Doubts about the popular Kissinger method of kinetic evaluation and its applicability for crystallization of cooling melts requiring equilibrium temperature

Abstract

The famous Kissinger’s kinetic evaluation method (Anal Chem 29:1702, 1957) is examined with respect to the feasible impact of the individual quantities and assumptions involved. It is accentuated that the missing term on heat inertia may change the resulting values when searching for activation energies. Particular attention is paid to the heating rate, β, particularly when applied under opposite process of cooling. In such case of melt solidification, an additional thermodynamic term for the melt undercooling is needed to be incorporated which provides an alternative form of evaluation. Despite as many as 8000 applications caused by the obvious methods simplicity, these affects was overlooked. It is surprising that anybody who evolved various alternatives of the Kissinger method did not find any reasons for its criticism.