Colloid particle electrokinetic phenomena

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. 

If the electric field E is applied to a system of colloidal particles in a closed cuvette where no streaming of the liquid can occur, the particles will move with velocity v. This phenomenon is termed electrophoresis. The force acting on a spherical colloidal particle with radius r in the electric field E is 4jrerE02 (for simplicity, the potential in the diffuse electric layer is identified with the electrokinetic potential). The resistance of the medium is given by the Stokes equation (2.6.2) and equals 6jtr]r. At a steady state of motion these two forces are equal and, to a first approximation, the electrophoretic mobility v/E is... 

A very useful type of phenomenon in the study of colloidal particles is the electrokinetic phenomenon that results from the movement of a solid phase with surface charge relative to an electrolyte-containing liquid phase. An applied electric field induces movement or, conversely, movement induces an electric field. The phenomena can be divided into two types ... 

The external screen is a diffusion layer in which the ions are poorly bonded as the distance from the Stem layer is increasing, and have the tendency to migrate into the solution. Therefore the electric potential in this layer decreases exponentially with the distance from the boundary of Stem layer. On this boundary it is called electrokinetic potential or potential. It can be derived from the measurements of the colloidal particles velocity in the electric field of intensity E. This phenomenon is known as electrophoresis. C potential can be determined from the formula given by Smoluchowski ... 

A fundamental electrokinetic phenomenon is the electroosmotic flow of a liquid electrolyte (solution of positive and negative ions) past a charged surface in response to a tangential electric field. Electrophoresis is the related phenomenon of motion of a colloidal particle or molecule in a background electric field, propelled by electroosmotic flow in the opposite direction. The basic physics is as follows ... 

Let us mention that dielectrophoresis has also found wide application in manipulation and sorting of particles and biological cells. Together with standard electrophoresis, it is perhaps the most often used electrokinetic phenomenon with practical applications in mind. Even particle separation can be achieved by using microelectrode arrays [55]. Based on the dielectrophoresis phenomenon, a new technique has recently become available for particle or cell separation, namely the dielectrophoresis/gravitational field-flow fractionation (DEP/G-FFF). In DEP/ G-FFF, the relative positions and velocities of unequal particles or cells are controlled by the dielectric properties of the colloid and the frequency of the applied field. The method has been applied to model polystyrene beads, but, most interestingly, to suspensions of different biological cells [56]. 

In Equation 19.12, Cq = 8.854 x j-i qi -1 jg jjjg dielectric constant in vacuum, e is the relative dielectric permittivity of the solvent (e = 78.5 for water at room temperature 298 K), and are the electrokinetic zeta potential defined at the shear plane (see Figure 19.3), r is the dynamic viscosity of the solvent (q = 8.91 x 10 kgm" s for water at room temperature 298 K), and E is the externally applied electric field. The first equation in Equation 19.12 represents the fluid motion in a stationary channel under the action of an externally appUed electric field. The motion is called electro-osmosis and the velocity is v. The second equation in Equation 19.12 gives the velocity v, of charged suspended colloidal particle (or a dissolved molecule) driven by the same electric field. This phenomenon is called electrophoresis. The EDL thickness 1/k depends on the concentration of background electrolyte [18,19,25,26]. 

The colloid vibration potential (difference) E or CVP is the a.c. potential difference measured between two Identical relaxed electrodes, placed in the dispersion if the latter Is subjected to an (ultra)sonlc field. CVP Is a particular case of the more general phenomenon, ultrasonic vibration potential (UVP), applying to any system, whether or not colloids are present. This field sets the particles into a vibrating motion, as a result of which the centres of particle charge and countercharge are periodically displaced with respect to each other. This phenomenon is the a.c. equivalent of that observed in the Dorn effect. Counterpart to this is the electrokinetic sonic amplitude, ESA, the amplitude of the (ultra)sonlc field created by an a.c, electric field in a dispersion. 

When an alternating voltage is applied to a colloid, the particles move back and forth with a velocity that depends on their size and zeta potential and on the frequency of the applied field. As they move, the particles generate sound waves. This phenomenon is called the electroacoustic effect, which can be measured and what was named electrokinetic sonic amplitude (ESA) [5],... 

Acoustics has a related field that is usually referred to as electroacoustics (8). Electroacoustics can provide particle size distribution as well as zeta potential. This relatively new technique is more complex than acoustics because an additional electric field is involved. As a result, both hardware and theory become more complicated. There are even two different versions of electroacoustics depending on what field is used as a driving force. Electrokinetic sonic amplitude (ESA) involves the generation of sound energy caused by the driving force of an applied electric field. Colloid vibration current (CVC) is the phenomenon where sound energy is applied to a system and a resultant eleetrie field or eurrent is created by the vibration of the colloid electric double layers. 

Marian von Smoluchowski (1872-1917). .. was a Polish physicist whose research on discrete state matter is still highly valued in modem science. He is particularly acknowledged for his theory on Brownian motion, which he developed independently of Einstein and which laid the foundation for the theory of stochastic processes. A similar rank is deserved by his discovery of density fluctuations in liquids and gases and their relevance for macroscopic scattering— most prominently explained by the phenomenon of critical opalescence. Both works proved veiy influential for the understanding of colloidal suspensions. Furthermore, he did pioneering work on the quantification of particle aggregation as well as in the field of electrokinetic phenomena. 

The Electrokinetic Sonic Amplitude (ESA) effect in this context refers to the generation of ultrasound by the application of an alternating electric field to a colloid. Previous reviews on the ESA have mainly focused on the determination of particle size and zeta potential from the ESA. While this is certainly a very important application of the ESA phenomenon, there is more information in the ESA spectmm than just particle size and zeta. It can be used, for instance, to determine the thickness of adsorbed polymer layers or the surface conductance under the shear plane. It is these other applications that will be our main interest here. To begin we will give an alternative explanation for the ESA phenomenon, one that allows a deeper understanding of the underlying physics. 

---