Kinetics of OH radical reaction with allyl alcohol (H2C=CHCH2OH) and propargyl alcohol (HC CCH2OH) studied by LIF

The rate constants for the reactions of hydroxyl radical (OH) with two unsa turated alcohols (ROH) namely, allyl alcohol (H2C=CHCH2OH) and propargyl al cohol (HC drop CCH2OH) in the gas phase have been measured. The kinetic mea surements were carried out using laser photolysis (LP) combined with laser induced fluorescence (LIF) technique at room temperature over a pressure ra nge of 10-20 Torr. The bimolecular rate constants for the reactions OH + RO H --> products, are determined at room temperature to be (3.7 +/- 0.5) x 10 (-11), (9.2 +/- 1.4) x 10(-12) cm(3) molecule(-1) s(-1), respectively, for allyl alcohol and propargyl alcohol. The measured rate constants in combina tion with ab initio molecular orbital calculation provide a better understa nding of the structure-reactivity rules. (C) 2001 Published by Elsevier Sci ence B.V.