Reaction of peroxyl radicals with ozone in water
2003 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 107, no 5, 676-681 p.Article in journal (Refereed) Published
The reactivity of alkylperoxyl radicals and -O3SOO* toward ozone was investigated. The peroxyl radicals were produced by steady-state gamma-radiolysis in the presence Of O-3. The rate constants were extracted from the decay rate of ozone measured during the irradiation. The rate constants vary between 7 x 10(3) and 2 x 10(5) M-1 s(-1) and there is a trend of increasing rate constant with electron-withdrawing substituent. Quantum chemical computations support a mechanism, according to which formation of an alkyl trioxide radical is the rate-determining step. This is followed by rapid expulsion Of O-2 to yield the alkoxyl radical. Conceivably, the alkyl trioxide radical is preceded by an extremely unstable alkyl pentoxide radical in equilibrium with the reactants.
Place, publisher, year, edition, pages
2003. Vol. 107, no 5, 676-681 p.
dissociating organic-compounds, oxygenated aqueous-solutions, pulse-radiolysis, rate constants, inorganic-compounds, gamma-radiolysis, mechanism, ho2, decomposition, oxidation
IdentifiersURN: urn:nbn:se:kth:diva-22227DOI: 10.1021/jp026323uISI: 000180755700010OAI: oai:DiVA.org:kth-22227DiVA: diva2:340925
QC 201005252010-08-102010-08-10Bibliographically approved