UnitII Canonical and Grand Canonical Ensembles

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UNIT - 2
Canonical ensemble & Grand-Canonical Ensemble
Microcanonical ensemble deals with the simplest system ie, isolated system and worked on
the hypothesis of equal – a - priori probability. But in actual practice, an isolated system does not occur
in laboratory and hence is of little practical interest except that other ensembles can be constructed
with microcanonical ensemble.
If we replace the constant energy constraint of microcanonical ensemble with constant

temperature constraint, we would have a system defined by parameters (N,V,T). This constant
temperature constraint will work only if the system is in thermal contact with a large heat reservoir.
Thus thermal energy flows between the system and the reservoir and hence the energy of the system
does not remain a constant. The reservoir is considered to be very large and so the energy transfer
between it and the system does not change its energy noticeably. The ensemble of such a system which
exchanges energy with a reservoir is called canonical ensemble. But the system does not share particles
with the reservoir. Thus the total number of particles and volume remains the same for the system as
well as the reservoir.
Let the reservoir at temperature T has energy Er and the system under observation be in the ith
energy level Ei. The system under observation along with the reservoir form a composite system with
constant energy Ee = Er + Ei. This composite system can be treated as a single isolated system, to which
the method of microcanonical ensemble can be applied. If c is the probability that the composite
system is in the region of t-space between ergodic surfaces Ec and Ec + D. let this volume be Dtc. Then
c (Ec) µ Dtc (Ec, Ei) = Dts (Ei) Dtr (Er)
= 0, otherwise (if Ec < E < Ec + D
where Ei is the unperturbed energy of the ith quantum level of the system. The number of states
accessible to the composite system will be equal to the number of states accessible to the reservoir ‘r’,
since Ei << Er
ie,  µ Dtr (Ec - Ei) ---- (2) (when Dtr is large , Dts will also be large, since both the systems
together will be in equilibrium.
Here i is the probability that the system is in the ith quantum state. Since Ei <<Ec we can expand
ln Dt (Ec- Ei) about Ec = Er into a Taylor series.
Thus ln Dt (Ec - Ei) = ln Dtr(Ec) - ln ∆ ( )
Terms with higher powers of Ei can be neglected and thus the above equation would become
ln Dtc (Ec-Ei) = ln Dtr (Ec)- ln Dtr (Er) = ln Dtr (Ec) - bEi --- (3)
Where b= ln ∆ ( )| = ----- (4)
where T is the temperature of the reservoir.
Taking exponential of equation (3), we get
Dtr (Ec - Ei) = Dtr (Ec) ----- (5)
Or Pi = C ----- (6)
where C = Dtr (Ec) x some constant  a constant. This constant is independent of Ei and is determined
from the normalization condition
= =1
∴ = -------- (7)
Thus the probability distribution is given by
( , )
Pi (N,V,T) = ------- (8)
( , , )
( , )
Where =∑ is called the partition function of the system
The canonical distribution is shown in figure above. It can be seen that higher the energy value,
the less likely the system to be in that state. But all the n-particle quantum states with same energy have
the same probability.
So, we can say that a canonical ensemble is constructed out of many microcanonical ensembles,
one representing each energy level and weighed according to equation (6). The probability of finding the
system in a given energy level Ei is the sum of the probabilities of all states having this energy. The
number of such states is the degeneracy of the level given by Ω(Ei). Thus the probability that the system
is in the ith state is
= Ω( )= Ω( )-
As is the product of an exponentially decreasing curve and a rapidly increasing curve, there is a sharp
peak over a narrow range of energy as shown in figure below.
Usually the system under observation is a macroscopic system with distinguishable particles and the
probability of the system being in the ith energy level is Pi. If there are mi elements in the canonical
ensemble corresponding to energy Ei, then Pi is also given by
= - -- (9)
Consider a canonical ensemble of M   elements in which mi elements correspond to energy

level Ei. Then the statistical weight associated with the distribution is
! !
Ω { }= = ∏
------ (10)
! !…. !
Subject to the constraint
∑ = ∑ = ------- (11)
The entropy
The entropy of the ensemble is defined as
!
= Ω =
!
Applying Stirling’s formula,

= ln − − ln +
= ln − ln
The average entropy per element of the ensemble is
1
= = ln − ln
=− ln =− ln
, = − ∑ ------- (12)
The energy Ei is a function of V & N. The partition function can be written as
= = + +⋯+ +⋯
Thus the partition function ‘Z’ is a function of V, N & b (Since energy Ei is in function of V & N). The terms
in the summation indicate how the ensemble is partitioned among various energy states.
The average value of any quantity R (Ei) is written as
= ( )
Using this,
.
= =
1
= −
Or = − (ln ) ------- (a)

From = − ∑ ln
we get = − ∑ ln
= − [– − ln ] = + E + ln
= + --- (14)
=1
\ dS = kb dE – KE db + k d(ln Z) --- (15)
Since Z = Z(b, V, N)
( ) ( ) (ln )
( )= + +
( , )
=
(ln ) å
∴ = × − = −
å
(ln ) = × −
å
& ( )= ×−
å å å
∴ (ln ) = − − −
., ln = − − −
\ = + − − −
= − −
If we write =U
= − ∑ − ∑ --- (16)
= + + --- (17)
, , ,
Comparing (16) and (17) We have
= b = - -- (a)
,
(18) = =− ∑ -- (b)
,
= − = − − − − −( )
,
Using b = = in eqn (14), we get
= + ln --- (d)
Or = +
Or – = − = , the Helmholtz free energy
ie, = − = − ( , , )
= = − ln = − (ln )
1 1
b = \ = −
=−
= = ln
= =−
Since = − , = exp (− )
1 /
=
/
( )= / /
∴ = .
( )= ( )/
------ (19)]
Ideal gas in canonical ensemble
For an ideal Boltzmann gas consisting of N molecules of mass m, any arbitrary energy E of the system is
= ,
2
∑
=∑ =∑ ∏
The summation over discrete states can be replaced by integration over phase space
1 … −−−
→
! ℎ
1 ( )
∴ =
!ℎ
/ / /
Z= !
∫ ∫ …. ∫
/
Z= !
∫
This integral can be evaluated using the identify

1
\ = √2 =
!ℎ !
Where is the single particle partition function, ie, with N = 1
ie,
(2 ) /
= =
ℎ
, = = =

Where = is the quantum concentration . That is nQ is the concentration associated with


a single particle in a cube of side  and = is the concentration. In general ‘
Z  zN due to N! in the denominator
The Helmholtz free energy of the system is
= − =− (2p )
!
By Stirling’s formula N! =
[ ! = ( ) = ( – ) = – ]
Or ! = − +1
Taking exponential != =
/
2p
∴ = − ln
ℎ
/
2p
= − ln
ℎ
= − ln
= − + ln( )
= − ln +1
= − ( / )–
= −
¶ ¶
∴ = − ln −
¶ ¶
¶
= ln
¶
¶
∴ ln =
¶
¶
∴ = − − ln
¶
¶
The entropy of the system in given by ∴ = −( )V
¶
p /
×
/
, = ln + p / ×
3
= ln + ×
2
3
= ln +
2
1 5
, = ln +
 2
This equation is in agreement with Sakur – Tetrode equation

Maxwell’s velocity distribution
When the method of canonical ensemble is applied to a single molecule of mass ‘ m’ in volume V, the
probability of finding the molecule in the entire volume of the container V in velocity interval dpx dpy dpz
around momentum P = ipx + jpy + kPz
( ) / /
=
ℎ
The probability of the molecule in a velocity range dcx dcy dcz at cx, cy, cz can be expressed as
( )( )= / ( )/
, /
= = 1, Z = z = V/3
p /
( )/
\ dn (cx, cy, cz) dcx dcy dcz= × × .
( ) ( )/
=
2p
( )/
= 4p
2p
Where = + +
The quantity dn(c)dc is the probability that a particle has speed in dc at c
Using ∈= , dÎ = mc dc
∈ /
and c = , we have
2∈ ∈ ∈
= × = √2 ∈ /
2∈
We get the probability distribution that a molecule has kinetic energy between Î and Î + dÎ is
/
∈/
∈
( )= × 4p × √2 ∈ /
2p √2p
2 ∈ ∈/
∈
=
√p
∈ ∈
≡
∈
Now is the product of two function – one an exponential decay function and another one
increasing with Î. So dn(Î) has a peak where the two curves intersect as shown in figure
∈ /
e-Î/kT is called Boltzanann factors and 2 is the density of states.
p
Equipartition of energy
Considering the case of a single particle, ie., N = 1, we have
−1 3
= = =
b 2
For a single particle, total energy is kinetic.
\H= where (P = P1, P2, P3)

Thus, each variable of the system like pi’s and qi’s contribute an average energy to the total energy
of the system if its Hamiltonian is expressed as a quadratic function of these variables.
Q: What is the total energy of a particle at temp T if the Hamiltonian of the system is H = ap2 + bx2
For example if H= ∑ +
the average energy due to is:
/
∫
=
/
∫
/
∫
=
/
∫
/
∫
=−
/
∫
/
=− ln
/
p
=− ln
p
=− ln
/ 1 √p
=− × − /
=
p 2
Similarly we can show for the term also
Thus each quadratic term in the expression for Hamiltonian contribute an energy to the
average energy of the system. This theorem is known as equipartition theorem of energy.
Grand canonical ensemble
In microcanonical ensemble method, we had a totally isolated system defined by macroscopic

variables N, V, E. In canonical ensemble method, the constant energy constraint was relaxed and energy
was allowed to vary as the system exchanged energy with a reservoir.
But in several chemical processes, the number of particles of the system under observation
varies. In Quantum Mechanics also, the number of particles of the system under observation varies, as
particles can either be created or destroyed. Thus we need an ensemble method to deal with systems
where neither energy nor number of particles remain constant ie, the system under observation
exchanges both energy and particles with a reservoir. The ensemble of such a system is called grand
canonical ensemble. But the system under observation along with the reservoir again form an isolated
system with total energy and total number of particles conserved. Now, the macroscopic state of the
system under observation is defined by (V,T,m) where m is the chemical potential per particle of the
system.
Thus = + and = +
Now, D ( , , , ) =D ( , )D ( , )
The phase space dimension now depends on the number of particles in the ith
quantum state of the system. A particular quantum state of the system is represented by with
energy and number of particles . If is the probability of finding the system in the ith quantum
state with energy Then
( , ) µ Dt [( - ), ( - )] ---- (1)
This is possible because the system under consideration will be in equilibrium when the
reservoir itself is in equilibrium as both are in contact and form an isolated system together.
The total number of microstates available to the composite system is very nearly equal to the
total number of microstates available to the reservoir itself because the system under consideration is
very small in comparison to the reservoir. ie, ≪ & << ≪ . Hence we can expand
ln Dt [( - ), ( - )] into a Taylor series in and abount = & = as

ln Dt [( - ), ( - )] = ln Dt ( , )- ln Dt − ln Dt ---- (2)
Now using substitution,
b = (ln Dt )
−bm = (ln Dt )
We have
ln Dt [( - ), ( - )] - ln Dt ( , ) = -b + bm + …….. (4)
Taking exponential,
Dt [( - ), ( - )]= Dt ( , ) b( m )
But Dt ( , ) is a constant independent of or . Thus equation (1) can be written as
( , )=C b( m )
--------- (5)
Where C = BDt ( , ) where B & C are constants independent of ( , ). Such an ensemble with
probability distribution of form given by eqn(5) is called Grand canonical Ensemble and the
corresponding distribution is grand canonical distribution. The constant C of equation (5) can be
determined from the normalization condition.
( , )= b( m )
=1
, ,
1
\ = b( )
∑ ,
m
b m
\ ( , )= ---- (7)
Where
= exp −b −
,
---- (8)
is the grand canonical partition function. It is the sum of canonical partition function Z(N) for canonical
ensemble with different Ns with a weighing factor of . That is,
= b bm = b bm
( ) bm
Thus the grand canonical ensemble can be thought of as made of a collection of canonical ensemble
with different values of N
= ( ) bm
ℎ ( )= b
Consider a grand canonical ensemble of elements where → ∞. The state of each element is
characterized by the energy and number of particles ‘N’ in it. The statistical weight Ω of the
ensemble associated with a particular macrostate { } is
!
Ω =
∏ ∏ !
subject to the constraints
=
,
= , =
, ,
Where is the total number of particles in the ensemble.

Thus
b( )
= = b( )
∑ ,
Then, the entropy is defined as
= − ln
b( )
− ln
,
=− b − bm +
, ,
= − b − mb + ln =1
,
Taking a small variation in entropy,
ds = kbdÎ - kmbdN + kd ln
(here b is held constant as entropy can be taken to be a function of maximum three variables.
Here  ( ) and  (V)
\  (V)
\dln (ln )
1 å b( m )
, ln =
1 b( m )
= × −b
,
\ = b Î − mb − b
, ,m
1
\ =
,
−m
=
,
−1
= =
,
,
−1
\ =
,
= b − bm + ln
Using = U and b=
S= −m + ln
\ = −m + ln
Putting - kT ln =Ω = − − , where Ω is called the grand canonical potential
/
\ =
But from 2nd law of thermodynamics, we have
= + − Ω = − − = −
From this equation
S=− Ω and N = − m
Ω
1
= , =
( )= b( m ) m /
In general, =
Ideal gas in grand canonical ensemble
The canonical partition function of an ideal gas of N molecules confined to a volume V is
/
2p
( )= =
! ℎ !
The grand canonical partition function Z is
= ( ) m /
m / m/
= =
! !
(  ) 
= =
!
Where a = e m/kT is the fugacity or absolute activity of the system and the identity
= is employed
!
\ = 
and ln = za
Now, Ω = - kT ln = - kTza
/
m/
2
., Ω = −
ℎ
/
m/
2 /
= −
ℎ
/ /
Ω m/
m 2 / m/
2 5
∴ = − =− × +
ℎ ℎ 2
/
m/
2 5 m
= −
ℎ 2
This is again another form of Sakur- Tetrode equation for the entropy of an ideal gas
/
Ω m/
1 2
=− = . × × .
ℎ
Ω
=−
From the above equation,
m 1 1
= \m = − ln
 
,m = − ln = ln
Where n = is the concentration of the particles and = 

is the quantum concentration or the
concentration associated with a single particle enclosed in a cube of side . Thus m increases with n and
a is directly proportional to n
Since Ω = - PV , P = - Ω
/
m/
2πmkT kTN
P = −kT e =
h V
Thus PV = is the ideal gas law
Photons
Photons are spin -1 particles and hence they are Bosons and obey BE statistics. The energy of a
g
photon of frequency g is E= hg and the associated momentum is = . The number of quantum state
Dt
between momentum range p and p + dp is
ie, The density of states between p and p + dp is
g(p) dp = 4pp dp
Since the photons have two independent directions of polarization,
4pV 8pV h g hdg

g(p)dp = 2 ( p dp) =
h h c c
ie, g(g)dg = g dg is the number of quantum states lying in this frequency range between g and
g + dg T hus the number of photons lying in this frequency range is
g(g)dg x (g) where (g) is the B-E probability distribution function
8πV 1
\dn = g(g)dg x (g) = g dg x (µ b )
C e −1
where for photons E = hg and  = 0
8πV 1
\ dn = g dg g/
c e −1
Thus the total energy of photon in this range is
dn x hg = hg dg × g/
Thus energy density for this range in g = ∈= g g × g/
This is Planck’s radiation law for photons
For hg << kT ie, for low frequency or high wave length region,
g/ g g/ g
e =1+ \ e −1=
p g g p
\ g = × g
= g g → This is Rayleigh – Jeans law
For hg >> kT , ehg/kT >> 1, one can be neglected compared to ehg/kT
p g g/
\ g = g → This is Wein’s law
The Total energy density is
U 8ph g dg
= u(g, T)dg = g/
V c e −1
g
Putting = x, g = , dg = dx
U 8ph kT x dx
\ =
V c h e −1
The integral evaluates to
U 8ph kT π 8π k T
\ = × =
V C h 15 15C h
or = where b = This is Stefan – Boltzmann radiation law

UnitII Canonical and Grand Canonical Ensembles

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UnitII Canonical and Grand Canonical Ensembles

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If we replace the constant energy constraint of microcanonical ensemble with constant

c (Ec) µ Dtc (Ec, Ei) = Dts (Ei) Dtr (Er)

= 0, otherwise (if Ec < E < Ec + D

ln Dt (Ec- Ei) about Ec = Er into a Taylor series.

Thus ln Dt (Ec - Ei) = ln Dtr(Ec) - ln ∆ ( )

Where b= ln ∆ ( )| = ----- (4)

where T is the temperature of the reservoir.

Taking exponential of equation (3), we get

Dtr (Ec - Ei) = Dtr (Ec) ----- (5)

Thus the probability distribution is given by

Consider a canonical ensemble of M   elements in which mi elements correspond to energy

Subject to the constraint

The entropy of the ensemble is defined as

Applying Stirling’s formula,

The average entropy per element of the ensemble is

The energy Ei is a function of V & N. The partition function can be written as

The average value of any quantity R (Ei) is written as

Or = − (ln ) ------- (a)

\ dS = kb dE – KE db + k d(ln Z) --- (15)

Comparing (16) and (17) We have

Using b = = in eqn (14), we get

Or – = − = , the Helmholtz free energy

Ideal gas in canonical ensemble

This integral can be evaluated using the identify

Where is the single particle partition function, ie, with N = 1

Where = is the quantum concentration . That is nQ is the concentration associated with

a single particle in a cube of side  and = is the concentration. In general ‘

Z  zN due to N! in the denominator

The Helmholtz free energy of the system is

This equation is in agreement with Sakur – Tetrode equation

Maxwell’s velocity distribution

The quantity dn(c)dc is the probability that a particle has speed in dc at c

Considering the case of a single particle, ie., N = 1, we have

For a single particle, total energy is kinetic.

\H= where (P = P1, P2, P3)

of the system if its Hamiltonian is expressed as a quadratic function of these variables.

the average energy due to is:

Similarly we can show for the term also

Grand canonical ensemble

In microcanonical ensemble method, we had a totally isolated system defined by macroscopic

ln Dt [( - ), ( - )] into a Taylor series in and abount = & = as

Now using substitution,

But Dt ( , ) is a constant independent of or . Thus equation (1) can be written as

subject to the constraints

Where is the total number of particles in the ensemble.

Then, the entropy is defined as

Taking a small variation in entropy,

Here  ( ) and  (V)

Putting - kT ln =Ω = − − , where Ω is called the grand canonical potential

But from 2nd law of thermodynamics, we have

From this equation

Ideal gas in grand canonical ensemble

The canonical partition function of an ideal gas of N molecules confined to a volume V is

The grand canonical partition function Z is

From the above equation,

Where n = is the concentration of the particles and = 

Thus PV = is the ideal gas law

ie, The density of states between p and p + dp is

Since the photons have two independent directions of polarization,

4pV 8pV h g hdg