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Carbon Monoxide PDF
Carbon Monoxide PDF
Detector types A. Nondispersive infrared (NDIR); see Table 1.7b for IR analyzer designs and applications
A1. Gas filter correlation (GFC)
B. Mercury vapor
C. Gas chromatography
D. Electrochemical fuel cell
E. Catalytic oxidation
F. Others include, from color change badges, dosimeter tubes, and radon canisters to mass spectrometers
Inaccuracy For NDIR sensors, ±1% of full scale for up to 1000 ppm and ±2% to 3% of full scale for higher ranges. For infrared stack
gas analyzers, 2%–4% of reading can be expected, whereas for electrochemical ambient monitors, 1%–3% of full scale
is usual.
Sensitivity Generally 1 ppm; chromatographs can provide 0.1 ppm and mercury vapor analyzers 0.05 ppm.
Application For ambient air monitoring, electrochemical sensors are used most often; for detecting stack gas concentration, infrared
sensors are the most popular.
Ranges (see Table 1.8a) A. From 0 to 1, 0 to 5, 0 to 10, 0 to 20, 0 to 50, and 0 to 100 ppm for ambient and 0 to 200, 0 to 500, 0 to 1000, 0 to 2000,
0 to 5000, and 0 to 10,000 ppm for other applications, including stack gas. (See Table 8.9b for overall range capability.)
A1. 0–100 ppb to 0–1,000 ppm.
B. 0–50 ppm
C. 0–200 ppm
D. 0–50 to 0–500 ppm or more
E. 0–500 ppm
Response times Infrared units are usually adjustable down to a few seconds, whereas electrochemical sensors require 30–60 sec.
Costs Manual spot sensor tubes: Under $100. Pocket-size, battery-operated personal toxic gas monitor—$200–$700; continuous
industrial electrochemical or infrared monitor/alarm/transmitter— $400–$2000; portable, battery-operated flue gas
analyzer—$2000–$5000; mercury vapor analyzer—$7500; NDIR with recorder included—about $10,000; and gas
chromatograph (see Chapter 227)—$25,000 and up.
132
1.8 Carbon Monoxide 133
Table 1.8a
Atmospheric Carbon Monoxide Analyzers
Detection Method Range, ppm Sensitivity, ppm Advantages Disadvantages
NDIR 0–25, 50, 100 0.5–1 U.S. reference method, Sensitive, water, and CO2 interferences
accurate, stable, dry gases (correctable), zero gas problems
Mercury vapor (hot HgO + CO 0–50 0.05 Sturdy, accurate, dry gases, Interferences by water and other gases
releasing Hg vapor) high sensitivity
Gas chromatography (reduction of CO 0–200 0.1 Accurate, high sensitivity, Complex and expensive
to CH4, flame ionization detection) also read CH4, dry gases
134 Analytical Measurement
carbon monoxide with nitrogen or helium, which are free A schematic diagram of a typical NDIR analyzer is shown
of carbon monoxide. If the volumes used in dilution are in Figure 1.8a. Infrared radiation from a hot filament is chopped
accurately known, the concentration may be calculated. to pass alternately through sample and reference cells, to be
A known small volume of pure carbon monoxide is absorbed in the detector cell divided by a pressure-sensitive
placed in an evacuated tank of known volume, and the tank diaphragm. If the sample contains carbon monoxide, it will
is then filled with the dilutor gas. The pressures of the carbon absorb part of the radiation, causing that half of the detector to
monoxide volume and the final mixture must be known (or exert less pressure on the diaphragm, whose distortion is con-
else known to be equal). Smaller samples may be prepared verted to an electrical signal for rectification and amplification.
in plastic bags by injecting pure carbon monoxide from a gas
syringe into a stream of dilutor gas metered accurately into Amplifier
the bag with a flow device such as a wet test meter.
Meter R
Because cylinder nitrogen commonly has small amounts of
carbon monoxide present in it, it must not be assumed to be pure
Condenser
without verification. Pure helium is reliably free of carbon mon- Radiation microphone
oxide. A useful procedure is to zero the detector using helium. source
After that, one can measure the CO content of the available Filter Sample
cylinder nitrogen and can make the required correction. This cell cell
permits using the less expensive nitrogen for most calibrations.
M Chopper
A reference gas mixture whose carbon monoxide
content is not accurately known can also be analyzed gravi-
metrically or volumetrically by various methods, but these Filter Reference
cell cell
techniques are usually less convenient and often require
large amounts of gas. Radiation
Receiver
source
gas filter Correlation (gfC) Carbon monoxide is oxidized by hot mercuric oxide as
follows:
When very accurate low-level measurements are needed,
or when background gases that have the potential to inter-
210° C )
fere with the measurement are present, gas filter correlation CO + HgO (s) ¾(¾¾¾ ® CO2 + Hg (g) 1.8(1)
(GFC) is used (Figure 1.8c). In these designs, the measuring
and reference filters are replaced by gas-filled cuvettes. The
The mercury vapor released may be measured photo-
reference cuvette is filled with CO and the measuring cuvette
metrically. An analyzer based on this principle (Figure 1.8d)
usually with nitrogen.
can be operated continuously. It has higher sensitivity than
Orifice
Room air
scrubber Detector
Vent/ Exhaust
calibrator Preamp/
demodulator Pump
Orifice
Shutoff Display
Spangas CPU RS-232
valve Analog data
Fig. 1.8c
GFC-type carbon monoxide analyzer. (Courtesy of Teledyne Technologies Co.)
Sample
in Charcoal
filter
Micron Diaphragm
filter pump Dryer Flow
Sampling system regulator
Sample Reacter
optical path (Red HgO, 200°C)
Sample
out
Preheater
Iodine Mercury
lamp Reference
charcoal optical path
filter 2537 Å
analyzer
Fig. 1.8d
Mercury vapor carbon monoxide analyzer.
136 Analytical Measurement
does the NDIR type, but it also suffers from some interference. that is the heart of a high precision and specificity system
Detection levels go down to 0.025 ppm, and changes of a measuring methane and carbon monoxide.
tenth of that can be observed. Oxygenated hydrocarbons, ole- A precolumn prevents carbon dioxide, water, and hydro-
fins, and hydrogen interfere with the measurement, but all carbons other than methane from reaching the molecular
are normally at much lower concentrations in air than carbon sieve separation column. After separation, a catalytic nickel
monoxide. Water also interferes and should be removed by a reactor converts carbon monoxide to methane, which is
dryer. This instrument has found particular use in nonurban detected by flame ionization. The system permits determi-
measurements where carbon monoxide levels are low. nation of both methane and carbon monoxide about once
every 5 min. The output is linear for both components
and can be read from 0.1 to 200 ppm. The instrument is
gas Chromatograph relatively complex and expensive, however, and requires
technically trained operators.
Gas chromatographs are discussed in detail in Chapter 1.10.
Figure 1.8e illustrates an automated gas chromatograph
Total
CH4 – CO hydrocarbon
sample sample
loop loop
5 μm filter Solenoid
valve
Exhaust
Air
Sample pump Inject
air in valves Holding
Backflush amplifiers Recorders
Solenoid
valve valve
CH4
CO
Calibration Pre-
Exhaust
gas column
Separation
Total
column Flame hydrocarbon
ionization
detector
0–10 MV
Catalytic
reactor Output
Electrometer
Fig. 1.8e
Methane and carbon monoxide analyzer.
1.8 Carbon Monoxide 137
electrochemical
150° C )
5CO + I 2O5 ¾(¾¾ ¾ ® 5CO2 + I 2 1.8(2)
PortABle MonItors
* EPA, Air Quality Criteria for Carbon Monoxide, http://nepis.epa.gov/ Fig 1.8g
Exe/ZyNET.exe/9100E2UA.TXT?ZyActionD=ZyDocument&Client= “Hands free” alarm monitors for carbon monoxide or other
EPA&Index=Prior+to+1976&Doc. dangerous gas applications. (Courtesy of Ketech.)
138 Analytical Measurement
Catalytic Analysis
sPeCIfICAtIon forMs