Thermal Decomposition of Energetic Materials. 17. A Relationship of Molecular Composition to HONO Formation: Bicyclo and Spiro Tetranitramines

摘要

The IR-active gas products from the rapid thermal decomposition of six cyclic nitramines, five of which contain bicyclic and spiro ring systems, were quantified. Four of the compounds are structural isomers C6H10N8O8. Combining these results with 11 nitramines from our previous studies led to the discovery of a relationship between the H/NO2 ratio of the parent molecule and the amount of HONO released in the initial 0.2 s of fast decomposition. Further analysis suggests that HONO forms largely from the adventitious encounter of H and NO2 rather than by a specific, well-defined reaction, that CH2 units may be more effective H donors than CH3 units in the nitramines studied to date, that by sterically crowding together the NO2 and CH2 units, the production of HONO might be enhanced, and that HONO is an effective source of NO via its secondary reactions.