Electron spin resonance study of the decay of methyl radical--bromide ion pairs in acetonitrile at low temperature

Journal Article · Thu Apr 05 04:00:00 EST 1979 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100470a017· OSTI ID:6255946

Sprague, E D

Methyl radicals adjacent to cyanide ions are generated upon photolysis of ..gamma..-irradiated, crystalline acetonitrile, and these radicals decay by hydrogen atom abstraction from neighboring matrix molecules. In this paper the kinetic consequences of a slight alteration in the immediate environment of the methyl radical are examined. It is found that replacement of the cyanide ion with a bromide ion causes the observed rate constant for abstraction to be lower by about a factor of 2 at low temperatures. Once again, the low activation energy and large deuterium kinetic isotope effect are indicative of very important tunnel effects in the abstraction reaction.

• Research Organization: Univ. of Cincinnati, OH
• OSTI ID: 6255946
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 83:7; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400600* -- Radiation Chemistry
ALKYL RADICALS
BROMIDES
BROMINE COMPOUNDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CYANIDES
DATA
DATA FORMS
DECOMPOSITION
DEUTERIUM
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
GAMMA RADIATION
HALIDES
HALOGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONIZING RADIATIONS
ISOLATED VALUES
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
METHYL RADICALS
NITRILES
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RESONANCE
STABLE ISOTOPES