THERMAL GAS-PHASE OXIDATION OF TRIFLUOROBROMOETHENE, CF2CFBr, INITIATED BY NO2

ARCE, V; DOS SANTOS AFONSO, M.; ROMANO, R.M.; CZARNOWSKI, J.

The Journal of the Argentine Chemical Society

Año: 2005 vol. 93 p. 123 - 136

0365-0375

The oxidation of CF2CFBr by molecular O2 initiated by the addition of NO2 to the double bond of the alkene was studied at 313.4 K, using a conventional static system. The initial pressure of CF2CFBr was varied between 18.8 and 43.9 torr, that of NO2 between 0.9 and 4.8 torr and that of O2 between 96.9 and 402.9 torr. The following products were formed: CF2BrC(O)F, as the main product, C(O)F2 and C(O)FBr and small amounts of peroxynitrate, CF2BrCFBrO2NO2, and trifluorobromoethene epoxide. CF2BrC(O)F was characterized by its IR spectrum consistent with both the proposed structure and the calculations carried out using ab initio and Density Functional Theory methods. In presence of CF2CFBr the reaction proceeded with a pressure decrease. After the alkene was consumed an increase of the pressure and formation of bromine was observed. The oxidation is a chain reaction of pseudo-zero order with respect to O2 as reactant at the pressure of oxygen used in this work. Its basic steps are: chain initiation by addition of NO2 to the double bond leading, through reaction sequence in presence of O2, to generation of bromine atoms and chain propagation by reaction of Br • with alkene, originating CF2BrCFBrO2  and CF2BrCFBrO radicals. The predominant fate of the latter is the bromine atoms extrusion, with C-C bond cleavage playing only a minor role. A full mechanism is postulated. The value of (2.2 ±1) x 10-5 s-1 was obtained for the room temperature rate constant for the unimolecular decomposition of  F2BrCFBrO2NO2.