ATMOSPHERIC CHEMISTRY OF CF3C(O)O2 RADICALS - KINETICS OF THEIR REACTION WITH NO2 AND KINETICS OF THE THERMAL-DECOMPOSITION OF THE PRODUCT CF3C(O)O2NO2

A pulse radiolysis technique has been used to measure a rate constant of (6.6 +/- 1.3) x 10(-12) cm3 molecule-1 s-1 for the association reac tion between CF3C(O)O2 radicals and NO2 at 295 K and one atmosphere to tal pressure of SF6 diluent. A FTIR/smog chamber system was used to st udy the thermal decomposition CF3C(O)O2NO2. The rate of decomposition of CF3C(O)O2NO2 was independent of the total pressure of N2 diluent ov er the range 100-700 Torr and was fit by the expression k-1 = (1.9(-1. 5)+7.6) x 10(16) exp[(-14000 +/- 480)/T] s-1. Implications for the atm ospheric chemistry of CFC replacements are discussed.