Nitrogen Radicals from Thermal and Photochemical Decomposition of Ammonium Perchlorate, Ammonium Dinitramide, and Cyclic Nitramines

Abstract

AbstractFree-radical thermal and photochemical decomposition products of ammonium dinitramide (ADN), an acyclic nitramine, are compared to that of cyclic nitramines (RDX, HMX, and HNIW) and to ammonium perchlorate (AP). Photochemical formation of NO2 from uvphotolysis of ADN at 77 K is found to follow first-order kinetics; whereas, zero-order NO2 formation is observed from the cyclic nitramines under the conditions of this experiment. Mechanisms are suggested for ADN decomposition. A general trend of cyclic nitramines to thermally decompose forming nitroxide radicals is supported by 15N-ring-labeled HNIW results. ADN thermally decomposes at 19° C to form free-radical reaction products in solution with tetrahydrothiophene-1,1-dioxide.