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Instructor: Prof.

Chi-Chung Hua
Instructor: Prof. Chi-Chung Hua
Molecular Rheology LAB
Advanced Thermodynamics
Advanced Thermodynamics
Complex Fluids & Molecular Rheology Laboratory,
Department of Chemical Engineering,
National Chung Cheng University, Chia-Yi 621, Taiwan, R.O.C.
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Course Outline
Course Outline
Instructor: 華 繼 中 教授 ( 工二館 Rm 412 Ext. 33412)
Textbook: Herbert B. Callen, 1985, “Thermodynamics and
Introduction to Thermostatistics”, 2nd ed., John
Wiley & Sons, Inc. ( 歐亞書局代理)
Grading: Homework (20 %)
Two Exams (80 %)
Teaching assistants: 李正光、林志榮 (Rm 301, Ext. 23471)
Molecular Rheology LAB
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Part one: Classic Thermodynamics
Chapter 1: Basic Concepts and Principles
Chapter 2: Thermodynamic potentials and Legendre
Transformations
Chapter 3: Stabilities, Phase Transitions, and Critical
Phenomena
Chapter 4: Applications to Material Properties
Part two: Statistic Thermodynamics
Chapter 5: Statistic Ensembles and Energy Representations
Chapter 6: Some Applications of Statistic Mechanics
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Basic Concepts and Principles
Chapter 1
Chapter 1
Molecular Rheology LAB
Contents
1-1 Thermodynamic Equilibrium and Postulate I
1-2 The Entropy Maximum and Postulates II & III
1-3 Intensive Parameters and Equations of State
1-4 The Euler Equation and the Gibbs-Duhem Relation
1-H Homework
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Thermodynamic Equilibrium and
Thermodynamic Equilibrium and
Postulate I
Postulate I
1-1.1 Thermodynamic coordinates
1-1.1 Thermodynamic coordinates
1-1
Variables
Experimental variables
Simulation variables
Macroscopic vs. Microscopic
Responses
Experimental results
Simulation data
1-1
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Q1: How to select variables of an experimental or simulation
system?
Q2: Select macroscopic or microscopic variables?
A1: 1. Use minimum number of measurable variables.
2. Each variables must be independent.
A2: The basis of selection is the scale of the phenomena or substances of
primary interest.
1-1
length scale
1 m μ
Microscopic Macroscopic
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1-1
Microscopic Macroscopic
Microscopic properties can spread to macroscopic properties
But macroscopic properties cannot spread to microscopic properties
We usually used macroscopic properties to describe engineering
problem, simply because it’s easier to do.
The price paid is, however, that small-scale problems cannot be
studied, and some macroscopic properties themselves become
difficult to understand.
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Molecular Rheology LAB
http://www.bibalex.org/English/lectures/printable/zewail.htm
Figure 1.1 Length and time scales of atoms and cats
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1-1.2 Definition of equilibrium states
1-1.2 Definition of equilibrium states
System has no external influences (such as flow, electrical fields).
All thermodynamic properties must be “time invariance” (time
independent).
1-1
When all properties have reached time independence in our selected time
scale, the system would seem to reach an equilibrium. Yet, since different
people may have different opinions of time scale, the viewpoint of equili-
brium could also be different.
Molecular Rheology LAB
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1-1.3 Limitations of thermodynamic equilibrium
1-1.3 Limitations of thermodynamic equilibrium
1-1
Scale limitation: Length scale must be greater than ca.10nm.
Time invariance: All variables and properties must be time
independent.
Postulate I:
All macroscopic properties of an equilibrium system can be completely
characterized by extensive parameters U, V, and N
1
,N
2
,…N
r
;
e.g., S = S(U, V, N) for a one-component system.
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The Entropy Maximum Postulates:
The Entropy Maximum Postulates:
Postulate II & III
Postulate II & III
1-2
1-2
Postulate III:
S is a monotonically increasing function of U.
Molecular Rheology LAB
Postulate II:
For an isolated system with constant V, N, U the equilibrium criterion
requires that the entropy S reaches a maximum value.
1
1
, , ... ,
( , , , ... , )
1
r
r
V N N
S S U V N N
S
U
·

¸ _
>


¸ ,
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1-2
S = S (U )
only
' '
1 1 1 1
'
1
'
1

?
?
U U U U
U
U
+ · +
·
·
By entropy
max.
Molecular Rheology LAB
V
1
U
1
N
1
V
2
U
2
N
2
thermodynamic constraints
The system may then be
further divided into two
sub-systems subject to
certain constraints:
S = S (U , V ,
N )
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1-2
1 1 1
1 1
1
1 1
1 1
( ) 1 1
1 1
( ) 1 1
dS dU dU dU
T T
dU
T T
· − · + ·
− · ≠
Q
Q
T
1
= T
2
An important equilibrium
condition
Molecular Rheology LAB
,
1 1 1 1
1 1
1 1 1 1
1 1 1 1
, ,
; is extreme value 1
( ) ( )
1 1
1
N V
N V N V
S
dS dU S dS
U
S S U S U
S S
dS dU dU dU dU
U U T T

¸ _
· → ·


¸ ,
· +
¸ _ ¸ _
∂ ∂
∴ · + · + ·

∂ ∂
¸ , ¸ ,
Q
Use d
2
S to check S is
max. or min.
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Molecular Rheology LAB
Others equilibrium conditions can be derived with fixed V
& U or N & U.
μ
1
= μ
2
for fixed V & U
P
1
= P
2
for fixed N & U
V
1
U
1
N
1
V
2
U
2
N
2
thermodynamic constraints
V
1
U
1
N
1
V
2
U
2
N
2
thermodynamic constraints
Fixed V & N Fixed U & N
1-2
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Intensive Parameters and Equations of
Intensive Parameters and Equations of
State
State
1-3
Molecular Rheology LAB
1-3
1-3.1 Extensive parameters & intensive parameters
1-3.1 Extensive parameters & intensive parameters
Extensive parameters
1
, , , : First order extensive parameters
( , , ) ( , , )
S U V N
S U V N S U V N λ λ λ λ ·
Example
:
( , , ) ( , , ) 1 1 1 1 S U V N S U V N ·
S S
S
S
S
S S
S
S
S
Enlarged 9 times
First order
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1-3
Molecular Rheology LAB
Intensive parameters
( , , ) ; ( , , ) S S U V N U U S V N · ·
, , ,
, , ,
1
; ;
; ;
N V U N U V
N V N S S V
S S P S
U T V T N T
U U U
T P
S V N
µ
µ
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ ≡ ≡ −

∂ ∂ ∂
¸ , ¸ , ¸ ,
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ ≡ ≡

∂ ∂ ∂
¸ , ¸ , ¸ ,
Fundamental equations
At first, people didn’t know the meanings of T, P and μ. Later, they
realized that T, P and μ were identical with temperature, pressure and
chemical potential in our ordinary life.
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1-3
Molecular Rheology LAB
, S V
U
N
µ

¸ _



¸ ,
Example
:
Liquid
Gas
Chemical potential:
The definition of chemical potential is the
energy change from a particle, molecule or
electron move into or leave the system.
If the overall system has reached an equili-
brium, the energy reduction in the liquid
phase due to the moving of a molecule into
the gas phase is the same as the energy
increase in the gas phase. So, the total
system energy remains unchanged.
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1-3
Molecular Rheology LAB
Fundamental equations
( , , )
( , , )
S S U V N
U U S V N
·
·
Entropy representation
Energy representation
Two equations are alternative forms of the fundamental relation, and each
contains all thermodynamic information about the system.
1-3.2 Fundamental equations & equations of state
The fundamental equations describe homogeneous first-order parameters.
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1-3
Molecular Rheology LAB
Equations of state
, , ,
( , , )
; ;
N V N S S V
U U S V N
U U U
T P
S V N
µ
·
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ ≡ ≡

∂ ∂ ∂
¸ , ¸ , ¸ ,
( , , )
( , , )
( , , )
T T S V N
P P S V N
S V N µ µ
·
·
·
Equations of state:
An intensive parameter is expressed in
terms of independent extensive
parameters.
Knowledge of a single equation of state does not constitute complete
knowledge of the thermodynamic properties of a system.
Knowledge of all independent equations of state is equivalent to the
knowledge of the fundamental equation.
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1-3
Molecular Rheology LAB
Figure 1.2 U vs. S & U vs. T in constant V & N
Each line of U(S) may yield the same U(T) curve (an equation of state).
But the reverse is not true.
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1-3
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1
, ,
( ) ( )
( ) ( )
N V N V
U U
T
S S
λ λ
λ
λ λ
∂ ∂
· ≡
∂ ∂
The equations of state describe homogeneous zero-order parameters.
U & S are first order parameters
Zero order
( , , ) ( , , )
( , , ) ( , , )
( , , ) ( , , )
T S V N T S V N
P S V N P S V N
S V N S V N
λ λ λ
λ λ λ
µ λ λ λ µ
·
·
·
Equations of state
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1-3.3 Unit of temperature
1-3
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T
h
T
c
dQ
h
dW
rev
Thermodynamic engine
rev
ε1
c
e
h h
dW T
dQ T
· · −

Thermodynamic engine
efficiency:
1 1
1 1
1 1
1 1
T T
T T
T T k
T T k
λ
λ
·
+

+
Used to define temperature scale.
Permissible scale (e.g. K, R)
Non-permissible scale (e.g.
o
C,
o
F)
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1-3
Molecular Rheology LAB
Question: All heat can be transfer to work?
Heat Molecular
Rotation
Vibration
Kinetic energy
Internal energy
Work
Answer: It is impossible unless T
c
= 0K
Heat Molecular
Rotation
Vibration
Kinetic energy
Internal energy = 0
All heat transfers to
produce work
T
c
≠ 0K
T
c
= 0K
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1-3
Molecular Rheology LAB
Unit of temperature
,

N V
U
T
S

¸ _



¸ ,
Unit of U is
energy.
What is the unit of
entropy?
Unit of entropy:
In classic thermodynamics, entropy
is dimensionless parameter.
In thermostatistics, unit of entropy
correlates with states.
So, unit of temperature is energy.
The temperature scale, Kelvin, was used in molecular scale.
e.g. Energy of a simple molecule = 3/2 k
B
T = 3/2 Kelvin
Joule/Kelvin = 1.38 x 10
-23
= k
B
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1-3
Molecular Rheology LAB
1-3.4 The general case of entropy max. in equilibrium
1 1 1 1 1 1
1 1 1 1 1 1 1 1
1 1
1 1 1
1 1 1
1 1 1
1 1 1
, , ,
1
1
( , , ) ( , , ) w.s.t. , ,
1


total
V N U N V U
S S U V N S U V N dU dV dN
P
T T T
S S S
dS dU dV dN
U V N
S
U
µ
· +

¸ _ ¸ _ ¸ _
∂ ∂ ∂
· + +

∂ ∂ ∂
¸ , ¸ , ¸ ,
¸

+

1 1 1 1 1 1
1 1
1 1 1
1 1
, , ,
1 1
1 1 1
1

V N U N V U
S S
dU dV dN
V N
P
T T T
µ
_ ¸ _ ¸ _
∂ ∂
+ +

∂ ∂
¸ , ¸ , ¸ ,

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1-3
Molecular Rheology LAB
at equilibrium
This equation always holds only if
1 1 1 1
1 1 1
1 1 1 1 1 1
1 1
1 1
1 1
1 1
1
P P
dS dU dV dN
T T T T T T
T T
P P
µ µ
µ µ
¸ _ ¸ _ ¸ _
· − + − + − − ·

¸ , ¸ , ¸ ,
·
·
·
If in reaching equilibrium
initial state
. 1
. 1
. 1
1 1 1 1 1 1 1
1 1 1 1 1 1 1
1 1 1 1 1 1 1
1
, , 1
, , 1
, , 1
dS
P P T T dU
P P T T dV
P P T T dN
µ µ
µ µ
µ µ
>
· · > <
> · · >
· > · <
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The Euler Equation and the Gibbs-Duhem
The Euler Equation and the Gibbs-Duhem
Relation
Relation
1-4
Molecular Rheology LAB
1-4.1 The Euler relation
1-4.1 The Euler relation
1-4
Homogenous first order property

differentiating w.r.t. ( )
1 1 1 1
( , , , , ...) ( , , , , ...) U S V N N U S V N N
d
λ λ λ λ λ
λ λ
·
1 1 1 1

( , , , , ...) ( ) ( , , , , ...) ( )
( ) ( )
( , ,
T S P V
U S V N N S U S V N N V
S V
U S V N
λ λ λ λ λ λ λ λ λ λ
λ λ λ λ
λ λ λ

∂ ∂ ∂ ∂
+
∂ ∂ ∂ ∂

+
1 1 1
1 1
1
1 1
, , ...) ( )
... ( , , , , ...)
( )

N N
U S V N N
N
N
λ λ
λ λ
µ

+ ·
∂ ∂
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Molecular Rheology LAB
1-4
j j
j = 1
i i j j
i = j = 1 1
i i
i = 1


Let

Another form:

1 1 1 1 1 1
1 1
1 1
( , , , , ...) ...
( , , , , ...)
( , , , , ...)
U S V N N TS PV N N
TS PV N
PX PV N
U S V N N TS PX
S U V N N
µ µ
µ
µ
· − + + +
· − +
· − +
· +

∑ ∑

j
j
j
1 P
U V N
T T T
µ
¸ _
¸ _ ¸ _
· − +


¸ , ¸ ,
¸ ,

The Euler relation is useful for deducing many important thermodynamic
relationships, including the famous Gibbs-Duhem equation.
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1-4
Molecular Rheology LAB
1-4.2 The Gibbs-Duhem equation
i i
i = 1
i i i i
i = i = 1 1
i i
i = 1
i i
i = 1
Euler relation:
Given that
One obtains
Another form
1 1
( , , , , ...)
1
1
U S V N N TS PX
dU TdS SdT PdX X dP
dU TdS PdX
SdT X dP
P
Ud Vd
T T
· +
· + + +
· +
+ ·
¸ _ ¸ _


¸ , ¸ ,

∑ ∑


j
j
j
1 N d
T
µ
¸ _
+ ·

¸ ,

the Gibbs-Duhem equation
Not all intensive properties are independent, but only n-1 of them are
independent. Another one can be deduced from the Gibbs-Duhem
equation.
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Molecular Rheology LAB
1-4
Example
:
For one-component systems (having int 1 ensive properties & )

unit number
,
1
& : &
T P
SdT VdP Nd
S V
d dT dP sdT vdP
N N
s v S V
µ
µ
µ
− + ·
· − + · − +
Only T & P are independent, μ
can be deduced from the Gibbs-
Duhem equation.
The Euler relation is useful for deducing many important thermodynamic
relationships, including the famous Gibbs-Duhem equation.
The Gibbs-Duhem relation specifies, in a differential form, the
relationship among all “intensive” properties of a thermodynamic system.
Clearly, μ is not independent of T and P in the previous example.
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1-4
Molecular Rheology LAB
1-4.3 Summary of formal structure
The fundamental equation U=U(S, V, N) contains “all” thermodynamic
information.
Equations of state + the Euler equation = The full expression of U
( , , )
( , , ) ( , , )
( , , )
i i
T T S V N
P P S V N U TS P X U U S V N
S V N µ µ
·
· · + ·
·

The totality of all equations of state can be used to reconstruct the
fundamental equation.
32
Homework
Homework
1-H
1-H
Molecular Rheology LAB
Problem 1.10-1: (a), (f), (g), (i)
Problem 2.2-1
Problem 3.3-2
Read Sec. 3-5 (The ideal van der Waals fluid)
33
Thermodynamic Potentials and
Thermodynamic Potentials and
Legendre Transformations
Legendre Transformations
Contents
2-1 Legendre Transformations
2-2 The Legendre Transformed Functions and Thermodynamic
Potentials
2-3 Minimum Principles for the Potentials
2-4 Applications of various Legendre Transformed Potentials
2-5 Maxwell Relations and Some Applications
Chapter 2
Chapter 2
Molecular Rheology LAB
34
Legendre Transformations
Legendre Transformations
2-1.1 The
2-1.1 The
S
S
max. principle & the
max. principle & the
U
U
min. principle
min. principle
2-1
2-1
Molecular Rheology LAB
An isolated system must conform with two
extremum criteria when equilibrium is reached.
Entropy max. principle:
Entropy is max. value for
given total energy.
Energy min. principle:
Energy is min. value for
given total entropy.
Equivalent
representations
35
2-1
Molecular Rheology LAB
Figure 2.1 The equilibrium state A as a point of max. S for constant
U & min. U for constant S.
Fundamental
surface
S max. principle U min. principle
S max. principle: The equilibrium value of any unconstrained internal parameter
is such as to maximize the entropy for a given value of the total internal energy.
U min. principle: The equilibrium value of any unconstrained internal parameter
is such as to minimize the energy for a given value of the total internal entropy.
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2-1
Molecular Rheology LAB
Question: How to prove the two principles are equivalent?
Answer: Using either physical argument or mathematical
exercise.
Physical argument
Assume: The system is in equilibrium but the energy does not have its
smallest possible value consistent with the given entropy.
The system would be restored to its
original energy but with an increased S.
So, it is inconsistent with the principle
that the initial equilibrium state is the
state of maximum entropy.
System
Can withdraw energy
dU = -dW
Return energy to
sys.
-dW = dQ = TdS
Energy
The original equilibrium state must have had min. energy consistent with
the prescribed entropy. The inverse argument is the same.
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2-1
Molecular Rheology LAB
Mathematical exercise
and : Particular extensive parameter
1
1
1 1
U
U
S S
X
X X
¸ _
∂ ∂ ¸ _
· <


∂ ∂
¸ ,
¸ ,
Entropy maximum principle:
1
U
S U
X
S
X U S
P T
S X X
U
∂ ¸ _

∂ ∂ ∂
¸ _ ¸ _ ¸ ,
≡ · − · − ·

∂ ∂ ∂ ¸ _
¸ , ¸ ,


¸ ,
By eqn. A.22 of Appendix A
1
S
U
X

¸ _
·


¸ ,
( , )
S
U
P P P U X
X

¸ _
≡ ∴ ·


¸ ,
Q
1
1
at 1
S X U U
S
U P P P P
P P
X X U X X
¸ _
∂ ∂ ∂ ∂ ∂ ¸ _ ¸ _ ¸ _ ¸ _
· · + · ·


∂ ∂ ∂ ∂ ∂
¸ , ¸ , ¸ , ¸ ,
¸ ,
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2-1
Molecular Rheology LAB
1
1
1
1
1 1
1 1
1 1
=
at & 1 1 1 1
U U
U U
U
X X
U X
U
S
S
S
X
X U P S
X U
S S X X X X
S
U U
U
S S S
T T
X X X
¸ _

1 ∂ ¸ _


1

¸ _ ∂ ∂ ∂ ∂ ∂ ¸ _ ¸ _ ¸ , ¸ ,
∂ ∂
1
· − · − +


∂ ∂ ∂ ∂ ∂ ∂ ¸ _ ¸ _ 1
¸ , ¸ , ∂ ¸ _ ¸ ,

1
∂ ∂
¸ , ¸ ,

¸ ] ¸ ,
¸ _
∂ ∂ ∂
· − > · < ≥

∂ ∂ ∂
¸ ,
Q
;
1
1
1 1
U
U
S S
X X
¸ _
∂ ∂ ¸ _
· <


∂ ∂
¸ ,
¸ ,
;
1
1
1 1
S
S
U U
X X
¸ _
∂ ∂ ¸ _
· >


∂ ∂
¸ ,
¸ ,
From S max. principle: U min.
princi
ple:
39
2-1
Molecular Rheology LAB
2-1.2 Legendre transformations
Motivation:
U(S, V, N) or S(U, V, N) both are extensive parameters. Some of these
parameters might be difficult to control or measure under usual experimental
conditions.
Basic idea:
Using Legendre transformations is to cast the above representation into
equivalent forms which, by contrast, utilize intensive parameters as
independent variables.
40
2-1
Molecular Rheology LAB
X, Y are extensive properties & Y=Y(X).
Let slope is ; : intersive properties
Y
P P
X

·

If one considers the slope and the
intercept at the same time, the
transformation from Y(X) to ψ(P) is an
unambiguous mapping.
Elimination of and yields
( )
1
( )
Y Y X
Y Y
P
X X
Y PX
X Y
P
ψ
ψ
ψ ψ
·
∂ −
· ·
∂ −
· −
·
Elimination of and yields
( )
( )
P
X
P
Y PX
P
Y Y X
ψ ψ
ψ
ψ
ψ
·

· −

· +
·
41
Generalization of the Legendre transformation
2-1
Molecular Rheology LAB

Elimination of and , ,
... , yields


1 1
1 1
1 1 1
( , , ... , )
( , , ... , , ,
... , )
t
k
k
k k
k
n
n n
t
Y Y X X X
Y
P
X
Y P X
Y X X
X
P P P X
X
ψ
ψ ψ
+
·

·

· −
·



Elimination of and , ,
... , yields

1 1 1
1 1
1 1
( , , ... , , ,
... , )
( , , ... , )
n n
t
k
k
k k
k
n
t
P P P X
X
X
P
Y P X
P P
P
Y Y X X X
ψ ψ
ψ
ψ
ψ
+
·

· −

· +
·

42
The Legendre Transformed Functions
The Legendre Transformed Functions
and Thermodynamic Potentials
and Thermodynamic Potentials
2-2
2-2
Molecular Rheology LAB
The energy representation of the
fundamental equation: ( , , ) U U S V N ·
Intensive parameters
, , ...
1 1
, , T P µ µ −

1 1
( , , ... , )
t
k
k
k k
k
Y Y X X X
Y
P
X
Y P X ψ
·

·

· −

Legendre transformed functions
Thermodynamic potentials



( , , )
( , , )
( , , )
F F T V N
H H S P N
G G T P N
·
·
·
43
The Helmholtz potential, F
2-2
Molecular Rheology LAB
( , , ) ( , , ) U S V N F T V N ⇒
Y X
ψ
P


( , , )
( , , )
U U S V N
U
T
S
F U TS
F F T V N
·

·

· −
·
, , ,
; ;
N V T N T V
F F F
S P
T V N
dF SdT PdV dN
µ
µ
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ − ≡ − ≡

∂ ∂ ∂
¸ , ¸ , ¸ ,
· − − +



1 1
1 1 1
( , , ... , )
( , , ... , , ,
... , )
t
k
k
k k
k
n n
t
Y Y X X X
Y
P
X
Y P X
P P P X
X
ψ
ψ ψ
+
·

·

· −
·

44
2-2
Molecular Rheology LAB
The Enthalpy, H
( , , ) ( , , ) U S V N H S P N ⇒
Y X
ψ
P


( , , )
( , , )
U U S V N
U
P
V
H U PV
H H S P N
·

·

· +
·
, , ,
; ;
P V S N P S
H H H
T V
S P N
dH TdS VdP dN
µ
µ
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ ≡ ≡

∂ ∂ ∂
¸ , ¸ , ¸ ,
· + +



1 1
1 1 1
( , , ... , )
( , , ... , , ,
... , )
t
k
k
k k
k
n n
t
Y Y X X X
Y
P
X
Y P X
P P P X
X
ψ
ψ ψ
+
·

·

· −
·

45
2-2
Molecular Rheology LAB
The Gibbs potential, G
( , , ) ( , , ) U S V N G T P N ⇒
Y X
2
ψ
P
2



( , , )
;
( , , )
U U S V N
U U
T P
S V
G U ST PV
G G T P N
·
∂ ∂
· − ·
∂ ∂
· − +
·
, , ,
; ;
P N T N P T
G G G
S V
T P N
dG SdT VdP dN
µ
µ
∂ ∂ ∂
¸ _ ¸ _ ¸ _
≡ − ≡ ≡

∂ ∂ ∂
¸ , ¸ , ¸ ,
· − + +
X
1
P
1



1 1
1 1 1
( , , ... , )
( , , ... , , ,
... , )
t
k
k
k k
k
n n
t
Y Y X X X
Y
P
X
Y P X
P P P X
X
ψ
ψ ψ
+
·

·

· −
·

46
The following equations are all fundamental equations:
2-2
Molecular Rheology LAB
The main spirit of the Legendre transformation is that the new
fundamental equation must be so derived that it does not lose any
thermodynamic information as incorporated in the original one.
( , , ) ( , , ) ( , , ) ( , , ) ( , , ) S U V N U S V N F T V N H S P N G T P N ≡ ≡ ≡ ≡
Typical applications of the derived fundamental equations:
F=F(T, V, N): Incompressible fluids
H=H(S, P, N): Heat transfer
G=G(T, P, N): Chemical reactions
47
Minimum Principles for the Potentials
Minimum Principles for the Potentials 2-3
2-3
Molecular Rheology LAB
Reservoir T
r
T
(1)
T
(2)
Thermal reservoir (C
p
→ ∞, T = T
r
)
Subsystem
The Helmholtz potential
Consider a subsystem in contact with a thermal reservoir.
Using U representation U=U(S, V, N) :
1
1
1
total
total
dU
d U
·
>
from the extremum
principle at equilibrium
48
2-3
Molecular Rheology LAB
( ) ( ) ( ) ( ) 1 1 1 1
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 1 1 1 1 1 1 1 1
( ) ( )
( ) ( ) 1
total r r r
dU dU dU T dS T dS T dS
P dV P dV dN dN µ µ
· + · + +
− + + + ·
r
dU dU



, , ,
r r r r r r
r r r
r r r r
r r r
V N S N V S
r r
U U U
dU dS dV dN
S V N
T dS
¸ _ ¸ _ ¸ _
∂ ∂ ∂
· + +

∂ ∂ ∂
¸ , ¸ , ¸ ,
·
Q
constant
The subsystem of interest ;
;
( ) ( ) 1 1
( ) ( ) 1 1
( ) ( ) ( ) ( ) 1 1 1 1
( ) ( ) ( ) ( ) 1 1 1 1
1
1 1
total total r r
r
S dS dS dS dS dS dS
dS dS dS
dV dV dN dN
dV dV dN dN
· ⇒ · + · + + ·
+ · −
⇒ + · + ·
· − · −
49
2-3
Molecular Rheology LAB
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 1 1 1 1 1 1 1 1 1 1
( ) ( ) 1 1
( ) ( ) 1 1
( ) ( ) 1 1
( ) ( ) ( ) ( ) 1

This equation always holds only if
r r
r
T T dS T T dS P P dV dN
T T T
P P
µ µ
µ µ
− + − − − + − ·
· ·
·
·
At equilibrium


1 1 1 1 1 1 1 1
1
( ) ( ) ( ) 1
1
( ) ( ) ( ) 1
1
total r r r r r
total r r
dU dU dU dU T dS d U T S d U TS
dF F U TS
d U d U U d U d U d U d U d TS d U TS
d F
· + · + · + · − ·
⇒ · · −
· + · + · · − · − >
⇒ >
Q
By eqn. A.9 of Appendix A ;
For thermal reservoir T = T
r
,

V
r
& N
r
= constant
50
2-3
Molecular Rheology LAB
Reservoir P
r
P
(1)
P
(2)
Reservoir T
r
& P
r
T
(1)
P
(1)
T
(2)
P
(2)
Subsystem
By the same way, consider a subsystem in contact with a pressure reservoir,
or with both pressure & thermal reservoirs.
1
( , , )
1
1
H H S P N
dH
d H
·
·
>
1
( , , )
1
1
G G T P N
dG
d G
·
·
>
51
2-3
Molecular Rheology LAB
The overall system:
The subsystem:
Representation: Experimental conditions: Extremum criteria:
,
1
( , , ) , ; 1 1
total total total total total
U U S V N V N S dU d U · · >
Representation: Experimental conditions: Extremum criteria:


1
( , , ) , , ; 1 1
( , , ) , ,
F F T V N T V N dF d F
H H S P N S P N
· · >
·

1
1
; 1 1
( , , ) , , ; 1 1
dH d H
G G T P N T P N dG d G
· >
· · >
52
2-3
Molecular Rheology LAB
The equilibrium value of any unconstrained internal parameter in contact
with a heat reservoir minimizes the Helmholtz potential over the manifold
of states for which T = T
r
Similarly, one can prove the Enthalpy minimum principle H(S, P, N) for
systems in contact with a pressure reservoir, as well as the Gibbs potential
minimum principle G(T, P, N) for systems in contact with both a heat and
pressure reservoir.
53
Applications of various Legendre
Applications of various Legendre
Transformed Potentials
Transformed Potentials
2-4.1 The Helmholtz potential
2-4.1 The Helmholtz potential
2-4
2-4
Molecular Rheology LAB
Question: What are the main applications?
Answer: Experiments carried out in rigid vessels with
diathermal walls, so that the ambient atmosphere
acts as a thermal reservoir.
Constant T Constant V, N (the
subsystem)
The F(T, V, N) is admirably suited.
54
2-4
Molecular Rheology LAB
Example
:
Two simple subsystems separated by a
movable, adiabatic, impermeable wall.
( ) 1
( ) 1
rev
?
?
?
V
V
W
·
·
·
( ) ( ) ( ) ( ) ( ) ( ) 1 1 1 1 1 1
( ) ( ) 1 1
( , , ) ( , , )
, a constant
r r
P T V N P T V N
V V V
·
+ ·
Can solve &
( ) ( ) 1 1
V V
The work delivered in a reversible process, by a system in contact with a
thermal reservoir, is equal to the decrease in the Helmholtz potential of
the system.
The number of independent variables: V & N
rev
( )

r r r r r
dW dU dU dU T dS dU T dS d U T S
dF
· − − · − − · − + · − −
· −
55
2-4
Molecular Rheology LAB
Focus our attention exclusively on the subsystem of interest, and relegate
the reservoir only to an implicit role.
As shown in Chap. 16, statistical mechanical calculations are enormously
simpler for such systems, permitting calculations that would otherwise be
totally intractable.
The Helmholtz potential is often referred to as the Helmholtz free energy,
though the term available work at constant temperature, would be less
subject to misinterpretation.
See Example.1 in page 159, which shows that one can increases the
entropy of a subsystem without changing the associated internal energy.
56
2-4
Molecular Rheology LAB
2-4.2 The enthalpy
At constant
1 1 1 1
...
,
i
dH TdS VdP dN dN
P N dH TdS dQ
µ µ · + + + +
⇒ · ·
As a potential for heat
Heating of a system is so frequently done while the system is maintained
at const. P. The enthalpy is generally useful in discussion of heat
transfers, and H is as a heat content of the system.


At constant
,
( , , )
( , , )
( , , ) ( , , ) ,
S N
i f f i
H S P N
H
V V S P N
P
Q H V P N H V P N P N

·
∂ ¸ _
· ·


¸ ,
· −
( , , ) H V P N
Using a similar argument, U is a potential for heat, too.
; at constant , dU TdS PdV dN V N dU TdS dQ µ · + + ⇒ · ·
57
2-4
Molecular Rheology LAB
The Joule-Thomson process
by conservation of energy ;
f i i i f f
f f f i i i
f i
u u Pv P v
u P v u Pv
h h
· + −
⇒ + · +
·
: initial molar energy
: molar volume
: molar enthalpy
u
v
h
A constant H process
We do not imply anything about the enthalpy during the process; the
intermediate states of the gas are non-equilibrium states for which the
enthalpy is not defined.
58
2-4
Molecular Rheology LAB
The isenthalpic curves
(“isenthalps”)

1 1
, , , ... H N N
T
dT dP
P

¸ _
·


¸ ,
( )
1
P
v
dT T dP
C
α · −
The final temperature T
f
can be
higher or lower then T
i
in this
process, depending on the
local relationship:
By eqn. A.22 of Appendix A
& Maxwell relations
If Tα >1, T will increase with a small increase in pressure, and vice versa.
For ideal gas, α = 1 / T, so that there will be no change in T.
59
2-4
Molecular Rheology LAB
2-4.3 The Gibbs potential
Most experiments are carried out under constant T & P.
is a particularly convenient choice . . . .
1 1
( , , , , ) G T P N N ⇒ ·
by defition:
the Euler relation:
i i
i
i i
i
G U TS VP
U TS VP N
G N
µ
µ
· − +
· − +
⇒ ·


As a potential for chemical potential
Consider the chemical
reaction:
1
1
r
j j
A ν ⇔

symbols for the chemical components
stoichiometric coefficients
:
:
j
j
A
ν
60
2-4
Molecular Rheology LAB
Change of G associated with changes in N
j
can be described by
j j
j
dG SdT VdP dN µ · − + +

since
1 1
1 1
...
j j
dN dN
dN dN dN ν
ν ν
· · · ⇒ ·
% %

or
1
1
j j
j
j j
j
dG dN µ ν
µ ν
· ·
·


%
One has for the equilibrium condition:
The final state of a chemical reaction can thus be determined if the
solution of the above equation is known, given that there is no depletion
of any species.
While G determines the equilibrium condition, H the heat of the reaction
can be obtained by the following relation:

1 1
1
, , , ...
r
j j
P N N
dH
T
dN T
ν µ
¸ _ ∂
· −


¸ ,

%
61
2-4
Molecular Rheology LAB
2-4.4 Compilations of empirical data
In practice, it is common to compile data on h (T, P), s (T, P), v (T, P);
v is redundant but convenient.
These relationships can, in principle, be utilized to construct the Gibbs
potential via g = h –Ts, and thus all thermodynamic may be obtained
using proper relationships, such as the Maxwell relationships.
62
Maxwell Relations and Some Applications
Maxwell Relations and Some Applications
2-5.1 The Maxwell relations & mnemonic diagram
2-5.1 The Maxwell relations & mnemonic diagram
2-5
2-5
Molecular Rheology LAB
Maxwell relations
( , , ) U U S V N ·
nd derivatives of potential 1
U U
S V V S
∂ ∂ ∂ ∂
¸ _ ¸ _
·

∂ ∂ ∂ ∂
¸ , ¸ ,

Maxwell relation equation
, , V N S N
P T
S V
∂ ∂
¸ _ ¸ _
− ·

∂ ∂
¸ , ¸ ,
P − T
Constant N
63
2-5
Molecular Rheology LAB
Table 2.1. Maxwell relations for several potentials with various pairs of
independent variables. (see also pp. 182 & 183 of the textbook)
In a similar way, we can derive other forms as shown below:
64
2-5
Molecular Rheology LAB
Mnemonic diagram
V F T
U G
S H P
Valid Facts Theoretical
Generate
Problems
Understanding
Hard Solutions
Pithy formula: “Valid Facts and Theoretical Understanding Generate
Solutions to Hard Problems”
65
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Molecular Rheology LAB


(" " arrow pointed away)
(" " arrow pointed toward)
,
,
S N
V N
U
T
S
U
P
V
∂ ¸ _
· +


¸ ,

¸ _
· − −


¸ ,
Example:
The first derivative of potential:
V F T
U G
S H P
Maxwell relations:
Example:

P S
T P
V T
S P
S V
P T
∂ ∂
¸ _ ¸ _
·

∂ ∂
¸ , ¸ ,
∂ ∂ ¸ _ ¸ _
· −

∂ ∂
¸ , ¸ ,
V
S P
T
S P
V
S P
T
P
T
(" ") + (" ") +
(" ") +
(" ") −
66
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Molecular Rheology LAB
If we are interested in Legendre transformations dealing with S and N
j
,
the mnemonic diagram takes the form shown as below in the left
diagram:
N
j
T
U
S
[ ] F U T ≡
[ ]
j
U µ
[ , ]
j
U T µ
X
1
P
1
U
X
2
P
2
1
[ ] U P
1
[ ] U P

1 1
[ , ] U P P
General-form mnemonic
diagram
U(S, N
j
) mnemonic diagram
j
µ
67
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Molecular Rheology LAB
2-5.2 Procedure for the reduction of derivatives
Thermal expansion coefficient:
Isothermal compressibility:
Molar leat capacity at constant pressure:
1 1
1 1
P P
T
T T
P
P
v V
v T V T
v V
v P V P
s T S
c T
T N
α
κ
∂ ∂ ¸ _ ¸ _
≡ ·

∂ ∂
¸ , ¸ ,
∂ ∂ ¸ _ ¸ _
≡ − · −

∂ ∂
¸ , ¸ ,
∂ ∂ ¸ _
≡ ·


¸ ,
Molar leat capacity at constant volume:
1
1
P P
V
V V V
dQ
T N dT
s T S dQ
c T
T N T N dT
¸ _ ¸ _
·


¸ , ¸ ,
∂ ∂ ¸ _ ¸ _ ¸ _
≡ · ·

∂ ∂
¸ , ¸ , ¸ ,
Four customarily used derivatives
68
For single-component systems and constant molecule numbers, the second
derivatives of Gibbs representation can be expressed by
2-5
Molecular Rheology LAB
, , and .
P T
c α κ
/ ; ;
1 1 1
1 1 P T
g g g
c T v v
T T P P
α κ
∂ ∂ ∂
· − · · −
∂ ∂ ∂ ∂
All first derivative, such as (involving both
extensive and intensive parameters), can be written in terms of three
independent second derivatives of the Gibbs potential (for the case of
single-component systems), conventionally chosen as .
( )
, V N
dT T P dP · ∂ ∂
and ,
P T
c α κ
69
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Molecular Rheology LAB
Reduction of derivatives
If the derivative contains any potential, bring them one by one to the
numerator and eliminate by the thermodynamic square.
Example:

Reduce the derivative
, G N
P
U
∂ ¸ _


¸ ,






1
, ,
1
, ,
1
, , , ,
G N G N
G N G N
S N P N V N P N
P U
U P
S V
T P
P P
G G G G
T P
P S P V



1
∂ ∂ ¸ _ ¸ _
·
1

∂ ∂
¸ , ¸ ,
1
¸ ]
1
∂ ∂ ¸ _ ¸ _
· −
1

∂ ∂
¸ , ¸ ,
1
¸ ]
1
∂ ∂ ∂ ∂ ¸ _ ¸ _ ¸ _ ¸ _
· − +
1

∂ ∂ ∂ ∂
¸ , ¸ , ¸ , ¸ ,
1
¸ ]
( )
( )
( )
( )


1
, ,
, ,
S N V N
P N P N
S T P V S T P V
T P
S T S S T V

1
− ∂ ∂ + − ∂ ∂ +
· − + 1
− ∂ ∂ − ∂ ∂
1
¸ ]
(See also pp. 187-188 of the textbook)
70
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Molecular Rheology LAB
If the derivative contains the chemical potential, bring it to the numerator
and eliminate by means of the Gibbs-Duhem relation, . d sdT vdP µ · − +
Example:

Reduce the derivative
, S N
V
µ ∂ ¸ _


¸ ,
, , , S N S N S N
T P
s v
V V V
µ ∂ ∂ ∂ ¸ _ ¸ _ ¸ _
· − +

∂ ∂ ∂
¸ , ¸ , ¸ ,
If the derivative contains the entropy, bring it to the numerator. If one of
the four Maxwell relations of the thermodynamic square now eliminates
the entropy, invoke it. If the Maxwell relations do not eliminate the
entropy put a under . The numerator will then be expressible as one
of the c
V
or c
P
.
T ∂ S ∂
Example:

Reduce the derivative
, S N
T
P
∂ ¸ _


¸ ,
, , , ,
P
T N P N P N S N
T S S V N
c
P T T T P
∂ ∂ ∂ ∂ ¸ _ ¸ _ ¸ _ ¸ _
· − ·

∂ ∂ ∂ ∂
¸ , ¸ , ¸ , ¸ ,
71
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Molecular Rheology LAB
Bring the volume to the numerator. The remaining derivative will be
expressible in terms of . and
T
α κ
Example:

Reduce the derivative
, V N
T
P
∂ ¸ _


¸ ,
, , ,
T
T N P N V N
T V V
P T P
κ
α
∂ ∂ ∂ ¸ _ ¸ _ ¸ _
· − ·

∂ ∂ ∂
¸ , ¸ , ¸ ,
The originally given derivative has now been expressed in terms of the
four quantities . The specific heat at constant volume
is eliminated by the follow equation.
and , , ,
P V T
c c α κ
1
V P
T
Tv
c c
α
κ
· −
72
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Molecular Rheology LAB
2-5.3 Some simple applications
I. Adiabatic compression
T
i
P
i
Adiabatic wall
T
f
=?
P
f
Adiabatic wall
Quasi-static process
If known: fundamental equation, , , and
i f i
P P T
Fundamental equation
Equations of state:
ΔT=T(S, P
f
, N)- T(S, P
i
, N)
T
If known: , , , , , and
i f i P
P P T c α κ

;
, ,
( )
S N P S N P
T Tv sTv
dT dP dP d d v dP
P c P c
α µ α
µ µ
∂ ∂ ¸ _ ¸ _
· · · · −

∂ ∂
¸ , ¸ ,
(see p. 190)
73
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Molecular Rheology LAB
II. Isothermal compression
P
i
P
f
Quasi-static process
Constant T


?
?
?
dS
dU
Q
·
·
∆ ·
If known: fundamental equation, , and
i f
P P
Fundamental equation
T
If known: , , , , and
i f P
P P c α κ

;

, ,
( )
f
i
T
T N T N
P
P
S U
dS dP VdP dU dP T v PV dP
P P
dQ T VdP Q T VdP
α α κ
α α
∂ ∂ ¸ _ ¸ _
· · − · · − +

∂ ∂
¸ , ¸ ,
· − ⇒ ∆ · −

Equations of state:



( , , )
( , , )
( , , ) ( , , )
f i
S S T P N
U U T P N
Q T S TS T P N TS T P N
·
·
∆ · ∆ · −
74
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Molecular Rheology LAB
III. Free expansion
Vacuum
Gas
V
i
; T
i
Gas
V
f
; T
f
=?
If known: fundamental equation, , , and
i f i
V V T
Fundamental equation
T
If known: , , , , , and
i f i P
V V T c α κ
Equations of state:
( , , ) ( , , )
f i f i
T T T U V N T U V N − · −
Constant U
Adiabatic wall
Adiabatic wall
, U N V V T
T P T
dT dV dV
V Nc Nc
α
κ
¸ _
∂ ¸ _
· · −



¸ ,
¸ ,
75
Homework
Homework
2-H
2-H
Molecular Rheology LAB
Problem 5.3-1
Problem 5.3-12
Problem 6.3-2
Problem 7.4-7
Problem 7.4-15
Problem 7.4-23
76
Molecular Rheology LAB
Stabilities, Phase Transitions, and
Critical Phenomena
Chapter 3
Chapter 3
Contents
3-1 Stability Conditions for Thermodynamic Potentials
3-2 Le Chaterlier’s Principle and Effects of Fluctuations
3-3 First-order Phase Transitions in Single-Component Systems
3-4 Thermodynamic States near Critical Points
77
Stability Conditions for Thermodynamic
Potentials
3-1.1 Intrinsic stability of thermodynamic systems
3-1.1 Intrinsic stability of thermodynamic systems
3-1
3-1
Molecular Rheology LAB
Basic extremum principle of thermodynamics:
1 dS · The S is an extremum value.
The extremum value is a maximum, which guarantees
the stability of predicted equilibrium states.
1
1 d S <
78
3-1
Molecular Rheology LAB
Initial state New state
S(U) S(U) S(U-ΔU) S(U+ΔU)
( )
1
Total
S S U · ( ) ( )
Total
S S U U S U U · + ∆ + − ∆
Remove ΔU from the
right subsystem and
transfer it to the left
subsystem.
( ) ( )
Stable
( ) 1 S U U S U U S U + ∆ + − ∆ ≤

( ) ( )
Unstable
( ) 1 S U U S U U S U + ∆ + − ∆ ≥

Convex
Concave
(see later dicussion
on phase separation)
(see later discussion on the
Le Chaterlier’s principle)
79
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Molecular Rheology LAB
The condition of stability is the concavity of the entropy.
( ) ( )
for all ( ) 1 S U U S U U S U + ∆ + − ∆ ≤ ∆

For
1
1
,
1 1
V N
S
U
U
¸ _

≤ ∆ →


¸ ,
By eqn. A.4 of Appendix A (refer to problem 8.1-1 of the textbook)
The same considerations apply to a transfer of volume.
( ) ( )

for all
For
1
1
,
( ) 1
1 1
U N
S V V S V V S V
S
V
V
+ ∆ + − ∆ ≤ ∆
¸ _

≤ ∆ →


¸ ,
The differential form is less restrictive than the concavity condition,
which must hold for all ΔU(ΔV) rather than for ΔU→ 0(ΔV→ 0) only.
80
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Molecular Rheology LAB
The portion BCDEF is unstable, because it violates the global form of
concavity of entropy. Yet, only the portion CDE fails to satisfy the differential
form of the stability condition.
The portions of the curve BC and EF are said to be “locally stable” but
“globally unstable.” (e.g., it is susceptible to large-amplitude perturbations)
Points on the straight line BHF correspond to a phase separation in which part
of the system is in state B and part in state F.
81
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Molecular Rheology LAB
If one simultaneously changes U and V:
( ) ( )

1
1 1 1
1 1
, , ( , ) 1
1
S U U V V S U U V V S U V
S S S
U V U V
+ ∆ + ∆ + − ∆ − ∆ ≤
¸ _¸ _ ¸ _
∂ ∂ ∂
− ≥

∂ ∂ ∂ ∂
¸ ,¸ , ¸ ,

1
1
,
1
V N
S
U
¸ _




¸ ,

1
1
,
1
U N
S
V
¸ _




¸ ,
The local conditions of stability ensure the
curve of the intersection of the entropy
surface with the plane of constant V or U
have a negative curvature.
But these two “ partial curvatures” are not sufficient to ensure concavity.
By eqn. A.4 of Appendix A (refer to
problem 8.1-1 of the textbook)
82
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Molecular Rheology LAB
3-1.2 Stability condition for thermodynamic potentials
Convexity of the energy surface:
( ) ( )
, , , , ( , , ) 1 U S S V V N U S S V V N U S V N + ∆ + ∆ + − ∆ − ∆ ≥


The local conditions of convexity:
For cooperative variations of and :
1
1
,
1
1
,
1
1 1 1
1 1
1
1
1
V N
S N
U T
S S
U P
V V
S V
U U U
S V S V
¸ _
∂ ∂
· ≥

∂ ∂
¸ ,
¸ _
∂ ∂
· − ≥

∂ ∂
¸ ,
¸ _¸ _ ¸ _
∂ ∂ ∂
− ≥

∂ ∂ ∂ ∂
¸ ,¸ , ¸ ,
83
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Molecular Rheology LAB
1
1 1 1
1 1
1
F F F
V T V T
¸ _ ¸ _ ¸ _
∂ ∂ ∂
− ≥

∂ ∂ ∂ ∂
¸ , ¸ , ¸ ,
Transform to other potential representations by Legendre
transformation :
( , , ) F T V N ·



; ; By the same way
1 1
1 1
, , ,
, ,
1 1 1
1 1 1
, , ,
1
1 1 1
1 1 1
V N V N V N
V N V N
V N V N T N
F S T U U
S S S T T
F U F
T S V
¸ _ ¸ _ ∂ ∂ ∂ ∂ ∂ ¸ _ ¸ _ ¸ _
· − · − · − · −

∂ ∂ ∂ ∂ ∂ ∂
¸ , ¸ , ¸ ,
¸ , ¸ ,
¸ _ ¸ _ ¸ _
∂ ∂ ∂
⇒ ≤ ≥ ≥

∂ ∂ ∂
¸ , ¸ , ¸ ,
Q
( ) ( )
, , , , ( , , ) 1 F T T V V N F T T V V N F T V N + ∆ + ∆ + − ∆ − ∆ ≥
Example:
By eqn. A.4 of Appendix A (refer to problem 8.1-1 of the textbook)
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Similarly, one has for other potentials


; ;
1
1 1 1 1 1
1 1 1 1
, ,
( , , )
1 1 1
V N V N
H S P N
H H H H H
S P S P S P
·
¸ _ ¸ _ ¸ _¸ _ ¸ _
∂ ∂ ∂ ∂ ∂
≥ ≤ − ≥

∂ ∂ ∂ ∂ ∂ ∂
¸ , ¸ , ¸ ,¸ , ¸ ,


; ;
1
1 1 1 1 1
1 1 1 1
, ,
( , , )
1 1 1
V N V N
G T P N
G G G G G
T P T P T P
·
¸ _ ¸ _ ¸ _¸ _ ¸ _
∂ ∂ ∂ ∂ ∂
≤ ≤ − ≥

∂ ∂ ∂ ∂ ∂ ∂
¸ , ¸ , ¸ ,¸ , ¸ ,
In summary, for constant N the thermodynamic potentials are convex
functions of their extensive variables and concave function of their
intensive variables.
85
Le Chaterlier’s Principle and the Effects
of Fluctuations
3-2.1 Le Chatelier’s principle
3-2.1 Le Chatelier’s principle
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Molecular Rheology LAB
Example:
The Le Chatelier’s principle: any inhomogeneity that somehow develops
will induce a process that eradicates the inhomogeneity.
Fluid
T
1
In equilibrium
state
Incident
photon
Container
T
1
T
1
Locally heating
the fluid
slightly.
Heat flows away
form heated
region.
The system restores
homogeneous state.
Fluid
T
1

86
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Molecular Rheology LAB
3-2.2 Effect of fluctuations
From the perspective of statistical mechanics all physical systems undergo
continual local fluctuations even in the absence of externally induced
vibrations, only to attenuate and dissipate in accordance with the Le
Chatelier principle.
The curvature of the potential well then plays a crucial and continual role,
restoring the system toward the “expected state” after each Brownian
impact (fluctuation).
87
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3-2.3 The Le Chatelier-Braun principle
The Le Chatelier-Braun principle: Various other secondary processes that
are also induced indirectly act to attenuate the initial perturbation.
T & P
reservoirs
P
i
; T
i
; V
i

Example:
Poston is moved outward slightly by
external agent or fluctuation.
Primary effect: The P
i
decreased-the pressure
difference across the piston then acts to push it
inward; this is the Le Chatelier principle.
P
o

Consider a subsystem contained within a cylinder with diathermal walls and
a loosely fitting piston.
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Molecular Rheology LAB
Secondary effect: An increased V
i
alters T
i
; heat flows inward if α >0 and
outward if α <0.
S V T
T T
dT dV dV
V Nc
α
κ
∂ ¸ _
· · −


¸ ,
;
1
1
S V T
P
dP dQ dQ TdS
T S NT c
dQ
κ
α ∂ ¸ _
· · ·


¸ ,
Then, P
i
is increased for either sing of α due to
the heat flow. Thus a secondary induced process
also acts to diminish the initial perturbation. This
is the Le Chatelier-Braun principle.
T & P
reservoirs
P
i
; T
i
; V
i

Poston is moved outward
slightly by external agent
or fluctuation.
P
o

Q
(note that is always
positive)
dQ α
89
First-order Phase Transitions in Single-
Component Systems
3-3.1 First-order & second-order phase transitions
3-3.1 First-order & second-order phase transitions
3-3
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Molecular Rheology LAB
Fluctuation
Fluctuations (e.g. Brownian motions) play an
important role bringing the system form one local
min. to the other. The possibility associated with a
successful jump is exponentially inverse to the energy
gap. It is therefore possible that the system trapped in
a metastable min. is effectively in stable equilibrium.
The system spends almost all the time in the more stable minimum.
Global min. is path independent state, yet the metastable one is path
dependent.
90
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First-order phase transitions
Definition: Shift of the equilibrium state from one local minimum to the other,
induced by a change in certain thermodynamic parameters.
Equilibrium state at constant T & P correspond to the min. in G(T, P, N).
The slope of the curve in the left figure is simply difference in pressure (?).
At T
4
, the molar Gibbs potential of two minima are equal, but other
properties (e.g. u, f, h, v ,s) are discontinuous across the transition.
High-density phase is more stable below the transition temperature, T
4
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Second-order phase transitions
Definition: At the so-called critical point (point D), the difference between two
distinct states disappears and there is only one equilibrium state.
Moving along the liquid-gas coexistence curve toward higher temperatures,
the discontinuities of two phase in molar volume and molar energy become
progressively smaller.
The existence of the critical point (D) precludes the possibility of a sharp
distinction between the generic term liquid and the generic term gas.
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3-3.2 Latent heat
At first-order phase transition:
I II
I II
I II
Discontinued in , , , , . But
( ) ( )
( ) ( )
( ) ( )
u f h v s P P
T T
µ µ ·
·
·
Example:
Latent heat of fusion:

since ; at phase transition point

( ) ( )
( ) ( )
( )
L S
LS
L S
LS
dQ Tds Q l T s s T s
h Ts
h T s l
µ µ µ
· ⇒ ∆ · · − · ∆
· − ⇒ ·
⇒ ∆ · ∆ ·
Ice Water Steam
kJ
. 11
kg-K
P
c · kJ
. 11
kg-K
P
c ·
cal
11
g
LS
l ·
cal
111
g
GL
l ·
Saturated steam table
Superheated steam table
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3-3.3 The Clapyron equation
Some interesting natural observations:
Ice skating: The pressure applied to ice on
the blade of the skate shifts the ice, providing
a lubricating film of liquid on which the
skate slides.
Mountain climbing: The pressure decreased
and the water boiling point decreased with
the higher altitude. Therefore, it is difficult to
cook on the high altitude mountain.
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The Clapron equation
Clapron equation is the slope of coexistence
curves.
Slope:
At phase equilibrium ;
;
'

'
and
the Cl
( )
( ) ( )
( )
A A B B
B A B A
B A B A
dP
dT
d sdT vdP
sdT vdP s dT v dP
dP s s s
v v dP s s dT
dT v v v
l
l T s s
T
dP l
dT T v
µ µ µ µ
µ µ µ µ µ
µ µ µ µ
′ ′
′ ′
′ ′
⇒ · ·
∴ − · − · − +
′ ′
⇒ − · − + · − · − +
− ∆
′ ′
− · − ⇒ · ·
− ∆
· ∆ ⇒ ∆ ·
·

apeyron equation
96
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Molecular Rheology LAB
The Clapeyron equation embodies the Le Chatelier principle. Consider a
solid-liquid transition with a positive latent heat (s
l
> s
s
):
If Slope
at constant System tends tow Increase more liquid ph ards the ase
( ) 1
l s
dP
P
v v
dT
T
< ⇒ · <

Increase dense (solid) phase
Increase entropic (liquid)
If Slope
at constant System tends towards the more
System tends towards the mo as re ph e
( ) 1
l s
dP
v v
d
P
T
T
T
> ⇒ · >


The Clapeyron-Clausius approximation:
; assume ideal gas
From Clapeyron equation
1
g l g g
RT
v v v v v
P
dP P
l
dT RT
∆ · − ≈ ⇒ ·
⇒ · ⋅
97
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Molecular Rheology LAB
3-3.4 1
st
phase transition based on van der Waals eq.
The van der Waals equation of state describes rather well the general
features of many gases and liquids.
van der Waals E.O.S.
1
( )
RT a
P
v b v
· −

Stability criteria: or 1 1
T
T
P
V
κ

¸ _
> <


¸ ,
Not all curves conform to the stability criteria. Clearly, portion FKM of T
1

curve violates the stability criterion.
Setting constant P will get one solution T in the T
9
curve, and three
solutions O, K and D in the T
1
curve. But only O and D have physical
meaning because K violates the stability criterion.
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Molecular Rheology LAB
The given P-v isotherms may be used to compute the molar Gibbs free
energy to better perceive the stability criterion.
It should be obvious that B, C, D are more stable than M, L, K and R, Q, O
are more stable than F, J, K etc.
or
is an undetermined function of the
( ) ( )
( )
d sdT vdP v P dP T
T T
µ µ φ
φ
· − + · +

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Molecular Rheology LAB
In general, for P < P
D
, the right-hand branch (ABCD) of the isotherm in
right figure is physically significant, whereas for P > P
D
the left-hand
branch (SRQD) is physically significant. The intermedium region is
physically unstable.
The area of region I is the same as that of region II, and for the region in
between liquid and gas (OD) coexist. This is the way to determine the
phase transition points (O, D).
( ) 1
O
D
v P dP ·

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Molecular Rheology LAB
The entropy change during the phase transition can be computed using the
following relation along hypothetical isotherm OMKFD.
The total change in the molar energy:
Limitation: Can’t apply near critical point.
the Maxwell relation
T
v T v OMKFD
s
ds dv
v
P s P
s dv
T v T
∂ ¸ _
·


¸ ,
∂ ∂ ∂
¸ _ ¸ _ ¸ _
∆ · ·

∂ ∂ ∂
¸ , ¸ , ¸ ,

Q
u T s P v ∆ · ∆ − ∆
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Molecular Rheology LAB
The O, D, O’, D’, O’’, D’’ are first-order phase transitions, and O’’’ (D’’’)
corresponds to the critical point, termination of the gas-liquid coexistence.
The component in each of the phases is governed by the lever rule.
; 1
g l g g l l z
g z
l
g l
z l
g
g l
x x x v x v v
v v
x
v v
v v
x
v v
+ · + ·

·


·

102
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Molecular Rheology LAB
3-3.5 Summary of stability criteria
U=U(x
1
, x
2
, …) or U=U(P
1
, P
2
, …) must be a “convex function” of its
“extensive parameters” and a “concave function” of its “intensive
parameter.”
Geometrically, the function must lie above its tangent hyper-planes in the
x
1
, … , x
s-1
subspace and below its tangent hyper-planes in the P
s
, … , P
t

subspace.
103
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Molecular Rheology LAB
3-3.6 First-order phase transitions in multi-component
systems
For a multi-component system the fundamental relation:
U = U(S, V, N
1
,N
2
, …,N
r
)
or the molar form:
u = u(s, v, x
1
,x
2
, …, x
r - 1
)
At the equilibrium stable the “energy” , i.e., the enthalpy and the
Helmholtz and Gibbs potentials are “convex functions” of the mole
fraction x
1
, x
2
, … , x
r - 1
.
The mole fractions, like the molar entropies and the molar volumes, differ
in each phase during a phase transition. Can be utilized for the purpose of
purification by distillation.
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Molecular Rheology LAB
Gibbs phase rule is the thermodynamic degrees of freedom (f).
Gibbs phase rule
[ ]
[ ]
: No. of components
: No. of phases
: No. of parameters capable of independent v
: , each phase have variations No. of phase
intensi ariati
:
v
s
o s e n
( ) ( - ) 1 1 1
( ) 1
( ) ( ) 1 1 1
( )
1 f M r r M r M
r
M
f
M r M
r M
r P T
· + − − − · −

+
+ − + ×
I II M
I II M
...

...
1 1 1
r r r
µ µ µ
µ µ µ
1
· · ·
1
1
1
· · ·
¸ ]
M
variations equations
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Molecular Rheology LAB
Application of the Gibbs phase rule
Example:
I. Single-component system (r =1)
a: M=2 → f =1 → at a given T, P must be unique
b: M=3 → f =0 → the triple point
II. Two-component system (r =2)
a: M=1 → f =3 → T, P, x
1
(or x
2
) can be arbitrarily assigned
b: M=2 → f =2 → T, P can be arbitrarily assigned
c: M=3 → f =1 → T, for example, can be arbitrarily assigned
d: M=4 → f =0 → four phases coexist at unique point
※There cannot be five phases coexist in this case
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Molecular Rheology LAB
3-3.7 Phase diagrams for binary systems
Example:
The three-dimensional phase diagram of a typical gas-liquid binary system.
The two-dimensional sections are constant P planes, with P
1
< P
2
< P
3
< P
4
.
The C state in the two-
phase state is composed
of A and B, and only A
and B are physical point.
107
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Molecular Rheology LAB
Example:
Typical phase diagram for a binary
system.
Phase diagram for a binary system
in equilibrium with its vapor
phase. (P is not constant)
108
Thermodynamic States near Critical
Thermodynamic States near Critical
Points
Points
3-4.1 Features in the vicinity of the critical point
3-4.1 Features in the vicinity of the critical point
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Molecular Rheology LAB
As the point approaches the critical point the two minima of the underlying
Gibbs potential coalesce.
The distinction in phases utilized in the first-order transition breaks.
109
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Molecular Rheology LAB
As the critical point is reached the single minimum is a flat bottom, which
implies the absence of a “restoring force” for fluctuations away from the
critical state.
In the critical region, long-range correlated fluctuation become the
dominant factor affecting the thermodynamic properties, and the short-
range atomistic feature becomes unimportant.
Universal scaling behavior is predicted by the “ renormalization group
theory” and verified in experiments for the behavior of the susceptibilities
“ near the critical point.”
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Molecular Rheology LAB
The generalized susceptibilities, such as c
p
, κ
T
and α diverge.
Example:
at first phase transition or near cri tical point
diverges; and diverge in a similar way.
1
T
T
T
T p
v
v P
v
P
c
κ
κ α
∂ ¸ _
·


¸ ,

¸ _
→∞


¸ ,

111
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Molecular Rheology LAB
3-4.2 The failure of the classical theory in predicting
the scaling behavior near the critical point.
Over-simplification of the extremum principle in classical
thermodynamics. It must be replaced by the associated “probability
distribution” and the consequent average properties.
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Molecular Rheology LAB
The basic postulate of thermodynamics incorrectly identifies the most
probable value of the energy as the equilibrium or average value.
The deviation becomes very pronounced near critical points when the
thermodynamic potentials become very shallow.
Renormalization-group theory demonstrates that the numerical values of
the scaling exponents for a large class of materials are identical, dependent
primarily on the dimensionality of the system and on the order parameter.
113
Homework
Homework
3-H
3-H
Molecular Rheology LAB
Problem 9.1-1
Problem 9.3-3
Problem 9.4-11
Problem 9.7-1
114
Applications to Material Properties
Applications to Material Properties
Contents
4-1 The general ideal gas
4-2 Small Deviations from Ideality—The Virial Expansion
4-3 Law of Corresponding States for Gases
4-4 Applications to Dilute Solutions—The van’t Hoff Relation
and the Raoult’s law
4-H Homework
Chapter 4
Chapter 4
Molecular Rheology LAB
115
The general ideal gas
The general ideal gas
4-1.1 The essence of ideal gas behavior
4-1.1 The essence of ideal gas behavior
4-1
4-1
Molecular Rheology LAB
Ideal gas behavior (which is good at sufficiently low density and fails
evidently in the vicinity of their critical points) means that the gas do not
interact, implying the following properties:
1. PV = NRT
2. For single-component ideal gas, T = T(u) or u = u(T)
3. The Helmholtz potential F(T, V, N
1
, …) is additive (Gibbs’s theorem)
4. have the same value for all ideal gas
, ,
1 1
T p v
c c R
P T
κ α · · − ·
116
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Molecular Rheology LAB
The , and of general multicomponent id eal gas:

: arbitrarily chosen standard temperatur e
1
1
1
1
1
( , ) ( ) ( , )
( ) ( )
1
( ) ln
j j
j j
T
j j j j j j vj
T
T
j j j vj j
T
j j j
F U S
F T V U T T S T V U TS
U N u T N u N c T dT
T
v
S N s N c T dT N R
T v
· + · −
′ ′
· · +
′ ′
− · +

∑ ∑

∑ ∑ ∑


1
1
1
1
( ) ln ln
j
T
v j j
T
j
N
N
v
N c T dT NR NR x x
T v
¸ _


¸ ,
′ ′
· + −



entropy of mixing
(see also Eq. (3.40)
(at the same temperature and particle density)
117
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Molecular Rheology LAB
In general, however, the heat capacity, for instance, depends on the
internal degrees of freedom, as well as on the system temperature which
has to do with different modes of excitation.
e.g. stretching of interatomic bond, kinetic energy of vibration, rotation,
translational motions of the molecules, other potential and kinetic energy
The heat capacity of real gases
approaches a constant value at high
temperatures. At intermediate
temperatures, each such mode
contributes additively and
independently to the heat capacity. This
accounts for a “step-like” feature in the
c
v
versus T curves.
Step-like
118
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Molecular Rheology LAB
4-1.2 Chemical reactions in ideal gases
Partial molar Gibbs poential:
Since at chemical equilibrium
Let , equilibrium constant, be defined b y
can in p
( ) ln ln
1
ln ln ln ( )
( ) ln ( ) ln ( )
( )
j j j
j j
j
j j j j j
j j j
j j
j
j
RT T P x
v
v x v P v T
K T K T v T
T
µ φ
µ
φ
φ
φ
1
· + +
¸ ]
·
⇒ · − −
· −

∑ ∑ ∑

rinciple be known, so that can be consi dered as known.
For given & together with each of ca n be determined.
The mass action law:
( )
1
( )
j j j
j j
j
v v
j
j
K T
T P x x
x P K T
·

⇒ ∏ ·

The only temperature-
dependent term
119
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Molecular Rheology LAB
reaction : ; reaction : 1 1
If can be obtained by summing the previ ous reaction,
that is, ; & are constant
Then it
( ) ( ) 1 1
( ) 1
( ) ( ) ( ) 1 1 1
1 1 1 1
1 1
1
( ) 1
j j j j
j j
j j j j j
v A v A
v A
v A B v B v A B B
÷÷→ ÷÷→
←÷÷ ←÷÷
÷÷→
←÷÷
÷÷→
≡ +
←÷÷ ∑
can be shown that:
The reaction heat can also be compute
(see an example in
d from as
(the van'
page of the textb 222
t Hoff relat
ook.
ion)
)
1 1 1 1 1
1
ln ( ) ln ( ) ln ( )
( )
ln ( )
K T B K T B K T
K T
dH d
RT K T
dN dT
· +
·
%
Can help tabulations of K(T)
for various chemical reactions.
Logarithmic additivity of K(T)
120
Small Deviations from Ideality—The Virial
Small Deviations from Ideality—The Virial
Expansion
Expansion
4-2
4-2
Molecular Rheology LAB
: "Second virial coefficient" which accounts for the contribution from
.
: "Third virial coefficient" which accounts for the con
two-body interactions
tribution
h
fr
t
om
1
( ) ( )
1
( )
( )
P R B T C T
T v v v
B T
C T
¸ _
· + + +⋅ ⋅ ⋅

¸ ,
ree-body interactions etc.
Ideal behavior
Correction
term for v
For simple gases, use of the second virial coefficient may suffice to
capture their physical behaviors; for complex fluids, more correction
terms must be introduced.
4-2.1 Virial expansion
4-2.1 Virial expansion
121
4-2
Molecular Rheology LAB
ideal
ideal
ideal
(from )
(from ; )
(fr
1 1
1 1 1
, 1 1 1 1 1
1
1 1
( ) ( ) ( )
1 1
( ) ( ) ( ) 1 1 1
1 1
1 1 1
1 1
v v
v
v
B T C T D T
f f RT
v v v
f
P
v
d BT d CT d DT
c c RT
v dT v dT v dT
s f
c T s
T T
dB dC dD
u u RT
v dT v dT v dT
¸ _
· + + + +⋅ ⋅ ⋅

¸ ,

· −

¸ _
· + + + +⋅ ⋅ ⋅

¸ ,
∂ ∂
¸ _
· − ·

∂ ∂
¸ ,
¸ _
· + + + +⋅ ⋅ ⋅

¸ ,
om ) u f Ts · −
(f is the molar Helmholtz potential)
4-2.2 Other thermodynamic quantities may be
expanded in a self-consistent fashion
122
4-2
Molecular Rheology LAB
The second virial coefficient vanishes at some special temperatures for
several simple gases.
123
Law of Corresponding States for Gases
Law of Corresponding States for Gases
4-3.1 Important observations for gases
4-3.1 Important observations for gases
4-3
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Molecular Rheology LAB
In the equation of state of a given fluid, there is one unique point -the
critical point—characterized by T
cr
, P
cr
, and v
cr
.
The dimensionless constant P
cr
v
cr
/R T
cr
has value on the order of 0.27 for
all “normal” fluids of the three parameters that characterizes the critical
point. It thus appears that “only two are independent”.
(see more data in
Table13.1 of the
textbook)
124
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Molecular Rheology LAB
4-3.2 The Law of corresponding states
There exists, at least semi-quantitatively, a universal equation of state
containing no arbitrary constants if expressed in the reduced variables
v

/v
cr
, P/P
cr
, and T/T
cr
. This empirical fact is known as the “Law of
corresponding state”.
e.g. It has been customary to plot the compressibility factor in a way
as functions of P/P
cr
, and T/T
cr
.
or . 111
cr cr cr
Pv P v T
Z Z
P v T RT
¸ _¸ _ ¸ _
≡ ·

¸ ,¸ , ¸ ,
125
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Molecular Rheology LAB
T
r
curve
126
4-3
Molecular Rheology LAB
A possible origin of the universal, two-parameter equations of state -the
“van der Waals force” of two spherical-like, non-polar molecules.
The force between two molecules can be parameterized by the radius of
the molecule, which describes the short-range repulsion, and the strength
of the long-range attraction.
The long-range attractive force falls with distance as 1/r
6
and has arisen
from the instaneous dipole moment fluctuations.
Attractive force
Repulsive force
1
11
1
1
r
r


The Lennard-Jones potential
127
Applications to Dilute Solutions—the van’t
Applications to Dilute Solutions—the van’t
Hoff Relation and the Raoult’s law
Hoff Relation and the Raoult’s law
4-4.1 the van’t Hoff relation for osmotic pressure
4-4.1 the van’t Hoff relation for osmotic pressure
4-4
4-4
Molecular Rheology LAB
Consider a single-component fluid system, the Gibbs potential of the dilute solution
can be written in the general form:
represents the effect of the interaction energy between the two types of molecules,
while the last two te


1 1
1 1 1 1 1 1
1 1
1
1
1 1
( , , , ) ( , ) ( , ) ln
ln
N
G T P N N N P T N P T N RT
N N
N
N RT
N N
ψ
µ ψ ≅ + +
+
+
+
rms accounts for the entropy of mixing
In dilute region ( )

1 1 1
1 1 1 1
1 1 1 1 1
1
1
1 1 1 1 1 1 1
1
ln , ln
( , , , ) ( , ) ( , ) ln
N N N
N N N N
N N N N N
N
G T P N N N P T N P T N RT N RT
N
µ ψ
<< ⇒ ≅ ≅ −
+ +
⇒ ≅ + − +
128
4-4
Molecular Rheology LAB
Solvent and solute partial molar Gibbs potentials:
, , ,
, , , ;
1
1 1
1
1
1
1 1
( ) ( )
( ) ( ) ln ( )
G
P T x P T xRT
N
N G
P T x P T RT x x
N N
µ µ
µ ψ

· · −


· · + ≅

The pressure on the pure solvent side is maintained
constant (=P), but the mixture side can alter by
change in height of the liquid level in a vertical
tube.
The equilibrium condition:
, , , ,
: The pressure on the solute side of the membrane
1 1
( ) ( ) 1 P T P T x
P
µ µ

·

129
4-4
Molecular Rheology LAB
, , , ,
Expanding , , around the pressure
, ,
, , , ,
, ,
Multiplying by

1 1
1
1
1 1
1
1
1
( ) ( ) 1 1
( ) 1
( ) 1
( ) ( ) ( ) 1 1
( ) ( ) 1
( )
P T P T xRT
P T P
P T
P T P T P P
P
P T P P v
P P v xRT
N
V P N RT
µ µ
µ
µ
µ µ
µ

· −


′ ′
· + × −


· + −

− ·
⇒ ∆ ·
the van’t Hoff relation for osmotic
pressure in dilute solutions
130
4-4
Molecular Rheology LAB
4-4.2 Application to vapor pressure
liq gas
liq gas
liq gas
liq
The vapor pressure reduced by addition of low concentration of nonvolatile solute:
, ,
, ,
Expanding , and , around the pressure
,
( ) ( )
( ) ( )
( ) ( )
(
P T P T
P T xRT P T
P T P T P
P
µ µ
µ µ
µ µ
µ
·
′ ′
⇒ − ·
′ ′

liq liq
gas gas gas
,
, ,
; (the ideal gas equation: )

) ( ) ( )
( ) ( ) ( )
g l
g l g
T P T v P P
P T P T v P P
xRT
P P
v v
RT
v v v
P
P
x
P
µ
µ µ

· + × −
′ ′
· + × −

− · −

>> ·

⇒ ≅ − Raoult’s law
131
Homework
Homework
4-H
4-H
Molecular Rheology LAB
Problem 13.2-2
Problem 13.5-2
Problem 13.5-3
132
Statistic Ensembles and Formulism
Statistic Ensembles and Formulism
Chapter 5
Chapter 5
Molecular Rheology LAB
Contents
5-1 The entropy representation—the Boltzmann’s law
5-1.1 Physical significance of entropy for closed system (15.1)
5-1.2 The Einstein model of a crystalline solid (15.2)
5-1.3 The two-state system (15.3); a polymer model (15.4)
5-2 The Canonical Formalism
5-2.1 The probability distribution (16.1)
5-2.2 The partition function (16.2)
5-2.3 The classical ideal gas (16.10)
5-3 Generalized Canonical Formulations
5-3.1 Entropy as a measure of disorder (17.1)
5-3.2 The grand canonical formalism (17.3)
133
The
The
E
E
ntropy
ntropy
R
R
epresentation—the
epresentation—the
Boltzmann’s law
Boltzmann’s law
5-1.1 Physical significance of entropy for closed system
5-1.1 Physical significance of entropy for closed system
5-1
5-1
Molecular Rheology LAB
Classical Thermodynamics
Statistical Thermodynamics
Erected on a basis of few hypotheses of entropy.
e.g. S=S(U, V, N) ; extremum principle
Statistical mechanics provides the physical interpretation of the
entropy and a heuristic justification for the extremum principle.
134
5-1
Molecular Rheology LAB
Macroscopic systems Atomic systems
Closed system
given V & N
U, V, and N are the
only constraints on
the system.
Quantum mechanics
If the system is macroscopic, there
may exist many discrete quantum
states consistent with the specified
values of U, V, and N.
Naively, we might expect the system in a particular quantum state would
remain forever in that state.
The apparent paradox is seated in the assumption of isolation of physical
system. No physical system is, or ever can be, truly isolated.
A realistic view of a macroscopic system is one in which the system
makes enormously rapid random transitions among its quantum states. A
macroscopic measurement senses only an average of the properties of
myriads of quantum states.
135
5-1
Molecular Rheology LAB
Equal probability assumption
Consider a “isolated” system and “constraint N, V, & U.” Not all of the
system microstates are determined, and hence one is concerned with the
probability associated with each of these microstates.
Equal probability assumption brought out by Boltzmann:
A macroscopic system samples every permissible quantum state with
equal probability.
The assumption of equal probability of all permissible microstates is the
fundamental postulate of statistical mechanics.
Equal probability assumption applies only to isolated systems.
136
5-1
Molecular Rheology LAB
Correlation of Ω & S
The No. of microstates (Ω) among which the system undergoes transitions,
and which thereby shares uniform probability of occupation, increases to the
max. permitted by the imposed constraints.
According to the postulate of the entropy increases to the max. permitted by
the imposed constraints.
It suggests that the entropy can be identified with the number of
microstates consistent with the imposed macroscopic
constraints.
137
5-1
Molecular Rheology LAB
Entropy ( )
additive (extensive)
S No. of microstates ( )
Multiplicative

6
6

6
6
×


ln
B
S k · Ω
The constant prefactor merely determines the scale of S, and agrees with
Boltzmann’s constant k
B
=R/N
A
=1.3807 × 10
-23
J/K.
Nevertheless, the microcanonical formulation establishes the clear and
basic logical foundation of statistical mechanics.
138
5-1
Molecular Rheology LAB
5-1.2 The Einstein model of a crystalline solid
Consider a nonmetallic crystalline solid, and just focus on the vibrational
modes. Electronic excitations, nuclear modes, and various other types of
excitations were ignored.
Assumed the atoms in the crystal are free to vibrate
around its equilibrium position in any of thr

ee coordinate
directions, and can be replaced b harmonic oscillato y
all with the
,

rs
same natural
1N
N
%
%
1
frequen y . c ω
1
1
Einstein introduced the energy of harmonic oscillators discretely:
= ;
; : Planck's constant
Discrete values of energy:
1
, , , ... 111
1
/ 1
n n
h h
n
ε ω
π
ω
¸ _
+ ·

¸ ,
·
h
h
h
139
5-1
Molecular Rheology LAB
Number of permutations of
( )
1
1 1 N U ω − +
%
h
If the energy of the system is it
can be considered as constituting
quanta. Theres quanta are
to be distributed among
vibrational modes.
1
1
U
U
N
ω h
%
( )
( )
( )
( )
( )
( )
( )
( )
( )
H C
( )
1
1 1
1
1 1 1
1
1 1
1 1
! 1 1
! ! 1 1
! ! 1 1 1
! ! ! ! 1 1 1
N U N
U U
N U
N U
N U N U
N
N U N U
ω
ω ω
ω
ω
ω ω
ω ω
+ −
+ −
· ·

+ − +
∴ Ω · ≅ → ∞

% %
h
h h
%
h
%
h
% %
h h
%
Q
% %
h h
140
5-1
Molecular Rheology LAB
;
From & if
1 1
1 1 1
ln ln 1 1 1 1 1
ln ln( !) ln ( ) 1
A
B
u u u
s R R u N
u u u
S k M M M M M
ω
¸ _ ¸ _
· + + + ≡

¸ , ¸ ,
· Ω ≅ − +⋅ ⋅ ⋅ >>
h
According to this equation, which is independent of the volume, the
pressure is identically zero. Such a nonphysical result is a reflection of the
naive omission of volume dependent effect from the model.
Thermal equation of state:
There are oscillator in the system
mean energy per oscillator
The quantity is ca Einstein tempe lled r the atur "
1
1
1
1
1
1 1
ln 1
1
1 1
B
B
A
A
T
B
k
A
k S N
N
T U U
NN
U
N
k
N e
ω
ω
ω
ω
ω

¸ _
· · +


¸ ,

⇒ · ·

h
h
h
h
h
" of the crystal,
and it generally is of the same order of magnitude as the melt point of the
e
solid.
141
5-1
Molecular Rheology LAB
c
v
approaches a
constant value (3R)
at high
temperature.
c
v
is zero at zero
temperature.
Einstein model is in qualitative agreement with experiment, but the rate of
increase of the heat capacity is not quantitatively correct.
At low temperature c
v
rises exponentially, whereas experimentally the
heat capacity rises approximately as T
3
.
142
5-1
Molecular Rheology LAB
5-1.2 The two-state system ; a polymer model
Two-state system
Ground state
(with energy 0)
Excited state
(with energy ε)
Total atoms N
%
: system energy U
( ) atoms are
in the ground state
-
U
N
ε
%
atoms are in
the excited state
U
ε
( )
( )
C
From & if
!
! !
ln ln 1
ln ln( !) ln ( ) 1
N
U
B
B
N
U N U
U U U U
S N k
N N
S k M M M M M
ε
ε ε
ε ε ε ε
∴ Ω · ·

¸ _ ¸ _
⇒ · − − −

¸ , ¸ ,
· Ω ≅ − +⋅ ⋅ ⋅ >>
%
%
%
%
% %
143
5-1
Molecular Rheology LAB
( )
( )
Thermal equation of state:
;
1 1
1
1 1
1 1 1
1
1
ln 1
( )
1
1
B
B
B B
B
B
k T
k T
k T k T
A A
k T
B B
k S N
T U U
N
U U N
e
du e
c N N e e
dT k T k T
e
ε
ε
ε ε
ε
ε
ε
ε
ε
ε ε


¸ _

· · −


¸ ,
⇒ · <
+
⇒ · · · +
+
%
%
%
Q
The energy approaches as the temperature approaches infinity in
this model.
At infinite temperature half the atoms are excited and half are in their
ground state.
1 Nε
%
144
5-1
Molecular Rheology LAB
Schottky hump
The max. is taken as an indication of a pair of low lying energy states,
with all other energy states lying at considerably higher energies.
It is an example of the way in which thermal properties can reveal
information about the atomic structure of materials.
145
5-1
Molecular Rheology LAB
A polymer model
Each monomer unit of the chain is permitted to lie +x, -x, +y, and –y.
The length between two monomer unit is a.
Represent interference by assigning a positive energy ε to such a
perpendicular monomer.
146
5-1
Molecular Rheology LAB
x x y y
x
x x x
y
y y y
y y
N N N N N
L
N N L
a
L
N N L
a
U
N N U
ε
+ − + −
+ −
+ −
+ −
+ + + ·

− · ·

− · ·

+ · ·
%
( )
( )
( )
( )
1
1
1
1
1
1
1
1
x x
x x
y y
y y
N N U L
N N U L
N U L
N U L
+

+

′ ′
· − +
′ ′
· − −
′ ′
· +
′ ′
· −
%
%
The number of configurations of the polymer
consistent with given corrdinates and
of its terminus and given energy :

!
( , , , )
! ! ! !
x y
x y
x x y y
L L
U
N
U L L N
N N N N
+ − + −
Ω ·
%
%
147
5-1
Molecular Rheology LAB
( ) ( )
( ) ( )
( ) ( )
( ) ( )

or



ln ln ln ln
ln ln
1 1
ln ln
1 1
1 1
ln
1 1
1 1
ln
1 1
1 1
ln
1 1
B B x B x x B x
y B y y B y
B x B x
x B x
y B y
y B y
S k Nk N N k N N k N
N k N N k N
S Nk N N U L k N U L
N U L k N U L
U L k U L
U L k U L
+ + − −
+ + − −
· Ω · − −
− −
1
′ ′ ′ ′
· − − + − +
1
¸ ]
1
′ ′ ′ ′
− − − − −
1
¸ ]
1
′ ′ ′ ′
− + +
1
¸ ]

′ ′ ′ ′
− − −
¸
% %
% % % %
% %
1
1
]
; ( )
&
ln 11
1
1 1
y y
B
y
y y
y
y y y y y y y y y
U L
k S
T L a U L
L
L L N N L a L L N N
a
τ
+ − + −
′ ′


− · · · ·
′ ′
∂ +
′ ′ ′
⇒ · ⇒ − · · ≠ ∴ · · ⇒ ·
Q
Q
T
148
5-1
Molecular Rheology LAB
( ) ( )
( )

1
1
1
1
1
ln
1
1
ln ln ln
1 1
x B
B
x x B
x x
a k T
x
B B B
x x
x
k T
N U L k S
T L a N U L
N U L
e
N U L
k k k S
N L U N L U U
T U
N U L
e
U
ε
ε ε ε

′ ′
− − ∂
− · ·
′ ′
∂ − +
′ ′
− −
⇒ ·
′ ′
− +

′ ′ ′ ′ ′
· · + − + − − −

′ ′
− −
⇒ ·
%
%
%
%
% %
%
T
T
( )
( )
( )
For small (relative to )
The modulus of elasticity of the rubber band:
1
1
1
sinh
cosh
1
1
1
1
B
B
B
x B
x
k T
x B
x
x B x k T
B
k T
x
x B
T
a k T
L
N a k T e
Na
a k T L
k T e
L a
e
N k T
ε
ε
ε





·
+
⇒ · + ⋅ ⋅ ⋅
+

¸ _

⇒ · +


¸ ,
%
%
%
T
T
T
T
T
149
The Canonical Formalism
The Canonical Formalism
5-2.1 The probability distribution
5-2.1 The probability distribution
5-2
5-2
Molecular Rheology LAB
Limitation of microcanonical formalism:
The microcanonical formalism is simple in principle, but it is computationally
feasible only for a few highly idealized models.
Isolated
system
Must calculate the no. of combinatorial ways that a given total
energy can be distributed in arbitrarily sized boxes.
Generally beyond our mathematical capabilities!
system
T reservoir
Remove the limitation on the amount of energy available
-to consider a system in contact with T reservoir rather
than an isolated system.
Canonical formalism (Helmholtz representation)
150
5-2
Molecular Rheology LAB
Canonical formalism
subsystem
T reservoir
Closed system
In “subsystem,” each “state” does not have the same probability, as for an
closed system” to which the principle of equal probability of
“microstates” applies.
i.e., the subsystem does not spend the same fraction of time in each state.
The key to the canonical formalism is the determination of the probability
distribution of the subsystem among its microstates.
Closed system = Subsystem + T
reservoir
(note that the energy of the subsystem fluctuates)
151
5-2
Molecular Rheology LAB
A Simple analogy
thrown
Sum of no. =12
Sum of no. 12
Record red dice
no.
What fraction of these recorded
throws has the red die shown a
one, a two,…, a six ?
2/25
3/25
4/25
5/25
6/25
5/25
Reservoir
subsystem
Sum is12 corresponds to
given total energy
The numbers shown
correspond to the
energy of the system
Each state does
not have the same
probability.
152
5-2
Molecular Rheology LAB
Probability of subsystem
( )
( )
( )
( )
{ }
( )
The probability of the subsystem in state :
; : the energy in state
; from
If is the average value of the su
res tot
tot tot
1
res tot
1
tot tot
exp
ln
exp
j
j
j j
B j
j B
B
f j
E E
f E j
E
k S E E
f S k
k S E
U


Ω −
·


⇒ · · Ω
( ) ( ) ( )
( )
( ) ( )
( )
( ) { } ( )
bsystem
Expanding around the equilibrium point :
tot tot res tot
res tot tot
res tot res tot res tot
1 ( ) 1
R j B
j
j
j j
k T E k T U TS U
j
S E S U S E U
S E E E U
U E
S E E S E U U E S E U
T
f e e
− −
⇒ · + −
− −

⇒ − · − + − · − +
⇒ ·
153
5-2
Molecular Rheology LAB
( ) { } ( )
1
define
is state-independent normalization factor
define
Fundamental relation in the canonical formali
1 ( ) 1
1
Z Z
R j B
j
j j
j
k T E k T U TS U
j
E
F
j
B
F
E E
F F
j
j j j
E
F
j
f e e
f e e
k T
e
f e e e e
e e
β
β
β
β β
β β
β
β
β
− −

− −


·
≡ ⇒ ·
∴ · · ·
≡ ⇒ ·
∑ ∑ ∑

Q
sm:
The probability of occupation of the -th state:
ln lnZ
j
j
i
E
j
E
E
j
i
F e
j
f e e
β
β
β
β



− · ≡
·


154
5-2
Molecular Rheology LAB
The average energy:
or
; & lnZ lnZ
j
i
E
E
j j j
j j i
U E f E e e
d F
U U F T F
d T
β
β
β
β


· ·
¸ _ ∂ ¸ _
· − · − − ·


¸ ,
¸ ,
∑ ∑ ∑
Q
Two equations are very useful in statistical mechanics,
but it must be stressed that these equations do not
constitute a fundamental relation.
The quantity β is merely the reciprocal temperature in “natural units.”
155
5-2
Molecular Rheology LAB
5-2.2 The partition function
Consider a system composed of Ñ “distinguishable elements,” an element
being an “independent (noninteracting) excitation mode” of the system.
System
Element
Each element can exist in a set of orbital states (use the term
orbital state to distinguish the states of an element from the
state of the collective system).
The identifying characteristic of an “element” is that the energy of the
system is a sum over the energies of the element, which are independent
and noninteracting.
156
5-2
Molecular Rheology LAB
( )



Each element is permitted to occupy any one of its orbitial states independently
of the orbital states of the other elements.
Then the partition sum:

1 1 1
1
ε ε ε
, , , ...
ε
Z
j j j
j
j j j
e
e
β
β
′ ′′
− + + +⋅⋅⋅
′ ′′

·
·






1 1
1 1 1
ε ε
, , , ...
ε ε ε
1 1 1
z z z
j j
j j j
j j j
j j j
e e
e e e
β β
β β β
′ ′′
′ ′′
− −
′ ′′
− − −
′ ′′
⋅ ⋅ ⋅
· ⋅ ⋅⋅ · ⋅ ⋅ ⋅

∑ ∑ ∑

: the energy of the -th element
in its -th orbitial state
ε
i j
i
j

; : the "partition sum of the -th element"
The Helmholtz potential :
ε
1 1
z z
lnZ lnz lnz
i j
i i
j
e i
F
β
β

·
− · · + + ⋅ ⋅ ⋅

The energy is additive over elements, and each element is permitted to
occupy and its orbital states independently.
157
5-2
Molecular Rheology LAB
Applied to two- state model:
Ground state
(with energy 0)
Excited state
(with energy ε)
Total atoms Ñ
( ) ( )
( )
1
&
1ε ε
ε
Z z 1
ln lnZ
ln 1
j
N N
N
E
j
B
N
B
e e e
F e
k T
F Nk T e
β β
β
β
β β
− −


· · + · +
− · ≡ ≡
⇒ · − +

% %
%
%
Q
%
If the number of orbitals had been three rather than two, the partition sum
per particle z would merely have contained three terms.

1 1 1
ε
ε ε ε
z
j
j
e e e e
β
β β β

− − −
· · + +

158
5-2
Molecular Rheology LAB
Applied to the Einstein
model:
1
Einstein introduced the energy of harmonic oscillators discretely:
= ;
; : Planck's constant
The "elements" are the vibrational modes.
1
, , , ... 111
1
/ 1
n n
h h
ε ω
π
¸ _
+ ·

¸ ,
·
h
h
( )
( )


1 1 1 1
1
1 1 1
1
1
1
1 1 1 1
1 1 1 1
1
1 1
1
1
1
1
1
1 1
1
z
1
1
z ( ) 1 11
1 1
1
lnz ln 1 1
1
n n
n
N
B B
e e e e
e e e e
e
x x x x x
x e
F Nk T Nk T e
β ω β ω β ω β ω
β ω
β ω β ω β ω
β ω
β ω
β ω
β β ω
− − − −

− − −



·
− −
· + + + + ⋅ ⋅ ⋅
· + + + + ⋅ ⋅ ⋅
· · · + + + ⋅ ⋅ ⋅ + + ⋅ ⋅ ⋅ − < <
− −
· − · + −

h h h h
h
h h h
h
h
%
h
Q
% %
h
159
5-2
Molecular Rheology LAB
5-2.3 The classical ideal gas
Definition of the classical ideal gas:
Can neglect the interactions between gas particles (unless such interactions
make no contribution to the energy -as, for instance, the instantaneous
collisions of hard mass points).
No. of atoms
Ñ( =NN
A
)
T reservoir
Container
volume
V
The energy is the sum of one-particle
“kinetic energies,” and the partition
sum factors.
Consider monatomic classical ideal gas:
Neglect interactions
between gas molecules
160
5-2
Molecular Rheology LAB
( )
; : generalized momentum
: Hamiltonian function
d d

1 1 1
transl internal
11 11
1
transl
1
1
p p
( , , , , , )
Z z z
1
z
1
x y z
x y z
j j
j
p p p m
x y z
k
x y z p p p
dq dp
e
h h
dxdydz dp p p e
h
d
h
β
β

∞ ∞ ∞
− + +
−∞ −∞ −∞
·
¸ _
· Π · +

¸ ,
⇒ ·
·

∫∫∫ ∫ ∫ ∫
h
H
H
[ ]
d d

( = )
a
1
1 1
1
1 1
11
1
-
1
y
z x
p m
p m p m
x y z
ax
B
xdydz e dp e p e p
V
mk T e
h
β
β β
π
π
∞ ∞ ∞

− −
−∞ −∞ −∞



·
∫∫∫ ∫ ∫ ∫

Q
The one-particle translational partition sum z
transl
:
V
161
5-2
Molecular Rheology LAB
Definition of indistinguishability in quantum mechanics:
Indistinguishability does not imply merely that the particles are “identical”
-it requites that the identical particles behave under interchange in ways
that have no classical analogue.
If one identifi as es and thereby
calculates
11
transl 1
Z z
z 1
.
B
N
V
mk T
h
F
π · 1
¸ ]
%
Finding is not extensive! F
To identify Z as z
Ñ
is to assume the particles to be distinguishable. To
correct this partition sum by taking indistinguishability into account, the
result must be further divided by Ñ!.
162
5-2
Molecular Rheology LAB
( )
The partition sum for a classical monatomic ideal gas:
transl
11
1
11
1
11
1
Z = z
!
1
lnZ ln
1 1
ln ln 1
1 1
N
B
B B B
B B
N
V mk T
F k T Nk T Nk T
N h
F U V
S Nk m Nk
T N
π
π
1
¸ _
⇒ · − · − −
1

¸ ,
1
¸ ]
¸ _

1
⇒ · − · − +

1

¸ ]
¸ ,
%
%
% %
%
% %
h
%
Thermodynamic context for monatomic ideal gases:

11 11
1
1 1 1
ln
U V N
S Ns NR
U V N
1
¸ _ ¸ _¸ _
1 · +

1
¸ , ¸ ,¸ ,
¸ ]
The constant s
0
, undetermined in classic thermodynamic context, has now
been evaluated in terms of fundamental constants.
163
5-2
Molecular Rheology LAB
Reflection on the problem of counting states reveals that division by Ñ! is a
rather crude classical attempt to account for indistinguishability.
1
2
1
2
1 2
1 2
Classical counting Fermi particles Bose particles
“Corrected” number
of states = 4 .1/2!
Orbital model
164
5-2
Molecular Rheology LAB
“Corrected classical counting” is incorrect for either type of real particle!
At sufficiently high temperature the particles of a gas are distributed over
many orbital states, form very low to very high energies.
The probability of two particles being in the same orbital state becomes
very small at high temperature. The error of classical counting then
becomes insignificant, as that error is associated with the occurrence of
more than one particle in a one-particle state.
All gases approach “ideal gas” behavior at “sufficiently high
temperature”.
1
2
1
2
1 2
1 2
Classical counting Fermi particles Bose particles
“Corrected” number
of states = 4 .1/2!
165
5-2
Molecular Rheology LAB
B B
Suppose the energy (Hamiltonian) to be of the form
Then, the classical partition function yields





1 1
1 1
/ 11
( )
~ ~
Aq Bp
E Aq Bp
dq dp k T k T
z e
h hA hB
β
π π
− +
· +
¸ _ ¸

¸ , ¸
∫∫
/ 11
_

,
The Equipartition Theorem
B
The significance is that, at sufficiently high temperature when the classical density of
states is ap every quadratic term in the energy contributes a term
to the heat c
plicable,
This i apacity.
1
1
Nk
%
s the " " of classical statistical mechanics.
A heteronuclear diatomic molecule has three translational modes,
one vibrational mode (with both kinetic
equiparti
and poten
tion
tial
theo
ener
Exp.
gy)
rem
, tw
B B B B
o rotational modes
(i.e., it requires two angles to specify its orientation and has only kinetic energy).
Therefore, the heat capacity per molecule at high temperature is
p

or
1 1 1 1 1
1 1 1 1 1
( k k k k R + + · er mole).
166
Generalized Canonical Formulations
Generalized Canonical Formulations
5-3.1 Entropy as a measure of disorder
5-3.1 Entropy as a measure of disorder
5-3
5-3
Molecular Rheology LAB
Information Theory
Define the information I in terms of the probability f
j
, subject to the
following requirements:
Information is a non-negative quantity, I(f
j
) 0 ≧ .
If an event has probability 1, it’s no information from the occurrence for
event, I(1) =0 .
If two independent events occur, then the information we get from observ-
ing the events is the sum of the two of them: I(f
1
× f
2
) = I(f
1
) + I(f
2
).
I(f
j
) is monotonic and continuous in f
j
.
167
5-3
Molecular Rheology LAB
( ) ( )
Four properties can thus be derived:
: the positive constant was used in different units
e.g.
units are bits (from "binary")
units are trits (from "trinary"
1
1
1
log log
log
log
j b b j
j
I f f
f
b b
¸ _
· · −


¸ ,
{ }
)
units are nats (from "natural logarithm")
units are Hartleys
Define the disorder (entropy) of the porbability distribution , , , is
11
1 1
1
log
log
1
log
e
j
n
j b
j
j
f f f
H f
f
·
¸ _
·


¸ ,

L
168
5-3
Molecular Rheology LAB
Several requirements of the measure of disorder reflect our qualitative
concepts:
The measure of disorder should be defined entirely in terms of the set of
numbers ﹛f
j
﹜.
The maximum disorder corresponds to all event have equal possibility.
Example:
{ } { }
( )
Given sample space and it's possibility distribution:
, , , ; possibility distribution , , ,
Situation I:


Situation II:
1 1 1 1 1 1 1 1
1 1 1 1
1 1 1 1
1
/ 11
1 1 1 1
log log log log 1 1 1 11
1 1 1 1
1
S
S s s s s f f f f
f f f f
H P bits
f
·
· · · ·
· + + + ·
·
( )
, ,

1 1 1
1 1 1 1
/ / / 11 11 1
1 1 1 1
log log log log . 1 1 1 11 11
1 1 1 1
f f f
H P bits
· · ·
· + + + ·
Have max.
disorder
169
5-3
Molecular Rheology LAB
The conceptual framework of “information theory,” erected by Claude
Shannon in 1948, provides a basis for interpretation of the entropy in
terms of Shannon’s measure of disorder.
Entropy in the case of two possibilities
with probabilities f and (1 -f).
C. E. Shannon, J. Bell Syst. Tech. 27, 379-423 (1948).
At max.

1 1
- / 1 11
1 1
log log 1 11
1 1
f f
H bits
· ·
· + ·
170
5-3
Molecular Rheology LAB
From the definition of disorder (entropy):
1 1
1
log ln
n n
j b j j
j j
j
H f k f f
f
· ·
¸ _
· · −


¸ ,
∑ ∑
If the system is isolated, it spends equal time in each of the permissible states.
; , ,
Microcanonical formalism:
1 1
1
11
1 1 1
ln ln ln ln
ln
ln
j
j j
j j
B
B
f j
H k f f k k k
H k
S k
k k
· ·
· ·

¸ _ ¸ _
· − · − · Ω × Ω · Ω

Ω Ω Ω
¸ , ¸ ,
⇒ · Ω
· Ω
⇒ ·
∑ ∑
K
For a closed system the “entropy” corresponds to “Shannon’s quantitative
measure of the maximum possible disorder” in the distribution of the
system over its permissible microstates.
171
5-3
Molecular Rheology LAB
If the system is in contact with a thermal reservoir, the probability of j-th sate is
( )
; , ,
1 1 1
1
11
ln ln lnZ
lnZ
j
j
E
j
E
B j j B j B j j
j j j
B j j B
j
e
f j
Z
H k f f k f e Z k f E
H k f E k
β
β
β
β


· · ·
·
· ·
· − · − · +
⇒ · +
∑ ∑ ∑

K
This agreement between entropy and disorder is preserved for all other
boundary conditions -that is for systems in contact with pressure
reservoirs, with particle reservoirs, and so forth.
Thus we recognize that the physical interpretation of the entropy is that
the entropy is a quantitative measure of the disorder in the relevant
distribution of the system over its permissible microstates.
In thermodynamics the entropy enters as a quantity that is maximum in
equilibrium. Identification of the entropy as the disorder simply brings
theses two viewpoints into concurrence for closed systems.
1
lnZ
B j j B
j
S k f E k β
·
· +

172
5-3
Molecular Rheology LAB
5-3.2 The grand canonical formalism
T & μ reservoir
subsystem
Consider a system of fixed V in contact with both energy and
particle reservoirs, and given energy E
j
and mole number N
j
.
Closed system = Subsystem + T
reservoir
Closed system
( )
( )
( )
( ) { }
( )
( )
Probability of a state of the system:




; from

Expanding &
res tot tot
tot tot tot
1
res tot tot
1
tot tot tot
res tot tot tot tot
,
,
exp ,
ln
exp ,
, ,
j j
j
B j j
j B
B
j j
E E N N
f
E N
k S E E N N
f S k
k S E N
S E E N N S E


Ω − −
·

− −
⇒ · · Ω
− −
( )
{ } ( )
tot
j j
E N
U TS N
j
N
f e e
β µ
β µ
− −
− −
⇒ ·
173
5-3
Molecular Rheology LAB
{ } ( )
[ ]
( )
( ) ( )
( )
defined = ; is the "grand canonical potential"
is state-independent normalizing factor
define
,
1
Z
j j
j j
j j j j
j j
E N
U TS N
j
E N
j
E N E N
j
j j j
E N
f e e
U TS N U T
f e e
e
f e e e e
e
β µ
β µ
β µ
β
β
β µ β µ
β β
β µ
µ µ
− −
− −
− −
Ψ
Ψ
− − − −
Ψ Ψ
− −
·
Ψ − − · Ψ
⇒ ·
∴ · · ·

∑ ∑ ∑
Q
: the grand canonical partition sum ; Z
Z
ln Z
j
e
β
β
− Ψ
⇒ ·
∴− Ψ ·

The conventional view is that Ψ(T, V, μ) is the Legendre transform of U,
or Ψ(T, V, μ) = U[T, μ].
174
5-3
Molecular Rheology LAB
Mnemonic figure
( )
Useful relationships :

lnZ
U
βµ
β
β β
∂ Ψ
¸ _ ∂
· · −

∂ ∂
¸ ,
[ ]
F U T ·
Multiplied
1
B
k
175
5-3
Molecular Rheology LAB
To corroborate the grand canonical formalism from maximizing the disorder
(entropy):
1
ln
B j j
j
S k f f
·
· −

( )
1
ln 11
B j j
j
S k f f δ δ
·
· − + ·

Taking differentials &
multiplying by Lagrange
multiplier λ
1
, λ
2
, λ
3
.
Auxiliary conditions:
1
1
1
1
1
1
1
1
1
j
j
j j
j
j
j
f
E f
N f
λ δ
λ δ
λ δ
·
·
·
·
·
·



Auxiliary conditions:
1
1
1
1
j
j
j j
j
j j
j
f
f E E
f N N
·
·
·
·
·
·



Taking differentials
176
5-3
Molecular Rheology LAB
( )
1 1 1
1
j j
E N
j
f e
λ λ λ − + + +
·

1
1
1
1 λ β
λ β
λ βµ
− − · Ψ
·
− ·
( )
j j
E N
j
f e e
β µ
β
− −
Ψ
·
( )
1
ln 11
B j j
j
S k f f δ δ
·
· − + ·

( )
( )
If this equation is always to hold true,
each term must be equal to zero.
1 1 1
1 1 1
1
1 1 1
1
ln 11
ln 11
j j
j j j
j
j j j
E N
j
f E N
f E N
f e
λ λ λ
λ λ λ
λ λ λ
·
− + + +
+ + + + ·
⇒ + + + + ·
⇒ ·

Auxiliary conditions:
1
1
1
1
1
1
1
1
1
j
j
j j
j
j
j
f
E f
N f
λ δ
λ δ
λ δ
·
·
·
·
·
·



Adding 4
equations
Compare the two
equations to identify λ
1
, λ
2
,
& λ
3
.
177
5-3
Molecular Rheology LAB
Example: Molecular Adsorption on a Surface
Consider a gas in contact with a solid surface. The molecules of the gas can
adsorb on specific sites on the surface.
T & μ reservoir
Solid surface
(system)
There are Ñ such sites, and each site can adsorb zero, one,
or two molecules.
the site is empty
Each site has an energy: singly occupied
doubly occupied
1
1
1
ε
ε
→ ¹ ¹
¹ ¹

' )
¹ ¹

¹ ¹
We seek the “fractional coverage” of the
surface.
The gaseous phase which bathes the surface establishes the values of T
and μ, being both a thermal and a particle reservoir.
In such a case μ, the Gibbs potential per particle of the gas, must first be
evaluated from the fundamental equation of the gas, if known, or from
integration of the Gibbs-Duhem relation if the equation of state are
known.
178
5-3
Molecular Rheology LAB
The surface sites do not interact, the grand partition sum:
( ) ( ) ( ) ( ) ( )
( )
( )
( ) ( ) ( )
( )

The mean number of molecules adsorbed per site is

1 1 1 1
1 1
1 1
1 1
1
1 1 1
Z z
z = 1
z
1 1 1
z z z
1
j j
j j
j j
N
E N
j
E N
E N
j
j j j
j j j
e e e e e e
e N
n f N e e N
e e e
e e
n
β µ
β ε µ β ε µ β ε µ β ε µ
β µ
β µ
β
β µ β ε µ β ε µ
β ε µ β ε
− −
− − − − − − − −
− −
− −
Ψ
− − − − − −
− − −
·
· + + · + +
· · ·
⋅ ⋅ ⋅
· + +
+
⇒ ·

∑ ∑ ∑
%
( )
( )
( ) ( )
The mean energy per site is

1 1
1
1
1 1
z
z
j j
E N
j j j
j j
e e
f E e e E
µ
β ε µ β ε µ
β µ
β
ε ε
ε ε

− − − −
− −
Ψ
+
· · ⇒ ·
∑ ∑
z e
β − Ψ
· Q
179
5-3
Molecular Rheology LAB
An alternative route to these two results, and to the general thermodynamics
of the system, is via calculation of the grand canonical potential:
. ln Z
B
k T Ψ · −
( ) ( )
( )
( )
( )
( )

The number of adsorbed atoms on the sites:
; is constant
1 1
1
ln Z = ln z ln 1
ˆ
ˆ
ˆ
N
B B B
k T k T k T e e
N N
N Nn T
U N
β ε µ β ε µ
β
βµ µ
β
ε
β
− − − −
Ψ · − − · − + +
∂ Ψ
∂Ψ
· · − · −
∂ ∂
∂ Ψ
· · −

%
%
%
Q
%
180
Homework
Homework
5-H
5-H
Molecular Rheology LAB
Problem 15.1-1
Problem 15.2-1
Problem 15.4-4
Problem 16.1-1
Problem 16.1-4
Problem 16.2-1
Problem 16.10-4
181
Statistical Fluctuations and Solution
Statistical Fluctuations and Solution
Strategies
Strategies
Chapter 6
Chapter 6
Molecular Rheology LAB
Contents
6-1 Fluctuations
6-1.1 The probability distribution of fluctuations (19.1)
6-1.2 Moments and the energy fluctuations (19.2)
6-2 Quantum Fluids
6-2.1 Quantum particle -fermions and bosons (18.1)
6-2.2 The ideal Fermi fluid (18.2)
6-2.3 The ideal Bose fluid (18.5)
6-2.4 The classical limit and the quantum criterion (18.3)
6-2.5 The strong quantum regime: electrons in a metal (18.4)
6-2.6 Bose condensation (18.7)
182
Fluctuations
Fluctuations
6-1.1 The probability distribution of fluctuations
6-1.1 The probability distribution of fluctuations
6-1
6-1
Molecular Rheology LAB
T reservoir
subsystem
The subsystem and the reservoir together undergo
incessant and rapid transitions among their joint
microstates.
The subsystem energy thereby fluctuates around its equilibrium value
reservoir
subsystem
The “subsystem” may, in fact, be a small portion
of a larger system, the remainder of the system
then constituting the “reservoir.”
In that case the fluctuations are local fluctuations
within a nominally homogeneous system.
183
6-1
Molecular Rheology LAB
The statistical mechanical form of the probability distribution for a fluctuating
extensive parameter is familiar.
T reservoir
subsystem
Case I:
The probability that the system occupies a particular
microstate of energy :
ˆ
ˆ
F E
E
f e
β β −
·
T, P reservoir
subsystem
Case
II:
( )
The probability that the system occupies a particular
microstate of energy and volume :
ˆˆ
ˆˆ
G E PV
E V
f e
β β − +
·
184
6-1
Molecular Rheology LAB
Generally, for a system in contact with reservoirs corresponding to the
extensive parameters , , , , the probability that the system
occupies a particular microstate with parameters , , ,
1 1
1 1
ˆˆ
s
X X X
X X
K
K :
ˆ
s
X
( ) { }
, ,
, , ,
=e
: the Massueu function
: the entropic intensive parameters
1 1
1 1 1 1 1
1 1
ˆˆˆ
, ,
ˆˆˆ
1
1
, ,
, ,
B s B s s
s
k S F F k F X F X F X
X X X
s
s
f
S F F
F F
− −
− − + 1
¸ ]
1
¸ ]
K K
K
K
K

1
1
ˆ
1
1
ˆˆ
F E
F
S
T T
F
T
X E
f e
β β −
1
− ·
1
¸ ]
·
·
⇒ ·
e.g.
( )
,
;
;
1 1
1 1
ˆˆ
1
1
ˆˆˆˆ
E N
S
T T T
F F
T T
X E X N
f e
β β µ
µ
µ
Ψ− −
Ψ
1
− ·
1
¸ ]
· ·
· · −
⇒ ·
( )
,
;
;
1 1
1 1
ˆˆ
1
1
ˆˆˆˆ
G E PV
G P
S
T T T
P
F F
T T
X E X V
f e
β β − +
1
− ·
1
¸ ]
· ·
· ·
⇒ ·
185
6-1
Molecular Rheology LAB
6-1.2 Moments and the energy fluctuations
Suppose that the Ê is the only fluctuating variable, all other extensive
parameters being constrained by restrictive walls.
( ) ( )
( )
( )
( )
( )
( )
( )
: the deviations
;
: the mean-square deviation (the second central moment)

1
1 1 1
1
ˆ
ˆˆ
1
ˆ
ˆ
ˆ
j
j
j
F E
j j j
j j
F E
j
j
F E
j
j
E U
E U E U
E U
E U E U f E U e
E U E U e F U
U
E U e
β
β
β
β
β β
β β




≡ − ·

− · − · −
¸ _ ∂ ∂
⇒ − · − − ·

∂ ∂
¸ ,
∂ ∂
· − − −
∂ ∂
∑ ∑


Q
186
6-1
Molecular Rheology LAB
( )
( )
( )
( )
( )
( )
( )

1
1
1
ˆ
1
ˆ
1
j
j
F E
j
j
F E
j j j
j j
B v
B
U
E U E U e
E U e E U f E U
U U
E U k T Nc
k T
β
β
β β
β


∂ ∂
− · − − −
∂ ∂
− · − · − ·
∂ ∂
∴ − · − · − · −
∂ ∂

∑ ∑
Q
The mean square energy fluctuations are proportional to the size of the
system.
The relative root-mean-square dispersion , which measures
the amplitude of the fluctuations relative to the mean energy, is
proportional to N
-1/2
.
For large systems (N→∞) the fluctuation amplitudes become negligible
relative to the mean values, and thermodynamics becomes precise.
( )
11
1
ˆ
E U U −
A very useful expression to estimate
the heat capability of a system in
computer simulations.
187
6-1
Molecular Rheology LAB
Higher-order moments of the energy fluctuations:
( )
( )
( )
( ) ( )
( )
( )
( )
( )
( ) ( )



e.g. the third moment:
1
1
1
ˆ
ˆ
j
j j
j
n n
F E
j
j
n n
F E F E
j j
j j
n
n F E
j
j
n n
E U E U e
E U e e E U
U
E U n e E U
U
E U n E U
E
β
β β
β
β
β β
β β
β β
+

− −




− · − −

∂ ∂
· − − + −
∂ ∂
∂ ∂
· − − + −
∂ ∂
∂ ∂
· − − + −
∂ ∂


∑ ∑

1
1 1 1
1
v
B v
c
U Nk T Tc T
T

¸ _
· +


¸ ,
The higher-order moments of the energy fluctuations can be generated
from the lower-order moments by the recursion relation.
188
6-1
Molecular Rheology LAB
For a system in which both E and V fluctuates:
B
B B B
B
B B
B




1
1
1
/ , ,...
1 1 1
1
/ , ,...
1
1
ˆ
( / ) 1
ˆˆ
( / ) 1
ˆ
( / )
P T N
p T
P T N
T
U
E k
T
k T Nc k T PV k TP V
V
E V k
T
k T V k TPV
V
V k
P T
α κ
α κ
¸ _ ∂
∆ · −


¸ ,
· − +
¸ _ ∂
∆ ∆ · −


¸ ,
· −
¸ ∂
∆ · −

B


1
/ , ,... 1T N
T
k T Vκ
_

¸ ,
·
The energy and the volume fluctuations are correlated, as expected.
189
Quantum Fluids
Quantum Fluids
6-2
6-2
Molecular Rheology LAB
As so often happens in physics, the formalism points the way to reality. The
awkwardness of the formalism is a signal that the model is unphysical -there
are no classical particles in nature!
Quantum Mechanical Particles
Bosons Fermions
Fermions are the quantum
analogues of the material
particles of classical physics.
e.g. electrons, protons, and
neutrons
Bosons are the quantum
analogues of the “waves” of
classical physics.
e.g. photons (quanta of light)
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(From Astro-group, department of physics of Hong Kong university)
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6-2.1 Fermions and bosons & ideal quantum fluids
Fermions
Fermions obey “law of impenetrability of matter”, only a single fermion can
occupy a given orbital state.
The intrinsic angular momentum for fermions:
, (odd multiples)
1
Spin quantum number : ( ), ( )
, , , 1 1 1
1 1
1 1
s
n n
m
× ·
↑ − ↓
h
K
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Molecular Rheology LAB
Consider a pre-gas model system in which only three spatial orbits are
permitted; particles in these spatial orbits have energies ε
1
, ε
2
, and ε
3
. The model
system is in contact with a T reservoir and a μ reservoir.
T & μ reservoir
subsystem
There are therefore six orbital states:
; ; ,
1 1
( , ) , , 111
1 1
s s
n m n m · · − +
( ) ( ) ( )
( ) ( )
( ) ( )

The Grand canonical partition sum factors:
, , , , , , 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1
,
,
,
,
Z z z z z z z
z 1
1
z
1 1
n n n n
s
s
n n
s
n n
s
N
n m
n m
n m
n m
e e e e
e e
f
e e
β ε µ β ε µ β ε µ
β ε µ β ε µ
β ε µ β ε µ
− − −
− − − − − −
− − − −
− − −
·
· · + · +
· · ·
+ +

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Molecular Rheology LAB
( ) ( ) ( )

Pair the two orbital states with the same but with :
1
1
, , 11 11
1
z z 111
n n n
s
n n
n m
e e e
β ε µ β ε µ β ε µ − − − − − −

· t
1
· + · + +
¸ ]
empty 2 singly occupied double occupied
( ) ( ) ( )
The fundamental equation:
1 1 1
1 1 1
Z 111 e e e e
β ε µ β ε µ β ε µ
β
− − − − − −
− Ψ
1 1 1
· · + + +
¸ ] ¸ ] ¸ ]
( ) ( )

1
1 1
n n
e e
β ε µ β ε µ − − − −
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( ) ( ) ( )
( ) ( ) ( )








or

or

By the same way,
1 1 1
1 1 1
,
,
,
,
, ,
,
1 1 1
, ,
,
1 1 1
1 1 1
1 1 1
1 1 1
n m
n m
n m
n m
n m n m
n m
n m n m
n m
N N f
N f
e e e
U U f
U f
e e e
S
T
β ε µ β ε µ β ε µ
βµ
β ε µ β ε µ β ε µ
µ
β
ε
β
ε ε ε
ε
− − −
− − −
−∂Ψ
· ·

· · + +
+ + +
¸ _ −∂ Ψ
· ·


¸ ,
· · + +
+ + +
−∂Ψ
·





% %
%
determines the entropy.
¸ _

¸ ,
The fundamental equation is an attribute of the thermodynamic system,
independent of boundary conditions. In general, the Fermi level μ as a
function of T and Ñ must be determined.
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Ideal Fermi fluids
The ideal Fermi fluid is a quantum analogue of the classical ideal gas; it is
a system of fermion particles between which there are no (or negligibly
small) interaction forces.
Composite “particles,” such as atoms, behave as fermion particles if they
contain an odd number of fermion constituents e.g.
3
He.
( ) ( ) ( )
( )
( )
The partition sum of orbital state , :

The partition sum factors:
The probability of occupation:
k k k k
k
k
1
k,
k,
k,
k,
k,
k,
k
z 1
Z z
1
z
1
s
s
s
s
s
s
s
N
m
m
m
m
m
m
m
e e e e
e
f
e
β ε µ β ε µ β ε µ
β ε µ
β ε µ
− − − − − −
− −

· · + · +
⇒ ·
· ·
+


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Molecular Rheology LAB
( )
The grand canonical potential:
The energy of an occuppied orbital state , :
, : wave vector (can refer to eq. 1. in textbook) 111
The density of
k
1
k k
1 1 1
,
lnZ ln 1
k
1 1
s
B B
s
k m
k T k T e
m
p k
k
m m
β ε µ
ε
− −
1
Ψ · − · − +
¸ ]
· ·
∑ ∑
h
( )
( )
( )
( )
orbital states: (see Chap. ) 11

which can be utilized to determine and .
11
1 1 1
1 1 1
1
11
11
1 1
1
1
1 1
ln 1 1
1
ln 1
1
B
B
V dk V m
D d k d d
d
k T e D d
V m
k T e d
U N U
β ε µ
β ε µ
ε ε ε ε ε
π ε π
ε ε
ε ε
π
β

− −

− −
¸ _
· ·

¸ ,
1
⇒ Ψ · − +
¸ ]
¸ _
1
· − +

¸ ]
¸ ,
∂ Ψ
·


h
h
%
; N
βµ
β µ
¸ _
¸ _ ∂Ψ
·


∂ ∂
¸ ,
¸ ,
%
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Molecular Rheology LAB
Bosons
Fermions as waves can be freely superposed, so an arbitrary number of bosons
can occupy a single orbital state.
The intrinsic angular momentum for fermi ons:
, (even multiples)
1
, , , 111 n n × ·
h
K
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Molecular Rheology LAB
Ideal Bose fluids
( ) ( ) ( )
( )
The partition sum of a single orbital st ate is independent of , and is, for
each value of
;
k k k
k
1 1 1 1
1
k k,
,
z z
1 1
1
1
s
s
s
m
n
n
m
m
e e e e
x
x
e
β ε µ β ε µ β ε µ
β ε µ
− − − − − −
− −
· · + + + +
· ·


L
Q
( )
,
The probability of occupation with various occupated no. in orbital state is
The average number of bonsons in the orb ital state , :
k
1
k, ,
k,
k k, ,
k,
z
k
s
s
s s
s
i i
m i
m
s
m m i
i
i m
e
f
m
n i f e
β ε µ
β ε

·
− −

¸ _

¸ ,
·
· × ·


( ) ( ) ( )

k k k
1 1 1 1
k,
k,
z
ln z
s
s
m
B m
e e
k T
µ β ε µ β ε µ
µ
− − − − −
1
+ + +
¸ ]

·

L
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Molecular Rheology LAB
( )
( )
( )
( )
( )
( )
( )
( )
( )
,
, ,

which determines and .
k
k
k
k
k
k
k k,
k k
1
11
11
1 1
1
ln z ln 1
1
1
1
1
1
ln 1
1 1
1
1 1
s s
s s
m B m B B
m m
e
n k T k T e k T
e
e
n f
e
e D d
V m
d U N
e
β ε µ
β ε µ
β ε µ
β ε µ
β ε µ
β ε µ
β ε µ
β
µ µ
β ε ε
ε
ε
π
− −
− −
− −



− −


∂ ∂ −
· · − − · −
∂ ∂

·

⇒ ≡ ·

1
⇒ Ψ · −
¸ ]
¸ _
⇒ Ψ · − ⇒

− ¸ ,


%
h
The quantity is not necessarily less than unity, and therefore is
more properly identified as a “mean occupation number” .
If μ were positive the orbital state with ε
k
equal to μ would have an
infinite occupation number! So, the molar Gibbs potential μ is always
negative.
,
s
k m
n
, k
s
m
f
occupation probability (or
mean occupation number)
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Molecular Rheology LAB
6-2.2 The classical limit and the quantum criterion
At low densities or high temperatures, the probability of occupation of
each orbital state is small, thereby minimizing the effect of the fermion
prohibition against multiple occupancy.
( )
( )
( )
( )
,
,
The probability of occupancy:
If fugacity ; classical regime
The occupation probability reduces to
The number of particles reduces to
k
k
1
1 1
1
1
1
1
1
s
s
m
m
f
e
e
f e e e
N
g V m
N
β ε µ
βµ
β ε µ
βµ βε
µ
π

− −

·
+
<<

· ·

∂Ψ
· − ·

%
%
h
; : the thermal wave length
11
11 1
1
1
λ
λλ
1
T
T T
B
g V
e e d e
h
mk T
βµ βε βµ
ε ε
π


¸ _
·

¸ ,
·

The Boltzmann distribution
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Molecular Rheology LAB
( )
( )
The energy reduces to
11
11 1
1 1 1
1
1 1 1

1
1
1
B
T
B
g V V m
U e e d k T e
U Nk T
βµ βε βµ
βµ
β
ε ε
β
π



1 ∂ Ψ
¸ _
· · ·
1


¸ ,
¸ ]
⇒ ·

h
%
The equation of state of
classical ideal gas
( )
The criterion that divides the quantum and classical regimes:
or classical-quantum boundary
1
1
1λ1
T
g V
e
N
βµ
¸ _
≈ ≈

¸ ,
%
The system is in the quantum regime if the thermal volume is larger than
the actual volume per particle (of a single spin orientation) either by virtue
of large Ñ or by virtue of low T (and consequently of large λ
T
).
The classical limit the fugacity is the ratio of the “thermal
volume” λ
3
T
to the volume per particleV/(Ñ/g
0
).
N
%
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Molecular Rheology LAB
6-2.3 Example of Fermi fluid: electrons in a metal
At T =0 K, to calculate the number of particles:
( )
( )
The number of conduction electrons per unit volume in metals is of the order
of the order of to electrons cm , th 11 11 e Fermi temperature is
to
1
11
11
11 11
1 1 1 1 1
1
11 11 1
1 1
1
1
1
K 11 11
F
F
B
m V
m V
N d
T
T
k
µ
ε ε µ
π π
µ
· ·
≡ ≈

%
h h
1
K
( )

for

for
1
1
1
1
,
1
T K
f T
ε µ
ε
ε µ
·
<
¹
·
'
>
¹
Metal T
F
(K)
Li 5.5×10
4
Na 3.7×10
4
K 2.4×10
4
Rb 2.1×10
4
Metal T
F
(K)
Cs 1.8×10
4
Cu 8.2×10
4
Ag 6.4×10
4
Au 6.4×10
4
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Molecular Rheology LAB
( )
The heat capacity:
1
1
1
1
1 1
B
B
k T
C Nk O T
π
µ
¸ _
· +

¸ ,
%
The prefactor 3Ñk
B
T/2 is the classical result, and the factor in parentheses
is the “quantum correction factor” due to the quantum properties of the
fermions, which is of the order of 1/10 at room temperature.
This drastic reduction of the heat capacity from its classically expected
value is in excellent agreement with experiment for essentially all metals.
All reasonable temperatures μ>> k
B
T, the electrons in a metal are an
example of an ideal Fermi gas in the strong quantum regime.
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Molecular Rheology LAB
6-2.4 Bose condensation
( )
( )
( )
The number of particles :
Fugacity , and
Expand the integral of equation of in powers of the fugacity:
11
11
1
1 1 1
1
11
11
1 1
1 1
1
1
1
1 1
1

1
e
e
e
e B
N
g V m
N d
e
e
N
g V g V m
N k T
βε
βµ
ε
ε
ξ
π
ξ ξ
π
π


¸ _
·


¸ ,
≡ < <
1
¸ _
1 · ·

¸ , 1
¸ ]

%
%
h
%
%
h
( )
( )
; : the thermal wave length
11 1
1 1
11 11
1
λλ
1
1 1 1 1
T
T T
B
r
r
F
h
mk T
F
r
ξ
π
ξ ξ ξ
ξ ξ

·
·
· · + + +

L
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Molecular Rheology LAB
( )
( )
( ) ( ) ( )
( )
The energy:
Expand the integral of equation of in powers of the fugacity:
11
11
1
1 1 1
1
11
11
1
11 11 1 1 1
1 1
11 11
1
1
1
1
1 1 1 1
1 1λ
1
1 1 1 1
B B
T
r
r
e
g V m
U d
e
U
g V V m
U k T F k T F
F
r
N
βε
ε
ε
ξ
π
π
ξ ξ
π
ξ ξ ξ
ξ ξ



·
¸ _
·


¸ ,
1
¸ _
1 · ·

¸ , 1
¸ ]
≡ · + + +
·


h
h
L
%
Q
( )
( )
( )
( )
1 1
11 1 1
11
11
11
λλ
1
1
e
T T
e B
g V g V N
F
F
F
U N k T
F
ξ
ξ
ξ
ξ
⇒ ·
⇒ ·
%
%
The ratio measures the deviation from the classical
equation of state.
( ) ( )
11 11
F F ξ ξ
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Molecular Rheology LAB
( ) ( )
( ) ( )
The two functions and satisfy the relation:
11 11
11 11
1
F F
d
F F
d
ξ ξ
ξ ξ
ξ ξ
·
At
11
11
1
. 1 1 1
. 1111
F
F
ξ ·
·
·
At
slope of
slope of
11
11
1
1
1
F
F
ξ ·
·
·
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Molecular Rheology LAB
If , to first evaluate the temperature at which the failure of the
"integral analysis" occurs.
Set
: the Bose condensation tempe
1
1
1
1
11
1
1
. 1111
. 1111
λ
1
1 1
. 1111
e T
e T
T
B
B c
c
g V
N
g V
N
h
mk T
N
k T
m g V
T
λ
λ
π
π

∴ ·
·
¸ _
⇒ ·

¸ ,
%
%
%
h
rature
For temperature greater than T
c
the “integral analysis” is valid. At and
below T
c
a “Bose condensation” occurs, associated with anomalous
population of the orbital ground state.
Example of Bose condensation of
4
He
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Molecular Rheology LAB
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Below T
c
the fluid flows freely through the finest capillary tubes, as its
name denotes, “superfluid.”
This component cannot easily dissipate energy through friction, as it is
already in the ground state.
The condensed phase has a quantum coherence with no classical
analogue.
These electron pairs then act as bosons. The Bose condensation of the
pairs leads to superconductivity, the analogue of the superfluidity of
4
He.
ρ
s
(T): superfluid density of
4
He
ρ
n
(T): normal fluid density of
4
He