Piercey D.G. Advanced Energetic Materials: Strategies and Compounds

Dissertation zur Erlangung des Doktorgrades der Fakultät Chemie und Pharmazie der Ludwig-Maximilians Universität München, 2012. — 219 p.There are three major methods of imparting potentially explosive energy into a molecule; fuel and oxidizer being contained in the same molecule, compounds possessing ring or cage strain, and high heat of formation compounds. These generally are used combined giving explosives with energy content resulting from multiple sources. In an explosive possessing both fuel and oxidizer, the separation of fuel (carbon) and oxidizer (oxygen) creates a thermodynamic downhill slope, and thus energy content, towards the formation of oxidized species upon detonation. When a caged or cyclic explosive compound possesses bond strain resulting from the geometry of the compound, this stored energy contributes to the energy released upon detonation. Similarly, nitrogen atoms in an explosive are at a higher potential energy compared to nitrogen gas as a result of the higher thermodynamic stability of a nitrogen-nitrogen triple vs. single or double bond, thus the formation of nitrogen gas from a nitrogenous explosive can create explosive energy release. The case of nitrogen is unique where higher bond order results in greater stability, carbon shows the opposing trend and small molecules containing carbon-carbon triple bonds such as acetylene and acetylides are explosive solely based on heat of formation!