Why Isothermal Heat Engines Are Nightmare in Thermodynamics

Any isothermal cycle involving swelling and collapsing of pH-sensitive polymers, if performed quasi-statically, can produce positive net work, in violation of the second law of thermodynamics:

http://image.slidesharecdn.com/1-sma...?cb=1461682420

Thermodynamicists love to evaluate the work extractable from various quasi-static cycles - this is traditional thermodynamics. But the cycle should be non-isothermal. If the cycle is isothermal, thermodynamicists don't even think of it:

"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/orw...hapter2.9.html

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Let us consider again the four-step quasi-static cycle:

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

Note that the operator, as he decreases and then increases the pH of the system (steps 1 and 3), does no NET work - he gains work if the hydrogen ions are transported from a high to a low concentration, e.g. in step 1, and then loses the same amount of work in the backward transport, in step 3. Still, even though the NET work is zero, the operator is involved in work production.

There are isothermal heat engines where the operator is NOT involved in work production. In this video he just switches the capacitor on and off and the water can cyclically lift floating weights, in violation of the second law of thermodynamics:

http://www.youtube.com/watch?v=T6KAH1JpdPg
"Liquid Dielectric Capacitor"

Isothermal heat engines where the operator is not involved in work production can generate perpetual motion. The following system is essentially identical to the capacitor system demonstrated above (in both cases we have water in an electric field):

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

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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]

The false second law of thermodynamics has driven the science of metabolism in the wrong "free energy" direction:

"Metabolite flow tends to be unidirectional. Living cells exist in a dynamic steady state in which average concentrations of metabolic intermediates remain relatively constant over time. I.e. nutrients go in, they move about getting converted and reconverted etc. and then wastes are excreted. The unidirectional flow of metabolites through a pathway with a large overall negative change in free energy is analogous to the flow of water through a pipe in which one end is lower than the other. Bends or kinks represent individual enzymatic steps. Despite these, the flow is unidirectional which corresponds to the overall change in free energy in the pathway." https://www.scribd.com/doc/61362780/Enzyme-Activity

The unidirectionality is not determined by free energy changes - it is due to the property of some enzymes to catalyze only the forward reaction, not the reverse. There are countless hints at this in the literature. Just an example:

"It seems exceedingly unlikely, therefore, that the final phosphorylation reaction is irreversible by reason of the endergonic character of the reverse reaction. Since the phosphorylating enzyme system is certainly capable of great activity in the forward direction, we are in the awkward position to postulate a unidirectional catalysis of a thermodynamically reversible reaction." Current Topics in Bioenergetics, Volume 1, Editors: D. R. Sanadi, p.. 108 https://www.elsevier.com/books/curre...-1-4831-9969-6

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"The second law of thermodynamics describes why a catalyst does not change the chemical equilibrium of a reaction. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to the system would result in a reaction to move to the new equilibrium, producing energy. [...] Then, removing the catalyst would also result in reaction, producing energy; i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the equilibrium would be a perpetual motion machine, a contradiction to the laws of thermodynamics." https://en.wikipedia.org/wiki/Catalysis

Adding and removing the catalyst are not processes in which work is done by or on the system - here again the operator is not involved in work production, as in the capacitor case:

"Liquid Dielectric Capacitor" http://www.youtube.com/watch?v=T6KAH1JpdPg

Accordingly, isothermal heat engines based on the property of catalysts to affect the forward and reverse reactions DIFFERENTLY can generate perpetual motion. For instance, in the picture below, A_2 perpetually flows towards the catalytic surface S1 while A flows towards the catalytic surface S2:

http://upload.wikimedia.org/wikipedi...SLTD-Fig1c.jpg

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