Entropy question: Does a substance at 0K have no entropy?

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Discussion Overview

The discussion revolves around the concept of entropy at absolute zero (0 K) and whether a substance can have no entropy at this temperature. Participants explore theoretical implications, mathematical formulations, and specific cases related to the third law of thermodynamics.

Discussion Character

  • Technical explanation, Conceptual clarification, Debate/contested

Main Points Raised

  • One participant questions whether a substance must have zero entropy at 0 K.
  • Another participant references Nernst's theorem, suggesting that entropy approaches zero as temperature approaches absolute zero, provided the ground state is non-degenerate.
  • Some participants note that if there is ground state degeneracy, the entropy at 0 K may not be zero, as indicated by the formula involving degeneracy.
  • It is mentioned that an imperfect crystal can retain non-zero entropy at 0 K due to the presence of defects in the lattice structure.
  • One participant provides a correction regarding Nernst's theorem, emphasizing that near absolute zero, entropy changes in a system at internal equilibrium approach zero.

Areas of Agreement / Disagreement

Participants express differing views on whether entropy is definitively zero at absolute zero, with some asserting it is contingent on the degeneracy of the ground state. The discussion remains unresolved with multiple competing perspectives.

Contextual Notes

Participants reference mathematical formulations and theoretical principles, but there are unresolved aspects regarding the implications of degeneracy and specific conditions under which entropy may not be zero.

Clovis
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Is it 0 K for a substance to have no entropy?Sorry. Just had to get that off my chest.
 
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Nernst's theorem, the 3rd theorem of thermodynamics:
https://en.wikipedia.org/wiki/Third_law_of_thermodynamics
(note the graphic in the section "absolute zero")
and here's the math which directly answers your question
(Google translate isn't perfect, but it works)
https://de.wikipedia.org/wiki/Nernst-Theorem
If the basic state of the system is not degenerate, then ##g = 1## and thus
$$
\lim_{T\to 0}S(T,p,V,\ldots)=S(T=0)=S_ {0}= k_B\cdot \log g = 0
$$
Thus, the entropy of a system disappears when the temperature approaches zero.
 
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As the link given above by @fresh_42 says, if there is ground state degeneracy, then the entropy need not be zero when the temperature is at absolute zero.
 
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An imperfect crystal can have a non-zero entropy at 0 K, which I suppose is because there are many ways to distribute the same number of dislocations/defects in the lattice.
 
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The formula provided by fresh42 is correct. However, when the ground state of a system is degenerate, the entropy at 0 K is not zero, it is ##k_B \cdot log (g)## where g is the degeneracy of the ground state.
 
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fresh_42 said:
Nernst's theorem, the 3rd theorem of thermodynamics...
A slight correction.
Nernst’s statement of the third law says:
Near absolute zero, all reactions in a system in internal equilibrium take place with no change in entropy.

That means: $$\lim_{T \rightarrow 0^+} {\Delta S}=0$$
 

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