 10^-2 M^-1 sec^-1 and 0.0012 M, respectively. In solutions which contain 1.2 M HClO₄, k₂ is 1.57 × 10^-2 M^-1 sec^-1, and in 2.0 M HClO₄, k₂ is 3.00 × 10^-2 M^-1 sec^-1. The results are discussed in terms of a detailed mechanism.