Second Law of Thermodynamics: Obviously False

http://bip.cnrs-mrs.fr/bip10/valevfaq.htm
Athel Cornish-Bowden 1998: "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 are analysed by Lukasz Salwinski (1, 2, 3, 4) and Petr Kuzmic (1, 2, 3, 4, 5, 6, 7). There were also some earlier comments from me (1)."

My career as an iconoclast started when I noticed that catalysts obviously can shift chemical equilibrium, which is fatal for the second law of thermodynamics. About 20 years ago I submitted a one-page article to Nature showing that, for the dissociation-association reaction

A - B + C,

a catalyst cannot speed up both the forward and reverse reaction rates equally, and the reason is that the forward and the reverse catalytic mechanisms are totally different. In the forward (dissociation) reaction, the catalyst should just meet and split A. So the forward rate can be increased substantially. In the reverse (association) reaction, the catalyst should first get together B and C, which, if the (reverse) reaction is diffusion-controlled, would have no effect. Diffusion control means that the affinity between B and C is so high that virtually any encounter between them produces A - no catalyst can increase the rate of such a reaction.

Nature immediately rejected my article - 20 years ago a person suggesting that catalysts can shift chemical equilibrium and so violate the second law was crank, crackpot, troll, or worse, by definition. Then things started to change, and nowadays the situation is entirely different:

https://en.wikipedia.org/wiki/Duncan%27s_Paradox
"Consider a dimeric gas (A2) that is susceptible to endothermic dissociation or exothermic recombination (A2 - 2A). The gas is housed between two surfaces (S1 and S2), whose chemical reactivities are distinct with respect to the gas. Specifically, let S1 preferentially dissociate dimer A2 and desorb monomer A, while S2 preferentially recombines monomers A and desorbs dimer A2. [...]

http://upload.wikimedia.org/wikipedi...SLTD-Fig1c.jpg

In 2014 Duncan's temperature paradox was experimentally realized, utilizing hydrogen dissociation on high-temperature transition metals (tungsten and rhenium). Ironically, these experiments support the predictions of the paradox and provide laboratory evidence for second law breakdown. These results are corroborated by other experiments that demonstrate anomalous (and differential) levels of hydrogen dissociation on heated transition metals; additional theoretical support can be found in the theory of epicatalysis. In 2015 Laboratory experiments verified examples of room temperature epicatalysis involving hydrogen-bonded diamonds on polymers. This could open the door to room temperature tests of Duncan's Paradox." [end of quotation]

Pentcho Valev