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Is the Kissinger Equation Applicable to the Processes that Occur on Cooling?
Author(s) -
Vyazovkin Sergey
Publication year - 2002
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/1521-3927(20020901)23:13<771::aid-marc771>3.0.co;2-g
Subject(s) - thermodynamics , activation energy , sign (mathematics) , materials science , physics , mathematics , chemistry , mathematical analysis
The activation energy, E , of nonisothermal crystallization of polymer melts has been frequently evaluated by the Kissinger equation with positive rates of temperature variation, β . It is demonstrated that dropping the negative sign for β is a mathematically invalid procedure that generally makes the Kissinger equation inapplicable to the processes that occur on cooling. Simulations and an experimental example demonstrate that the use of this invalid procedure may result in erroneous values of E . Alternative methods of estimating the correct E values are suggested.