Calorimetric study of skutterudite (CoAs2.92) and heazlewoodite (Ni3S2)

Majzlan, Juraj; Kiefer, Stefan; Lilova, Kristina; Subramani, Tamilarasan; Navrotsky, Alexandra; Tuhý, Marek; Vymazalová, Anna; Chareev, Dmitriy A.; Dachs, Edgar; Benisek, Artur

doi:10.2138/am-2022-8337

Calorimetric study of skutterudite (CoAs2.92) and heazlewoodite (Ni3S2)

Journal Article · 01 December 2022 · American Mineralogist

DOI:https://doi.org/10.2138/am-2022-8337· OSTI ID:2419473

Majzlan, Juraj ^[1]; Kiefer, Stefan; Lilova, Kristina; Subramani, Tamilarasan; Navrotsky, Alexandra; ; Vymazalová, Anna; Chareev, Dmitriy A.; Dachs, Edgar; Benisek, Artur

OSTI

Abstract

Nickel and cobalt arsenides, sulfarsenides, and sulfides occur in many hydrothermal ore deposits, but their thermodynamic properties are not well known, in some cases not known at all. In this work, we determined a full set of thermodynamic properties for heazlewoodite and skutterudite. Both phases were synthesized in evacuated silica tubes at elevated temperatures, and electron microprobe analyses gave their compositions as Ni3S2 and CoAs2.92, respectively. Enthalpies of formation were measured by high-temperature oxide-melt solution calorimetry. The reference phases were pure elements, thus eliminating any systematic errors related to such phases. The enthalpies of formation at T = 298.15 K and P = 105 Pa are –216.0 ± 8.4(2σ) and –88.2 ± 6.1 kJ·mol−1 for Ni3S2 and CoAs2.92, respectively. Entropies were calculated from low-temperature heat capacity (CP) data from relaxation (PPMS) calorimetry and are 133.8 ± 1.6 and 106.4 ± 1.3 J·mol–1·K–1, respectively. The calculated Gibbs free energies of formation are –210.0 ± 8.4 and –79.9 ± 6.2 kJ·mol−1 for Ni3S2 and CoAs2.92, respectively. The PPMS CP data, together with a set of differential scanning calorimetry measurements, were used to derive CP polynomials up to 700 K with the Kieffer model based on previously published frequencies of acoustic and optic modes. Equilibrium constants for selected reactions with an aqueous phase were calculated up to 700 K. Geochemical modeling in these systems, however, should await until more reliable data for other phases from the system Co-Ni-As-S are available.

Research Organization:: Univ. of California, Davis, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: FG02-97ER14749

OSTI ID:: 2419473

Journal Information:: American Mineralogist, Journal Name: American Mineralogist Journal Issue: 12 Vol. 107; ISSN 0003-004X

Publisher:: Mineralogical Society of America

Country of Publication:: United States

Language:: English

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