15 Statistical thermodynamics 1:

the concepts
Statistical thermodynamics provides the link between the microscopic
properties of matter and its bulk properties.
Two key ideas:
First:

Boltzmann distribution

Second:

Ensemble

Statistical thermodynamics:
The crucial step in going from the quantum mechanics of individual
molecules to the thermodynamics of bulk samples is to recognize that
the latter deals with the average behavior of large numbers of
molecules.

The distribution of molecular states

Population
Principle of equal a priori probabilities
Assumption: All possibilities for the distribution of energy are equally
probable.

15.1

Configurations and weights

(a)

Instantaneous configurations
Configuration

{3,2,0, }

in 10 ways:

Configuration
W=

{N 0 , N 1 , }

in

different ways

N!
N0 ! N1! N2 !

The weight of a configuration

ln W =ln N ! ln N i !
i

N i ln N i
(N i)
( N ln N N )
i

N ln N N i ln N i
i

Using Stirlings approximation:

ln x !=x ln x x

(b)

The Boltzmann distribution

Under the two restrictions:
Constant total energy:
N i i =E
i

Constant total number of molecules:

N i=N
i

The populations in the configuration of greatest weight depend on the

energy of the state according to the Boltzmann distribution:
Ni
e
=
N e
i

1
kT

The thermodynamic temperature is the unique parameter that governs

the most probable populations of states at thermal equilibrium.

15.2

The molecular partition function

Population of state:
pi=

e
q

Definition of molecular partition function:

q= e

q= gI e

level I

(a) An interpretation of the partition function

lim q=g0
T0

That is, at

T =0

, the partition function is equal to the degeneracy of the

ground state.
In general.
lim q=
T

However, when the molecules have only a finite number of states, the upper
limit of

At

T =0

is equal to the number of states.

, only the ground state level is accessible and

q=g0

At very high temperature, virtually all states are accessible, and

is

correspondingly large.

Partition function of a uniform array of states:

q=

1
1e

pi =

=( 1e

) e

Population of two-state system:

p0=

1
( 1+e )

p1=

e
( 1+e )

(b)

Approximations and factorizations

Population function for translation in one dimension:

qX=

2 m
2
h

1/ 2

( )

X=

1/ 2

2 mkT
2
h

)
(Z)
n , n ,n =(nX ) + (Y
n + n
1

( X)
n1

(Y )
n2

q= e

(Z )
n3

alln

( X)
n1

(Y )
n2

e
e
e

(
)(
)(

2 m
h2

( )

nY

( )

nZ

all n

n1

n2

3 /2

( )

q=

( )

nX

= e

n3

2 m
h2

)=q q q
X

3 /2

( )

XYZ=

(Z )
n3

Partition function for translation in three dimension:

q=

=h
3
2
m

1 /2

( )

h
( 2 mkT )1 /2

The Internal energy and the entropy

15.3 The internal energy
The importance of the molecular partition function is that it contains all the
information needed to calculate the thermodynamic properties of a system
of independent molecules.
Statistical thermodynamics:

Quantum mechanics: wavefunction

The relation between U and q

(a)

E ( T ) = N i i
i

E (T )=

N
i e

q i

i e =
i

E (T )=

d
e
d

N
d N d
N d q
e =
e = q d
q
d

q
d

i
i
i

U ( T )=U ( 0 )+ E (T )

Internal energy in terms of the partition function:

U ( T )=U ( 0 )

N q
q

( )

In an alternative version:
U ( T )=U ( 0 )N

( lnq )

(b)

The value of

Fundamentals F.5:
3
U ( T )=U ( 0 )+ nRT
2

Justification 15.3:
U ( T )=U ( 0 )+
=

3N
2

nN A
N
1
=
=
nRT n N A kT kT

15.4

The statistical entropy

Boltzmann formula of the entropy:

S=k ln W

Entropy in terms of partition function:

S (T ) =

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

The temperature variation of the entropy of an equally spaced energy system

The temperature variation of the entropy of a two-level system

The canonical partition function

15.5 The canonical ensemble
The crucial new concept we need when treating systems of interacting
particles is the ensemble.

(a)

The concept of ensemble

The total energy of all the systems is

~
E

and, because they are in thermal

equilibrium with one another, they all have the same temperature,

. This

imaginary collection of replications of the actual system with a common

temperature is called the canonical ensemble.
Definitions of ensembles:
Microcanonical ensemble: N, V, E common
Canonical ensemble: N, V, T common
Grand canonical ensemble: , V, T common

(b)

Dominating configurations
~
E

: the total energy of the ensemble

~
N

: the number of imaginary replications

Ei

: the energy state of each member

~
Ni

: the number of members with energy

: the number of molecules in the actual system

Ei

~
W

: the total weigh of a configuration of the ensemble

~
N!
~
W =~ ~ ~
N 0! N1 ! N 2!

Definition of canonical partition function:

~
N i e E
=
Q= e E
~
Q
N
i

(c)Fluctuations from the most probable distribution

The probability of a member of an ensemble having a specified energy (as

distinct from being in a specified state) is given by

~
N i e E
=
~
Q
N

, a sharply

decreasing function, multiplied by a sharply increasing function.

Therefore, the overall distribution is a sharply peaked function. We conclude
that most members of the ensemble have an energy very close to the mean
value.

15.6

The thermodynamic information in the partition function

Like the molecular partition function, the canonical partition function carries
all the thermodynamic information about a system. However,
general than
independent.

is more

because it does not assume that the molecules are

The internal energy

~
~
U ( T )=U ( 0 )+ E (T )=U ( 0 )+ E(T )/ N

Because

Ei

e
~
pi=

as

~
N

U ( T )=U ( 0 )+ ~pi E i=U ( 0 ) +

i

1
Ei e E

Q i

Internal energy in terms of the canonical ensemble:

U ( T )=U ( 0 )

1 Q
ln Q
=U ( 0 )
Q V

( )

(a)

The entropy
The total weight of,

~
W

, of a configuration of the ensemble is the

product of the average weight

of each member of the ensemble,

~
~
W =W N

Hence,
~1/~N k ~
S=k lnW =k ln W = ~ ln W
N

Entropy in terms of the canonical partition function:

S (T ) =

U ( T )U ( 0 )
+ k ln Q
T

Independent molecules

(a)

Distinguishable and indistinguishable molecules

Relation between

and

For indistinguishable independent molecules;

Q=q N / N !

For distinguishable independent molecules;

Q=q N

(b)

The entropy of a monatomic gas

Sackur-Tetrode equation for the entropy of a monatomic gas:

S (T )=nR ln

e 5/ 2 V
h
=
3
1 /2
nNA
( 2 mkT )

) (

In terms of pressure,
S (T )=nR ln

e 5/ 2 kT
p 3

The Sackur-Tetrode equation implies that, when a monatomic perfect gas

expands isothermally from
S=nR ln ( a V f )nR ln ( a V i )=nR ln

Vi
Vf
Vi

( )

to

Vf

, its entropy changes by

16

Statistical thermodynamics 2: applications

Apply the concepts of statistical thermodynamics to the calculation of chemically significant quantities:
1. Establish the relation between thermodynamic functions and partition functions.
2. The molecular partition function can be factorized into contributions from each mode of motion and
establish the formulas for the partition functions for translational, rotational, vibrational modes of the
motion and the contribution of electronic excitation.
3. Specific applications: the mean energies of modes of motion, the heat capacities of substances, and
residual entropies.
4. Calculate the equilibrium constant of a reaction and through that calculation understand some of the
molecular features that determine the magnitudes of equilibrium constants and their variation with
temperature.

Fundamental relations
16.1

The thermodynamic functions

( lnQ )

UU ( 0 )=

S=

(c)

UU ( 0 )
+ k lnQ
T

Helmholtz energy
A=U TS

A A ( 0 )=kT ln Q

(d)

The pressure
A=U TS

dA= pdV SdT

Because

( VA )

p=

Pressure in terms of
p=kT

( lnVQ )

(e)

The enthalpy
H=U + pV

Enthalpy in terms of

( lnQ ) +kTV ( Vln Q )

HH ( 0 )=

(f)The Gibbs energy

G=H TS= A+ pV

Gibbs energy in terms of

GG ( 0 )=kT ln Q+kTV

( lnQ
V )

GG ( 0 )=kT ln Q+nRT

Because

Q=q N / N !

GG ( 0 )=NkT lnq +kT ln N !+ nRT

nRT ln q+ kT ( N ln NN ) + nRT
nRT ln

q
N

Gibbs energy of independent molecules:

GG ( 0 )=nRT ln

qm
NA

16.2

The molecular partition function

The energy of a molecule is the sum of contributions from its different modes of motion:
i = Ti + iR + Vi + iE

The electronic contribution is not actually a mode of motion, but it is convenient to

include it here.
The separation of terms in the equation above is only approximate (except for translation)
because all modes are not completely independent, but in most cases it is satisfactory.

The separation of the electronic and vibrational motions is justified provided only the ground
electronic state is occupied (for otherwise the vibrational characteristics depend on the
electronic state) and, for the electronic ground state, and the Born-Oppenheimer
approximation is valid.
The separation of the vibrational and rotational modes is justified to the extent that the
rotational constant is independent of the vibrational state.

Given that the energy is a sum of independent contributions, the partition function factorizes
into a product of contributions:
q= e =
i

i ( all states )

qT q R qV q E

T
i

i i i

(c)

The translational contribution

Translational contribution to
qT =

=h
3
2 m

1 /2

( )

h
( 2 mkT )1/ 2

qT as T

At room temperature

q 2 10

for an O2 molecule in a vessel of volume

28

100 cm3.
The thermal wavelength,

, should be much less than the average

separation of the molecules in the sample in order for the approximations

that led to the expression of

(d)

The rotational contribution

qT

are valid.

The partition function of a nonsymmetrical (AB) linear rotor:

~
hc B J (J+ 1)

q = (2 J +1)e
J

Rotational contribution to
qR=

in the high temperature limit (linear rotors):

T
R

: symmetric number
Characteristic rotational temperature
R=

~
hc B
k

Rotational contribution to
molecules):
R

q =

1 kT
hc

3 /2

( )(

~~ ~
ABC

1 /2

in the high temperature limit (nonlinear

(e)

The vibrational contribution

The vibrational energy levels:

( 12 ) hc ~ =0,1, 2,

E = +

Vibrational contribution to
The partition function:
~

qV = ehc = ( ehc )

qV =

1
hc ~
1e

In many molecules the vibrational wavenumbers are so great that

hc ~> 1

, the

vibrational partition function for a single mode is very close to 1, implying that
only the zero-point level is significantly occupied.
When bonds are so weak that
approximated into:
qV =

1
1( 1hc ~
+ )
x

because e 1+ x + when x is very samll.

hc ~ kT

, the partition function may be

Vibrational contribution to
qV =
V

q =

in the high temperature limit:

1
kT
= ~
~
hc hc
T
V

Characteristic vibrational temperature

V =

hc ~

(f)The electronic contribution

If we denote the energies of two levels as

E1 /2=0

and

E3 /2=

, the partition

function is:
E

q =

energy levels

g je

=2+2 e

(g)

The overall partition function

The overall partition function for a diatomic molecule with no low-lying

electronically excited states and
q=g E

V
3

T
R

( )( )(

1
1e

/T

T R

Under the assumptions :

the rotational levels are ver y close together
the vibrational levels are harmonic

Using statistical thermodynamics

Calculate partition functions
Any thermodynamic quantities
Gaining insight into a variety of physical, chemical, biological processes
Four important properties:
1. Mean energies
2. Heat capacities
3. Equations of state
4. Molecular interactions in liquids

16.3

Mean energies

The mean energy is the sum of contributions from:

i.

Translation

ii.

Rotation

iii.

Vibration

Mean energy of a mode of motion:

M =1M
q

( ) M =T , R ,V ,E
q

(c)

The mean translational energy

For a one-dimensional system of length

X

with =h

2 m

1 /2

( )
= ( X ) =
X
qT =
T

=
1/ 2

h
( 2 mkT )1 /2

d
1
1 1
= = kT
1/ 2
d
2 2

( )

For a molecule free to move in three dimensions,

Mean translational energy: (agrees to the equipartition theorem)
T = 3 kT
2

(d)

The mean rotational energy

Rotational partition function:

q = ( 2 J +1 ) e
R

~
hc B J ( J+1 )

q =1+ 3 e2 hc B +5 e6 hc B +

Hence, mean rotational energy is:

hc ~
B ( 6 e2 hc B + 30 e6 hc B + )
~

=
R

~
2 hc B

1+3 e

~
6 hc B

+5 e

At high temperature
R

q =

( T R )

~
T
hc B
with R=
R
k

Mean rotational energy (high temperature limit)

R = 1R d q
q

=hc ~
B

d
1
1
= =kT
d hc ~
B

is independent of

, so the partial derivatives have been replaced by

complete derivatives.)
Agree to the equipartition theorem

(e)

The mean vibrational energy

The vibrational partition function in the harmonic approximation:

qV =

1
hc ~
1e

~
d qV
d
1
hc ~
ehc
=
=
~
~ 2
d d 1ehc
( 1ehc )

Mean vibrational energy:

V
~ hc ~ hc ~ ehc ~
1
d
q
hc ~
hc e
= V
)
=( 1e
=
~ 2
hc ~

q d
1e
( 1ehc )
hc ~

V = hc
~

e 1
V

The zero-point energy,

1 ~
hc
2

, can be added to the right side if the mean energy

is to be measured from 0 rather than the lowest attainable level (the zero-point
level).

At high temperature, when

expanded

( e x 1+ x+ )

T V

or

hc ~ 1

, the exponential functions can be

and all but the leading terms discarded.

Mean vibrational energy (high temperature limit)

V =

hc ~

hc ~
1
=
=kT
~
hc
~
e 1 ( 1+ hc + )1

Agrees to the classical equipartition theorem, too.

16.4

Heat capacities

(a)

The individual contributions

The constant-volume heat capacity:

( U
T )

CV =

d
d d
1 d
d
=
= 2
=k 2
d T d T d kT d
d

It follows,
CV =k 2

( U
)

Contribution of a mode M to the constant-volume heat capacity:

CVM =N

M
M
=Nk 2
T V

Translational contribution to
CTV ,m =N A

d
dT

d
=N A

CV

( 32 kT ) = 3 R
dT

In the same way, when

rotational contribution to
CVR ,m =R for a linear rotar
3
CVR ,m = R for a non linear molecules
2

T R
CV

Vibrational contribution to
C

V
V ,m

=Rf ( T ) f ( T )= V
T

Where

( )(

V =hc ~ /k

V / 2 T

1e

/2 T

CV

(b)

The overall heat capacity

When equipartition is valid (when the temperature is well above the

characteristic temperature of the mode,

T M

) we can estimate the heat

capacity by counting the numbers of modes that are active.

Total heat capacity (at high temperatures)

CV ,m =

1
( 3+ R +2 V ) R
2

, where

is the number of active modes for each M mode

In most case,

V 0

16.5

Equations of state

16.6

Molecular interpretations in liquids

16.7

Residual entropies

Residual entropy:
The entropy at

that is greater than zero

T =0

Little energy difference:

AB AB AB AB AB BA BA AB

The total number of ways of achieving the same energy:

N

W =2

S=k ln 2N =Nk ln 2=nR ln 2

Residual entropy if
S m (0)=R ln s

orientations are possible,

An FClO molecule can adopt four orientation with the same energy (with the F
atom at any of the four corners of a tetrahedron):
S ( 0 )=R ln 4=11.5 J K mol
is in good agreement with the experiment value (
10.1 J K mol )
3

For CO , the measured residual entropy is 5 J K mol , which is very close to

, the value expected for a random structure of the form . .. CO CO OC CO OC OC .. .
1

R ln 2

16.8

Equilibrium constants

Gibbs energy of independent molecules:

GG ( 0 )=nRT ln

(a)

qm
NA

The relation between K and the partition function

Gm (J )Gm ( J , 0 )=RT ln

qm
NA

The equilibrium constant for the reaction

function:
K=

K=

q C ,m
NA

q D ,m
NA

( )( )
( )( )
{ ( ) }
a

A ,m

q
NA

B ,m

q
NA

qJ ,m
NA

e E / RT
r

e E / RT
r

r E 0=cU m (C , 0 ) +dU m ( D , 0 )aU m ( A ,0 )bU m ( B , 0 )

, which is themolar reactioninteranl energy at T =0.

a A+b B c C+ d D

in terms of partition

(b)

A dissociation equilibrium

An equilibrium in which a diatomic molecule:

2

X2 (g ) 2 X (g ) K =

pX
pX p

K=

q X , m
NA

( )
q X , m
NA
2

r E 0
RT

( qX ,m )
qX

NA
,m

r E0
RT

K=

qC , m
NA

q A , m
NA

qD , m
NA

qB ,m
NA

( )( )
( )( )

r E0
RT

with

r E 0=2 U m ( X , 0 )U m ( X 2 ,0 )=D0 ( X X )
where D0 ( XX ) is the dissociation energy of the X X bond .

The standard molar partition functionsare :

q

X ,m

X 2 ,m

=g X

V m

( )
( )

=g X

3
X

V m

3
X2

RT g X
p 3X
R
X2

V
X2

q q =

RT g X q RX qVX
2

3
X2

The equilibrium constant is :

2

K=

kT g X X 2

p gX qX qX X
2

D0
RT

where we have used R/ N A =k .

(c)

Contributions to the equilibrium constant

Consider a simple
N p q P E /RT
= e
N R qR
r

K=

q P E / RT
e
qR
r

RP

gas-phase equilibrium: