Supplement

Statistical Thermodynamics


Contents
1. Introduction
2. Distribution of Molecular States
3. Interacting Systems Gibbs Ensemble
4. Classical Statistical Mechanics
1. Introduction
Mechanics : Study of position, velocity, force and
energy
Classical Mechanics (Molecular Mechanics)
Molecules (or molecular segments) are treated as rigid object
(point, sphere, cube,...)
Newtons law of motion
Quantum Mechanics
Molecules are composed of electrons, nuclei, ...
Schrodingers equation Wave function
1. Introduction
Methodology of Thermodynamics and Statistical Mechanics
Thermodynamics
study of the relationships between macroscopic properties
Volume, pressure, compressibility,
Statistical Mechanics (Statistical Thermodynamics)
how the various macroscopic properties arise as a consequence of the microscopic nature of
the system
Position and momenta of individual molecules (mechanical variables)
Statistical Thermodynamics (or Statistical Mechanics) is a link between microscopic
properties and bulk (macroscopic) properties

Methods of QM
Methods of MM
A particular
microscopic model
can be used
r
U
P T V
Statistical
Mechanics
Pure mechanical variables
Thermodynamic Variables
1.Introduction
Equilibrium Macroscopic Properties
Properties are consequence of average of individual
molecules
Properties are invariant with time Time average
Mechanical
Properties of
Individual
Molecules
position, velocity
energy, ...
Thermodynamic
Properties
temperature, pressure
internal energy, enthalpy,...
average
over molecules
average
over time
statistical
thermodynamics
2 3 4
1. Introduction
Description of States
Macrostates : T, P, V, (fewer variables)
Microstates : position, momentum of each particles (~10
23
variables)
Fundamental methodology of statistical mechanics
Probabilistic approach : statistical average
Most probable value
Is it reasonable ?
As N approaches very large number, then fluctuations are negligible
Central Limit Theorem (from statistics)
Deviation ~1/N
0.5

2. Distribution of Molecular States
Statistical Distribution
n : number of occurrences
b : a property
b
n
i

1 2 3 4 5 6
if we know distribution
we can calculate the average
value of the property b
2. Distribution of Molecular States
Normalized Distribution Function
Probability Distribution Function
b
P
i

b
1
b
5
b
4
b
3
b
2
b
6

=
= =
i
i i
i
i i
i i i i
i i
b P
b n
b n
n
b n
b P
1 ) (
) (
) ( ) (
) (

>= <
>= <
i
i i
i
i i
P b F b F
P b b
) ( ) (
Finding probability (distribution) function is
the main task in statistical thermodynamics
2. Distribution of Molecular States
Quantum theory says ,
Each molecules can have only discrete values of energies
Evidence
Black-body radiation
Planck distribution
Heat capacities
Atomic and molecular spectra
Wave-Particle duality

Energy
Levels
2. Distribution of Molecular States
Configuration ....
At any instance, there may be n
o
molecules at c
0
, n
1

molecules at c
1
, n
2
molecules at c
2
,
{n
0
, n
1
, n
2
} configuration

c
0
c
2
c
1
c
3
c
4
c
5
{ 3,2,2,1,0,0}
2. Distribution of Molecular States
Weight ....
Each configurations can be achieved in different ways

Example1 : {3,0} configuration 1



Example2 : {2,1} configuration 3

c
0
c
1
c
0
c
1
c
0
c
1
c
0
c
1
2. Distribution of Molecular States
Calculation of Weight ....
Weight (W) : number of ways that a configuration can be achieved in
different ways
General formula for the weight of {n
0
, n
1
, n
2
} configuration
[
= =
i
i
n
N
n n n
N
W
!
!
!... ! !
!
3 2 1
Example1
{1,0,3,5,10,1} of 20 objects
W = 9.31E8
Example 2
{0,1,5,0,8,0,3,2,1} of 20 objects
W = 4.19 E10
Principles of Equal a Priori Probability
All distributions of energy are equally probable
If E = 5 and N = 5 then

0

1

2

3

4

5

0

1

2

3

4

5

0

1

2

3

4

5

All configurations have equal probability, but
possible number of way (weight) is different.
A Dominating Configuration
For large number of molecules and large number of energy
levels, there is a dominating configuration.
The weight of the dominating configuration is much more
larger than the other configurations.

Configurations
W
i

{n
i
}
Dominating Configuration
0

1

2

3

4

5

0

1

2

3

4

5

0

1

2

3

4

5

W = 1 (5!/5!) W = 20 (5!/3!) W = 5 (5!/4!)
Difference in W becomes larger when N is increased !
In molecular systems (N~10
23
) considering the
most dominant configuration is enough for average
How to find most dominant
configuration ?
The Boltzmann Distribution
Task : Find the dominant configuration for given N and
total energy E
Method : Find maximum value of W which satisfies,

=
=
i
i i
i
i
n E
n N
c
0
0
=
=

i
i i
i
i
dn
dn
c
Stirling's approximation
A useful formula when dealing with factorials of
large numbers.

N N N N = ln ! ln
i
i
i
i
i i
i
i
i
i
n n N N
n n n N N N
n N
n n n
N
W

=
+ =
= =
ln ln
ln ln
! ln ! ln
!... ! !
!
ln ln
3 2 1
Method of Undetermined
Multipliers
Maximum weight , W
Recall the method to find min, max of a function




Method of undetermined multiplier :
Constraints should be multiplied by a constant and
added to the main variation equation.

0
ln
0 ln
=
|
|
.
|

\
|
c
=
i
dn
W
W d
Method of Undetermined
Multipliers
0
ln
ln
ln
=
)
`

+
|
|
.
|

\
|
c
=
+
|
|
.
|

\
|
c
=

i
i i
i
i
i i
i
i
i
i
i
dn
dn
W
dn dn dn
dn
W
W d
|c o
c | o
0
ln
= +
|
|
.
|

\
|
c
i
i
dn
W
|c o
undetermined multipliers
Method of Undetermined
Multipliers

c
c

c
c
=
|
|
.
|

\
|
c
c
=
j
i
j j
i i
i i
n
n n
n
N N
n
W
n n N N W
) ln (
ln ln
ln ln ln
1 ln
1
ln
ln
+ =
|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=
c
c
N
n
N
N
N N
n
N
n
N N
i i i

+ =

|
|
.
|

\
|
c
c
+
|
|
.
|

\
|
c
c
=
c
c
j
i
i
j
j
j j
i
j
j
i
j j
n
n
n
n
n n
n
n
n
n n
1 ln
1
ln
) ln (
N
n
N n
n
W
i
i
i
ln ) 1 (ln ) 1 (ln
ln
= + + + =
c
c
Method of Undetermined
Multipliers
0 ln = + +
i
i
N
n
|c o
i
e
N
n
i
|c o
=

=
= =
j
j j
j
j
j
e
e
e Ne n N
|c
o
|c
o
1

= =
j
i
i
j
i
e
e
N
n
P
|c
|c
Boltzmann Distribution
(Probability function for
energy distribution)
Normalization Condition
The Molecular Partition Function
Boltzmann Distribution


Molecular Partition Function


Degeneracies : Same energy value but different states (g
j
-
fold degenerate)

q
e
e
e
N
n
p
i
j
i
j
i
i
|c
|c
|c

= = =

=
j
j
e q
|c

=
j
levels
j
j
e g q
|c
How to obtain the value of beta ?
Assumption :

T 0 then q 1

T infinity then q infinity

The molecular partition function gives an indication of the
average number of states that are thermally accessible to a
molecule at T.

kT / 1 = |
2. Interacting Systems
Gibbs Ensemble
Solution to Schrodinger equation (Eigen-value problem)
Wave function
Allowed energy levels : E
n

Using the molecular partition function, we can calculate
average values of property at given QUANTUM STATE.

Quantum states are changing so rapidly that the observed
dynamic properties are actually time average over
quantum states.

+ = + + + V
i
i
i
E U
m
h
2
2
2
8t
Fluctuation with Time
time
states
Although we know most probable distribution of energies of individual
molecules at given N and E (previous section molecular partition
function) it is almost impossible to get time average for interacting
molecules
Thermodynamic Properties
Entire set of possible quantum states




Thermodynamic internal energy

,... ,... , ,
1 1 1 i
+ + + +
,... ,..., , ,
3 2 1 i
E E E E

A =

i
i i
t E U
t
t
1
lim
Difficulties
Fluctuations are very small
Fluctuations occur too rapidly

We have to use alternative, abstract approach.

Ensemble average method (proposed by Gibbs)

Alternative Procedure
Canonical Ensemble
Proposed by J. W. Gibbs (1839-1903)
Alternative procedure to obtain average
Ensemble : Infinite number of mental replica
of system of interest

Large reservoir (constant T)
All the ensemble members have the same (n, V, T)
Energy can be exchanged but
particles cannot
Number of Systems : N
N
Two Postulate
E
1
E
2
E
3
E
4
E
5
time
Fist Postulate
The long time average of a mechanical variable M is
equal to the ensemble average in the limit N
Second Postulate (Ergodic Hypothesis)
The systems of ensemble are distributed uniformly for (n,V,T) system
Single isolated system spend equal amount of time
Averaging Method
Probability of observing particular quantum state i


Ensemble average of a dynamic property


Time average and ensemble average

=
i
i
i
i
n
n
P
~
~
i
i
i
P E E

>= <
i
i
i
n
i i
P E t E U


= A = lim lim
t
How to find Most Probable
Distribution ?
Calculation of Probability in an Ensemble
Weight



Most probable distribution = configuration with maximum weight

Task : find the dominating configuration for given N and E
Find maximum O which satisfies

[
= = O
i
i
n
N
n n n
N
!
~
!
~
!...
~
!
~
!
~
!
~
3 2 1

=
=
i
i i t
i
i
n E E
n N
~
~
~
0
~
0
~
=
=

i
i i
i
i
n d E
n d
Canonical Partition Function
Similar method (Section 2) can be used to get most
probable distribution

= =
j
E
E
i
i
j
i
e
e
N
n
P
|
|
Q
e
e
e
N
n
P
i
j
i
E
j
E
E
i
i
|
|
|

= = =

=
j
E
j
e Q
|
Canonical Partition Function
How to obtain beta ?
Another interpretation
rev
i
i i
i
i
i
i i
i
i i
i
rev
N
i
i
i
i i
dq TdS dP P dP Q dP P dP E
w PdV dV
V
E
P dE P
= = = + =
= =
|
.
|

\
|
c
c
=


ln
1
) ln ln (
1
| |
o

+ = =
i
i i
i i
i i i i
dE P dP E P E d dU ) (
pdV TdS w q dU
rev rev
= = o o
The only function that links heat (path integral) and
state property is TEMPERATURE.
kT / 1 = |
Properties from Canonical Partition
Function
Internal Energy
V N V N
qs i
E
i
V N
qs i
E
i i
i
i
Q Q
Q
U
e E
Q
e E
Q
P E E U
i
i
, ,
) (
,
) (
ln 1
1
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
=
|
|
.
|

\
|
c
c
== >= =<

| |
|
|
|
Properties from Canonical Partition
Function
Pressure
N
i
i
i i i N i
i i N i
V
E
P
w dV P dx F dE
dx F dV P w
|
.
|

\
|
c
c
=
= = =
= =
o
o
) (
) (
dx
dV
i
F
V
i
dE
i
E
Small Adiabatic expansion of system
|
.
|

\
|
c
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
= =
>= =<

V
Q
P
e
V
E
Q V
Q
e
V
E
Q
e P
Q
P
P P P
i
E
N
i
N
i
E
N
i
i
E
i
i
i
i
i i
ln
ln 1
ln
1 1
P
,
i
|
|
|
|
| |
Thermodynamic Properties from
Canonical Partition Function
i j
N V T
i
i
N T
N T N V
N V
N V
N
Q
kT
V
Q
Q kT G
Q kT A
V
Q
T
Q
kT H
T
Q
Q k S
T
Q
kT U
=
|
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
=
|
.
|

\
|
c
c
+
c
c
=
|
.
|

\
|
c
c
+ =
c
c
=
, ,
,
, ,
,
,
ln
)
ln
ln
( ln
ln
)
ln
ln
( )
ln
ln
(
)
ln
ln
( ln
)
ln
ln
(

Grand Canonical Ensemble

Ensemble approach for open system
Useful for open systems and mixtures
Walls are replaced by permeable walls
Large reservoir (constant T )
All the ensemble members have the same (V, T,
i
)
Energy and particles can be exchanged
Number of Systems : N
N
Grand Canonical Ensemble
Similar approach as Canonical Ensemble
We cannot use second postulate because systems are not isolated
After equilibrium is reached, we place walls around ensemble and treat
each members the same method used in canonical ensemble

After
equilibrium
T,V,
T,V,N
1
T,V,N
2
T,V,N
3
T,V,N
4
T,V,N
5
Each members are (T,V,N) systems
Apply canonical ensemble methods for each member
Grand Canonical Ensemble
Weight and Constraint
[
(

= O
N j
j
N j
j
N n
N n
,
,
)! (
! ) (

=
=
=
N j
j t
N j
j j t
N j
j
N N n N
N V E N n E
N n
,
,
,
) (
) , ( ) (
) ( N
Number of ensemble members
Number of molecules after
fixed wall has been placed
Method of undetermined multiplier
with o, | ,
N
V N E
j
e e e N n
j
|
o

=
) , (
*
) ( N

= = =
N j
N
V N E
N
V N E
j j
j
e e
e e
N n N n
N P
j
j
,
) , (
) , ( *
) ( ) (
) (

|

|
N N
Grand Canonical Ensemble
Determination of Undetermined Multipliers

= =
N j
j j
V N E N P E U
,
) , ( ) (

+ =
N j
j j
N j
j j
V N dE N P N dP V N E dU
, ,
) , ( ) ( ) ( ) , (
| |

c
c
+ + + =
N j
j
j
N j
j j
dV
V
V N E
N P N dP N P N dU
, ,
) , (
) ( ) ( ln ) ( ln
1

=
N j
N
V N E
e e
j
,
) , (

|
dN pdV TdS dU =
Comparing two equation gives,
kT

=
kT
1
= |

=
N j
kT N
kT V N E
e e
j
,
/
/ ) , (

Grand Canonical Partition Function
4. Classical Statistical Mechanics
The formalism of statistical mechanics relies very much at the
microscopic states.
Number of states , sum over states
convenient for the framework of quantum mechanics
What about Classical Sates ?
Classical states
We know position and velocity of all particles in the system
Comparison between Quantum Mechanics and Classical Mechanics

E H =
QM Problem Finding probability and discrete energy states
ma F = CM Problem
Finding position and momentum of individual molecules
Newtons Law of Motion
Three formulations for Newtons second law of motion
Newtonian formulation
Lagrangian formulation
Hamiltonian formulation

i
i
i
i i
t
m t
F
p
p r
=
c
c
=
c
c

=
=
=
=
=
i j
j
ij i
z y x
z y x
p p p
r r r
1
) , , (
) , , (
F F
p p
r r
) ,..., , (
2
) , (
energy) al PE(potenti energy) KE(kinetic ) , (
2 1 N
i
i
i N N
N N
U
m
H
H
r r r
p
p r
p r

+ =
+ =
i
i
i
i
H
H
r
p
p
r

=
(

c
c
=
(

c
c
Classical Statistical Mechanics
Instead of taking replica of systems, use abstract phase space
composed of momentum space and position space (total 6N-space)
N
p
N
r
1
t
2
t
1
I
2
I
{ }
N N
r r r r p p p p ,..., , , , ,..., , ,
3 1 1 3 2 1
= I
Phase space
Classical Statistical Mechanics
Classical State : defines a cell in the space (small volume of
momentum and positions)

Ensemble Average
simplicity for State" Classical "
3 3
r pd d dr dr dr dq dq dq
z y x z y x
=
I I I = I =
} }

d E d E U
N
n
) ( ) ( lim ) (
1
lim
0
P
t
t
t
t
I I d
N
) ( P
Fraction of Ensemble members in this range
(I to I+dI)
} }
I
I
= I I
d kT H
d kT H
d
N
) / exp( ...
) / exp(
) ( P
Using similar technique used for
Boltzmann distribution
Classical Statistical Mechanics
Canonical Partition Function
} }
I = d kT H ) / exp( ... T
Phase Integral
} }
I = d kT H c ) / exp( ... Q
Canonical Partition Function
} }

=

d kT H
kT E
i
i
T
) / exp( ...
) / exp(
lim c
Match between Quantum
and Classical Mechanics
NF
h N!
1
= c
For rigorous derivation see Hill, Chap.6 (Statistical Thermodynamics)
Classical Statistical Mechanics
Canonical Partition Function in Classical Mechanics
} }
I = d kT
h N
NF
) / exp( ...
!
1
H Q
Example ) Translational Motion for
Ideal Gas

=
+ =
+ =
N
i i
i
N
i i
i N N
N N
m
p
H
U
m
H
H
3
2
2 1
2
) ,..., , (
2
) , (
energy) al PE(potenti energy) KE(kinetic ) , (
r r r
p
p r
p r
N
N
N
V
N
i
N
i
N N
i
i
N
V
h
mkT
N
dr dr dr dp
m
p
h N
dr dr dp dp
m
p
h N
Q
2 / 3
2
0
3 2 1
3
3
1 1
2
3
2
!
1
)
2
exp(
!
1
... ... )
2
exp( ...
!
1
(

=
(

=
=
} }
} }

t
No potential energy, 3 dimensional
space.
We will get ideal gas law
pV=nRT
Semi-Classical Partition Function
The energy of a molecule is distributed in different modes
Vibration, Rotation (Internal : depends only on T)
Translation (External : depends on T and V)
Assumption 1 : Partition Function (thus energy distribution) can be separated
into two parts (internal + center of mass motion)

) , ( ) , , (
) exp( ) exp( ) exp(
int
int int
T N Q T V N Q Q
kT
E
kT
E
kT
E E
Q
CM
i
CM
i i
CM
i
=
=
+
=

Semi-Classical Partition Function
Internal parts are density independent and most of the
components have the same value with ideal gases.



For solids and polymeric molecules, this assumption is not
valid any more.



) , 0 , ( ) , , (
int int
T N Q T N Q =
Semi-Classical Partition Function
Assumption 2 : for T>50 K , classical approximation can be
used for translational motion
N
N
i
N N iz iy ix
N
N
i
iz iy ix
CM
dr dr dr kT U Z
mkT
h
Z
N
dr kT U dp
mkT
p p p
h N
Q
r r r U
m
p p p
H
3 2 1
2 / 1
2
3
3 3
2 2 2
3
3 2 1
2 2 2
... ) / ( ...
2
!
) / ( ... )
2
exp( ...
!
1
) ,..., , (
2
} }
} }

} }

=
|
|
.
|

\
|
= A
A
=

+ +
=
+
+ +
=

t
Z Q
N
Q
N 3
int
!
1

A =
Configurational Integral
Another, Different Treatment
Statistical Thermodynamics:
the basics
Nature is quantum-mechanical
Consequence:
Systems have discrete quantum states.
For finite closed systems, the number of
states is finite (but usually very large)
Hypothesis: In a closed system, every
state is equally likely to be observed.
Consequence: ALL of equilibrium
Statistical Mechanics and
Thermodynamics

Basic assumption
Each individual
microstate is
equally probable
, but there are not
many microstates that
give these extreme
results
If the number of
particles is large (>10)
these functions are
sharply peaked
Does the basis assumption lead to something
that is consistent with classical
thermodynamics?
1
E
Systems 1 and 2 are weakly coupled
such that they can exchange energy.

What will be E
1
?
( ) ( ) ( )
1 1 1 1 2 1
, E E E E E E O =O O
BA: each configuration is equally probable; but the number of
states that give an energy E
1
is not know.
2 1
E E E =
( ) ( ) ( )
1 1 1 1 2 1
, E E E E E E O =O O
( ) ( ) ( )
1 1 1 1 2 1
ln , ln ln E E E E E E O = O + O
( )
1 1
1 1
1
,
ln ,
0
N V
E E E
E
| | c O
=
|
c
\ .

clnO
1
E
1
( )
cE
1
|
\

|
.
|
N
1
,V
1
+
clnO
2
E E
1
( )
cE
1
|
\

|
.
|
N
2
,V
2
= 0
( ) ( )
1 1 2 2
1 1 2 1
1 2
, ,
ln ln
N V N V
E E E
E E
| | | | c O c O
=
| |
c c
\ . \ .
Energy is conserved!
dE
1
=-dE
2

This can be seen as an
equilibrium condition
( )
,
ln
N V
E
E
|
| | c O

|
c
\ .
1 2
| | =
Conjecture:
Almost right.
Good features:
Extensivity
Third law of thermodynamics comes for free
Bad feature:
It assumes that entropy is dimensionless but (for
unfortunate, historical reasons, it is not)

Entropy and number of
configurations
ln S = O
We have to live with the past, therefore
With k
B
= 1.380662 10
-23
J/K
In thermodynamics, the absolute (Kelvin)
temperature scale was defined such that
But we found (defined):
( )
ln
B
S k E = O
,
1
N V
S
E T
c
| |
=
|
c
\ .
( )
,
ln
N V
E
E
|
| | c O

|
c
\ .
dE = TdS-pdV +
i
dN
i
i =1
n

And this gives the statistical definition of temperature:

In short:
Entropy and temperature are both related to
the fact that we can COUNT states.
( )
,
ln
1
B
N V
E
k
T E
| | c O

|
c
\ .
Basic assumption:
1. leads to an equilibrium condition: equal temperatures
2. leads to a maximum of entropy
3. leads to the third law of thermodynamics
How large is O?
For macroscopic systems, super-astronomically large.
For instance, for a glass of water at room temperature:



Macroscopic deviations from the second law of
thermodynamics are not forbidden, but they are
extremely unlikely.



Number of configurations
25
2 10
10

O ~
Canonical ensemble
Consider a small system that can exchange heat with a big reservoir
i
E
i
E E
( ) ( )
ln
ln ln
i i
E E E E
E
c O
O = O +
c
( )
( )
ln
i
i
B
E E
E
E k T
O
=
O
1/k
B
T
Hence, the probability to find E
i
:
( )
( )
( )
( )
( )
exp
exp
i i B
i
j j B
j j
E E E k T
P E
E E E k T
O
= =
O

( ) ( )
exp
i i B
P E E k T
Boltzmann distribution
Example: ideal gas
( )
( )
3
1
, , d exp
!
N N
N
Q N V T U r
N
|
(
=

A
}
r
3 3
1
d 1
! !
N
N
N N
V
N N
= =
A A
}
r
Free energy:
3
3 3
ln
!
ln ln ln ln
N
N
V
F
N
N
N N N N
V
|

| |
=
|
A
\ .
| |
~ A + = A +
|
\ .
Pressure:
T
F N
P
V V |
c
| |
= =
|
c
\ .
Energy:
3 3
2
B
F N
E Nk T
|
| |
| | c cA
= = =
|
c A c
\ .
Thermo recall (3)
Helmholtz Free energy:
T
F
P
V
c
| |
=
|
c
\ .
d d d F S T p V =
1
F T F
E
T
|
|
| | | | c c
= =
| |
c c
\ . \ .
Energy:
Pressure
Ensembles
Micro-canonical ensemble: E,V,N
Canonical ensemble: T,V,N
Constant pressure ensemble: T,P,N
Grand-canonical ensemble: T,V,
Basic assumption
Each individual
microstate is
equally probable
, but there are not
many microstates that
give these extreme
results
If the number of
particles is large (>10)
these functions are
sharply peaked
Does the basis assumption lead to something
that is consistent with classical
thermodynamics?
1
E
Systems 1 and 2 are weakly coupled
such that they can exchange energy.

What will be E
1
?
( ) ( ) ( )
1 1 1 1 2 1
, E E E E E E O =O O
BA: each configuration is equally probable; but the number of
states that give an energy E
1
is not know.
2 1
E E E =
( ) ( ) ( )
1 1 1 1 2 1
, E E E E E E O =O O
( ) ( ) ( )
1 1 1 1 2 1
ln , ln ln E E E E E E O = O + O
( )
1 1
1 1
1
,
ln ,
0
N V
E E E
E
| | c O
=
|
c
\ .

clnO
1
E
1
( )
cE
1
|
\

|
.
|
N
1
,V
1
+
clnO
2
E E
1
( )
cE
1
|
\

|
.
|
N
2
,V
2
= 0
( ) ( )
1 1 2 2
1 1 2 1
1 2
, ,
ln ln
N V N V
E E E
E E
| | | | c O c O
=
| |
c c
\ . \ .
Energy is conserved!
dE
1
=-dE
2

This can be seen as an
equilibrium condition
( )
,
ln
N V
E
E
|
| | c O

|
c
\ .
1 2
| | =
Conjecture:
Almost right.
Good features:
Extensivity
Third law of thermodynamics comes for free
Bad feature:
It assumes that entropy is dimensionless but (for
unfortunate, historical reasons, it is not)

Entropy and number of
configurations
ln S = O
We have to live with the past, therefore
With k
B
= 1.380662 10
-23
J/K
In thermodynamics, the absolute (Kelvin)
temperature scale was defined such that
But we found (defined):
( )
ln
B
S k E = O
,
1
N V
S
E T
c
| |
=
|
c
\ .
( )
,
ln
N V
E
E
|
| | c O

|
c
\ .
dE = TdS-pdV +
i
dN
i
i =1
n

And this gives the statistical definition of temperature:

In short:
Entropy and temperature are both related to
the fact that we can COUNT states.
( )
,
ln
1
B
N V
E
k
T E
| | c O

|
c
\ .
Basic assumption:
1. leads to an equilibrium condition: equal temperatures
2. leads to a maximum of entropy
3. leads to the third law of thermodynamics
How large is O?
For macroscopic systems, super-astronomically large.
For instance, for a glass of water at room temperature:



Macroscopic deviations from the second law of
thermodynamics are not forbidden, but they are
extremely unlikely.



Number of configurations
25
2 10
10

O ~
Canonical ensemble
Consider a small system that can exchange heat with a big reservoir
i
E
i
E E
( ) ( )
ln
ln ln
i i
E E E E
E
c O
O = O +
c
( )
( )
ln
i
i
B
E E
E
E k T
O
=
O
1/k
B
T
Hence, the probability to find E
i
:
( )
( )
( )
( )
( )
exp
exp
i i B
i
j j B
j j
E E E k T
P E
E E E k T
O
= =
O

( ) ( )
exp
i i B
P E E k T
Boltzmann distribution
Example: ideal gas
( )
( )
3
1
, , d exp
!
N N
N
Q N V T U r
N
|
(
=

A
}
r
3 3
1
d 1
! !
N
N
N N
V
N N
= =
A A
}
r
Free energy:
3
3 3
ln
!
ln ln ln ln
N
N
V
F
N
N
N N N N
V
|

| |
=
|
A
\ .
| |
~ A + = A +
|
\ .
Pressure:
T
F N
P
V V |
c
| |
= =
|
c
\ .
Energy:
3 3
2
B
F N
E Nk T
|
| |
| | c cA
= = =
|
c A c
\ .
Thermo recall (3)
Helmholtz Free energy:
T
F
P
V
c
| |
=
|
c
\ .
d d d F S T p V =
1
F T F
E
T
|
|
| | | | c c
= =
| |
c c
\ . \ .
Energy:
Pressure
Ensembles
Micro-canonical ensemble: E,V,N
Canonical ensemble: T,V,N
Constant pressure ensemble: T,P,N
Grand-canonical ensemble: T,V,