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Obvious Falsehood of the Second Law of Thermodynamics



 
 
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  #1  
Old October 19th 17, 06:20 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Obvious Falsehood of the Second Law of Thermodynamics

Non-isothermal heat engines - apparently do not violate the second law of thermodynamics:

http://readingpenrose.files.wordpres...and-engine.gif

"All materials react to heat in some way. But this new shape-changing polymer reacts to temperatures as small as the touch of human skin to contract - in the process lifting as much as 1,000 times its own weight." http://gizmodo.com/this-new-shape-ch...-it-1759165438

"Stretchy Science: A Rubber Band Heat Engine. Learn how a rubber band can turn heat into mechanical work with this simple activity. [...] Your blow dryer essentially turned your rubber band into a heat engine - a machine that turns thermal energy into mechanical work." https://www.scientificamerican.com/a...ber-band-heat/

ISOTHERMAL analogs - pH-sensitive polymers - do violate the second law of thermodynamics:

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

"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

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." https://www.ncbi.nlm.nih..gov/pmc/ar...00645-0017.pdf

The following four-step isothermal cycle, if carried out quasi-statically (reversibly), 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). That is, the net work involved in steps 1 and 3 is zero, and the net work extracted from steps 2 and 4 is positive, in violation of the second law of thermodynamics.

Pentcho Valev
  #2  
Old October 20th 17, 09:14 AM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Obvious Falsehood of the Second Law of Thermodynamics

"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/

Catalysts cannot accelerate the forward and the reverse reaction EQUALLY - this is an absurd implication of the second law of thermodynamics. Here is a catalyst accelerating the recombination reaction (2H - H2) and SUPPRESSING the reverse dissociation reaction (H2 - 2H):

https://images.nature.com/m685/natur...mms3500-f1.jpg

The publication in Natu

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

Since the catalyst affects the forward and the reverse reaction DIFFERENTLY, the second law of thermodynamics is false.

Catalysts rhenium and tungsten also affect the dissociation reaction (H2 - 2H) and the recombination reaction (2H - H2) DIFFERENTLY:

"A small, closed, high temperature cavity contained two metal catalysts (rhenium and tungsten), which were known to dissociate molecular hydrogen (H2) to different degrees (Figure 1). (Rhenium dissociates hydrogen molecules into atoms better than tungsten does; conversely, tungsten recombines hydrogen atoms back into hydrogen molecules better than rhenium.) Because the dissociation reaction (H2 - 2H) is endothermic (absorbs heat), and the recombination reaction (2H - H2) is exothermic (liberates heat), when hydrogen was introduced into the cavity, the rhenium surfaces cooled (up to more than 125 K) relative to the tungsten (Figure 2). Because the hydrogen-metal reactions were ongoing in the sealed cavity, the rhenium stayed cooler than the tungsten indefinitely. This permanent temperature difference - this steady-state nonequilibrium - is expressly forbidden by the second law, not just because the system won't settle down to a single-temperature equilibrium, but because this steady-state temperature difference can, in principle, be used to drive a heat engine (or produce electricity) solely by converting heat back into work, which is a violation of one of the most fundamental statements of the second law (Kelvin-Planck formulation)." http://microver.se/sse-pdf/edgescience_24.pdf

Perpetual flow of the dimer A2 and the monomer A between two catalytic surfaces, S1 and S2:

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

See the explanation he https://en.wikipedia.org/wiki/Duncan%27s_Paradox

One of the absurd implications of the second law of thermodynamics 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 mechanisms. The absurd 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...um/revision/2/

Scientists should have exposed the absurdity of this implication of the second law of thermodynamics long ago. How can the catalyst increase the rates of the forward and reverse reactions BY THE SAME AMOUNT 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 - the rate of the forward (dissociation) reaction increases by a factor of 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 consisting of

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. The second law of thermodynamics is obviously false.

The false second law of thermodynamics has imposed the wrong and confusing "free energy" interpretation of metabolism:

"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 many 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

Pentcho Valev
  #3  
Old October 20th 17, 10:16 PM posted to sci.astro
Pentcho Valev
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Posts: 8,078
Default Obvious Falsehood of the Second Law of Thermodynamics

Here is vigorous motion of water in an electric field, obviously able to produce work - e.g. by rotating a waterwheel:

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

"The water movement is bidirectional, i.e., it simultaneously flows in both directions." https://www.wetsus.nl/home/wetsus-ne...n-innovation/1

The work (rotating a waterwheel) will be done at the expense of what energy? The first hypothesis that comes to mind is:

At the expense of electric energy. The system is, essentially, an electric motor.

However close inspection would suggest that the hypothesis is untenable. Scientists use triply distilled water to reduce the conductivity and the electric current passing through the system to minimum. If, for some reason, the current is increased, the motion stops - such system cannot be an electric motor.

If the system is not an electric motor, then it is a heat engine violating the second law of thermodynamics. Here arguments describing such heat engines as impossible, idiotic, etc. are irrelevant - the following conditional is valid:

IF THE SYSTEM IS NOT AN ELECTRIC MOTOR, then it is a a heat engine violating the second law of thermodynamics.

In other words, if the work is not done at the expense of electric energy, it is done at the expense of ambient heat. No third source of energy is conceivable.

In the electric field between the plates of a capacitor, the same turbulent motion can be seen:

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

In the capacitor system the rising water can repeatedly do work, e.g. by lifting floating weights. The crucial question is:

The work (lifting floating weights) will be done at the expense of what energy?

Obviously "electric energy" is not the correct answer - the capacitor is not an electric motor. Then the only possible answer remains "ambient heat". The system is a heat engine violating the second law of thermodynamics!

Pentcho Valev
 




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