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Statistical

Thermodynamics
Physical Chemistry IV
728343

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Introduction
 Macroscopic picture
 Bulk material
 Thermodynamic properties
 Kinetic properties
 Microscopic picture
 Electron, Neutron, Proton
 Atom, Molecule, Ion
 Position, Energy, Momentum
 Link between micro- and macro pictures
 Statistical method

2
Energy of a System
 Energy of a macroscopic system
depends on …
 Energy of a microscopic system
depends on …
 A macroscopic system comprises of
countless microscopic systems (x1023)

EMacro = ∑ Ei
i

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Other Properties
 Mass
 Temperature
 Pressure
 Conductivity Extensive or
 Thermodynamic Intensive
properties Properties ?
 Heat capacity
 Gibbs free energy
 Enthalpy
 Etc.

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 Macroscopic description can be derived
statistically from microscopic descriptions
of a collection of microscopic systems
 Description on average
 Fluctuation of microscopic properties
 Microscopic properties depends on a set of
parameters of each microscopic system
 Macroscopic properties depend on a small set
of macroscopic parameters !!!

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The Distribution of Molecular States
A system composed of N molecules
 Total energy (E) is constant
 Energy of each molecule (Ei)
Ei = E/N ?
Ei is fluctuated due to molecular collision
Constraint: Summation of Ei = E

 Molecules in different states possess different


energy levels
 The distribution of energy is the population of
a state (there are ni molecules in εi energy
level)
{0,1,5,7,1,0}

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Configuration and Weights
 Configuration  Weights
Conf. 1

ε6 ε6
ε5 ε5
ε4 ε4
ε3 ε3
ε2 ε2
ε1 ε1
Conf.1 Conf. 2 Conf.3 … w.1 w. 2 w.3 …

Different configurations Number of ways in


have different achieved a particular
population of state configuration
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Real life problem
 English Premier League
 20 football clubs
 Host-Guest matches
 How many matches for each club?
 How many matches for the whole league?

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Real life problem
 1, 2, 5, 10 baht coins
 How many configurations achieving 7 bahts
 How many ways to distribute 7 bahts to 5
persons? (if each person can get only 1 coin)
Conf. 1
{3,0,1,1,0} {2,2,0,1,0} {1,2,0,1,0} 10
10
5
5
2
2
1
1
0

Conf.1 Conf. 2 Conf.3 … w.1 w. 2 w.3 …


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Dice
 Chance to get 5 from 1 dice
 Probability to get 5 from 1 dice
 How many way (chance) to get 5 from 2
die?
 1,4 2,3 4,1 3,2
 What is the probability to get 5 from 2 dice?
 Probabilities to get 1,4 and 2,3 are equal?
 How many way to get 6 from 3 die?
 (1,2,3) 2,2,2 (1,1,4)
 Probabilities to get 2,2,2 and 1,2,3 are equal?

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Configuration
 Configuration of throwing dice
 to get 6 with 3 die
{2,0,0,1,0,0} {1,1,1,0,0,0} {0,3,0,0,0,0}

 Probabilities to get {2,0,0,1,0,0} and


{0,0,0,0,2,1} are equal
 Probability to get each configuration doesn’t
depend on the face of dice!

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 All possible chance to throw 6 die = 6!
 All possible chances to get {0,6,0,0,0,0}

6!

 All possible chances to get {0,4,0,1,1,0}

4!
1! 1! 0!
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 To get 10 from 3 die
 All F
possible chances are 24
ace Configuration
1   1 1    
2 2     1  
3   1 1 2
4     1 1
5     1 1  
6 1 1      
W 2 6 6 6 3
 The most likely configurations are
{0,1,1,0,1,0}, …
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 To get 10 from 4 die
 All possible
F chances are 40
ace Configuration
1 2 1 2 2 1     1
2 1 2     1 3 2
3   1   1   2 3
4       2 1 1  
5   1 1        
6 1
1  
1  
1   2     
W 2 2 2 6 4 4 6 4
 The most likely configuration is {1,1,1,1,0,0}

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Instantaneous Configuration
 Possible energy level (ε0, ε1, ε2 …)
 N molecules
 n0 molecules in ε0 state
n1 molecules in ε1 state …
 The instantaneous configuration is {n0,n1,n2…}
 Constraint: n0+n1+n2+… = N
# ways to achieve instantaneous conf. (W)
N! N!
W { n0 , n1 , n2 ...} = =
n0 !n1!n2 ! Π ni !
i

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Principle of Equal a priori
 All possibilities for the distribution of
energy are equally probable
 The populations of states depend on a
single parameter, the temperature.
 If at temperature T, the total energy is 3
 Energy levels: 0, 1, 2, 3
{0,3,0,0} {1,1,1,0} {2,0,0,1}
3 3 3

2 2 2

1 1 1

0 0 0

W=1 W=6 W=3 16


Examples
 {2,1,1}

4! 24
W { 2,1,1} = = = 12
2!1!1! 2

 {1,0,3,5,10,1}

20!
W {1,0,3,5,10,1} = = 9.31× 108
1!0!3!5!10!1!

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The Dominating Configuration
 Some specific configuration have much
greater weights than others
 There is a configuration with so great a
weight that it overwhelms all the rest
 W is a function of all ni: W(n0, n1, n2 …)
 The dominating configuration has the values
of ni that lead to a maximum value of W
The number of molecule constraint : ∑i ni = N
The energy constraint : ∑
i
niε i = E

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Possible configurations for N molecules
1 5 4 4 3 3 3 3 2 2 2      
2   1   2 1     3   1 1 1  
3     1   1 1     3 1 1 2  
4             1     1 1 1  
5             1       1 1  
6           1         1   5
N 5 5 5 5 5 5 5 5 5 5 5 5 5
E 5 6 7 7 8 12 12 8 11 11 20 17 30
W 1 5 5 10 20 20 20 10 10 60 120 60 1

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f’(x) –
f’(x) +

 Function of x: f(x)
 First derivative: f ’
 Second derivative: f ’’
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Maximum & Minimum Point
f as a function of x and y: f(x,y)

Maximum point: f’ 0 ; f’’ Minimum point: f’ 0 ; f’’


– +

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 Instead of W, we are looking for the best
set of ni that yields maximum value of lnW

 ∂ ln W 
∑ ε dni i =0
d ln W = ∑ 
i
dni = 0
i  ∂ni 
∑ dn
i
i =0

 Method of undetermined multipliers


 ∂ ln W 
d ln W = ∑  dni + α ∑ dni − β ∑ ε i dni
i  ∂ni  i i

 ∂ ln W  
= ∑   + α − βε i dni
i  ∂ni  
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Stirling’s Approximation
 Natural logarithmic of the weight
N!
W { n0 , n1 , n2 ...} =
n0 !n1!n2 !
ln W = ln N !−( ln n0 !+ ln n1!+ ln n2 !)
= ln N !−∑ ln ni !
i

 Stirling’s Approximation ln x!≈ x ln x − x If x is large

 The approximation for the weight


ln W = ( N ln N − N ) − ∑ ( ni ln ni − ni )
i

= N ln N − ∑ ni ln ni
i
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 ∂ ln W  
d ln W = ∑   + α − βε i dni = 0
i  ∂ni  
 ∂ ln W 
  + α − βε i = 0
 ∂ni 
 ∂ ln W  ∂ ( N ln N ) ∂ ( n j ln n j )
  = −∑
 ∂ni  ∂ni j ∂ni
∂ ( n j ln n j )  ∂n   ∂ ln n j 
∂ ( N ln N )  ∂N 
=   ln N +
∂N
= ln N + 1
∑ ∂ni
= ∑  j
j  ∂ni
 ln n j + n j  
j   ∂ni 
∂ni ∂n
 i ∂ni
= ln ni + 1
∂ ln W n
= −( ln ni + 1) + ( ln N + 1) = − ln i
∂ni N
ni n α − βε
− ln + α − βε i = 0 → i = e i
N N

ni = Neα − βε i → N = ∑ n j = Neα ∑ e
− βε j

j j

1
eα =

− βε j
e
j
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The Boltzmann Distribution
 The populations in the configuration of the
greatest weight depend on the energy of the
state according to the Boltzmann distribution:
ni e − βε i
=
N ∑ e −βε i
i

 The fraction of molecules in the state i


ni e − βε i
pi = =
N Z Sum over all possible
energy levels
The Molecular
Z = ∑ e − βε i No degeneracy
Partition Function
i 1
β=
= ∑ g je
− βε j
kT
sum over energy
j
level j
Boltzmann constant =
1.38x10-23 J/K
degeneracy 26
The Molecular Partition Function
Z = ∑ g je
− βε j 1
β=
j kT

 An interpretation of the partition function


 at very low T ( T→0)
lim e − βε i = 0 lim Z = g 0
β→∞ T →0 T →0

 at very high T ( T→∞)


lim e − βε i = 1 lim Z = ∞
β→0 T →0 T →0

 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
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The Partition Function for Uniform Energy Levels
 Equally spaced non-degenerate energy levels
ε0= 0 ε1= ε ε2= 2ε ε3= 3ε …
 Finite number n
ε3
Z = ∑ e − βε i ε2
i ε
ε1
 Infinite number ε0


Z = ∑ e − βε i Infinite # of
Si = 1 + x + x + 2 energy levels

e − βε=0 x+ +
= xS e −xβε21 +
+ ex−3βε+2 
+= S −1
= 1 + e − βε S+ − e −12 βε + e −3βε + 
⇒S=
= 1 + ( e ) +x ( e
− βε
) + (e )
− βε 2 − βε 3
+ Finite # of
energy levels
1
=
1 − e − βε
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The Possibility *
 The possibility of molecules in the state
with energy εi (pi)
Z of infinite # of energy levels*
e − βε i
pi =
Z
( )
= 1 − e − βε e − βε i

 Thepossibilities of molecules in the 2-level


system
1
p0 =
(
1 + e − βε )
e − βε
p1 =
(
1 + e − βε )
As T → ∞ the populations of
all states (pi’s) are equal.
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 The possibilities of molecules in the
infinite-level system*

(
p0 = 1 − e − βε )
( )
p1 = 1 − e − βε e − βε
p2 = (1 − e ) e
− βε − β 2ε

As T → ∞
the populations of
all states are equal.

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Examples
 Vibration of I2 in the ground, first- and second
excited states (Vibrational wavenumber is 214.6 cm-1)

for v = 0,1, 2 and T = 298.15 K


kT
= 207.226 cm −1
hc
hcν 214.6 cm −1
βε = = −1
= 1.036
kT 207.226 cm
Relative
energy pv = (1 − e − βε )e − vβε
p0 = 0.645
p1 = 0.229
p2 = 0.081

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Approximations and Factorizations
 Ingeneral, exact analytical expression for
partition functions cannot be obtained.
Why ?
 Closed approximation expressions to estimate
the value of the partition functions are
required for each systems
 Energy levels of a molecule in a box of length X

n2h2
En = n = 1, 2, 
8mX 2
h2
E1 = → ε1 = 0
8mX 2

( )
2
h
ε n = n2 − 1 ε ε = Relative
8mX 2 energy
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Translational Partition Function
 Partition function of a molecule in a box of length X

( ) qX = ∑ e ( )
2
h − n 2 −1 εβ
ε n = n −1 ε ε =
2
n = 1, 2, 
8mX 2 n =1
 The translation energy levels are very close together,
together therefore the
sum can be approximated by an integral.

∞ ∞
qX ≈ ∫ e ( ) dn = e − n εβ dn

2 2
− n −1 εβ

1 0

 Make substitution: x2=n2βε and dn = dx/(βε)1/2

∞ 1/ 2
π   2πm 
( ) ∫e ( )
1/ 2
2
1 1/ 2 1 1/ 2
qX = βε
−x
dx = βε
  =  2  X
0  2  h β 

34
 When the energy of a molecule arises
from several different independent sources
 E = Ex+Ey+Ez
 q = qxqyqz
A molecule in 3-d box
 ε nx ,n y ,nz = ε n( xX ) + ε n(Yy ) + ε n( Zz )
 − βε n( X )  − βε n( Y )  − βε n( Z ) 
q =  ∑ e x  ∑e
 y 
∑ e z 
 n  n 
 nx  y   z 
= qx q y qz
3/ 2
 2πm 
q =  2  XYZ
h β 
35
3/ 2
 2πm 
q =  2  XYZ
h β 
V
q= 3
Λ
1/ 2
 β  h
Λ = h  =
 2π m  ( 2πmkT ) 1/ 2

 Λ iscalled the thermal wavelength


 The partition function increases with
 The mass of particle (m3/2)
 The volume of the container (V)
 The temperature (T3/2)
36
Example
 Calculatethe partition function of an H2
molecule in 100 cm3 vessel at 25°C
h
Λ=
( 2πmkT ) 1/ 2
6.626 × 10 − 34 Js
=
{( 2π × 2.016 × 1.6605 × 10 − 27
)
kg × 1.38 × 10 − 23 JK −1 × 298 K } 1/ 2

= 7.12 × 10 −11 m

V 1.00 × 10 −4 m 3
q= 3 = = 2.77 × 10 26

Λ ( 7.12 × 10 −11 m ) 3

 About 1026 quantum states are thermally accessible at


room temperature
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The Internal Energy and Entropy
 The molecular partition function contains all
information needed to calculate the
thermodynamic properties of a system of
independent particles
 q ≈ Thermal wave function
 The Internal Energy
e − βε i
E = ∑ niε i Boltzmann distribution→ ni = N ×
q
i

N
E = ∑ ε i e − βε i N
E=− ∑
d − βε i N d
q i q i dβ
e =−
q dβ
∑i
e − βε i

de − βε i N dq
ε i e − βε i =− E=−
dβ q dβ
38
Relative
 Total energy energy
N dq
E = ∑ niε i = − ε3 3ε
i q dβ
ε2 2ε
 εi is relative energy (ε0=0) ε
ε1 ε
 E is internal energy relative ε0 0
to its value at T=0
 The conventional Internal Energy (U)
U = U (0) + E
A system with N
N  ∂q  independent molecules
U = U ( 0) −  
q  ∂β V • q=q(T,X,Y,Z,…)
 ∂ ln q 
U = U (0) − N  
 ∂β V
Only the partition function is required to determine the internal energy
relative to its value at T=0.
39
Example
 The two-level partition function
E=−
N dq
q dβ
 N  d
= − − βε  (1 + e − βε
)
 1 + e  dβ
Nεe − βε Nε
E=− − βε
=−
1+ e 1 + e βε
0.5

0.4

0.3
 At T = 0 : E → 0
all are in lower state (ε=0)
E/Nε

0.2
 As T → 0 : E → ½ Nε
0.1 two levels become equally
populated
0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00
kT/ε

40
The value of β
 The internal energy of monatomic ideal
gas N  ∂q 
U = U ( 0) −   = U (0) + 32 nRT
q  ∂ β V
V
 For the translational partition function q = 3
Λ
 ∂q   ∂ V  ∂ 1 V dΛ
  =  
3 
= V = − 3
 ∂ β V  ∂ β Λ  V ∂β Λ3 Λ4 dβ
3nRT 3N
dΛ d  hβ 
1/ 2
1 h Λ =
=   = × = 2 2β
dβ dβ  ( 2πm ) 1/ 2  2β 1/ 2 ( 2πm ) 1/ 2 2β
N nN A 1
 ∂q  3V β= = =
  = − nRT nRT kT
 ∂ β V 2β Λ3
R
k=
 Λ3  − 3V  3N
NA
U = U (0) − N   
3 
= U ( 0 ) +
 V  2 β Λ V 2β This result is
also true for
general cases. 41
Temperature and Populations
 When a system is heated,
 The energy levels are unchanged
 The populations are changed

HEAT

ε 10 ε 10
ε9 ε9
ε8 ε8
ε7 ε7
ε6 Increas
ε6
eT
ε5 ε5
ε4 ε4
ε3 ε3
ε2 ε2
ε1 ε1
ε0 0 0.2 0.4 0.6 0.8 ε0 0 0.2 0.4 0.6 0.8

42
Volume and Populations
ε = ( n − 1)
2
 Translational energy levels
h (X ) 2
n
8mX 2
 When work is done on a system,
 The energy levels are changed
 The populations are changed

WORK

ε 10 ε5
ε9
ε8 ε4
ε7
ε6 decreas
eV ε3
ε5
ε4 ε2
ε3
ε2 ε1
ε1
ε0 0 0.2 0.4 0.6 0.8 ε0 0 0.2 0.4 0.6 0.8

43
The Statistical Entropy
 The partition function contains all
thermodynamic information.
 Entropy is related to the disposal of energy
 Partition function is a measure of the number
of thermally accessible states
 Boltzmann formula for the entropy
S = k ln W
As T → 0, W → 1 and S → 0

44
Entropy and Weight
A change in internal energy
U = U (0) + ∑ niε i → dU = dU (0) + ∑ ni dε i + ∑ ε i dni
i i i

 When the system is heated at constant V, the energy


levels do not change. dU = ∑ ε i dni
i
 From thermodynamics,

dU = dqrev = TdS = ∑ ε i dni ∂ ln W


i dS = k ∑ dni = k d ( ln W )
dU ∂ni
= kβ ∑ ε i dni
i
dS =
T i

∂ ln W
+ α − βε i = 0 S = k ln W
∂ni
∂ ln W U − U ( 0)
dS = k ∑ dni + kα ∑ dni S= + Nk ln q
i ∂ni i T

45
Calculating the Entropy
 Calculatethe entropy of N independent
harmonic oscillators for I2 vapor at 25ºC
 Molecular partition function: q=
1
1 − e − βε

 The internal energy: N  ∂q  Nεe − βε Nε


U − U (0) =   = =
q  ∂β V 1 − e − βε e βε − 1
 The entropy: Entropy

35

U − U (0)
S= + Nk ln q 30

T S(J K-1 mol-1)


25

 βε
( ) 20

S = Nk  βε − ln 1 − e − βε 
 e −1
15
 10

0
0 1000 2000 3000 4000 5000
T(K)
46