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High-Temperature Crystal Chemistry of Na2SO4–K2SO4 Sulfate System


In the Na2SO4–K2SO4 system, nine phases are known. In this study, for the first time, the values of the thermal expansion coefficients of continuous high-temperature solid solutions crystallizing in the P63/mmc crystal system, low-temperature limited solid solutions based on natroaphthitalite and aphthitalite (P3-m1), and polymorph II Na2SO4 (Pbnm) in the Na2SO4–K2SO4 system are provided. The genetic succession of polymorphs P3m1 and P3-m1 ↔ P63/mmc, which manifested itself in the double sulfates of this system, is revealed.

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  1. Eysel, W., Höfer, H.H., Keester, K.L., and Hahn, Th., Crystal chemistry and structure of Na2SO4 (I) and its solid solutions, Acta Crystallogr., Sect. B, 1985, vol. 41, pp. 5–11.

    Article  Google Scholar 

  2. Okada, K. and Ossaka, J., Structures of potassium sodium sulphate and tripotassium sodium disulphate, Acta Crystallogr., 1980, vol. 36, pp. 919–921.

    Article  Google Scholar 

  3. Gossner, B., Ueber die Kristallstruktur von Glaserit und Kaliumsulfat, Neues Jahrb. Mineral., Geol. Palaeontol., 1928, vol. 57, pp. 89–116.

    CAS  Google Scholar 

  4. Pekov, I.V., Shchipalkina, N.V., Zubkova, N.V., Gurzhiy, V.V., Agakhanov, A.A., Belakovskiy, D.I., Chukanov, N.V., Lykova, I.S., Vigasina, M.F., Koshlyakova, N.N., Sidorov, E.G., and Giester, G., Alkali sulfates with aphthitalite-like structures from fumaroles of the Tolbachik volcano, Kamchatka, Russia. I. Metathénardite, a natural high-temperature modification of Na2So4, Can. Mineral., 2020, vol. 57, no. 6, pp. 885–901.

    Article  Google Scholar 

  5. Shchipalkina, N.V., Pekov, I.V., Chukanov, N.V., Belakovskiy, D.I., Zubkova, N.V., Koshlyakova, N.N., Britvin, S.N., and Sidorov, E.G., Alkali sulfates with aphthitalite-like structures from fumaroles of the Tolbachik volcano, Kamchatka, Russia. II. A new mineral, natroaphthitalite, and new data on belomarinaite, Can. Mineral., 2020, vol. 58, no. 2, pp. 167–181.

    CAS  Article  Google Scholar 

  6. Filatov, S.K., Shablinskii, A.P., Vergasova, L.P., Saprikina, O.U., Bubnova, R.S., Moskaleva, S.V., and Belousov, A.B., Belomarinaite KNaSO4: A new sulphate from 2012–2013 Tolbachik fissure eruption, Kamchatka peninsula, Russia, Mineralog. Mag., 2019, vol. 83, pp. 569–575.

    CAS  Article  Google Scholar 

  7. Gorelova, L.A., Vergasova, L.P., Krivovichev, S.V., Avdontseva, E.Yu., Moskaleva, S.V., Karpov, G.A., and Filatov, S.K., Bubnovaite, K2Na8Ca(SO4)6, a new mineral species with modular structure from the Tolbachik volcano, Kamchatka peninsula, Russia, Eur. J. Mineral., 2016, vol. 28, pp. 677–686.

    CAS  Article  Google Scholar 

  8. Arnold, H., Kurtz, W., Richter-Zinnius, A., Bethke, J., and Heger, G., The phase transition of K2SO4 at about 850 K, Acta Crystallogr., Sect. B, 1981, vol. 37, pp. 1643–1651.

    Article  Google Scholar 

  9. Krivovichev, S.V. and Filatov, S.K., Structural principles for minerals and inorganic compounds containing anion-centered tetrahedra, Am. Mineralog., 1999, vol. 84, nos. 7–8, pp. 1099–1106.

    CAS  Article  Google Scholar 

  10. Rasmussen, S.E., Jorgensen, J.E., and Lundtoft, B., Structures and phase transition of Na2SO4, J. Appl. Crystallogr., 1996, vol. 29, pp. 42–47.

    CAS  Article  Google Scholar 

  11. Tanaka, K., Naruse, H., Morikawa, H., and Marumo, F., Phase-transition process of Na2SO4 (III) to Na2SO4 (I) and anharmonic thermal vibration, Acta Crystallogr., Sect. B, 1991, vol. 47, pp. 581–588.

    Article  Google Scholar 

  12. Ogg, M.A., The crystal structure of the isomorphous sulphates of potassium, ammonium, rubidium, and cesium, Philos. Mag. J. Sci., 1928, vol. 5, pp. 354–367.

    CAS  Article  Google Scholar 

  13. Chen, B., Liu, T.-H., Jiao, H., and Jing, X.-P., Phase transitions and energy storage properties of some compositions in the (1 – x)Li2SO4-xNa2SO4 system, Phase Trans., 2014, vol. 87, pp. 629–640.

    CAS  Article  Google Scholar 

  14. Solans, X., Calvet, T.M., Martinez-Sarrion, M.L., Mestres, L., Bakkali, A., Bocanegra, E.H., Mata, J., and Herraiz, M., Thermal analysis and X-ray diffraction study on LiKSO4: A new phase transition, J. Solid State Chem., 1999, vol. 148, pp. 316–324.

    CAS  Article  Google Scholar 

  15. Zachariasen, W.H. and Ziegler, G.E., The crystal structure of anhydrous sodium sulfate, Z. Kristallogr., 1932, vol. 81, p. 92.

    CAS  Article  Google Scholar 

  16. Belousova, M.G., Saprykina, O.Yu., Bubnova, R.S., Shablinskii, A.P., Vergasova, L.P., Belousov, A.B., and Filatov, S.K., Thermal study of the new mineral KNaSO4 belmarinaite, Vulkanol. Seismol., 2021, no. 1, pp. 57–64.

  17. Filatov, S.K., Vysokotemperaturnaya kristallokhimiya (High Temperature Crystal Chemistry), Leningrad: Nedra, 1990.

  18. Bubnova, R.S., Firsova, V.A., Volkov, S.N., and Filatov, S.K., RietveldToTensor: Program for processing powder X-ray diffraction data under variable conditions, Glass Phys. Chem., 2012, vol. 38, no. 5, pp. 33–40.

    Google Scholar 

  19. Shannon, R.D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr., Sect. A, 1976, vol. 32, pp. 751–767.

    Article  Google Scholar 

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The studies were carried out using the equipment of the resource center “X-ray diffraction methods of research” of St. Petersburg State University. This study was supported by the Russian Foundation for Basic Research (project no. 19-35-90094) and as part of a state task (no. 0097-2019-0013, IHS RAS) of the Ministry of Science and Higher Education of the Russian Federation.

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Correspondence to R. S. Bubnova.

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Shorets, O.Y., Filatov, S.K., Krzhizhanovskaya, M.G. et al. High-Temperature Crystal Chemistry of Na2SO4–K2SO4 Sulfate System. Glass Phys Chem 48, 130–139 (2022).

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  • alkali metal sulfates
  • thermal expansion
  • thermoradiography