Experimental and theoretical studies of the reactions of chlorine atoms with 1,2-dichloroethane and 1,2-dichloroethane-d(4) in the gas phase. The kinetics of hydrogen atom abstraction from the -CH2Cl group in chloroethane and 1,2-dichloroethane

Sarzynski DS; Fojcik L; Gola AA; Berkowski R; Jodkowski JT; Latajka Z

Chemical Physics Letters, Vol.597, 86-93, 2014

DOI10.1016/j.cplett.2014.02.026 Export Citation

Experimental and theoretical studies of the reactions of chlorine atoms with 1,2-dichloroethane and 1,2-dichloroethane-d(4) in the gas phase. The kinetics of hydrogen atom abstraction from the -CH2Cl group in chloroethane and 1,2-dichloroethane

Sarzynski DS, Fojcik L, Gola AA, Berkowski R, Jodkowski JT, Latajka Z

The rate constant for H-abstraction (k(H)) from CH2ClCH2Cl and D-abstraction (k(D)) from CD2ClCD2Cl by chlorine atoms is described by the expressions: k(H) = (1.99 +/- 0.12) x 10(-11) exp(-777 +/- 23/T) cm(3) molecule(-1) s(-1) and k(D) = (1.73 +/- 0.12) x 10(-11) exp(-1148 +/- 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 -CH2Cl 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. (C) 2014 Elsevier B.V. All rights reserved.