Imperfections of Kissinger evaluation method and crystallization kinetics.

The famous Kissinger's kinetic evaluation method (Anal. Chem. 1957) is examined with respect to: a) the relation between the DTA signal θ ( t) and the reaction rate r( t) ≡ dα/d t; b) the requirements on reaction mechanism model f(α); and c) the relation of starting kinetic equation to the equilibrium behavior of sample under study. Distorting effect of heat inertia and difference between the temperature T of extreme DTA deviation and the temperature T at which the reaction rate is maximal are revealed. The kinetic equations respecting the influence of equilibrium temperature T, especially fusion temperature T, are tested as bases for a modified Kissinger-like evaluation of kinetics. [ABSTRACT FROM AUTHOR]