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m v 2x + v 2y + v z 2
m 2
r
exp
dN(v, T ) =
2k BT
2 k BT
v2
]dv dv dv
= 3k BT/m
Degrees of freedom
cv
Translational
3 RT
1.5R
Rotational
3 RT
1.5R
Vibrational
6 RT
3R
Total cv = 6R
Vibration
Translation
Vibration
The table shows the vibrational
frequencies of water along with the
population of the first excited state at
600 K.
Translation
(cm-1)
Exp(-h/kBT)
3825
1.0 x 10-4
1654
1.9 x 10-2
3936
8.0 x 10-5
P( t ) = K ( t ) =
3
k BT
2
The molar internal energy is then U = 3NAkBT = 3RT and the molar
constant volume heat capacity is cv = [U/T]v =3R
Although cv for many elements at room T are indeed close to 3R, low-T
measurements found a strong temperature dependence of cv. Actually,
cv 0 as T 0 K.
U( t ) =
h
e h k B T 1
There are three degrees of freedom per oscillator, so the total internal
energy per mol is
3 N A h
U = h k BT
e
1
U
cV =
T V
h h
e
3 N A k B
k BT
=
2
e h k B T 1
k BT
e h k BT 1 +
h
k BT
cV
h h
e
3 N A k B
k BT
=
2
e h k B T 1
k BT
h
h
1 +
3 N A k B
k BT
k BT
=
2
h
k BT
3 N A k B = 3 R
= 3 N A k B 1 +
k BT
cV
T
= 9 N A k B
D
3 /T
D
(e
0
x 4e x
x
dx
124NAkB T
For low temperatures, Debye's model predicts cV =
5
D
- good agreement with experimental results.
We can see that cv depends
on T/D with D as the
scaling factor for different
materials.
T/D
D ~ D ~ strength of the
interatomic interaction, ~
1/(atomic weight).
For a harmonic oscillator
1
=
2
force constant
reduced mass
Summary (1)
Make sure you understand language and concepts:
Degrees of freedom
Equipartition of energy
Heat capacity of ideal gas
Heat capacity of solids: Dulong-Petit law
Quantum mechanical corrections: Einstein and Debye models
Summary (2)
Equipartition theory is only valid if all degrees of freedom are fully
excited.
Quantized energy levels
High T, Cv 3R
Energy
24.9
Pn ~ eE/kBT
Low T, Cv 0
T