A mechanism based on electrochemical, spectrophotometric and scanning electron microscopy (SEM) data in alkaline media is proposed for the generation of Ag(III) in the form of Ag(OH)(4)(-). The formation of Ag(III) from Ag is a rather complex multistep process that involves several steps. The presence of soluble Ag(I) species as Ag(OH)(2)(-) is of paramount importance for the production of soluble Ag(OH)4-, whose decomposition time is shown to exceed 8 h. (C) 2013 Elsevier Ltd. All rights reserved.