Hermann von Helmholtz (1821-1894) participated in two of the most significant developments in physics and in the philosophy of science in the 19th century: the proof that Euclidean geometry does not describe the only possible visualizable and physical space, and the shift from physics based on actions between particles at a distance to the field theory. Helmholtz achieved a staggering number of scientific results, including the formulation of energy conservation, the vortex equations for fluid dynamics, the notion of free energy (...) in thermodynamics, and the invention of the ophthalmoscope. His constant interest in the epistemology of science guarantees his enduring significance for philosophy. (shrink)

Roughly speaking, classical statistical physics is the branch of theoretical physics that aims to account for the thermal behaviour of macroscopic bodies in terms of a classical mechanical model of their microscopic constituents, with the help of probabilistic assumptions. In the last century and a half, a fair number of approaches have been developed to meet this aim. This study of their foundations assesses their coherence and analyzes the motivations for their basic assumptions, and the interpretations of their central concepts. (...) The most outstanding foundational problems are the explanation of time-asymmetry in thermal behaviour, the relative autonomy of thermal phenomena from their microscopic underpinning, and the meaning of probability. A more or less historic survey is given of the work of Maxwell, Boltzmann and Gibbs in statistical physics, and the problems and objections to which their work gave rise. Next, we review some modern approaches to (i) equilibrium statistical mechanics, such as ergodic theory and the theory of the thermodynamic limit; and to (ii) non-equilibrium statistical mechanics as provided by Lanford's work on the Boltzmann equation, the so-called Bogolyubov-Born-Green-Kirkwood-Yvon approach, and stochastic approaches such as `coarse-graining' and the `open systems' approach. In all cases, we focus on the subtle interplay between probabilistic assumptions, dynamical assumptions, initial conditions and other ingredients used in these approaches. (shrink)

This is an extensive review of recent work on the foundations of statistical mechanics.

In a previous work (M. Campisi. Stud. Hist. Phil. M. P. 36 (2005) 275-290) we have addressed the mechanical foundations of equilibrium thermodynamics on the basis of the Generalized Helmholtz Theorem. It was found that the volume entropy provides a good mechanical analogue of thermodynamic entropy because it satisfies the heat theorem and it is an adiabatic invariant. This property explains the ``equal'' sign in Clausius principle ($S_f \geq S_i$) in a purely mechanical way and suggests that the volume entropy (...) might explain the ``larger than'' sign (i.e. the Law of Entropy Increase) if non adiabatic transformations were considered. Based on the principles of microscopic (quantum or classical) mechanics here we prove that, provided the initial equilibrium satisfy the natural condition of decreasing ordering of probabilities, the expectation value of the volume entropy cannot decrease for arbitrary transformations performed by some external sources of work on a insulated system. This can be regarded as a rigorous quantum mechanical proof of the Second Law. We discuss how this result relates to the Minimal Work Principle and improves over previous attempts. The natural evolution of entropy is towards larger values because the natural state of matter is at positive temperature. Actually the Law of Entropy Decrease holds in artificially prepared negative temperature systems. (shrink)

Based on the property of extensivity , we derive in a mathematically consistent manner the explicit expressions of the chemical potential μμ and the Clausius entropy S for the case of monoatomic ideal gases in open systems within phenomenological thermodynamics. Neither information theoretic nor quantum mechanical statistical concepts are invoked in this derivation. Considering a specific expression of the constant term of S, the derived entropy coincides with the Sackur–Tetrode entropy in the thermodynamic limit. We demonstrate, however, that the former (...) limit is not contained in the classical thermodynamic relations, implying that the usual resolutions of Gibbs paradox do not succeed in bridging the gap between the thermodynamics and statistical mechanics. We finally consider the volume of the phase space as an entropic measure, albeit, without invoking the thermodynamic limit to investigate its relation to the thermodynamic equation of state and observables. (shrink)

A gas relaxing into equilibrium is often taken to be a process in which a system moves from an “improbable” to a “probable” state. Given that the thermodynamic entropy increases during such a process, it is natural to conjecture that the thermodynamic entropy is a measure of the probability of a macrostate. For nonideal classical gases, however, I claim that there is no clear sense in which the thermodynamic entropy of a macrostate measures its probability. We must therefore reject the (...) idea that thermodynamic entropy and probability are connected in a deep and general way. (shrink)