Hexamethylene triperoxide diamine

Structural formula
General
Surname	Hexamethylene triperoxide diamine
other names	1,6-Diaza-3,4,8,9,12,13-hexaoxa bicyclo [4.4.4] tetradecane ( IUPAC ) HMTD
Molecular formula	C 6 H 12 N 2 O 6
Brief description	white crystals
External identifiers / databases
CAS number 283-66-9 PubChem 61101 ChemSpider 55052 Wikidata Q409654
properties
Molar mass	208.1 g mol −1
Physical state	firmly
density	1.57 g cm −3
Melting point	rapid decomposition from 150 ° C
solubility	almost insoluble in water and organic solvents
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 .

Hexamethylene triperoxide diamine , often abbreviated as HMTD , is an organic compound, an amine with three peroxide groups.

Hexamethylene triperoxide diamine was first produced in 1885 by Ludwig Legler in Dresden from ammonia and lamp acid (a mixture of acetic acid , acetaldehyde and formic acid ). In 1900, Baeyer and Villiger succeeded in preparing it from ammonium sulfate , formaldehyde and hydrogen peroxide . Conway Freiherr von Girsewald from Berlin-Halensee applied for a patent as an initial explosive in 1912 and developed a synthesis method that is still used today.

Extraction and presentation

It is represented according to the process first described in 1912 by reacting hexamethylenetetramine with hydrogen peroxide and citric acid as a catalyst . During production, it should be noted that the reaction is highly exothermic. If the temperature rises, the formation of HMTD first decreases; if the temperature is too high, an explosion can occur during the synthesis.

properties

Pure hexamethylene triperoxide diamine is a crystalline, white solid. The compound is only sparingly soluble in water and most organic solvents. HMTD is a relatively stable organic peroxide. However, already hot water leads to decomposition with evolution of oxygen. Dried hexamethylene triperoxide diamine is an extremely effective initial explosive; exposure to shock, heat, friction, or sparks can cause detonation. The peroxide - like almost all initial explosives - can also detonate when pressure is applied with metal spatulas or other hard objects or when exposed to UV light. HMTD never forms large crystals by itself. Even after longer storage for more than 12 months at 40 ° C, the sublimation rate is only 0.02% with the crystal size unchanged, but decomposition takes place.

Approx. 2 g of HMTD on a watch glass

Table with important explosion-relevant properties:

Educational energy	−1610.6 kJ kg −1
Enthalpy of formation	−1729.7 kJ kg −1
Oxygen balance	−92.2%
Nitrogen content	13.46%
Normal gas volume	1247 l kg −1
Explosion heat	3369 kJ kg −1 (H 2 O (l)) 3128 kJ kg −1 (H 2 O (g))
Specific energy	855 kJ kg −1 (87.2 mt / kg)
Lead block bulge	33 cm 3 g −1 ( picric acid 31.5 cm 3 g −1 )
Deflagration point	200 ° C (decomposition from 149 ° C, explosion from 130 ° C possible)
Detonation velocity	4500-5100 m · s −1
Sensitivity to impact	0.6 Nm
Rubbing sensitivity	0.1 N

use

HMTD was tested as an initial explosive for less sensitive explosives and proved to be superior to mercury fulminate . In an open accumulation, it only evaporates in larger quantities (a few grams), while it will readily detonate with little inclusion or even when pressed. Nevertheless, it has not found any practical use because it is mechanically unstable and against moisture and gradually decomposes on storage. It is less sensitive to impact than many other initial explosives , but has considerable explosive power and in the sand test it crushes about 2.5 to 3 times more sand than mercury fulminate . HMTD explodes on so-called drop hammer test already cm with a 2 kg monkey from a height of 10 degrees.

safety instructions

Hexamethylene triperoxide diamine is an initial explosive and therefore particularly explosive. An explosion can occur due to increased temperature, ignition sources or mechanical effects such as friction or impact, but also when it is exposed to UV radiation or sunlight. It can also detonate when it comes into contact with other chemical compounds and elements, especially metals, or due to its own decomposition products during prolonged storage. If there is insufficient cooling during the manufacturing process, it can also react in undesirable ways. Great caution and care must be exercised when handling and special precautions must be taken. It is explosive even when stored under water, but decomposes slowly at room temperature. Dealing with more than the smallest amounts is irresponsible, as the risk of a spontaneous reaction is omnipresent.

Law

In Germany, HMTD is subject to the law on explosives (in particular the authorization requirement according to § 7 and § 27 of the Explosives Act , unless there are exceptions for research and teaching according to the 1st Ordinance on the Explosives Act).

literature

• Alfred Stettbacher: The guns and explosives. 2nd, revised edition. Barth, Leipzig 1933

Individual evidence

1. ↑ ^{a b c d e f g h i j k l m n o p q} Josef Köhler, Rudolf Meyer, Axel Homburg: Explosivstoffe. 10th, completely revised edition. Wiley-VCH, Weinheim 2008, ISBN 978-3-527-32009-7 , p. 158, doi : 10.1002 / 9783527623402.ch8 .
2. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
3. ↑ Martin Martens: About the products of the slow combustion of alcohol and ether around a platinum wire. In: Archives of Pharmacy . Vol. 70 = Series 2, Vol. 20, No. 1, 1839, pp. 181-188 .
4. ↑ Ludwig Legler: About products of the slow combustion of ethyl ether. In: Reports of the German Chemical Society . Vol. 18, No. 2, 1885, pp. 3343-3351 , doi : 10.1002 / cber.188501802306 .