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The Butler-Volmer equation in electrochemical theory: Origins, value, and practical application

Dickinson, E J F; Wain, A J (2020) The Butler-Volmer equation in electrochemical theory: Origins, value, and practical application. Journal of Electroanalytical Chemistry, 872. 114145 ISSN 15726657

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We review the use of the Butler-Volmer equation to describe electrode kinetics. Across all fields of electrochemistry, this equation is deployed in diverse mathematical forms whose mutual interrelation is infrequently expressed and often unclear. The plurality of forms of the Butler-Volmer equation sometimes engenders misunderstanding in the literature, such as misuse of terminology or inappropriate mathematical expression of the kinetic equations. We express the basis of the Butler-Volmer equation as an empirical expression for a two-way activated redox process, and illustrate the constraints that limit applications of this equation for many electrocatalytic or electrochemical solid-insertion processes not equating to a simple one-electron transfer. Preferences towards different parametric expressions of the Butler-Volmer equation between the fields of electroanalytical chemistry and electrochemical engineering are correlated to both the different types of electrochemical processes commonly encountered in these fields, and their different scientific motivations. We further discuss briefly the scope of recent experimental efforts towards verification of the Butler-Volmer equation, considering the sensitivity (or relative lack thereof) of common experimental techniques to its component parameters.

Item Type: Article
Subjects: Advanced Materials > Electrochemistry
Divisions: Electromagnetic & Electrochemical Technologies
Identification number/DOI: 10.1016/j.jelechem.2020.114145
Last Modified: 15 Jan 2021 15:29
URI: http://eprintspublications.npl.co.uk/id/eprint/9010

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