Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of
Department of Chemistry, University of Alabama at Birmingham, 901 S. 14th Street, Birmingham, AL 35294, USA
Academic Editor: Giuseppe Cirillo
Molecules 2020, 25(12), 2813; https://doi.org/10.3390/molecules25122813
Received: 25 May 2020
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Revised: 16 June 2020
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Accepted: 16 June 2020
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Published: 18 June 2020
(This article belongs to the Special Issue Exclusive Papers of the Editorial Board Members (EBMs) of the Materials Chemistry Section of Molecules)
The Kissinger method is an overwhelmingly popular way of estimating the activation energy of thermally stimulated processes studied by differential scanning calorimetry (DSC), differential thermal analysis (DTA), and derivative thermogravimetry (DTG). The simplicity of its use is offset considerably by the number of problems that result from underlying assumptions. The assumption of a first-order reaction introduces a certain evaluation error that may become very large when applying temperature programs other than linear heating. The assumption of heating is embedded in the final equation that makes the method inapplicable to any data obtained on cooling. The method yields a single activation energy in agreement with the assumption of single-step kinetics that creates a problem with the majority of applications. This is illustrated by applying the Kissinger method to some chemical reactions, crystallization, glass transition, and melting. In the cases when the isoconversional activation energy varies significantly, the Kissinger plots tend to be almost perfectly linear that means the method fails to detect the inherent complexity of the processes. It is stressed that the Kissinger method is never the best choice when one is looking for insights into the processes kinetics. Comparably simple isoconversional methods offer an insightful alternative.
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Keywords:
crosslinking polymerization (curing); decomposition; degradation; liquid and solid state; phase transitions; thermal analysis
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MDPI and ACS Style
Vyazovkin, S. Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of. Molecules 2020, 25, 2813. https://doi.org/10.3390/molecules25122813
AMA Style
Vyazovkin S. Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of. Molecules. 2020; 25(12):2813. https://doi.org/10.3390/molecules25122813
Chicago/Turabian StyleVyazovkin, Sergey. 2020. "Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of" Molecules 25, no. 12: 2813. https://doi.org/10.3390/molecules25122813
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