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Nitrogen Tetroxide

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Nitrogen Tetroxide Basic information
Nitrogen Tetroxide Chemical Properties
  • Melting point:−11 °C(lit.)
  • Boiling point:21 °C(lit.)
  • Density 2.62 g/mL at 25 °C(lit.)
  • vapor density 1.58 (21 °C, vs air)
  • vapor pressure 14.33 psi ( 20 °C)
  • form gas
  • Water Solubility reac H2O [CRC10]
  • EPA Substance Registry SystemNitrogen tetroxide (10544-72-6)
Safety Information
  • Hazard Codes T+
  • Risk Statements 26-34
  • Safety Statements 9-26-28-36/37/39-45
  • RIDADR UN 1067 2.3
  • WGK Germany 1
  • RTECS QX1575000
  • HS Code 28112900
Nitrogen Tetroxide Usage And Synthesis
  • Chemical Propertiescol liquid [CRC10]
  • Physical propertiesColorless liquid or gas; exists in equilibrium with NO2; density 1.45 g/mL at 20°C; boils at 21.25°C; freezes at -9.35°C to a colorless diamagnetic solid; critical temperature 157.85°C; critical pressure 99.64 atm; critical volume 167 cm3/mol; reacts with water.
  • UsesNitrogen tetroxide is a solvent and a powerful and selective oxidizing agent. It’s adducts with organic solvents are used to synthesize nitrates of noble metals.
  • PreparationNitrogen tetroxide always is formed along with nitrogen dioxide during preparation of the dioxide (See Nitrogen Dioxide.) Mixed oxides are produced by oxidation of nitric oxide (NO) in air, heating metal nitrates, or by metals reacting with nitric acids or nitrates.
  • DefinitionA colorless gas that becomes a pale yellow liquid below 21°C and solidifies below –11°C. On heating, the gas dissociates to nitrogen dioxide molecules:
    N2O4(g) = 2NO2(g)
    This dissociation is complete at 140°C. Liquid dinitrogen tetroxide has good solvent properties and is used as a nitrating agent.
  • Definitiondinitrogen tetroxide: A colourlessto pale yellow liquid or a brown gas,N2O4; r.d. 1.45 (liquid); m.p. –11.2°C;b.p. 21.2°C. It dissolves in water withreaction to give a mixture of nitricacid and nitrous acid. It may be readilyprepared in the laboratory by thereaction of copper with concentratednitric acid; mixed nitrogen oxidescontaining dinitrogen oxide may alsobe produced by heating metal nitrates.The solid compound is whollyN2O4 and the liquid is about 99%N2O4 at the boiling point; N2O4 is diamagnetic.In the gas phase it dissociatesto give nitrogen dioxideN2O4?2NO2Because of the unpaired electron thisis paramagnetic and brown. LiquidN2O4 has been widely studied as anonaqueous solvent system (selfionizesto NO+ and NO3-). Dinitrogentetroxide, along with other nitrogenoxides, is a product of combustionengines and is thought to be involvedin the depletion of stratosphericozone.
  • General DescriptionRed-brown liquid with a sharp, unpleasant chemical odor. Low-boiling (boiling point 21.15°C) and held as a liquid by compression. Density 1.448 g / cm3. Consists of an equilibrium mixture of brown NO2 (nitrogen dioxide) and colorless N2O4 (diNITROGEN DIOXIDE). Evolves poisonous brown vapors. Cylinders and ton containers may not be equipped with a safety relief device. Prolonged exposure of the containers to fire or heat may result in their violent rupturing and rocketing.
  • Air & Water ReactionsReacts with water to form nitric acid and nitric oxide.
  • Reactivity ProfileLiquid NITROGEN DIOXIDE is an oxidizing agent consisting of an equilibrium mixture of colorless dinitrogen tetraoxide (N2O4) and red-brown nitrogen dioxide (NO2). The exact composition of the mixture depends on the temperature with higher temperature favoring conversion to NO2. Vaporizes readily to give NO2, also an oxidizing agent. Noncombustible but can accelerate the burning of combustible materials. Reacts with reducing agents to generate heat and products that may be gaseous (causing pressurization of closed containers). The products may themselves be capable of further reactions (such as combustion in the air). Reacts with alkalis to form nitrates and nitrites [Merck 11th ed. 1989]. Corrodes steel if wet, but can be stored in steel cylinders if dry [Merck]. Reacts explosively with liquid ammonia even at very low temperatures (below its freezing point) [Mellor, 1940, Vol. 8, 54]. Reacts energetically with boron trichloride [Mellor, 1946, Vol. 5, 132]. Mixtures with metal carbonyls are hypergolic (enflame immediately). Mixtures with halocarbons, hydrazine derivatives, heterocyclic bases (pyridine), isopropyl nitrite/propyl nitrite, active metals (magnesium, calcium, etc.), nitroaromatics, nitrogen trichloride, phosphorus, triethylamine, unsaturated hydrocarbons may react explosively. Accidental mixing with hot cyclohexane caused an explosion [MCA Case History 128. 1962]. A mixture with acetonitrile and indium showed no evidence of change for a time and then detonated when shaken (ascribed to the catalyzed oxidation of acetonitrile) [Chem. & Ind., 1958, 1004]. Mixture with alcohols produced a violent explosion [Chem. Eng. News, 1955, 33, 2372]. Vapor reacts with barium oxide incandescently [Mellor, 1940, Vol. 8, 545]. A slow reaction between the vapor and formaldehyde became explosive near 180°C [Trans. Faraday Soc. 45:767-770. 1949]. Manganese and potassium both ignite in the vapor [Ann. Chem. et Phys.(2) 2:317]. The vapor and ozone react with the evolution of light and often explode when mixed [J. Chem. Phys. 18:366. 1920].
  • HazardSee Nitrogen Dioxide, Hazard.
  • Health HazardVery concentrated fumes produce coughing, choking, headache, nausea, pain in chest and abdomen; otherwise, few symtoms appear at time of exposure. After symptom-free period of 5-72 hours, pulmonary edema gradually develops, causing fatigue, restlessness, coughing, difficulty in breathing, frothy expectoration, mental confusion, lethargy, bluish skin, and weak, rapid pulse. Since NOX interferes with gas exchange in lungs, unconscious- ness and death by asphyxiation can result, usually within a few hours after onset of pulmonary edema.
  • Safety ProfileA poison. Moderately toxic by inhalation. When heated to decomposition it emits toxic fumes of NOx. See also NITROGEN MONOXIDE.
  • Purification MethodsPurify it by oxidation at 0o in a stream of oxygen until the blue colour changes to red-brown. Alternatively distil it from P2O5, then solidify it by cooling in a deep-freeze (at –78o, giving nearly colourless crystals). Oxygen can be removed by alternate freezing and melting. TOXIC VAPOUR. [Schenk in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I pp 488-489 1963.]
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