(224g) Diffusiophoresis: A Colloidal Perspective

Diffusiophoresis, the motion of a colloidal particle in response to an externally imposed concentration gradient of a solute species, is analyzed from both the traditional coarse-grained macroscopic (i.e. continuum) perspective and from a fine-grained micromechanical level in which the colloidal particle and the solute are treated on the same footing as Brownian particles dispersed in a solvent. It is shown that although the two approaches agree when the solute is much smaller in size than the colloidal particle and is present at very dilute concentrations, the micromechanical colloidal perspective relaxes these restrictions and applies to any size ratio and any concentration of solute. The different levels of description also provide different mechanical analyses of phoretic motion. At the continuum level the macroscopic hydrodynamic stress and interactive force with the solute sum to give zero total force, a condition for phoretic motion. At the colloidal level, the particle's motion is shown to have two contributions: 1) a 'back-flow' contribution composed of the motion of the colloidal particle due to the solute chemical potential gradient force acting on it and a compensating fluid motion driven by the long-range hydrodynamic velocity disturbance caused by the chemical potential gradient force acting on all the solute particles, and 2) an indirect contribution arising from the mutual interparticle and Brownian forces on the solute and phoretic particle; that contribution being nonzero because the distribution of solute about the phoretic particle is driven out of equilibrium by the chemical potential gradient of the solute. At the colloidal level the forces acting on the phoretic particle -- chemical potential gradient, Brownian, interparticle, etc. -- do not sum to zero, but rather are balanced by the Stokes drag of the solvent to give the net phoretic velocity. The analysis is applied to particles undergoing self-phoresis or autonomous motion, as can result from chemical reactions occurring asymmetrically on a particle surface, e.g. catalytic nanomotors, where it shown that the back-flow contribution is absent and the indirect Brownian and interparticle forces contribution is responsible for the motion.