Integral equation-based simulation of transient experiments for an EC2 mechanism: beyond the steady state simplification
Authors:
- Lesław K. Bieniasz,
- Michael Vynnycky,
- Sean McKee
Abstract
Transient electrochemical experiments are usually described theoretically by systems of reaction–diffusion partial differential equations. Converting them to integral equations is a classical and valuable modelling approach. Unfortunately, if any reaction–diffusion equation contains nonlinear reaction rate terms, up to now such a conversion has only been possible by assuming a steady state for the equation. Consequently, only sufficiently fast homogeneous reactions could be handled. In this work a novel integral equation-based modelling approach is described. The steady state assumption is replaced by a two-term singular perturbation expansion of the concentration–flux relationship, recently published by the authors. The expansion is valid for homogeneous reactions of (integer) order m>=1, occurring at planar electrodes. An example simulation of cyclic voltammetry for an EC2 reaction mechanism involving a second order dimerization reaction is performed. It is found that in this way the voltammograms can be satisfactorily simulated for homogeneous reaction rate constants smaller by about one order of magnitude than was previously possible.
- Record ID
- CUTcf1af3cf90fa45118c4cc4e7ad2647bf
- Publication categories
- ;
- Author
- Journal series
- Electrochimica Acta, ISSN 0013-4686, e-ISSN 1873-3859
- Issue year
- 2022
- Vol
- 428
- Pages
- [1-7]
- Article number
- 140896
- Other elements of collation
- wykr.; Bibliografia (na s.) - 7; Bibliografia (liczba pozycji) - 36; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 428
- Keywords in English
- nonlinear reaction–diffusion, cyclic voltammetry, integral equations, singular perturbation, computational electrochemistry
- ASJC Classification
- ;
- DOI
- DOI:10.1016/j.electacta.2022.140896 Opening in a new tab
- URL
- https://www.sciencedirect.com/science/article/pii/S0013468622010544 Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 100
- Score source
- journalList
- Score
- Publication indicators
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUTcf1af3cf90fa45118c4cc4e7ad2647bf/
- URN
urn:pkr-prod:CUTcf1af3cf90fa45118c4cc4e7ad2647bf
* presented citation count is obtained through Internet information analysis, and it is close to the number calculated by the Publish or PerishOpening in a new tab system.