INVESTIGATION OF CHARGE-TRANSPORT ACROSS THE AG-VERTICAL-BAR-AGI-INTERFACE .1. OCCURRENCE OF PERIODIC PHENOMENA DURING ANODIC-DISSOLUTION OF SILVER

By drawing a constant electric current through a symmetric electrochem ical cell of the type Ag\alpha-AgI\Ag we observed, under certain exper imental conditions, strong periodic oscillations of the voltage across the cell. Depending on current density and applied mechanical force, these oscillations show either periodic or irregular behaviour. Furthe r experiments show that these strong voltage oscillations are caused b y the anodic interface at which Ag-metal is dissolved electrochemicall y into the solid electrolyte, The phenomenon itself is reproducible, b ut the appearance of the oscillations is very sensitive to the experim ental conditions. We present experimental results for different experi mental conditions and cell types and discuss a possible mechanism for the observed phenomenon. An important element of the attempt to find a microscopic explanation is the basic process of forming lattice vacan cies in the metal at the anodic interface. The behaviour of these vaca ncies is crucial for the kinetic properties of the metal-solid electro lyte interface under non-equilibrium conditions.