The Second Law of Thermodynamics Is Unreasonable in a Structured World

https://www.edge.org/response-detail/27023
WHAT SCIENTIFIC TERM OR CONCEPT OUGHT TO BE MORE WIDELY KNOWN? Steven Pinker: "The Second Law of Thermodynamics. The Second Law of Thermodynamics states that in an isolated system (one that is not taking in energy), entropy never decreases. (The First Law is that energy is conserved; the Third, that a temperature of absolute zero is unreachable.) Closed systems inexorably become less structured, less organized, less able to accomplish interesting and useful outcomes, until they slide into an equilibrium of gray, tepid, homogeneous monotony and stay there."

This is simply not true. Thanks to conservative forces, systems will always remain STRUCTURED. That is, at the structural level, there will always be gradients and discontinuity. This suggests that there will always be temperature and concentration gradients, even at equilibrium.

Here is a version of the second law of thermodynamics which says that catalysts cannot shift the position of chemical equilibrium - below the key words are "BY THE SAME AMOUNT" and "EQUALLY":

"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/

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 unrealistic, even idiotic! In the reverse reaction the catalyst's function is entirely different - now it must get together B and C and then join them to form A. So it would be nonsense to expect getting-together-B-and-C to produce a rate increase by exactly the same factor, 745492.

There is no reason why the catalyst should increase the rates of the forward and reverse reactions "by the same amount" - some catalysts accelerate the forward reaction to a greater extent, others may favor the reverse reaction. Example:

"Rhenium dissociates hydrogen molecules into atoms better than tungsten does; conversely, tungsten recombines hydrogen atoms back into hydrogen molecules better than rhenium."

Here is more explanation:

http://microver.se/sse-pdf/edgescience_24.pdf
"A small, closed, high temperature cavity contained two metal catalysts (rhenium and tungsten), which were known to dissociate molecular hydrogen (H2) to different degrees (Figure 1). (Rhenium dissociates hydrogen molecules into atoms better than tungsten does; conversely, tungsten recombines hydrogen atoms back into hydrogen molecules better than rhenium.) Because the dissociation reaction (H2 - 2H) is endothermic (absorbs heat), and the recombination reaction (2H - H2) is exothermic (liberates heat), when hydrogen was introduced into the cavity, the rhenium surfaces cooled (up to more than 125 K) relative to the tungsten (Figure 2). Because the hydrogen-metal reactions were ongoing in the sealed cavity, the rhenium stayed cooler than the tungsten indefinitely. This permanent temperature difference - this steady-state nonequilibrium - is expressly forbidden by the second law, not just because the system won’t settle down to a single-temperature equilibrium, but because this steady-state temperature difference can, in principle, be used to drive a heat engine (or produce electricity) solely by converting heat back into work, which is a violation of one of the most fundamental statements of the second law (Kelvin-Planck formulation)."

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." [end of quotation]

Clearly, macroscopic catalytic surfaces can violate the second law of thermodynamics by accelerating reversible chemical reactions in one direction but failing to produce the same acceleration in the opposite direction.

Pentcho Valev