- Kinetics and Mechanism of the Thermal Gas-phase Oxidation of Trichloroethene by Molecular Oxygen in Presence of Trifluoromethylhypofluorite, CF3OF
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The oxidation of trichloroethene by molecular oxygen in presence of CF3OF has been studied at 293.8, 313.8 and 333.5 K.The initial pressure of CF3OF was varied between 0.8 and 9.5 Torr, that of CHClCCl2 between 5.4 and 54.6 Torr and that of O2 between 19.9 and 603.5 Torr.Several runs were made adding N2 at pressures varying from 96.4 to 663.2 Torr.The major product was CHCl2C(O)Cl, COCl2, HCl and CO were formed in minor amounts.Traces of CF3OCHClC(O)Cl, CHClFC(O)Cl, CF3OCHClCCl2F and CHClFCCl2F were detected.The oxidation is a chain reaction, whose rate increases with total pressure.The following mechanism, where E = CHClCCl2, R = CHClFCCl2, CF3OCHClCCl2 or CHCl2CCl2, R' = CHClF, CF3OCHCl or CHCl2 and M = effective pressure, explains the experimental results: (1) CF3OF + E = R + CF3O, (2) CF3O + E = R, (3,7) R + O2 + M = RO2 + M, (4,8) 2RO2 = 2RO + O2, (5,9) RO = R'C(O)Cl + Cl, (6) Cl + E = R, (10) 2R = recombination products, (11) R + CF3OF = RF + CF3O, (12) RO2 + E = RO2(E), (13) RO2(E) = products (e.g., R, HCl, CO, COCl2), k9 = 1.1 +/- 1E14 exp(-39.5 +/- 10 kJ mol-1/RT) s-1, k12 = 9.4 +/- 8E8 exp(-27.0 +/- 11 kJ mol-1/RT) dm3 mol-1 s-1. - Keywords: Gas-phase, Oxidation, Trichloroethene, Trifluoromethylhypofluorite, Chlorine atoms
- Czarnowski, J.
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p. 103 - 118
(2007/10/03)
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- REACTION OF ALKYL 2-CHLORO-1,1,2-TRIFLUOROETHYL ETHERS WITH LEWIS ACIDS
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Ethyl 2-chloro-1,1,2-trifluoroethyl ether heated with boron trifluoride etherate gave ethyl fluoride and chlorofluoroacetyl fluoride.When heated with aluminium chloride, it afforded a mixture of ethyl fluoride, ethyl chloride, chlorofluoroacetyl fluoride, and chlorofluoroacetyl chloride.Treatment of the acyl halides with ethanol yielded ethyl chlorofluoroacetate.Butyl and octyl 2-chloro-1,1,2-trifluoroethyl ethers gave directly butyl and octyl chlorofluoroacetates, respectively, under similar conditions.
- Hudlicky, Milos
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p. 349 - 354
(2007/10/02)
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