Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah

1

Heat Capacities of Solids
Experimental Facts
- Cp is measured (subject to atmosphere pressure)
- Cv is calculated easily from dE/dT from stat mech
- At the end of Chapter 5, there is a relation for the exact expression relating Cv and Cp.
2
0
0
1 1

T P V
P T T
TV V V
K C C
V T V P K
|
|
c c | | | |
=
| |
c c
\ . \ .

for a perfect gas:
P V
C C R =
- At room temperature, the heat capacity of most solids is close to 3k
B
per atom.
- The molar heat capacity of most solids at room temperature is:
-23 -1
-1 -1
~ 3 3
where
number of atoms per molecule
number of molecules in the solid
Boltzmann constant 1.38 10 J K
Gas Constant 8.314 J K mol
P B
B
C nNk nR
n
N
k
R
=
=
=
=
=

- Some experimental measurements:
Table 6.1 Molar Heat Capacity
( )
-1 -1
J mol K at 298 K
P
C
Follow Rule Exceptions
Element Cp (J /K mol) Element Cp (J /K mol)
Al 24.4 S 22.7
Au 25.4 Si 19.9
Cu 24.5 C(Diamond) 6.1

- At low temperatures, the heat capacities decrease and are zero at T=0K.
- Heat capacities can be fit to the functional form:
3
3
where
contribution due to lattice vibrations
contribution due to conduction electrons
V
C T T
T
T
o
o

= +
=
=

- Examples: KCl has
3
0,
V
C T o = = characteristic of insulators; Copper has both terms
because it is a conductor.

Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
2

Dulong and Petits Law
Dulong and Petits Law states that at room temperature (for most solids):
-1 -1
~ 3
~ 24.9 J mol K for molecules with 1 atom
P
P
C nR
C

The table above shows the rule followers and the exceptions.
Classical statistical mechanics, using equipartition theorem leads to the constant atomic heat capacity
3R at all temperatures, in violation of experiments and the third law.
Phenomena that give rise to Heat Capacity
Contributions arise from:
- Lattice vibrations of crystalline solids
- Conduction electrons
- Orientational ordering in paramagnetic salts
Here only considering lattice vibrations. We are not considering heat capacity of conduction electrons
because we need to have the Fermi dirac statistics that we get towards the end of the course.
Equipartition Theorem and Dulong-Petit Law
The internal energy of a solid is dominated by 3 independent vibrations. By equipartition theory, the
vibrational energy of an atom is 3kT. The vibrational energy of N atoms is 3NkT. Thus:
-23 -1
3
where
number of atoms per molecule
number of molecules in the solid
Boltzmann constant 1.38 10 J K
vib vib
V B
B
E
C nNk
T
n
N
k
c
= =
c
=
=
=

Vibrational Heat Capacity
The number of degrees of freedom are the number of vibrational states.
Theorem of classical mechanics, for small oscillations for any system with normal coordinates, you can
write the vibrational energy as the sum of simple harmonic oscillator energies:
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
3

2 3
2 2
1
1
2 2
the normal coordinate
the canonical momentum
N
p
E m q
m
q
L
p
q
o
o o o
o
o
o
o
o
e
=
| |
= +
|
\ .
=
c
= =
c

The amplitude can be anything so that E .
Energy of radiation in a cavity is also the sum of oscillators, but over infinite degrees of freedom. The
electromagnetic field DOF is as N .
According to quantum mechanics, the energy of a harmonic oscillator is:
( )
3 3
1
2
1 1
N N
E n
o o o
o o
c e
= =
= = +



Math Tools Used to solve:
( )
( )
( )
2 3
2 3 4
2 3
1 ...
...
1
1 1
1
1
1
1 ...
1
y y y
y
let
S x x x
Sx x x x x
S Sx
S x
S
x
e e e
e

= + + + +
= + + +
=
=
=

+ + + + =

34
1.055 10 Js
2
h
t

= =
To solve:
1. Regard it as a system and a heat bath, where 1 harmonic oscillator is the system and the rest of
the oscillators are the heat bath. There are 3N normal modes of e
o
, just take one as the system.
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
4

2. Apply the partition function using:
( )
1
2
3
1
1
canonical partition function
1 1
non-degenerate quantum states
r B
r B r
B
N
E k T
r
E k T E
r
n k T
Z e
p e e
Z Z
Z e
o o
|
e
o
o

+
=
=
= =
=

3. Although it is infinite, the summation can be evaluated using the summation trick.
2
1
1
B
B
k T
k T
Z e
e
o
o
e
o e

4. Once you have the partition function, you can get <E> and a bunch of other parameters. Here
we are getting the average energy of a simple harmonic oscillator in thermal equilibrium with a
heat bath.
ln
ln 1 1 1
1 2 1 2
B
B B
r r
r
k T
k T k T
Z
E p E
Z Z e
Z e e
o
o o
e
o o o o
o o o e e
|
e e
c e e
| |

c
= =
c
c c
= = = + = +
c c

5. If we neglect the zero point energy:
1
B
k T
e
o
o
o e
e
c =

6. Show that in the high temperature limit we get the classical limit of this quantum mechanical
expression, and therefore, Dulong-Petits rule is obtained from the classical limit.
2
as 0, 1 at any temperature!
1 ...
1
B
B
B
k T
B B
B k T
B
k T
e
k T k T
k T
e k T
o
o
o
e o o
o o
o e
o
e
e e
e e
c
e

| |
+ + +
|
\ .
= = =

7. Using the exact expression (no approximations) the heat capacity can be found:
( )
( )
( )
( )
3 3
1 1
3
2 2
1
2
3
2
1
dimensionless sum
1
1
1
1
1
B
B
B
B
B
N N
k T
N
k T
V
k T
V
k T N
V
k T
E
e
E
C e
T k T
e
e
C k
kT
e
o
o
o
o
o
o
o e
o o
e o o
e
o
e
o
e
o
e
c
e e
e
= =
=
=
= =

c | |
= =
|
c
\ .

| |
=
|
\ .

Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
5

8. Simplification of Cv is possible in the classical limit.
( )
2
3 3
2
1 1
for all '
1 3
1
B
B
k T N N
V
k T
T s
k
e
C k k Nk
kT
e
o
o
o
o
e
o
e
o o
e
e
e
= =
| |
= = =
|
\ .



This shows that the Dulong-Petit rule is explained by simple harmonic oscillators where hw/kT << 1. The
E
e depend on the interatomic forces. Atmospheric pressure gives a different between Cp and there is
an exact relation for Cp and Cv above.
Einsteins Model Class Notes
Einstein made the approximation that all the
o
e are the same:
for all
E o
e e o =
Then the summation above is greatly simplified:
( ) ( )
( )
( )
3 3
1 1
2 2
3 3
2 2
1 1
2
3
2
1
2
2
1
1 1
1
1
3
1
B
B E B
E B B
E B
E B
E B
E B
N N
k T
k T k T N N
E
V
k T k T
V
k T N
E
V
k T
k T
E
V
k T
E
e
E e e
C k k
T kT kT
e e
e
C k
kT
e
e
C k N
kT
e
o
o
o
o
o e
o o
e e
o
e e
o o
e
e
o
e
e
e
c
e e
e
e
= =
= =
=
= =

c | | | | | |
= = =
| | |
c
\ . \ . \ .

| |
=
|
\ .

| |
=
|
\ .

Einstein was able to calculate
E
e for an elastic solid. He defined the Einstein temperature (derived
later) as a characteristic property of the solid.
E
E
k
e
O =
( )
2
2
3
1
E
E
T
E
V
T
e
C Nk
T
e
O
O
O | |
=
|
\ .

Einsteins Model Book Notes Mandl
Einstein made the approximation that all the
o
e are the same and that they vibrate independently of
eachother:
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
6

for all
E o
e e o =
This models the system as a system of atoms vibrating about lattice sites with the equations of motion,
where the
E
e depends on the strength of the restoring force acting on the atom:
2
0 for all
E
r r
o o
e o + =
Einstein treated the 3N independent oscillators using quantum theory:
1
for all , 0,1, 2,...
2
E
n n
o o o
c e o
| |
= + =
|
\ .

The oscillators are assumed to be non-interacting (except for the weak interaction that establishes
thermal equilibrium), and there is a zero-point energy arising from Heisenbergs uncertainty principle.
Any atom in the solid at temperature T can be regarded as a system in a heat bath at temperature T.
The partition function for one oscillator:
1
2
2 2
0 0 0
1
E
n
E
x
n
x xn
n x
n n n
E
E
Z e
e
Z e e e e
e
x
kT
o
|
o
| e
|c
e
| e

| |

+
|

\ .

= = =

= = = =

= =

From the definition of the Helmholtz free energy:
( ) ( ) ( )
( )
( )
2
2
ln ln ln ln 1
1
ln 1
2
1
ln 1
2
E
x
x x
n x
x
E
e
F kT Z kT kT e e
e
kTx
F kT e
F e
| e
e
|

| |
(
= = =
|

\ .
= +
= +

From the definition of the mean energy of the system in its heat bath we get the mean energy per
oscillator:
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
7

( )
( )
ln
ln
ln 1
2
2 1
E
E
r r
r
n E
E E
Z
E p E
F
Z
e
e
| e
| e
|
|
e |
c
| | |
e e
c

c
=
c
c
c c
= = = +
`
c c c
)
= +

Energy is extensive, and for N atoms there are 3N oscillators:
3 3
3
2 1
E
E E
N N
E N
e
| e
e e
c = = +

From the energy, you can get the heat capacity at constant volume:
( )
( )
( )
( )
2
2
2
2 2
2
2
1
3 3
1
3
2 1
1
3
1
3
1
E
E
E
V V
V
V V
E E
V
E
V
x
V
x
E
C C T N N
T T kT
C N
kT e
e
C N
kT
e
x e
C Nk
e
| e
| e
| e
c | c
| |
e e
|
e
| | | | c c c c | |
= = = =
| | |
c c c c
\ .
\ . \ .
c | |
= +
|
c
\ .
=

Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
8

Matlab plot generated with this code (note that x-axis is 1/x, that is T/O
E
). Note: Cv/3R = 0.92 at T=O
E
so
Dulong and Petits Law holds at roughly room temperatures because the Einstein temperature for most
substances is about 200 to 300 K.
gcf = figure(3);
hold off;t = zeros(101);Cv = zeros(101);
for i=0:100
x=100.0/i;
t(i+1)=1/x;
Cv(i+1) = x*x*exp(x)/(exp(x)-1)^2;
end
plot(t,Cv,'color','b');
ylim([0 1]);
xlim([0 1]);
title(['Einstein Model']);
ylabel('C_V/3R');
xlabel('T/\Theta_E');

The high temperature limit:
( )
( )
( )
( )
2
2
2 2
1
2
2
0 2
1
2
3
1
1
1
lim3 3 1 3
x
E E
V
x
E
V
x
x e
C Nk x
kT T
e
T x
x x x
C Nk Nk Nk
x x
e

O
=

O
+ + +
= = =
+ +

This is the classical limit, and Dulong-Petits Law.
The low temperature limit goes to zero as T goes to zero as required by the third law of
thermodynamics:
( )
( )
2
2
2
2 2
2
2 2
3
1
1
lim3 3 3 3
1
E
x
E E
V
x
E
x x
x T E
V x
x x
x e
C Nk x
kT T
e
T x
x e x e
C Nk Nk Nkx e Nk e
e T
e
e
O | |

\ .

O
=

O
O | |
= = = =
|
\ .

Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
9



gcf = figure(3);
hold off;t = zeros(101);Cv = zeros(101);
for i=0:100
x=100.0/i;
t(i+1)=1/x;
Cv(i+1) = x*x*exp(-x);
end
plot(t,Cv,'color','b');
ylim([0 1]);
xlim([0 1]);
title(['Einstein Model Low Temperature Limit']);
ylabel('C_V/3R');
xlabel('T/\Theta_E');

Einsteins temperature can be estimated from the elastic constants of a solid:
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
10

2 2
1 2
1 2
1 3
0 1 6 1 3
3
stress
strain
stress/strain Young's modulus
mass
constant of the material
displacement from equilibrium
interatomic distance
dens
E E
E
E
x
kT T
m x a
x a
aY Y
A AN
m M
Y
m a
A
x
a
e
o e
c
e

o
c
o c

O

| |
=
|
\ .
=
=
=
=
=
=
=
=
0
ity
gram-atomic weight M M mN = =

The speed of sound is related to youngs modulus, so the Einstein temperature can also be related to
the speed of sound (velocity of plane elastic waves in an isotropic medium longitudinal waves in a thin
rod):
0
0
E
Y
v
v
A
a

e
=
=

Debyes Model Class Notes
Debyes model is successful at low temperatures and works best for small normal mode frequencies.
Treat the solid as a homogeneous medium. Elastic waves modeled by wave equations:
2
2
2 2
1
0
displacement of atom in solid
phase velocity of wave
phase
phase
v t
v

c
V =
c
=
=

For standing waves:
Notes from October 23 and 28, 2008 and Chapter 6 of Mandl & Chapter 4 of Kittel Meg Noah
11

( )
( )
( ) ( )
( ) ( )
2 2
2 2 2 2
2 2
2
2 1
1 1 1 1 1 1
2 2
2 2 2 2 2 2
3
( ) ( , , ) cos sin ( , , )
0 0 0
( ) ( ) ( )
" " "
"
cos sin ,
"
cos sin ,
"
phase phase
f t x y z A t B t x y z
k
v v
X x Y y Z z
X Y Z
k
X Y Z
n X
k X A k x B k x k
X L
n Y
k Y A k y B k y k
Y L
Z
k
Z
| e e |
e e
| |
|
t
t
= = +
| | | |
V + = V + = V + =
| |
| |
\ . \ .
=
+ + =
= = + =
= = + =
= ( ) ( )
2 3
3 3 3 3 3
2 2 2 2
1 2 3
cos sin ,
displacement of atom in solid
phase velocity of wave
phase
phase
n
Z A k z B k z k
L
k k k k
v
k v
t

e
= + =
+ + =
=
=
=

It will look like a cubic lattice with only allowed n1, n2, n3 sites. Every point on the lattice corresponds
to a normal mode. There is only 1 mode per unit cell in k space.
( )
( )
2
1
8
3
3 2 2
2 2 3
2
2 3 3
4 volume of spherical shell
#
volume of one unit cell
assume no dispersion
2 2
1 2
2
L
phase
phase
L T
k dk
k vectors
k v
d dk v
L k dk V d
n k
v
V d
dn
v v
t
t
e
e
e e
t t
e e
t
= =
=
=
= =
| |
=
|
\ .