2025 - Sustainable Industrial Processing Summit
SIPS2025 Volume 13. Intl. Symp on Solid State Chemistry, Physical Chemistry, Corrosion and Coating
| Editors: | F. Kongoli, I. Chung, H. Kageyama, M.G. Kanatzidis, F. Marquis, A. Navrotsky, A. Tressaud, J. Atwood, G. Duca, R. Kuroda, A. Legocki, J. Lipkowski, M. Zaworotko, R. Singh, R. Gupta, M. Halama, D. Macdonald, F. Wang |
| Publisher: | Flogen Star OUTREACH |
| Publication Year: | 2025 |
| Pages: | 262 pages |
| ISBN: | 978-1-998384-62-4 (CD) |
| ISSN: | 2291-1227 (Metals and Materials Processing in a Clean Environment Series) |
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SYNTHESIS OF COMPLEX SULFUR(IV) CHLORIDES WITH CERTAIN METAL CHLORIDES
Alexander Salyulev1; Emma Vovkotrub2;1INSTITUTE OF HIGH TEMPERATURE ELECTROCHEMISTRY, URAL BRANCH OF RUSSIAN ACADEMY OF SCIENCE, Ekaterinburg, Russian Federation; 2INSTITUTE OF HIGH TEMPERATURE ELECTROCHEMISTRY, URAL BRANCH OF RUSSIAN ACADEMY OF SCIENCE, Ekaterinburg, Russian Federation;
Type of Paper: Regular
Id Paper: 13
Topic: 52
Abstract:
Low-melting molten mixtures of sulfur chlorides with chlorides of other elements are promising for use in power sources and environmentally friendly processes for obtaining noble and rare metals [1]. Sulfur in compounds with chlorine may have different valences. The higher (IV, for chlorides) valence state of sulfur is unstable already at room temperature, at which SCl4 dissociates into SCl2 and Cl2 even in the presence of the strongest oxidizer - liquid chlorine. The higher valence state of sulfur can be stabilized by the inclusion of sulfur in the composition of outer-sphere cations SCl3+ in compounds of the [SCl3]k·[MmCln] type, where M = Al, Sb, Zr, Nb, Fe, Au, Ir and some other [1-3].
In the present work, a search for new chloride complexes was carried out. Sulfur together with the corresponding element (Be, In, Ga, V, Ti, Sn, Ge), red phosphorus or some chlorides (ZnCl2, PbCl2, GaCl3, AlCl3, HfCl4) were kept for several days at 18–150 °C in sealed quartz ampoules with anhydrous liquid or gaseous Cl2 at elevated pressures (up to 60 atm). Under these conditions, the indicated elements were chlorinated. Some of the chlorides formed (SCl2, GaCl3, VCl4, TiCl4, SnCl4, and GeCl4) are highly soluble in liquid chlorine.
The formation of ionic compounds of the [SCl3]k·[MmCln] type, which have low solubility in liquefied chlorine and therefore crystallize from solutions, was recorded by the appearance of characteristic bands of their SCl3+ complex cations and MmClnk– anions in the Raman spectra of solid samples [4]. They were recorded using a Renishaw U1000 spectrometer microscope (laser power 25 mW, λ = 514.5 nm) directly through the glass walls of sealed reactionary ampoules with liquid Cl2.
Several new and known compounds have been synthesized according to the described method, for example [SCl3].[BeCl3], [SCl3].[AlCl4], [SCl3].[GaCl4], [SCl3].[Ga2Cl7], [SCl3].[InCl4], [SCl3].[Ti2Cl9], [SCl3]2.[SnCl6], [SCl3]2.[HfCl6], [SCl3].[Hf2Cl9], containing the pyramidal group SCl3+ [4]. It was established, in particular, that sulfur chlorides do not form complex compounds with germanium and vanadium tetrachlorides, since the Raman spectra of solutions at room temperature only show bands of chlorides of these metals, sulfur dichloride and chlorine. Accordingly, crystalline deposits were also not observed.
The spectroscopic characteristics of all synthesized chloride complexes, in which the highest valence state (IV) of sulfur is stabilized as a result of complex formation, have been systematized.