Voltammograms of silver reduction from complex thiourea electrolytes with the ligand to metal concentration ratio varied from 1 to 50 were measured on the freshly prepared surface of silver electrode. The results were analyzed using the numerical model of this electrode process which takes into account homogeneous chemical reactions proceeding in solution, diffusion-migration transfer of the species present in solution, and electrode reactions participated by electroactive components of the electrolyte. We estimated the values of standard exchange current density for partial electrode reactions in which silver complexes with different number of ligands can take part. The highest electrochemical activity is exhibited in solutions with the low concentration of complex-forming agent - by silver aqua complexes, while in solutions with high thiourea concentration - by silver complexes with one ligand. It was found that kinetic hindrances to discharge of the thiourea silver complexes unlikely to be due to the adsorption of thiourea molecules blocking the growth sites or to the adsorption of complex silver ions. The results admit interpretation of the mechanism of electrode process either from the viewpoint of simultaneous discharge of all the complex silver ions present or from the viewpoint of discharge of silver complex with one ligand in combination with rapid chemical reactions of dissociation of other, non-discharging silver complexes. (c) 2013 Elsevier B.V. All rights reserved.