MSEG 803

Equilibria in Material Systems

9: Ideal Gas Quantum Statistics

Prof. Juejun (JJ) Hu

hujuejun@udel.edu
Ideal gas: systems consisting of particles with
negligible mutual interactions
Classical ideal gas (Maxwell-Boltzmann MB statistics)
All particles are distinguishable
Quantum statistics
Indistinguishable particles: interchanging two particles does not
lead to a new state
Particles with integral spin (Bosons in Bose-Einstein BE
statistics)
Particles with half-integral spin (Fermions in Fermi-Dirac FD
statistics): one single particle state can only be occupied by one
particle (Pauli exclusion principle)
Microscopic states of ideal gas systems
Example: a 2-particle system with 3 single particle states
Single particle states are different from microscopic states of
a multi-particle system!
MB Statistics BE Statistics FD Statistics
State 1 State 2 State 3 State 1 State 2 State 3 State 1 State 2 State 3
AB AA A A

AB AA A A
AB AA A A
A B
A A
B A
A A
A B There isA a greater
A tendency for particles
B A to bunch together in the BE case
A B
Classical case: Maxwell-Boltzmann distribution
Take an individual system in a canonical ensemble as
one single classical ideal gas particle. The probability of
finding the particle in a specific single-particle level with
energy Er (in this case also the energy level of the
system) is given by the canonical probability distribution
function:
e Er 1 Er
Pr e
e
r
Er
Z

Assumptions: no interactions between particles (ideal

gas), all particles are distinguishable
Two methods of deriving distribution functions
Model the systems as canonical ensembles

Calculate
Calculate
Fix partition
average particle
temperature # which
function Z
minimizes Z

Model the systems as micro-canonical ensembles

Calculate
Fix internal Calculate # of average particle
energy states # which
maximizes
Quantum statistics: problem formulation
Quantum states/levels of a single particle: r, s
Energy of single particle levels r or s: r ors
Number of particles in state r or s: nr or ns
Quantum state of the entire ideal gas system: R
Energy of the system in state R :
ER n11 n2 2 n3 3 ... nr r
r
Canonical partition function:
Z exp ER exp n11 n2 2 n3 3 ...
R R

Mean number of particles in a single particle state r :

1 1 ln Z
nr nr
exp n11 n2 2 n3 3
...
Z R r
Fermi-Dirac distribution
ns = 0 or 1, n
s
s N; define:

Z r N ( r ) exp n11 ... nr 1 r 1 nr 1 r 1 ...

R

n exp n n ...
r 1 1 2 2
0 exp r Z r ( N 1)
nr R

exp n n ...
1 1 2 2 Z r ( N ) exp r Z r ( N 1)
R

ln Z r ln Z r
ln Z r N 1 ln Z r N Z r N 1 Z r N exp
N N
ln Z r ln Z
In macroscopic systems: ~
N N
exp r Z r ( N 1) 1
nr
Z r ( N ) exp r Z r ( N 1) exp r 1
Fermi-Dirac distribution: alternative derivation
The different number of ways to distribute ni particles
over gi degenerate sub-levels of an energy level i :
gi !
i
ni ! g i ni !
The total number of ways the set of occupation numbers
{ ni } can be realized:
gi !
i
i i ni ! gi ni !

Maximizing subjected to the constraints:

n i N n i i E
ni 1
nr
i i

gi exp i 1
d ln d ln i 0
i
Partition function of Fermion ideal gas
Z ( N ) exp ER exp n11 n2 2 n3 3 ...
R R

Constraint: n N
r
r

Define Z Nsharply
' exp peaking
N ' at N = N
N'

exp n
n1 0,1
1 1 exp

n2 0,1
2 n2
...

1 exp r
r

ln Z N ' exp N ' ln Z ln Z

0
N ' N N
ln ~ ln Z N exp N
N ~ ln Z
N
ln Z N ln N ln 1 exp r
r
Properties of Fermi-Dirac distribution
At T = 0 K, FD distribution
is a step function and the
chemical potential defines
the Fermi surface
Electrons in metals
When r ,FD
distribution
kT
can be approximated by
the classical MB
distribution
Electrons in the conduction
band of semiconductors or
insulators
Bose-Einstein distribution
nr can be any positive integer, n
r
r N

0 exp r Z r ( N 1) 2
exp 2 r Zr ( N ...
2)
nr
Z r ( N ) exp r Z r ( N 1) exp 2 r Z r ( N 2)
...
Z r ( N ) 0 exp r 2
exp 2 r 2 ...

Z r ( N ) 0 exp r exp 2 r 2 ...

n exp n r
1
n

exp n
n
r exp r 1

Chemical potential is determined by nr N

r
For a system comprised of conservative Bosons, is
always lower than any single-particle energy level
Partition function: ln Z N ln 1 exp r
r
Bose-Einstein condensate (BEC)
At low temperature, Bosons tends to cluster at the
lowest energy quantum mechanical state

Velocity-distribution data of a gas

of Rb atoms. Left: just before the
appearance of BEC. Center: just
after the appearance of BEC.
Right: nearly pure BEC.
Photon statistics (Planck statistics)
Photons are Bosons
The total number of photons is NOT conserved: = 0
In equilibrium:
dG SdT VdP dN 0
0
dN 0
1 1
nr
exp r 1 exp h 1
Note that the condition = 0 only applies to photons in
thermal equilibrium with a blackbody!
Statistics of blackbody radiation
Blackbody: an idealized physical body that absorbs all
incident electromagnetic radiation
Wave vector quantization condition: L
uu
r
k x nx nx Z
L
r uu
r 2 uu
r 2 uur 2 2
k kx k y kz nx 2 n y 2 nz 2
L
Photon energy:
2 hc
Eh h hkc nx 2 n y 2 nz 2
L
Statistics of blackbody radiation (contd)

The volume each state occupies in L
ky
the phase space:
3
E + dE
1 3
3
Vstate E
2 L 2 L3 2V
Photon Density of States (PDOS): kx
E hc
1 4 E hc dk
2

E dE
8 Vstate
1 4 E hc
2
dE VE 2
2 3 3 dE

8 3 2V hc hc
Statistics of blackbody radiation (contd)
Total # of photons with energy between E to E + dE :
1 VE 2
nr E dE 2 3 3 dE

exp E 1 h c
Total number of photons with frequency between to
+ d per unit volume:
8 V h
2
1 8 2 1
d h
3 h kT d
exp h 1 h 3c 3 c e 1
Total energy of photons having frequencies between
to + d per unit volume:
8 h 3 1
u , T d h kT
d

c 3
e 1
Plancks law and the Stefan-Boltzmann law
Blackbody spectral irradiance:
8 h 3 1
u , T d d

c 3
exp h 1

Total energy emitted from a blackbody per unit area per

unit time:

I T u , T d
0

8 5 k 4
T 4
aT 4

15c 3 h3

a = 7.57 10-16 Jm-3K-4

Heaven is hotter than Hell a thermodynamic
proof
The Bible, Isaiah 30:26:
Moreover, the light of the moon shall be as the light of the sun
and the light of the sun shall be sevenfold as the light of seven
days.
Theaven Tearth 7 7 1 50 Theaven ~ 525 oC
4

The Bible, Revelations 21:8:

But the fearful and unbelieving... shall have their part in the
lake which burneth with fire and brimstone.
A lake of sulfur (brimstone):

Thell TS ,b ~ 445 oC
Appl. Opt. 11(8), A14 (1972).
Classical limit of quantum distribution
In a dilute ideal gas, nr 1 nr exp r
Q nr exp r exp exp r N
r r r

N exp r
kT ln nr N
exp r
r
exp r
r
Partition function

ln Z N N N ln N N N ln
r
exp r

Maxwell-Boltzmann partition function
r
ln Z MB N ln
r
e ln Z ( N ln N N ) ln Z ln N ! ln Z

Thermodynamic properties of ideal gas: MB
classical treatment
p2
Internal energy of monatomic gas: E Ekinetic
N 2m

1 2 d 3q1...d 3 p N
Z MB ... exp p 3N
2 m N h0

1 2 2
3 N exp p1 d p1
3
... exp pN d3 p N 1

d 3
q ...
d 3
qN
h0 2m 2m
N
V N
2
N
2 m
32

3N exp p d 3 p V 2 N
h0 2m h0

3 3 2 m
ln Z MB N ln V ln ln 2
: Single molecule
2 2 h0 partition function
Thermodynamic properties of ideal gas: MB
classical treatment (contd)
3 3 2 m
Partition function: ln Z MB N ln V ln ln
2 2 h0 2
1 ln Z MB 1 N NkT
Pressure: P Ideal gas equation
V V V

Internal energy: E ln Z MB 3 N 3 NkT cV

3
R
2 2 2

Entropy: S MB k ln Z MB E Nk ln V 3 ln T 0
2

where 3 ln 2 mk 3
0 2
2 h0 2
Thermodynamic properties of ideal gas:
classical limit of quantum statistics
Partition function:

ln Z N ln N N N ln
r
exp r

V 3 3 2 m N
N ln ln ln
1 Z
N 2 2 h2 N!

Internal energy: E ln Z 3 N 3 NkT

2 2

Entropy: S k ln Z E Nk ln V 3 ln T

N 2
where 3 ln 2 mk 5 S MB
3
Nk ln V ln T S
2
2 h 2 2
Gibbs paradox
Mixing two parts of ideal gas of identical composition
Maxwell-Boltzmann statistics
Before mixing: S MB ,i 2 Nk ln V 3 ln T

2
After mixing: S 3
MB , f 2 Nk ln 2V ln T S MB ,i
2
Quantum statistics in the classical limit
Before mixing: S 2 Nk ln V 3 ln T
i 0
N 2
After mixing: V 3
S f 2 Nk ln ln T 0 Si
N 2
Vapor-solid phase equilibrium
Equilibrium condition: s v
Partition function of vapor: Z N

v Different from MB !
N!
Chemical potential of vapor:
Fv ln Z
v kT 2 mkT
32

v kT kT ln
N v T ,V N v P h2
Chemical potential of solid:

Fs ln Z
s
s kT
N s T ,V N s
ln Z s 2 ln Z s T Es
Es kT ln Z s ln Z s T0 dT
T 2
T0 kT
Vapor-solid phase equilibrium (contd)
Chemical potential of solid:
T
Es Es T0 N s c T dT
T0

Es T0 1 1 T dT T
ln Z s ln Z s T0 N s
T0 kT 2 T0
c T dT
k T T0
Fs T0 Es T0
ln Z s T0 T0 0 K
kT0 kT0
Es T0 T dT T
ln Z s N s
T0 kT 2 T0
c T dT
kT
ln Z s Es T0 T dT T
s kT T T0 kT 2 T0
c T dT
N s Ns
Vapor-solid phase equilibrium (contd)
Equilibrium condition: s v
kT 2 mkT 3 2 Es T0 T dT T
kT ln T 2 T
c T dT
0 kT
2
P h Ns
T 0

Equilibrium vapor pressure:

Es T0
32
2 mkT 1 T dT T
P kT
h2

exp


kTN s

k T0 kT 2 T0 c T dT

Saturated vapor (equilibrium):

the rate of molecules impinging on
the solid/liquid surface = the rate of
vaporization from solid/liquid
Density of states for single-particle levels
Consider ideal gas occupying a volume V
Plane wave solution time-independent Schrdinger
equation:
r r ur r
A exp ik r p hk
h2 k 2 Lx
2m
Periodic boundary condition:
x x Lx
uu
r
Quantization of wave vector k : k x 2 nx nx Z
Lx
Density of states:
2m
32
V V
k d 3 k 1 2d

2
3
4 2 h3