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Phys 221 Exercises

1. The partition function for a mixture of two ideal gases A and B is the product of the individual partition functions for each gas raised to the number of particles of that gas, divided by the factorial terms to avoid overcounting indistinguishable states. The free energy and mixing entropy are derived, showing an additional entropy term due to the indistinguishability of the particles. 2. For a system of N non-interacting spin-1/2 particles in a magnetic field B, the partition function is derived as (2cosh(μB/kBT))^N. The entropy is then calculated, showing it depends only on μB/kBT. Therefore, reducing the field adiabatically will
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0% found this document useful (0 votes)
97 views4 pages

Phys 221 Exercises

1. The partition function for a mixture of two ideal gases A and B is the product of the individual partition functions for each gas raised to the number of particles of that gas, divided by the factorial terms to avoid overcounting indistinguishable states. The free energy and mixing entropy are derived, showing an additional entropy term due to the indistinguishability of the particles. 2. For a system of N non-interacting spin-1/2 particles in a magnetic field B, the partition function is derived as (2cosh(μB/kBT))^N. The entropy is then calculated, showing it depends only on μB/kBT. Therefore, reducing the field adiabatically will
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1. Consider a mixture of two ideal monoatomic gases.

The partition function can be written


( Z Na Nb
a Zb )
as Z n= where Za is the partition function of a single particle of gas a of which
( N a! N b! )
there are Na particles and Zb is the partition function of a single particle of gas b of which
there are Nb particles. The total number of particles is N = Na + Nb. If the particles were
Z
identical the partition function would be Z N = a .
N!
(a) Calculate the free energy in the two cases, assuming that Za = Zb.
1
(b) Show that the factor lead to an extra mixing entropy of the form
N a! N b!

[
Smixing =−k B N a ln ( NN )+ N ln ( NN )] .
a
b
b

( Z Na a
Z Nb b
)
(a) The partition function of the mixture is: ZN =
( N a! Nb ! )

( Z Na Z Nb )
[ ]
a b

The Helmholtz free energy is: F=−k B T ln Z N =¿−k B T ln


( N a ! N b !)

Z Naa

For identical particles: Za = Zb, N = N a + Nb  ZN =


N!

Z Na
( )
a

F identical =−k B T ln
N!

(b) The difference in the free energies if Za = Zb even if the particles are not identical:
Z Na a
Z aN a

∆ F=k B T ln
N! ( )
−¿ k B T ln
N a! Nb ! (
¿ )
Na Na

∆ F=−k B T ln
[(
Za
Na ! N b!
Z
−ln a
N! ) ( )]
Z Na a

∆ F=−k B T ln
[ ] Na! N b!
Z
Na
a
N!
=−k B T
[ N!
N a! Nb ! ]
Apply Stirling’s approximation:
∆ F=−k B T [ N ! ln N !−N a ! ln N a !−N b ! ln N b ! ]

∆ F=−k B T [ N ln N −N−( N a ln N a −N a )− ( N b ln N b−N b ) ]

∆ F=−k B T [ ( N a+ N b ) ln ( N a + N b ) −( N a + N b ) −( N a ln N a −N a )−( N b ln N b−N b ) ]

∆ F=−k B T [ ( N a+ N b ) ln ( N a + N b ) −N a ln N a−N b ln N b ]

The mixing entropy due to the particles is:

S= ( ∂∂ TF )
V

S=−k B [ ( N a + N b ) ln ( N a + N b ) −N a ln N a−N b ln N b ]

S=−k B ¿

N N
[ ( ) ( )]
S=−k B N a ln
Na
+ N b ln
Nb

2. Consider a system of N identical, non-interacting, magnetic ions of spin ½, magnetic


moment , in a crystal at temperature T in a uniform magnetic induction field B.
Calculate the partition function ZN for this system and from it obtain a formula for the
entropy S.

The crystal is initially in thermal equilibrium with a reservoir T = 1 K, in a


magnetic induction field of 10 tesla. The crystal is thermally isolated, and the field is
reduced adiabatically (so entropy is constant) until the field is 10-2 tesla. What
temperature do the spins reach at the end of the process?

At fixed temperature (canonical ensemble), consider N spins in a constant magnetic field B.


Each spin has only two states:

(i) spin up with energy:ϵ ↑=−μB


(ii) spin down with energy ϵ ↓=+ μB
For a single ion:

−E r μB −μB
kB T k BT k BT
Z1 =∑ e =e +e
r

e x + e−x
Apply hyperbolic trigonometric identity: cosh x=
2

Z1 =2cosh ( kμBT )
B

For ions: Z N =( Z 1 ) N

N
μB
(
Z N = 2 cosh
kB T )
The Helmholtz free energy is given by:

F=−k B T ln Z N =−N k B T ln Z 1

μB
F=−¿ Nk B T ln 2 cosh
Hence the entropy S is:
kB T ( )
S=− ( ∂∂TF ) =N k ln (2 cosh kμBT )−( N k T ) kμBT tanh ( kμBT )
B
B
B
B
B
2
B

S=N k B ln 2 cosh
[{ ( )} μB
kB T

μB
kB T
tanh
( )]
μB
kBT

The entropy S is a function of B/kBT. Hence, if the entropy of the spin states is maintained
constant then the temperature of the spin state can be lowered by reducing the magnetic field
adiabatically. In the crystal, the decrease in the temperature of the spin states can result in a
decrease of the temperature of the crystal vibrations by heat transfer. Therefore the whole
crystal is cooled by an adiabatic reduction of the magnetic field. That is:

T1 T 2
=
B1 B 2

10−2 T
T 2= ( 1 K ) ( 10 T )
T 2=0.001 K
3. Two identical particles of mass m interact with an external potential which is harmonic,
but they do not interact with each other. The Hamiltonian of the system is:
p21 p22 mω 2 2 2
H=
^ +
2m 2m
+
2
( x 1 + x 2 ).
(a) What are the energy levels of the system?
(b) Given that the particle are bosons, determine the partition function.
(c) Repeat the calculation given that the two particles are fermions.

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