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Commonplace Violations of the Second Law of Thermodynamics



 
 
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Old August 28th 17, 07:58 AM posted to sci.astro
Pentcho Valev
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Default Commonplace Violations of the Second Law of Thermodynamics

Just three examples, without much explanation:

1. WATER IN AN ELECTRIC FIELD.

The non-conservative force (pressure) that emerges between the cathode and the anode can do work at the expense of heat absorbed from the surroundings:

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."

http://www.youtube.com/watch?v=T6KAH1JpdPg
"Liquid Dielectric Capacitor". The rising water can do useful work, e.g. by lifting some floating weight. Since, by switching the field on and off, the operator does no work on the system, the energy supplier can only be the ambient heat.

https://www.youtube.com/watch?v=17UD1goTFhQ
"The Formation of the Floating Water Bridge including electric breakdowns".. The vigorous cyclic motion is obviously able to produce work, e.g. by rotating a waterwheel.

2. CATALYSTS CAN SHIFT CHEMICAL EQUILIBRIUM.

Here is a publication in Nature describing a catalyst accelerating the forward and suppressing the reverse reaction:

http://images.nature.com/m685/nature...mms3500-f1.jpg

https://www.nature.com/articles/ncomms3500
Yu Hang Li et al. Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters

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. [...]

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]

3. pH-SENSITIVE POLYMERS SWELLING AND CONTRACTING CYCLICALLY.

By regularly changing the pH of the system, the operator is able to extract unlimited amount of work from pH-sensitive polymers:

http://www.researchgate.net/profile/...se-network.png

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

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."

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 operator, 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 operator gains work if the hydrogen ions are transported from a high to a low concentration and then loses the same amount of work in the backward transport).

Pentcho Valev
 




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