AbstractElectrode processes of free radicals formed by a short pulse of high energy electrons are influenced bya) diffusion of the radicals,b) second order disappearance of the radicals,c) hindrance of the transfer reaction.Approximations for the evaluation of polarographic current‐time curves are discussed. The Birk‐Perone approximation developed for flash photo‐polarography is applied to describe the kinetics of electrode processes which have a large transfer rate constant. Experiments are carried out on the oxidation of the radical anions C6H5COCH3and CH3COCH3and on the reduction of CH3COCOCH3(at potentials where the transfer reaction is fast). The second order rate constants for radical‐radical reactions derived from the polarographic current‐time curves agree to within 20% with the optically determined rate constants. The reduction of CH3COCOCH3(at potentials where the rate of the transfer reaction is slow) is investigated as an example for electrode processes which depend on all three effects a), b), and c) mentioned above. The absolute rate constant of the transfer reaction was obtained for various potentials. The transfer coefficient amounts to 0.21 atpH = 6 for the reduction of C