Diffusiophoresis of a Spherical Soft Particle in Electrolyte Gradients

Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan, Republic of China.
The Journal of Physical Chemistry B (Impact Factor: 3.38). 05/2012; 116(25):7575-89. DOI: 10.1021/jp302836g
Source: PubMed

ABSTRACT An analytical study of the diffusiophoresis (consisting of electrophoresis and chemiphoresis) of a charged soft particle (or composite particle) composed of a spherical rigid core and a surrounding porous shell in an electrolyte solution prescribed with a uniform concentration gradient is presented. In the solvent-permeable and ion-penetrable porous surface layer of the particle, idealized frictional segments with fixed charges are assumed to distribute at a constant density. The electrokinetic equations that govern the electric potential profile, ionic concentration distributions, and fluid flow field inside and outside the porous layer of the particle are linearized by assuming that the system is only slightly distorted from equilibrium. Using a regular perturbation method, these linearized equations are solved with the fixed charge densities on the rigid core surface and in the porous shell as the small perturbation parameters. An analytical expression for the diffusiophoretic mobility of the soft sphere in closed form is obtained from a balance between its electrostatic and hydrodynamic forces. This expression, which is correct to the second order of the fixed charge densities, is valid for arbitrary values of κa, λa, and r(0)/a, where κ is the reciprocal of the Debye screening length, λ is the reciprocal of the length characterizing the extent of flow penetration inside the porous layer, a is the radius of the soft sphere, and r(0) is the radius of the rigid core of the particle. It is shown that a soft particle bearing no net charge can undergo diffusiophoresis (electrophoresis and chemiphoresis), and the direction of its diffusiophoretic velocity is decided by the fixed charges in the porous surface layer of the particle. In the limiting cases of large and small values of r(0)/a, the analytical solution describing the diffusiophoretic mobility for a charged soft sphere reduces to that for a charged rigid sphere and for a charged porous sphere, respectively.

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