Photochemical Smog

WHAT IS PHOTOCHEMICAL SMOG?

Photochemical smog is a type of air pollution that happens when sunlight reacts with certain
chemicals in the air. It is different from the old smog caused by burning coal, which had a lot of
smoke and sulfur. This smog contains chemicals like ozone and nitrogen oxides.
HOW DOES PHOTOCHEMICAL SMOG AFFECT US?
• It reduces visibility, making it hard to see clearly.
• It causes eye irritation and discomfort.
• It can damage rubber and other materials.
• It harms plants and causes a bad smell in the air.
WHEN DOES PHOTOCHEMICAL SMOG OCCUR?
Photochemical smog usually happens on warm, sunny days with light winds and low air movement.
It is more common when the humidity is below 60% and visibility drops below 3 miles. The smog
forms when sunlight breaks down nitrogen dioxide and reacts with other chemicals in the air.
MAIN INGREDIENTS NEEDED FOR PHOTOCHEMICAL SMOG
• Ultraviolet (UV) light from the sun
• Hydrocarbons (pollutants from cars and factories)
• Nitrogen oxides (pollutants from vehicles and industry)
HOW PHOTOCHEMICAL SMOG FORMS
Sunlight causes nitrogen dioxide to break apart, which then reacts with hydrocarbons and other
chemicals. This creates ozone and other harmful substances like organic peroxides. These
chemicals build up and cause the smog.
EFFECTS OF PHOTOCHEMICAL SMOG ON THE ENVIRONMENT
• It produces aerosols (tiny particles) that reduce visibility.
• It causes damage to plants and materials.
• It creates a strong, unpleasant smell.
ADDITIONAL INFORMATION
High levels of ozone in the atmosphere are a sign of photochemical smog. Ozone is created during
sunlight reactions but can also be destroyed by other chemical reactions. Some harmful chemicals
like PAN and ozonides are also formed during these processes.
Chemical Reactions in a Contaminated Atmosphere
1. What Happens in Polluted Air?
In cities, the air often contains harmful chemicals. These chemicals react with each other and cause
problems like eye irritation, less clear air, damage to plants, and even cracking of rubber.
2. Types of Chemicals in the Air
Chemicals in the air can be divided into two groups:
• Natural parts: These are found in large amounts in the air.
• Pollutants: These are usually found in very small amounts.
The difference between the amounts of these two groups can be very big, from 10,000 to 100,000
times.

3. How Reactions Are Studied

Scientists study how these chemicals react by looking at data about how fast reactions happen and
how sunlight affects them. For example, when nitrogen dioxide is hit by ultraviolet light, it changes
into other chemicals like oxygen and nitric oxide.
4. Important Reaction Constants
The table below shows some important numbers (constants) that describe how fast certain
reactions happen and how much energy they need.
Reaction A (Rate Constant) E (Energy in
kcal)
2NO + O2 → 2NO2 8.0 × 109 0 or negative
NO + O3 → NO2 + O2 8.0 × 1011 2.5
2NO2 + O3 → N2O6 + O2 5.9 × 1012 7.0
N3 + H3C → CH2 + Products 3.5 × 105 0.0
O3 + H3C (CH2)3 CH → Products 5.6 × 104 0.0
O3 + HC = CH → Products 3.0 × 107 and 4.5 × 1013 4.8 and —
CH3 + CH3 → C2H6 8.0 × 1011 0.0
CH3 + NO → Products 1.0 × 1010 0.0
CH3 + O2 → CH3O2 — 0.0

5. Units of the Constants

Most of the constants in the table are measured in cubic centimeters per mole per second (cm3
mole-1 s-1). But the reaction of nitric oxide with oxygen is a bit different and uses different units
(cm6 mole-2 s-1).
6. How Sunlight Affects Reactions
Sunlight near the earth’s surface has light waves between 2,900 and 7,000 angstroms (Å). Chemicals
that absorb light in this range can start photochemical reactions. These chemicals work by passing
the absorbed energy to other molecules.
If a chemical is in small amounts, it needs to absorb light strongly to start reactions. If it is in large
amounts, it can absorb light weakly but still cause reactions. These reactions are important for
understanding pollution.
7. Predicting Reactions
Scientists can often predict if a reaction will happen by studying how fast it goes and the energy
involved. If a reaction hasn’t been studied, they use information about energy and heat changes to
guess if it will happen.
The energy and heat data for many chemicals are known and help calculate changes during
reactions. These values are shown in another table (Table 12.2) for chemicals found in polluted air.

Overview of Smog Formation: Smog forms when hydrocarbons and nitrogen oxides (NO)
react in sunlight and still air. This creates oxidants that cause smog.
Photochemical Oxidants in the Atmosphere
Photochemical oxidants are chemicals made by sunlight in the air. These include ozone, hydrogen
peroxide (H2O2), organic peroxides (ROOR'), hydroperoxides (ROOH), and peroxyacyl nitrates
(PAN).
Role of Nitrogen Dioxide (NO2)
Nitrogen dioxide is not a strong photochemical oxidant. It is about 15% as effective as ozone in
changing iodide to iodine. Scientists adjust measurements because of positive interference of NO2.
Sulphur Dioxide and Its Effect
Sulphur dioxide (SO2) reacts with ozone (O3) in the air. This reaction causes a problem called
negative interference, which means it affects how scientists measure pollution. Because of this,
they need to correct their measurements to get accurate results.
What is PAN and Related Chemicals?
• PAN stands for peroxyacetyl nitrate. It is made in the air from chemicals like alkenes and
nitrogen oxides (NOx). PAN and similar chemicals like PBN can irritate the eyes and are strong
oxidants, which means they can cause chemical changes in the air. Other related chemicals
include:
• Peroxypropionyl nitrate (PPN)
• Peracetic acid
• Acetylperoxide
• Butyl hydroperoxide
• Tert-butylhydroperoxide
These chemicals are important in polluted air and help form smog.
How Pollution Changes During the Day
• Pollution levels change at different times of the day. Here is what happens:
• Right after sunrise, the amount of nitrogen monoxide (NO) drops quickly.
• At the same time, nitrogen dioxide (NO2) levels go up and reach a peak.
• During midday, NO levels stay very low.
• Aldehydes and oxidants increase during midday.
• Total hydrocarbons are highest in the morning but go down as the day goes on.
Why These Changes Happen
These changes happen because sunlight causes chemical reactions in the air. For example, NO
reacts with oxygen and other chemicals to form NO2 and oxidants. This makes the levels of
different pollutants go up and down during the day.
Hydrocarbons are high in the morning but decrease because they react with other chemicals when
sunlight is strong.
Summary of Smog Formation
The process of smog forming is complicated. Scientists explain it using examples of chemical
reactions that happen in the air. These examples help us understand how pollution changes during
the day, even if the exact details are not fully known.
Reactivity of Hydrocarbons
• Hydrocarbons react in smog formation. Some hydrocarbons are more reactive than others.
Knowing which hydrocarbons react more helps in controlling smog. Less reactive hydrocarbons,
like propane, can cause smog far away from where they are released.
• Hydrocarbon reactivity means how easily hydrocarbons react with other chemicals. Methane is
the least reactive gas and lasts a long time in the air (more than 10 days). It has a reactivity value
of 1.0. Methane is very common in the atmosphere.
• Some other hydrocarbons react much faster than methane. For example, β-pinene (from pine
trees) reacts about 9,000 times faster, and d-limonene (from orange peel) reacts about 19,000
times faster.
• Hydrocarbons are grouped into five classes (I to V) based on how reactive they are with hydroxyl
radicals (OH·). Class I is the least reactive, and Class V is the most reactive.
Reactivity Classes and Examples
Class I: Reactivity less than 10, lasts more than 10 days. Example: Methane.
Class II: Reactivity 10–100, lasts 24 hours to 10 days. Examples: Carbon monoxide (CO), acetylene,
ethane.
Class III: Reactivity 100–1000, lasts 2.4 to 24 hours. Examples: Benzene, propane, n-butane,
isopentane, methyl ethyl ketone, toluene, n-propylbenzene, ethene, n-hexane, ethylbenzene.
Class IV: Reactivity 1,000–10,000, lasts 15 minutes to 2.4 hours. Examples: p-xylene, p-
ethyltoluene, o-ethyltoluene, o-xylene, methyl isobutyl ketone, m-ethyltoluene, m-xylene,
trimethylbenzenes, propene, cis-2-butene, β-pinene, 1,3-butadiene.
Class V: Reactivity greater than 10,000, lasts less than 15 minutes. Examples: 2-methyl-2-butene,
2,4-dimethyl-2-butene, d-limonene.

Inorganic Products from Smog

Smog produces two main types of inorganic products: sulphates and nitrates. These come from
sulphur and nitrogen oxides in the air. They can cause acid rain, damage buildings, reduce visibility,
and harm health.
The process of turning sulphur dioxide (SO2) into sulphates is slow in clean air but happens faster
in smoggy conditions. During heavy smog, oxidation rates can be 5% to 10% per hour, which is
much faster than normal.
This fast reaction can create very high amounts of sulphates, making air pollution worse.
How Smog Oxidizes Sulphur Dioxide
Smog contains many oxidants that react with sulphur dioxide (SO2). These include ozone (O3),
nitrogen oxides (NO3, N2O5), and reactive radicals like HO·, HOO·, O, RO·, and ROO·.
The main reactions are:
SO2 + O (from O, RO·, ROO·) → SO3 → H2SO4 (sulphates)
Another important reaction is when HO· adds to SO2 to form a reactive species that can react
further to make sulphates or other sulphur and nitrogen compounds.
HO· + SO2 → HOSOO·
What is HO· and Its Role in Smog
HO· (hydroxyl radical) is a very reactive chemical found in the air. It is usually present at low levels
but can be higher in smoggy air. HO· reacts with sulfur dioxide (SO2) and other chemicals to form
harmful sulfur compounds in the atmosphere.
Fast Reaction of H2S with HO·
Hydrogen sulfide (H2S) reacts quickly with HO·. Normally, H2S lasts about half a day in the air, but
in smog, it breaks down much faster because of this reaction.

Formation of Nitrates and Nitric Acid in Smog

In smog, nitrogen compounds like N2O5 react with water to form nitric acid. Nitric acid can also
form when nitrogen oxides (NO and NO2) react with water or get absorbed by tiny droplets in the
air. Nitric acid then reacts with ammonia to make ammonium nitrate, a type of salt.
Other Nitrate Salts
Besides ammonium nitrate, other nitrate salts can form in smog. These salts can cause damage to
plants, animals, and materials.

Harmful Effects of Smog on Health and Materials

Smog harms human health by causing coughing, wheezing, and irritation in the lungs and eyes. It
also damages materials like rubber, which can crack and age faster when exposed to smog. Smog
affects plants and the atmosphere negatively as well.
Ozone’s Effect on Rubber
Ozone, a harmful gas in smog, attacks natural rubber by breaking its chemical bonds. This causes
the rubber to crack and become weak. Because of this, cracking rubber is used as a test to detect
ozone in the air.
Chemical Reaction of Ozone with Rubber
The reaction happens when ozone breaks the double bonds in rubber molecules. This breaks the
rubber into smaller parts, making it weaker and damaged.
[H - C = C - C - C - H]n + O3 → R - C - OH + H3C - C - R'
(Rubber polymer reacts with ozone to form smaller molecules)
Smog Particles and Reduced Visibility
Smog creates tiny particles called aerosols that make the air hazy and reduce how far we can see.
These particles form when small molecules join together during smog-forming chemical reactions.
Oxygen-Containing Chemicals in Smog
Many smog reactions involve breaking down hydrocarbons (compounds made of hydrogen and
carbon). This leads to the formation of oxygen-containing chemicals, which make up most of the
smog.
What Are Smog Aerosols?
Smog aerosols are tiny particles that form when gases in the air condense on small existing particles.
These particles often have a liquid droplet with a solid core inside. They come from sources like
pollution and can affect the air quality.
What Do Smog Aerosols Contain?
Smog aerosols contain different chemicals such as alcohols, aldehydes, ketones, organic acids,
esters, and organic nitrates. These chemicals come from pollution and can harm the environment.
How Do Smog Aerosols Affect Plants?
Smog can harm plants in many ways. The main harmful chemicals are ozone, PAN (Peroxyacetyl
Nitrate), and nitrogen oxides. PAN is especially harmful because it attacks young leaves, causing
damage like "bronzing" and "glazing" on the leaves. Even small amounts of PAN (0.02 to 0.05 ppm)
can damage plants.
Why Is PAN Dangerous?
PAN damages important proteins in plants by reacting with them. It is usually found in low
amounts, but it can still cause harm. Nitrogen oxides are also present in smog but are less harmful
to plants compared to PAN.
What Are Alkyl Hydroperoxides?
Alkyl hydroperoxides are chemicals that form in smoggy air. They can damage DNA, which may
cause genetic problems. These chemicals form when alkyl peroxy radicals react with hydroperoxy
radicals in the air.
Testing Hydroperoxides
Scientists have tested different hydroperoxides (methyl, ethyl, n-propyl, and n-butyl) and found
they might cause mutations in certain bacteria. This means they could be harmful, so we should be
careful.
Ozone and Plant Damage
Ozone is the biggest threat to plants from smog. Even small amounts of ozone (about 0.06 ppm)
can reduce how well plants make food through photosynthesis. This can slow down plant growth,
even if the plants don’t show visible damage.

Effects of Photochemical Oxidants on Humans

1. What are PAN and Ozone?
PAN (Peroxy Acyl Nitrate) and ozone are harmful chemicals in the air. They irritate the eyes and
cause tearing (lachrymation). They also affect the lungs and breathing.
2. Exposure to Ozone and Health Risks:
Breathing 50 parts per million (ppm) of ozone for several hours can cause serious lung problems,
including fluid buildup (pulmonary edema) and can be deadly.
3. Effects of NO2 and NOx:
NO2 causes a brown haze and irritation in the nose and eyes. NOx gases cause chronic diseases
affecting the heart, lungs, and eyes.
4. Ozone Irritation Levels:
Low ozone levels irritate the nose and throat, causing headaches, cough, chest pain, and difficulty
breathing. Exposure to 0.2 ppm causes no harm, but 0.3 ppm is the level where irritation starts.
Exposure to 1.0 to 3.0 ppm for two hours causes fatigue and poor coordination.
5. Harm from Aromatic Hydrocarbons:
Aromatic hydrocarbons in smog irritate the mucous membranes and cause injury to the trachea
(windpipe).
6. Peroxy Benzoyl Nitrate (PBN):
PBN is a secondary pollutant found in polluted air. It irritates the eyes and causes tearing.

Effects of Photochemical Oxidants on Plants

1. PAN and NOx Damage to Plants:
PAN and NOx are produced in the air and harm plants by attacking young leaves. They cause
"bronzing" and "glazing" on leaf surfaces.
2. Photochemical Smog Effects:
Smog produces brown hazy fumes that crack rubber and damage plants. Exposure to 0.02 to 0.05
ppm PAN causes serious damage to vegetation.
3. Damage to Plant Proteins:
PAN damages sulph hydryl groups in plant proteins, which are important for plant health.
4. Ozone as a Toxic Oxidant:
Ozone is very harmful to plants. It causes bleached or spotted leaves, especially on mature leaves.
It also causes diseases like white pine tip burn.
5. Early Aging and Leaf Damage:
Smog containing ozone and PAN causes plants to age faster and lose leaves early.
6. Injuries to Various Crops:
Even low smog levels (0.01 ppm) can harm petunia, lettuce, pinto bean, citrus, salad crops, and
coniferous trees. PAN damages many plants like beets, spinach, celery, pepper, lettuce, alfalfa,
aster, and primrose.
7. Effects on Forest Trees:
PAN and NO cause death in forest trees by stopping photosynthesis and increasing water loss
from leaves.
8. How Pollutants Harm Plants:
These pollutants destroy leaf cells and shoots, interfere with the plant’s metabolism, and reduce
growth.
9. Ozone and PAN Block Photosynthesis:
Ozone and PAN form smog that blocks sunlight, reducing the plant’s ability to make food. This
harms vegetables like radish, carrot, tobacco, and carnation.
10. Harmful Chemicals in Smog
Smog contains harmful chemicals called sulphates and nitrates. These come from sulfur
compounds like SO2 and H2S, and nitrogen oxides like NO2, N2O3, and N2O5. These chemicals
are toxic and can harm plants, crops, and animals.

Effects of Photochemical Oxidants on Materials

1. What is Weathering?
Weathering means materials get damaged over time. Scientists now know that photochemical
pollutants in smog cause much of this damage. Smoke, fog, dust, mist, and soot in smog reduce
visibility and cause metals, stones, paper, rubber, leather, and painted surfaces to break down or
corrode.
2. How Polymers Are Affected
Polymers are long chains of molecules found in materials like rubber and textiles. Ozone in the air
attacks these chains, breaking them and making the materials weaker and less stretchy. This
happens especially in materials with double bonds, like olefins.
3. Ozone Damages Rubber
Even small amounts of ozone can break the chains in rubber. This makes rubber less elastic and
more brittle. When rubber is stretched and exposed to ozone levels between 0.01 and 0.02 ppm,
cracks can form if the rubber is stretched 2 to 3%.
4. Protecting Rubber from Ozone
Rubber can be protected by coating it with a mix of rubber and ozone called ozonide. This stops
ozone from getting inside. Also, special chemicals called anti-ozonants are added to rubber to
prevent damage, but these are expensive.
5. Damage to Textile Fabrics
Photochemical pollutants also harm fabrics made from cotton, nylon, terrycot, and polyester.
Ozone exposure causes damage to these fabrics. This problem happens in many cities, especially
those with lots of sunshine.
6. Smog Problems in Cities
Cities like Los Angeles have serious smog problems because of many vehicles and pollution
sources. The city's spread-out design and lots of sunshine make it easier for smog and pollutants
to build up.
7. Health Effects of Smog
Smog caused serious health problems in cities like Tokyo, New York, Rome, and Sydney in 1970. It
led to diseases like asthma and bronchitis spreading quickly.
8. Tokyo-Yokohama Asthma
After World War II, American soldiers in Yokohama, Japan, suffered from asthma caused by smog.
They also had emphysema, a lung disease caused by damage to tiny air sacs in the lungs. This
damage made it hard to breathe and sometimes caused death.

Control of Photochemical Pollutants

Photochemical pollutants like ozone and PAN are formed from primary pollutants such as nitrogen
oxides (NOx) and hydrocarbons. To reduce these pollutants, different methods are used to control
hydrocarbon emissions from sources like factories and vehicles.
1. Incineration Method
This method burns hydrocarbons in a flame to turn them into carbon dioxide (CO2) and water.
Sometimes, a catalyst is used after the burner to help the reaction happen at a lower temperature.
This method is efficient and costs less fuel, but the catalyst can sometimes get poisoned during the
process.
2. Adsorption Method
Exhaust gases pass through a bed of activated carbon, which traps hydrocarbon vapors on its surface.
These trapped hydrocarbons stay there until they are removed by passing steam through the carbon.
The hydrocarbons then turn into liquids that can be reused.
3. Absorption Method
In this method, a liquid absorbs dissolved hydrocarbons from exhaust gases. The exhaust gases pass
through a scrubbing liquid that traps the hydrocarbons. This process usually happens in tall towers
where the liquid and gases come into close contact.
4. Condensation Method
This method cools the exhaust gases to a low temperature so that gaseous hydrocarbons turn into
liquids. These liquids are then collected and reused.
Controlling Hydrocarbons from Vehicles
Controlling hydrocarbon emissions from cars is more difficult. Special catalysts are used to convert
carbon monoxide (CO) and hydrocarbons into carbon dioxide (CO2) and water. Other catalysts help
convert nitrogen oxides (NOx) into harmless nitrogen gas (N2).
Final Products of Combustion
The goal is to convert harmful hydrocarbons and carbon monoxide into safe carbon dioxide and
water through combustion.
Future Developments
New methods are being developed to better convert and use smog-forming gases and hydrocarbons
to reduce pollution.