Acetone peroxide

• Trimeric acetone peroxide
• Dimeric acetone peroxide
• Triacetone ( TATP )
• Tricycloacetonperoxid ( 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 - hexaoxonan ( trimer)
• 3,3,6,6,9,9 - hexamethyl- 1,2,4,5,7,8 - hexaoxacyclononan
• Acetonperoxyd (APEX)

• C6H12O4 (dimer)
• C9H18O6 ( trimer)

Colorless monoclinic crystals with " spicy " odor

• 222.24 g · mol -1 ( trimer)

Fixed

1.22 g · cm -3

91 ° C ( trimer)

• 6.46 Pa ( 30 ° C, the trimer )
• 45,53 Pa (50 ° C, the trimer )

• Insoluble in water, sparingly soluble in ethanol, isopropanol, glycerol and acetic acid
• Soluble in acetone, ether, ethyl acetate, hexane and benzene

Template: Infobox chemical / molecular formula search available

Acetone (also known as APEX or TATP ) is a highly explosive substance to the impact sensitivity of an initial explosive.

Like most organic peroxides acetone peroxide is also unstable and can decay by shock, heat or friction and violently detonate, but is in contrast to less dangerous peroxides such as dibenzoyl much more sensitive to shock and heat.

It differs dimeric, trimeric and tetrameric acetone peroxide, which are formed under different conditions ( for example, depending on the used catalyst).

Acetone is classified as explosive in accordance with the Explosives Act and the substance group A was assigned.

Properties

• Volatile air ( spicy smell, loss of substance by sublimation 6.5 % in 24 hours)
• Volatile with steam or ether. Trimeric acetone peroxide decomposes on heating with dilute acids (H2SO4 10%) under reflux quantitatively in acetone and hydrogen peroxide
• It is not changed by acetic anhydride and does not react with potassium iodide - acetic acid.
• It is of 1 N sodium hydroxide solution not attacked when heated.
• Zinc dust and caustic soda reduce dimeric acetone peroxide slowly in the cold.
• Irritant (with only low acute toxicity), flammable, highly explosive
• Particularly sensitive to ignition by flame, heat, shock and friction
• Storage under water reduces the sensitivity and prevents the sublimation.
• Detonation velocity: 5290-5400 m · s -1 ( density 1.18 to 1.2 g · cm -3) ( trimer)
• Oxygen balance: -151.3 %
• Lead block expansion: 250 ml/10 g ( trimer)
• Impact sensitivity: 0.03 kg · m = 0.3 Nm ( trimer)
• Friction sensitivity: 0.01 kgf = 0.1 N load pin ( trimer)

Education

Trimeric acetone peroxide (melting point 97 to 131.5 ° C ) is created by the action of hydrogen peroxide on acetone in the presence of dilute acids as a catalyst:

In the presence of hydrochloric acid, sulfuric acid or phosphoric acid, the reactions, how much was added by the catalyst in dependence, strongly exothermic ( risk of explosion). If sufficient cooling occurs in the reaction with hydrochloric acid by boiling the tear gas chlorine acetone.

The possibility of preparation of the dimeric product is the reaction of acetone with peroxomonosulphuric acid ( Caro's acid ) and the oxidation of diisopropyl ether by atmospheric oxygen or ozonolysis. Improper storage of diisopropyl ether acetone peroxide may therefore arise. For destruction of such peroxides copper (I) compounds used for the reduction.

Acetone tetramer obtained in the above reaction with the use of Lewis acid as a catalyst a few years ago.

Acetone peroxide can occur after several days of storage of the mixture with hydrogen peroxide - containing solutions in substantial quantities at the mere mixing of acetone. It discovered the Berlin chemist Richard Wolff stone already in 1895.

Specific hazards

Acetone peroxide is like other similarly constructed extremely explosive peroxides.

Trimeric acetone peroxide sublimes even at 14-18 ° C, which is below room temperature, and detonates still wet with a water content of 25%. At room temperature and about storage in a closed vessel formed by the sublimation of the Acetonperoxids in the field of vascular occlusion fast small crystals, which can already run by the friction when opening the vessel detonated. The mere breaking of the fine crystals in the closure area will then cause an explosion of the entire vessel contents. Since the acetone peroxide crystals are generally not stable for the same reason, crystal breaks can come at any time ( by temperature and light differences about ) that can lead to a spontaneous explosion of the entire vessel contents.

The explosive force of acetone peroxide is, depending on the test method at 80-100 % of the explosive power of trinitrotoluene ( TNT). With the explosion of acetone peroxide responsible for the explosive effect gas molecules are formed without the usual in many explosives heat.

Already at 130 ° C it may decompose explosively. At elevated storage temperatures it decomposes within a few hours. In direct contact with a flame of a crystal, however, is only a relatively harmless deflagration.

In a monkey experiment with a 1 kg drop hammer ( studies with a 2 kg drop hammer are common in normal explosives ) it detonates on impact of just 3 cm height.

APEX is subject to the Explosives Act (in particular, the licensing requirement of § 27 of the Explosives Act, ) where no exceptions after the first prescription pick up the Explosives Act for research and teaching.

As a chemical experiment, the heating damp trimeric Acetonperoxids in the milligram range is occasionally free paraded on a stable iron plate to the peroxide to detonate at schools and universities. Alternatively, can be avoided on Hexamethylentriperoxiddiamin ( HMTD ), all in a smaller impact sensitivity and lack of tendency to sublime the same didactic demonstration value in terms of detonation has. Due to the handling of uncertainty acetone peroxide and HMTD well as the partly problematic destruction of residual amounts of the two substances for educational experiments, however, are generally not recommended.

Acetone can be combined with conventional explosives detectors sensitive to nitro compounds, not detected.

History

Acetone peroxide was discovered in 1895 by Richard Wolff stone at the Technical University Berlin in the investigation of the oxidation of coniine with hydrogen peroxide in acetone as solvent at random. A production method for acetone peroxide was by him in 1895 under the number DRP 84953 registered in Germany for a patent. Baeyer and Villiger published in 1899 and 1900 some articles about the formation of dimeric and trimeric Acetonperoxids. In 1925 it was taking the number DRP 423.176 registered in Germany and various other countries of the explosives works Dr. R. Nahnsen & Co. AG, Hamburg as an allegedly safe and stable primary explosive for a patent, but the extreme sensitivity to impact, volatility ( 6.5 % in 24 h at 14-18 ° However, C) and lack of stability prevented any practical use (see Rohrlich / sour milk ) due to the great danger.

A. E. Thiemann proposed in 1942 the use of acetone peroxide as an additive to improve the ignitability of diesel fuel before.

Acetone has repeatedly due to accidental formation of spectacular accidents, such as 2001 in a laboratory at the University of Bonn, where a 55- gallon waste drum was filled with chemical waste, which could make acetone peroxide. However, here was no evidence whether in fact a peroxide was carried out.

In a planned attack on several aircraft during the flight to the U.S., that could be prevented on 10 August 2006 in London, possibly acetone peroxide should be used. The bombers would infiltrate the raw materials ( acetone and hydrogen peroxide) in liquid form in drinking vessels in the aircraft and there can make the explosives without additional catalyst. The practicality of such an undertaking is to experts, however, could doubt without acid catalysis, however, the mixture of acetone and hydrogen peroxide occurs only after standing for several days, a reaction, as already Wolffenstein 1895 prove; it would be additionally an acid have been needed. And the peroxide may have to be filtered off after the preparation of the solution. The following necessary drying would take on the filter for several hours. Thus, the " aircraft variant" in this version is very unlikely. Similarly, it was supposed in very large quantities (700 kg) are used in an assassination attempt in Germany. The actual feasibility of this plan, however, is to look very critically. The extreme sensitivity of the substance effectively prevents actual use.

Acetone can be best introduced into acetone and its solubilization in diesel or biodiesel. However, the solubility in acetone is limited and should not exceed 25%. In diesel fuel oil or vegetable oil, it increases the cetane number. Since there are cheaper and safer solutions, it is not used for this purpose.

Trivia

Acetone peroxide is easy to mix from household cleaners and is therefore repeated theme of detective novels and films.

It should also, according to initial information provided by the security authorities ( APEX was in later opinions no more talk ) are used in the attacks on London's aircraft in 2006; However, it is unlikely that it would be the terrorists managed to dry the explosives on time.

Also it should be used in the planned attacks by the so-called " Sauerland group " that tried to buy for this purpose larger amounts of hydrogen peroxide.