Republic of the Philippines

CAGAYAN STATE UNIVERSITY

Carig Campus, Tuguegarao City
College of Engineering

Course CHEM111E (Chemistry for Engineers)

Title of the
Unit IV. ENVIRONMENTAL CHEMISTRY – Part 1 (Atmosphere)
Module
At the end of this module, the student shall be able:
Learning a. Describe the atmospheric reactions with the environment.
Objectives b. Explain greenhouse effect.
c. Illustrate the depletion of ozone layer
I. CHEMISTRY OF THE ATMOSPHERE
II. GREENHOUSE EFFECT
Content 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 currently that demand urgent consideration. There are many
environmental problems currently that demand urgent consideration. These traditional issues can be
dealt with from the chemical point of view
There are four environmental segments. These are:
a. Atmosphere - It is the protective blanket of gases, suspended liquids and solids that entirely
envelopes the earth, sustains life on earth, and saves it from the hostile environment of outer
space.
b. Hydrosphere – it consist of all types of water resources such as oceans, seas, rivers, lakes,
streams, reservoirs, polar ice caps and water below the earth’s surface which includes all
surface and ground water.
c. Lithosphere – it is the outer mantle or the soil of the solid earth, consisting of minerals occurring
in the earth’s crust.
d. Biosphere – it is the realm of living organisms and their interactions with the atmosphere,
hydrosphere and lithosphere.
. The relationship between these four environmental segments will be learned in this chapter.

I. THE CHEMISTRY OF THE ATMOSPHERE

A. ATMOSPHERE
The atmosphere is a vital mechanism that seeks to monitor and sustain the temperature of the
Earth, the balance of radiation by the absorption of electromagnetic radiation released by the sun
and re-emitted by the earth, as well as the transfer of heat across the globe It filters unhealthy
tissues that destroy ultraviolet (UV) radiation. It's even warming the world by day and cooling it by
night.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

B. COMPOSITION OF THE ATMOSPHERE

According to NASA, the gases in Earth's atmosphere include:
• 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

C. STRUCTURE OF THE ATMOSPHERE

The atmosphere is divided into four major regions on the basis of temperature profile. The different
atmospheric regions and their characteristics are summarized in the table below.
Altitude Important
Temperature
Region range chemical Description
range (ºC)
(km) species
▪
the layer closest to Earth's surface
▪
Contains half of Earth's atmosphere.
N2, O2, CO2, ▪ Air is warmer near the ground and gets
Troposphere 0–11 15 to -56 H 2O colder higher up.
▪
Nearly all of the water vapor and dust
in the atmosphere are in this layer and
that is why clouds are found here.
▪ Ozone is abundant here and it heats
the atmosphere while also absorbing
harmful radiation from the sun .
Stratosphere 11–50 -56 to -2 O3 ▪ The air here is very dry, and it is about
a thousand times thinner here than it is
at sea level. Because of that, this is
where jet aircraft and weather
balloons fly.
▪ the top of the mesosphere, called the
mesopause, is the coldest part of
Earth's atmosphere
Mesosphere 50–85 -2 to -92 O2+,NO+ ▪ This layer is hard to study. Jets and
balloons don't go high enough, and
satellites and space shuttles orbit too
high.
▪
The thermosphere is considered part of
Earth's atmosphere, but air density is
so low that most of this layer is what is
normally thought of as outer space.
▪ This is where the space shuttles flew
and where the International Space
Station orbits Earth. This is also the
Thermosphere 85 – 500 -92 to 1200 O2+, O+,NO+ layer where the auroras occur. Charged
particles from space collide with atoms
and molecules in the thermosphere,
exciting them into higher states of
energy. The atoms shed this excess
energy by emitting photons of light,
which we see as the colorful Aurora
Borealis and Aurora Australis.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

Has very high

Above ▪
temperature Also known as outer space.
Exosphere thermosph H2, He
due to
ere
radiation

Figure 1.

Figure 1 shows that the temperature and pressure of the Earth's

atmosphere change in function of altitude. Air pressure is decreasing
at altitude. https://www.thinglink.com/scene/343846388821393409

1. Air pressure decreases as we increase altitude. Why?

It is because the pressure of the air can be related to the weight of
the air in a given place. When we raise altitude through the
atmosphere, there is some air underneath us and some air above us.
Yet there is still less air above us than there was at a lower altitude.

2. The air temperature is highest near the surface and decreases

as altitude increases. Why?
It is because variations in the properties of the air reach outward from
the center of the Earth. The sun heats the earth's atmosphere, and part of this heat is heated by the
air near the surface. The hot air is either diffused or convected into the atmosphere. There's even
less air to breathe.

D. EARTH’S RADIATION/ENERGY BALANCE

The sun provides solar energy that is used within the world, even though much of the intensity
of the sun never hits the surface of the earth.

Figure 2.
Shows that the Earth absorbs a part of this energy while the rest is emitted back into the space.
https://www.worldatlas.com/articles/what-is-the-earth-s-energy-budget.html

The earth receives solar energy in the form of short-wave radiation and consumes about 70% of the
sun. Although the Earth constantly receives solar energy or radiation, it will not begin to heat up;
the Earth releases the remaining 30% of solar radiation in the form of long-wave radiation into
space, which allows the Earth to cool down. The proportion of solar radiation that is absorbed and
distributed out into space is also known as Albedo.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

The sum of solar energy per unit time flowing through the unit area at right angles to the path of
the solar beam measured just outside the Earth's atmosphere is known as the solar flux, also known
as the solar constant. The solar radiation hitting the upper Earth's atmosphere is roughly 1340 watts
/ m2•min.
II. GREENHOUSE EFFECT
Sun rays comprise of UV rays, visible light and IR radiations. Ozone layer absorbs damaging UV
radiations and allows visible and IR radiations to pass through it towards the Earth.
The gases in the atmosphere are Carbon dioxide, water vapor, methane, tropospheric ozone, and
chlorofluoro carbon (CFC).
Although carbon dioxide is just a trace gas in the Earth's atmosphere, with a concentration of
approximately 0.033 per cent by volume, it plays a vital role in regulating our environment. The
so-called greenhouse effect explains the absorption of heat above Earth's surface by atmospheric
gases, in particular carbon dioxide. The glass roof of the greenhouse transmits visible sunlight and
collects some of the outgoing infrared (IR) radiation, trapping the heat.
The sinks of CO2 are:
1. Oceans: Which dissolves CO2 as carbonates

2. Biomass: Living green plants use CO2 in photosynthesis

→

These sinks are responsible for only 50% of the expected increase in the CO2 content in
atmosphere.
Carbon dioxide behaves much like a glass cover, except that the raise of temperature in the
greenhouse is mostly due to the reduced passage of air within. Calculations indicate that if the
atmosphere didn’t contain carbon dioxide, the Earth would be 30 °C cooler! Without CO2, the
earth would be as cold as moon.

Figure 3 . http://geologylearn.blogspot.com/2015/07/what-cause-global-warming-effect.html

Green house is a body which allows the short wavelength incoming radiations but does not allow
long wave radiations to escape.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

GREENHOUSE GASES AND THEIR SOURCES

Table 2. Relative contributions of greenhouse gases and their uses
% Contribution
Gases towards Major Sources
greenhouse effect
Fossil fuel combustion, Deforestation,
CO2 49 %
Respiration, Fermentation
Wet lands, Marshy places, Anaerobic
CH4 18%
decomposition of organic wastes, Forest fires
Refrigerant, Aerosol propellent,
CFC 17%
Manufacturing foams
Natural soils, fertilizers, fossil fuel
N2O 6%
combustion, burning of biomass
Photochemical reaction in stratosphere and
O3 8%
diffusion into troposphere
H2O 2%` Vapourisation process
With rapid manufacturing and technical developments, the production of greenhouse gasses is
rising at an unprecedented pace, which has a detrimental impact on the global environment.

III. OZONE LAYER

Ozone (O3) is concentrated in stratosphere at various heights from 16 – 40km at different
latitudes. This layer of atmosphere enveloped by ozone is known as ozone layer. It is also known
as ozonosphere or ozone umbrella.
The thickness of ozone layer is measured in Dobson units (DU). 1 DU = 0.01 mm of the
compressed gas at 0°C and 760mm Hg pressure.
A. Formation of Ozone.
It is formed naturally in stratosphere by the action of ultraviolet radiation.
→ (1)
(2)
Where ‘M’ is a third body (O2 or N 2) which absorbs the excess energy liberated by the
reaction (1) and thereby stabilize the ozone molecule.

B. Advantage of Ozone Layer.

• It acts as protective shield as is absorbs the UV-radiation responsible for DNA
mutation and skin cancer. The UV – radiation may also cause global warming, faster
degradation of plastics, fabrics, etc.

C. Depletion of Ozone Layer

The three main reasons where human activity has influenced the ozone layer are the
following:
1. Direct emission of NOx by supersonic transport. They just fly over the tropopause to
maintain their speed because of low resistance.
2. Use of cholofluorocarbons
3. Increased use of nitrogenous fertilizers.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

If the thickness of ozone layer becomes less than 200 DU, it is known as ozone hole.

D. Mechanism of Ozone Depletion

i. Nitric Oxide converts ozone into O2 and NO2.

ii. NO2 formed reacts with nascent oxygen

iii. NO is regenerated which again reacts with
ozone and the depletion continues by the chain
reaction.

Figure. 4: Ozone depletion by NOx

CFC’s are inert in normal physical conditions.

But under the influence of UV-radiation they
form chloride radical and the following
reactions takes place.
→

Regenerated

The chloride free radical (·Cl) regenerated is

highly stable and one chloride free radical can
break 1 molecule of ozone.

E. Global Action 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
• Then, in 1987, 43 countries signed the Montreal Protocol.
• The Protocol is ratified today by 197 Members.
• Ozone-depleting substances (as mentioned above) have been established for phase-out
and are to be replaced by HFCs (Hydrofluorocarbons).
• With the introduction of the Montreal Protocol, CFC concentrations in the atmosphere
have been undergoing a steady decline since peaking in 1994.
• Efficient Equivalent Chlorine (EECl) levels in the atmosphere had declined by around
10% by 2008.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

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 for crops and marine species.
Many well-documented cases demonstrate significantly how acid rain has ruined farm and timber land
and killed marine species.
Since atmospheric CO2 will not be expected to result in a pH lower than 5.5, sulfur dioxide (SO 2) 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. Often, there are many metals in nature mixed with sulfur. The extraction of
metals also includes the smelting or roasting of ores— that is, the boiling of metal sulfide in the air to
form metal oxides and SO2.
Figure 6. Sulfur dioxide and other air pollutants being released into the atmosphere from a coal-
burning power plant.(Chang, R: Chemistry, 10th ed)
While smelting is a significant source of SO2, much of the SO2
released to the atmosphere is compensated for by 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 aerosol, resulting in heavy precipitation or acid
rain.

Figure 7.https://www.yourarticlelibrary.com/essay/essay-on-air-pollution-sources-causes-effects-and-control/30186

V. PHOTOCHEMICAL SMOG
The term "smog" was coined to describe the mixture of smoke and fog that engulfed London in
the 1950s. Today, though, we are more familiar with the photochemical smog produced by the
reactions of vehicle emissions in the presence of sunlight.

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 Republic of the Philippines
CAGAYAN STATE UNIVERSITY
Carig Campus, Tuguegarao City
College of Engineering

Automotive exhaust consists primarily of NO, CO and various unburned hydrocarbons. These gasses are
called 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.
A. Mechanism of Photochemical smog
Hydrocarbon oxidation
produces various chemical
intermediates, such as
alcohols and carboxylic
acids, which are all less
fragile 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 the
sunlight and decreases
visibility. This interaction
sometimes lets the environment seem hazy. As the mechanism for photochemical smog
formation has been better known, significant attempts have been made to reduce the
build-up of primary contaminants. Most cars are now fitted with catalytic converters
engineered to oxidize CO and unburned hydrocarbons to CO 2 and H 2O and to reduce NO
and NO2 to N2 and O2.

References:

1. Goel, N. & Kumar, S. (2006). Concise Engineering Chemistry (2nd Ed). AITBS Publishers and
Distributors, India. ISBN 81-7473-233-2
2. Chang, Raymond (2010). Chemistry (10th ed). The McGraw-Hill Companies, Inc., 1221 Avenue
of the Americas, New York, NY 10020.

Self-Assessment Activity:

1. Describe the regions of Earth’s Atmosphere.

2. What processes give rise to aurora borealis and aurora australis?
3. Discuss briefly ozone hole and its effect on human health.
4. How to CFCs and nitrogen oxide destroy ozone in the atmosphere?
5. Why is more emphasis placed on the role of carbon dioxide in the greenhouse effect
than that of water?
6. Name the gas that is largely responsible for the acid rain phenomena.
7. List three detrimental effects of acid rain.
8. Suggest ways to minimize the formation of photochemical smog.

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