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

• Published in: Chemical physics letters Vol. 597; pp. 86 - 93
• Main Authors: Sarzyński, Dariusz S., Fojcik, Łukasz, Gola, Agnieszka A., Berkowski, Ryszard, Jodkowski, Jerzy T., Latajka, Zdzisław
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 28.03.2014
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2014.02.026

[Display omitted] •The kinetics of the hydrogen abstraction was studied in the range of 298–528.5K.•Values of the kinetic isotope effect were determined in the range of 298–528.5K.•No pressure dependence was observed for the rate of abstraction.•Theoretical calculations explained the mechanism of reaction.•Various values of rate constants can be a result of significant differences in appropriate potential energy barrier heights. The rate constant for H-abstraction (kH) from CH2ClCH2Cl and D-abstraction (kD) from CD2ClCD2Cl by chlorine atoms is described by the expressions: kH=(1.99±0.12)×10−11exp(−777±23/T)cm3molecule−1s−1 and kD=(1.73±0.12)×10−11exp(−1148±16/T)cm3molecule−1s−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.