Calorimetric study of the thermodynamic properties of Mn 5 O 8

Zhang, Pinghui; Liu, Jue; Page, Katharine; Navrotsky, Alexandra

doi:10.1111/jace.15951

Title: Calorimetric study of the thermodynamic properties of Mn ₅ O ₈

Journal Article · 29 July 2018 · Journal of the American Ceramic Society

DOI: https://doi.org/10.1111/jace.15951 · OSTI ID:1462130

Zhang, Pinghui ^[1]; Liu, Jue ^[2]; Page, Katharine ^[2];

^[1]

Peter A. Rock Thermochemistry Laboratory and NEAT ORU University of California Davis Davis California
Neutron Scattering Division Oak Ridge National Laboratory Oak Ridge Tennessee

Abstract Manganese oxides occur widely in nature and have technical applications in various areas. This study quantitatively evaluates the thermodynamic properties of Mn ₅ O ₈ , a binary manganese oxide that has a layered structure and contains coexisting divalent and tetravalent manganese. Three samples of the Mn ₅ O ₈ phase with slightly different manganese average oxidation states (Mn AOS) were synthesized using a wet chemical method and annealing. Synchrotron X‐ray analysis revealed that the samples contain a small amount of a secondary MnO ₂ phase that cannot be identified using laboratory X‐ray diffraction. High‐temperature oxide melt solution calorimetry in molten sodium molybdate at 700°C showed that all three samples are slightly higher in enthalpy than an isochemical mixture of bixbyite (Mn ₂ O ₃ ) and pyrolusite (MnO ₂ ), probably rendering them metastable in free energy with respect to isochemical mixtures of bixbyite and pyrolusite. However, the energetic metastability (endothermic enthalpy) of Mn ₅ O ₈ is very small (<6 kJ/mol) and does not depend significantly on the Mn AOS. Thus, although Mn ₅ O ₈ probably does not appear on the equilibrium Mn‐O phase diagram, its small metastability allows its synthesis by a variety of low temperature reactions.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; FG02-97ER14749

OSTI ID:: 1462130

Alternate ID(s):: OSTI ID: 1569078

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 3 Vol. 102; ISSN 0002-7820

Publisher:: Wiley-BlackwellCopyright Statement

Country of Publication:: United States

Language:: English

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