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The thermal behaviour of solvates in the LiCI(MgCl2, AlCl3) water-1,4-dioxane systems

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Abstract

The thermal behaviour of the solvates and mixed solvates in the LiCl(MgCl2, AlCl3)-water-1,4-dioxane systems was investigated by means of DTA measurements of the melting behaviour and by quasi-isothermal and quasi-isobaric investigations of the thermal decomposition processes.

The compounds melt incongruently. The positions of the melting points and the processes of thermal decomposition confirm the assumption that 1,4-dioxane is bonded in the first coordination sphere in the mixed solvate of lithium, but in the cases of magnesium and aluminium chloride it is bonded via hydrogen-bonds and not directly to the cations. Only for the lithium and magnesium compounds does the decomposition of the anhydrous solvates result in anhydrous chlorides.

Zusammenfassung

Das thermische Verhalten der Solvate und Mischsolvate der Systeme LiCl, (MgCl2, AlCl3)-Wasser-1,4 Dioxan wurde mit Hilfe von DTA-Messungen zum Schmelzverhalten, und quasi-isothermen und quasi-isobaren Untersuchungen zum Ablauf der thermischen Zersetzung Untersucht. Die Verbindungen schmelzen inkongruent. Die Lage der Schmelzpunkte und der Verlauf der thermischen Zersetzung bekräftigen die Vorstellungen, daß 1,4 Dioxan im Mischsolvat des Lithiums in der ersten Koordinationsphäre direkt am Kation, hingegen bei Magnesium und Aluminium über Wasserstoffbrücken gebunden ist. Die Zersetzung der wasserfreien Solvate führt nur im Fall der Lithium- und Magnesiumverbindungen zu den wasserfreien Chloriden.

Резюме

Термическое поведен ие сольватов и смешан ных сольватированных си стем хлористый литий (хлорид магния, х лорид алюминия)-вода-1,4-диоксан было исследовани ДТА измерениями их плавления, а квази-и зотермическими и квази-изобарными мет одами — процесс их термического разлож ения. Соединения плав ятся инконгруэнтно. Полож ение их точек плавлен ия и процесс термическо го разложения подтве рждают предположение, что 1,4-ди оксан связан с литием в первой коорд инационной сфере его смешанного сольвата. В случае же х лоридов магния и алюминия, он связан с катионами не прямо, а посредством водород ных связей. Только для соединений лития и ма гния термическое раз ложение безводных сольватов приводит к образованию безводн ых хлоридов.

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Authors and Affiliations

  1. Bergakademie Freiberg, Sektion Chemie, Wissenschaftsbereich Anorganische Chemie, 9200, Freiberg, DDR

    H. -H. Emons, R. Naumann, K. Köhnke, K. Pollmer & M. Siedler

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  1. H. -H. Emons
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  2. R. Naumann
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  3. K. Köhnke
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  4. K. Pollmer
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  5. M. Siedler
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Additional information

The valuable assistance of Dr. Frahghänel in the separation of the solid phase by means of the hightemperature centrifuge is gratefully acknowledged.

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Emons, H.H., Naumann, R., Köhnke, K. et al. The thermal behaviour of solvates in the LiCI(MgCl2, AlCl3) water-1,4-dioxane systems. Journal of Thermal Analysis 32, 1969–1978 (1987). https://doi.org/10.1007/BF01913989

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