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Second Law of Thermodynamics: Obviously False



 
 
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  #1  
Old September 5th 16, 08:50 AM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Second Law of Thermodynamics: Obviously False

As a rule, scientists are silent about violations of the second law of thermodynamics, no matter how convincing they are. Here is a perpetual motion machine of the second kind published in a prestigious journal (no reaction at all from the scientific community):

http://scitation.aip.org/content/aip...1063/1.4825269
Electricity generated from ambient heat across a silicon surface, Guoan Tai, Zihan Xu, and Jinsong Liu, Appl. Phys. Lett. 103, 163902 (2013): "We report generation of electricity from the limitless thermal motion of ions across a two-dimensional (2D) silicon (Si) surface at room temperature. [...] ....limitless ambient heat, which is universally present in the form of kinetic energy from molecular, particle, and ion sources, has not yet been reported to generate electricity. [...] This study provides insights into the development of self-charging technologies to harvest energy from ambient heat, and the power output is comparable to several environmental energy harvesting techniques such as ZnO nanogenerator, liquid and gas flow-induced electricity generation across carbon nanotube thin films and graphene, although this remains a challenge to the second law of thermodynamics..."

There are even obvious violations of the second law of thermodynamics. In this video one switches the capacitor on and off and the system can repeatedly lift floating weights:

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.

The liquid-dielectric-capacitor perpetuum mobile (of the second kind) 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:

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 presumably violating the second law of thermodynamics:

http://proceedings.aip.org/resource/...cs/643/1/430_1
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

Pentcho Valev
  #2  
Old September 6th 16, 12:08 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Second Law of Thermodynamics: Obviously False

Catalysts can shift chemical equilibrium, which is fatal for the second law of thermodynamics:

http://jointheparadigm.com/wp-conten...of-Physics.pdf
Experimental Test of a Thermodynamic Paradox, D. P. Sheehan et al, Foundations of Physics, March 2014, Volume 44, Issue 3, pp 235-247: "...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. Here we report on the first experimental realization of this paradox, involving the dissociation of low-pressure hydrogen gas on high-temperature refractory metals (tungsten and rhenium) under blackbody cavity conditions. The results, corroborated by other laboratory studies and supported by theory, confirm the paradoxical temperature difference and point to physics beyond the traditional understanding of the second law."

The second law of thermodynamics is obviously false for chemical systems. Consider the (valid) argument that, if catalysts can shift chemical equilibrium, the second law is 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...."

It is evident that, 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. In the reverse (association) reaction, the catalyst should first get together B and C, which, if the diffusion factor is predominant, could be highly improbable.

Catalysts do shift chemical equilibrium, in violation of the second law of thermodynamics.

I have started the same discussion (and it has developed in an interesting way) he

https://www.youtube.com/watch?v=aL_iNGh8CNo
Chemical Thermodynamics - Second Law / Entropy Review

Pentcho Valev
  #3  
Old September 7th 16, 07:49 AM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Second Law of Thermodynamics: Obviously False

Catalysts do shift chemical equilibrium, in violation of the second law of thermodynamics:

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)."

Pentcho Valev
  #4  
Old September 17th 16, 02:00 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Second Law of Thermodynamics: Obviously False

http://bip.cnrs-mrs.fr/bip10/valevfaq.htm
Athel Cornish-Bowden 1998: "Can a catalyst shift the position of an equilibrium? No. Absolutely not if it is a true catalyst present at very low concentrations. If it is present at a concentration comparable with that of one or more of the reactants then it may appear to shift the position of equilibrium by mass action effects. However, when it does this it is acting as a reactant, not as a catalyst. Mr Valev’s claims to have shown otherwise are analysed by Lukasz Salwinski (1, 2, 3, 4) and Petr Kuzmic (1, 2, 3, 4, 5, 6, 7). There were also some earlier comments from me (1)."

My career as an iconoclast started when I noticed that catalysts obviously can shift chemical equilibrium, which is fatal for the second law of thermodynamics. About 20 years ago I submitted a one-page article to Nature showing that, for the dissociation-association reaction

A - B + C,

a catalyst cannot speed up both the forward and reverse reaction rates equally, and the reason is that the forward and the reverse catalytic mechanisms are totally different. In the forward (dissociation) reaction, the catalyst should just meet and split A. So the forward rate can be increased substantially. In the reverse (association) reaction, the catalyst should first get together B and C, which, if the (reverse) reaction is diffusion-controlled, would have no effect. Diffusion control means that the affinity between B and C is so high that virtually any encounter between them produces A - no catalyst can increase the rate of such a reaction.

Nature immediately rejected my article - 20 years ago a person suggesting that catalysts can shift chemical equilibrium and so violate the second law was crank, crackpot, troll, or worse, by definition. Then things started to change, and nowadays the situation is entirely different:

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]

Pentcho Valev
 




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