PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

Assignment 7 of Thermodynamics and Statistical Mechanics1

(Due on October 11 2024 at 2pm. Submit your solution to Canvas as a PDF file.)

Problem 1 (10 points). In class, we have learnt the Gibbs-Duhem relation, i.e., SdT − V dP + N dµ = 0.
To better understand the meaning of this relation, in this problem, we explicitly check this relation for a
monatomic ideal gas. Denote the particle number of this gas by N , the energy of the gas by U and the
volume of the gas by V . The entropy of this gas as a function of N , U and V is
"  3 ! #
V 4πmU 2 5
S(N, U, V ) = N k ln + (1)
N 3N h2 2

where m is the mass of a particle.

(1) (1 points) Calculate the temperature T , pressure P and chemical potential µ of this gas. Express the
answer in terms of N , U and V .
(2) (2 points) Calculate the three differentials dT , dP and dµ. Express the answer in terms of N , U and V
as well as their differentials dN , dU and dV .
(3) (2 points) Explicitly show that SdT − V dP + N dµ = 0 using the results of part (2).
(4) (1 points) In the above, we express everything in terms of N , U and V and their differentials. Below we
would like to express everything in terms of P , T and V and their differentials. Write down the expressions
of S, N and µ in terms of P , T and V .
(5) (2 points) Calculate the differential dµ. Express the answer in terms of P , T and V and their differentials.
(6) (2 points) Explicitly show that SdT − V dP + N dµ = 0 using the results of part (5).
Solution:
1 P µ
(1) By using dS = T dU + T dV − T dN , we have
 −1
∂S 2U
T = = (2)
∂U V,N 3N k
 
∂S 2U
P =T = (3)
∂V U,N 3V
    32 !
∂S 2U V 4πmU
µ = −T =− ln (4)
∂N U,V 3N N 3N h2

(2) By using the results of (1), we have

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

     
∂T ∂T ∂T
dT = dU + dV + dN (5)
∂U V,N ∂V U,N ∂N U,V
2 2U
= dU − dN (6)
3N k 3N 2 k

     
∂P ∂P ∂P
dP = dU + dV + dN (7)
∂U V,N ∂V U,N ∂N U,V
2 2U
= dU − dV (8)
3V 3V 2

     
∂µ ∂µ ∂µ
dµ = dU + dV + dN (9)
∂U V,N ∂V U,N ∂N U,V
  32 ! !   32 ! !
2 V 4πmU 1 2U 2U V 4πmU 5U
= − ln − dU − dV + ln + dN (10)
3N N 3N h2 N 3V N 3N 2 N 3N h2 3N 2

(3) In this question, we check SdT − V dP + N dµ = 0.

"  3 ! #!
2S 2 2 V 4πmU 2
SdT − V dP + N dµ = − − ln +1 dU (11)
3N k 3 3 N 3N h2
 
2U 2U
+ − dV (12)
3V 3V
"  3 ! #!
2U S 2U V 4πmU 2 5U
+ − + ln + dN (13)
3N 2 k 3N N 3N h2 3N
=0 (14)

(4) In terms of T , P and V , we have

3
U (T, P, V ) = PV (15)
2

PV
N (T, P, V ) = (16)
kT
"   32 ! #
PV kT 2πmkT 5
S(T, P, V ) = ln + (17)
T P h2 2

  32 !
kT 2πmkT
µ(T, P, V ) = −kT ln (18)
P h2

2
PC2135 Lecturer: Liujun Zou TA: Jiulin Tang

(5) By using the results of (4), we have

     
∂µ ∂µ ∂µ
dµ = dT + dP + dV (19)
∂T P,V ∂P T,V ∂V T,P
 3 ! !
kT 2πmkT 2 5 kT
= −k ln − k dT + dP (20)
P h2 2 P

(6) Thus, again, we have

"   32 ! #!  
kT 2πmkT 5 N kT
SdT − V dP + N dµ = S + −N k ln − Nk dT + −V dP (21)
P h2 2 P
=0 (22)