Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

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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) × 10−11cm3molecule−1s−1in 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 NOxgives 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CH2double bond with most of the addition occurring to the terminal carbon.