Rate constants for the reaction HO2 + NO2 + N2 HO2NO2 + N2: the temperature dependence of the falloff parameters

Journal Article · Thu Jun 04 04:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100296a052· OSTI ID:6368853

Kurylo, M J; Ouellette, P A

Rate constants for the title reaction were measured by flash photolysis ultraviolet absorption spectroscopy at N2 pressures of 25, 50, and 100 Torr over the temperature range 228-358 K. The data were fit to an expression suitable for describing the pressure dependence of reactions in the falloff region with the temperature dependence of the falloff parameters given by k/sub 0,N2/(T) = k/sub 0,N2/(300K))T/300)/sup -n/ and k/sub infinity/(300K))T/300)/sup -m/. The inert gas pressures in this study were low enough to permit a precise determination of n (which describes the temperature dependence of the low-pressure, limiting third-order rate constant). The same rate constant data, however, were less sensitive to the determination of m (associated with the limiting high-pressure rate constant). For this reason, their final analysis utilizes a composite fit of their temperature dependent data along with similar data at 100 and 700 Torr of N2 obtained by Sander and Peterson to yield K/sub 0,N2/(T) = 1.8 x 10 T)T/300)/sup -(3.2 +/- 0.4)/ cmW molecule: S s and K/sub infinity/(T) = 4.7 x 10 S)T/300)/sup -(1.4 +/- 1.0)/ cmT molecule s .

• Research Organization: National Bureau of Standards, Gaithersburg, MD
• OSTI ID: 6368853
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:12; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
500200 -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
EXPERIMENTAL DATA
HYDROPEROXY RADICALS
INFORMATION
KINETICS
LOW PRESSURE
MEDIUM TEMPERATURE
NITROGEN
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NONMETALS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS
SPECTRA
SPECTROSCOPY
ULTRAVIOLET SPECTRA
YIELDS