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All gas chromatographs are designed to operate over relatively wide ranges
of temperature (e.g., -20oC to 400oC). Consequently, to avoid solute
condensation in the detector or detector-connecting tubes, the detector
should be capable of operating at least 20oC higher than the maximum
column temperature. Temperature programming is used in many analyses
and to assure temperature stability, the detector is usually thermostatted in
a separate oven. Few GC analyses are carried out at sub–ambient
temperatures but when they are, care must be taken to avoid
condensation, particularly in areas where there are electrical connections to
the detector.
The detector consists primarily of two parts, the sensor and the associated
signal conditioning electronics. The two parts can be integral or discrete.
Although to minimize dispersion, the sensor should be situated as close to
the column as possible. The electronic system can be situated some
distance from the sensor if more convenient. Nevertheless, the signal must
be transmitted in an appropriate manner to avoid any electrical interference
that might provide extra noise or signal distortion. The associated
electronics may contain an A/D converter to provide a binary output that
can be addressed and acquired by a computer or the analog signal may be
passed to a computer that has its own A/D converter. In general the sooner
the signal is digitized the better, as digital data is far more immune to
external interference than analog signals.
It has been suggested that Katharometer be merged into this article or section.
(Discuss)
The thermal conductivity detector (TCD) is a bulk property detector and a chemical
specific detector commonly used in gas-liquid chromatography. [1]This detector senses
changes in the thermal conductivity of the column effluent and compares it to a
reference flow of carrier gas. Since most compounds have a thermal conductivity much
less than that of the common carrier gases of helium or hydrogen, when an analyte
elutes from the column, the effluent thermal conductivity is reduced and produces a
detectable signal.
[edit]Operation
Since all compounds, organic and inorganic, have a thermal conductivity different from
helium, all compounds can be detected by this detector. The TCD is often called a
universal detector because it responds to all compounds. Also, since the thermal
conductivity of organic compounds are similar and very different from helium, a TCD will
respond similarly to similar concentrations of analyte. Therefore the TCD can be used
without calibration and the concentration of a sample component can be estimated by
the ratio of the analyte peak area to all components (peaks) in the sample.
The TCD is a good general purpose detector for initial investigations with an unknown
sample. Since the TCD is less sensitive than the flame ionization detector and has a
larger dead volume it will not provide as good resolution as the FID. However, in
combination with thick film columns and correspondingly larger sample volumes, the
overall detection limit can be similar to that of an FID. The TCD is not as sensitive as
other detectors but it is non-specific and non-destructive.
The TCD is also used in the analysis of permanent gases (argon, oxygen, nitrogen,
carbon dioxide) because it responds to all these pure substances unlike the FID which
cannot detect compounds which do not contain carbon-hydrogen bonds.
Katharometer
From Wikipedia, the free encyclopedia
It has been suggested that this article or section be merged into Thermal conductivity
detector. (Discuss)
A katharometer is a thermal conductivity device for determining one gas in a binary or pseudo-binary mixture.
The thermal conductivity of a gas is inversely related to itsmolecular weight[1]. Hydrogen has approximately six
times the conductivity of nitrogen for example.
Contents
[hide]
1 Process description
2 Applications
3 See also
4 References
5 External links
[edit]Process description
It functions by having two parallel tubes both containing gas and heating coils. The gases are examined by
comparing the rate of loss of heat from the heating coils into the gas. The coils are arranged in a bridge
circuit so that resistance changes due to unequal cooling can be measured. One channel normally holds a
reference gas and the mixture to be tested is passed through the other channel.
Hydrogen H2 2.0158
Oxygen O2 31.998
[edit]Applications
In the oil industry katharometers have been used for a long time for hydrocarbon detection but have a history of
unstable calibrations in non stationary oil related applications. In normal drilling practice, 5 hydrocarbon gases,
plus a couple of non-hydrocarbon gases, are expected in normal samples resulting in cross-talk between the
methane absorption line and the ethane. Hence the current use of flame ionization detectors.
Katharometers are used medically in lung function testing equipment and in gas chromatography. The results
are slower to obtain compared to a mass spectrometer, but the device is inexpensive, and has good accuracy
when the gases in question are known, and it is only the proportion that must be determined.
The katharometer was developed in the late 1940s for measuring carbon
dioxide in the flue gasses produced from various types of industrial
furnaces. A knowledge of the carbon dioxide content allowed the
combustion conditions to be changed to improve burning efficiency. With
the introduction of gas chromatography, its use as a possible GC detector
was explored by Ray (11). T he sensor is a simple device and is depicted in
figure 12.
Figure 12. The Katharometer Detector
There are two types of sensor design, the "in-line" sensor where the
column eluent actually passes directly over the filament (as shown in figure
12) and the "off-line" cell where the filaments are situated away from the
main carrier gas stream and the gases or vapors only reach the sensing
element by diffusion.(as shown in figure 13). Due to the high diffusivity of
vapors in gases, the diffusion process can be considered as almost
instantaneous. The filament wire is usually made from tungsten or platinum
as both metals have high temperature coefficients of resistance and at the
same time are relatively inert. The column and reference filaments are
situated in the arms of a Wheatstone Bridge and a suitable current is
passed through the filaments to heat them significantly above ambient
temperature. To ensure temperature stability, the sensors and their
conduits are installed in a high thermal conductivity metal block which is
thermostatted by means of a separate oven. The performance of the in-line
sensor is almost identical to that of the off-line sensor.
For maximum sensitivity hydrogen or helium is used as the carrier gas. The
katharometer sensitivity is only about 10-6g/ml (probably the least sensitive
of all GC detectors) and has a linear dynamic range of about 500 (the
response index being between 0.98 and 1.02).
Courtesy of Supelco Inc.
Figure 14. The Separation of the Compounds of Hydrogen,
Deuterium and Tritium
Despite its sensitivity shortcomings the katharometer can be used in most
GC analyses that utilize packed columns and where there is no limitation in
sample availability. The device is simple, reliable, rugged and relatively
inexpensive. An example of the use of a katharometer to monitor the
separation of various compounds of hydrogen, deuterium and
tritium,employinggas solid chromatography is shown in figure 14. The
stationary phase was activated alumina [treated with Fe(OH)2], and the
column was 3 m long and 4 mm I.D. The carrier gas was neon, the flow
rate 200 ml/min (at atmospheric pressure) and the column temperature
was -196oC.