Vaporizing sample injection techniques

In case liquid samples are applied to GC or GC-MS, the most widely used injection technique evaporates the liquid sample in the inlet liner of the injector in order to transfer the analytes into the analytical column. Classical injection techniques involve applying the sample solution in constantly heated injectors. Both the solvent and the dissolved analytes evaporate in an evaporation tube specially 

The transfer can only be partial for concentrated extracts (split mode), or a total transfer of the sample into the column for trace analysis is performed (splitless mode). Both injection methods require a different parameter setting, choice of inlet liners and oven program start temperature to achieve the optimum performance. Also the possible injection volumes need to be considered. The operating procedures of split injection and total sample transfer (splitless) differ according to whether there is partial or complete transfer of the solvent/sample on to the column. 

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The foregoing discussion relates to the flash vaporization sample introduction technique that involves injection of sample into a precolumn zone that is kept at a temperature of 30-50° C higher than that of the column. This facilitates instantaneous sample vaporization. Samples also may be introduced by on-column injection where the sample is injected directly into the head of the column, which results in better precision than flash vaporization. " ... 

Cool on-column injection is used for trace analysis. Ah. of the sample is introduced without vaporization by inserting the needle of the syringe at a place where the column has been previously stripped of hquid phase. The injection temperature must be at or below the boiling point of the solvent carrying the sample. Injection must be rapid and no more than a very few, usuahy no more than two, microliters may be injected. Cool on-column injection is the most accurate and reproducible injection technique for capihary chromatography, but it is the most difficult to automate. 

Numerous types of GC injectors have been manufactured over the past four decades. The most commonly used injection techniques have been reviewed and described by Grob, who correctly states that analysts must fully understand the techniques before they can make the most appropriate choice for their particular application(s). For most GC capillary column applications, the split/splitless, programmed-temperature vaporization (PTV) and on-column injectors remain the most popular. However, over the last few years, technology has progressed rapidly to provide injectors that allow more of the sample extract on to the GC column without overloading it. 

Certainly, the precision and accuracy of the PTV techniques are generally superior to those of the classical hot split and splitless techniques and approach those obtained by cold on-column Injection [ 34,36,37, -54-57,62,64]. However, less is known concerning optimization of PTV injection and probably more parameters have to be considered than for cold on-column injection. The latter is, consequently, the preferred injection technique for most samples, except those contaminated by larg< amounts of involatile Impurities and for headspace vapors. 

Solubilizing all or part of a sample matrix by contacting with liquids is one of the most widely used sample preparation techniques for gases, vapors, liquids or solids. Additional selectivity is possible by distributing the sample between pairs of immiscible liquids in which the analyte and its matrix have different solubilities. Equipment requirements are generally very simple for solvent extraction techniques. Table 8.2 [4,10], and solutions are easy to manipulate, convenient to inject into chromatographic instruments, and even small volumes of liquids can be measured accurately. Solids can be recovered from volatile solvents by evaporation. Since relatively large solvent volumes are used in most extraction procedures, solvent impurities, contaminants, etc., are always a common cause for concern [65,66]. 

Gas chromatograph systems are composed of an inlet, carrier gas, a column within an oven, and a detector (O Figure 1-1). The inlet should assure that a representative sample reproducibly, and frequently automatically, reaches the column. This chapter will cover injection techniques appropriate for capillary columns. These include direct, split/splitless, programmed temperature vaporization, and cool on-column injection (Dybowski and Kaiser, 2002). 

Automatic headspace samplers are available from manufacturers of gas chromatographs. These devices are based on the technique of sampling an amount of vapor above the sample itself. Samples are sealed, neat or in a suitable solvent, in containers, and hold at a preset temperature in a thermostatted liquid bath. The headspace vapor results as a partition equilibrium is established between the liquid or solid and the gaseous phase of the volatiles. As each sample is presented to the analyzer, the vessel is punctured and a portion of the headspace gas is withdrawn by a pneumatic injection technique and forced into the column. The main application for those samplers is in the routine analysis of low-boiling fractions in samples containing nonvolatile solids or high-boiling components. Some of the more popular applications today are ... 

There are three injection techniques for introducing a sample into a GC equipped with a capillary column split injection, splitless injection, and on-column injection. Split injection is the most often used injection technique. When a certain amount of FAME sample (1 to 3 ll) is introduced into the GC injector that is normally set at a temperature much higher than the boiling point of the solvent, the solvent vaporizes instantly in the carrier gas and creates a large volume of gas that contains all of the injected FAME in it. The carrier gas that contains the FAME is then divided into two streams from the injector one is directed onto the column, and the second is vented to the atmosphere, clearing the sample out of the injection chamber momentarily. This way, only a limited amount of sample is introduced into the column, to avoid column overloading, and injection time is short, to avoid peak broadening. 

Involves a sample being vaporized and injected into the head space of the chromatographic column. The sample is transported through the column by the flow of an inert gas (mobile phase). The column itself contains a liquid stationary phase which is adsorbed onto the surface of an inert solid. Retention time with detection techniques (spectrophotometer, mass spectrometry, fluorescence) identifies the compound. 

Direct injection simply transfers the entire sample to the analytical column. Direct injection techniques include direct flash vaporization (hot direct injection) and cold on-column. Direct flash vaporization has become popular used with wide-bore capillary columns (> 530 /xm ID) having phase ratios less than 80 and high sample volume capacity and can easily accommodate injections of up to 10 /xl of sample. 

Splitless injection involves keeping the injector split vent closed during the time the sample is deposited on the column, after which the vent is reopened and the inlet purged with carrier gas. In splitless injection, the inlet temperature is elevated with respect to the column temperature. The sample is focused at the head of the column with the aid of the solvent effect. The solvent effect is the vaporization of sample and solvent matrix in the injection port, followed by trapping of the analyte in the condensing solvent at the head of the column. This trapping of the analyte serves to refocus the sample bandwidth and is only achieved after proper selection of the solvent, column and injector temperatures. Splitless injection techniques have been reviewed in References 29 and 30. 

Even a technique of higher detection power as ET-AAS may require some sort of previous analyte enrichment for difficult elements. In the determination of As and Se in mineral waters described by Hudnik and Gomiscek [23], coprecipitation of both elements on hydrated Fe(III) oxide was employed to improve LoDs, otherwise impaired by matrix effects. A graphite tube furnace was the atomization cell, with the atomic vapor sampled with element electrodeless discharge lamps. After treatment of the sample with Fe(III) solution at the appropriate pH, the oxide precipitate was filtered and dissolved and the solution volume reduced to 5 mL of 0.2 M H2SO4. Ten-microliter volume aliquots of sample and standard solutions were injected into the furnace. Reported LoDs were 0.2 and 0.5 p,g l-1 for As and Se, respectively. 

An alternative for achieving a lower column load and enough analyte in the detector is to perform an additional separation before the analytes reach the analytical column. In this separation, part of the sample that is not of interest can be eliminated, and at the same time the important analytes can be kept. This preliminary separation can be done using bidimensional chromatography (see further), but simpler techniques are also reported, such as programmed temperature vaporization (PTV) injection, etc. 

It has been shown that the PTV injector is a very useful technique for large-volume injection, especially for the analysis of a dirty sample. Because the vaporization of the solvent is carried out at a low temperature, nonvolatile matrix constituents remaining in the liner will not contaminate the GC column. However, the PTV injection technique is less suited when analyzing volatile compounds because only components with volatility significantly below that of the solvent are trapped in the cold liner, unless liners packed with a selective adsorbent is used [4]. 

Because of the low sample capacities and carrier-gas flow rates used with capillary columns, split and sphtless injection techniques are used to introduce samples into the columns. In the split mode (Figure 6-11), only a small portion of the vaporized sample enters the column, whereas in the splitless mode most of the sample enters the column (Figure 6-12). Operationally the spht flow mode is used for samples that contain relatively high concentrations of the target analyte(s) the sphtless mode is used for samples that contain relatively low levels of the target analyte(s). 

Submicroliter samples are needed for the capillary on-column injection technique. To counter a general scepticism following the development of this injection technique, excellent quantitative results have been reported [42). The major advantages of this injection procedure seem to be in minimizing thermal decomposition of labile compounds as well as the lack of sample discrimination toward the later eluting components. This latter problem, observed frequently with the vaporizing injector... 

Formation of artifacts in GC analysis is perhaps encountered more frequently than many investigators acknowledge. While some artifacts could be formed even prior to the GC terminal analysis, the most critical point seems to be the rapid vaporization following the sample injection. A wider utilization of the on-coIumn sampling techniques is desirable. 

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