The mechanism of thermal dehydrochlorination. Pyrolysis of 1‐Chloro‐1‐fluoroethane and 1‐chloro‐1, 1‐difluoroethane

The thermal decompositions of 1‐chloro‐1‐fluoroethane and 1‐chloro‐1,1‐difluorethane at atmospheric pressure have been studied in the temperature range 500–600°C in a flow system. The dehydrochlorinations are homogenous in a carbonaceous reactor and unimolecular. The rate constants are given by\documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm I} = 10^{13.94 \pm 0.05} \exp (- 57,015 \pm 200/RT)^{\sec - 1}$$\end{document} and\documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm II}} = 10^{14.35 \pm 0.12} \exp (- 60,200 \pm 500/RT)^{\sec - 1}$$\end{document} The criteria for molecular or chain processes in thermal dehydrochlorinations are discussed.