Stationary phases high-capacity

An overview of capillary gas chromatography is presented. Selected environmental applications, such as PCB s in water, PAH s in airborne particulate matter, and TCDD s at the part-per-trillion level illustrate the separation and analysis of complex mixtures. The chromatographic performance, characteristics, and trade-offs of packed and capillary columns are described in terms of permeability and efficiency, sample capacity, choice of stationary phase, high temperature capabilities, quantitative accuracy, and the development of GC separation methods. 

Pioneering work in the field of adsorbing crown ethers onto chemically bonded reversed phases and PS/DVB polymers have been carried out by Kimura et al. [69]. They employed dodecyl-substituted crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6, all of which have a highly hydrophobic side chain that enables these molecules to adsorb onto the stationary phase. The capacity of the separator column can be controlled by the amount of adsorbed crown ether. Stationary phases of this type are stable over a longer period of time only when used with purely aqueous eluents. If the mobile phase contains more than 40%... 

In capillary GC the phase ratio describing the ratio of the internal volume of a column (volume of the mobile phase) to the volume of the stationary phase. High-performance columns are characterized by high-phase ratios. A table showing different combinations of internal diameters and film thicknesses can be used to optimize the choice of column with regard to analysis time, resolution and capacity. 

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. 

The peak capacity is not pertinent as the separation was developed by a solvent program. The expected efficiency of the column when operated at the optimum velocity would be about 5,500 theoretical plates. This is not a particularly high efficiency and so the separation depended heavily on the phases selected and the gradient employed. The separation was achieved by a complex mixture of ionic and dispersive interactions between the solutes and the stationary phase and ionic, polar and dispersive forces between the solutes and the mobile phase. The initial solvent was a 1% acetic acid and 1 mM tetrabutyl ammonium phosphate buffered to a pH of 2.8. Initially the tetrabutyl ammonium salt would be adsorbed strongly on the reverse phase and thus acted as an adsorbed ion exchanger. During the program, acetonitrile was added to the solvent and initially this increased the dispersive interactions between the solute and the mobile phase. 

Some advice can be formulated for the choice of organic modifier, (i) Acetonitrile as an aprotic solvent cannot interact with residual silanols, whereas the protic methanol can. Thus, when measuring retention factors, methanol is the cosolvent of choice, as it reduces the secondary interactions between the solutes and the free silanol groups, (ii) For the study of the performance of new stationary phases one should use acetonitrile, as the effects of free silanol groups are fuUy expressed [35]. (iri) Acetonitrile with its better elution capacity can be considered as the best organic modifier for Hpophilicity measurements of highly Hpophihc compounds with adequate stationary phases [36]. 

Retention in HIC can be described in terms of the solvophobic theory, in which the change in free energy on protein binding to the stationary phase with the salt concentration in the mobile phase is determined mainly by the contact surface area between the protein and stationary phase and the nature of the salt as measured by its propensity to increase the surface tension of aqueous solutions [331,333-338]. In simple terms the solvopbobic theory predicts that the log u ithn of the capacity factor should be linearly dependent on the surface tension of the mobile phase, which in turn, is a llne2u function of the salt concentration. At sufficiently high salt concentration the electrostatic contribution to retention can be considered constant, and in the absence of specific salt-protein interactions, log k should depend linearly on salt concentration as described by equation (4.21)... 

Normal alkanes or fatty acid methyl esters are generally used as the standard homologous compounds. The column separation number is dependent on the nature of the stationary phase, the column length, column temperature, and carrier gas flow rate [42-44]. Referring to Figure 1.2, at a sufficiently high capacity factor value either n, N, or SN provides a reasonable value for comparing... 

The large surface area of whisker colusuts enables any stationary phase to be coated efficiently without droplet fomation and their sa >le capacity is such higher than HCOT columns. On the debit side, whisker surfaces are extremely active and very difficult to deactivate, and, because of the high degree of roughening, they are less efficient than MOOT columns. 

As yet, the number of applications is limited but is likely to grow as instrumentation, mostly based on existing CE systems, and columns are improved and the theory of CEC develops. Current examples include mixtures of polyaromatic hydrocarbons, peptides, proteins, DNA fragments, pharmaceuticals and dyes. Chiral separations are possible using chiral stationary phases or by the addition of cyclodextrins to the buffer (p. 179). In theory, the very high efficiencies attainable in CEC mean high peak capacities and therefore the possibility of separating complex mixtures of hundreds of... 

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