THERMOCHEMICAL KINETICS OF BROMINE NITRATE, BROMINE NITRITE, HALOGEN HYDROPEROXIDES, DICHLORINE PENTOXIDE, PEROXYCARBOXYLIC ACIDS, AND DIACYL PEROXIDES

Heats of formation of BrONO2, BrONO, BrOOH, FOOH, FOOCl, CF3C(O)OOH, H C(O)OOH, CH3C(O)OOH, and [CH3C(O)O](2) are estimated from bond contrib utions taken from I Phys. Chem., 100, 10150 (1996). They agree within +/-2 kcal/mol with recent experimental or ab initio data. The resultin g BDE(O-O) = 36 kcal/mol value in diacetyl peroxide requires the conce rted assistance of exothermic C-C(O) weakening in the transition state of its decomposition into Free radicals. It also implies the existenc e of a previously unrecognized 12 kcal/mol nonbonded repulsion in acyl anhydrides. The formation of chloryl chlorate with Delta H-f(O2ClOClO 2) = 50 kcal/mol, a marginally stable species toward dissociation into (ClO3 + OClO), may account for observations made in the [O(P-3) f OCl O] system at low temperatures. (C) 1998 John Wiley & Sons, Inc.