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(5) :-M. Georgiev, Tsv. Bancheva, D. Marinova, R. Stoyanova, D. Stoilova

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.

Authors and Affiliations

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

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

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Publication Details

Published in : Volume 2 | Issue 5 | September-October 2016
Date of Publication : 2016-10-30
License:  This work is licensed under a Creative Commons Attribution 4.0 International License.
Page(s) : 279-282
Manuscript Number : IJSRST162561
Publisher : Technoscience Academy

Print ISSN : 2395-6011, Online ISSN : 2395-602X

Cite This Article :

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), Print ISSN : 2395-6011, Online ISSN : 2395-602X, Volume 2, Issue 5, pp.279-282, September-October-2016. Available at doi : 10.32628/IJSRST162561
Journal URL : http://ijsrst.com/IJSRST162561

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