View source for Acetone peroxide

{{chembox
| ImageFile = acetone peroxide.png
| ImageSize = 180px
| ImageFileL2 = acetone-peroxide-trimer-3D-balls.png
| ImageSizeL2 = 180px
| ImageNameL2 = Acetone peroxide trimer
| ImageFileR2 = acetone peroxide.jpg
| ImageSizeR2 = 180px
| IUPACName = 3,3,6,6-Tetramethyl-1,2,4,5-tetraoxane<br>(dimer)<br>3,3,6,6,9,9-Hexamethyl-1,2,4,<br>5,7,8-hexaoxacyclononane<br>(trimer)
| OtherNames =
| Section1 = {{Chembox Identifiers
| CASNo = 17088-37-8
| PubChem = 536100
| SMILES = CC1(C)OOC(C)(C)OO1 (dimer)<br>CC1(C)OOC(C)(C)OOC(C)(C)OO1 (trimer)
}}
| Section2 = {{Chembox Properties
| Formula = C<sub>6</sub>H<sub>12</sub>O<sub>4</sub> (dimer)<br>C<sub>9</sub>H<sub>18</sub>O<sub>6</sub> (trimer)
| MolarMass = 148.157&nbsp;g/mol&nbsp;(dimer)<br>222.24&nbsp;g/mol (trimer)
| Appearance = White crystalline solid
| Density =
| MeltingPtC = 91
| BoilingPt = 97–160 °C
| Solubility = }}
| Section3 = {{Chembox Hazards
| MainHazards = Explosive
| FlashPt =
| Autoignition = }}
| Section6 = {{Chembox Explosive
| ShockSens = Very high / moderate when wet
| FrictionSens = Very high / moderate when wet
| ExplosiveV = 5300 [[metre per second|m/s]]<br>17,384 ft/s<br>3.29 miles per second
| REFactor = .83}}
}}
'''Acetone peroxide''' ('''triacetone triperoxide''', '''peroxyacetone''', '''TATP''', '''TCAP''') is an [[organic peroxide]] and a [[primary explosive|primary]] [[high explosive]]. It takes the form of a white crystalline powder with a distinctive acrid odor.

It is susceptible to heat, friction, and [[Shock (mechanics)|shock]]. However the instability is greatly altered by impurities. It is normally  fairly stable when pure. It is not easily soluble in water.  It is more stable and  less sensitive when wet.

== History ==

Acetone peroxide was discovered in 1895 by [[Richard Wolffenstein (chemist)|Richard Wolffenstein]].<ref>{{cite journal| first=R| last=Wolffenstein| title=Über die Einwirkung von Wasserstoffsuperoxyd auf Aceton und Mesityloxyd (On the effect of hydrogen peroxide on acetone and mesityl oxide)| journal=Chemische Berichte| volume=28| pages= 2265| year=1895 | doi = 10.1002/cber.189502802208}}</ref><ref>See also:  Richard Wolffenstein, Deutsches Reich Patent 84,953 (1895).</ref> He was the first chemist to use inorganic acids as catalysts. He was also the first researcher to receive a patent for using the peroxide as an explosive compound. In 1900 Bayer and Villiger described in the same journal the first synthesis of the [[Dimer (chemistry)|dimer]] and also described use of acids for the synthesis of both peroxides.<ref>Adolf Baeyer and Victor Villiger (1900) "Über die Einwirkung des Caro'schen Reagens auf Ketone" (On the effect of Caro's reagent on ketones), ''Berichte der deutschen chemischen Gesellschaft'', vol. 33, pages 858-864. See also:  Adolf Baeyer and Victor Villiger (1900) "Über die Nomenclatur der Superoxyde und die Superoxyde der Aldehyde," ''Berichte der deutschen chemischen Gesellschaft'', vol. 33, pages 2479-2487.</ref> Information about these procedures including the relative proportions of [[monomer]], [[Dimer (chemistry)|dimer]], and trimer is also available in an article by Milas and Golubović.<ref>{{cite journal
| title = Studies in Organic Peroxides. XXVI. Organic Peroxides Derived from Acetone and Hydrogen Peroxide
| author = Milas N. A., Golubović A.
| journal = [[Journal of the American Chemical Society]]
| year = 1959
| volume = 81
| issue = 24
| pages = 6461–6462
| doi =  10.1021/ja01533a033
}}</ref> Other sources include [[crystal]] structure and 3d analysis in ''The Chemistry of Peroxides'' edited by [[Saul Patai]] (pp.&nbsp;396–7), as well as the ''Textbook of Practical Organic Chemistry'' by [[Arthur Israel Vogel|Vogel]].

==Chemistry==
"Acetone peroxide" most commonly refers to the [[Alicyclic compound|cyclic]] [[Trimer (chemistry)|trimer]] TCAP (tri-cyclic acetone peroxide, or tri-cyclo, [[Carbon|C]]<sub>9</sub>[[hydrogen|H]]<sub>18</sub>[[oxygen|O]]<sub>6</sub>) obtained by a reaction between [[hydrogen peroxide]] and [[acetone]] in an acid-[[catalyst|catalyzed]] [[nucleophilic addition]].<ref>{{cite web
| url=http://www.roguesci.org/megalomania/explo/acetoneperoxide.html
| title=Megalomania's Method of Making Acetone Peroxide| work=Megalomania's Controversial Chem Lab
| date=January 31, 2004}}</ref> The [[Dimer (chemistry)|dimer]] (C<sub>6</sub>H<sub>12</sub>O<sub>4</sub>) and open [[monomer]] are also formed, but under proper conditions the cyclic trimer is the primary product. A [[oligomer|tetrameric]] form was also described.<ref name="Jiang H., Chu G., Gong H., Qiao Q. 1999 288–289">{{cite journal
| author = Jiang H., Chu G., Gong H., Qiao Q.
| title = Tin Chloride Catalysed Oxidation of Acetone with Hydrogen Peroxide to Tetrameric Acetone Peroxide
| journal = [[Journal of Chemical Research]]
| volume =28
| pages = 288–289
| year =1999
| doi =10.1039/a809955c}}</ref> In mildly [[acid]]ic or neutral conditions, the reaction is much slower and produces more [[monomer]]ic [[organic peroxide]] than the reaction with a strong acid catalyst. Due to significant [[angle strain|strain]] of the [[covalent bond|chemical bonds]] in the dimer and especially the monomer, they are even more unstable than the trimer.<ref>{{cite journal
| title = Trace Analysis of Peroxide-Based Explosives
| author = Schulte-Ladbeck, R.; Kolla, P.; Karst, U.
| journal = [[Analytical Chemistry]]
| year = 2003
| volume = 75
| issue =4
| pages = 731–735
| doi =  10.1021/ac020392n}}</ref>

At room temperature, the trimeric form slowly [[sublimation (physics)|sublimes]], reforming as larger crystals of the same peroxide.

Acetone peroxide is notable as a high explosive not containing [[nitrogen]]. This is one reason why it has become popular with terrorists,<ref name="mother of satan">{{cite web
  | last = Genuth
  | first = Iddo
  | coauthors = Lucille Fresco-Cohen
  | title = TATP: Countering the Mother of Satan
  | publisher = The Future of Things
  | date = 6 November 2006
  | url = http://thefutureofthings.com/articles/35/tatp-countering-the-mother-of-satan.html
  | quote = 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
  | accessdate = 24 September 2009}}</ref> as it can pass through scanners designed to detect nitrogenous explosives.<ref>{{cite web
  | last =
  | first =
  | title = Feds are all wet on airport security
  | publisher = Star-Ledger
  | date = 24 August 2006
  | url = http://results.factiva.com/index/index.aspx?ref=NSL0000020060824e28o0001y
  | quote = At the moment, Watts said, the screening devices are set to detect nitrogen-based explosives, a category that doesn't include TATP
  | accessdate = 11 September 2009}}</ref>

TCAP generally burns when ignited, unconfined, in quantities less than about 2&nbsp;grams. More than 2&nbsp;grams will usually [[Explosive material|detonate]] when ignited; smaller quantities might detonate when even slightly confined. Completely dry TCAP is much more prone to detonation than the fresh product still wetted with water or acetone. The [[oxidation]] that occurs when burning is:

:2 {{chem|C|9|H|18|O|6}} + 21 {{chem|O|2}} → 18 {{chem|H|2|O}} + 18 {{chem|CO|2}}

Theoretical examination of the explosive [[chemical decomposition|decomposition]] of TCAP, in contrast, predicts in "formation of [[acetone]] and [[ozone]] as the main decomposition products and not the intuitively expected oxidation products."<ref name=http://www.technion.ac.il/~keinanj/pub/122.pdf>{{cite journal
| title = Decomposition of Triacetone Triperoxide Is an Entropic Explosion
| author = F. Dubnikova, R. Kosloff, J. Almog, Y. Zeiri, R. Boese, H. Itzhaky, A. Alt, E. Keinan
| journal = [[Journal of the American Chemical Society]]
| year = 2003
| volume = 127
| issue = 4
| pages = 1146–1159
| doi =  10.1021/ja0464903
| url = http://www.technion.ac.il/~keinanj/pub/122.pdf
| pmid = 15669854}}</ref>  But even in 1943 German researcher(s) described in the case of detonation of the trimer the formation of formaldehyde which is clearly a result of a fragmentation of primary formed oxyradicals{{Citation needed|date=March 2007}}. This result is in good agreement with the results of 60 years of the study of controlled decompositions in various organic peroxides. It is the rapid creation of gas from a solid that creates the explosion. Very little heat is created by the explosive decomposition of TCAP. Recent research describes TCAP decomposition as an [[entropic explosion]].<ref name=http://www.technion.ac.il/~keinanj/pub/122.pdf/>

The extreme shock, heat, and friction sensitivity are due to the [[instability]] of the [[molecule]]. Big crystals, found in older mixtures, are more dangerous, as they are easier to shatter—and initiate—than small ones.

Due to the cost and ease with which the precursors can be obtained, acetone peroxide can be manufactured by those without the resources needed to manufacture or buy more sophisticated explosives.{{Citation needed|date=July 2008}} When the reaction is carried out without proper equipment the risk of an accident is significant. Simply mixing sulfuric acid, hydrogen peroxide, and acetone can create the substance. The mixture starts as a liquid that quickly crystallizes into a powder.

There is a common myth that the only "safe" acetone peroxide is the trimer, made at low temperatures:

<blockquote>"The mixture must be kept below 10 degrees Celsius. If the crystals form at this temperature, it forms the isomer called tricycloacetone peroxide, which is relatively stable and safe to handle. If the crystals form above this temperature, the dimeric form, called dicycloacetone peroxide. This isomer is much more unstable, and could go off at the touch, making it not safe enough to be considered a practical explosive. As long as the temperature is kept below 10 degrees Celsius, then there is little to worry about."<ref>{{cite web
  | last =
  | first = unstable247
  | title = Detailed Description of the Synthesis of Acetone Peroxide
  | publisher = totse.com
  | date = 
  | url = http://www.zoklet.net/totse/en/bad_ideas/ka_fucking_boom/162660.html
  | accessdate = May 29, 2010}}</ref></blockquote>

In reality, the acid-catalyzed peroxidation of acetone always produces a mixture of the  dimeric and trimeric forms.{{Citation needed|date=July 2008}}

The trimer is the more stable form, but not much more so than the dimer. All forms of acetone peroxide are  sensitive to [[initiation (chemistry)|initiation]]. Organic peroxides are sensitive, dangerous explosives; due to their sensitivity they are rarely used by well funded militaries. Even for those who synthesize [[explosives]] as a hobby there are far safer explosives with syntheses nearly as simple as that of acetone peroxide.  It is commonly combined with nitrocellulose by dissolving the nitrocellulose in acetone and then mixing in the acetone peroxide and letting it dry, this results in a mixture that is both more stable and somewhat more powerful than acetone peroxide by itself. This mixture is commonly referred to as APNC.

'''Tetrameric''' acetone peroxide is more chemically stable (heating to 120°C for 4 hours), but despite this, it is still a very dangerous [[primary explosive]]. It can be prepared using [[tin(IV) chloride]] (without acid present) as a catalyst with up to 40% yield if [[Radical (chemistry)|radical]] [[Enzyme inhibitor|inhibitor]] such as [[hydroquinone]], or a [[chelator]] such as [[EDTA]] is added.<ref name="Jiang H., Chu G., Gong H., Qiao Q. 1999 288–289"/>

It evaporates 6.5% in 24 h at 14-18°C. Openly at air at 25°C has a loss by sublimation of 68.6% in 14 days.<ref>http://www.economypoint.org/a/acetone-peroxide.html</ref>Many accidents resulted from the fact that acetone peroxide detonates due to its sublimation characteristics within fewer days by crystallization in the range of the container cap, when opening the same. Keeping it wet, stops the sublimation, and can prevent this type of accidents.

== Industrial occurrence ==
Acetone peroxides are common and unwanted [[by-product]]s of oxidation reactions, such as those used in [[phenol]] syntheses. Due to their explosivity, they are hazardous. Numerous methods are used to reduce their production - shifting the [[pH]] to more alkaline, adjusting the reaction temperature, or adding a soluble [[copper]](II) compound.<ref>[http://www.freepatentsonline.com/5003109.html Destruction of acetone peroxide patent]</ref>

Acetone peroxide and [[benzoyl peroxide]] are used as [[flour bleaching agent]]s to [[bleach]] and "mature" [[flour]].<ref>Food additives list from the codex alimentarius, http://www.codexalimentarius.net/web/more_info.jsp?id_sta=7</ref>

[[organic peroxide|Ketone peroxides]], including acetone peroxide, [[methyl ethyl ketone peroxide]], and [[benzoyl peroxide]], find applications as [[Radical initiator|initiator]]s for [[polymerization]] reactions of e.g. [[silicone]] or [[polyester]] [[resin]]s, often encountered when making [[fiberglass]]-reinforced composites. For these uses, the peroxides are typically in the form of a dilute solution in an organic solvent, however, even commercial products with higher concentrations of organic peroxides can form crystals around the lid when older, making the can shock-sensitive. Methyl ethyl ketone is more common for this purpose, however, as it is stable in storage.

== Accidental byproduct ==
Acetone peroxide can also occur accidentally, when suitable chemicals are mixed together, for example when [[methyl ethyl ketone peroxide]] is mixed with acetone while making fiberglass composites, and left to stand for some time, or when a mixture of peroxide and hydrochloric acid from [[printed circuit board]] etching is mixed with waste acetone from cleaning the finished board and allowed to stand. While amounts obtained this way are typically much smaller than from intentional production, they are also less pure and prepared without cooling, and hence very unstable.

It is also a hazardous by-product of [[isosafrole]] oxidation in acetone, a step in the synthesis of [[MDMA]].

== Terrorist incidents ==
TATP is relatively easy to make and has been used in various [[terrorism|terrorist]] acts.<ref>[http://www.timesonline.co.uk/article/0,,22989-1695442,00.html July 15, 2005 TimesOnline]</ref> Due to its high susceptibility to accidental detonation by shock, friction, or sparks, acetone peroxide has earned the nickname "Mother of Satan" among certain [[Islamic terrorism|Islamic militant groups]].<ref name="mother of satan"/>

* [[Richard Reid (shoe bomber)|Richard Reid]] of al-Qaeda targeted the Dec 22, 2001 [[American Airlines Flight 63]] with a bomb concealed in his shoe with a TATP trigger.
* It is also believed that TATP was used as the explosive in the [[7 July 2005 London bombings]].<ref>[http://observer.guardian.co.uk/uk_news/story/0,,1769440,00.html "The real story of 7/7"], ''[[The Observer]]'', May 7, 2006</ref>
* On September 5, 2006, homemade TATP was found during the arrest of [[Vollsmose terrorists|seven suspected terrorists in Vollsmose]], a neighborhood in the Danish city [[Odense]].<ref>http://politiken.dk/indland/article171600.ece ''Explosives found in Vollmose.'' (in Danish)</ref>
* On September 4, 2007, homemade TATP was found during the arrest of eight suspected al-Qaeda collaborators in [[Copenhagen]], [[Denmark]].<ref>[http://politiken.dk/indland/article373632.ece ''"Satan's Mother" found at the Residence of Suspected Terrorist.'' (in Danish)]</ref>
* The [[2006 transatlantic aircraft plot]] was a terrorist plot to detonate liquid explosives carried on board at least 10 airliners travelling from the United Kingdom to the United States and Canada.
* A member of the French anti-[[traffic enforcement camera|speed camera]] group, [[FNAR|Front national anti-radars]] (FNAR), was hospitalised after losing both hands to an accidental explosion of his bomb based on TATP.<ref>{{fr icon}} [http://www.lefigaro.fr/actualite-france/2008/05/29/01016-20080529ARTFIG00667-front-antiradar-un-troisieme-homme-interroge.php Front antiradar : un troisième homme interrogé] , Le Figaro, 2008-05-29</ref>
* The [[Northwest Airlines Flight 253]] attempted al-Qaeda bombing on Christmas Day, December 25, 2009, was by a bomb that in part contained TATP.<ref name=indict>{{cite news| url= http://www.cbsnews.com/htdocs/pdf/Abdulmutallab_Indictment.pdf  |date=January 6, 2010  |title= Indictment in U.S. v. Abdulmutallab |work=  |accessdate=January 10, 2010}}</ref>
* On September 10, 2010, A TATP bomb accidently exploded injuring the bombmaker in a toilet at Hotel Jørgensen in the Danish capital [[Copenhagen]].<ref>http://politiken.dk/indland/1059409/avis-bombemand-havde-frygtet-spraengstof-paa-sig/ ''Bomber carried feared explosive.'' (in Danish)</ref>

==Notable accidents==
A 13-year-old student in Hong Kong was injured on March 28, 2009 when he tried to light some TATP powder provided by a 14-year-old boy. Police found six more bottles of TATP from his apartment. Police believe those bottles of TATP were homemade by the 14-year-old boy for curiosity's sake. The injured boy and two other teenagers were later arrested on charges of possession of explosives.<ref>[http://www.rthk.org.hk/rthk/news/englishnews/news.htm?all&20090328&56&570003 3 arrested after teen injured in blast], RTHK English News, 2009-03-28</ref><ref>[http://appledaily.atnext.com/template/apple/art_main.cfm?iss_id=20090329&sec_id=4104&subsec_id=11866&art_id=12565696 3 arrested after teen injured in TATP blast (in Chinese)], Apple Daily, 2009-03-29</ref>

== References ==
{{Reflist}}

== External links ==
{{Commons category|Acetone peroxide}}

{{DEFAULTSORT:Acetone Peroxide}}
[[Category:Explosive chemicals]]
[[Category:Ketals]]
[[Category:Organic peroxides]]
[[Category:Oxygen heterocycles]]

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[[it:Perossido di acetone]]
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[[ja:過酸化アセトン]]
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[[pt:Triperóxido de triacetona]]
[[ru:Перекись ацетона]]
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[[Category:2Fix]]