The relationship between the potential of the cell reaction (Ecell), the entropy change (ΔS), and the enthalpy change (ΔH) is well established. Yet, there is surprisingly a very narrow range of experimental aqueous galvanic cells that follow thermodynamic predictions. The redox and equilibrium reactions used within Pourbaix diagrams are presented a priori to establish the limitations and application range of thermodynamic relationships within complex electrochemical systems, the Zn-Cu (Daniell cell) and Pb-Cu cells. These are then tested to validate the theoretical discussion. Specifically, the electromotive force of both cells is measured as a function of the temperature in order to calculate the thermodynamic properties of the reaction: concomitantly to the voltage measurements, the temperature, the pH, and the surface state of the electrodes.
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We also acknowledge Dr. Samuel Perry for manuscript editing.
We thank the NSERC, CFI, CSACS, and CQMF for financial support.
The Supporting Information is available free of charge on the Springer Publications website. Scheme of the different cells that were used,the galvanic measurements preformed using the Pb-Cu couple, XPS Oxygen measurements of the Pb substrate, SEM measurements of Pb substrate before and after 90min immersion in Pb(NO)3 solution and the oxygen:lead ratios measured by EDS. (DOCX 2200kb)
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Noyhouzer, T., Bellemare-Alford, D., Payne, N.A. et al. Unfolding the Hidden Reactions in Galvanic Cells. Electrocatalysis 9, 531–538 (2018). https://doi.org/10.1007/s12678-018-0459-1
- Pourbaix diagrams
- Galvanic cells
- Open circuit potential
- Thermodynamic measurements