Statistical Physics Vishnu Jejjala

Assignment 1
Solutions should be prepared in LATEX.

1. Let pi (t) be the probability that at time t the system is in a state |i⟩. Define the canonical
entropy as X
S = −kB pi log pi . (1)
i

• Show that in equilibrium for an isolated system, the principle of equal a priori proba-
bilities implies that this definition reduces to the formula S = kB log Ω, where Ω is the
total number of states.
• Let Vij be the probability per unit time of a transition from the initial state |i⟩ to a
state |j⟩. Starting from the master equation
dpi X
= [Vji pj − Vij pi ] , (2)
dt
j

show that the canonical entropy S is a non-decreasing function in time by explicitly

calculating Ṡ. State the assumptions that inform your computation.

2. a. Consider a ball of mass m moving on a spring with spring constant k. The Hamiltonian,
which is a constant because of energy conservation, is
p2 kq 2
H= + , (3)
2m 2
where q is the displacement and p is the momentum. Let q = 0 at time t = 0.

• Write the Hamilton equations of motion. For convenience, you can set k = 1 and m = 1.
• Draw the trajectory of this system in phase space.
• Show that any trajectory (q(t), p(t)) in phase space will spend, on average, equal time
in all regions of the surface with constant energy E.

b. Now, consider two equal masses connected by a spring free to move in three dimen-
sions. The positions and momenta of the balls are given by the vectors (q1 , p1 ) and (q2 , p2 ),
respectively. The Hamiltonian is
1 k
H= (p21 + p22 ) + (q1 − q2 )2 . (4)
2m 2
• Write second order equations of motion for this system. Again, for convenience, you
can set k = 1 and m = 1.
• Consider the combinations q± = q1 ± q2 . This choice of coordinates simplifies the
equations of motion you have just found. What is the phase space of the system?
• Show that any trajectory (q(t), p(t)) in phase space will not visit all regions of the surface
with constant energy E.

3. a. Let the internal energy U of a gas be a function of its temperature and volume. We wish
to show that   
∂p 
dU = CV (T, V ) dT + T − p dV . (5)
∂T V
We will proceed in steps.

1
Statistical Physics Vishnu Jejjala

• Suppose that the internal energy U is some function of T and V . Write an expression
for dU in terms of dT and dV . What is CV (T, V )?
• The entropy S is also a function of T and V . Write an expression for dS in terms of dT
and dV . Using the fact that dU = T dS − p dV , write the coefficients of dT and dV in
terms of p, T , and derivatives of U .
• Compute
∂2S
(6)
∂T ∂V
in two different ways: firstly, by taking the V derivative and then the T derivative and
secondly, the other way around. Use these expressions to obtain (5).

b. An ideal gas treats the molecules as point particles with no intermolecular interactions. In
a van der Waals gas, we take into account the finite size of molecules and the forces between
them. The equation of state for a van der Waals gas is
"  2 #
N
p+ a (V − N b) = N kB T . (7)
V

Here, a is a measure of the attraction between the molecules and b accounts for the space
the molecules take up. Given the internal energy and the entropy at a temperature T0 and
volume V0 , we seek to derive expressions for the internal energy and entropy at a temperature
T and a volume V in terms of an integral of the heat capacity and a function of the volume.
Assume that the particle number N is constant. Again let us proceed in steps.

• Compute 
∂p 
T −p (8)
∂T V
for a van der Waals gas.
• Show that the heat capacity of a van der Waals gas is independent of the volume.
• Using the above, integrate (5) to obtain U (T, V ).
• Write an expression for dS and integrate this to obtain S(T, V ).

4. You visit friends who are cooking outside by fire. There is a metal bucket of water on the
ground immediately next to the flames. Strangely, you measure that the bucket is much
warmer on the side facing away from the fire. How is this possible? Why am I asking this
question?