UP204: Some past assignment and exam problems

Posted on : April 07, 2019

1. ideal gases in thermal contact

Two particular systems have the following equations of state:
1 3 n1 1 5 n2
= R and = R
T 2 E1 T 2 E2
where R is the gas constant. The mole number of the first system is n1 = 2 and
that of the second is n2 = 3. The two systems are separated by a diathermal
wall, and the total energy of the composite system is 2.5 × 103 J. What is the
internal energy of each system in equilibrium?
Now consider the situation in which the initial temperatures of the first and
second systems are T1 = 250K and T2 = 350K, respectively. What are the
values of E1 and E2 after equilibrium has been established? What is the
equilibrium temperature?

2. ideal gas in mechanical contact - 1

A gas in a vertical cylinder supports a freely moving piston of mass m. The
common cross-sectional area is A. Atmospheric pressure is P0 and in equilib-
rium, the volume of the gas is V0 . The piston is now given a small displacement
and it is found to oscillate with frequency ω. The frequency is low enough for
internal equilibrium, but high enough for the gas not to be able to exchange
heat with its surroundings. Find ω assuming that the gas is monatomic and
ideal. What will happen if the gas is not ideal?

3. ideal gas in Mechanical contact - 2

A vertical cylinder contains ν moles of an ideal monatomic gas, and is closed
off by a piston of mass M and area A. The acceleration due to gravity is
g. The molar specific heat cV (at constant volume) of the gas is a constant
independent of temperature. The heat capacities of the piston and cylinder are
negligibly small, and any frictional forces between the piston and the cylinder
walls can be neglected. The pressure of the atmosphere can also be neglected.
The whole system is thermally insulated.
Initially, the piston is clamped in position so that the gas has a volume V0 ,
and a temperature T0 . The piston is now released, and, after some oscillations,
comes to rest in a final equilibrium situation corresponding to a larger volume
of the gas.

(a) [1 point] Does the temperature of the gas increase, decrease, or remain
the same?
(b) [1 point] Does the entropy of the gas increase, decrease, or remain the
same?

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 (c) [4 points] Show that the final temperature of the gas is
!
cV T0 M gV0
 
+
cV + R νA(cV + R)
where R is the molar ideal gas constant.
4. maximum work
(a) [4 points] One mole of a monatomic ideal gas is contained in a cylinder
of volume 10−3 m3 at a temperature of 400 K. The gas is to be brought to a
final state of volume 2×10−3 m3 and temperature 400 K. A thermal reservoir
or heat bath of temperature 300 K is available. What is the maximum work
that can be extracted from the gas?
(b) [2 points] Suggest a sequence of processes by which all this work can
actually be extracted.
5. exact differentials and thermodynamics of ideal gases
The infinitesimal change in a variable f , which might be a smooth function of
two variables x and y is written as
df = a(x, y) dx + b(x, y) dy
What condition needs to be satisfied by a(x, y) and b(x, y) for f to be actually
a function of x, y so that df is an exact differential?
Now, consider a reversible process in an ideal gas in which the pressure P and
the temperature T change by infinitesimal amounts dP and dT , respectively.
Write the heat exchanged in this process as
6 dQr = A(P, T ) dP + B(P, T ) dT.
Obtain explicit expressions for the functions A(P, T ) and B(P, T ) and show,
using the condition derived above that 6 dQr is not an exact differential. In a
similar way, show that 6 dQr /T is an exact differential.
6. thermodynamics in the S, V, N ensemble
Consider a system for which the internal energy E is related to the entropy S,
the volume V and the number of particles N by the equation
!
v0 θ S3
E= ,
R2 NV
where v0 , θ and R are positive constants. Obtain expressions for the tempera-
ture T , the pressure P and the chemical potential µ as functions of S, V and
N , and verify that T , P and µ are intensive parameters.
What is the equation of state (relationship involving the pressure, volume and
temperature) for this system? Show by a diagram (drawn to arbitrary scale)
the dependence of pressure on volume for fixed temperature for this system.
Draw two such “isotherms” corresponding to two values of the temperature
and indicate which isotherm corresponds to the higher temperature.

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 7. Entropy changes for model systems in thermal contact
Consider two systems A and B, initially at equilibrium at temperatures TA
and TB respectively. In the temperature range of interest, the volumes of the
two systems do not change with changes of temperature, and their respective
heat capacities CA and CB are temperature-independent. These two systems
are now placed in thermal contact and allowed to reach the final equilibrium
state.

(a) Calculate the temperature T in the final equilibrium state. Express your
answer in terms of TA , TB , CA and CB .
(b) Calculate the entropy changes ∆SA and ∆SB of systems A and B, re-
spectively, in going from the initial to the final state.
(c) Show that the total entropy change ∆S = ∆SA + ∆SB can never be
negative and that it will be zero only if TA = TB .

8. Cascade of heat engines

A cascade of reversible engines are operated sequentially and reversibly be-
tween two systems, of equal heat capacity C, initially at temperatures T1 and
T2 , respectively, until the two systems reach a common final temperature Tf .
What is the net entropy change for the process? Obtain an expression for Tf
in terms of T1 and T2 . Calculate the total amount of work delivered by the
engine.
Contrast the above results with the results for the entropy change and the final
temperature that would result if the two systems were to be simply placed in
contact.

9. Heat pumps
(a) A building is maintained at a temperature T by means of an ideal heat
pump which uses a river at temperature T0 as a source of heat. The heat pump
consumes power W , and the building loses heat to its surroundings at a rate
α(T − T0 ), where α is a positive constant. Show that T is given by
W q
T = T0 + (1 + 1 + 4αT0 /W )
2α

(b) Derive the expression for T in the slightly more complicated (and perhaps
more realistic) case that the surroundings of the building are at a different
temperature TS than the river, and check that it reduces to the above when
TS = T0 . What considerations determine whether you should use the river or
the surroundings as the source of heat?

10. Entropy and Number of Microstates

Calculate the entropy of 0.1 mol of helium gas at 300 K in a container of
volume 1 m3 . Express you answer in terms of the gas constant R.
Suppose the energy of the gas is being measured accurate to 1 part in a billion.
What is the uncertainty δE in the energy of the system in Joules? How many

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 microstates of the system are there in this energy interval? What is the average
spacing between the energies of the microstates?

11. Canonical Ensemble and Helmholtz Free energy

(a) [6 points] Starting from the Gibbs principle of equal apriori probabilities
for all microstates of an isolated system with energies within a width δE of E,
show that for a system with fixed volume V and fixed number of particles N
in contact with a heat bath of temperature T , the most probable macrostate
is the one that minimizes the constrained Helmholtz free energy F ≡ E −
T S(E, V, N ; X) with respect to the energy E, and X which stands for any
other macro-variable that is free to vary spontaneously.
(b) [5 points] Denoting the minimised Helmholtz Free energy as F (T, V, N ),
show by considering fluctuations in the volumes of two subsystems (of mean
volume V each) that make up a combined system that the extremum princi-
ple for the constrained free energy obtained in part (a) implies the stability
condition !
∂ 2F
≥ 0.
∂V 2 T,N
What is the physical implication ( in terms of a measured property) of this
relation?
(c) [3 points] Write down the 3 Maxwell relations that can be derived from the
differential of F .

12. Joule-Thomson Process

[5 points] The fundamental equation for the entropy of a gas is given by S =
1
B
(EV N )1/3 where B is a positive constant, and E, V and N have their usual
meanings. The gas, at an initial temperature Ti and initial pressure Pi is passed
through a "porous plug" in a Joule-Thomson process. The final pressure is Pf .
Calculate the final temperature Tf .

13. GCE reasoning

A glass bulb of volume V1 contains air at room temperature (T0 ) at a pressure
of 1 atmosphere. An experimenter places it inside a chamber of volume V0 ,
evacuates the chamber, and fills it with He gas, also at 1 atmosphere and
room temperature. The chamber is covered with insulating material, and is
thermally isolated from its surroundings. A few months later, he comes to
know that the particular glass of which the bulb is made is quite permeable to
Helium, although not to any other gases. Assuming that equilibrium has been
attained by this time, what pressures and temperatures will the experimenter
measure inside and outside the bulb when he goes back to check? What is the
entropy change of the whole system in the process?

14. particle number fluctuations

Consider an ideal gas of N molecules in a container of volume V . The volume
V is divided into two parts, V1 and V2 , so that V = V1 + V2 , but either with

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 holes in the wall or a permeable membrane so that the molecules can move
between the partitions.

(a) Find the probability P (N1 ) that N1 molecules are in V1 .

(b) Calculate hN1 i, the average value of N1 , and h(N1 − hN1 i)2 i1/2 , the root-
mean-square fluctuation of N1 .
(c) How small is the probability that (1/2) the number of molecules are in
(1/4)th of the volume if N = 2 × 1023 ?
(d) Show that for (V1 /V )  1, P (N1 ) can be approximated by the Poisson
distribution
hN1 iN1
P (N1 ) = exp[−hN1 i].
N1 !
15. Thermodynamics of a photon gas
The fundamental equation for a gas of photons enclosed in a volume V made
up of insulating walls with internal surfaces that are nearly perfect reflectors
is given by
4
S = b1/4 E 3/4 V 1/4 .
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Here S and E represent the entropy and the internal energy of the system
respectively, and b is a constant. (Note that N does not enter the picture here
as the number of photons is not a conserved quantity.)
(a) Determine the temperature T and pressure P of the system as functions
of E and V . What is the constant volume heat capacity CV of the system?
(b) One of the walls of such a system is a horizontal piston of area A which
can move nearly without friction inside an enclosure. The piston supports a
weight M g, and is initially pegged. The peg is released. If the system has
initial energy E0 and volume V0 , determine the final energy E and the volume
V at which the system comes to equilibrium.
(c) Two photonic gas systems, one (system A) with energy 32 mJ in a volume
2 m3 , and the other (system B) with energy 1 mJ in a volume 1 m3 , are
separated by a fixed, adiabatic partition that prevents energy exchange. The
partition is now made diathermal so that the exchange of energy between
A and B becomes possible and the combined system is allowed to come to
equilibrium. What are the values of the energies of the two systems in the
equilibrium state?
(d) Suppose the photon gas, rather than the ideal gas, were to be used as the
“working fluid" of a Carnot cycle operating between temperatures Th and Tl .
Sketch the resulting cycle as a (P, V ) diagram for the photon gas. Indicate on
the graph the equations governing the four paths of the cycle.
How does the efficiency of such an engine compare with that of the standard
ideal gas Carnot engine?

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16. Thermodynamic Potentials for an ideal gas
The fundamental equation for a monatomic ideal gas obtained from counting
the number of microstates in the micro-canonical ensemble is given by:
5 V 3 4πmE
    
S(E, V, N ) = N kB + ln + ln
2 N 2 3N h2
Deduce from this the fundamental equations for the five thermodynamic po-
tentials E, F, Φ, H and G as functions of their appropriate arguments. In each
case find all the equations of state by differentiating the fundamental equa-
tions.

17. Legendre Transforms and Massieu Functions

Starting with the entropy S as a function of E, V and N , define the three Leg-
endre transforms A(1/T, V, N ), B(E, P/T, N ) and C(1/T, P/T, N ) of the en-
tropy. These functions, analogous to the thermodynamic potentials F (T, V, N ),
H(S, P, N ) and G(T, P, N ) defined as Legendre transforms of the internal en-
ergy E(S, V, N ), are called Massieu functions. Find the extremum principles
for these Massieu functions.

18. consequences of Maxwell Relations - 1

Show that the adiabatic compressibility κS = κT (CV /CP ) where κT is the
isothermal compressibility, and CV and CP are the specific heats at constant
volume and pressure respectively. Hence, deduce that

V T α2
κT − κS =
CP
where α is the volume coefficient of expansion.

19. consequences of Maxwell Relations - 2

Deduce the following relations:
! !
∂α ∂κT
+ =0
∂P T
∂T P
!
∂E
= CP − P V α
∂T P
!
∂E κT
= P V κT − (CP − CV )
∂P T
α

20. Speed of sound

The speed of sound in dry air at 20o C is measured to be 343 m/sec. Modeling
sound as corresponding to density oscillations in a fluid medium, it is not hard
to show (as was first done by Newton!) that the speed is given by cs = (ρκ)−1/2
where ρ is the mass density of the fluid, and κ is its volume compressibility.
The key question is which compressibility to use. Modeling air as an ideal

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 gas,
q show that
q using the isothermal compressibility leads to the formula cs =
(P/ρ) = RT /M where R is the molar ideal gas constant, T the absolute
temperature and M the molecular weight. How will this formula change if the
adiabatic compressibility were to be used? Which one gives better agreement
with experiment? (Use the web for all the relevant information needed for the
numerical estimate.) Does the composition of air make a difference? Discuss
the dependence of the sound speed on the gas temperature, T , at a fixed
pressure, and on the gas pressure, P , at fixed temperature.

21. Stability Conditions

(a) Starting from the entropy maximization principle derive the stability con-
ditions !2
∂ 2S ∂ 2S ∂ 2S ∂ 2S ∂ 2S
≤ 0; ≤ 0; − ≥0
∂E 2 ∂V 2 ∂E 2 ∂V 2 ∂E∂V
(b) Express these conditions in terms of the measured quantities CP (specific
heat at constant pressure), κT (isothermal compressibility) and α (thermal
volume expansion coefficient in the Gibbs ensemble)

22. Maxwell-Boltzmann distribution for a classical gas

(a) Consider an isolated monatomic classical ideal gas of N atoms with total
energy E confined in a cube of volume V . What is the probability that
a single gas atom has energy ? What is the ratio between its most
probable energy and its mean energy?
(b) The system above is allowed to come to thermal equilibrium with a bath
at room temperature (300 K). What is the mean kinetic energy per atom
in eV if the gas consists of (i) He atom, (ii) Xe atom, (iii) Ar atom and
(iv) Kr atom.

23. Classical gas under gravity

A “classical monatomic” ideal gas consisting of N identical particles of mass
m is enclosed in an infinitely tall cylindrical container with cross-sectional area
A. A uniform gravitational field is present, so that the potential energy of a
particle at height z is given by U (z) = mgz, z ≥ 0. The gas is in thermal
equilibrium at temperature T .

(a) (4 pts) Calculate the canonical partition function and the Helmholtz free
energy of this system.
(b) (3 pts) Calculate the internal energy and the heat capacity of this system.
(c) (3 pts) Define and calculate the pressure in the gas as a function of the
height z.

24. Heat capacities of classical gases

The results for the molar heat capacities in JK −1 mol−1 for a variety of sub-
stances, all measured at constant pressure at 298 K, are given in the following

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 list. Al 24.35, Ar 20.79, Au 25.42, Cu 24.44, He 20.79, H2 28.82, Fe 25.10, Pb
26.44, Ne 20.79, N2 29.13, O2 29.36, Ag 25.53, Xe 20.79, Zn 25.40. Discuss
how these results could possibly arise from the states these systems are in.

25. Classical ideal gas in 2-dimensions

Monatomic molecules adsorbed on a surface of area A move freely on the
surface and may be treated as a classical two-dimensional ideal gas. Obtain
an expression for the partition function and hence the specific heat per mole
for this system.

26. Classical ideal gas + vibrations treated quantum mechanically

The linear CO2 molecule has four vibrational modes with associated vibra-
tional temperatures Tvib = ~ωvib /kB of 3498 K, 1908 K and two degenerate
modes at 954 K. Obtain the molar specific heat for this gas at a temperature
of 400 K. Assume that the rotational and translational degrees of freedom can
be treated in the high-temperature limit.

27. Extremely Relativistic Classical ideal gas

Consider an extremely relativistic ideal gas consisting of N indistinguishable
particles with energy-momentum relation (p) = cp, c being the speed of light,
contained in a three-dimensional volume V . Use the classical ideal gas limit.

(a) Obtain the equation of state of this system (i.e. calculate the pressure P
in terms of N , V and the temperature T ).
(b) Calculate the internal energy E as a function of T .
(c) Calculate the value of γ ≡ Cp /CV , the ratio of the heat capacities at
constant pressure and constant volume.

28. Adsorbed He treated as a Classical gas

Helium atoms can be adsorbed on the surface of a metal, an amount of work
Φ then being necessary for removing a helium atom from the metal surface
to infinity. The helium atoms are completely free to move, without mutual
interaction, on the two-dimensional metal surface. If such a metal surface is in
contact with helium gas at a pressure P , and the whole system is in equilibrium
at temperature T , what is the mean number of helium atoms adsorbed per
unit area of the metal surface? Express your answer in terms of the quantities
given in the problem and fundamental constants.

29. Classical ideal gas in a piecewise constant potential

Consider a system of N classical particles confined in a box. The Hamiltonian
of the system is
X |~pi |2
H= Hi , Hi = + U (xi , yi , zi ),
i 2m

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 where

U (x, y, z) = U1 for − l1 ≤ x ≤ 0, −b ≤ y ≤ b, −c ≤ z ≤ c,
= U2 for 0 < x ≤ l2 , −b ≤ y ≤ b, −c ≤ z ≤ c,
= ∞ for x > l2 or x < −l1 or |y| > b or |z| > c.

The particles are at equilibrium at temperature T .

(a) Let ν denote the difference between the numbers of particles with x > 0
and x < 0. Find the mean value hνi and the fluctuation h(ν − hνi)2 i.
(b) Calculate the work ∆W done on the system if U2 is changed isothermally
and quasistatically from the initial value U1 to the final value U1 + ∆U .
(c) Calculate ∆W (∆U → ∞), and compare the result with that obtained
from thermodynamics for an isothermal compression.

30. van der Walls gas vs ideal gas - 1

One mole of a monatomic ideal gas is in a cylinder with a movable piston on
the other side of which is a pressure reservoir with Pr = 1 atm. How much heat
must be added to the gas to increase its volume from 20 to 40 liters via a quasi
static reversible process? Also calculate the heat required for the same process
assuming that the gas obeys the van der Waals equation of state. Which one
is larger?

31. van der Walls gas vs ideal gas - 2

Find the relationship between the volume and the temperature of a monatomic
van der Waals gas in a quasi-static adiabatic expansion (i.e., in an isentropic
expansion). Does the gas cool more or less compared to an ideal gas?

32. van der Waals gas vs. ideal gas - 3

One mole of an ideal gas (label-1) and one mole of Cl2 gas (label-2) are con-
tained in a rigid cylinder of volume 2V and are separated by a movable internal
piston. If the gases are at some particular temperature T , the piston is ob-
served to be precisely at the centre of the cylinder.
(a) [6 points] Assuming that Cl2 gas obeys the van der Waals equation of state
with molecular parameters a and b, obtain expressions for the temperature T ,
pressures P1 , P2 , and the energies E1 , E2 of each gas in terms of a, b and V
and the Avogadro Number NA . (Assume that kB T is high compared to the
rotational energy levels of the Chlorine molecules, but low compared to their
vibrational energy levels.)
(b) [2 points] In which direction will the piston move if the temperature is
slightly decreased to T − ∆T ?

33. Vapor pressure and coexistence conditions

(a) Show using the Clausius-Clapeyron equation and some reasonable as-
sumptions that the temperature dependence of the vapor pressure of a

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 liquid or a solid (i.e., the pressure of the vapor in coexistence with the liq-
uid or the solid) is approximately given by the equation ln p̄ = A − B/T .
What are A and B?
(b) The dependence on temperature of the vapour pressure p̄ (in millimeters
of mercury) of solid ammonia is given by ln p̄ = 23.03 − 3754/T (T is
the absolute temperature) and that of liquid ammonia is given by ln p̄ =
19.49 − 3063/T . Use this information to answer the following questions.
i. What is the temperature of the triple point of ammonia?
ii. What are the latent heats of sublimation and vaporization of ammo-
nia at the triple point?
iii. What is the latent heat of melting of ammonia at the triple point?
34. phase coexistence in van der Waals fluid
Two moles of a van der Waals fluid are maintained at a temperature T = 0.95Tc
in a volume of 200 cm3 . Show that the system has coexisting liquid and vapour
phases and find the mole number and volume of each phase. Use the molar
van der Waals parameters of oxygen (a = 0.138 Pa.m6 , b = 32.6 × 10−6 m3 ).
35. (5 pts) application of Clausius-Clapyeron
A long vertical glass tube closed at the bottom and open at the top is partially
filled with a liquid kept at temperature T . At this temperature, the liquid
solidifies below a particular level, remaining liquid above this level. The density
of the solid is higher than that of the coexisting liquid. As the temperature
is lowered by a small amount to T − ∆T , the solid-liquid interface moves up
by a small amount ∆h. Obtain an expression for ∆h, in terms of the mass
densities ρs and ρl of the solid and the liquid, respectively, the latent heat per
unit mass ` of the solid-liquid transition, the acceleration due to gravity g, T
and ∆T .
36. Liquid-drop Vapor coexistence
A gas can coexist with a droplet of radius r of its own liquid if the pressure of
the gas is Pr (T ). The purpose of this problem is to calculate the dependence
of Pr (T ) on r. The Gibbs potential of the system consisting of the gas and
the liquid droplet can be written as

Gtot = M2 g2 + M1 g1 + 4πSr2 ,

where M1 and M2 are the masses of the droplet and the vapor, respectively,
g1 and g2 are the respective Gibbs potentials per unit mass in the infinite
volume limit, and S is the coefficient of surface tension. Use the extremization
condition on G for equilibrium to obtain the relation
2S
g2 − g1 = ,
ρr
where ρ is the liquid density. Differentiate with respect to pressure at constant
temperature, and using the ideal gas law for the vapor whose density is much

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 smaller than ρ, obtain the relation

Pr (T ) = P∞ (T ) exp[2Sm/(ρkB T r)],

where m is the mass of a gas molecule.

37. Clausius-Clapyron equation extension

A substance whose state is specified by P , V , T can exist in two distinct
phases. At a given temperature T , the two phases can coexist if the pressure
is P (T ). The following information is known about the two phases: at the
temperature and pressure where they can coexist in equilibrium,

(a) there is no difference in the specific volumes of the two phases.

(b) there is no difference in the specific entropies of the two phases.
(c) the specific heat cp and the volume expansion coefficient α are different
for the two phases.

Using this information, find dP (T )/dT as a function of T .

38. Universal forms for the properties of a van der Waals gas
An approximation for the entropy S(E, V, N ) of real gases that is consistent
with the Van der Waals equation of state can be obtained by using the same
formula as for the ideal gas entropy, but with the volume replaced by (V −N b)
and the energy replaced by just the kinetic energy, EK = (E + aN 2 /V ).
Work out the “universal” equations for various properties of the van der Waals
gas by working with appropriately scaled or dimensionless, “reduced” versions
of the entropy, energy, free energies, etc., per particle, i.e., s̃ ≡ S/(N kB ),
˜ ≡ E/(N kB Tc ), f˜ ≡ F/(N kB Tc ), g̃ ≡ G/(N kB Tc ), g̃ ≡ G/(N kB Tc ) etc., as
well as ṽ ≡ V /Vc , P̃ ≡ P/Pc and T̃ ≡ T /Tc . Here

G(T, P, N ) = minV G(T, P, N ; V ) ≡ minV [F (T, V, N ) + P V ].

Show that g̃(T̃ , P̃ ) has two solutions g̃1 (T̃ , P̃ ) and g̃2 (T̃ , P̃ ) for a range of
reduced pressures if T̃ < 1. Produce equations (where possible) and plots for
s̃(˜, ṽ), f˜(T̃ , ṽ), P̃ (T̃ , ṽ), the universal coexistence curve P̃ (T̃ ), and [ṽg − ṽl ] as
a function of T̃ along the coexistence curve.

39. Critical phenomena in the van der Waals gas

The critical phenomena arising from the van der Waals equation are most
conveniently explored by working entirely in terms of the reduced variables
discussed above, in problem 5. Furthermore, close to the critical point, it is
convenient to express all the thermodynamic quantities in terms of variables
corresponding to small deviations from the critical point, namely t̂ ≡ T̃ − 1 =
(T − Tc )/Tc , p̂ ≡ P̃ − 1 = (P − Pc )/Pc and v̂ ≡ ṽ − 1 = (V − Vc )/Vc , and
expand in powers of t̂, p̂ and v̂. Show using such expansions that

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 (a) For temperatures T < Tc , (ṽg (t̂) − ṽg (t̂)), the difference or discontinuity
between the reduced specific volumes of the coexisting liquid and gas
phases vanishes as T → Tc from below as ∝ (−t̂)1/2
(b) The compressibility κ̃ ≡ −[ṽ∂ P̃ /∂ṽ]−1 diverges as T → Tc at P = Pc or
as P → Pc at T = Tc . Determine the corresponding critical exponents.

40. Magnetic ensembles

The thermodynamic potential appropriate for describing a magnetic material,
using the temperature T , the magnetic field B and the number of spins N as
the independent variables, is the Gibbs free energy

G(T, B, N ) = min (E − T S(E, M, N ) − M B).

(E,M )

(Note that in this notation, E = 0 for non-interacting spins, as the −M B term,

with M being the total magnetization, is being kept track of separately. For
the Ising model, in this notation E = −J <ij> σi σj , i.e, without the magnetic
P

field term. For this notation, the first law reads dE = T dS + B dM + µ dN .

See Hoch, Section 2.6 for a discussion of the different ways of defining the
energy of magnetic systems.) For the rest of this problem set, we suppress N
as an argument.

(a) Write down the Maxwell relation that can be obtained from the differen-
tial of G(T, B).
(b) Using the above result and standard thermodynamic manipulations, de-
rive the relation ! !
∂T T ∂M
=− ,
∂B S CB ∂T B
where CB is the heat capacity at constant magnetic field.
(c) Show that the specific heats at constant magnetic field and constant
magnetization are in general different, the difference being given by
!2 !
∂M ∂B
CB − CM = T
∂T B
∂M T

41. Ideal paramagnet

(a) Show that, for the simplest model for an ideal paramagnet consisting of
N non-interacting spin- 12 spins, the entropy is given by
" #
N M N M N M N M
Sid (M, N ) = kB N ln N − ( + ) ln( + )−( − ) ln( − )
2 2µB 2 2µB 2 2µB 2 2µB

where µB is the Bohr magneton.

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 (b) Show from the expression for G in the previous problem that minimizing
with respect to M (recall that E = 0) leads to the result that derived
directly from the partition function:

Gid (T, B) = −N kB T ln[2 cosh(βµB B)],

where β = 1/(kB T ).
 
∂T
(c) Evaluate ∂B S
for this system.
(d) The ideal paramagnet, initially at equilibrium at temperature Ti in mag-
netic field Bi , is thermally isolated from the environment and the mag-
netic field is slowly changed to Bf . What is the new temperature Tf of
the paramagnet?
(e) What is Tf if the magnetic field is reduced to zero (Bf = 0)? Is the result
you get physical? If it is not, explain why this calculation leads to an
unphysical result.

42. (9 pts) Ideal spin-1 paramagnet

The energy of an ideal spin-1 paramagnet consisting of N noninteracting mag-
netic atoms (or ions) each with partially filled electronic shells of total angular
momentum 1, when subject to an external magnetic field B, is given by
N
X
−µm B Siz ,
i=1

where each Siz takes values equal to −1, 0 or +1, and µm is the magetic
moment per spin. The system is in contact with a heat bath of temperature
T.

(a) [5 pts] Show that the magnetization M as a function of B and T has the
form M = N µm f ( µkm
BT
B
). What is f (x)?
(b) [3 pts] Determine the behaviour of this expression for small and large
magnetic fields ( µm B  kB T and µm B  kB T respectively) and sketch
the dependence of M on B at fixed T .
(c) [1 pt] What is the (zero field) susceptibility as a function of temperature?

43. (14 pts) Classical ideal gas with internal spin degrees of freedom
Consider an ideal monatomic gas made of N atoms, each of which in addition
carries a Spin 1/2, with a magnetic moment µB per spin. In the presence of a
magnetic field B, the Hamiltonian or Energy function of the gas can therefore
be written as
N N
X (~pi )2 X
H= − µB B σi ,
i=1 2m i=1

where p~i is the momentum of the ith particle, and each σi takes values equal to
−1 or +1. The system is enclosed in a volume V and is in equilibrium with a

13
 heat bath of temperature T . Determine the expressions for (i)the Free energy
F , (ii) the average energy E, (iii) the Entropy S, (iv) the magnetization M ,
and (v) the (zero field) susceptibility χ, as functions of T, V, N and B
44. (6 points) Quenching of classical gas with internal spin degrees of freedom
The gas is the previous problem is subjected initially to a very large magnetic
field (µB B  kB T ) such that all the atoms are essentially in the spin-state σi =
1, but the kinetic energy of the atoms has a thermal distribution corresponding
to the temperature T . The system is now removed from contact with the heat
bath and thermally isolated so that it has no energy exchange with the outside
world. The magnetic field is now suddenly changed to a much smaller value
Bf and the system is allowed to come to equilibrium, so that both the kinetic
energy and the spins have a common temperature Tf .
(a) (2 pts) Find the equation that determines the final temperature Tf
(b) (2 pts) In the circumstance that µB Bf  kB T calculate the difference
Tf − T up to order µB Bf /(kB T ). Is the system hotter or cooler finally
compared to T ?
(c) (2 pts) Within the same approximation as above, find the change in the
entropy of the gas, after the complete thermalization, which is correct up
to order µB Bf /(kB T ). Does the entropy increase or decrease?
45. Mean field Theory for phase transition in the Ising model
The mean-field approximation for the Ising model, with the energy given by
E = −J <ij> σi σj , can be obtained by replacing σi and σj by their mean
P

values, equal to M/(µB N ) ≡ m/µB , where m is the magnetisation per site;

i.e, by setting E ' −zc JM 2 /(2µ2B N ), where zc is the coordination number
of the lattice; and continuing to use the ideal paramagnetic expression given
above for the entropy.
(a) Show that the minimization with respect to M in the expression for G
given in the earlier problem now leads to the Curie-Weiss equation for M
given by
m m
= tanh[β(µB B + zc J )]
µB µB
(b) Derive the “universal form” of this equation by choosing the scaled dimension-
less variables m̃ ≡ m/µB , T̃ ≡ kB T /(zc J), and B̃ ≡ µB B/(zc J)
(c) Plot the solutions of this equation (you will need to use softwares such
as mathematica or matlab) eg.,m̃ versus T̃ for various values of B̃ and m̃
versus B̃ for various values of T̃ . Show that there is a first order phase
transition with a jump ∆m̃ across B̃ = 0 for T̃ < 1, with a critical point
at B̃ = 0, T̃ = 1 (⇒ Bc = 0, kB Tc = zc J). Draw the resulting phase
diagram.
(d) Determine the critical exponents for the vanishing of ∆m̃ as T̃ → 1− , the
divergence of the susceptibility χ̃(T̃ ) ≡ (∂ m̃/∂ B̃)|B̃=0 as T̃ → 1+ and the
vanishing of m̃(T̃ = 1, B̃) as B̃ → 0+ .

14
46. "Negative" temperatures
Consider a system of N non-interacting distinguishable particles in which the
energy of each particle can assume two distinct values, 0 and  > 0. The total
energy of the system is E.
(a) Find the entropy of this system as a function of E.
(b) Find the temperature as a function of E and show that it can be negative.
(c) Discuss what would happen when a system with negative temperature
is allowed to exchange energy with a system with positive temperature.
[Reference: N. F. Ramsey, Phys. Rev. 103, 20 (1956).]
47. Defects in a crystal
In a perfect crystal, the atoms are located at the lattice sites. By moving some
atoms from their original lattice sites to interstitial sites (which lie in-between
the lattice sites), one obtains an imperfect crystal with defects. The number of
possible interstitial sites, N 0 , is of the same order as N , the number of lattice
sites (N is also the number of atoms). Let 0 be the energy required to move
an atom from a lattice site to an interstitial site.
(a) Calculate the number of defects when the system is in equilibrium at
temperature T .
(b) Calculate the entropy and the heat capacity due to the defects.
48. collection of harmonic oscillators
Consider a two-dimensional square lattice of spacing a. A walker starts from
the point (0) and reaches the point (N a, M a) after taking N steps in the +x
direction and M steps in the +y direction. The first step is in the +x direction
and the remaining steps can be taken in any arbitrary sequence. Calculate the
total number, ν(M, N ), of distinct paths the walker can take.
Now consider a system of N non-interacting distinguishable quantum mechan-
ical one-dimensional harmonic oscillators, each with frequency ω. Show that
the total number of states with energy E = (M + N/2)~ω is given by ν(M, N )
calculated above. Use this result to calculate the entropy per oscillator and the
temperature as functions of the energy per oscillator. Discuss what happens
in the limit ~ω/ → 0 where  is the energy per oscillator.
49. Thermodynamics of a Debye Solid
Use the Debye approximation to calculate the contribution of lattice vibrations
to the thermodynamic functions of a crystal with one atom per unit cell.
(a) To be more specific, show that
9 θD θD
ln Z = N − 3N ln (1 − e−θD /T ) + N D( ),
8 T T
9 θD
E = N kB θD + 3N kB T D( ),
8 " T #
−θD /T θD
S = N kB −3 ln (1 − e ) + 4D( )
T

15
 Here, N is the number of atoms in the solid, T the absolute temperature, Z
the partition function, E the mean energy, S the entropy, θD = ~ωD /kB where
ωD is the Debye frequency, and D(y) ≡ (3/y 3 ) 0y x3 dx/(ex − 1).
R

(b) Find the first few terms in appropriate expansions of these expressions in
the limits T  θD and T  θD
(c) Show that P = E/(3V ) where P is the pressure and V is the volume of
the solid.
50. Thermodynamics of a photon gas
(a) Determine the Free energy F , the energy E and entropy S of a photon
gas in a cavity of volume V as functions of the temperature T and V either
by using the results of the previous problem carefully reexamining the limit of
θD → ∞ remembering there is no predetermined N now, or by an independent
calculation similar to the above.
(b) Show that the results are consistent with the fundamental relation
4 1/4 3/4 1/4
S= b E V
3
given in an earlier problem. Determine the parameter b in terms of the fun-
damental constants.
51. photon gas in n dimensions
As you found in the previous problem, in three dimensions, the energy density
of photon gas depends on the temperature T as T k with k = 4. Derive the
value of the exponent k in the temperature dependence of the energy density
for photon gas if space were to have n dimensions.
52. More properties of the photon gas
Show that the total (average) number of photons in a radiation-filled cavity of
volume V, whose walls are held at temperature T, is
!3
kB T
N = 16πζ(3)V ,
hc
where Z ∞ n−1
1 x dx
ζ(n) =
(n − 1)! 0 ex − 1
is a Riemann zeta function. Given that ζ(3) ' 1.202, demonstrate that the
mean energy per photon and the entropy per photon are
Ē π4
= kB T = 2.70 kB T
N 30ζ(3)
and
S 2π 4
= kB = 3.60 kB
N 45ζ(3)
respectively. Note that the entropy per photon is a constant, independent of
the temperature.

16
53. Heat shield for radiation
A black (non-reflective) plane at temperature Tu is parallel to a black plane
at temperature Tl < Tu . The net energy flux density in vacuum between the
two planes is JU = σ(Tu4 − Tl4 ), where σ is the Stefan-Boltzmann constant. A
third black plane is inserted between the other two, and is allowed to come to
a steady-state temperature Tm . Find Tm in terms of Tu and Tl , and show that
the net energy flux is cut in half because of the presence of this plane. This
is the principle of the heat shield, and is widely used to reduce radiant heat
transfer.
54. CMB and the expansion of the universe
The cosmic background microwave radiation spectrum is well fit by the Planck
equation for black body radiation with a temperature close to 3 K. Models for
the evolution of the universe predict that, following the Big Bang, conden-
sation of particles occurred as the universe expanded and cooled. After 300
million years, the temperature had dropped sufficiently that electrons became
bound in atoms and the universe became transparent to electromagnetic radi-
ation. Estimate the radiation temperature at this time, assuming the average
ionization energy is close to that of hydrogen 13.6 eV. Use this temperature
and the present radiation temperature to estimate by how much the universe
has expanded in the past 14 billion years.
55. Specific heat of Ferromagnetic magnons
For the quantized lattice waves (phonons) in the Debye theory of specific heats,
the frequency, ωs of a propagating accoustic wave is related to its wavevector,
~k, by the dispersion relation ω = cs k, where cs is the velocity of sound. On the
other hand, in a ferromagnetic solid at low temperatures, quantized waves of
magnetic excitations (spin waves), called magnons, have their frequencies, ω,
related to their wave-vectors, ~k, according to the dispersion relation ω = Ak 2 ,
where A is a constant. Show that, at low temperatures, the contribution of
spin waves to the heat capacity of the ferromagnet varies as T 3/2 .
56. Quantum ideal gas of 2 and 3 particles
(a) Consider a quantum ideal “gas” of only two particles confined in a cubic
box of volume V = L3 . Obtain explicit expressions for the canonical partition
function for this system, assuming that the particles are (i) fermions, and
(ii)bosons. For simplicity, ignore the spin degrees of freedom. (b) Carry out
the same exercise for three particles.
57. Pressure and compressibility of a Fermi gas
Demonstrate that the mean pressure of the conduction electrons in a metal in
their ground state can be written
2 N kB TF
P = ,
5 V
where TF is the Fermi temperature. Show that for silver (see earlier exercise),
P = 2.1 × 10 10 Pa. Show that the contribution of these conduction electrons

17
 to the isothermal compressibility is
3
κT =
5P
Estimate κT for silver. Compare your estimate to the experimental value
0.99 × 10 11 Pa−1 .

58. Size of Fermi energy in different systems

Give numerical estimates for the Fermi energy, Fermi temperature and Fermi
velocity of

(a) electrons in a typical metal, eg., Silver;

(b) nucleons in a heavy nucleus, eg., Lead;
(c) He3 atoms in liquid He3 (atomic volume = 46.2 Å3 per atom).
(d) Electrons in the sun.
(e) Electrons in a solar mass white dwarf
(f) A neutron star with mass twice that of the sun

Assume the particles to be non-interacting in all the cases, and look up any
data that you need, but is not given, from the Web. Is the approximation of
ignoring relativistic effects justified in the above cases?

59. Two Fermi gases in equilibrium

A cylinder is separated into two compartments by a freely sliding piston. Two
ideal Fermi gases are placed in the two compartments, numbered 1 and 2. The
particles in compartment 1 have spin 12 and those in compartment 2 have spin
3
2
. They all have the same mass. Find the equilibrium relative density of the
two gases (i.e. the ratio of the two equilibrium densities) at T = 0 and at
T → ∞.

60. Quantum ideal Fermi gas in 2 dimensions

Quantum particles can be confined in one of their space dimensions such that
at low enough temperatures they effectively “move” only in the other two
dimensions, say inside a macroscopic box of area A = L × L, which we can
treat using periodic boundary conditions. If the particles have mass m then
the energy-momentum relation determining the single particle eigen states is

|~p|2 ~2 |~k|2 ~ 2π 2π
(~p) = = ; k = ( nx , ny ),
2m 2m L L
where nx and ny are integers.

(a) (2 pts) Calculate the single-particle density of states D() of this system,
and show that it is a constant, independent of , for  > 0 (and 0 for
 < 0).

18
(b) Consider N such identical non-interacting fermions of spin-S (where S
is a half-integer).
i. (2 pts) Calculate the Fermi wave-number kF and the Fermi energy
F as functions of the areal number density n = N/A.
ii. (5 pts) Calculate the chemical potential µ as a function of n and
temperature T . (The relevant integrals over ~k or  can be done
exactly analytically for this case!). Sketch µ as a function of the
temperature for a fixed value of n.
(c) (2 pts) Show that in the "high temperature" limit , the leading order
result for the chemical potential of the form µ(T ) = B1 T − B2 T ln T ,
where B1 and B2 are constants. Evaluate B1 and B2 . endenumerate
(d) (12 pts) massless fermi gas
Consider a gas of N massless fermions of spin S confined in a cubic box
of volume V . In other words, ~k = c~|~k| ≡ c~k. (There are actually
materials where the electrons have this form of dispersion near special
points in the Brillouin zone.)
i. (3 pts) Calculate the Fermi energy F as a function of N , V and S.
ii. (3 pts) Calculate the Pressure at zero temperature.
iii. (3 pts) Suppose that S = 1/2, and a magnetic field B pointing
along the z direction that couples to the spin of the fermions via
the usual Zeeman interaction −µB σB where σ = ±1 is turned on.
Calculate the magnetization and the magnetic susceptibility at zero
temperature.
iv. (3 pts) Suppose we start with this gas very close to zero temperature,
and now open a valve, allowing the gas to undergo a free expansion
and come to equilibrium in a larger volume 2V . Assuming that no
work is done or no heat is transferred during this process, does the
temperature of the gas increase, decrease, or stay the same? Explain!
(e) Model of a semi conductor
Model a 2-dimensional semiconductor of area A with one valence band
with one electron energies −∆/2 − W <  < −∆/2 and one conduction
band with one electron energies ∆/2 <  < ∆/2 + W in terms of the
same constant density of states D per unit area per spin for both the
bands. These are to be filled with Ne electrons, which is sufficient to
fully occupy (i.e., two electrons per energy level) the valence band and
leave the conduction band empty at zero temperature.
i. What is the relationship between the variables defined above?
ii. Determine the chemical potential µ and the number of electrons in
the valence and conduction bands as a function of temperature.
iii. What will be the electronic specific heat as a function of temperature?
(f) A semiconductor with donor impurities
N “Donor” impurities are introduced into the semiconductor modeled as

19
 in the previous problem, leading to a new set of N degenerate one elec-
tron levels, all with energy 0 ( ∆) below the bottom of the conduction
band. There are an additional set of N electrons that “accompany” the
impurities.
i. What is the occupancy of the electronic levels at zero temperature?
ii. Determine the chemical potential µ and the number of electrons in
the valence and conduction bands as a function of temperature and
contrast with the case above.
(g) Electron emission from a hot metal
Model a metal with a surface as N noninteracting electrons trapped in a
potential well of depth −U0 and volume V , such that the energy levels as a
function of wave-vector ~k can now be written ~k = [~2~k 2 /(2m)] − U0 with
~k determined by periodic boundary conditions as usual. Furthermore,
assume that any electron with energy greater than 0 (“the vacuum level”)
will escape from the metal. Determine the flux of electrons emitted from
the metal at a temperature T such that kB T is much smaller than U0 or
the Fermi energy as measured from the vacuum level.
(h) Bose gas in 2-dimensions
For a two-dimensional gas of non-interacting bosons of mass m, find the
chemical potential µ at temperature T in terms of the number density n.
Check to see that your answer for the chemical potential correctly reduces
to the to the same classical limit as the Fermi gas discussed in the previous
problem set as T → ∞. Discuss what happens at low temperatures. Is
there a bose condensation phase transition in this case?
(i) Bose condensation in cold atoms
The Bose-Einstein (BE) condensation was first observed in an atomic
system in 1995 [Anderson, M.H., Ensher, J.R., Matthews, M.R., Wieman,
C.E., and Cornell, E.A. (1995). Science, 269, 198–202]. 87 Rb atoms
were confined in a magneto-optical trap and using special techniques
were cooled to below 1µ K. Evidence for BE condensation was obtained
at a temperature of 100 nK with the atoms confined to a volume of
10˘15 m3 . Estimate the required number of 87 Rb atoms in the trap for
Bose condensation to be observed. (The confining potential used in the
experiments was a three dimensional harmonic potential but simplify the
problem by assuming a box potential).
(j) Pressure and temp dependence of transport coefficients in a classical gas
In elementary kinetic theory, the viscosity η, the thermal conductivity κ,
and the diffusion constant D of a dilute non-ideal gas of particles of mass
m are determined in terms of its mean free path λ, the mean density
n, the molecular specific heat c̄ and the mean molecular speed v̄ by the
expressions
1 1 1
η = nmλv̄ ; κ = nc̄λv̄ ; D = λv̄ .
3 3 3

20
 The consideration that while traversing a distance l a molecule has as
many collisions on average as the number of particles inside a cylinder of
length l and cross-section equal to an effective area of cross section σ0 of
the molecule leads to the estimate: λ ≈ 1/(σ0 n). Using these discuss the
pressure and temperature dependence of the above transport coefficients.

Some open ended problems that also involve Conceptual Questions

(a) Think of an inflated helium balloon rising up from the earth’s surface
through the earth’s atmosphere. Consider two possibilities regarding the
material the balloon is made of: (a) it is a perfect thermal insulator
(b) it is not, and will permit heat exchange between the helium and the
atmosphere. Discuss how the state variables will change with time in the
two cases. Challenge yourself and see how quantitative you can get using
the simplifying assumptions of (1) an isothermal atmosphere and (2) an
adiabatic atmosphere
(b) Suppose a dilute gas consists of atoms that carry a spin of 1/2 and a
magnetic moment µB in the presence of an external uniform magnetic
field H oriented along the z-axis. Discuss how one needs to modify the
description of the macrostates and the microstates of the system. What
is the expression for the energy?
(c) Suppose instead that the dilute gas consists of asymmetric molecules that
carry an electric dipole moment d~ in the presence of an external uniform
~ Discuss how one needs to modify the description of the
electric field E.
macrostates and the microstates of the system. What is the expression
for the energy?
(d) Neon atoms crystallize into a face centered cubic lattice. Consider mod-
elling the low energy vibrations of the lattice in terms of springs of spring
constant K connecting nearest neighbor atoms. What variables will you
use to describe the micro-states of the system? What is the expression
for the energy? What do you think will be the macrostate variables of
such a system?

21