Sample Introduction Inlet System

Gas chromatographic samples are generally introduced onto GC column through an injection port, in which there is a self-sealing septum to ensure no 

There are two general classifications of gas chromatographic columns, packed and capillary or open tubular columns. 

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To examine a sample by inductively coupled plasma mass spectrometry (ICP/MS) or inductively coupled plasma atomic-emission spectroscopy (ICP/AES) the sample must be transported into the flame of a plasma torch. Once in the flame, sample molecules are literally ripped apart to form ions of their constituent elements. These fragmentation and ionization processes are described in Chapters 6 and 14. To introduce samples into the center of the (plasma) flame, they must be transported there as gases, as finely dispersed droplets of a solution, or as fine particulate matter. The various methods of sample introduction are described here in three parts — A, B, and C Chapters 15, 16, and 17 — to cover gases, solutions (liquids), and solids. Some types of sample inlets are multipurpose and can be used with gases and liquids or with liquids and solids, but others have been designed specifically for only one kind of analysis. However, the principles governing the operation of inlet systems fall into a small number of categories. This chapter discusses specifically substances that are normally liquids at ambient temperatures. This sort of inlet is the commonest in analytical work. 

Sample introduction system. A system used to introduce sample to a mass spectrometer ion source. Sample introduction system, introduction system, sample inlet system, inlet system, and inlet are synonymous terms. 

Gas chromatographic analysis starts with introduction of the sample on the column, with or without sample preparation steps. The choice of inlet system will be dictated primarily by the characteristics of the sample after any preparation steps outside the inlet. Clearly, sample preparation has a profound influence on the choice of injection technique. For example, analysts may skip the solvent evaporation step after extraction by eliminating solvent in the inlet with splitless transfer into the column. Sample introduction techniques are essentially of two types conventional and programmed temperature sample introduction. Vogt et al. [89] first described the latter in 1979. Injection of samples, which... 

General texts on GC are numerous [118,119] narrow-bore GC was addressed by van Es [120]. Sample introduction techniques and GC inlet systems have been reviewed [25,90] and split/splitless [121] and on-column injection [122] were considered specifically. Stationary phases [123], multiple detection [103], derivatisation [124,125], and quantitative analysis in GC [109] have been described. High-speed GC has recently been reviewed [126]. For a compendium of GC terms and techniques, see Hinshaw [127]. 

Section 6.4 deals with other EI-MS analyses of samples, i.e. analyses using direct introduction methods (reservoir or reference inlet system and direct insertion probe). Applications of hyphenated electron impact mass-spectrometric techniques for poly-mer/additive analysis are described elsewhere GC-MS (Section 7.3.1.2), LC-PB-MS (Section 7.3.3.2), SFC-MS (Section 13.2.2) and TLC-MS (Section 7.3.5.4). 

Before describing the single parts, let us examine the general features of a mass spectrometer (Figure 2.1). In every MS experiment the first step is the introduction of the sample into the mass spectrometer. It follows that the first part of every instrument is the inlet system that allows the introduction of the sample, generally molecules, into the mass spectrometer. There are different ways to introduce the sample, depending on its purity and properties. 

Inlet System and Sample Introduction in a Mass Spectrometer... 

The most straightforward tool for the introduction of a sample into a mass spectrometer is called the direct inlet system. It consists of a metal probe (sample rod) with a heater on its tip. The sample is inserted into a cmcible made of glass, metal, or silica, which is secured at the heated tip. The probe is introduced into the ion source through a vacuum lock. Since the pressure in the ion source is 10-5 to 10-6 torr, while the sample may be heated up to 400°C, quite a lot of organic compounds may be vaporized and analyzed. Very often there is no need to heat the sample, as the vapor pressure of an analyte in a vacuum is sufficient to record a reasonable mass spectrum. If an analyte is too volatile the cmcible may be cooled rather than heated. There are two main disadvantages of this system. If a sample contains more than one compound with close volatilities, the recorded spectrum will be a superposition of spectra of individual compounds. This phenomenon may significantly complicate the identification (both manual and computerized). Another drawback deals with the possibility of introducing too much sample. This may lead to a drop in pressure, ion-molecule reactions, poor quality of spectra, and source contamination. 

The system used by these workers consisted of a Microtek 220 gas chromatograph and a Perkin-Elmer 403 atomic absorption spectrophotometer. These instruments were connected by means of stainless steel tubing (2mm o.d.) connected from the column outlet of the gas chromatograph to the silica furnace of the a.a.s. (Fig. 13.2). A four-way valve was installed between the carrier gas inlet and the column injection port so that a sample trap could be mounted, and the sample could be swept into the gas chromatographic column by the carrier gas. The recorder (lOmV) was equipped with an electronic integrator to measure the peak areas, and was simultaneously actuated with the sample introduction so that the retention time of each component could be used for identification of peaks. 

The MC-ICP-MS consists of four main parts 1) a sample introduction system that inlets the sample into the instrument as either a liquid (most common), gas, or solid (e.g., laser ablation), 2) an inductively coupled Ar plasma in which the sample is evaporated, vaporized, atomized, and ionized, 3) an ion transfer mechanism (the mass spectrometer interface) that separates the atmospheric pressure of the plasma from the vacuum of the analyzer, and 4) a mass analyzer that deals with the ion kinetic energy spread and produces a mass spectrum with flat topped peaks suitable for isotope ratio measurements. 

When an analyte is transferred into the ion source by means of any sample introduction system it is in thermal equilibrium with this inlet device. As a result, the energy of the incoming molecules is represented by their thermal energy. Then, ionization changes the situation dramatically as comparatively large amounts of energy need to be handled by the freshly formed ion. 

Note Sample introduction systems such as reservoir inlets, chromatographs, and various types of direct probes (Chap. 5.3) are of equal importance to other ionization methods. The same holds valid for the concepts of sensitivity, detection limit, and signal-to-noise ratio (Chap. 5.2.4) and finally to all sorts of ion chromatograms (Chap. 5.4). 

For the purpose of sample introduction, any sample introduction system (also sample inlet system or inlet) suitable for the respective compound can be employed. Hence, direct probes, reservoir inlets, gas chromatographs and even liquid chromatographs can be attached to an El ion source. Which of these inlet systems is to be preferred depends on the type of sample going to be analyzed. Whatever type the inlet system may be, it has to manage the same basic task, i.e., the transfer of the analyte from atmospheric conditions into the high vacuum of the El ion source Table 5.1 provides an overview. 

Mass spectrometry is a sensitive analytical technique which is able to quantify known analytes and to identify unknown molecules at the picomoles or femto-moles level. A fundamental requirement is that atoms or molecules are ionized and analyzed as gas phase ions which are characterized by their mass (m) and charge (z). A mass spectrometer is an instrument which measures precisely the abundance of molecules which have been converted to ions. In a mass spectrum m/z is used as the dimensionless quantity that is an independent variable. There is still some ambiguity how the x-axis of the mass spectrum should be defined. Mass to charge ratio should not lo longer be used because the quantity measured is not the quotient of the ion s mass to its electric charge. Also, the use of the Thomson unit (Th) is considered obsolete [15, 16]. Typically, a mass spectrometer is formed by the following components (i) a sample introduction device (direct probe inlet, liquid interface), (ii) a source to produce ions, (iii) one or several mass analyzers, (iv) a detector to measure the abundance of ions, (v) a computerized system for data treatment (Fig. 1.1). 

The values of H and V are known, r is determined experimentally and e is assumed to be unity thus permitting us to determine the mass m. In practice the magnetic field is scanned so that streams of ions of different mass pass sequentially to the detecting system (ion collector). The whole system (Figure 4.1) is under high vacuum (less than 10 Torr) to permit the volatilisation of the sample and so that the passage of ions is not impeded. The introduction of the sample into the ion chamber at high vacuum requires a complex sample inlet system. 

Figure 3.9 Measurement of the enantiomeric purity of the pharmaceutical intermediate SB-240093 using CD-modified CE. The electropherogram shows the analysis of the chiral system suitability standard containing 0.5% w/w of the R-enantiomer. (Conditions PVA-coated fused silica capillary, 50 cm effective length, 57 cm total length, 50 pm i.d. buffer sodium phosphate [pH 7.0, 100 mM] containing 1.75 mM dimethyl-/l-CD voltage —30 kV [reversed polarity] temperature 20°C detection UV at 200 nm sample preparation 0.5 mg/ml in water DMSO (95 5, v/v) sample introduction 6 s at 35 mbar, capillary inlet at cathode.)...

Splitless injection is used when the sample is dilute and cannot be introduced into the GC system with stream splitting. In practice, the column temperature is set 10° to 30°C below the boiling point of the solvent at the time of injection. When sample is introduced into the injector inlet, vaporized solvent together with the FAME condense at the beginning of the column along with the carrier gas flow. The condensed solvent plus the stationary phase of the column forms a diluted stationary phase that traps the FAME in it. After the initial sample introduction period, the column temperature is raised to normal operating conditions, and chromatographic separation starts from there. 

Although ICP-MS has been used for analysis of nuclear materials, often the entire instrument must be in an enclosed hot enclosure [350]. Sample preparation equipment, inlets to sample introduction systems, vacuum pump exhaust, and instrument ventilation must be properly isolated. Many of the materials used in the nuclear industry must be of very high purity, so the low detection limits provided by ICP-MS are essential. The fission products and actinide elements have been measured by using isotope dilution ICP-MS [351]. Because isotope ratios are not predictable, isobaric and molecular oxide ion spectral overlaps cannot be corrected mathematically, so chemical separation is required. 

The interfaces that effectively replaced the transport system were the thermospray and electrospray sample introduction systems. The thermospray interface, a diagram of which is shown in figure 23, is a development from the direct inlet system of McLafferty. The successful use of the thermospray interface was first reported by... 

Interfacing micro-LC and MS via a capillary inlet interface coimected to a GC-MS jet separator was described in 1978 by Takeuchi et al. [55]. In the period until 1982, this system was subsequently developed towards a vacuum nebuhzer, in which the column effluent is pneumatically nebulized into a modified jet-separator type of device [56-57]. The instrumental developments of the vacuum nebulizer interfaces are discussed in Ch. 4.3. Pneumatic nebulization of column effluents directly into the Cl somce was described by a number of groups [58-61]. A so-called helium interface for the introduction of organic solvents was described by Apffel et al. [59]. It was primarily applied to the analysis of pesticides in aqueous samples. Although the system was commercially available, it did not find wide application. 

Vaporize compounds of varying volatility. This is accomplished in the inlet system. Introduction of the sample is done by direct insertion probe, reservoir inlet, or following a chromatographic separation (GC, HPLC, and CE). As mentioned earlier, to introduce the LC flow to the mass spectrometer on-line, we need an appropriate interface. Development of appropriate interfaces was the utmost for evolution of the LC-MS coupling. 

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