18.6
A zinc-copper galvanic cell at standard conditions has a cell potential of +1.10 V and a ΔG value of −212 kJ, indicating that it operates spontaneously. However, as the reactant’s concentration changes during the cell’s discharge, it leads to a gradual decrease of cell potential until the reaction stops completely.
Conditions like these are called nonstandard. Here, the established standard values of cell potential, Gibbs free energy, and the equilibrium constant are no longer valid.
Nonstandard conditions are prevalent in many reactions ranging from redox reactions to ion gradients in neuronal membranes. But how is an accurate cell potential determined in such systems?
If the concentration of a reactant is greater, and the concentration of a product is smaller compared to standard conditions, then Le Châtelier’s Principle is used to determine the reaction’s direction qualitatively; however, it cannot be used for quantifying the deviating cell potential.
Thus, this necessitates establishing a relationship between the cell potentials for cells under standard and nonstandard conditions. Recall that the free energy changes under standard and nonstandard conditions are related.
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Nonstandard Reaction Conditions
The interconnection between standard cell potentials and various thermodynamic parameters such as the standard free en…
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