A study of the self reaction of CH2ClO2 and CHCl2O2 radicals at 298 K

Biggs, Peter J.; Canosa‐Mas, Carlos E.; Percival, CJ; Shallcross, Dudley E.; Wayne, Richard P.

doi:10.1002/(sici)1097-4601(1999)31:6<433::aid-kin5>3.3.co;2-5

Cited by 2 publications

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“…The initial radical products (CH 2 Cl, CHCl 2 , CCl 3 , and CH 2 ClCHCl) are rapidly oxidized under tropospheric conditions to peroxy radicals (i.e., CH 2 ClO 2 , CHCl 2 O 2 , CCl 3 O 2 , and CH 2 ClCHClO 2 , respectively). These peroxy radicals may react with NO, HO 2 , other peroxy species (e.g., CH 3 O 2 ), or with themselves [e.g., Catoire et al ., ; Biggs et al ., ]. The expected major organic products from oxidation of the above source gases are (i) phosgene (CCl 2 O), following CHCl 3 oxidation, and (ii) formyl chloride (CHClO), following CH 3 Cl, CH 2 Cl 2 , and CH 2 ClCH 2 Cl oxidation [e.g., Catoire et al ., ; Bilde et al ., ; Ko et al , ].…”

Section: Model and Experimentsmentioning

confidence: 99%

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

et al. 2016

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Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by ~2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea‐salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub‐ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1–5 × 104 atoms cm−3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to ~4320 Gg Cl/yr, sustaining a background surface [Cl] of <0.1 to 0.5 × 103 atoms cm−3 over large areas. Globally, we estimate a tropospheric methane sink of ~12–13 Tg CH4/yr due the CH4 + Cl reaction (~2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for ~10 to >20% of total boundary layer CH4 oxidation in some locations.

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Section: Model and Experimentsmentioning

confidence: 99%

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

et al. 2016

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“…3,4 The kinetics of the reactions of chloromethylperoxy radical with itself and with HO 2 were studied, and the reaction rate constants were measured. [3][4][5] The mechanism of the reaction of chloromethylperoxy radical with HO 2 was investigated using Fourier transform infrared spectroscopy. 6 Both the CH 2 ClOOH and HC(O)Cl molecules were identified as the reaction product.…”

Section: Introductionmentioning

confidence: 99%

“…The chloromethylperoxy radical could further react with itself and with various atmospheric constituents such as HO 2 , NO, and NO 2 . The chloromethylperoxy radicals were produced via photolysis of Cl 2 /CH 3 Cl/O 2 mixtures in the gas phase, and the UV absorption spectra were obtained. , The kinetics of the reactions of chloromethylperoxy radical with itself and with HO 2 were studied, and the reaction rate constants were measured. − The mechanism of the reaction of chloromethylperoxy radical with HO 2 was investigated using Fourier transform infrared spectroscopy . Both the CH 2 ClOOH and HC(O)Cl molecules were identified as the reaction product.…”

Section: Introductionmentioning

confidence: 99%

Reaction of Chloromethyl Radical with Dioxygen: Formation of the Chloromethylperoxy Radical and Its Photodissociation in Solid Argon

Zhou

Dong-mei

et al. 2009

J. Phys. Chem. A

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The reaction of chloromethyl radical with molecular oxygen in solid argon has been studied using matrix isolation infrared absorption spectroscopy. The chloromethyl radical was produced via codeposition of chloromethane with high frequency discharged argon atoms. The chloromethyl radical reacted with dioxygen spontaneously on annealing to form the chloromethylperoxy radical, which was characterized on the basis of isotopic splitting (Cl and O) as well as quantum chemical calculations. The chloromethylperoxy radical dissociated to give the weakly bound ClCO-H2O complex under UV light irradiation. The calculations predicted that the ClCO-H2O complex was produced by hydrogen atom transfer from a CHCl(O)-OH intermediate.

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A study of the self reaction of CH2ClO2 and CHCl2O2 radicals at 298 K

Cited by 2 publications

References 0 publications

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

Reaction of Chloromethyl Radical with Dioxygen: Formation of the Chloromethylperoxy Radical and Its Photodissociation in Solid Argon

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