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GC Ensemble With Ideal Gas 2 PDF

This lecture discusses the grand canonical ensemble, which describes a system in contact with a reservoir that can exchange energy and particles. The key properties are: 1) The probability of a system having N particles and energy Ej is proportional to e−β(Ej −μN) , where β is 1/kT, μ is the chemical potential, and Ej is the energy of state j. 2) The grand canonical partition function Q is defined as the sum of e−β(Ej −μN) over all states. The grand potential Ω is -kTlnQ. 3) For a macroscopic system, the sums can be replaced by integrals, and the integr

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81 views2 pages

GC Ensemble With Ideal Gas 2 PDF

This lecture discusses the grand canonical ensemble, which describes a system in contact with a reservoir that can exchange energy and particles. The key properties are: 1) The probability of a system having N particles and energy Ej is proportional to e−β(Ej −μN) , where β is 1/kT, μ is the chemical potential, and Ej is the energy of state j. 2) The grand canonical partition function Q is defined as the sum of e−β(Ej −μN) over all states. The grand potential Ω is -kTlnQ. 3) For a macroscopic system, the sums can be replaced by integrals, and the integr

Uploaded by

Brandon Stephens
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Physics 127a: Class Notes

Lecture 9: Grand Canonical Ensemble


This describes a system in contact with a reservoir with which it can exchange energy and particles. The
equilibrium is characterized by the reservoir temperature T and chemical potential . As for the canonical
ensemble, we can derive properties of the grand canonical ensemble by treating system plus reservoir as an
isolated system together described by the microcanonical ensemble. The results are:
Probability for the system to have N particles and be in state j with energy Ej(N ) is
(N )

Pj,N e(Ej

N )

(1)

(remember this comes from counting the number of states in the reservoir)
Define the grand canonical partition function
X X (E (N ) N )
j
Q=
e
,
N

(2)

and the corresponding grand potential


 = kT ln Q.
For a macroscopic system we can replace the sums by integrals
Z
Z
dE (EN T S(E,N )
Q ' dN
e
1

(3)

(4)

where eS/k is the number of states in the energy shell 1. For large N the integrand is dominated by
E ' E and N ' N which minimize E N T S given by differentiation


S
=T
,
(5)
N E


S
1=T
.
(6)
E N
N , and tell us the physical result that the temperature and
These two equations implicitly give E,
chemical potential of the system are given by the results of the isolated system at the most probable E
and N. Furthermore in evaluating ln Q only the value of the integrand at its maximum contributes at
O(N )
 ' U T S N
(7)
N,
but can replace them by the means U, N since
(strictly we should use the most probable values E,
the distribution is so narrow).
Differentiating and using dU = T dS P dV + dN gives the thermodynamic identity in the form
d = SdT N d P dV .

(8)

Making a system at T , , V by adding little volumes dV at the same T , P gives us (since then
dT = d = 0)
 = P V .
(9)
1

Grand Potential for the Classical Ideal Gas


We can write
Q=

z N QN

(10)

with z = e known as the fugacity and QN the canonical partition function for N particles. Also, for the
classical ideal gas
(Q1 )N
QN =
,
(11)
N!
so that
X (zQ1 )N
Q=
(12)
= ezQ1 .
N
!
N
Thus


PV
=
= ln Q = zQ1 .
kT
kT

For a monatomic gas we found


Q1 = V

2 mkT
h2

(13)

3/2
.

(14)

This is the ideal gas lawbut in terms of rather than N . Normally we would eliminate in terms of the
mean N using



N =
.
(15)
T ,V
From Eq. (13) we see that the only dependence of  is in the fugacity z = e , and differentiating gives
N = zQ1

(16)

which with Eq. (14) gives the same expression for (N, T , V ) as we found before, and with Eq. (13) gives
the ideal gas law in the familiar form.
Number fluctuations
In the grand canonical ensemble, the probability of finding N particles in the system is
P

(N )

e(Ej N )
z N QN
P (N ) = P P
.
=
(N )
(Ej N )
Q
e
N
j
j

For the ideal gas


QN =

(Q1 )N
N!

(17)

(18)

and

zQ1
P (N) = zN QN
.
(19)
1 e
P
As we have seen hN i = zQ1 (this can of course be derived as N NP (N) from equation (19)), so that for
the ideal gas the number fluctuations are described by the Poisson distribution

P (N) =

hN iN ehNi
.
N!

(20)

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