Tetranitromethane

Last updated
Tetranitromethane [1]
Tetranitromethane.png
Tetranitromethane-3D-vdW.png
Names
IUPAC name
Tetranitromethane
Other names
TNM
Tetan
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.007.359 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 208-094-7
KEGG
PubChem CID
RTECS number
  • PB4025000
UNII
UN number 1510
  • InChI=1S/CN4O8/c6-2(7)1(3(8)9,4(10)11)5(12)13 Yes check.svgY
    Key: NYTOUQBROMCLBJ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/CN4O8/c6-2(7)1(3(8)9,4(10)11)5(12)13
    Key: NYTOUQBROMCLBJ-UHFFFAOYAA
  • C([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-]
Properties
C(NO2)4
Molar mass 196.04 g/mol
AppearanceColorless 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)
insoluble
Vapor pressure 8 mmHg (20°C) [2]
-43.02·10−6 cm3/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Oxidant, can form explosive mixtures
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H271, H301, H315, H319, H330, H335, H351
P201, P202, P210, P220, P221, P260, P261, P264, P270, P271, P280, P281, P283, P284, P301+P310, P302+P352, P304+P340, P305+P351+P338, P306+P360, P308+P313, P310, P312, P320, P321, P330, P332+P313, P337+P313, P362, P370+P378, P371+P380+P375, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
3
1
2
OX
Lethal dose or concentration (LD, LC):
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]
Safety data sheet (SDS) ICSC 1468
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Tetranitromethane or TNM is an organic oxidizer with chemical formula C(NO2)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

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 Fig. 2.png
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 NO2 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−NO2 units versus the three-fold symmetry of the C(NO2)3 unit, as well as the close proximity of the NO2 groups hindering their free rotation, is the source for a very complicated mutually hindered movement of the NO2 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 TNM 2.jpg
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.
ParameterGEDXRD (range)
rC–N1.509(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_1105.1(16)108.2(3) – 110.9(3)
∡NCN_2111.7(8)107.3(3) – 111.4(2)
∡NCN_3106.6(2) – 107.1(3)
∡ONO129.2(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. [17]

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. [18]

See also

Related Research Articles

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RDX (abbreviation of "Research Department eXplosive") or hexogen, among other names, is an organic compound with the formula (O2N2CH2)3. It is white, odorless and tasteless, widely used as an explosive. Chemically, it is classified as a nitroamine alongside HMX, which is a more energetic explosive than TNT. It was used widely in World War II and remains common in military applications.

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

<span class="mw-page-title-main">TNT</span> Impact-resistant high explosive

Trinitrotoluene, more commonly known as TNT, more specifically 2,4,6-trinitrotoluene, and by its preferred IUPAC name 2-methyl-1,3,5-trinitrobenzene, is a chemical compound with the formula C6H2(NO2)3CH3. TNT is occasionally used as a reagent in chemical synthesis, but it is best known as an explosive material with convenient handling properties. The explosive yield of TNT is considered to be the standard comparative convention of bombs and asteroid impacts. In chemistry, TNT is used to generate charge transfer salts.

<span class="mw-page-title-main">Ammonium nitrate</span> Chemical compound with formula NH4NO3

Ammonium nitrate is a chemical compound with the formula NH4NO3. It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, although it does not form hydrates. It is predominantly used in agriculture as a high-nitrogen fertilizer.

<span class="mw-page-title-main">Dinitrogen tetroxide</span> Chemical compound

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

<span class="mw-page-title-main">Red fuming nitric acid</span> Chemical compound

Red fuming nitric acid (RFNA) is a storable oxidizer used as a rocket propellant. It consists of 84% nitric acid, 13% dinitrogen tetroxide and 1–2% water. The color of red fuming nitric acid is due to the dinitrogen tetroxide, which breaks down partially to form nitrogen dioxide. The nitrogen dioxide dissolves until the liquid is saturated, and produces toxic fumes with a suffocating odor. RFNA increases the flammability of combustible materials and is highly exothermic when reacting with water.

<span class="mw-page-title-main">Oleum</span> Corrosive liquid of excess sulfur trioxide in solution.

Oleum, or fuming sulfuric acid, is a term referring to solutions of various compositions of sulfur trioxide in sulfuric acid, or sometimes more specifically to disulfuric acid.

<span class="mw-page-title-main">Nitrogen dioxide</span> Chemical compound with formula NO₂

Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.

Nitromethane, sometimes shortened to simply "nitro", is an organic compound with the chemical formula CH
3
NO
2
. It is the simplest organic nitro compound. It is a polar liquid commonly used as a solvent in a variety of industrial applications such as in extractions, as a reaction medium, and as a cleaning solvent. As an intermediate in organic synthesis, it is used widely in the manufacture of pesticides, explosives, fibers, and coatings. Nitromethane is used as a fuel additive in various motorsports and hobbies, e.g. Top Fuel drag racing and miniature internal combustion engines in radio control, control line and free flight model aircraft.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

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<span class="mw-page-title-main">Nitration</span> Chemical reaction which adds a nitro (–NO₂) group onto a molecule

In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols and nitric acid. The difference between the resulting molecular structures of nitro compounds and nitrates is that the nitrogen atom in nitro compounds is directly bonded to a non-oxygen atom, whereas in nitrate esters, the nitrogen is bonded to an oxygen atom that in turn usually is bonded to a carbon atom.

<span class="mw-page-title-main">Hexanitrobenzene</span> Chemical compound

Hexanitrobenzene, also known as HNB, is a nitrobenzene compound in which six nitro groups are bonded to all six positions of a central benzene ring. is a high-density explosive compound with chemical formula C6N6O12, obtained by oxidizing the amine group of pentanitroaniline with hydrogen peroxide in sulfuric acid.

<span class="mw-page-title-main">Nitro compound</span> Organic compound containing an −NO₂ group

In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.

<span class="mw-page-title-main">Barium nitrate</span> Chemical compound

Barium nitrate is the inorganic compound with the chemical formula Ba(NO3)2. It, like most barium salts, is colorless, toxic, and water-soluble. It burns with a green flame and is an oxidizer; the compound is commonly used in pyrotechnics.

<span class="mw-page-title-main">Ethylene glycol dinitrate</span> Chemical compound

Ethylene glycol dinitrate, abbreviated EGDN and NGC, also known as Nitroglycol, is a colorless, oily, explosive liquid obtained by nitrating ethylene glycol. It is similar to nitroglycerine in both manufacture and properties, though it is more volatile and less viscous. Unlike nitroglycerine, the chemical has a perfect oxygen balance, meaning that its ideal exothermic decomposition would completely convert it to low energy carbon dioxide, water, and nitrogen gas, with no excess unreacted substances, without needing to react with anything else.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

<span class="mw-page-title-main">Hexanitroethane</span> Chemical compound

Hexanitroethane (HNE) is an organic compound with chemical formula C2N6O12 or (O2N)3C-C(NO2)3. It is a solid matter with a melting point of 135 °C.

<span class="mw-page-title-main">Trinitromethane</span> Chemical compound

Trinitromethane, also referred to as nitroform, is a nitroalkane and oxidizer with chemical formula HC(NO2)3. It was first obtained in 1857 as the ammonium salt by the Russian chemist Leon Nikolaevich Shishkov (1830–1908). In 1900, it was discovered that nitroform can be produced by the reaction of acetylene with anhydrous nitric acid. This method went on to become the industrial process of choice during the 20th century. In the laboratory, nitroform can also be produced by hydrolysis of tetranitromethane under mild basic conditions.

<span class="mw-page-title-main">Titanium(IV) nitrate</span> Chemical compound

Titanium nitrate is the inorganic compound with formula Ti(NO3)4. It is a colorless, diamagnetic solid that sublimes readily. It is an unusual example of a volatile binary transition metal nitrate. Ill defined species called titanium nitrate are produced upon dissolution of titanium or its oxides in nitric acid.

<span class="mw-page-title-main">Zirconium nitrate</span> Chemical compound

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

References

  1. Merck Index, 11th Edition, 9164.
  2. 1 2 3 4 NIOSH Pocket Guide to Chemical Hazards. "#0605". National Institute for Occupational Safety and Health (NIOSH).
  3. "Tetranitromethane". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  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.
  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. Bibcode:1976RuCRv..45.1052A. doi:10.1070/RC1976v045n11ABEH002759. S2CID   250859816.
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  8. Mahoney vs Nitroform Co., 114A.2d 863 (NJ Appellate Div1955).
  9. F. D. Chattaway (1910). "A simple method of preparing tetranitromethane". Journal of the Chemical Society . 97: 2099–2102. doi:10.1039/CT9109702099.
  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.
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  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". Angewandte Chemie International Edition. 56 (32): 9619–9623. doi:10.1002/anie.201704396. PMID   28557111.
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  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. Gakh, A. A.; Bryan, J. C.; Burnett, M. N.; Bonnesen, P. V. (2000). "Synthesis and structural analysis of some trinitromethanide salts". Journal of Molecular Structure. 520 (1–3): 221–228. Bibcode:2000JMoSt.520..221G. doi:10.1016/S0022-2860(99)00333-6.
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