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Kinetic analysis of thermogravimetric data. X

Thermal decomposition of some tris-ethylenediamine-cobalt(III) and chromium(III) complexes

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Abstract

A study was made of the thermal decompositions of 22 derivatives of[M(en) 3]X 3 type complexes. Partial de-amination leading to the formation of[M(en) 2 X 2]X type complexes occurs in the case ofM=Cr(III) ifX=Cl, Br, I orNCS, but in the case ofM=Co(III) it is possible only ifX=Cl. In other cases redox reactions hinder the formation of stable intermediates. Kinetic parameters were derived for the dehydration of 19 compounds.

The validity of a linear kinetic compensation law was observed. The dependence of the kinetic compensation parameters on the nature of the thermal process is discussed.

Résumé

On a étudié la décomposition thermique de 22 dérivés des complexes du type[M(en) 3]x 3. La réaction de désamination partielle qui amène la formation des complexes du type[M(en) 2 X 2]X se produit dans le cas deCr(III), siX=Cl, Br, I ouCNS, mais dans le cas deCo(III) elle n'est possible que siX=Cl. Dans les autres cas, la formation d'intermédiaires stables est empêchée par des réactions d'oxydo-réduction. On a calculé les paramètres cinétiques pour la déshydratation de 19 composés.

On a constaté la validité d'une loi de compensation cinétique linéaire. On discute la manière dont les paramètres de compensation cinétique dépendent de la nature du processus thermique.

Zusammenfassung

Die thermische Zersetzung von 22 Derivaten des Komplextyps[M(en) 3]X 3 wurde untersucht. Die partielle Deaminierungsreaktion, welche zur Bildung von Komplexen des Typs[M(en) 2 X 2]X führt, tritt beiCr(III)-Komplexen in dem FalleX=Cl, Br, I oderNCS auf, ist aber beiCo(III)-Komplexen nur beiX=Cl möglich. In anderen Fällen wird die Bildung von stabilen Zwischenprodukten durch Redoxreaktionen verhindert. Für die Dehydratation von 19 Verbindungen wurden kinetische Parameter abgeleitet.

Die Gültigkeit eines linearen kinetischen Kompensationsgesetzes wurde beobachtet. Die Abhängigkeit kinetischer Kompensationsparameter von der Beschaffenheit des thermischen Vorganges wird erörtert.

Резюме

Исследован терморас пад 22 производных комплексов типа [М(ен) 3] Х3. Реакция, приводящая к образов анию комплексов типа [М(ен) 3] Х3 X, имеетместо в случае Сr (III) комплексов, в которыхX=Cl, Br, I илиNCS, в случае же производныхСо (III) эта реакция возможна тол ько приX=Сl. В других сл учаях окислительно-восста новительные реакции мешают образ ованию стабильных пр омежуточных соединений. Рассчита ны кинетические параметры дегидрата ции 19 соединений.

Обнаружена справедл ивость закона линейн ой кинетической компен сации. Обсуждается зависимость парамет ров кинетической ком пенсации от характера термическ ого процесса.

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Authors and Affiliations

  1. Faculty of Chemistry, “Babeş-Bolyai” University, Cluj, Romania

    J. Zsakó, Cs. Várhelyi & K. Szilágyi

  2. Department of Applied Chemistry, Technical University, Budapest

    G. Liptay

Authors
  1. J. Zsakó
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  2. Cs. Várhelyi
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  3. G. Liptay
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  4. K. Szilágyi
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Zsakó, J., Várhelyi, C., Liptay, G. et al. Kinetic analysis of thermogravimetric data. X. Journal of Thermal Analysis 7, 41–51 (1975). https://doi.org/10.1007/BF01911623

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  • DOI: https://doi.org/10.1007/BF01911623

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