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Unit 4 – The Chemistry of the Environment

The Chemistry of the Atmosphere

LEARNING OBJECTIVES

• Determine the structure and composition of the atmosphere
and understand the Earth's Atmospheric Cycle.
• Identify the sources and effects of air pollutants and discuss
the existing treatment technologies.




1.0 The Earth's Atmospheric Cycle
Earth is unique among the planets of our solar system in having an atmosphere that
is chemically active and rich in oxygen.
The atmosphere is a protective blanket which nurtures life on the Earth and protects
it from the hostile environment of outer space. It is generally believed that three billion or
four billion years ago, Earth’s atmosphere consisted mainly of ammonia, methane, and water.
There was little, if any, free oxygen present. Ultraviolet (UV) radiation from the sun probably
penetrated the atmosphere, rendering the surface of Earth sterile. However, the same UV
radiation may have triggered the chemical reactions (perhaps beneath the surface) that
eventually led to life on Earth. Primitive organisms used energy from the sun to break down
carbon dioxide (produced by volcanic activity) to obtain carbon, which they incorporated in
their own cells. The major by-product of this process, called photosynthesis, is oxygen.
Another important source of oxygen is the photodecomposition of water vapor by UV light.
Over time, the more reactive gases such as ammonia and methane have largely disappeared,
and today our atmosphere consists mainly of oxygen and nitrogen gases. Biological
processes determine to a great extent the atmospheric concentrations of these gases, one of
which is reactive (oxygen) and the other unreactive (nitrogen).
Molecular nitrogen, with its triple bond, is a very stable molecule. However, through
biological and industrial nitrogen fixation, the conversion of molecular nitrogen into
nitrogen compounds, atmospheric nitrogen gas is converted into nitrates and other

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compounds suitable for assimilation by algae and plants. Another important mechanism for
producing nitrates from nitrogen gas is lightning.

The steps are:

About 30 million tons of HNO3 are produced this way annually. Nitric acid is
converted to nitrate salts in the soil. These nutrients are taken up by plants, which in turn
are ingested by animals. Animals use the nutrients from plants to make proteins and other
essential biomolecules. Denitrification reverses nitrogen fixation to complete the cycle. For

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example, certain anaerobic organisms decompose animal wastes as well as dead plants and
animals to produce free molecular nitrogen from nitrates.
The main processes of the global oxygen cycle is complicated by the fact that oxygen
takes so many different chemical forms. Atmospheric oxygen is removed through respiration
and various industrial processes (mostly combustion), which produce carbon dioxide.
Photosynthesis is the major mechanism by which molecular oxygen is regenerated from
carbon dioxide and water.

Scientists divide the atmosphere into several different layers according to
temperature variation and composition. As far as visible events are concerned, the most
active region is the troposphere, the layer of the atmosphere that contains about 80 percent
of the total mass of air and practically all of the atmosphere’s water vapor. The troposphere is
the thinnest layer of the atmosphere (10 km), but it is where all the dramatic events of
weather—rain, lightning, hurricanes—occur. Temperature decreases almost linearly with
increasing altitude in this region.
Above the troposphere is the stratosphere, which consists of nitrogen, oxygen, and
ozone. In the stratosphere, the air temperature rises with altitude. This warming effect is the
result of exothermic reactions triggered by UV radiation from the. One of the products of this
reaction sequence is ozone (O3), which, as we will see shortly, serves to prevent harmful UV
rays from reaching Earth’s surface. In the mesosphere, which is above the stratosphere, the
concentration of ozone and other gases is low, and the temperature decreases with

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increasing altitude. The thermosphere, or ionosphere, is the uppermost layer of the

atmosphere. The rise in temperature in this region is the result of the bombardment of
molecular oxygen and nitrogen and atomic species by energetic particles, such as electrons
and protons, from the sun.

2.0 AIR POLLUTANTS AND TREATMENT
The demands of increasing population coupled with the desire of most people for a
higher material standard of living are resulting in worldwide pollution on a massive scale.
Environmental pollution can be divided among the categories of water, air, and land
pollution. All three of these areas are linked. For example, some gases emitted to the
atmosphere can be converted to strong acids by atmospheric chemical processes, fall to the
earth as acid rain, and pollute water with acidity. Improperly discarded hazardous wastes
can leach into groundwater that is eventually released as polluted water into streams. In
some cases pollution is a clear-cut phenomenon, whereas in others it lies largely in the eyes
of the beholder.
A reasonable definition of a pollutant is a substance present in greater than natural
concentration as a result of human activity that has a net detrimental effect upon its
environment or upon something of value in that environment. Contaminants, which are not
classified as pollutants unless they have some detrimental effect, cause deviations from the

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normal composition of an environment. Every pollutant originates from a source. The source
is particularly important because it is generally the logical place to eliminate pollution. After
a pollutant is released from a source, it may act upon a receptor. The receptor is anything
that is affected by the pollutant. Humans whose eyes smart from oxidants in the atmosphere
are receptors. Eventually, if the pollutant is long-lived, it may be deposited in a sink, a long-
time repository of the pollutant. Here it will remain for a long time, though not necessarily
permanently.
Some air pollutants, particularly those that may result in irreversible global warming
or destruction of the protective stratospheric ozone layer, are of such a magnitude that they
have the potential to threaten life on earth.
Modern technology has provided the means for massive alteration of the
environment and pollution of the environment specifically the atmosphere. However,
technology intelligently applied with a strong environmental awareness also provides the
means for dealing with problems of environmental pollution and degradation.
Oxides of carbon, sulfur, and nitrogen are important constituents of the atmosphere
and are pollutants at higher levels. Of these, carbon dioxide, CO2, is the most abundant. It is
a natural atmospheric constituent, and it is required for plant growth. However, the level of
carbon dioxide in the atmosphere, now at about 360 parts per million (ppm) by volume, is
increasing by about 1 ppm per year. This increase in atmospheric CO2 may well cause general
atmospheric warming—the “greenhouse effect,” with potentially very serious consequences
for the global atmosphere and for life on earth. Though not a global threat, carbon monoxide,
CO, can be a serious health threat because it prevents blood from transporting oxygen to
body tissues. The two most serious nitrogen oxide air pollutants are nitric oxide, NO, and
nitrogen dioxide, NO2, collectively denoted as “NOx.” These tend to enter the atmosphere as
NO, and photochemical processes in the atmosphere can convert NO to NO2. Further
reactions can result in the formation of corrosive nitrate salts or nitric acid, HNO3. Nitrogen
dioxide is particularly significant in atmospheric chemistry because of its photochemical
dissociation by light with a wavelength less than 430 nm to produce highly reactive O atoms.
This is the first step in the formation of photochemical smog. Sulfur dioxide, SO2, is a reaction
product of the combustion of sulfur-containing fuels such as high-sulfur coal. Part of this
sulfur dioxide is converted in the atmosphere to sulfuric acid, H2SO4, normally the
predominant contributor to acid precipitation.
The most abundant hydrocarbon in the atmosphere is methane, CH4, released from
underground sources as natural gas and produced by the fermentation of organic matter.
Methane is one of the least reactive atmospheric hydrocarbons and is produced by diffuse
sources, so that its participation in the formation of pollutant photochemical reaction
products is minimal. The most significant atmospheric pollutant hydrocarbons are the
reactive ones produced as automobile exhaust emissions. In the presence of NO, under
conditions of temperature inversion low humidity, and sunlight, these hydrocarbons
produce undesirable photochemical smog manifested by the presence of visibility-

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obscuring particulate matter, oxidants such as ozone, and noxious organic species such as
aldehydes.
Particles ranging from aggregates of a few molecules to pieces of dust readily visible
to the naked eye are commonly found in the atmosphere. Some atmospheric particles, such
as sea salt formed by the evaporation of water from droplets of sea spray, are natural and
even beneficial atmospheric constituents. Very small particles called condensation nuclei
serve as bodies for atmospheric water vapor to condense upon and are essential for the
formation of rain drops. Colloidal-sized particles in the atmosphere are called aerosols.
Those formed by grinding up bulk matter are known as dispersion aerosols, whereas
particles formed from chemical reactions of gases are condensation aerosols; the latter tend
to be smaller. Smaller particles are in general the most harmful because they have a greater
tendency to scatter light and are the most respirable (tendency to be inhaled into the lungs).
Much of the mineral particulate matter in a polluted atmosphere is in the form of oxides and
other compounds produced during the combustion of high-ash fossil fuel. Smaller particles
of fly ash enter furnace flues and are efficiently collected in a properly equipped stack
system. However, some fly ash escapes through the stack and enters the atmosphere.
Unfortunately, the fly ash thus released tends to consist of smaller particles that do the most
damage to human health, plants, and visibility.
The removal of particulate matter from gas streams is the most widely practiced
means of air pollution control. A number of devices have been developed for this purpose
which differ widely in effectiveness, complexity, and cost. The selection of a particle removal
system for a gaseous waste stream depends upon the particle loading, nature of particles
(size distribution), and type of gas-scrubbing system used.

Particle Removal by Sedimentation and Inertia
The simplest means of particulate matter removal is sedimentation, a phenomenon
that occurs continuously in nature. Gravitational settling chambers may be employed for the
removal of particles from gas streams by simply settling under the influence of gravity. These
chambers take up large amounts of space and have low collection efficiencies, particularly
for small particles.
Gravitational settling of particles is enhanced by increased particle size, which occurs
spontaneously by coagulation. Thus, over time, the sizes of particles increase and the number
of particles decreases in a mass of air that contains particles. Brownian motion of particles
less than about 0.1 µm in size is primarily responsible for their contact, enabling coagulation
to occur. Particles greater than about 0.3 µm in radius do not diffuse appreciably and serve
primarily as receptors of smaller particles. Inertial mechanisms are effective for particle
removal. These depend upon the fact that the radius of the path of a particle in a rapidly
moving, curving air stream is larger than the path of the stream as a whole. Therefore, when
a gas stream is spun by vanes, a fan, or a tangential gas inlet, the particulate matter may be

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collected on a separator wall because the particles are forced outward by centrifugal force.
Devices utilizing this mode of operation are called dry centrifugal collectors (cyclones).

Particle filtration
Fabric filters, as their name implies, consist of fabrics that allow the passage of gas
but retain particulate matter. These are used to collect dust in bags contained in structures
called baghouses. Periodically, the fabric composing the filter is shaken to remove the
particles and to reduce back-pressure to acceptable levels. Typically, the bag is in a tubular
configuration. Numerous other configurations are possible. Collected particulate matter is
removed from bags by mechanical agitation, blowing air on the fabric, or rapid expansion
and contraction of the bags.

Although simple, baghouses are generally effective in removing particles from
exhaust gas. Particles as small as 0.01 µm in diameter are removed, and removal efficiency
is relatively high for particles down to 0.5 µm in diameter. Aided by the development of
mechanically strong, heat-resistant fabrics from which the bags are fabricated, baghouse
installations have increased significantly in the effort to control particulate emissions.

Scrubbers
A venturi scrubber passes gas through a device which leads the gas stream through a
converging section, throat, and diverging section. Injection of the scrubbing liquid at right
angles to incoming gas breaks the liquid into very small droplets, which are ideal for
scavenging particles from the gas stream. In the reduced-pressure (expanding and,
therefore, cooling) region of the venturi, some condensation can occur of vapor from liquid
initially evaporated in the generally hot waste gas, adding to the scrubbing efficiency. In
addition to removing particles, venturis may serve as quenchers to cool exhaust gas, and as
scrubbers for pollutant gases. Ionizing wet scrubbers place an electrical charge on particles

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upstream from a wet scrubber. Larger particles and some gaseous contaminants are
removed by scrubbing action. Smaller particles tend to induce opposite charges in water
droplets in the scrubber and in its packing material and are removed by attraction of the
opposite charges.



ASSESSMENT TASK



1. Which size range encompasses most of the particulate matter mass in the
atmosphere?


2. Why are aerosols in the 0.1–1 µm size range especially effective in scattering
light?

3. Make a brief discussion about air pollutants and treatment technologies






References:
Chang, Raymond and Kenneth A. Goldsby, (2017) Chemistry, (12th International Edition),
New York: McGraw-Hill.

Manahan, S. E. (2010). Environmental Chemistry. CRC press.

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