College of Engineering, Architecture and Technology

Name: __________________________________ Course & Year: ______________

Module 7 : Chemistry of Atmosphere

Course Title : Chemistry for Engineers
Course Number : Chemistry Lecture 111
Course Description : This course provides the students with core concept of
chemistry that are important in the practice of
engineering profession.
Total Learning Time : 3 units (3 hours lecture per week)
Pre-requisites : None

Overview:

In this module, it will discuss the major components of Earth’s atmosphere, and its
characteristics. It will further discuss the major pollutants of atmosphere and what can
we do to minimize air pollution.

Learning Outcomes:

At the end of this module, the student should be able to:

1. Have a working knowledge to determine the layer of atmosphere.

2. Have a working knowledge to determine the air pollutants thus the size of particles
makes a difference.
3. Convert into low-level of concentrations of pollutants present in air in terms of ppm or
ppb.

Indicative Content:

This module discusses the following topics: Atmospheric Region; Source of pure gases;
Types of Air pollutants and Determination of concentrations of air pollutants in terms of
part per million (ppm) or part per billion (ppb).

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 College of Engineering, Architecture and Technology
Name: ____________________________________ Date Submitted: __________
Course & Year: _____________________________Rating: __________

Pre-Assessment:

1. Define the following terms:

a) Polluted air
b) Photochemical smog
c) Aerosol

2. Name the three major pollutants and give each source.

3. Describe what a thermal inversion is and explain how can it aggravate the problems
caused by smog.

4. How is an industrial-type smog different from a photochemical smog?

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5. What are the main sources of nitrogen oxides in the atmosphere?

6. What is an aerosol and how does it play a role in the atmosphere?

7. Write the equation for the reaction that occurs when lightning causes nitrogen to
react with oxygen.

8. Describe two sources of carbon monoxide.

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9. What health risks are posed by breathing air contaminated with particulates?

10. Write the chemical equation for the reaction between carbon and oxygen when an
insufficient amount of oxygen is present. What is the name of the product of this
reaction?

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Discussion

In the beginning, there was no molecular oxygen (O2). From its formation roughly 4.5
billion years ago to about 1.5 billion years ago. Earth’s atmosphere was quite different than
it is today. There was gaseous nitrogen (N2), water vapour (H2O), carbon dioxide (CO2),
methane (CH4), and ammonia (NH3). In the beginning, not all life required oxygen and life
was limited to deep in the oceans.

We have just begun our exploration of chemistry. We will focus on air, a precious
commodity that as has become increasingly apparent is at considerable risk. Have we
begun to pollute our atmosphere to such an extent that our health and way of life are
endangered? We will look at our air, the life-sustaining chemical canopy that surrounds
Earth, and address some of the issues related to its composition and our influence on it.

Atmospheric chemistry is a branch of atmospheric science in which the chemistry of

the Earth's atmosphere and that of other planets is studied. It is a multidisciplinary
approach of research and draws on environmental chemistry, physics, meteorology,
computer modeling, oceanography, geology and volcanology and other disciplines.
Research is increasingly connected with other arenas of study such as climatology.

The composition and chemistry of the Earth's atmosphere is of importance for several
reasons, but primarily because of the interactions between the atmosphere and living
organisms. The composition of the Earth's atmosphere changes as result of natural
processes such as volcano emissions, lightning and bombardment by solar particles from
corona. It has also been changed by human activity and some of these changes are
harmful to human health, crops and ecosystems.

Examples of problems which have been addressed by atmospheric chemistry include

acid rain, ozone depletion, photochemical smog, greenhouse gases and global warming.
Atmospheric chemists seek to understand the causes of these problems, and by obtaining
a theoretical understanding of them, allow possible solutions to be tested and the effects
of changes in government policy evaluated.

In the 20th century atmospheric science moved on from studying the composition of
air to a consideration of how the concentrations of trace gases in the atmosphere have
changed over time and the chemical processes which create and destroy compounds in
the air.

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 In the 21st century the focus is now shifting again. Atmospheric chemistry is
increasingly studied as one part of the Earth system. Instead of concentrating on
atmospheric chemistry in isolation the focus is now on seeing it as one part of a single
system with the rest of the atmosphere, biosphere and geosphere.

Atmospheric layers

1. Troposphere - is the lowest layer of Earth's atmosphere, and is also where nearly
all weather conditions take place. It contains approximately 75% of the
atmosphere's mass and 99% of the total mass of water vapor and aerosols.

2. Stratosphere - The stratosphere is the second major atmospheric layer above the
troposphere, extending in altitude from about 8 to 30 miles high. No weather
occurs in the stratosphere. The stratosphere contains over 15% of the total mass of
the atmosphere, and is where the ozone layer is located.

3. Mesosphere - is directly above the stratosphere and below the thermosphere

extends from around 50-85 km above our planet (31-53 miles) possess
temperatures that decrease with height throughout the mesosphere contains strong
zonal winds (east-west), atmospheric tides, planetary waves, and gravity waves.

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4. Thermosphere - is the layer of the Earth's atmosphere directly above the mesosphere
and below the exosphere. Within this layer of the atmosphere, ultraviolet radiation
causes photoionization/photodissociation of molecules, creating ions in the
ionosphere.

5. Exosphere - is the uppermost region of Earth's atmosphere as it gradually fades into

the vacuum of space. Air in the exosphere is extremely thin - in many ways it is
almost the same as the airless void of outer space.

Chemical composition of atmosphere

Nitrogen accounts for 78% of the atmosphere, oxygen 21% and argon 0.9%. Gases like
carbon dioxide, nitrous oxides, methane, and ozone are trace gases that account for about
a tenth of one percent of the atmosphere. Air is nothing but a mixture of a variety of
gasses.

The air in the atmosphere consists of nitrogen, oxygen, which is the life-sustaining
substance for animals and humans, carbon dioxide, water vapor and small amounts of
other elements (argon, neon, etc.).

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 Air is made up of a mixture of gases. There is no chemical formula for air as it is a
mixture of many different compounds with varying percentages thereof. The major
components would be Nitrogen (N₂), Oxygen (O₂), Carbon Dioxide (CO₂), Water (H₂O),
and many others in minute amounts. Air plays a vital role in recycling one of Earth's most
important substances: carbon. Animals and humans also release carbon dioxide into the
air when they breathe. Through a process called photosynthesis, plants extract carbon
dioxide from the air and use it to produce energy.

Air Pollution. "Smog" is a contraction of the words "smoke" and "fog," and was
originally used to describe air pollution caused by coal burning in London. Urban smog is
photochemical because many of the chemicals found in urban air are formed by chemical
reactions driven by sunlight. A heterogeneous mixture is a type of mixture in which the
components can be seen, as there are two or more phases present. One example of a
mixture is air. Air is a homogeneous mixture of the gaseous substances nitrogen, oxygen,
and smaller amounts of other substances.

Before we consider atmospheric pollutants, let’s examine the normal composition of

dry air in more detail. As shown in Table 4-1, nitrogen and oxygen make up 99% of
Earth’s atmosphere. There are lesser amounts of many other gaseous substance.

Composition (by volume)

Gas Percentage ppm
Nitrogen (N2) 78.084 780,840
Oxygen (O2) 20.948 209,480
Argon (Ar) 0.934 9340

Carbon dioxide(CO2) 0.037 370

Neon (Ne) 0.00182 18.2
Helium (He) 0.00052 5.2
Methane (CH4) 0.0002 2

Hydrogen (H2) 0.0001 1

Krypton (Kr) 0.0001 1

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 Carbon monoxide (CO) 0.00001 0.1
Xenon (Xe) 0.000008 0.08
Ozone (O3) 0.000002 0.02
Ammonia (NH3) 0.000001 0.01
Nitrogen dioxide (NO2) 0.0000001 0.001
Sulfur dioxide (SO2) 0.00000002 0.0002

The concentration values in Table 4.1 are listed as percentages and as parts per
million. All of us are familiar with percentages. For instance, in a class composed of 136
females and 64 males, we can easily determine the percentage of female by dividing the
number of females by the total class membership (200) and multiplying by 100 to get
68%. This means that out of every 100 students, there are 68 females. Thus, 68% is 68
parts per hundred.

Many constituents of air are present at concentrations far less than 1%. It gets quite
awkward to deal with such small numbers; for example, neon is present at a level of
0.00182 %. It is easier to express such low-level concentration in parts per
million(ppm) or parts per billion(ppb).

parts per million (ppm): 1 part out of every million parts

parts per billion(ppb): 1 part out of every billion parts

To convert 0.00182% to ppm, we are really converting parts per hundreds to ppm. In
other words, we are asking the following questions: If 0.00182 out of every 100 particles
in the air are Ne atoms, what number would that be out 0f 1,000,000 particles?

A simple proportional equation can be set up as:

0.00182/100 = x/1,000,000
x = 18.2 ppm

This is the same as saying that if we could reach into the air and grab 1,000,000
particles, 18.2 would, on average, be Ne atoms. Of course, we can’t actually have two-
tenths of a neon atom, but this is a statistical average. With a little practice, you should be
easily able to convert among percent, ppm and ppb in either direction.

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Example 1. Conversions between percent, ppm &ppb

a) On a particular humid day, the water vapour concentration in the air

might be 0.85%. How would this concentration of water be expressed
in ppm and ppb?
Solution:

0.85/100 = x/ 1,000,000
x = 8500 ppm

and

0.85/100 = x/1,000,000,000
x = 8,500,000 ppb

By solving the proportional equations above, you can see that 0.85% is the same as
8500 ppm or 8,500,000 ppb.

b) Breathing air that contains 1000ppm of carbon monoxide for about four hours
will probably cause death in most adults. To what percentage of carbon monoxide
does 1000 ppm correspond?

Solution: The ff. equation is another way of stating out of every 1,000,000 particles in air
are CO, (x) of every or100 particles are CO

1000/1,000,000 = x/100
x= 0.1 or 0.1%

In this example, every 100 particles in the air, an average of 0.1 is CO. Of course, we
can’t have 0.1 molecules. To make this statistical average more realistic, we might choose
to convert 0.1% to parts per thousand (ppt) to see that this corresponds to 1 molecule per
thousand.

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Air: A Source of Pure Gases

Before air can be separated into pure nitrogen, oxygen, and other gases by the process
known as fractionation of air, water vapour and carbon dioxide must be removed. This
is usually done by precooling the air to separate ice and frozen carbon dioxide.
Afterward, the air is compressed to more than 100 times normal atmospheric pressure,
cooled to room temperature, and allowed to expand into chamber.

Overcoming the forces that attract molecules to each other requires energy, so as the
gas expands, the molecules lose energy, they slow down, and the gas gets cooler. If the
compression and expansion are repeated many times and controlled properly, the
expanding air cools to the point of liquefaction. Once the air has been liquefied, its pure
gases can be separated by taking advantage of their different boiling points.

When liquid air is allowed to warm up, nitrogen (boiling point -196°C) vaporizes first,
and the liquid becomes more concentrated in oxygen and argon. Further processing
allows separation of high-purity oxygen (bp-183°C) and argon(bp-189°C). The less
abundant gases (neon, bp-246°C; xeon, bp -108°C; and krypton, bp-153°C) are also
separated from liquid air.

Helium (bp-271°C) is not commercially recovered from air because it is cheaper to

isolate it from natural gas, where it is sometimes present in as much as 7% by volume in
the natural gas fields of West Texas.

Oxygen

Most oxygen produced by the fractionation of liquid air is used in steelmaking. Some
is also used in rocket propulsion and in other controlled reactions with oxygen. Liquid
oxygen (LOX) can be stored and shipped at its boiling temperature of -183°C under
atmospheric pressure.

Substances this cold is called cryogens ( from the Greek kryos-” icy cold”). Cryogens
present special hazards, since contact produces instantaneous frostbite and structural
materials such as plastic, rubber gaskets, and some metals become brittle and fracture
easily at these low temperatures. Because liquid oxygen can react explosively with some
substances, contact must be prevented between it and substances that can ignite and burn
in air.

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Nitrogen

Nitrogen gas is so chemically unreactive, it is used as an inert atmosphere for

applications such as welding and other high-temperature metallurgical processes. If air is
not from these processes, unwanted reactions of hot metals with oxygen would occur.
Liquid nitrogen is used in medicine (cryosurgery) for example, in cooling a localized area
of skin prior to removal of a wart or other unsightly or pathogenic tissue.

Because of its low temperature and inertness, liquid nitrogen is also widely used in
frozen food preparation and preservation during transit. Trucks or railroad boxcars with
nitrogen atmosphere present health hazards, since they contain little (if any) oxygen to
support life. Workers must either enter such areas with breathing apparatus or first allow
fresh air to enter.

Nitrogen is an essential element for plants, but they cannot derive it from gaseous
nitrogen. It must first be “fixed”.
Nitrogen fixation – is the process of changing atmosphere nitrogen into compounds
that dissolve in water and can be absorbed through plant roots.

Noble Gases

Approximately 250,000 of argon, the most abundant of the noble gases in the air, are
recovered each year in the US. Most of the argon is used to provide inert atmosphere for
metallurgical processes. It is also used as a filler gas in incandescent light bulbs to
prolong the life of the hot filament. Neon is used in many “neon” signs but argon,
krypton, and xenon are also used for this purpose.

A “neon” sign utilizing several noble gases

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Natural Versus Anthropogenic Air Pollution

Nature pollutes the air on a massive scale with ash, mercury vapour, hydrogen chloride,
and hydrogen sulphide, which released during volcanic eruptions. Carbon dioxide and
chlorinated organic compounds are released during forest and grasslands fires. Many
reactive organic compounds are naturally released into the atmosphere from coniferous
and deciduous plants. We can do little to control these natural events, so our main
concern is pollution that results from human activity, known as anthropogenic pollution.

Human activity, especially in heavily populated (urban) areas, seems to have most
noticeable effects on the quality of the air we breathe. Automobiles, fossil fuel-burning
power plants, smelting plants, other metallurgical plants, and petroleum refineries add
significant quantities of polluting chemicals to the atmosphere.

These atmospheric pollutants especially in the concentration found in urban areas, and
increasingly in rural areas, can cause people to experience such symptoms as burning
eyes, coughing, breathing difficulties, and even death. Air pollution is nothing new.

Air Pollutants: Particles Size Makes a Difference

Air pollutants particles range in size from fly ash particles, which is enough to see,
down to individual molecules, ions, or atoms. Many pollutants are attracted into the water
droplets of fog. Solids and liquid droplets suspended in the atmosphere are collectively
known as particulates. The solids may be metal oxides, soil particles, sea salt, fly ash
from electric generating plants and incinerators, elemental carbon, or even small metal
particles.

Aerosol particles range upward from a diameter of 1(nm) to about 10,000 nm and may
contain as many as a trillion atoms, ions, or small molecules. Particles in the 2000-nm
range are largely responsible for the deterioration of visibility. Aerosol particles are small
enough to remain suspended in the atmosphere for long periods. Such particles are easily
breathable and can cause lung disease. They may also contain mutagenic or carcinogenic
compounds. Because of their relatively large surface area, aerosol particles have great
capacities to absorb and concentrate chemicals on their surfaces.

Liquid aerosols or particles covered with a thin coating of water may absorb air
pollutants into the water, thereby concentrating them and providing a medium in which
reactions may occur. Millions of tons of soot, dust and smoke particles are emitted into
the atmosphere in the US each year. The average suspended particulate concentrations in
the US vary from about 0.00001 g/m³ of air in rural areas to about six times as much in

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urban locations. In heavily polluted areas, concentrations of particulates my increase to
0.002 g/m³.
Particulates in the atmosphere can cool Earth by scattering and partially reflecting
light from the sun. Large volcanic eruptions such as those from Mt. St. Helens in 1980
and Mt. Pinatubo in 1991 had measurable cooling effects on Earth. Particulates and
aerosol are removed naturally from the atmosphere by gravitational settling and by rain
and snow. Industrial emissions of particulates can be prevented by treating the emissions
with one or more of a variety of physical methods such as filtration, centrifugal
separation, and scrubbing.

Another method often used is electrostatic precipitation, which is more than 98%
effective in removing aerosols and dust particulates even smaller than 1µm from exhaust
gases. The effects of an efficient electrostatics precipitator can be quite dramatic.

Factory Smokestack

Electrostatic Precipitator
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Smog

The poisonous mixture of smoke, fog, air, and other chemicals is called smog. The
chemical ingredients of smog vary depending on the source of the pollutants certain
geographical and meteorological conditions exist in nearly every instance of smog.

There must be a period of windlessness so that pollutants can collect without being
dispersed vertically or horizontally. This sets the conditions for a thermal inversion,
which is an abnormal temperature arrangement for air masses. Normally, warmer air is on
the bottom, nearer the warm earth, and this warmer, less dense air rises and transports
most of the pollutants to the upper troposphere, where they dispersed.

In a thermal inversion, the warmer air is on the top, and the cooler, denser air retains
its position nearer Earth. The air becomes stagnated. If the land is bowl shaped
(surrounded by mountains, cliff, or the like), a stagnant air mass can remain in place for
quite sometime. When these atmospheric conditions exist, the pollutants supplied by
combustion in automobile, electric power plants, and industrial plants accumulated to
form smog.

Two General Kinds of Smog

1. Combustion of coal and oil and contains sulphur dioxide mixed with soot, fly ash,
smoke and partially oxidized organic compounds is called Industrial smog or
“London” smog. It was first characterized in and around the city of London,
because of its association with industrial activity, generally diminishes in intensity
and frequency as less coal is burned and more controls are installed on industrial
emissions.The main ingredient in industrial smog is sulphur dioxide. Laboratory

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 experiments have shown that sulphur dioxide increases aerosol formation,
particularly in the presence of mixtures of hydrocarbons and nitrogen oxide.

For example, mixture of 3 ppm hydrocarbon, 1 ppm NO₂, and 0.5 ppm SO₂ at 50%
relative humidity form aerosols that have sulphuric acid (H₂ SO₄) as a major product.
Breathing a sulphuric acid aerosol is very harmful, especially for people suffering from
respiratory diseases such as asthma or emphysema. At a concentration of 5 ppm for 1
hour, this kind of aerosol can cause constriction of bronchial tubes. A level of 10 ppm for
1 hour can cause severe breathing distress.

A notorious case of London smog occurred in 1952. On Thursday, Decenber4 of that

year, a thermal inversion, a particularly foggy night, and freezing temperatures along the
Thames River valley prompted Londoners to stoke their house fires with large amounts
of coal. As was later revealed, low-quality coal had been supplied to the citizenry so that
higher quality coal could be exported. This low-quality coal had a high sulphur content,
which contributed to the resultant problems.

In response to the continuing cold, fires continued to burn throughout the weekend,
adding their smoke and chemical fumes to an increasingly polluted atmosphere. Accounts
of the incidents indicated that no sunlight shone through the smog for miles around the
London as early as Saturday. As the weekend wore on and weather conditions persisted,
things only got worse. Respiratory problems mounted, and people resorted to sleeping in
upright position to ease their breathing.

Hospitals were flooded with people gasping for breath, and more than 100 people died
from respiration-related heart conditions on Monday. Weather condition began to
improve on Tuesday, December 9, but much damage had been done by that time. An
estimated 4000 deaths were initially attributed to the smog, but some recent (2001)
estimates, based on a new assessment of the data, put the total death count, including
belated deaths directly related to the smog at 11,000 to 12,000 people. There have been
other deadly cases of London smog since then, but none has ever matched the magnitude
of the 1952 disaster.

For comparison, consider that the London smog death total from this single incident
almost doubled to combined tolls of the Japanese attack on Pearl Harbour in 1941 and the
collapse of New York City’s World Trade Center twin towers following the terrorist
attacks in 2001. And yet, this is an event that most people have never even heard of.
Pollution may not be as glamorous or newsworthy as war or terrorism, but it can be more
deadly.

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 2. The second type of smog is typical in Los Angeles and other urban centers where
exhaust fumes from internal combustion engines are highly concentrated in the
atmosphere. This predominantly urban smog is called photochemical because
light- sunlight in this instance- is important in initiating several chemical reactions
that together make the smog harmful. Photochemical smog is practically free of
sulphur dioxide but contains substantial amounts of nitrogen oxides, ozones,
oxygenated and ozonated hydrocarbons, and organic peroxide compounds,
together with unreacted hydrocarbons of varying complexity. The automobile is a
direct or indirect source of many of the components of photochemical smog.

Many of the chemical reactions that create photochemical smog take place in aerosol
particles. These reactions produce secondary pollutants- pollutants that are not directly
released from some source but are formed by reactions with other components in the air.
One process by which primary pollutants from the secondary pollutants of photo-
chemical smog begins with the absorption of light energy by a molecule of nitrogen
dioxide. Nitrogen dioxide reacts with light with a wavelength between 280nm and
430nm.

This photodissociation reaction (photo, light; dissociation, breaking apart) produces

nitric oxide and free oxygen atoms that can react with a molecule of oxygen to produce a
molecule of ozone (O₃), which is an important secondary pollutant.

light
NO₂₍g₎ NO₍g₎ + O₍g₎

O₂ ₍g₎ + O₍g₎ O₃₍g₎

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 Atomic oxygen can also react with hydrocarbons to form other chemicals that are toxic
and also impart an odor to the air. On a sunny day, only about 0.2 ppm of nitrogen oxides
and 1 ppm of reactive hydrocarbons are sufficient to initiate these photochemical smog
reactions. The hydrocarbons involved in these reactions come mostly from unburned
petroleum products such as gasoline, and the nitrogen oxides come from the exhausts of
internal combustion engines.

Nitrogen Oxides

There are eight known oxides of nitrogen, three of which are recognized as important
components of the atmosphere: dinitrogen oxide (N₂O), nitric oxide (NO), and nitrogen
dioxide (NO₂). These oxides of nitrogen are collectively known as “NOₓ”. About 97% of
the nitrogen oxides in the atmosphere are naturally produced; only 3% result from human
activity. Certain bacteria can produce N₂O, so this oxide of nitrogen is also commonly
found in the atmosphere.

One of the key culprits in the formation of photochemical smog is NO (nitric oxide), a
colorless but reactive gas. Its nominal concentration in our atmosphere is quite low, and
there are natural source of nitric oxide about which we can do little. It is the
anthropogenic nitric oxide about which we are most concerned, as it is a pollutant over
which we may have some control. Where does this nitric oxide come from? You are
probably aware that an internal combustion engine takes in huge amounts of air as it runs.

This air comprises about 78% nitrogen gas, which is unreactive under normal
circumstances. About 21% of the air sucked into the engine is oxygen gas. Nitrogen and
oxygen do not react with each other at normal air temperature, but the combustion
chamber of an engine may reach temperature as high as 2500°C( the average is probably
around 400-600°C).

Under these conditions, the reaction that forms nitric oxide, which requires heat, takes
place quite readily. The same reaction is triggered in our atmosphere by lightning strikes.

energy
N₂₍g₎ + O₂₍g₎ 2NO₍g₎

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 Nitric oxide itself is a toxic pollutant, and the US Environmental Protection Agency
(EPA) includes it among the primary toxic pollutants it attempt to regulate.
If this nitric oxide is able to escape the exhaust system of the engine, it reacts rapidly
with atmosphere oxygen to produce nitrogen oxide, a reddish brown-highly toxic gas.

energy
2NO₍g₎ + O₂₍g₎ 2NO₂₍g₎
nitrogen dioxide
Almost anyone who has ever observed the skyline of a major city such as Houston,
LA, or Mexico City has seen a reddish-brown haze hanging over the city at times. This
haze is composed largely of nitrogen dioxide, an ocular and respiratory irritant. The EPA
has set the allowable yearly average exposure to all nitrogen oxides at 53ppb. A city or
state whose level of nitrogen oxides exceeds this number is subject to fine and
government intervention.

Normally, the atmospheric concentration of NO₂ is a few ppb or less; most of the
nitrogen oxides formed during lightning storms are washed out by rain. This is one of the
ways nitrogen is made available to plants. Looking at all the sources of oxides of nitrogen
(Table 4-2), it is apparent that combustion process are their primary sources. In the US,
most oxides of nitrogen from sources other than nature are produced from fossil fuel
combustion in vehicles, industry, and power plants.

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 A primary role of nitrogen dioxide as a pollutant is in the formation of the secondary
pollutant ozone and photochemical smog. Nitrogen dioxide can also react with water to
form nitric acid and nitrous acid. This reaction takes place readily in aqueous aerosols,
producing acids that help to stabilize the droplet.

2NO₂₍g₎ + H₂O₍l₎ HNO₃₍aq) + HNO₂₍aq₎

nitric acid nitrous acid
Breathing air containing these aerosol droplets is harmful because of the corrosive
nature of acids. The acids in turn react with ammonia or metallic particles in the
atmosphere to produce nitrate or nitrite salts.

For example:

NH₃₍g) + HNO₃₍aq₎ NH₄ NO₃₍aq₎

ammonia ammonium nitrate

Both acids and the salts stabilize the aerosol particles, which eventually settle from
the air or dissolve in larger raindrops. Nitrogen dioxide, besides causing the formation of
ozone, is a primary cause of haze in urban or industrial atmosphere because of its
participation in the process of aerosol formation.

Table 4-2 Emissions of NO₂ Emissions

(millions of tons)

Source United States

Fossil fuel combustion 66
Biomass burning 1.1

Lightning 3.3
Microbial activity in soil 3.3

Input from the stratosphere 0.3

Total (uncertainty in estimates) 74 (±1)

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Ozone as a pollutant

Ozone consists of three oxygen bound together in a molecule with formula O₃. It is an
allotrope a different molecular form of an oxygen. It has a pungent odor that we often
smell near sparking electrical appliances or after a thunderstorm when rainfall washes
lightning-produced ozone out of the troposphere.

As you have seen, any nitric oxide that escapes into our atmosphere can react with
oxygen to form nitrogen dioxide. Nitrogen dioxide can, under the intensity of the bright
summer Sun, be photochemically degraded into nitric oxide and very reactive oxygen
atoms (O).
As stated earlier, the reaction between these oxygen atoms and oxygen molecules
leads to the formation of ozone and because it is generated by chemical reactions in the
atmosphere, ozone is one of the most difficult pollutants to control.

Ozone concentration,ppm Air Quality Air Quality Descriptor

(8 hr average unless noted) Index Values

0.00 – 0.064 0-50 Good

0.065 – 0.084 51 – 100 Moderate

0.085 – 0.104 101 – 150 Unhealthy for sensitive
group
0.105 – 0.124 151 – 200 Unhealthy

0.125 –(8 hr) – 0.404 (1 hr) 201 - 300 Very unhealthy

Table 4-3 Air Quality Index and Air Quality Descriptors for Ozone

Table 4-3 shows the relationship between the local ozone concentration in the
atmosphere, air quality indices, and air quality descriptors in common use. A period of
unhealthy air may be quite short or quite lengthy depending on weather conditions,
intensity of sunlight, prevailing winds, topography, and the level of nitrogen dioxides
emitted into the air in a given area by automobiles, buses, trucks, trains, ships, industry,
and even lawn mowers.

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Sulfur Dioxide: A Major Primary Pollutant

Sulfur doxide is produced when sulphur or compounds containing sulphur are burned in
air:
S₍s₎ + O₂₍g₎ SO₂₍g₎
Although volcanoes put large amount of SO₂ into the atmosphere annually, human
activities probably account for up to 70% of all emissions on a global basis.

Once formed, SO₂ generally becomes distributed in aerosol droplets, which are
numerous enough to distribute to significantly reduced visibility and can affect both
global and regional climate causing the scattering of sunlight that would otherwise warm
Earth. Emissions of SO₂, cause the mean temperature in US to be about 1° C cooler than
it would be otherwise. Most of the coal burned in US contains sulphur in the form of the
mineral pyrite (FeS₂). The pyrite is oxidized as coal burns, forming SO₂.

4FeS₂₍s₎ + 11O₂₍g₎ 2FeO₃₍s₎ + 8SO₂

Large amounts of coal are burned in this country to generate electricity. A 1000
megawatt (MW) coal-fired generating plant can burn about 700 tons of coal an hour. If
the coal contains 4% sulphur, that equals 56 tons of SO₂ an hour, or 490,560 tons of SO₂
every year. About 800 million tons of coal are burned each year to produce electricity.

Oil- burning electric generating plants can also produce comparable amount of SO₂
because some fuel oils can contain up to 4% of sulfur. The sulphur in the oil is in the
form of compounds in which sulphur atoms are bound to carbon and hydrogen.

Gasoline contains relatively low concentration of sulphur containing compounds. The

removal of sulphur from high sulphur coal is costly and incomplete. One method is to
pulverize the coal to the consistency of talcum powder and remove the pyrite by magnetic
separation.

Reducing the sulfur content of fuel oil is also costly. It involves the formation of
hydrogen sulfite (H₂S) by bubbling hydrogen through the oil in the presence of metal
catalyst. At present, most sulfur-containing coal is burned without prior treatment, and
SO₂ is removed from the exhaust gases. In one method, lime (calcium oxide) reacts with
SO₂ to form calcium sulfite, a solid particulate, which we can be removed from an
exhaust stack by an electrostatic precipitator.

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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 Lime is prepared by heating limestone, which is mainly calcium carbonate.

Heat
CaCO₃₍s₎ CaO₍s₎ + CO₂₍g₎
Limestone Lime

CaO₍s₎ + SO₂₍g₎ CaSO₂₍s₎

Calcium sulfite
Most of the SO₂ that does not get into the atmosphere reacts with oxygen to form
sulphur trioxide (SO₃). This compound has a strong affinity for water and dissolves in
aqueous aerosol particles, forming sulphuric acid, which in turn contributes to acid rain.

SO₃₍g₎ + H₂O₍l) H₂SO₄₍aq₎

Hydrocarbons and Air Pollution

Hydrocarbons enter the atmosphere from both natural sources and human activities.
Certain natural hydrocarbons are produced in large quantities by both coniferous and
deciduous trees. Methane gas (CH₄) is produced by such diverse sources as termites, ants,
rice growing, ruminant animals such as cows, and decay-causing bacteria acting on dead
plants and animals.

Human activities such as the use of industrial solvents, petroleum refining and
distribution, and the release of unburned gasoline and diesel fuel components account for
a large amount of hydrocarbons in the atmosphere. In addition to simpler hydrocarbons,
some larger hydrocarbon molecules pollutant released into the atmosphere, primarily
from motor vehicle exhaust. The greatest danger of some of these pollutants and the
organic, derivatives formed from them is their toxicity.

Although it is practically impossible to control hydrocarbon emission from living plants

and other natural sources, hydrocarbon emissions from automobiles can be controlled. Two
means of control are in use at present. First, the spouts and hoses on gasoline pumps have
been redesigned to prevent gasoline from entering the air. Second, catalytic converters that
reduce emissions of hydrocarbons, Co, and NOₓ are now part of every automobile’s exhaust
system.

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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Carbon Monoxide

Like ozone, carbon monoxide is one of the most difficult pollutants to control. Carbon
monoxide is always produced when carbon or carbon containing compounds are burned
using an insufficient quantity of oxygen,

2C₍s₎ + O₂₍g₎ 2CO₍g₎

Gasoline engine are notorious source of CO. This is because the rapid combustion
inside the combustion chamber does not burn all the carbon to CO₂ before the exhaust
gases are swept out. Modern catalytic converters convert much of this carbon monoxide
to carbon dioxide, but the amounts that are not converted make being near a heavily
travelled street dangerous because of the carbon monoxide concentrations.

At peak traffic times, concentrations as high as 50 ppm occur. In the countryside,

carbon dioxide levels are closer to the global average of 0.1 ppm. The only effective
means of controlling carbon monoxide concentrations in urban air is to control the major
emitters-automobiles. Carbon monoxide is a colorless, odorless gas at room temperature.
Thus, carbon monoxide has no warning properties, because it is a gas, it mixes with air, is
inhaled, and comes in contact with the blood while in the lungs.

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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 The interference of carbon monoxide with oxygen transport in the blood is one of the
best understood kinds of metabolic poisoning. Carbon monoxide, like oxygen, combines
with the haemoglobin in red blood cells. Carbon monoxide exposures are quite common.
In fact low exposures are almost impossible to avoid. This means that some of the
haemoglobin molecules in your blood are always bound to carbon monoxide.

Any organic material that undergoes incomplete combustion will liberate carbon
monoxide. Sources include auto exhausts, smoldering leaves, lighted cigars or cigarettes,
and charcoal burners. A victim of carbon monoxide poisoning can be saved if he or she is
quickly exposed to fresh air or still better, pure oxygen.

In some occupations, it is difficult to avoid long-term exposure to

carbon monoxide

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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A Look Ahead

The quality of the air we breathe can be dramatically affected by the presence of the
air pollutants. Both legislative and technological efforts to reduce the concentrations of
these pollutants have shown positive results, but there is clearly still much to be done.

We don’t normally think of carbon monoxide as a pollutant, but it is having a major

impact on our environment in the form of global warming. Although the concentration
of CO₂ in our atmosphere is low, as is its toxicity, its ability to trap heat the surface of
Earth may be of even more concern than the pollutants.

Lastly, some chemical known as chlorofluorocarbons (CFC’s) are pollutants of major

concern in an entirely different region of our atmosphere. These chemicals, whose effect
at troposphere levels is minimal, play havoc with the protective ozone layer of our
stratosphere.

It is only by staying informed that we can ensure that our air is clean
and clear for centuries to come.

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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 College of Engineering, Architecture and Technology
Name: ____________________________________ Date Submitted: __________
Course & Year: _____________________________Rating: __________

Evaluation:

1. Which of these would not be considered a primary pollutant of our atmosphere-

nitric oxide (NO), carbon monoxide (CO), ozone (O3), hydrocarbons, or sulfur
dioxide (SO2)?

2. Explain how ozone is formed in the troposhere.

3. Place the four reactions below in a sequence that explains the production of ozone
in a typical urban environment,

a) NO2 + sunlight NO + O
b) 2NO + O2 2NO2
c) N2 + O2 2NO
d) O + O2 O3

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

27
4. Name two sources of hydrocarbons in the atmosphere. Which one is more readily
controlled?

5. Describe how ozone can be harmful when it is present in the air we breathe.

6. What are the names of the two regions of the atmosphere? Which one is closer to
the surface of the Earth?

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

28
7. Describe how pure oxygen can be obtained from air.

8. How are the harmful effects of SO2, containing aerosol, NO2 and ozone similar?

9. What happens when a photon of light strike a molecule of NO2? Write the reaction.

10. A human forced to breathe air that is 7% carbon dioxide would probably become
unconscious, suffer brain damage, and die within a few minutes. However, we are
worried that Earth’s atmosphere may approach 400ppm of carbon dioxide within
the next few years. Which of the following statements is correct?
a) 400ppm of carbon dioxide is greater than 7% carbon dioxide
b) 7% is equal to 0.04%
c) 400ppm of carbon dioxide in our air means that percentage of oxygen will drop
by 4%, making it harder to breathe.
d) 400ppm is equal to 40,000ppb.

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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Additional Readings:

http://www.chemistryexplained.com/Ne-Nu/Nuclea html#ixzz6Rqn6EiOh

References:

Brown, Lawrence S. ; Holme, Tom,; Petersen, James F.;Sack, Dorothy,; Gabler, Robert E.;
(2018), Chemistry for Engineering Students, Third Edition, Philippines: C&E Publishing
Inc.

Williams, Linda D. , (2003), Chemistry DeMystified, Second Edition, New York,

Mc Graw Hill

Hoffman, D. C.; Ghiorso, A.; and Seaborg, Glenn T., eds. (2000). The Transuranium
People: An Intimate Glimpse. London: Imperial College Press.

Morrissey, D.; Loveland, W. T.; and Seaborg, Glenn T. (2001). Introductory Nuclear
Chemistry. New York: John Wiley & Sons.

Rydberg, J.; Liljenzin, J.-O.; and Choppin, Gregory R. (2001). Radiochemistry and
Nuclear Chemistry, 3rd edition. Woburn, MA: Butterworth-Heinemann.

Melvin Joesten, John Hogg, (2012). The World of Chemistry, Cengage Learning Asia Pte
Ltd

Askeland, Donald R., Fulay, Pradeep P., Wright, Wendelin J., (2012). Science and
Engineering of Materials, 6th Edition, Cengage Learning Asia Pte Ltd

ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE

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ENGR. MA. INEZ STEPHANY UVAS, CHE,MEE
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