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The Grand Canonical Ensemble

Ahmed Maarouf
February 4, 2017

Abstract
Lecture notes. Books: Pathria, Reif, and Scott Shell.

Contents
1 Introduction 1

2 Equilibrium between a system and a particle-energy reser-


voir 2

3 A system in the grand canonical ensemble 3

4 Physical significance of the various statistical examples 5

5 Examples 7

6 Density and energy fluctuations in the grand canonical en-


semble 7

1 Introduction
We have previously studies the microcanonical and canonical ensembles. In
the microcanonical ensemble, our system did not exchange anything wit hits
surroundings; its energy and number of particles were fixed. In the canonical
ensemble, we allowed of the exchange of energy between our system and a
much larger system. We attempted to describe an equilibrium situation in
which our system was in thermal equilibrium with a much larger system,
a reservoir. Thermal equilibrium was reached when both systems reached
the same temperature (remember that temperature of a system is the in-
verse derivative of the entropy of system with respect to its energy). In the

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grand canonical ensemble, we allow for the exchange of energy and number
of particles with the surroundings of our system. Therefore, as the energy of
the system was the variable of interest in the canonical ensemble, the energy
and the number of particles are now our variables of interest in the grand
canonical ensemble.
We will investigate our new situation in two ways: (1) by considering a
given system A to be immersed in a much larger reservoir A0 with which it
can exchange energy and particles, and (2) by considering that our system is
a member of a grand canonical ensemble made up from mental copies of our
system of interest A, where the members of the ensemble exchange energy
and particles.

2 Equilibrium between a system and a particle-


energy reservoir
Consider a given system A immersed in a large reservoir A0 , with which it
can exchange energy and particles, as we see in Fig. ??. After some time,
equilibrium will be reached, which means that the system and the reser-
voir will have the same temperature T (from thermal equilibrium) and same
chemical potential (from chemical equilibrium) (you may need to revise
this part any of the SM-I books, or in section 1.3 of Pathria). The different
states of the system A and reservoir A0 can be labeled by the corresponding
energy and number of particles. Thus, we say that at any instant in time,
if system A has energy Es and number of particles Nr , where s and r are
natural numbers, then the reservoir will have Es0 and Nr0 , such that:

Nr + Nr0 = N (0) (1)


and
Es + Es0 = E (0) (2)
Recall that the reservoir is much larger than our system, by definition. As
such, Es and Nr will be very small compared to the corresponding reservoir
variables. In other words, we can write:

Nr  Nr0 
= 1 1 (3)
N (0) N (0)
and 
Es Es0 
= 1 (0)  1 (4)
E (0) E

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We now ask, what is the probability that our system A is in any of its
microstates; one that is characterized by a number of particles Nr and energy
Es ? Let call this Prs . This probability will be proportional to the number
of microstates 0 (Nr0 , Es0 ) that the system A0 can have for its macrostate
characterized by (Nr0 , Es0 ). Therefore, we write:

Pr,s 0 (Nr0 , Es0 ) 0 (N (0) Nr , E (0) Es ) (5)

Now, we can Taylor-expand the logarithm of the number of states 0 around


the values N (0) and E (0) (why ln 0 and not 0 ?):

ln 0 (N (0) Nr , E (0) Es ) = ln 0 (N (0) , E (0) )


 ln 0   ln 0 
+ (Nr ) + (Es ) + ...
N 0 N 0 =N (0) E 0 N 0 =E (0)
0 1
ln 0 (N (0) , E (0) ) + 0
Nr Es
kT kT 0
(6)

Notice that we are at equilibrium, so 0 and T 0 are the chemical potentials


and temperature of the reservoir and the system A. We can now write the
probability Pr,s as:
Pr,s \exp(Nr Es ) (7)
We already know = 1/kT , and we define = /kT (you may recall
we encountered in our first treatment of quantum statistics, but we did
not correlate it to the chemical potential). We can now use (or enforce) the
proper normalization of Pr,s and write:

exp(Nr Es )
Pr,s = P (8)
r,s exp(Nr Es )

The sum goes over all states r, s accessible to our system A.

3 A system in the grand canonical ensemble


Let us now calculate the probability Pr,s in another way; by constructing
what we call the grand canonical ensemble. We create many mental copies
of our system, and label them from 1 to N . The ensemble has an average
number of particles given by N , and an average energy E,
and therefore
and the total energy
the total number of particles in the ensemble is N N

is N E. We now define nr,s as the number of systems in the ensemble that

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have a number of particles Nr and energy Es . As such, we have these three
constraints: X
nr,s = N , (9)
r,s
X
,
nr,s Nr = N N (10)
r,s

and X

nr,s Es = N E, (11)
r,s

Obviously, there will be many choices (sets) for the nr,s , but each one
of these choices must satisfy the above constraints. A set {nr,s } of these
numbers is a way of distributing the total number of particles or total energy
among the members of the ensemble. Let us focus on one of these sets, {nr,s },
which distributes our total number of particles and total energy such that
we have n00 members having N0 particles and energy E0 .
As an example, consider an ensemble made of 10 copies of our system,
i.e. N = 10. Let the total number of particles in the ensemble be 123 so
N = 123/N = 12.3. Similarly, a total ensemble energy of 456 units means

E = 456/N = 45.6. We can have one system with the 123 particles, and
energy 456 units, where all other systems have no particles (hence no energy).
Is this the only way of having this mode? Another mode of distribution could
be with 1 particle in one system, with 2 units of energy (assuming 2 units
of energy is one of the system energy levels), and 122 particles in another
system with 454 energy units). Again, how many ways can we have this
mode? These two modes, and a variation of the second mode are shown
below:
{123,456} {1,2} {0,0}
{0,0} {122,454} {122,454}
{0,0} {0,0} {1,2}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
{0,0} {0,0} {0,0}
Therefore, any set {nr,s } satisfying our and particle and energy conserva-
tion constraints can be realized in different ways W ({nr,s }),
N
W ({nr,s }) = Q (12)
r,s (nr,s !)

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The most probable mode of distribution will be the one that maximizes W
while abiding by our constraints. We have done this before (Reif, chapter 1,
or you may read section 3.2 of Pathria). The results is:

nr,s exp(Nr Es )
=P (13)
N r,s exp(Nr Es )

Here is another path for deriving this result. Let us calculate the expectation
value of the numbers nr,s in the given distribution W (recall, when we say
expectation value, we MUST specify a state, or a distribution)
P0
{n } nr,s W ({nr,s })
hnr,s i = P0r,s (14)
{nr,s } W ({nr,s })

where the prime is to remind us to respect our conservation constraints while


performing the sums.

4 Physical significance of the various statis-


tical examples
We will now do what we did with other formalisms before, namely establish a
link between the statistics of a system and its thermodynamics. Recall that
we have done this in the microcanonical ensemble, where the entropy was the
link (S = k ln ), and in the canonical ensemble, where the Helmholtz free
energy was the link (F = kT ln Z). Therefore, it looks like we need to define
a new quantity that will take the role of number of states and the partition
function Z in the microcanonical and canonical ensembles, respectively. Let
us define q as: X 
q ln exp(Nr Es ) (15)
r,s

Let us now take the differential of q (Needs some math details from scratch
book. Prove on the board and add later)
X
dq = N
d Ed hnr,s idEs (16)
N r,s

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+ E),
Making use of the differentials of d(q + N we can write

d(q + N + E)
= dq + dN +N d
X
+dE + Ed
= dN + dE hnr,s idEs
N r,s (17)
 X 
= dN + dE 1 hnr,s idEs
N r,s

Let us now recall that the first law of thermodynamics reads:

dE = Q W + dN
(18)

rewriting it,
+ dE + W )
Q = (dN (19)
Now we can argue that
1 X
W = hnr,s idEs (20)
N r,s

= / (21)
giving us:
+ E)
d(q + N = Q (22)
but
kQ = dS (23)
+ E is actually S/k, and therfore,
Accordingly, q + N

E = T S + N E
q = S/k N (24)
kT
Now, N is the Gibbs free energy G, which is also equal to E T S + P V ,
therefore,
X  PV
q = ln exp(Nr Es ) = (25)
r,s
kT

This is our main bridge between the statistics of a given system and its
thermodynamics in the grand canonical ensemble. We now define the fugacity
of a system as:
z e = e/kT (26)

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5 Examples
6 Density and energy fluctuations in the grand
canonical ensemble
References
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