Heat capacity and thermodynamic functions of sodium rare earth ternary fluorides

• Published in: The Journal of chemical thermodynamics 2024-01, Vol.188 (C), p.107154, Article 107154
• Main Authors: Gibson, Alexis, Yang, Shuhao, Riman, Richard E., Navrotsky, Alexandra, Woodfield, Brian F.
• Format: Article
• Language: English
• Subjects: Heat capacity; Hyperfine field splitting; Rare earth; Schottky anomaly; Ternary fluoride; Thermodynamic stability
• ISSN: 0021-9614; 1096-3626
• DOI: 10.1016/j.jct.2023.107154

•We report heat capacity measurements on NaNdF4, NaYbF4, and NaYF4.•We find a Schottky anomaly attributed to a nuclear contribution of varying intensity in each sample.•We demonstrate the stability of these compounds relative to the elements and fluorides. Sodium rare earth ternary fluorides, NaREF4 (RE = rare earth), are intermediate phases for rare earth element extraction and have important technological applications. To better understand their physical properties, energetics, and stability, we measured the heat capacity of three β-structured NaREF4 compounds, NaNdF4, NaYbF4, and NaYF4, from 1.8 to 300 K. Our measurements show an upturn in the low-temperature heat capacity of each sample which we attribute to the splitting of degenerate nuclear magnetic states. We provide calculations of the effective field causing the splitting for each sample. We also report standard entropy, enthalpy, and Gibbs energy increments at selected temperatures from 0 to 300 K. The enthalpy of formation of the three NaREF4 from the elements (ΔΗ°f,el) and the fluorides (ΔΗ°f,fl) were measured previously, enabling us to calculate the Gibbs energies of formation from the elements and fluorides. The Gibbs energy of NaREF4 relative to the elements at 298.15 K was calculated to be −1483.5 kJ∙mol−1, −1502.2 kJ∙mol−1, and −1497.8 kJ∙mol−1 with an estimated standard uncertainty of 1% for NaNdF4, NaYF4, and NaYbF4 respectively. The Gibbs energy of NaREF4 relative to the fluorides at 298.15 K was calculated to be –5.39 kJ∙mol−1, −18.12 kJ∙mol−1, and −19.1 kJ∙mol−1 with an estimated standard uncertainty of 1% for NaNdF4, NaYF4, and NaYbF4 respectively. Each sample’s negative Gibbs energy relative to both the elements and the fluorides indicates stability relative to these compounds. The results confirm that these three NaREF4 compounds are thermodynamically stable relative to the elements and binary fluorides.