Rate constants for the reactions of free radicals with oxygen in solution
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10/sup 9/; benzyl, 2.36 x 10/sup 9/ (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10/sup 9/ M/sup -1/ s/sup -1/. The reaction of butyl-tin (n-Bu/sub 3/Sn.) radicals is unusually fast (7.5 x 10/sup 9/ M/sup -1/ s/sup -1/), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table.
- Research Organization:
- National Research Council, Ottawa, Ontario
- OSTI ID:
- 5614522
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:15; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500* -- Photochemistry
400600 -- Radiation Chemistry
ALKANES
ALKENES
ALKYL RADICALS
AROMATICS
ARYL RADICALS
BENZENE
BENZYL RADICALS
BUTYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
CYCLOALKENES
CYCLOHEXANE
DATA
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IONIZATION
KINETICS
LASER RADIATION
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
OXYGEN
PHOTOIONIZATION
RADIATIONS
RADICALS
REACTION KINETICS
SOLVENTS
TIN COMPLEXES
YIELDS
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500* -- Photochemistry
400600 -- Radiation Chemistry
ALKANES
ALKENES
ALKYL RADICALS
AROMATICS
ARYL RADICALS
BENZENE
BENZYL RADICALS
BUTYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
CYCLOALKENES
CYCLOHEXANE
DATA
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
IONIZATION
KINETICS
LASER RADIATION
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
OXYGEN
PHOTOIONIZATION
RADIATIONS
RADICALS
REACTION KINETICS
SOLVENTS
TIN COMPLEXES
YIELDS