Gas-phase rate coefficients for the reaction of 3-hydroxy-2-butanone and 4-hydroxy-2-butanone with OH and Cl

The reactions of the OH radicals and the Cl atoms with 3-hydroxy 2-butanone (3H2B) and 4-hydroxy 2-butanone (4H2B) were investigated in the gas-phase using relative rate method. The kinetic study on the OH-reactions was carried out using a Pyrex atmospheric chamber at 600-760 Torr of purified air. The temperature ranges were 298-338 K for 3H2B and 278-333 K for 4H2B. A slight negative dependence of the rate coefficients behaviour was observed and the Arrhenius expressions obtained are (in cm(3) molecule(-1) s(-1)): k(3H2B(OH)) = (1.25 +/- 0.20) x 10(-12)exp(612 +/- 50/T-1) and k(4HB) (OH) = (7.50 +/- 2.0) x 10(-1)2exp(196 +/- 20/T-1). Rate coefficients for the gas-phase reactions of Cl atoms with 3H2B and 4H2B were measured using an atmospheric simulation chamber made of Teflon at 298 +/- 3 K and 760 Torr. The obtained rate coefficients (in cm(3) molecule(-1) s(-1)) were (4.90 +/- 0.45) x 10(-11) and (1.45 +/- 0.15) x 10(-1) for 3H2B and 4H2B, respectively. The obtained data are presented, compared to those reported in the literature and the reactivity trends discussed. The estimated tropospheric lifetimes obtained in this work suggest that once emitted into the atmosphere, 3H2B and 4H2B will be oxidized near the emission sources. (C) 2013 Elsevier Ltd. All rights reserved.