The physical model of an inert electrode partially activated with hemispherical microelectrodes was formed by the deposition of silver grains on a graphite substrate. It is shown that the process on the microelectrodes can be under activation control despite the fact that the overall rate is determined by the diffusion layer of the macroelectrode. On the basis of this conclusion a mathematical model of mass transfer on an inert electrode partially covered with active hemispherical particles (microclectrodes) is given and verified qualitatively by appropriate experiments. It was found that the degree of activation does not depend on the size of the particles, but on the ratio of the radius of the particles to the interparticle distance. This means that the quantity of catalyst required for the transformation of an inert electrode into an active one decreases strongly with decreasing active particle size. It was also shown that the maximum current density to the activated inert electrode was equal to the limiting diffusion one to the massive active electrode, as well as that the activity of the modified inert electrode at the same coverage of catalyst strongly depends on the exchange current density of the electrochemical process taking place on it. The larger is the exchange current density, the lower is the quantity of catalyst required for the same effect on the activity of the modified electrode. (c) 2007 Elsevier Ltd. All rights reserved.