Air Pollution from Internal Combustion Engines and its control

Anoop Kumar
Mechanical Engg. Department
IT Hamirpur
History
Air pollution was never considered to be of great importance in early times. During the 1940s,
air pollution as a problem was first recognized in California basin.
Smoke and other pollutants from the many factories and automobiles combined with fog that was
common in this ocean area, and smog resulted. During the 1950s, the smog problem increased
along with the increase in population density and automobile density.
It was recognized that the automobile was one of the major contributors to the problem, and by
the 1960s emission standards were beginning to be enforced. During the next decades, emission
standards were adopted in the rest of the United States and in Europe and Japan.
By making engines more fuel efficient, and with the use of exhaust after treatment, emissions per
vehicle of HC, CO, and NOx were reduced by about 95% during the 1970s and 1980s. Lead, one
of the major air pollutants, was phased out as a fuel additive during the 1980s.
Air Pollution: definition
Pollution is a harmful change in the natural environment caused by human activities. Pollution is
the introduction into the air, water or ground of toxic substances that are damaging to human
health and ecosystems. It is mainly linked with human activity (discharge of domestic, industrial
and agricultural waste, application of pesticides by farmers; leaks of radioactive materials, gas
emissions into the atmosphere etc).

These emissions pollute the environment and contribute to global warming, acid
rain, smog, odors, and respiratory and other health problems.

The major causes of these emissions are non-stoichiometric combustion, dissociation
of nitrogen, and impurities in the fuel and air.
There are many substances in the air which may impair the health of plants and animals
(including humans), or reduce visibility. These arise both from natural processes and human
activity. Substances not naturally found in the air or at greater concentrations or in different
locations from usual are referred to as pollutants.
Pollutants can be classified as either primary or secondary. Primary pollutants are substances
directly emitted from a process, such as ash from a volcanic eruption or the carbon monoxide gas
from a motor vehicle exhaust.
Secondary pollutants are not emitted directly. Rather, they form in the air when primary
pollutants react or interact. An important example of a secondary pollutant is ground level ozone
- one of the many secondary pollutants that make up photochemical smog.
Note that some pollutants may be both primary and secondary: that is, they are both emitted
directly and formed from other primary pollutants.
Major primary pollutants produced by human activity include:
• Sulfur oxides (SOx) especially sulfur dioxide are emitted from burning of coal and oil.
• Nitrogen oxides (NOx) especially nitrogen dioxide are emitted from high temperature
combustion. Can be seen as the brown haze dome above or plume downwind of cities.
• Carbon monoxide is colourless, odourless, non-irritating but very poisonous gas. It is a
product by incomplete combustion of fuel such as natural gas, coal or wood. Vehicular
exhaust is a major source of carbon monoxide.
• Carbon dioxide (CO2), a greenhouse gas emitted from combustion.
• Volatile organic compounds (VOC), such as hydrocarbon fuel vapors and solvents.
• Particulate matter (PM), measured as smoke and dust. PM10 is the fraction of suspended
particles 10 micrometers in diameter and smaller that will enter the nasal cavity. PM2.5
has a maximum particle size of 2.5 µm and will enter the bronchies and lungs.
• Toxic metals, such as lead, cadmium and copper.
• Chlorofluorocarbons (CFCs), harmful to the ozone layer emitted from products currently
banned from use.
• Ammonia (NH3) emitted from agricultural processes.
• Odors, such as from garbage, sewage, and industrial processes
• Radioactive pollutants produced by nuclear explosions and war explosives, and natural
processes such as radon.
Secondary pollutants include:
• Particulate matter formed from gaseous primary pollutants and compounds in
photochemical smog, such as nitrogen dioxide.
• Ground level ozone (O3) formed from NOx and VOCs.

2
 • Peroxyacetyl nitrate (PAN) similarly formed from NOx and VOCs.
Minor air pollutants include:
• A large number of minor hazardous air pollutants. Some of these are regulated in USA
under the Clean Air Act and in Europe under the Air Framework Directive.
• A variety of persistent organic pollutants, which can attach to particulate matter.
Anthropogenic and atural Emissions
Most pollutants are emitted both by natural as well as by anthropogenic sources. Natural sources
are not influenced by humans or by human-induced activities. Volcanoes are a good example of
this type of source. Many emissions are biogenic, i.e., produced by living organisms, but these
emissions are very often influenced by human’s activities. Nitrous oxide (N2O) is a greenhouse
gas that is for a large part emitted during nitrification and de-nitrification processes (the
conversion of ammonium to nitrate and of nitrate to N2O and ammonium respectively), which
take place in the soil. The largest N2O emissions are observed where nitrogen-containing
fertilizer is applied in agriculture.
The ratio between anthropogenic and natural emissions is very important, as only the
anthropogenic portion can be influenced, e.g., by abatement measures. A good example is
provided by abatement measures for photochemical smog, with ozone and peroxyacyl nitrates
(PAN) as important secondary products. Photochemical smog is caused by nitrogen oxide (NOx)
and volatile organic compound (VOC) emissions. Therefore, the U.S. Environmental Protection
Agency (EPA) decided, some 20 years ago, to combat photochemical smog in the U.S. by
stringent reduction of VOC emissions and to a lesser extent, reduction of NOx; however, this
policy did not produce the desired results. Natural emissions, especially of terpenes and
isoprenes, proved to be so large that sufficient VOC concentrations were available in the
atmosphere for oxidant production, despite efforts to limit anthropogenic sources.
Anthropogenic sources (human activity) mostly related to burning different kinds of fuel
• "Stationary Sources" as smoke stacks of power plants, manufacturing facilities, municipal
waste incinerators.
• "Mobile Sources" as motor vehicles, aircraft etc.
• Marine vessels, such as container ships or cruise ships, and related port air pollution.
• Burning wood, fireplaces, stoves, furnaces and incinerators .
• Oil refining, and industrial activity in general.

3
 • Chemicals, dust and controlled burn practices in agriculture and forestry management,
(see Dust Bowl).
• Fumes from paint, hair spray, varnish, aerosol sprays and other solvents.
• Waste deposition in landfills, which generate methane.
• Military, such as nuclear weapons, toxic gases, germ warfare and rocketry.
atural sources
• Dust from natural sources, usually large areas of land with little or no vegetation.
• Methane, emitted by the digestion of food by animals, for example cattle.
• Radon gas from radioactive decay within the Earth's crust.
• Smoke and carbon monoxide from wildfires.
• Volcanic activity, which produce sulfur, chlorine, and ash particulates.
The following table shows some of the most polluted cities in the world in terms of particulate
matter.
Table 1: Most Polluted World Cities by [PM] Particulate matter, µg/m³ (2004)
City
169 Cairo, Egypt
150 Delhi, India
128 Kolkata, India (Calcutta)
125 Tianjin, China
123 Chongqing, China
109 Kanpur, Lucknow, India
104 Jakarta, Indonesia
101 Shenyang, China

4
 Figure 1: Dust Storm in Texas , USA

Table 2: Carbon dioxide emissions

Total CO2 emissions 106 Tons of CO2 per year:
United States: 2,790
China: 2,680
Russia: 661
India: 583
Japan: 400
Germany: 356
Australia: 226
South Africa: 222
United Kingdom: 212
South Korea: 185

5
 Table 3: Per capita CO2 emissions, Tons of CO2 per year per capita

Australia: 10
United States: 8.2
United Kingdom: 3.2
China: 1.8
India: 0.5
Health effects
The World Health Organization states that 2.4 million people die each year from causes directly
attributable to air pollution; with 1.5 million of these deaths attributable to indoor air pollution. A
study by the University of Birmingham has shown a strong correlation between pneumonia
related deaths and air pollution from motor vehicles. Worldwide more deaths per year are linked
to air pollution than to automobile accidents. Published in 2005 suggests that 310,000 Europeans
die from air pollution annually. Direct causes of air pollution related deaths include aggravated
asthma, bronchitis, emphysema, lung and heart diseases, and respiratory allergies. The US EPA
estimates that a proposed set of changes in diesel engine technology (Tier 2) could result in
12,000 fewer premature mortalities, 15,000 fewer heart attacks, 6,000 fewer emergency room
visits by children with asthma, and 8,900 fewer respiratory-related hospital admissions each year
in the United States.
The worst short term civilian pollution crisis in India was the 1984 Bhopal Disaster. Leaked
industrial vapors from the Union Carbide factory, belonging to Union Carbide, Inc., U.S.A.,
killed more than 2,000 people outright and injured anywhere from 150,000 to 600,000 others,
some 6,000 of whom would later die from their injuries. The United Kingdom suffered its worst
air pollution event when the December 4 Great Smog of 1952 formed over London. In six days
more than 4,000 died, and 8,000 more died within the following months. An accidental leak of
anthrax spores from a biological warfare laboratory in the former USSR in 1979 near Sverdlovsk
is believed to have been the cause of hundreds of civilian deaths. The worst single incident of air
pollution to occur in the United States of America occurred in Donora, Pennsylvania in late
October, 1948, when 20 people died and over 7,000 were injured.
The health effects caused by air pollutants may range from subtle biochemical and physiological
changes to difficulty in breathing, wheezing, coughing and aggravation of existing respiratory

6
and cardiac conditions. These effects can result in increased medication use, increased doctor or
emergency room visits, more hospital admissions and premature death. The human health effects
of poor air quality are far reaching, but principally affect the body's respiratory system and the
cardiovascular system. Individual reactions to air pollutants depend on the type of pollutant a
person is exposed to, the degree of exposure, the individual's health status and genetics
Effects on cystic fibrosis
A study from 1999 to 2000 by the University of Washington showed that patients near and
around particulate matter air pollution had an increased risk of pulmonary exacerbations and
decrease in lung function. Patients were examined before the study for amounts of specific
pollutants like P. aeruginosa or B. cepacia as well as their socioeconomic standing. Participants
involved in the study were located in the United States in close proximity to an Environmental
Protection Agency .During the time of the study 117 deaths were associated with air pollution. A
trend was noticed that patients living closer or in large metropolitan areas to be close to medical
help also had higher level of pollutants found in their system because of more emissions in larger
cities. With cystic fibrosis patients already being born with decreased lung function everyday
pollutants such as smoke emissions from automobiles, tobacco smoke and improper use of
indoor heating devices could add to the dissemination of lung function.
Effects on COPD
Chronic obstructive pulmonary disease (COPD) include diseases such as chronic bronchitis,
emphysema, and some forms of asthma. Two researchers Holland and Reid conducted research
on 293 male postal workers in London during the time of the 1952 London Fog incident and 477
male postal workers in the rural setting. The amount of the pollutant FEV1 was significantly
lower in urban employees however lung function was decreased due to city pollutions such as
car fumes and increased amount of cigarette exposure. It is believed that much like cystic
fibrosis, by living in a more urban environment serious health hazards become more apparent.
Studies have shown that in urban areas patients suffer mucus hypersecretion, lower levels of lung
function, and more self diagnosis of chronic bronchitis and emphysema.
Effects on children
Cities around the world with high exposure to air pollutants has the possibility of children living
within them to develop asthma, pneumonia and other lower respiratory infections as well as a
low initial birth rate. Protective measures to ensure the youths health is being taken in countries

7
such as New Delhi where buses now use compressed natural gas to help eliminate the “pea-
soup” fog. Research by the World Health Organization shows there is the greatest concentration
of particulate matter particles in countries with low economic world power and high poverty and
population rates. Examples of these countries include Egypt, Sudan, Mongolia, and Indonesia.
The Clean Air Act was passed in 1970, however in 2002 at least 146 million Americans were
living in areas that did not meet at least one of the “criteria pollutants” laid out in the 1997
National Ambient Air Quality Standards. Those pollutants included: ozone, particulate matter,
sulfur dioxide, nitrogen dioxide, carbon monoxide, and lead. Because children are outdoors more
and have higher minute ventilation they are more susceptible to the dangers of air pollution.

Air Quality in India

Urban Air Pollution

Nationwide, at over 90 per cent of the monitoring stations, the annual mean concentration
of Suspended Particulate Matters (SPM) has exceeded WHO’s specified limit (75 micro-
gm/m3).

In cities like Mumbai, Ahmedabad and agpur, the annual average of SPM is at least
three times higher than WHO standards and in Delhi, Kolkata and Kanpur, the annual
average SPM values are over five times the standards.

However, the annual average concentration of SOx and NOx are generally low in terms
of WHO specified limits.

Parikh & Parikh (1999) estimated that 82 per cent of SO2, 38 per cent of NO2, 88 per
cent of volatile organic compound (VOC) and 96 per cent of particulate matter emission
in India come from the household sector.

Women, children and the older generation, who spend most of their time indoors, are
badly affected.

The major reasons for indoor air pollution are inefficient burning of inferior fuels like
cowdung, agricultural residue, coal and fuel wood, along with poor ventilation systems
inside the house.
Indoor Air Pollution
According to a TERI study, particulate matter concentrations in kitchens due to the burning of
bio-fuels are known to be as high as 30 times the WHO standards, while concentrations at the

8
workplace for primary workers can be as high as 12 times the WHO standard, though outdoor
concentrations are about 2.5 times the WHO standard in urban and rural areas, and 8 times the
standard in slums in India.
Air Pollution in Delhi- A Fact File

Delhi is arguably the most polluted city of the four metropolises (Kolkata, Chennai &
Mumbai the other three).

Delhi’s air - as sampled at one of Delhi's greenest areas, namely Lodhi Road - is dirtier
now than what it was in March 2000.

The concentration of very fine particles, finer than 10 micrometers (PM10), has gone up
by as much as 50%, as shown in the analysis of the latest results of monitoring air
pollution carried by researchers at TERI
TERI scientists compared the quality of air before the Supreme Court's ban on old commercial
vehicles came into force from 1st April 2000 with that after the ban. Their results also show that
whereas the concentration of fine particles has gone up, that of NOx, a pollutant given off mainly
by diesel vehicles, has come down by as much as 40%.
Air quality monitoring at various traffic intersections in Delhi revealed that while SO2
concentration was within limits at all locations, the concentration of NO2 exceeded the standard
at Connaught Place, Windsor Place and Pusa Road. CO concentration was recorded much higher
than the permissible limit at all locations. Concentration of these air pollutants was found to be
high between 8-11 AM and 4-9 PM indicating the impact of vehicular density on air quality.
The causes of increasing air pollution in Delhi are:

the rapid pace of urbanization

and even faster pace of motorization.
Delhi’s urban population, which was 3.65 million in 1970/71, increased to 5.73 million in
1980/81 and 8.47 million in 1990/91 indicating a more than twofold increase in the last two
decades
The corresponding figures of the increase in the vehicle population accounts for 0.20 million,
0.56 million, and 1.8 million, respectively, which indicates more than a nine times increase in
vehicles in the last two decades.

In 1991 the air pollutants emitted daily were 1,450 metric tonnes.

9

Recent estimates show that about 3,000 metric tonnes of air pollutants are emitted
everyday in Delhi.

Thus it can be seen that the emissions have more than doubled in less than 10 years.
The major sources of air pollutants in Delhi are:

1. Emissions from vehicles (67%),

2. Coal based thermal power plants (13%),

3. Industrial units (12%) and

4. Domestic (8%).
Vehicular emissions constitute a very important component of any strategy to control air
pollution especially in Delhi. It is notable that two thirds of the vehicles in Delhi are two-
wheelers, operated on two stroke engines accounting for 70% of hydrocarbon and 50% of
carbon monoxide emissions. The Central Pollution Control Board (CPCB) has been monitoring
carbon monoxide at the ITO traffic intersections since 1989. The concentrations of carbon
monoxide in 1996 show an increase of 92% over the values observed in 1989.
Who Pollutes the Air

Air pollution is the effect of unsustainable economic activities of production and
consumption.

Burning of fossil and bio-fuels,

Industrial process and

Vehicles in the transport sector
Nearly 62 per cent of Indian power generation is from coal fired thermal power plants and 70 per
cent of the coal produced every year in India has been used for thermal generation. Although,
fortunately, most of the Indian coal has a low sulfur content, burning of coal has been the source
of serious environmental problems including the emission of CO2, NOx, fly-ash etc.
It is reported that the transport sector contributed most of the pollution load (27 per cent NOx, 74
per cent carbon monoxide [CO], 11 per cent volatile organic compound and 100 per cent lead) in
urban areas
Vehicular pollution: causes

Many vehicles are in poor condition, creating more particulates and burning fuel
inefficiently.

10

Two-stroke engines are inefficient with respect to four-stroke engines and emit
hydrocarbons and smoke at a much higher rate.

Lower quality fuel is used, leading to the emissions of far greater quantities of pollutants.

Motor vehicles are concentrated in a few large cities.

There is a lack of public transport and travel demand management.

Bad road conditions and poor infrastructure
Realising that vehicles, i.e., IC Engines are one of the major sources of air pollution, especially
in cities, let us understand the emissions from them.
Composition of Exhaust from IC Engines
1. Hydrocarbons
2. Carbon monoxide
3. Oxides of Nitrogen
4. Particulate matter
5. Other emissions

Hydrocarbons
Exhaust gases leaving the combustion chamber of an SI engine contain up to 6000 ppm of
hydrocarbon components, the equivalent of 1-1.5 % of the fuel. About 40% of this is unburned
gasoline fuel components. The other 60% consists of partially reacted components that were not
present in the original fuel. These consist of small non-equilibrium molecules which are formed
when large fuel molecules break up (thermal cracking) during the combustion reaction. When
hydrocarbon emissions get into the atmosphere, they act as irritants and odorants; some are
carcinogenic. All components except CH4 react with atmospheric gases to form photochemical
smog.
Causes of Hydrocarbon emission are :
1. on stoichiometric air-fuel ratio
2. Incomplete combustion
3. Crevice volume
4. Other sources
on stoichiometric air-fuel ratio

11
 A fuel rich air-fuel ratio does not have enough oxygen to react with all the carbon and
hydrogen, and both HC and CO emissions increase. HC emissions also increase at very lean
mixtures due to poor combustion and misfires. The generation of nitrogen oxide emissions is a
function of the combustion temperature, being greatest near stoichiometric conditions when
temperatures are the highest. Peak NOx emissions occur at slightly lean conditions, where the
combustion temperature is high and there is an excess of oxygen to react with the nitrogen.
With a fuel-rich mixture there is not enough oxygen to react with all the carbon, resulting
in high levels of HC and CO in the exhaust products. For e.g., in engine startup, when the air-
fuel mixture is purposely made very rich or during rapid acceleration under load. If AF is too
lean poor combustion occurs, again resulting in HC emissions. The extreme of poor combustion
for a cycle is total misfire. It occurs more often as AF is made more lean. One misfire out of
1000 cycles gives exhaust emissions of 1 gm/kg of fuel used.
Incomplete Combustion
Even when the fuel and air entering an engine are at the ideal stoichiometric mixture, perfect
combustion does not occur and some HC ends up in the exhaust. There are several causes of this.
Incomplete mixing of the air and fuel results in some fuel particles not finding oxygen to react
with. Flame quenching at the walls leaves a small volume of unreacted air-and-fuel mixture. The
thickness of this unburned layer is on the order of tenths of a mm. Some of this mixture, near the
wall that does not originally get burned as the flame front passes, will burn later in the
combustion process as additional mixing occurs due to swirl and turbulence.
Flame quenching
A cause of flame quenching is the expansion which occurs during combustion and power stroke.
As the piston moves away from TDC, expansion of the gases lowers both temperature and
pressure within the cylinder. This slows combustion and finally quenches the flame somewhere
late in the power stroke. This leaves some fuel particles unreacted. High exhaust residual causes
poor combustion and a greater likelihood of expansion quenching. This is experienced at low
load and idle conditions. High levels of EGR will also cause this.
It has been found that HC emissions can be reduced if a second spark plug is added to an engine
combustion chamber. By starting combustion at two points, the flame travel distance and total
reaction time are both reduced, and less expansion quenching results.
Crevice Volume

12
During the compression stroke and early part of the combustion process, air and fuel are
compressed into the crevice volume of the combustion chamber at high pressure. As much as 3%
of the fuel in the chamber can be forced into this crevice volume. Later in the cycle during the
expansion stroke, pressure in the cylinder is reduced below crevice volume pressure, and reverse
blow by occurs. Fuel and air flow back into the combustion chamber, where most of the mixture
is consumed in the flame reaction.
However, by the time the last elements of reverse blow by flow occur, flame reaction has
been quenched and unreacted fuel particles remain in the exhaust.
Location of the spark plug relative to the top compression ring gap will affect the amount of HC
in engine exhaust, the ring gap being a large percent of crevice volume. The farther the spark
plug is from the ring gap, the greater is the HC in the exhaust. This is because more fuel will be
forced into the gap before the flame front passes.
Crevice volume around the piston rings is greatest when the engine is cold, due to the differences
in thermal expansion of the various materials. Up to 80% of all HC emissions can come from
this source.
Other sources
Leak Past the Exhaust Valve :
As pressure increases during compression and combustion, some air-fuel is forced into the
crevice volume around the edges of the exhaust valve and between the valve and valve seat. A
small amount even leaks past the valve into the exhaust manifold.

Valve overlap
When the exhaust valve opens, the air-fuel which is still in this crevice volume gets
carried into the exhaust manifold, and there is a momentary peak in HC concentration at the start
of blow down.

During valve overlap, both the exhaust and intake valves are open, creating a path where
air-fuel intake can flow directly into the exhaust. A well-designed engine minimizes this
flow, but a small amount can occur.

The worst condition for this is at idle and low speed, when real time of overlap is
greatest.
Deposits on Combustion Chamber Walls :

13
Gas particles, including those of fuel vapor, are absorbed by the deposits on the walls of the
combustion chamber. The amount of absorption is a function of gas pressure, so the maximum
occurs during compression and combustion.
Later in the cycle, when the exhaust valve opens and cylinder pressure is reduced,
absorption capacity of the deposit material is lowered and gas particles are desorbed back into
the cylinder. These particles, including some HC, are then expelled from the cylinder during the
exhaust stroke.
Oil on Combustion Chamber Walls:
A very thin layer of oil is deposited on the cylinder walls of an engine to provide lubrication
between them and the moving piston. During the intake and compression strokes, the incoming
air and fuel comes in contact with this oil film. In much the same way as wall deposits, this oil
film absorbs and desorbs gas particles, depending on gas pressure.
Two-Stroke Cycle Engines:
Apart from the above factors two stroke cycle engines produce more hydrocarbon emission due
to following reasons:
1. Simultaneous opening of intake and exhaust ports during scavenging process.
2. Crankcase compression in some of the engines. As piston and cylinder are lubricated with
oil, so during compression oil gets vaporized and burns along with the fuel. But, due to
its higher molecular weight it is not completely combusted and some hydrocarbons are
added to exhaust.
CI Engines:
Because they operate with an overall fuel-lean equivalence ratio, CI engines have only about
one-fifth the HC emissions of an SI engine. The components in diesel fuel have higher molecular
weights on average than those in a gasoline blend, and this results in higher boiling and
condensing temperatures. This allows some HC particles to condense onto the surface of the
solid carbon soot that is generated during combustion.
Most of this is burned as mixing continues and the combustion process proceeds. Only a small
percent of the original carbon soot that is formed is exhausted out of the cylinder. The HC
components condensed on the surface of the carbon particles, in addition to the solid carbon
particles themselves, contribute to the HC emissions of the engine.

14
Some local spots in the combustion chamber will be too lean to combust properly, and other
spots will be too rich, with not enough oxygen to consume all the fuel. Less than total
combustion can be caused by undermixing or overmixing.
With undermixing, some fuel particles in fuel-rich zones never find oxygen to react with. In
fuel-lean zones, combustion is limited and some fuel does not get burned. With overmixing,
some fuel particles will be mixed with already burned gas and will therefore not combust totally.
In general, a CI engine has about a 98% combustion efficiency, with only about 2% of the HC
fuel being emissions.
Carbon Monoxide
Carbon monoxide is a colorless, odorless, Poisonous gas which is formed when engine is run
with fuel rich composition. Maximum CO is generated when is running rich like during starting
or when accelerating under high load.
Typically the exhaust of SI engine contains about 0.2%-0.5% of CO. Poor mixing, Local rich
regions and incomplete combustion will generate CO. Under ideal condition, a good SI engine
can have an exhaust mole fraction CO as 0.001 mole fraction. The formation of carbon
monoxide also represents loss of energy as it shall burn to produce some more energy.

CI engines operate at overall lean ratio and so have very low CO emission.

15
Figure: Emissions from an SI engine as a function of equivalence ratio.

OXIDES OF ITROGE (Ox)

Exhaust gases of an engine can have up to 2000 ppm of oxides of nitrogen. Most of this will be
nitrogen oxide (NO), with a small amount of nitrogen dioxide (NO2), and traces of other
nitrogen-oxygen combinations. These are all grouped together as NOx (or Ox), with x
representing some suitable number. NOx is a very undesirable emission, and regulations that
restrict the allowable amount continue to become more stringent. Released NOx reacts in the
atmosphere to form ozone and is one of the major causes of photochemical smog. NOx is created
mostly from nitrogen in the air. Nitrogen can also be found in fuel blends, which may contain
trace amounts ofNH3, NC, and HCN, but this would contribute only to a minor degree. There are

16
a number of possible reactions that form NO, all of which are probably occurring during the
combustion process and immediately after. These include but are not limited to:

At the very high temperatures that occur in the combustion chamber of an engine, some diatomic
nitrogen (N2) breaks down to monatomic nitrogen (N) which is reactive. Although maximum
flame temperature will occur at a stoichiometric air-fuel ratio (AF= 1), maximum NOx is formed
at a slightly lean equivalence ratio of about AF = 0.95. At this condition flame temperature is
still very high, and in addition, there is an excess of oxygen that can combine with the nitrogen to
form various oxides. If ignition spark is advanced, the cylinder temperature will be increased and
more NOx will be created. The Ox-versus-time relationship shown in the figure below
supports the fact that NOx is reduced in modern engines with fast-burn combustion chambers.

17
PARTICULATES

The exhaust of CI engines contains solid carbon soot particles. These are seen as exhaust smoke
and are an undesirable odorous pollution. Soot particles are clusters of solid carbon spheres.
These spheres have diameters from 10 nm to 80 nm (1 nm = 10-9 m), with most within the
range of 15-30 nm. The spheres are solid carbon with HC and traces of other components
absorbed on the surface. A single soot particle will contain up to 4000 carbon Spheres. Carbon
spheres are generated in the combustion chamber in the fuel-rich zones where there is not
enough oxygen to convert all carbon to CO2:

CxHy + z 02 ~a CO2 + bH20 + cCO + dC(s)

18
Maximum density of particulate emissions occurs when the engine is under load at WOT. At
this condition maximum fuel is injected to supply maximum power, resulting in a rich mixture
and poor fuel economy. This can be seen when a truck accelerates uphill or from a start.
Then, as turbulence and mass motion continue to mix the components in the combustion
chamber, most of these carbon particles find sufficient oxygen to further react and are consumed
to CO2:
C(s) + O2 ~ CO2
Over 90% of carbon particles originally generated within an engine are thus consumed and
never get exhausted. Up to about 25% of the carbon in soot comes from lubricating oil
components which vaporize and then react during combustion. The rest comes from the fuel and
amounts to 0.2-0.5% of the fuel.

Other emissions
Aldehyde: A major problem in alcohol as fuel is the generation of aldehyde which is an eye and
respiratory irritant.
Sulphur: Many fuels used in CI engines contain sulphur, which when exhausted contributes to
the acid rain problem of the world. Unleaded gasoline contains 140-160 ppm of sulphur by
weight and some diesel even contain upto 5000 ppm of sulphur by weight, but in US and some
other countries it is restricted to one tenth of this value. At high temperatures sulphur combines
with hydrogen and oxygen.

Engine exhaust may contain upto 20 ppm of SO2. this then reacts with oxygen to give :

These oxide then react with water to give various acids.

S03 + H2O ~ H2S04
SOz + H2O ~ H2S03
Lead :
Lead was a major gasoline additive from its introduction in 1923 to when it was phased out in
the 1980s. The additive TEL (tetraethyllead) was effectively used to increase gasoline octane

19
number, which allowed higher compression ratios and more efficient engines. However, the
resulting lead in the engine exhaust was a highly poisonous pollutant. Leaded gasoline contains
about 0.15 gm/liter of lead in the fuel. Between 10% and 50% of this gets exhausted out with the
other combustion products. The remaining lead gets deposited on the walls of the engine and
exhaust system.
AFTERTREATMET
After the combustion process stops, those components in the cylinder gas mixture that have not
fully burned continue to react during the expansion stroke, during exhaust blbwdown, and into
the exhaust process. Up to 90% of the HC remaining after combustion reacts during this time
either in the cylinder, near the exhaust port, or in the upstream part of the exhaust manifold. CO
and small component hydrocarbons react with oxygen to form COz and Hz0 and reduce
undesirable emissions. The higher the exhaust temperature, the more these secondary reactions
occur and the lower the engine emissions. Higher exhaust temperature can be caused by
stoichiometric air-fuel combustion, high engine speed, retarded spark, and/or a low expansion
ratio.

Thermal Converters
Secondary reactions occur much more readily and completely if the temperature is high, so some
engines are equipped with thermal converters as a means of lowering emissions. Thermal
converters are high-temperature chambers through which the exhaust gas flows. They promote
oxidation of the CO and HC which remain in the exhaust.
CO + ~ Oz ~ COz
For this reaction to occur at a useful rate, the temperature must be held above 700°C [58].
CxHy + Z Oz ~ X COz +hHzO
where Z = x + ~ y.

This reaction needs a temperature above 600°C for at least 50 msec to substantially reduce HC. It
is therefore necessary for a thermal converter not only to operate at a high temperature but to be
large enough to provide adequate dwell time to promote the occurrence of these secondary
reactions. Most thermal converters are essentially an enlarged exhaust manifold connected to the
engine immediately outside the exhaust ports. This is necessary to minimize heat losses and keep

20
the exhaust gases from cooling to non-reacting temperatures. However, in automobiles this
creates two very serious problems for the engine compartment. In modern, low-profile,
aerodynamic automobiles, space in the engine compartment is very limited, and fitting in a large,
usually insulated thermal converter chamber is almost impossible.
Secondly, because the converter must operate above 700°C to be efficient, even if it is insulated
the heat losses create a serious temperature problem in the engine compartment.
Some thermal converter systems include an air intake which provides additional oxygen to react
with the CO and HC. This increases the complexity, cost, and size of the system. Flow rate of air
is controlled by the EMS as needed. Air addition is especially necessary during rich operating
conditions such as startup. Because exhaust from engines is often at a lower temperature than is
needed for efficient operation of a thermal converter, it is necessary to sustain the high
temperatures by the reactions within the system. Adding outside air, which is at a lower
temperature, compounds this problem of maintaining the necessary operating temperature. NOx
emissions cannot be reduced with a thermal converter alone.

CATALYTIC COVERTERS
The most effective aftertreatment system for reducing engine emissions is the catalytic
converter found on most automobiles and other modern engines of medium or large size. HC and
CO can be oxidized to Hz0 and COz in exhaust systems and thermal converters if the
temperature is held at 600°-700°C. If certain catalysts are present, the temperature needed to
sustain these oxidation processes is reduced to 250°-300°C, making for a much more attractive
system. A catalyst is a substance that accelerates a chemical reaction by lowering the energy
needed for it to proceed. The catalyst is not consumed in the reaction and so functions
indefinitely unless degraded by heat, age, contaminants, or other factors. Catalytic converters are
chambers mounted in the flow system through which the exhaust gases flow. These chambers
contain catalytic material, which promotes the oxidation of the emissions contained in the
exhaust flow.

Generally, catalytic converters are called three-way converters because they promote the
reduction of CO, HC, and NOx. Most consist of a stainless steel container mounted somewhere
along the exhaust pipe of the engine. Inside the container is a porous ceramic structure through

21
which the gas flows. In most converters, the ceramic is a single honeycomb structure with many
flow passages. Some converters use loose granular ceramic with the gas passing between the
packed spheres. Volume of the ceramic structure of a converter is generally about half the
displacement volume of the engine. This results in a volumetric flow rate of exhaust gas such
that there are 5 to 30 changeovers of gas each second, through the converter. Catalytic converters
for CI engines need larger flow passages because of the solid soot in the exhaust gases. The
surface of the ceramic passages contains small embedded particles of catalytic material that
promote the oxidation reactions in the exhaust gas as it passes.
Aluminum oxide (alumina) is the base ceramic material used for most catalytic converters.
Alumina can withstand the high temperatures, it remains chemically neutral,
it has very low thermal expansion, and it does not thermally degrade with age. The catalyst
materials most commonly used are platinum, palladium, and rhodium. Palladium and platinum
promote the Oxidation of CO and HC, platinum especially active in the HC reactions. Rhodium
promotes oxidation of NOx in one of the following reactions :

Also, often used is cerium oxide which promotes the so called water gas shift

This reduces the CO with the help of water vapour instead of oxygen, which is very important
when the engine is running rich. Efficiency of a catalytic converter is very dependent on
temperature. When a converter in good working condition is working at full temperature of 400
°C or more, it will remove 98-99% of CO, 95% of NOx and more than 95% of HC from exhaust.
Appropriate equivalence ratio is also necessary to get high converter efficiency.

22
Figure: Conversion efficiency of catalytic converters as a function of converter temperature

Conclusions
Effective control of HC and CO occurs with stoichiometric or lean mixtures, while control of
NOx requires near stoichiometric conditions. Very poor NOx control occurs with lean mixtures.
Catayltic converters are effective device for emission control. However, it is important that a
catalytic converter be operated hot to be efficient, but no hotter. Engine malfunctions can cause
poor efficiency and overheating of converters.
A poorly tuned engine can have misfires and periods of too lean and/or too rich conditions.
These cause the converter to be inefficient at the very time emissions are very high and maximum
converter efficiency is needed. A turbocharger lowers the exhaust temperature by removing
energy, and this can make a catalytic converter less efficient.
Many other methods viz. chemical treatment, change of fuel, mixing of fuel, hybrid vehicles,
exhaust gas recirculation etc. are also areas of active research.

23