359-32-0Relevant articles and documents
Kinetics and Mechanism of the Thermal Gas-phase Oxidation of Trichloroethene by Molecular Oxygen in Presence of Trifluoromethylhypofluorite, CF3OF
Czarnowski, J.
, p. 103 - 118 (2007/10/03)
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
