Hydrogen abstraction by tert-butoxy radicals. A laser photolysis and electron spin resonance study

Journal Article · Wed Jul 05 04:00:00 EDT 1978 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00482a033· OSTI ID:6740847

Paul, H; Small, Jr, R D; Scaiano, J C

The absolute rates of reaction of tert-butoxy radicals with a variety of organic substrates in solution have been determined using laser flash photolysis techniques. The relative rates agree well with values obtained from studies of hydrocarbon halogenation by tert-butyl hypochlorite or by ESR in the case of ethers and alcohols, while the absolute rates are considerably higher than suggested by previous reports. The absolute rate constants reaffirm the similarity between the behavior of alkoxy radicals and carbonyl triplets. Di-tert-butyl peroxide photosensitizes the decomposition of carbon tetrachloride into trichloromethyl radicals and chlorine atoms. The process involves excited peroxide molecules, rather than tert-butoxy radicals. 8 figures, 4 tables.

• Research Organization: Univ. of Notre Dame, IN
• OSTI ID: 6740847
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Journal Issue: 14 Vol. 100:14; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKOXY RADICALS
BUTOXY RADICALS
CARBON TETRACHLORIDE
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
HALOGENATED ALIPHATIC HYDROCARBONS
LASER RADIATION
MAGNETIC RESONANCE
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
RADICALS
RESONANCE