Discussion:
Catalysts Against the Second Law of Thermodynamics
(trop ancien pour répondre)
Pentcho Valev
2018-02-13 11:21:30 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://www.boundless.com/chemistry/textbooks/boundless-chemistry-textbook/chemical-equilibrium-14/factors-that-affect-chemical-equilibrium-106/the-effect-of-a-catalyst-447-3459/

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

Pentcho Valev
Pentcho Valev
2018-02-14 14:54:56 UTC
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Perpetual (limited only by the deterioration of the system) motion of dimer A_2 and monomer A between two catalytic surfaces, S1 and S2:

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See the explanations here: https://en.wikipedia.org/wiki/Duncan%27s_Paradox

That catalysts can violate the second law of thermodynamics by shifting chemical equilibrium is presented by Wikipedia as a fact:

"Epicatalysis is a newly identified class of gas-surface heterogeneous catalysis in which specific gas-surface reactions shift gas phase species concentrations away from those normally associated with gas-phase equilibrium. [...] A traditional catalyst adheres to three general principles, namely: 1) it speeds up a chemical reaction; 2) it participates in, but is not consumed by, the reaction; and 3) it does not change the chemical equilibrium of the reaction. Epicatalysts overcome the third principle..." https://en.wikipedia.org/wiki/Epicatalysis

Scientists should have exposed the absurdity of this 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 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.

The second law of thermodynamics is OBVIOUSLY false.

Pentcho Valev

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