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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

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}

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 …

have different achieved a particular

population of state configuration

7

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?

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

9

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?

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}

{0,0,0,0,2,1} are equal

Probability to get each configuration doesn’t

depend on the face of dice!

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

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!

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

d ln W = ∑ dni + α ∑ dni − β ∑ ε i dni

i ∂ni i i

∂ 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

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

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

at very low T ( T→0)

lim e − βε i = 0 lim Z = g 0

β→∞ T →0 T →0

lim e − βε i = 1 lim Z = ∞

β→0 T →0 T →0

indication of the average number of states

that are thermally accessible to a molecule at

the temperature of the system

27

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

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

system

1

p0 =

(

1 + e − βε )

e − βε

p1 =

(

1 + e − βε )

As T → ∞ the populations of

all states (pi’s) are equal.

29

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.

30

31

Examples

Vibration of I2 in the ground, first- and second

excited states (Vibrational wavenumber is 214.6 cm-1)

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

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

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

room temperature

37

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

levels do not change. dU = ∑ ε i dni

i

From thermodynamics,

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

U − U (0) = = =

q ∂β V 1 − e − βε e βε − 1

The entropy: Entropy

35

U − U (0)

S= + Nk ln q 30

25

βε

( ) 20

S = Nk βε − ln 1 − e − βε

e −1

15

10

0

0 1000 2000 3000 4000 5000

T(K)

46

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