The State of silver particles in aqueous dispersions and the course of their coagulation can be followed on voltammetric curves recorded with hanging mercury drop electrode. Sharp irregular cathodic current peaks produced by partial electroreduction of the species adsorbed on the surface of silver particles during their fortuitous impingements upon the electrode surface appear in time sequence on the curves. A change in the electrochemical behavior of silver sols in the time course of particles aggregation and growth was interpreted in agreement with the data of UV-vis spectroscopy and electron microscopy observations. (C) 2009 Elsevier Ltd. All rights reserved.