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The Second Law of Thermodynamics Is Unreasonable in a Structured World



 
 
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  #1  
Old January 31st 17, 01:12 PM posted to sci.astro
Pentcho Valev
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Default 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
  #2  
Old January 31st 17, 01:59 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default The Second Law of Thermodynamics Is Unreasonable in a Structured World

A simple structure consisting in a parallel-plate capacitor immersed in water produces various effects violating the second law of thermodynamics. In the following two videos one switches the capacitor on and off and the system can repeatedly lift floating weights:

https://www.youtube.com/watch?v=aHNwvfXUYb4
Rise in Liquid Level Between Plates of a Capacitor

http://www.youtube.com/watch?v=T6KAH1JpdPg
Liquid Dielectric Capacitor

Switching the capacitor on and off involves no work done on the system so the energy for the work done BY the system (if it repeatedly lifts floating weights) can only come from the environmental heat, in violation of the second law of thermodynamics.

The violation of the second law can be described in a different way. When a constant-charge parallel-plate capacitor is immersed in a liquid dielectric, e.g. water, a mysterious pressure emerges between the plates, pushes them apart and so counteracts their electrostatic attraction:

http://farside.ph.utexas.edu/teachin...es/node46.html
"However, in experiments in which a capacitor is submerged in a dielectric liquid the force per unit area exerted by one plate on another is observed to decrease... [...] This apparent paradox can be explained by taking into account the difference in liquid pressure in the field filled space between the plates and the field free region outside the capacitor."

So we have a high pressure between the plates and a lower pressure outside the capacitor - then what if one punches a small hole in one of the plates? Will there be an eternal flow through the hole, from inside to outside?

If the plates are vertical and only partially immersed, the same mysterious pressure forces the liquid between the plates to rise above the surface of the water pool, as seen in the videos above and in Fig. 1 and Fig. 2 he

http://www.academia.edu/25650739/Flu..._and_stability
I. Brevik, Fluids in electric and magnetic fields: Pressure variation and stability, Can. J . Phys. (1982): "Fig. 1. Two charged condenser plates partly immersed in a dielectric liquid. [...] Fig. 2. The hydrostatic pressure variation from point 1 to point 5 in Fig. 1."

In 2002 I proposed the following device violating the second law of thermodynamics:

http://adsabs.harvard.edu/abs/2002AIPC..643..430V
AIP Conf. Proc. 643, pp. 430-435, Pentcho Valev 2002: "...as two vertical constant-charge capacitor plates partially dip into a pool of a liquid dielectric (e.g. water), the liquid between them rises high above the surface of the rest of the liquid in the pool. Evidently, if one punches a macroscopic hole in one of the plates, nothing could prevent the liquid between the plates from leaking out through the hole and generating an eternal waterfall outside the capacitor. This hypothesis has been discussed on many occasions but so far no serious counter-argument has been raised."

Here is a schematic picture of the "eternal waterfall":

http://energythic.com/usercontent/3/...PU_caphole.gif

In 2004 I tried to explain the molecular mechanism behind the effect:

http://www.gsjournal.net/old/valev/valev2.pdf
Biased Thermal Motion and the Second Law of Thermodynamics (August 12, 2004)

Generally, water in an electric field has a tendency to rise - if there is some weight floating on the surface, it will be lifted:

https://www.youtube.com/watch?v=ACDxurDAmyg
Chapter 11.6.2: Force on a liquid dielectric

Since switching the field on and off involves no work done on the system, the system does work for us (lifts floating weights) at the expense of heat absorbed from the surroundings, in violation of the second law of thermodynamics.

The "floating water bridge" is essentially the same phenomenon - water absorbs heat from the surroundings and uses it to "climb out of the beakers":

http://phys.org/news/2007-09-bridge-...h-voltage.html
"When exposed to a high-voltage electric field, water in two beakers climbs out of the beakers and crosses empty space to meet, forming the water bridge. The liquid bridge, hovering in space, appears to the human eye to defy gravity."

https://www.youtube.com/watch?v=FhBn1ozht-E
The Floating Water Bridge

Pentcho Valev
  #3  
Old February 2nd 17, 02:05 PM posted to sci.astro
Pentcho Valev
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Default The Second Law of Thermodynamics Is Unreasonable in a Structured World

Thermodynamics contributed to the destruction of human rationality just as vigorously as Einstein's relativity did:

http://www.bourbaphy.fr/price.pdf
Huw Price, Time's Arrow and Eddington's Challenge, p. 122: "A lot of time and ink has been devoted to the question how entropy should be defined, or whether it can be defined at all in certain cases (e.g., for the universe as a whole). It would be easy to get the impression that the puzzle of the thermodynamic asymmetry depends on all this discussion - that whether there's really a puzzle depends on how, and whether, entropy can be defined, perhaps."

http://philsci-archive.pitt.edu/archive/00000313/
Jos Uffink, Bluff your Way in the Second Law of Thermodynamics, p. 94: "This summary leads to the question whether it is fruitful to see irreversibility or time-asymmetry as the essence of the second law. Is it not more straightforward, in view of the unargued statements of Kelvin, the bold claims of Clausius and the strained attempts of Planck, to give up this idea? I believe that Ehrenfest-Afanassjewa was right in her verdict that the discussion about the arrow of time as expressed in the second law of the thermodynamics is actually a RED HERRING. The only way to evaluate such a proposal is by making up a balance-sheet. What would we loose and what would we gain? It is clear that in fact all concrete applications of the second law in classical thermodynamics, even in the work of the most outspoken proponents of the claim that this law implies universal irreversibility, are restricted to systems in equilibrium. This holds for Kelvin and Planck, but also more recent text books (e.g. (Becker 1967)). A general opinion among thermodynamicists is even that the theory is incapable of dealing with systems out of equilibrium; (see the quotation from Bridgman on page 3). Clearly, in terms of concrete applications, we would loose very little. What, then, do we gain with this proposal? The main advantage is, to my mind, that the second law would no longer represent an obstacle to the reconciliation of different theories of physics."

ftp://ftp.esat.kuleuven.ac.be/pub/SI...orts/06-46.pdf
"From the pedagogical point of view, thermodynamics is a disaster. As the authors rightly state in the introduction, many aspects are "riddled with inconsistencies". They quote V.I. Arnold, who concedes that "every mathematician knows it is impossible to understand an elementary course in thermodynamics". Nobody has eulogized this confusion more colorfully than the late Clifford Truesdell. On page 6 of his book "The Tragicomical History of Thermodynamics" 1822-1854 (Springer Verlag, 1980), he calls thermodynamics "a dismal swamp of obscurity". Elsewhere, in despair of trying to make sense of the writings of some local heros as De Groot, Mazur, Casimir, and Prigogine, Truesdell suspects that there is "something rotten in the (thermodynamic) state of the Low Countries" (see page 134 of Rational Thermodynamics, McGraw-Hill, 1969)."

And yet:

http://web.mit.edu/keenansymposium/o...und/index.html
Arthur Eddington: "The law that entropy always increases, holds, I think, the supreme position among the laws of Nature. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell's equations - then so much the worse for Maxwell's equations. If it is found to be contradicted by observation - well, these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of thermodynamics, I can give you no hope; there is nothing for it but to collapse in deepest humiliation."

Pentcho Valev
 




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