All You Need to Know about the Kinetics of Thermally Stimulated Reactions Occurring on Cooling

In this tutorial overview article the authors share their original experience in studying the kinetics of thermally stimulated reactions under the conditions of continuous cooling. It is stressed that the kinetics measured on heating is similar to that measured on cooling only for single-step reactions. For multi-step reactions the respective kinetics can differ dramatically. The application of an isoconversional method to thermogravimetry (TGA) or differential scanning calorimetry (DSC) data allows one to recognize multi-step kinetics in the form of the activation energy that varies with conversion. Authors’ argument is supported by theoretical considerations as well as by experimental examples that include the reactions of thermal decomposition and crosslinking polymerization (curing). The observed differences in the kinetics measured on heating and cooling ultimately manifest themselves in the Arrhenius plots of the opposite curvatures, which means that the heating kinetics cannot be used to predict the kinetics on cooling. The article provides important background knowledge necessary for conducting successful kinetic studies on cooling. It includes a practical advice on optimizing the parameters of cooling experiments as well as on proper usage of kinetic methods for analysis of obtained data.