Advanced Thermodynamics

Advanced Thermodynamics
Instructor: Prof. Chi-Chung Hua

Complex Fluids & Molecular Rheology Laboratory,
Department of Chemical Engineering,
National Chung Cheng University, Chia-Yi 621, Taiwan, R.O.C.
Molecular Rheology LAB

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: 易函柳 (Rm414, Ext. 23482 )

2
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 Formulism
Chapter 6: Statistical Fluctuations and Quantum Fluids
3
Chapter 1 Basic Concepts and Principles
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
4
1-1
Thermodynamic Equilibrium and
1-1
Postulate I
1-1.1 Thermodynamic coordinates
Macroscopic vs. Microscopic
Variables Responses
Experimental variables Experimental results

Simulation variables Simulation data
5
1-1
Q1: How to select variables of an experimental or simulation
system?
A1: 1. Use minimum number of measurable variables.

2. Each variables must be independent.
Q2: Select macroscopic or microscopic variables?
A2: The basis of selection is the scale of the phenomena or substances of

primary interest.
Microscopic 1μm Macroscopic
length scale
6
1-1
Microscopic properties can spread to macroscopic properties
Microscopic Macroscopic
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.
7
Figure 1.1 Length and time scales of atoms and cats
http://www.bibalex.org/English/lectures/printable/zewail.htm 8
1-1
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).
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.
9
1-1
1-1.3 Limitations of thermodynamic equilibrium
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 N1,N2,…Nr;
e.g., S = S(U, V, N) for a one-component system.
10
1-2
The Entropy Maximum Postulates:
1-2
Postulate II & III
Postulate II:
For an isolated system with constant V, N, U the equilibrium criterion requires
that the entropy S reaches a maximum value.
Postulate III:
S is a monotonically increasing function of U.
S  S (U , V , N 1 , ... , N r )
 S 
 U  0
 V , N1 , ... , N r
11
1-2
The system may then be V1 V2

further divided into two
sub-systems subject to U1 U2
certain constraints: N1 N2
S ＝ S（U , V , N） thermodynamic constraints
U1  U 2  U1'  U 2'
S ＝ S（U） only U1'  ?
By entropy
U ?
'
2 max.
12
1-2
 S 
dS    dU ; S is extreme value  dS  0
 U  N ,V
Use d2S to check S is
S  S1 (U 1 )  S2 (U 2 ) max. or min.
 S1   S 2  1 1
 dS    dU1    dU 2  dU 1  dU 2  0
 U1  N ,V  U 2  N ,V T1 T2
1 1
dS  (  )dU1  0 dU1  dU 2  0
T1 T2
1 1
(  )0 dU1  0
T1 T2
An important equilibrium
T1 ＝ T2 condition
13
1-2
Fixed V & U Fixed U & N
V1 V2 V1 V2
U1 U2 U1 U2
N1 N2 N1 N2
thermodynamic constraints thermodynamic constraints
Others equilibrium conditions can be derived with fixed V

& U or N & U.
μ1 ＝ μ2 for fixed V & U
P1 ＝ P2 for fixed N & U
14
1-3
Intensive Parameters and Equations of
1-3
State
1-3.1 Extensive parameters & intensive parameters

Extensive parameters
S , U , V , N : First order extensive parameters

S (U , V ,  N )   1 S (U , V , N ) First order
Example: S (9U , 9V , 9N )  9 S (U , V , N )
Enlarged 9 times S S S
S S S S
S S S 15
1-3
Intensive parameters
S  S (U , V , N ) ; U  U ( S , V , N ) Fundamental equations
 S  1  S  P  S  
 U   ;    ;   
  N , V T  V U , N T  N U , V T
 U   U   U 
 S  T ;    P ;   
 N , V  V  N , S  N  S , V
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.
16
1-3
Chemical potential:
 U 
The definition of chemical potential is the  N  
energy change from a particle, molecule or  S, V
electron move into or leave the system.
Example:
If the overall system has reached an equili-

Gas brium, the energy reduction(increase) in
the liquid phase due to the moving of a
Liquid molecule into the gas phase is the same as
the energy increase(reduction) in the gas
phase. So, the total system energy remains
unchanged.
17
1-3
1-3.2 Fundamental equations & equations of state
Fundamental equations
S  S (U , V , N ) Entropy representation
U  U(S, V , N ) Energy representation
Two equations are alternative forms of the fundamental relation, and each
contains all thermodynamic information about the system.
The fundamental equations describe homogeneous first-order parameters.
18
1-3
Equations of state
U  U  S ,V , N 
 U   U   U 
 S   T ;  V    P ;  N  
 N , V  N , S  S, V
T  T(S, V , N ) Equations of state:
P  P( S , V , N ) An intensive parameter is expressed in

terms of independent extensive parameters.
  ( S , V , N )
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.
19
1-3
Figure 1.2 U vs. S & U vs. T in constant V & N
20
1-3
Zero order
 (U )  (U )
   0T
 ( S ) N , V  ( S ) N , V
U & S are first order parameters
T ( S , V ,  N )  T ( S , V , N )
P ( S , V ,  N )  P ( S , V , N ) Equations of state
 ( S , V ,  N )   ( S , V , N )
The equations of state describe homogeneous zero-order parameters.
21
1-3
1-3.3 Unit of temperature
Thermodynamic engine
Th Thermodynamic engine efficiency:

dQh
dWrev Tc
εe   1
dWrev dQh Th
Used to define temperature scale.

Tc
T1  T1
 Permissible scale (e.g. K, R)
T2  T2
T1 T1  k
 Non-permissible scale (e.g. oC, oF)
T2 T2  k
22
1-3
Question: All heat can be transfer to work?
Answer: It is impossible unless Tc = 0K
Rotation
Tc ≠ 0K Internal energy
Heat Molecular Vibration
Kinetic energy Work
Rotation
Tc = 0K Internal energy = 0
Heat Molecular Vibration
Kinetic energy All heat transfers to

produce work
23
1-3
Unit of temperature
Unit of U is energy. So, unit of temperature is energy.
 U 
 S  T Unit of entropy:
 N , V
In classic thermodynamics, entropy
What is the unit of
is dimensionless parameter.
entropy?
In thermostatistics, unit of entropy
correlates with states.
The temperature scale, Kelvin, was used in molecular scale.

e.g. Energy of a simple molecule = 3/2 kBT = 3/2 Kelvin
Joule/Kelvin = 1.38 x 10-23 = kB
24
1-3
1-3.4 The general case of entropy max. in equilibrium
S total  S1 (U 1 , V1 , N 1 )  S 2 (U 2 , V2 , N 2 ) w.s.t. dU , dV , dN
1 P1 1

T1 T1 T1
 S1   S1   S1 
dS    dU 1    dV1    dN 1
 U 1 V1 , N1  V1 U1 , N1  N 1 V1 ,U1
 S 2   S 2   S 2 
  dU 2    dV2    dN 2
 U 2 V2 , N 2  V2 U 2 , N 2  N 2 V2 ,U 2
1 P2 2

T2 T2 T2
25
1-3
 1 1  P1 P2   1 2 
dS     dU1     dV1      dN 1  0 at equilibrium
 T1 T2   T1 T2   T1 T2 
T1  T2
This equation always holds only if P1  P2
1  2
If dS  0 in reaching equilibrium
initial state
1. P1  P2 , 1  2 , T1  T2 dU1  0
2. P1  P2 , 1  2 , T1  T2 dV1  0
3. P1  P2 , 1  2 , T1  T2 dN 1  0
26
1-4
The Euler Equation and the Gibbs-Duhem
1-4
Relation
1-4.1 The Euler relation

Homogenous first order property
U ( S , V ,  N 1 ,  N 2 , ...)  U ( S , V , N 1 , N 2 , ...)
differentiating w.r.t.  (d  )
T S P V
U ( S , V ,  N 1 ,  N 2 , ...)  ( S ) U (  S , V ,  N 1 ,  N 2 , ...) ( V )

 ( S )   (V ) 
U ( S , V ,  N 1 ,  N 2 , ...)  (  N 1 )
  ...  U ( S , V , N 1 , N 2 , ...)
 ( N 1 ) 
1 N1
27
1-4
U ( S , V , N 1 , N 2 , ...)  TS  PV  1 N 1  2 N 2  ...
 TS  PV    j N j
j=1
Let PX
i=1
i i   PV    j N j
j=1
U ( S , V , N 1 , N 2 , ...)  TS   Pi X i
i=1
Another form:
1 P  j 
S (U , V , N 1 , N 2 , ...)    U    V     N j
T  T  j  T 
The Euler relation is useful for deducing many important thermodynamic

relationships, including the famous Gibbs-Duhem equation.
28
1-4
1-4.2 The Gibbs-Duhem equation
Euler relation: U ( S , V , N 1 , N 2 , ...)  TS   Pi X i
i=1
dU  TdS  SdT   PdX

i i   X i dPi
i=1 i=1
Given that dU  TdS   PdX

i i
i=1
One obtains SdT   X i dPi  0 the Gibbs-Duhem equation

i=1
1 P  j 
Another form Ud    Vd     N jd    0
T  T  j T 
Not all intensive properties are independent, but only n-1 of them are
independent. Another one can be deduced from the Gibbs-Duhem
equation.
29
1-4
Example:
For one-component systems (having 3 intensive properties T , P &  )
SdT  VdP  Nd   0
S V Only T & P are independent, μ
d    dT  dP   sdT  vdP can be deduced from the Gibbs-
N N Duhem equation.
s & v : unit number S & V
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.
30
1-4
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

T  T(S, V , N )
P  P( S , V , N ) U  TS   Pi X i U  U(S, V , N )
  ( S , V , N )
The totality of all equations of state can be used to reconstruct the

fundamental equation.
31
1-H
1-H Homework
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)
32
Thermodynamic Potentials and
Chapter 2 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
33
2-1
2-1 Legendre Transformations
2-1.1 The S max. principle & the U min. principle
An isolated system must conform with two

extremum criteria when equilibrium is reached.
Entropy max. principle: Energy min. principle:

Entropy is max. value for Energy is min. value for
given total energy. Equivalent given total entropy.
representations
34
2-1
S max. principle U min. principle
Fundamental
surface
Figure 2.1 The equilibrium state A as a point of max. S for constant

U & min. U for constant S.
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.
35
2-1
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.
Can withdraw energy The system would be restored to its

dU = -dW original energy but with an increased S.
Energy So, it is inconsistent with the principle
System that the initial equilibrium state is the
Return energy to sys. state of maximum entropy.
-dW = dQ = TdS
The original equilibrium state must have had min. energy consistent with
the prescribed entropy. The inverse argument is the same.
36
2-1
Mathematical exercise
Entropy maximum principle:
 S   2S 
 X   0 and  X 2   0 X : Particular extensive parameter
 U  U
 S 
 X   U 
 U   U  S 
 X     T  X   0  X   0
 S   S   U  S
 U 
 X
By eqn. A.22 of Appendix A
37
2-1
Chain Rule
  S    2S   2
S
   2 
  2U     X U

 
X  U   S   X  U
 2 
=   
 X  S X    S       X  U   S 
2
S
  U 
X   U 
 X  U 
 S  X
2S S  2S 
 T 0 at 0  2 
0 & T 0
X 2
X  X  U
From S max. principle: U min. principle:

 S   2S   U    2U 
 X   0 ;  X 2   0  X   0 ;  X 2   0
 U  U  S  S
38
2-1
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.
39
2-1
X, Y are extensive properties & Y=Y(X).

Y
Let slope is P  ; P: intersive properties
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.
Y  Y(X )   (P)
Y Y   
P  X 
X X  0 P
  Y  PX Y    PX
Elimination of X and Y yields Elimination of P and  yields
  (P) Y  Y(X )
40
2-1
Generalization of the Legendre transformation
Y  Y ( X 0 , X 1 , ... , X t )    ( P0 , P1 , ... , Pn , X n1 ,

Y ... , X t )
Pk 
X k 
Xk  
  Y   Pk X k Pk
Y     Pk X k
k
Elimination of Y and X 0 , X 1 , k
... , X n yields Elimination of  and P0 , P1 ,

   ( P0 , P1 , ... , Pn , X n1 , ... , Pn yields
... , X t ) Y  Y ( X 0 , X 1 , ... , X t )
41
2-2
The Legendre Transformed Functions
2-2
and Thermodynamic Potentials
Legendre transformed functions
The energy representation of the

Y  Y ( X 0 , X 1 , ... , X t )
fundamental equation: U  U ( S , V , N )
Y Intensive parameters
Pk 
X k T ,  P , 1 , 2 , ...
Thermodynamic potentials
F  F (T , V , N )
  Y   Pk X k
k H  H (S, P, N )
G  G (T , P , N )
42
2-2
The Helmholtz potential, F
U(S, V , N )  F (T , V , N )
Y X ψ P
Y  Y ( X 0 , X 1 , ... , X t )
Y U  U(S, V , N )
Pk 
X k U
T
  Y   Pk X k S
k F  U  TS
   ( P0 , P1 , ... , Pn , X n1 , F  F (T , V , N )
... , X t )
 F   F   F 
 T    S ;  V    P ;  N  
 N , V  T , N  T , V
dF   SdT  PdV   dN
43
2-2
The Enthalpy, H
U(S, V , N )  H (S, P, N )
Y X ψ P
Y  Y ( X 0 , X 1 , ... , X t )
Y U  U(S, V , N )
Pk 
X k U
P 
  Y   Pk X k V
k H  U  PV
   ( P0 , P1 , ... , Pn , X n1 , H  H (S, P, N )
... , X t )
 H   H   H 
 S   T ;  P   V ;  N   
 P, V  S, N  P, S
dH  TdS  VdP   dN
44
2-2
The Gibbs potential, G
U(S, V , N )  G (T , P , N )
Y X1 X2 ψ P1 P2
Y  Y ( X 0 , X 1 , ... , X t )
Y U  U(S, V , N )
Pk 
X k U U
T ; P
  Y   Pk X k S V
k G  U  ST  PV
   ( P0 , P1 , ... , Pn , X n1 , G  G (T , P , N )
... , X t )
 G   G   G 
 T    S ;  P   V ;  N  
 P, N  T , N  P, T
dG   SdT  VdP   dN
45
2-2
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.
The following equations are all fundamental equations:

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 & Phase equilibrium
46
2-3
2-3 Minimum Principles for the Potentials
The Helmholtz potential
Consider a subsystem in contact with a thermal reservoir.
Reservoir T r Thermal reservoir (Cp → ∞, T ＝ T r )
T(1) T(2) Subsystem
Using U representation U=U(S, V, N) :
dU total  0 from the extremum

d 2U total  0 principle at equilibrium
47
2-3
dU r dU
dU total  (dU r  dU )  (T r dS r  T (1)dS (1)  T (2)dS (2) )
( P (1)dV (1)  P (2) dV (2) )  (  (1) dN (1)   (2) dN (2) )  0
 U r
  U r
  U r

dU   r 
r
dS  
r
 dV r
   dN r
 S V r , N r  V  S r , N r  N V r , S r
r r
 T r dS r
S total  constant  dS total  dS  dS r  dS (1)  dS (2)  dS r  0

dS (1)  dS (2)   dS r
The subsystem of interest  dV (1)  dV (2)  0 ; dN (1)  dN (2)  0

dV (1)   dV (2) ; dN (1)   dN (2)
48
2-3
(T (1)  T r )dS (1)  (T (2)  T r )dS (2)  ( P (1)  P (2) )dV (1)  (  (1)   (2) )dN (1)  0
T (1)  T (2)  T r
This equation always holds only if P (1)  P (2)
 (1)   (2)
At equilibrium
dU total  (dU  dU r )  dU  T r dS r  d (U  T r S r )  d (U  TS )  0
 dF  0 F  U  TS
d 2U total  d 2 (U  U r )  d 2U  d 2U r  d 2U  d 2U  d 2 (TS )  d 2 (U  TS )  0
 d 2F  0 By eqn. A.9 of Appendix A ;
For thermal reservoir T = T r, V r & N r = constant
49
2-3
By the same way, consider a subsystem in contact with a pressure reservoir,

or with both pressure & thermal reservoirs.
Reservoir P r Reservoir T r & P r
P(1) P(2) Subsystem T(1) P(1) T(2) P(2)
H  H (S, P, N ) G  G (T , P , N )
dH  0 dG  0
d 2H  0 d 2G  0
50
2-3
The overall system:
Representation: Experimental conditions: Extremum criteria:

U  U ( S ,V , N ) V total , N total , S total dU total  0 ; d 2U total  0
The subsystem:
Representation: Experimental conditions: Extremum criteria:

F  F (T ,V , N ) T, V , N dF  0 ; d 2 F  0
H  H (S, P, N ) S, P, N dH  0 ; d 2 H  0
G  G (T , P , N ) T , P, N dG  0 ; d 2G  0
51
2-3
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.
52
2-4
Applications of various Legendre
2-4
Transformed Potentials
2-4.1 The Helmholtz potential
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.

53
2-4
Example:
Two simple subsystems separated by a
movable, adiabatic, impermeable wall.
V (1)  ?
V ( 2)  ?
Wrev  ?
P (1) (T r , V (1) , N (1) )  P (2) (T r , V (2) , N (2) )

Can solve V (1) & V (2)
V (1)  V (2)  V , a constant
dWrev   dU  dU r   dU  T r dS r   dU  T r dS   d (U  T r S )
  dF
The number of independent variables: V & N
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.
54
2-4
Focus our attention exclusively on the subsystem of interest, and relegate

the reservoir only to an implicit role.
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.
As shown in Chap. 16, statistical mechanical calculations are enormously

simpler for such systems, permitting calculations that would otherwise be
totally intractable.
See Example.1 in page 159, which shows that one can increases the
entropy of a subsystem without changing the associated internal energy.
55
2-4
2-4.2 The enthalpy
dH  TdS  VdP  1dN 1  2dN 2  ...
At constant P , N i  dH  TdS  dQ As a potential for heat
H  (S, P, N )
 H  H (V , P , N )
V    V (S, P, N )
 P  S , N
Qi  f  H (V f , P , N )  H (Vi , P , N ) At constant P , N
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.
Using a similar argument, U is a potential for heat, too.

dU  TdS  PdV   dN ; at constant V , N  dU  TdS  dQ
56
2-4
The Joule-Thomson process
u f  ui  Pi vi  Pf v f ; by conservation of energy u: initial molar energy

 u f  Pf v f  ui  Pi vi v: molar volume
h f  hi A constant H process h: molar enthalpy
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.
57
2-4
The isenthalpic curves (“isenthalps”)
The final temperature Tf can be

higher or lower then Ti in this
process, depending on the local
relationship:
 T 
dT    dP
 P  H , N1 , N 2 , ...
By eqn. A.22 of Appendix A
& Maxwell relations
v
dT  T  1 dP
CP
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.
58
2-4
2-4.3 The Gibbs potential
Most experiments are carried out under constant T & P.

 G  (T , P , N1 , N 2 , ...) is a particularly convenient choice.
by defition: G  U  TS  VP
the Euler relation: U  TS  VP   i N i
i
 G   i N i As a potential for chemical potential

i
r
Consider the chemical reaction: 0   j A j
1
Aj : symbols for the chemical components

 j : stoichiometric coefficients
59
2-4
Change of G associated with changes in Nj can be described by
dG   SdT  VdP    j dN j
j
dN1 dN 2
since   ...  dN  dN j   j dN
1 2
dG  dN   j j  0
j
One has for the equilibrium condition:
or  
j
j j 0
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:
dH   r 
 T  j j 
 
dN T  1  P , N1 , N 2 , ...
60
2-4
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.
61
2-5
2-5 Maxwell Relations and Some Applications
2-5.1 The Maxwell relations & mnemonic diagram

Maxwell relations
U  U(S, V , N )
Constant N
2nd derivatives of potential

  U    U  Maxwell relation equation

S  V  V  S 
    P   T 
    
P T  S V , N  V  S , N
62
2-5
In a similar way, we can derive other forms as shown below:
Table 2.1. Maxwell relations for several potentials with various pairs of
independent variables. (see also pp. 182 & 183 of the textbook)
63
2-5
Mnemonic diagram
Valid Facts Theoretical

V F T
Understanding U G Generate
S H P
Solutions Hard Problems
Pithy formula: “Valid Facts and Theoretical Understanding Generate

Solutions to Hard Problems”
64
2-5
The first derivative of potential:
Example:
V F T
 U 
 S  T ("  " arrow pointed away)
 S, N
U G
 U 
 V   P ("  " arrow pointed toward)
 V , N S H P
Maxwell relations:
Example: V T
 V   T 
 S    
  P  P  S
("  ") S P S P ("  ")
T V T ("  ")
 S   V 
 P     T 
 T  P
S P ("  ") P 65
2-5
If we are interested in Legendre transformations dealing with S and Nj ,

the mnemonic diagram takes the form shown as below in the left diagram:
Nj F  U [T ] T X1 U [ P2 ] P1
U U [T ,  j ] U U[ P1 , P2 ]
S U [ j ] j X2 U[ P1 ] P2
U(S, Nj) mnemonic diagram General-form mnemonic

diagram
66
2-5
2-5.2 Procedure for the reduction of derivatives
Four customarily used derivatives
1  v  1  V 
  
v  T  P V  T  P
Thermal expansion coefficient:
1  v  1  V 
T      
V  P T
Isothermal compressibility:
v  P  T
 s  T  S  1  dQ 
Molar leat capacity at constant pressure: cP  T        
 T  P N  T  P N  dT  P
 s  T  S  1  dQ 
Molar leat capacity at constant volume: cV  T        
 T V N  T V N  dT V
67
2-5
For single-component systems and constant molecule numbers, the second

derivatives of Gibbs representation can be expressed by cP ,  , and  T .
2g 2g 2g

  c P /T ;  v ;   v T
T 2
T P P 2
All first derivative, such as dT   T P V , N dP (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  , cP and  T .
68
2-5
Reduction of derivatives
If the derivative contains any potential, bring them one by one to the
numerator and elimin2 e by the thermodynamic square.
Example:
 P 
Reduce the derivative   (See also pp. 187-188 of the textbook)
 U  G , N
1
 P    U  
 U     
 G , N   P G , N 
1
  S   V  
 T    P  
   P G , N   P G , N 
1
  G   G   G   G  
  T    S   P  P   V  
  P  S , N  P, N  V , N   P , N 
1
  S  T P  S , N  V  S  T P V , N  V 
  T P 
  S   T  S P, N  S   T  V  P , N  69
2-5
If the derivative contains the chemical potential, bring it to the numerator
and eliminate by means of the Gibbs-Duhem relation, d    sdT  vdP .
Example:
  
Reduce the derivative  
 V  S , N
    T   P 
 V    s  V   v  V 
 S, N  S, N  S, N
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 T under S. The numerator will then be expressible as one
of the cV or cP.
Example:
 T 
 P  S , N
 T   S   S   V  N
 P     P       c
 S, N   T , N  T  P , N  T  P , N T P
70
2-5
Bring the volume to the numerator. The remaining derivative will be

expressible in terms of  and  T .
Example:
 T 
 P V , N
 T   V   V  T
 P     P    
 V , N   T , N  T  P , N 
The originally given derivative has now been expressed in terms of the
four quantities cP , cV ,  , and  T . The specific heat at constant volume is
eliminated by the follow equation.
Tv 2
cV  c P 
T
71
2-5
2-5.3 Some simple applications
I. Adiabatic compression
Adiabatic wall Adiabatic wall
Quasi-static process
Ti Tf =?
Pi Pf
If known: fundamental equation, Pi , Pf , and Ti
Equations of state:
Fundamental equation (see p. 190)
ΔT=T(S, Pf , N)- T(S, Pi , N)
If known: Pi , Pf , Ti ,c P ,  , and  T
 T  Tv    sTv
dT    dP  dP ; d    P  dP  ( v  )dP
  P S, N c P  S, N c P
72
2-5
II. Isothermal compression
Quasi-static process dS  ?
Pi Pf dU  ?
Constant T Q  ?
If known: fundamental equation, Pi , and Pf

Equations of state:
S  S (T , P , N )
Fundamental equation
U  U (T , P , N )
Q  T S  TS (T , Pf , N )  TS (T , Pi , N )
If known: Pi , Pf ,c P ,  , and  T
 S   U 
dS    dP  VdP ; dU    dP  ( T v  PV  T )dP
 P T , N  P  T , N
dQ  TVdP  Q  T  VdP
Pf
Pi 73
2-5
III. Free expansion
Adiabatic wall Adiabatic wall
Gas Gas
Vacuum
Vi ; Ti Constant U Vf ; Tf =?
If known: fundamental equation, Vi , V f , and Ti
Equations of state:
Fundamental equation
T f  Ti  T (U , V f , N )  T (U , Vi , N )
If known: Vi , V f ,Ti , c P ,  , and  T
 T   P T 
dT    dV     dV
 V U , N  NcV NcV  T 
74
2-H
2-H Homework
Problem 5.3-1
Problem 5.3-12
Problem 6.3-2
Problem 7.4-7
Problem 7.4-15
Problem 7.4-23 75
Stabilities, Phase Transitions, and
Chapter 3 Critical Phenomena
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
3-H Homework
76
3-1
Stability Conditions for Thermodynamic
3-1
Potentials
3-1.1 Intrinsic stability of thermodynamic systems
Basic extremum principle of thermodynamics:
dS  0 The S is an extremum value.
The extremum value is a maximum, which guarantees

d 2S  0
the stability of predicted equilibrium states.
77
3-1
Initial state Remove ΔU from the New state
right subsystem and
transfer it to the left
subsystem.
S(U) S(U) S(U+ΔU) S(U-ΔU)
S Total  2 S U  S Total  S U  U   S U  U 
Convex
Concave
S  U  U   S U  U   2 S (U ) S  U  U   S U  U   2 S (U )
(see later dicussion (see later discussion on the
 Unstable on phase separation)  Stable Le Chaterlier’s principle)
78
3-1
The condition of stability is the concavity of the entropy.

S U  U   S U  U   2S (U ) for all 
By eqn. A.4 of Appendix A (refer to problem 8.1-1 of the textbook)
 2S 
 2 
0 For U  0
 U V , N
The same considerations apply to a transfer of volume.

S V  V   S V  V   2 S (V ) for all 
 2S 
 2 
0 For V  0
 V U , N
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.
79
3-1
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.
80
3-1
If one simultaneously changes U and V:
 2S 
 2 
0
 U V , N
The local conditions of stability ensure the
curve of the intersection of the entropy
surface with the plane of constant V or U
 2S 
 2 
0 have a negative curvature.
 V U , N
But these two “ partial curvatures” are not sufficient to ensure concavity.
S  U  U , V  V   S  U  U , V  V   2 S (U , V )
By eqn. A.4 of Appendix A (refer to
problem 8.1-1 of the textbook)
2
 2S  2S   2S 
 2  2 
  0
 U   V   U V 
81
3-1
3-1.2 Stability condition for thermodynamic potentials
Convexity of the energy surface:
U  S  S , V  V , N   U  S  S , V  V , N   2U ( S , V , N )
The local conditions of convexity:

  2U  T
 2  0
  S V , N  S
  2U  P
 2 
  0
 V  S , N V
For cooperative variations of S and V :

2
  2U    2U    2U 
 2  2 
  0
 S   V   S V 
82
3-1
Transform to other potential representations by Legendre

transformation :
Example:
F  (T , V , N )
  2F   S   T  1  U    2U 
 2 
    1    1    1  2 
 T V , N  T V , N  S V , N   S V , N  S V , N
  2F    2U    2F 
 2 
0 ;  2 0 ; By the same way  2 
0
 T V , N  S V , N  V T , N
F T  T , V  V , N   F T  T , V  V , N   2F (T , V , N )
By eqn. A.4 of Appendix A (refer to problem 8.1-1 of the textbook)
2
  2F    2F    2F 
 2  2 
  0
 V   T   V T 
83
3-1
Similarly, one has for other potentials
H  (S, P, N )
2
 2H   2H   2H   2H   2H 
 2 
0 ;  2 
0 ;  2  2 
  0
 S V , N  P V , N  S   P   S P 
G  (T , P , N )
2
  2G    2G    2G    2G    2G 
 2 0 ;  2   0 ;  2  2     0
 T V , N  P V , N  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.
84
3-2
Le Chaterlier’s Principle and the Effects
3-2
of Fluctuations
3-2.1 Le Chatelier’s principle

The Le Chatelier’s principle: any inhomogeneity that somehow develops
will induce a process that eradicates the inhomogeneity.
Example:
Incident
photon
Container
Fluid Fluid
T1 T1
T1 T1’
In equilibrium Locally heating Heat flows away The system restores

state the fluid slightly. form heated region. homogeneous state.
85
3-2
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).
86
3-2
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.
Example:
Consider a subsystem contained within a cylinder with diathermal walls and
a loosely fitting piston. Piston is moved outward slightly by
external agent or fluctuation.
Primary effect: The Pi decreased-the pressure Po

difference across the piston then acts to push it
inward; this is the Le Chatelier principle.
Pi ; Ti ; Vi
T&P
reservoirs 87
3-2
Secondary effect: An increased Vi alters Ti ; heat flows inward if α＞0 and

outward if α＜0.
 T  T
dT    dV   dV
 V  S NcV  T Piston is moved outward
slightly by external agent
or fluctuation.
Then, Pi 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 Po
Le Chatelier-Braun principle.
1  P   Pi ; Ti ; Vi
dP    dQ  dQ ; dQ  TdS
T  S  S NT cV  T
2
Q
T&P
(note that  dQ is always positive) reservoirs
88
3-3
First-order Phase Transitions in Single-
3-3
Component Systems
3-3.1 First-order & second-order phase transitions

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.
• Global min. is path independent state, yet the metastable one is path
dependent.
The system spends almost all the time in the more stable minimum.
89
3-3
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 T4, 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, T4. 90
3-3
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. 91
3-3
3-3.2 Latent heat
At first-order phase transition:
 ( I )   ( II )
Discontinued in u, f , h, v , s. But P ( I )  P ( II )
T ( I )  T ( II )
Example:
Latent heat of fusion:
dQ  Tds  Q  l LS  T ( s ( L )  s ( S ) )  T s
since h  Ts   ; at phase transition point   ( L )   ( S )
 h  T s  l LS
l LS  80 cal lGL  540 cal

g g
Ice Water Steam
cP  2.1kJ cP  4.2 kJ
Saturated steam table
kg-K kg-K
Superheated steam table
92
3-3
93
3-3
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.
94
3-3
The Clapron equation
Clapron equation is the slope of coexistence curves.

dP
Slope:
dT
At phase equilibrium   A   A ;  B   B
  B   A   B   A ; d    sdT  vdP
  B   A   sdT  vdP   B   A   sdT  v dP
dP ( s'  s ) s
(v   v )dP  ( s  s )dT   
dT (v'  v ) v
l
and l  T s  s 
T
dP l
 The Clapeyron equation
dT T v
95
3-3
The Clapeyron equation embodies the Le Chatelier principle. Consider a

solid-liquid transition with a positive latent heat (sl > ss):
dP
If (vl  v s )  Slope  0
dT
Increase P at constant T  System tends towards the more dense (solid) phase
Increase T  System tends towards the more entropic (liquid) phase
dP
If (vl  v s )  Slope  0
dT
Increase P at constant T  System tends towards the more liquid phase
The Clapeyron-Clausius approximation:

RT
v  v g  vl  v g ; assume ideal gas  v g 
P
dP P
From Clapeyron equation   2
l
dT RT
96
3-3
3-3.4 1st 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.
RT a
P  2 van der Waals E.O.S.
(v  b) v
 P 
Stability criteria:  T  0 or   0
 V T
Not all curves conform to the stability criteria. Clearly, portion FKM of T1
curve violates the stability criterion.
Setting constant P will get one solution T in the T9 curve, and three
solutions O, K and D in the T1 curve. But only O and D have physical
meaning because K violates the stability criterion.
97
3-3
The given P-v isotherms may be used to compute the molar Gibbs free
energy to better perceive the stability criterion.
d    sdT  vdP or    v ( P )dP   (T )
 (T ) is an undetermined function of the T
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).

O
v( P )dP  0
D 98
3-3
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.
In general, for P < PD, the right-hand branch (ABCD) of the isotherm in
right figure is physically significant, whereas for P > PD the left-hand
branch (SRQD) is physically significant. The intermedium region is
physically unstable.
99
3-3
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.
x g  xl  1 ; x g v g  xl v l  v z
v g  vz
xl 
v g  vl
v z  vl
xg 
v g  vl
100
3-3
The entropy change during the phase transition can be computed using the
following relation along hypothetical isotherm OMKFD.
 s 
ds    dv
 v T
 P   s   P 
s     dv  v    T  the Maxwell relation
OMKFD 
T  v  T  v
The total change in the molar energy:

u  T s  Pv
Limitation: Can’t apply near critical point. 101
3-3
3-3.5 Summary of stability criteria
U=U(x1, x2, …) or U=U(P1, P2, …) 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
x1, … , xs-1 subspace and below its tangent hyper-planes in the Ps, … , Pt
subspace.
102
3-3
3-3.6 1st phase transitions in multi-component system
For a multi-component system the fundamental relation:

U = U(S, V, N1 ,N2, … ,Nr)
or the molar form:
u = u(s, v, x1, x2, … , xr－1)
At the equilibrium stable the “energy” , i.e., the enthalpy and the
Helmholtz and Gibbs potentials are “convex functions” of the mole
fraction x1, x2, … , xr－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.
103
3-3
Gibbs phase rule

Gibbs phase rule is the thermodynamic degrees of freedom (f).
f   2  M ( r  1)  r ( M  1)  r  M  2
variations equations
r : No. of components
M : No. of phases
f : No. of intensive parameters capable of independent variations
 2  M ( r  1): P , T  each phase have (r - 1) variations  No. of phases ( M )

 1I  1II  ...  1M 
 
r ( M  1):  
 rI   rII  ...   rM 
 
104
3-3
Application of the Gibbs phase rule

Example:
I. Single-component system (r＝1)
a: M＝2 → f＝1 → at a given T, another variable 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, x1 (or x2) 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
105
3-3
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 P1 < P2 < P3 < P4.
The C state in the two-

phase state is composed
of A and B, and only A
and B are physical point.
106
3-3
Example:
Typical phase diagram for a binary Phase diagram for a binary system
system. in equilibrium with its vapor phase.
(P is not constant)
107
3-4
Thermodynamic States near Critical
3-4
Points
3-4.1 Features in the vicinity of the critical point
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.
108
3-4
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.” 109
3-4
The generalized susceptibilities, such as cp, κT and α diverge.

Example:
1  v 
T  
v  P T
 v 
 P    at first phase transition or near critical point
 T
  T diverges;  and c p diverge in a similar way.
110
3-4
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.
111
3-4
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.
112
3-H
3-H Homework
Problem 9.1-1
Problem 9.3-3
Problem 9.4-11
Problem 9.7-1
113
Chapter 4 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
114
4-1
4-1 The general ideal gas
4-1.1 The essence of ideal gas behavior

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, N1, …) is additive (Gibbs’s theorem)
1 1
4.  T  ,   , c p  cv  R have the same value for all ideal gas
P T
115
4-1
The F , U and S of general multicomponent ideal gas:

F (T , V )   U j (T )  T  S j (T , V )  U  TS
j j
U j  N j u j (T )  N j u j 0  N j  cvj (T )dT 
T
T0
T0 : arbitrarily chosen standard temperature
1  v N 
S   N j s j0   N j  c (T  )dT    N j R ln 
T
T0 T  vj  
j j j  v0 N j  (see also Eq. (3.40)
T 1 v
 N c v (T  )dT   NR ln  NR  x j ln x j
T0 T  v0 j
entropy of mixing
(at the same temperature and particle density) 116
4-1
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
Step-like cv versus T curves.
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
117
4-1
4-1.2 Chemical reactions in ideal gases
Partial molar Gibbs poential:  j  RT  j (T )  ln P  ln x j 
Since  v j  j  0 at chemical equilibrium
j
  v j ln x j    v j ln P   v j ln  j (T ) The only temperature-

j j j dependent term
Let K (T ), equilibrium constant, be defined by ln K (T )    v j ln  j (T )

j
 j (T ) can in principle be known, so that K (T ) can be considered as known.

For given T & P together with x
j
j  1 each of x j can be determined.
 The mass action law:  x j j  P  j j K (T )

v v
118
4-1
Logarithmic additivity of K(T)



reaction1: 0  v (1)
 j j A ; reaction2: 0 


(2)
 j Aj
v

 v (3)
If 0 
 j A j can be obtained by summing the previous reaction,

 v (3)
that is, 0 
 j A j   ( B v
1 j
(1)
 B v (2)
2 j )A j ; B1 & B2 are constant
Then it can be shown that:

Can help tabulations of K(T)
ln K 3 (T )  B1 ln K 1 (T )  B2 ln K 2 (T )
for various chemical reactions.
The reaction heat can also be computed from K (T ) as

dH d
 RT 2 ln K (T ) (the van't Hoff relation)
dN dT
(see an example in page 295 of the textbook.)
119
4-2
Small Deviations from Ideality—The Virial
4-2
Expansion
4-2.1 Virial expansion

P R B(T ) C (T ) 
 1  2  
T v v v 
Ideal behavior Correction

term for v
B(T ): "Second virial coefficient" which accounts for the contribution from
two-body interactions.
C (T ): "Third virial coefficient" which accounts for the contribution from
three-body interactions etc.
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. 120
4-2
4-2.2 Other thermodynamic quantities may be
expanded in a self-consistent fashion
 B(T ) C (T ) D(T )  (f is the molar Helmholtz potential)

f  f ideal  RT        
 v 2v 2 3v 2 
f
(from P   )
v
 1 d 2 ( BT ) 1 d 2 (CT ) 1 d 2 ( DT ) 
cv  cv ,ideal  RT  2
 2 2
 2 2
 
 v dT 2v dT 3v dT 
 s  f
(from cv  T   ; s )
 T  v T
 1 dB 1 dC 1 dD 
u  uideal  RT 2   2  2  
 v dT 2v dT 3v dT 
(from u  f  Ts )
121
4-2
The second virial coefficient vanishes at some special temperatures for

several simple gases.
122
4-3
4-3 Law of Corresponding States for Gases
4-3.1 Important observations for gases

In the equation of state of a given fluid, there is one unique point－the
critical point—characterized by Tcr, Pcr, and vcr.
The dimensionless constant Pcr vcr/R Tcr 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)
123
4-3
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 /vcr, P/Pcr, and T/Tcr. 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

Pv  P  v   T 
Z or Z  0.27     
RT  cr   cr   cr 
P v T
as functions of P/Pcr, and T/Tcr.
124
4-3
Tr curve
125
4-3
The Lennard-Jones potential
1
Attractive force 
r6
1
Repulsive force  12
r
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/r6 and has arisen
from the instaneous dipole moment fluctuations.
126
4-4
Applications to Dilute Solutions—the van’t
4-4
Hoff Relation and the Raoult’s law
4-4.1 the van’t Hoff relation for osmotic pressure

Consider a single-component fluid system, the Gibbs potential of the dilute solution
can be written in the general form:
N1
G (T , P , N 1 , N 2 )  N 1 10 ( P , T )  N 2 ( P , T )  N 1 RT ln
N1  N 2
N2
 N 2 RT ln
N1  N 2
 represents the effect of the interaction energy between the two types of molecules,
while the last two terms accounts for the entropy of mixing
N1 N N1
In dilute region (N 2  N 1 )  ln  2 , N 1 ln   N2
N1  N 2 N1 N1  N 2
N2
 G (T , P , N 1 , N 2 )  N 1 10 ( P , T )  N 2 ( P , T )  N 2 RT  N 2 RT ln
N 1 127
4-4
Solvent and solute partial molar Gibbs potentials:

G
1 ( P , T , x )   10 ( P , T )  xRT
N 1
G N
2 ( P , T , x )    ( P , T )  RT ln x ; ( x  2 )
N 2 N1
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:
1 ( P , T , 0)  1 ( P , T , x )
P : The pressure on the solute side of the membrane
128
4-4
1 ( P , T , 0)  1 ( P , T , 0)  xRT
Expanding 1 ( P , T , 0) around the pressure P

1 ( P , T , 0)
1 ( P , T , 0)  1 ( P , T , 0)   (P  P )
P
 1 ( P , T , 0)  ( P   P )v
( P   P )v  xRT
Multiplying by N 1
the van’t Hoff relation for osmotic
 V P  N 2 RT
pressure in dilute solutions
129
4-4
4-4.2 Application to vapor pressure
The vapor pressure reduced by addition of low concentration of nonvolatile solute:
 liq ( P , T )   gas ( P , T )
  liq ( P , T )  xRT   gas ( P , T )
Expanding  liq ( P , T ) and  gas ( P , T ) around the pressure P

 liq ( P , T )   liq ( P , T )  v liq  ( P   P )
 gas ( P , T )   gas ( P , T )  v gas  ( P   P )
xRT
P  P  
v g  vl
RT
v g  vl ; (the ideal gas equation: v g  )
P
P
  x Raoult’s law
P
130
4-H
4-H Homework
Problem 13.2-2
Problem 13.5-2
Problem 13.5-3
131
Chapter 5 Statistic Ensembles and Formulism
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)
132
5-1
The Entropy Representation—the
5-1
Boltzmann’s law
5-1.1 Physical significance of entropy for closed system
Classical Thermodynamics
Erected on a basis of few hypotheses of entropy.

e.g. S=S(U, V, N) ; extremum principle
Statistical Thermodynamics
Statistical mechanics provides the physical interpretation of the

entropy and a heuristic justification for the extremum principle.
133
5-1
Atomic systems Macroscopic systems
Closed system
Quantum mechanics
given V & N
If the system is macroscopic, there
may exist many discrete quantum U, V, and N are the
states consistent with the specified only constraints on
values of U, V, and N. the system.
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.
134
5-1
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.
135
5-1
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.
136
5-1
Entropy (S ) No. of microstates ( )

additive (extensive) Multiplicative
6 6
＋？
＝ ×
6 6
S  kB ln 
The constant prefactor merely determines the scale of S, and agrees with
Boltzmann’s constant kB ＝R/NA=1.3807 × 10-23 J/K.
Nevertheless, the microcanonical formulation establishes the clear and

basic logical foundation of statistical mechanics.
137
5-1
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 N atoms in the crystal are free to vibrate

around its equilibrium position in any of three coordinate
directions, and can be replaced by 3N harmonic oscillators,
all with the same natural frequency 0 .
Einstein introduced the energy of harmonic oscillators discretely:

 =n 0 ; n  0, 1, 2, ...
 h / 2 ; h: Planck's constant
Discrete values of energy: n 0
138
5-1
If the energy of the system is U it

can be considered as constituting
U  0 quanta. Theres quanta are
to be distributed among 3 N
vibrational modes.
Number of permutations of
(3 N  1  U 0 )
H 3N
C 

3 N  U 0 1
3 N  U   1 !
0
U 0 U 0
 3 N  1 !  U   !
0
 
 3 N  U   1 !  3 N  U   !
0

0
( N  )
 3 N  1 !  U   !  3 N  !  U   !
0 0
139
5-1
 u u  u
s  3 R ln  1    3 R ln  1   ; u0  3 N A 0
 u0  u0  u0 
From S  k B ln  & ln( M !)  M ln M  M     (if M  1)
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.
1 S k  3N 
Thermal equation of state:   B ln  1  N A 0 
T U 0  U 
 There are 3 NN A oscillator in the system
U 0
 mean energy per oscillator   0 k BT
3 NN A e 1
The quantity  0 k B is called the "Einstein temperature" of the crystal,
and it generally is of the same order of magnitude as the melt point of the solid.
140
5-1
cv approaches a
constant value (3R)
at high temperature.
cv 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 cv rises exponentially, whereas experimentally the heat
capacity rises approximately as T 3.
141
5-1
5-1.2 The two-state system ; a polymer model
Two-state system
Total atoms N
U : system energy
(N - U ) atoms are Ground state Excited state U

  atoms are in
in the ground state (with energy 0) (with energy ε) the excited state
N!
   CUN  
U   ! N  U  !
U   U  U U
 S    N  k B ln  1    ln
   N   N
From S  k B ln  & ln( M !)  M ln M  M     (if M  1)
142
5-1
1 S k B  N  
Thermal equation of state:   ln   1
T U   U 
N
U  ; ( U  N )
1  e  k BT
2 e  k BT 2
e 
du 2
 2 k BT   2 k BT
c  NA  NA e
 
2
dT k BT 2 1  e  2 k B T k BT 2
The energy approaches N  2 as the temperature approaches infinity in

this model.
At infinite temperature half the atoms are excited and half are in their
ground state.
143
5-1
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.
144
5-1
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.
145
5-1
N x  N x  N y  N y  N N x 
1
2
 N  U   L 
x
Lx
N x  N x   Lx
a

Nx 
1
2
 N  U   L 
x
Ly
 Ly
 U   L 
 
Ny  Ny  N y 
1
a 2 y
U
N y  N y   U 
 N y 
1
2
 U   L 
y
The number of configurations of the polymer

consistent with given corrdinates Lx and Ly
of its terminus and given energy U :
N!
(U , Lx , Ly , N ) 
N x ! N x ! N y ! N y !
146
5-1
S  k B ln   Nk B ln N  N x k B ln N x  N x k B ln N x
 N y k B ln N y  N y k B ln N y
or
1 
1
S  Nk B ln N 
2
  
N  U   Lx k B ln  N  U   Lx 
2 

1 
1
2
   
 N  U  Lx k B ln  N  U   Lx 
2



1 
1
2
 
U   Ly k B ln  U   Ly 

2 
 
1 
1
 
 U   Ly k B ln  U   Ly 
2 2 
 
Ty S k B U   Ly
   ln  0 ; (  y  0)
T Ly 2a U   Ly
Ly
 Ly  Ly  N y  N y   Ly & a  0  Ly  Ly  0  N y  N y
a 147
5-1
TxS k B N  U   Lx
   ln
T Lx 2a N  U   Lx
N  U   Lx
 2 Tx a k B T
e 
N  U   L
1 S k B
 
T U 2

ln N  Lx  U  
kB
2
 
ln N  Lx  U 
kB


ln U   
 
2
N U  Lx 2
 e 2 k BT

U2
Lx sinh  Tx a k BT 

N cosh  Tx a k BT   e  k BT
2
1 Tx Na
For small Tx a (relative to k BT )  Lx   
k BT 1  e   k BT
 The modulus of elasticity of the rubber band:

1  Lx  a2
 
1

    1  e k BT
N  Tx T k BT
148
5-2
5-2 The Canonical Formalism
5-2.1 The probability distribution

Limitation of microcanonical formalism:
The microcanonical formalism is simple in principle, but it is computationally
feasible only for a few highly idealized models.
Isolated Must calculate the no. of combinatorial ways that a given total
system energy can be distributed in arbitrarily sized boxes.
Generally beyond our mathematical capabilities!
Canonical formalism (Helmholtz representation)
T reservoir Remove the limitation on the amount of energy available

－to consider a system in contact with T reservoir rather
system than an isolated system.
149
5-2
Canonical formalism
Closed system
T reservoir
Closed system ＝ Subsystem ＋ T reservoir
subsystem
(note that the energy of the subsystem fluctuates)
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.
150
5-2
A Simple analogy
Sum of no. =12 Record red dice no.

thrown
Sum of no. 12 What fraction of these recorded

throws has the red die shown a
one, a two,…, a six ?
Sum is12 corresponds to

2/25
given total energy
3/25
Reservoir
The numbers shown 4/25 Each state does
correspond to the not have the same
energy of the system 5/25 probability.
subsystem 6/25
5/25
151
5-2
Probability of subsystem
The probability f j of the subsystem in state j:
fj 

 res Etot  E j  ; E j : the energy in state j
 tot  Etot 
 fj 
 
exp k B1 S res Etot  E j 
;  from S  k B ln  

exp k Stot  Etot 
1
B 
If U is the average value of the subsystem
 Stot  Etot   S  U   S res  Etot  U 
 
Expanding S res Etot  E j around the equilibrium point Etot  U :
U  Ej
   
 S res Etot  E j  S res Etot  U  U  E j  S res  E tot  U  
T
1 k BT U TS ( U )   1 k RT  E j
 f j  e e
152
5-2
1 k BT U TS ( U )   1 k RT  E j
f j  e e
1  Ej
define    f j  e F e
k BT
e  F is state-independent normalization factor
  f j  e  F e  e F  e
 Ej  Ej
1
j j j
define Z   e
 Ej
 e F  Z
j
Fundamental relation in the canonical formalism:

  F  ln  e
 Ej
 ln Z
j
The probability of occupation of the j -th state:


 Ej   Ei
fj  e e
i
153
5-2
The average energy:

U   E j f j   E je e
 Ej   Ei
j j i
or
 d   F 
U    ln Z ; U  F T   &   F  ln Z
 d   T 
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.”
154
5-2
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.
155
5-2
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:
   ε  ε   ε    ε i j : the energy of the i -th element
Z   e 1j 2j 3j
j , j  , j  , ... in its j -th orbitial state

  ε1 j   ε 2 j   ε 3 j
 e e e 
j , j  , j  , ...
 e e e
  ε1 j   ε 2 j   ε 3 j
   z1z 2 z 3   
j j j 
zi   e
  εi j
; z i : the "partition sum of the i -th element"
j
The Helmholtz potential :

  F  ln Z  ln z1  ln z 2    
The energy is additive over elements, and each element is permitted to
occupy and its orbital states independently.
156
5-2
Applied to two- state model:
   
N N
ε ε
Zz  e e
N 0
 1 e Total atoms Ñ
1
  F  ln  e
 Ej
 ln Z & 
j k BT
 
N
ε
 F   Nk BT ln 1  e Ground state Excited state
(with energy 0) (with energy ε)
If the number of orbitals had been three rather than two, the partition sum
per particle z would merely have contained three terms.
z  e
ε j
 e   ε1  e   ε2  e   ε3
j
157
5-2
Applied to the Einstein model:

Einstein introduced the energy of harmonic oscillators discretely:
 1
 = 0  n   ; n  0, 1, 2, ...
 2
 h / 2 ; h: Planck's constant
The "elements" are the vibrational modes.
1 3 5 7
  0   0   0   0
ze 2
e 2
e 2
e 2
 
1
1  e 
  0
  0
e 2
 e 2  0
 e 3  0
 
1
  0
2 
e 1
z   xn  1  x  x2      xn     (1  x  1)
1  e 0
1  x n 0
F    1 ln z 3 N
3
  0 Nk BT  3 Nk BT ln 1  e   0
2
 
158
5-2
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).
Neglect interactions
Consider monatomic classical ideal gas:
between gas molecules
T reservoir
The energy is the sum of one-particle
“kinetic energies,” and the partition
No. of atoms
sum factors.
Ñ(＝NNA)
Container
volume V
159
5-2
The one-particle translational partition sum ztransl:
k  p ; p: generalized momentum
H( x , y , z , p x , p y , pz ): Hamiltonian function
 dq j dp j 
Z   e   1 2 1 2   z transl  z internal
H
j
h h 
1       p 2x  p 2y  pz2  2 m
 z transl  3  dxdydz    dp x dp y dpz e
h   
1     p2 2 m    p2
 3  dxdydz  e   p 2x 2 m
dp x  e y
dp y  e z 2m
dpz
h   
V
V  
 3 2 mk BT  
32
e  ax =
2
( )
h - a
160
5-2
V

32
z transl   
h3  B 
2 mk T
If one identifies Z as z N and thereby

Finding F is not extensive!
calculates F .
To identify Z as zÑ 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!.
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.
161
5-2
The partition sum for a classical monatomic ideal gas:

Z= 1 N! N
z transl
 V  2 mk BT  3 2 
 F   k BT ln Z   Nk BT ln      Nk BT
 N   
2
h
F 5 3   U 3 2V 
S
T
 Nk B   ln 3
2 2
 2

m   Nk B ln  5 2 
  N 
Thermodynamic context for monatomic ideal gases:

 U  3 2  V   N  5 2 
S  Ns0  NR ln      
 U 0   V0   N 0  
The constant s0, undetermined in classic thermodynamic context, has now

been evaluated in terms of fundamental constants.
162
5-2
Orbital model
Reflection on the problem of counting states reveals that division by Ñ! is a
rather crude classical attempt to account for indistinguishability.
Classical counting Fermi particles Bose particles

1
2
1
2
1 2
2 1
“Corrected” number
of states = 4．1/2!
163
5-2
Classical counting Fermi particles Bose particles
1
2
1
2
1 2
“Corrected” number
2 1
of states = 4．1/2!
“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”.
164
5-2
The Equipartition Theorem
Suppose the energy (Hamiltonian) to be of the form
E  Aq  Bp
2 2
Then, the classical partition function yields
  k BT    kBT 
1/ 2 1/ 2
dq dp

  ( Aq  Bp )
2 2
z~ e ~   
h  hA   hB 
The significance is that, at sufficiently high temperature when the classical density of
1
states is applicable, every quadratic term in the energy contributes a term Nk
2 B
to the heat capacity. This is the "equipartition theorem" of classical statistical mechanics.
Exp. A heteronuclear diatomic molecule has three translational modes,
one vibrational mode (with both kinetic and potential energy), two 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
3 2 2 7 7
k B  k B  k B  k B ( or R per mole).
2 2 2 2 2 165
5-3
5-3 Generalized Canonical Formulations
5-3.1 Entropy as a measure of disorder

Information Theory
Define the information I in terms of the probability fj, subject to the
following requirements:
Information is a non-negative quantity, I(fj) ≧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(f1 × f2) ＝ I(f1) ＋ I(f2).
I(fj) is monotonic and continuous in fj.
166
5-3
Four properties can thus be derived:

 1 
 
I f j  log b     log b f j
 fj   
 
b: the positive constant b was used in different units
e.g.
log 2 units are bits (from "binary")
log 3 units are trits (from "trinary")
log e units are nats (from "natural logarithm")
log10 units are Hartleys
Define the disorder (entropy) of the porbability distribution f ,f ,

1 2 
, f j is
n  1 
H  f j log b  
 fj 
j 1  
167
5-3
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 ﹛fj﹜.
The maximum disorder corresponds to all event have equal possibility.
Example:
Given sample space S and it's possibility distribution:
S   s1 , s2 , s3 , s4  ; possibility distribution  f1 , f 2 , f 3 , f 4 
Situation I:
f1  f 2  f 3  f 4  1 / 4 Have max.
1 1 1 1 disorder
H P  log 2 4  log 2 4  log 2 4  log 2 4  2 bits
4 4 4 4
Situation II:
f1  1 / 2, f 2  1 / 4, f 3  f 4  1 / 8
1 1 1 1
H P  log 2 2  log 2 4  log 2 8  log 2 8  1.75 bits
2 4 8 8 168
5-3
At max.
f  1- f  1/ 2
1 1
H  log 2 2  log 2 2  1 bits
2 2
Entropy in the case of two possibilities

with probabilities f and (1－f).
C. E. Shannon, J. Bell Syst. Tech. 27, 379-423 (1948).
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.
169
5-3
From the definition of disorder (entropy):

n  1  n
H   f j log b     k  f j ln f j
 fj 
j 1   j 1
If the system is isolated, it spends equal time in each of the permissible states.
1
fj  ; j  1, 2,

1 1 1 
H   k  f j ln f j   k  ln    k    ln    k ln 
j 1 j 1    
 H  k ln 
Microcanonical formalism: S  k B ln 
 k  kB
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.
170
5-3
If the system is in contact with a thermal reservoir, the probability of j-th sate is
 Ej
e
fj  ; j  1, 2,
Z
H   k B  f j ln f j   k B  f j ln e
j 1 j 1
  Ej
 
Z  k B  f j  E j  ln Z
j 1

 H  k B   f j E j  k B ln Z S  k B   f j E j  k B ln Z
j 1 j 1
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.
171
5-3
5-3.2 The grand canonical formalism
Closed system
T & μ reservoir Closed system ＝ Subsystem ＋ T reservoir

Consider a system of fixed V in contact with both energy and
subsystem
particle reservoirs, and given energy Ej and mole number Nj.
Probability of a state of the system:
fj 

 res Etot  E j , N tot  N j 
 tot  Etot , N tot 
 fj 
 
exp k B1 S res Etot  E j , N tot  N j 
;  from S  kB ln  

exp k Stot  Etot , N tot 
1
B 

Expanding S res Etot  E j , N tot  N j  & S E
tot tot , N tot 

 U TS   N    E j   N j 
 fj  e e
172
5-3

 U TS   N    E j   N j 
fj  e e
defined  =U  TS   N  U T ,   ;  is the "grand canonical potential"

 E j N j 
 f j  e  e
e  is state-independent normalizing factor
  E j N j     E j  N j 
  f j   e  e  e   e 1
j j j
 
define Z   e
 E j N j
; Z : the grand canonical partition sum
j
 e    Z
     ln Z
The conventional view is that Ψ(T, V, μ) is the Legendre transform of U,

or Ψ(T, V, μ) ＝ U[T, μ].
173
5-3
Mnemonic figure
F  U T 
Useful relationships :
     lnZ 
1 U   
Multiplied
kB     
174
5-3
To corroborate the grand canonical formalism from maximizing the disorder

(entropy):
 S   kB   ln f j  1  f j  0
Taking differentials
S   k B  f j ln f j
j 1 j 1
Auxiliary conditions: Auxiliary conditions:

f j 1 1   f j  0
j 1 j 1
fE j j E 2  E j f j  0
j 1 j 1
Taking differentials &
f j Nj  N multiplying by Lagrange 3
multiplier λ1, λ2, λ3.
N  f 0
j 1
j
j 1
175
5-3
 S   kB   ln f j  1  f j  0
j 1
Auxiliary conditions: Adding 4

equations
1   f j  0
j 1
  ln f
j 1
j  1  1  2 E j  3 N j  0 
2  E j f j  0 If this equation is always to hold true,
j 1
each term must be equal to zero.
3  N j f  0
j 1  ln f j  1  1  2 E j  3 N j  0

 1 1  2 E j  3 N j 
 fj  e

 1 1  2 E j  3 N j 
fj  e
1  1   
2  
Compare the two

  E j  N j   3  
f j  e  e equations to identify λ1, λ2,
& λ3.
176
5-3
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.
There are Ñ such sites, and each site can adsorb zero, one,
or two molecules.
T & μ reservoir  the site is empty  0 
 
Solid surface Each site has an energy: singly occupied   1 
 doubly occupied   
(system)  2
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.
177
5-3
The surface sites do not interact, the grand partition sum:
Z  zN
 
z = e
 E j N j   1       2  2     1       2  2  
 e0  e e  1 e e
j
The mean number of molecules adsorbed per site is

  E j N j 
    E j   N j 
e Nj
n   fjN j  e e Nj   e    z
j j j z
   0  0   1       2  2  
0e 1 e 2e
  
z z z
  1   
 2e  2 
   2
e
n
z
The mean energy per site is
   1e     1  
  2e
   2  2  
   fjEj  e e    E j   N j
Ej  
j j z
178
5-3
An alternative route to these two results, and to the general thermodynamics

of the system, is via calculation of the grand canonical potential:
   k BT ln Z .

   k BT ln Z =  k BT ln z N   k BT ln 1  e
  1   
e
   2  2  

The number Nˆ of adsorbed atoms on the N sites:
    
ˆ
N  Nn    ;  T is constant 
    
   
Uˆ  N   

179
Density of States
" sum "    ...  e

 Ej
The quantity in the parenthesis is unity

 " sum "    1 e
 Ej
Z
j
The quantity in the parenthesis is the energy ,and the "sum" divided by Z
" sum "   Ej 
   E j e   Z U
Z  j 
Under the circumstance that   E j 1  E j   1 ,the sum can be replaced
by integral.

" sum " ≈  Emin
 ...  e   E j
D  E  dE Density of state
180
Example: Problem 16.10-4
Consider a particle of mass m in a cubic container of volume V.
2
2
Show that  E ≈ 2mV 2 3
h
Momentum : P  k k
2
Just consider the kinetic energy
Planck constant : h  2
p2 Substitute P for k 
Wave factor : k   1 3   n1 , n2 , n3 
 Ej 
2m V 

 
2
k2 2 2
n1  0,1, 2, ...
  n 2
 n 2
 n 2
2m 2mV 2 3 1 2 3
n2  0,1, 2, ...
n3  0,1, 2, ...
2
 2
 E  E j  1  E j ≈
2mV 2 3
181
Example: Problem 16.10-4
Show that the partition sum can be approximated well by an
integral under certain temperature criterion.
Under the circumstance that   E j 1  E j   1 ,the sum can be replaced

by integral.
 ztransl   e
 Ej 
D  E  dE
 Ej
j
≈  Emin
e

 
2 2
1
  E j 1  E j   E   2 3
 1
kbT 2mV
2
2
 T 
2kb mV 2 3
182
5-H
5-H Homework
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 16.10-4 183

Statistical Fluctuations and Solution
Chapter 6 Strategies
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)
184
6-1
6-1 Fluctuations
6-1.1 The probability distribution of fluctuations

T reservoir The subsystem and the reservoir together undergo
incessant and rapid transitions among their joint
subsystem microstates.
The subsystem energy thereby fluctuates around its equilibrium value
The “subsystem” may, in fact, be a small portion

reservoir of a larger system, the remainder of the system
then constituting the “reservoir.”
subsystem In that case the fluctuations are local fluctuations
within a nominally homogeneous system.
185
6-1
The statistical mechanical form of the probability distribution for a fluctuating
extensive parameter is familiar.
Case I:
The probability that the system occupies a particular
T reservoir
microstate of energy Eˆ :
ˆ
subsystem f  e F  E
Case II:
The probability that the system occupies a particular
T, P reservoir
microstate of energy Eˆ and volume Vˆ :
subsystem f e

 G   Eˆ  PVˆ 
186
6-1
Generally, for a system in contact with reservoirs corresponding to the

extensive parameters X 0 , X 1 , , X s , the probability that the system
occupies a particular microstate with parameters Xˆ , Xˆ , , Xˆ : 0 1 s
f Xˆ =e
 k 1
B S
 F0 , 
, Fs  k B1 F0 Xˆ 0  F1 Xˆ 1 , , Fs Xˆ s 
0, Xˆ 1 , , Xˆ s
S  F0 , , Fs : the Massueu function

F0 , , Fs : the entropic intensive parameters
e.g.
F 1  1  G 1 P
  S    S ,    S , 
T T  T T T  T T T 
1 1  1 P
F0  F0  ; F1  F0  ; F1 
T T T T T
Xˆ 0  Eˆ Xˆ 0  Eˆ ; Xˆ 1   Nˆ Xˆ 0  Eˆ ; Xˆ 1  Vˆ
 f  e F  E
ˆ
 f e

   Eˆ   Nˆ   f e

 G   Eˆ  PVˆ 
187
6-1
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.
 Eˆ  U  : the deviations
Eˆ  U ; Eˆ  U  0
 
2
Eˆ  U : the mean-square deviation (the second central moment)
    Ej U   fj   Ej U    
2 2 2  FEj
Eˆ  U e
j j
  FEj    
       F   U 
2
 Eˆ  U Ej U e 
j    
   U
   FEj
 Ej U e 
 j 
188
6-1
 U
    
 F Ej 
2
Eˆ  U  Ej U e 
 j 
 
 E  
  Ej U fj   E U
 F Ej
j U e 0
j j
U U
 
2
 Eˆ  U     k BT 2 Ncv A very useful expression to estimate
   1 k BT  the heat capability of a system in
computer simulations.
The mean square energy fluctuations are proportional to the size of the
system.
The relative root-mean-square dispersion  Ê  U 
2 12
U , 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.
189
6-1
Higher-order moments of the energy fluctuations:

  F Ej 
   
n1
  E j  U
n
Eˆ  U e
j 
     
 E   e  
n  FEj  FEj n
 U e Ej U
 j
j
j 
   U
 
n 1
E U  n e
n  F Ej
 Ej U
 j 
 U
E U E U
n n 1
 n
 
2  cv 
  
3
Eˆ  U  Nk T  2Tcv  T
2 2
T 
e.g. the third moment: B

The higher-order moments of the energy fluctuations can be generated

from the lower-order moments by the recursion relation.
190
6-1
For a system in which both E and V fluctuates:
 U 
 
2
Eˆ   kB  
  (1 / T )  P / T , N1 ,...
 kBT 2 Nc p  kBT 2 PV   kBTP 2V  T
 V 
 
2
Eˆ Vˆ   kB  
  (1 / T )  P / T , N1 ,...
 kBT 2V   kBTPV  T
 V 
 
2
Vˆ   kB  
  ( P / T ) 1/ T , N1 ,...
 kBT V  T
The energy and the volume fluctuations are correlated, as expected.

191
6-2
6-2 Quantum Fluids
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
Fermions Bosons
Fermions are the quantum Bosons are the quantum
analogues of the material analogues of the “waves” of
particles of classical physics. classical physics.
e.g. electrons, protons, and e.g. photons (quanta of light)
neutrons 192
6-2
(From Astro-group, department of physics of Hong Kong university)
193
6-2
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:
n , n  1, 3, 5, (odd multiples)
2
1 1
Spin quantum number m s : (  ),  (  )
2 2
194
6-2
Consider a pre-gas model system in which only three spatial orbits are permitted;
particles in these spatial orbits have energies ε1, ε2, and ε3. The model system is
in contact with a T reservoir and a μ reservoir.
T & μ reservoir There are therefore six orbital states:

1 1
( n, ms ) ; n  1, 2, 3 ; m s   , 
subsystem 2 2
The Grand canonical partition sum factors:

Z  z1, 1 2 z1, 1 2 z 2, 1 2 z 2, 1 2 z 3, 1 2 z 3, 1 2
   n   N n     n       n   
z n , ms   e
n ,ms
 e 0
 e  1  e
e n  e n 
     
1
f n ,ms      n   
     
z n , ms 1 e e n 1
195
6-2
Pair the two orbital states with the same n but with ms  1:
 1  e  n    1  2e  n   e  n 
2
        2    
z n, 1 2 z n, 1 2
 
2e  n 
    2    n   
1 e
empty 2 singly occupied double occupied
The fundamental equation:

  1       2       3   
2 2 2
e  
 Z  1  e  1  e  1  e 
     
196
6-2

N

or N f
n, m
n, m
2 2 2
N f
n, m
n, m 
e
 1   
1

e
  2   
1

e  3  1
  
   
U  
   
or U 
n, m
n, m f n, m
2 1 2 2 2 3
U 
n, m
n, m f n, m 
e
 1   
1

e
  2   
1

e  3  1
  
  
By the same way,  S   determines the entropy.
 T 
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.
197
6-2
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. 3He.
The partition sum of orbital state k , ms :

z k , ms   e
   k   Nk 
k , ms
 e 0
 e
   k   
 1  e
   k   
 The partition sum factors: Z   z k , ms

k , ms
e k 
  
1
The probability of occupation: fk , ms       
z k , ms e k 1
198
6-2
The grand canonical potential:
   k BT  lnZ   k BT  ln 1  e
   k   
2

k k
 
The energy of an occuppied orbital state k , m s :
p2 2 2
k
 k , ms   , k: wave vector (can refer to eq. 16.43 in textbook)
2m 2m
The density of orbital states: (see Chap. 16)
32
V 2 dk V  2m 
D    d  d   1 2d 
4 2  2 
k
2 2
d

   2k BT  ln 1  e    D    d 
   
0
32
V  2m  
ln 1  e 
 
 1 2 d 

 
  k BT
2 2  2  0  
      
which can be utilized to determine U and N .  U    ;N  
       
  
199
6-2
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 fermions:
n , n  0, 2, 4, (even multiples)
2
200
6-2
Ideal Bose fluids

The partition sum of a single orbital state is independent of m s , and is, for
each value of m s ,
z k  z k , ms  e 0  e  k   e  k   e  k  
     2  2    3  3 
1  1 
n

1 e
  k   
; 
 1  x
 
n 0
x 

The probability of occupation with various occupated no. i in orbital state k, m s is
e  k 
  i  i 
f k , ms , i 
z k , ms
The average number of bonsons in the orbital state k , m s :
nk , ms   i  f k , ms ,i   e  k   e  k   e  k    zk , m
     2  2    3  3 
i
  s

 k BT
ln z k , ms
 201
6-2
 e  k 
   
nk , ms  k BT


ln z k , ms   k BT


ln 1  e 
   k   

  k BT
1 e  k 
   
1
     
e k 1
1 occupation probability (or
 nk , ms  fk , ms       
e k 1 mean occupation number)

     ln 1  e    D    d 
   
0
32
32
2 V  2m  

3  2  2  2  
0
e
 k   
1
d   which determines U and N .
The quantity fk , ms is not necessarily less than unity, and therefore is more
properly identified as a “mean occupation number” .nk , ms
If μ were positive the orbital state with εk equal to μ would have an
infinite occupation number! So, the molar Gibbs potential μ is always
negative.
202
6-2
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.
1
The probability of occupancy: f k , ms       
e 1
If fugacity e   1 ;  classical regime 
 The occupation probability reduces to
     
f k , ms  e  e    e The Boltzmann distribution
 The number of particles N reduces to
32
 g V  2m   g0V 
N   0 2 2  e   e    1 2 d   e
  2    0 λT3
h
λT  ; λ T : the thermal wave length
2 mk BT
203
6-2
 The energy reduces to

      2V  2m 
32
 3 g0V 
U   2  2 
e  e  d   k BT 3 e
   3 2
N
     2    2 λT
0
3 The equation of state of

U  Nk BT
2 classical ideal gas
The criterion that divides the quantum and classical regimes:

 gV 
e   1 or λ T3  0   1  classical-quantum boundary 
 N 
The classical limit the fugacity is the ratio of the “thermal
volume” λ3T to the volume per particleV/(Ñ/g0).
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 λT).
204
6-2
6-2.3 Example of Fermi fluid: electrons in a metal
At T＝0 K, to calculate the number of particles: T  0K
 2m  for   0
32
2m 3 2V 0 V 1
f T ,    
 2 3 0
N  d 
12
 32
3 2 3 0
0 for   0
The number of conduction electrons per unit volume in metals is of the order
of the order of 1022 to 1023 electrons cm 3 , the Fermi temperature  TF  is
0
TF   104 K to 105 K
kB
Metal TF (K) Metal TF (K)

Li 5.5×104 Cs 1.8×104
Na 3.7×104 Cu 8.2×104
K 2.4×104 Ag 6.4×104
Rb 2.1×104 Au 6.4×104
205
6-2
All reasonable temperatures μ>> kBT, the electrons in a metal are an

example of an ideal Fermi gas in the strong quantum regime.
The heat capacity:

  2 k BT 
3
C  Nk B  O T 
3
2  3 0 
The prefactor 3ÑkBT/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.
206
6-2
6-2.4 Bose condensation
The number of particles N e :
1 2
32
g V  2m  
Ne  0 2  2 
 2    
0 1 
 e 1
d
Fugacity   e  , and 0    1
Expand the integral of equation of N e in powers of the fugacity:
 g V  2m  3 2   g0V
 k BT   λ 3 F3 2   
32
Ne   0
2  2 

  2     2 T
h
λT  ; λ T : the thermal wave length
2 mk BT

r 2 3
F3 2      32
   
r 1 r 2 2 3 3
207
6-2
The energy:
32
32
g0V  2m  
U
 2 
2 

2 


0 1 
 e 1
d
Expand the integral of equation of U in powers of the fugacity:

 2V  2m  3 2  3  3 g0V
     F5 2   
52
U 2  2 
 k T F  k T
  2  
B 52 B
  4 2 λT3

r 2 3
F5 2      52
   
r 1 r 4 2 9 3
g0V g0V Ne
Ne  F     
λ T3 3 2 λ T3 F3 2   
3 F5 2   
 U  N e k BT
2 F3 2   
The ratio F5 2   F3 2   measures the deviation from the classical

equation of state.
208
6-2
At   1
F5 2  1.34
F3 2  2.612
At   0
slope of F5 2  1
slope of F3 2  1
The two functions F5 2    and F3 2    satisfy the relation:

d 1
F     F3 2   
d 5 2 
209
6-2
g0V
If  2.612, to first evaluate the temperature at which the failure of the
N e T
3
"integral analysis" occurs.

gV
 Set 0 3  2.612
N e T
h
λT 
2 mk BT
23
2  1 2
N 
 k BTc   
m  2.612 g0V 
Tc : the Bose condensation temperature

Example of Bose condensation of 4He
For temperature greater than Tc the “integral analysis” is valid. At and

below Tc a “Bose condensation” occurs, associated with anomalous
population of the orbital ground state.
210
6-2
211
6-2
ρs(T): superfluid density of 4He

ρn(T): normal fluid density of 4He
Below Tc 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 4He.
212

Advanced Thermodynamics

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Advanced Thermodynamics

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Advanced Thermodynamics

Instructor: Prof. Chi-Chung Hua

Molecular Rheology LAB

Textbook: Herbert B. Callen, 1985, “Thermodynamics and

Grading: Homework (20 %)

Teaching assistants: 易函柳 (Rm414, Ext. 23482 )

Part two: Statistic Thermodynamics

1-1.1 Thermodynamic coordinates

Macroscopic vs. Microscopic

Experimental variables Experimental results

A1: 1. Use minimum number of measurable variables.

Q2: Select macroscopic or microscopic variables?

A2: The basis of selection is the scale of the phenomena or substances of

Microscopic 1μm Macroscopic

But macroscopic properties cannot spread to microscopic properties

We usually used macroscopic properties to describe engineering

System has no external influences (such as flow, electrical fields).

All thermodynamic properties must be “time invariance” (time

Scale limitation: Length scale must be greater than ca.10nm.

Time invariance: All variables and properties must be time

The system may then be V1 V2

S ＝ S（U , V , N） thermodynamic constraints

thermodynamic constraints thermodynamic constraints

Others equilibrium conditions can be derived with fixed V

1-3.1 Extensive parameters & intensive parameters

S , U , V , N : First order extensive parameters

At first, people didn’t know the meanings of T, P and μ. Later, they

If the overall system has reached an equili-

U  U(S, V , N ) Energy representation

The fundamental equations describe homogeneous first-order parameters.

T  T(S, V , N ) Equations of state:

P  P( S , V , N ) An intensive parameter is expressed in

Knowledge of a single equation of state does not constitute complete

Figure 1.2 U vs. S & U vs. T in constant V & N

U & S are first order parameters

The equations of state describe homogeneous zero-order parameters.

Th Thermodynamic engine efficiency:

Used to define temperature scale.

Question: All heat can be transfer to work?

Answer: It is impossible unless Tc = 0K

Kinetic energy Work

Kinetic energy All heat transfers to

Unit of U is energy. So, unit of temperature is energy.

The temperature scale, Kelvin, was used in molecular scale.

1-4.1 The Euler relation

The Euler relation is useful for deducing many important thermodynamic

dU  TdS  SdT   PdX

Given that dU  TdS   PdX

One obtains SdT   X i dPi  0 the Gibbs-Duhem equation

The Euler relation is useful for deducing many important thermodynamic

The fundamental equation U=U(S, V, N) contains “all” thermodynamic

Equations of state + the Euler equation = The full expression of U

The totality of all equations of state can be used to reconstruct the

Problem 1.10-1: (a), (f), (g), (i)

Read Sec. 3-5 (The ideal van der Waals fluid)

2-1.1 The S max. principle & the U min. principle

An isolated system must conform with two

Entropy max. principle: Energy min. principle:

Figure 2.1 The equilibrium state A as a point of max. S for constant

S max. principle: The equilibrium value of any unconstrained internal parameter

Can withdraw energy The system would be restored to its

Entropy maximum principle:

By eqn. A.22 of Appendix A