Gas-phase oxidation of CH2 = C(CH3 )CH2 Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Abstract

Relative kinetics of the reactions of OH radicals and Cl atoms with 3-chloro-2-methyl-1-propene has been studied for the first time at 298 K and 1 atm by GC-FID. Rate coefficients are found to be (in cm3 molecule−1 s−1): k1 (OH + CH2 = C(CH3)CH2Cl) = (3.23 ± 0.35) × 10−11, k2 (Cl + CH2 = C(CH3)CH2Cl) = (2.10 ± 0.78) × 10−10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC-MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2-hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.