University of South Carolina

Department of Physics and Astronomy

Phys 706, Thermodynamics and Statistical Physics.
Final Exam
April 27, 2011
The test is open book/notes. You can use any materials you like. If you need extra
paper or you forgot a calculator please ask.
There are 3 problems, each worth 10 points. It is enough to solve one problem to get a
full credit. Choose any one you like. If you solve more, you will get extra credit. If you have
a question about the problems formulation please do not hesitate to ask. I will either
answer your question or will tell you that I cannot do it without revealing the solution.
Your solutions should have a readable form showing the ow of argument. You have to
be able to express yourself in writing. Writing skills are important for any scientist. They
are not just making your solutions look nicer. If you cannot explain yourself clearly, you
probably do not understand what you are doing.
You can still try to guess the answer for a problem. If the solution is a number or an
expression, I will accept your answer (guessing will not be accepted for problems where the
answer is yes or no). However, if no explanations are given, only correct answers will
be graded positively. There will be no partial credit in the absence of correct, readable
explanations.
GOOD LUCK!
1 Ideal gas with gravity eld
You have a cylindrical container of height h and bottom area A lled with classical, ideal,
single-atomic gas. The total number of atoms is N, the mass of each atom is m, and the
temperature is T. Since every molecule is attracted to the Earth with the force mg, there
will be more molecules at the bottom of the cylinder than at the top.
(a)[2 points] Calculate the dependence of the gas concentration n(z) as a function of
height z. (The uneven n has to create pressures which balance the gravity force acting on
each element of gas.)
(b)[8 points] In addition to the kinetic energy the gas has some potential energy in the
gravity eld. Find the total heat capacity of the gas in the cylinder. Find the limits at
T and T 0.
Solution:
(a) If you consider a thin horizothal slice of gas of between the planes z and z +dz, the
dierence between the pressures at its bottom and top has to be equal to the weight of the
gas. This gives
mgn(z)dz = P(z) P(z + dz) =
dP
dz
dz
Using P = nk
B
T we transform this to a dierential equation
dn
dz
=
mg
k
B
T
n(z)
The solution is
n(z) = n(0)e
(mg/k
B
T)z
= n(0)e
z/z
0
where n(0) is the concentration at the bottom of the cylinder and z
0
k
B
T/mg is a
characteristic length of concentration decay.
The bottom concentration n(0) is related to the total number of particles by the require-
ment
N = A
_
h
0
n(z)dz = Az
0
n(0)(1 e
h/z0
)
which gives
n(0) =
N
Az
0
(1 e
h/z0
)
Note that for T one has z
0
and n(0) N/Ah. At high temperatures the gas is
distributed over the cylinder almost uniformly and its concentration is simply the number
of particles divided by the total volume. At low temperatures z
0
0, so n(0) N/Az
0
.
Most of the atoms are concentrated in a thin layer of width z
0
near the bottom and occupy
the volume Az
0
.
(b) Since the gas is non-uniform in vertical direction, we have to calcfulate the energy of
each slice of gas in the interval (z, z +dz) and then sum all such contributions. The kinetic
energy of each slice is dK = (3/2)nk
B
Tn(z)Adz. The total kinetic energy is
K =
3
2
k
B
TA
_
h
0
n(z)dz =
3
2
k
B
TN
The potential energy of the slice is d = mgzn(z)Adz, which gives
= mg
_
h
0
zn(z)dz = mgn(0)A
_
h
0
ze
z/z
0
dz
To calculate the integral we employ a standard trick. Consider the easier integral
I(a) =
_
h
0
e
az
dz =
1 e
ah
a
then
_
h
0
ze
az
dz =
d
da
I(a) =
hae
ah
(1 e
ah
)
a
2
=
1 hae
ah
e
ah
a
2
Using this formula in the expression for we get
= mgn(0)Az
2
0
_
1
h
z
0
e
h/z
0
e
h/z
0
_
= mg
NAz
2
0
_
1 h/z
0
e
h/z
0
e
h/z
0
_
Az
0
(1 e
h/z
0
)
=
= k
B
TN
_
1 h/z
0
e
h/z
0
e
h/z
0
_
(1 e
h/z0
)
= k
B
TN
_
1
he
h/z
0
z
0
(1 e
h/z0
)
_
= k
B
TN
mghNe
h/z0
1 e
h/z
0
The total energy can now be written as
E = K + =
5
2
k
b
TN
mghN
e
h/z0
1
To nd the heat capacity we dierentiate w.r.t. T and get
c =
E
T
= k
B
N
_
5
2

_
h
z
0
_
2
e
h/z
0
(e
h/z
0
1)
2
_
For T (z
0
) the second term in the brackets goes to unity and one gets c
(3/2)Nk
B
, i.e., to the heat capacity of the gas without gravity. For T 0 (z
0
0) the
second term in the brackets goes to zero and c (5/2)Nk
B
. In this example the heat
capacity is larger at lower temperatures.
The physical meaning of this result is as follows. At low temperatures the gas is eectively
concentrated in the bottom layer of thickness z
0
. As the temperature is increased, the
thickness of the layer grows and so does the potential energy of the gas atoms. The potential
energy increase gives a contribution to heat capacity, which happens to be equal to k
B
TN
according to our calculation. At very high temperatures the atoms are distributed almost
uniformly in the vertical direction and occupy the whole cylinder. The further increase
of temperature does not lead to the increase of potential energy, this contribution in heat
capacity is absent, and we recover the heat capacity of the gas in the absence of gravity
eld.
The Nernst theorem states that the heat capacity should vanish at T 0. Our classical
model does not obey the Nernst theorem. The real gas at low temperatures will start
developing quantum corrections to our results. One of these corrections will appear when
z
0
will approach the temperature wavelength (T) of the atoms. The other when the
distance between the atoms l n
1/3
becomes comparable to (T). As a result of these
quantum corrections the Nernst theorem will be satised and the heat capacity will drop to
zero at T 0.
2 1D gas of multi-atomic molecules
(A) Gas of 2-atomic molecules
(B) Molecules stick together and form 3-atomic molecules
A one dimensional (1D) ideal gas of two-atomic molecules is shown in the Figure (A).
Each molecule consists of one atom of mass m and another atom of mass M = 10
4
m,
connected by a spring of constant k. In each molecule the heavier atom is located on the
left. Calculate the heat capacity c
1
(T) of the gas of N such molecules taking into account
the discrete nature of the energy levels of the vibrational motion. Since M m holds, you
can always make approximations like M + m M, etc.
Assume now that the gas undergoes a transition where each two molecules stick together
forming a larger molecule of three atoms (see Figure B). The total number of molecules is
now N/2. Calculate the heat capacity c
2
(T) of the gas in the new state.
Find the dierence c = c
1
(T) c
2
(T) in the limits
(a) T
(b)
_
k
M
k
B
T
_
k
m
(c) T 0
Solution: To calculate the vibrational contribution we have to know the eigenfrequencies
of the systems oscillations. In the case of two-atomic molecules it is well known that the fre-
quency is determined by the spring constant k and the eective mass m
eff
= Mm/(M +m)
as
0
=
_
k/m
eff
. Since M m, in our approximation m
eff
m and
0

_
k/m. Phys-
ically, the condition M m means that the large atom almost does not move. Therefore
the small atom moves as if it is attached by the spring to a stationary wall. The formula

0

_
k/m then becomes obvious.
After the three-atoms molecules are formed, each of them has two modes of oscillations.
The mode frequencies can be calculated exactly by writing down Newtons equations for
every atom or by any other method studied in classical mechanics. However, due to the
condition M m one can easily nd the approximations for the mode frequencies. In one
mode the two heavy atoms with masses M and M +m are almost immobile, while the light
atom oscillates. This mode is close to the oscillation of the light atom attached to the wall
and its frequency
1

0

_
k/m. In another mode, the heavy atoms move slowly. The
motion of the light atom then tracks the motion of the middle atom. The oscillations of the
system are close to those of a diatomic molecule with atoms of masses M and M + 2m. In
our approximation of M + 2m M we need to nd the oscillation frequency of two atoms
of mass M connected by a spring with a constant k which is equal to
2

_
2k/M. Notice
that
2

0
.
We now proceed to the calculation of heat capacity. In 1D the translational motion gives
a contribution k
B
/2 per molecule. The vibrational heat capacity is given by the oscillator
formula
c
0
(T, ) = k
B
_

k
B
T
_
2
e
/k
B
T
(e
/k
B
T
1)
2
per each vibrational degree of freedom. For the case of N two-atomic molecules we get
c
1
(T) = N
_
k
B
2
+ c
0
(T,
0
)
_
In the case of N/2 three-atomic molecules
c
2
(T) =
N
2
_
k
B
2
+ c
0
(T,
0
) + c
0
(T,
2
)
_
Now we can nd the answers to the questions of the problem.
(a) At T one has c
0
(T,
0
) k
B
, c
0
(T,
2
) k
B
, so c
1
(3/2)k
B
N and
c
2
(5/4)k
B
N, so
c =
k
B
N
4
(b) Here the temperature is chosen so that the high frequency vibration is frozen,
c
0
(T,
0
) 0, and the low frequency vibration is still classical, c
0
(T,
2
) k
B
. This choice
was possible because
2

0
holds. We get c
1
(1/2)k
B
N, c
2
(3/4)k
B
N, so
c =
k
B
N
4
(c) In the T 0 limit c
0
(T,
0
), c
0
(T,
2
) 0. Only the translational degrees of freedom
contribute to the heat capacity c
1
(1/2)k
B
N, c
2
(1/4)k
B
N. We have
c =
k
B
N
4
(same result as for high temperatures).
3 Three fermion system
You have three fermion particles at temperature T. They do not interact with each other
and are subject to an external potential. This potential is such that a single particle can
be in one of the four distinct states which have the energies
1
= 0,
2
=
3
= ,
4
= 2.
No other single-particle states are available. (In real life the nite number of single-particle
states can be eectively realized if all other states have much higher energies
i
k
B
T
(i = 5, 6, ...) and thus do not play a role at this particular temperature).
(a)[2 points] Find the possible quantum mechanical states of the three fermions and their
energies.
(b)[8 points] Calculate the partition function of the system and nd its heat capacity.
Solution:
(a) The many particle state is given by a set of occupation numbers for each single-
particle state, (n
1
, n
2
, n
3
, n
4
) in our case. They have to satisfy n
1
+n
2
+n
3
+n
4
= 3 (total
of 3 particles) and n
i
= 0, 1 (fermions). Thus we will always have 3 single-particle states
lled and the fourth state being empty. Consequently any many-particle state is completely
characterized by specifying which state is empty, and we have 4 possible many-particle states.
When the state |i is empty, the many-particle energy is E
i
= (
1
+
2
+
3
+
4
)
i
= 4
i
.
(b) The partition function is
Z =
4

i=1
e
Ei
= e
4
_
1 + 2e

+ e
2
_
= e
4
(1 + e

)
2
The average energy is
E =
4

i=1
E
i
e
E
i
Z
=
1
Z
4

i=1
(4
i
)e
E
i
= 4
e

+ e

+ 2e
2
(1 + e

)
2
= 4
2
1 + e

The heat capacity is obtained by dierentiating w.r.t. T

c =
E
T
= 2k
B
_

k
B
T
_
2
e
/k
B
T
(1 + e
/k
B
T
)
2