Kinetics of the thermal decompositions of 4-chlorocyclohexene and 3-chlorocyclohexene

Abstract

The gas-phase thermal decompositions of 4-chlorocyclohexene in the temperature range 320–370 °C and of 3-chlorocyclohexene in the range 250–310 °C are homogeneous and unimolecular in a ‘seasoned’ reaction vessel. The rate constants for the elimination of hydrogen chloride are given by the equations k₁= 10^{13·17 ± 0·25} exp –(48,380 ± 700)/RT s^–1 and k₁= 10^{11·16 ± 0·22} exp –(36,950 ± 550)/RT s^–1 respectively. The double bond when β to the chlorine atom has no effect on the rate of elimination of hydrogen chloride but when α to it increases the rate ca. 100-fold.