Polydisperse Colloids Two-Moment Diffusion Model Through Irreversible Thermodynamics Considerations

This study deals with the problem of diffusion for polydisperse colloids. The resolution of this complex problem usually requires computationally expensive numerical models. By considering the number of colloidal particles and their mass as independent variables, the equations of state for a dilute polydisperse colloid are derived on a statistical mechanics basis. Irreversible thermodynamics is then applied to obtain a simple two-moment diffusion model. The validity of the model is illustrated by comparing its results with those obtained by a classical size spectrum approach, in a sedimentation equilibrium problem and in an unsteady one-dimensional diffusion problem in Stokes–Einstein regime, and under the hypothesis that the size spectrum distribution is stochastic. In the first problem, the two-moment diffusion problem allows to represent rigorously the vertical size segregation induced by gravity, while in the second one, it allows a convenient description of the diffusion of polydisperse colloids by using two coupled diffusion equations, with an accuracy comparable with that of the classical size spectrum approach. The contribution of our work lies primarily in the application of a non-equilibrium thermodynamics methodology to a challenging issue of colloid modeling, namely, polydispersity, by going from statistical mechanics to the derivation of phenomenological coefficients, with the two-moment approach as a guideline.