CAGAYAN STATE UNIVERSITY

Carig Campus
College of Engineering

CHEMISTRY FOR ENGINEERS

CHEM111
UNIT IV
ENVIRONMENTAL CHEMISTRY:
THE ATMOSPHERE
Learning Objectives:
At the end of this unit, the students will be able to:
1. Describe the reactions of the atmosphere with the environment.
2. Explain the greenhouse effect.
3. Adequately illustrate the mechanisms behind the depletion of the ozone layer.
4. Explain how acid rain and photochemical smog are formed.
CONTENTS:
I. The Atmosphere
II. Greenhouse Effect
III. Ozone Layer Depletion
IV. Acid Rain
V. Photochemical Smog

INTRODUCTION
Environmental chemistry is a branch of chemical science which deals with the development,
transport, reactions, effects and fates of chemical species in the water, air, soil, and biological
environment and the effects of human activities on them. It is an interdisciplinary field of research
including environmental engineering, chemistry, physics, biology, biotechnology, life sciences,
medical science, agriculture, and public health.
There are many environmental problems that currently demand urgent consideration. These
traditional issues can be dealt with from the chemical point of view which is why environmental
chemistry is heavily reliant on analytical chemistry as well as on the concepts of various
environmental sciences.
There are four environmental segments being studied under this discipline and we will be discussing
the relationships between them as well as the reactions occurring in them in this unit. These are the:
1. Atmosphere - the protective blanket of gases, suspended liquids, and microscopic solids that
entirely envelopes the earth, helps sustain life on it, and saves it from the hostile environment
of outer space.
2. Hydrosphere – refers to all types of water resources and environments such as the oceans, seas,
rivers, lakes, streams, reservoirs, polar ice caps and the water below the earth’s surface which
includes all surface and ground water.
3. Lithosphere – the outer mantle or the soil of the solid earth, consisting of minerals occurring in
the earth’s crust.
4. Biosphere – the realm of living organisms and their interactions with the atmosphere,
hydrosphere, and lithosphere.

Module 16_Chemistry of the Atmosphere: Page 1 of 10

I. THE ATMOSPHERE
The atmosphere is a vital mechanism that helps regulate and sustain the temperature of the
Earth as well as the transfer of heat across the globe. It is also vital in shielding the earth from
unhealthy levels of radiation by reflecting off a significant portion of the electromagnetic radiation
released by the sun. It filters off the ultraviolet (UV) radiation which harms skin tissues and it even
keeps the world warm by day and cool at night.
A. COMPOSITION
According to studies conducted by NASA, the gases in Earth's atmosphere are comprised of the
following elements and compounds:
▪ Nitrogen — 78 percent
▪ Oxygen — 21 percent
▪ Argon — 0.93 percent
▪ Carbon dioxide — 0.04 percent
▪ Trace amounts of neon, helium, methane, krypton and hydrogen, as well as water vapor
B. STRUCTURE
The atmosphere is divided into four major regions based on temperature profile. The different
atmospheric regions and their characteristics are summarized in the table below.

Table 4A.1.1. The different atmospheric regions

Important
Altitude Temp.
Region Chem. Species Description
Range Range
Present
Troposphere 0 — 11 km -56 — 15ºC N2, O2, CO2, H2O ▪ The layer closest to the
Earth's surface
▪ Contains half of Earth's
atmosphere (by mass).
▪ Air is warmer near the ground
and gets colder the higher up
it gets.
▪ Nearly all of the water vapor
and dust in the entire
atmosphere are in this layer
and that is why clouds are
found here.
Stratosphere 11 — 50 km -2 — -56ºC O3 ▪ Ozone is abundant here. It
helps trap heat while also
absorbing harmful radiation
from the sun.
▪ The air here is very dry, and
it is about a thousand times
thinner than at sea level.
Because of that, this is where
jet aircraft and weather
balloons fly.
Mesosphere 50 — 85 km -2 — -92ºC O2+, NO+ ▪ The top of the mesosphere,
called the mesopause, is the
coldest part of Earth's
atmosphere.
▪ This layer is hard to study; jets
and weather balloons cannot

Module 16_Chemistry of the Atmosphere: Page 2 of 10

 go high enough, and satellites
and space shuttles orbit too
high above it.
Thermosphere 85 — 500 -92 — O2+, O+, NO+ ▪ The thermosphere is
km 1200ºC considered the uppermost
part of Earth's atmosphere,
but air density here is so low
that most of this layer is what
is normally thought of as
outer space.
▪ This is where space
shuttles/satellites fly up to
and where the International
Space Station orbits Earth.
▪ This is the layer where the
auroras occur. Charged
particles from space collide
with the atoms and molecules
in the thermosphere, exciting
them into higher states of
energy. The atoms then shed
this excess energy by emitting
photons/light. This display is
what we see as the colorful
Aurora Borealis/Aurora
Australis.
Exosphere Above the Has very H2, He OUTER SPACE.
thermospher high temp.
e due to
radiation

Figure 4a.1.1 The temperature and pressure of

the Earth's atmosphere as a function of altitude.
https://www.thinglink.com/scene/343846388821393409

1) Why does air pressure decrease as altitude

increases?
This is because the pressure is akin to the weight
of all the air pushing down in a given place. As
we go higher, there is a smaller layer (and
amount) of air pushing down and exerting
pressure.

2) Why is the air temperature highest near the

surface? Why does temperature decrease as
altitude increases?
Aside from the outermost layer of the
atmosphere where sunlight and radiation is
strongest, temperature generally decreases as
you go higher. This is because the farther you
get from the surface of the earth, the
thinner the atmosphere becomes. This means that the higher you go, the less molecules/atoms of
Module 16_Chemistry of the Atmosphere: Page 3 of 10
 air are present, hence lower heat absorption. Moreover, most of the incoming solar radiation is
absorbed by the ground, which in turn heats the tropospheric air by conduction and convection.

C. EARTH’S RADIATION/ENERGY BALANCE

The sun provides solar energy that is used around the world. Much of this energy is filtered
out and never hits the surface of the earth, however, enough still reaches us to provide warmth
and to facilitate important processes.

https://www.worldatlas.com/articles/what-is-the-earth-s-energy-budget.html
Figure 4a.1.2. How the atmosphere affects the behavior of incoming solar radiation

The earth is an oblate spheroid and due to this uneven shape, the different areas around the
earth receive different amounts of energy. The solar energy being received is in the form of short-
wave radiation where ~70% is utilized by the earth. The Earth releases the remaining 30% of solar
radiation in the form of long-wave radiation back into space, which allows the Earth to cool down.
The ratio of the amount of solar radiation that is absorbed vs. that which is distributed out into
space is also known as the Albedo. It so happens that this ratio indicates that the absorption and
release of heat is close to being balanced in a state of radiative equilibrium.
The average solar electromagnetic radiation hitting the earth per unit area is approximated
by a constant called the solar constant or solar flux. It is a flux density which is measured on a
surface perpendicular to the sun’s rays at 1 AU away from the sun (1 AU = the average distance of
the earth from the sun), usually from satellites as they are well outside of the atmosphere. It’s
usually estimated to be 1.366 kW/m2.

II. GREENHOUSE EFFECT

The sun’s rays are comprised of visible light as well as ultraviolet and infrared radiations. The
ozone layer in the stratosphere absorbs damaging UV radiation and allows visible light and IR
radiation to pass through to reach the Earth’s surface.
Although carbon dioxide is just a trace gas in the Earth's atmosphere, with a concentration of
approximately 0.033% by volume, it plays a vital role in regulating our environment and its
temperature. The so-called greenhouse effect is defined as the absorption of heat above the Earth's
surface by certain atmospheric gases, particularly carbon dioxide.
Carbon dioxide behaves much like the glass roof of a greenhouse; although in an actual
greenhouse, the increase in temperature is mostly due to the reduced passage of air within, in the

Module 16_Chemistry of the Atmosphere: Page 4 of 10

atmosphere, CO2 ‘collects’ some of the outgoing IR radiation being reflected by the surface, thereby
trapping the heat within the atmosphere.

Fig. 4a.2.1 The Greenhouse Effect

Greenhouse gases are an essential part of the temperature control of the planet. Calculations
indicate that were the atmosphere be totally devoid of carbon dioxide, the Earth would be 30°C
cooler! Without CO2, the earth would be as cold as the moon. However, these greenhouse gases
must be present in moderation and there are ways for the Earth to decrease the amount of CO2 in
the atmosphere.
These CO2 sinks are:
1. Oceans: any body of water in contact with air dissolves CO2 gas into carbonates (to be
discussed further in future modules).
𝐶𝑂2 + 𝐶𝑎2+ + 2𝑂𝐻 − → 𝐶𝑎𝐶𝑂3 + 𝐻2 𝑂

2. Biomass: living green plants on land and in the water use CO2 in photosynthesis.
ℎ𝑣
6𝐶𝑂2 + 6𝐻2 𝑂 → 𝐶6 𝐻12 𝑂6 + 6𝑂2

These sinks soak up excess CO2. But they are being saturated and at the unprecedented rate that
we are producing CO2, these sinks can only account for ~50% of these expected increases. This rapid
increase in greenhouse gases is proving detrimental to the global environment by causing global
warming.
Table 4a.2.1. Greenhouse gases and their sources
Gases % contribution to Major Sources
greenhouse effect
Fossil fuel combustion, respiration,
CO2 49%
deforestation, fermentation
Wetlands and marshes, anaerobic
CH4 18% decomposition of organic wastes,
forest fires
Refrigerants, aerosol propellants,
CFC 17%
manufacturing (foams)
Natural soils, combustion of fossil
N2O 6%
fuels and biomass, fertilizers
Photochemical reactions in the
O3 8% stratosphere and diffusion into
troposphere

Module 16_Chemistry of the Atmosphere: Page 5 of 10

 H2O 2% Vaporization reactions
.
III. OZONE LAYER DEPLETION
Ozone (O3) is found concentrated in the stratosphere at altitudes from 16–40km (at different
latitudes). This layer of the atmosphere where ozone is abundant is known as the ozone layer. It is
also known as ozonosphere or ozone umbrella.
The ozone layer acts as protective shield around the earth as it absorbs majority of the UV-
radiation responsible for DNA mutations and skin cancer. UV–radiation may also cause global
warming, faster degradation of plastics, fabrics, etc.
The thickness of the ozone layer is measured in Dobson units (DU) where 1DU = 0.01mm of the
compressed ozone gas at 0°C and 760mm Hg (1 atm) pressure.

A. Formation of Ozone
Ozone is formed naturally in the stratosphere through a 2-step process by the action of UV
radiation:
ℎ𝑣,𝜆= 242 𝑛𝑚
𝑂2 → 𝑂+𝑂 (1)
𝑂2 + 𝑂 + 𝑀 → 𝑶𝟑 + 𝑀 (2)
Where ‘M’ is a third body (usually O2 or N2) which ‘participates’ in the reaction by absorbing
the excess energy liberated by reaction (1) and thereby stabilizing the ozone molecule.

B. Thinning of Ozone Layer

If the thickness of the ozone layer becomes less than 200 DU, that area is called an ozone hole.
Human activity has influenced the thickness of the ozone layer mainly through the following ways:
1. Direct emission of NOx by supersonic transport. These transport fly over the tropopause to
maintain their speed because of low air resistance.
2. Use of chlorofluorocarbons (CFCs), HCFCs.
3. Increased use of nitrogenous fertilizers.

C. Mechanism of Ozone Depletion

OZONE DEPLETION BY NOx

i. Nitric Oxide converts ozone into O2
and NO2.
ii. The NO2 formed reacts with nascent
oxygen.
iii. NO, the catalyst molecule, is
regenerated, which will again react
with ozone. The depletion chain
reaction continues.

Module 16_Chemistry of the Atmosphere: Page 6 of 10

 D. Global Actions Against Ozone Depletion
1. Vienna Convention
▪ The convention laid a framework for
global cooperation on arresting ozone
depletion.
▪ 20 nations, including most of the major
CFC producers, signed the Vienna
Convention in 1985
2. Montreal Protocol
▪ In 1987, 43 countries signed the
Montreal Protocol. It is ratified today
by 197 members. OZONE DEPLETION BY CFCs
▪ Ozone-depleting substances (as CFC’s are inert under normal physical
mentioned above) have been declared conditions. But under the influence of UV-
for phase-out and are to be replaced by radiation they form chloride radicals and
HFCs (Hydrofluorocarbons) then by HFC’s. the following reactions take place:
▪ With the introduction of the Montreal ℎ𝑣
Protocol, CFC concentrations in the 𝐶𝐹3 − 𝐶𝑙 → ∙ 𝐶𝐹3 + ∙ 𝐶𝑙
atmosphere have been undergoing a ∙ 𝐶𝑙 + 𝑂3 →∙ 𝐶𝑙𝑂 + 𝑂2
steady decline since peaking in 1994.
∙ 𝐶𝑙𝑂 + 𝑂 → 𝑂2 + ∙ 𝑪𝒍
▪ Efficient Equivalent Chlorine (EECl)
levels in the atmosphere had declined The chloride free radical (·Cl) regenerated
by around 10% by 2008. is highly stable. Note that 1 chloride free
radical can break 1 molecule of ozone.

IV.ACID RAIN
Every year, acid rain does hundreds of millions of dollars’ worth of damage to stone structures
and monuments all around the world. Some environmental chemists use the word "stone leprosy" to
describe the degradation of stone by acid rain. Acid rain is also harmful to crops and marine species.
Many well-documented cases demonstrate how acid rain has significantly ruined farm and timber
land and killed marine species.
Since atmospheric CO2 when dissolved in water is not expected to result in a pH lower than 5.5,
sulfur dioxide (SO2) and, to a lesser degree, auto-emission nitrogen oxides are thought to be
responsible for elevated rainwater acidity. Acid oxides, such as SO2, react with water to create the
related acids.
There are a variety of sources of atmospheric SO2. Nature itself contributes a lot of SO2 in the
form of volcanic eruptions. There are also many metals in nature mixed with sulfur and the extraction
of metals, which involves the smelting or roasting of ores, may form SO2 along with the metal oxides.
While smelting is a significant source of SO2, much of the SO2 released to the atmosphere is from
the combustion of fossil fuels in agriculture, power plants and households. The sulfur content of coal
varies from 0.5 to 5 per cent by bulk, based on the source of the coal.
In the troposphere, SO2 is nearly always oxidized to H2SO4 in the form of aerosols, resulting in
heavy precipitation of acid rain.

Module 16_Chemistry of the Atmosphere: Page 7 of 10

 https://www.yourarticlelibrary.com/essay/essay-on-air-pollution-sources-causes-effects-and-control/30186
Figure 4a.4.1. How acid rain is formed

V. PHOTOCHEMICAL SMOG
The term "smog" was coined to describe the intense air pollution which is a mixture of smoke
and fog. It was originally intended to be used to refer to the pollution problem in London from the
19th to the mid-20th which was a smoky fog that was yellowish/greenish in color and was composed
of NOx, SOx, O3, smoke and other suspended particulates. This type of smog caused respiratory
problems to significant portions of the population.
Because of the adoption of clean air acts worldwide, today we no longer experience this type
of ‘smog’. We are instead more familiar with the photochemical smog which results from the
reactions of vehicle emissions in the presence of sunlight.
Automotive exhaust consists primarily of NO, CO, and various hydrocarbons. These gases are
classified as major pollutants because they set in motion a series of photochemical reactions that
create secondary pollutants. The secondary pollutants — mainly NO2 and O3—are responsible for the
build-up of smog.

Mechanism of Photochemical Smog Formation

The oxidation of hydrocarbons produces various chemical intermediates, such as alcohols and
carboxylic acids, which are all less fragile (less volatile) than the hydrocarbons themselves. These
liquids are gradually reduced into tiny droplets of liquids.
The dispersion of these droplets in the air, called aerosols, disperses sunlight and decreases
visibility. This interaction sometimes makes the environment seem hazy.
As the mechanism for photochemical smog formation has become better known, significant
attempts have been made to reduce the build-up of primary contaminants in the air. Most cars are
now fitted with catalytic converters engineered to oxidize CO and unburned hydrocarbons to CO2
and H2O and to convert NO and NO2 to N2 and O2.

Module 16_Chemistry of the Atmosphere: Page 8 of 10

 CH3C(O)OONO2

ROO-, R is alkyl

Figure 4a.5.1. The formation of photochemical smog and its effects

Self-learning Evaluation 18
1. Describe the layers of the Earth’s Atmosphere.
2. What processes give rise to aurora borealis and aurora australis?
3. How do CFCs and nitrogen oxide destroy ozone in the atmosphere?
4. Why is more emphasis placed on the role of carbon dioxide in the greenhouse effect than that
of water or ozone?
5. Name the gas that is largely responsible for the acid rain phenomena.
6. List three detrimental effects of acid rain.
7. Suggest ways to minimize the formation of photochemical smog.

SUMMARY
The atmosphere is composed mainly of nitrogen and oxygen and ~1% other gases.
Regions of the atmosphere (lowest altitude to highest):
1. Troposphere – layer where we are
2. Stratosphere – where ozone layer exists
3. Mesosphere – contains the mesopause (coldest layer of atmosphere); difficult to study
4. Thermosphere – where the ISS and satellites are located; the aurora displays happen here

▪ Air pressure and temperature both decrease as altitude increases!

▪ Greenhouse effect - the absorption of heat above the Earth's surface by certain atmospheric
gases, particularly carbon dioxide. Necessary for temperature regulation.
▪ Excess CO2 is absorbed by carbon sinks like: bodies of water (oceans) and plants.
▪ Ozone layer (ozonosphere/ozone umbrella) – absorbs harmful UV radiation in the stratosphere.
- Being thinned out due to NOx and CFCs which break down ozone molecules
▪ Acid rain – happens when there are significant amounts of SO2 (and nitrogen oxides) in the air
which when dissolved in water becomes sulfuric acid.
▪ Photochemical smog – happens as a result of secondary pollutants acting as aerosols and diffusing
sunlight, decreasing overall visibility.

Module 16_Chemistry of the Atmosphere: Page 9 of 10

References:
1. Andrews, et. al. An Introduction to Environmental Chemistry, 2nd Ed. Blackwell Science Ltd.
2004.
2. Harrison, Roy. Principles of Environmental Chemistry. The Royal Society of Chemistry.
Cambridge. 2007.
3. Goel, N. & Kumar, S. (2006). Concise Engineering Chemistry (2nd Ed). AITBS Publishers and
Distributors, India. ISBN 81-7473-233-2
4. Manahan, Stanley. Fundamentals of Environmental Chemistry, 2nd Ed. Boca Raton: CRC Press
LLC. 2001.

Module 16_Chemistry of the Atmosphere: Page 10 of 10