Kinetics of the Reactions of Chlorinated Very Short-Lived Substances (VSLSs) with Chlorine Atoms.

Abstract

Chlorinated very short-lived substances (VSLSs), which are not controlled by the Montreal Protocol, are of current concern with regard to recovery of stratospheric ozone. Further study is needed on the temperature dependences of chlorinated VSLSs relevant to atmospheric conditions. Here, the kinetics of chlorinated VSLSs, such as chloroform (CHCl3), dichloromethane (CH2Cl2), dichloroethane (CH2ClCH2Cl), and trichloroethene (C2HCl3) reacting with chlorine atoms, were investigated between 180 and 400 K, expanding the range of temperatures relative to previous studies. RRKM/Master Equation and Canonical Variational Transition State Theory were utilized to calculate the rate coefficients using the MultiWell suite of programs. CCSD(T), QCISD(T), and M062X with aug-cc-pV(T+d)Z levels of theory were used to calculate the kinetic parameters. Arrhenius equations obtained from fits to the calculated rate coefficients are k1 = (2.66 ± 0.7) × 10-12 exp [(-927 ± 131)/T] cm3 molecule-1 s-1, k2 = (8.99 ± 0.3) × 10-12 exp [(-957 ± 19)/T] cm3 molecule-1 s-1, k3 = (1.51 ± 0.16) × 10-11 exp [(-714 ± 54)/T] cm3 molecule-1 s-1, and k4 = (9.17 ± 1.8) × 10-12 exp [(612 ± 101)/T] cm3 molecule-1 s-1 for the reactions of CHCl3, CH2Cl2, CH2ClCH2Cl, and C2HCl3 with Cl atoms, respectively. The rate coefficients for the reactions of chlorinated VSLSs with Cl atoms from this study are compared with the most recent recommended values from the NASA/JPL and IUPAC evaluations and with literature values. The reactivity trends of the reactions are discussed.