Distinguishability plays a major role in quantum and statistical physics. When particles are identical their wave function must be either symmetric or antisymmetric under permutations and the number of microscopic states, which determines entropy, is counted up to permutations. When the particles are distinguishable, wavefunctions have no symmetry and each permutation is a different microstate. This binary and discontinuous classification raises a few questions: one may wonder what happens if particles are almost identical, or when the property that distinguishes between (...) them is irrelevant to the physical interactions in a given system. Here I sketch a general answer to these questions. For any pair of non-identical particles there is a timescale, \, required for a measurement to resolve the differences between them. Below \, particles seem identical, above it - different, and the uncertainty principle provides a lower bound for \. Thermal systems admit a conjugate temperature scale, \. Above this temperature the system appears to equilibrate before it resolves the differences between particles, below this temperature the system identifies these differences before equilibration. As the physical differences between particles decline towards zero, \ and \. (shrink)

In this essay I critically examine the role of entropy of mixing in articulating a macroscopic criterion for the sameness and difference of chemical substances. Consider three cases of mixing in which entropy change occurs: isotopic variants, spin isomers, and populations of atoms in different orthogonal quantum states. Using these cases I argue that entropy of mixing tracks differences between physical states, differences that may or may not correspond to a difference of substance. It does not provide a criterion for (...) the sameness and difference of substance that is appropriate to chemistry. (shrink)

The long history of ergodic and quasi-ergodic hypotheses provides the best example of the attempt to supply non-probabilistic justifications for the use of statistical mechanics in describing mechanical systems. In this paper we reverse the terms of the problem. We aim to show that accepting a probabilistic foundation of elementary particle statistics dispenses with the need to resort to ambiguous non-probabilistic notions like that of (in)distinguishability. In the quantum case, starting from suitable probability conditions, it is possible to deduce elementary (...) particle statistics in a unified way. Following our approach Maxwell-Boltzmann statistics can also be deduced, and this deduction clarifies its status.Thus our primary aim in this paper is to give a mathematically rigorous deduction of the probability of a state with given energy for a perfect gas in statistical equilibrium; that is, a deduction of the equilibrium distribution for a perfect gas. A crucial step in this deduction is the statement of a unified statistical theory based on clearly formulated probability conditions from which the particle statistics follows. We believe that such a deduction represents an important improvement in elementary particle statistics, and a step towards a probabilistic foundation of statistical mechanics.In this Part I we first present some history: we recall some results of Boltzmann and Brillouin that go in the direction we will follow. Then we present a number of probability results we shall use in Part II. Finally, we state a notion of entropy referring to probability distributions, and give a natural solution to Gibbs' paradox. (shrink)

This article considers the Gibbs paradox and its implications for three definitions of entropy in statistical mechanics: the “classical” Boltzmann entropy ; the modified Boltzmann entropy that is usually proposed in response to the paradox ; and a generalized version of the latter. It is argued that notwithstanding a recent suggestion to the contrary, the paradox does imply that SB1 is not a satisfactory definition of entropy; SB2 is undermined by “second-order” versions of the paradox; and SB2G solves the paradox (...) but is not a satisfactory definition of entropy. (shrink)

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

This is a systematic review of the concept of indistinguishability, in both classical and quantum mechanics, with particular attention to Gibbs paradox. Section 1 is on the Gibbs paradox; section 2 is a defense of classical indistinguishability, notwithstanding the widely-held view, that classical particles can always be distinguished by their trajectories. The last section is about the notion of object more generally, and on whether indistinguishables should be thought of as objects at all.

The Gibbs Paradox is essentially a set of open questions as to how sameness of gases or fluids are to be treated in thermodynamics and statistical mechanics. They have a variety of answers, some restricted to quantum theory, some to classical theory. The solution offered here applies to both in equal measure, and is based on the concept of particle indistinguishability. Correctly understood, it is the elimination of sequence position as a labelling device, where sequences enter at the level of (...) the tensor product of one-particle state spaces. In both cases it amounts to passing to the quotient space under permutations. ‘Distinguishability’, in the sense in which it is usually used in classical statistical mechanics, is a mathematically convenient, but physically muddled, fiction. (shrink)