Pentaerythritol tetranitrate

Pentaerythritol tetranitrate
IUPAC name [3-Nitrooxy-2,2-bis(nitrooxymethyl)propyl] nitrate
Identifiers
CAS number	78-11-5 Y
PubChem	6518
ChemSpider	6271 Y
ChEMBL	CHEMBL466659 Y
ATC code	C01DA05
Jmol-3D images	{{#if:C(C(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-])O[N+](=O)[O-]|Image 1
SMILES C(C(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-])O[N+](=O)[O-]
InChI InChI=1S/C5H8N4O12/c10-6(11)18-1-5(2-19-7(12)13,3-20-8(14)15)4-21-9(16)17/h1-4H2 Y Key: TZRXHJWUDPFEEY-UHFFFAOYSA-N Y InChI=InChI=1S/C5H8N4O12/c10-6(11)18-1-5(2-19-7(12)13,3-20-8(14)15)4-21-9(16)17/h1-4H2
Properties
Molecular formula	C5H8N4O12
Molar mass	316.14 g mol−1
Appearance	White crystalline solid[1]
Density	1.77 g/cm3 at 20 °C
Melting point	141.3 °C; 286.3 °F; 414.4 K
Boiling point	180 °C; 356 °F; 453 K (decomposes above 150 °C)
Explosive data
Shock sensitivity	Medium
Friction sensitivity	Medium
Explosive velocity	8400 m/s (density 1.7 g/cm3)
RE factor	1.66
Hazards
Autoignition temperature	190 °C; 374 °F; 463 K
Y (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

Pentaerythritol tetranitrate (PETN), also known as PENT, PENTA, TEN, corpent, penthrite (or—rarely and primarily in German—as nitropenta), is the nitrate ester of pentaerythritol, and is structurally very similar to nitroglycerin. Penta refers to the five carbon atoms of the neopentane skeleton.

PETN is best known as an explosive. It is one of the most powerful high explosives known, with a relative effectiveness factor of 1.66.^[2]

PETN mixed with a plasticizer forms a plastic explosive.^[3] As a mixture with RDX and other minor additives, it forms another plastic explosive called Semtex as well. The compound was discovered in the bombs used by the 2001 Shoe Bomber, in the 2009 Christmas Day bomb plot, and in the 2010 cargo plane bomb plot.^[4] On 7 September 2011, a bomb suspected to have used PETN exploded near the High Court of Delhi in India claiming 13 lives and injuring more than 70.^[5]

It is also used as a vasodilator drug to treat certain heart conditions, such as for management of angina.^[6][7]

History

Penthrite was first synthesized in 1891 by Bernhard Tollens and P. Wigand by nitration of pentaerythritol.^[8] The production of PETN started in 1912, when it was patented by the German government. PETN was used by the German Army in World War I.^[9]

Properties

PETN is practically insoluble in water (0.01 g/100 ml at 50 °C), weakly soluble in common nonpolar solvents such as aliphatic hydrocarbons (like gasoline) or tetrachloromethane, but soluble in some other organic solvents, particularly in acetone (about 15 g/100 g of the solution at 20 °C, 55 g/100 g at 60 °C) and dimethylformamide (40 g/100 g of the solution at 40 °C, 70 g/100 g at 70 °C). PETN forms eutectic mixtures with some liquid or molten aromatic nitro compounds, e.g. trinitrotoluene (TNT) or tetryl. Due to its highly symmetrical structure, PETN is resistant to attack by many chemical reagents; it does not hydrolyze in water at room temperature or in weaker alkaline aqueous solutions. Water at 100 °C or above causes hydrolysis to dinitrate; presence of 0.1% nitric acid accelerates the reaction. Addition of TNT and other aromatic nitro derivatives lowers thermal stability of PETN.^{[citation needed]}

The chemical stability of PETN is of interest, because of the use of PETN in aging stockpiles of weapons. A review has been published.^[10] Neutron radiation degrades PETN, producing carbon dioxide and some pentaerythritol dinitrate and trinitrate. Gamma radiation increases the thermal decomposition sensitivity of PETN, lowers melting point by few degrees Celsius, and causes swelling of the samples. Like other nitrate esters, the primary degradation mechanism is the loss of nitrogen dioxide; this reaction is autocatalytic.^{[citation needed]}. Studies were performed on thermal decomposition of PETN.^[11]

In the environment, PETN undergoes biodegradation. Some bacteria denitrate PETN to trinitrate and then dinitrate, which is then further degraded.^{[citation needed]} PETN has low volatility and low solubility in water, and therefore has low bioavailability for most organisms. Its toxicity is relatively low, and its transdermal absorption also seems to be low.^[1] It poses a threat for aquatic organisms. It can be degraded to pentaerythritol by iron metal.^[12]

Production

Production is by the reaction of pentaerythritol with concentrated nitric acid to form a precipitate which can be recrystallized from acetone to give processable crystals.^[13]

C(CH₂OH)₄ + 4 HNO₃ → C(CH₂ONO₂)₄ + 4 H₂O

Variations of a method first published in a US Patent 2,370,437 by Acken and Vyverberg (1945 to Du Pont) forms the basis of all current commercial production.

PETN is manufactured by numerous manufacturers as a powder about the consistency of fine popcorn salt, or together with nitrocellulose and plasticizer as thin plasticized sheets (e.g. Primasheet 1000 or Detasheet). PETN residues are easily detectable in hair of people handling it.^[14] The highest residue retention is on black hair; some residues remain present even after washing.^[15][16]

Explosive use

The most common use of PETN is as an explosive with high brisance. It is more difficult to detonate than primary explosives, so dropping or igniting it will typically not cause an explosion (at atmospheric pressure it is difficult to ignite and burns relatively slowly), but is more sensitive to shock and friction than other secondary explosives such as TNT or tetryl.^[13][17] Under certain conditions a deflagration to detonation transition can occur.

It is rarely used alone, but primarily used in booster and bursting charges of small caliber ammunition, in upper charges of detonators in some land mines and shells, and as the explosive core of detonation cord.^[18] PETN is the least stable of the common military explosives, but can be stored without significant deterioration for longer than nitroglycerin or nitrocellulose.^[19]

During World War II, PETN was most importantly used in exploding-bridgewire detonators for the atomic bombs. These exploding-bridgewire detonators gave more precise detonation, compared with primacord. PETN was used for these detonators because it was safer than primary explosives like lead azide: while it was sensitive, it would not detonate below a threshold amount of energy.^[20] Exploding bridgewires containing PETN remain used in current nuclear weapons. In spark detonators, PETN is used to avoid the need for primary explosives; the energy needed for a successful direct initiation of PETN by an electric spark ranges between 10–60 mJ.

Its basic explosion characteristics are:

• Explosion energy: 5810 kJ/kg (1390 kcal/kg), so 1 kg of PETN has the energy of 1.24 kg TNT.
• Detonation velocity: 8350 m/s (1.73 g/cm³), 7910 m/s (1.62 g/cm³), 7420 m/s (1.5 g/cm³), 8500 m/s (pressed in a steel tube)
• Volume of gases produced: 790 dm³/kg (other value: 768 dm³/kg)
• Explosion temperature: 4230 °C
• Oxygen balance: -6.31 atom -g/kg
• Melting point: 141.3 °C (pure), 140–141 °C (technical)
• Trauzl lead block test: 523 cm³ (other values: 500 cm³ when sealed with sand, or 560 cm³ when sealed with water)
• Critical diameter (minimal diameter of a rod that can sustain detonation propagation): 0.9 mm for PETN at 1 g/cm³, smaller for higher densities (other value: 1.5 mm)

In mixtures

PETN is used in a number of compositions. It is a major ingredient of the Semtex plastic explosive. It is also used as a component of pentolite, a 50/50 blend with TNT; a shaped charge of 8 ounces (0.23 kg) of pentolite, used in the M9A1 (bazooka) rockets, can penetrate up to 5 inches (130 mm) of armor.^{[citation needed]} The XTX8003 extrudable explosive, used in the W68 and W76 nuclear warheads, is a mixture of 80% PETN and 20% of Sylgard 182, a silicone rubber.^[21] It is often phlegmatized by addition of 5–40% of wax, or by polymers (producing polymer-bonded explosives); in this form it is used in some cannon shells up to 30 mm caliber, though unsuitable for higher calibers. It is also used as a component of some gun propellants and solid rocket propellants. Nonphlegmatized PETN is stored and handled with approximately 10% water content. PETN alone cannot be cast as it explosively decomposes slightly above its melting point, but it can be mixed with other explosives to form castable mixtures.

PETN can be initiated by a laser.^[22] A pulse with duration of 25 nanoseconds and 0.5–4.2 joules of energy from a Q-switched ruby laser can initiate detonation of a PETN surface coated with a 100 nm thick aluminium layer in less than half microsecond.^{[citation needed]}

PETN has been replaced in many applications by RDX, which is thermally more stable and has longer shelf life.^[23] PETN can be used in some ram accelerator types.^[24] Replacement of the central carbon atom with silicon produces Si-PETN, which is extremely sensitive.^[25][26]

Terrorist use

In 1983, the "Maison de France" house in Berlin was brought to a near-total collapse by the detonation of 24 kilograms (53 lb) of PETN by terrorist Johannes Weinrich.^[27]

In 1999, Alfred Heinz Reumayr used PETN as the main charge for his fourteen improvised explosive devices that he constructed in a thwarted attempt to damage the Trans-Alaska Pipeline System.

In 2001, al-Qaeda member Richard Reid, the "Shoe Bomber", used PETN in the sole of his sneaker in his unsuccessful attempt to blow up American Airlines Flight 63 from Paris to Miami.^[16][28] He had intended to use the solid triacetone triperoxide (TATP) as a detonator.^[17]

In 2009, PETN was used in an attempt by al-Qaeda in the Arabian Peninsula to murder the Saudi Arabian Deputy Minister of Interior Prince Muhammad bin Nayef, by Saudi suicide bomber Abdullah Hassan al Asiri. The target survived and the bomber died in the blast. The PETN was hidden in the bomber's rectum, which security experts described as a novel technique.^[29][30][31]

On December 25, 2009, PETN was found in the underwear of Umar Farouk Abdulmutallab, the "Underwear bomber", a Nigerian with links to al-Qaeda in the Arabian Peninsula.^[32] According to U.S. law enforcement officials,^[33] he had attempted to blow up Northwest Airlines Flight 253 while approaching Detroit from Amsterdam.^[34] Abdulmutallab had tried, unsuccessfully, to detonate approximately 80 grams (2.8 oz) of PETN sewn into his underwear by adding liquid from a syringe;^[35] however, only a small fire resulted.^[17]

In the al-Qaeda in the Arabian Peninsula October 2010 cargo plane bomb plot, two PETN-filled printer cartridges were found at East Midlands Airport and in Dubai on flights bound for the U.S. on an intelligence tip. Both packages contained sophisticated bombs concealed in computer printer cartridges filled with PETN.^[4][36] The bomb found in England contained 400 grams (14 oz) of PETN, and the one found in Dubai contained 300 grams (11 oz) of PETN.^[36] Hans Michels, professor of safety engineering at University College London, told a newspaper that 6 grams (0.21 oz) of PETN—"around 50 times less than was used—would be enough to blast a hole in a metal plate twice the thickness of an aircraft's skin".^[37] In contrast, according to an experiment conducted by a BBC documentary team designed to simulate Abdulmutallab's Christmas Day bombing, using a Boeing 747 airplane, even 80 grams of PETN was not sufficient to materially damage the airplane's fuselage.^[38]

Detection

In the wake of terrorist PETN bomb plots, an article in Scientific American noted that even if all cargo were screened, PETN is difficult to detect because it has a very low vapor pressure at room temperature, meaning very little of it gets into the air around the bomb, where it can be detected.^[4] The Los Angeles Times noted in November 2010 that because of its more stable molecules, and lower vapor, it is more difficult to detect by bomb-sniffing dogs and the trace swabs then used by the U.S. Transportation Security Administration.^[16]

Many technologies can be used to detect PETN,^[39] a number of which have been implemented in public screening applications, primarily for air travel. PETN is just one of a number of explosive chemicals typically of interest in that area, and it belongs to a family of common nitrate-based explosive chemicals which can often be detected by the same tests.

One technology, detectors that test swabs wiped on passengers and their baggage for traces of explosives, is generally reserved for travelers who are thought to merit additional scrutiny. A second type of machine, whole-body imaging scanners, use radio-frequency electromagnetic waves, low-intensity X-rays, or T-rays of terahertz frequency to detect objects under clothing; these devices were of limited availability because of cost, privacy groups' opposition and industry concerns about bottlenecks.^[40]

Both parcels in the 2010 cargo plane bomb plot were x-rayed without the bombs being spotted.^[41] Qatar Airways said the PETN bomb "could not be detected by x-ray screening or trained sniffer dogs".^[42] The Bundeskriminalamt received copies of the Dubai x-rays, and an investigator said German staff would not have identified the bomb either.^[41][43] New airport security procedures followed in the U.S., largely to protect against PETN.^[16]

Medical use

Like nitroglycerin (glyceryl trinitrate) and other nitrates, PETN is also used medically as a vasodilator in the treatment of heart conditions.^[6][7] These drugs work by releasing the signaling gas nitric oxide in the body. The heart medicine Lentonitrat is nearly pure PETN.^[44]

Monitoring of oral usage of the drug by patients has been performed by determination of plasma levels of several of its hydrolysis products, pentaerythritol dinitrate, pentaerythritol mononitrate and pentaerythritol, in plasma using gas chromatography-mass spectrometry.^[45]

See also

• Erythritol tetranitrate
• Pentaerythritol
• RDX
• RE factor

References

Further reading

Wikimedia Commons has media related to Pentaerythritol tetranitrate.

• Cooper, Paul (1997). Explosives Engineering. Weinheim: Wiley-VCH. ISBN 0-471-18636-8.