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The General Properties of GC Detectors

The GC detector is designed to respond to very small quantities of vapor


contained in a permanent gas. Because the physical and chemical
properties of permanent gases differ widely from those of a vapor, a very
wide range of detection methods can be employed including the
measurement of standard physical properties such as thermal conductivity
and light adsorption to more specific properties such as ionization potentials
and heats of combustion.
The response of a GC detector can be general or specific but a detector with
a catholic response is generally more useful in routine
analyses. Aspecificdetector(e.g.,the nitrogen-phosphorus detector (NPD))
can be extremely useful for selectively monitoring compounds such as
herbicides and pesticides, when the compounds are not eluted discretely
but mixed with a number of other contaminating compounds.
GC detectors should be insensitive to changes in flow rate but,
unfortunately, few detectors have this attribute although some, for example
the FID, are virtually insensitive to changes in column flow rate. This allows
the use of flow programming development if so desired. Flow programming,
attempts to achieve the same result as temperature programming which is
to accelerate the strongly retained peaks through the column (see Gas
Chromatography). Some detectors require no other gas than that used as
the carrier gas, other require specific gases to be added to the columns
eluent for them to function. In some cases the detector prescribes a certain
gas to be used as the carrier gas (e.g., thesensitivity of the katharometer is
greater when helium is used as the carrier gas). In addition, if the gas
chromatograph is being used for permanent-gas analysis, then helium must
be used to differentiate the carrier gas from the other gases being
analyzed.

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.

Thermal conductivity detector


From Wikipedia, the free encyclopedia

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

The TCD consists of an electrically heated filament in a temperature-controlled cell.


Under normal conditions there is a stable heat flow from the filament to the detector
body. When an analyte elutes and the thermal conductivity of the column effluent is
reduced, the filament heats up and changes resistance. This resistance change is often
sensed by a Wheatstone bridge circuit which produces a measurable voltage change.
The column effluent flows over one of the resistors while the reference flow is over a
second resistor in the four-resistor circuit.
TCD Schematic

A schematic of a classic thermal conductivity detector design utilizing a wheatstone


bridge circuit. The reference flow across resistor 4 of the circuit compensates for drift
due to flow or temperature fluctuations. Changes in the thermal conductivity of the
column effluent flow across resistor 3 will result in a temperature change of the resistor
and therefore a resistance change which can be measured as a signal.

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.

Name Chemical composition Mass (g/mole)

Hydrogen H2 2.0158

Oxygen O2 31.998

Water vapor H2O 17.0069


Nitrogen N2 28.014

Carbon dioxide CO2 44.009

Carbon monoxide CO 28.010

Methane CH4 16.0426

[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.

Monitoring of hydrogen purity in hydrogen-cooled turbogenerators.

The Katharometer Detector

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

A filament carrying a current is situated in a tubular cavity through which


flows the column eluent. Under equilibrium conditions, the heat generated
in the filament is equal to the heat lost and consequently the filament
assumes a constant temperature. The heat lost from the filament will
depend on both the thermal conductivity of the gas and its specific heat.
Both these parameters will change in the presence of a different gas or
solute vapor and as a result the temperature of the filament changes,
causing a change in potential across the filament. This potential change is
amplified and either fed to a suitablerecorder or passed to an appropriate
data acquisition system.As the detector filament is in thermal equilibrium
with its surroundings and the device actually responds to the heat lost from
the filament, the detector is
extremely flow andpressure sensitive. Consequently, all katharometer
detectors must be carefully thermostatted and must be fitted with reference
cells to help compensate for changes in pressure or flow rate.
Figure 13. The Off-Line Katharometer Sensor

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.

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