Rate constants and kinetic isotope effects for hydrogen/deuterium abstraction by chlorine atoms from the chloromethyl group in CH2ClCH2Cl, CD2ClCD2Cl, CH2ClCHCl2, and CH2ClCDCl2

The abstraction of hydrogen and deuterium from 1,2‐dichloroethane, 1,1,2‐trichloroethane, and two of their deuterated analogs by photochemically generated ground state chlorine atoms has been investigatedin the temperature range 0–95°C using methane as a competitor. Rate constants and their temperature coefficients are reported for the following reactions equation image Over the temperature range of this investigation an Arrhenius law temperature dependence was observed in all cases. Based on the adopted rate coefficient for the chlorination of methane [L.F. Keyser, J. Chem. Phys., 69, 214 (1978)] which is commensurate with the present temperature range, the following rate constant values (cm3 s−1) are obtained: The observed pure primary, and mixed primary plus α‐ and β3‐secondary kinetic isotope effects at 298 K are k3/k6 = 2.73 ± 0.08, and k1/k2 = 4.26 ± 0.12, respectively. Both show a normal temperature dependence decreasing to k3/k6 = 2.39 ± 0.06 and k1/k2 = 3.56 ± 0.09 at 370 K. Contrary to some simple theoretical expectations, the kinetic isotope effect for H/D abstraction decreases with increasing number of chlorine substituents in the geminal group in a parallel manner to the trend established previously for C1‐substitution in the adjacent group. The occurrence of a β‐secondary isotope effect, k4/k5, is established; this effect suggests a slight inverse temperature dependence.