Thermodynamics and Statistical Physics Exam
You may use your textbook (Thermal Physics by Schroeder) and a
calculator.
1. Short questions. No calculation needed.
(a) Two rooms A and B in a building are connected by an open door.
One room (say, A) is on the sunny side of the building and is warmer
than the other room. Which room has more oxygen per unit volume?
Explain.
SOLUTION: The system must at least be in mechanical equilibrium,
even if not in thermal equilibrium. Thus, the pressures must be equal.
This means that A, being at a higher temperature, will have a lower
density of nitrogen and oxygen.
(b) The room-temperature heat capacity of 1 kg of iron (Fe) is about 450
J/K, while the heat capacity of 1 kg of lead (Pb) is only about 125
J/K. Explain the difference (qualitatively).
SOLUTION: What counts for the heat capacity is the number of de-
grees of freedom. Lead atoms are heavier, implying a smaller number
of them per kg. Thus, the heat capacity is expected to be lower per
kg.
2. Starting from the Clausius-Clapeyron equation (5.47), consider the case
of a liquid-gas phase transition, in which the latent heat L is constant and
the volume Vg of the gas phase is much larger than the volume Vl of the
liquid. By approximating ∆V = Vg −Vl ' Vg and assuming that the gas is
ideal, derive a differential equation for the vapor pressure P as a function
of T , and show that the solution is
P (T ) = const. × e−`/kT ,
where ` is the latent heat per molecule.
SOLUTION: This was essentially one of your homework problems. See
the solutions to problem 5.35.
3. The following is a simple model of an electrically polarizable solid. Con-
sider N independent, identical charges q that are each bound to lattice
sites by identical springs with spring constant K. In the presence of an
electric field E, the energy of a charge is
1
U= Kx2 − Eqx,
2
where x is the displacement of the charge.
(a) Apart from an overall constant, what is the probability as a function
of x of an individual charge at fixed temperature T and applied field
E?
SOLUTION: The probability
1 2 2
P(x) ∝ e−β( 2 Kx −Eqx)
= const. × e−βK(x−x0 ) /2
,
where x0 = Eq/K.
(b) Find the average displacement hxi for one charge, and the total po-
larization of the solid P = N qhxi.
SOLUTION: Due to the symmetry of the distribution above, the
average hxi = x0 , which also corresponds to the maximum of the dis-
tribution. Since the charges are assumed to be independent of each
other, the total polarization simply adds, as indicated above.
(c) Calculate the partition function Z(T, E) and find the average energy
hU i.
Z r
1
βKx 2
− 1
βK(x−x ) 2 1
βKx 2 2πkT
Z(T, E) = e 2 0 e 2 0
dx = e 2 0 .
K
From this, we find
∂ 1 1
U =− log Z = − Kx20 + kT.
∂β 2 2
2
4. The following is a somewhat more realistic model of a rubber band than
you considered in a homework problem. Here, the entropy S as a function
of energy U and end-to-end distance x is given by
x2
S(U, x) = −k + N k log U + constant.
2N a2
Here, k is Boltzmann’s constant, N represents the number of links in the
chain-like molecules making up the rubber band, and a is a molecular size.
(a) Find the energy U as a function of temperature T .
SOLUTION:
1 ∂S Nk
= = ,
T ∂U U
or
U = N kT.
(b) Consider a small, adiabatic (dQ = 0) expansion of the rubber band
from x to x + dx, were x > 0 and dx > 0. Does the temperature
increase or decrease? By how much?
SOLUTION: From the first law, dU = dQ + f dx = f dx for an adia-
batic process (see solutions to problem 3.34). Thus, dU = N kdT =
f dx = NkTa2 xdx, or
T xdx
dT = 2 2 > 0,
N a
where I have used
∂S kT
f = −T = x
∂x N a2
(again, see problem 3.34). Thus, the system heats up.
We could have derived this another way. An adiabatic expansion is
reversible, and S remains constant. Thus,
x2
k = N k log U + constant.
2N a2
Using this, we find
kx Nk Nk
dx = dU = dT,
N a2 U T
which is equivalent to the expression for dT above.
3
5. (a) In the nineteenth century, using Maxwell’s equations, it was already
known that the electromagnetic pressure exerted on the walls of an
evacuated container of volume V was related to the energy U by the
formula
1
P = U/V.
3
Assuming that the entropy S(U, V ) is a function of the energy and
volume, and that the energy density
U
= AT λ ,
V
where both A and λ are constants, show that λ must be 4. (This is
a result first derived by Boltzmann.)
SOLUTION: If S is a function only of U and V (no N ), then we can
invert this to obtain U as a function only of S and V (again, no N ).
Then, from the first law,
dU = T dS − P dV
represents a complete and general expression for dU . But, by the
assumption above, U = AV T λ , and
dU = AV λT λ−1 dT + AT λ dV = T dS − P dV.
Solving this for dS gives
4
dS = AV λT λ−2 dT + AT λ−1 dV.
3
4
Thus, ∂S/∂T = AV λT λ−2 and ∂S/∂V = 3 AλT
λ−1
. By equating
∂ 2 S/∂V ∂T and ∂ 2 S/∂T ∂V , we have
4
AλT λ−2 = A(λ − 1)T λ−2 ,
3
the only solution of which is λ = 4.
4
(b) Photons in one dimension. Consider a one-dimensional box of
size L at temperature T . In equilibrium, this box will be filled with
a gas of photons characterized by energy
hc
= j,
2L
where j = 1, 2, . . .. Show that the photon energy in the box is
U = A × L × T λ,
where A and λ are constants. Find λ. (You do not need to give a
precise value for A. You only need to show that it is finite and that
it depends on only mathematical and physical constants.)
SOLUTION: Here,
∞ Z ∞
(kT )2
X hc 1 x
U= j βhcj/2L − 1
→ 2 L x−1
dx.
j=1
2L e hc 0 e
I am neglecting a possible number of polarization states (in 1D?),
but I am only asking for an answer up to a possible multiplicative
constant. The integrand above is finite near x = 0, so the integral is
certainly finite. Thus,
U = ALT λ
and λ = 2.