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The pressure dependence of the rate constant for the reaction: HO + CO → H + CO2

✍ Scribed by Walter H. Chan; William M. Uselman; Jack G. Calvert; John H. Shaw

Publisher
Elsevier Science
Year
1977
Tongue
English
Weight
503 KB
Volume
45
Category
Article
ISSN
0009-2614

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✦ Synopsis

Relative rate measurements of the reactions of the HO-radical with CO [HO + CO -+ H + COa (1) ] and with isobutane [HO f iso-C4H10 -t Hz0 f f-(or iso-)CaHg ( 3)J have been made through the photolysis of dilute mixtures of HONO with CO, ixo-Cd H ro, N0a, and NO in simulated air at 700 and 100 torr pressure and 25 f 2°C. In situ, long path, FT-IR analysis of the reactants and products provided essentially continuous monitoring of the reactions during the course of the experiments. The kinetic analysis of the data coupled with Greiner's estimate of k3 give new estimates ofX_r = 439 + 24 ppm-' min-' in air at 700 torr and kt = 203 f 29 ppm-' min-t in air at 100 tot-r. The results confii the recent conclusions of Cos and Sic and their co-workers that the rate constant for reaction (1) is pressure dependent. Modeliers of the chemical changes which occur in the troposphere should adopt a new value for the rate constant kr which is about a factor of two huger than that in current use by most groups.

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