Discussion:
Catalysts Do Violate the Second Law of Thermodynamics
(trop ancien pour répondre)
Pentcho Valev
2018-07-13 17:19:20 UTC
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"In the presence of a catalyst, both the forward and reverse reaction rates will speed up EQUALLY... [...] 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/introchem/chapter/the-effect-of-a-catalyst/

In many cases 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):

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

More examples:

https://www.americanscientist.org/article/maxwell-zombies-conjuring-the-thermodynamic-undead

https://en.wikipedia.org/wiki/Epicatalysis

https://en.wikipedia.org/wiki/Duncan%27s_paradox

Scientists should have exposed the absurdity 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 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 and unsurpassable value.

That catalysts can shift chemical equilibrium (and violate the second law) was my first heretical idea, about 25 years ago. I believed my argument was convincing and enthusiastically submitted a short paper to Nature - they rejected it without reading it (let alone giving it to referees). My efforts to publish continued, mainly in The Journal of Physical Chemistry, and I was also active on Internet forums. The main result was this:

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
Pentcho Valev
2018-07-14 09:54:36 UTC
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"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. Here we report on the first experimental realization of this paradox, involving the dissociation of low-pressure hydrogen gas on high-temperature refractory metals (tungsten and rhenium) under blackbody cavity conditions. The results, corroborated by other laboratory studies and supported by theory, confirm the paradoxical temperature difference and point to physics beyond the traditional understanding of the second law." https://link.springer.com/article/10.1007/s10701-014-9781-5

Pentcho Valev

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