Abstract
This chapter discusses a method for the identification of autocatalytic decompositions that has been tested on 100 compounds. This method, based on dynamic Differential Scanning Calorimetry (DSC) measurements, consists of fitting a first order kinetic model to the measured heat release rate curve (dynamic DSC measurement) and determines the apparent activation energy. When an endothermic process precedes the exothermic decomposition, no fitting is possible because the real onset of the exothermic reaction necessary to perform the fit cannot be determined. If the apparent activation energy is higher than 220 kJ/mol, the decomposition is autocatalytic. The proposed method is a rapid and easily applicable tool and allows to differentiate between autocatalytic and non-autocatalytic decompositions. However, the new method cannot be applied in cases where the decomposition under investigation is directly preceded by an endothermal signal, and has to be used very carefully in case of consecutive reactions. Another important point of thermal risk is the identification of autocatalytic reactions. This type of reactions requires a special attention and should be clearly distinguished from nth order reactions.
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