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

Abstract

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 air. Using 1,3,5-trimethylbenzene as the reference compound, the rate constants (in units of 10-11 cm3 molecule-1 s-1) were: allyl alcohol, 5.46±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 least-squares standard deviations and do not include the uncertainty in the rate constant for 1,3,5-trimethylbenzene. The H-atom abstraction products acrolein and methyl vinyl ketone were observed from the allyl alcohol and 3-buten-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 ≤1.2 and ≤0.5%, respectively, being determined. Reaction mechanisms are discussed.