Maxwell's Demon as a Biased Catalyst

"In the philosophy of thermal and statistical physics, Maxwell's demon is a thought experiment created by the physicist James Clerk Maxwell in which he suggested how the Second Law of Thermodynamics might hypothetically be violated. In the thought experiment, a demon controls a small door between two chambers of gas. As individual gas molecules approach the door, the demon quickly opens and shuts the door so that fast molecules pass into the other chamber, while slow molecules remain in the first chamber. Because faster molecules are hotter, the demon's behavior causes one chamber to warm up as the other cools, thus decreasing entropy and violating the Second Law of Thermodynamics." https://en.wikipedia.org/wiki/Maxwell%27s_demon

"The passage of a gas molecule through the membrane is essentially a chemical reaction due to a change of configuration of the system and an accompanying change in potential energy, and we can write for the forward and reverse reactions: G_A ⇆ G_B, where G is the gas and the subscripts denote location." http://www.mdpi.com/1099-4300/6/1/96/htm

The second quotation implies that a biased catalyst - stimulating only the forward reaction but not the reverse - would be an efficient Maxwell's demon. Are there such catalysts? The answer is "yes".

The false restrictive principle called "Second law of thermodynamics", apart from preventing humankind from understanding fundamental energy conversions in Nature, has produced collateral damages as well. One of its idiotic implications 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 strategies. The idiotic implication is usually referred to as "Catalysts do not shift chemical equilibrium".

The restriction imposed on catalysts by the second law has led to the false and essentially tautological "free energy" interpretation of the unidirectionality of metabolism:

https://www.scribd.com/doc/61362780/Enzyme-Activity
"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."

The unidirectionality is not determined by free energy changes - it is due to the property of biased enzymes to catalyze only the forward reaction, not the reverse.

A paradigmatic example of the inability of catalysts to accelerate both - forward and reverse - reactions to the same extent are diffusion-controlled reactions:

https://en.wikipedia.org/wiki/Diffus...olled_reaction
"Diffusion-controlled (or diffusion-limited) reactions are reactions that occur so quickly that the reaction rate is the rate of transport of the reactants through the reaction medium (usually a solution). As quickly as the reactants encounter each other, they react. The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency."

Can a catalyst accelerate a diffusion-controlled reaction? Obviously not - catalysts do not accelerate diffusion. On the other hand, nothing prevents the catalyst from accelerating the reverse reaction, which means shifting the equilibrium and is tantamount to violating the second law of thermodynamics:

Consider the association-dissociation reaction

A + B - C

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

A + B - C

is diffusion-controlled. The reverse

C - A + B

is not diffusion-controlled, obviously.

We add a catalyst, e.g. a macroscopic catalytic surface, and it starts splitting C so efficiently that the rate of the reverse (dissociation) reaction increases by a factor of, say, 745492. If the second law of thermodynamics is obeyed, the catalyst must increase the rate of the forward (association) reaction by exactly the same factor, 745492, which is impossible - the catalyst cannot accelerate the forward (diffusion-controlled) reaction at all!

The forward reaction may not be diffusion-controlled and the catalyst may be able to accelerate it to some extent, but if the diffusion factor still plays some role in determining the rate of the forward reaction, it would be unrealistic, even idiotic, to assume that the catalyst increases both rates - of the forward and reverse reaction - by a factor of 745492.

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. In such cases, even at equilibrium, there will be local temperature and concentration gradients (e.g.. at the catalytic surface) that can in principle be harnessed to do work.

Scientists have always known that catalysts do shift chemical equilibirum:

https://www.facebook.com/ParadigmEne...49600938581128
"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."

The second-law-violating effect 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]

Parpetual-motion machines based on the property of biased catalysts to shift chemical equilibrium have even entered a commercialization phase (without much success - the effect is too weak to be of technological use):

https://www.google.com/patents/US20140352682
"An Epicatalytic Thermal Diode (ETD) includes one or more ETD cells. Each cell comprises first and second surfaces with a cavity between them, which contains a gas that is epicatalytically active with respect to the pair of surfaces. The surfaces chemically interact with the gas such that the gas dissociates at a faster rate proximate to the first surface than it does proximate to the second surface. Thus, a steady-state temperature differential between the first surface and the second surface is created and maintained.. In various applications, multiple ETD cells are connected in series and/or parallel."

http://aip.scitation.org/doi/abs/10.1063/1.4954971
"Recently, a new mode of gas-surface heterogeneous catalysis (epicatalysis) has been identified, having potential applications ranging from industrial and green chemistry to novel forms of power generation. This article describes an inexpensive, easily constructed, vacuum-compatible apparatus by which multiple candidate gas-surface combinations can be rapidly screened for epicatalytic activity."

Pentcho Valev

The violation of the second law of thermodynamics by catalysts can be as simple as this:

"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

Pentcho Valev

"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 should have noticed long ago that this consequence of the second law of thermodynamics is idiotic. How can the catalyst increase the rates of the forward and reverse reactions BY THE SAME AMOUNT (EQUALLY) if these two reactions are entirely different? Consider, again, 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 so efficiently that the rate of the forward (dissociation) reaction increases by a factor of, say, 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 involving just

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 (EQUALLY). The second law of thermodynamics is obviously false.

That catalysts can shift chemical equilibrium was my first heretical idea, about 20-25 years ago. I believed my argument was convincing and enthusiastically submitted a short paper to Nature - they rejected it without reading it (let alone giving it to referees). My efforts to publish continued, mainly in The Journal of Physical Chemistry, and I was also active on Internet forums. The main result was this:

http://bip.cnrs-mrs.fr/bip10/valevfaq.htm
Athel Cornish-Bowden 1998: "Reading Mr Valev's postings to the BTK-MCA and other news groups and trying to answer all the nonsense contained in them incurs the risk of being so time-consuming that it takes over one's professional time completely, leaving none for more profitable activities. On the other hand, not answering them incurs the even greater risk that some readers of the news group may think that his points are unanswerable and that thermodynamics, kinetics, catalysis etc. rest on as fragile a foundation as he pretends. [...] Can a catalyst shift the position of an equilibrium? No. Absolutely not if it is a true catalyst present at very low concentrations. If it is present at a concentration comparable with that of one or more of the reactants then it may appear to shift the position of equilibrium by mass action effects. However, when it does this it is acting as a reactant, not as a catalyst. Mr Valev's claims to have shown otherwise... [...] Suffice it to say that if Mr Valev really believed what he was saying he would not be writing nonsense on this news group, he would be building the machine that would make him the richest man in Bulgaria (or even the world)."

Pentcho Valev

Here is water placed in an electric field. Vigorous cyclic motion can be seen, obviously able to produce unlimited amount of work at the expense of heat absorbed from the surroundings (no other source of energy is conceivable - no electric current passes through the system). Also, heat flows from cold (surroundings) to hot (the bridge) - the heat accumulated in the bridge can come from nowhere else:

https://www.youtube.com/watch?v=QULP3GVJTMI
Floating Water Bridge - Wasserfadden - Physics Experiment

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

http://www.anl.gov/articles/scientis...troubled-water
"One thing that the researchers did notice is that the water in the bridge tends to get quite hot as the bridge forms – in some cases exceeding 50 degrees Celsius (122 degrees Fahrenheit). According to Benmore, there have been cases in which boiling floating water bridges have formed."

https://www.youtube.com/watch?v=PXJcSt8VYpo
Floating water bridge / thermography

Physicists watch the videos - not one could think of a reason why the second law of thermodynamics should be questioned. Actually there is no thought at all in physicists' heads at that moment:

http://ebooks.adelaide.edu.au/o/orwe...hapter2.9.html
"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."

The floating water bridge is a relatively complicated system - it would be difficult to extract the underlying fundamental physics from it. Fortunately, the same fundamental physics is present in the much simpler capacitor-in-dielectric-liquid system.

In the electric field between two capacitor plates (or, generally, two opposite electric charges) water develops a specific force (pressure) which, like other forces, can cause motion and produce work:

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.amazon.com/Classical-Elec...iglink21401-20
Wolfgang K. H. Panofsky, Melba Phillips, Classical Electricity and Magnetism, pp.115-116: "Thus the decrease in force that is experienced between two charges when they are immersed in a dielectric liquid can be understood only by considering the effect of the PRESSURE OF THE LIQUID ON THE CHARGES themselves."

http://www.amazon.com/Introduction-T.../dp/0763738271
Tai Chow, Introduction to Electromagnetic Theory: A Modern Perspective, p. 267: "The strictly electric forces between charges on the conductors are not influenced by the presence of the dielectric medium. The medium is polarized, however, and the interaction of the electric field with the polarized medium results in an INCREASED FLUID PRESSURE ON THE CONDUCTORS that reduces the net forces acting on them."

Crucial questions a If the pressure that emerges between the plates is allowed to produce work, what source of energy will be used? And what molecular mechanisms will be responsible for the work production? I tried to answer such questions in 2004 but the paper was not very well written:

http://www.gsjournal.net/old/valev/valev2.htm
Biased Thermal Motion and the Second Law of Thermodynamics (August 12, 2004)

Let me offer a clearer (I believe) explanation. Consider a constant-charge parallel-plate capacitor with a polarized SOLID dielectric between the plates:

http://www.gsjournal.net/old/valev/val1.gif

Since the molecules of the dielectric material are polarized, they generate an electric field which counteracts the original field and so reduces the voltage between the plates. On the other hand, the attraction between the plates increases (the polarization obviously reinforces the original attraction).

If the dielectric is LIQUID and the plates are totally immersed in it, the attraction between the plates surprisingly decreases, due to the pressure that emerges in the space between the plates. We have a high pressure between the plates and a lower pressure outside the capacitor so if we punch a small hole in one of the plates, there will be an ETERNAL FLOW through the hole, from inside (between the plates) to outside. In other words, we will have a SYSTEM IN DYNAMIC EQUILIBRIUM. The eternal flow can be harnessed to do work, in violation of the second law of thermodynamics.

The system can violate the second law in a more traditional way. If the plates of the capacitor are only partially immersed, the pressure between them pushes the liquid upwards:

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."

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

But the rising dielectric liquid can do useful work, e.g. by lifting some floating weight, and here is the crucial question again: 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.

What is the molecular mechanism behind the effect? Here is a schematic presentation of water dipoles in the electrical field:

http://www.gsjournal.net/old/valev/val2.gif

If it were not for the indicated (with an arrow) dipole, other dipoles in the picture are perfectly polarized as if there were no thermal motion. Of course, this is an oversimplification – thermal motion is a factor which constantly disturbs the polarization order. However the crucial point is that, as can be inferred from the picture, any thermal disturbance contributes to the creation of a pressure between the plates. Consider the indicated dipole. It has just received a strong thermal stroke and undergone rotation. As a result, it pushes adjacent dipoles electrostatically, towards the plates. Macroscopically, the sum of all such disturbances is expressed as a pressure exerted on the plates. One can also say, somewhat roughly, that the indicated dipole has absorbed heat and now, by pushing adjacent dipoles, is trying to convert it into work.

In general terms, electric fields manage to channel the chaotic thermal motion into a macroscopically expressed force capable of doing macroscopic work. In 2002 I tried, for the first time, to call the attention of the scientific community to the effect (but failed):

"In the chemical example, dynamical equilibrium is established in the presence of catalysts that selectively favor either the forward or reverse reaction - a property that is by no means indisputable. (Rather, the denial of this property is an essential dogma in chemistry). Yet there is another example in which the principle of dynamical equilibrium is, in my view, obvious.. [...] ...as two vertical constant-charge capacitor plates partially dip into a pool of a liquid dielectric (e.g. water), the liquid between them rises high above the surface of the rest of the liquid in the pool. Evidently, if one punches a macroscopic hole in one of the plates, nothing could prevent the liquid between the plates from leaking out through the hole and generating an eternal waterfall outside the capacitor. This hypothesis has been discussed on many occasions but so far no serious counter-argument has been raised." Pentcho Valev, The Law of Self-Acting Machines and Irreversible Processes with Reversible Replicas. http://adsabs.harvard.edu/abs/2002AIPC..643..430V

Pentcho Valev