Abstract
The standard Gibbs free energies of formation of CuAlO2 and CuAl2O4 were determined in the range 700° to 1100°C, using emf measurements on the galvanic cells (1) Pt,CuO +] Cu2O/CaO‐ZrO2/O2,Pt; (2) Pt,Cu +] CuAlO2+] Al2O3/CaO‐ZrO2/ Cu +] Cu2O,Pt; and (3) Pt,CuAl2O4+] CuAlO2+]Al2O3/CaO‐ZrO2/O2,Pt. The results are compared with published information on the stability of these compounds. The entropy of transformation of CuO from tenorite to the rock‐salt structure is evaluated from the present results and from earlier studies on the entropy of formation of spinels from oxides of the rock‐salt and corundum structures. The temperatures corresponding to 3‐phase equilibria in the system Cu2O‐CuO‐Al2O3 at specified O2 pressures calculated from the present results are discussed in reference to available phase diagrams.

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