We study and explain shapes of voltammogram spikes, observed during underpotential deposition (UPD) on electrode surfaces, as averaged envelopes of mutually shifted spikes associated with first-order phase transitions that occur in crystalline domains of various sizes that are formed on the electrode surface. This concept, already used in our previous work for two-phase systems and symmetric voltammogram spike shapes, is here substantially generalized to systems with multiple-phase coexistence and asymmetric spike shapes, using the rigorous statistical mechanical techniques of Borgs and Kotecky. Rather than mere numerical plots, we extract explicit functions that accurately describe the spike shapes. For the sake of clarity, we present our analysis and apply our results to fit the voltammogram of the UPD of Cu on Au(111) in sulfuric acid medium. This voltammogram shows two distinct spikes with a broad foot region near the spike at higher potentials. As was done in earlier treatments, we explain each of the two spikes as a result of a first-order transition. Here, though, the spikes are obtained as envelopes of closely spaced spikes resulting from crystals of various sizes. In contrast to earlier studies, however, we also explain the foot region in the same way. The foot's shape, despite its large width and small height, can be equally well obtained as an envelope of shifted crystal spikes that are broader and smaller than those giving rise to the two distinct spikes. We achieve very good agreement with experiment. (C) 2003 American Institute of Physics.