| | 2,4,6-Trinitrotoluene Basic information |
| Product Name: | 2,4,6-Trinitrotoluene | | Synonyms: | TNT;1-Methyl-2,4,6-trinitrobenzene;2,4,6-TNT;2,4,6-Trinitrotolueen;2,4,6-trinitro-toluen;2,4,6-Trinitrotoluol;2,4,6-TRINITROTOLUENE;4-Methyl-1,3,5-trinitrobenzene | | CAS: | 118-96-7 | | MF: | C7H5N3O6 | | MW: | 227.13 | | EINECS: | 204-289-6 | | Product Categories: | Nitro;Organics;8000 Series Solidwaste Methods;Analytical Standards;AromaticsEnvironmental Standards;Chemical Class;Industrial/Fine Chemicals;Environmental Standards;ExplosivesEPA;Method 8330Analytical Standards;Nitro CompoundsChromatography;Solid WasteAlphabetic;TP - TZMore...Close...;Volatiles/ Semivolatiles | | Mol File: | 118-96-7.mol |  |
| | 2,4,6-Trinitrotoluene Chemical Properties |
| Melting point | 80.9℃ | | Boiling point | 335–340°C | | density | 1.654g/cm3 | | vapor pressure | 0.2 at 20 °C (NIOSH, 1997)4.26 at 54.76 °C, 2.557 at 72.49 °C, 4.347 at 76.06 °C (Knuden effusion method, Lenchitz andVelicky, 1970) | | refractive index | 1.5500 (estimate) | | Fp | 2 °C | | storage temp. | 2-8°C | | solubility | Solubility Very sparingly soluble in water; soluble in acetone, benzene; less soluble in ethanol | | form | crystals | | color | Yellow | | PH Range | Colorless (11.5) to orange (14.0) | | Water Solubility | 0.12g/L(20.0 ºC) | | Exposure limits | TLV-TWA (skin) 0.5 mg/m3 (ACGIH and MSHA), 1.50 mg/m3 (OSHA). | | Stability: | Unstable. Risk of explosion if heated or struck. Reacts violently - potentially explosively - with reducing agents. Reacts with heavy metals. | | Major Application | Explosive, energetic materials, preparation of diamond | | LogP | 1.65 at 20℃ | | CAS DataBase Reference | 118-96-7(CAS DataBase Reference) | | IARC | 3 (Vol. 65) 1996 | | EPA Substance Registry System | Trinitrotoluene (118-96-7) |
| | 2,4,6-Trinitrotoluene Usage And Synthesis |
| Description | 2,4,6-Trinitrotoluene (TNT) is a yellow, odourless, unstable solid. TNT does not occur
naturally in the environment. TNT is an explosive used in military shells, bombs, and
grenades; in industrial uses; and in underwater blasting. TNT is a high explosive that is
unaffected by ordinary shocks and therefore must be set off by a detonator. TNT is often
mixed with other explosives such as ammonium nitrate to form amatol. Because it is
insensitive to shock and must be exploded with a detonator, it is the most favoured explosive
used in munitions and construction. TNT reacts violently, is potentially explosively,
reacts with heavy metals, and is a chemical with risk of explosion if heated or struck. | | Chemical Properties | TNT exists in five isomers; 2,4,6-trinitrotoluene
is the most commonly used. It is a colorless to pale yellow
odorless solid (pellets, cast blocks, and cast slabs) or
crushed flakes. | | Physical properties | Colorless to light yellow, odorless monoclinic crystals. Soluble in alcohol and ether; insoluble in water. | | History | TNT is the abbreviation of the aromatic nitrated aromatic compound 2,4,6-trinitrotoluene. It is a pale-yellow crystalline solid that was first synthesized in 1863 by the German chemist Joseph Wilbrand (1811 1894), but it was not immediately used as an explosive. TNT is made by nitrating toluene using nitric acid, sulfuric acid, and oleum (a mixture of sulfuric acid and SO3). Nitration of toluene occurs in stages, with the nitro units added sequentially in a stepwise process as the reaction proceeds. The last nitro unit is accomplished by using oleum (SO3 dissolved in sulfuric acid). After nitration, unused acids are recycled, and the product is washed with sodium sulfite and water to remove impurities.
TNT is one of the most common explosives. Unlike nitroglycerin, TNT will not explode when subjected to signifi cant shock and friction. It is classifi ed as a secondary explosive, which means it requires an initiating explosive to detonate. The Germans began production of TNT in the last decade of the 19th century, and it was used in the mining industry. Military engineers adapted mining explosives for use in warfare, and TNT started to be incorporated in munitions in 1902. The first widespread use of TNT occurred during World War I. Between World War I and II, TNT replaced picric acid as the explosive of choice in munitions.
It was also mixed with other compounds to produce more powerful explosives with
unique characteristics. Amatol is a mixture containing between 40% and 80% ammonium
nitrate and TNT. Pentolite is a mixture of PETN (pentaerythritol tetranitrate) and TNT.
Another common explosive mixture is RDX (cyclotrimethylenetrinitramine) and TNT. RDX
is an abbreviation for Royal Demolition Explosive. | | Uses | TNT has limited use as a chemical intermediate in pharmaceuticals and for photographicchemicals. It is used to produce other nitrated compounds. Removing the methylgroup from TNT produces 1,3,5-trinitobenzene, and removing methyl and a nitro groupproduces 1,3-dinitrobenzenze (1,3-DNB). Both trinitrobenzene and dinitrobenzene can beused as explosives. Trinitrobenzene is more powerful than TNT but less sensitive to impact.Dinitrobenzene has been used in the production of nitrocellulose, which is used for smokelessgunpowder and guncotton. | | Uses | 2,4,6-Trinitrotoluene (TNT) is used as a high explosive in mining and in military. It is produced by nitration of toluene with a mixture of nitric and sulfuric acids. | | Uses | Explosive, intermediate in dyestuffs and photographic
chemicals. | | Definition | ChEBI: 2,4,6-trinitrotoluene is a trinitrotoluene having the nitro groups at positions 2, 4 and 6. It has a role as an explosive. It is functionally related to a 1,3,5-trinitrobenzene. | | Definition | triton: A nucleus of a tritium atom,consisting of a proton and two neutronsbound together; the ion T+ formed by ionization of a tritium atom. See also hydron. | | General Description | A slurry of a yellow water-insoluble crystalline solid. Can burn, although difficult to ignite. When water has been driven off or evaporated the residue is easily ignited, burns vigorously, and is highly explosive . Produces toxic oxides of nitrogen during combustion. May explode under exposure to intense heat. Primary hazard is blast of an explosion, not flying projectiles or fragments. | | Reactivity Profile | TRINITROTOLUENE may begin a vigorous reaction that culminates in a detonation if mixed with reducing agents, including hydrides, sulfides and nitrides. May explode in the presence of a base such as sodium hydroxide or potassium hydroxide even in the presence of water or organic solvents. | | Health Hazard | Some are toxic and may be fatal if inhaled, swallowed or absorbed through skin. Contact may cause burns to skin and eyes. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may cause pollution. | | Health Hazard | The toxic effect of TNT are dermatitis, cyanosis, gastritis, yellow atrophy of the liver, somnolence, tremor, convulsions, and aplastic anemia. Sneezing, sore throat, and muscular pain have also been noted in people exposed to this compound. It is an irritant to skin, respiratory tract, and urinary tract. Prolonged exposure may produce liver damage. The oral LD50 value in rats is in the range 800 mg/kg.
Levine and coworkers (1990) have conducted a 6-month oral toxicity test of TNT in beagle dogs. The major toxic effects observed were hemolytic anemia, methemoglobinemia, liver injury, splenomegaly, and death. A dose of 32 mg/kg/day was lethal to the dogs.
TNT tested nongenotoxic to the bone marrow of mice and the liver of rats (Ashby et al. 1985). It produced a negative response at dose levels up to 1000 mg/kg in the liver assay. High levels of hemoglobin and red-colored urine in the TNT-treated rats suggest a possible carcinogenic hazard to the hemopoietic and urinary tissues of animals at toxic levels on chronic exposure (Ashby et al. 1985). . | | Fire Hazard | TNT is a high explosive. In comparison to many other high explosives, it is insensitive to heat, shock, or friction. Small amounts may burn quietly without detonation. However, when heated rapidly or subjected to strong shock, it detonates. Its detonation temperature is 470°C (878°F) and its velocity is between 5.1 and 6.9 km/s. In combination with other explosives, TNT is widely used as a military and industrial explosive. Amatol, cyclonite, and tetrytol are some of the examples of such explosive combinations. Amatol is a composition of 80% ammonium nitrate and 20% TNT by mass. TNT itself has a very high brisance.
Products from the detonation of 1.5-2.0 kg of TNT in air- and oxygen-deficient atmospheres consisted of low-molecularweight gases and high-molecular-weight polycyclic aromatic hydrocarbons (Johnson et al. 1988). Greiner and associates (1988) examined the soots produced from the detonation of cast composites of TNT mixed with nitroguanidine or RDX in 1 atmosphere of argon. The soot contained 25 wt% diamond 4-7 nm in diameter, the IR spectrum and particle size of which resembled those from meteorites.
. | | Safety Profile | Suspected carcinogen.
Poison by subcutaneous route. Moderately
toxic by ingestion. Human systemic effects
by ingestion: hallucinations or distorted
perceptions, cyanosis, and gastrointestinal
changes. Experimental reproductive effects.
Mutation data reported. A skin irritant. Has
been implicated in aplastic anemia. Can
cause headache, weakness, anemia, liver
injury. May be absorbed through skin. Flammable or explosive when exposed to
heat or flame. Moderate explosion hazard;
will detonate under strong shock. It
detonates at around 24O℃ but can be
distilled safely under reduced pressure. It is a
comparatively insensitive explosive. In small
quantities it will burn quietly if not confined.
However, sudden heating of any quantity
will cause it to detonate; the accumulation of
heat when large quantities are burning will
cause detonation. In other respects it is one
of the most stable of all high explosives, and
there are but a few restrictions for its
handling. It is for this reason, from the
military standpoint, that TNT is
quantitatively the most used. It requires a
fall of 130 cm for a 2 kg weight to detonate
it. It is one of the most powerful high
explosives. It can be detonated by the usual
detonators and blasting caps (at least a No.
6). For full efficiency, the use of a highvelocity
initiator, such as tetryl, is required.
TNT is one of those explosives containing
an oxygen deficiency. In other words, the
addition of products that are oxygen rich
can enhance its explosive power. Also
monoand dinitrotoluene may be added for
reduction of the temperature of the
explosion and to make the explosion
flashless. Various materials are added to
TNT to make what are known as
permissible explosives. TNT may be
regarded as the equivalent of 40% dynamite
and can be used underwater. It is also used
in the manufacture of a detonator fuse
known as cordeau detonant. For the
military, TNT finds use in all types of
bursting charges, includmg armor-piercing
types, although it is somewhat too sensitive
to be ideal for this purpose and has since
been replaced to a great extent by
ammonium picrate. It is a relatively
expensive explosive and does not compete
seriously with dynamite for general
commercial use.
Highly dangerous; explodes with shock or
heating to 297°C. Various materials can
reduce the explosive temperature: red lead -
(to 192℃), sodium carbonate (to 218℃),
potassium hydroxide (to 192°C). Mixtures
with sodium dichromate + sulfuric acid may
ignite spontaneously. Reacts with nitric acid
+ metals (e.g., lead or iron) to form
explosive products more sensitive to shock,
friction, or contact with nitric or sulfuric
acids. Reacts with potassium hydroxide
dissolved in methanol to form explosive acinitro
salts. Bases (e.g., sodium hydroxide,
potassium iodide, tetramethyl ammonium
octahydrotriborate) induce deflagration in
molten TNT. Can react vigorously with
reducing materials. When heated to
decomposition it emits highly toxic fumes of
NOx. See also NITRO COMPOUNDS of
AROMATIC HYDROCARBONS and
EXPLOSIVES, HIGH. | | Potential Exposure | TNT is used as an explosive, that is,
as a bursting charge in military explosive shells, bombs,
grenades, and mines; and an intermediate in dyestuffs and
photographic chemicals. | | Carcinogenicity | In bacterial and mammalian in vitro cell
systems TNT is a direct-acting mutagen.
However, inclusion of exogenous metabolic
activation appears to abolish the genotoxicity.
In vivo assays of TNT have not shown it to be
genotoxic, suggesting that TNT may be
reduced to nonmutagenic metabolic products
in the whole animal. | | Source | Generated as a waste from munitions and defense industries, leaching from unexploded
land mines.
Drinking water standard: No MCLGs or MCLs have been proposed, however, a DWEL of 20
μg/L was recommended (U.S. EPA, 2000). | | Environmental fate | Biological. 4-Amino-2,6-dinitrotoluene and 2-amino-4,6-dinitrotoluene, detected in
contaminated groundwater beneath the Hawthorne Naval Ammunition Depot, NV, were reported
to have formed from the microbial degradation of 2,4,6-trinitrotoluene (Pereira et al., 1979). 2,4,6-
Trinitrotoluene (220 μM) degraded in aerobic sludge containing molasses (3.3 g/L). Though 2,4,6-
trinitrotoluene disappeared completed in 15 h, only 0.1% was mineralized to carbon dioxide.
Under aerobic conditions, intermediate compounds reported in the biotransformation of 2,4,6-
trinitrotoluene to 2,4,6-triaminotoluene were 4-hydroxyamino-2,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene,
2,4-diamino-6-nitrotoluene, 2-hydroxyamino-4,6-dinitrotoluene, 2-amino-4,6-
dinitrotoluene, 2,6-diamino-4-nitrotoluene. Under abiotic conditions (pH 2 to 3), the following
hydroxylated compounds formed: 2-hydroxy-4,6-diaminotoluene, 2,6-dihydroxy-4-aminotoluene,
4-hydroxy-2,6-diaminotoluene, 2,4-dihydroxy-6-aminotoluene, and 2,4,6-trihydroxytoluene.
Under biotic conditions (pH 7.0), two azo derivatives were produced: 2,2′,4,4′-tetraamino-6,6′-
azotoluene and 2,2′,6,6′-tetraamino-4,4′-azotoluene (Hawari et al., 1998).
Chemical. Although no products were identified, 2,4,6-trinitrotoluene (1.5 x 10-5 M) was
reduced by iron metal (33.3 g/L acid washed 18 to 20 mesh) in a carbonate buffer (1.5 x 10-2 M) at
pH 5.9 and 15 °C. Based on the pseudo-first-order disappearance rate of 0.0330/min, the half-life
was 21.0 min (Agrawal and Tratnyek, 1996). 2,4,6-Trihydroxytoluene was detected after 2,4,6-
trinitrotoluene in water was heated to 100 °C (Hawari et al., 1998).
Will detonate upon heating (NIOSH, 1997).
2,4,6-Trinitrotoluene will not hydrolyze in water because it does not contain a hydrolyzable
funcational group. | | storage | TNT is stored in a permanent magazine, separated from combustible and oxidizable materials, initiators, and heat sources. It is shipped in amounts not exceeding 60 lb (27 kg) in weight in metal containers enclosed in wooden or fiberboard boxes. | | Shipping | UN1356 Trinitrotoluene, wetted with not <30%
water, by mass, Hazard Class: 4.1; Labels: 4.1-Flammable
solid. UN0209 Trinitrotoluene or TNT, dry or wetted with
< 30% water, by mass, Hazard Class: 1D; Labels:1DExplosive
(with a mass explosion hazard); D-Substances or
articles which may mass detonate (with blast and/or fragment
hazard) when exposed to fire. | | Purification Methods | Crystallise TNT from *benzene and EtOH. Then fuse (CARE) and allow to crystallise under vacuum. Gey, Dalbey and Van Dolah [J Am Chem Soc 78 1803 1956] dissolved TNT in acetone and added cold water (1:2:15), the precipitate was filtered off, washed free from solvent and stirred with five parts of aqueous 8% Na2SO3 at 50-60o for 10minutes. This was filtered, washed with cold water until the effluent was colourless, and air dried. The product was dissolved in five parts of hot CCl4, washed with warm water until the washings were colourless and TNT was recoverd by cooling and filtering. It was recrystallised from 95% EtOH and carefully dried over H2SO4. The dry solid should not be heated without taking precautions for a possible EXPLOSION. Work with small quantities. [Beilstein 5 H 347, 5 I 172, 5 II 268, 5 III 767, 5 IV 873.] | | Toxicity evaluation | TNT increases UDP glucuronyl transferase in the liver and
kidneys. It increases renal epoxide hydrolase activity. Animal
studies have suggested covalent binding between TNT and
macromolecular proteins, including serum albumin, hemoglobin
(Hb), hepatic and renal proteins, and possibly lens
protein. The Hb adduct was dose dependent. Macromolecular
binding is likely to be correlated with toxic effects; however, it is
unclear if a cause and effect relationship can be established.
Formation of organic nitro radicals was also hypothesized
based on hemolysis in glucose 6 phosphate dehydrogenase
(G6PD)-deficient TNT workers. G6PD is a limiting factor in the
maintenance of cellular glutathione, which protects against
oxidative damage. TNT was also found to be oxidized oxyhemoglobin,
resulting in methemoglobin formation. | | Incompatibilities | Sensitive to shock and heat. Incompatible
with initiating explosives, combustible materials. Aromatic
nitro compounds, such as trinitrobenzene, range from slight to
strong oxidizing agents. Keep away from strong reducing
agents, including hydrides, alkali metals; aluminium and
other metal powder; phosphorus; sulfides and nitrides, alkaline
material, strong bases; contact may initiate vigorous reactions
that culminates in a detonation. The aromatic nitro
compounds may explode in the presence of a base such as
sodium hydroxide or potassium hydroxide even in the presence
of water or organic solvents. The aromatic nitro
compounds may explode in the presence of a base such as
sodium hydroxide or potassium hydroxide even in the presence
of water or organic solvents. Incompatible with
strong oxidizers (chlorates, nitrates, peroxides, permanganates,
perchlorates, chlorine, bromine, fluorine, etc.); contact
may cause fires or explosions. | | Waste Disposal | TNT is dissolved in acetone
and incinerated. The incinerator should be equipped with
an afterburner and a caustic soda solution scrubber. |
| | 2,4,6-Trinitrotoluene Preparation Products And Raw materials |
|
