Time-resolved ESR study of the kinetics of spin trapping by nitromethane aci-anion
The kinetics of spin trapping by the aci-anion of nitromethane have been studied for some representative radicals in aqueous solution by using time-resolved ESR with in situ radiolysis. In nearly all cases, reaction of a radical R produced an adduct RCH/sub 2/NO/sub 2//sup -/. However, these time-resolved experiments showed that /sup ./CH/sub 2/O/sup -/ produces both an adduct and the radical anion of nitromethane. Second-order rate constants varied from 1.4 x 10/sup 7/ M/sup -1/ s/sup -1/ for CO/sub 2//sup -/ to 3.8 x 10/sup 8/ for the p-carboxyphenyl radical. Reducing radicals (CO/sub 2//sup -/, CH/sub 2/O/sup -/, (CH/sub 3/)/sup 2/COH, and (CH/sub 3/)/sub 2/CO/sup -/) react less rapidly than alkyl radicals (CH/sub 2/CO/sub 2//sup -/, CH/sub 3/) which in turn react less rapidly than sigma radicals (p-carboxyphenyl and CONH/sub 2/).
- Research Organization:
- Univ. of Notre Dame, IN (USA)
- OSTI ID:
- 6975287
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:9; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400600 -- Radiation Chemistry
ANIONS
AQUEOUS SOLUTIONS
CHARGED PARTICLES
CHEMICAL EXPLOSIVES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DISPERSIONS
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
EXPLOSIVES
INFORMATION
IONS
KINETICS
MAGNETIC RESONANCE
MIXTURES
NITRO COMPOUNDS
NITROMETHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
RESONANCE
SOLUTIONS