Free volume of the hard spheres gas

Abstract

The Enskog factor χ plays a central role in the theory of dense gases, quantifying how the finite size of molecules causes many physical quantities, such as the equation of state, the mean free path, and the diffusion coefficient, to deviate from those of an ideal gas. We suggest an intuitive but rigorous derivation of this fact by showing how all these instances of χ amount to different ways of looking at the derivative of the free volume with respect to the packing density. We show how to compute the free volume explicitly for finitely many molecules in a finite box and demonstrate excellent agreement between its derivative and mean free paths obtained from computer simulations, where the number of molecules N varies from 1000 down to 2, and where the mean free paths vary from many times the molecular diameter at low density down to a small fraction of the molecular diameter at high density. Since the boundary corrections involved are relatively simple and intuitive this strengthens the link between the teaching of large N theory for real physical systems, and the running of small N simulations in undergraduate physics laboratories.