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R. J. GORDON (1974, 1982) B. G. LIPTÁK (1995, 2003) NOX
Flow Sheet Symbol
Costs: The installation and the upkeep costs are normally larger than the first costs of purchasing.
A. Single-beam portable or laboratory units, $4,000 to $5,000; an industrial NDIR,
$8,000; a multi-gas analyzer pulling in up to five gases from 150 ft (50 m) distance,
$25,000 to $27,000; FTIR, $75,000 to $125,000
B. Laboratory spectrophotometers, from $2500 to $5000; industrial units, about $20,000
C. About $10,000 to $20,000
D. About $50,000
E. Pocket-sized personal monitors begin at $750; remote sensor heads begin at $1500;
on-site monitors with data loggers begin at $5000; stack gas analyzer with printer,
auto calibration, and probe costs $6000 to $8000
G. Installed cost in the range of $50,000 to $100,000
Partial List of Suppliers: Also refer to the Sections 8.4, 8.12, 8.15, 8.27, devoted to electrochemical analyzers,
chromatographic analyzers, colorimetric analyzers, infrared analyzers, and ultraviolet
analyzers.
1474
© 2003 by Béla Lipták
8.37 Nitrogen Oxide Analyzers 1475
The oxides of nitrogen are measured both in ambient air and The absorbance of nitrogen dioxide in the ultraviolet range
in the gases emitted by industry. While the types of analyzers is shown in Figure 8.37a. Because, in most combustion pro-
used for these two applications do overlap, here, an attempt cesses, there is an interest in determining the concentrations
will be made to separate them. Therefore, in this section the of the both NOx and SO2, some of the suppliers of ultraviolet
devices more often used for industrial emission monitoring will analyzers have combined the two tasks into a single analyzer
be discussed first. These include infrared, ultraviolet, chemilu- whereby their concentrations are simultaneously measured
minescent, gas chromatographic, and electrochemical devices. (Figure 8.37b). Because nitric oxide (NO) is essentially trans-
Colorimetric and coulometric analysis is more often used for parent in the visible and ultraviolet regions, it must be con-
ambient air analysis and will be discussed later in this section. verted to NO2 before it can be measured.
In Figure 8.37b, this conversion is achieved by contacting
the sample gas with oxygen pressurized to five atmospheres.
INDUSTRIAL EMISSION MONITORING Once the NO is converted, the total NO2 concentration is
measured as NOx. Ranges can be as narrow as 0 to 100 ppm
Paramagnetic Analyzers or as wide as 0 to 100% NOx, and the measurement error is
about 2% of full scale.
Nitrogen oxide is attracted by the magnetic field and therefore
is detectable by a paramagnetic analyzer. This instrument is Chemiluminescent Analyzers
described in this chapter under Oxygen Analyzers (Section
1
8.42) and is not widely used for the measurement of nitrogen Another method of nitrogen oxides determination makes use
oxide concentration. of the fact that nitric oxide (NO) reacts with ozone to form
nitrogen dioxide (NO2), and this reaction is accompanied
Thermal Conductivity Analyzers with the release of light (chemiluminescence).
The thermal conductivity (see Section 8.57) of nitric oxide NO + O3 → NO2 + hv (light 0.6 − 3µ ) 8.37(1)
(NO) is slightly less than that of air—about 90%. Therefore,
although thermal conductivity measurements have been If excess ozone is present, the light emission is proportional
attempted for NO analysis, it is neither a sensitive nor a selective to the amount of nitric oxide present in the sample. Instru-
means of measurement. ments that operate on the basis of this principle are commer-
cially available.
Nondispersive Infrared Analyzers For the determination of NO2 (which reacts with ozone
rather slowly), some analyzers are provided with a catalytic
Nondispersive infrared (NDIR) analyzers are suitable for the converter to first reduce NO2 to NO and then determine the
determination of nitric oxide (NO) concentration. These sum of NO2 and NO directly. The apparatus is schematically
devices are most often used in stack gas analyzer packages, shown in Figure 8.37c.
which, in addition to NOx, also detect the concentrations of
carbon dioxide, carbon monoxide, sulfur dioxide, and opac- Electrochemical Sensors
ity. Section 8.27 described the nondispersive infrared analyz-
ers, and Figures 8.27h and 8.27t show some of their stack- Portable or permanently installed probe-type electrochemical
mounted variations. sensors are available for NO, NO2, and NOx measurement
2.0
1.8
1.6
SO2
1.4
ABSORBANCE
1.2 NO2
1.0
0.8
0.6
0.4
280 436 578
0.2
0.0
250 300 350 400 450 500 550 600
WAVELENGTH (nm)
FIG. 8.37a
The absorbance of SO2 and NO2 in the ultraviolet range.
RECORDER
CONTROL CONTROL
STATION STATION
TIMER
STATION
LIGHT
NO2 SAMPLE CELL SOURCE
PHOTOMETER
STACK
AIR
O2
TANK
TO ELEC
SOLENOIDS
PRESSURE REGULATOR PRESSURE REGULATOR
SAMPLE IN
ASPIRATOR
POWER
SUPPLY TRAP PHOTOMETER
HEATED TUBING
115 V AC
EXTERNAL
FIG. 8.37b
Ultraviolet analyzer used for the simultaneous measurement of NOx and SO2.
TABLE 8.37d
Nitrogen Oxide Analyzers
General Method Type Advantages Disadvantages
Colorimetric Griess–Saltzman Precise, thoroughly tested, widely used, Short life of collected sample, sensitive reagents,
Jacobs–Hochheiser continuous analysis NO oxidation required.
Precise, stable after collection Not adapted to continuous analysis, sensitive
reagents, NO oxidation required.
Coulometric Simple apparatus, continuous analysis Sensitive to other oxidants, NO oxidation
required.
Chemiluminescent Dry gases only, sensitive photometry, Requires ozone generator NO2 catalytic
continuous analysis reduction.
Gas chromatography Specific, frequent analysis Not a developed instrument, expensive and
complex.
Electrochemical Simple apparatus, continuous analysis Sensitivity not high, NO oxidation required.
SERIES MODE
Bibliography
Portable Monitors
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York, 1990.
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lists the ranges, resolutions, and alarm set points for a number Landa, I., Visible (VIS) near infrared (NIR) rapid spectrometer for laboratory
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