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This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous rea...
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This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous reaction with a surface. Typically the surface exists as a dispersion or matrix of particulate matter or pores, and a determination of the heterogeneous chemistry of the system must address the extent to which the complexity of the environmental surface affects the reaction rates. Reactions that are of current interest are the series of chlorine nitrate reactions important in polar ozone depletion. The authors have applied surface spectroscopic techniques developed at LANL to address the chemistry of chlorine nitrate reactions on porous nitric and sulfuric acid ice surfaces as a model study of the measurement of complex, heterogeneous reaction rates. The result of the study is an experimental determination of the surface coverage of one adsorbed reagent and a mechanism of reactivity based on the dependence of this coverage on temperature and vapor pressure. The resulting mechanism allows the first comprehensive modeling of chlorine nitrate reaction probability data from several laboratories.
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Ammonium nitrate is being studied as an alternative for ammonium perchlorate as an oxidizing agent in Department of Defense 1.1 and 1.3 rocket propellants. Use of ammonium nitrate would eliminate the HCl produced by ammonium perch...
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Ammonium nitrate is being studied as an alternative for ammonium perchlorate as an oxidizing agent in Department of Defense 1.1 and 1.3 rocket propellants. Use of ammonium nitrate would eliminate the HCl produced by ammonium perchlorate upon thermal decomposition. To stabilize the ammonium nitrate, which suffers from phase instability, potassium dinitramide (KDN) is added. This increased use of ammonium nitrate will ultimately create a need for environmentally responsible processes to reuse ammonium nitrate extracted from demilitarized rocket motors. Ammonium Nitrate was investigated as an oxidizing agent for methanol, acetic acid and phenol. High removal of organic, ammonia and nitrate was achieved at stoichiometric concentrations. The oxidation of ammonia by nitrate was much faster than the oxidation of either methanol or acetic acid. Phenol, however, was in strong competition with ammonia for the oxidizer (nitrate). Nitrogen products included N(sub 2), N(sub 2)O, NO(sub 2(sup (minus))) as well as toxic NO and trace amounts of NO(sub 2). Carbon products were CO(sub 2), HCO(sub 3(sup (minus))), CO(sub 3)(sup 2(minus)), and CO.
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Hydrothermal Processing (HTP) is an attractive approach for the treatment of Hanford tank sludge. Hydrothermal Processing refers to a waste treatment technique in which an aqueous waste stream is fed through a chemical reactor at ...
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Hydrothermal Processing (HTP) is an attractive approach for the treatment of Hanford tank sludge. Hydrothermal Processing refers to a waste treatment technique in which an aqueous waste stream is fed through a chemical reactor at elevated temperatures and pressures to effect desired chemical transformations and separations. Transformations such as organic and nitrate destruction and sludge reformulation have been demonstrated at pilot scale using simulants of Hanford tank wastes. At sufficiently high temperatures and pressures organics and nitrates are destroyed in seconds, producing primarily simple products such as CO(sub 3)(sup 2(minus)), H(sub 2)O, N(sub 2), N(sub 2)O and OH(sup (minus)), and sludges are reduced in volume and reformulated as rapid settling oxides amenable to downstream separation, or in some cases reformulated as soluble products. This report describes the hydrothermal dissolution of chromium and chromium oxide; the hydrothermal oxidation of chromium with nitrate; hydrothermal dissolution of aluminum-bearing sludges; the solubility of aluminum compounds in caustic hydrothermal media; experimental techniques for the study of solubility and phase behavior; optical cell studies of basic aluminate solution solubilities; and high temperature, low density salt solubility in the packed-bed flow apparatus. (ERA citation 19:032482)
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Traditional methods for disposing of PEPs have been open burning or open detonation (OB/OD); however, regulatory agencies are likely to prohibit OB/OD because of the uncontrolled air emissions and soil contaminations. Likewise, co...
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Traditional methods for disposing of PEPs have been open burning or open detonation (OB/OD); however, regulatory agencies are likely to prohibit OB/OD because of the uncontrolled air emissions and soil contaminations. Likewise, controlled incineration carries a liability for air pollution because large quantities of NO(sub x) are produced in the conventional combustion chemistry of PEPS. Soil and ground water have already been contaminated with PEPs through normal operations at manufacturing plants and military bases. Incineration can be used for decontamination of these soils, with the associated liability for air pollution, but few satisfactory and economic methods exist for ground water decontamination. A clear need exists for improved disposal and destruction methods. The destruction of energetic materials, including propellants, explosives and pyrotechnics (PEPS) by oxidation in supercritical water is described. The focus is on the chemistry of the process. The destruction efficiencies and products of reaction contained in the aqueous and gaseous effluents of several representative PEPs are reported.
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