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tech / sci.math / Re: Entropy Means...Nothing!

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* Entropy Means...Nothing!Pentcho Valev
`- Re: Entropy Means...Nothing!Pentcho Valev

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Entropy Means...Nothing!

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Subject: Entropy Means...Nothing!
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 by: Pentcho Valev - Sun, 12 Feb 2023 17:49 UTC

Athel Cornish-Bowden https://en.wikipedia.org/wiki/Athel_Cornish-Bowden: "The concept of entropy was introduced to thermodynamics by Clausius, who deliberately chose an obscure term for it, wanting a word based on Greek roots that would sound similar to "energy". In this way he hoped to have a word that would mean the same to everyone regardless of their language, and, as Cooper [2] remarked, he succeeded in this way in finding a word that meant the same to everyone: NOTHING. From the beginning it proved a very difficult concept for other thermodynamicists, even including such accomplished mathematicians as Kelvin and Maxwell; Kelvin, indeed, despite his own major contributions to the subject, never appreciated the idea of entropy [3]. The difficulties that Clausius created have continued to the present day, with the result that a fundamental idea that is absolutely necessary for understanding the theory of chemical equilibria continues to give trouble, not only to students but also to scientists who need the concept for their work." https://www.beilstein-institut.de/download/712/cornishbowden_1.pdf

Any thermodynamicist would (reluctantly) agree that, if the entropy is not a state function, then it is nonsense. But then the thermodynamicist would say that the entropy IS a state function and that this has been proved since Clausius. At the end the thermodynamicist might even quote Einstein and Eddington who highly valued the ideology of thermodynamics as a prototype of the ideology of relativity.

Is there any proof that the entropy is a state function? There is none. Here is the oversimplified history of the entropy concept:

If you define the entropy S as a quantity that obeys the equation dS=dQrev/T, you will find that, so defined, the entropy is a state function FOR AN IDEAL GAS: https://socratic.org/questions/is-entropy-state-function-how-prove-it Clausius decided to prove that the entropy (so defined) is a state function for ANY system. He based his proof on the assumption that any cycle can be disintegrated into small Carnot cycles, and nowadays this proof remains the only justification of "Entropy is a state function":

"Carnot Cycles: S is a State Function. Any reversible cycle can be thought of as a collection of Carnot cycles - this approximation becomes exact as cycles become infinitesimal. Entropy change around an individual cycle is zero. Sum of entropy changes over all cycles is zero." http://mutuslab.cs.uwindsor.ca/schurko/introphyschem/lectures/240_l10.pdf

The assumption on which "Entropy is a state function" is based - that any cycle can be subdivided into small Carnot cycles - is obviously false. An isothermal cycle CANNOT be subdivided into small Carnot cycles, a cycle involving the action of conservative forces CANNOT be subdivided into small Carnot cycles, etc. etc.

Conclusion: The belief that the entropy is a state function is totally unjustified. Any time scientists use the term "entropy", they don't know what they are talking about:

"My greatest concern was what to call it. I thought of calling it 'information', but the word was overly used, so I decided to call it 'uncertainty'. When I discussed it with John von Neumann, he had a better idea. Von Neumann told me, 'You should call it entropy, for two reasons: In the first place your uncertainty function has been used in statistical mechanics under that name, so it already has a name. In the second place, and more important, nobody knows what entropy really is, so in a debate you will always have the advantage." https://en.wikipedia.org/wiki/History_of_entropy

Here Sabine Hossenfelder extensively uses the term "entropy" (nobody knows what entropy really is so she sounds very convincing):

https://www.youtube.com/watch?v=2QnRpinVmo4&t=8s

Pentcho Valev

Re: Entropy Means...Nothing!

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Subject: Re: Entropy Means...Nothing!
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 by: Pentcho Valev - Mon, 13 Feb 2023 09:37 UTC

Arthur Eddington: "The law that entropy always increases—the Second Law of Thermodynamics—holds, I think, the supreme position among the laws of Nature. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell’s equations—then so much the worse for Maxwell’s equations. If it is found to be contradicted by observation—well these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of thermodynamics I can give you no hope; there is nothing for it but to collapse in deepest humiliation." https://todayinsci.com/E/Eddington_Arthur/EddingtonArthur-Entropy-Quotations.htm

The version of the second law of thermodynamics known as "Entropy always increases" is in fact a theorem deduced by Clausius in 1865:

Jos Uffink, professor at the University of Minnesota, p. 37: "Hence we obtain: THE ENTROPY PRINCIPLE (Clausius' version) For every nicht umkehrbar [irreversible] process in an adiabatically isolated system which begins and ends in an equilibrium state, the entropy of the final state is greater than or equal to that of the initial state. For every umkehrbar [reversible] process in an adiabatical system, the entropy of the final state is equal to that of the initial state." http://philsci-archive.pitt.edu/archive/00000313/

Clausius' deduction was predicated on three postulates:

Postulate 1 (implicit): The entropy is a state function.

Postulate 2: Clausius' inequality (formula 10 on p. 33 in Uffink's article) is correct.

Postulate 3: Any irreversible process can be closed by a reversible process to become a cycle.

The three postulates remain totally unjustified even nowadays. Postulate 1 can easily be disproved by considering cycles (heat engines) converting heat into work in ISOTHERMAL conditions. Postulate 3 is repudiated even in official thermodynamics:

Uffink, p.39: "A more important objection, it seems to me, is that Clausius bases his conclusion that the entropy increases in a nicht umkehrbar [irreversible] process on the assumption that such a process can be closed by an umkehrbar [reversible] process to become a cycle. This is essential for the definition of the entropy difference between the initial and final states.. But the assumption is far from obvious for a system more complex than an ideal gas, or for states far from equilibrium, or for processes other than the simple exchange of heat and work. Thus, the generalisation to all transformations occurring in Nature is somewhat rash."

Note that the theorem only holds for "an adiabatically isolated system which begins and ends in an equilibrium state". This means that, even if Clausius's postulates were true (they are not), all applications of "Entropy always increases" to processes which do not begin and end in equilibrium would still be unjustified!

Pentcho Valev

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