The radiolysis of aqueous solutions of oxybromine compounds; the spectra and reactions of BrO and BrO 2

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Pulse radiolysis supplemented by steady state radiolysis of aqueous solutions containing some of the following solutes: N 2 O, Br - , BrO - , BrO - 2 , BrO - 3 , CO 2- 3 , and OH - has been used to identify the absorption spectra of BrO ( λ max = 350 nm) and BrO 2 ( λ max = 475 nm) and to evaluate the following rate constants (units, M -1 s -1 ): e - aq. + BrO - → Br - + O - (2.3 ± 0.5 x 10 10 ); e - aq. + BrO - 2 → BrO + O 2- (1.8 ± 0.2 x 10 10 ); e - aq. + BrO - 3 → BrO 2 + O 2- (4.1 ± 0.2 x 10 9 ); OH + BrO - → OH - + BrO (4.5 x 10 9 ); O - + BrO - → BrO + O 2- (4.6 x 10 9 ); OH + BrO - 2 → OH - + BrO 2 (1.9 x 10 9 ); Br - 2 + BrO - → BrO + 2Br - (8.0 ± 0.7 x 10 7 ); Br - 2 + BrO - 2 → BrO + Br - + BrO - (8.0 ± 0.8 x 10 7 ); BrO + BrO - 2 → BrO - + BrO 2 (3.4 ± 0.7 x 10 8 ); 2BrO 2 ⇌ Br 2 O 4 ( k = 1.4 x 10 9 and K = 19 M -1 ); Br 2 O 4 + OH - → H + + BrO - 2 + BrO - 3 (7 x 10 8 ); 2BrO + H 2 O → BrO - + BrO - 2 + 2H + (4.9 ± 1.0 x10 9 ); CO - 3 + BrO - → CO 2- 3 + BrO (4.3 ± 0.4 x 10 7 ); CO - 3 + BrO - 2 → CO 2- 3 + BrO 2 (1.1 ± 0.1 x 10 8 ). In contrast to their chlorine analogues, little is known of the chemistry of the bromine oxides in aqueous solution. In this paper we describe the methods of formation and identification of the radicals BrO and BrO 2 , and their reactions with various oxybromine species, as elucidated by the techniques of pulse radiolysis and kinetic spectroscopy applied to aqueous solutions containing oxybromine anions.