1a the chemiluminescence technique", NO reacts rapidly with ozone to form NO2 and

About
oxygen. Abou 7o of the
NO, produced by
this reaction is an excited state and reverts
to the ground-state with the emission of radiant energy: in

NO+Og NO, +02 ..(4.7)

NO NO, +hv ..4.8)

The emitted radiation is received by a

photomultiplier tube whose output is amplhfied
and fed to a recorder. The intensity of radiation is proportional to the amount of nitricC
Oxide. The chemiluminescence reaction with ozone is specific for NO and if there is any
NO, present in the sample gas, it has to be dissociated first into NO before the gas enters
the reaction chamber. A thermal converter made of stainless steel coil is provided with the
instrument and the NO, content of the sample can be measured by taking the difference
in readings when the gas flows through the converter and when it is bypassed. Fig. 4.15
is a schematic diagram of a typical NO-NO, chemiluminescent analyzer.

Air/Oxygen
Ozonator

Power
Flowmeter supply
Optical
filter

Electro w.
PMT meter

Recorder

Reaction chamber

Flow meter
(1)
Pump

Converter
NO NO

Air sample

4.15 Chemiluminescent analyzer

Fig.

4.4.3 Carbon Monoxide monoxide levels is the

for measuring atmospheric carbon
ne standard method
 138 Environmental Pollution Control Engineering
nondispersive infrared spectrophotometry (NDIR). This method allows continuous
inuous analy.
sis
based on the capacity of carbon monoxide to absorb infrared radiation. A typical NDID
analyzer (Fig. 4.16) consists ofa sample cell and a reference cell, two infrared sources
a
a detector cell. The reference cell is filled with a non-absorbing gas, such as nitrogen.a
the sample cell is continuously flushed with the sample containing carbon monoxide whit
absorbs radiation at 4.6 um. The detector consists of two compartments separated hu .
thin metal diaphragm and filled with carbon monoxide.
by a
IR Source IR Source

Chopper

o - Gas inlet

Reference Sample cell

cell

Gas outlet

Absorbs IR energy
Detector o Other molecules

Diaphragm

www
Control
unit

Recorder
Fig. 4.16
Non-dispersive infrared analyzer
In operation, an optical chopper alternately exposes the to
the infrared sources. The reference cell reference and sample ce
passes almost all of the infrared energy on one

compartment of the detector cell, while

varying amount of infrared
a rsely
proportional to CO concentration in the sample energy, nt
Since radiation enters cell, reaches the other detector compa
more the reference cell side of the detector cO
contained therein expands causing a compartmench in
pressure differential across the
turn causes the diaphragm to
pulse back and forth in phase with the diaphragm The
magnitude diaphragm distention is a
of chopper ain the
function of the absorbing CO
concentrau
 Air Polution Sampling and Measurement 139
eell. The mechanical movement of the
B8mple c e
e

gamhich can be amplified and

diaphragm is converted into an electrical
signal whi
recorded.
mmercial
Com instruments can detect CO
concentrations from 1.0 ppm upto 25 to 100
depending path length, operating pressures and electronic amplification.
on
Water
vap is the main cause of interference and it can be removed by providing a drying stage
kefore measurements are made. NDIR analyzers have rapid response and good sensitivity
fore measur

w i d e range of concentrations but suffer from the problems of drift.

Another instrumental technique that has
recently become available as a commerci1a
analyzer is that involving gas chromatographie analysis. CO is separated from methane
and converted to methane subsequently by hydrogenation. The methane thus formed is
detected by a tlame 1onization unit. This technique is quite suitable for measuring ambi-
ent CO concentrations and is specifie to CO. The limit of detection ranges from a mini-
mum of 0.05 ppm to the highest urban concentration levels. The analyzer is relatively
expensive and requires hydrogen for the conversion of CO into CH, and also for the flame
in the flame ionization unit.
Other techniques for measuring CO levels include the electrochemical analysis, the
80 called ultraviolet mercury replacement method, and the catalytic analysis. In the
hot iodine pentoxide at 150 °C
electrochemical analysis12 the gas sample is passed over
when iodine gas is liberated:
LOs +5CO-> 5C0, +I2 (4.9)
reduced at the cathode of an
The liberated iodine is absorbed by an electrolyte and is
amperometric cell by the electrode reaction:
+2e > 21 ..(4.10)
I2
m e a s u r e of the CO content of the sample.
The current produced is a quantitative
with commercial instruments, but the
Minimunm detectable concentration is 0.1 ppm
is relatively slow.
response time of the analyser
method is based on the reduction of
mercuric
The ultraviolet mercury replacement
and mercury vapour.
Oxide by CO at 210°C to produce CO,
.(4.11)
CO+HgO(s)--210CC0+Hg(g)
of radiation from a
formed is determined through its absorption
The mercury vapour 0.025 to 10 ppm of CO.
of applicability of this method is from
mercury lamp. The range known as Hopcalite
the oxidation of CO by catalyst
a
involves
The catalytic analysis oxides (CuO and MnO,).
The resultant temperature
mixture of a metal
Which contains a
the carbon
monoxide concentration.
1 e can be used to measure
on the expected concentration and
depend
for stack gas analysis and a wet chemical
The techniques used The common
methods are NDIR absorption
de
Sred degree of accuracy. method of analysis is useful for
CO
Orsat method. The Orsat In the Orsat analyser
ennique known as the 0.2 per cent by volume, or 2000 ppm.
centrations greater than and the difference in volume
solution of cuprous chloride
absorbed in a
gives the amount of CO
DOn monoxide is and after the absorption step
readingstaken before
ween
present in the sampie