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Formation of ozone in the reaction of OH with O/sub 3//sup -/ and the decay of ozonide ion radical at pH 10-13

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j150646a021· OSTI ID:6922097

Ozone forms in aqueous alkaline solution, pH 10-13, by a reaction between OH and O/sub 3//sup -/ radicals. The reaction, OH + O/sub 3//sup -/ ..-->.. O/sub 3/ + OH/sup -/, is about 30% of the total reaction. A second reaction is OH + O/sub 3//sup -/ + OH/sup -/ ..-->.. 2O/sub 2//sup -/ + H/sub 2/O. The ozone formation is demonstrated by a high-pressure pulse radiolysis technique using a 4-..mu..s, 40-krd pulse. The ozone rapidly disappears in a reaction with the simultaneously formed O/sub 2//sup -/ re-forming O/sub 3//sup -/. The product resulting from the O/sub 3//sup -/ decay is the peroxy radical, O/sub 2//sup -/. The overall rate constant, k(OH + O/sub 3//sup -/), is (8.5 +/- 1.0) X 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/. Computer simulations of the high-pressure system as well as of the atmospheric-pressure oxygenated system with high and low pulse intensity support a mechanism for the O/sub 3//sup -/ decay based on the above-mentioned reactions. The protonation rate constant of the O/sub 3//sup -/ radical ion, k(O/sub 3//sup -/ + H/sup +/), is (9.0 +/- 1.0) X 10/sup 10/ dm/sub 3/ mol/sup -1/ s/sup -1/. 6 figures, 2 tables.

Research Organization:
Riso National Lab., Roskilde, Denmark
OSTI ID:
6922097
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 88:2; ISSN JPCHA
Country of Publication:
United States
Language:
English