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An FTIR study of the Cl-atom-initiated reaction of glyoxal

✍ Scribed by H. Niki; P. D. Maker; C. M. Savage; L. P. Breitenbach

Publisher: John Wiley and Sons
Year: 1985
Tongue: English
Weight: 564 KB
Volume: 17
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550170507

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✦ Synopsis

The kinetics and mechanism of C1-atom-initiated reactions of CHO-CHO were studied using the FTIR detection method to monitor the photolysis of Cl,-CHO-CHO mixtures in 700 torr of N2-0, diluent at 298 ? 2 K. The observed product distribution in the [021 pressure of 0-700 torr combined with relative rate measurements provide evidence that: (1) the primary step is C1 + CHO-CHO -+ HC1 + CHO-CO with a rate constant of [3.8 ? 0.3((r)] x lo-" cm3 molecule^'^-^; (2) the primary product CHO-CO unimolecularly dissociates to CHO and CO with an estimated lifetime of sca. 1 x s; (3) alternatively, the CHO-CO reacts with O2 leading to the formation of CO, C02, and most likely the HO radical, but no stable products containing two carbon atoms; (4) the H02 radical, formed in the secondary reaction CHO + O2 + HO, + CO, reacts with the CHO-CHO with a rate constant ca. 5 x cm3 molecule-' s-l to form HCOOH and a new transient product resembling that detected previously in the H 0 2 reaction with HCHO.

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