Free Radical Formation in the Peroxynitrous Acid (ONOOH)/Peroxynitrite (ONOO-) System

Abstract
The rate constant of homolysis of peroxynitrite, ONOO-, into O2- and NO was determined to be 0.017 s-1 at 20 °C. In combination with other experimental data taken from the literature, this value yields the Gibbs free energy of formation of ONOO-, ΔfG°(ONOO-) = 16.6 kcal/mol. On the basis of this result, we conclude that peroxynitrous acid homolyzes to yield nitrogen dioxide (NO2) and hydroxyl (OH) free radicals and derive ΔfG°(ONOOH) = 7.7 kcal/mol. The rate constant of the reaction between NO and ONOO- was found to be 5 × 10-2 M-1 s-1 at most. The implications of the two homolysis reactions are discussed.