Chem 521 Statistical Mechanics

Fall 2014
Homework
1. This le is a list of suggested problems for the entire course.
2. I will periodically update this list.
3. A subset of these problems will be assigned as homework, please make sure you check the
most up to date version of the le for assigned homework. 4. Assignments are due at noon
on Fridays, unless otherwise stated. You can drop them in the box in front of my oce room
248, chem 73 building.
5. Some of these problems may be used in the rst midterm and the nal exam. As
such I strongly encourage you to also try to solve problems that have not been assigned as
homework.
6. I will only provide solutions for the problems that are assigned. Feel free to stop by the
oce hours to ask questions about the rest of them.
7. If you notice a typo or a mistake, please let me know.
1. Reif 1.9
2. Reif 1.10
3. Reif 1.13
4. Reif 1.16
5. Reif 1.17
6. Reif 1.22
7. Reif 1.23
8. Reif 1.29 hint:
_

0
sin x
2
x
2
dx =

2
9. Evaluation of the integral
_

0
e
x
x
n
dx:
(a) Show that
_

0
e
x
x
n
dx = n
_

0
e
x
x
n1
dx = n!
(b) Dene: (n) =
_

0
e
x
x
n1
dx = (n 1)! , show that (1) = 1 and (
1
2
) =

(Hint: use x = y
2
and use the Gaussian integral)
10. Using a programing language of your choice, for N=10,100 and p =
1
2
,
1
3
,
2
3
;
(a) Generate a number N

of trajectories, calculate m for those trajectories and gen-

erate a histogram of P
N
(m)
(b) Discuss the accuracy of P
N
(m) as you increase N

and N.
(c) Fit the data to a Gaussian function f(m) = ae
(x)
2
/2
2
. Calculate and as
a function of N

. How does this compare with your expectation of these values

based on the probability p?
11. Repeat the problem above with N = 100 and p =
1
2
0,
1
2
00. Does a Gaussian t still
work? What about a Poisson function?
12. Assume that the probability density of a process is given by a Gaussian function
(x)dx e
(x)
2
/2
2
dx.
(a) Show that < x >= and
_
< (x )
2
> = . Make sure that you start with a
normalized probability function.
(b) In a random walk, = N(p q)l and = 2

Npql, where N is the number of

steps, p is the probability of moving forward and q = 1 p. Using a program of
your choice (Matlab, Wolfram, Maple) plot this function for a p >
1
2
and three
dierent N values. Space N in a logarithmic fashion (e.g. 1000, 10000, 100000)
to visualize the evolution of the function. Try this with p =
1
2
13. Consider a container that can be divided by an imaginary partition into two parts
with volumes V
1
and V
2
, respectively. There are N molecules in the gas state in the
container.
(a) On average how many molecules are there in partition 1? How many are there in
partition 2?
(b) What is the probability that N
1
of the molecules are in partition 1 and N
2
=
N N
1
are in partition 2?
(c) Using Stirlings formula to derive an expression for the probability above when
V
2
V
1
and N
2
N
1
. Assume that N
2
1 but do not make the same
assumption about N
1
. Let both N
2
and V
2
approach innity in such a way that
their ratio approaches a limiting value equal to n. (Credit: Liu)
14. Reif 2.1
15. Reif 2.2
16. Reif 2.4
17. Reif 2.5
18. Reif 2.6
19. Reif 2.7
20. (a) A classical particle is free to move in one dimension in a box with walls located at
x = 0 and x = L and has a known energy that lie between E and E +E. Draw
the classical phase space of the particle, indicating regions of the space that is
available to the particle. What is the probability that the particle is found within
a distance L
0
from x = 0? (L
0
< L)
(b) Consider the same box now with two weakly interacting particles, each of mass
m and free to move in one dimension. Denote the respective position coordinates
of the two particles by x
1
and x
2
and their respective momenta by p
1
and p
2
. The
total energy of the system lie between E and E + E. The phase space of this
system is a four-dimensional one. Plot three projections of this phase space. The
one involving x
1
and x
2
, the one involving p
1
and p
2
and a last one involving x
1
and p
1
. Indicates in each regions accessible to the system. What is the probability
that a single particle lie within a distance L
0
from x = 0? What is the probability
of nding both particles in that space?
(c) Solve part (a) for a quantum mechanical particle with an energy that lie on one
of the eigenvalues of the system E
n
. What is the answer for the limit of really
large n?
21. Reif 3.2
22. Reif 3.5
23. Reif 3.6
24. Reif 4.3
25. Consider an ideal gas of N noninteracting particles in d dimensions (d is an arbitrary
positive integer) contained in a (hyper) volume V . From the partition function, cal-
culate F (free energy), P, S, E (energy), and = C
p
/C
v
and notice which quantities
depend on d. Numerical factors in the partition function are unimportant. (Credit:
Kamien)
26. A system with temperature-independent heat capacity C is initially at temperature T
1
and a system with temperature-independent heat capacity 2C is initially at tempera-
ture T
2
, where T
2
< T
1
.
(a) The systems are placed in thermal contact and exchange heat until they are in
thermal equilibrium. What is the nal temperature of those two bodies?
(b) A heat engine is run in innitesimal cycles between the two bodies leading to
a slow reversible approach to a nal common temperature. What is the nal
temperature?
(c) How much work is extracted in this process? (credit: Liu)
27. For a pure substance in an external magnetic eld H the Helmholtz free energy can
be written as
dF = SdT PdV V MdH
In most practical cases where the substance is liquid or solid the term PdV is negligi-
ble because the substance is highly incompressible. We may dene the two heat capaci-
ties, one at constant eld and the other at constant magnetization M as C
H
= T
_
S
T
_
H
and C
M
= T
_
S
T
_
M
show that (credit: Liu)
C
H
C
M
= TV
_
M
T
_
H
_
H
T
_
M
28. The work done on a rubber band when it is stretched can be written as dL were is
the tension and L is the length of the rubber band.
(a) Neglecting PV terms, setup an expression for dE for a rubber band. Bt a legendre
transformation obtain an expression for dF where F is the Helmholtz free energy.
(b) Derive two Maxwell relation from the above equations.
(c) Experiments show that a rubber band heats up when it is stretched adiabatically.
From this fact determine whether a rubber band will contract or expand when it is
cooled at constant tension. (Hint: Use considerations of thermal and mechanical
stability to show that certain thermodynamic derivatives are positive.) (credit:
Liu)
29. Chandler 1.16
30. Chandler 1.17
31. When a particle with spin 1/2 is in a magnetic eld H, it has two energy levels H.
Consider a system of N such particles in a magnetic eld H. Assume that a fraction
x of particles are in the spin up ( = H ) state.
(a) What is the total number of available states of the system?
(b) What is the entropy of the system? Plot the entropy as a function of x.
(c) Calculate the averate temperature T as a function of x. Plot the temperature as
a function of x. Explain your results.
(d) Using these results calculate average magnetization M per spin, for the system as
a function of H and T. Sketch your result as a function of T for xed H. Sketch
your results as a function of H for constant T. Discuss the results. (credit: Liu)
32. Reif 5.1
33. Reif 5.2
34. Reif 5.4
35. Reif 5.6
36. Reif 5.7
37. Reif 5.15
38. Reif 5.19
39. Reif 5.20
40. Reif 5.23
41. Reif 5.26
42. The Stirling Engine: An Stirling engine toy as shown in the gure is placed on a coee
mug that contains 1/4 liters of boiling water. Assume that the mugs opening is 10cm
in diameter and the mug is well insulated. (The only heat loss is through contact with
the engine.)
http://www.howstuffworks.com/stirling-engine.htm
(a) Explain why a full cycle of the Strilings engine can be described by the following
cycle:
http://en.wikipedia.org/wiki/Stirling_engine
(b) Calculate the work done in one cycle of the engine and show that it is equal to
W = nRln
V
1
V
2
(T
H
T
C
).
Where V
1
and V
2
are the initial and nal volumes of the engine, and T
H
and T
C
are the temperatures of the hot and the cold surfaces of the engine.
(c) Calculate the head lost in the heat reservoir (the mug) and the temperature change
in the mug as a result.
(d) Using realistic values calculate the eciency of this engine in one cycle.
(e) One cycle of this engine takes time T to complete (period). Assuming that the
engine has negligible friction, it is safe to assume that the period remains constant.
After an elapsed time t T the temperature of the water in the mug has changed
to T

H
. Show that
T

H
= C exp
__
nRln
V
1
V
2
C
V
(Water)
+ C
V
(gas)
_
t
_
+
C
V
T
C
C
V
(gas)nRln
V
1
V
2
In this equation C is a constant. Hint: To show this assume innitesimal changes
in the heat, and nd a dierential equation based on the derivative of the tem-
perature as a function of time.
(f) Based on reasonable assumption about the initial and nal temperatures of water,
nd the total number of cycles that the engine will rotate before stopping.
(g) What is the eciency of one cycle at some intermediate temperature T

H
?
(h) What is the total eciency of the engine after it stops?
43. Reif 6.1
44. Reif 6.2
45. Reif 6.3
46. Reif 6.6
47. Reif 6.10
48. Reif 6.11
49. Reif 6.13
50. Suppose N atoms are arranged regularly to form a perfect crystal. If one moves n
atoms among them, where 1 n N, from lattice sites to interstitial sites one forms
n defects called Frenkel defects. Suppose there are N

interstitial sites an atom can

enter. Let w be the energy necessary to remove an atom from a lattice site to an
interstitial site. Consider the system held at temperature T such that w k
B
T.
(a) Construct the canonical partition function in terms of a sum over n. (Hint: Start
from calculating the degeneracy)
(b) What is the average number of defects at this temperature? (credit: Liu)
51. A simple one dimensional quantum oscillator has energy levels given by
E
n
=
_
n +
1
2
_

where is the characteristic frequency of the oscillator and the quantum number n
has possible integral values n = 1, 2, ...
(a) Derive an expression for the canonical partition function of a single quantum
oscillator.
(b) Using the results of part a, nd the average energy E for the system of N oscilla-
tors. Plot as E/(N) as function of k
B
T/(). This is known as Planck result
for the thermal average energy of photons in a single mode of frequency .
(c) Find the Helmholts free energy, specic heat and entropy of the N oscillator
system. Plot F/(N), C/(Nk
B
) and S/(Nk
B
) as a function of k
B
T/(). What
is the high-temperature limit of the heat capacity? (credit: Liu)
52. Reif 7.1
53. Reif 7.3
54. Reif 7.5
55. Reif 7.6
56. Reif 7.10
57. The rotational energy levels of a diatomic molecule are given by E
j
= j(j + 1) where
j is a non negative integer. The degeneracy of each rotational level is 2j +1. Consider
N diatomic molecules at temperature T.
(a) Write the canonical partition function Z for the rotational states of one molecule
in terms of a sum over the quantum number j.
(b) Evaluate Z approximately for high temperature by converting the sum to an
integral.
(c) Evaluate Z approximately for low temperature by truncating the sum after the
second term.
(d) Find expressions for the energy E and the specic heat C in both limits. Sketch
the behavior of E/Nk
B
T and C/Nk
B
T as a function of /k
B
T. (credit:Liu)
58. In the grand canonical ensemble, with boundary conditions of (V, , ) (constant vol-
ume, constant temperature and constant average number of particles) the probability
of nding a particle in the state N, j, where N is the number of particles and j is the
state of energy the assembly of particles are taking is given by
P
N,j
(V, , ) =
e
E
N,j
e
N

j
e
E
N,j
e
N
where the sum is over all possible number of particles and all possible states of energy
and = where is the chemical potential. Using this probability function show
that
(a) E(V, , ) =
_
ln Z
G

_
V,
(b) P(V, , ) =
1

_
ln Z
G
V
_
,
(c) N(V, , ) =
_
ln Z
G

_
V,
=
1

_
ln Z
G

_
V,
where Z
G
=

j
e
E
N,j
e
N
is the grand canonical partition function.
59. consider the function f = ln Z
G
, based on the ndings of previous question,
(a) Show that df = Ed Nd + PdV .
(b) Using the relationship between the extensive and intensive variables, write the
derivative of a new function dA such that A = A(E, V, N). What is this function?
(c) Show that the entropy of a grand canonical ensemble, under the condition of
constant (V, T, ) is given by S = k
B
(ln Z
G
+ E N). Compare you answer
with the entropy obtained for the canonical ensemble.
(d) Calculate the Helmholtz free energy based on the partition function of a grand
canonical ensemble.
60. The Gibbs free energy is dened as G(P, T, N) = E + pV TS. Show that G = N
and therefore pV = k
B
T ln Z
G
. Note that in the Gibbs free energy for a system with
constant number of particles N is a function of p and T.
61. (E, V, N) is the density of states with energy E in a container of volume V and number
of particles N. Entropy can be dened as S = k
B
ln (E, V, N) in micro-canonical en-
semble. We showed how minimizing the Helmholtz free energy F(, V, N) = k
B
ln Z
where Z =

E
(E, V, N)e
E
is identical to maximizing entropy, if one assumes the
function (E, V, N)e
E
is only non-zero close to its maximum. Similarly we calculated
the Helmholtz free energy F(, V, ) through another Lagrange multiplier that relates
the chemical potential to the average number of particles and showed =
F
N
. Use
similar methods to dene the ishothermal-isobaric partition function = (N, T, P)
such that G(N, P, T) = k
B
ln . Show that the new multiplier is in the form of
p
k
B
T
where p is the average pressure.
62. Obtain the pressure of a classical ideal gas as a function of N, V and T using the
grand canonical partition function.
63. Reif 8.12
64. Reif 8.13
65. Reif 8.14
66. Reif 8.15
67. Reif 8.16
68. Reif 8.19
69. When water containing a small amount of surfactant is placed in contact with air, the
surfactant molecules adsorb to the air-water interface, forming a Langmuir monolayer.
To a good approximation the surfactant solution is an ideal gas of noninteracting
surfactant molecules. The following system is a simple model of Langmuir trough at
submonolayer coverage. Consider an adsorbent surface of N sites, each of which can
adsorb one surfactant molecule. Suppose that the surface is in contact with an ideal
gas of surfactants with chemical potential . Assuming that an adsorbed molecule has
energy
0
compared to one in the free state, determine the covering ration (the ratio
of adsorbed molecules to adsorbing sites). use the grand canonical ensemble. (Credit:
Liu)
70. Consider a gas of hydrogen molecules, enclosed in a box of volume V and in thermal
equilibrium with a heat reservoir at temperature T.
(a) Calculate the partition function for the gas, assuming ideal gas conditions.
(b) What is the probability that the rotational quantum number is J at temperature
T?
(c) What is the most probable value for J at 300K and 1000K?
(d) What is the probability that the vibrational quantum number is n at temperature
T?
(e) What is the most probable value for n at 300K and 1000K?
(f) Using the results of the above calculations, calculate the dissociation rate constant
for hydrogen molecule H
2
.
(g) At 1000K what percent of the molecules are dissociated compared to room tem-
perature?
(h) What is the percentage of dissociated molecules at 10000K?
(i) Compare your results from part 70h with the percentage of hydrogen atoms that
are dissociated at this temperature into an electron and a proton.
Note that the bond dissociation energy of hydrogen molecule is about 100Kcal/mol.
The dissociation energy for electron in a hydrogen molecule is given by
0
=
e
2
2a
0
where a
0
is the Bohr radius.
(j) Calculate the dissociation rate constant for the molecule HD.
(k) Calculate the rotational contribution to the entropy of HD at 20K and 300K
71. Show that the entropy of an ideal gas in thermal equilibrium is given by the formula
S = K
B

[n

+ 1 ln n

+ 1 n

ln n

]
in the case of bosons and by the formula
S = K
B

[n

1 ln n

1 +n

ln n

]
in the case of fermions. (The sum is over all allowed energy levels .) Verify that these
results are consistent with the general formula
S = K
B

n
P

(n) ln P

(n)
_
where P

(n) is the probability that there are exactly n particles in the energy state
(credit: Kamien)
72. Reif 9.1
73. Reif 9.4
74. Reif 9.7
75. Reif 9.17
76. Reif 9.23