An obviously absurd consequence of the second law of thermodynamics is that a catalyst speeds up the forward and reverse reactions equally (by exactly the same factor):

"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/

Actually, things are far from "equally". Here is a catalyst that speeds up the forward reaction, 2H+ → H_2, but SUPPRESSES the reverse reaction, H_2 → 2H+ (violation of the second law of thermodynamics par excellence):

https://www.nature.com/articles/ncomms3500/figures/1

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

An analogous example (the forward and reverse reactions are not sped up "equally"):

"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." https://link.springer.com/article/10.1007/s10701-014-9781-5

Scientists should have noticed the obvious absurdity of this particular consequence of the second law of thermodynamics 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!

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

Pentcho Valev

On 2021-11-13 15:31:00 +0000, Pentcho Valev said:

> An obviously absurd consequence of the second law of thermodynamics is
> that a catalyst speeds up the forward and reverse reactions equally (by
> exactly the same factor):

Oh dear. Back to your old obsession, Pentcho. Probably you're hoping
that no one here will know about how your belief that the 2nd law of
thermodynamics was wrong convinced absolutely no one when you argued
endlessly about it 25 years ago. However, I'm here and I remember
perfectly well. I'm not going to go over the same ground yet again. If
anyone is interested, I finish with your favourite parting shot:

See more here: ...

For some reason the server didn't like a full URL (I got "437 html
post", but I've no idea what that means). If you do a search for
Pentcho Valev you'll find it.

>
> "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/
>
>
> Actually, things are far from "equally". Here is a catalyst that speeds
> up the forward reaction, 2H+ → H_2, but SUPPRESSES the reverse
> reaction, H_2 → 2H+ (violation of the second law of thermodynamics
> par excellence):
>
> https://www.nature.com/articles/ncomms3500/figures/1" rel="nofollow" target="_blank">https://www.nature.com/articles/ncomms3500/figures/1
>
> Yu Hang Li et al. Unidirectional suppression of hydrogen oxidation on
> oxidized platinum clusters https://www.nature.com/articles/ncomms3500
>
> An analogous example (the forward and reverse reactions are not sped up
> "equally"):
>
> "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."
> https://link.springer.com/article/10.1007/s10701-014-9781-5
>
> Scientists should have noticed the obvious absurdity of this particular
> consequence of the second law of thermodynamics 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!
>
> See more here: https://twitter.com/pentcho_valev
>
> Pentcho Valev

--
Athel -- French and British, living mainly in England until 1987.

On Saturday, November 13, 2021 at 5:17:38 PM UTC+1, Athel Cornish-Bowden wrote:

> Oh dear. Back to your old obsession, Pentcho. Probably you're hoping
> that no one here will know about how your belief that the 2nd law of
> thermodynamics was wrong convinced absolutely no one when you argued
> endlessly about it 25 years ago. However, I'm here and I remember
> perfectly well.

Surely you do, Cornish. You don't understand anything in thermodynamics (let alone relativity) so cataloguing other people's opinions is the only thing you can do.

The fact that catalysts speed up the forward and reverse reactions unequally (shift the position of chemical equilibrium) is proved experimentally: https://www.youtube.com/watch?v=HoswY9pgqrU&t=699s

You would not write "Daniel Sheehan FAQ", would you?

Pentcho Valev