Significance of Theoretical Decomposition Enthalpies for Predicting Thermal Hazards

Abstract

Much effort is currently put into the development of models for predicting decomposition enthalpies measured using differential scanning calorimetry (DSC). As an alternative to the purely empirical schemes reported so far, this work relies on theoretical values obtained on the basis of simple assumptions. For nitroaromatic compounds (NACs) studied in sealed sample cells, our approach proves clearly superior to previous ones. In contrast, it correlates poorly with data measured in pin-hole sample cells. Progress might be obtained through a combination of the present approach with the usual Quantitative Structure-Property Relationships (QSPR) methodologies. This work emphasizes the significance of the theoretical decomposition enthalpy as a fundamental descriptor for the prediction of DSC values. In fact, the theoretical value provides a valuable criterion to characterize thermal hazards, as a complement to experimental decomposition temperatures.