Gradient solid electrolytes for thermodynamic measurements: system Na₂CO₃-Na₂SO₄

Abstract

The thermodynamic properties of Na₂CO₃-Na₂SO₄ solid solution with hexagonal structure have been measured in the temperature range of 873 to 1073 K, using a composite-gradient solid electrolyte. The cell used can be represented as Pt, CO₂′ + O₂∥ Na₂CO₃Na₂ (CO₃)_x(SO₄)_1-x) ∥ CO₂″ + O₂″, Pt The composite-gradient solid electrolyte consisted of pure Na₂CO₃ at one extremity and the solid solution under study at the other, with variation in composition across the electrolyte. A CO₂+ O₂ + Ar gas mixture was used to fix the chemical potential of sodium at each electrode. The Nernstian response of the cell to changes in partial pressures of CO₂ and O₂ at the electrodes has been demonstrated. The activity of Na₂CO₃ in the solid solution was measured by two techniques. In the first method, the electromotive force (emf) of the cell was measured with the same CO₂ + O₂ + Ar mixture at both electrodes. The resultant emf is directly related to the activity of Na₂CO₃ at the solid solution electrode. By the second approach, the activity was calculated from the difference in compositions of CO₂ + O₂ + Ar mixtures at the two electrodes required to produce a null emf. Both methods gave identical results. The second method is more suitable for gradient solid electrolytes that exhibit significant electronic conduction. The activity of Na₂CO₃ exhibits positive deviation from Raoult’s law. The excess Gibbs’ energy of mixing of the solid solution can be represented using a subregular solution model such as the following: ΔG^E = X(1 - X)[6500(±200)X + 3320(±80)(l - X)] J mol^-1 whereX is the mole fraction of Na₂CO₃. By combining this information with the phase diagram, mixing properties of the liquid phase are obtained.