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Thermodynamic properties of lanthanum, neodymium, gadolinium hafnates (Ln2Hf2O7): Calorimetric and KEMS studies

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Abstract

Using the data obtained by Knudsen effusion mass spectrometry, the standard formation thermodynamic properties of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 were calculated in the present study at high temperatures. Based on the results obtained, it was shown that the standard formation Gibbs energies of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 from the elements at the temperature 2445 K were consistent with the empirical rule concerning decrease of stability of pyrochlore hafnate phase with decrease in lanthanoid ionic radius. The La2Hf2O7 and Gd2Hf2O7 heat capacities were obtained in the present study by differential scanning calorimetry. These data were used along with those found earlier to evaluate the standard formation Gibbs energies of La2Hf2O7 and Gd2Hf2O7 from the elements at the temperature 298 K, which equal (−3937 ± 10) kJ/mol and (−3895 ± 10) kJ/mol, respectively. The thermodynamic properties of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 estimated in a wide temperature range allowed consideration of reliability of data available in the literature.

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Acknowledgments

This study was financially supported by the Russian Foundation for Basic Research through Grant Nos. 16-03-00940 and 19-03-00721. Determination of the La2Hf2O7 and Gd2Hf2O7 heat capacities was performed at the Thermogravimetric and Calorimetric Research Center of the Research Park of Saint Petersburg State University. Authors are very grateful to K.A. Sakharov, V.G. Sevastyanov, and N.T. Kuznetsov for supplying the La2Hf2O7 and Gd2Hf2O7 synthesized and identified samples used in the present study.

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  1. Institute of Chemistry, Saint Petersburg State University, Saint Petersburg, 199034, Russia

    Viktor A. Vorozhtcov, Valentina L. Stolyarova, Mikhail V. Chislov & Irina A. Zvereva

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

    Elizaveta P. Simonenko & Nikolay P. Simonenko

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  1. Viktor A. Vorozhtcov
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Correspondence to Valentina L. Stolyarova.

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Supplementary information: Thermodynamic properties of lanthanum, neodymium, gadolinium hafnates (Ln2Hf2O7) using the KEMS results (approximately 409 KB)

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Vorozhtcov, V.A., Stolyarova, V.L., Chislov, M.V. et al. Thermodynamic properties of lanthanum, neodymium, gadolinium hafnates (Ln2Hf2O7): Calorimetric and KEMS studies. Journal of Materials Research 34, 3326–3336 (2019). https://doi.org/10.1557/jmr.2019.206

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