RnT PV =

w q U + =
T
q
T
U
C
q U
V
V
V
c
c
=
c
c
=
= A
T
q
T
H
C
pdV H pdV q U
p
p
p
c
c
=
c
c
=
+ A = + = A
T
q
T
H
C
p
p
c
c
=
c
c
=
0 0 0
S T H G A A = A
mol kJ
g G g CO G g CO G G
/ 2 . 257
)] , 0 (
2
1
) , ( [ ) , (
2
0 0
2
0 0
=
= A + A A = A
Francisco Rivadulla
Qumica-Fisica IV

Then why statistical thermodynamics ?
The velocity of every molecule in a perfect gas
2 / 1
3
|
.
|

\
|
=
M
RT
V
or the mean quadratic velocity?
|
.
|

\
|
=
M
RT
V
3 2
The link between microscopic and bulk (thermodynamic) properties of matter
Key ideas of the chapter:

1.- The Boltzmann distribution function

2.- The Partition Function
Francisco Rivadulla
Qumica-Fisica IV

Introduction to Statistical Thermodynamics
Francisco Rivadulla
Qumica-Fisica IV

Then why statistical thermodynamics ?
|
.
|

\
|
=
M
RT
V
3 2
Although the total energy of a system with a fixed number of particles is constant, E
the distribution of energy among the molecules is not known or fixed.
Although the total energy of a system with a fixed number of particles is constant, E
the distribution of energy among the molecules is not known or fixed.
We can calculate the AVERAGE population
of the different states
This is a measurement of the energy
distribution among the particles
of the system
the individual molecules in each state may
change after a collision.
BUT WE CAN CALCULATE AVERAGES,
THAT IS, DISTRIBUTIONS !
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The distribution of molecular states
Francisco Rivadulla
HYPOTHESYS: We can calculate the average population of molecules at an energy state,
at thermal equilibrium.
Assumptions:
-Interactions are negligible
- Occupation of different states are equally probable if they have the same E
N=47

{25, 12, 6, 3, 1} instantaneous configuration of the system
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The distribution of molecular states
Francisco Rivadulla
N=5

{5, 0, 0, 0}

{3, 2, 0, 0}

{2, 0, 2, 1}

There are 4 (N-1) possibilities
for the remaining balls
There are 5 (N) possibilities for the first ball
There are N! different combinations. But, if we introduce a restriction (there are n
0
at
the ground level, n
1
at the first excited level, n
2
at the second

!... ! !
!
2 1 0
n n n
N
W =
W = {5, 0, 0, 0} = 1

W = {3, 2, 0, 0} = 10

W = {2, 0, 2, 1} = 6

Weight of the configuration
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The distribution of molecular states
Francisco Rivadulla
The distribution with larger Weight will dominate over all other at a give T
How should we proceed to calculate the most probable distribution over
the available energy states?
0 =
c
c
i
n
W
But all the n
i
are not independent

=
=
i
i i
i
i
E n
N n
c
We apply the method of undetermined (Lagrange) multipliers
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The most probable distribution:
Boltzmann distribution function
Francisco Rivadulla
=
c
c

c
c

For g(x)=cte a restriction of the original function
So we can multiply them by a constant and add to the original derivative equation
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The most probable distribution:
Boltzmann distribution function
Francisco Rivadulla
=
c
c
=
(

+
c
c
=
c
c

c
c
+
c
c

| o
| o
Doing some math we can arrive to:
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The most probable distribution:
Boltzmann distribution function
Francisco Rivadulla
N
n
n
W
i
i
ln
ln
=
c
c
And at dlnW=0
The Boltzmann distribution function

=
j
Ej
E
i
e
e
N
n
i
|
|
T k
B
1
= |
The fraction of molecules occupying a state of a
given energy is absolutely determined by (temperature!!)

=
i
Ei
i
e g q
|
The molecular patition function
(g
i
is the degeneracy of a state)
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The molecular partition function
Francisco Rivadulla
The molecular partition function gives an indication of the number
of states that are thermally accessible to a molecule at the temperature
of the system

=
i
Ei
i
e g q
|
Equally spaced
Non-degenerate system
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The molecular partition function
Francisco Rivadulla
The molecular partition function gives an indication of the number
of states that are thermally accessible to a molecule at the temperature
of the system

=
i
Ei
i
e g q
|
2- Level system
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
Occupation of energy levels
Francisco Rivadulla
q
e
p
i
E
i
|
=
Equal populations (infinite temperature), not inverse populations (negative temperature)
2- Level system
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The most probable distribution:
Boltzmann distribution function
Francisco Rivadulla

Occupation of energy levels
Francisco Rivadulla
A couple of examples:

=
j
Ej
E
i
e
e
N
n
i
|
|


= =
+ =
i
E
i
i
i i
i
e E
q
N
E n E
E U U
|
) 0 (
| |
|
c
c
=
c
c
=


q
q
N
e
q
N
E
i
E
i
V
q
q
N
U U
|
|
.
|

\
|
c
c
=
|
) 0 (
V P U H q
V P U q V P q U
p
p p
A + A = A =
A + A = A = A
w q U
r
+ = A

Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The internal energy and entropy
Francisco Rivadulla

= =
= =
i
i i B
rev
dn E k
dT
dU
dS
TdS dq dU
|
i
i
i
n
W
E
c
c
+ =
ln
o |
W k S
B
ln =
W d k dn
n
W
k dS
B i
i
i
i
B
ln
ln
=
c
c
=

q Nk
T
U U
S
B
ln
) 0 (
+

=
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The Canonical Ensemble
Francisco Rivadulla

=
E
=

=
E
Qumica-Fisica IV
Introduction to Statistical Thermodynamics
The Canonical Ensemble
Francisco Rivadulla
V
Q
Q
U U
|
|
.
|

\
|
c
c
=
|
1
) 0 (
Q k
T
U U
S
B
ln
) 0 (
+

=
W
N
k
S
B
ln =

=
i
E
i
e E N Q
|
) (

Qumica-Fisica IV
Introduction to Statistical Thermodynamics
Key concepts of the chapter
Francisco Rivadulla

Qumica-Fisica IV
Introduction to Statistical Thermodynamics
Key concepts of the chapter
Francisco Rivadulla