Question: The measured decomposition voltage of HBr is less than the reversible voltage, and the prediction of the second law of thermodynamics is exactly the opposite. Do you have any other examples that do not comply with the second law of thermodynamics (prompt: in Physical Chemistry)?
The following is the answer from ChatGPT:
I apologize for my previous response which might have been incorrect. The relationship between experimentally measured decomposition potential and reversible potential does not necessarily always conform simultaneously to the predictions of the Second Law of Thermodynamics, Faraday's laws and the Nernst equation. Thus, decomposition reactions with lower measured potentials do not necessarily indicate that some decomposition reactions do not conform to the Second Law of Thermodynamics.
In addition to the example of HBr, other anti-thermodynamic reversible reactions like the electrochemical deposition of thallium, where the reaction enthalpy is negative, also violate the prediction of the Second Law of Thermodynamics. Moreover, in cases involving biochemical reactions, some enzymes drive high entropy reactions (i.e. different types of molecules are combined to form larger, more complex molecules) by consuming energy molecules such as ATP, which is also an example of a violation of the Second Law of Thermodynamics.
However, it is important to note that these examples do not mean that the Second Law of Thermodynamics is incorrect, but rather that it is not applicable to all chemical reactions in the real world.
ChatGPT also provided the original literature discussion:
"The calculation of the free energy of the electrodeposition of metals from non-aqueous solutions has shown that thallium and lead should not be deposited at room temperature from any of the solvents tried in this investigation excepting when these metals were previously reduced from their salts. Despite these predictions Tl and Pb were found to deposit in good yields from the electrolytes investigated...The electrode potentials encountered were sufficiently negative so that the heats of deposition computed...were negative. It is thus apparent that the electrodeposition of thallium and lead from non-aqueous solutions is thermodynamically impossible at room temperatures, unless catalyzed by a surface of previously deposited metal."
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I suggest you to discuss this question with ChatGPT. This site is designed for communications between humans (professionals in their fields).
There is no reaction in which the second law of thermodynamics is violated. Just the example with the biochemical reactions and the cells, seems at first sight to violate the second law. However, this is a dissipative system, which in turn consists of several systems. These are permanently in exchange with each other and organize themselves or maintain themselves without lowering the entropy. This approach is sometimes better transferable to the real world. I do not know if ChatGPT, knows the theory of dissipative structures of Ilya Prigogine, but would be here in the discussion perhaps a possible answer?
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