On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide.
Artikel i vetenskaplig tidskrift, 2010
Mechanistic pathways for the thermal decompn. of the solid-state energetic oxidizers ammonium dinitramide (ADN) and potassium dinitramide (KDN) are deciphered by carefully considering previously performed exptl. studies and using state of the art quantum chem. modeling of mol. clusters. Decompn. is governed by surface chem. processes, involving polarized (twisted) dinitramide anions of reduced stability. Under atm. and low-pressure conditions, the rate-detg. step for the decompn. of these dinitramide salts is the dissocn. into NO2 and NNO2- radicals. The activation barriers for these steps are estd. to be 30 and 36 kcal/mol for ADN and KDN, resp. The known stabilizing effect of water is explained by its hydrogen bonding ability, which counteracts polarization of surface dinitramides. The reactivity of ADN toward various chem. environments is likely explained through metastable decompn. radical intermediates. Donation of hydrogen bonds, antioxidant character, and basicity are properties believed to correlate with a compd.'s ability to act as a stabilizer for dinitramide salts. [on SciFinder(R)]
density functional theory