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Practical Calculations For Ideal Systems

The document discusses the partition function for an ideal gas system. It begins by deriving the partition function for a single particle in terms of the thermal de Broglie wavelength. It then extends this to the partition function for an ideal gas of N indistinguishable particles. The document discusses several properties that can be derived from the partition function, including the equation of state and expressions for internal energy, heat capacity, and entropy of the ideal gas. It also discusses the Gibbs paradox regarding the entropy change when mixing distinguishable versus indistinguishable gases.

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22 views20 pages

Practical Calculations For Ideal Systems

The document discusses the partition function for an ideal gas system. It begins by deriving the partition function for a single particle in terms of the thermal de Broglie wavelength. It then extends this to the partition function for an ideal gas of N indistinguishable particles. The document discusses several properties that can be derived from the partition function, including the equation of state and expressions for internal energy, heat capacity, and entropy of the ideal gas. It also discusses the Gibbs paradox regarding the entropy change when mixing distinguishable versus indistinguishable gases.

Uploaded by

W-d Dom
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Practical Calculations for Ideal

Systems

The Ideal Gas ~ Quantised Phase Space


The partition function for a particle: Z e

For closely packed states it is more convenient to


express this as an integral over the density of energy

states:

Z g ( )e d
i

For a 3D system with volume V:


1
3
V
2
2

g ( )
2m

4 2 3

1
3
V
2 2 e d

Z
2
m
2 3

4
0

V 2mkT

2
2
4

2mkT

2
h

It is instructive to write this as:

V
Z 3

where

2mkT

x
0

2 x

3
2 2

These nasty
integrals will
be provided!!

Question:
What is the
dimensionality
of Z?

The quantity is the thermal de Broglie


wavelength of the particle
A particle of momentum p has de Broglie wavelength:
h

p

h
2m tr

According to the equipartition theorem, in 3D:


3
kT
2

Therefore:

h
h

3mkT
2mkT

Condition for Classical Mechanics


The classical regime is valid when the mean
1
separation between molecules
V 3
l

is much bigger than the de Broglie wavelength

Classical: l >>
Particles appear pointlike

QM: l ~
Wavefunctions overlap and
interference effects are important

Quantum or Classical ~ You Decide!!


1. A gas under normal conditions ~ say helium at
273K and a density of 1020 molecules per cm3
2. Liquid helium which has an atomic volume
V/N~ 510-23 per cm3 per atom (the boiling point
of He = 4.2K
3. The conduction electrons in a metal at normal
temperatures. Assume one conduction electron
per atom, so V/N~10-23 cm3 per electron.

Combining Thermodynamic Quantities


Microcanonical

Canonical

S k ln

F kT ln Z

Entropies and free energies are additive:

ST S1 S 2 S3 ...
NS1

FT F1 F2 F3 ...

For N copies of the


system

NF1

Statistical weights and partition functions multiply:

T 1 2 3 ...

Z T Z1 Z 2 Z 3 ...

Take care with indistinguishable


(gas) particles!!!

Z1
ZT
N!

Partition Function for N Particles


The partition function for a single particle:
V
h
Z1 3 where

2mkT
For a gas of N particles:

1 N
ZN
Z1
N!

The N! is needed as gas particles are indistinguishable

Particles localised in a solid are distinguishable.


Particles which are free to move are not so we must
divide by N! to correctly count the states

Using Your Partition Function


1.Use Stirlings formula to write down the free
energy.
2. Obtain the equation of state for the ideal gas.
3. Calculate the internal energy and the heat
capacity and comment on your result.
4. Calculate the entropy of the ideal gas (you will
need this for the next lecture!)

Results for an Ideal Gas


The partition function for a single particle:
V
h
Z1 3 where

2mkT
For a gas of N particles:

1 N
ZN
Z1
N!

Stirlings formula
e
2mkT

ZN
V

2
N
h

N !

e
2mkT
Z N V

2
h

Helmholtz Free Energy

F kT ln Z N

eV 2mkT
F NkT ln

2
h

F
P
V

Equation of
State

PV NkT

e
2mkT
Z N V

2
h

ln Z N
E

Internal energy
3
E NkT
2

As expected from the Classical Equipartition


Theorem

To obtain the entropy of the ideal gas:


eV 2mkT
F NkT ln

2
h

From the definition


of the Free Energy

and

3
E NkT
2

F E TS

3 2mkT
5
S Nk ln V ln
ln N
2
2
h
2

The Gibbs Paradox ~ The Entropy of Mixing


Consider two gases A and B which each contain N
particles or masses ma and mb respectively, and each
occupies a volume V.
They are separated by a partition which is removed so
that the gases are allowed to mix.
N particles volume V

ma

N particles volume V

mb

What is the entropy change if the two gases are:


i) Different? ii) The same?

Before the removal of the partition, the total


entropy is just the sum of the two separate
entropies:

S I S a Sb
3 2m A kT
5
Nk ln V ln
ln N
2
2
h
2

3 2mB kT
5
Nk ln V ln
ln N
2
2
h
2

SA
SB

When mixing occurs, then the volume occupied is


2V for each gas:

3 2m A kT
5
S F Nk ln 2V ln
ln N
2
2
2
h

3 2m B kT
5
Nk ln 2V ln
ln N
2
2
2
h

S I 2 Nk ln 2

Increase in entropy

Intuitively, if the gases are different the entropy


should increase when the partition is removed.
However, if the gases are the same, then the entropy
change should be zero!
In both cases, when the partition is removed there
will then be two gases, each with N particles,
occupying a volume 2V.
The paradox is resolved by the different manner in
which partition functions are combined for the
different and identical gases

The partition function of the mixed system is:

ZT=ZAZB
when the gases are distinguishable from each other.
However, even when the gases are different the
particles are still indistinguishable amongst
themselves.
N

zA
ZA
N!

and

N
B

z
ZB
N!

where za and zb are the single particle partition


functions for gas A and B

Therefore:

Z Total

N
A

N
B

z z

N !N !

where each single particle partition function is


now proportional to 2V.
When both gases are the same, there are 2N
indistinguishable particles in a total volume 2V.
Therefore:

Z Total

z A2 N

(2 N )!

For identical particles, there is no change in


entropy when the partition is removed because of
the difference between:

Z Total

z A2 N

2
(N !)

Identical
Not Identical

Extra 2N ln 2

Z Total

z A2 N

(2 N )!

Extra factor cancels


out entropy increase
from V2V

(in this artifical thought experiment we are in the limit


when zA and zB are almost identical, so zA=zB but we can
still distinguish the particles!)

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