Zeta-potential determination via electrophoretic light scattering

Theory: Electrophoresis is the measurement of the movement of colloidal particles when there are placed in an electric field. The application of an external voltage causes the charged particles to move toward one of the electrodes, wheras a negative particle moves to the anode and a positive one to the cathode. In case of microelectrophoresis the migration of the particles is determined optically. The velocity is measured by timing individual particles between marks on a grid placed in the microscope eyepiece. The sample has to be high diluted, so that individual particles can be observed. Progress in microscopy and the combination with photon correlation spectroscopy opened the possibility for determining particles in the range between 3nm and 5m [1]. From the point of view of the electrophoretic cell, microelectrophoresis is a capillary electrophoresis. The experiment in capillaries is complicated by the fact that a streaming potential occurs and the applied voltage causes the liquid in the cell to move. This movement, called electroosmosis, occurs because the glass walls of the cell are negatively charged. There is only one particular point between the cell wall and the centre of the cell, the stationary layer at a distinct distance x (x=r/2), where the particles move with their true velocity which is due solely to their own charge. To get a true result, the microscope must be focused in this layer and the particles measured must be in focus. As an optical detection system electrophoretic light scattering is frequently used in the last years [2]. In that case, the collected signal of the particles' movement shifted to higher or lower frequencies depending of their charge.The frequencies are then converted to electrophoretic mobilities, velocities, and finally zeta potentials. The velocity (v0) obtained equals the product of electrophoretic mobility (E) and the applied electrical field (E0): v0 = E E0 (1)

For calculating the zeta potential the following theoretical assumptions are necessary: In the modified Stokes-equation the electrical field is the driving force for the movement of the particles:

v0 /E0 = E = Q/(6a)

(2)

Q - particle charge a - particle radius - viscosity

The "thickness" of the double layer is determined by the Debye-Hckel-parameter 1/ = [4e2nizi2/ 0 kT]1/2

(3)

e - elementary charge zi - number of charge of the ion - permittivity

The dimensionless product

a describes the ratio of the particle radius to the

"thickness" of the double layer. Assuming a low charge, Q may be described using the Henry-equation: - zeta potential

E = (2/3) f(a)

(4)

For a low a the Henry-function approches the value 1, for large a it approches 1.5. These values correspond to the both borderline cases known as Hckel- and Smoluchowski equation. However, the Smoluchowski approximation is that one, which is usually used for the calculation of zeta potentials of dispersed colloidal systems containing spherical particles.

References: [1] [2] R.J. Hunter, Potential in Colloidal Science, Principles and Applications. 3rd ed. London: Academic Press Limited, 1988, p 35 ibid, pp17-42
2

Experimental part:
Chemicals: 0.01 % polystyrene latex (aqueous dispersion), 0.1% chitosan in 0.025 M HCl (Mv = 64 000 g/mol) Procedure: 1) Proof, if the cell is sufficiently clean by measuring pure destilled water (zeta potential should be around zero) 2) Add defined amounts of the chitosan solution to 10 ml polystyrene latex and measure the zeta potential five times. Measure at first the initials latex! volume of chitosan to be added: 1 l, 3l, 5l, 7l, 10l, 15l, 25l, 30l, 40l, 50l, 60l each of the samples has to be stirred about 5 min before measuring Discussion: 1) Calculate from the repeated measurements the average of the zeta potential! 2) The polystyrene latex was made by a radical emulsion polymerisation by using potassiumperoxidisulfate as initiator and sodium dodecylsulfate as emulgator. Discuss the initial zeta potential of the latex with respect to this recipe! 3) Discuss the dependence of the zeta potential () on the chitosan-concentration by using a /c-plot! What can be said about the surface coverage of the polystyrene particles? 4) Which concentration of mol ionic groups of chitosan is needed for a recharching of the latex particles (charge density of chitosan = 4.89 10-3 mol ion. groups/g) 5) How a flocculation can be explained?