Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures

Abstract

The kinetics of reactions of the OH radical with ethene, ethyne (acetylene), propyne (methyl acetylene) and t-butyl-hydroperoxide were studied at temperatures of 69 and 86 K using laser flash-photolysis combined with laser-induced fluorescence spectroscopy. A new pulsed Laval nozzle apparatus is used to provide the low-temperature thermalised environment at a single density of similar to 4 x 10(16) molecule cm(-3) in N-2. The density and temperature within the flow are determined using measurements of impact pressure and rotational populations from laser-induced fluorescence spectroscopy of NO and OH. For ethene, rate coefficients were determined to be k(2) = (3.22 +/- 0.46) x 10(-11) and (2.12 +/- 0.12) x 10(-11) cm(3) molecule(-1) s(-1) at T = 69 and 86 K, respectively, in good agreement with a master-equation calculation utilising an ab initio surface recently calculated for this reaction by Cleary et al. (P. A. Cleary, M. T. Baeza Romero, M. A. Blitz, D. E. Heard, M. J. Pilling, P. W. Seakins and L. Wang, Phys. Chem. Chem. Phys., 2006, 8, 5633-5642) For ethyne, no previous data exist below 210 K and a single measurement at 69 K was only able to provide an approximate upper limit for the rate coefficient of k(3) < 1 x 10(-12) cm(3) molecule(-1) s (-1), consistent with the presence of a small activation barrier of similar to 5 kJ mol (-1) between the reagents and the OH-C2H2 adduct. For propyne, there are no previous measurements below 253 K, and rate coefficients of k(4) = (5.08 +/- 0.65), (5.02 +/- 1.11) and (3.11 +/- 0.09) x 10(-12) cm(3) molecule(-1) s(-1) were obtained at T = 69, 86 and 299 K, indicating a much weaker temperature dependence than for ethene. The rate coefficient k(1) = (7.8 +/- 2.5) x 10(-11) cm(3) molecule(-1) s (-1) was obtained for the reaction of OH with t-butyl-hydroperoxide at T = 86 K. Studies of the reaction of OH with benzene and toluene yielded complex kinetic profiles of OH which did not allow the extraction of rate coefficients. Uncertainties are quoted at the 95% confidence limit and include systematic errors