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8.

37 Nitrogen Oxide Analyzers TO RECEIVER

AT
R. J. GORDON (1974, 1982) B. G. LIPTÁK (1995, 2003) NOX
Flow Sheet Symbol

Analysis Methods: A. Infrared


B. Ultraviolet
C. Chemiluminescent
D. Colorimetric
E. Electrochemical
F. Coulometric
G. Gas chromatography

Reference Method: Colorimetric, applied to integrated samples collected in alkaline solution

Ranges: A. 0–500 ppm to 0–10%


B. 0–100 ppm to 0–100%
C. 0–50 ppb to 0–10,000 ppm
D. Down to ppb
E. 0–500 ppm to 0–2500 ppm
G. Down to ppb

Inaccuracy: Generally 1 to 2% of span, but some microprocessor-based electrochemical designs


can be accurate within 2% of reading, and some chemiluminescent units are accurate
within 0.5% of span.

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.

ABB Process Analytics-Bomem (A) (www.abb.com\analytical)


Ametek (A) (www.westernreseach.com)
Anarad (A) (www.anarad.com)
Antek Instruments (C) (www.antek.com)
Bran and Luebbe, Inc. (B, D, G) (www.branluebbe.com)
Bruel & Kjaer (A) (kbinfo@spectristech.com)
CEA (A) (ceainstr@aol.com)
Cole-Parmer Instrument Co. (www.coleparmer.com)
Cosa Instrument Corp. (E) (www.cosa-instrument.com)
Foxboro (A) (www.foxboro.com)
Hamilton Sundstrand (AIT division, Analect) (A) (AIT@HS.utc.com)
Horbia Instruments (A, C) (www.horiba.com)

1474
© 2003 by Béla Lipták
8.37 Nitrogen Oxide Analyzers 1475

Ionics (C) (www.ionics.com)


Leco Corp. (F) (www.leco.com)
LI-Cor (A) (www.licor.com), Midac (A) (www.Midac.com)
MKS Instruments (A) (mks@mksinst.com)
MSA Instruments (A) (www.msanet.com)
Ocean Optics (A) (www.oceanoptics.com)
Remspec Corp. (A) (www.remspec.com)
Rosemont (A) (www.rauniloc.com)
Sensidyne (A, E) (www.sensidyne.com)
Servomex (A) (www.servomex.com)
Shimadzu Corporation (C) (www.shimadzu.com)
Siemens (A) (www.sea.siemens.com)
Sierra Monitor Inc. (www.sierrainstruments.com)
Teledyne (A) (www.teledyne-ai.com)
Wilks Enterprise (A) (www.WilksIR.com)
Zellweger Analytics (A, C) (www.zelana.com)

INTRODUCTION Ultraviolet Analyzers

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

© 2003 by Béla Lipták


1476 Analytical Instrumentation

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

BALL VALVES FLOW HEATED


VACUUM INDIC-
(PNEUMATIC COMPARTMENT
BREAKER OPERATED) ATOR
FILTER
PROBE
SO2
SAMPLE
CELL

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.

© 2003 by Béla Lipták


8.37 Nitrogen Oxide Analyzers 1477

CALIBRATION difficult. This is because, in high concentrations, nitric oxide


GAS OXYGEN
FLOWMETER (NO) is rapidly oxidized to nitrogen dioxide (NO2) by air, and
NO2 condenses and dimerizes at high concentrations. For these
SOLENOID OZONATOR reasons, dynamic calibration for NO and NO2 requires great
VALVE
care. In colorimetric or coulometric analysis, the NO in fact is
HIGH-VOLTAGE not measured directly at all but is measured only after its oxi-
CATALYTIC POWER SUPPLY
NO2 NO
dation to NO2, so these analyzers are calibrated only for NO2.
CONVERTERa REACTOR PHOTO TUBE
Dynamic Calibration Dynamic calibration for NO2 requires
SAMPLE OPTICAL preparation of a sample of inert gas containing a known
AIR FILTER concentration of NO2. This sample may be obtained by gas-
OPTICAL
VACUUM WINDOW
dilution techniques (with special precautions in handling
TIME PUMP NO2), gravimetrically, electrolytically, or by use of a permeation
READ-OUT
PROGRAMMER tube. The permeation tube (as used with hydrocarbons) is
a CONVERTER CAN BE OMITTED IF ONLY NO IS MEASURED described in Section 8.25. However, NO2 permeation tubes are
moisture sensitive. Therefore, during storage, these tubes
FIG. 8.37c should be protected from moisture, and only dry gases should
Chemiluminescence nitric oxide analyzer. be used for dilution. If these precautions are observed, the
permeation tube is probably the most convenient method for
in stacks. These units are microprocessor based, are available the dynamic calibration of NO2.
with 4 to 20 mA transmitter outputs, and include self-diagnostic
and self-calibration features. The probe can be exposed to Static Calibration Static calibration is carried out with stan-
continuous temperatures of 1550°F (850°C), which for short dard solutions of nitrite. Because this procedure does not
periods can rise to 2200°F (1200°C). detect the components of the gas in the sampling line, it is
not as complete a test as is the dynamic calibration, but it is
Gas Chromatography much simpler. The stoichiometric ratio of nitrite to NO2 under
There have been a limited number of reports of applications controlled conditions is usually a constant value.
for analysis of oxides of nitrogen by gas chromatography. Such In the Griess–Saltzman method, the consensus (although
chromatographic columns are fairly short and are provided with there has been controversy) is that 0.72 mole of nitrite gives
electron capture detectors. These are the same types of chro- the color of 1 mole of NO2. Using the Jocobs–Hochheiser
matographs that are used for the analysis of peroxyacyl nitrates. method, this factor has been found to be 0.63.
For added details on gas chromatography, see Section 8.12.
NO–NO2 Combination Analysis

AMBIENT AIR MONITORING In continuous analysis, it is customary to determine both NO


and NO2 as NO2 (Table 8.37d). The NO is oxidized to NO2
Calibration Methods by means of potassium permanganate or dichromate or by
chromium trioxide, in various formulations. The efficiencies
The reliability of dynamic calibration of gas analyzers is always of conversion seem to depend on the length of service and,
superior to that of static calibration, but it is also much more for the chromium oxidizers, they also depend on humidity.

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.

© 2003 by Béla Lipták


1478 Analytical Instrumentation

SERIES MODE

NO2 NO NO2 NO2


AIR IN SEPARATOR SEPARATOR
ANALYZER OXIDIZER ANALYZER
CONTACTOR CONTACTOR CONTROL
VALVE
NO2 NO OXIDIZER
CONCENTRATION CONCENTRATION EXHAUST

PARALLEL MODE I OPTICAL


CELLS
NO2 SAMPLE PUMP
AIR IN
ANALYZER AIR IN
REF. SAMPLE REF. SAMPLE
NO2
CONCENTRATION DIFFERENCE
NO
CONCENTRATION
AIR IN NO NO2 NO2
ANALYZER
OXIDIZER
PUMP PUMP
NOX CONCENTRATION
(= NO + NO2)
SOLUTION FLOW

PARALLEL MODE II REAGENT SPENT AIR FLOW


RESERVOIR REAGENT
NO2
AIR IN ANALYZER
FIG. 8.37f
NO2
Colorimetric nitrogen oxides analyzer.
CONCENTRATION

AIR IN NO2 NO2


NO NO2
ABSORBER
OXIDIZER
ANALYZER The Griess–Saltzman Method The Griess–Saltzman method
is used in most continuous colorimetric NO2 analyzers. It is
NO based on the reaction of NO2 with sulfanilic acid to form a
CONCENTRATION
diazonium salt that couples with N-(1-napthy1)-ethylenedi-
FIG. 8.37e amine dihydrochloride to form a deeply colored azo dye. Air
Nitrogen oxides analyzer modes. is passed into the reagent solution for not over 30 min. After
that, time is allowed for development, and the color is measured
at 550 nm.
Aqueous permanganate seems to be the best choice, even The measurable range of concentrations is from 0.02 to
though it may not be completely efficient (hence, NO may be 0.75 ppm. In manual use, the color is developed for 15 min and
underestimated). should be read within 1 hr (on a colorimeter or spectropho-
tometer). In a continuous analyzer (Figure 8.37f ), the gas
Series Analysis In series analysis for NO and NO2 (Figure and liquid flow rates are adjusted for optimal response, and
8.37e), the air passes through an NO2 analyzer for measurement the developed color is potentiometrically read in a flow cell
and removal of NO2, then through an oxidizer to convert NO using a 550 nm filter. Response times are usually 5 to 15 min.
to NO2, and finally through a second NO2 analyzer. The second
analyzer gives a measure of NO concentration. In one type The Jacobs–Hochheiser Method The Jacobs–Hochheiser
of parallel analysis, two equal air streams are analyzed for
method is the standard reference method used for U.S.
NO2, one of them after passage through an oxidizer. The latter
National Air Quality Standards. The reason for this is that the
gives total oxides of nitrogen (NO + NO2) from which NO
standards are based on the annual average, and this method
is found by difference from the other parallel analyzer. In a
allows collection of up to 24-hr integrated samples and delays
second type of parallel analysis, one stream is analyzed
in analysis of at least 2 weeks. In contrast, with the Griess–
directly for NO2, and the second is scrubbed free of NO2 by
Saltzman method, samples must be quickly analyzed.
passage through ascarite, followed by oxidation of NO to
In the Jacobs–Hochheiser method, the air is passed through
NO2 and NO2 analysis.
aqueous sodium hydroxide so that the NO2 is concerted to
nitrite ion. Sulfur dioxide is removed from the solution by
Colorimetric Determination treatment with hydrogen peroxide and is acidified. The rest
of the procedure is the same as for the Griess–Saltzman method
2
There are two important colorimetric methods for NO2 deter- except that sulfanilamide is used instead of sulfanilic acid.
mination. They are the Griess–Saltzman and the Jacobs– Efficiencies found with this procedure in the U.S. National
Hochheiser methods. Air Surveillance Network are approximately 35%.

© 2003 by Béla Lipták


8.37 Nitrogen Oxide Analyzers 1479

various oxidizer columns, the most commonly used is the


TABLE 8.37g permanganate one, but none is completely satisfactory. It is
Typical Range, Sensitivity, and Alarm Setpoints of Portable
important to calibrate it over a range of nitric oxide concen-
Personal Protection Monitors*
trations and at various humidity levels.
Alarm Set Points The chemiluminescent method utilizes the reaction between
Gas Range Resolution (low/high)
ozone and nitric oxide. This is a dry gas method requiring
O2 0–30% 0.1% 19.5/23.5% an ozone generator and compressed gas. In the chemilumi-
CO 0–500 ppm 1 ppm 35/200 ppm nescent method, a catalytic reduction of nitrogen dioxide to
H2S 0–100 ppm 1 ppm 10/20 ppm nitric oxide is required.
SO2 0–20 ppm 1 ppm 2/10 ppm For industrial applications, the most often used analyzers
NO 0–250 ppm 1 ppm 25/50 ppm
are the nondispersive infrared, ultraviolet, and electrochemical
types. The chemiluminescent and gas chromatographic tech-
NO2 0–20 ppm 0.1 ppm 1/10 ppm
niques are less frequently used.
NH3 0–50 ppm 1 ppm 25/50 ppm
PH3 0–5 ppm 0.1 ppm 1/2 ppm
References
Cl2 0–10 ppm 0.1 ppm 0.5/5 ppm
HCN 0–100 ppm 1 ppm 4.7/50 ppm 1. Fontijn, A., Sabadell, A. J., and Ronco, R. J., Analytical Chem., 42.
2. Air Quality for Nitrogen Oxides, U.S. Environmental Protection
* Abstracted from Cole-Parmer Catalog 2001/2002, Vernon Agency, Air Pollution Control Office Publication No. AP-84, Chap. 5.
Hills, IL, 2001.

Bibliography
Portable Monitors
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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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Skoog, D. A. and Leary, J. L., Principles of Instrumental Analysis, 4th ed.,
The most widely used conventional method of ambient air Saunders College Publishing, 1992.
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© 2003 by Béla Lipták