Erythritol tetranitrate

Last updated
Erythritol tetranitrate
Erythritol tetranitrate.png
Erythritol tetranitrate 3D ball.png
Names
IUPAC name
[(2R,3R)-1,3,4-Trinitrooxybutan-2-yl] nitrate
Other names
Erythrityl tetranitrate (INN)
Identifiers
3D model (JSmol)
1730082
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.027.940 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 230-734-9
KEGG
PubChem CID
UNII
  • InChI=1S/C4H6N4O12/c9-5(10)17-1-3(19-7(13)14)4(20-8(15)16)2-18-6(11)12/h3-4H,1-2H2/t3-,4+ Yes check.svgY
    Key: SNFOERUNNSHUGP-ZXZARUISSA-N Yes check.svgY
  • InChI=1/C4H6N4O12/c9-5(10)17-1-3(19-7(13)14)4(20-8(15)16)2-18-6(11)12/h3-4H,1-2H2/t3-,4+
    Key: SNFOERUNNSHUGP-ZXZARUISBH
  • C(C(C(CO[N+](=O)[O-])O[N+](=O)[O-])O[N+](=O)[O-])O[N+](=O)[O-]
Properties
C4H6N4O12
Molar mass 302.108 g·mol−1
Density 1.7219 (±0.0025) g/cm3
Melting point 61 °C (142 °F; 334 K)
Boiling point Decomposes at 160 °C
Hazards
GHS labelling:
GHS-pictogram-explos.svg GHS-pictogram-rondflam.svg GHS-pictogram-exclam.svg
NFPA 704 (fire diamond)
1
1
3
OX
Explosive data
Shock sensitivity Medium (2.0 Nm)
Friction sensitivity Medium
Detonation velocity 8200  m/s
RE factor 1.60
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Erythritol tetranitrate (ETN) is an explosive compound chemically similar to PETN, [1] though it is thought to be slightly more sensitive to friction and impact.

Contents

Like many nitrate esters, ETN acts as a vasodilator, and was the active ingredient in the original "sustained release" tablets, made under a process patent in the early 1950s, called "nitroglyn".[ citation needed ] Ingesting ETN or prolonged skin contact can lead to absorption and what is known as a "nitro headache".

Properties

ETN has a relatively high velocity of detonation of 8206 m/s at a density of 1.7219 (±0.0025) g/cm3. [2] It is white in color and odorless. ETN is commonly cast into mixtures with other high explosives. It is somewhat sensitive to shock and friction, so care needs to be taken while handling. ETN dissolves readily in acetone and other ketone solvents. The impact and friction sensitivity is slightly higher than the sensitivity of pentaerythritol tetranitrate (PETN). The sensitivity of melt cast and pressed ETN is comparable. Lower nitrates of erythritol, such as erythritol trinitrate, are soluble in water, so they do not contaminate most ETN samples.

Much like PETN, ETN is known for having a very long shelf life. Studies that directly observed the crystalline structure saw no signs of decomposition after four years of storage at room temperature. ETN has a melting point of 61 °C, compared to PETN which has a melting point of 141.3 °C. Recent studies of ETN decomposition suggested a unimolecular rate-limiting step in which the O−NO2 bond is cleaved and begins the decomposition sequence. [3]

ETN can and should be recrystallized, as to remove the trapped acids from synthesis. Warm ethanol or methanol is a viable solvent (close to 10 g of ETN/100 ml EtOH). ETN will precipitate as big platelets with bulk density of about 0.3 g/cm3 (fluffy material) when the ETN/ethanol solution is quickly poured into several liters of cold water. Smaller, fine crystals are produced by slow addition of water in said ETN/ethanol solution with intense mixing. Very fine crystals can be prepared by shock cooling of warm ETN/ethanol solution in a below −20 °C cooling bath. ETN can be easily hand pressed to about 1.2 g/cm3 (with a slight risk of accidental detonation).

Even small samples of ETN on the order of 20 mg can cause relatively powerful explosions verging on detonation when heated without confinement, e.g. when placed on a layer of aluminium foil and heated with flame from below.

ETN can be melt-cast in warm (about 65 °C) water. Slight decomposition is possible (often displayed by change in color from white to very light yellow). Nonetheless, no reports of runaway reactions leading to explosion have been confirmed (when melt-casting using only a bucket of warm water and recrystallized ETN). Melt-cast ETN, if cooled down slowly over a period of 10–30 minutes, has density of 1.70 g/cm3, detonation velocity of 8040 m/s, and Pcj detonation pressure of about 300 kbar. Its brisance is far higher than that of Semtex (about 220 kbar, depending on brand) [2] [4] [5] Mixtures of melt-cast ETN with PETN (about 50:50% by weight) are about the most brisant explosives that can be produced by moderately equipped amateurs. These mixtures have Pcj slightly above 300 kbar and detonation velocity above 8 km/s. This is close to the maximum of fielded military explosives like LX-10 or EDC-29 (about 370 kbar and close to 9 km/s). [6]

ETN is often plasticized using PIB/synthethic oil binders (very comparable to the binder system in C4) or using liquid nitric esters. The PIB-based plastic explosives are nontoxic and completely comparable to C4 or Semtex with Pcj of 200–250 kbar, depending on density (influenced by crystal size, binder amount, and amount of final rolling). EGDN/ETN/NC systems are toxic to touch, quite sensitive to friction and impact, but generally slightly more powerful than C4 (Pcj of about 250 kbar and Edet of 5.3 MJ/kg) and more powerful than Semtex (Pcj of about 220 kbar and Edet below 5 MJ/kg) with Pcj of about 250–270 kbar and Edet of about 6 MJ/kg.[ citation needed ] Note that different explosive software[ clarification needed ] and different experimental tests will yield absolute detonation pressures that can vary by 5% or more with the relative proportions being maintained.

125 g of ETN based plastic explosive with EGDN/NC/camphor binder system with creamer on top of it

Melt-cast ETN gives invalid results in the Hess test, i.e. the deformation is greater than 26 mm, with the lead cylinder being completely destroyed. Semtex 1A gives only 21 mm in the same test, i.e. melt-cast ETN is at least 20% more brisant than Semtex 1A. [7]

Melt-cast ETN or high density/low inert content ETN plastic explosives are one of the materials on "watch-lists" for terrorism.

Oxygen balance

One quality this explosive has, that PETN does not, is a positive oxygen balance, which means that ETN possesses more than enough oxygen in its structure to fully oxidize all of its carbon and hydrogen upon detonation. This can be seen in the schematic chemical equation below.

2 C4H6N4O12 → 8 CO2 + 6 H2O + 4 N2 + 1 O2

Whereas PETN decomposes to:

2 C5H8N4O12 → 6 CO2 + 8 H2O + 4 N2 + 4 CO

The carbon monoxide (CO) still requires oxygen to complete oxidation to carbon dioxide (CO2). A detailed study of the decomposition chemistry of ETN has been recently elucidated. [3]

Thus, for every two moles of ETN that decompose, one free mole of O2 is released. This oxygen could be used to oxidize an added metal dust, or an oxygen-deficient explosive, such as TNT or PETN. A chemical equation of how the oxygen from ETN with oxidizes PETN is shown below. The extra oxygen from the ETN oxidizes the carbon monoxide (CO) to carbon dioxide (CO2).

2 C4H6N4O12 + 1 C5H8N4O12 → 13 CO2 + 10 H2O + 6 N2

Manufacture

Like other nitrated polyols, ETN is made by nitrating erythritol either through the mixing of concentrated sulfuric acid and a nitrate salt, or by using a mixture of sulfuric and nitric acid.

See also

Related Research Articles

Explosive Substance that can explode

An explosive is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An explosive charge is a measured quantity of explosive material, which may either be composed solely of one ingredient or be a mixture containing at least two substances.

Nitroglycerin Chemical compound

Nitroglycerin (NG), also known as trinitroglycerin (TNG), nitro, glyceryl trinitrate (GTN), Nobel Oil, or 1,2,3-trinitroxypropane, is a dense, colorless, oily, explosive liquid most commonly produced by nitrating glycerol with white fuming nitric acid under conditions appropriate to the formation of the nitric acid ester. Chemically, the substance is an organic nitrate compound rather than a nitro compound, but the traditional name is retained. Invented in 1847 by Ascanio Sobrero, nitroglycerin has been used ever since as an active ingredient in the manufacture of explosives, namely dynamite, and as such it is employed in the construction, demolition, and mining industries. Since the 1880s, it has been used by the military as an active ingredient and gelatinizer for nitrocellulose in some solid propellants such as cordite and ballistite. It is a major component in double-based smokeless propellants used by reloaders. Combined with nitrocellulose, hundreds of powder combinations are used by rifle, pistol, and shotgun reloaders.

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

Pentaerythritol tetranitrate Explosive chemical compound

Pentaerythritol tetranitrate (PETN), also known as PENT, PENTA, TEN, corpent, or penthrite, is an explosive material. It 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 a very powerful explosive material with a relative effectiveness factor of 1.66. When mixed with a plasticizer, PETN forms a plastic explosive. Along with RDX it is the main ingredient of Semtex.

Ammonium nitrate Chemical compound with formula NH4NO3

Ammonium nitrate is a chemical compound with the chemical formula NH4NO3. It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, although it does not form hydrates. It is predominantly used in agriculture as a high-nitrogen fertilizer. Global production was estimated at 21.6 million tonnes in 2017.

ANFO Explosive

ANFO ( AN-foh) (or AN/FO, for ammonium nitrate/fuel oil) is a widely used bulk industrial explosive. It consists of 94% porous prilled ammonium nitrate (NH4NO3) (AN), which acts as the oxidizing agent and absorbent for the fuel, and 6% number 2 fuel oil (FO). The use of ANFO originated in the 1950s.

Nitromethane, sometimes shortened to simply "nitro", is an organic compound with the chemical formula CH
3NO
2. It is the simplest organic nitro compound. It is a polar liquid commonly used as a solvent in a variety of industrial applications such as in extractions, as a reaction medium, and as a cleaning solvent. As an intermediate in organic synthesis, it is used widely in the manufacture of pesticides, explosives, fibers, and coatings. Nitromethane is used as a fuel additive in various motorsports and hobbies, e.g. Top Fuel drag racing and miniature internal combustion engines in radio control, control line and free flight model aircraft.

A triggering sequence, also called an explosive train or a firing train, is a sequence of events that culminates in the detonation of explosives. For safety reasons, most widely used high explosives are difficult to detonate. A primary explosive of higher sensitivity is used to trigger a uniform and predictable detonation of the main body of the explosive. Although the primary explosive itself is generally a more sensitive and expensive compound, it is only used in small quantities and in relatively safely packaged forms. By design there are low explosives and high explosives made such that the low explosives are highly sensitive and high explosives are comparatively insensitive. This not only affords inherent safety to the usage of explosives during handling and transport, but also necessitates an explosive triggering sequence or explosive train. The explosive triggering sequence or the explosive train essentially consists of an 'initiator', an 'intermediary' and the 'high explosive'.

An entropic explosion is an explosion in which the reactants undergo a large change in volume without releasing a large amount of heat. The chemical decomposition of triacetone triperoxide (TATP) is an example of an entropic explosion. It is not a thermochemically highly favored event because little energy is generated in chemical bond formation in reaction products, but rather involves an entropy burst, which is the result of formation of one ozone and three acetone gas phase molecules from every molecule of TATP in the solid state.

Mannitol hexanitrate Chemical compound

Mannitol hexanitrate is a powerful explosive. Physically, it is a powdery solid at normal temperature ranges, with density of 1.73 g/cm3. The chemical name is hexanitromannitol and it is also known as nitromannite, MHN, and nitromannitol, and by the trademarks Nitranitol and Mannitrin. It is more stable than nitroglycerin, and it is used in detonators.

Hexamethylene triperoxide diamine Chemical compound

Hexamethylene triperoxide diamine (HMTD) is a high explosive organic compound. HMTD is an organic peroxide, a heterocyclic compound with a cage-like structure. It is a primary explosive. It has been considered as an initiating explosive for blasting caps in the early part of 20th century, mostly because of its high initiating power and its inexpensive production. As such, it was quickly taken up as a primary explosive in mining applications. However, it has since been superseded by more (chemically) stable compounds such as dextrinated lead azide and DDNP. HMTD is widely used in amateur-made blasting caps.

Ethylene glycol dinitrate Chemical compound

Ethylene Glycol Dinitrate, abbreviated EGDN and NGC, also known as Nitroglycol, is a chemical compound a colorless, oily explosive liquid obtained by nitrating Ethylene Glycol. It is similar to Nitroglycerin in both manufacture and properties, though it is more volatile and less viscous. Unlike Nitroglycerine, the chemical has a perfect (0) Oxygen balance, meaning that its ideal exothermic decomposition would completely convert it to low energy CO2, H2O, and N2, with no excess unreacted O2, H2, C, or other substances, without needing to react with anything else.

Rocket Candy, or R-Candy, is a type of rocket propellant for model rockets made with sugar as a fuel, and containing an oxidizer. The propellant can be divided into three groups of components: the fuel, the oxidizer, and the additive(s). In the past, sucrose was most commonly used as fuel. Modern formulations most commonly use sorbitol for its ease of production. The most common oxidizer is potassium nitrate (KNO3). Potassium nitrate is most commonly found in tree stump remover. Additives can be many different substances, and either act as catalysts or enhance the aesthetics of the liftoff or flight. A traditional sugar propellant formulation is typically prepared in a 65:35 (13:7) oxidizer to fuel ratio.

Pentolite

Pentolite is a composite high explosive used for military and civilian purposes, e.g., warheads and booster charges. It is made of PETN phlegmatized with TNT by melt casting.

A pyrotechnic composition is a substance or mixture of substances designed to produce an effect by heat, light, sound, gas/smoke or a combination of these, as a result of non-detonative self-sustaining exothermic chemical reactions. Pyrotechnic substances do not rely on oxygen from external sources to sustain the reaction.

Xylitol pentanitrate Chemical compound

Xylitol pentanitrate (XPN) is a nitrated ester primary explosive first synthesized in 1891 by Gabriel Bertrand. Law enforcement has taken an interest in XPN along with erythritol tetranitrate (ETN) and pentaerythritol tetranitrate (PETN) due to their ease of synthesis, which makes them accessible to amateur chemists and terrorists.

Explosive materials are produced in numerous physical forms for their use in mining, engineering, or military applications. The different physical forms and fabrication methods are grouped together in several use forms of explosives.

Nitrate ester

A nitrate ester is the organic functional group with the formula RONO2, where R stands for any organic residue. They are the esters of nitric acid and alcohols. A well-known example is nitroglycerin, which is not a nitro compound, despite its name.

2,4-Dinitroaniline is a chemical compound with a formula of C6H5N3O4. It is used as an explosive and as a reagent to detect and characterize aldehydes and ketones.

Nickel hydrazine nitrate Chemical compound

Nickel hydrazine nitrate (NHN), (chemical formula: [Ni(N2H4)3](NO3)2 is an energetic material having explosive properties in between that of primary explosive and a secondary explosive. It is a salt of a coordination compound of nickel with a reaction equation of 3N2H4·H2O + Ni(NO3)2 →〔Ni(N2H4)3〕(NO3)2 ＋ 3H2O

References

  1. ↑ Erythritol tetranitrate was first synthesized by British chemist John Stenhouse (1809-1880) in 1849. He extracted the simple sugar erythritol (which he called "erythroglucin") from lichen and then studied its chemistry. See: John Stenhouse (1 January 1849) "Examination of the proximate principles of some of the lichens. Part II," Philosophical Transactions of the Royal Society (London), vol. 139, pages 393-401. Reprinted in German as: John von Stenhouse (1849) "Über die näheren Bestandtheile einige Flechten," Justus Liebigs Annalen der Chemie und Pharmacie, vol. 70, no. 2, pages 218-228. Condensed version (in German): John Stenhouse (12 Sept. 1849) "Über die näheren Bestandtheile einige Flechten," Pharmaceutisches Centralblatt, vol. 20, no. 40, pages 625–628.
  2. 1 2 Oxley, Jimmie C.; Smith, James L.; Brady, Joseph E.; Brown, Austin C. (February 2012). "Characterization and Analysis of Tetranitrate Esters". Propellants, Explosives, Pyrotechnics. 37 (1): 19–39. CiteSeerX   10.1.1.653.6239 . doi:10.1002/prep.201100059. ISSN   0721-3115.
  3. 1 2 Furman, David; Kosloff, Ronnie; Zeiri, Yehuda (2016-12-22). "Effects of Nanoscale Heterogeneities on the Reactivity of Shocked Erythritol Tetranitrate". The Journal of Physical Chemistry C. 120 (50): 28886–28893. doi:10.1021/acs.jpcc.6b11543. ISSN   1932-7447.
  4. ↑ Künzel, Martin; Matyas, Robert; Vodochodský, Ondřej; Pachman, Jiri (2017-05-04). "Explosive Properties of Melt Cast Erythritol Tetranitrate (ETN)". Central European Journal of Energetic Materials. 14 (2): 418–429. doi: 10.22211/cejem/68471 . ISSN   1733-7178.
  5. ↑ Oxley, Jimmie C.; Furman, David; Brown, Austin C.; Dubnikova, Faina; Smith, James L.; Kosloff, Ronnie; Zeiri, Yehuda (2017-07-18). "Thermal Decomposition of Erythritol Tetranitrate: A Joint Experimental and Computational Study". The Journal of Physical Chemistry C. 121 (30): 16145–16157. doi:10.1021/acs.jpcc.7b04668. ISSN   1932-7447.
  6. ↑ https://permalink.lanl.gov/object/tr?what=info:lanl-repo/lareport/LA-UR-09-04939 [ bare URL PDF ]
  7. ↑ Matyáš, Robert; Künzel, Martin; Růžička, Aleš; Knotek, Petr; Vodochodský, Ondřej (2014). "Explosive Properties of Erythritol Tetranitrate". Propellants, Explosives, Pyrotechnics: n/a. doi:10.1002/prep.201300121.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.