UNIT V EMISSIONS FROM S.

I ENGINES

EMISSION STANDARDS
The vehicle emission standards were implemented for the first time in 1965 when control of crankcase
hydrocarbon emissions from gasoline passenger cars was required as per the law. Use of positive crankcase
ventilation (PCV) system on the gasoline passenger cars became necessary to prevent emission of hydrocarbon
rich crankcase blow by gases into atmosphere. At the same time, the exhaust gas emission standards for new cars
were also established in the state of California and in 1968, US enacted legislation to implement nationwide
vehicle emission regulations. In Europe, vehicle emission standards were implemented beginning from the year
1970. Over the years, the emission standards have become more and more stringent and have driven the
development of advanced engine designs and emission control technology. Now, nearly all the countries all over
the world have enforced vehicle emission regulations of varying severity following largely either the US or the
European regulations. The emission limits that are in force in the US and Europe and the trends thereof over the
years are discussed below.
Light Duty Vehicles
European Standards
European emission standards for the light duty vehicles are given in the Table. Before1992 i.e. prior to Euro 1
standards, emission limits were based on ECE-15 cycle and varied with vehicle reference weight, the higher
emissions was permitted for the heavier passenger cars. From 1992 however, the same limits for all the passenger
cars irrespective of vehicle weight as in the US were introduced. EU standards up to Euro 3 stage require
durability demonstration for 80,000 km or 5 years, whichever occurs first. In lieu of actual durability test, the
manufacturers may use the following deterioration factors:
• Gasoline cars: 1.2 for CO, HC and NO x
• Diesel cars: 1.1 for CO, NO x and HC+ NO x , 1.2 for PM
Euro 5 stage requires durability of 160,000 km or 5 years, whichever occurs first. The emission standards for the
light duty trucks and medium duty vehicles also, have been laid down and can be found in the European
regulations.
European Emission Standards for Passenger Cars, g/km

Since 1991/1992 when the European vehicles needed catalytic exhaust after treatment to meet the regulations
drastic reductions in emission limits have been enforced. Relative emissions limits since 1990 (pre-Euro1) to Euro
4 limits are shown on Fig 4.8. The Euro 4 limits were only about 5 to 15 % of the pre 1990 limits. Beyond Euro 4
standards, drastic reductions in diesel NOx and PM emissions are required. The diesel passenger car NOx would
be reduced to just 1/3 rd and PM to 1/5 th of Euro 4 limits.
Heavy Duty Engines
Most heavy-duty vehicles are powered by the diesel engines. Hence, the heavy duty engine emission regulations
have been directed more towards reduction in NOx and PM emissions.
European Standards
The European regulations for new production heavy-duty diesel engines since Euro 1 stage are given in Tables
4.5 and 4.6. These standards apply to both heavy-duty highway vehicles as well as to urban buses. The test cycle
was changed with the implementation of Euro 3 standards in the year 2000. To meet the Euro 4 standards and
beyond, diesel engines need some form of after treatment devices such as oxidation catalysts, particulate filters,
de-NOx catalysts etc. From Euro 3 regulations, heavy-duty engines operating on gaseous fuels are tested also on
ETC in addition to ESC cycle. However, for compliance with Euro 4 or later standards, all heavy-duty engines are
to meet ESC, ELR and ETC test limits. Evolution of European emission regulations for heavy duty vehicles is
shown on Figure
Emission standards for CI and SI engine, ETC test, g/kWh

(1) for natural gas engines only; (2) not applicable for gas fuelled engines for approval to Euro 3 and Euro 4
standards; (3) for engines of less than 0.75 litre/cylinder swept volume and rated speed above 3000 rpm; .(4) THC
(total hydrocarbons) limits apply for diesel; (5) particle number limit may apply to prevent ultra fine particles
from flow through ( or partial flow) filters.

Evolution of European Heavy duty Emission Standards

Emission Standards in India
India has adopted the European emission limits on a slightly modified driving cycle for the light duty vehicles.
The overall emission limits and test procedures for the heavy duty vehicles however are the same as those in
Europe. In India, the emission limits are being enforced by a time lag of around 5 years as shown in Table.
Indian Emission Regulations
(light duty emission standards with a modified EUDC maximum speed limited to 90 km h)

(1) Delhi, Mumbai, Kolkata, Chennai

(2) Bangalore, Hyderabad, Ahmadabad, Pune, Surat , Kanpur , Agra ; added from the year 2005- Sholapur and
Lucknow
Motorcycle Emission Standards
Asian countries have a very large population of motorcycles and mopeds and these vehicles are estimated to
contribute very heavily to urban air pollution. Taiwan and India have lead enforcement of stringent emission
limits for two wheelers. Although the USA and Europe have implemented emission regulations for the two
wheelers many decades back, but the number of these vehicles not being very large the standards were not
tightened for a long time. However, now in these countries too very stringent limits are being enforced.
Motorcycle emission standards in some countries are given in Table 4.8. Presently, most countries follow
different test procedures. However, as discussed earlier, a world motorcycle test cycle has been developed and in
future most countries are expected to use WMTC.
Worldwide Motorcycle Emission Standards
Major sources of Air pollution:
1. Automotive Engines
2. Electrical power generating stations
3. Industrial and domestic fuel consumption
4. Refuse burning of industrial processing, wastes etc.,
Sources of Pollutants from Gasoline Engine:
There are four possible sources of atmospheric pollution from a petrol engine powered vehicle. They are
1. Fuel Tank
2. Carburettor
3. Crank case
4. Engine
The amount of pollutants contributed by the above mentioned sources are as follows.
a.. Fuel tank evaporative loss - 5 to 10 % of HC
b. Carburettor evaporative loss - 5 % of HC
c. Crank case blow by - 20 to 35 % of HC
d. Tail Pipe exhaust - 50 to 60 % of HC and almost all Co and NOx

Emittant as a Pollutant:
 An emittant is said to be a pollutant when it has some harmful effect upon our surroundings.
 The primary source of energy for our automotive vehicles is crude oil from underground which typically
contains varying amounts of sulphur. Much of the sulphur is removed during refining of automotive fuels.
Thus the final fuel is hydrocarbon with only a small amount of sulphur. If we neglect sulphur and consider
complete combustion, only water and carbon dioxide would appear in the exhaust.
 Water is not generally considered undesirable and therefore it is not considered as a pollutant. Likewise
carbon dioxide is also not considered as pollutant in earlier days. But due to increase in global warming due to
CO2 which is a green house gas, now a days CO2 is also considered as unwanted one.
 Then apart from this we get sulphur dioxide a pollutant which is a product of complete combustion. Apart
from this all the compounds currently considered as pollutants are the result of imperfect or incomplete
combustion.
Pollutants Pollutant Effects
Unburned Hydro Carbons (UBHC) Photochemical Smog
Nitric Oxide Toxic , Photochemical Smog
Carbon monoxide Toxic
Lead compounds Toxic
Smoke combines with fog and forms a dense invisible layer in the atmosphere which is known as Smog.
The effect of Smog is that it reduces visibility.
Effect of Pollutants on Environment:
a. Unburned Hydro Carbons ( UBHC ):
 The major sources of UBHC in an automobile are the engine exhaust, evaporative losses from fuel system,
blow by loss and scavenging in case of 2-stroke petrol engines.
 Unburned or partially burned hydrocarbons in gaseous form combine with oxides of nitrogen in the presence
of sunlight to form photochemical smog.
UBHC + NOx → Photochemical smog
 The products of photochemical smog cause watering and burning of the eyes and affect the respiratory
system, especially when the respiratory system is marginal for other reasons.
 Some of the high molecular weight aromatic hydrocarbons have been shown to be carcinogenic in animals.
Some of the unburned hydrocarbons also serve as particulate matter in atmosphere.
b. Carbon monoxide:
Carbon monoxide is formed during combustion in engine only when there is insufficient supply of air.
The main source is the engine exhaust.
The toxicity of carbon monoxide is well known. The hemoglobin the human blood which carries oxygen
to various parts of the body has great affinity towards carbon monoxide than for oxygen. When a human is
exposed to an atmosphere containing carbon monoxide, the oxygen carrying capacity of the blood is reduced and
results in the formation of carboxy hemoglobin. Due to this the human is subjected to various ill effects and
ultimately leads to death.
The toxic effects of carbon monoxide are dependent both on time and concentration as shown in the
diagram.

C. Oxides of Nitrogen (NOx):

Oxides of nitrogen (NO, NO2, N2O2 etc) are formed at higher combustion temperature present in engines
and the engine exhaust is the major source.
Like carbon monoxide, oxides of nitrogen also tend to settle on the hemoglobin in blood. Their most
undesirable effect is their tendency to join with moisture in the lungs to form dilute nitric acid. Because the
amounts formed are minute and dilute, their effect is very small but over a long period of time cam be
cumulatively undesirable, especially when the respiratory problems for other reasons are found.
Another effect is that, the oxides of nitrogen are also one of the essential component for the formation of
photochemical smog.

GASOLINE ENGINE EMISSIONS

The emissions form gasoline powered automobiles are mainly
1. Unburned Hydro Carbons
2. Carbon monoxide
3. Oxides of nitrogen
4. Oxides of sulphur and
5. Particulates including smoke
Pollutant formation in Gasoline engine:
1. HYDROCARBONS:
Incomplete combustion:
Under operating conditions, where mixtures are extremely rich or lean, or exhaust gas dilution is
excessive, incomplete flame propagation occurs during combustion and results in incomplete combustion of the
charge. Normally, the carburettor supplies air fuel mixture in the combustible range. Thus incomplete combustion
usually results from high exhaust gas dilution arising from high vacuum operation such as idle or deceleration.
However during transient operation, especially during warm up and deceleration it is possible that some times too
rich or too lean mixture enters the combustion chamber resulting in very high HC emission.
Factors which promote incomplete flame propagation and misfire include:
a. Poor condition of the ignition system, including spark plug
b. Low charge temperature
c. Poor charge homogeneity
d. Too rich or lean mixture in the cylinder
e. Large exhaust residual quantity
f. Poor distribution of residuals with cylinder
Carburetion and mixture preparation, evaporation and mixing in the intake manifold, atomization at the
intake valve and swirl and turbulence in the combustion chamber are some factors which influence gaseous
mixture ration and degree of charge homogeneity including residual mixing. The engine and intake system
temperature resulting from prior operation of the engine affect charge temperature and can also affect fuel
distribution.
Valve overlap, engine speed, spark timing, compression ratio, intake and exhaust system back pressure
affect the amount and composition of exhaust residual. Fuel volatility of the fuel is also one of the main reasons.
Scavenging:
In 2-stroke engine a third source of HC emission results from scavenging of the cylinder with fuel air
mixture. Due to scavenging part of the air fuel mixture blows through the cylinder directly into exhaust port and
escapes combustion process completely. HC emission from a 2-Stroke petrol engine is comparatively higher than
4-Stroke petrol engine.
Flame Quenching in SI Engines
Photographic studies of flame region in a spark ignition engine immediately after arrival of flame close to
the combustion chamber walls have shown existence of a thin non-radiating layer adhering to the combustion
chamber. Flame propagates through unburned charge when the energy released on combustion is able to maintain
the reaction zone temperatures at a high enough level to sustain the rapid combustion reactions. However, as the
flame approaches combustion chamber walls, more and more heat is lost from the flame to the walls. Due to heat
transfer from the flame to the walls, temperature of the reaction zone gets lowered that slows down combustion
reactions reducing heat release rate. Finally, as the flame reaches in close proximity of the walls, the gas
temperature ahead of flame falls below ignition point and the flame gets extinguished. This phenomenon is known
as flame quenching.
The flame propagating normal to the single wall will quench at some distance away. When the flame is
propagating through a tube it may not propagate if the tube diameter is smaller than a critical value. Similarly,
flame may not propagate between the two parallel plates if the distance between the plates is below a critical limit.
The normal distance from the wall where flame gets quenched, or the gap between two parallel plates, or diameter
of the tube in which flame is just unable to propagate under the given charge conditions, is called quench distance
or quench layer thickness. The wall-quenching effects are primarily due to heat transfer and not due to diffusion
of species.
HC Emissions from Wall Quenching
Single wall quench layer thickness typically varies from 0.05 to 0.1 mm. It decreases with increase of
engine load as higher wall temperature results at higher engine loads, which reduces heat loss to the walls from
the reaction zone, and consequently a smaller quench layer thickness is obtained. However, at top dead centre the
surface to volume ratio of the combustion chamber is at its maximum and at this point the wall quench layer may
comprise of 0.1 to 0.2 percent of the total charge inducted into the cylinder.
Studies on combustion of pre-mixed fuel air mixtures in combustion bombs show that when all the
crevices in the bomb are eliminated by filling with solid material, unburned HC concentrations were just about 10
ppmC only. Such low concentrations result as after flame quenching the hydrocarbons in the quench layer
thickness on the single walls diffuses in the hot burned gas quite early and get oxidized. Typically, most
hydrocarbons would get oxidized on diffusion in the high temperature burned gases within 2-3 milliseconds of the
flame quench. These studies showed that the contribution of single wall quench layers to the total unburned HC
emission is quite small.
Crevice HC
• Crevices in the combustion chamber are narrow regions into which fuel-air mixture can flow but flame
cannot propagate due to their high surface to volume ratio causing high heat transfer rates to walls.
• The largest crevice in the combustion chamber is between cylinder wall and piston top land, and second
land.
• Other crevices present are along the gasket between cylinder head and block, around intake and exhaust
valve seats, threads around spark plug and space around the central electrode of the spark plug.
Piston - ring - cylinder crevice is shown schematically in Fig. 2.12. Table 2.3 gives typical volumes contained in
different the crevice regions in the cylinder of a production engine. Total crevice volume is about 3 to 5 percent of
the clearance volume and the piston and cylinder crevice constitutes around 70 to 80 percent of the total crevice
volume.

Typical Volume Contained in Engine Crevices, cm3

(Engine Displacement Volume/ Cylinder = 352 cm3, CR = 9:1)
Volume, Percent
cm3
Clearance volume per 44 100
cylinder
Volume above first ring (top 0.51 1.32
land)
Volume behind first ring 0.32 0.86
Volume between 1st and 2nd 0.40 0.88
rings (Second land)
Volume behind second ring 0.32 0.86
Total ring crevice volume 1.55 3.5
Spark plug thread crevice 0.20 0.45
Head gasket crevice 0.20 0..45
Total crevice volume 1.95 4.4
During compression and combustion, unburned charge is pushed into these crevices and at peak pressure,
maximum gas would be stored in the crevices. The gas composition into the crevices depends on the location of
spark plug. In the piston-cylinder crevices mostly unburned charge would be filled in unless the flame has reached
piston top in some location nearest to the spark plug before the peak pressure occurs, which would result also in
small amounts of burned gas being pushed into the crevice in this location. The other crevices close to spark plug
would be filled with a larger fraction of the burned gas. During expansion, the stored gases in the crevices begin
to flow back into the cylinder. Part of the unburned charge from crevices that expands back into the combustion
chamber is oxidized on mixing with the hot burned gases.
Combustion Chamber Deposits HC
Deposits are formed in the intake system, on the valves, combustion chamber and piston crown after
engine operation for several thousand kilometres. The combustion chamber deposits are carbonaceous in
composition and porous in nature. Olefins, aromatics and heavier fuels result in higher deposit build up. Engine
operation for 50 to 100 hours under cyclic and variable load and speed conditions can result in deposit thickness
of around 100 mm in the combustion chamber.
The fuel-air-residual gas charge is compressed into pores of deposits. As the pore size is smaller than the
quench distance, the flame cannot penetrate into deposit pores. The unburned mixture comes out of pores during
expansion and diffuses back into burned gases. Some of these hydrocarbons will burn up on mixing with the hot
burned gases. But, as the temperatures drop on expansion a large fraction of these may fail to get oxidized and are
emitted from the engine.
On the other hand, the deposits formed on the combustion chamber surface reduce heat transfer and it
may decrease quench layer thickness. Prevention of heat transfer by the combustion chamber deposits increases
charge temperatures and hence lower HC emissions. However, the overall effect of deposits is to increase HC
emissions.
In the engine and vehicle tests, combustion chamber deposits are seen to increase HC emissions by 10 to
25 percent
HC from Misfired Combustion
Engine may misfire under engine idling and low load operation as the residual gas dilution is high.
Presence of high residual gas content retards combustion and more fuel burns during expansion stroke. However,
during expansion as the cylinder pressure falls the temperature of the unburned mixture ahead of the flame also
decreases which may result in extinction of flame and consequently in partially misfired combustion. Such bulk
flame quenching in spark-ignition engines leads to very high HC emissions. Use of excessively lean mixtures also
decreases burning rates and increases incidence of bulk gas flame quenching. The propensity to partial misfiring
increases under transient engine operation. Use of large amounts of exhaust gas recirculation (EGR) or high
residual gas dilution though reduces NO formation but results in high HC emissions.
2. CARBON MONOXIDE:
Carbon monoxide remains in the exhaust if the oxidation of CO to CO2 is not complete. This is because
carbon monoxide is an intermediate product in the combustion process. Generally this is due to lack of sufficient
oxygen. The emission levels of CO from gasoline engine are highly dependent on A/F ratio.
The amount of CO released reduces as the mixture is made leaner. The reason that the CO concentration
does not drop to zero when the mixture is chemically correct and leaner arises from a combination of cycle to
cycle and cylinder to cylinder mal distribution and slow CO reaction kinetics. Better carburetion and fuel
distribution are key to low CO emission in addition to operating the engine at increased air-fuel ratio.
FORMATION OF CARBON MONOXIDE
Carbon monoxide is formed during combustion of fuel-rich mixtures due to deficiency of oxygen.
Combustion of hydrocarbon fuels may be considered as a two-step process leading to complete combustion when
carbon dioxide is the final product.
Step 1 Conversion of hydrocarbons to CO: oxidation reactions involving intermediate species like smaller
hydrocarbon molecules, aldehydes, ketones etc lead to formation of CO as schematically shown below are.

RH represents a hydrocarbon where R stands for the hydrocarbon radical

Step 2 Conversion of CO to CO2: when sufficient oxygen is available. Hydroxyl radical OH is one the principal
oxidizing species and converts CO to CO2,

The reaction is quite fast and is under equilibrium at high temperatures. In fact, the reactions involving C-
O-H system may be taken in chemical equilibrium during combustion and large part of expansion stroke when
temperatures are above 1800 K. CO emitted is higher than the equilibrium concentrations corresponding to the
temperature and pressure conditions at the end of expansion. The calculations show that until about 60 degrees
after top dead centre, the burned gases are close to equilibrium. However, late in the expansion stroke and during
exhaust blow down on opening of the exhaust valve as the gases cool down, the CO concentrations differ from the
equilibrium value. The predicted CO levels at the end of expansion computed by equilibrium considerations
during early part of expansion and CO oxidation kinetics ( Reaction 2.29) in the later part of expansion correlated
well with the experimental data as shown on Fig. 2.11 These CO values may be considered as partial equilibrium
vales. Detailed investigations have shown: For rich mixtures (f>1), the average exhaust CO concentrations are
close to equilibrium concentrations during expansion. For near stoichiometric mixtures (f ~1) exhaust CO is close
to computed partial equilibrium values. For lean mixtures the measured CO is higher than the computed values
using kinetic models. This discrepancy may occur due to partial oxidation of unburned hydrocarbons released
from crevices and lubricating oil film and deposits on the combustion chamber walls during expansion. For
estimation of CO concentration a good approximation is to assume chemical equilibrium frozen at 1750 K

Comparison of calculated CO using partial equilibrium and Experimental data

CO emissions in real engines:
 Mixture mal-distribution in multicylinder engines causes cylinder-to-cylinder variation in air-fuel ratio. It
results in significant increase in the average CO emissions. This is especially prominent in the carburetted or
single point throttle body-injected (TBI) engines.
 Another contributing factor to higher CO emissions is non-uniform mixture distribution within the cylinder.
 During cold start of engine and acceleration rich mixtures are used resulting in higher CO emissions.
Overall, the air-fuel ratio is the most important engine parameter affecting CO emissions. Other factors influence
CO mostly indirectly through changes in mixture composition and/or promotion of slow oxidation reactions
resulting in incomplete combustion.
3. OXIDES OF NITROGEN:
Nitric oxide is formed within the combustion chamber at the peak combustion temperature and persists
during expansion and exhaust in non-equilibrium amount. Upon exposure to additional oxygen in the atmosphere,
nitrogen dioxide ( NO2) and other oxides may be formed.
It should be noted that although many oxides of nitrogen may be also formed in low concentrations like,
Nitrogen trioxide (N2O3 ), Nitrogen pent oxide (N2O5 ) etc., they are unstable compounds and may decompose
spontaneously at ambient condition to nitrogen dioxide.
A study of the equilibrium formation of the different nitrogen oxides showed that No is the only
compound having appreciable importance with respect to engine combustion. In engine terminology an unknown
mixture or nitrogen oxides usually NO and NO2 is known as NOx. It is expected that higher temperature and
availability of oxygen would promote the formation of oxides of nitrogen.
Mechanism of NO formation:
The nitric oxide formation during the combustion process is the result of group of elementary reaction
involving the nitrogen and oxygen molecules. Different mechanisms proposed are discussed below.
Simple reaction between N2 and O2

This mechanism proposed by Eyzat and Guibet predicts NO concentrations much lower that those
measured in I.C engines. According to this mechanism, the formation process is too slow for NO to reach
equilibrium at peak temperatures and pressures in the cylinders.
b. Zeldovich Chai Reaction mechanism:

The chain reactions are initiated by the equation ( 2 ) by the atomic oxygen, formed in equation ( 1 ) from
the dissociation of oxygen molecules at the high temperatures reached in the combustion process. Oxygen atoms
react with nitrogen molecules and produces NO and nitrogen atoms. In the equation ( 3 ) the nitrogen atoms react
with oxygen molecule to form nitric oxide and atomic oxygen.
According to this mechanism nitrogen atoms do not start the chain reaction because their equilibrium
concentration during the combustion process is relatively low compared to that of atomic oxygen. Experiments
have shown that equilibrium concentrations of both oxygen atoms and nitric oxide molecules increase with
temperature and with leaning of mixtures. It has also been observed that NO formed at the maximum cycle
temperature does not decompose even during the expansion stroke when the gas temperature decreases.
In general it can be expected that higher temperature would promote the formation of NO by speeding the
formation reactions. Ample O2 supplies would also increase the formation of NO. The NO levels would be low in
fuel rich operations, i.e. A/F 15, since there is little O2 left to react with N2 after the hydrocarbons had reacted.
The maximum NO levels are formed with AFR about 10 percent above stoichiometric. More air than this reduces
the peak temperature, since excess air must be heated from energy released during combustion and the NO
concentration fall off even with additional oxygen. Measurements taken on NO concentrations at the exhaust
valve indicate that the concentration rises to a peak and then fall as the combustion gases exhaust from the
cylinder. This is consistent with the idea that NO is formed in the bulk gases. The first gas exhausted is that near
the exhaust valve followed by the bulk gases. The last gases out should be those from near the cylinder wall and
should exhibit lower temperatures and lower NO concentration.

Emission Controlling Techniques:

Design changes:
The effects of engine design and operating variables on exhaust emission were discussed in a detailed
manner already. Based on the discussions made already the engine design modifications approaches to control the
pollutants are discussed below.
1. NOx is decreased by
A. Decreasing the combustion chamber temperature,
The combustion chamber temperature can be decreased by
1. Decreasing compression ratio
2. Retarding spark timing
3. Decreasing charge temperature
4. Decreasing engine speed
5. Decreasing inlet charge pressure
6. Exhaust gas recirculation
7. Increasing humidity
8. Water injection
9. Operating the engine with very lean or very rich air fuel ratio 10. Decreasing the coolant temperature
11. Decreasing the deposits
12. Increasing S/V ratio
B. By decreasing oxygen available in the flame front
The amount of oxygen available in the chamber can be controlled by
1. Rich mixture
2. Stratified charge engine
3. Divided combustion chamber
2. Hydrocarbon emission can be decreased by
1. Decreasing the compression ratio
2. Retarding the spark
3. Increasing charge temperature
4. Increasing coolant temperature
5. Insulating exhaust manifold
6. Increasing engine speed
7. Lean mixture
8. Adding oxygen in the exhaust
9. Decreasing S/V ratio
10. Increasing turbulence
11. Decreasing the deposits
12. Increasing exhaust manifold volume
13. Increasing exhaust back pressure
3. CO can be decreased by
1. Lean air fuel ratio
2. Adding oxygen in the exhaust
3. Increasing coolant temperature.

EVAPORATIVE EMISSIONS AND CONTROL

Hydrocarbon evaporative emissions from a vehicle arise from two sources as evaporation of fuel in the
carburettor float bowl (5-10 percent ) of fuel in the fuel tank ( about 5 percent ).
CARBURETTOR EVAPORATIVE LOSSES:
Carburettor hydrocarbon vapour losses arise from distillation of fuel from the float bowl. Carburettor fuel
temperature often reaches 55°C during warm weather engine operation and may rise up to 80°C during a hot soak.
Hot soak is a condition when a running car is stopped and its engine turned off. During the soak a significant
fraction of the fuel will boil off and a large portion of the loss finds its way into the atmosphere. There is a
considerable rise in fuel system temperature following shut down after a hard run.
The basic factors governing the mass of fuel distilled from carburettor during a hot soak period are
maximum fuel bowl temperature
· amount of fuel in the bowl
· amount of after-fill and
· distillation curve of the fuel
Tests have indicated that a less volatile fuel would reduce the evaporative losses considerably. A fuel with
20% distilled at 72 °C would give 22% less losses as compared to a fuel which distilled 25% at 72 °C .
The carburettor bowl volume has a significant effect on evaporative losses. Increase in the volume of the
bowl increases the losses linearly. If an insulated spacer is placed between the carburettor and the inlet manifold,
almost 50% reduction can be observed.
Filling of the carburettor (after-fill) to the original liquid level is similar to an increase in the bowl volume
and the distillation losses would increase by about 15%.
FUEL TANK EVAPORATIVE LOSSES:
Fuel tank losses occur by displacement of vapour during filling of petrol tank, or by vaporization of fuel
in the tank, forcing the vapour through a breather vent to the atmosphere. When the temperature is low, the fuel
tank breathes in air. When the temperature goes high it breathes out air, loaded with petrol vapours. Fuel tank
losses occur because the tank temperature is increased during the vehicle operation which causes an increase in
the vapour pressure and thermal expansion of tank vapour.
The mechanism of tank loss is as follows: When a partially filled fuel tank is open to atmosphere, the
partial pressure of vapour phase hydrocarbons and vapour pressure of the liquid phase are equal and they are in
equilibrium. If the temperature of the liquid is increased, say by engine operation, the vapour pressure of the
liquid will increase and it will vaporize in an attempt to restore equilibrium. As additional liquid vaporize the
total pressure of the tank increases and since the tank is open to atmosphere, the vapour will flow out of the tank.
This outflow to the vapour will increase if in addition to liquid temperature rise, the vapour temperature is also
increased.
The evaporation from the tank is affected by a large number of variables of which the ambient and fuel
tank temperature, the mode of vehicle operation, the amount of fuel in the tank and the capacity, design and
location of the fuel tank with reference to exhaust system and the flow pattern of the heated air underneath the
vehicle. Less the tank fill, greater is the evaporative loss. This reflects the difference in the tank vapour space.
Also when a car is parked in a hot location, the evaporation of gasoline in the tank accelerates and so the
evaporation loss is greater.
EVAPORATIVE EMISSION CONTROL DEVICES:
Evaporative emission control devices are designed to virtually eliminate the hydrocarbon vapours emitted
by the carburettor and fuel tank during both running and hot soak. During running, fuel tank vapours are inducted
and burned in the engine. Carburettor losses are vented to intake system. Vehicles without evaporative controls
are estimated to 10se 30 g/day of HC from fuel tank filling and breathing. Another 40 g/day is lost by evaporation
from the carburettor ( hot soak loss ) when the vehicle is parked after being operated. ON this basis, evaporative
losses are estimated to be 23% of total HC emissions. The device as shown in the figure consists of an absorbent
chamber, the pressure balance valve and the purge control valve. The absorbent chamber which consists of a
charcoal bed or foamed poly-urethane holds the hydrocarbon vapour before they can escape to atmosphere. The
carburettor bowl and the fuel tank are directly connected to the absorbent chamber.
 During hot soaks, vapours from the fuel tank are routed to a storage device. Carburettor vapours may be
vented to the storage system or retained internally in the carburettor or induction system volume. A schematic
diagram of this arrangement is shown in the figure.
Upon restart, filtered air is drawn through the stored vapours and the mixture is metered into the intake
system and burned in the engine. In this manner the storage device is purged (removed off the retained vapour).
The operations of the purge control valve are controlled by the exhaust back pressure. The storage system consists
of a canister containing activated charcoal located in the engine compartment. Activated charcoal has an affinity
for HC and on a recycle basis can store 30-35 grams of fuel per 100 grams of charcoal without breakthrough.
Typically 700-800 grams of charcoal are used in a vehicle system.

EXHAUST GAS RECIRCULATION:

In exhaust gas recirculation a portion of the exhaust gas is recirculated to the cylinder intake charge. This
reduces the peak combustion temperature, since the inert gas serves as a heat sink. This also reduces the quantity
of oxygen available for combustion. The exhaust gas for recirculation is passed through the control valve for
regulation of the rate and inducted down to the intake port, The recycle rate control valve is connected to the
throttle shaft by means of appropriated linkage and the amount of valve opening is regulated by throttle position.
The link is designed so that recycled exhaust is normally shut off during idle to prevent rough engine operation.
This is also shut off during full throttle, acceleration to prevent loss of power when maximum performance is
needed.
The NOx concentration will vary with the amount of recycling of gas at various air fuel ratios. About
15% recycle will reduce NOx emission by about 80%. The maximum percentage which can be circulated is
limited by rough engine operation and loss of power.
The figure shows a vacuum controlled EGR valve used to control the recycle rate. A special passage
connects the exhaust manifold with the intake manifold. This passage is opened or closed by a vacuum controlled
EGR valve. The upper part of the valve is sealed. It is connected by a vacuum line to a vacuum port in the
carburettor. When there is no vacuum the port, there is no vacuum applied to the diaphragm in the EGR valve.
Therefore, the spring holds the valve closed. No exhaust gas recirculates. This is the situation during engine idling
when little NOx is formed.
 As the throttle valve opens it passes the vacuum port in the carburettor. This allows intake manifold
vacuum to operate the EGR valve. Then vacuum raises the diaphragm, which lifts the attached valve off its seat.
Now exhaust gas flows into the intake manifold. There the exhaust gas mixes with the air fuel mixture and enter
the engine cylinders.
At wide open throttle, there is little vacuum in the intake manifold. This produces a denser mixture which
burns cooler during the combustion process. Therefore at wide open throttle there is less need for exhaust gas
recirculation. Due to low vacuum, the EGR valve is nearly closed.

Selective Catalytic Reduction:

The selective catalytic reduction of NOx using ammonia or urea as reducing agent has been used since
1980s in the stationary applications like gas turbines, utility boilers, diesel engines used for power generation.
Recently, this technology is being applied to the transport diesel engine used in ships, locomotives and prototype
heavy duty road vehicles. In this technology, ammonia or urea is continuously injected upstream of the catalyst.
Then the ammonia reacts on the SCR catalyst with the NOx present in the exhaust to convert it to nitrogen. The
basic chemical reactions in the urea SCR process are as follows:
Urea hydrolysis:
(NH2)2 CO + H2O  CO2 + 2NH3
NOx Conversion:
4NO + 4 NH3 + O2  4N2 + 6H2O
6NO2 + 8NH3  7N2 + 12H2O
Urea concentrations of 30 to 40% in water solution are usually employed, although higher concentration
of urea would help in reducing the weight to be carried aboard vehicle. The crystallization temperature of urea on
cooling is minimum (-11oC) at 33% concentration. For lowering of the freezing point of the urea –water solution
below -30oC when the climatic conditions so demand, small amount of additives could be used.
The SCR catalyst is typically a vanadium and titanium oxide mixture (V2O5 + TiO2 + WO3), Coated on a
ceramic honeycomb substrate of 200 – 400 cpsi. During vehicle operation on road, concentration of NOx in the
exhaust gases varies all the time requiring continues variation in the urea injection rate. The NOx in diesel engines
consist of around 10% NO2. Based on the stoichiometric considerations, for 90% conversion of NOx the
NH3/NOx molar ratio of about 0.9 is required. The excess urea injection rate would result in emissions of
unreacted ammonia in the exhaust, which is called ‘ammonia slip’. To minimize slip, a dynamic urea dosage
strategy based on engine operating conditions is to be employed. Even with such a strategy if high conversion
rates are required needing use of high urea dosages, ammonia slip occurs during transient operation.
Typical conversion efficiency at different NH3/NO molar ratio and ammonia slip are shown in figure
with increase in NH3/NO molar ratio (alpha), NOx conversion efficiency increases and so also the ammonia slip.
An oxidation catalyst is therefore, added to SCR catalyst system to prevent secondary emissions of ammonia
during dynamic engine operation. Although, the basic SCR system using urea would be composed of thee catalyst
viz., a hydrolysis catalyst, a SCR catalyst and a guard oxidation catalyst, the NOx conversion efficiency can be
improved below 300oC catalyst temperature when a pre-oxidation catalyst upstream of SCR system is used. Such
a SCR system for heavy-duty engines, NOx conversions of more than 70% have been obtained. When urea – SCR
was employed to a heavy duty truck of 31.7 ton GVW, on-road emission measurement showed overall NOx
reduction of 63% on a mountain highway, 68% on a level highway and 72% during urban operation. Over 1200
miles operation, urea consumption was about 5.5% of the fuel consumption.

Acceptance of urea-SCR technology by the regulatory agencies depends on the control of the potential
secondary pollutants such a nitrous oxide (N2O), cyanic acid (HCN) and formaldehyde (HCHO). Investigations
however, have shown the absence of these secondary emissions. The urea-SCR catalyst operate on relatively low
space velocities of around 10,000 to 30,000 hr-1, requiring a relatively large catalyst volume compared to the
conventional catalytic converters used on gasoline fueled passenger cars. Therefore, due to packaging problems
this technology is more likely to find its application on heavy-duty vehicles. Other important concerns such as
urea-distribution network, system durability, temper proof system and the high cost of the system are also related
to urea-SCR technology implementation.

Fumigation technique:
This method consists of introducing a small amount of fuel into the intake manifold. This starts
precombustion reactions before and during the compression stroke resulting in reduced chemical delay, because
the intermediate products such as peroxides and aldehydes react more rapidly with oxygen than original
hydrocarbons. The shortening of delay period curbs thermal cracking which is responsible for soot formation.
Fumigation rate of about 15% gives best smoke improvement. However this improvement varies greatly
with engine speed. At low engine speeds 50 to 80% smoke reduction is obtained. This decrease as speed increases
until a speed at which there is no effect of fumigation.
Secondary Air Injection:
The mechanism by which exhaust emissions are controlled depends on the method of injection and the
point at which air enters the exhaust system, and has varied during the course of the development of the
technology. The first systems injected air very close to the engine, either in the cylinder head's exhaust ports or in
the exhaust manifold. These systems provided oxygen to oxidize (burn) unburned and partially burned fuel in the
exhaust before its ejection from the tailpipe. There was significant unburned and partially burned fuel in the
exhaust of 1960s and early 1970s vehicles, and so secondary air injection significantly reduced tailpipe emissions.
However, the extra heat of recombustion, particularly with an excessively rich exhaust caused by misfiring or a
maladjusted carburetor, tended to damage exhaust valves and could even be seen to cause the exhaust
manifold to incandesce.
As emission control strategies grew more sophisticated and effective, the amount of unburned and partially
burned fuel in the exhaust stream shrank, and particularly when the catalytic converter was introduced, the
function of secondary air injection shifted. Rather than being a primary emission control device, the secondary air
injection system was adapted to support the efficient function of the catalytic converter. The original air injection
point became known as the upstream injection point. When the engine is cold, air injected at this point cleans up
the extra-rich exhaust and raises the temperature of the exhaust so as to bring the catalytic converter to operating
temperature quickly. Once the engine is warm, air is injected to the downstream location — the catalytic
converter itself — to assist with catalysis of unburned hydrocarbons and carbon monoxide.
1. Aspirated air injection
Air injection can also be achieved by taking advantage of the negative pressure pulses in the exhaust system at
engine idle. A sensitive reed valve assembly called the aspirator valve is placed in the air injection pumping,
which draws its air directly from the clean side of the air filter.
2. Pumped air injection
Pumped air injection systems use a vane pump called the air pump, AIR pump, or colloquially "smog pump"
turned by the engine via a belt or electric motor. The pump's air intake is filtered by a rotating screen to exclude
dirt particles large enough to damage the system. Air is delivered under light pressure to the injection point(s).
CRANKCASE EMISSION AND CONTROL
During the compression and combustion strokes, highly corrosive blowby gases are forced past the piston
rings into the crankcase. The amount of blowby entering the crankcase generally increases with engine speed. The
amount of blowby also depends on other conditions including piston, ring and cylinder wear. The actual amount
of wear may be small, perhaps only a few thousands of an inch. But almost any wear is enough to weaker the
sealing effect of the rings and permit blowby to increase. Blowby gases contain burned and unburned fuel, carbon
and water vapour from the combustion chamber. When the engine is cold, some of the water vapour of the
blowby condenses on the cylinder walls and crankcase. It forms into droplets and runs down into the oil pan.
Gasoline vapour also condenses on cold engine parts and drips down into the oil pan. This gasoline dilutes and
thins the oil, reducing its lubricating ability.
The churning action of the rotating crank shaft can whip the water and engine oil into thick, gummy
substance called sludge. The acid compounds from the blowby can get into the sludge and cause corrosion and
faster wear of engine parts. Sludge can also clog oil passages and prevent normal engine lubrication, thereby
leading to early engine failure.
Blowby causes pressure in the crankcase. If this pressure is allowed to build up, engine oil is forced past
the oil seals and gaskets and out of the engine. To help to control the effect of blowby, there must be a way to
relieve the crankcase pressure caused by blow by gases.

CRANKCASE VENTILATION
To avoid the above said problems, the unburned and partly burned gasoline and the combustion gases and
water vapour must be cleared out of the crankcase by providing crankcase ventilation systems.
In early engines, the crankcase ventilation system was very simple. It provided crankcase breathing by
passing fresh oil through the crankcase. On almost all American made automobile engines built prior to 1961, the
fresh air entered through an air inlet at the top front of the engine. The fresh air is mixed with the blowby fumes
and other vapours in the crankcase. These vapours were routed out of the crankcase through a large hollow tube
called the road draft tube, which discharged under the car into the atmosphere.
The fresh air inlet was usually the crankcase breather cap. On most engines it also served as the cap for
the crankcase oil filler tube. The cap was open, or vented with holes
on both sides to let fresh air to pass through. The cap was filled with oil soaked steel wool or similar material to
serve as an air filter. The filter prevented dust particle in the air from getting into the crankcase oil and causing
engine wear.
THERMAL REACTORS:
Thermal reactor is a chamber in the exhaust system designed to provide sufficient residence time to allow
appreciable homogeneous oxidation of HC and CO to occur. In order to improve CO conversion efficiency, the
exhaust temperature is increased by retarding spark timing. This however results in fuel economy loss.
The air is supplied from an engine driven pump through a tube to a place very near to the exhaust valve.
To achieve a high degree of exhaust system oxidation of HC and CO, a high exhaust temperature coupled with
sufficient oxygen and residence time to complete the combustion is needed. Oxides of nitrogen are not reduced. In
fact, they may be increased if sufficiently high exhaust temperature results from the combustion of CO and HC
with the added air or if the injected air enters the cylinder during the overlap period, thereby leaning the mixture
in the cylinder.

Warren has derived the following equation for the concentration of hydrocarbons leaving the exhaust
system.
Co = Ci X exp Kr O2 P 2V K3 T2W
Where,
Co = Concentration of HC leaving the thermal reactor
Ci = Concentration of HC leaving cylinders and entering the thermal reactor Kr = Specific
reaction rate ft3/lbm – mole/sec
K3 = constant
O2 = oxygen concentration in exhaust gases. Volume percent P = exhaust
pressure ( Psi)
V = thermal reactor volume available for reaction Cu.ft T = Absolute
temperature C
W = Mass flow rate of air ( lb/sec)
Note the importance of pressure term. Increasing exhaust system back pressure promote after reaction.
However commercially, the possible back pressure increase is small.
 The graph shows the effect of temperature on specific reaction rate Kr, calculated from the above
equation by warren from his experimental data. The nearness of his curve to a straight line suggests the equation
is a good approximation for the overall reactions occurring. Note that a decrease in exhaust temperatures from
1100oC to 1000F decreases the reaction rate by a factor of 10.
The minimum HC concentrations occurred at rich mixtures. When too much air was injected, especially
at lean mixtures, excessive cooling of the exhaust increased HC concentrations above those with no air. Thus the
normal oxidation process was apparently inhibited by this cooling. A small increase in CO occurred slightly richer
than stoichiometric. At stoichiometric mixtures and leaner, CO was very low. Best results occurred for rich
mixtures with air injection at 20-30% of inlet air flow. The air-fuel ratio for best emission reduction was 13.5:1.
Normally engine operation at such a rich mixture would reduce fuel economy by 10%.

CATALYTIC CONVERTER
A catalytic converter is a vehicle emissions control device that converts toxic pollutants in exhaust gas to
less toxic pollutants by catalyzing a redox reaction (oxidation or reduction). Catalytic converters are used
with internal combustion engines fueled by either petrol (gasoline) or diesel—including lean-burn engines.
Although catalytic converters are most commonly applied to exhaust systems in automobiles, they are also used
on electrical generators, forklifts, mining equipment, trucks, buses, locomotives and motorcycles. They are also
used on some wood stoves to control emissions.
The catalytic converter's construction is as follows:
1. The catalyst support or substrate. For automotive catalytic converters, the core is usually a
ceramic monolith with a honeycomb structure. Metallic foil monoliths made of Kanthal (FeCrAl) are
used in applications where particularly high heat resistance is required. Either material is designed to
provide a large surface area.
2. The washcoat: A washcoat is a carrier for the catalytic materials and is used to disperse the materials over
a large surface area. Aluminum oxide, titanium dioxide, silicon dioxide, or a mixture
of silica and alumina can be used. The catalytic materials are suspended in the washcoat prior to applying
to the core. Washcoat materials are selected to form a rough, irregular surface, which greatly increases
the surface area compared to the smooth surface of the bare substrate. This in turn maximizes the
catalytically active surface available to react with the engine exhaust. The coat must retain its surface
area and prevent sintering of the catalytic metal particles even at high temperatures (1000 °C).
3. The catalyst itself is most often a mix of precious metals. Platinum is the most active catalyst and is
widely used, but is not suitable for all applications because of unwanted additional reactions and high
cost. Palladium and rhodium are two other precious metals used. Rhodium is used as a reduction catalyst,
palladium is used as an oxidation catalyst, and platinum is used both for reduction and
oxidation. Cerium, iron, manganese and nickel are also used, although each has limitations. Nickel is not
legal for use in the European Union because of its reaction with carbon monoxide into toxic nickel
tetracarbonyl. Copper can be used everywhere except North America, where its use is illegal because of
the formation of dibenzodioxins
A 3-way catalytic converter is a sophisticated device used in the exhaust system of many modern petrol
engine vehicles. It converts harmful gases in the engine exhaust to relatively harmless gases.
Why should we use 3-way catalytic converters?
The exhaust gases from an engine contain harmful substances such as oxides of nitrogen (NO x), carbon
monoxide (CO) and Hydrocarbons (HC). These substances produce extreme environment hazards. 3-way catalytic
converters convert these harmful substances to less harmful nitrogen (N2), carbon-di-oxide (CO2) and water
(H2O).
Working:
A three-way catalytic converter makes use of two catalysts to convert harmful gases to harmless gases. They are:
1. Reduction Catalyst and
2. Oxidation Catalyst
The reduction catalyst is made of platinum and rhodium while the oxidation catalyst is made of platinum and
palladium. Both the catalysts have a ceramic honeycomb structure.
Block Diagram of a 3-way Catalytic Converter

Stages:
Stage 1 – Reduction Catalyst:
The exhaust gases are first sent over the reduction catalyst (which is made of platinum and rhodium). It
converts oxides of nitrogen (NOx) to nitrogen (N2) and oxygen (O2). The following reactions take place when the
exhaust gases pass over the reduction catalyst.
2NO → N2 + O2
2NO2 → N2 + 2O2
The reduction catalyst simply rips off nitrogen and oxygen from the oxides of nitrogen. As you might
know, nitrogen and oxygen are harmless gases while oxides of nitrogen are really harmful to the environment.
Stage 2 – Oxidation Catalyst:
Exhaust gases that are free of oxides of nitrogen (NOx) are then sent over the oxidation catalyst (made
of platinum and palladium). The oxidation catalyst coverts carbon-monoxide (CO) and hydrocarbons (HC) in the
gases into carbon-di-oxide (CO2) and water (H2O).
The following reaction takes place when the exhaust gases pass over the oxidation catalyst:
 2CO + O2→ 2CO2
HC + O2 → CO2 + H2O
The second reaction (above) is a generalized reaction. In it, HC stands for hydrocarbon. HC might be
methane, ethane or other hydrocarbon.
The gases that finally come out of the catalyst chamber are N2, CO2, and H2O. 3-way catalytic converters
are so named because they are capable of eliminating three pollutants – NOx, CO and HC.
If you still have any confusion in understanding the working of 3-way catalytic converter, refer the block
diagram above or watch the animation video found below.
NO-Reduction Catalysts:
From the literature, it is seen that the following materials have been tried successfully as reduction
catalysts in the vehicle emission control
1. Copper oxide-chromia
2. Copper oxide – Vanadia
3. Iron oxide – Chromia
4. Nickel oxide pelleted on monolithic ceramic and metallic supports
5. Monel metal
6. Rare earth oxides
HC/CO oxidation catalysts:
1. Noble metal catalysts such as activated carbon, palladium or platinum
2. Transition metal oxide catalysts such as copper, cobalt, nickel and iron chromate as well as vanadium
or manganese promoted versions of these metals.
3. Copper chromite-alumina and platinum oxide –alumina catalysts were developed with sufficient
activity, stability and mechanical strength.
The catalysts chosen for vehicle emission control should satisfy the following:
1. High conversion efficiency under transient conditions
2. Effective for wide range of temperature ( for ambient to 1600 F)
3. Must withstand the poisoning action of additives in the gasoline that are emitted in the exhaust
4. Must be able to withstand thermal shock
5. Be attrition resistant to highly turbulent flows through the converter
6. Vehicle operation for 50,000 miles
7. Convert into harmless products
8. Cheap and readily available.
Draw backs of the catalytic converter system:
1. Generally catalysts are active only at relatively high temperature. Emissions during warm-up cannot
be catalyzed and this period has particularly heavy emissions.
2. Catalysts operate over a wide but not unlimited temperature range. A temperature control is required
to avoid burnout temperature at high speeds and loads.
3. Catalysts are poisoned by exhaust constituents in particular lead compounds. Hence conversion
efficiency decreases with use.
4. The catalytic bed offers considerable back pressure which increases with use.
5. Catalytic converters are expensive.
Importance of unleaded Petrol:
Vehicles equipped with catalytic converters must use only un-leaded gasoline. If the gasoline contains
lead, the lead will coat the catalyst and the converter will stop working.
EMISSION MEASUREMENT
The emission regulations specify the type, principle of operation used and generic construction of the
exhaust gas analyzers which can be employed for emission certification of vehicles and engines.
CO and CO2 NDIR Analyzers
Beer-Lambert's Law is used for operation of NDIR analyzers by measuring the degree of absorption of
infrared (IR) radiations when they pass through a column of gas. The fraction of incident radiations absorbed is
given by,

Non Dispersive Infrared analyzer

As the absorption of IR radiations is measured only in a narrow range of wavelengths (not the entire
range of wavelength of IR radiations) which has specifically a high absorbance for the particular gas, the
technique is called as ‘Non-dispersive infra-red'. For example carbon monoxide has a strong absorbance
in the wavelength band of 4.5-5 μm.
 The analyzer measures differential in absorption of energy from two columns of gas; (i) the gas to be
analyzed in the ‘sample cell' and (ii) a gas of fixed composition like N2 contained in the reference cell which
is free of the gas of interest and relatively non-absorbing in the infrared region.
 The infrared beam from a single source is usually split into two beams of the same intensity, one each for the
sample and reference cells.
 The detector is divided in two compartments separated by a flexible diaphragm; one section receives
transmitted IR energy from the sample cell and the other from the reference cell.
 The detector is filled with the gas of interest, so that the energy transmitted to the detector is fully absorbed.
 The flexible diaphragm of the detector senses the differential pressure between the two sections of the
detector caused by the difference in the amount of transmitted IR energy absorbed. The deflection in the
diaphragm is used to generate an electrical signal that determines the concentration of the gaseous species of
interest.
 A rotating interrupter in the path of IR beam is put to generate AC signal output that can be amplified.
 NDIR analyzers enable accurate measurements of CO and CO2in the exhaust gases.

Schematic of an NDIR analyzer for measurement of CO and CO2 concentration.

 NDIR instruments are seldom used for measurement of hydrocarbons except in the garage type analyzers
as the IR absorbance to different hydrocarbons varies substantially. The unsaturated hydrocarbons are primarily
responsible for photochemical smog but they do not have an adequate absorption in the IR wavelength range that
is specific to the saturated hydrocarbons and vice versa. Sensitivity and response of NDIR to the exhaust HC is
typically only half of the probable true value. NO absorbs only weekly in the infrared region. Moreover, CO,
CO2and water vapours interfere seriously; hence NDIR analyzers are also not used for NO measurement.

Flame Ionization Detector (FID)

Pure hydrogen-air flames are practically ion-free but on introduction of even little amount of
hydrocarbons the flame causes considerable ionization and becomes electrically conducting. The ionization
current is proportional to the number of carbon atoms present in the hydrocarbon molecules.
Thus, FID is effectively a carbon atom counter e.g., one molecule of propane generates three times the response
generated by one molecule of methane. The measurement of HC by FID is expressed as parts per million of
methane i.e. as ppmC 1 i.e., ppm of hydrocarbon containing equivalent of one carbon atom. The HC concentration
is commonly written as ppmC. HC concentration measured as ppm propane (C3 ) is to be multiplied by a factor of
3 to convert it to ppmC. All classes of hydrocarbons i.e., paraffin, olefins, aromatics, etc. show practically the
same response to FID. Oxygenates, e.g. aldehydes and alcohols however, have a somewhat lower response.
FID essentially consists of a hydrogen-air burner and an ion collector assembly as shown in Fig. 4.11. Sample gas
is introduced with hydrogen in the burner assembly and the mixture is burned in a diffusion flame. An electric
potential is applied between the collector plates that makes the ionization current to flow and generate signal
proportional to HC concentration in the sample gas. This current is amplified and the output signal is measured.
A well-designed burner will generate ionization current that is linearly proportion to hydrocarbon content over a
dynamic range of almost 1 to 10 6 . The commercial FID analyzers have the most sensitive range set at about 0-50
ppmC and the maximum range reaching 0-100,000 ppmC. Hydrogen is mixed with helium in ratio of 40:60 to
decrease flame temperature that increases flame stability. The FID analyzer is calibrated with propane or methane
mixtures in nitrogen. For the measurement of hydrocarbons in diesel exhaust, sampling line and FID are heated to
a temperature of 191± 11°C to minimize condensation of heavy hydrocarbons present in the diesel exhaust in the
sampling system.

Figure 4.11 FID for HC measurement.

Chemiluminescence Analyzer (CLA)
When NO and ozone (O3) react a small fraction (about 10% at 26.7° C) of excited NO2* molecules is
produced as per the following reactions:

As the excited molecules of NO2* decay to ground state, light in the wavelength region 0.6-3.0 μm is emitted. The
quantity of excited NO2 produced is fixed at a given reaction temperature and the intensity of light produced
during decay of excited NO2 is proportional to the concentration of NO in the sample.
 Figure 4.12 Schematic and flow diagram of a chemiluminescence NOx analyzer.
 The sample containing NO flows to a reactor where it reacts with ozone produced from oxygen in ‘ozonator'.
In the reactor NO is converted to NO2 .
 A photomultiplier tube detects the light emitted by the excited NO2 . The signal is then amplified and fed to
recorder or indicating equipment.
 For the measurement of nitrogen oxides (NOx ), NO2in the sample is first converted to NO by heating in a
NO2- to-NO converter prior to its introduction into the reactor. At 315º C, about 90 percent of NO 2 is
converted to NO. The total concentration of NOx in the sample is thus, measured as NO. When the sample is
introduced in the reactor bypassing the NO2 - to- NO converter, concentration of NO alone is determined. The
difference between the two measurements provides the concentration of NO2in the sample.
 The response of the instrument is linear with NO concentration. The technique is very sensitive and can detect
up to 10-30 ppm of NOx.
 The output signal is proportional to the product of sample flow rate and NO concentration. As the method is
flow sensitive an accurate flow control is necessary. The calibration and operation are done at the same flow
rate and reactor temperature.

Smoke meters
In the filtration type smoke meters like Bosch smoke meter a fixed volume of the exhaust gas is drawn
through a white filter paper of specified quality. The density of smoke stain obtained on the filter paper is
evaluated using a reflectance meter which gives the measure of smoke density of diesel exhaust gas. Now, mostly
light extinction/absorption smoke meters based on Beer-Lambert Law are used. The light extinction type smoke
meters are more commonly called as ‘opacimeters' as these provide a more realistic measurement of the visible
smoke emissions from diesel engines. Both the sampling type and full flow type opacimeters are in use. The
construction requirements, installation and operational details of opacimeters are described in the relevant
international standards. A sampling type smokemeter is shown schematically in Fig. 4.13.

Figure 4.13 Schematic of a sampling type light extinction smoke meter.

 An incandescent lamp with a colour temperature in the range of 2 800 K to 3 250 K or a green light
emitting diode (LED) with a spectral peak between 550 nm and 570 nm is used as light source. The transmitted
light is received on a photocell or a photo diode (with filter if necessary). When the light source is an incandescent
lamp, the receiver should have maximum response in the range 550 nm to 570 nm wavelength as is for the human
eye.
When light from a source is transmitted through a certain path length of the exhaust gas, smoke opacity is
the fraction of light that is absorbed in the exhaust gas column and does not reach the light detector of smoke
meter. The absolute smoke density is given by the absorption coefficient, ks which has units of m -1 and is given
by:

Where L is length of smoke column in meter through which light from the source is made to pass, I0 is the
intensity of incident light, I is the transmitted light falling on the smokemeter receiver. In the full flow type smoke
meter, the light source and detector are placed directly across the exhaust gas stream usually at the end of exhaust
pipe. In this case, path length of smoke measurement varies with the cross sectional size of the exhaust gas stream
or tail pipe. Hence, conversion charts of the measured value to the absolute smoke density, ks for different exhaust
pipe diameter or path lengths are made available for the full flow smoke meters.

Measurement OF Non-Methane Hydrocarbons (NMHC)

Presently, the emission standards are specified in terms of non-methane hydrocarbons. Methane content of
HC emissions is determined by one of the following methods:
 Gas chromatographic (GC) method or
 Non-methane cutter (NMC) method
In the GC method, sample is injected into GC column which separates the sample into two parts:
(i) CH 4 -air-CO, and
(ii) NMHC–CO2 –H2O.
A molecular sieve column separates methane from air and CO before passing it to FID. Thus methane
content is measured that is deducted from the total hydrocarbon content.
In the NMC method, all hydrocarbons except CH4 are oxidized to CO2and water on a catalyst, so that when the
gas sample is passed through NMC only CH4 is detected by HFID. The NMC cutter is calibrated for catalytic
effect on CH4 and higher hydrocarbon (ethane) mixtures in presence of water vapours with values typical of
exhaust gas at or above 600 K. The sample can be alternatively passed through NMC or bypasses the NMC. In
this manner, the total HC and methane alone present in the exhaust gas sample are determined.

Gas chromatography
Chromatography is a technique for separating chemical substances that relies on differences in
partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a
mixture. The sample is carried by a moving gas stream through a tube packed with a finely divided solid or may
be coated with a film of a liquid. Because of its simplicity, sensitivity, and effectiveness in separating components
of mixtures, gas chromatography is one of the most important tools in chemistry. It is widely used for quantitative
and qualitative analysis of mixtures, for the purification of compounds, and for the determination of such
thermochemical constants as heats of solution and vaporization, vapour pressure and activity coefficients.
Gas chromatography is also used to monitor industrial processes automatically: gas streams are analyzed
periodically and manual or automatic responses are made to counteract undesirable variations.
Many routine analyses are performed rapidly in environmental and other fields. For example, many
countries have fixed monitor points to continuously measure the emission levels of for instance nitrogen dioxides,
carbon dioxide and carbon monoxide. Gas chromatography is also useful in the analysis of pharmaceutical
products, alcohol in blood, essential oils and food products. The method consists of, first, introducing the test
mixture or sample into a stream of an inert gas, commonly helium or argon, that acts as carrier. Liquid samples
are vaporized before injection into the carrier stream. The gas stream is passed through the packed column,
through which the components of the sample move at velocities that are influenced by the degree of interaction of
each constituent with the stationary nonvolatile phase. The substances having the greater interaction with the
stationary phase are retarded to a greater extent and consequently separate from those with smaller interaction. As
the components elute from the column they can be quantified by a detector and/or collected for further analysis.
 Two types of gas chromatography are encountered: gas-solid chromatography (GSC) and gas-liquid
chromatography (GLC). Gas-solid chromatography is based upon a solid stationary phase on which retention of
analyses is the consequence of physical adsorption. Gas-liquid chromatography is useful for separating ions or
molecules that are dissolved in a solvent. If the sample solution is in contact with a second solid or liquid phase,
the different solutes will interact with the other phase to differing degrees due to differences in adsorption, ion-
exchange, partitioning or size. These differences allow the mixture components to be separated from each other
by using these differences to determine the transit time of the solutes through a column.

Gas Chromatography - Carrier gas

The choice of carrier gas depends on the type of detector that is used and the components that are to be
determined. Carrier gases for chromatographs must be of high purity and chemically inert towards the sample
e.g., helium (He), argon (Ar), nitrogen (N2), carbon dioxide (CO2) and hydrogen (H2). The carrier gas system can
contain a molecular sieve to remove water or other impurities.

Particulate Emission Measurement

For measurement of particulate emissions, the gas is diluted with air in a dilution tunnel and, a sample is
continuously collected from the diluted gas and filtered to collect particulate matter. The mass of the collected PM
is measured to determine specific PM emissions in terms of g/km or g/kWh.
The dilution tunnels are of two types
 Partial flow, and
 Full flow dilution tunnel