Stationary phases principles

The situation is much more complicated for a vibrational wavepacket launched from a r" 0 initial eigenstate (see Fig. 9.7). However, a simple picture based on the classical Franck-Condon (stationary phase) principle (see Section 5.1.1) captures the essential details of the wavepacket produced at to on the electronically excited potential surface. First, there is the limiting case of an excitation pulse sufficiently short that an exact replica of the electronic ground state vibrational eigenstate, (R v" / 0), is created at to on the excited potential surface,... 

Chromatographic technique Mobile phase Stationary phase Principle... 

In the course of mixture separation, the composition and properties of both mobile phase (MP) and stationary phase (SP) are purposefully altered by means of introduction of some active components into the MP, which are absorbed by it and then sorbed by the SP (e.g. on a silica gel layer). This procedure enables a new principle of control over chromatographic process to be implemented, which enhances the selectivity of separation. As a possible way of controlling the chromatographic system s properties in TLC, the pH of the mobile phase and sorbent surface may be changed by means of partial air replacement by ammonia (a basic gaseous component) or carbon dioxide (an acidic one). 

The two examples that have been given are simple and basic, and illustrate the principles of a TLC separation. Ion exchange material can also be bonded to the silica, allowing ionic interactions to be dominant in the stationary phase and, thus. 

On the basis of the principle of grafted TLC, reversed-phase (RP) and normal-phase (NP) stationary phases can also be coupled. The sample to be separated must be applied to the first (2.5 cm X 20 cm) reversed-phase plate (Figure 8.16(a)). After development with the appropriate (5ti 5yi) mobile phase (Figure 8.16(b)), the first plate must be dried. The second (20 cm X 20 cm) (silica gel) plate (Figure 8.16(c)) must be clamped to the first (reversed-phase) plate in such a way that by use of a strong solvent system (Sj/, SyJ the separated compounds can be transferred to the second plate (Figure 8.16(d)). Figure 8.16(e) illustrates the applied, re-concentrated... 

The coupling of supercritical fluid extraction (SEE) with gas chromatography (SEE-GC) provides an excellent example of the application of multidimensional chromatography principles to a sample preparation method. In SEE, the analytical matrix is packed into an extraction vessel and a supercritical fluid, usually carbon dioxide, is passed through it. The analyte matrix may be viewed as the stationary phase, while the supercritical fluid can be viewed as the mobile phase. In order to obtain an effective extraction, the solubility of the analyte in the supercritical fluid mobile phase must be considered, along with its affinity to the matrix stationary phase. The effluent from the extraction is then collected and transferred to a gas chromatograph. In his comprehensive text, Taylor provides an excellent description of the principles and applications of SEE (44), while Pawliszyn presents a description of the supercritical fluid as the mobile phase in his development of a kinetic model for the extraction process (45). 

A variety of chromatographic techniques are now in common use, all of which work on a similar principle. The mixture to be separated is dissolved in a solvent, called the mobile phase, and passed over an adsorbent material, called the stationary phase. Because different compounds adsorb to the stationary phase to different extents, they migrate along the phase at different rates and are separated as they emerge (elute) from the end of the chromatography column. 

The two examples of sample preparation for the analysis of trace material in liquid matrixes are typical of those met in the analytical laboratory. They are dealt with in two quite different ways one uses the now well established cartridge extraction technique which is the most common the other uses a unique type of stationary phase which separates simultaneously on two different principles. Firstly, due to its design it can exclude large molecules from the interacting surface secondly, small molecules that can penetrate to the retentive surface can be separated by dispersive interactions. The two examples given will be the determination of trimethoprim in blood serum and the determination of herbicides in pond water. 

Tswett s initial column liquid chromatography method was developed, tested, and applied in two parallel modes, liquid-solid adsorption and liquid-liquid partition. Adsorption ehromatography, based on a purely physical principle of adsorption, eonsiderably outperformed its partition counterpart with mechanically coated stationary phases to become the most important liquid chromatographic method. This remains true today in thin-layer chromatography (TLC), for which silica gel is by far the major stationary phase. In column chromatography, however, reversed-phase liquid ehromatography using chemically bonded stationary phases is the most popular method. 

Confirmation of suspected residue findings relies on the various chromatographic principles of cleanup and determination (GPC, NP-LC, GC), and is further supported by re-analysis of the final extract(s) on a GC stationary phase of different polarity, providing modified selectivity, or by the use of GC with specific mass spectrometric detection [GC/MS or gas chromatography/tandem mass spectrometry (GC/MS/MS)]. 

Principles and Characteristics Solid-phase microextraction (SPME) is a patented microscale adsorp-tion/desorption technique developed by Pawliszyn et al. [525-531], which represents a recent development in sample preparation and sample concentration. In SPME analytes partition from a sample into a polymeric stationary phase that is thin-coated on a fused-silica rod (typically 1 cm x 100 p,m). Several configurations of SPME have been proposed including fibre, tubing, stirrer/fan, etc. SPME was introduced as a solvent-free sample preparation technique for GC. 

Principles and Characteristics Column liquid chromatography is the parent of all other types of chromatography. The technique used by Tswett is now called classical open-column liquid chromatography or simply LC. In column chromatography the stationary phase is contained in a column and the mobile phase flows... 

In principle the wide range of stationary phases used in GLC can be used in liquid-liquid partition systems, but problems can arise from mutual solubility effects which may result in the stationary phase being stripped from the column. 

Gas-Liquid Chromatography. In gas-liquid chromatography (GLC) the stationary phase is a liquid. GLC capillary columns are coated internally with a liquid (WCOT columns) stationary phase. As discussed above, in GC the interaction of the sample molecules with the mobile phase is very weak. Therefore, the primary means of creating differential adsorption is through the choice of the particular liquid stationary phase to be used. The basic principle is that analytes selectively interact with stationary phases of similar chemical nature. For example, a mixture of nonpolar components of the same chemical type, such as hydrocarbons in most petroleum fractions, often separates well on a column with a nonpolar stationary phase, while samples with polar or polarizable compounds often resolve well on the more polar and/or polarizable stationary phases. Reference 7 is a metabolomics example of capillary GC-MS. 

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