Catalysts Topple the Second Law of Thermodynamics

The false restrictive principle called "Second law of thermodynamics", apart from preventing humankind from understanding fundamental energy conversions in Nature, has produced collateral damages as well. One of its idiotic implications is that, if a catalyst increases the rate of the forward reaction by a factor of, say, 745492, it obligatorily increases the rate of the reverse reaction by the same factor, 745492, despite the fact that the two reactions - forward and reverse - may be entirely different (e.g. the diffusion factor is crucial for one but not important for the other) and accordingly require entirely different catalytic strategies. The idiotic implication is usually referred to as "Catalysts do not shift chemical equilibrium":

"A catalyst reduces the time taken to reach equilibrium, but does not change the position of the equilibrium. This is because the catalyst increases the rates of the forward and reverse reactions BY THE SAME AMOUNT."
http://www.bbc.co.uk/bitesize/higher...um/revision/2/

"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/...lyst-447-3459/

Scientists should have exposed the absurdity of this implication of the second law of thermodynamics long ago. How can the catalyst increase the rates of the forward and reverse reactions BY THE SAME AMOUNT (EQUALLY) if these two reactions are entirely different? 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 so efficiently that the rate 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 of the reverse (association) reaction by exactly the same factor, 745492. But this is obviously absurd! In the reverse reaction the catalyst's function is entirely different - the catalyst must first get together B and C and then join them to form A. It is nonsense to expect the process involving

getting-together-B-and-C

to have exactly the same rate increase, by a factor of 745492, as the process involving just

splitting-A.

The catalyst may be able to increase the rates of both - forward and reverse - reactions, this is realistic, but not BY THE SAME AMOUNT (EQUALLY). The second law of thermodynamics is obviously false.

Actually scientists have always known that catalysts can shift chemical equilibrium, in violation of the second law of thermodynamics:

"For 50 years scientists have seen in experiments that some monomers and dimers split apart and rejoin at different rates on different surfaces. The eureka moment came when we recognized that by placing two different surfaces close together in a way that effectively eliminates the gas cloud, the energy balance would be different on each of the two surfaces. One surface would have more molecules breaking apart, cooling it, while the other surface would have more molecules joining back together, warming it." https://www.facebook.com/ParadigmEne...49600938581128

Here is a publication in Nature describing a catalyst catalyzing the forward and suppressing the reverse reaction:

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

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

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

https://en.wikipedia.org/wiki/Epicatalysis
"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/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." [end of quotation]

Pentcho Valev

Heat engines capable of violating the second law of thermodynamics are COMMONPLACE. This would be an obvious fact if misleading education had not diverted the attention from relevant examples:

"A necessary component of a heat engine, then, is that two temperatures are involved. At one stage the system is heated, at another it is cooled." http://physics.bu.edu/~duffy/py105/Heatengines.html

Not true. There are heat engines functioning in ISOTHERMAL conditions - e.g.. the work-producing force is activated by some chemical agent, not by heating.

All isothermal heat engines, except for analogs of ideal gas systems, can violate the second law of thermodynamics.

Just an example. By regularly changing the pH of the system, the experimentalist is able to extract unlimited amount of work from pH-sensitive polymers:

http://www.researchgate.net/profile/...se-network.png

http://www.gsjournal.net/old/valev/val3.gif

http://www.ncbi.nlm.nih.gov/pmc/arti...00645-0017.pdf
A. KATCHALSKY, POLYELECTROLYTES AND THEIR BIOLOGICAL INTERACTIONS, p. 15, Figure 4: "Polyacid gel in sodium hydroxide solution: expanded. Polyacid gel in acid solution: contracted; weight is lifted."

http://www.google.com/patents/US5520672
"When the pH is lowered (that is, on raising the chemical potential, μ, of the protons present) at the isothermal condition of 37°C, these matrices can exert forces, f, sufficient to lift weights that are a thousand times their dry weight."

The second law of thermodynamics is violated unless the following is the case:

The experimentalist, as he decreases and then increases the pH of the system, does (loses; wastes) more work than the work he gains from weight-lifting.

However electrochemists know that, if both adding hydrogen ions to the system and then removing them are performed quasi-statically, the net work involved is virtually zero (the experimentalist gains work if the hydrogen ions are transported from a high to a low concentration and then loses the same amount of work in the backward transport).

Pentcho Valev