| Revision as of 15:47, 23 February 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Script assisted update of identifiers from ChemSpider, CommonChemistry and FDA for the Chem/Drugbox validation project - Updated: ChEMBL.← Previous edit |
Latest revision as of 20:22, 1 January 2025 edit undoDulciana (talk | contribs)Extended confirmed users5,424 editsm →Properties as an explosive: sentence order |
| (182 intermediate revisions by 85 users not shown) |
| Line 1: |
Line 1: |
|
|
{{Use dmy dates|date=November 2020}} |
|
{{chembox |
|
{{chembox |
|
| verifiedrevid = 400104548 |
|
| verifiedrevid = 415524053 |
|
|
| Name = |
|
| ImageFile = HMTD structure.png |
|
|
| ImageSize = 150px |
|
| ImageFile = |
|
|
| ImageFile1 = HMTD structure.png |
|
| IUPACName = 3,4,8,9,12,13-Hexaoxa-1,6-<br>diazabicyclotetradecane |
|
|
|
| ImageSize1 = 150px |
|
| OtherNames = |
|
|
|
| ImageFile2 = Heksametylenotriperoksydiamina.JPG |
|
|
| ImageSize2 = |
|
|
| ImageFile3 = |
|
|
| ImageSize3 = |
|
|
| PIN = 3,4,8,9,12,13-Hexaoxa-1,6-diazabicyclotetradecane |
|
|
| OtherNames = |
|
|
| SystematicName = |
|
| Section1 = {{Chembox Identifiers |
|
| Section1 = {{Chembox Identifiers |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| Line 10: |
Line 18: |
|
| InChI = 1/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2 |
|
| InChI = 1/C6H12N2O6/c1-7-2-11-13-5-8(4-10-9-1)6-14-12-3-7/h1-6H2 |
|
| InChIKey = HMWPNDNFTFSCEB-UHFFFAOYAC |
|
| InChIKey = HMWPNDNFTFSCEB-UHFFFAOYAC |
|
|
| ChEMBL_Ref = {{ebicite|correct|EBI}} |
|
| ChEMBL = 346085 |
|
| ChEMBL = 346085 |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
| Line 15: |
Line 24: |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey = HMWPNDNFTFSCEB-UHFFFAOYSA-N |
|
| StdInChIKey = HMWPNDNFTFSCEB-UHFFFAOYSA-N |
|
|
| CASNo_Ref = {{cascite|correct|??}} |
|
| CASNo = 283-66-9 |
|
| CASNo = 283-66-9 |
|
| PubChem = 61101 |
|
| PubChem = 61101 |
| Line 23: |
Line 33: |
|
| MolarMass = 208.17 g/mol |
|
| MolarMass = 208.17 g/mol |
|
| Appearance = White crystalline solid |
|
| Appearance = White crystalline solid |
|
| Density = 0.88 g/cm<sup>3</sup> |
|
| Density = 1.57 g/cm<sup>3</sup> |
|
| MeltingPt = Decomposes at 75 °C<br>Ignites spontaneously at 133 °C |
|
| MeltingPt = Decomposes at 75 °C<br>Ignites spontaneously at 133 °C |
|
| BoilingPt = |
|
| BoilingPt = |
|
| Solubility = }} |
|
| Solubility = }} |
|
| Section3 = {{Chembox Hazards |
|
| Section3 = {{Chembox Hazards |
|
|
| GHSPictograms = {{GHS01}} {{GHS07}} |
|
| MainHazards = |
|
|
|
| GHSSignalWord = '''DANGER''' |
|
| FlashPt = |
|
|
|
| HPhrases = {{H-phrases|202|205|241|300|315|318|335}} |
|
| Autoignition = }} |
|
|
|
| PPhrases = {{P-phrases|102|220|243|250|261|264|280|283|370+380|372|404}} |
|
|
| NFPA-F = 1 |
|
|
| NFPA-H = 1 |
|
|
| NFPA-R = 4 |
|
|
| MainHazards = Explosive |
|
|
| FlashPt = |
|
|
| AutoignitionPt = }} |
|
|
| Section4 = |
|
|
| Section5 = |
|
| Section6 = {{Chembox Explosive |
|
| Section6 = {{Chembox Explosive |
|
| ShockSens = High |
|
| ShockSens = High |
|
| FrictionSens = High |
|
| FrictionSens = Very High |
|
| ExplosiveV = ~4511 ] |
|
| DetonationV = ~2800 ] (at around 0.4 g/cm<sup>3</sup>) - 5100 ] at around 1.1 g/cm<sup>3</sup> |
|
| REFactor = }} |
|
| REFactor = 0.74}} |
|
}} |
|
}} |
|
|
|
|
|
|
'''Hexamethylene triperoxide diamine''' ('''HMTD''') is a <!-- note to editors: "high explosive", not "highly explosive", is the correct term --> ] ]. HMTD is an ], a ] with a cage-like structure. It is a ]. It has been considered as an initiating explosive for ] in the early part of 20th century, mostly because of its high initiating power (higher than that of ]) and its inexpensive production. As such, it was quickly taken up as a primary explosive in mining applications.<ref>Taylor, C. A.; Rinkenbach, W. H. ''Army Ordnance'' '''1924'''. ''5'', 463–466{{Verify source|Is 1924 the volume or the year? What is the title of the article? Is Army Ordnance really the magazine/journal title? Or is it just Ordnance?|date=March 2009}}</ref> However, it has since been superseded by more (chemically) stable compounds such as dextrinated ] and ] (which contains no lead or mercury). HMTD is widely used in amateur-made blasting caps. |
|
'''Hexamethylene triperoxide diamine''' ('''HMTD''') is a |
|
|
<!-- note to editors: "high explosive", not "highly explosive", is the correct term --> |
|
|
] ], first synthesised in 1885 by Legler.<ref>{{cite journal |last=Legler |first=L . |year=1885 |title=Ueber Producte der langsamen Verbrennung des Aethyläthers |url=http://gallica.bnf.fr/ark:/12148/bpt6k90703s/f1537.chemindefer |journal=Berichte der deutschen chemischen Gesellschaft |volume=18 |pages=3343–3351 |doi=10.1002/cber.188501802306}}</ref> The theorised structure lent itself well to acting as an initiating, or ]. While still quite sensitive to shock and friction, it was relatively stable compared to other initiating explosives of the time, such as ], and proved to be relatively inexpensive and easy to synthesise. As such, it was quickly taken up as a primary explosive in mining applications.<ref>Taylor, C. A.; Rinkenbach, W. H. ''Army Ordnance'' '''1924'''. ''5'', 463-466{{Verify source|Is 1924 the volume or the year? What is the title of the article? Is Army Ordnance really the magazine/journal title? Or is it just Ordnance?|date=March 2009}}</ref> However, it has since been superseded by even more stable compounds such as ]. |
|
|
|
|
|
|
==Preparation and properties== |
|
==Preparation and structure== |
|
HMTD may be prepared by the reaction of an aqueous solution of ] and ] in the presence of ] or dilute ] as a ]. |
|
First synthesised in 1885 by the German chemist Ludwig Legler,<ref>{{cite journal |last=Legler |first=L. |year=1885 |title=Ueber Producte der langsamen Verbrennung des Aethyläthers |url=http://gallica.bnf.fr/ark:/12148/bpt6k90703s/f1537.chemindefer |journal=Berichte der Deutschen Chemischen Gesellschaft |volume=18 |issue=2 |pages=3343–3351 |doi=10.1002/cber.188501802306}}</ref> HMTD may be prepared by the reaction of an aqueous solution of ] and ] in the presence of an acid ], such as ], acetic acid or dilute ]. 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 ] geometry.<ref>{{cite journal|last=Schaefer|first=William P.|author2=Fourkas, John T. |author3=Tiemann, Bruce G. |title=Structure of hexamethylene triperoxide diamine|journal=Journal of the American Chemical Society|date=April 1985|volume=107|issue=8|pages=2461–2463|doi=10.1021/ja00294a043|bibcode=1985JAChS.107.2461S }}</ref> |
|
No peroxide has found practical use as an explosive, a consequence of the weak oxygen– |
|
|
oxygen bond leading to poor thermal and chemical stability and a high sensitivity to impact. HMTD is a more powerful |
|
|
initiating explosive than mercury fulminate but its poor thermal and chemical stability prevents |
|
|
its use in detonators.<ref name="Organic Chemistry of Explosives">{{cite book |
|
|
|author=Hodgson,Robert ; Agrawal,Jai P. |
|
|
|title=Organic Chemistry of Explosives |
|
|
|publisher=Wiley |
|
|
|location= |
|
|
|year=2007 |
|
|
|pages=414 |
|
|
|isbn= |
|
|
|oclc= |
|
|
|doi= |
|
|
|accessdate= |
|
|
}}</ref> |
|
|
|
|
|
|
|
==Properties as an explosive== |
|
Like other organic peroxides such as ], HMTD is an unstable compound that is sensitive to shock, friction, and heat. This makes the substance extremely dangerous to manufacture. It also reacts with most common metals, which can lead to detonation. HMTD is very stable when pure (acid free) and does not quickly sublime like its acetone counterparts. |
|
|
|
Like other organic peroxides, such as ] (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.<ref>Stúpajúci trend podomáckej výroby výbušnin a udalosti s tým spojené, Kriminalistický a expertízny ústav Policajného zboru, p. 8 http://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf {{Webarchive|url=https://web.archive.org/web/20210923170016/https://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf |date=23 September 2021 }}, written in Slovak</ref> Common static electricity discharges have been reported to cause detonation.<ref>Explosive Properties of Primary Explosives - Springer, p.21, section 2.33, {{ISBN|978-3-642-28436-6}}, https://www.springer.com/cda/content/document/cda_downloaddocument/9783642284359-c1.pdf?SGWID=0-0-45-1379807-p174306459 {{Webarchive|url=https://web.archive.org/web/20180721191834/https://www.springer.com/cda/content/document/cda_downloaddocument/9783642284359-c1.pdf?SGWID=0-0-45-1379807-p174306459 |date=21 July 2018 }}</ref> It is, however, less unstable than many other peroxides under normal conditions; exposure to ultraviolet light increases its sensitivity. It also reacts with most common metals, which can lead to ]. HMTD is chemically very stable when pure (free of acids, bases, and metal ions) and does not quickly sublime like its acetone counterparts. |
|
|
|
|
|
|
HMTD is a more powerful initiating explosive than mercury fulminate, but its poor thermal and chemical stability prevents its use in ]s.<ref name="Organic Chemistry of Explosives">{{cite book |
|
==Terrorism== |
|
|
|
|author1=Hodgson, Robert |author2=Agrawal, Jai P. | title=Organic Chemistry of Explosives |
|
], the al-Qaeda Millennium Bomber, used HMTD as one of the components in the explosives that he prepared to bomb Los Angeles International Airport on ] 1999/2000; the explosives could have produced a blast 40x greater than that of a devastating ].<ref name="febninth">{{cite web|url=http://www.nefafoundation.org/miscellaneous/US_v_Ressam_9thcircuitappeals0210.pdf|title=U.S. v. Ressam|last=U.S. Court of Appeals for the Ninth Circuit|date=February 2, 2010|accessdate=February 27, 2010}}</ref><ref name="comp">{{cite web|url=http://nefafoundation.org/miscellaneous/FeaturedDocs/U.S._v_Ressam_Complaint.pdf|title=Complaint; U.S. v. Ressam|date=December 1999|publisher=NEFA Foundation|accessdate=February 26, 2010}}</ref> |
|
|
|
| publisher=Wiley |
|
|
| year=2007 |
|
|
| pages=414 |
|
|
| isbn= |
|
|
| oclc= |
|
|
}}</ref> Nevertheless, HMTD is one of the three most widely used primary explosives in improvised, amateur made blasting caps, the others being ] and ]. |
|
|
|
|
|
|
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.<ref>Stúpajúci trend podomáckej výroby výbušnin a udalosti s tým spojené, Kriminalistický a expertízny ústav Policajného zboru, p. 8 http://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf {{Webarchive|url=https://web.archive.org/web/20210923170016/https://www.unms.sk/swift_data/source/dokumenty/skusobnictvo/upravy_2009/odborne_seminare_2008/KEU_BA_01_10_2008.pdf |date=23 September 2021 }}, written in Slovak</ref> |
|
Despite no longer being used in any official application, it remains a fairly popular ] and has been used in a large number of ]s throughout the world, and was possibly used in the ].<ref> ], 4 August 2005, retrieved 16 April 2006</ref> The '']'' reported it as the planned explosive in the ].<ref>{{cite news |first=Don, Jr. |last=Van Natta |authorlink=Don Van Natta, Jr. |coauthors=] and ] |date=28 August 2006 |title=Details Emerge in British Terror Case |url=http://www.nytimes.com/2006/08/28/world/europe/28plot.html |accessdate=7 February 2009 |work=]}}</ref> |
|
|
|
|
|
|
Calculated (Explo5) detonation pressure P<sub>cj</sub> at crystal density 1.597 g/cm<sup>3</sup> is 218 kbar with velocity of detonation VoD = 7777 m/s. Explosion temperature is 3141 K, energy of explosion is 5612 kJ/kg (or 3400 - 4000 kJ/kg per various sources) and volume of explosion gases at STP is calculated to be 826 L/kg. Loose powder has density close to 0.4 g/cm<sup>3</sup>, hence the common detonation velocities are closer to 3000 m/s and P<sub>cj</sub> is closer to 15 kbar.<ref>{{Cite book | url=https://books.google.com/books?id=hX3mBgAAQBAJ&q=HMTD+detonation+pressure+pressure&pg=PA524 |title = The Chemistry of Peroxides|isbn = 9781118412718|year=2015| publisher=John Wiley & Sons }}</ref> |
|
|
|
|
|
{{multiple image |
|
|
| align = left |
|
|
| direction = |
|
|
| width = 200 |
|
|
| image1 = |
|
|
| alt1 = 2 |
|
|
| caption1 = |
|
|
| image2 = |
|
|
| alt2 = 3 |
|
|
| caption2 = |
|
|
| footer = Detonation velocity of HMTD at given density. Detonation pressure at given density (estimate). |
|
|
}} |
|
|
|
|
|
==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. |
|
|
|
|
|
{{multiple image |
|
|
| align = center |
|
|
| direction = |
|
|
| width = 238 |
|
|
| image1 = |
|
|
| alt1 = 2 |
|
|
| caption1 = |
|
|
| image2 = |
|
|
| alt2 = 3 |
|
|
| caption2 = |
|
|
| image3 = |
|
|
| alt3 = 4 |
|
|
| footer = Sensitivity of HMTD compared to other primary explosives an PETN.}} |
|
|
|
|
|
==Terrorism== |
|
|
Despite no longer being used in any military application, and despite its shock sensitivity, HMTD remains a common ] and has been used in a large number of ]s 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 ]<ref name="febninth">{{cite web|url=http://www.nefafoundation.org/miscellaneous/US_v_Ressam_9thcircuitappeals0210.pdf |title=U.S. v. Ressam |last=U.S. Court of Appeals for the Ninth Circuit |date=2 February 2010 |accessdate=27 February 2010 |url-status=dead |archiveurl=https://web.archive.org/web/20121004023628/http://www.nefafoundation.org/miscellaneous/US_v_Ressam_9thcircuitappeals0210.pdf |archivedate=4 October 2012}}</ref><ref name="comp">{{cite web|url=http://nefafoundation.org/miscellaneous/FeaturedDocs/U.S._v_Ressam_Complaint.pdf|title=Complaint; U.S. v. Ressam|date=December 1999|publisher=NEFA Foundation|accessdate=26 February 2010|url-status=dead|archiveurl=https://web.archive.org/web/20120301162643/http://nefafoundation.org/miscellaneous/FeaturedDocs/U.S._v_Ressam_Complaint.pdf|archivedate=1 March 2012}}</ref> |
|
|
and the ],<ref>{{cite news|date=20 September 2016|title=7 questions we have about bombings in New York and New Jersey|url=http://www.cnn.com/2016/09/20/us/new-york-new-jersey-bomb-questions/|accessdate=20 September 2016|work=]|first=Susannah|last=Cullinane|author2=Shimon Prokupecz|author3=Emanuella Grinberg|author4=Holly Yan|author2-link=Shimon Prokupecz}}</ref> as well as one of the components of the explosives attempted to be made by the ] terrorist organization ] in the United States.<ref>{{Cite AV media|url=https://www.pbs.org/wgbh/frontline/film/documenting-hate-new-american-nazis/|title=Documenting Hate: New American Nazis|minutes=15|publisher=]/]|series= ]|first=A.C.|last=Thompson|language=en-US|date=2018-11-20|access-date=2019-02-19}}</ref> |
|
|
|
|
|
==References== |
|
==References== |
|
|
{{reflist|colwidth=30em}} |
|
{{Reflist}} |
|
|
{{Use dmy dates|date=September 2010}} |
|
|
|
|
|
|
{{DEFAULTSORT:Hexamethylene Triperoxide Diamine}} |
|
{{DEFAULTSORT:Hexamethylene Triperoxide Diamine}} |
|
] |
|
] |
|
] |
|
] |
|
] |
|
] |
|
|
] |
|
|
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|