Gas chromatographic columns

Another important characteristic of a gas chromatographic column is the thickness of the stationary phase. As shown in equation 12.25, separation efficiency improves with thinner films. The most common film thickness is 0.25 pm. Thicker films are used for highly volatile solutes, such as gases, because they have a greater capacity for retaining such solutes. Thinner films are used when separating solutes of low volatility, such as steroids. 

As described above, the mobile phase carrying mixture components along a gas chromatographic column is a gas, usually nitrogen or helium. This gas flows at or near atmospheric pressure at a rate generally about 0,5 to 3.0 ml/min and evenmally flows out of the end of the capillary column into the ion source of the mass spectrometer. The ion sources in GC/MS systems normally operate at about 10 mbar for electron ionization to about 10 mbar for chemical ionization. This large pressure... 

Dynamic headspace GC/MS. The distillation of volatile and semivolatile compounds into a continuously flowing stream of carrier gas and into a device for trapping sample components. Contents of the trap are then introduced onto a gas chromatographic column. This is followed by mass spectrometric analysis of compounds eluting from the gas chromatograph. 

Passed at least twice through a gas chromatographic column for small quantities, or fractionally distd under reduced pressure. 

If interfering peaks hinder sample quantitation on the gas chromatogram, better resolution could be obtained by using an FFAP or DB-17 gas chromatographic column. 

Figure 2.10 Standardized bleed test for gas chromatographic columns (aee text tor details). (Reproduced vith permission from ref. 298. Copyright Elsevier Scientific Publishing Co.)...

One of the main problems of the pyrolysis technique is related to the low volatility of pyrolysis products arising from natural and some synthetic macromolecules. In fact, the polar acidic, alcoholic and aminic moieties are not really suitable for gas chromatographic analysis. Their poor volatility and their polarity cause a rather low reproducibility of the pyrograms, low sensitivity for specific compounds, and strong memory effects. Memory effects need to be borne in mind when the pyrolysis of polar molecules is performed. Polar pyolysis products may not be completely eluted by the gas chromatographic column, and... 

In a typical pulse experiment, a pulse of known size, shape and composition is introduced to a reactor, preferably one with a simple flow pattern, either plug flow or well mixed. The response to the perturbation is then measured behind the reactor. A thermal conductivity detector can be used to compare the shape of the peaks before and after the reactor. This is usually done in the case of non-reacting systems, and moment analysis of the response curve can give information on diffusivities, mass transfer coefficients and adsorption constants. The typical pulse experiment in a reacting system traditionally uses GC analysis by leading the effluent from the reactor directly into a gas chromatographic column. This method yields conversions and selectivities for the total pulse, the time coordinate is lost. 

The gas phase limitation imposed by the very nature of the GC-MS experiment limits its applicability to chemical space. The Venn diagram in Fig. 19.4 illustrates an approximate mapping of applicability of the combined chromatography-mass spectrometry techniques discussed here. Using only relative molecular mass and polarity as two dimensions that can map chemical space, the figure indicates that the applicability of GC-MS is limited to those relatively small, thermally stable, nonpolar compounds that can be readily volatized (or made to volatilize by derivatization [26]) to pass through a gas chromatographic column. 

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