COURSE: ENVIRONMENTAL CHEMISTRY-209 2022

The Atmosphere

LECTURE 10
Structure of the atmosphere, Chemical composition of the atmosphere, Solid in air
and liquid in air colloidal solutions. Particles in the atmosphere and their impact on
health, Changes in the composition and temperature with the altitude, Energy balance
of the atmosphere and the earth

Instructor: Prof. Dr. Mohammad Rafiq Khan

 DISCUSSION ON FINER DETAILS

The blanket of gases in the atmosphere extends up to a height of about1000 Km.

Major and minor components
Table 3.1: Standard composition of clean and dry air (Near sea level)

Gas Symbol/ Percentage Percentage Parts per Microgram/M3

Formula by Volume by Weight Million-ppm
(Volume)

Nitrogen N2 78.08 75.45 780,805 8.95x108

Oxygen O2 20.95 23.20 209,450 2.74x108

Argon Ar 0.93 1.28 9,340 1.52x107

Carbon dioxide CO2 0.038 0.0590 380 5.67x105

Neon Ne 0.0018 0.0012 18.21 1.49x104

Helium He 0.0005 0.0007 5.24 8.5x102

Krypton Kr 0.0001 0.0003 1.14 3.43x102

Hydrogen H2 0.00005 Negligible 0.50 4.13x10

Xenon Xe 8.7x10-6 0.00004 0.087 4.29x102

The proportions of the components remain almost the same up to an altitude of 16 Km. Above
this altitude begins the effect of the gravitational separation that manifests its significance at
the altitude of about 130 Km from the earth’s surface.
The gaseous components of the atmosphere, being very light as compared to the liquid and
solid components of earth, the weight of the atmosphere is very small in comparison with
that of the earth It is 5.5×1015 tons that is equal to about one millionth of the weight of the
earth. About 90% of the mass of the atmosphere lies in the region up to 30 Km altitude from
the earth’s surface.

Table 3.2: The temperature changes in different environmental segments of the atmosphere
with the change in altitude from the earth’s surface.
Source: Encyclopedia Americana Volume 2, (International Edition)
Atmospheric Region Range of Altitude in Km Range of Temperature in C0
Troposphere 0 to11 15 to – 56

Stratosphere 11 to 50 – 56 to –2

Mesosphere 50. to 85 –2 to –92

Thermosphere 85 to 500 –92 to 1,200

Fig.3.1: The temperature profile of the atmosphere exhibiting complete changes in
different environmental segments of the atmosphere.
The atmosphere undergoes changes in its general characteristics with the increase in
altitude from the earth’s surface. These changes are highlighted below.

•Four zones: Troposphere, Stratosphere, Mesosphere and Thermosphere respectively. These four
zones of the atmosphere are not clearly defined and there is a considerable overlap between
them. The troposphere, stratosphere and mesosphere are fairly uniform in composition, but the
troposphere is of particular interest from the point of view of the environmental chemistry.
•Table 3.2 and changes in temperature. The thermosphere exhibits an relationship
exponential and is governed by the equation
P = P o e-mgh / RT Where
P=Pressure at the height at which the pressure is to be calculated. Po=
Pressure at the earth’s surface (Zero height) m=
Average molecular weight of air expressed in g (28.97g/mol) g=
Acceleration due to gravity that is 981 cm per second.
R = Gas constant (8.314 ×107 per degree per mol)
h = Height at which the pressure is to be calculated.
•The density of the mixture is the lowest nearest to the hottest region in, which the
temperature rises and finally goes as high as about 1200oC.
•The atmospheric pressure decreases exponentially with the altitude from the surface of the
earth. The density of air decreases with the rise in the altitude. The density is about 0.0013g/
cubic meter at the sea level. It decreases sharply and so much that at an altitude of 600
kilometers the atoms and the molecules exhibit free elliptical motion in the earth’s
gravitational field. This means that the gaseous mixture goes on thinning as we move to the
higher altitudes.
 Troposphere

Its upper limit may vary by an addition or subtraction of a few kilometers depending
upon the temperature, nature of the terrestrial surface, etc. Its thickness at the equator is
greater than that at the poles. Its depth at the equator is 15 km, while that at poles is 8
km. The mass of the troposphere is 70% of the mass of the whole atmosphere.

The temperature in the troposphere decreases with the increase in the altitude and falls
to 217oK (-56oC) at the upper end of the troposphere.
Lapse Rate: The change of temperature with the altitude.
Positive Lapse Rate; Decrease of temperature with the increase in altitude
Negative Lapse Rate: Increase of temperature with the increase in altitude
Adiabatic Lapse Rate: It is the lapse rate if air is not saturated with water vapors,
The temperature, in the troposphere, decreases at the lapse rate of 9.8oC/Km, which is
the adiabatic lapse rate.
Temperature Inversion: The transition from the positive to the negative lapse rate.
Tropopause: The point at which the temperature inversion takes place It is a narrow
transition layer at the top of the troposphere at 10 to 20 Km altitude in which the
temperature starts suddenly increasing as indicated by the temperature-altitude curve
in Fig. 3.1. The temperature in the tropopause is the minimum at the equator.

The troposphere is heated by the solar radiation through conduction (Transmission of

light or heat energy to a target without heating the medium)
The troposphere starts heating from the surface of the earth. That is why the
temperature is the highest near the earth’s surface and decreases with the altitude.

The temperature at the equator is the highest, while that at the poles is the lowest. This
is due to the vertical fall of solar radiation on equator and lateral fall on the poles
(Differential heating and cooling rates).
The difference in temperature and differential heating and cooling rates cause
the convection currents in the troposphere. The convection currents also
contribute to the fall of temperature with the increase in the altitude. As a
consequence of the convection current, the air rises up in Equatorial Region
and descends in the Polar Regions. The rise of air is associated with expansion
and loss of its internal energy, which ultimately translates into the fall of
temperature.

The composition of air in the troposphere is quite uniform. It contains 78%

nitrogen, 21% oxygen and 1% argon. In addition, it contains water vapors and
carbon dioxide. The carbon dioxide is also uniformly distributed in the
troposphere. Its concentration is 0.03%.
The troposphere contains most of the atmospheric water, clouds and particulates. The
mass of these gases is responsible for about three quarter of the mass of the total
atmosphere. This mass is concentrated in the lower atmosphere up to an altitude of
approximately 10 Km.

The water vapors present in the atmosphere exhibit some distinguished

characteristics. For example, it is the major gaseous component in the lower
atmosphere that absorbs significant proportion (About 10% of total) solar radiation
passing through air to reach the earth.

At high altitudes, the water vapors undergo photo-dissociation caused by the intense
ultraviolet radiation to form atomic hydrogen and hydroxyl free radicals according to
the reaction:

H2O + hυ → H. + HO.
 The hydroxyl free radical reacts with many other normal constituents and pollutants
present in the stratosphere resulting into many products. The atomic hydrogen may combine to
form molecular hydrogen or may undergo different reactions. The hydrogen thus may be
eliminated from the atmosphere. The loss of hydrogen from the atmosphere is prevented by the
tropopause. It condenses water vapors and freezes them to ice particles before they reach the
lower altitudes to form the clouds or melt to take the form of rainfall.

The pollutants in the atmosphere mix with air in the troposphere. The convection currents
are mostly set up in about one Km boundary layer from the earth’s surface. The pollutants in
this layer mix with air at a faster rate. Most of the pollutants are of natural or anthropogenic
origin. These include the oxides of nitrogen and sulfur, particulates and ground level ozone
formed as a result of the following photolytic reactions.

NO2 + hν → NO + O.

O2 + O. + M → O3 + M where M is a third body

The conditions of the troposphere are most suitable for the existence of life and
survival of the living organisms including plants, animals and microorganisms.
If life is made possible in the upper regions, it is done by creation of artificial
tropospherical conditions in these regions. Example: Jets fly in the stratosphere,
inside temperature and pressure suitable for the persons on board and supply of
adequate quantities of oxygen and with the systems to exhaust the products of
respiration and the smoke, etc, resulting from the smoking activity of the passengers.

Disturbance of normal living activity by pollutants “Air Pollution.”

Stratosphere
It is situated above the troposphere, tropopause and constitutes a buffering strip and is
responsible for transition from one major environmental segment to the other. The is
called Stratopause: It is the region present immediately above the stratosphere. It marks
transition from the stratosphere to the next major region called “Mesosphere.” On the
whole, the stratopause constitutes the second transitional layer in the atmosphere. It
reflects the sound waves from earth back to the earth’s surface and thus plays a major
role in radio and television broadcast. The same forms the basis of the radar and that of
the radio based controls of different devices.

In the stratosphere–2oC is the temperature of the upper boundary of this region (Negative lapse
rate). The warming in the stratosphere occurs due to the absorption of the ultraviolet radiation by
the ozone that forms about 1 to 5 ppm in the region. The ozone present in the stratosphere, thus, is
responsible for the negative lapse rate in it. The air in this region is almost dry and the clouds do
not enter into it and the convection currents of the troposphere do not affect it.
 The major components of the stratosphere are nitrogen, oxygen and ozone. Here may be
present traces of water vapors, which are highly activated due to the absorption of ultraviolet
radiation from the solar radiation keeping the air in the stratosphere almost dry. The absence of
convection currents from stratosphere makes it quiescent as compared to the troposphere that is
highly turbulent.

The nitrogen and oxygen present in the stratosphere remove from the solar radiation (far
UV with wavelength less than 190 nm) before reaching the troposphere. These may undergo
many photochemical reactions due to the photo-energy supplied by the ultraviolet radiation. The
products may be the oxides of nitrogen and ozone as shown by the reactions given below.

O2 → [O] + [O]

O2 + [O] + M→ O3 + M
 Where M is a third inert entity (such as N2 or O2), whose availability is essential for the
survival of ozone. Here, it is the nitrogen present in the atmosphere that takes up the excess
energy.
As ozone also absorbs UV radiation, the reversal of the Step 1 may occur as given below.

hν
O3 → O2 + [O]
hν
NO2 → NO +[ O]

NO + O3 (Air) → NO2 + O2

O2 (Air) + O → O3

The formation of ozone thus is a cyclic phenomenon

3O2 (Air) → 2O3

2O3 → 3O2
Important role of ozone
The pollutants undergo many chemical reactions in the stratosphere as a result of
which, these may be either consumed or led to the formation of species either
harmless or even more harmful than the primary pollutants. The cause of these
reactions is lack of turbulence in the stratosphere. The pollutants sink earlier and thus
have short average life periods. Due to no turbulence in the stratosphere and relatively
calm environment, there is little intermixing of the pollutants that rise from the
troposphere. That is why after rising, they remain in the stratosphere for long periods,
some of them even for years. The particulates such as dust particles are important
examples having life more than a year. The accumulation of dust particles in the
stratosphere may translate into a blackout due to hindrance in the way of solar
radiation and that may result into the reduction in the rate of photosynthesis of plants
and ultimately into radiation traveling to the earth’s surface. The reduction in the light
intensity may reduce agricultural production.
Mesosphere
It contains nitrogen, oxygen, ozone and nitric oxide as the principal species. The
ozone is present in low concentration. On its top is the third transitional layer of the
atmosphere called “Mesopause.”
The major characteristic of the mesosphere is the temperature.
The temperature starts decreasing again with the start of the mesosphere and the
temperature profile exhibits a positive lapse rate. The temperature continues falling up
to the end of the mesopause, where the temperature encountered is from -80 to -100 oC
with an average of -92oC. The coldest temperature encountered in the mesopause is
about -100oC and this is the coldest temperature in the whole atmosphere. The low
temperature in this region is due to less absorption of the solar radiation by ozone and
other species as both ozone and other species are present in low concentrations.
From the end of the mesopause, the temperature starts increasing again and exhibits a
negative lapse rate. This marks the start of the thermosphere.
Thermosphere
The principal chemical species encountered in its composition are nitrogen, oxygen
both in the atomic and molecular form, O2+, O+, O- NO+, etc. There is thus also a
significantly high concentration of negatively charged ions and electrons in
thermosphere. The conditions of the atmosphere being highly rarified, the charged
species in the thermosphere persist for long periods. Due to the presence of ions in
significantly high concentrations, this region is also called “Ionosphere.” The
ionization occurs due to the absorption of short wavelength (less than 200nm, far UV
region) by the gaseous components such as oxygen and nitric oxide in the lower
layers of the thermosphere. That is why some environmental scientists call this layer
located between 50 to 100 kilometers as Ionosphere.
The temperature in the thermosphere is also the major consideration. It rises rapidly
with the altitude and goes as high as 1200oC. The rise in temperature, thus, exhibits a
negative lapse rate. The density of air and pressure are the lowest in this region as the
temperature here is the highest. The density, for example, is 10-9 to 10 -15 of that on the
surface of the earth. The heat retention in this region is less. Thus, the objects are
subject to high temperature in sunlight during the day and to low temperature at night.

Division on the Basis of Nature of Chemical Composition of Air and Altitude:

Homosphere, Heterosphere and Exosphere.
Homosphere
It is the lower region of the atmosphere that extends from the earth’s surface to about
100 Km altitude. The basis of its nomenclature is the homogeneous composition of air
in this region. The uniformity of the composition is shown in Table 3.3. There is a
region of the homosphere where most of the chemical reactions like the formation of
ozone; oxides of nitrogen, etc, take place. This region is called Chemosphere.
Table 3.3:- The uniform composition of the homosphere
Source: Encyclopedia Americana Volume 2, (International Edition)
Major Components Minor Components Trace Components
Component Volume % Component Volume % Component Volume %
Nitrogen 78.09 Argon 9.3x10-1 Neon 1.8x10-4
Oxygen 20.95 Carbon Dioxide 3.1x10-2 Helium 5.2 x10-4
Methane 2.0 x10-4
Krypton 1.1 x10-4
Nitrous Oxide 2.5 x10-5
Hydrogen 5.0 x10-5
Xenon 0-8.7 x10-5
Sulfur Dioxide 0-1.0 x10-4
Ozone 0-2.0 x10-6
Nitrogen Peroxide 0-2.0 x10-6
Ammonia 0-Trace
Carbon Monoxide 0-Trace
Iodine 0-Trace
Heterosphere
It extends from 100 to 500 Km altitude and is situated just above the homosphere. In
this region, there is a high degree variation in the composition of the air and this
heterogeneity forms the basis of its nomenclature. It includes a part of the
mesosphere and most of the ionosphere. Thus, the air in this region contains a
number of anions, cations and electrons. The ions constitute a charged belt that
reflects the radio waves and helps in the radio communication. The television waves
are not reflected by the ionosphere and thus are not relayed to different parts of the
globe. To fulfill the purpose of the telecommunication, man-made satellites are floated
in space, which reflect the television waves for global television transmission.
Exosphere
The exosphere is the region in which the species acquire sufficient energy to free
themselves from the gravitational pull of the earth to escape in to the space. It is
situated above 500 Km and extends to about 1000 Km altitude. The air in this region
contains the species like hydrogen, helium and atomic oxygen as pointed out above.
The species in this region are in the extremely rarified form. Their density is 10- 20 times
of that on the surface of the earth.