Direct frequency comb measurement of OD + CO arrow right DOCO kinetics

The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2016-10, Vol.354 (6311), p.444-448
Main Authors: Bjork, B J, Bui, T Q, Heckl, OH, Changala, P B, Spaun, B, Heu, P, Follman, D, Deutsch, C, Cole, G D, Aspelmeyer, M, Okumura, M, Ye, J
Format: Article
Language:English
Subjects:
Broadband
Carbon monoxide
Combustion chemistry
Formations
Hydroxyl radicals
Radicals
Reaction kinetics
Time dependence
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Summary:The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed under thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observed deuteroxyl radical (OD) + CO reaction kinetics and detected stabilized trans-DOCO, the deuterated analog of trans-HOCO. By simultaneously measuring the time-dependent concentrations of the trans-DOCO and OD species, we observed unambiguous low-pressure termolecular dependence of the reaction rate coefficients for N2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.
ISSN:0036-8075
DOI:10.1126/science.aag1862