AIR POLLUTION

AIR POLLUTION
There are five primary pollutants which together contribute more than 20% of
global air pollution.

1. CO
2. NOx (Nitrogen oxides)
3. HC (Hydrocarbon)
4. SOx (Sulphur oxides)
5. Particulates

CO (Carbon mono-oxide)
It is a colorless, odourless and tasteless gas , It is 96.5% as heavy as air and is not
soluble in water.
Incomplete combustion of fuel or C- containing compounds.
2C + O2 2CO2 (complete combustion)
Reaction between CO2 and carbon–containing materials at elevated temps. in
industrial process e.g. in blast furnace.
CO2 + C→ 2CO
Dissociations of CO2 at high temperatures.
CO2 CO + O
• Natural processes that contribute CO in the atmosphere
1.Volcanic action
2.Natural gas emission
3.electrical discharge during storm
4.seed germination
5.marsh-gas production etc.
• The significant contribution is from human activities.
1. Transportations contribution about 64%
2. Misc sources (Agricultural burning , forest fires etc) 16.9 %
3. Industrial processes 9.6 %
Control of CO pollution
Modification of internal contribution engines to reduce the amount of pollutants
formed during fuel combustion.
Development of exhaust system reactors which will complete the combustion
process.
Development substitute fuels for gasoline (Reforming, cracking of crude gasoline).
Development of pollution – free power sources to replace the internal engine.
Use of catalytic converters in two stages helps in eliminating pollutants for exhaust
gases before they are discharged into the atmosphere.
Gasoline containing pb(C2H5)4 is the major source of Pb pollution in the
environment. Pb–free gasoline should be introduced.
The possible approach to CO pollution is a substitute fuel for gasoline . May be
compressed natural gas (CNG) & Liquefied natural gas (LNG).
 NITROGEN OXIDES NOX
NOx represents as composite atmospheric gases, nitric oxides & nitrogen dioxide , which are
primarily involved in air pollution .
NO is colorless , odorless gas
NO2 has a reddish – Brown-color and pungent suffocating odor . The
basic chemical reaction leading to Formation of NO & NO2 are

N2 + O 2 1210-1765 º C 2NO

2NO + O2 2NO2
The 2nd reaction Is also favored at temps. About 1100⁰C

uv NO Air

NO2 sun light (O2) O3

O
O2

The distribution of NOx from natural sources is more or less uniform on a global basic lent man- made
sources varies depending Urban / rural areas . In Urban atmospheres , NOx is 10-100 times greater than
in rural areas.
 NITROGEN OXIDES NOX
The end product in HNO3. A possible mechanism for the formation of HNO3 is show below in
which O3 plays an important role.

O3 + NO2 NO3 + O2
NO3 + NO2 N2O5
N2O5 + H20 2HNO3

1. Before day light NO & NO2 levels remain fruity stable at concentration slightly higher
than the daily minimum .
2. As the traffic rush begins & increases (6-8 am) , the level of NO increases & becomes
maximum.
3. At mid-morning with increased ultraviolet light , the NO2 level increases due to conversion
of NO into NO2.
4. In the evening the NO level again goes up during the evening traffic rush.
5 O3 accumulated during day times, reacts with NO during night with the result that NO2
concentration goes slightly up & O3 level drops.
Busy cities heavy automobile traffic has revealed that the maximum values of NO & NO2
levels are 1-2 and 0.5 ppm, respectively.
 Nitrogen oxides NOx
Sources of NOx pollution :
Natural bacteria action discharges.
Man made source release 50*107 tones of NOx .man made some in combustion of coal,
oil, natural gas & gasoline.
By photo chemical reaction.

Control of NOx pollution :

a) The use of catalytic converts for control of automobile emissions provides for
removals of ( NO)x.
b) Power plants emit about 50-1000 ppm of (NO)x. Such emission can be reduced
to 90% by a two stage combustion process.
(i) The fuel (coal/gas/oil) is fired at a relatively high temp .with a sub-
stoichiometric amount of air. This yield of NO is limited in the absence of excess of O2.
(ii) Fuel burn out is completed at a relatively low temperature in excess air,Under
this condition NO is not favored. A possible approach to NOx removed from stack gas
is the chemical sorption process using H2SO4 solutions or alkaline scrubbing solution
containing Ca(OH)2 & Mg(OH)2.Simultaneously SO2 is also removed. NO is converted
into N2O3 which is easily absorbed.
 Nitrogen oxides NOx

Control of NOx pollution :

NO2 is recycled. Four steps are involved in scrubbing process . Flue gas and NO2
and introduced into an oxidizer.
NO2 +SO2 +H2O H2SO4 +NO

NO & NO2 react to form N2O3 which is scrubbed by H2SO4 in a scrubber.

The cleaned flue gas is released into the atmosphere.
NO2 + NO N2O3
N2O3 + 2H2SO4 2NOHSO4 + H2O
The reaction product is decomposed & the resulting H2SO4 recycled to the scrubber.
2NOHSO4 + ½ O2 +H2O 2H2SO4 + 2NO2

NO2 produces HNO3 in HNO3 reactor.

3NO2 + H2O 2HNO3 +NO
Excess NO2 & NO are recirculated through the oxidizer in first step.
 SULPHUR DIOXIDE SO2

Colorless
gas
Have a pungent odour
Produced from the combination of sulphur-bearing material.
S+O SO2
2SO2 + O2 2S03
SO3 + H2O H2SO4

1. Naturalprocess e.g. volcanoes. Provide SOx pollution

2. Men sources 33%. Fuel combustion, transportation, coal fired power station.

+H2O
SO2 + O2 SO3 + O2 H2SO4 (H2SO4)n

SO2 + 1/2 O2 Soot dust SO3 + H2O H2SO4 (H2SO4)n

Or metal oxide
This gives rise to the phenomenon of acid rain.
 CONTROL
4 possible ways to the removal & control of SOX emissions.
Removal of Sox from flue gases.
Removal of S from fuel before burning.
Uses of low sulphur fuels
Substitution of other energy sources of fuel combustion.

SOx from flue gases can be conveniently eliminated by using chemical scrubbers. The
flue stack are passed through a slurry of limestone, CaCO3, which absorbs SO2 quite
efficiently.
CaCO3 + SO2 + O2 → CaSO4 + CO2
ACID RAIN
Much of the NOx and SOx entering into the atmosphere are converted into HNO3 &
H2SO4
respectively. The detailed photochemical reactions in the atmosphere are summarized:
NO + O3 → NO2 + O2
NO2 + O2 → NO3 + O2
NO2 + NO3 → N2O5
N2O5 + H2O → HNO3

SO2 +1/2 O2 + H2O→H2SO4

EFFECTS OF ACID RAIN

1.Acid Rain damage to buildings materials like marble, limestone, slate, mortar etc.
These materials become pitted and weakened mechanically as the soluble
sulphates are leached out by rainwater.
 2. HNO3 & H2SO4 Combine with HCl emission to generate acidic precipitation
which is widely known as acid rain. Acid rain is now a major problem in some
area.
 Particulates
Small, solid particles and liquid droplets are collectively termed
particulates. These are presents in the atmosphere in fairly large
numbers and sometimes pose a serious air pollution problem.

Sources:
Numerous natural processes injecting particulate matter in the
atmosphere
(800-2000 million tones each year)
Natural Sources :
volcanic eruption
blowing dust & soil by the wind
spraying salt & other solid particles by the seas & oceans.

Man-made Sources :

ning operation

1. Inorganic particulate matter: Metal oxide

They are produced whenever fuels containing metals are
burnt. Thus particulate
Fe3O4 in formed during the combustion of pyrite containing
coal.
 3FeS2 + 8O2 Fe3O4 + 6SO2 CaCO3 CaO + CO2
Pb(C2H5)4 + O2 + C2H4Cl2 + C2H4Br2 CO2 + H2O + PbCl2 +
PbBrCl2+PbBr2

Pb-halides which are volatile & emerge through exhaust system which
condenses to form
particles. This is basic of Pb pollutions in the atmosphere. Due to presence
of H2SO4
& basic air pollutant, such as NH3 OR CaO, Salts are formed
H2SO4 +NH3 (NH4)2SO4
H2SO4 + CaO CaSO4 + H2O

. Organic particulate matter :

These are benzene extracted substances poly cyclic aromatic
hydrocarbon (PAH) are important components of organic particulate
matter because of their carcinogenic nature. Some typical PAH
compounds are Banzo pyrene,.
Most of PAH compounds are absorbed into soot particles.
Control: There are 4 types of equipment used for the control of particulates.
Gravity setting chamber
cyclone collector
wet scrubbers
Electro static precipitators.

Effects of particulates on materials:

Air borne particles including soot, fumes and mist are potentially harmful
for a variety of materials. The extent & type of damage depend upon
chemical composition & physical state of the pollutant. Extensive
damage occurs when the particulates themselves are corrosive or when
they carry toxic substances along with them

Monitoring
Analysis of CO :
(i)Infrared spectrosphotometry. It is based on the principle that CO
strongly absorbs infra-red radiation at certain wavelengths. When IR
radiation is passed through a long cell containing a trace of CO, part
of the energy is absorbed by the gas. At higher CO level more of the
IR energy is absorbed.
 (ii)Gas chromatography : 10 ppm or lower levels of CO can be
conveniently measured by gas chromatography

HYDROCARBON AND PHOTOCHEMICAL SMOG

Natural source
Particularly trees, emit large quantities of hydrocarbons in the
atmosphere.
Methane is the major naturally occurring hydrocarbon emitted into the
atmosphere. It is produced in considerable quantities by bacteria in the
anaerobic decomposition of organic matter in water, sediments and
soil.

2{CH20} bacteria CO2 + CH4

Man-made source
Automobiles are the major sources of hydrocarbon emitted to the
atmosphere.
CONTROL

Hydrocarbons are removed from the atmosphere by several

chemical & photochemical reactions. The end product are CO2, solid
organic particulate matter that settles from the atmosphere or water-
soluble products e.g. acids & aldehydes which are washed by rain .

The majority of the harmful effects of hydrocarbon pollution are not

due to the hydrocarbon themselves, but the products of
photochemical reactions.

An important characteristics of atmosphere which are loaded with

large quantities of automobiles exhausts, trapped by an inversion
layer (stagnant air masses) and at the same time exposed to intense
sunlight, is the formation of photochemical oxidants in the
atmosphere. This gives rise to the phenomenon of photochemical
smog.

Photochemical smog is characterized by brown, hazy fumes which

irritate in eyes & lungs, lead to the cracking of rubber and extensive
damage of plant life.
The probable mechanism of smog forming reactions as follows.
a) Reactive hydrocarbon ( those with C=C group ) from auto exhaust
interact with O3 to from a hydrocarbon free radical RCH2•
b) RCH2• rapidly reacts with O2 to from another free radical RCH2O2•
c) RCH2O2• reacts with NO to produce NO2 & the free radical
RCH2O•
d) This new free radical next interacts with O2 to yield a stable
aldehyde, RCHO, and hydroperoxyl radical, HO2•
e) HO2• then react with another molecule of NO to give NO2 & HO•
f) HO• is extremely reactive & rapidly reacts with a stable hydrocarbon
RCH3 to yield H2O & regenerate the hydrocarbon free radical RCH2• ,
thereby completing cycle.
 Reactive hydrocarbon
O3

RCH3 RCH2• O2 RCH2O2•

NO

NO2 + HO• RCH2O• + NO2

NO O2

HO2•
+
RCHO
Stable aldehyde
Control of hydrocarbon & photochemical pollutants:
O3 & PAN secondary pollutants, so their control ultimately depends on the control of
their primary precursors, hydrocarbons & nitrogen oxides. The control of NOx has been
described earlier & that of HC in connection with the control of auto exhaust emissions.

ROUTE OF PAN FORMATION

RCHO
HO•
RC• = O acyl radical
O2 peroxyacyl radical
RC = O
OO•
NO2
RC = O
OONO2 peroxyacyl nitrate (PAN)
The aldehyde RCHO may initiate another route by interaction with the HO• Radical, leading to the
formation of an acyl radical RC=O, peroxyacyl radical RCOO2 ( by reaction with O2) & finally
peroxyacyl nitrate PAN ( by reaction with NO2). PAN is one of the most potent eye irritants found
smog