The solid electrolyte conducts oxide ions. Equilibrating oxygen at the two interfaces couples one molecule to four electrons. Taking the positive measured electromotive force as the air-reference potential relative to the Ni/NiO side, the Nernst equation isAssume air at one bar with , pure solid phases of unit thermodynamic activity, and . For the reaction normalized to one mole of oxygen,The negative sign is physically consistent with a strongly reducing Ni/NiO equilibrium relative to air. Using the supplied and givesThe tabulated free energies are per mole of , not per mole of NiO. Values normalized to one mole of NiO would be half as large. A reliable oxygen concentration cell measurement requires reversible interfaces, calibrated uniform temperature, a known reference oxygen pressure and predominantly ionic rather than electronic conduction through yttria-stabilized zirconia. Air is not pure oxygen: dropping the term changes the inferred entropy.
Yttria-stabilized zirconia 2026-10-20
Zirconia stabilized by addition of yttria. At suitable elevated temperatures, oxygen vacancies allow oxide-ion transport, making the material useful in an oxygen concentration cell. Its oxide-ion transference number must remain sufficiently close to one for a simple ionic Nernst equation interpretation.