nitroglycerin

Nitroglycerin
IUPAC name	1,2,3-trinitroxypropane
Other names	1,3-dinitrooxypropan-2-yl nitrate propane-1,2,3-triyl trinitrate
Identifiers
CAS number	55-63-0 Y
PubChem	4510
UN number	0143, 0144, 1204, 3064
SMILES	C(C(CO[N+](=O)[O-])O[N+](=O)[O-])O[N+](=O)[O-]
Properties
Molecular formula	C3H5N3O9
Molar mass	227.09 g mol−1
Appearance	Clear yellow/colorless oily liquid
Density	1.6 g/cm³ at 15 °C
Melting point	13.2 °C, 286 K, 56 °F
Boiling point	Decomposes at 50-60 °C (122-140 °F)
Explosive data
Shock sensitivity	high
Friction sensitivity	high
Explosive velocity	7700 m/s
RE factor	1.50
Hazards
NFPA 704	3 3 4
Y (what is this?)  (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Nitroglycerin (NG), (United States spelling) also known as nitroglycerine, (UK spelling), trinitroglycerin, trinitroglycerine, 1,2,3-trinitroxypropane and glyceryl trinitrate, is a heavy, colorless, oily, explosive liquid obtained by nitrating glycerol. Since the 1860s, it has been used as an active ingredient in the manufacture of explosives, specifically dynamite, and as such is employed in the construction and demolition industries. Similarly, since the 1880s, it has been used by the military as an active ingredient, and a gellatinizer for nitrocellulose, in some solid propellants, such as Cordite and Ballistite.

Nitroglycerin is also used medically as a vasodilator to treat heart conditions, such as angina and chronic heart failure.

History

Nitroglycerin was the first practical explosive stronger than black powder. It was synthesized by chemist Ascanio Sobrero in 1847, working under TJ Pelouze at the University of Turin. Sobrero initially called his discovery pyroglycerine, and warned vigorously against its use as an explosive. It was later adopted as a commercially useful explosive by Alfred Nobel. He experimented with safer ways to handle the dangerous substance; his younger brother Emil and several workers were killed in 1864 in a nitroglycerin explosion at the family's armaments factory in Heleneborg, in Sweden.^[1]

A year later, Nobel founded Alfred Nobel & Company in Germany, building an isolated factory in the Krümmel hills of Geesthacht near Hamburg. This business exported a liquid combination of nitroglycerin and gunpowder known as "Blasting Oil", but it was extremely unstable and difficult to transport, as shown in numerous catastrophes. The buildings of the Krümmel factory itself were destroyed on two occasions.^[2]

In April 1866, three crates of nitroglycerin were shipped to California for the Central Pacific Railroad, who wished to experiment with its blasting capability to speed the construction of the 1,659-foot (506 m) Summit Tunnel through the Sierra Nevada. One of the crates exploded, destroying a Wells Fargo office in San Francisco and killing fifteen people, leading to a complete ban on the transport of liquid nitroglycerin in California. The on-site manufacture of nitroglycerin was thus required for the remaining hard-rock drilling and blasting required for the completion of America's First Transcontinental Railroad.^[3]

Liquid nitroglycerin was widely banned elsewhere as well and this finally led to Alfred Nobel & Company's development of dynamite in 1867, made by mixing the nitroglycerin with the diatomaceous earth (kieselguhr) found in the Krümmel hills. Similar mixtures, such as dualine (1867), lithofracteur (1869), and gelignite (1875), mixed nitroglycerin with other inert absorbents—many different combinations were tried in order to get around Nobel's tightly controlled patents. Dynamites containing nitrocellulose, which increase the viscosity of the mix, are commonly known as "gelatins."

Following discoveries that amyl nitrite helped to alleviate chest pain, Doctor William Murrell experimented with the use of nitroglycerin to alleviate angina pectoris and reduce blood pressure. He began treating patients with small doses in 1878, and it was soon adopted into widespread use after he published his results in The Lancet in 1879. The medical establishment used the name "glyceryl trinitrate" or "trinitrin" to avoid alarming patients who associated nitroglycerin with explosions.^[4]

Instability and desensitization

In its pure form, it is a primary contact explosive (physical shock can cause it to explode) and degrades over time to even more unstable forms. This makes it highly dangerous to transport or use. In this undiluted form, it is one of the more powerful explosives, comparable to the more recent RDX and PETN, as well as the plastic explosive C-4—which contains over 90% RDX as its active ingredient.

Early in the history of this explosive it was discovered that liquid nitroglycerin can be "desensitized" by cooling to 5 to 10 °C (40 to 50 °F), at which temperature it freezes, contracting upon solidification. However, later thawing can be extremely sensitizing, especially if impurities are present or if warming is too rapid^[5]. It is possible to chemically "desensitize" nitroglycerin to a point where it can be considered approximately as "safe" as modern high explosive formulations, by the addition of approximately 10-30% ethanol, acetone^[6], or dinitrotoluene (percentage varies with the desensitizing agent used). Desensitization requires extra effort to reconstitute the "pure" product. Failing this, it must be assumed that desensitized nitroglycerin is substantially more difficult to detonate, possibly rendering it useless as an explosive for practical application.

A serious problem in the use of nitroglycerin results from its high freezing point 13 °C (55 °F). Solid nitroglycerin is much less sensitive to shock than the liquid, a feature common in explosives; in the past it was often shipped in the frozen state, but this resulted in a high number of accidents during the thawing process by the end user just prior to use. This disadvantage is overcome by using mixtures of nitroglycerin with other polynitrates; for example, a mixture of nitroglycerin and ethylene glycol dinitrate freezes at -29 °C (-20 °F).^[7]

Detonation

Nitroglycerin and any dilutents can certainly deflagrate, i.e. burn. However, the explosive power of nitroglycerin is derived from detonation: energy from the initial decomposition causes a pressure wave or gradient that detonates the surrounding fuel. This is a self-sustained shock wave that propagates through the explosive medium at some 30 times the speed of sound as a near-instantaneous pressure-induced decomposition of the fuel into a white hot gas. Detonation of nitroglycerin generates gases that would occupy more than 1,200 times the original volume at ordinary room temperature and pressure; moreover, the heat liberated raises the temperature to about 5,000 °C (9,030 °F).^[8] This is totally different from deflagration, which depends solely upon available fuel regardless of pressure or shock.

Manufacturing

The industrial manufacturing process often uses a nearly 50:50 mixture of concentrated sulfuric acid and concentrated nitric acid. This can be produced by mixing white fuming nitric acid (quite costly pure nitric acid in which oxides of nitrogen have been removed, as opposed to red fuming nitric acid) and concentrated sulfuric acid. More often, this mixture is attained by the cheaper method of mixing fuming sulfuric acid, also known as oleum, (sulfuric acid containing excess sulfur trioxide) and azeotropic nitric acid (consisting of around 70% nitric acid, the rest being water).

The sulfuric acid produces protonated nitric acid species, which are attacked by glycerin's nucleophilic oxygen atoms. The nitro group is thus added as an ester C-O-NO₂ and water is produced. This is different from an aromatic nitration reaction in which nitronium ions are the active species in an electrophilic attack of the molecules' ring system.

The addition of glycerin results in an exothermic reaction (i.e., heat is produced), as usual for mixed acid nitrations. However, if the mixture becomes too hot, it results in runaway, a state of accelerated nitration accompanied by the destructive oxidizing of organic materials of nitric acid and the release of very poisonous brown nitrogen dioxide gas at high risk of an explosion. Thus, the glycerin mixture is added slowly to the reaction vessel containing the mixed acid (not acid to glycerin). The nitrator is cooled with cold water or some other coolant mixture and maintained throughout the glycerin addition at about 22 °C (72 °F), much below which the esterification occurs too slowly to be useful. The nitrator vessel, often constructed of iron or lead and generally stirred with compressed air, has an emergency trap door at its base, which hangs over a large pool of very cold water and into which the whole reaction mixture (called the charge) can be dumped to prevent an explosion, a process referred to as drowning. If the temperature of the charge exceeds about 30 °C (86 °F) (actual value varying by country) or brown fumes are seen in the nitrator's vent, then it is immediately drowned.

Use as an explosive and a propellant

Alfred Nobel's patent application from 1864.

The main use of nitroglycerin, by tonnage, is in explosives such as dynamite and in propellants.

Alfred Nobel developed the use of nitroglycerin as a blasting explosive by mixing the nitroglycerine with inert absorbents particularly diatomaceous earth. He named this explosive dynamite and patented it in 1867. It was supplied ready for use in the form of sticks, individually wrapped in greased water-proof paper. Dynamite and similar explosives were widely adopted for civil engineering tasks, such as building railway tunnels and cuttings; and for quarrying.

Nitroglycerin was also adapted as a military propellant, for use in guns and rifles. Poudre B, invented in France in 1886, was one of the first military propellants to replace gunpowder; but it was based on nitrocellulose, not nitroglycerin. It was later found to be unstable.

Nitroglycerin is a high explosive that is so unstable, at the slightest jolt, friction or impact can cause it to detonate. The molecule contains oxygen, nitrogen, and carbon so when it explodes a lot of energy is released as the atoms rearrange to form new molecules with strong, stable bonds like N₂ and CO. However, it is the speed of the decompostition reaction which makes it such a violent explosive. A supersonic wave passing through the material is what causes the high explosive material to decompose almost instantaneously. This instantaneous destruction of all molecules is called a detonation, and what causes the destructive blast is a result from the rapid expansion of hot gases. Nitroglycerin has an advantage over some other high explosives, that no visible smoke is produced, therefore being able to be a "smokeless powder" ^[9].

Alfred Nobel then developed ballistite, by combining nitroglycerin and guncotton. He patented it in 1887. Ballistite was adopted by a number of European governments, as a military propellant. Italy was the first to adopt it. However, it was not adopted by the British Government. They, together with the British Commonwealth countries, adopted cordite, which had been developed by Sir Frederick Abel and Sir James Dewar, in 1889. The original Cordite Mk I consisted of 58% nitroglycerine, 37% guncotton and 5% petroleum jelly. Ballistite and cordite were both manufactured in the forms of cords.

Smokeless powders were originally developed using nitrocellulose as the sole explosive ingredient; and were therefore known as single base propellants. A range of smokeless powders that contain both nitrocellulose and nitroglycerin, known as double base propellants, were also developed. Smokeless powders were originally supplied only for military use; however they were also soon developed for civilian use and were quickly adopted for sport. Some are known as sporting powders.

Blasting gelatin, also known as gelignite, was invented by Nobel in 1875, using nitroglycerine, wood pulp, and sodium or potassium nitrates. This was an early low-cost, flexible explosive.

War time production rates

Large quantities of nitroglycerin were manufactured in both World Wars for use in military propellants.

World War I

In World War I HM Factory, Gretna, the largest propellant factory in the United Kingdom was producing 800 tons (812 tonne) of Cordite RDB per week. This required 336 tons of nitroglycerin per week (assuming no losses in production). The Royal Navy had its own factory at Royal Navy Cordite Factory, Holton Heath.

A large cordite factory was also built in Canada in World War I. The Canadian Explosives Limited Cordite factory at Nobel, Ontario was designed to produce 1,500,000 lb (681 tonne) of Cordite per month. It required 286 tonnes of nitroglycerin per month.

Medical implications

Medical use

Nitroglycerin belongs to a group of drugs called nitrates, which includes other nitrates like isosorbide dinitrate (Isordil) and isosorbide monoitrate (Imdur, Ismo, Monoket)^[10]. In medicine, where it is generally called glyceryl trinitrate, nitroglycerin is used as a heart medication (under the trade names Nitrospan, Nitrostat, and Tridil, amongst others). It is used as a medicine for angina pectoris (ischaemic heart disease) in tablets, ointment, solution for intravenous use, transdermal patches (Trinipatch, Transderm Nitro, Nitro-Dur), or sprays administered sublingually (Nitrolingual Pump Spray, Natispray). Nitroglycerin was synthesized in 1846, and was first used to treat anginal attacks in 1879.

Angina pectoris is due to an inadequate flow of blood and oxygen to the heart which is essential for the production of energy. The heart muscle must produce and use the energy in order to be able to pump blood through the lungs and into the arteries. It is believed that nitroglycerin corrects the imbalance between the flow of oxygen and blood to the heart ^[11]. The principal action of nitroglycerin is vasodilation—widening of the blood vessels. Nitroglycerin will dilate veins more than arteries because dilation of the viens help so that the heart does less work and requires less oxygen and blood. It also lowers the pressure in the artieris against which the heart must pump ^[12]. Dilating the veins, decreases cardiac preload and leads to the following therapeutic effects during episodes of angina pectoris:

• subsiding of chest pain
• decrease of blood pressure
• increase of heart rate.
• orthostatic hypotension

These effects arise because nitroglycerin is converted to nitric oxide in the body by mitochondrial aldehyde dehydrogenase,^[13] and nitric oxide is a natural vasodilator. Recently, it has also become popular in an off-label use at reduced (0.2%) concentration in ointment form as an effective treatment for anal fissure.

The side effects of Nitroglycerin include lack of sexual desire, head ache, painful urination and increased bowel movements.^{[citation needed]} Patients are often told to sit or lie down during and immediately after taking nitroglycerin to reduce the risk of low blood pressure. A drop in blood pressure can be accompanied by weakness or dizziness ^[14].

Industrial exposure

Infrequent exposure to high doses of nitroglycerin can cause severe headaches known as "NG head". These headaches can be severe enough to incapacitate some people; however, humans develop a tolerance to and dependence on nitroglycerin after long-term exposure. Withdrawal can (rarely) be fatal; withdrawal symptoms include headaches and heart problems; with re-exposure to nitroglycerin, these symptoms may disappear.

For workers in nitroglycerin (NTG) manufacturing facilities, this can result in a "Monday morning headache" phenomenon for those who experience regular nitroglycerin exposure in the workplace leading to the development of NTG tolerance for the vasodilating effects. Over the weekend the workers lose the tolerance to NTG and when they are reexposed on Monday the prominent vasodilation produces tachycardia, dizziness, and a headache.

See also

• Erythritol tetranitrate
• Ethylene glycol dinitrate
• Mannitol hexanitrate
• Methyl nitrate
• Xylitol pentanitrate

References

External links

• "Nitroglycerine! Terrible Explosion and Loss of Lives in San Francisco". Central Pacific Railroad Photographic History Museum. http://CPRR.org/Museum/Newspapers/Nitroglycerine.html. Retrieved 2005-03-23.  - 1866 Newspaper article
• WebBook page for C3H5N3O9
• Computational Chemistry Wiki
• The Tallini Tales of Destruction Detailed and horrific stories of the historical use of nitroglycerin-filled torpedoes to restart petroleum wells.