scholarly journals The Gibbs Paradox

Entropy ◽  
2018 ◽  
Vol 20 (8) ◽  
pp. 552 ◽  
Author(s):  
Simon Saunders

The Gibbs Paradox is essentially a set of open questions as to how sameness of gases or fluids (or masses, more generally) are to be treated in thermodynamics and statistical mechanics. They have a variety of answers, some restricted to quantum theory (there is no classical solution), some to classical theory (the quantum case is different). The solution offered here applies to both in equal measure, and is based on the concept of particle indistinguishability (in the classical case, Gibbs’ notion of ‘generic phase’). Correctly understood, it is the elimination of sequence position as a labelling device, where sequences enter at the level of the tensor (or Cartesian) 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.

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Benjamin Yadin ◽  
Benjamin Morris ◽  
Gerardo Adesso

AbstractThe classical Gibbs paradox concerns the entropy change upon mixing two gases. Whether an observer assigns an entropy increase to the process depends on their ability to distinguish the gases. A resolution is that an “ignorant” observer, who cannot distinguish the gases, has no way of extracting work by mixing them. Moving the thought experiment into the quantum realm, we reveal new and surprising behaviour: the ignorant observer can extract work from mixing different gases, even if the gases cannot be directly distinguished. Moreover, in the macroscopic limit, the quantum case diverges from the classical ideal gas: as much work can be extracted as if the gases were fully distinguishable. We show that the ignorant observer assigns more microstates to the system than found by naive counting in semiclassical statistical mechanics. This demonstrates the importance of accounting for the level of knowledge of an observer, and its implications for genuinely quantum modifications to thermodynamics.


Entropy ◽  
2018 ◽  
Vol 20 (6) ◽  
pp. 392 ◽  
Author(s):  
Andrea Puglisi ◽  
Alessandro Sarracino ◽  
Angelo Vulpiani

Author(s):  
N. B. Slater

SynopsisThe writer's theory of unimolecular dissociation rates, based on the treatment of the molecule as a harmonically vibrating system, is put in a form which covers quantum as well as classical mechanics. The classical rate formulæ are as before, and are also the high-temperature limits of the new quantum formulæ. The high-pressure first-order rate k∞ is found first from the Gaussian distribution of co-ordinates and momenta of harmonic systems, and is justified for the quantum-mechanical case by Bartlett and Moyal's phase-space distributions. This leads to a re-formulation of k∞ as a molecular dissociation probability averaged over a continuum of states, and to a general rate for any pressure of the gas.The high-pressure rate k∞ is of the form ve-F/kT, where v and F depend, in the quantum case, on the temperature T; but v is always between the highest and lowest fundamental vibration frequencies of the molecule. Concerning the decline of the general rate k with pressure at fixed temperature, k/k∞ is to a certain approximation the same function of as was tabulated earlier for the classical case, apart from a constant factor changing the pressure scale in the quantum case.


Sign in / Sign up

Export Citation Format

Share Document