Kinetic analysis of thermogravimetric data XIII. Thermal decomposition of complexes of type [Co(en)2(pyridine)Cl]X2 |
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Authors: | J Zsakó Maria Várhelyi Cs Várhelyi |
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Institution: | (1) Faculty of Chemical Technology, Babes-Bolya University, Cluj-Napoca, Romania |
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Abstract: | Kinetic parameters of the dehydration of AC12.1.5 H2O, and of the substitution of pyridine by the outer sphere anion, have been derived from the TG curves of ACI2. 1.5 H2O, ABr2 and AI2 (A=Co(en)2(pyridine)Cl]) by using the author's nomogram method and the Coats-Redfern method. The influences of sample weight and of heating rate have been studied. Statistical analysis of the results shows the apparent activation energyE of the substitution reaction to decrease in the order CI > Br > I, while bothE and the pre-exponential factor values decrease with increasing sample weight and increasing heating rate. The kinetic compensation effect is discussed.
Zusammenfassung Kinetische Parameter der Dehydratationsreaktion von AC12 · 1.5H2O und der Substitutionsreaktion von Pyridin für das Anion der Äusseren SphÄre wurden aus den TG-Kurven von AC12 · 1.5H2O, ABr2 und AI2 (A=Co(en)2(pyridin)Cl] unter Anwendung der Nomogramm-Methode der Autoren sowie der von Coats-Redfern abgeleitet. Der Einfluss des Probengewichts und der Aufheizgeschwindigkeit wurde untersucht. Die statistische Analyse der Ergebnisse zeigte eine Abnahme der scheinbaren Aktivierungsenergie der Substitutionsreaktion in der Reihenfolge Cl > Br > I, sowie die Abnahme vonE und des prÄ-exponentiellen Faktors mit zunehmendem Gewicht der Probe und zunehmender Aufheizgeschwindigkeit. Der kinetische Kompensationseffekt wird diskutiert.
Résumé On déduit des courbes TG d'ACl2 · 1.5 H2O, ABr2 et AI2 ( A =Co(en)2(pyridine)Cl]) en se servant de la méthode nomographique des auteurs et de celle de Coats-Redfern, les paramètres cinétiques de la réaction de déshydratation d'ACl2 -1.5 H2O et de la réaction de substitution de la pyridine à l'anion de la sphère externe. On a étudié l'influence du poids du prélèvement et de la vitesse du chauffage. L'analyse statistique des résultats montre que l'énergie d'activation apparenteE de la réaction de substitution diminue dans l'ordre Cl > Br > I et queE et les valeurs du facteur pré-exponentiel diminuent toutes deux avec l'augmentation du poids du prélèvement et de la vitesse de chauffage. On discute l'effet de la compensation cinétique .
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![Ncy](/content/y41w26744j18318l/xxlarge1053.gif) ![scy](/content/y41w26744j18318l/xxlarge1089.gif) ![Acy](/content/y41w26744j18318l/xxlarge1040.gif) ![tscy](/content/y41w26744j18318l/xxlarge1094.gif) ![Icy](/content/y41w26744j18318l/xxlarge1048.gif) ![Ocy](/content/y41w26744j18318l/xxlarge1054.gif) ![Ncy](/content/y41w26744j18318l/xxlarge1053.gif) ![Ncy](/content/y41w26744j18318l/xxlarge1053.gif) ![ycy](/content/y41w26744j18318l/xxlarge1099.gif) ![IOcy](/content/y41w26744j18318l/xxlarge1025.gif) ![Fcy](/content/y41w26744j18318l/xxlarge1060.gif) ![IEcy](/content/y41w26744j18318l/xxlarge1045.gif) ![kcy](/content/y41w26744j18318l/xxlarge1082.gif) ».
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