Atmospheric chemistry at 4.2 K: a matrix isolation study of the reaction between peroxytrifluoromethane radicals and nitric oxide

Abstract

A novel pathway is proposed for the reaction between CF/sub 3/OO 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 (lambda > 265 nm) of trifluoronitrosomethane in 5% O/sub 2/-doped argon matrices at 4.2 K gives rise to the twin production of CF/sub 2/O and FNO/sub 2/ from a common intermediate. Although isotopic labeling experiments show that CF/sub 3/ONO/sub 2/ is produced, the observed chemistry can also be explained in terms of the decomposition of CF/sub 3/OONO. 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 CF/sub 3/ radicals to CF/sub 2/O in the atmosphere.