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Statistical Thermodynamics
Atkins, P. & de Paulo, J. (2009). Physical Chemistry. 9th edition.
Oxford: Oxford University Press. (Chapters 15, 16)
The Distribution of Molecular States
Configurations and Weights
The Dominating Configuration
Boltzmann Distribution
Molecular Partition Function & its
 Partition Function for Independent Molecules
Perfect Gas
 Translational, Electronic & Nuclear Partition Function
Partition Function for Diatomic Gas
 Factorization
 Vibrational Partition Function
 Statistical Thermodynamics & Thermodynami Quantities
The Internal Energy
Heat Capacity
Entropy
2

Introduction
 By solving the Shrodinger equation (H =E ), one can calculate the energy of
molecules & then related the result to their structures.
 Thus, The next step is to see how this knowledge can be used to calculate the
properties of matter.
 Statistical thermodynamics provides the link between the individual molecular
properties and its bulk thermodynamic properties.
It means that how the average behavior of large number of molecules will change.
 For example, the pressure of the gas depends on the average force exerted by its
molecules & there is no need to specify which molecules happen to be striking the
wall at any instant.
 Therefore, for a large number of molecules the change in any thermodynamic
properties can be negligible compared to the average values.
3

The Distribution of Molecular States


 Consider a system composed of N molecules with a constant total energy, E.
 These molecules are independent, i.e. no interactions exist among the molecules.
 Countless collisions occur.
 It is hopeless to keep a track of positions, momenta, and internal energies of all
molecules.
 The Principle of equal a priori probabilities:
 All possibilities for the distribution of energy are equally probable.
 By this, the number of molecules and the total energy are kept the same.
Here, a Priori means as far as one knows.
Democracy among microscopic states !!!
4

 For example, consider four molecules in a three-level system. The following


two arrangements have the same probability.
---------l-l-------- 2
---------l----------
---------l---------- 0

---------l--------- 2
---------1-1-1----
------------------- 0

 Configurations and Weights


Imagine that there are N molecules in the system.
 n0 molecules with energy 0; n1 molecules with energy 1; n2 molecules
with energy 2, and so on.
 where 0 < 1 < 2 < ... are the energies of different states.
 The average number of molecules occupying a state is called population. So,
the energy of the state is denoted as i .
 The specific distribution of molecules is called configuration of the system,
denoted as { n0, n1, n2, ......}
5

 For example, in the system below, there is 17 molecules, and each molecule has
four states. The above configuration is thus: { 4, 6, 4, 3 }

STATE

10

14

15

2
13
12

11

5
16

17

4
6

 Now the question is how to determine the population ?


 For example,
 A configuration such as {N, 0, 0, ...} means that every molecule is in the
ground state, so there is only one way to achieve this configuration.
 But a configuration such as {N-2, 2, 0, ......} means that there are two
molecule is in the first excited state, and the rest in the ground state which can
be achieved in N(N-1)/2 ways.
A configuration { n0, n1, n2, ......} can be achieved in W different ways.
W is called the weight of the configuration and can be evaluated as follows,
W = N! / (n0! n1! n2! ...)
1. It means that there is N! different ways to arrange N molecules.
2. ni! arrangements of ni molecules with energy i correspond to the same
configuration.
7

 Question. Calculate the number of ways of distributing


20 objects into six boxes with the arrangement {1, 0, 3, 5,
10, 1}. Recall that; 0! = 1.

Answer:
20! / 1! 0! 3! 5! 10! 1! = 931,170,240

Question. Calculate the number of ways of distributing 3 objects a, b, and c


into two boxes with the arrangement {1, 2}.
Answer:
| a | b c |, | b | c a |, | c | a b |.
Therefore, there are three ways 3! / 1! 2!
To eliminate over-counting
these configurations

of

| a | c b |, | b | a c |, | c | b a |

 But what if the number of objects is so large ?!!

 Stirlings Approximation:
When x is large: ln x! x ln x - x
x

ln x!

x ln x x

ln A

1
2
4
6
8
10

0.000
0.693
3.178
6.579
10.605
15.104

-1.000
-0.614
1.545
4.751
8.636
13.026

0.081
0.65
3.157
6.566
10.595
15.096

Note that : A = (2
)1/2 (x+1/2)x e-x
10

Therefore:
ln W ( N ln N - N ) - ( ni ln ni - ni ) = N ln N - ni ln ni

x
1
16
20
30

ln x!
19.987
30.672
42.336
74.658

x ln x - x
17.819
28.361
39.915
72.036

ln A
19.980
30.666
42.332
74.656

Note that : A = (2
)1/2 (x+1/2)x e-x

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The Dominating Configuration


 Imagine that there are N molecules distribute among two states. The
possible configurations are;
{N, 0}
{N-1, 1},
{N-k, k},
{1, N-1}
{0, N}
 And their weights are 1; N; ... , N! / (N-k)! k!; ... ; N; 1, respectively.
 For example, N=8,
the weight distribution is:

N=8

60

40

20

8
12

12000

N =16

10000

8000
6000
4000
2000
0
0

9 1 01 11 21 31 41 51 6

6 .0 0 E + 0 0 8

N = 32

5 .0 0 E + 0 0 8
4 .0 0 E + 0 0 8
3 .0 0 E + 0 0 8
2 .0 0 E + 0 0 8
1 .0 0 E + 0 0 8
0 .0 0 E + 0 0 0
0

12

16

20

24

28

32

k
13

 When N is even, the weight is maximum at k = N/2, therefore;

Wk=N/2 = N! / [(N/2)!]2
 When N is odd, the maximum is at k = N/2 1.
 Therefore, as N increases, the maximum becomes sharper!
 The weight for k = N/4 is Wk=N/4 = N! / [(N/4)! (3N/4)!]
 The ratio of the two weights is equal to:
R(N) Wk=N/2 / Wk=N/4 =(N/4)! (3N/4)! / [(N/2)!]2
| N |4
| 8 | 16 | 32 | 256
| 6.0 x 1023
|R(N) | 1.5 | 2.5 | 7.1 | 57.1 | 3.5 x 1014 | 2.6 x 103e+22

14

Therefore, for a macroscopic molecular system ( N ~ 1023 ), there are


dominating configurations, so that the system is almost always found in
or near the dominating configurations, i.e. equilibrium.
 What if the system has more states?
 Constraints for the system
There are two constraints for the system:
1.

The total energy of a system is constant; ni i = E = constant

2.

The total number of molecules is conserved; ni = N = constant

 How to maximize W or lnW under these constraints?

15

The Boltzmann Distribution


 The Boltzmann distribution states;
ni / N = Pi = exp (
- i )
 Pi is the probability.
 is defined as; 1/
= kT ; Where k is the Boltzmann constant.

is a coefficient that makes the total probability equals ONE.
1 = i ni / N = i exp(
-
i)
exp(
) = 1 / i exp(-
i)
= - ln [
i exp(-
i)]
16

 In summary, using the principle of equal a priori probabilities, the


probabilities of different configurations can be evaluated by simple counting.
 Then, the dominating configuration whose population follows the Boltzmann
distribution can be found.
 The Boltzmann distribution relates the macroscopic physical properties to the
microscopic molecular properties, and it is capable of explaining the equilibrium
properties of all materials.
 To find the most important configuration, one need to vary { ni } to seek the
maximum value of W. But how?
 For example, consider a one-dimensional function such as F(x) = x2
dF/dx = 0
Is this enough?

17

 How about a two-dimensional case;

 For example, finding the minimum point of the surface of a half


watermelon which is F(x,y).
F/
x = 0
F/
y = 0
 If you have multi-dimensional function: F(x1, x2, , xn);
F/
xi = 0

i = 1,2,,n

 To find the maximum value of W or lnW, we should have:


lnW / ni = 0

i=1,2,3,...

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 The method of Lagrange Multipliers

 It is used to minimize or maximize a function F(x1, x2, , xn) under


constraints:
C1(x1, x2, , xn) = Constant1
C2(x1, x2, , xn) = Constant2
.
.
.
Cm(x1, x2, , xn) = Constantn
L = F(x1, x2, , xn) - i iCi(x1, x2, , xn)
L/
xi = 0

i=1,2, ...,

19

 Lets see the water melons surface case. How to find the minimum

or maximum of F(x, y) under a constraint x = a ?


L = F(x, y) - x
L/x=0
L/y=0
 Therefore;
dL = dF (x,y) - i i dCi
 Under constraint of x=a, dCi = 0, thus dF = 0.
It means that F is at its maximum or minimum.

20

The method of Lagrangian Multiplier based on the Boltzmann


distribution function;
 First, construct a new function, L.
L = lnW + i ni - i ni i
 Next, we need to find the maximum of L by changing ni .
 Finding and is equivalent to finding the maximum of W under the
two constraints defined before, i.e.;
L/
ni = lnW/
ni + -
i = 0
 Assignment 1. Prove this equation is correct.

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ln W ( N ln N - N ) - i ( ni ln ni - ni )

 Since,

= N ln N - i ni ln ni
lnW/
ni = (N ln N)/
ni - (ni ln ni)/ ni
= - ln (ni/N)
 Therefore,

ln (ni / N) + -
i = 0
ni / N = exp(
-
i)

 By this,

E = N < > = 3N/2

- where < > is the average kinetic energy of a molecule.


Therefore,

< > = <mv2/2> = 3/2

22

 On the other hand, according to the Maxwell distribution of speed,

the average kinetic energy of a molecule at an equilibrium is:


<mv2>/2 = 3kT/2
 This is actually the definition of the temperature where k is the
Boltzmann constant.
 Thus, 1 / = kT. This is the physical meaning of , the reciprocal
temperature.

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Q. Consider a molecule whose ground state energy is -10.0 eV, the first excited

state energy -9.5 eV, the second excited state energy -1.0 eV. Calculate the
probability of finding the molecule in its first excited state at T = 300, 1000,
and 5000 K.
Hint;
The energies of second, third and higher excited states are much higher than those of
ground and first excited states, for instance, at T = 5,000 K, the probability of finding
the first excited state is,
p2 = exp(
-
2)
with 2 = -9.5 eV
And, the probability of finding the second excited state is,
p3 = exp(
-
3)
with 3 = -1.0 eV
If you calculate the ratio of probabilities between second & first excited states at this
temperature and then compared that to the first excited state, you will see the chance
that the molecule is in second excited state is exceedingly slim. Thus, we consider
only the ground and first excited states, a two-state problem.
Note that: [ 1 eV = 1.60 x 10-19 J; k = 1.38 x 10-23 J.K-1]
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Therefore, the probability of finding the molecule in the first excited state is:
p = exp(-
2) / [exp(-
1) + exp(-
2)]; where, 1 = -10.0 eV, and 2 = -9.5 eV
(1) T = 300 K
p =

(2) T = 1000 K
p =

0.5 11600
exp

300

0.5 11600
+ exp

300

0.5 11600
exp

1000

0.5 11600
+ exp

1000

0.5 11600
exp

5000

0.5 11600
+ exp

5000

(3) T= 5000 K
p =

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The Molecular Partition Function


 The Boltzmann distribution function can be written as;
pi = exp (-
i) / q
 where pi is the probability of a molecule being found in a state i with
energy i.
 q is called the molecular partition function;
q = i exp (-
i)
 The summation is over all possible states (not just the energy levels).
 For example, if the energy level is gi-fold degenerate, then the molecular
partition function can be re- written as;
q = i gi exp(-
i)
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 It means that:

 As T 0,

q g0

Meaning at T = 0, the partition function is equal to the degeneracy of


the ground state.
 As T ,

q the total number of states.

 Therefore, the molecular partition function gives an indication of the


average number of states that are thermally accessible to a molecule at
the temperature of the system.
 The larger the value of the partition function is, the more the number
of thermally accessible states is.
 Thus, The relationship between q and : exp(
) = q-1
27

28

-2

q=e +e
=q-1

-3

+e

+ ......

Therefore,
-

q=1/(1-e

)
29

Partition Function for Independent Molecules


 Consider a system which is composed of N identical & indistinguishable

molecules with no interaction between them.


 We may generalize the molecular partition function q to the partition
function of the system Q (=1/kT);
Q = i exp(-
Ei)
 where Ei is the energy of a state i of the system, and summation is over
all the states.
 Since there is no interaction among molecules, Ei can be expressed as;
Ei = i(1) + i(2) +i(3) + + i(N)
 where i( j) is the energy of molecule j in its molecular state.
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The partition function Q:


Q = i exp[-
i(1) - i(2) - i(3) - -
i(N)]
= {
i exp[-
i(1)]}{
i exp[-
i(2)]} {
i exp[-
i(N)]}
= {
i exp(-
i)}N
= qN
 where q i exp(-
i) is the molecular partition function.
 This equality (Q= qN) is satisfied because the molecules are
independent of each other.

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Perfect Gas
 Perfect gas is an idealized gas where an individual molecule is treated as a point
mass which randomly moving and no interaction exists among molecules (PV=nRT).

 Molecular energy; the total energy of each molecule is defined as the sum of the
translational (kinetic) and internal energies;

= trans + int
 The internal energies include rotational, vibrational, electronic, and nuclear
energies

int = rot + vib + elect + nucl

electronic

vibrational

rotational

translational

32

Translational Partition Function (qT) of a monoatomic gas


 A molecule moves in a three-dimensional space, but first consider onedimensional case.
 Imagine a molecule of mass m moves along the x direction between x= 0 &
x= X, but it has been confined in the y- and z- direction. What is its partition
function qx?
 From particle in a box calculation, the energy levels are;
En = n2h2 / (8mX2)

n = 1, 2, 3,

 If the lowest energy equals to zero point energy, the relative energies can
then be expressed as;
n = (n2-1)

with

= h2 / (8mX2)

qx = n exp [ -(n2-1)
]
33

 is very small, thus;


qx = dn exp [ -(n2-1)
]
= dn exp [ -n2 ] = (2
m/h22)1/2 X
 Now consider a molecule of mass m, free to move in a container of volume,
V=XYZ.
 Its partition function qT can be expressed as;
qT = qx qy qz
= (2
m/h22)1/2 X (2
m/h22)1/2 Y (2
m/h22)1/2 Z
= (2
m/h22)3/2 XYZ = (2
m/h22)3/2 V
= V/
3
 where, = h(
/2
m)1/2 or (h2/2
mkT)1/2, the thermal wavelength. The thermal
wavelength is small compared with the linear dimension of the container.
 Partition function of a perfect gas (N molecules);

Q = (qT) N = V N / 3N

34

 For example, calculate the molecular partition function q for He in a cubical


box with sides 10 cm at 298 K.
 Answer;
 The volume of the box is V=0.001m3. The molar mass of the He molecule is
0.004/(6.0221023)=6.646610-27kg. Substituting these numbers and the proper
natural constants, we have;
27

2 6.6466 10 1.38 10
q=
(6.626 10 34 ) 2

23

298

3/ 2

0.001 = 7.820 10 27

N
n =
NA

nRT NkT
V=
=
p
p

8.2052 107 N M
1
kg
mol

qt =
p
Pa

(T K )

5
2

35

 Electronic Partition Function


 The electronic partition function is usually written as a sum over
energy levels rather than a sum over states (Where gi is the
degeneracy of the ith electronic level);

qelect = gi e i
Recall that the first electronic level is the ground state & the
remaining energy levels are expressed in terms of their spacing
relative to that.

qelect = g1 + g 2 e 12 + L

At ordinary temperatures, usually only the ground state and perhaps
the first excited state need to be considered.
36

 Nuclear Partition Function


The nuclear partition function has a form similar to that of the
electronic partition function.

qelect = gi e i
 Nuclear energy levels are separated by millions of electron volts.
 It means that temperatures on the order of 1010 K need to be
reached before the first excited state becomes populated to any
significant degree.

qelect = g1 + g 2 e 12 + L
Therefore, at ordinary temperatures we can simply express the
nuclear partition function in terms of the degeneracy of the ground
state.
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Table below shows the electronic energies for a number of atoms

38

Diatomic Gas
 Consider a diatomic gas made of two atoms A and B with N identical

molecules. A and B may be the same (homonuclear) or different


(heteronuclear).
 The mass of a diatomic molecule is M. These molecules are
indistinguishable. Thus, the partition function Q of the gas can be
expressed in terms of the molecular partition function q;

Q = q / N!
N

 The molecular partition q;

q = exp(i )
i

where, i is the energy of a molecular state i, =1/kT, and is the


summation over all the molecular states.
39

Modes of motions; translation, vibration, rotation

40

Molecular Partition Function; Factorization


 The energy of a molecule j is the sum of contributions from its different
modes of motion; T (translation), R (rotation), V (vibration), E, (electronic)

( j) = T ( j) + R ( j) + V ( j) + E ( j)
 The separation of the electronic and vibrational motions is justified by
different time scales of electronic and atomic dynamics.
 Rotational motion is approximated based on rigid rotor in QM. It
means rotary motion is about the center of mass.
 Vibrational motion is approximated based on harmonic oscillator. It
means relative vibratory motion of the two atoms.

q = i exp( i ) = i exp[ ( iT + iR + iV + iE )]
= [ i exp( iT )][ i exp( iR )][ i exp( iV )][ i exp( iE )]
= q T q R qV q E
41

The translational partition function of a molecule


T
exp(

i
i )

qT
sums over all the translational states of a molecule.
The vibrational partition function of a molecule

qV

sums over all the vibrational states of a molecule.


The rotational partition function of a molecule

qR

sums over all the rotational states of a molecule.


The electronic partition function of a molecule

qE

sums over all the electronic states of a molecule.

V
exp(

i
i )

R
exp(

i
i )

E
exp(

i
i )

42

 A polyatomic molecule containing N atoms has 3N degrees of freedom


totally.
 Three of these degrees of freedom can be assigned to translational
motion.
 Two (linear molecules) or three (for nonlinear molecules) are for
rotational motion.
 Thus, there are (3N-5) (linear molecule) and 3N-6 (nonlinear molecule)
for vibrational motion.
43

 For example, CO2 has 33-5 = 4 degrees of freedom of vibration;


nonlinear molecule of H2O has 33-6 = 3 degrees of freedom of
vibration.

44

 Recall rigid rotor & harmonic oscillator energy levels and degeneracy's
for rotational and vibrational motion.
Rigid Rotor

h 2 J ( J + 1)
J =
8
I

Harmonic Oscillator

J = 0,1, 2,K

I = re2

B rotational const.

12

v frequency

re bond length
m reduced mass

n = 0,1, 2,K

n = 1

J = 2 J + 1
I moment of inertia

v = h ( n + 12 )

m1m2
=
m1 + m2

1 k
v=
2

k force constant

B = h 8 2 Ic wave number

v
=
c
45

Vibrational Partition Function


 Two atoms vibrate along an axis connecting the two atoms. The
vibrational energy levels; n= 0, 1, 2, .

nV = (n +1/ 2)hv

 If we set the ground state energy to zero or measure energy from the
ground state energy level, the relative energy levels can be expressed as;

nV = nhv
5--------------5hv
4--------------4hv
3--------------3hv
2--------------2hv
1--------------hv
0--------------0

= hv
46

Then, the molecular partition function can be evaluated;

e q v = e + e 2 + e 3 + .... = q v 1
q v = 1 + e + e 2 + e 3 ...
q v = n exp( n ) = n exp(nhv) = 1 /[1 exp( hv)]
Assignment 2;

q = 1 /( 1 e
v

1
)=
1 e hv

 At very high temperature where kT >>hv, i.e.,

hv << 1, q 1
v

e hv 1 h

 The vibrational temperature, v hv/k,


is often used instead of the vibrational
frequencies.

v/K
v/cm-1

2
309
215

F2
HCl
H2
1280 4300 6330
892 2990 4400
47

Q. Calculate the proportion of I2 molecules in their ground, first excited,


and second excited vibrational states at 25oC. The vibrational
wavenumber is 214.6 cm-1.

n = (n+1/2) h
q = n exp(-
n) = exp (-
h
/2) n exp (-n
h
)
= exp (-
h
/2) / [1- exp (-
h
)]
Portion of I2 is in n-th vibrational state is
n) / q = exp (-n
h
) [1- exp (-
h
)]
pn = exp (-
Therefore, at T = 25oC = 298.15 oK,
h
= 1.036
p0 =0.645

p1 = 0.229

p2 = 0.081
48

 For Example, evaluate the vibrational partition functions at 1500 K. We


know that there are three normal modes of H2O vibrational partition
function.

kT hc = 1042.6 cm 1

At 1500 K:

1594.8 cm-1

3656.7 cm-1

3755.8 cm-1

Mode

~ cm 1
hc~ kT

3656.7

1594.8

3755.8

3.507

1.530

3.602

qV

1.031

1.276

1.028

qV = 1.0311.276 1.028 = 1.353

49

 Table below shows the molecular constants for several diatomic


molecules.

50

Connection between Thermodynamic & Statistical Quantities


 Thermodynamics is the science of energy conversion involving heat and
other forms of energy.
 A thermodynamic system is defined by a macroscopic region of the universe,
often called a physical system studied by using the principles of
thermodynamics.
 Statistical thermodynamics, or statistical mechanics, is the study of the
microscopic behaviors of thermodynamic systems using statistical methods and
probability.
 The essential problem in statistical thermodynamics is to determine the
distribution of a given amount of energy E over N particles in a system.
 The macroscopic properties such as internal energy, heat capacity, & can
be calculated in terms of partition functions.
 By this, statistical thermodynamics is a bridge between macroscopic and
microscopic properties of a system.
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