Chapter 12 – Interactions of model organic species and explosives with clay minerals

Energetic compounds used in the synthesis of fungicides, insecticides, herbicides, pharmaceuticals, and dyes. They are metastable and always decompose at some rate. Therefore, the properties of energetic materials are controlled by reaction kinetics. These materials are susceptible to initiation, or self-sustained energy release, when present in sufficient quantifies and exposed to stimuli such as heat, shock, friction, chemical incompatibility, or electrostatic discharge. Each of these materials reacts differently to the aforementioned stimuli; all of these burn, but explosives and propellants can detonate under certain conditions Explosives are classified as primary or secondary, based on their susceptibility to initiation. The most studied kinds of explosives are nitroaromatic explosives and their metabolites. Therefore, the emphasis of this chapter is on properties of nitroaromatic explosives and their interactions with soils. Nitroaromatic explosives are toxic, and their environmental transformation products, including arylamines, arylhydroxyl-amines, and condensed products such azoxy- and azo-compounds, are equally or more toxic than the parent nitroaromatic. Aromatic amines and hydroxylamines are implicated as carcinogenic intermediates as a result of nitrenium ions formed by enzymatic oxidation. Aromatic nitro compounds are resistant to chemical or biological oxidation and to hydrolysis because of their electron-withdrawing nitro groups. Consequently, they are environmentally persistent. The chapter discusses the interactions of energetic materials with soils. An approach has emerged for studying the properties of energetic materials and reactions with soils and water at the atomistic level that relies on the use of predictive simulations of clay-energetic material systems. The chapter discusses this approach. There are also details on interactions of clay minerals with water molecules, organic molecules, and energetic materials—experimental and theoretical study. Both experimental and quantum chemical studies have showed the structure, dynamic interaction of interlayer water in clay minerals. The interlayer counterion has a significant effect on the location and interactions of water molecules.

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