Atmospheric Chemistry at 4.2 K: A Matrix Isolation Study of the Reaction between CF3O2 Radicals and NO

Article abstract of DOI:10.1021/j100297a037

A novel pathway is proposed for the reaction between CF3OO^. radicals and NO to give carbonyl fluoride and nitryl fluoride.It has been shown in a series of matrix isolation experiments that unfiltered medium-pressure mercury lamp photolysis (λ > 265 nm) of trifluoronitrosomethane in 5percent O2-doped argon matrices at 4.2 K gives rise to the twin production of CF2O and FNO2 from a common intermediate.Although isotopic labeling experiments show that CF3ONO2 is produced, the observed chemistry can also be explained in terms of the decomposition of CF3OONO.The overall reaction discussed in this work is exothermic and therefore contrasts with all other mechanisms hitherto suggested for the oxidation by molecular oxygen of ^.CF3 radicals to CF2O in the atmosphere.