Metallurgical Transactions A

, Volume 23, Supplement 1, pp 3325–3335 | Cite as

Variation of the partial thermodynamic

  • Tom Mathews
  • K. T. Jacob
Physical Chemistry


The variation of equilibrium oxygen potential with oxygen concentration in YBa2Cu3O7-δ has been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of the YBa2Cu3O7-δ sample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a mag- nesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non- stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with compo- sition. The partial enthalpy for δ = 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu306.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.


Metallurgical Transaction Oxygen Partial Pressure Solid Electrolyte Pure Oxygen Oxygen Potential 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



moles of i


chemical potential of i


temperature, K


pressure, Pa

standard pressure (1.01 × 105 Pa)


mole fraction of component


relative integral molar Gibbs' energy of mixing


relative partial molar Gibbs' energy of mixing of component i


relative partial molar enthalpy of mixing of component i


relative partial molar entropy of mixing of component i


oxygen nonstoichiometric parameter in YBa2Cu3O7-δ


emf, V


Faraday constant, 96,486.7 J/V


gas constant, 8.3143 J mol-1 deg-1


number of electrons


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Copyright information

© The Minerals, Metals & Materials Society - ASM Materials - The Materials Information Society 1992

Authors and Affiliations

  • Tom Mathews
    • 1
  • K. T. Jacob
    • 1
  1. 1.Department of MetallurgyIndian Institute of ScienceBangaloreIndia

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