The photolysis of CF3COCl in the presence of O2 and CO: catalytic oxidation of CO to CO2 and the formation of polyoxygenated intermediates

FABIO E. MALANCA; GUSTAVO A. ARGÜELLO; EDUARDO H. STARICCO; RICHARD P. WAYNE

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY

Elsevier Science

Lugar: Holanda; Año: 1998 vol. 117 p. 163 - 163

1010-6030

p>Photolysis of CF3COCl in the presence of O2 yields the radical CF3O, which then reacts in the presence of CO and O2 to yield a variety of CF3-containing species initiated by the following reactions: CF3O + CO -> CF3OCO  CF3OCO + O2 -> CF3OC(O)O2. The reactions of various oxygenated CF3-containing radicals give rise to two different compounds with the general composition CF3OC(O)OyCF3 (y=4 and 3) that show increased thermal stability as the number of oxygen atoms in the peroxidic bonding bridge decreases. A further species of the formula CF3OC(O)O2C(O)OCF3 is also invoked. Parallel reactions lead to the formation of CF3OC(O)O radicals that decompose to give CF3O and CO2, thus providing a way of maintaining the chain reaction that catalytically converts CO into CO2. Experimental evidence for the formation and thermal decay of these intermediates is presented.