Rate constants of the reaction of ozone with trans‐1,2‐dichloroethene and vinyl chloride in air

Abstract

AbstractKinetic studies on reactions of ozone with trans‐1,2‐dichloroethene (DCE) and vinyl chloride (VC) were performed in air. In the presence of scavengers of radicals, such as CH3CHO, the rates for both reactions are second order (first order in each reactant). Observed rate constants are (1.80 ± 0.29) X 10−19 cm3/molecule·s for DCE and (2.45 ± 0.45) × 10−19 cm3/molecule·s for VC. In the presence of CH3CHO, propene ozonide \documentclass{article}\pagestyle{empty}\begin{document}$ ({\rm CH}_3 \overline {{\rm CHOOCH}_2 {\rm O}}) $\end{document} was observed as a product in the case of VC. Peroxyformic acid (HC)O(OOH) was detected in both reactions. The Criegee mechanism was proposed to play a major role in the reaction of ozone with chloroolefins. The branching ratio of O3 + CH2=CHCl → CH2OO + HCOCl (6a), CHClOO + HCHO (6b) was obtained as 76:24, and the fraction of the stabilized CH2OO was estimated to be 0.25 of that produced in reaction (6a).