Discussion:
Isothermal Heat Engines Violate The Second Law of Thermodynamics
(trop ancien pour répondre)
Pentcho Valev
2017-08-05 18:23:15 UTC
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By regularly changing the pH of the system, the experimentalist is able to extract unlimited amount of work from pH-sensitive polymers:

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1367611/pdf/biophysj00645-0017.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 but then loses the same amount of work in the backward transport).

Pentcho Valev
Pentcho Valev
2017-08-05 21:24:53 UTC
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Is the scientific community ready for a revolution in thermodynamics? There was a sensation in 2012 - researchers had described a graphene-based device converting ambient heat into electricity, in violation of the second law of thermodynamics. Yet only the technological aspects were discussed - the violation of the second law was not mentioned in the original paper and the comments (not even in Nature's publication):

https://www.technologyreview.com/s/427140/graphene-battery-turns-ambient-heat-into-electric-current/
"Graphene Battery Turns Ambient Heat Into Electric Current. Physicists have built a graphene battery that harvests energy from the thermal movement of ions in solution."

http://arxiv.org/abs/1203.0161
Self-Charged Graphene Battery Harvests Electricity from Thermal Energy of the Environment, Zihan Xu et al: "Moreover, the thermal velocity of ions can be maintained by the external environment, which means it is unlimited. However, little study has been reported on converting the ionic thermal energy into electricity. Here we present a graphene device with asymmetric electrodes configuration to capture such ionic thermal energy and convert it into electricity. [...] To exclude the possibility of chemical reaction, we performed control experiments... [...] In conclusion, we could not find any evidences that support the opinion that the induced voltage came from chemical reaction. The mechanism for electricity generation by graphene in solution is a pure physical process..."

http://blogs.nature.com/news/2012/03/sparks-fly-over-graphene-energy-device.html
Nature: "Although materials scientist Yury Gogotsi of Drexel University in Philadelphia, Pennsylvania, doubts the latest claim, he points out that the mystery should at least be relatively easy to clear up. "The device described by Xu's group is very simple and numerous labs can easily repeat this experiment to check the validity of the results," he says. [...] Comments are closed."

Comments were really closed in 2012, and no labs checked the validity of the results.

In 2013 Zihan Xu and co published a similar paper, in a prestigious journal, and this time the violation of the second law WAS mentioned. This was fatal. Any violation of the second law of thermodynamics acts like the face of Medusa the Gorgon - on seeing it, scientists get petrified and unable to react. So the second paper did not become a sensation - there were no comments at all:

http://scitation.aip.org/content/aip/journal/apl/103/16/10.1063/1.4825269
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..."

Pentcho Valev
Pentcho Valev
2017-08-06 07:37:26 UTC
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"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/ParadigmEnergy/posts/249600938581128

That is, for 50 years scientists have known that catalysts can shift chemical equilibrium, in violation of the second law of thermodynamics. No reaction - just crimestop:

"Crimestop means the faculty of stopping short, as though by instinct, at the threshold of any dangerous thought. It includes the power of not grasping analogies, of failing to perceive logical errors, of misunderstanding the simplest arguments if they are inimical to Ingsoc, and of being bored or repelled by any train of thought which is capable of leading in a heretical direction. Crimestop, in short, means protective stupidity." http://ebooks.adelaide.edu.au/o/orwell/george/o79n/chapter2.9.html

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/chemistry/reactions/equilibrium/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/textbooks/boundless-chemistry-textbook/chemical-equilibrium-14/factors-that-affect-chemical-equilibrium-106/the-effect-of-a-catalyst-447-3459/

Scientists should have noticed long ago that this consequence of the second law of thermodynamics is idiotic. 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.

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. [...]

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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]

Parpetual-motion machines based on the property of biased catalysts to shift chemical equilibrium have even entered a commercialization phase (without much success - the effect is too weak to be of technological use):

https://www.google.com/patents/US20140352682
"An Epicatalytic Thermal Diode (ETD) includes one or more ETD cells. Each cell comprises first and second surfaces with a cavity between them, which contains a gas that is epicatalytically active with respect to the pair of surfaces. The surfaces chemically interact with the gas such that the gas dissociates at a faster rate proximate to the first surface than it does proximate to the second surface. Thus, a steady-state temperature differential between the first surface and the second surface is created and maintained. In various applications, multiple ETD cells are connected in series and/or parallel."

http://aip.scitation.org/doi/abs/10.1063/1.4954971
"Recently, a new mode of gas-surface heterogeneous catalysis (epicatalysis) has been identified, having potential applications ranging from industrial and green chemistry to novel forms of power generation. This article describes an inexpensive, easily constructed, vacuum-compatible apparatus by which multiple candidate gas-surface combinations can be rapidly screened for epicatalytic activity."

Pentcho Valev
Pentcho Valev
2017-08-06 16:12:09 UTC
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"A plane capacitor with rectangular plates is fixed in a vertical position. [...] The capacitor is charged and disconnected from the battery. [...] The lower part of the capacitor is now brought into contact with a dielectric liquid:

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When the plates contact the liquid's surface, a force in the upward direction is exerted on the dielectric liquid. The total charge on each plate remains constant and there is no energy transferred to the system from outside." http://electron6.phys.utk.edu/PhysicsProblems/E&M/2-Dielectrics/capacitors_with_dielectrics.html

The energy for the work done by the rising liquid (e.g. some floating object can be lifted) can only come from the ambient heat - there is no other "energy transferred to the system from outside".

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

"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." https://phys.org/news/2007-09-bridge-exposed-high-voltage.html

Here are more references. Vigorous cyclic motion can be seen in the video, obviously able to produce unlimited amount of work at the expense of heat absorbed from the surroundings:


"The Formation of the Floating Water Bridge including electric breakdowns"

https://www.wetsus.nl/home/wetsus-news/more-than-just-a-party-trick-the-floating-water-bridge-holds-insight-into-nature-and-human-innovation/1
"Taking some more time to watch the bridge in action, one is stupefied by the complexity. The water movement is bidirectional, i.e., it simultaneously flows in both directions..."

Adam Wexler's article (the last reference) is extremely instructive, both for what it says explicitly and for what it only implies:

"There is practically nothing ordinary about the water in an active floating bridge, and this is no esoteric experiment, as the strength and shape of the electric field we apply in the water bridge is nearly ubiquitous throughout nature. It turns out that if we examine the electric fields present in nature, such as those in living cells, around soil particles, or in clouds, we find that the field strengths are on the same order of magnitude - megavolts per meter. Which incidentally is the same in the water bridge, not to mention inside many electrochemical and biochemical fuel cells that are now being used to develop the next generation of resource recovery technologies. Megavolts per meter seems to be this kind of universal constant of field strength in aqueous systems. It's such an enticing observation that, during my defense, one of my opponents made a point to ask whether I thought this was just a coincidence or indicated some deeper truth that we are as yet unaware. Of course I had to answer the latter, as I am a firm believer that nature is quite deliberate in its construction and there are really no accidents. [...] The floating water bridge is a long-lost piece of the puzzle in understanding why water is such an unusual substance. What we had missed was that, in liquids there exists an intrinsic disequilibrium which continuously drives the system around within a big basin of possible configurations; and water is again exceptional. When we apply the electric field, we perturb the dynamics and change the shape of the attractor basin. This in turn changes the flow of energy through the system and may even liberate stored energy that is inaccessible when the liquid is in the ground state."

Note that some "stored energy" was "inaccessible" and is now "liberated". This "stored energy" is AMBIENT HEAT. We have a fundamental mechanism of utilization of ambient heat (no need for a temperature gradient) that has remained hidden for too long, thanks to the inclination of mankind to blind itself by imposing false restrictive principles - in this case the second law of thermodynamics. In an electric field, water is capable of undergoing eternal motion and the energy source behind this is heat absorbed from the surroundings. The absorbed heat eventually returns to the surroundings, due to friction. However the eternal motion can be harnessed - then heat absorbed from the surroundings will be converted into work, in violation of the second law of thermodynamics.

Pentcho Valev
Pentcho Valev
2017-08-07 07:20:51 UTC
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The non-conservative force (pressure) that emerges between two opposite electric charges immersed in water is perhaps fundamental for life on Earth so it makes sense to try to explain it in more detail.

When two opposite charges (or capacitor plates) are immersed in a dielectric liquid, e.g. water, some additional force (pressure) emerges between them, pushes them apart and so counteracts their electrostatic attraction:

http://farside.ph.utexas.edu/teaching/jk1/lectures/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."

http://www.amazon.com/Classical-Electricity-Magnetism-Second-Physics/dp/0486439240?tag=viglink21401-20
Wolfgang K. H. Panofsky, Melba Phillips, Classical Electricity and Magnetism, pp.115-116: "Thus the decrease in force that is experienced between two charges when they are immersed in a dielectric liquid can be understood only by considering the effect of the PRESSURE OF THE LIQUID ON THE CHARGES themselves."

http://www.amazon.com/Introduction-To-Electromagnetic-Theory-Perspective/dp/0763738271
Tai Chow, Introduction to Electromagnetic Theory: A Modern Perspective, p. 267: "The strictly electric forces between charges on the conductors are not influenced by the presence of the dielectric medium. The medium is polarized, however, and the interaction of the electric field with the polarized medium results in an INCREASED FLUID PRESSURE ON THE CONDUCTORS that reduces the net forces acting on them."

There is a high pressure between the plates and a lower pressure outside the capacitor so if we punch a small hole in one of the plates, there will be ETERNAL FLOW through the hole, from inside (between the plates) to outside. In other words, we will have a SYSTEM IN DYNAMIC EQUILIBRIUM. The eternal flow can be harnessed to do work, at the expense of heat absorbed from the surroundings (no electric energy is used) and therefore in violation of the second law of thermodynamics. The flows in the floating-water-bridge system are essentially analogous:

http://youtu.be/17UD1goTFhQ
"The Formation of the Floating Water Bridge including electric breakdowns" x

https://www.wetsus.nl/home/wetsus-news/more-than-just-a-party-trick-the-floating-water-bridge-holds-insight-into-nature-and-human-innovation/1
"Taking some more time to watch the bridge in action, one is stupefied by the complexity. The water movement is bidirectional, i.e., it simultaneously flows in both directions..." x

The capacitor-in-water system can violate the second law in a more traditional way. If the plates of the capacitor are vertical and only partially immersed, the pressure forces the liquid between the plates to rise above the surface of the pool:

http://electron6.phys.utk.edu/PhysicsProblems/E&M/2-Dielectrics/capacitors_with_dielectrics.html
"A plane capacitor with rectangular plates is fixed in a vertical position. [...] The capacitor is charged and disconnected from the battery. [...] The lower part of the capacitor is now brought into contact with a dielectric liquid of...

http://electron6.phys.utk.edu/PhysicsProblems/E&M/2-Dielectrics/Images/Image4.gif

When the plates contact the liquid's surface, a force in the upward direction is exerted on the dielectric liquid. The total charge on each plate remains constant and there is no energy transferred to the system from outside." [end of quotation]

http://www.academia.edu/25650739/Fluids_in_electric_and_magnetic_fields_Pressure_variation_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."


Rise in Liquid Level Between Plates of a Capacitor


Liquid Dielectric Capacitor


Chapter 11.6.2: Force on a liquid dielectric

The rising dielectric liquid can do useful work, e.g. by lifting some floating weight. Since, by switching the field on and off, we do no work on the system, the energy supplier can only be the ambient heat. That is, the system can cyclically lift floating weights at the expense of heat absorbed from the surroundings, in violation of the second law of thermodynamics.

What is the molecular mechanism behind the effect? Here is a schematic presentation of water dipoles in the electrical field:

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If it were not for the indicated (with an arrow) dipole, other dipoles in the picture are perfectly polarized as if there were no thermal motion. Of course, this is an oversimplification – thermal motion is a factor which constantly disturbs the polarization order. However the crucial point is that, as can be inferred from the picture, any thermal disturbance contributes to the creation of a pressure between the plates. Consider the indicated dipole. It has just received a strong thermal stroke and undergone rotation. As a result, it pushes adjacent dipoles electrostatically, towards the plates. Macroscopically, the sum of all such disturbances is expressed as a pressure exerted on the plates. One can also say, somewhat roughly, that the indicated dipole has absorbed heat and now, by pushing adjacent dipoles, is trying to convert it into work.

Pentcho Valev

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