Week Date Schedules Ch.

HW
1 9/9 中秋節遇例假日補假
2 9/16 0th law of thermodynamics; 1st law of thermodynamics 1, 2 √
3 9/23 Heat engine; Carnot engine; Efficiency; Thermodynamic temperature 3
4 9/30 2nd law of thermodynamics; Entropy; Combination of 1st and 2nd law 3 √
2nd law of thermodynamics; Auxiliary functions (H, A, G)
Calendar

5 10/7 3, 5
6 10/14 Auxiliary functions (H, A, G); Maxwell equation 5 √
7 10/21 Conditions for equilibrium -
8 10/28 期中考(請親自出席應考)
9 11/4 Statistical thermodynamics; Macro and micro states 4
10 11/11 Configurational entropy; thermal entropy; Boltzmann equation; U, Cv 4, 6 √
11 11/18 Heat Capacity, enthalpy, entropy as a function of T 6
12 11/25 S(T) and 3rd law of thermodynamics; Effect of P; Phase equilibria 6 √
13 12/2 台大運動會放假 6, 7
14 12/9 Phase equilibria; Unary (one-component) heterogeneous systems 7 √
15 12/16 Behavior of ideal gases to real gases 8
16 12/23 期末考(請親自出席應考)
Feedback

2
 Entropy again!

One step back, we recall that

𝐵 𝛿𝑄
∆𝑆𝐴→𝐵,𝑟𝑒𝑣 = ‫𝐴׬‬ + 𝑆𝑔𝑒𝑛
𝑇

Previously we kind of understand entropy from the point of

view of “classical” thermodynamics, where we look at the
system assuming that it’s a black box. That is to say,
previously we looked at the “macroscopic” state, yet
ignoring individual atoms or molecules. Is the approach
correct actually?

3
 A simple feeling about entropy
From solid to liquid to gas of water of the same amount:

Latent heat of melting under constant P

𝑆𝑔𝑎𝑠 > 𝑆𝑙𝑖𝑞𝑢𝑖𝑑 > 𝑆𝑠𝑜𝑙𝑖𝑑

∆𝐻𝑚
∆𝑆𝑚 = > 0 when melting happens.
𝑇𝑚
𝐵𝑢𝑡 𝑤ℎ𝑒𝑛 𝑠𝑜𝑙𝑖𝑑𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛 ℎ𝑎𝑝𝑝𝑒𝑛𝑠, 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒𝑠?
Gibbs: Entropy is a measure of degree of “mixed-up-ness” 熵ㄉㄧ
4
 Entropy from the microscopic point of view

We then look at systems that contain large number of

atoms or molecules.
Then, what we want to study are the distribution of the
microscopic states and also the most probable state.
Think of one mole of aluminum atoms (6.023 × 1023 atoms)
at room temperature, 1 atm. The occupied volume is about
10 cm3. And do these atoms all have the same energy? (Of
course not!)

Note: Now we tend to look at systems of constant V, U, and n. Why?

Microcanonical ensemble
5
 Most probable state ‒ An example
Example: Let’s look at one example. There are four energy levels: 𝜀0 , 𝜀1 , 𝜀2 , 𝜀3 , of
four different energies, 0, 1u, 2u, 3u, respectively. There are 3 distinguishable
states at each level, but the 3 atoms are indistinguishable. Macroscopically we
measure that the system has an energy of 3u. What is the most probable state?

State I State II State III

3u 𝜀3 𝜀3 𝜀3
2u 𝜀2 𝜀2 𝜀2
1u 𝜀1 𝜀1 𝜀1
0 𝜀0 𝜀0 𝜀0
Microstates
Distinguishable state numbers: 1 6 3
Macrostate
 How about for n particles?

𝑛𝑟 𝜀𝑟 ෍ 𝑛𝑖 = 𝑛
𝑖=0
……

𝑛!
𝑛3 𝜀3 Ω=
ς𝑖=𝑟
𝑖=0 𝑛𝑖 !
𝑛2 𝜀2
Where Ω is the number of arrangements.
𝑛1 𝜀1
For example, Ω for the most probable state in
𝑛0 𝜀0 the previous case is 6. But what about 1 mole,
i.e., 6.023 × 1023 atoms …?
7
 Stirling’s approximation
When X is huge, ln 𝑋! = 𝑋 ln 𝑋 − 𝑋
Taking ln here is on purpose! 𝑖=𝑟

ln Ω = 𝑛 ln 𝑛 − 𝑛 − ෍(𝑛𝑖 ln 𝑛𝑖 − 𝑛𝑖 )
𝑖=0
Our final goal is to know what is the condition for the
most probable case, i.e., when Ω is at a maximum.
𝑖=𝑟 𝑖=𝑟

𝑑 ln Ω = − ෍ 𝑑𝑛𝑖 ln 𝑛𝑖 + 𝑑𝑛𝑖 − 𝑑𝑛𝑖 = − ෍ ln 𝑛𝑖 𝑑𝑛𝑖 = 0

𝑖=0 𝑖=0

8
 Two constraints
𝑖=𝑟 𝑖=𝑟
Particle number: ෍ 𝑛𝑖 = 𝑛 ෍ 𝑑𝑛𝑖 = 0
𝑖=0 𝑖=0
𝑖=𝑟 𝑖=𝑟

Total energy: ෍ 𝑛𝑖 𝜀𝑖 = 𝑈 ෍ 𝜀𝑖 𝑑𝑛𝑖 = 0

𝑖=0 𝑖=0
𝑖=𝑟 0 Lagrange multiplier, where 𝛼, 𝛽 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠

𝑑 ln Ω = − ෍(ln 𝑛𝑖 + 𝛼 + 𝛽𝜀𝑖 )𝑑𝑛𝑖 = 0

𝑖=0

What does this equation imply?

9
 Particle distribution with energy
−𝛼−𝛽𝜀𝑖
ln 𝑛𝑖 + 𝛼 + 𝛽𝜀𝑖 = 0 𝑛𝑖 = 𝑒
Partition function, P
𝑖=𝑟 𝑖=𝑟

෍ 𝑛𝑖 = 𝑛 = 𝑒 −𝛼 ෍ 𝑒 −𝛽𝜀𝑖
𝑖=0 𝑖=0

−𝛼
𝑛
𝑒 =
𝑃
𝑛 −𝛽𝜀
𝑛𝑖 = ∙ 𝑒 𝑖
𝑃 10
 The influence of T is reflected in β
𝑛 −𝛽𝜀
𝑛𝑖 = ∙ 𝑒 𝑖
𝑃

𝛽 is a function of temperature, it seems! But what are 𝛼 and 𝛽,exactly?

11
 What is β
𝑖=𝑟

Recall that ln Ω = 𝑛 ln 𝑛 − 𝑛 − ෍(𝑛𝑖 ln 𝑛𝑖 − 𝑛𝑖 )

𝑖=0
𝑖=𝑟

ln Ω = 𝑛 ln 𝑛 − ෍(𝑛𝑖 ln 𝑛𝑖 )
𝑖=0 𝑛 −𝛽𝜀
𝑛𝑖 = ∙ 𝑒 𝑖
𝑃
𝑖=𝑟
𝑛 −𝛽𝜀 𝑛 −𝛽𝜀
ln Ω = 𝑛 ln 𝑛 − ෍[ ∙ 𝑒 𝑖 ∙ ln ∙𝑒 𝑖 ]
𝑃 𝑃
𝑖=0

12
 What is β – con’d
𝑖=𝑟
𝑛 −𝛽𝜀 𝑛 −𝛽𝜀
ln Ω = 𝑛 ln 𝑛 − ෍ ∙ 𝑒 𝑖 ∙ ln ∙𝑒 𝑖
𝑃 𝑃
𝑖=0
𝑖=𝑟
𝑛 −𝛽𝜀 𝑛
ln Ω = 𝑛 ln 𝑛 − ෍ ∙ 𝑒 𝑖 ∙ (ln − 𝛽𝜀𝑖 )
𝑃 𝑃
𝑖=0
𝑖=𝑟
𝑛 𝑛 −𝛽𝜀 𝑛 −𝛽𝜀
ln Ω = 𝑛 ln 𝑛 − ෍ ( ∙ ln ∙ 𝑒 𝑖 − ∙ 𝑒 𝑖 ∙ 𝛽𝜀𝑖 )
𝑃 𝑃 𝑃
𝑖=0 P ?
𝑖=𝑟 𝑖=𝑟
𝑛 𝑛 −𝛽𝜀𝑖
𝑛𝛽
ln Ω = 𝑛 ln 𝑛 − ( ∙ ln ∙ ෍ 𝑒 − ∙ ෍ 𝑒 −𝛽𝜀𝑖 ∙ 𝜀𝑖 )
𝑃 𝑃 𝑃
𝑖=0 𝑖=0 13
 What is β – con’d
P ?
𝑖=𝑟 𝑖=𝑟
𝑛 𝑛 −𝛽𝜀𝑖
𝑛𝛽
ln Ω = 𝑛 ln 𝑛 − ( ∙ ln ∙ ෍ 𝑒 − ∙ ෍ 𝑒 −𝛽𝜀𝑖 ∙ 𝜀𝑖 )
𝑃 𝑃 𝑃
𝑖=0 𝑖=0

𝑖=𝑟
𝑛 𝑛 −𝛽𝜀
ln Ω = 𝑛 ln 𝑛 − (𝑛 ∙ ln − 𝛽 ∙ ෍ ∙ 𝑒 𝑖 ∙ 𝜀𝑖 )
𝑃 𝑃
𝑖=0

𝑖=𝑟 𝑖=𝑟
𝑛 −𝛽𝜀
𝑈 = ෍ 𝑛𝑖 𝜀𝑖 = ෍ ∙ 𝑒 𝑖 ∙ 𝜀𝑖
𝑃
𝑖=0 𝑖=0
14
 What is β – con’d
𝑛
ln Ω = 𝑛 ln 𝑛 − 𝑛 ∙ ln + 𝛽 ∙ 𝑈
𝑃
ln Ω = 𝑛 ln 𝑃 + 𝛽 ∙ 𝑈

𝒅 𝐥𝐧 𝜴 = 𝛽 ∙ 𝑑𝑈 = 𝜷 ∙ 𝑻𝒅𝑺

1 1
𝑺= ln 𝜴 = 𝒌 𝒍𝒏 𝜴 𝛽=
𝛽𝑇 𝑘𝑇
Boltzmann constant
𝑅
= =
𝑁0
15
 α, β, P, and ni

𝑖=𝑟 𝑖=𝑟
1 −𝛽𝜀𝑖 −
𝜀𝑖
𝛽= 𝑃 = ෍𝑒 = ෍ 𝑒 𝑘𝑇
𝑘𝑇
𝑖=0 𝑖=0

𝜀𝑖 𝜀𝑖
𝑖=𝑟 −𝑘𝑇 −
σ𝑖=0 𝑒 𝑛𝑖 𝑒 𝑘𝑇
𝛼 = ln =
𝑛 𝑛 𝑃

16
Boltzmann equation

17
 An example: heat flow

Reached equilibrium
Towards equilibrium
A B A B A B

TA > TB TA > TB TA = TB
ΩA ΩB ΩA ΩA
𝑑𝑆 = 𝑘 ∙ 𝑑 ln Ω𝐴 Ω𝐵 = 𝑘(𝑑 ln Ω𝐴 + 𝑑 ln Ω𝐵 ) 𝑑𝑆 = 𝑘 ∙ 𝑑 ln Ω𝐴 Ω𝐵 = 0
𝑇𝐴𝑑𝑆𝐴 + 𝑇𝐵𝑑𝑆𝐵 = 𝑇𝐴 ∙ 𝑘 ∙ 𝑑 ln Ω𝐴 + 𝑇𝐵 ∙ 𝑘 ∙ 𝑑 ln Ω𝐵 = 0
𝑇𝐴 − 𝑇𝐵
𝑑𝑆 = 𝑑 ln Ω𝐵 > 0
𝑇𝐴 18
 Thermal versus configurational entropy

Up to now, entropy was considered as number of ways

by which energy can be distributed among identical
particles. And such entropy is called “thermal entropy”.
Nevertheless, entropy can also be considered in terms
of number of ways particles are distributed in space,
named “configurational entropy”. Check the next page
for an example:

19
 An example: Configurational entropy

Way: 1 Ways: 16 Ways: 36

Total: 70

8!
𝐴𝑙𝑠𝑜,
4! 4!
Ways: 16 Way: 1 20
 An example: Configurational entropy

U, V, n all remain constant

Way: 1 Ways: 36
The only change from left to right is the “mix-up-ness”. Recall that
𝑆 = 𝑘 ln Ω, where Ω is all the probable states, then from the unmixed
state to the mixed state, dS = 𝑘 ln 36, which is positive.
21
 The total entropy

Therefore, a short conclusion is that the total entropy of a system

consists of thermal part Sth and configurational part, Sconf.

𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑡ℎ + 𝑆𝑐𝑜𝑛𝑓

= 𝑘 ln Ω𝑡ℎ + 𝑘 ln Ω𝑐𝑜𝑛𝑓

= 𝑘 ln(Ω𝑡ℎ ∙ Ω𝑐𝑜𝑛𝑓 )
※Beware of the “non-ideal” mixing!
22
 Week Date Schedules Ch. HW
1 9/9 中秋節遇例假日補假
2 9/16 0th law of thermodynamics; 1st law of thermodynamics 1, 2 √
3 9/23 Heat engine; Carnot engine; Efficiency; Thermodynamic temperature 3
4 9/30 2nd law of thermodynamics; Entropy; Combination of 1st and 2nd law 3 √
2nd law of thermodynamics; Auxiliary functions (H, A, G)
Calendar

5 10/7 3, 5
6 10/14 Auxiliary functions (H, A, G); Maxwell equation 5 √
7 10/21 Conditions for equilibrium -
8 10/28 期中考(請親自出席應考)
9 11/4 Statistical thermodynamics; Macro and micro states 4
10 11/11 Configurational entropy; thermal entropy; Boltzmann equation; U, Cv 4, 6 √
11 11/18 Heat Capacity, enthalpy, entropy as a function of T 6
12 11/25 S(T) and 3rd law of thermodynamics; Effect of P; Phase equilibria 6 √
13 12/2 台大運動會放假 6, 7
14 12/9 Phase equilibria; Unary (one-component) heterogeneous systems 7 √
15 12/16 Behavior of ideal gases to real gases 8
16 12/23 期末考(請親自出席應考)
Numerical example – 1

24
 𝜀𝑖 𝑖+0.5 ℎ𝑣
− −
𝑛𝑖 𝑒 𝑘𝑇 𝑒 𝑘𝑇
= =
𝑛 𝑃 𝑃
0.5 ℎ𝑣
− 𝑛0 ℎ𝑣
𝑛0 𝑒 𝑘𝑇 = 𝑒 𝑘𝑇 = 4
= =1 𝑛1
𝑛 𝑃
1.5 ℎ𝑣
− ℎ𝑣
𝑛1 𝑒 𝑘𝑇 = 1.386
= = 0.25 𝑘𝑇
𝑛 𝑃
25
 ℎ𝑣
= 1.386
𝑘𝑇
2.5 ℎ𝑣
−
𝑛2 𝑒 𝑘𝑇 −
ℎ𝑣
= = 0.25 × 𝑒 𝑘𝑇 = 0.0625
𝑛 𝑃
3.5 ℎ𝑣
−
𝑛3 𝑒 𝑘𝑇 −
ℎ𝑣
= = 0.0625 × 𝑒 𝑘𝑇 = 0.015625
𝑛 𝑃

𝑇 = 2424.6 𝐾
26
 Numerical example – 2

N0 = 6.023 × 1023
(𝑁0 )!
𝑆 = 𝑘 ln(Ω𝑐𝑜𝑛𝑓 ) = 𝑘 ln
(0.015𝑁0 )! (0.236𝑁0 )! (0.226𝑁0 )! (0.523𝑁0 )!

= (1.38 × 10−23 ) × (6.498 × 1023 )

= 8.97 𝐽/𝐾
27
A from P (partition function)
Recall that ln Ω = 𝑛 ln 𝑃 + 𝛽 ∙ 𝑈
𝑇𝑘 ln Ω = 𝑛𝑘𝑇 ln 𝑃 + 𝑈
S
𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝐴 = 𝑈 − 𝑇𝑆
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑤𝑒 𝑔𝑒𝑡 𝑨 = −𝒏𝒌𝑻 𝒍𝒏 𝑷
Once we know i,
𝑖=𝑟 we know P, and A
𝜀𝑖
− can be derived!!
𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝑃 = ෍ 𝑒 𝑘𝑇
𝑖=0
28
 S, U, Cv from P (partition function)
𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝑑𝐴 = −𝑆 ∙ 𝑑𝑇 − 𝑃 ∙ 𝑑𝑉
𝜕𝐴 𝝏 𝐥𝐧 𝑷
𝑺 = −( )𝑉 = 𝒏𝒌 𝐥𝐧 𝑷 + 𝒏𝒌𝑻( )𝑽
𝜕𝑇 𝝏𝑻
𝟐
𝝏 𝐥𝐧 𝑷
𝑼 = A + TS = 𝒏𝒌𝑻 ( )𝑽
𝝏𝑻
𝟐
𝜕𝑈 𝝏 𝐥𝐧 𝑷 𝟐
𝝏 𝐥𝐧 𝑷
𝒄𝑽 = ( )𝑉 = 𝟐𝒏𝒌𝑻( )𝑽 +𝒏𝒌𝑻 ( 𝟐
)𝑽
𝜕𝑇 𝝏𝑻 𝝏𝑻
𝑇𝑉𝛼 2
(𝑐𝑃 − 𝑐𝑉 = )
𝛽 29
 An example: Two energy levels
Assume that a system has two energy levels, 𝜀1 = 𝜀; 𝜀2 = 2𝜀.
Please calculate n1, n2, ( A, S, U, Cv ) of the system.
HW!
First calculate the partition function, P.
𝑖=2
𝜀 𝜀 𝜀
− 𝑖 − −
𝑃= ෍ 𝑒 𝑘𝑇 =𝑒 𝑘𝑇 (1 + 𝑒 𝑘𝑇 )
𝑖=1
Since later on we will use frequently ln 𝑃, so it’s better to calculate it.
𝜀 −
𝜀
ln 𝑃 = − + ln(1 + 𝑒 𝑘𝑇 )
𝑘𝑇
30
 𝜀1 𝜀
− −
𝑛1 𝑒 𝑘𝑇 𝑒 𝑘𝑇 1
= = 𝜀 𝜀 = 𝜀
𝑛 𝑃 − − −
𝑒 𝑘𝑇 (1 + 𝑒 𝑘𝑇 ) (1 + 𝑒 𝑘𝑇 )
𝜀2 2𝜀
− −
𝑛2 𝑒 𝑘𝑇 𝑒 𝑘𝑇 1
= = 𝜀 𝜀 = 𝜀 𝜀
𝑛 𝑃 − − + −
𝑒 𝑘𝑇 (1 + 𝑒 𝑘𝑇 ) 𝑒 𝑘𝑇 (1 + 𝑒 𝑘𝑇 )

Let’s consider two extremely, T = 0 and T = .

For T = 0, n1/n → 1 and n2/n → 0

For T = , n1/n → 0.5 and n2/n → 0.5
They are quite in line with our feelings, right?
31
 DeHoff Ch. 6

Einstein’s model Gaskell Ch. 6

𝑖=𝑟 𝑖=𝑟 Gaskell

Crystalline solid 𝑛 −𝛽𝜀
𝑈 = ෍ 𝑛𝑖 𝜀𝑖 = ෍ ∙ 𝑒 𝑖 ∙ 𝜀𝑖
𝑃
𝑖=0 𝑖=0

Einstein: for a simple cubic, No

atoms have 3No bonds (oscillators).
1
He shows that 𝜀𝑖 = 𝑖 + ℎ, which
2
means that the energy is related to
the frequency and is quantized.
32
 DeHoff Ch. 6

Einstein’s model
𝝏 𝐥𝐧 𝑷
𝟐
𝑼 = A + TS = 𝒏𝒌𝑻 ( )𝑽
𝝏𝑻
𝑖=𝑟
𝜀𝑖 DeHoff
−
𝑃= ෍ 𝑒 𝑘𝑇
𝑖=0

Einstein: for a simple cubic, No atoms

have 3No bonds (oscillators), and
1
assume that 𝜀𝑖 = 𝑖 + ℎ
2
33
 DeHoff Ch. 6
Einstein’s model
𝑖+ ℎ
𝑖=𝑟 1 𝑖=𝑟
2 ℎ 𝑖ℎ
− − −
𝑃= ෍𝑒 𝑘𝑇 =𝑒 2𝑘𝑇 ෍𝑒 𝑘𝑇
𝑖=0 𝑖=0

Now we assume that r →  (cf, the two energy level case

we have just met), and then we’ll have by math:
∞
−𝑖𝑥
1
෍𝑒 =
1 − 𝑒 −𝑥
𝑖=0
ℎ 1
−
𝑃= 𝑒 2𝑘𝑇 ∙ ℎ
−
1−𝑒 𝑘𝑇
34
 DeHoff Ch. 6
Einstein’s model
ℎ 1
−
𝑃= 𝑒 2𝑘𝑇 ∙ ℎ
−
1−𝑒 𝑘𝑇

ℎ ℎ
−
ln 𝑃 = − − ln(1 − 𝑒 𝑘𝑇 )
2𝑘𝑇

ℎ
−
2
𝜕 ln 𝑃 3 [1 + 𝑒 𝑘𝑇 ]
𝑈 = 3𝑁0 𝑘𝑇 ( )𝑉 = 𝑁0 ℎ ℎ
𝜕𝑇 2 −
[1 − 𝑒 𝑘𝑇 ]

HW 35
 DeHoff Ch. 6
How about Cv?

𝜕𝑈 3 1 ℎ ℎ
−
𝑐𝑉 = ( )𝑉 = 𝑁0 ℎ[ ℎ ∙ 𝑒 𝑘𝑇
2
−
𝜕𝑇 2 − 𝑘𝑇
1 − 𝑒 𝑘𝑇

ℎ ℎ −2 ℎ ℎ
− − −
(1 + 𝑒 𝑘𝑇 ) 1− 𝑒 𝑘𝑇 (−𝑒 𝑘𝑇 ) 2
]
𝑘𝑇

ℎ ℎ
− +
ℎ 2 𝑒 𝑘𝑇 ℎ 2 𝑒 𝑘𝑇
= 3𝑁0 𝑘( ) ∙ = 3𝑁0 𝑘( ) ∙
𝑘𝑇 ℎ 2 𝑘𝑇 ℎ 2
1− 𝑒 − 𝑘𝑇 𝑒 +
𝑘𝑇 −1
DeHoff Gaskell 36
 DeHoff Ch. 6
How about Cv?
ℎ
Set = 𝜃𝐸𝑖𝑛𝑠𝑡𝑒𝑖𝑛 , called Einstein temperature:
𝑘
𝜃𝐸
+
𝜃𝐸 2 𝑒 𝑇
𝑐𝑉 = 3𝑁0 𝑘( ) ∙ 2
𝑇 𝜃
+ 𝐸
𝑒 𝑇 −1
Dulong-Petit Rule: for solid elements, when T, cv → 3R

1. Single frequency
2. Independent vibration

37
 DeHoff Ch. 6
Einstein versus Debye models
Gaskell Ch. 6
9𝑁 2
𝑔  = 3  , 𝑤ℎ𝑒𝑟𝑒 𝑚 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦
𝑚
𝜃𝐷
𝑇
𝑇 3 𝑥 4 ∙ 𝑒 −𝑥
𝑐𝑉 = 9𝑅( ) ∙ න 𝑑𝑥 ℎ
𝜃𝐷 (1 − 𝑒 )−𝑥 2 𝑥=
𝑘𝑇
0
25.98

𝑇 3
𝑐𝑉 = 1944( )
𝜃𝐷
(Debye’s T3 law)
38
 DeHoff Ch. 6
Monatomic ideal gas model

Kinetic energies not quantized

39
V
 DeHoff Ch. 6
Monatomic ideal gas model

40
 DeHoff Ch. 6
Monatomic ideal gas model
𝐴 𝑃

41
 DeHoff Ch. 6
Monatomic ideal gas model

42
 DeHoff Ch. 6
Ideal gas equation
𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝑑𝐴 = −𝑆 ∙ 𝑑𝑇 − 𝑃 ∙ 𝑑𝑉

𝜕𝐴 1
−𝑃 = = −𝑁0 𝑘𝑇
𝜕𝑉 𝑇
𝑉
𝑃𝑉 = 𝑁0 𝑘𝑇 = 𝑅𝑇

Avogadro’s number Gas constant

Boltzmann constant

It is shown that two constants are linked by 𝑁0 .

43
 How about diatomic gas molecule?
equipartition theorem
Besides translational energy…

44
 Homework 4 (due date: 11/19)
1. (Stirling’s approximation) Show that when X is huge, ln 𝑋! =
𝑋 ln 𝑋 − 𝑋
2. A system consists of totally 1 mole of atoms A and B, i.e., XA +
XB = 1 (mole). Show that the configurational entropy can be
expressed as ∆𝑆 = −𝑅(𝑋𝐴 𝑙𝑛 𝑋𝐴 + 𝑋𝐵 𝑙𝑛 𝑋𝐵 )
3.

45
(4.1, 4.3, 4.4 from Gaskell 6th edition)
 Homework 4 (due date: 11/19)
4.

5.

46
(4.1, 4.3, 4.4 from Gaskell 6th edition)
 Homework 4 (due date: 11/19)
6. We derived n1 and n2 in the class, please derive on your own A,
S, U, Cv for two-energy level system.
ℎ
7. −
𝜕 ln 𝑃
2
3 [1 + 𝑒 𝑘𝑇 ]
𝑆ℎ𝑜𝑤 𝑡ℎ𝑎𝑡 𝑈 = 3𝑁0 𝑘𝑇 ( )𝑉 = 𝑁0 ℎ ℎ
𝜕𝑇 2 −
[1 − 𝑒 𝑘𝑇 ]
8. At ordinary temperatures and pressures the constant pressure
heat capacity of ammonia (NH3) is 35 J/mol. Apply the principle of
equipartition of energy to speculate on the spatial arrangement of
the atoms in the ammonia molecule. (Adapted from 6.11 from DeHoff 2nd edition)
47