Classical & Statistical Thermodynamics

x
Thermodynamics in Solids
Welcome!

Nien-Ti Tsou

Department of Materials Science and Engineering, National Chiao Tung University

 Information

• Lecturer: Nien-Ti Tsou

• Email: tsounienti@nctu.edu.tw

• Office: Room 308, Engineering Building VI

• Lectures: 9:00-12:00 Wednesday

• Download the slides from the E3 platform

http://dcpc.nctu.edu.tw/

MSE-NCTU Thermodynamics in Solids

 Course Syllabus
Lecture 0. Welcome!
Lecture 1. Review of Classical Thermodynamics
Lecture 2. Review of Classical Thermodynamics
Lecture 3. Review of Classical Thermodynamics
Midterm 1
Lecture 4. Introduction to Statistical Thermodynamics
Lecture 5. The Connection between Classical & Statistical Thermodynamics
Lecture 6. Maxwell-Boltzmann Distribution
Lecture 7. Bose-Einstein Distribution
Lecture 8. Fermi-Dirac Distribution
Midterm 2
Lecture 9. The  Classical  Statistical  Treatment  of  an  Ideal  Gas  
Lecture 10. The  Classical  Statistical  Treatment  of  an  Ideal  Gas  
Lecture 11. Diatomic  Gas  
Lecture 12. Diatomic  Gas  
Lecture 13. Heat  Capacity  of  a  Solid
Final Exam

MSE-NCTU Thermodynamics in Solids

 References
• Classical and Statistical Thermodynamics, Ashley H. Carter

• Thermodynamics in Materials Science, Robert DeHoff

• An Introduction to Thermal Physics, Daniel V. Schroeder

• Thermal Physics, Charles Kittel / Herbert Kroemer

• Thermodynamics of Materials, John B. Hudson

MSE-NCTU Thermodynamics in Solids

 Grading and Homework
• Grading:

• 10%+10% Quiz

• 25% Midterm 1

• 25% Midterm 2

• 30% Final Exam.

MSE-NCTU Thermodynamics in Solids

 Thermodynamics in Solids
Introduction

Nien-Ti Tsou

Department of Materials Science and Engineering, National Chiao Tung University

 What Is Thermodynamics?

“A theory is the more impressive the greater the simplicity of

its premises, the more different kinds of things it relates,
and the more extended its area of applicability. Therefore
the deep impression that classical thermodynamics made
upon me. It is the only physical theory of universal content
which I am convinced that, within the applicability of its
basic concepts, it will never be overthrown.”

MSE-NCTU Thermodynamics in Solids

 What Is Thermodynamics?
• Thermodynamics is
the study of equilibrium properties in which Temperature
is an important variable. It is a phenomen logical theory.

• Great simplicity and generality: Not trying to explain

underlying causes.

• The statistical approach takes account of the molecular

constitution of matter and reveals a deeper foundation on
which the laws of thermodynamics.

• Macroscopic measurements are averages of the behavior of

astronomical numbers of particles.

• It tells you what will happen, but you will never know how
long it will happen.

MSE-NCTU Thermodynamics in Solids

 Macroscopic and Microscopic
Approach Macroscopic Microscopic

Theory Classical thermodynamics Statistical thermodynamics

Treats the as a as a collection of

system whole .
discrete entities
depends largely on models
requires direct experimental
Limitation which may not be adequate
thermodynamic data
enough to describe the reality

or ?

MSE-NCTU Thermodynamics in Solids

 System
• System:
a part of the world which is isolated from the rest of the
world by definite boundaries.
e.g. a container of gas, a piece of metal

• Surroundings:
Outside of a given system

• Universe:
the system along with its surroundings.

MSE-NCTU Thermodynamics in Solids

 Types of Systems

Surroundings

Exchange Exchange
mass energy
System System System Open Yes Yes
1 2 3
Closed No Yes
Isolated No No

MSE-NCTU Thermodynamics in Solids

 Properties
• Properties: the quantities used to describe the macroscopic
behavior of a system
*

•
"

Extensive properties: propottonal to the mass, IT ,work

V=Ih

:
volume mass in kilomo
Specific n :

value of the extensive property

Specific value ⌘
mass of the system
-
x :

• Intensive properties: independent of the mass, T.P.rs

•
State density
a system is defined as condition
a
uniquely specified by
a set of properties , e.g. pressure, volume and temp.
Generally, only the minimum number of properties necessary
to describe the state.
P V = nRT
MSE-NCTU Thermodynamics in Solids
 Equilibrium
• Equilibrium state:
the properties of the system are uniform
throughout and do not change with time unless
the system is acted upon by external influences

• Non-equilibrium state:

a system in which gradients exist and whose

properties vary with time
T
zquikbnum
• Equation of state: .
-
1 state
a funtional relationship among the state .

s
.

variables for a system in equilibrium

f (P, V, T ) = 0
P V = nRT f (P, V, T ) = 0
V
P
MSE-NCTU Thermodynamics in Solids
 System Wall
• Adiabatic wall:a 
 boundary that permits no heats
interaction with the surroundings

• Diathermal wall:
a boundary that freely allows heat to be
exchanged with the surroundings

Adiabatic wall Diathermal wall

System

Heat bath

MSE-NCTU Thermodynamics in Solids

 T Equilibrium
Process state

"
• Process:a change of state expressed f (P, V, T ) = 0
in terms of path along the surface V
of the equation of state P
• Cyclical process:the initial and final states are the same

• Quasi-static process:a process in which, at each instant, the

system departs only infinitesimally
from an equilibrium state
• Reversible process:a process whose direction can be
reversed by an infinitesimal change
in some properties
Reversible process
= (Quasi-static process) + (No dissipative force )
MSE-NCTU Thermodynamics in Solids
 Quasi-static Process
• Quasi-static process: The process is sufficiently slow. The
system is in equilibrium at all time (the macro-parameters
are well-defined for all intermediate states).
T
• For example, in a quasi-equilibrium
2
process for the ideal gas, P, V, T are
well-defined. The path between two
states is a continuous lines in the P, V, T
space. V
P 1

MSE-NCTU Thermodynamics in Solids

 Reversible and Irreversible Processes
• Irreversible process:
involves a finite change in a properties in a given step
and includes dissipation ( energy loss )
• For a reversible process, there is no permanent changes in
the universe, while irreversible processes are accompanied
by permanent changes in the universe.

Reversible Irreversible

MSE-NCTU Thermodynamics in Solids

 Process
• Adiabatic process: No heat flow into or out of the system.

• Isobaric process: a process in which the pressure is constant

volume
• Isochoric process: a process in which the is constant

• Isothermal process: a process in which the temperatureis

constant
Ex :
Diathermal wall P V = nRT
slowly P static
friction (Pf,Vf) quasi -

no
compressed
.

reversible

Gas Piston isothermal process

(Pi,Vi)
Heat bath
V
MSE-NCTU Thermodynamics in Solids
 Units

(SI) International System of Units Vacuum

length: m
mass: kg
IN =/ kg he
time: sec
.

pressure: Pa (pascal) = 1Nm 2

h P
1 bar ⌘ 105 Pa
1 atm ⌘ 1.01 ⇥ 105 Pa
1 torr ⌘ 133.3 Pa
Mercury

MSE-NCTU Thermodynamics in Solids

 Logic in Thermodynamics
Initial state,
Equilibrium System Surrounding

Change surrounding

System Surrounding

Change system

Final state,
Equilibrium System Surrounding

MSE-NCTU Thermodynamics in Solids

 Equation of State
• An equation of state details the mathematical relationship
between the physical observables pressure P, volume V, and
-

temperature T.
, -

for example .

The ideal gas obeys P V = nRT *

scalar : ital :c

or vector
:
bold
matrix .

V
P v = RT , v = n
upright
V N P T

• At constant V, n the ratio of P and T must be constant

. - - .

(Amonton’s Law)

P1 P2
= , (constant V, n)
T1 T2

MSE-NCTU Thermodynamics in Solids

 Temperature and The Gas Constant
Pv
• Operational definition of temperature: T = lim

)
P !0 R
• Using Amonton’s law, can extrapolate P vs T for a sealed, fixed
volume to P=0 in order to define T=0

extrapolate

At low all
| 273.15 K measurements
ideal behavior
pressures .

gases converge to

MSE-NCTU Thermodynamics in Solids

 Van Der Waals Equation of State
Indianhead intermolecular

interaction
a
(P + 2
)(v b) = RT
v l
molecular size

MSE-NCTU Thermodynamics in Solids

 ↳
PHNRT
PV Diagram for Carbon Dioxide
Real Theory
isotherms, teg÷Bs4B Van Der Waals Equation of State
plot of P vs v at constant T a

curve
(P + 2 )(v b) = RT
v

RT a ab
v3 (b + P )v 2 + P v P =0

'n#t°n
work done

thesysten

liquid & gas

Coexistence Release
the work
#§ Maxwell
equal area construction

v
MSE-NCTU Thermodynamics in Solids