Direct measurements of DOCO isomers in the kinetics of OD + CO

Quantitative and mechanistically detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studi...

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Published in:Science advances 2018-01, Vol.4 (1), p.eaao4777-eaao4777
Main Authors: Bui, Thinh Q, Bjork, Bryce J, Changala, P Bryan, Nguyen, Thanh L, Stanton, John F, Okumura, Mitchio, Ye, Jun
Format: Article
Language:English
Subjects:
Chemistry
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary:Quantitative and mechanistically detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studies for accurate determination of the reaction rate coefficient and its pressure and temperature dependence at thermal reaction conditions. This intricate dependence can be traced directly to details of the underlying dynamics (formation, isomerization, and dissociation) involving the reactive intermediates - and -HOCO, which can only be observed transiently. Using time-resolved frequency comb spectroscopy, comprehensive mechanistic elucidation of the kinetics of the isotopic analog deuteroxyl radical (OD) with CO has been realized. By monitoring the concentrations of reactants, intermediates, and products in real time, the branching and isomerization kinetics and absolute yields of all species in the OD + CO reaction are quantified as a function of pressure and collision partner.
ISSN:2375-2548
2375-2548
DOI:10.1126/sciadv.aao4777