Abstract
Rate coefficients have been measured for the reactions of Cl atoms with methanol (k1) and acetaldehyde (k2) using both absolute (laser photolysis with resonance fluorescence) and relative rate methods at 295 ± 2 K. The measured rate coefficients were (units of 10−11 cm3 molecule−1 s−1): absolute method, k1 = (5.1 ± 0.4), k2 = (7.3 ± 0.7); relative method k1 = (5.6 ± 0.6), k2 = (8.4 ± 1.0). Based on a critical evaluation of the literature data, the following rate coefficients are recommended: k1 = (5.4 ± 0.9) × 10−11 and k2 = (7.8 ± 1.3) × 10−11 cm3 molecule−1 s−1 (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 Cl2 with CH2OH, k5 = (2.9 ± 0.6) × 10−11 and CH3CO, k6 = (4.3 ± 1.5) × 10−11 cm3 molecule−1 s−1, by observing the regeneration of Cl atoms in the absence of O2. Based on these results and those from a previous relative rate study, the rate coefficient for CH3CO + O2 at the high pressure limit is estimated to be (5.7 ± 1.9) × 10−12 cm3 molecule−1 s−1. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 776–784, 1999
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