The use of TA — GLC — MS as a quantitative specific EGA technique for the investigation of complex thermal decomposition reactions: The thermal decomposition of calcium propanoate |
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Authors: | P A Barnes G Stephenson S B Warrington |
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Institution: | (1) Chemistry Section, School of Health and Applied Sciences, Leeds Polytechnic, Calverley Street, LS1 3HE Leeds, UK;(2) Present address: Laboratory of the County AnalystZ, County Hall, TA1 4DY Taunton, UK |
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Abstract: | A versatile and flexible system is described for evolved gas analysis using a GLC, MS (mass scan and SIM modes) and GLC-MS. Gases evolved from materials in two differential thermal analysis units, a thermobalance or a micro-furnace linked directly to the MS or GLC can be analysed. Details are given of computer controlled data acquisition and processing. The techniques are applied to the thermal decomposition of calcium propanoate. Mechanisms are suggested to account for the observed decomposition products and the solid state process. Evidence is presented to support the view that the latter occurs via nucleation followed by two-dimensional growth with an activation energy of 315 kJ mol–1 and a pre-exponential factor of 4.8×1021s–1.
Zusammenfassung Ein vielseitiges und flexibles System zur Analyse von gebildeten Gasen wird beschrieben, das GLC, MS (in Massen-scanning und SIM Betriebsweise) und GLC-MS umfaßt. Damit können die in zwei differentialthermoanalytischen Einheiten, einer Thermowaage oder einem direkt mit dem MS- oder GLC-Gerät gekoppelten Mikroofen aus den zu untersuchenden Substanzen entwickelten Gase analysiert werden. Einzelheiten der komputerkontrollierten Datengewinnung und Steuerung werden angegeben. Die Techniken werden zur Untersuchung der thermischen Zersetzung von Calciumpropionat herangezogen. Mechanismen werden vorgeschlagen, die die beobachteten Zersetzungsprodukte und die Festkörperreaktion erklären. Beweise werden dafür erbracht, daß bei letzterer eine Keimbildung und darauffolgendes zweidimensionales Wachstum vor sich geht, wobei die Aktivierungsenergie 315 kJ·mol–1 und der präexponentielle Faktor 4.8·1021·s–1 beträgt.
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![rcy](/content/n24h14r763p547g1/xxlarge1088.gif) ![ncy](/content/n24h14r763p547g1/xxlarge1085.gif) ![ycy](/content/n24h14r763p547g1/xxlarge1099.gif) ![rcy](/content/n24h14r763p547g1/xxlarge1088.gif) ![ocy](/content/n24h14r763p547g1/xxlarge1086.gif) ![scy](/content/n24h14r763p547g1/xxlarge1089.gif) ![ecy](/content/n24h14r763p547g1/xxlarge1101.gif) ![ncy](/content/n24h14r763p547g1/xxlarge1085.gif) ![iecy](/content/n24h14r763p547g1/xxlarge1077.gif) ![rcy](/content/n24h14r763p547g1/xxlarge1088.gif) ![gcy](/content/n24h14r763p547g1/xxlarge1075.gif) ![icy](/content/n24h14r763p547g1/xxlarge1080.gif) ![iecy](/content/n24h14r763p547g1/xxlarge1077.gif) ![acy](/content/n24h14r763p547g1/xxlarge1072.gif) ![kcy](/content/n24h14r763p547g1/xxlarge1082.gif) ![tcy](/content/n24h14r763p547g1/xxlarge1090.gif) ![icy](/content/n24h14r763p547g1/xxlarge1080.gif) ![vcy](/content/n24h14r763p547g1/xxlarge1074.gif) ![acy](/content/n24h14r763p547g1/xxlarge1072.gif) ![tscy](/content/n24h14r763p547g1/xxlarge1094.gif) ![icy](/content/n24h14r763p547g1/xxlarge1080.gif) 315 ![kcy](/content/n24h14r763p547g1/xxlarge1082.gif) ![dcy](/content/n24h14r763p547g1/xxlarge1076.gif) .![mcy](/content/n24h14r763p547g1/xxlarge1084.gif) ![ocy](/content/n24h14r763p547g1/xxlarge1086.gif) ![lcy](/content/n24h14r763p547g1/xxlarge1083.gif) –1 ![pcy](/content/n24h14r763p547g1/xxlarge1087.gif) ![rcy](/content/n24h14r763p547g1/xxlarge1088.gif) ![iecy](/content/n24h14r763p547g1/xxlarge1077.gif) ![dcy](/content/n24h14r763p547g1/xxlarge1076.gif) ![ecy](/content/n24h14r763p547g1/xxlarge1101.gif) ![kcy](/content/n24h14r763p547g1/xxlarge1082.gif) ![shcy](/content/n24h14r763p547g1/xxlarge1096.gif) ![ncy](/content/n24h14r763p547g1/xxlarge1085.gif) ![iecy](/content/n24h14r763p547g1/xxlarge1077.gif) ![ncy](/content/n24h14r763p547g1/xxlarge1085.gif) ![tscy](/content/n24h14r763p547g1/xxlarge1094.gif) ![icy](/content/n24h14r763p547g1/xxlarge1080.gif) ![acy](/content/n24h14r763p547g1/xxlarge1072.gif) ![lcy](/content/n24h14r763p547g1/xxlarge1083.gif) ![softcy](/content/n24h14r763p547g1/xxlarge1100.gif) ![ncy](/content/n24h14r763p547g1/xxlarge1085.gif) ![ycy](/content/n24h14r763p547g1/xxlarge1099.gif) ![fcy](/content/n24h14r763p547g1/xxlarge1092.gif) ![acy](/content/n24h14r763p547g1/xxlarge1072.gif) ![kcy](/content/n24h14r763p547g1/xxlarge1082.gif) ![tcy](/content/n24h14r763p547g1/xxlarge1090.gif) ![ocy](/content/n24h14r763p547g1/xxlarge1086.gif) ![rcy](/content/n24h14r763p547g1/xxlarge1088.gif) 4,8·1021 ![scy](/content/n24h14r763p547g1/xxlarge1089.gif) ![iecy](/content/n24h14r763p547g1/xxlarge1077.gif) –1.
The authors gratefully acknowledge the provision of an equipment grant and Research Studentships to G.S. and S.B.W. by the SERC. |
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