What do you

think why such a

difference is
there?

L-30 UNIT-VI
Photochemical smog

Air Pollution and Control

(Elective - I)

Unit- VI
L-29 Chemistry of air pollution, Chain
reactions of hydrocarbons, nitrogen
oxide, Sulphuric oxides and
intermediates, photochemical smog
formation
L-30 Air pollution indices -aerosols,
fog, smog index.

Smog
The word smog comes from two words:
smoke and fog.
Characterize visible combination of smoke and
fog
Occurs in highly motorised areas and where
inversion conditions prevail in the
atmosphere.
e.g. Los Angeles
It is because of action of sunlight on H-C
(Hydrocarbons) and Nitrogen Oxides (NOx)
emitted from the automobiles

smog
primary
pollutants

volatile
hydrocarbons VOC
nitrogen oxides

secondary
pollutants

ketones,
aldehydes,
PANs,
peroxides,
ozone,

Smog Formation
Sun

Composition of smog

Nitrogen oxides
Ozone
Aldehydes
Unreacted carbon
Particular matter
Peroxyaceyl nitrate (PAN)

Chemical compounds involved

Molecule Name
and Formula

Nitric Oxide, NO
Nitrogen Dioxide,
NO2
Ozone, O3

ThreeTwo-Dimensional
Dimensional
Representation
Representation

Acetaldehyde,
C2H4O (an example of
an Aldehydes)

Peroxyacetyl Nitrate,
C2H3O5N

1,3-Butadiene,
C4H6 (an example of a
volatile organic
hydrocarbon)

smog: variation in day

Early morning traffic increases the emissions

of both nitrogen oxides and VOCs as people
drive to work.
Later in the morning, traffic dies down and
the nitrogen oxides and volatile organic
compounds begin to be react forming nitrogen
dioxide, increasing its concentration.
As the sunlight becomes more intense later in
the day, nitrogen dioxide is broken down and
its by-products form increasing
concentrations of ozone.

At the same time, some of the nitrogen

dioxide can react with the volatile organic
compounds to produce toxic chemicals such
as PAN.
As the sun goes down, the production of
ozone is halted. The ozone that remains in
the atmosphere is then consumed by several
different reactions.

Colour

Nitrogen dioxide is responsible for the brownish

colour of the haze.
The particulates formed and the brown colour of
nitrogen dioxide give the air a dirty, smoggy
appearance.

Los Angeles

Photochemical smog / LA smog

18

Photochemical smog / LA smog

LA
Santiago
Las Vegas

Reaction with NO2

UV light energy is absorbed by NO

It moves into high energy state and becomes
unstable.
Then decomposes in to NO and O (nascent oxygen)
Nascent oxygen quickly reacts with atmospheric
oxygen to form ozone.
This reaction takes place in presence of third body
(X).
If nitric oxide is present it reacts with ozone to form
NO2 and O2

Chemical reactions :NO2 + hv

NO*

O + O2

O3

O3 + NO

NO2 +O2

NO2 behaves like catalyst

NO + O

Aldehydes
Peroxyacyl radical
Acetyl radical

Acetaldehyde

Acetone

Methyl

Methyl

Formyl radical

Acetyl

Factors affecting photochemical

reactions

Light intensity
Hydrocarbon reactivity.
Ratio of H-C to nitric oxide
Presence of light absorbers
Meteorological variables
Height and intensity of atmospheric
inversion

smog: effects

Effects on human health

Headaches
Eyes, nose and throat irritations
Impaired lung function
Coughing and wheezing

PANs cause eyes to water and respiratory

problems, also catalyses formation of
sulphuric acid,
ozone in the troposphere is:

an eye irritant and also irritates respiratory system

causes deterioration of rubber as it breaks C=Cand bleaches dyes
affects leaves and therefore growth/damages crops

reduced visibility
secondary pollutants are toxic to plants
corrosion of building materials by acids
and ozone.

Objective Questions
1.

2.
3.

4.

5.

_________________ is main driving factor

for photochemical smog formation.
NO2 acts as ________________.
Increase in ozone concentration during day
time indicates _____________________
formation.
Cracking of rubber takes place because of
______.
Photochemical smog occurs in highly
_________area.

Theory Questions
Q1. Write detailed short note on Photo-chemistry of
air pollution
OR
Explain Photochemical reactions in detail.
Q2. Explain effects of photochemical smog.

Video Clip-1

Video Clip-2