Solid-state decomposition studies on fluoroperoxo species of transition metals part II |
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Authors: | G V Jere S M Kaushik |
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Institution: | (1) Department of Chemistry, Indian Institute of Technology, 110029 New Delhi, India |
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Abstract: | The kinetics of isothermal decomposition of solid K2Zr2(O2)2F6·2H2O have been studied in the temperature range 100–226° under vacuum. The fractional decomposition has been determined by measuring the pressure of evolved oxygen during pyrolysis with the help of a McLeod gauge. The values ranged from 0.05 to 0.62. The vs. t data showed that the kinetics are deceleratory throughout the course of the reaction. The initial part of the decomposition reaction could be best described by a unimolecular decay law, while the later stages obey contracting volume kinetics. The activation energies have been determined and the respective values for the above stages are 13.6 and 6.9 kcal·mole–1.
Zusammenfassung Die Kinetik der isothermen Zersetzung von festen K2Zr2(O2)2F6·2H2O wurde im Temperaturbereich von 100–226° im Vakuum untersucht. Die fraktionierte Zersetzung wurde durch Messung des Druckes des während der Pyrolyse entwickelten Sauerstoffs mit einem McLeod-Manometer bestimmt. Die -Werte variierten von 0.05 bis 0.62. Die -t Daten zeigen, daß die Kinetik im Verlauf der Reaktion herabgesetzt wird. Der erste Teil der Zersetzungsreaktion konnte am besten durch ein unimolekulares Zerfallgesetzt beschrieben werden, während die späteren Phasen der Kinetik der Volumenkontraktion gehorchten. Die Aktivierungsenergien wurden berechnet und die entsprechenden Werte für obige Reaktionen ergaben sich 13.6 bzw. 6.9 Kcal mol–1.
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![rcy](/content/g2301p0q1rp17424/xxlarge1088.gif) ![ycy](/content/g2301p0q1rp17424/xxlarge1099.gif) , ![scy](/content/g2301p0q1rp17424/xxlarge1089.gif) ![ocy](/content/g2301p0q1rp17424/xxlarge1086.gif) ![ocy](/content/g2301p0q1rp17424/xxlarge1086.gif) ![tcy](/content/g2301p0q1rp17424/xxlarge1090.gif) ![vcy](/content/g2301p0q1rp17424/xxlarge1074.gif) ![iecy](/content/g2301p0q1rp17424/xxlarge1077.gif) ![tcy](/content/g2301p0q1rp17424/xxlarge1090.gif) ![scy](/content/g2301p0q1rp17424/xxlarge1089.gif) ![tcy](/content/g2301p0q1rp17424/xxlarge1090.gif) ![vcy](/content/g2301p0q1rp17424/xxlarge1074.gif) ![ncy](/content/g2301p0q1rp17424/xxlarge1085.gif) ![ncy](/content/g2301p0q1rp17424/xxlarge1085.gif) , ![rcy](/content/g2301p0q1rp17424/xxlarge1088.gif) ![acy](/content/g2301p0q1rp17424/xxlarge1072.gif) ![vcy](/content/g2301p0q1rp17424/xxlarge1074.gif) ![ncy](/content/g2301p0q1rp17424/xxlarge1085.gif) 13.6 6.9 ![kcy](/content/g2301p0q1rp17424/xxlarge1082.gif) ![kcy](/content/g2301p0q1rp17424/xxlarge1082.gif) ![acy](/content/g2301p0q1rp17424/xxlarge1072.gif) .![mcy](/content/g2301p0q1rp17424/xxlarge1084.gif) ![ocy](/content/g2301p0q1rp17424/xxlarge1086.gif) ![lcy](/content/g2301p0q1rp17424/xxlarge1083.gif) –1.
One of the authors (SMK) is grateful to I.I.T. Delhi for a research scholarship. |
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