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Molecular Rheology LAB
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
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1-1
Thermodynamic Equilibrium and
1-1
Postulate I
Variables Responses
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1-1
Q1: How to select variables of an experimental or simulation
system?
length scale
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1-1
Microscopic properties can spread to macroscopic properties
Microscopic Macroscopic
When all properties have reached time independence in our selected time
scale, the system would seem to reach an equilibrium. Yet, since different
people may have different opinions of time scale, the viewpoint of equili-
brium could also be different.
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Molecular Rheology LAB
1-1
1-1.3 Limitations of thermodynamic equilibrium
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.
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Molecular Rheology LAB
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
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Molecular Rheology LAB
1-2
U1 U 2 U1' U 2'
S = S(U) only U1' ?
By entropy
U ?
'
2 max.
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Molecular Rheology LAB
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
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1-2
Fixed V & U Fixed U & N
V1 V2 V1 V2
U1 U2 U1 U2
N1 N2 N1 N2
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1-3
Intensive Parameters and Equations of
1-3
State
Example: S (9U , 9V , 9N ) 9 S (U , V , N )
Enlarged 9 times S S S
S S S S
S S S 15
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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
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:
Fundamental equations
S S (U , V , N ) Entropy representation
Two equations are alternative forms of the fundamental relation, and each
contains all thermodynamic information about the system.
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1-3
Equations of state
U U S ,V , N
U U U
S T ; V P ; N
N , V N , S S, V
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1-3
Zero order
(U ) (U )
0T
( S ) N , V ( S ) N , V
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 )
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1-3
1-3.3 Unit of temperature
Thermodynamic engine
T1 T1
Permissible scale (e.g. K, R)
T2 T2
T1 T1 k
Non-permissible scale (e.g. oC, oF)
T2 T2 k
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1-3
Rotation
Tc ≠ 0K Internal energy
Heat Molecular Vibration
Rotation
Tc = 0K Internal energy = 0
Heat Molecular Vibration
Unit of temperature
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.
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
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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
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1-4
The Euler Equation and the Gibbs-Duhem
1-4
Relation
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
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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
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1-4
1-4.2 The Gibbs-Duhem equation
Euler relation: U ( S , V , N 1 , N 2 , ...) TS Pi X i
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.
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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
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1-4
1-4.3 Summary of formal structure
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1-H
1-H Homework
Problem 2.2-1
Problem 3.3-2
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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
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2-1
2-1 Legendre Transformations
Fundamental
surface
Physical argument
Assume: The system is in equilibrium but the energy does not have its
smallest possible value consistent with the given entropy.
The original equilibrium state must have had min. energy consistent with
the prescribed entropy. The inverse argument is the same.
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2-1
Mathematical exercise
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
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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
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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.
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2-1
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 )
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2-1
Elimination of Y and X 0 , X 1 , k
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2-2
The Legendre Transformed Functions
2-2
and Thermodynamic Potentials
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 )
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2-2
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 n1 , 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
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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 n1 , 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
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2-2
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 n1 , 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
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2-2
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2-3
2-3 Minimum Principles for the Potentials
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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
(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
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2-3
H H (S, P, N ) G G (T , P , N )
dH 0 dG 0
d 2H 0 d 2G 0
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2-3
The subsystem:
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
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2-3
Similarly, one can prove the Enthalpy minimum principle H(S, P, N) for
systems in contact with a pressure reservoir, as well as the Gibbs potential
minimum principle G(T, P, N) for systems in contact with both a heat and
pressure reservoir.
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2-4
Applications of various Legendre
2-4
Transformed Potentials
See Example.1 in page 159, which shows that one can increases the
entropy of a subsystem without changing the associated internal energy.
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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
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.
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2-4
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.
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2-4
2-4.3 The Gibbs potential
by defition: G U TS VP
the Euler relation: U TS VP i N i
i
r
Consider the chemical reaction: 0 j A j
1
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
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2-5
2-5 Maxwell Relations and Some Applications
U U(S, V , N )
Constant N
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2-5
Table 2.1. Maxwell relations for several potentials with various pairs of
independent variables. (see also pp. 182 & 183 of the textbook)
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2-5
Mnemonic diagram
Understanding U G Generate
S H P
Solutions Hard Problems
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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
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2-5
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
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2-5
2-5.2 Procedure for the reduction of 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
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2-5
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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
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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
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
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2-5
2-5.3 Some simple applications
I. Adiabatic compression
Adiabatic wall Adiabatic wall
Quasi-static process
Ti Tf =?
Pi Pf
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
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2-5
Quasi-static process dS ?
Pi Pf dU ?
Constant T Q ?
Pi 73
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2-5
III. Free expansion
Adiabatic wall Adiabatic wall
Gas Gas
Vacuum
Vi ; Ti Constant U Vf ; Tf =?
Equations of state:
Fundamental equation
T f Ti T (U , V f , N ) T (U , Vi , N )
T P T
dT dV dV
V U , N NcV NcV T
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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
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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
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3-1
Stability Conditions for Thermodynamic
3-1
Potentials
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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)
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3-1
2S
2
0 For U 0
U V , 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.
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3-1
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
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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 )
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
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3-1
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
Example:
Incident
photon
Container
Fluid Fluid
T1 T1
T1 T1’
The curvature of the potential well then plays a crucial and continual role,
restoring the system toward the “expected state” after each Brownian
impact (fluctuation).
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3-2
3-2.3 The Le Chatelier-Braun principle
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.
T&P
reservoirs 87
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3-2
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
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3-3
First-order Phase Transitions in Single-
3-3
Component Systems
• 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.
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3-3
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3-3
3-3.3 The Clapyron equation
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3-3
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.
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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
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3-3
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.
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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
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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
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3-3
3-3.6 1st phase transitions in multi-component system
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.
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3-3
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3-3
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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.
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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)
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3-4
Thermodynamic States near Critical
3-4
Points
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.
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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
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3-4
Problem 9.1-1
Problem 9.3-3
Problem 9.4-11
Problem 9.7-1
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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
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4-1
4-1 The general ideal gas
1 1
4. T , , c p cv R have the same value for all ideal gas
P T
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4-1
U j N j u j (T ) N j u j 0 N j cvj (T )dT
T
T0
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
Molecular Rheology LAB
4-1
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
Molecular Rheology LAB
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
118
Molecular Rheology LAB
4-1
v (3)
that is, 0
j A j ( B v
1 j
(1)
B v (2)
2 j )A j ; B1 & B2 are constant
121
Molecular Rheology LAB
4-2
124
Molecular Rheology LAB
4-3
Tr curve
125
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4-3
1
Attractive force
r6
1
Repulsive force 12
r
128
Molecular Rheology LAB
4-4
1 ( P , T , 0) 1 ( P , T , 0) xRT
( 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
Molecular Rheology LAB
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 )
Problem 13.2-2
Problem 13.5-2
Problem 13.5-3
131
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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
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5-1
The Entropy Representation—the
5-1
Boltzmann’s law
5-1.1 Physical significance of entropy for closed system
Classical Thermodynamics
Statistical Thermodynamics
133
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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
Molecular Rheology LAB
5-1
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.
135
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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.
136
Molecular Rheology LAB
5-1
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.
138
Molecular Rheology LAB
5-1
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
Molecular Rheology LAB
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)
cv is zero at zero
temperature.
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
143
Molecular Rheology LAB
5-1
Schottky hump
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
Molecular Rheology LAB
5-1
N x N x N y N y N N x
1
2
N U L
x
Lx
N x N x Lx
a
Nx
1
2
N U L
x
Ly
Ly
U L
Ny Ny N y
1
a 2 y
U
N y N y U
N y
1
2
U L
y
146
Molecular Rheology LAB
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 Lx k B ln N U Lx
2
1
1
2
N U Lx k B ln N U Lx
2
1
1
2
U Ly k B ln U Ly
2
1
1
U Ly k B ln U Ly
2 2
Ty S k B U Ly
ln 0 ; ( y 0)
T Ly 2a U Ly
Ly
Ly Ly N y N y Ly & a 0 Ly Ly 0 N y N y
a 147
Molecular Rheology LAB
5-1
TxS k B N U Lx
ln
T Lx 2a N U Lx
N U Lx
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 Lx 2
e 2 k BT
U2
Lx 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
N Tx T k BT
148
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5-2
5-2 The Canonical Formalism
Isolated Must calculate the no. of combinatorial ways that a given total
system energy can be distributed in arbitrarily sized boxes.
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
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5-2
A Simple analogy
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
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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 B1 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
Molecular Rheology LAB
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
153
Molecular Rheology LAB
5-2
j j i
or
d F
U ln Z ; U F T & F ln Z
d T
154
Molecular Rheology LAB
5-2
5-2.2 The partition function
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).
155
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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
N N
ε ε
Zz 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
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Molecular Rheology LAB
5-2
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
Molecular Rheology LAB
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
Molecular Rheology LAB
5-2
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
Molecular Rheology LAB
5-2
V
32
z transl
h3 B
2 mk T
161
Molecular Rheology LAB
5-2
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
Orbital model
Reflection on the problem of counting states reveals that division by Ñ! is a
rather crude classical attempt to account for indistinguishability.
1 2
2 1
“Corrected” number
of states = 4.1/2!
163
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5-2
Classical counting Fermi particles Bose particles
1
2
1
2
1 2
“Corrected” number
2 1
of states = 4.1/2!
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
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5-3
5-3 Generalized Canonical Formulations
166
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5-3
At max.
f 1- f 1/ 2
1 1
H log 2 2 log 2 2 1 bits
2 2
169
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5-3
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
Molecular Rheology LAB
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
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5-3
5-3.2 The grand canonical formalism
Closed system
fj
res Etot E j , N tot N j
tot Etot , N tot
fj
exp k B1 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
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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
Mnemonic figure
F U T
Useful relationships :
lnZ
1 U
Multiplied
kB
174
Molecular Rheology LAB
5-3
S kB ln f j 1 f j 0
Taking differentials
S k B f j ln f j
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
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Molecular Rheology LAB
5-3
S kB ln f j 1 f j 0
j 1
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
fjEj e e E j N j
Ej
j j z
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Molecular Rheology LAB
5-3
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
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Density of States
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
Molecular Rheology LAB
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
Molecular Rheology LAB
Example: Problem 16.10-4
Show that the partition sum can be approximated well by an
integral under certain temperature criterion.
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
Molecular Rheology LAB
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
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
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6-1
6-1 Fluctuations
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
Molecular Rheology LAB
6-1
f Xˆ =e
k 1
B S
F0 ,
, Fs k B1 F0 Xˆ 0 F1 Xˆ 1 , , Fs Xˆ s
0, Xˆ 1 , , Xˆ s
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 FEj
Eˆ U e
j j
FEj
F U
2
Eˆ U Ej U e
j
U
FEj
Ej U e
j
188
Molecular Rheology LAB
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
Molecular Rheology LAB
6-1
T
e.g. the third moment: B
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
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!
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
Molecular Rheology LAB
6-2
193
Molecular Rheology LAB
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.
n , n 1, 3, 5, (odd multiples)
2
1 1
Spin quantum number m s : ( ), ( )
2 2
194
Molecular Rheology LAB
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.
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
Molecular Rheology LAB
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
196
Molecular Rheology LAB
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
k , ms
e 0
e
k
1 e
k
e k
1
The probability of occupation: fk , ms
z k , ms e k 1
198
Molecular Rheology LAB
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
Molecular Rheology LAB
6-2
Bosons
Fermions as waves can be freely superposed, so an arbitrary number of bosons
can occupy a single orbital state.
n , n 0, 2, 4, (even multiples)
2
200
Molecular Rheology LAB
6-2
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
Molecular Rheology LAB
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
Molecular Rheology LAB
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
Molecular Rheology LAB
6-2
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
Molecular Rheology LAB
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
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
Molecular Rheology LAB
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
Molecular Rheology LAB
6-2
The energy:
32
32
g0V 2m
U
2
2
2
0 1
e 1
d
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
At 1
F5 2 1.34
F3 2 2.612
At 0
slope of F5 2 1
slope of F3 2 1
211
Molecular Rheology LAB
6-2
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
Molecular Rheology LAB