Abstract
Triangulation of the Ag-Pb-Ge-S system in the Ag8GeS6-Ge-GeS2-PbS part was performed by differential thermal analysis, XRD and EMF methods. The serpentine-like shape of the concentration variation of Gibbs partial energy of silver \(- \Delta \overline{G}_{\text{Ag}}^{ \circ }\) in the alloys of the Ag8GeS6-PbS system in the Ag8GeS6-(Ag8GeS6)0.79(PbS)0.21 part at T = const (T = 518, 538, 556 K) is the consequence of the kinetically metastable state of the alloys of the limited solid solution range Ag8GeS6-(Ag8GeS6)0.81(PbS)0.19. According to the principles of continuity and correspondence, the \(- \Delta \overline{G}_{\text{Ag}}^{ \circ }\) extremum of the alloy (Ag8GeS6)0.84(PbS)0.16 determines the composition of the intermediate phase Ag6.72Pb0.16Ge0.84S5.20 of the equilibrium system Ag8GeS6-PbS. Potential-forming processes were performed in electrochemical cells (ECCs) of the type C|Ag|Ag2GeS3 glass|D|C (where C are current (graphite) electrode; Ag and D are the electrodes of ECCs; Ag2GeS3 glass is a membrane with ionic Ag+ conductivity; D are silver-containing single-, two- and four-phase alloys). Linear EMF dependences of cells in the 510-560 K range were used to calculate integral values of the thermodynamic functions of saturated solid solutions of the phases Ag2PbGeS4, Ag0.5Pb1.75GeS4, Ag6.72Pb0.16Ge0.84S5.20 (the composition of Ag6.48Pb0.19Ge0.81S5.05 from the PbS side). A significant excess of integral standard energy Gibbs \(\Delta_{\text{f}} G_{{298,\;{\text{Ag}}_{ 6. 4 8} {\text{Pb}}_{ 0. 1 9} {\text{Ge}}_{ 0. 8 1} {\text{S}}_{ 5. 0 5} }}^{\circ}\) = (−401.8 ± 1.5) kJ mol−1 over the values of \(\Delta_{\text{f}} G_{298,\;{\text{A}}{{\text{g}}_{\text{8}}}{\text{Ge}}{{\text{S}}_{\text{6}}}}^{\circ}\) = (−345.0 ± 2.2) kJ mol−1 and \(\Delta_{\text{f}} G_{{298,\;{\text{PbS}}}}^{\circ}\) = (−96.994 ± 0.005) kJ mol−1 is considered as the confirmation of the existence of a quaternary phase in the equilibrium system Ag8GeS6-PbS. The contribution of the entropy factor \(T\Delta_{\text{f}} S_{{298,\;{\text{Ag}}_{ 6. 4 8} {\text{Pb}}_{ 0. 1 9} {\text{Ge}}_{ 0. 8 1} {\text{S}}_{ 5. 0 5} }}^{\circ}\) into the value of \(\Delta_{\text{f}} G_{{298,\;{\text{Ag}}_{ 6. 4 8} {\text{Pb}}_{ 0. 1 9} {\text{Ge}}_{ 0. 8 1} {\text{S}}_{ 5. 0 5} }}^{\circ}\) exceeds 33%.
References
J.A. Aitken, P. Larson, S.D. Mahanti, and M.G. Kanatzidis, Li2PbGeS4 and Li2EuGeS4: Polar Chalcopyrites with a Severe Tetragonal Compression, Chem. Mater., 2001, 13, p 4714-4721
A.-M. Lamarche, A. Willsher, L. Chen, G. Lamarche, and J.C. Woolley, Crystal Structures of I2·Mn·IV·VI4 Compounds, J. Solid State Chem., 1991, 94, p 313-318
O.V. Parasyuk, L.V. Piskach, Y.E. Romanyuk, I.D. Olekseyuk, V.I. Zaremba, and V.I. Pekhnyo, Phase Relations in the Quasi-Binary Cu2GeS3–ZnS and Quasi-Ternary Cu2S–Zn(Cd)S–GeS2 Systems and Crystal Structure of Cu2ZnGeS4, J. Alloys Compd., 2005, 397, p 85-94
J.C. Woolley, A.-M. Lamarche, G. Lamarche, C. Church, I.P. Swainson, and T.M. Holden, Crystal Symmetry of Ag2MnGeTe4 Phases, J. Solid State Chem., 1995, 115, p 192-196
M. Quintero, A. Barreto, P. Grima, R. Tovar, E. Quintero, G.S. Porras, J. Ruiz, J.C. Woolley, G. Lamarche, and A.-M. Lamarche, Crystallographic Properties of I2–Fe–IV–VI4 Magnetic Semiconductor Compounds, Mater. Res. Bull., 1999, 34, p 2263-2270
O.V. Parasyuk, L.D. Gulay, L.V. Piskach, and O.P. Gagalovska, The Ag2S–HgS–GeS2 System at 670 K and the Crystal Structure of the Ag2HgGeS4 Compound, J. Alloys Compd., 2002, 336, p 213-217
O.V. Parasyuk, I.D. Olekseyuk, L.V. Piskach, S.V. Volkov, and V.I. Pekhnyo, Phase Relations in the Ag2S–CdS–SnS2 System and the Crystal Structure of the Compounds, J. Alloys Compd., 2005, 399, p 173-177
O.V. Parasyuk, A.O. Fedorchuk, Y.M. Kogut, L.V. Piskach, and I.D. Olekseyuk, The Ag2S–ZnS–GeS2 System: Phase Diagram, Glass-Formation Region and Crystal Structure of Ag2ZnGeS4, J. Alloys Compd., 2010, 500, p 26-29
Y. Kogut, A. Fedorchuk, O. Zhbankov, Y. Romanyuk, I. Kityk, L. Piskach, and O. Parasyuk, Isothermal section of the Ag2S–PbS–GeS2 system at 300 K and the crystal structure of Ag2PbGeS4, J. Alloys Compd., 2011, 509, p 4264-4267
S. Greil, Untersuchungen an Ternären und Quaternären Kupfer-, Lithium-, und Silbersulfiden mit Diamantstruktur, PhD, Universität Regensburg, 2016, p. 120
J.A. Aitken, G.A. Marking, M. Evain, L. Iordanidis, and M.G. Kanatzidis, Flux Synthesis and Isostructural Relationship of Cubic Na1.5Pb0.75PSe4, Na0.5Pb1.75GeS4, and Li0.5Pb1.75GeS4, J. Solid State Chem., 2000, 153, p 158-169
J.A. Aitken and M.G. Kanatzidis, α-Na6Pb3(PS4)4, a Noncentrosymmetric Thiophosphate with the Novel, Saucer-Shaped [Pb3(PS4)4]6− Cluster, and Its Metastable, 3-Dimensionally Polymerized Allotrope β-Na6Pb3(PS4)4, Inorg. Chem., 2001, 40, p 2938-2939
R.G. Iyer, J.A. Aitken, and M.G. Kanatzidis, Noncentrosymmetric Cubic Thio- and Selenogermanates: A0.5M1.75GeQ4 (A = Ag, Cu, Na; M = Pb, Eu; Q = S, Se), Solid State Sci., 2004, 6, p 451-459
G.E. Davydyuk, G.L. Myronchuk, I.V. Kityk, S.P. Danyl’chuk, V.V. Bozhko, and O.V. Parasyuk, Ag2CdSnS4 Single Crystals as Promising Materials for Optoelectronic, Opt. Mater., 2011, 33, p 1302-1306
Y. Kogut, O.Y. Khyzhun, O.V. Parasyuk, A.H. Reshak, G. Lakshminarayana, I.V. Kityk, and M. Piasecki, Electronic Spectral Parameters and IR Nonlinear Optical Features of Novel Ag0.5Pb1.75GeS4 Crystal, J. Cryst. Growth, 2012, 354, p 142-146
A.H. Reshak, Y.M. Kogut, A.O. Fedorchuk, O.V. Zamuruyeva, G.L. Myronchuk, O.V. Parasyuk, H. Kamarudin, S. Auluck, K.J. Plucinski, and J. Bila, Electronic and Optical Features of the Mixed Crystals Ag0.5Pb1.75Ge(S1–xSex)4, J. Mater. Chem. C, 2013, 1, p 4667-4675
Y.M. Kogut, A.O. Fedorchuk, O.V. Parasyuk, A.A. Albassam, A.M. El-Naggar, and I.V. Kityk, Laser Operated Piezoelectricity in Ag0.5Pb1.75GeS4 and Ag0.5Pb1.75GeS3Se Crystals, J. Mater. Sci. Mater. Electron., 2016, 27, p 9589-9592
O.V. Parasyuk, L.D. Gulay, Y.E. Romanyuk, I.D. Olekseyuk, and L.V. Piskach, The Ag2Se–HgSe–GeSe2 System and Crystal Structures of the Compounds, J. Alloys Compd., 2003, 351, p 135-144
L.D. Gulay, I.D. Olekseyuk, and O.V. Parasyuk, Crystal Structures of the Ag6HgGeSe6 and Ag6HgSiSe6 Compounds, J. Alloys Compd., 2002, 343, p 116-121
O.V. Parasyuk, L.D. Gulay, Y.E. Romanyuk, and I.D. Olekseyuk, The Ag2Se–HgSe–SiSe2 System in the 0–60 mol.% SiSe2 Region, J. Alloys Compd., 2003, 348, p 157-166
L.V. Piskach, O.V. Parasyuk, I.D. Olekseyuk, Y.E. Romanyuk, S.V. Volkov, and V.I. Pekhnyo, Interaction of Argyrodite Family Compounds with the Chalcogenides of II-b Elements, J. Alloys Compd., 2006, 421, p 98-104
W.F. Kuhs, R. Nitsche, and K. Scheunemann, The Argyrodites—A New Family of Tetrahedrally Close-Packed Structures, Mater. Res. Bull., 1979, 14, p 241-248
A. Kroupa, Modelling of Phase Diagrams and Thermodynamic Properties Using Calphad Method—Development Of Thermodynamic Databases, Comput. Mater. Sci., 2013, 66, p 3-13
H. Ipser, A. Mikula, and I. Katayama, Overview: The Emf Method as a Source of Experimental Thermodynamic Data, Calphad, 2010, 34, p 271-278
I. Barin, Thermochemical Data of Pure Substance, VCH, Weinheim, 1995
M.B. Babanly, Y.A. Yusibov, and N.B. Babanly, in Electromotive Force and Measurement in Several Systems, ed by S. Kara (InTech, 2011) p. 57–78. doi:10.5772/2109
NKh Abrikosov and L.E. Shelimova, Semiconductor Materials Based on A IV B VI Compounds, Nauka, Moscow, 1975 (in Russian)
O.P. Kokhan, Interaction in Ag2X–BIVX2 Systems (BIV – Si, Ge, Sn; X – S, Se) and Properties of Compounds, Ph. D. Thesis (Inorganic Chemistry), Uzhgorod State University, Uzhgorod, 1996.
H. Preston-Thomas, The International Temperature Scale of 1990 (ITS-90), Metrologia, 1990, 27, p 3-10
Diffractometr Stoe WinXPOW Version 221 Stoe Cie GmbH Darmstadt, 2007.
W. Kraus and G. Nolze, PowderCell Window Version 23 Berl, Fed. Inst. Mater. Res. Test, Febr, 1999
E. Robinel, A. Kone, M.J. Duclot, and J.L. Souquet, Silver Sulfide Based Glasses:(II). Electrochemical Properties of GeS2-Ag2S-Agl Glasses: Transference Number Measurement and Redox Stability Range, J. Non-Cryst. Solids, 1983, 57, p 59-70
M.V. Moroz, M.V. Prokhorenko, P.Y. Demchenko, and O.V. Reshetnyak, Thermodynamic Properties of Saturated Solid Solutions of Ag7SnSe5Br and Ag8SnSe6 Compounds in the Ag–Sn–Se–Br System Measured by the EMF Method, J. Chem. Thermodyn., 2017, 106, p 228-231
M.V. Moroz, M.V. Prokhorenko, and S.V. Prokhorenko, Determination of thermodynamic properties of Ag3SBr superionic phase using EMF technique, Russ. J. Electrochem., 2015, 51, p 886-889
F. Tesfaye, P. Taskinen, M. Aspiala, and D. Feng, Experimental Thermodynamic Study of Intermetallic Phases in the Binary Ag–Te System by an Improved EMF Method, Intermetallics, 2013, 34, p 56-62
E.G. Osadchii and E.A. Echmaeva, The System Ag-Au-Se: Phase Relations Below 405 K and Determination of Standard Thermodynamic Properties of Selenides by Solid-State Galvanic Cell Technique, Am. Mineral., 2007, 92, p 640-647
A.G. Morachevskiy, G.F. Voronin, V.A. Geiderich, and I.B. Kutsenok, Electrochemical Methods of Investigation in Thermodynamics of Metal Systems, Academkniga, Moscow, 2003
V.Ya. Anosov, M.I. Ozerova, and Yu.A. Fialkov, The Basics of Physico-Chemical Analysis, Nauka, Moscow, 1976 (in Russian)
R. Fairman and B. Ushkov, Semiconducting Chalcogenide Glass I: Glass Formation, Structure, and Simulated Transformations in Chalcogenide Glasses, Academic Press, London, 2004
Z.M. Aliyeva, S.M. Bagheri, Z.S. Aliev, I.J. Alverdiyev, Y.A. Yusibov, and M.B. Babanly, The Phase Equilibria in the Ag2S–Ag8GeS6–Ag8SnS6 System, J. Alloys Compd., 2014, 611, p 395-400
V.A. Kireyev, Course of Physical Chemistry, Khimiya, Moscow, 1975, in Russian
MKh Karapetyantz, Chemical Thermodynamics, Goskhimizdat, Moscow, 1953 (in Russian)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Moroz, M.V., Demchenko, P.Y., Prokhorenko, M.V. et al. Thermodynamic Properties of Saturated Solid Solutions of the Phases Ag2PbGeS4, Ag0.5Pb1.75GeS4 and Ag6.72Pb0.16Ge0.84S5.20 of the Ag-Pb-Ge-S System Determined by EMF Method. J. Phase Equilib. Diffus. 38, 426–433 (2017). https://doi.org/10.1007/s11669-017-0563-6
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11669-017-0563-6