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Student's notebook on Statistical Physics

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 Statistical Physics
students of PH506 course in 22W semester

Preface
This lecture note on Statistical Mechanics is made by BTech and MSc stu-
dents of PH506 course, taught by instructor Dr. Sabyasachi Ghosh in Winter
semester of 2022 with the help of teaching assistant Mr. Cho Win Aung.

Contents
1 Revisit Thermodynamical Relations for ideal gas 2

2 Micro Canonical Ensemble (MCE) calculation for ideal Gas 4

2.1 Gibb’s paradox . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3 Canonical Ensemble 13
3.1 Micro to Macro connecting relation for CE . . . . . . . . . . . . 17
3.2 CE Partition function for non-interacting or ideal gas . . . . . . 19
3.3 CE Partition function for Classical Harmonic Oscillator (CHO) . 22
3.4 CE Partition function for quantum Harmonic Oscillator (QHO) . 24

4 Grand-Canonical Ensemble 26
4.1 Micro to Macro connecting relations for GCE . . . . . . . . . . . 27

5 Equivalence between CE and GCE 29

6 Quantum mechanical version of partition function 33

6.1 quantum version of thermodynamical relation for Bosons and
Fermions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
6.2 Photon Gas : example Boson system . . . . . . . . . . . . . . . . 38
6.3 Calculation of average temperature inside Sun . . . . . . . . . . . 42
6.4 Degenerate density, pressure, internal energy for non-relativistic
(NR) case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
6.5 Degenerate density, pressure, internal energy for ultra-relativistic
(UR) and relativistic (R) cases . . . . . . . . . . . . . . . . . . . 47
6.5.1 Extreme Relativistic Case: E = |⃗ p|c . . . . . . . . . . . . 47
1
6.5.2 General Case: E = (⃗ p2 c2 + m2 c4 ) 2 . . . . . . . . . . . . . 47

1
1 Revisit Thermodynamical Relations for ideal
gas
Here, we will quickly revisit our old Thermodynamical understanding. Let us
start with Euler thermodynamical relation:

T S = U + P V − µN
=⇒ U = T S − P V + µN
(1)

The various quantities used in the above equation are as follows :

U = Internal energy
T = Temperature
S = Entropy
P = Pressure
V = Volume
µ = Chemical potential
N = Number of particles

Taking total differential on both sides, we get :

dU = T dS + SdT − P dV − V dP + µdN + N dµ (2)

From the 2nd law of thermodynamics, we get :

T dS = dU + P dV − µdN (3)

Substituting T dS = dU + P dV − µdN in (2), we obtain :

dU = dU + P dV − µdN + SdT − P dV − V dP + µdN + N dµ

=⇒ SdT − V dP + N dµ = 0

The above relation is called the Gibb’s Duhem relation.

In thermodynamics, the Gibbs–Duhem equation describes the relationship

between changes in chemical potential for components in a thermodynamic sys-
tem. However, it cannot be used for small thermodynamic systems due to the
influence of surface effects and other microscopic phenomena.

2
From eqn.(1), we get :
U P µ
S= +V −N
T T T

1 P µ 1 P µ
=⇒ dS = U d( ) + V d( ) − N d( ) + ( )dU + ( )dV − ( )dN (Product Rule)
T T T T T T

1 P µ 1 P µ
=⇒ dS = U d( ) + V d( ) − N d( ) + dS (Using dS = ( )dU + ( )dV − ( )dN from (3))
T T T T T T

1 P µ
=⇒ U d( ) + V d( ) − N d( ) = 0
T T T
(4)
3N KB
We know that U = 23 N KB T (Internal energy of ideal gas) i.e. 1
T = 2U and
P N KB
T = V (from Ideal Gas equation).

Substituting these values in eqn.(4), we get :

3N KB N KB µ
U d( ) + V d( ) − N d( ) = 0
2U V T
µ 3 N N
=⇒ N d( ) = KB U d( ) + KB V d( )
T 2 U V
µ 3 N N
=⇒ N d( ) = U d( ) + V d( )
KB T 2 U V
µ 3U N V N
=⇒ d( )= d( ) + d( )
KB T 2N U N V
µ 3U dN N dU V dN N dV
=⇒ d( )= [ − 2
]+ [ − ]
KB T 2N U U N V V2
µ 3U dN N dU V dN N dV
=⇒ d( )= [ − ]+ [ − ]
KB T 2N U U2 N V V2
µ 3 dN 3 dU dN dV
=⇒ d( )= − + −
KB T 2 N 2 U N V
µ 5 dN 3 dU dV
=⇒ d( )= − −
KB T 2 N 2 U V
After integrating both sides we get :
µ 5 3
= ln N − ln U − ln V − ln C
KB T 2 2
" 5
#
µ N 2
=⇒ = ln 3 (5)
KB T U 2V C
" 5
#
µ N2
=⇒ = KB ln 3
T U 2V C

3
Again, from eqn.(1), we obtain :

U P µ
S= +V −N
T T T
3
N K B T µ
=⇒ S = 2 + N KB − N ( )(Using Ideal Gas Equation)
T " T #
5
5 N2
=⇒ S = N KB − N KB ln 3 (Using eq.(5))
2 U 2V C
" 3
! #
U 2V C 5
=⇒ S = N KB ln 5 +
N2 2

Thus, we have obtained an expression for entropy in terms of other macroscopic

quantities like internal energy, volume and number of particles.

2 Micro Canonical Ensemble (MCE) calculation

for ideal Gas
Hamiltonian of a system comprising of N-ideal gas molecules is given by,

H =T +V
3N N
X p2i X
H(qi , pi ) = + ϕ(xi ) (6)
i=1
2m i=1

where H represents the Hamiltonian, T represents the kinetic energy and V

represents the potential energy of the particle. The above expression is obtained
from the Hamiltonian formalism in classical mechanics. Another important
assumption that we are making here is as this is an ideal gas, there will be no
interaction between the molecules of the gas. As a result we can replace ϕ with
zero. However with the application of the boundary condition for the box we
get the following revised equation of the potential,
(
0 for x inside box
ϕ(x) = (7)
∞ for x outside box

Thus the expression for Hamiltonian inside the volume of the container is given
by,
3N
X p2i
H= (8)
i=1
2m

4
But for our system of particles we know,

H(qi , pi ) = E (9)
3N
X p2i
=E
i=1
2m
3N
X
p2i = 2mE = R (10)
i=1

Eqn.(9) is the constant energy equation which imposes constraint on the sys-
tem limiting the available the momentum space to the surface of sphere. This
geometric symmetry is evident from the close resemblance of the eqn.(10) with
the equation of sphere.

p21 + p22 + p23 + ...... = 2mE (11)

2 2 2 2
x +y +z =R (12)

On comparing the eqn.(12) and eqn.(11) we can deduce the value of the radius
of the analogous sphere in the 3-N dimensional space.
√
R = 2mE (13)

Using symmetry and applying constraints to our system we have reduced the
problem from abstract integral over 3-N dimensional space to integration over
a surface of 3-N dimensional hyper-sphere.
For a micro-canonical ensemble, the equilibrium density distribution represented
by ρeq is assumed to be constant in between two constant energy surfaces sep-
arated by a very small distance in the phase space.The equilibrium density
distribution is analogous to to the probability distribution function from the
quantum mechanics. In order to understand how ρeq evolves with time we need
to first revisit a few properties of the phase space. A given space is represented
by a trajectory in the phase space. Some of the important properties of the
trajectories in the phase space are as follows,
• Flow lines are deterministic, i.e. there is no intersections between the
trajectories which may give rise to the uncertainty in the sate of the system
in phase space.
• Liouvilles’ theorem states that there can be no points of convergence in
the phase space,i.e.
dρ
=0 (14)
dt

If a small volume with constant density is allowed to evolve with time every
point in the system will have moved a certain distance. However from liouville’s
theorem we van say that the density of the system will stay constant, but the

5
Figure 1: Intersection of flow lines is strictly not permitted and it gives rise to
uncertainty in the state of the system

Figure 2: Such points where phase space trajectories converge are not
permitted according to Liouvilles’ theorem implying absence of source or sink

new topology of the system will be quite complicated due to the constraint on
the system. Thus for our micro-canonical ensemble density will be constant
between two constant energy surfaces. The equilibrium density distribution can
be used to obtain the following properties of the system,

• Ensemble Averages- These are the macroscopically measure quantities

which we actually measure.
• Statistical distributions of parameters such as momentum, etc.
• Other thermodynamic properties.
(
C ′ E ≤ H(µ) ≤ E + δE
ρeq (µ) = (15)
0 otherwise

6
 Figure 3: Figure depicting the area of interest between two constant energy
surfaces bounded by E and E + δE

In order to determine the value of the equilibrium density distribution we first

need to figure out the value of the constant in the eqn.(15). To obtain the value
of C ′ we use the following normalisation condition,
Z
ρeq (µ)d6N µ = 1 (16)

Thus we have a integral of a function dependent on the variable µ where µ

represents a generalised coordinate in a phase space, in a 6N dimensional space.

7
Substituting the value of eqn.(15) in eqn.(16)
Z
ρeq (µ)d6N µ = 1
Z
C ′ d6N µ = 1
E≤H(µ)≤E+δ
Z
C′ d6N µ = 1
E≤H(µ)≤E+δE
h i
Ω̃(E + δE) − Ω̃(E) × C ′ = 1
1
C′ = (17)
Ω̃(E + δE) − Ω̃(E)

As equilibrium density distribution function is zero everywhere except in the

regions between the two constant energy surfaces represented by E and E + δE.
According to Noether’s theorem time invariant or symmetric systems have their
energy conserved. So for a system varying with time, we can understand its
evolution with time by understanding how it responds to change in the energy
of the system.Thus to understand the time dependence of ρeq we try to observe
the effects of change in energy on the value of ρeq . The Ω̃(E) term used in the
above expression is the integration term written in a more compact form.

Eq.(18) represents the generalised expression for finding the ensemble average.
The macroscopic quantity to be measured is represented by the A(µ)and mul-
tiplied by the equilibrium density distribution to obtain the ensemble average.
The procedure followed is analogous to the method of finding expectation values
in the quantum mechanics using the probability distribution function.
Z
⟨A⟩eq = A(µ)ρeq (µ)d6N µ (18)

Ω̃(E) represents the volume enclosed by the boundary condition H(µ) ≤ E

in the integral eqn.19. We will try to further evaluate the integral in detail what
each term in the eqn.19 represents.
Z
Ω̃(E) = d6N µ (19)
H(µ)≤E

µ is the generalised coordinate in the phase space as mentioned previously.

It can be written in the expanded form as shown below, by splitting it into
it’s constituents i.e. momentum and position. In d3 xN the 3 represents the
three coordinates required to uniquely determine the position of the particle. N
represents the no. of particles. In quantum mechanics each particle is defined
using its own set of coordinates , as result for N particles we need 3N coordi-
nates. Similarly for momentum to we need another 3N coordinates to define
the particle in phase space. As a result the total number of coordinates end up

8
being 6N which represents the 6N dimensional phase space through which our
system of N-particles is defined.

d6N µ ⇒ d3 x1 d3 x2 d3 x3 ....d3 xN d3 p1 d3 p2 d3 p3 ....d3 pN (20)

Integration of position coordinates gives us the volume of the closed system. For
a single particle integral over a volume is represented by V . As all the particles
are identical, using symmetry the value of the integral over position will give
same results for all the other particles. Thus the total value of the integral is
V N. Z
dx1 dx2 dx3 ...dx3N = V N (21)

As energy is not dependent on the value of the position of the particle, hence the
integral of the position dependent terms can be treated separately. The value
of this separated integral was already obtained above in the eq.(21). Thus to
obtain the value of the integral we need to obtain the value of the momentum
integral. Z
Ω̃(E) = V N P dp1 dp2 dp3 ....dp3N (22)
3N
i=1 p2i ≤2mE

As discussed previously, due to the boundary conditions applied on our system

it is spherically symmetric in the momentum space. Thus in order to find out
the value of the value of the integral in the eqn.(22) we need to find out the
value of the hyper-sphere. The equation for the value of the hyper-sphere is
given by-
d
π 2 Rd
Vsp (R, d) = (23)
Γ( d2 + 1)
where R denotes the radius of the hyper-sphere and d denotes the dimensions.
Z
dp1 dp2 dp3 ....dp3N (24)
3N
p2i ≤2mE
P
i=1

From eqn.(24) and eqn.(23) we get the following simplified expression for the
value of integral in the momentum space.
3N
π 2 R3N √
Vsp (R, 3N ) = where R= 2mE (25)
Γ( 3N
2 + 1)

Replacing the volume of momentum integral from eqn.(25) in eqn.(22) we get

the following final expression for the value of Ω̃(E).
3N
N π 2 R3N √
Ω̃(E) = V where R= 2mE (26)
Γ( 3N
2 + 1)

In the phase space the momentum and position cannot take up any small value
indiscriminately. The uncertainty principle puts a limiting condition on the
minimum values of the momentum and position of the molecules in the phase

9
space. This is obtained by dividing our final expression for the no. of micro-
states by h3N as shown below.

1 ∂ Ω̃(E)
Ω= × × δE (27)
h3N ∂E
Thus eqn.(27) represents the final form for obtaining the number of micro-states
in the micros-canonical ensemble. The value of the entropy can be obtained
using the following procedure. From eqn.(27) and eqn.(26) we get,

3N 3N
−1
dΩ̃ (2πm) 2 E 2
=VN (28)
dE ( 3N
2 − 1)!

From eqn.(28) and eqn.(26) we get the value of number of micro-states in an

ensemble given by,
3N 3N
−1
VN (2πm) 2 E 2
Ω= × × δE (29)
h3N
( 3N
2 − 1)!

Using logarithm operator on both sides of the above equation,

 
3N 3N
log(Ω) = −3N log(h) + log(2πm) + − 1 log(E)
2 2
 
3N
− log − 1 ! + N log(V ) + log(δE) (30)
2

Applying Stirling’s approximation on the above equation, and keeping only the
lower order terms of N,
   
3 3 3N 3N
log(Ω) ≈ −N log(h ) + N log(2πmE) − 2 log
2 2
 
3N
+N log(V ) + (31)
2

Replacing the constants like π, m, E with another single constant C. Therefore

above equations transforms to,
" 3
! #
E2V C 3
log(Ω) = N log 3 + (32)
N2 2

Using Boltzmann expression for entropy we get,

" 3
! #
E2V C 3
S = N KB log 3 + (33)
N2 2

where KB is known as Boltzmann’s constant.

10
2.1 Gibb’s paradox
There are two identical boxes of volume V1 and V2 and the number of molecules
in it are N1 and N2 respectively.
After mixing two system at same temperature(T),

V1 + V2 = Vf and N1 + N2 = Nf

Entropy Change:-
3 3
Sf −(S1 +S2 ) = KNf (ln[V1 ( 23 KT ) 2 ]+ 32 )+ 32 Nf Kln( 4πm 3 2
3h2 )−KN1 (ln[V1 ( 2 KT ) ]+
3
3
2 + 32 ln( 4πm 3
3h2 )) − KN2 (ln[V2 ( 2 KT ) ] +
2 3
2 + 32 ln( 4πm
3h2 ))

=⇒ ∆S = KNf ln[V1 ] − KN1 ln[V1 ] − KN2 ln[V2 ] + K( 32 ln[ 32 KT ] + 3

2 +
3 4πm
− N1 − N2 )
2 ln[ 3h2 ])(Nf

We know that, Nf − N1 − N3 = 0
Therefore,
V V
∆S = KN1 ln[ Vf1 ] + KN2 ln[ Vf2 ] ——– eqn.[A]

For V1 = V2 and Vf = 2V ,N1 = N2 = N and Nf = 2N

from eqn.[A],
V V
∆S = KN1 ln[ Vf1 ] + KN2 ln[ Vf2 ]
Now the equation becomes,
∆S = KN1 ln[ 2V 2V
V ] + KN2 ln[ V ]
∆S = KN1 ln[2] + KN2 ln[2]
Since N1 = N2 ,
∆S = 2KN ln2 ——— from eqn.[A]

∆S = 0 (expected)

But [A] shows that,

∆S = 2KN ln2 > 0 (34)
Since for Carnot Entropy,
V 3
Sf − (S1 + S2 ) = KNf (ln[ Nff ( 32 KT ) 2 ] + 5 3 4πm
2 + 2 ln[ 3h2 ]) −
V1 3 3 5 V2 3 3
KN1 (ln[ N ( KT ) ] +
1 2
2
2 + 23 ln[ 4πm
3h2 ]) − KN2 (ln[ N ( KT ) 2 ] + 25 + 32 ln[ 4πm
2 2 3h2 ])

V V1 V2
∆S = KNf ln[ Nff ]−KN1 ln[ N 1
]−KN2 ln[ N 2
]+K( 32 ln[ 32 KT ]+ 25 + 32 ln[ 4πm
3h2 ])(Nf −
N1 − N2 )

We know that, Nf − N1 − N3 = 0
V N1 V N2
Therefore, ∆S = KN1 ln[ Vf1 Nf ] + KN2 ln[ Vf2 Nf ]

11
Now for V1 = V2 = V and Vf = 2V, N1 = N2 = N and Nf = 2N

∆S = KN ln[ 2V
V
N
2N ] + KN ln[ 2V
V
N
2N ] =0 ∵ ln1 = 0

V 3 3
So, to get Scarnot = N K[ln[ N ( 2 KT ) 2 ] + 52 ] + C

Ω 3
N! = ΩGibbs ←− Ω = (V ( 2πmυ 2 N
3 ∆ 1
h2 ) ) 2 N U Γ 3N ! 2

3
SB ↑= N K[ln(V ( 32 KT ) 2 ) + 3
2 + 3 4πm
2 ln[ 3h2 ]]

Since KlnN ! = KN lnN − KN

V 3 3 5
SB − KlnN ! = N K[ln( N ( 2 KT ) 2 ) + 2 + 32 ln[ 4πm
3h2 ]]
...................

12
3 Canonical Ensemble
In the above sections, we have discussed the basic thermodynamic relations
and derived an expression of entropy as a function of number of particles (N ),
volume (V ) and total internal energy of the system (U ) for a micro-canonical
ensemble. In the micro-canonical ensemble, the thermodynamic properties U ,
V , N remain constant throughout the process. In the canonical ensemble how-
ever, the internal energy of the system ceases to be a constant parameter, as
the system is allowed to exchange energy with the surroundings while keeping
the number of particles and volume of the system constant.

In the canonical ensemble, the system is in thermal equilibrium with the sur-
roundings (heat reservoir). Both the system and heat reservoir attain the same
temperature at the equilibrium condition. Hence, to derive all the thermody-
namic properties of this type of system configuration, we need to define a state
function at the macroscopic level which is a function of T , V and N . But before
that, it would be a good idea to define a function at the microscopic level, and
then derive a relationship between the microscopic function and its macroscopic
counterpart.

Let us consider a system immersed into a very large heat reservoir. At equi-
librium, the system and the reservoir attain the same temperature T , but their
energies would be variable at any instant. The energy values of system and
reservoir will lie between 0 and E0 , where E0 is the combined total energy of
the system and reservoir. At any instant, the system and reservoir will have the
energy values E and ER such that

E + ER = E0

where E0 is constant at any instant. Now, since the reservoir is much larger
than the system, ER is much greater than E. It also implies that

E ≪ E0

i.e., the energy of the system E is a very small fraction of the combined total
energy E0 .

Now let us focus on the energy configuration of the reservoir. The probability
of the reservoir assuming a particular energy value ER is directly proportional
to the number of micro states having the energy value ER .

Mathematically, the above statement can be represented as

p ∝ ΩR (ER )

We can also write p in terms of E as

p ∝ ΩR (E0 − E)

13
Now, if we take the ratio of the probabilities of the reservoir assuming the energy
states Ej and Ek respectively, then we can write it as follows

p(Ej ) ΩR (E0 − Ej )
=
p(Ek ) ΩR (E0 − Ek )

Using the famous Boltzmann expression for entropy, we can write the number
of micro states of a reservoir having the energy value E as a function of entropy
of the reservoir at that particular energy value.

SR = kB ln ΩR (E0 − E)
 
SR (E0 − E)
⇒ ΩR (E0 − E) = exp
kB
Hence we can write the probability ratios at Ej and Ek as
 
p(Ej ) (SR (E0 − Ej ) − SR (E0 − Ek ))
= exp
p(Ek ) kB

We have already proved above that E ≪ E0 for all practical purposes. In this
case, we can expand the entropy term as
 
∂SR
SR (E0 − E) = SR (E0 ) − E
∂E V,N

From the second law of thermodynamics, we can see that

 
∂E
T =
∂S V,N

Hence, we get the final expression of entropy of the reservoir as

E
SR (E0 − E) = SR (E0 ) −
T
From the above results, we get
 
p(Ej ) Ej Ek
= exp − +
p(Ek ) kB T kB T

By the above equation, we can see that

 
Ej
p(Ej ) ∝ exp − ≡ exp (−βEj )
kB T

1
where β =
kB T
We have discussed the relationship between probability at a particular energy

14
value p(E) and energy of the system E. Now, it would be great if could ob-
tain a complete expression of p(E) by normalizing it. We can write p(E) at a
particular energy value E as

e−βE
p(E) =
Z
where Z is the normalizing constant.

To compute the value of Z, we add up all the probabilities at all possible energy
values. This can be represented mathematically as given below
X
p(Ej ) = 1
j

e−βEj
P
j
⇒ =1
Z
X
⇒ Z= e−βEj
j

In the above equation, Z signifies the sum of all the possible energy states in
the system at equilibrium, and is also known as the ”Canonical Partition Func-
tion”. To avoid confusion with the Grand Canonical Partition Function ZGCE ,
we shall represent canonical partition function by ZCE hereafter.

Since we know the probability distribution of states corresponding to an en-

ergy value, we can calculate the expectation value of energy (mean energy) of
the system. X
⟨E⟩ = Ej p(Ej )
j

Ej e−βEj
P
j
⇒ ⟨E⟩ = P
j e−βEj
Now we already know that
X
ZCE = e−βEj
j

On differentiating ZCE wrt β, we get

∂ZCE X
=− Ej e−βEj
∂β j

Hence we can write ⟨E⟩ as

 
1 ∂ZCE
⟨E⟩ = −
ZCE ∂β V,N

15
or  
∂ (ln ZCE )
⟨E⟩ = −
∂β V,N

The calculations done above were based on the assumption that each state has
its own distinct energy values, which is not true in reality. We always have a
certain degeneracy in the number of states Ω(E) corresponding to an energy
value. So, to account for all these degenerate states, we need to modify the
expression of canonical partition function ZCE by multiplying the number of
states Ω(E) with the exponential term in the former expression of ZCE .

Mathematically, the above statement can be represented as

X
ZCE = Ω(Eν )e−βEν
ν

We already know that  

S(Eν )
Ω(Eν ) = exp
kB
Substituting this value in the expression of ZCE , we get
 
X S(Eν )
ZCE = exp − βEν
ν
kB

The above expression of canonical partition function can be approximated by

taking the peak value of energy U and its corresponding entropy value S(U ) in
place of the summation of the exponential terms for different energy values Eν .
This can be shown mathematically as
 
S(U )
ZCE ≈ exp − βU
kB

Substituting the value of β in the above expression, we get

 
S U
ZCE = exp −
kB kB T
or  
U − TS
ZCE = exp −
kB T
So far, we have derived the general expression for the canonical partition func-
tion ZCE . We wish to develop a relationship between the above statistical
(microscopic) quantity and a thermodynamic (macroscopic) quantity. Let us
introduce a new thermodynamic property A, or the Helmholtz free energy. The
mathematical expression of A is as given below:

A = U − TS

16
Now, by substituting the above relation in the expression for ZCE and taking
log on both sides, we get

A(T, V, N ) = −kB T ln(ZCE (T, V, N ))

We have successfully developed a relationship between the canonical partition

function (microscopic quantity) and Helmholtz free energy (macroscopic quan-
tity). Now we can derive all the thermodynamic properties as a function of
Helmholtz free energy A, the details of which are discussed in the further sec-
tions.

3.1 Micro to Macro connecting relation for CE

In statistical physics, a canonical ensemble is the statistical ensemble that rep-
resents the possible states of a mechanical system in thermal equilibrium with
a heat bath at a fixed temperature.The system can exchange energy with the
heat bath, so that the states of the system will differ in total energy.

Figure 4: Canonical Ensemble

A = −KT lnZ (35)

A = U − TS (36)

A = −P V + µN (37)

17
 From the second law of thermodynamics, we know that :

T dS = dU + P dV − µdN (38)

Now, from above

dA = dU − T dS − SdT

dA = −P dV + µdN − SdT [using (38)]

   
∂A ∂(T lnZ)
⇒S=− = KB (39)
∂T V,N ∂T V,N

   
∂A ∂(lnZ)
⇒P =− = KB T (40)
∂V T,N ∂V N,T

   
∂A ∂(lnZ)
⇒µ= = −KB T (41)
∂N V,T ∂N V,T

Now,

U = A + TS

 
∂(T lnZ)
U = −KB T lnZ + T KB
∂T V,N

 
2 ∂(lnZ)
U = T KB (42)
∂T V,N

18
3.2 CE Partition function for non-interacting or ideal gas
Now we are going to calculate the partition function for the Canonical En-
semble and derive the physical macro quantities like Helmholtz free energy,
Entropy,Pressure and internal energy form that partition function of canonical
ensemble.

Formula for canonical partition function is:

X
Z= e−βEi (43)
i

X
Z= Ω(Ev )e−βEv (44)
v

X  d3N xd3N p 
Z= e−βEv (45)
N !h3N v

d3N xd3N p p2
Z  
Z= e−βEv whereE = (46)
N !h3N v 2m

 N
∞
−βp2
VN
Z
−
Z= 4πp2 dpe 2m  (47)
 
N !h3N

0

βp2 2m
But = z =⇒ pdp = dz;
2m β
N
1 1

N Z ∞ 
V 2m 2 m
Z= 4π z 2 dz e−z  (48)
 
N !h3N β β

0

N
3 Z ∞ 1

N
 √ m 2

V
Z= 4π 2 z 2 dze−z  (49)

N !h3N β 0

Z ∞ √ √
π
since zdze−z = 2
0

19
 N
3

N

V  2πm 2 
Z= (50)
N !h3N β
 

3 N
 
1 V 1
Z= [2πmkT ] 2  as = kT (51)
N ! h3 β

3 N
 
1 V
Z= [2πmkT ] 2  (52)
N ! h3

Helmholtz free Energy:

Formula for Hamiltonian free energy is :

A(N, V, T ) = −KT ln Z (53)

   
V
A(N, V, T ) = −N KT ln 3 + ln N − 1 (54)
λ

using the Striling formula

ln(N !) = N ln N − N
h
and Here λ = √ which is ”Thermal de-Broglie wavelength”
2mπkT

N λ3

 

A(N, V, T ) = N KT ln −1 (55)
V

N λ3
   
A = N KT ln −1 (56)
V

20
Entropy:

Formula for Entropy :

 
∂A
S=− (57)
∂T N,V

N λ3
   
3
S = −N k ln[ − 1 + N KT (58)
V 2T

  
V 5
S = N K ln + (59)
N λ3 2

  
V 5
S = N K ln + (60)
N λ3 2
Pressure :

Formula for pressure :

 
∂A
P =− (61)
∂V N,T

1
P = N KT (62)
V

N KT
P = (63)
V

P V = N KT (64)

Internal energy :

Formula for Internal energy:

21
 U = A + TS (65)

N λ3
      
V 5
U = N KT ln − 1 + N KT ln + (66)
v N λ3 2

3N KT
U= (67)
2

3
U= N KT (68)
2

3.3 CE Partition function for Classical Harmonic Oscilla-

tor (CHO)
Now, in the next two sections we are going to replace our system with simple
harmonic oscillator (SHO), first classical and then quantum.

So, consider N non-interacting classical SHOs in equilibrium at temperature

T. Each one has two degrees of freedom (x, p), and hamiltonian
1 2 p2 1 p2
H1 = H1 (x, p) = kx + = mω 2 x2 + (69)
2 2m 2 2m
here p
m is the mass and is the spring constant; in the second expression,
ω ≡ k/m is the natural frequency. Assume their locations are fixed so they
are distinguishable, although identical.

Thus, we know that Then Z = Z1N where Z1 is the partition function of one of
them and is given by the following equation:
Z
dxdP
Partition function, Z1 = e−βH (70)
h

Solving the above integral equation:

Z
dxdP
Z1 = e−βH
h
"Z #" Z #
∞ ∞
1 −βmω 2 x2 /2 −βp2 /2m
=⇒ Z1 = e dx e dp
h −∞ −∞

22
 " Z #" Z #
∞  −1 −1 ∞  m  12 −1
1 −Z

2 2 −Z
=⇒ Z1 = 2 e 2βmω z 2 dz 2 e z 2 dz
h 0 0 2β
This is two Gaussian integrals:
" #" #
1  1  12 √  m  21 √
Z1 = 2 π 2 π
h 2βmω 2 2β
" #" #
1  2πKT  12   12
=⇒ Z1 = 2πKT m
h mω 2
Thus, we get:
2πKT K T 
B
Z1 = =
hω ℏω
Note that in the last step, we re-wrote the answer in terms of the natural fre-
quency of the oscillator.(Note that this is a ratio of energies.)

Now consider many oscillators (like positions of atoms in a crystal), and let’s
extract the thermodynamics:
 K T N
B
Z = Z1N =
ℏω
also,
∴ A = −KT lnZN (71)
 ℏω 
=⇒ A = N KT ln (72)
KT
Also P, S, V and U can be calculated from the above equation as follows:
∂A
P =− = 0, Since A(V ) = constant (73)
∂V
Above equation holds true since, A(V ) = constant.
 
∂A
S=− (74)
∂T N,V
       
ℏω 1 KT
S = −N K ln( ) + N KT = N K ln +1 (75)
KT T ℏω

U = A + T S = N KT (76)

For Ideal Gas :

Now if the system is composed of Ideal Gas, then the following calculations

23
hold:
CP is heat capacity at constant pressure
    
∂ ∂ 3 5
CP = (U + P V ) ⇒ CP = N KT + N KT ⇒ CP = N K
∂T P ∂T 2 2

Similarly,
CV is heat capacity at constant volume
    
∂U ∂ 3 3
CV = ⇒ CV = N KT ⇒ CV = N K
∂T V ∂T 2 2

This implies:
CP − CV = N K = R (77)

But here, that means in case of classical harmonic oscillator

∂U
CP = CV = = NK = R (78)
∂T

since, A(V ) = constant.

3.4 CE Partition function for quantum Harmonic Oscilla-

tor (QHO)

Quantum harmonic oscillator:

Energy eigen value for QHO
 
1
ϵn = n+ ℏω (79)
2

where n = 0, 1, 2, 3, ..........
Partition function of single particle :

 
∞
e−βkω/2 1
e−β (
n+ 21 )ℏω
X
z1 = = =  (80)
1 − e−βℏω

n=0 2 sinh βℏω
2

24
Total partition function:

 N
1 N
  e−( 2 βℏω) 1 − e−βℏω
N N 
zn = (z1 ) =  (81)
βℏω
2 sinh 2

Helmholtz free energy:

 
ℏω  −βℏω
A = −KT ln 2 = N KT β + ln 1 − e (82)
2

Therefore, using above formula we get,

 
∂A
Ṗ = − =0 (83)
∂V N,T

 N KT e−βℏω (ℏω/kT 2 )
 
∂A
= −N K ln 1 − e−βℏω +

S=−
∂T V,N 1 − e−βℏω
"
#
ℏω
KT −βℏω

S = NK − ln 1 − e (84)
eβℏω − 1
 
ℏω ℏω
U = TS + A = N + βℏω (85)
2 e −1

25
4 Grand-Canonical Ensemble
According to grand canonical ensemble,
E + ER = E0 = Constant
N + NR = N0 = Constant

The Probability of system = Probability of R

Here, ρ(E, N ) = ρ(E0 − E, N0 − N )

ρ(Ej , Nj ) ΩR (E0 − Ej , N0 − Nj ) eSR (E0 −Ej ,N0 −Nj )/KB

= = S (E −E ,N −N )/K
ρ(Ek , Nk ) ΩR (E0 − Ek , N0 − Nk ) e R 0 k 0 k B
   
∂SR ∂SR
Now SR (E0 − Ej , N0 − Nj ) = SR (E0 , N0 ) − Ej − Nj
∂Ej N ∂Nj E

26
∵ T
dS = dU + P dV − µdN
 
∂S 1 ∂S µ
⇒ = and =−
∂U V,N T ∂N V,U T

Ej µNj
∴ SR (E0 − Ej , N0 − Nj ) = SR (E0 , N0 ) − +
T T
  
ρ(Ej , Nj ) SR Ej µNj SR Ek µNk
∴ = exp − + − − +
ρ(EK , NK ) KB KB T KB T KB KB T KB T
(E − µN )
−
⇒ ρ(E, N ) ∝ e kT

∝ e−β(E−µN )

e−β(Ej −µNj ) X
⇒ ρj = P −β(E −µN ) ⇒ Z = e−β(Ej −µNj )
je
j j
j
Partition Function
Now,P
Z = j e−β(Ej −µNj )
Z = γ ω(Eγ )e−β(Eγ −µNγ ) (This is Density of states concept)
P
 
P S(Eγ ) Eγ µNγ
Z = γ exp − +
K KT KT
 
S γ µN
Z ≃ exp − +
K KT KT
=⇒ T S − U + µN = KT lnZ = P V = Φ which is Grand Canonical poten-
tial.

4.1 Micro to Macro connecting relations for GCE

In statistical physics,a grand canonical ensemble (also known as the macro
canonical ensemble) is the statistical ensemble that is used to represent the
possible states of a mechanical system of particles that are in thermodynamic
equilibrium (thermal and chemical) with a reservoir.The system is said to be
open in the sense that the system can exchange energy and particles with a
reservoir, so that various possible states of the system can differ in both their
total energy and total number of particles. The system’s volume, shape, and
other external coordinates are kept the same in all possible states of the system.

27
 Figure 5: Grand Canonical Ensemble

Φ = −KT lnZ(T, µ, V ) (86)

Φ = −P V (87)

Φ = U − T S − µN (88)

From the second law of thermodynamics, we know that :

T dS = dU + P dV − µdN (89)
From above,

dΦ = dU − T dS − SdT − µdN − N dµ

dΦ = −P dV − SdT − N dµ

   
∂Φ ∂(T lnZ)
⇒S=− = KB (90)
∂T µ,V ∂T µ,V

28
    
∂Φ ∂(lnZ)
⇒P =− = KB T (91)
∂V µ,T ∂V µ,T

   
∂Φ ∂(lnZ)
⇒N =− = KB T (92)
∂µ V,T ∂µ V,T

Now,

U = Φ + T S + µN

   
∂(T lnZ) ∂(lnZ)
U = −KB T lnZ + T KB + µKB T
∂T µ,V ∂µ V,T

   
∂(lnZ) ∂(lnZ)
U = T 2 KB + µT KB
∂T µ,V ∂µ V,T

Here Finally,

 
∂(lnZ) ∂(lnZ)
U = KB T T +µ (93)
∂T ∂µ

5 Equivalence between CE and GCE

Partition Function : In physics, a partition function describes the statistical
properties of a system in thermodynamic equilibrium. Partition functions are
functions of the thermodynamic state variables, such as the temperature and
volume. Most of the aggregate thermodynamic variables of the system, such as
the total energy, free energy, entropy, and pressure, can be expressed in terms
of the partition function or its derivatives. The partition function is dimension-
less. Each partition function is constructed to represent a particular statistical
ensemble (which, in turn, corresponds to a particular free energy). The most
common statistical ensembles have named partition functions.

For Canonical Ensemble :

The canonical partition function applies to a canonical ensemble, in which the
system is allowed to exchange heat with the environment at fixed temperature,

29
volume, and number of particles.
X
CE
ZN = e−(βEi ) (94)
i=0
X d3N xd3N p
= 3N
e(−βEν ) (Eν = N ϵ)
ν
N !h
VN
Z
= [ d3 pe−βϵ ]N
N !h3N
CE
ZN
= (95)
N!
For Grand Canonical Ensemble :
The grand canonical partition function applies to a grand canonical ensemble,
in which the system can exchange both heat and particles with the environment,
at fixed temperature, volume, and chemical potential.
X
Z GCE = e−β(E−µ) (96)

X d3N xd3N p
= ( 3N
)Eν ,Nα e−β(Eν −µα )
ν,α
N α !h
X VN Z
= 3N
[ d3 pe−β(E−µ) ]N (∵ µα = N µ)
α
N !h
X (eβµ ZCE )Nα
=
α
Nα !
p2
Z
V V
where Z1CE = d3 pe−βϵ = for ϵ = (97)
h3 λ3 2m
is one particle partition function of CE system with
h
λ= √ (thermal de-Broglie wavelength) (98)
2πmKT
So if we take all Nα from 0 to α
∞
X (eβµ ZCE )Nα
Z GCE (µ, T, V ) = (99)
Nα !
Nα =0

= exp{eβµ ZCE }
⇒ −P V = Φ = −KT lnZ GCE = −KT {eβµ ZCE }
V d3 p −β(ϵ−µ)
Z
= −KT e
h3
V d3 p −β(ϵ−µ)
Z
where N = e (100)
h3
GCE (Classical Ideal Gas) :

30
 1. For one-particle: Partition function is written as:
X
Z1 = e−β(ϵ−µ) (101)
Z 3 3
d xd p −β(ϵ−µ)
= e
h3

d3 xd3 p
X Z
Remember, =
h3

2. For many or N particle: Partition function is written as:

ZN = Z1 × Z2 × Z3 ... (102)
Y
= Zi
i
Y (ϵi −µi )
= e−β
i

Φ = −P V = −KT lnZN (103)

Y
= −KT ln{ Zi }
i
X
= −KT lnZi
i
d3 xd3 p
Z
= −KT ln(Z)
h3
where,

Z = exp{e−β(ϵ−µ) }
α
X {e−β(ϵ−µ) }Nα
=
Nα !
Nα

This imples,

d3 p −β(ϵ−µ)
Z
KT N
P = KT 3
e = (104)
h V

V d3 p −β(ϵ−µ)
Z
Φ = −P V = −KT e
h3
Z
KT V
⇒P = N, where N = 3 d3 pe−β(ϵ−µ)
V h
Z
V
= d3 pfo (ϵ)
h3

31
where fo (ϵ) is Maxwell distribution function
Now,
 
dΦ
N = −
dµ V,T
V d3 p −β(ϵ−µ)
Z
= −(−KT )β e
h3

p2
Z
V 1
N= 3 d3 pfo (ϵ) = V for ϵ = (105)
h λ3 (T ) 2m
(Thermal distribution of function of particle with energy ϵ)

Since,
 dΦ 
S = − (106)
dT µ,V
V d3 p −β(ϵ−µ) (µ − ϵ) V d3 p −β(ϵ−µ)
Z Z
= K e +KT e
h3 −KT 2 h3
| {z } | {z }
N N

when the above equation is multiplied with T, we get

V d3 p
Z
T S = KT N − µN + ϵfo (ϵ)
h3
| {z }
U
=⇒ T S = P V − µN + U (107)

Internal Energy:

V d3 p
Z
U = [ϵ]fo (108)
h3
3
= N KT
2
p2
 
3 V
= KT f or ϵ= (109)
2 λ3 (T ) 2m

After knowing N , U , we get:

U + P V − µN
S =
T
5 µN
= NK − (110)
2 T

32
6 Quantum mechanical version of partition func-
tion
According to classical physics, the partition function for a single particle is
defined mathematically as :
Z = e−β(ϵ−µ) (111)
In quantum mechanics, an energy level is degenerate if it corresponds to two
or more different measurable states of a quantum system. Conversely, two or
more different states of a quantum mechanical system are said to be degenerate
if they give the same value of energy upon measurement.

If quantum degeneracy is n for energy state ϵ, then its partition function is:
X
Z= e−βn(ϵ−µ) (112)
n

Pauli exclusion principle states that no two electrons in an atom can be at

the same time in the same state or configuration.The exclusion principle subse-
quently has been generalized to include a whole class of particles.

Subatomic particles fall into two classes, based on their statistical behaviour.
Those particles which follow the Pauli exclusion principle are called fermions
while those that do not obey this principle are called bosons.

According to Pauli Exclusion Principle, n = 1 for fermion i.e only one particle
is allowed in a particular energy level. But, for Boson, the quantum degeneracy
of energy levels,n can take any value from 1, 2, 3, ...∞. The classical definition
also misses the possibility of n = 0. But this is a valid quantum degeneracy
value for both boson and fermion. Hence, the partition function for each energy
level for fermions and bosons is given by :

(i) Fermion -
1
X
Z= e−βn(ϵ−µ) = [1 + e−β(ϵ−µ) ] (113)
n=0

(ii) Boson -
∞
X 1
Z= e−βn(ϵ−µ) = (114)
n=0
1 − e−β(ϵ−µ)
(Using the formula for sum of infinite G.P.)

The total partition function, Zt for all particles is given by the expression below :
Y Y X
Zt = Zi = Z1 × Z2 × Z3 × ... =⇒ ln Zt = ln { Zi } = ln Zi (115)
i i i

33
The above calculation of ln Zt will be useful for the calculation of Grand Canon-
ical Potential i.e Φ since we know that Φ = −KT ln Zt

6.1 quantum version of thermodynamical relation for Bosons

and Fermions

Bosons are particles which have integer spin and which therefore are not con-
strained by the Pauli exclusion principle like the half-integer spin fermions.

Boson → spin is integer ℏ =⇒ s = (0,1,2,3,...)ℏ

Fermions are particles which have half-integer spin and therefore are constrained
by the Pauli exclusion principle.

Fermion → spin is half integer of ℏ =⇒ s= (1,3,5,7,...) ℏ2

So now we can calculate -PV:

X
− P V = Φ = −KT ln Zt = −KT ln Z (116)

For Fermion :
X
ϕf ermion = −KT ln [1 + e−β(ϵ−µ) ] (117)

For Boson :
X
ϕboson = −KT ln [1 − e−β(ϵ−µ) ]−1 (118)

In general, we can write:

−KT X
− PV = Φ = ln [1 + ηe−β(ϵ−µ) ] (119)
η
Z 3
−KT d p
= V ln [1 + ηe−β(ϵ−µ) ] (120)
η h3
where η = +1 for Fermion and -1 for Boson

Now we know that:

1 X ηe−β(ϵ−µ) V d3 p
  Z
∂Φ X 1 1
N =− = −β(ϵ−µ)
= β(ϵ−µ)
= 3 β(ϵ−µ)
∂µ T,V η 1 + ηe e +η h e +η
(121)

34
The Fermi-Dirac distribution applies to fermions, particles with half-integer
spin which must obey the Pauli exclusion principle. It is a type of quantum
statistics that applies to the physics of a system consisting of many identical
particles.

Number of molecules (using Fermi-Dirac distribution) where η= +1:

Z 3 Z 3
d p d p 1
NF D = V fFD = V (122)
h3 h3 eβ(ϵ−µ) + 1

The Bose-Einstein distribution describes the statistical behavior of integer

spin particles (bosons). At low temperatures, bosons can behave very differently
than fermions because an unlimited number of them can collect into the same
energy state, a phenomenon called ”condensation”.

Number of molecules (using Bose-Einstein distribution) where η= -1:

Z 3 Z 3
d p d p 1
NBE = V fBE = V (123)
h3 h3 eβ(ϵ−µ) − 1

The Maxwell–Boltzmann distribution describes the distribution of speeds

among the particles in a sample of gas at a given temperature. The distri-
bution is often represented graphically, with particle speed on the x-axis and
relative number of particles on the y-axis.The distribution function implies that
the probability dp that any individual molecule has an energy between ϵ and ϵ
+ dϵ.The total energy (ϵ) usually is composed of several individual parts, each
corresponding to a different degree of freedom of the system.

Number of molecules (using Maxwell-Boltzmann distribution) where η= 0:

Z 3 Z 3
d p d p −β(ϵ−µ)
NM B = V 3
fMB = V e (124)
h h3
We discussed indistinguishability before in the context of the second law of ther-
modynamics and the Gibbs paradox. In that, we found that we could decide if
we want to treat particles as distinguishable or indistinguishable. If we want to
treat the particles as distinguishable, then we must include the entropy increase
from measuring the identity of all the particles to avoid a conflict with the sec-
ond law of thermodynamics. We do this by adding a factor of N1 ! to the number
of states Ω, i.e. instead of Ω ∼ V N we take Ω ∼ N1 ! V N ; then there is automati-
cally no conflict with the second law of thermodynamics. This kind of classical
indistinguishable-particle statistics, with the N! included, is known as Maxwell-
Boltzmann statistics. Quantum identical particles is a stronger requirement,
since it means the multiparticle wavefunction must be totally symmetric or to-
tally antisymmetric. In a classical system, the states are continuous, so there is

35
exactly zero chance of two particles being in the same state. Thus, the difference
among Fermi-Dirac, Bose-Einstein and Maxwell-Boltzmann statistics arises en-
tirely from situations were a single state has a nonzero change of being multiply
occupied.

Classical distribution (M.B) → Quantum distribution ( B.E and F.D )

f0 = e−β(ϵ−µ) [f or M B distribution] (125)

For Fermi-Dirac distribution,

1
f0 = (126)
eβ(ϵ−µ) + 1

For Bose-Einstein distribution,

1
f0 = (127)
eβ(ϵ−µ) −1
Now, we formulate a general equation for the number of molecules N for differ-
ent types of distribution as follows:
Z
X V
f0 = N = 3 d3 pf0 (ϵ) (128)
h
Now we substitute the value of f0 where the value of η can be varied to get the
value of N for different quantum distributions.
the equation (107) becomes,
Z  
V 3 1
N= 3 d p β(ϵ−µ) (129)
h e +η

for MB distribution, the value of η is 0

for FD distribution, the value of η is 1
for BE distribution, the value of η is −1

Now we can calculate the internal energy

Z Z
X V 3 V 1
ϵf0 = U = 3 d p[ϵ]f0 (ϵ) = 3 d3 p[ϵ] β(ϵ−µ) (130)
h h e +η

Calculating the value of PV:

KT X
P V = −Φ = ln{1 + ηeβ(µ−ϵ) } (131)
η

V dp
Z Z
KT V 1
PV = ln{1 + ηeβ(µ−ϵ) } = 3 d3 p[?] (132)
η h3 h eβ(ϵ−µ)+η

36
Now we can cross check through the value of PV deduced above if it is same
as that of -KTln z and calculate pressure for fermi-dirac, bose-einstein and
maxwell-boltzmann accordingly:
P ∂
−1 X β(µ−ϵ)
− i ∂η ln[1 + ηeβ(µ−ϵ) ]
ln z = ln[1 + ηe ] = lim ∂η
(133)
η i η→0
∂η

It will give us
X eβ(µ−ϵ) X
ln z = − lim =− eβ(µ−ϵ) (134)
η→0 1 + ηeβ(µ−ϵ)
i i

Hence:

d3 xd3 p −β(ϵ−µ)
X Z
−β(ϵ−µ)
P V = Φ = −KT ln z = KT e = KT e (135)
i
h3

d3 xd3 P −β(ϵ−µ)
R
where N = h3 e

Now we know that:

  Z 3 3
∂Φ X d xd p −β(ϵ−µ)
N =− = KT ∗ β e−β(ϵ−µ) = e (136)
∂µ T,V h3

Now, similarly we apply the three distributions individually and find the Pres-
sure for respective distributions.
Pressure for Fermi-Dirac(PF D ):
Z 3
d p
PF D = KT V (ln{1 + e−β(ϵ−µ) }) (137)
h3

Pressure for Bose-Einstein(PBE ):

d3 p
Z
PBE = −KT V ln{1 − e−β(ϵ−µ) } (138)
h3

Pressure for Maxwell-Boltzmann(PM B ):

Z 3
d p −β(ϵ−µ)
PM B = KT V e (139)
h3

37
6.2 Photon Gas : example Boson system
In the previous sections, we have explored the realms of the Grand Canonical
Ensemble, and have ventured into the quantum mechanical aspects of statistical
mechanics. We are also familiar with some of the statistical distributions used
to calculate the macroscopic variables from microscopic variables.

Before proceeding to the next topic, it would be great if we go through the sta-
tistical distributions part once again as a primer to the next topic. In the Grand
Canonical Ensemble, Maxwell-Boltzmann distribution is used for classical sys-
tems (systems under the domain of classical mechanics), while Fermi-Dirac and
Bose-Einstein distributions are used for quantum systems. In addition, Fermi-
Dirac distribution is applicable on Fermions (electrons, protons, muons etc.),
while Bose-Einstein distribution is applicable on Bosons (photons, gluons etc.)

The statistical distributions can be written as

1
f = β(ϵ−µ) (140)
e +η
If η = 1, eqn.(140) becomes Fermi-Dirac distribution
If η = 0, eqn.(140) becomes Maxwell-Boltzmann distribution
If η = −1, eqn.(140) becomes Bose-Einstein distribution

Now that we have gone through the statistical distributions used in the Grand
Canonical Ensemble, let us proceed to the application of the theories that we
have studied above. One of the most prominent applications of the Bose-Einstein
statistical distribution is the study of photon gas and calculation of macroscopic
variables for the same. As it is already known, light constitutes of energy packets
known as photons, which are basically Bosons with spin 1. Hence we can con-
sider light to be a gas of photons, with each photon having energy-momentum
relation as
ϵ = pc
We can use the above energy-momentum relation to calculate the macroscopic
parameters such as number of particles (N ), total internal energy (U ) and pres-
sure (P ). Let us start with the calculation of the number of particles in the
system. Z 3 3
d xd p 1
N =2 3 βϵ
(141)
h e −1
In eqn.(141), the general expression for number of particles is multiplied by 2
to account for two spin states (+1 and −1) of the photons. We already know
that Z
d3 x = V

Plugging this value in eqn.(141), we get

Z
2V 1
N= 3 4πp2 dp βpx (142)
h e −1

38
 Let βpc = x
kT
=⇒ dp = dx
c
On substituting these values in eqn.(142), we get
8πV (KT )3 ∞ x2
Z
N= dx (143)
h3 c3 0 ex − 1
In the above equation, the integral term is a special integral also known as
Riemann Zeta function, and it is denoted by ζ (n). The Riemann Zeta-function
is defined as Z ∞ n−1
1 x
ζ(n) = dx
Γ (n) 0 ex − 1
On comparing the above equation with the integral term in eqn.(143), we can
clearly see that n=3.

On dividing both sides of eqn.(143) by V and substituting the value of Rie-

mann Zeta function in place of the integral term, we get
 3
N kT
= 8π ζ (3) Γ (3)
V hc
 3
kT
= 16π ζ (3) ∝ T 3
hc
Hence from the above equation, we can see that the number density of a photon
gas system is directly proportional to the third power of Temperature (T ).

Let us now proceed to the calculation of internal energy of the photon gas.
The microscopic variable in this case is the energy of a single photon. The total
internal energy of the photon gas system is defined as
Z 3 3
d xd p ϵ
U =2
h3 eβϵ − 1
Z
2V ϵ
=⇒ U = 3 4πp2 dp βϵ
h e −1
Dividing both sides by V , we get
p3
Z Z
U 8πc
= 3 dp = uV dν (144)
V h eβpc − 1
where
8πc p3
uν dν = dp
h3 eβpc − 1
hν hdν
Substituting p = c and dp = c in the above equation, we get
 8πν 3 h  dν
uν dν = (145)
c3 eβhν−1

39
In eqn.(145), the term uν represents the spectral distribution of energy in the
black body radiation. It is now very clear that we can easily calculate the total
energy density by integrating the spectral distribution from 0 to infinity.

Let us now solve eqn.(144)

Z
U
= uν dν
V
(146)
p3 dp
Z
8πc
= 3 βpc
h e −1
Let βpc = x
kT
=⇒ dp = dx
c
On substituting the above values in eqn.(146), we get

8πc kT 4 α x4−1
Z
U
= 3 ( ) x
dx
V h c 0 e −1
8π
= 3 3 (kT )4 ζ(4) ∝ T 4 (147)
h c
8π
= 3 3 (kT )4 ζ(4)
h c
Here
π4
ζ(4) =
90

Hence
U 8(π)5
= (kT )4
V 15h3 c3
(148)
π2
= (kT )4 ∝ T 4
15(ℏc)3
Hence we are able to get a relationship between energy density and temperature
in the above equation. We can clearly see from eqn.(148) that the energy den-
sity is directly proportional to the fourth power of temperature. This relation
goes a long way in deriving the Stefan-Boltzmann law of radiation.

Now that we have already ventured into the total internal energy of the photon
gas, let us try to calculate the value of Stefan constant. For a blackbody, the
intensity is given by
cU
I= (149)
4V
By Stefan-Boltzmann’s law, we already know that the intensity of a blackbody
can be written as
I(T ) = σT 4 (150)

40
On comparing eqns. (149) and (150), we get
π2 k4
σ= (151)
60h3 c2
Now, let us try to calculate the pressure of the photon gas.

Φ
Pressure, P = −
V
2d3 pd3 x 

1 −KT
Z
−β ϵ
=− ln 1 − e
V −1 h3
Z
2KT
d3 p ln 1 − e−β ϵ

=− 3
h

Here, ϕ = −P V , is the grand chemical potential, ϵ, is the single particle energy.

Now, we substitute ϵ = pc(relativistic value) where p is momentum and c is the
1
speed of light. We also know that, β = KT .

8π ∞ 2
Z
P
P dP ln 1 − e−βpc ,

=− 3 ϵ= pc
KT h 0
∞ Z ∞ 3
8π p3  p βce−βpc
 
−βpc
=− 3 ln 1 − e − dp
h 3 0 0 3 1 − e−βpc
∞
p3 
Here,| ln 1 − e−βpc =0
3 0
8π ∞ βp3
Z
c KT
= 3 βpc
dp, βpc = x and dp = dx
h 0 3 e −1 c
  4 Z ∞ 4−1
8π βc KT x
= 3 x−1
dx
h 3 c 0 e

Here, we brought βc outside of integral as they are constants.

Then, we multiplied and divided by β 3 c3 to convert the integral into Γ(4)ζ(4) .Solved
using Riemann zeta function

8π 1 1U 1
P = 3 3
(KT )4 Γ(4)ζ(4) = , PV = U
3 h c 3V 3
Now, lets substitute the value of Γ(4)ζ(4) in the above equation
 4
16π π
= 3 3 K 4T 4
h c 90
 5 4
8π K
= T4
45h3 c3

41
This is the value of pressure of photon gas wich is directly proportional to T 4

6.3 Calculation of average temperature inside Sun

From photon gas calculation, either from Stefan-Boltzmann’s law or Wein’s
displacement law, one can easily able to calculate surface temperature of Sun
(∼ 5 × 103 K ) or any stars. However, as we go towards the core of the Sun
or star, the temperature will increase gradually. Here we will calculate average
temperature of Sun or any (young) star.
Let us take average mass density :
M
ρ(r) ≈ ⟨ρ⟩ = 4 3
3 πR
RR
0
ρ(r)4πr2 dr M
⟨ρ⟩ = RR = 4 3
3 πR
4πr 2 dr
0

where ρ is the density,M is the mass of the object, R is its radius. Here we
have considered a small sphere inside a big sphere,as its density is constant
we can integrate over the radius from 0 to R to get the average mass density.
Calculating the Gravitational potential energy of the sun. Ω
Z R
GM (r)
Ω=− 4πr2 ρ(r)dr
0 r·
Z R
4
≈− G πr3 ρ(r)4πrρ(r)dr
0 3
 5
4π R
= −G 4π⟨ρ⟩2
3 5
 2
3 4π 3
=− R ⟨ρ⟩
5R 3

Here G is the Gravitational constant. Using M (r) = 43 πr3 ρ(r) and ρ(r) ≈ ⟨ρ⟩

2
Ω = − 35 GM
R (152)

Now the Internal energy/Kinetic energy:

Z R
3 3
U= PV = P (r)4πr2 dr
2 2 0

here we have assumed the Pressure to be a function of r.

⟨ρ⟩
P= KBT
m

42
where m = mass of gas Particles

3K B R
Z
U= T (r)⟨ρ⟩4πr2 dr
2m 0
3 KB
U= M ⟨T ⟩
2 m

1
RR
⟨T ⟩ = M 0
4πr2 dr⟨ρ⟩T (r) (153)

The virial theorem relates the total kinetic energy of a self-gravitating body due
to the motions of its constituent parts, U to the gravitational potential energy,
Ω of the body.
Here the Virial theorem 2U + Ω = 0 become −2U = Ω

3 M 3 GM 2
⇒ −2( K B ⟨T ⟩ ) = −
2 m 5 R

1 GM m
⟨T ⟩ =
5 KBR
3M
Where ⟨ρ⟩ 43 πR3 = M ⇒ R3 =
4π⟨ρ⟩

1 Gm  4π⟨ρ⟩  13
⟨T ⟩ = M
5 kB 3M

Where ⟨T ⟩ is directly proportional to M and ⟨ρ⟩ as follows :

2 1
⟨T ⟩ ∝ M 3 ⟨ρ⟩ 3

⇒ Now, Calculating of average temperature inside Sun:

If we calculate the AU fraction from the Sun’s ”edge” to its center, R over, and
substitute this into the formula, the Sun’s temperature would be about 4100K.
Not very close to your 5776 K, but utilizes the square root of the R D fraction.
The formula reflects effective temperature as shown below:

mH = 1.6 × 10−27 kg

23
G = 6.67 × 10−11 m3 /kg/s2 , k B = 1.38 × 10− m2 kgs−2 k −1

43
Now, the Values of the SUN:

M = 1.9 × 1030 kg, R = 6.9 × 108 m

1 6.6 × 10−11 × 1.9 × 1030

⟨T ⟩ = × 1.6 × 10−27
5 1.38 × 10−23 × 6.9 × 108
 6.6 × 1.9 × 1.6  10−8
= −23
× −15
5 × 1.38 × 10 10
Finally the average Temperature of inside sun is :

4 ×106 ◦ K

6.4 Degenerate density, pressure, internal energy for non-

relativistic (NR) case
In this section we derive the expressions for the density,pressure and internal
energy of a non-relativistic(NR) case.
The problem of pressure in stars, also known as the equation of state: an equa-
tion that specifies the pressure in a gas given its density and temperature. You’re
all familiar with the most common of these, the ideal gas law: P = nkB T . While
this works well under terrestrial conditions, inside a star things get a bit trickier.
So we discuss from the beginning.
According to Heisenberg uncertainty principle.

∆x∆p ≥ h (154)

where h = 6.63 X 10− 27 erg s is Planck’s constant. In 3D, we can write this as

∆V ∆3 p ≥ h3 (155)

To get the pressure in this fully degenerate state, we need to know the momen-
tum distribution d3 p.
Since the shell has volume 4πp2 dp, and each grid point takes up a volume
∆3 p = h3 /∆V , the number of electrons inside the shell is

4πp2 dp 4πp2 dp
Ne = = .∆V (156)
∆3 p h3

To change this to a number density, we just divide both sides by ∆V , which

gives
dn(p) 4πp2
= 3 (157)
dp h

To figure out the momentum pF where this distribution stops, we simply set

44
it by the condition that, when we integrate over all momenta, we get the right
number of particles. Z pF
4πp2
n=g dp (158)
0 h3
4π 3
n=g .p (159)
3h3 F
4π 3
n=g .[2mEF ] 2 (160)
3h3
p2F
As EF = 2m for non relativistic gases

 32
4π EF2

2 2
n = g 3. −m c (161)
3h c2
p
As EF = p2F c2 − m2 c4 for relativistic gases.

 13
3h3 n

pF = (162)
4πg

For ultra relativistic

4π Ef
n=g
3ℏ3 c3
Calculating the internal energy ϵ
pF
d3 p
Z
ϵ=g dp.E (163)
0 h3
pF
p2
Z
ϵ=g 4πp2 dp (164)
0 2m.h3
g 4π PF5
 
ϵ= 3 . (165)
h 2m 5
 
g 4π 5
ϵ= 3 .[2mEP ] 2 (166)
5h 2m
Average energy calculation :

ϵ 3
< E >= = EF (167)
n 5

Calculating the pressure of degenerate non-relativistic gas

Z pF 3
d p pv
P =g (168)
0 h3 3

45
 Z pF
g p.p
P = 4πp2 dp (169)
3h3 0 m
here p=mv momentum of gas

g 4π p5F
P = (170)
3h3 m 5
1
15P h3 m 5

pF = (171)
g.4π
5
g4π 3h3 n 3

P = (172)
15h3 4πg
 3  53
g4π 3h n
P = (173)
15h3 m 4πg
2
1 3h3 3 5

P = .n 3 (174)
5m 4πg
Hydro dynamical Equilibrium :
1 dpe GM
. = 2 (175)
ρe dr R
4 3
AS M= πR ρe (176)
3
M
ρe = 4 3
(177)
3 πR
M
ρe ∝ (178)
R3
Z R Z R
dpe GM M
.dr = . .dr (179)
0 dr 0 R2 43 πR3
GM 2 R−5+1
 
P = 4 (180)
3π
−5 + 1
M2
Pe ∝ (181)
R4
5
But degenerate pressure Pe ∝ ρe3
5
M3
Pe ∝ (182)
R5
−1
M 3 Pe
=> ∝ (183)
R Pe

46
 1
1
=> M 3 ∝ (184)
R
M
=> ρe ∝ 3 (185)
R
=> ρe ∝ M 2 (186)

6.5 Degenerate density, pressure, internal energy for ultra-

relativistic (UR) and relativistic (R) cases
In this section we briefly summarize the relativistic Fermi gas, the extreme
relativistic case and a simple approximate form which often suffices to connect
the non-relativistic and relativistic cases.

6.5.1 Extreme Relativistic Case: E = |⃗

p|c
It is easy to repeat the general analysis of DYNAMICS AT ZERO-TEMPERATURE
with the results:

gp3F
n(kF ) =
6π 2 ℏ3
gcp4F
u(kF ) =
8π 2 ℏ3
µ = pF c
1
P = u
3
dP 1 1
= pF c = u
dn 3 3
4
γ=
3
Note that the relativistic gas is more compressible than the non-relativistic one
   
dn dn
>
dP REL dP N R

provided one is comparing systems at the same density and pressure.

1
6.5.2 p2 c2 + m2 c4 ) 2
General Case: E = (⃗
1
p2 + m2 ) 2 . In this case
For convenience, use relativistic units, c = 1, so E = (⃗
the integrals are complicated, though elementary functions,
Z pF
4πg p
ū(pF ) = 3
p2 dp p2 + m2
(2πℏ) 0

47
[Note that for p2F << m2 this reduces to the non-relativistic result including
the rest mass energy.]

4πgm4 xF 2 p 2 gm4
Z
ū = 3
x dx x + 1 ≡ f (xF )
(2π) 0 2π 2
kF
where xF ≡ m . f (xF ) can be evaluated by elementary means,
1 3 1 1 1 p
f (x) = x(1 + x2 ) 2 − x(1 + x2 ) 2 − ln(x + 1 + x2 )
4 8 8
but we can evaluate the compressibility without knowing this integral

dP 1 p2
= p 2F (187)
dn 3 pF + m2

p2
which interpolates between the non-relativistic result, 3m F
, and the relativistic
pF
result, 3 . Not surprisingly, the adiabatic index, γ, slowly changes from 35 to 43
as xF goes from 0 to ∞.

48
 Academic Section
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Course Code: PH506

Course Name: Statistical Physics

S.No. Roll No. Student Name Credits Course Reg .Type

129. 11940440 HARSH GOUR 6.00 Regular

130. 11940450 HARSH SANJAY PANDEY 6.00 Regular

131. 11940460 HARSH VARDHAN 6.00 Regular

132. 11940520 JAINAM KHATRI 6.00 Regular

133. 11940550 KANDREGULA SAI RAVEENDRA 6.00 Regular

134. 11940580 KONATHAM YASWANTHKUMAR 6.00 Regular

135. 11940590 KRISHNA BHATTA 6.00 Regular

136. 11940600 KRISHNAPRABHU SATWIK TALLURI 6.00 Regular

137. 11940630 KUMARI DIKSHA 6.00 Regular

138. 11940640 LAVISH 6.00 Regular

139. 11940650 M ANKITH KUMAR 6.00 Regular

140. 11940680 MD ARBAAZ 6.00 Regular

141. 11940700 MRINAL GUPTA 6.00 Regular

142. 11940710 MULAMALLA DEEPAK REDDY 6.00 Regular

143. 11940720 MULUKALA VIVEK 6.00 Regular

144. 11940730 NEPPALLI BALA KRISHNA PRASAD 6.00 Regular

145. 11940760 OM PRAKASH KUMAR 6.00 Regular

146. 11940770 PALADUGU SATWIK CHOWDARY 6.00 Regular

147. 11940780 PARTH JOSHI 6.00 Regular

148. 11940790 PASAM DIVYA SRI 6.00 Regular

149. 11940800 PEDDIREDDY ANJUSHA REDDY 6.00 Regular

150. 11940810 PENDEM SIDDARTHA 6.00 Regular

151. 11940900 PRANJAL 6.00 Regular

152. 11940920 PUJARI MAHI PRANAV 6.00 Regular

153. 11940930 PUJARI NIKITHA 6.00 Regular

154. 11940940 PULKIT KHANDELWAL 6.00 Regular

155. 11940960 RAHUL PAMMINA 6.00 Regular

156. 11940970 RAJAT KUMAR KHARWAR 6.00 Regular

157. 11940980 RAJSHEKHAR BHARGAVA 6.00 Regular

158. 11940990 RAMAVATH ABHI NAIK 6.00 Regular

159. 11941010 RISHABH KUMAR 6.00 Regular

160. 11941020 RISHABH RANJAN 6.00 Regular

 Academic Section
Indian Institute of Technology Bhilai
IIT Bhilai Government Engineering College Campus Old Dhamtari Road,
Chhattisgarh, India

Course Wise Student List

Dec-21 to May-22

Course Code: PH506

Course Name: Statistical Physics

S.No. Roll No. Student Name Credits Course Reg .Type

161. 11941030 ROHIT BOSE 6.00 Regular

162. 11941040 RUCHIT PRAKASH SAXENA 6.00 Regular

163. 11941070 SANKARASETTY VENKATA KOUSHIK 6.00 Regular

164. 11941110 SHIVAM CHAUDHARY 6.00 Regular

165. 11941130 SHREYASH DINESH HAMBARDE 6.00 Regular

166. 11941150 SHUBHAM PATEL 6.00 Regular

167. 11941180 SONTI YASWANTH 6.00 Regular

168. 11941190 SRILEKHA KADAMBALA 6.00 Regular

169. 11941210 SWANINDA GHOSH 6.00 Regular

170. 11941220 SYAMANTAK BERA 6.00 Regular

171. 11941240 TELAGAREDDY MANI NAGA SATISH 6.00 Regular

KUMAR
172. 11941260 THIRUVEEDULA SAI VIKAS 6.00 Regular

173. 11941280 UTKARSH NIGAM 6.00 Regular

174. 11941290 UTKARSH SANJEEV KUMAR ALPURIA 6.00 Regular

175. 11941300 VAISHNAVI GUPTA 6.00 Regular

176. 11941310 VANSHIKA SAHGAL 6.00 Regular

177. 11941320 VATSALYA MEENA 6.00 Regular

178. 11941330 VEMPALA SURYATEJA 6.00 Regular

179. 11941350 VIKASH MEENA 6.00 Regular

180. 11941360 VIPEEN KUMAR 6.00 Regular

181. 11941400 YEMBEY MANJUNATHA 6.00 Regular

182. 11941410 YOGESH MEENA 6.00 Regular

183. 12110510 THANDAR ZAW WIN 6.00 Regular

184. 12142050 BHARAT KUKKAR 6.00 Regular

185. 12142090 GAURAV KHANDAL 6.00 Regular

186. 12142130 NINAD KHOBREKAR 6.00 Regular

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