Rate constants for the reactions of chlorine atoms with hydrochloroethers at 298 k and atmospheric pressure

Abstract

AbstractThe relative rate technique has been used to determine the rate constants for the reactions Cl + CH3OCHCl2 → products and Cl + CH3OCH2CH2Cl → products. Experiments were carried out at 298 ± 2 K and atmospheric pressure using nitrogen as the bath gas. The decay rates of the organic species were measured relative to those of 1,2‐dichloroethane, acetone, and ethane. Using rate constants of (1.3 ± 0.2) × 10−12 cm3 molecule−1 s−1, (2.4 ± 0.4) × 10−12 cm3 molecule−1 s−1, and (5.9 ± 0.6) × 10−11 cm3 molecule−1 s−1 for the reactions of Cl atoms with 1,2‐dichloroethane, acetone, and ethane respectively, the following rate coefficients were derived for the reaction of Cl atoms (in units of cm3 molecule−1 s−1) with CH3OCHCl2, k= (1.04 ± 0.30) × 10−12 and CH3OCH2CH2Cl, k= (1.11 ± 0.20) × 10−10. Errors quoted represent two σ, and include the errors due to the uncertainties in the rate constants used to place our relative measurements on an absolute basis. The rate constants obtained are compared with previous literature data and used to estimate the atmospheric lifetimes for the studied ethers. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 420–426, 2005