Beruflich Dokumente
Kultur Dokumente
Subramanian
MODULE 3.2
Air Pollutants
Carbon Oxides 1
Carbon monoxide 1
Sources of CO pollution 1
Industrial processes 1
CO emission from vehicle exhaust 2
Natural processes 2
Sinks 3
Toxicity of CO 4
Control of CO emissions 4
Carbon Dioxide And Global Warming 5
Sulphur Dioxide Sources And Removal 9
Sulphur dioxide reactions in the atmosphere 9
Effects of atmospheric sulphur dioxide 10
Nitrogen Oxides In The Atmosphere 11
Harmful effects of nitrogen oxides 13
Control of NOx emissions 13
Acid Rain 15
Particles In The Atmosphere 16
Particle formation 18
Radioactive particles 19
MODULE 3.2
Air Pollutants
A wide range of chemicals can pollute the air, but only those pollutants
which are generally viewed as needing control measures are discussed in this
chapter and in the next chapter. Air pollutants can be arbitrarily classified
according to chemical composition as (1) inorganic air pollutants and (ii) organic
air pollutants
Carbon Oxides:
Carbon monoxide:
Sources of CO pollution
Industrial processes:
containing compounds.
2C + O2 → 2CO ....................................................................................(1)
temperature.
Most of the CO in the ambient air comes from vehicle exhaust. Internal
combustion engines do not burn completely to CO2 and water; some unburnt fuel
Natural processes:
seed germination, marsh-gas production etc, are the natural processes that
Sinks:
hydroxyl radical. This process is however rather slow and the reduction in CO
level away from the source area is almost entirely a function of atmospheric
dilution processes.
and it is removed from the atmosphere by reaction with hydroxyl radical, HO•:
O2 + H + M → HOOi + M ..........................................................(5)
regenerate HO• :
Toxicity of CO:
effects on materials or plants, but those levels can adversely affect human
health. After entering the blood stream through the lungs, carbon monoxide
haemoglobin (COHb).
Carbon monoxide, infact, has a much greater affinity for haemoglobin than
does oxygen, so that even small amounts of CO can seriously reduce the
amount of oxygen conveyed throughout the body. With this blood stream carrying
less oxygen, brain function is affected and heart rate increases in an attempt to
Control of CO emissions:
As mentioned earlier since major contribution to CO pollution is from
accountable for it, control measures have been concentrated on the automobiles.
mixture, that is one in which the weight ratio of air to fuel is relatively high. At air
monoxide emissions. Excess air is pumped into the exhaust gas and the mixture
oxidation of CO to CO2.
sufficiently durable (50,000 driven miles) catalytic material. The catalysts now in
their surfaces. One of the most effective catalytic poisons is lead and this is one
and other gases and particles. If we focus our attention on other gases, Carbon
temperature rise
The figure shows that the main influence is by CO2 but the contribution of
IR radiation emitted
from earth's surface
I J
H2O absorption
CO2 absorption
4 8 12 16 20 24
Wavelength (µm)
H2O and CO2. The watervapour strongly absorbs thermal radiation with
wavelengths less than 8 µm amd greater than 18 µm. CO2 shows a strong
band centered at 2.7 and 4.3 µm. Between 7 and 12 µm there is relatively clear
called green house gases. As the fig.2 suggests, CO2 and watervapour trap good
portion of the outgoing thermal radiation attempting to leave the earth's surface.
Thus these green house gases act as thermal blanket around the globe raising
increasing each year, the largest effect is still due to CO2. Anthropogenic
production of CO2 from burning fossil fuels exceeds that of the other green house
gases. Although the natural flux of CO2 to the atmosphere due to the constant
biomass and it rises to a maximum in winter when the dead vegetation days,
releasing its stored carbon as CO2 . The oscillatory pattern is regular from year to
which increased from 314 ppm in 1958 to 365 ppm in 2000, a 17.5 percent
CO2
CO2
CO2 CO2
Industries
Plants
Auto
Ocean
(Bio-mass)
CO2 HCO3-
organic
CO32-
carbon
The major important sink for CO2 is ocean (Fig.2). Because sea water is
alkaline and CO2 is acidic, the oceans are vast reservoir of CO2. However only
the surface layer of ocean, the top 75 meters, is in equilibrium with the
atmosphere and its capacity to absorb CO2 is limited. Exchange of surface layer
with deep oceans takes hundreds of years. The location of the remaining carbon
dioxide has been a subject of considerable debate, but it is now widely accepted
that vegetation absorbs much of the CO2. But even with this natural sink sources,
warming can shift the climate zones and the existing forests may not be able to
adapt, especially if the shift is rapid and again the result may be loss of biomass.
Some important industrial sources of SO2 are (1) nonferrous smelters (2)
oil refining and (3) paper and pulp manufacture.
Nonferrous smelters: With the exception of iron and aluminium, metal ores are
sulphur compounds. When the ore is reduced to the pure metal, its sulphur is
ultimately oxidised to SO2. Thus when Cus ore is reduced to copper, its sulphur
is oxidised to SO2 .
Oil refining: Sulphur and hydrogen sulphide are constituents of crude oil and
more toxic than SO2 it is burned to produce SO2 before release to the ambient
air.
Pulp and paper manufacture: The sulphite process for wood pulping uses hot
H2SO3 and thus emits SO2 in air. The kraft pulping process produces H2S, which
Sulphur trioxide react quickly with H2O to form sulphuric acid, which is the
occurring inside water aerosol droplets, which proceed faster in the presence of
ammonia and catalysts such as manganese (II), iron (II), nickel (II), copper (II),
etc.
reach far deeper into the lungs. The combination of particulate matter and
sulphur oxides can then act synergistically, with the effects of both together being
much more detrimental than either of them separately. Sulphur dioxide is one of
the serious air pollutants which is responsible for smog formation, which has
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made of marble, limestone and mortar, as the carbonates of these materials are
replaced by sulphates,
that are important in the study of air pollution are nitric oxide (NO) and nitrogen
dioxide (NO2). The most abundant oxide is nitrous oxide. This is however
chemically rather unreactive and is formed from the natural biological processes
in the soil. Nitrous oxide first undergoes photochemical reaction. The formed
atomic oxygen reacts with another molecule of N2O to give NO. The formed nitric
oxide reacts with ozone, thereby causing ozone depletion. They can be
N2O + hυ → N2 + O .................................................................................(16)
N2O + O → NO + NO ..............................................................................(17)
NO + O3 → NO 2 + O 2 ...............................................................................(18)
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1210 −1765
⎯⎯⎯⎯⎯→ 2NO ……………………………………………..….(19)
N2 + O2 ←⎯⎯⎯⎯⎯
Thus all high temperature processes produce NO, which is then oxidised to NO2
⎯⎯
2NO + O2 ←⎯→ 2NO2 …………………………………………….………(20)
⎯
NO2 + hυ → NO + O ……………………………………………………(21)
The principal reactions among NO,NO2, and HNO3 are indicated below:
Reactions of NO:
Reactions of NO2:
12
Nitric oxide and nitrogen dioxide are important constituents of polluted air.
These oxides collectively designated as NOx, enter the atmosphere mainly from
exposures ranging from several minutes to one hour, a level of 50 – 100 ppm
NO2 causes inflammation of lung tissue for a period of 6 – 8 weeks, after which
time the subject normally recovers. Exposure of the subject to 150 – 200 ppm of
after exposure. Death generally results within 2 – 10 days after exposure to 500
several parts per million of NO2 in the laboratory causes leaf spotting and break
down of plant tissue. It also causes fading of dyes and inks used in some
nitric acid.
the ratio of air to fuel in the combustion chamber is varied. The NO production
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oxidise the fuel), where the highest temperature is reached. If less air is admitted
to the combustion zone ("fuel-rich"), the NO production rate falls along with the
two stages, the first of which is rich in fuel and the second of which is rich in air.
In this way the fuel is burned completely, but the temperature is never as high as
incorporated in power plants; it has been tried in cars but with less success.
In order to deal with both NO and unburned gases the converter has two
In the oxidation chamber, air added, and the CO and unburned hydrocarbons are
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Acid Rain:
We have seen that in polluted regions the main causes for acid rain are
sulphur dioxide and nitrogen oxides in the atmosphere. Acid rain results when
these gases are oxidised in the atmosphere and return to the ground dissolved in
rain drops. SO2 falls as H2SO3 and H2SO4 while NOx falls as HNO3. A night time
route
1
SO2 + O2 + H2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
(soot particle metal oxide)
→ H2SO4 …………………………..(27)
2
1
NO2 + H2O → 1 HNO2 + HNO3 …………………………………………..…(28)
2 2
X −H
NO2 + O3 → NO3 ⎯⎯⎯→ HNO3 ……………………………………………..(29)
nitrate free radical. In water droplets ions such as Mn(II), Fe(II), Ni(II) and Cu(II)
catalyse the oxidation reaction. Soot particles are also known to be strongly
involved in catalysing the oxidation of SO2. HNO3 and H2SO4 combine with HCl
air pollution problem for smog and a global one for ozone-destroying chlorofluoro
15
hydrocarbons and green house gases. Acid rain causes major damages to our
• It acidifies the lake water with toxic effects especially to fish fingerlings.
ornamental materials. The hydrogen ions from the acid rain dissolve the
the troposphere and have a diameter of 0.001µm to 10µm. Aerosol particles from
natural sources have a diameter of less than 100µm. These particles originate
from sea sprays, smokes, dusts and the evaporation of organic materials from
16
bacteria, fog, pollen grains, and volcanic ash. Thus particulate matter may be
both organic or inorganic and both types are very important atmospheric
contaminants.
• Particles in the size 0.1 to 1µm cause serious health hazards. These
particles penetrate the lungs, blocking and irritating air passages and can
have toxic effects. Soot particles pose particular problem because they
can abosrb significant amounts of toxic chemicals on their irregular
surfaces. Coal fires release soot as well as SO2 and in foggy conditions,
the resulting aerosol can combine with soot to produce a toxic smog, with
serious health consequences.
• They are very much involved in several chemical interactions taking place
in the atmosphere such as neutralisation reactions taking place in water
droplets thus providing a surface, and they provide active catalytic surface
upon which heterogeneous chemical reactions can occur.
17
Particle formation:
carbonaceous material, metal oxides and glases, dissolved ionic species, and
ionic solids.
oxide. Part of the calcium carbonate in the ash fraction of coal is converted to
The direct reaction of SO2 with O2 is very slow, and the oxidation is carried
out by more reactive species particularly the hydroxyl radical. Some of the
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When the humidity is low water is lost from these droplets and a solid
compounds, several metals and radio nuclides are present in polluted urban
atmospheres.
Radioactive particles:
The source for these radioactive particles arise from mining and
During the processing of uranium large amounts of uranium tailings are produced
The fly ash introduced into the atmosphere during the combustion of fossil
fuels, contain several radionuclides. For example large coal-fired power plants
radionuclides into the atmosphere each year, far more than either an aquivalent
Nuclear weapon testing whether in the air or underground can give rise to
90
radioactive fall out. For example Sr, which is a longlived component of
radioactive fall out is chemically similar to calcium. The 90Sr mixes with calcium in
the soil and is taken by plants, animals and finally by man. By virtue of its
similarity to calcium it enters into bones and cause disorders in blood cell
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Radon being a noble gas readily escapes from soil and porous rock and diffuses
into the lower atmosphere. There the nuclides decay with half-lives of 3.8 days
subsequent α and β emissions can irradiate and damage the lung tissue.
20