| | TETRANITROMETHANE Basic information |
| | TETRANITROMETHANE Chemical Properties |
| Melting point | 13-14 °C(lit.) | | Boiling point | 126 °C(lit.) | | density | 1.637 g/mL at 25 °C(lit.) | | vapor pressure | 8.4 mm Hg ( 20 °C) | | refractive index | n20/D 1.438(lit.) | | Fp | >230 °F | | storage temp. | 2-8°C | | solubility | Miscible with alcohol and ether (Hawley, 1981) | | form | liquid | | Merck | 13,9305 | | Exposure limits | NIOSH REL: TWA 1 ppm, IDLH 4 ppm; OSHA PEL: TWA 5 ppb (adopted). | | Dielectric constant | 23.1（Ambient） | | Stability: | Stability Oxidizer. Reacts with a wide variety of materials including organics, brass, zinc, cotton, sodium, pyridine, toluene, aluminium, finely powdered metals. Heat, friction and shock sensitive. May decompose or react with other chemicals violently. | | CAS DataBase Reference | 509-14-8(CAS DataBase Reference) | | IARC | 2B (Vol. 65) 1996 | | EPA Substance Registry System | Tetranitromethane (509-14-8) |
| | TETRANITROMETHANE Usage And Synthesis |
| 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. |
| | TETRANITROMETHANE Preparation Products And Raw materials |
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