title: Can O=NOOH undergo homolysis?
abstract: Recent thermodynamic calculations of Merenyi and Lind [(1997) Chem. Res. Toxicol. 10, 1216-1220] suggest that O=NOOH can undergo homolysis to form the hydroxyl radical and nitrogen dioxide. This result is based in part on our statement that the enthalpy of ionization of O=NOOH is close to zero [Koppenol et al. (1992) Chem. Res. Toxicol. 5, 834-842]. As the ionization of O=NOOH is sensitive to the milieu and the rate of isomerization (to nitrate) to the total concentration of O=NOOH and O=NOO- [Kissner et al. (1997) Chem. Res. Toxicol. 10, 1285-1292], we reinvestigated the temperature dependence of the ionization constant and determined a deltaHo of 4+/-2 kcal mol(-1). This results in a standard Gibbs energy of homolysis of 16 kcal mol(-1) and a rate of homolysis of 1 x 10(-2) s[-1]. Given the uncertainty in the Gibbs energy of homolysis, upper and lower rates are 1 x 10(-4) and 0.6 s(-1), slower than the rate of isomerization, 1.2 s(-1) at 25 degrees C. The recombination of the homolysis products NO2. and HO. is known to lead to mainly peroxynitrous acid. If one assumes that a few percent of the recombinations lead to nitrate instead, then the rate of homolysis must be much higher than the rate of isomerization. We conclude therefore that homolysis is unlikely.
authors.affiliation: Laboratorium für Anorganische Chemie, Eidgenössische Technische Hochschule-Zürich, Switzerland. koppenol@inorg.chem.ethz.ch
authors.forename: W H
authors.initials: WH
authors.lastname: Koppenol
authors.forename: R
authors.initials: R
authors.lastname: Kissner
mesh_terms: D019277:Entropy; D017665:Hydroxyl Radical; D009566:Nitrates / Q000737:chemistry*; D009585:Nitrogen Dioxide; D011522:Protons; D013816:Thermodynamics
chemical_list: D009566:Nitrates; D011522:Protons; C039642:peroxynitric acid; D017665:Hydroxyl Radical; D009585:Nitrogen Dioxide