Abstract
The peroxyl radicals Cl3COO·, Cl2CHOO·, ClCH2OO·, CH3OO; ·OOCCl2CO2–, ·OOCHClCO2–, ·OOCH2CO2–, ·OOCF2CO2–, and (CH3)2C(OH)CH2OO· have been generated in aqueous alcohol solutions by pulse radiolysis using the Brunel and Hahn-Meitner accelerators. The absolute rate constants of the one-electron transfer reactions of related aliphatic peroxyl radicals with ascorbate, promethazine, phenol, and tyrosine have been found to increase with increasing substitution of chlorine atoms. For the reaction of the radical Cl3CO2· and promethazine, at pH 6, k 6.0 ± 0.4 × 108 l mol–1 s–1 has been measured. For the analogous reaction of the radical ClCH2O2·, k 3.3 ± 0.2 × 107 l mol–1 S–1 has been determined.
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