Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2017 / Paper 1 / Section A(iii) / 6 / i

The solid electrolyte conducts oxide ions. Equilibrating oxygen at the two interfaces couples one ${\mathrm{O}}_2$ 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 $p_{\mathrm{air}}/p^{\circ }=0.21$, pure solid phases of unit thermodynamic activity, and $p^{\circ }=1\mathrm{bar}$. 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 $R$ and $F$ givesThe tabulated free energies are per mole of ${\mathrm{O}}_2$, 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 $RT\ln 0.21$ term changes the inferred entropy.