[Physics] Why doesn’t the entropy increase when two similar gases mix with each other

entropyidentical-particlesstatistical mechanicsthermodynamics

Entropy increases when two substances mix with each other.

For example, the entropy of mixing of two different gases are given by $$\Delta S= 2Nk\ln\frac{V_f}{V_i}\;.$$

But, the entropy doesn't increase when the two gases mixing are same.

This is pointed by Daniel V Schroeder:

It's important to note that this result applies only if the two gases are different like helium and argon. If you start with the same gas on both sides, the entropy doesn't increase at all when you remove the partition.

Now, why is this so? Both the gases, though the same, increase their individual entropies when they expand, don't they?

So, why did Schroeder say there is no entropy of mixing? What actually happens such that there is no change in entropy when the gases are the same?

Best Answer

When two identical gases mix, the state is generally indistinguisable from the previous state. If one molecule from the left of the partition changes places with a molecule from the right of the partition, does the mixture actually look any different? If the left and right molecules are identical, you would never know which ones started where.

So entropy doesn't change. It doesn't change because you can't tell the two states apart.

Contrast this with the mixing between two different gases. When a partition is removed and an argon and several helium molecules switch places in space due to collisions, now you can actually see a difference. The state is identifiable and different from the previous state. This means the entropy has changed.