Thermal Activation of the High Explosive NTO: Sublimation, Decomposition, and Autocatalysis

Abstract

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) show that the heating of 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) leads to competitive sublimation and condensed-phase exothermic decomposition. Model-free isoconversional analysis has determined activation energies (Eα) for these processes as a function of the extent of conversion, α. Sublimation occurs most readily in an open pan; although more than simple sublimation was observed, a global activation energy of Eα = 130−140 kJ mol-1 for sublimation was determined. Nonisothermal TGA and DSC traces run on pierced pan samples provide convincing evidence for competitive sublimation and condensed-phase decomposition of NTO. Confining NTO samples in a closed pan results in condensed-phase decomposition that leads to the formation of gaseous reaction products and shows autocatalytic behavior during the latter stages. Isoconversional analysis of DSC traces of closed pan samples yield activation energies for exothermic decomposition that increase from Eα = 273 kJ mol-1 for α = 0.01 to a plateau of 333 kJ mol-1 for 0.17 ≤ α ≤ 0.35 prior to decreasing to 184 kJ mol-1 for α = 0.99. The decrease in Eα with α during the latter stages of decomposition agrees with previous reports of autocatalytic behavior.