Reactions between some inorganic radicals and oxychlorides studied by pulse radiolysis and laser photolysis

Abstract

Rate constants for the reactions of free radicals, including e_aq^-, OH, SO₄^-, NO₃ and Cl₂^- (Cl^Nsbd), with oxychloride compounds have been determined. The free radicals were generated by pulse radiolysis and laser photolysis. Most of the reactions have nearly diffusion-controlled rate constants (>10⁹ dm3 mol^-1 s^-1). ClO^- has relatively higher reactivity than its acid form. e_aq^- reacts with oxychloride compounds to form their electron adducts which dissociate easily. Electron transfer reactions occur between OH, SO₄^-, NO₃ and Cl₂^- (Cl^Nsbd) radicals and the oxychloride ions. The kinetics results obtained here can be used in simulation work to understand the radiation-induced reactions taking place in groundwater which are relevant to the geological aspects of radioactive waste storage and disposal.

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