Motion of a particle generated by chemical gradients. Part 2. Electrolytes

When immersed in a non-uniform electrolyte solution, a rigid charged sphere migrates toward higher or lower concentration of the electrolyte depending on the relative ionic mobilities and the charge borne by the sphere. This motion has a twofold origin: first, a macroscopic electrolyte gradient produces an electric field which acts on the charged sphere (electrophoresis); secondly, the electrolyte gradient polarizes the cloud of counterions surrounding the charged sphere by making the cloud thinner on the high-concentration side (chemiphoresis). In this paper, we compute the terminal velocity of a non-conductive sphere through a slightly non-uniform solution of a symmetrically charged binary electrolyte. The analysis proceeds through an expansion in the small parameter λ (defined as the ratio of the counterion-cloud thickness to the particle radius). Results to O (λ) are presented. The only property of the sphere's surface that affects the velocity is its zeta potential ζ when the electrolyte gradient vanishes; no information concerning the dependence of ζ upon ionic strength is needed. While the chemiphoretic effect always directs the particle toward higher electrolyte concentration, the electrophoretic contribution can move the particle in either direction depending on the sign of βζ, where β is a normalized difference in mobilities between cation and anion of the elecytrolyte; thus particle movement could be directed toward either higher or lower electrolyte concentration depending on the physical properties of the system. With slight algebraic rearrangement, our results are also applicable to conventional electrophoresis (particle motion in an applied electric field) and show excellent agreement with the numerical calculations of O'Brien & White (1978).