Nonisothermal decomposition kinetics and computational studies on the properties of 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3,3,1]onan-3,7-dione (TNPDU).

Abstract The thermal decomposition and the nonisothermal kinetics of the thermal decomposition reaction of 2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3,3,1]onan-3,7-dione (TNPDU) were studied under the nonisothermal condition by differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG) methods. The kinetic model function in differential form and the value of Ea and A of the decomposition reaction of TNPDU are f(alpha) = 3(1 - alpha)[-ln(1 - alpha)](2/3), 141.72 kJ mol(-1), and 10(11.99) s(-1), respectively. The critical temperature of thermal explosion of the title compound is 232.58 degrees C. The values of DeltaS(++), DeltaH(++), and DeltaG(++) of this reaction are -15.50 J mol(-1) K(-1), 147.65 kJ mol(-1), and 155.26 kJ mol(-1), respectively. The theoretical investigation on the title compound as a structure unit was carried out by the DFT-B3LYP/6-311++G** method. The IR frequencies and NMR chemical shift were performed and compared with the experimental results. The heat of formation (HOF) for TNPDU was evaluated by designing isodesmic reactions. The detonation velocity (D) and detonation pressure (P) were estimated by using the well-known Kamlet-Jacobs equation, based on the theoretical densities and HOF. The calculation on bond dissociation energy suggests that the N-N bond should be the trigger bond during the pyrolysis initiation process.