Calculation of Zeta Potential from Electrokinetic Measurements on Titania Plugs

The O'Brien theory developed for the electrical conductivity and electro-osmosis in porous plugs consisting of nonconducting particles has been applied for the calculation of zeta-potentials from conductivity and streaming potential measurements at two pH values, 3.3 and 6.5 or 5.8, on plugs composed of titania (undoped and doped with W6+ and Li+ ions) particles. The particles have been prepared both by precipitation (continuous crystallization at constant supersaturation) and by the sol-gel method. It was found that O'Brien's theory is also applicable in n-type semiconductor particles, such as titania (doped and undoped). Specifically, for the correct determination of zeta-potentials measured in solutions of relatively low ionic strength, it is necessary to take into account surface conduction behind the shear plane, for all samples measured at pH 3.3, a value considerably lower than the isoelectric point (i.e.p.) of titania. Under these conditions the surface charge of the suspended titania particles is high, and consequently the contribution of surface conductance to the conductivity of the plug is significant. The effect of surface conduction behind the shear plane on the calculation of zeta-potential is enhanced for the Li+-doped preparations due to the increase of surface conductivity caused by doping with Li+. Measurements of the streaming potential for the samples prepared with the sol-gel method were made at pH 6.5 (5.8 for the undoped titania); i.e., near the pH corresponding to the i.e.p., correct values of zeta-potential may be obtained in suspensions even at low ionic strength without taking into account the polarization of the double layer due to surface conduction, by applying the primitive Smoluchowski theory. This treatment is valid because at pH values near the i.e.p. the surface charge of the particles is very low, and consequently surface conductance is negligible compared with the conductivity of the plug. Copyright 1999 Academic Press.