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©NIST, 2013
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Author(s):   Lockhart, J.; Blitz, M.; Heard, D.; Seakins, P.; Shannon, R.
Title:   Kinetic Study of the OH plus Glyoxal Reaction: Experimental Evidence and Quantification of Direct OH Recycling
Journal:   J. Phys. Chem. A
Volume:   117
Page(s):   11027 - 11037
Year:   2013
Book Title:   ''
Editor:   ''
Publisher:   ''
Publisher address:   ''
Comments:   ''
Reference type:   Journal article
Squib:   2013LOC/BLI11027-11037

Reaction:   O2 + HC(O)CO → CO2 + CO + ·OH
Reaction order:   2
Temperature:   212 - 295 K
Pressure:  6.67E-3 - 0.11 bar
Rate expression:   no rate data available
Category:  Experiment
Data type:   Mechanistic information only
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Laser induced fluorescence
Comments:   The kinetics of the OH + glyoxal have been studied by monitoring the OH decay via laser induced fluorescence. Rate coefficient measurements were observed to be independent of total pressure but decreased following the addition of molecular oxygen to the reaction cell, consistent with direct OH recycling. OH yields were quantified experimentally as a function of total pressure, temperature, and molecular oxygen concentration. The experimental results have been parametrized using a chemical scheme where a fraction of the HC(O)CO population promptly dissociates to HCO + CO, the remaining HC(O)CO either dissociates thermally or reacts with molecular oxygen to give carbon dioxide, CO, and regenerate OH. A maximum OH yield of (0.38 ± 0.02) was observed at 212 K, independent of total pressure, suggesting that ∼60% of the HC(O)CO population promptly dissociates upon formation. Qualitatively similar behavior is observed at 250 K, with a maximum OH yield of (0.31 ± 0.03); at 295 K, the maximum OH yield decreased further to (0.29 ± 0.03). Experimental evidence suggests that the system is influenced by chemical activation and cannot be fully described by thermal rate coefficients.

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