Ethylenedinitramine

Structural formula
General
Surname	Ethylenedinitramine
other names	N , N ′ -Dinitroethylenediamine; Haleite; EDNA; 1,4-dinitro-1,4-diazabutane;
Molecular formula	C 2 H 6 N 4 O 4
Brief description	colorless crystals
External identifiers / databases
EC number	208-018-2
ECHA InfoCard	100.007.290
PubChem	10462
Wikidata	Q4532975
properties
Molar mass	150.09 g mol −1
Physical state	firmly
density	1.71 g cm −3
Melting point	177 ° C
solubility	soluble in 1,4-dioxane and nitrobenzene ; slightly soluble in water and ethanol ; insoluble in diethyl ether ;
safety instructions
H and P phrases	H: 201-302
	P: ?
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Ethylendinitramin is an organic compound that the substance group of nitramines can be assigned. Like other substances in this group, it has explosive properties and is used as an explosive .

history

The compound was first described in 1887 by APN Franchimont and EA Klobbie. It was used as a military explosive from 1935.

Presentation and extraction

In the first step, the synthesis starts from urea 1 and ethylene carbonate 2 , from which ethylene urea is formed under pressure. This is then nitrated with mixed acid . The resulting dinitroethylene urea then gives the end product ethylenedinitramine 3 with elimination of carbon dioxide .

properties

Ethylenedinitramine forms orthorhombic , colorless crystals. It's not hygroscopic . The compound melts at 177 ° C with a melting enthalpy of 29.5 kJ mol ⁻¹ . As a dibasic acid, it forms the corresponding salts. The acid constants are pK _a1 5.31 and pK _a2 6.64. The lead and silver salts are sensitive to impact. The connection is particularly explosive due to shock, friction, fire and other sources of ignition and, when handled, falls under the Explosives Act . Important explosion parameters are:

Table with important explosion-relevant properties:
Oxygen balance	−32%
Nitrogen content	37.33%
Normal gas volume	1047 l kg ⁻¹
Explosion heat	4699 kJ kg ⁻¹ (H ₂ O (l)) 4281 kJ kg ⁻¹ (H ₂ O (g))
Specific energy	1260 kJ kg ⁻¹ (128.5 mt kg ⁻¹ )
Lead block bulge	41.0 cm ³ g ⁻¹
Detonation velocity	7570 m · s ⁻¹
Deflagration point	180 ° C
Sensitivity to impact	8 Nm

The kinetics of thermal decomposition were investigated for the melt in the temperature range of 184 ° C and 254 ° C. The decomposition process can be described with a first-order time law. The activation energy is 127.7 kJ · mol ⁻¹ , the Arrhenius factor 6.31 · 10 ¹² s ⁻¹ . The half-lives are 43 s at 184 ° C and 0.5 s at 254 ° C. The decomposition proceeds much more slowly in the solid. From the analysis of the decomposition gases, a decomposition course according to

{\ displaystyle \ mathrm {C_ {2} H_ {6} N_ {4} O_ {4} \ rightarrow 2 \, N_ {2} O + CH_ {3} CHO + H_ {2} O}}

postulated, whereby side reactions with the formation of NO and N _{2 also} take place.

use

The compound can be used in pressed cargoes. In combination with trinitrotoluene , pourable mixtures called ednatol can be obtained.

Individual evidence

↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k ^l ^m ⁿ ^o ^p ^q ^r J. Köhler, R. Meyer, A. Homburg: Explosivstoffe , tenth, completely revised edition. Wiley-VCH, Weinheim 2008, p. 122, ISBN 978-3-527-32009-7 .
↑ ^a ^b ^c ^d ^e Entry on ethylenedinitramine. In: Römpp Online . Georg Thieme Verlag, accessed on July 30, 2015.
↑ Template: CL Inventory / not harmonized There is not yet a harmonized classification for this substance . A labeling of N, N'-dinitroethylenediamine Template: link text check / apostrophe in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on July 19, 2019, is shown, which is derived from a self-classification by the distributor .
↑ Oyumi, Y .; Brill, TB: Thermal decomposition of energetic materials. 23. Thermochemical differentiation of cyclic and acyclic nitramines by their phase transitions in Thermochim. Acta 116 (1987) 125-130, doi : 10.1016 / 0040-6031 (87) 88171-6 .
↑ Ivshin, VP; Ivshina, TN; Smirnova, LG; Ponomareva, MG: in Zh. Org. Khim. 20, 7-13 (1984).
↑ Aakeröy, CB; Wijethunga, TK; Desper; J .: Crystal Engineering of Energetic Materials: Co-crystals of Ethylenedinitramine (EDNA) with Modified Performance and Improved Chemical Stability in Chem. Eur. J. 21 (2015) 11029-11037, doi : 10.1002 / chem.201501721 .
↑ ^a ^b Roth, L .; Weller, U .: Hazardous Chemical Reactions , 65th supplement, ecomed-Verlag 2011.
↑ ^a ^b ^c ^d Robertson, AJB: The thermal decomposition of explosives. Part I. Ethylenedinitramine and tetryl in Trans. Faraday Soc. 44 (1948) 677-682, doi : 10.1039 / TF9484400677 .

[Explosivstoffe-1] ↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j ^k ^l ^m ⁿ ^o ^p ^q ^r J. Köhler, R. Meyer, A. Homburg: Explosivstoffe , tenth, completely revised edition. Wiley-VCH, Weinheim 2008, p. 122, ISBN 978-3-527-32009-7 .

[Roempp-2] Entry on ethylenedinitramine. In: Römpp Online . Georg Thieme Verlag, accessed on July 30, 2015.

[3] Template: CL Inventory / not harmonized There is not yet a harmonized classification for this substance . A labeling of N, N'-dinitroethylenediamine Template: link text check / apostrophe in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on July 19, 2019, is shown, which is derived from a self-classification by the distributor .

[4] Oyumi, Y .; Brill, TB: Thermal decomposition of energetic materials. 23. Thermochemical differentiation of cyclic and acyclic nitramines by their phase transitions in Thermochim. Acta 116 (1987) 125-130, doi : 10.1016 / 0040-6031 (87) 88171-6 .

[5] Ivshin, VP; Ivshina, TN; Smirnova, LG; Ponomareva, MG: in Zh. Org. Khim. 20, 7-13 (1984).

[Aakeröy-6] Aakeröy, CB; Wijethunga, TK; Desper; J .: Crystal Engineering of Energetic Materials: Co-crystals of Ethylenedinitramine (EDNA) with Modified Performance and Improved Chemical Stability in Chem. Eur. J. 21 (2015) 11029-11037, doi : 10.1002 / chem.201501721 .

[Roth-Weller-7] Roth, L .; Weller, U .: Hazardous Chemical Reactions , 65th supplement, ecomed-Verlag 2011.

[Robertson-8] Robertson, AJB: The thermal decomposition of explosives. Part I. Ethylenedinitramine and tetryl in Trans. Faraday Soc. 44 (1948) 677-682, doi : 10.1039 / TF9484400677 .