The formation of ClO2 from the reaction of Cl2 with ClO2-has a rate constant of k 1=(5.7±0.2)× 105 M-1 s-1. The reaction proceeds by Cl+ transfer to form a metastable ClOClO intermediate. Kinetic data indicate that electron transfer between Cl2 and ClO2-is negligible compared to the Cl+-transfer pathway. A much slower formation of ClO2 occurs due to the general-acid-assisted formation of steady-state amounts of Cl2 from HOCl and ...