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 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 on H and S 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

TA 維晏 will post the correct reference answer to NTUCool.

So please check the answer first and if there is still doubt
or question please contact me!

Instead of Actually I am more like

By quick thinking no. Why not?

I will try to improve it now!

2
Feedback – correction

3
Feedback – clarification

4
 Feedback – T(K)
1. We can design a sophisticated
experiment to measure the amount of q1 0.6% atm
and q2. 0.01°C
2. Definition by the triple point of the phase
diagram of ice-liquid-gas of pure water.

By definition (10th General

Conference on Weights
and Measures, 1954):
273.16 °K

By definition (13th General

Conference on Weights and
Measures, 1967): The kelvin,
unit of thermodynamic
temperature, is equal to the
fraction 1/273.16 of the
thermodynamic temperature
of the triple point of water.
5
 Recap
From a Carnot engine, η = η(TH,TL)
𝑄𝐿 𝑓 𝑇𝐿 𝑇𝐿
1 − η 𝑇𝐻, 𝑇𝐿 = = = 𝑏𝑦 𝑐𝑜𝑛𝑣𝑒𝑛𝑡𝑖𝑜𝑛 =
𝑄𝐻 𝑓 𝑇𝐻 𝑇𝐻

For a normal engine:

𝑄𝐿,𝑖𝑟𝑟 𝑇𝐿
η=1− ≤1−
𝑄𝐻,𝑖𝑟𝑟 𝑇𝐻

6
 Clausius inequality

𝐹𝑟𝑜𝑚 𝑡ℎ𝑒 𝐶𝑎𝑟𝑛𝑜𝑡 𝑒𝑛𝑔𝑖𝑛𝑒 𝑒𝑥𝑒𝑟𝑐𝑖𝑠𝑒, 𝑤𝑒 𝑔𝑒𝑡

𝑄𝐻,𝑖𝑟𝑟 𝑄𝐿,𝑖𝑟𝑟
− ≤0
𝑇𝐻 𝑇𝐿
Gradually, we see the form of entropy.

𝛿𝑄
𝑚𝑜𝑟𝑒 𝑔𝑒𝑛𝑒𝑟𝑎𝑙𝑙𝑦, 𝑤𝑒 𝑐𝑎𝑛 𝑤𝑟𝑖𝑡𝑒 ර ≤0
𝑇

7
 Example - 1
A heat engine receives 800 kJ heat from a 1200 K
heat reservoir and uses 300 kJ to do work. The rest
500 kJ is dumped to a 300 K lower-temperature
1200 K sink. Try to use (a) Carnot engine principle and (b)
High-temp heat reservoirs
Clausius inequality to tell whether the engine exists.
800 kJ
QH 𝑇𝐿 300
η (𝑟𝑒𝑣) = 1 − =1− = 0.75
W 𝑇𝐻 1200
300 kJ
𝑄𝐿 500
η (𝑒𝑛𝑔𝑖𝑛𝑒) = 1 − =1− = 0.375
𝑄𝐻 800
500 kJ QC
Low-temp heat reservoirs
300 K 𝑄𝐻,𝑖𝑟𝑟 𝑄𝐿,𝑖𝑟𝑟 800 500
− = − = 0.666 − 1.666 < 0
𝑇𝐻 𝑇𝐿 1200 300
8
 Definition of entropy
𝛿𝑄
𝑅𝑒𝑐𝑎𝑙𝑙 ර = 0 𝑖𝑓 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑠 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒.
𝑇
B 𝛿𝑄 𝐵
𝛿𝑄 𝐴
𝛿𝑄
Process 1 ර =න +න =0
𝑇 𝐴 𝑇 𝐵 𝑇
(Process 1) (Process 2)

Process 1 is exactly the same as process 2 (with

𝛿𝑄
Process 2 opposite signs), which means that the function is
𝑇
path independent, hence called state function, and
A let’s give it a name:
Entropy (S) 9
 Increase-in-entropy principle
Now, process 1 is a random process (reversible or
not), but process 2 still stays reversible.
𝛿𝑄
Process 1 B Tℎ𝑒𝑛 ර ≤0 ∆𝑆 = 𝑆𝐴 − 𝑆𝐵
𝑇
𝐵 𝐴
𝛿𝑄 𝛿𝑄 𝛿𝑄
ර =න +න ≤0
𝑇 𝐴 𝑇 𝐵 𝑇 𝑟𝑒𝑣
𝐵
𝛿𝑄 𝛿𝑄
Process 2 ∆𝑆 ≥ න ≡ 𝑑𝑆 ≥
𝐴 𝑇 𝑇
𝐵 𝐵
A 𝛿𝑄 𝛿𝑄
∆𝑆 ≥ න =න + 𝑆𝑔𝑒𝑛
𝐴 𝑇 𝐴 𝑇 10
 Adiabatic & Closed system

In an adiabatic and closed system, there is no heat

Process 1 B transfer between the system and the surroundings.
𝐵
𝛿𝑄
∆𝑆 ≥ න + 𝑆𝑔𝑒𝑛 = 𝑆𝑔𝑒𝑛 ≥ 0
𝐴 𝑇
Note that 𝑆𝑔𝑒𝑛 is path dependent.

Process 2
This statement of entropy increase also holds true
for isolated systems, and the root reason that ∆𝑆 ≥
0 is because of the irreversibility of the processes.
A
11
 Application to other system?
Okay! Now it is clear that the entropy increase is true
for both adiabatic & closed systems and also isolated
systems, but how about others, e.g. open systems?
∆𝑆 ≥ 0 ℎ𝑜𝑙𝑑𝑠 𝑡𝑟𝑢𝑒

Surroundings
System (open) (isolated 1)
Surroundings (open)

System (isolated 1) System 2

System 3

… 12
 Notes about entropy
- A reversible and adiabatic process is also termed
isentropic process.
- In a closed system, heat loss is the only reason in which
entropy may decrease.
- Entropy is not a conservative property for irreversible
processes.
- The more irreversible the process is, the higher the
entropy it has.

∆𝑆 > 0: Irreversible processes

∆𝑆 = 0: Reversible processes
∆𝑆 < 0 : Such an process does not exist. 13
 Example - 2
A frictionless cylinder and piston system contains a mixture of 100°C liquid
water and vaporous water. During isobaric compression, 800 kJ is
transferred to the surroundings, 25 °C air. Thus, some vapor condenses.
Determine: (a) Entropy changes of water; (b) Entropy changes of air; (c) Is
the process reversible or not?
−800 𝑘𝐽
(a) ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = = −2.14 𝑘𝐽/𝐾
373 𝐾
800 𝑘𝐽
gas (b) ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = = +2.68 𝑘𝐽/𝐾
298 𝐾
800 kJ

liquid (c) ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0.54 𝑘𝐽/𝐾

14
 Example - 3
A 900 K heat source loses 1000 kJ to a heat sink of (a) 400 K and
(b) 800 K. Determine which process is more irreversible.
−1000 𝑘𝐽
(a) ∆𝑆𝑠𝑜𝑢𝑟𝑐𝑒 = 900 𝐾
= −1.11 𝑘𝐽Τ𝐾
900 K 1000 𝑘𝐽
∆𝑆𝑠𝑖𝑛𝑘 = = 2.5 𝑘𝐽Τ𝐾
400 𝐾
1.39 𝑘𝐽Τ𝐾
1000 kJ −1000 𝑘𝐽
(b) ∆𝑆𝑠𝑜𝑢𝑟𝑐𝑒 = 900 𝐾
= −1.11 𝑘𝐽Τ𝐾
1000 𝑘𝐽
400 K 800 K ∆𝑆𝑠𝑖𝑛𝑘 = = 1.25 𝑘𝐽Τ𝐾
800 𝐾
0.14 𝑘𝐽Τ𝐾
15
 Entropy changes in the Carnot cycle
For 1 mole of ideal gas: A→B; C→D: Isothermal; 𝑑𝑈 = 0
B→C; D→A: Adiabatic; δ𝑞 = 0
A
𝑉
q1 𝛿𝑞1 𝑅𝑇1 ln 𝑉𝐵 𝑉𝐵
𝐴
A→B 𝑑𝑆 = = = 𝑅 ln
𝑇1 𝑇1 𝑉𝐴
B
B→C 0
𝑉𝐷
𝛿𝑞2 𝑅𝑇2 ln 𝑉𝐷
D 𝑑𝑆 = =
𝑉𝐶
= 𝑅 ln
C→D 𝑇2 𝑇2 𝑉𝐶

q2 C D→A 0
𝑑𝑆𝑟𝑒𝑣,𝑡𝑜𝑡𝑎𝑙 = 0
16
 Combined 1st and 2nd laws

𝑑𝑈 = 𝛿𝑞 − 𝑃 ∙ 𝑑𝑉 = 𝑇 ∙ 𝑑𝑆 − 𝑃 ∙ 𝑑𝑉

𝑑𝑈 𝑃 ∙ 𝑑𝑉
𝑇 ∙ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ∙ 𝑑𝑉 𝑑𝑆 = +
𝑇 𝑇
𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝐻 = 𝑈 + 𝑃𝑉
𝑑𝐻 𝑉 ∙ 𝑑𝑃
𝑇 ∙ 𝑑𝑆 = 𝑑𝐻 − 𝑉 ∙ 𝑑𝑃 𝑑𝑆 = −
𝑇 𝑇

17
 Example - 4
5 moles of monatomic ideal gas are contained adiabatically at 50
atm and 300 K. The pressure is suddenly released to 10 atm, and
the gas undergoes an irreversible expansion, during which it
performs 4000 J of work. Cv = 1.5R

(a) Show that the final temperature of the gas after the
irreversible expansion is greater than that which the
gas would attain if the expansion had been
conducted reversibly.
(b) Calculate the entropy produced as a result of the
irreversible expansion.

18
 (a) Show that the final temperature of the gas after the irreversible
expansion is greater than that which the gas would attain if the
expansion had been conducted reversibly.

𝑃𝑉 = 𝑛𝑅𝑇 = 50 𝑎𝑡𝑚 ∙ 𝑉1 = 5 ∙ 0.082 ∙ 300

𝑉1 = 2.46 (𝑙𝑖𝑡𝑒𝑟𝑠)

Reversible: 𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑎𝑡 𝑃𝑉 γ = 𝑐𝑜𝑛𝑠𝑡. , ℎ𝑒𝑟𝑒 𝑤ℎ𝑒𝑟𝑒 γ = 5/3

γ γ γ
𝑃1 𝑉1 = 50 ∙ 2.46 = 10 ∙ 𝑉2, 𝑟𝑒𝑣 𝑉2,𝑟𝑒𝑣 = 6.47 (𝑙𝑖𝑡𝑒𝑟𝑠) 𝑇2,𝑟𝑒𝑣 = 158 𝐾

Irreversible: −4000 𝐽 = 5 ∙ 𝑐𝑉 ∙ 𝑑𝑇 𝑑𝑇 = −64 𝑇2,𝑖𝑟𝑟𝑒𝑣 = 236 𝐾

19
(b) Calculate the entropy produced as a result of the irreversible
expansion.
1→a: Constant volume
0
𝑑𝑈 𝑃 ∙ 𝑑𝑉 𝑛 ∙ 𝑐𝑣
𝑑𝑆 = + = 𝑑𝑇
𝑇 𝑇 𝑇
236
∆𝑆 = 5 ∙ 1.5 ∙ 8.314 ∙ ln = −14.95 𝐽/𝐾
300

2, rev
2, irrev a→2, irrev: isothermal
9.7
𝛿𝑞2 𝑛𝑅𝑇2,𝑖𝑟𝑟𝑒𝑣 ln 2.46
𝑑𝑆 = = = 57.0 𝐽/𝐾
𝑇2,𝑖𝑟𝑟𝑒𝑣 𝑇2,𝑖𝑟𝑟𝑒𝑣
2.46
9.7
6.47 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 42.0 𝐽/𝐾
20
(b) Calculate the entropy produced as a result of the irreversible
expansion.
1→2, rev: Adiabatic (rev)

∆𝑆 = 0

2, rev → 2, irrev: isobaric

2, irrev
𝛿𝑞𝑝 𝑛𝑐𝑝 𝑑𝑇
𝑑𝑆 = =
2, rev 𝑇 𝑇
236
∆𝑆 = 𝑛 ∙ 𝑐𝑝 ∙ ln = 5 ∙ 2.5 ∙ 8.314 ∙ 0.4
158
2.46
9.7
6.47 ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 41.7 𝐽/𝐾
21
 Example - 5

At a pressure of 1 atm, the equilibrium melting temperature of lead

is 600 K, and at this temperature, the latent heat of melting of lead
is 4810 J/mole. Calculate the entropy produced when 1 mole of
supercooled liquid lead spontaneously freezes at 590 K and 1 atm.

Given:
(a) 𝑐𝑝(𝑙) = 32.4 − 3.1 × 10−3 𝑇 𝐽/𝐾
(b) 𝑐𝑝(𝑠) = 23.56 + 9.75 × 10−3 𝑇 𝐽/𝐾

22
 Isothermal melting
4810
∆𝑆 = = 8.017 𝐽/𝐾
600
T Cooling
Heating Ss,600 8.017 J/K Sl,600
600 K
Melting/solidification of lead
600
23.56 + 9.75 × 10−3 𝑇 590
32.4 − 3.1 × 10−3 𝑇
∆𝑆 = න 𝑑𝑇 ∆𝑆 = න 𝑑𝑇
590 𝑇 600 𝑇
0.494 J/K -0.514 J/K
590 K
Ss,590 ? Sl,590

S ?=-7.999 J/K
Isothermal solidification
Negative?
23
 Isothermal melting
∆𝐻 = 4810 J

T Cooling
Heating Ss,600 Sl,600
600 K
Melting/solidification of lead
600 590
∆𝐻 = න (23.56 + 9.75 × 10−3 𝑇) 𝑑𝑇 ∆𝐻 = න (32.4 − 3.1 × 10−3 𝑇) 𝑑𝑇
590 600
294 J - 306 J
590 K
Ss,590 Sl,590

∆𝑆𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 = 8.134 𝐽/𝐾 ∆𝐻 = −4798 J

S
∆𝑆𝑡𝑜𝑡𝑎𝑙 = 0.137 𝐽/𝐾
Isothermal solidification 24
 HW 2 (due date: 10/8)
! Important: Please detail your thoughts and the calculation processes. Do not give just the final answers. !

1. Please prove the following principle: “Efficiencies of two heat

engines that are run reversibly at two identical temperatures (TH
and TL) are the same”.

2. Show that for a Carnot

𝑉𝐵 𝑉𝐶
cycle on the right, = ,
𝑉𝐴 𝑉𝐷
where V means molar volume.

25
 HW 2 (due date: 10/8)
! Important: Please detail your thoughts and the calculation processes. Do not give just the final answers. !

3. For a reversible isothermal expansion process (from 𝑉𝐴 𝑡𝑜 𝑉𝐵 ) of

an ideal gas, show that ∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0

4.

(3.1, 3.2, 3.4 from Gaskell 6th edition)

 HW 2 (due date: 10/8)
5.

(Note that please calculate all individual processes a, b, c, d, and the overall sum a→d)

6.

(3.1, 3.2, 3.4 from Gaskell 6th edition)