Electrochemical kinetics, microkinetics modelling -A tutorial from basics to practical implementation
Abstract
Electrochemistry is at the root of many industrial processes, especially related to energy and environmental applications. Electrochemical kinetics provides a mathematical frame to electrochemistry, enabling to model charge-transfer reactions and to extract kinetics parameters from experimental measurements. Though the approach is widely used in the literature, it is not always attempted in the proper manner. This tutorial details what an electrochemical system is, how to write electrochemical reactions, express their rates and rate constants in the Butler-Volmer formalism, define species conversion rates and current density, and model mass-transport. This paves the way towards comprehensive microkinetics modelling, which is firstly adapted to the Redox E reaction. The numerous steps needed to determine the Butler-Volmer equation (and related Tafel equation) are described, together with their conditions of applications. This theoretical approach is completed by relevant examples of applications, where kinetic constants of charge-transfer or mass-transport can be determined. The tutorial also provides extension of the Butler-Volmer formalism into more complex ones (for example, the Marcus-Hush-Chidsey theory), that become necessary when the Butler-Volmer kinetics does not apply experimentally.
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BibTeX
@article{bonnefont2026electrochemical,
title = {{Electrochemical kinetics, microkinetics modelling -A tutorial from basics to practical implementation}},
author = {Antoine Bonnefont and Marian Chatenet},
journal = {Electrochimica Acta},
year = {2026},
month = sep,
doi = {10.1016/j.electacta.2026.149713},
url = {https://univ-grenoble-alpes.hal.science/hal-05766754v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Electrochemical kinetics, microkinetics modelling -A tutorial from basics to practical implementation
AU - Antoine Bonnefont
AU - Marian Chatenet
PY - 2026
DA - 2026/09/28
JO - Electrochimica Acta
DO - 10.1016/j.electacta.2026.149713
UR - https://univ-grenoble-alpes.hal.science/hal-05766754v1
AB - Electrochemistry is at the root of many industrial processes, especially related to energy and environmental applications. Electrochemical kinetics provides a mathematical frame to electrochemistry, enabling to model charge-transfer reactions and to extract kinetics parameters from experimental measurements. Though the approach is widely used in the literature, it is not always attempted in the proper manner. This tutorial details what an electrochemical system is, how to write electrochemical reactions, express their rates and rate constants in the Butler-Volmer formalism, define species conversion rates and current density, and model mass-transport. This paves the way towards comprehensive microkinetics modelling, which is firstly adapted to the Redox E reaction. The numerous steps needed to determine the Butler-Volmer equation (and related Tafel equation) are described, together with their conditions of applications. This theoretical approach is completed by relevant examples of applications, where kinetic constants of charge-transfer or mass-transport can be determined. The tutorial also provides extension of the Butler-Volmer formalism into more complex ones (for example, the Marcus-Hush-Chidsey theory), that become necessary when the Butler-Volmer kinetics does not apply experimentally.
SN - 0013-4686
ER -