Generation and reactions of the chlorine atom in aqueous solution

Abstract

The chlorine atom (Cl^˙) has been generated in aqueous solution by reaction of Cl^– with SO^˙–₄ and H₂PO^˙₄, obtained by metal-catalysed decomposition of the appropriate peroxides. E.s.r. experiments in conjunction with a fast-flow method establish that Cl^˙ is highly reactive, readily undergoing rapid addition, hydrogen-abstraction and electron-transfer reactions (k≈ 10⁸–10⁹ dm³ mol^–1 s^–1). The factors which influence the observed selectivity (energetics and polar effects) are discussed.