Intermediate Exam T4

Thermodynamics and
Statistical Physics
2021-2022
Tuesday December 25, 2022
16:00-18:00

Read these instructions carefully before answering the questions!

• Write your name and student number on every sheet.

• Make sure to write readable for other people than yourself. Points will
NOT be given for answers in illegible writing.
• Language; your answers have to be in English.
• Use a separate sheet for each problem.
• Use of a (graphing) calculator is allowed.
• This exam consists of 4 problems.
• The weight of the problems is Problem 1 (P1=30 pts); Problem 2
(P2=25 pts); Problem 3 (P3=20 pts); Problem 4 (P3=25 pts). Weights
of the various subproblems are indicated at the beginning of each
problem.
• The grade of the exam is calculated as (P1+P2+P3 +P4)/10.
• For all the problems you have to write down your arguments and the
intermediate steps in your calculation, else the answer will be
considered as incomplete and points will be deducted.
PROBLEM 1
Score: a+b+c+d+e =6+6+6+6+6=30

A gas of photons is confined to a cavity with volume 𝑉. The cavity is kept at a constant
temperature 𝑇.

HINT 1: The density of states for a spinless particle confined to an enclosure with volume
𝑉 is (expressed as a function of the particle’s momentum p):

𝑉
𝑔(𝑝)𝑑𝑝 = 4𝜋𝑝2 𝑑𝑝
ℎ3

1
HINT 2: The mean number of photons in a state with energy 𝜀 = ℏ𝜔 is equal to: 𝑒 𝛽𝜀 −1

a) Show that density of states of a photon in the cavity can be written as,

𝑉𝜔2 𝑑𝜔
𝑔(𝜔)𝑑𝜔 = 2 3
𝜋 𝑐

b) Show that the total mean energy 𝑈 of the photons in the cavity is given by,

𝜋2𝑘4
𝑈 = 𝑎𝑉𝑇 4 with 𝑎 =
15ℏ3 𝑐 3

c) Why is the chemical potential of the photon gas zero?

The logarithm of the partition function 𝑍𝑃ℎ of a photon gas can be written as,
∞

ln 𝑍𝑝ℎ = − ∑ ln(1 − 𝑒 −𝛽𝜀𝑖 ) with 𝜀𝑖 = ℏ𝜔𝑖 the single photon energy levels.
𝑖=1

d) Show that this logarithm can be expressed as,

𝜋2𝑘3
ln 𝑍𝑝ℎ = 𝑉𝑇 3
45ℏ3 𝑐 3

(ANOTHER HINT: transform the sum in an integral, use the density of states from a)
and use the table of integrals)

e) Calculate the Helmholtz free energy 𝐹 and the entropy 𝑆 of the photon gas. Check that
𝐹 = 𝑈 − 𝑇𝑆.
PROBLEM 2
Score: a+b+c+d =7+7+4+7=25

An alternative to the van der Waals equation of state for a real gas is the Berthelot equation:

𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑇𝑉 2

in which 𝑃, 𝑉, 𝑇 are the pressure, the molar volume and the temperature of the gas,
respectively. The constant 𝑎 controls the attractive molecular interactions and the constant
𝑏 corrects for the volume of the gas molecules.

a) Show that for a gas described by the Berthelot equation (a Berthelot gas) the constants
𝑎 and 𝑏 are related to the critical temperature 𝑇𝑐 , the critical pressure 𝑃𝑐 and the critical
volume 𝑉𝑐 by

27 𝑅 2 𝑇𝑐3 𝑅 𝑇𝑐 𝑉𝑐
𝑎= ;𝑏 = =
64 𝑃𝑐 8 𝑃𝑐 3

b) Show that the second virial coefficient 𝐵(𝑇) of a Berthelot gas is given by:

𝑉𝑐 27 𝑇𝑐 2
𝐵(𝑇) = (1 − ( ) )
3 8 𝑇

c) For a certain Berthelot gas the critical temperature is measured to be 150 K. Calculate
the Boyle temperature 𝑇𝑏 of this Berthelot gas. Why is this called the Boyle
temperature?

The second virial coefficient is related to the intermolecular potential 𝑣(𝑟) by:

1
𝐵(𝑇) = ∫(1 − 𝑒 −𝛽𝑣(𝑟) )𝑑 3 𝑟
2

A crude model for the intermolecular potential is the square well potential that is defined
by:

𝑣(𝑟) = ∞; 0<𝑟<𝜎
𝑣(𝑟) = −𝜀; 𝜎<𝑟<𝑅
𝑣(𝑟) = 0; 𝑟>𝑅

d) Show that for the square well potential the second virial coefficient is given by:
𝜀
𝐵(𝑇) = 𝐴 − 𝐵𝑒 𝑘𝑇

Express 𝐴 and 𝐵 in terms of 𝜎 and 𝑅.

PROBLEM 3
Score: a+b+c+d =5+5+5+5=20

The figure on the right gives a typical

pressure (𝑃) – temperature (𝑇) phase liquid
diagram of a one-component system with P solid critical point

only one triple point.

triple point

vapour

The Clausius-Clapeyron equation is: T

𝑑𝑃 ∆𝑆
=
𝑑𝑇 ∆𝑉

a) Derive the Clausius-Clapeyron equation starting from the premises that the Gibbs free
energy per molecule (𝑔) in phase 1 and phase 2 is equal in the situation when
equilibrium between these phases exists. Thus, 𝑔1 (𝑇, 𝑃) = 𝑔2 (𝑇, 𝑃).

b) Use the Clausius-Clapeyron equation to determine whether the substance in the phase
diagram expands or contracts upon melting. Explain your answer.

Consider the vapour curve in the phase diagram. Assume that 1) the latent heat 𝐿 (in Joule
per mole) for vaporization is independent of temperature, 2) the vapour obeys the ideal gas
law and 3) the volume of the liquid is small compared to the volume of the vapour.

c) Show that under these assumptions the vapour pressure is given by:
𝐿
𝑃𝑣𝑎𝑝 = 𝐶𝑒 −𝑅𝑇
where 𝐶 is a constant.

d) Calculate the latent heat for vaporization of water from the data in the table below. You
may assume that the latent heat is independent of temperature in the range 50-90 °C.

Vapour pressure of water

Temperature (°C) Pressure (kPa)
60 19.9
80 47.3
PROBLEM 4 Score: a+b+c+d+e =4+4+5+6+6=25

Consider a system of three identical non-interacting particles. Each particle can be in one
of three single particle states: 𝜑1 , 𝜑2 and 𝜑3 with energies 0, 𝜀 and 𝜀, respectively. Note:
identical implies that if the particles have spin this is also pointing in the same direction!

Use the notation (𝑛1 , 𝑛2 , 𝑛3 ) for three particle states with 𝑛𝑖 (𝑖 = 1,2,3) the occupation
number of single-particle state 𝜑𝑖 (𝑖 = 1,2,3), respectively. For example: (1,1,1) means
that one particle is in state 𝜑1 , one particle is in state 𝜑2 and one particle is in state 𝜑3 .

List all three-particle states with their energy and degeneracy in case the three particles are:

a) Indistinguishable fermions
b) Indistinguishable bosons

c) Give the partition functions for situations a), and b)

d) Calculate the mean energy as a function of temperature for situations a) and b).
Compare the mean energies for situations a) and b) in the limit 𝑇 → ∞. Is this what you
expected? Why?

A gas of 𝑁 (a large number) non-interacting bosons with spin 𝑆 = 1 is trapped in an

enclosure of volume 𝑉 and in equilibrium with a heat bath at temperature 𝑇 and a particle
reservoir with chemical potential 𝜇. The potential that results in the trapping of the bosons
leads to a density of states of the form:

𝑔(𝐸)𝑑𝐸 = 𝐶𝐸 4 𝑑𝐸

where 𝐶 is a positive constant and 𝐸 is the energy of the state.

e) Show that the total number of bosons can be written as:

∞
𝐶𝐸 4
𝑁 = 𝑁0 + ∫ 𝑑𝐸
𝑒𝛽(𝐸−𝜇) − 1
0

where 𝑁0 is the number of bosons in the ground state with 𝐸 = 0. Give an expression for
𝑁0 and explain why the ground state should be treated in this way.
Solutions

PROBLEM 1

a)
For photons the momentum 𝑝 is related to energy 𝜀 = ℏ𝜔 = 𝑝𝑐. Using this in HINT 1 in
combination with the fact that the photon has two polarization states leads to,

𝑉 ℏ𝜔 2 ℏ𝜔 𝑉 ℏ 3 2 𝑉𝜔2 𝑑𝜔
𝑔(𝜔)𝑑𝜔 = 2 3 4𝜋 ( ) 𝑑 ( ) = 2 3 ( ) 𝜔 𝑑𝜔 = 2 3
ℎ 𝑐 𝑐 𝜋 ℏ 𝑐 𝜋 𝑐
b)
Using the density of states in a) and the mean number of photons in each state 𝑛(𝜔)
(from HINT 2) and using 𝜀 = ℏ𝜔 we find,

The total mean energy 𝑈 in the cavity is,

∞ ∞
ℏ𝜔 𝑉𝜔2 𝑑𝜔
𝑈 = ∫ ℏ𝜔 𝑛(𝜔)𝑔(𝜔)𝑑𝜔 = ∫
𝑒𝛽ℏ𝜔 − 1 𝜋 2 𝑐 3
0 0

Using the substitution 𝑥 = 𝛽ℏ𝜔 this leads to,

∞ ∞
ℏ𝑉 1 𝑥 3 𝑑𝑥 𝑉𝑘 4 𝑇 4 𝑥 3 𝑑𝑥
𝑈= 2 3 ∫ = ∫
𝜋 𝑐 (𝛽ℏ)4 𝑒 𝑥 − 1 𝜋 2 ℏ3 𝑐 3 𝑒 𝑥 − 1
0 0

𝜋4
The integral is equal to 15, this follows from the table with the integrals and constants,
thus,

𝑉𝑘 4 𝑇 4 𝜋 4 𝑉𝜋 2 𝑘 4 𝑇 4
𝑈= 2 3 3 = 3 3
= 𝑎𝑉𝑇 4
𝜋 ℏ 𝑐 15 15ℏ 𝑐

c)
The number of photons in not conserved. We have a constant 𝑇 and 𝑉 system in
equilibrium. Thus, the system is at a minimum of the Helmholtz free energy with respect
to variations in the number of photons. Implying,

𝜕𝐹
( ) = 0⇒𝜇 = 0
𝜕𝑁 𝑉,𝑇

d)
Use the hint and make the energy levels continuous and replace the sum with an integral
and use the density of states from a),
 ∞ ∞
−𝛽ℏ𝜔 −𝛽ℏ𝜔
𝑉𝜔2 𝑑𝜔
ln 𝑍𝑝ℎ = − ∫ ln(1 − 𝑒 )𝑔(𝜔)𝑑𝜔 = − ∫ ln(1 − 𝑒 ) 2 3
𝜋 𝑐
0 0

With the substitution 𝑥 = 𝛽ℏ𝜔 this leads to,

∞
𝑉 1
ln 𝑍𝑝ℎ =− 2 3 ∫ ln(1 − 𝑒 −𝑥 )𝑥 2 𝑑𝑥
𝜋 𝑐 (𝛽ℏ)3
0

Use the table with the integrals and constants,

∞
𝜋4
∫ ln(1 − 𝑒 −𝑥 )𝑥 2 𝑑𝑥 = −
45
0

To find:
𝑉 1 𝜋4 𝜋2𝑘3
ln 𝑍𝑝ℎ = = 𝑉𝑇 3
𝜋 2 𝑐 3 (𝛽ℏ)3 45 45ℏ3 𝑐 3

e)
𝜋2𝑘4 4
1 𝜋2𝑘4 1
𝐹 = −𝑘𝑇 ln 𝑍𝑝ℎ = − 3 3
𝑉𝑇 = − 3 3
𝑉𝑇 4 = − 𝑎𝑉𝑇 4
45ℏ 𝑐 3 15ℏ 𝑐 3

From 𝐹 = 𝑈 − 𝑇𝑆 we have

𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇

Thus,
1
𝜕𝐹 𝜕 (− 3 𝑎𝑉𝑇 4 ) 4
𝑆 = −( ) = −( ) = 𝑎𝑉𝑇 3
𝜕𝑇 𝑉 𝜕𝑇 3
𝑉
And,
1 4
𝐹 = − 𝑎𝑉𝑇 4 = 𝑎𝑉𝑇 4 − 𝑇 𝑎𝑉𝑇 3 = 𝑈 − 𝑇𝑆
3 3

Check.
PROBLEM 2

a)
The critical point is found when the isotherm of the gas has an infliction point, thus as,

𝜕𝑃 𝜕 2𝑃
( ) = ( 2) = 0
𝜕𝑉 𝑇 𝜕𝑉 𝑇

This gives (together with the Berthelot equation of state) three equations with three
unknowns namely:

𝑅𝑇 𝑎
𝑃= − eq(1)
𝑉 − 𝑏 𝑇𝑉 2

𝜕𝑃 −𝑅𝑇 2𝑎
( ) = 2
+
𝜕𝑉 𝑇 (𝑉 − 𝑏) 𝑇𝑉 3

𝜕𝑃
Thus (𝜕𝑉) = 0 leads to
𝑇
−𝑅𝑇 2𝑎 2𝑅𝑇 2 4𝑎
( + ) = 0 ⇒ = eq(2)
(𝑉 − 𝑏)2 𝑇𝑉 3 (𝑉 − 𝑏)2 𝑉 3

𝜕 2𝑃 2𝑅𝑇 6𝑎
( 2) = ( − )
𝜕𝑉 𝑇 (𝑉 − 𝑏)3 𝑇𝑉 4

𝜕2 𝑃
And (𝜕𝑉 2 ) = 0 leads to
𝑇
2𝑅𝑇 6𝑎 2𝑅𝑇 2 6𝑎(𝑉 − 𝑏)
( − ) = 0 ⇒ = eq(3)
(𝑉 − 𝑏)3 𝑇𝑉 4 (𝑉 − 𝑏)2 𝑉4

Combining 2 and 3 leads to

4𝑎 6𝑎(𝑉 − 𝑏)
= ⇒ 4𝑉 = 6(𝑉 − 𝑏) ⇒ 𝑉𝑐 = 3𝑏
𝑉3 𝑉4

Substituting this in equation 2 gives,

 2𝑅𝑇 2 4𝑎 2𝑅𝑇 2 4𝑎 2 2 𝑎
= = 0 ⇒ = ⇒ 𝑇𝑐 = √
(3𝑏 − 𝑏)2 (3𝑏)3 4𝑏 2 27𝑏 3 3 3 𝑏𝑅

2 2 𝑎
and 𝑇𝑐 = 3 √3 𝑏𝑅 and 𝑉𝑐 = 3𝑏 in equation 1 gives,

2 2 𝑎
𝑅 3 √3 𝑎 1 2 𝑎𝑅 3𝑎 3 𝑏𝑅
𝑏𝑅 √
𝑃𝑐 = − = √ −
3𝑏 − 𝑏 2 √2 𝑎 3𝑏 3 𝑏 18𝑏 2 2 𝑎
(3𝑏)2
3 3 𝑏𝑅
1 2 𝑎𝑅 9 2 𝑎𝑅 1 2 𝑎𝑅
= √ − √ = √
3𝑏 3 𝑏 36𝑏 3 𝑏 12𝑏 3 𝑏

And thus,
2 3 𝑎 1 3 𝑎𝑅
𝑇𝑐2 = ( ) and 𝑃𝑐2 = ( ) ⇒
3 𝑏𝑅 2 × 3 𝑏3

2 3 𝑎
𝑇𝑐2 (3) 𝑏2 𝑅 𝑇𝑐
= 𝑏𝑅 6
= (2) 2 ⇒ 𝑏 =
3
𝑃𝑐2 1 𝑎𝑅 𝑅 8 𝑃𝑐
(2 × 3) 3
𝑏
And,

𝑏𝑅𝑇𝑐2
𝑅𝑇𝑐2 𝑅 𝑇𝑐 27 𝑅 2 𝑇𝑐3
𝑎= = =
2 3 2 3 8 𝑃𝑐 64 𝑃𝑐
(3) (3)

b)
Rewrite the Berthelot equation as:

𝑃𝑉 1 𝑎
= −
𝑅𝑇 (1 − 𝑏 ) 𝑅𝑇 2 𝑉
𝑉
1
and expand the first term on the right hand side in powers of 𝑉:

𝑃𝑉 𝑏 𝑏 2 𝑎
= (1 + + ( ) + ⋯ ) − ⇒
𝑅𝑇 𝑉 𝑉 𝑅𝑇 2 𝑉

𝑃𝑉 𝑎 1
= 1 + (𝑏 − ) +⋯
𝑅𝑇 𝑅𝑇 2 𝑉

Thus,
 𝑎 𝑉𝑐 27 𝑅 2 𝑇𝑐3 1
𝐵(𝑇) = 𝑏 − = −
𝑅𝑇 2 3 64 𝑃𝑐 𝑅𝑇 2
Using
𝑅 𝑇𝑐 𝑅 𝑇𝑐 3𝑅 𝑇𝑐
𝑏= ⇒ 𝑃𝑐 = =
8 𝑃𝑐 8𝑏 8 𝑉𝑐
We find

𝑉𝑐 27 𝑅 2 𝑇𝑐3 1 𝑉𝑐 27 𝑇𝑐 2
𝐵(𝑇) = − = (1 − ( ) )
3 64 (3𝑅 𝑇𝑐 ) 𝑅𝑇 2 3 8 𝑇
8 𝑉𝑐

c) The temperature at which the second virial coefficient is zero is called the Boyle
temperature.

27 𝑇𝑐 2 27
𝐵(𝑇) = 0 ⇒ 1 − ( ) = 0 ⇒ 𝑇𝑏 = √ 𝑇𝑐 = 1.84 × 150 = 276 K
8 𝑇 8

At this temperature Boyle’s law (𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) approximately holds for a real gas.

d)

1
𝐵(𝑇) = ∫(1 − 𝑒 −𝛽𝑣(𝑟) )𝑑3 𝑟
2
𝜎 𝑅 ∞
1 1 1
= ∫ 4𝜋𝑟 2 𝑑𝑟 + ∫(1 − 𝑒 𝛽𝜀 )4𝜋𝑟 2 𝑑𝑟 + ∫ 0 ∙ 4𝜋𝑟 2 𝑑𝑟 ⇒
2 2 2
0 𝜎 𝑅

𝜎 𝑅
2𝜋 3
𝐵(𝑇) = 2𝜋 ∫ 𝑟 2 𝑑𝑟 + 2𝜋(1 − 𝑒 𝛽𝜀 ) ∫ 𝑟 2 𝑑𝑟 + 0 = (𝜎 + (1 − 𝑒 𝛽𝜀 )(𝑅 3 − 𝜎 3 )) ⇒
3
0 𝜎

2𝜋 3 2𝜋 3 2𝜋 3 𝜀
𝐵(𝑇) = (𝑅 − 𝑒 𝛽𝜀 (𝑅 3 − 𝜎 3 )) = 𝑅 − (𝑅 − 𝜎 3 )𝑒 𝛽𝜀 = 𝐴 − 𝐵𝑒 𝑘𝑇
3 3 3
PROBLEM 3

a)
Take two points 𝑎 and 𝑏 at the equilibrium curve separated by 𝑑𝑇 and 𝑑𝑃 (see figure).
Then at point 𝑎: 𝑔1𝑎 = 𝑔2𝑎 and at point 𝑏: 𝑔1𝑏 = 𝑔2𝑏 which leads to 𝑑𝑔1 = 𝑑𝑔2 when moving
from point 𝑎 to point 𝑏.

Gibbs free energy is given by,

𝐺 = 𝐸 + 𝑃𝑉 − 𝑇𝑆 ⇒ 𝑑𝐺 = 𝑑𝐸 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

And using the fundamental thermodynamic relation for a system with variable particle
number:

𝑑𝐸 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝜇𝑑𝑁

We find,
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑑𝑁

Which holds for each phase and using (𝜇 = 𝑔) this results in (𝑖 = 1,2):

𝑑𝐺𝑖 = −𝑆𝑖 𝑑𝑇 + 𝑉𝑖 𝑑𝑃 + 𝑔𝑖 𝑑𝑁

We also have 𝐺𝑖 = 𝑁𝑖 𝑔𝑖 ⇒ 𝑑𝐺𝑖 = 𝑁𝑖 𝑑𝑔𝑖 + 𝑔𝑖 𝑑𝑁𝑖

Combining both expressions for 𝑑𝐺𝑖 we derive: 𝑁𝑖 𝑑𝑔𝑖 = −𝑆𝑖 𝑑𝑇 + 𝑉𝑖 𝑑𝑃 or 𝑑𝑔𝑖 =

−𝑠𝑖 𝑑𝑇 + 𝑣𝑖 𝑑𝑃 where 𝑠𝑖 and 𝑣𝑖 are the entropy and volume per molecule.

Thus,
𝑑𝑃 ∆𝑠
𝑑𝑔1 = −𝑠1 𝑑𝑇 + 𝑣1 𝑑𝑃 = 𝑑𝑔2 = −𝑠2 𝑑𝑇 + 𝑣2 𝑑𝑃 ⇒ =
𝑑𝑇 ∆𝑣

which is the Clausius-Clapeyron equation with ∆𝑆 and ∆𝑉 expressed on a per molecule

basis.

b)
The Clausius-Clapeyron equation gives the slope of the melting curve. From the figure we
see that this slope is positive, In the transformation from solid to liquid the entropy
increases (∆𝑆 = 𝑆𝑙𝑖𝑞𝑢𝑖𝑑 − 𝑆𝑠𝑜𝑙𝑖𝑑 > 0). For a positive slope we should have ∆𝑉 = 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 −
𝑉𝑠𝑜𝑙𝑖𝑑 > 0, and thus the volume of the substance increases upon melting.

c)
𝐿
The entropy change per mole is ∆𝑆 = 𝑇.
The volume change is ∆𝑉 = 𝑉𝑣𝑎𝑝𝑜𝑢𝑟 − 𝑉𝑙𝑖𝑞𝑢𝑖𝑑 ≈ 𝑉𝑣𝑎𝑝𝑜𝑢𝑟 .
The ideal gas law for one mole of vapour is : 𝑃𝑉𝑣𝑎𝑝𝑜𝑢𝑟 = 𝑅𝑇.
Then from the Clausius-Clapeyron equation we find,

𝑑𝑃 ∆𝑆 𝐿 1 𝐿𝑃
= = = ⇒
𝑑𝑇 ∆𝑉 𝑇 𝑉𝑣𝑎𝑝𝑜𝑢𝑟 𝑅𝑇 2

𝑑𝑃 𝐿𝑑𝑇 −𝐿 −𝐿 −
𝐿
= ⇒ 𝑑 ln 𝑃 = 𝑑 ⇒ ln 𝑃 = + 𝐶 ⇒ 𝑃 = 𝐶𝑒 𝑅𝑇
𝑃 𝑅𝑇 2 𝑅𝑇 𝑅𝑇

d)
𝑇1 = 60°C = 333.15 K; 𝑇2 = 80°C = 353.15 K
𝑃1 = 19.9 kPa; 𝑃2 = 47.3kPa

Using c)

𝑃
𝑃1 𝐿 1 1 𝑅 ln (𝑃1 )
− ( − ) 2
= 𝑒 𝑅 𝑇1 𝑇2 ⇒ 𝐿 = − ⇒
𝑃2 1 1
(𝑇 − 𝑇 )
1 2
19.9
8.314 × ln (47.3)
𝐿=− ≈ 42 kJ per mole
1 1
( − )
333.15 353.15
PROBLEM 4

a) (1,1,1) with energy 2𝜀, and degeneracy: 1

b) (1,1,1) with energy 2𝜀, and degeneracy: 1

(2,1,0) with energy 𝜀, and degeneracy: 1
(1,2,0) with energy 2𝜀, and degeneracy: 1
(1,0,2) with energy 2𝜀 and degeneracy: 1
(2,0,1) with 𝜀 and degeneracy:1
(0,2,1) with 3𝜀 and degeneracy:1
(0,1,2) with energy 3𝜀, and degeneracy: 1
(3,0,0) with energy 0, and degeneracy: 1
(0,3,0) with energy 3𝜀, and degeneracy: 1
(0,0,3) with energy 3𝜀, and degeneracy: 1

c)

Situation a) 𝑍 = 𝑒 −2𝛽𝜀
Situation b) 𝑍 = 1 + 2𝑒 −𝛽𝜀 + 3𝑒 −2𝛽𝜀 + 4𝑒 −3𝛽𝜀

d)
Situation a)
𝜕 ln 𝑍 2𝑒 −2𝛽𝜀
〈𝐸〉 = − = 𝜀 −2𝛽𝜀 = 2𝜀
𝜕𝛽 𝑒
Situation b)
𝜕 ln 𝑍 2𝑒 −𝛽𝜀 + 6𝑒 −2𝛽𝜀 + 12𝑒 −3𝛽𝜀
〈𝐸〉 = − =𝜀
𝜕𝛽 1 + 2𝑒 −𝛽𝜀 + 3𝑒 −2𝛽𝜀 + 4𝑒 −3𝛽𝜀

In the limit 𝑇 → ∞
Situation a)

〈𝐸〉 → 2𝜀
Situation b)
2 + 6 + 12 20
〈𝐸〉 → 𝜀 = 𝜀 = 2𝜀
1 + 2 + 3 + 4 10
At high temperatures the system becomes classical and all states are equally probable and
thus have on average 1 particle (because there are 3 states and three particles) and thus the
mean energy becomes (0 + 𝜀 + 𝜀) = 2𝜀.
The total number of bosons is given by:

∞ ∞
𝐶𝐸 4
𝑁 = ∫ 𝑛(𝐸) 𝑔(𝐸)𝑑𝐸 = ∫ 𝑑𝐸
𝑒𝛽(𝐸−𝜇) − 1
0 0

However, the ground state with 𝐸 = 0 has zero weight in this integral because of the 𝐸 4
factor and is thus completely neglected. To fix this we consider the ground state separately:
∞
1 𝐶𝐸 4
𝑁 = 𝑁0 + 𝑁(𝐸 > 0) = +∫ 𝑑𝐸
𝑒 −𝛽𝜇 − 1 𝑒𝛽(𝐸−𝜇) − 1
0