Kinetics studies of the reactions of CH/sub 3/O/sub 2/ with NO, NO/sub 2/, and CH/sub 3/O/sub 2/ at 298 K
Journal Article
·
· J. Phys. Chem.; (United States)
The flash photolysis/ultraviolet absorption technique was used to measure the rate constants for the reactions CH/sub 3/O/sub 2/ + NO ..-->.. CH/sub 3/O + NO/sub 2/ (1), CH/sub 3/O/sub 2/ + NO/sub 2/ + M ..-->.. CH/sub 3/O/sub 2/NO/sub 2/ + M (2), and CH/sub 3/O/sub 2/ + CH/sub 3/O/sub 2/ ..-->.. products (3) at 298 K over the pressure range 50 to 700 torr. Values for k/sub 1/ and k/sub 3/ were determined to be (7.1 +- 1.4) x 10/sup -12/ cm/sup 3/ molecule/sup -1/s/sup -1/ and (3.6 +- 0.7) x 10/sup -13/ cm/sup 3/ molecule/sup -1/s/sup -1/, respectively, where k/sub 3/ is defined by the relation -d(CH/sub 3/O/sub 2/)/dt = 2k/sub 3/(CH/sub 3/O/sub 2/)/sup 2/; k/sub 2/ was found to vary strongly with pressure, indicating that the reaction occurs primarily by addition and is in the falloff region between second- and third-order kinetics. Experimentally determined parameters describing the shape of the falloff curve for k/sub 2/ were in reasonable agreement with those obtained by using theoretical methods developed by Troe and co-workers. An upper limit of 7 x 10/sup -18/ cm/sup 3/ molecule/sup -1/s/sup -1/ was determined for the rate constant for the reaction CH/sub 3/O/sub 2/ + CO ..-->.. products.
- Research Organization:
- Jet Propulsion Lab., Pasadena, CA
- OSTI ID:
- 6810117
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 84:13; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
500200* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
INFORMATION
KINETICS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS
400500 -- Photochemistry
500200* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
INFORMATION
KINETICS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS