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Tafel slopes from first principles

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journal contribution
posted on 2008-10-09, 08:16 authored by Stephen Fletcher
Tafel slopes for multistep electrochemical reactions are derived from first principles. The derivation takes place in two stages. First, Dirac’s perturbation theory is used to solve the Schrödinger equation. Second, current-voltage curves are obtained by integrating the single-state results over the full density of states in electrolyte solutions. Thermal equilibrium is assumed throughout. Somewhat surprisingly, it is found that the symmetry factor that appears in the Butler-Volmer equation is different from the symmetry factor that appears in electron transfer theory, and a conversion formula is given. Finally, the Tafel slopes are compiled in a convenient look-up table.

History

School

  • Science

Department

  • Chemistry

Citation

FLETCHER, S., 2009. Tafel slopes from first principles. Journal of Solid State Electrochemistry, 13 (4), pp. 537–549

Publisher

© Springer Berlin / Heidelberg

Publication date

2009

Notes

This is a journal article. It was published in the journal, Journal of Solid State Electrochemistry [© Springer] and the original publication is available at: http://www.springerlink.com/content/101568/

ISSN

1432-8488;1433-0768

Language

  • en