Journal of Solution Chemistry

, Volume 39, Issue 10, pp 1549–1561 | Cite as

Raman Spectra of Tungsten-Bearing Solutions



Raman spectroscopy at 25 °C was performed to analyze speciation in quenched solutions after experiments on sodium tungstates and sodium tungstate bronze dissolution at t=500 °C, p=1000 bar. The experiments were conducted under different oxidation-reduction conditions in sodium chloride solution media. The spectra of the quenched solutions were different from those of the reference solutions of 0.02 mol⋅kg−1 W(VI) (H2O) in the pH range 2.3–7.2. Thermodynamic models were established and the fields of predominance of different isopolytungstate species at 25–50 °C were determined. The experimental results of tungstate dissolution demonstrates that reduced tungstate solutions may contain a significant amount of tungsten species with valence states lower than W(VI).


Raman spectroscopy Tungsten Sodium tungstate Sodium tungstate bronze Speciation Isopolytungstate species Thermodynamic calculations 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Busey, R.H., Keller, D.L. Jr.: Structure of the aqueous pertechnetate ion by Raman and infrared spectroscopy. Raman and infrared spectra of crystalline KTcO4, KReO4, Na2MoO4, Na2WO4, Na2MoO4⋅2H2O, and Na2WO4⋅2H2O. J. Chem. Phys. 41, 215–225 (1964) CrossRefGoogle Scholar
  2. 2.
    Ivanova, G.F., Khodakovsky, I.L.: Transport of tungsten in hydrothermal solutions. Geokhimiya 8, 930–940 (1968) (in Russian) Google Scholar
  3. 3.
    Chuvaev, V.F., Gazarov, R.A., Spitsyn, V.I.: Investigation of the interaction of molybdate and tungstate ions with water. Inorg. Chem. Izv. Akad. Nauk SSSR, Ser. Khim. 8, 1679–1683 (1974) Google Scholar
  4. 4.
    Rafalskiy, R.P., Brizgalin, O.V., Fedorov, P.L.: Tungsten migration and scheelite deposition under hydrothermal conditions. Geochem. Int. 21, 1–13 (1984) Google Scholar
  5. 5.
    Galkin, A.V., Kolonin, G.R., Shironosova, G.P.: The estimation of constants solubility of tungsten and iron bearing minerals at high temperature chloride solutions. In: Abstracts of XI All-Union meeting on experimental mineralogy. Chernogolovka (1986) (in Russian) Google Scholar
  6. 6.
    Wood, S.A., Vlassopoulos, D.: Experimental determination of the solubility and speciation of tungsten at 500 °C and 1 kbar. Geochim. Cosmochim. Acta 53, 303–312 (1989) CrossRefGoogle Scholar
  7. 7.
    Jander, G., Mojert, D., Aden, T.: Über amphotere Oxydhydrate, deren wäßrige Lösungen und kristallisierende Verbindungen. VIII. Mitteilung. über wolframate, isopoly- und heteropoly-wolframsäuren. Z. Anorg. Allg. Chem. 180, 129–149 (1929) CrossRefGoogle Scholar
  8. 8.
    Souchay, P.: Study of the tungsten heteropoly acids conditions of existence and properties of various ions contained in tungsten solutions. Ann. Chim. Sér. II. 18, 61–72 (1943) Google Scholar
  9. 9.
    Duncan, J.F., Kepert, D.L.: Polyanion equilibria in aqueous solution. Part I. The quantitative analysis of acidified tungstate solutions. J. Chem. Soc. 1050, 5317–5325 (1961) CrossRefGoogle Scholar
  10. 10.
    Duncan, J.F., Kepert, D.L.: Polyanion equilibria in aqueous solution. Part II. A thermodynamic study of the paratungstate A anion. J. Chem. Soc. 39, 205–214 (1962) CrossRefGoogle Scholar
  11. 11.
    Arnek, R., Sasaki, Y.: Equilibrium studies of polyanions. 20. A recalculation of emf data on the reactions of H+ and \(\mathrm{WO}_{4}^{2-}\) in 3 M NaClO4 at 25 °C. Acta Chem. Scand. A28, 20–22 (1974) CrossRefGoogle Scholar
  12. 12.
    Jensen, J.B., Lou, J.: Anomalous behavior of saturated aqueous tungstate solutions. J. Solution Chem. 14, 513–530 (1985) CrossRefGoogle Scholar
  13. 13.
    Pizzio, L.R., Cáceres, C.V., Blanco, M.N.: Tungsten-alumina based catalysts. I. Genesis by impregnation with different tungsten solutions. Catal. Letters 33, 175–192 (1995) CrossRefGoogle Scholar
  14. 14.
    Yamase, T.: Photo- and electrochimism of polyoxometalates and related materials. Chem. Rev. 98, 307–325 (1998) CrossRefGoogle Scholar
  15. 15.
    Kim, D.S., Ostromecki, M., Wachs, I.E., Kohler, S.D., Ekerdt, J.G.: Preparation and characterization of WO3/SiO2 catalysts. Catal. Letters 33, 209–215 (1995) CrossRefGoogle Scholar
  16. 16.
    Smith, B.J., Patrick, V.A.: Quantitative determination of sodium metatungstate speciation by 183W N.M.R. spectroscopy. Aust. J. Chem. 53, 965–970 (2000) CrossRefGoogle Scholar
  17. 17.
    Smith, B.J., Patrick, V.A.: Quantitative determination of sodium dodecatungstate speciation by 183W nuclear magnetic. resonance spectroscopy. Aust. J. Chem. 55, 281–286 (2002) CrossRefGoogle Scholar
  18. 18.
    Fedotov, M.A., Maksimovskaya, R.I.: NMR structural aspects of the chemistry of V, Mo, W polyoxometalates. J. Struct. Chem. 47, 952–978 (2006) CrossRefGoogle Scholar
  19. 19.
    Hastings, J.J., Howarth, O.W.A.: 183W, 1H, and 17O nuclear magnetic resonance study of aqueous isopolytungstates. J. Chem. Soc. Dalton Trans. 2, 209–215 (1992) CrossRefGoogle Scholar
  20. 20.
    Nolan, A.L., Wilkes, E.N., Hambley, T.W., Allen, Ch.C., Burns, R.C., Lawrance, G.A.: Crystal structure of Na9[H3W12O42]⋅24H2O, a compound containing the protonated paratungstate B anion (‘acid paratungstate’), and cyclic voltammetry of acidified [H2W12O42]10− solutions. Aust. J. Chem. 52, 955–964 (1999) CrossRefGoogle Scholar
  21. 21.
    Aveston, J.: Hydrolysis of tungsten(VI): Ultracentrifugation, acidity measurements, and Raman spectra of polytungstates. Inorg. Chem. 3, 981–986 (1964) CrossRefGoogle Scholar
  22. 22.
    Baes, C.J., Mesmer, R.E.: The Hydrolysis of Cations. Wiley, New York (1976) Google Scholar
  23. 23.
    Walanda, D.K., Burns, R.C., Lawrance, G.A., von Nagy-Felsobuki, E.I.: Electrospray mass spectrometry of aqueous solutions of isopolyoxotungstates. J. Clust. Sci. 11, 5–28 (2000) CrossRefGoogle Scholar
  24. 24.
    Wesolowski, D., Drummond, S.E., Mesme, R.E., Ohmoto, H.: Hydrolysis equilibria of tungsten (VI) in aqueous sodium chloride solutions to 300 °C. Inorg. Chem. 23, 1120–1130 (1984) CrossRefGoogle Scholar
  25. 25.
    Wood, S.A., Samson, I.M.: The hydrothermal geochemistry of tungsten in granitoid environments. I. Relative solubilities of ferberite and scheelite as a function of T, P, pH and mNaCl. Econ. Geol. 95, 143–182 (2000) Google Scholar
  26. 26.
    Zimin, P.A., Kazanskii, L.P.: X-ray electron spectroscopy of corrosion inhibitors on metal surfaces. Communication 2. Adsorption of inorganic oxianions on the surface of aluminum. Izv. Akad. Nauk SSSR, Ser. Chem. 9, 1943–1949 (1983) Google Scholar
  27. 27.
    Picquart, M., Castro-Garsia, S., Lilage, J., Julien, C., Haro-Poniatowski, E.: Structural studies during gelation of WO3 investigated by in-situ Raman spectroscopy. J. Sol-Gel Sci. Technol. 18, 199–206 (2000) CrossRefGoogle Scholar
  28. 28.
    Schrötterová, D., Nekovář, P.: Tungsten (VI) extraction equilibrium in the system polytungstates–primene JMT sulfate–benzene. J. Radioanal. Nucl. Chem. 246, 671–674 (2000) CrossRefGoogle Scholar
  29. 29.
    Timofeeva, E.V., Tsirlina, G.A., Petrii, O.A.: Formation of rechargeable films on platinum in sulfuric acid solutions of isopolytungstates. Rus. J. Electrochem. 39, 716–726 (2003) CrossRefGoogle Scholar
  30. 30.
    Solarska, R., Alexander, B.D., Augustynski, J.: Electrochromic and structural characteristics of mesoporous WO3 films prepared by a sol-gel method. J. Solid State Electrochem. 8, 748–756 (2004) CrossRefGoogle Scholar
  31. 31.
    Zeng, J.L., Xiong, Z.T., Zhang, H.B., Lin, G.D., Tsai, K.R.: Nonoxidative dehydrogenation and aromatization of methane over W/HZSM-5-based catalysts. Catal. Letters 53, 119–124 (1998) CrossRefGoogle Scholar
  32. 32.
    Ostroushko, A.A., Vilkova, N.V., Mogil’nikov, U.V.: Structure and properties of molybdate and tungstate complexes of polyvinyl alcohol. Rus. J. Gen. Chem. 72, 1–8 (2002) CrossRefGoogle Scholar
  33. 33.
    Ohtsuka, T., Wakabayashi, T.O., Einaga, H.: Optical characterization of polypyrrole-polytungstate anion composite films. Synth. Met. 79, 235–239 (1996) CrossRefGoogle Scholar
  34. 34.
    Redkin, A.F., Ponomarev, V.I., Kostromin, N.P.: Hydrothermal synthesis and properties of sodium pentatungstate monohydrate Na2W5O16⋅H2O. Russ. J. Inorg. Chem. 45, 1297–1303 (2000) Google Scholar
  35. 35.
    Mamedova, A.M., Ivanov, V.M., Akhmedov, S.A.: Interaction of tungsten(VI) and vanadium(V) with pyrogallol red and brompyrogallol red in the presence of surfactants. MSU, Chem. Bull. 45, 117–123 (2004) (in Russian) Google Scholar
  36. 36.
    Oelkers, E.H., Helgeson, H.C.: Triple-ion anions and polynuclear complexing in supercritical electrolyte solutions. Geochim. Cosmochim. Acta 54, 727–738 (1990) CrossRefGoogle Scholar
  37. 37.
    Cruywagen, J.J., van der Merwe, I.F.J.: Tungsten(VI) equilibria: a potentiometric and calorimetric investigation. J. Chem. Soc. Dalton Trans. 7, 1701–1705 (1987) CrossRefGoogle Scholar
  38. 38.
    Shvarov, Yu.V.: HCh: New potentialities for the thermodynamic simulation of geochemical systems offered by Windows. Geochem. Int. 46, 834–839 (2008) CrossRefGoogle Scholar
  39. 39.
    Glushko, V.P.: Thermodynamic Constants of Individual Substances: A Handbook, 3rd ed. AN SSSR and VINiTI, Moscow (1982) Google Scholar
  40. 40.
    Shock, E.L., Sassani, D.C., Willis, M., Sverjensky, D.A.: Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes. Geochim. Cosmoshim. Acta. 61, 907–950 (1997) CrossRefGoogle Scholar
  41. 41.
    Barré, T., Arurault, L., Sauvage, F.X.: Chemical behavior of tungstate solutions. Part 1. A spectroscopic survey of the species involved. Spectrochim. Acta, Part A: Mol. Biomol. Spectrosc. 61, 551–557 (2005) Google Scholar
  42. 42.
    Bryzgalyn, O.V.: On the solubility of tungstic acid in a aqueous salt solution at high temperatures. Geochem. Int. 13, 155–159 (1976) Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  1. 1.Institute of Experimental MineralogyRussian Academy of SciencesChernogolovkaRussia

Personalised recommendations