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NOx

This article is about nitrogen oxides produced during cal smog, a significant form of air pollution, especially
combustion. For other definitions see Nox
in the summer. Children, people with lung diseases such
See also: Nitrogen oxide
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]
NOx 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
1.1 Formation of nitric acid and acid rain
in the air during combustion, especially at high temperatures. In areas of high motor vehicle traffic, such as in
Mono-nitrogen oxides eventually form nitric acid when
large cities, the amount of nitrogen oxides emitted into
dissolved in atmospheric moisture, forming a component
the atmosphere as air pollution can be significant. NOx
of acid rain. This chemical reaction occurs when nitrogen
gases are formed whenever combustion occurs in the
dioxide reacts with water:
presence of nitrogen – as in an air-breathing engine; they
also are produced naturally by lightning. In atmospheric
2 NO2 + H2 O → HNO2 + HNO3
chemistry, the term means the total concentration of NO
and NO2 . NOx gases react to form smog and acid rain
as well as being central to the formation of tropospheric Nitrous acid then decomposes as follows:
ozone.
3 HNO2 → HNO3 + 2 NO + H2 O
NOx should not be confused with nitrous oxide (N2 O),
which is a greenhouse gas and has many uses as an
oxidizer, an anesthetic, and a food additive.
where nitric oxide will oxidize to form nitrogen dioxNOy (reactive, odd nitrogen) is defined as the sum of NOx ide that again reacts with water, ultimately forming nitric
plus the compounds produced from the oxidation of NOx acid:
which include nitric acid.
NO + 2 O2 + H2 O → 2 HNO3

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

Formation and reactions

Oxygen and nitrogen do not react at ambient temper- This nitric acid may end up in the soil, where it makes
atures. But at high temperatures, they undergo an nitrate, where it is of use to growing plants.
endothermic reaction producing various oxides of nitrogen. Such temperatures arise inside an internal combustion engine or a power station boiler, during the com- 2 Sources
bustion of a mixture of air and fuel, and naturally in a
lightning flash.
2.1 Natural sources
In atmospheric chemistry, the term NOx means the total
concentration of NO and NO2 . During daylight, these Nitric oxide is produced during thunderstorms due to the
concentrations are in equilibrium; the ratio NO/NO2 is extreme heat of lightning,[4] and is caused by the splitting
determined by the intensity of sunshine (which converts of nitrogen molecules. This can result in the production
NO2 to NO) and the concentration of ozone (which reacts of acid rain, if nitrous oxide forms compounds with the
water molecules in precipitation.
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 ).
2.2 Biogenic sources
The time required depends on the concentration in air as
shown below:[1]
Agricultural fertilization and the use of nitrogen fixing
When NOx and volatile organic compounds (VOCs) re- plants also contribute to atmospheric NOx, by promoting
act in the presence of sunlight, they form photochemi- nitrogen fixation by microorganisms.[5][6]
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reaction occurs much more slowly than the volatile phase. ing the combustion of fuels. Zeldovich was the first kJ/mol) to suggest the importance of the first two reactions.3. which is nearly tribution of prompt NOx is normally considered negligi. Heywood and Keck to the mechanism and makes a significant contribution to Competing Reactions : the formation of thermal NOx.1 Thermal CH2 fragments derived from fuel. N2 .NOx reacts with ammonia. which have a Only around 20% of the char nitrogen is ultimately emitsignificant nitrogen content. ble. Fuel NOx can contribute as much as 50% of total Small particles can penetrate deeply into sensitive lung . and other comleased as a free radical and ultimately forms free N2 . N2 O + O → NO + N (thermal NO) 2.3. was added by Lavoie. with radicals such as C.3 Environmental effects sion of fuel bound nitrogen to NOx during combustion.(cyano temperature. rather than NOx.tion. nitrogen reacts to • fuel NOx form several intermediaries which are then oxidized into NO. • prompt NOx the nitrogen evolved can readily be made to form nitrogen gas. where this cannot be explained by either the aforementioned thermal or fuel Thermal NOx refers to NOx formed through high tem.Although the complete mechanism is not fully undercesses: stood.process is reduced to nitrogen by the char. particularly when burned in ted as NOx. The first involves the oxidation of volatile nitrogen species during • thermal NOx the initial stages of combustion. Fuel NOx tends to dominate dur. During the release and prior to the oxidation of the volatiles. The second path involves the Thermal NOx formation.3. NO.processes.3 Prompt it is also a minor contributor. H2 CN (dihydrogen cyanide) and CN. is the conver. this results in the formation of fixed species of nitrobustion air.4 NO from N2 O N2 + O → NO + N N + O2 → NO + O N + OH → NO + H At high pressures NO formation via N2 O becomes important: N2 + O + M → N2 O + M N2 O + O → 2 NO (activation energy 97 All three reactions are reversible. In fuels that contain °C (2900 °F).combustion of nitrogen contained in the char matrix durpendent. The three primary sources of NOx in combustion pro. called feed NOx is associated with the combustion of nitrogen present in the feed material of cement rotary kilns. moisture. such as coal. or pounds to form nitric acid vapor and related particles. CH.2 2. The three principal reactions (the extended Zeldovich mechanism) producing thermal NOx are: 2. A fourth source. where 2. there are two primary paths of formation. usually above 1600 radical) which can oxidize to NO. HCN (hydrogen of temperature and the residence time of nitrogen at that cyanide). since much of the NOx that forms during this combustors designed to minimise thermal NOx.[7] During combustion. acting emission targets. At high temperatures.pure carbon. The con. This combusting natural gas. and 2. at between 300° and 800 °C. which is highly temperature de. the incidence of prompt NOx is especially minin the combustion air disassociate into their atomic states imal and it is generally only of interest for the most exand participate in a series of reactions. The N 2 O + O → N2 + O 2 last reaction of atomic nitrogen with the hydroxyl radi• cal.2 Fuel N2 O + O + M → N2 O2 + M The major source of NOx production from nitrogenbearing fuels such as certain coals and oil. the nitrogen bound in the fuel is re. HO.3. If the volatiles evolve into a reducing atmosphere. Occurring in the earliest stage of combusperature oxidation of the diatomic nitrogen found in com. is recognized as the most relevant source when ing the combustion of the char portion of the fuels. This third source is attributed to the reaction of atmospheric nitrogen.[7] The formation rate is primarily a function gen such as NH (nitrogen monohydride).3 3 Industrial sources ENVIRONMENTAL EFFECTS emissions when combusting oil and as much as 80% when combusting coal. molecular nitrogen (N2 ) and oxygen (O2 ) nitrogen.

James M.116-a288. trieved 2010-05-18.1016/0004-6981(84)90355-X.1998. Recently another pathway. Fowler. NOAA. [4] Joel S. “A global inventory of nitric oxide emissions from soils”. Environmental protection agency. Retrieved 2008-12-10. New Phytologist 139: 11–23. Andersont. 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). “Nitrogen cycles: past. Inhalation of such particles may cause or worsen ers in motor vehicle engines have significantly reduced respiratory diseases. doi:10. via NOx. Alternatively.14698137. doi:10. to form a wide variety of toxic products: nitroarenes. [3] D. Nitrogen oxides emissions standards for domestic gas appliances background study Combustion Engineering Consultant. Kingerlee (1997). air and fuel gas are premixed at a ratio greater than or equal to the stoichiometric combustion requirement. and future”. such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) reduce post combustion NOx by reacting the exhaust with urea or ammonia to produce nitrogen and water. and Dana A. United States Environmental Protection Agency. Inline emulsified fuel/water mixtures show NOx reductions between 4 and 83%.[8] NOx reacts with volatile organic compounds in the presence of sunlight to form ozone. may also aggravate existing heart disease. [13] Bob Joynt & Stephen Wu. and even ozone. [5] J. (September 2004).3 tissue and damage it. Re- . Hoell Jr.N.[12] 4 Regulation and emission control technologies Technologies such as flameless oxidation (FLOX) and staged combustion significantly reduce thermal NOx in industrial processes. doi:10. Branch Environmental Corp. “Tropospheric sources of NOx: Lightning and biology”. [9] Ozone. Retrieved 2007-12-26. or vehicular emissions. Retrieved 2007-12-26.00167. nitrosamines and also the nitrate radical some of which may cause biological mutations. instead. Environmental Protection Agency. the water (e. Retrieved 2009-09-04. Biogeochemistry 70 (2): 153– 226.x. February 2000 [14] “NOx-Reduction by Oil/Water-Emulsification”.1046/j. 2009 [11] “Ozone layer”. [7] Milton R. Davidson & W. doi:10. Levine. NOx is formed in the stratosphere from photolysis of nitrous oxide. [2] “Health and Environmental Impacts of NOx”. Archived from the original on 2008-07-16.. Ozone can be transported by wind currents and cause health impacts far from the original sources.A. PMID 11540827.1289/ehp. [6] E.[14] Other technologies. [10] NOAA Study Shows Nitrous Oxide Now Top OzoneDepleting Emission.g. asthmatics). Archived from the original on 2007-10-08. Bowin low NOx technology is a hybrid of staged-premixed-radiant combustion technology with a major surface combustion preceded by a minor radiant combustion. The American Lung Association estimates that nearly 50 percent of United States inhabitants live in counties that are not in ozone compliance. Galloway. In the Bowin burner. to ozone has been found that predominantly occurs in coastal areas via formation of nitryl chloride when NOx comes into contact with salt mist.1023/A:1009738715891. “Air Pollution: Salt Mist Is the Right Seasoning for Ozone”. “NOX emission from fuel combustion controlled”. Iris C. [8] “How nitrogen oxides affect the way we live and breathe”. August 27. PMID 18629329.[13] Water Injection technology.[10] Ozone in the stratosphere absorbs ultraviolet light. doi:10. present. Tommy R. (1998).[9] NOx destroys ozone in the stratosphere. Retrieved 2007-09-23. SCR is now being used in diesel trucks and in some diesel cars. “The atmospheric budget of oxidized nitrogen and its role in ozone formation and deposition”. is also becoming an important means of NOx reduction through increased efficiency in the overall combustion process. Ozone can cause adverse effects such as damage to lung tissue and reduction in lung function mostly in susceptible populations (children. et al.[11] NOx from combustion sources does not reach the stratosphere. The Oil and Gas Journal: 53–56. Environ Health Perspect 116 (7): A288.[10] NOx also readily reacts with common organic chemicals. 10 to 50%) is emulsified into the fuel oil prior to the injection and combustion. causing premature death in extreme The use of exhaust gas recirculation and catalytic convertcases. Nutrient Cycling in Agroecosystems 48: 37–50. et al. Atmospheric Environment 18 (9): 1797–1804. whereby water is introduced into the combustion chamber. Beychok (March 1973).1007/s10533-004-0370-0. elderly. Augustsson. 5 References [1] “NOx Removal”. PMC 2453175. such as emphysema or bronchitis. Brewer (1984). which is potentially damaging to life on earth. [12] Carol Potera (2008).

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