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Subject Chemistry

Paper No and Title 4: Environmental Chemistry

Module No and Title 1, Atmosphere

Module Tag CHE_P4_M1

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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
2.1. What is ‘Atmosphere’?
2.2. Significance of the Atmosphere
2.3. Composition of the Atmosphere
3. Evolution of the Atmosphere
3.1. Primitive or First Atmosphere
3.2. Reducing or Second Atmosphere
3.3. Oxidizing or Present Day Atmosphere
4. Structure of the Atmosphere and vertical temperature
4.1. Troposphere
4.2. Stratosphere
4.3. Mesosphere
4.4. Thermosphere
4.5. Exosphere
5. Heat budget of the earth’s atmosphere
5.1 Energy budget
5.2 Earth’s energy imbalance
5.3 Natural greenhouse effect
5.4 Climate sensitivity and forcing

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1. Learning Outcomes
After studying this module, you shall be able to:

• Differentiate between air and atmosphere

• Know the functions and composition of atmosphere
• Identify the layered structure of atmosphere
• Learn about the importance of each layer for human activity
• Evaluate the effect of human activities on the atmosphere

2. Introduction

2.1. What is ‘Atmosphere’?

The thick blanket of air which envelopes our planet and helps sustain life is called ‘the
atmosphere’. Atmosphere behaves as a protecting shield for all life on Earth, making it unique in
the solar system. The atmospheric gases which are used in respiration and photosynthesis are
called ‘air’.

The atmosphere of earthcontains mixture of gases which are forced to be maintainednear the
earth’s surface by gravity. An increase in altitude will decrease the density of atmosphere.
Maximumatmosphereis located close to the surface, within 16 kilometres. Though the atmosphere
extends into outer space and there is no distinct border between them, but an imaginary line
called the Kármán Line which is approximately at the height of 100 km iscalled as the boundary
of Earth’s atmosphere.

2.2. Significance of the Atmosphere

The atmosphere protects life on earth by serving the following functions:

• Absorbs the energetic ultraviolet radiation while allow thepassing of important visible
radiations.
• Keeps the earth’s surface warm through heat retention, making possible a comfortable
mean temperature of ±15°C
• Prevents excessive heating of surface of the earth at day and excessive cooling at night
thereby reducing the temperature variations
• Contains nitrogen, oxygen and carbon dioxide gases essential for plant growth and for
respiration
• It protects the surface of earth and all life existing on earth from small meteorites that
heat up in the atmosphere due to friction
• Serves an integral part in the bio-geo chemical cycles of C, N, O, P and S
• Helps in flow of energy and water vapours through dynamic processes of air flow
• Helps in radio communication
• Helps in movement of air crafts
• Aids in dissipation, dispersion and decomposition of pollutants

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2.3. Composition of the Atmosphere

The atmosphere is having 78.08% nitrogen (N2), 20.95% oxygen (O2) and about 1% other gases.

21%
78%

1%
Fig 1 Composition of the Atmosphere
Evolution of the

3. Evolution of the atmosphere

In present day, the evolution of the atmosphere is a long process, spanning over millions of years
and related with the earth origin and evolution. The evolution process can be divided into three
eras or stages:

3.1. Primitive or First Atmosphere

The formation of earth took place about 5 billion years ago from the solar nebula. The
atmosphere at that time would have consisted of primarily hydrogen (H2),water vapor (H2O),
nitrogen (N2), carbon dioxide (CO2)and carbon monoxide (CO). These gases deliver to the space
because temperatures were too high and earth’s gravity was weak because earth did not have a
differentiated core. The accretion of earth took place about 3.5 billion years ago. It was an
exothermic process therefore, heat will be released and absorbed by noble gases most of which
escaped out. Other constituents chemically combined to form gases which held on the earth under
its gravitational pull. The atmosphere consisted of H2, N2, methane (CH4), ammonia (NH3), H2O
and noble gases.

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3.2. Reducing or Second Atmosphere

This atmosphere existed from 3.5 to 2 billion years ago. The hydrosphere formed about 4 billion
years ago resulting in huge oceans from condensed water vapor. During this period, the earth
cooled down and differentiation of layers took place into a solid core, liquid mantle and thin
crust. The solid core resulted in a strong gravitational force. The energy released from accretion
of particles and decay of radioactive isotopes caused massive volcanic eruptions. Gases dissolved
in the molten magma were reduced while passing through the mantle. Large amounts of N2
andCO2were released into the atmosphere. Most of the CO2 dissolved in water and carbonate
sediments built up. Free oxygen (O2) was not present. The other gases present were H2, N2, CH4,
NH3 and carbon monoxide (CO) in trace amounts, hydrogen sulphide (H2S), sulphur dioxide
(SO2), chlorine (Cl2) etc.

3.3. Oxidizing or Present Day Atmosphere

Around 2.4 billion years ago, free O2 starts forming in the atmosphere. Though photosynthesizing
cyanobacteria were present around 2.7 billion years ago, but the O2 released during
photosynthesis was used in oxidation of metals like iron. The atmosphere became oxidizing and
O2 consuming life forms began appearing in the oceans on earth. O2 was being generated by
photolysis of water from ultraviolet (UV) radiation and also from photosynthesis by plants and
cyanobacteria. However, higher in the atmosphere, O2 molecules were absorbing the UV
radiations and getting converted to ozone (O3). Soon, an ozone layer was formed, which protects
surface of the earth from high energy UV radiations making it feasible also for development of
life on land. As higher life forms emerged on land, plants added to the atmospheric O2 while
animals used it up for breathing and the O2 level stabilized around the 21% we know today.

4. Structure of the Atmosphere

There are five layers of the earth’s atmosphere (Fig 4.) based on the variation in vertical
temperature in each layer:

4.1. Troposphere

Troposphere is closest layer to the earth’s surface. So, the layer in which we live is troposphere. It
is about 18 km above the sea level at the equator and 7 km at poles.75% of the atmospheric gases
are present in this layer and almost all of the dust particles and water vapors. All weather
phenomenon like cloud formation, winds, rainfall, snowfall takes place in this layer.

The air below this layer is warmer than any other layer because it is heated from the earth’s
surface below. The layer of air which is warm tends to rise up, and a pocket of cold air flows to
cover the space, giving rise to wind movement. The temperature will decrease at a rate of about
6.5 °C per km as the altitude increases. The average temperature near the surface is 15°C while it
is -57° C at the top. Pressure, moisture content and density of air also decrease with height
thinning of air. That is why people experience breathlessness at high altitudes in mountains.

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The troposphere ends when there is variation in temperature with height. This area, which is the
top of troposphere and bottom of stratosphere, is known as tropopause. The inversion of
temperature beyond tropopause prevents further convection of air thereby confining most of the
weather phenomenon in troposphere.

4.2. Stratosphere

Stratosphere is the second layer of earth’s atmosphere. It starts at the top of tropopause and is 50
km above the sea level. The term stratosphere is derived from a Greek word “strata” which
means arrangement in horizontal layers. Approximately 99% of the atmosphere is located up to
this height which includes almost all the gases. Weather balloons and jet aircrafts fly in this
region as the air present in this layer is very thin. This increases the fuel efficiency of the
aircrafts.

The stratosphere also contains the ozone layer; at a height of about 30 km. The density or
thickness of ozone layer above the surface of earth is measured in Dobson Units (DU). The ozone
layer is thinnest near the equator (~260 DU) and its thickness increases towards the poles, though
there are seasonal fluctuations. Ozone – which is a mainly formed photochemical smog – is
considered to be dangerous for health if reached the ground level or near the surface of earth.
However, in the stratosphere, the high energy UV radiation is absorbed by the ozone layer and
heats up the stratosphere. This also prevent skin cancer and damage to vegetation.

The ozone layer is created in the stratosphere when the oxygen molecules (O2) absorb UV
radiations (240 nm) and dissociate to give atomic oxygen (O) which immediately react with
another O2 molecule and results in the formation of an ozone (O3) molecule:

Although, the absorption of UV radiation in the stratosphere leads to dissociation of ozone

molecules, the ozone layer density is maintained by the reformation of ozone:

As the height increases temperature in the stratosphere also increases, with the base temperature
being close to −60 °C and close to freezing at the top. This is because, the top layer is hottest and

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bottom is coldest, the temperature stratification takes place with little or no mixing of layers. The
stratification has a disadvantage too. Because there is no vertical convection in the stratosphere,
so dissipation and dispersion of materials do not take place. Chlorofluorocarbons (CFCs) and
aerosols from volcanic eruptions and meteorite impacts can stay in the stratosphere for prolonged
periods of time resulting in damage to the ozone layer and alteration of global climate. The
periods of existence of ozone hole have also seen a considerable increase in the reported incidents
of skin cancer.

The layer which is top of the stratosphere and bottom of mesosphere (the next layer to
stratosphere) is known as stratopause. Here, the temperature becomes constant with altitude till it
again starts increasing in the mesosphere (fig2).

Fig.2 variation of temperature and pressure with the height of atmospheric layer from the
surface of the earth

4.3. Mesosphere

It is the middle layer of the earth’s atmosphere. The name derives from the Greek word ‘misos’
meaning middle. This layer starts at 50 km above the sea level and extends to about 85 km.The
air in this layer is very thin and molecules are at long distance from each other. Not much is
known about this layer because weather balloons and jet aircrafts do not fly so high and it is too
low an orbit for satellites and space shuttles. Some scientific studies have been made using
sounding rockets that are not required to go into orbit. It is found that meteors generally burn up
in the mesosphere. Thus, this layer protects the surface of earth from being pockmarked with
craters.

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The temperature of this layer also decreases with increase in altitude.The temperature of upper
layer of mesosphere is even less than -100°C. At these low temperatures, freezing of water
vapour will take place and polar-mesospheric clouds are formed. They are known to be the
highest water-based aerosols and ends at mesopause. It marks the minimum temperature of
mesosphere (making it the coldest part of earth also) and is the bottom of the next layer – the
thermosphere − of the atmosphere.

4.4. Thermosphere

It is the fourth and widest among all layers of the atmosphere. It is at 90 km or starts from the top
of mesopause to between 500 and 1,000 km, varying with solar activity. When more high energy
radiations are emitted by the sun, the thermosphere expands under heat and thus, its height at top
varies. The air is so thin in this layer, that it is generally considered to be part of outer space. The
Kármán Line at about 100 km is called as boundary of the atmosphere also lies in this region.
Layer is consist of many satellites and space shuttles orbit.

Temperature inversion takes place in thermosphere and temperature increases as one goes up. The
temperatures can range from 500 °C to 2,000 °C or higher, depending upon the position and
activity of the sun. However, the air feels cold because the molecules are so far apart that a
molecule may travel up to 1 km before collision with another molecule.

Most of the X-rays and UV radiations emitted by the sun are absorbed in the thermosphere. In
this layer dissociation of the molecules into atoms, ions and free electrons is done by high energy
radiation. The ionization process increases with increase in sun’s activity. The ions create an
electrical layer, known as the ionosphere, which can reflect radio waves back to the earth making
radio communication possible.In the thermosphere theatoms and molecules get excited to higher
energy states after collisions with charged particles from space. Transfer of thermal energy takes
place during the collisions. The excess energy of atoms and molecules are lost as radiations in the
visible region of spectrum.The top of thermosphere is called thermopause. It is also called as
exobase, because it is the bottom of the exosphere.

4.5. Exosphere

This is the outermost layer of earth’s atmosphere. It starts from the top of thermosphere and
extends up to a height of 10,000 km into space. The atmosphere mainly consists of hydrogen and
helium which can escape into space. So, the air is so thin here that it is almost a vacuum. Thus,
the atoms and molecules have to cover hundreds of kilometers before colliding with each other.

Temperature of exosphere is very high because the particles are directly heated from solar
radiation. However, it doesn’t appear so high because there are too few particles and so there is
not much transfer of energy because inter-molecular collisions are limited.

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5. Heat budget of earth’s atmosphere

Heat budget of earth describes the net flow of energy into earth which is mainly in the form of
shortwave radiation and infrared longwave radiation. This is because the energy flux is important
for understanding the climate change which is also define as earth’s energy balance.

The radiation received by earth is not uniformly distributed because the equatorial region of the
earth is more heated by sun than the Polar Regions. Earth’s heat engine is the energy absorbed by
the atmosphere. This process is coupled with imbalanced solar heating through evaporation,
rainfall, winds, and ocean circulation.
Stability is attained in the global temperature when the incoming solar energy is balanced by an
equal flow of heat to space. The earth radiative equilibrium is distributed in such a way that heat-
trapping gases rise in concentration which result in changing the global temperature. The energy
absorbed by greenhouse gases is radiated back to the space this is known as greenhouse effect
This do not occur rapidly due to the inertia of the oceans. This is in continuation until a new
equilibrium state is established between the incoming and outgoing radiative forcing.

5.1 Energy budget

5.1.1 Incoming radiant energy (shortwave)

The total solar energy received by earth is measured in watts and denoted as the solar constant. It
is estimated that total solar radiation received by the earth is approximately 340 W/m², out of
which approximately 77 W/m² is reflected back to space by clouds and the atmosphere also
23 W/m² is reflected by the surface of earth. Hence only 240 W/m² of solar energy is left which is
added to the Earth's energy budget.
It is estimated that the earth’s geothermal heat flux from the interior of the earth is about 47
terawatts. This is only 0.087 watt/square meter, and represents only 0.027% of Earth's total
energy budget at the surface. The minor sources of radiate energy are usually ignored which
includes solar wind, light from distant stars and thermal radiation.
5.1.2 Outgoing radiant energy (Longwave)
Longwave radiation are those radiation which leaves the planet and also known as outgoing
infrared energy. The atmosphere of the earth partially absorbs as cover of cloud can reflect
radiation. Generally, transportation of heat energy takes place between the surface layers of the
planet to the atmospheric layer by the process of evapotranspiration, latent heat fluxes and
conduction/convention process. Ultimately, results in the transportation of longwave infrared
radiation back into space.

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5.2 Earth’s energy imbalance

If the outgoing thermal radiation and the incoming energy flux are not equal, unbalancing of
energy takes place and results in the adding of net heat to the planet. But this possible only if the
incoming flux is larger than the outgoing flux.
The absorbed and radiated energy by earth can be measured indirectly by satellites which are
launched into Earth's orbit.

5.3 Natural greenhouse effect

The major atmospheric gases such as Oxygen and nitrogen are transparent to both incoming and
outgoing thermal infrared sunlight.
On the other hand H₂O (water vapor), CO₂, CH₄ and other trace gases can absorb large thermal
infrared energy. 17% of the incoming solar energy is radiated by the surface of earth as thermal
infrared. However, 12% of it is directly escapes to the space. The remaining fraction of incoming
solar energy i.e. 5-6% is absorbed by molecules of greenhouse gases which is radiated by the
earth’s surface.
The greenhouse gases then radiate an increased amount of thermal infrared energy in all
directions. Which results in spreading of radiation and they ultimately comes back to earth’s
surface. This causes heating of earth’s surface even more than the direct solar heating. This is
known as natural greenhouse effect.
At an altitude of roughly 5–6 kilometers, greenhouse gas concentration is too small to freely
radiated heat to the space.

5.4 Climate sensitivity and forcings

Basically change in the incident or radiated portion of the energy from heat budget of the earth is
known as radiative forcing. On the other hand climate sensitivity is change in the equilibrium
temperature due to changes in the energy budget.
The earth’s radiative equilibrium is altered by Changes occurring in the Earth's climate system.
These changes can affect the entering and exiting of energy and hence force temperatures to rise
or fall, this is known as climate forcings. Natural climate forcings are change in the brightness of
sun, variation of earth’s axis of rotation and large volcanic eruptions. On the other hand man-
made forcings include particle, responsible for absorption and reflection of incoming solar
radiation; deforestation, responsible for change in reflection and absorption of solar radiation and
increasing concentration of carbon dioxide and other greenhouse gases.
This can give either a positive or negative feedback. Positive feedback is intensifying of original
forcing and negative feedback is weakening of the original forcing. This can be explained as loss
of ice at the poles makes the original forcing less reflective, which is an example of positive
feedback.
The anthropogenic sources of greenhouse gases are responsible for a positive radiative forcing
that reduces the net longwave radiation hence the radiative equilibrium is disturbed.

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6. Summary

• Atmosphere is like a thick blanket of air which envelopes our planet and helps sustain life
• It is spread in the outer space above the surface of earth
• Kármán Line (at about 100 km from the earth’s surface) is considered to be the boundary
of Earth’s atmosphere
• It serves many functions − like absorption ofUV radiations, maintaining temperature on
earth, decreasing diurnal temperature variations etc.− crucial for survival of all life forms
• It consists of 78.08% nitrogen (N2), 20.95% oxygen (O2) and about 1% other gases
• Present atmosphere evolved over millions of years, related to the evolution of earth
• The closest layer to the surface of the earth is Troposphere; temperature decreases with
altitude; contains almost 75% by mass of the atmosphere; most weather phenomenon takes
place in this layer; upper limit is tropopause.
• The second layer is Stratosphere which extends from tropopause to stratopause; here,
temperature increases with altitude, so stratification of layers takes place; ozone layer is
present – responsible for absorbing the harmful UV radiations; weather balloons and jet
aircrafts fly in this layer owing to thinning of air
• Mesosphere; layer present in the middle of the atmosphere; extends from top of
stratopause to mesopause; temperature decreases with altitude
• Thermosphere, the fourth layer, extends from top of mesopause to thermopause;
temperature increases with altitude; contains the ionosphere where radio communication
takes place; satellites and space shuttles orbit in this layer; auroras occur in this layer
• Exosphere is the outermost layer; starts from top of thermopause and extends into space;
air is so thin that it is almost vacuum.

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