Time evolution of the Boltzmann entropy for a nonequilibrium dilute gas

Abstract

We investigate the time evolution of the Boltzmann entropy of a dilute gas of N particles, N>>1, as it undergoes a free expansion doubling its volume. The microstate of the system, a point in the 4N dimensional phase space, changes in time via Hamiltonian dynamics. Its entropy, at any time $t$, is given by the logarithm of the phase space volume of all the microstates giving rise to its macrostate at time $t$. The macrostates that we consider are defined by coarse graining the one-particle phase space into cells $\Delta_\alpha$. The initial and final macrostates of the system are equilibrium states in volumes $V$ and $2V$, with the same energy $E$ and particle number $N$. Their entropy per particle is given, for sufficiently large systems, by the thermodynamic entropy as a function of the particle and energy density, whose leading term is independent of the size of the $\Delta_\alpha$. The intermediate (non-equilibrium) entropy does however depend on the size of the cells $\Delta_\alpha$. Its change with time is due to (i) dispersal in physical space from free motion and to (ii) the collisions between particles which change their velocities. The former depends strongly on the size of the velocity coarse graining $\Delta v$: it produces entropy at a rate proportional to $\Delta v$. This dependence is investigated numerically and analytically for a dilute two-dimensional gas of hard discs. It becomes significant when the mean free path between collisions is of the same order or larger than the length scale of the initial spatial inhomogeneity. In the opposite limit, the rate of entropy production is essentially independent of $\Delta v$ and is given by the Boltzmann equation for the limit $\Delta v\rightarrow 0$. We show that when both processes are active the time dependence of the entropy has a scaling form involving the ratio of the rates of its production by the two processes.