Continuum-statistical dynamics of colloidal suspensions under kinematic reversibility

Abstract

We present a linear response theory that establishes the continuum-mechanical origin of Onsager reciprocity in colloidal motion. By decoupling hydrostatic and hydrodynamic stress, we show that Onsager reciprocal relations emerge when the Lorentz reciprocal theorem is applied under kinematic reversibility to the auxiliary flow problem of colloidal sedimentation. Our framework applies to suspensions containing multiple species of microparticles and derives all non-equilibrium contributions to colloidal diffusion from a single application of the Lorentz reciprocal theorem, irrespective of whether a slip or no-slip hydrodynamic boundary condition is imposed at the colloidal surface. Furthermore, a boundary-layer treatment is only assumed for ciliary motion, while the hydrostatic forces giving rise to non-equilibrium thermodynamic motion are fully resolved beyond the boundary-layer approximation. In particular, our framework is consistent with classical osmosis through a semi-permeable membrane, where fluid flow occurs without interfacial potential interactions. For diffusiophoresis due to volume exclusion of a solute, our results therefore predict colloidal motion towards higher solute concentration for thin excluded-volume layers, whereas the opposite trend is recovered for longer-ranged, moderately repulsive potentials.