Tetranitromethane

Tetranitromethane[1] |  |

|

Names
IUPAC name

Tetranitromethane

Other names

TNM
Tetan

Identifiers

CAS Number

* 509-14-8 Y

3D model (JSmol)

* Interactive image

ChEMBL |

* ChEMBL261663 Y

ChemSpider |

* 13842838 Y

EC Number |

* 208-094-7

KEGG |

* C19300 Y

PubChem CID

* 10509

RTECS number |

* PB4025000

UNII |

* K1G7CKU98F Y

UN number | 1510

InChI

* InChI=1S/CN4O8/c6-2(7)1(3(8)9,4(10)11)5(12)13 Y

Key: NYTOUQBROMCLBJ-UHFFFAOYSA-N Y

* InChI=1/CN4O8/c6-2(7)1(3(8)9,4(10)11)5(12)13

Key: NYTOUQBROMCLBJ-UHFFFAOYAA

SMILES

* C([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-]

Properties

Chemical formula

| C(NO

Molar mass | 196.04 g/mol
Appearance  | Colorless to pale-yellow liquid or solid
Odor | Pungent
Density | 1.623 g/cm3
Melting point |  13.8 °C (56.8 °F; 286.9 K)
Boiling point |  126 °C (259 °F; 399 K)

Solubility in water

| insoluble
Vapor pressure | 8 mmHg (20°C)[2]

Magnetic susceptibility (χ)

| -43.02·10−6 cm3/mol
Hazards
Main hazards | Oxidant, can form explosive mixtures
Safety data sheet | ICSC 1468
GHS pictograms |
GHS Signal word | Danger

GHS hazard statements

| H271, H301, H315, H319, H330, H335, H351

GHS precautionary statements

| P201, P202, P210, P220, P221, P260, P261, P264, P270, P271, P280, P281, P283, P284, P301+310, P302+352, P304+340, P305+351+338, P306+360, P308+313, P310, P312, P320, P321, P330
NFPA 704 (fire diamond)  |

Lethal dose or concentration (LD, LC):

LC50 (median concentration)

| 18 ppm (rat, 4 hr)
100 ppm (cat, 20 min)
54 ppm (mouse, 4 hr)[3]
NIOSH (US health exposure limits):

PEL (Permissible)

| TWA 1 ppm (8 mg/m3)[2]

REL (Recommended)

| TWA 1 ppm (8 mg/m3)[2]

IDLH (Immediate danger)

| 4 ppm[2]
Related compounds

Related compounds

| Hexanitroethane
Octanitropentane
Trinitromethane

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

N verify (what is YN ?)
Infobox references

Tetranitromethane or TNM is an organic oxidizer with chemical formula C(NO

4. Its chemical structure consists of four nitro groups attached to one carbon atom. In 1857 it was first synthesised by the reaction of sodium cyanoacetamide with nitric acid.[4]

## Contents

* 1 Uses
* 2 Preparation
* 3 Structure
* 4 Safety
* 5 See also
* 6 References
* 7 External links

## Uses

It has been investigated for use as an oxidizer in bipropellant rockets; however, its low melting point makes it unsuitable. Highly purified tetranitromethane cannot be made to explode, but its sensitivity is increased dramatically by oxidizable contaminants, such as anti-freezing additives. This makes it effectively unusable as a propellant.[5] In the laboratory it is used as a reagent for the detection of double bonds in organic compounds and as a nitrating reagent. It has also found use as an additive to diesel fuel to increase the cetane number.[6]

## Preparation

TNM is a pale yellow liquid that can be prepared in the laboratory by the nitration of acetic anhydride with anhydrous nitric acid (Chattaway's method).[7] This method was attempted on an industrial scale in the 1950s by Nitroform Products Company in Newark, USA, but the entire plant was destroyed by an explosion in 1953.[8]

The first industrial scale production was started in Germany during World War II in an effort to improve the cetane number of diesel fuel. This process improved the original method, which started with acetic acid and nitric acid.[9] Without regard to yield or cost, approximately 10 tons of TNM were produced in a few weeks. However, this production process has not been used again industrially after the end of the war, because of high associated costs.[10]

For commercial use a cheaper method starting from acetylene has been used.[11] First, nitric acid containing mercuric nitrate is reduced by acetylene, resulting in trinitromethane (nitroform) and a mixture of carbon dioxide and nitrogen oxide as waste gas. The nitrogen oxides are valuable and normally recovered as nitric acid in an absorption tower. The resulting nitroform is converted to TNM by adding nitric and sulfuric acid at higher temperatures. With this method a yield of 90% (based on nitric acid) before purification can be reached.[12]

## Structure

Figure 1: Disordered appearance of TNM molecules in the crystalline state

TNM is a prime example of molecular flexibility. It brought structural methods to the limits of their applicability as is shown by the fact that the structure of TNM was attempted to be determined for a period of more than 70 years in various phases.[13]

Early investigations by gas electron diffractions were unable to describe the observed diffraction pattern in full and only the application of a four-dimensional model concerning the correlated movement of the four NO
2 groups about the C–N bonds was able to describe the experimental observations fully. The problem occurs, because the two-fold local symmetry of the C–NO
2 units versus the three-fold symmetry of the C(NO

3 unit, as well as the close proximity of the NO
2 groups hindering their free rotation, is the source for a very complicated mutually hindered movement of the NO
2 groups.

The crystal structure has also been attempted several times. A first decent solution of the problem required a model describing a highly disordered high‐temperature crystalline phase of a high-temperature phase (>174.4 K) as is shown in Figure 1. Reduction of symmetry and analysis of the twinning of the crystals led finally to a resolved disorder of the structure shown in Figure 2.

Figure 2: Resolved disorder of the high-temperature phase of TNM

The structure of an ordered low‐temperature phase contains three independent molecules in the asymmetric unit. Structural parameters of the gaseous and solid phases are listed in the following table for comparison.

Structural parameters of TNM determined by gas electron diffraction (GED) and single crystal X-ray diffraction (XRD). Distances are in Å angles in deg.  Parameter  | GED  | XRD (range)

|
|

rC–N  | 1.509(5)  | 1.502(4) – 1.554(5)
rN–O(eclip)  | 1.201(3)  | 1.198(4) – 1.215(5)
rN–O(stag)  | 1.199(3)  | 1.178(5) – 1.222(4)
∡NCN_1  | 105.1(16)  | 108.2(3) – 110.9(3)
∡NCN_2  | 111.7(8)  | 107.3(3) – 111.4(2)
∡NCN_3  |  | 106.6(2) – 107.1(3)
∡ONO  | 129.2(17)  | 128.0(4) – 132.3(4)

## Safety

The ability of TNM to detonate is greatly affected by the presence of impurities, even in small quantities. TNM forms extremely powerful explosive mixtures when fuels are added in stoichiometric proportions. Many of these mixtures show sensitivity to impact even higher than that of nitroglycerine.[14]

Tetranitromethane can be used as a component of highly explosive liquid explosives as an oxidizing agent. It forms highly explosive mixtures with all flammable substances. When experimenting with this substance, paper filters should not be used for filtration. Even small impurities make tetranitromethane an explosive that explodes on impact or friction. A tragic lecture experiment at the University of Münster in 1920 is well known, where a small steel tube containing tetranitromethane, toluene and absorbent cotton detonated shortly before burning out in such a way that more than 30 students were injured, some seriously;[15] however, on the basis of the rector's office records, as many as 10 deaths and more than a dozen injuries are documented.[16] Thereupon the German Chemical-technical Reichsanstalt determined a detonation speed of 9300 meters per second. Alfred Stettbacher then proved comparatively that this mixture was far more explosive than hexogen, pentrite, blasting gelatine or panclastite and thus represented the most destructive explosive of all.

TNM reacts with moisture at elevated pH to produce trinitromethane (nitroform) which reacts easily with metals to form highly unstable and explosive salts.

Tetranitromethane is highly toxic. Absorption of as little as 2.5 mg/kg can cause methemoglobinemia, pulmonary edema, and damage to liver, kidney, and central nervous system. It is reasonably expected to be a human carcinogen.[17]

## See also

* Hexanitroethane
* Trinitramide

## References

1. ↑ Merck Index, 11th Edition, 9164.
2. ↑ 2.0 2.1 2.2 2.3 NIOSH Pocket Guide to Chemical Hazards. "#0605". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0605.html.
3. ↑ "Tetranitromethane". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/idlh/509148.html.
4. ↑ L. N. Shishkov (1857). "Sur la constitution de l'acetic fulminique et un nouvelle serie de corps derives de l'acide acetique". Annales de chimie et de physique 49 (11): 310. http://gallica.bnf.fr/ark:/12148/bpt6k347908/f309.table.
5. ↑ J. G. Tschinkel (1956). "Tetranitromethane as Oxidizer in Rocket Propellants". Industrial and Engineering Chemistry 48 (4): 732–735. doi:10.1021/ie50556a022.
6. ↑ K. V. Altukhov, V. V. Perekalin (1976). "The Chemistry of Tetranitromethane". Russian Chemical Reviews 45 (11): 1052–1066. doi:10.1070/RC1976v045n11ABEH002759. Bibcode: 1976RuCRv..45.1052A.
7. ↑ Liang, P. (1941). "Tetranitromethane". Organic Syntheses 21: 105. http://www.orgsyn.org/Content/pdfs/procedures/CV3P0803.pdf. ;  Collective Volume, 3, pp. 803
8. ↑ Mahoney vs Nitroform Co., 114 A.2d 863 (NJ Appellate Div 1955).
9. ↑ F. D. Chattaway (1910). "A simple method of preparing tetranitromethane". Journal of the Chemical Society 97: 2099–2102. doi:10.1039/CT9109702099. https://zenodo.org/record/2054355.
10. ↑ K. F. Hager (1949). "Tetranitromethane". Industrial and Engineering Chemistry 41 (10): 2168–2172. doi:10.1021/ie50478a028.
11. ↑ K. J. P. Orton, P. V. McKie (1920). "The action of nitric acid on unsaturated hydrocarbons. The action of nitric acid on acetylene". Journal of the Chemical Society 117: 283–297. doi:10.1039/CT9201700283. https://zenodo.org/record/2410940.
12. ↑ Urbanski, Tadeusz (1964). Chemistry and Technology of Explosives. I. Pergamon Press. pp. 589–594.
13. ↑ Vishnevskiy, Yury V.; Tikhonov, Denis S.; Schwabedissen, Jan; Stammler, Hans-Georg; Moll, Richard; Krumm, Burkhard; Klapötke, Thomas M.; Mitzel, Norbert W. (2017-08-01). "Tetranitromethane: A Nightmare of Molecular Flexibility in the Gaseous and Solid States" (in en). Angewandte Chemie International Edition 56 (32): 9619–9623. doi:10.1002/anie.201704396. PMID 28557111.
14. ↑ Urbanski, Tadeusz (1964). Chemistry and Technology of Explosives. I. Pergamon Press. p. 593.
15. ↑ Royal Society of Chemistry: Explosion Accident at the Chemical Institute, University of Munster i.W., and Its Cause. In: J. Chem. Soc., Abstr., 1920, 118, ii457-ii483. doi:10.1039/CA9201805457
16. ↑ Universitätsarchiv Münster, NU E I 9 spec., Explosionsunglück im Chemischen Institut am 27. Mai 1920, Rüst, A. Ebert, K. Egli: Unfälle beim chemischen Arbeiten. Rascher, 1948, S. 23.
17. ↑ National Toxicology Program (2011). "Tetranitromethane". Report On Carcinogens. National Toxicology Program. https://ntp.niehs.nih.gov/ntp/roc/content/profiles/tetranitromethane.pdf.

## External links

* WebBook page for CN4O8
* CDC - NIOSH Pocket Guide to Chemical Hazards

* v
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Blood|

* Cyanogen
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Blister|

* Arsenicals
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* HN1
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* TL-301
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Nerve|

| G-agents|

* Tabun (GA)
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V-agents|

* EA-2192
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Novichok agents|

* A-230
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Carbamates|

* EA-3887
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Other|

* EA-2012
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* 2-Ethoxycarbonyl-1-methylvinyl cyclohexyl methylphosphonate
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Precursors|

* Chlorosarin
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* Cyclohexanol
* 1,8-Dibromooctane
* N,N-Diisopropylaminoethanol
* Dimethylamidophosphoric dichloride
* Dimethylamidophosphoric dicyanide
* Isopropyl alcohol
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* Methylphosphonic acid dichloride
* Methylphosphonyl difluoride
* Pinacolone
* Pinacolyl alcohol
* QL
* 3,3,5-Trimethylcyclohexanol

Neurotoxins|

* Saxitoxin (TZ)
* Botulinum toxin (BTX)
* Tetanospasmin (TeNT)
* Chlorophenylsilatrane
* Tetrodotoxin

Nettle|

* Phosgene oxime (CX)

Pulmonary/Choking agent|

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Vomiting agent|

* Adamsite
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* Diphenylcyanoarsine
* Diphenylaminecyanoarsine

Incapacitating|

* Agent 15 (BZ)
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Riot control|

* Xylyl bromide
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* CN
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* CNS

Other|

* Methyl fluoroacetate
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Fuel types|

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Fuel additives|

* Butyl rubber
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* 2,4-Dimethyl-6-tert-butylphenol
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* Ecalene
* Ethylenediamine
* Metal deactivator
* Methyl tert-butyl ether
* Nitromethane
* Tetraethyllead
* Tetranitromethane

Fluids|

* Motor oil
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Retail|

* Fuel card
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Original source: https://en.wikipedia.org/wiki/Tetranitromethane. Read more

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Retrieved from "https://handwiki.org/wiki/index.php?title=Chemistry:Tetranitromethane&oldid=440013"
*[CID]: Compound ID
*[H271]: May cause fire or explosion: strong oxidizer
*[H301]: Toxic if swallowed
*[H315]: Causes skin irritation
*[H319]: Causes serious eye irritation
*[H330]: Fatal if inhaled
*[H335]: May cause respiratory irritation
*[H351]: Suspected of causing cancer
*[P201]: Obtain special instructions before use
*[P202]: Do not handle until all safety precautions have been read and understood
*[P210]: Keep away from heat/sparks/open flames/hot surfaces – No smoking
*[P220]: Keep/Store away from clothing/…/combustible materials
*[P221]: Take any precaution to avoid mixing with combustibles
*[P260]: Do not breathe dust/fume/gas/mist/vapours/spray
*[P261]: Avoid breathing dust/fume/gas/mist/vapours/spray
*[P264]: Wash … thoroughly after handling
*[P270]: Do not eat, drink or smoke when using this product
*[P271]: Use only outdoors or in a well-ventilated area
*[P280]: Wear protective gloves/protective clothing/eye protection/face protection
*[P281]: Use personal protective equipment as required
*[P283]: Wear fire/flame resistant/retardant clothing
*[P284]: Wear respiratory protection
*[P301+310]: IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician
*[P302+352]: IF ON SKIN: Wash with soap and water
*[P304+340]: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
*[P305+351+338]: IF IN EYES: Rinse continuously with water for several minutes. Remove contact lenses if present and easy to do – continue rinsing
*[P306+360]: IF ON CLOTHING: Rinse immediately contaminated clothing and skin with plenty of water before removing clothes
*[P308+313]: IF exposed or concerned: Get medical advice/attention
*[P310]: Immediately call a POISON CENTER or doctor/physician
*[P312]: Call a POISON CENTER or doctor/physician if you feel unwell
*[P320]: Specific treatment is urgent (see … on this label)
*[P321]: Specific treatment (see … on this label)
*[P330]: Rinse mouth
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