Tetranitromethane

Structural formula
General
Surname	Tetranitromethane
other names	Tetranitro carbon TNM
Molecular formula	CN 4 O 8
Brief description	colorless, pungent smelling liquid
External identifiers / databases
CAS number 509-14-8 EC number 208-094-7 ECHA InfoCard 100.007.359 PubChem 10509 Wikidata Q412241
properties
Molar mass	196.03 g mol −1
Physical state	liquid
density	1.6229 g cm −3
Melting point	14 ° C
boiling point	126 ° C
Vapor pressure	11.2 h Pa (20 ° C) 20 hPa (30 ° C) 57 hPa (50 ° C)
solubility	practically insoluble in water soluble in ethanol and diethyl ether (violent reaction with bases, possible formation of explosive mixtures) Risk of explosion with benzene , hydrocarbons, nitrotoluene , toluene , aniline , pyridine , dinitrobenzene and nitrobenzene
Refractive index	1.4384
safety instructions
GHS labeling of hazardous substances danger H and P phrases H: 271-301-315-319-330-335-351 P: 210-280-301 + 330 + 331 + 310-304 + 340 + 310-370 + 378-371 + 380 + 375
MAK	No classification as it is carcinogenic in animal experiments Switzerland: 1 ml m −3 or 8 mg m −3
Thermodynamic properties
ΔH f 0	38.4 kJ / mol
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Tetranitromethane , C (NO ₂ ) ₄ , is a nitro derivative of methane and thus a nitroalkane . The compound is the four-substituted representative of the series of nitromethanes with nitromethane , dinitromethane , trinitromethane and tetranitromethane.

Extraction and presentation

Tetranitromethane can in good yield by nitration of acetic anhydride or isopropanol are produced. In a more recent method, the compound is obtained by introducing ketene into 100% nitric acid . The syntheses require strict adherence to the reaction conditions and are not without risk. Distillation of the compound should be avoided.

properties

Physical Properties

Tetranitromethane is a colorless to yellowish, pungent smelling, extremely strongly oxidizing liquid . According to Antoine, the vapor pressure function results from log ₁₀ (P) = A− (B / (T + C)) (P in bar, T in K) with A = 4.54919, B = 1582.071 and C = −49 , 74 in the temperature range from 313 K to 373 K or A = 1.75688, B = 498.772 and C = −158.538 in the temperature range from 273 K to 313 K. The heat of vaporization is 43.1 kJ mol ⁻¹ .

Explosion parameters

Important explosion indicators are:

• Heat of explosion : 2193 kJ kg ⁻¹ (H ₂ O (g)) .
• Detonation velocity : 6360 m · s ⁻¹ at a density of 1.65 g · cm ⁻³
• Normal gas volume : 686 l kg ⁻¹ .
• Specific energy : 675 kJ kg ⁻¹
• Deflagration point : 140 ° C
• Impact sensitivity : 19 Nm

The connection alone is not very explosive. With hydrocarbons, however, mixtures of very high explosiveness are formed. Mixtures with propellants are extremely sensitive to impact and friction .

toxicity

The vapors strongly attack the respiratory tract, which must be taken into account given the high volatility of the compound. The substance has shown carcinogenic effects in animal experiments because the DNA is nitrated by this substance . According to Appendix II, No. 6 of the German Ordinance on Hazardous Substances (GefStoffV), tetranitromethane is classified as a particularly dangerous carcinogenic substance and may only be manufactured or used in closed facilities.

Use and handling

An important use in chemistry is based on the ability of tetranitromethane to display olefinic double bonds . As can be seen from the structural formula, the carbon atom is located in an electron deficiency center that forms charge transfer complexes with double bonds , which can be recognized by a strong yellow color. This fact is used in the analysis as an indicator of double bonds.

Tetranitromethane may be used as part of liquid explosives as large explosive oxidizing agent to be used. It forms highly explosive mixtures with all combustible substances. Paper must not be used for filtering in experiments with this substance. Even minor impurities turn tetranitromethane into an explosive that explodes when hit or rubbed. A tragic attempt at a lecture at the University of Münster in 1920 is known where a small steel tube containing tetranitromethane, toluene and cotton wool detonated shortly before it burned out so that over 30 students were injured, some seriously; According to the rectorate's files, however, there are even 10 dead and more than a dozen injured. Thereupon the chemical-technical Reichsanstalt determined a detonation speed of 9300 meters per second. Alfred Stettbacher then demonstrated that this mixture was far more explosive than hexogen , pentrite , blasting gelatine or panclastite and thus represented the most destructive explosive of all.

It can be used as a nitrating agent in synthetic organic chemistry , especially under basic reaction conditions. However, only one nitro group is used for nitration, the mesomeric stabilized trinitromethidione ( trinitromethane , common name nitroform) no longer has a nitrating effect.

Individual evidence

1. ↑ ^{a b c} Entry on tetranitromethane. In: Römpp Online . Georg Thieme Verlag, accessed on November 22, 2016.
2. ↑ ^{a b c d e f g h i j} Entry on tetranitromethane in the GESTIS substance database of the IFA , accessed on January 9, 2019(JavaScript required) .
3. ↑ J. Timmermans, M. Hennaut-Roland: Work of the International Bureau of Physical-Chemical Standards. IX. The Physical Constants of Twenty Organic Compounds. In: J. Chim. Phys. Phys.-Chim. Biol. 52, 1955, p. 223.
4. ↑ ^{a b c d e f g h i j k} J. Köhler, R. Meyer, A. Homburg: Explosivstoffe. tenth, completely revised edition. Wiley-VCH, Weinheim 2008, ISBN 978-3-527-32009-7 .
5. ↑ Swiss Accident Insurance Fund (Suva): Limit values ​​- current MAK and BAT values (search for 509-14-8 or tetranitromethane ), accessed on November 2, 2015.
6. ↑ David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Standard Thermodynamic Properties of Chemical Substances, pp. 5-20.
7. ^ Poe Liang: Tetranitromethane In: Organic Syntheses . 21, 1941, p. 105, doi : 10.15227 / orgsyn.021.0105 ; Coll. Vol. 3, 1955, p. 803 ( PDF ).
8. ↑ PG Urben; MJ Pitt: Bretherick's Handbook of Reactive Chemical Hazards . 8th edition, Vol. 1, Butterworth / Heinemann 2017, ISBN 978-0-08-100971-0 , p. 139.
9. ^ ^{A b} G. Edwards: The Vapor Pressure of Tetranitromethane. In: Trans. Faraday Soc. 48, 1952, pp. 513-515, doi: 10.1039 / TF9524800513 .
10. ^ AJC Nicholson: Some Physical Properties of Tetranitromethane. In: J. Chem. Soc. 1949, pp. 1553-1555, doi: 10.1039 / JR9490001553 .
11. ↑ Hazardous Substances Ordinance (GefStoffV) - as of April 2017 .
12. ^ Royal Society of Chemistry : Explosion Accident at the Chemical Institute, University of Munster iW, and Its Cause. In: J. Chem. Soc., Abstr. , 1920, 118, ii457-ii483. doi : 10.1039 / CA9201805457
13. ^ University archive Münster, NU EI 9 spec., Explosion accident in the Chemical Institute on May 27, 1920, Rüst, A. Ebert, K. Egli: Accidents during chemical work. Rascher, 1948, p. 23.