The one-electron transfer redox potentials of free radicals. I. The oxygen/superoxide system

The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibrium constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones-semiquinones are calculated, as well as the standard redox potential of the peroxy radical. EoO2O2− = −0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O2O2− is higher by more than 0.2 V than earlier estimates, which has important implications on the possible role of O2− in biological processes of O2 fixation.