Phase relations in Cu- RO_1.5- O (R < Ho, Er, Yb) and gibbs energy of formation of Cu₂R₂O₅ (R < Ho, Er, Yb) between 1000 and 1325K

Abstract

Phase relations in Cu-RO_1.5-O(R < Ho,Er,Yb) ternary systems at 1273K have been established by isothermal equilibration of samples containing different ratios of Cu:R(R < Ho,Er,Yb) in flowing air or high purity argon atmosphere for four days. The samples were then rapidly cooled to ambient temperature and the coexisting phases were identified by powder x-ray diffraction analysis. Only one ternary oxide, Cu₂R₂O₅(R < Ho,Er,Yb) was found to be stable. The chemical potential of oxygen for the coexistence of the three phase assemblage, Cu₂O + R₂O₃ + Cu₂R₂O₅(R < Ho,Er,Yb) has been measured by employing the solid-state galvanic cells,< (−) Pt, Cu₂O + Ho₂O₃+ Cu₂Ho₂O₅//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Er₂O₃+ Cu₂Er₂O//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Yb₂O₃ + Cu₂Yb₂O₅//CSZ//Air (Po₂ < 2.12 × 10⁴ Pa), Pt (+) in the temperature range of 1000 to 1325K. Combining the measured emf of the above cells with the chemical potential of oxygen at the reference electrode, using the Nernst relationship, gives for the reactions, 2Cu₂O(s) + 2Ho₂O₃(s) + O₂(g) → 2Cu₂Ho₂O₅(s) (1) 2Cu₂O(s) + 2Er₂O₃(s) + O₂(g) → 2Cu₂Er₂O₅(s) (2) and 2Cu₂O(s) + 2Yb₂O₃(s) + O₂(g) → 2Cu₂Yb₂O₅(s) (3) δΜo₂ = −219,741.3 + 145.671 T (±100) Jmol⁻¹ (4) δΜo₂ = −222,959.8 + 147.98 T(±100) Jmol⁻¹ (5) and δΜo₂ = −231,225.2 + 151.847 T(±100) Jmol⁻¹ (6) respectively. Combining the chemical potential of oxygen for the coexistence of Cu₂O + R₂O₃ + Cu₂R₂O₅(R− Ho,Er,Yb) obtained in this study with the oxygen potential for Cu₂O + CuO equilibrium gives for the reactions, 2 CuO(s) + Ho₂O₃(s) → Cu₂Ho₂O₅(s) (7) 2 CuO(s) + Er₂O₃(s) → Cu₂Er₂O₅(s) (8) and 2 CuO(s) + Yb₂O₃(s) → Cu₂Yb₂O₅(s) (9) δG‡ < 22,870.3 − 23.160 T (±100) Jmol⁻¹ (10) δG‡ < 21,261.1 − 22.002 T (±100) Jmol⁻¹ (11) and δG‡ < 17,128.4 - 20.072 T (±100) Jmol^-1 (12) It can be clearly seen that the formation of Cu₂R₂O₅R < Ho,Er,Yb) from the component oxides is endothermic. Further, Cu₂R₂O₅(R < Ho,Er,Yb) are an entropy stabilized phases. Based on the results obtained in this study, the oxygen potential diagram for Cu-R-O(R < Ho,Er,Yb) ternary system at 1273K has been composed.