NITROGEN DIOXIDE

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

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.

Physical properties

Reddish-brown gas; pungent irritating odor; liquefies to a yellow liquid at 21.2°C; liquefies under pressure to a brown fuming liquid, commercially known as nitrogen tetroxide which actually is an equilibrium mixture of nitrogen dioxide and dinitrogen tetroxide, N₂O₄; converts to a colorless crystalline solid at -11.2°C; refractive index 1.40 at 20°C; density of gas in air 1.58 (air=1); density of liquid 1.449 g/mL at 20°C; critical temperature 158.2°C; critical pressure 99.96 atm; decomposes in water forming nitric acid; reacts with alkalies; soluble in concentrated nitric and sulfuric acids; soluble in chloroform and carbon disulfide.

Occurrence

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.

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 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.

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

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.

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.

Materials Uses

When dry (0.1 percent moisture or less), nitrogen dioxide is not corrosive to mild steel at ordinary temperatures and pressures. Numerous metals and alloys such as carbon steel, stainless steel, aluminum, nickel, and Inconel are satisfactory for handling and storage. Under wet conditions, stainless steels resistant to about 60 percent nitric acid serve best.
Equipment parts, such as valve stems, which are partly in contact with the atmosphere, should be stainless steel with sufficient chromium content to resist corrosion caused by leaks through stuffing boxes. Good quality ceramic bodies and Pyrex are satisfactory for handling wet or dry nitrogen dioxide.
Among the plastics, Teflon and Kel-F films are most satisfactory. Koroseal and Saran are useful but have a limited service life. In general, the vinyl plastics do not hold up well with nitrogen dioxide. Asbestos and asbestos-graphite are satisfactory for valve stuffing boxes. Koroseal has given reasonably good service in this use. For use on pipe threads, graphite-disodium silicate (waterglass) is recommended, and hydrocarbon lubricants should be avoided.

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.

Raw materials

Preparation Products