Journal
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
Volume 83, Issue 1, Pages 45-51Publisher
SPRINGER
DOI: 10.1007/s10973-005-7044-6
Keywords
activation energy; condensed phase; DSC; reaction kinetics; solids; thermogravimetry
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The paper presents the model-free kinetic approach in the context of the traditional kinetic description based on the kinetic triplet, A, E, and f(alpha) or g(alpha). A physical meaning and interpretability of the triplet are considered. It is argued that the experimental values of f(alpha) or g(alpha) and A are unlikely to be interpretable in the respective terms of the reaction mechanism and of the vibrational frequency of the activated complex. The traditional kinetic description needs these values for making kinetic predictions. Interpretations are most readily accomplished for the experimental value of E that generally is a function of the activation energies of the individual steps of a condensed phase process. Model-free kinetic analysis produces a dependence of E on a that is sufficient for accomplishing theoretical interpretations and kinetic predictions. Although model-free description does not need the values of A and f(alpha) or g(a), the methods of their estimating are discussed.
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