TETRANITROMETHANE

Description

Tetranitromethane (TNM) is a nitroalkane compound that is a colorless to pale-yellow liquid or solid (below 57
F) with a biting, pungent odor at room temperature. TNM is not known to occur as a natural product and is generated during the manufacture of trinitrotoluene (TNT) as an undesired byproduct that can be separated by means of its higher vapor pressure. It can be prepared by different reactions, the nitration of acetic anhydride or acetylene with nitric acid being the less problematic. It was synthesized in large amounts (as an industrial-scale production) for the first time in Germany during World War II during the development of the V2 rocket for use as a substitute for nitric acid in rocket fuel and due to the observation that its addition to diesel fuel increased the cetane number. A pilot-scale manufacture was set up by Nitroform Inc. (Newark, NJ, USA), but in 1953 was destroyed by an explosion. In 1994, TNM was produced by only one company in the United States and another one in Russia.

Chemical Properties

Tetranitromethane, a nitroparaffin, is a colorless to pale yellow liquid or solid with a pungent odor. It causes tears.

Physical properties

Colorless to pale yellow to yellow-orange liquid with a pungent odor. Sensitive to heat, friction, and shock. Explosive in presence of impurities.

Uses

Oxidizer in rocket propellants; explosive in admixture with toluene; reagent for detecting presence of double bonds in organic compounds.

Uses

Reagent for nitration of enol silyl ethers7 and aromatic compounds.8 Employed in the photooxidation of sulfides to sulfoxides.9

Uses

Oxidizer in rocket propellants. As explosive in admixture with toluene. To increase cetane number of diesel fuels. Reagent for detecting the presence of double bonds in organic Compounds and for mild nitrations. Has been proposed as irritant war gas.

Definition

ChEBI: Tetranitromethane is an organonitrogen compound.

General Description

A pale yellow liquid. Irritates skin and respiratory tract. Very toxic by inhalation. Difficult to ignite. Burns at a steady rate once ignited. Under prolonged exposure to fire or heat containers may rupture violently and rocket Produces toxic oxides of nitrogen during combustion.

Air & Water Reactions

Highly Flammable. Insoluble in water.

Reactivity Profile

Self-reactive. TETRANITROMETHANE is a weak, but highly sensitive explosive [Van Dolah 1967]. May decompose explosively if contaminated with combustible material. A propellant. Ignites upon contact with alcohols, amines, ammonia, beryllium alkyls, boranes, dicyanogen, hydrazines, hydrocarbons, hydrogen, nitroalkanes, powdered metals, silanes, or thiols [Bretherick 1979 p.174].

Hazard

Dangerous fire and explosion risk. Toxic by ingestion, inhalation, skin absorption. Eye and upper respiratory tract irritant. Upper respiratory tract cancer. Possible carcinogen.

Health Hazard

Acute effects include irritation of the eyes and respiratory passages and mild burns to the skin. After more prolonged inhalation, headache and respiratory distress may occur. After prolonged exposure, central nervous system, heart, liver, and kidney damage can occur as well as pulmonary edema.

Fire Hazard

Spontaneous chemical reaction may produce fire. Material is a strong oxidizer. The potential for explosion is severe, especially when exposed to heat or to powerful oxidizing or reducing agents; or when shocked or heated. TETRANITROMETHANE is more easily detonated than TNT. Impurities can also cause explosion. The material is highly sensitive; hydrocarbons exposed to TETRANITROMETHANE form exceedingly sensitive explosives. When heated to decomposition, TETRANITROMETHANE emits highly toxic fumes of oxides of nitrogen. Shock will explode it. Avoid hydrocarbons, aluminum, toluene, cotton, aromatic nitro compounds, alkalis, metals and rubber. Avoid impurities, shock, heat, and reducing agents.

Safety Profile

Confirmed carcinogen with carcinogenic and neoplastigenic data. Poison by ingestion, inhalation, intravenous, and intraperitoneal routes. Irritating to the skin, eyes, mucous membranes, and respiratory passages, and does serious damage to the liver. Mutation data reported. It occurs as an impurity in crude TNT, and is thought to be mainly responsible for the irritating properties of that material. It can cause pulmonary edema, mild methemoglobinemia, and fatty degeneration of the liver and hdneys. A powerful oxidizer. A very dangerous fire hazard. A severe explosion hazard when shocked or exposed to heat. May explode during distillation. Potentially explosive reaction with ferrocene, pyridine, sodium ethoxide. mxtures with amines (e.g., aniline) ignite spontaneously and may explode. Mixtures with cotton or toluene may explode when ignited. Forms sensitive and powerful explosive mixtures with nitrobenzene, l-nitrotoluene, 4-nitrotoluene, 1,3-dinitrobenzene, 1 -nitronaphthalene, other oxygen-deficient explosives, hydrocarbons. Can react vigorously with oxidizing materials. Incompatible with aluminum. When heated to decomposition it emits highly toxic fumes of NOx. Used as an oxidizer in rocket propellants and as an explosive. See also NITRATES; EXPLOSIVES, HIGH.

Potential Exposure

Tetranitromethane is used as a solvent for polymers and as a stabilizer; as an oxidizer in rocket propellant combinations. It is also used as an explosive in admixture with toluene.

Carcinogenicity

Tetranitromethane is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in experimental animals.

Environmental Fate

TNM is almost insoluble in water (0.9 g l^-1), and soluble in ethanol, carbon tetrachloride, diethyl ether, and alcoholic potassium hydroxide. Some other relevant physicochemical properties of TNM are the following: melting point 13.8°C, boiling point 126°C, estimated Koc value of 100, log Kow of 0.791, estimated Henry’s law constant of 2.4×103 atmm3 mol1 at 25°C, and its vapor pressure (8.42mmHg) is lesser than that of water.
Production and use of TNM may result in its release to the environment through various waste streams. The physical and chemical properties will lead to its fate in the environment. If released to air, TNM will exist solely as a vapor in the atmosphere and could be degraded by reaction with photochemically produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 31 days. TNM may be susceptible to direct photolysis. If released to soil, TNM is expected to have high mobility. It may volatilize from dry soil surfaces, and volatilization from moist soil surfaces is expected to be an important fate process. If released into water, TNM is not expected to adsorb to suspended solids and sediment, and volatilization from water surfaces is expected to be an important fate process (half-lives of 2 h and 6 days, for river and lake models, respectively). TNM is not expected to undergo hydrolysis in the environment due to the lack of functional groups that hydrolyze under environmental conditions. An estimated bioconcentration factor of 13 suggests the potential for bioconcentration in aquatic organisms is low.

Shipping

UN1510 Tetranitromethane, Hazard Class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 5.1-Oxidizer, Inhalation Hazard Zone B.

Purification Methods

Shake tetranitromethane with dilute NaOH, wash, steam distil, dry with Na2SO4 and fractionally crystallise it by partial freezing. The melted crystals are dried with MgSO4 and fractionally distilled under reduced pressure. Alternatively, shake it with a large volume of dilute NaOH until no absorption attributable to the aci-nitro anion (from monodiand trinitromethanes) is observable in the water. Then wash it with distilled water, and distil it at room temperature by passing a stream of air or nitrogen through the liquid and condensing it in a trap at -80o. It can be dried with MgSO4 or Na2SO4, fractionally crystallised from the melt, and fractionally distilled under reduced pressure. [Liang Org Synth Coll Vol III 803 1955, Beilstein 4 H 80, 4 I 21, 4 II 45, 4 III 116, 4 IV 107.] Potentially explosive (when impure e.g. with toluene), toxic, carcinogenic.

Toxicity evaluation

TNM is a severe respiratory and eye irritant in humans and animals, although its precise mechanism of toxicity is unknown. TNM toxicity occurred predominantly in the respiratory tract, where it caused pulmonary edema, hemorrhage, and death at sufficiently high concentrations. Methemoglobinemia formation reported following oral administration may be a result of reduction of TNM in the gut. TNM selectively binds tyrosine residues in proteins and peptides and can inactivate various enzymes. In vitro data using rat alveolar macrophages suggested that nitration of cell membrane tyrosine residues and subsequent inhibition of tyrosine kinase pathways may be a mechanism of TNM toxicity.

Incompatibilities

Tetranitromethane is a powerful oxidizer. It is more easily detonated than TNT. Contact with hydrocarbons, alkalis, or metals form explosive mixtures. Contact with toluene or cotton may cause fire andexplosion. Combustible material wet with tetranitromethane may be highly explosive. The potential for explosion is severe, especially when exposed to heat, powerful oxidizers, or reducing agents; or, when subject to mild shock. Impurities can also cause explosives. Attacks some plastics, rubber and coatings.

Waste Disposal

Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Open burning at remote burning sites is not entirely satisfactory since it makes no provision for the control of the toxic effluents, nitrogen oxides and HCN. Suggested procedures are to employ modified closed pit burning, using blowers for air supply and passing the effluent combustion gases through wet scrubbers.

Raw materials

Preparation Products