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