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Rate coefficients for the reactions of chlorine atoms with methanol and acetaldehyde

✍ Scribed by G. S. Tyndall; J. J. Orlando; C. S. Kegley-Owen; T. J. Wallington; M. D. Hurley

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
159 KB
Volume
31
Category
Article
ISSN
0538-8066

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✦ Synopsis

Rate coefficients have been measured for the reactions of Cl atoms with methanol (k 1 ) and acetaldehyde (k 2 ) using both absolute (laser photolysis with resonance fluorescence) and relative rate methods at 295 Ϯ 2 K. The measured rate coefficients were (units of 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 ): absolute method, k 1 ϭ (5.1 Ϯ 0.4), k 2 ϭ (7.3 Ϯ 0.7); relative method k 1 ϭ (5.6 Ϯ 0.6), k 2 ϭ (8.4 Ϯ 1.0). Based on a critical evaluation of the literature data, the following rate coefficients are recommended: k 1 ϭ (5.4 Ϯ 0.9) ϫ 10 Ϫ11 and k 2 ϭ (7.8 Ϯ 1.3) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 (95% confidence limits). The results significantly improve the confidence in the database for reactions of Cl atoms with these oxygenated organics. Rate coefficients were also measured for the reactions of Cl 2 with CH 2 OH, k 5 ϭ (2.9 Ϯ 0.6) ϫ 10 Ϫ11 and CH 3 CO, k 6 ϭ (4.3 Ϯ 1.5) ϫ 10 Ϫ11 cm 3 molecule Ϫ1 s Ϫ1 , by observing the regeneration of Cl atoms in the absence of O 2 . Based on these results and those from a previous relative rate study, the rate coefficient for CH 3 CO ϩ O 2 at the high pressure limit is estimated to be (5.7 Ϯ 1.9) ϫ 10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 .

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