Rate constants for the gas-phase reactions of OH radicals with a series ofunsaturated alcohols

Using a relative rate method, rate constants for the gas-phase reactions of OH radicals with allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, and 2-methyl-3 -buten-2-ol have been measured at 296 +/- 2 K and atmospheric pressure of a ir. Using 1,3,5-trimethylbenzene as the reference compound, the rate consta nts tin units of 10(-11) cm(3) molecule(-1) s(-1)) were: allyl alcohol, 5.4 6 +/- 0.35; 3-buten-1-ol, 5.50 +/- 0.20: 3-buten-2-ol, 5.93 +/- 0.23: and 2 -methyl-3-buten-2-ol, 5.67 +/- 0.13: where the indicated errors are two lea st-squares standard deviations and do not include the uncertainty in the ra te constant for 1,3,5-trimethylbenzene. The H-atom abstraction products acr olein and methyl vinyl ketone were observed from the allyl alcohol and 3-bu ten-2-ol reactions, respectively, with respective yields of 5.5 +/- 0.7 and 4.9 +/- 1.4%. No evidence For formation of acrolein from 3-buten-1-ol or 3 -buten-2-ol was obtained, with upper limits to the acrolein yields of less than or equal to1.2 and less than or equal to0.5%, respectively, being dete rmined. Reaction mechanisms are discussed. (C) 2001 John Wiley & Sons.