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A Kinetic and Thermodynamic Interpretation of Gibbs Free Energy and Electrode Potential

Author:

Manjunath, R

Category:

Research Papers

Sub-Category:

Biomechanics

Language:

English

Date Published:

December 28, 2025

File:

/Research Papers-Biomechanics/Download/7931

Downloads:

1351

Keywords:

Cell potential; electrochemistry; chemical thermodynamics; law of mass action; rate of reaction

Abstract:

The document shows how thermodynamics and kinetics together govern chemical and electrochemical reactions. For elementary reversible reactions, ΔG depends on the ratio of the forward and backward rates, linking spontaneity to whichever rate dominates. For non-elementary reversible reactions, ΔG also includes concentration terms, so equal forward and backward rates do not always imply ΔG = 0. The same kinetic–thermodynamic connection is applied to electrochemical systems, where electrode potential is influenced by reaction rates, ion concentration, and temperature in addition to enthalpy and entropy. A generalized equation is developed that extends the Nernst equation by incorporating kinetic effects. Case studies on zinc, silver, germanium, and platinum confirm that ion concentration affects both electrode potential and the reduction-to-oxidation rate balance. The document also relates the actual entropy change to temperature-dependent shifts in electrode potential and to the ratio of the actual enthalpy change plus the kinetic term to the standard enthalpy change plus the equilibrium term, offering a unified view of electrode behaviour.

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