Hexamethylene triperoxide diamine

Last updated

Contents

Hexamethylene triperoxide diamine
HMTD structure.png
Heksametylenotriperoksydiamina.JPG
Names
Preferred IUPAC name
3,4,8,9,12,13-Hexaoxa-1,6-diazabicyclo[4.4.4]tetradecane
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
PubChem CID
  • InChI=1S/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2 Yes check.svgY
    Key: HMWPNDNFTFSCEB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2
    Key: HMWPNDNFTFSCEB-UHFFFAOYAC
  • C1N2COOCN(COO1)COOC2
Properties
C6H12N2O6
Molar mass 208.17 g/mol
AppearanceWhite crystalline solid
Density 1.57 g/cm3
Melting point Decomposes at 75 °C
Ignites spontaneously at 133 °C
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Explosive
GHS labelling:
GHS-pictogram-explos.svg GHS-pictogram-exclam.svg
Danger
H202, H205, H241, H300, H315, H318, H335
P102, P220, P243, P250, P261, P264, P280, P283, P370+P380, P372, P404
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 4: Readily capable of detonation or explosive decomposition at normal temperatures and pressures. E.g. nitroglycerinSpecial hazards (white): no code
1
1
4
Explosive data
Shock sensitivity High
Friction sensitivity Very High
Detonation velocity ~2800 m/s (at around 0.4 g/cm3) - 5100 m/s at around 1.1 g/cm3
RE factor 0.74
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 ?)

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 (higher than that of mercury fulminate) and its inexpensive production. As such, it was quickly taken up as a primary explosive in mining applications. [1] However, it has since been superseded by more (chemically) stable compounds such as dextrinated lead azide and DDNP (which contains no lead or mercury). HMTD is widely used in amateur-made blasting caps.

Preparation and structure

First synthesised in 1885 by the German chemist Ludwig Legler, [2] HMTD may be prepared by the reaction of an aqueous solution of hydrogen peroxide and hexamine in the presence of an acid catalyst, such as citric acid, acetic acid or dilute sulfuric acid. The hydrogen peroxide needs to be at least 12% w/w concentration, as lower concentrations lead to poor yields. Citric acid is overall superior to other acids, providing a yield of up to about 50%.

The molecule adopts a cage-like structure with the nitrogen atoms having an unusual trigonal planar geometry. [3]

Properties as an explosive

Like other organic peroxides, such as acetone peroxide (TATP), HMTD is unstable and detonated by shock, friction, static electricity discharges, concentrated sulfuric acid, strong UV radiation and heat. Cases of detonation caused by the simple act of screwing a lid on a jar containing HMTD have been reported.[ citation needed ] Common static electricity discharges have been reported to cause detonation. [4] It attacks aluminum, tin, zinc, brass, copper, lead and iron. [5] It does not quickly sublime like its acetone counterparts.[ citation needed ]

HMTD is very unstable in storage, with decomposition rate increasing with temperature. Samples lost 79% of their weight in 300 days at 50 °C (122 °F), in 150 days at 70 °C (158 °F), and in only 5-20 days at 90 °C (194 °F). It is unstable even when stored under water. [5]

HMTD is a more powerful initiating explosive than mercury fulminate, but its poor thermal and chemical stability prevents its use in detonators. [6] Nevertheless, HMTD is one of the three most widely used primary explosives in improvised, amateur made blasting caps, the others being TATP and silver acetylide.[ citation needed ]

HMTD is a common source of injury, particularly finger amputations, among amateur chemists. Most of these injuries are caused by small amounts of HMTD that inadvertently detonate in close proximity of fingers, since small amounts (grams) are generally not powerful enough to amputate fingers from distances larger than 5–10 cm (2.0–3.9 in).[ citation needed ]

Reported explosive properties are a detonation velocity of 4,511 m/s (14,800 ft/s) in a 0.22 in (5.6 mm) column compressed to a density of 0.88 g/cm3 and 5,100 m/s (17,000 ft/s) at a density of 1.1 g/cm3. Its power is 60% that of TNT in the Trauzl test. [5]

Sensitivity

HMTD is overall slightly more sensitive than fresh TATP and can be considered to be slightly more dangerous than an average primary explosive. The variance of friction force between different surfaces (e.g. different kinds of paper) is often greater than the variance between the friction sensitivity of a given pair of primary explosives. This leads to different values for friction sensitivity measured at different laboratories.

Terrorism use

Despite no longer being used in any military application, and despite its shock sensitivity, HMTD remains a common home-made explosive and has been used in a large number of suicide bombings and other attacks throughout the world. For example, it was one of the components in the explosives intended to bomb Los Angeles International Airport in the 2000 millennium attack plots [7] [8] and the 2016 New York and New Jersey bombings, [9] as well as one of the components of the explosives attempted to be made by the neo-Nazi terrorist organization Atomwaffen Division in the United States. [10]

References

  1. ↑ Taylor, C. A.; Rinkenbach, W. H. Army Ordnance1924. 5, 463–466[ verification needed ]
  2. ↑ Legler, L. (1885). "Ueber Producte der langsamen Verbrennung des Aethyläthers". Berichte der Deutschen Chemischen Gesellschaft. 18 (2): 3343–3351. doi:10.1002/cber.188501802306.
  3. ↑ Schaefer, William P.; Fourkas, John T.; Tiemann, Bruce G. (April 1985). "Structure of hexamethylene triperoxide diamine". Journal of the American Chemical Society. 107 (8): 2461–2463. Bibcode:1985JAChS.107.2461S. doi:10.1021/ja00294a043.
  4. ↑ Matyáš, Robert; Pachmáň, Jiří; Matyáš, Robert (2013). "2.33". Primary explosives (PDF). Berlin New York: Springer. p. 21. ISBN   978-3-642-28436-6. Archived from the original (PDF) on 21 July 2018.
  5. 1 2 3 Fedoroff, Basil T.; Sheffield, Oliver E.; Kaye, Seymour M. (1 January 1978). "H - Hexamethylenetriperoxidediamine". Encyclopedia of Explosives and Related Items (PDF) (Report). Vol. 7, H2 to Lysol. Dover, NJ: Picatinny Arsenal. p. H83-4. ADA019502, PATR 2700.
  6. ↑ Agrawal, J. P.; Hodgson, R. D. (2007). Organic chemistry of explosives. Chichester, England ; Hoboken, NJ: John Wiley & Sons Ltd. p. 414. ISBN   9780470029671.
  7. ↑ U.S. Court of Appeals for the Ninth Circuit (2 February 2010). "U.S. v. Ressam" (PDF). Archived from the original (PDF) on 4 October 2012. Retrieved 27 February 2010.
  8. ↑ "Complaint; U.S. v. Ressam" (PDF). NEFA Foundation. December 1999. Archived from the original (PDF) on 1 March 2012. Retrieved 26 February 2010.
  9. ↑ Cullinane, Susannah; Shimon Prokupecz; Emanuella Grinberg; Holly Yan (20 September 2016). "7 questions we have about bombings in New York and New Jersey". CNN . Retrieved 20 September 2016.
  10. ↑ Thompson, A.C. (20 November 2018). Documenting Hate: New American Nazis. Frontline. PBS/ProPublica. 15 minutes in. Retrieved 19 February 2019.
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.