# Catalysts Will Topple Thermodynamics One Day

#### Pentcho Valev

"Suppose that, as indicated in the figure, the catalyst affects only the forward reaction. In its presence, the sum of the forward rates would clearly be larger than otherwise, while the backward rate would be unchanged. The position of equilibrium would therefore shift to the right, by the law of mass action. If we suppose further that the reaction produces heat q when it occurs, then a violation of the second law would be possible. We first allow equilibrium to be reached without the catalyst...and then add the catalyst, and heat δq is produced as the equilibrium is shifted. This heat is used to run a machine, and thus do work, cooling the system back to its original temperature in the process. We then remove the catalyst and the equilibrium shifts back. Heat δq is now extracted from the surroundings, which must warm the system back to the ambient temperature. A cycle has therefore been completed for which the net effect has been the isothermal conversion of heat energy into work, and a perpetual motion machine of the second kind has been found. We conclude that the supposed situation is impossible and that the catalyst must accelerate the forward and backward reactions equally." https://dtk.tankonyvtar.hu/bitstream/handle/123456789/8903/B9780120442621500128.pdf

The conclusion that "the catalyst must accelerate the forward and backward reactions equally" is absurd, so we have refutation of the second law of thermodynamics through reductio ad absurdum. Scientists should have exposed the absurdity of this particular consequence of the second law long ago. Consider the dissociation-association reaction

A ⇌ B + C

which is in equilibrium. We add a catalyst and it starts splitting A - the rate constant 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 constant of the reverse (association) reaction by exactly the same factor, 745492. But this is insane! The reverse reaction is entirely different from the forward one: B and C must first get together, via diffusion, and only then can the catalyst join them to form A. Catalysts don't speed up diffusion!

There are countless examples of biased and even unidirectional catalysis in the literature but authors universally suppress information allowing one to unequivocally conclude that the second law is violated. There are exceptions of course:

"In 2000, a simple, foundational thermodynamic paradox was proposed: a sealed blackbody cavity contains a diatomic gas and a radiometer whose apposing vane surfaces dissociate and recombine the gas to different degrees (A_2 ⇌ 2A). As a result of differing desorption rates for A and A_2 , there arise between the vane faces permanent pressure and temperature differences, either of which can be harnessed to perform work, in apparent conflict with the second law of thermodynamics. Here we report on the first experimental realization of this paradox, involving the dissociation of low-pressure hydrogen gas on high-temperature refractory metals (tungsten and rhenium) under blackbody cavity conditions. The results, corroborated by other laboratory studies and supported by theory, confirm the paradoxical temperature difference and point to physics beyond the traditional understanding of the second law." https://link.springer.com/article/10.1007/s10701-014-9781-5

"A simple device is introduced that utilizes the phenomenon of epicatalysis to establish a stationary temperature difference by which ambient environmental thermal energy might be converted into useful work...Traditional catalysis is a central pivot around which much of the industrial and biological worlds turn. Positive catalysts satisfy three general principles. First, they increase reaction rates by providing lower activation energies for rate-limiting steps. Second, they are not consumed by their net reactions although they are intimately involved in them. Third, they do not alter final thermodynamic equilibria of their reactions. Epicatalysts bend this third principle in that they shift the final gas-phase equilibria of reactions." D. P. Sheehan, T. M. Welsh, Epicatalytic thermal diode: Harvesting ambient thermal energy, Sustainable Energy Technologies and Assessments, Volume 31, February 2019, Pages 355-368 https://www.sciencedirect.com/science/article/pii/S2213138818301838

Far from accelerating the forward and backward reactions "equally", in this experiment

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

a catalyst accelerates only the forward reaction, 2H+ → H_2, and SUPPRESSES the backward reaction, H_2 → 2H+. Violation of the second law par excellence.

#### Pentcho Valev

View: https://youtu.be/FP0VjeRap04?t=1130

There is no separate group of "epicatalysts" - actually all catalysts shift the equilibrium to some extent and so violate the second law of thermodynamics (even though the effect is, generally, very difficult to prove). A major function of enzymes, apart from speeding up metabolic reactions, is to make some of these reactions unidirectional: the forward reaction is accelerated, the reverse is not.

#### Pentcho Valev

Post-truth science: "Since a reverse chemical reaction may proceed by reversal of the steps constituting the mechanism of the forward reaction, the catalyst for a given reaction accelerates the reaction in both directions equally. Therefore, a catalyst does not affect the position of equilibrium of a chemical reaction; it affects only the rate at which equilibrium is attained." https://www.britannica.com/science/catalysis

The consequent, "the catalyst for a given reaction accelerates the reaction in both directions equally", does not follow from the antecedent, "a reverse chemical reaction may proceed by reversal of the steps constituting the mechanism of the forward reaction". The argument is clearly invalid. Consider the dissociation-association reaction

A ⇌ B + C

The catalyst can accelerate B and C moving away from one another (by splitting A and letting diffusion finish the job), but it can by no means accelerate the reverse process - B and C moving towards each other. If the reverse reaction, B+C→A, is diffusion-controlled, the catalyst cannot accelerate it at all.

That "the catalyst for a given reaction accelerates the reaction in both directions equally" is perhaps the most preposterous consequence of the second law of thermodynamics.

#### Pentcho Valev

"I listened to the lecture about enzymes. Professor downplayed the question in the subject. He said that enzymes are able to work both ways, but practically speaking reactions with overwhelming probability flow in only one direction. He said that a variety of factors cause this, and there is nothing interesting there beyond this." https://chemistry.stackexchange.com/questions/108094/why-enzyme-catalyzed-reactions-mostly-go-one-way

Is one allowed to assume that most enzymes are unidirectional catalysts - accelerate the forward reaction but don't accelerate the backward? No. One is not allowed to even think about that:

George Orwell: "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."

Deepest humiliation awaits anyone who challenges the second law of thermodynamics:

Arthur Eddington: "The law that entropy always increases—the Second Law of Thermodynamics—holds, I think, the supreme position among the laws of Nature. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell’s equations—then so much the worse for Maxwell’s equations. If it is found to be contradicted by observation—well these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of thermodynamics I can give you no hope; there is nothing for it but to collapse in deepest humiliation." https://todayinsci.com/E/Eddington_Arthur/EddingtonArthur-Entropy-Quotations.htm

#### Pentcho Valev

"In enzymology, there has been much interest in trying to elucidate what makes a particular enzyme faster in one direction (a property sometimes called the “catalytic bias”)." http://frenchbic.cnrs.fr/2022/09/22/2023-workshop-on-bidirectional-catalysis-from-molecular-machines-to-enzymes/

"This has resulted in a deeper understanding of the hydrogenase model system and the ability to directly influence catalytic bias. Thus, the work presented here represents key progress towards developing unidirectional catalysts, and demonstrates the possibility of targeted, rational design and implementation of unidirectional catalysts." https://scholarworks.montana.edu/xmlui/handle/1/14621

If enzymologists cared about the preposterous implications of the second law of thermodynamics, the above texts would not exist. The second law says that a particular enzyme is faster, e.g. by a factor of 1794538, in one direction because the uncatalyzed reaction is precisely 1794538 times faster in that direction. Accordingly, no "progress towards developing unidirectional catalysts" is possible. It all depends on the uncatalyzed reaction. Insane, isn't it?

#### Pentcho Valev

The second law of thermodynamics predicts:

"It is important to recognize that when an enzyme (or any catalyst) lowers the activation energy for the reaction A → B, it also lowers the activation energy for the reaction B → A by exactly the same amount (see Figure 2-44). The forward and backward reactions will therefore be accelerated by the same factor by an enzyme..." https://www.ncbi.nlm.nih.gov/books/NBK26838/

Here is what actually happens:

"A research team from three U.S. Department of Energy (DOE) national laboratories and four universities found that subtle changes to the environment surrounding some enzymes can not only change the rate of a cellular reaction by a staggering six orders of magnitude but also its direction. That reversal—the root of the catalytic bias dilemma—is like speeding in one direction at 10 miles-per-second, then going in the opposite direction at 1,000,000 miles-per-second." https://www.pnnl.gov/news-media/remarkable-rate-return-catalytic-bias

Is the second law in trouble, theoretical physicists?

Theoretical physicists:

#### Pentcho Valev

"Enzymes are the catalysts of biological systems and are extremely efficient and specific as catalysts. In fact, typically, an enzyme accelerates the rate of a reaction by factors of at least a million compared to the rate of the same reaction in the absence of the enzyme...the enzyme accelerates the forward and reverse reaction by precisely the same factor." http://www.columbia.edu/itc/chemistry/ARCHIVE/chem-c2407_f99/problems/kinetics1.pdf

If a catalyst does not accelerate the forward and reverse reaction "by precisely the same factor", the second law of thermodynamics is false.

"Precisely the same factor" is perhaps the most preposterous corollary of the second law, easily refutable both theoretically and experimentally.