Variations in the overall charge and open-circuit potential of a palladium electrode during the adsorption of iodine and iodide anions

Abstract

Transients of the current and the open-circuit potential during the adsorption of I– and I2 on Pd/Pt (supporting electrolyte 0.5 M H2SO4) are measured and so are potentiodynamic and galvanostatic charging curves, in the presence and absence of adlayers. Dependences of the overall electrode charge on potential are constructed. After the adsorption of both I– and I2, values of the electrode surface charges at potentials of the double-layer region turn negative and considerably differ in their magnitude. The latter is connected with different character of adlayers, which is shown by experiments on the adsorption of silver atoms at underpotentials after a preliminary adsorption of I– and I2 on the electrode surface. Certain discrepancies between experimentally-found and theoretically-expected values of transients are attributed to a substantial increase in the irreversibility of sorption and desorption of hydrogen and oxygen in the presence of iodine atoms adsorbed on the surface.