Thermal conductivity detector

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The thermal conductivity detector (TCD), also known as a katharometer, is a bulk property detector and a chemical specific detector commonly used in gas chromatography. [1] This detector senses changes in the thermal conductivity of the column eluent 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.

Contents

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 Thermal Conductivity Detector 1.svg
TCD schematic

A schematic of a classic thermal conductivity detector design utilizing a Wheatstone bridge 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 or hydrogen, virtually all compounds can be detected. That's why the TCD is often called a universal detector.

Used after a separation column (in a chromatograph), a TCD measures the concentrations of each compound contained in the sample. Indeed, the TCD signal changes when a compound passes through it, shaping a peak on a baseline. The peak position on the baseline reflects the compound type. The peak area (computed by integrating the TCD signal over time) is representative of the compound concentration. A sample whose compounds concentrations are known is used to calibrate the TCD: concentrations are affected to peak areas through a calibration curve.

The TCD is a good general purpose detector for initial investigations with an unknown sample compared to the FID that will react only to combustible compounds (Ex: hydrocarbons). Moreover, the TCD is a non-specific and non-destructive technique. The TCD is also used in the analysis of permanent gases (argon, oxygen, nitrogen, carbon dioxide) because it responds to all these substances unlike the FID which cannot detect compounds which do not contain carbon-hydrogen bonds.

Considering detection limit, both TCD and FID reach low concentration levels (inferior to ppm or ppb). [2]

Both of them require pressurized carrier gas (Typically: H2 for FID, He for TCD) but due to the risk associated with storing H2 (high flammability, see Hydrogen safety), TCD with He should be considered in locations where safety is crucial.

Considerations

One thing to be aware of when operating a TCD is that gas flow must never be interrupted when the filament is hot, as doing so may cause the filament to burn out. While the filament of a TCD is generally chemically passivated to prevent it from reacting with oxygen, the passivation layer can be attacked by halogenated compounds, so these should be avoided wherever possible. [3]

If analyzing for hydrogen, the peak will appear as negative when helium is used as the reference gas. This problem can be avoided if another reference gas is used, for example argon or nitrogen, although this will significantly reduce the detector's sensitivity towards any compounds other than hydrogen.

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.

Applications

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.

Detection of helium loss from the helium vessel of an MRI superconducting magnet.

Also used within the brewing industry to quantify the amount of carbon dioxide within beer samples.

Used within the Energy Industry to quantify the amount (Calorific Value) of Methane within Biogas Samples

Used within the Food and Drink Industry to quantify and/or validate food packaging gases.

Used within the Oil&Gas industry to quantify the percentage of HCs when drilling into a formation.

Related Research Articles

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<span class="mw-page-title-main">Size-exclusion chromatography</span> Chromatographic method in which dissolved molecules are separated by their size & molecular weight

Size-exclusion chromatography, also known as molecular sieve chromatography, is a chromatographic method in which molecules in solution are separated by their size, and in some cases molecular weight. It is usually applied to large molecules or macromolecular complexes such as proteins and industrial polymers. Typically, when an aqueous solution is used to transport the sample through the column, the technique is known as gel-filtration chromatography, versus the name gel permeation chromatography, which is used when an organic solvent is used as a mobile phase. The chromatography column is packed with fine, porous beads which are commonly composed of dextran, agarose, or polyacrylamide polymers. The pore sizes of these beads are used to estimate the dimensions of macromolecules. SEC is a widely used polymer characterization method because of its ability to provide good molar mass distribution (Mw) results for polymers.

<span class="mw-page-title-main">High-performance liquid chromatography</span> Technique in analytical chemistry

High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify specific components in mixtures. The mixtures can originate from food, chemicals, pharmaceuticals, biological, environmental and agriculture, etc, which have been dissolved into liquid solutions.

TCD can be used as:

Gel permeation chromatography (GPC) is a type of size-exclusion chromatography (SEC), that separates high molecular weight or colloidal analytes on the basis of size or diameter, typically in organic solvents. The technique is often used for the analysis of polymers. As a technique, SEC was first developed in 1955 by Lathe and Ruthven. The term gel permeation chromatography can be traced back to J.C. Moore of the Dow Chemical Company who investigated the technique in 1964. The proprietary column technology was licensed to Waters Corporation, who subsequently commercialized this technology in 1964. GPC systems and consumables are now also available from a number of manufacturers. It is often necessary to separate polymers, both to analyze them as well as to purify the desired product.

<span class="mw-page-title-main">Gas chromatography</span> Type of chromatography

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<span class="mw-page-title-main">Gas chromatography–mass spectrometry</span> Analytical method

Gas chromatography–mass spectrometry (GC–MS) is an analytical method that combines the features of gas-chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC–MS include drug detection, fire investigation, environmental analysis, explosives investigation, food and flavor analysis, and identification of unknown samples, including that of material samples obtained from planet Mars during probe missions as early as the 1970s. GC–MS can also be used in airport security to detect substances in luggage or on human beings. Additionally, it can identify trace elements in materials that were previously thought to have disintegrated beyond identification. Like liquid chromatography–mass spectrometry, it allows analysis and detection even of tiny amounts of a substance.

<span class="mw-page-title-main">Column chromatography</span> Method to isolate a compound in a mixture

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<span class="mw-page-title-main">Electron capture detector</span> Device for detecting atoms and molecules in a gas

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<span class="mw-page-title-main">Flame ionization detector</span> Type of gas detector used in gas chromatography

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A chromatography detector is a device that detects and quantifies separated compounds as they elute from the chromatographic column. These detectors are integral to various chromatographic techniques, such as gas chromatography, liquid chromatography, and high-performance liquid chromatography, and supercritical fluid chromatography among others. The main function of a chromatography detector is to translate the physical or chemical properties of the analyte molecules into measurable signal, typically electrical signal, that can be displayed as a function of time in a graphical presentation, called a chromatograms. Chromatograms can provide valuable information about the composition and concentration of the components in the sample.

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References

  1. Grob, Robert L. Ed.; "Modern Practice of Gas Chromatography", John Wiley & Sons, C1977, pg. 228,
  2. Budiman, Harry; Zuas, Oman (1 January 2015). "Comparison between GC-TCD and GC-FID for the determination of propane in gas mixture". Procedia Chemistry. 16: 465–472. doi: 10.1016/j.proche.2015.12.080 .
  3. http://ipes.us/used/58904.pdf [ bare URL PDF ]