THE ATMOSPHERE

There are different levels within the atmosphere. The atmosphere extends several
hundred kilometres above the surface of the earth. The different layers of the
atmosphere are shown below
below.

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The troposphere contains most of the atmospheric molecules and this is where
important chemicals changes such as nitrogen fixation take place. The troposphere
is well mixed by convection. This layer of the atmosphere contains 78.08%
nitrogen, 20.95% oxygen, 0.
0.03%
03% carbon dioxide, 0.93% argon and 0.0003% of
other gases such as hydrogen, methane, neon and zenon. The air in the troposphere
is what we breathe. The region of atmosphere that has distinct layers or strata is
called the stratosphere.

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Above about 120km turbulent mixing is so weak that individual gases can separate
under gravitational settling. The part where gravitational settling occurs is termed
the heterosphere because of the varying composition.

The better mixed part of the atmosphere below is called the homosphere. The
turbosphere is the boundary that separates these two parts.

OZONE

The formation of ozone is a photochemical process. It utilizes the energy involved

in light. The shorter the wavelength of light, the larger the amount of energy it
carries. It requires UV radiation of wavelengths less than 242nm to have sufficient
energy to split the oxygen molecule apart.

O2(g) + hv → O(g) + O(g).

The UV photon is symbolized by hv. Once oxygen atoms have been formed, they
react with oxygen molecules, O2.

O2(g)+ O(g) → O3(g).

The production of ozone, O3(g), by this photochemical process can be balanced

against the reactions that destroy ozone, as seen below.

1. O3(g) + hv → O2(g) + O(g).

2. O3(g) + O(g) → 2O2(g).

CHLOROFLOROCARBONS, CFCs

Natural chlorine in the stratosphere is mainly transferred as methyl chloride which

possibly comes from marine and terrestrial biological sources. Another source of
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CFCs are aerosol propellants and refrigerants which had become widely distributed
throughout the troposphere. Compounds such as CF3Cl, Freon-11, and CF2Cl2,
Freon-12, absorb radiation in the 190 to 220nm range which results in photo
dissociation reactions.

CFCl3(g) + hv → CFCl2(g) + Cl(g).

CF2Cl2(g) + hv → CF2Cl(g) + Cl(g).

These reactions produce the free chlorine atoms that react with ozone in the
catalytic manner, i.e.

O3(g) + Cl(g) → O2(g) + ClO(g).

ClO(g) + O(g) → O2(g) + Cl(g).

They result in:

O3(g) + O(g) → 2O2(g).

However, the chlorate, ClO, produced on reaction with ozone may not always
react with the atomic oxygen but can interact with nitrogen compounds instead.

ClO(g) + NO2(g) + M → ClONO2(g) + M.

M is the third body in the reaction which carries away excess energy. It can be an
oxygen gas molecule or a nitrogen gas molecule. The reaction is very important
because it effectively removes nitrogen and chlorine species involved in the cycles
that destroy ozone.

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 EFFECT OF OZONE ON LIFE

Ozone in the stratosphere is important to life because it absorbs UV radiation from

the sun. UV light can cause skin cancer, eye disorders and serious sunburn. UV
light can also destroy phytoplanktons which are primary producers in aquatic food
chains.

Thinning of the ozone layer resu

results
lts in more UV radiation of wavelengths below
320nm reaching the earth’s surface. UV radiation in the wavelength range 290 to
320nm is known as UV –B.
B. In living tissue, this is absorbed by nucleic acids and
may affect genetic information leading to increas
increasee skin cancers in humans. Fair
skinned people are more likely to develop skin cancers since they do not have the
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pigments that are present in dark skinned people which help to screen out UV rays.
Another effect of UV-B
B is that it appears to affect normal iimmune
mmune responses in the
skin and other parts of the body.

Large ozone depletion and hence increased UV radiation will also affect crop yield
in plants due to cell damage. A significant increase in the level of UV radiation
reaching the oceans could cause so
some
me microscopic life to become extinct.
Planktons are very important as they are the beginning of the food chain for all
aquatic animals. Phytoplanktons give out oxygen in the water and into the
atmosphere. They need only water, dissolved carbon dioxide gas
gas,, salts and sunlight
to make their vital substances.

Zooplanktons feed on these microscopic plants and are in turn eaten by fish. The
fish are then eaten by humans and other animals. The effect of an upset on the
ecological balance of planktons would be pa
passed
ssed up the food chain and would be
profound.

CARBON DIOXIDE AND THE ATMOSPHERE

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The concentration of carbon dioxide in the troposphere depends on various
processes involved in the carbon cycle. Carbon dioxide is removed from the
atmosphere in photosynthesis and returns to the atmosphere by respiration in living
things. Atmospheric carbon dioxide is in dynamic equilibrium with carbon dioxide
dissolved in surface water. Dynamic equilibrium means that the concentration of
gaseous and aqueous carbon dioxide remains constant even though there is
constant movement of individual molecules between the atmosphere and the
surface water.

CO2(g) ↔ CO2(aq).

Cold surface water found in oceans at higher altitudes have a higher density than
warmer water and so this surface water sinks rapidly to great depths taking
dissolved carbon dioxide with it. When a chemical species is removed from the
atmosphere, the place where it ends up is called an atmospheric sink. Cold oceans
are an important sink for the removal of atmospheric carbon dioxide.

Dissolved carbon dioxide reacts further with water and establishes a dynamic
equilibrium.

CO2(g) + H2O(l)↔ H+(aq) + HCO-3(aq) ↔ 2H+(aq) + CO2-3(aq).

In general the concentrations of carbon are imbalanced in different sections of the

cycle but variations in the carbon dioxide content of air do occur. There is more
carbon dioxide at night and in the winter. Carbon dioxide concentration is
increased by combustion of fossil fuels.

CH4(g) + 2O2(g) → 2H2O(g) + CO2(g).

And the removal of large areas of tropical rain forest where photosynthesis is
particularly rapid.
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 THE GREENHOUSE EFFECT

The combined effect of the atmosphere’s transparency to most of the incoming

solar radiation and the absorption of much of the earth’s emitted radiation by the
water and carbon dioxide molecules in the atmosphere is often referred to as the
greenhouse effect.
ct. Of the energy which enters the earth’s atmosphere,
approximately 47% reaches the earth’s surface. Incoming energy has a maximum
intensity at wavelength 483nm. Energy reemitted is in the infra
infra-red
red region (2,000 –
40,000nm) with a maximum intensity at 10
10,000nm.

Some of this radiation is absorbed by water vapour and carbon dioxide in the air
and then reemitted. This reemitted radiation helps to maintain the temperature of
the earth’s surface at 14oC. If not for the reemitted radiation the temperature of the
earth would be between -20oC to-40oC.

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There is great concern that the rising levels of carbon dioxide in the atmosphere
together with other greenhouse gases have led to global warming with potentially
disastrous climatic effects.

PHOTOCHEMICAL SMOG

The mixture of smoke and fog is called smog. Water, particulate materials and
sulphur dioxide are all necessary for the creation of smog. All these together will
wi
create a more serious effect than they do individually. The water vapour condenses
on the particles,
icles, which also act as a large surface area for the catalytic oxidation of
sulphur dioxide and sulphur trioxide. Sulphuric acid is formed in the water droplets
and can have serious effects on plants and animals. If these droplets penetrate the
respiratoryy system, severe distress and death can result. Sulphur dioxide absorbed
on to particles can also be inhaled into the respiratory tract. It is then converted
into sulphuric acid in the lungs. This leads to respiratory infections such as,

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asthma, bronchitis and emphysema. It also reduces lung function and causes
irritation to the eyes and respiratory tract.

Sulphur dioxide can cause difficulty in breathing as well as it destroys leaf tissues
of plants. This is because it inhibits enzymes involved in photosy
photosynthesis
nthesis and
respiration.

The quality of air which we breathe is determined by the levels of pollutants in the
atmosphere. Pollutants get into the atmosphere by:

1. Human activities and

2. Natural activities example
(a) lightning converts nitrogen into nitrogen oxides
(b) Volcanoes emit SO2, HCl and CO2 into the atmosphere.

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Pollutants are either primary (emitted directly into the atmosphere) or secondary
(formed indirectly by reactions in the atmosphere).

AIR POLLUTION

Man made pollution is divided into two types:

1. Industrial type (occurs where there is an industrialized area)

2. Photochemical

In the industrial type, the two pollutants are:

(a) Sulphur dioxide, SO2, caused by acid rain

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 (b) Particulate matter (which includes dust, soot and fly ash) causes dirty
neighbourhoods
eighbourhoods and respiratory problems.

Sulphur dioxide arises mainly from:

(i) Burning of sulphur containing fuels mainly coal

S(in coal) + O2(g) → SO2(g).

(ii) The melting of a metal sulphide ore

CuS(s) +O2(g) → Cu(s) + SO2(g).

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The reduction of the emission of sulphur dioxide into the atmosphere is achieved
by either of three methods:

1. Using sulphur free coal example Anthracite (this is limited and therefore
expensive)
2. Removing the sulphur from coal before burning. This is difficult since
sulphur is present in covalently bonded compounds
3. Removing sulphur dioxide by combustion products prior to release in the
atmosphere. The use of scrubbers by industrial or power plants to trap
sulphur dioxide by dissolving sulphur dioxide in water or by reacting it with
another chemical.

SO2 +H2O → H2SO3.

SO2 + 2NaHCO3 → Na2SO3 + CO2 + H2O.

SO2 + CaCO3 → CaSO3 + CO2.

Particulates are released when coal is burnt. The two main substances comprising
particulates are:

(i) Soot formed from incomplete combustion

(ii) Inorganic minerals present in most coals - exist as a fine powdered ash
called fly ash.

Particulates are usually removed from effluent smoke stack gases by the use of
filters.

Examples include:

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 (a) Electrostatic precipita
precipitators – in this device negative charges are imparted to
the particles which become attracted to the positively charged chimney walls
or electrodes.
(b) Bag filters – effluent passes through a porous filter usually shaped like a bag
which entraps the particles.

PHOTOCHEMICAL TYPE POLLUTION

The main pollutants are nitrogen oxides ( e.g. N2O, NO2, N2O4), ozone,
hydrocarbons, aldehydes and peroxynitrates. The main source of these pollutants is
automobile emissions. When these pollutants are combined with fog, a distinctive
dis
brownish haze called a photochemical smog is formed. Some of the reactions that
take place in a photochemical smog include:

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1. 2NO2 + H2O (from atmospheric water) → HNO3 + HNO2. NO2 causes
eye and lung irritation (safety limit for NO2 is 5 ppm)

2. NO2 + sunlight → NO + O
O + O2 → O3 (extremely toxic) (safety limit for O3 is 0.08 ppm)

Photochemical pollution can be reduced by removing NO 2 from the exhaust

gases of automobiles. This is achieved by placing a catalytic converter in the
automotive exhaust system.

V2O5 catalyst
2NO2 → N2 + O 2 .
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 Abnormally high air pollution levels are usually aligned with a thermal or
temperature inversion weather pattern that traps pollutants in a community.
Thermal inversion requires a valley or nearby mountain range. As cold air
passes over the valley it cools the upper levels of the warmer air causing it to
sink. Thus the air, with its pollutants, is trapped in the valley.

Atmospheric pollutants can be reduced as well by:

1. Turning to alternative forms of energy (solar energy, hydrogen cells, etc.)
2. The use of washers to prevent leakage of a gas which is polluted from a
joint
3. Sequesters – these bind to a metal ion, which is toxic, so that it cannot
react.

NITROGEN FIXATION

The nitrogen cycle:

The approximate 78% of the earth’s atmospheric nitrogen becomes a part of

biological matter, almost entirely by nitrogen fixation. The fixation of nitrogen is
the conversion of atmospheric nitrogen into a water soluble form which plants can
take up through their roots.

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Nitrogen gas, N2, is very stable because it contains a triple bond of
dissociation energy +945 kJmol-1. The nitrogen has ionization energy of
1505kJmol-1 for the process,

N2(g) → N+2(g) + e-.

This energy is almost the same as that of the noble gas argon so nitrogen
fixation does not take place easily. Over half the annual fixation of nitrogen
in the world occurs naturally. The remainder is brought about by fertilizer
production and combustion.

Biological fixation occurs in soils using nitrogenase enzymes. Nitrogenase

enzymes occur in such bacteria as clostridium and azotobacter or in most
nodules of plants such as legumes. The direct value of nitrogen fixation to
humans is in the growth of crops. Nitrogen is essential for the formation of
amino acids and proteins.

If the biological nitrogen fixation is insufficient for crop needs, it is

necessary to add fertilizers at certain times of the year. Nitrogenase enzymes
reduce nitrogen to ammonia. Some ammonia is taken into plants through the
root systems and used in the biosynthesis of amino acids.

2NH3(aq) + 2H2O(l) + 4CO2(g) → 2NH2CH2COOH(aq) + 3O2(g).

(Aminoethanoic acid, glycine).

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Nitrification in the soil oxidized the ammonia to nitrite, NO-2, then nitrate
NO-3.
2NH3(aq) + 3O2(g) → 2H+(aq) + 2NO-2(aq) + 2H2O(l).

2NO-2(aq) + O2(g) → 2NO-3(aq).

These reactions are also catalysed by bacterial enzymes. Some 4% of

nitrogen is fixed by the action of lightning. Nitrogen and oxygen from the
atmosphere combines directly to form nitrogen monoxide (nitric oxide), NO.
Lightning
N2(g) + O2(g) → 2NO(g).

The nitrogen monoxide formed is only slowly oxidized to nitrogen dioxide

at the low concentration that exists in the atmosphere. The quantities of
nitrogen oxides in the atmosphere are decreased by reaction with water to
form very dilute nitric acid:

3NO2(g) + H2O(l) → 2HNO3(aq) + NO(g).

Much of the nitrogen that has been fixed is returned to the atmosphere when
nitrates and nitriles are broken down in the soil. This is also catalyzed by
bacterial enzymes and the process is called denitrification.

4NO-3(aq) + 2H2O(l) → 2N2(g) + 5O2(g) + 4OH-(aq).

All these reactions are linked in the nitrogen cycle given earlier.

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The need for the addition of nitrogenous fertilizers has already been
mentioned. There is concern that the increased use of nitrogenous fertilisers
may be leading to an increase of dinitrogen oxide, N2O, in the atmosphere
via the soil denitrification process:

6NO-3(aq) + C6H12O6(aq) → 6CO2(g) + 3H2O(l) 6OH-(aq) + 3N2O(g).

Dinitrogen oxide is unreactive in the troposphere, but may rise into the
stratosphere, where it can influence ozone levels.

SULPHUR DIOXIDE

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Sulphur dioxide is a dangerous primary pollutant. It causes harm to people
plants and materials and has been a major constituent of most air pollutant
disasters. The residence time of sulphur dioxide is 3 – 7 days, depending on
the weather conditions. Wet conditions will remove sulphur dioxide from the
air more rapidly.
Sulphur dioxide is oxidized to sulphur trioxi
trioxide,
de, a secondary pollutant, which
then reacts with water to form sulphuric acid. The overall oxidation reaction:

2SO2(g) + 2H2O(l) + O2(g) → 2H2SO4(aq).

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which is slow but is catalyzed by aerosols containing metal ions e.g. Mn2+,
Fe3+, Cu2+ and oxides of chromium, aluminum, lead and calcium. Surfaces
of buildings can act as catalytic centers and high humidity increases reaction
rates. The sulphur dioxide is oxidized in water droplets and occurs best at a
pH greater than 7, so as sulphuric acid is produced the reaction slows down.
When sulphur dioxide dissolves in water droplets, the reactions are:

SO2(g) + H2O ↔ H2SO3(aq) ……………………………….. (1)

H2SO3(aq) + H2O(l) ↔ H3O+(aq) + HSO-3(aq) …….…... (2)

HSO-3(aq) + H2O(l) ↔ H3O+(aq) + SO2-3(aq) …………. (3)

2HSO-3(aq) ↔ S2O2-5(aq) + H2O(l) …………………….……. (4)

Reactions (2) and (3) show that the solubility of sulphur dioxide in the water
droplet is reduced by increased acidity. Additional H+(aq) shifts these
reactions to the left.
The presence of ammonia increases the rate of oxidation by reducing the
acidity resulting in the formation of ammonium sulphate, (NH4)2SO4, and
ammonium hydrogen sulphate, NH4HSO4, in aerosols. It is actually the
hydrogen sulphite ion, HSO-3(aq), in the water droplet which is oxidized
rather than the SO2 directly.

HSO-3(aq) + H2O(l) → HSO-4(aq) + 2H+(aq) + 2e

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The H+ ions formed are removed by reacting with oxygen.

O2(g) + 4H+(aq) + 4e → 2H2O(l).

PHOTOCHEMICAL OXIDATION
Sulphur dioxide absorbs radiation producing an excited state:
SO2 → SO2*.

This has a relatively long life and reacts in a variety of ways to give sulphur
trioxide (all species in the gaseous state)

SO2* + O2 → SO3 + O*.

SO2* + SO2 → SO3 + SO

SO + SO2 → SO3 + S

Other ways in which sulphur dioxide is oxidized are:

- SO2 + O3 → SO3 + O2. (slow in the gas phase but rapid in water
droplets)

- SO2 + NO2 → SO3 + NO.

Thus nitrogen dioxide from motor vehicle emissions can increase the rate of
oxidation of sulphur dioxide.

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 ACID RAIN

Acid rain is produced by sulphur dioxide dissolving in water to give

sulphurous, H2SO3, and sulphuric acid, H2SO4. Pure rain water has a pH of
approximately 5.6,, but sulphur dioxide emissions can cause it to fall as low
as 2. Sulphur dioxide is the main cause of acid rain, but nitrogen dioxide
emissions from power stations and motor vehicles also contribute to its
formation (the nitrogen oxides dissolve in the wa
water
ter droplets by a series of
complex reactions to form nitric acid).

Acid rain leaches nutrients from soils and enables many toxic metal ions to
dissolve more readily in soil solutions. These ions may then enter food
chains. E.g. aluminium released in Scand
Scandinavian
inavian lakes causes death of many
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fishes. Acid rain increases the rate corrosion of metals and buildings
containing limestone or marble and affects the growth of trees.

INTERNAL COMBUSTION ENGINE

Pollutants emitted from internal combustion engine are pa

particulate,
rticulate, carbon
monoxide, oxides of nitrogen, oxides of sulphur and lead. Most of these
pollutants are emitted from the exhaust. The engine draws a mixture of fuel
and air into the combustion chamber where it is ignited. The hot gas present
after emissions
ns are then expelled before a new charge is introduced. In the
petrol, ignition is initiated by a sparking plug. In the diesel engine the
mixture ignites spontaneously on compression. The air fuel ratio plays an
important part in determining the relative eemission
mission of pollution.

The most common ratios are between 12:1 and 15:1. The stoichiometric
ratio is 15:1. At this ratio emissions of nitrogen oxides are high and those of
CO and hydrocarbons are low. To reduce nitrogen oxide emissions and to
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keep emissions of CO and hydrocarbons low a high air-fuel ratio should be
used. When there is more air than the stoichiometric ratio it is referred to as
a “lean” mixture. The trouble is that a lean mixture will lead to miss firing.
A richer mixture (a lower air fuel ratio than 15:1) reduces the nitrogen
oxides but increases the CO and hydrocarbon.

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