title: Homolysis of the peroxynitrite anion detected with permanganate.
abstract: The reaction of peroxynitrite with violet-colored MnO4- leads to the formation of green MnO42-. The rate constant for the reaction at pH 11.7, 5.5 mM ionic strength, and 25 degrees C, 0.020 +/- 0.001 s(-1), is independent of the MnO4- concentration; homolysis of ONOO- to NO* and O2*- is the rate-determining step. Both NO* and O2*- react with MnO4- with rate constants of (3.5 +/- 0.7) x 10(6) M(-1)s(-1) and (5.7 +/- 0.9) x 10(5) M(-1)s(-1), respectively. The activation volume and activation energy for breaking the N-O bond are 12.6 +/- 0.8 cm(3)mol(-1) and 102 +/- 2 kJ mol(-1), respectively. In combination with the known standard Gibbs energies of formation of NO* and O2*-, the rate of the reaction of NO* and O2*-, and the pKa of ONOOH, we find a standard Gibbs energy of formation of ONOO- of +68 +/- 1 kJ mol(-1), and of ONOOH of +31 +/- 1 kJ mol(-1).
authors.affiliation: Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland.
authors.forename: Manuel
authors.initials: M
authors.lastname: Sturzbecher
authors.forename: Reinhard
authors.initials: R
authors.lastname: Kissner
authors.forename: Thomas
authors.initials: T
authors.lastname: Nauser
authors.forename: Willem H
authors.initials: WH
authors.lastname: Koppenol