Mechano-elektrochemische Effekte,VI. Einfluß der Elektrodengeometrie auf Potentialverschiebungen bei der plastischen Deformation von Kupfer und Hinweise auf die Systemorganisationen

Summary Plastic deformation of a copper electrode in an aqueous 10^–4 M Cu(ClO₄)₂ solution leads to greater potential shifts, to smaller post strain effects and to greater relaxation rates as the ratio interfacial area: volume of copper is increased. It is suggested that its system organization is improved, as the interfacial area is increased. The system organization appears also to be improved as oxidic superstructures are developing at the interface, where the highest hierarchic levels of both electrode and electrolyte are in immediate contact. Further hints as to the system organization of the whole system Cu/CuSO₄ solution are obtained from the fact that atpH=2 andc _Cu + +=10^–1 mol/l the redox potential is independent of the pretreatment of the electrode and independent of the presence of oxidic superstructures. It is underlined that the passivity due to the presence of an oxidic superstructure is maintained only atpH >2, whereas at lowerpH-values copper is more readily dissolved. It is suggested that atpH=2 the system is in an optimal state of system organization (OSO), similar to those reported in the course of phase transformations, in extremely thin metal films and in solutions at the isokinetic temperature.