Keywords

semi-differentiation, fractional calculus misapplication, electrochemical reaction analysis

Abstract

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, rigorous treatment and validation of the theory of semi-differential analysis of 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 in this paper are shown to agree with those calculated using the Berzins-Delahay equation.

Original Publication Citation

Tyler Williams et al 2023 J. Electrochem. Soc. 170 042502. https://doi.org/10.1149/1945-7111/accc59.

Document Type

Peer-Reviewed Article

Publication Date

2023-04-19

Publisher

Journal of The Electrochemical Society

Language

English

College

Ira A. Fulton College of Engineering

Department

Chemical Engineering

University Standing at Time of Publication

Assistant Professor

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