Thermodynamics and kinetics of thermal decomposition of diamylamyl phosphonate-nitric acid systems

Thermal decomposition of neat diamylamyl phosphonate (DAAP), nitric acid-solvates of DAAP and 1.1 M DAAP/n-dodecane was studied calorimetrically in heat-wait-search mode for the first time. The neat DAAP decomposed beyond 500 K while DAAP·0.7HNO3, DAAP·HNO3 and DAAP·2.1HNO3 decomposed exothermally at 386, 381 and 366 K respectively, indicating the role of amount of nitric acid on decomposition. Mixture of DAAP and 8 M nitric acid decomposed at a lower temperature than the acid solvates with a larger excursion in temperature and pressure yielding hydrocarbons, CO2, CO, NOx and a reddish liquid or a black solid residue. Enthalpy of decomposition of DAAP·0.7HNO3, DAAP·HNO3 and DAAP·2.1HNO3 were found to be −237.7 ± 4.8, −348.9 ± 3.4 and −1002.1 ± 2.6 kJ mol−1 and the activation energy and pre-exponential factors were 127.5 ± 1.5, 121.8 ± 0.8 and 105.3 ± 1.2 kJ mol−1 and 9.0 × 1013, 1.4 × 1012 and 2.2 × 1010 lit mol−1 s−1, respectively. Heat capacity (Cp) of acid solvates were measured and used for deriving the enthalpy change.

► The thermal hazard characteristics of DAAP has been evaluated for the first time.
► The thermodynamic and kinetic parameters have also been derived wherever possible.
► The onset of decomposition of the acid-solvates depended on the nitric acid content.
► A clear trend was seen in the decomposition of acid-solvates of TBP, TiAP and DAAP.