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Commonplace Violations of the Second Law of Thermodynamics



 
 
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Old February 21st 17, 08:47 AM posted to sci.astro
Pentcho Valev
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Default Commonplace Violations of the Second Law of Thermodynamics

Violations of the second law of thermodynamics would be regarded as commonplace if it were not for misleading education:

http://physics.bu.edu/~duffy/py105/Heatengines.html
"A necessary component of a heat engine, then, is that two temperatures are involved. At one stage the system is heated, at another it is cooled."

This is simply not true. There are heat engines functioning in isothermal conditions - e.g. the work-producing force is activated by some chemical agent, not by heating. For instance, there are macroscopic contractile polymers which, on adding acid (H+) to the system, develop a huge work-producing force, contract and light a weight:

http://www.gsjournal.net/old/valev/val3.gif

See Figure 4 he

http://www.ncbi.nlm.nih.gov/pmc/arti...00645-0017.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."

Mineral acid (hydrogen ions, H+) is added to the system and "the polymolecule contracts and lifts the attached weight through a distance ΔL". Then the acid can be removed and the macromolecule resumes its initial stretched state, ready to lift another weight. The work involved in adding and removing (electrochemically) hydrogen ions, if performed reversibly, is virtually zero, while the net work extracted from contracting and stretching is obviously positive - the system is cyclically lifting weights at the expense of heat absorbed from the surroundings, in violation of the second law of thermodynamics.

A capacitor immersed in a liquid dielectric (water) obviously violates the second law of thermodynamics:

http://citeseerx.ist.psu.edu/viewdoc...=rep1&type=pdf
I. BREVIK, EXPERIMENTS IN PHENOMENOLOGICAL ELECTRODYNAMICS AND THE ELECTROMAGNETIC ENERGY-MOMENTUM TENSOR, pp. 143-144: "We shall first give some supplementary comments on the well known situation shown in fig. 1, where two parallel condenser plates are partially immersed in a dielectric liquid. When a horizontal electric field E is applied between the plates, the liquid will rise within the condenser to some equilibrium height h. [...] What makes the liquid rise between the plates? Certainly not the electrostriction force."

The rising dielectric liquid can do useful work, e.g. by lifting some floating weight, and the crucial question is: At the expense of what energy is the work done? 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.

More illustrations:

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

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

Special attention should be paid to the difference in pressure between the inside and outside of the capacitor:

http://farside.ph.utexas.edu/teachin...es/node46.html
"However, in experiments in which a capacitor is submerged in a dielectric liquid [e.g. water] 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.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."

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? There will be an ETERNAL FLOW through the hole, from inside (between the plates) to outside. We have a SYSTEM IN DYNAMIC EQUILIBRIUM obviously violating the second law of thermodynamics.

Catalysts (enzymes) also obviously violate the second law of thermodynamics.. Consider the dissociation-association reaction

A - B + C

which is in equilibrium. Let us assume that the forward reaction

A - B + C

is exothermic while the reverse

B + C - A

is endothermic. We add a catalyst, e.g. a macroscopic catalytic surface, and it starts splitting A efficiently but is unable to get together B and C and join them into A. In other words, the catalytic surface accelerates the forward reaction but fails to accelerate the reverse. This looks realistic - the probability that a B molecule and a C molecule will hit the catalytic center simultaneously, so that the center can combine them, could be vanishingly small. Yet, if this is so, the second law is obviously violated - even at equilibrium, there will be local temperature and concentration gradients at the catalytic surface that can in principle be harnessed to do work.

The above scenario is oversimplified - it is assumed that the reverse reaction is not catalyzed at all. This is not necessary. The reverse reaction can be catalyzed as well, but if the catalytic acceleration in one direction is smaller than the catalytic acceleration in the other, the second law is violated.

That is, catalysts (enzymes) can violate the second law of thermodynamics by accelerating reversible chemical reactions in one direction and failing to produce the same acceleration in the opposite direction. The effect sounds self-evident and is experimentally confirmed - Wikipedia is now presenting it 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..."

Pentcho Valev
 




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