Abstract
In slightly alkaline solution the ozonide radical ion, O/sub 3//sup -/, forms as a product of the hydroxyl radical reaction with ozone. For each O/sub 3//sup -/ formed, two O/sub 3/ molecules are consumed. In acid solution the product of this reaction is the perhydroxyl radical, HO/sub 2/, formed from one O/sub 3/ molecule. Our results are consistent with the gas-phase reaction where the products are HO/sub 2/ and O/sub 2/. A rate constant of (1.1 +/- 0.2) x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/ is found for the reaction OH + O/sub 3/ ..-->.. HO/sub 2/ + O/sub 2/. This rate constant was obtained by three systems, by buildup of O/sub 3//sup -/ in basic solutions, by competition of the OH radical with the carbonate ion, and directly by O/sub 3/ consumption in acid solution. The rate constant for the reaction of HO/sub 2/ with O/sub 3/ is very low, < 10/sub 4/ dm/sup 3/ mol/sup -1/ s/sup -1/. At pH greater than or equal to 1, HO/sub 2/ reacts with O/sub 3/ preferentially in its dissociated form, O/sub 2//sup -/. No spectroscopic evidence has been found for the HO/sub 3/ and HO/sub 4/ free-radical intermediates. 24more » references, 4 figures, 2 tables.« less
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