Abstract
Thermal decomposition of neat diamylamyl phosphonate (DAAP), nitric acid-solvates of DAAP and 1.1M DAAP/n-dodecane was studied calorimetrically in heat-wait-search mode for the first time. The neat DAAP decomposed beyond 500K while DAAP·0.7HNO3, DAAP·HNO3 and DAAP·2.1HNO3 decomposed exothermally at 386, 381 and 366K respectively, indicating the role of amount of nitric acid on decomposition. Mixture of DAAP and 8M 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±2.6kJmol−1 and the activation energy and pre-exponential factors were 127.5±1.5, 121.8±0.8 and 105.3±1.2kJmol−1 and 9.0×1013, 1.4×1012 and 2.2×1010 litmol−1s−1, respectively. Heat capacity (Cp) of acid solvates were measured and used for deriving the enthalpy change.
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