Grand Canonical Ensemble

Prof. Dr. Narayan Prasad Adhikari

Professor
Central Department of Physics
Tribhuvan University Kirtipur, Kathmandu, Nepal

July 9, 2021

1
 Recalling from last lecture

NVE/NVT Ensemble

• Density functions in NVE/NVT Ensemble

• Distribution of energy in NVT ensemble

• Generalized equipartition theorem: Virial Theorem :

its Applications in classical ideal gas, Boltzmann’s
equipartition theorem of energy

2
 Limitations of NVT ensemble

Can you think of performing an experiment in which

particle number varies?

• Which Ensemble you may use?

• NVT or NVE

• Perhaps it is better to think of another ensemble

which allows fluctuations of particles directly

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4
• Consider an open system which can exchange particle
and energy both as shown in previous figure.

E = ES + EB (1)

N = N1 + N2 (2)
ES ≪ EB and N1 ≪ N2
5
The Density function ρ1 (p1 , q1 , N1 ) ∝ QN 2 (V2 , T )
i.e.
ρ1 (p1 , q1 , N1 )
∝ QN −N1 (E − E1 , N − N1 )
exp(−βH1 (p1 , q1 , N1 )) dp3N 3N2
R
2 dq2
2
exp (−βH2 (p2 , q2 , N2 )))
=
(h3N1 ).QN (V, T ) h3N2
(3)

The factor h3N1 ensures the normalization of ρ1 ,

i.e.
N Z
dp3N 3N1
X
1 dq1 ρ1 (p1 , q1 , N1 ) = 1
1

N1 =0

. OR
N
X
QN1 (V, T )QN −N1 (V, T ) = QN (V, T )
N1 =0

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∴ we get

QN2 (V, T ). exp(−βH1 (p1 , q1 , N1 )

ρ1 (p1 , q1 , N1 ) = (4)
QN (V, T ).h3N1

Now,
QN2 (V, T ) QN −N1 (V − V 1, T )
=
QN (V, T ) QN (V, T )
exp(−βF (N − N1 , V − V1 , T ))
=
exp(−βF (N, V, T ))
= exp(β[F (N, V, T ) − F (N − N1 , V − V1 , T )])
∂F ∂F
= exp(β[F (N, V, T ) − F (N, V, T ) + N1 . + V1 ])
∂N1 ∂V
= exp(βµN1 − βP V1 )
(5)

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From Equations 4 and 5 we get

exp(−βH1 (p1 , q1 , N1 ) + βµN1 − βP V1 )

ρ1 (p1 , q1 , N1 ) = (6)
h3N1
Dropping the suffix to make the equation general we get

exp(−βH(p, q, N ) + βµN − βP V )
ρ(p, q, N ) = (7)
h3N
For identical and indistinguishable particles (Classical ideal gas) we
need to divide equation 7 by a factor of N! in RHS. Therefore in this
case :

exp(−βH(p, q, N ) + βµN − βP V )
ρ(p, q, N ) = (8)
N ! .h3N

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The normalization condition;
∞ Z
d3N pd3N qρ(p, q.N ) = 1
X
(9)
N =0

and equation 7 give;

∞ Z
X d3N pd3N q exp(−βH(p, q, N ) + βµN )
= exp(βP V ) (10)
N =0 h3N

LHS of above equation is called ”GRAND PARTITION FUNCTION”

and here I denote it by Z. It is function of ( µ, V, T) OR (z=eβµ ,
V,T). z is called fugacity. Note the difference in z and Z.

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 ∞ Z
X d3N pd3N q exp(−βH(p, q, N ) + βµN )
Z(µ, V, T ) = (11)
N =0 h3N

OR
∞ Z
X d3N pd3N q exp(−βH(p, q, N )).z N
Z(z, V, T ) = (12)
N =0 h3N

OR ∞
z N QN (V, T )
X
Z(z, V, T ) = (13)
N =0

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Therefore we get

βP V = ln Z(z, V, T ) = ln Z(µ, V T ) (14)

This proves another usefulness of the µVT ensemble as it gives direct

access to equation of State.
Now, average number of particles is given by

N̄ = hN i
P∞ 0 N0
N 0 =0 N z QN 0 (V, T )
= P∞ 0N
(15)
N 0 =0 z QN 0 (V,
!
T)
∂ ln Z(z, V, T )
=z
∂z V,T

Note:
∂ 1 ∂
z →
∂z β ∂µ

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OR !
∂ ln Z(µ, V, T )
N = kB T (16)
∂µ V,T

The equation of state is obtained from equations 14 and 15 or 16.

The internal energy is
U = hH(p, q, N )i
∞
1 X z N 1 Z 3N 1 3N 1
= d pd q exp(−βH(p, q, N 1))H(p, q, N 1)
Z N 1=0 h3N 1
!
∂ ln Z(z, V, β)
=−
∂β z,V
(17)

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 Evaluation of Thermodynamic quantities
in µVT ensemble
We have;
P V = kB T ln Z(µ, V, T ) = −φ(µ, V, T )(say) (18)
From Thermodynamics;
PV = G − F
OR
P V = µN − U + T S
OR
d(P V ) = −dφ(µ, V, T )
= d(µN − U + T S) (19)
= µdN + N dµ − dU + T dS + SdT
OR −dφ = N dµ + P dV + SdT
13
Therefore we get;
∂φ
N (µ, V, T ) = −( )V,T (20)
∂µ
Similarly
∂φ
P (µ, V, T ) = −( )µ,T (21)
∂V
and
∂φ
S(µ, V, T ) = −()V,µ (22)
∂T
Now,G = N µ, F = G − P V , U = F + T S and so on ........

14
 Recipe of µV T Ensemble

From the knowledge of Hamiltonian, H(p,q,N) obtain;

∞
X
Z(µ, V, T ) = exp(βµN )QN (V, T )
N =0

Then
φ(µ, V, T ) = −kB T ln Z(µ, V, T )
Then obtain all the thermodynamic quantities S, P, N, ...... CW:
What changes do you think for a classical ideal gas in above formulas
?

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 Classical ideal gas in µV T Ensemble

The Hamiltonian is;

3N
X p2i
H(p, q) = (23)
i=1 2m

Therefore (referring the NVT ensemble) we get

 !3/2 N
1  2πmkB T
QN (V, T ) = V  (24)
N! h2

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 ∞
 !3/2 N
X zN  2πmkB T
∴ Z(µ, V, T ) = V 
N =0 N ! h2
∞
 !3/2 N
X1  2πmkB T (25)
= V exp(βµ) 
N =0 N ! h2
 !3/2 N
2πmkB T
= exp V exp(βµ) 
h2
 !3/2 N
2πmkB T
=⇒ ln Z(µ, V, T ) = V exp(βµ)  (26)
h2
CW/HW: Now you can find φ(µ, V, T ), and hence S, P, N and all
other thermodynamic quantities. Which N is this? Can you guess? I
mean N fluctuates.

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 Classical N Harmonic oscillators in µV T
Ensemble - one dimension

The Hamiltonian is;

N
!
p2i 1
+ mω 2 qi2
X
H(p, q) = (27)
i=1 2m 2

HW: Find QN (V, T ), then Z(µ, V, T ) and φ(µV, T ) hence solve this
problem in µV T Ensemble.
Hints: There is no 1/N! factor so you need to use the formula for
algebraic infinite series. Further (1- 1/N N/(1+N)).

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 Fluctuations of number of Particles in
µV T ensemble
The fluctuations of number of particles is;

(∆N )2 = hN 2 i − hN i2 (28)

Further we have;
!
∂ ln Z(z, V, T )
hN i = N̄ = z (29)
∂z V,T

Therefore (HW)
!
2 ∂ ∂ ln Z(z, V, T )
∴ (∆N ) = z z (30)
∂z ∂z V,T

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 ∂ ∂
Since z ∂z → kB T ∂µ We get
!
2 2 ∂ 2 ln Z(µ, V, T )
∴ (∆N ) = (kB T )
∂µ2 V,T
! (31)
∂ 2P
= kB T V
∂µ2 V,T

F (v,T ) V
Now, letting a(v, T ) = N
where v = N
= ρ1 .
!
∂F (v, T )
µ=
∂N T
∂ (N a(v, T )) (32)
=
∂N
∂a
= a(v, T ) − v
∂v

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 ∂µ ∂ 2a
∴ = −v 2 (33)
∂v ∂v
And
∂F ∂a
P =− =−
∂V ∂v
∂P ∂P ∂v 1
∴ = =
∂µ ∂v ∂µ v
(34)
! !
2
∂ P ∂ ∂P ∂v
∴ 2
= .
∂µ ∂v ∂µ ∂µ
1
= −  ∂P 
3
v ∂v
T

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Now from the definition of isothermal compressibility, we get
!
1 ∂V 1
κT = − = −  ∂P 
V ∂P T v ∂v
T (35)
!
2
∂ P κT
∴ = 2
∂µ2 T
v

Therefore from equation 31 and 35 we get

s s
kB T V κT N kB T κT
∆N = ∼ (36)
v2 v
Therefore we get
√
∆N N 1
' = √ = 0 as N → ∞ (37)
N N N

22
 Fluctuations of energy in µVT ensemble
We have;
!
∂ ln Z(z, V, T )
U = hH(p, q, N )i = − (38)
∂β V,z

Therefore,
! !
∂ 2 ln Z(z, V, T ) ∂U
=−
∂β 2 V,z
∂β
2
! !2 (39)
1 ∂ Z(z, V, T ) 1 ∂Z
= − 2
Z ∂β 2 V,z
Z ∂β z,V

Further, !
2 1 ∂ 2Z
hH i =
Z ∂β 2 z,V

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 !
2 2 ∂U 2
(∆U ) = hH i − hHi = −
∂β z,V
! (40)
2 ∂U
= kB T
∂T z,V

Think: Is there any difference in this expression and that we obtained

for canonical ensemble ?
!
2 2 ∂U
(∆U ) = kB T (41)
∂T N,V

Is there any relation U (N, V, T )andU(z, V, T) ?

N of µVT ensemble is N (T, z(µ), V ). Therefore U (z, V, T ) can be
transformed to U(N,V,T) i.e.
U ≡ U (T, V, N (T, V, z))
.
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 ! ! ! !
∂U ∂U ∂U ∂N
= + ×
∂T z,V
∂T N,V
∂N T,V
∂T z,V
! ! (42)
∂U ∂N
= CV + ×
∂N T,V
∂T z,V

Now we need to find !

∂N
.
∂T z,V

(In this lecture I follow Pathria for this particular calculation, for a
long time I was following a bit longer process which was developed
myself). Since Pathria is doing the same in a bit shorter I follow that
one.

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 1
Define: β = kB T
and α = −µβ. Therefore,

Z(z, V, T ) ≡ Z(α, V, β)
! !
∂ ln Z(z, V, β) ∂ ln Z(µ, V, β)
N =z = kB T
∂z V,β
∂µ V,β
! (43)
∂ ln Z(α, β, V )
=−
∂α β,V

And, !
∂ ln Z(α, V, β)
U =− (44)
∂β α,V

Therefore,
! !
∂N (α, V, β) ∂U (α, V, β)
= (45)
∂β α,V
∂α β,V

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 ! !
2 ∂N (α, V, T ) ∂U (µ, V, T )
−kB T = −kB T
∂T z,V
∂µ V,T
! !
∂N (z, V, T ) 1 ∂U (µ, V, T )
= × (46)
∂T z,V
T ∂µ V,T
! !
1 ∂U (µ, V, T ) ∂N (µ, V, T )
= × ×
T ∂N V,T
∂µ V,T

Further, !
∂N (µ, V, T ) (∆N )2
=
∂µ V,T
kB T

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Therefore from equations 42 and 46 we get
! ! ! !
∂U ∂U 1 ∂U ∂N (µ, V, T )
= CV + × × ×
∂T z,V
∂N T,V
T ∂N V,T
∂µ V,T
!2
1 ∂U (∆N )2
= CV + ×
T ∂N T,V
kB T
(47)

Therefore:
!2
2 ∂U
2
(∆U ) = kB T CV + × (∆N )2
∂N T,V
2 !2 (48)
2
(∆U) kB T CV ∂U 1
OR, 2
= 2
+ × (∆N)2 × 2
U U ∂N T,V
U

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Now CV ∼ N, and(∆N)2 ∼ N, U ∼ N.

∆U 1
∴, ∼√
U N
. This means the relative fluctuations of energy in µV T ensemble
also goes to zero in the thermodynamic limits.

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 Homework and Conclusions

HW: 1. Compare thermodynamic properties of classical ideal

gas and N - Classical Harmonic Oscillators obtained in NVE,
NVT and µV T ensembles. Also comment on your results.
Why did we get same results in all three ensembles?

HW: 2. If you need to carry on an experiments for real gas

(say water ) to study its heat capacity at (say 500 C) which
ensemble you may choose? Also give reasons why did you opt
that ensemble.

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HW: 3. Obtain an expression for number of fluctuations of
particles in classical ideal gas in µV T ensemble. Hence use it
to find ∆N and ∆N N
for average N to be equal to 10, 100,
4 6 12 16
10 , 10 , 10 10 . Hence comment on your results. HW: 4.

Find fluctuations of energy in classical ideal gas in µV T

ensemble. Hence use it to find ∆U and ∆U U
for average N to
4 6 12 16
be equal to 10, 100, 10 , 10 , 10 10 . Use room
temperature. Hence comment on your results. HW: 5.

Repeat 2 & 3 for classical Harmonic Oscillators. Solve Ex 7

(7.1 - 7.7)

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Thank you !!!

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