NOx

This article is about nitrogen oxides produced during cal smog, a signicant form of air pollution, especially
combustion. For other denitions 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 eects 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 trac, 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 signicant. 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 dened 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

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 ash.
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 xing
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 xation by microorganisms.[5][6]
1

2.3

Industrial sources

ENVIRONMENTAL EFFECTS

emissions when combusting oil and as much as 80% when

combusting coal.

The three primary sources of NOx in combustion pro- Although the complete mechanism is not fully undercesses:
stood, there are two primary paths of formation. The rst
involves the oxidation of volatile nitrogen species during
thermal NOx
the initial stages of combustion. During the release and
prior to the oxidation of the volatiles, nitrogen reacts to
fuel NOx
form several intermediaries which are then oxidized into
NO. If the volatiles evolve into a reducing atmosphere,
prompt NOx
the nitrogen evolved can readily be made to form nitrogen gas, rather than NOx. The second path involves the
Thermal NOx formation, which is highly temperature de- combustion of nitrogen contained in the char matrix durpendent, is recognized as the most relevant source when ing the combustion of the char portion of the fuels. This
combusting natural gas. Fuel NOx tends to dominate dur- reaction occurs much more slowly than the volatile phase.
ing the combustion of fuels, such as coal, which have a Only around 20% of the char nitrogen is ultimately emitsignicant nitrogen content, particularly when burned in ted as NOx, since much of the NOx that forms during this
combustors designed to minimise thermal NOx. The con- process is reduced to nitrogen by the char, which is nearly
tribution of prompt NOx is normally considered negligi- pure carbon.
ble. A fourth source, called feed NOx is associated with
the combustion of nitrogen present in the feed material of
cement rotary kilns, at between 300 and 800 C, where 2.3.3 Prompt
it is also a minor contributor.
This third source is attributed to the reaction of atmospheric nitrogen, N2 , with radicals such as C, CH, and
2.3.1 Thermal
CH2 fragments derived from fuel, where this cannot be
explained by either the aforementioned thermal or fuel
Thermal NOx refers to NOx formed through high tem- processes. Occurring in the earliest stage of combusperature oxidation of the diatomic nitrogen found in com- tion, this results in the formation of xed species of nitrobustion air.[7] The formation rate is primarily a function gen such as NH (nitrogen monohydride), HCN (hydrogen
of temperature and the residence time of nitrogen at that cyanide), H2 CN (dihydrogen cyanide) and CN- (cyano
temperature. At high temperatures, usually above 1600 radical) which can oxidize to NO. In fuels that contain
C (2900 F), molecular nitrogen (N2 ) and oxygen (O2 ) nitrogen, 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.
acting emission targets.
The three principal reactions (the extended Zeldovich
mechanism) producing thermal NOx are:
2.3.4 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. Zeldovich was the rst
kJ/mol)
to suggest the importance of the rst two reactions. The
N 2 O + O N2 + O 2
last reaction of atomic nitrogen with the hydroxyl radi
cal, HO, was added by Lavoie, Heywood and Keck to
the mechanism and makes a signicant contribution to Competing Reactions :
the formation of thermal NOx.
N2 O + O NO + N (thermal NO)
2.3.2

Fuel

N2 O + O + M N2 O2 + M

The major source of NOx production from nitrogenbearing fuels such as certain coals and oil, is the conver- 3 Environmental eects
sion of fuel bound nitrogen to NOx during combustion.[7]
During combustion, the nitrogen bound in the fuel is re- NOx reacts with ammonia, moisture, and other comleased as a free radical and ultimately forms free N2 , or pounds to form nitric acid vapor and related particles.
NO. Fuel NOx can contribute as much as 50% of total Small particles can penetrate deeply into sensitive lung

3
tissue and damage it, causing premature death in extreme The use of exhaust gas recirculation and catalytic convertcases. Inhalation of such particles may cause or worsen ers in motor vehicle engines have signicantly reduced
respiratory diseases, such as emphysema or bronchitis, or vehicular emissions.
may also aggravate existing heart disease.[8]
NOx reacts with volatile organic compounds in the presence of sunlight to form ozone. Ozone can cause adverse eects 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.[9]
NOx destroys ozone in the stratosphere.[10] Ozone in
the stratosphere absorbs ultraviolet light, which is potentially damaging to life on earth.[11] NOx from combustion
sources does not reach the stratosphere; instead, NOx is
formed in the stratosphere from photolysis of nitrous oxide.[10]
NOx 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.[12]

Regulation and emission control

technologies

Technologies such as ameless oxidation (FLOX) and

staged combustion signicantly reduce thermal NOx in
industrial processes. Bowin low NOx 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
NOx reduction through increased eciency in the overall combustion process. Alternatively, the water (e.g. 10
to 50%) is emulsied into the fuel oil prior to the injection and combustion. This emulsication 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 emulsied fuel/water
mixtures show NOx reductions between 4 and 83%.[14]
Other technologies, 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. SCR is
now being used in diesel trucks and in some diesel cars.

5 References
[1] NOx Removal. Branch Environmental Corp. Archived
from the original on 2007-10-08. Retrieved 2007-12-26.
[2] Health and Environmental Impacts of NOx. United
States Environmental Protection Agency. 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: 1123. doi:10.1046/j.14698137.1998.00167.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): 17971804.
doi:10.1016/0004-6981(84)90355-X. PMID 11540827.
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:
3750.
doi:10.1023/A:1009738715891.
[7] Milton R. Beychok (March 1973). NOX emission from
fuel combustion controlled. The Oil and Gas Journal:
5356.
[8] How nitrogen oxides aect the way we live and breathe.
Environmental protection agency. Archived from the
original on 2008-07-16. Retrieved 2008-12-10.
[9] Ozone, Environmental Protection Agency.
[10] NOAA Study Shows Nitrous Oxide Now Top OzoneDepleting Emission, NOAA, August 27, 2009
[11] Ozone layer. Retrieved 2007-09-23.
[12] Carol Potera (2008). Air Pollution: Salt Mist Is the
Right Seasoning for Ozone. Environ Health Perspect 116
(7): A288. doi:10.1289/ehp.116-a288. PMC 2453175.
PMID 18629329.
[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-Emulsication.
trieved 2010-05-18.

Re-

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