Electrode Reactions that Deviate from Complete Equilibrium

Abstract

The example that was discussed earlier, the reaction of lithium with iodine to form LiI, dealt with elements and thermodynamically stable phases. By knowing a simple parameter, the standard Gibbs free energy of formation of the reaction product, the cell voltage under equilibrium and near-equilibrium conditions can be calculated for this reaction. If the cell operates under a fixed pressure of iodine at the positive electrode and at a stable temperature, the Gibbs phase rule indicates that the number of the residual degrees of freedom F in both the negative and positive electrodes is zero. Thus, the voltage is independent of the extent of the cell reaction.