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Thermodynamics
Physical Chemistry IV
728343
1
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
3
Other Properties
Mass
Temperature
Pressure
Conductivity Extensive or
Thermodynamic Intensive
properties Properties ?
Heat capacity
Gibbs free energy
Enthalpy
Etc.
4
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 !!!
5
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
6
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 …
8
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
10
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}
11
All possible chance to throw 6 die = 6!
All possible chances to get {0,6,0,0,0,0}
6!
4!
1! 1! 0!
12
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}, …
13
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}
14
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
15
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
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!
17
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
18
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
19
f’(x) –
f’(x) +
Function of x: f(x)
First derivative: f ’
Second derivative: f ’’
20
Maximum & Minimum Point
f as a function of x and y: f(x,y)
21
22
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
∂ ln W
= ∑ + α − βε i dni
i ∂ni
23
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
= N ln N − ∑ ni ln ni
i
24
∂ 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
25
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
∞
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
28
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
(
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.
30
31
Examples
Vibration of I2 in the ground, first- and second
excited states (Vibrational wavenumber is 214.6 cm-1)
32
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
33
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
∞ 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
= 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
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
∂ 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
35
U − U (0)
S= + Nk ln q 30
βε
( ) 20
S = Nk βε − ln 1 − e − βε
e −1
15
10
0
0 1000 2000 3000 4000 5000
T(K)
46