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.

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.