Gibbs "Paradox" and the Entropy of mixing

In summary, Gibbs' paradox is resolved by the fact that particles are indistinguishable and their bosonic or fermionic nature.
  • #1
rentier
5
1
(not a paradox nowadays, but it was an issue for years)
https://en.m.wikipedia.org/wiki/Gibbs_paradox
The two gases may be arbitrarily similar, but the entropy from mixing does not disappear unless they are the same gas - a paradoxical discontinuity.

It's not a question about a formula. I don't understand the motivation in physics to claim Gibbs mixing "paradox", the discontinuity point. What bothers the physicist to ask for a continuous transition between distinguishable and indistinguishable particles mixing (entropy).
Is it paradox that a sieve separates larger particles and smaller ones? No matter how small the difference is (in theory)? Is it paradox that 0. (real number) is different from any even the smallest number?
Either I can distinguish the particles or not. It's a binary statement/situation. Of course, it's discontinuous by definition. Two different systems; one with distinguishable particles, the other not.
Neither does it clash with the understanding of entropy as a measure of ignorance. If I can somehow differentiate particles, there is a decrease in entropy. I could (more or less laboriously) separate them and reverse the mixing.

I can't catch a logical link to the paradox.
 
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  • #3
The ironic thing is that classical statistical physics is more complicated than quantum statistical physics because of such issues.

One should be aware of the fact that before the "quantum revolution" there was no idea that particles are indistinguishable at all. The reason is simple: Within classical mechanics you can label each individual particle and exactly follow its trajectory. So each particle is individually labelled, e.g., by assigning its initial coordinates at some time ##t=0## to it.

Consequently when Boltzmann invented his "counting method" for microstates, he treated the particles as distinguishable, which lead to the problem with the nonadditivity of entropy and an apparent change of macroscopic state where in fact there is none (with the usual Gibbs paradox, leading to mixing energy where in fact nothing is mixed). Ingenious as Boltzmann was he put another factor ##1/N!## in his counting, i.e., assuming that there's no way to distinguish in the macrostate the individual particles in the container, but that's in fact a clear contradiction to classical mechanis, where the particles are in principle distinguishable. The puzzle thus was, how to justify this additional factor, and the answer was finally given by the modern quantum theory of many-body systems, i.e., the indistinguishability of particles and their bosonic or fermionic nature. The classical limit of course does not lead to distinguishable particles at all, and that solves the problem in saying that you need to keep some quantum aspects also in classical statistical physics, among them the indistinguishability of particles of the same sort. Of course if you have particles of different sort the mixing entropy is real and measurable and also comes out in quantum statistics as it must be.
 
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Likes etotheipi, rentier and Lord Jestocost
  • #4
Thanks a lot to you three: Jaynes (tribute), vanhees71, Andy.
I started reading Jaynes, appreciate it so far, interesting and readable, as you recommended, Andy.

@vanhees71: thanks once more for your detailed explanations. I think it is crucial, your remark that the Old Geniuses had just started to explain such subjects. I try to adjust some things in my head, and follow. Thanks.
 

What is the Gibbs Paradox?

The Gibbs Paradox is a paradox in thermodynamics that deals with the concept of entropy and mixing. It states that the entropy of mixing two identical gases should be zero, but experimental evidence shows that it is not. This paradox highlights the limitations of classical thermodynamics and the need for a more comprehensive understanding of entropy.

How does the Gibbs Paradox relate to entropy?

The Gibbs Paradox is directly related to the concept of entropy. Entropy is a measure of the disorder or randomness in a system. In the case of mixing two identical gases, classical thermodynamics predicts that there should be no increase in entropy since the gases are identical. However, experimental evidence shows that there is an increase in entropy, leading to the paradox.

What is the significance of the Gibbs Paradox?

The Gibbs Paradox is significant because it highlights the limitations of classical thermodynamics and the need for a more comprehensive understanding of entropy. It also raises questions about the nature of entropy and its relationship to the microscopic behavior of particles. This paradox has led to further research and developments in the field of thermodynamics and statistical mechanics.

How has the Gibbs Paradox been resolved?

The Gibbs Paradox has been resolved through the use of statistical mechanics. Statistical mechanics takes into account the microscopic behavior of particles and explains the increase in entropy when mixing two identical gases. This resolution has been confirmed through experimental evidence and has furthered our understanding of entropy and thermodynamics.

What are the practical implications of the Gibbs Paradox?

The Gibbs Paradox has practical implications in fields such as chemical engineering and material science. It has led to a better understanding of the behavior of mixtures and the design of more efficient processes. It has also influenced the development of new technologies and materials, such as polymers, that rely on the principles of thermodynamics and entropy.

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