Lecture 2

Grand Canonical Ensemble GCE

2.1 Thermodynamic Functions

Continuing on from last day we also note that

dΩ = dF − N dµ − µdN
= −SdT − P dV − N dµ (2.1)
thus,
µ ¶
∂Ω
P = − (2.2)
∂V T,µ
µ ¶
∂Ω
N = − (2.3)
∂µ T,V
µ ¶
∂Ω
S = − (2.4)
∂T V,µ
¡ ∂Ω ¢
From the expression for the entropy, we therefore find E − N µ = Ω + T S = Ω − T ∂T V,µ
.
But recall that,
µ ¶
2 ∂ ln Ξ
E − N µ = kT
∂T
µ,V
µ ¶
∂kT ln Ξ
= T − kT ln Ξ
∂T µ,V

which therefore implies that,

Ω = −kT ln Ξ (2.5)

or
PV
= ln Ξ (2.6)
kT
LECTURE 2. GRAND CANONICAL ENSEMBLE GCE 7

2.2 Particle Fluctuations

2.2.1 Mean-square deviation in N
h(∆N )2 i = hN 2 i − hN i2 (2.7)
On your assignment you will show that,

¶µ
2 ∂N
h(∆N ) i = kT
∂µ T,V
µ ¶
∂N
= z (2.8)
∂z T,V
µ 2 ¶
∂ Ω
= −kT
∂µ2 T,V

and the relative fluctuations are then,

³ ´1/2
∂2Ω
∆N −kT ∂µ2
= ³ ´ . (2.9)
N − ∂Ω
∂µ

Now the Grand Potential is an extensive quantity (recall that Ω ≡ Ω(T, V, µ), but the
chemical potential is clearly an intensive quantity,
µ ¶ µ ¶
∂F ∂G
µ= =
∂N T,V ∂N T,P

since F and G are extensive.

• Thus the relative fluctuations in particle number must scale as:

∆N N 1/2 1
∝ ∝ 1/2
N N N

2.2.2 Gibbs-Duhem Equation

• We will now do an alternative derivation of the above result 2.9

• Start with the Gibbs free energy, G = N µ = N µ

• More generally, for a multicomponent system, since G is extensive we have,

G(λN1 , λN2 , . . . , λNm , T, P ) = λG(N1 , N2 , . . . , Nm , T, P ) (2.10)

where λ is an arbitrary scale factor.
LECTURE 2. GRAND CANONICAL ENSEMBLE GCE 8

• Differentiate 2.10 w.r.t. λ to find,

L.H.S.:

Xm µ ¶ Xm µ ¶
∂αi ∂G ∂G
(αi = λNi ) = Ni
i=1
∂λ ∂αi T,P,Nj6=i i=1
∂λNi T,P,Nj6=i
Xm µ ¶
∂G
= Ni (f orλ = 1)
i=1
∂N i T,P,Nj6=i
m
X
= µ i Ni
i

R.H.S.:
∂λG
= G(N1 , . . . , Nm , T, P )
∂λ
Therefore, most generally for a multicomponent system
m
X
G (N1 , N2 , . . . , Nm , T, P ) = µi N i (2.11)
i

Now take differential of the above expression

m
X
dG = [µi dNi + Ni dµi ] (2.12)
i

But if G = G (N1 , . . . , Nm , T, P ) then,

µ ¶ µ ¶ m
X µ ¶
∂G ∂G ∂G
dG = dT + dP + dNi
∂T P,N1 ,...,Nm ∂P T,N1 ,...,Nm i
∂Ni T,P
Xm
= −SdT + V dP + µi dNi (2.13)
i

Comparing 2.12 and 2.13 gives us the famous Gibbs-Duhem equation:

m
X
Ni dµi = −SdT + V dP (2.14)
i

For a single component system, this becomes:

N dµ = −SdT + V dP (2.15)
LECTURE 2. GRAND CANONICAL ENSEMBLE GCE 9

At constant temperature, this reduces to

N dµ = V dP
V
dµ = dP = vdP
N
where v is the volume per molecule
µ ¶ µ ¶
∂µ ∂P
∴ = v
∂N V,T ∂N V,T
µ ¶
∂v ∂P
= v (∵ P = P (v, T ))
∂N ∂v T
µ ¶
−v 2 ∂P
= .
N ∂v T
Inverting the above expression gives us,
µ ¶ µ ¶
∂N −N ∂P N
= 2 ≡ κT (2.16)
∂µ V,T v ∂v T v
where κT is the Isothermal Compressibility
kT N κT
h(∆N )2 i = hN 2 i − hN i2 = (2.17)
v
N.B. h(∆N )2 i = hN 2 i − hN i2 > 0, ∴ κt > 0
Once again, from 2.17 it is clear that the relative fluctuations in particle number scale as,
µ ¶1/2
∆N kT κT 1
= ∝√ ! (2.18)
N vN N
• For a macroscopic system, where N ∼ 10−11 , the relative fluctuations are therefore
extremely small.
Picture:

P(N)

<N> N

z N QN
where the probability of finding the system with N particles is P (N ) = Ξ
LECTURE 2. GRAND CANONICAL ENSEMBLE GCE 10

• Small fluctuations means that P (N ) should be sharply peaked around N ' N

P
• Therefore, with Ξ = ∞ N
N =0 z QN , the sum will be dominated by terms with N ' N
which implies that,

Ξ ' z N QN
−kT ln Ξ ' −kT N ln z − kT ln QN
= −N µ + F (N , V, T )
= −P V

which agrees with our earlier result 2.6

• This demonstrates consistency between the Grand Canonical and and Canonical en-
sembles.

2.3 Comments about κT : Particle fluctuations

• There are exceptions when the scaling arguments 2.18 breakdown because the isother-
mal compressibility diverges and one obtains large particle fluctuations.

• This can happen at a phase transition or when system is in a two-phase state (where
system is a mixture of two phases with different v 0 s, but existing at the same pressure).

• For such cases, µ ¶

∂P
=0
∂v T