Chapter 10.

The Boltzmann distribution law

1
Chapter 10. The Boltzmann distribution law

Example 10.2

2
Chapter 10. The Boltzmann distribution law

The Boltzmann distribution law

probability distributions from the energy levels for the system under consideration

3
Chapter 10. The Boltzmann distribution law

The Boltzmann distribution law

probability distributions from the energy levels for the system under consideration

Derivation:
System with:
N particle of a single type
t different energy levels
E j , j = 1, 2, 3, ..., t .

What to know probability p j that the system is in each level j .

(T , V , N ) are held constant
t
dF =dU − TdS =0 S = − k ∑ p j ln p j
j =1
t t

∑p j =1 =
U =
E ∑p E
j =1
j j
j =1
4
Chapter 10. The Boltzmann distribution law

The Boltzmann distribution law

probability distributions from the energy levels for the system under consideration

− E j / kT − E j / kT
e e
=p =
t
*
j

∑e
− E j / kT Q
j =1

t
Q = ∑e
− E j / kT
partition function
j =1

5
Chapter 10. The Boltzmann distribution law
Application (Example 10.2)
Maxwell-Boltzmann distribution of particle velocities.

1
ε (v) = mv 2
2

e −ε ( vx )/ kT e − mvx / 2 kT
2 1/ 2
 m  − mvx2 / 2 kT
p ( vx ) = =   e
+∞ +∞
 2π kT 
∫ ∫
− ε ( vx )/ kT − mvx / 2 kT
2
e dvx e dv x
−∞ −∞

+∞

∫e dx = π / a
− ax 2

−∞

6
Chapter 10. The Boltzmann distribution law
Application (Example 10.2)
Maxwell-Boltzmann distribution of particle velocities.

+∞ 1/ 2 +∞
 m 
∫−∞ x x x  2π kT  ∫ve
2 − mvx2 / 2 kT
v 2
x =v 2
p ( v ) dv x dvx width of the distribution
−∞

kT
vx2 =
m
1 1
m vx = kT
2
v 2 = vx2 + v y2 + vz2
2 2
1 3
m v 2 = kT
2 2
Velocity components are independent
3/ 2
 m  − mv 2 / 2 kT
p ( v) p=
( vx ) p ( v y ) p ( vz )   e
 2π kT 
7
Chapter 10. The Boltzmann distribution law

Example 10.2

8
Chapter 10. The Boltzmann distribution law
Partition function

∑e
− E j / kT
Q= = e − E1 / kT + e − E2 / kT + e − E3 / kT + ...... + e − Et / kT
j =1

• Link between macroscopic thermodynamic properties and microscopic model

• Specify how particles are partitioned through the accessible states

1 + e − ( E2 − E1 )/ kT + e − ( E3 − E1 )/ kT + ...... + e − ( Et − E1 )/ kT
Q=

Q: number of states that are effectively accessible for the system

9
Chapter 10. The Boltzmann distribution law
Q: number of states that are effectively accessible for the system

Ej → 0  Ej 1
⇒ →0 ⇒ p → ⇒ Q→t
*
j
T → ∞  kT t

E j ≠1 → ∞  E j ≠1 
 j=1
p
*
→1
⇒ →∞ ⇒  * ⇒ Q →1
T → 0  kT 
 p j≠1 → 0

t
Q = ∑e
− E j / kT

j =1

10
Chapter 10. The Boltzmann distribution law
Density of states
W (E)

Density of states, total number of

ways a system can occur in
energy level E

W ( E ) > 1 degenerate energy level

lmax
W ( El )e − El / kT
Q = ∑ W ( El )e − El / kT
sum over energy levels pl = lmax
l =1
∑ l
W (
l =1
E ) e − El / kT

11
Chapter 10. The Boltzmann distribution law
Density of states
W (E)

Density of states, total number of

ways a system can occur in
energy level E

W ( E ) > 1 degenerate energy level

lmax
W ( El )e − El / kT
Q = ∑ W ( El )e − El / kT
sum over energy levels pl = lmax
l =1
∑ l
W (
l =1
E ) e − El / kT

12
Chapter 10. The Boltzmann distribution law
Partition function

N distinguishable particles (atoms in crystals )

Q = qn

N indistinguishable particles (particles in gas )

qn
Q=
N!

13
Chapter 10. The Boltzmann distribution law
Partition function predicts thermodynamic properties

Internal energy  ∂ ln Q 
U = kT 2  
 ∂T V , N
Entropy = U
S k ln Q +
T
Helmholtz free energy F =−U TS = − k ln Q
 ∂F   ∂ ln Q 
Chemical potential µ µ=   = − kT  
 ∂N T ,V  ∂N T ,V
 ∂F   ∂ ln Q 
Pressure p=
−  =
kT  
 ∂V T , N  ∂V T , N

14
Chapter 10. The Boltzmann distribution law
Partition function predicts thermodynamic properties

Internal energy  ∂ ln Q 
U = kT 2  
 ∂T V , N
Entropy = U
S k ln Q +
T
Helmholtz free energy F =−U TS = − k ln Q
 ∂F   ∂ ln Q 
Chemical potential µ µ=   = − kT  
 ∂N T ,V  ∂N T ,V
 ∂F   ∂ ln Q 
Pressure p=
−  =
kT  
 ∂V T , N  ∂V T , N

t
Q = ∑e
− E j / kT

j =1
15
Chapter 11. Statistical mechanics of simple gases and solids

Energy fall into classes

Translation, rotation, vibration, electronic excitation

16
Chapter 11. Statistical mechanics of simple gases and solids

𝐻𝐻𝜓𝜓 = 𝐸𝐸𝜓𝜓 Schrödinger equation

𝜓𝜓 = 𝜓𝜓(𝑥𝑥, 𝑦𝑦, 𝑥𝑥) Wave function

𝜓𝜓 2 Spatial probability distribution

𝑝𝑝2 2
−ℎ2 𝑑𝑑 2
𝐻𝐻 = + 𝑉𝑉 𝑥𝑥 𝑝𝑝 =
2𝑚𝑚 4𝜋𝜋 2 𝑑𝑑𝑑𝑑 2

−ℎ2 𝑑𝑑 2 𝜓𝜓(𝑥𝑥)
𝐻𝐻 = + 𝑉𝑉 𝑥𝑥 𝜓𝜓(𝑥𝑥)
8𝜋𝜋 2 𝑚𝑚 𝑑𝑑𝑑𝑑 2

−ℎ2 𝑑𝑑 2 𝜓𝜓(𝑥𝑥)
+ 𝑉𝑉 𝑥𝑥 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝜓𝜓 𝑥𝑥 (11.4)
8𝜋𝜋 2 𝑚𝑚 𝑑𝑑𝑑𝑑 2

Only certain function 𝜓𝜓 can satisfy Eq (11.4) if E is constant.

There are multiple 𝐸𝐸𝑗𝑗 , eigenvalues of the equation. Those are energy levels we need.
𝑗𝑗 - quantum number.
17
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)

𝑉𝑉 𝑥𝑥 = 0 0 < 𝑥𝑥 < 𝐿𝐿

−ℎ2 𝑑𝑑 2 𝜓𝜓(𝑥𝑥)
+ 𝑉𝑉 𝑥𝑥 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝜓𝜓 𝑥𝑥
8𝜋𝜋 2 𝑚𝑚 𝑑𝑑𝑑𝑑 2

𝑑𝑑 2 𝜓𝜓(𝑥𝑥) 8𝜋𝜋 2 𝑚𝑚𝜀𝜀

+ 𝐾𝐾𝜓𝜓 𝑥𝑥 = 0 𝐾𝐾 =
𝑑𝑑𝑑𝑑 2 ℎ2
𝜀𝜀 – single particle

𝜓𝜓 𝑥𝑥 = 𝐴𝐴 sin 𝐾𝐾𝐾𝐾 + 𝐵𝐵 cos 𝐾𝐾𝐾𝐾

𝜓𝜓 2 0 = 𝜓𝜓 2 0 = 0 Boundary conditions

18
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)

𝑛𝑛𝑛 2
𝜀𝜀𝑛𝑛 = energy levels
8𝑚𝑚𝑚𝑚2

1
2 2 𝑛𝑛𝑛𝑛𝑛𝑛
𝜓𝜓 𝑥𝑥 = sin wave function
𝐿𝐿 𝐿𝐿

𝑛𝑛 = 1,2,3 … … …

19
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)

𝑛𝑛𝑛 2
𝜀𝜀𝑛𝑛 =
8𝑚𝑚𝑚𝑚2

20
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)
1
2 2 𝑛𝑛𝑛𝑛𝑛𝑛
𝜓𝜓 𝑥𝑥 = sin
𝐿𝐿 𝐿𝐿

21
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)
𝑛𝑛𝑛 2
𝜀𝜀𝑛𝑛 =
8𝑚𝑚𝑚𝑚2
𝑛𝑛=∞ 𝑛𝑛=∞
−𝜀𝜀𝑛𝑛 −𝑛𝑛2 ℎ2
𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = � 𝑒𝑒 𝑘𝑘𝑘𝑘 = � 𝑒𝑒 8𝑚𝑚𝐿𝐿2𝑘𝑘𝑘𝑘
𝑛𝑛=1 𝑛𝑛=1

−ℎ2
𝜃𝜃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = transition temperature
8𝑚𝑚𝐿𝐿2 𝑘𝑘

𝜃𝜃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
≪ 1 sum can be approximated as an integral
𝑇𝑇

𝑛𝑛=∞ −𝑛𝑛2 ℎ2 1/2

2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋
𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = � 𝑒𝑒 8𝑚𝑚𝐿𝐿2𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑 = 𝐿𝐿
𝑛𝑛=0 ℎ2

22
Chapter 11. Statistical mechanics of simple gases and solids
Model for translation motion (particle in a box)

−ℎ2 𝜕𝜕 2 𝜕𝜕 2 𝜕𝜕 2
+ + 𝜓𝜓 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 + 𝑉𝑉 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 𝜓𝜓 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 = ℰ𝜓𝜓 𝑥𝑥, 𝑦𝑦, 𝑧𝑧
8𝜋𝜋 2 𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝑦𝑦 2 𝜕𝜕𝑧𝑧 2

𝑉𝑉 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 = 𝑉𝑉 𝑥𝑥 + 𝑉𝑉 𝑦𝑦 + 𝑉𝑉(𝑧𝑧)

𝐻𝐻𝑥𝑥 𝜓𝜓𝑥𝑥 = ℰ𝑥𝑥 𝜓𝜓𝑥𝑥

𝐻𝐻𝑦𝑦 𝜓𝜓𝑦𝑦 = ℰ𝑦𝑦 𝜓𝜓𝑦𝑦
𝐻𝐻𝑧𝑧 𝜓𝜓𝑧𝑧 = ℰ𝑧𝑧 𝜓𝜓𝑧𝑧

𝜓𝜓 = 𝜓𝜓𝑥𝑥 𝜓𝜓𝑦𝑦 𝜓𝜓𝑧𝑧

ℎ 2 𝑛𝑛𝑥𝑥 2 𝑛𝑛𝑦𝑦 2 𝑛𝑛𝑧𝑧 2
ℰ𝑛𝑛𝑥𝑥 ,𝑛𝑛𝑦𝑦,𝑛𝑛𝑧𝑧 = + 2 + 2
8𝑚𝑚 𝑎𝑎2 𝑏𝑏 𝑐𝑐

3/2 3/2
2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 𝑉𝑉
𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑞𝑞𝑥𝑥 𝑞𝑞𝑦𝑦 𝑞𝑞𝑧𝑧 = 𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑉𝑉 = 3
ℎ2 ℎ2 Λ
23
Chapter 11. Statistical mechanics of simple gases and solids
Model for vibrations (Harmonic oscillator)

𝑘𝑘𝑠𝑠 𝑥𝑥 2
𝑉𝑉(𝑥𝑥) = square-law or parabolic potential
2

−ℎ2 𝑑𝑑 2 𝜓𝜓(𝑥𝑥) 𝑘𝑘𝑠𝑠 𝑥𝑥 2

+ 𝜓𝜓 𝑥𝑥 = 𝜀𝜀𝑣𝑣 𝜓𝜓 𝑥𝑥
8𝜋𝜋 2 𝑚𝑚 𝑑𝑑𝑑𝑑 2 2

1
𝜀𝜀𝑣𝑣 = 𝑣𝑣 + ℎ𝜈𝜈
2
𝑣𝑣 = 0,1,2,3, … …

1/2
1 𝑘𝑘𝑠𝑠
𝜈𝜈 = Vibrational frequency of the harmonic oscillator
2𝜋𝜋 𝑚𝑚

24
Chapter 11. Statistical mechanics of simple gases and solids
Model for vibrations (Harmonic oscillator)

25
Chapter 11. Statistical mechanics of simple gases and solids
Model for vibrations (Harmonic oscillator)

26
Chapter 11. Statistical mechanics of simple gases and solids
Model for vibrations (Harmonic oscillator)

1/2 1/2
1 𝑘𝑘𝑠𝑠 1 𝑘𝑘𝑠𝑠
𝜈𝜈 = → 𝜈𝜈 =
2𝜋𝜋 𝑚𝑚 2𝜋𝜋 𝜇𝜇
𝑚𝑚1 𝑚𝑚2
𝜇𝜇 =
𝑚𝑚1 + 𝑚𝑚2

𝑛𝑛=∞
−𝜈𝜈ℎ𝑣𝑣 −ℎ𝑣𝑣 −2ℎ𝑣𝑣 −3ℎ𝑣𝑣
𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 = � 𝑒𝑒 𝑘𝑘𝑘𝑘 =1+ 𝑒𝑒 𝑘𝑘𝑘𝑘 + 𝑒𝑒 𝑘𝑘𝑘𝑘 + 𝑒𝑒 𝑘𝑘𝑘𝑘 + ⋯ = 1 + 𝑥𝑥 + 𝑥𝑥 2 + ⋯
𝑣𝑣=1
0 < 𝑥𝑥 < 1

1
𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 = −ℎ𝜈𝜈
1− 𝑒𝑒 𝑘𝑘𝑘𝑘

27
Chapter 11. Statistical mechanics of simple gases and solids
Model for rotations. Rigid rotor.

𝑙𝑙 𝑙𝑙 + 1 ℎ2
𝜀𝜀𝑙𝑙 = 𝐼𝐼 = 𝜇𝜇𝑅𝑅2 moment of inertia
8𝜋𝜋 2 𝐼𝐼

For each 𝑙𝑙 there is degeneracy 2𝑙𝑙 + 1

𝑙𝑙=∞
−𝜀𝜀𝑙𝑙
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = � (2𝑙𝑙 + 1)𝑒𝑒 𝑘𝑘𝑘𝑘
𝑙𝑙=1

8𝜋𝜋 2 𝐼𝐼𝑘𝑘𝑘𝑘
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =
𝜎𝜎ℎ2

𝜎𝜎 nuclear and rotation symmetry factor

1 3
𝜋𝜋𝐼𝐼𝑎𝑎 𝐼𝐼𝑏𝑏 𝐼𝐼𝑐𝑐 2 8𝜋𝜋 2 𝑘𝑘𝑘𝑘 2
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =
𝜎𝜎 ℎ2
nonlinear molecules with three principal inertia moments 28
Chapter 11. Statistical mechanics of simple gases and solids
The electronic partition function

−Δ𝜀𝜀1 −Δ𝜀𝜀2
𝑞𝑞𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 = 𝑔𝑔𝑜𝑜 + 𝑔𝑔1 𝑒𝑒 𝑘𝑘𝑘𝑘 + 𝑔𝑔2 𝑒𝑒 𝑘𝑘𝑘𝑘 +⋯

𝑔𝑔1 electronic degeneracies

−Δ𝜀𝜀𝑖𝑖
≈ 104 -105 K
𝑘𝑘

𝑞𝑞𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 ≈ 𝑔𝑔𝑜𝑜

29
Chapter 11. Statistical mechanics of simple gases and solids
Total partition function
𝜀𝜀𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝜀𝜀𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 + 𝜀𝜀𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 + 𝜀𝜀𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 + 𝜀𝜀𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒

𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑞𝑞𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒

3/2 linear diatomic molecular

2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 1
𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑉𝑉
ℎ2
1
𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 = −ℎ𝜈𝜈
1 − 𝑒𝑒 𝑘𝑘𝑘𝑘
1 3
2
𝜋𝜋𝐼𝐼𝑎𝑎 𝐼𝐼𝑏𝑏 𝐼𝐼𝑐𝑐 2 8𝜋𝜋 𝑘𝑘𝑘𝑘 2
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 =
𝜎𝜎 ℎ2

3/2
2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 8𝜋𝜋 2 𝐼𝐼𝐼𝐼𝐼𝐼 1
𝑞𝑞𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑉𝑉 −ℎ𝜈𝜈
ℎ2 𝜎𝜎ℎ2
1 − 𝑒𝑒 𝑘𝑘𝑘𝑘

30
Chapter 11. Statistical mechanics of simple gases and solids
Ideal gas free energy

𝑞𝑞 𝑁𝑁
𝑄𝑄 =
𝑁𝑁!

𝑞𝑞 𝑁𝑁 𝑒𝑒𝑒𝑒 𝑁𝑁 𝑒𝑒𝑒𝑒
𝐹𝐹 = −𝑘𝑘𝑘𝑘ln𝑄𝑄 = −𝑘𝑘𝑘𝑘ln = −𝑘𝑘𝑘𝑘ln = −𝑁𝑁𝑘𝑘𝑘𝑘ln
𝑁𝑁! 𝑁𝑁 𝑁𝑁
𝑁𝑁
𝑁𝑁
Stirling’s approximation 𝑁𝑁! ≈
𝑒𝑒

Ideal gas presure

𝑞𝑞 = 𝑞𝑞0 𝑉𝑉
𝑒𝑒𝑞𝑞0
𝐹𝐹 = −𝑁𝑁𝑁𝑁𝑁𝑁ln𝑉𝑉 − 𝑁𝑁𝑁𝑁𝑁𝑁ln
𝑁𝑁
𝜕𝜕𝜕𝜕 𝑁𝑁𝑘𝑘𝑘𝑘
𝑝𝑝 = − = Ideal gas law!
𝜕𝜕𝜕𝜕 𝑇𝑇,𝑁𝑁
𝑉𝑉

31
Chapter 11. Statistical mechanics of simple gases and solids
Ideal gas
𝜕𝜕𝜕𝜕 𝑁𝑁𝑘𝑘𝑘𝑘
𝑝𝑝 = − = Ideal gas law
𝜕𝜕𝜕𝜕 𝑇𝑇,𝑁𝑁
𝑉𝑉

3
𝑈𝑈 = 𝑁𝑁𝑁𝑁𝑁𝑁 Ideal gas internal energy
2
3
𝑈𝑈𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 (𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛) = 𝑁𝑁𝑁𝑁𝑁𝑁
2
𝑈𝑈𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟(𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙) = 𝑁𝑁𝑁𝑁𝑁𝑁

Ideal gas entropy (Sackur-Tetrode equation)

3/2
2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 𝑒𝑒 5/2 𝑉𝑉1
𝑆𝑆 = 𝑁𝑁𝑁𝑁 ln 𝑉𝑉 ∆𝑆𝑆 = 𝑁𝑁𝑁𝑁 ln
ℎ2 𝑁𝑁 𝑉𝑉2

32
Chapter 11. Statistical mechanics of simple gases and solids
Ideal gas chemical potential

𝑝𝑝
𝜇𝜇 = 𝑘𝑘𝑘𝑘 ln 𝑜𝑜
𝑝𝑝𝑖𝑖𝑖𝑖𝑖𝑖

3/2
𝑜𝑜 2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 standard state pressure
𝑝𝑝𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑘𝑘𝑘𝑘 𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑞𝑞𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
ℎ2

33
Chapter 11. Statistical mechanics of simple gases and solids
The equipartition theorem

3
𝑈𝑈 = 𝑁𝑁𝑁𝑁𝑁𝑁 Ideal gas internal energy
2
3
𝑈𝑈𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 (𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛) = 𝑁𝑁𝑁𝑁𝑁𝑁
2
𝑘𝑘𝑘𝑘
Average energies are integral multipliers of
2

−𝜀𝜀(𝑥𝑥)
∑𝑥𝑥 𝜀𝜀(𝑥𝑥)𝑒𝑒 𝑘𝑘𝑘𝑘
𝜀𝜀 = −𝜀𝜀(𝑥𝑥)
𝑥𝑥 degree of freedom
∑𝑥𝑥 𝑒𝑒 𝑘𝑘𝑘𝑘

+∞ −𝜀𝜀(𝑥𝑥)
∫−∞ 𝜀𝜀(𝑥𝑥)𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑
𝜀𝜀 = in many cases 𝜀𝜀 𝑥𝑥 = 𝑐𝑐𝑥𝑥 2
+∞ −𝜀𝜀(𝑥𝑥)
∫−∞ 𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑

34
Chapter 11. Statistical mechanics of simple gases and solids
The equipartition theorem

+∞ −𝜀𝜀(𝑥𝑥)
∫−∞ 𝜀𝜀(𝑥𝑥)𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑
𝜀𝜀 =
+∞ −𝜀𝜀(𝑥𝑥)
in many cases 𝜀𝜀 𝑥𝑥 = 𝑐𝑐𝑥𝑥 2
∫−∞ 𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑

−𝑐𝑐𝑥𝑥 2
+∞ 2
∫−∞ 𝑐𝑐𝑥𝑥 𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑 1 1
𝜀𝜀 = 2 = 𝑘𝑘𝑘𝑘 Energy stored in every degree of freedom is 𝑘𝑘𝑘𝑘
+∞ −𝑐𝑐𝑥𝑥 2 2
∫−∞ 𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑

1 𝑘𝑘𝑘𝑘
𝜀𝜀 = 𝑐𝑐 𝑥𝑥 2 = 𝑘𝑘𝑘𝑘 𝑥𝑥 2 = fluctuations
2 2𝑐𝑐

ℎ2 2 ℎ2
𝜀𝜀𝑛𝑛𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑛𝑛 𝜀𝜀𝑙𝑙𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 2 𝑙𝑙(𝑙𝑙 + 1)
8𝑚𝑚𝑚𝑚2 8𝜋𝜋 𝐼𝐼

35
Chapter 11. Statistical mechanics of simple gases and solids
The equipartition theorem. Vibrations

1
𝜀𝜀𝑣𝑣 = 𝑣𝑣 + ℎ𝜈𝜈 linear dependence on quantum number
2

+∞ −𝑐𝑐𝑐𝑐
∫−∞ 𝑐𝑐𝑐𝑐𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑
𝜀𝜀 = 2 = 𝑘𝑘𝑘𝑘
+∞ −𝑐𝑐𝑥𝑥
∫−∞ 𝑒𝑒 𝑘𝑘𝑘𝑘 𝑑𝑑𝑑𝑑

At low 𝑇𝑇 assumption might not be valid !

Degrees of freedom are “frozen out”

36
Chapter 11. Statistical mechanics of simple gases and solids
The equipartition theorem.

37
Chapter 11. Statistical mechanics of simple gases and solids
The Einstein model of solids

If there are 𝑁𝑁 atoms in solid and each vibration should contribute 𝑘𝑘𝑘𝑘 to the energy.
The heat capacity should be 𝐶𝐶𝑣𝑣 = 3𝑁𝑁𝑁𝑁, independent of 𝑇𝑇

38
Chapter 11. Statistical mechanics of simple gases and solids
The Einstein model of solids

If there are 𝑁𝑁 atoms in solid and each vibration should contribute 𝑘𝑘𝑘𝑘 to the energy.
The heat capacity should be 𝐶𝐶𝑣𝑣 = 3𝑁𝑁𝑁𝑁, independent of 𝑇𝑇

Consider 3𝑁𝑁 distinguishable independent oscillators

1
𝑞𝑞𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 = −ℎ𝜈𝜈
this obtained from QD consideration!
1− 𝑒𝑒 𝑘𝑘𝑘𝑘

1 𝜕𝜕𝑞𝑞 𝑒𝑒 −𝛽𝛽𝛽𝛽𝛽 1
𝜀𝜀 = − = ℎ𝑣𝑣 𝛽𝛽 =
𝑞𝑞 𝜕𝜕𝛽𝛽 1 − 𝑒𝑒 −𝛽𝛽𝛽𝛽𝛽 𝑘𝑘𝑘𝑘

2
𝜕𝜕 𝜀𝜀 ℎ𝜈𝜈 𝑒𝑒 −ℎ𝜈𝜈/𝑘𝑘𝑘𝑘
𝐶𝐶𝑉𝑉 = 3𝑁𝑁 = 3𝑁𝑁𝑁𝑁
𝜕𝜕𝑇𝑇 𝑘𝑘𝑘𝑘 1 − 𝑒𝑒 −ℎ𝜈𝜈/𝑘𝑘𝑘𝑘 2

39
Chapter 11. Statistical mechanics of simple gases and solids
The Einstein model of solids

2
𝜕𝜕 𝜀𝜀 ℎ𝜈𝜈 𝑒𝑒 −ℎ𝜈𝜈/𝑘𝑘𝑘𝑘
𝐶𝐶𝑉𝑉 = 3𝑁𝑁 = 3𝑁𝑁𝑁𝑁
𝜕𝜕𝑇𝑇 𝑘𝑘𝑘𝑘 1 − 𝑒𝑒 −ℎ𝜈𝜈/𝑘𝑘𝑘𝑘 2

40