Abstract
The historical origin of the Nernst equation can be traced back to Helmholtz’ treatment of the thermodynamics of galvanic cells and to Gibbs’ masterwork “On the Equilibrium of Heterogeneous Substances”. However, Nernst himself used a model of the metal/solution interface based on Arrhenius’ dissociation theory, together with some aspects of van’t Hoff’s osmotic pressure theory. Bancroft performed some initial studies of redox chains (cells) in Ostwald’s laboratory. Peters has advanced these studies and published an equation correctly describing the potential of an inert electrode in a solution containing a dissolved reversible redox pair. Riesenfeld has treated interfaces of immiscible electrolyte solutions and the partition equilibria of ions. Luther has shown how standard potentials of elements possessing several redox states are related. Fredenhagen was the first to understand that the series of standard potentials are solvent dependent. Nernst, Bancroft, Peters, Luther and Fredenhagen were pupils of Ostwald; Riesenfeld and Fredenhagen were students of Nernst. Indeed, the presiding genius of the whole endeavour was clearly Friedrich Wilhelm Ostwald. This new survey of the genesis and evolution of what we now call Nernst equation reveals the influence of Ostwald’s ideas on the theorizing process, and it is concluded that his share in the development of the modern theory deserves greater recognitions.
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Acknowledgements
I am very thankful to Professor Stephen Fletcher (Loughborough, UK) and Professor György Inzelt (Budapest, Hungary) for most valuable suggestions and comments, and to Dr. Elza Arminovna Zakharova (Tomsk, Russia) for providing copies of papers published by von Türin in Russian journals and for providing the obituary of von Türin, published by Shreder.
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Scholz, F. Wilhelm Ostwald’s role in the genesis and evolution of the Nernst equation. J Solid State Electrochem 21, 1847–1859 (2017). https://doi.org/10.1007/s10008-017-3619-y
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DOI: https://doi.org/10.1007/s10008-017-3619-y