Grand-canonical ensemble

Consider a system of interest in contact with a thermal and particle reservoir – a system separated from
the reservoirs by a permeable wall which is thermally conducting as well as allow the particles to
transfer. Let 𝐸, 𝑁 be the energy and number of particles of the system, and 𝐸! − 𝐸 and 𝑁! − 𝑁 be the
energy and number of particles, respectively, of the reservoir. Total energy 𝐸! is fixed. Then,

𝑑𝐸
Ω ! (E ! , N ! ) = , Ω(E, N) Ω" (E ! − E , N ! − N)
∆

Here, Ω(E) is the total number of microstates of the system

and Ω" (E ! − E, N ! − N) is the total number of microstates
of the reservoir.
Note that E ! = E" + E is the total energy, i.e., system + reservoir. Similarly, N ! = N" + N. In the above
equation, the integration is over all the available energy of the system.

The probability that the system has energy E with the number of particles N is therefore,

P(E, N) ∝ Ω(E, N) Ω" (E ! − E , N ! − N) = Ω(E, N) 𝑒 #!(%" '% ,)" '))/,#

Where we have used that 𝑆" = 𝑘- ln Ω" (E ! − E , N ! − N). This implies

Ω" (E ! − E , N ! − N) = 𝑒 #! (%" '% , )" '))/,# .
Since the reservoir is large E ≪ E ! and N ≪ N ! , we can expand Ω" (E ! − E , N ! − N) (Taylor
expansion) at the point (E ! , N ! )

1 𝜕𝑆" 𝜕𝑆"
Ω" (E ! − E , N ! − N) ≈ exp < >𝑆" (𝐸! , 𝑁! ) − 𝐸 − 𝑁 + ℎ𝑖𝑔ℎ𝑒𝑟 𝑜𝑟𝑑𝑒𝑟 𝑡𝑒𝑟𝑚𝑠HI
𝑘- 𝜕𝐸" 𝜕𝑁"

1 𝐸 𝜇𝑁
Ω" (E ! − E , N ! − N) ≈ exp < >𝑆" (𝐸! , 𝑁! ) − + HI
𝑘- 𝑇 𝑇
1 (𝐸 − 𝜇𝑁) 𝐸 − 𝜇𝑁
Ω" (E ! − E , N ! − N) ≈ exp < >𝑆" (𝐸! , 𝑁! ) − HI = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 exp <− I
𝑘- 𝑇 𝑘- 𝑇

So,
Ω(E, N) ' .'/0
∆ 𝑒 ,# !
P(E, N) =
Z
Where the grand canonical partition function is

2
𝑑𝐸 .'/0
'
Z1 = P , Ω(E, N) 𝑒 ,# !
∆
034

It can be expressed as
2 2
𝑑𝐸 . /0 /0
'
Z1 = P , Ω(E, N) 𝑒 ,# ! 𝑒 ,# ! = P 𝑍567879:6; 𝑒 ,# !
∆
034 034
2

Z1 = P 𝑍567879:6; 𝜁 0
034
0
where 𝜁 is called fugacity, it is a convenient measure of chemical potential.

Consider the following

2
∂Tln Z1 U<,/ 1 ∂ Z1 1 ∂ 𝑑𝐸 '
.'/0
− = − =−
.'/0 ∂β Y P , Ω(E) 𝑒 ,# ! Z
∂β Z1 ∂β 𝑑𝐸 ' ∆
∑2 ( )
∆ Ω E 𝑒
, !
034 ∫
# 034

.'/0
∂Tln Z1 U<,/ 𝑑𝐸 '
∑2
034 ∫ Ω(E) (𝐸 − 𝜇𝑁) 𝑒 ,# !
− = ∆
∂β .'/0
𝑑𝐸 '
∑2
034 ∫ ∆ Ω ( E ) 𝑒 , # !

∂Tln Z1 U<,/
− = 〈𝐸〉 − 𝜇 〈𝑁〉 (1)
∂β
This is one of the useful relations.
Now, consider the following
2
1 ∂Tln Z1 U 1 1 ∂ Z1 1 1 ∂ 𝑑𝐸 '
.'/0
= =
.'/0 ∂𝜇 Y P , Ω(E) 𝑒 ,# ! Z
β ∂𝜇 β Z1 ∂𝜇 β 𝑑𝐸 ' ∆
∑2 ( )
∆ Ω E 𝑒
, !
034 ∫
# 034

.'/0
𝑑𝐸 ' , !
1 ∂Tln Z1 U ∑2 Ω
034 ∫ (E ) 𝑁 𝑒 #
= ∆
β ∂𝜇 .'/0
2 𝑑𝐸 '
∑034 ∫ ( )
∆ Ω E 𝑒
,# !

1 ∂Tln Z1 U
= 〈𝑁〉 (2)
β ∂𝜇
From Thermodynamics, the grand potential is

Ξ = E − T S − 𝜇 N
𝜕 Ξ ∂ (β Ξ)<,/
E − 𝜇 N = Ξ + T S = Ξ − T a b =
𝜕𝑇 <,/ ∂β
 ∂ (β Ξ)<,/
E − 𝜇 N = (3)
∂β
Also,

𝜕 Ξ
a b = −𝑁 (4)
𝜕𝜇 !,<
Comparing (1) & (3) and (2) & (4) we get
Ξ = −k - T ln Z1
As we did before in the canonical ensemble, here we equated the 〈𝐸〉 and 〈𝑁〉 in the grand canonical
ensemble with the thermodynamic E and N.

From the Euler’s relation 𝐸 = 𝑇 𝑆 − 𝑃 𝑉 + 𝜇 N, and the grand potential Ξ = E − T S − 𝜇 N, we get

Ξ = −P V
This implies, the pressure is given by

k - T 1
P = ln Z1 𝑜𝑟 P = ln Z1
𝑉 𝑉 β

Note that the grand canonical in the thermodynamic limit 𝑁 → ∞, computing in the grand canonical
ensemble, with a fixed µ, determining an average 〈N〉, gives the same result as computing in the
canonical ensemble with fixed 𝑁 = 〈N〉.

Grand canonical partition function for distinguishable and indistinguishable particles

We have
2

Z1 = P 𝑍567879:6; 𝜁 0
034

For indistinguishable particles we saw that

1
𝑍567879:6; = [𝑄 (𝑇, 𝑉)]0
𝑁 ! =
For distinguishable particles we saw that
𝑍567879:6; = [𝑄= (𝑇, 𝑉)]0
Where 𝑄= (𝑇, 𝑉) is the single particle partition function.
Thus, for indistinguishable particles
2 2
1 (𝑄= 𝜁)0
Z1 = P 𝑍567879:6; 𝜁 0 = P = 𝑒 >$ ?
𝑁! 𝑁 !
034 034
For distinguishable particles
2 2
1
Z1 = P 𝑍567879:6; 𝜁 = P(𝑄= 𝜁)0 =
0
1 − 𝑄= 𝜁
034 034

Here, 𝑄= 𝜁 < 1 for series to converge.

For the ideal gas we have

𝑉 3
𝑄= = 3 (2 𝑚 𝜋 𝑘𝐵 𝑇)2
ℎ
𝑉
𝑄= = 3
𝜆
Here, 𝜆(𝑇) = rℎ@ /(2 𝑚 𝜋 𝑘- 𝑇) or 𝜆(β) = rβ ℎ@ /(2 𝑚 𝜋 ) is the thermal wavelength.
3
Consider the case of indistinguishable particles, i.e., Z1 = 𝑒 >$ ? = 𝑒 < ?/𝜆 . The average particle
number is expressed as
1 ∂Tln Z1 U 1 ∂𝜁 ∂Tln Z1 U 1 ∂Tln Z1 U 3
〈𝑁〉 = = = 𝜁 = 𝑉 𝜁/𝜆
β ∂𝜇 β ∂𝜇 ∂𝜁 β ∂𝜁
So, using the relation
PV = k - T ln Z1
𝜁
PV = k - T 𝑉 3 = 〈𝑁〉 k - T
𝜆

Similarly,
∂Tln Z1 U 3 𝑉 𝜁 ∂𝜆
〈𝐸〉 = 𝜇 N − = 4
∂β 𝜆 ∂β
3
〈𝐸〉 = 〈𝑁〉 k - T
2
We can calculate the corresponding entropy for the system which will be same as that we have
obtained for Microcanonical and Canonical ensembles as it should be.

Number fluctuations

We have
1 ∂Tln Z1 U
〈𝑁〉 =
β ∂𝜇
Consider
1 ∂〈𝑁〉 1 ∂@ Tln Z1 U
= @
β ∂𝜇 β ∂𝜇@
 1 ∂ 1 ∂ Z1
= u v
β@ ∂𝜇 Z1 ∂𝜇
@
1 1 ∂@ Z1 1 ∂ Z1
= @ Y @ − @ u v Z
β Z1 ∂𝜇 Z1 ∂𝜇

Here,
1 ∂Z1
〈𝑁〉 =
β Z1 ∂𝜇
and we can easily show that
1 ∂@ Z1
〈𝑁 @ 〉 =
β@ Z1 ∂𝜇@
So, the number fluctuations are
1 ∂〈𝑁〉
= 〈𝑁 @ 〉 − 〈𝑁〉 = 𝜎0 @
β ∂𝜇
This can be written as
𝜎0 @ 𝑘- 𝑇 ∂〈𝑁〉 𝑘- 𝑇 ∂(𝑉/𝑣)
= =
〈𝑁〉 @ 〈𝑁〉 @ ∂𝜇 〈𝑁〉@ ∂𝜇
<
Where we have expressed 𝑣 = 〈0〉

𝜎0 @ 𝑘- 𝑇 𝑉 ∂ 𝑣
= −
〈𝑁〉@ 〈𝑁〉@ 𝑣 @ ∂𝜇
𝑘- 𝑇 ∂ 𝑣
= −
𝑉 ∂𝜇
Using Gibbs-Duhem relation, 𝑁 𝑑𝜇 = 𝑉 𝑑𝑝 − 𝑆 𝑑𝑇, we can write 𝑑𝜇 = 𝑣 𝑑𝑝 at constant temperature.
Using it, we get
𝜎0 @ 𝑘- 𝑇 1 ∂ 𝑣
= −
〈𝑁〉 @ 𝑉 𝑣 ∂𝑝
𝜎0 @ 𝑘- 𝑇
= 𝑘 !
〈𝑁〉 @ 𝑉
= C<
Where 𝑘 ! is called Isothermal compressibility which is defined as 𝑘 ! = − < zCD{ . This is an
!,0

important relation related to the phase transitions.