Pulse Radiolysis and Polarography: Polarograms and Structure of Short‐Lived Free Radicals

Abstract

Abstract The irreversible oxidation and reduction waves of some 20 radicals have been investigated. They are discussed with respect to the structure of the radicals and the mechanisms of the electrode processes involved. The effects that influence the position and shape of polarographic waves include double bond formation during the electron transfer, protonation of the radicals, differences in the atomic configuration, and solvent interactions between the radicals and their electrochemical products. The observed polarographic waves are also discussed with respect to possible distributions of occupied and unoccupied electronic levels of the systems R → R + and R → R − (R = radical).