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  • How Theoretical Physicists Paralyzed Energetics

    From Pentcho Valev@21:1/5 to All on Sun Jan 30 07:29:27 2022
    For the last 170 years, theoretical physicists have been paralyzing energetics by worshiping the false second law of thermodynamics. An obviously absurd corollary that should have invalidated this law is:

    "Catalysts don't shift the position of chemical equilibrium" https://youtu.be/usAPBgT3aDc?t=1101

    That catalysts can shift chemical equilibrium (and thereby violate the second law of thermodynamics) was my first heretical idea, about 30 years ago. I believed my argument was convincing and enthusiastically submitted a short paper to Nature - they
    rejected it, as it were, before receiving it. My efforts to publish continued, mainly in The Journal of Physical Chemistry, and I was also active on Internet forums. The only result was this (recently the site disappeared from Internet; problems with
    conscience, Athel?):

    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)." http://bip.cnrs-mrs.fr/bip10/valevfaq.htm

    See more here: https://twitter.com/pentcho_valev

    Pentcho Valev

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  • From Pentcho Valev@21:1/5 to All on Mon Jan 31 13:02:36 2022
    An obviously absurd (even idiotic) consequence of the second law of thermodynamics is that any catalyst speeds up the forward and reverse reaction rates equally (by exactly the same factor). In other words, the catalyst does not shift the position of
    equilibrium:

    "In the presence of a catalyst, BOTH THE FORWARD AND REVERSE REACTION RATES WILL SPEED UP EQUALLY, thereby allowing the system to reach equilibrium faster. However, it is very important to keep in mind that the addition of a catalyst has no effect
    whatsoever on the final equilibrium position of the reaction. It simply gets it there faster. [...] If the addition of catalysts could possibly alter the equilibrium state of the reaction, this would violate the second rule of thermodynamics..." https://
    courses.lumenlearning.com/introchem/chapter/the-effect-of-a-catalyst/

    Scientists should have noticed the obvious absurdity of this particular consequence of the second law long ago, and applied reductio ad absurdum: Since the consequence is absurd, the underlying premise, the second law of thermodynamics, is false.

    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!

    Far from speeding up the forward and reverse reactions "equally", here a catalyst speeds up only the forward, 2H+ → H_2, and SUPPRESSES the reverse reaction, H_2 → 2H+ (violation of the second law of thermodynamics par excellence):

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

    More here: https://twitter.com/pentcho_valev

    Pentcho Valev

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