09/19/2001 Notes from R.T.

DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

Chapter 6
Statistical Thermodynamics
Notes on
Thermodynamics in Materials Science
by
Robert T. DeHoff
(McGraw-Hill, 1993).
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Combinatorial Analysis
Consider a system of N particles that are
allowed to occupy r states.
Microstate --- The description of the system
that provides the state of each particle.
Number of possible microstates =
N
r
! !... !... ! !
!
3 2 1 r i
j
n n n n n
N
Macrostate --- The description of how many
particles, n
i
, are in each of the r states.
Number of microstates in a macrostate:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N=3, r=3
E1=1 E2=2 E3=3 Esum Omega %
I 3 0 0 3 1 3.7%
II 2 1 0 4 3 11.1%
III 2 0 1 5 3 11.1%
IV 1 2 0 5 3 11.1%
V 0 3 0 6 1 3.7%
VI 1 1 1 6 6 22.2%
VII 1 0 2 7 3 11.1%
VIII 0 2 1 7 3 11.1%
IX 0 1 2 8 3 11.1%
X 0 0 3 9 1 3.7%
27 100%
N= 3, r= 3
E 1 E 2 E 3
I A B C - -
11 A B C -
A C B -
B C A -
III A B - C
A C - B
B C - A
IV A B C -
B A C -
C A B -
V - A B C -
V I A B C
A C B
B A C
B C A
C A B
C B A
V II A - B C
B - A C
C - A B
V III - B C A
- A C B
- A B C
IX - A B C
- B A C
- C A B
X - - A B C
N=3 and r=3
0
1
2
3
4
5
6
7
8
2 4 6 8 10
Sum
O
m
e
g
a
Combinatorial
Analysis
Microstates
Macrostates
Distribution N=3, r=3
27
N
r
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Assumptions
Consider all particles to be identical.
The net value of a macroscopic property depends
on the number of particles (n
i
) in each state (i).
Exchanging the specific identity of the particles in
a state does not change the value of the property.
On average the fraction of time each particle
spends in any energy state is the same.
Probability of a macrostate is equal to the
fraction of time the system of particles
spends in that macrostate
Hypothesis
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Probability of Macrostates
Hypothesis
Fraction of time in a macrostate =
probability of that macrostate.
s microstate of total
j macrostate in s microstate of
P
j
#
#

r
1
! n
N!

r
P
N r
1 i
i
N
j
j
1
]
1

1
1
1
1
]
1

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Probability of Macrostates

r
1
! n
N!
P
N r
1 i
i
j
1
]
1

1
1
1
1
]
1

Sharp distribution --- Most probable state and/or

those near it are observed most of the time.
N=10, r=3
0%
2%
4%
6%
8%
10%
12%
14%
16%
9 11 13 15 17 19 21 23 25 27 29 31
Sum
P
N=10, r=2
0%
5%
10%
15%
20%
25%
30%
9 11 13 15 17 19 21
Sum
P
N=3, r=3
0%
5%
10%
15%
20%
25%
30%
2 4 6 8 10
Sum
P
N=6, r=3
0%
5%
10%
15%
20%
25%
5 7 9 11 13 15 17 19
Sum
P
N=4, r=3
0%
5%
10%
15%
20%
25%
3 5 7 9 11 13
Sum
P
N=10, r=4
0%
2%
4%
6%
8%
10%
12%
9 13 17 21 25 29 33 37 41
Sum
P
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N=3, r=3
0%
5%
10%
15%
20%
25%
30%
0% 20% 40% 60% 80% 100%
Sum
P
N=10, r=3
0%
2%
4%
6%
8%
10%
12%
14%
16%
0% 20% 40% 60% 80% 100%
Sum
P
N=6, r=3
0%
5%
10%
15%
20%
25%
0% 20% 40% 60% 80% 100%
Sum
P
N=4, r=3
0%
5%
10%
15%
20%
25%
0% 20% 40% 60% 80% 100%
Sum
P
Plot probability as function of fractional range.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N-3, r=3
E1 E2 E3 Esum Omega %
I 3 0 0 3 1 3. 7%
II 2 1 0 4 3 11.1%
III 2 0 1 5 3 11.1%
IV 1 2 0 5 3 11.1%
V 0 3 0 6 1 3. 7%
VI 1 1 1 6 6 22.2%
VII 1 0 2 7 3 11.1%
VIII 0 2 1 7 3 11.1%
IX 0 1 2 8 3 11.1%
X 0 0 3 9 1 3. 7%
N=4, r=3
E1 E2 E3 Esum Omega %
I 4 0 0 4 1 1.2%
II 3 1 0 5 4 4.9%
III 3 0 1 6 4 4.9%
IV 2 2 0 6 6 7.4%
V 1 3 0 7 4 4.9%
VI 2 1 1 7 12 14.8%
VII 0 4 0 8 1 1.2%
VIII 2 0 2 8 6 7.4%
IX 1 2 1 8 12 14.8%
X 0 3 1 9 4 4.9%
XI 1 1 2 9 12 14.8%
XII 1 0 3 10 4 4.9%
XIII 0 2 2 10 6 7.4%
XIV 0 1 3 11 4 4.9%
XV 0 0 4 12 1 1.2%
N=6, r=3
E1 E2 E3 Esum Omega %
I 6 0 0 6 1 0.1%
II 5 1 0 7 6 0.8%
III 5 0 1 8 6 0.8%
IV 4 2 0 8 15 2.1%
V 3 3 0 9 20 2.7%
VI 4 1 1 9 30 4.1%
VII 4 0 2 10 15 2.1%
VIII 2 4 0 10 15 2.1%
IX 3 2 1 10 60 8.2%
X 1 5 0 11 6 0.8%
XI 3 1 2 11 60 8.2%
XII 2 3 1 11 60 8.2%
XIII 0 6 0 12 1 0.1%
XIV 3 0 3 12 20 2.7%
XV 1 4 1 12 30 4.1%
XVI 2 2 2 12 90 12.3%
XVII 0 5 1 13 6 0.8%
XVIII 1 3 2 13 60 8.2%
XIX 2 1 3 13 60 8.2%
XX 0 4 2 14 15 2.1%
XXI 2 0 4 14 15 2.1%
XXII 1 2 3 14 60 8.2%
XXIII 0 3 3 15 20 2.7%
XXIV 1 1 4 15 30 4.1%
XXV 1 0 5 16 6 0.8%
XXVI 0 2 4 16 15 2.1%
XXVII 0 1 5 17 6 0.8%
XXVIII 0 0 6 18 1 0.1%
N=10, r=3
E1 E2 E3 Esum Omega %
I 10 0 0 10 1 0.00%
II 9 1 0 11 10 0.02%
III 9 0 1 12 10 0.02%
IV 8 2 0 12 45 0.08%
V 8 1 1 13 90 0.15%
VI 7 3 0 13 120 0.20%
VII 8 0 2 14 45 0.08%
VIII 7 2 1 14 360 0.61%
IX 6 4 0 14 210 0.36%
X 7 1 2 15 360 0.61%
XI 6 3 1 15 840 1.42%
XII 5 5 0 15 252 0.43%
XIII 7 0 3 16 120 0.20%
XIV 4 6 0 16 210 0.36%
XV 6 2 2 16 1260 2.13%
XVI 5 4 1 16 1260 2.13%
XVII 3 7 0 17 120 0.20%
XVIII 6 1 3 17 840 1.42%
XIX 5 3 2 17 2520 4.27%
XX 4 5 1 17 1260 2.13%
XXI 2 8 0 18 45 0.08%
XXII 6 0 4 18 210 0.36%
XXIII 3 6 1 18 840 1.42%
XXIV 5 2 3 18 2520 4.27%
XXV 4 4 2 18 3150 5.33%
XXVI 1 9 0 19 10 0.02%
XXVII 2 7 1 19 360 0.61%
XXVIII 3 5 2 19 2520 4.27%
XXIX 5 1 4 19 1260 2.13%
XXX 4 3 3 19 4200 7.11%
XXXI 0 10 0 20 1 0.00%
XXXII 1 8 1 20 90 0.15%
XXXIII 2 6 2 20 1260 2.13%
XXXIV 5 0 5 20 252 0.43%
XXXV 3 4 3 20 4200 7.11%
XXXVI 4 2 4 20 3150 5.33%
XXXVII 0 9 1 21 10 0.02%
XXXVIII 1 7 2 21 360 0.61%
XXXIX 2 5 3 21 2520 4.27%
XL 4 1 5 21 1260 2.13%
XLI 3 3 4 21 4200 7.11%
XLII 0 8 2 22 45 0.08%
XLIII 4 0 6 22 210 0.36%
XLIV 1 6 3 22 840 1.42%
XLV 3 2 5 22 2520 4.27%
XLVI 2 4 4 22 3150 5.33%
XLVII 0 7 3 23 120 0.20%
XLVIII 3 1 6 23 840 1.42%
XLIX 2 3 5 23 2520 4.27%
L 1 5 4 23 1260 2.13%
LI 3 0 7 24 120 0.20%
LII 0 6 4 24 210 0.36%
LIII 2 2 6 24 1260 2.13%
LIV 1 4 5 24 1260 2.13%
LV 2 1 7 25 360 0.61%
LVI 1 3 6 25 840 1.42%
LVII 0 5 5 25 252 0.43%
LVIII 2 0 8 26 45 0.08%
LIX 1 2 7 26 360 0.61%
LX 0 4 6 26 210 0.36%
LXI 1 1 8 27 90 0.15%
LXII 0 3 7 27 120 0.20%
LXIII 1 0 9 28 10 0.02%
LXIV 0 2 8 28 45 0.08%
LXV 0 1 9 29 10 0.02%
LXVI 0 0 10 30 1 0.00%
27
N
r
81
N
r
729
N
r
049 , 59
N
r
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N=10, r=4
0%
2%
4%
6%
8%
10%
12%
0% 20% 40% 60% 80% 100%
Sum
P
N=10, r=3
0%
2%
4%
6%
8%
10%
12%
14%
16%
0% 20% 40% 60% 80% 100%
Sum
P
N=10, r=2
0%
5%
10%
15%
20%
25%
30%
0% 20% 40% 60% 80% 100%
Sum
P
Plot probability as
function of
fractional range.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N=10, r=2
I E1 E2 Esum Omega %
II 10 0 10 1 0.10%
III 9 1 11 10 0.98%
IV 8 2 12 45 4.39%
V 7 3 13 120 11.72%
VI 6 4 14 210 20.51%
VII 5 5 15 252 24.61%
VIII 4 6 16 210 20.51%
IX 3 7 17 120 11.72%
X 2 8 18 45 4.39%
XI 1 9 19 10 0.98%
XII 0 10 20 1 0.10%
024 , 1
N
r
N=10, r=4
E1 E2 E3 E4 Esum Omega %
I 10 0 0 0 10 1 0.000%
II 9 1 0 0 11 10 0.001%
III 9 0 1 0 12 10 0.001%
IV 8 2 0 0 12 45 0.004%
V 9 0 0 1 13 10 0.001%
VI 8 1 1 0 13 90 0.009%
VII 7 3 0 0 13 120 0.011%
VIII 8 0 2 0 14 45 0.004%
IX 8 1 0 1 14 90 0.009%
X 7 2 1 0 14 360 0.034%
XI 6 4 0 0 14 210 0.020%
XII 8 0 1 1 15 90 0.009%
XIII 7 2 0 1 15 360 0.034%
XIV 7 1 2 0 15 360 0.034%
XV 6 3 1 0 15 840 0.080%
XVI 5 5 0 0 15 252 0.024%
XVII 8 0 0 2 16 45 0.004%
XVIII 7 0 3 0 16 120 0.011%
XIX 7 1 1 1 16 720 0.069%
XX 4 6 0 0 16 210 0.020%
XXI 6 3 0 1 16 840 0.080%
XXII 6 2 2 0 16 1,260 0.120%
XXIII 5 4 1 0 16 1,260 0.120%
XXIV 3 7 0 0 17 120 0.011%
XXV 7 0 2 1 17 360 0.034%
XXVI 7 1 0 2 17 360 0.034%
XXVII 6 1 3 0 17 840 0.080%
XXVIII 6 2 1 1 17 2,520 0.240%
XXIX 5 4 0 1 17 1,260 0.120%
XXX 4 5 1 0 17 1,260 0.120%
XXXI 5 3 2 0 17 2,520 0.240%
XXXII 2 8 0 0 18 45 0.004%
XXXIII 7 0 1 2 18 360 0.034%
XXXIV 6 0 4 0 18 210 0.020%
XXXV 3 6 1 0 18 840 0.080%
XXXVI 6 2 0 2 18 1,260 0.120%
XXXVII 6 1 2 1 18 2,520 0.240%
XXXVIII 4 5 0 1 18 1,260 0.120%
XXXIX 5 2 3 0 18 2,520 0.240%
XL 5 3 1 1 18 5,040 0.481%
XLI 4 4 2 0 18 3,150 0.300%
XLII 1 9 0 0 19 10 0.001%
XLIII 7 0 0 3 19 120 0.011%
XLIV 2 7 1 0 19 360 0.034%
XLV 6 0 3 1 19 840 0.080%
XLVI 3 6 0 1 19 840 0.080%
XLVII 6 1 1 2 19 2,520 0.240%
XLVIII 5 1 4 0 19 1,260 0.120%
XLIX 5 3 0 2 19 2,520 0.240%
L 3 5 2 0 19 2,520 0.240%
LI 5 2 2 1 19 7,560 0.721%
LII 4 4 1 1 19 6,300 0.601%
LIII 4 3 3 0 19 4,200 0.401%
LIV 0 10 0 0 20 1 0.000%
LV 1 8 1 0 20 90 0.009%
LVI 2 7 0 1 20 360 0.034%
LVII 6 1 0 3 20 840 0.080%
LVIII 6 0 2 2 20 1,260 0.120%
LIX 2 6 2 0 20 1,260 0.120%
LX 5 0 5 0 20 252 0.024%
LXI 5 1 3 1 20 5,040 0.481%
LXII 3 5 1 1 20 5,040 0.481%
LXIII 5 2 1 2 20 7,560 0.721%
LXIV 4 4 0 2 20 3,150 0.300%
LXV 4 2 4 0 20 3,150 0.300%
LXVI 3 4 3 0 20 4,200 0.401%
LXVII 4 3 2 1 20 12,600 1.202%
LXVIII 0 9 1 0 21 10 0.001%
LXIX 1 8 0 1 21 90 0.009%
LXX 1 7 2 0 21 360 0.034%
LXXI 6 0 1 3 21 840 0.080%
LXXII 2 6 1 1 21 2,520 0.240%
LXXIII 5 0 4 1 21 1,260 0.120%
LXXIV 4 1 5 0 21 1,260 0.120%
LXXV 5 2 0 3 21 2,520 0.240%
LXXVI 3 5 0 2 21 2,520 0.240%
LXXVII 2 5 3 0 21 2,520 0.240%
LXXVIII 5 1 2 2 21 7,560 0.721%
LXXIX 3 3 4 0 21 4,200 0.401%
LXXX 4 3 1 2 21 12,600 1.202%
LXXXI 4 2 3 1 21 12,600 1.202%
LXXXII 3 4 2 1 21 12,600 1.202%
LXXXIII 0 9 0 1 22 10 0.001%
LXXXIV 0 8 2 0 22 45 0.004%
LXXXV 1 7 1 1 22 720 0.069%
LXXXVI 6 0 0 4 22 210 0.020%
LXXXVII 4 0 6 0 22 210 0.020%
LXXXVIII 1 6 3 0 22 840 0.080%
LXXXIX 2 6 0 2 22 1,260 0.120%
XC 5 0 3 2 22 2,520 0.240%
XCI 3 2 5 0 22 2,520 0.240%
XCII 5 1 1 3 22 5,040 0.481%
XCIII 2 5 2 1 22 7,560 0.721%
XCIV 2 4 4 0 22 3,150 0.300%
XCV 4 1 4 1 22 6,300 0.601%
XCVI 4 3 0 3 22 4,200 0.401%
XCVII 3 4 1 2 22 12,600 1.202%
XCVIII 4 2 2 2 22 18,900 1.802%
XCIX 3 3 3 1 22 16,800 1.602%
C 0 8 1 1 23 90 0.009%
C I 0 7 3 0 23 120 0.011%
C II 1 7 0 2 23 360 0.034%
C III 3 1 6 0 23 840 0.080%
C IV 1 6 2 1 23 2,520 0.240%
C V 5 1 0 4 23 1,260 0.120%
C VI 1 5 4 0 23 1,260 0.120%
C VII 4 0 5 1 23 1,260 0.120%
C VIII 5 0 2 3 23 2,520 0.240%
C IX 2 3 5 0 23 2,520 0.240%
C X 2 5 1 2 23 7,560 0.721%
C XI 3 4 0 3 23 4,200 0.401%
C XII 4 2 1 3 23 12,600 1.202%
C XIII 4 1 3 2 23 12,600 1.202%
C XIV 2 4 3 1 23 12,600 1.202%
C XV 3 2 4 1 23 12,600 1.202%
C XVI 3 3 2 2 23 25,200 2.403%
C XVII 0 8 0 2 24 45 0.004%
C XVIII 3 0 7 0 24 120 0.011%
C XIX 0 7 2 1 24 360 0.034%
C XX 0 6 4 0 24 210 0.020%
C XXI 2 2 6 0 24 1,260 0.120%
C XXII 1 6 1 2 24 2,520 0.240%
C XXIII 5 0 1 4 24 1,260 0.120%
C XXIV 1 4 5 0 24 1,260 0.120%
C XXV 2 5 0 3 24 2,520 0.240%
C XXVI 1 5 3 1 24 5,040 0.481%
C XXVII 3 1 5 1 24 5,040 0.481%
C XXVIII 4 0 4 2 24 3,150 0.300%
C XXIX 4 2 0 4 24 3,150 0.300%
C XXX 4 1 2 3 24 12,600 1.202%
C XXXI 2 3 4 1 24 12,600 1.202%
C XXXII 2 4 2 2 24 18,900 1.802%
C XXXIII 3 3 1 3 24 16,800 1.602%
C XXXIV 3 2 3 2 24 25,200 2.403%
C XXXV 0 7 1 2 25 360 0.034%
C XXXVI 2 1 7 0 25 360 0.034%
C XXXVII 0 6 3 1 25 840 0.080%
C XXXVIII 1 6 0 3 25 840 0.080%
C XXXIX 3 0 6 1 25 840 0.080%
C XL 1 3 6 0 25 840 0.080%
C XLI 5 0 0 5 25 252 0.024%
C XLII 0 5 5 0 25 252 0.024%
C XLIII 1 5 2 2 25 7,560 0.721%
C XLIV 2 2 5 1 25 7,560 0.721%
C XLV 4 1 1 4 25 6,300 0.601%
C XLVI 1 4 4 1 25 6,300 0.601%
C XLVII 4 0 3 3 25 4,200 0.401%
C XLVIII 3 3 0 4 25 4,200 0.401%
C XLIX 2 4 1 3 25 12,600 1.202%
C L 3 1 4 2 25 12,600 1.202%
576 , 048 , 1
N
r
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
C LI 3 2 2 3 25 25,200 2.403%
C LII 2 3 3 2 25 25,200 2.403%
C LIII 2 0 8 0 26 45 0.004%
C LIV 0 7 0 3 26 120 0.011%
C LV 1 2 7 0 26 360 0.034%
C LVI 0 4 6 0 26 210 0.020%
C LVII 0 6 2 2 26 1,260 0.120%
C LVIII 2 1 6 1 26 2,520 0.240%
C LIX 0 5 4 1 26 1,260 0.120%
C LX 4 1 0 5 26 1,260 0.120%
C LXI 3 0 5 2 26 2,520 0.240%
C LXII 1 5 1 3 26 5,040 0.481%
C LXIII 1 3 5 1 26 5,040 0.481%
C LXIV 4 0 2 4 26 3,150 0.300%
C LXV 2 4 0 4 26 3,150 0.300%
C LXVI 1 4 3 2 26 12,600 1.202%
C LXVII 3 2 1 4 26 12,600 1.202%
C LXVIII 2 2 4 2 26 18,900 1.802%
C LXIX 3 1 3 3 26 16,800 1.602%
C LXX 2 3 2 3 26 25,200 2.403%
C LXXI 1 1 8 0 27 90 0.009%
C LXXII 0 3 7 0 27 120 0.011%
C LXXIII 2 0 7 1 27 360 0.034%
C LXXIV 0 6 1 3 27 840 0.080%
C LXXV 1 2 6 1 27 2,520 0.240%
C LXXVI 1 5 0 4 27 1,260 0.120%
C LXXVII 0 4 5 1 27 1,260 0.120%
C LXXVIII 4 0 1 5 27 1,260 0.120%
C LXXIX 0 5 3 2 27 2,520 0.240%
C LXXX 3 2 0 5 27 2,520 0.240%
C LXXXI 2 1 5 2 27 7,560 0.721%
C LXXXII 3 0 4 3 27 4,200 0.401%
C LXXXIII 1 4 2 3 27 12,600 1.202%
C LXXXIV 1 3 4 2 27 12,600 1.202%
C LXXXV 3 1 2 4 27 12,600 1.202%
C LXXXVI 2 3 1 4 27 12,600 1.202%
C LXXXVII 2 2 3 3 27 25,200 2.403%
C LXXXVIII 1 0 9 0 28 10 0.001%
C LXXXIX 0 2 8 0 28 45 0.004%
C XC 1 1 7 1 28 720 0.069%
C XCI 0 6 0 4 28 210 0.020%
C XCII 4 0 0 6 28 210 0.020%
C XCIII 0 3 6 1 28 840 0.080%
C XCIV 2 0 6 2 28 1,260 0.120%
C XCV 0 5 2 3 28 2,520 0.240%
C XCVI 2 3 0 5 28 2,520 0.240%
C XCVII 3 1 1 5 28 5,040 0.481%
C XCVIII 1 2 5 2 28 7,560 0.721%
C XCIX 0 4 4 2 28 3,150 0.300%
C C 1 4 1 4 28 6,300 0.601%
CC I 3 0 3 4 28 4,200 0.401%
CC II 2 1 4 3 28 12,600 1.202%
CC III 2 2 2 4 28 18,900 1.802%
CC IV 1 3 3 3 28 16,800 1.602%
CC V 0 1 9 0 29 10 0.001%
CC VI 1 0 8 1 29 90 0.009%
CC VII 0 2 7 1 29 360 0.034%
CC VIII 3 1 0 6 29 840 0.080%
CC IX 1 1 6 2 29 2,520 0.240%
CC X 0 5 1 4 29 1,260 0.120%
CC XI 1 4 0 5 29 1,260 0.120%
CC XII 0 3 5 2 29 2,520 0.240%
CC XIII 2 0 5 3 29 2,520 0.240%
CC XIV 3 0 2 5 29 2,520 0.240%
CC XV 2 2 1 5 29 7,560 0.721%
CC XVI 0 4 3 3 29 4,200 0.401%
CC XVII 1 2 4 3 29 12,600 1.202%
CC XVIII 2 1 3 4 29 12,600 1.202%
CC XIX 1 3 2 4 29 12,600 1.202%
CC XX 0 0 10 0 30 1 0.000%
CC XXI 0 1 8 1 30 90 0.009%
CC XXII 1 0 7 2 30 360 0.034%
CC XXIII 3 0 1 6 30 840 0.080%
CC XXIV 0 2 6 2 30 1,260 0.120%
CC XXV 2 2 0 6 30 1,260 0.120%
CC XXVI 0 5 0 5 30 252 0.024%
CC XXVII 1 1 5 3 30 5,040 0.481%
CC XXVIII 1 3 1 5 30 5,040 0.481%
CC XXIX 2 1 2 5 30 7,560 0.721%
CC XXX 2 0 4 4 30 3,150 0.300%
CC XXXI 0 4 2 4 30 3,150 0.300%
CC XXXII 0 3 4 3 30 4,200 0.401%
CC XXXIII 1 2 3 4 30 12,600 1.202%
CC XXXIV 0 0 9 1 31 10 0.001%
CC XXXV 3 0 0 7 31 120 0.011%
CC XXXVI 0 1 7 2 31 360 0.034%
CC XXXVII 1 0 6 3 31 840 0.080%
CC XXXVIII 1 3 0 6 31 840 0.080%
CC XXXIX 2 1 1 6 31 2,520 0.240%
CC XL 0 4 1 5 31 1,260 0.120%
CC XLI 0 2 5 3 31 2,520 0.240%
CC XLII 2 0 3 5 31 2,520 0.240%
CC XLIII 1 2 2 5 31 7,560 0.721%
CC XLIV 1 1 4 4 31 6,300 0.601%
CC XLV 0 3 3 4 31 4,200 0.401%
CC XLVI 0 0 8 2 32 45 0.004%
CC XLVII 2 1 0 7 32 360 0.034%
CC XLVIII 0 4 0 6 32 210 0.020%
CC XLIX 0 1 6 3 32 840 0.080%
CC L 2 0 2 6 32 1,260 0.120%
CC LI 1 2 1 6 32 2,520 0.240%
CC LII 1 0 5 4 32 1,260 0.120%
CC LIII 0 3 2 5 32 2,520 0.240%
CC LIV 1 1 3 5 32 5,040 0.481%
CC LV 0 2 4 4 32 3,150 0.300%
CC LVI 0 0 7 3 33 120 0.011%
CC LVII 2 0 1 7 33 360 0.034%
CC LVIII 1 2 0 7 33 360 0.034%
CC LIX 0 3 1 6 33 840 0.080%
CC LX 1 1 2 6 33 2,520 0.240%
CC LXI 0 1 5 4 33 1,260 0.120%
CC LXII 1 0 4 5 33 1,260 0.120%
CC LXIII 0 2 3 5 33 2,520 0.240%
CC LXIV 2 0 0 8 34 45 0.004%
CC LXV 0 3 0 7 34 120 0.011%
CC LXVI 1 1 1 7 34 720 0.069%
CC LXVII 0 0 6 4 34 210 0.020%
CC LXVIII 1 0 3 6 34 840 0.080%
CC LXIX 0 2 2 6 34 1,260 0.120%
CC LXX 0 1 4 5 34 1,260 0.120%
CC LXXI 1 1 0 8 35 90 0.009%
CC LXXII 0 2 1 7 35 360 0.034%
CC LXXIII 1 0 2 7 35 360 0.034%
CC LXXIV 0 1 3 6 35 840 0.080%
CC LXXV 0 0 5 5 35 252 0.024%
CC LXXVI 0 2 0 8 36 45 0.004%
CC LXXVII 1 0 1 8 36 90 0.009%
CC LXXVIII 0 1 2 7 36 360 0.034%
CC LXXIX 0 0 4 6 36 210 0.020%
CC LXXX 1 0 0 9 37 10 0.001%
CC LXXXI 0 1 1 8 37 90 0.009%
CC LXXXII 0 0 3 7 37 120 0.011%
CC LXXXIII 0 1 0 9 38 10 0.001%
CC LXXXIV 0 0 2 8 38 45 0.004%
CC LXXXV 0 0 1 9 39 10 0.001%
CC LXXXVI 0 0 0 10 40 1 0.000%
576 , 048 , 1
N
r
4 , 10 r N
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
N r r
N
3 4 6 . 4 x 1 0
1
1 5 4 1 . 0 7 3 7 4 1 8 2 4 x 1 0
9
4 1 5 5 . 0 6 2 5 x 1 0
4
5 0 3 0 7 . 1 7 8 9 7 9 8 7 6 9 1 8 5 3 x 1 0
7 3
1 , 0 0 0 1 0 0
6 . 0 x 1 0
2 3
1 . 0 x 1 0
1 0
3 3
1 0 6
1 0 0 . 1
x
x
0 0 0 , 2
1 0 0 . 1 x
Problem 6.4
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Boltzman Hypothesis
where
S is the entropy.
is the # of microstates in a macrostate.
The Boltzman constant, k = R/N
O
.
N
O
is Avogardos number.
R is the ideal gas constant.
Provides a sharp extremum.
Range is compressed by assuming logarithmic relation.
Average energy of particles is fixed.
ln k S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Probl e m 6. 5
n 0 1 2 3 4 5 6 7 8 9
n+ 1/ 2 0. 5 1. 5 2. 5 3. 5 4. 5 5. 5 6. 5 7. 5 8. 5 9. 5 N U

1
0 0 1 2 4 2 1 0 0 0 10 45 37, 800

2
0 1 1 2 2 2 1 1 0 0 10 45 453, 600

n 0 1 0 0 -2 0 0 1 0 0 0

U 0 1. 5 0 0 -9 0 0 7. 5 0 0 0
0 U
12 ln ln
1
2
k k S

,
_

0 N
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Find Conditions for
Equilibrium

Find an expression for change in entropy of

the system.

Determine the constraints.

Apply the constraints and the extremum

criterion:
. 0 ) (
i
n dS

Solve the remaining equations for the

conditions for equilibrium.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Find an expression for dS(n
i
)
Substitute for :
1
1
1
1
]
1

r
i 1
i
! n
N!
ln k S
Expand:
1
]
1

r
1 i
i
! n ln - N! ln k S
Note the Stirling approximation:
x - x ln x x! ln
1
]
1

+

r
1 i
i
r
1 i
i i
n n ln n N - N ln N k S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Find an expression for dS(n
i
)
Rearranging:
Note:

r
1 i
i
n N
1
]
1

r
1 i
i i
N ln N n ln n k S
and x ln -
x
1
ln
1
]
1

,
_

r
1 i
i
i
N
n
ln n k S
Taking the
derivative:
1
]
1

,
_

r
1 i
i
N
n
ln k dS
i
dn
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Isolation Constraints
Consider an isolated system.
Closed system ---

r
1 i
i sys
n N

r
1 i
i i sys
n e U
Insulated system ---

r
1 i
i
? V
Rigid system ---
0 d? dV
r
1 i
i

Closed system ---

Insulated system ---
Rigid system ---
0 dn e n e d dU
r
1 i
i i
r
1 i
i i sys

0 dn dN
r
1 i
i sys

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Constrained Maximum Entropy
Apply Lagrange multipliers to constraints &
add to condition for entropy maximum.
Rearrange, raise to power of e to yield r equations:
0 dU dN dS
sys sys
r) , 1,2, (i ]
k
e
exp[ ]
k
exp[
N
n
i
sys
i


Substitute for entropy and constraints:
0 dn e dn
N
n
ln k
r
1 i
r
1 i
i i i
r
1 i
i

+ +

,
_

i
dn
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Constrained Maximum Entropy

r
1 i
i sys
n N

r
1 i
sys
i
N
n
1
Apply:
and
Solve for :
P
1
k
e
exp
k
exp
1
r
1 i
i

1
]
1

,
_

,
_

k
e
exp Function Partition
r
1 i
i

,
_

P
Define:
Yielding:
P
1
]
1

k
e
exp

N
n
i
sys
i

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
i
dn PdV TdS dU
By analogy.
Compare phenomenological & statistical
expressions for dS to evaluate & :
Constrained Maximum Entropy

+
r
1 i
i
dn P
r
i
i i
k dn e dS
1
ln
sys
N k dU dS Pd ln
sys
N
T
dV
T
p
dU
T
dS d
1
T
1
P ln k
T
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
All equilibrium thermodynamic functions can be
derived if the partition function is known.
Complete expression equilibrium distribution
of particles over energy levels:
Constrained Maximum Entropy
1
]
1

kT
e -
exp
1

N
n
i
sys
i
P

kT
e
exp Function Partition
r
1 i
i

P
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Problem 6.6
N 10 20 30 60 80 100 150 170
Ex a ct N! 3.63E+062.43E+182.65E+328.32E+817.16E+1189.33E+1575.71E+2627.26E+306
Ex a ct lnN! 1.51E+014.23E+017.47E+011.89E+02 2. 74E+02 3.64E+02 6.05E+02 7.07E+02
Stirling NlnN-N 1.30E+013.99E+017.20E+011.86E+02 2. 71E+02 3.61E+02 6.02E+02 7.03E+02
Stirling N! 4.54E+052.16E+171.93E+314.28E+803.19E+1173.72E+1561.86E+2612.22E+305
%err -13.76% -5.72% -3.51% -1.57% -1.14% -0.89% -0.57% -0.49%
Probl e m 6. 7
i 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 N l n

n
i
14 18 27 38 51 78 67 54 32 27 23 20 19 17 15 500 -1. 36E + 03

n
i
0 0 -1 -1 -2 0 1 1 2 2 1 0 -1 -1 -1 0 -1. 86E + 00
n
i
/
14 18 26 37 49 78 68 55 34 29 24 20 18 16 14 500 -1. 36E + 03
l n(n
i
/ N)

n
i
0. 00 0. 00 2. 92 2. 58 4. 57 0. 00 -2. 01 -2. 23 -5. 50 -5. 84 -3. 08 0. 00 3. 27 3. 38 3. 511. 57
( ) K mole J x k k S

,
_

/ 10 57 . 2 ln ln ln
23
1 2
1
2
K mole J x n
N
n
k S
i
r
i
O
i

,
_

/ 10 17 . 2 ln
23
1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Thermodynamic Functions in
Terms of Partition Function
1
1
]
1

,
_

r
1 i
sys
i
i
N
n
ln n k S
kT
e -
exp
1

N
n
i
sys
i
P

+
r
1 i
P
1
1
ln
T
1
S n k n e
r
i
i i
sys
N k U P ln
T
1
S +
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Thermodynamic Functions in
Terms of Partition Function
Deduce F from S:
ln kT N - F
sys
P
Apply:

T
F
- S
V

,
_

V
T
kT
P ln
N ln k N S
sys sys
P
TS - F U
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Thermodynamic Functions in
Terms of Partition Function
Apply:

T
U
C
V
V

,
_

V
T
kT
2
2
2
sys V sys V
ln
N
T
ln
T k 2N C
P P
Apply:
TS U F
V
T
kT
P ln
N U
2
sys
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Monatomic Gas Model
Assumptions:
All particles are identical.
Volume = l
x
x l
y
x l
z
Energy of the system is not quantized & is
equal to kinetic energies of the particles.

z z y y x x dv kT mv dv kT mv dv kT mv
lx
dxdydz
ly
lz
) 2 /
2
( exp[ ) 2 /
2
( exp[ ) 2 /
2
( exp[
0 0 0
P
3/2
m
kT 2
V
1
]
1

P
2
v m
2
1
KE
1/2
x
-
2
m
kT 2
dv
2
exp
1
]
1

,
_

x
v
kT
m
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Thermodynamic Properties
of Ideal Monatomic Gases
Apply

'

1
]
1

3/2
m
kT 2
V ln ln

P
T
1
2
3

T
ln
V

,
_

P
ln kT N - F
sys
P
1
1
]
1

,
_

3/2
sys
m
kT 2
V ln kT N - F

Apply
V
T
kT

,
_

+
P ln
N ln k N S
sys sys
P
k N
2
3

m
kT 2
V ln k N S
sys
3/2
sys
+
1
1
]
1

,
_

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
kT N
2
1
U
O

R
2
3
k N
2
3
C
O V
Thermodynamic Properties
of Ideal Monatomic Gases
V
T
kT

,
_

P ln
N U
2
sys
Apply:
Apply:

T
U
C
V
V

,
_

Equipartition of energy:
freedom of degree per kT
2
1
U
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Einsteins Model of a Crystal
Consider a simple cubic crystal --- 6 nearest
neighbors, 1 atom & 3 bonds per unit cell.
Hypothesis --- Energy of crystal is the sum of the
energies of its bonds. The atoms vibrate
around equilibrium positions as if bound by
vibrating springs. Only certain vibrational
frequencies are allowed in coupled springs.
The energies (
i
) of the bonds are proportional
to their vibrational frequencies ().

i
= (i + 1/2) h
where h = Plancks constant.
The adjustable parameter is set by assuming an
Einstein temperature:
E
= h/k
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
Einsteins Model of a Crystal

1
1
1
]
1

r
0 i
kT
h )
2
1
(i
- exp

P
Evaluate
the
partition
function:
i
r
i
1
]
1

,
_

1
]
1

0
kT
h
- exp
kT
h
2
1
- exp

P Factor:
Approximate
as infinite
series:
i
i

1
]
1

,
_

1
]
1

kT
h
- exp
kT
h
2
1
- exp

P

,
_

1
]
1

kT
h

exp 1
1
kT
h
2
1
- exp P
Substitute
for infinite
series:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
1
]
1

,
_

2kT
h
- exp - 1 ln -
kT
h
2
1
- ln

P
Einsteins Model of a Crystal
Take ln of
both sides:
For simple cubic:
O sys
N N 3
Apply
ln kT N - F
sys
P
1
]
1

,
_

+
kT
h
kT N
O

exp 1 ln 3 h N
2
3
F
O
Apply
V
T
kT

,
_

+
P ln
N ln k N S
sys sys
P
exp - 1 ln k 3N -
exp - 1
exp
k 3N S
O O 1
]
1

,
_

,
_

,
_

,
_

kT
h
kT
h
kT
h
kT
h

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
2
2
O
exp 1
exp
kT
h
3N C
1
]
1

,
_

,
_

,
_

kT
h
kT
h
k
V

V
T
kT

,
_

P ln
N U
2
sys
Apply
Einsteins Model of a Crystal
1
1
1
1
]
1

,
_

,
_

kT
h
kT
h

exp 1
exp 1
h N
2
3
U
O
Apply:

T
U
C
V
V

,
_