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Study of the spontaneous crystallization of Na2SO4·7H2O and Na2SeO4·7.5H2O

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Abstract

The effects of temperature, cooling rate, and solution concentration on the spontaneous crystallization of Na2SO4·7H2O and Na2SeO4·7.5H2O from their supersaturated solutions was studied. It was found that the crystallization of Na2SO4·7H2O almost always occurs prior to that of Na2SO4·10H2O (except at high cooling rates), while the crystallization of Na2SeO4·7.5H2O is rather hindered. Raman spectroscopic studies on υ1 vibrations of SO4 2−/SeO4 2− ions in their respective samples revealed that the totally symmetric υ1 vibrations are shifted to the higher frequencies in the order: υ1 (Na2SO4 solution) < υ1 (Na2SO4·7H2O) < υ1 (Na2SO4·10H2O) < υ1 (Na2SO4) and υ1 (Na2SeO4 solution) < υ1 (Na2SeO4·7.5H2O) < υ1 (Na2SeO4·10H2O) < υ1 (Na2SeO4), respectively, which is an evidence of the order in which the deformation of the SO4 2−, respectively, SeO4 2− ions, increases. This fact gives grounds to assume the existence of a closer proximity between the structures of the corresponding solutions and those of the metastable Na2SO4·7H2O and Na2SeO4·7.5H2O, than with their decahydrates. In this way, the preferred crystallization of Na2SO4·7H2O, respectively, Na2SeO4·7.5H2O, in comparison with that of Na2SO4·10H2O, respectively, Na2SeO4·10H2O, can be explained. The hindered crystallization of Na2SeO4·7.5H2O in comparision with that of Na2SO4·7H2O may be attributed to the lower symmetry of its crystal structure (monoclinic space group C2/c) in comparison with that of Na2SO4·7H2O (tetragonal space group P41212).

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Acknowledgements

This study was carried out with financial support from the Foundation of Alexander von Humboldt, which allowed Prof. Dr. Christo Balarew and Ph.D. student Stoyan Kamburov a research stay in the Institute of Inorganic Chemistry, TU Bergakademie, Freiberg, Germany. We are grateful to Prof. Dr. Miroslav Abrashev and Dr. Neno Todorov from Sofia University “St. Kliment Ohridski” for their help with the Raman spectroscopic measurements.

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Authors and Affiliations

  1. Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry, Sofia, Bulgaria

    Christo Balarew, Stefka Tepavitcharova & Stoyan Kamburov

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  1. Christo Balarew
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  2. Stefka Tepavitcharova
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  3. Stoyan Kamburov
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Correspondence to Christo Balarew.

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In memory of Prof. H. Gamsjäger.

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Balarew, C., Tepavitcharova, S. & Kamburov, S. Study of the spontaneous crystallization of Na2SO4·7H2O and Na2SeO4·7.5H2O. Monatsh Chem 149, 289–298 (2018). https://doi.org/10.1007/s00706-017-2090-x

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  • DOI: https://doi.org/10.1007/s00706-017-2090-x

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