Photochemistry of perfuoroacetyl fuorideKinetics of the reaction between CF3 and FCO radicals

K.L. BIERBRAUER; M.S. CHIAPPERO; F.E. MALANCA; GUSTAVO A. ARGUELLO

Journal of Photochemistry and Photobiology A: Chemistry

Elsevier

Año: 1999 vol. 122 p. 73 - 78

The photolysis at 254 nm of perfuoroacetyl fuoride (CF3COF) in the gas phase yields C2F6, CF2O and CO as products. An excess of O23COF) in the gas phase yields C2F6, CF2O and CO as products. An excess of O2 added to the system leads to the formation of CF2O and CO2 as main products. If, instead of O2, c-C6H12 were added, the main products are CF3H and HC(O)F. In both cases a faster rate of CF3COF dissapearance is observed. The measurement of the quantum yield for CF3COF consumption as well as for products formation are: for CF3COF alone, -CF3COF . 2-C2F6 . 2-CF2O . 0:43 +/- 0:05; in the presence of c- C6H12 -CF3COF . -CF3H . 1.02 +/- 0.02 and in the presence of O2, -CF3COF . 1:02 +/- 0:05. The low quantum yield observed for pure CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 C6H12 -CF3COF . -CF3H . 1.02 +/- 0.02 and in the presence of O2, -CF3COF . 1:02 +/- 0:05. The low quantum yield observed for pure CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 consumption as well as for products formation are: for CF3COF alone, -CF3COF . 2-C2F6 . 2-CF2O . 0:43 +/- 0:05; in the presence of c- C6H12 -CF3COF . -CF3H . 1.02 +/- 0.02 and in the presence of O2, -CF3COF . 1:02 +/- 0:05. The low quantum yield observed for pure CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 C6H12 -CF3COF . -CF3H . 1.02 +/- 0.02 and in the presence of O2, -CF3COF . 1:02 +/- 0:05. The low quantum yield observed for pure CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3COF suggests the occurence of the recombination reaction: CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3 + FCO ->CF3COF for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 for which we calculated the rate constant as (6.9 +/- 0.8) 10-12 cm3 molecule-1 s-1 CF3H and HC(O)F. In both cases a faster rate of CF3COF dissapearance is observed. The measurement of the quantum yield for CF3COF consumption as well as for products formation are: for CF3COF alone, -CF3COF . 2-C2F6 . 2-CF2O . 0:43 +/- 0:05; in the presence of c- C6H12 -CF3COF . -CF3H . 1.02 +/- 0.02 and in the presence of O2, -CF3COF . 1:02 +/- 0