8.

Carbon Dioxide
R. A. HERRICK

(1974, 1982)

To Receiver

B. G. LIPTK

(1995, 2003)

AT
co2
Flow Sheet Symbol

1242
2003 by Bla Liptk

Types of Sensors:

a) Nondispersive infrared (NDIR); see Table 8.9a for IR analyzer designs and
applications
b) Gas filter correlation (GFC)
c) Orsat

Sample Pressure:

Up to 15 PSIG (104 kPa), but atmospheric or near atmospheric is normal

Sample Temperature:

Up to approximately 120F (49C) not a consideration when freeze-out trap is used

Sample Flow Rate:

Generally less than 0.5 acfm (2.35 10 m /sec); typically 1 to 2 l/min

Inaccuracy:

a) Can be as high as 0.2 ppm; typically 1% to 2% of full-scale range

b) 1% to 2% of full scale, including drift
c) Laboratory procedure

Ranges:

a) 0 to 2000 ppm, 0 to 3000 ppm, 0 to 5000 ppm, 0 to 1%, 0 to 2%, 0 to 5%, 0 to

10%, 0 to 20%, and 0 to 100% (see Table 8.9b for overall capability)
b) 0 to 5 ppm, 0 to 10 ppm, 0 to 20 ppm, 0 to 50 ppm, 0 to 100 ppm, 0 to 500 ppm,
0 to 1000 ppm, 0 to 2000 ppm
(low detectable limit is 0.1 ppm)

Response:

a) Determined by cell volume and sampling rate; typically less than 30 sec
b) 90 sec with 30-sec signal averaging time

Costs:

Portable, battery-operated, diffusion type monitor with two alarm settings, digital
display, and 4- to 20-mA output is $1500; permanently installed, explosion-proof
NDIR analyzer with recorder is about $10,000.

Partial List of Suppliers:

Advanced Pollution Instruments API (www.teledyne-api.com)

AMC (Armstrong Monitoring Corp.) (www.armstrongmonitoring.com)
Ametek/Thermox (www.thermox.com)
Bran & Luebbe (www.branluebbe.com)
CEA Instruments (www.ceainstr.com)
Dasibi Environmental Corp. (www.dasibi.com)
Delphian Corp. (www.delphian.com)
Ecotech (www.ecotech.com.au)
E&E Process (www.process-controls.com)
EMS (Environmental Monitoring Systems) (www.emssales.com)
Enviro Technology (www.et.co.uk)
Foxboro-Invensys (www.foxboro.com)
Horiba Instrument Inc. (www.nettune.net)
Innova Air Tech Instruments (www.inniva.dk)
International Sensor Technology (www.intlsensor.com)
IT Group (www.theitgroup.com)
MSA Instrument Div. (www.msanet.com)
Purafil Inc. (www.purafilonguard.com)
Sensidyne Inc. (www.sensidyne.com)
Servomex Co. (www.servomex.com)

8.9 Carbon Dioxide

1243

Sieger Gasalarm; Siemens Energy & Automation (www.sea.siemens.com)

Sierra Monitor Corp. (www.sierramonitor.com)
Sigrist-Photometer Ltd. (www.photometer.com)
Teledyne Analytical Instruments (www.teledyne-ai.com)
Thermo Environmental Instruments (www.thermoei.com)
Thermo Gas Tech (www.thermo.com)
Topac (www.topac.com)
Yokogawa Corp. of America (www.yca.com)

INTRODUCTION

AMBIENT AIR MEASUREMENT

The measurement of carbon dioxide in the ambient air is the

primary concern of geophysicists, rather than of the air pollution control engineer. The precise measurement of the carbon dioxide content of the atmosphere is of significant concern in determining long-term changes in the composition of
the atmosphere. The measurement techniques used by geophysicists are highly precise compared to the techniques used
for air quality- or air pollution-related measurements.
Air quality-related measurements can be used to monitor
the return air quality from occupied spaces and, based on
those measurements, to modulate the rate at which fresh air
is being introduced. In air pollution-related applications, carbon dioxide is hardly ever measured in the ambient air. It is
usually measured at emission points since some combustion
equipment regulations are stated in terms of allowable pollutant discharges corrected to 50% excess air.

The precise knowledge of the carbon dioxide concentration

in the atmosphere is necessary. An increase in global carbon
dioxide concentration of only 1% (or about 3 ppm) has significant consequences on the weather. The instruments used
to measure atmospheric carbon dioxide concentrations must,
of necessity, be highly precise, such as the gas filter correlation (GFC) units discussed later.

Nondispersive Infrared Type

These instruments are discussed in detail in Section 8.27.
Since the absorption bands of water and carbon dioxide
somewhat overlap, a freeze-out trap (80C or 112F) is
often used in the sample preparation system to remove the
water prior to the measurement.

TABLE 8.9a
IR Analyzer Applications Summary
Organic Vapors
Analyzer

Carbon
Monoxide

Carbon
Dioxide

Simple
Molecules

NDIR

Mid-IR filter

Complex
Molecules

2003 by Bla Liptk

Comments

Single-component analysis: same as above,

including ammonia, vinyl chloride,
carbon tetrachloride, methyl ethyl ketone,
ethylene dichloride, etc.

Single-component analysis: ethylene

dichloride, water, phenol, methyl alcohol,
etc.; moisture in solids
Stack analysis, single-component gas
analysis

Multiple-filter near-IR
Multiple-filter mid-IR

Solids
(Reflection)

Single-component analysis: ethylene, CO,

acetylene, methane, etc.

Near-IR filter

Correlation
spectrometer

Organic
Liquids

Multiple components for cereal, meat, and

paper analysis

Automotive exhaust analysis (CO, CO2,

CH); multiple components for mike
analysis, multiple components of gases
using a programmable circular variable
filter

1244

Analytical Instrumentation

TABLE 8.9b
Typical Applications for NDIR Analyzers
Gas
Ammonia (NH3)

Minimum Range (ppm)

010

Butane (C4H10)

0300

0100

Carbon dioxide (CO2)

010

0100

Carbon monoxide (CO)

050

0100

Ethane (C2H6)

020,000

010

Ethylene (C2H4)

0500

0100

Hexane (C6H14)

0200

05

Methane (CH4)

02000

0100

Nitrogen oxide (NO)

0500

010

Propane (C3H8)

0300

0100

Sulfur dioxide (SO2)

0500

030

Water vapor (H2O)

03000

05

When using prepared calibration standard mixtures of

carbon dioxide in nitrogen, an inaccuracy of 0.2 ppm is
attainable. At normal atmospheric CO2 concentration levels
of approximately 314 ppm, this error is equivalent to 0.06%.
Nondispersive infrared (NDIR) type CO2 monitors for heating, ventilation, and air conditioning (HVAC) and industrial
applications are available in both portable and permanently
installed designs. The portable units are usually battery operated,
and their ambient sample is received by a combination of diffusion and convection effects in the sensor head, without any pumps
or filtering. These units are usually provided with digital displays,
one or two alarm settings, and analog or digital output signals.
The more expensive, permanently installed or wall-mounted
NDIR units often include data loggers, which can store about
1000 readings along with their times and dates. Some of these
units can also detect other gases, such as CO, H2S, or O2.
Gas Filter Correlation Type
When very accurate low-level measurements are needed, or
when background gases that have the potential to interfere
with the measurement are present, GFC is used. In these
designs, the measuring and reference filters are replaced by
gas-filled cuvettes. The reference cuvette is filled with CO2
and the measuring cuvette usually with nitrogen.
In addition to being unaffected by the presence of background gases, both the accuracy and the response time of
these instruments are better than those using filters. If DFC
is used in combination with single-beam, dual-wavelength
technology, it is virtually immune to obstruction of the optics.
This, in turn, prevents drift and thereby reduces the frequency
at which recalibration is needed.
SOURCE MEASUREMENT
Measurement of the carbon dioxide, carbon monoxide, and
oxygen concentration of flue gases from boilers has been

2003 by Bla Liptk

Maximum Range (%)

0300

done for many years (see Figure 8.3k). These measurements

allow precise setting of boiler operating variables for maximum fuel economy.
Before the use of the infrared analyzer became accepted
practice, mechanical instruments were used to continuously
determine the carbon dioxide content of flue gases. Their
operation was based on the reduction in gas volume resulting
from the absorption of carbon dioxide in a strong alkaline
solution. This is the principle of the Orsat analyzer, still used
as the standard method for manual determination of combustion gas composition.
For air pollution testing purposes, the carbon dioxide
content of the flue gas is determined only during the few
hours of the test. The usual procedure is to slowly withdraw
a low-volume integrated sample into a plastic bag over the
duration of the test. The bag sample is then analyzed manually using an Orsat analyzer or instrumentally using a NDIR
analyzer.
Bibliography
Annual Book of ASTM Standards, West Conshohocken, PA: American Society for Testing and Materials, 2002.
Ewing, G., Analytical Instrumentation Handbook, New York: Marcel Dekker,
1990.
Gas Detectors and Analyzers, Measurement and Control, October 1991.
Liptk, B. G., Ed., Environmental Engineers Handbook, 2nd ed., Chelsea,
MI: Lewis Publishers, 1996.
Liptk, B. G., Saving through CO2 Based Ventilation, ASHRAE Journal,
July 1979.
Lodge, J. P., Methods of Air Sampling and Analysis, Chelsea, MI: Lewis
Publishers, 1988.
Meyers, R. A., Ed., Encyclopedia of Analytical Chemistry: Instrumentation
and Applications, New York: John Wiley & Sons, 2000.
Sherman, R. E., Process Analyzer Sample-Conditioning System Technology,
New York: John Wiley & Sons, 2002.
Van den Berg, F. W. J., Hoefsloot, H. C. J. and Smilde, A. K., Selection
of Optimal Process Analyzers for Plant-Wide Monitoring, Analytical
Chemistry, 74(13), 31053111, 2002.