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Rate constants for one‐electron oxidation by methylperoxyl radicals in aqueous solutions
Author(s) -
HUIE Robert E.,
NETA P.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550181007
Subject(s) - chemistry , radiolysis , radical , reaction rate constant , aqueous solution , redox , one electron reduction , solvated electron , photochemistry , inorganic chemistry , kinetics , electrochemistry , organic chemistry , physics , quantum mechanics , electrode
Rate constants for one‐electron oxidation by the methylperoxyl radicals (CH 3 O 2 , HOCH 2 O 2 , − O 2 CCH 2 O 2 , and CCI 3 O 2 ) in aqueous solutions have been measured by pulse radiolysis and found to be in the range of 3 × 10 5 to 6 × 10 8 M −1 s −1 for compounds with redox potentials between 0.6 and 0.1 V. Substitution on the methylperoxyl radical with OH or CO 2 − has only a minor effect on the rate of oxidation but substitution with three chlorines increases the rate constants by two orders of magnitude. The redox potential of the CH 3 O 2 radical is estimated to be 0.6–0.7 V.