Thermal conductivity detector
Encyclopedia
The thermal conductivity detector (TCD), also known as a Katharometer, is a bulk property detector and a chemical specific detector commonly used in gas-liquid chromatography. 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 a detectable signal is produced.

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
Wheatstone bridge
A Wheatstone bridge is an electrical circuit used to measure an unknown electrical resistance by balancing two legs of a bridge circuit, one leg of which includes the unknown component. Its operation is similar to the original potentiometer. It was invented by Samuel Hunter Christie in 1833 and...

 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.

A schematic of a classic thermal conductivity detector design utilizing a wheatstone bridge
Wheatstone bridge
A Wheatstone bridge is an electrical circuit used to measure an unknown electrical resistance by balancing two legs of a bridge circuit, one leg of which includes the unknown component. Its operation is similar to the original potentiometer. It was invented by Samuel Hunter Christie in 1833 and...

 circuit is shown. 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
Flame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....

 and has a larger dead volume it will not provide as good resolution as the FID
Flame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....

. However, in combination with thick film columns and correspondingly larger sample volumes, the overall detection limit can be similar to that of an FID
Flame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....

. 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
Flame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....

 which cannot detect compounds which do not contain carbon-hydrogen bonds.

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
Bridge circuit
A bridge circuit is a type of electrical circuit in which two circuit branches are "bridged" by a third branch connected between the first two branches at some intermediate point along them. The bridge was originally developed for laboratory measurement purposes and one of the intermediate...

 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
Gram
The gram is a metric system unit of mass....

/mole
Molar mass
Molar mass, symbol M, is a physical property of a given substance , namely its mass per amount of substance. The base SI unit for mass is the kilogram and that for amount of substance is the mole. Thus, the derived unit for molar mass is kg/mol...

)
Hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

 
H2 2.0158
Oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 
O2 31.998
Water vapor
Water vapor
Water vapor or water vapour , also aqueous vapor, is the gas phase of water. It is one state of water within the hydrosphere. Water vapor can be produced from the evaporation or boiling of liquid water or from the sublimation of ice. Under typical atmospheric conditions, water vapor is continuously...

 
H2O 17.0069
Nitrogen
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

 
N2 28.014
Carbon dioxide
Carbon dioxide
Carbon dioxide is a naturally occurring chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom...

 
CO2 44.009
Carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...

 
CO 28.010
Methane
Methane
Methane is a chemical compound with the chemical formula . It is the simplest alkane, the principal component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel...

 
CH4 16.0426

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 detector
Flame ionization detector
A flame ionization detector is a type of gas detector used in gas chromatography. The first flame ionization detector was developed in 1957 by scientists working for the CSIRO in Melbourne, Australia....

s.

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
Hydrogen purity
Hydrogen purity or hydrogen quality is a term to describe the lack of impurities in hydrogen as a fuel gas. The purity requirement varies with the application, for example a H2 ICE can tolerate low hydrogen purity where a hydrogen fuel cell requires high hydrogen purity to prevent catalyst...

 in hydrogen-cooled turbogenerator
Hydrogen-cooled turbogenerator
A hydrogen-cooled turbo generator is a turbo generator with gaseous hydrogen as a coolant. Hydrogen-cooled turbo generators are designed to provide a low-drag atmosphere and cooling for single-shaft and combined-cycle applications in combination with steam turbines...

s.
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