Electrochemistry of capillary systems with narrow pores V. Streaming potential: Donnan hindrance of electrolyte transport

Abstract

The electrochemical theory of capillary systems with narrow pores outlined in Part I of this series is applied to the streaming potential and the electrical hindrance of electrolyte transport across ion selective membranes (Donnan hindrance). Both phenomena are related to the fixed ion concentration. Streaming potentials were measured while using collodion membranes of graded porosity and graded fixed ion concentration. The bulk phases consisted of aqueous KCl solutions with a concentration 2×10 −4 n. The streaming potentials were calculated theoretically by using the electrical conductivity data of the membranes given in Part III of this series. The agreement between the experimental results and the predictions of the theory is good. Theory also predicts that a volume flow across the membrane caused by a hydrostatic pressure difference generates a filtration effect the concentration c s of the electrolyte in the solution leaving the membrane on the low pressure side is lower than the concentration c on the high pressure side. The concentration ratio ( c s/ c) is equal to the ratio ( κ/ κ i ) of the electrical conductivity of the high pressure phase κ and that of the pore fluid κ i . The hindrance of the electrolyte transport is a transient phenomenon. It disappears slowly if the experiment is continued over a long period of time. This phenomenon, which is of importance in the understanding of ultrafiltration processes using membranes, is discussed in detail. It is compared with the observed changes in the streaming potential as a function of time. The influence of the electrical convection conductivity (electrical surface conductivity) on the streaming potential can be neglected under the chosen experimental conditions. Its influence will be discussed in Part VI of this series.