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NITROGEN DIOXIDE

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NITROGEN DIOXIDE Basic information

Product Name:
NITROGEN DIOXIDE
CAS:
10102-44-0
MF:
NO2 *
MW:
46.01
EINECS:
233-272-6
Mol File:
10102-44-0.mol
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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
Odor
Pungent, acrid odor detectable at 0.12 ppm
Odor Threshold
0.12ppm
Water Solubility 
decomposes in H2O to HNO3 and releases NO; soluble conc H2SO4, HNO3 [MER06]
Exposure limits
TLV-TWA 3 ppm (~6 mg/m3) (ACGIH), ceiling in air 5 ppm (MSHA and OSHA); STEL 5 ppm (ACGIH); IDLH 50 ppm (NIOSH).
CAS DataBase Reference
10102-44-0(CAS DataBase Reference)
EPA Substance Registry System
Nitrogen dioxide (10102-44-0)
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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

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NITROGEN DIOXIDE Usage And Synthesis

Preparation

Nitrogen 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.

Reaction

The 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

Description

nitrogen dioxide is a reddish-brown gas (or yellow liquid) with a strong, acrid odor. Nitrogen dioxide readily dimerizes to produce N2O4.nitrogen dioxide are nonfl ammable, toxic gases.The federal government has established air quality standards for nitrogen dioxide at 0.053 partsper million (ppm), which equals 100μg (micrograms) per cubic meter.Nitrogen dioxide is highly soluble in water and forms nitric acid (HNO3), and nitric oxide is slightly soluble and forms nitrous acid (HNO2).
Nitrogen dioxide is a strong oxidizing agent and causes corrosion.Nitrogen dioxide is used as an oxidizing agent, a catalyst in oxidation reactions, an inhibitor, as a nitrating agent for organic reactions, as a flour bleaching agent, and in increasing the wet strength of paper.

Chemical Properties

Red 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 Properties

Nitrogen 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.

History

nitrogen dioxide was prepared in 1772 by Joseph Priestley (1733–1804) and described in his volumes Experiments and Observations of Different Kinds of Air published between 1774 and 1786. Priestley called nitric oxide nitrous air, nitrogen dioxide nitrous acid vapor, and nitrous oxide phlogisticated nitrous air, but also referred to the dioxide. Priestley prepared nitric oxide by reacting nitric acid with a metal such as copper: 3Cu(s) + 8HNO3(aq) → 2NO(g) + 3Cu(NO3)2(aq) + 4H2O(l).

Uses

Nitrogen dioxide is produced by the reactionof nitric acid with metals or other reducingagents; decomposition of nitrates; when airis heated to high temperatures; and duringfire. It occurs in the exhausts of internalcombustion engines and in cigarette smoke.It is used as an intermediate in the productionof nitric and sulfuric acids, in rocket fuels,as a nitrating and oxidizing agent, and inbleaching flour.

Uses

Nitrogen 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.

Production Methods

Nitric oxide (nitrogen monoxide, mononitrogen monoxide; NO) and nitrogen dioxide [nitrogen peroxide, nitrogen tetroxide (NTO); NO2] are often found in dynamic equilibrium. Historically, these compounds sometimes have been erroneously described as “nitrous fumes.” In air, NO is readily oxidized to NO2, and liquefied NO2 (existing principally as its dimer nitrogen tetroxide, N2O4) releases NO2 at room temperature. Thus, these compounds are often grouped as nitrogen oxides (NOx). Other nitrogen oxides include nitrogen trioxide (NO3), dinitrogen trioxide (N2O3), and dinitrogen pentoxide (N2O5). Of all the oxides of nitrogen, NO2 is the most acutely toxic and has been most extensively studied. Accordingly, much of this section focuses on the toxicity of this compound.
Discoveries on the role forNOin biology and medicine led to a 1998 Nobel Prize for Robert Furchgott, Louis J. Ignarro, and Ferid Murad. Nitric oxide and NO2 occur naturally by bacterial degradation of nitrogenous compounds and to a lesser extent from fires, volcanic action, and fixation by lightning. NO has been the subject of intense and extensive research in a vast array of fields including chemistry, molecular biology, pharmaceuticals, and gene therapy. Formed endogenously, NO has a physiological role in blood flow regulation, thrombosis, and neurotransmission, and a pathophysiological role in inflammation, oxidative stress, and host defense. NO is derived from the amino acid L-arginine by five-electron oxidation catalyzed by NO synthase (requiring reduced pyridine nucleotides, reduced biopteridines, and calmodulin). The by-product, citrulline, is recycled back to L-arginine. In the bloodstream, NO binds primarily hemoglobin, is converted to NO3, and is eliminated in the urine with a half-life of 5–8 h.
Nitric oxide is manufactured by passing air through an electric arc or by oxidation of ammonia over platinum gauze.

Definition

A brown gas produced by the dissociation of dinitrogen tetroxide (with which it is in equilibrium), the dissociation being complete at 140°C. Further heating causes dissociation to colorless nitrogen monoxide and oxygen:
2NO2(g) = 2NO(g) + O2(g)
Nitrogen dioxide can also be made by the action of heat on metal nitrates (not the nitrates of the alkali metals or some of the alkaline-earth metals).

General Description

A 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 Reactions

Combines 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 Profile

NITROGEN 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.

Hazard

Inhalation may be fatal. Can react strongly with reducing materials. Lower respiratory tract irritant. Questionable carcinogen.

Health Hazard

Severe 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 Hazard

The 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.

Health Hazard

Nitrogen dioxide is a highly toxic gas. It is anirritant to the eyes, nose, and throat and to therespiratory system. The toxic symptoms arecough, frothy sputum, chest pain, dyspnea,congestion, and inflammation of lungs andcyanosis. Even a short exposure can causehemorrhage and lung injury. Death mayresult within a few days after exposure. Toxicsymptoms may be noted in humans followinga 10-minute exposure to a 10 ppm concentration in air. One or two minutes of exposureto 200 ppm can be lethal to humans.

Fire Hazard

Nitrogen 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.

Flammability and Explosibility

Nitrogen 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 Profile

Experimental 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 Exposure

Nitrogen 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.

storage

Cylinders of nitrogen dioxide should be stored and used in a continuously ventilated gas cabinet or fume hood.

Shipping

UN1067/124 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.

Incompatibilities

A 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 Disposal

Destroy 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

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