Model Selection and Parameters Estimation in Kinetic Thermal Evaluations using semi-empirical models

The minimum number of thermoanalytical experiments that should be considered with the aim of performing a complete and reliable kinetic analysis when using semiempirical models is the problem of concern. It is shown by means of a series of numerical experiments that three differential scanning calorimetric (DSC) dynamic runs performed at different heating rates provide a complete and reliable kinetic analysis while the topological structure of two DSC curves is enough to determine the semiempirical model (among reaction order and Sestack-Bergrenn) that better describe the experimental data. The procedure is analyzed by means of the simulation of a complex kinetic scheme and the results verified considering the thermal decomposition of cumene hydroperoxide. The proposed approach can be easily generalized to different kinetic models and is provided with a possible criterion devoted to identify autocatalytic processes by means of dynamical DSC experiments