Thermodynamics of Materials – I

材料熱力學一 MSE 2001 (507 20100)

Semester: 111-1
Lectures: Fri. 13:20 – 16:20 @ 綜501
Instructor: Dr. Shao-Pu Tsai
TA: Wei-Yen Tsai (蔡維晏) r11527022@ntu.edu.tw
Level: Undergraduate / Graduate
Homework 30% (5% for each)
Gradings: Midterm exam 35%
Final exam 35%
Office hours: anytime (33664673 / shaoputsai@ntu.edu.tw)
 Textbooks
書名：Introduction to the Thermodynamics of Materials, 6th edition
作者：David R. Gaskell, David E. Laughlin
出版者：CRC Press
出版日期：2017

書名：Thermodynamics in Materials Science, 2nd edition

作者：Robert DeHoff
出版者：CRC Press
出版日期：2006
 Homework
~ Every two weeks, there will be a problem set for you to answer.
The due date is the next Friday, before which you have to submit
your answers to NTUCool. Discussion in groups is highly
welcome. Plagiarism is strongly prohibited! If caught, you will be
assigned other homework or have to submit a research report
related to thermodynamics. There’ll be 6 HWs.

Midterm and final exams

A lot of different modules will be there, e.g., yes/no; multiple
choices; problem sets needing calculation etc. Details will be
announced before exams. There will be mid- and final exams.
 Beforehand…
When it comes to thermodynamics, what do you have in mind?
 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 3 √
2nd law of thermodynamics; combination of 1st and 2nd law
Calendar

5 10/7 3
6 10/14 Auxiliary functions (H, A, G); Maxwell equation 5 √
7 10/21 Conditions for equilibrium -
8 10/28 期中考
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 6 √
13 12/2 Effect of P on H and S; phase equilibria 6, 7
14 12/9 Unary (one-component) heterogeneous systems 7 √
15 12/16 Behavior of ideal gases to real gases 8
16 12/23 期末考
 5W1H about learning
thermodynamics: Why?
Unary phase diagram Binary Ag-Mg phase diagram Pourbaix diagram

Only one component Two components (‘Ag’, ’Mg’)

 Who, (where) and when?
Otto von Guericke (1601–1674) Robert Boyle (1627–1691) Sadi Carnot (1796–1832) Rudolf Clausius (1822-1888)

Magdeburg hemispheres 𝑃 ∝ 1/𝑉 Carnot engine Entropy

William Thomson (1824-1907) Ludwig Boltzmann (1844-1906)
James Clerk Maxwell (1831-1879) Josiah Willard Gibbs (1839-1903)

Lord Kelvin
2nd law of thermodynamics Statistical thermodynamics
 What to learn and how to learn it?

Classical thermodynamics is a phenomenological study

that is based on the macro states of the system. In
Some useful tips:
comparison, statistical mechanics focuses on knowing - Read the textbooks
the micro states, i.e., the masses, velocities of
particles and how they interact (interatomic potential). - Discuss in groups
In order to fix a macro state of a system, an enormous - Go through derivations /
amount of information have to be known. Yet, these
variables are not all independent. Some are equations / homework on
independent while others are simply not. Later on we your own
will have a lot of examples to illustrate this point.
In the following few slides, we will try to give some
- Something unclear? Raise
definitions to common terminologies that are hands(s) immediately in
essential yet confusing at times.
the class or just… shout!
 Systems
Surroundings
Surroundings

? System Isolated system

System
Heat / work (energies)

Closed system
Check:
Heat / work (energies)
- Unary vs. multicomponent
- Homogeneous vs. heterogeneous Mass
- Open vs. closed vs. isolated
- Reacting vs. non-reacting Open system
 System properties and SI units

Extensive properties
Values depend on the size of the system
- Volume, V
- Mass, M
- Mole, n

Intensive properties
Values that do not depend on the size of the system
- Temperature, T
- Pressure, P
- Density, ρ
- Volume per unit mass (specific volume)
- Molar xxx, e.g., molar volume, molar entropy
 Processes

- Isobaric 定壓 dV = 0
- Isothermal 定溫 dT = 0
- Isochoric/isometric 定體積 dV = 0
- Isentropic 定熵 dS = 0
- Adiabatic 絕熱 dq = 0
- (Ir)Reversible 可逆/不可逆
- Quasi-static 近似靜態
- Endothermic / Exothermic 吸熱/放熱
 State function (or function of state)
𝑉 = 𝑉 𝑃, 𝑇 → 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑎𝑡𝑒 isothermal
∆V = V2 − V1 = (Va − V1) + (V2 − Va)
Const. P Const. T

𝑇2 𝜕𝑉 𝑃2 𝜕𝑉
∆V = ‫𝑇𝑑 𝑇𝜕 𝑇׬‬ + ‫𝑃𝑑 𝑃𝜕 𝑃׬‬
1 𝑃1 1 𝑇2
ර 𝑑𝑉 = 0
𝑃2 𝜕𝑉 𝑇2 𝜕𝑉
∆V = ‫𝑃𝑑 𝑃𝜕 𝑃׬‬ + ‫𝑇𝑑 𝑇𝜕 𝑇׬‬
1 𝑇1 1 𝑃2

𝜕𝑉 𝜕𝑉
So generally, 𝑑V = dP + dT isobaric
𝜕𝑃 𝑇 𝜕𝑇 𝑃
 State function (or function of state)
It seems that the value ∆V does not depend on the path
the process takes. Taking an extreme example shown
on the right, the value would still be exactly the same.
This kind of function is called state function.

Being an exact differential is a necessary

and sufficient condition for a state function.

dV is exact → V is a state function

 Equation of state of ideal gas
1
Boyle’s law (1660): At const. T: 𝑃 ∝
𝑉
Charles’ law (1787): At const. P: 𝑉 ∝ 𝑇
For one mole of ideal gas,
P T2 > T1 V
T2 P3
P2 P1> P2> P3

T1
P1
V 0°C T (K)
 Equation of state of ideal gas

V
P3 By Joseph-Luis Gay-Lussac (1802):
P2 P1> P2> P3
1 𝜕𝑉
𝛼= = 𝐶𝑜𝑛𝑠𝑡.
𝑉0 𝜕𝑇 𝑃
P1 𝑉0 𝑖𝑠 𝑡ℎ𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑎𝑡 0°𝐶

0K 0°C T (K)

α is finally shown for hypothetical ideal gas to be 1/273.15

 Equation of state of ideal gas

PV = RT for one mole of ideal gas

PV’ = nRT for n moles of ideal gas

Recall the intensive and extensive variables.

intensive extensive

V’ is called volume of the system, while

V is called molar volume of the system.
 HW 1-1
1. What is state function? What is path function?
2. Why is heat a process variable?
3. Name 3 intensive and 3 extensive properties.
4. Show that for ideal gas, α equaling 1/273.15 sets a limit on the
thermal contraction of the ideal gas. And show that as a
consequence, we set -273.15 °C to be the absolute zero
temperature.
5. At standard temperature and pressure (STP, 0°C and 1 atm)
condition, one mole of ideal gas occupies 22.414 liters. Show
the value of gas constant, R, in terms of (liter·atm/degree ·mole)
and (joules/degree ·mole).