Salts, electromigration

For obtaining internal or external mobilities, the corresponding transport numbers are usually measured. There are several methods for determining transport numbers in molten salts that is, the Kleimn method (countercurrent electromigration method or column method), the Hittorf method (disk method), the zone electromigration method (layer method), the emf method, and the moving boundary method. These are described in a comprehensive review. ... 

There is difficulty in defining the absolute mobilities of the constituent ions in a molten salt, since it does not contain fixed particles that could serve as a coordinate reference. Experimental means for measuring external transport numbers or external mobilities are scarce, although the zone electromigration method (layer method) and the improved Hittorf method may be used. In addition, external mobilities in molten salts cannot be easily calculated, even from molecular dynamics simulation. 

The progress achieved in the field of isotope electromigration in metals, salts, and aqueous solutions since the meeting on isotope separation in Paris in 1963 is reported. It is shown that the temperature dependence of the isotope effect in liquid metals leads to the conclusion that it is a result of classical atom—atom interactions. Isotope effects in molten salts are smaller than in classical ionic gases. A three stage model is proposed for an explanation of the temperature dependences of the isotope effects in molten salts. The available data of the relative difference in mobilities of isotopes in aqueous solutions are summarized. 

In liquid salts the isotope factor is in principle measurable by electrotransport (electromigration). Since many such measurements are available (13), it is especially tempting to study thermotransport in molten ionic media. One must bear in mind, however, the possibility of the following complications (a) the mechanisms of electrotransport, thermotransport, and self-diffusion may be non-identical see Reference 16) b) the isotope factors, as determined by electrotransport, are dependent, via transport numbers, on the reference system and (c) severe experimental difficulties may be encountered in liquid salt thermotransport, mainly corrosion and convection effects. 

The impact of different surfactants (SDS, DOSS, CTAB and hexadimethrine bromide, bile salts °), nonionic and mixed micelles, and additives (neutral and anionic CDs," " tetraalkylammonium salts, organic solvents in EKC separations has been demonstrated with phenol test mixtures. In addition, phenols have been chosen to introduce the applicability of more exotic EKC secondary phases such as SDS modified by bovine serum albumin, water-soluble calixarene, " starburstdendrimers, " " cationic replaceable polymeric phases, ionenes, amphiphilic block copolymers,polyelectrolye complexes,and liposome-coated capillaries. The separation of phenols of environmental interest as well as the sources and transformations of chlorophenols in the natural environment have been revised. Examples of the investigation of phenols by EKC methodologies in aquatic systems, soil," " and gas phase are compiled in Table 31.3. Figure 31.3 illustrates the electromigration separation of phenols by both CZE and EKC modes. 

On-tube detection is almost universally used in CE, and the short detection path lengths provided by fused silica capillaries result in a 100- to 400-foId reduction in detection sensitivity compared with HPLC. Although various techniques are employed in CE to regain most of this sensitivity, detectivity remains a serious concern. Therefore concentration steps are often necessary in sample preparation for CE. It should be emphasized that some concentration techniques such as evaporation and lyophilization will not change the sample ion/salt ion ratio for nonvolatile salts, so no effective concentration is achieved when electromigration injection is used. The use of transient isotachophoresis has been proposed for on-line preconcentration of proteins prior to CZE separation [41,42],... 

A more simplified model was presented in Ref. 10, where the membrane was assumed to be perfectly permselective toward the counter-ion, and the salt concentration in the macropores of the electrode assumed to be unvarying in time. A basic element in the modeling of the membranes in MCDI is that in the membrane the cation concentration is different from the anion concentration, with the difference compensated by the fixed membrane charge density, X. Except for this difference, the same ion transport model can be used as in free solution (Nemst-Planck equation), thus, with ions moving under the influence of a concentration gradient and because of an electrical field (electromigration). At the edges of the membranes, a Donnan potential difference develops between the outside solution and inside the membrane. For more information on MCDI, see Section 15.4.3, where a porous electrode is modeled which has an ideally permselective membrane layer in front. 

---