Pressure and temperature dependence of the reaction CH/sub 3/ + O/sub 2/ + M. -->. CH/sub 3/O/sub 2/ + M over the range 334 less than or equal to T/K less than or equal to 582
The rate constant of the reaction between methyl radicals and molecular oxygen has been determined over the pressure range 20-600 Torr (in argon) and at six temperatures in the range 334 less than or equal to T/K less than or equal to 582 by excimer laser flash photolysis coupled with time-resolved absorption spectroscopy of the methyl radical. The data were analyzed according to the factorization method of Troe: two fitting techniques are described, the more satisfactory of which determines a global fit to the whole k(P,T) data set. An unweighted nonlinear least-squares fit to all the falloff data gives the limiting rate constants k/sub 1//sup in equilibrium/ = ((1.2 +/- 0.2) x 10/sup -12/)(T/300 K)/sup 1.2 +/- 0.4/ cm/sup 3/ molecule/sup -1/ s/sup -1/ and k/sub 1//sup 0/ = ((1.0 +/- 0.3) x 10/sup -30/)(T/300 K)/sup -3.3 +/- 0.4/ cm/sup 6/ molecule/sup -2/ s/sup -1/. Parameters are provided that enable the rate constant k to be calculated as a function of pressure and temperature.
- Research Organization:
- Physical Chemistry Lab., Oxford, England
- OSTI ID:
- 5940985
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:23; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Pyrolysis
& High-Temperature Chemistry
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
ALKYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
EXCIMER LASERS
EXPERIMENTAL DATA
GAS LASERS
HIGH TEMPERATURE
INFORMATION
KINETICS
LASERS
LOW PRESSURE
MEDIUM TEMPERATURE
METHYL RADICALS
NONMETALS
NUMERICAL DATA
OXYGEN
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
RADICALS
REACTION KINETICS
SPECTROSCOPY
TEMPERATURE DEPENDENCE