Gas‐phase reactions of Cl atoms with hydrochloroethers: relative rate constants and their correlation with substituents' electronegativities

Abstract

AbstractRate constants for the reactions of Cl atoms with CH3OCHCl2 and CH3OCH2CH2Cl were determined at (296 ± 2) K and atmospheric pressure using synthetic air as bath gas. Decay rates of these organic compounds were measured relative to the following reference compounds: CH2ClCH2Cl and n‐C5H12. Using rate constants of 1.33 × 10−12 and 2.52 × 10−10 cm3 molecule−1 sec−1 for the reaction of Cl atoms with CH2ClCH2Cl and n‐C5H12, respectively, the following rate coefficients were derived: k(Cl + CH3OCHCl2) = (1.05 ± 0.11) × 10−12 and k(Cl + CH3OCH2CH2Cl) = (1.14 ± 0.10) × 10−10, in units of cm3 molecule−1 s−1. The rate constants obtained were compared with previous literature data and a correlation was found between the rate coefficients of some CH3OCHR1R2 + Cl reactions and ΔElectronegativity of CHR1R2. Copyright © 2008 John Wiley & Sons, Ltd.