Acetone peroxide

from Wikipedia, the free encyclopedia
Structural formula
Structure of acetone peroxide, dimer and trimer
The dimer (top) and the trimer (TATP, bottom)
General
Surname Acetone peroxide
other names
  • trimeric acetone peroxide
  • dimeric acetone peroxide
  • Triacetone tripperoxide (TATP)
  • Tricycloacetone peroxide (TCAP)
  • IUPAC : 3,3,6,6-tetramethyl-1,2,4,5-tetraoxane (dimer)
  • IUPAC : 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxonane (trimer)
  • 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane
  • Acetone peroxide (APEX)
Molecular formula
  • C 6 H 12 O 4 (dimer)
  • C 9 H 18 O 6 (trimer)
Brief description

colorless monoclinic crystals with a “spicy” smell

External identifiers / databases
CAS number
  • 1336-17-0 (unspec.)
  • 1073-91-2 (dimer)
  • 17088-37-8 (trimer)
PubChem 15908632
Wikidata Q329022
properties
Molar mass 222.24 g mol −1 (trimer)
Physical state

firmly

density

1.22 g cm −3

Melting point

91 ° C (trimer)

Vapor pressure
  • 6.46 Pa (30 ° C, trimer)
  • 45.53 Pa (50 ° C, trimer)
solubility
safety instructions
GHS hazard labeling
no classification available
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Acetone peroxide or APEX is a highly explosive substance with the impact sensitivity of an initial explosive . It occurs in the forms of di-, tri- and tetrameric cyclic acetone peroxide, which are formed in different proportions under different conditions (e.g. depending on the catalyst used). After its mainly occurring trimeric form, it is also known under the name triacetone triperoxide or TATP for short . Dimethyldioxirane , which is only stable in solution, can be regarded as the monomeric acetone peroxide.

Acetone peroxide, like most other organic peroxides and in contrast to less dangerous peroxides such as dibenzoyl peroxide , is very sensitive to impact, friction and heat. It disintegrates easily, which can lead to violent detonations . TATP is a frequently used explosive in attacks by Islamist terrorists .

history

Acetone peroxide was discovered by accident in 1895 by Richard Wolffenstein at the Technical University of Charlottenburg while investigating the oxidation of coniin with hydrogen peroxide in acetone as a solvent. He applied for a patent for a manufacturing process for acetone peroxide in 1895 under the number DRP 84953 in Germany. In 1899 and 1900, Adolf von Baeyer and Victor Villiger published several articles on the formation of dimeric and trimeric acetone peroxide. In 1925 it was sold under the number DRP 423,176 in Germany and various other countries by the Sprengstoffwerke Dr. R. Nahnsen & Co. AG, Hamburg, has applied for a patent as an allegedly safe and stable initial explosive, but the extreme impact sensitivity, volatility (6.5% in 24 h at 14-18 ° C) and lack of stability prevented any practical use.

A. E. Thiemann suggested the use of acetone peroxide as an additive to improve the ignitability of diesel fuel in 1942 ; H. to increase the cetane number . As there are cheaper and safer solutions, it is not used for this purpose.

presentation

Acetone peroxide can be formed in considerable amounts when simply mixing acetone with hydrogen peroxide-containing solutions after storing the mixture for several days. The Berlin chemist Richard Wolffenstein discovered it as early as 1895.

Trimeric acetone peroxide (melting point 91.5 ° C) is formed when hydrogen peroxide acts on acetone in the presence of dilute acids as a catalyst :

Formation of trimeric acetone peroxide from acetone and hydrogen peroxide.

In the presence of hydrochloric acid , sulfuric acid or phosphoric acid , the reactions are exothermic to different degrees depending on the pH value ( risk of explosion ). If there is insufficient cooling, the reaction with hydrochloric acid under boiling produces the tear gas chloroacetone .

The dimeric product can be produced either by reacting acetone with peroxomonosulfuric acid (Caro's acid), by oxidizing diisopropyl ether with atmospheric oxygen or by ozonolysis . If diisopropyl ether is improperly stored, acetone peroxide can therefore be formed. To destroy such peroxides, copper (I) compounds are used for reduction .

Tetrameric acetone peroxide was obtained in 1998 in the above reaction using Lewis acids as a catalyst.

properties

Acetone peroxide crystals

Acetone peroxide is volatile in air (spicy smell, loss of substance through sublimation 6.5% in 24 hours) and volatile with steam or ether . Trimeric acetone peroxide decomposes quantitatively into acetone and hydrogen peroxide when heated with dilute acids (H 2 SO 4 10%) under reflux .

It is not changed by acetic anhydride and does not react with potassium iodide - acetic acid . It is not attacked by 1 molar sodium hydroxide solution even when heated. Zinc dust and sodium hydroxide solution slowly reduce dimeric acetone peroxide in the cold.

Acetone peroxide is irritating (with only low acute toxicity ), flammable and highly explosive. It is particularly sensitive to ignition by flame, heat, impact and friction. Storage under water reduces sensitivity and prevents sublimation. The detonation velocity is 5290–5400 m · s −1 (density 1.18–1.20 g · cm −3 ) (trimer). The oxygen balance is −151.3%. The lead block bulge is 250 ml / 10 g for the trimer. The impact sensitivity is 0.3  J (trimer), the friction sensitivity 0.1 N pin load (trimer).

The explosive force of acetone peroxide is, depending on the test method in 80-100% of the explosive power of trinitrotoluene (TNT). When acetone peroxide explodes, the gas molecules responsible for the explosive effect are created without the extreme heat being generated, as is common with many other explosives.

In a drop hammer test with a 1 kg drop hammer (tests with a 2 kg drop hammer are common for normal explosives), it detonates when hit from a height of just 3 cm.

Acetone peroxide can not be detected with conventional explosives detectors that are sensitive to nitro compounds .

Analytics

For the reliable forensic identification of TATP at crime scenes or persons exposed to the substance, the coupling of gas chromatography with UV spectroscopy or mass spectrometry is used after adequate sampling . The coupling of HPLC with mass spectrometry is also suitable for determining TATP. A recently developed specific electrochemical process also allows the TATP to be differentiated from explosives such as PETN , RDX , HMX and TNT .

Special dangers

Acetone peroxide, like other similar peroxides, is extremely explosive. Acetone peroxide crystals are generally not stable; at any time, for example due to differences in temperature and light, crystal fractures can occur, which lead to a spontaneous explosion. Trimeric acetone peroxide already sublimes at 14-18 ° C, which is why small crystals quickly form in a closed vessel in the area of ​​the vessel closure at room temperature, which break through the friction when the vessel is opened and trigger an explosion of the vessel contents.

At elevated storage temperatures, acetone peroxide decomposes within a few hours. If a temperature of 130 ° C is reached, this leads to an explosion; it detonates when it is wet, even with a water content of 25%. On the other hand, if a single small crystal comes into direct contact with a flame, a relatively harmless deflagration occurs .

As a chemical experiment at schools and universities, the heating of moist trimeric acetone peroxide in the milligram range was occasionally demonstrated on a stable iron plate until the peroxide detonated. Alternatively, you can switch to hexamethylene triperoxide diamine (HMTD), which has the same didactic demonstration value in terms of detonation with lower impact sensitivity and no tendency to sublimation. Due to the uncertainty of handling acetone peroxide and HMTD as well as the sometimes problematic destruction of residual amounts, however, both substances must generally be subjected to a critical examination for teaching tests.

Legal status

Acetone peroxide is classified as explosive according to the SprengG and has been assigned to substance group A. It is subject to the law on explosives (in particular the authorization requirement from Section 27 of the Explosives Act), provided that no exceptions apply according to the 1st Ordinance to the Explosives Act for research and teaching.

literature

  • Richard Escales: Initial Explosives. Survival Press, Radolfzell 2002, ISBN 3-8311-3939-3 .
  • Beilstein's Handbook of Organic Chemistry. Edited by Beilstein Inst. for organic chemistry literature. 31 volumes. 4th edition. Springer, Berlin 1918–31.
  • Alfred Rieche, Kurt Koch: The oxidation of diisopropyl ether. (XIV. Communication) on ethyl peroxides. In: Reports of the German Chemical Society (A and B Series). 75, 1942, p. 1016, doi: 10.1002 / cber.19420750815 .
  • R. Criegee, W. Schnorrenberg, J. Becke: On the constitution of ketone peroxides. In: Justus Liebig's Annals of Chemistry. 565, 1949, p. 7, doi: 10.1002 / jlac.19495650103 .
  • Rudolf Criegee, Karl Metz: About a third, crystallized acetone peroxide. In: Chemical Reports. 89, 1956, p. 1714, doi: 10.1002 / cber.19560890720 .
  • Tadeusz Urbanski: Chemistry and Technology of Explosives. Volume 3, German publishing house for basic industry, Leipzig 1964, p. 194 ff.
  • M. Rohrlich, W. Sauermilch: Explosive properties of tricycloacetone peroxide. In: Journal for the entire gun and explosives industry. 38, 1943, pp. 97-99.
  • J. Gartz: From Greek fire to dynamite - a cultural history of explosives. ES Mittler & Sohn, Hamburg 2007, ISBN 978-3-8132-0867-2 .

Web links

Commons : Acetone Peroxide  - Collection of Pictures, Videos and Audio Files

Individual evidence

  1. ↑ a b c d e f g Entry on acetone peroxide. In: Römpp Online . Georg Thieme Verlag, accessed on June 1, 2014.
  2. ↑ a b c d J. Köhler, R. Meyer, A. Homburg: Explosivstoffe. 10th, completely revised edition. Wiley-VCH, 2008, ISBN 978-3-527-32009-7 .
  3. ↑ a b c H. Félix-Rivera, ML Ramírez-Cedeño, RA Sánchez-Cuprill, SP Hernández-Rivera: Triacetone triperoxide thermogravimetric study of vapor pressure and enthalpy of sublimation in 303-338 K temperature range. In: Thermochim. Acta . 514, 2011, pp. 37-43, doi: 10.1016 / j.tca.2010.11.034 .
  4. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
  5. ↑ Anis Amri: The truck was just plan B. In: Zeit-Online. December 13, accessed December 21, 2018.
  6. ↑ a b c Richard Wolffenstein: About the action of hydrogen peroxide on acetone and mesityl oxide. In: Reports of the German Chemical Society. 28, 1895, p. 2265, doi: 10.1002 / cber.189502802208 . (Digitized version)
  7. ^ A b Adolf Baeyer, Victor Villiger: Effect of Caro's reagent on ketones. In: Reports of the German Chemical Society. 32, 1899, p. 3625, doi: 10.1002 / cber.189903203151 . (Digitized version)
  8. ^ A b Adolf Baeyer, Victor Villiger: About the nomenclature of super oxides and the super oxides of aldehydes. In: Reports of the German Chemical Society. 33, 1900, p. 2479, doi: 10.1002 / cber.190003302185 . (Digitized version)
  9. ↑ Patent DE423176 : Process for the production of initial ignition means. Registered on March 8, 1925 , published on December 21, 1925 , applicant: Dr. R. Nahnsen & Co. AG, Gottfried Pyl. ‌
  10. ↑ M. Rohrlich, W. Sauermilch: Explosive properties of tricycloacetone peroxide. In: Journal for the entire gun and explosives industry. 38, 1943, pp. 97-99.
  11. ^ AE Thiemann: About fuel additives in diesel oils. In: ATZ Automobiltechnische Zeitschrift . Volume 45 (16), 1942, pp. 454-457.
  12. ↑ Robert W. Murray, Ramasubbu Jeyaraman: Dioxiranes: synthesis and reactions of methyldioxiranes. In: The Journal of Organic Chemistry. 50, 1985, pp. 2847-2853, doi: 10.1021 / jo00216a007 .
  13. ↑ Heng Jiang, Gang Chu, Hong Gong, Qingdong Qiao: Tin Chloride Catalysed Oxidation of Acetone with Hydrogen Peroxide to Tetrameric Acetone Peroxide . In J. Chem. Res. (S), 1999, pp. 288-289, doi: 10.1039 / a809955c .
  14. ↑ Faina Dubnikova, Ronnie Kosloff, Joseph Almog, Yehuda Zeiri, Roland Boese, Harel Itzhaky, Aaron Alt, Ehud Keinan: Decomposition of Triacetone Triperoxide Is an Entropic Explosion. In: J. Am. Chem. Soc. 127 (4), 2005, pp. 1146-1159. doi: 10.1021 / ja0464903 .
  15. ↑ Peter Podjavorsek: Detection method for plastic explosives. In: Deutschlandfunk . Retrieved July 28, 2016.
  16. ^ FS Romolo, L. Cassioli, S. Grossi, G. Cinelli, MV Russo: Surface-sampling and analysis of TATP by swabbing and gas chromatography / mass spectrometry. In: Forensic Sci Int. 224 (1-3), Jan 10, 2013, pp. 96-100. PMID 23219697
  17. ↑ JC Oxley, JL Smith, LJ Kirschenbaum, S. Marimiganti, I. Efremenko, R. Zach, Y. Zeiri: Accumulation of explosives in hair - Part 3: Binding site study. In: J Forensic Sci. 57 (3), May 2012, pp. 623-635. PMID 22235760
  18. ↑ J. Andrasko, L. Lagesson-Andrasko, J. Dahlén, BH Jonsson: Analysis of Explosives by GC-UV. In: J Forensic Sci. 62 (4), Jul 2017, pp. 1022-1027. PMID 28070907
  19. ↑ A. Stambouli, A. El Bouri, T. Bouayoun, MA Bellimam: Headspace-GC / MS detection of TATP traces in post-explosion debris. In: Forensic Sci Int. 146 Suppl, Dec 2, 2004, pp. S191-S194. PMID 15639574
  20. ^ D. Muller, A. Levy, R. Shelef, S. Abramovich-Bar, D. Sonenfeld, T. Tamiri: Improved method for the detection of TATP after explosion. In: J Forensic Sci. 49 (5), Sep 2004, pp. 935-938. PMID 15461093
  21. ↑ L. Widmer, S. Watson, K. Schlatter, A. Crowson: Development of an LC / MS method for the trace analysis of triacetone triperoxide (TATP). In: Analyst. 127 (12), Dec 2002, pp. 1627-1632. PMID 12537371
  22. ↑ SK Mamo, J. Gonzalez-Rodriguez: Development of a molecularly imprinted polymer-based sensor for the electrochemical determination of triacetone triperoxide (TATP). In: Sensors. (Basel). 14 (12), Dec 5, 2014, pp. 23269–23282. PMID 25490589 .
  23. ↑ Notice of assessment no. 413 of February 26, 2002 of the Federal Institute for Materials Research and Testing (PDF online ; 53 kB).