Abstract
The oxidation of Br− by Cl2˙− is investigated by pulse radiolysis in aqueous solutions of NaCl and NaBr. Depending on the ratio of the concentration of Br− to Cl−, the main product being observed is either Cl2˙−, ClBr˙− or Br2˙−. The mixed radical anion ClBr˙− exhibits a broad absorption band at 350 nm with e350 = 9300 dm3 mol−1 cm−1. The rate constants of the equilibrium Cl2˙− + Br− ⇌ ClBr˙− + Cl− are determined to be kf = 4 × 109 and kb = 1.1 × 102 dm3 mol−1 s−1.
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