Homework 2

Problem I.

Consider a system of three particles. Assume each particle can occupy either of 3 energy
levels, , 2, and 3.

1. What are the possible values of the total energy E of this system?
2. What is the number of microstates
dist
(E) available for each value of the total energy
assuming the particles are distinguishable.
3. What is the number of microstates
indist
(E) available for each value of the total
energy assuming the particles are indistinguishable.

Solution.

We can distribute 3 particles over 3 levels by the following ways

3 0 0 0 0 1 2 2 1 3 1
2 0 1 2 3 0 0 1 2 0 1
3 2 1 0 2 1 0 0 0 1
E= 3 4 5 6 5 7 8 7 9 6

So the available total energies are 3, 4, 5, 6, 7, 8, 9
If the particles are distinguishable, each of the configuration can be realized by the
following ways (corresponding to each column of the above table)

= 1 3 3 1 3 3 3 3 1 6

As we see, the total energy 3 can be realized by one way, 4 by 3 ways, and so on.
We obtain:

dist
(3)=1

dist
(4)=3

dist
(5)=6

dist
(6)=7

dist
(7)=6

dist
(8)=3

dist
(9)=1

If the particles are indistinguishable, each of the configuration can be realized by the
following ways (corresponding to each column of the above table)

= 1 1 1 1 1 1 1 1 1 1

As we see now, the total energy 3 can be realized by one way, 4 by 1 way, and so on.
We obtain:

indist
(3)=1

indist
(4)=1

indist
(5)=2

indist
(6)=2

indist
(7)=2

indist
(8)=1

indist
(9)=1


Problem II.

Suppose the number of microstates (E,N,V) of a system is described by the following
formula:

(E,N,V)= (E/a)
N
/N!

where a is some parameter having the dimension of energy.

Assuming the number of particles N is very large (so that lnN! can be approximated by
Stirling formula) derive basic thermodynamical properties of the system:

1. Entropy S(E,N,V),
2. Internal energy E(S,N,V)
3. Temperature T,
4. Pressure P,
5. Specific heat coefficients C
V
and C
P
6. Based on the expression for the specific heat how can you characterize the system in
terms of degrees of freedom for each particle?

Solution.

1. Find the entropy:

S(E,N,V)=k ln= kNln(E/a)-k lnN! = kN ln(E/a)- kN ln N + kN = kN [ln(E/aN) + 1]

2. Find the internal energy

E(S,N,V)=aN exp(S/kN-1)

3. Temperature of the system follows by differentiating the energy with respect to
entropy:

T=a/k exp(S/kN-1) =E/kN or E=kNT as the connection between energy and temperature.

4. Pressure in the system is equal to zero since there is no dependence on volume

P=0

5. Specific heat at constant volume and constant pressure are equivalent and are given by
the derivative of the energy with respect to temperature:

C
V
= C
P
= kN

6. As we obtained the specific heat which is just 2(1/2kN) we can say that the system has
two degrees of freedom. At first glance that could be either a set of particles moving in
two dimensions (2 kinetic degrees of freedom) or a set of 1 dimensional harmonic
oscillators having one kinetic and one potential degree of freedom. Indeed the case of 2D
gas does not work because it should produce some pressure P in the system, while we
obtained P=0. As a result, the system is in fact represented by N classical 1D harmonic
oscillators.

Problem III.

Let us study the statistical mechanics of an extreme relativistic gas of N particles
confined in a box of size L and characterized by the single particle energy states

(n
x
,n
y
,n
z
)=hc/2L (n
x
2
+n
y
2
+n
z
2
)
0.5


(The fact that the gas is relativistic is reflected in linear dependence of its energy from the
momentum, i.e =cp.)

Assume N is very large.

1. How the entropy scales with energy E and volume V?
2. What is the temperature T of the gas?
3. What is the pressure P and the equation of states for the gas ?
4. What are the specific heat coefficients C
V
and C
P
?



Solution.

The total energy E can be obtained by considering the sum over all particles

2 2 2 1/2
1/3
1
( )
2
N
rx ry rz
r
hc
E n n n
V
=
= + +

So that the number of microstates can be obtained by finding every possible combination
of integers n
r
which satisfies the equation above. Note that the condition
2 2 2 1/2
1/3
1
( )
2
N
rx ry rz
r
hc
E n n n
V
=
= + +

can be rewritten in the form

* 1/3 2 2 2 1/2
1
2 / ( )
N
rx ry rz
r
E EV hc n n n
=
= = + +

Following arguments given in 1.4 of the textbook, instead of evaluating the number of
microstates which come from solving the last equation one can evaluate the number of
microstates (E) for all energies from 0 till E which is proportional to the volume of this
3N dimensional object. Given the logarithmic nature of the entropy, this is sufficient to
evaluate the properties when N goes to infinity. It is then clear then the volume inside this
3N-dimensional object scales as E*
3N
or as E
3N
V
N
.


1. The number of available microstates would scale with the energy and volume as
follows
3
( , , ) ( )
N N
E N V N V E = where (N) is a function of the number of particles
only. As a result the entropy of the system is given by
( , , ) ln 3 ln ln ( ) S E N V kN V kN E k N = + +
As long as we keep the number of particles constants we dont have to differentiate the
last (unknown expression) but can easily answer the remaining questions of the problem.

2. The (inverse) temperature of the gas can be obtained by differentiating the entropy
with respect to energy: 1/T=3kN/E or E=3kNT which is remarkably different from the
expression for the non-relativistic gas (E=3/2kNT)

3. The pressure in the gas can be obtained by evaluating the derivative of the entropy by
volume: P/T=kN/V or PV=kNT which is the same as for the non-relativistic case.

4. The specific heat at constant volume is the derivative on internal energy with respect to
temperature: E(T)= 3kNT, C
V
=3kN. The C
P
can be obtained as the derivative of enthalpy
H with respect to temperature. Since H(T)=E(T)+PV=3kNT+kNT=4kNT, we obtain
C
P
=4kN. Both expressions are different from the corresponding numbers in non-
relativistic case.



Problem IV.

Four moles of nitrogen and one mole of oxygen at pressure P= 1 atm and T=300 K are
mixed together to form an air of the same temperature and pressure. Calculate the entropy
of the mixing per mole of the air formed.





Note here that the limit when nitrogen and oxygen are replaced by the same kind of
atoms (i.e. we expect the entropy of the mixing to be equal zero) is not obeyed here! This
is because the particles become indistinguishable, and while the evaluation of S
b
is still
valid, the formula for S
a
is not valid as one would have to write the entropy after mixing
in the form
3/2
2
2
( ) ln
O N
a O N
O N
V V mkT
S N N k
N N h

+
= +


+




As a result
3/2
, 2
3/2 3/2
2 2
2
( ) ( ) ln
2 2
ln ln
( ) ln ln ln
O N
P T O N
O N
O N
O N
O N
O N O N
O N O N
O N O N
V V mkT
S N N k
N N h
V mkT V mkT
N k N k
N h N h
V V V V
N N k N k N k
N N N N

+
= +


+

+
+

+

0 =

under the assumption of the same density!