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Old October 27th 16, 03:08 PM posted to sci.astro
Pentcho Valev
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Default Two Falsehoods That Killed Physics

Catalysts ("apposing vane surfaces" in this case) can violate the second law of thermodynamics:

http://link.springer.com/article/10....701-014-9781-5
"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://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]

Here is the (valid) argument that, if catalysts can shift chemical equilibrium, the second law would be violated:

https://www.boundless.com/chemistry/...lyst-447-3459/
"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. [...] To reiterate, catalysts do not affect the equilibrium state of a reaction. In the presence of a catalyst, the same amounts of reactants and products will be present at equilibrium as there would be in the uncatalyzed reaction. To state this in chemical terms, catalysts affect the kinetics, but not the thermodynamics, of a reaction. If the addition of catalysts could possibly alter the equilibrium state of the reaction, this would violate the second rule of thermodynamics...."

Yet, for for the dissociation-association reaction

A - B + C,

a catalyst cannot speed up both the forward and reverse reaction rates equally, due to the entirely different forward and reverse catalytic mechanisms.. In the forward (dissociation) reaction, the catalyst should just meet and split A. So the rate of the forward reaction can be substantially increased by the catalyst. In the reverse (association) reaction, the catalyst should first get together B and C. However, if the reverse reaction is diffusion-controlled (virtually any encounter between B and C produces A), the catalyst cannot accelerate it - the rate is already at its maximum.

Conclusion: Catalysts can OBVIOUSLY violate the second law of thermodynamics.

Pentcho Valev