Trinitrotoluene oxidation

Industrial. Nitric acid is itself the starting material for ammonium nitrate, nitroglycerin [55-63-0] trinitrotoluene [118-96-7]., nitroceUulose [9004-70-0] and other nitrogen compounds used in the manufacture of explosives (see Explosives and propellants). Nitric acid is made by oxidation of ammonia to nitrogen dioxide [10102-44-0] which is subsequently absorbed by water. 

The action of hydroxylamine and sodium acetate in ethanol upon picryl chloride was stated to give 4,6-dinitrobenzofuroxan, and probably some of this compound was formed, although it was later shownthat much of the original work was faulty. A report that hydroxylamine and 2,4,5-trinitrotoluene give 5-methyl-6-nitro-benzofuroxan has been found to be incorrect. Benzofuroxan has not been prepared by V-oxidation of benzofurazan, and it seems unlikely that this could be achieved, since benzofuroxan itself is oxidizable by powerful reagents to o-dinitrobenzene (Section VI, B). A report of the oxidation by nitric acid of anthraceno[l,2-c]furazan to the furoxan is incorrectlv abstracted. 

Lang PS, W-K Ching, DM Willberg, MR Hoffmann (1998) Oxidative degradation of 2,4,6-trinitrotoluene by ozone in an electrohydraulic discharge reactor. Environ Sci Technol 32 3142-3148. 

Toluidines 2,4,6-Trinitrotoluene 1,3,5-Trioxane Urea Vinylidene chloride Nitric acid Sodium dichromate, sulfuric acid Oxidizing materials, acids Sodium nitrite, phosphorus pentachloride Chlorosulfonic acid, nitric acid, oleum... 

Trinitrobenzoic acid has been prepared by heating trinitrotoluene with fuming acid in a sealed tube to ioo°, for two weeks,1 the oxidation being only partial. It can also be prepared by heating trinitrotoluene under a reflux condenser, with a mixture of 5 parts of concentrated nitric acid and 10 1 Ber. 8, a 3 (1870). 

TACOM TBA TCLP THC TNB TNBA TNT TOC TRBP TW-SCWO Tank-Automotive and Armaments Command tributylamine toxicity characteristic leaching procedure total hydrocarbons trinitrobenzene trinitrobenzoic acid trinitrotoluene (an energetic material) total organic carbon thermal reduction batch processor transpiring-wall supercritical water oxidation... 

Wang, C. J., Thiele, S., and Bollag, J. M., 2002, Interaction of 2,4,6-trinitrotoluene (TNT) and 4-amino-2,6-dinitrotoluene with humic monomers in the presence of oxidative enzymes. Arch. Environ. Contam. Toxicol. 42 1-8. 

Parathion, Phorate Sulfur oxides, see Malathion Tartaric acid monoamide p-TCCH, see Lindane y-TCCH, see Lindane TCDD, see 2,4,5-Trichlorophenol Terbufos sulfone, see Terbufos Terbufos sulfoxide, see Terbufos Terephthalic acid, see p-Xylene o-Terphenyl, see Phthalic anhydride 2,2, 4,4 -Tetraamino-6,6 -azotoluene, see 2,4,6-Trinitrotoluene... 

The chemical structures of some common mifttary explosives are shown in Figure 1. These include the nitrate esters such as nitrocellulose (NC), NG, EGDN, and (PETN) nitroarenes such as trinitrotoluene (TNT, CH3—C6H2(N02)3), picric acid (HO—C5H2(N02)3), and 2,4,6-trinitrophenylmethylnitramine (tetryl) and nitramines such as RDX (C3H6N6O6), HMX (C4H8N8O8), and hexanitrohexa-azaisowurtzitane (CL— 20). Of these, only CL— 20 is new , that is, less than 50 years old [3]. Mixtures of oxidizers and fuels, such as AN and FO (called ANFO), are also secondary explosives. 

Trinitrobenzene is present in crude TNT manufactured by mixed acid nitration and results from methyl group oxidation followed by decarboxylation." In fact, a convenient method for the synthesis of 1,3,5-trinitrobenzene involves oxidation of 2,4,6-trinitrotoluene with a solution of sodium dichromate in sulfuric acid, followed by decarboxylation of the resulting 2,4,6-trinitrobenzoic acid in boiling water." 1,3,5-Trinitrobenzene is prepared from 2,4,6-trinitro-m-xylene by a similar route." 2,4,6-Trinitroanisole can be prepared from the... 

The displacement of alkoxy groups from polynitroarylenes has been used for the indirect synthesis of some highly nitrated polynitroarylenes. Holleman synthesized 2,3,4,6-tetranitrotoluene (57) by treating 3-methoxy-2,4,6-trinitrotoluene (132) with ammonia in methanol, followed by oxidation of the resulting product (56) with peroxymonosulfuric acid. 

Before anything else can be said about IEs, some rudimentary chemistry is needed. From a cookbook perspective, all explosives (be they military, commercial, or improvised) require the same chemical building blocks, which consist of a fuel and an oxidizer. Some explosives have the fuel and oxidizer as part of the same molecule, such as trinitrotoluene (TNT), and some explosives are comprised of mixtures of separate fuels and oxidizers, such as ammonium nitrate-fuel oil (ANFO). The oxidizer employed by the vast majority of explosives tends to be the NO2 (nitro) group. It is so predominant as an explosive ingredient that the primary focus of detection methods traditionally has been to look for nitro-derived properties. IEs tend to utilize a more diverse range of oxidizers. Table 3.1 gives a list of the numerous oxidizer possibilities. 

At the Sierra Army Depot in Herlong, California, groundwater had been contaminated by trinitrotoluene (TNT) and trichloroethylene (TCE). The 28-acre plume of contaminated ground-water was located about 70 ft underground. The U.S. Army evaluated the cost difference between conventional pump-and-treat systems, ultraviolet (UV) oxidation, granular activated carbon (GAC) filters, and MNA. The active treatments were estimated to cost between 6 and 10 million while MNA costs were estimated to be approximately 1 million (D17451Q). 

The most important of these explosive isomers is the alpha-trinitrotoluene, known as TNT. In crude, commercial TNT, 4 to 5% of impurities are present, consisting mainly of. a mixture of beta-, or 2,3,4-, and gamma, or 3,4,6-trinitrotoluenes. These impurities may be removed by treating the crude TNT with an aqueous solution of sodium sulfite. Ac-, cording to Davis (Ref 3) the beta- and gamma-isomers react with lead oxide in alcohol to form lead dinitrocresolates, while alpha-TNT remains unaffected under similar conditions Refs 1) M. Copisarow, Chem News 118, 13-14 (1919) CA 13, 791 (1919) 2) M.M. Kos-tevitch, Trinitrobenzene Trinitrotoluene, Paris (1927) 3) Davis (1943) p 147... 

In spite of being hydrolysed so readily its chemical stability is exceptionally high. Haid, Becker and Dittmar [67] report that dinitrodimethyloxamide, like trinitrotoluene, tetryl and penthrite, does not evolve oxides of nitrogen on being heated at 100°C for 30 days. 

Nitrotoluenes, Van No strand, NY(1918) 2)M.Kostevitch, "Tarry Matter of Alpha Trinitrotoluene, Part II, Imprd Art Vol-taire,P aris( 1927), 8 3)Sidgwick( 19 37), 259 et seq 4)Davis(1943), 136-7, 147, 149-51 170-1 5>negering( 1950), 139 seq 6) Dept of the Army TM 9-1910( 1955), 146 Alkalies, Action on Nitric Esters. Organic nitrates in general are readily saponified by alkaline solns. A simple metathetical reaction to yield the alkali nitrate and alcohol does not take place instead, as a result of simultaneous oxidation and reduction, alkali nitrite and a variety of products are formed depending on the conditions of the reaction. The resistance of different nitric esters to alkalies varies considerably. Thus, starch nitrate is decomposed much more slowly than cellulose nitrate and amylopectin nitrate still more alowly... 

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