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NITROGEN DIOXIDE

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CAS:10102-44-0
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NITROGEN DIOXIDE Basic information
Preparation Reaction
Product Name:NITROGEN DIOXIDE
Synonyms:NITROGEN DIOXIDE;Azote;NA 1067;Nitrito;Nitro;Nitrogen oxide;Nitrous gas or air;Oxoazane oxide
CAS:10102-44-0
MF:NO2 *
MW:46.01
EINECS:233-272-6
Product Categories:Inorganics
Mol File:10102-44-0.mol
NITROGEN DIOXIDE Structure
NITROGEN DIOXIDE 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 brown gas
OdorPungent, acrid odor detectable at 0.12 ppm
Water Solubility decomposes in H2O to HNO3 and releases NO; soluble conc H2SO4, HNO3 [MER06]
CAS DataBase Reference10102-44-0(CAS DataBase Reference)
Safety Information
Hazard Codes T+,O
Risk Statements 26-34-8
Safety Statements 9-26-28-36/37/39-45
RIDADR UN 1067 2.3
WGK Germany 1
RTECS QX1575000
HazardClass 2.3
HS Code 28112900
Toxicity LC50 inhal (rat)
88 ppm (4 h)
PEL (OSHA)
5 ppm (9 mg/m3; ceiling)
TLV-TWA (ACGIH)
3 ppm (5.6 mg/m3)
STEL (ACGIH)
5 ppm (9.4 mg/m3)
MSDS Information
ProviderLanguage
SigmaAldrich English
NITROGEN DIOXIDE Usage And Synthesis
PreparationNitrogen dioxide may be prepared by several methods. It is produced when an electric discharge is passed through air. It is made commercially from nitric oxide and air. Nitric oxide made by various processes (See Nitric Oxide) rapidly oxidizes to nitrogen dioxide. It is formed by decomposing nitric acid or by oxidizing ammonia with air:
HNO3 → NO2 + H2O
4NH3 + 7O2 → 4NO2 + 6H2O
Also, nitrogen dioxide can be made by heating copper with nitric acid.
In the laboratory, nitrogen dioxide is formed by heating lead nitrate or nitrate of another heavy metal:
2Pb(NO3)2 → 2PbO + 4NO2 + O2
Gaseous mixture of nitrogen dioxide and oxygen is passed through a U-tube placed in a freezing mixture. Nitrogen dioxide condenses and is collected as liquid.
ReactionThe oxidation state of nitrogen in nitrogen dioxide is +4. The molecule has an unpaired electron. Both these factors contribute to its reactivity. Nitrogen dioxide readily converts to other forms of nitrogen oxides. It coexists in equilibrium with its dimeric form, N2O4. The latter is more stable at ordinary temperatures.
When heated above 150°C, nitrogen dioxide dissociates to nitric oxide and oxygen:
2NO2 → 2NO + O2
Nitrogen dioxide dissolves in cold water, forming a mixture of nitrous acid and nitric acid:
2NO2 + H2O → HNO2 + HNO3
Nitrous acid readily decomposes to nitric acid and nitric oxide:
3HNO2 → HNO3 + NO + H2O
The overall reaction is as follows:
3NO2 + H2O → 2HNO3 + NO
When dissolved in warm water, no nitrous acid forms.
Nitrogen dioxide is a strong oxidizing agent. It oxidizes both nonmetals and metals, forming their oxides and itself reduced to nitrogen. Thus, sulfur, phosphorus and charcoal burn in nitrogen dioxide to yield oxides of these elements and nitrogen:
2NO2 + 2S → 2SO2 + N2
2NO2 + 2C → 2CO2 + N2
Copper, zinc, iron and many other metals are similarly converted to their oxides when heated with nitrogen dioxide:
2NO2 + 2Cu → 2CuO + N2
2NO2 + 4Zn → 4ZnO + N2
Nitrogen dioxide oxidizes an aqueous solution of iodide to iodine, hydrogen sulfide to sulfur, and carbon monoxide to carbon dioxide. In such reaction, it is reduced to nitric oxide, rather than nitrogen:
NO2 + 2I¯ + H2O → I2 + NO + 2OH¯
NO2 + H2S → NO + H2O + S
NO2 + CO → NO + CO2
With stronger oxidizing agents, nitrogen dioxide acts as a reducing agent.
Thus, it reduces per manganate, MnO4¯, to Mn2+ ion, decolorizing its solution. In this reaction, it is oxidized to nitrate ion:
MnO4¯ + 5NO2 + H2O → Mn2+ +2H+ + 5NO3¯
Reaction with fluorine forms nitryl fluoride, NO2F:
2NO2 + F2 → 2NO2F
Nitrogen dioxide reacts with alkalies, giving a mixture of nitrite and nitrate:
2NO2 + 2OH¯ → NO2¯ + NO3¯ + H2O
Chemical PropertiesRed to brown gas above 21.1C, brown liquid below 21.1C; colorless solid approximately ?11C.The pressurized liquid is nitrogen tetroxide (dinitrogen tetroxide) because of admixture of N 2O4 with NO2,Noncombustible but supports combustion.
Chemical PropertiesNitrogen dioxide (and nitrogen tetroxide, the solid dimer) is a dark brown gas (above 21 C) or a yellow, fuming liquid or colorless solid with a pungent, acrid odor. The solid form is colorless below about 11 C; it is found structurally as N2O4.
UsesNitrogen dioxide is an intermediate in producing nitric acid. It also is used in the lead chamber process for making sulfuric acid. It is used as a nitrating and oxidizing agent, in rocket fuels, in the manufacture of hemostatic cotton and other oxidized cellulose compounds, and in bleaching flour. Nitrogen dioxide occurs in trace concentrations in the atmosphere due to oxidation of nitric oxide in air. It also is found in exhaust gases of internal combustion engines, in industrial waste gases from plants using nitric acid, and in cigarette smoke. Brown color of smog in many industrial urban areas is attributed to nitrogen dioxide.
General DescriptionA reddish brown gas or yellowish-brown liquid when cooled or compressed. Shipped as a liquefied gas under own vapor pressure. Vapors are heavier than air. Toxic by inhalation (vapor) and skin absorption. Noncombustible, but accelerates the burning of combustible materials. Cylinders and ton containers may not be equipped with a safety relief device.
Air & Water ReactionsCombines with oxygen to form NITROGEN DIOXIDE, a brown gas that is deadly poisonous [Merck 11th ed. (1989]. Decomposes in water to form nitric acid and nitric oxide, reacts with alkalis to form nitrate and nitrites [Merck 11th ed. 1989]. The liquid nitrogen oxide is very sensitive to detonation, in the presence of water.
Reactivity ProfileNITROGEN DIOXIDE (nitrogen peroxide) is a strong oxidizing agent. Powdered aluminum burns in the vapor of carbon disulfide, sulfur dioxide, sulfur dichloride, nitrous oxide, nitric oxide, or nitrogen peroxide [Mellor 5:209-212. 1946-47]. Boron trichloride reacts energetically with nitrogen peroxide, phosphine, or fat and grease [Mellor 5:132. 1946-47]. Nitrogen peroxide and acetic anhydride reacted to form tetranitromethane, but resulted in an explosion [Van Dolah 1967]. Nitrogen peroxide forms explosive mixtures with incompletely halogenated hydrocarbons [Chem. Eng. News 42(47):53. 1964]. During an experiment to produce lactic acid by oxidizing propylene with nitrogen peroxide, a violent explosion occurred. These mixtures (olefins and nitrogen peroxide) form extremely unstable nitrosates or nitrosites [Comp. Rend. 116:756. 1893]. Contact of very cold liquefied gas with water may result in vigorous or violent boiling of the product and extremely rapid vaporization due to the large temperature differences involved. If the water is hot, there is the possibility that a liquid "superheat" explosion may occur. Pressures may build to dangerous levels if liquid gas contacts water in a closed container [Handling Chemicals Safely 1980]. Corrosive to steel when wet, but may be stored in steel cylinders when moisture content is 0.1% or less.
HazardInhalation may be fatal. Can react strongly with reducing materials. Lower respiratory tract irritant. Questionable carcinogen.
Health HazardSevere exposures may be fatal. Contact may cause burns to skin and eyes. Contact with liquid may cause frostbite. NITROGEN DIOXIDE was reported to react with blood to form methemoglobin. The lowest lethal human inhalation dose has been reported at 200 ppm/1 min.
Health HazardThe acute toxicity of nitrogen dioxide by inhalation is high. Inhalation may cause shortness of breath and pulmonary edema progressing to respiratory illness, reduction in the blood's oxygen carrying capacity, chronic lung disorders and death; symptoms may be delayed for hours and may recur after several weeks. Toxic effects may occur after exposure to concentrations of 10 ppm for 10 min and include coughing, chest pain, frothy sputum, and difficulty in breathing. Brief exposure to 200 ppm can cause severe lung damage and delayed pulmonary edema, which may be fatal. Nitrogen dioxide at concentrations of 10 to 20 ppm is mildly irritating to the eyes; higher concentrations of the gas and liquid NO2-N2O4 are highly corrosive to the skin, eyes, and mucous membranes. Nitrogen dioxide can be detected below the permissible exposure limit by its odor and irritant effects and is regarded as a substance with adequate warning properties. Animal testing indicates that nitrogen dioxide does not have carcinogenic or reproductive effects. It does produce genetic damage in bacterial and mammalian cell cultures; however, most studies in animals indicate that it does not produce heritable genetic damage.
Fire HazardNitrogen dioxide is not combustible (NFPA rating = 0) but is a strong oxidizing agent and will support combustion. Cylinders of NO2 gas exposed to fire or intense heat may vent rapidly or explode.
Safety ProfileExperimental poison by inhalation. Moderately toxic to humans by inhalation. An experimental teratogen. Other experimental reproductive effects. Human systemic effects by inhalation: pulmonary vascular resistance changes, cough, dpspnea, and other pulmonary changes. Mutation data reported. Violent reaction with cyclohexane, F2, formaldehyde, alcohols, nitrobenzene, petroleum, toluene. When heated to decomposition it emits toxic fumes of NOx. See also NITRIC OXIDE.
Potential ExposureNitrogen dioxide is found in automotive and diesel emissions. Nitrogen dioxide is an industrial chemical used as an intermediate in nitric and sulfuric acid manufacture; it is used in the nitration of organic compounds; it is used as an oxidizer in liquid propellant rocket fuel combinations. It is also used in firefighting, welding and brazing.
First aidIf this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 minutes, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. Give large quantities of water and do not induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 24 48 hours after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a drug or other inhalation therapy. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water.
storageCylinders of nitrogen dioxide should be stored and used in a continuously ventilated gas cabinet or fume hood.
ShippingUN1067/124 Dinitrogen tetroxide, Hazard Class: 2.3; Labels: 2.3-Poisonous gas, 5.1-Oxidizer, 8-Corrosive material, Inhalation Hazard Zone A. UN1975 Nitric oxide and dinitrogen tetroxide mixtures or Nitric oxide and nitrogen dioxide mixtures, Hazard Class: 2.3; Labels: 2.3-Poisonous gas, 5.1-Oxidizer, 8-Corrosive material, Inhalation Hazard Zone A. Cylinders must be transported in a secure upright position, in a well-ventilated truck. Protect cylinder and labels from physical damage. The owner of the compressed gas cylinder is the only entity allowed by federal law (49CFR) to transport and refill them. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner.
Flammability and ExplosibilityNitrogen dioxide is not combustible (NFPA rating = 0) but is a strong oxidizing agent and will support combustion. Cylinders of NO2 gas exposed to fire or intense heat may vent rapidly or explode.
IncompatibilitiesA strong oxidizer. Reacts violently with combustible matter, chlorinated hydrocarbons; ammonia, carbon disulfide; reducing materials. Reacts with water, forming nitric acid and nitric oxide. Attacks steel in the presence of moisture.
Waste DisposalDestroy by incineration with the addition of hydrocarbon fuel, controlled in such a way that combustion products are elemental nitrogen, CO2, and water. 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.
NITROGEN DIOXIDE Preparation Products And Raw materials
Preparation Products2,4,6-TRIFLUOROPHENYL ISOTHIOCYANATE
Raw materialsNITROGEN DIOXIDE
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