Radiolysis of frozen solutions containing oxybromine anions
Abstract
The radiolysis of oxybromine-anions (BrO–n, n= 1–4) and ClO–4 in glassy and polycrystalline aqueous solutions has been investigated by e.s.r. BrO2 is the main product in BrO–3 and BrO–2 solutions. The thermal stability of BrO2 varied with the structure and composition of the solution. The e.s.r. spectrum of BrO2 in aqueous solutions has been simulated with data for BrO2 in single crystals. BrO was not detected in BrO–2 or BrO– solutions. ClO3, ClO4, and ClO2–4 were identified in irradiated polycrystalline KClO4 solutions, but these radicals were not observed in glassy or polycrystalline NaClO4 solutions, polycrystalline CsClO4 solutions or in 10 M NaOH solutions containing 0.1 M KClO4. KBrO4 solutions behaved similarly to KClO4 solutions. KBrO4 reacts with electrons in glassy 10 M NaOH solutions but no bromine-containing radicals are observed. The radicals observed in irradiated polycrystalline KClO4 and KBrO4 solutions are assumed to arise from reactions between the water radicals and precipitated salts. Effects of precipitation are also observed in polycrystalline solutions saturated with NaBrO3 or KBrO3.