ENVIRONMENTAL

CHEMISTRY (209)22
Chemistry of Gaseous Pollutants
LECTURE 13

Instructor :Prof. Dr. Mohammad

Rafiq Khan
 Air Pollution
NATURAL EMISSIONS
 Major Sources: Volcanoes, microorganisms, biomass burning,
photochemical reactions, etc.
Ozone
Chemical Formula O3
 Formed in the stratosphere
 Detectability: At levels as low as 0.01ppm by spectroscopy.
 Principal Structure
O
O O
+ –
This structure is a charged species that arises
from the shift of an electronic pair from one bond to the other.
 Ozone formation in the stratosphere results from the following
reactions:
 OZONE
Step 1: Absorption of UV radiation by molecular oxygen to produce highly reactive
atomic oxygen.
hν

O2 → [O] + [O]
Step 2: Collision of O2 with molecular oxygen to form ozone.
O2 + [O] + M→ O3 + M
` M is a third inert entity (such as N2 or O2), whose availability
essential, N2 takes up excess energy. Both atomic oxygen and ozone are, sometimes,
referred to as ‘Odd oxygen.’

Step 3: As ozone also absorbs UV radiation, the reversal of the Step 1and 2 may occu
as given below.
hν
O3 → O2 + [O]
 Sulfur compounds

 Major: Sulfur dioxide and hydrogen sulfide.

 Sources: Volcanoes (SO2) Sulfur bacteria (H2S) during their
action on dead plants and animals in shallow aquatic
environment. Large amounts of sulfur are thrown into the sea
in the form of sea spray (Sea spray is a spray of water that
forms when ocean waves crash. As a result, salt spray contains
a high concentration of mineral salts) and also from the
biological processes.
 Natural Processes: 50 million tons of sulfur per annum that
makes about 67% of the SOx pollution.
 Global emissions/Ann = 146 million tons per annum.
 Nitrogen Species
 Nitrogen Oxides from Electrochemical Reactions (8 million NOx / Ann.): NO,
NO2, N2O, etc.
 Bacterial processes and the biomass burning(10 million).
 Fundamental Reactions
1200 to 1800oC
. N2 + O2 → 2NO – Heat (Endothermic)
2NO + O2 → 2NO2
 The oxidation of nitric oxide to nitrogen peroxide is also favored by high
temperature around 1100oC. NO2 formed is less than 0.5% of the total
amount of the oxides of nitrogen.
 Formation as a result of photolytic reactions:
UV- Radiation
NO2 → NO + O
NO + O3 (Air) → NO2 + O2
O2 (Air) + O → O3 (Ground level, photochemical smog)
 Hydrocarbons

 Major : Methane and its formation through anaerobic

fermentation in swamps and rain forests, biomass burning, etc.
 Reaction:
Bacteria
2(CH2O) n → nCO2 + nCH4
Carbohydrate
 The quantity of methane added is about 600 million ton per year
out of which the domestic animals contribute about 170 million
tons each year. It has an average life of 3 to 7 years in the
atmosphere. Plants and forests are responsible for the production
of terpene hydrocarbons up to 170 million tons per annum.
 Particulate matter
 The particulate pollutants are composed of small solid particles and
liquid droplets of hazardous substances in air. These pollutants cover
a wide range of chemical composition and include smoke, grit, dust,
fumes, mist, sprays, metallic particles, metallic oxides, etc. These may
be organic or inorganic in nature and are present in the atmosphere in
fairly large amounts to pose air pollution problems to all forms of life
on earth. In the urban areas, the particulate mass may range from 60
to 2000 μg per cubic meter. From the damage point of view, the total
mass load of the particulates is not as important as is their chemical
nature and the size of the particles.
 Polycyclic organic particulates are particularly hazardous as these
may be both carcinogenic and toxic. That is why these are classified as
“Nuisance Particulates” Many inorganic particulates are also placed
in this category. The list of inorganic and organic pollutants is given
below.
 Nuisance particles

Alumina Graphite Pentaerythritol Titanium dioxide

Calcium carbonate Gypsum Plaster of Paris Vegetable oil mists
= Calcium silicate Kaolin Silicon except castor oil,
Cellulose as paper fiber Limestone Silicon carbide cashew nut oil, etc
Cement Magnesite Starch Zinc steara
Emery Marble Sucrose Zinc oxide
Glycerine mist Mineral wool fiber Tin oxide
 Sources of particulates
 Volcanic activity, blowing of dust, sand and mud by wind and spraying
of salt and other solid particles by the seas and the oceans. Natural
sources: 800 to 2000 tons/ annum.
 The particulates exhibit special and highly significant physical
properties.
 Particle Size: This is considered as the most important property of the
particulates. Their size ranges from a diameter of 0.0002μ to 500 μ. The
variation is from the size of a chemical molecule to that of a colloidal
particle.
 Average Life: It varies from a few seconds to several months. It may
depend on their settling rates, which in turn may depend on the density and
the size of the particles and also on the extant of turbulence in the air.
 Surface Area: The particulates usually present large surface area. That is
why they offer good sites for sorption of organic and inorganic matter.
 Optical Properties: The optical properties of particulates such as ability to
scatter light and reduce visibility are important determinants of their effects
on human vision and solar radiation.
 Inorganic pollutants
Particulate pollutants
 Major Sources: Power plants, smelters, mining
operations, metallurgical processes including blast
and other furnaces, mining operations, incomplete
combustion processes, etc. Most of them throw fly
ash and smoke in the atmosphere.
 Available estimates: The fuel combustion from the
stationary sources ( fuel oil, coal, and natural gas,
industrial processes) and miscellaneous sources
(forest fires, structural fires, coal refuse burning,
agricultural burning, etc,) the total particulate
emission amounts to 200 to 450 million tons per
annum.
 Inorganic pollutants
Particulate pollutants
 Smoke: Smoke is mainly composed of carbon particles that are spread in the
atmosphere from the exhausts of the industries, which use coal or petroleum
products as fuel or reducing agents. Apart from industries, other sources are the
transport vehicles, household fires based on coal and wood, etc.
 Other components: Grit, dust, metallic particles, metallic oxides, etc.
 Engines using coal or petroleum products: A major source of carbon particles.
Smoke emitted from motor vehicles: It may also contain lead tetra-ethyl as it is
added to the petrol as an anti-knocking agent. The smoke from automobile exhausts
may also contain volatile lead dihalides, which are the products of combustion and
even the metallic lead.
 The chemical structure of the lead tetra-ethyl is as under:

Pb (C2H5)4

The lead halides are formed as a result of following combustion reaction:

Pb (C2H5)4 +C2H5 Cl2 + C2H5Br2 + O2 → PbCl2 + PbBr2 +PbBrCl + CO2 + H2O
Dichloroethane and dibromoethane
Dichloroethane and dibromoethane are formed from gasoline
hydrocarbons and are called halogenated scavengers.
 Metallurgical Establishments: Carbon in the form of coal or coke as fuel
as well as reducing agent.
 Major examples: Iron and copper industries (Coal as a fuel as well as a
reducing agent in smelting of metallic ores

C + O2 → C O2 + Heat (C as fuel)
C O2 + C → 2CO
Fe O + CO → Fe + CO2
Cu2O + CO → 2Cu + C O2
 As the fuels contain earth minerals, they release many metallic oxides from
the stacks into the atmosphere. These oxides are the major inorganic
pollutants encountered in the atmosphere.
Incomplete Oxidation of the Petroleum
Products:
 C5H12 + 3O2→ 5C + 6H2O (Incomplete oxidation)
 C5H12 + 8O2→ 5CO2 + 6H2O (Complete oxidation)
Burning of Wood and Agricultural Wastes in Houses and Other Places:
Formation of smoke due to emission of un-burnt carbon as smoke

Mentioning of Smoke due to Wars:

Example of Gulf War 1990 - 91 and American-Afghanistan War 2001:
Turning of Kuwaiti oil fields to fire by Iraq
 Estimates: 1991Conference held in London by Greenpiece and Campaign for Nuclear
Disarmament, burning of three million barrels of oil per day would yield 15,000 ton of
black smoke daily. Later, a more detailed report estimated it as 16.000 tons per day,
which was an equivalent of burning of two ton of oil per day. In this report, the daily oil-
storage was assumed to produce 10,000 tons of smoke per day.
 The smoke may be produced as a result of the burning of the organic matter set on fire
after the nuclear explosion. According to an estimate, the smoke emission after the
burning of the cities as a result of a single nuclear explosion could be 20 to 50 million
ton. It could even go up to 150 million ton.
 Dust particles
 The dust particles may emit as a part of the smoke that vents out of
the major industrial establishments. The smaller dust particles are
also called ‘Fly Ash.’ The dust particles and fly ash are the naturally
occurring silicates. These may emerge from the stacks not equipped
with the dust collectors. The dust may also include asbestos particles
released by some industries. Asbestos is a silicate based fibrous
material that exhibits long average life in the environment. The
composition of the fly ash depends on the nature of the fuel burnt in a
combustion unit.

 The dust particles are the finely divided aluminosilicates, which may
be charged. These also include metallic oxides from the burning of
fossil fuels as narrated above. A large number of heavy metals may be
present in dust or smoke as such or in the form of their salts.
 Aerosals
 Aerosol mists are formed wherever acid mists are formed. The mist
may contain the acid droplets or their salts formed as a result of the
neutralization of the acids with basic air pollutants as evident from the
following reactions:

2SO2 + O2 → 2SO3
2SO3 + 2H2O → 2H2SO4
H2SO4 + 2NH3→ (NH4)2 SO4
H2SO4+CaO → CaSO4 + H2O

 Aerosols are the suspensions of finely divided particles in the air. Some
of their natural constituents are dust, pollens, bacteria and viruses.
The size of the aerosol particles may vary from 0.001 to 100 microns.
Mist and the fog are the examples of naturally occurring aerosols.
 LEAD
 Lead is a hazardous substance present in air dust, water wastes or in solid
wastes. That is why it is treated as a priority chemical for control. The lead
may be present in the atmosphere or wastes in the form of metal or its
inorganic salts and also as organic salts

 The metallic lead is used for lining of tanks, pipes and other equipment for
which pliability and corrosion resistance is the major concern on the
production line. Important examples are the manufacture of sulfuric acid,
petroleum refining, halogenation, sulfonation, extraction industries, etc. It is
also used as one of the ingredients of solders, as filler in automobile industry,
as shielding material for X-rays and atomic radiators, etc. It is also used in the
manufacture of tetraethyl lead, paint pigments, electricity storage batteries,
glazes, alloys, etc.

 The exposure may occur during its mining, smelting and refining, welding,
spray coating of metals, etc. The exposure may also occur during work in the
industries producing electrical batteries, lead accumulators and rubber.
 Mercury
 Mercury: Mercury is the only metal that is liquid at room
temperature. It is a silvery grayish mobile liquid that boils at
356 to 357oC. It is a highly hazardous substance present in the
wastes that need immediate attention
Examples of Industries.
 The caustic soda industry uses mercury as cathode for the
electrolysis of brine. Both metallic mercury and its salt
Hg2Cl2 formed as a result of chemical combination
between mercury and chlorine, which is one of the major
products of electrolysis of NaCl.
 The industries involved in the manufacture of control
instruments such as thermometers, switches, barometers,
mercury based laboratory equipment, etc, are the sites
where the workers are exposed to mercury poisoning.
 Chromium
 Chromium is a carcinogenic and hazardous metal
if present in the environment. Being carcinogenic,
it is listed as a priority toxic pollutant. It exists as
metal or in the form of divalent, trivalent or
hexavalent salts in the industries that use
chromium or its salts as raw material. The
examples of the industries where there are the
chances of potential exposure include chrome
plating, aluminium anodizing, leather tanning,
refractories, photographic equipment, etc. The
typical industrial hazards due to chromium occur
because of inhalation of dust and fumes
particularly in the industrial environment.
 Nicotine and Nitrosamines
 Nicotine: Nicotine is an alkaloid whose chemical structure is
given below.
It is a hazardous waste that has been enlisted on priority basis.
Potential exposure to smoking is personal as well social evil.
Nicotine may be taken into the lungs by anyone who smokes with
his own will. He may hand over nicotine and other harmful
compounds to others in the environment in the form of exhaled
smoke. The other contributors may be drugs, insecticides and
tanning industry.

 Nitrosamines: A large number of compounds fall in this

category. The smokers also release these compounds in the
environment. It is the suspected carcinogenic class of organic
compounds that affects the human beings. These are the
components of the priority hazardous wastes.
 Gaseous Pollutants
 Sulfur Dioxide (SO2) and Sulfur Trioxide (SO3): Sulfur dioxide is a
colorless gas with strong suffocating odor. It is soluble in water and
organic solvents. It is a non-inflammable gas.

 Sulfur dioxide is one of the major air pollutants that vents out of many
industries. Its 67%, of course, is contributed by volcanoes and other
natural processes and remaining 33% comes from the anthropogenic
activity. The major anthropogenic sources are combustion of fuels,
coal-fired power stations, transport vehicles, refineries, metallurgical
operations, etc. The annual global emissions from the man-made
sources are 45 million tons of NOx. Out of the man-made sources the
stationary combustion of coal accounts for 74%, industries for 22%,
while, the transportation accounts for 2%. That means the coal-fired
power stations are the major contributors to the man-made emissions
in air
 Sulfur
 Sulfur may be present in the elemental form as an impurity in the ores of a
large number of metals. It extensively occurs in nature in the combined form as
sulfide or pyrite ores. That is why, large amounts of sulfur dioxide is formed
during the processes such as roasting and smelting involved in the metallurgy of
a number of metals and also in the chemical industries such as manufacture of
sulfuric acid. Most of the sulfur dioxide released in the atmosphere is the
feature of the urban areas. The pure sulfur is also burnt to produce sulfur
dioxide in the manufacture of sulfuric acid. A few reactions that occur in the
processes narrated above are given below.
CuFeS2 + 3O2 → Cu O + Fe O + 2 SO2
FeS2 + 3O2 → Fe2O3 + 8 SO2
S + O2 → SO2
 The oxides formed are reduced to metals by coke or coal, which is also a fuel. In
sulfuric acid and fertilizer industries, which use sulfuric acid for the
preparation of ammonium sulfate, super-phosphate, etc. Sulfur dioxide formed
as a result of burning sulfur or pyrites is converted into sulfur trioxide, which is
subsequently dissolved in water to form sulfuric acid. Sometimes, both sulfur
dioxide and sulfur trioxide may vent to atmosphere to cause extensive gaseous
pollution.
 Sulfur dioxide
 Another important industry responsible for polluting the atmosphere with sulfur dioxide is the pulp
and paper industry particularly when the Acid Sulfite Pulping Process accomplishes pulping. In this
process, sulfur dioxide formed at the cooking stage is recovered by the use of an efficient absorption
system yet; small quantities are lost through the vents of the digestion and absorption towers. Most
of the sulfur dioxide that is difficult to control is formed in the waste liquor burning plants.
 Apart from industry, motor vehicles and railway engines are also the major sources of sulfur
dioxide. These, in Pakistan, account for three fourth of atmospheric sulfur dioxide.
 Most of sulfur dioxide released in the atmosphere as a result of burning of liquid and gaseous fuels
and about 80% of the solid fuels exhausts as SOx. Its concentration in the exhaust depends on the
nature of the chemical industry. The concentration of sulfur dioxide in the exhausts is usually from
0.05 to 0.4%, but exhausts from the sulfide ore based metallurgical industries may contain sulfur
dioxide from 5 to 10%.
 Sulfur dioxide is one of the precursors of the acid rains. It is an irritant for eyes, nose, throat and
lungs. Its concentration in the effluent gases depends on the sulfur content of the fuel or on. The
reactions that lead to the formation of acid rain are given below.
SO2 + O2 → 2SO3
SO3 + H2O→H2SO4

 SO3 is thus absorbed by the water vapors if sufficiently present, to form droplets of sulfuric acid that
result in the acid rain. SO2 and SO3 are collectively represented as SOx,
 Sulfur Dioxide and Sulfur
Trioxide
 It may be pointed out here that SO2 is partially oxidized to SO3 in air as a
result of the photochemical and catalytic reactions that involve O3,
hydrocarbons and oxides of nitrogen. These reactions are mainly responsible
for the formation of photochemical smog. The oxides of nitrogen catalyze the
reactions that a chemical technologist comes across in the manufacture of
sulfuric acid by the lead chamber process. It, of course, takes place on soot
dust or in presence of metal oxides. The mechanism is illustrated below.
n H2 O
↑ ↓
n SO2 + nO3 → nSO3 + nO2 nH2SO4 → (H2SO4) n

2nH2O (Aerosol droplets)

↑ ↓
Soot dust
2nSO2 + O2 → 2nSO3 2 n H2SO4 → 2(H2SO4) n
Metal oxide Aerosol droplets
 Hydrogen Sulfide (H2S) and Bivalent
Sulfur Compounds:
 H2S is present in natural gas and other fuel gases as an
impurity. H2S and other odorous compounds such as
dimethyl sulfide, methyl mercaptans, etc, are the major air
contaminants spread in the atmosphere by the pulp and
paper mills based on the Kraft Pulping Process. These
sulfur compounds are formed as a result of the breaking of
the disulfide bonds (─ S ─ S ─ ) of the organic sulfur
compounds present in the material that binds the cellulose
fibers in wood by the cooking liquor composed of Na2S and
Na OH as principal chemicals. In Kraft process, Na2SO4 is
used as a make up chemical. Other sources of H2S are
petroleum refineries, tanneries and mines.
 Oxides of Nitrogen (NOx):
 Like oxides of sulfur, the oxides of nitrogen are generally represented as NOx.
Out of eight known oxides of nitrogen, N2O, NO and NO2 are the potential
primary pollutants. Their background concentrations are 0.25 ppm, 0.1 to 2
ppm and 0.5 to 4 ppm respectively. The global concentration of NOx is 0.03
ppm. The continuous monitoring of the heavy traffic in the urban areas have
revealed that the maximum concentration of NO and NO2 may be 1 to 2 and
o.5 ppm respectively. The major human activity contributing to the level of
these pollutants in air is the combustion of fossil fuels such as wood and other
organic matter, coal, oil, natural gas and gasoline. Thus, the major sources are
automobile exhausts, incinerators, furnace stacks, coal based power plants,
etc. The burning of fossil fuels in air also leads to the formation of NO as a
result of the combination of some nitrogen with oxygen. The quantity of NO
formed depends on the temperature of the flame and the rate of cooling or
quenching of the combustion products as these conditions favor the formation
of NO. The anthropogenic activity adds 5×107 tons of NOx per annum. The
distribution of nitrogen oxides from natural sources in the world is uniform
but that from the anthropogenic sources depends on whether the area under
assessment is urban or rural. In urban areas the concentration of nitrogen
oxides is 10 to 100 times that in the rural areas.
 The average life of NO and NO2 is 4 and 3 days respectively. The most
dangerous out of the nitrogen oxides is nitrogen peroxide. It is a dark
brown gas or fuming liquid with a pungent odor. It is a poisonous gas.
 The reactions involved in the formation of nitric oxide and nitrogen
peroxide have been already discussed under he natural sources. The
combination between nitrogen and oxygen to form NO, being an
endothermic process, is favored by high temperature. Similarly, the
oxidation of NO to NO2 is also favored by high temperature. That is
why NO is usually formed in the combustion chambers of the internal
combustion engines and the transport vehicles claim to be the major
source of oxides of nitrogen as primary pollutants. The immediate
cooling of the combustion products prevents the dissociation of NO.
Thus, low temperature in the combustion chamber translates into less
formation of nitrogen oxides while rapid cooling into their
sustainability.
 Oxides of Nitrogen (NOx)
 The reactions that nitrogen peroxide undergoes after its activation by light are given
below. It, being very reactive, absorbs light in the UV region to undergo photolysis.
398nm
NO2 + hν → NO + O
242nm
O2 + hν → NO + O
O2 + O + M → O3 + M where M is a third body
O3 + NO → NO3 + O2
2NO2 + O3 → N2O5 + O2
 The rainwater washes nitrogen peroxide to produce a mixture of nitric acid and nitrous
acid.
2NO2 + H2O → HNO3 +HNO2
HNO2 + O → HNO3
 In presence of ozone, the oxidation is even more rapid and ultimate end is the formation
of nitric acid.
NO2 + O3 →NO3 + O2
NO2 + NO3 → N2 O5
N2O5 + H2O → 2HNO3
 Concentration Profile NOx:
 The traffic density has been found to be the major determinant of the
concentration of oxides of nitrogen in air. Their concentration profile
has been reported to follow a regular pattern depending on the time of
the day and the traffic density. The level of nitrogen oxides remains
stable before daylight, as there is little traffic on the roads. Their level
starts increasing with the beginning of the traffic (6 to 8 AM) and
elevates to the maximum in the peak traffic hours. The nitrogen
peroxide level drops by mid morning (9 to 10 AM) due to its
photodecomposition of NO2 and the formation of ozone. This, of
course, is preceded by the conversion of more nitric oxide to nitrogen
peroxide due to the strong UV radiations. The net result is the increase
in the concentration of nitrogen peroxide and a drop of NO level to 0.1
ppm. With the onset of the rush of evening traffic (5 to 8PM), the
nitric oxide levels again go up. During night, nitrogen peroxide
concentration increases slightly due to the oxidation of nitric oxide by
ozone.
 Carbon Monoxide
 Carbon Monoxide (CO): Carbon monoxide is a colorless,
odorless and tasteless gas. It is partially soluble in water
and is inflammable in air.
 The total annual emission of CO in the atmosphere is on
global level is 350 million tons per annum. The breakdown
for the natural and man-made sources is 75 and 275
million tons respectively. The USA is the major
contributing country with annual release of 100 tons per
annum. The natural sources include volcanic activity,
natural gas emissions, electrical discharge during storms,
seed germination, marsh gas, production, etc. The man-
made sources are accounted for below.
 Carbon Monoxide
 The transportation accounts for 64% of the man-made component
with a breakdown; motor vehicles 59.2%, aircrafts 2.4%, railroads
0.1% and miscellaneous 2.3%. If considered on the entire global basis,
including the natural sources also, the transport sector accounts for
about 74% of the total CO emissions.
 The second major source includes forest fires and agricultural
burning. Former including the burning of forest debris, crop residues,
bushes, weeds and vegetation is responsible for 7.2 %, while latter for
8.3%. These figures along with other minor contributions make
16.9%.
 The iron and steel industry, petroleum and paper industry collectively
contribute 9.6% of the atmospheric CO and thus qualify as the third
major contributor.
 The atmospheric background of CO is o.1 to 0.12 ppm. The average
concentration of CO in the urban atmospheric air is 55 ppm. It may
reach the level of 100 ppm during the peak traffic hours.
 Carbon monoxide
 Carbon monoxide is formed due to incomplete oxidation of coal
during the process of combustion. That is why it is encountered as a
waste gas in the industries where coal is used as the major fuel. The
examples may be iron and steel and other metallurgical industries,
thermal powerhouses, foundries, fluid catalytic cracking of petroleum
refining, lime kilns, Kraft paper mills, etc. The reactions are as
follows:
2C + O2 → 2CO ----- Incomplete combustion
C +O2 → CO2
CO2 +C → 2CO ----- Reduction of CO2 to CO by C
Heat
2CO2 → 2CO + O2 ---- Thermal decomposition of CO2
 Cabon Monoxide
 These reactions occur in the blast furnace, where metals
are produced by the reduction of their oxides. The
examples of iron and copper are given below.
Fe O + C → Fe + CO
TCu O + C → Cu + CO
 Similarly, the calcinations of limestone produce carbon
dioxide and that after reduction with coke being used as
fuel is converted into carbon monoxide:
CaCO3 → CaO + CO2
CO2 + C → 2CO
 Concentration Profile of CO
 The concentration of CO in a specific area
mainly depends on three factors:

 Source
 Population
 Time of the day
 Carbon Monoxide
 As the automobiles source is the largest contributor to the CO
concentration and the traffic density is a function of population, the
highest ambient concentrations of CO are encountered in the urban
areas. The concentration profile of CO exhibiting variation of
concentration with the variation in the hourly average is shown in Fig.
3.2. The variation in the traffic density expressed in terms of the
hourly traffic count with the change in hours of the day is also plotted
for comparison.
 The average concentrations are reported on 8-hour period basis as the
body absorbs and desorbs CO slowly. At low levels of CO, the values
of time intervals required are from 4 to 12 hours as these intervals are
adequate for the establishment of the equilibrium between the
concentrations of COHb inside the body and the average CO
concentration of the inhaled air.
 The profiles indicate that the average concentrations are the lowest
from 12 PM to 8 AM as in this interval there is the lowest average
traffic density. It increases rapidly with the onset of peak hours and
attains the first maximum around 10 AM and continues this trend
between 10 AM to 12 Noon. It starts increasing after 12 and after
showing small rises and falls it reaches the highest value at 5 PM. This
is due to the increase in the number of vehicles on road for the
business transportation. At 5 PM.
 The people start returning from business and transport of business
goods, etc, the rise may continue. Thus, this is the time of almost
bumper-to-bumper traffic. That is why this time is that of highest
traffic density and thus, of highest CO concentration. The
concentration of CO falls with fall in the traffic density at night and
touches lowest values at the midnight due to the
 Carbon Dioxide (CO2):
 CO2 and water vapors are the major products of combustion of fossil
fuels for the production of energy. About 5300 million tons of carbon
dioxide is added to the atmosphere as result of fuel burning. It is also
vented from a large number of industries such as lime industry, soda
ash industry, alcoholic fermentation industry, etc. The reactions are as
follows:
Heat
CaCO3 → CaO + CO2 (Lime industry)
Limestone Lime
Heat
2NaHCO3 → Na2CO3 + H2O + CO2 (Solvay’s Ammonia Soda
Process)
Yeast
C6H12O6 → 2C2H5OH + 2 CO2
Glucose Ethanol
 Carbon Dioxide
 One of the important industries adding carbon dioxide to the
atmosphere is the thermo-electric power industry based on the
burning of fossil fuels. In the recent past, it was thought that the
hydroelectric power dams were the safest source of electrical energy,
as it did not contribute greenhouse gases to the atmosphere. This
version has, now, undergone revision after the observation that the
dams submerge huge areas of vegetation and thus translate into the
emission of large quantities of carbon dioxide into the atmosphere to
cause greenhouse effect.
 Carbon dioxide is the normal constituent of the atmospheric air. It is
present in the air up to 0.032% %. Its proportion in the air remains
under control due to the entry of its excess in the CO2 cycle in the
Biosphere. Its presence beyond the tolerable control is harmful due to
greenhouse effect as result of which, the earth is undergoing global
warming.
 Organic pollutants
 A large number, A bulk of these compounds is in the respirable range
as their size is about 1μ.
 Important components: Polycyclic aromatic hydrocarbons (PAH). The
PAH and their derivatives have been found to occur in the urban
atmospheres in concentration of about 20 μg per cubic meter (Solid
phases). They are sorbed on the soot particles that consist of several
thousand interconnected crystallites made up of the graphitic platelets. The
soot is usually associated with the metals such as Be, Cd, Cr, Mn, Ni, V
and also the organic compounds.

 Hydrocarbons: Hydrocarbons are the compounds of carbon and

hydrogen. The gaseous hydrocarbons and their oxy derivatives such as
aldehydes and ketones are released in the atmosphere from most of the
boilers and central heating units.
 Organic pollutants
 Methane: Primary importance- major contributors to the global greenhouse effect.
Its concentration in the atmosphere is 1.7 ppm.
 Major human sources: Natural gas processing plants, sewage disposal plants,
biogas production units, etc.
 Anthropogenic activity: It is responsible for about 15% of the total methane
released in the atmosphere. The automobile exhausts are the major contributors to
the anthropogenic atmospheric methane. That is why the Contributions: Petroleum
contributes 55%, coal 3.3%, wood 2.2%, incinerators 28.3%and solvent
evaporation about 11.3% of the total global hydrocarbons.
 The hydrocarbons from the anthropogenic activity are generally found in the
highly populated areas particularly, where the traffic density is high. The
topography and the climatic conditions also contribute significantly to the load
of the ambient hydrocarbons. There are the areas, where maximum damage to
the humans and the plants may be encountered.
 Hydrocarbons in areas with high traffic density: Methane, ethane, ethylene,
acetylene, propane, n-butane, iso-butane, n-pentane, iso-pentane, toluene and m-
xylene. The overall number has been found to be around 20. The concentration of
each of these hydrocarbons is a function of the traffic density, which varies with the
hour of the day.
 Methane
 The chemistry of methane in air involves a strong
role of the hydroxyl free radical. It is produced as
a result of the photolysis of ozone to produce
nascent and reactive oxygen that subsequently
interacts with water vapors. The hydroxyl free
radical which abstracts a hydrogen free radical to
produce a methyl free radical.
 hν
O3 → O2 + O.
O. + H2O → HO . + .OH
CH4 + .OH → CH3 . + H2O
 Free Radicals
 The methyl free radical captures an oxygen
molecule to form a peroxy methyl free radical.
The normal course of peroxy methyl free radical is
to interact with another to liberate oxygen.
CH3. + O2 → CH3 ─ O ─ O.
CH3─ O ─ O. + CH3─ O ─ O. → CH3─ CH3 +2 O2
 Of course, in presence of the nitric oxide pollutant,
the course of reaction changes as follows:
 CH3─ O ─ O. + NO → CH3─ O. + NO2
 Free Radicals
 The net result is the formation of a methoxy free radical.
The reaction is of a general nature. Thus, any alkyl radical
involved will ultimately translate into the formation of an
alkoxy radical RO. The alkoxy free radicals finally form
the carbonyl compounds as follows.
H
|‌ H
H─ C ─ O. + M → C ═ O + MH+
|‌ H
H
 Where M is an accepter molecule
 PAN
 In case the hydrocarbons are higher alkanes, the
course of reactions is the same.
O2N─ O─O
C═O
CH3
PAN (Peroxyacyl Nitrate)
 PAN is formed by the natural photo-oxidation of
plant terpenes but at level well below its toxic limit
of 1 ppm. PAN is highly phototoxic. It causes
extensive leaf damage to the plants.
 Aromatic Compounds
 Aromatic hydrocarbons containing up to three benzene rings are not toxic but their
derivatives such as aldehydes and phenols are highly toxic. Benzene itself, for example, is
a significant air pollutant and thus is worth considering. It is these days being used to
frame lead free patrols. It is not toxic itself but it is transformed into toxic phenol.
 Aromatic Compounds
 The hydrocarbons containing the side chains fair like methane and produce
aldehydes in which benzene ring remains intact and side chain is converted
into the carbonyl species. Thus, toluene, after passing though the series of
reactions, as did methane, will produce benzaldehyde. Benzaldehyde has the
structure as shown below.

Organic Solvents and Asphyxiates:
 Organic solvents find wide applications in different industries. These
are also used in homes for different purposes. Small businessmen such
as dry cleaners, painters, etc, operating even on the cottage scale make
extensive use of organic solvents. That is why these are being produced
in large quantities all over the world. Most of them have serious
repercussions in environmental context.
 The asphyxiates are the gases that are not toxic themselves but when,
present in high concentrations, reduce the percentage of oxygen in the
surrounding air below the normal level and thus make breathing for
the living organism difficult. If the fall in oxygen level is below a
critical limit, death may occur due to the total block of the supply of
oxygen. The examples are argon, methane, hydrogen, carbon
monoxide and nitrogen. The requirement of oxygen to safely expel
carbon dioxide from the blood varies from 100 to 250 liters per person.
The danger is enhanced, when too many people gather in a limited
space without ventilation.
 Viruses and Bacteria
 Viruses: Viruses are the tiny living organisms with size
0.005 micron in diameter. They are actually living DNA or
RNA molecules having structure and make-up of such
nature that they are fully functional as living beings. An
example of such a living cell is Pleuropneumonic like
organisms (PPLO). These cells have the mass of 5× 10–16
and size 0.01 micron in diameter.
 Bacteria: Bacteria are the minute organisms with size of
the order 0.2 micron diameter and length 30 micron. Most
of the pathogenic organisms responsible for infectious
diseases belong to this group of organisms. These are
transmitted through all media. The most dominant is the
air transport.