Thermodynamics : Dismal Swamp of Obscurity and Fraud

Dec 27, 2022
438
12
185
Visit site
The metastases of Einstein's 1905 constant-speed-of-light malignancy definitively killed physics, but this branch of science was already in agony in 1905, overwhelmed by the metastases of another malignancy - the second law of thermodynamics:

Jos Uffink: "I therefore argue for the view that THE SECOND LAW HAS NOTHING TO DO WITH THE ARROW OF TIME...Before one can claim that acquaintance with the Second Law is as indispensable to a cultural education as Macbeth or Hamlet, it should obviously be clear what this law states. This question is surprisingly difficult. The Second Law made its appearance in physics around 1850, but a half century later it was already surrounded by so much confusion that the British Association for the Advancement of Science decided to appoint a special committee with the task of providing clarity about the meaning of this law. However, its final report (Bryan 1891) did not settle the issue. Half a century later, the physicist/philosopher Bridgman still complained that there are almost as many formulations of the second law as there have been discussions of it. And EVEN TODAY, THE SECOND LAW REMAINS SO OBSCURE that it continues to attract new efforts at clarification." http://philsci-archive.pitt.edu/313/1/engtot.pdf

Clifford Truesdell, The Tragicomical History of Thermodynamics, 1822-1854, p. 6: "Finally, I confess to a heartfelt hope - very slender but tough - that even some thermodynamicists of the old tribe will study this book, master the contents, and so share in my discovery: Thermodynamics need never have been the DISMAL SWAMP OF OBSCURITY that from the first it was and that today in common instruction it is; in consequence, it need not so remain."...p. 333: "Clausius' verbal statement of the "Second Law" makes no sense, for "some other change connected therewith" introduces two new and unexplained concepts: "other change" and "connection" of changes. Neither of these finds any place in Clausius' formal structure. All that remains is a Mosaic prohibition. A century of philosophers and journalists have acclaimed this commandment; a century of mathematicians have shuddered and averted their eyes from the unclean." https://www.amazon.com/Tragicomical-Thermodynamics-1822-1854-Mathematics-Physical/dp/1461394465

One cannot expect the "dismal swamp of obscurity" to be inhabited by honest creatures, can one? Consider the most preposterous prediction of the second law of thermodynamics:

"As is true of any catalyst, enzymes do not alter the equilibrium point of the reaction. This means that 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

Since the prediction is obviously absurd (both common sense and empirical reality contradict it), scientists should have applied reductio ad absurdum and rejected the false underlying premise, the second law of thermodynamics, long ago (logic forbids the combination "true premise, absurd prediction"):

"Catalysis is usually construed to facilitate equilibrium being attained more easily and quickly, or occasionally less so (anticatalysis), but not to alter the position of equilibrium, i.e., not to alter the equilibrium constant Keq. Indeed, it is sometimes stated that if catalysis could alter Keq, then it could be employed to violate the Second Law of Thermodynamics. Consider the following cycle, executed isothermally. Insert a catalyst that alters a system’s position of equilibrium or Keq. Then withdraw the catalyst, allowing the system to return (albeit more slowly in the absence of catalysis) to its initial state. The catalyst can then be re-inserted, and the cycle repeated. If, for example, the volume of the system is a function of Keq, then such a cycle could be employed to drive the motion of a piston, thus doing work. It is sometimes stated that such a cycle would violate the Second Law of Thermodynamics, because it represents a heat engine doing work while operating in a cycle despite isothermality [1]. Nevertheless, cases wherein catalysis does alter Keq are known." https://www.longdom.org/open-access...ational-system-a-secondlaw-paradox-31803.html

"CpI is a good catalyst for both H+ reduction and H2 oxidation, exhibiting kcat values of 5800 s−1 and 19 500 s−1, respectively (Table S2, Supporting Information). Not all hydrogenases are good catalysts for both H+ reduction and H2 oxidation, with several examples exhibiting a distinct and often dramatic “catalytic bias” exerting a disproportionate rate acceleration in one direction of the reaction relative to the other." https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8653774/

"Catalytic bias refers to the relative rate preference of a catalyst for either the forward or reverse direction. In enzymatic metal cofactor-based oxidation–reduction catalysis, the tuning of catalytic bias plays an underlying role in controlling rates of reactivity. For this, enzymes have evolved complex active sites that can exist in multiple oxidation states with differing reduction potentials in order to achieve challenging multi-step, oxidation–reduction reactions. Conceivably, the relative stability of the intermediates that contribute to determining the rate-limiting step of the catalytic cycle could impose catalytic bias, although mechanisms for this concept are just beginning to be realized. As one example, recent work on Clostridium pasteurianum [FeFe]-hydrogenases which catalyze reversible hydrogen oxidation have shown that the differential stabilization/destabilization of active site oxidation states through either static or dynamic protein interactions can preferentially promote either the hydrogen oxidation or proton reduction direction of the reaction." https://onlinelibrary.wiley.com/doi/abs/10.1002/9781119951438.eibc2770

"However, many enzymes reversibly convert their substrate and product, and if one is interested in catalysis in only one direction, it may be necessary to prevent the reverse reaction...This is the first demonstration, on a specific example, that slowing a step that is rate limiting only when the enzyme works in one direction is a general mechanism for biasing the enzyme in the other direction." https://hal.science/hal-01977597/document

"PtO-clusters were found to have a pivotal role in unidirectional suppression of undesirable H2 oxidation [the backward reaction] in photocatalytic water cleavage process. More importantly, these PtO-clusters can also demonstrate excellent efficiency in hydrogen evolution rate [the forward reaction]." https://www.nature.com/articles/ncomms3500

"Interestingly, although [FeFe]-hydrogenases all possess the same active site H cluster, they display a large range of H2 gas oxidation and proton reduction activities, with some displaying a dramatic catalytic bias, that is, the propensity of a catalyst to effect rate of acceleration in one reaction direction over the other. " https://europepmc.org/article/pmc/pmc8653774

"The protein scaffold around an enzyme’s catalytic core exquisitely controls reactivity, including the direction and rate of chemical processes. Scientists refer to this fine tuning as “catalytic bias”—and how it occurs remains widely debated...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

"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." https://www.sciencedirect.com/science/article/pii/S2213138818301838

"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

"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

"When enzymes are optimized for biotechnological purposes, the goal often is to increase stability or catalytic efficiency. However, many enzymes reversibly convert their substrate and product, and if one is interested in catalysis in only one direction, it may be necessary to prevent the reverse reaction...We evidence a novel strategy for tuning the catalytic bias of an oxidoreductase, which consists in modulating the rate of a step that is limiting only in one direction of the reaction, without modifying the properties of the active site." https://pubs.acs.org/doi/10.1021/ja301802r
 
Dec 27, 2022
438
12
185
Visit site
Clausius' famous version of the second law, "Entropy always increases", is based on the assumption that any irreversible process can be closed by a reversible process to become a cycle:

Jos Uffink, professor at the University of Minnesota, p.39: "A more important objection, it seems to me, is that Clausius bases his conclusion that the entropy increases in a nicht umkehrbar [irreversible] process on the assumption that such a process can be closed by an umkehrbar [reversible] process to become a cycle. This is essential for the definition of the entropy difference between the initial and final states. But the assumption is far from obvious for a system more complex than an ideal gas, or for states far from equilibrium, or for processes other than the simple exchange of heat and work. Thus, the generalisation to all transformations occurring in Nature is somewhat rash." http://philsci-archive.pitt.edu/archive/00000313/

Uffink's courage and honesty deserve a lot of admiration, and yet it should be noted that his text is misleadingly euphemistic. Except for cases where spontaneous isothermal expansion is pushed back by reversible isothermal compression, the cycles dealt with in Clausius' assumption simply do not exist. No irreversible process can be closed by a reversible process to become a cycle. The concept of entropy is relevant to an ideal gas and to NOTHING in the physical reality:

"The concept of entropy was introduced to thermodynamics by Clausius, who deliberately chose an obscure term for it, wanting a word based on Greek roots that would sound similar to "energy". In this way he hoped to have a word that would mean the same to everyone regardless of their language, and, as Cooper [2] remarked, he succeeded in this way in finding a word that meant the same to everyone: NOTHING. From the beginning it proved a very difficult concept for other thermodynamicists, even including such accomplished mathematicians as Kelvin and Maxwell; Kelvin, indeed, despite his own major contributions to the subject, never appreciated the idea of entropy [3]. The difficulties that Clausius created have continued to the present day, with the result that a fundamental idea that is absolutely necessary for understanding the theory of chemical equilibria continues to give trouble, not only to students but also to scientists who need the concept for their work." https://www.beilstein-institut.de/download/712/cornishbowden_1.pdf

"My greatest concern was what to call it. I thought of calling it 'information', but the word was overly used, so I decided to call it 'uncertainty'. When I discussed it with John von Neumann, he had a better idea. Von Neumann told me, 'You should call it entropy, for two reasons: In the first place your uncertainty function has been used in statistical mechanics under that name, so it already has a name. In the second place, and more important, nobody knows what entropy really is, so in a debate you will always have the advantage." https://en.wikipedia.org/wiki/History_of_entropy

And for a century and a half the nothing called "entropy" has been humiliating and destroying true scientists (nowadays this species is extinct):

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
 
Dec 27, 2022
438
12
185
Visit site
Theoretical physicists would (reluctantly) agree that, if the entropy is not a state function, then it is nonsense. Is there any valid proof that the entropy is a state function? There is none. Here is an oversimplified history of the entropy concept:

If you define the entropy S as a quantity that obeys the equation dS=dQrev/T, you will find that, so defined, the entropy is a state function FOR AN IDEAL GAS: https://socratic.org/questions/is-entropy-state-function-how-prove-it. Clausius decided to prove that the entropy (so defined) is a state function for ANY system. He based his argument on the false assumption that any cycle can be disintegrated into small Carnot cycles, and nowadays this remains the only "proof" that entropy is a state function:

"Carnot Cycles: S is a State Function. Any reversible cycle can be thought of as a collection of Carnot cycles - this approximation becomes exact as cycles become infinitesimal. Entropy change around an individual cycle is zero. Sum of entropy changes over all cycles is zero." http://mutuslab.cs.uwindsor.ca/schurko/introphyschem/lectures/240_l10.pdf

The statement "Any reversible cycle can be thought of as a collection of Carnot cycles" is a blatant lie. An isothermal cycle CANNOT be thought of as a collection of Carnot cycles, a cycle involving action of conservative forces CANNOT be thought of as a collection of Carnot cycles, etc. etc.

Conclusion: The belief that the entropy is a state function is totally unjustified. Any time scientists use the term "entropy", they don't know what they are talking about:

"Von Neumann told me, 'You should call it entropy, for two reasons: In the first place your uncertainty function has been used in statistical mechanics under that name, so it already has a name. In the second place, and more important, nobody knows what entropy really is, so in a debate you will always have the advantage." https://en.wikipedia.org/wiki/History_of_entropy
 
Dec 27, 2022
438
12
185
Visit site
Jos Uffink: "I therefore argue for the view that the second law has nothing to do with the arrow of time...This summary leads to the question whether it is fruitful to see irreversibility or time-asymmetry as the essence of the second law. Is it not more straightforward, in view of the unargued statements of Kelvin, the bold claims of Clausius and the strained attempts of Planck, to give up this idea? I believe that Ehrenfest-Afanassjewa was right in her verdict that the discussion about the arrow of time as expressed in the second law of the thermodynamics is actually a red herring." http://philsci-archive.pitt.edu/313/1/engtot.pdf

A red herring that converted science into a "dismal swamp of obscurity" but, on the other hand, ensured the subsistence of generations of scientists and their families. Bad and good go together, don't they?
 
Conclusion: The belief that the entropy is a state function is totally unjustified. Any time scientists use the term "entropy", they don't know what they are talking about:

"Von Neumann told me, 'You should call it entropy, for two reasons: In the first place your uncertainty function has been used in statistical mechanics under that name, so it already has a name. In the second place, and more important, nobody knows what entropy really is, so in a debate you will always have the advantage." https://en.wikipedia.org/wiki/History_of_entropy
Entropy is of a piece with time travel in reverse. Example: A more perfect lawn that will always be trying to go back to less perfect weeds . . . or vice-versa as to what 'perfection' is. It is built-in inescapable, inexorable, time reversal exactly equaling all time's inescapable, inexorable, forward advancement. Complexity Science's [ever continuing] inescapable, inexorable and inevitable collapse of a complexity that is just as [ever continuing] in its inescapable, inexorable and inevitable build of complexity. A piece of the always cyclic universe of "is" rather than "was.". Ultimate picture forward (+) / back (-), T=0.
---------------

"Brevity is the soul of wit, but repetition is the heart of instruction." -- Gen. George Patton.
 
Last edited:
Dec 27, 2022
438
12
185
Visit site
"Past work has shown that ions can pass through a membrane more readily in one direction than the other. We demonstrate here in a model and an experiment that for a mixture of small and large particles such asymmetric diffusion can arise solely from an asymmetry in the geometry of the pores of the membrane." https://arxiv.org/abs/0704.3766

This, if true, is violation of the second law of thermodynamics par excellence.

Post-truth scientists: Who cares?
 
Dec 27, 2022
438
12
185
Visit site
Philip Ball: "In all of physical law, there’s arguably no principle more sacrosanct than the second law of thermodynamics — the notion that entropy, a measure of disorder, will always stay the same or increase. “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,” wrote the British astrophysicist Arthur Eddington in his 1928 book The Nature of the Physical World. “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.” No violation of this law has ever been observed, nor is any expected." https://www.quantamagazine.org/physicists-trace-the-rise-in-entropy-to-quantum-information-20220526/

But this surpasses Eddington's dishonesty! Philip Ball, a powerful godfather in post-truth science, has exercised himself in crimestop all his life:

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...He set to work to exercise himself in crimestop. He presented himself with propositions - "the Party says the earth is flat", "the party says that ice is heavier than water" - and trained himself in not seeing or not understanding the arguments that contradicted them. It was not easy. It needed great powers of reasoning and improvisation. The arithmetical problems raised, for instance, by such a statement as "two and two make five" were beyond his intellectual grasp. It needed also a sort of athleticism of mind, an ability at one moment to make the most delicate use of logic and at the next to be unconscious of the crudest logical errors. Stupidity was as necessary as intelligence, and as difficult to attain."

Does Philip Ball know the truth about modern science? Yes he does - there are moments of honesty from time to time:

Philip Ball: "Did Einstein discover E=mc2?...The biggest revelation for me was not so much seeing that there were several well-founded precursors for the equivalence of mass and energy, but finding that this equivalence seems to have virtually nothing to do with special relativity. Tony Rothman said to me that "I've long maintained that the conventional history of science, as presented in the media, textbooks and by the stories scientists tell themselves is basically a collection of fairy tales." I'd concur with that." http://philipball.blogspot.com/2011/08/did-einstein-discover-emc2.html

Philip Ball: "And by making the clock's tick relative - what happens simultaneously for one observer might seem sequential to another - Einstein's theory of special relativity not only destroyed any notion of absolute time but made time equivalent to a dimension in space: the future is already out there waiting for us; we just can't see it until we get there. This view is a logical and metaphysical dead end, says [Lee] Smolin." http://www.guardian.co.uk/books/2013/jun/10/time-reborn-farewell-reality-review
 

Latest posts