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• W2008597952 abstract "Abstract The primary product formation of the reactions CH 2 Cl + O and CHCl 2 + O in the gas phase has been studied around room temperature. The coupling of a conventional discharge flow reactor via a molecular sampling system to a mass spectrometer with electron impact ionization allowed the determination of labile and stable species (set-up A). The radicals are formed by H atom abstraction in the reactions CH 3 Cl + F and CH 2 Cl 2 + F. The product analysis leads to the following branching fractions relative to precursor consumption: For CH 2 Cl + O, the channel HCHO + Cl yields 19 % and CO + HCl + H yields 43 %, the contributions of the labile species HCO is found but not quantified. For CHCl 2 + O the channel CO + HCl + Cl yields 70 %, ClCHO and the labile ClCO are detected but not quantified. The comparison to CH 3 + O shows the stepwise increase of channel fractions for the CO forming routes by chlorination of the methyl radical. The rates of the reactions have been studied relative to CH 3 + O and CH 3 OCH 2 + O. Laser-induced multiphoton ionization combined with TOF mass spectrometry and molecular beam sampling from a flow reactor (set-up B) was used for the specific and sensitive detection of the CH 2 Cl, CHCl 2 , CH 3 , and CH 3 OCH 2 radicals. The rate coefficient of the reactions CH 2 Cl + O was derived with reference to the reaction CH 3 OCH 2 leading to k = (8.1±1.8)×10 13 cm 3 /(mol·s) and for CHCl 2 + O with reference to CH 3 + O leading to k = (3.8±1.9)×10 13 cm 3 /(mol·s). For CH 3 Cl + F and CH 2 Cl 2 + F the rate coefficients have been determined with set-up A leading to k = (4.3±0.9)×10 13 cm 3 /(mol·s) for CH 3 Cl + F and k = (8.4±3.8)×10 13 cm 3 /(mol·s) for CH 2 Cl 2 + F. Only a negligible temperature dependence in the temperature range from 250–360 K was observed for all reactions studied." @default.
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• W2008597952 date "2009-05-01" @default.
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• W2008597952 title "CH₂Cl and CHCl₂ Radical Chemistry: The Formation by the Reactions CH₃Cl + F and CH₂Cl₂ + F and The Destruction by the Reactions CH₂Cl + O and CHCl₂ + O" @default.
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• W2008597952 doi "https://doi.org/10.1524/zpch.2009.6044" @default.
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