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The system Ag-Au-Se: Phase relations below 405 K and determination of standard thermodynamic properties of selenides by solid-state galvanic cell technique

  • Evgeniy G. Osadchii EMAIL logo and Ekaterina A. Echmaeva
Published/Copyright: April 1, 2015
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American Mineralogist
From the journal American Mineralogist Volume 92 Issue 4

Abstract

The existence of the only ternary compound, Ag3AuSe2 (fischesserite), in the Ag-Au-Se system was confirmed by solid-state annealing method. The selenium analog of petrovskaite (AgAuS) was not observed under the experimental conditions (in the temperature range of 350-773 K and own vapor pressure).

The solid-state reactions

2Ag(cr) + Se(s) = Ag2Se(cr)

Ag(cr) + Ag3AuSe2(cr) = 2Ag2Se(cr) + Au(cr)

3Ag(cr) + 2AuSe(s) = Ag3AuSe2(cr) + Au(cr)

were studied by the electromotive force (EMF) technique in all solid-state galvanic cells with Ag4RbI5 as a solid electrolyte. The experiments were run in a dry argon gas flow at atmospheric pressure.

The following standard thermodynamic properties of the stable phases were determined at 298.15 K and 1 bar (105 Pa):

ΔfG°(Ag2Se, low naumannite) = -49470 (±130) J/mol,

S°(Ag2Se, low naumannite) = 149.99 (±0.56) J/(K·mol);

ΔfG°(Ag2Se, high naumannite) = -47430 (±290) J/mol,

S°(Ag2Se, high naumannite) = 169.01 (±0.78) J/(K·mol);

ΔfG°(Ag3AuSe2, fischesserite) = -86450 (±320) J/mol,

S°(Ag3AuSe2, fischesserite) = 290.80 (±1.26) J/(K·mol);

ΔfG°(β-AuSe) = -4110 (±1300) J/mol;

S°(β-AuSe) = 75.49 (±3.55) J/(K·mol).

The phase transition point for low naumannite-high naumannite was determined at Ttrs = 405.4 K, with the enthalpy of transition of ΔtrsH = -7713 (±550) J/mol.

Keywords: Thermodynamic data; naumannite; fischesserite; AuSe; EMF-method; solid-state galvanic cell
Received: 2006-1-8
Accepted: 2006-11-16
Published Online: 2015-4-1
Published in Print: 2007-4-1

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2007.2209
Keywords for this article
Thermodynamic data; naumannite; fischesserite; AuSe; EMF-method; solid-state galvanic cell

Articles in the same Issue

  1. New constraints on metamorphic history of Adirondack diopsides (New York, U.S.A.): Al and δ18O profiles
  2. Hammadah al Hamra 193: The first amphibole-bearing winonaite
  3. Crystal chemistry of trioctahedral micas in alkaline and subalkaline volcanic rocks: A case study from Mt. Sassetto (Tolfa district, Latium, central Italy)
  4. Magnetic excitations and heat capacity of fayalite, Fe2SiO4
  5. The barometer tremolite + tschermakite + 2 albite = 2 pargasite + 8 quartz: Constraints from experimental data at unit silica activity, with application to garnet-free natural assemblages
  6. In-situ measurement of dissolution of anorthite in Na-Cl-OH solutions at 22 °C using phase-shift interferometry
  7. Experimental investigation of the breakdown of dolomite in rock cores at 100 MPa, 650-750 °C
  8. Dissolution of the (001) surface of galena: An in situ assessment of surface speciation by fluid-cell micro-Raman spectroscopy
  9. An infrared spectroscopic study of the OH stretching frequencies of talc and 10-Å phase to 10 GPa
  10. Co2+-Cu2+ substitution in bieberite solid-solution series, (Co1-xCux)SO4·7H2O, 0.00 ≤ x ≤ 0.46: Synthesis, single-crystal structure analysis, and optical spectroscopy
  11. Clinoenstatite exsolution in diopsidic augite of Dabieshan: Garnet peridotite from depth of 300 km
  12. Heat-pulse calorimetry measurements on natural chlorite-group minerals
  13. Low-temperature behavior of NaGaSi2O6
  14. Single-crystal elasticity of zoisite Ca2Al3Si3O12(OH) by Brillouin scattering
  15. The effect of valence state and site geometry on Ti L3,2 and O K electron energy-loss spectra of TixOy phases
  16. Characterization of defects and the local structure in natural and synthetic alunite (K, Na, H3O)Al3(SO4)2(OH)6 by multi-nuclear solid-state NMR spectroscopy
  17. Using a mineral lifetime diagram to evaluate the persistence of olivine on Mars
  18. Complexity in 15- and 30-sectors polygonal serpentine: Longitudinal sections, intrasector stacking faults and XRPD satellites
  19. Light-induced alteration of arsenic sulfides: A new product with an orthorhombic crystal structure
  20. Transmission electron microscopy study of magnetites in a freshwater population of magnetotactic bacteria
  21. Anomalous behavior at the I2/a to Imab phase transition in SiO2-moganite: An analysis using hard-mode Raman spectroscopy
  22. The system Ag-Au-Se: Phase relations below 405 K and determination of standard thermodynamic properties of selenides by solid-state galvanic cell technique
  23. Rhombohedral (9R) and hexagonal (6H) perovskites in barium silicates under high pressure
  24. Structural effects of pressure on monoclinic chlorite: A single-crystal study
  25. Neptunium incorporation in sodium-substituted metaschoepite
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  27. Symmetry and crystal structure of biaxial elbaite-liddicoatite tourmaline from the Transbaikalia region, Russia
  28. Letter: Onion morphology and microstructure of polyhedral serpentine
  29. Letter: Ion microprobe analysis of (231Pa)/(235U) and an appraisal of protactinium partitioning in igneous zircon
  30. Letter: Structural investigation of Mg local environments in silicate glasses by ultra-high field 25Mg 3QMAS NMR spectroscopy
  31. Letter: Entropies of mixing and subsolidus phase relations of forsterite–fayalite (Mg2SiO4–Fe2SiO4) solid solution
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