Nitrogen oxide
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This section refers to the chemical term for nitrogen oxides produced during
combustion. For other definitions see Nox
The term nitrogen oxide typically refers to any binary compound of oxygen and
nitrogen, or to a mixture of such compounds:
Nitric oxide (NO), nitrogen(II) oxide
Nitrogen dioxide (NO2), nitrogen(IV) oxide
Nitrous oxide (N2O), nitrogen (I) oxide
Dinitrogen trioxide (N2O3), nitrogen(III) oxide
Dinitrogen tetroxide (N2O4), nitrogen(IV) oxide
Dinitrogen pentoxide (N2O5), nitrogen(V) oxide
(Note that the last three are unstable.)
Chemical reactions that produce nitrogen oxides often produce several different
compounds, the proportions of which depend on the specific reaction and conditions.
For this reason, secondary[clarification needed] production of N2O is undesirable, as NO and
NO2 — which are extremely toxic — are liable to be produced as well.
Nitrous oxide, Dinitrogen trioxide,
Nitric oxide, NO Nitrogen dioxide, NO2
N2O N2O3
Dinitrogen tetroxide, Dinitrogen pentoxide,
N2O4 N2O5
Contents
[hide]
1 NOx
2 Definition of NOx, NOy, NOz in atmospheric chemistry
3 Industrial sources of NOx
o 3.1 Thermal NOx
o 3.2 Fuel NOx
o 3.3 Prompt NOx
4 Health effects
5 Regulation and emission control technologies
6 Biogenic sources
7 See also
8 References
9 External links
[edit] NOx
NOx is a generic term for mono-nitrogen oxides (NO and NO2). These oxides are
produced during combustion, especially combustion at high temperatures.
At ambient temperatures, the oxygen and nitrogen gases in air will not react with each
other. In an internal combustion engine, combustion of a mixture of air and fuel
produces combustion temperatures high enough to drive endothermic reactions between
atmospheric nitrogen and oxygen in the flame, yielding various oxides of nitrogen. In
areas of high motor vehicle traffic, such as in large cities, the amount of nitrogen oxides
emitted into the atmosphere can be quite significant.
In the presence of excess oxygen (O2), nitric oxide (NO) will be converted to nitrogen
dioxide (NO2), with the time required dependent on the concentration in air as shown
below:[1]
NO concentration in air Time required for half NO
(ppm) 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 NOx 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 susceptible to adverse effects of smog such as damage to lung tissue
and reduction in lung function.[2]
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:
2NO2 + H2O → HNO2 + HNO3
(nitrogen dioxide + water → nitrous acid + nitric acid).
Nitrous acid then decomposes as follows:
3HNO2 → HNO3 + 2NO + H2O
(nitrous acid → nitric acid + nitric oxide + water),
where nitric oxide will oxidize to form nitrogen dioxide that again reacts with water,
ultimately forming nitric acid:
4NO + 3O2 + 2H2O → 4HNO3 (nitric oxide + oxygen + water → nitric acid).
Mono-nitrogen oxides are also involved in tropospheric production of ozone.[3]
NOx should not be confused with NOS, a term used to refer to nitrous oxide (N2O) in
the context of its use as a power booster for internal combustion engines.
[edit] Definition of NOx, NOy, NOz in atmospheric
chemistry
In atmospheric chemistry the term NOx is used to mean the total concentration of NO
plus NO2. During daylight NO and NO2 are in equilibrium with the ratio NO/NO2
determined by the intensity of sunshine (which converts NO2 to NO) and the
concentration of ozone (which reacts with NO to give back NO2). NO and NO2 are also
central to the formation of tropospheric ozone. This definition excludes other oxides of
nitrogen such as nitrous oxide (N2O). NOy (reactive odd nitrogen) is defined as the sum
of NOx plus the compounds produced from the oxidation of NOx which include nitric
acid and peroxyacetyl nitrate and alkyl nitrates. In this context nitrous oxide and
ammonia are not considered as reactive nitrogen compounds. Occasionally the term
NOz is used to refer to the quantity NOy - NOx.
[edit] Industrial sources of NOx
The three primary sources of NOx in combustion processes:
thermal NOx
fuel NOx
prompt NOx
Thermal NOx formation, which is highly temperature dependent, is recognized as the
most relevant source when combusting natural gas. Fuel NOx 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 NOx. The
contribution of prompt NOx is normally considered negligible. 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 it is also a minor contributor.
[edit] Thermal NOx
Thermal NOx refers to NOx 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 producing thermal NOx are:
(Extended Zeldovich Mechanism)
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 Hydroxyl radical, OH, was
added by Lavoie, Heywood and Keck to the mechanism and makes a significiant
contribution to the formation of thermal NOx.
[edit] Fuel NOx
The major source of NOx production from nitrogen-bearing fuels such as certain coals
and oil, is the conversion of fuel bound nitrogen to NOx during combustion. During
combustion, the nitrogen bound in the fuel is released as a free radical and ultimately
forms free N2, or NO. Fuel NOx 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 NOx. 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 NOx, since much of the
NOx that forms during this process is reduced to nitrogen by the char, which is nearly
pure carbon.
It is possible to revert NOx emitted from a diesel engine back into Nitrogen and Water
by using an SCR Selective Catalytic Reduction Unit. This requires the addition of an
urea based liquid re-agent namely AdBlue to initialise the chemical reaction.
[edit] Prompt NOx
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 NOx is especially minimal and it is generally only of interest for the
most exacting emission targets.
[edit] Health effects
NOx react 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.[4]
NOx react with volatile organic compounds in the presence of heat and 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. Millions of Americans live in areas that do not meet the health standards for
ozone.
NOx also readily react 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.
[edit] Regulation and emission control technologies
The Kyoto Protocol, ratified by 54 nations in 1997, classifies N2O as a greenhouse gas,
and calls for substantial worldwide reductions in its emission.[5]
As discussed above, atmospheric NOx eventually forms nitric acid, which contributes to
acid rain.[6] NOx 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 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. [7]
Water Injection technology, wherby water is introduced into the combustion chamber, is
also becoming an important means of NOx 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). Other technologies, such as
selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) reduce
post combustion NOx.
The use of Exhaust gas recirculation and catalytic converters in motor vehicle engines
have significantly reduced emissions.
[edit] Biogenic sources
Agricultural fertilization and the use of nitrogen fixing plants also contribute to
atmospheric NOx, by promoting nitrogen fixation by microorganisms.[8][9]
[edit] See also
Nitrogen oxide sensor
[edit] References
1. ^ "NOx Removal". Branch Environmental Corp.
http://www.branchenv.com/nox/nox_info.asp. Retrieved on 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 on 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. ^ "How nitrogen oxides affect the way we live and breathe". Environmental protection
agency. http://www.epa.gov/air/urbanair/nox/noxfldr.pdf. Retrieved on 2008-12-10.
5. ^ Gerrard, Michael B. (2007-09-25). Global Climate Change and U.S. Law. American
Bar Association. pp. 38. ISBN 1590318161.
6. ^ Blankenship, Karl (1997-10). "NOx in the Air: Multiple Effects". Chesapeake Bay
Journal. http://www.bayjournal.com/article.cfm?article=2179. Retrieved on 2008-06-
04.
7. ^ Bob Joynt & Stephen Wu, Nitrogen oxides emissions standards for domestic gas
appliances background study Combustion Engineering Consultant; February 2000
8. ^ 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.
9. ^ 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.
[edit] External links
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