Tracking Thermal Decomposition Chemistry in Secondary Solid Explosives with X-ray Diffraction

We present an approach for measuring thermal decomposition kinetics in crystalline solids using X-ray diffraction to track the loss of crystallinity that accompanies condensed phase decomposition chemistry. We apply this method to systems for which extracting thermodynamic parameters has been historically difficult: organic molecular crystals that thermally decompose below their melting points, such as solid explosives. To demonstrate this method, we measured the rate of solid, thermal decomposition versus temperature in three different secondary solid explosives and the sugar fructose. In all cases, we observed an acceleration in the thermal decomposition rate with increasing temperature, which forms a vertical asymptote, a phenomenon known as melt acceleration. We show that observing the vertical asymptote in the thermal decomposition rate allows for identifying the thermodynamic melting point, which is not trivial to determine when melting and thermal decomposition happen simultaneously. We expect this method to be useful for studying thermal decomposition and for extracting thermodynamic data for secondary solid explosives, data that are needed for modeling and understanding faster phenomena, such as detonation. We also expect this method to be relevant to other organic molecular crystals in which thermal decomposition and melting overlap, such as sugars or pharmaceuticals.