Electron microscope investigations of silver electrodeposition on a (111) silver single crystal

The electrodeposition of silver from four selected baths with almost the same composition except for the anion was examined electrochemically and electron microscopically. The baths were prepared mainly from aqueous cyanide solutions containing silver cyanide, silver chloride, silver bromide and silver iodide. The results reveal that the electrodeposited silver grains become finer in the order Cl^- < Br^- < I^-, in good agreement with measurements of the electrochemical properties such as cathodic polarization, cathodic current efficiency and throwing power. This can be attributed to the adsorption sensitivity of the anions on the silver surface owing to their increasing polarizabilities and ionic radii.