Energy and Entropy Homework 4

Due Friday 4/26

Problem 4.1 Entropy change (quiz) For the following processes, in which the system
is designated in italics:
Is the change in entropy of the system positive, negative, zero or impossible to deter-
mine?
Is the change of entropy of the surroundings positive, negative, zero, or impossible to
determine?
Is the change in entropy of system plus surroundings posistive, negative, zero, or im-
possible to determine?
For each question, give a brief explanation. Answers without explanation will not receive
credit.
a) A hot potato is left on the counter top.
b) A sealed steel piston of air is slowly compressed.
Problem 4.2 Internal energy change (quiz) For the following processes, in which the
system is designated in italics, is the change in the internal energy of the system positive,
negative, zero or impossible to determine? Give a brief explanation. Answers without
explanation will not receive credit.
a) A hot potato is left on the counter top.
b) A sealed steel piston of air is slowly compressed.
c) A sealed, insulated piston of air is slowly compressed.
Problem 4.3 A non-ideal gas The equation of state of a gas that departs from ideality
can be approximated by
p =
NkT
V
_
1 +
NB
2
(T)
V
_
where B
2
(T) is called the second virial coecient which increases monotonically with tem-
perature. Find
_
U
V
_
T
and determine its sign.
Physics 423 1 Friday 4/26/2013
Solution to problem 4.3 A non-ideal gas We are given the pressure, so we should rst
ask ourselves what we know about the pressure. We know that
dU = TdS pdV (10.19)
and therefore
p =
_
U
V
_
S
(10.20)
Unfortunately, we are asked about
_
U
V
_
T
, which is something quite dierent. We could also
consider the Helmholtz free energy, which gives a second denition of pressure:
F = U TS (10.21)
dF = SdT pdV (10.22)
p =
_
F
V
_
T
(10.23)
=
_
U
V
_
T
+ T
_
S
V
_
T
(10.24)
_
U
V
_
T
= T
_
S
V
_
T
p (10.25)
This would be great, if we could only nd this particular derivative of the entropy. Fortu-
nately, when we examine the total dierential of the Helmholtz free energy, we can see that
this particular derivative of the entropy is part of a Maxwell relation!
_
S
V
_
T
=
_

_
F
T
_
V
V
_
T
(10.26)
=
_

_
F
V
_
T
T
_
V
(10.27)
=
_
p
T
_
V
(10.28)
=
Nk
V
_
1 +
NB
2
(T)
V
_
+
N
2
kT
V
2
dB
2
dT
(10.29)
=
p
T
+
N
2
kT
V
2
dB
2
dT
(10.30)
(10.31)
Putting these together, we nd that
_
U
V
_
T
= T
_
S
V
_
T
p (10.32)
Physics 423 2 Friday 4/26/2013
= T
_
p
T
+
N
2
kT
V
2
dB
2
dT
_
p (10.33)
=
N
2
kT
2
V
2
dB
2
dT
(10.34)
Since we are told that B
2
(T) is a monotonically increasing function, its slope is always
positive, and the internal energy increases as we increase the volume at xed temperature.
i.e.
_
U
V
_
T
0 (10.35)
Problem 4.4 Nucleus in magnetic eld Nuclei of a particular isotope species contained
in a crystal have spin I = 1, and thus, m = {+1, 0, 1}. The interaction between the nuclear
quadrupole moment and the gradient of the crystalline electric eld produces a situation
where the nucleous has the same energy, E = , in the state m = +1 and the state m = 1,
compared with an energy E = 0 in the state m = 0, i.e. each nucleus can be in one of 3
states, two of which have energy E = and one has energy E = 0.
a) Find the Helmholtz free energy F = U TS for a crystal containing N nuclei which
do not interact with each other.
b) Find an expression for the entropy as a function of temperature for this system. (Hint:
use results of part a.)
c) Indicate what your results predict for the entropy at the extremes of very high tem-
perature and very low temperature.
Solution to problem 4.4 Nucleus in magnetic eld
a) We can nd the free energy for a single spin from
F
1
= k
B
T ln Z (10.36)
= k
B
T ln
_
1 + 2e

_
(10.37)
Since we have N nuclei and the free energy is extensive,
F = Nk
B
T ln
_
1 + 2e

_
(10.38)
b) We can nd the entropy from
dF = SdT pdV (10.39)
S =
_
F
T
_
V
(10.40)
Physics 423 3 Friday 4/26/2013
= Nk
B
ln
_
1 + 2e

_
+ Nk
B
T
2e
d
dT
1 + 2e

(10.41)
= Nk
B
ln
_
1 + 2e

_
+ Nk
B
T
2e
1
k
B
T
2
1 + 2e

(10.42)
S = Nk
B
ln
_
1 + 2e

_
+ N

T
2e

1 + 2e

(10.43)
c) At low temperatures 1, and we nd the entropy is:
S Nk
B
2e

+ 2N

T
e

(10.44)
= 2N
_
k
B
+

T
_
e

(10.45)
This is very small, since e

is way tinier than /T is huge.

At high temperatures 1, which means we can Taylor expand the exponentials:
S Nk
B
ln(1 + 2(1 )) + 2N

T
1
1 2 + 2
(10.46)
= Nk
B
ln(3 2) 2Nk
B

1
1 2
(10.47)
Nk
B
ln 3 + Nk
B
ln
_
1
2
3

_
2Nk
B
(10.48)
Nk
B
ln 3
8
3
Nk
B
(10.49)
So at high temperatures, the entropy approaches k
B
ln 3 per nuclei, as we should expect.
It is also interesting to note that the entropy is always less than this value.
Problem 4.5 A rubber band model Consider a model in which rubber is composed of
segments of xed length a, each of which can be oriented in any of the six cardinal directions
( x, y or z). We will assume that the rubber band is aligned in the x direction, and
there is an energetic penalty for segments to be in any of the y or z directions, but that
there is no interaction involving the orientations of neighboring segments.
1
E
x
= 0 (10.50)
E
x
= 0 (10.51)
E
anything else
= (10.52)
a) Using these energies, nd the probability for each alignment using the Boltzmann factor
and their energies.
1
This model is actually considerably more accurate (taking = 0) for long linear polymers such as DNA
in solution.
Physics 423 4 Friday 4/26/2013
b) Find the mean displacement in the x direction of a molecule composed of N segments
based on the above probabilities. Why does it have this value?
c) If we pull on the molecule with tension in the + x direction, we will need to adjust
the Boltzmann factors to include terms such as a. You should do this by adjusting
your probabilities according to the following formulas, which account for the fact that
some states have dierent displacements than others.
P
i
=
e
(E
i
r
i
x)
Z
(10.53)
Z =

i
e
(E
i
r
i
x)
(10.54)
where r
i
is the displacement of state i. Work out the probabilities under tension .
d) What is the mean displacement in the x direction L of a molecule composed of N
segments under tension ?
e) What is the entropy S of this system, as a function of and ? Keep in mind that
the entropy is given by
S = k
B
all states

i
P
i
ln P
i
f) What is the internal energy U of this system, as a function of and ?
g) What is the Helmholtz free energy of this system, F U TS?
Solution to problem 4.5 A rubber band model
a)
P
x
= P
x
=
1
Z
(10.55)
P
anything else
=
e

Z
(10.56)
Z = 2 + 4e

(10.57)
Here I use the fact that there are four states with energy and two with energy 0.
b) To nd the mean displacement of of the molecule, we rst need to nd the mean
displacement of a particular segment of the molecule, and then multiply by N. Thats
easy enough to calculate, as there are only two states that have non-zero displacements:
x =

i
P
i
x
i
(10.58)
Since the probabilities of being oriented right and left are the same, the mean displace-
ment is zero.
Physics 423 5 Friday 4/26/2013
c) When we pull on the molecule we get
P
x
=
e
a
Z
(10.59)
P
anything else
=
e

Z
(10.60)
Z = e
a
+ e
a
+ 4e

(10.61)
where Ive just substituted a for 0 in the Boltzmann factors where there is a
dierence in the displacement in the x direction.
d) To nd the mean displacenment we use the same formula as before, but the symmetry
is now broken. The mean displacement of a single link is:
x =

i
P
i
x
i
(10.62)
= a
e
a
e
a
Z
(10.63)
L = Na
e
a
e
a
e
a
+ e
a
+ 4e

(10.64)
Where Ive used the fact that the total displacement L is just N times the mean
displacement of a single segment.
e) Because there is no interaction between segments, the entropy per segment is given by
S
N
= k
B
all states

i
P
i
ln P
i
(10.65)
= k
B

i
P
i
ln
_
e
h
i
Z
_
(10.66)
= k
B

i
P
i
_
ln
_
e
h
i
_
ln Z
_
(10.67)
= k
B

i
P
i
(h
i
ln Z) (10.68)
= k
B

i
P
i
(h
i
+ ln Z) (10.69)
= k
B
_
ln Z +

i
h
i
P
i
_
(10.70)
= k
B
ln Z +
1
T

i
h
i
P
i
(10.71)
= k
B
ln Z +
1
ZT
_
ae
a
ae
a
+ 4e

_
(10.72)
Physics 423 6 Friday 4/26/2013
= k
B
ln Z +
1
T
ae
a
ae
a
+ 4e

e
a
+ e
a
+ 4e

(10.73)
To nd the total entropy, we just multiply by N, which is all right because entropy is
extensive and there is no interaction between segments in this model so they can be
treated independently.
f) To nd the internal energy is quite simple. Again, we will start by computing the
internal energy per segment, which is computed in a manner analogous to how we
found the total displacement. The one tricky thing here is that the internal energy
does not contain the terms, because that describes the work done by (or on) the
external environment.
E =

i
E
i
P
i
(10.74)
= 4
e

Z
(10.75)
U = 4N
e

e
a
+ e
a
+ 4e

(10.76)
Note that the internal energy does depend on the external tension !
g) The Helmholtz free energy is just
F = U TS (10.77)
= N
e

e
a
+ e
a
+ 4e

NT
_
k
B
ln Z +
1
T
ae
a
ae
a
+ 4e

e
a
+ e
a
+ 4e

_
(10.78)
=
Ne

e
a
+ e
a
+ 4e

Nk
B
T ln Z N
ae
a
ae
a
+ 4e

e
a
+ e
a
+ 4e

(10.79)
= Nk
B
T ln Z Na
e
a
e
a
e
a
+ e
a
+ 4e

(10.80)
(10.81)
Physics 423 7 Friday 4/26/2013