title: Reaction of ozone with hydrogen peroxide (peroxone process): a revision of current mechanistic concepts based on thermokinetic and quantum-chemical considerations.
abstract: The reaction of ozone with the anion of H(2)O(2) (peroxone process) gives rise to (*)OH radicals (Staehelin, J.; Hoigne, J. Environ. Sci. Technol. 1982, 16, 676-681). Thermokinetic considerations now suggest that the electron transfer originally assumed as the first step has to be replaced by the formation of an adduct, HO(2)(-) + O(3) --> HO(5)(-) (DeltaG degrees = -39.8 kJ mol(-1)). This decomposes into HO(2)(*) and O(3)(*-) (DeltaG(0) = 13.2 kJ mol(-1)). HO(2)(*) is in equilibrium with O(2)(*-) + H(+), and O(2)(*-) undergoes electron transfer to O(3) giving rise to further O(3)(*-). The decay of O(3)(*-) into (*)OH is now discussed on the basis of the equilibria O(3)(*-) right arrow over left arrow O(2) + O(*-) and O(*-) + H(2)O right arrow over left arrow (*)OH + OH(-), excluding HO(3)(*) as the intermediate originally assumed. To account for the observation of the peroxone process being only 50% efficient, the decay of HO(5)(-) into 2 O(2) + OH(-) (DeltaG(0) = -197 kJ mol(-1)) is proposed to compete with the decay into HO(2)(*) and O(3)(*-).
authors.affiliation: School of Chemistry, Nuclear Chemistry, The Royal Institute of Technology, 10044 Stockholm, Sweden. gm@nuchem.kth.se
authors.forename: Gábor
authors.initials: G
authors.lastname: Merényi
authors.forename: Johan
authors.initials: J
authors.lastname: Lind
authors.forename: Sergej
authors.initials: S
authors.lastname: Naumov
authors.forename: Clemens von
authors.initials: Cv
authors.lastname: Sonntag
mesh_terms: D004583:Electrons; D006358:Hot Temperature; D006860:Hydrogen Bonding; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D017665:Hydroxyl Radical; D007700:Kinetics; D008956:Models, Chemical; D010100:Oxygen / Q000737:chemistry; D010126:Ozone / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D012997:Solvents; D017665:Hydroxyl Radical; D010126:Ozone; D006861:Hydrogen Peroxide; D010100:Oxygen