Reactions of chloroethenes with atomic chlorine in air at atmospheric pressure

Abstract

Relative rate method at the temperature of 298 K and pressure of 1013 hPa and GC MS detection were used for the study of kinetics of the reactions of Cl atoms with H 2 C=CCl 2 , cis ClHC=CHCl, trans ClHC=CHCl, ClHC=CCl 2 , and Cl 2 C=CCl 2 . The reaction products were identified by FTIR spectroscopy. A mechanism for the atmospheric degradation of chloro ethenes has been suggested.

Atmospheric chemistry of (Z)- and (E)-1,2-dichloroethene: kinetics and mechanisms of the reactions with Cl atoms, OH radicals, and O3

“…The product distribution reported by Morozov et al 21 is in sharp contrast to the observations in the present work. Morozov et al 21 suggests that the fate of the OCHClCHCl 2 is either decomposition to give HC(O)Cl and CHCl 2 (in line with reaction (R19)), or reaction with O 2 :OCHClCHCl 2 + O 2 → CHCl 2 C(O)Cl + HO 2 …”

“…However, their value of k 8 for the ( E )-isomer, is significantly (about 25%) lower than any of the other results in the literature. The situation is just the opposite in the work of Morozov et al 21 , where their value for k 8 is in good agreement with the rest of the literature and the value determined in the present work, but their value of k 7 is significantly (about 25%) higher than the rest of the values reported in the literature. It is not clear why this is the case.…”

“…Morozov et al 21 used a stainless-steel smog-chamber in combination with FTIR and GC-MS analysis to determine the products of the reactions ( Z )-CHClCHCl and ( E )-CHClCHCl with Cl, and reported CHCl 2 C(O)Cl as the major product with C(O)Cl 2 , HC(O)Cl, CO, and HCl as very minor products. The product distribution reported by Morozov et al 21 is in sharp contrast to the observations in the present work.…”

“…Morozov et al 21 used a stainless-steel smog-chamber in combination with FTIR and GC-MS analysis to determine the products of the reactions ( Z )-CHClCHCl and ( E )-CHClCHCl with Cl, and reported CHCl 2 C(O)Cl as the major product with C(O)Cl 2 , HC(O)Cl, CO, and HCl as very minor products. The product distribution reported by Morozov et al 21 is in sharp contrast to the observations in the present work. Morozov et al 21 suggests that the fate of the OCHClCHCl 2 is either decomposition to give HC(O)Cl and CHCl 2 (in line with reaction (R19)), or reaction with O 2 :OCHClCHCl 2 + O 2 → CHCl 2 C(O)Cl + HO 2 …”

Relative Rate Studies of the Reactions of Atomic Chlorine with Acetone and Cyclic Ketones

“…The reference compounds employed were isobutane, trans ‐1,2‐dichloroethene, ethene, 1,2‐dichloroethane, and dichloromethane. Rate constants and error limits were taken from the most recent measurements, which yielded k ref values of (1.40 ± 0.08) × 10 −10 cm 3 molecule −1 s −1 for isobutane , (9.8 ± 0.4) × 10 −11 cm 3 molecule −1 s −1 for trans ‐1,2‐dichloroethene , (1.47 ± 0.21) × 10 −12 cm 3 molecule −1 s −1 for 1,2‐dichloroethane , and (3.5 ± 0.2) × 10 −13 cm 3 molecule −1 s −1 for dichloromethane . We used ethene at two pressures, 667 and 933 mbar, and took rate constants at these pressures from the Troe fit to the measurements by Glowacki et al to obtain 8.6 and 9.9 × 10 −11 cm 3 molecule −1 s −1 , respectively.…”