J. H. Flynn Scientific Thermal research & Data Analysis (Strda) 5309 Iroquois Road 20816 Bethesda Maryland USA

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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.

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
per Year
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Founder Akadémiai Kiadó
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)

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