Butler-Volmer Equation: Simplifications and Interpretations

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Description

This lecture covers the Butler-Volmer equation and its simplifications, such as the Tafel kinetics and the Arrhenius relationship. It explains the interpretation of the frequency factor kº and its impact on reaction rates. The lecture also delves into the effect of equilibrium reference potential on the Butler-Volmer equation, mass transport contributions, and the physiochemical interpretations of various parameters involved in electrochemical reactions.

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Related concepts (125)

Tafel equation

The Tafel equation is an equation in electrochemical kinetics relating the rate of an electrochemical reaction to the overpotential. The Tafel equation was first deduced experimentally and was later shown to have a theoretical justification. The equation is named after Swiss chemist Julius Tafel." It describes how the electrical current through an electrode depends on the voltage difference between the electrode and the bulk electrolyte for a simple, unimolecular redox reaction ".

Pre-exponential factor

In chemical kinetics, the pre-exponential factor or A factor is the pre-exponential constant in the Arrhenius equation (equation shown below), an empirical relationship between temperature and rate coefficient. It is usually designated by A when determined from experiment, while Z is usually left for collision frequency. The pre-exponential factor can be thought of as a measure of the frequency of properly oriented collisions. It is typically determined experimentally by measuring the rate constant at a particular temperature and fitting the data to the Arrhenius equation.

Electrochemical kinetics

Electrochemical kinetics is the field of electrochemistry that studies the rate of electrochemical processes. This includes the study of how process conditions, such as concentration and electric potential, influence the rate of oxidation and reduction (redox) reactions that occur at the surface of an electrode, as well as an investigation into electrochemical reaction mechanisms.

Electrochemical cell

An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells which generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells. Both galvanic and electrolytic cells can be thought of as having two half-cells: consisting of separate oxidation and reduction reactions.

Exchange current density

In electrochemistry, exchange current density is a parameter used in the Tafel equation, Butler–Volmer equation and other electrochemical kinetics expressions. The Tafel equation describes the dependence of current for an electrolytic process to overpotential. The exchange current density is the current in the absence of net electrolysis and at zero overpotential. The exchange current can be thought of as a background current to which the net current observed at various overpotentials is normalized.