Abstract

Consider a gas that is adiabatically isolated from its environment and confined to the left half of a container. Then remove the wall separating the two parts. The gas will immediately start spreading and soon be evenly distributed over the entire available space. The gas has approached equilibrium. Thermodynamics (TD) characterizes this process in terms of an increase of thermodynamic entropy, which attains its maximum value at equilibrium. The second law of thermodynamics captures the irreversibility of this process by positing that in an isolated system such as the gas entropy cannot decrease. The aim of statistical mechanics (SM) is to explain the behavior of the gas and, in particular, its conformity with the second law in terms of the dynamical laws governing the individual molecules of which the gas is made up. In what follows these laws are assumed to be the ones of Hamiltonian classical mechanics. We should not, however, ask for an explanation of the second law literally construed. This law is a universal law and as such cannot be explained by a statistical theory. But this is not a problem because we..