136649-69-9Relevant articles and documents
Kinetics and mechanism of the thermal gas-phase oxidation of tetrachloroethene by molecular oxygen in presence of trifluoromethylhypofluorite, CF3OF
Czarnowski, Joanna
, p. 183 - 197 (1998)
The oxidation of tetrachloroethene by molecular oxygen in presence of CF3OF has been studied at 314.0, 324.2, 334.1 and 344.3 K. The initial pressure of CF3OF was varied between 2.0 and 8.2 Torr, that of CCl2CCl2 between 8.7 and 21.7 Torr, that of O2 between 33.2 and 730.7 Torr. Several runs were made adding N2 at pressure varying between 250.4 and 525.9 Torr. The major products were CCl3C(O)Cl and COCl2. CF3OCCl2C(O)Cl, CCl2FC(O)Cl, CF3OCCl2CCl2F and CCl2FCCl2F were formed in traces. The oxidation is a chain reaction. Its rate increases with total pressure. The following mechanism, where E = CCl2CCl2, R = CCl2FCCl2, CF3OCCl2CCl2 or CCl3CCl2, R′ = CCl2F, CF3OCCl2 or CCl3 and M = effective pressure, explains the experimental results: 1) CF3OF+E → R+CF3O 3, 7) R+O2+M → RO2+M 5) RO → R′C(O)Cl+Cl 9) CCl3CCl2O → CCl3C(O)Cl+Cl 11) CCl3+O2+M → CCl3O2+M 13) CCl3O → COCl2+Cl 15) R+CF3OF → RF+CF3O 2) CF3O+E → R 4, 8) 2RO2 → 2RO+O2 6) Cl+E → CCl3CCl2 10) CCl3CCl2O → CCl3+COCl2 12) CCl3O2+RO2 → CCl3O+RO+O2 14) 2R → recombination products, k9 = (3.0±1.4) × 1013 exp(-9.66±1 kcal mol-1/RT) s-1. by R. Oldenbourg Verlag, Muenchen 1998.
Relative Rate Constants for the Reactions of CF3OF with Olefins in Solution
Navarrini, W.,Russo, A.,Tortelli, V.
, p. 6441 - 6443 (2007/10/03)
The addition reactions of CF3OF to chloro fluoro olefins have been studied in solution at low temperature (-78, -105 deg C), and their relative rate constants have been determined using the kinetic approach of competition reactions.The reactivity and regio- and stereoselectivity are consistent with a free radical chain-propagating reaction in which the alkenes are attacked by the CF3O* radical generated by homolytic cleavage of the O-F bond in the CF3OF molecule.