Experimental and theoretical studies of the reactions of chlorine atoms with 1,2-dichloroethane and 1,2-dichloroethane-d4 in the gas phase. The kinetics of hydrogen atom abstraction from the –CH2Cl group in chloroethane and 1,2-dichloroethane

摘要

The rate constant for H-abstraction (k_H) from CH_2ClCH_2Cl and D-abstraction (k_D) from CD_2ClCD_2Cl by chlorine atoms is described by the expressions: k_H = (1.99 ± 0.12) × 10~(-11) exp(-777 ± 23/T) cm~3 molecule ~(-1) s~(-1) and k_D = (1.73 ± 0.12) × 10~(-11) exp(~(-1)148 ± 16/T) cm~3 molecule~(-1) s~(-1). The experiment revealed significant differences in the values of the rate constants for the abstraction of H-atom from the –CH_2Cl group in chloroethane and 1,2-dichloroethane. The explanation of these differences was the subject of theoretical studies. The calculated potential energy barriers for the abstraction reaction confirmed the experimental results.