title: Oxyradical reactions: from bond-dissociation energies to reduction potentials.
abstract: Destructive radical reactions involve alkyl, alkoxyl and alkylperoxyl radicals, as well as alkylhydroperoxides. From bond energies the following reduction potentials vs NHE at neutral pH are derived: E0'(RO./ROH) = 1.6 V, E0'(ROO./ROOH) = 1.0 V, E0(ROOH/RO., H2O) = 1.9 V, and the two-electron reduction potential E0'(ROOH/ROH, H2O) = 1.7 V. Hydrogen abstraction from a bis-allylic methylene group by alkoxyl and alkylperoxyl radicals is favourable with Gibbs energies of -23 and -9 kcal/mol, respectively. Similarly, alkoxyl radicals can oxidize alkylhydroperoxides, delta G0' = -14 kcal/mol.
authors.affiliation: Biodynamics Institute, Louisiana State University, Baton Rouge 70803-1800.
authors.forename: W H
authors.initials: WH
authors.lastname: Koppenol
mesh_terms: D005609:Free Radicals; D006860:Hydrogen Bonding; D013816:Thermodynamics
chemical_list: D005609:Free Radicals