Nitrogen dioxide

Nitrogen dioxide is a chemical compound with the formula and is one of several nitrogen oxides. is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year for use (primarily in the production of fertilizers). At higher temperatures, nitrogen dioxide is a reddish-brown gas. It can be fatal if inhaled in large quantities. The LC50 (median lethal dose) for humans has been estimated to be 174 ppm for a 1-hour exposure. Nitrogen dioxide is a paramagnetic, bent molecule with C2v point group symmetry.
It is included in the NOx family of atmospheric pollutants.
Properties
Nitrogen dioxide is a reddish-brown gas with a pungent, acrid odor above and becomes a yellowish-brown liquid below . It forms an equilibrium with its dimer, dinitrogen tetroxide, and converts almost entirely to below .
The bond length between the nitrogen atom and the oxygen atom is 119.7 pm. This bond length is consistent with a bond order between one and two.
Unlike ozone the ground electronic state of nitrogen dioxide is a doublet state, since nitrogen has one unpaired electron, which decreases the alpha effect compared with nitrite and creates a weak bonding interaction with the oxygen lone pairs. The lone electron in also means that this compound is a free radical, so the formula for nitrogen dioxide is often written as .
The reddish-brown color is a consequence of preferential absorption of light in the blue region of the spectrum (400–500 nm), although the absorption extends throughout the visible (at shorter wavelengths) and into the infrared (at longer wavelengths). Absorption of light at wavelengths shorter than about 400 nm results in photolysis (to form , atomic oxygen); in the atmosphere the addition of the oxygen atom so formed to results in ozone.
Preparation
Nitrogen dioxide typically arises via the oxidation of nitric oxide by oxygen in air (e.g. as result of corona discharge):
+
Nitrogen dioxide is formed in most combustion processes using air as the oxidant. At elevated temperatures nitrogen combines with oxygen to form nitrogen dioxide:
In the laboratory, can be prepared in a two-step procedure where dehydration of nitric acid produces dinitrogen pentoxide:
which subsequently undergoes thermal decomposition:
The thermal decomposition of some metal nitrates also generates :
is generated by the reduction of concentrated nitric acid with a metal (such as copper):
Formation from decomposition of nitric acid
Nitric acid decomposes slowly to nitrogen dioxide by the overall reaction:
The nitrogen dioxide so formed confers the characteristic yellow color often exhibited by this acid.
Selected reactions
Thermal properties
exists in equilibrium with the colourless gas dinitrogen tetroxide:
The equilibrium is characterized by , which is exothermic. is favored at higher temperatures, while at lower temperatures, predominates. can be obtained as a white solid with melting point −11.2 °C. is paramagnetic due to its unpaired electron, while is diamagnetic.
At , decomposes with release of oxygen via an endothermic process:
As an oxidizer
As suggested by the weakness of the N–O bond, is a good oxidizer. Consequently, it will combust, sometimes explosively, in the presence of hydrocarbons.
Hydrolysis
NO2 reacts with water to give nitric acid and nitrous acid:
This reaction is one of the steps in the Ostwald process for the industrial production of nitric acid from ammonia. This reaction is negligibly slow at low concentrations of NO2 characteristic of the ambient atmosphere, although it does proceed upon NO2 uptake to surfaces. Such surface reaction is thought to produce gaseous HNO2 (often written as HONO) in outdoor and indoor environments.
Conversion to nitrates
is used to generate anhydrous metal nitrates from the oxides:
Alkyl and metal iodides give the corresponding nitrates:
Ecology
is introduced into the environment by natural causes, including entry from the stratosphere, bacterial respiration, volcanos, and lightning. These sources make a trace gas in the atmosphere of Earth, where it plays a role in absorbing sunlight and regulating the chemistry of the troposphere, especially in determining ozone concentrations.
Uses
is used as an intermediate in the manufacturing of nitric acid, as a nitrating agent in the manufacturing of chemical explosives, as a polymerization inhibitor for acrylates, as a flour bleaching agent, and as a room temperature sterilization agent. It is also used as an oxidizer in rocket fuel, for example in red fuming nitric acid; it was used in the Titan rockets, to launch Project Gemini, in the maneuvering thrusters of the Space Shuttle, and in uncrewed space probes sent to various planets.
Human-caused sources and exposure
For the general public, the most prominent sources of are internal combustion engines, as combustion temperatures are high enough to thermally combine some of the nitrogen and oxygen in the air to form . Outdoors, can be a result of traffic from motor vehicles.
Indoors, exposure arises from cigarette smoke, and butane and kerosene heaters and stoves.
Workers in industries where is used are also exposed and are at risk for occupational lung diseases, and NIOSH has set exposure limits and safety standards. Workers in high voltage areas especially those with spark or plasma creation are at risk. Agricultural workers can be exposed to arising from grain decomposing in silos; chronic exposure can lead to lung damage in a condition called "silo-filler's disease".
Toxicity
diffuses into the epithelial lining fluid (ELF) of the respiratory epithelium and dissolves. There, it chemically reacts with antioxidant and lipid molecules in the ELF. The health effects of are caused by the reaction products or their metabolites, which are reactive nitrogen species and reactive oxygen species that can drive bronchoconstriction, inflammation, reduced immune response, and may have effects on the heart.
Acute harm due to exposure is rare. 100–200 ppm can cause mild irritation of the nose and throat, 250–500 ppm can cause edema, leading to bronchitis or pneumonia, and levels above 1000 ppm can cause death due to asphyxiation from fluid in the lungs. There are often no symptoms at the time of exposure other than transient cough, fatigue or nausea, but over hours inflammation in the lungs causes edema.
For skin or eye exposure, the affected area is flushed with saline. For inhalation, oxygen is administered, bronchodilators may be administered, and if there are signs of methemoglobinemia, a condition that arises when nitrogen-based compounds affect the hemoglobin in red blood cells, methylene blue may be administered.
It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and it is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.
Health effects of exposure
Exposure to low levels of over time can cause changes in lung function.
Chronic exposure to can cause respiratory effects including airway inflammation in healthy people and increased respiratory symptoms in people with asthma.
The effects of toxicity on health have been examined using questionnaires and in-person interviews in an effort to understand the relationship between and asthma. The influence of indoor air pollutants on health is important because the majority of people in the world spend more than 80% of their time indoors. The amount of time spent indoors depends upon on several factors including geographical region, job activities, and gender among other variables. Additionally, because home insulation is improving, this can result in greater retention of indoor air pollutants, such as . With respect to geographic region, the prevalence of asthma has ranged from 2 to 20% with no clear indication as to what's driving the difference. This may be a result of the "hygiene hypothesis" or "western lifestyle" that captures the notions of homes that are well insulated and with fewer inhabitants. Another study examined the relationship between nitrogen exposure in the home and respiratory symptoms and found a statistically significant odds ratio of 2.23 (95% CI: 1.06, 4.72) among those with a medical diagnosis of asthma and gas stove exposure.
A major source of indoor exposure to is the use of gas stoves for cooking or heating in homes. According to the 2000 census, over half of US households use gas stoves and indoor exposure levels of are, on average, at least three times higher in homes with gas stoves compared to electric stoves with the highest levels being in multifamily homes. Exposure to is especially harmful for children with asthma. Research has shown that children with asthma who live in homes with gas stoves have greater risk of respiratory symptoms such as wheezing, cough and chest tightness. Additionally, gas stove use was associated with reduced lung function in girls with asthma, although this association was not found in boys. Using ventilation when operating gas stoves may reduce the risk of respiratory symptoms in children with asthma.
In a cohort study with inner-city minority African American Baltimore children to determine if there was a relationship between and asthma for children aged 2 to 6 years old, with an existing medical diagnosis of asthma, and one asthma related visit, families of lower socioeconomic status were more likely to have gas stoves in their homes. The study concluded that higher levels of within a home were linked to a greater level of respiratory symptoms among the study population. This further exemplifies that toxicity is dangerous for children.
Environmental effects
Interaction of and other with water, oxygen and other chemicals in the atmosphere can form acid rain which harms sensitive ecosystems such as lakes and forests. Elevated levels of can also harm vegetation, decreasing growth, and reduce crop yields.
See also
Dinitrogen tetroxide
Nitric oxide – pollutant that is short lived because it converts to in the presence of ozone
Nitrite
Nitrous oxide – "laughing gas", a linear molecule, isoelectronic with but with a nonsymmetric arrangement of atoms
Nitryl
References
Cited sources
External links
International Chemical Safety Card 0930
National Pollutant Inventory – Oxides of nitrogen fact sheet
NIOSH Pocket Guide to Chemical Hazards
WHO-Europe reports: Health Aspects of Air Pollution (2003) (PDF) and "Answer to follow-up questions from CAFE (2004) (PDF)
Nitrogen Dioxide Air Pollution
Current global map of nitrogen dioxide distribution
A review of the acute and long term impacts of exposure to nitrogen dioxide in the United Kingdom IOM Research Report TM/04/03
Nitrogen oxides
Bleaches
Hazardous air pollutants
Smog
Free radicals
Food additives
Gases with color