Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols |
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Authors: | Kenshi Takahashi Michael D Hurley Timothy J Wallington |
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Institution: | 1. Pioneering Research Unit and Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, 611‐0011, Japan;2. System Analytics & Environmental Sciences Department, Ford Motor Company, P. O. Box: 2053, Dearborn, MI 48121‐2053 |
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Abstract: | Smog chamber relative rate techniques were used to measure rate coefficients of (5.00 ± 0.54) × 10?11, (5.87 ± 0.63) × 10?11, and (6.49 ± 0.82) × 10?11 cm3 molecule?1 s?1 in 700 Torr air at 296 ± 1 K for reactions of OH radicals with allyl alcohol, 1‐buten‐3‐ol, and 2‐methyl‐3‐buten‐2‐ol, respectively; the quoted uncertainties encompass the extremes of determinations using two different reference compounds. The OH‐initiated oxidation of allyl alcohol in the presence of NOx gives glycolaldehyde in a molar yield of 0.85 ± 0.08; the quoted uncertainty is two standard deviations. Oxidation of 2‐methyl‐3‐buten‐2‐ol gives acetone and glycolaldehyde in molar yields of 0.66 ± 0.06 and 0.56 ± 0.05, respectively. The reaction of OH radicals with allyl alcohol, 1‐buten‐3‐ol, and 2‐methyl‐3‐buten‐2‐ol proceeds predominately via addition to the >C?CH2 double bond with most of the addition occurring to the terminal carbon. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 151–158, 2010 |
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