PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Solution to assignment 5 of Thermodynamics and Statistical Mechanics1

(Due on September 20 2024 at 2pm. Submit your solution to Canvas as a PDF file.)

Problem 1 (10 points). In class, we have learnt how to express the temperature and
pressure of a gas
∂S
from the perspective of statistical mechanics. Namely, the temperature T = 1/ ∂U V
and the pressure
∂S ∂T ∂P




P = T ∂V U . We have also learnt one of Maxwell’s relations, ∂V S = − ∂S V . To better understand
these concepts, we explicitly verify this Maxwell’s relation in the context of a monoatimic ideal gas made
of N particles, each of which has a mass m. Recall that the entropy of such an ideal gas as a function of
the energy U and volume V is
"  3/2 ! #
V 4πmU 5
S(U, V ) = N k ln + . (1)
N 3N h2 2

∂S


(1) (3 points) Use the microscopic definition of the temperature, T = 1/ ∂U V
, and Eq. (1) to calculate
the temperature T of the ideal gas as a function of U and V . Then show that T as a function of S and V is
 32
h2

N S −5
T = e Nk 2 . (2)
2πkm V

∂T


(2) (2 points) Calculate ∂V S
.
∂S


(3) (3 points) Use the relation P = T ∂V U
and Eq. (1) to calculate the pressure P of the ideal gas as a
function of U and V . Then show that P as a function of S and V is
2
N h2

N S −5 3
P = e N k 2 . (3)
2πV m V

(4) (2 points) Calculate ∂P

∂S V
. Comparing this result with the result in part (2), does Maxwell’s relation
∂T ∂P



∂V S = − ∂S V hold for the ideal gas?

Solution:
∂S


(1) By using T = 1/ ∂U V , we have T in terms of U and V .

2U
T = (4)
3N k
It is just the equipartition theorem for monoatimic ideal gas, and T in terms of S and V
 32
3N h2

N S −5
U= e Nk 2 (5)
4πm V

 23
h2

2U N S −5
T = = e Nk 2 (6)
3N k 2πkm V
1 You are welcome to get back with questions and clarifications if the wording of problems is ambiguous.

1
PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

(2)
 23
h2
  
∂T N S −5
=− e Nk 2 (7)
∂V S 3πkmV V

∂S


(3) By using P = T ∂V U , we have P in terms of U and V .

N kT
P = (8)
V
It is the ideal gas law, and P in terms of S and V
 23
N h2

N S −5
P = e Nk 2 (9)
2πV m V

(4)
2
h2
  
∂P 2 N S −5 3
= P = e Nk 2 (10)
∂S
V 3N k 3πkmV V
 
∂T
=− (11)
∂V S
∂T
= − ∂P



Thus, the Maxwell’s relation ∂V S ∂S V holds for the ideal gas.

Problem 2 (10 points). In class, we have learnt how to calculate the change of entropy during a quasi-
static process. In this problem, we apply it to a real example.
The heat capacity of one mole of graphite at constant pressure takes the following form over a fairly wide
range of temperatures
c
CP = a + bT − (12)
T2
where a = 16.86 J/K, b = 4.77 × 10−3 J/K2 , and c = 8.54 × 105 J·K. Suppose that a mole of graphite is
slowly heated at constant pressure from 298 K to 500 K. Calculate the increase in its entropy during this
process.
Solution: In this process,
Z T2
CP
∆S = T (13)
T1 T
T2 c 1 1
= a ln + b(T2 − T1 ) + ( 2 − 2 ) (14)
T1 2 T2 T1
≈ 6.59 J/K (15)

Problem 3 (10 points). In class, we often discuss quasi-static processes, but also briefly talk about
non-quasi-static processes. In this problem, we consider an example of non-quasi-static process.

2
PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

A cylinder contains one liter of air at room temperature (300 K) and atmospheric pressure (105 N/m2 ). At
one end of the cylinder is a massless piston, whose surface area is 0.01 m2 . Suppose that you push the piston
in very suddenly, exerting a force of 2000 N. The piston moves only one millimeter, before it is stopped by
an immovable barrier of some sort.
(1) (2 points) How much work have you done on this system?
(2) (2 points) How much heat has been added to the gas?
(3) (2 points) Assuming that all the energy added goes into the gas (not the piston or cylinder walls), by
how much does the internal energy of the gas increase?
(4) (4 points) Use the thermodynamic identity to calculate the change in the entropy of the gas (once it has
again reached equilibrium).

Solution:
(1) For the work done to the gas W ,

W =F·x=2 J (16)

(2) The gas doesn’t absorb any heat in the sudden process, Q = 0
(3) For the change of the internal energy ∆U , we have

∆U = W + Q = 2 J (17)

(4) For the change of the entropy ∆S, we can construct a reversible process between the initial state and
the final state. If the cylinder is not adiabatic. After reaching the equilibrium, the final state is still at the
room temperature T0 , so we can assume the reversible process is a isothermal process. Then, we have the
thermodynamic identity
Z f
dU + P dV
∆S = (18)
i T
Z Vf
∆U Nk
= + dV (19)
T0 Vi V
∆U Pi Vi Vf
= + ln (20)
T0 T0 Vi

, where ∆U = 0 (∆T = 0), Pi = 105 Pa, Vi = 10−3 m3 , Vf = 0.99 × 10−3 m3 and T0 = 300 K. Thus, we
have
∆S ≈ −3.35 × 10−3 J/K (21)
If the cylinder is adiabatic. We construct an adiabatic reversible compression process.
Z f
dQ
∆S = (22)
i T
=0 (23)