Electrical double-layer repulsive force

It is important to note that the concept of osmotic pressure is more general than suggested by the above experiment. In particular, one does not have to invoke the presence of a membrane (or even a concentration difference) to define osmotic pressure. The osmotic pressure, being a property of a solution, always exists and serves to counteract the tendency of the chemical potentials to equalize. It is not important how the differences in the chemical potential come about. The differences may arise due to other factors such as an electric field or gravity. For example, we see in Chapter 11 (Section 11.7a) how osmotic pressure plays a major role in giving rise to repulsion between electrical double layers here, the variation of the concentration in the electrical double layers arises from the electrostatic interaction between a charged surface and the ions in the solution. In Chapter 13 (Section 13.6b.3), we provide another example of the role of differences in osmotic pressures of a polymer solution in giving rise to an effective attractive force between colloidal particles suspended in the solution. 

The concentration and nature of the electrolyte also has a significant impact on the stability of charged colloid dispersions. This was discussed in Section 3.3.2, where the concept of electric double layers was introduced. The electric double layer results from the atmosphere of counterions around a charged colloid particle. The decay of the potential in an electric double layer is governed by the Debye screening length, which is dependent on electrolyte concentration (Eq. 3.8). In the section that follows, the stability of charged colloids is analysed in terms of the balance between the electrostatic (repulsive) forces between double layers and the (predominantly attractive) van der Waals forces. 

The DLVO theory of stability takes into account the interaction of two kinds of long-range forces which determine the closeness of contact of two particles approaching as a result of Brownian movement. The forces concerned are (i) the London-van der Waals forces of attraction, and (ii) the electrostatic repulsion between electrical double layers. 

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). 

Electrostatic Repulsive Forces. As the distance between two approaching particles decreases, their electrical double layers begin to overlap. As a first approximation, the potential energy of the two overlapping double layers is additive, which is a repulsive term since the process increases total energy. Electrostatic repulsion can also be considered as an osmotic force, due to the compression of ions between particles and the tendency of water to flow in to counteract the increased ion concentration. 

Two kinds of barriers are important for two-phase emulsions the electric double layer and steric repulsion from adsorbed polymers. An ionic surfactant adsorbed at the interface of an oil droplet in water orients the polar group toward the water. The counterions of the surfactant form a diffuse cloud reaching out into the continuous phase, the electric double layer. When the counterions start overlapping at the approach of two droplets, a repulsion force is experienced. The repulsion from the electric double layer is famous because it played a decisive role in the theory for colloidal stabiUty that is called DLVO, after its originators Derjaguin, Landau, Vervey, and Overbeek (14,15). The theory provided substantial progress in the understanding of colloidal stabihty, and its treatment dominated the colloid science Hterature for several decades. 

Surface forces measurement is a unique tool for surface characterization. It can directly monitor the distance (D) dependence of surface properties, which is difficult to obtain by other techniques. One of the simplest examples is the case of the electric double-layer force. The repulsion observed between charged surfaces describes the counterion distribution in the vicinity of surfaces and is known as the electric double-layer force (repulsion). In a similar manner, we should be able to study various, more complex surface phenomena and obtain new insight into them. Indeed, based on observation by surface forces measurement and Fourier transform infrared (FTIR) spectroscopy, we have found the formation of a novel molecular architecture, an alcohol macrocluster, at the solid-liquid interface. 

A force-distance curve between layers of the ammonium amphiphiles in water is shown in Figure 8. The interaction is repulsive and is attributed to the electric double-layer... 

Certain negative ions such as Cl , Br, CNS , N03 and SO2 show an adsorption affinity to the mercury surface so in case (a), where the overall potential of the dme is zero, the anions transfer the electrons from the Hg surface towards the inside of the drop, so that the resulting positive charges along the surface will form an electric double layer with the anions adsorbed from the solution. Because according to Coulomb s law similar charges repel one another, a repulsive force results that counteracts the Hg surface tension, so that the apparent crHg value is lowered. 

The physicochemical forces between colloidal particles are described by the DLVO theory (DLVO refers to Deijaguin and Landau, and Verwey and Overbeek). This theory predicts the potential between spherical particles due to attractive London forces and repulsive forces due to electrical double layers. This potential can be attractive, or both repulsive and attractive. Two minima may be observed The primary minimum characterizes particles that are in close contact and are difficult to disperse, whereas the secondary minimum relates to looser dispersible particles. For more details, see Schowalter (1984). Undoubtedly, real cases may be far more complex Many particles may be present, particles are not always the same size, and particles are rarely spherical. However, the fundamental physics of the problem is similar. The incorporation of all these aspects into a simulation involving tens of thousands of aggregates is daunting and models have resorted to idealized descriptions. 

Various anionic compounds such as halides, carboxylates or polyoxoanions, generally dissolved in aqueous solution, can establish electrostatic stabilization. Adsorption of these compounds onto the metallic surface and the associated countercations necessary for charge balance produces an electrical double-layer around the particles (Scheme 9.1). The result is a coulombic repulsion between the particles. At short interparticle distances, if the electric potential associated with the double layer is sufficiently high, repulsive forces opposed to the van der Waals forces will be significant to prevent particle aggregation. 

The solubility of an ionic dye in water normally increases with temperature, since the enhanced mobility favours electrostatic repulsion between ions rather than closer approach to form aggregates by means of the short-range attractive forces. Addition of a simple inorganic electrolyte, on the other hand, normally lowers the solubility limit at a given temperature. Such additions enhance the ionic character of the aqueous phase and help to stabilise the structure of dye aggregates by forming an electrical double layer within the sheath of clustered water molecules around them. 

The state of stability under these conditions can be qualitatively described as follows. As two oil droplets approach each other, the negative charge gives rise to a repulsive effect (Figure 7.4). The repulsion will take place within the electrical double-layer (EDL) region. It can thus be seen that the magnitude of double-layer distance will decrease if the concentration of ions in the water phase increases. This is because the electrical double layer region decreases. However, in all such cases in which two bodies come closer, there exists two different kinds of forces that must be considered ... 

Two charged particles approaching each other sense the presence of each other through the overlap of their electrical double layers. This double-layer overlap results in a repulsive force between similarly charged particles. 

The secondary electroviscous effect is often interpreted in terms of an increase in the effective collision diameter of the particles due to electrostatic repulsive forces (i.e., the particles begin to feel the presence of other particles even at larger interparticle separations because of electrical double layer). A consequence of this is that the excluded volume is greater than that for uncharged particles, and the electrostatic particle-particle interactions in a flowing dispersion give an additional source of energy dissipation. 

As we saw in Chapter 11, surfaces of colloidal particles typically acquire charges for a number of reasons. The electrostatic force that results when the electrical double layers of two particles overlap, if repulsive, serves to counteract the attraction due to van der Waals force. The stability in this case is known as electrostatic stability, and our task is to understand how it depends on the relevant parameters. 

If there are sufficiently strong repulsive interactions, such as from Ihe electric double-layer lorce. then the gas bubbles at the lop of u froth collect together without bursting. Furthermore, their interfaces approach as closely as these repulsive forces allow typically on the order of 100 nm. Thus bubbles on top of a froth can pack together very closely and still allow most uf the liquid to escape downward under the influence of gravity while maintaining their spherical shape. Given sufficient liquid, such a foam can resemble the random close-packed structure formed by hard spheres. 

---