WHAT IS POLLUTANT?

 THE TERM POLLUTANT IS NORMALLY

APPLIED TO ANY SUBSTANCE ADDED TO
THE ENVIROMENT IN SUFFICIENT
CONCENTRATION TO HAVE MEASURABLE
EFFECT ON HUMAN, ANIMALS,
VEGETATION OR BUILDING MATERIALS.

 HENCE AIR POLLUTANTS INCLUDE ALL

NATURAL AND ARTIFICIAL AIRBORNE
SUBSTANCES INCLUDING GAS, SOLID
PARTICLES, LIQUID DROPLETS AND
MIXTURE OF DIFFERENT ITEMS.
 TYPES OF POLLUTANTS
 PRIMARY POLLUTANTS : EMITTED
DIRECTLY FROM IDENTIFIABLE SOURCES
 SECONDARY POLLUTANTS : PRODUCED
AT THE ATMOSPHERE BY
i) Interaction between various primary
pollutants or,
ii) Reaction between pollutants and the normal
constituents of the atmosphere
 PRIMARY POLLUTANTS
 CARBON COMPOUNDS > CO, CO2
 NITROGEN COMPOUNDS > NO,NO2 etc
 SULPHER COMPOUNDS > SO2, SO3 etc
 ORGANIC COMPOUNDS > Hydrocarbons
 METALLIC COMPOUNDS > PbO
 FINE PARTICLES (Φ< 100µm)
 COARSE PARTICLES (Φ> 100µm)
 MAIN POLLUTANTS CONTRIBUTED BY
AUTOMOBILES (IC ENGINES) ARE
CO,UBHC,NOX AND SPM
 Carbon monoxide (CO) > 1-2%,Mostly from

SI engines, 200/30 gm/kg of fuel

 Hydrocarbons (HC) > More in SI engines, but

HC from CI engines are more toxic, 50/6

gm/kg of fuel. Evaporative and blowby
emissions are considerable in uncontrolled
engines.
SOME OF THE HYDROCARBONS WHICH ARE
GENERALLY FOUND IN IC ENGINES ARE

 MHC
 NMHC
 PAH
 Carboxyl Compounds
 Benzene
 Aldehydes and Ketones
 Other Pollutants from IC engines are

 NOX > Mostly NO, more in CI engines. 15/3

gm/kg of fuel
 SOX
 SPM
 Smoke
 EMISSIONS FROM SI ENGINES
One of the toxic exhaust constituent of SI engine
is carbon monoxide. It is a colorless, odorless,
and highly toxic gas, with a density close to
that of air. It is produced under excessively
rich combustion conditions.
Wood Combustion –
Automobiles
Other sources
 CONTD
 CO from SI engine tailpipe is very high when
i) Mixture is rich
ii) Engine speed is high
iii) CO increases significantly when there is cylinder to
cylinder variations in air fuel ratio
iv) During engine starting
v) During idling
vi) During acceleration and deceleration
 MECHANISM OF CO FORMATION

CO formation is one of the principal reaction

step in hydrocarbon combustion
mechanism which may be summarized by
RH→R →RO2 →RCHO →RCO →CO
R → hydrocarbon radical
CO forms via this path then oxidized to CO2
CO + OH → CO2 + H
 CONTD.
CO forms via this path than oxidized to CO2
CO + OH → CO2 + H
CO forms just after the peak flame temperature
reaches 2800 K and pressure 15 to 40 bar
Burned gases cooled during expansion and
exhaust stroke.
Some of the CO do not oxidized.
 CO formations Contd.
 CO is a product of intermediate reaction of hydro-
carbons. In oxidation of hydrocarbons CO forms just
after the peak temperatures reaches. If there is a
deficiency in the availability of oxygen some of the
CO is not oxidized to CO2.
 Also burned gases cooled during expansion and
exhaust stroke. If it cools too much CO is not
oxidized to form CO2 even if sufficient oxygen is
available.
 If the time available is not sufficient for the
intermediate product of CO to oxidized then also CO
will result in the exhaust.
 Nitrogen compounds
 NO and NO2 are usually analyzed
simultaneously and expressed in the form of
NOx with 1<x<2. NO is the most abundant of
all nitrogen derivatives present in the
atmosphere and it represents about 95% of
NOx emissions.
 NOX forms during combustion process when
the flame temp is > 1500 K and oxygen is also
available in the comb zone.
 Mechanism of formation of NO
O + N2 ↔ NO + N-----(i)
N + O2 ↔ NO + O-----(ii)
N + OH ↔ NO + H -----(iii)
NO forms when the flame temperature and the
temperature of the burned gas leaving the flame
is very high
Reaction (iii) takes place when the mixture is
very rich
Reactions (i) and (ii) occur in lean mixtures
 CONTD
 Most of the NO is generated in the gases leaving the
flame and not in the flame except in rich mixture
zone.
 In engines where combustion takes place under high
pressure the reaction zone in the flame is very thin, of
the order of 0.1 mm and short lived.
 As pressure rises during the combustion and flame
propagation the temperature of the burnt gases are
much more than one reached immediately after the
combustion.
 Formation of NO2
NO formed in the flame zone can be rapidly
converted to NO2 via reactions such as
NO + HO2 ↔ NO2 + OH ------(i)
Subsequently NO2 converted NO
NO2 + O ↔ NO + O2--------(ii)
Reactions (ii) will not place if the flame is
quenched y mixing cooler fluid.
 Hydrocarbons

From the exhaust normally total HCs are

measured. However, it is not necessarily
a significant index of pollutant emissions.
Engine exhaust gases contain variety of
HCs. Average break down by class of
HCs in a gasoline engine are
Paraffins 33%, olefins 27%, Aromatics 32%
and acetylene 8% and in terms of carbon
number in a diesel engine are
 CONTD
Compound Idling, mole Full load,
% Mole %
C2 – C 5 32 44
C6 – C11 14 2
C12 – C18 35 38
C18 – C24 10 15
0thers 9 1
 POSSIBLE HC FORMATION MECHANISMS

 Wall quenching → quenched layer thickness

in the range of 0.05 to 0.4 mm
 Misfiring
 Short circuiting
 Poor combustion quality / Flame quenching
 Crevice HC mechanisms
 Absorption of HCs in oil layer
 Poor combustion quality / Flame
quenching
Flame extinction in the bulk gas in certain
operating conditions is one of the major source
of HC emissions. As cylinder pressure falls
during the exp stroke the temp of the unburned
mixture ahead of the flame decreases. If the
temp falls too rapidly, the flame may extinguish
This phenomenon during idling and light load
conditions where RGFs are high, if mixture is
very lean, and substantially retarded conditions.
 Crevice HC mechanisms
Crevices in the combustion chamber walls are
small volume with narrow entrances where flame
is unable to penetrate, is one of the major
source of HC emissions.
Crevice regions are volume between the piston
and the cylinder, thread around the spark plug,
space around the spark plug electrode, crevices
around the intake and exhaust valve heads and
head gasket crevice.
 V-6 engine crevice data
Location of crevices Area, cm3 Percentage
Displ vol./cylinder 632
Clearance vol./cylinder 0.89 1.00
Vol. above Ist ring 0.93 1.05
Vol. below Ist ring 0.47 0.52
Vol. between rings 0.68 0.77
Vol..behind IInd ring 0.47 0.52
Total ring crevice volume 2.55 2.9
Spark plug thread crevice 0.25 0.28
Head gasket crevice 0.3 0.34
Total crevice volume 3.1 3.5
 Mechanism
As cylinder pressure increases during
compression stroke, unburned mixture is forced
into the crevice regions. Since this crevices has
large S/V ratio, the gas flowing in each crevice
cools by heat transfer to the wall. During
combustion the pressure in the cylinder
continues to rise more and more with a result
more unburned mixture flows to the crevices.
Since the crevices has very narrow passages
flame can not penetrate there.
 Mechanism contd.
Unburned gases flow into the crevices until
cylinder pressure starts to decreases.
Once crevice gas pressure is higher than
cylinder gas pressure gas flows back from
each crevices to the cylinder. Normally,
cylinder gas pressure start to decrease
from 15 to 20 degree crank angle after
TDC. 5 to 10% of the total cylinder
charge is normally trapped in these
crevices.
Absorption of HC in engine oil
During compression stroke oil layer in the
cylinder wall will absorb fuel vapour.
Absorption continues till halfway of flame
propagation.
This absorbed fuel vapour starts desorbing at
the end of flame propagation and continues to
desorb throughout expansion and exhaust
stroke.
Summary of CO, HC, & NOx formation in SI engines
 Benzene
 Benzene represents a special case due to its toxicity and its
carcinogenic effect.
 Although it is also emitted in other industrial activities, it is
estimated that 80 to 85% of the benzene in the atmosphere
comes from the automobile.
 In heavy traffic, up to 20 to 30 µg/m3 of benzene can be found
in the air.
 Despite the limitation of its maximum content to 5% by
volume and an average value of around 2 to 3% by weight.
 All the aromatics act to form benzene at the exhaust, whereas
the other hydrocarbons, alcohols and lead have no effect.
 Three possible sources of benzene
emissions
 Due refuelling losses.
 Due evaporation losses.
 Benzene from exhaust.
 Refuelling losses.
 Refuelling losses depend on the ambient temperature at the
time and can be determined by the following equation:

Bze  0.23Bz d  0.21 Bz r

 Where Bze = mass fraction of Bz in the HC vapor emitted.

 Where Bzd = mass fraction of Bz in the gasoline distributed
 Where Bzr = mass fraction of Bz in gasoline in the tank.
 Evaporation losses
 Evaporation losses from the carburetor and the fuel tank, which result
from the dissipation of heat when the engine is turned off and from
variations in temperature between day and night (respiration).
 The following equations have been established:
 Engine stopped:
 % weight of Bz in vapor = 0.45% of the weight of Bz in gasoline
 Respiration:
 % weight of Bz in vapor = 0.89% of the weight of Bz in gasoline
 Benzene in the exhaust.
 With an equation of the following type:

Bzexh  0.50  0.44 Bz gas  0.04 Ar

Where:
 Bz
exh = % weight of Bz in the exhaust
 Bzgas = % weight of Bz in the gasoline
 Ar = % weight of other aromatics in the gasoline.
 On a European vehicle fueled with gasoline containing 3.1%
by weight of benzene and 30% by weight of other aromatics,
it has been found that 44% of the benzene emitted has
survived combustion, and that 56% was created during
combustion from other aromatics, olefins and cycloparaffins.
Polynuclear aromatic hydrocarbons
(PAH)
 PAHs are aromatic hydrocarbons with two or more Benzene or
Cyclopentatne rings.
 Most PAHs are formed in high temperature reactions
involving pyrolysis and incomplete combustion of organic
matters and carbon compounds.
 Presence of aromatic compounds in fuel favours the formation
of PAH.
 Depending on the urban locations, it is estimated that 35% to
100% of the PAH measured is generated by automobiles
 Diesel engines emit 5 times more PAH than gasoline engine.
 Most PAHs are found absorbed on the carbon particles
produced by the combustion.
 Carboxyl compounds
 By definition, these are organic
compounds containing
carboxyl groups. There are two
carboxyl compounds , namely
Aldehydes and Ketones which
are found in urban areas.
 Aldehydes
 Aldehydes are products of the incomplete combustion
of carbon compounds, either wood, coal, gas, gasoline,
diesel, etc.
 Hence they are found in automotive exhausts.
 The main aldehyde – most frequently found in air – is
formaldehyde HCHO, which is also formed in the
atmosphere by a reaction between the hydroxyl radical
and methane.
 It is also found in the effluents of a specialized
chemical plants that use it as a synthesis intermediate
and in many widely – consumed products.
 Ketones
 Ketones are compounds that are
practically absent from the combustion
effluents, especially in exhaust gases.
 Their presence in the atmosphere is
essentially due to their use as solvents.
 Control of vehicular emissions
 Fuel intake system design modifications
 Engine operating variables modifications
 Engine design modifications
 Use of after treatment devices
 Fuel modification and
 Use of alternative fuels
Intake system design modifications --- Variation of CO, HC
and NOx with the variations of A/F ratio
 Intake system design modifications ---
Contd.
 Air-fuel ratio is one of the most important
parameters, which significantly influence fuel
economy and exhaust gas emissions.
 Leaner mixture gives lower CO and HC
emissions until combustion quality become
poor. Eventually misfire occurs, HC emissions
rise sharply and combustion become erratic.
 Intake system design modifications ---
Contd.
To reduce CO and HC emissions attention is
required in the following areas
i) Efficient atomization of fuel to ensure proper
mixing with air
ii) Reduction of richness during deceleration
and idling
iii) Proper mixture strength during sudden
acceleration and deceleration
iv) Improved cold start system
 Intake system design modifications ---
Contd.
 Initially jets were modified to provide lean or
stoichiometric mixture specially bet 20% to 30%
load
 Mix. distribution was improved 2/3 barrel
carburettor
 Recently c’tors are being replaced by MPFI.
Mostly electronically controlled inj. System
 Due to very strict emission norms most recent
trend is to use feedback control systems
 Engine operating variables
modifications
 Apart from intake system design modifications
other techniques like retarded spark timing,
idle mixture adjustment, faster idle speed, lean
mixture operation etc. can reduce exhaust
emissions
 Retarded spark timing can reduce NOX as well
as HC emissions simultaneously
 Engine design modifications
 Engine design modifications such
as compression ratio, combustion
chamber design, lean burn engine
and charge stratified engine help
greatly in reducing exhaust
emissions.
 Effect of design and operating
variables on emissions
NOX emission is affected by the following variables
 Intake temperature

 Compression ratio

 Amount of supercharging

 Air-fuel ratio

 Ignition timing

 Engine load and speed

 EGR
Effect of temp & A\F on NO formation rate
Effect of CR on NOx Formation
5000
4500
4000
3500
3000
2500
Nox ,ppm
2000
1500
1000
500
0
6 7 8 9 10
NO and NO2 concentrations in SI engine exhaust as function of A\F
Variations of NO with crank angle: W2 closer to spark plug:
: * initial conditions
NO2 as percentage of NOx in diesel exhaust as function of load and speed
Variation of NOX with EGR
 HC emissions are affected by the following
variables
 Engine load and speed
 Spark timing
 CR, cyl dia, type of comb chamber etc.
 Water jacket temperature
 Crevices area
 Deposits on piston head, SP, cylinder wall etc.
 Valve overlap
 Type of fuel
 Air-fuel ratio
Effect of ignition delay on HC emissions in SI engines
CO emission is affected by the
following variables

 Air-fuel ratio

 Engine load, speed and other operating

conditions

 Fuel quality