A new axiomatic treatment of equilibrium thermodynamics—thermostatics—is presented. The equilibrium states of a thermal system are assumed to be represented by a differentiable manifold of dimensionn + 1 (n finite). The empirical temperature is defined by the notion of thermal equilibrium. Empirical entropy is shown to exist for all systems with the property that the total work delivered along closed adiabats is zero. Absolute entropy and temperature follow from the additivity of heat and energy for two separate systems in thermal (...) equilibrium considered as a whole. The absolute temperature is defined up to a multiplicative constant. The exterior differentiable calculus of Cartan is introduced and in a subsequent paper its use for the derivation of standard results in thermostatics will be explained. (shrink)

This paper presents a new foundation of equilibrium thermodynamics based on certain ideas of T. Ehrenfest. The main result is the proof for the existence of entropy as a consequence of the conservation of energy for conservative thermal systems.

Gases reach equilibrium when left to themselves. Why do they behave in this way? The canonical answer to this question, originally proffered by Boltzmann, is that the systems have to be ergodic. This answer has been criticised on different grounds and is now widely regarded as flawed. In this paper we argue that some of the main arguments against Boltzmann's answer, in particular, arguments based on the KAM-theorem and the Markus-Meyer theorem, are beside the point. We then argue that something (...) close to Boltzmann's original proposal is true for gases: gases behave thermodynamic-like if they are epsilon-ergodic, i.e., ergodic on the entire accessible phase space except for a small region of measure epsilon. This answer is promising because there are good reasons to believe that relevant systems in statistical mechanics are epsilon-ergodic. (shrink)

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

The aim of this article is to analyse the relation between the second law of thermodynamics and the so-called arrow of time. For this purpose, a number of different aspects in this arrow of time are distinguished, in particular those of time-reversal (non-)invariance and of (ir)reversibility. Next I review versions of the second law in the work of Carnot, Clausius, Kelvin, Planck, Gibbs, Caratheodory and Lieb and Yngvason, and investigate their connection with these aspects of the arrow of time. It (...) is shown that this connection varies a great deal along with these formulations of the second law. According to the famous formulation by Planck, the second law expresses the irreversibility of natural processes. But in many other formulations irreversibility or even time-reversal non-invariance plays no role. I therefore argue for the view that the second law has nothing to do with the arrow of time. (shrink)

This paper investigates what the source of time-asymmetry is in thermodynamics, and comments on the question whether a time-symmetric formulation of the Second Law is possible.

Statistical mechanics is one of the crucial fundamental theories of physics, and in his new book Lawrence Sklar, one of the pre-eminent philosophers of physics, offers a comprehensive, non-technical introduction to that theory and to attempts to understand its foundational elements. Among the topics treated in detail are: probability and statistical explanation, the basic issues in both equilibrium and non-equilibrium statistical mechanics, the role of cosmology, the reduction of thermodynamics to statistical mechanics, and the alleged foundation of the very notion (...) of time asymmetry in the entropic asymmetry of systems in time. The book emphasises the interaction of scientific and philosophical modes of reasoning, and in this way will interest all philosophers of science as well as those in physics and chemistry concerned with philosophical questions. The book could also be read by an informed general reader interested in the foundations of modern science. (shrink)

An important contemporary version of Boltzmannian statistical mechanics explains the approach to equilibrium in terms of typicality. The problem with this approach is that it comes in different versions, which are, however, not recognized as such and not clearly distinguished. This article identifies three different versions of typicality‐based explanations of thermodynamic‐like behavior and evaluates their respective successes. The conclusion is that the first two are unsuccessful because they fail to take the system's dynamics into account. The third, however, is promising. (...) I give a precise formulation of the proposal and present an argument in support of its central contention. †To contact the author, please write to: Department of Philosophy, Logic, and Scientific Method, London School of Economics, Houghton Street, London WC2A 2AE, England; e‐mail: [email protected]. (shrink)

Philosophers of physics are very familiar with foundational problems in quantum mechanics and in the theory of relativity. In both fields, the puzzles, if not solved, are at least reasonably well formulated and possess well-characterized solution strategies. Sklar’s book Physics and Chance focuses on a pair of theories, thermodynamics and statistical mechanics, for which puzzles and foundational paradoxes abound, but where there is very little agreement upon the means with which they may best be approached. As he notes in the (...) introduction. (shrink)

In the usual procedure of deriving equilibrium thermodynamics from classical statistical mechanics, Gibbsian fine-grained entropy is taken as the analogue of thermodynamical entropy. However, it is well known that the fine-grained entropy remains constant under the Hamiltonian flow. In this paper it is argued that we need not search for alternatives for fine-grained entropy, nor do we have to reject Hamiltonian dynamics, in order to solve the problem of the constancy of fine-grained entropy and, more generally, to account for the (...) non-equilibrium part of the laws of thermodynamics. Rather, we have to weaken the requirement that equilibrium be identified with a stationary probability distribution. (shrink)

We introduce a simple model for so-called spin-echo experiments. We show that the model is a mincing system. On the basis of this model we study fine-grained entropy and coarse-grained entropy descriptions of these experiments. The coarse-grained description is shown to be unable to provide an explanation of the echo signals, as a result of the way in which it ignores dynamically generated correlations. This conclusion is extended to the general debate on the foundations of statistical mechanics. We emphasize the (...) need for an appropriate mechanism to explain the gradual suppression over time of the correlations in a thermodynamic system. We argue that such a mechanism can only be provided by the interventionist approach, in which the interaction of the system with its environment is taken into account. Irreversible behavior is then seen to arise not as a result of limited measurement accuracy , but as a result of the fact that thermodynamic systems are limited systems which interact with their environment. A detailed discussion is given of recent objections to the interventionist approach in the literature. (shrink)

In this paper I first argue that the objection which is most commonly levelled against the coarse-graining approach-viz. that it introduces an element of subjectivity into what ought to be a purely objective formalism-is ultimately unfounded. I then proceed to argue that two different objections to the coarse-graining approach indicate that it is an inadequate approach to statistical mechanics. The first objection is based on the fact that the appeal to appearances by the coarse-graining approach fails to justify the coarse-graining (...) strategy of ignoring the physical differences between so-called quasi-equilibrium distributions and equilibrium distributions. The second objection is centred on the notion of a coarse-grained entropy. I will argue that the required increase in the coarse-grained entropy is obtained by disregarding the dynamical constraints on the system. This undermines the very task statistical mechanics has set out to accomplish, viz. to provide a microdynamical underpinning of thermodynamics. (shrink)

A gas prepared in a non-equilibrium state will approach equilibrium and stay there. An influential contemporary approach to Statistical Mechanics explains this behaviour in terms of typicality. However, this explanation has been criticised as mysterious as long as no connection with the dynamics of the system is established. We take this criticism as our point of departure. Our central claim is that Hamiltonians of gases which are epsilon-ergodic are typical with respect to the Whitney topology. Because equilibrium states are typical, (...) we argue that there follows the desired conclusion that typical initial conditions approach equilibrium and stay there. (shrink)

This paper discusses the mistake of understanding the laws and concepts of thermodynamics too literally in the foundations of statistical mechanics. Arguing that this error is still made in subtle ways, the article explores its occurrence in three examples: the Second Law, the concept of equilibrium and the definition of phase transitions.

Why do systems prepared in a non-equilibrium state approach, and eventually reach, equilibrium? An important contemporary version of the Boltzmannian approach to statistical mechanics answers this question by an appeal to the notion of typicality. The problem with this approach is that it comes in different versions, which are, however, not recognised as such, much less clearly distinguished, and we often find different arguments pursued side by side. The aim of this paper is to disentangle different versions of typicality-based explanations (...) of thermodynamic behaviour and evaluate their respective success. My conclusion will be that the boldest version fails for technical reasons, while more prudent versions leave unanswered essential questions. (shrink)