On the Formation of Solid Solutions with blödite- and kröhnkite-type Structures. I. Synthesis, Vibrational and EPR Spectroscopic Investigations of Na2Zn1-xCux(SO4)2×4H2O (0< x < 0.14)

Authors

  • M. Georgiev  Department of Inorganic Chemistry, University of Chemical Technology and Metallurgy, 1756 Sofia, Bulgaria
  • Tsv. Bancheva  Department of Inorganic Chemistry, University of Chemical Technology and Metallurgy, 1756 Sofia, Bulgaria
  • D. Marinova  Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
  • R. Stoyanova  Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
  • D. Stoilova  Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria

Keywords:

Na2Zn1-xCux(SO4)2 4H2O solid solutions; Solubility diagram; Vibrational spectra; Hydrogen bond strength; EPR spectra.

Abstract

The solubility diagram of the Na2Zn(SO4)2-Na2Cu(SO4)2-H2O system at 25 ºC reveals that the copper ions are incorporated in the crystals of blödite-type structure, thus forming solid solutions of the type Na2Zn1-xCux(SO4)2×4H2O (0 < x < 0.14). However, the zinc cations do not accept the coordination environment of the copper ions in the strongly distorted CuO6 octahedra (effect of Jahn-Teller) and as a consequence Na2Cu(SO4)2×2H2O free of zinc ions crystallizes in a wide concentration range.

Infrared spectra of the double salts, Na2Zn(SO4)2×4H2O and Na2Cu(SO4)2×2H2O, as well as those of the solid solutions are presented and discussed with respect to the normal vibrations of the sulfate ions and water motions. The experimental results show that new bands corresponding to n3 of sulfate ions appear in the spectra of the solid solutions due to the new bands Cu-OSO3. The strength of the hydrogen bonds as deduced from the frequencies of nOH and nOD of matrix-isolated HDO molecules (spectral range of 2500-2200 cm-1) is discussed and the influence of the metal-water interactions (synergetic effect) on the hydrogen bond strength in both double sulfates is commented. The water librations are also briefly discussed.

The EPR spectra of Na2Cu(SO4)2×2H2O and Na2Zn1-xCux(SO4)2×4H2O are presented and discussed with respect to the crystal sites of the Cu2+ cations. The EPR measurements confirm the claim that the Zn cations are not incorporated in the crystals of the kröhnkite-type structure.

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International Journal of Scientific Research in Science and Technology

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2016-10-30

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Volume 2, Issue 5, September-October-2016

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[1]
M. Georgiev, Tsv. Bancheva, D. Marinova, R. Stoyanova, D. Stoilova "On the Formation of Solid Solutions with blödite- and kröhnkite-type Structures. I. Synthesis, Vibrational and EPR Spectroscopic Investigations of Na2Zn1-xCux(SO4)2×4H2O (0< x < 0.14)" International Journal of Scientific Research in Science and Technology(IJSRST), Online ISSN : 2395-602X, Print ISSN : 2395-6011,Volume 2, Issue 5, pp.279-282, September-October-2016.