Thermodynamic and structural variations along the olivenite–libethenite solid solution

[Marco E. Ciriotti]

Referenza:
▪ Majzlan, J., Plumhoff, A., Števko, M., Steciuk, G., Plášil, J., Dachs, E., Benisek, A. (2023): Thermodynamic and structural variations along the olivenite–libethenite solid solution. European Journal of Mineralogy, 35, 157-169.

Abstract:
Many natural secondary arsenates contain a small fraction of phosphate. In this work, we investigated the olivenite–libethenite (Cu2(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 (Xlib=0) to libethenite (Xlib=1). Acid-solution calorimetry determined that the excess enthalpies are non-ideal, with a maximum at Xlib=0.6 of +1.6 kJ mol−1. This asymmetry can be described by the Redlich–Kister equation of Hex= Xoli⋅Xlib [A+B(Xoli−Xlib)], with A=6.27 ± 0.16 and B=2.9 ± 0.5 kJ mol−1. Three-dimensional electron diffraction analysis on the intermediate member with Xlib=0.5 showed that there is no P–As ordering, meaning that the configurational entropy (Sconf) can be calculated as ). The excess vibrational entropies (), determined by relaxation calorimetry, are small and negative. The entropies of mixing () also show asymmetry, with a maximum near Xlib=0.6. Autocorrelation analysis of infrared spectra suggests local heterogeneity that arises from strain relaxation around cations with different sizes (As5+  P5+) in the intermediate members and explains the positive enthalpies of mixing. The length scale of this strain is around 5 Å, limited to the vicinity of the tetrahedra in the structure. At longer length scales (≈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) drop in enthalpies of mixing in the region of Xlib=0.7–0.8 confirms the change from monoclinic to orthorhombic symmetry.