Diffusion in fluids with large mean free paths: Non-classical behavior between Knudsen and Fickian limits

Diffusion in fluids is analyzed at non-classical conditions, intermediate between the Knudsen and Fickian limits. The fluid is considered in the framework of the Einstein's diffusion evolution equation involving expansions of the density distribution in powers of displacement and time. The standard truncation of these expansions results in the classical model of diffusion; however, higher-order terms lead to a departure from classical behavior. This has not been studied or discussed adequately in the literature previously. Here, we present an exact solution of the Einstein's diffusion evolution equation without truncation of the density expansions. This solution illustrates limitations in the classical truncations and demonstrates non-classical effects due to large mean free paths, lambda. In particular, this new solution shows that, at large lambda, there are significant quantitative deviations from classical diffusion profiles. In addition, this solution demonstrates a dramatic change in the diffusion mechanism from the state where the molecular motions are predominantly ballistic to one of molecular chaos. This has implications for fundamentals of fluids between the Knudsen and Fickian limits, and for a variety of fields where evolution of a system includes random, multi-scale displacement of particles, such as nanotechnology, vacuum techniques, turbulence, and astrophysics. (C) 2009 Elsevier B.V. All rights reserved.