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

Correction for 'Atmospheric chemistry of (Z)- and (E)-1,2-dichloroethene: kinetics and mechanisms of the reactions with Cl atoms, OH radicals, and O3' by Mads P. Sulbaek Andersen et al., Phys. Chem. Chem. Phys., 2022, 24, 7356-7373, https://doi.org/10.1039/D1CP04877E.

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

Smog chambers interfaced with in situ FT-IR detection were used to investigate the kinetics and mechanisms of the Cl atom, OH radical, and O3 initiated oxidation of (Z)- and (E)-1,2-dichloroethene (CHClCHCl) under atmospheric conditions. Relative and absolute rate methods were used to measure k(Cl + (Z)-CHClCHCl) = (8.80 ± 1.75) × 10-11, k(Cl + (E)-CHClCHCl) = (8.51 ± 1.69) × 10-11, k(OH + (Z)-CHClCHCl) = (2.02 ± 0.43) × 10-12, k(OH + (E)-CHClCHCl) = (1.94 ± 0.43) × 10-12, k(O3 + (Z)-CHClCHCl) = (4.50 ± 0.45) × 10-21, and k(O3 + (E)-CHClCHCl) = (1.02 ± 0.10) × 10-19 cm3 molecule-1 s-1 in 700 Torr of N2/air diluent at 298 ± 2 K. Pressure dependencies for the Cl atom reaction kinetics were observed for both isomers, consistent with isomerization occurring via Cl atom elimination from the chemically activated CHCl-CHCl-Cl adduct. The observed products from Cl initiated oxidation were HC(O)Cl (117-133%), CHCl2CHO (29-30%), and the corresponding CHClCHCl isomer (11-20%). OH radical initiated oxidation gives HC(O)Cl as a major product. For reaction of OH with (E)-CHClCHCl, (Z)-CHClCHCl was also observed as a product. A significant chlorine atom elimination channel was observed experimentally (HCl yield) and supported by computational results. Photochemical ozone creation potentials of 12 and 11 were estimated for (Z)- and (E)-CHClCHCl, respectively. Finally, an empirical kinetic relationship is explored for the addition of OH radicals or Cl atoms to small alkenes. The results are discussed in the context of the atmospheric chemistry of (Z)- and (E)-CHClCHCl.

Atmospheric chemistry of (Z)-CF3CH[double bond, length as m-dash]CHCl: products and mechanisms of the Cl atom, OH radical and O3 reactions, and role of (E)-(Z) isomerization.

The chemical mechanisms of the OH radical, Cl-atom and O3 initiated oxidation of (Z)-CF3CH[double bond, length as m-dash]CHCl were studied at 296 ± 1 K in 10-700 Torr air of N2/O2 diluent. Cl atoms add to the [double bond splayed left]C[double bond, length as m-dash]C[double bond splayed right] double bond: 12 ± 5% to the terminal carbon and 85 ± 5% to the central carbon. In 700 Torr of air the products are CF3CHClCHO, HCOCl, CF3COCl, CF3CHO, (E)-CF3CH[double bond, length as m-dash]CHCl, CF3C(O)CHCl2, and CF3CHClCOCl. The yield of (E) isomer was dependent on total pressure, but independent of O2 partial pressure; consistent with isomerization occurring via Cl atom elimination from the chemically activated rather than the thermalized CF3CHCHCl-Cl adduct. The rate constant for (Z)-CF3CH[double bond, length as m-dash]CHCl + Cl was measured at low pressure (10-15 Torr) and found to be indistinguishable from that determined at 700 Torr total pressure, whereas the low pressure rate constant for (E)-CF3CH[double bond, length as m-dash]CHCl was 36% smaller. G4MP2 ab initio calculations showed that the (E) isomer is 1.2 kcal mol-1 more stable than the (Z) isomer. Cl atom elimination from the adduct will preferentially form the (E) isomer and hence the rate of CF3CH[double bond, length as m-dash]CHCl loss will be more sensitive to pressure for the (Z) than the (E) isomer. Reaction of (Z)-CF3CH[double bond, length as m-dash]CHCl with OH radicals gives CF3CHO, HCOCl, (E)-CF3CH[double bond, length as m-dash]CHCl, and HCl. A significant chlorine atom elimination channel was observed experimentally, and supported by computational results. The oxidation products of the reaction of O3 with (Z)- and (E)-CF3CH[double bond, length as m-dash]CHCl were determined with no evidence of isomerization. The results are discussed with respect to the atmospheric chemistry and environmental impact of (Z)- and (E)-CF3CH[double bond, length as m-dash]CHCl.