Simple Applications of Statistical Mechanics

Kumneger T.

Adama Science and Technology University

June 29, 2021

Kumneger T. (ASTU) June 29, 2021 1 / 30

Partition function
A system at constant temperature can be characterized by its
partition function Z ; X
Z= e −βEr (1)
r
where the summation is over all possible states r of the system and
Er is the enrgy of the system in state r .
Any other physical quantities of the system can be obtained from Z .
To evaluate the sum in the above equation we need to know the
quantum states of the system which can be determined from the
information about the particles which constitute the system and the
interactions between them.
In the classical approximation, energy of a system containing N
molecules can be given by
E = E (q1 , q2 , ..., qn , p1 , p2 , ..., pN ) (2)
where qi is generalized coordinate and pi is generalized momenta of
the constituting molecules.
Kumneger T. (ASTU) June 29, 2021 2 / 30
If an element of volume (dq1 , ..., dqN , dp1 , ..., dpN ) at the point
(q1 , q2 , ..., qN , p1 , p2 , ..., pN ) of phase space is subdivided in to cells of
volume hoN , the number of cells is then

dq1 , ..., dqN , dp1 , ..., dpN

(3)
hoN

All those cells have nearly the same energy

E (q1 , q2 , ..., qN , p1 , p2 , ..., pN ).
Thus by summing over all such elements of volume, the partition
function, in the classical approximation, becomes
Z Z
dq1 ...dqN dp1 ...dpN
Z = ... exp(−βE (q1 , ..., pN )) (4)
hoN

Remarks on Z :
(I) If the energy states of a given system are shifted by a constant
amount εo ;
Er∗ = Er + εo (5)
Kumneger T. (ASTU) June 29, 2021 3 / 30
The partition function is then
∗
X X X
Z∗ = e −βEr = e −β(Er +εo ) = e −βεo e −βEr
r r r
∗ −βεo
=⇒ Z = e Z (6)
∗
ln Z = ln Z − βεo (7)

Systems in canonical ensemble are distributed over their accessible

states in accordance with canonical distribution.
The probability of finding a system in state r is then

Pr = Ce −βEr (8)
X X
Pr = C e −βEr = 1
r r
1
=⇒ C = P −βEr
re
e −βEr
=⇒ Pr = P −βE (9)
re
r

Kumneger T. (ASTU) June 29, 2021 4 / 30

The mean energy is then given by
− r ∂βe∂−βEr
P
Er e −βEr
P
r
Ē = P −βE = P −βE
re re
r r

1 ∂Z ∂ ln Z
= − =− (10)
Z ∂β ∂β
Mean energy of the new state is then
∂ ln Z ∗ ∂
Ē ∗ = − = − (ln Z − βεo )
∂β ∂β
∂Z
= − + εo = Ē + εo (11)
∂β
(II)
X
Z = e −βEr
r
=⇒ Z = Z (β, Er )
But Er = Er (x), where x is external parameter of the system
Kumneger T. (ASTU) June 29, 2021 5 / 30
 =⇒ Z = Z (β, x)
∂ ln Z ∂ ln Z
d ln Z = dx + dβ (12)
∂x ∂β

For a system whose external parameters have values x1 , x2 , ..., xn , its

energy in state r is Er = Er (x1 , x2 , ..., xn ).
Then the change in Er due to infinitesimal change in the external
parameters is given by
n
X ∂Er
dEr = = dxi (13)
∂xi
i=1

If the system is characterised by a single external parameter x and if

the parameter changed quasistatically from x to x + dx, then change
in energy in state r is
∂Er
dW = −dx Er = − dx (14)
∂x
Kumneger T. (ASTU) June 29, 2021 6 / 30
whose mean value can be obtained by averaging over all accessible
states r
P −βEr ∂Er
re (− dx)
dW = P −βE∂x
re
r
P −βEr ∂Er
− re dx
= P −βE∂x
re
r

1 ∂ P −βEr
−(− β ∂x r e )dx
= P −βE
re
r

1 ∂Z 1 ∂ ln Z
= dx = dx (15)
βZ ∂x β ∂x
∂ ln Z
=⇒ dx = βdW (16)
∂x
From equations (10), (12) and (16) one can obtain

d ln Z = βdW − Ē dβ
= βdW − d(Ē β) + βd Ē
Kumneger T. (ASTU) June 29, 2021 7 / 30
 dQ
d(ln Z + Ē β) = β(dW + d Ē ) = βdQ =
kB T
dQ
=⇒ d[kB (ln Z + Ē β)] = (17)
T

For a quasistatic process Second Law of Thermodynamics states

dQ
dS = (18)
T
Comparing equations (17) and (18) yields
S = kB (ln Z + Ē β) (19)
For the shifted state this entropy becomes
S ∗ = kB (ln Z ∗ + Ē ∗ β) = kB (ln Z − βεo + Ē β + βεo )
= kB (ln Z + β Ē ) (20)
Therefore entropy of the system remain unchanged when the state of
the system is shifted.
Kumneger T. (ASTU) June 29, 2021 8 / 30
If a system A is made up of two weakly interacting parts A0 and A00
which are in states r and s respectively, then state of A can be
specified by the pair r , s with corresponding energy Ers given by

Ers = Er0 + Es00 (21)

The partition function of the total system A is then

0 00 0 00
X X X
Z= e −βErs = e −β(Er +Es ) = e −βEr e −βEs
r ,s r ,s r ,s
0 00
X X
=( e −βEr )( e −βEs ) = Z 0 Z 00
r s
=⇒ ln Z = ln Z 0 + ln Z 00 (22)

Thus for a system consisting distinct non-interacting or weakly

interacting parts, the partition function is simply the product of that
of each parts.

Kumneger T. (ASTU) June 29, 2021 9 / 30

Calculation of Thermodynamic Quantities
Consider a system of gas consisting of N identical monoatomic
molecules of mass m enclosed in a container of volume V .
The total energy of the system is then
N
X P2i
E= + U(r1 , r2 , ..., rN ) (23)
2m
i=1

where ri and Pi stands for position and momentum of the molecules.

For sufficiently dilute gas interaction between molecules is negligible,
U → 0.
The classical partition function of this system is
Z Z
1
Z = ... exp −β[ (P2 + P22 + ... + P2N ) + U(r1 , r2 , ..., rN )]
2m 1
d 3 r1 ...d 3 rN d 3 P1 ...d 3 PN
.
ho3N
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 −βP2 −βP2
Z Z
1 1 N
= e 2m d 3 P1 ... d 3 PN
e 2m
ho3N
Z
. e −βU(r1 ,r2 ,...,rN ) d 3 r1 ...d 3 rN
Z ∞ Z ∞ Z ∞
1 −βP2
3 N 3
= ( e 2m d P) d r1 ... d 3 rN ; for dilute gas
ho3N −∞ −∞ −∞
Z ∞
1 −βP2
3 N N
= ( e 2m d P) V
ho3N −∞
Z ∞
V −βP2
= ( 3 e 2m d 3 P)N
ho −∞
= ξN (24)

R∞ −βP2
V
Where ξ = ho3 −∞ e
2m d 3 P is partition function of a particle.

Kumneger T. (ASTU) June 29, 2021 11 / 30

Z ∞ −βP2
Z ∞ −β
3 2 2 2
e 2m d P = e 2m (Px +Py +Pz ) dPx dPy dPz
−∞ −∞
Z ∞ −βPx2
Z ∞ −βPy2
Z ∞ −βPz2
= e 2m dPx e 2m dPy e 2m dPz
−∞ −∞ −∞
s
∞
Z r
2mπ 3 −ax 2 π
= ( ) ; e dx =
β −∞ a
V 2mπ 3 2mπ 3
=⇒ ξ = 3
( )2 = V ( 2 )2 (25)
ho β βho
ln Z = N ln ξ
2mπ 3
= N ln(V ( 2 ) 2 )
βho
3 3 2πm
= N[ln V − ln β + ln 2 ] (26)
2 2 ho

Kumneger T. (ASTU) June 29, 2021 12 / 30

From equation (16) we have

1 ∂ ln Z
dW = dx
β ∂x
If the external parameter is taken to be volume of the system, then
one can write
1 ∂ ln Z
dW = dV = P̄dV
β ∂V
where P̄ is mean pressure of the system
1 ∂ ln Z 1N kB TN
P̄ = = =
β ∂V βV V
P̄V = NkB T = nRT

From equation (10)

∂ ln Z 3N 3 3
Ē = − = = NkB T = nRT (27)
∂β 2β 2 2

Kumneger T. (ASTU) June 29, 2021 13 / 30

Heat capacity at constant volume is then

∂Q ∂ Ē
CV = ( )V = ( )V
∂T ∂T
If the external parameter, volume, of the system is constant, first law
of thermodynamics reduce to dQ = dE . Thus the above equation can
be rewritten as
∂ Ē
CV = ( )V
∂T
∂ 3 3 3
= ( NkB T ) = NkB = nR (28)
∂T 2 2 2
Molar specific heat at constant volume is then
1 3
cV = CV = R (29)
n 2

Kumneger T. (ASTU) June 29, 2021 14 / 30

Gibbs Paradox

Entropy of a system is given by

S = kB (ln Z + β Ē ) (30)

Substituting ln Z and Ē from equations (26) and (27) yields

3 3 2πm 3
S = NkB (ln V − ln β + ln 2 + T )
2 2 ho 2
3 3 2πm 3
= NkB (ln V − ln β + σ); (whereσ = ln 2 + T ) (31)
2 2 ho 2

All thermodynamic relations remain valid when the size of a system

under consideration increased by a scale factor α.
This is valid for the mean energy Ē , equation (25), if the independent
extensive parameters V and N are multiplied by α.

Kumneger T. (ASTU) June 29, 2021 15 / 30

But equation (27) doesnot satisfy this condition. This implies that
equation (31) is not correct representation for entropy of the system.
Moreover equation (27) shows that for a fixed volume V , S is
proportional to N. But this is wrong implication. This can be proven
as follows.
Consider a system A divided in to two parts A0 and A00 by a partition.
Thus one can write
S = S 0 + S 00 (32)
Suppose the partition divides the system in to two equal parts each
containing N 0 molecules in volume V 0 .
3
S 0 = S 00 = N 0 kB (ln V 0 − ln β + σ) (33)
2
The entropy of the whole system is then
3
S = 2N 0 kB (ln(2V 0 ) − ln β + σ) (34)
2

Kumneger T. (ASTU) June 29, 2021 16 / 30

 3 3
S − 2S 0 = 2N 0 kB (ln(2V 0 ) − ln β + σ) − 2N 0 kB (ln(V 0 ) − ln β + σ)
2 2
= 2N 0 kB (ln(2V 0 ) − ln(V 0 ))
= 2N 0 kB ln 2 6= 0 (35)

Thus equation (32) is not satisfied. Therefore N dependence of

entropy exhibited in equation (31) is incorrect. This is called Gibbs
paradox.
Gibbs paradox is a consequence of the fact that initially a molecule of
each subsystem could only be found in a volume V 0 , while removing
the partition leads to diffusion of the molecules throughout the whole
volume V = 2V 0 , which obviously increase the entropy of the whole
system since process is irreversible.

Kumneger T. (ASTU) June 29, 2021 17 / 30

Gibbs paradox can be avoided by correcting the partition function.
Because of the indestinguishability of molecules the N! permutations
of molecules among themselves do not lead to physically distinct
situations. The corrected partition function is then given by

Z ξN
Z0 = = (36)
N! N!
=⇒ ln Z 0 = N ln ξ − ln N!
= n ln ξ − N ln N + N (37)

Entropy of the system is then

3
S = kB (ln Z 0 + β Ē ) = NkB (ln ξ − ln N + 1 + )
2
3 3 2πm 3 5
= NkB (ln V − ln β + ln( 2 ) 2 − ln N + )
2 2 h0 2
V 3
= NkB (ln( ) − ln β + σ0 ) (38)
N 2

Kumneger T. (ASTU) June 29, 2021 18 / 30

 3
3
Where σ0 = σ + 1 = 2 ln( 2πm
h2
) 2 + 52 .
0

The entropy S given by equation (38) behaves properly like an

extensive quantity, it does get multiplied by a factor α if both V and
N are multiplied by α.

Specific heat of solids

For a system solid containing NA atoms the total energy due to
lattice vibrations is give by
3NA
X p2 1
E= ( i + ki qi2 ) (39)
2m 2
i=1

If the system is at high temperature where classical approximation is

applicable, one can write
1 1
Ē = 3NA ( kB T + kB T ) = 3NA kB T = 3RT (40)
2 2

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The molar specific heat at constant volume of the solid is then

∂ Ē
cv = ( )v = 3R (41)
∂T
According to this equation molar specific heat is the same for all
simple solids at high temperature. This is called Dulong-Petit law.
However, Third Law of Thermodynamics requires that cV must
approach zero as T → 0.
Thus equation (41) doesnot hold for law temperature.
The bahaviour of CV at all temperature can be approximated by
assuming all atoms in the solid vibrate with the same angular
frequency ω, hence ki in equation (39) can be given by

ki = mω 2 (42)

Moreover a mole of solid can be considered as an assembly of 3NA

independent 1D harmonic oscillators.

Kumneger T. (ASTU) June 29, 2021 20 / 30

Thus the total mean energy is given by 3NA times that of a single
oscillators
1 1
Ē = 3NA h( + βhω ) (43)
2 e −1
The molar specific heat of solids become

∂ Ē ∂ Ē ∂β 1 ∂ Ē
cV = ( )V = ( )V ( )=− 2
( )V
∂T ∂β ∂T kB T ∂β
1 ∂ 1 1
= − 2
( )V [3NA h( + βhω )]
kB T ∂β 2 e −1
3NA hω ∂ 1 1
= − 2
( )V ( + βhω )
kB T ∂β 2 e −1
3NA hω hωe βhω
= − [− ]
kB T 2 (e βhω − 1)2
hω 2 e βhω
= 3NA kB ( ) βhω
kB T (e − 1)2

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 ΘE
ΘE 2 eT
=⇒ cV = 3R( ) ΘE (44)
T (e T − 1)2

hω
where ΘE = kB is called Einstein temperature.

General Calculation of Magnetization

Consider a system of N noninteracting atoms at absolute temperature
T.
Suppose the system is placed in an external magnetic field.
If the local magnetic field on an atom is H, then the magnetic energy
of the atom is
 = −µH (45)
where µ is magnetic moment of the atom which is proportional to
angular momentum of the atom and given by

µ = g µo J (46)

Kumneger T. (ASTU) June 29, 2021 22 / 30

 eh
where µo is Bohr magneton; µo = 2mc

 = −g µo J.H = −g µo Jz H (47)

Jz can has descrete values

Jz = m (48)
where m = −J, −J + 1, ..., J − 1, J
The possible magnetic energies of the atom are then

m = −g µo Hm (49)

For an atom with a single net electron spin J = 21 , thus there are only
two possible energies corresponding to m = ± 12
The probability of an atom to be in a state m is

Pm ∝ e −βm = e βg µo Hm (50)

Kumneger T. (ASTU) June 29, 2021 23 / 30

The Z component of the magnetic moment of the atom in this state
is then
µz = g µo m
PJ βµo gHm g µ m
m=−J e o
=⇒ µ̄z = PJ βµ gHm
m=−J e
o

1 ∂ PJ βµo gHm
β ∂H m=−J e
= PJ βµo gHm
m=−J e
1 ∂Za 1 ∂ ln Za
= = (51)
βZa ∂H β ∂H
PJ
where Za = m=−J e βµo gHm . Let η = βµo gH,
J
X
Za = e ηm = e −ηJ + e −η(J−1) + ... + e ηJ
m=−J
e −ηJ − e η(J+1)
= ; by finite geometric series (52)
1 − eη
Kumneger T. (ASTU) June 29, 2021 24 / 30
 −η
Dividing both numerator and denumenator by e 2 yields
1 1
e −η(J+ 2 ) − e η(J+ 2 )
Za = −η η
e 2 −e2
sinh(J + 21 )η
=
sinh 12 η
1 1
=⇒ ln Za = ln(sinh((J + )η)) − ln(sinh( η)) (53)
2 2
From equation (51) we have
1 ∂ ln Za ∂η
µ̄z = (54)
β ∂η ∂H
∂η
Since η = βg µo H, ∂H = βg µo

∂ ln Za (J + 21 ) cosh(J + 12 )η 1 1
2 cosh 2 η
µ̄z = g µo = g µo [ − ]
∂η sinh(J + 12 )η sinh 12 η
= g µo JBJ (η) (55)
Kumneger T. (ASTU) June 29, 2021 25 / 30
where
1 (J + 12 ) cosh(J + 1
2 )η
1
cosh 12 η
2
BJ (η) = [ − ]
J sinh(J + 12 )η sinh 12 η
1 1 1 1 1
= [(J + ) coth(J + )η − coth( η)] (56)
J 2 2 2 2
For y  1, coth y ≈ 1, hence for η  1
1 1 1
BJ (η) = [(J + ) − ] = 1 (57)
J 2 2
For y  1
e y + e −y (1 + y + 12 y 2 + ...) + (1 − y + 21 y 2 − ...)
coth y = =
e y − e −y (1 + y + 12 y 2 + ...) − (1 − y + 21 y 2 − ...)
2(1 + 12 y 2 ) 1 1 1
= 1 3
= (1 + y 2 )(1 + y 2 )−1
2(y + 3! y ) y 2 3!
1 1 1 1 1 1 1 1
= (1 + y 2 )(1 − y 2 ) = (1 + y 2 − y 2 ) = (1 + y 2 )
y 2 6 y 2 6 y 3
Kumneger T. (ASTU) June 29, 2021 26 / 30
Thus for η  1
1 1 1 1 1 1 1 1 1
BJ (η) = [(J + ) 1
(1 + (J + )2 η 2 ) − 1 (1 + ( η 2 ))]
J 2 (J + 2 )η 3 2 2 2η 3 2
1 1 1 1 1 η2
= [ (1 + (J + )2 η 2 ) − (1 + )]
J η 3 2 η 12
η 1 2 1 1
= [ (J + J + − )]
J 3 4 4
η 2 1
= (J + J) = (J + 1)η (58)
3J 3
For a system of NA atoms per unit volume, the mean magnetic
moment per unit volume, called magnetization, becomes
M̄z = NA µ¯z = NA g µo JBJ (η) (59)
For η  1,
1
M̄z = NA g µo J (J + 1)βg µo H
3
1 2 2
= NA g µo βHJ(J + 1) = χH (60)
3
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where χ = 13 NA g 2 µ2o βJ(J + 1).
For η  1
M̄z = NA g µo J (61)

Pressure and Momentum Transfer

Consider a system of gas enclosed in a container. We want to
calculate the mean force F̄ exerted by the gas on a small element of
area dA of the container wall. This can be obtained by calculating the
net mean momentum delivered to the element of the wall per unit
time by the impinging molecules. If we consider an element of area
dA lying inside the gas at infinitesimal distance inside the wall, the
mean rate of change in momentum of the wall element can be
obtained from the difference between the mean molecular momentum
crossing dA per unit time from left to right, G + , and that of from
right to left G − .
F̄ = G + − G − (62)

Kumneger T. (ASTU) June 29, 2021 28 / 30

The mean number of molecules with velocity between v and v + dv
which cross the area dA whith in time interval dt is given by
f (v)d 3 vdAvdt cos θ (63)
The mean momentum transported across dA per unit time by
molecules whose velocity lie in the range (v, dv) can be obtained by
multiplying eqn (63) by mv
dt , where mv is momentum of each molecule.
Z
+
G = f (v)d 3 vdAv cos θmv
vx >0
Z
= dA f (v)|vx |mvd 3 v
vx >0
Z
= dA f (v)vx mvd 3 v
Zvx >0
−
=⇒ G = dA f (v)|vx |mvd 3
vx <0
Z
= −dA f (v)vx mvd 3 v
vx >0

Kumneger T. (ASTU) June 29, 2021 29 / 30

 Z Z
+ − 3
=⇒ F̄ = G − G = dA[
f (v)vx mvd v + f (v)vx mvd 3 v]
vx >0 vx <0
Z
= dA f (v)vx mvd 3 v
Z
¯
=⇒ Fx = dA f (v)vx2 md 3 v

F¯x
Z
=⇒ P̄ = = f (v)vx2 md 3 v = nmv¯x2 (64)
dA

where v¯x2 = 1
f (v)vx2 d 3 v
R
n

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