Radiation chemistry of xenon trioxide, xenate and perxenate, and photochemistry of perxenate. A pulse radiolysis and laser flash photolysis study

Abstract

Unstable species containing xenon in the formal oxidation states five, XeV, and seven, XeVII, were observed by pulse radiolysis of aqueous solutions of xenon trioxide, XeO3, at pH 8–9 and of xenate, HXeO–4, at pH 11–13. XeVII and species containing xenon in the formal oxidation state nine, XeIX, were observed in pulse radiolysis and flash photolysis of aqueous solutions of perxenate, HXeO3–6, at pH 11–13. The formulae HXeO3 and H3XeO2–7 are assumed for XeV and XeIX, whereas the observations suggest that XeVII corresponds to three different species for which the formulae HXeO4, HXeO2–5 and H3XeO2–6 are assumed. HXeO3 and H3XeO2–6 are formed in reactions of the hydrated electron with XeO3 and HXeO3–6, respectively. HXeO4 and H3XeO2–7 are formed in reactions of the hydroxyl radical with XeO3 and HXeO3–6 in which the hydroxyl radical adds to a ligand oxygen atom to form peroxy compounds. HXeO2–5 is formed in a reaction with the hydroxyl radical anion in which the hydroxyl radical anion adds to the xenon atom and by photolysis of HXeO3–6: HXeO3–6 [graphic omitted] HXeO2–5+ O–. XeV, XeVII and XeIX and corresponding iodine species in the oxidation states four, six and eight have similar spectra and kinetics of disappearance. Estimated values of standard Gibbs energy of formation of the xenon species are used for selecting thermodynamically feasible mechanisms for one-electron reduction of perxenate and for the decomposition of perxenate in acid solution.