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Chapter 1 Trinitrotoluene

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"TNT" redirects here. For other uses, see TNT (disambiguation).
Trinitrotoluene

Names
IUPAC name
2-Methyl-1,3,5-trinitrobenzene
Other names
2,4,6-Trinitrotoluene,
TNT, Trilite, Tolite, Trinol, Trotyl, Tritolo, Tritolol,
Triton, Tritone, Trotol, Trinitrotoluol,
2,4,6-Trinitromethylbenzene
Identifiers
Abbreviations
TNT
CAS Registry
118-96-7
Number
ChEMBL
ChEMBL1236345
ChemSpider
8073
DrugBank
DB01676
EC number
204-289-6
InChI[show]
Jmol-3D images
Image
KEGG
C16391
PubChem
11763
RTECS number
XU0175000
SMILES[show]
UNII
H43RF5TRM5
0209 Dry or wetted with <
30% water
UN number
0388, 0389 Mixtures with
trinitrobenzene,
hexanitrostilbene
Properties
Molecular formula C7H5N3O6

Molar mass
Appearance
Density
Melting point
Boiling point
Solubility in water
Solubility in ether,
acetone, benzene,
pyridine

227.13 gmol1
Pale yellow solid. Loose
"needles", flakes or prills before
melt-casting. A solid block after
being poured into a casing.
1.654 g/cm3
80.35 C (176.63 F; 353.50 K)
240.0 C (464.0 F; 513.1 K)
(decomposes)[1]
0.13 g/L (20 C)
soluble

Explosive data
Shock sensitivity
Insensitive
Friction sensitivity Insensitive to 353 N
Detonation velocity 6900 m/s
RE factor
1.00
Hazards
MSDS
ICSC 0967
EU Index
609-008-00-4
Explosive (E)
Toxic (T)
EU classification
Dangerous for the environment
(N)
R-phrases
R2, R23/24/25, R33, R51/53
S-phrases
(S1/2), S35, S45, S61

NFPA 704

4
2
4

Flash point

167 C (333 F; 440 K)


Related compounds
picric acid
Related compounds hexanitrobenzene
2,4-Dinitrotoluene
Except where noted otherwise, data is given for
materials in their standard state (at 25 C (77 F),
100 kPa)
verify (what is: / ?)
Infobox references

Trinitrotoluene /tranatrtlj.in/ (TNT), or more specifically 2,4,6-trinitrotoluene, is a chemical


compound with the formula C6H2(NO2)3CH3. This yellow-colored solid is sometimes used as a reagent in

chemical synthesis, but it is best known as a useful explosive material with convenient handling properties.
The explosive yield of TNT is considered to be the standard measure of strength of bombs and other
explosives. In chemistry, TNT is used to generate charge transfer salts.

Contents

1 History
2 Preparation
3 Applications
4 Explosive character
5 Energy content
6 Detection
7 Safety and toxicity
8 Ecological impact
o 8.1 Aqueous solubility
o 8.2 Soil adsorption
o 8.3 Chemical breakdown
o 8.4 Biodegradation
9 See also
10 References
11 External links

History

Trinitrotoluene melting at 81 C

M107 artillery shells. All are labelled to indicate a filling of "Comp B" (mixture of TNT and RDX) and have
fuzes fitted

Breakdown of production by branch of TNT in the German army between 1941 and the first quarter of 1944
by thousands of tons per month

Detonation of the 500-ton TNT explosive charge as part of Operation Sailor Hat in 1965. The white blastwave is visible on the water surface and a shock condensation cloud is visible overhead.

World War I-era HE artillery shell for a 9.2 inch howitzer. The red band indicates it is filled and the green
band (marked "Trotyl") indicates that the filling is TNT
TNT was first prepared in 1863 by German chemist Julius Wilbrand[2] and originally used as a yellow dye.
Its potential as an explosive was not appreciated for several years mainly because it was so difficult to
detonate and because it was less powerful than alternatives. TNT can be safely poured when liquid into shell
cases, and is so insensitive that in 1910, it was exempted from the UK's Explosives Act 1875 and was not
considered an explosive for the purposes of manufacture and storage.[3]
The German armed forces adopted it as a filling for artillery shells in 1902. TNT-filled armour-piercing
shells would explode after they had penetrated the armour of British capital ships, whereas the British
lyddite-filled shells tended to explode upon striking armour, thus expending much of their energy outside the
ship.[3] The British started replacing lyddite with TNT in 1907.
The United States Navy continued filling armor piercing shells with explosive D after some other nations
had switched to TNT; but began filling naval mines, bombs, depth charges, and torpedo warheads with
burster charges of crude grade B TNT with the color of brown sugar and requiring an explosive booster
charge of granular crystallized grade A TNT for detonation. High explosive shells were filled with grade A
TNT, which became preferred for this other use as industrial chemical capacity became available for
removing xylene and similar hydrocarbons from the toluene feedstock and other nitrotoluene isomer
byproducts from the nitrating reactions.[4]
TNT is still widely used by the United States military, as well as construction companies around the world.
The majority of TNT currently used by the US military is manufactured by Radford Army Ammunition
Plant near Radford, Virginia.[citation needed]

Preparation
In industry, TNT is produced in a three-step process. First, toluene is nitrated with a mixture of sulfuric and
nitric acid to produce mononitrotoluene (MNT). The MNT is separated and then renitrated to dinitrotoluene
or DNT. In the final step, the DNT is nitrated to trinitrotoluene or TNT using an anhydrous mixture of nitric
acid and oleum. Nitric acid is consumed by the manufacturing process, but the diluted sulfuric acid can be
reconcentrated and reused. Subsequent to nitration, TNT is stabilized by a process called sulfitation, where
the crude TNT is treated with aqueous sodium sulfite solution in order to remove less stable isomers of TNT
and other undesired reaction products. The rinse water from sulphitation is known as red water and is a
significant pollutant and waste product of TNT manufacture.[5]
Control of nitrogen oxides in feed nitric acid is very important because free nitrogen dioxide can result in
oxidation of the methyl group of toluene. This reaction is highly exothermic and carries with it the risk of a
runaway reaction leading to an explosion.
In the laboratory, 2,4,6-trinitrotoluene is produced by a two step process. A nitrating mixture of concentrated
nitric and sulfuric acids is used to nitrate toluene to a mixture of mono- and di-nitrotoluene isomers, with
cooling to maintain careful temperature control. The nitrated toluenes are then separated, washed with dilute
sodium bicarbonate to remove oxides of nitrogen, and then carefully nitrated with a mixture of fuming nitric
acid and sulfuric acid. Towards the end of the nitration, the mixture is heated on a steam bath. The

trinitrotoluene is separated, washed with a dilute solution of sodium sulfite and then recrystallized from
alcohol.

Applications
TNT is one of the most commonly used explosives for military and industrial applications. It is valued partly
because of its insensitivity to shock and friction, which reduces the risk of accidental detonation, compared
to other more sensitive high explosives such as nitroglycerin. TNT melts at 80 C (176 F), far below the
temperature at which it will spontaneously detonate, allowing it to be poured as well as safely combined
with other explosives. TNT neither absorbs nor dissolves in water, which allows it to be used effectively in
wet environments. Additionally, it is stable compared to other high explosives.
In order to initiate an explosion, TNT must first be detonated using a pressure wave from a more sensitive
explosive called an explosive booster.
Although blocks of TNT are available in various sizes (e.g. 250 g, 500 g, 1,000 g), it is more commonly
encountered in synergistic explosive blends comprising a variable percentage of TNT plus other ingredients.
Examples of explosive blends containing TNT include:

Amatex: (ammonium nitrate and RDX) [6]


Amatol:(ammonium nitrate [7])
Ammonal: (ammonium nitrate and aluminium powder plus sometimes charcoal).
Baratol: ( barium nitrate and wax [8])
Composition B ( RDX and paraffin wax [9] )
Composition H6
Cyclotol (RDX) [10]
Ednatol
Hexanite [11](hexanitrodiphenylamine[12][13]).
Minol
Octol
Pentolite
Picratol
Tetrytol
Torpex
Tritonal

Explosive character
Upon detonation, TNT decomposes as follows:
2 C7H5N3O6 3 N2 + 5 H2O + 7 CO + 7 C
2 C7H5N3O6 3 N2 + 5 H2 + 12 CO + 2 C
The reaction is exothermic but has a high activation energy in the gas phase (~62 kcal/mol). The condensed
phases (solid or liquid) show markedly lower activation energies of roughly 35 kcal/mol due to unique
bimolecular decomposition routes at elevated densities.[14] Because of the production of carbon, TNT
explosions have a sooty appearance. Because TNT has an excess of carbon, explosive mixtures with
oxygen-rich compounds can yield more energy per kilogram than TNT alone. During the 20th century,
amatol, a mixture of TNT with ammonium nitrate was a widely used military explosive.
Detonation of TNT can be done using a high velocity initiator or by efficient concussion.[15]

For many years, TNT used to be the reference point for the Figure of Insensitivity. TNT had a rating of
exactly 100 on the F of I scale. The reference has since been changed to a more sensitive explosive called
RDX, which has an F of I of 80.

Energy content
See also: TNT equivalent

Cross-sectional view of Oerlikon 20 mm cannon shells (dating from circa 1945) showing color codes for
TNT and pentolite fillings
Pentolite is a high explosive used for military and civilian purposes e.g. warheads and booster charges. TNT
is reported to contain 2.8 mega joules per kilogram explosive energy.[16] The actual heat of combustion is
14.5 megajoules per kilogram, which requires that some of the carbon in TNT react with atmospheric
oxygen, which does not occur in the initial event.[16] The explosive energy utilized by NIST is 4184 J/g
(4.184 MJ/kg).[17] The energy density of TNT is used as a reference-point for many other types of
explosives, including nuclear weapons, the energy content of which is measured in kilotons (~4.184
terajoules) or megatons (~4.184 peta joules) of TNT equivalent.
For comparison, gunpowder contains 3 megajoules per kilogram, dynamite contains 7.5 megajoules per
kilogram, and gasoline contains 47.2 megajoules per kilogram (though gasoline requires an oxidant, so an
optimized gasoline and O2 mixture contains 10.4 megajoules per kilogram).

Detection
Various methods can be used to detect TNT including optical and electrochemical sensors and explosivesniffing dogs.
In 2013, researchers from the Indian Institutes of Technology using noble-metal quantum clusters could
detect TNT at the sub-zeptomolar (1018 mol/m3) level.[18]

Safety and toxicity


TNT is poisonous, and skin contact can cause skin irritation, causing the skin to turn a bright yellow-orange
color. During the First World War, munition workers who handled the chemical found that their skin turned
bright yellow, which resulted in their acquiring the nickname "canary girls" or simply "canaries."
People exposed to TNT over a prolonged period tend to experience anemia and abnormal liver functions.
Blood and liver effects, spleen enlargement and other harmful effects on the immune system have also been
found in animals that ingested or breathed trinitrotoluene. There is evidence that TNT adversely affects male
fertility.[19] TNT is listed as a possible human carcinogen, with carcinogenic effects demonstrated in animal
experiments (rat), although effects upon humans so far amount to none [according to IRIS of March 15,
2000]. [20] Consumption of TNT produces red urine through the presence of breakdown products and not
blood as sometimes believed.[21]
Some military testing grounds are contaminated with TNT. Wastewater from munitions programs including
contamination of surface and subsurface waters may be colored pink because of the presence of TNT. Such
contamination, called "pink water", may be difficult and expensive to remedy.

TNT is prone to exudation of dinitrotoluenes and other isomers of trinitrotoluene. Even small quantities of
such impurities can cause such effect. The effect shows especially in projectiles containing TNT and stored
at higher temperatures, e.g. during summer. Exudation of impurities leads to formation of pores and cracks
(which in turn cause increased shock sensitivity). Migration of the exudated liquid into the fuze screw thread
can form fire channels, increasing the risk of accidental detonations; fuze malfunction can result from the
liquids migrating into its mechanism.[22] Calcium silicate is mixed with TNT to mitigate the tendency
towards exudation.[23]

Ecological impact
Because of its use in construction and demolition, TNT has become the most widely used explosive, and
thus its toxicity is the most characterized and reported. Residual TNT post explosion can partition between
multiple environmental including water, soil, atmosphere, biosphere.
The concentration of TNT in contaminated soil can reach 50 g/kg of soil, where the highest concentrations
can be found on or near the surface. In the last decade, the United States Environmental Protection Agency
(USEPA) has declared TNT a pollutant whose removal is priority.[24] The USEPA maintains that TNT levels
in soil should not exceed 17.2 gram per kilogram of soil and 0.01 milligrams per liter of water.[25]

Aqueous solubility
Dissolution involves how rapidly solid TNT in contact with water is solubilized. The relatively low aqueous
solubility of TNT causes the dissolution of solid particles to be continuously released to the environment
over extended periods of time.[26] Studies have shown that the TNT dissolved slower in saline water than in
freshwater. However, when salinity was altered, TNT dissolved at the same speed.[27] (Figure 2) Because
TNT is moderately soluble in water, it can migrate through subsurface soil, and cause groundwater
contamination.[28]

Soil adsorption
Adsorption measures the distribution between soluble and sediment sorbed contaminants following
attainment of equilibrium. Explosives such as TNT and its transformation products are known to adsorb to
surface soils and sediments, where they undergo reactive transformation or remained stored.[29] The
movement or organic contaminants through soils is a function of their ability to associate with the mobile
phase (water) and a stationary phase (soil). Materials that associate strongly with soils move slowly through
soil. Materials that associate strongly with water move through water with rates approaching that of ground
water movement.
The association constant for TNT with a soil is: 2.7-11 liters per kilogram of soil.[30] This means that TNT
has 1-10-fold tendency to adhere to a soil particulates than not when introduced into the soil.[26] Hydrogen
bonding and ion exchange are two suggested mechanisms of sorption between the nitro functional groups
and soil colloids.
The number of functional groups on TNT influences the ability to adsorb into soil. Adsorption coefficient
values have been shown to increase with an increase in the number of amino groups. Thus, sorption of the
TNT decomposition product 2,4-diamino-6-nitrotoluene (2,4-DANT) was greater than that for 4-amino-2,6dinitrotoluene (4-ADNT), which was greater than that for TNT.[26] Lower adsorption coefficients for 2,6DNT compared to 2,4-DNT can be attributed to the steric hindrance of the NO3 group in the ortho position.
Research has shown that in freshwater environments, with a high abundances of Ca2+, the sorption of TNT
and its transformation products to soils and sediments may be lower than observed in a saline environment,
dominated by K+ and Na+. Therefore, when considering the adsorption of TNT, the type of soil or sediment
and the ionic composition and strength of the ground water are important factors.[31]

The association constants for TNT and its degradation products with clays have been determined. Clay
minerals have a significant effect on the sorption of energetic compounds. and can be ranked, as seen in
Table 2. It should be noted that soil properties, such as organic carbon content and cation exchange capacity
had significant impacts of the adsorption coefficients reported in the table below.
Additional studies have shown that the mobility of TNT degradation products is likely to be lower than
TNT in subsurface environments where specific adsorption to clay minerals dominates the sorption
process.[31] Thus, the mobility of TNT and its transformation products are dependent on the characteristics
of the sorbent.[31] The mobility of TNT in groundwater and soil has been extrapolated from sorption and
desorption isotherm models determined with humic acids, in aquifer sediments, and soils.[31] From these
models, it is predicted that TNT has a low retention and transports readily in the environment.[24]
Compared to other explosives, TNT has a higher association constant with soil, meaning it adheres more
with soil than with water. Conversely, other explosives, such as RDX and HMX with low association
constants (ranging from 0.06-7.3 L/kg and 0-1.6 L/kg respectively) can move more rapidly in water.[26]

Chemical breakdown
TNT is a reactive molecule and is particularly prone to react with reduced components of sediments or
photodegradation in the presence of sunlight. TNT is thermodynamically and kinetically capable of reacting
with a wide number of components of many environmental systems. This includes wholly abiotic reactants,
like photons, hydrogen sulfide, Fe2+, or microbial communities, both oxic and anoxic.
Soils with high clay contents or small particle sizes and high total organic carbon content have been shown
to promote TNT transformation. Possible TNT transformations include reduction of one, two, or three nitromoieties to amines and coupling of amino transformation products to form dimers. Formation of the two
monoamino transformation products, 2-ADNT and 4-ADNT are energetically favored, and therefore are
observed in contaminated soils and ground water. The diamino products are energetically less favorable, and
even less likely are the triamino products.
The transformation of TNT is significantly enhanced under anaerobic conditions as well as under highly
reducing conditions. TNT transformations in soils can occur both biologically and abiotically.[31]
Photolysis is a major process that impacts the transformation of energetic compounds. The alteration of a
molecule in photolysis occurs in the presence of direct absorption of light energy by the transfer of energy
from a photosensitized compound. Phototransformation of TNT results in the formation of nitrobenzenes,
benzaldehydes, azodicarboxylic acids, and nitrophenols, as a result of the oxidation of methyl groups,
reduction of nitro groups, and dimer formation.[26]
Evidence of the photolysis of TNT has been seen due to the color change to pink of the wastewaters when
exposed to sunlight. Photolysis was more rapid in river water than in distilled water. Ultimately, photolysis
affects the fate of TNT primarily in the aquatic environment but could also affect the reaction when exposed
to sunlight on the soil surface.[31]

Biodegradation
The ligninolytic physiological phase and manganese peroxidase system of fungi can cause a very limited
amount of mineralization of TNT in a liquid culture; though not in soil. An organism capable of the
remediation of large amounts of TNT in soil has yet to be discovered.[32] Both wild and transgenic plants can
phytoremediate explosives from soil and water.[33]