Environmental Chemistry

Air Pollution
The Bhopal Gas Disaster
• In December 1984, the city of Bhopal, India, experienced the effects of one of the most serious
cases of point source atmospheric pollution. The American Union Carbide Company had
established a factory in the city, which made pesticides for Third World countries. One of the
chemicals involved was liquid methyl isocyanate, CH3NCO, a highly reactive, inflammable, volatile
and toxic organic compound. As well as being toxic and an acute irritant, it causes pulmonary
oedema, asthma and nausea. Although the material was stored in underground tanks, the vapours
were accidentally leaked into the atmosphere causing the death of at least 3,300 people and
affecting over 200,000 others. Many of these people were blinded and suffered kidney failure. The
death toll was so great that the Indian Government had to call for volunteers to help the armed
forces to clear the corpses of people and animals from the streets. For some time after the
accident, the skies over Bhopal were described as glowing red from the hundreds of funeral pyres.
It was the worst industrial accident in history. Unfortunately, this accident occurred at a time when
there was a temperature inversion. Temperature inversions commonly occur within the
troposphere as a result of some meteorological event and are short term. The effects of air
pollution caused either by the intentional or accidental release of materials to the atmosphere are
normally greatly reduced by natural atmospheric mixing, i.e. dilution. The degree of mixing
depends on a variety of weather conditions, e.g. temperature, wind speed, and the movement of
high and low atmospheric pressure systems and their interactions with local topology such as
mountains and valleys. Normally, the temperature of air in the troposphere decreases with altitude.
Sometimes a cold layer of air can settle under a warm layer and produce a temperature inversion.
The result of this is the poor mixing of pollutants with air causing a build-up of the pollutants near
ground level.
• An inversion can last some time if it lies under a stationary high
pressure system and there is little or no wind. The consequences of the
accident in Bhopal were thus far greater than they might otherwise
have been. There have been numerous cases of human activities such
as this, which have caused the emission of gases, solid, liquids, noise,
heat and radiation to the atmosphere.
• Such emissions have:
– attacked the fabric of buildings/structures & paper,
– reduced visibility:
– produced offensive smells,
– affected the health of living organisms &
– in some cases caused death.

• Qn. Mention and briefly describe any four disasters caused by human
activities which have led to grave air pollution elaborating on the extent
of the after-effects of each of the incidences.
• There are a number of natural sources that cause atmospheric pollution,
but only one is currently recognized as a major health threat and that is
the radioactive gas radon.
• Because of its localized source and restricted nature of the pollution, the
accident at Bhopal is described as an example of point source pollution.
Such cases result in obvious immediate effects and do not usually pose
national or international pollution problems.
• Industrial companies or others can be made accountable, legal action
taken and appropriate penalties imposed. The cleaning up of the
environment may be problematical but does tend to be confined to a
locality.
• Other emissions, however, cause problems on an international scale and
are referred to as diffuse source pollution. The atmosphere contains a
range of solid and liquid particulate matter together with gases as a result
of both natural and human activities.
• When materials become concentrated enough to reduce air quality they
are referred to as pollutants. Many of these pollutants are capable of
undergoing chemical reactions with other chemicals present in the
atmosphere to produce new harmful products
Particulate Matter
• Particulate matter is defined as single particles or
aggregates of particles with diameters greater than 2 × 10-
10 m.

• Some particulate matter is natural, i.e.

– rain, snow, fog, hail & mist,
• Whilst others are often the result of anthropogenic
processes,
– e.g. smoke, soot and fumes.
• Some natural particulates are affected by human actions,
– such as fog and wind-blown soils.
• Smoke and soot are the products of incomplete combustion
of
– coal, petrol and diesel fuels in furnaces, domestic heating
systems and vehicle engines.
• Atmospheric particulate matter penetrate the respiratory system of
humans and other animals
• Particles in the size range 30 × 10-6 to
• 100 × 10-6 m lodge in the nasal cavity, larynx and trachea.
– Examples of such particles include pollen, fungal spores, cement dust
and coal dust.

• Particles less than 15 × 10-6 m find their way into the bronchus and
bronchioles
– Examples: tobacco smoke and fumes

• Particles with diameter of 4 × 10-6 m and less can enter the alveoli
where gaseous exchange takes place between the bloodstream and
air.
– Examples: asbestos dust, glass fibre & viruses.
Sulphur Dioxide, SO2
• Sulphur dioxide is a colourless, toxic, non-flammable gas at normal temperatures
• and pressures
• It has an irritating, pungent smell &it is very soluble in water(0.166 mole per 100 g of water
at 293 K)
• The gas is easily adsorbed on to the surfaces of solid matter.
• Sulphur dioxide is emitted to the atmosphere from a number of natural sources:
– Geothermal activity releases vast amounts of sulphur dioxide, together with smaller
amounts of SO3, elemental sulphur, H2S and particulate sulphates.
• Such activity accounts for less than 1% of the global atmospheric burden of volatile sulphur
compounds.
• The main sources include the;
– oxidation of organic material that contains sulphur
– reduction of sulphur to H2S under anaerobic conditions
– combustion of solid fuels and petroleum products.
• Other contributions originate from:
– the smelting of sulphide ores, especially those of zinc, copper and lead,
– refinery processes
– sulphuric acid production and transport.
Contribution SO2 to Acid Rain
• When sulphur dioxide enters the atmosphere, it can be
easily oxidised to sulphur trioxide, SO3, which dissolves in
water to form sulphuric acid.
• The oxidation of SO2 can proceed via catalytic oxidation.
• The catalysts are aerosols that contain metal ions
• (e.g. Mn2+, Fe3+ and Cu2+) and metal oxides (Cr, Al, Pb and
Ca).
• The process is thermodynamically favourable, but
kinetically slow, and can be written as;

2SO2(g) + 2H2O(l) + O2(g) = 2H2SO4(aq)

• The surfaces of building materials act as catalytic centres, &

high humidity increases the rate of reaction
• When SO2 dissolves in water, the following equilibria are formed;
• SO2(g) + H2O(l) = H2SO3(aq)
• H2SO3(aq) + H2O(l) = H3O+(aq) + HSO3- (aq)
• HSO3- (aq) + H2O(l) = H3O+(aq) + SO32-(aq)
• 2HSO3- (aq) = S2O52-(aq) + H2O(l)

• Sulphur dioxide reacts with marble with the corresponding liberation of

carbon dioxide.
• CaCO3(s) + SO2(g) = CaSO3(s) + CO2(g)

• The sulphite is oxidized to calcium sulphate which is then washed

away by rain.
• 2CaSO3(s) + O2(g) = 2CaSO4(s)

• The reaction of SO2 with marble are responsible for the loss of carving
details of statues.
• Sulphur dioxide can also undergo oxidation
photochemically. Here, electromagnetic
radiation of the appropriate wavelength is
absorbed by SO2 molecules, which become
energetically excited (represented by SO2*)
which then reacts with dioxygen molecules to
produce SO3,
The Nitrogen Oxides
The Nitrogen oxides… cont’d
• As indicated by the positive sign of Gibbs free energy at 298 K, the
position of the equilibrium lies well over to the left-hand side. Since
it is an endothermic reaction, an increase in temperature will move
the equilibrium position to the right and more NO will be produced.
• For example, in the motor car engine
– when the spark plug is fired to ignite the petrol–air mixture, high
enough temperatures are generated to enable the equilibrium to lie
on the right-hand side,
– and so significant amounts of NO are generated.
• Upon being passed to the exhaust system and then to the
atmosphere where the temperatures are much lower,
– the NO cannot be decomposed & thus becomes a primary pollutant.
• There are also natural sources of NO;
– when lightning occurs both NO and NO2 are produced.
• Upon exposure to the air, NO combines rapidly with dioxygen to
form the secondary pollutant red-brown nitrogen(IV) oxide, NO2,

• At lower temperatures, nitrogen(IV) oxide dimerises to form

colourless N2O4,

• Nitrogen(IV) oxide is a poisonous, choking gas, which causes some

of the colour in smog. It dissolves readily in water, where it
disproportionates to form nitric(V) acid and nitric(III) acid,
• Nitrogen(I) oxide, N2O, is a colourless gas which is fairly soluble in water
– (130 cm3 in 100 g of water at 0 °C).
• It is tasteless with a slight sweetish smell. N2O is used as an anaesthetic and,
because it is not toxic, is also used as a foaming agent in whipped cream.
• It is unreactive at ordinary temperatures.
• Nitrogen(I) oxide is a greenhouse trace gas
– because it absorbs infrared radiation at 8.6 × 10-6 m and 7.8 × 10-6 m wavelength.
– It is 270 times more effective in this respect than is carbon dioxide.
• The atmospheric concentration of this gas is currently 310 ppb but it is apparently
increasing by about 0.25 % p.a.
• Nitrogen(I) oxide is released to the atmosphere from;
– the oceans, & tropical soils in particular.
– It is a by-product of both biological denitrification under aerobic conditions and nitrification
under anaerobic conditions.
– It is also released during the manufacture of adipic acid & nitric acid
The London Smog
Smog = Smoke + fog
• A smog is normally a mixture of smoke and fog. It is formed when the water content of air is
high and it is so calm that smoke and fumes accumulate near their emission source.
• Smog reduces visibility and often irritates the eyes and respiratory tract
• Between 4 December and 9 December 1952 occurred the most infamous ‘pea-souper’ smogs
recorded in the UK.
• This smog caused a range of cardiovascular and respiratory disorders which ultimately
resulted in 4,000 deaths above what would normally be expected for that time of year.
• Ninety per cent of these deaths occurred in people who were 45 years old or over, and the
deaths of infants below the age of one doubled.
• People were killed by inhaling water droplets that were at least as acidic as lemon juice.
• The smog was again caused by a temperature inversion, which when coupled with no wind
held down a vast acidic cloud.
• By 9 December, the radius of this cloud extended some 30 km from the centre of London.
The acid which caused the deaths was probably sulphuric acid since the levels of sulphur
dioxide in the smog proved to be very high.

• The incident prompted legislation to be implemented and resulted in the Clean Air Acts of
1956 and 1968.
Types of Smog
• There are two types of smog :
– Sulphurous smog &
– Photochemical smog
• Sulphurous smog results from high concentrations of sulphur
dioxide
– caused by the burning of sulphur containing fossil fuels.
– It is aided by damp conditions and the presence of particulate matter.
– In highly populated urban areas, the death rate may rise considerably
during prolonged periods of smog, particularly when, a temperature
inversion creates a smog-trapping ceiling over a city.
– Smog occurs most often in, and near, coastal cities and is an especially
severe air pollution problem in:
• Athens, Los Angeles and Tokyo
– The number of dangerous chemicals found in smog include;
• ozone, sulphur dioxide, hydrogen cyanide and hydrocarbons &
• products formed by their partial oxidation
 Photochemical Smog
• Photochemical smog is a whitish yellow to brown haze, which irritates sensitive
membranes and damages plants.

• It contains a variety of potentially harmful organic compounds.

•
• This type of smog does not need either smoke or fog to form.
•
• It is formed when two of the primary pollutants nitrogen monoxide and hydrocarbons
undergo reaction because of the energy supplied by ultraviolet and other types of
radiation from the Sun.

• The conditions necessary for this type of smog to form are the presence of the
pollutants themselves, sunlight, a stable temperature inversion and land enclosed by
hills.

• Petrol and diesel engines are regarded as one of the main contributors to this smog
problem since they emit large amounts of unburned hydrocarbons and oxides of
nitrogen.
The Chemistry of Photochemical Smog
• The main pollutants that cause photochemical smog are NO, NO2,
hydrocarbons (RH), PAN (peroxyethanoyl nitrate), ozone and the
aldehydes.
• The high temperatures found in combustion engines can give rise to
highly reactive free radicals.
• Dioxygen and dinitrogen may undergo the following reactions,
where M represents some molecule that absorbs the excess energy
of the reactions,

• The resulting nitrogen and oxygen atoms then react to form NO•,

• .
• Other reactions are also possible, such as

• Atomic oxygen can react with the hydrocarbon molecules that

represent unburnt petrol fumes thus,

• One of the products of the incomplete combustion of petrol is

carbon monoxide, CO. The •OH radical can react with the CO,

• The free radical HO2• is also found in the atmosphere and will react
with NO•,
• Any hydrocarbons present in the atmosphere can also react with •OH radicals,

• The free radical R• then reacts with dioxygen

• The peroxy radical, ROO•(g) will react with NO•,

• Aldehydes, RCHO, are formed by the reaction of the alkoxyl radical with oxygen

• Peroxy compounds, e.g. peroxyethanoyl nitrate (peroxyacetyl nitrate or PAN), are formed by the
reaction,

• Petrol and similar fumes contain the reactive unsaturated alkenes. Ozone readily attacks the double
bond to form a range of compounds,

• .
The Oxides of Carbon
• There are two major oxides of carbon: CO and CO2
• They are among the most common atmospheric pollutants.
• Carbon monoxide is;
– a colourless,
– tasteless,
– odourless gas,
– flammable &
– almost insoluble in water.
• It is mainly of concern because it;
– is both toxic to humans and
– has a role in the formation of ozone in the troposphere.
• The main sources of carbon monoxide are from
– the incomplete combustion of fossil fuels and wood,
– the oxidation of methane and
– the decomposition of organic matter.
• The combustion of carbon can occur via two steps;
• C(s) + 1/2 O2(g) = CO(g)
• CO(g) + 1/2 O2(g) = CO2(g)
• More CO is produced naturally by the oxidation of methane, CH4, in swamps and by the oxidation of
organic matter in tropical areas than by anthropogenic actions. The processes are,

• At higher altitudes, a major source of CO is via the photochemical decomposition of carbon dioxide,

• In the tropopause about 50 per cent of the CO is removed by reaction with hydroxyl free radicals,
• The origin of the HO•(g) radicals comes from the decomposition of water
molecules,

• where O* is an energetically excited oxygen atom.

• On the surface of soil CO is converted to CO2 by the rapid uptake and action of
bacteria and fungi,

• CO is also removed by reaction with dioxygen in the presence of a third molecule

M,

• .
• Plants also convert CO to:
– CO2 during the hours of darkness, &
– amino acids in the presence of sunlight.
• When humans are exposed to CO,
– it forms carboxy-haemoglobin at the expense of oxyhaemoglobin.
– Tissues are thus deprived of oxygen and asphyxiation occurs.
• If the victim continues to receive a high dosage of CO, then:
– permanent brain damage and even death will result.
• Initial symptoms include:
– dizziness, headache, nausea and faintness.

• Carbon dioxide is:

– a non-toxic, colourless gas with a slight odour.
– It is soluble in water and
– is about 1.5 times more dense than air.
• It is used in the production of:
– sodium carbonate,
– urea and
– mineral waters,
• It is also used as a refrigerant and in fire extinguishers
• Carbon dioxide is a major ‘greenhouse gas’ and is believed to contribute to global warming.
The Greenhouse Effect
• Qn1. Write notes on each of the following,
stipulating the theory, sources and effect of
the aspect:
– (a) acid rain
– (b) greenhouse effect
Management of air Pollution

• Qn2. Discuss the various approaches of

managing air pollution.