Colloidal diffusiophoresis in crossed electrolyte gradients: Experimental demonstration of an “action-at-a-distance” effect predicted by the Nernst-Planck equations

In an externally imposed electrolyte (salt) concentration gradient, charged colloids drift at speeds of order one micrometre per second. This phenomenon is known as diffusiophoresis. In systems with multiple salts and “crossed” salt gradients, a nonlocal component of the electric field associated with a circulating (solenoidal) ion current can arise. This is in addition to the conventional local component that depends only on the local salt gradients. Here we report experimental observations verifying the existence of this nonlocal contribution. To our knowledge this is the first observation of nonlocal diffusiophoresis. The current develops quasi-instantaneously on the timescale of salt diffusion. Therefore, in systems with multiple salts and crossed salt gradients, one can expect a nonlocal contribution to diffusiophoresis which is dependent on the geometry of the system as a whole and appears as a kind of instantaneous “action-at-a-distance” effect. The interpretation is aided by a magnetostatic analogy. Our experiments are facilitated by a judicious particle-dependent choice of salt (potassium acetate) for which the two local contributions to diffusiophoresis almost cancel, effectively eliminating conventional diffusiophoresis. This enables us to clearly identify the novel, nonlocal effect and may be useful in other contexts, for example, in sorting particle mixtures.