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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
---------l--------- 2
---------1-1-1----
------------------- 0
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
Answer:
20! / 1! 0! 3! 5! 10! 1! = 931,170,240
of
| a | c b |, | b | a c |, | c | b a |
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
11
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
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
2.
15
17
i = 1,2,,n
i=1,2,3,...
18
i=1,2, ...,
19
Lets see the water melons surface case. How to find the minimum
20
21
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,
22
23
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]
24
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 =
25
It means that:
As T 0,
q g0
28
-2
q=e +e
=q-1
-3
+e
+ ......
Therefore,
-
q=1/(1-e
)
29
31
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
electronic
vibrational
rotational
translational
32
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
Q = (qT) N = V N / 3N
34
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
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
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.
37
38
Diatomic Gas
Consider a diatomic gas made of two atoms A and B with N identical
Q = q / N!
N
q = exp(i )
i
40
( 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
i
i )
qT
sums over all the translational states of a molecule.
The vibrational partition function of a molecule
qV
qR
qE
V
exp(
i
i )
R
exp(
i
i )
E
exp(
i
i )
42
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
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
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
hv << 1, q 1
v
e hv 1 h
v/K
v/cm-1
2
309
215
F2
HCl
H2
1280 4300 6330
892 2990 4400
47
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
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
49
50