Second Law of Thermodynamics – How It Functions at Maximum Entropy

entropystatistical mechanicsthermodynamics

The second law of thermodynamics states that

the entropy in an isolated system cannot decrease

This seems intuitive when considering a low entropy system transitioning to a higher entropy state, but very counterintuitive when considering a system that is currently at the greatest possible entropy because the system can only transition to another maximum entropy state by first passing through a lower entropy state.
Consider, for example, the system shown in "Entropy: Why the 2nd Law of Thermodynamics is a fundamental law of physics" by Eugene Khutoryansky.
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This system starts with $500$ balls in the left container and intuitively we can understand that these balls will spread evenly between the two containers, but what happens when the balls are distributed evenly: $250$ in the left container and $250$ in the right container?

Does the second law of thermodynamics prohibit any ball from moving to another container because that would shift the system into a lower entropy configuration?

EDIT: I believe (although answers seem to indicate that this believe is incorrect) that the state in between has lower entropy because $$\Omega_1 = \binom{1000}{500} > \binom{1000}{501} = \Omega_2$$

Best Answer

The second law of thermodynamics does not prohibit any ball from moving to another container because that would shift the system into a lower entropy configuration.

The question originated from a widespread misconception. There is nothing like the entropy of one configuration in statistical mechanics. Entropy is a property of the macrostate. Therefore, it is a collective property of all the microscopic configurations consistent with the macroscopic variables uniquely identifying the equilibrium state. The physical system visits all the accessible microstates as a consequence of its microscopic dynamics. Among these states, there are states with an unbalanced number of particles in the two containers. People refer to such states as fluctuations around the average equally distributed case. It is an effect of the macroscopic size of thermodynamic systems that the overwhelming majority of the microscopic states does not show large fluctuations.

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