Absorption spectrum and rates of formation and decay of the CH/sub 3/O/sub 2/ radical

Journal Article · Thu Jan 13 04:00:00 EST 1977 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100516a002· OSTI ID:7227926

Hochanadel, C J ^[1]; Ghormley, J A; Boyle, J W; Ogren, P J

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1. Oak Ridge National Lab., TN

Flash photolysis of azomethane was used to produce CH/sub 3/ radicals which reacted with O/sub 2/ to form CH/sub 3/O/sub 2/. The CH/sub 3/O/sub 2/ radical was found to have a broad absorption spectrum centered at 2350 A, with a maximum extinction coefficient of 870 M/sup -1/ cm/sup -1/ based on loss of azomethane. The rate constant at 295 +- 2 K for the formation reaction CH/sub 3/ + O/sub 2/ + M ..-->.. CH/sub 3/O/sub 2/ + M (k/sub 2/) in the second-order limit was found to be 1.3 +- 0.2 x 10/sup 9/ M/sup -1/ s/sup -1/. The rate constant for the combination of peroxy radicals, CH/sub 3/O/sub 2/ + CH/sub 3/O/sub 2/ ..-->.. products (k/sub 3/), was 2.3 +- 0.3 x 10/sup 8/ M/sup -1/ s/sup -1/, and for the combination of methyl radicals, CH/sub 3/ + CH/sub 3/ + M ..-->.. C/sub 2/H/sub 6/ + M (k/sub 1/), it was 3.1 +- 0.6 x 10/sup 10/ M/sup -1/ s/sup -1/. The reactions were monitored by kinetic spectrophotometry of CH/sub 3/ absorption at 2160 A and CH/sub 3/O/sub 2/ absorption at 2480 A.

• OSTI ID: 7227926
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 81:1; 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
400500 -- Photochemistry
400600* -- Radiation Chemistry
ABSORPTION SPECTRA
ALKYL RADICALS
AZO COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECAY
DECOMPOSITION
KINETICS
MEDIUM TEMPERATURE
METHYL RADICALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PEROXY RADICALS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
SPECTRA
SYNTHESIS