The Electron Capture Detector

The eluent from the column passes directly into a nebulizer, the outlet tube from the column terminating at the nozzle of the nebulizer. A portion of the atomized eluent passes directly into an ECD and then out to waste. The ECD is operated under the same conditions as those that would be used if it were employed as a GC detector. The work of Nota and Palombari established the system as a viable LC detector and showed that the solvents benzene, hexane, cyclohexane, pyridine, methanol, ethanol, diethyl ether and acetone could all be employed as components of the mobile phase without significantly affecting the standing current of the detector. The disadvantage of this system was that by employing a 

On leaving the column, the eluent passes into a stainless-steel transfer tube (1000 mm x 1.59 mm O.D. x 0.25 mm I.D.), enclosed in the oven, the temperature of which (300°C) is such that the liquid is completely vaporized. The increase in volume involved in this transition, forces the vapor into a 3 1 ECD, which is maintained at 300°C in the same oven as the transfer tube. A purge of 30 ml/min of nitrogen sweeps the vapor through the detector into a coil of stainless-steel tubing (2000 mm X 2.3 I.D.) from which it is collected as a liquid. 

The ECD signal is amplified using either pulse mode amplifier or a constant current amplifier. The latter can operate with 60 V pulses having a nominEd width of 1 jisec over a frequency range 0-130 kHZ. The standing current could be varied between zero and 5 x lO a. These conditions are normal for its use as a GC detector. 

The detector described by Willmott and Dolphin (72) is now manufactured commercially by Pye Unicam. The sensitivity to electron capturing substances it extremely high (1.2 x 10 10 g/ml) but the linear dynamic range is only about 100. 

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Selectivity Because it combines separation with analysis, gas chromatography provides excellent selectivity. By adjusting conditions it is usually possible to design a separation such that the analytes elute by themselves. Additional selectivity can be provided by using a detector, such as the electron capture detector, that does not respond to all compounds. 

Electron capture detector. Most ionisation detectors are based on measurement of the increase in current (above that due to the background ionisation of the carrier gas) which occurs when a more readily ionised molecule appears in the gas stream. The electron capture detector differs from other ionisation detectors in that it exploits the recombination phenomenon, being based on electron capture by compounds having an affinity for free electrons the detector thus measures a decrease rather than an increase in current. 

Electron Capture Detector In the electron capture detector (ECD), a beta emitter such as tritium or 63Ni is used to ionize the carrier gas. Electrons from the ionization migrate to the anode and produce a steady current. If the GC effluent contains a compound that can capture electrons, the current is reduced because the resulting negative ions move more slowly than electrons. Thus, the signal measured is the loss of electrical current. The ECD is very sensitive to materials that readily capture electrons. These materials frequently have unsaturation and electronegative substituents. Because the ECD is sensitive to water, the carrier gas must be dry. 

RELATIVE RESPONSE OF THE ELECTRON-CAPTURE DETECTOR TO ORGANIC COMPOUNDS... 

Bronlc acids containing electron-capturing subsitituents were developed by Poole and co-workers. Table 8.19 (451,535,536). In terms of volatility, stability of derivatives, and response to the electron-capture detector the 3,5-bis(trifluoromethyl)benzeneboronic acid, 2,4-dichlorobenzeneboronic acid, and 4-bromo-benzeneboronic acid were recommended for general applications. In particular, the 3,5-bis(trifluoromethyl)benzeneboronate derivatives are remarkably volatile, more so than the benzeneboronates, and are suitable for the analysis of bifunctional compounds of low volatility. All the benzeneboronate derivatives are susceptible to solvolysis which is the primary limitation to their general use for trace analysis. 

The relative response of the electron-capture detector to some haloalkylacyl derivatives is sumi rized in Table 8.17 [451]. In general terms, the monochloroacetyl and chlorodifluoroacetyl derivatives provide a greater response than the trifluoroacetyl derivatives. Increasing the fluorocarbon chain length of the fluorocarbonacyl derivatives increases t ir electron-capture detector response without inconveniently increasing their retention times. The heptafluorobutyryl and pentafluoropropionyl derivatives are considered to be the best compromise between detector sensitivity and volatility for most applications. 

Detectors are composed of a sensor and associated electronics. Design and performance of any detector depends heavily on the column and chromatographic system with which it is associated. Because of the complexity of many mixtures analysed and the limitation in regard to resolution, despite the use of high-resolution capillary columns and multicolumn systems, specific detectors are frequently necessary to gain selectivity and simplify the separation system. Many detectors have been developed with sensitivities toward specific elements or certain functional groups in molecules. Those detectors that exhibit the highest sensitivity are often very specific in response, e.g. the electron capture detector in GC or the fluorescence detector in LC. Because... 

An ion mobility spectrometer offers to prospective users an attractive detector for a GC, from the perspective of detection limits and specificity. A mobility spectrometer, even with low resolution, allows interrogation of compound identities and imparts better specificity than the electron-capture detector. When gaseous analytes are delivered individually to IMS, the mobility spectrum contains information for identification, provided that operating conditions are kept constant for the unknown and reference spectra. The connection of a GC column to an ion mobility spectrometer is... 

Andreae [712] used four different detectors in his investigations the electron capture detector (for the methylarsines), the quartz cuvette atomic absorption detector (for arsenic and antimony species), the graphite furnace atomic... 

The electron-capture detector was originally found to be a sensitive detector for the methylarsines [716]. After improvements of the atomic absorption detectors had been made (especially concerning adsorptive losses and peak shapes of the methylarsines), it was found that this detector could be used to replace the electron-capture detector, which because of its lack of specificity and its sensitivity to contamination and changes in operating conditions was very inconvenient to work with. 

Most often the sterols have been collected by liquid-liquid extraction using petroleum ether and ethyl acetate [408], chloroform and methanol [409], -hexane [410,411] or chloroform [412,413]. After concentration, gas chromatography was generally used for the final separation and determination, although thin-layer chromatography has also been employed. The extra sensitivity of the electron capture detector could be used by reacting the concentrated sterols with bromomethyldimethylchlorosilane (BMDS) before separation and measurement [414],... 

The electron capture detector (ECD) is most frequently used to identify hexachloroethane. A flame ionization detector (FID) may also be used (NIOSH 1994). When unequivocal identification is required, an MS coupled to the GC column may be employed. 

GC is coupled with many detectors for the analysis of pesticides in wastewater. At the present time the most popular is GC-MS, which will be discussed in more detail later in this section. The flame ionization detector (FID) is another nonselective detector that identifies compounds containing carbon but does not give specific information on chemical structure (but is often used for quantification because of the linear response and sensitivity). Other detectors are specific and only detect certain species or groups of pesticides. They include electron capture,nitrogen-phosphorus, thermionic specific, and flame photometric detectors. The electron capture detector (ECD) is very sensitive to chlorinated organic pesticides, such as the organochlorine compounds (OCs, DDT, dieldrin, etc.). It has a long history of use in many environmental methods,... 

One of the most commonly used detection systems in a gas chromatography laboratory is the electron capture detector. The first paper [25] to be published demonstrating the use of an electron capture detector with supercritical fluid chromatography showed that with supercritical fluid chromatography sensitivity to about 50pg minimum detection limit on column was obtainable. 

A third type of detector, required for some environmental and biomedical applications, is the electron capture detector (ECD). This detector is especially useful for large halogenated hydrocarbon molecules since it is the only one that has an acceptable sensitivity for such molecules. Thus, it finds special utility in the analysis of halogenated pesticide residues found in environmental and biomedical samples. 

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