Why the Second Law of Thermodynamics Still Holds

Heat engines capable of violating the second law of thermodynamics are COMMONPLACE. This would be an obvious fact if misleading education had not diverted the attention from relevant examples:

"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."
http://physics.bu.edu/~duffy/py105/Heatengines.html

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. Simple analysis of isothermal cycles in which such heat engines produce work would show that they are essentially perpetual-motion machines of the second kind.

There is a clear and unambiguous formulation of the second law of thermodynamics given by Sadi Carnot himself:

"A cold body is necessary"

That is, heat cannot be cyclically converted into work unless some temperature gradient is present - a hot body, source of heat, and a cold body, receiver of heat, must be available. The problem is that in 1824 Carnot deduced "A cold body is necessary" from a postulate that eventually turned out to be false:

Carnot's (false) postulate: Heat is an indestructible substance (caloric) that cannot be converted into work by the heat engine.

Unpublished notes written in the period 1824-1832 reveal that, after realizing that his postulate was false, Carnot found "A cold body is necessary" implausible:

http://www.nd.edu/~powers/ame.20231/carnot1897.pdf
Sadi Carnot, REFLECTIONS ON THE MOTIVE POWER OF HEAT, p. 225: "Heat is simply motive power, or rather motion which has changed form. It is a movement among the particles of bodies. Wherever there is destruction of motive power there is, at the same time, production of heat in quantity exactly proportional to the quantity of motive power destroyed. Reciprocally, wherever there is destruction of heat, there is production of motive power." p. 222: "Could a motion (that of radiating heat) produce matter (caloric)? No, undoubtedly; it can only produce a motion. Heat is then the result of a motion. Then it is plain that it could be produced by the consumption of motive power, and that it could produce this power. All the other phenomena - composition and decomposition of bodies, passage to the gaseous state, specific heat, equilibrium of heat, its more or less easy transmission, its constancy in experiments with the calorimeter - could be explained by this hypothesis. But it would be DIFFICULT TO EXPLAIN WHY, IN THE DEVELOPMENT OF MOTIVE POWER BY HEAT, A COLD BODY IS NECESSARY; why, in consuming the heat of a warm body, motion cannot be produced."

Generally, a cold body is not necessary, that is, the second law of thermodynamics is false. The cold body is only TECHNOLOGICALLY necessary as it makes heat engines fast-working. Heat engines working under isothermal conditions (in the absence of a cold body) are commonplace but are too slow and impuissant to be of any technological importance. Except, perhaps, for the case where water is placed in an electric field - the non-conservative force (pressure) that emerges between the cathode and the anode, able to convert ambient heat into work, seems to be quite vigorous:

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

https://www.youtube.com/watch?v=17UD1goTFhQ
"The Formation of the Floating Water Bridge including electric breakdowns"

Pentcho Valev

Thermodynamicists have found an easy way to protect their "science". Non-isothermal work-producing cycles (involving hot and cold heat reservoirs) are taught and analyzed – students learn how the second law of thermodynamics is gloriously confirmed. Isothermal work-producing cycles are not analyzed – it is suggested that, instead of analysis, a device that solves the world's energy problems should be built and demonstrated to a jury. And even this would be meaningless since such devices are impossible by definition. A catch-22 situation.

Still the insanity cannot go on forever. Consider an isothermal cycle in which, by regularly changing the pH of the system, the operator activates and deactivates a non-conservative "elastic" force and so 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 following four-step isothermal cycle, if carried out quasi-statically, clearly violates the second law of thermodynamics:

1. The polymer is initially stretched. The operator adds hydrogen ions (H+) to the system. The force of contraction increases.
2. The polymers contracts and lifts a weight.
3. The operator removes the same amount of H+ from the system. The force of contraction decreases.
4. The operator stretches the polymer and restores the initial state of the system.

The net work extracted from the cycle is positive unless the following is the case:

The operator, as he decreases and then increases the pH of the system (steps 1 and 3), 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

If a catalyst affects the forward and reverse reactions differently - e.g. accelerates the forward but suppresses the reverse, or accelerates the forward more than the reverse, then the second law of thermodynamics is false:

"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/

Scientists have always known that some catalysts affect the forward and reverse reactions DIFFERENTLY, in violation of the second law of thermodynamics:

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

"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/ParadigmEne...49600938581128

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]

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Richard Feynman: "The whole subject of thermodynamics depends essentially upon the following kind of consideration: because a rubber band is "stronger" at higher temperatures than it is at lower temperatures, it ought to be possible to lift weights, and to move them around, and thus to do work with heat." http://www.feynmanlectures.caltech.edu/I_44.html

http://www.feynmanlectures.caltech.e...01_tc_big.svgz

This is a non-isothermal heat engine - at least qualitatively, it does not violate the second law of thermodynamics. However it has isothermal analogs which do violate the second law:

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

POLYELECTROLYTES AND THEIR BIOLOGICAL INTERACTIONS, A. KATCHALSKY, pp. 13-15: "Let the polymolecule be a negatively charged polyacid in a stretched state and have a length L. Now let us add to the molecule a mineral acid to provide hydrogen ions to combine with the ionized carboxylate groups and transform them into undissociated carboxylic groups according to the reaction RCOO- + H+ = RCOOH. By means of this reaction, the electrostatic repulsion which kept the macromolecule in a highly stretched state vanishes and instead the Brownian motion and intramolecular attraction cause a coiling up of the polymeric chains. Upon coiling, the polymolecule contracts and lifts the attached weight through a distance ΔL. On lifting the weight, mechanical work f*ΔL was performed... [...] FIGURE 4: Polyacid gel in sodium hydroxide solution: expanded. Polyacid gel in acid solution: contracted; weight is lifted."
http://www.ncbi.nlm.nih.gov/pmc/arti...0645-0017..pdf

"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." http://www.google.com/patents/US5520672

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Philip Ball: "Patterns, regularities and order appear spontaneously in the universe over an immense range of scales in space and time. Not only does such organization seem to challenge the universal thermodynamic tendency towards an inexorable increase in entropy and disorder, but these patterns often share similar forms and features in systems that seem to have no relation to one another. It has become increasingly clear that there are organizing processes in nature that operate according to very general principles, insensitive to (or at best merely fine-tuned by) the details of a particular system." https://www.ongrowthandform.org/even...owth-and-form/

Is this the former editor of Nature Philip Ball, once unrelenting defender of the second law of thermodynamics? Times change, obviously.

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