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Ahmed Maarouf
February 4, 2017
Abstract
Lecture notes. Books: Pathria, Reif, and Scott Shell.
Contents
1 Introduction 1
5 Examples 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
1
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.
Nr Nr0
= 1 1 (3)
N (0) N (0)
and
Es Es0
= 1 (0) 1 (4)
E (0) E
2
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:
exp(Nr Es )
Pr,s = P (8)
r,s exp(Nr Es )
3
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 !)
4
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 })
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
5
+ 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
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)
6
5 Examples
6 Density and energy fluctuations in the grand
canonical ensemble
References
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