Department of Mechanical Engineering, CUET 1

Exhaust Emission

The SIE exhaust gases contain:

• Oxides of nitrogen
→NO
→NO2
• Carbon monoxide
• Organic compounds
→ Unburned or partially burned hydrocarbons.

The relative amounts depend on engine design and operating

conditions.
• NOx: 500 – 1000 ppm or 20 gm/kg fuel.
• CO: 1 – 2% or 200 gm/kg fuel.
• HC: 1000 – 3000 ppm (as C1) or 25 gm/kg fuel.

In diesel engine exhaust

• NOx: Comparable to those from SIEs.
• HC: Significant though concentrations are lower by about a
factor of 5 than typical SIE levels.
• Particulate: 0.2 – 0.5% mass of fuel (∼ 0.1 μm diameter).
Primarily of soot with some additional absorbed hydrocarbon
material.
• CO: Not significant source of CO.
Currently used fuels, gasoline and diesel, contain sulfur. The sulfur is
oxidized (or burned) to produce SO2, of which a fraction can be
oxidized to sulfur trioxide, SO3, which combines with water to form a
sulfuric acid aerosol.

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 2

HC, CO and NO pollution formation mechanism in a SIE

NO forms throughout the high-temperature burned gases behind the
flame. The higher the burned gas temperature, the higher the rate of
formation of NO. As the burned gas cool during the expansion stroke
the reactions involving NO freeze.

Fig. 1: HC, CO, and NO pollutant formation mechanism in a SIE.

(Ref: Heywood)

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 3

CO normally forms from rich fuel-air mixtures, when there is

insufficient O2 to burn fully all the carbon in the fuel to CO2. In the
high temperature products, even with lean mixtures dissociation of
CO2 produces CO.
The unburned hydrocarbon emissions have several different
sources:
(i) Crevices, or narrow volumes, connected to the combustion
chamber.
(ii) Combustion chamber walls.
(iii) Engine oil left in a thin film on the cylinder wall, piston.

Nitrogen oxides
Kinetics of NO formation: NO formation requires three things:
nitrogen, oxygen, and high temperature and the principal source of
NO is the oxidation of atmospheric nitrogen. However if the fuel
contains significant nitrogen, the oxidation of the fuel nitrogen-
containing compounds is an additional source of NO.
In combustion of near-stoichiometric fuel-air mixtures (where the
reaction temperature is high) the principal reactions governing the
formation of NO from nitrogen are:
O + N2 = NO + N
N + O2 = NO + O
N + OH = NO + H

Formation of NO2: NO2/NO is negligibly small for SIE. In diesels

NO2 can be 10 – 30% of the total exhaust oxides of nitrogen
emissions. NO formed in the flame zone can be rapidly converted to
NO2 via reactions such as,
NO + HO2 → NO2 + OH
Subsequently, conversion of this NO2 to NO occurs via,
NO2 + O → NO + O2

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 4

unless the NO2 formed in the flame is quenched by mixing with

cooler fluid.

1500 rpm
WOT

Fig. 2: NO and NO2 concentrations. (Ref: Heywood).

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 5

When load increases (↑) temperature increases (↑) NO 2 decreases (↓)

When speed decreases (↓) heat loss increases (↑)

NO 2
temperature decreases (↓) NO2 increases (↑) increases (↑)
NO x
NOx concentrations of the exhaust gas from an SIE is primarily a
function of temperature and composition and is decreased:
A. By decreasing the combustion temperature
(i) by decreasing the compression ratio
(ii) by retarding the spark
(iii) by decreasing the speed
(iv) by exhaust gas recirculation
(v) by very rich or very lean air-fuel ratios
(vi) by increase in air humidity
(vii) by decreasing the inlet charge pressure.
B. By decreasing the oxygen available in the flame front.
(i) by using rich mixtures.
(ii) by decreasing homogeneity of the mixture.

Carbon monoxide
CO emissions from ICEs are controlled primarily by the F/A ratio.
For fuel-rich mixtures CO concentrations in the exhaust increase
steadily with increasing equivalence ratio (φ), as the amount of excess
fuel increases. For fuel-lean mixtures, CO concentrations in the
exhaust vary little with equivalence ratio and are of order 10-3 mole
fraction.
Since SIEs often operate close to stoichiometric at part load and fuel
rich at full load, CO emissions are significant and must be controlled.
RH → R → RO2 → RCHO →RCO → CO
R = hydrocarbon radical

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 6

φ-1

φ-1

Fig. 3: Variation of SIE CO emissions with eleven fuels of different

H/C ratio. (Ref: Heywood).

Unburned hydrocarbon emissions

Hydrocarbon emissions are the consequence of incomplete
combustion of the hydrocarbon fuel. Fuel composition can
significantly influence the composition and magnitude of hydrocarbon
emissions. Fuels containing high proportions of aromatics and olefins
produce relatively higher concentrations of reactive HCs. However,
many of the organic compounds found in the exhaust are not present
in the fuel, indicates that significant pyrolysis and synthesis occur
during the combustion process.

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 7

Hydrocarbon emission mechanisms in diesel engines

Diesel fuel contains hydrocarbon compounds with higher boiling
points, and hence higher molecular weight than gasoline. Also,
substantial pyrolysis of fuel compounds occurs within the fuel sprays
during the diesel combustion process. Thus, the composition of
unburned and partially burned hydrocarbons in the diesel exhaust is
much more complex than in the spark-ignition engine and extends
over a larger molecular size range.

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 8

Fig. 4: Diesel hydrocarbon formation mechanisms (a) for fuel injected

during delay period, (b) for fuel injected while combustion is
occurring. (Ref: Heywood).

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 9

Particulate emissions
SIE particulates: 3 types of particulates.
(i) Lead
(ii) Organic particulates (including soots)
(iii) Sulfates

Diesel particulates: Diesel particulates consist principally of

combustion generated carbonaceous material (soot) on which some
organic compounds have become absorbed. Most particulate material
results from incomplete combustion of fuel hydrocarbons; some is
contributed by lubricating oil.
Soot form primarily from the carbon in the diesel fuel. Thus the
formation process starts with a fuel molecule containing 12 to 22
carbon atoms and an H/C ratio of about 2.
Soot formation takes place in the diesel combustion environment at
temperatures between about 1000 and 2800 K, at pressures of 50 to
100 atm.

Particulate formation: Condensed phase material arises from the

fuel molecules via their oxidation and/or pyrolysis products. These
products typically include various unsaturated hydrocarbons,
particularly acetylene and its higher analogues (C2nH2), and
polycyclic aromatic hydrocarbons. These two types of molecules are
considered the most likely precursors of soot in flames. First particles
are very small (d < 2 nm).

Particle growth: Includes both surface growth, coagulation, and

aggregation. Surface growth, by which the bulk of the solid-phase
material is generated, involves the attachment of gas-phase species to
the surface of particles and their incorporation into the particulate
phase.

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 10

SIE

Fig. 5: Variation of HC, CO and NO concentration. (Ref: Heywood).

DI diesel
1000 rpm

Fig. 6: NOx and NO concentrations (Ref: Heywood).

Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam

Department of Mechanical Engineering, CUET 11

References
Heywood, John B., Internal Combustion Engine Fundamentals, 1988, McGraw-Hill Book
Com., Singapore.

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Applied Thermodynamics (Exhaust Emission) Dr. Bodius Salam