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    Róg, G. and Potoczek-Dudek, M. 2001. Determination of the standard molar Gibbs energy of formation of calcium zirconate by a galvanic cell involving calcium-ion conducting solid electrolyte. The Journal of Chemical Thermodynamics, Vol. 33, Issue. 1, p. 77.

    Róg,, G. Kozlowska-Róg,, A. and Bucko, M. 2000. Determination of the activities of {xCaO+ (1−x)LaCrO3} in the temperature range 1073 K to 1273 K by e.m.f. measurements. The Journal of Chemical Thermodynamics, Vol. 32, Issue. 6, p. 799.

    Raj, P Markondeya 1995. A critical assessment of the standard molar gibbs free energy of formation of NiWO4. Bulletin of Materials Science, Vol. 18, Issue. 5, p. 623.

    Pratt, J. N. 1990. Applications of solid electrolytes in thermodynamic studies of materials: A review. Metallurgical Transactions A, Vol. 21, Issue. 5, p. 1223.

    Pratt, J. N. 1990. Applications of solid electrolytes in thermodynamic studies of materials: A review. Metallurgical Transactions A, Vol. 21, Issue. 4, p. 1223.


Use of metastable equilibria for determination of Gibbs energy of solids

  • K. T. Jacob (a1) and S. Srikanth (a1)
  • DOI:
  • Published online: 01 January 2011

Attempts are made to measure activities of both components of a binary alloy (A–B) at 650 K using a solid-state galvanic cell incorporating a new composite solid electrolyte. Since the ionic conductivity of the composite solid electrolyte is three orders of magnitude higher than that of pure CaF2, the cell can be operated at lower temperatures. The alloy phase is equilibrated in separate experiments with flourides of each component and fluorine potential is measured. The mixture of the alloy (A–B) and the fluoride of the more reactive component (BF2) is stable, while (A–B) + AF2 mixture is metastable, Factors governing the possible use of metastable equilibria have been elucidated in this study. In the Co–Ni system, where the difference in Gibbs energies of formation of the fluorides is 21.4 kJ/mol, emf of the cell with metastable phases at the electrode is constant for periods ranging from 90 to 160 ks depending on alloy composition. Subsequently, the emf decreases because of the onset of the displacement reaction. In the Ni–Mn system, measurement of the activity of Ni using metastable equilibria is not fully successful at 650 K because of the large driving force for the displacement reaction (208.8 kJ/mol). Critical factors in the application of metastable equilibria are the driving force for displacement reaction and diffusion coefficients in both the alloy and fluoride solid solution.

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1C. Chatillon C. Senillou M. Allibert and A. Pattoret Rev. Sci. Instrum. 47, 334 (1976).

3N. Vaidehi R. Akila A. K. Shukla and K. T. Jacob Mater. Res. Bull. 21, 909 (1986).

4K. T. Jacob and J. P. Hajra Bull. Mater. Sci. 9, 37 (1987).

6K. T. Jacob S. Srikanth and G. N. K. Iyengar Bull. Mater. Sci. 8, 71 (1986).

9K. T. Jacob Metall. Trans. B 13, 283 (1982).

13R. Akila and K. T. Jacob Solid State Ionics 25, 217 (1987).

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Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
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