SM

Qualification Exam: Statistical Mechanics
Name: , QEID#18978097:
August, 2017
Qualification Exam QEID#18978097 2
1 Undergraduate level
Problem 1. 1983-Fall-SM-U-1 ID:SM-U-2
1. Two containers of equal volume are filled with an equal number of moles of
two different ideal classical gasses. The containers are in thermal contact. The
molecules of one of the gasses are diatomic, the other monoatomic. Which
container has greater
(a) pressure
(b) internal energy
(c) heat capacity at constant volume
(d) entropy
2. Discuss and criticize, using examples, the following statement: “In equilibrium,
nature seeks the equipartition of energy, in which each degree of freedom con-
tains an average amount of energy 12 kB T .”

1. Two containers of equal volume are filled with an equal number of moles of
two different ideal monoatomic classical gasses. The containers are in ther-
mal contact. The molecules of one of the gasses obey classical (Maxwellian,
Boltzmann) statistics, while the molecules of the other gas obey Fermi-Dirac
statistics. Which container has greater
(a) pressure
(b) internal energy
(c) heat capacity at constant volume
(d) entropy
2. Answer the same questions as for previous part, but comparing classical statis-
tics and Bose-Einstein statistics. Do any of your answers depend on the tem-
perature?

An engine with one mole of a monoatomic gas as the working fluid undergoes the
following cycle:
• An adiabatic expansion from pressure P0 , volume V0 to a volume 2V0 ;
• An isothermal compression from 2V0 to V0 ;
• At constant pressure to the original state.
1. Find the efficiency of the engine
Statistical Mechanics QEID#18978097 August, 2017

2. What is the change in the entropy of the gas during the second leg of the cycle?
3. What is the change in internal energy of the gas in the first leg of the cycle?
Problem 4. 1983-Spring-SM-U-1 ID:SM-U-45

1. Define the thermodynamic energy function H (enthalpy), G (Gibbs free energy),
and F (Helmholtz free energy) for a homogeneous system in term of U (internal
energy) and the thermodynamic variables (S, T, P, V ). What are the natural
variables for each function?
2. Derive the Maxwell relations between the partial derivatives of the thermody-
namic variables. Justify each step in words.

An engine with one mole of a monoatomic ideal gas as a working substance undergoes
the following process:
1 → 2 isobaric expansion V0 → 2V0
2 → 3 isothermal expansion P0 → P0 /2
3 → 4 isobaric compression at P0 /2
4 → 1 isothermal compression at T0
1. Find the net work done in the process in terms of P0 , V0 .

2. Find the net heat absorbed in the total process in terms of P0 , V0 .
3. Find the entropy change in going from 1 to 2 in terms of R.
4. Find the entropy change in going from 2 to 3 in terms of R.
5. What is the net entropy change in the total process?

The heat capacity of a normal metal Cn at low temperatures is given by Cn = γT ,
where γ is a constant. If the metal is superconducting below Tc , then the heat capacity
CS in the temperature range 0 < T < Tc is given by the relation CS = αT 3 , where
α is a constant. The entropy Sn , SS of the normal metal and superconducting metal
are equal at Tc , also Sn = SS as T → 0.
1. Find the relation between CS and Cn at Tc .
2. Is the transition first or second order?


A cylinder closed at both ends equipped with insulating (adiabatic) walls, and is
divided into two parts with a frictionless, insulating, movable piston. The gases on
both sides are initially at equilibrium with identical pressure, volume, and tempera-
ture (P0 , V0 , T0 ). The gas is ideal with CV = 3R/2 and CP /CV = 5/3. By means of
a heating coil in the gas on the left hand side, heat is slowly supplied to the gas on
the left until the pressure reaches 32P0 . In terms of P0 , V0 , and T0
1. What is the final right hand volume?
2. What is the final right hand temperature?
3. What is the final left hand temperature?
4. How much heat must be supplied to the gas on the left?
5. How much work is done on the gas on the right?
6. What is entropy change of the gas on the right?
7. Compute the entropy change of the gas on the left.

This problem refers to a classical monoatomic gas.
1. On a T − S diagram, draw an isothermal expansion, an isobaric expansion, and
a constant volume process.
2. Draw a Carnot cycle on a T −S diagram. Assume that the Carnot cycle operates
between T1 and T2 , with T1 > T2 .
3. Derive the expression for the efficiency of a Carnot cycle using this T − S
diagram.

The van der Waals equation of state for a mole of gas is given by (P + a/V 2 )(V − b) =
RT , where V is the molar volume of the gas.
1. Define the critical point Tc , Vc , and Pc in terms of (∂p/∂v)T and (∂ 2 P/∂V 2 )T .
2. Express a and b in terms of Tc and Vc .
3. Express Pc in terms of Tc and Vc .
4. Calculate the compressibility κT = −V −1 (∂V /∂P )T and the thermal expan-
sion coefficient β = V −1 (∂V /∂T )P for the van der Waals gas. What do these
quantities do at the critical point?


1. If lS is latent heat of sublimation per mole, and the vapor phase can be consid-
ered to be an ideal gas, show by using Clausius-Clapeyron equation that
dP lS d(log P )
= dT, and lS = −R ,
P RT 2 d(1/T )
where the volume occupied by the solid can be neglected compared to that
occupied by the vapor.
2. Iodine vapor can be assumed to be an ideal diatomic gas with constant CP . At

301K, the vapor pressure is 51.5N/m2 and at 299K it is 43.5N/m2 . Compute
the latent heat of sublimation at 300K.
3. Assuming constant latent heat, calculate the vapor pressure at 305K, assuming
no phase transition exist in the intervening temperature range.

1. A body of finite, temperature independent, heat capacity is originally at tem-
perature T1 which is higher than the temperature of a heat reservoir T2 . Suppose
that a heat engine operates in infinitesimal cycles between the body and the
reservoir, until it lowers the temperature of the body from T1 to T2 extracting Q
(heat) and does work W during the process. Prove that the maximum amount
of work obtainable is
Wmax = Q − T2 (S1 − S2 ),
where S1 − S2 is the entropy decrease of the body.
2. Two identical bodies, each of constant heat capacity C are at the same initial
temperature Ti . A refrigerator operates between these two bodies until one
of them is cooled to T2 . Calculate using the same principle as the one in the
previous question the final temperature of the high temperature body in terms
of Ti and T2 . Show that the minimum amount of work needed is
2
Ti
W =C + T2 − 2Ti .
T2

1. Write down differential equations for the internal energy U , the enthalpy H,
the Helmholtz free energy F , and the Gibbs function G.
2. Derive, showing your reasoning the four Maxwell’s Relations.
3. Show that
∂U ∂P
=T − P.
∂V T ∂T V

4. For a van der Waals gas, show that the internal energy increases as the volume
increases. The van der Waals equation of state is
RT a
P = − 2.
V −b V

1. A membrane separates two chambers of equal volume. Only one side contains
gas, the other is a vacuum. The system as a whole is thermally isolated from
the world, and its walls are rigid. If the membrane is burst (neglect the energy
associated with the membrane) which of the following quantities will remain
unchanged after the system adjusts to the doubled volume?
(a) total entropy S

(b) total particle number N
(c) total energy E
(d) temperature T
(e) pressure P
(f) chemical potential µ
2. During which periods of time can one describe the entropy of the system as
a unique function of energy, volume, and particle number? Comment on your
answers for each part.
(a) Initially.
(b) During the expansion.
(c) After the adjustment to the doubled volume.

What is the thermal efficiency of an engine that operates by taking an ideal gas the
following cycle?
1. Start with n moles at P0 , V0 , T0 .
2. Change to 2P0 , V0 , at constant volume.
3. Change 2P0 , 2V0 , at constant pressure.
4. Change to P0 , 2V0 , at constant volume.
5. Change P0 , V0 , at constant pressure.


◦
Heat is added to 0.5kg of ice at 0 C until it is all melted. If you don’t know the heat
of melting, call it l.
1. What is the change in entropy of the water?
2. If the source of heat is a very massive body at a temperature of 20◦ C, what is

the change in entropy of this body?
3. What is the total change in entropy of the water and the heat source?

A system possesses three energy levels E1 = , E2 = 2, E3 = 3 with degeneracies
g(E1 ) = g(E2 ) = 1 and g(E3 ) = 2. Write down
1. The partition function for the system
2. The energy of the system
3. The heat capacity of the system
4. What is the ”low temperature” temperature dependence of the heat capacity?
5. What is the ”high temperature” temperature dependence of the heat capacity?

For a ferromagnetic solid at low temperatures, the quantized waves of magnetization
(spin waves) have their frequency ω related to their wave number k according to
ω = Ak 2 where A is a constant.
1. For a 3-dimensional solid, write down the density of states D(ω) for such an
excitation.
2. Write an expression for the energy density for the spin waves.
3. Determine an expression for the heat capacity, and what is its temperature
dependence at low temperatures?
4. At sufficiently low temperatures, which terms should give the largest contribu-
tion to the specific heat: phonons, electrons, or spin waves? Which would give
the smallest contribution?


According to quantum mechanics, the molecules of a diatomic gas possess rotational
energy levels
er = ~2 r(r + 1)/2I, where r = 0, 1, 2, . . .
and I is a constant, the level r being (2r + 1)-fold degenerate.
1. Write down the expression for the partition function of the rotational motion.
2. Using the previous part find the molar rotational heat capacity of the gas at
low and at high temperatures.
3. For CO, the constant, I has a value 1.3 × 10−39 gm·cm2 . What is the molar
rotational heat capacity for CO at room temperature?

Consider an ideal gas.
1. Show that the heat transferred during an inflniteslsal quasi-static process c an

be written as
CV CP
dQ = V dP + P dV
R R
2. Apply the above equation to show that P V γ = const. far an adiabatic process.
What is γ?

−3
A vessel contains 10 cubic meters of helium gas at 3K and 103 Pa. Take the zero of
internal energy of helium to be at this point. You may assume that helium acts as a
monoatomic ideal gas. R = 8.31 J/mole-K.
1. The temperature is raised to 300K at constant volume. Hou much heat Q is

absorbed, and what is the internal energy of helium?
2. The helium is now expanded adiabatically to 3K. What ls the final volume? H
ow much work W is done by the gas and what is the new internal energy of the
gas?
3. The helium is now compressed isothermally to its original volume. What are
Q, W , and ∆U during this process?
4. Sketch the process on a P V diagram. What is the efficiency of the cycle?

Compare this efficiency to that of an ideal Carnot cycle operating between the
two temperature extremes.


On a mountainside, air is enclosed in a limp, massless, plastic bag and then is carried
down 100m, in a time too short for heat to flow across the plastic bag, but slow
enough that the pressure inside the bag is in equilibrium with its surroundings at
all times. If air weights 29.3g/mole, and has CP = 29.3J/K, by how much does the
temperature in the air change? Give a brief explanation for the sign of the rise or fall
in temperature.

1. Find the Fermi energy at T = 0, εF , of a gas of N noninteracting spin one-half
particles constrained to move in two dimensions within an area A.
2. Recall that the surface tension, σ, in two dimensions is analogous to pressure

in three dimensions so that the surface tension contribution from a particle in
state n is given by −∂n /∂A. Show that the surface tension at T = 0 is given
by N εF /2A.

Derive the general expression for CP − CV in terms of αT , KT where αT is the
isothermal expansion coefficient and KT is the isothermal compressibility coefficient
of the material. Prove that (CP − CV )/T must approach zero as T approaches zero.

The work done by a long solenoid in magnetizing a thin rod shaped magnetic sample
inside it is
δWsol = µ0 V Ha dM,
where µ0 is the permeability of free space, V the sample volume, Ha , the applied field
and M the magnetization of the sample (magnetic moment per unit volume), The
magnetic induction inside the sample is given by
B = µ0 (Ha + M ) = µ0 (1 + χ)Ha ,
where χ is the magnetic susceptibility of the material. For most ordinary metals in
the normal state, χ is rather small. (For this problem it can be set equal to zero.)
If the metal goes into the superconducting state, however, it would usually exhibit a
Meissner effect which means that B = 0 inside the superconductor, i.e. χ = −1. At
temperatures below the superconducting transition temperature, T < Tc , an applied
field Ha = Hc , (the critical field) is sufficient to destroy superconductivity. The
phase boundary between the superconducting state and the normal state can be
approximated by
Hc = H0 1 − (T /Tc )2

1. For this phase boundary in the Ha , T plane. Write the defining expression for
the magnetic Gibbs free energy G(T, P, Ha ) and its differential.

2. What is the relationship between GN (T, P0 , Hc ) and Gs (T, P0 , Hc ), the Gibbs

free energies for the normal and superconducting phases along this phase bound-
ary. P0 is an arbitrary, fixed pressure at which the relation for Hc , given above
was determined. Find the relationship between GN (T, P0 , Ha ) and GN (T, P0 , 0)
and between GS (T, P0 , Ha ) and GS (T, P0 , 0).
3. Use the results of the previous parts to show that
(a) there must be a jump discontinuity in the heat capacity of a metal when
it undergoes the superconducting transition at T = Tc . (Relate this jump
to dHc /dT at T = Tc , Ha = 0);
(b) there must be a latent heat of transformation when the superconductor is
driven from the superconducting state to the normal state by a magnetic
field applied at a constant temperature T . (Relate this latent heat to the
slope of the phase boundary as a function of temperature.)

Starting from ideal gas law and the first law of thermodynamocs, derive the relation
between pressure P and volume V for an adiabatic process in terms of γ ≡ (cV +
R)/cV = cP /cV .

1. Assuming that water is incompressible, estimate the change in Gibbs energy
∆G in joules of 100cm3 of water at 25o when the pressure is changed from 1atm
to 100atm. (Note that 1atm = 1.013 × 105 N/m2 .)
2. In fact the volume of a sample does change when it is subjected to pressure, and
so we ought to see how to take the effect into account, and then judge whether it
is significant. The volume varies in a way that can be determined by specifying
the isothermal compressibility κ = −V −1 (∂V /∂P )T , and we may assume that
this is virtually constant over a pressure range of interest. Deduce an expression
for the Gibbs energy Gf at the pressure pf in terms of its value Gi at the initial
pressure pi , the original volume of the sample Vi , and the compressibility κ.
Take the limit of κ → 0 in your expression for ∆G ≡ Gf − Gi , and show that
it reduces to the expression used in the first part.

A hydrogen atom in equilibrium with a radiation field at temperature T can be in its
ground state orbital level (the “1 − s” level, which is two-fold spin degenerate with
energy 0 ), or it can be in its first excited state energy level (the “2 − p” level, which is
six-fold degenerate with energy 1 ). For the purpose of this problem we shall assume
that theis atom does not have any other excited states (i.e., no 2s level and no levels
with the principal quantum number n > 2).
1. (a) What is the probability that the atom will be in an “orbital s−state”?

(b) What is the probability that the atom will be in an “orbital p−state”?
(c) What is the probability that the atom will be in an “orbital s−level”?
(d) What is the probability that the atom will be in an “orbital p−level”?
2. If the temperature is such that kB T = 1 − 0 , then show and state which of the
two orbital levels is occupied more.
3. Derive an expression for the mean energy of the atom at temperature T and
obtain the limiting value of this mean energy as T → ∞.
4. Derive an expression for the entropy of the atom at temperature T and also,
from the definition of entropy, state what should be the values of the entropy for
this atom in the limits of T → 0 and T → ∞. (If you do not know the answer
for the last question, you may obtain the limits from your general expression of
entropy.)

Consider a single component system with two phases 1 and 2
1. Starting from the condition of equilibrium for the two phases that the Gibbs
free energies g1 and g2 are the same, i.e. g1 = g2 , derive the Clausius-Clapeyron
equation:
dP l1,2
=
dT T ∆v
where l1,2 is the heat absorbed when one mole of phase 1 is transformed to
phase 2, ∆v = v2 − v1 is the corresponding volume change, and P and T are,
respectively, the pressure and temperature of the system.
2. Using the above equation show that the slope of any vapor pressure curve (liquid
or solid) is positive.
3. Show that the melting curve for water has a negative slope.
4. The slope of a vapor pressure curve near the critical point is finite. Using the
above equation find the expected numerical value for l1,2 at the critical point.

Consider a thermally isolated cylinder of length l and area S shown in the figure. The
piston is semi-permeable, allowing gas A only to pass through. The cylinder contains
classical ideal gases A, B and C, so that gas B is contained on the left, and gas C
on the right, as shown. The cylinder and piston have small heat capacity compared
to the gases.
1. Find the equilibrium piston position, x0 , given the mole amounts of the three
gases, NA , NB , NC .

2. If the piston is moved adiabatically from its equilibrium position (x0 ), find the
temperature vs. x, in terms of the initial temperature T0 , and the constant volume
molar heat capacities of the three gases CA , CB , and CC . (Assume that the three
gases attain a mutual temperature.)
3. What is the total entropy change in the process (S vs. x)?
4. For the system of B molecules only, what is the entropy change (SB vs. x)?

Consider a system of N non-interacting fermions for which the single-particle density
of states N () is a sum of delta functions:
∞
X
N () = N0 δ( − n0 ),
n=0
where 0 is a constant of the dimension of energy, and N0 is proportional to the total

volume V of the system and is otherwise a dimensionless constant.
1. What is the relation which determines the chemical potential µ of this system
as a function of N , V , and the temperature T ?
2. Sketch the dependence of µ on N at fixed V and T assuming that T 0 , so
one is in the low temperature regime (but not exactly at T = 0). You may
sketch the inverse function N (µ) if you so choose to do so.
3. What is the relation which determines the total energy E of the system as a
function of T , V , and µ?
4. Use the above relations to show that the total heat capacity at constant volume
of the system is given by:
 2 

 P∞ n 

∞
2 X 2 n=0 cosh2 [ 1 β(n0 −µ)]

N0 0 n 2

CV = − ∞
cosh2 21 β(n0 − µ) 1
P
4kB T  n=0 n=0 cosh2 [ 1 β(n0 −µ)] 


 2 

[Note: cosh x ≡ 21 [ex + e−x ].]


Imagine a set of N independent spins, with fixed positions and J = 1. In a uniform
magnetic field, the spin energies are E = µHs, where s = (1, 0, −1) labels the spin
component along the magnetic field, H is the applied field, and µ is the magnetic
moment. N is a very large number.
1. Find a general form for n+ , n0 , and n− , the expectation values for the numbers
of spins with each of the three spin components, at a given temperature and
field. Do not assume the high-temperature limit here.
2. What is hEi, the total energy expectation value, in the high temperature limit
(first temperature-dependent term)?
3. Find an expression for the entropy S, in the high-temperature limit. Here we

are looking for two terms, the temperature-independent T ≈ ∞ term and the
first temperature-dependent term. (You may need Stirling’s approximation,
log N ! ≈ N log N − N , although one can do the problem without needing this
formula.)
4. From the previous result, find the temperature dependence on the field H, as H
is varied in an adiabatic process. For decreasing H, what is the process called?

A particular system obeys the following relations: For internal energy;
U = PV
and for the pressure,

P = BT 2
where V is volume, T absolute temperature, and B is a constant.
1. Find the fundamental equation of this system, that is how the entropy S depends
on U and T and an arbitrary constant Sc .
2. Discuss and show whether S obeys the Third Law of Thermodynamics.
3. Calculate how much heat is transferred into the system when the volume changes
from V0 to 2V0 during an isobaric process (P = P0 ).
4. Calculate the amount of work done by the system when V changes from V0 to
2V0 under isobaric condition (P = P0 ).
5. Show that your results from the previous two parts obey the First Law of
Thermodynamics.


Consider an extremely relativistic gas consisting of weakly interacting N identical
monoatomic molecules with energy momentum relationship E = cp, where c is the
speed of light. The gas is confined to a volume V and is in thermal equilibrium at
temperature T .
1. Calculate the partition function ZN (V, T ) for the gas.
2. Calculate the Helmholz free energy F .
3. Derive an equation of state of the gas.

Consider the properties of a rubber band with tension λ(x, T ), extension x, entropy
S, and temperature T .
1. Find the work done by the rubber band when stretched from x to x + dx.
2. Formulate the first law of thermodynamics for the system.
3. Show that
∂S ∂λ
=− .
∂x T ∂T x
4. Show that
∂x ∂x ∂T
= .
∂S T ∂λ T ∂x λ
5. If now the rubber band obeys Hooks’s law as an ideal spring, with the force
constant K independent of temperature, what is implied about the functional
form of S = S(x, T )?

A horizontal insulating cylinder contains a frictionless, thermally insulating piston.
On each side of the piston there are V0 cubic meters of a monoatomic ideal gas at
a pressure P0 and absolute temperature T0 . The gas on the left hand side is heated
slowly until the piston has compressed the right hand side to a pressure of 32P0 .
1. How much work is done on the gas on the right hand side? Express the answer
in units of P0 V0 .
2. What is the final temperature of the gas on the right hand side in units of T0 ?
3. What is the change in entropy for the gas on the right hand side in units of the
number of moles times the gas constant, nR?
4. What is the final temperature of the gas on the left hand side in units of T0 ?

5. How much heat is added to the gas on the left hand side? Express the answer
in units of P0 V0 .

The relation between the frequency ν and the wavelength λ for surface tension waves
on the surface of a liquid of density ρ and surface tension σ is
2πσ
ν2 = .
ρλ3
Use a method analogous to the Debye theory of specific heats to find a formula,
analogous to the Debye T 3 law, for the temperature dependence of the surface energy
E of a liquid at low temperatures. The surface tension of liquid helium at 0K is 0.352×
10−3 N/m and its density is 0.145g·cm−3 . From these data estimate the temperature
range over which your formula for E(T ) is valid for liquid helium, assuming that each
helium atom in the surface of the liquid possesses one degree of freedom.
You may assume Z ∞ 4/3
x
dx = 1.68.
0 ex − 1
Bohzmann’s constant kB = 1.38 × 10−16 erg·K−1
Avogadro’s number N = 6.02 × 1023 mole−1
Planck’s constant ~ = 1.05 × 10−27 erg·sec

One liter of an ideal gas under a pressure of 1 atm is expanded isothermally until its
volume is doubled. It is then compressed to its original volume at constant pressure
and further compressed isothermally to its original pressure. Plot the process on a
P − V diagram and calculate the total work done on the gas. If 50J of heat, were
removed during the constant- pressure process, what would be the total change in
internal energy? (1 atm = 1.013 × 105 N/m2 )

1. For a general (non-ideal) gas, derive the formula

∂P
dE = nCV dT + T − P dV.
∂T V
CV is the constant-volume specific heat, assumed here to be a constant, and n
denotes the number of moles of gas. You may want to use the Maxwell relation,

∂S ∂P
= .
∂V T ∂T V
2. For the van-der-Waals equation of state,

n2 a

P + 2 (V − b) = nRT,
V

derive a specific form for dE given above. CV is again a constant (valid, pre-
sumably, over a limited temperature range).
3. Find, for the van-der-Waals gas, the constant-pressure specific heat CP (T, V ),
using your result from the previous part. Note that CP is not a constant, but
show that it reduces to the expected form for the ideal gas case.

In an isolated system of N identical particles (N large) each particle can be in two
energy states: 1 = 0 and 2 = > 0. The total energy of the system is E. Find, as
a function of E,
1. The entropy of the system.
2. The tmnperature of the system.
Note that log n! = n log n − n.

A substance is found to have two phases N and S. In the normal state, the N phase,
the magnetization M is negligible. At a fixed temperature T < Tc , as the external
magnetic field H is lowered below the critical field
" 2 #
T
Hc (T ) = H0 1 −
Tc
the normal state undergoes a phase transition to a new state, the S phase. In the S
state, it is found that B = 0 inside the material. The phase diagram is shown below.
1. Show that the difference in Gibbs free energies (in cgs units) between the two
phases at temperature T ≤ Tc , is given by
1 2
H − Hc2 (T ) .

GS (T, H) − GN (T, H) =
8π
(You may express your answer in another system of units. The Gibbs free
energy in a magnetic field is given by G = U − T S − HM .)
2. Compute the latent heat of transition L from the N to the S phase.

[Hint: one approach is to consider a vClausius-Clapeyron” type of analys is.]
3. At H = 0, compute the discontinuity in the specific heat as the material trans-

forms from the N to the S phase.
4. Is the phase transition first or second order at H = 0? What is the basis of

your conclusion?


A thermally conducting, uniform and homogeneous bar of length L, cross section A,
density ρ and specific heat at constant pressure cP is brought to a steady state by
contact at one end with a hot reservoir at a temperature TH and at the other end
with a cold reservoir at a temperature TC . The bar is removed from the reservoirs,
thermally insulated and kept at constant pressure.
1. Find the equilibrium temperature Tf of the bar.
2. Show that the change in entropy of the bar is

TC TH
∆S = CP 1 + log Tf + log TC − log TH ,
TH − TC TH − TC
where CP = cP ρAL. Assume cP and thermal conductivity are constants.

1. Show that the Hamiltonian of an LC circuit is that of a harmonic oscillator.
Identify the resonance frequency, and obtain the discrete energy levels of this
system if it is quantized.
2. Calculate the mean energy of this system if it is at thermodynamic equilibrium

with its surroundings which are at an absolute temperature T .
3. Show how the root-mean-square voltage Vrms , across the capacitor of this circuit
can be used as a thermometer to measure the absolute temperature T of its
surroundings, by showing that Vrms is a monotonically increasing function of

T , and therefore Vrms can uniquely determine T . Neglect any temperature

dependence of L or C.

Find the change of temperature of a quantity of water carried by a downward current
to a depth of 1km in a lake at 27o C. For water at this temperature

1 ∂V
= 0.00013 deg−1
V ∂T P
and you may assume: ”no heat exchange” (∆S = 0).

Given: g = 980 cm/s2 , and ρ = 1 gm/cm3 , cP ∼ 1 cal/g·deg for water, and
1cal = 4.18 × 107 erg.

Measuring the tension J of a rubber band stretched at a constant length l, it is found
that J = AT , where A is a positive constant depending only on l; T is the absolute
temperature.
1. Show that the internal energy U is a function of the temperature only.
2. Show that the entropy S decreases with increasing length at constant temper-
ature.
3. When the rubber band is stretched adiabatically, does the temperature increase,
decrease or stay unchanged, and why?

The molecuies of one mole of a certain gas consist of two different atoms, each of zero
nuclear spin, bound together. Measurements of the specific heat of this material, over
a wide range of temperatures, give the graph shown below. (The values marked on
the vertical scale correspond to the height of the curve in each of the plateau regions.)

1. Describe the physical reason for each of the three difierent plateaus in the figure.
2. At temperature T0 , the gas undergoes a phase transition directly to an ideal

classical solid. Sketch the typical behavior of CV below T0 , down to 0K, includ-
ing the magnitude just below T0 and the temperature dependence just above
the absolute zero temperature, and give physical justifications.
3. Given the first excited state of the rotational spectrum of this molecule is at
the energy kTe above the ground rotational state, and Te = 64K, calculate
from basic theory the rotational contribution to the specific heat capacity per
molecule (in units of the Boltzmann constant kB ) at T = 10K and T = 500K.
~2
(Note that Te = 2θr , where θr ≡ 2Ik B
is the rotational temperature, and you
may make reasonable approximations in answering this part. If you don’t have
a calculator for the explicit evaluations, indicate what numerical expressions
you would have to compute with a calculator.)

A gas is described by the following equations of state
U
P = , U = bV T 4
3V
where b is a constant and P , U , V , and T are the thermodynamic pressure, internal
energy, volume and temperature.
1. Determine the entropy S as a function of U and V .

2. Determine the functional relationship between P and V along an adiabatic path.
3. Determine the functional relationship between P and V along an isothermal

path.
4. Determine the work done by the system as it expands from an initial volume
V0 to a final volume 2V0 along an isothermal path with temperature T0 .
5. Determine the heat added to the system as it expands from an initial volume
V0 to a final volume 2V0 along an isothermal path with temperature T0 .

Consider a gas of non-interacting Bose particles with spin S = 0 and mass m. In the
ultrarelativistic limit, one can approximate the dispersion relation by E(p) = cp.
1. Write down a general integral expression for the statistical average of the total
number of particles not in the zero-energy ground state.
2. Determine the Bose-Einstein condensation temperature T0 of the gas as a func-

tion of the gas density ρ = N/V .
3. Determine the fraction N0 /N of the particles in the zero-energy ground state

as a function of temperature T and density ρ.
You may gnd the following formula useful:

Z ∞ x−1
z
dz = Γ(x)ξ(x)
0 ez − 1
x 3/2 5/2 3 5
√ √
Γ π/2 3 π/4 2 24
ξ 2.612 1.341 1.202 1.037

A chamber, that is adiabatically isolated from the outside universe, is partitioned
into two volumes V0 and ∆V . Initially the volume V0 is filled with N particles of a
gas and the volume ∆V is completely empty. The partition between the volumes V0
and ∆V is punctured so that the gas freely expands into the additional volume ∆V
so that its final volume is V0 + ∆V .
1. Assuming ∆V is small, calculate a general expression for the change in tem-

perature ∆T . Express your answer in terms of the following thermodynamic
quantities which you can assume to be known.

Temperature T
Volume V
Pressure P
1 ∂V

Thermal Expansion α= V ∂T P
− V1 ∂V

Isothermal Compressibility κT = ∂P T
2. Evaluate your expression for ∆T in the previous part for a monoatomic ideal
gas.

An ensemble of non-interacting pairs of Ising spins is in a magnetic field h and at
temperature T . Each spin variable szi can only take on values sz = ±1. The two spins
within each pair interact according to the Hamiltonian
H = −Jsz1 sz2 − µB h (sz1 + sz2 ) , with J > 0
1. Enumerate the possible states of a single pair and compute their corresponding
energies.
2. Derive an expression for the average value of a spin, hszi i, (i = 1, 2) as a function

of J, T and h.
3. Given the above model, determine whether there exists a temperature Tc for
which hszi i can be non-zero at h = 0. Evaluate Tc .

1. Show that the number of photons, N , in equilibrium at temperature T in a
cavity of volume V is proportional to
3
kB T
V
~c
2. Show that the heat capacity for this system is proportional to T 3 .

Consider a system of non-interacting spin 1/2 fermion particles, electrons, adsorbed
on a surface with specific adsorption sites. At each site, an electron can occupy any
one of three distinct orbital states corresponding to energies 1 , 2 , and 3 (1 > 0,
2 > 0, and 3 > 0). The surface is in contact with a gas of electrons that acts as a
thermal and particle reservoir.
1. Determine a general expression for the average number of particles adsorbed
per site if the reservoir is at a temperature T and has a chemical potential µ.

2. If 1 < 2 and 2 = 3 within what range of values must µ(T = 0) lie if at T = 0

the average number of electrons adsorbed per site is 2.
3. If the average number of electrons adsorbed per site is maintained at 2 for small
nonzero temperatures, determine the precise limiting value of µ as T approaches
zero.

Consider the following equations of state for an ideal gas:
U = cN kB T, P V = N kB T,
where c is a constant.
1. Determine the entropy as a function of U , V , and N . Let S = 0 when U =

N u0 , and V = N v0 , where constants u0 and v0 are the energy/particle and
volume/particle respectively.
2. Determine the entropy as a function of P , T , and N . Let S = 0 when T = T0

and P = P0 .
3. If the number of particles N varies, then calculate the chemical potential in

terms of P , T , P0 , T0 , and constants c and kB .

When we apply a magnetic field H to a solid body, it is permissible under many
circumstances to neglect the −P dV term in comparison to the HdM term in the
fundamental thermodynamic equation. Hence for a magnetizable solid body we can
simply write
dU = T dS + HdM
where the magnetization M = χH is related to H through the susceptibility χ =
χ(H, T ). Let CH denote the heat capacity at constant field H, CM the heat capacity
at constant M , and define the differential isothermal susceptibility as Π = (∂M/∂H)T .
1. Find an expression for CH − CM in terms of T , H, χ, and Π.
2. Show for a paramagnetic material, where χ = α/T with a = constant, that the
expression in the first part reduces to CH − CM = M H/T .

1. Shown in the figure below is a set of available single-particle states and their
energies. By properly filling these single-particle states, find the energies and
degeneracies for a system of four identical non-interacting particles in the sys-
tem’s lowest energy level and in its first excited energy level, assuming that
these particles are:

(a) identical spinless bosons,

(b) identical spinless fermions.
2. At a finite temperature T, calculate the ratio r = P1 /P0 , again for the two cases
defined above. P1 is the probability for finding the four-particle system in the
first excited energy level, and P0 is the probability for finding the same system
in the lowest energy level.

One is given two containers. Each contains N moles of water at the same pressure.
Initially the temperature of the water in each container is T1 , and T2 (T2 ≥ T1 ).
The entire system is kept at a constant pressure and is thermally isolated from the
surroundings. The heat capacity of water per mole, CP , can be taken to be a constant
for T1 ≤ T ≤ T2 .
First, consider a process when the two bodies of water are brought into thermal
contact so they can exchange heat between themselves.
1. Calculate the final temperature of the resulting mixture.
2. Calculate the change in the total entropy of the two bodies of water.
3. Now, determine the theoretical maximum amount of total work that could have
been obtained from this system.


During a process in which the volume of a system of N molecules is expanded from
V1 to V2 , the temperature is observed to decrease linearly with the volume from T1
to T2 , that is,
T = T1 + A(V − V1 )
−T1
where A = VT22 −V1
.
Express the heat transfer during this process in terms of definite integrals of

T ∂S 1 ∂V 1 ∂V
CP = , α= , κT = − ,
N ∂T P,N V ∂T P,N V ∂P T,N
which are assumed to be known functions of T and V .

A simple statistical mechanical model can be used to describe thermal denaturation
(strand separation) of DNA molecules. The DNA molecule is represented as a chain
of two kinds of base pairs, NA pairs of type A and NB pairs of type B, in a given
sequence. Each pair can be in two states (n = 0, 1), ether bound (n = 0) or unbound
(n = 1), as shown in the figure. The average fraction of unbound pairs (f ) can be
easily measured experimentally.
1. Sketch qualitatively, using only physical arguments, f as a function of temper-

ature T for a pure A (NB = 0) and a pure B (NA = 0) DNA. Be sure to state
the limiting values at T = 0 and ∞ explicitly.
2. Derive the partition function for a single DNA molecule assuming that the
energy n of each base pair is independent of the state of other pairs, and that
the unbinding energy depends only on whether the base is of type A or B,

0, if n = 0
n = .
∆A or ∆B , if n = 1
In this model, does the partition function (and the other physical properties)
depend on the particular sequence of the bases?
3. Derive a closed analytical expression for f as a function of T and c ≡ NA /N ,
where N = NA + NB .
[Hint: You may find the following identity useful: e−x /(1 + e−x ) = 1/(1 + ex ) =
1
2
(1 − tanh(x/2))].

4. Using the result in the previous part and the phenomenological form β∆A =
aA (TA − T ) and β∆B = aB (TB − T ), indicate the phenomenological parameters
aA , aB , TA and TB in your figures in the first part, and sketch f (T ) assuming
c = 1/4, TB = 1.5TA , a−1 −1
A = 0.1TA , and aB = 0.1TB .

Consider a classical system of N point particles of mass m in a volume V at temper-
ature T . The particles interact through a two-body repulsive central potential
r n
0
φ(r) = φ0 ,
r
where φ0 > 0, r0 > 0, and n > 0.
1. Calculate the partition function Z(T, V ) for this system and show explicitly
that Z(T, V ) = Z0 (T, V )q(T V n/3 ), where Z0 is the ideal gas partition function
and the function q(x) (which you can not express in a closed form!) depends
on T and V only through x = T V n/3 .
2. Given the result of the previous part, show that the internal energy U and the
pressure P are related as U = U0 + n3 (P − P0 )V , where the subscript 0 refers to
the ideal gas.
3. What is the potential φ(r) as n → ∞? Explain the result obtained in the

previous part in this limit. Is it correct?

A material, in a certain range of temperature T and pressure P , has a volume expan-
sivity (or thermal expansion coefficient) given by
α = (R/P v) + (a/RvT 2 ),
and an isothermal compressibility given by
κT = [T f (P ) + (b/P )]/v,
where R, a, and b are (non-dimensionless) constants independent of pressure P the

specific volume v ≡ V /N , and the absolute temperature T , and f (P ) f(P) is an
unknown function of P .
1. Determine f (P ).
2. Determine v(P, T ).


The ground state density of a free-electron Fermi gas is conveniently parametrised by
specifying the volume per conduction electron according to
4 3 V
πrs ≡
3 N
1. Find the Fermi wavevector, kF in terms of the electron density parameter rs .
2. Find expressions for the following quantities, in terms of the dimensionless den-
sity parameter (rs /a0 ), where a0 is the Bohr radius, and with the units indicated:
(a) the Fermi momentum kF (in Å), [Given: 1a0 = 0.529Å.]

(b) the Fermi energy F (in eV ), [Given: 1Rydberg = 13.6eV .j
(c) the Fermi temperature TF (in K). [Given: 1eV = kB x1.16 × 104 K.]
In each case, a detailed expression for the coefficient involved should be found
so that if you had a calculator you would be able to evaluate the coefficient
numerically.
3. Starting from the equation of state

2
P V = hEi,
3
where hEi is the total internal energy of the gas, express the T = 0value of the
bulk modulus
∂P
B ≡ −V ,
∂V T,N
which is the inverse of the isothermal compressibility κT ≡ − V1 (∂V /∂P )T,N , in
terms of the Fermi energy F and the density parameter rs .

Using some simple reasoning, obtain the functional dependencies of the low- and high-
temperature behaviors (i.e., for T F and T F ) of the following quantities for
a three-dimensional ideal Fermi gas, in terms of N (the total number of particles), T
(the absolute temperature), F (the Fermi energy), and kB (the Boltzmann constant):
1. the total specific heat at a constant volume CV ,
2. the total entropy S,
3. the total internal energy E.
In each expression, you may introduce any number of un-determined numerical con-
stants, but not any un-determined dimensional quantities. For each of the three
physical quantities listed above, drew also a qualitative sketch of its T -dependence

from T = 0 up to a temperature T F , based on the low- and high-temperature

behaviors of it you have deduced.

Over some range of parameters a system is described by the following fundamental
equation:
s = Au1/3 v 1/3 ,
where s, u, and v are the molar entropy, molar energy, and molar volume, respectively
and A is a constant. N moles of this fluid is initially confined to a volume Vi at pressure
Pi . It then expands reversibly at consonant temperature T0 to a final volume Vf > Vi .
1. Determine the final pressure Pf in terms of Vi , Vf , and Pi .
2. Determine an expression for either the chemical potential µ or an expression

for the change in chemical potential, dµ, and explain whether the chemical
potential of this system increases or decreases for this process?

For a system in an electric field E the differential of the internal energy is
dU = T dS + EdΠ
where Π is the electric polarization of the system. Define the generalized Helmholtz
free energy F (T, Π), the generalized enthalpy H(S, E) and the generalized Gibbs free
energy G(T, E) for this system in terms of the variables T , S, E, and Π. Write the
differentials for these thermodynamic functions and use these to find the four Maxwell
relations between derivatives of these variables. (Note: for this particular system the
pressure P and volume V are not relevant variables, so don’t include them in your
work.)

For an isotropic three-dimensional solid whose velocity of sound c is the same for all
three modes, find the expression for the Debye temperature θD (where ~ωmax = kB θD ).
Show that the number of phonons exceed in this solid is proportional to T 3 for T θD
and proportional to T for T θD .

The figure shows the pressure versus molar volume isotherms for the Van der Waals
gas
RT a
P = − 2
v−b v
1. Which of the isotherms in the figure contains regions that do not satisfy the
thermodynamic stability conditions?
2. Which isotherm represents the critical temperature?

3. Sketch on the graph the region in which the system is unstable to local pertur-
bations (spinodal line).
4. Sketch on the graph the region in which the system is globally unstable.
5. What is physically occurring within this region of global instabilities?
6. Sketch the qualitative behavior of the molar volume against temperature for an
isobar at P = 0.02 and P = 0.06.

An ideal gas is expanded adiabatically from (P1 , V1 ) to (P2 , V2 ) [AB in figure below].
Then it is compressed at constant pressure to (P2 , V1 ) [BC]. Finally the pressure is
increased to P1 at constant volume V1 [CA].

1. Calculate WBC , the work done by gas in going from B to C.
2. Calculate WCA , the work done by gas in going from C to A.
3. For an ideal gas, show that CP = CV + N k, and hence that CV = N k/(γ − 1),
where γ ≡ CP /CV . (Here N is the number of molecules and k is the Boltzmann
constant. )
4. Calculate WAB the work done by gas in going from A to B, in terms of γ, P2 ,

V2 , P1 , and V1 .
5. Calculate QCA , the heat absorbed by gas in going from C to A, in terms of γ,

V1 , V2 , P2 and P1 .
6. Calculate the efficiency η ≡ W/QCA of the engine, and show that it is given by
1 − V2 /V1
η =1−γ
1 − P1 /P2
(Why do you need to divide by QCA and not by QCA + QBC ?)

Molecules do not all pile up at the bottom of the atmosphere, but rather have a
density n that decreases as one moves higher in the atmosphere The pull of gravity
is countered by upward diffusion.
Consider a monoatomic gas of molecules of mass m, in a uniform downward grav-
itational field g. Take the y-direction to be upward.
1. Using N as the number of molecules in a gas, V as its volume, and kB as the

Boltzmann constant, write down the ideal gas law.
2. Find the differential equation for the pressure P (y) under gravity by finding the
equilibrium condition for the matter in a slab of area A and thickness dy.
3. For an isothermal atmosphere if P = P0 at y = 0, find P (y).

4. Find the density n(y).

5. If the drift velocity due to gravity is v = µmg, where µ is called the mobility,
write down the number current density Jg due to the pull of gravity, including
its direction.
6. The number current density due to diffusion is Jdif f = −D∂y n, where D is
called the diffusion constant. Setting to zero the sum of the number current
densities due to gravity and due to diffusion, find a relationship between D and
µ.

Consider a set of N indistinguishable spin-1 objects, each with energy
E = ASz + BSz2 ,
where S, is given in units where ~ = 1. Thus A and B are energies.
1. With (n1 , n0 , n−1 ) the numbers of spins in the states with Sz = 1, 0, −1 respec-
tively, find the number of arrangements W of the spins that will produce these
numbers.
2. Write down the free energy F for this system, in terms of n1 , n0 , n−1 the tem-
perature T , and N . Use log(m!) = m log(m) − m for large m. Set kB = 1.
3. Using ni and n0 as independent variables, minimize F to find n1 , n0 , and n−1 ,
in equilibrium at a given temperature T .

Consider a one-dimensional (non-harmonic) oscillator with energy given by
p2
E= + bx4 ,
2m
where p is the momentum and b is some constant. Suppose this oscillator is in thermal
equilibrium with a heat bath at a sufficiently high temperature T so that classical
mechanics is valid.
1. Compute its mean kinetic energy as a fraction of kT .
2. Compute its mean potential energy as a fraction of kT .
3. Consider a collection of such non-interacting oscillators all at thermal equilib-
rium in one-dimension. What is the specific heat (per particle) of this system?
[Hint: You might use
Z ∞
xn−1 e−x dx = Γ(n), n 6= −1, −2, . . .
0
or an integration by parts in solving this problem.]


The equation of state for an ideal gas is P V = nRT .
1. Prove that the internal energy U (V, T ) is s function of T only.
2. If the entropy at T0 , V0 is S0 , find the entropy at any other T , V assuming

the molar specific heat CV is a given constant. (Express the answer for S as a
function of the variables T , V .)
3. Show that the reversible work done in an isothermal expansion is equal to the
negative of the change in free energy.

1. Determine the chemical potential, at temperature T = 0 and at number density
n for a non-interactmg, non-relativistic Fermi gas of spin-1/2 and mass m ( =
p2 /2m).
2. Repeat the previous part for the relativistic case ( = cp).
3. Show that, at some critical density n, and T = 0, the proton-electron plasma

starts a transition into the degenerate neutron gas. Neglect any interaction
between the particles and consider the electron and proton systems as Fermi-
gases. Take into account the mass difference ∆M between the neutron and
proton. Since me ∆M , the electrons must be treated relativistically. Assume
that neutrons created in the course of this transformation leave the system.
Neglect gravity.
4. Consider such a system in a box of volume V , with n < nc . Determine the

number of electrons Ne and their pressure as the volume is decreased somewhat
below the volume where the transition occurs. Do not consider compression so
high that complete conversion occurs.

The 1-dimensional Ising model is defined as a chain with “spins” σn , on each site n
(n = 1, 2 . . . N ) independently taking one of two values σn = ±1. The energy of this
system can be written as follows:
N
X −1
H = −J σn σn+1 ,
n=1
where J is a positive constant.
1. Introduce “spins on a bond” τn = σn σn+1 as new variables. Explain why the

τ ’s are independent. Find the partition function.
2. Find the free energy and the heat capacity per site.

3. Find the asymptotic behavior of the heat capacity at T J and at T J.

Give a physical explanation for the dominant behavior at T J.

The total entropy S for a system of N particles in a container of volume V , with total
energy E, is
S = aE 1/3 V 1/3 N 1/3 ,
where a is a constant.
1. Compute the temperature, pressure, and chemical potential as functions of S,
V , and N .
2. Stability, the Third Law, and the extensivity property provide some constraints
on allowable thermodynamic quantities (Extensivity refers to how various quan-
tities scale when two identical systems am combined.) Discuss how the results
from the previous part satisfy or do not satisfy these constraints.
3. Compute the Helmholtz free energy F (T, V, N ), and from F compute S(T, V, N ).
Show that this is consistent with the entropy S(E, V, N ) given initially.

Consider a cylinder of water that undergoes a slow adiabatic compression
1. What thermodynamic property of the water will be constant during an adiabatic
compression? Use this to write a simple equation connecting small temperature
changes, ∆T , to pressure changes, ∆P , to first order.
2. The temperature change in an adiabatic compression can be related to the wa-
ter’s compressibility, α ≡ V1 (∂V /∂T )P , and its specific heat at constant pressure,
CP . To do so, first find a Maxwell relation which will connect the compressibility
to a derivative of the entropy.
3. Now transform your equation from the first part, in order to express small
temperature changes, ∆T , to adiabatic pressure changes, ∆P , in terms of the
temperature, volume, CP , and the compressibility. Consider α, and CP , to be
essentially constant during the process.

Specific heat of a gas-liquid system:
1. What general expression relates pressure and temperature changes for conden-
sation and evaporation along an equilibrium liquid-gas coexistent curve?
2. Consider a liquid and its vapor, and assume that the vapor behaves as an
ideal gas. Express the slope (∂P/∂T ) along the coexistence curve, in terms of
the latent heat of vaporization (Lv ) of the system, plus other thermodynamic
quantities.

3. Now find an expression for the specific heat of the gas, following the coexistence
curve (that is, the specific heat calculated from the heat into the gas only, as
it contacts the liquid), in terms of T , Lv , and the specific heat at constant
pressure (CP ). CP , (assumed to apply only to the gas) and Lv may be taken to
be constant.
[Hint: a Maxwell relation may be used to obtain the final answer.]
4. Show from your result that there is a temperature regime in which the specific
heat of the gas is negative. Does this mean that the gas is thermodynamically
unstable?

Consider a classical gas, in equilibrium at temperature T , with no interactions be-
tween gas particles. Each particle has mass m.
1. Write down the general form of the velocity (not speed) distribution function
for such a gas. This should be a probability function per unit volume, per d3~v .
Assume the gas as a whole is at rest in your coordinate system. Determine the
normalizing constant.
2. Obtain vrms , which is the root-mean-square velocity for this gas, using your
distribution function (You get credit for demonstrating the method, not for
recalling the result.)
3. Find the probability that a gas particle will have a positive x velocity component
that exceeds vrms . (There is a table of values in the CRC tables that can be
used to evaluate the integral.)

In so-called intrinsic semiconductors at T = 0, electrons fill the lower (valence) band,
whereas the upper (conducting) band is empty. Let the maximal energy of the valence
band and the minimal energy of the conducting band correspond to the momentum
p~ = 0 and be separated by the energy gap Eg . Assume that near the minimum
(maximum) the energy (p) can be represented approximately by an expansion:
Eg p2 Eg p2
c = + ; v = − − ,
2 2mc 2 2mv
where Eg , is the gap in the electron spectrum and mc,v , are effective masses of electrons
and holes respectively.
1. Using the electro-neutrality condition, (i.e., the number of thermally excited

holes in the valence band equals the number of thermally excited electrons in
the conduction band.), calculate the chemical potential µ for electrons as a
function of temperature at a temperature T Eg .

2. Calculate the density of electrons in the conducting band and the density of
holes in the valence band at a temperature T Eg .

Calculate the efficiency of a Stirling engine using a classical ideal gas. In the Stirling
engine the gas is compressed isothermally from a volume V1 , to a smaller volume V2
at a temperature T2 then it is heated at a fixed volume V2 to a higher temperature T2 ;
then it performs work, expanding isothermally to the initial volume V1 , and finally it
returns to the initial temperature T1 by cooling at fixed volume V1 .

A 2-dimensional classical ideal gas of N particles at a temperature T , is contained to
an area A in the x − y plane.
1. Find the partition function and the free energy for this system.
2. Determine the surface tension as a function of temperature and density (numbe

r of particles per unit area) n = N/A.
3. If the same gas is placed in a field of constant force per particle, F , directed
along the x-axis, determine the density n as a function of x.
4. Find how the surface tension varies with x.

Consider a solid with N , atoms each having a mass m. Assume that each atom has
three independent modes of oscillation, each at the same frequency ω0 . This is known
as the Einstein model. Let the solid be in equilibrium with a vapor of the same type
of atom, and let 0 > 0 be the sublimation energy per atom, i.e. the energy which
is necessary to remove an atom from the solid to the vapor with zero final kinetic
energy.
The vapor can be treated as an ideal gas. Its free energy is
√
Vg 2π~
Fg = −kB T Ng log + 1 , Λ T = √ ,
Ng Λ3T mT
where we have assumed that the vapor contains Ng particles occupying a volume Vg .
1. Find the free energy Fs of the solid.
2. Find the equilibrium vapor pressure as a function of temperature if the volume

Vg is maintained constant. Neglect any volume changes in the solid, due to
evaporation.


The surface of the sun has the temperature 6000K. The sun’s radius is R ≈ 106 km.
1. Assuming that the sun is a black body, what is the emitted power per cycle
dP/df at a wavelength of 3cm? (Please give a simple approximate expression.)
2. What is the emitted power per cycle dP/df at the wave-length 3 × 10−6 cm?
3. Indicate how you would determine the power P integrated over all frequencies.

One mole of an ideal gas, with internal energy U = 52 nRT (n = 1mole), is taken from
an initial state i, with pressure P0 and volume V0 to a final state f with Pf = 2P0
and Vf = 2V0 by two different paths:
Path 1: The gas undergoes an isothermal expansion from V0 to 2V0 , and then the pres-
sure is increased to its final value Pf at constant volume.
Path 2: The gas undergoes an isothermal compression to Pf , and then is expanded at

constant pressure to its final volume Vf .
1. Sketch P − V diagrams for each case.
2. Find the heat Q added to the system in each step of the above two processes in
terms of P0 , V0 , and other constants.
3. Find the change in entropy of the gas in going from the initial to the final state.

The cycle of a highly idealized gasoline engine can be approximated by the Otto
cycle. Steps 1 → 2 and 3 → 4 are adiabatic compression and expansion, respectively.
Steps 2 → 3 and 4 → 1 are isochoric (constant volume) processes. Treat the working
medium as an ideal gas with constant γ = CP /CV = 5/3 and take V1 = 3liters,
P1 = 1atm (105 N/m2 ), and P3 = 2P2 .
1. Sketch the cycle on a P − V diagram.
2. Compute the efficiency of this cycle for compression ratio r = V1 /V2 = 4.
3. Calculate the work done on the gas during the two steps 1 → 2 and 2 → 3.
4. Calculate the entropy changes of the gas during the two step 1 → 2 and 2 → 3.


A cylindrical container of height L and radius R contains many identical non-interacting
particles of mass m at temperature T . If the container rotates about its axis at an-
gular velocity ω, the single-particle Hamiltonian in the rotating frame is given by
p2 mω 2 r2
H= − ,
2m 2
where r is the radial coordinate, and p is the total momentum.
1. The earth’s atmosphere thins out with increasing height, because of gravity. A
similar effect occurs for the gas within this rotating container. Determine how
the pressure and density vary with radial coordinate r.
2. If the system has N particles, obtain the density as a function of r.
3. Obtain an approximate expression for the density distribution at high rates of

rotation, i.e, mω 2 R2 /2 kB T . In this case, essentially all of the gas is com-
pressed into a region of characteristic thickness d R close to the wall. How
does d scale with m, ω, and T ? For hydrogen molecules at room temperature,
in a container with R = 5cm, estimate the numerical value of ω where d equals
0.1R.
Boltzmann constant kB = 1.38 × 10−23 J/K

Speed of light c = 3.0 × 108 m/s
Proton mass mp = 1.67 × 10−27 kg

A horizontal wire of length L is fixed at both ends and tightened to a tension F . It
is in equilibrium with a heat bath at temperature T .
1. Because of thermal fluctuation, the midpoint of the wire is sometimes displaced

vertically by a distance y (y L). Find the work done by the heat bath to the
wire.
2. Find the probability for such displacement to happen.
3. Find the root-mean-square displacement of the midpoint of the wire.

In a “hot quark-gluon plasma”, the gluons are massless spin-1 particles (energy-
momentum relation = cp), with eight degenerate “colors”, and quarks are relativistic
spin-1/2 particles with three degenerate “colors” and two degenerate “flavors”.
1. Determine the degeneracy factors dG and dC for the gluons and the quarks.
In what follows, consider only the gluons, and take volume V.

2. Determine the thermal average for the total energy E for the gluons. (Gluons
are not conserved; from this one can show that their chemical potential µG = 0.)
Leave any integrals in dimensionless form; do not evaluate them.
3. Determine the heat capacity CV , and the entropy S.
4. Determine the free energy F and the pressure P associated with the gluons.
Show that P = 13 E/V

Consider a crystal with p identical hydrogen atoms distributed over J identical bulk
sites and K identical surface sites. Let p J. The atoms do not interact, but they
have an energy B at the bulk sites, and an energy S at the surface sites. Let b be
the number of atoms at bulk sites, and let r be the number of atoms at surface sites
, so p = b + s.
1. If B = S , what is the ratio b/s at all temperatures? Explain your reasoning.

In what follows, do not assume that B = S .
2. Find the number of ways W (J, b) that b atoms can be distributed over the J
bulk sites. Find the bulk entropy SB (J, b), the bulk energy EB (J, b), and the
bulk free energy FB (T, J, b).
3. Find the number of ways W (K, s) that s atoms can be distributed over the K
surface sites. Find the surface entropy SS (K, s), the surface energy ES (K, s)
and the surface free energy FS (T, K, s).
4. Minimize the total free energy FB (T, J, b) + FS (T, K, s) with respect to b at

fixed b + s = p. Find b/s for p J, K. Note that, for large integer z, ln(n!) =
z ln(z) − z.
5. Find b/s in the following limits: at high T ; at low T if S B ; at low T if

S B .

A set of N non-interacting molecules are fixed in space. Each has a permanent electric
dipole moment of magnitude p0 that is free to rotate in three dimensions. They are
~ = E0 ẑ.
in a uniform electric field E
1. Find the thermal average, at temperature T , of their total electric dipole mo-
ment P~ .
2. Evaluate P~ at low T , and explain your result physically. Define “low T” in

terms of the parameters of the problem.
3. Evaluate P~ at high T .

4. At “high” T find the electric polarizability α = ∂P/∂E, taking P~ and E

~ along
ẑ.

Find the entropy rise ∆S of a monoatomic ideal gas of N molecules occupying the
volume V1 when it expands to a volume V2 under constant pressure.

1. Using the extensivity/intensivity properties of the thermodynamic quantities,
show that U = ST − P V + µN .
2. Using this result, prove the following thermodynamic identity:

1 ∂n 1 ∂V
=− ,
n2 ∂µ T V ∂P N,T
where −V −1 (∂V /∂P )T,N is the isothermal compressibility and n = N/V is the
particle number density. Here P denotes the pressure, T the absolute temper-
ature, and µ the chemical potential.

Consider a two-dimensional ideal neutron gas with areal umber density ( i.e., number
per unit area) n at temperature T and zero magnetic field. Each neutron has a mass
m.
1. Derive a closed-form expression for the chemical potential µ as a function of T
and n.
2. A magnetic field H is now applied to the system. Each neutron has a mag-
netic moment µN whose direction is opposite to its spin. Derive a relation
which gives implicitly the function µ(T, n, H). Use this relation to show that
(∂µ/∂H)T,n|H=0 = 0.
3. Derive a closed-form expression for the zero-fold spin-susceptibility χS ≡ (∂M/∂H)T,n|H=0
of the system as a function of T and n. Note, that the definition of χS has n
kept constant and not µ, so you must properly use the result of the previous
part to do this part correctly.

You should express your answers for this problem in terms of any of the following
Temperature T
Volume V
Pressure P
Heat capacity at constant volume CV
κT = − V1 ∂V

Isothermal Compressibility ∂P
T
Thermal Expansion α = V1 ∂V
∂T P

1. Express the incremental heat δQ absorbed by a gas if the pressure of the gas is
increased incrementally from P to P + δP while maintaining a fixed volume.
2. For the same process, determine the incremental change in the enthalpy of the
gas, δH where H = U + P V .
3. Evaluate your answers in for the first and the second parts for the case of an
ideal monoatomic gas.

It is given that the equation of state of a certain photon-like gas is given by
P = a(T ),
where P denotes pressure, a > 0 is a constant, and (T ) is the internal energy per
unit volume of the photon gas at temperature T .
1. Calculate the temperature dependence of the total internal energy U for the
whole gas using the equation

∂U ∂P
=T − P.
∂V T ∂T V
One unknown constant is allowed to appear in your answer, but no unknown

functions of either T or V or both are allowed to appear.
2. Calculate the entropy S of the system as a function of T and V .

[Hint: Start from the equation

1 1 ∂U 1 ∂U
dS = (dU + P dV ) = dT + P+ dV,
T T ∂T V T ∂V T
evaluate (∂S/∂T )V , and (∂S/∂V )T , and then integrate them to obtain S. Use
the third law of thermodynamics to fix any unknown integration constant(s) of
this step.]

1 2
A molecule has energy E = 2 mv + λj, where v is the velocity, λ is a constant with
the dimension of energy, and j is an internal quantum number which can take all
odd integer values (no degeneracy). It is in a cubic box of volume V with its walls
maintained at the absolute temperature T .
1. Calculate the average energy of the molecule as a function of T assuming that

it is in thermodynamic equilibrium with the walls of the box.
2. Calculate the free energy of the molecule as a function of T .

3. Calculate the entropy S of the molecule as a function of T .

In thermodynamics, all physical properties can be calculated once one of the thermo-
dynamic potentials is known as a function of appropriate variables (e.g. U (S, V, N )).
Unfortunately, the thermodynamic potentials can not be directly measured but need
to be calculated from experimentally accessible quantities, such as the specific heat at
a constant volume cv = T (∂s/∂T )v , the isothermal compressibility κT = −v −1 (∂v/∂P )T
and the thermal expansion coefficient at constant pressure α = v −1 (∂v/∂T )P , where
N is the particle number, P is the pressure, T is the temperature, s = S/N is the
specific entropy and v = V /N is the specific volume.
Given the following values for these quantities:
1/2
4v0 P0 T v 2 4
cv = 2
, κT = , α=
T0 v0 P T
and that the pressure, specific volume and temperature are all known at a particular
reference state (i.e., P0 , v0 , and T0 ), determine
1. The specific volume as a function of T and P and the constants of the reference
state, P0 , v0 , and T0 .
2. The specific entropy as a function of T and P and the constants of the reference
state, P0 , v0 , and T0 . (You may assume that the third law of thermodynamics
is valid for this system, and use it to fix an integration constant.)
[Hint: First obtain S(T, v) and then convert it to S(T, P )].
3. The specific Gibbs free energy g as a function of T and P and the constants of
the reference state, P0 , v0 , T0 , and g0 .

The fundamental thermodynamic relation for a rubber band is
dU = T dS + τ dl
where U is the internal energy, T is the absolute temperature, S is the entropy, τ is
the tension and l is the length of the rubber band.
1. What is dH, where the generalized enthalpy for this system is H = U − τ l.
2. Derive the Maxwell relation that is associated with the expression for dH. State
clearly what variable is held constant in each partial derivative.
3. Using the known fact that a rubber band contracts when it is heated at constant
tension, deduce from the Maxwell relation obtained in the previous part that a
rubber band warms when it is stretched adiabatically.


Consider a classical ideal monoatomic gas at temperature T in a uniform gravitational
field (i.e, an isothermal atmosphere). Assume that the gas atoms have mass, m, and
that their distribution overall all possible heights from z = 0 (the surface of the
earth) to z = ∞ is an equilibrium one. Denote the magnitude of the gravitational
acceleration by g and assume that it can be taken to be a constant for all values of z.
1. Find the probability density governing the fraction of atoms per unit height at
a height z.
2. Find the mean potential energy per atom.
3. Find the total internal energy and total heat capacity of the gas (i.e., the total
amount of heat energy required to increase the temperature of the entire gas
column by 1K).

The intersection of two Gibbs free energy surfaces is a line where Gα = Gβ , along
which two phases α and β coexist. Let the phases α and β be the liquid phase and
the gas phase, respectively.
Along the liquid-gas coexistence line in the P − T plane, show that, to a vary
good approximation,
P Lvap 1 1
log = − ,
P0 R Tb T
where P is the vapor pressure of the liquid present, P0 , is the atmospheric pressure
(1atm), R is the ideal gas constant, T is the absolute temperature, Tb is the boiling
point of the system (at atmospheric pressure), and Lvap , is the heat of vaporization
per mole (whose dependence on T and P may be neglected). You may assume that
the gas phase obeys the ideal gas law.

You are given two objects with the same total heat capacity, C0 which is temperature
independent. (These objects are finite and should not be treated as thermal reser-
voirs.) The two objects are initially at temperatures T1 and T2 (T1 > T2 ) respectively.
1. What type of heat engine would you operate between these two objects so that
the maximum total amount of useable work ts extracted?
2. Using this type of heat engine, determine the final temperatures of the two
objects.
3. Using this type of heat engine, determine the total amount of useable work
extracted.


According to the principles of quantum statistical mechanics, the pressure of black-
body radiation inside a volume V may be calculated by treating the radiation as a
photon gas, and using the relation
1 ∂ log Z
p̄ = ,
β ∂V
where p̄ is the mean pressure, Z the partition function, and β = 1/kB T is kept
constant. You may assume that the volume V is a cubic box of edge length L = V 1/3 ,
with walls maintained at temperature T .
1. Express the partition function Z in terms of the energies s , of a set of inde-

pendent photon states (i.e., normal modes) in the volume, and use it to show
that
X ∂s
p̄ = − n̄s ,
s
∂V
where ns is the mean population of the state s with energy s .
2. Using the above result, obtain an explicit relation between the mean pressure
p̄ and the mean energy density ū (= Ē/V ) of the photon gas.

Let
N2 1 N3
F = −A T − B 2 T 2 − CN
V 2 V
describe the Helmholtz free energy of a system of N particles in a volume V at
temperature T , for a finite interval of temperature not including absolute zero. Here
A, B, and C are positive constants.
1. Find S, P , and µ in terms of N , V , and T , where S is the total entropy, P is

pressure, and µ is the chemical potential.
2. Find the energy U in terms of N , V , and S.
3. Find T in terms of N , V , and S, and verify that it is consistent with the results
of the first part.
4. Find the isothermal compressibility κT = −V −1 (∂V /∂P )T,N .
5. Find the total heat capacity CV .


It is given that
N (T, V, z) = V T 3 f1 (z)
and
U (T, V, z) = V T 4 f2 (z),
where N is the total particle number, U is the total internal energy, T is the absolute
temperature, V is the total volume of the system, and z ≡ eβµ is the fugacity, with
β ≡ 1/kB T , and µ the chemical potential. Let CV ≡ (∂U/∂T )V,N denote the total
heat capacity of the system at constant volume, find CV in terms of T , V , f1 (z),
f2 (z), and the derivatives of f1 (z) and f2 (z).

Consider a system of N independent harmonic oscillators with the same frequency ω.
The system is at, temperature T .
1. Show that the partition function of the system is

−N
~ω
QN = 2 sinh .
2kB T
2. Using this result, obtain the internal energy U of the system as a function of T
and N .
3. Show that the heat capacity is

2
e~ω/kB T

~ω
C = N kB 2
(e~ω/kB T − 1) kB T
and it approaches to 0 as T → 0.
4. Determine its Helmholtz free energy F .
5. Determine its entropy S.

An unknown substance ts experimentally found to satisfy the following equations of
state:
T (u, v) = au2/3 v −1/2 and P (u, v) = buv −1 ,
where a and b are some constants, T and P are the substance’s temperature and
pressure as functions of its internal energy per particle, u, and volume per particle,
v, respectively.
1. Find the condition(s) under which the above two equations of state are con-
sistent with each other, and then determine the entropy per particle of the
substance, s(u, v), to within an additive constant.

2. Fix the constant in your answer to the previous part by invoking some law in
thermodynamics.

A non-ideal gas has a fundamental relation given by
1 2 −1/2 −1/2
U (S, V, N ) = S V N ,
2A
where U is the total internal energy, S is the total entropy V is the volume, N is the
number of molecules, and A is a constant.
1. Determine the following equations of state
U (T, V, N ) and P (T, V, N ).
2. Consider a rigid chamber of volume V0 which is subdivided by an impermeable

membrane into volumes V0 /3 and 2V0 /3. The chamber is isolated from the rest
of the universe so that no heat or work can be transferred between them. (You
may assume that the walls of the chamber have negligible heat capacity) A
number N0 of molecules of the gas of the previous part is placed in the smaller
section (volume V0 /3), and the larger section is evacuated. Initially, the gas
has internal energy U0 , temperature T0 and entropy S0 . Solve the following two
parts of this problem under these conditions.
(a) If the membrane separating the two sections is broken, so that the gas
can freely expand to fill the entire chamber, what is the final values of
the internal energy Uf , temperature Tf , and entropy Sf of the gas after
equilibrium has been reached? Express your answer in terms of U0 , T0 ,
and S0 .
(b) If the gas is then slowly compressed isothermally back to its original vol-
ume, how much work is done by the piston compressing the gas? Express
your answer in terms of U0 , T0 , and S0 .

1. A gas of N inert atoms (such as N e or Ar) is contained in a volume V which
may be taken as a cube of side L = V 1/3 with periodic boundary conditions.
The gas is in thermal equilibrium with the walls of the container which are
maintained at (absolute) temperature T . Calculate the number of atoms in
this gas with atomic kinetic energy larger than rkB T , where r is some posi-
tive rational number (such as 2.0). Your answer may contain a dimensionless,
unevaluated integral. You may neglect any interaction between the gas atoms,
and treat the gas with Boltzmann statistics.
2. Will your answer change if the gas is made of N diatomic molecules (such as
N2 or CO), if by kinetic energy we now mean the center-of-mass kinetic energy
of a molecule? Briefly justify your answer.

Problem 107. Quantum oscillator ID:SM-U-1840

2
A quantum particle of charge q is in the potential V (x) = mω
2
x2 in 1D at temperature
T.
a. Find the heat capacity of this system.
b. Find the electric dipole susceptibility of the system. (d = −(∂F/∂E)V,N,T , χ =

(∂d/∂E)V,N,T , where E is the electric field.)
c. For the oscillator state ψn in the presence ofPelectric field E calculate xn =

hψn |x̂|ψn i, and then average displacement x̄ = n xn wn .

2 Graduate level
Problem 108. 1983-Fall-SM-G-4. ID:SM-G-3
a. Show that
∂S
= −αV,
∂P T
where α is the coefficient of thermal expansion.
b. Show that for an isothermal compression
dE = (−T αV + P V βT )dP,
where βT is the isothermal compressibility. To get the full credit for this problem
you must start with dE = T dS − P dV .
Problem 109. 1983-Fall-SM-G-5 ID:SM-G-20

a. What is the average energy of a system at temperature T with two quantum states,
with an energy difference separating the levels?
b. In a highly disordered solid it is believed that a large number of two-level “tunnel-

ing” systems are present with a distribution of energy differences. If the number
of these two level systems per unit volume of the solid with energy separations
between and + d, D(), is a constant, show that their contribution to the heat
capacity of the solid will be linear in temperature.
Problem 110. Distribution function. 1983-Fall-SM-G-6 ID:SM-G-27

A classical one dimensional particle, confined to the region y ≥ y0 is in a potential
V (y) = V0 log (y/y0 )
The statistical distribution is given by %(p, q) = Ae−E(p,q)/T , where A is a normal-

ization parameter, T is a parameter which is called temperature, and E(p, q) is the
particle’s energy.
a. Find the normalization constant A. Determine the critical temperature Tc above
which the particle escapes to infinity (You need to figure out what it means.).
b. Write down the normalized positional distribution function f (y) (i.e. the proba-
bility per unit distance to find the particle between y and y + dy) for this particle
for T < Tc .
c. Find the average distance hyi for the particle. What happens if 0 < Tc /2 − T
Tc /2

Problem 111. 1983-Spring-SM-G-4 ID:SM-G-44

A thermodynamic system consists of N spatially separated noninteracting subsys-
tems. Each subsystem has non-degenerate energy levels 0, , 2, and 3. The system
is in thermal equilibrium with a heat reservoir of absolute temperature T = /kB .
Calculate the partition function, the mean energy, and the entropy of the thermody-
namic system.
Problem 112. 1983-Spring-SM-G-5. ID:SM-G-48

At T = 0, all the N atoms in a crystal occupy a lattice site of a simple cubic lattice
with no vacancies. At higher temperature, it is possible for an atom to move from a
lattice site to an interstitial site in the center of a cube (the interstitial atom does not
have to end up close to vacancy). An atom needs energy to make this transition.
a. Compute the number of different ways of making n vacancies (and correspondingly

fill n interstitial sites) in the lattice.
b. Calculate the entropy of a state with energy E = n.
c. Calculate the average hni in equilibrium at temperature T .
d. Calculate the free energy of the lattice at temperature T .

24
A paramagnetic salt contains a total of 10 non-interacting magnetic ions, each with
a magnetic moment of 1 Bohr magneton (9.273 × 10−24 Am2 ) which can be aligned
either parallel or anti-parallel to a magnetic field. A magnetic field of magnetic
induction 1T is applied at a temperature 3K.
a. Calculate the partition function.
b. Compute the magnetic energy.
c. Compute the heat capacity.
[Hint: You will be given more credit for this problem if you can also give numerical
values for the last two parts.]

a. Find the mean speed of the fermions in an ideal D-dimensional fermi gas at T = 0
(the dispersion is p = p2 /2m) in terms of vF – Fermi velocity (velocity at F ).
b. Find the average kinetic energy of a fermion in terms of vF .


The single particles energy levels for a particular Hamiltonian are n = n. where
n = 1, 2, 3 . . . . For a system of three non-interacting identical particles in the
same spin state, find the energy and the degeneracy of the ground state and the
first four excited states if the particles are:
a. Bosons.
b. Fermions.
c. What is the energy and degeneracy of the ground state and the first four excited
states if the system consists of spin 1/2 particles which are not constrained to be
in the same spin state?

Remembering that the free energy F will be minimized in a given phase, and that the
“order parameter” is defined to be zero above a phase transition, consider a system
whose free energy F depends on an order parameter φ according to
F (φ, T ) = F0 + a(T − Tc )φ2 + bφ4 ,
where F0 , a, and b are all positive constants. Show that there is a phase transition
at a temperature Tc and deduce the temperature dependence of the order parameter.
Calculate the jump in the heat capacity at T = Tc .
[Hint: C = −T (∂ 2 F/∂T 2 ).]

A system consists of N weakly interacting particles each of which can be in either of
the two states with respective energies 1 and 2 , with 1 < 2 .
1. Make a qualitative plot of the mean energy ¯ of the system as a function of

the temperature T . What is ¯ in the limit of very low and very high temper-
atures? Roughly at what temperature does ¯ changes from its low to its high
temperature value?
2. Using the result of the previous part make qualitative plot of the heat capacity
CV as a function of the temperature T .
3. Calculate explicitly an expression for the mean energy ¯(T ) and heat capac-
ity CV (T ) for this system. Verify that your expression exhibit the qualitative
features discussed in the previous parts.


1. For a photon gas, show that the average number of photons in a particular
state, s, is given by
1
ns = βs ,
e −1
where s is the energy of the state s, and β = 1/kB T .
2. Calculate the density of modes i.e. the number of modes per unit volume
between ω and ω + dω for a three dimensional photon gas.
3. Show that the average energy density ū of the gas can be written as
hω 3 dω
ū(ω, T )dω =
π 2 c3 (eβhω − 1)
4. Show that hωmax /kB T ≈ 3, where ωmax represents the peak in the energy
density functional.
5. Show that the energy density functional is proportional to T 4 .

[Hint: Change the energy hω to a dimensionless variable.]

Suppose we have some type of wavelike excitation in a solid which is characterized by
a free quasiparticle of spin 3. The total number of quasiparticles in the system is not
conserved. Furthermore, the excitation (quasiparticle) obeys the dispersion relation
ω = Ak 3 , where ω is the angular frequency of the excitation, k is its wave number,
and A is a constant of proportionality. If the solid has a volume V and is macroscopic
in size, then determine the temperature dependence of both the internal energy and
heat capacity in the limit of very low temperatures.

There are three quantum states of energies 0, , and 2. Consider a system of two
indistinguishable non-interacting particles which can occupy these states. The system
is coupled with the heat bath at temperature T .
a. Calculate the free energy of the system in case the particles are Bosons.
b. Calculate the free energy of the system in case the particles are Fermions.
c. What is the ration of occupation probability of the highest energy state of the
system to the lowest energy state in each of these cases?


A sample of water is placed in an external magnetic field B. Each proton has a spin
1/2 and a magnetic moment µ. An applied radio-frequency field can induce transitions
between the magnetic (Zeeman) energy levels, (How many possible energy levels per
proton are there?), if the frequency ν satisfies the Larmor condition hν = 2µB. The
power absorbed from the radiation field is then proportional to the difference in the
number of protons in the energy levels. Assume that the protons in the water are in
thermal equilibrium at temperature T such that µB kB T .
1. Give an expression for the partition function.
2. How does the absorbed power depend on the temperature of the water?

If D() is a density of states function, find an expression for the heat capacity of a
fermion gas at kB T 0F , even if D() is a complicated function of energy .
[Hint: The expression for the heat capacity should contain D(), T , and some
constants. 0F is the chemical potential at absolute zero. You may need the integral
Z ∞
x2 ex π2
x 2
dx = .
−∞ (e + 1) 3

In one-dimension, a mass m is attached to a spring of spring constant k. The system
is in thermal equilibrium at a temperature T .
1. Assuming the classical statistics hold, what is the rms displacement of the
mass from equilibrium, if T = 70o F , m = 2g, and k = 50g/s2 ? Take kB ≈
1.4 × 10−16 cgs. and ~ ≈ 10−27 cgs.
2. Treating this system using quantum statistics, where the energy of the system
is E = ~ω(n + 1/2) for n = 0, 1, . . . , and there is only one state at each energy,
calculate the partition function of this system. (ω is the oscillation frequency
of the mass on the spring.)
3. What is the average energy Ē of the system? Does this come close to the
classical value for the system in the first part?
4. From the previous part, find the average occupation number n̄. Must n̄ be large
or small for Ē to be close to its classical value?
5. Give an approximate criterion for the validity of the classical result.


A 3D harmonic oscillator has mass m and the same spring constant k for all three
directions. Thus, its quantum-mechanical energy levels are given by
E = ~ω(n1 + n2 + n3 + 3/2)
Neglect the zero point energy in what follows.

1. What are the energy E0 and degeneracy g0 of the ground sate? Of the first
excited state? Of the second excited state?
2. What is the partition function for this system if only the lowest two (ground
and the first exited) energy levels are important? When this approximation
valid?
3. What is the free energy in this case?
4. What is the entropy in this case?
5. What is the rms fluctuation δE ≡ (E 2 − (Ē)2 )1/2 in the energy in this case?

Consider a large number N of identical non-interacting particles, each of which can be
in only one of two states, with energies 0 and 1 . Denote by n0 and n1 the occupation
numbers of each of these states.
1. Find the total energy E as a function of n0 .
2. Find the number of states N available to the system, as a function of n0 .
3. Find S, the entropy, as a function of E.
4. Find the temperature T as a function of E.
5. Using E0 = N 0 and ∆ = (1 − 0 ), show that

N ∆
E = E0 +
1 + exp[∆/kB T ]
[Hint: log n! ≈ n log n − n, for large n.]

1. Find the Fermi energy at T = 0, f , of a gas of N non-interacting spin one-half
particles constrained to move in two dimensions.
2. Recall that the surface tension, σ, in two dimensions is analogous to pressure

in three dimensions so that the surface tension contribution from a particle in
a state n is given by −∂n /∂A. Shaw that the surface tension at T = 0 is given
by N f /2A, where A is the area that the particles occupy.


1. Show that for an ideal gas, for a quasistatic adiabatic process
dP P
= −γ ,
dV V
where γ = CP /CV .
2. Write down the expression for the work done by one mole of a monoatomic ideal
gas during an adiabatic expansion from a state (P1 , V1 ) to a state with volume
V2 .
3. The molar energy of a monoatomic gas which obeys van der Waals’ equation of
state is given by
3 a
E = RT − ,
2 V
where V is the molar volume at a temperature T and a is a constant of the gas.
If initially, one mole of the gas is at the temperature T1 and occupies volume
V1 , and the gas is allowed to expand irreversibly into a vacuum in an isolated
container, so that it occupies a total volume V2 , what is the final temperature
T2 of the gas?
4. Calculate the change of the temperature in this process for the ideal gas. Give
the reason for your answer explaining concisely the origin of the differences (In
one short(!!!!) sentence.).

For a vapor in equilibrium with its solid phase, find the relation between the pressure
P and the temperature T , if the molar latent heat q is constant. The vapor is close
to the ideal gas, and the molar volume of the gas is much larger than that of solid.

A thermally isolated container is divided by a partition into two compartments, the
right hand compartment having a volume b times larger than the left one. The left
compartment contains ν moles of an ideal gas at temperature T , and pressure P .
The right compartment also contains ν moles of an ideal gas at temperature T . The
partition is now removed. Calculate:
a. The final pressure
b. The total change in the entropy if the gases are different.
c. The total change in the entropy if the gases are the same.
d. What is the total change in the entropy if the gases are the same and b = 1? Can
you explain the result?


N Classical particles are constrained to move on a frictionless flat surface of area A.
1. What is the partition function for the system at the temperature T , assuming
that the particles are distinguishable?
2. Same as above, if the particles are indistinguishable.
3. For indistinguishable particles, compute the free energy F .
4. For indistinguishable particles, compute the entropy S.
5. Verify that, if N → 2N and A → 2A, then S → 2S. What role indistinguisha-

bility have to play in this result?
6. Let σ represent the two-dimensional pressure, or surface tension, of this system.

Find σ as a function of N , T , and A.

Consider a system of N 1 noninteracting bosons of spin zero, with quantum states
at the single particle energies 0 and . The thermal average population of the lowest
state is twice the population of the state with energy . Find approximate values of
the chemical potential µ and the temperature T .

A model for a vacancy formation in an otherwise perfect crystal is as follows. An
energy Es is required to produce a vacancy by taking an atom from the interior and
putting it on the surface. Let the number of lattice sites in the bulk N greatly exceed
the number of vacancies n, and let n 1.
1. In how many ways can one take n atoms from the interior? Treat the atoms as
indistinguishable.
2. What is the entropy S associated with this?
3. What is the energy of the system, assuming that E = 0 in the absence of

vacancies?
4. For a given temperature T , what is the thermal average value of n?

Consider a cyclic engine operating with one mole of an ideal monoatomic gas in
between two baths with temperatures Ta and 2Ta in the cycle a → b → c → d → a.
Va and Ta are the volume and the temperature of the gas in point a.
a → b is isobaric increase of temperature from Ta to 2Ta
b → c isothermal expansion to the volume 3Va

c → d decrease of temperature back to Ta at constant volume
d → a isothermal compression back to the volume Va
All processes are reversible.
a. Calculate the efficiency of this engine and compare it to the maximum possible
efficiency for an engine operating between Ta and 2Ta .
b. What is the net entropy change of the gas in one cycle?
c. What is the net change of the energy of the gas in one cycle?
d. What is the net change of the entropy of the hot thermal bath during one cycle,
if all processes are reversible?
e. What is the net change of the entropy of the cold thermal bath during one cycle,
if all processes are reversible?

Write down the partition function for an ideal gas of N monoatomic molecules in a
volume V in a classical limit where you have treated the particles as distinguishable.
What is the partition function in the classical limit if the particles are indistinguish-
able? Use both partition functions to calculate the entropy of the ideal gas in each
case. Why is the result for the distinguishable particles physically unacceptable?

1. Consider a particle which can take one of only two energy levels (E = 0 or E =
). Find and sketch as a function of T the average energy Ē(N, T ) and the heat
capacity CV (N, T ) for a system of N particle. The particles are distinguishable.
2. Suppose that the value of the excited state energy varies for different particles
in a system of N particles. Furthermore, assume that the number of particles
with a particular value of the excited state energy between and + d is n()d
and suppose that n() is a constant for all energies between 0 and 0 , and that
there is no states with > 0 , i.e.

n0 , for 0 < ≤ 0
n() =
0, for > 0
R∞
and N = 0 n()d = n0 0 . Find the temperature dependence of the specific
heat of these N particles at low temperature, T 0 /kB .


Consider a system of N noninteracting particles in a volume V at an absolute tem-
perature T . The single particle energy states are described by i = ~2 ki2 /2m. For
convenience, assume that the ki are determined by periodic boundary conditions.
1. Show that the mean pressure P̄ of the system is given quite generally in terms
of the average kinetic energy Ē by
2Ē
P̄ = .
3V
independent of whether the particles obey classical, Fermi-Dirac, or Bose-Einstein
statistics.
2. Show that the dispersion in pressure of this system, (∆P )2 = (P − P̄ )2 , is given

by
2

2k B T ∂ P̄
(∆P )2 = .
3V ∂T N,V

Consider N identical and independent particles of spin 1/2 in a magnetic field so that
the energy of each particle is either + or − depending upon the orientation of the
spin: down or up respectively. The probability of the energy − is p and of + is
q = 1 − p.
1. Find the probability that N1 spins are up and N2 are down, with N1 + N2 = N .
2. From this probability find the average or expected value of the energy in terms
of p, , and N .
3. By considering that N1 and N2 are continuous rather than discrete variables,

find the most likely (i.e., maximal probability) for the values N1 and N2 using
the approximation that log(x!) ≈ x log(x) − x.
4. Write down a partition function for this system at a temperature T .
5. Find the free energy, the entropy, and the total energy from this partition
function. For what value of p will your result in the second part agree with
your result for the total energy in this part?

Consider a classical system of N weakly interacting particles. Each isolated particle
can be in n states. Assume the ground state degeneracy of the system is aN , where
1 ≤ a < n. The excited energy levels are on the average evenly distributed around
a characteristic energy E1 . there are no phase changes in the phase diagram for the
system.

1. Sketch entropy per particle (N → ∞) as function of temperature in the entire

temperature range. Write and denote on the graph the values of entropies and
of characteristic temperature you can determine from the given information.
2. Sketch the specific heat CV as function of temperature using CV /T and T as
coordinate axes. What is the total area under the curve?
3. Answer the first part now assuming that the levels are not all evenly distributed,
but rather m out of n states have characteristic energy E2 at least an order of
magnitude larger than the characteristic energy E1 of the remaining states.

An incompressible fluid of density ρf is confined to a very long (infinite) cylinder
of cross section A with which it rotates at a constant angular velocity ω around
a perpendicular axis through the middle-point of the cylinder. Small number of
microscopic spheres each of volume v and density ρs < ρf are immersed in the rotating
fluid at temperature T. Neglect any interaction between the spheres, find the average
distance of a sphere from the rotation axis.

A certain solid material has an isothermal compressibility

1 ∂V
κT = −
V ∂P T
Prove that adiabatic volume and pressure changes are related by
dV CV
= −κT dP,
V CP
where CV and CP are the specific heats of the material at constant volume and
pressure respectively.


Consider a monoatomic van der Waals gas whose equation of state is
a RT
P =− 2
+ .
V V −b
If this gas undergoes free expansion,
1. What is the change in temperature in terms of the initial volume V1 and final
volume V2 ?
2. Determine the change in entropy.
[Hint: CV for a monoatomic van der Waals gas is a temperature and volume inde-
pendent constant.]

Let p~ = ρ(|px |+|py |+|pz |) be the energy-momentum relation of a conducting electrons
in a certain (fictitious) metal, where ρ is a constant with the dimensions of velocity,
and |x| denotes the absolute value of x.
1. Draw a picture of a typical constant-energy surface p~ = , for the above dis-
persion p~ .
2. Express the Fermi energy F as a function of the electron density n for this
metal. (Note, that electrons have spin 1/2.)
3. Calculate the electronic density of states (per unit volume) as a function of

for this metal. Denote it as D().
4. Calculate the total energy of N electrons at T = 0 in this metal. Express E0 /N

in terms of F .
5. Now let the temperature T be finite. Express N and the total energy E as func-
tions of T and the chemical potential µ. The expressions can involve integrals
which you do not have to evaluate.

Show that the van der Waals equation of state can be derived from a mean field
theory: Assume that the potential felt by each particle in a gas is

∞, for r < r0
u(r) = ,
−ū, otherwise
where
ū = cN/V.
Here N/V is the number of particles per unit volume, and c is a constant. (First
evaluate the classical partition function Z, and then use it to find pressure P .) Give

physical interpretation of your finite answer (the van der Waals equation), and show
that it reduces to the correct result when u(r) = 0.

A system of ideal Boltzmann gas containing N monoatomic molecules (of mass
m each) is trapped in a three-dimensional harmonic potential well V (x, y, z) =
1
2
K (x2 + y 2 + z 2 ), so it will form a spherical cloud whose room-mean-square radius
1/2
r̄rms ≡ (hx2 + y 2 + z 2 i) will be the function of temperature. Calculate:
1. The (quantum) canonical partition function, (which no longer has volume V as

an independent variable due to the trapping potential).
2. The free energy F (N, T );
3. The total entropy of the cloud S(N, T );
4. Take the high-temperature approximation of S(N, T ) to the leading order in

some small parameter, and use it to obtain the specific heat C(N, T ) in this
limit to the same order. (Note: the specific heat is not of constant volume,
nor of constant pressure, but of constant K, the force constant, and, of course,
constant N .)
5. Interpret your result from the previous part in light of the equipartition theorem.
6. Given that hn|x2 |yi = (n + 1/2)~ω0 /K for a quantum mechanical harmonic

oscillator of mass m and force constant K, calculate r̄rms , and hence the “mean”
volume V̄ ≡ 4π r̄3 , of the above cloud as a function of N and T . What is the
3 rms
smallest V̄ at any temperature, and what is the behavior of V̄ with respect to
T in the high-temperature limit?

Show that in two dimensions, the heat capacity CV at low temperatures is the same
for fermions and bosons.
[Hint: Z ∞ 2 x Z ∞ 2 x
x e dx x e dx π2
= =
0 (ex − 1)2 x
−∞ (e + 1)
2 3
]

A system has only two energy levels. The lower energy level with energy E = −E0 is
non-degenerate, and the higher energy level with energy +2E0 is three-fold degener-
ate.
1. Assuming that the system is in thermodynamic equilibrium with its surround-

ings which are maintained at an absolute temperature T , what are the proba-
bilities that the system is found in each of the two energy levels?

2. If the volume of this system is V0 when it is in the lower energy state, but it
increases to 1.2V0 when it is in the higher energy state, calculate the mean vol-
ume hV i of this system as a function of temperature, and its thermal expansion
coefficient α as a function of temperature.
3. What is expected limiting value of α as T → ∞? What about hV i itself? Use

these limiting behaviors to check your results of the previous part.

A system contains two different types of excitations whose numbers are not conserved.
One type consists of bosons such that the number of excitation modes with energy
between and + d is
V 2
d.
2π 2 c3
The other consists of fermions such that the number of excitation modes with energy
between and + d is
0 for < 0
2V
3π 2 b
d for > 0
V is the volume of the system and b and c are constants.
1. Calculate the average energy of the system as a function of temperature T .
2. Calculate the specific heat per unit volume of the system as a function of tem-
perature.
[Hint: One of the integrals can only be done after a series expansion, using
∞ Z ∞
1 X 1 1
= (−1)n+1 e−nx , xe−ax dx = x0 e−ax0 + 2 e−ax0 .
ex + 1 n=1 x0 a a
Also you might need some of the following definite integrals:

Z ∞ Z ∞ 2 Z ∞ 3 ∞
π2 π4 x4 dx
Z
xdx x dx x dx
= , = 2ζ(3), = , = 24ζ(5)
0 ex − 1 6 0 ex − 1 0 ex − 1 15 0 ex − 1
where ζ(x) is the Riemann zeta function. ]

Consider a system of N non-interacting nuclei with a spin quantum number I. Find an
expression for the magnetization M and the entropy S of these nuclei at a temperature
T in a magnetic field B. Express your answer in terms of g, the Laudé g-factor for
this nucleus, and µB , the Bohr magneton. Indicate the high temperature and low
temperature limits for M and S. How could the nuclear magnetic moments be used
to cool the material?
[Hint: Useful relations:
1 + x + x2 + · · · + xn = (1 − xn+1 )/(1 − x),

sinh x ≡ (ex − e−x )/2,

d sinh x
= cosh x ≡ (ex + e−x )/2.
dx
]

Consider N spin-1/2 (fermionic) atoms of a monoatomic gas that might be physically
adsorbed on a homogeneous surface of area A. Assume that the atoms are nonin-
teracting and that the energy of a single such atom would be described quantum
mechanically by
= (p2x + p2y )/2m − 0 ,
where 0 is the binding energy of the atom to the surface and is same for all of the
atoms.
1. Calculate the T = 0 value of the chemical potential µ for these atoms as a
function of the area density N/A, binding energy 0 , and mass m.
2. At temperatures very close to T = 0 (i.e., so that you can ignore any tem-
perature dependence of the quantities you might calculate for the adsorbed
fermions,) find the areal coverage N/A of adsorbed atoms as a function of the
density ρ ≡ N 0 /V 0 and temperature T of a dilute (three-dimensional) gas of
the same atoms that is in thermal equilibrium with the adsorbed gas. Assume
that the dilute gas can be treated classically at the given temperature with the
partition function
3N 0 /2
1 m N0
Z= 0 2
(2V 0 )
N ! 2π~ β
and β ≡ 1/kB T .

Consider an ideal classical gas of rigid dipolar molecules in an electric field E. The
dipole moment of each molecule is µ. Calculate the linear dielectric constant of the
gas as a function of temperature T and density ρ = N/V .

In experiments on the absorption spectrum of gases at finite temperature, atoms
are always moving either towards or away from the light source with distribution of
velocities vx . As a consequences the frequency of the photon seen by an electron in a
Bohr atom is Doppler shifted to a value νD according to the classical formula
νD = ν0 (1 + vx /c).
1. Write down the normalized Maxwell distribution for vx .
2. Determine the distribution function g(νD ) for the fraction of gas atoms that
will absorb light at frequency νD .

3. Determine the fractional linewidth

s
∆ν (νD − ν0 )2
≡ .
ν0 rms ν02
4. Estimate the fractional linewidth for a gas of hydrogen (M ≈ 938M eV /c2 ,

1eV /kB ≈ 11600K) atoms at room temperature.

A system obeys the van der Waals equation of state,
RT a
P = − 2,
v−b v
where P is pressure, v is the molar volume, T is the absolute temperature, and R, a,
and b are all constants. The molar heat capacity at constant volume cV is given as a
constant independent of P , T , and v.
1. One mole of this system is expanded isothermally at temperature T from an
initial volume vi to a final volume vf . Find heat transfer to the system in this
process.
2. One mole of this system is expanded from an initial volume vi to a final volume
vf in a process that conserves the enthalpy H = U +P V . Such a process is often
referred to a Joule-Thomson expansion, or a “throttling” process. Determine
the change in the temperature T if the change in the volume is small vf −vi vf .
The He3 melting curve (solid-liquid coexistence curve) is shown above, left.. The
general shape of the melting curve is well understood in term of the physical properties
of solid and liquid He3 and the Clausius-Clapeyron equation
dP ∆s
= ,
dT ∆v

where ∆s and ∆v are the molar entropy and molar volume differences between the
two phases.
At low temperatures the molar volumes of the solid and liquid do not vary sub-
stantially along the coexistence curve such that below 40mK vl − vs is essentially a
constant at 1.3cm3 /mole.
The thermal properties of the solid can be modeled by a system of N independent
2-level systems with the energy gap of 1mK, where N corresponds to the number of
He3 atoms.
The thermal properties of the liquid at low temperatures are well described by a
degenerate Fermi gas. In particular, the heat capacity of the liquid at temperatures
below 40mK is known to be linear in temperature, i.e. cv ∝ T .
You are given that the slope of the melting curve at P0 = 33.66 bar and T0 =
20mK is
dP/dT = −38.43bar/K
1. Estimate the molar entropy of the solid ss at P0 and T0 .
2. Using your result and the Clausius-Clapeyron equation, estimate the molar
entropy sl of the liquid at P0 and T0 .
3. Draw entropy as a function of the temperature along the P0 isobar from T = 0K

to T = 0.1K. Important features in your graph should be labeled with the
numerical values. Please use the graph provided.

The energy-momentum dispersion relation for electrons in the extreme relativistic
limit ( m0 c2 ) is well approximated by
= pc.
Assuming this relation is valid at all energies of interest, find:
1. The Fermi energy F at absolute zero in terms of the gas density, n = N/V .
2. The average energy per electron in the ground state of the gas at T = 0 as a
function of F .
3. Derive the equation of state for an electron gas in the extreme relativistic limit
which is valid at any temperature when the dispersion relation given above
applies.


A gas consists of two molecular types, A and B, which are intermixed in a volume V
at a constant temperature T . This is a non-ideal gas, but each molecular type acts
as an independent indistinguishable particle system so that the energy for each type
A molecule is given by
p2
A = + αnA
2mA
and for each type B molecule as
p2
B = + αnB + 0 .
2mB
Here α is a constant and 0 is a constant energy for a B-type molecule. The number
densities of molecules A and B are nA = NA /V , and nB = NB /V respectively.
1. Determine the N -particle classical canonical partition function for this mixed
gas. Since the partition function is to be determined classically, you can assume
that there is only one state per volume of the phase space h3 for each of the
two types of molecules.
2. Determine the Helmholtz free energy of this gas form the partition function.
3. Now, allow A and B type molecules to interconvert by simple reaction A B
(e.g. B might be excited state of A and vice verse). Also assume A and B
have equal masses. Given that A and B are in equilibrium (at fixed V , T , and
total number of molecules, N = NA + NB ), determine the equilibrium ratio,
R = NA /NB .
[Hint: Stirling’s approximation, ln N ! = N ln N − N . ]
A particular ideal gas is characterized by the following equations of state:

P V = N kB T and U = cN kB T,
where c is a constant. The gas is used as a medium in a heat engine/refrigerator
whose cycle an be represented on a P − V diagram as shown in the figure.

1. Determine the change in the internal energy of the gas for one complete cycle
(A → B → C → D → A).
2. Determine the equation of the adiabats.
3. Determine the thermodynamic efficiency of the above heat engine. Express your
answer in terms of c, P1 , and P2 .

3
Consider a monolayer He (spin= 1/2) film of a large area A, and assume that it
behaves like a two-dimensional ideal gas.
1. Determine the Fermi energy (T = 0) as a function of the coverage density

σ = N/A.
2. Determine the chemical potential (T 6= 0) as a function of the coverage density

σ = N/A.
3. Determine how the heat capacity scales with temperature as T → 0 using the
fact that the derivative of the Fermi function is sharply peaked around F in
this limit.

4
Consider a non interacting gas of He (spin= 0) confined to a film (i.e., confined in ẑ
direction, but infinite in the x and y directions). Because of the confinement, the pz
component of the momentum is quantized into discrete levels, n = 0, 1, . . . , so that
the energy spectrum is
p2
n (p) = + n ,
2m
where p is the two-dimensional (px , py ) momentum, and 0 = 0 < 1 < . . . n < . . . .
a. Write down the density of states for the system.
b. Write down the expression which determines the density of He4 atoms n as a
function of a chemical potential µ and temperature T . Evaluate integrals explicitly.
c. As T → 0, i.e. T 1 find the limiting value of µ and how the specific heat
depends on T in this limit.
d. Determine µ(N, V, T ) in the limit |µ| T (classical limit) assuming n = n.

A two dimensional fictitious “polymer” is constructed as follows: It consists of N

identical monomers of length a each, joined into a chain. (See figure.) Starting from
the left end of the “polymer”, which corresponds to the coordinates x = 0, y = 0,
each new monomer added prefers to extend the “polymer” to the right (i.e., to the
+x direction) with energy = 0, or upward (i.e., to the +y direction), with energy
= J > 0. It is given that no monomer added will extend the polymer to the left or
downward.
1. A macro state of this “polymer” is characterized by N and m, where m denotes
the number of monomers which extend the “polymer” upward. Find the entropy
of this macro state as a function of N and m. Assume that both N and m are
1, and use Stirling’s formula ln N ! ≈ N (ln N − 1) to simplify your result.
2. Write down the free energy of this macro-state of the “polymer”, as a function
of N , m, and the temperature T .
3. From minimizing this free energy, calculate the equilibrium value of m as a

function of N and T .
4. Calculate the equilibrium value of the free energy as a function of N and T , and
from which, calculate the specific heat of this “polymer” as a function of N and
T . (Note: Simplify your expression for the free energy to something quite simple
before calculating specific heat! Make sure your result has the right dimension,
or else you get no credit for this point.)
5. Show that in the limit kB T J, the specific heat of this “polymer” is inversely
proportional to T 2 , and obtain the coefficient of proportionality.

1. Explain why a three dimensional ideal Bose gas exhibit Bose-Einstein conden-
sation at finite temperature, and yet in two or one dimension, an ideal Bose gas
cannot undergo a Bose-Einstein condensation at any finite temperature. (Or, to
put it in another way, they can only undergo the transition at T = 0, which is of
course, meaningless, since the absolute zero temperature can never be reached.)

2. Show that in two-dimensions, the relation between the chemical potential µ,

the total number of particles N , and the absolute temperature T , of an ideal
gas, can be evaluated in close form (i.e., with the momentum or energy integral
doable in close form).

Consider a system of fixed volume V in thermal equilibrium with a reservoir at tem-
perature T .
1. Evaluate the mean-squared fluctuations in the system’s energy
h(∆E)2 i = h(E − hEi)2 i
in terms of its partition function Z(T, V ).
2. Show that these mean-squared fluctuations may be expressed in terms of the
system’s heat capacity as
h(∆E)2 i = kB T 2 CV .
3. How does the ration of the RMS fluctuation to the mean energy depend on the
number of particles if the system is a classical ideal gas?
4. By expanding S(E, V ) in a Taylor series around the mean energy hEi, find the
expression for the mean-squared entropy fluctuation h(∆S)2 i in terms of the
heat capacity CV and the Boltzmann constant kB .

1. Find an expression for the chemical potential µg of an ideal gas as function of
P and T .
2. Consider an absorbent surface having N sites, each of which can adsorb one gas
molecule. This surface is in contact with an ideal gas with chemical potential
µg (determined by the pressure P and temperature T ). Assuming that the
absorbed molecule has energy −0 compared to one in a free state, find the gran
partition function (sometimes called the grand canonical sum) that describes
the absorbing surface in terms of T , N , 0 , and µa , the chemical potential of
the absorbed molecules.
3. Calculate the covering ration R(P, T ), i.e., the ration of the absorbed molecules
to the total number N of absorbing sites on the surface.
[Hint: What is the relation between the chemical potential of the molecules in
the gas µg and these absorbed µa ?
A useful expression:
N
N
X N!
(1 + x) = xn .
n=0
n!(N − n)!
]


Consider a system of n classical noninteracting identical homonuclear diatomic molecules
enclosed in a box of volume V , and held at temperature T . The Hamiltonian of a
single molecule is taken to be:
1 1
H(~p1 , p~2 , ~r1 , ~r2 ) = p~21 + p~22 + κ|~r1 − ~r2 |2 ,
2m 2
where p~1 , p~2 , and ~r1 , ~r2 are the momenta and positions, respectively, for the two
indistinguishable atoms comprising a molecule, and κ is an effective spring constant.
Determine the following:
1. The classical partition function for a single

√ molecule. Express your answer in
terms of the thermal wavelength, λth = h/ 2πmkB T .
R∞ p
[Hint: 0 dx exp (−ax2 ) = π/4a]
2. The mean square molecule diameter h|~r1 − ~r2 |2 i.
3. The Helmholtz free energy for N molecule system.

n 2
There are approximately (N M ) /(n!) ways of removing n atoms from a crystal
lattice with N sites and distribute them over M interstitial sites to obtain n Frenkel
defects. The energy of an atom at an interstitial site is + relative to the energy at
the lattice site, taken as zero.
1. Obtain an expression for the (Boltzmann) entropy SB (E) of the system in the
microcanonical ensemble.
2. Calculate the temperature T as a function of E, and find the most probable

excitation energy E and defect number n as a function of T .
[Hint: You may need to use: ln(n!) ≈ n ln(n) − n.]

Consider a system of noninteracting electrons constrained to have following density
of states:
ρ() = constant ≡ D, ≥ 0;
ρ() = 0, <0
where is the one particle energy, and ρ() is the density of states for either spin.
1. Calculate the Fermi energy F at temperature T = 0, in terms of D and the

number of electrons, N .
2. Find U0 , the total energy of this electron system at T = 0.

3. Calculate the chemical potential µ at arbitrary temperature T , assuming N and

D are fixed. Find an expression in terms of D, N , and T (an exact solution,
rather than an expansion). Show also that your expression reduces to the result
of the first part in the limit T → 0.
4. Find CV , the heat capacity at constant volume, in the small-T limit (kT
N/D) and show that CV is proportional to T in this regime. Assume that
constant volume means D does not change.
[Hint: solve first for U − U0 in this limit.]

The gas of N identical particles is in a volume V at temperature T . The particles
interact weakly through two-body potentials
2 /a2
Uij = De−(~ri −~rj ) ,
where D and a are constants, and ~ri s are particles’ coordinates. Determine the leading
correction in D to the (Helmholtz) Free energy F of the system at high temperatures,
and the resulting change in the pressure of the gas.

Consider a chemical reaction AB ⇐⇒ A + B. Treating the system as a multicompo-
nent ideal gas, show that
nAB V zAB
= ,
nA nB zA zB
where nAB , nA , nB are the concentrations (number of molecules per volume) for each
molecule respectively, ZAB , ZA , ZB are the
P partition functions per molecule and V is
the volume. Note, that for equilibrium, i µi dNi = 0 where the µi are the chemical
potentials of the various species and the Ni are their numbers.

1. Sketch the temperature dependence of the chemical potential (at fixed N and
V ) i the whole temperature range from T = 0 to T = ∞, fro a three dimensional
non-relativistic ideal Fermi gas (spin 12 ), and a three-dimensional ideal Bose gas
(spin 0).
2. Derive, using statistical mechanics, a formula describing the high temperature

limiting behavior of each of these two curves (to leading order in the expansion
only); the independent variables should be T , N , and V , and no unknown
constants should appear in your result.
3. Find the zero temperature (T = 0) limiting values of these two curves as func-
tion of N and V , and state the qualitative initial T -dependence of these two
curves as T is increased from zero.

[Hint: Z ∞ √
2
e−x dx = π
−∞
ln N ! ≈ N (ln N − 1), for N 1.

]

Consider a molecular clock that can take on four angular positions θ = n(π/2), for
n = 0, 1, 2, 3. Its energy is given by
E = −A cos θ.
It is subject to thermal fluctuations at a temperature T .
1. Determine the value of hcos θi. Give the high-temperature and low-temperature
limits. Interpret your results physically.
2. Determine the value of hcos2 θi. Give the high-temperature and low-temperature
limits. Interpret your results physically.

A system of N non-interacting Fermi particles with spin 1/2 and mass m, is confined
to a volume V . It is at temperature T = 0. The particles have an energy-momentum
dispersion given by = p2 /2m.
1. Determine the chemical potential.
2. Determine the internal energy.
3. The original volume V adjoins a vacuum region with volume δV V . Both

chambers are thermally isolated from the environment. The Fermi gas now
freely expands into the vacuum region. Assume that the internal energy as a
function of the temperature can be parametrized at low temperatures by
U = α(V ) + β(V )T 2 ,
where α(V ) and β(V ) are functions of volume. Determine the final temperature
of the gas after the expansion. Your answer should be expressed in terms of the
functions α(V ) and β(V ).
4. Determine α(V ).
5. Determine β(V ).

[Hint: The following integral expressions may prove useful:

Z ∞ ∞ 2k−1
φ(x)dx X 2 −1 7
x −1
= 2k−2
ζ(2k)Φ(2k) (ln z) ≈ Φ(ln z)+ζ(2)Φ(2) (ln z)+ ζ(4)Φ(4) (ln z),
0 e z + 1 k=0 2 4
Rξ ∂ 2n Φ(x)
where Φ(ξ) = 0
φ(x)dx, and Φ(2n) (ξ) = ∂x2n
.
x=ξ
∞ ∞
xn−1 dx k
Z
k+1 z
X
= Γ(n) (−1)
0 ex z −1 + 1 k=1
kn
∞ ∞ ∞
π2 xn−1 dx zk
Z Z
xdx X
= , = Γ(n)
0 ex + 1 12 0 ex z −1 − 1 k=1
kn
" ∞
#
Z ∞ n−1 k k
x dx [− ln z] z
X
= Γ(n) Γ(1 − n)[− ln z]n−1 + (−1)k ξ(n − k)
0 ex z −1 −1 k=0
Γ(k + 1) k n
]

Consider a relativistic quantum Fermi gas, in three dimensions, with spin 1/2. The
energy of a relativistic fermion is = cp, where p is the momentum.
1. Find an integral expression for the internal energy U of such a gas.
2. Find the equation of state relating volume, pressure and internal energy of this
gas.
[Hint: Find an expression for the thermodynamic potential Ω for the grand
canonical ensemble, and relate this to U .]

The Joule-Thomson process is the flow of a gas through a porous membrane sepa-
rating two chambers, in which constant pressure p1 and p2 is maintained by external
conditions. In such a process the enthalpy H = U + P V is conserved.
1. Given that a change of temperature and pressure is small, it is regulated by the
∂T

derivative ∂P H
. Show that this derivative is:

∂T 1 ∂V
= T −V .
∂P H CP ∂T P
∂T

2. Calculate ∂P H
for the Van-der Waals gas with the equation of state:
(P + an2 )(1 − bn) = T n,

where n = N/V is the density, and a and b are positive constants (also 1 − nb
is supposed to be positive). In this part assume CP is given, and leave your
answer in terms of this parameter.


0
Find the final temperature T of a Van-der Waals gas expanding to the vacuum when
it changes its volume from V to V 0 > V , if the initial temperature was T . Assume
that no heat is exchanged with the container. You may assume that CV is a given
constant.
For Van-der Waals gas the equation of state is
(P + an2 )(1 − bn) = T n,
where n = N/V is the density, and a and b are positive constants (also 1 − nb is
supposed to be positive).

In the Debye model of the phonons (sound quanta) in a solid it is assumed that
there exist two degenerate transverse branches and one longitudinal branch of sound
oscillations. The oscillation frequencies ωt , ωl are linear isotropic functions of the wave
vector ωl,t (~q) = cl,t q, where cl and ct are the velocities of longitudinal and transverse
sound, respectively. The frequencies of each branch are assumed to be limited by a
maximal frequency ωD (Debye frequency). The value of ωD is determined by equating
the total number of degrees of freedom 3N j (j is the number of particles per unit
cell) to the number of phonon states.
1. Find the total number of states for transverse and longitudinal phonons, Nt and
Nl .
2. Find ωD .
3. Find the density of phonon states as a function of energy .
4. Find the integral form for the energy and specific heat CV of the phonons at
very low temperatures and at high temperature.

Consider a system described by energy states with energies En . Using the canonical
ensemble at temperature T,
1. Derive an expression
p for the root-mean-square fluctuation of the internal energy,
∆E|rms ≡ h(∆E)2 i in terms of En , where ∆E = En − hEi.
2. Determine the relationship between the specific heat at constant volume and
∆E|rms .
3. How does the relative fluctuation in energy, ∆E|rms /hEi depend on volume for
large system?
4. Under what conditions might you expect the relative fluctuation in energy to
be large?


Consider N particles of a non-interacting spin-1 Bose gas of mass m. They are
confined in three dimensions to a volume V . Take = p2 /2m.
1. In the high-temperature, low-density limit, determine the partition function,

the free energy, and the entropy.
2. In 1926, Einstein predicted that, at sufficiently low temperatures, a non-interacting

Bose gas can undergo condensation in which the occupation number N0 of the
p = 0 state is macroscopic: i.e. N0 /N is finite as N → ∞. Taking the chemical
potential to be zero, derive N0 /N as a function T . Determine TE , the Einstein
condensation temperature, from the condition that N0 (TE ) = 0.
Any integrals that arise should be put in dimensionless form, but need not be
evaluated.

Consider N particles of a non-interacting spin-1/2 Fermi gas of mass m confined to
a two dimensional plane of area A. Take = 0 (p/p0 )3/2 .
1. Determine the T = 0 energy of this Fermi gas.
2. Determine the T = 0 surface pressure, σ, of the Fermi gas. This surface pressure
is the force per unit length acting on the confining boundary of the gas.

Consider an atom trap containing two electrons, where such a large magnetic field
is applied, so that only spin-up states are occupied. The spin-down states are inac-
cessibly high in energy, so they need not be considered in this problem. The lowest
energy one-electron state of the trap has energy E0 and is doubly degenerate. The
first excited one-electron state has energy E1 and is four-fold degenerate. To simplify
the math set E0 = 0.
1. Find the thermal average energy of the two electrons.
2. Obtain an approximate expression for the previous result in the high temper-
ature limit, i.e., |E1 − E0 | kB T . Find the heat capacity of the electrons in
this limit.
3. Find the thermal average energy and heat capacity of the two electrons also in
the low temperature limit, i.e., |E1 − E0 | kB T .


Consider a spin-1 Bose gas with energy-momentum relation = v|p| in a space of
dimensionality D = 1 and D = 2.
1. In one of these spaces Bose-Einstein condensation will occur, and in the other
case it won’t. Determine which is which, and why. Note: For this part, you
need not explicitly evaluate the integrals involved, but merely verify if they are
well-behaved.
2. For the space in which Bose-Einstein condensation occurs, find the Bose-Einstein
transition temperature TBE . Express your results in terms of a dimensionless
integral, which you need not evaluate.
3. Find the fraction of Bose-Einstein particles as a function of temperature T , for

T < TBE .

Consider a soap film supported by a wire frame of fixed length l along one direction
and of varying length x along the other direction. Because of surface tension σ, there
is a force 2σl tending to contract the film. Take σ(T, x) = σ0 − αT , where σ0 and α
are independent of T and x.
1. In one sentence, explain why the force is 2σl, rather than σl.
2. Express the energy change dE of the film due to work δW associated with the
surface tension and heat δQ absorbed by the film through the atmosphere.
3. Calculate the work W done on the film when it is stretched at a constant

temperature T0 from length 0 to x.
4. Calculate the entropy change of the film when it is stretched at constant tem-
perature T0 from length 0 to x.
5. Calculate the change in energy ∆E = E(x) − E(0) when the film is stretched
at constant temperature T0 from length 0 to x.

Consider a cyclic engine operating with one mole of an ideal monoatomic gas in the
following reversible cycle:
a → b: expansion at constant pressure, the temperature going from Ta to 3Ta .
b → c: expansion at constant temperature 3Ta , the volume going to 4Va .
c → d: cooling at constant volume 4Va , the temperature going to Ta .
d → a: compression at constant temperature, the volume going from 4Va to Va .

1. Sketch the cycle on a P − V diagram.

2. Find the entropy change and the change in internal energy of the gas for each
part of the cycle. Find the net entropy change and the net change in internal
energy over the full cycle.
3. Calculate the thermodynamic efficiency of this engine and compare it to the
ideal efficiency of an engine operating between Ta and 3Ta .
4. What is the net change of the entropy of the hot thermal bath during one cycle?
5. What is the net change of the entropy of the cold thermal bath during one
cycle?

An ideal monoatomic gas is composed of N atoms each of which has additional degrees
of freedom that must be taken into account when calculating the thermodynamics
properties of the gas. (For example, the atoms might have electronic excited states.)
For the following questions, use Zint (T ) to denote the partition function of the
internal degrees of freedom of a single atom and Z0 (T, V, N ) to denote the canonical
partition function of an ideal monoatomic gas composed of N atoms with no internal
degrees of freedom.
1. Determine the difference between the Helmholtz free energy of the gas composed
of atoms with internal degrees of freedom, F (T, V, N ) = U − T S, and the
Helmholtz free energy of an ideal monoatomic gas composed of atoms with no
internal degrees of freedom, F0 (T, V, N ); i.e. determine
∆F = F (T, V, N ) − F0 (T, V, N )
in terms of Z0 (T, V, N ) and Zint (T ).
2. Similarly, determine the corresponding difference in the entropies
∆S = S(T, V, N ) − S0 (T, V, N )
3. Determine the corresponding difference in the chemical potentials

∆µ = µ(T, V, N ) − µ0 (T, V, N )
4. Determine the corresponding difference in the pressures

∆P = P (T, V, N ) − P0 (T, V, N )
5. Evaluate Zint (T ) for an atom with two internal energy states separated by
energy ∆E.


N spin 1/2 fermions with positive charge +e placed in a magnetic field with field
strength B in the ẑ-direction. The single particle energy levels are Landau levels, are
characterized by two quantum numbers and can be written as
p2z
n (pz ) = (n + 1/2)~ωc +
2m
where pz (−∞ ≤ pz ≤ ∞) is the continuous projection of the momentum on the
ẑ direction and non-negative integer n = 0, 1, 2 . . . is associated with the motion in
x − y plane. Here m is the mass of the particle and ωc = eB/mc is the cyclotron
frequency.
The degeneracy of each level is given by
mωc
g [n (pz )] = A,
2π~
where A = V /L is the area of the system in the x − y plane, V is the volume of the
system, and L is the length of the system in the ẑ direction.
Assuming the BOLTZMANN statistics in canonical ensemble is valid, determine
a. The equation of state.
b. The magnetization of the gas.
c. What condition on the chemical potential must be true so that the use of the
Boltzmann statistics is justified?

A polymer is a molecule composed of a long chain of identical molecular units, called
monomers. For simplicity, assume the polymer consists of a long chain of N rod-
like monomers, each of length l, attached end to end. Assume that the connectors
between the monomers are completely flexible so that each monomer can make any
angle with respect to its neighbors. One end of the polymer is fixed while the other
end is attached to a weight (mg) providing a constant force in the negative ẑ direction.
Except for an arbitrary constant which can be ignored, the potential energy of any
configuration of the polymer can be written as,
N
X
E(θ1 , φ1 , θ2 , φ2 , . . . θN , φN ) = mgl(1 − cos(θi )),
i=1
where θi , φi represent angles in the spherical coordinates that the ith monomer makes
with the negative ẑ direction. Each angle can take all possible values 0 < θi < π and
0 < φi < 2π.
1. Determine the classical canonical partition function Z(T, N ) for this polymer
in contact with a temperature bath at temperature T .

2. Determine the thermodynamic energy U (T, N ) and entropy S(T, N ) of the sys-
tem. Find the temperature dependence of U and S for very small and very
large temperatures.
3. If the polymer is isolated from the temperature bath and the mass at the end
of the polymer is increased adiabatically from its initial value of m to a final
value of 2m, determine the final temperature of the polymer.

A gas of N identical non-interacting, spin-1/2 fermions in three dimensions obey the
dispersion relation = Apα , where p is the magnitude of the momentum, A and α
are positive constants. assuming that these particles are in a box of volume V with
periodic boundary conditions.
1. Calculate the density of states of this gas as a function of .
2. Calculate the Fermi energy of this gas as a function of n ≡ N/V , which is the
density of the gas.
3. Write down as many integral expressions as needed which can, together and
implicitly, give the internal energy U of this system as a function of N , V ,
and the temperature T . You are not required to evaluate these expressions in
the order to find U (N, V, T ) explicitly.
4. Take the high temperature limit of the expressions you gave in the previous
part, and then evaluate them in order to obtain U (N, T, V ) explicitly in this
limit only.
R∞
[Hint: Γ(s) = 0 xs−1 e−s ds = (s − 1)Γ(s − 1)]


~ = B ẑ with
Consider a dipole with a fixed magnitude µ = |~µ|, in a magnetic field B
~ Assume the dipole is in equilibrium with a thermal
interaction energy U = −~µ · B.
reservoir at temperature, T .
1. Without doing any calculations but using only simple physical reasoning, de-
scribe in words the behavior of h~µi, the thermal average value of µ
~ , in the limit
as the temperature approaches zero, T → 0.
2. If µ
~ is treated classically and can point in any direction in 3-dimensional space,
find h~µi as a function of temperature. In particular, what are the values of hµx i,
hµy i, hµz i? Show that as T → 0, µ ~ has the behavior predicted in the previous
part.
3. Now assume that magnetic moment is that of a spin-1/2 particle with non-
vanishing gyromagnetic ratio γ, so it can only point parallel or anti-parallel to
~ Find h~µi as a function of temperature and show that it has the expected
B.
behavior as T → 0. Also show that

∂hµz i
~
h~µi · B
χ= →
∂B T ~ 2
|B|
as T → ∞. (Keep the leading non-trivial term.)

Consider a box of volume V containing electron-positron pairs and photons at tem-
perature T = 1/kB β. Assume that the equilibrium is established by the process
γ e+ + e−
This process does not occur in free space, but could be considered to be catalyzed
by the walls of the box. Ignore the walls except insofar as they allow this process to
occur and answer the following questions in sequence:
1. By minimizing the appropriate potential at fixed T and V give the thermody-

namic proof to show that
µγ = µe+ + µe− ,
which relates the chemical potentials of the three types of particles.
2. What should be the value of µγ in view of the fact that there is no number
conservation for photons?
3. What should be the values of µe+ and µe− be if all the positrons and electrons
in the box are due to pair creation? (Remember that a positron and an electron
have the same rest mass me .)

4. Using the relativistic energy of the particles, write down the integral expression
for the number of e+ in term of T , V , and µe+ and for the number of e− in term
of T , V , and µe− .
5. Using the values of µe+ and µe− from the third part and the integral expressions
from the fourth part, calculate the mean number of electron-positron pairs, in
the two limits kB T me c2 and kB T me c2 . (You may leave your answers in
terms of dimensionless definite integrals.

A box of volume V contains N molecules of a classical gas. The molecules can either
be bound to the walls of the box with binding energy b and dispersion relation of
a 2D gas (p) = (p2x + p2y )/2m, or move freely within the volume of the box with
dispersion relation of a 3D gas (p) = (p2x + p2y + p2z )/2m.
Find what portion of the molecules are stuck to the surface. Obtain an explicit
results in two limiting cases of low and high temperature.

A system consists of 2 single particle states with energies 0 and 1 (0 < 1 ) that can
be independently occupied by spin-1/2 (non-interacting) fermions.
1. Determine the grand partition function for this system.
2. Determine the average number of fermions in the system as a function of the

temperature, T , and the chemical potential, µ.
3. Assume that the average number of particles in the system is two. Determine the
limiting value of the chemical potential in the low temperature limit (T → 0).
[Hint: Convince yourself that based on the low temperature behavior of the
Fermi function, the value of µ should lie between 0 and 1 . Then determine its
precise value. ]
4. Assume that the average number of particles in the system is three, determine
the limiting value of the chemical potential in the high temperature limit.
[Hint: Knowing that at the high temperatures, the particle occupancy should
be described by a classical probability, determine the precise value of µ.]

A single-particle Hamiltonian has six degenerate eigenstates at energy 1 , and another
six degenerate eigenstates at energy 2 > 1 . All other eigenstates are of very high
energy relative to kB T . Eight non-interacting identical fermions are described by this
Hamiltonian. (The spin degeneracy is already included in the given degeneracies.)
1. Compute the ground state energy and degeneracy for this eight-fermion system.
2. Repeat for the first excited state of this system.

3. Repeat for the second excited state of this system.

4. At low temperatures, where kB T < 0.1(2 − 1 ), write down an approximate
expression for the canonical partition function of this system, which can give
the leading non-trivial-order contribution to the specific heat.
5. Repeat for the average total energy of the system.

1. Derive the grand thermodynamic potential ΩG (T, V, µ) for an ideal non-relativistic
Maxwell-Boltzmann gas in three dimensions, assuming that the particles have
no internal degrees of freedom. From the result, obtain S(T, V, µ) and N (T, V, µ),
and show that they obey the relation

5kB µ
S=N − .
2 T
2. Begin with the entropy expression for an ideal gas:

X
S = −kB [hnj i loghnj i + (1 − hnj i) log (1 − hnj i)] .
j
Show that in the high temperature limit it reduces to the Maxwell-Boltzmann

result obtained in the first part.

A solid thin rectangular parallelepiped has dimensions a×b×b, where a b. Assume
that it has three types of acoustic vibrations (phonons), all having velocity v. Thus
~
ω = vk for all displacements of the form ~u = ~u0 ei(k·~r−ωt) , with ~u0 along ~k for the
longitudinal mode and ~u0 normal to ~k for the two transverse modes.
1. Compute the total density of states dN /dω (number of modes per unit angular-
frequency range).
Rω
2. Define the Debye frequency ωD by 0 D (dN /dω)dω = 3N , where N is the
number of atoms. Find ωD . (Note, that N and N have different meaning here!)
3. Assuming that dN /dω = 0 for ω > ωD , find the internal energy U (T ) due to the
phonons in this solid. You may express your answer in terms of a dimensionless
unevaluated integral.
4. Find the specific heat CV (T ) due to the phonons in the solid. You may express
your answer in terms of a dimensionless unevaluated integral.
5. Evaluate the cross-over temperature Tx below which the system must be treated
as two dimensional.


N electrons in a box of dimensions L × L × L obey the energy-momentum relation
= p2 /2m, where m is the electron mass. The system is at absolute zero temperature.
a. Find the maximum occupied momentum pF in terms of N and V = L3 .
b. Find the internal energy U of the system as function of N and V .
c. Find the pressure P from U .
d. Calculate the rate at which x̂ component of momentum px crosses a surface area

A = L2 perpendicular to x̂ in the +x̂ direction due to all N electrons.
e. How does pressure relate to the rate calculated in the previous part? Give physical
explanation.
Problem 194. Rotating gas. ID:SM-G-1175

The canonical partition function of a classical, monoatomic, ideal gas in a cylinder
rotating with angular velocity ω is given by (see Kubo chapter 2, problem 4)
" 3/2 x #N
1 2πmT e − 1
Z= πR2 L
N! h2 x
mω 2 R2
where x = 2T
.
a. Find the angular momentum M of the rotating gas as a function of temperature

and angular velocity.
b. Consider the limits of the obtained expression for M corresponding to very high
and very low temperatures. Give the physical interpretation of obtained results.
What is the criterion of high and low in this case?
c. How much energy one should supply to heat the gas from a very low temperature
T0 to a very high temperature Tf ? Denote the initial angular velocity of the
cylinder as ω0 . Neglect the moment of inertia of the cylinder (vessel) itself.
Problem 195. Quantum oscillator ID:SM-G-1195

mω 2 2
A quantum particle of charge q is in the oscillator potential V (x) = 2
x in 1D at
temperature T .
a. Find the heat capacity of this system.
b. Find the electric dipole susceptibility of the system. (d = −(∂F/∂E)V,N,T , χ =

(∂d/∂E)V,N,T ).
c. For the oscillator state ψn in the presence ofPelectric field E calculate xn =

hψn |x̂|ψn i, and then average displacement x̄ = n xn wn .

Problem 196. Bricks ID:SM-G-1203

1. There are three identical bricks with temperatures T1 , T2 , and T3 . You are
allowed to use any number of ideal engines, but you cannot supply external
heat or work to the system. What is the highest temperature you can give to
one of the bricks. Give answer as a root of a single algebraic equation. (You do
not need to sole the equation.)
2. Now you have N identical bricks with temperatures Ti , i = 1 . . . N . What is the

highest temperature you can give to one of the bricks. Give answer as a root of
a single algebraic equation. (You do not need to solve the equation.)
3. If all of the initial temperatures are in a small interval T0 < Ti < T0 + ∆T ,

where ∆T T0 , find the highest temperature of previous part for N → ∞.
Problem 197. String. ID:SM-G-1212

A 3D string of length L has a temperature dependent tension f (T ).
a. What is the average value of the amplitude aαk of the kth harmonic of a small
deformation of the string?
b. What is haαk aβk0 i for two harmonics k and k 0 ?
c. Calculate e~n~ak .
Problem 198. Membrane ID:SM-G-1220

A circular membrane has a temperature dependent surface tension σ(T ). How does
the heat capacity of the membrane depend on the small displacement h of the center
of the membrane perpendicular to the membrane?
Problem 199. Membrane ID:SM-G-1224

A circular membrane has a temperature dependent surface tension σ(T ). How does
the heat capacity of the membrane depend on the small displacement h of the center
of the membrane perpendicular to the membrane?
Problem 200. Circle. ID:SM-G-1225

A body undergoes a thermodynamic reversible cycle along the path given by
(P − P0 )2 (V − V0 )2
2
+ 2
= r2 ,
P0 V0
where r 1. The adiabatic compressibility βS , the heat capacity at constant pressure

CP , and the coefficient of thermal expansion α of the body at P0 , V0 are known.
a. What is the total change of the energy of the body after a full cycle?
b. What is the total change of the entropy of the body after a full cycle?

c. What is the total work done by the body during the full cycle?
d. On the path ABC the body receives heat. On the path CDA it gives up heat.
What is the angle φ between the line AC and the axis V ?
e. What is the efficiency of this engine?
f. What would the efficiency of this engine be if the body were a monoatomic ideal
gas?
Problem 201. Gas and vacuum ID:SM-G-1230

A cylinder of volume V0 + V1 is divided by a partition into two parts of volume V0 and
V1 , where V1 V0 . The volume V0 contains 1 mole of a gas at temperature T0 and
pressure P0 . The volume V1 has vacuum. You know the gas’s coefficient of thermal
expansion α(P0 , T0 ), its βT (P0 , T0 ), and its heat capacity CV (T, V ). At some moment
the partition disappears.
1. What will be the temperature of the gas after it equilibrates?
2. A piston now adiabatically returns the gas back to the volume V0 , what will be
it’s temperature?
3. What are these results for the ideal gas?

Problem 202. Distribution, average, and fluctuations ID:SM-G-1235

You through a dice N times count the number of times you have a “3”. You repeat
this activity many many times.
a. With what probability the number of 3s is n?
b. What is the average number of 3s?
c. What is the standard deviation (r.m.s. fluctuation)?
Problem 203. Distribution function of an oscillator. ID:SM-G-1240

mω 2 x2
A classical one dimensional oscillator (V (x) = 2 ) has a statistical distribution
function %(p, q) = Ae−E(p,q)/T , where A is a normalization parameter, T is a parameter
which is called temperature, and E(p, q) is the oscillator’s energy.
a. Find the normalization constant A.
b. Find the average coordinate of the particle.
c. Find the average momentum of the particle.
d. Find the r.m.s. fluctuations of the particle’ coordinate and momentum.
e. Find the average energy of the particle. Find the heat capacity.
f. Find the distribution function for a quantity f = f (p, x), where f (p, x) = p−ωmx.
Problem 204. Traveling frog. ID:SM-G-1245

Consider a one dimensional frog. After every τ seconds it hops with probability 1/2
one meter to the left and with probability 1/2 one meter to the right. At t = 0 the
frog is at x = 0.
1. Consider a function p(x, t) – the probability for the frog to be at point x at time
t. Find p(x, t + τ ).
2. Consider a limit of large distances and long times. Find a differential equation
for p(x, t).
3. What is the initial condition for this equation?
4. Solve the equation.
5. What is the average coordinate of the frog? How does it change with time?
6. What is the average deviation of the frog’s coordinate? How does it change
with time?
7. Repeat all the steps for the situation when the frog hops with probability q to
the left and probability 1 − q to the right.

Problem 205. Electrons in wire ID:SM-G-1250

A current I flows in the wire. Treat electrons as point like classical particles.
1. What is the probability that exactly n electrons cross through a wire cross-
section in time T .
2. What is the average number of electrons which crossed a wire cross-section in

time T ?
3. What is the standard deviation of that number?

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Qualification Exam: Statistical Mechanics

Problem 2. 1983-Fall-SM-U-2 ID:SM-U-16

Problem 3. 1983-Fall-SM-U-3 ID:SM-U-31

• An isothermal compression from 2V0 to V0 ;

• At constant pressure to the original state.

1. Find the efficiency of the engine

Statistical Mechanics QEID#18978097 August, 2017

Problem 4. 1983-Spring-SM-U-1 ID:SM-U-45

Problem 5. 1983-Spring-SM-U-2 ID:SM-U-54

1. Find the net work done in the process in terms of P0 , V0 .

Problem 6. 1983-Spring-SM-U-3 ID:SM-U-72

Statistical Mechanics QEID#18978097 August, 2017

Problem 7. 1984-Fall-SM-U-1 ID:SM-U-81

Problem 8. 1984-Fall-SM-U-2 ID:SM-U-96

Problem 9. 1984-Fall-SM-U-3 ID:SM-U-107

Statistical Mechanics QEID#18978097 August, 2017

Problem 10. 1984-Spring-SM-U-1 ID:SM-U-118

2. Iodine vapor can be assumed to be an ideal diatomic gas with constant CP . At

Problem 11. 1984-Spring-SM-U-2 ID:SM-U-132

Problem 12. 1984-Spring-SM-U-3 ID:SM-U-147

2. Derive, showing your reasoning the four Maxwell’s Relations.

Statistical Mechanics QEID#18978097 August, 2017

Problem 13. 1985-Fall-SM-U-1 ID:SM-U-163

(a) total entropy S

Problem 14. 1985-Fall-SM-U-2 ID:SM-U-184

2. Change to 2P0 , V0 , at constant volume.

3. Change 2P0 , 2V0 , at constant pressure.

4. Change to P0 , 2V0 , at constant volume.

5. Change P0 , V0 , at constant pressure.

Statistical Mechanics QEID#18978097 August, 2017

Problem 15. 1985-Fall-SM-U-3 ID:SM-U-195

1. What is the change in entropy of the water?

2. If the source of heat is a very massive body at a temperature of 20◦ C, what is

Problem 16. 1985-Spring-SM-U-1 ID:SM-U-204

1. The partition function for the system

2. The energy of the system

3. The heat capacity of the system

4. What is the ”low temperature” temperature dependence of the heat capacity?

5. What is the ”high temperature” temperature dependence of the heat capacity?

Problem 17. 1985-Spring-SM-U-2 ID:SM-U-225

Statistical Mechanics QEID#18978097 August, 2017

Problem 18. 1985-Spring-SM-U-3 ID:SM-U-244

Problem 19. 1986-Spring-SM-U-1 ID:SM-U-265

1. Show that the heat transferred during an inflniteslsal quasi-static process c an

Problem 20. 1986-Spring-SM-U-2 ID:SM-U-281

1. The temperature is raised to 300K at constant volume. Hou much heat Q is

4. Sketch the process on a P V diagram. What is the efficiency of the cycle?

Statistical Mechanics QEID#18978097 August, 2017

Problem 21. 1986-Spring-SM-U-3 ID:SM-U-303

Problem 22. 1987-Fall-SM-U-1 ID:SM-U-309

2. Recall that the surface tension, σ, in two dimensions is analogous to pressure

Problem 23. 1987-Fall-SM-U-2 ID:SM-U-323

Problem 24. 1987-Fall-SM-U-3 ID:SM-U-327

Statistical Mechanics QEID#18978097 August, 2017

2. What is the relationship between GN (T, P0 , Hc ) and Gs (T, P0 , Hc ), the Gibbs

3. Use the results of the previous parts to show that

Problem 25. 1988-Fall-SM-U-1 ID:SM-U-361

Problem 26. 1988-Fall-SM-U-2 ID:SM-U-366

Problem 27. 1988-Fall-SM-U-3 ID:SM-U-376

Statistical Mechanics QEID#18978097 August, 2017

where 0 is a constant of the dimension of energy, and N0 is proportional to the total

2. If 1 < 2 and 2 = 3 within what range of values must µ(T = 0) lie if at T = 0