High-pressure falloff curves and specific rate constants for the reactions H + O/sub 2/ in equilibrium HO/sub 2/ in equilibrium HO + O

Journal Article · Thu Jan 17 04:00:00 EST 1985 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100248a033· OSTI ID:5787793

Cobos, C J; Hippler, H; Troe, J

The recombination reaction H + O/sub 2/ + M ..-->.. HO/sub 2/ + M is studied by laser flash photolysis in the bath gases M = Ar, N/sub 2/, and CH/sub 4/ at pressures between 1 and 200 bar. By extrapolation of the falloff curves, a limiting high-pressure rate coefficient k/sub infinity/ = 7.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is derived at 298 K. An analysis of this result in terms of the statistical adiabatic channel model leads to a looseness parameter of a similarly ordered 0.94 A/sup -1/. The corresponding specific rate constants k(E,J) for dissociation of HO/sub 2/ are constructed and compared with trajectory calculations. The results are also compared with data on the reaction HO + O ..-->.. H + O/sub 2/ for which a nearly temperature-independent rate constant of 2.8 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is predicted. An analysis of the limiting low-pressure rate coefficients with respect to energy-transfer properties is made. The results are compared with trajectory calculations of energy transfer of excited HO/sub 2/. 77 references, 8 figures, 5 tables.

• Research Organization: Universitaet Goettingen, West Germany
• OSTI ID: 5787793
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:2; 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
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400500 -- Photochemistry
400600* -- Radiation Chemistry
500200 -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTRA
ALKANES
ARGON
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
DATA
DECOMPOSITION
ELEMENTS
EVALUATED DATA
EXPERIMENTAL DATA
FLUIDS
GAS LASERS
GASES
HIGH PRESSURE
HYDROCARBONS
HYDROGEN
HYDROPEROXY RADICALS
HYDROXYL RADICALS
INFORMATION
KINETICS
LASERS
MATHEMATICAL MODELS
MEDIUM PRESSURE
MEDIUM TEMPERATURE
METHANE
NITROGEN
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
RADICALS
RARE GASES
REACTION KINETICS
RECOMBINATION
SPECTRA
TEMPERATURE DEPENDENCE