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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ON THE INTERACTION OF AlCl3 WITH ALKALI 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: 265
Topic: 52
Abstract:
Aluminum trichloride is one of the strongest complexing agents. In a medium of molten alkali metal chlorides, it forms strong complex anions AlCl4− (Td) and Al2Cl7− (D3d or C2v). In the solid state, binary compounds of only one composition are known: M[AlCl4] with M = Cs–Li [1–3]. However, compounds of the M[Al2Cl7] type, where M is a large organic cation, are well known. The existence of solid complexes M[A2Г7], where A denotes Al, Ga; Г denotes halogen, was found in the related systems MBr–AlBr3 and MCl–GaCl3 (M = Cs, Rb, K), for which the AlBr4−, Al2Br7−, GaCl4−, and Ga2Cl7− ions are also present in molten mixtures. This prompted us to study further the products of the interaction between AlCl3 and alkali metal chlorides obtained in two different ways.
High-purity AlCl3 was fused with alkali metal chlorides in sealed quartz ampoules and then cooled. A new method was also tested. Aluminum trichloride together with CsCl, RbCl, KCl or NaCl powders were exposed from two to three weeks at 20–25 °C in sealed quartz ampoules in an anhydrous liquefied hydrogen chloride environment, in which AlCl3 is quite soluble. The ampoules were then opened and HCl evaporated. The solid reaction products were examined under a microscope of a Renishaw U1000 spectrometer (Ar+ laser) through the walls of glass reaction ampoules.
In the Raman spectra of solid samples obtained by both methods, only the bands of the complex anions [AlCl4]– (~ 488, 355, 190, 129 cm–1) of the compounds Cs[AlCl4], Rb[AlCl4], K[AlCl4] and Na[AlCl4] were recorded. Under the described conditions, complex compounds of the composition M[Al2Cl7] did not form, since the bands of the anions [Al2Cl7]– (~ 430, 310, 160, 100 cm–1 [1, 2]) were absent in the spectra.
Our data, obtained using a new preparative method and Raman spectroscopy, confirm the existing information on the type of chlorocomplexes and supplement the information on the conditions of their formation during the interaction of components in binary systems AlCl3–MCl (M is an alkali metal).