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Ternary Chlorides of the Trivalent Early Lanthanides. Phase diagrams, crystal structures and thermodynamic properties

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Abstract

A comprehensive review on phase diagrams, crystal structures and thermodynamics of ternary chlorides formed in systems ACl/LnCl3 (A=Cs, Rb, K, Na; Ln=La−Gd) is presented. The review summarizes the author’s own studies, published since 1985, and original papers of other scientists. With the larger alkali metal ions compounds such as A3LnCl6, A2LnCl5 and ALn2Cl7were obtained. With sodium additional compounds NaLnCl4 and Na3Ln5Cl18 were obtained. The crystal structures are discussed with the concept of ionic radii, which determine the coordination numbers of Ln3+ and A+ cations against Cl− anions. The formation enthalpies of the compounds from ACl and LnCl3 were determined by solution calorimetry. Gibbs’ free energies and entropies for these reactions were obtained by e.m.f. measurements vs. temperature.

The stability of a ternary chloride in a systemACl−LnCl3 is given by the ‘free enthalpy of synproportionation’, that is, the formation of a compound from its neighbour compounds in the system. This ΔG 0 syn must be negative. A surprising result is, that the highest-melting compounds in the systems, A3LnCl6, are formed from ACl+A2LnCl5 by a loss in lattice energy. They exist as high-temperature compounds due to sufficiently high gain in entropy at temperatures whereTΔS>ΔH.

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  1. Inorganic Chemistry, University Kassel, D-34109, Kassel, Germany

    H. J. Seifert

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Seifert, H.J. Ternary Chlorides of the Trivalent Early Lanthanides. Phase diagrams, crystal structures and thermodynamic properties. Journal of Thermal Analysis and Calorimetry 67, 789–826 (2002). https://doi.org/10.1023/A:1014341829611

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