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Semi-differentiation, or convolution as it is sometimes known, is a mathematical technique commonly used to disentangle overlapping peaks in cyclic or linear-sweep voltammograms. However, this technique is often misapplied due to misunderstandings of fractional calculus. Additionally, literature that applies this technique to reversible, soluble-insoluble electrochemical reactions is lacking. Peculiarities of semi-differentiation are explored, theoretical relations for semi-differentiated voltammograms are given, the exponential nature of the theoretical curve is explored, theoretical relations are compared to experimental voltammograms for AgNO3 in 1 M nitric acid at 298 K, NiCl2 in LiCl at 974 K, and LaCl3 in LiCl at 971 K, and the diffusion coefficients calculated from theoretical relations developed ihere are shown to agree with those calculated using the Berzins-Delahay equation.

Voltammetry studies of electrodeposition are growing rapidly. Yet, relations for the analysis of electrodeposition reactions in voltammetry remain relatively obscure in the literature. The existing cyclic and square wave voltammetry relations for electrodeposition and their limitations are discussed to increase awareness. A retrospective analysis is performed to demonstrate the impact of model selection in improving the analysis of electrodeposition behavior with voltammetric data. A repository for voltammetry models of electrodeposition is proposed to further increase familiarity and application of the most appropriate models, which would support a rapidly growing area of research and technological development.