Erythritol tetranitrate

ETN was discovered by John Stenhouse in 1849 by nitrating erythritol he recently discovered.{{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|url-access=subscription }} He described its explosive properties but suggested an incorrect formula due to atomic weights not yet being accurately determined.

Its vasodilator properties have been researched since 1895.{{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}}

DuPont researched the explosive after the war, getting a patent in 1928,{{US patent|1691954A}} 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.

ETN has a relatively high velocity of detonation of {{convert|8206|m/s|ft/s|abbr=on}} at a density of {{val|1.7219|0.0025|u=g/cm3}}). It is white in color and odorless. ETN is commonly cast into mixtures with other high explosives. 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.{{citation needed|date=June 2025}} Lower nitrates of erythritol, such as erythritol trinitrate, are soluble in water, so they do not contaminate most ETN samples.{{relevance?|date=June 2025}}

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 {{convert|61|C|F}}, compared to PETN which has a melting point of {{convert|141.3|C|F}}. Recent studies of ETN decomposition suggested a unimolecular rate-limiting step in which the {{chem2|O\sNO2}} bond is cleaved and begins the decomposition sequence.{{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}}

Even small samples of ETN on the order of {{val|20|u=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.{{citation needed|date=June 2025}}

ETN can be melt-cast in warm (about {{convert|65|C|F}}) water. Slight decomposition is possible (often displayed by change in color from white to very light yellow). No reports of runaway reactions leading to explosion have been confirmed.{{by who?|date=June 2025}} However, the handling sensitivity in molten state is extremely poor (e. g., much worse than acetone peroxide) and it makes melt-casting it impractical for commercial applications.{{Cite journal |last1=Cawkwell |first1=M. J. |last2=Manner |first2=V. W. |date=2024-04-04 |title=Properties of Erythritol Tetranitrate from Molecular Dynamics Simulation |journal=The Journal of Physical Chemistry C |volume=128 |issue=13 |pages=5749–5758 |doi=10.1021/acs.jpcc.4c00489 |issn=1932-7447 |pmc=11000242 |pmid=38595775}}{{Cite journal |last1=Lease |first1=Nicholas |last2=Kay |first2=Lisa |last3=Chavez |first3=David E. |last4=Robbins |first4=David |last5=Manner |first5=Virginia W. |date=2019-04-05 |title=Increased handling sensitivity of molten erythritol tetranitrate (ETN) |url=https://www.sciencedirect.com/science/article/pii/S0304389418312597 |journal=Journal of Hazardous Materials |volume=367 |pages=546–549 |doi=10.1016/j.jhazmat.2018.12.110 |pmid=30641424 |issn=0304-3894|doi-access=free }}

Melt-cast ETN, if cooled down slowly over a period of 10–30 minutes, has a density of {{val|1.70|u=g/cm3}}, detonation velocity of {{convert|8,040|m/s|ft/s|abbr=on}}, and P_cj detonation pressure of about {{convert|300000|bar|psi}}. Its brisance is far higher than that of Semtex (about {{convert|220000|bar|psi}}, depending on brand).{{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}}{{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}}{{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}}

Mixtures of 50:50 PETN:ETN have P{{sub|cj}} slightly above {{convert|300000|bar|psi}} and detonation velocity above {{convert|8|km/s|ft/s|abbr=on}}. This is close to the maximum of fielded military explosives like LX-10 or EDC-29 (about {{convert|370000|bar|psi}} and close to {{convert|9|km/s|ft/s|abbr=on}}).{{Cite conference |last=Gustavsen |first=Richard L. |last2=Bartram |first2=Brian D. |last3=Sanchez |first3=Nathaniel J. |date=2009 |title=Detonation wave profiles measured in plastic bonded explosives using 1550 nm photon doppler velocimetry (PDV) |url=https://www.osti.gov/servlets/purl/991280 |conference=Shock Compression of Condensed Matter |osti=991280 |via=OSTI}}

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 P{{sub|cj}} of {{convert|200000-250000|bar|psi}}, 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 (P{{sub|cj}} of about {{convert|250000|bar|psi}} and E{{sub|det}} of {{val|5.3|u=MJ/kg}}) and more powerful than Semtex (P{{sub|cj}} of about {{convert|220000|bar|psi}} and E{{sub|det}} below {{val|5|u=MJ/kg}}) with P{{sub|cj}} of about {{convert|250000-270000|bar|psi}} and E{{sub|det}} of about {{val|6|u=MJ/kg}}.{{citation needed|date=May 2018}} Note that explosion modeling software and experimental tests{{which?|date=June 2025}} will yield absolute detonation pressures that can vary by 5% or more with the relative proportions being maintained.{{relevance?|date=June 2025}}

File:125 g ETN plastic explosive.webm

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.{{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}}

Melt-cast ETN or high density/low inert content ETN plastic explosives are one of the materials on "watch-lists" for terrorism.{{relevance?|reason=since HE materials require licensing everywhere, what situation does this legitimately come up in?|date=June 2025}}

One positive characteristic of ETN that PETN does not possess 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.

:{{chem2|2 C4H6N4O12 -> 8 CO2 + 6 H2O + 4 N2 + O2}}

Whereas PETN decomposes to:

:{{chem2|2 C5H8N4O12 -> 6 CO2 + 8 H2O + 4 N2 + 4 CO}}

The carbon monoxide (CO) still requires oxygen to complete oxidation to carbon dioxide ({{chem2|CO2}}). A detailed study of the decomposition chemistry of ETN has been recently elucidated.

Thus, for every two moles of ETN that decompose, one free mole of {{chem2|O2}} is released. This oxygen could be used to oxidize an added metal dust, or an oxygen-deficient explosive, such as TNT or PETN. The extra oxygen from the ETN oxidizes the carbon monoxide (CO) to carbon dioxide ({{chem2|CO2}}).

:{{chem2|2 C4H6N4O12 + C5H8N4O12 -> 13 CO2 + 10 H2O + 6 N2}}

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.

• Mannitol hexanitrate
• Xylitol pentanitrate

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{{Nitric oxide signaling}}

{{DEFAULTSORT:Erythritol Tetranitrate}}

Category:Explosive chemicals

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