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Kinetics and mechanisms of the reactions of OH with some oxygenated compounds of importance in tropospheric chemistry

✍ Scribed by S. M. Saunders; D. L. Baulch; K. M. Cooke; M. J. Pilling; P. I. Smurthwaite

Publisher: John Wiley and Sons
Year: 1994
Tongue: English
Weight: 662 KB
Volume: 26
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550260112

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✦ Synopsis

The kinetics of the reactions (1) OH + (CH3)3COH -.+ products (2) OH + (CH~)ZCHCH~CH~OHproducts 0 // (3) 0 OCH3 4 products (4)

OH + CH2 =CH-C, have been studied in a discharge flow system under pseudo-first-order conditions. The OH concentration was monitored by laser induced fluorescence and helium was used as the carrier gas. Values of k l = (8.1 2 1.7) X 10-13, k2 = (1.31 ? 0.26) X 1O-l1, k3 = (2.6 2 0.5) X and kq = (2.5 2 0.4) X 10-l1 cm3 molecule-l s-l, at 298 K and 1 torr total pressure, were obtained.

To validate the newly constructed system the rate constant for the reaction

was determined in a similar manner. The value of k5 = (6.7 ? 0.9) X cm3 molecule-' s-l at 298 K and 1 torr total pressure is in very good agreement with other literature values.

The mechanisms for the atmospheric degradation of these compounds have been constructed to allow their incorporation in a photochemical trajectory computer model, to assess their impact on photochemical ozone creation in the troposphere.

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