15-1 Assuming that, O, the number of possible combinations of particle energies in a

macrostate is
#
!
i
N levels
i
i i
g
N
O =
[

it is shown in Section 15.4 that the most probable distribution of energy levels is the
Maxwell-Boltzmann distribution, ( ) exp
i i i
N B g | c = . Derive the corresponding
relationship for N
i
using the Bose-Einstein model defined by
( )
( )
#
1
1 !
1 ! !
levels
i i
BE
i i i
g N
g N
O
=
+
=

[



S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-2 Four indistinguishable particles are to be placed in two energy levels, each of which has a
degeneracy of three. There is no restriction on the number of particles that can occupy an
energy state. Determine the thermodynamic probability of all possible arrangements and
identify the most probable arrangement.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-3 A system consists of eight particles that can occupy five different energy levels. The
energy levels are equally spaced and differ by units with the value of the first level
being zero. The degeneracy of each of the energy five energy levels is provided in Table
15-3. The total energy of the system is 24. Calculate the total number of macrostates
and microstates assuming that a.) the particles are distinguishable, b.) the particles are
indistinguishable and c.) the particles are indistinguishable and only one particle can
occupy a microstate. What is the most likely macrostate? What happens to the number
of microstates as the energy of the system is increased, all else being the same? What
happens to the number of microstates as the spacing between energy levels increases with
the total energy remaining the same? What happens to the number of microstates as the
number of particles is increased with the total energy remaining the same?
Table 15-3: Degeneracy of each energy level
Energy level Degeneracy
0 1



12


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-4 Sound travels through a gas as a wave at an average velocity that depends on the
temperature. What is the quantum number n of a neon molecule traveling at the speed of
sound at 300 K in a cubic enclosure that is 10 m on a size?


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15.5 Prepare a plot of the velocity of an argon atom that is contained in a cube of length L on a
side if its three quantum numbers are each 1e8 for L=1 cm to 1 m.

S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-6 Air at 101 kPa, 298 K circulates freely in a large box subdivided into leaky cells each of
volume 1 cm
3
. The thermodynamic probability for the distribution of equal numbers of
molecules, N
eq
, in each of the cells should exceed the value for the non-equilibrium
situation in which the numbers in the cells differ. Consider a non-equilibrium situation in
which in which one cell contains 1% more molecules and a second cell contains 1%
fewer molecules than the N
eq
and all other cells contain N
eq
molecules. Calculate and
compare:
a) the difference in entropy between the equilibrium and non-equilibrium states using
classical thermodynamics, and
b) the difference in the logarithms of the thermodynamic probabilities for the
equilibrium and non-equilibrium states.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-7 The Sackur-Tetrode equation fails to provide an accurate estimate of the specific entropy
of monatomic oxygen because this molecule has internal energy modes due to its excited
electron state, in addition to its translation energy modes. The electronic states of
molecule can be determined by solving the wave equation based on a Coulomb potential
in spherical polar coordinates. The Pauli exclusion principle must be applied to disallow
two electrons in a single atom to simultaneously have an identical set of quantum
numbers. The solution for monatomic oxygen results in the energy levels and atomic
momentum numbers, J provided in Table 15-7. The degeneracy for each energy level is
2J+1. The partition function, f, is defined in general as
#
exp( /( ))

levels
i i
f g k T .
Using the information in the table above for the degeneracies and energy levels for
monatomic oxygen, calculate and plot the specific heat and specific entropy for
monatomic oxygen for temperatures between 200 K and 2000 K at atmospheric pressure
and compare these values to the values provided in with the NASA external procedure in
EES.
Table 15-7: Energy levels and atomic momentum numbers for monatomic oxygen
Energy/(h c)
[1/mm]
J
Atomic momentum number
0 2
15.85 1
22.65 0
1586.77 2


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-8: Calculate and plot the specific enthalpy and specific entropy of mercury vapor at a
pressure of 5 atm as a function of temperature for temperatures between 300 K and 1000
K based on statistical thermodynamics. Compare the results with the values provided by
the NASA external procedure in EES and explain any discrepancies.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-9 The specific entropy of an ideal monatomic gas as determined from statistical
thermodynamics is

1.5
2
2
ln 2.5
t
(
| |
= +
(
|
\ .
(

MkT kT
s R R
h P

a.) Indicate how the specific entropy varies as the mass of the gas molecules (M)
increases at fixed temperature and pressure and provide an explanation for this trend
from statistical thermodynamics.
b.) Indicate how the specific entropy varies as the temperature approaches absolute zero
at fixed pressure and provide an explanation for this trend from statistical
thermodynamics.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-10 As a first approximation, the quantum-mechanical energy contribution resulting from
one-dimensional atomic vibrations in a solid at constant frequency v is:

1
0, 1, 2,.....
2
i
i h i c v
| |
= + =
|
\ .

where h is Planck's constant. The partition function corresponding to these vibrations,
assuming only one microstate is allowed per energy level, is

exp
2
1 exp
h
k T
f
h
k T
v
v
| |

|
\ .
=
| |

|
\ .

Derive a relation for the constant volume specific heat of a substance that has this
partition function.



S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-11 A system has available energy levels of 0, 1, and 2 units and each of the energy levels has
a degeneracy of 10,000. Consider a thermodynamic state consisting of 2000 particles
having a total energy of 1000 units.
a.) Determine the values of N
0
, N
1
and N
2
that will result in the most probable macrostate
where N
i
is the number of particles with energy level i.
b.) Determine the entropy of the system for the conditions of part a.
c.) In words, indicate how the distribution of energy levels will be affected if the total
energy of the particles is increased.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-12 The partition function for rotation of a symmetric diatomic molecule, like N
2
, can be
represented as

( )
0
1
2 1
exp
2 2

=
+ | | + | |
= ~
| |
\ .
\ .

r
rot
j
r
j j T
j T
f
T T

where T
r
is a characteristic temperature which is a constant for each substance. T
r
=2.89
K for diatomic nitrogen gas. The approximation at the right of the above equation is
valid when T >>T
r.
. Assume that the partition function for diatomic nitrogen can be
represented by translational and rotational contributions at 300 K and 100 kPa (i.e., the
vibrational contributions are negligible).
a.) Prepare a plot of f
rot
versus the number of terms in the summation. How many terms
are needed in order for the approximation for f
rot
to be accurate?
b.) Derive analytical expressions for the specific heat and entropy of nitrogen gas based
on principles of statistical thermodynamics.
c.) Compare the results of the expressions with the accepted values.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-13 The sun can be considered a sphere of diameter 1.4e9 m with a equivalent blackbody
surface temperature of 5780 K. As you know, radiation has both particle and wave-like
behavior. The particle-like behavior is exhibited by the pressure exerted on a surface that
reflects the radiation. It has been proposed that this radiation pressure could be harnessed
to propel a vehicle for space travel. This option is explored in this problem. Consider a
vehicle having a sail with an effective area of 20 m
2
coated with an aluminized film that
has a reflectivity of 0.90. Assume that the sail is always oriented perpendicular to the
sun. The vehicle has a mass of 184 kg. The vehicle is initially located (at zero velocity)
just outside of earths atmosphere at a distance of 1.5E11 meters from the sun. The solar
wind will be harnessed to propel the vehicle towards Mars which is 142 million miles
distant from the Sun.
a.) Estimate the solar radiation per unit area incident on the sail at the earth-sun distance
(1.5E11 m). This is the so-called solar constant for earth.
b.) Calculate the force per unit area exerted on the sail when the vehicle is located at the
earth-sun distance.
c.) Estimate the solar constant for Mars
d.) Calculate the force per unit area exerted on the sail when the vehicle is located just
outside of the Mars atmosphere
e.) Calculate the distance traveled by the vehicle in 10 years (ignoring relativistic
effects). What is the vehicle velocity at this time?
f.) Calculate the time required for the vehicle to travel to Mars


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-14 A system consists of 15 particles that can occupy energy levels 0, and 3. The total
energy of the system is 10 and the degeneracy of each energy level is equal to (energy
level/ +1). (The degeneracy for the 0 energy level is 1.) Calculate the total number of
macrostates and microstates for this system if: a.) the particles are distinguishable and b.)
the particles are indistinguishable. For each case:
a.) Identify the most likely macrostate for each case.
b.) How are the results changed if there is no degeneracy in the energy levels?
c.) What happens to the number of microstates as the energy of the system is increased,
all else being the same?
d.). What happens to the number of microstates as the spacing between energy levels
increases with the total energy remaining the same? Provide an explanation for your
observations.


S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-15 Assuming that, , the number of possible combinations of particle energies in a
macrostate is
#
!
i
N levels
i
i i
g
N



it is shown in Section 15.4 that the most probable distribution of energy levels is the
Maxwell-Boltzmann distribution, exp
i i i
N B g . Derive the corresponding
relationship for N
i
using the Fermi-Dirac model defined by

# levels
1
!
! !
i
FD
i i i i
g
g N N

S.A. Klein and G.F. Nellis
Cambridge University Press, 2011
15-16 In order to establish a simple algebraic relation for the thermodynamic probability, we
assumed that the degeneracy of an energy level is much greater than the number of
particles in that energy level. Prove that this is true for Argon gas at 1 atm and 300 K.



S.A. Klein and G.F. Nellis
Cambridge University Press, 2011