TNT preparation

Impurities Present in TNT Prepared by Continuous Nitration and Purification a... 

In practice, in the TNT preparation, the mononitration is carried out in a batch process by nitrating 1,600 lb of toluene with 11,000 lb of the acid listed above. The nitric ratio is then... 

It is prepared by the direct nitration of toluene with a mixture of nitric and sulphuric acids. TNT is a very stable, violent and powerful high explosive, but less sensitive to shock and friction than picric acid. It is widely used as a filling for shells, bombs, etc. often mixed with ammonium nitrate and other high explosives. The lower grades of TNT may contain isomers which under hot storage conditions may give rise to exudation. 

Hexanitrostilbene may be prepared by a dding a solution of TNT ia tetrahydrofuran and methanol at 5°C to aqueous sodium hypochlorite. To this mixture a 20% solution of trimethyl amine hydrochloride is added at 5—15°C. Hexanitrostilbene precipitates, and is filtered and washed with methanol and... 

The Siindberg indole synthesis using aromadc azides as precursors of nitrenes has been used in synthesis of various indoles. Somekmds of aryl azides are readily prepared by S Ar reacdon of aromadc nitro compounds v/ilh an azide ion. For example, 2,4,6-trinitrotoliiene (TNT can be converted into 2-aryl-4,6-dinitroindole, as shovmin Eq. 10.60. ... 

The best yield, 95%, was obtained with the K salt (Ref 38). It is formed in small amts during the nitration of toluene to prepare TNT (Refs 37 38), and has been held responsible for exp Ins which have occurred in TNT mfg plants. 

A three-step nitration process of toluene is described. The advantages of the modified process are reduced waste, less hazardous operation, reduced oleum requirement, partial replacement of coned HN03 with dil HN03, and higher rate of toluene flow into the reactor (Ref 86) The continuous process of H.C. Prime (Ref 73) for preparing TNT was studied by thin-layer chromatography on silica gel with a starch binder and a fluorescent indicator. The nitration... 

A linear relationship between Chapman-Jouguet pressure and density was confirmed for Cyclotol and Octol (Ref 28). Despite the near-equal performance of RDX and HMX at equal densities there appears to be no economical way of making the density of RDX equal to the cast density of HMX. Dinitrobenzene (DNB) has been evaluated as an economical or emergency substitute for TNT but charges prepared with DNB gave somewhat poorer performance than... 

Pandastites were inexpensive and easy to prepare, and were very powerful, some possessing a greater brisance and higher detonation velocity than either TNT or PA... 

Pyridine Perchlorate is almost as powerful as TNT (Pb block expansion 95% TNT, 87% PA), but is much more sensitive to impact (FI 40% PA), being comparable to PETN in this respect (Refs 4 5). Kuhn (Ref 7) states that it can be detonated on impact, but is normally considered a stable intermediate, suitable for purification of pyridine. Occasionally explns have occurred when the salt was disturbed (Ref 11), which have been variously attributed to the presence of ethyl perchlorate, AP or chlorates. A safer preparative modification is described (Ref 8). It explds on heating to above 335°, or at a lower temp if AP is present (Ref 10). According to Mellor (Ref 9), the salt can expld violently in contact with metals, while Zacherl (Ref 6) describes a lab expln which occurred during the distn of pyridine liberated from its perchlorate... 

Pure PETN is too sensitive to friction and impact for direct application for military purposes. It can usefully be mixed with plasticised nitrocellulose, or with synthetic rubbers to obtain plastic or mouldable explosives. The commonest application, however, is in conjunction with TNT in the form of pentolites. Pentolites are usually obtained by incorporating PETN into molten TNT. A small amount of the PETN goes into solution, but the bulk remains suspended in the liquid and the whole mix can suitably be used in preparing cast charges. Pentolites containing 20-50% PETN are the commonest in practice. 

The preparation and properties of TNT are described in Chapter 3. Next to nitroglycerine, TNT is the most important sensitising constituent of commercial explosives. For such purposes it does not need to have the high purity demanded for the military product, but otherwise the material is identical. 

A 20 g sample, prepared and stored in a dry box for several months, developed a thin crust of oxidation/hydrolysis products. When the crust was disturbed, a violent explosion occurred, later estimated as equivalent to 230 g TNT. A weaker explosion was observed with potassium tetrahydroaluminate. The effect was attributed to superoxidation of traces of metallic potassium, and subsequent interaction of the hexahydroaluminate and superoxide after frictional initiation. Precautions advised include use of freshly prepared material, minimal storage in a dry diluent under an inert atmosphere and destruction of solid residues. Potassium hydrides and caesium hexahydroaluminate may behave similarly, as caesium also superoxidises in air. 

A rubber glove and a box of cotton waste fell into a tank of spent nitrating acid from the preparation of TNT. The total contents of the tank ignited, leading to a series of explosions which caused severe damage and some 900 casualties, including 82 killed. 

Prepare a charge of TNT or plastic explosive % to 1 pound in weight. 

Figure 6.13. Experimental arrangement of the hot-explosive compaction method for the preparation of consolidated Ni-Al alloys (after Kecskes etal. 2004). (a) Precursor powder sample inside a steel-tube container placed in, (b) an asbestos thermal insulation sheet (c) a concentric card-box filled with the powdered explosive (80% NH4NO3 + 20% TNT) (d) threaded steel plugs serving as contacts for the preliminary heating and to be lifted off just before detonating the explosive (e) detonating cords.

Fluorescent cellulose triacetate membranes were prepared by incorporation of pyrene-butyric acid (219), and were applied to in situ detection of ground water contamination by explosives, based on fluorescence quenching by the nitro groups LOD 2 mg/L of DNT (220) and TNT (221) and 10 mg/L for RDX (276) the response follows the Stern-Volmer law for DNT and TNT442. 

The tests with the 12-kW system in Demo II successfully confirmed that this technology is capable of destroying the components (nitrocellulose and nitroglycerine) of M28 propellant. For tetrytol, the destruction of TNT and tetryl was good. However, recalcitrant intermediate products were formed during the treatment of tetrytol, which AEA was still evaluating at the time the Demo II report was prepared (NRC, 2001b). 

Olah and Lin reported obtaining pure TNB (2) in 50 % yield from the nitration of m-dinitrobenzene (32) with nitronium tetrafluoroborate in fluorosulfuric acid at 150 °C higher yields of TNB can be obtained by reducing reaction time but the product then contains some unreacted m-dinitrobenzene. A solution of dinitrogen pentoxide in sulfuric acid at 160 °C is also reported to effect the conversion of m-dinitrobenzene to TNB. TNB is rarely prepared via these routes and is best obtained from TNT via an indirect route (Section 4.9). 

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... 

For the terrorist, TATP and HMTD offer easy sources of primary explosives. Consulting the do-it-yourself literature, it can be seen that there are two other commonly recommended primary explosives—lead azide Pb(N3)2 and mercury fulminate Hg(ONC)2, but these are difficult to prepare cleanly. The synthesis of diazodinitrophenol (DDNP) (Fig. 2.5), common in commercial detonators, is reported in such publications, but apparently is rarely attempted by clandestine chemists. Typically, the brisance of a primary is less than TNT, but the efficacy is the fact that a shock wave can result from a relatively mild insult. 

TATP is unique in that it is a material that never received any serious consideration for military or commercial applications. It was studied by numerous groups, but primarily for academic reasons. Minimal literature references exist on it. TATP was first reported by Wolfenstein in 1895 [6], Since that time, numerous recipes have been developed for its preparation. One of the most useful studies of its properties as an explosive was conducted by Rohrlich and Sauermilch [7], They determined that TATP had a TNT equivalency of approximately 88% based on lead block expansion. They prepared a firing train consisting of 0.05 g TATP (pressed at 250 kg/cm2) in contact with pentaerythrital tetranitrate (PETN) to produce reliable blasting caps. Other experiments determined that a 0.16-g portion of the peroxide (density = 1.35 g/cm3) could initiate TNT. 

On the final day of testing a TNT demolition charge was substituted for the test target constructed from the TNT simulant. The block of explosive was prepared in a manner consistent with how the block would normally be deployed for use. The block was then deployed from the post as previously described. The sensor was positioned at the downcurrent side of the post at a distance of approximately 3 ft. The sensor immediately indicated a strong response to the explosive. 

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