Lecture 5

04/09/23
Lecture# 05
Free Radicals
Free radicals are highly reactive chemical species (atoms, molecules and
ions) that have one unpaired electron. They are unstable as there is a
tendency for unpaired electrons to pair up and so the free radicals react
very quickly.
Radicals can be formed when a covalent bond is broken by energy

supplied by UV light. Due to their reactivity, they are able to cause chain
reactions, as they often react to produce other free radicals.
Role of free radicals in the atmosphere
Free radicals play a very important role in the chemistry of all regions of the atmosphere:
Ozone Depletion: The most well-known example of free radicals in the atmosphere is the destruction of ozone (O3)
in the ozone layer. Chlorofluorocarbons (CFCs) and other ozone-depleting substances release chlorine and bromine
free radicals when they are broken down by ultraviolet (UV) radiation in the upper atmosphere. These free radicals
catalytically destroy ozone molecules, leading to the thinning of the ozone layer. This thinning allows more harmful
UV radiation to reach the Earth's surface, which can have detrimental effects on human health and the environment.
Removal of Air Pollutants: Free radicals are involved in various chemical reactions in the atmosphere, including
those that control the lifetimes of gases and the composition of the atmosphere. For example, the hydroxyl radical
(OH•) is often referred to as the "detergent of the atmosphere" because it reacts with volatile organic compounds
(VOCs) and carbon monoxide (CO) and helps remove these atmospheric pollutants.
Natural Sources: Free radicals can also be generated by natural processes, such as lightning strikes, forest fires, and
volcanic eruptions. These natural sources release various radicals into the atmosphere, which can have complex
effects on atmospheric chemistry.
Combustion Processes: Free radicals are produced during combustion processes, such as those in car engines and
industrial facilities. These radicals can affect the formation of pollutants, including nitrogen oxides and particulate
matter.
Photochemical Smog
• Photochemical smog is a brownish-gray haze caused by the action of solar ultraviolet
radiation on atmosphere polluted with hydrocarbons and oxides of nitrogen.
• It contains anthropogenic air pollutants, mainly ozone, nitric acid, and organic
compounds, which are trapped near the ground by temperature inversion.
• These pollutants can affect human health and cause damage to plants. Photochemical
smog often has an unpleasant odour due to some of its gaseous components.
• The term smog (not to be confused with photochemical smog) is commonly used to
represent a near-ground haze made of a combination of smoke and fog rather than
ozone, nitric acid, and organic compounds. Smog can happen both during the day and at
night, but photochemical smog only happens in the presence of sunlight.
• Photochemical smog appears to be initiated by nitrogen oxides that are emitted into the
air as pollutants mainly from internal combustion engines.
There are different chemical reactions involved in the formation of
photochemical smog:
1. NOx reacts with oxygen (O2) in the presence of sunlight to form nitrogen
dioxide (NO2):
NO + O2 + sunlight → NO2
2. One of the most critical reactions in photochemical smog is the formation of

ground-level ozone (O3). Ozone is produced when NO2 reacts with oxygen
atoms and other molecules:
NO2 + sunlight → NO + O (oxygen atom) O + O2 → O3 (ozone)
3. VOCs, like hydrocarbons, react with oxygen and sunlight to form peroxyacyl
nitrates (PANs) and other reactive compounds:
VOC + O2 + sunlight → PANs and other compounds
Summer Photochemical Smog
• Summer photochemical smog typically results in the classic brownish haze
associated with smog. The combination of sunlight, high temperatures, and
emissions of NOx and VOCs leads to the production of ground-level ozone
(O3),PAN and other secondary pollutants.
• Cities with a geography that does not allow proper dispersal of emissions by
wind and helps the smoke get trapped by extreme weather conditions
experience summer smog.
• The abundance of sunlight and high temperatures during the summer speeds up
chemical reactions in the atmosphere, which, mingled with humidity, creates
dense smog.
• Coastal cities surrounded by hills or mountain are prime candidates for summer
smog.
Winter Photochemical Smog
• Winter smog is essentially created by the excessive use of fossil fuels to heat up homes and buildings.
• The winter photochemical smog also known as the "London-type smog" or "sulfurous smog“.
• Winter photochemical smog forms during extreme weather conditions, particularly during the height of
winter. This is because during extremely cold conditions, populations of cities which have a large number
of hearth-heated homes use coal or other combustibles that generate considerable amounts of smoke
and pollutants. These air pollutants appear at the lower levels in the atmosphere. The cold and moist air
retains the emissions for a longer time through the chemical reactions that take place at a slower rate.
• The primary components of winter photochemical smog are sulfur dioxide (SO2), particulate matter, and
fog or mist. Unlike summer photochemical smog, this type does not contain significant amounts of
ozone or PAN.
• London-type smog appears as a dense, grayish mixture of smoke, fog, and suspended particles. It can
reduce visibility and create a choking sensation.
• Cities boxed in by surrounding higher elevations, which experience heavy snowfalls, face smog regularly.
Effects of Photochemical Smog
• Harmful Air Quality: Photochemical smog reduces air quality and can lead to
respiratory problems, eye irritation, and other health issues in humans. It is
particularly harmful to individuals with pre-existing respiratory conditions.
• Environmental Impact: It can damage vegetation, especially in urban areas.
Ozone, a major component of photochemical smog, can harm plants by
interfering with their ability to photosynthesize. The acidic nature of the
smog can also cause environmental damage and structural decay of
buildings.
• Visibility Reduction: Photochemical smog reduces visibility due to the
scattering and absorption of light by the smog particles, making distant
objects less visible.

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04/09/23

Radicals can be formed when a covalent bond is broken by energy

2. One of the most critical reactions in photochemical smog is the formation of

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