Acetone peroxide

From Wikipedia, the free encyclopedia
Jump to: navigation, search
Acetone peroxide
Acetone peroxide.svg

[Cyclic dimer and trimer examples]
Acetone peroxide trimer
Acetone peroxide.jpg
Names
IUPAC names
3,3-Dimethyl-1,2-dioxacyclopropane
(monomer)
3,3,6,6-Tetramethyl-1,2,4,5-tetraoxane
(dimer)
3,3,6,6,9,9-Hexamethyl-1,2,4,
5,7,8-hexaoxacyclononane
(trimer)
3,3,6,6,9,9,12,12-Octamethyl-1,2,4,
5,7,8,10,11-octaoxacyclododecane
(tetramer)
Other names
Triacetone Triperoxide
Peroxyacetone
Mother of Satan
Identifiers
17088-37-8 N
ChemSpider 3582942 YesY
Jmol interactive 3D dimer: Image
trimer: Image
PubChem 536100
Properties
C6H12O4 (dimer)
C9H18O6 (trimer)
C12H24O8 (tetramer)
Molar mass 148.157 g/mol (dimer)
222.24 g/mol (trimer)
Appearance White crystalline solid
Melting point 91 °C (196 °F; 364 K)
Boiling point 97 to 160 °C (207 to 320 °F; 370 to 433 K)
insoluble
Hazards
Main hazards Explosive
Explosive data
Shock sensitivity High / moderate when wet
Friction sensitivity High / moderate when wet
Detonation velocity 5300 m/s
17,384 ft/s
3.29 miles per second
RE factor 0.83
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Acetone peroxide is a chemical term used to refer to a small family of explosive organic peroxides that are tetrameric, trimeric, dimeric, and monomeric peroxides of acetone, which can take cyclic or open chain forms. One frequently studied is the trimer, tri-cyclic acetone peroxide (TCAP; synonyms triacetone triperoxide, TATP; peroxyacetone). Some forms of these peroxides take the form of a crystalline powders. Most can explode if subjected to heat, friction, or shock. TCAP has been implicated as the primary high explosive used in terrorist attacks in Europe in 2016 and earlier.

History[edit]

Acetone peroxide[clarification needed] was discovered in 1895 by Richard Wolffenstein.[2][non-primary source needed] [3][non-primary source needed] He was the first researcher to receive a patent for using the peroxide as an explosive compound.[citation needed]

In 1900 Bayer and Villiger described the first synthesis of the dimer and described use of acids for the synthesis of both peroxides.[4][non-primary source needed] Work on this methodology, and on the various products obtained, was further investigated in the mid-20th century by Milas and Golubović.[1][non-primary source needed]

Chemistry[edit]

Synthesis of tri-cyclic acetone peroxide.

The chemical name acetone peroxide is most commonly used to refer to the cyclic trimer tri-cyclic acetone peroxide (TCAP) obtained by a reaction between hydrogen peroxide and acetone in an acid-catalyzed nucleophilic addition, although various further monomeric and dimeric forms are possible.[citation needed]

Specifically, two dimers, one cyclic (C6H12O4)[citation needed] and one open chain (C6H14O4), as well as an open chain monomer (C3H8O4), can also be formed; under a particular set of conditions of reagent and acid catalyst concentration, the cyclic trimer is the primary product.[1][non-primary source needed] A tetrameric form has also been described, under different catalytic conditions.[5][non-primary source needed][better source needed] Under neutral conditions, the reaction is reported to produce the monomeric organic peroxide.[1][non-primary source needed] Due to significant angle strain of the chemical bonds in the dimer and monomer,[clarification needed] they are even more unstable than the trimer.[citation needed]

Tetrameric acetone peroxide

Organic peroxides in general are sensitive, dangerous explosives, and all forms of acetone peroxide are sensitive to initiation.[citation needed] TCAP decomposes explosively; examination of the explosive decomposition of TCAP predicts "formation of acetone and ozone as the main decomposition products and not the intuitively expected oxidation products."[6] Very little heat is created by the explosive decomposition of TCAP; the foregoing computational analysis suggests that TCAP decomposition as an entropic explosion.[6] However, this hypothesis has been challenged as not conforming to actual measurements.[7] The tetrameric form of acetone peroxide, prepared under neutral conditions using a tin catalyst (with a chelator or general inhibitor of radical chemsitry present), is reported to be more chemically stable, although still a very dangerous primary explosive.[5]

Some forms of acetone peroxide are prone to loss by sublimation and evaporation.[citation needed]

Industrial uses[edit]

Ketone peroxides, including acetone peroxide and methyl ethyl ketone peroxide, find application, alongside other compounds such as benzoyl peroxide, as initiators for polymerization reactions—e.g. silicone or polyester resins, in the making of fiberglass-reinforced composites.[citation needed] For these uses, the peroxides are typically in the form of a dilute solution in an organic solvent; methyl ethyl ketone is more common for this purpose, as it is stable in storage.[citation needed]

Acetone peroxides are common and unwanted by-products of oxidation reactions, such as those used in phenol syntheses.[citation needed]

Acetone peroxide and benzoyl peroxide are used as flour bleaching agents to bleach and "mature" flour.[8][dead link][citation needed]

Due to their explosive nature, their presence in chemical processes creates potential hazardous situations.[citation needed] Numerous methods are used to reduce their appearance as byproducts—for instance, shifting pH to more alkaline, adjusting reaction temperature, or adding inhibitors of their production.[9][non-primary source needed]

Use in improvised explosive devices[edit]

See also: Improvised explosive device

Acetone peroxide has earned the nickname "Mother of Satan"[10] as it can pass through scanners designed to detect nitrogenous explosives.[11] for its high susceptibility to accidental detonation, but is used by terrorists due to the low cost and ease with which the precursors can be obtained; and because it is one of the few high explosives not containing nitrogen,[10] so can pass undetected through scanners designed to detect nitrogenous explosives.[12] It can be made from readily available ingredients such as hair bleach and nail polish remover, and with relatively basic equipment. However, due to the highly unstable nature of both the desired end product -and even more unstable impure forms that may result from imprecise manufacture or unpredictable ingredients - attempting its creation, even with expert training, is highly dangerous. [13]

[14]

TATP has been used in bomb and suicide attacks and in improvised explosive devices, including in Israel and the London bombings on 7 July 2005, in which four suicide bombers killed 52 people and injured more than 700.[15][16] It was one of the explosives used by the "shoe bomber" Richard Reid[16] and was also used by the suicide bombers in the November 2015 Paris attacks and the March 2016 Brussels attacks.[14]

Several methods can be used for trace analysis of TATP,[17] including gas chromatography/mass spectrometry (GC/MS)[18][19][20][21][22] high performance liquid chromatography/mass spectrometry (HPLC/MS),[23][24][25][26][27] and HPLC with post-column derivitization.[28]

References[edit]

  1. ^ a b c d Milas N. A., Golubović A. (1959). "Studies in Organic Peroxides. XXVI. Organic Peroxides Derived from Acetone and Hydrogen Peroxide". Journal of the American Chemical Society 81 (24): 6461–6462. doi:10.1021/ja01533a033. [non-primary source needed]
  2. ^ Wolffenstein, R (1895). "Über die Einwirkung von Wasserstoffsuperoxyd auf Aceton und Mesityloxyd (On the effect of hydrogen peroxide on acetone and mesityl oxide)". Berichte der Deutschen chemischen Gesellschaft 28 (2): 2265–2269. doi:10.1002/cber.189502802208. [non-primary source needed]
  3. ^ Wolffenstein, Richard (1895) Deutsches Reich Patent 84,953.[non-primary source needed]
  4. ^ Baeyer, Adolf; Villiger, Victor (1900). "Über die Einwirkung des Caro'schen Reagens auf Ketone" [On the effect of Caro's reagent on ketones]. Berichte der deutschen chemischen Gesellschaft 33 (1): 858–864. doi:10.1002/cber.190003301153. ;[non-primary source needed] See also Baeyer, Adolf; Villiger, Victor (1900). "Über die Nomenclatur der Superoxyde und die Superoxyde der Aldehyde" [On the nomenclature of peroxides and the peroxide of aldehyde]. Berichte der deutschen chemischen Gesellschaft 33 (2): 2479–2487. doi:10.1002/cber.190003302185. [non-primary source needed]
  5. ^ a b Jiang H., Chu G., Gong H., Qiao Q. (1999). "Tin Chloride Catalysed Oxidation of Acetone with Hydrogen Peroxide to Tetrameric Acetone Peroxide". Journal of Chemical Research 28 (4): 288–289. doi:10.1039/a809955c. [non-primary source needed]
  6. ^ a b Dubnikova, F.; Kosloff, R.; Almog, J.; Zeiri, Y.; Boese, R.; Itzhaky, H.; Alt, A. and Keinan, E. (2003). "Decomposition of Triacetone Triperoxide Is an Entropic Explosion" (PDF). Journal of the American Chemical Society 127 (4): 1146–1159. doi:10.1021/ja0464903. PMID 15669854. 
  7. ^ Sinditskii, V.P.; Kolesov, V.I.; Egorshev, V.Yu.; Patrikeev, D.I. and Dorofeeva, O.V. (2014). "Thermochemistry of cyclic acetone peroxides". Thermochimica Acta 585: 10–15. doi:10.1016/j.tca.2014.03.046. 
  8. ^ [1][dead link]
  9. ^ Costantini, Michel (1991-03-26) Destruction of acetone peroxide. United States Patent 5003109. Freepatentsonline.com. Retrieved on 2013-02-03.[non-primary source needed]
  10. ^ a b Genuth, Iddo & Fresco-Cohen, Lucille (2006-11-06). "TATP: Countering the Mother of Satan". The Future of Things. Retrieved 24 September 2009. The tremendous devastative force of TATP, together with the relative ease of making it, as well as the difficulty in detecting it, made TATP one of the weapons of choice for terrorists 
  11. ^ "Feds are all wet on airport security". Star-Ledger (Newark, New Jersey). 2006-08-24. Retrieved 11 September 2009. At the moment, Watts said, the screening devices are set to detect nitrogen-based explosives, a category that doesn't include TATP 
  12. ^ "Feds are all wet on airport security". Star-Ledger (Newark, New Jersey). 2006-08-24. Retrieved 11 September 2009. At the moment, Watts said, the screening devices are set to detect nitrogen-based explosives, a category that doesn't include TATP 
  13. ^ http://uk.businessinsider.com/paris-attack-tatp-chemical-bombs-2015-11
  14. ^ a b "A View of ISIS’s Evolution in New Details of Paris Attacks". The New York Times. 2016-03-19. 
  15. ^ Naughton, Philippe (2005-07-15)TATP is suicide bombers' weapon of choice. Timesonline.co.uk.
  16. ^ a b Vince, Gaia (15 July 2005). "Explosives linked to London bombings identified". New Scientist. 
  17. ^ Schulte-Ladbeck R, Vogel M, Karst U (2006). "Recent methods for the determination of peroxide-based explosives". Analytical and Bioanalytical Chemistry 386 (3): 559–65. doi:10.1007/s00216-006-0579-y. PMID 16862379. 
  18. ^ Muller, D; Levy, A; Shelef, R; Abramovich-Bar, S; Sonenfeld, D; Tamiri, T (2004). "Improved method for the detection of TATP after explosion". Journal of forensic sciences 49 (5): 935–8. PMID 15461093. 
  19. ^ Stambouli, A; El Bouri, A; Bouayoun, T; Bellimam, M. A. (2004). "Headspace-GC/MS detection of TATP traces in post-explosion debris". Forensic Science International. 146 Suppl: S191–4. doi:10.1016/j.forsciint.2004.09.060. PMID 15639574. 
  20. ^ Oxley, Jimmie C.; Smith, James L.; Shinde, Kajal; Moran, Jesse (2005). "Determination of the Vapor Density of Triacetone Triperoxide (TATP) Using a Gas Chromatography Headspace Technique". Propellants, Explosives, Pyrotechnics 30 (2): 127. doi:10.1002/prep.200400094. 
  21. ^ Sigman, M. E.; Clark, C. D.; Fidler, R; Geiger, C. L.; Clausen, C. A. (2006). "Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization". Rapid Communications in Mass Spectrometry 20 (19): 2851–7. doi:10.1002/rcm.2678. PMID 16941533. 
  22. ^ Romolo, F. S.; Cassioli, L; Grossi, S; Cinelli, G; Russo, M. V. (2013). "Surface-sampling and analysis of TATP by swabbing and gas chromatography/mass spectrometry". Forensic Science International 224 (1–3): 96–100. doi:10.1016/j.forsciint.2012.11.005. PMID 23219697. 
  23. ^ Widmer, Leo; Watson, Stuart; Schlatter, Konrad; Crowson, Andrew (2002). "Development of an LC/MS method for the trace analysis of triacetone triperoxide (TATP)??Crown copyright???Dstl and Swiss Scientific Research Service, 2002". The Analyst 127 (12): 1627. doi:10.1039/B208350G. PMID 12537371. 
  24. ^ Xu, X; Van De Craats, A. M.; Kok, E. M.; De Bruyn, P. C. (2004). "Trace analysis of peroxide explosives by high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (HPLC-APCI-MS/MS) for forensic applications". Journal of forensic sciences 49 (6): 1230–6. PMID 15568694. 
  25. ^ Cotte-Rodríguez, I; Hernandez-Soto, H; Chen, H; Cooks, R. G. (2008). "In situ trace detection of peroxide explosives by desorption electrospray ionization and desorption atmospheric pressure chemical ionization". Analytical Chemistry 80 (5): 1512–9. doi:10.1021/ac7020085. PMID 18247583. 
  26. ^ Sigman, M. E.; Clark, C. D.; Caiano, T; Mullen, R (2008). "Analysis of triacetone triperoxide (TATP) and TATP synthetic intermediates by electrospray ionization mass spectrometry". Rapid Communications in Mass Spectrometry 22 (2): 84–90. doi:10.1002/rcm.3335. PMID 18058960. 
  27. ^ Sigman, M. E.; Clark, C. D.; Painter, K; Milton, C; Simatos, E; Frisch, J. L.; McCormick, M; Bitter, J. L. (2009). "Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry". Rapid Communications in Mass Spectrometry 23 (3): 349–56. doi:10.1002/rcm.3879. PMID 19125413. 
  28. ^ Schulte-Ladbeck, R.; Kolla, P.; Karst, U. (2003). "Trace Analysis of Peroxide-Based Explosives". Analytical Chemistry 75 (4): 731–735. doi:10.1021/ac020392n. PMID 12622359. 

External links[edit]

Wikimedia Commons has media related to Acetone peroxide.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Acetone_peroxide&oldid=711556711"