Insights into the Second Law of Thermodynamics from Anisotropic Gas-Surface Interactions

Thermodynamic implications of anisotropic gas-surface interactions in a closed molecular flow cavity are examined. Anisotropy at the microscopic scale, such as might be caused by reduced-dimensionality surfaces, is shown to lead to reversibility at the macroscopic scale. The possibility of a self-sustaining nonequilibrium stationary state induced by surface anisotropy is demonstrated that simultaneously satisfies flux balance, conservation of momentum, and conservation of energy. Conversely, it is also shown that the second law of thermodynamics prohibits anisotropic gas-surface interactions in “equilibrium”, even for reduced dimensionality surfaces. This is particularly startling because reduced dimensionality surfaces are known to exhibit a plethora of anisotropic properties. That gas-surface interactions would be excluded from these anisotropic properties is completely counterintuitive from a causality perspective. These results provide intriguing insights into the second law of thermodynamics and its relation to gas-surface interaction physics. Sandia National Laboratories is the author’s employer, but is not officially affiliated with this work.