TROPOSHERIC REACTIONS

AND POLLUTION
TOPIC 3
 LESSON OUTCOMES FOR TOPIC 3
At the end of this topic, students should be able
to:
1. Define what is a radical and give examples
as well as functions of important
atmospheric radicals.
2. Explain important troposheric reactions
using appropriate equations.
3. Define and explain what is a photochemical
smog.
 Tropospheric Reactions
• Chemical pathways for formation and removal of
gaseous pollutants in the troposphere are
controlled largely by atoms and free radicals,
despite the fact that they are present at low
concentrations.
• Free radical refers to any atom or group of
atoms that has an odd number of electrons and
is capable of independent existence.
• The high reactivity of free radicals is responsible
for their low concentrations in the troposphere
and also for their importance as intermediates in
tropospheric reactions.
 Tropospheric Reactions
• Free radicals are denoted by a ‘dot’ next to the appropriate chemical
symbol – the dot indicating the presence of an unpaired electron in
the outer orbit around the nucleus.

• Examples of free radicals include:

O. oxygen radical
.OH hydroxyl radical
.O  superoxide radical
2
.F  fluoride radical
2

Of these, the most important free radical in the troposphere is the

hydroxyl radical, which is formed continuously by a series of
photochemical reactions.
Hydroxyl Radical
 Hydroxyl Radical
• Hydroxyl in chemistry stands for a molecule consisting
of an oxygen atom and a hydrogen atom connected by a
covalent bond. The neutral form is a hydroxyl radical and
the hydroxyl anion is called a hydroxide.
• Hydroxyl radicals are highly reactive and consequently
short-lived.
• The hydroxyl radical is often referred to as the
"detergent" of the troposphere because it reacts with
many pollutants, often acting as the first step to their
removal.
• They constitute the main pathways for the removal of
most oxidizable molecules in this region of the
atmosphere, including methane (CH4), carbon monoxide
and sulfur dioxide.
 Reactions of the Hydroxyl Radical
• The destruction of formaldehyde by hydroxyl
radical.
HCHO + .OH  HCO + H2O
HCO + O2  HO2 + CO

• The oxidation of methane by hydroxyl radical

CH4 + .OH  CH3 + H2O

CH3 + O2 + M  CH3O2 + M
where M is a third body that acts only to collisionally stabilize the association
complex.
 Production of Hydroxyl Radical
The two main pathways for hydroxyl radical production are:
a) Photolysis (chemical rxn involving photons) of ozone.
hv

O3  O. + O2
O. + H2O  2.OH

b) Photolysis of carbonyl compounds in the presence of

NO
hv
HCHO  CHO. + H.
H. + O2  HO2. (hydroperoxyl radical)
HO2. + NO  NO2 + .OH
Production of Tropospheric ozone
• Can be produced by photolysis of nitrogen
dioxide
NO2 + hv  NO + O
O + O2  O3
This accounts for 90% of the ozone in the
troposphere. The remaining 10% comes
from the stratosphere.
Production of NO2 (Precursor of Ozone)

NO2 is produced by the oxidation of NO

which is largely emitted by combustion
sources
NO + O3  NO2 + O2
Here O3 is used to produce NO2, so a
stationary phase is present for ozone.
Production of NO2 (Precursor of Ozone)

However, in the following overall reaction in

the presence of a reactive hydrocarbon (RH)

RH + 2NO + 2O2  carbonyl + 2NO2 +H2O

NO2 can be produced without consuming ozone.

This disturbs the stationary phase resulting in net
ozone production. RH can be a VOC compound.
 Tropospheric ozone
• The majority of tropospheric ozone formation occurs
when nitrogen oxides (NOx), and volatile organic
compounds (VOCs), such as xylene, react in the
atmosphere in the presence of sunlight.
• NOx and VOCs are called ozone precursors. Motor
vehicle exhaust, industrial emissions, and chemical
solvents are the major anthropogenic sources of these
chemicals
• Tropospheric ozone, or "bad ozone," is an air pollutant
that damages human health, vegetation, and many
common materials.
• Trosposheric ozone is a powerful greenhouse gas as
well as a key ingredient in photochemical smog.
 Tropospheric ozone –Summary
• The natural background levels of tropospheric
ozone plays a beneficial role for the global
ecosystem.
• Ozone is the primary source of hydroxyl radical
(OH.) as well as metastable oxygen atoms.
• The decomposition of many pollutants, such as
carbon monoxide (CO) and methane (CH4), is
initiated by reactions with OH. and metastable
oxygen.
• Thus, tropospheric ozone plays a key role in the
ability of the ecosystem to cleanse itself.
 Tropospheric ozone –Summary

• Ozone is highly toxic

• Harmful effects to crop production
• Harmful effects to forest growth
• Harmful effects to humans
• Damaging effects of direct exposure to
tropospheric ozone outweighs the
beneficial effects.
INDUSTRIAL SMOG/GRAY-AIR SMOG
• Smog – type of air pollution
• The industrial revolution has been a great cause of the
increase in pollutants in the atmosphere over the last
three centuries. Most of the pollution was created from
the burning of coal), cooking and transportation.
• Under suitable conditions, industrial smog occurs when
the smoke and sulfur dioxide produced from burning
coal merges with fog and creates a yellowish-brown-
colored haze close to ground level. Industrial smog
pollutes the air and SO2, its main pollutant causes acid
precipitation which damages the environment.
• Today, Industrial smog is far less common, but the
burning of fossil fuels such as petroleum can create
another atmospheric problem known as photochemical
smog.
 Photochemical smog/Brown Smog
• Photochemical smog was discovered in 1950’s
• A photochemical reaction is any chemical reaction
activated by light.
• Photochemical smog is a mixture of air pollutants
which have been chemically altered into further
noxious compounds (secondary pollutants) by
exposure to sunlight.
• All modern cities have some photochemical smog but
it is much more common in cities with sunny, warm
and dry climates and a great number of motor
vehicles.
• Some of the constituents of smog can also be
carried by the winds far from where they were
formed, inflicting rural regions with the pollutants from
large cities.
 Industrial smog

London

Burning of large amts of coal within a city, releases soot particles

from smoke, sulfur dioxide and other components.
 Photochemical smog

New York City.

A type of vehicular emission from internal combustion engines &
industrial fumes that react in the atmosphere with sunlight.
 Photochemical smog
The main components of photochemical smog are:

• Nitrogen oxides
• Volatile Organic Compounds (VOCs)
• Tropospheric ozone
• PAN (peroxyacylnitrates)
• Aldehydes

All are chemically reactive and are irritating to humans

and other living things, They degrade materials, cause
respiratory problems and illness as well as irritate the
eyes and other mucous membranes.
 VOCs
• Volatile Organic Compounds or VOCs are organic
chemicals that form a gas at room temperature
• Comprise of volatile hydrocarbons and other organic
molecules released into the atmosphere.
• They may have biogenic or anthropogenic sources.
• Biogenic sources include terpenes and isoprenes.
• Anthropogenic sources include butane, toluene, methane,
pentane, propane, ethanol, methanol, formaldehyde and
benzene.
• Gasoline and natural gas are a major source of VOCs.
• VOCs are given off by many types of products including:
paints and lacquers, paint strippers, cleaning supplies,
pesticides, building materials and furnishings, office
equipment, and craft materials like glue and markers.
 VOCs
• Some VOCs are quite dangerous, like benzene,
polycyclic aromatic hydrocarbons (PAHs) and
butadiene.
• Benzene may increase your chances of getting
leukemia.
• PAHs can cause cancer.
• Butadiene is found in gasoline engine exhaust
and cigarette smoke, and can cause cancer too.
• In addition to the health problems, VOCs in the
air can react with ultraviolet light and nitrogen
oxides to form tropospheric ozone.
 PAHs
• PAHs are a class of organic compounds
produced by incomplete combustion or
high-pressure processes.
• Often, PAHs consist of three or more
fused benzene rings containing only
carbon and hydrogen.
• PAHs are solids with low volatility at room
temperature. They are relatively insoluble
in water, and most can be photo-oxidized
and degraded to simpler substances.
 PAN
• PAN (peroxyacylnitrates) is part of smog.
• PAN makes people's eyes hurt and it is
bad for your lungs. It also damages plants.
• Nitrogen dioxide (NO2), oxygen (O2) and
hydrocarbons (unburnt petrol) react in the
presence of sunlight to produce
peroxyacetylnitrate (CH3CO-OO-NO2):

NO2(g) + O2(g) + hydrocarbons + sunlight

----------> CH3CO-OO-NO2(g)
 PHOTOCHEMICAL /BROWN-AIR SMOG
• The formation of photochemical smog begins when exhaust from
morning traffic releases large amounts of VOCs and NO into the
air. NO is converted to reddish NO2 and this is why photochemical
smog is sometimes called brown-air smog.

• In UV light, NOx reacts with VOCs released by trees, motor

vehicles and business to form a mixture of ozone, nitric acid,
aldehydes, peroxyacyl nitrates (PANs) and other secondary
pollutants.

• NO2, O3 and PANs in this chemical brew are called photochemical

oxidants because these damaging chemicals can react with , and
oxidize, certain compounds in the atmosphere or inside our lungs.

• Hotter days lead to higher levels of ozone and other components of

smog.

• All hot cities have some photochemical smog but it is much more
common in cities with sunny, warm and dry climates.
 PHOTOCHEMICAL SMOG FORMATION
The necessary ingredients for photochemical smog formation are (1)
nitrogen oxides, (2) sunlight, and (3) hydrocarbons

• Photochemical smog formation proceeds through a sequence of reactions,

all involving a free radical mechanism.
• Free radicals are generated by photodissociation of nitrogen dioxide, a
process that generates ozone and oxygen atom.

NO2 → NO + O
O + O2 → O3

• Oxygen atoms also react with water to form hydroxyl radicals, which in turn
react with hydrocarbons to form hydrocarbon radicals.
• Hydrocarbon radicals form hydrocarbon peroxides.
• Hydrocarbon peroxides form aldehydes
• Aldehydes form aldehyde peroxides
• Aldehyde peroxides form peroxyacylnitrates (PAN)
 PHOTOCHEMICAL SMOG FORMATION
Certain conditions are required to create photochemical smog
• The time of day is also a very important factor when
considering the amount of photochemical smog.
– 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 start to react
forming nitrogen dioxide or increasing it's concentration .
– As the sunlight becomes stronger later in the day, the
nitrogen dioxide is broken down and it's by-products are
formed.
PHOTOCHEMICAL SMOG FORMATION
• Some environmental factors can affect production of
photochemical smog.

– Precipitation can decrease photochemical smog as

the pollutants are washed out of the atmosphere by
rainfall
– Winds can blow photochemical smog away replacing
it with fresh air. However problems may arise in other
areas
– Temperature changes can change dramatically the
severity of the pollution.