Erythritol tetranitrate

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Names

IUPAC name

[(2R,3R)-1,3,4-Trinitrooxybutan-2-yl] nitrate

Other names

Erythrityl tetranitrate (INN)

Identifiers

CAS Number  7297-25-8 

3D model (JSmol)  Interactive image

Beilstein Reference 1730082

ChEBI  CHEBI:60072 

ChEMBL  ChEMBL2107583
ChemSpider  4447608 

DrugBank  DB01613

ECHA InfoCard 100.027.940 

EC Number  230-734-9

KEGG  D04051

PubChem CID  5284553

UNII  35X333P19D 

CompTox  DTXSID9022990 
Dashboard (EPA)

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InChI

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SMILES

Properties

Chemical formula 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:

Pictograms

   

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).

 verify (what is   ?)

Infobox references

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.
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".

Contents

 1Properties
 2Oxygen balance
 3Manufacture
 4See also
 5References

Properties[edit]
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 betrayed 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 (P cj 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
softwares[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[edit]
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[edit]
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[edit]
 Mannitol hexanitrate
 Xylitol pentanitrate

References[edit]
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. ^ Jump up to:a b 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/pr
ep.201100059.  ISSN  0721-3115.
3. ^ Jump up to:a b 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 19
32-7447.
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 19
32-7447.
6. ^ https://permalink.lanl.gov/object/tr?
what=info:lanl-repo/lareport/LA-UR-09-04939
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.
 show

Nitric oxide signaling modulators
Categories: 
 Explosive chemicals
 Nitrate esters
 Sugar alcohol explosives
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