Electrical properties of Interfaces

This section deals with the principles involved with the surfaces that are charged in relation to their surrounding liquid environment. Study of electrical properties find application in: 1. Stabilization of colloidal dispersions. 2. Preparation of flocculated suspensions. 3. Stabilization of emulsions.

Particles dispersed in liquid media may become charged in the following ways: 1. Selective adsorption of a particular ionic species present in solution. This may be the ion added to the solution or it may be the hydronium or hydroxyl ions of pure water. The majority of particles dispersed in water acquire a negative charge due to adsorption of hydroxy ions.

2. Charges on particles may arise from ionization of groups (such as COOH) that may be situated at the surface of the particle. In both cases, charge is a function of pKa & pH.

3. Rare cases: Origin of charge on particle surface may arise when there is a difference in dielectric constant between the particle & its dispersion medium.
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The electric double layer

The electrical double layer is a structure that describes the variation of electric potential near a surface. It has a large bearing on the behavior of colloids & other surfaces in contact with solutions & solid state fast ion conductors. The earliest model of the electrical double layer is attributed to Helmholtz (1879). Helmholtz treated the double layer

Consider a solid surface in contact with a polar solution containing ions. E.g. Assume that some of the cations are adsorbed onto the surface giving positive charge. Remaining in solution are the rest of the cations plus the total no. of anions added. These anions are attracted to the positively charged surface by electric forces that also serve to repel the approach of any further cations once the initial adsorption is

At a particular distance from the surface, the conc of anions & cations are equal. i.e. electric neutrality prevails. Inner Helmholtz Plane (IHP) The whole system is electrically neutral, (OHP) Outer Helmholtz plane even though there are regions of unequal Tightly bound layer distribution of anions & cations. It is illustrated as follows:

Solid - liquid interface

Shear plane

In the diagram, aa is the surface of the solid or solid-liquid interface. The adsorbed ions give the surface its positive charge & are referred as potentialdetermining ions. Immediately adjacent to this surface layer is a region of tightly bound solvent molecules, together with some negative ions, also tightly bound to the surface. The limit of this region is given by bb. These ions, having a charge opposite to the potential determining ions are known as counter ions

The degree of attraction of the solvent molecules & counter ions is such that if the surface is moved relative to the liquid, the shear plane is bb rather than aa, the true surface. In the region bounded by the lines bb & cc, there is an excess of negative ions. The potential at bb is still positive, since there are fewer anions in the tightly bound layer than the cations adsorbed on to the surface of the solid. Beyond cc, the distribution of ions is

Two situations other than that represented are possible: 1.If the counter ions in the tightly bound solvated layer equals the positive charge on the solid surface, then electric neutrality occurs at the plane bb rather than cc. 2.Should the total charge of the counter ions in the region aa bb exceed the charge due to the potential determining ions, then the net charge at bb will be negative, rather than less positive. This means that, for electric neutrality to be

The changes in potential with difference from the surface of the various situations as discussed earlier may be represented as follows:

From the figure, it can be inferred that the

E, electrothermodynamic , electrokinetic

Zeta potential at solid liquid boundary

Zeta,

Nernst, E

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The potential at the solid surface aa due to the potential determining ion is the electro thermodynamic potential & is defined as the difference in potential between actual surface & the electro neutral region of the solution. This potential is termed as NERNST POTENTIAL E. The potential located at the shear plane bb is known as electro kinetic or ZETA POTENTIAL . It is defined as the difference in potential

Nernst & Zeta potential

In general, Zeta potential is more imp in the field of pharmacy compared to Nernst potential, because the electrical double layer also moves when the particle is under motion. Zeta potential has practical application in the stability of systems containing dispersed particles, since this potential governs the degree of repulsion between adjacent, similarly charged, dispersed particles. Hence, it is used to predict particle-particle interaction. An optimum zeta potential is desirable for max stability. If the zeta potential reduces below a certain value, the attractive forces exceed the