Energetics of melting of Yb2O3 and Lu2O3 from drop and catch calorimetry and first principles computations. (May 2019)

• Record Type: Journal Article
• Authors: Fyhrie, Matthew; Hong, Qi-Jun; Kapush, Denys; Ushakov, Sergey V.; Liu, Helena; van de Walle, Axel; Navrotsky, Alexandra
• Is Part Of: Journal of chemical thermodynamics. Volume 132(2019)
• Page Start: 405
• Page End: 410
• Publication Date: 2019-05
• Subjects: Thermodynamics -- Periodicals; Thermochemistry -- Periodicals; Thermodynamique -- Périodiques; Thermochimie -- Périodiques; Thermochemistry; Thermodynamics; Periodicals; 541.369
• DOI: 10.1016/j.jct.2019.01.008
• Languages: English
• ISSNs: 0021-9614

Abstract

Highlights: Δfus H°Yb2 O3 =102 ± 9 kJ/mol & Δfus H°Lu2 O3 =125 ± 11 kJ/mol from Drop'n Catch calorimetry. Δfus H°Yb2 O3 =124 ± 2 kJ/mol & Δfus H°Lu2 O3 =124 ± 3 kJ/mol from Ab initio computations. Computations determined high temperature Cp ° and ΔV on melting for Yb2 O3 and Lu2 O3 . Experimental results indicate substantial dissolution of oxygen in liquid Lu2 O3 . Konings et al. (2014) assessment for Δfus H° is in best agreement with these results. Abstract: The energetics of melting of Yb2 O3 (T fus 2707 ± 20 K) and Lu2 O3 (T fus 2762 ± 15 K) were studied experimentally by drop-and-catch (DnC) calorimetry and computationally by ab initio molecular dynamic (AI MD) techniques. Fusion enthalpies for Yb2 O3 (102 ± 10) kJ∙mol −1 and Lu2 O3 (125 ± 10) kJ∙mol −1 were derived from the steps in enthalpy increments from DnC experiments performed on liquid and solid samples laser heated in an argon flow. Fusion enthalpy values for Yb2 O3 and Lu2 O3 obtained from AI MD computations were 124 ± 2 kJ/mol and 124 ± 3 kJ/mol, respectively. High temperature heat capacity values for solid and liquid phases and volume change on melting were obtained from AI MD. Computed volume change on melting for both oxides is less than 1%, prompting an experimental investigation due to difference with prior experimental results. Experimental results indicate substantial dissolution of oxygen in liquid Lu2 O3.