On the (Boltzmann) entropy of non-equilibrium systems

Boltzmann defined the entropy of a macroscopic system in a macrostate M as the log of the volume of phase space (number of microstates) corresponding to M. This agrees with the thermodynamic entropy of Clausius when M specifies the locally conserved quantities of a system in local thermal equilibrium (LTE). Here we discuss Boltzmann's entropy, involving an appropriate choice of macro-variables, for systems not in LTE. We generalize the formulas of Boltzmann for dilute gases and of Resibois for hard sphere fluids and show that for macro-variables satisfying any deterministic autonomous evolution equation arising from the microscopic dynamics the corresponding Boltzmann entropy must satisfy an H-theorem. (C) 2004 Published by Elsevier B.V.