Statistical method for modeling Knudsen diffusion in nanopores

This paper presents a statistical method for the calculation of gaseous flux and diffusion coefficients through a Knudsen-regime cylindrical nanopore. A general integral formula for the flux is derived in terms of collision frequency, molecular density, and a scattering path length probability distribution. Under appropriate steady-state assumptions, the general formula simplifies to Fick's first law, from which an expression for the diffusion coefficient is derived. The model is shown to be dimensionally consistent with the Einstein relation. The conditions for agreement with Fick's second law are investigated. Using a model probability distribution the model leads to an expression for the diffusion coefficient for a pore of finite length. This result is shown to compare favorably with a classic formula from the literature.