Trinitrotoluenes

6-trinitrotoluene (two four six try-nye-troh-TOL-yoo-een), or TNT, is a yellow odorless solid that occurs in the form of crystalline needles. Its major use is in the manufacture of explosives. It may be used alone or in combination with other explosive chemicals. Although not as powerful as some other explosives, it has the advantage of being relatively insensitive to shock. Workers can handle the explosive without fear that it will suddenly explode if dropped or jarred. In fact, a blasting cap or detonator is needed to cause TNT to explode. Blasting caps and detonators are very sensitive explosives that can be attached to less sensitive explosives like TNT. Any small shock to the blasting cap or detonator will cause it to explode. That explosion, in turn, causes the less sensitive explosive, such as TNT, to blow up. 

TNT was discovered by the German chemist Joseph Wil-brand (1811-1894) in 1863, although the compound was not recognized as an explosive until almost thirty years later. The compound was first produced commercially in Germany 

6 Trinitrotoluene. Red atoms are oxygen white atoms are hydrogen black atoms are carbon and blue atoms are nitrogen. Gray sticks indicate double bonds. Striped sticks indicate a benzene ring. 

The method developed by Wilbrand for manufacturing TNT is simple, efficient, and inexpensive, and remains the 

During World War I (1914-1918), people who made explosives for the military (usually women and girls) were sometimes called canary girls. Their name came from the fact that their skin turned yellow when exposed to solid TNT. Women with red hair also found their hair turning an orangish or ginger color because of exposure to TNT. 

Other Names Toluene, 2,4,6-trinitro- a-TNT 1-Methyl-2,4,6-trinitrobenzene 2,4,6-Trinitrotoluene 2-Methyl-l,3,5-trinitrobenzene 4-Methyl-l,3,5-trinitrobenzene Gradetol NSC 36949 TNT ToUt Tolite Trinitrotoluene Tritol Tritol (explosive) Trotyl Trotyl oil sym-Trinitrotoluene sym-Trinitrotoluol 

CA Index Name Benzene, 2-metliyl-l,3,5-trinitro-CAS R istry Number 118-96-7 Merck Index Number 9730 Chemical Structure 

Chemical/Dye Class Nitro Molecular Formula C7H5N3O5 Molecular Weight 227.13 pH Range 11.5-14.0 

Solubility Very sparingly soluble in water soluble in acetone, benzene less soluble in ethanol Melting Point 80.1°C Boiling Point 335-340°C Synthesis Synthetic methodsi-  

Major Applications Explosive,3 -io energetic materials, - 2 preparation of diamond -is Safety/Toxicity Ecotoxicity,i6 genotoxicity, cytotoxicity,oral toxicity, phytotoxicity,2o human toxicological effect, enviromnental pollutants, soil toxicity, mutagenicity  

Toluene is easily nitrated since it has an alkyl (-CH3) group attached to the benzene ring. It can be prepared by direct nitration of toluene with a mixture of nitric acid and sulfuric acid. 

The nitration mechanism is similar to that of the nitration of benzene. 

Trinitrotoluene is a crystalline solid that melts at 81°C. It is widely used as an explosive (TNT, tritol) in shells and bombs. It is not as sensitive to shock and friction as other explosives can be. 

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Trinitrotoluene (TNT) is made by nitration of toluene. Display electrostatic potential maps for toluene, 4-nitrotoluene (the first nitration product) and 2,4-dinitrotoluene (the second nitration product). Are the second and third nitration steps likely to be easier or more difficult than the initial nitration of toluene Explain. 

The only known example of this type of cyclization is the synthesis of dibenz[, /]azepines 457 from appropriate salicylaldehyde 454 and 2,4, 6-trinitrotoluene (455) via the corresponding intermediate 456 (Scheme 72) (62M766). 

Included are four samples of NC of different degrees of nitration and one sample each of the high expls TNT (2,4,6-trinitrotoluene) and HMX (1,3,5,7-tetranitro-l, 3,5,7-tetrazacyclooctane). 

The flash photolysis-of 2,4,6-trinitrotoluene solns (TNT) indicated a photochemically induced isomerization leading to the aci-quinoid isomer... 

Red Water — which can be almost black at times - also contains dissolved TNT however, it is not an incidental stream like Pink Water it is a major by-product stream from TNT manuf. The mixed-acid nitration of toluene yields not only 2,4,6-trinitrotoluene, the desired product, but also a host of other isomers and by-products amounting to approx 4.5% of the total yield and it is necessary to remove them from the product. They are removed by extraction with a Na sulfite—Na carbonate soln which sulfonates and dissolves them the extract is called Red Water. Red Water is a very complex and somewhat variable mixt containing 15% or so of sulfonated or sellited nitrobodies and a number of inorganic salts. Typical components are w, NajSOj—NaS04, NaN02— NaNOj, sulfonated or... 

Some interesting results have been obtained by Akand and Wyatt56 for the effect of added non-electrolytes upon the rates of nitration of benzenesulphonic acid and benzoic acid (as benzoic acidium ion in this medium) by nitric acid in sulphuric acid. Division of the rate coefficients obtained in the presence of nonelectrolyte by the concentration of benzenesulphonic acid gave rate coefficients which were, however, dependent upon the sulphonic acid concentration e.g. k2 was 0.183 at 0.075 molal, 0.078 at 0.25 molal and 0.166 at 0.75 molal (at 25 °C). With a constant concentration of non-electrolyte (sulphonic acid +, for example, 2, 4, 6-trinitrotoluene) the rate coefficients were then independent of the initial concentration of sulphonic acid and only dependent upon the total concentration of non-electrolyte. For nitration of benzoic acid a very much smaller effect was observed nitromethane and sulphuryl chloride had a similar effect upon the rate of nitration of benzenesulphonic acid. No explanation was offered for the phenomenon. 

This reaction cannot be elementary. We can hardly expect three nitric acid molecules to react at all three toluene sites (these are the ortho and para sites meta substitution is not favored) in a glorious, four-body collision. Thus, the fourth-order rate expression 01 = kab is implausible. Instead, the mechanism of the TNT reaction involves at least seven steps (two reactions leading to ortho- or /mra-nitrotoluene, three reactions leading to 2,4- or 2,6-dinitrotoluene, and two reactions leading to 2,4,6-trinitrotoluene). Each step would require only a two-body collision, could be elementary, and could be governed by a second-order rate equation. Chapter 2 shows how the component balance equations can be solved for multiple reactions so that an assumed mechanism can be tested experimentally. For the toluene nitration, even the set of seven series and parallel reactions may not constitute an adequate mechanism since an experimental study found the reaction to be 1.3 order in toluene and 1.2 order in nitric acid for an overall order of 2.5 rather than the expected value of 2. 

The reduction of 2,4,6-trinitrotoluene with Fe° has been extensively studied (references in Bandstra et al. 2005), and it has hnally produced 2,4,6-triaminotoluene that could undergo polymerization. 

Bandstra JZ, R Miehr, RL Johnson, PG Tratnyek (2005) Reduction of 2,4,6-trinitrotoluene by iron metal kinetic controls on product distributions in batch experiments. Environ Sci Technol 39 230-238. 

Godejohann M, M Astratov, A Preiss, K Levsen, C Miigge (1998) Application of continuous-flow HPLC-proton-nuclear magnetic resonance spectroscopy and HPLC-thermospray spectroscopy for the structrual elucidation of phototransformation products of 2,4,6-trinitrotoluene. Anal Chem 70 4104-4110. 

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. 

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