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Reaction rate constant for OH + HOONO/sub 2/. -->. products over the temperature range 246 to 324 K

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100206a035· OSTI ID:6770587

Absolute bimolecular reaction rate constants for the title reaction have been determined for temperatures ranging from 246 to 324 K. The laser flash-photolysis resonance-fluorescence (LFPRF) technique was used to generate O(/sup 1/D) which reacted with H/sub 2/ and/or H/sub 2/O to produce OH radicals. The bimolecular rate constants for the title reaction showed no dependence on total (He) pressure over the range approx. 3 to 15 torr, and they did not depend upon initial (OH) or upon its mode of formation. The H/sub 2/O/sub 2/ impurity was explicitly measured in all experiments, and the rate constants were corrected for its contribution. A weighted least-squares analysis of the data obtained at nine temperatures (226 data points) gave the Arrhenius expression (k +- 1sigma) = (8.05 +- 5.69) x 10/sup -12/ exp (-193 +- 194/T) cm/sup 3/ s/sup -1/ with covariance 1.098 x 10/sup -9/. A simple weighted average (temperature independent) fits the data just as well, and when the effects of systematic errors are taken into account, our recommended rate constant is (k +- 2sigma) = (4.0 +- 1.6) x 10/sup -12/ cm/sup 3/ s/sup -1/.

Research Organization:
SRI International, Menlo Park, CA
OSTI ID:
6770587
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:9; ISSN JPCHA
Country of Publication:
United States
Language:
English