Measurement of Exhaust

MEASUREMENT OF EXHAUST
EMISSIONS
By
Sreeram Nandakumar
14TH13F
NITK
NITK SURATHKAL
CONTENTS
Automobile
Sampling
NDIR
FID
exhaust
of exhaust gas
analyzer
analyzer
Chemiluminescence
Orsat
analyzer
apparatus
NITK SURATHKAL
KEYWORDS
N2
: Nitrogen
O2
: Oxygen
H2 O
: Water
CO2
: Carbon dioxide
CO
: Carbon monoxide
NOX
: Nitrogen oxides
SO2
: Sulphur dioxide
HC
: Hydrocarbons
PM
: Particulate matter
NITK SURATHKAL
AUTOMOBILE EXHAUST
Exhaust gasorflue gasis emitted as a result of

thecombustionof fuels such asnatural
gas,gasoline/petrol,diesel fuel,fuel oilorcoal. According
to the type of engine, it is discharged into the atmosphere
through anexhaust pipe,flue gas stackorpropelling
nozzle.
FIG 1:Sources of emission
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COMBUSTION PROCESS
Gasoline and diesel fuels are mixtures of hydrocarbons, compounds which

contain hydrogen and carbon atoms. In a perfect engine, oxygen in the air
would convert all the hydrogen in the fuel to water and all the carbon in the
fuel to carbon dioxide. Nitrogen in the air would remain unaffected. In reality,
the combustion process cannot be perfect, and automotive engines emit
several types of pollutants.
Perfect Combustion
FUEL (hydrocarbons) + AIR (oxygen and nitrogen)
CARBON DIOXIDE + water + unaffected nitrogen
Typical Engine Combustion

FUEL + AIR UNBURNED HYDROCARBONS + NITROGEN OXIDES+
CARBON MONOXIDE + CARBON DIOXIDE + water
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EXHAUST POLLUTANTS
Fig 2:Exhasut from SI engine
Fig 3: Exhaust from CI engine
HYDROCARBONS
Hydrocarbon emissions result when fuel molecules in the engine do not burn or
burn only partially.
Hydrocarbons react in the presence of nitrogen oxides and sunlight to form

ground-level ozone, a major component of smog.
Ozone irritates the eyes, damages the lungs, and aggravates respiratory problems.
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NITROGEN OXIDES (NOx)
Under the high pressure and temperature conditions in an engine,

nitrogen and oxygen atoms in the air react to form various nitrogen
oxides, collectively known as NOx.
They are a major contributor to acid rain
Action taken to reduce fuel consumption has, unfortunately, often led

to a rise in nitrogen oxide concentrations.
CARBON MONOXIDE
Carbon monoxide (CO) is a product of incomplete combustion and

occurs when carbon in the fuel is partially oxidized rather than fully
oxidized to carbon dioxide (CO ).
Carbon monoxide reduces the flow of oxygen in the bloodstream and is

particularly dangerous to persons with heart disease.
CARBON DIOXIDE
In recent years Carbon dioxide a product of perfect combustion is

considered as a pollution concern.
Carbon dioxide does not directly impair human health, but it is a

greenhouse gas that traps the earths heat and contributes to the
potential for global warming.
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SAMPLING OF EXHAUST GAS
CONSTANT VOLUME SAMPLING:
Fig 4:Constant volume sampling

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The entire exhaust gas from the vehicle is diluted with the filtered
room air. The dilution with air lowers partial pressure of unburned
hydrocarbons and water, and prevents their condensation in the
sampling line.
The diluted exhaust gas is drawn by a constant volume pump

system employing either a positive displacement pump (PDP) or a
critical flow venturi (CFV) and a blower.
The volume flow rate of the diluted exhaust (exhaust gas + air) is
maintained constant throughout the test .
From the diluted gas a small sample is continuously withdrawn and

collected in evacuated Teflon bags. A small part of the dilution air is
sampled simultaneously and collected in a separate bag to correct
for any background concentration of pollutant present in the
dilution air.
The sample bags are analyzed after the test is completed.

The mass of individual pollutants is determined from its measured
concentration in the sample bag, its density and the total volume
flow rate of the diluted exhaust during the test through CVS.
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FUNCTIONS OF SAMPLING
Condition the sample to meet the inlet sample specifications of the

particular analytical instruments.
Removing of particulate matter.
Some of the analytical instruments require that the sample is cooled

and dried. Water vapour should be condensed and removed from the
sample in a way that minimizes losses of acidic gases (NOx, SOx) due
to their solubility in the condensate. This can be achieved through very
rapid cooling in Peltier coolers.
Several instrumentsincluding FID hydrocarbon analyzers and

chemiluminescence NOx analyzerare also available in heated (wet)
versions to prevent losses due to condensation in the sampling system.
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NON DIPERSIVE INFRARED ANALYZER(NDIR)
NDIR analyzer is used in the measurement of CO (Carbon monoxide).
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,
where
I = Radiation energy absorbed
Io = Incident radiation energy
k = characteristic absorption constant for the gas, m 2 /gmol
c = concentration of the gas, gmol/m3
d = length of the gas column, m
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Fig 5:NDIR 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 m.
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.
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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.
Why not used for other gases?
IR absorbance to different hydrocarbons varies substantially
HCs do not have an adequate absorption in the IR wavelength range

that is specific to the saturated hydrocarbons and vice versa
NO absorbs only weekly in the infrared region.
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FLAME IONIZATION DETECTOR

(FID)
FID analyzer is mainly used in the measurement of HC (Hydro
carbons ) in the exhaust gas.
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 ppmC1 i.e., ppm of hydrocarbon containing equivalent
of one carbon atom.
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Fig 6:FID analyzer
FID essentially consists of a hydrogen-air burner and an ion

collector assembly .
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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.
ADVANTAGES:
Cost: Flame ionization detectors are relatively inexpensive to

acquire and operate.
Low maintenance requirements: Apart from cleaning or replacing

the FID jet, these detectors require no maintenance.
Rugged construction: FIDs are relatively resistant to misuse.
Linearity and detection ranges: FIDs can measure organic substance

concentration at very low and very high levels, having a linear
response of 106
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DISADVANTAGES
Flame ionization detectors cannot detect inorganic substances
In some systems, CO and CO2 can be detected in the FID using

a methanizer, which is a bed of Ni catalyst that reduces CO and
CO2 to methane, which can be in turn detected by the FID.
Another important disadvantage is that the FID flame oxidizes all

compounds that pass through it
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CHEMILUMINISCENCE
ANALYZER
Used for the measurement of NOx emissions
When NO and ozone (O 3 ) react a small fraction (about 10% at

26.7 C) of excited NO2* molecules is produced as per the
following reactions:
NO + O3
NO2*
NO2* + O2
NO2 + h
As the excited molecules of NO2 * decay to ground state, light in

the wavelength region 0.6-3.0 m 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.
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Fig7:Chemiluminescence 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 NO 2 . The

signal is then amplified and fed to recorder or indicating equipment.
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For the measurement of nitrogen oxides (NOx ), NO 2 in the sample is

first converted to NO by heating in a NO 2- to-NO converter prior to
its introduction into the reactor. At 315 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 NO 2 - toNO converter, concentration of NO alone is determined. The
difference between the two measurements provides the concentration
of NO2 in the sample.
The response of the instrument is linear with NO concentration. The

technique is very sensitive and can detect up to 10-3 ppm of NOx.
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ORSAT APPARTUS
An Orsats apparatus consists of the following:
A burette
A gas cleaner
Four absorption pipettes 1, 2, 3, 4.

PIPETTE 1:
Contains KOH (caustic soda) to absorb CO 2 (carbon
dioxide)
PIPETTE 2:
Contains an alkaline solution of pyrogallic acid to
absorbO2 (oxygen)
PIPPETTE 3, 4 :
Contain an acid solution of cuprous chloride to absorb
CO(carbon monoxide)
Furthermore the apparatus has a levelling bottle and a
three way cock to connect the apparatus either to gases or
toatmosphere
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Fig 8: Orsat Apparatus
100 cm3 of gas whose analysis is to be made is drawn into the bottle by
lowering the levelling bottle. The stop cock S4 is then opened and the
whole flue gas is forced to pipette 1. The gas remains in this pipette for
some time and most of the carbon dioxide is absorbed.
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The levelling bottle is then lowered to allow the chemical to come to its
original level. The volume of gas thus absorbed is read on the scale of the
measuring bottle.
The flue gas is then forced through the pipette 1 for a number of times to
ensure that the whole of the CO2 is absorbed.
Further, the remaining flue gas is then forced to the pipette 2 which
contains pyrogallic acid to absorb whole of O 2.The reading on the measuring
burette will be the sum of volume of CO2 and O2.
The oxygen content can then be found out by subtraction. Finally, as before,
the sample of gas is forced through the pipettes 3 and 4 to absorb carbon
monoxide completely.
The amount of nitrogen in the sample can be determined by subtracting from

total volume of gas the sum of CO2, CO and O2 contents.
NITK SURATHKAL
REFERENCES
1.http://en.wikipedia.org/wiki/Exhaust_gas
2.Automobile emissions: an overview, U.S
environmental protection agency
3.Motor Vehicle Exhaust Emissions, Self-Study
Programme 230,AUDI
4.Nptel lectures, Module 4:Vehicle emission
standards and measurement
Lecture 18:Emission measurement.
5.www.dieselnet.com/tech/measure_sample.php
6.http://en.wikipedia.org/wiki/Flame_ionization_detec
tor
7.www.scribd.com/doc/170513990/Orsat-GasAnalysis
NITK SURATHKAL
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MEASUREMENT OF EXHAUST

Exhaust gasorflue gasis emitted as a result of

FIG 1:Sources of emission

Gasoline and diesel fuels are mixtures of hydrocarbons, compounds which

Typical Engine Combustion

Fig 2:Exhasut from SI engine

Fig 3: Exhaust from CI engine

Hydrocarbons react in the presence of nitrogen oxides and sunlight to form

NITROGEN OXIDES (NOx)

Under the high pressure and temperature conditions in an engine,

They are a major contributor to acid rain

Action taken to reduce fuel consumption has, unfortunately, often led

Carbon monoxide (CO) is a product of incomplete combustion and

Carbon monoxide reduces the flow of oxygen in the bloodstream and is

In recent years Carbon dioxide a product of perfect combustion is

Carbon dioxide does not directly impair human health, but it is a

SAMPLING OF EXHAUST GAS

CONSTANT VOLUME SAMPLING:

Fig 4:Constant volume sampling

The diluted exhaust gas is drawn by a constant volume pump

From the diluted gas a small sample is continuously withdrawn and

The sample bags are analyzed after the test is completed.

Condition the sample to meet the inlet sample specifications of the

Removing of particulate matter.

Some of the analytical instruments require that the sample is cooled

Several instrumentsincluding FID hydrocarbon analyzers and

NON DIPERSIVE INFRARED ANALYZER(NDIR)

NDIR analyzer is used in the measurement of CO (Carbon monoxide).

Beer-Lambert's Law is used for operation of NDIR analyzers by

Fig 5:NDIR analyzer

wavelengths (not the entire range of wavelength of IR radiations) which has

The analyzer measures differential in absorption of energy from two columns of

The detector is divided in two compartments separated by a flexible

The flexible diaphragm of the detector senses the differential

Why not used for other gases?

IR absorbance to different hydrocarbons varies substantially

HCs do not have an adequate absorption in the IR wavelength range

NO absorbs only weekly in the infrared region.

FLAME IONIZATION DETECTOR

Pure hydrogen-air flames are practically ion-free but on introduction

The ionization current is proportional to the number of carbon atoms

The measurement of HC by FID is expressed as parts per million of

Fig 6:FID analyzer

FID essentially consists of a hydrogen-air burner and an ion

Sample gas is introduced with hydrogen in the burner assembly and

An electric potential is applied between the collector plates that

Cost: Flame ionization detectors are relatively inexpensive to

Low maintenance requirements: Apart from cleaning or replacing

Rugged construction: FIDs are relatively resistant to misuse.

Linearity and detection ranges: FIDs can measure organic substance

Flame ionization detectors cannot detect inorganic substances

In some systems, CO and CO2 can be detected in the FID using

Another important disadvantage is that the FID flame oxidizes all

Used for the measurement of NOx emissions

When NO and ozone (O 3 ) react a small fraction (about 10% at

As the excited molecules of NO2 * decay to ground state, light in

The quantity of excited NO2 produced is fixed at a given reaction

The sample containing NO flows to a reactor where it reacts with ozone