Substituent effects on rates of one-electron oxidation of phenols by the radicals ClO/sub 2/, NO/sub 2/, and SO/sub 3//sup -/
Rate constants for the reactions of ClO/sub 2/, NO/sub 2/, and SO/sub 3//sup -/ radicals with several substituted phenoxide ions have been measured by pulse radiolysis. They vary from the immeasurably slow (<10/sup 4/) to almost diffusion-controlled rates (>10/sup 9/ M/sup -1/s/sup -1/) and depend on the redox potentials of the phenoxide ions and the inorganic radicals. With the weak oxidant SO/sub 3//sup -/ reverse reactions were observed in certain cases; i.e., the phenoxyl radical oxidizes sulfite ions. An attempt is made to correlate the rate constants with Hammett's substituent constants and the results are compared with those obtained previously for the reactions of various inorganic radicals with phenols and phenoxide ions.
- Research Organization:
- National Bureau of Standards, Gaithersburg, MD
- OSTI ID:
- 5458703
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:17; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AROMATICS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
PHENOLS
RADICALS
REACTION KINETICS
SYNTHESIS