The Reactivity of Energetic Materials at Extreme Conditions

Chemistry, Materials Science, and Life Sciences Directorate Lawrence Livermore National Laboratory, Livermore, California 

Understanding the condensed-phase properties of HE materials is important for determining stability and performance. Information regarding HE material properties [such as the physical, chemical, and mechanical behaviors of the constituents in plastic-bonded explosive (PBX) formulations] is necessary for efficiently building the next generation of explosives as the quest for more powerful energetic materials (in terms of energy per volume) moves forward.1 

There is a need to better understand the physical, chemical, and mechanical behaviors when modeling HE materials from fundamental theoretical principles. Among the quantities of interest in PBXs, for example, are thermodynamic stabilities, reaction kinetics, equilibrium transport coefficients, mechanical moduli, and interfacial properties between HE materials and the 

Reviews in Computational Chemistry, Volume 25 edited by Kenny B. Lipkowitz and Thomas R. Cundari Copyright 2007 Wiley-VCH, John Wiley 6C Sons, Inc. 

A purely thermodynamic treatment of detonation ignores the important question of reaction time scales. The finite time scale of reaction leads to strong deviations in detonation velocities from values based on the Chapman-Jouguet theory.16 The kinetics of even simple molecules under high-pressure conditions is not well understood. 

---

Laurence E. Eried, The Reactivity of Energetic Materials at Extreme Conditions. 

High-pressure experiments promise to provide insight into chemical reactivity under extreme conditions. For instance, chemical equilibrium analysis of shocked hydrocarbons predicts the formation of condensed carbon and molecular hydrogen.17 Similar mechanisms are at play when detonating energetic materials form condensed carbon.10 Diamond anvil cell experiments have been used to determine the equation of state of methanol under high pressures.18 We can then use a thermodynamic model to estimate the amount of methanol formed under detonation conditions.19... 

---