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

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.

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).

The Uses of NITROGEN DIOXIDE

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.

The Uses of NITROGEN DIOXIDE

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.

The Uses of NITROGEN DIOXIDE

Nitrogen dioxide has been used as a catalyst in certain oxidation reactions, as an inhibitor to prevent polymerization of acrylates during distillation, as a nitrating agent for organic compounds, as an oxidizing agent, and as an oxidizer for rocket fuel. It is also used as a flour bleaching agent in the manufacture of liquid explosives and for increasing the wet strength of paper.

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).

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.

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.

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.

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.

Physiological effects

A major hazard regarding exposure to nitrogen dioxide is that serious effects are not felt until several hours after the exposure. Exposure to nitrogen dioxide at levels of 90 ppm and higher has resulted in delayed pulmonary edema occurring anywhere from a few hours to 72 hours after exposure ceases. Symptoms include cyanosis, shortness of breath, restlessness, headache, and the production of a frothy yellow or brown sputum. With appropriate treatment, symptoms usually resolve rapidly, but can persist for several weeks.
Exposures to nitrogen dioxide of 10 minutes or less at a level of about 150 ppm produces cough, nose and throat irritation, tearing, headache, nausea, and vomiting. Exposures ranging from 50 ppm to 150 ppm have been associated with moderate irritation to the eyes and mucous membranes. Permanent eye damage can occur, however, if exposures at these levels are prolonged. Delayed pulmonary edema may follow exposure to 100 ppm to 150 ppm for only 30-60 minutes, while a few breaths at a concentration of 200 ppm to 700 ppm will produce severe pulmonary damage that may result in fatal pulmonary edema after 5 to 8 hours have elapsed.
Nitrogen dioxide in 10 ppm to 20 ppm concentrations in air is slightly irritating to mucous membranes and the upper respiratory tract. The odor is distinct in concentrations of 5 ppm.Concentrations above 100 ppm in air cause immediate distress. Exposure of the skin to liquid nitrogen dioxide can cause severe bums.
ACGIH recommends the Threshold Limit Value-Time-Weighted Average (TLV-TWA) of 3 ppm (5.6 mg/m3) for nitrogen dioxide. The TLV-TWA is the time-weighted average concentration for a normal 8-hour workday and a 40-hour workweek, to which nearly all workers may be repeatedly exposed, day after day, without adverse effect. ACGIH also recommends the Threshold Limit Value-Short Term Exposure Limit (TLV-STEL) of 5 ppm (904 mg/m3) for nitrogen dioxide. The TLV-STEL is the IS-minute TWA exposure that should not be exceeded at any time during a workday even if the 8-hour TWA is within the TLV-TWA. Exposures above the TLV- TWA up to the STEL should not be longer than 15 minutes and should not occur more than 4 times per day. There should be at least 60 minutes between successive exposures in this range.
OSHA lists a Ceiling Value of 5 ppm (9 mg/m3) for nitrogen dioxide. The Ceiling Value is the exposure limit that shall not be exceeded at any time during the working day. If instantaneous monitoring is not feasible, then the ceiling shall be assessed as a IS-minute TWA exposure that shall not be exceeded at any time during the working day.

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.

GRADES AVAILABLE

Nitrogen dioxide is available in grades of 99.5 percent or 99.995 percent.