1.

The Statistical Basis of Thermodynamics

1. The Macroscopic & the Microscopic States

2. Contact between Statistics & Thermodynamics:
Physical Significance of the Number (N,V,E)
3. Further Contact between Statistics & Thermodynamics
4. The Classical Ideal Gas
5. The Entropy of Mixing & the Gibbs Paradox
6. The Correct Enumeration of the Microstates

1.1.

The Macroscopic & the Microscopic States

System of N identical particles in volume V, with

N ,V ,

N
finite
V

(Thermodynamic limit )

E.g., Non-interacting particles:

N

N ni
i 1

E ni i
i 1

i = single particle energies

ni = # of pcles with energy i

A macrostate is specified by parameters ( N, V, E, ... ).

Postulate of equal a priori probabilities:
All microstates satisfying the macrostate parameters are equally likely to occur.
Let

N ,V , E , = # of all microstates that give rise to the

macrostate (extensive) parameters N, V, E, ... .

1.2.

Contact between Statistics & Thermodynamics:

Physical Significance of the Number (N,V,E)

Consider 2 systems A1 & A2 in thermal contact with each other,

i.e., partition is fixed, impermeable but heat conducting.
( Nj , Vj & E(0) = E1 + E2 are fixed )

E E
E

denotes properties of
the composite system

A2
( N2 , V2 , E2 )

A1
( N1 , V1 , E1 )

(0)

0
E E1 E2

Equilibrium is achieved if E1 ( with E2 = E(0) E1 ) maximizes (0) :

1 E1
2 E2
0

E
0
2 2
1 1
E1
E2
E1

2 E2
2 E2

E1
E2

 1 E1
2 E2
2 E2 1 E1
0
E1
E2

Let

2 E2
1 1 E1
1

1 E1 E1
2 E2 E2

ln E
E

2 systems are in thermal equilibrium

if they have the same .

S k ln

Planck :

ln 1 E1 ln 2 E2

E1
E2

S
1

N ,V T

Thermodynamics :

Boltzmann :

k = Boltzmann constant

1
kT

S k ln

0th law ( thermal eqm.)

3rd law

1.3. Further Contact between Statistics & Thermodynamics

For an impermeable but movable & heat conducting partition,
Nj , V(0) = V1 +V2 & E(0) = E1 + E2 are fixed.
Equilibrium is achieved, i.e., (0) is maximized, if

0
E1

0
V1

and

ln

N , E

i.e., both system have the same values of &

1st law:

dE T dS P dV dN
S
PT

N , E

chemical potential

P
kT

~ mech. eqm.

For a permeable, movable & heat conducting partition,

N(0) = N1 + N2 , V(0) = V1 +V2 & E(0) = E1 + E2 are fixed.
Equilibrium is achieved, i.e., (0) is maximized, if

0
0
E1

0
0
V1

0
0
N1

i.e., Both system have the same values of , , &

1st law:

ln

N V , E

dE T dS P dV dN

V , E

kT

~ chemical eqm.

Summary

Connection between statistical mechanics & thermodynamics is

S k ln
Once is written in terms of the independent thermodynamical variables,
all other thermodynamic quantities can be obtained via the Maxwell relations.

Mnemonics for the Maxwell Relations

Good Physicists Have Studied Under Very Fine Teachers

T P
V S

S
V
2

U
S V

G = F ( P) V Y X = H TS
Gibbs free energy
P, Y

dH TdS Vd P Y dX

F = U TS
Helmholtz
free energy

V,X

T
V

S
P G

S
T P

x y z
1

y z z x x y

H = U ( P) V Y X
Enthalpy

U = U(V,S,X)
Internal Energy

S
P

V
T

dU TdS P dV Y dX
U
S T

F var var W var

1.4.

The Classical Ideal Gas

Non-interacting, classical ( distinguishable), point particles:

S k N ln V const

N , E ,V V N

const here means indep. of V.

S
P
N

k
V
V

N ,E T
Cf

PV n R T

R
nR
8.31 J / mol K
23

1.38

10
J /K
k

23
N
N
6.02 10 / mol
A
8.62 105 eV / K

Quantum (Obeying Schrodinger Eq) Free Particles

Let these particles be confined within a cube of edge L.
Dirichlet boundary conditions: 0 at walls ( where x,y,z = 0,L ).

n x
L

A sin

n n
x sin y y sin z
L L

ni 1, 2,3, ; i x, y , z

Neumann boundary conditions: n 0 at walls.

n x
L

A cos

n
x cos y y cos z

L
L

ni 0,1, 2, 3,
2

1-particle energy :

2k 2 2 2
2
2
nx , n y , nz

n x n y nz
2m 2m L
h2
2
2
2

x
y
z
8m V 2/3

V L3

Let

h2
h2
2
2
2
*

x
y
z
8m V 2/3
8m V 2/3
i.e.

* n x2 n 2y nz2

( * is a positive integer )

N 1, E ,V # of { nx, ny, nz } satisfying

8m V 2/3
n n n
h2
*

2
x

2
y

2
z

For N non-interacting particles

N
h2
h2
2
2
2
*
E
n

ix
iy
iz
8m V 2/3 i 1
8m V 2/3
N

E n n n
*

2
ix

2
iy

2
iz

3N

i 1

2
r

r 1

8m V 2/3 E
E n n n
h2
i 1
N

N , E ,V # of { nix, niy, niz } satisfying

N , E ,V N , V 2/3 E

2
ix

2
iy

2
iz

 N , E ,V N , V 2/3 E

S N , E ,V S N , V 2/3 E

For reversible adiabatic processes, S & N are kept constant.

V 2/3 E const f N , S

2 E

2/3
dV

V
dE

0
1/3
3V
N ,S

E
2E

V
3V

N , S

E
P

V N , S

2E
3V

PV 5/3 const

(adiabatic processes)
Valid for both classical
& quantum statistics

Counting States:

Distinguishable Particles

State labels { nix, niy, niz } form a lattice in the 3N-D n-space.
( N,E,V) = # of lattice points with non-negative coordinates & lying on the
surface of a sphere, centered at the origin, and with radius

8m V 2/3 E
*
2
h

fluctuates wildly even for small E changes unless N >>1.

Better behaved quantity is ( N,E,V),
defined as the # of lattice points with non-negative coordinates & lying within
the volume bounded by the surface of a sphere, centered at the origin, and
with radius R

As R , the lattice points become a continuum.

1 4 * 3/2 * 3/2
1 * N 1, *

8 3
6
Better approximations:

1 *

4

Number of points on the x-y, y-z, z-x planes is 3

Since these points are shared by 2 neighboring sectors, the

volume integral counts each as half a point.

1 *

1 *

* 3/2

3 *

Neumann B.C.
(include all nj = 0 points )

* 3/2

3 *

Dirichlet B.C.
(exclude all nj = 0 points )

( Density of states
in n-space is 1. )

Volume of an n-D sphere of radius R is

Volume of points with

non-negative coordinates

Vsph

1
V Vsph
2

1
N , E*
2

3N

3 N /2
3N

!
2

n /2
n
!
2

Rn

( see App.C )

n ! n 1

( Take non-negative-half
of every dimension )

E * 3 N /2

8mV 2/3 E
V
*
N,V, E N, E

3
2
h
h

2 m E

3 N /2

3N

!
2

V
N ,V , E 3
h

2 m E

3 N /2

3N

!
2

3/2
V
3N
ln N ,V , E N ln 3 2 m E ln
!
h
2

ln n ! n ln n n

Stirlings formula:
3
2

3N
3N 3N
ln
!

N
ln

2
2
2

for n >>1

V 4 m E 3/2 3N
ln N ,V , E N ln 3

h 3N 2

Let (N,V,E) = # of states lying between E & E+ .

N ,V , E
3N
N ,V , E

N ,V , E
E
2 E
V 4 m E 3/2 3N
ln N ,V , E N ln 3

h
3
N
2

ln N ,V , E ln N ,V , E

 V 4 m E 3/2 3N
ln N ,V , E N ln 3

h 3N 2

V 4 m E 3/2 3N k
S N ,V , E k ln N k ln 3

2
h 3N

2S

3h 2 N
E S ,V , N
exp

1
3N k

4 m V 2/3

2
E

E
T

3N k
S N ,V
E
3
CV

Nk

2
T N ,V

2
E

E
P

3V
V N , S

E N k T n R T
2

3
nR
2

PV

2
E N kT n RT
3

H
E PV
5
CP

nR

n
R

N , P
2

N , P

CP 5

CV 3

 V 4 m E 3/2 3N k
S N ,V , E N k ln 3

h
3
N
2


E const

Isothermal processes ( N, T = const ) :

S
S
V

V N , E

E N kT
2

Nk
V N k ln V
V

S f Si N k ln V f ln Vi

N k ln

Vf
Vi

Adiabatic processes ( N, S = const ) :

V E

3/2

PV n R T
Alternatively,

const

dE N ,S P dV

VT

3/2

const V T

5
3

P V 5/2 const P V
2E

dV
3V

also leads to

V E 3/2 const

1.5.

The Entropy of Mixing & the Gibbs Paradox

V 4 m E 3/2 3N k
S N k ln 3

2
h 3N
3
E NkT
2

4 m E
3
N k ln V N k 1 ln

2
2
3
h
N

2 m k T 3/2 3
V 3
S N k ln V

N
k

ln 3

2
h
2

2

This S is not extensive, i.e.,

S N , V , E S N ,V , E

Thermal
wavelength

Mixing of 2 ideal gases 1 & 2 (at fixed T ) :

before
total

after
total

Vi 3
Si k N i ln 3
i 2
i
i

Smixed

V 3
k N i ln 3
i 2
i

2 2
m kT

V Vi
i

before
total

Vi 3
Si k N i ln 3
i 2
i
i

Entropy of mixing of gases :

S mixing S

after
total

after
total

V 3
k N i ln 3
i 2
i

Ni N

Vi V
before
total

N i ln
i

V
0
Vi

Irreversible process: S > 0 is expected.

Gibbs paradox :
For the mixing of different parts of the same gas in equilibrium (Ni / Vi = N / V ,

i = ), the formula still applies & we also have S > 0, which is unacceptable.

For the mixing of different parts of the same gas in eqm.,

before
total

N i ln
i

V 3
after
Stotal
k N ln 3
2

V 3
k N i ln i3
2

i

S mix k

V
Vi

N i ln
i

N
Ni

k N ln N k

N ln N
i

Smixed k N ln N Si k N i ln N i 0
i

or

Ni N
, i
Vi V

N ln N N ln N !

Smixed k N ln N N Si k N i ln N i N i 0
i

Thus, Gibbs paradox is resolved using Gibbs recipe :

S S k ln N !

V 4 m E 3/2 3
S N ,V , E N k ln
1 N k
3
N h 3N 2

Sackur-Tetrode eq.

S is now extensive, i.e.,

S N , V , E S N ,V , E

Revised Formulae
In general, relations derived using the previous definition of S
are not modified if they do not involve explicit expression of S.
Gibbs recipe is cancelled by removing all terms in red.

V 4 m E 3/2 3
S N ,V , E N k ln
1 N k
3
N h 3N 2
2/3

2S 2
3h 2 N N
E S ,V , N
1
exp
4 mV
3
N
k
3

extensive

E
E 2 2 S

N V , S N 3 3 N k

intensive

E
2E
T

N ,V 3 N k

E
2E
P

V
3V

N , S

E
N

2 2 S
1 3 3 N k

E 2E 2E S

N 3N 3N N k

2E
3N k

2E
3V

1
E PV ST
N

V 4 m E 3/2 3

V
3

N
k
ln

1
S N k ln

1
N
k

3
3
2
N h 3N 2
N

2 2 S
2 2 V 2
3
1

k
T
1 ln
1
3 3 N k

3 3 N 3
N 3
k T ln
V

N 3
A G P V N P V N N kT N k T ln 1

V

2 2
m kT

1.6.

The Correct Enumeration of the Microstates

Elementary particles are all indistinguishable.

In the distribution of N particles such that ni particles occupy the i state,

N!
ni !

for distinguishable particles

1
In the classical (high T ) limit,

Gibbs recipe corresponds to

for indistinguishable particles

ni 0 i

D
N!

D N !