Inorganic Materials

, Volume 43, Issue 2, pp 95–104 | Cite as

Phase diagram of the As-S system

  • A. L. Emelina
  • A. S. Alikhanian
  • A. V. Steblevskii
  • E. N. Kolosov


Thermodynamic modeling of phase equilibria is used to consistent p-T-x phase diagram of the As-S system. Experimental evidence is presented that As2S5 is a metastable phase at moderate pressures. Analytical expressions are derived for the subsolidus phase equilibria in the As-S system. It is shown for the first time that crystalline As4S3 sublimes congruently and that two liquid-vapor azeotropes exist in the As-S system.


Arsenic Phase Diagram Moderate Pressure Convex Envelope Orpiment 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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  1. 1.
    Shpak, I.I., Studenyak, I.P., and Kranjčec, M., Optical Absorption Edge and Structural Disorder in Electron-Irradiated As2S3 Chalcogenide Glasses, J. Opt. Adv. Mater., 2003, vol. 5, no. 5, pp. 1135–1138.Google Scholar
  2. 2.
    Holomb, R.M. and Mitsa, V.M., Simulation of Raman Spectra of AsxS100−x Glasses by the Results of Ab Initio Calculations of AsnSm Clusters Vibrations, J. Opt. Adv. Mater., 2004, vol. 6, no. 4 P, pp. 1177–1184.Google Scholar
  3. 3.
    Timofeeva, N.V., Vinogradova, G.Z., Feklichev, E.M., et al., Sovrem. Probl. Fiz. Khim., 1972, vol. 6, pp. 234–259.Google Scholar
  4. 4.
    Abrikosov, N.Kh., Bankina, V.F., Poretskaya, L.V., et al., Poluprovodnikovye khal’kogenidy i splavy na ikh osnove (Semiconducting Chalcogenides and Their Alloys), Moscow: Nauka, 1975, pp. 146–147.Google Scholar
  5. 5.
    Von Blachnik, R., Hoppe, A., and Wickel, U., Die Systeme Arsen-Schwefel und Arsen-Selen und die thermodynamischen Daten ihrer Verbindungen, Z. Anorg. Allg. Chem., 1980, vol. 468, pp. 78–90.CrossRefGoogle Scholar
  6. 6.
    Fedorova, Zh.N. and Epova, E.I., Thermoanalytical Study of the As-S System, in Issledovaniya po eksperimental’noi geologii (Research in Experimental Geology), Novosibirsk: Inst. Geologii i Geofiziki Sib. Otd. Akad. Nauk SSSR, 1978, pp. 12–18.Google Scholar
  7. 7.
    Street, G.B. and Munir, Z.A., The Structure and Thermal Properties of Synthetic Realgar (As4S4), J. Inorg. Nucl. Chem., 1970, vol. 32, pp. 3769–3774.CrossRefGoogle Scholar
  8. 8.
    Kirkinskii, V.A., Ryaposov, A.P., and Yakushev, V.G., Phase Diagram of Arsenic Trisulfide at Pressures up to 20 kbar, Izv. Akad. Nauk SSSR, Neorg. Mater., 1967, vol. 3, no. 10, pp. 1931–1933.Google Scholar
  9. 9.
    Gospodinov, G.G. and Pashinkin, A.S., Saturated Vapor Pressure over Solid As2S3, Izv. Akad. Nauk SSSR, Neorg. Mater., 1974, vol. 10, no. 11, pp. 2074–2075.Google Scholar
  10. 10.
    Isakova, R.A., Davlenie para i dissotsiatsiya sul’fidov metallov (Vapor Pressure and Dissociation of Metal Sulfides), Alma-Ata: Nauka, 1968, pp. 174–179.Google Scholar
  11. 11.
    Steblevskii, A.V., Alikhanian, A.S., Gorgoraki, V.I., and Pashinkin, A.S., Thermodynamic Properties of the Binary System As-S, III Vsesoyuznaya konferentsiya “Termodinamika i materialovedenie poluprovodnikov” (III All-Union Conf. on Semiconductor Thermodynamics and Materials Research), Moscow, 1986, pp. 105–106.Google Scholar
  12. 12.
    Steblevskii, A.V., Gorgoraki, V.I., Pashinkin, A.S., and Malyusov, V.A., Thermodynamics of Arsenic Chalcogenide Vaporization, IV Vsesoyuznaya konferentsiya po mass-spektrometrii (IV All-Union Conf. on Mass Spectrometry), Sumy, 1986, pp. 46–47.Google Scholar
  13. 13.
    Steblevskii, A.V., Alikhanyan, A.S., Pashinkin, A.S., and Malyusov, V.A., Vapor Composition in the Arsenic-Sulfur System, Zh. Neorg. Khim., 1986, vol. 31, no. 10, pp. 2451–2456.Google Scholar
  14. 14.
    Malkova, A.S., Zharov, V.V., Alikhanyan, A.S., et al., Termodinamicheskie funktsii gazoobraznykh khal’kogenidov mysh’yaka (Thermodynamic Functions of Gaseous Arsenic Chalcogenides), Available from NIITEKhIM, 1985, Cherkassy, no. 350khp-85.Google Scholar
  15. 15.
    Muniz-Miranda, M., Sbrana, G., Bonazzi, P., et al., Spectroscopic Investigation and Normal Mode Analysis of As4S4 Polymorphs, Spectrochim. Acta, Part A, 1996, vol. 52, pp. 1391–1401.CrossRefGoogle Scholar
  16. 16.
    Chattopadhyay, T.K., Gmelin, F., and von Schnering, H.G., Thermal Properties of As4S4 and As4S3, J. Phys. Chem. Solids, 1982, vol. 43, no. 9, pp. 925–932.CrossRefGoogle Scholar
  17. 17.
    Brittain, R.D., Lau, K.H., and Hildenbrand, D.L., Vaporization in the As-S System, J. Electrochem. Soc., 1983, vol. 130, no. 5, pp. 1206–1210.CrossRefGoogle Scholar
  18. 18.
    Pashinkin, A.S., Shchergin, A.A., Amirov, R.A., et al., Saturated Vapor Pressure and Heat of Formation of As4S4, Izv. Akad. Nauk SSSR, Neorg. Mater., 1982, vol. 18, no. 8, pp. 1253–1256.Google Scholar
  19. 19.
    Godovikov, A.A., Fedorova, Zh.N., and Gurov, V.V., Eksperimental’nye issledovaniya sul’fidnykh i silikatnykh sistem (Experimental Studies of Sulfide and Silicate Systems), Novosibirsk: Inst. Geologii i Geofiziki Sib. Otd. Akad. Nauk SSSR, 1981, pp. 26–32.Google Scholar
  20. 20.
    Pashinkin, A.S., Fedorov, V.A., Zviadze, G.N., et al., Saturated Vapor Pressure over As4S3, Izv. Akad. Nauk SSSR, Neorg. Mater., 1972, vol. 8, no. 10, pp. 1850–1854.Google Scholar
  21. 21.
    Shunk, F.A., Constitution of Binary Alloys: Second Supplement, New York: McGraw-Hill, 1969, p. 100.Google Scholar
  22. 22.
    Voronin, G.F., Advances in Thermodynamic Assessment and Phase-Diagram Studies of Heterogeneous Systems, Zh. Fiz. Khim., 2003, vol. 77, no. 10, pp. 1874–1883.Google Scholar
  23. 23.
    Belov, G.V., Voronin, G.F., Emelina, A.L., et al., Convex Envelope Algorithm for Phase Diagram Calculations and Its Software Implementation, Mat. Model., 2006, vol. 18, no. 1, pp. 67–78.Google Scholar
  24. 24.
    Dinsdale, A.T., SGTE Data for Pure Elements, CALPHAD: Comput. Coupling Phase Diagrams Thermochem., 1991, vol. 15, no. 4, pp. 317–425.Google Scholar
  25. 25.
    Nesmeyanov, A.N., Davlenie para khimicheskikh elementov (Vapor Pressures of Pure Elements), Moscow: Akad. Nauk SSSR, 1961, pp. 254, 370.Google Scholar
  26. 26.
    Schreinemakers, F.A.H., In-, Mono-, and Divariant Equilibria, New York: Nordemann, 1946.Google Scholar
  27. 27.
    Niggli, P., Das Magma und seine Produkte, Leipzig: Akademische Verlagsgesellschaft, 1937.Google Scholar
  28. 28.
    Anosov, V.Ya. and Pogodin, S.A., Osnovnye nachala fiziko-khimicheskogo analiza (Fundamental Principles of Physicochemical Analysis), Moscow: Akad. Nauk SSSR, 1947.Google Scholar
  29. 29.
    Fizicheskaya khimiya (Physical Chemistry), Krasnov, K.S., Ed., Moscow: Vysshaya Shkola, 2001, vol. 1, p. 433.Google Scholar
  30. 30.
    Grokeen, N.A., The As System, Bull. Alloy Phase Diagrams, 1989, no. 10, pp. 11–12.Google Scholar

Copyright information

© Pleiades Publishing, Inc. 2007

Authors and Affiliations

  • A. L. Emelina
    • 1
  • A. S. Alikhanian
    • 1
  • A. V. Steblevskii
    • 1
  • E. N. Kolosov
    • 1
  1. 1.Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussia

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