The Zeta Potential

The stability of many colloidal solutions depends critically on the magnitude of the electrostatic potential ( /q) at the surface of the colloidal particles. One of the most important tasks in colloid science is therefore to obtain an estimate of V /o under a wide range of electrolyte conditions. In practice, one of the most convenient methods for obtaining /o uses the fact that a charged particle will move at some constant, limiting velocity under the influence of an applied electric field. Even quite small particles (i.e. 1 pm) can be observed using a dark-field micro- 

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Calculate the zeta potential for the system represented by the first open square point (for pH 3) in Fig. V-8. 

Hydrolysis. The surfaces of metal oxides and hydroxides can take up or release or OH ions and become charged. Potentials as high as 100 mV may be sustained ia aqueous solutions. For aqueous solutions this is a function of the pH the zeta potential for the particle is positive if the solution pH is below the particle s isoelectric pH (pH ), and negative if the pH is above pH Isoelectric poiats for metal oxides are presented ia several pubheations (22,23). Reactions of hydroxyl groups at a surface, Q, with acid and base may be written as follows ... 

Response to Electric and Acoustic Fields. If the stabilization of a suspension is primarily due to electrostatic repulsion, measurement of the zeta potential, can detect whether there is adequate electrostatic repulsion to overcome polarizabiUty attraction. A common guideline is that the dispersion should be stable if > 30 mV. In electrophoresis the appHed electric field is held constant and particle velocity is monitored using a microscope and video camera. In the electrosonic ampHtude technique the electric field is pulsed, and the sudden motion of the charged particles relative to their counterion atmospheres generates an acoustic pulse which can be related to the charge on the particles and the concentration of ions in solution (18). 

The well-known DLVO theory of coUoid stabiUty (10) attributes the state of flocculation to the balance between the van der Waals attractive forces and the repulsive electric double-layer forces at the Hquid—soHd interface. The potential at the double layer, called the zeta potential, is measured indirectly by electrophoretic mobiUty or streaming potential. The bridging flocculation by which polymer molecules are adsorbed on more than one particle results from charge effects, van der Waals forces, or hydrogen bonding (see Colloids). 

Not all of the ions in the diffuse layer are necessarily mobile. Sometimes the distinction is made between the location of the tme interface, an intermediate interface called the Stem layer (5) where there are immobilized diffuse layer ions, and a surface of shear where the bulk fluid begins to move freely. The potential at the surface of shear is called the zeta potential. The only methods available to measure the zeta potential involve moving the surface relative to the bulk. Because the zeta potential is defined as the potential at the surface where the bulk fluid may move under shear, this is by definition the potential that is measured by these techniques (3). 

Electroosmotic flow is also dependent on the zeta potential at the immobilized surface and the strength of the electric field. For electroosmosis, the flow rate generated is... 

This energy maximum is calculated from the electric surface potential. An approximation of this surface potential is the zeta potential, which is experimentally deterrnined with commercial instmments. For o/w emulsions with low electrolyte content in the aqueous phase, a zeta potential of 40 mV is sufficient to bring the energy maximum to this level. 

Streaming Current Detectors These units produce a measurement closely related to the zeta potential of a suspension and are used successfully in optimizing the coagulant dose in clarification applications. 

The potential difference across the mobile part of the diffuse-charge layer is frequently called the zeta potential, = E(0) — E(oo). Its value depends on the composition of the electrolytic solution as well as on the nature of the particle-hquid interface. 

For many particles, the diffuse-charge layer can be characterized adequately by the value of the zeta potential. For a spherical particle of radius / o which is large compared with the thickness of the diffuse-charge layer, an electric field uniform at a distance from the particle will produce a tangential electric field which varies with position on the particle. Laplace s equation [Eq. (22-22)] governs the distribution... 

Nature of a Fog. Fog, like smoke, is a colloid. Once a fog is formed, it is very difficult to knock down. It will go right through packed columns, mist eliminators, or other such devices. Special devices are required to overcome a fog, such as an electric precipitator with charged plates. This can overcome the zeta potential of the charged particles and make them coalesce. 

Zeta potentials of floe produeed in the plant may also be measured as a means of eontrol. The zeta potential value for optimum eoagulation must be determined for a given wastewater by aetual correlation with jar tests or with plant performance. The control point is generally in the range of 0 to 10 millivolts. If good correlations can be obtained between some zeta potential values and optimum plant performance, then it is possible to make rapid measurements of particle charge to compensate for major variations in wastewater composition due to storm flows or other causes. 

Electroviscous effect occurs when a small addition of electrolyte a colloid produces a notable decrease in viscosity. Experiments with different salts have shown that the effective ion is opposite to that of the colloid particles and the influence is much greater with increasing oxidation state of the ion. That is, the decrease in viscosity is associated with decreased potential electrokinetic double layer. The small amoimt of added electrolyte can not appreciably affect on the solvation of the particles, and thus it is possible that one of the determinants of viscosity than the actual volume of the dispersed phase is the zeta potential. 

It is very difficult and scarce to find literature to study the electrokinetic phenomena of proteins or macromolecules in solution therefore limit us to the basic concepts of electrokinetic changes observed, they are conformational change because of the presence of salts and the zeta potential change in pH. 

The deposition-reduction (DR) method is based on the weak electrostatic interactions of polymer surfaces with the oppositely charged Au(III) complex ions, leading to the reduction of Au(III) exclusively on the polymer surfaces. Appropriate anionic or cationic Au(III) precursors are chosen based on the zeta potentials of polymer supports (Figure 3.6) [43]. 

An important reason for this lack of experimental work is that the zeta-potential cannot be easily determined independent of the electrophoretic mobility [284] however, in the case of proteins (as well as some other charged colloids), the intrinsic charge obtained by titration is a parameter that can be measured independent of the electrophoretic mobility. The charge obtained from electrophoretic measurements (i.e., the net charge) via the preceding theories is generally not the same as the charge obtained from titration (i.e., the in-... 

As the particle moves relative to the electrolyte solution, the layer of water mol-ecnles that is directly adjacent to the particle surface is strongly bonnd and will be pnlled along. The thickness of this bonnd layer is approximately one or two diameters of a water molecule. We shall write x, for the x-coordinate of this layer s outer boundary, which is the slip plane. The electrostatic potential at this plane relative to the potential in the bulk solution is designated by the Greek letter and called the zeta potential or electrokinetic potential of the interface discussed. This potential is a very important parameter characterizing the electrokinetic processes in this system. 

It follows from the definition cited that the size of the zeta potential depends on the structure of the diffuse part of the ionic EDL. At the outer limit of the Helmholtz layer (at X = X2) the potential is j/2, in the notation adopted in Chapter 10. Beyond this point the potential asymptotically approaches zero with increasing distance from the surface. The slip plane in all likelihood is somewhat farther away from the electrode than the outer Helmholtz layer. Hence, the valne of agrees in sign with the value of /2 but is somewhat lower in absolute value. 

All factors influencing the potentials of the inner or outer Helmholtz plane will also influence the zeta potential. For instance, when, owing to the adsorption of surface-active anions, a positively charged metal surface will, at constant value of electrode potential, be converted to a negatively charged surface (see Fig. 10.3, curve 2), the zeta potential will also become negative. The zeta potential is zero around the point of zero charge, where an ionic edl is absent. 

The charges present on the insulator surface in contact with the solution give rise to an accumulation of ions of opposite sign in the solution layer next to the surface, and thus formation of an electric double layer. Since straightforward electrochemical measurements are not possible at insulator surfaces, the only way in which this EDL can be characterized quantitatively is by measuring the values of the zeta potential in electrokinetic experiments (see Section 31.2). 

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