NOx

This article is about nitrogen oxides produced during combustion. For other definitions see Nox

See also: Nitrogen oxide

NO_x is a generic term for the mono-nitrogen oxides NO and NO₂ (nitric oxide and nitrogen dioxide). They are produced from the reaction of nitrogen and oxygen gases in the air during combustion, especially at high temperatures. In areas of high motor vehicle traffic, such as in large cities, the amount of nitrogen oxides emitted into the atmosphere as air pollution can be significant. NOx gasses are formed everywhere where there is combustion – like in an engine. In atmospheric chemistry, the term means the total concentration of NO and NO₂. NO_x react to form smog and acid rain. NO_x are also central to the formation of tropospheric ozone.

NO_x should not be confused with nitrous oxide (N₂O), which is a greenhouse gas and has many uses as an oxidizer, an anesthetic, and a food additive.

NO_y (reactive, odd nitrogen) is defined as the sum of NO_x plus the compounds produced from the oxidation of NO_x which include nitric acid.

Formation and reactions

The oxygen and nitrogen do not react at ambient temperatures. But at high temperatures, they have an endothermic reaction producing various oxides of nitrogen. Such temperatures arise inside an internal combustion engine, combustion of a mixture of air and fuel.

In atmospheric chemistry, the term NO_x means the total concentration of NO and NO₂. During daylight, these concentrations are in equilibrium; the ratio NO/NO₂ is determined by the intensity of sunshine (which converts NO₂ to NO) and the concentration of ozone (which reacts with NO to again form NO₂).

In the presence of excess oxygen (O₂), nitric oxide (NO) reacts with the oxygen to form nitrogen dioxide (NO₂). The time required depends on the concentration in air as shown below:^[1]

NO concentration in air (ppm)	Time required for half NO to be oxidized to NO2 (min)
20,000	0.175
10,000	0.35
1,000	3.5
100	35
10	350
1	3500

When NO_x and volatile organic compounds (VOCs) react in the presence of sunlight, they form photochemical smog, a significant form of air pollution, especially in the summer. Children, people with lung diseases such as asthma, and people who work or exercise outside are particularly susceptible to adverse effects of smog such as damage to lung tissue and reduction in lung function.^[2]

Formation of nitric acid and acid rain

Mono-nitrogen oxides eventually form nitric acid when dissolved in atmospheric moisture, forming a component of acid rain. The following chemical reaction occurs when nitrogen dioxide reacts with water:

2 NO₂ + H₂O → HNO₂ + HNO₃

Nitrous acid then decomposes as follows:

3 HNO₂ → HNO₃ + 2 NO + H₂O

where nitric oxide will oxidize to form nitrogen dioxide that again reacts with water, ultimately forming nitric acid:

4 NO + 3 O₂ + 2 H₂O → 4 HNO₃

Mono-nitrogen oxides are also involved in tropospheric production of ozone.^[3]

This nitric acid may end up in the soil, where it makes nitrate, where it is of use to growing plants.

Sources

Natural sources

Nitric oxide is produced during thunderstorms due to the extreme heat of lightning,^[4] and is caused by the splitting of nitrogen molecules. This can result in the production of acid rain, if nitrous oxide forms compounds with the water molecules in precipitation, thus creating acid rain.

Biogenic sources

Agricultural fertilization and the use of nitrogen fixing plants also contribute to atmospheric NO_x, by promoting nitrogen fixation by microorganisms.^[5][6]

Industrial sources

The three primary sources of NO_x in combustion processes:

• thermal NO_x
• fuel NO_x
• prompt NO_x

Thermal NO_x formation, which is highly temperature dependent, is recognized as the most relevant source when combusting natural gas. Fuel NO_x tends to dominate during the combustion of fuels, such as coal, which have a significant nitrogen content, particularly when burned in combustors designed to minimise thermal NO_x. The contribution of prompt NO_x is normally considered negligible. A fourth source, called feed NO_x is associated with the combustion of nitrogen present in the feed material of cement rotary kilns, at between 300° and 800°C, where it is also a minor contributor.

Thermal

Thermal NO_x refers to NO_x formed through high temperature oxidation of the diatomic nitrogen found in combustion air. The formation rate is primarily a function of temperature and the residence time of nitrogen at that temperature. At high temperatures, usually above 1600°C (2900°F), molecular nitrogen (N₂) and oxygen (O₂) in the combustion air disassociate into their atomic states and participate in a series of reactions.

The three principal reactions (the extended Zeldovich mechanism) producing thermal NO_x are:

N₂ + O → NO + N

N + O₂ → NO + O

N + OH → NO + H

All 3 reactions are reversible. Zeldovich was the first to suggest the importance of the first two reactions. The last reaction of atomic nitrogen with the hydroxyl radical, OH, was added by Lavoie, Heywood and Keck to the mechanism and makes a significant contribution to the formation of thermal NO_x.

Fuel

The major source of NO_x production from nitrogen-bearing fuels such as certain coals and oil, is the conversion of fuel bound nitrogen to NO_x during combustion. During combustion, the nitrogen bound in the fuel is released as a free radical and ultimately forms free N₂, or NO. Fuel NO_x can contribute as much as 50% of total emissions when combusting oil and as much as 80% when combusting coal.

Although the complete mechanism is not fully understood, there are two primary paths of formation. The first involves the oxidation of volatile nitrogen species during the initial stages of combustion. During the release and prior to the oxidation of the volatiles, nitrogen reacts to form several intermediaries which are then oxidized into NO. If the volatiles evolve into a reducing atmosphere, the nitrogen evolved can readily be made to form nitrogen gas, rather than NO_x. The second path involves the combustion of nitrogen contained in the char matrix during the combustion of the char portion of the fuels. This reaction occurs much more slowly than the volatile phase. Only around 20% of the char nitrogen is ultimately emitted as NO_x, since much of the NO_x that forms during this process is reduced to nitrogen by the char, which is nearly pure carbon.

Prompt

This third source is attributed to the reaction of atmospheric nitrogen, N₂, with radicals such as C, CH, and CH₂ fragments derived from fuel, where this cannot be explained by either the aforementioned thermal or fuel processes. Occurring in the earliest stage of combustion, this results in the formation of fixed species of nitrogen such as NH (nitrogen monohydride), HCN (hydrogen cyanide), H₂CN (dihydrogen cyanide) and CN- (cyano radical) which can oxidize to NO. In fuels that contain nitrogen, the incidence of prompt NO_x is especially minimal and it is generally only of interest for the most exacting emission targets.

NO from N₂O

At high pressures NO formation via N₂O becomes important:

N₂ + O + M → N₂O + M

N₂O + O → 2NO + Activation Energy = 97kJ/mol

N₂O + O → N₂ + O₂

Competing Reactions :

N₂O + O → NO + N Thermal NO

N₂O + O + M → N₂O + M

d[N₂]/dt = k[O][N₂] α pressure²

d[N₂]/dt = k[O][N₂][M] α pressure³

Health effects

NO_x reacts with ammonia, moisture, and other compounds to form nitric acid vapor and related particles. Small particles can penetrate deeply into sensitive lung tissue and damage it, causing premature death in extreme cases. Inhalation of such particles may cause or worsen respiratory diseases such as emphysema, bronchitis it may also aggravate existing heart disease.^[7]

NO_x reacts with volatile organic compounds in the presence sunlight to form Ozone. Ozone can cause adverse effects such as damage to lung tissue and reduction in lung function mostly in susceptible populations (children, elderly, asthmatics). Ozone can be transported by wind currents and cause health impacts far from the original sources. The American Lung Association estimates that nearly 50 percent of United States inhabitants live in counties that are not in ozone compliance.^[8]

NO_x destroys ozone in the stratosphere.^[9] Ozone in the stratosphere absorbs ultraviolet light, which is potentially damaging to life on earth.^[10] NO_x from combustion sources does not reach the stratosphere; instead, NO_x is formed in the stratosphere from photolysis of nitrous oxide.^[9]

NO_x also readily reacts with common organic chemicals, and even ozone, to form a wide variety of toxic products: nitroarenes, nitrosamines and also the nitrate radical some of which may cause biological mutations. Recently another pathway, via NOx, to ozone has been found that predominantly occurs in coastal areas via formation of nitryl chloride when NOx comes into contact with salt mist.^[11]

Regulation and emission control technologies

As discussed above, atmospheric NO_x eventually forms nitric acid, which contributes to acid rain.^[12] NO_x emissions are regulated in the United States by the Environmental Protection Agency, and in the UK by the Department for Environment, Food and Rural Affairs.

Technologies such as flameless oxidation (FLOX) and staged combustion significantly reduce thermal NO_x in industrial processes. Bowin low NO_x technology is a hybrid of staged-premixed-radiant combustion technology with a major surface combustion preceded by a minor radiant combustion. In the Bowin burner, air and fuel gas are premixed at a ratio greater than or equal to the stoichiometric combustion requirement.^[13] Water Injection technology, whereby water is introduced into the combustion chamber, is also becoming an important means of NO_x reduction through increased efficiency in the overall combustion process. Alternatively, the water (e.g. 10 to 50%) is emulsified into the fuel oil prior to the injection and combustion. This emulsification can either be made in-line (unstabilized) just before the injection or as a drop-in fuel with chemical additives for long term emulsion stability (stabilized). Inline emulsified fuel/water mixtures show NO_x reductions between 4 and 83%.^[14] Other technologies, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) reduce post combustion NO_x.

The use of exhaust gas recirculation and catalytic converters in motor vehicle engines have significantly reduced emissions.

References

1. ^ "NOx Removal". Branch Environmental Corp. Archived from the original on 2007-10-08. http://web.archive.org/web/20071008211011/http://www.branchenv.com/nox/nox_info.asp. Retrieved 2007-12-26. 
2. ^ "Health and Environmental Impacts of NOx". United States Environmental Protection Agency. http://www.epa.gov/airprogm/oar/urbanair/nox/hlth.html. Retrieved 2007-12-26. 
3. ^ D. Fowler, et al. (1998). "The atmospheric budget of oxidized nitrogen and its role in ozone formation and deposition". New Phytologist 139: 11–23. doi:10.1046/j.1469-8137.1998.00167.x. 
4. ^ Joel S. Levine, Tommy R. Augustsson, Iris C. Andersont, James M. Hoell Jr., and Dana A. Brewer (1984). "Tropospheric sources of NOx: Lightning and biology". Atmospheric Environment 18 (9): 1797–1804. doi:10.1016/0004-6981(84)90355-X. PMID 11540827. http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B757C-488FRK0-2N&_user=10&_rdoc=1&_fmt=&_orig=search&_sort=d&_docanchor=&view=c&_searchStrId=1001036955&_rerunOrigin=google&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=05e7b4ab4444bada8188d84c8a19ccc0. Retrieved 2009-09-04. 
5. ^ J.N. Galloway, et al. (September 2004). "Nitrogen cycles: past, present, and future". Biogeochemistry 70 (2): 153–226. doi:10.1007/s10533-004-0370-0. 
6. ^ E.A. Davidson & W. Kingerlee (1997). "A global inventory of nitric oxide emissions from soils". Nutrient Cycling in Agroecosystems 48: 37–50. doi:10.1023/A:1009738715891. 
7. ^ "How nitrogen oxides affect the way we live and breathe". Environmental protection agency. Archived from the original on 2008-07-16. http://web.archive.org/web/20080716063437/http://www.epa.gov/air/urbanair/nox/noxfldr.pdf. Retrieved 2008-12-10. 
8. ^ Ozone, Environmental Protection Agency.
9. ^ ^{a b} NOAA Study Shows Nitrous Oxide Now Top Ozone-Depleting Emission, NOAA, August 27, 2009
10. ^ "Ozone layer". http://www.nas.nasa.gov/About/Education/Ozone/ozonelayer.html. Retrieved 2007-09-23. 
11. ^ Carol Potera (2008). "Air Pollution: Salt Mist Is the Right Seasoning for Ozone". Environ Health Perspect 116 (7): A288. PMC 2453175. http://www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=2453175. 
12. ^ Blankenship, Karl (1997-10). "NOx in the Air: Multiple Effects". Chesapeake Bay Journal. http://www.bayjournal.com/article.cfm?article=2179. Retrieved 2008-06-04. 
13. ^ Bob Joynt & Stephen Wu, Nitrogen oxides emissions standards for domestic gas appliances background study Combustion Engineering Consultant; February 2000
14. ^ "NOx-Reduction by Oil/Water-Emulsification". http://www.hielscher.com/ultrasonics/oil_nox_reduction.htm. Retrieved 2010-05-18.