Excluded-volume effects can play an important role in determining transport properties in diffusion of particles. Here, the diffusion of finite-sized hard-core interacting particles in two or three dimensions is considered systematically using the method of matched asymptotic expansions. The result is a nonlinear diffusion equation for the one-particle distribution function, with excluded-volume effects enhancing the overall collective diffusion rate. An expression for the effective (collective) diffusion coefficient is obtained. Stochastic simulations of the full particle system are shown to compare well with the solution of this equation for two examples.

Filters whose porosity decreases with depth are often more efficient at removing solute from a fluid than filters with a uniform porosity. We investigate this phenomenon via an extension of homogenization theory that accounts for a macroscale variation in microstructure. In the first stage of the paper, we homogenize the problems of flow through a filter with a near-periodic microstructure and of solute transport owing to advection, diffusion and filter adsorption. In the second stage, we use the computationally efficient homogenized equations to investigate and quantify why porosity gradients can improve filter efficiency. We find that a porosity gradient has a much larger effect on the uniformity of adsorption than it does on the total adsorption. This allows us to understand how a decreasing porosity can lead to a greater filter efficiency, by lowering the risk of localized blocking while maintaining the rate of total contaminant removal.

Stochastic models of diffusion with excluded-volume effects are used to model many biological and physical systems at a discrete level. The average properties of the population may be described by a continuum model based on partial differential equations. In this paper we consider multiple interacting subpopulations/species and study how the inter-species competition emerges at the population level. Each individual is described as a finite-size hard core interacting particle undergoing brownian motion. The link between the discrete stochastic equations of motion and the continuum model is considered systematically using the method of matched asymptotic expansions. The system for two species leads to a nonlinear cross-diffusion system for each subpopulation, which captures the enhancement of the effective diffusion rate due to excluded-volume interactions between particles of the same species, and the diminishment due to particles of the other species. This model can explain two alternative notions of the diffusion coefficient that are often confounded, namely collective diffusion and self-diffusion. Simulations of the discrete system show good agreement with the analytic results.

The problem of diffusion in a porous medium with a spatially varying porosity is considered. The particular microstructure analyzed comprises a collection of impenetrable spheres, though the methods developed are general. Two different approaches for calculating the effective diffusion coefficient as a function of the microstructure are presented. The first is a deterministic approach based on the method of multiple scales; the second is a stochastic approach for small volume fraction of spheres based on matched asymptotic expansions. We compare the two approaches, and we show good agreement between them in a number of example configurations.

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