Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm(3) molecule(-1) s(-1)): k(1)(OH+CH2 = CHC(O)OH) = (1.75 +/- 0.47) x 10(-11) , k(2)(Cl + CH2 = CHC(O)OH) = (3.99 +/- 0.84) x 10(-10), k(3)(OH + CH2 = CHCN) = (1.11 +/- 0.33) x 10(-11) and k(4)(Cl + CH2 = CHCN) = (1.11 +/- 0.23) x 1 0(-10) with uncertainties representing +/- 2 sigma. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds. (c) 2007 Elsevier Ltd. All rights reserved.