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Lecture 3

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Lecture 3

Uploaded by

teferatamene21
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chemical and Photochemical

Reactions in the Atmosphere


Chemical and Photochemical Reactions in the Atmosphere

• Due to low concentrations involved detections


and analysis of products is extremely difficult
• Chemicals in the atmoshere take part in
photochemical rxn by absorption of solar
radiation
• The atmosphere is tremendously dynamic
system with wide fluctuations of parameters
(composition, T0 ,humidity, & sunlight)
Cont…
• The chemistry of the following substances in
the atmosphere shall be covered:
– Oxygen and ozone
– Sulfur dioxide
– Nitrogen oxide and Nitrogen
– Organic compounds
– Acid base rxn in the atmosphere
Oxygen and Ozone Chemistry

Oxygen exchange among the atmosphere, geosphere, hydrosphere, and biosphere.


Cont…
 Ozone absorbs UV light in the range of 200–
300 nm
 It has a maximum concentration of about 10 ppm in
the atmosphere at about 35 km height (in the
stratosphere).
 Thus, ozone acts as the Earth’s UV shield (or
sunscreen), preventing UV radiation damage to the
biosphere.
• If we lose the ozone sunscreen, we might have an
increase in skin cancer and eye cataracts and a
decrease in photosynthesis.
Cont…
• As it is mentioned earlier, atmosphere is
dynamic. Many chemical and physical
processes are taking place in the atmosphere.
• UV radiation causes photochemical
dissociation, ionization, etc
• The main set of reactions that describe the
production and loss of ozone in the
stratosphere are the following:
Chapman Mechanism
O2  hv  O  O
 The atomic oxygen thus produced will combine with un-split oxygen
molecule (O2) to produce ozone molecule (O3) once again.

O  O2  M ( N 2 orO2 )  O3  M

In this reaction a third body, M plays a crucial role in absorbing the excess
energy liberated
 Thus formed ozone will be split by striking ultra-violet radiation at the
wavelength around 308 nm into a molecule of O2 and an atom of oxygen.

O3  hv  O  O2
Cont…
• By this ozone-oxygen cycle, the concentration of ozone is
maintained.
• Ozone in the stratosphere is maintained as a result of a
dynamic balance between these formation and destruction
processes.
 From 1930 to 1975, this was the basis for our understanding
of the ozone layer.
 We now know that the loss mechanism from the Chapman
scheme accounts for only 20% of ozone loss.
• Due to photochemical dissociation by ultra-violet radiation,
other forms of oxygen are also present in stratosphere:
• O+, O• and O• 2 – ionic form and excited form. These reactions
are as shown below:
Cont…
O+hv  O++ e
 O2+hv  O2++ e
 O2+hv  O+O
• They are also part of the ozone-oxygen cycle.
• O+ is a predominant +ve ion in some regions of the ionosphere. It
may react with molecular oxygen or nitrogen to form other +ve ions

O+ + O2 -------O2+ + O
O+ + N2-------NO+ + N
• The diatomic oxygen ion (O2+) can also be produced by the following
reaction:
N2+ + O2--------N2 + O2+
• This entire cycle is presented in the figure below.
Figure - Ozone-oxygen cycle
OZONE LAYER DEPLETION
• Recall that stratospheric ozone, O3, serves as a shield to
absorb harmful ultraviolet radiation
• Today, due to human activities, this ozone layer is becoming
thin. This thinning is called, ozone depletion. At the zones,
where thinning is too severe, they are termed as “Ozone
holes”.
• Chloro-fluoro carbons (CFC) used in refrigerators, air
conditioners, propellants etc. and oxides of nitrogen emitted
by air crafts flying near stratosphere are found to be the
causes for ozone layer depletion.
• Ozone layer is depleted by free radical catalysts – nitric oxide
(NO), hydroxyl (OH), atomic chlorine (Cl), and atomic bromine
(Br).
• Halogens have the ability to catalyze ozone breakdown
OZONE LAYER DEPLETION BY CFCs
• The major culprit in ozone depletion consists of
chlorofluorocarbon (CFC) compounds, commonly
known as “Freons.”
• CFCs is stable compound and live long in the
atmosphere
• As it lives longer it is able to rise to the stratosphere.
• Cl radicals are liberated from these compounds by
the action of ultraviolet radiation.
• These radicals initiate and catalyze breaking the
ozone molecules.
Cont…
• One single radical is capable of breaking down over
100,000 ozone molecules.
• CFCs have long life time 50 to 100 years. As they remain
for such a long duration, they deplete ozone layer
continuously.
• Moreover, this depletion rate keep increasing as more
and more CFCs are released.
• Ozone depletion is by chlorine atom is illustrated in the
figure below.
• The chemical reactions that lead to destruction of O3 by
CFCl3 are shown below. Similar reactions take
place with other CFCs (CF2Cl2 )
Chlorine-catalyzed ozone depletion mechanism
Cont…
*
CFCl3  hv  CFCl2  Cl
Cl *  O3  ClO * O 2
ClO *  O  Cl *  O2
After realizing the seriousness of this problem, countries have
come forward to ban completely the use of CFCs
This effort has yielded positive result.
Depletion of ozone layer had slowed down due to the ban on
CFCs.
Scientists have developed HCFC to replace CFC for the same
purpose.
These HCFCs are short-lived in the atmosphere to reach the
stratosphere and damage ozone layer
OZONE LAYER DEPLTION BY NITRIC OXIDE
• Chemistry of ozone depletion by nitric oxide is shown below:

O3  NO  NO2  O2
NO2  O3  NO3  O2
M
NO3  NO2   N 2O5
NO  NO3  2 NO2
M
O  NO   NO2

When a nitric oxide (NO) molecule combines with O3, it is oxidized to nitrogen
dioxide (NO2).
This NO2 now combines with another O3 molecule to become NO3 and O2.

Both NO2 and NO3 may combine to form N2O5.


Even if atomic oxygen is available, it readily combines with NO2 to yield NO3.

 Thus, O3 is completely utilized for the above reactions and thereby depleted
Consequences Of Ozone Depletion
• Ozone depletion has a number of
consequences for human health and
agriculture.
• These include :
 Increased rate of skin cancer and eye cataracts,
 Weakening of immune systems
 Damage to crops
 Reductions in primary produces (plankton) in
the ocean and
 Increasing air pollution
Sulfur dioxide
• Sources : natural and industrial sources
• Natural: volcanic eruptions and sulphur-
containing geothermal sources and biological
decay of organic matter and reduction of
sulfate
• Industrial: Some important industrial sources
of SO2 are
(1) nonferrous smelters
(2) oil refining and coal firing
(3) paper and pulp manufacture
Sulphur dioxide reactions in the atmosphere:

• Some of the possible ways in which SO2 may


react in the atmosphe are :
1. Photochemical rxns
2. Photochemical & chemical rxns in the
presence of NOX or hydrocarbons
3. Chemical processes in water droplets
containing metal salts & NH3
4. Reaction on solid particles in the atmosphere
Cont…
• SO2once released can convert to SO3, in a series of
reaction which, once again, involve a free radical such as
OH•
SO2+ OH• → HOSO2•
HOSO2• +O2 →SO3+HO2•
• SO3 react quickly with H2O to form sulphuric acid, which
is the principal cause of acid rain.
SO3+H2O →H2SO4
• The formation is promoted by the presence of
hydrocarbons and nitrogen oxides, which are key
components of photochemical smog.
Cont…
• In relatively humid atmospheres:
• SO2 is probably oxidized by reactions occurring inside
water aerosol droplets, which proceed faster in the
presence of NH3 and catalysts such as manganese (II),
iron (II), nickel (II), copper (II),etc
NH3+SO2+H2O → NH4+ + HSO3-
NH3+HSO3- →NH4++SO32-

 SO2 is a serious pollutant responsible for Smog


 It also contributes for Acid rain (H2SO4 from SO2,HNO3 from NO2
& H2CO3 from CO2)

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