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Temperature dependence of the rate of reaction in thermal analysis

The Arrhenius equation in condensed phase kinetics

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Abstract

Special problems are encountered in modeling the temperature dependence of the kinetics of heterogeneous, condensed phase systems. In the division of the model for the reaction rate into two parts, a)f(α) which is physical (translational) and b)k(T) which is chemical (vibrational), complications arise in defining the temperature dependence of part a) which may take various mathematical forms and then in coupling it with the Arrhenius temperature dependence of part b). The role off(α) in thermal analysis systems is discussed. The concept of rate-controlling step is applied to the simplification of the temperature dependent term. The significance of the compensation effect in these systems is described and an heuristic rationalization for it is suggested. Maximum practical temperature ranges for thermal analysis experiments and the effect of temperature measurement imprecision on obtaining meaningful Arrhenius parameters are discussed. The WLF and other equations used to describe the temperature dependence off(α) are not found to couple compatibly with the Arrhenius equation.

Zusammenfassung

Bei der Modellierung der TemperaturabhÄngigkeit der Kinetik bei heterogenen, kondensierten Phasen treten spezielle Probleme auf. In der Unterteilung des Modelles für die Reaktionsgeschwindigkeit in zwei Teile: a)f(α) ist physikalisch (Translation) und b)k(T) ist chemisch (Vibration) treten bei der Definierung der TemperaturabhÄngigkeit von Teil a) und dann bei der Verknüpfung mit der Arrhenius-schen TemperaturabhÄngigkeit von Teil b) Komplikationen auf. Es wird die Rolle vonf(α) in thermoanalytischen Systemen besprochen. An einer Vereinfachung des temperaturabhÄngigen Termes wurde das Konzept des geschwindigkeitsbestimmenden Schrittes angewendet. Es wird die Bedeutsamkeit des Kompensationseffektes in diesen Systemen beschrieben und dafür eine heuristische Vereinfachung vorgeschlagen. Praktisch gesehen maximale Temperaturbereiche für thermoanalytische Experimente sowie der Einflu\ der Ungenauigkeit der Temperaturmessung für die erhaltenen Arrhenius-Parameter wird diskutiert. Die zur Beschreibung der TemperaturabhÄngigkeit vonf(α) benutzten WLF und anderen Gleichungen stellen keine KompatibilitÄt mit der Arrhenius-schen Gleichung her.

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  1. Scientific Thermal research & Data Analysis (Strda), 5309 Iroquois Road, 20816, Bethesda, Maryland, USA

    J. H. Flynn

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Flynn, J.H. Temperature dependence of the rate of reaction in thermal analysis. Journal of Thermal Analysis 36, 1579–1593 (1990). https://doi.org/10.1007/BF01914077

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  • DOI: https://doi.org/10.1007/BF01914077

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