Kinetic analysis of isothermal,non-isothermal and catalysed thermal decomposition of malonic acid |
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Authors: | A M El-Awad R M Mahfouz |
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Institution: | (1) Chemistry Department, Faculty of Science, Assiut, Egypt |
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Abstract: | A comparative study of the isothermal and non-isothermal decompositions of malonic acid has been carried out using the gasometric technique at atmospheric pressure. Under isothermal conditions, the results indicate two different mechanisms. At lower operating temperatures the decomposition process is governed by first-order kinetics, while at higher temperatures it is controlled by the random nucleation Erofeev equation. Analysis of the non-isothermal TG curves proved the advantageous use of this technique. It provides quick and valid information about the thermal decomposition kinetics of malonic acid, both in the pure state and when catalysed by solid 12-molybdophosphoric acid and its bismuth salts. Via the applicability of a non-isothermal kinetic equation, it was demonstrated that the factor causing the enhancement effect of these catalysts is mainly electronic in nature.
Zusammenfassung Mittels Gasometertechnik bei atmosphärischem Druck wurde eine vergleichende Betrachtung der isothermen und nichtisothermen Zersetzung von Malonsäure durchgeführt. Die Ergebnisse zeigen unter isothermen Bedingungen zwei verschiedene Mechanismen. Während die Zersetzungsprozesse bei niedrigeren Temperaturen durch eine Reaktionskinetik erster Ordnung bestimmt werden, findet bei höheren Temperaturen die Randomkeimbildungsgleichung von Erofeev Anwendung. Diese Technik konnte bei der Auswertung der nichtisothermen TG-Kurven vorteilhaft angewendet werden. Sie liefert schnelle und stichhaltige Informationen über die thermische Zersetzungkinetik von Malonsäure sowohl rein als auch in Gegenwart eines Katalysators, der in Form von 12-Molybdatophosphorsäure oder deren Bismutsalzen als Feststoffkatalysator beigemischt wird. Auf der Basis der Anwendbarkeit der nichtisothermen Kinetikgleichung konnte gezeigt werden, daß der Verstärkungseffekt dieser Katalysatoren hauptsächlich auf Faktoren elektronischer Natur zurückgeführt werden kann.
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![dcy](/content/r3q3x042786w5566/xxlarge1076.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![pcy](/content/r3q3x042786w5566/xxlarge1087.gif) ![rcy](/content/r3q3x042786w5566/xxlarge1088.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![mcy](/content/r3q3x042786w5566/xxlarge1084.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![mcy](/content/r3q3x042786w5566/xxlarge1084.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![scy](/content/r3q3x042786w5566/xxlarge1089.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![zcy](/content/r3q3x042786w5566/xxlarge1079.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) 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![gcy](/content/r3q3x042786w5566/xxlarge1075.gif) ![ucy](/content/r3q3x042786w5566/xxlarge1091.gif) ![rcy](/content/r3q3x042786w5566/xxlarge1088.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![vcy](/content/r3q3x042786w5566/xxlarge1074.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) , ![bcy](/content/r3q3x042786w5566/xxlarge1073.gif) ![ycy](/content/r3q3x042786w5566/xxlarge1099.gif) ![lcy](/content/r3q3x042786w5566/xxlarge1083.gif) ![pcy](/content/r3q3x042786w5566/xxlarge1087.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![kcy](/content/r3q3x042786w5566/xxlarge1082.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) , ![chcy](/content/r3q3x042786w5566/xxlarge1095.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![ucy](/content/r3q3x042786w5566/xxlarge1091.gif) ![scy](/content/r3q3x042786w5566/xxlarge1089.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![lcy](/content/r3q3x042786w5566/xxlarge1083.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![vcy](/content/r3q3x042786w5566/xxlarge1074.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![yucy](/content/r3q3x042786w5566/xxlarge1102.gif) ![shchcy](/content/r3q3x042786w5566/xxlarge1097.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) ![vcy](/content/r3q3x042786w5566/xxlarge1074.gif) ![lcy](/content/r3q3x042786w5566/xxlarge1083.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![yacy](/content/r3q3x042786w5566/xxlarge1103.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![ecy](/content/r3q3x042786w5566/xxlarge1101.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![kcy](/content/r3q3x042786w5566/xxlarge1082.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![lcy](/content/r3q3x042786w5566/xxlarge1083.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![rcy](/content/r3q3x042786w5566/xxlarge1088.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![ocy](/content/r3q3x042786w5566/xxlarge1086.gif) ![scy](/content/r3q3x042786w5566/xxlarge1089.gif) ![icy](/content/r3q3x042786w5566/xxlarge1080.gif) ![ecy](/content/r3q3x042786w5566/xxlarge1101.gif) ![lcy](/content/r3q3x042786w5566/xxlarge1083.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) ![kcy](/content/r3q3x042786w5566/xxlarge1082.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![rcy](/content/r3q3x042786w5566/xxlarge1088.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![ncy](/content/r3q3x042786w5566/xxlarge1085.gif) ![ycy](/content/r3q3x042786w5566/xxlarge1099.gif) ![khcy](/content/r3q3x042786w5566/xxlarge1093.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![rcy](/content/r3q3x042786w5566/xxlarge1088.gif) ![acy](/content/r3q3x042786w5566/xxlarge1072.gif) ![kcy](/content/r3q3x042786w5566/xxlarge1082.gif) ![tcy](/content/r3q3x042786w5566/xxlarge1090.gif) ![iecy](/content/r3q3x042786w5566/xxlarge1077.gif) .
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