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{{chembox |
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| Watchedfields = changed |
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| verifiedrevid = 443734409 |
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| verifiedrevid = 445341558 |
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| Name = |
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| ImageFile = Erythritol tetranitrate.png |
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| ImageFile = Erythritol tetranitrate.png |
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| ImageSize = 200px |
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| ImageSize = 200px |
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| ImageAlt = Skeletal formula of erythritol tetranitrate |
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| IUPACName = nitrate |
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| ImageFile1 = Erythritol tetranitrate 3D ball.png |
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| OtherNames = |
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| ImageAlt1 = Ball-and-stick model of the erythritol tetranitrate molecule |
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| IUPACName = nitrate |
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| OtherNames = Erythrityl tetranitrate (]) |
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| SystematicName = |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 7297-25-8 |
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| Beilstein = 1730082 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 60072 |
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| ChEMBL = 2107583 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 4447608 |
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| ChemSpiderID = 4447608 |
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| DrugBank = DB01613 |
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| EINECS = 230-734-9 |
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| KEGG = D04051 |
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| PubChem = 5284553 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 35X333P19D |
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| UNII = 35X333P19D |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = SNFOERUNNSHUGP-ZXZARUISSA-N |
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| StdInChIKey = SNFOERUNNSHUGP-ZXZARUISSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| ⚫ |
| CASNo = 7297-25-8 |
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| PubChem = 5284553 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 60072 |
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| SMILES = C(C(C(CO(=O))O(=O))O(=O))O(=O) |
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| SMILES = C(C(C(CO(=O))O(=O))O(=O))O(=O) |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| C = 4 | H = 6 | N = 4 | O = 12 |
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| C=4 | H=6 | N=4 | O=12 |
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| MolarMass = 302.11 g/mol |
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| Appearance = |
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| Appearance = |
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| Density = |
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| Density = 1.7219 (±0.0025) g/cm<sup>3</sup> |
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| MeltingPtC = 61 |
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| MeltingPtC = 61 |
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| BoilingPt = Decomposes at 160 °C |
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| BoilingPt = Decomposes at 160 °C |
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| Solubility = }} |
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| Solubility = 0.00302 g/100 mL}} |
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| Section3 = {{Chembox Hazards |
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| Section3 = {{Chembox Hazards |
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| GHSPictograms = {{GHS01}} {{GHS03}} {{GHS07}} |
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| NFPA-F = 1 |
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| NFPA-H = 1 |
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| NFPA-R = 3 |
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| NFPA-S = OX |
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| MainHazards = |
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| FlashPt = |
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| FlashPt = |
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| Autoignition = }} |
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| AutoignitionPt = }} |
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| Section4 = |
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| Section5 = |
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| Section6 = {{Chembox Explosive |
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| Section6 = {{Chembox Explosive |
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| ShockSens = Medium (2.0 Nm) |
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| ShockSens = Medium (2.0 Nm) |
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| FrictionSens = Medium |
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| FrictionSens = Medium |
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| ExplosiveV = 8000-8100 ] |
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| DetonationV = 8200 ] |
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| REFactor = 1.60}} |
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| REFactor = 1.60}} |
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'''Erythritol tetranitrate''' (ETN) is an explosive compound chemically similar to ].<ref>Erythritol tetranitrate was first synthesized by British chemist ] (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, .</ref> It is however thought to be 1/3 more sensitive to friction and impact. ETN is not well known, but in recent years has been used by amateur experimenters to replace PETN in improvised ] or in boosters to initiate larger, less sensitive explosive charges. Due to the availability of ] as a natural sweetener and its relative ease of production in relation to ], ETN is a favoured home made explosive compound to the amateur experimenter. |
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'''Erythritol tetranitrate''' ('''ETN''') is an explosive compound chemically similar to ],<ref>Erythritol tetranitrate was first synthesized by British chemist ] (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, .</ref> though it is thought to be slightly more sensitive to friction and impact. |
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Like many nitric esters, ETN acts as a ], and was the active ingredient in the original "]" tablets, made under a process patent in the early 50's, called "]". Ingesting ETN or prolonged skin contact can lead to absorption and what is known as a "nitro headache". |
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Like many ]s, ETN acts as a ], and was the active ingredient in the original "]" tablets, made under a process patent in the early 1950s, called "]".{{citation needed|date=September 2019}} Ingesting ETN or prolonged skin contact can lead to absorption and what is known as a "nitro headache". |
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== History == |
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ETN was discovered by ] in 1849 by nitrating erithrytol he recently discovered.<ref>{{Cite journal |date=1849-12-31 |title=Examination of the proximate principles of some of the lichens. — Part II |url=https://books.google.com/books?id=Km8zm5uZwpIC&pg=PA393 |journal=Philosophical Transactions of the Royal Society of London |language=en |volume=139 |pages=393–401 |doi=10.1098/rstl.1849.0020 |issn=0261-0523}}</ref> He described its explosive properties but suggested an incorrect formula due to atomic weights not yet being accurately determined. |
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Its vasodilator properties have been researched since 1895.<ref>{{Cite book |last=Oettingen |first=Wolfgang Felix Von |url=https://books.google.com/books?id=MfmS6zDjw_MC&pg=PA53 |title=The Effects of Aliphatic Nitrous and Nitric Acid Esters on the Physiological Functions: With Special Reference to Their Chemical Constitution |date=1946 |publisher=U.S. Government Printing Office |language=en}}</ref> |
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] researched the explosive after the war, getting a patent in 1928,<ref>{{US patent|1691954A}}</ref> but it was never commercialized due to the difficulty of erythritol synthesis. Only due to genetically-engineered yeasts in the 1990s did it become possible for the carbohydrate to become widely available. |
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==Properties== |
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==Properties== |
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ETN has a relatively high ] of 8000-8100 m/s at a density of 1.6 g/cm<sup>3</sup>. It is white in color and odorless. ETN is commonly cast into mixtures with other ]. It is somewhat sensitive to shock and friction, so care should be taken while handling. ETN dissolves readily in ] and other ] solvents though for the purpose of recrystallization, slow cooling of a saturated solution in ] from 55 °C gives much better results with purer and better formed crystals. |
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ETN has a relatively high ] of 8,206 m/s at a density of 1.7219 (±0.0025) g/cm<sup>3</sup>.<ref name="Oxley" /> It is white in color and odorless. ETN is commonly cast into mixtures with other ]. It is somewhat sensitive to shock and friction, so care must be taken while handling. ETN dissolves readily in ] and other ] solvents. The impact and friction sensitivity is slightly higher than the sensitivity of ] |
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(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. |
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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−NO<sub>2</sub> bond is cleaved and begins the decomposition sequence.<ref name=":0">{{Cite journal|last1=Furman|first1=David|last2=Kosloff|first2=Ronnie|last3=Zeiri|first3=Yehuda|date=2016-12-22|title=Effects of Nanoscale Heterogeneities on the Reactivity of Shocked Erythritol Tetranitrate|journal=The Journal of Physical Chemistry C|volume=120|issue=50|pages=28886–28893|doi=10.1021/acs.jpcc.6b11543|issn=1932-7447}}</ref> |
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ETN can and should be recrystallized, as to remove the trapped acids from synthesis. Warm ] or ] 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/cm<sup>3</sup> (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/cm<sup>3</sup> (with a slight risk of accidental detonation). |
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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. |
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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 a density of 1.70 g/cm<sup>3</sup>, detonation velocity of 8,040 m/s, and P<sub>cj</sub> detonation pressure of about 300 kbar. Its ] is far higher than that of Semtex (about 220 kbar, depending on brand).<ref name="Oxley">{{Cite journal |last1=Oxley |first1=Jimmie C. |last2=Smith |first2=James L. |last3=Brady |first3=Joseph E. |last4=Brown |first4=Austin C. |date=February 2012 |title=Characterization and Analysis of Tetranitrate Esters |journal=Propellants, Explosives, Pyrotechnics |volume=37 |issue=1 |pages=19–39 |doi=10.1002/prep.201100059 |issn=0721-3115 |citeseerx=10.1.1.653.6239}}</ref><ref>{{Cite journal|last1=Künzel|first1=Martin|last2=Matyas|first2=Robert|last3=Vodochodský|first3=Ondřej|last4=Pachman|first4=Jiri|date=2017-05-04|title=Explosive Properties of Melt Cast Erythritol Tetranitrate (ETN)|journal=Central European Journal of Energetic Materials|volume=14|issue=2|pages=418–429|doi=10.22211/cejem/68471|issn=1733-7178|doi-access=free}}</ref><ref>{{Cite journal|last1=Oxley|first1=Jimmie C.|last2=Furman|first2=David|last3=Brown|first3=Austin C.|last4=Dubnikova|first4=Faina|last5=Smith|first5=James L.|last6=Kosloff|first6=Ronnie|last7=Zeiri|first7=Yehuda|date=2017-07-18|title=Thermal Decomposition of Erythritol Tetranitrate: A Joint Experimental and Computational Study|journal=The Journal of Physical Chemistry C|volume=121|issue=30|pages=16145–16157|doi=10.1021/acs.jpcc.7b04668|issn=1932-7447}}</ref> |
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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 P<sub>cj</sub> slightly above 300 kbar and detonation velocity above 8 km/s. This is close to the maximum of fielded military explosives like ] or ] (about 370 kbar and close to 9 km/s).<ref>https://permalink.lanl.gov/object/tr?what=info:lanl-repo/lareport/LA-UR-09-04939 {{Bare URL PDF|date=March 2022}}</ref> |
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ETN is often plasticized using ]/synthethic oil binders (very comparable to the binder system in ]) or using liquid nitric esters. The PIB-based plastic explosives are nontoxic and completely comparable to C4 or ] with P<sub>cj</sub> of 200–250 kbar, depending on density (influenced by crystal size, binder amount, and amount of final rolling). ]/ETN/] systems are toxic to touch, quite sensitive to friction and impact, but generally slightly more powerful than C4 (P<sub>cj</sub> of about 250 kbar and E<sub>det</sub> of 5.3 MJ/kg) and more powerful than ] (P<sub>cj</sub> of about 220 kbar and E<sub>det</sub> below 5 MJ/kg) with P<sub>cj</sub> of about 250–270 kbar and E<sub>det</sub> of about 6 MJ/kg.{{citation needed|date=May 2018}} Note that explosion modeling software and experimental tests will yield absolute detonation pressures that can vary by 5% or more with the relative proportions being maintained. |
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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.<ref>{{Cite journal | url=https://www.researchgate.net/publication/260409695 | doi=10.1002/prep.201300121| title=Explosive Properties of Erythritol Tetranitrate| journal=Propellants, Explosives, Pyrotechnics| year=2014| last1=Matyáš| first1=Robert| last2=Künzel| first2=Martin| last3=Růžička| first3=Aleš| last4=Knotek| first4=Petr| last5=Vodochodský| first5=Ondřej| pages=n/a| doi-broken-date=3 December 2024}}</ref> |
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Melt-cast ETN or high density/low inert content ETN plastic explosives are one of the materials on "watch-lists" for terrorism. |
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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. |
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==Oxygen balance== |
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==Oxygen balance== |
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One quality this explosive has, that PETN does not, is a positive ]. Having a positive oxygen balance means that ETN possesses more than enough oxygen in its structure to fully oxidize all of its ] and ] upon ]. This can be seen in the equation below. |
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One positive characteristic of ETN that PETN does not possess is a positive ], which means that ETN possesses more than enough oxygen in its structure to fully oxidize all of its ] and ] upon ]. This can be seen in the schematic chemical equation below. |
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:C<sub>4</sub>H<sub>6</sub>N<sub>4</sub>O<sub>12</sub> → 4 CO<sub>2</sub> + 3 H<sub>2</sub>O + 2 N<sub>2</sub> + ½ O<sub>2</sub> |
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:2 C<sub>4</sub>H<sub>6</sub>N<sub>4</sub>O<sub>12</sub> → 8 CO<sub>2</sub> + 6 H<sub>2</sub>O + 4 N<sub>2</sub> + 1 O<sub>2</sub> |
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Whereas PETN decomposes to: |
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Whereas PETN decomposes to: |
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:C<sub>5</sub>H<sub>8</sub>N<sub>4</sub>O<sub>12</sub> → 3 CO<sub>2</sub> + 2 CO + 4 H<sub>2</sub>O + 2 N<sub>2</sub> |
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:2 C<sub>5</sub>H<sub>8</sub>N<sub>4</sub>O<sub>12</sub> → 6 CO<sub>2</sub> + 8 H<sub>2</sub>O + 4 N<sub>2</sub> + 4 CO |
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The ] (CO) still requires oxygen to complete oxidation to ] (CO<sub>2</sub>). |
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The ] (CO) still requires oxygen to complete oxidation to ] (CO<sub>2</sub>). A detailed study of the decomposition chemistry of ETN has been recently elucidated.<ref name=":0" /> |
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Thus for every mole of ETN that decomposes, 1/2 free mole of O<sub>2</sub> is released. This could be used to oxidize an added metal dust or an oxygen deficient explosive such as ] or PETN. |
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Thus, for every two moles of ETN that decompose, one free mole of O<sub>2</sub> is released. This oxygen could be used to oxidize an added metal dust, or an oxygen-deficient explosive, such as ] 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 (CO<sub>2</sub>). |
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:2 C<sub>4</sub>H<sub>6</sub>N<sub>4</sub>O<sub>12</sub> + 1 C<sub>5</sub>H<sub>8</sub>N<sub>4</sub>O<sub>12</sub> → 13 CO<sub>2</sub> + 10 H<sub>2</sub>O + 6 N<sub>2</sub> |
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==Manufacture== |
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==Manufacture== |
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Like other nitrated ], ETN is made by nitrating erythritol through the mixing of concentrated ] and a ] salt. ] is commonly used for this type of reaction. The erythritol is added to the mixture to begin its nitration. Much better yields can be obtained by using concentrated ] in place of the nitrate salt, in which case the ] is used simply to absorb water and act as a catalyst from the resulting ], driving the reaction. |
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Like other nitrated ], ETN is made by nitrating ] either through the mixing of concentrated ] and a ] salt, or by using a mixture of sulfuric and nitric acid. |
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== See also == |
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== See also == |
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* ] |
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==References== |
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==References== |
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{{reflist}} |
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{{reflist}} |
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{{Nitric oxide signaling}} |
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{{DEFAULTSORT:Erythritol Tetranitrate}} |
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{{DEFAULTSORT:Erythritol Tetranitrate}} |
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