Electrokinetics

Electrokinetics is an in situ remediation technology applicable to soil or soil-like material with low hydraulic conductivities (e.g., clay) contaminated with heavy metals, radionuclides, and selected organic pollutants. The technique has been used in the past in the oil recovery industry and to remove water from soils. 

The technology involves the application of low-intensity, direct electrical current across electrode pairs that have been implanted on each side of the contaminated soil. The electrical current induces electroosmosis and ion migration between the two implanted electrodes. Depending on their charge, the contaminants accumulate on one of the electrodes and are extracted to a recovery system (Fig. 14.4). Improved performance of electrokinetics could be attained by the introduction of surfactants. 

There are four electrokinetic effects that are all due to the electric charge of the double layer at the soUd/liquid interphase (cf Section 7.5). 

Electrophoresis is the migration of charged particles through a liquid. 

Electro-osmosis is a bulk liquid flow through a pore caused by a migrating ionic sheath. 

Sedimentation (streaming) potential is generated because of falling (moving) charged particles. 

Sedimentation electric current is generated when a liquid is pressed through a pore. 

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A number of electrokinetic phenomena have in common the feature that relative motion between a charged surface and the bulk solution is involved. Essen-... 

The relationship between the various electrokinetic effects are summarized in Table V-3. 

The most familiar type of electrokinetic experiment consists of setting up a potential gradient in a solution containing charged particles and determining their rate of motion. If the particles are small molecular ions, the phenomenon is called ionic conductance, if they are larger units, such as protein molecules, or colloidal particles, it is called electrophoresis. 

The simple treatment of this and of other electrokinetic effects was greatly clarified by Smoluchowski [69] for electroosmosis it is as follows. The volume flow V (in cm /sec) for a tube of radius r is given by applying the linear velocity V to the body of liquid in the tube... 

Streaming potentials, like other electrokinetic effects, are difficult to measure reproducibly. One means involves forcing a liquid under pressure through a porous plug or capillary and measuring E by means of electrodes in the solution on either side [6, 23, 71-73]. 

The final and less commonly dealt-with member of the family of electrokinetic phenomena is the sedimentation potential. If charged particles are caused to move relative to the medium as a result, say, of a gravitational or centrifugal field, there again will be an induced potential E. The formula relating to f and other parameters is [72, 77]... 

E. Interrelationships in Electrokinetic Phenomena In electroosmosis, the volumetric flow and current are related through... 

The presence of surface conductance behind the slip plane alters the relationships between the various electrokinetic phenomena [83, 84] further complications arise in solvent mixtures [85]. Surface conductance can have a profound effect on the streaming current and electrophoretic mobility of polymer latices [86, 87]. In order to obtain an accurate interpretation of the electrostatic properties of a suspension, one must perform more than one type of electrokinetic experiment. One novel approach is to measure electrophoretic mobility and dielectric spectroscopy in a single instrument [88]. 

Two nucleation processes important to many people (including some surface scientists ) occur in the formation of gallstones in human bile and kidney stones in urine. Cholesterol crystallization in bile causes the formation of gallstones. Cryotransmission microscopy (Chapter VIII) studies of human bile reveal vesicles, micelles, and potential early crystallites indicating that the cholesterol crystallization in bile is not cooperative and the true nucleation time may be much shorter than that found by standard clinical analysis by light microscopy [75]. Kidney stones often form from crystals of calcium oxalates in urine. Inhibitors can prevent nucleation and influence the solid phase and intercrystallite interactions [76, 77]. Citrate, for example, is an important physiological inhibitor to the formation of calcium renal stones. Electrokinetic studies (see Section V-6) have shown the effect of various inhibitors on the surface potential and colloidal stability of micrometer-sized dispersions of calcium oxalate crystals formed in synthetic urine [78, 79]. 

Protein adsorption has been studied with a variety of techniques such as ellipsome-try [107,108], ESCA [109], surface forces measurements [102], total internal reflection fluorescence (TIRE) [103,110], electron microscopy [111], and electrokinetic measurement of latex particles [112,113] and capillaries [114], The TIRE technique has recently been adapted to observe surface diffusion [106] and orientation [IIS] in adsorbed layers. These experiments point toward the significant influence of the protein-surface interaction on the adsorption characteristics [105,108,110]. A very important interaction is due to the hydrophobic interaction between parts of the protein and polymeric surfaces [18], although often electrostatic interactions are also influential [ 116]. Protein desorption can be affected by altering the pH [117] or by the introduction of a complexing agent [118]. 

In particular, in polar solvents, the surface of a colloidal particle tends to be charged. As will be discussed in section C2.6.4.2, this has a large influence on particle interactions. A few key concepts are introduced here. For more details, see [32] (eh 13), [33] (eh 7), [36] (eh 4) and [34] (eh 12). The presence of these surface charges gives rise to a number of electrokinetic phenomena, in particular electrophoresis. 

Injecting the Sample The mechanism by which samples are introduced in capillary electrophoresis is quite different from that used in GC or HPLC. Two types of injection are commonly used hydrodynamic injection and electrokinetic injection. In both cases the capillary tube is filled with buffer solution. One end of the capillary tube is placed in the destination reservoir, and the other is placed in the sample vial. 

Electrokinetic injections are made by placing both the capillary and the anode into the sample vial and briefly applying an electric fleld. The moles of solute injected into the capillary, nj, are determined using... 

Micellar Electrokinetic Capillary Chromatography One limitation to CZE is its inability to separate neutral species. Micellar electrokinetic chromatography... 

The elution order for neutral species in MEKC depends on the extent to which they partition into the micelles. Hydrophilic neutrals are insoluble in the micelle s hydrophobic inner environment and elute as a single band as they would in CZE. Neutral solutes that are extremely hydrophobic are completely soluble in the micelle, eluting with the micelles as a single band. Those neutral species that exist in a partition equilibrium between the buffer solution and the micelles elute between the completely hydrophilic and completely hydrophobic neutrals. Those neutral species favoring the buffer solution elute before those favoring the micelles. Micellar electrokinetic chromatography has been used to separate a wide variety of samples, including mixtures of pharmaceutical compounds, vitamins, and explosives. 

Kovat s retention index (p. 575) liquid-solid adsorption chromatography (p. 590) longitudinal diffusion (p. 560) loop injector (p. 584) mass spectrum (p. 571) mass transfer (p. 561) micellar electrokinetic capillary chromatography (p. 606) micelle (p. 606) mobile phase (p. 546) normal-phase chromatography (p. 580) on-column injection (p. 568) open tubular column (p. 564) packed column (p. 564) peak capacity (p. 554)... 

The last set of experiments provides examples of the application of capillary electrophoresis. These experiments encompass a variety of different types of samples and include examples of capillary zone electrophoresis and micellar electrokinetic chromatography. 

Vogt, C. Conradi, S. Rhode, E. Determination of Caffeine and Other Purine Compounds in Pood and Pharmaceuticals by Micellar Electrokinetic Chromatography, /. Chem. Educ. 1997, 74, 1126-1130. 

Electrogalvanizing Electrography Electrogravimetry Electrohydrodynamics Electro-Katadyn process Electrokinetics Electroless deposition Electroless nickel Electroless plating... 

The 2eta potential (Fig. 8) is essentially the potential that can be measured at the surface of shear that forms if the sohd was to be moved relative to the surrounding ionic medium. Techniques for the measurement of the 2eta potentials of particles of various si2es are collectively known as electrokinetic potential measurement methods and include microelectrophoresis, streaming potential, sedimentation potential, and electro osmosis (19). A numerical value for 2eta potential from microelectrophoresis can be obtained to a first approximation from equation 2, where Tf = viscosity of the liquid, e = dielectric constant of the medium within the electrical double layer, = electrophoretic velocity, and E = electric field. 

Electrokinetics. Electrokinetics is a tested technology that has been used for over half a century to dewater and stabilize soils, and has recently been investigated for in situ use at hazardous waste sites (23). Primarily used for metals removal, the technology utilizes an electrical field to generate a flow and concentration gradient in porous and semiporous soils. 

An innovative technology called the "lasagna" process is based on the electrokinetic phenomenon called electro osmosis. The lasagna process was created to treat difficult wastes in low permeabiUty, sdt- and clay-laden soils (40). The lasagna process is so named because it consists of a number of layered subsurface electrodes and treatment zones. These layers can be constmcted either horizontally where contaminants are forced to more upward or in vertical position where lateral contaminant movement is desired. 

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