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ASSIGNMENT 1

Environmental Management

Photochemical smog is a major local or regional air pollution phenomenon characterized by


oxidants, irritating vapors, and visibility-obscuring particles that occurs in urban areas where
the combination of pollution-forming emissions and appropriate atmospheric conditions are
right for its formation. Though not a treat to the global atmosphere as such, in some urban
areas photochemical smog is highly detrimental to health and to the quality of life. Smog
originally was used to describe the unpleasant combination of smoke and fog laced with sulfur
dioxide, a chemically reducing atmosphere, which was formerly prevalent in London when highsulfur coal was the primary fuel used in that city.

One of the most common urban air pollution problems in the production of photochemical
smog. This condition occurs in dry, stagnant air masses, usually stabilized by a temperature
inversion, that are subjected to intense sunlight. A smoggy atmosphere contains ozone, organic
oxidants, nitrogen oxides, aldehydes, and other noxious species. In latter stages of smog
formation, visibility in the atmosphere is lowered by the presence of a haze of fine particles
formed by the oxidation of organic compounds in smog.
The chemical ingredients of smog are nitrogen oxides (NOx) and volatile organic compounds
(VOCs), both are released from the automobile, as well as from other sources. The driving
energy force behind smog formation is electromagnetic radiation with a wavelength ar around
400 nm or less. In the ultraviolet region, just shorter than the lower limit for visible light. Energy
Absorbed by a molecule from this radiation can result in the formation of active species, thus
initiating photochemical reactions that lead to the noxious products characteristic of smog.
The process by which photochemical smog is formed is shown in Figure 1. Methane (CH4) is one
of the least active hydrocarbons in terms of forming smog, it will be used here to show the
smog formation process because it is the simplest hydrocarbon molecule. Smog is produced in
a series of chain reactions. The first of these occurs when a photon of electromagnetic radiation
with a wavelength less than 398nm is absorbed by a molecule of nitrogen dioxide (NO2), to
produce an oxygen atom, O.
NO2 + hv NO + O
The oxygen atom is very reactive species that can abstract a hydrogen atom from methane,
CH4 + O CH3 + OH

SAYED ASADULLAH

UNISEL, FACULTY OF ENGINEERING, CIVIL DIVISION

ASSIGNMENT 1

Environmental Management

produce a methyl radical (CH3) and a hydroxyl radical (OH). In these formulas, the dot shows a
single unpaired electron. The Hydroxyl radical is especially important in the formation of smog
and in a wide variety of other kinds of photo chemical reactions. The methyle radical car react
with an oxygen molecule,
CH3 + O2 H3COO
To produce a methylperoxyl radical (H3COO) This is a strongly oxidizing, reactive species. One
of the very important reactions of peroxyl radicals are there reaction with NO, produced in the
photochemical dissociation of NO2.
NO + H3COO NO2 + H3CO
To generate NO2, which can undergo photo-dissociation, re-initiating the series of chin
reactions by which smog is formed. Literally hundreds of other reactions can occur, leading
eventually to oxidized organic matter that constitutes the small particulate matter
characteristic of smog.
As the process of smog formation occurs, numerous noxious intermediates are generated. One
of the main ones of these is ozone and it is the single species most characteristic of smog.
Whereas ozone is an essential species in the stratosphere, where it filters out undesirable
ultraviolet radiation, it is a toxic species in the troposphere that is bad for both animals and
plants. Another class of materials formed with smog consists of Oxygen-rich organic
compounds containing nitrogen of which peroxyacetyl nitrate PAN

H O
H

C C O O NO2

H
Peroxyacetyl Nitrate (PAN)
Is the most common example. This compound and ones similar to it are potent oxidizers and
higly irritating to eyes and mucous membranes of the respiratory tract. Also associated with
smog are aldehydes, which are irritants to eyes and the respiratory tract. The simplest
aldehyde, and one commonly found in smoggy atmospheres is Formaldehyde:
O
HCH
Formaldehyde
SAYED ASADULLAH

UNISEL, FACULTY OF ENGINEERING, CIVIL DIVISION

ASSIGNMENT 1

Environmental Management

Figure 1. Outline of the process by which photochemical smog is formed. R


represents hydrocarbon groups. The automobile emits nitrogen oxides and
hydrocarbons, the two main ingredients required to produce Photochemical Smog.

Stanley E. Manahan, Environmental Science and Technology: A Sustainable Approach to Green


Science and Technology, Second Edition.
Lawrence P, Bevy Trends in Catalysis Research [Editor].

SAYED ASADULLAH

UNISEL, FACULTY OF ENGINEERING, CIVIL DIVISION