QM vs. the second law of thermodynamics

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SUMMARY

The discussion centers on the relationship between quantum mechanics (QM) and the second law of thermodynamics, specifically addressing the principle that entropy never decreases. It is established that while QM allows for momentary fluctuations in entropy, such as gas particles spontaneously arranging themselves in one half of a container, these occurrences do not violate the second law when considered over time. The entropy is defined as a measure of the number of accessible states in a system, and although specific states may exhibit low entropy temporarily, the overall entropy remains consistent when averaged over time.

PREREQUISITES
  • Understanding of quantum mechanics principles
  • Familiarity with the concept of entropy in thermodynamics
  • Knowledge of Gibbs states and statistical mechanics
  • Basic grasp of the laws of thermodynamics
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  • Research the implications of quantum fluctuations on thermodynamic laws
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This discussion is beneficial for physicists, students of thermodynamics, and researchers interested in the intersection of quantum mechanics and classical thermodynamic principles.

zhermes
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One of the most classical and verified principles of physics is that entropy never decreases. E.g. gas occupying half of a 1L container will quickly disperse quite-evenly throughout the container. It seems however, that QM easily allows momentary violations of this principle. For instance (the classical QM-for-the-laymen idea) is that such a collection of particles (gas in a 1L container) could spontaneously arrange itself into half of the container, with some small probability.
If that happened, wouldn't it be a drastic decrease in entropy?
 
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Entropy is an averaged quantity -- averaged with respect to time. There will always be fluctuations with respect to the 'average' state of the system (the so-called Gibbs state). You cannot speak of the entropy at a specific instance of time, because at any given time the system will be in a definite state which would imply zero entropy. Rather, the entropy arises as a measure of the number of states accessible to the system. As the system evolves it will explore, for lack of a better word, the space of accessible states. The size of this space determines the entropy. If the specific state you mentioned is part of this space of accessible states, then the system will -- at some point -- sit in this state.

But even if the particles arrange themself into half of the container, you're guarenteed that at a later time the system will be in some other state. Averaged over time, the entropy hasn't decreased.
 

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