Fast Reactions In Energetic Systems

This book presents the formal lectures and contributed papers given at the NATO Advanced Study Institute on Fast Reactions in Energetic Systems, which took place in Preveza, Greece, during the period 6-19 July 1980. The material describes experimental observations and the more advanced theoretical aspects of certain types of fast reactions and energy or charge transfer processes which are usually complete 6 12 in periods of 10- - 10- seconds. Furthermore, it discusses the role of macroscopic and molecular processes in the ignition, combustion, deflagration, and detonation of solid, liquid, and gaseous chemical systems. Various papers deal with the ability of molecules to absorb and transmit the different forms of energy provided by shock, light, thermal, or electron pulses, and to contribute to the propagation of reactions under high temperatures and pressures. The role of energy pumped or transferred to electronic or vibrational states is discussed in terms of excitation, ionization, bond scission, and the formation of free radicals. The dynamics and reactivity of ionic species, electronically and vibrationally excited states, and free radicals are described for various gaseous, liquid, and solid systems. The proceedings include presentations of theoretical and experimental techniques to describe and observe the phenomena.

Modern energetic materials include explosives, blasting powders, pyrotechnic m- tures and rocket propellants [1, 2]. The study of high-temperature decomposition of condensed phases of propellants and their components (liquid, solid and hybrid) is currently of special importance for the development of space-system engineering [3, 4]. To better understand the burning mechanisms (stationary, nonstationary, - steady) of composite solid propellants and their components, information about the macrokinetics of their high-temperature decomposition is required [5]. To be able to evaluate the ignition parameters and conditions of safe handling of heat-affected explosives, one needs to know the kinetic constants of their high-temperature - composition. The development of new composite solid propellants characterized by high performance characteristics (high burning rates, high thermal stability, stability to intrachamber perturbations, and other aspects) is not possible without quanti- tive data on the high-temperature decomposition of composite solid propellants and their components [6]. The same reasons have resulted in signi?cant theoretical and practical interest in the high-temperature decomposition of components of hybrid propellants. It is known that hybrid propellants have not been used very widely due to the low bu- ing (pyrolysis) rates of the polymer blocks in the combustion chambers of hybrid rocket engines. To increase the burning rates it is necessary to obtain information about their relationships to the corresponding kinetic and thermophysical prop- ties of the fuels.

This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidation of reaction dynamics and structural changes occurring during the course of ultrafast chemical reactions; propagation of turbulent flames and detonations in gaseous· energetic systems are also discussed in some detail. In addition a large portion of the program was devoted to current experimental and theoretical studies of the structure of the transition state as inferred from product state distributions; translational energy release in the photodissociation of aromatic molecules; intramolecu lar and intraionic dynamic processes.

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