Acetone peroxide
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{{explosivebox |
|Image = acetone peroxide.png
|IUPAC_name = 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)
|chemical_formula = [[Carbon|C]]<sub>6</sub>[[Hydrogen|H]]<sub>12</sub>[[Oxygen|O]]<sub>4</sub> (dimer)<br>[[Carbon|C]]<sub>9</sub>[[hydrogen|H]]<sub>18</sub>[[oxygen|O]]<sub>6</sub> (trimer)
|molecular_weight = 148.157 [[gram|g]]/[[mole (unit)|mol]] (dimer)<br>222.24 g/mol (trimer)
|shock_sensitivity = Very high / moderate when wet
|friction_sensitivity = Very high / moderate when wet
|density = 1.18 g/cm³
|explosive_velocity = 5300 [[metre per second|m/s]] 17,384 fps 3.29 Miles per second
|RE_factor = .83
|melting point = 91 [[Celsius|°C]]
|boiling_point = 97-160 degrees Celsius
|appearance = white crystalline solid
|CAS_number = 17088-37-8
|UNNumber = ''none''
|PubChem = 536100
|SMILES = {{SMILES|S=CC1(C)OOC(C)(C)OOC(C)(C)OO1}}<br>{{SMILES|S=CC1(C)OOC(C)(C)OO1}}
}}
[[Image:acetone peroxide.jpg|250px|right|thumb|Acetone peroxide]]
[[Image:acetone-peroxide-trimer-3D-balls.png|thumb|right|250px|[[Ball-and-stick model]] of the acetone peroxide trimer (TATP)]]
'''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 smell.
It is highly susceptible to heat, friction, and [[Shock (mechanics)|shock]]. For its instability, it has been called the "Mother of Satan".<ref>[http://www.timesonline.co.uk/article/0,,22989-1695442,00.html July 15, 2005 TimesOnline]</ref> It has perhaps sprung into notoriety due to its alleged use in the [[July 2005 London bombings]] and has also been reported as the explosive favored by suspects arrested on [[August 10]], [[2006]] who allegedly intended to [[2006 transatlantic aircraft plot|destroy aeroplanes flying from the United Kingdom to the United States]].<ref> [http://www.time.com/time/nation/article/0,8599,1225453,00.html Time (online): Thwarting the Airline Plot: Inside the Investigation 10 August 2006 (accessed 3 July 2007)] </ref>
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| journal=Chemische Berichte| volume=28| pages= 2265| year=1895}}</ref> He was the first chemist who used inorganic acids as a catalyst. He was also the first researcher who received a patent for using the peroxide as an explosive compound. In 1900 Bayer and Villiger described in some articles in the same journal the first synthesis of the [[dimer]] and used acids for the synthesis of both peroxides too. Information about it including the relative proportions of [[monomer]], [[dimer]], and trimer is also available an article of 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. 396–7), as well as the "Textbook of Practical Organic Chemistry" by [[Arthur Israel Vogel|Vogel]].
==Chemistry==
Also known as '''peroxyacetone''', acetone peroxide most commonly refers to the [[Alicyclic compound|cyclic]] [[Trimer (chemistry)|trimer]] '''TCAP''' (tri-cyclic acetone peroxide, or tri-cyclo), also called '''triacetone triperoxide''' ('''TATP'''), 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
| year=January 31, 2004}}</ref> The cyclic dimer ([[Carbon|C]]<sub>6</sub>[[hydrogen|H]]<sub>12</sub>[[oxygen|O]]<sub>4</sub>) and open [[monomer]] and [[dimer]] are also formed, but under proper conditions the cyclic [[trimer]] is the primary product. A [[oligomer|tetrameric]] form was also described.<ref>{{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,{{Fact|date=July 2008}} as it can pass through scanners designed to detect nitrogenous explosives.
TCAP generally burns when ignited, unconfined, in quantities less than about 2 grams. More than 2 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 [[carbon|C]]<sub>9</sub>[[hydrogen|H]]<sub>18</sub>[[oxygen|O]]<sub>6</sub> + 21 [[oxygen|O]]<sub>2</sub> → 18 [[hydrogen|H]]<sub>2</sub>[[oxygen|O]] + 18 [[carbon|C]][[oxygen|O]]<sub>2</sub>
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}}</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{{Fact|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 is commonly manufactured{{Fact|date=July 2008}} by those without the resources needed to manufacture or buy more sophisticated explosives. When the reaction is carried out without proper equipment the risk of an accident is significant.
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 dimerric 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>[http://www.totse.com/en/bad_ideas/ka_fucking_boom/162660.html "Detailed description of the synthesis of Acetone Peroxide"]</ref></blockquote>
In reality, the acid-catalyzed peroxidation of acetone always produces a mixture of dimeric and trimeric forms.{{Fact|date=July 2008}}
The trimer is the more stable form, but not much more so than the dimer. All forms of acetone peroxide are very sensitive to [[initiation (chemistry)|initiation]]. Organic peroxides are sensitive, dangerous explosives, due 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.
'''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 a particular [[Radical (chemistry)|radical]] [[inhibitor]] is added.<ref>{{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>
== Industrial occurrence ==
Acetone peroxides are common and unwanted [[by-product]]s of oxidation reactions, eg. 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]]. <!-- This article isn't about: Benzoyl peroxide is the active ingredient in anti-zit (acne) creams, in concentrations as high as 10%.<ref>{{cite journal | last = Mills | first = OH Jr | coauthors = Kligman AM, Pochi P, Comite H | year = 1986 | title = Comparing 2.5%, 5%, and 10% benzoyl peroxide on inflammatory acne vulgaris | journal = International Journal of Dermatology | volume = 25 | issue = 10 | pages = 664–667 | url = http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=pubmed&cmd=Retrieve&list_uids=2948929 | doi = 10.1111/j.1365-4362.1986.tb04534.x}}</ref> -->
[[organic peroxide|Ketone peroxides]], including acetone peroxide, [[methyl ethyl ketone peroxide]], and [[benzoyl peroxide]], find applications as [[initiator]]s for [[polymerization]] reactions of eg. [[silicone]] or [[polyester]] [[resin]]s, often encountered when making [[fiberglass]]. 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 when making fiberglass, and left to stand for some time, or when a mixture of peroxide and hydrochloric acid from [[printed circuit board]] etching (the [[iron trichloride|FeCl<sub>3</sub>]] method is less smelly, more accurate, but slower) 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]].
== Use in crime ==
TATP has been identified in explosive devices in a number of cases involving terrorists. [[Richard Reid (shoe bomber)|Richard Reid]], who attempted to down [[American Airlines Flight 63]] with a bomb concealed in his shoe, possessed a device containing plastic explosive with a TATP trigger. It is also believed that acetone peroxide 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> as well as on September 4, 2007, 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> In addition, the participants in the [[2006 transatlantic aircraft plot]] may have planned to use TATP as the liquid bombs that would destroy U.S. airliners flying from London to the United States.<ref>[http://www.rsc.org/chemistryworld/News/2006/August/11080602.asp "Terror plot sparks frenzied speculation about liquid explosives"], ''[[Royal Society of Chemistry|Chemistry World]], August 11, 2006</ref>
Initial speculation was that the explosive would be mixed in airplane lavatories. It is highly questionable whether such a plot could have been executed, due to the supplies needed, the smell mixing would create, and the time it would take to prepare without drawing suspicion from passengers and the flight crew.<ref>[http://www.theregister.co.uk/2006/08/17/flying_toilet_terror_labs/ "Mass murder in the skies: was the plot feasible?"], ''[[The Register]]'', August 17, 2006</ref>
UK prosecutors recently revealed that the plan was for the explosive to be synthesized outside security and introduced into apparently sealed bottles using a hypodermic needle.<ref>[http://www.timesonline.co.uk/tol/news/uk/crime/article3678807.ece "Terror plot: recipe for terror: batteries, a camera and a fruity drink"], ''[[Times Online]]'', April 4, 2008</ref>
Trace elements of what may have been TATP was also found on a contractor in a [[Sweden|Swedish]] [[nuclear power plant]] on the 21st of may 2008 <ref>[http://www.reuters.com/article/latestCrisis/idUSL21501478 Swedish police hold two men over nuclear scare], ''[[Reuters]]'', May 21, 2008</ref> during a routine inspection. The man and another man working with him were detained but released the day after since no evidence of them possessing any actual explosives could be obtained.
A member of the French anti-speed camera group, Front national anti-radars (Fnar), was hospitalised after losing both hands to an accidental explosion of his bomb based on TATP. <ref>[http://www.lefigaro.fr/actualite-france/2008/05/29/01016-20080529ARTFIG00667-front-antiradar-un-troisieme-homme-interroge.php : In french]</ref>
== References ==
<references />
== See also ==
*[[Methyl ethyl ketone peroxide]]
== External links ==
*[http://www.timesonline.co.uk/article/0,,22989-1695442,00.html TATP is Suicide bombers weapon of Choice] The Times Online UK
*[http://www.time.com/time/nation/article/0,8599,1225453,00.html Thwarting the Airline Plot: Inside the Investigation] TIME magazine
*[http://www.technion.ac.il/~keinanj/pub/122.pdf Decomposition of Triacetone Triperoxide Is an Entropic Explosion (PDF-800KB)], [[Journal of the American Chemical Society]], [[January 5]], [[2005]].
*[http://www.theregister.co.uk/2006/08/17/flying_toilet_terror_labs/ Mass murder in the skies: was the TATP plot feasible?], [[The Register]], [[August 17]], [[2006]].
*[http://www.tfot.info/content/view/92/ TATP – Countering the Mother of Satan] - Comprehensive article covering different aspects of TATP identifying it in the field.
[[Category:Heterocyclic compounds]]
[[Category:Organic peroxides]]
[[Category:Explosive chemicals]]
[[Category:Ketals]]
[[bg:Ацетонов пероксид]]
[[cs:Peroxidy acetonu]]
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[[es:Peróxido de acetona]]
[[fr:Peroxyde d'acétone]]
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[[pt:Triperóxido de triacetona]]
[[ru:Перекись ацетона]]
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