The van der Waals equation of state is

$$p=\frac{k T}{v-b}-\frac{a}{v^{2}}$$

where $p$ is the pressure, $v=V / N$ is the volume divided by the number of particles, $T$ is the temperature, $k$ is Boltzmann's constant and $a, b$ are positive constants.

(i) Prove that the Gibbs free energy $G=E+p V-T S$ satisfies $G=\mu N$. Hence obtain an expression for $(\partial \mu / \partial p)_{T, N}$ and use it to explain the Maxwell construction for determining the pressure at which the gas and liquid phases can coexist at a given temperature.

(ii) Explain what is meant by the critical point and determine the values $p_{c}, v_{c}, T_{c}$ corresponding to this point.

(iii) By defining $\bar{p}=p / p_{c}, \bar{v}=v / v_{c}$ and $\bar{T}=T / T_{c}$, derive the law of corresponding states:

$$\bar{p}=\frac{8 \bar{T}}{3 \bar{v}-1}-\frac{3}{\bar{v}^{2}} .$$

(iv) To investigate the behaviour near the critical point, let $\bar{T}=1+t$ and $\bar{v}=1+\phi$, where $t$ and $\phi$ are small. Expand $\bar{p}$ to cubic order in $\phi$ and hence show that

$$\left(\frac{\partial \bar{p}}{\partial \phi}\right)_{t}=-\frac{9}{2} \phi^{2}+\mathcal{O}\left(\phi^{3}\right)+t[-6+\mathcal{O}(\phi)] .$$

At fixed small $t$, let $\phi_{l}(t)$ and $\phi_{g}(t)$ be the values of $\phi$ corresponding to the liquid and gas phases on the co-existence curve. By changing the integration variable from $p$ to $\phi$, use the Maxwell construction to show that $\phi_{l}(t)=-\phi_{g}(t)$. Deduce that, as the critical point is approached along the co-existence curve,

$$\bar{v}_{\text {gas }}-\bar{v}_{\text {liquid }} \sim\left(T_{c}-T\right)^{1 / 2}$$