ChiChung Hua
Instructor: Prof. ChiChung Hua
Molecular Rheology LAB
Advanced Thermodynamics
Advanced Thermodynamics
Complex Fluids & Molecular Rheology Laboratory,
Department of Chemical Engineering,
National Chung Cheng University, ChiaYi 621, Taiwan, R.O.C.
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Course Outline
Course Outline
Instructor: ( Rm 412 Ext. 33412)
Textbook: Herbert B. Callen, 1985, Thermodynamics and
Introduction to Thermostatistics, 2nd ed., John
Wiley & Sons, Inc. ( )
Grading: Homework (20 %)
Two Exams (80 %)
Teaching assistants: (Rm 301, Ext. 23471)
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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
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Contents
11 Thermodynamic Equilibrium and Postulate I
12 The Entropy Maximum and Postulates II & III
13 Intensive Parameters and Equations of State
14 The Euler Equation and the GibbsDuhem Relation
1H Homework
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Thermodynamic Equilibrium and
Thermodynamic Equilibrium and
Postulate I
Postulate I
11.1 Thermodynamic coordinates
11.1 Thermodynamic coordinates
11
Variables
Experimental variables
Simulation variables
Macroscopic vs. Microscopic
Responses
Experimental results
Simulation data
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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.
11
length scale
1 m
Microscopic Macroscopic
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11
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 its easier to do.
The price paid is, however, that smallscale problems cannot be
studied, and some macroscopic properties themselves become
difficult to understand.
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http://www.bibalex.org/English/lectures/printable/zewail.htm
Figure 1.1 Length and time scales of atoms and cats
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11.2 Definition of equilibrium states
11.2 Definition of equilibrium states
System has no external influences (such as flow, electrical fields).
All thermodynamic properties must be time invariance (time
independent).
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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.
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11.3 Limitations of thermodynamic equilibrium
11.3 Limitations of thermodynamic equilibrium
11
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 onecomponent system.
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The Entropy Maximum Postulates:
The Entropy Maximum Postulates:
Postulate II & III
Postulate II & III
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12
Postulate III:
S is a monotonically increasing function of U.
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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
_
>
,
12
12
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
subsystems subject to
certain constraints:
S S U , V ,
N
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12
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
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,
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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Others equilibrium conditions can be derived with fixed V
& U or N & U.
1
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
12
15
Intensive Parameters and Equations of
Intensive Parameters and Equations of
State
State
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13.1 Extensive parameters & intensive parameters
13.1 Extensive parameters & intensive parameters
Extensive parameters
1
, , , : First order extensive parameters
( , , ) ( , , )
S U V N
S U V N S U V N
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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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
_ _ _
, , ,
_ _ _
, , ,
Fundamental equations
At first, people didnt know the meanings of T, P and . Later, they
realized that T, P and were identical with temperature, pressure and
chemical potential in our ordinary life.
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, S V
U
N
,
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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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.
13.2 Fundamental equations & equations of state
The fundamental equations describe homogeneous firstorder parameters.
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Equations of state
, , ,
( , , )
; ;
N V N S S V
U U S V N
U U U
T P
S V N
_ _ _
, , ,
( , , )
( , , )
( , , )
T T S V N
P P S V N
S V N
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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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
, ,
( ) ( )
( ) ( )
N V N V
U U
T
S S
The equations of state describe homogeneous zeroorder 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
Equations of state
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13.3 Unit of temperature
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T
h
T
c
dQ
h
dW
rev
Thermodynamic engine
rev
1
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
+
Used to define temperature scale.
Permissible scale (e.g. K, R)
Nonpermissible scale (e.g.
o
C,
o
F)
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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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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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13.4 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
_ _ _
+ +
, , ,
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
_ _ _
+ +
, , ,
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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
_ _ _
+ +
, , ,
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
>
> <
> >
> <
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The Euler Equation and the GibbsDuhem
The Euler Equation and the GibbsDuhem
Relation
Relation
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14.1 The Euler relation
14.1 The Euler relation
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Homogenous first order property
differentiating w.r.t. ( )
1 1 1 1
( , , , , ...) ( , , , , ...) U S V N N U S V N N
d
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
+
1 1 1
1 1
1
1 1
, , ...) ( )
... ( , , , , ...)
( )
N N
U S V N N
N
N
+
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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
+ + +
+
+
+
j
j
j
1 P
U V N
T T T
_
_ _
+
, ,
,
, ,
j
j
j
1 N d
T
_
+
+
+ +
Only T & P are independent,
can be deduced from the Gibbs
Duhem equation.
The Euler relation is useful for deducing many important thermodynamic
relationships, including the famous GibbsDuhem equation.
The GibbsDuhem relation specifies, in a differential form, the
relationship among all intensive properties of a thermodynamic system.
Clearly, is not independent of T and P in the previous example.
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14.3 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
,
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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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:
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21.2 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.
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X, Y are extensive properties & Y=Y(X).
Let slope is ; : intersive properties
Y
P P
X
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Generalization of the Legendre transformation
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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
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
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The Legendre Transformed Functions
The Legendre Transformed Functions
and Thermodynamic Potentials
and Thermodynamic Potentials
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The energy representation of the
fundamental equation: ( , , ) U U S V N
Intensive parameters
, , ...
1 1
, , T P
1 1
( , , ... , )
t
k
k
k k
k
Y Y X X X
Y
P
X
Y P X
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The Helmholtz potential, F
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( , , ) ( , , ) U S V N F T V N
Y X
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
_ _ _
, , ,
+
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
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The Enthalpy, H
( , , ) ( , , ) U S V N H S P N
Y X
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
_ _ _
, , ,
+ +
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
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The Gibbs potential, G
( , , ) ( , , ) U S V N G T P N
Y X
2
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
_ _ _
, , ,
+ +
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
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The following equations are all fundamental equations:
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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
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Minimum Principles for the Potentials
Minimum Principles for the Potentials 23
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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
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( ) ( ) ( ) ( ) 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
+ + +
+ + +
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
+ + +
+
+ +
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( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 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
+ +
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
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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
>
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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
>
>
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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.
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Applications of various Legendre
Applications of various Legendre
Transformed Potentials
Transformed Potentials
24.1 The Helmholtz potential
24.1 The Helmholtz potential
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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.
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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
+
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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.
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24.2 The enthalpy
At constant
1 1 1 1
...
,
i
dH TdS VdP dN dN
P N dH TdS dQ
+ + + +
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 + +
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The JouleThomson 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
+
+ +
,
( )
1
P
v
dT T dP
C
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 T >1, T will increase with a small increase in pressure, and vice versa.
For ideal gas, = 1 / T, so that there will be no change in T.
59
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Molecular Rheology LAB
24.3 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
+
+
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Molecular Rheology LAB
Change of G associated with changes in N
j
can be described by
j j
j
dG SdT VdP dN + +
since
1 1
1 1
...
j j
dN dN
dN dN dN
% %
or
1
1
j j
j
j j
j
dG dN
%
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
_
%
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Molecular Rheology LAB
24.4 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
25.1 The Maxwell relations & mnemonic diagram
25.1 The Maxwell relations & mnemonic diagram
25
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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
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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:
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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
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25
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
(" ") + (" ") +
(" ") +
(" ")
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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
[ , ]
j
U T
X
1
P
1
U
X
2
P
2
1
[ ] U P
1
[ ] U P
1 1
[ , ] U P P
Generalform mnemonic
diagram
U(S, N
j
) mnemonic diagram
j
67
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Molecular Rheology LAB
25.2 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
_ _
, ,
_ _
, ,
_
,
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 singlecomponent systems and constant molecule numbers, the second
derivatives of Gibbs representation can be expressed by
25
Molecular Rheology LAB
, , and .
P T
c
/ ; ;
1 1 1
1 1 P T
g g g
c T v v
T T P P
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
singlecomponent systems), conventionally chosen as .
( )
, V N
dT T P dP
and ,
P T
c
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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. 187188 of the textbook)
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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 GibbsDuhem relation, . d sdT vdP +
Example:
Reduce the derivative
, S N
V
_
,
, , , S N S N S N
T P
s v
V V V
_ _ _
+
, , ,
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
_ _ _ _
, , , ,
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Molecular Rheology LAB
Bring the volume to the numerator. The remaining derivative will be
expressible in terms of . and
T
Example:
Reduce the derivative
, V N
T
P
_
,
, , ,
T
T N P N V N
T V V
P T P
_ _ _
, , ,
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
1
V P
T
Tv
c c
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Molecular Rheology LAB
25.3 Some simple applications
I. Adiabatic compression
T
i
P
i
Adiabatic wall
T
f
=?
P
f
Adiabatic wall
Quasistatic process
If known: fundamental equation, , , and
i f i
P P T
Fundamental equation
Equations of state:
T=T(S, P
f
, N) T(S, P
i
, N)
T
If known: , , , , , and
i f i P
P P T c
;
, ,
( )
S N P S N P
T Tv sTv
dT dP dP d d v dP
P c P c
_ _
, ,
(see p. 190)
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Molecular Rheology LAB
II. Isothermal compression
P
i
P
f
Quasistatic 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
;
, ,
( )
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
_ _
+
, ,
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
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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
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
_
_
,
,
75
Homework
Homework
2H
2H
Molecular Rheology LAB
Problem 5.31
Problem 5.312
Problem 6.32
Problem 7.47
Problem 7.415
Problem 7.423
76
Molecular Rheology LAB
Stabilities, Phase Transitions, and
Critical Phenomena
Chapter 3
Chapter 3
Contents
31 Stability Conditions for Thermodynamic Potentials
32 Le Chaterliers Principle and Effects of Fluctuations
33 Firstorder Phase Transitions in SingleComponent Systems
34 Thermodynamic States near Critical Points
77
Stability Conditions for Thermodynamic
Potentials
31.1 Intrinsic stability of thermodynamic systems
31.1 Intrinsic stability of thermodynamic systems
31
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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 <
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Molecular Rheology LAB
Initial state New state
S(U) S(U) S(UU) S(U+U)
( )
1
Total
S S U ( ) ( )
Total
S S U U S U U + +
Remove U 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 Chaterliers principle)
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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 8.11 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 U(V) rather than for U 0(V 0) only.
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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 largeamplitude 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.
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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 8.11 of the textbook)
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Molecular Rheology LAB
31.2 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
_
,
_
,
_ _ _
, , ,
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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 8.11 of the textbook)
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Molecular Rheology LAB
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 Chaterliers Principle and the Effects
of Fluctuations
32.1 Le Chateliers principle
32.1 Le Chateliers principle
32
32
Molecular Rheology LAB
Example:
The Le Chateliers 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
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Molecular Rheology LAB
32.2 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).
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Molecular Rheology LAB
32.3 The Le ChatelierBraun principle
The Le ChatelierBraun 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
decreasedthe 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 0 and
outward if 0.
S V T
T T
dT dV dV
V Nc
,
;
1
1
S V T
P
dP dQ dQ TdS
T S NT c
dQ
,
Then, P
i
is increased for either sing of due to
the heat flow. Thus a secondary induced process
also acts to diminish the initial perturbation. This
is the Le ChatelierBraun 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
89
Firstorder Phase Transitions in Single
Component Systems
33.1 Firstorder & secondorder phase transitions
33.1 Firstorder & secondorder phase transitions
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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.
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Molecular Rheology LAB
Firstorder 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.
Highdensity phase is more stable below the transition temperature, T
4
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Molecular Rheology LAB
Secondorder phase transitions
Definition: At the socalled critical point (point D), the difference between two
distinct states disappears and there is only one equilibrium state.
Moving along the liquidgas 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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Molecular Rheology LAB
33.2 Latent heat
At firstorder phase transition:
I II
I II
I II
Discontinued in , , , , . But
( ) ( )
( ) ( )
( ) ( )
u f h v s P P
T T
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
Ice Water Steam
kJ
. 11
kgK
P
c kJ
. 11
kgK
P
c
cal
11
g
LS
l
cal
111
g
GL
l
Saturated steam table
Superheated steam table
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Molecular Rheology LAB
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Molecular Rheology LAB
33.3 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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Molecular Rheology LAB
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
+
+ +
apeyron equation
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Molecular Rheology LAB
The Clapeyron equation embodies the Le Chatelier principle. Consider a
solidliquid 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
< <
Stability criteria: or 1 1
T
T
P
V
_
> <
,
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 Pv 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
+ +
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Molecular Rheology LAB
In general, for P < P
D
, the righthand branch (ABCD) of the isotherm in
right figure is physically significant, whereas for P > P
D
the lefthand
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: Cant 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 firstorder phase transitions, and O (D)
corresponds to the critical point, termination of the gasliquid 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
+ +
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Molecular Rheology LAB
33.5 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 hyperplanes in the
x
1
, , x
s1
subspace and below its tangent hyperplanes in the P
s
, , P
t
subspace.
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Molecular Rheology LAB
33.6 Firstorder phase transitions in multicomponent
systems
For a multicomponent 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
1
1
1
1
]
M
variations equations
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Molecular Rheology LAB
Application of the Gibbs phase rule
Example:
I. Singlecomponent system (r 1)
a: M2 f 1 at a given T, P must be unique
b: M3 f 0 the triple point
II. Twocomponent system (r 2)
a: M1 f 3 T, P, x
1
(or x
2
) can be arbitrarily assigned
b: M2 f 2 T, P can be arbitrarily assigned
c: M3 f 1 T, for example, can be arbitrarily assigned
d: M4 f 0 four phases coexist at unique point
There cannot be five phases coexist in this case
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Molecular Rheology LAB
33.7 Phase diagrams for binary systems
Example:
The threedimensional phase diagram of a typical gasliquid binary system.
The twodimensional 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.
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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
34.1 Features in the vicinity of the critical point
34.1 Features in the vicinity of the critical point
34
34
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 firstorder transition breaks.
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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, longrange 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.
110
34
Molecular Rheology LAB
The generalized susceptibilities, such as c
p
,
T
and 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
111
34
Molecular Rheology LAB
34.2 The failure of the classical theory in predicting
the scaling behavior near the critical point.
Oversimplification of the extremum principle in classical
thermodynamics. It must be replaced by the associated probability
distribution and the consequent average properties.
112
34
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.
Renormalizationgroup 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
3H
3H
Molecular Rheology LAB
Problem 9.11
Problem 9.33
Problem 9.411
Problem 9.71
114
Applications to Material Properties
Applications to Material Properties
Contents
41 The general ideal gas
42 Small Deviations from IdealityThe Virial Expansion
43 Law of Corresponding States for Gases
44 Applications to Dilute SolutionsThe vant Hoff Relation
and the Raoults law
4H Homework
Chapter 4
Chapter 4
Molecular Rheology LAB
115
The general ideal gas
The general ideal gas
41.1 The essence of ideal gas behavior
41.1 The essence of ideal gas behavior
41
41
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 singlecomponent ideal gas, T T(u) or u u(T)
3. The Helmholtz potential F(T, V, N
1
, ) is additive (Gibbss theorem)
4. have the same value for all ideal gas
, ,
1 1
T p v
c c R
P T
116
41
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
41
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 steplike feature in the
c
v
versus T curves.
Steplike
118
41
Molecular Rheology LAB
41.2 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
1
+ +
]
+
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 IdealityThe Virial
Small Deviations from IdealityThe Virial
Expansion
Expansion
42
42
Molecular Rheology LAB
: "Second virial coefficient" which accounts for the contribution from
.
: "Third virial coefficient" which accounts for the con
twobody interactions
tribution
h
fr
t
om
1
( ) ( )
1
( )
( )
P R B T C T
T v v v
B T
C T
_
+ + +
,
reebody 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.
42.1 Virial expansion
42.1 Virial expansion
121
42
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)
42.2 Other thermodynamic quantities may be
expanded in a selfconsistent fashion
122
42
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
43.1 Important observations for gases
43.1 Important observations for gases
43
43
Molecular Rheology LAB
In the equation of state of a given fluid, there is one unique point the
critical pointcharacterized 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
43
Molecular Rheology LAB
43.2 The Law of corresponding states
There exists, at least semiquantitatively, 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
43
Molecular Rheology LAB
T
r
curve
126
43
Molecular Rheology LAB
A possible origin of the universal, twoparameter equations of state the
van der Waals force of two sphericallike, nonpolar molecules.
The force between two molecules can be parameterized by the radius of
the molecule, which describes the shortrange repulsion, and the strength
of the longrange attraction.
The longrange 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
+ +
+
+
+
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
<<
+ +
+ +
128
44
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
129
44
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
the vant Hoff relation for osmotic
pressure in dilute solutions
130
44
Molecular Rheology LAB
44.2 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
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
+
+
>>
Raoults law
131
Homework
Homework
4H
4H
Molecular Rheology LAB
Problem 13.22
Problem 13.52
Problem 13.53
132
Statistic Ensembles and Formulism
Statistic Ensembles and Formulism
Chapter 5
Chapter 5
Molecular Rheology LAB
Contents
51 The entropy representationthe Boltzmanns law
51.1 Physical significance of entropy for closed system (15.1)
51.2 The Einstein model of a crystalline solid (15.2)
51.3 The twostate system (15.3); a polymer model (15.4)
52 The Canonical Formalism
52.1 The probability distribution (16.1)
52.2 The partition function (16.2)
52.3 The classical ideal gas (16.10)
53 Generalized Canonical Formulations
53.1 Entropy as a measure of disorder (17.1)
53.2 The grand canonical formalism (17.3)
133
The
The
E
E
ntropy
ntropy
R
R
epresentationthe
epresentationthe
Boltzmanns law
Boltzmanns law
51.1 Physical significance of entropy for closed system
51.1 Physical significance of entropy for closed system
51
51
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
51
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
51
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
51
Molecular Rheology LAB
Correlation of & S
The No. of microstates () 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
51
Molecular Rheology LAB
Entropy ( )
additive (extensive)
S No. of microstates ( )
Multiplicative
6
6
6
6
ln
B
S k
The constant prefactor merely determines the scale of S, and agrees with
Boltzmanns 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
51
Molecular Rheology LAB
51.2 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
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
_
+
,
h
h
h
139
51
Molecular Rheology LAB
Number of permutations of
( )
1
1 1 N U +
%
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
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
+
+
+ +
% %
h
h h
%
h
%
h
% %
h h
%
Q
% %
h h
140
51
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
_ _
+ + +
, ,
+ >>
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
_
+
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
51
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
51
Molecular Rheology LAB
51.2 The twostate system ; a polymer model
Twostate system
Ground state
(with energy 0)
Excited state
(with energy )
Total atoms N
%
: system energy U
( ) atoms are
in the ground state

U
N
%
atoms are in
the excited state
U
( )
( )
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
_ _
, ,
+ >>
%
%
%
%
% %
143
51
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
,
<
+
+
+
%
%
%
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 N
%
144
51
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
51
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 to such a
perpendicular monomer.
146
51
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
+ +
+
+
+
+ + +
+
%
( )
( )
( )
( )
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
+ +
%
%
147
51
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
+ +
+ +
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
+ +
+
Q
Q
T
148
51
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
+
+
+ +
%
%
%
%
% %
%
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
+
+
+
,
%
%
%
T
T
T
T
T
149
The Canonical Formalism
The Canonical Formalism
52.1 The probability distribution
52.1 The probability distribution
52
52
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
52
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
52
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
52
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
( ) ( ) ( )
( )
( ) ( )
( )
( ) { } ( )
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
52
Molecular Rheology LAB
( ) { } ( )
1
define
is stateindependent 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
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
154
52
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
_ _
,
,
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 is merely the reciprocal temperature in natural units.
155
52
Molecular Rheology LAB
52.2 The partition function
Consider a system composed of 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
52
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
, , , ...
Z
j j j
j
j j j
e
e
+ + +
1 1
1 1 1
, , , ...
1 1 1
z z z
j j
j j j
j j j
j j j
e e
e e e
: the energy of the th element
in its th orbitial state
i j
i
j
; : the "partition sum of the th element"
The Helmholtz potential :
1 1
z z
lnZ lnz lnz
i j
i i
j
e i
F
+ +
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
+ +
+
% %
%
%
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
z
j
j
e e e e
+ +
158
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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
_
+
,
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
+ + + +
+ + + +
+ + + + + < <
+
h h h h
h
h h h
h
h
%
h
Q
% %
h
159
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Molecular Rheology LAB
52.3 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
( NN
A
)
T reservoir
Container
volume
V
The energy is the sum of oneparticle
kinetic energies, and the partition
sum factors.
Consider monatomic classical ideal gas:
Neglect interactions
between gas molecules
160
52
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
+ +
_
+
,
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
Q
The oneparticle translational partition sum z
transl
:
V
161
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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
1
]
%
Finding is not extensive! F
To identify Z as z
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
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Molecular Rheology LAB
Reflection on the problem of counting states reveals that division by ! 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
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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 oneparticle 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
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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
+
+
_
,
/ 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
53.1 Entropy as a measure of disorder
53.1 Entropy as a measure of disorder
53
53
Molecular Rheology LAB
Information Theory
Define the information I in terms of the probability f
j
, subject to the
following requirements:
Information is a nonnegative quantity, I(f
j
) 0 .
If an event has probability 1, its 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
53
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
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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
53
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 Shannons measure of disorder.
Entropy in the case of two possibilities
with probabilities f and (1 f).
C. E. Shannon, J. Bell Syst. Tech. 27, 379423 (1948).
At max.
1 1
 / 1 11
1 1
log log 1 11
1 1
f f
H bits
+
170
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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
_ _
, ,
K
For a closed system the entropy corresponds to Shannons quantitative
measure of the maximum possible disorder in the distribution of the
system over its permissible microstates.
171
53
Molecular Rheology LAB
If the system is in contact with a thermal reservoir, the probability of jth 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
+
+
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
172
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Molecular Rheology LAB
53.2 The grand canonical formalism
T & 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
( )
{ } ( )
tot
j j
E N
U TS N
j
N
f e e
173
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Molecular Rheology LAB
{ } ( )
[ ]
( )
( ) ( )
( )
defined = ; is the "grand canonical potential"
is stateindependent 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
Q
: the grand canonical partition sum ; Z
Z
ln Z
j
e
_
,
[ ]
F U T
Multiplied
1
B
k
175
53
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
Auxiliary conditions:
1
1
1
1
j
j
j j
j
j j
j
f
f E E
f N N
Taking differentials
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53
Molecular Rheology LAB
( )
1 1 1
1
j j
E N
j
f e
+ + +
1
1
1
1
( )
j j
E N
j
f e e
( )
1
ln 11
B j j
j
S k f f
( )
( )
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
+ + +
+ + + +
+ + + +
Auxiliary conditions:
1
1
1
1
1
1
1
1
1
j
j
j j
j
j
j
f
E f
N f
Adding 4
equations
Compare the two
equations to identify
1
,
2
,
&
3
.
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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 & reservoir
Solid surface
(system)
There are 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
' )
We seek the fractional coverage of the
surface.
The gaseous phase which bathes the surface establishes the values of T
and , being both a thermal and a particle reservoir.
In such a case , 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 GibbsDuhem relation if the equation of state are
known.
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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
+ + + +
+ +
+
%
( )
( )
( ) ( )
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
+
z e
Q
179
53
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
( ) ( )
( )
( )
( )
( )
The number of adsorbed atoms on the sites:
; is constant
1 1
1
ln Z = ln z ln 1
N
B B B
k T k T k T e e
N N
N Nn T
U N
+ +
%
%
%
Q
%
180
Homework
Homework
5H
5H
Molecular Rheology LAB
Problem 15.11
Problem 15.21
Problem 15.44
Problem 16.11
Problem 16.14
Problem 16.21
Problem 16.104
181
Statistical Fluctuations and Solution
Statistical Fluctuations and Solution
Strategies
Strategies
Chapter 6
Chapter 6
Molecular Rheology LAB
Contents
61 Fluctuations
61.1 The probability distribution of fluctuations (19.1)
61.2 Moments and the energy fluctuations (19.2)
62 Quantum Fluids
62.1 Quantum particle fermions and bosons (18.1)
62.2 The ideal Fermi fluid (18.2)
62.3 The ideal Bose fluid (18.5)
62.4 The classical limit and the quantum criterion (18.3)
62.5 The strong quantum regime: electrons in a metal (18.4)
62.6 Bose condensation (18.7)
182
Fluctuations
Fluctuations
61.1 The probability distribution of fluctuations
61.1 The probability distribution of fluctuations
61
61
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
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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 :
F E
E
f e
T, P reservoir
subsystem
Case
II:
( )
The probability that the system occupies a particular
microstate of energy and volume :
G E PV
E V
f e
+
184
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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
s
X X X
X X
K
K :
s
X
( ) { }
, ,
, , ,
=e
: the Massueu function
: the entropic intensive parameters
1 1
1 1 1 1 1
1 1
, ,
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
1
1
F E
F
S
T T
F
T
X E
f e
1
1
]
e.g.
( )
,
;
;
1 1
1 1
1
1
E N
S
T T T
F F
T T
X E X N
f e
1
1
]
( )
,
;
;
1 1
1 1
1
1
G E PV
G P
S
T T T
P
F F
T T
X E X V
f e
+
1
1
]
185
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Molecular Rheology LAB
61.2 Moments and the energy fluctuations
Suppose that the is the only fluctuating variable, all other extensive
parameters being constrained by restrictive walls.
( ) ( )
( )
( )
( )
( )
( )
( )
: the deviations
;
: the meansquare deviation (the second central moment)
1
1 1 1
1
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
_
,
Q
186
61
Molecular Rheology LAB
( )
( )
( )
( )
( )
( )
( )
1
1
1
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
Q
The mean square energy fluctuations are proportional to the size of the
system.
The relative rootmeansquare 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
E U U
A very useful expression to estimate
the heat capability of a system in
computer simulations.
187
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Molecular Rheology LAB
Higherorder moments of the energy fluctuations:
( )
( )
( )
( ) ( )
( )
( )
( )
( )
( ) ( )
e.g. the third moment:
1
1
1
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
+
+
+
1
1 1 1
1
v
B v
c
U Nk T Tc T
T
_
+
,
The higherorder moments of the energy fluctuations can be generated
from the lowerorder moments by the recursion relation.
188
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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
( / ) 1
( / ) 1
( / )
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
_
,
+
_
B
1
/ , ,... 1T N
T
k T V
_
,
+ +
+ +
193
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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
t
1
+ + +
]
empty 2 singly occupied double occupied
( ) ( ) ( )
The fundamental equation:
1 1 1
1 1 1
Z 111 e e e e
1 1 1
+ + +
] ] ]
( ) ( )
1
1 1
n n
e e
194
62
Molecular Rheology LAB
( ) ( ) ( )
( ) ( ) ( )
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
+ +
+ + +
_
,
+ +
+ + +
% %
%
determines the entropy.
_
,
The fundamental equation is an attribute of the thermodynamic system,
independent of boundary conditions. In general, the Fermi level as a
function of T and must be determined.
195
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Molecular Rheology LAB
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
+ +
+
196
62
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
1
+
]
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
_
,
1
+
]
_
1
+
]
,
h
h
%
; N
_
_
,
,
%
197
62
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
198
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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
+ + + +
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
_
,
( ) ( ) ( )
k k k
1 1 1 1
k,
k,
z
ln z
s
s
m
B m
e e
k T
1
+ + +
]
L
199
62
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
1
]
_
,
%
h
The quantity is not necessarily less than unity, and therefore is
more properly identified as a mean occupation number .
If were positive the orbital state with
k
equal to would have an
infinite occupation number! So, the molar Gibbs potential is always
negative.
,
s
k m
n
, k
s
m
f
occupation probability (or
mean occupation number)
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62
Molecular Rheology LAB
62.2 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
+
<<
%
%
h
; : the thermal wave length
11
11 1
1
1
1
T
T T
B
g V
e e d e
h
mk T
1
_
1
,
]
h
%
The equation of state of
classical ideal gas
( )
The criterion that divides the quantum and classical regimes:
or classicalquantum boundary
1
1
11
T
g V
e
N
_
,
%
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 or by virtue of low T (and consequently of large
T
).
The classical limit the fugacity is the ratio of the thermal
volume
3
T
to the volume per particleV/(/g
0
).
N
%
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Molecular Rheology LAB
62.3 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
%
h h
1
K
( )
for
for
1
1
1
1
,
1
T K
f T
<
'
>
Metal T
F
(K)
Li 5.510
4
Na 3.710
4
K 2.410
4
Rb 2.110
4
Metal T
F
(K)
Cs 1.810
4
Cu 8.210
4
Ag 6.410
4
Au 6.410
4
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62
Molecular Rheology LAB
( )
The heat capacity:
1
1
1
1
1 1
B
B
k T
C Nk O T
_
+
,
%
The prefactor 3k
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 >> 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
62.4 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
1
e
e
e
e B
N
g V m
N d
e
e
N
g V g V m
N k T
,
< <
1
_
1
, 1
]
%
%
h
%
%
h
( )
( )
; : the thermal wave length
11 1
1 1
11 11
1
1
1 1 1 1
T
T T
B
r
r
F
h
mk T
F
r
+ + +
L
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62
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 1
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
,
1
_
1
, 1
]
+ + +
h
h
L
%
Q
( )
( )
( )
( )
1 1
11 1 1
11
11
11
1
1
e
T T
e B
g V g V N
F
F
F
U N k T
F
%
%
The ratio measures the deviation from the classical
equation of state.
( ) ( )
11 11
F F
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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
At
11
11
1
. 1 1 1
. 1111
F
F
At
slope of
slope of
11
11
1
1
1
F
F
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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
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
_
,
%
%
%
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
209
62
Molecular Rheology LAB
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.
s
(T): superfluid density of
4
He
n
(T): normal fluid density of
4
He