Kinetics and Mechanisms of OH-Initiated Oxidation of Small Unsaturated Alcohols

Smog chamber relative rate techniques were used to measure rate coefficients of (5.00 +/- 0.54) x 10(-11). (5.87 +/- 0.63) x 10(-11), and (6.49 +/- 0.82) x 10(-11) cm(3) 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 (C) 2010 Wiley Periodicals, Inc Int J Chem Kinet. 42 151-158, 2010