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Kinetics and mechanism of the thermal gas-phase oxidation of perfluorobutene-2 in presence of trifluoromethyl hypofluorite

✍ Scribed by Rosana M. Romano; Carlos O. Della Védova; Joanna Czarnowski

Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
126 KB
Volume
35
Category
Article
ISSN
0538-8066

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✦ Synopsis

The oxidation of perfluorobutene-2 (C 4 F 8 ) initiated by trifluoromethyl hypofluorite (CF 3 OF) in presence of O 2 has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF 3 OF was varied between 4.8 and 23.6 Torr, that of C 4 F 8 between 48.7 and 302.4 Torr, and that of O 2 between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5-451.2 Torr of N 2 . The main products were COF 2 , CF 3 C(O)F, and CF 3 OC(O)F. Small amounts of compound containing CF(CF 3 ) O C(O)CF 3 group were also formed, as detected by 13 C NMR spectroscopy. The oxidation is a homogeneous short-chain reaction, attaining, at the pressure of O 2 used, the pseudo-zero-order condition with respect to O 2 as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF 3 O • radicals by the abstraction of fluorine atom of CF 3 OF by

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