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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
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
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
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
,
_