KINETICS AND THERMOCHEMISTRY OF CHLORINE-CONTAINING AND NITROGEN-CONTAINING OXIDES AND PEROXIDES

A valence bond additivity scheme based on established thermochemical data is able to reproduce the heats of formation of novel species such as O2ClONO2, ClOClO2, ONONO2, ClOONO, HOONO, FOClO3, and FONO within +/- 2 kcal/mol. This finding, together with recently obtained values of DELTAH(f)-degrees-(ClO3(g)) and DELTAH(f)-degrees-(ClO4-(g)), makes possible a general analysis of the thermal stabilities of known or conceivable chlorine and nitrogen oxides of potential atmospheric significance. Radical mechanisms for the decompositions of chlorine hexoxide and perchloric acid are also discussed.