Gas-chromatographic

Durand, J.P., Y. Boscher and N. Petroff (1987), Automatic gas chromatographic determination of gasoline components. Application to octane number determination . Journal of chromatography, No. 395, p. 229. 

If there are hydrocarbons present in the formation that is being drilled, they will show in the cuttings as oil stains, and in the mud as traces of oil or gas. The gas in the mud is continuously monitored by means of a gas detector. This is often a relatively simple device detecting the total combustible gas content. The detector can be supplemented by a gas chromatograph, which analyses the composition of the gas. 

The reaction product is cooled to room temperature, is washed with 10 ml of H2O to the purpose of removing lithium iodide and is then dehydrated over NaiS04. 3.57 g is obtained of dimethoxy-phenylacetone (III), as determined by gas-chromatographic analysis with an inner standard of 4,4 -dimethoxybeniophenone. The yield of ketone (III) relative to the olefin ( ) used as the starting material is of 87.1%. 

The most stable protected alcohol derivatives are the methyl ethers. These are often employed in carbohydrate chemistry and can be made with dimethyl sulfate in the presence of aqueous sodium or barium hydroxides in DMF or DMSO. Simple ethers may be cleaved by treatment with BCI3 or BBr, but generally methyl ethers are too stable to be used for routine protection of alcohols. They are more useful as volatile derivatives in gas-chromatographic and mass-spectrometric analyses. So the most labile (trimethylsilyl ether) and the most stable (methyl ether) alcohol derivatives are useful in analysis, but in synthesis they can be used only in exceptional cases. In synthesis, easily accessible intermediates of medium stability are most helpful. 

FIGURE 13 44 Diagram of a gas chromatograph When connected to a mass spectrometer as in GC/MS the effluent is split into two streams as it leaves the column One stream goes to the detector the other to the mass spectrometer (Adapted with permission from H D Durst and G W Gokel Experimental Organic Chemistry Inti eti McGraw Hill New York 1987)... 

Solid-phase microextractions also have been developed. In one approach, a fused silica fiber is placed inside a syringe needle. The fiber, which is coated with a thin organic film, such as poly(dimethyl siloxane), is lowered into the sample by depressing a plunger and exposed to the sample for a predetermined time. The fiber is then withdrawn into the needle and transferred to a gas chromatograph for analysis. 

Two examples from the analysis of water samples illustrate how a separation and preconcentration can be accomplished simultaneously. In the gas chromatographic analysis for organophosphorous pesticides in environmental waters, the analytes in a 1000-mL sample may be separated from their aqueous matrix by a solid-phase extraction using 15 mb of ethyl acetate. After the extraction, the analytes are present in the ethyl acetate at a concentration that is 67 times greater than that in... 

Caffeine is extracted from beverages by a solid-phase microextraction using an uncoated fused silica fiber. The fiber is suspended in the sample for 5 min and the sample stirred to assist the mass transfer of analyte to the fiber. Immediately after removing the fiber from the sample it is transferred to the gas chromatograph s injection port where the analyte is thermally desorbed. Quantitation is accomplished by using a C3 caffeine solution as an internal standard. 

In gas chromatography (GC) the sample, which may be a gas or liquid, is injected into a stream of an inert gaseous mobile phase (often called the carrier gas). The sample is carried through a packed or capillary column where the sample s components separate based on their ability to distribute themselves between the mobile and stationary phases. A schematic diagram of a typical gas chromatograph is shown in Figure 12.16. 

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. 

Three considerations determine how samples are introduced to the gas chromatograph. First, all constituents injected into the GC must be volatile. Second, the analytes must be present at an appropriate concentration. Finally, injecting the sample must not degrade the separation. 

The final part of a gas chromatograph is the detector. The ideal detector has several desirable features, including low detection limits, a linear response over a wide range of solute concentrations (which makes quantitative work easier), responsiveness to all solutes or selectivity for a specific class of solutes, and an insensitivity to changes in flow rate or temperature. 

Although each gas chromatographic method has its own unique considerations, the following description of the determination of trihalomethanes in drinking water provides an instructive example of a typical procedure. 

Accuracy The accuracy of a gas chromatographic method varies substantially from sample to sample. For routine samples, accuracies of 1-5% are common. For analytes present at very low concentration levels, for samples with complex matrices, or for samples requiring significant processing before analysis, accuracy may be substantially poorer. In the analysis for trihalomethanes described in Method 12.1, for example, determinate errors as large as +25% are possible. ... 

Precision The precision of a gas chromatographic analysis includes contributions from sampling, sample preparation, and the instrument. The relative standard deviation due to the gas chromatographic portion of the analysis is typically 1-5%, although it can be significantly higher. The principal limitations to precision are detector noise and the reproducibility of injection volumes. In quantitative work, the use of an internal standard compensates for any variability in injection volumes. 

The following data have been reported for the gas chromatographic analysis of p-xylene and methylisobutylketone (MIBK) on a capillary column. ... 

A variable-size simplex optimization of a gas chromatographic separation using oven temperature and carrier gas flow rate as factors is described in this experiment. 

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... 

By connecting a gas chromatograph to a suitable mass spectrometer and including a data system, the combined method of GC/MS can be used routinely to separate complex mixtures into theii individual components, identify the components, and estimate their amounts. The technique is widely used. 

Direct GC/MS interface. An interface in which all the effluent from a gas chromatograph passes into the mass spectrometer ion source during an analysis, without any splitting of the effluent. 

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. 

GC/MS interface. An interface between a gas chromatograph and a mass spectrometer that provides continuous introduction of effluent gas from a gas chromatograph to a mass spectrometer ion source. 

Separator GC/MS interface. An interface in which the effluent from the gas chromatograph is enriched in the ratio of sample to carrier gas. Separator, molecular separator, and enricher are synonymous terms. A separator should generally be defined as an effusion separator, a jet separator, or a membrane separator. 

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