Photochemical Smog

Learning Outcome :
Write equations for the formation of
nitrogen oxides, NO and NO2.
Describe and write equations showing the
role of nitrogen oxides in the formation of
ozone in the troposhere.
 Explain the terms primary pollutants and
secondary pollutants with reference to
the harmful effects of nitrogen oxides and
ozone in the troposhere.

Describe how catalytic converters

reduce the quantities of nitrogen oxides
generated by cars.
Photochemical Smog
The poisonous mixture of smoke, fog, air
and other chemicals such as
- nitrogen oxides,
- volatile organic compounds (VOCs),
- peroxyacyl nitrates (PANs),
- ketones, aldehydes
- ground level ozone
(Topospheric ozone O3)
 Geographical and meterological conditions
for photochemical smog to occur :
1. Sunlight photochemical reaction
2. Warm temperature increase reaction rate
3. Lack of wind accumulate chemicals
4. Hills/ mountain accumulate chemicals
Primary pollutants
Primary pollutants are emitted directly
into the atmosphere from a source such
as combustion chambers of engines or
furnaces.
Examples :

CO, CO2, SO2, NO and unburnt

hydrocarbons.
Secondary pollutants
Secondary pollutants are formed in the
atmosphere by chemical reaction of the
primary pollutants photochemical smog

Examples : O3 (tropospheric ozone), NO2,

H2SO4 and HNO3.
How to form photochemical
smog ?
Chemical Reactions
1. Oxidation of nitrogen gas
Due to high temperature/ pressure,
Triple bond in nitrogen gas can be
broken down and react with oxygen.

N2 (g) + O2 (g) 2 NO (g)

2. Further oxidation of NO

NO gas will be further oxidised to form

NO2

2NO (g) + O2 (g) 2NO2 (g)

3. Photolysis of Nitrogen dioxide

UV light from the Sun will break the

molecule into nitric oxide and radical

NO2 (g) NO + O
4. Formation of ozone, O3

Radical = species with unpaired

electrons, very reactive.
Radical attack the molecule oxygen in the
air to form tropospheric ozone.

O2 (g) + O O3 (g)
5. Formation of other chemicals/
Pollutants

a)With volatile organic compounds (VOCs) or

unburnt hydrocarbons

CH3CH2CH3 + O3 CH2=CHCHO + 2H2O

b) With VOCs and NO2

CxHy + O3 + NO2 CxHyO3NO2

Peroxyacyl nitrates PANs

Effects of Photochemical smog
Ozone can attack the double bonds of the
polymer chain such as natural rubber.
Breaking the chains and forming more
cross-links between chains.
This causes cracking of the rubber.
 Ozone with concentration > 0.15ppm can
cause respiratory problems such as
coughing, wheezing and constriction.
Ozone can turn plant leaves yellowish
and photosynthesis rates are significantly
reduced.
Nitrogen dioxide has similar effects to
ozone on plants and animal health.
 PANs can interfere the enzymes systems
and cell wall metabolism of plants.
It also can cause eye irritation and
respiratory problems.
VOCs are carcinogenic.
Solutions
Catalytic converters in cars

2NO (g) + 2CO (g) N2(g) + 2CO2(g)

2CO (g) + O2 (g) 2CO2 (g)
2CH3(CH2)6CH3 + 25O2
16CO2 (g) + 18H2O (l)
Alternative fuels solar energy
Catalytic converter

Air (N2 & O2) + Fuel NO, CO.

CO2 and
not burnt
Hydroca
rbons
H2O

N2, CO2 and H2O

Catalytic converter
The role of catalytic converter: to remove
the primary pollutants CO, HCs and NO by
catalysing their conversion to CO2, H2O
and N2.
Catalysts inside catalytic converters are
expensive metals : Platinum, palladium and
rhodium coated on the surface of ceramic
honeycomb structures.
 It can be used at temperature up to
1300C.
The honeycomb structure provides a large
surface for the metal catalyts and allows for
a flow of exhaust gases pass through it.
Questions
The usage of motor vehicles has led to an
increase in the concentration of pollutants in the
lower atmosphere. One of the pollutants is
tropospherical ozone, which can lead to the
formation of photochemical smog. Describe with
the aid of chemical equations, how ozone can be
formed by oxides of nitrogen in the
troposphere. State one harmful effect of ozone
towards living organisms. (8%)
Exercise
During a low-level fly-past over the Adelaide Grand Prix
circuit the exhaust gases emitted from an F111 aircraft
were orange in colour. This orange colour may be
attributed to an oxide of nitrogen.
(i) Name this oxide and give its chemical formula (2 marks)
(ii) Explain,with the help of equations, its formation in this
case. ( 4 marks)
(iii) Provide, with equations, two reasons why oxides of
nitrogen are undesirable in the atmosphere. ( 4 marks)