12/20/2008

chapter 8

Dr. I. Nasser

Classical Statistics of Maxwell-Boltzmann

-
Classical Statistics of Maxwell-Boltzmann

i
ii
II

) (

i
ii
iii
iv
v
vi
vii

III

178
181
182
183
183
184
185
186
186
187
188

188

193

177

12/20/2008

chapter 8

Dr. I. Nasser

Classical Statistics of Maxwell-Boltzmann

-
Classical Statistics of Maxwell-Boltzmann
-
. ni

i .
. -
.

- -
.

I -
:

-1 )(Identical
-2 )(Distinguishable

-3 ). (Pauli exclusion principle

) (
) (

. .

!
.

178

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Dr. I. Nasser

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Classical Statistics of Maxwell-Boltzmann

) (:

#
n3

3
2
1

n2
n1

-1 ) " (1 , 2 , 3 ,
-2

) "(1 < 2 < 3 ,

) " (n1 , n 2 , n 3 ,

:
-I N :

N = ni ,

)(1

-II U :

U = ni i

)(2

) ( C N
j n1 n 2
:

!N

)(3

= } i = {n

i =1

. ni

179

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

" . i
" i

} . {n i = 0

i

ni ni + n i ) (1):(2

N = ni = 0

)(4

U = i n i = 0

)(5

i =0
ln

)(6

i = 0
:
)( " "Monotonic function . i

i
ln .

: ) (3 ln( z !) = z ln( z ) z :

i ) = N ln N n ln n
ln(
i i

)(7

i ) = ln n n
ln(
i i

)(8

: ) (3 :

!N

)! ) = ln(N !) ln( n i
n
i =1
! ni

(i ) = ln
ln(

i =1

]! = ln(N !) ln [ n1 ! n 2 !"" n n
)! = ln(N !) [ ln(n1 !) + ln(n 2 !) + .......] = ln(N !) ln(n i
i

180

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

) i ) = N ln N N ( n ln n n
ln(
i i i
i

= N ln N N n i ln n i n i
i
i
N
N

= N ln N n i ln n i

)(7a

) ( 7a n i:

) i ) = ( N ln N ) ln n n n (ln n
ln(
i i i
i

 

1
ni
ni

= 0 ln n i n i n i
i
i


=0

= ln n i n i

)(8a

) ( 8a ) i
ln(

n i .

: ) (1) (2
)(3 .

) (

) ( Non Degenerate levels

.
ni
) ( B ) (1 )(2
) (8 :

181

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

i) + n n = 0
ln(
i i i

)(11

"" .

) (11 ) (4) (5) (8 :

+ i ] n i = 0

[ ln n
i

. n i
n i :

n i = e i

)(12

) (12 - .

e i

ii

) ( Degenerate States

" " i g i
n i
j

. g ini . g ini
i =1

g ini
! i } = N
! i =1 n i
j

)(13

i {n

! N :

)(13a

j
N ! j g ini
g ini
=

! N ! i =1 n i ! i =1 n i

= } i {n

182

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

:
-1 ) (13 :

i ) = n ln g i + 1
ln(
i i n
i

gi
ni
ni

)(14

i ) = ln
ln(

) (1) (2) (14 ""

-2

- :

n i = g i e i

)(15

- ) (12 ) (15
.

II

) (15 :

N = n i = g i e i = e g i e i
i

183

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Dr. I. Nasser

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Classical Statistics of Maxwell-Boltzmann

N
N
=
,
i
Z sp
gie

Z sp = g i e i
i

= e

Z sp " . "Single particle Z sp

" "Partition function .

" "Zustandsumme )( .
" " .

- ) (15 :

)(16

Z sp

ni = N

)(17

ii

n i = Ng i

Z sp

1-

= i g i e i

g e
i

= i g i e i

)(18

Z sp

Z sp

2-

V T ,N

)(19

= g i e

i
T ,N

V T ,N

g e
i

Z sp

=

V T ,N V

Z sp
= g i e

i
V T ,N
184

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

iii

:
i

g e
i

1 Z sp
Z sp

1
Z sp

n
i

g e
i

1
N

1
Z sp

]) [ln( Z sp

)(20

= E

E =

]) [ln( Z sp

)(21

U = N E = N

:
-1

1 Z sp
Z sp 2
2

= E2

-2

2
ln Z sp
2

= ) 2 = E 2 (E
2

iv

185

 Dr. I. Nasser

12/20/2008

chapter 8

Classical Statistics of Maxwell-Boltzmann

E
P =

V S , N
1
Z sp

g e
i

V T ,N

1 Z sp 1 ln( Z sp )

Z sp V V T ,N

P=

1 ln( Z sp )

V T ,N

(22)

:( 16)

ln( n i ) = ln N ln Z sp i
:( 7)

i ) = k N ln N n ln n
S = k B ln(
i i i
B

S = k B N ln N n i

ln N ln Z sp i
ln n i
N

= k B N ln N ln N n i + ln Z sp n i + n i i
i
i
i

N
N




N
N
U

S = k B N ln Z sp + k B U
186

(23)

chapter 8

Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

) (1).(2

vi
:

-1 TdS = dU + PdV :

1 S
=

T U V

)(a

-2 ) (23 :

U V

d ln Z sp
S

= kBN

+ k B + k BU
d U V
U V

 

U
N

= kB

)(b
U

N
1
) (b :
k BT

d ln Z sp
d

) .(21 )(a

1
=
:
k BT

1
=
,
T
k BT 2
T

=
= k BT 2
T
T

[ln( Z sp )] = kT 2
]) [ln( Z sp

187

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Classical Statistics of Maxwell-Boltzmann

vii F

F = U TS
) = U T ( k B N ln Z sp + k B U
= U Nk BT ln Z sp k BT U
N
1/

)(24

F = Nk BT ln Z sp

III :

-1
- N .T
- T 0 .T

- n1 n 2
N:

N = n1 + n 2

.
:

n1 = cNe = cN ,
0

n 2 = cNe
N = n1 + n 2 :

1
:

1 + e / k BT

188

=c

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

E total = 0 E 1 + N 2 = N 2
:
2

dE total
dN 2 N 2
e / k BT
= C
=
=
dT
dT
k BT 2 (1 + e / k BT

- T 0 1

BT

1 + e / k :

N / k BT
e
k BT 2
2

- T 1

BT

= C

e / k :

N 2
= C
4 k BT 2

-2 4000 ) (1 = 0, 2 = , 3 = 2
. g i = g
-
. 2300

- n 2
n1 . n 3

- :

n i = g i e i
n1 = ge , n 2 = ge , n 3 = ge 2
x = e n 2 = n1x . n 3 = n1x 2
:

n1 + n 2 + n 3 = n1 + n1x + n1x = 4000,

2

)(a

n1 (1 + x + x 2 ) = 4000
189

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Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

n1 0 + n 2 + n 3 2 = n1 0 + n1x + n1x 2 2
= 2300 ,

)(b

n1 ( x + 2x 2 ) = 2300

n1 ) (a ) (b :

57x 2 + 17x 23 = 0
x = 0.5034 . x = 0 .8 0 2
:

2300
2277,
0.5034 + 2(0.5034) 2
n 2 = n1x = 1146,
= n1

n 3 = n1x 2 = 577

g 4000
)!( 2277!) (1146!) ( 577

=i
1=

- n 2 n1
n 3:
4000

g
)!( 2278!) (1144!) ( 578
1 2:

= 2

2
= 0.9966
1

1
.
.

190

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Classical Statistics of Maxwell-Boltzmann

-3
.V 0, 1 , 2
. g 1 = 2, g 2 = 1, g 3 = 1,:

-
-

- .

) ( a,b
: g 1 = 2

4
0
0
b

) ( Microstates
2
3
0
0
0
0
0 ab
a b

8
0
a
0

0
2

2
191

0
= E0
)(Energy

5
0
b
0

= E1

) ( Microstates
10
11
12
a
b
a
0
0
0
b 0
0 a
0 b
2

1
0
0
ab 0
0

) ( Microstates
6
7
0
0
a
b
b 0
0 a

13
0
ab

)(Energy

)(Energy
9
b
0
a

0
2

0
= E2

chapter 8

Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

) ( Microstates
14
15
16
b
a
ab
a
b
0
0 0
0 0
0 0
E 4 = 4

)(Energy
2

0
= E3

- :
= ) (

g N = (2 + 1 + 1) 2 = 42 = 16 microstates
-

Z MB = e E i
i =0

= 4e E o + 4e E1 + 5e E 2 + 2e E 3 + e E 4
= 4 + 4e + 5e 2 + 2e 3 + e 4
- :
1 Z
Z
) (as T

E MB =

4 e + 10 e 2 + 6 e 3 + 4 e 4
3


2
3
4
4 + 4e + 5e
+ 2e
+e
2

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 Dr. I. Nasser

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chapter 8

Classical Statistics of Maxwell-Boltzmann

Z sp = g i e

-1

Quantity

Symbol

Formula

ln Z sp
U =N E =N

V , N

ln Z sp
Nk BT 2

T V ,N

i)
S = k B ln(

Nk B ln Z sp + k BU

F = U TS

Nk BT ln Z sp

F
P =

V T , N

ln Z sp
Nk BT

V T ,N

N T ,V

ln Z sp
Nk BT

N V ,T

G = F + PV

F
= F V

V T ,N

ln Z sp

Nk BT
ln
Z

sp
lnU T ,N

ln Z sp
ln Z sp
Nk BT
+

lnT V ,N lnV T ,N

H = U + PV

S
CV = T

T V ,N
2F
= T
2
T V , N
193

ln Z sp
2 ln Z sp
+
Nk BT 2
T

2
T V
T
V

chapter 8

Dr. I. Nasser

12/20/2008

Classical Statistics of Maxwell-Boltzmann

-2 :

1 = 0

2 = 100 k B

3 = 200 k B . g 3 = 5 g 2 = 3 g 1 = 1
" "Relative population .T = 100 K
: ) (15 :
j
i

g je
gie

g je

g i e i

nj
ni

= 3 e 1

100 k B /100 k B

n 2 3e
=
1e 0
n1

n 3 5 e 200 k B /100 k B
=
= 5 e 2
0
1e
n1
n 3 5 e 200 k B /100 k B
= 100 k B /100 k B 1.7 e 1
n 2 3e

194

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Classical Statistics of Maxwell-Boltzmann

195

chapter 8