Homework #8 Solutions

Question 1) K+K, Chapter 5, Problem 6 Gibbs sum for a 2-level system

has the following list of states:
1) Un-occupied N = 0; = 0
2) Occupied with energy 0; N = 1, = 0
3) Occupied with energy ; N = 1, =
a) The Gibbs sum can be written explicitely using the above list of all states.
Z
g
(T, ) =

X
N=0
X
S(N)
e
(N
s
)/
(1)
= e
(00)/
+e
(10)
+e
(1)/
(2)
= 1 + + e
/
(3)
where we have dened e
/
and Z
g
denotes the grand canonical partition
function.
b) Find the thermal average occupancy.
< N > =
d
d
log Z
g
(4)
=
1
Z
g
d
d
Z
g
(5)
=
+ e
/
Z
g
(T, )
(6)
c) Average thermal occupancy of state of energy .
P(1, ) =
e
/
Z
g
This is the probability of occupancy of the state with N = 1 and energy .
d)The thermal average of the system is given by a weighted sum of energies
and corresponding probabilities of occupation. In this case there is only one
term
U =
e
/
Z
g
e) Now suppose that there can be an N = 2 state in which energy levels 0
and can be occupied simultaneously. This will add an N = 2 term to the sum:
e
(2(0+))/
=
2
e
/
And the total Gibbs function becomes
Z
g
= 1 + + e
/
+
2
e
/
1
Question 2) K+K, Chapter 5, Problem 7 As usual we start by forming the
partition function.
Z
g
=
2
X
N=0
X

s
(N)
e
(N
s
)/
(7)
= e
(0+/2)
+e
(+/2)/
+e
(/2)/
+e
(2/2)/
(8)
= e
/2
+ 2e
/
cosh

+e
(2/2)/
(9)
We can use eq(5) for < N >.
Z
g
= e
/2
+ 2cosh

+
2
e
/2
(10)
Z
g

= 2 cosh

+ 2e
/2
(11)
< N > =
1
Z
g

2 cosh

+ 2e
/2

(12)
Now enforce < N >= 1. Using the explicit form of Z
g
we get
Z
g
= 2cosh

+ 2
2
e
/2
= e
/2
+ 2cosh

+
2
e
/2
(13)

2
e
/2
= e
/2
(14)

2
= e
/
(15)
Since = e
/
we get = /2 .
Question 3a) K+K, Chapter 5, Problem 8 First consider the case with O
2
only. In this case this is a two state system. The heme site can be occupied or
unoccupied. The Gibbs sum has only two terms:
Z
g
= 1 +e
(
A
)/
= 1 + e

A
/
(16)
We want to nd
A
such that < N >= 0.9N. Again using eq(5):
< N > =

log Z
g
=

Z
g
e

A
/
(17)
=
e

A
/
1 + e

A
/
=
1
1 +
1
e

A
/
= 0.9 (18)
Note that in the last equality we used 0.9 instead of 0.9N. The reason for this is
the following. Z
g
we used above is that for a single site (for N sites there would
be more than 2 states). We are assuming that the heme sites are distinguishable
and independent. Hence the average occupancy of N sites is just N times that
of one site.
2
Now solve for
A
to get:

A
= log

(19)
= 1.38 10
23
J
K
(273.16 + 37)K log

10
5
9

(20)
= 5.87 10
20
J = 0.37eV (21)
This is the bonding energy of O
2
on Hb.
b) Now allow CO as well. The Gibbs sum now has 3 terms. The heme site
can be un-occupied, occupied by O
2
or occupied by CO.
Z
g
= 1 +
O
2
e

A
/
+
CO
e

B
/
(22)
We are looking for the condition on
B
such that only 10% of the heme sites
are occupied by O
2
.
< N
O
2
> =

O
2
e

A
/
Z
g
=

O
2
e

A
/
1 +
O
2
e

A
/
+
CO
e

B
/
= 0.1 (23)
Again it is to be understood that this calculation is done for one heme site.
Solving this for
B
we get:

B
= log

9
O
2
e

A
/
1

CO

= 0.548 eV =
B
(24)
Discussion: An alternative method: N sites rather than one site
If we study the system with N sites for part a), the partition function will
be:
Z =
l=N
X
l=0
X
s

l
e
l
A
/
(25)
=
l=N
X
l=0
N!
l!(N l)!
(e

A
/
)
l
(26)
= (e

A
/
+ 1)
N
(27)
Then, we can use the formula for average < N >:
< N >=
1
Z
Z

= 0.9N (28)
The same method for part (b), but the math will be more complicated.
3
Question 4a) K+K, Chapter 5, Problem 10
< N > =

Z
g
Z
g

,V
(29)
Z
g
=
X
N
X

s
(N)
e
(N
s
)/
(30)

Z
g

=
X
N
X

s
(N)
Ne
(N
s
)/
(31)

2
Z
g

2
=
X
N
X

s
(N)
N
2
e
(N
s
)/
(32)
< N
2
> =
P
N
P

s
(N)
N
2
e
(N
s
)/
Z
g
=

2
Z
g

2
Z
g

2
(33)
b) Consider
< N >

P
ASN
Ne
(N
s
)/
Z
g
(34)
=

Z
g

P
ASN
Ne
(N
s
)/
Z
2
g
+
1
Z
g

X
ASN
N
2
e
(N
s
)/
(35)

< N >

Z
g

2
Z
2
g
+

2
Z
g

2
Z
g

2
=< (N)
2
> (from above) (36)
Question 5) K+K, Chapter 5, Problem 12 Ascent of sap in trees.
Assume the water is in diusive equilibrium in the tree. The vapor at the
base has a chemical potential given by that of the ideal gas
= log(n/n
Q
)
n = n
0
at the pool.

pool
= log(n
o
/n
Q
) (internal chem. pot. of water at the base)
The external chemical potential due to gravity is Mgh, where M is the mass of
the water molecule, and h is the height of the tree.
At the top of the tree, the total chemical potential of the water molecule is

top
= log(rn
0
/n
Q
) +Mgh
where r is the relative humidity at the top of the tree.
In diusive equilibrium, is uniform in the tree, so:

pool
=
top
(37)
log(n
o
/n
Q
) = log(rn
o
/n
Q
) +Mgh (38)
4
Solve for the maximum height of the tree
h =
1
Mg
log

n
0
/n
Q
rn
0
/n
Q

=

Mg
log(r) = h (39)
For the mass of the water molecule we will use M = 18 amu = 18 1, 66
10
27
kg (Back inside cover of K+K). r = 0.9 is given in the problem. If you
plug in everything in eq(39) you get
h = 1, 480 meters
That is one tall tree!
In practice trees rarely get over 100 meters in height, 110 meters is about
the maximum.
This is an over-estimate because the tree does not grow in water, and there
is often a temperature gradient between the roots and top. Other mechanical
limitations may come into play as trees grow taller.
Question 6) K+K Chapter 6, Problem 1 FD Distribution f() =
1
e
()/
+1
.

=
1
(e
()/
+ 1)
2
1

e
()/
Evaluate the derivative at the chemical potential:

( = ) =

1
e
0
(e
0
+ 1)
2
=
1
4
Question 7a) K+K Chapter 6, Problem 3 Suppose such a system is in
thermal and diusive contact with a reservoir at and . There are 3 distinct
states:
1) Un-occupied with energy 0
2) Single occupancy with energy .
3) Double occupancy with energy 2.
The Gibbs sum is calculated as follows:
Z
g
=
2
X
N=0
X

s
(N)
e
(N
s(N)
)/
(40)
= e
(00)/
+e
(1)/
+e
(22)/
(41)
= 1 + e
/
+
2
e
2/
(42)
We can calculate < N > by hand
< N > =
0 1 + 1 e
/
+ 2
2
e
2/
Z
g
(43)
=
e
/
(1 + 2e
/
)
1 + e
/
+
2
e
2/
(44)
5
b) Note that this is a dierent case than part a). Now there are a total of
4 states.
1) No occupancy, 0 energy
2) Single occupancy, energy
3) Single occupancy, energy
4) Double occupancy, 2 energy
In 2) and 3) only one of the degenerate states is occupied, the other one being
un-occupied. In 4) both degenerate states are occupied. Keeping this in mind
we can write down the partition function as:
Z
g
= e
(00)/
+e
()/
+e
()/
+e
(22)/
(45)
= (1 + e
/
)
2
(46)
Note that this is the product of two single-orbital Gibbs sums. Now calculate
< N > by hand
< N >=
0 1 + 2 (1 e
/
) + 2
2
e
2/
Z
g
(47)
Using eq(46) for Z
g
and after some math we obtain:
< N >=
2e
/
1 + e
/
=
2
e
()/
+ 1
(48)
A factor of 2 greater than the Fermi distribution function. This arises from the
double dgeneracy of the orbital.
Question8) K+K Chapter 6, Problem 5 For xed N the thermodynamic
identity reads :
d =
dU

+
PdV

(49)
Write
dU =
U

V
d +
U
V

dV
so
d =
U

V
d +
U
V

dV +
PdV

For the ideal gas we know that U = 3N/2, so

U

V
=
3
2
N (50)
U
V

= 0 (51)
(52)
Hence
d =
3N
2
d +
N
V
dV
6
Now integrate both sides

1
=
Z
d =
3N
2
Z
d

+N
Z
dV
V
=
3N
2
log() +N log(V ) (53)
Note that C
V
= 3N/2, so
= C
V
log() +N log(V ) +
1
where
1
is a constant independent of and V .
Question 9) K+K Chapter 6, Problem 6 Entropy of Mixing.
Initially the two systems have the same temperature and volume and are
made up of dierent species, but the same number of particles. Each has an
entropy given by the ideal gas value:

A
= N

log

n
QA
n

+
5
2

B
= N

log

n
QB
n

+
5
2

where n = N/V is the concentration of particles and n

Q
= (M/2h
2
)
3/2
are
the quantum concentration for particle A and B (they are dierent) . The
entropies are additive:

initial
=
A
+
B
= N

log

n
QA
n

+
5
2
+ log

n
QB
n

+
5
2

(54)
After they are placed in diusive contact and equilibrium is reached, we have the
same temperature , twice the volume 2V , and half the particle concentrations
n
A
N/2V and n
B
N/2V . The entropy after mixing can be obtained from
eq(54) by making these changes.

final
= N

log

n
QA
(n/2)

+
5
2
+ log

n
QB
(n/2)

+
5
2

The dierence is easily calculated using the property of logarithm: log(ab) =

log(a) + log(b):
=
final

initial
= 2N log(2) (55)
This is the change in entropy upon mixing.
Upon interdiusion the A atoms have more accessible states than before,
similarly for the B atoms (at the same temperature). This is the reason for the
increase in entropy.
In the case of identical atoms we dont observe any increase in entropy. In
this case the nal state has 2N particles in a volume 2V.Whats more,
QA
+
QB
7
Hence the concentration is the same as before mixing. The entropy is then given
by the standard formula

final
= 2N

log

n
Q
n

+
5
2

I want to emphasize this is not the sum of two terms (as is the case before
mixing for A = B or in the case of A 6= B before and after the mixing). It is
simply the entropy of a gas of 2N particles in volume 2V.
This result is expected since macroscopically inserting/removing a partition
in a box lled with a uniform gas does not change anything. This is called
the Gibbs Paradox. The resolution lies in the indistinguashibility of identical
particles. After mixing, the states per atom seems to have increased, but the
indistinguahibility prevents us from overcounting (recall the 1/N! factors), and
reduces the total amount of states to that of the case with two compartments.
Discussion : You can also use the formula as:
= N log V +cons
But you should pay attention to the constant here:
= N[log V + log
n
Q
N
+ 5/2]
cons = N[log
n
Q
N
+ 5/2]
which means the constant is also related with N, which will be useful in the
case A = B.
8