Vapor-phase decomposition of dimethyl methylphosphonate (DMMP), a sarin surrogate,in presence of metal oxides

Chemical warfare agents (CWA) are stockpiled in large quantities across the globe. Agents stored in inaccessible facilities need to be destroyed rapidly without dispersing the compounds to surrounding areas. Metal-based energetic formulations are used in such prompt defeat applications to rapidly decompose the CWA by generating a high temperature environment. An alternate, and possibly a more effective decomposition pathway could be provided by chemicidal action of aerosolized condensed combustion products, which typically consist of metal oxides. Toxic fumes that escape the high tem-perature blast zone can be neutralized by smoke generated during combustion, depending on the par-ticle size, surface characteristics, chemical properties, and concentration of this smoke. This review considers relevant experimental and modeling studies quantifying decomposition of CWA comprising organophosphorus compounds and their surrogates on the surface of various metal oxides. Dimethyl methylphosphonate (DMMP), a sarine surrogate, was used most commonly for such experiments. Many reported efforts focused on the mechanisms of adsorption of DMMP to various metal oxides and initial reaction steps cleaving various bonds from the chemisorbed molecules. For selected oxides, these ex-periments were supported by quantum-mechanical calculations. In other studies, the capacity of oxide surfaces to adsorb and decompose DMMP was quantified. In most cases, porous catalysts were used although limited experimental data are available for aerosolized nonporous oxide particles. The reported experimental data applicable to scenarios involving prompt decomposition of CWA are summarized. It is noted that information is lacking describing respective heterogeneous reaction kinetics. Preliminary estimates of aerosolized smoke particle concentrations required to destroy CWA are made considering gas phase diffusion rates and reported values of the oxide capacity to decompose CWA or their surrogates.     

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