Nitrogen dioxide

Nitrogen dioxide

Nitrogen dioxide at −196 °C, 0 °C, 23 °C, 35 °C, and 50 °C. (NO
2) converts to the colorless dinitrogen tetroxide (N
2O
4) at low temperatures, and reverts to NO
2 at higher temperatures.
Names
IUPAC name
Nitrogen dioxide
Other names
Nitrogen(IV) oxide,[1] Deutoxide of nitrogen
Identifiers
10102-44-0 YesY
ChEBI CHEBI:33101 YesY
ChemSpider 2297499 YesY
EC Number 233-272-6
976
Jmol 3D model Interactive image
Interactive image
PubChem 3032552
RTECS number QW9800000
UN number 1067
Properties
NO•
2
Molar mass 46.0055 g mol−1
Appearance Vivid orange gas
Odor Chlorine like
Density 1.88 g dm−3[2]
Melting point −11.2 °C (11.8 °F; 261.9 K)
Boiling point 21.2 °C (70.2 °F; 294.3 K)
Hydrolyses
Solubility soluble in CCl
4, nitric acid,[3] chloroform
Vapor pressure 98.80 kPa (at 20 °C)
1.449 (at 20 °C)
Structure
C2v
Bent
Thermochemistry
37.5 J/mol K
240 J mol−1 K−1[4]
+34 kJ mol−1[4]
Hazards
Main hazards Poison, oxidizer
Safety data sheet ICSC 0930
GHS pictograms
GHS signal word Danger
H270, H314, H330
P220, P260, P280, P284, P305+351+338, P310
O T+
R-phrases R26, R34, R8
S-phrases (S1/2), S9, S26, S28, S36/37/39, S45
NFPA 704
Lethal dose or concentration (LD, LC):
30 ppm (guinea pig, 1 hr)
315 ppm (rabbit, 15 min)
68 ppm (rat, 4 hr)
138 ppm (rat, 30 min)
1000 ppm (mouse, 10 min)[5]
64 ppm (dog, 8 hr)
64 ppm (monkey, 8 hr)[5]
US health exposure limits (NIOSH):
PEL (Permissible)
 C 5 ppm (9 mg/m3)[6]
REL (Recommended)
 ST 1 ppm (1.8 mg/m3)[6]
IDLH (Immediate danger)
 20 ppm[6]
Related compounds
Dinitrogen pentoxide

Dinitrogen tetroxide
Dinitrogen trioxide
Nitric oxide
Nitrous oxide

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Nitrogen dioxide is the chemical compound with the formula NO
2. It is one of several nitrogen oxides. NO
2 is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year. At higher temperatures it is a reddish-brown gas that has a characteristic sharp, biting odor and is a prominent air pollutant.[7] Nitrogen dioxide is a paramagnetic, bent molecule with C2v point group symmetry.

Properties

Nitrogen dioxide is a reddish-brown gas above 70 °F (21 °C; 294 K) with a pungent, acrid odor, becomes a yellowish-brown liquid below 70 °F (21 °C; 294 K), and converts to the colorless dinitrogen tetroxide (N
2O
4) below 15 °F (−9 °C; 264 K).[6]

It has a molar mass of 46.0055, which makes it heavier than air, whose average molar mass is 28.8.

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, O3, the ground electronic state of nitrogen dioxide is a doublet state, since nitrogen has one unpaired electron,[8] which decreases the alpha effect compared with nitrite and creates a weak bonding interaction with the oxygen lone pairs. The lone electron in NO
2 also means that this compound is a free radical, so the formula for nitrogen dioxide is often written as •NO
2.

Preparation and reactions

Nitrogen dioxide typically arises via the oxidation of nitric oxide by oxygen in air:[9]

2 NO + O
2 → 2 NO
2

Nitrogen dioxide is formed in most combustion processes using air as the oxidant. At elevated temperatures nitrogen combines with oxygen to form nitric oxide:

O
2 + N
2 → 2 NO

In the laboratory, NO
2 can be prepared in a two-step procedure where dehydration of nitric acid produces dinitrogen pentoxide, which subsequently undergoes thermal decomposition:

2 HNO
3 → N
2O
5 + H
2O
2 N
2O
5 → 4 NO
2 + O
2

The thermal decomposition of some metal nitrates also affords NO
2:

2 Pb(NO
3)
2 → 2 PbO + 4 NO
2 + O
2

Alternatively, reduction of concentrated nitric acid by metal (such as copper).

4 HNO
3 + Cu → Cu(NO
3)
2 + 2 NO
2 + 2 H
2O

Or finally by adding concentrated nitric acid over tin; hydrated tin dioxide is produced as byproduct.

4 HNO3 + Sn → H2O + H2SnO3 + 4 NO2

Main reactions

NO
2 is highly reactive.[7]

Basic thermal properties

NO
2 exists in equilibrium with the colourless gas dinitrogen tetroxide (N
2O
4):

2 NO
2 ⇌ N
2O
4

The equilibrium is characterized by ΔH = −57.23 kJ/mol, which is exothermic. NO2 is favored at higher temperatures, while at lower temperatures, dinitrogen tetroxide (N2O4) predominates. Dinitrogen tetroxide (N
2O
4) can be obtained as a white solid with melting point −11.2 °C.[9] NO2 is paramagnetic due to its unpaired electron, while N2O4 is diamagnetic.

The chemistry of nitrogen dioxide has been investigated extensively. At 150 °C, NO
2 decomposes with release of oxygen via an endothermic process (ΔH = 114 kJ/mol):

2 NO
2 → 2 NO + O
2

As an oxidizer

As suggested by the weakness of the N–O bond, NO
2 is a good oxidizer. Consequently, it will combust, sometimes explosively, with many compounds, such as hydrocarbons.

Hydrolysis

It hydrolyses to give nitric acid and nitrous acid:

2 NO
2/N
2O
4 + H
2O → HNO
2 + HNO
3

This reaction is one step in the Ostwald process for the industrial production of nitric acid from ammonia.[10] Nitric acid decomposes slowly to nitrogen dioxide, which confers the characteristic yellow color of most samples of this acid:

4 HNO
3 → 4 NO
2 + 2 H
2O + O
2

Conversion to nitrates

NO
2 is used to generate anhydrous metal nitrates from the oxides:[9]

MO + 3 NO
2 → M(NO
3)
2 + NO

Conversion to nitrites

Alkyl and metal iodides give the corresponding nitrites:

2 CH
3I + 2 NO
2 → 2 CH
3NO
2 + I
2
TiI
4 + 4 NO
2 → Ti(NO
2)
4 + 2 I
2

Ecology

NO
2 is introduced into the environment by natural causes, including entry from the stratosphere, bacterial respiration, volcanos, and lightning. These sources make NO
2 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.[11]

Uses

NO
2 is used as an intermediate in the manufacturing of nitric acid, as a nitrating agent in manufacturing of chemical explosives, as a polymerization inhibitor for acrylates, and as a flour bleaching agent.[12]:223 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 unmanned space probes sent to various planets.[13]

Human-caused sources and exposure

For the general public, the most prominent sources of NO
2 are internal combustion engines burning fossil fuels.[7]

Indoors, exposure arises from cigarette smoke,[14] and butane and kerosene heaters and stoves.[15]

Workers in industries where NO
2 is used are also exposed and are at risk for occupational lung diseases, and NIOSH has set exposure limits and safety standards.[6] Astronauts in the Apollo–Soyuz Test Project were almost killed when NO
2 was accidentally vented into the cabin.[13] Agricultural workers can be exposed to NO
2 arising from grain decomposing in silos; chronic exposure can lead to lung damage in a condition called "Silo-filler's disease".[16][17]

Historically, nitrogen dioxide was also produced by atmospheric nuclear tests, and was responsible for the reddish colour of mushroom clouds.[18]

Toxicity

Gaseous NO
2 diffuses into the epithelial lining fluid (ELF) of the respiratory epithelium and dissolves, and chemically reacts with antioxidant and lipid molecules in the ELF; NO
2's health effects 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.[19]:Section 4

Pathways indicated by a dotted line are those for which evidence is limited to findings from experimental animal studies, while evidence from controlled human exposure studies is available for pathways indicated by a solid line. Dashed lines indicate proposed links to the outcomes of asthma exacerbation and respiratory tract infections. Key events are subclinical effects, endpoints are effects that are generally measured in the clinic, and outcomes are health effects at the organism level. NO2 = nitrogen dioxide; ELF = epithelial lining fluid.[19]:4–62

Acute harm due to NO
2 exposure is only likely to arise in occupational settings. Direct exposure to the skin can cause irritations and burns. Only very high concentrations of the gaseous form cause immediate distress: 10–20 ppm can cause mild irritation of the nose and throat, 25–50 ppm can cause edema leading to bronchitis or pneumonia, and levels above 100 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.[20][21]

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.[22][23]

For the public, chronic exposure to NO
2 can cause respiratory effects including airway inflammation in healthy people and increased respiratory symptoms in people with asthma. NO
2 creates ozone which causes eye irritation and exacerbates respiratory conditions, leading to increased visits to emergency departments and hospital admissions for respiratory issues, especially asthma.[24]

Environmental limits

The U.S. EPA has set safety levels for environmental exposure to NO
2 at 100 ppb, averaged over one hour, and 53 ppb, averaged annually.[7] As of February 2016, no area of the US was out of compliance with these limits and concentrations ranged between 10–20 ppb, and annual average ambient NO2 concentrations, as measured at area-wide monitors, have decreased by more than 40% since 1980.[25]

However, NO
2 concentrations in vehicles and near roadways are appreciably higher than those measured at monitors in the current network. In fact, in-vehicle concentrations can be 2–3 times higher than measured at nearby area-wide monitors. Near-roadway (within about 50 metres (160 ft)) concentrations of NO2 have been measured to be approximately 30 to 100% higher than concentrations away from roadways. Individuals who spend time on or near major roadways can experience short-term NO2 exposures considerably higher than measured by the current network. Approximately 16% of U.S. housing units are located within 300 feet (91 m) of a major highway, railroad, or airport (approximately 48 million people). This population likely includes a higher proportion of non-white and economically-disadvantaged people. Studies show a connection between breathing elevated short-term NO2 concentrations, and increased visits to emergency departments and hospital admissions for respiratory issues, especially asthma. NO2 exposure concentrations near roadways are of particular concern for susceptible individuals, including asthmatics, children, and the elderly.[24]

See also

References

  1. ↑ "nitrogen dioxide (CHEBI:33101)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute. 13 January 2008. Main. Retrieved 4 October 2011.
  2. ↑ Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). CRC Press. p. 4.79. ISBN 1439855110.
  3. ↑ Mendiara, S. N.; Sagedahl, A.; Perissinotti, L. J. (2001). "An electron paramagnetic resonance study of nitrogen dioxide dissolved in water, carbon tetrachloride and some organic compounds". Applied Magnetic Resonance 20: 275. doi:10.1007/BF03162326.
  4. 1 2 Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A22. ISBN 0-618-94690-X.
  5. 1 2 "Nitrogen dioxide". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
  6. 1 2 3 4 5 "NIOSH Pocket Guide to Chemical Hazards #0454". National Institute for Occupational Safety and Health (NIOSH).
  7. 1 2 3 4 "Nitrogen dioxide". United States Environmental Protection Agency. Feb 23, 2016.
  8. ↑ Chemistry of the Elements, N.N. Greenwood, A. Earnshaw, p.455
  9. 1 2 3 Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  10. ↑ Thiemann, Michael; Scheibler, Erich and Wiegand, Karl Wilhelm (2005) "Nitric Acid, Nitrous Acid, and Nitrogen Oxides" in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim doi:10.1002/14356007.a17_293.
  11. ↑ WHO Air Quality Guidelines - Second Edition. Chapter 7.1 Nitrogen Dioxide
  12. ↑ Subcommittee on Emergency and Continuous Exposure Guidance Levels for Selected Submarine Contaminants; Committee on Toxicology; Board on Environmental Studies and Toxicology; Division on Earth and Life Studies; National Research Council. Chapter 12: Nitrogen Dioxide in Emergency and Continuous Exposure Guidance Levels for Selected Submarine Contaminants. National Academies Press, 2007. ISBN 978-0-309-09225-8
  13. 1 2 Simon Cotton for RSC Chemistry World. 21 March 2013 Nitrogen dioxide
  14. ↑ US Dept. of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry, Division of Toxicology. April 2002 ATSDR Nitrous Oxides
  15. ↑ "The Impact of Unvented Gas Heating Appliances on Indoor Nitrogen Dioxide Levels in 'TIGHT' Homes". ashrae.org. Retrieved 2013-04-11.
  16. ↑ Chan-Yeung M, Ashley MJ, Grzybowski S. Grain dust and the lungs. Can Med Assoc J. 1978 May 20;118(10):1271-4. Review. PMID 348288 Free PMC Article
  17. ↑ Gurney JW, et al. Agricultural disorders of the lung. Radiographics. 1991 Jul;11(4):625-34. Review. PMID 1887117
  18. ↑ Effects of Nuclear Explosions. Nuclearweaponarchive.org. Retrieved on 2010-02-08.
  19. 1 2 U.S. EPA. Integrated Science Assessment for Oxides of Nitrogen – Health Criteria (2016 Final Report). U.S. Environmental Protection Agency, Washington, DC, EPA/600/R-15/068, 2016. Federal Register Notice Jan 28, 2016 Free download available at Report page at EPA website.
  20. ↑ Toxnet Nitrogen dioxide: Human Health Effects Page accessed March 28, 2016
  21. ↑ CDC NIOSH International Chemical Safety Cards (ICSC): Nitrogen Dioxide Page last reviewed: July 22, 2015; Page last updated: July 1, 2014
  22. ↑ Agency for Toxic Substances and Disease Registry via the CDC Medical Management Guidelines for Nitrogen Oxides Page last reviewed: October 21, 2014; Page last updated: October 21, 2014
  23. ↑ University of Kansas Hospital, Poison Control Center Poison Facts: Medium Chemicals: Nitrogen Dioxide page accessed March 28, 2016
  24. 1 2 EPA Nitrogen Dioxide: Health Last updated on 2/23/2016
  25. ↑ EPA Nitrogen Dioxide Basic Information. Last updated on 2/23/2016

External links

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