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

Rate constants for the reactions of Cl atoms with CH 3 OCHCl 2 and CH 3 OCH 2 CH 2 Cl 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: CH 2 ClCH 2 Cl and n ‐C 5 H 12 . Using rate constants of 1.33 × 10 −12 and 2.52 × 10 −10  cm 3  molecule −1  sec −1 for the reaction of Cl atoms with CH 2 ClCH 2 Cl and n ‐C 5 H 12 , respectively, the following rate coefficients were derived: k (Cl + CH 3 OCHCl 2 ) = (1.05 ± 0.11) × 10 −12 and k (Cl + CH 3 OCH 2 CH 2 Cl) =  (1.14 ± 0.10) × 10 −10 , in units of cm 3  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 CH 3 OCHR 1 R 2  + Cl reactions and ΔElectronegativity of CHR 1 R 2 . Copyright © 2008 John Wiley & Sons, Ltd.