Charge mobility measurements

Surface active electrolytes produce charged micelles whose effective charge can be measured by electrophoretic mobility [117,156]. The net charge is lower than the degree of aggregation, however, since some of the counterions remain associated with the micelle, presumably as part of a Stem layer (see Section V-3) [157]. Combination of self-diffusion with electrophoretic mobility measurements indicates that a typical micelle of a univalent surfactant contains about 1(X) monomer units and carries a net charge of 50-70. Additional colloidal characterization techniques are applicable to micelles such as ultrafiltration [158]. 

Electroultrafiltration (EUF) combines forced-flow electrophoresis (see Electroseparations,electrophoresis) with ultrafiltration to control or eliminate the gel-polarization layer (45—47). Suspended colloidal particles have electrophoretic mobilities measured by a zeta potential (see Colloids Elotation). Most naturally occurring suspensoids (eg, clay, PVC latex, and biological systems), emulsions, and protein solutes are negatively charged. Placing an electric field across an ultrafiltration membrane faciUtates transport of retained species away from the membrane surface. Thus, the retention of partially rejected solutes can be dramatically improved (see Electrodialysis). 

Experimentally, the charge mobilities are obtained by time-of-hight-measure-ments or by characterizing held-effect-transistor devices made of the materials. In time-of flight experiments, the mobility p is directly given by... 

The main experimental elfects are accounted for with this model. Some approximations have been made a higher-level calculation is needed which takes into account the fact that the charge distribution of the trapped electron may extend outside the cavity into the liquid. A significant unknown is the value of the quasi-free mobility in low mobility liquids. In principle, Hall mobility measurements (see Sec. 6.3) could provide an answer but so far have not. Berlin et al. [144] estimated a value of = 27 cm /Vs for hexane. Recently, terahertz (THz) time-domain spectroscopy has been utilized which is sensitive to the transport of quasi-free electrons [161]. For hexane, this technique gave a value of qf = 470 cm /Vs. Mozumder [162] introduced the modification that motion of the electron in the quasi-free state may be in part ballistic that is, there is very little scattering of the electron while in the quasi-free state. 

This means that studies of the conductivity alone are insufficient to obtain a complete understanding of the mechanism of charge transfer. Other techniques such as photoconductivity, thermoelectric effect and mobility measurements are required for a deeper understanding of the phenomenon. 

The specific conductivity (y) is a measure of the mobility of ions in an electrolyte or electrons in a metallic conductor. Thus, y is about 1 or 107 S/m for a 0.1 kmol/m3 aqueous salt solution or for a metal such as iron, respectively. Such a difference in charge mobility makes the temperature dependence of % [i-e.,(l/x)3x/97k] positive for ions of about 2.5% per K, but negative for metals and alloys of approximately an order of magnitude lower (Prentice, 1991). 

As mentioned above, Edelhauser (7) showed that the concentration gradient across the dialysis membrane must exceed a critical value to make the dialysis proceed at a practical rate. In contrast, Ottweill and Shaw (12) found from electrophoretic mobility measurements and desorption of radioactive emulsifier that all of the emulsifier was removed by dialysis or at least that a constant surface charge was obtained. 

---