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.

In Boltzmannian statistical mechanics macro-states supervene on micro-states. This leads to a partitioning of the state space of a system into regions of macroscopically indistinguishable micro-states. The largest of these regions is singled out as the equilibrium region of the system. What justifies this association? We review currently available answers to this question and find them wanting both for conceptual and for technical reasons. We propose a new conception of equilibrium and prove a mathematical theorem which establishes in full generality (...) -- i.e. without making any assumptions about the system's dynamics or the nature of the interactions between its components -- that the equilibrium macro-region is the largest macro-region. We then turn to the question of the approach to equilibrium, of which there exists no satisfactory general answer so far. In our account, this question is replaced by the question when an equilibrium state exists. We prove another -- again fully general -- theorem providing necessary and sufficient conditions for the existence of an equilibrium state. This theorem changes the way in which the question of the approach to equilibrium should be discussed: rather than launching a search for a crucial factor, the focus should be on finding triplets of macro-variables, dynamical conditions, and effective state spaces that satisfy the conditions of the theorem. (shrink)

Boltzmannian statistical mechanics partitions the phase space of a sys- tem into macro-regions, and the largest of these is identified with equilibrium. What justifies this identification? Common answers focus on Boltzmann’s combinatorial argument, the Maxwell-Boltzmann distribution, and maxi- mum entropy considerations. We argue that they fail and present a new answer. We characterise equilibrium as the macrostate in which a system spends most of its time and prove a new theorem establishing that equilib- rium thus defined corresponds to the largest (...) macro-region. Our derivation is completely general in that it does not rely on assumptions about a system’s dynamics or internal interactions. (shrink)

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

On the observational equivalence of continuous-time deterministic and indeterministic descriptions Content Type Journal Article Pages 193-225 DOI 10.1007/s13194-010-0011-5 Authors Charlotte Werndl, Department of Philosophy, Logic and Scientific Method, London School of Economics, Houghton Street, London, WC2A 2AE UK Journal European Journal for Philosophy of Science Online ISSN 1879-4920 Print ISSN 1879-4912 Journal Volume Volume 1 Journal Issue Volume 1, Number 2.

The central question of this paper is: are deterministic and indeterministic descriptions observationally equivalent in the sense that they give the same predictions? I tackle this question for measure-theoretic deterministic systems and stochastic processes, both of which are ubiquitous in science. I first show that for many measure-theoretic deterministic systems there is a stochastic process which is observationally equivalent to the deterministic system. Conversely, I show that for all stochastic processes there is a measure-theoretic deterministic system which is observationally equivalent (...) to the stochastic process. Still, one might guess that the measure-theoretic deterministic systems which are observationally equivalent to stochastic processes used in science do not include any deterministic systems used in science. I argue that this is not so because deterministic systems used in science even give rise to Bernoulli processes. Despite this, one might guess that measure-theoretic deterministic systems used in science cannot give the same predictions at every observation level as stochastic processes used in science. By proving results in ergodic theory, I show that also this guess is misguided: there are several deterministic systems used in science which give the same predictions at every observation level as Markov processes. All these results show that measure-theoretic deterministic systems and stochastic processes are observationally equivalent more often than one might perhaps expect. Furthermore, I criticise the claims of the previous philosophy papers Suppes (1993, 1999), Suppes and de Barros (1996) and Winnie (1998) on observational equivalence. (shrink)