Thermodynamic and structural variations along the olivenite–libethenite solid solution

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Abstract 2 (AsO4)(OH)–Cu2 (PO4)(OH)) solid solution as a model system for the P–As substitution in secondary minerals. The synthetic samples spanned the entire range from pure olivenite (X lib = 0) to libethenite (X lib = 1). Acid-solution calorimetry determined that the excess enthalpies are non-ideal, with a maximum at X lib = 0.6 of + - 1 ex =  X oli ⋅ X lib A + B (X oli - X lib A = 6.27  ± B = 2.9  ± - 1 X lib = 0.5 showed that there is no P–As ordering, meaning that the configurational entropy (S conf - R (X oli ln⁡ X oli + X lib ln⁡ X lib S vib ex S conf + S vib ex X lib = 0.6. Autocorrelation analysis of infrared spectra suggests local heterogeneity that arises from strain relaxation around cations with different sizes (As5 +/5 + ≈ 15  Å), the strain is partially compensated by the monoclinic–orthorhombic transformation. The volume of mixing shows complex behavior, determined by P–As substitution and symmetry change. A small (0.9 kJ mol- 1 X lib = 0.7 –0.8 confirms the change from monoclinic to orthorhombic symmetry.

Location
Deutsche Nationalbibliothek Frankfurt am Main
Extent
Online-Ressource
Language
Englisch

Bibliographic citation
Thermodynamic and structural variations along the olivenite–libethenite solid solution ; volume:35 ; number:2 ; year:2023 ; pages:157-169 ; extent:13
European journal of mineralogy ; 35, Heft 2 (2023), 157-169 (gesamt 13)

Creator
Majzlan, Juraj
Plumhoff, Alexandra
Števko, Martin
Steciuk, Gwladys
Plášil, Jakub
Dachs, Edgar
Benisek, Artur

DOI
10.5194/ejm-35-157-2023
URN
urn:nbn:de:101:1-2023033005331145212021
Rights
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Last update
14.08.2025, 11:03 AM CEST

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