Triacetone triperoxide explosive

G.A. Buttigieg, A.K. Knight, S. Denson, C. Pommier and M.B. Denton, Characterization of the explosive triacetone triperoxide and detection by ion mobility spectrometry. Forensic Science International 135(1) (2003) 53-59. 

Recent events in London, as reported in the international press, in which an attempt was made to fabricate the explosive triacetone triperoxide (TATP) in-flight from the liquids acetone and a concentrated hydrogen peroxide solution, have forced the topic of the identification of liquids firmly into the public consciousness. XRD identification of liquids is thus the topic of this section. Several parameters by which XRD profiles of liquids may be characterized will be described here. 

The requirement for an explosive train, that is, a primary explosive to initiate the secondary explosive, is a safety feature. In the past, people wishing to illegally use explosives usually had to steal the detonators (e.g., Timothy McVey). Consequently, the effective control of access to detonators has been widely regarded as a key pubhc safety measure by many governments and law enforcement agencies. However, recently, triacetone triperoxide (TATP) has been used as the primary explosive (e.g., Richard Reid s shoe bomb) and TATP is readily, although hazardously, synthesized from acetone, hydrogen peroxide, and acid. 

Triacetone triperoxide (TATP) is a powerful explosive manufactured in clandestine laboratories and used by terrorists. As TATP subHmes easily, analysis was performed by SPME trapping of its vapor, using polydimethylsiloxane/divinyl benzene (PDMS/DVB) fiber, followed by desorption into a GC/MS injector [10]. Figure 6 shows the TIC, mass chromatogram and the El mass spectmm of headspace from a debris sample containing TATP [11]. The El mass spectmm contains a molecular ion at m/z 222 and several fragment ions. In the chemical ionization mass spectmm of TATP [12], the m or ions were at m/z 223 (100%), 222 (20%), 133 (20%), 117 (40%), 115 (20%), 103 (75%) and 100 (50%). 

Figure 6 TIC, mass chromatogram and El mass spectrum of a debris sample containing triacetone triperoxide (TATP) (Reproduced from T. Tamiri et al., Proc. 6th Int. Symp. on Analysis and Detection of Explosives, Prague, Czech Republic, 1998. With permission).

Some ketone-derived peroxides have explosive properties, of which the most interesting are obtained from acetone. Four acetone-derived peroxides have been synthesized. Acetone peroxide dimer (48) is obtained in 94 % yield by treating acetone with a slight excess of 86 % hydrogen peroxide in acetonitrile in the presence of concentrated sulfuric acid at subambient temperature. The reaction of acetone with potassium persulfate in dilute sulfuric acid also yields acetone peroxide dimer (48). Acetone peroxide trimer (49), also known as triacetone triperoxide (TATP), has been obtained as a by-product of these reactions or by the addition of... 

Oxley, J. C., J. L. Smith, and H. Chen. Decomposition of multi-peroxidic compound Triacetone triperoxides (TATP). Propellants, Explosives Pyrotechnics 27, 209-216 (2002). 

Peroxide explosives are potent explosives that can be made starting from common and easy to obtain raw materials. The analysis of triacetone triperoxide (TATP) and hexamethylenetriper-oxidediamine (HMTD) was successfully carried out by HPLC-APCI-MS in a powder sample as well as in post-blast extracts originating from a forensic case [134]. After RP separation on a C18 column using a methanohwater (75 25 v/v) mobile phase containing ammonium acetate (2.5mM) at a 0.4mL/min flow rate, detection was carried out in positive ion mode. MS-MS analysis of [TATPh-NH4]+ and [HMTD - H]+ as precursor ions was necessary in order to achieve the required sensitivity in the analysis of postblast extracts (LOD 0.8 and 0.08 ng on column, respectively). 

Inspired by the effective post-column photochemical conversion of hydroperoxides and peroxides to H2O2 just described, a method was developed for trace analysis of peroxide explosives, such as triacetone triperoxide (251) and hexamethylene triperoxide diamine (252). These are powerful explosives with no commercial or military applications because... 

Transport of dangerous goods (TDG), 745-6 Trauma, plasma oxidation level, 631 Triacetone triperoxide explosive, 707-8 Triacylglycerides, mass spectrometry, 689 Triarylgermyl hydroperoxide, formation, 822 Triarylphosphine, hydroperoxide determination, 679... 

Both X-ray crystallography and electronic structure calculations using the cc-pVDZ basis set at the DFT B3LYP level have been employed to study the explosive properties of triacetone triperoxide (TATP) and diacetone diperoxide (DADP).32 The thermal decomposition pathway of TATP has been investigated by a series of calculations that identified transition states, intermediates, and the final products. Calculations predict that the explosion of TATP is not a thermochemically highly favoured event. It rather involves entropy burst, which is the result of formation of one ozone and three acetone molecules from every molecule of TATP in the solid state. 

Dubnikova, F., R. Kosloff, J. Almog, Y. Zeiri, R. Boese, H. Itzhaky, A. Alt, and E. Keinan (2005). Decomposition of triacetone triperoxide is an entro-pic explosion. JACS127,1146-1159. 

Explosives that were detectable included TNT, dinitrotoluene (DNT), RDX, HMX, PETN, EGDN, NG, Tetryl, ammonium nitrate fuel oil (ANFO), triacetone triperoxide (TATP), and hexamethylene triperoxide diamine (HMTD). Analysis time is less than 15 s. Figure 6 shows schematically how such a portal works ... 

Fig. 16. Gas chromatography-differential mobility spectrometry (GC-(DMS) topographic plot [retention time (v-axis), compensation voltage (y-axis), intensity (z-axis)] of a mixture of seven explosives (lOOng in acetonitrile) hexamethylene triperoxide diamine (HMTD), ethylene glycol dinitrate (EGDN), triacetone triperoxide (TATP), 2-mononitrotoluene (2-MNT), 4-MNT, 2,4-dinitrotoluene (2,4-DNT), and 2,4,6-trinitrotoluene (TNT).

Triacetone triperoxide (TATP, Fig. 1.14) is formed from acetone in sulfuric acid solution when acted upon by 45 % (or lower concentration) hydrogen peroxide (the acid acts as a catalyst). Like most other organic peroxides TATP has a very high impact (0.3 J), friction (0.1 N) and thermal sensitivity. TATP has the characteristics of a primary explosive. For this reason and because of its tendency to sublime (high volatility) it is not used in practice (apart from terrorist and suicide bomber activities). 

Typical organic peroxides, which have been or may be used by terrorists are so-called homemade explosives (HMEs) triacetone triperoxide (TATP), hexameth-ylene triperoxide diamine (HMTD), methyl ethyl ketone peroxide (MEKP) and diacetone diperoxide (DADP) (Fig. 1.14). 

Usually explosives can be categorized as military, commercial and homemade (HME) explosives. HMEs are energetic formulations that can be created at home . The term HME has been used to cover a wide range of materials from pure explosive compounds, such as triacetone triperoxide (TATP), that can be synthesized from readily available articles of commerce or pentaerythritol tetranitrate (PETN), as pentaerythritol can be purchased in bulk for paint use to home-made variants of explosive formulations, such as ammonium nitrate fuel oil (ANFO), that are used in very large commercial blasting operations. 

These examples show that mass addition is not essential for an interferometer s response. Such schemes could find use in sensing. For example, a monomeric sensing film could be used to amplify the response to an analyte capable of directly or indirectly leading to polymerization. A sensing film composed of a monomeric species could remain unperturbed until a free radical initiator was detected. A peroxide such as triacetone triperoxide (TATP), the explosive... 

In recent times because of restrictions placed upon conventional military explosives there has been an increase in the use of home made bomb materials. Perhaps none is more notorious that triacetone triperoxide (TATP). This crystalline material can be produced from common acetone, peroxide, and citric acid, yet it has the explosive power of RDX. The most publicized account was that of Richard Reid, the shoe bomber, but TATP is often used by Hamas human bombers in Israel. 

Improvised high explosives vary from the relatively simple to prepare but highly shock-sensitive-triacetone triperoxide or hexamethylene triperoxidediamine to obsolete explosives such as tetranitroaniline. In general, if an adequate collection of reference spectra is available, the pure material is probably best identified by IR spectroscopy as a micro-KBr pellet or by mass spectral techniques. 

ANALYSIS OF TRIACETONE TRIPEROXIDE EXPLOSIVE BY MASS SPECTROMETRY... 

In 1895, Wolfenstein first synthesized 3,3,6,6,9,9-hexamethyl-l,2,4,5,7,8-hexaoxacyclononane, otherwise known as triacetone triperoxide (TATP) [1], TATP is classified as a primary high explosive, meaning that it is highly sensitive to heat and friction. Owing to its instability, the peroxide is of little or no industrial or military use and it is not possible to purchase bulk quantities from commercial sources. Dilute solutions of analytical standards are available commercially. 

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