Air Pollution

Man’s Needs:
• The average body requirements of air per day to sustain its need for O2 is
about 23kg air/day.

• The daily requirement of air by mankind:

109
23 × × 7 (𝑏𝑖𝑙𝑙𝑖𝑜𝑛) = 161 × 106 𝑡𝑜𝑛𝑛𝑒𝑠/𝑑𝑎𝑦
1000

• The annual requirement:

161 × 106 × 365 = 58.765 × 109 𝑡𝑜𝑛𝑛𝑒𝑠

• The table below shows the amount of air that a man weighing 68.5kg
actually inhales per day:
State Litre/day Litre/day Kg/day
Resting 7.4 10,600 12
Light work 28.0 40,000 45
Heavy work 43.0 62,000 69
Composition Of Air:
• A knowledge of the composition of air is required in any study of air
pollution. Air composition varies with local conditions.

• Table 1-1 shows the composition of Normal Dry Ambient Air:

TABLE 1-1
Composition of Normal Ambient Air (Dry)
Total Mass
Substance Component By volume By weight
(gm x 10-20)
Nitrogen N2 78.084 ± 0.0004% 75.51% 33.648
Oxygen O2 20.946 ± 0.0002% 23.15% 11.841
Argon A 0.934 ± 0.0010% 1.28% 0.6555
Carbon
CO2 0.033 ± 0.0010% 0.046% 0.0233
dioxide
Neon Ne 18.180 ± 0.040 ppm 12.50 ppm 6.36 x 10-4
Helium He 5.240 ± 0.004 ppm 0.72 ppm 3.70 x 10-5
Krypton Kr 1.140 ± 0.010 ppm 2.90 ppm 1.46 x 10-4
Zenon Xe 0.087 ± 0.001 ppm 0.36 ppm 1.80 x 10-5
Nitrous
N2O 0.500 ± 0.110 ppm 1.50 ppm 7.70 x 10-5
Oxide
Methane CH4 2 ppm 1.20 ppm 6.20 x 10-5
Hydrogen H2 0.5 ppm 0.02 ppm 2.00 x 10-6
Ozone O3 0.01 ppm -- --
Radon
Rn 10-13 ppm -- --
(222)
Zones Of Earth’s Atmosphere:

• Zones may be divided according to height above the earth:

1. Troposphere: about 11km above the earth, it is part of the

atmosphere, and the temperature decreases with height.

2. Stratosphere: above the troposphere, has little change of

temperature with height, and has no clouds. (about 40 km in
thickness)
▪ Air pollution analysis is concerned with the lower 8km
portion of the troposphere, or 70% of the total air by weight.

3. Mesosphere: above 48km, temperature decreases with height.

• Global effects of Air Pollution

TABLE 1-3 Aerosol residence times
SCEP (1970) Newell (1971) Removal
mechanism
Lower 6 - 14 days 6 – 10 days Rain, gravity fall
troposphere out for particles >
10μ
Upper 2 – 4 weeks 30 days Rain
troposphere
Lower 6 months to 1 4 months ---
stratosphere year at the
equator
Upper 3 - 5 years 1 year to 3 ---
stratosphere years*
Mesosphere 5 – 10 years --- ---
* Residence time is a function of latitude and is greater near the equator.
* Study of Critical Environmental Problems (SCEP) 1970
Temperature decreases with height

T nearly constant, or increases with

height

Temperature decreases with height,

except for inversion conditions
Importance Of Air:
(1) Air serves as a storehouse and carrier of all gases required for mankind.
(2) Air carries away the waste products of the oxidation reaction.
(3) Air contains injected waste in the atmosphere.
(4) Air carries sound and lights.
(5) Air is a medium for flying objects.

Factors Responsible For Air Pollution Problem:

(1) Population growth.

More people → more manufactured goods and services → leads to
second factor.

(2) Expansion in Industries and Technology.

Growth of Industrial Expansion of Increase of New

Activity Existing Plant Manufacturing
Capacity Establishments

New

Processes Methods Products

Air Air Borne

Borne Toxicity
wastes
 (3) Social changes.

a. Urbanization.
Rural → urban → Metropolitan complexes

b. Rising in the standard f living.

Higher quality of nutrition → Housing → Transportation → Labour.

Saving devices → Cars → Television sets, refrigeration → automatic

washing and drying machines → Demands Electric Power

Thermal power Plants

Oil Coal Combustion Natural

Nuclear of solid Gas
waste

Air Pollution Categories:

(1) Personal air pollution, Exposure

Dust, Cigarette,
Fumes, Cigar, Pipe
Gases Smoking

(2) Occupational air pollution:

Exposure of individuals to potentially harmful concentrations of aerosols,
vapour, and gases in their working environment → industrial hygiene.

(3) Community Air Pollution:

Most complex, involves assortment of pollution sources and
contaminants, meteorological factors, adverse social, economic and
health effects.
Meaning Of Air Pollution:
Is the presence in the outdoor atmosphere of one or more contaminants, such as
dust, fumes, gas, mist, odour, smoke in quantities, of characteristics, and duration
such as to be injurious to human, plant, or animal life, or to property or which
unreasonably interferes with the comfortable enjoyment of life and property.

Units For Quantification Of Air Pollution:

1. mg/m3, milligrams per cubic metre, used for stack gas concentrations of
particulates, which are usually rather high.

2. mg = 10-3 gm, milligram.

3. µg = 10-6 gm = 10-3 mg = microgram.

4. ppm (ppmv), part per million by volume, used for gaseous material.

1 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡𝑠

1 𝑝𝑝𝑚 =
106 𝑉𝑜𝑙𝑢𝑚𝑒𝑠 (𝑃𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡𝑠 + 𝐴𝑖𝑟)

• At 25 °C and 760 mm Hg (1 atmosphere) pressure the relationship between

parts per million and microgram per cubic meter is:

𝜇𝑔 𝑝𝑝𝑚 × 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡

3
= × 103
𝑚 24.5

• The constant in the denominator is 24.41 at 0 °C and 760 mm Hg pressure,

since 1 mole of any ideal gas has a volume of 22.41 liters at the specified
pressure and temperature. The value is 24.5 due to the change in the
temperature from 0 C (273 °K) to 25 °C (298 °K)
• Example 1: Convert 60 μg/m3 of SO2 at STP (standard Temperature and
Pressure: 0 °C and 760 mm Hg) to ppm. Molecular weight of SO2 = 64.

𝜇𝑔 𝑝𝑝𝑚 × 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡

3
= × 103
𝑚 24.1
𝜇𝑔 𝑝𝑝𝑚 × 64
60 3 = × 103
𝑚 24.1
𝜇𝑔
60 3 = 0.00225 𝑝𝑝𝑚
𝑚

• Example 2: The average concentration of SO2 is 400 μg/m3 of at 25 °C

and 1 atmosphere. Express the concentration in ppm.

𝜇𝑔 𝑝𝑝𝑚 × 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡

= × 103
𝑚3 24.5
𝜇𝑔 𝑝𝑝𝑚 × 𝑔64
400 3 = × 103
𝑚 24.5
𝜇𝑔
400 3 = 0.154 𝑝𝑝𝑚
𝑚

• Example 3: The Ozone concentration is observed to be 80 μg/m3 at an

urban monitoring station. If the standard clean air should not have more
than 0.02 ppm of Ozone, is this standard violated? Molecular weight of O3
= 48.
𝜇𝑔 𝑝𝑝𝑚 × 48
80 3 = × 103
𝑚 24.5
𝜇𝑔
80 3 = 0.04 𝑝𝑝𝑚 > 0.02 𝑝𝑝𝑚
𝑚
The Clean Air Standards are violated!

• Example 4: An automobile exhaust contains 1.0% by volume of carbon

monoxide. What is the concentration of CO in mg/m3 at 25 °C and 1 atm
pressure? Molecular weight of CO = 28.

1 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡𝑠 104

𝐶𝑂 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 = 2
× 4
= 104 𝑝𝑝𝑚
10 𝑉𝑜𝑙𝑢𝑚𝑒𝑠 (𝑃𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡𝑠 + 𝐴𝑖𝑟) 10

𝜇𝑔 𝑝𝑝𝑚 × 𝑔𝑎𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡

3
= × 103
𝑚 24.5
𝜇𝑔 104 × 28
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑎𝑟𝑡𝑖𝑜𝑛 𝑖𝑛 3 = × 103 = 11.4 × 106
𝑚 24.5
𝑚𝑔
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑎𝑟𝑡𝑖𝑜𝑛 𝑖𝑛 = 11.4 × 103
𝑚3
General Classification Of Air Pollution Sources:
Important factors, several factors must be considered in emissions in air
pollution:

A. Type of source, reference considerations of natural and man-made

sources.

B. Number of spatial distribution of sources. There are three major

categories:
1. Single or point sources: power plant, petroleum refinery, steel mill.
2. Area–wide or multiple sources: collectively, large number of smaller
sources over well-defined area, residential area, commercial buildings.
3. Line sources: freeways, highways, steady stream of moving vehicles.

C. Types of Emission. Problem of air pollution area the nature and

characteristics of the contaminant emitted to atmosphere. Emissions can
be: Solid, Liquid, or Gaseous.

Types Of Air Pollutants:

1. Particulate matter (PM): PM20, PM10, and PM2.5

2. Carbon monoxide (CO).

3. Nitrogen oxides (NOx):

𝑁𝑂𝑥 + 𝐻2 𝑂 → 𝐻𝑁𝑂3 {𝑁𝑖𝑡𝑟𝑖𝑐 𝑎𝑐𝑖𝑑}

4. Sulfur oxides (SOx).

𝑆𝑂𝑥 + 𝐻2 𝑂 → 𝐻𝑆𝑂3 → 𝐻𝑆𝑂4 {𝑆𝑢𝑙𝑓𝑢𝑟𝑜𝑢𝑠 𝑎𝑛𝑑 𝑠𝑢𝑙𝑓𝑢𝑟𝑖𝑐 𝑎𝑐𝑖𝑑𝑠}

5. Volatile organic compounds (VOCs).

6. Lead.
 Table 12-3: Percentage Estimates Of Criteria Pollutants From
Various Sources.
Source Particulate SOx NOx VOC CO Lead
Transportation 21.0 4.0 44.0 33.0 70.0 41.5
Stationary
source fuel 26.0 81.0 52.0 12.0 12.0 6.0
combustion
Industrial
37.0 15.0 3.0 41.0 7.0 22.0
processes
Solid waste
4.0 0 0.5 3.0 3.0 31.0
disposal
Miscellaneous 12.0 0 0.5 11.0 8.0 0.0

Table 12-1 National Ambient Air Quality Standards.

Pollutant Average Primary Secondary Objective
time
To limit
Carbon
8h 10 mg/m3 (9ppm) None carboxy-
monoxide
hemoglobin
To prevent
1h 40 mg/m3 (35ppm) 23 mg/m3
Nitrogen health risks and
dioxide improve
Annual 100 μg/m3 (0.053 ppm) Same
visibility
To prevent eye
irritation and
Ozone 1h 235 μg/m3 (0.12 ppm) Same
breathing
difficulties
To prevent
increase in
respiratory
Sulfur
Annual 80 μg/m3 (0.03 ppm) None disease, plant
dioxide
damage, and
damage to
structures
To improve
24 h 365 μg/m3 (0.14 ppm) Same
visibility and to
PM-10
prevent health
Annual 50 μg/m3
effects
24 h 150 μg/m3 Same
To prevent
Lead
health problems
3 month 1.5 μg/m3 Same
Primary: designed to protect public health with an adequate margin of safety.
Secondary: designed to protect public welfare (plants, animals, and properties).
Air Pollution Episodes:

(1) Classical smog:

Complete mixture of partially combusted coal with high sulfur content
that builds up and forms under stagnant cold weather condition.

(2) Photo-chemical Smog:

A complete mixture of products formed from the interaction of
sunlight with 2 major automobile exhaust emission (nitric oxide and
hydrocarbons) and are favoured under stable weather conditions.

(3) Sea-Land Breeze:

Sea Breeze During Daytime:

The opposite happens during night-time: Land Breeze

The Sea-Land Breeze phenomenon results in trapping of

pollutants!
(4) Mountain-Valley Breeze:

During Daytime: Valley Breeze

During Night-time: Mountain Breeze

The Mountain-Valley Breeze phenomenon results in trapping of

pollutants!
(5) Carbon Monoxide (CO)
• It is a very stable chemical compound.
• When CO is introduced into the blood stream; CO is absorbed 210 times
more than oxygen.
• Define [HbCO] as concentration of carboxyhemoglobin in the blood.
• The concentration [HbCO] can be estimated using the following formula:

%𝐻𝑏𝐶𝑂 = 0.005 [𝐶𝑂]0.85 (𝛼́ 𝑡)0.63

Where:
[CO] = concentration of CO in the ambient air; ppm.
t = time of exposure.
𝛼́ = activity factor (1 for high work – 3 for heavy work).

Example 12 – 1
The concentration of CO in a street intersection reaches the federal ambient
standard of 35 ppm. Crewmen from the department of public works are
repairing a break in the water line. Estimate the CO concentration in their
blood after 1 h of work and make conclusion as to their work performance.

Solution
%𝑯𝒃𝑪𝑶 = 𝟎. 𝟎𝟎𝟓 [𝑪𝑶]𝟎.𝟖𝟓 (𝜶́ 𝒕)𝟎.𝟔𝟑
let 𝜶́ = 2, then
%𝐻𝑏𝐶𝑂 = 0.005 [35]0.85 (2 × 60)0.63 = 2.1%
hence; according to table 12-2; their work performance is impaired.
(6) Ozone Depletion (Destruction Of Ozone Layer):
• The earth’s atmosphere may be divided into four layers: the troposphere, stratosphere,
mesosphere, and thermosphere.

• The troposphere occupies the layer closest to the surface starting from zero to about
16 km above the ground. This thickness, however, is not constant throughout the
globe. In the midlatitudes, it can range from 10 to 12 km (about the altitude of a
typical airplane flight).

• In the poles, due to a heavier density, it can range from 5 to 6 km, and in the equator
due to lighter density, the thickness of the troposphere layer may go as high as 18 km.
the troposphere has a dry adiabatic lapse rate of -9.57 ℃/km

• The troposphere is the layer where clouds form. It is normally turbulent, due to the
presence of a favorable lapse rate, enabling the pollutant to mix relatively fast.

• In contrast, above the troposphere is a calm, stable layer called the stratosphere. From
the figure, the layer stretches from an altitude of approximately 16 km to about 49 km
above the surface of the earth. The reason for the stability of the stratosphere is the
inverted lapse rate that occurs in this layer. The temperature increases as the altitude
increases.
 • Figure 10-6b shows the atmospheric absorption of radiation on a clear day. As indicated
ozone and molecular O2 effectively absorbs the sun’s ultraviolet radiation in the range
below 0.30 μm.

• This absorption causes a series of photochemical reaction to occur, liberating heat. This
heat liberation is the cause of the temperature rise in the stratosphere layer.

• Because of the temperature inversion, the stratosphere is very stable. Pollutants that come
into this layer from the troposphere may become trapped here for years.
• There is no mechanism for scavenging any pollutant by rain since this layer is very dry and
the limit of cloud formation is the troposphere.
• The only way that a pollutant may decay is through photolytic decomposition and by a
chance-drifting back to the troposphere.
• Once returned to the troposphere, it can be removed by rainfall scavenging and dissolution.
The troposphere and the stratosphere comprise about 99.9% of the mass of the
atmosphere.
• Above the startosphere is the mesosphere which extends from approximately 49 km to
about 86 km above the surface of the earth.
• With respect to temperature variation, stratosphere is similar to the troposphere. As the air
expands, it cools.
• If as the air expands, however, a reaction releases heat, the air may heat up or stay cool,
depending on the amount of heat released. In the stratosphere, the heat from the
photochemical reaction exceeds the heat required for expansion; hence the layer heats up.
• In the mesosphere, however, the situation is different; the heat requirement for expansion
exceeds the heat released by reaction and the air cools. Hence the temperature decreases
with altitude, as in the troposphere.
• Above the mesosphere is the thermosphere, the temperature rises. The reason for this rise is
the absorption of solar energy by atomic oxygen. The heating effect caused by this absorption
exceeds the heat requirement for expansion, heating the atmosphere. (Within the
thermosphere is a relatively dense layer of charged particles. This layer is called the
ionosphere.)
• Ozone effectively absorbs the short-wavelength ultraviolet (UV) spectrum of less than 0.30
μm. This process occurs in the stratosphere.
• There is good evidence that a UV-induced alteration of deoxyribonucleic acid (DNA) causes
skin cancer. The most useful function of ozone is therefore in the stratosphere.
• The reactions below illustrate the formation of ozone in the stratosphere, O2 absorbs the sun’s
short-UV wavelength of 0.24 μm and below;

𝑂2 + ℎ𝑣 → 𝑂 + 𝑂 (10-86)

• The atomic oxygen, in turn, rapidly reacts with molecular O2 to form ozone.
𝑂 + 𝑂2 + 𝑀 → 𝑂3 + 𝑀 (10-87)

• Radiation on the order of 0.30 μm (0.300 to 0.315 μm) has been linked to skin cancer:
nonmelanoma and the more life-threatening malignant melanoma. Absorption in this range of
wavelength therefore protects life on earth from the damaging biological effects of radiation.
The damaging effect of radiation includes, in addition to skin cancer, eye cataracts and retinal
degeneration and immune system suppression. A milder form of biological damage is human
sunburn. The equation below portrays the absorption of UV radiation in the range 0.300 to
0.315 μm.

𝑂3 + ℎ𝑣 → 𝑂2 + 𝑂 (10-88)

• Scientists first expressed concern over the possible destruction of the ozone layer in the
1970s. they found that species such as Cl, Br, OH, and NO react with ozone, destroying it.
Then, in 1985, an announcement was made of the creation of a hole in the ozone layer over
Antarctica the size of the United States. This aroused the world to begin acknowledging the
seriousness of the problem. Using X to represent the species Cl, Br, OH (hydroxyperoxyl
radical), and NO (nitric oxide), following are the reactions of ozone destruction:
𝑋 + 𝑂3 → 𝑂2 + 𝑋𝑂 (10-89)

𝑋𝑂 + 𝑂 → 𝑋 + 𝑂2 (10-90)

• As seen from these reactions, the species X has been regenerated. Hence this catalyst can go
on destroying thousands more O3 molecules. The only way that the destruction can cease is
when a species appears that is capable of undergoing a terminating reaction with X, or for X
to return to the troposphere, where it may be removed by rain. It must also be remembered
that X is composed of Cl, Br, OH-, and NO- thus, the reactions above can be compounded
several times over.
6.1 Chlorofluorocarbons (CFCs):
• The dominant sources of the chlorine atom are CH3Cl, the chlorofluorocarbons CFC-11 and
CFC-12, and carbon tetrachloride (CCl4).
• The CH3Cl is mostly of natural origin, whereas the chlorofluorocarbons are man-made.
Carbon tetrachloride is both of natural and man-made origin.
• Anthropogenic sources of less importance are the cleaning solvents trichloroethylene
(CCl2=CHCl), methyl chloroform, and CFC-113.
• CFC-113 is used in the electronic industry in various critical cleaning and degreasing
operations.
• The key chlorine species for ozone destruction are CFC-11 and CFC-12.
• A source of bromine atoms are Halons, fluorocarbons that contain bromine atoms and used in
fire extinguishers.
• Although they are in the troposphere, they can diffuse into the stratosphere to cause ozone
damage.
• CFCs are molecules that contain chlorine, fluorine, and carbon. They are very important
commercially. Although banned by the US Environmental Protection Agency since 1979,
they have been used extensively in the past. CFC-11 and CFC-12 are believed to lifetimes of
60 and 110 years, respectively; hence. They do not just disappear from the atmosphere.
• To determine the chemical formula for a CFC, simply add 90 to its suffix number and
interpret the resulting three-digit number as follows: the leftmost digit is the number of C
atoms, the middle digit is the number of hydrogen atoms, the rightmost digit is the number of
fluorine atoms. To determine the number of chlorine atoms, subtract the number of hydrogen
and fluorine atoms plus the number of single carbon-to-carbon bonds from the total possible
number of single bonds that the carbon atoms can have. Thus, for CFC-12: 90 + 12 = 102.
Therefore, there are one C, zero H, and two F atoms. The H and F are two, and since there is
only one C, there are no carbon-to-carbon bonds. The total possible number of single bonds of
C is four. Therefore, the total number of chlorine atoms is 4 – (2 + 0) = 2. Hence, the formula
is CCl2F2.

Example 10-9
What is the chemical composition of CFC-113?
Solution
90 +113 = 203. Therefore, C = 2, H = 0, and F = 3. H + F = 0 +3 = 3.
Since there are two C, total C-to-C bonds = 1, and the total possible single C bonds = 7.
Thus, the number of Cl atoms = 7 – (3+1) = 3, and the formula is C2Cl3F3.
• CFCs are used as aerosol propellants, refrigerants, and solvents. They are also used in foamed
plastics.
• After CFCs were banned in 1979, replacement propellants such as carbon dioxide, isobutane,
and propane were used.
• However, CO2 is an important agent of the greenhouse effect. The hydrocarbons isobutane
and propane are constituent species in photochemical smog reactions. Daily use of these
aerosols in the home may also result in substantial problems of indoor air pollution. Presently,
simple pumps have been used to propel contents instead of aerosols.
• The creation of the ozone hole over Antarctica may be explained as follows: CFCs are very
stable molecules that are not normally degraded in the usual processes taking place in the
troposphere. When found in the stratosphere, however, they are broken down by UV,
releasing the chlorine atom. Using CFC-12, the reaction is
𝐶𝐶𝑙2 𝐹2 + ℎ𝑣 → 𝐶𝑙 + 𝐶𝐶𝑙𝐹2 (10-91)

• Cl then reacts according to reaction (10-89) destroying ozone and producing ClO. The
product ClO reacts further with NO2, forming chlorine nitrate:
𝐶𝑙𝑂 + 𝑁𝑂2 → 𝐶𝑙𝑂𝑁𝑂2 (10-92)

• At this stage Cl is effectively trapped in ClONO2, an inert compound that can do no damage
to the ozone. Over Antarctica, however, a phenomenon of atmospheric circulation called the
circumpolar or polar vortex forms. The formation of the polar vortex blocks the warmer
midlatitude air from mixing with the air above the pole. Thus, the polar air is trapped with no
connections to the outside warmer air. This condition cools the air in the stratosphere, which
can go down to -90℃. Even though stratospheric air is very dry, ice crystals can form at this
very low temperature, providing reaction surfaces for chlorine nitrate to react with water to
form HOCl and HNO3:
𝐶𝑙𝑂𝑁𝑂2 + 𝐻2 𝑂 → 𝐻𝑂𝐶𝑙 + 𝐻𝑁𝑂3 (10-93)

• As long as the polar vortex exists, reaction (10-93) continues to operate, accumulating HOCl:
this accumulation is simply waiting for the Antarctica spring.
• As the sun first rises in the Antarctica spring of August or September, HOCl photolyzes,
forming Cl and the hydroxyperoxyl radical, which destroys the ozone. The sequence of
reaction are as follows:
𝐻𝑂𝐶𝑙 + ℎ𝑣 → 𝐶𝑙 + 𝑂𝐻 (10-94)

𝐶𝑙 + 𝑂3 → 𝐶𝑙𝑂 + 𝑂2 (10-95)

𝑂𝐻 + 𝑂3 → 𝑂2 + 𝐻𝑂2 (10-96)

(10-97)
𝐶𝑙𝑂 + 𝐻𝑂2 → 𝐻𝑂𝐶𝑙 + 𝑂2

• With this formation of HOCl, the cycle starts all over again. It is clear that even one molecule
of CFC-12 can destroy thousands of molecules of ozone.
(7) Greenhouse effect
(Global Warming or Climate Change):
• The sun emits solar radiation in all directions, with a wavelength of about
0.15 µm to about 4.8 µm (short wave radiations).
• The earth absorbs the energy coming from the sun, and as the earth is
heated its temperature rises.
• This makes the earth capable of re-radiating back energy into space. The
radiations from the earth range from about 2.8 µm to about 4.8 µm (long
wave radiations).
• The earth albedo is about 30%.
• The phenomenon of the greenhouse effect can be explained as follows:
The short-wave radiation of the sun is absorbed by the earth, heating it to
a temperature of about 255 °K (-18 °C). Because of the heat it absorbs,
the earth reradiates energy back into space in the form of a long-wave
radiation. In the atmosphere, however, are molecules that can absorb this
radiated energy, converting it to heat. Being heated, the molecules can
now also radiate the heat they absorb back into earth, producing the
perturbation differential temperature of 33 °K. This temperature
differential is due to the greenhouse effect.
• The molecules that produce this effect are called greenhouse gases:
o Carbon dioxide, CO2
o Water vapor, H2O
o Dinitrogen oxide, N2O
o Methane, CH4
o CFC-11 and CFC-12
• Because of the greenhouse effect, the overall average annual temperature
has been raised from 288 °K (-18 °C) to 288 °K (15 °C).
• To solve the problem of greenhouse effect (climate change):
o Use less fossil fuel (produce less CO2),
o Use sources of energy that do not produce CO2:
▪ Wind power,
▪ Hydroelectric power,
▪ Solar energy,
▪ Nuclear energy.
Empirical equations have been derived to predict the equilibrium-incremental
increase in temperature ∆T caused by these pollutants. These The formula is:

∆𝑇𝑑 {𝐶𝑂2 }
∆𝑇 = ln + 0.057 ({𝑁2 𝑂}0.5 − {𝑁2 𝑂}0.5
0 ) + 0.019({𝐶𝐻4 }
0.5
− {𝐶𝐻4 }0.5
0 )
ln 2 {𝐶𝑂 }
2 0
+ 0.14({𝐶𝐹𝐶 − 11} − {𝐶𝐹𝐶 − 11}0 ) + 0.16({𝐶𝐹𝐶 − 12} − {𝐶𝐹𝐶 − 12}0 )

Where ∆𝑇𝑑 is the equilibrium-incremental change in temperature for a doubling

in CO2 concentration and the zero subscripts refer to the initial value of the
parameter affected. The temperature is in degrees Celsius and the
concentrations are in ppb.

Example 10-10
In 1850 the concentrations of the greenhouse gases were as follows: CO2=280 ppm,
CH4=1150 ppb, N2O=285 ppb, CFC-11=0, and CFC-12=0. In 1985 they were CO2=345 ppm,
CH4=1790 ppb, N2O=305 ppb, CFC-11=0.24 ppb, and CFC-12=0.4 ppb. By 207514 they are
estimated to be CO2=576 ppm, CH4=4402 ppb, N2O=478 ppb, CFC-11=2.28 ppb, and CFC-
12=3.80 ppb.
(a) Calculate the equilibrium-incremental increase in temperature from 1850 to 2075.
(b) Calculate the equilibrium-incremental increase in temperature from 1985 to 2075.
Assume that ∆𝑇𝑑 = 3℃.

Solution
∆𝑇𝑑 {𝐶𝑂2 }
∆𝑇 = ln + 0.057 ({𝑁2 𝑂}0.5 − {𝑁2 𝑂}0.5
0 ) + 0.019({𝐶𝐻4 }
0.5
− {𝐶𝐻4 }0.5
0 )
ln 2 {𝐶𝑂2 }0
+ 0.14({𝐶𝐹𝐶 − 11} − {𝐶𝐹𝐶 − 11}0 ) + 0.16({𝐶𝐹𝐶 − 12} − {𝐶𝐹𝐶 − 12}0 )

3.0 576
∆𝑇1850−2075 = ln + 0.057 ({478}0.5 − {285}0.5 ) + 0.019({4402}0.5 − {1150}0.5 )
ln 2 280
+ 0.14(2.28 − 0) + 0.16(3.80 − 0)
= 3.12 + 0.284 + 0.62 + 0.32 + 0.61 = 4.95℃

3.0 576
∆𝑇1985−2075 = ln + 0.057 ({478}0.5 − {305}0.5 ) + 0.019({4402}0.5 − {1790}0.5 )
ln 2 345
+ 0.14(2.28 − 0.24) + 0.16(3.80 − 0.40)
= 2.22 + 0.25 + 0.46 + 0.29 + 0.54 = 3.76℃