When accounting for the excluded volume for in the Van der Waals equation, it is assumed that the molecules are hard spheres and are of diameter. If we consider a cube of volume V, then we can say that the side of this cube is of length $V^{1/3}$. Consider the diameter of the molecules to be $\sigma$. Suppose that the number of molecules in this box to be $N$. If we anchor $N-1$ molecules at their positions and look at the excluded volume from the perspective of the $N^{th}$! molecule, we see that the center of this molecule can approach the walls of the cube only upto a distance of $\sigma/2$ and can approach the anchored molecules upto a distance of $\sigma$ from their centers as shown:.
Then the excluded volume for this molecule should be $V_{ex}=(V^{1/3}-\sigma)^{3}-(N-1)(\frac{4}{3}\pi\sigma^{3})$. This follows even if we consider any other molecule and anchor the rest. But, according to wikipedia, we would be overcounting. I don't see how. The correct expression should be $V_{ex}=(V^{1/3}-\sigma)^{3}-(N/2)(\frac{4}{3}\pi\sigma^{3})$. Can anyone please explain?
Answer
As mentioned in the wikipedia page $4 \times \frac{4 \pi r^3}{3}$ is the excluded volume per particle, so you have to sum over all the particles and divide by the number of particles. While summing up you divide by 2, because a pair of particles only contribute once to the excluded volume.
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