Competitive Vaporization and Decomposition of Liquid RDX

• Published in: The journal of physical chemistry. B Vol. 104; no. 11; pp. 2570 - 2574
• Main Authors: Long, Gregory T, Vyazovkin, Sergey, Brems, Brittany A, Wight, Charles A
• Format: Journal Article
• Language: English
• Published: American Chemical Society 23-03-2000
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp993334n

The thermal decomposition of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Activation energies as a function of the extent of conversion, α, have been determined by model-free isoconversional analysis of these data. In open pans, evaporation is a prevalent process with an activation energy of ∼100 kJ mol-1. Confining the system in either a pierced pan or a closed pan promotes liquid state decomposition of RDX that occurs with an activation energy of ∼200 kJ mol-1, which suggests scission of an N−N bond as the primary decomposition step. In such a confined environment, gas phase decomposition is a competing channel with an activation energy estimated to be ∼140 kJ mol-1. In a closed pan, RDX generates a heat release of ∼500 kJ mol-1 that is independent of both the heating rate, β, and the mass.