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Thermodynamic Functions of Complex Zirconia Based Lanthanide Oxides—Pyrochlores Ln2Zr2O7 (Ln = La, Pr, Sm, Eu, Gd) and Fluorites Ln2O3 · 2ZrO2 (Ln = Tb, Ho, Er, Tm)

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Abstract

The review of the thermodynamic properties of complex lanthanide–zirconium oxides, namely, Ln2Zr2O7 (Ln = La, Pr, Sm, Eu, Gd) with a pyrochlore structure and Ln2O3 · 2ZrO2 solid solutions (Ln = Tb, Ho, Er, Tm) with a fluorite structure, is presented on the basis of our and literature data. The heat capacity was experimentally studied for Ln2Zr2O7 (for the cerium subgroup lanthanides) with a pyrochlore structure (Fd3m) and Ln2O3 · 2ZrO2 (for the yttrium subgroup lanthanides) with a fluorite structure (Fm3m), which were characterized by X-ray diffraction and elemental analyses, scanning electron microscopy, and adiabatic and differential scanning calorimetry. The temperature dependences of the thermodynamic functions (entropy, enthalpy change, and reduced Gibbs energy) were calculated within a broad range of temperatures from smoothed heat capacity values. The available thermodynamic data were compared, and some recommended values were given. The contribution of low-temperature magnetic transitions was taken into account for Ln2Zr2O7 (Ln = Pr, Nd, Sm, Gd). The effect of the Schottky anomaly on the heat capacity of lanthanide compounds was analyzed.

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ACKNOWLEDGMENTS

The authors are grateful to A.V. Shlyakhtina (Doctor of Chemistry, Semenov Institute of Chemical Physics, Russian Academy of Sciences) for providing us with the lanthanum zirconate sample, A.V. Tyurin (Candidate of Chemistry) and A.V. Khoroshilov (Candidate of Chemistry) for the calorimetric experiment, and V.M. Gurevich (Candidate of Chemistry) for help in calculating the thermodynamic functions.

Funding

This work was performed within the state task for the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences in the field of fundamental research under financial support of the Russian Foundation for Basic Research (project no. 15-03-04388) on the equipment of the Shared Facilities Center of the Kurnakov Institute of General and Inorganic Chemistry.

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  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991, Moscow, Russia

    V. N. Guskov, K. S. Gavrichev, P. G. Gagarin & A. V. Guskov

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  1. V. N. Guskov
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  2. K. S. Gavrichev
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Translated by E. Glushachenkova

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Guskov, V.N., Gavrichev, K.S., Gagarin, P.G. et al. Thermodynamic Functions of Complex Zirconia Based Lanthanide Oxides—Pyrochlores Ln2Zr2O7 (Ln = La, Pr, Sm, Eu, Gd) and Fluorites Ln2O3 · 2ZrO2 (Ln = Tb, Ho, Er, Tm). Russ. J. Inorg. Chem. 64, 1265–1281 (2019). https://doi.org/10.1134/S0036023619100048

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