Kissinger kinetic analysis of data obtained under different heating schedules

The dynamic heating rate method developed by TA Instruments (Hi-Res^TM) is a kind of sample controlled thermal analysis in which a linear relationship between the logarithm of the heating rate and the rate of mass change is imposed. It is shown in this paper that the reacted fraction at the maximum reaction rate strongly depends on the parameters selected for the Hi-Res heating algorithm, what invalidates the use of the Kissinger method for analysing Hi-Res data unless that the reaction fits a first order kinetic law. Only in this latter case, it has been demonstrated that it is not required that a constant value of the reacted fraction at the maximum reaction rate is fulfilled for determining the activation energy from the Kissinger method. In such a case the Kissinger plot gives the real activation energy, independently of both the heating schedule used and the value of the reacted fraction, α_m, at the maximum.