Paper 4, Section II, A

Statistical Physics
Part II, 2020

Consider a classical gas of NN particles in volume VV, where the total energy is the standard kinetic energy plus a potential U(x1,x2,,xN)U\left(\mathbf{x}_{1}, \mathbf{x}_{2}, \ldots, \mathbf{x}_{N}\right) depending on the relative locations of the particles {xi:1iN}\left\{\mathbf{x}_{i}: 1 \leqslant i \leqslant N\right\}.

(i) Starting from the partition function, show that the free energy of the gas is

F=Fideal Tlog{1+1VN(eU/T1)d3Nx}F=F_{\text {ideal }}-T \log \left\{1+\frac{1}{V^{N}} \int\left(e^{-U / T}-1\right) d^{3 N} x\right\}

where Fideal F_{\text {ideal }} is the free energy when U0U \equiv 0.

(ii) Suppose now that the gas is fairly dilute and that the integral in ()(*) is small compared to VNV^{N} and is dominated by two-particle interactions. Show that the free energy simplifies to the form

F=Fideal +N2TVB(T)F=F_{\text {ideal }}+\frac{N^{2} T}{V} B(T)

and find an integral expression for B(T)B(T). Using ( \dagger ) find the equation of state of the gas, and verify that B(T)B(T) is the second virial coefficient.

(iii) The equation of state for a Clausius gas is

P(VNb)=NTP(V-N b)=N T

for some constant bb. Find the second virial coefficient for this gas. Evaluate bb for a gas of hard sphere atoms of radius r0r_{0}.