Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate. 2011

Chanat Chokejaroenrat, and Steve D Comfort, and Clifford E Harris, and Daniel D Snow, and David Cassada, and Chainarong Sakulthaew, and Tunlawit Satapanajaru
Department of Civil Engineering, University of Nebraska-Lincoln , Lincoln, Nebraska 68588-0531, United States.

The chemical oxidant permanganate (MnO(4)(-)) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO(4)(-) with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ∼ 7, 25 °C) verified that RDX-MnO(4)(-) reaction was first-order with respect to MnO(4)(-) and initial RDX concentration (second-order rate: 4.2 × 10(-5) M(-1) s(-1)). Batch experiments showed that choice of quenching agents (MnSO(4), MnCO(3), and H(2)O(2)) influenced sample pH and product distribution. When MnCO(3) was used as a quenching agent, the pH of the RDX-MnO(4)(-) solution was relatively unchanged and N(2)O and NO(3)(-) constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N(2)O produced under neutral pH (molar ratio N(2)O/NO(3) ∼ 5:1), no strong pH effect on RDX-MnO(4)(-) reaction rates, a lower activation energy than the hydrolysis pathway, and previous literature on MnO(4)(-) oxidation of amines, we propose that RDX-MnO(4)(-) reaction involves direct oxidation of the methylene group (hydride abstraction), followed by hydrolysis of the resulting imides, and decarboxylation of the resulting carboxylic acids to form N(2)O, CO(2), and H(2)O.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D010087 Oxides Binary compounds of oxygen containing the anion O(2-). The anion combines with metals to form alkaline oxides and non-metals to form acidic oxides. Oxide
D014227 Triazines Heterocyclic rings containing three nitrogen atoms, commonly in 1,2,4 or 1,3,5 or 2,4,6 formats. Some are used as HERBICIDES. Triazine,Benzotriazines
D014874 Water Pollutants, Chemical Chemical compounds which pollute the water of rivers, streams, lakes, the sea, reservoirs, or other bodies of water. Chemical Water Pollutants,Landfill Leachate,Leachate, Landfill,Pollutants, Chemical Water
D053834 Explosive Agents Substances that are energetically unstable and can produce a sudden expansion of the material, called an explosion, which is accompanied by heat, pressure and noise. Other things which have been described as explosive that are not included here are explosive action of laser heating, human performance, sudden epidemiological outbreaks, or fast cell growth. Explosive,Explosives,Agents, Explosive
D017895 Manganese Compounds Inorganic chemicals that contain manganese as an integral part of the molecule. Compounds, Manganese

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