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Violations of the Second Law of Thermodynamics



 
 
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  #1  
Old June 9th 19, 06:53 PM posted to sci.astro
Pentcho Valev
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Default Violations of the Second Law of Thermodynamics

An obviously absurd implication of the second law of thermodynamics is that a catalyst accelerates the forward and reverse reactions by exactly the same factor:

"In the presence of a catalyst, BOTH THE FORWARD AND REVERSE REACTION RATES WILL SPEED UP EQUALLY, thereby allowing the system to reach equilibrium faster. However, it is very important to keep in mind that the addition of a catalyst has no effect whatsoever on the final equilibrium position of the reaction. It simply gets it there faster. [...] If the addition of catalysts could possibly alter the equilibrium state of the reaction, this would violate the second rule of thermodynamics..." https://courses.lumenlearning.com/in...of-a-catalyst/

Actually things are far from "EQUALLY". Here is a catalyst that accelerates the forward reaction, 2H+ - H_2, but SUPPRESSES the reverse reaction, H_2 - 2H+ (violation of the second law of thermodynamics par excellence):

Yu Hang Li et al. Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters https://www.nature.com/articles/ncomms3500

http://images.nature.com/m685/nature...mms3500-f1.jpg

An analogous example (the forward and reverse reactions are not accelerated "EQUALLY"):

"In 2000, a simple, foundational thermodynamic paradox was proposed: a sealed blackbody cavity contains a diatomic gas and a radiometer whose apposing vane surfaces dissociate and recombine the gas to different degrees (A_2 ⇌ 2A). As a result of differing desorption rates for A and A_2 , there arise between the vane faces permanent pressure and temperature differences, either of which can be harnessed to perform work, in apparent conflict with the second law of thermodynamics." https://link.springer.com/article/10...701-014-9781-5

"Third, they [catalysts] do not alter final thermodynamic equilibria of their reactions. Epicatalysts bend this third principle in that they shift the final gas-phase equilibria of reactions..." https://www.sciencedirect.com/scienc...13138818301838

https://ars.els-cdn.com/content/imag...301838-gr1.jpg

Scientists should have noticed the obvious absurdity of this particular implication of the second law of thermodynamics long ago. Consider the dissociation-association reaction

A ⇌ B + C

which is in equilibrium. We add a catalyst, e.g. a macroscopic catalytic surface, and it starts splitting A - the rate constant of the forward (dissociation) reaction increases by a factor of, say, 745492. If the second law of thermodynamics is obeyed, the catalyst must increase the rate constant of the reverse (association) reaction by exactly the same factor, 745492. But this is obviously absurd! The reverse reaction is entirely different from the forward one - B and C must first get together, via diffusion, and only then can the catalyst join them to form A. Catalysts don't accelerate diffusion! If, in the extreme case, the reverse reaction is diffusion-controlled, the catalyst cannot accelerate it at all - the rate constant already has a maximal value determined by diffusion.

That catalysts can shift chemical equilibrium (and thereby violate the second law of thermodynamics) was my first heretical idea, 25-30 years ago. I believed my argument was convincing and enthusiastically submitted a short paper to Nature - they rejected it, as it were, before receiving it. My efforts to publish continued, mainly in The Journal of Physical Chemistry, and I was also active on Internet forums. The only result was this (I didn't take it seriously initially but in the end it proved fatal):

Athel Cornish-Bowden 1998: "Reading Mr Valev's postings to the BTK-MCA and other news groups and trying to answer all the nonsense contained in them incurs the risk of being so time-consuming that it takes over one's professional time completely, leaving none for more profitable activities. On the other hand, not answering them incurs the even greater risk that some readers of the news group may think that his points are unanswerable and that thermodynamics, kinetics, catalysis etc. rest on as fragile a foundation as he pretends. [...] Can a catalyst shift the position of an equilibrium? No. Absolutely not if it is a true catalyst present at very low concentrations. If it is present at a concentration comparable with that of one or more of the reactants then it may appear to shift the position of equilibrium by mass action effects. However, when it does this it is acting as a reactant, not as a catalyst. Mr Valev's claims to have shown otherwise... [...] Suffice it to say that if Mr Valev really believed what he was saying he would not be writing nonsense on this news group, he would be building the machine that would make him the richest man in Bulgaria (or even the world)." http://bip.cnrs-mrs.fr/bip10/valevfaq.htm

Pentcho Valev
  #2  
Old June 9th 19, 11:45 PM posted to sci.astro
Pentcho Valev
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Default Violations of the Second Law of Thermodynamics

Misleading education:

"A necessary component of a heat engine...is that two temperatures are involved" http://physics.bu.edu/~duffy/py105/Heatengines.html

Actually one-temperature (isothermal) heat engines are commonplace - e.g. pH-sensitive polymers can do work, at the expense of ambient heat, as they swell or contract. No "two temperatures" involved:

https://pbs.twimg.com/media/Dqasx5_WoAAV6XY.jpg

By adding and removing hydrogen ions (H+) one can cyclically extract work from pH-sensitive polymers:

https://pbs.twimg.com/media/DmP8OHKXcAAerSI.jpg

(This is Fig. 4 on p. 15 he https://www.ncbi.nlm.nih.gov/pmc/art...00645-0017.pdf)

Adding and removing H+, per se, consumes no work if done QUASISTATICALLY. This means that the work lost e.g. in adding is compensated by the work gained in removing, and the net work involved is zero.

In his lectures http://www.feynmanlectures.caltech.edu/I_44.html Feynman discusses the non-isothermal analog which, at least apparently, doesn't violate the second law:

http://readingpenrose.files.wordpres...and-engine.gif

In the isothermal case the two temperatures are replaced by "adding and removing H+" which, if performed QUASISTATICALLY, consumes no work. So the system just lifts weights for us, at the expense of ambient heat and in violation of the second law of thermodynamics.

Heat engines working under isothermal conditions (no "two temperatures") and able to violate the second law of thermodynamics are commonplace. They are too slow and impuissant to be of any technological importance, and this is one of the reasons why scientists pay them no attention. Yet there seems to be an exception: When water is placed in an electric field, the non-conservative force (pressure) that emerges in the bulk triggers turbulent motion apparently able to convert ambient heat into work quite vigorously:

https://www.youtube.com/watch?v=17UD1goTFhQ

Pentcho Valev
  #3  
Old June 10th 19, 03:14 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Violations of the Second Law of Thermodynamics

The only reason why the false second law is still invincible is that thermodynamics is a "dismal swamp of obscurity" - rational criticism is impossible. There are countless versions of the second law incompatible with one another, countless entropies incompatible with one another, etc:

Clifford Truesdell, The Tragicomical History of Thermodynamics, 1822-1854, p. 6: "Finally, I confess to a heartfelt hope - very slender but tough - that even some thermodynamicists of the old tribe will study this book, master the contents, and so share in my discovery: Thermodynamics need never have been the DISMAL SWAMP OF OBSCURITY that from the first it was and that today in common instruction it is; in consequence, it need not so remain." [....] p. 333: "Clausius' verbal statement of the "Second Law" makes no sense, for "some other change connected therewith" introduces two new and unexplained concepts: "other change" and "connection" of changes. Neither of these finds any place in Clausius' formal structure. All that remains is a Mosaic prohibition. A century of philosophers and journalists have acclaimed this commandment; a century of mathematicians have shuddered and averted their eyes from the unclean." https://www.amazon.com/Tragicomical-.../dp/1461394465

Jos Uffink, Bluff your way in the Second Law of Thermodynamics: "I therefore argue for the view that THE SECOND LAW HAS NOTHING TO DO WITH THE ARROW OF TIME. [...] Before one can claim that acquaintance with the Second Law is as indispensable to a cultural education as Macbeth or Hamlet, it should obviously be clear what this law states. This question is surprisingly difficult. The Second Law made its appearance in physics around 1850, but a half century later it was already surrounded by so much confusion that the British Association for the Advancement of Science decided to appoint a special committee with the task of providing clarity about the meaning of this law.. However, its final report (Bryan 1891) did not settle the issue. Half a century later, the physicist/philosopher Bridgman still complained that there are almost as many formulations of the second law as there have been discussions of it. And EVEN TODAY, THE SECOND LAW REMAINS SO OBSCURE that it continues to attract new efforts at clarification." http://philsci-archive.pitt.edu/313/1/engtot.pdf

Pentcho Valev
 




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