D. Noel Buckley
D. Noel Buckley
University of Limerick and Case Western Reserve University
Date: August 27, 2025
Time: 1000–1100h ET
The Butler–Volmer equation is commonly the standard model of electrochemical kinetics. Typically, the effects of applied voltage on the free energies of activation of the forward and backward reactions are analyzed and used to derive a current-voltage relationship. Traditionally, specific properties of the electrode metal were not considered in this derivation and consequently the resulting expression contained no information on the variation of exchange current density with electrode-material-specific parameters such as work function Φ. In recent papers, Buckley and Leddy revisited the classical derivation of the Butler–Volmer equation to include the effect of the electrode metal. We considered in detail the complementary relationship of the chemical potential of electrons μ_e and the Galvani potential φ and so derived expressions for the current-voltage relationship and the exchange current density that include μ_e. The exchange current density j_0 appears as an exponential function of Δμ_e. Making the approximation Δμ_e≈-FΔΦ yields a linear relationship between ln〖. This linear increase in ln〖j_0 〗 with Φ had long been reported but had not been explained. In this webinar, these recent modifications of the Butler-Volmer equation and their consequences are discussed.
Why attend?
- Learn how the classical Butler–Volmer equation may be extended to account for specific effects of electrode material.
- Understand the complementary relationship of the chemical potential of electrons μ_e and the Galvani potential φ and its fundamental effects on the kinetics of electrode processes.
- Explore how a recent adaptation of the Butler–Volmer equation can explain a longstanding puzzle in electrochemical kinetics.
Presenter
D. Noel Buckley is Professor Emeritus of Physics at the University of Limerick (UL) and Adjunct Professor of Chemical and Biomolecular Engineering at Case Western Reserve University (CWRU). He has over 50 years of research experience on a range of topics.
Prof. Buckley’s PhD research on oxygen electrochemistry at University College Cork was followed by postdoctoral research on high-temperature corrosion at the University of Pennsylvania. From 1979 to 1996, he worked at Bell Laboratories, initially on lithium batteries, then mainly on III-V semiconductors for electronics and photonics. His research at UL has been on semiconductor electrochemistry, stress in electrodeposited nanofilms and electrochemical energy storage, principally vanadium flow batteries in collaboration with Bob Savinell’s group at CWRU. Prof. Buckley’s recent interest in the theory of electron transfer kinetics arose from collaboration with Johna Leddy at the University of Iowa. He has taught courses in scientific writing since 2006 at UL and Short Courses at several ECS Meetings. The recipient of the ECS Europe Section Heinz Gerischer Award and ECS Electronics and Photonics Division Award, he is an ECS Fellow and Past President. Prof. Buckley served as an editor of the Journal of The Electrochemical Society and Electrochemical and Solid State Letters. Recently, he led Poetry Evenings at ECS Meetings in Gothenburg and Montréal.
Interested in presenting in the ECS Webinar Series? Email your presentation title and abstract to education@electrochem.org for consideration.