Homework #3 (Due on 13th Nov.

, 5pm)

1. The equation-of-states of van der Waals fluid can be written as 𝑝 = 𝑘𝐵 𝑇𝜌/(1 − 𝑏𝜌) − 𝑎𝜌2 ,
where 𝑎, 𝑏 are positive constants and 𝜌 = 𝑁/𝑉 is the density of molecules in the fluid. (i)
Find the change in energy per molecule Δ𝑢 upon isothermal expansion from per-molecule-
volume 𝑣1 to 𝑣2 (𝑣2 > 𝑣1 ). (ii) Find the change in energy per molecule Δ𝑢 upon an adiabatic
expansion between the same two volumes. (iii) Which is greater?

2. Show that the constant-volume heat capacity 𝐶𝑉 of a van der Waals fluid is (i) independent
𝜕𝐶
of volume, i.e., ( 𝜕𝑉𝑉) = 0, but (ii) the constant-pressure heat capacity 𝐶𝑝 is dependent on
𝑇
𝜕𝐶𝑝
pressure, i.e., ( 𝜕𝑝 ) ≠ 0.
𝑇

3. By a set of experiments, it is determined that the molar heat capacity of a substance obeys
the empirical relation: 𝑐𝑉 (𝑇, 𝑣) = 𝑎𝑇 2 𝑣 2 , where 𝑎 is a constant and 𝑣, 𝑇 the molar volume
and temperature, respectively. Assume that the entropy and energy are zero at absolute zero
temperature, work out the molar thermodynamic functions 𝑢(𝑠, 𝑣), 𝑓(𝑇, 𝑣), and ℎ(𝑠, 𝑝).

4. The Helmholtz free energy of a solid can be approximated as 𝐹(𝑇, 𝑉, 𝑁) =

3𝑁𝑘𝐵 𝑇 ln[(𝑁𝑉)𝑚 𝑏𝑇], where 𝑏 and 𝑚 are constants. Find the expressions of the
thermodynamic potentials of (i) 𝑈(𝑆, 𝑉, 𝑁), the internal energy, and (ii) 𝐺(𝑇, 𝑝, 𝑁), the
Gibbs free energy.