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 isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials.

The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR spectra of (CF(3))(2)CHOC(O)F and FC(O)OCHF(2) are reported for the first time. The atmospheric lifetimes of CF(3)CHClOCHF(2), CF(3)CHFOCHF(2), and (CF(3))(2)CHOCH(2)F (sevoflurane) are estimated at 3.2, 14, and 1.1 years, respectively. The 100 year time horizon global warming potentials of isoflurane, desflurane, and sevoflurane are 510, 2540, and 130, respectively. The atmospheric degradation products of these anesthetics are not of environmental concern.

Medical intelligence article: assessing the impact on global climate from general anesthetic gases.

Although present in the atmosphere with a combined concentration approximately 100,000 times lower than carbon dioxide (i.e., the principal anthropogenic driver of climate change), halogenated organic compounds are responsible for a warming effect of approximately 10% to 15% of the total anthropogenic radiative forcing of climate, as measured relative to the start of the industrial era (approximately 1750). The family of anesthetic gases includes several halogenated organic compounds that are strong greenhouse gases. In this short report, we provide an overview of the state of knowledge regarding the impact of anesthetic gas release on the environment, with particular focus on its contribution to the radiative forcing of climate change.

Atmospheric chemistry of HCF2O(CF2CF2O)xCF2H (x=2-4): kinetics and mechanisms of the chlorine-atom-initiated oxidation.

Smog chamber/FTIR techniques were used to measure k(Cl+HCF(2)O(CF(2)CF(2)O)(x)CF(2)H)=(5.3±1.5)×10(-17) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296±1 K. The Cl-initiated atmospheric oxidation of HCF(2)O(CF(2)CF(2)O)(x)CF(2)H, x=2,3 and 4, gave COF(2) in molar yields of (593±41)%, (758±71)% and (939±73)%, respectively, with no other observable carbon-containing products (i.e., essentially complete conversion of the hydrofluoropolyethers into COF(2)). Quantitative infrared spectra for HCF(2)O(CF(2)CF(2)O)(x)CF(2)H (x=2-4) were recorded and used to estimate the radiative efficiencies of the title compounds (1.07, 1.33, and 1.36 W m(-2) ppb(-1)). Global warming potentials (100 year time horizon) of 3870, 4730 and 5060 were estimated for HCF(2)O(CF(2)CF(2)O)(x)CF(2)H, x=2, 3 and 4, respectively. The results are discussed with respect to the atmospheric chemistry and environmental impact of hydrofluoropolyethers.

CHF2OCHF2 (HFE-134): IR spectrum and kinetics and products of the chlorine-atom-initiated oxidation.

Smog chamber/FTIR techniques were used to measure k(Cl + CHF(2)OCHF(2)) = (5.7 +/- 1.5) x 10(-16) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 1 K. This result is 100 times lower than the previous literature value. The chlorine-atom-initiated atmospheric oxidation of CHF(2)OCHF(2) gives COF(2) in a molar yield of (185 +/- 22) %. The IR spectrum was recorded, and a radiative efficiency of 0.44 W m(-2) ppb(-1) was determined. The results are discussed with respect to the atmospheric chemistry and environmental impact of CHF(2)OCHF(2).

Photochemistry of 2,2-dichloroethanol: kinetics and mechanism of the reaction with Cl atoms and OH radicals.

Smog chamber/FTIR techniques were used to investigate the kinetics and mechanism of the Cl atom and OH radical initiated oxidation of 2,2-dichloroethanol at (296 ± 1) K. Relative rate methods were used to measure k(Cl + CHCl2CH2OH) = (5.87 ± 0.96) × 10-12 and k(OH + CHCl2CH2OH) = (5.54 ± 1.94) × 10-13 cm3 molecule-1 s-1. Chlorine atom initiated oxidation of CHCl2CH2OH in one atmosphere of air gives HCOCl, CHCl2CHO, and COCl2 in yields of (62 ± 5)%, (39 ± 10)%, and (8 ± 2)%, respectively. The rate constant k(Cl + CHCl2CHO) = (8.3 ± 16) × 10-12 cm3 molecule-1 s-1 was determined and the IR spectra of CHCl2CHO is reported for the first time. The atmospheric lifetime for CHCl2CH2OH is estimated as 21 days. The experimental results are discussed in the context of the atmospheric chemistry of chlorinated alcohols.