Limitations of model-fitting methods for kinetic analysis: Polystyrene thermal degradation

In this paper, some clarifications regarding the use of model-fitting methods of kinetic analysis are provided in response to the lack of plot linearity and dispersion in the activation energy values for the thermal degradation of polystyrene found in the literature and some results proposing an nth order model as the most suitable one. In the present work, two model-fitting methods based on the differential and integral forms of the general kinetic equation are evaluated using both simulated and experimental data, showing that the differential method is recommended due to its higher discrimination power. Moreover, the intrinsic limitations of model-fitting methods are highlighted: the use of a limited set of kinetic models to fit experimental data and the ideal nature of such models. Finally, it is concluded that a chain scission model is more appropriate than first order.

► Integral and differential model-fitting methods are tested with simulated data.
► Calculated activation energy is independent of the heating rate.
► Some limitations of model-fitting methods are highlighted.
► The degradation of polystyrene is described by a chain scission model.