Reactions of Atmospheric

Chemistry
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Reactions of Atmospheric Chemistry!

Atmospheric Chemistry:
From natural and man-made sources gaseous and particulate matters
are emitted mainly into the troposphere. The larger and heavier
particulate matters settle down quickly after emission due to
gravitational force. The finer and lighter particles remain suspended
for a longer period. Some of these particles settle down while the
others, particularly, the hygroscopic ones act as cloud forming nuclei
and are precipitated along with rain.

The gaseous pollutants emitted into the troposphere mostly undergo

chemical transformation due to oxidation reactions (either thermally
or photo-chemically) and the transformed substances return back to
the earth’s surface either as dry particle or along with rain. The
substances which reach the ground as dry particles are referred to as
‘dry depositions’, whereas the substances which come down with rain
or snow are termed as ‘wet depositions’.

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When rain water contains dissolved acids it is referred to as acid rain.

Normally rain contains some dissolved carbon dioxide (CO 2) and has a
pH level of about 5.6. When rain contains other dissolved acids and
salts the pH may be around four. In very polluted atmospheric
conditions rain water pH may be as low as three. The sinks of some
common primary and secondary gaseous pollutants are listed in Table
2.5.
Tropospheric Reactions:
Solar radiation initiates dissociation of some gas molecules present in
the troposphere and thereby produces some free radicals. These free
radicals then carry on chain reactions with nitrogen oxides, carbon
monoxide, hydrocarbons and sulphurous compounds.

Carbon bearing compounds are oxidized to CO2 H2O, aldehydes, acids,

esters, etc. NOx is oxidized to nitrogen dioxide to nitric acid, and
sulphur compounds to sulphur trioxide to sulphuric acid. The acids
produced may combine with ammonia and air-borne alkaline particles
to form salts. The probable intermediate steps through which some of
the air-borne gaseous pollutants may undergo chemical
transformation and the end products produced are listed hereunder.
Polluted urban atmosphere contains NOx, hydrocarbons and other
pollutants. The NOx molecules absorb solar radiation and produce
oxidants take O3, O; OH’. These oxidants oxidize the hydrocarbons to
aldehydes, peroxides and per-nitrates. Nox are oxidized to nitric acid.
Sulphur compounds are oxidized to sulphuric acid. Under favourable
temperature and humid conditions the secondary pollutants produce
smog.
Stratospheric Reactions:
Only high altitude aircrafts and rockets discharge their exhaust into
the stratosphere directly. These exhausts may contain NO x,
hydrocarbons, CO, CO2 and H2O. Some pollutants, which have not
completely reacted in the troposphere and CFC, which is less reactive
under tropospheric conditions, diffuse into the stratosphere from the
troposphere.
All of these undergo chemical transformation by reacting with ozone
(O3) and some free radicals produced photo chemically in the
stratosphere. Some of the probable reactions through which
transformations take place and the end products produced are listed
hereunder.
I. Free Radical Formation:

II. Hydrocarbons:
III. Nitrogen Oxides:

IV. Chlorofluorocarbons (CFCs):

The transformed products diffuse back to the troposphere from where

they are precipitated to the earth’s surfaces.

Green chemistry
Green chemistry (sometimes referred to as sustainable chemistry) is the branch of chemistry that
deals with the design and optimization of processes and products in order to lower, or remove
altogether, the production and use of toxic substances. Green chemistry is not the same as
environmental chemistry. The former focuses on the environmental impact of chemistry and the
development of sustainable practices that are environment-friendly (such as a reduction in the
consumption of non-renewable resources and strategies to control environmental pollution). The
latter focuses on the effects that certain toxic or hazardous chemicals have on the environment.
The 12 Key Principles of Green Chemistry
The twelve principles put forward by the American chemists’ Paul Anastas and John Warner in the
year 1998 to lay the foundation for green chemistry are listed below.

 Prevention of waste: preventing the formation of waste products is always preferable to the

clean-up of the waste once it is generated.
 Atom economy: the synthetic processes and methods that are devices through green
chemistry must always try to maximize the consumption and incorporation of all the raw
materials into the final product. This must strictly be followed in order to minimize the waste
generated by any process.
 Avoiding the generation of hazardous chemicals: reactions and processes that involve the
synthesis of certain toxic substances that pose hazards to human health must be optimized
in order to prevent the generation of such substances.
 The design of safe chemicals: during the design of chemical products that accomplish a
specific function, care must be taken to make the chemical as non-toxic to humans and the
environment as possible.
 Design of safe auxiliaries and solvents: the use of auxiliaries in processes must be avoided
to the largest possible extent. Even in the circumstances where they absolutely need to be
employed, they must be optimized to be as non-hazardous as possible.
 Energy efficiency: The amount of energy consumed by the process must be minimized to
the maximum possible extent.
 Incorporation of renewable feedstock: the use of renewable feedstock and renewable raw
materials must be preferred over the use of non-renewable ones.
 Reduction in the generation of derivatives: the unnecessary use of derivatives must be
minimalized since they tend to require the use of additional reagents and chemicals,
resulting in the generation of excess waste.
 Incorporation of Catalysis: in order to reduce the energy requirements of the chemical
reactions in the process, the use of chemical catalysts and catalytic reagents must be
advocated.
 Designing the chemicals for degradation: when designing a chemical product in order to
serve a specific function, care must be taken during the design process to make sure that
the chemical is not an environmental pollutant. This can be done by making sure that the
chemical breaks down into non-toxic substances.
 Incorporating real-time analysis: processes and analytical methodologies must be
developed to the point that they can offer real-time data for their monitoring. This can enable
the involved parties to stop or control the process before toxic/dangerous substances are
formed.
 Incorporation of safe chemistry for the prevention of accidents: While designing chemical
processes, it is important to make sure that the substances that are used in the processes
are safe to use. This can help prevent certain workplace accidents such as explosions and
fires. Furthermore, this can help develop a safer environment for the process to take place in.
Examples of the Impact of Green Chemistry

Use of Green Solvents

Many chemical synthesis reactions that are carried out on an industrial scale require large amounts
of chemical solvents. Furthermore, these solvents are also used industrially for degreasing and
cleaning purposes. However, many traditional solvents that have been used for such purposes in the
past are known to be toxic to human beings. Some such solvents are also known to be chlorinated.

Click here to learn about the different examples of solvents.

The advancement of green chemistry has brought forward many alternatives to these toxic solvents.
The green solvents that are coming up as alternatives are known to be derived from renewable
sources and are also known to be biodegradable. Thus, green chemistry has great potential in
lowering the toxicity of certain industrial environments by developing safer alternatives.

Development of Specialized Synthetic Techniques

The development of specialized synthetic techniques can optimize processes in order to make them
more environment friendly by making them adhere to the principles of green chemistry. An important
example of such an enhanced synthetic technique is the development of the olefin metathesis
reaction in the field of organic chemistry. This reaction, developed by Robert Grubbs, Richard
Schrock, and Yves Chauvin, won the Nobel Prize for Chemistry in the year 2005.

Other notable developments brought forward by advancements in green chemistry include:

 The employment of supercritical carbon dioxide as a green solvent (as an alternative to other
toxic solvents).
 Incorporating the use of hydrogen in Enantioselective synthesis reactions (also known as
asymmetric synthesis).
 Incorporating aqueous solutions of hydrogen peroxide (a chemical compound with the
formula H2O2) to drive relatively clean oxidation reactions.
Other notable applications of green chemistry include supercritical water oxidation (often
abbreviated to SCWO), dry media reactions (also known as solid-state reactions and solvent fewer
reactions), and on water reactions.

Production of Hydrazine
Initially, the most popular method for the production of hydrazine (an inorganic chemical compound
with the chemical formula N2H4) was the Olin Raschig process, which involved the use of ammonia
and sodium hypochlorite. However, with the development of green chemistry, a more environment-
friendly alternative to this process was discovered.

In the peroxide process for the production of hydrazine, ammonia is reacted with hydrogen peroxide.
In this alternate method, water is produced as the only side product. It can also be noted that the
peroxide process does not require any auxiliary extracting solvents.