PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Solution to assignment 3 of Thermodynamics and Statistical Mechanics1

(Due on September 6 2024 at 2pm. Submit your solution to Canvas as a PDF file.)

Problem 1 (10 points). In the class, we have calculated the multiplicity of a magnet made of N two-state
systems, if it has a magnetization M > 0 (namely, the number of up-pointing dipoles minus the number of
down-pointing dipoles is M ). This multiplicity is given by N +M N! !N −M ! . In this problem, we will consider
( 2 )( 2 )
two interacting magnets A and B, which are made of NA two-state systems and NB two-state systems,
respectively, where both NA and NB are large. Denote the magnetizations of A and B by MA and MB ,
respectively. Suppose |MA | ≫ 1 and |MB | ≫ 1, as well as |NA − MA | ≫ 1 and |NB − MB | ≫ 1. Assume
M = MA + MB , the total magnetization of the combined system is fixed, and 1 ≪ |M | < NA + NB . We
will explore how the multiplicity of the combined system behaves as a function of MA .
(1) (2 points) Without making any approximation, show that the multiplicity of the combined system is
Ω =  NA +MA NA!NA −MA   NB +MB N
B!
NB −MB
 . What is the entropy of the combined system?
2 ! 2 ! 2 ! 2 !

(2) (4 points) Applying the Stirling formula (i.e., ln n! ≈ n ln n − n for n ≫ 1) to the entropy, show that the
entropy under this approximation is

NA + M A NA + M A NA − MA NA − MA
S = k NA ln NA − ln − ln
2 2 2 2
! (1)
NB + M B NB + M B NB − MB NB − MB
+NB ln NB − ln − ln
2 2 2 2

Fixing NA , NB and M = MA + MB , show that MA /NA = MB /NB for the most probable macrostate.
Remark: This result makes sense, because it means that in thermal equilibrium the system tends to be
uniform with the same magnetization density everywhere.
(3) (4 points) Denoting the most probable value of MA by MA∗ and δMA = MA − MA∗ . Expand Eq. (1) to
the second order of δMA and show that

k (NA + NB )3
S = S∗ − δMA2 + O(δMA3 ) (2)
2 NA NB (NA + NB + M )(NA + NB − M )

where S ∗ is the entropy for the most probable macrostate. Show that this result implies that near the most
probable macrostate where δMA is small,qthe multiplicity Ω as a function of δMA can be viewed as a normal
2
/σ 2
distribution with a width of the order of NA NB (N −A+N B +M )(NA +NB −M )
(NA +NB )3 . That is, Ω(δMA ) ∝ e−(δMA )
q
B +M )(NA +NB −M )
with σ of the order of NA NB (NA +N (NA +NB )3 .
Remark: Suppose NA and NB are of the same order, and typically M is an extensive quantity of the order
of NA , then the number of different macrostates is of the order of√NA . Therefore, the ratio between the
above width and the number of all macrostates is of the order of 1/ NA , which is quite small for large NA .
Namely, we will almost surely only observe the most probable macrostate.
1 You are welcome to get back with questions and clarifications if the wording of problems is ambiguous.

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Solution:
(1) In this question, we aim to write the multiplicity of the combined system as a function of MA . We
can firstly pick NA +M
2
A
up-pointing dipoles from NA total dipoles of A magnet, and then pick NB +M2
B

up-pointing dipoles from NB total dipoles of B magnet. Without any approximation about the interaction
between these two magnets, we think this two steps are independent to get the maximal multiplicity Ω:

NA +MA NB +MB
Ω = CNA 2 CNB 2 (3)
NA ! NB !
= NA +MA
NA −MA
NB +MB

NB −MB
(4)
2 ! 2 ! 2 ! 2 !

Thus, the entropy S is

S = k ln(Ω) (5)
(2) In this question, we apply the Stirling formula to further simplify the entropy we get from the last
question (N ≫ 1):

S =k ln(Ω) (6)
        
NA + MA NA − M A NB + MB NB − M B
=k ln NA ! − ln ! − ln ! + ln NB ! − ln ! − ln !
2 2 2 2
(7)

NA + MA NA + MA NA + MA
=k NA ln NA − NA + NB ln NB − NB − ln +
2 2 2
NA − MA NA − MA NA − M A NB + M B NB + M B
− ln + − ln (8)
2 2 2 2  2
NB + MB NB − M B NB − M B NB − M B
+ − ln +
2 2 2 2
NA + MA NA + MA NA − MA NA − MA
=k NA ln NA − ln − ln
2 2 2 2
! (9)
NB + M B NB + M B NB − M B NB − M B
+ NB ln NB − ln − ln
2 2 2 2

∂S
With the most probable macrostate, the derivative of entropy should be zero, which is ∂MA ∗
= 0.
MA

 
∂S 1 NA + M A 1 1 NA − MA 1 1 NB + M − M A 1 1 NB − M + MA 1
=k − ln − + ln + + ln + − ln −
∂MA 2 2 2 2 2 2 2 2 2 2 2 2
(10)
k (NA − MA )(NB + MB )
= ln (11)
2 (NA + MA )(NB − MB )

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Thus, for the most probable macrostate, we have

NA − MA∗ NB − MB∗
∗ = (12)
NA + M A NB + MB∗
It is just
NA↑ NB↑
= (13)
NA↓ NB↓
∗ ∗
MA MB
Thus, we have NA = NB .
NA
(3) We perform a Taylor expansion for entropy at the most probable value MA∗ = NA +NB M .

∂S 1 ∂2S
S = S∗ + δMA + δ 2 MA + o(δ 3 MA ) (14)
∂MA ∗
MA 2 ∂MA2 ∗
MA

For the second derivative in Eq. (14),

∂2S
 
k 1 1 1 1
=− + + + (15)
∂MA2 M ∗ 2 NA − M A NA + M A NB + M − M A NB − M + M A ∗
MA
A

(NA + NB )3
=−k (16)
NA NB (NA + NB + M )(NA + NB − M )

∂S
We also have ∂MA ∗
= 0, so
MA

k (NA + NB )3
S =S ∗ − δMA2 + O(δMA3 ) (17)
2 NA NB (NA + NB + M )(NA + NB − M )

Then, the multiplicity Ω as a function of δMA can be viewed as a normal distribution

Ω =eS/k (18)
2 2
∝e−(δMA ) /σ
(19)
q q
2NA NB (NA +NB +M )(NA +NB −M ) NA NB (NA +NB +M )(NA +NB −M )
where σ = (NA +NB )3 , with the order (NA +NB )3 .

Problem 2 (10 points). In the class, we have learnt that the entropy of an ideal gas made of N identical
monatomic particles with total energy U and volume V is
"  3 ! #
V 4πmU 2 5
S = N k ln + (20)
N 3N h2 2

and the multiplicity is

Ω = f (N )V N U 3N/2 (21)

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Figure 1: Two ideal gases made of the same type of monatomic particles are separated by a plate (represented
by the red vertical line) that allows energy exchange but no particle exchange. The position of the plate can also
move horizontally without encountering any friction.

π 3N/2
where f (N ) = N !h3N (3N/2)!
(2m)3N/2 .
In this problem, we will examine the thermal equilibrium state of two ideal gases made of the same type
of monatomic particle with mass m. These two gases are separated by a plate that allows energy exchange
and can move without friction (see Fig. 1). Suppose the left side contains NA particles, has energy UA and
volume VA , and the right side contains NB particles, has energy UB and volume VB . Suppose there is no
particle exchange between the two containers, so that NA and NB are fixed. Also supposed the total energy
U = UA + UB and total volume V = VA + VB are both fixed.
(1) (2 points) Show that the total entropy of the two gases is
"  3 ! # "   23 ! #
VA 4πmUA 2 5 VB 4πmUB 5
S = NA k ln + + NB k ln + (22)
NA 3NA h2 2 NB 3NB h2 2

(2) (4 points) Take the derivatives of the total multiplicity with respect to UA and VA to show that UA /NA =
UB /NB and VA /NA = VB /NB in the most probable macrostate. Use the equipartition theorem and ideal
gas law to show that the temperatures on the two sides of the plate are the same, and the pressures on the
two sides of the plate are also the same.
Remark: Again, this result makes sense because it means that in thermal equilibrium the system tends to
be uniform.
(3) (4 points) For the most probable macrostate, calculate the second order derivatives of Eq. (22), the
∂2S ∂2S ∂2S
total entropy of the two gases, with respect to UA and VA , i.e., ∂U 2 , ∂U ∂V
A A
and ∂V 2 . You should find, for
A A
the most probable macrostate,
∂2S 3k(NA + NB )3 ∂2S ∂2S k(NA + NB )3
2 =− , = 0, 2 =− . (23)
∂UA 2NA NB U 2 ∂UA ∂VA ∂VA NA NB V 2
Show that these results imply that near the most probable macrostate, q the multiplicity Ω as a function of
NA NB U 2
UA and VA is a two-variable Gaussian function with a width of the order (N A +NB )
3 along the UA direction

(U −U ∗ )2 (V −V ∗ )2
− A 2A − A 2A
q
NA NB V 2
(NA +NB )3 along the VA direction. That is, Ω ∝ e
σ σ
and a width of the order U V , where
∗ ∗
U
qA and VA are the
q most probable values of UA and V A , respectively, and σ U and σ V are of the order of
NA NB U 2 NA NB V 2
(NA +NB )3 and (NA +NB )3 , respectively.
Remark: Again, consider the case where NA and NB are of the same order, typically the energy U and
volume V are extensive quantities, i.e., they are also of the same order of NA and NB . So the total number

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

of all macrostates will be proportional to U V . Therefore, the above widths suggest that the fluctuations
around the most probable macrostates are concentrating in a narrow window. Namely, we will almost surely
only observe the most probable macrostate.
Solution:
(1) The total multiplicity Ω = ΩA ΩB , so the total entropy S = SA + SB
"  3 ! # "  3 ! #
VA 4πmUA 2 5 VB 4πmUB 2 5
S = NA k ln + + NB k ln + (24)
NA 3NA h2 2 NB 3NB h2 2

∂S ∂S
(2) For the most probable macrostate, we have ∂UA = 0 and ∂VA =0

∂S 3 3
= NA k − NB k (25)
∂UA 2UA 2(U − UA )

∂S 1 1
= NA k − NB k (26)
∂VA VA V − VA
Thus, we have UA /NA = UB /NB and VA /NA = VB /NB in the most probable macrostate. With U = 23 N kT ,
we have TA = TB . With the ideal gas law P V = N kT , we have PA = PB .
(3) In this question, we also perform a Taylor expansion for the entropy at the most probable macrostate.
!
∗ ∂S ∂S 1 ∂2S 2 ∂2S ∂2S
S=S + δUA + δVA + δ UA + 2 δUA δVA + δ VA +o3
2
∂UA U ∗ ∂VA V ∗ 2 ∂UA2 U ∗ ∂UA ∂VA U ∗ ,V ∗ ∂VA2 V ∗
A A A A A A
(27)
For the second derivatives, we have
∂2S
 
3k NA NB
=− + (28)
∂UA2 2 UA2 (U − UA )2

∂2S 3k (NA + NB )3
=− (29)
∂UA2 ∗
UA 2 NA NB U 2

∂2S
 
NA NB
= −k + (30)
∂VA2 VA2 (V − VA )2
∂2S (NA + NB )3
= −k (31)
∂VA2 VA∗ NA NB V 2

∂2S
=0 (32)
∂UA ∂VA
Then, near the most probable macrostate, the multiplicity Ω behaves like a two-variable Gaussian function
δUA2 δVA2
− −
σ2 σ2
Ω∝e U V (33)
q q
NA NB U 2 NA NB V 2
, where σU and σV are of the order of (NA +NB )3 and (NA +NB )3 , respectively.

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Figure 2: Initially, two ideal gases made of two different types of monatomic particles are separated by a plate
(represented by the red verticle line) that allows neither energy exchange nor particle exchange. There is also
no energy or particle exchange between the gases and the environment outside. After some time, the plate is
removed.

Problem 3 (10 points). In the class, we have mostly been discussing ideal gases made of the same type of
particles. In this problem, we consider ideal gases made of different types of monatomic particles A and B
with mass mA and mB , respectively (for example, A can be helium and B can be argon). Suppose the two
ideal gases are initially separated by a plate that does not allow either energy exchange or particle exchange
(see Fig. 2). There is also no energy or particle exchange between the gases and the environment outside
through the walls of the container. On the left side of the plate, the number of particles is NA , the energy
is UA and the volume is VA . On the right side of the plate, the number of particles is NB , the energy is UB
and the volume is VB . The two gases are in thermal equilibrium initially, and then the plate is removed.
(1) (2 points) According to the equipartition theorem, what are the temperatures of the two ideal gases
before the plate is removed? After the plate is removed and the system reaches thermal equilibrium again,
what is the final temperature according to the equipartition theorem? What is UA′ , the final energy of
particle type A after thermal equilibrium is reached after the plate is removed?
(2) (4 points) Use the result of part (1) to answer the following questions. What is the total entropy of the
combined system before and after the plate is removed? What is their difference, which is also known as
the entropy of mixing?
(3) (4 points) In the previous parts, we have used the fact that the entire system will share a single final
temperature after thermal equilibrium. In this part, we do not assume this, and we will derive it by using the
fundamental assumption of statistical mechanics and the equipartition theorem. Suppose after the plate
is removed, there is a macrostate where the energy of type-A particles is UA′ , and the energy of type-B
particles is UB′ . From the total multiplicity of the entire system, calculate the most probable value of UA′
and verify that it is identical to the answer obtained in part (1).
Solution: (1) Before we remove the plate, according to the equipartition theorem U = 32 N kT , we have

2UA
TA = (34)
3NA k
2UB
TB = (35)
3NB k
After the plate is removed, and the thermal equilibrium is reached

2(UA + UB )
T = (36)
3(NA + NB )k

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PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

The final energy of type A particle UA′ is

3
UA′ = NA kT (37)
2
NA
= (UA + UB ) (38)
NA + NB

(2) For the total entropy of the combined system before (S) and after (S ′ ) the plate is removed, we have
"  3 ! # "  3 ! #
VA 4πmA UA 2 5 VB 4πmB UB 2 5
S = NA k ln + + NB k ln + (39)
NA 3NA h2 2 NB 3NB h2 2
"  32 ! # "  32 ! #
4πmA UA′ 4πmB UB′
 
′ VA + VB 5 VA + VB 5
S = NA k ln + + NB k ln + (40)
NA 3NA h2 2 NB 3NB h2 2
The entropy of mixing ∆S is

∆S = S ′ − S (41)
  32 !   32 !
VA + VB (UA + UB )NA VA + VB (UA + UB )NB
= NA k ln + NB k ln (42)
VA UA (NA + NB ) VB UB (NA + NB )

′
∂S
(3) After the plate is removed, the most probable macrostate is featured by ∂U ′ = 0, which is similar to
A
′ ′
question 2. Thus, we also have UA /UB = NA /NB . Then, by using the equipartition theorem, we get the
thermal equilibrium TA′ = TB′ and UA′ = NAN+N
A
B
(UA + UB ).