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The Chemistry of Photochemical Smog

Key Concepts

Photochemical smog is a type of air pollution produced when sunlight acts upon motor vehicle
exhaust gases to form harmful substances such as ozone (O3), aldehydes and
peroxyacetylnitrate (PAN).

Ozone causes breathing difficulties, headaches, fatigue and can aggrevate respiratory
problems.

The peroxyacetylnitrate (CH3CO-OO-NO2) in photochemical smog can irritate the eyes, causing
them to water and sting.

Ozone Production

Motor vehicles produce exhaust gases containing oxides of nitrogen such as nitrogen dioxide
(NO2) and nitric oxide (NO).

At the high temperatures of the car's combustion chamber (cylinder)or during


lightning,nitrogen and oxygen from the air react to form nitric oxide(free radical) (NO):

N2(g) + O2(g) -----> 2NO(g) Some of the nitric oxide (NO) reacts with oxygen to form
nitrogen dioxide (NO2):

2NO(g) + O2(g) -----> 2NO2(g) The mixture of nitric oxide (NO) and nitrogen dioxide
(NO2) is sometimes referred to as NOx.

When the nitrogen dioxide (NO2) concentration is well above clean air levels and there is
plenty of sunlight, then an oxygen atom splits off from the nitrogen dioxide molecule:

sunlight
NO2(g) NO(g) + O(g)
----------> This oxygen atom (O) can react with oxygen molecules
(O2) in the air to form ozone (O3):

O + O2 -----> O3 Nitric oxide can remove ozone by reacting with it to form


nitrogen dioxide (NO2) and oxygen (O2):

NO(g) + O3(g) -----> NO2(g) + O2(g) When the ratio of NO2 to NO is greater than 3, the
formation of ozone is the dominant reaction. If the ratio is less than 0.3, then the nitric oxide
reaction destroys the ozone at about the same rate as it is formed, keeping the ozone
concentration below harmful levels.

The reaction of hydrocarbons (unburnt petrol) with nitric oxide and oxygen produce nitrogen
dioxide also in the presence of sunlight, increasing the ratio of nitrogen dioxide to nitric oxide.

Peroxyacetylnitrate Production
Nitrogen dioxide (NO2), oxygen (O2) and hydrocarbons (unburnt petrol) react in the presence
of sunlight to produce peroxyacetylnitrate (CH3CO-OO-NO2):

sunlight
NO2(g) + O2(g) + hydrocarbons CH3CO-OO-NO2(g)
----------> Catalytic
Converters

Catalytic converters on motor vehicle exhausts are a way of trying to reduce the carbon
monoxide and nitrogen oxide emissions.

The catalyst used is either platinum or a combination of platinum and rhodium.

The platinum catalyses the reaction of unburnt hydrocarbon (such as pentane) and oxygen
(O2) to produce carbon dioxide (CO2) and water vapour (H2O):

C5H12 platinum catalyst


+ 8O2 5CO2 + 6H2O
(pentane) -------------------> The rhodium catalyses the reaction
of carbon monoxide (CO) and nitric oxide (NO) to form carbon dioxide (CO2) and nitrogen gas
(N2):

rhodium catalyst
2CO + 2NO 2CO2 + N2
-------------------> The reduction of nitric oxide (NO) to nitrogen gas
(N2) must proceed more quickly than the oxidation of carbon monoxide (CO) to carbon dioxide
(CO2) or else all the carbon monoxide will be oxidised to carbon dioxide before it can be used
to reduce the nitric oxide.

Motor vehicles can only use catalytic converters if they use unleaded petrol since the lead in
petrol renders the catalyst inactive

These are the equations in the formation of photochemical smog.


Photochemical Smog
What follows is a brief description of photochemical smog formation,
from a non-chemist. For those who want to pursue this topic, there are
also some links to follow for more information.

Photochemical smog is brown smog, the gray-brown haze that fills the
air in many cities. It is especially a problem in warm, sunny regions where
there are lots of cars burning gasoline. Researchers in the 1940's and
1950's in Los Angeles noticed that the kinds of pollutants in the air varied
over the course of the day. Some pollutants increased in the morning, as
people started driving their cars. Other pollutants, including the visible,
brown smoggy haze, were most common in the middle of the day. The mix
of pollutants changed again in the late afternoon and evening. It became
apparent that the chemical reactions among the various pollutants were
related to sunlight. Smog is worse in Los Angeles--and everywhere--in the
summer, because the light energy from the sun moves some of the
reactions along.

To form photochemical smog, three main ingredients are needed:


nitrogen oxides (NOx), hydrocarbons, and energy from the sun in the form
of ultraviolet light (UV).

The first thing that starts the chain of events is that people start driving
in the morning. As gasoline is burned, nitrogen (N2) in the atmosphere is
also burned, or oxidized, forming nitric oxide (NO)

N2 + O2=2NO

Hydrocarbons and carbon monoxide (CO) will also be emitted by cars.


Hydrocarbons are volatile organic compounds that may include
acetaldehyde, formaldehyde, ethylene, and many other compounds.

In the air, nitric oxide combines with molecular oxygen to form nitrogen
dioxide within a few hours.

2NO + O2--------->2NO2

Nitrogen dioxide absorbs light energy and splits to form nitric oxide and
atomic oxygen:

NO2-->NO + O

Then, in sunlight, the atomic oxygen combines with oxygen gas to form
ozone (O3):

O+ O2--->O3
If no other factors are involved, ozone and nitric oxide then react to form
nitrogen dioxide and oxygen gas.

O3 + NO<------>NO2 + O2

This last reaction can go in either direction, depending on temperature and


the amount of sunlight. If there is a lot of sunlight, the equation moves to
the left, and more ozone is produced. If nothing else gets in the way, an
equilibrium is reached, and the ozone level stabilizes.

However, there is something else involved. Remember that the cars are
also emitting hydrocarbons as well as oxides of nitrogen. Hydrocarbons
are the other main ingredient in photochemical smog. When hydrocarbons
are present, nitric oxide reacts with them instead of the ozone. This
reaction produces a variety of toxic products, such as a volatile compound
known as PAN (peroxyacetyl nitrate).

NO + hydrocarbons----------------->PAN and various other compounds. Also,

NO2 +hydrocarbons------------------>PAN and various other compounds

So, there are two results (at least) from the reaction of nitrogen oxides with
hydrocarbons. One is that a lot of volatile, reactive organic compounds
are generated directly. The other is that when the nitric oxide (NO) is busy
reacting with hydrocarbons, it is not reacting with ozone to break it back
down to molecular oxygen. So the amount of ozone in the air increases.
With nitric oxide reacting with hydrocarbons, ozone may accumulate to
damaging levels. (Ozone may also be released into the air naturally by
forest fires. But in a natural situation, ozone would react with nitric oxide
and be broken down to oxygen, as noted above).

The result, then, is an accumulation of ozone and volatile organic


compounds such as PAN. These are referred to as secondary pollutants,
because they are formed by the reaction of primary pollutants, nitrogen
oxides and hydrocarbons, emitted by burning fossil fuels. The energy from
the sun moves the reactions along. This forms photochemical smog, the
brown gunk we see in the sky, especially on hot sunny days.

Photochemical smog can cause eye irritation and poor visibility. Strong
oxidants such as ozone can damage the lungs. The oxidants irritate the
linings of lungs. Damage to the lungs may stress the heart. Health damage
is worse for people with existing lung and heart conditions. Other health
implications may include loss of immune system function, increased
susceptibility to infections, and fatigue. The damage can be caused by
exposure to large amounts of the pollutant over a short time span, and also
by chronic exposure to small amounts over long periods of time. Oxidants
can kill plant cells, causing leaves to develop brown spots or drop off the
plant, reduce plant growth, and make plants more susceptible to damage
from other causes. Oxidants such as ozone can also corrode and destroy
many materials such as rubber, nylon, fabric, and paint.

Photochemical Smog
To fully appreciate photochemical smog formation, one must first recognize that
nitrogen is transformed between many different substances in the atmosphere.
Automobile exhausts release nitrous oxide (NO) along with small amounts of
nitrogen dioxide (NO2). These two substances form the starting materials for a
vast array of chemical reactions that lead to products with higher oxidation
states. In a straight forward process, nitrogen oxide (NO) is converted to nitrogen
dioxide (NO2), nitrogen dioxide is transformed to nitrogen trioxide (NO3), and
nitrogen trioxide in transformed into dinitrogen pentoxide (N2O5). Each of these
four simple nitrogen oxides then reacts through a photochemical process, or
direct physical contact, with atmospheric substances to form and an impressive
list of biological irritants. The list of irritants includes: (1) alkyl nitrite; (2)
peroxyalkyl nitrate; (3) alkyl nitrate; (4) peroxyacetyl nitrate; (5) nitrous acid; (6)
peroxynitric acid; (7) nitric acid, and; (8) ammonium nitrate. These chemical
transformations are shown graphically in Figure 40.1.

Figure 40.1
Chemical
Transformations of
Nitrogen Oxides in
the Troposphere.
The substances that react with nitrogen oxides to form oxidants (the final product
of photochemical smog) are trace hydrocarbons (from incomplete combustion)
and the hydroxyl radical. The necessary ingredients for photochemical smog
formation are (1) nitrogen oxides, (2) sunlight, and (3) hydrocarbons.
Photochemical smog formation proceeds through a sequence of reactions, all
involving a free radical mechanism. Free radicals are generated by
photodissociation of nitrogen dioxide, a process that generates ozone and
oxygen atoms. Oxygen atoms react with water to form hydroxyl radicals, which in
turn react with hydrocarbons to form hydrocarbon radicals. Oxidation of
hydrocarbons by the hydroxyl radical leads to the formation of aldehydes. The
aldehydes are oxidized further to form aldehyde peroxides and aldehyde
peroxyacids. These final substances are the compounds that are so irritating to
sensitive biological tissues and cause most of the health problems associates
with photochemical smog. Figure 40.3, shown below, is a diagram showing the
changes in atmospheric concentrations for nitrogen oxide, nitrogen dioxide, non-
methane hydrocarbons, aldehydes, and oxidants. Analysis of the data shown in
Figure 40.3 led to the equations for photochemical smog formation (equations 1-
8, shown below).

Figure 40.2 Cartoon illustrating the main components of Photochemical


Smog formation.
Figure 40.3 Daily Chemical Transformations Occurring in the Formation of
Photochemical Smog.
Generalized Reaction Scheme for Photochemical Smog Formation

This is a cyclic process that needs light and nitrogen oxides to generate oxygen
atoms. Once formed, the oxygen atoms react with water to form hydroxyl
radicals. The hydroxyl radicals then react with hydrocarbons according to
equations 5 through 8 to form peroxyacyl nitrates (or PAN).

then
In summary, this is what happens in photochemical smog formation

1) Nitrogen oxides generate oxygen atoms

2) Oxygen atoms form hydroxyl radicals


3) Hydroxyl radicals generate hydrocarbon radicals

4) Hydrocarbon radicals form hydrocarbon peroxides

5) Hydrocarbon peroxides form aldehydes

6) Aldehydes form aldehyde peroxides

7) Aldehyde peroxides form peroxyacylnitrates

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