Studies of adsorption and electron transfer processes in metal dissolution and passivation mechanisms often involve estimation of electrochemical parameters and model validation. Before parameter estimation can take place, we have to examine whether the parameters are structurally identifiable and also if the mechanism is distinguishable from others. In this paper necessary and sufficient conditions to check global identifiability and distinguishability of such electrochemical systems, using input-output models, are given through a simple test based on a systematic procedure. The method is based on the similarity transformation approach. The procedure is illustrated with examples.