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The Structure of Gallium in Strongly Alkaline, Highly Concentrated Gallate Solutions—a Raman and 71Ga-NMR Spectroscopic Study

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Abstract

Highly concentrated alkaline gallate solutions with 0.23≤[Ga(III)]T≤2.32 mol⋅dm−3 and 1≤[NaOH]T≤15 mol⋅dm−3 have been prepared and investigated by Raman and 71Ga-NMR spectroscopy. Both the Raman and 71Ga-NMR spectra are consistent with the presence of only one Ga-bearing species in these solutions, the tetrahedral hydroxocomplex, Ga(OH) 4 . Contact ion pairs were found to cause variations in the Raman and 71Ga-NMR parameters that are at the edge of detectability. Other species that have been claimed to exist in the literature, like higher hydroxo complexes (i.e., Ga(OH) 3−6 ) or the μ-oxo-bridged dimer (i.e., (OH)3Ga-O-(OH) 2−3 ), were not detected by these spectroscopic techniques. If such solution species exist at all, their concentrations are below the detection limit of Raman and 71Ga-NMR spectroscopy. The behavior of gallium appears to be very similar to that of aluminium under identical conditions, except that the dimeric species detected in aluminate solutions is undetectable in analogous gallates.

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References

  1. Pokrovski, G.S., Schott, J., Hazemann, J.-L., Farges, F., Pokrovsky, O.S.: An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solutions. Geochim. Cosmochim. Acta 66, 4203–4222 (2002)

    Article  CAS  Google Scholar 

  2. Baes, C.F. Jr., Mesmer, R.E.: The Hydrolysis of Cations. Wiley, London (1976)

    Google Scholar 

  3. Diakonov, I., Pokrovski, G.S., Benezeth, P., Schott, J., Dandurand, J.-L., Escalier, J.: Gallium speciation in aqueous solution. Experimental study and modelling Part 1. Thermodynamic properties of Ga(OH) 4 to 300 °C. Geochim. Cosmochim. Acta 61, 1333–1343 (1997)

    Article  CAS  Google Scholar 

  4. Benezeth, P., Diakonov, I., Pokrovski, G.S., Dandurand, J.-L., Schott, J., Khodakovsky, I.L.: Gallium speciation in aqueous solution. Experimental study and modelling Part 2. Solubility of α-GaOOH in acidic solutions from 150 °C to 300 °C and hydrolysis constants of Ga(III) to 300 °C. Geochim. Cosmochim. Acta 61, 1345–1357 (1997)

    Article  CAS  Google Scholar 

  5. Selvi, P., Ramasami, M., Samuel, M.H.P., Sripriya, R., Senhilkumar, K., Adaikkalam, P., Srinivasan, G.N.: Gallium recovery from Bayer liquor using hydroxamic acid resin. J. Appl. Polym. Sci. 92, 847–855 (2004)

    Article  CAS  Google Scholar 

  6. Akitt, J.W.: Multinuclear studies of aluminium compounds. Prog. NMR Spectrosc. 24, 1–149 (1989)

    Article  Google Scholar 

  7. Bradley, S.M., Kydd, R.A., Yamdagni, R.: Comparison of the hydrolysis of Ga(III) and Al(III) solutions by nuclear magnetic resonance spectroscopy. J. Chem. Soc., Dalton Trans. 2653–2656 (1990)

  8. Akitt, J.W., Kettle, D.: 71Ga-NMR investigation of aqueous Ga(III) and its hydrolysis. Magn. Reson. Chem. 27, 377–379 (1989)

    Article  CAS  Google Scholar 

  9. Biryuk, E.A., Nazarenko, V.A.: Determination of the hydrolysis constant of monomeric gallium(III) ions in solution with 0.1–1.0 M ionic strength. Zh. Neorg. Khim. 18, 2964–2967 (1973)

    CAS  Google Scholar 

  10. Akitt, J.W., Elders, J.M.: Multinuclear magnetic resonance studies of the hydrolysis of aluminium 8. Base hydrolysis monitored at very high magnetic field. J. Chem. Soc., Dalton Trans. 347–1355 (1988)

  11. Öhman, L.-O., Edlund, U.: In: Grant, D.M., Harris, R.K. (eds.) Encyclopedia of NMR, p. 742. Wiley, London (1996)

    Google Scholar 

  12. Bradley, S.M., Kydd, R.A., Yamdagni, R.: Detection of a new polymeric species formed through the hydrolysis of Ga(III)-salt solutions. J. Chem. Soc., Dalton Trans. 413–417 (1990)

  13. Parker, W.O. Jr., Millini, R., Kiricsi, I.: Metal substitution in Keggin-type tridecameric aluminium-oxo-hydroxy clusters. Inorg. Chem. 36, 571–575 (1997)

    Article  CAS  Google Scholar 

  14. Chretien, A., Bizot, D.: Existence of the Ga(OH) 4 ion. Ser. C.: Sci. Chim. 266, 1688–1690 (1968)

    CAS  Google Scholar 

  15. Yatsenko, S.: Equilibrium constants for the reaction of Ga(OH)3 with NaOH solution. Akad. Nauk SSSR, Ural. Fil. 20, 153–156 (1970)

    Google Scholar 

  16. Sipos, P., May, P.M., Hefter, G.: Quantitative determination of an aluminate dimer in concentrated alkaline aluminate solutions by Raman spectroscopy. Dalton Trans. 368–375 (2006)

  17. Moolenaar, R.J., Evans, J.C., McKeever, L.D.: The structure of the aluminate ion in solutions at high pH. J. Phys. Chem. 74, 3629–3636 (1970)

    Article  CAS  Google Scholar 

  18. Gale, J.D., Rohl, A.L., Watling, H.R., Parkinson, G.M.: Theoretical investigation of the nature of aluminium containing species present in alkaline solution. J. Phys. Chem. B 102, 10372–10382 (1998)

    Article  CAS  Google Scholar 

  19. Johansson, G.: The structure of the potassium aluminate K2[Al2O(OH)6]. Acta Chem. Scand. 20, 505–515 (1966)

    Article  CAS  Google Scholar 

  20. Ivanov-Jemin, B.N., Zaitsev, B.E., Kaziev, G.Z., Gerasimova, T.Yu.: Alkali metzal gallates (MGaO2). Zh. Neorg. Khim. 24, 3230–3233 (1979)

    Google Scholar 

  21. Ivanov-Jemin, B.N., Kaziev, G.Z., Ivlieva, V.I., Aksenova, T.B.: X-ray diffraction study of cesium hydroxyaluminate- and hydroxygallate. Zh. Neorg. Chim. 26, 544–555 (1981)

    Google Scholar 

  22. Ivanov-Jemin, B.N., Kaziev, G.Z., Zaitsev, B.E., Nikolaeva, O.A.: Hydroxyaluminates and hydroxygallates of heavy alkaline metals. Koord. Khim. 7, 218–221 (1981)

    Google Scholar 

  23. Romanov, G.A., Kopylova, E.A., Zazubin, A., Nikolskaya, M.P.: IR-spectroscopic study of the properties and structure of gallate solutions. Trud. Inst. Matall. Obog., Akad. Nauk Kazakh. SSR 50, 13–22 (1975)

    CAS  Google Scholar 

  24. Brintzinger, H., Wallach, J.: About the hydroxo compounds. Angew. Chem. 47, 61–63 (1934)

    Article  CAS  Google Scholar 

  25. Ljubimova, L.A., Ruzinov, L.P., Selokhova, N.P., Fomina, N.A.: Conductometric studies of gallium containing alkaline solutions. Elektrokhimiya 3, 1045–1047 (1967)

    Google Scholar 

  26. Sheka, I.A., Chaus, I.S., Mityureva, T.T.: The Chemistry of Gallium, p. 46. Elsevier, London (1966)

    Google Scholar 

  27. Gessner, W., Weinberger, M., Muller, D., Ni, L.P., Chaljapina, O.B.: On the crystalline phases of the systems K2O-Al2O3-H2O and Na2O-Al2O3-H2O. Z. Anorg. Allg. Chem. 547, 27–44 (1987)

    Article  CAS  Google Scholar 

  28. Zabel, V., Schneider, M., Weinberger, M., Gessner, W.: Nonasodium-bis(hexahydroxoaluminate) trihydroxide hexahydrate. Acta Cryst. C 52, 747–749 (1996)

    Article  Google Scholar 

  29. Weinberger, M., Schneider, M., Zabel, V., Muller, D., Gessner, W.: Nonasodium-bis (hexahydroxoaluminate) trihydroxide hexahydrate Na9[Al(OH)6]2(OH)3⋅6H2O—crystal structure. NMR spectroscopy and thermal behaviour. Z. Anorg. Allg. Chem. 622, 1799–1805 (1996)

    Article  CAS  Google Scholar 

  30. Ivanov-Emin, B.N., Kaziev, G.Z., Ivlieva, V.I., Gerasimova, T.Yu.: X-ray diffraction studies of Ca- and Sr-hexahydroxo-aluminates and gallates. Zh. Fiz. Khim. 55, 255–257 (1981)

    CAS  Google Scholar 

  31. Ivanov-Emin, B.N., Rabovik, Ya.I.: Chemistry of gallium II. Hydroxy gallates of alkali and alkali earth metals. Zh. Obs. Khim. 17, 1061–1069 (1974)

    Google Scholar 

  32. Loeper, M., Gessner, W., Muller, D., Schneider, M.: About crystalline sodium hydroxyl-gallates. Z. Anorg. Allg. Chem. 623, 1483–1488 (1997)

    Article  CAS  Google Scholar 

  33. Loeper, M., Schneider, M., Gessner, W., Reck, G.: Crystal structure of nonasodium-bis (hexahydroxoaluminate) trihydroxide hexahydrate Na9[Al(OH)6]2(OH)3⋅6H2O. Z. Krist. 211, 709–710 (1996)

    CAS  Google Scholar 

  34. Ivanov-Emin, B.N., Kaziev, G.Z., Gerasimova, T.Yu.: Study of the interaction of Ga(OH)3 and Ca(OH)2 in water at 25 °C. Izv. Vyss. Uch. Zaved., Khim. Khim. Techn. 25, 915–917 (1982)

    CAS  Google Scholar 

  35. Greenwood, N.N., Earnshow, A.: Chemistry of the Elements, p. 253. Pergamon Press, Elmsford (1984)

    Google Scholar 

  36. Cotton, F.A., Wilkinson, G.: Comprehensive Inorganic Chemistry, p. 217. Wiley, New York (1988)

    Google Scholar 

  37. Akitt, J.W., Gessner, W.J.: Aluminium-27 nuclear magnetic resonance investigation of highly alkaline aluminate solutions. J. Chem. Soc., Dalton Trans. 147–148 (1984)

  38. Sipos, P., Hefter, G., May, P.M.: 27Al-NMR and Raman spectroscopic studies of alkaline aluminate solutions with extremely high caustic content—does the octahedral species Al(OH) 3−6 exist in solution? Talanta 70, 761–765 (2006)

    Article  CAS  Google Scholar 

  39. Watling, H.R., Fleming, S.D., van Bronswijk, W., Rohl, A.: Ionic structure in caustic aluminate solutions and the precipitation of gibbsite. J. Chem. Soc., Dalton Trans. 3911–3917 (1998)

  40. Sheka, I.A., Chaus, I.S., Mityureva, T.T.: The Chemistry of Gallium, p. 77. Elsevier, London (1966)

    Google Scholar 

  41. Sipos, P., May, P.M., Hefter, G.T.: Carbonate removal from concentrated hydroxide solutions. The Analyst 125, 955–958 (2000)

    Article  CAS  Google Scholar 

  42. Sipos, P., Hefter, G.T., May, P.M.: Viscosities and densities of highly concentrated aqueous MOH solutions (M+ = Na+, Li+, K+, Cs+ and (CH3)4N+). J. Chem. Eng. Data 45, 613–617 (2000)

    Article  CAS  Google Scholar 

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Sipos, P., Megyes, T. & Berkesi, O. The Structure of Gallium in Strongly Alkaline, Highly Concentrated Gallate Solutions—a Raman and 71Ga-NMR Spectroscopic Study. J Solution Chem 37, 1411–1418 (2008). https://doi.org/10.1007/s10953-008-9314-y

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