Physics 112 Thermodynamics

Physics 112: Thermodynamics
Served by Roger Grifth

Nutritional Facts:
Serving size: 1 Semester (16 weeks)
Servings per container: many problems and solutions
ofce hours for John Clarke Wed 3-4 349 Birge
Preamble for this course
Why do we need statistical mechanics?
Quantum Mechanics: Particle in a box, Harmonic oscillator, H-atom. The SE gives us our solutions.
||
2
gives us the probability of nding a particle somewhere with some speed. But this is not
statistics. But for a cm
3
of air ~ 3 10
19
molecules, this is a hopeless problem to solve the SE.
But for a macroscopic system we must use a statistical approach. e.g to nd the heat capacity or
paramagnetic susceptibility. Statistically this turns out to yield exceedingly accurate results.
Road Map
1. Dene states of the system, probability, binomial distribution, gaussian, and mean value theorem.
2. Entropy: The measure of the number of states that are accesible for a given system and energy. The
corner stone of the theory is that the system is equally likely to be in any one of these states.We
will call the number of given states g. They also introduce the entropy = lng. We will also talk
about systems in thermal contact. This will lead us into the second law of thermodynamic. The
temperature is dened as
1
=
_
u
_
N,V
where u is the internal energy.
3. The Boltzman factor: Imagine we have a small system in a hot bath, we nd that the probability that
it will be found in a given state is given by
p() e
/
4. The Planck Distribution:
5. Systems in both thermal and diffusive contact. This leads to a new concept called the chemical
potential. The chemical potential we call which is dened as
=
_
N
_
U,V
This leads us to something called the Gibbs factor. the probabilty of nding one particle having
some energy in some state
p(1, ) e
()/
1
6. Ideal classical gas
7. Quantum Gases: They come in two avors, Fermi gas and Bose gas. The Fermi gas is for fermions
and the Bose gas is for bosons. they have profoundly different behaviours.
8. Heat and Work: heat engines and refrigerators
2
Chapter 1
States of A Model System
1.1 Number Of States
1.1.0.1 Stationary Quantum State
The rst thing we must talk about is the multiplicity or also known as degeneracy, we will call this g of a
system with given energy which is equal to the number of quantum states with that energy . e.g Particle
in 3D box
n
x
n
y
n
z
1 1 1
1 1 2
1 2 1
2 1 1
the rst energy state is non degenerate g = 1 the second energy state is three-fold degenerate g = 3.
Quantum states of a one-particle are called orbitals. For Non interacting Spins
N=
the total number of arrangements is given by 2
N
, the total magnetic moment is given by M = Nm for all
spins that are and M =Nm for all spins that are . How many ways can we get M = (N2)m (ip
over any one spin). We will call g the number of ways in which we can get a particular value of a
magnetic moment. Lets dene the following
n
=
_
N
2
+s
_
n
=
_
N
2
s
_
where N is even and M = (n
)m = 2sm where the 2s = spin excess = n
. If we assume each
spin has a probability P
of being and a probability of P
of being . we also know that P
+P
= 1. In
the presence of a magnetic eld , P
> P
. The probability of a conguartion with spin excess 2s is

P
N/2+s
and P
N/2s
. The probability of nding a magnetic moment M = (2s)m is given by the following

P(N, s) = g(N, s)P
N/2+s
P
N/2s
we need to nd what the multiplicity g(N, s) is. In how many ways can we distribute n
= N/2+s spins
over N places. we can assume that they are distinguishable spins. So we can assume that the rst spin can
be on any one of the N sides.
3
1st spin can be in any one of the N sides
2nd spin can be in any one of the (N 1) sides
3rd spin can be in any one of the (N2) sides
4th spin can be in any one of the (N3) sides
nth spin can be in any one of (Nn
+1) sides
Thus the total number of the arrangements is
total = N(N 1)(N2)...(Nn
+1)(Nn
)
=
N!
(Nn
)!
We have to be careful of overcounting, we can address this in the following way. If we dont care about
the color of the spin or about which spin goes where, we have overcounted. The rst of these spins
1st of spin up could have been any one of the n
magnets
2nd of spin up could have been any one of the n
1 magnets
nth of spin up could have been any one of the 1 magnets
Thus we have overcounted by n
(n
1)(n
2)... 1 = n
!. Thus
g(N, s) =
N!
(Nn
)!n
!
This is known as the multiplicity function; it is the number of states having the same value s. If we
replace
n
=
N
2
+s
yields
g(N, s) =
N!
_
N
2
s
_
!
_
N
2
+s
_
!
This is the number of ways of achieving a spin excess of 2s. Hence
P(N, s) =
N!
_
N
2
s
_
!
_
N
2
+s
_
!
P
N/2+s
P
N/2s
For the moment lets assume that we dont apply any eld B = 0then P
= P
=
1
2
, thus we nd
P(N, s) =
N!
_
N
2
s
_
!
_
N
2
+s
_
!
1
2
N
If we have the following spins
N spins
the probability is given as
P(N, s) =
g(N, s)
2
N
2s = spin excess
where
g(N, s) =
N!
_
N
2
s
_
!
_
N
2
+s
_
!
4
1.2 Gaussian Distribution
we rst need to assume
N 1, N even |s| N P
= P
=
1
2
we will use ln as the natural logrythim, thus
lng(N, s) = lnN! ln
_
N
2
+s
_
! ln
_
N
2
s
_
!
working on this expression yields
_
N
2
+s
_
! =
_
1, 2, 3...
N
2
__
N
2
+1
_
, ...
_
N
2
+s
_
=
_
N
2
_
!
_
N
2
+1
_
, ...
_
N
2
+s
_
ln
_
N
2
+s
_
! = ln
_
N
2
_
! +
s
k=1
ln
_
N
2
+k
_
and now we need to do it for the other one
_
N
2
s
_
=
1, 2, 3, ..
_
N
2
s
__
N
2
s +1
_
, ...
N
2
N
2
....
_
N
2
s +1
_
=
_
N
2
_
!
N/2......
_
N
2
s +1
_
ln
_
N
2
s
_
! = ln
_
N
2
_
!0
s
k=1
ln
_
N
2
k +1
_
hence
ln
_
N
2
+s
_
! +ln
_
N
2
s
_
! = 2ln
_
N
2
_
! +
s
k=1
ln
_
1+
2k
N
1
2k
N
+
2
N
_
and since we know that s N and also k N, we can expand the expression
s
k=1
_
ln
_
1+
2k
N
_
ln
_
1
2k
N
+
2
N
__

s
k=1
_
2k
N

_
2k
N
+
2
N
__
4
N
s
k=1
_
k
1
2
_
when we add all these terms together and nd that there are s terms, thus the sum is given by
4
N
s
k=1
_
k
1
2
_
=
2s
2
N
putting this all together yields
lng(N, s) = lnN! 2ln
_
N
2
_
!
2s
2
N
5
thus
ln
_
g(N, s)
__
N
2
_
!
2
N!
_
=
2s
2
N
and
g(N, s) =
N!
_
N
2
_
!
_
N
2
_
!
e
2s
2
/N
and to summarize
g(N, s) = g(N, 0)e
2s
2
/N
where g(N, 0) =
N!
_
N
2
_
!
_
N
2
_
!
we also know that this function falls of as 1/e when
2s
2
N
= 1, s =
_
N
2
_
1/2
s
N
=
_
1
2N
_
1/2
thus, if N is very large, the peeking is exceedingly sharp. For large N, thermodynamic quantities (heat
capacity,paramagnetic susceptibility are very well dened. To take an example, lets assume that
N = 10
20
(1 cm
3
air)
s
N
10
11
How to evaluate N!? There is a useful approximation called Sterlings approximation, it is dened as
for large N N! (2N)
1/2
N
N
e
N
we need to work with this until we make it look like the multiplicity g(N, s)
lnN! = NlnNN +
1
2
ln(2N)
note that the error is less the 1% for N = 10 and it gets much better for higher N. Lets use this to evaluate
g(N, 0)
lng(N, 0) = ln
_
N!
_
N
2
_
!
_
N
2
_
!
_
= NlnN N+
1
2
ln(2N) 2
_
N
2
ln
N
2

N
2
+
1
2
ln(N)
_
let us do
lng(N, 0) = Nln2+
1
2
ln(2N)
1
2
ln(N)
2
= Nln2+
1
2
ln
_
2
N
_
or more compactly
lng(N, 0) = ln
_
2
N
_
2
N
_
1/2
_
and nally
g(N, 0) = 2
N
_
2
N
_
1/2
6
1.2.1 Notes on The Gaussian
g(x, ) = Ae
(x x)
2
/2
2
where
x = mean value
= 0 for P
= P
= 0 for P
= P
= standard deviation
where is used for error analysis, this is a method of expressing the condence in your results.
68.3%
2 98.4%
3 99.7%
1.3 The Central Limit Theorem
The Gaussian distribution holds for any distribution provided that three things are true
N is very large
P(x) falls off sufcently rapidly as x
Events are statistically independent
1.4 Mean Values
Suppose that function f (s) has a probability of P(s) of occuring. Then the mean value is
f =

f =
s
f (s)P(s) where

s
p(s) = 1
e.g, the toss of a die
n =
6
n=1
np(n) = (1+2+3+4+5+6)
1
6
= 3
1
2
Example: Spin system
for P
= P
(i.e equally likely for spins to be or )

thus
P(N, s) =
g(N, s)
2
N
and using the denition
f =

f =
s
f (s)
g(N, s)
2
N
7
if we let
f (s) = s
2
then
s
2
=s
2
but
s
2
=

s
s
2
2
N
_
2
N
_
1/2
e
2s
2
/N
1
2
N
=
_
2
N
_
1/2
Z

s
2
e
2s
2
/N
ds
if we let
x
2
=
2s
2
N
s =
_
N
2
_
1/2
x ds =
_
N
2
_
1/2
dx
and so we nd
s
2
=
_
2
N
_
1/2
N
2
_
N
2
_
1/2
Z

x
2
e
x
2
dx =
N
4
now lets calculate the spin excess
(2s)
2
= N mean square
(2s)
2
1/2
=
N root mean square

to nd the fractional rms spin excess
(2s)
2
N
=
1
N
1.5 Summary
1. Multiplicity for N spins 1/2 with spin excess 2s is given by
g(N, s) =
N!
_
N
2
+s
_
!
_
N
2
s
_
!
but for N 1, and s N we can write
g(N, .s) = g(N, 0)e
2s
2
/N
where
g(N, 0) =
N!
_
N
2
_
!
_
N
2
_
!
= 2
N
_
2
N
_
1/2
and using Sterlings approximation
lnN! = NlnNN +
1
2
ln(2N)
2. the Mean value
f =
s
f (s)P(s), where

s
P(s) = 1
and the spin system
(2s)
2
N
=
1
N
8
1.6 Problems and Solutions
Problem # 1
A penny is tossed 400 times. Use the Gaussian distribution to nd the probability of getting 215 heads.
A graphical representation of this is given as
Since we know that the Gaussian distribution is given as
g(N, s) =
_
2
N
_
1/2
2
N
e
2s
2
/N
And the probability is given as
P(N, s) =
g(N, s)
2
N
and since we know that
N = 400 s = x x = 215200 = 15
we nd that the probability of getting 215 heads is given as
P(400, 15) =
_
2
(400)
_
1/2
e
2(15)
2
/400
1.3%
9
Problem # 2
The Berkeley Campus has 2000 telephones (a very conservative estimate!). To guarantee access to the
outside world, 2000 telephone lines would be required, a rather extravagant number. Suppose that during
the peak use hour of the day, each campus phone is used to make a single two-minute call at a random
time. Find the minimum number of telephone lines required so that at most only 1% of callers fail to have
immediate access to a line. (Hint: approximate the distribution by a Gaussian distribution, and use tables
or your computer.).
Method 1
Since we know that in any 2 given minutes, the average number of people using a telephone line is
given by x =x = Np =
2000
30
. We nd that this distribution can be modeled as a Gaussian distribution of
the form
The distribution plotted above is given by
p(x) =
1
2
2
e
(x x)
2
/2
2
where
2
= Np(1p)
where p is the probability that a phone line will be used which is
p =
1
30
N = 2000
so all we have to do is integrate this function to some value of x that will yield 99%, thus
p(x < x
l
) =
1
2
2
Z
x
0
e
(x x)
2
/2
2
dx
10
using IDL we are able to plot this function and integrate to get
x = 85.3 86 lines
thus we would need a minimum of 86 lines so that at the most 1% of the people are not able to make a
call.
N = 86 lines
Method 2
If we say that n
are the number of phone lines being used

n
=
N
2
+s n
=
N
2
s
and if we let
n
=
N
2
+s = N s =
N
2
and we also know that the probability is given as
P(N, s) = g(N, s)P
N/2+s
P
N/2s
where the probability of the number of lines being used is given by

P
=
2 min
60 min
2000 lines
N lines
=
200
3N
and the other probability is given as
P
= 1P
=
3N200
3N
The Gaussian approximation for the multiplicity is given as
g(N, s) = 2
N
_
2
N
_
1/2
e
2s
2
/N
but since we know that s =
N
2
we get
g(N, N/2) = 2
N
_
2
N
_
1/2
e
N/2
thus we nd that the probability is given by
P(N, s) = 2
N
_
2
N
_
1/2
e
2s
2
/N
_
200
3N
_
N/2+s
_
3N200
3N
_
N/2s
(1.1)
given that s =
N
2
this simplies into
P(N, N/2) = 2
N
_
2
N
_
1/2
e
N/2
_
200
3N
_
N
11
and since we know that the probability needs to be 0.01% we can just write this as
2
N
_
2
N
_
1/2
e
N/2
_
200
3N
_
N
= 0.01
This can only be solved numerically, the numerical solution to this is
N = 83.0125 84 lines
Thus we know that
P(83, 83/2) = 0.01
Method 3
If we model this as a binomial distribution
p(n) =
N!
(Nn)!n!
p
n
(1p)
Nn
to nd the minimum number of phone lines that will be needed so that fewer than 1 % of the callers fail to
get thru requires us to take a sum
p(n < n
l
) =
N
n
l
+1
N!
(Nn
l
)!n
l
!
p
n
l
(1p)
Nn
l
< 0.01
where n
l
is the minimum number of phone lines required to satisfy this criterion. This can easily be put
into Mathematica, but I dont have it so I will quote the solution as
n
l
= 86
Method 4
If we look at the following function
p(x) =
1
2
2
Z
x
0
e
(x x)
2
/2
2
dx
We can see that this function resembles the error function
erf(x) =
2
Z
x
0
e
u
2
du
and the soultion for x of this function is given by the inverse error function
x = erf
1
(erf(x))
but we know that erf(x) is simply the probability that we are looking for, which in our case we are looking
for an x that will give us 99%. Thus we know that
u = erf
1
(erf(x)) = erf
1
(0.99) = 1.822
but we know that our u is simply
x x
2
= 1.822
12
since we know that
=
_
Np(1p) x =
2000
30
thus we nd
x =
2(1.822) + x
thus we nd that in order to get 99% we need
x = 86.681 = 87 lines
we have just basically shown that this problem can be done 4 different ways all yielding similar result,
it is just a matter of the approximation that we make.
Problem # 3
The binomial distribution can be written in the form
P(N, n) =
_
N
n
_
p
n
(1p)
Nn
_
N
n
_
=
N!
n!(Nn)!
where p is the probability that some single event occurs.
Assume that p 1, and N n. Show that P(N, n) can be written in the approximate form
P(N, n) =

n
e
n!
where = Np. This is the well-known Poisson distribution (rst derived to study the death rate from
horse kicks in the French army!). Sketch P(N, n) vs. n for < 1 and > 1.
Since we know that
P(N, n) =
_
N
n
_
p
n
(1p)
Nn
where the binomial coefcient is
_
N
n
_
=
N!
(Nn)!n!
or using Newtons generalized binomial theorem
_
N
n
_
=
N(N 1)(N2)...(N(n1))
n!
but since we know that N n this is simply
_
N
n
_
=
N
n
n!
thus we can write our original expression as
P(N, n) =
(Np)
n
n!
(1p)
Nn
we can see that that
(1p)
Nn
=
k=0
_
Nn
k
_
(p)
k
13
but we can see that
_
N n
k
_
=
(Nn)(Nn1)(Nn2)...(Nn(k 1))..
k!
=
N
k
k!
since we know that N n. Thus we nd
(1p)
Nn
=
k=0
(Np)
k
k!
= e
(Np)
thus we nd
P(N, n) =
(Np)
n
n!
e
(Np)
but if we let Np = then we recover what we were looking for
P(N, n) =

n
n!
e
and the Poisson curves are given by

We can see from the plots that the Poisson distribution is well dened for large values of N, in actuallity
the Binomial distribution becomes the Poisson distribution for large value of N.
Problem # 4 The Meaning of Never
It has been said that six monkeys, set to strum unintellegently on typewriters for for millions of years,
would be bound in time to write all the books in the British Museum. This statement is nonsense, for it
gives a misleading conclusion about very, very large numbers. Could all the monkeys in the world have
typed out a single specied book in the age of the universe?
Suppose that 10
10
monkeys have been seated at typewriters throughout the age of the universe, 10
18
s.
This numner of monkeys is about three times greater then the present human population of the Earth. We
suppose that a monkey can hit 10 typewriter keys per second. A typewriter may have 44 keys; we accept
lowercase letters in place of capital letters. Asuuming that Shalespears Hamlet has 10
5
characters, will
the monkeys hit upon Hamlet?
14
a) Show that the probability that any given sequence of 10
5
characters typed at random will come out in
the correct sequence (the sequence of Hamlet) is of the order
_
1
44
_
100000
= 10
164345
where we have used log
10
44 = 1.64345.
Since we know that there are a total of 44 keys then we know that the probability that a key will land upon
the right place is given by
p(1) =
1
44
but since we know that there are a total of 10
5
characters in total for Hamlet we know that the total
probability of this happening is given by
p(N) =
_
1
44
_
N
but since we know that N = 10
5
this is simply
p(N) =
_
1
44
_
100000
but we know that
log
10
p(N) = 100000log
10
_
1
44
_
164, 345
thus
p(N) = 10
164345
b) Show that the probability that a monkey Hamlet will be typed in the age of the universe is approxi-
mately 10
164316
. The probability of Hamlet is therefore zero in any operational sense of an event,
so that the original statement at the beggining of this problem will never occur in the total literary
production of the monkeys
Since we know that there is
N
monkeys
= 10
10
t
universe
= 10
18
s N
keys
/s =
10 keys
s monkey
thus the total number of keys that these monkeys can type in the total age of the universe is
N
keys
= 10
10
monkeys 10
18
s
10 keys
s monkey
= 10
29
keys
the probability that a monkey Hamlet will be typed in the age of the universe is given by
p(monkey Hamlet) = 10
29
10
164345
= 10
164316
Problem # 5 Coin Flips revisited
15
a) You ip 10 coins. What is the probability of obtaining exactly 5 heads and 5 tails?
We know that N = 10 and that the spin excess 2s = n
= 0. We also know that the probability of this

two-state system is given by
P(N, s) =
g(N, s)
2
N
we also know that
g(N, s) =
N!
_
N
2
+s
_
!
_
N
2
s
_
!
thus
g(10, 0) =
10!
5!5!
and the probability is given as
P(10, 0) =
10!
5!5!
1
2
10
= 0.25
b) You ip 1000 coins. What is the probability of obtaining exactly 500 heads and 500 tails?
We know that N = 1000 and the spin excess is 2s = 0. Since we also know that s N allows us to make
teh Sterling approximation
g(N, s) = g(N, 0)e
2s
2
/N
where
g(N, 0) = 2
N
_
2
N
_
1/2
and so the probability is given by
P(N, s) =
g(N, s)
2
N
=
_
2
N
thus we nd
P(1000, 0) =
_
2
1000
= 0.025
c) Why is the answer to a) more than b), yet we say the multiplicity function sharpens with increasing N.
The probability of getting exactly zero spin excess, i.e 50 % heads and 50 % tails decreases as N
increases. But the probability of being very close to s = 0 increases as 1/
N. It is the fractional width of

the distribution which decreases.
16
Chapter 2
Entropy and Temperature
Entropy and Temperature (Roadmap)
1. Denitions
2. Equal a priori probaility
3. Two systems in thermal equlibrium: Most probable conguration (MPC)
4. Thermal equilibrium: Entropy and Temperature
Denition of Entropy
Denition of temperature
Justication of MPC approximation
5. Laws of thermodynamics,0th,2nd,3rd
1. Some denitions
2.1 A Closed System
The energy, number of particles, external parameters( Electric elds and Magnetic elds are xed)
2.1.1 A quantum state is accesible
if its properties ( energy, number of particles) satisfy the specications of a system. e.g lets take a cubic
box: for 1 particle the energy of the state is identied by three quantum number, n
x
, n
y
, and n
z
.
One particle would remain in its state indefenitely
Now we add more particles- ecah one of these is in a state specied by these quantum numbers (n
x
, n
y
, n
z
)
with a total xed energy
Collisions cause transitons of the particles among quantum states
The total energy of a particle must be conserved
Those states with that given xed energy are accessible states.
17
2.2 Macroscopic Properties
The macroscopic propertie that we measure (heat capacity, suceptibility,...) are time averages of these
systems. However, in statistical mechanics we consider an ensemble average. The ensemble contains g
identical systems. One for each accesible state, where g is the multiplicity. We then average over the
ensemble to obtain a given macroscopic properties.
Example
we have 4 spin (1/2) with 2s = 2, the number of accesible states
g(N, s) = g(4, 1) =
N!
n
!n
!
=
4!
3!1!
= 4
Thus there are 4 possible states, so lets now take four systems, where each one is accesible to system

This is our ensemble, lets suppose that the probability of nding the system i an accesible state k with
spin excess 2 is
2 = p(k)
where
k
p(k) = 1
Lets suppose that we have a parameter x that takes the value x(k) when the system is i the state k, this
could be the magnetic suceptibility or the heat capacity. Then the expectation value of x is
x =
k
p(k)x(k) ensemble average
It is reasonable to suppose that the time average is the same as the ensemble average, this is known as
Ergodic Hypothesis, but there is no proof.
2.3 Postulate of Equal Apriori Probability
a priori - before testing, before hand, inate..
"A closed system is equaly likely to be in any one of its accesible states"
We have to bear in mind that this is a postulate and cannot be derived. i.e Newtons three laws, or
Maxwells equations. All we can do is to build a theory based on this postulate and then we can com-
pare the results with the experiments. If we get predictions that are correct, than we ca say our postulate
is justied a posteori (after testing). Thus
p(k) =
1
g
18
and thus
x =
1
g
k
x(k)
Example
Lets suppose that we have the four magnetic spins all with different electric dipole moments. Lets let x
be the electric dipole moment d, 2d, 3d, and 4d. For the four systems we have the following net electric
dipole moments

d +2d +3d +4d = 8d
22d +3d +4d = 6d
d +2d 3d +4d = 4d
d +2d +3d 4d = 2d
So the expectation value is
d =
x(k)
g
=
8d +6d +4d +2d
4
= 5d
2.4 Two Systems in Thermal Contact: Most Probable Conguration
(MPC)
As an example, consider spin system. Lets suppose that there is a magnetic eld B
N
1,
u
1
, s
1
system 1 N
2
, u
2
, s
2
system 2
where S is the spin excess, this is a closed system with a total energy E
T
. When we put this two together
we get a new system
N
1
, u
1
N
2
, u
2
This is also a closed system in thermal contact. But we have the constraint that
u
1
+u
2
= u
1
+u
2
= u
s
1
+s
2
= s
1
+s
2
= S
19
the total energy
u =2smB =2(s
1
+s
2
)mB =2(s
1
+s
2
)mB
We also need to assume that N
1
< N
2
, and thus we have the following constraint
|s
1
|
N
1
2
or N
1
2w N
1
lets write down the multiplicity
g
1
(N
1,
s
1
) system 1
g
2
(N
2
, s
2
) system 2
so the multiplicity of the combined system is given by the following
g(N, s) =
N
1
/2
s
1
=N
1
/2
g
1
(N
1
, s
1
)g
2
(N
2
, s
2
) =
N
1
/2
s
1
=N
1
/2
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
)
We have removed S
2
. These products have a maximum value which is to be determined for some value of
S
1
, this is what is called the most probable conguartion (MPC). For large values of N we will show that
we need to keep only the most probable conguration of the sum. i.e
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
)
lets write this in terms of a Gaussian, we saw that
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
) = g
1
(N
1
, 0)g
2
(N
2
, 0)e
2s
2
1
/N
1
e
2(ss
1
)
2
/N
2
Lets plot s
1
versus g(N, s).The maximum value correspond to where these two curves intersect. This is
known as the most probable conguration.
s
1
= s
1
+
s
2
= s
2
s
2
1
= s
1
2
+2 s
1
+
2
s
2
2
= s
2
2
2 s
2
+
2
Thus
g
1
(N
1
, s
1
+)g
2
(N
2
, s
2
) = g
1
(0)g
2
(0)exp
_
2 s
1
2
N
1
4 s
1
N
1
2 s
1
N
1
2 s
1
2
N
1
+
4 s
2
N
2
2
2
N
2
_
= (g
1
g
2
)exp
_
2
2
N
1
2
2
N
2
_
In the general case we know that
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
) = g
1
(N
1
, 0)g
2
(N
2
, 0)e
[2s
2
1
/N
1
2(ss
1
)
2
/N
2
]
As we increase s
1
this exponetial grows, thus we get a maximum value s
1
. What we need to do is gure
out this value, where we get the following result.
g
1
(N
1
, s
1
+)g
2
(N
2
, s
2
) = (g
1
g
2
)exp
_
2
2
N
1
2
2
N
2
_
20
Lets plug some numbers in to evaluate this, lets take a cm
3
of a solid, the number of atoms in this solid is
N
1
= N
2
= 10
22
lets suppose that is
= 10
12
s
N
1
= 10
10
Thus
2s
2
N
= 200
i.e
g
1
g
2
(g
1
g
2
)
max
= e
400
10
173
we can get a bit of insight in the following way, we can say that this conguration will never occur! The
system works its way through all possible values of g
1
and g
2
, so for this particular conguration to reach
the conguration g
1
and g
2
once, the system will be in (g
1
g
2
)
max
10
173
times. So if we suppose that any
spin ips every 10
12
seconds. Thus the number of congurations per second will be
10
22
10
12
= 10
34
/sec
so the time taken to get this deviation of
N
1
= 10
10
10
173
10
34
10
139
sec 10
132
yrs
where we know that the age of the universe is approximately 10
18
seconds, thus we can conclude that this
conguartion will never occur. This is a very important result and tells us why we will only consider the
most probable conguartion MPC.
2.4.1 Find maximum value of g
1
and g
2
We know that g
1
and g
2
can be written in the form
g
1
g
2
= g
1
(0)g
2
(0)exp
_
2s
2
N
1
2(s s
1
)
2
N
2
_
if we take the log of both sides we get
lng
1
g
2
= ln[g
1
(0)g
2
(0)
2s
2
N
1
2(s s
1
)
2
N
2
if we take the derivative we nd
s
1
[lng
1
g
2
] =
4s
1
N
1
+
4(s s
1
)
N
2
= 0
s
1
N
1
=
s s
1
N
2
=
s
2
N
2
thus the fractional spin excess are equal, if we take the second derivative we nd
2
s
2
1
[lng
1
g
2
] =
4
N
1
4
N
2
< 0
21
so at
s
1
N
1
=
s
2
N
2
=
s
N
which is the fractional excess of the combined system, thus we have
s
1
N
1
=
s
2
N
2
=
s s
1
N
2
=
s s
1
N N
1
which becomes
s
1
_
1
N
1
+
1
NN
1
_
=
s
NN
1
thus
s
1
=
_
N
1
N
1
+N
1
N
1
(NN
1
)
_
=
s
NN
1
which simplies into
s
1
N
1
=
s
N
using this result we nd
s
1
2
N
1
+
s
2
2
N
2
=
s
1
s
1
N
1
+
s
2
s
2
N
2
=
s
N
( s
1
+ s
2
) =
s
2
N
thus we can conclude that
(g
1
g
2
)
max
= g
1
(0)g
2
(0)e
2s
2
/N
2.5 Thermal Equilibrium: Entropy and Temperature
We have the expression for the multiplicity of the two systems given as
g(N, u) =

u
1
u
g
1
(N
1
, u
1
)g
2
(N
2
, u
2
)
if we assume that we keep only the most probable conguration, we can drop the sum to get
g(N, u) = g
1
(N
1
, u
1
)g
2
(N
2
, u
2
) MPC
if we take the derivative we nd
dg(N, u) =
_
g
1
u
1
_
g
2
du
1
+
_
g
2
u
2
_
g
1
du
2
= 0
where
du
1
+du
2
= 0
if we now take this expression and devide
1
g
1
_
g
1
u
1
_
N
1
=
1
g
2
_
g
2
u
2
_
N
2
this relates the derivative of the rst system to the second system, hence
_
lng
1
u
1
_
N
1
=
_
lng
2
u
2
_
N
2
22
this is the condition for thermal equilibrium. This is where we will introduce entropy
(N, u) = lng(N, u) Entropy
the entropy is the measure of the degree of randomness in a system. It is the natural log of the multiplicity.
Most people dene entropy as
S = k
B
lng
as a nal remark, Entropy is additive
(N, u) = ln[g
1
(N
1
, u
1
)g
2
(N
2
, u
2
)
= lng
1
(N
1
, u
1
) +lng
2
(N
2
, u
2
)
=
1
(N
1
, u
1
) +
2
(N
2
, u
2
)
We can dene the temperature as
1
=
_
u
_
N
thus in equilibrium
1
=
2
conventionally is written as
= k
B
T
we will relate to the Kelvin scale of absolute temperature.
2.5.1 Jusitication for keeping only the MPC
If we assume that
g =
u
1
g
1
(N
1
, u
1
)g
2
(N
2
, u
2
) = (g
1
g
2
)
max
we also assumed in our discussion of entropy that
= lng(N, u) = ln(g
1
g
2
)
max
=
1
+
2
the correct expression is really
= ln
_
g
1
(N
1
, u
1
)g
2
(N, uu
1
)
=
1
+
2
Why can we neglect all the other terms? How valid is our approximation? We have the following expres-
sion
g
1
(N
1
, s
1
)g
2
(N
2
, s
2
) = (g
1
g
2
)
max
exp
_
2
2
N
1
2
2
N
2
_
= s
1
s
1
lets suppose that we write
N
1
= N
2
=
N
2
we get
g(N, s) =

g
1
(N/2, s
1
+)g
2
(N/2, s
1
)
= (g
1
g
2
)
max
Z

e
8
2
/N
d
23
so in our analysis we have just ignored the gaussian, the integral is
Z

e
8/N
d =
_
N
8
Z

e
x
2
dx =
_
N
8
hence
g(N, s) = (g
1
g
2
)
max
_
N
8
next we can use Sterlings approximation
g(N, 0) = 2
N
_
2
N
_
1/2
N
N
2
we get the following
g(N/2, 0) =
_
2
N/2
_
4
N
_
2
_
N
8
= 2
N
4
N
_
N
8
nally we need to form the entropy
(N, s) = lng(N, s) = Nln2+ln
_
4
N
_
+
1
2
ln
_
N
8
_
we can rewrite this as follows
(N, s) = Nln2lnN+
1
2
lnN+
1
2
ln(/8) +ln(4/)
= Nln2
1
2
lnN
if we take a big number N = 10
22
Nln2 10
22
lnN 2.3log
10
10
22
50
thus the only term we really care about is
(N, s) Nln2
this term dominates all others for large N, thus we can conclude that only the most probable congu-
ration contributes to the entropy and the temperature.
We have been talking about thermal equilibrium of two systems, the system was dominated by the
MPC. We have dened the Entropy and the temperature of the system. We will concentrate on is the laws
of thermodynamics
Zeroth Law- two systems in thermal equilibrium with a third system then they are all in thermal
equilibrium
1
=
3
2
=
3
1
=
2
24
The First Law- Heat is a form of energy
The Second Law- The Entropy of a closed system will either remain constant or increases when a
constraint is removed.
If we remember the two system multiplicity
g =
u
g
1
(u
1
)g
2
(uu
1
)
somewhere in this sum is the term that corresponds to the starting point. What we will call that as
g(u) = g
i
1
(u
1
(t = 0))g
i
2
(uu
1
(t = 0)) +

u
1
=u
1(t=0)
g
1
(u
1
)g
2
(uu
1
)
what we have is two terms, where the rst term is the entropy
f
= ln(g) = ln(g
i
1
g
i
2
) +ln
_
g
1
g
2
_
where
i
= ln(g
i
1
g
i
2
)
we know that the nal value of the entropy is
f

i
If we can imagine having two systems where
1
>
2
and that u is removed from system and added to
system 2. What happens to the entropy when we do this
=
_

u
1
_
N
1
(u) +
_

u
2
_
N
2
(u)
= u
_
1
1
_
0
when
1
>
2
then u > 0
The Third Law of Thermodynamics- The entropy of a system approaches a constant value as the
temperature goes to zero.
This will follow from our statistical approach if temperature is an increasing function of energy
_
T
u
_
N
> 0
again we will have two systems where we have u removed from system 2
u
1
= u u
2
=u
1
=
2
=
again we have to go back to our law of increase of entropy, what happens to
1
and
2
, this are the
values at t = 0. We can do this by using a Taylor expansion
1
=
0
+
_
1
u
1
_
u
u
0
+
1
2
_
1
u
2
1
_
u
0
(u)
2
+..
2
=
0
+
_
2
u
2
_
(u)
u
0
+
1
2
_
2
u
2
2
_
u
0
(u)
2
+..
25
and
1
=
u
+
(u)
2
2
u
_
1
u
1
_
u
0
2
=
u
+
(u)
2
2
u
_
2
u
2
_
u
0
and nally
=
1
+
2
is
u
_
u
_
=

u
_
1
_
=
1
u
thus
=
(u)
2
2
_
1
u

1
2
u
_
=
(u)
2
2
2
_
1
u
+

2
u
_
< 0
the above function is evaluated at u
0
, thus we have just shown that
u
0
As is lowered then the energy decreases, thus at absolute zero = 0 then the system is in the lowest
energy state and it is in a non degenerate state.
ln(1) = 0
0
2.6 Summary
Equal a priori probability -
Ergodic hypothesis - This is simply that the time average = ensemble average. The ensemble average
is simply
x =
s
X(s)p(s)
which is a weighted average over all possible congurations
Multiplicity function of combined system
g(N, u) =

u
1
<u
g
1
(N
1
, u
1
)g
2
(N
2
, uu
1
)
for large N the sum was dominated by one term, and this term was called the most probable cong-
uration MPC.
From the multiplicity function we dened the entropy as
= ln(g(u)) S = k
B
this was an extensive property, andsince we use the log then this made this an additive quantity.
26
We then dened the temperature as
1
=
_
u
_
N
= k
B
T
With these two notions we are able to talk about thermal equilibrium
1
=
2
is maximized
we can consider temperature to be an intensive property that increases with energy.
Finally we also talked about the law of increase of entropy. Two system is thermal equilibrium
0
The laws of thermodynamics
0th
1
=
3

2
=
3

1
=2
1st = heat = energy
2nd = 0
3rd = lim
0
=
0
Problem # 1 Entropy and Temperature
Suppose g(U) =CU
3N/2
, where C is a constant and N is the number of particles.
a) Show that
U =
3
2
N
Since we know
g(U) =CU
3N/2
we can take the natural log of both sides
lng(U) = ln
_
CU
3N/2
_
= ln(C) +
3N
2
ln(U)
Taking the partial derivative on both sides with respect to U yields
U
lng(U) =

U
_
ln(C) +
3N
2
ln(U)
_
=
3N
2
U
ln(U)
we know that the left hand term is simply the entropy
= lng(U)
27
thus
U
=
3N
2
1
U
thus
U =
3N
2
U
but we know that the temperature is dened as

1
=
_
U
_
N,V
thus we have just showed that
U =
3N
2

b) Show that
_
U
2
_
N
< 0
show that it is negative. This form of g(U) actually applies to an ideal gas.
We can simply take a double derivative of g(U)
U
_

U
lng(U)
_
=

U
_
3N
2
U
ln(U)
_
this becomes
U
2
=

U
_
3N
2
1
U
_
=
3N
2U
2
since we know that N can only be positive and the energy can only be positive we have just shown
_
U
2
_
N
< 0
Problem # 2 Paramagnetism
Find the equilibrium value at temperature of the fractional magnetization
M
Nm
=
2s
N
of the system of N spins each of magnetic moment m in a magnetic eld B. The spin excess is 2s. Take
the entropy as the logarithim of the multiplicity g(N, s) as given
(s) logg(N, 0)
2s
2
N
(2.1)
for |s| N. Hint : Show that in this approximation
(U) =
0
U
2
2m
2
B
2
N
(2.2)
28
with
0
= logg(N, 0). Further, show that 1/ = U/m
2
B
2
N, where U denotes U, the thermal average
energy.
Since we know that
0
= logg(N, 0) U =2smB
thus
s =
U
2mB
thus Equation 1 becomes Equation 2, i.e
(U) =
0
U
2
2m
2
B
2
N
if we take a differential on both sides with respect to U we nd
(U)
U
=
U
m
2
B
2
N
but we know that
1
=

U
=
U
m
2
B
2
N
so we nd that the average thermal energy is given by
U =
m
2
B
2
N
this is related to the spin excess and the magnetic moment by

s =
U
2mB
=
mBN
2
we nd that the equilibrium value at temperature of the fractional magnetization is given as
M
Nm
=
mB
Problem # 3 Addition of entropy for two spin systems

Given two systems of N
1
N
2
=10
22
spins with multiplicity functions g
1
(N
1
, s
1
) and g
2
(N
2
, ss
1
), the
product g
1
g
2
as a function of s
1
is relatively sharply peaked at s
1
= s
1
. For s
1
= s
1
+10
12
, the product g
1
g
2
is reduced by 10
174
from its peak value. Use the Gaussian approximation to the multiplicity function;
the form
g
1
(N
1
, s
1
+)g
2
(N
2
, s
2
) = (g
1
g
2
)
max
e
_
2
2
N
1

2
2
N
2
_
(2.3)
may be useful.
a) Compute g
1
g
2
/(g
1
g
2
)
max
for s
1
= s
1
+10
11
and s = 0.
29
For s
1
= s
1
+ we know that = 10
11
= 10
11
N
1
N
2
= 10
22
s
1
+s
2
= s s
1
=s
2
We can see that Equation 3 can be written as
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
)
(g
1
g
2
)
max
= e
4
2
/N
1
0.018
For s = 0 we know that = 0 thus we know that
g
1
g
2
(g
1
g
2
)
max
= 1
b) For s = 10
20
, by what factor must you multiply (g
1
g
2
)
max
to make it equal to
s
1
g
1
(N
1
, s
1
)g
2
(N
2
, s
s
1
); give the factor to the nearest order of magnitude.
Method 1
since we know that
g
1
(N
1
, s
1
)g
2
(N
2
, s
2
) = g
1
(N
1
, s
1
+)g
2
(N
2
, s
2
) = (g
1
g
2
)
max
e
_
2
2
N
1
2
2
N
2
_
since
s
1
= s
1
+ s
2
= s
2
thus
s
1
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
) = (g
1
g
2
)
max
e
_
2
2
N
1
2
2
N
2
_
= (g
1
g
2
)
max
Q
where Q is the factor we need to multiply (g
1
g
2
)
max
so that it is equal to
s
1
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
). So
we can just turn this sum into an integral
Q =
Z

e
_
2
2
N
1

2
2
N
2
_
d =
Z

e
_
4
2
N
1
_
d
this is simply a Gaussian integral with a solution
Q =
_
N
1
4
= 8.8610
10
10
11
Method 2
We know that
Q(g
1
g
2
)
max
=
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
) (2.4)
but we know that we can write the sum as
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
) = g(N, s)
since we know that
N = N
1
+N
2
= 2N
1
30
thus we nd
g(2N
1
, s) = g(2N
1
, 0)e
2s
2
/2N
1
= g(2N, 0)e
s
2
/N
1
we also know that
(g
1
g
2
)
max
= g
1
(N
1
, 0)g
2
(N
2
, 0)e
2s
2
/2N
1
= g
1
(N
1
, 0)g
2
(N
2
, 0)e
s
2
/N
1
thus Equation 4 can be written as
Q =
g
1
(N
1
, s
1
)g
2
(N
2
, s s
1
)
(g
1
g
2
)
max
=
g(2N
1
, 0)
g
1
(N
1
, 0)g
2
(N
2
, 0)
(2.5)
but we know that
g(N, 0) =
_
2
N
2
N
and Equation 5 becomes
Q =
_
2
2N
1
2
2N
1
_
2
N
1
_
2
N
1
2
2N
1
=
_
N
1
4
= 8.8610
10
10
11
c) How large is the fractional error in the entropy when you ignore this factor?
We know that the fractional error is dened as
where
= ln(g
1
g
2
)
max
Q = ln(g
1
g
2
)
max
thus we nd
=
lnQ
ln(g
1
g
2
)
max
Q
=
lnQ
lnQ+ln(g
1
g
2
)
max
=
lnQ
lnQ+lng
1
(N
1
, 0)g
2
(N
2
, 0)
s
2
N
1
but we know that
(g
1
g
2
)
max
= g
1
(N
1
, 0)g
2
(N
2
, 0)e
s
2
/N
1
and we also know that
g
1
(N
1
, 0) =
_
2
N
1
2
N
1
g
1
(N
1
, 0) =
_
2
N
2
2
N
2
since we know that N
1
= N
2
= 10
22
, plugging this into some calculating machine we nd
1.8310
21
this shows us that the extra factor does not affect the entropy very much.
31
Chapter 3
Boltzman Distribution & Helmholtz Free
Energy
Resevoirs and systems
Boltzman factor
Partition Function
Example of a paramagnetic system
Pressure
Thermodynamic identity
Helmholtz free energy
Classical Ideal Gas
Equipartition Theorem
3.1 Resevoir & Systems
We have a resevoir in a large system, what we assume is that they are in thermal contact at some temper-
ature and also that the energy of the system is
l
u
0
. We must consider an entire ensemble of such
systems and then we must take the average of these. If we keep N xed then we call this the cononical
ensemble. We must write down the multiplicity of the combinbed system
g(u
0
) = g
R
(u
0
l
)g
s
(
l
)
what we are specifying with l is the label of a particular quantum state of a system. Thus there is only one
way for it to be in that state which means
g
s
(
l
) = 1
thus
g(u
0
) = g
R
(u
0
l
)
and since this total system is equally likely to be in any of of these states thus the probability is
p
l
= Ag
R
(u
0
l
)
32
and since this is a probability
l
p
l
= 1
again we have an approximation which implies that we will have to do a Taylor expansion, but we will
nd that these multiplicity functions will begin to get out of hand when Taylor expanded. We will instead
Taylor expand the entropy
= ln[g
R
(u
0
l
)] ln[g
R
(u
0
)]
_
l
ln[g
R
]
u
_
u
0
+...
= ln
_
g
R
(u
0
l
)
g
R
(u
0
)
_
=
If we raise both sides to the exponetial

g
R
(u
0
l
) = g
r
(u
0
)e
l
/
thus the probability is given as
p
l
e
l
/
This is known as the Boltzman factor
Last time we talked about resevoirs, where we made the assumption that the energy in the system is much
smaller than the energy in the resevoir
l
U
0
where l is to denote the state of the system. What we are looking for is the ensemble average X
X =
l
X(l)p(l)
we need to nd the multiplicity function of the combined system
g(U
0
) = g
R
(U
0
l
)g
s
(l)
where
g
s
(l) = 1
by denition. Thus the probability we are looking for is proportional to g(U
0
), and to do this we must
Taylor expand to nd
g(U
0
l
) = Ae
l
/
where the probability is
p(l) e
l
/
which is known as the Boltzman factor.If we look at some simple model systems, i.e SHO
n
=
_
n+
1
2
_
we can see that the higher the energy the lower the probability of nding this system in this state
p
n+1
p
n
=
e
(n+3/2)/
e
(n+1/2)/
= e
/
33
and we can see
0
p
n+1
p
n
0

p
n+1
p
n
1
l
p
l
=
l
Ae
l
/
A
_
l
e
l
/
_
1
where
p
l
=
e
l
/
l
e
l
/
where the denominator is known as the partition function
Z
l
e
l
/
this is useful if you start with a microscopic model where we know how to calculate the microstate
energies. From these microstate energies we can use the partition function to get the thermodynamic
properties of this system. If we dene the energy states then we can use the partition function as
Z
n
=
n
g
s
(
n
)e
n
/
where g
s
(
n
) is how many states have =
n
. Lets nd the average energy given the partition function
U =
where
=
l
p(l) =
1
Z
l
e
l
/
where we often use = 1/, using this we get
=
l
p(l) =
1
Z
l
e
and the trick we can use
=
l
e
and now we can write

=
1
Z
_
_
=
lnZ
to put this back in terms of we just simply need to use the chain rule
Z
=
Z
=
Z
2
_
thus
=
1
Z
2
Z
=
2
lnZ
We will need to calculate what the scale of the energy uctuations are, we will use a method that was
used in quantum mechanic.
34
3.2 Energy Fluctuations
()
2
mean squared energy uctuation
where
( )
and
()
2
=
2
2 +
2
=
2
2 +
2
=
2

2
we can use the same trick we have done before
2
=
1
Z
2
l
e
l
where the trick is
2
e
l
=
2
l
e
l
thus
2
=
1
Z
_
2
Z
2
_

_
1
Z
Z
_
=
1
Z
2
_
Z
_
2
+
1
Z
2
Z
2
we can write this as
1
Z
2
_
Z
_
2
+
1
Z
2
Z
2
=
_
1
Z
Z
_
2
+
2
=
2
+
2
to nish up
()
2
=

_
lnZ
_
=

2
lnZ
2
3.3 Paramagnetic System
We have N number of atoms in a volume where each atom has a spin of 1/2 and a magnetic moment m. We
apply a magnetic eld H and we need to nd m(). The system consist of a single spin and the resevoir
has all the other spins with respect to . We will also neglect all the spin-spin interactions.
m() =
1
Z
l
m
l
e
l
what are the states? there are only two states, 1 toward the eld and one opposing the eld
m
= +m
=mB spin up
m
= m
= mB spin down
and we also know that B = H, now we nd the partition function to be
Z = e
+e
= e
mB
+e
mB
35
so the expectation value is now
m() =
me
mB
me
mB
e
mB
+e
mB
= m
sinh(mB)
cos(mB)
= mtanh(mB)
thus
m() = mtanh(mB)
but we are looking for the moment for all N spins
M() = Nm() = Nmtanh
_
m
_
we can also nd the suceptibility to be
=
dM
dB
=
Nm
2
sech
2
_
mB
_
if we look at the limits of the hyporbolic tangent function
tanh(x) =
e
x
e
x
e
x
+e
x
thus for small x we nd
lim
x0
tanh(x) =
(1+x) (1x)
1+x +1x
=
2x
2
= x
and for large x we nd
lim
x
tanh(x) 1
In the limit that mB/ 1 or high temperature
M() Nm
_
Bm
_
=
Nm
2
B
and
=
Nm
2
Curies law
in the limit of low temperature we nd
M() = Nm
and
= 0
another thing we are interested in is to nd the average energy U =
=M()B =NmBtanh
_
mB
_
thus the heat capacity is dened as
C
V
=
_
U
T
_
V
k
B
_
U
_
=
_
U
T
_
36
where
U
=NmBsech
2
_
mB
__
mB
2
_
thus the heat capacity is
C
V
=
k
B
Nm
2
B
2
2
sech
2
_
mB
_
lets look at what the heat capacity does in the extremes. At high temperatures
sech(x) =
2
e
x
+e
x
=
2
1+x +1x
= 1
and
C
V
=
Nm
2
B
2
2
and at low temperatures
sech(x) =
2
e
x
= 2e
x
in this case the heat capacity is roughly
C
V
=
Nm
2
B
2
2
_
2e
mB/
_
2
=
4Nm
2
B
2
2
e
2mB/
if we look at this graphically we can see that there is a maximum that is known as the Schotkki anomoly.
If you have interaction we get another phenomenom

1

C
where
C
is known as the Curie temperature. This form tells us that when the temperature is lower than
the Curie temperature forces a negative susceptibility and we have a feromagnetic material and not para-
magnetic.
At high temperatures the magnetic spins are all equally divided in up states and down states. At low
temperatures all of the spins are in the up (high energy) state and the magnetic energy is higher than the
thermal energy. If all the spins are aligned with he eld it will lower the energy and if all the spins are
anti-aligned that raises the energy.
3.4 Calculating the average energy using the partition function
we can write the average energy as

1
Z
Z
=
lnZ
=
2
lnZ
Z
where we know that the partition function is given as
Z = e
mB
+e
mB
= 2cosh(mB)
and thus
Z
= 2mBsinh(mB)
so we have
=
1
Z
Z
=
2mBsinh(mB)
2cosh(mB)
=mBtanh(mB)
which is the exact result we have already obtained.
37
3.4.1 Negative Temperature
We know that the energy is always an increasing function of temperature. We will need to consider a two
level quantum system. We can write the ratio of the number of particles in one energy state to the number
of particles in the other energy state
N
2
N
1
=
e
E
2
/
e
E
1
/
= e
(E
2
E
1
)/
> 1
where E
2
E
1
is assumed positive, for this to be true means that < 0. The negative temperature means
that we have a higher population in the high energy state than in the lower energy state. This is known as
a non-equilibrium system. This happens in lasers because we need more atoms in the high energy state
than in the lower energy state. To get laser action we must have all of the atoms in the upper state making
transitions to the lower energy state that. This is also know as population inversion. We also know that
negative temperatures require an upper bound on the energy, where this is given by NmB. This also means
that the multiplicity is bounded. This would not be true in the case of a gas, because as you raise the
temperature you also raise the energy. There is no negative temperatures for systems that have kinetic
energy or that the value of the multiplicity increases without bound. Negative temperatures do have more
energy than positive energies. If we have two systems, one with negative temperature and one with positive
temperature that are in thermal contact we nd thet heat ows from the < 0 to >0.
3.5 Pressure
We dene quantities such as and in terms of thermodynamic varaibles. But the pressure p must be
dened so as to be consistent with Newtons laws.
Newtons laws
If we have a cylinder with a gas at an initial position x and we expand the volume by an amount x with a
constant area and a constant force pushing down on the gas. If the piston moves up by a distance x then
we know that the work done on the gas is given by
W =Fx =F
V
A
=pV
we also nd this to be equal to
W = U
which is the increase of the energy of the system, and hence the pressure is given by
p =
U
V
we need to go through a slightly different approach to get to the thermodynamic relationships.
3.5.1 Thermodynamics
Consider a system in a quantum state l. If we let V V +V (quasistatically), this means that the system
remains in thermal equilibrium. Imagine a box with distinct energy levels that are populated by the atoms
or molecules of the gas. If we now expand the system we know that the energy levels will get closer
38
together. Because the system remained in thermal equilibrium than on the average the population of this
energy levels will not change. This is know as the adiabatical approximation where the state of the
system remains the same and hence the entropy remains xed. We can now wrtite the energy as
l
(V)
l
(V +V)
in the same state as l, we can now do a Taylor expansion to nd
l
(V +V) = (V) +dV
_
l
V
_
where the lower case sigma means that this process is at constant entropy. The ensemble average is given
by
U(V +V) = U(V) +dV
_
U
V
_
= U(V) pdV
and thus
p =
_
U
V
_
we need to know how to get pressure in terms of entropy. What we know is that we can write
= (U,V, N) where N is constant
If we let
0 = d =
_
U
_
V,N
(dU)
+
_
V
_
U,N
(dV)
and now if we do
0 =
_
U
_
V,N
_
U
V
_
+
_
V
_
U,N
where we know that
1
=
_
U
_
V,N
p =
_
U
V
_
and we nally nd
p
=
_
V
_
U,N
3.6 Thermodynamic Identity
To simplify this we will write = (U,V) and we will keep N xed, thus
d =
_
U
_
V
dU +
_
V
_
U
dV
=
1
dU +
p
dV
we can now write this as
d = dU + pdV
thus we can write the change in the energy as
dU =dpdV
where d is the heat added to the system and pdV is the work done on the system.
39
3.7 Helmholtz Free Energy
We have used the free energy in the thermodynamic identity as
dU(,V) =dpdV
this does not always have to be the case, imagine a systme at constant temperature. We could write this
instead as
dU = d() d pdV
where
d(U ) =d pdV
and
dF(,V) =d pdV
so the quantity
F(,V) =U
this is known as Helmholtz free energy. If we take a derivative of this we get the following
dF(,V) =
_
F
_
V
d +
_
F
V
_
dV
and hence
=
_
F
_
V
p =
_
F
V
_
where F is the appropriate energy for isothermal systems (xed ). If we look at the denition for the
pressure
p =
_
F
V
_
=
_
(U )
V
_
=
_
U
V
_
+
_
V
_
where the rst term is the energy part and the second term is the entropy part. The rst tirm tends to
dominate for solids, wheras if you had a gas, this term would be really small. On the other hand the
second term dominates for a gas. There is one nal thing we can get from this algebra, this is what is
called the Maxwells relations
3.8 The Maxwell Relations
From
=
_
F
_
V
p =
_
F
V
_
If we differentiate
_
V
_
=
_

2
F
V
_ _
p
_
V
=
_

2
F
V
_
thus we can see
_
V
_
=
_
p
_
V
40
Why is the Helmholtz free energy interesting? We know that the free energy is a minimum for a system in
thermal equilibrium with a resevoir.
F =U
imagine a resevoir where
dF
s
= dU
s
s
xed temperature
we also have the following
1
=
_
U
_
V
dU
s
=
s
constant volume
if we substitute this into the above equation we nd
dF
s
= 0
is this a maximum or a minimum? Lets consider the total energy of the system
U = U
R
+U
s
=
R
+
s
=
R
(U U
s
) +
s
(U
s
)
if we assume U
s
U
R
then we can simply do a Taylor expansion
=
R
U
s
_
R
U
R
_
V
+
s
(U
s
)
we can recall that
1
=
_
R
U
R
_
V
putting this in gives
=
R
(U)
1
(U
s
s
)
we can see that
=
R
F
s
this is because that we are assuming that

R
(U) is a xed quantity. We know that in thermal equilibrium
that the entropy is a maximum, therefor, if we consider a small deviation from
=
R
F
s
=
F
s
thus for > 0 then if is a maximum means that F

s
is a minimum. On the other hand the energy of the
system corresponds to a minimum.
Example: Paramagetism
Lets nd the Helmholtz free energy F and the average magnetization M of N spins at mB (high
temperature). We can write the free energy as
F(s, , B) =U(s, , B) (s, , B)
41
where we know that
U(s, , B) =2smB
and also
g(N, s) = g(N, 0)e
2s
2
/N
this is the Gaussian approximation in the high temperature limit. Lets put all this together
F(s, , B) =2smBlng(N, 0) +
2s
2
N
nally, in thermal equilibrium we can take the derivative
_
F
s
_
,B
=2mB+
4s
N
= 0
thus
2s =
mBN
where
M = 2sm =
m
2
BN
this is the same thing we found in the high temperature limit before tanh 1.
3.9 Helmholtz free energy and the Partition Function
If we let
F =U =
_
F
_
V
thus
F =U +
_
F
_
V
and we also know
_
F
_
V
=F +
_
F
_
V
and we nd
F =U +
2

_
F
_
V
+F
and nally
U =
2

_
F
_
V
but recall that
U =
2
lnZ
and thus we nd
F
=lnZ
42
this is a nice way to relate the microscopic properties Z to the macroscopic properties F. We can also write
this expression as
Z = e
F/
if we remember the probability
p(
l
) =
e
l
/
Z
= e
(F
l
)/
thus we are able to calculate the Boltzman factor if we know the free energy of the system without ever
knowing what the partition function is.
3.10 One Particle in a Box
For simplicity we assume that our box is a cube, with sides l. There is one particle with mass M. We all
know how to write down the Schrodinger Equation and we can nd the energies as
m
=

2
2m
_
L
_
2
(n
2
x
+n
2
y
+n
2
z
) n
2
= n
2
x
+n
2
y
+n
2
z
n
2
x
+n
2
y
+n
2
z
1
we can now write the partition function
Z
1
=
n
x
n
y
n
z
e
2
2mL
2
(n
2
x
+n
2
y
+n
2
z
)
since we know that the temperature is much greater than te energy spacing allows us to turn this sum into
an integral. This is know as the classic limit approximation. If we let
2
=

2
2
2mL
2
thus we can write

Z
1
=
Z

0
dn
x
Z

0
dn
y
Z

0
dn
z
e
2
(n
2
x
+n
2
y
+n
2
z
)
but this can also be written as
Z
1
=
_
Z

0
e
2
n
2
x
dn
x
_
3
the solution is
Z
1
=

3/2
8
2
3/2
M
3/2
L
3
3/2
3
=Vn
Q
where n
Q
is known as the quantum concentration and dened as
n
Q
=
_
M
2
2
_
3/2
43
3.11 Average energy
U =
2
_
lnZ
1
_
V
now
lnZ
1
=
3
2
ln + independent terms
thus
_
lnZ
1
_
V
=
3
2
1
or
U =
2
3
2
=
3
2
=
3
2
k
B
T
and the specic heat is given by
C
V
=
3
2
k
B
this allows us to measure the mean square velocity
1
2
Mv
2
=
3
2
k
B
T
thus
v
2
=
3k
B
T
M
We want to know what the meaning of the concentration is? Recall the Debroigle wavelength
D
=
h
p

h
M(3k
B
T/M)
1/2

h
(3M)
1/2
and
3
D
h
3
(3M)
3/2

1
n
Q
thus
n
Q
3
D
this means that the concentration corresponds to one particle in a volume of
3
D
. This allows us to under-
stand degeneracy in gases. If 2 particles are separated by a distance much greater then
D
then their wave
functions do not overlap and they are in the classical regime, and the results do not depend whether they
are bosons or fermions. On the other hand if they are separated by less than the Debriogle wavelength
then their wave functions overlap and they are in the quantum regime. Now the results depend crucially
on whether they are bosons or fermions.
3.11.1 Example: N particles in a box
Imagine that we have a number of particles N
2
at standard pressure and temperature STP. we know that
n
610
23
molecules/mole
22.410
3
cm
3
/mole
310
19
molecules/cm
3
44
what is the quantum concentration? we know that the mass is given by
M (1.6710
27
kg) 28 410
26
kg
and
n
_
410
26
1.410
23
300
2(10
34
)
2
_
10
26
molecules/cm
3
thus we are very strongly in the classical limit. The seperation is given by
= 10
2
3.12 Equipartition Theorem

we know that the energy for a single atom is given by
U =
3
2
and that each square term in momentum and position coordinates has a mean energy /2 (k
B
T/2) in
the classical limit. For an ideal gas, the hamiltonian is given by
H =
p
2
x
2m
+
p
2
y
2m
+
p
2
z
2m
and
U =
3
2
Lets imagine that we only have one dimension. Thus the Hamiltonian is given by
H =
p
2
2m
+
1
2
kx
2
and we have an energy given by
U =
Proof
Lets imagine a one dimensional gas with a Hamiltonian
H =
p
2
2m
= Bp
2
i
which is just a general expression for a quadratic term. The energy is given by

i
=
R
i
e
i
dp
i
R
0
e
i
dp
i
=
i
dp
i
R
i
dp
i
this is simplied as

i
=

ln
_
Z

i
e
i
dp
i
_
45
and now
Z

i
e
i
dp
i
=
Z

i
e
Bp
2
i
dp
i
if we let
y =
1/2
p
i
we get
Z

i
e
i
dp
i
=
1
_
i
e
By
2
dy
but we know that
ln
_
1
_
i
e
By
2
dy
_
=
1
2
ln+terms independent of
thus the average energy is

i
=

1
2
ln
_
=
1
2
=

2
now we would like to apply this to the idea that all resistor generate Johnson noise or Nyquist noise.
3.13 Johnson Noise or Nyuist noise
Imagine that you have some resistor with a value of R and if we were to measure the noise across a V
N
,
so as a function of time we would get something in which its average is zero, but the mean square value
is not zero. We could then measure the current noise by connecting a wire at the end of the circuit. We
will once again see a signal that uctuates. This provides an absolute limitation on how accurately you
can measure something. We will apply the equipartition function to see how this works. We will calculate
the power spectrum which is also known as the spectral density. This is usually given as S
( f ) but in our
case it is convenient to write it as S
V
() the following relationships are
S
V
()d = S
V
( f )d f
where
S
v
() = S
V
( f )
d f
d
we want to look at a narrow window that has a 1 Hz bandwidth, thus this is the mean square voltage in a
1 Hz bandwidth, as you will see, as we scan the frequency the value of S will vary. If we can imagine a
circuit with a resistor, a conductor and a capacitor. The quality factor for this circuit is given by
Q =

0
L
R

2
0
=
1
LC
we can also write Q as
Q =

0
=
R
L
Now using the equipartition we can see that there will be two square terms, thus we get the following
1
2
CV
2
N
=
1
2
k
b
T V
2
N
=
k
B
T
C
and
1
2
LI
2
N
=
1
2
k
B
T I
2
N
=
k
B
T
L
46
all frequencies add up to contribute to the square terms. The task is to go from the mean square term to
the spectral density. So Lets write down themean square value for the current source
I
2
N
=
k
B
T
L
=
Z

0
S
V
()d
|Z()|
2
this takes a voltage squared and devide by the impedence squared. We all remember that we can write
Z() = R+iL+
1
iC
and we also rember that
1
C
=
2
0
L
thus we nd that
Z() = R+
iL
(
2
0
)
2
but
|Z()|
2
= L
2
_
R
2
L
2
+
(
2
2
0
)
2
2
_

2
=
R
2
L
2
this allows us to write
I
2
N
=
Z

0
S
V
()
L
2
d
2
+
(
2
2
0
)
2
2
this function is sharply peaked about
0
for high Q. If we take the limit we nd
S
V
() S
V
(
0
)
if we look at
(
2
2
0
)
2
2
=
((
0
)(+
0
))
2
2
if we let
0
we nd
(
2
2
0
)
2
2
= 4(
0
)
2
given this we get the following result
k
B
T
L
=
S
V
(
0
)
4L
2
Z

0
d
(
0
)
2
+R
2
/4L
2
x =
0
= d a = R/2L
as you can see this now looks more tractable, thus we can now write this as
S
V
(
0
)
4L
2
Z

0
dx
x
2
+a
2
where we all know that
Z

0
dx
x
2
+a
2
=

a
thus we nd
k
B
T
L
=
S
V
(
0
)
4L
2
(R/2L)
=
S
V
(
0
)
2LR

47
thus we nd that the spectral
S
V
(
0
) =
2
k
B
TR
this answer does not depend on either L or C, thus this is true for all values of L and C. This is true for all
values of . This is avery good example of what is called white noise. Thus we have the nal result
S
V
() =
2
k
B
TR S
V
( f ) = 4k
b
TR
this is the famous results called Nyquist noise or Johnson noise. The current noise is given by
S
I
( f ) =
4k
B
T
R
The Nyquist noise sets a fundamental limit on the smallest voltage or current that one can measure. For
example if we have some experiment that can be modeled with a resistor connected to an amplier then
the smallest value of the voltage will always be limited by the Nyquist noise. What we will see is that
the magnitude scales linear with the absolute temperature. Thus to make more accurate measurements we
must decrease the tempearture. This enables us to measure lower voltages or anything else we might want
to measure. If we lower the temperature enough then we will reach the quantum limit of the noise, which
will take over when h f k
B
T. As a nal remark because of the linear dependence with temperature than
the Nyquist noise is used as an absolute thermometer.
3.14 Summary
The Boltzman factor
p(
l
) =
e
l
/
Z
is the probability using the Boltzman factor. We then introduced the partition function
Z =
s
e
s
/
we then intruduced the concept of pressure, the pressure is given by
p =
_
U
V
_
=
_
V
_
U
where we have the identity given by
dU =dpdV
this allows us to write the Helmholtz free energy
F =U
this is only for isolated thermal systems. We also dened the entropy as
=
_
dF
d
_
V
48
and
p =
_
dF
dV
_
the Maxwell relations are given by

_
V
_
=
_
dp
d
_
V
where the free energy is
F =lnZ
and the probability is given by
p(
l
) = e
(F
l
)/
we then went to a particle in a box, where
Z
1
= n
Q
V n
Q
=
_
M
2
2
_
3/2
where the energy of one particle is given by
U =
3
2
we then move on to the Equipartition theorem

U =

2
per quadratic term. Finally we talked about the Nyquist noise
S
V
( f ) = 4k
B
TR S
I
( f ) =
4k
B
T
R
Problem # 1
A dilute solution of macromolecules at temperature T is placed in a centrifuge rotating with angular
velocity . The mass of each molecule is m. The equivalent centrifugal force on each particle in the
rotating frame of reference is m
2
r, where r is the radial distance from the axis of rotation.
Find how the relative density of molecules (r) varies with r.
The probability that a system will be in a specic quantum state s of energy
s
is proportional to the
Boltzman factor. The ratio of the probability that the system is an a quantum state 1 at energy
1
to the
probability that the system is in quatum state 2 at energy
2
is just the ratio of the two multiplicities
P(
1
)
P(
2
)
=
g
R
(U
0
1
)
g
R
(U
0
2
)
(3.1)
the multiplicity is the number of states having the same value s. This is a direct consequence of what is
called the fundemental assumption. If the resevoir is very large, than the multiplicities are very large. We
can write Equation 1 in terms of the entropy of the resevoir
= lng
R
g
R
= e
49
thus Equation 1 now becomes
P(
1
)
P(
2
)
=
e
(
R
(U
0
1
))
e
(
R
(U
0
2
))
(3.2)
we can dene
R
=
R
(U
0
1
)
R
(U
0
2
) (3.3)
this allows us to write Equation 2 as
P(
1
)
P(
2
)
= e
R
since we know that U
0
allows us to Taylor expand the entropy (Equation 3). The Taylor expansion is
dened as
f (x
0
+a) = f (x
0
) +a
_
d f
dx
_
x=x
0
+
1
2!
a
2
_
d
2
f
dx
2
_
x=x
0
+...
thus we nd
R
(U
0
1
) =
R
(U
0
)
1
(
R
/U)
V,N
+...
=
R
(U
0
)
1
/
R
(U
0
2
) =
R
(U
0
)
2
(
R
/U)
V,N
+...
=
R
(U
0
)
2
/
thus we nd
R
=(
1
2
)/
and we nally nd that
P(
1
)
P(
2
)
= e
(
1
2
)/
thus the ratio of the number of particles in a particular quantu state 1 to the number in a particular state 2
is given by the ratios of their probabilities
N
1
N
2
=
P(
1
)
P(
2
)
= e
(
1
2
)/
we know that the density is dened as
=
m
V
N
thus we know that
1
=
m
V
N
1

2
=
m
V
N
2
and the relative density is given by
=

1
2
=
N
1
N
2
= e
(
1
2
)/
which is simply the Boltzman factor. Since we also know that the centrifugal force is dened as
F
c
= m
2
r
and the energy is given by
=
Z
F dr =
1
2
2
r
2
50
thus we know that
=
(r)
(0)
= e
1
/
thus we nd the relative density to be given as
= e
1
2
m
2
r
2
a plot is given as
Problem # 2
Show that for a system in thermal contact with a resevoir = lnZ +U/. This is a very useful result,
as you will see in (b) below.
Consider a crystalline solid containing N atoms whose nuclei have spin one, so hat each nucleus can
be in one of the three states m
s
= 1, 0, 1. We assume that the electric charge distribution in the nucleus
is ellipsoidal, so that the energy of a nucleus depends on its spin orientation with respect to the internal
electric eld of the crystal. Thus, the energy is for m
s
= 1 or -1, and zero for m
s
= 0.
a) Find an expression for the nuclear contribution to the internal energy, U.
First we need to show that
= lnZ +
U
we can do this by knowing that the free energy is dened

F =lnZ F =U
putting these two expressio equal to each other yields
lnZ =U
51
which reduces to
= lnZ +
U
Next we need to nd the average energy of the system (ensemble average) this is given by
U =
s
=
where
=
l
p(l) =
1
Z
l
e
l
/
where we often use = 1/, using this we get
=
l
p(l) =
1
Z
l
e
and the trick we can use
=
l
e

=
1
Z
_
_
=
lnZ
to put this back in terms of we just simply need to use the chain rule
Z
=
Z
=
Z
2
_
thus
=
1
Z
2
Z
=
2
lnZ
Thus the energy is given by

U = =
2
lnZ
(3.4)
This results allows us to write the energy of a system by just knowing what the partition function is.
b) Write down the partition function Z, of a single nucleus, and hence the partition function Z for N
nuclei. Hence, nd the entropy of the solid.
We know that the partition function is dened as
Z =
s
e
s
/
and we know the m
s
=1
s
= and for m
s
= 0
s
= 0. Thus we nd thet the partition function for this
system is given by
Z
N
= (1+2e
/
)
N
and the entropy of the solid is given by
= NlnZ +
U
52
using Equation 4 and the partition function we nd the entropy to be given as
= Nln(1+2e
/
) +
ln(1+2e
/
)
now we just need to nd

ln(Z
N
)
=
N
Z
Z
and we nd
(1+2e
/
) = 2

(e
/
)
letting
u =
2
thus we nd
ln(1+2e
/
)
=
2N
e
/
1+2e
/
thus we nd the total entropy to be given as
= Nln(1+2e
/
) +
2N
e
/
1+2e
/
a plot is given by
Where we plot / instead of /.
c) By directly counting the number of accessible states, calculate the entropy as 0 and . Show
that your expression in (b) reduces to these values.
Since we know that the probability goes as
p =
1
g
thus the multiplicity for 1 particle goes as
g =
1
p
53
and the multiplicity for N particles is given by
g(N) =
_
1
p
_
N
and as we know all the states are equally probable thus
g(N) = 3
N
p =
1
3
and thus at this limit the entropy is
= lng = Nln3
at the other extreme when 0 we know that all particles will all be in the ground state and thus the
probability is
p = 1 g = 1
N
and the entropy is
= lng = Nln1 = 0
now to show this with our previous solutions we just need to take the limits of our function to nd
In the limit that goes to 0
lim
0
ln(1+2e
/
) +
2
e
/
1+2e
/
0
this makes sense because we know if the temperature goes to 0 then the entropy goes 0.
In the limit that we nd
lim
ln(1+2e
/
) +
2
e
/
1+2e
/
ln3
which also makes sense, as the temperature goes to innity the entropy converges to a constant number.
d) Calculate the heat capacity C
V
of the crystal, and nd its temperature dependence for high . Make a
sketch of C
V
vs .
We know that the heat capacity is dened as
C
V
=
_
U
_
V
at constant volume. We know that the energy is given as
U =
2
lnZ
= 2N
e
/
1+2e
/
we need to nd
U
= 2N

_
e
/
1+2e
/
_
54
Using the quotient rule
x
_
f
g
_
=
g f
g
g
2
if we say
f = e
/
f
2
e
/
and
g = 1+2e
/
g
=
2
2
e
/
thus
U
= 2N
_
(1+2e
/
)(/
2
)e
/
e
/
(2/
2
)e
/
(2e
/
+1)
2
_
this can be simplied by factoring out a term
U
=
2N
2
2
e
/
_
1+2e
/
2e
/
(2e
/
+1)
2
_
=
2N
2
2
e
/
(1+2e
/
)
2
thus the heat capacity for this system is given by
C
V
=
2N
2
2
e
/
(1+2e
/
)
2
in order to sketch this function we can write it in a more suggestive form and use IDL to plot it, if we let
x =

we can write the heat capacity as

C
V
= 2Nx
2
e
x
(1+2e
x
)
2
and the plot is given as
55
Problem # 3 Free energy of a two state system
a) Find an expression for the free energy as a function of of a system with two states, one at energy 0
and one at energy .
Since we know that the partition function gives
Z = 1+e
/
and the free energy is dened as
F =lnZ
thus the free energy is given by
F =ln(1+e
/
)
b) From the free energy, nd expressions for the energy and entropy of the system.
The entropy is dened as
= lnZ +
U
but we know the energy is dened as

U =
2
lnZ
56
thus
= lnZ +
lnZ
where
lnZ
_
e
/
1+e
/
_
thus the entropy is dened as
= ln(1+e
/
) +

_
e
/
1+e
/
_
with a plot given by
Problem # 4 Magnetic susceptibility
a) Use the partition function to nd an exact expression for the magnetization M and the susceptibility
dM/dB as a function of temperature and magnetic eld. The result for the magnetization is
M = nmtanh(mB/), as derived in (46) by another method. Here n is the particle concentration.
We know that the average magnetic moment is given as
m() =
1
Z
l
m
l
e
l
57
what are the states? there are only two states, 1 toward the eld and one opposing the eld
m
= +m
=mB spin up
m
= m
= mB spin down
and we also know that B = H, now we nd the partition function to be
Z = e
+e
= e
mB
+e
mB
so the expectation value is now
m() =
me
mB
me
mB
e
mB
+e
mB
= m
sinh(mB)
cos(mB)
= mtanh(mB)
thus
m() = mtanh(mB)
but we are looking for the moment for all N spins
M() = Nm() = Nmtanh
_
Bm
_
but we know that
M() =
Nm()
V
= nmtanh
_
Bm
_
n =
N
V
thus
M() = nmtanh
_
Bm
_
we can also nd the suceptibility to be
=
dM
dB
=
nm
2
sech
2
_
mB
_
thus
=
nm
2
sech
2
_
mB
_
b) Find the free energy and express the result as a function only of and the parameter x M/nm.
We know that the free energy is given as
F =lnZ
and we know that the partition function is given as
Z = e
mB
+e
mB
thus the free energy is given as
F =ln(e
mB
+e
mB
) =ln2cosh
_
mB
_
58
and to put it in terms of x M/Nm we simply do
x =
M
Nm
= tanh
_
mB
_
thus
mB
= tanh
1
(x)
we also know that
cosh
2
(x) sinh
2
(x) = 1 cosh(x) =
1
_
1tanh
2
(x)
and nally we nd that
F =ln(
2
1x
2
)
c) Show that the susceptibility is = nm
2
/ in the limit mB .
we know that for large x we nd
lim
x
tanh(x) 1
In the limit that mB/ 1 or high temperature
M() nm
_
Bm
_
=
nm
2
B
and
=
nm
2
we plot M/nm vs mB/

59
Problem # 6
N molecules of N
2
are condensed onto a surface of area LL. The molecules do not interact with each
other, so each molecule is completely free to move translationally in 2 dimensions (along the surface) and
to vibrate, with vibrational frequency = 10
12
Hz and non-degenerate energy levels = s with s
being any positive integer (ignoring zero point energy). Assume the N
2
are distinguishable and that L is
large so that
2
2M
_
L
_
2
the following relationship will be useful
n=0
aq
n
=
a
1q
for |q| < 1
this is known as a geometric series.
a) Write down an exact expression for the energy U as a function of temperature . You do not need to
derive this expression but please justify either in words or from simple mathematical expressions
where it comes from.
We know that the translational energy given by a 1-D ideal gas is given by
U =
1
2
N
but since we have a 2-D system (2 degrees of freedom) we nd the total translational energy to be
U
tran
= N
This comes from solving for the energy levels and wavefunctions for particles in an LL box. For N
distinguishable particles, the partition function is
Z
N
=
_

s=0
(e
/
)
s
_
N
and using the expression for the geometric series we nd
Z
N
=
_
1
1e
/
_
N
we know that the energy is given as
U
vib
=
2
lnZ
=
2
N
(1e
/
)
(1e
)
2
e
/
2
=
N
e
/
1
thus the total energy of this system is given by
U
tot
= N +
N
e
/
1
60
b) Calculate the exact specic heat C
V
as a function of temperature and plot this showing units and
values on the axes.
We know that the specic heat is dened as
C
V
=
_
U
_
V
= N+
N
(e
/
1)
2
e
/
2
thus the specic heat is given by
C
V
= N
_
1+
_
_
2
e
/
(e
/
1)
2
_
Problem # 7
Consider N particles, each of which can be found in one of four states: the ground state has energy
1
=0 and is non-degenerate. The rst excited state has energy
2
= and is triply degenerate. The system
is in thermal contact with a resevoir at temperature .
a) Find the partition function for the system.
We know that the partition function of this system is given by
Z =
s
e
s
/
= 1+3e
/
= 1+3e
and for N particles we nd

Z
N
=
_
1+3e
_
N
b) Find U, F, and as a function of .
We know that the energy is dened as
U =
2
lnZ
=
1
Z
Z
we know what Z is now we need to nd

Z
= N[1+3e
]
N1
[3e
]
which can simplify into
U =
3N
e
/
+3
To nd the free energy we know that
F =lnZ
N
= N[1+3e
/
]
and the entropy is given as
= lnZ
N
+
U
= Nln[1+3e
/
] +
3N
_
1
e
/
+3
_
61
c) Find the specic heat C
V
as a function of and calculate its low and high limits.
We know that the heat capacity is given as
C
V
=
_
U
_
V
where we can see that
U
=
3N
(e
/
+3)
2
e
/

2
= 3N
_
_
2
e
/
(e
/
+3)
2
thus the heat capacity is given as
C
V
= 3N
_
_
2
e
/
(e
/
+3)
2
for high temperature limit we can see that
e
/
1+

1
thus
C
V
=
3N
16
_
_
2
for the low temperature limit we can see that gives
e
/
3
thus
C
V
= 3N
_
_
2
e
/
Problem # 8
Consider again the system described in Problem 7. For each particle, the ground state is a spin singlet
with s = 0 and = 0 and the rst excited state is a spin triplet with s = 1. With the applied magnetic eld
B =0, the three s = 1 states have equal energy as described above. (The energysplitting in B =0 is due
to effects other than magnetiuc eld, specically what are called crystal eld splittings). In a magnetic
eld, the s = 0 state still has energy 0 (m
s
= 0), but the s = 1 states split into three states (m
s
= 1, 0) ,
with energies
s
= +2
B
B, , 2
B
B for m
s
=1, , +1 respectively where
B
is the Bohr magneton.
a) Calculate the partition function as a function of B and .
We know that the partition function for this system is given by
Z
N
=
s
e
s
/
= [1+e
(+2
B
B)/
+e
(2
B
B)/
+e
/
]
N
b) Calculate the expectation value of the moment M of the system as a function of eld B (at xed
temperature ). Hint M = Nm
s
62
Since we know that the expectation of the moment is given as
M = Nm
s
= N
1
Z
s=0
m
s
e
= N
1
Z
[e
(2
B
B)/
e
(+2
B
B)/
]
this becomes
M = N
e
(2
B
B)/
e
(+2
B
B)/
Z
N
=
Ne
/
Z
N
[e
2
B
B/
e
2
B
B/
] =
Ne
/
2sinh(2
B
B/)
Z
N
Problem # 9
Consider a system that has 5 possible states, with two energy levels. The lowest energy level is doubly
degenerate (two states) with energy
1
= 0. The next energy level has threefold degeneracy (three states)
with energy
2
. It is in thermal contact with a resevior at temperature .
a) What is the probability ( as a function of temperature) that the system has energy 0?
We know that the probability that the system will have energy = 0 is given by
p( = 0) =
e
/
Z
=
2
Z
where the partition function is given by
Z =
s
e
s
/
= 2+3e
2
/
thus the probability is given as
p(0) =
2
2+3e
2
/
b) Calculate the energy U and the entropy (as a fucntion of ).
We know that the energy is given by
U =
1
Z
Z
where
Z
=3
2
e
2
thus the energy is given as
U =
3
2
e
2
/
2+3e
2
/
And we know that the entropy is dened as
= lnZ +
U
= ln[2+3e
2
/
] +
3
2
_
e
2
/
2+3e
2
/
_
thus we nd
= ln[2+3e
2
/
] +
3
2
_
e
2
/
2+3e
2
/
_
63
c) Calculate the energy and the entropy as goes to 0 and goes to innity. Briey discuss/explain your
answers.
We can see that as goes to 0 we nd
e
2
/
0
thus
U 0 ln2
as goes to 0, the system goes into the ground state which have = 0 U 0. As
e
/
1
thus we nd
U
3
2
(1
)
2+3(1
)
=
3
2
(1/)
53(/)
the entropy is found using the same method.
Problem # 10
a) Prove the Maxwell relation
_
V
_
=
_
p
_
V
for all systems. To do this, please start from
d(U,V) =
_
U
_
V
dU +
_
V
_
U
dV dU =dpdV
and the thermodynamic denition
F =U
calculate dF. From this, calculate p and in terms of derivatives of F (show your calculations of
the derivatives explicitely, i.e where they come from, dont just state the result) and from this, prove
the Maxwell relation.
We know that
d(U,V) =
_
U
_
V
dU +
_
V
_
U
dV =
dU
+
p
dV
we also know that
dU =dpdV
and
F =U
where
dF = dU dd =dpdV dd =pdV d
thus
_
F
V
_
=p
_
F
_
V
=
64
if we take the cross-derivatives
_

(p)
_ _

()
_
which yields
2
F
V
=
_
p
_
V
2
F
v
=
_
V
_
the order of the secon derivatives do not matter and thus we nd

_
p
_
V
=
_
V
_
b) There is one important variable which is held constant in the above Maxwell relation- what is it?
It is N that is held constant.
c) Show that the Maxwell relation is true for the ideal monatomic gas by explicitly calculating F, and p
and their derivatives for the ideal monatomic gas. Start from Z for the ideal monatomic gas, which
you do not need to re-derive
Z =
1
N!
(n
Q
V)
N
n
Q
=
_
M
2
2
_
3/2
We know that the free energy is given by
F =lnZ =ln
1
N!
(n
Q
V)
N
= [lnN! +Nlnn
Q
+NlnV]
we also know that the entropy is dened as
=
_
F
_
V,N
= N
lnn
Q
=N
1
n
q
n
Q
=N
3
2
n
Q
=
3
2
N
thus
= [lnN! +Nlnn
Q
+NlnV] +
3
2
N
and for the pressure we nd
p =
_
F
V
_
,N
=N
lnV
V
=
N
V
and we can nally show that
_
V
_
,N
= N
lnV
V
=
N
V
and
_
p
_
V,N
=
N
V
65
Chapter 4
Thermal Radiation and The Planck
Distribution
Roadmap
1. Electromagnetic Modes
2. Density of Nodes
3. The Rayleigh-Jeans classical theorem of electro-magnetic radiation
4. Planck theory of electro-magnetic theorem (Quantum theory)
5. Absorption and Emission of EM radiation
6. Phonos in a solid.
4.1 Electromagnetic Modes
If we have some cavity in thermal equilibrium then it is lled with EM radiation, if it is in thermal equi-
librium then the modes only depend on the temperature. We need to calculate this which gives rise to the
Planck distribution. The rst thing we need to do is nd the density of modes. The second thing is to nd
the mean oocupancy or mean energy of each mode using the Boltzman distribution. What are modes? You
get resonances with the length of the cavity or of the string is equal to an integer of its wavelength
L
1
=

2
L
2
= L
3
=
3
2
or a general expression is given by
= n
2
L
, n = 1, 2, 3, ...
where
= 2f =
2c
= n
c
L
to do this calculation we need to regard each mode as being equivalent to the simpe harmonic oscillator of
energy levels at that frequency. The energy of the SHO is given by
= n n = 1, 2, 3, ...
where n is the number of photons in that energy states.
66
4.2 Density of modes
Lets consider a cavity with sides L, lets have the waves propgate in the z direction. We have the electric
eld and the magnetic eld that are orthogonal to each other. There are also two different polarization that
are independent. Lets consider (for example) E
x
, next we write down the wave equation
2
E
x
=
_

2
x
2
+

2
y
2
+

2
z
2
_
E
x
=
1
c
2
2
E
x
t
2
but we know that
E
x
(x, y, z, t) = E
x
0
sin(t)sin
_
n
x
x
L
_
sin
_
n
y
y
L
_
sin
_
n
z
z
L
_
writing this in this form already places boundary conditions. Where they are that E
z
vanishes on all the
walls. Now we must substitute E
x
into the wave equation. We get the following
2
L
2
(n
2
x
+n
2
y
+n
2
z
) =
2
c
2
this gives us a relationship between all of then, , and the cavity. Thus
n
2
=
L
2
2
c
2
2
n =
L
c
n 0
we need to remember that this is in three dimensions. We now want to calculate the density of nodes for
this box.
D()d = number of modes between , +d
we now need to cosider an octant of a sphere, in fact we want to consider a shell that has a thickness dn
and a radius that we will call n, this shell contains a certain number of nodes. We need to nd
D()d = 2
1
8
4n
2
dn =n
2
dn
the 2 comes about from the two independent modes of polirization, then we need to consider that the
surface area is 1/8 times the surface of the sphere and the dn, thus we have
D() = n
2
dn
d
but we know what this is
dn
d
=
L
c
thus
D() =
L
2
2
c
2
2
L
c
=
_
L
c
_
3
2
and we nd
D() =
V
2
c
3
2
this is a very important result. This is step one of our calculation, we must now go to step two.
67
4.3 Rayleigh-Jeans Theory (1900) classical
By the Equipartition theorem, there is an average energy k
B
T per mode because of the two quadratic term
in E
2
and B
2
, this immideatley gives us a result for the energy in the black body spectrum
u() = D()k
B
T =
V
2
c
3
2
k
B
T
if we integrate over the entire spectrum to get the energy we will get the following
u
T
() =
Z

0
D()k
B
Td =
V
2
c
3
k
B
T
Z

0
2
d
we can see that this integral diverges. This cannot be true. It was know that the spectrum does not go to
innity. The classical theory worked well at low frequencies, but not at high frequencies. Then came Max
Planck who introduced the high frequency limit
u
T
()
2
e
/k
B
T
we now need to show where this came from.
4.4 Planck Theory (1903) Quantum Theory
This results will be the same as the QSHO. Lets consider a mode in our box with frequency , we want
to know what the average energy at a temperature T. Lets consider a resevior with one mode in a system
(box) and the resevoir is all the other modes. We know that we can solve this using the partition function
Z =
n=0
e
n/
where n is the number of photons in the mode and the energy is quantized. Thus =n, this is really the
difference between the classical theory and quantum theory. Lets nd the mean occupancy of that mode
n =

n=0
ne
n/
n=0
e
n/
if we write
y = e
/
thus
n =
ny
n
y
n
there is a simple trick to do this
n = y
d
dy
ln
n=0
y
n
these two expressions are equivalent. Now we know that
n=0
y
n
=
1
1y
68
and so we are left with
n =y
d
dy
ln(1y)
thus
n =
y
1y
=
1
1/y 1
and thus we get the result
n =
1
e
/
1
this is known as the Planck distribution. There are two points to make, This function takes care of the
ultraviolet catastrophe
1. Occupancy tends to zero as goes to zero
2. This whole theory dependend on the fact that we quantized the energy. Thus EM radiation can be
represented by photons of discrete energy. The results implies that the energy is in fact quantized in
units of (photons). This was the introduction in Quantum theory.
We can now write the energy density as
u()d =nD()d
where is th energy of the mode and n is the average number of photons with some energy. Thus
u()d =
V
3
d
2
c
3
(e
/
1)
we can write this more suggestively as
x =

this gives
u()d =
V
2
c
3
_
_
4
_
x
2
dx
e
x
1
_
thus we can see that the energy goes to the fourth power of the temperature. It will also give us a very useful
scaling argument. The derivative of this function gives us the turning point of the energy distribution. We
nd the maximum to be given by
d
dx
_
x
2
e
x
1)
_
x
max
=

max
= 2.82
this gives us the following scaling law This results gives us what is known as Wiens law
max
1
=

max
2
this enables one to measure temperatures from the black body spectrum, e.g stars and pyrometers. Lets
look atb this results at the limits.
69
The classical limit / 1, the discrete energy levels is smeared out. We get the following form
u() =
V
3
2
c
3
(/)
=
V
2
2
c
3
rst we can see that drops out and also this is precisely the Rayleight-Jeans result.
The Quantum limit / 1, energy levels are very discrete
u() =
V
3
2
c
3
e
/
this also comes from Wiens law (1896).
The nal thing we need to do is integrate this to nd the total energy in the cavity. Thus the total energy
in the cavity is given by
u
=
Z

0
u()d
it is convinient to take the formed introduced previoulsy
u
=
V
2
c
3
_
_
4
Z

0
x
3
e
x
1
dx
=

2
V
4
15
3
c
3

4
where we have said
Z

0
x
3
e
x
1
dx =

4
15
thus we nd the total energy of the cavity is given by
u
=

2
V
4
15
3
c
3
this result is independent of the nature of the cavity or of materials placed inside of it. One othet thing that
we can work out is the entropy.
4.5 Entropy
We know that
d = du+ pdV
thus, at constant volume we have
d =
du
where
u
=

2
V
4
15
3
c
3
du
=
4
2
V
3
15
3
c
3
d
and so we nd
d =
4
2
V
2
15
3
c
3
d
if we now integrate both sides we nd
=
4
45
2
V
3
3
c
3
70
4.6 Absorption and Emission of Blackbody radiation
The Energy emmited by a blackbody, where the number of photons emmtitted per unit area per second
N() =
1
4
n()c
we can compare this with the kinetic theory of gases. With this in mind it is simle to write the power
emmited for the blackbody. Where the power emmited per unit area in the frequency range of + is
given by
P
l
()d =
1
4
n()c()d
now we know that
n() =
u
T
()
V
energy per unit volume
thus the total energy is given by the following
total emmited power =
Z

0
P
l
()d =
1
4
c
Z

0
u
T
()d
V
=
1
4
u
tot
V
where
u
tot
=

2
V
4
15
3
c
3
thus we nd
P
tot
=

2
4
60
3
c
2
=
SB
T
4
this expressions denes the Stephan-Boltzman constant
B
=

2
k
4
B
60
3
c
2
= 5.6710
8
W
m
2
K
4
this quantity is know very precisely. We will now spend a few minutes talking about absorption and
emmision of blackbodies.
4.7 Absorption and Emission
These are the kinds of objects that we might expect to nd.
1. Blackbody-is an object that absorbs/radiates all the radiation incident on it. We dene this property
in terms of an absorption coefcient.
a() = 1 aborptivity
we also have what is called a grey body
a() < 1
we also have colored blackbodies
a() depends on frequency
and lastly we have what is called a mirror
a() = 0
given these different properties, how is it that all this objects are at the same temperature in the box?
71
4.7.1 Kirchoffs Laws
We can dene emmisivity e(), which is simply the fraction of electromagnetic radiation compared to
that emitted by a black body emmited at the same temperature. Kirchoffs law gives
a() = e()
what happens at the microscopic level? If we suppose that we have a solid with many atoms that also have
vibration. There are two energy levels. This means that we absorb and emit strongly at some frequency .
This is know as the principle of detailed balance. There are lots of good example of this, i.e a silver tea
pot should be polished to keep your tea warm for a long time. This is because if the tea pot is very shiny
than it will be a poor observer, thus it is also a bad emmiter. Another example is the green house effect.
If you have a green house and it is made of glass and inside you have some bushes. What happens is that
UV and optical can pass relatively easy, thus the plants absorb and then re-emit at different frequency.
This re-emmited radiation is not able to escape thru the glass because of the glass. Thus the UV is trapped
inside the green house. The glass absorbs and emmits strongly in the infrared, hence the green house
warms up. There is also Global Warming, this is due to the gases and clouds in the atmosphere. On
clear nights it gets colder than if it is cloudy. The clouds act as an absorbing and emmiting medium for
infrared radiation.
4.8 Phonos: Debye Model
If we think of latice waves then we are really thinking about sound waves, thus they propogate at the
velocity of sound v
s
, there are three possible independent modes. The rst is a longitudinal wave, back
and forth motion (spings). An alternative is a transverse vibration, of which there are two (up and down)
or perpendicular (in and out). We need to apply the theory of EM radiation to this situation. We need to
gure out the density of modes for this picture.
4.8.1 Density of Modes
There is a distinction between solids and EM radiation. For EM waves, there is an unlimited numer of
possible modes. On the other hand, sound waves in a solid, the number of modes is bounded. Each
atom has three degrees of freedom, thus the maximum number of modes for each atom there are 3 modes
and for N atoms there are 3N modes. If we consider a single transverse wave, it takes discrete points to
identify that wave. If we try to draw the frequency with only 2 points, then this has no meaning. There is
a minimum wavelength. We can recall that for photons (2 modes)
D() =
V
2
2
c
3
but for phonons (3 modes)
D() =
3V
2
2
2
v
3
s
there is an additional twist. This is cut off at
D
, which is the Debye frequency (highest frequency where
we can have vibrations). Thus
3N =
Z

D
0
D()d =
3V
2
2
v
3
s
Z

D
0
2
d =
V
3
D
2
2
v
3
s
72
thus the Debye frequency is given by
D
=
_
6
2
v
3
s
_
N
V
__
1/3
this results is independent of the size of the solid. The velocity of sound is
v
3
s
=
V
3
D
6
2
N
if we plug this into the previous equation we nd
D() =
3V
2
2
2
6
2
N
V
3
D
= 9N

2
3
D
thus this scales as N
2
where
2
as for photons. The second step is to gure out the population of these
modes.
4.9 Total Energy
The total energy at temperature T is given by
u
tot
(T) =
Z

D
0
D()nd
where n is the average number of phonos in a mode, is the phonon energy, and D() is the density
of modes. Thus we nd
u
tot
(T) =
9N
3
D
Z

D
0
3
d
e
/k
B
T
1
so we can write this integral in a dimensionless form
x =

k
B
T
, x
D
=

D
k
B
T
=
k
B
T
D
k
B
T
=

D
T
where
D
is the Debye temperature
D
=

D
k
B
=
xk
B
T
d =
k
B
T
dx
thus we will get the following
u(T) =
9N(k
B
T)
4
3
D
Z
x
D
0
x
3
e
x
1
dx
where
Z
x
D
0
x
3
e
x
1
dx
is dimension-less, this can only be solved numerically or by lookin at the extremes (limits).
73
4.9.1 Low temperature
x
D
1 or k
B
T
D
= k
B
D
, we can replace x
D
by innity in the upper limit, and hence
Z

0
x
3
e
x
1
dx =

4
15
thus in this limit
u(T) =
9N(k
B
T)
4
3
D
4
15
thus
u(T) =
3
4
N(k
B
T)
4
5(
D
)
3
this is the total energy of a solid at low temperatures. It is more useful to talk about the heat capacity
C
V
=
_
U
T
_
V
=
12
4
Nk
B
5
_
k
B
T
D
_
3
thus
C
V
=
12N
4
5
k
B
_
T
D
_
3
this is called the Debye T
3
law. All non-magnetic insulator obey this law. But metals do not obey this
because they have electronic contribution.
4.9.2 High Temperature
x
D
1 or k
B
T
D
or T
D
, this is a simple case
Z
x
D
0
x
3
e
x
1
dx
thus we can expand e
x
as 1+x
Z
x
D
0
x
2
dx =
x
3
D
3
and we nd the total energy to be
u(T) =
9N(k
B
T)
4
3
D
x
3
D
3
which yields
u(T) = 3Nk
B
T
wher 3N is the total number of atoms in the crystal. We have N atoms that act as 1D harminic oscillator,
this is in fact a 3D problem. This is the equipartition theorem applied to N 3 dimensional simple harmonic
oscilator. We can easily derive the heat capacity
C
V
= 3Nk
B
this is a very important results, this is known in chemistry as the Dulong and Petit law which is
25 joule deg
1
mole
1
74
we can also plot C
V
vs the temperature we nd, at low temperature we have the famous T
3
law and at high
temperature we nd that this is independent of temperature.
D
is a measured quantity, a few examples
are given as
Indium 108K
Copper 343K
Diamond 1500K
there is a clear temperature dependence and hardness of the material. Hard materials are stiff therefore
they have a high value of spring constant, thus high
D
high
D
. We should expect that there should
also be a contribution from the electric contribution to the heat capacity. The metals have free electrons
that apperently do not contribute signicantly to C
V
at room temperature.
4.10 Fluctuations in Phonon Energy for Temperatures
D
in T
3
Limit
We have a resevoir and a system, we want to see howthe uctuations scale with temperature. We remember
that
(u)
2
=
_
u
_
=
2
_
u
_
= (k
B
T)
2
_
u
k
B
T
_
= k
B
T
2
C
V
we need to recall the expressio for the energy in this limit
u(T) =
3
4
(k
B
T)
4
N
5(
D
)
3
=
3
4
5
k
B
T
4
N
3
D
we know that the energy is in the form of
u = AT
4
C
V
=
_
u
T
_
= 4AT
3
(u)
2
u
2
=
k
B
T
2
4AT
3
uAT
4
=
4k
B
T
u
=
20k
B
T
3
D
3
4
k
B
T
4
N
=
20
3
4
1
N
3
D
T
3
=
_
20
3
4
__
D
T
_
3
1
N
if we take a small thin lm with l = 100m w = 10m, and h = 0.1m which gives us a volume of
V = 10
16
m
3
where the typical density is 10
28
m
3
, thus we hav e approximately N 10
12
atoms, and also
D
300 K T = 0.01 K
if we put all these number in we nd
(u)
2
u
2

1
15
_
300
0.01
_
3
10
12
2
thus we have large uctuations in the energy, in fact, uctuations results break down because the energy
of the system cannot be negative.
75
4.11 Summary
We started talking about electromagnetic radiation. The rst thing was the density of modes
D() =
V
2
2
C
3
we then found the famous Planck distribution
n =
1
e
/k
B
T
1
and the energy density is given by
u() =nD() =
V
3
2
c
3
(/)
and the total energy is given by
u
=

2
V
4
15
3
c
3
We also found the total power to be given as
P =
SB
T
4
where
SB
=

2
k
4
B
60
3
c
2
= 5.67810
8
Wm
2
K
4
we also derived Kirchoffs laws
a() = e()
we also discussed phonos
C
V
=
12
4
5
Nk
B
_
T
D
_
3
T
D
and
C
V
= 3Nk
B
T
D
Problem # 1
A wire of a radius r
0
is coincident with the axis of a metal cylinder of radius R and length L. The
wire is maintained at a positive potential V with respect to the cylinder. The whole system is at some high
temperature T. As a result, electrons emitted from the hot metals form a dilute gas lling the cylindrical
container and in equilibrium with it. The density of these electrons is so low that their mutual electrostatic
interactions can be neglected.
76
a) Use Gausss theorem to obtain an expression for the electrostatic eld which exists at points at a radial
distance r from the wire (r
0
< r < R). The cylinder of length L may be assumed to be very long so
that end effects are negligable.
We know that Gausss law is given by
Z
E da =
q
enc
0
where we know that
Z
da = A = 2rL
thus we nd the electric eld to be given by
E =
q
enc
2rL
0
but we know that the charge enclosed can be found through the potential
V =
Z
E dl =
q
enc
2L
0
Z
R
r
0
1
r
dr =
q
enc
2L
0
ln
_
R
r
0
_
thus
q
enc
=
2L
0
ln(R/r
0
)
V
thus we nd the electric eld to be given by
E =
V
r ln(R/r
0
)
(4.1)
b) In thermal equilibrium, the electrons form a gas of variable density which lls the entire space between
the wire and cylinder. Using the result of part (a), nd the dependence of the electric charge density
(relative density) on the radial distance r.
We know that the relative density is given by the Boltzman factor, since we can assume that there are N
1
and N
2
particles having energy
1
and
2
respectively then we can write the relative density as
=
(r
1
)
(r
2
)
= e
((r
1
)(r
2
))/
77
we have proved this result elsewhere. Thus we need to nd what the energy is at distance r
1
and r
2
. We
know that the energy due to some charge and potential is given by
(r) =
p
2
2m
qV(r)
thus we nd that
= q[V(r
2
) V(r
1
)]
if we let
V(r) =C
Z
r
r
0
1
r
dr =Cln
_
r
r
0
_
thus
V(r
1
) =Cln
_
r
1
r
0
_
V(r
2
) =Cln
_
r
2
r
0
_
this allows us to nd thet the change in energy is given by
=Cq
_
ln
_
r
2
r
0
_
ln
_
r
1
r
0
__
where we know that C is given from Equation 1 as
C =
V
ln(R/r
0
)
thus we nd the relative density to be given as
=
(r
1
)
(r
2
)
= e
/
= e
Cq
_
ln
_
r
2
r
0
_
ln
_
r
1
r
0
__
/
if we choose appropriate radius r
1
= r
0
and r
2
= r
2
we nd the the relative density is given by
=
(r
0
)
(r
2
)
= e
V
ln(R/r
0
)
q
_
ln
_
r
2
r
0
__
/
Problem # 2 Zipper Problem
A zipper has N links; each link has a state in which it is closed with energy 0 and a state in which it
is open with energy . We require, however, that the zipper can only unzip from the left end, and that the
link number s can only open if all links to the left (1,2,...,s-1) are already open.
a) Show that the partition function can be summed in the form
Z =
1exp((N+1)/]
1exp(/)
First of all, we know that the number of states is given by s = (1, 2, 3, ..., s 1) and we also know that the
total energy is given by
s
= n, thus we can write the partition function as
Z =
N
s=0
e
s
/
=
N
n=0
e
n/
=
N
n=0
(e
/
)
n
78
this resembles a geometric series of the form
k
n=0
ar
n
= a
1r
k+1
1r
thus we can see that the partition function is simply
Z =
1exp((N+1)/]
1exp(/)
b) In the limit , nd the average number of open links. The model is a very simplied model of the
unwinding of two-stranded DNA molecules.
We know that at this limit, the partition function reduces to
Z =
1
1exp(/)
and we know that the average number of open links is given by
N =
N
n=0
np(l) =

N
n=0
ne
n/
Z
if we expand the numerator to the rst few terms we nd
N = (e
/
+2e
2/
+3e
3/
)(1e
/
)
if we let
x = e
/
we nd that the average number of open links is given by
N = (x +2x
2
+3x
3
)(1x)
Problem # 3 Elasticity of Polymers
The hermodynamic identity for a one-dimensional system is
d = dU f dl
when f is the external force exherted on the line and dl is the extension of the line. By analogy with
p =
_
V
_
U
we form
f =
_
l
_
U
the direction of the force is opposite to the conventional of the pressure, this is due to the fact that (/l)
is always negative.
We consider a polymeric chain of N links each of length , with each link equally likely to be directed
to the right and to the left.
79
a) Show that the number of arrangements that give a head-to-tail length of l = 2|s| is
g(N, s) +g(N, s) =
2N!
(
1
2
N+s)!(
1
2
Ns)!
we know that the multiplicity is dened as
g(N, s) =
N!
(
1
2
N+s)!(
1
2
N s)!
we can also see that
l = N = 2|s| 2|s| = N
we can also see that this system can only be in two possible states
g(N, s) state 1 g(N, s) state 2
we can add these two multiplicity functions (which gives the total multiplicity of the system), we simply
get
g(N, s) +g(N, s) =
2N!
(
1
2
N+s)!(
1
2
Ns)!
b) For |s| N show that
(l) = ln[2g(N, 0)]
l
2
2N
2
since we know that the entropy is dened as
= ln[g(N, s)]
and the Sterling approximation to the multiplicity is given by
g(N, s) g(N, 0)e
2s
2
/N
s =
l
2
we nd that the multiplicity is given as
g(N, s) = g(N, 0)e
l
2
2N
2
thus the entropy yields
= ln[g(N, 0]
2s
2
N
in our case we know that
g(N, s) = g(N, s) +g(N, s) = 2g(N, s)
thus we nd that the entropy for this system is given by
= ln[2g(N, 0)]
l
2
2N
2
80
c) Show that the force at extension l is
f =
l
N
2
The force is proportional to the temperature. The force arises because the polymer wants to curl up: the
entropy is higher in a random coil than in an uncoiled conguration. Warming a rubber band makes it
contract; warming a steel wire makes it expand.
Since we know what the entropy is for our system and we also know that the force is given by
f =
_
l
_
we simply need to differentiate the entropy as a functio of length, which yields
l
=
l
N
2
Substituting this into the force yields
f =
l
N
2
Problem # 4 Earths Steady State Temperature
The surface temperature of the Sun is T
0
= 5500 K; its radius is R
sun
= 710
10
cm while the radius of
the Earth is R
earth
=6.3710
8
cm. The mean distance between the Sun and the Earth is r =1.510
13
cm.
In the rst approximation one can assume that both the Sun and the Earth absorb all electromagnetic
radiation incident upon them. The Earth has reached a steady state so that its mean temperature T does
not change in time in spite of the fact that the Earth constantly absorbs and emits radiation.
a) Find an approximate expression for the temperature T of the Earth in terms of the astronomical
paramters mentioned above.
We know that the power recieved at the Earth from the sun is given by
P(earth) = F
sun
A
earth
=
L
sun
4r
2
R
2
earth
=
L
sun
4r
2
R
2
earth
where r is the distance from the Sun to the Earth r = 1 AU. We also know that the luminosity of an object
is given by
L
sun
= 4R
2
sun
T
4
sun
thus the power the Earth receives from the sun is given by
P(earth) =
R
2
sun
T
4
sun
R
2
earth
r
2
we know that the power emmited by the Earth is given
P(earth) = 4R
2
earth
T
4
earth
setting these two expressions together we nd that the temperature of the Earth is given by
R
2
sun
T
4
sun
R
2
earth
r
2
= 4R
2
earth
T
4
earth
81
thus
T
earth
= T
sun
_
R
sun
2r
b) Calculate this temperature T numerically.
Since we know that R
sun
= 710
8
m and r = 1.510
11
m and T
sun
= 5500 K we nd the temperature of
the Earth to be
T
earth
= 5500 K
(710
8
)
2(1.510
11
)
this is simply
T
earth
= 265.67 K
Problem # 5 Number of Thermal Photons
Show that the number of photons s
n
in equilibrium at temperature in a cavity of volume V is
N = 2.404
2
V(/c)
3
where we know that the entropy is given by
=
_
4
2
V
45
_
_

c
_
3
whence /N 3.602. It is believed that the total number of photons in the universe is 10
8
larger than the
total number of nucleons (protons, neutrons). Because both entropies are of the order of the respective
number of particles, from
= N
_
ln(n
Q
/n) +
5
2
_
the photons provide the dominent contribution to the entropy of the universe, although the particles domi-
nate the total energy. We believe that the entropy of the photons is essentially constant, so that the entropy
of the universe is approximately constant with time.
We know that
s
n
=
1
e
n
/
1
thus we can see that
N =
n
s
n
=
n
1
e
n
/
1
where the sum is over the triplet of integers n
x
, n
y
, n
z
. Positive integers alone will describe all independent
modes. We replace the sum over n
x
, n
y
, n
z
by an integral over the volume element dn
x
, dn
y,
dn
z
in the
space of the mode indices. That is we set
N =
Z

0
n
2
dn
e
n
/
1
d
82
where d is the solid angle given by
d =
Z
2
0
d
Z

0
sind = 4
thus we nd
N = 4
Z

0
n
2
dn
e
n
/
1
to make our lives easier, lets just integrate over one octant, this gives us
N =
4
8
Z

0
n
2
dn
e
n
/
1
since we know that
n
=
nc
L
n
2
=
_
L
n
c
_
2
dn =
L
c
d
we are now able to write
N =

2
Z

0
n
2
dn
e
nc/L
1
if we introduce the unitless quantity
x =
cn
L
n =
L
c
x dn =
L
c
dx
using these identities we are now able to write
N =
_
L
c
_
3
1
2
Z

0
x
2
e
x
1
dx =
2
V
_

c
_
3
Z

0
x
2
e
x
1
dx
where we have looked up the solution to
Z

0
x
2
e
x
1
dx 2.404
thus we nd
N = 2.404
2
V
_

c
_
3
Problem # 6 Average Temperature of the Interior of the Sun
a) Estimate by a dimensional argument or otherwise the order of magnitude of the gravitational self-
energy of the Sun, with M
sun
= 2 10
33
g and R
sun
= 7 10
10
cm. The gravitational constant G
is 6.6 10
8
dyne cm
2
g
2
. The self-energy will be negative referred to atoms at rest at innite
seperation.
The energy due to a gravitational eld produced my some mass M is given by
U =
GM
2
r
given the quantities for M, G and R we nd
U =
GM
2
r
3.8110
41
Joules
83
b) Assume that the total thermal kinetic energy of the atoms in the Sun is equal to
1
2
times the gravita-
tional energy
K =
1
2
U Virial Theorem
this is a result of the Virial Theorem in mechanics. Estimate the average temperature of the Sun.
Take the number of particles as 1 10
57
. This estimate gives somewhat too low a temperature,
because the density of the Sun is far from uniform. The range in central temperature for different
stars, excluding only those composed of degenarate matter for which the law of perfect gases does
not hold (white dwarfs) and those which have excessively small average densities (giants and super
giants), is between 1.5 and 3.010
7
degrees.
Since we know that the total therma kinetic energy is given by
K = Nk
B
T =
1
2
U = 1.910
41
joules
thus we nd that the temperature will be given as
T =
U
2Nk
B
=
1.910
41
joules
Nk
B
since we know the number of particles and what the constant k
B
we nd that the temperature is
T =
1.910
41
joules
110
57
1.3810
23
joules
K 7.2410
6
K
Problem # 7 Angular Distribution of Radiant Energy Flux
a) Show that the spectral density of the radiant energy ux that arrives in the solid anle d is cu
cos
d/4, where is the angle the normal to the unit area makes with the incident ray, and u
is the
energy denisty per unit frequency range.
84
Since we know that the differential energy dE is given by
dE = cdtu
ddA
where we also know that the incident beam will not contribute anything to the ux if the angle of
incidence is 90 degrees or /2. Thus I know that my differential area dA is really given by dA = cosdA,
this will account for any angle dependence on the incidence of the beam. Thus we nd
dE = cdtu
dcosdA
or this can also be written as
dE
dt
= cu
cosddA
we must also normalize this over all solid angle 4 ster-radians, thus we nd
dE
dt
= cu
cosdA
d
4
we also know that the ux is dened as
F() =
dE
dtdA
thus we nd that the ux density is given as
F() = cu
cos
d
4
85
b) Show that the sum of this quantity over all incident rays is (1/4)cu
.
We know that the sum of this quantity will be given by the integral
F
tot
=
cu
4
Z
2
0
d
Z
/2
0
sincosd
this is given as
F
tot
=
cu
2
Z
/2
0
sincosd
we know that the integral
Z
/2
0
sincosd =
1
2
thus we nd the total ux integrated over the solid angle is given by
F =
1
4
cu
Problem # 8 Free energy of a photon gas

a) Show that the partition function of a photon gas is given by
Z =
n
[1e
n
/
]
1
where the product is over the modes n.
We know that the partition function for a photon in a mode n is given by
Z =
n
e
n
/
This sum is of the form x
n
with x exp(c/L). Because x is smaller than 1, the innite series may
be summed and has the value
Z =
1
1e
n
/
= [1e
n
/
]
1
since we know that for many photons in a gas the partition function can be written as
Z
n
= Z
1
Z
2
Z
3
...Z
n
since this are distinguishable photons in a given energy state n. Thus the partition can be expressed as a
product of the form
Z =
n
[1e
n
/
]
1
b) The Helmholtz free energy is found directly as
F =
n
ln[1e
n
/
]
86
Transform the sum to an integral; integrate by parts to nd
F =
2
V
4
45
3
c
3
turning this sum into an integral yields
F = 2
1
8
4
Z

0
n
2
ln[1e
n
/
]dn
where the 2 comes from the two polirizations, the 1/8 comes from the fact that we are only integrat-
ing over one octant and the 4 comes from integrating over the entire solid angle of a sphere. We
also know that
n
=
nc
L
thus the free energy (in integral form) is
F =
Z

0
n
2
[1e
nc/L
]dn
letting
x =
nc
L
dn =
L
nc
dx n
2
=
_
L
c
_
2
x
2
yields
F =

2
_
L
c
_
3
Z

0
x
2
ln[1e
x
]dx
integration by parts yields
F =

2
_
L
c
_
3
__
x
3
3
1e
x
_
1
3
Z

0
x
3
1e
x
dx
_
\right]since we know that
x
3
3
ln[1e
x
]
0
0
Z

0
x
3
1e
x
dx =

4
15
we nd that the free energy is
F =
2
V
4
45
3
c
3
Problem # 9 Heat capacity of liquid
4
He at low temperatures
The velocity of longitudinal sound waves in liquid
4
He at temperatures below 0.6 K is
2.38310
4
cm s
1
. There are no transverse sound waves in the liquid. The density is 0.145 gm cm
3
.
a) Calculate the Debye temperature.
87
In order to calculate the Debye temperature for
4
He we must begin with the total number of elastic modes
equaling N
4
8
Z
n
max
0
n
2
dn = N
we nd that
6
n
3
D
= N n
D
=
_
6N
_
1/3
the thermal energy of the phonon is
U =
n
=
s
n
n
=

n
e
n
/
1
for this problem we nd the thermal energy to be given as
U =
4
8
Z
n
D
0
n
e
n
/
1
n
2
dn
if we let
D
=
vn
D
L
we nd the energy to be given as
U =
vn
D
L
2
Z
n
D
0
n
2
D
e
n
D
v/L
1
dn
if we let
x
D
=
n
D
v
L
=
v
L
_
6N
_
1/3
=

T
=
k
B
where is called the Debye temperature expressed as

=
v
k
B
_
6
2
N
V
_
1/3
since we know that
N =
M
tot
m
1
N
V
=
M
tot
V
1
m
1
=

m
1
where m
1
is the atomic mass unit of a helium atom. Since we know
= 1.0510
34
Js
k
B
= 1.3810
23
J/K
m
1
= 41.6610
24
g
v = 2.38310
4
cm s
1
= 0.145 gm cm
3
we nd the Debye temperature to be given as
= 19.71 K
88
b) Calculate the heat capacity per gram on the Debye theory and compare with the experimental value
C
V
= 0.0204T
3
, in J g
1
K
1
. The T
3
dependence of the experimental value suggest that phonos
are the most important excitations in liquid
4
He below 0.6 K. Note that the experimental value has
been expressed per gram of liquid.
The energy in the low temperature limit for this case is given as
U =

4
N
4
5(k
B
)
3
we can see that the heat capacity is given as
C
V
=
_
U
_
V
=
4
4
N
3
5(k
B
)
3
=
4
5
4
k
B
N
T
3
3
to nd the heat capacity per gram we use
C
V
g
=
4
4
k
B
5
3
N
mass
T
3
where
N
mass
=
1
m
1
where m
1
is the atomic mass unit for helium, thus we nd
C
V
g
=
4
4
k
B
5
3
m
1
T
3
= 0.0211 J g
1
K
3
the error is given by
C
V
3.3%
89
Chapter 5
Chemical Potential and the Gibbs Distribution
This happens in a system that can change both energy and number of particles.
Road map
1. Denition of chemical potential
2. Thermodynamic identity (expanded) and the free energy
3. Tow kind of chemical potential: Internal and external chemical potential
4. Gibbs factor and the grand partition function.
5.1 Denition of Chemical Potential
Lets consider two system in thermal and diffusive contact. We have two systems that are seperated by a
permeable material where particles can go through it. We have
N
1
, u
1
and N
2
, u
2
where
u = u
1
+u
2
N = N
1
+N
2
these are both constant. We will proceed by writing down the most probable conguration MPC occurs
when
g
1
(N
1
, u
1
)g
2
(N
2
, u
2
)
is a maximum. If we diferentiate this, we know that
d(g
1
, g
2
) =
__
g
1
N
1
_
dN
1
+
_
g
1
u
1
_
du
1
_
g
2
+
__
g
2
N
2
_
dN
2
+
_
g
2
u
2
_
du
2
_
g
1
we will also now say
du
1
=du
2
dN
1
=dN
2
if we now divided by g
1
, g
2
we nd
_
1
g
1
_
g
1
N
1
_
1
g
2
_
g
2
N
2
__
dN
1
+
_
1
g
2
_
g
1
u
1
_
1
g2
_
g
2
u
2
__
du
1
= 0
90
but now we note the following
1
g
1
_
g
1
u
1
_
=
_
lng
1
N
1
_
=
_
1
N
1
_
if we now this for all these terms we get the following
1
g
2
_
g
2
u
2
_
=
_
lng
2
N
2
_
=
_
2
N
2
_
thus we nd
__
1
N
1
_
2
N
2
__
dN
1
+
__
1
u
1
_
2
u
2
__
du
1
= 0
now we know that dN
1
and du
1
are independent. Hence each term in the brackets is independent of 0.
_
1
u
1
_
=
_
2
u
2
_
1
=
1
2
but we nd a new term
_
1
N
1
_
=
_
2
N
2
_
thus we can now dene the chemical potential as
=
_
N
_
u
this is the chemical potential. The chemical potential has dimensions of energy. We know that particles
will diffuse from a higher until
1
=
2
at thermal equilibrium. We can remove N particles from 2 and
add to 1. Thus
N
1
=N
2
= N > 0
and
=
1
+
2
=
_
1
N
1
_
N
_
2
N
2
_
N =
_
+

2
_
N
if initially
2
>
1
thus the entropy would increase and is positive and thus we are moving to thermal equilibrium. As a
consequence particles will ow from higher to lower until they reach equilibrium.
5.2 Thermodynamic Identity and Denition of
We know that we can write the entropy as
= (u,V, N)
if we take the derivative
d =
_
u
_
du+
_
V
_
dV +
_
N
_
dN
91
thus
d =
1
du+
p
dV
dN
we ca now simply write this
du = dpdV +dN
this is now our thermodynamic identity.
We have just derived the thermodynamic identity. This is really the rst law of thermodynamics, it
also implies conservation of energy. This also gives us a denition of the chemical potential
=
_
u
N
_
,V
lets recall the Helmholtz free energy
F = u
if we differentiate we nd
dF = dudd
= dpdV +dNdd
dF = d pdV +dN
thus we nd
dF =d pdV +dN
this makes the free energy a function of the entropy, temperature, and chemical potential. Hence
=
_
F
N
_
,V
what we see is that the two different denitions of the chemical potential allow you to consider as the
increase in the internal energy u when 1 particle is added to the system at constant and V. It is also the
increase in the Helmholts free energy to the system at constant and V. You can have both internal and
external contributions to the chemical potentials.
5.3 Internal and Total Chemical Potential.
This is two say that there are two kind (contribution) of chemical potential,namely, internal and external.
Lets suppose that we have two boxes of gas that have initially
1,
N
1
,
1
and the second has
2
, N
2
,
2
,
initially
(initial) =
2
(initial)
1
(initial) > 0
thus we have a ow of particles from 2 to 1. Lets also assume that they have a charge q. Lets now connect
a battery between the two boxes with an EMF V. We can assume that the chemical potential is xed. If
we add a potential to them the chemical potential will increase. If we consider a few of the energy levels
of the system. If we now add a potential than we simply raise all of the energy levels, so that subsequently
we have a situation where we have simply increased the energy of all the particles by an amount qV.
We thus have both an internal and external contribution to the chemical potential. We apply a voltage
difference V to cancel , thus
qV = (initial)
92
we can see that
1
( f inal) =
1
(initial) +(initial) =
2
(initial) =
2
( f inal)
the chemical potential is simply a potential energy. This reenforces the notion that the chemical potential
is nothing more than a potential energy. So the total chemical potential is
tot
=
int
+
ext
where
ext
is the potential energy of the particle due to an external source of energy and
int
is the energy
per particle without the external energy. The externla contribution could be, electric, magnetic, gravitati-
nal, etc. The total potential is often referred to as the electric-chemical potential if the external contribution
comes from electric potential.
5.4 The Lead-Acid Battery
We must understand that the ow of charge is carried by the ions in the solution (chemical potential). The
hydrogen ions ow to the right and the sulfate ions ow to the left. The chemical reactions are as follows
Pb+SO
4
PbSO
4
+2e
cathode
where the electrons ow thru the external circuits. At the anode we have the following
PbO
2
+2H
+
+H
2
SO
4
+2e
PbS0
4
+2H
2
O anode
the net result is that we use up the lead sulfate and produce water. The electrons come from the external
circuit. The cathode is a sink for sulfate ions, therefore the chemical potential is lower at the cathode (lead
surface) (SO
4
) < (SO
4
) in the electrolyte. If we sketch the chemical potential, we can see that there
is a step given by (SO
4
). We dont know what this is, this is something we must measure. The same
thing happens at the anode, because the anode is now a sink for the hydrogen atoms. So that the chemical
potential (H
+
) at Pb surface is less than (H
+
) in electrolyte. Thus there is a step at (H
+
). The
chemical potential steps drive the ions toward the electrodes and hence the current through the resistor,
or more generally, your external circuit. What happens if we disconnect the external circuit? The current
stops, obviously, how can we stop the chemical reactions? What will happen is that electrons will leave the
anode into the electrolyte until they build up a potential difference that exactly cancels chemical potential
and make the total chemical potential zero, this happens when
(H
+
) +eV
+
= 0
Electrons enter the cathode until the total chemical potential is zero
(SO
4
) +2eV
= 0
when it is all nished we will have
V = V
+
+V
which is our total potential difference between the two terminals. Where the terms on the right are usually
referred to as the half-cell potentials, where
V
=0.4V V
+
= 1.6V
and
V = 2.0V
We can see that the battery takes chemical energy to drive electric circuits. The electric chemical potential
is zero to produce zero current ow. The charging process reverses the chemistry and discharge process
and it takes sulfate ions and produces sulfuric acid. Removes SO
4
from the electrodes to produce sulfuric
acid.
93
5.5 The Gibbs Factor
We know that gives us the Boltzman factor and we will now see that the chemical potential gives us the
Gibbs factor. We assume that we have a resevior in thermal contact with a system. Where the number of
particles in the resevoir is N
0
N and energy u
0
l
. The system is diffusive and in thermal contact. We
want to nd the ensemble average, where the system has N particles with energy
l,N
. We will start of by
assuming that there is only one state that has energy
l
so that we have a non-degenarate system. Thus the
multiplicity is equal to 1. We can say that the probability that this is in some state
l
with N particles is
proportional to multiplicity of the resevoir
P g(N
0
N, u
0
l
) 1
i.e
P(N,
l
) = Ag(N
0
N, u
0
l
)
we can now do a rst order Taylor expansion
lng(N
0
N, u
0
l
) = lng(N
0
, u
0
)
_
lng
N
_
u
0
N
_
lng
u
_
N
0
l
lng(N
0
N, u
0
l
) = lng(N
0
, u
0
) +
N
if we now take exponetial of both sides we nd

g(N
0
N, u
0
l
) = g(N
0
, u
0
)e
(N
l
)/
thus we nd the probability is given as
P(N,
l
) = Ad(N
0
, u
0
)e
(N
l
)/
= Be
(N
l
)/
this is exactly the form of the Boltzman factor, except that we now have the extra term given by the
chemical potential. We can now make a couple of immediate conclusions. You rst need the ratios of the
probability
P(N
1
,
1
)
P(N
2
,
2
)
=
e
(N
1
1
)/
e
(N
2
2
)/
we sometimes get degeneracies, where we can use the same trick as for the Boltzman factor. If we suppose
that we have energy
1
and
1
and
2
and
2
. Thus the ratios of the probabilities of the system having
energies
1
and
2
is given by
W(N
1
,
1
)
W(N
2
,
2
)
=

1
e
(N
1
1
)/
2
e
(N
2
2
)/
where we now weight the factors.
What is B? We need to sum
N
0
N=0
l
P(N,
l
) = B
N
0
N=0
l
e
(N
l
)/
= 1
thus
B =
1
where =
N
0
N=0
l
e
(N
l
)/
94
this we call the Grand Partition Function or the Grand Sum. Finally we have the results for the Gibbs
factor
P(N,
l
) =
e
(N
l
)/
this is known as the Gibbs factor it resembles the the Boltzman factor. We want to nd the average number
of particles and the average energy of the system.
Mean Number of particles N
We know that the average nuber of particles is given as
N =

N
l
Ne
(N
l
)/
this is the standard result for nding the average number of particles. This is simple if we make some
algabreac manipulation. Consider
=
N
=
1
l
N
(N
l
)/
_
=
N
what we see is that the average value of N is given by

N =

=
ln
we will also calculate the average energy. The mea energy

=

N
l
Ne
(N
l
)
lets consider the following derivative
l
(N
l
)e
(N
l
)
= [N]
thus
N =
1
=
ln
and we nd the average energy to be given as

=N
ln
=
ln

ln
and nally
=
ln

ln
a result from all this is for the uctuations

(N)
2
=
N
this is left as a homework assigment.

95
5.6 Summary
This are some very important relationships
d(u,V, N) =
_
_
V,N
d+
_
V
_
,N
dV +
_
N
_
V,
dN
=
du
+
P
dV
dN
this gives us the following identity
d = dPdV dN
and also
dF = d(u) = dudd
= d pdV +dN
if we now make a table of all these results
(u,V, N) u(,V, N) F(,V, N)
=
_
_
V,N
=
_
_
V,N
p
p
=
_
V
_
,N
p =
_
V
_
,N
p =
_
F
V
_
,N

=
_
N
_
,V
=
_
N
_
,V
=
_
F
N
_
,V
We then talked about the total chemical potenial
tot
=
int
+
ext
we then talked about the Gibbs factor
P(N,
l
) =
e
(N
l
)/
where is the grand sum

=
l
e
(N
l
)/
and we found the average number of particles
N =

=
ln
and the average energy is given as

=
ln

ln
and the uctuations are given by

(N)
2
=
N
96
Problem # 1 States of positive and negative ionization
Consider a lattice of xed hydrogen atoms; suppose that each atom can exist in four states:
state Numbe o f electrons Energy
ground 1
1
2
Positive ion 0
1
2
Negative ion 2
1
2
Excited 1
1
2
Find the condition that the average number of electrons per atom be unity. The condition will involve
, , and .
The grand partion function is given as
Z =
e
(N
n
)/
= e
(+
1
2
)/
+e
1
2
/
+e
(2
1
2
)/
+e
(
1
2
)/
if we let
= e
/
which is the absolute activity, allows us to simplify the partition function to
Z = e
1
2
/
+e
1
2
/
+e
1
2
/
2
+e
1
2
/
Z = [e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
2
we know that the average number of particles is given by
N =

lnZ =

ln
_
_
e
1
2
/
+e
1
2
/
_
+e
1
2
/
+e
1
2
/
2
_
we know that
ln
_
[e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
2
_
=
e
1
2
/
+e
1
2
/
+2e
1
2
/
[e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
thus we nd that the average number of particles is

N =
_
e
1
2
/
+e
1
2
/
+2e
1
2
/
[e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
2
_
setting this expression equal to 1 yields
_
e
1
2
/
+e
1
2
/
+2e
1
2
/
[e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
2
_
= 1
thus
[e
1
2
/
+e
1
2
/
+2e
1
2
/
] =[e
1
2
/
+e
1
2
/
] +e
1
2
/
+e
1
2
/
2
97
2
2
e
1
2
/
= e
1
2
/
+
2
e
1
2
/
we nd
2
e
1
2
/
= e
1
2
/
thus
= e
/2
Problem # 2 Carbon monoxide poisoning
In carbon monoxide poisoning the CO replaces the O
2
adsorbed on hemoglobin (Hb) molecules in the
blood. To show the effect, consider a model for which each adsorption site on a heme may be vacant or
may be occupied either with energy
A
by one molecule O
2
or with energy
B
by one molecule CO. Let N
xed heme sites be in equilibrium with O
2
and CO in the gas phases at concentrations such that the
activities are (O
2
) = 110
5
and (CO) = 110
7
, all at body temperature 37
0
C. Neglect any spin
multiplicity factors.
a) First consider the system in the absence of CO. Evaluate
A
such that 90 percent of the Hb sites are
occupied by O
2
. Express the answer in eV per O
2
.
We know that the grand partition function for this system is dened as
Z = 1+e
(
A
)/
where this represents the occupied states, where we know that the probability is given by
P(N
1
,
1
) =
e
(
A
)/
1+e
(
A
)/
using the denition for the absolute activity
= e
/
we can write the probability as
P(1,
A
) =
e
A
/
1+e
A
/
= 0.9
= 0.9(e
A
/
+)
which simplies to
ln
_

0.9
_
=
A
=13.71 =13.71k
B
T
since we know that T = 310 K thus we nd that the energy is
A
=.364 eV/O
2
b) Now admit the CO under the specied conditions. Find
B
such that only 10 percent of the Hb sites
are occupied by O
2
.
98
In this case we know that the grand partition function can be expressed as
Z = 1+
O
2
e
A
/
+
CO
e
B
/
where the rst term is for an unoocupied state, the second term is when it is occupied by O
2
and the third
term is for when it is occupied by CO. thus we can see that the probability is given by
P(N,
A
) =

O
2
e
A
/
1+
O
2
e
A
/
+
CO
e
B
/
= 0.1
thus we nd that
O
2
e
A
/
= 0.1[1+
O
2
e
A
/
+
CO
e
B
/
]
we can see that the energy is given by
B
=ln
__
O
2
e
A
/
0.1
1
O
2
e
A
/
_
1
CO
_
using the energy found in part (a) we nd that the energy is
B
=0.543 eV/CO
Problem # 3 Concentration Fluctuations
The number of particles is not constant in a system in diffusive contact with a resevoir. We have seen that
N =

_
,V
from
N =

=
ln
a) Show that
N
2
=

2
2
the mean-square deviation (N
2
) of N from N is dened by
(N)
2
= (NN)
2
= N
2
2NN +N
2
= N
2
N
2
(N)
2
=
2
_
1
2
_
_
2
_
since we know that
N
2
=(N)
2
+N
2
(5.1)
99
we can see that
(N)
2
=
2
_
1
2
_
_
2
_
and also we can see that
N
2
=

2
2
putting this into equation 1 we nd
N
2
=
2
_
1
2
_
_
2
_
+

2
2
doing the math yields the solution we were looking for
N
2
=

2
2
b) Show that this may be written as
(N)
2
=
N
in Chapter 6 we apply this result to the ideal gas to nd that

(N)
2
N
2
=
1
N
is the mean square fractional uctuation in the population of an ideal gas in diffusive contact wit a
resevoir. If N is of the order of 10
20
atoms, then the fractional uctuation is exceedingly small. In
such a system the number of particles is well dened even though it cannot be rigorously constant
because diffusive contact is allowed with the resevoir. When N is low, this relation can be used
in the experimental determination of the molecular weight of large molecules such as DNA of MW
10
8
10
10
.
Since we know that
N =


N
_
using the product rule we nd
N
2
thus we nd that
(N)
2
=
2
_
2
_
thus we have just shown that
(N)
2
=
N
=
2
_
2
_
100
Problem # 4 Multiple binding of O
2
A hemoglobin molecule can bind four O
2
molecules. Assume the is the energy of each bound O
2
,
relative to O
2
at rest at innite distance. Let denote the absolute activity e
/
of the free O
2
(in solution).
a) What is the probability that one and only one O
2
is adsorbed on a hemoglobin molecule? Sketch the
result qualitatively as a function of .
We know that the grand partition function for this system is given by
Z =

ASN
e
(N
s(N)
)/
= 1+4e
()/
+6e
2()/
+4e
3()/
+e
4()/
This is because we know that if there are no molecules attached then we get the rst term, the second term
is assuming that there is one oxygen atom attached we nd the multiplicity to be 4, if there are two atoms
attached then the multiplicity is 6, if there are 3 atoms attached then the multiplicity is 4, and if there are
four atoms attached then the multiplicity is 1. Since we know that the absolute activity is dened as
= e
/
allows us to write the grand partition function as
Z = 1+4e
/
+6
2
e
/
+4
3
e
/
+
4
e
/
we know that the probability that one atome is attached is given by
P(N = 1, ) =
4e
/
1+4e
/
+6
2
e
/
+4
3
e
/
+
4
e
/
=
4
e
/
+4+6
2
+4
3
+
4
The plot is given
0 200 400 600 800 1000 1200
0.00
0.01
0.02
0.03
0.04
P
(
)
b) What is the probability that four and only four O
2
are adsorbed? Sketch this result also.
101
This probability is given by
P(N = 4, ) =

4
e
/
+4+6
2
+4
3
+
4
the plot is given by
102
Chapter 6
The Ideal Gas
Roadmap
Identical Particles: Bosons and Fermions
Fermi-Dirac Distribution
Bose-Einstein Distribution
Classical Limit and the Chemical Potential
Ideal Classical Gas, F, p, , ,C
V
Expansion of Gases
Polytomic gases: Internal degrees of freedom and Equipartitio Theorem
6.1 Identical Particles: Bosons and Fermions
Lets start of by considering a three dimensional space with two identical particles. This are particles
that cannot be labeled, they are strictly identical. We can write down a Shrodinger equation that is time
independent
2
2m
2
1

2
2m
2
2
T
+(V
1
+V
2
)
T
= E
T
T
we are assuming that this particles are i some electric eld that give them the potential energy. We can
solve by writing down the wave functios by bte product of the two wave functionc
T
=
(1)
(2)
where and are te quantum numbers of each particle. If we plug this in we get the following result
2
2m
(2)
2
1
(1)

2
2m
(2)
2
2
(2) +(V
1
+V
2
)
(1)
(2) = E
T
(1)
(2)
we can see that this two equations seperate. This can be written as
2
2m
2
1
(1)
(1)
+V
1
= E
1

2
2m
2
2
(2)
(2)
+V
2
= E
2
E
T
E
1
+E
2
103
this is for non-interacting particles only. So far so good, we found a wave function that satisfy the SE.
This are identical particles and QM will not allow us to label them, it only allows us to distinguish their
states. We cannot label identical particles, so an equaly good wave function is of the form
(2)
(1) so
the general solution is of the form
T
=
1
2
[
(1)
(2)
(1)
(2)]
this brings us to the question of the symmetry of the wave function, symmetric and anti-symmetric. The
consequencies of this is very profound. What we learn emperical is that ther are two general classes of
behaviours. The rst is for fermions. Fermions have a 1/2 integer spins, some examples are electrons,
protons,neutrons, and helium 3. All of these have 1/2 spin. The other class are the bosons with integer
spins, i.e photons, deuterons, and helium 4 nucleus. So the rst class, the fermions have anit-symmetric
wave functions and the bosons have symmetric wave functions. What difference does this make? If
we interchange the symmetric wave functions we can see that there is no change, on the other hand
interchanging the anti-symmetric wave functions we can see that there is a change
. What
happens if we let = . For the symmetric case, there is nothing that is violated, the total wave function
simply becomes
T
=
2
(1)
(2)
if we do this for the anti-symmetric case we see that the wave function vanishes. This is a result of the
Pauli exclusion principle, you cannot have two identical particles in the same quantum state. There is no
restriction for bosons.
6.2 Fermi-Dirac Distribution
We will use the grand canonical ensemble, we must consider a a lot of particles in discrete quantu levels.
We will pick out 1 state that we will call the system and the rest we will consider the resevoir. Our goal is
to nd the average occupancy that has an energy
l
. Since these are fermios means that we can only have
1 particle in a given state. We know that N = 0 or N = 1. This system is in thermal equilibriums that can
exchange energy and particles. We want to nd the average number of particles in this system.
N(
l
)
we must write down the grand partition function.
= 1+e
(
l
)/
these are the only two allowed states
N(
l
) =
e
(
l
)/
1+e
(
l
)/
this is know as f ()
f () =
1
e
()/
+1
this is known as the Fermi-Dirac distribution function. We can see that this result involves the potential
energy. This formula has tow different interpretations, one is that the probability that the state with energy
104
is occupied, or it is the averagge occupancy of state with energy . What is the form of this distribution?
What will this look like at = 0? If we take energy
< e
()/
= e
= 0 f ( < ) = 1
> e
()/
= e
= f ( < ) = 0
if we were to plot this we would get a step function at . Secondly, at any temperature
f ( = ) =
1
e
0
+1
=
1
2
thus is the energy for which the occupancy is 1/2. What happens with increasing temperature? Lets
suppose that we have a 3-D gas with a Fermi gas. Lets take spin 1/2 with a lot of energy levels and we
also have an even number of Fermions. The lowest energy level will have only two electrons (exclusion
principle). The next two will go into the rst excited state etc. We will see that the electrons in the higher
energy state will move to even higher energy states. We will smear out the distribution around the energy
levels (k
B
T). The Fermi level is
F
, and at T = 0 it is exactly the same as the chemical potential . This
smearing is symmetric around the chemical potential.
Symmetry of Filled and Vacant states
What is the probability that the state = is
f () =
1
e
/
+1
f (+) =
1
e
/
+1
this is the probability that these two states will be occupied. What is the probability that at + is vacant?
p(+) = 1 f (+) =
(e
/
+1) 1
e
/
+1
=
e
/
e
/
+1
=
1
e
/
+1
= f ()
if we now imagine what happens to this distribution as we increase the temperature. We can see that there
will be a smearing of the dsitribution that is of the order of . The chemical potential will eventually start
to change, as is increased than drops.
6.3 Bose-Einstein Distribution
This applies to bosons (particles with integer spins), where the Pauli exclusion principle does not apply.
Once again we must consider a resevoir and a system. We can put as many bosons as we like in any
quantum state. As before we consider 1 quantum state l that is in thermal equilibrium with all the other
states in the resevoir. We ca now write down the grand partition function
= 1+e
(
l
)/
+2e
2(
l
)/
+...
both and get multiplied by the number
=
N
0
n=0
e
n(
l
)/
105
we will assume that N
0
. If we now let
x = e
(
l
)/
thus we nd
=
n=0
x
n
=
1
1x
this only works if x < 1, otherwise this function blows up. We can see that
< 0 <
what we now want to calculate the average occupancy of the state l.
n() = probability of state being occupied
this is given as
n() =
nx
n
x
n
=
x
d
dx
x
n
x
n
=
x
d
dx
_
1
1x
_
1
1x
=
x
(1x)
2
1
1x
=
1
x 1
thus we nd the Bose-Einstein distribution
n() = n() =
1
e
()/
1
the Bose-Einstein distribution will always have >. The Bose-Einstein distribution blows up as e
()/
1, this function converges the the Fermi-Dirac distribution when . The Bose-Einstein condensa-
tion refers to the the fact that at low enough temperatures all of the bosons will condense into the ground
state.
6.4 The Classical Limit and the Chemical Potential
We would like to recap the 1 particle in the box solutions. We derived the quantum concentration
n
Q
=
_
m
2
2
_
3/2
3
D
thus for 2 particles seperated by more than the Debroigle wavelength, we nd that the concentration of
the particles n n
Q
. If we have two particles that are very close with respect to the Debroigle wavelength
we must consider the quantum effects and must utilize quantum statistics. If we have two particles that
are seperated by much more than the Debroile wavelength than we will be in the classical limit n n
Q
.
These scales are set by the Debroigle wavelength. In the context of 1 particle we found
Z
1
=

n=0
e
n
/
= n
Q
V
where n
2
= n
2
x
+n
2
y
+n
2
z
and V is the volume of the box. Once again we must remember that we are in
the tail of the distribution where the average occupancy is much less than 1. We dene the calssical gas is
one in which f () or n() is 1. This is a low density level, at this level, both distributions give the same
results. So that
e
()/
1
106
thus we nd
n() = e
/
e
/
this is the distribution function for a classical gas. We want to nowgure something out about the chemical
potential. Lets conne our attention to a monotomic gas, i.e He. What is ? We can nd from the
following
N =N =
n
f (
n
)
we simply add the occupancies of all the states. We nd
N = e
/
n
e
n
/
= e
/
Z
1
= n
Q
Ve
/
this is rather neat, we can devide by the volume on both sides to get
N
V
= n
Q
e
/
n
n
Q
= e
/
taking logs on both sides
= ln
_
n
n
Q
_
this links the classical potential to the densities. If we we look at our previous expression
n() = f () = e
/
e
/
=
_
n
n
Q
_
e
/
thus f () 1 provided n n
Q
. We can see from the expression of the chemical potential that for a
classical gas, the chemicla potential is negative. This is yet another signature between the classical gas
and the quantum gas. If we lower n/n
Q
we can see that the chemical potential changes signs at n = n
Q
,
where we go from classical to quantum regimes. The denition of the chemical potential always involves
n
Q
which always involve . Thus even at the classical limit, the particles remember that they are made
up of indistinguishable particles.
Example: Variation of the Pressure of the Earths Atmosphere with Height
We know the chemical potential is given by two quantities
tot
=
int
+
ext
we will make a an assumption that is xed. If we consider two layers of gas that are in diffusive contact,
which allows particles and energy to be transferrable through the layer. The layer is lled with monotomic
particles in thermal equilibrium. If we also assume that we have zero potential energy at sea level. We can
see that the particles above sea level will have
ext
= mgd
thus the total chemical potential is
tot
= ln
_
n
n
Q
_
+mgd
107
now, in thermal equilibrium, the total chemical potential must be constant. We can see that as we go up
in altitude,
ext
increases and
int
will decrease. We can make the following statement: if we consider the
upper level
ln
_
n(d)
n
Q
_
+mgd =ln
_
n(0)
n
Q
_
combining the two log terms we nd
ln
_
n(d)
n(0)
_
=mgd
that is to say that
n(d) = n(0)e
mgd/
we know that at a given temperature, the pressure will be proportional to
p(d) = p(0)e
mgd/
= p(0)e
d/d(0)
where d(0) =/mg, if we put some numbers, i,.e N
2
we nd
d(0) =
290 K
281.710
27
kg9.8 m/s
2
8.7
6.5 Ideal Classical Gas:Free Energy, Pressure, Internal Energy, En-
tropy, and Heat Capacity
The word ideal means that there are no interaction between the particles, and classical mean that we are
in the low energy limit. The free energy is the most important quantity one will derive. Recall that the
chemical potential is
= ln(n/n
Q
) n
Q
=
_
M
2
2
_
3/2
the rst thing we need to nd is the free energy
6.5.1 Free Energy
=
_
F
N
_
,
where
=
_
lnNlnV
3
2
ln
3
2
ln
M
2
2
_
this is for later convenience, so we can then write
F(N, ,V) =
Z
N
0
dN(N, ,V) =
Z
N
0
dN
_
lnNlnV
3
2
ln +
3
2
ln
_
2
2
M
__
lets recall the following result
Z
lnxdx = xlnx x
108
we get the following
F(N, ,V) =
_
NlnNN NlnV
3N
2
ln +
3N
2
ln
_
2
2
M
__
(6.1)
the rst two terms give you
Nlnn = NlnNN NlnV
and the last two terms give you-
Nlnn
Q
=
3N
2
ln +
3N
2
ln
_
2
2
M
_
thus
F(N, ,V) = NlnnNlnn
Q
= N[lnnlnn
Q
]
thus
F(N, ,V) = N
_
ln
_
n
n
Q
_
1
_
this is the free energy.
6.5.2 Pressure
The pressure is dened as
p =
_
F
V
_
,N
using Equation 6.1 we nd
p =
_
N
V
_
thus we get the ideal gas law
pV = N = Nk
B
T = RT
where R is the gas constant for 1 mole. We can immediatly gure out that
R = N
A
k
B
= 6.0210
23
atoms/mole1.3810
23
J/K = 8.31 J/K mole
6.5.3 Internal Energy
Lets write down the thermodynamic identity
dF =d pdV +dN
this enables us to gure out the free energy very easily
F = u u = F + =
_
F
_
V,N
thus the internal energy is
u = F
_
F
_
109
there is a trick, lets consider
2
_

_
F
__
=
2
_
2
F +
_
F
_
V,N
_
= F
_
F
_
thus
u =
2
_

_
F
__
V,N
but from Equation 6.1 we can see that there is only one term in , thus
u =
2
_
3N
2
_
1
=
3
2
N
which is the same result we have derived before from the equipartition theory.
u =
3
2
N
Note: The internal energy of an ideal gas only depends on the temperature.
6.5.4 Entropy
We can go back to the thermodynamic identity, we nd that the entropy is given by
=
_
F
_
V,N
once again looking at Equation 6.1, and differentiating with respect to , hence
=
_
NlnNN NlnV
3
2
N +
3
2
Nln
_
2
2
M
_
3N
2
1
_
where the last term came from
_
3N
2
ln
_
thus we can see that the entropy is given by
=
_
Nlnn
3
2
Nln() +
3
2
Nln
_
2
2
M
__
+
5
2
N
we also know that
ln(n
Q
)N =
3
2
N +
3
2
Nln
_
2
2
M
_
putting all these together we have
= N
_
ln
_
n
Q
n
_
+
5
2
_
this result is called the Sackus-Tetrode Equation. This is the central result of the ideal gas, which will
allow you to derive all the other quantities. Note: Gibbs paradox ( 1875) was the rst indication of
problems with classical physics (indistinguishibility)
110
6.5.5 Heat Capacity
We have
du = dpdV
where the rst term is the heat added and the second term is the work done on the gas. There are two kinds
of heat capacity
Heat capacity at constant volume. We have a box with a bunsen burner, the heat increases but the
volume stays the same
Heat capacity at constant pressure. We have a piston with pressure being applied, along with a
bunsen burner that adds heat to the system.
In the rst case there is no mechanical work, and in the second case there is mechanical work that is
applied in pushing back the piston against constant pressure. We can see that
C
P
>C
V
lets start with C
V
. If we want to increase the temperature d then the internal energy must increase by du.
The internal energy depends only on the temperature. We can see
_
u
_
V
=
_
_
V
thus
C
V
=
_
u
_
V
=
_
_
V
we rember that the entropy is
= N
_
lnn
Q
lnn+
5
2
_
= N
_
3
2
ln +terms independent of
_
_
_
=
3
2
N
1

C
V
=
3
2
N =
3
2
Nk
B
now for the heat capacity at constant pressure C
P
, we begin with
d = du+ pdV
thus
C
P
=
_
_
P
we can now write this as follows
C
P
=
_
u
_
P
+ p
_
V
_
111
the rst term is once again C
V
, that is because the internal energy depends only on the temperature. The
second term is the work done in expanding the gas, which we must gure out, thus
C
p
=C
V
+ p
_
V
_
P
pV = N V =
N
p
thus
p
_
V
_
P
= p
N
p
= N
thus
C
P
=C
V
+N =
5
2
N =
5
2
Nk
B
and we can see that
C
P
>C
V
this is only for a monotomic gas. The nal thing is to dene the ratio of C
P
to C
v
where
=
C
P
C
V
=
5
3
6.6 Expansion of Gases
There are two kinds of expansion in gases, one in which we keep the temperature xed and the other where
we keep the pressure xed.
6.6.1 Isothermal Quasistatic Expansion
Quasistatic implies slowwhich implies that this is in thermal equilibriumduring expansion. We have some
resevoir that we keep at constant temperature T
0
, we then have some cylinder with a piston that applies a
constant pressure on the system. What we know is that pV = N and since we know that the temperature
is constant we know that p
i
V
i
= p
f
V
f
, this is known as Boyles Law. What we know is
= N
_
ln
_
n
Q
n
_
+
5
2
_
= NlnV +terms independent of V
in this context the entropy only depends on the rst term. The change in the entropy is given as
gas
= NlnV
f
NlnV
i
= Nln
_
V
f
V
i
_
if the nal volume is bigger then the initial volume then we can see that the entropy increases. What is the
work done on the gas?
W =
Z
V
f
V
i
Fdx =
Z
V
f
V
i
F
A
dV =
Z
V
f
V
i
pdV
going back to the ideal gas law we nd
W =
Z
V
f
V
i
N
V
dV =Nln
_
V
f
V
i
_
112
apart from the this is the same as the entropy, thus
W =
gas
and nally the change in the internal energy
u = 0
because the temperature of the gas did not change. We could have guessed this result if we think about the
internal energy
u =
3
2
N
thus
u = 0
from this we can talk about the heat ow from or into the gas, if the change in the internal energy is zero
we see right away that we have the following result
Q
gas
+W = 0
or
Q
gas
=W
if we now do work to push up the piston, we can see that we will do work to make this happen. This is
part of the thermal cycle of a heat engine. This is the heat ow during expansion. The nal thing we can
ask is what is the change i the entropy of the resevoir, this is given by
change in entropy of resevoir =
Q
gas
=
Q
gas
=
W
=
gas
and we can see that
res
+
gas
= 0
which implies
= 0
this implies that this is an entirely reversible process. We will now turn to the adiabatic expansion.
6.6.2 Adiabatic Quasistatic Expansion
The word adiabatic is tricky, in the case of QM this is a very slow process, in the case of thermodynamics
the word adiabatic means that it is thermally isolated. Conceptually, we have a cylinder and a piston with
gas atoms inside, but there is no heat exchange with the system and the resevoir. When we change the
volume V
i
V
f
there is no heat exchange (Q = 0 and
gas
= 0) with the environment and thus this is
an adiabatic process. We want to nd a relationship between the pressure and the volume. Lets gure out
what this is, we will end up using C
P
,C
V
and =C
P
/C
V
. We will begin using the thermodynamic identity
du = dpdV
we know that d = 0 and we also know
C
V
=
_
u
_
V
du =C
V
d
113
and we can see that
C
V
d + pdV = 0
we need to eliminate d, we can use the ideal gas equation
d(pV) = d(N)
pdV +Vdp = Nd
we can see
C
V
(pdV +Vdp) +NpdV = 0
we can rewrite this as follows
pdV(C
V
+N) +C
V
Vdp = 0
we can see that this simplies to
C
P
C
V
pdV +Vdp = 0
pdV +Vdp = 0
dV
V
+
dp
p
= 0
lnV +ln p = C
which gives
pV
=Constant
this is the result used for adiabatic expansions. Also, lets consider
pV = N p =
N
V

we can see that
V
1
=Constant
or
V
=
N
which yields
p
1
=Constant
the last thing we should work out is the work done on the gas. We use
W = u
f
u
i
this is simply
W =
3
2
N(
f
i
)
=
3
2
N
i
_
i
1
_
=
3
2
N
i
_
_
V
f
V
i
_
1
1
_
114
which gives
W =
3
2
N
i
_
_
V
f
V
i
_
2/3
1
_
when the gas expands there is a increase in due to the increase in the volume. If the temperature drops,
this gives a decrease in which exactly cancels the increase in due to the volume increase.
Comment on adiabatic process in QM
lets imagine that we have many energy levels in a box that are populated with gas atoms. We will expand
the box very slowly so that the energy levels are all lower. The result of doing time dependent pertubation
tells us that the atoms do not change energy levels, and thus the distribution of the particles over the
quantum states on the average does not change. The consequence is that the entropy is constant.
6.6.3 Sudden Expansion in a Vacuum
Once again this is an isolated system. Lets imagine that we have a box with a partition in it. Initially all
the atoms are conned to the left hand side, we than remove the partition very suddenly. We thus go into a
new state in whihc the particles are distributed uniformly over the volume of the box. We can see that this
is an irreversible process, i.e placing the partition back in will not give us the same distribution. First of
all, there is no work done during this process, and thus the energy of the system does not change u = 0,
this is because the internal energy only depends on the temperature. By the same token = 0, but the
change in the entropy is not zero, it is
= Nln
_
V
f
V
i
_
this is analogous to what happens in QM, we can compare this to the sudden approximation in QM, i.e
beta decay which gives rise to a new set of atomic states.
6.7 Polyatomic Gases: Internal Degree of Freedom
Example: N
2
(Dumbell)
The rst thing is that we can have vibration and the second thing is that they can rotate. This gives rise
to signicant changes in the heat capacity. If we think of this classically we will need energy kT to excite
the vibration. We will imagine a set of distinct energy levels given by
=
1
2
n n = 1, 3, 5, ...
in the classical limit we know that u = k
B
T thus the heat capacity is C
V
= k
B
, this of course is in the limit
k
B
T . What about rotation? There are two degrees of rotation for polyatomic gases, thus the energy
of a rotator is given as
u
rot
=
1
2
I
2
where I is the moment of inertia, there is nonly a kinetic energy term. We can also write this as
u
rot
=
1
2
(I)
2
I
115
in QM we have the following
(I)
2
= r(r +1)
2
where r is an integer and I is the angular momentum. Thus the rotational energy is given by
u
rot
=
r(r +1)
2
2I
r = 0, 1, 2, 3, ...
once again since this is in the classical limit we will have
1
2
k
B
T for each degree of rotation, thus
u
rot
(2 modes) = k
B
T
and the heat capacity will be
C
V
= k
B
the rotation mode about the axis through the atoms is never excited, it would take an innite amount of
energy since the moment of inertia is approximately 0. If we were to go to NH
3
we would have 3 modes
of rotation. Given this result we can now ask how big is the rotational energy.
Rotational energy of N
2
Lets consider the seperation between the center of rotation and one atome be 10
10
meters. What is the
moment of inertia, we know that M
N
2
210
26
kg, we nd the moment of inertia to by
I = 2(10
10
)
2
210
26
kg 410
26
m
2
kg
thus the energy of the rst excited state
u =
2(10
34
)
2
2410
26
210
22
J 10 K
this gives a reasonable temperature above which you would get rotation.
6.7.1 The Grand Partition Function for the ideal Gas with Internal Degrees of
Freedom
This is used when the problem implies that there are internal degrees of freedom. The grand sum for
bosons and fermions become the same in the classical limit. For he case o the fermions when you have
two energy levels you can have at most one particles in the ground state. For fermions
= 1+e
(
n
)/
for bosons we have
= 1+e
(
n
)/
+e
2(
n
)/
+...
in the case of a classical gas we can see that the higher order terms are negligable and that the grand
partition functions are the same. Since f (
n
) 1 we can neglect the higher order terms. Hence in the
classical gas we take as the grand partition function
= 1+e
(
n
)/
116
what do we do if we have additional terms? We must add another term that describes internal degrees of
freedom. For the polyatomic case
n
n
+
int
, where this corresponds to the vibrational and rotational
energy, thus we now have
1+
int
e
(
n
int
)/
thus we must sum over all the possible internal degrees of freedom. We can now write this in the form
= 1+e
(
n
)/
int
/
we will call the multiplying factor Z
int
, which yields
= 1+Z
int
e
(
n
)/
we can use this to nd a new expression for the chemical potential. The probability that the state n is
occupied for any state of its internal motion is given by the following
f (
n
) =
Z
int
e
(
n
)/
1+Z
int
e
(
n
)/
but now by hypothesis we have agreed that the grand partition function is very small, thus we nd
f (
n
) = Z
int
e
(
n
)/
this is the result for the monotomic gas multiplied by the factor representing the internal degrees of free-
dom. We can now relate this to the average occupancies
N =N =
f (
n
) = Z
int
e
/
n
/
= Z
int
e
/
Z
1
which gives
N = Z
1
Z
int
e
/
but we remember that
Z
1
= n
Q
V
we can now write
N = n
Q
VZ
int
e
/
rearranging gives us the following
n
n
Q
= Z
int
e
/
taking the log of both sides give
=
_
ln
_
n
n
Q
_
lnZ
int
_
we can see that we now have an additional term that accounts for the internal degrees of freedom, without
this term we simply recover the result for the monotomic gas.
117
6.7.1.1 Example 1 (Diesel Engine)
This is a process in which gas is compressed adiabatically to a high enough temperature to ignite the diesel
fuel that is then injected. If we start we air at T = 300 K and lets suppose that the compression ratio is 16,
which means that we reduce the volume to 16 times smaller. We have seen that we get the following result
T
i
V
1
i
= T
f
V
1
f
thus
T
f
= T
i
_
V
i
V
f
_
1
we know that = 7/5 for air, which is nitrogen and oxygen, this is because
C
V
=
3
2
Nk
B
+Nk
B
where the second term is added for the rotational mode, and we know that
C
P
=C
V
+Nk
B
=
7
2
Nk
B
and
=
7
5
if we put the number in we get
T
f
= 300(16)
2/5
= 909 K
6.7.1.2 Example 2
We need to show that
p =
3
2
U
V
this is done in three steps.
a) Find that the average pressure in a system in thermal contact with a heat resevior. Recall
p
s
=
_
s
V
_
N
thus the average pressure is equal to
p =
s
p
s
P(
s
)
where p is the pressure and P is the probability that state s is occupied. We nd
p =
s
_
s
V
_
N
e
s
/
Z
this is step 1.
118
b) Show that for an ideal gas
_
s
V
_
N
=
2
3
s
V
there are various ways of getting this. If we have a cube of side L we nd
s
=

2
2m
2
L
2
(n
2
x
+n
2
y
+n
2
z
)
1
V
2/3
for all n
x
, n
y
, and n
z
. If we take logs of both sides we nd
ln
s
=
2
3
lnV
if we differentiate both sides we nd
d
s
s
=
2
3
dV
V
which gives
_
s
V
_
N
=
2
3
s
V
c) the result of the pressure
p =
1
Z
s
_
2
3
s
V
_
e
s
/
=
2
3V
_
s
e
s
/
Z
_
=
2U
3V
if we go for a monotomic gas, the energy U =
3
2
Nk
B
T we can see that
pV = Nk
B
T
which is the ideal gas law.
6.8 Summary
The rst thing we learned is
f () =
1
e
()/
1
where 1 account for either a boson or fermion. In the classical limit we can see that
f () = e
/
e
/
=e
/
where is the absolute acitivity. we also found
=ln(n/n
Q
)
also
F = N[ln(n/n
Q
) 1]
and
pV = N
119
also the internal energy
U =
3
2
N
and the entropy is
= N
_
ln(n/n
Q
) +
5
2
_
the heat capacity is
C
V
=
3
2
N
and
C
p
=C
V
+N =
5
2
N
we also learned about isothermal expansion
p
i
V
i
= p
f
V
f
we also saw that
res
=Nln(V
f
/V
i
)
gas
= Nln(V
f
/V
i
)
which gives
= 0
we also talked about the adiabatic expansion
p
i
V
i
= p
f
V
f
=
C
P
C
V
where this process is a reversible process. We also talked about the free expansion, this is where we rupture
a membrane in some box. We found that there is no change in the internal energy and no change in the
temperature
U = 0 = 0 = Nln(V
f
/V
i
)
this process is irreversible. We also talked about diatomic gases. We found
C
V
=
3
2
N +N+N
where these are for rotational, vibrational and translational energies. We also nd
= [ln(n/n
Q
) lnZ
int
]
we can also remember that the ideal gas does not exist.
Problem # 1 Distribution Function for Double Occupancy Statistics
Let us imagine a new mechanics in which the allowed occupancies of an orbital are 0,1, and 2. The
values of the energy associated with these occupancies are assumed to be 0, , and 2, respectively.
a) Derive an expression for the ensemble average occupancy N, when the system composed of this
orbital is in thermal and diffusive contact with a reservoir at temperature and chemical potential .
120
We know that the average occupancy is dened as
N =

N
s
Ne
(N
s
)/
where is the grand partition function

=
s
e
(N
s
)/
(6.2)
the average occupancy can also be acquired witha bit of algebreac manipulation, Consider
=
N
=
1
l
N
(N
l
)/
_
=
N
what we see is that the average value of N is given by

N =

=
ln
thus we simply need to know what the grand sum is. This is given by Equation 1, we nd (if we let
= e
/
)
= 1+e
/
+
2
e
2/
where the derivative is given as
ln
=
1
=
1
_
1
e
/
+
2
2
e
2/
_
thus we can see that the average occupnacy is given as
N =
e
/
+2
2
e
2/
1+e
/
+
2
e
2/
b) Return now to the usual quantum mechanics, and derive an expression for the ensemble average occu-
pancy of an energy level which is doubly degenerate; that is, two orbitals have the identical energy
. If both both orbitals are occupied the total energy is 2.
We can write the grand partition function for this system, if we know that s = 0,
s
= 0 and s = 1,
s
=
and this is doubly degenerate, and for the last orbital s = 2,
s
= 2 allows us to write the grand sum as
= 1+2e
/
+
2
e
2/
and the ensemble average is given by
N = 2
_
e
/
+
2
e
2/
1+2e
/
+
2
e
2/
_
Problem # 2 Energy of Gas of Extreme Relativistic Particles
121
Extreme relativistic particles have momentum p such that pc Mc
2
, where M is the rest mass of the
particle. The de Broglie relation = h/p for the quantum wavelength continues to apply. Show that the
mean energy per particle of an extreme relativistic ideal gas is 3 if pc, in contrast to
3
2
for the
nonrelativistic problem.
We know that
=
h
p
= pc =
hc
but we know that

L =
n
2
=
2L
n
thus
(n) =
hcn
2L
We know that the mean energy is given as
U =
2
lnZ
thus we must nd the partition function, which is given as

Z =
n
e
n
/
=

2
Z

0
n
2
e
hcn/2L
dn
if we let
x =
hcn
2L
dn =
2L
hc
dn n
2
= x
2
_
2L
hc
_
2
thus we nd that the partitio function is given by
Z =
_
2L
hc
_
3
2
Z

0
x
2
e
x
dx
where
Z

0
x
2
e
x
dx =
_
x
2
e
x
2xe
x
2e
x
0
= 2
thus we nd that the partition function is
Z =
_
2L
hc
_
3
Z
= 3
2
_
2L
hc
_
2
thus we nd
U =

2
Z
Z
=
3
4
3
= 3
Problem # 3 Entropy of Mixing
122
Suppose that a system of N atoms of type A is placed in diffusive contact with a system of N atoms of
type B at the same temperature and volume. Show that after diffusive equilibrium is reached the total
entropy is increased by 2Nlog2. The entropy increase 2Nlog2 is known as the entropy of mixing. If the
atoms are identical (A B), show that there is no increase in entropy when diffusive contact is
established. The difference in the results has been called the Gibbs paradox.
We know that the entropy of an ideal gas is given by
= N
_
ln
_
n
Q
n
_
+
5
2
_
and we also know that the total entropy before the mixing is just the sum of the individual entropies
which is given by
T
=
A
+
B
this is simply
T
= N
A
_
ln
_
n
Q
n
A
_
+
5
2
_
+N
B
_
ln
_
n
Q
n
A
_
+
5
2
_
we also know
N = N
A
= N
B
n
A
=
N
A
V
n
B
=
N
B
V
n = n
A
= n
B
thus we nd that the total entropy is given by
T
= 2N
_
ln
_
n
Q
n
_
+
5
2
_
the entropy after mixing can be found by assuming
N
T
= 2N n =
N
V
n
f
= 2n
thus the entropy is now given as
mix
= 2N
_
ln
_
n
Q
2N
V
_
+
5
2
_
and we nd that the change in the entropy is given as
=
T
mix
= 2N
_
ln
_
n
Q
n
_
+
5
2
_
2N
_
ln
_
n
Q
2n
_
+
5
2
_
thus we can see that this is simply
= 2Nln2
Problem # 4 Time for a Large Fluctuation
We quoted Boltzmann to the effect that two gases in a 0.1 liter container will unmix only in a time
enormously long compared to 10
(10
10
)
years. We shall investigate a related problem: We let a gas of
atoms of
4
He occupy a container of volume of 0.1 liter at 300 K and a pressure of 1 atm, and we ask how
long it will be before the atoms assume a conguration in which all are in one-half of the container.
a) Estimate the number of states accesible to the system in this initial condition.
123
We know that the number of accesible states is given by
= lng g = e
where the entropy is dened as

= N
_
ln
_
n
Q
n
_
+
5
2
_
where the quantum concentration is given as
n
Q
=
_
M
2
2
_
3/2
n =
N
V
thus we nd
= N
_
lnn
Q
lnn+
5
2
_
= N
_
3
2
ln
_
M
2
2
_
ln
_
N
V
_
+
5
2
_
where we also know
N =
pV
k
B
T
M = 4amu = 41.6610
27
kg 0.1L = 10
4
m
3
1 atm = 1.0110
5
Pa
thus we nd the entropy to be given as
=
pV
k
B
T
_
3
2
ln
_
Mk
B
T
2
2
_
ln
_
p
k
B
T
_
+
5
2
_
= 3.6910
22
and the number of accesible states is given by
g = e
3.6910
22
b) The gas is compressed isothermally to a volume of 0.05 liter. How many states are accessible now?
We need to nd what the change in the entropy is for this, this is given by
2
= Nln
_
V
2
V
1
_
+
1
= Nln
_
1
2
_
+
1
where these becomes
2
=
pV
k
B
T
ln
_
1
2
_
+
1
= 3.5210
22
thus we nd that the number of accesible states is now given by
g
2
= e
3.5210
22
c) For the system in the 0.1 liter container, estimate the value of the ratio
number of states for which all atoms are in one-half of the volume
number of states for which the atoms are anywhere in the volume
We know that this is simply
ratio =
g
2
g
= e
1.7010
21
124
d) If the collision rate of an atom is 10
10
s
1
, what is the total number of collisions of all atoms in the
system in a year? We use this as a crude estimate of the frequency with which the state of the system
changes.
We know that the total number of collisions of all atoms is given by
total collisions for all atoms = Nr = 2.41510
21
10
10
_
10
7
s
yr
_
= 7.5810
38
collisions
yr
e) Estimate the number of years you would expect to wait before all atoms are in one-half of the volume,
starting from the equilibrium conguration.
We can do this by knowing that the ratio we calculated in c gives us the probability that all of the atoms
will be in half of the container, and we can see that the time is given by
t = (p f )
1
=
1
p f
where p is the probability that the atoms will be in 1/2 of the container and f is the frequency we found in
part d, so we nd that the time is
t =
e
1.710
21
7.5810
38
yrs
Problem # 5 Gas of atoms with internal degree of freedom
Consider an ideal monotomic gas, but one for which the atom has two internal energy states, one energy
above the other. There are N atoms in volume V at temperature . Find the (a) chemical potential; (b)
free energy; (c) entropy; (d) pressure; (e) heat capacity at constant pressure.
a) Chemical potential?
We know that the chemical potential is found from the condition that the thermal average of the total
number of atoms equals the number of atoms known to be present. This number must be the sum over all
orbitals of the distribution function f (
s
)
N =N =
s
f (
s
)
The Gibbs sum for this system is given as
= 1+e
n
/
= 1+
int
e
(
n
+
int
)/
= 1+Z
int
e
n
/
where
Z
int
=
int
e
int
/
The probabiliy that the translational orbital n is occupied is given by the ratio of the term in to the Gibbs
sum
f (
n
) =
Z
int
e
n
/
1+Z
int
e
n
/
Z
int
e
n
/
125
if we assume that f (
n
) 1. Thus we can see that
N = Z
int
n
e
n
/
(6.3)
where
Z
int
=
int
e
int
/
= 1+e
/
1
= 0
2
=
and
n
e
n
/
= n
Q
V
we can see from Equation 1 that the chemical potential is given as
=ln
_
n
n
Q
Z
int
_
=
_
ln
_
n
n
Q
_
lnZ
int
_
which simply becomes
=
_
ln(n/n
Q
) ln(1+e
/
_
b) The free energy is dened as
F
int
=NlnZ
int
= Nln(1+e
/
)
and the total free energy is given by
F
tot
= N
_
ln
_
n
n
Q
_
ln(1+e
/
) 1
_
c) The Entropy is dened as
int
=
_
F
_
V,N
= N

_
ln(1+e
/
)
_
= N
_
ln(1+e
/
) +

[ln(1+e
/
]
_
where
[ln(1+e
/
)] =

2
e
/
1+e
/
thus we nd the entropy to be
int
= N
_
ln(1+e
/
) +

_
e
/
1+e
/
__
and the total entropy is dened as
tot
= N
_
ln
_
n
Q
n
_
+
5
2
+ln(1+e
/
) +

_
e
/
1+e
/
__
126
d) The pressure is given as
p =
_
F
tot
V
_
we can see from b that the total free energy is given as
F
tot
= N[ln(n) ln(n
Q
) ln(1+e
/
) 1] = N
_
ln
_
N
V
_
ln(n
Q
) ln(1+e
/
) 1
_
we can see that the derivative in terms of the volume removes every term except the rst one, thus
F
V
=
N
V
thus the pressure is given as
p =
N
V
e) The heat capacity at constant pressure is given as
C
P
=
5
2
N+
_
int
_
P
where the rst term comes from the ideal gas solution without any degrees of freedom. Thus we
need to solve
int
= N

_
ln(1+e
/
) +

_
e
/
1+e
/
__
which becomes
int
= N
_
2
e
/
1+e
/
2
_
e
/
1+e
/
_
+

_
e
/
1+e
/
__
= N
_
e
/
1+e
/
_
= N
_
(1+e
/
)
2
e
/
e
/
2
e
/
(1+e
/
)
2
_
= N
()
2
3
_
e
/
(1+e
/
)
2
_
thus we nd that the heat capacity at constant pressure to be given as
C
P
= N
_
5
2
+
()
2
2
_
e
/
(1+e
/
)
2
__
Problem # 6 Isentropic relations of ideal gas
127
a) Show that the differential changes for an ideal gas in an isentropic process satisfy
dp
p
+
dV
V
= 0
d
+( 1)
dV
V
= 0
dp
p
+

1
d
= 0
where =C
P
/C
V
. These relations apply even if the molecules have internal degrees of freedom.
We know that for an isentropic gas
pV
= constant
/(1)
p = constant V
1
= constant
V
(pV
) =V
dp
dV
+ pV
1
= 0
dp
dV
=
p
V
thus we can see tha
dp
p
+
dV
V
= 0
for the temperature and the volume relationship we can use
V
(V
1
) =V
1
d
dV
+( 1)V
2
= 0
thus
d
+( 1)
dV
V
= 0
and nally for the temperature pressure relationship we can use
(
/(1)
p) =
/1
dp
d
+ p

1
(

1
1)
= 0
thus we can see that this simplies into
dp
p
+

1
d
b) The isentropic and isothermal bulk moduli are dened as

B
=V
_
p
V
_
=V
_
p
V
_
Show that for an ideal gas B
=p; B
= p. The velocity of sound in a gas is given as c = (B
/)
1/2
;
there is very little heat transfer in a sound wave. For an ideal gas of molecules of mass M we have
p = /M, so that c = (/M)
1/2
. Here is the mass density.
We have shown that
dp
dV
=
p
V
thus the isentropic bulk moduli is given as
B
=V
_
p
V
_
= p
128
for the isothermal bulk moduli we must consider
pV = N
and we know that for a constant temperature
dp
dV
V + p = 0
dp
dV
=
p
V
thus the bulk moduli is given as
B
=V
_
p
V
_
= p
Problem # 7 Convective isentropic equilibrium of the atmosphere
The lower 10-15 km of the atmosphere-the troposphere-is often in a convective steady state at constant
entropy, not constant temperature. In such equilibrium pV
is independent of altitude, where =C

P
/C
V
.
Use the condition of mechanical equilibrium in a uniform gravitational eld to
a) Show that dT/dz = constant, where z is the altitude. This quantity, important in meteorology, is called
the dry adiabatic lapse rate. (Do not use the barometric pressure relation that was derived in Chapter
5 for an isothermal atmosphere.)
We know that the condition of mechanical equilibrium in a uniform gravitational eld is given as
Vdp =Nmgdz
where the left hand term is for the energy due to the expansion and the right hand term is due the the
gravitational potential. We can see that
dp
dz
=
Nmg
V
dT
dz
=
dT
dp
dp
dz
where
d
dp
=
1
p
dT
dp
=
1
T
p
thus
dT
dz
=
1
T
p
Nmg
V
but we know that
V =
Nk
B
T
p
thus we nd that
dT
dz
=
1
mg
k
B
which is constant.
129
b) Estimate dT/dz, in
0
C per km. Take = 7/5.
Using our previous result we nd, also using = 7/5 yields
dT
dz
=
2
7
mg
k
B
we nd the molecular mass of air to be 28.97 amu, thus we nd
dT
dz
=
2
7
28.971.6610
27
kg(9.8ms
2
)
1.3810
23
(m
2
kgs
2
K
1
)
=9.75
K
km
= 9.75
C
km
c) Show that p
, where is the mass density.

For an isentropic process we know that
pV
= constant
we know that the mass density is dened as
=
M
V
= m
N
V
thus the volume is given as
V =
mN
which allows us to substitute into the previous expression as

p
_
mN
= constant
p =

(mN)
so
p
If the actual temperature gradient is greater than the isentropic gradient, the atmosphere may be unsta-
ble with respect to convection.
Problem # 8 Ideal gas calculations
Consider one mole of an ideal monotomic gas at 300 K and 1 atm. First, let the gas expand isothermally
and reversibly to twice the initial volume; second, let this be followed by an isentropic expansion from
twice to four times the initial volume.
Process 1 is isothermal and reversible thus we know that the pressure after expansion is given as
p
i
V
i
= p
f
V
f
p
f
=
1
2
p
i
thus the nal pressure is half of the initial pressure. We also know that the entropy is given as
=
2
1
= Nln(V
2
/V
2
)
130
the work done by the gas in the expansion is given as
W =
Z
V
2
V
1
pdV =
Z
V
2
V
1
(N/V)dV =Nln(V
2
/V
1
)
and the heat is found by assuming that
Q+W = 0 Q =W = Nln(V
2
/V
1
) (6.4)
Process 2 is an isentropic process, which is a process that happens under constant entropy. we know
that under isentropic conditions that
= 0 Q = 0
we can nd the temperature using the entropy
(,V) = N(ln
3/2
+lnV +constant)
so that the entropy remains constant if
ln
3/2
V = constant
thus
3/2
V = constant
so for an expansion at constant entropy fromV
1
to V
2
we have
3/2
1
V
1
=
3/2
2
V
2
(6.5)
a) How much heat (in joules) is added to the gas in each of the two processes?
From Equation 2 we can see that the heat added for process 1 is given as
Q
1
= Nln(2) = Nk
B
T ln(2)
where we know that this can also be expressed as
Q
1
= nRT ln(2)
where R is the molar gas constant, thus we nd
Q
1
= 1 mole8.31 J/K mole300 Kln2 1728 Joules
and for process 2 we have shown that the heat added is
Q
2
= 0
b) What is the temperature at the end of the second process?
131
The nal temperature for process two can be found by using Equation 3, as
f
=
i
_
V
1
V
2
_
2/3
or
T
f
= T
i
_
V
1
V
2
_
2/3
= 300 K
_
1
2
_
2/3
thus the nal temperature is
T
f
= 189 K
c) Suppose the rst process is replaced by an irreversible expansion into a vacuum, to a total volume twice
the initial volume. What is the increase of entropy in the reversible expansion, in joules per kelvin?
If we replace process 1 by an irreversible expansion into a vacuum we know that the following properties
hold
U = 0 W = 0 Q = 0
no means of doing external work is provided so that the work done is zero. If no work is done than no heat
is added in the expansion. Because the energy is also unchanged than the temperature is unchanged. The
increase of entropy when the volume goes from V
1
to V
2
is given by
1
= Nln(V
2
/V
1
) = Nln(2)
where
N = 1 mole
6.0210
23
atoms
mole
= 6.0210
23
atoms
thus the change in entropy is given as
= 4.1710
23
in standard units this is simply
= k
B
4.1710
23
this is simply
= 5.75
J
K
132
Chapter 7
Fermi and Bose Gases
Roadmap
a) Fermi Gas
1. Metals: Fermi level, density of states, ground state energy, pressure of a fermi gas, heat capacity,
and paramagnetic succeptibility.
2. White Dwarfs
3. Nuclei
b) Bose Gas
1. Bose Einstein condensation in liquid helium 4
2. Chemical potential and the temperature at which this condensation occurs
7.1 Fermi Gas
we know that the quantum concentration is given by
n
Q
=
_
m
2
2
_
3/2
we know that when n > n
Q
then this is when quantum behaviours become important. We can also write
this as
m
2
2
< n
2/3
or
<
2
2
m
n
2/3
=
0
if
0
we call this a degenerate gas and when
0
we call this a classical gas.
133
7.1.1 Metals
Metals contain free electrons that are donated by atoms in the lattice. This gives properties of high
eloectric conductivity. Lets consider two kinds of metals. The alkili metas which are Li, Na,K and Ca
each donate 1 s electrons where for N atoms we have N free electrons. The alkili earth Be,Mg,Ca,Sr, and
Ba each donate 2 s electrons. Thus N atoms give 2N free electrons. At room temperature, the mean free
path is 40 nm or > 100 lattice spacings. At low temperatures, the mean free path 400, 000 nm = 400
m, thus we can see that the electrons are very free. We will now derive the Fermi energy
7.1.2 Fermi Energy
Lets take a box that have a set of well dened energy levels. We know that since it is fermions that we are
constrained by the exclusion principle. The lowest energy level is called the fermi energy level
F
. We
know that the energy in the box is given by
=

2
2
2mL
2
(n
2
x
+n
2
y
+n
2
z
) =

2
2
2mL
2
n
2
to relate the number of states in energy to the number of states that lie in n and n+dn
N(n)dn = 2
1
8
4n
2
dn =n
2
dn
F
=

2
2mL
2
2
n
2
F
7.1.3 Fermi Gas
the Fermi energy is given as
F
=

2
2m
_
3
2
N
V
_
3/2
the density of states is given as
D() =
V
2
_
2m
2
_
3/2
1/2
the Fermi density of states is given as
D(
F
) =
3
2
N
F
and the energy is given as
u(0) =
3
5
N
F
=
3
5
Nk
B
T
7.1.4 Pressure of the Fermi gas (T = 0)
We recall that the pressure p is given as
p =
_
u(0)
V
_
,N
134
once again we have u(0) can be written as
u(0) =
3
2
N
F
=
3
5
_

2
2m
(3
2
)
2/3
_
N
5/3
V
2/3
so we simply need to take the derivative to nd
p =
3
5
_
2
3
__
2
2m
(3
2
)
2/3
__
N
V
_
5/3
=
2
5
_
2
2m
_
3
2
N
V
_
2/3
_
N
V
where
F
=
_
2
2m
_
3
2
N
V
_
2/3
_
thus the pressure is given as
p =
2
5
F
N
V
or
pV =
2
5
Nk
B
T
F
it might be instructive to see how big this pressure really is. Lets work out the pressure for an ideal gas
7.1.4.1 Pressure of ideal gas at STP
we know that the pressure is given as
p =
RT
V
=
8.3 J mole
1
K
1
233
22.410
3
m
3
10
5
Pa
now what how does this relate to the Fermi pressure? Lets take sodium as our example, thus
V = 23 cm
3
= 2310
6
m
3
T
F
= 35, 000 K
thus
p =
2
5
RT
F
V
510
9
Pa
thus the pressure of the Fermi gas to the pressure of an ideal gas at STP is given as
p
F
p

T
F
T

22, 400
23
10
5
7.1.5 Specic Heat of Fermi Gas
For insulators at room temperature is C
V
= 3Nk
B
and for metals the result is basically the same.
135
7.1.5.1 Approximate argument for C
V
the number of lectrons that are excited is given by an increase in temperature is
N
k
B
T
F
N
T
T
F
thus the change in the energy is
N
T
T
F
k
B
T
and thus the heat capacity is
C
V
=

T
_
Nk
B
T
2
T
F
_
Nk
B
T
T
F
T
T
F
classical value 0.01(Nk
B
)
for sodium at room temperature. The exact result is given as
C
V
=

2
2
Nk
B
T
T
F
= T
where is given as
=

2
2
Nk
B
T
F
the total heat capacity of a metal
C
V
= T +AT
3
where the rst term come from the electrons and the second term comes from the phonon contribution. At
room temperature, the phonos dominate and at low temperature, the elctrons dominate.
7.1.6 Paramagnetic Susceptibility
Calssically
=
N
2
k
B
T
Curies Law
when we increasee B, only electrons within k
B
T of
F
ca ip spins, thus
F

N
2
B
k
B
T
_
T
T
F
_
=
N
2
B
k
B
T
F
this is known as Pauli paramagnetism.
7.1.7 White Dwarfs
White dwarfs are stars that have undergone gravitational collapse and is help up under degeneracy pressure.
The density is typically 10
5
10
6
gm cm
3
. This was rst discovered from Sirius Bwhich was emperically
determined from the pertubations from Sirius B. We nd that the mass of Sirius B is M
B
= 210
33
g and
the radius is given as r
B
= 210
9
cm.This can be acquired from the Planck distribution and Wienss law.
From this, we nd that the density 7 10
4
g cm
3
. We believe that all matter is ionized and thus we
136
have Fermi gases. We must consider the protons and electrons as being two distinct samples of Fermi
gases. If we have
1 g cm
3
l 10
10
m
10
6
g cm
3
l 10
12
m
and
N
V

_
1
10
12
_
3
m
3
10
36
m
3
and the Fermi energy is
F

F
_
10
36
10
28
_
2/3
310
5
eV T
F
310
9
K
where we know that the temperature needed for fusion is T 10
7
K. Since T T
F
this is a highly
degenerate gas. Lets do this for protons, lets rst assume that the nuclie are protons. The mass of the
proton is approximately 2000m
e
. We can see that
F

1
m
thus for the protons
T
F

310
9
2000
1.510
6
K
which is treated as a classical gas.
7.1.8 Neutron Stars (The Nucleus)
The atomic number A is the number of protons and neutrons. The radius is given as
r = (1.310
13
cm)A
1/3
then
N
V
=
3A
4(1.310
13
cm)
3
A
10
38
cm
3
10
44
m
3
since N
p
N
n
thus
N
V
510
43
m
3
plugging in the numbers yield
F
= 310
7
eV 30 MeV T
F
410
11
K
7.1.9 Bose-Einstein Condensation in Liquid
4
He
The helium nucleus has 2 neutrons and 2 protons with a spin of 0 and obeys Bose-Einstein statistics.
This was historically discovered when people started measuring the heat capacity. They measured that
something spectacular happened as you lowered the temperature of the helium liquid, when theyt got to
2.18 K they saw a weird behavior in the heat capacity. They named this transition point, the lambda point.
137
Justication for treating Helium 4 as a gas
We will treat Helium 4 as a gas rather than a liquid in order to model its charactersitics. there are three
main points
Computer simulations predict the density from known quantum properties. In fact, the measured
density is about three times less. Interactions will be weakened as they are pushed apart. The
zero point uctuations in the atoms increase their kinetic energy, thus pushing them further apart
(increase their seperation). 0.1 g/cm
3
.
Even for T > T
, the thermal conductivity and the viscosity are roughly the same as those of a gas
of the same density.
It is very hard to solidify helium, helium liquid will always remain liquid at atmospheric pressure
down to arbitrarily low temperatures (lowest temperatures possible). This implies weak interactions
between helium atoms. To solify helium you must apply a pressure greater than 25 atm.
Lets consider 1 cm
3
cube, the ground state energy is given as
0
=

2
2
2mL
2
(1
2
+1
2
+1
2
) =
3
2
2
2mL
2
the rst excited state is given as
1
=
6
2
2
2mL
2
and the difference is
0
=
3
2
2
2mL
2
10
37
J 10
18
eV 10
14
K
if we were to cool this to 10
16
K (impossible) vertually all of the atoms will be i the ground state. In fact,
at 1 K virtually all of the atoms are in the ground state. The entire behavior of this gas is controlled mainly
by the chemical potential. The above calculation is wrong because it is a Bose gas.
7.1.10 Bose Einstein Distribution
The BE distribution si given as
f () =
1
e
()/
1
it is a requirment that the chemical potential always be less then the energy ( < ). For convinience we
will set
0
= 0 f (0, T) =
1
e
/k
B
T
1
lets suppose that the temperature T becomes very small. In the limit
T 0 f (0, 0) = N
where N is the number of atoms in the box, so
f (0, 0) = N = lim
T0
1
e
/
1
where /k
B
T 1
138
we are really concerned with the behavior of the chemical potential rather than the temperature. Given the
above condition allows us to expand the exponetial
1
1(/k
B
T) 1

k
B
T
hence

k
B
T
N
this tells us that the chemical potential is just below the ground state energy, but very very close to it.
Hence < 0, but very close to
0
= 0.
Example
lets take
T = 1 K N 10
22
thus
10
45
J
which is very close to the ground state energy. Thus the probability of the number of particles in the rst
excited state is as follows
f (
1
, 1K) =
1
e
(
!
)/
1

k
B
T

1 K
10
14
K
10
14
thus, at 1 K only 1 atom in 10
8
is in the rst excited state. We can nally calculate the occupancy of the
ground state as a function of temperature.
7.1.11 Temperature dependence of f (0, T)
The rst thing we need to do is write down the density of states, this is given as
D() =
V
4
2
_
2m
2
_
3/2
1/2
spin 0
once again lets consider a few energy levels, a ground state and higher energy states, where the total
number of particles is given as
N = N
0
+N
e
whereN
0
ar the atoms in the ground state and N
e
are the atoms in the excited state. Thus
N = N
0
(T) +
Z

0
D() f (, T)d
we must now evaluate this, this is equal to
N =
1
e
/k
B
T
1
+
V
4
2
_
2m
2
_
3/2
Z

0
1/2
e
()/k
B
T
1
d
as before, we can neglect the chemical potential because it is negligable, thus we have
x =

k
B
T
139
which allows us to write
N
e
(T) =
V
4
2
_
2m
2
_
3/2
(k
B
T)
3/2
Z

0
x
1/2
e
x
1
dx =
V
4
2
_
2m
2
_
3/2
(k
B
T)
3/2
(1.31
1/2
)
which can be simplied as
N
e
= 0.17V
_
mk
B
T
2
_
3/2
the fraction of excited states is
N
e
N
0.17
V
N
_
mk
B
T
2
_
3/2
2.61
n
Q
n
this a very useful simple result
N
e
N
2.61
n
Q
n
wha this shows us is that the number of excited atoms increases as the temperature to the 3/2. This gives
us a prediction of the transition point for helium. T
is given by
N
e
N
= 1
thus
T
=

2
2m
_
N
0.17V
_
2/3
3 K
where the observed value is T
= 2.18 K. If we write
N
e
N
=
_
T
T
_
3/2
and
N
0
N
= 1
_
T
T
_
3/2
qualitatively this result is correct, but quantitatively it is incorrect. The model is too simple. What we
have seen is that at low temperatures we have a high concentration of atoms in the ground state. Thus we
have what is called a macroscopic quantum state. The Bose-Einstein condensation is this, that is to say,
we have some (one) quantum mechanical wave function
(r, t) =|(r, t)|e
i(r,t)
for all atoms in the ground state. There are two other kinds of systems that have the same properties.
Helium 3 atoms are fermions but it turns out that at low enough temperatures these helium 3 atoms can
pair together to give bosons and they can also undergo a condensation to the ground state to create a
super uid (1972). The third example is super conductivity, this is where we have electrons that become
cooper pairs which act like bosons. (
k ,
k ), where they have zero momentum and zero spin. This was
understood theoretically in 1957 BCS.
140
7.1.12 Properties of
4
He Superuids: Thermomechanical effects
Lets suppose we have two resevoirs of helium that are connected by a narrow capillary (pipe). It blocks
nromal atoms but it passes superuid atoms. We then cool the helium down and put pressure on one
side of the resevoir. We see that we will have an abundance of superuid atoms on one side of the resevoir.
The side which contains the most superuid atoms will lower its temperature while the side that has
less superuid atoms will increase its temperature. Suppose we take the same equipment and increase the
temperature on one side. Initially both resevoirs are at temperature T and we then increase the temperature
by T on one side. This will create an osmotic pressure of superuid helium. The level on one side falls
while the level on the other side increases to take care of the pressure difference.
7.2 Summary
For the Fermi gas
F
=

2
2m
_
3
2
N
V
_
2/3
the density of states is given as
D() =
V
2
2
_
2m
2
_
3/2
1/2
and
D(
F
) =
3N
2
F
the ground state energy is given as
u(0) =
3
5
N
F
also
pV =
2
5
Nk
B
T
F
the heat capacity is given as
C
V
=

2
2
Nk
B
T
T
F
= T
and also

2
B
k
B
T
F
for the Bose gas
T 0 =
k
B
T
N
and
N
e
N
0.17
V
N
_
mk
B
T
2
_
3/2
2.61
n
Q
n
141
7.3 Problems
Problem # 1 Energy of relativistic Fermi gas
For electrons with an energy mc
2
, where m is the rest mass of the electron, the energy is given by
pc, where p is the momentum. For electrons in a cube of volume V = L
3
the momentum is of the
form (/L), multiplied by (n
2
x
+n
2
y
+n
2
z
)
1/2
, exactly as for the nonrelativistic limit.
a) Show that in this extreme relativistic limit the Fermi energy of a gas of N electrons is given by
F
= c(3n/)
1/3
= c
_
3N
V
_
1/3
where n = N/V.
Since we know that we are in the relativistic case that the energy is dened as
=
c
L
n
but we know that the Fermi density is related to the number of particles by
N = 2
1
8
4
3
n
3
F
=

3
n
3
F
n
F
=
_
3N
_
1/3
The factor of two arises because an electron has two possible spin orientations. The factor of 1/8 arises
because only triplets in the positive ocatant of the sphere in n space are to be counted, thus the Fermi
energy is given by
F
=
c
L
n
F
= c
_
3N
L
3
_
1/3
which simplies to
F
= c
_
3N
V
_
1/3
= c(3n/)
1/3
b) Show that the total energy of the ground state of the gas is
U
0
=
3
4
N
F
We know that this can be solved by knowing that the total energy of the system in the ground state is given
by
U
0
= 2

nn
F
n
= 2
1
8
4
Z
n
F
0
n
2
dn
n
=

2
c
L
Z
n
F
0
n
3
dn =

2
c
4L
n
4
F
=

2
c
4L
n
3
F
n
F
=
3c
4L
Nn
F
which simplies into
U
0
=
3
4
N
F
142
Problem # 2 Energy, heat capacity, and entropy of degenerate boson gas
Find expressions as a function of temperature in the region <
E
for the energy, heat capacity, and
entropy of a gas of N noninteracting bosons of spin zero conned to a volume V. Put the defenite integral
in dimensionless form; it need not be evaluated. The calculated heat capacity above and below
E
is
shown in Figure 7.12. The difference between the two curves is marked: It is ascribed to the effect of
interactions between the atoms.
We know that the density of modes is given by
D() =
V
4
2
_
2m
2
_
3/2
1/2
for a particle of spin 0. The total number of atoms in the ground and excited orbitals is given by the sum
of the occupancies of all orbitals
N =
n
f
n
= N
0
() +N
e
()
and the total energy is given by
U =
n
f
n
= N
0
0
() +N
e
()
but we know that the number of atoms in the excited state is given by
N
e
() =
Z

0
D() f (, )d
thus the total energy is given by
U =
Z

0
D() f (, )()d
we also know that the Bose-Einstein distribution is given as
f (, ) =
1
e
()/
1
thus we nd that the total energy is given as
U =
V
4
2
_
2m
2
_
3/2
Z

0
1
1
e
/
1
3/2
d
where = e
/
and if we let x = / we nd
U =
V
4
2
_
2m
2
_
3/2
5/2
Z

0
1
1
e
x
1
x
3/2
dx
For we can see that
= 1
this is because we can Taylor expand the activity to nd
1+

= 1
1
N
143
but we have seen that
=

N
N 1
The integral can now be written as
Z

0
e
x
1e
x
x
3/2
dx =
s=1
Z

0
x
3/2
e
sx
dx
if we let y = sx then
s=1
Z

0
x
3/2
e
sx
dx =
_

s=1
s
5/2
_
Z

0
e
y
y
3/2
dy
if we now let y = u
2
then we nd
Z

0
e
y
y
3/2
dy = 2
Z

0
e
u
2
u
4
du =
3
4
and we also nd that

_

s=1
s
5/2
_
1.34
thus we nd that the total energy is given by
U =
4.02V
16
_
2m
2
_
3/2
5/2
and we know that the heat capacity is given by
C
V
=
U
=
5
2
4.02V
16
_
2m
2
_
3/2
3/2
which simplies into
C
V
= 0.63V
_
2m
2
_
3/2
3/2
and the entropy is given by
C
V
=
_
_
V
thus we can see that the total entropy is given by
=
Z

0
C
V
d = 0.61V
_
2m
2
_
3/2
Z

1/2
d =
2
3
(0.63)V
_
2m
2
_
3/2
3/2
or
= 0.42V
_
2m
2
_
3/2
3/2
Problem # 3 Fluctuations in a Fermi gas
144
Show for a single orbital of a fermion system that
(N)
2
=N(1N)
if N is the average number of fermions in that orbital. Notice that the uctuation vanishes for orbitals
with energies deep enough below the Fermi energy so that N = 1. By denition, N = NN
From Equation 5.83 we know that the uctuations go as
(N)
2
=
N
Equation 6.2 gives that the average number of particles is given by

N() = f () =
1
e
()/
1
where the + is for fermions and the - is for bosons, f () is the average occupancy that denotes the thermal
average number of particles in an orbital of energy . Thus for a Fermi gas we nd that
N =
1
e
()/
+1
and
N
=
d
d
_
1
e
()/
+1
_
=
d
d
_
1
K
_
if we let
K = e
()/
+1
dK
d
=
1
e
()/
thus
dN
d
=
dN
dK
dK
d
N =
1
K
dN
dK
=
1
K
2
we nd
N
=
1
e
()/
(e
()/
+1)
2
thus the uctuations is given as
(N)
2
=
e
()/
(e
()/
+1)
2
to write it in a more suggestive form we can simply do
(N)
2
=
e
()/
+11
(e
()/
+1)
2
=
1
e
()/
+1
_
1
1
e
()/
+1
_
which can also be written as
(N)
2
=N(1N)
Problem # 4 Fluctuations in a Bose gas
145
If N as in (11) is the average occupancy of a single orbital of a boson system, then from 5.83 show that
(N)
2
=N(1+N)
thus, if the occupancy is large, with N 1, the fractional uctuations are of the order unity:
(N)
2
/N 1, so that the actual uctuations can be enormous. It has been said that bosons travel in
ocks.
As before we know that
N = f () =
1
e
()/
1
and as before
N
=
1
e
()/
(e
()/
1)
2
thus the uctuation is given as
(N)
2
=
e
()/
(e
()/
1)
2
written in a more suggestive way
(N)
2
=
e
()/
1+1
(e
()/
1)
2
=
1
e
()/
1
_
1+
1
e
()/
1
_
which can also be expressed as
(N)
2
=N(1+N)
146
Chapter 8
Heat and Work
Roadmap
1. Heat and Work: Exact and inexact differentials
2. Heat engines and refrigerators: 2nd law revisited
3. Carnot cycle for the ideal gas
4. Work and heat at constant temperature or at constant temperature and pressure: Enthalpy and Gibbs
free energy
8.1 Heat and Work: Exact and inexact differentials
We know that heat is a transfer of energy by thermal contact, which is usually denoted as dQ. Work is
a transfer of energy by changes of external parameters, i.e volume, electric eld or magnetic elds. For
reversible process, the rst law tell us that the total change is given by
du = dQ+dW
where the rst term is for the heat and the second term is for the work. du is what we call an exact
differential. If we start at some point a to some point b it doesnt matter what path we take, the change in
the energy is independent of the path. But for the change in heat or the cahnge in the work are dependent on
the path chosen. The internal energy u is a function of state while the heat and the work are not functions
of states. An exact differential is of the following form
dF = F(x +dx, y +dy) F(x, y) = A(x, y)dx +B(x, y)dy
anything that can be written in this form is an exact differential. But not all functions of the form
C(x, y)dx +D(x, y)dy are of the form as before G(x +dx, y +dy) G(x, y). We want to now take two
examples to illustrate this point.
8.1.1 Example 1
Lets let
dG =dx +
x
y
dy = dx +x(d lny)
147
where and are cosntants. If we now take the integral, via (1,1) to (1,2) to (2,2)
Z
f
i
dG = +2(ln2ln1) = +2ln2
If we now take the integral, via (1,1) to (2,1) to (2,2)
Z
f
i
dG =(ln2) + =+ln2
this is an example of an inexact differential. The real problem is in the term of . Now for an exact
differential
dF =
dG
x
=

x
dx +
dy
y
= d(lnx +lny)
now if we dow the same thing as last time we nd If we now take the integral, via (1,1) to (1,2) to (2,2)
Z
f
i
dG = ln2+ln2 =ln2+ln2
If we now take the integral, via (1,1) to (2,1) to (2,2)
Z
f
i
dG = ln2+ln2 =ln2+ln2
where we can see that these are exactly the same. Any type of work can be converted to any other type of
work (in principle) and entropy is conserved. Lets imagine that we are compressing a gas in a cylinder
via some magnetic interaction. If we attach a bar magnet to the piston and then we move a second
magnet to the rst which compresses the gas, thus we have used magnetic work to create mechanical
work. Work can be also be completely converted into heat, i.e stirring your coffee in the morning.
However, the converse is not true, heat cannot be converted completely into work in a reversible process.
Thus it is really the study of this third point that is the subject of study of heat engines and refrigerators.
8.2 Heat Engines and Refrigerators
8.2.1 Engines
This is some kind of cyclic device which takes in heat to convert to mechanical work and reject some heat
at a lower temperature. We have some thermal resevoir at some temperature T
1
with some other resevoir at
T
2
, and we also have heat Q
1
and Q
2
and we get out the work W. Where Q
1,
Q
2
, and W are all magnitudes.
The entropy is given as
1
=
Q
1
2
=
Q
2
2
hence, the work W is simply
W = Q
1
Q
2
= Q
1
1
Q
1
= Q
_
1
_
where this is known as the Carnot efciency
C
=
W
Q
=

1
1
this is the maximum possible efciency that an engine can run on. In practice all engines will have
additional losses and this efciency can never be achieved. A car engine where
1
= 600 K and
2
= 300
K, we can see that the maximum efciency is about 1/2. We can reverse the process to make a refrigerator.
148
8.2.2 Refrigerators
A refrigerator is simply a heat engine in reverse. So we have a resevoir at T
1
and another at T
2
, we also
have Q
1
and Q
2
and we put in work W. The Carnot efciency is the following,
C
=
Q
2
W
=
Q
2
Q
1
Q
2
the exact relationships for the entropy still hold, hence
C
=
Q
2
2
Q
2
Q
2
=

2
2
this is the maximum efciency of a refrigerator. Lets suppose that
1
= 300 K and
2
= 260 K, we can see
that
C
=
260
40
= 6.5
This is also how air conditioners work, where T
2
is the temperature in the room and T
1
is the temperature
of the outside. We can also consider a heat pump where T
2
is the temperature outside and T
1
is the
temperature T
2
and we nd that the Carnot efciency is now given by
C
=
Q
1
W
=
Q
1
Q
1
1
Q
1
=

1
2
we can take an example of
2
= 270 K and
1
= 300 K, thus the Carnot efciency is
C
= 10. We can see
that a heat pump is very efcient.
8.2.3 Non ideal case for Heat engine
Just to reacp very briey, we know that
=
Q
1
1
+
Q
2
2
= 0 Q
2
= Q
1
2
and the efciency is given as
C
=
W
Q
1
=

1
1
if we have losses then
> 0
2
>
1
if we now go back we can see that
Q
2
> Q
1
1
for eaxmple, lets set
Q
2
= Q
1
_
1
+
_
where is the inefciency, thus we can see that
=
Q
1
Q
1
_
1
+
_
Q
1
<
C
149
thus we can see that the Carnot efciency is the maximum one can get from heat engines.

C

C
these are statements of the second law of thermodynamics. Thus
0
8.3 Carnot Cycle
8.3.1 The Ideal Gas
If we assume that we have an isothermal expansion of a gas from
low
to
hi
and a xed temperature
hi
. We then do a second expansion which is adiabatic from
hi
and
hi
to
low
. We then have to do two
different compressions, the rst one is isothermal going from
hi
to
low
and at
low
, we then do another
adiabatic compression from
low
to
h
at
low
. This are the four steps of the Cranot cycle. We know that
around the entire cycle, the change in energy is equal to zero
0 =
I
du
this must also be equal to
I
du =
I
d
I
pdV = 0
where the rst term is for the heat and the second term is for the work. Thus the work done by the gas is
W =
I
d =
hi
(
low
hi
) +
low
(
hi
low
)
and thus the work done by the gas is given as
W
gas
= (
hi
low
)(
low
hi)
which is simpy the area of a rectangle. We can replicate this entire process for N molecules and gas using
a p and V diagram. The rs thing is to expand the gas isothermally, thus we know that the pressure drops
and the volume increases. In order to do this we have to apply heat Q
1
. We then do an adiabatic expansion
where the volume increases more and the pressure drops more. We then do an isothermal compression at
the low temperature end, thus the volume decreases and the pressure increases, and thus heat is rejected.
Finally we do the adiabatic compression to get back to the starting point. As before, the area tells us the
work done by the gas. We want to gure out the work done by the gas in each of these 4 processes
W
12
=
Z
V
2
V
1
pdV = N
hi
Z
V
2
V
1
dV
V
= N
hi
ln
_
V
2
V
1
_
= Q
1
then we have the work done during the adiabatic expansion
W
23
= [u(
hi
) u(
low
)] =
3
2
N(
hi
low
)
next we go from point 3 to point 4, which is an isothermal expansion
W
34
= N
low
ln
_
V
4
V
3
_
= Q
2
150
and nally we nd
W
41
= [u(
low
) u(
hi
)] =
3
2
N(
low
hi
)
and the total work is given as
W = N
hi
ln
_
V
2
V
1
_
+N
low
ln
_
V
4
V
3
_
The goal of this calculation is to rederive the Carnot efciency for this process. To nd the Carnot
efciency we must nd a relationship among V
1
...V
4
. Lets assume that we have an ideal monotomic gas.
We then want to use a relationship derived a while ago that we said was useful. At constant entropy we
found the following result
V
2/3
= constant
we now consider where we have processes at constant entropy, this is for 2 going to 3 and we start with
H
V
2/3
2
=
L
V
2/3
3
in other words
V
3
V
2
=
_
L
_
3/2
and now if we look at 4 to 1 we nd
L
V
2/3
4
=
H
V
2/3
1
thus
V
4
V
1
=
_
L
_
3/2
=
V
3
V
2
if we now go back to the expression for the work done we nd
V
2
V
1
=
V
3
V
4
and nally, what we see is the following
ln
_
V
2
V
1
_
=ln
_
V
4
V
3
_
therefore the work done by the gas is given by
W = N(
H
L
)ln
_
V
2
V
1
_
we nally nd the Carnot efciency
C
=
W
Q
1
=
N(
H
L
)ln(V
2
/V
1
)
N
H
ln(V
2
/V
1
)
which reduces to what we found previously
C
=

H
H
151
8.4 Heat and Work at Constant Temperature or Pressure
8.4.1 Isothermal
Isothermal conversion of work into heat. We have a resevoir at a temperature and a piston that will
compress the gas isothermally. For an isolated system, the internal energy is given as
u = u(,V)
and
du(,V) =dpdV thermodynamic identity
which reduces to
du = d() pdV
and the free energy is
dF(, u) = d(u) =pdV
which is the change in work for the system. Thus the work done on the gas is
dW = dF
we can see that heat is an inexact differential. These two thermodynamic functions play different roles,
where dF is a function of state while dW is not. This is why the Helmholtz free energy is such a useful
function.
8.4.2 Isobaric (constant pressure)
Boiling water, chemical reactions are usually at constant pressure. If we impoise a constant pressure on
our system with a piston at a constant force.
F = pA
initially we have some water and we apply heat from underneath. If we start boiling the water, this will
provide a pressure on the piston from the vapor. This moves the piston by an amount dx which will give
us dV = Ada. We need to supply heat to evaporate the water and expand the volume to accomdidate the
gas. We must now write down the work done on the vapor
W =pdV =d(pV) dp = 0
thus the change in the internal energy of the liquid and the vapor is given by
du = dQd(pV)
we will now dene a new quantity H which is
dH = d(u+ pV) = dQ
where this new quantity H is known as the enthalpy, thus
dQ = dH
152
8.4.3 Work and Heat at constant Pressure
If we take our previous system, where we apply some heat, but now we also apply some work to the
system, i.e a paddle moving the water. So
du = dQd(pV) +dW
we can therefore write this as follows
dW = du+d(pV)
and also
dQ = d = d() constant
putting this all together gives
dW = d(u+ pV ) = dG
where
G = u+ pV = F + pV
where this is known as the Gibbs Free Energy. Thus the work done on the system is simply
dW = dG
8.4.4 Gibbs Free energy for varying N
We know that
dG = du+ pdV +Vdpdd
recall that
du = dpdV +dN
this is the thermodynamic identity when N varies. We can now insert this into the previous line to nd
dG =d +Vdp+dN
so we nowhave this new termthat is very useful. We see immideately that we can write down the following
three results
=
_
G
_
p,N
V =
_
G
p
_
,N
=
_
G
N
_
, p
the last result is also very useful, if we integrate
G(, p, N) = N(p, )
this shows us that the chemical potential is the Gibbs free energy per particle. This is really what makes
phase transformations tick.
153
8.5 Summary
We now summarize the important results. We begin with heat as
dQ = d
is the transfer of energy by thermal contact with a resevoir. We also talked about work, which is another
inexact differential which is the transfer of energy by the change in external parameters, we also found
d = 0
we also found for an ideal heat engine
C
=

1
2
1
>
2
for a refrigirator we nd
C
=

2
2
can be > 1
we then showed for an isothermal process that the work
dW = dF
we also talked about isobaric heat and work allowed us to introduce the enthalpy H which is given by
H(, p) = u+ pV
and the heat of vaporization
dQ = dH
we also introduced the Gibbs free energy
G(, p) = u+ pV = F + pV
and the work done on the system at constant pressure and temperature is
dW = dG
and nally we discussed what happens when the number of particles change, we nd
dG(, p, N) =d +Vdp+dN
and hence, we nd three very useful results
=
_
G
_
p,N
V =
_
G
p
_
,N
=
_
G
N
_
, p
154
8.6 Problems
Problem # 1 Photon Carnot Engine
Consider a Carnot engine that uses as the working substance a photon gas. The Carnot cycle can be
represented as
isentropic
1
2
3
4
h l
l
h
i
s
o
t
h
e
r
m
a
l
i
s
o
t
h
e
r
m
a
l
isentropic
The cycle consists of two expansion phases (1 2 and 2 3) and two compression phases (3 4 and
4 1). There are two isentropic phases and two isothermal phases. The work done is given by the area
of the rectangle created by the solid line and the heat consumed at
h
is the area sorrounded by the broken
line. Since we are considering a photon gas as the working substance of the engine we must consider the
energy density of a photon gas which is given as
U =

2
V
15
3
c
3
4
(8.1)
but we know that
d = dU
+ pdV
thus at constant volume we have
d =
4
2
V
2
15
3
c
3
d
integrating both sides yield
=
4
45
2
V
3
c
3
3
(8.2)
a) Given
h
and
l
as well as V
1
and V
2
, determine V
3
and V
4
.
155
We know that the entropy is the same at both 1 and 4 and 2 and 3 thus
4
=
1

2
=
3
using Equation 2 we nd
V
4
3
l
=V
1
3
h
V
2
3
h
=V
3
3
l
thus
V
4
=V
1
_
l
_
3
V
3
=V
2
_
l
_
3
b) What is the heat Q
h
taken up and the work done by the gas during the rst isothermal expansion? Are
they equal to each other, as for the ideal gas?
We know that
Q
h
=
Z
dQ =
Z
pdV =
Z
d
thus
Q
h
=
Z
2
1
d = (
2
1
) =
4
2
45
3
c
3
4
h
(V
2
V
1
) =
4
45
4
h
(V
2
V
1
)
where
=

2
3
c
3
so we nd that the heat taken up is
Q
h
=
4
45
4
h
(V
2
V
1
)
and the work is found by using
dW = dU dQ
thus the work is
W
12
=
_
Z
2
1
dU
Z
2
1
d
_
the minus sign comes because this is the work done on the gas, thus we can solve to nd
W
12
=
_
U
2
U
1
_
4
45
4
h
(V
2
V
1
)
__
the change in energy is given by Equation 1 as
U
2
U
1
=

15
4
h
(V
2
V
1
)
thus the work is
W
12
=
_

15
4
h
(V
2
V
1
)
_
4
45
4
h
(V
2
V
1
)
__
or
W
12
=
1
45
4
h
(V
2
V
1
)
we can see that these two quantities are not equal as in the case of the ideal gas.
156
c) Do the two isentropic stages cancel each other, as for the ideal gas?
The work for the two isentropic phases is given by
W
23
=
Z
3
2
dU W
41
=
Z
1
4
dU
since d = 0, as before the minus sign comes from the fact that work is being done on the gas we nd
W
23
= [U
3
U
2
]
=
_
1
15
[
4
l
V
3
4
h
V
2
]
_
W
23
=
_
1
15
4
l
V
2
_
l
_
3
4
h
V
2
__
W
23
=
1
15
3
h
V
2
[
h
l
]
and also
W
41
= [U
1
U
4
]
=
_
1
15
[
4
l
V
1
4
h
V
4
]
_
W
41
=
_
1
15
4
l
V
1
4
h
V
1
_
l
_
3
__
W
41
=
1
15
3
h
V
1
[
h
l
]
thus
W
23
+W
41
=
1
15
3
h
[
h
l
][V
2
V
1
]
we can see that they do not cancel each other out as in the case for the ideal gas.
d) Calculate the total work done by the gas during one cycle. Compare it with the heat taken up
h
and
show that the energy conversion efciency is the Carnot efciency.
To nd the total work done we must nally consider the work done during
W
34
=
_
Z
4
3
dU
Z
4
3
d
_
=(U
4
U
3
l
(
4
3
))
which yields
W
34
=
_

15
4
l
(V
4
V
3
)
4
45
4
l
(V
4
V
3
)
_
=
_

45
4
l
(V
3
V
4
)
_
=
_

45
4
l
_
V
2
_
l
_
3
V
1
_
l
_
3
__
=
45
3
h
(V
2
V
1
)
157
where the total energy is given by
W = W
12
+W
23
+W
34
+W
41
=
1
45
4
h
(V
2
V
1
) +
1
15
3
h
[
h
l
][V
2
V
1
]
1
45
3
h
(V
2
V
1
)
=
1
45
3
h
[
h
l
][V
2
V
1
] +
1
15
3
h
[
h
l
][V
2
V
1
]
W =
4
45
3
h
[
h
l
][V
2
V
1
]
and comparing this to the Carnot efciency yields
C
=
W
Q
h
=

h
h
=
T
h
T
l
T
h
Problem # 2 Geothermal Energy
A very large mass M of porous hot rock is to be utilized to generate electricity by injecting water and
utilizing the resulting hot steam to drive a turbine. As a result of heat extraction, the temperature of the
rock drops, according to dQ =MCdT
h
, where C is the specic heat of the rock, assume to be
temperature independent. If the plant operates at the Carnot limit, calculate the total amount W of
electrical energy extractable from the rock, if the temperature of the rock was initially T
h
= T
i
, and the
plant is to be shut down when the temperature has dropped to T
h
= T
f
. Assume that the lower resevoir
temperature T
l
stays constant.
At the end of the calculation, give a numerical value, in kWh, for M = 10
14
kg (about 30 km
3
), C =
1 J g
1
K
1
, T
i
= 600
0
C, T
f
= 110
0
C, T
l
= 20
0
C. Watch the units and explain all steps! for comparison:
The total electricity produced in the world in 1976 was between 1 and 2 times 10
14
kWh.
Since we know that this engine operates at the Carnot efciency then
C
=
T
h
T
l
T
h
=
W
Q
h
thus the work is given as
dW =
T
h
T
l
T
h
dQ =
T
h
T
l
T
h
MCdT
h
thus the total work is given as
W =MC
Z
T
f
T
i
T
h
T
l
T
h
dT
h
= MC
_
[T
i
T
f
] +T
l
ln[
T
f
T
i
]
_
plugging in numbers given by
T
i
= 873 K T
f
= 383 K T
l
= 293 K
W = 2.4810
16
kg J
g
= 2.4810
19
J
in kWh this is simply
1 kWh = 3.610
6
J
thus the work done is given by
W = 6.8810
12
kWh
158
Chapter 9
Phase Transformations
This is when we transform from one phase to another, .e water to ice, water to vapor. We do this by
changing the temperature and pressure. We can also go from ice to vapor, this is known as sublimation
(frost). Another example is going from paramagnetic to ferromagnetic. Also going from normal to super-
conducter. Finally normal Helium 4 to superuid Helium 4.
Road map
1) Gas/liquid/solid phase transformations.
p vs V isothermal
p vs T coexistance curves- triple point
2) Clausis-Clapeyon Equation
Latent heat, vp vs T. Change is boiling point with pressure and latent heat of vaporization of ice
3) Van Der Walls Equations
departures from ideal gas
predictions of p vs V
critical points at which all hree phases can exist
9.1 Gas, Liquid, and Solid Phase Transformations
9.1.1 p vs V
If we look at a plot of the pressure versus the volume for a liquid curve we nd that at low volumes we
have an isotherm. The reason is due to the incompressability of liquid. We start in a liquid state with a
piston pushing hard against it. As we keep removing the pressure we get to a point where the piston is
raised above the liquid. The pressure than becomes constant, and this is where we can have both liquid
and gas (this all occurs in T < T
c
). The place where the pressure becomes constant will be denoted p
0
and this depends on the temperature, we also get what are called metastable phases. And nally as we
159
decrease the pressure and increase the volume we have only gas. The chemical potentail determines all of
these transitions. In liquid stage we nd
l
<
g
in the liquid and gas stage we nd
l
=
g
and nally in the gas stage
g
<
l
9.1.2 Coexistence Curve p vs T
If we look at a plot of prsseure versus temperature we nd that at low temperatures, we have a line that is
very nearly to verticle hat drops down to 0 degrees. Anything on the left we have ice, so that the chemical
potential of the ice is less then the liquid
ice
<
liq
if we now go up from 0 degrees we see that the pressure is exponential in temperature. Everything on the
left of this curve is liquid
liq
<
ice

liq
<
gas
and to the right of te curve we nd gas, also
gas
<
liq
we also have what is known as the critical pressure and critical temperature, P
c
and T
c
374 degrees
celsius. We also have no distinction between the liquid and the gas. To recover the previous plot we
simply need to just take a slice in our current plot to get what are known as coexistence curves. The
particularly interesting things happen at the origin where we have have all three phases of water occuring
at the same point. This is known as the triple point of water P
t
and T
t
. The triple point is actually used to
dene the temperature scale. For water
T
t
= 273.16 K = 0.01
0
C
and
P
t
= 4.58 mm Hg
this is used in thermometry. The line between solid and the liquid is called the fusion curve, we also have
the sublimation curve, that is the line along which gas can be turned directly to a solid, and nally we
have the vaporization curve, that is the line which liquid is transformed into a gas. The fusion curve is
called the ice line, the sublimation curve is called the frost line and the vaporization curve is caled the
steam line. These are some basic features of phase transformations.
9.1.3 Clausius-Clapeyron Equation
Lets consider two neighboring points on our coexistence curve, the rst one has P
o
and T
0
and the second
has P
0
+dP and T
0
+dT. We can say the following that the chemical potential of these two points must
be the same. At the lower point
g
(P
0
, T
0
) =
l
(P
0
, T
0
)
the higher point we nd
160
g
(P
0
+dP,
0
+d) =
l
(P
0
+dP,
0
+d)
we will now do a rst order Taylor expansion to get
g
(P
0
,
0
) +
_
g
P
_
dP+
_
_
P
d =
l
(P
0
,
0
) +
_
l
P
_
dP+
_
_
P
d
we can see that the rst terms go away, we can now collect terms to get
dP
d
=
_
_
P
_
P
_
g
P
_
l
P
_
we can use our knowledge of the Gibbs free enery to solve this, where it was dened as
G(N, P, ) = N(P, )
and also
dG = dNd +VdP
as before
V =
_
G
P
_
,N
=
_
G
_
N,P
and we can see that
V = N
_
P
_
,N
=N
_
_
N,P
we can now dene the volume per molecule and entropy per molecule
v =
V
N
=
_
P
_
,N
this is the volume per molecule, and similarly
s =

N
=
_
_
N,P
which is the entropy per molecule. We can now substitute these results into our initial result. We nd
dP
d
=
s
g
s
l
v
g
v
l
now we have the pressure and temperature in a simple form. The numerator
s
g
s
l
corresponds to the increase in the entropy when one molecule changes from a liquid to a gas. And corre-
spondingly
v
g
v
l
161
corresponds to the increase in the volume when one molecule changes from a liquid to a gas. We can now
look at the latent heat of vaporization L, this is the heat required to transfomr one molecule from the
liquid to the gas phase. We can relate this to d
L =(s
g
s
l
) = s
or
dQ = d
we thus nd
v = v
g
v
l
and
dP
d
=
L
v
this is known as the Clausius-Clapeyron Equation. This conrms the results from the Coexistence
curves. We can also write this in various forms that are approximations.
9.1.3.1 Approximate results
We must assume that v
g
v
l
, an example, at 1 atm v
g
1000v
l
. Therefore we can write
v = v
g
=
v
g
N
g
=

P
this assumes the ideal gas law. Hence
dP
d
=
L
v
=
LP
2
lets also assume that the latent heat is independent of the temperature over the range we are interested in.
We can write the equation as follows
dP
P
= L
Z
d
2
if we take water for example, at 0 degrees celsius, the latent heat is 2520 J/g and at 100 degrees celsius the
latent heat is 2260 J/g. We can see that this is approximately 12 percent change. We now see that
lnP =
L
+lnP
0
and nally
P = P
0
e
L/
this conrms the exponential behaviour of our coexistence curve. It is quite common to see this expression
written as
L
0
= N
A
L (N
A
is Avegadros number)
gives us
P = P
0
e
L
0
/RT
we can easily plot this function. The above expression is not completely correct but should be expressed
as
lnPlnP
0
=
L
+
L
0
thus
P = P
0
e
L
_
1
0
_
162
9.1.4 Examples
9.1.4.1 Calculate dT/dP for water
If we assume that the pressure is 1 atm and the temperature is 377 K
P = 1 atm
T = 377 K
L = 2260 J/g
thus
dP
dT
=
L
0
P
RT
2
L
0
= 2260 J/g18 = 4.0710
4
J/mole
also R = 8.31 (J/K mole)thus we can see that
dT
dP
=
RT
2
L
0
P
= 28.4 K/atoms
9.1.4.2 Heat of vaporization for ice
We are given the following
P(2 celsius) = 3.88 mm Hg
P(0 celsius) = 4.58 mm Hg
from this, nd L of ice at -1 degrees centigrade. We will use our result
dP
dT
=
L
0
P
RT
2
thus
L
0
=
RT
2
P
dP
dT
=R
d lnP
d(1/T)
lets consider
d lnP
d(1/T)
=
d lnP
dT
dT
d(1/T)
we can write the following
d(1/T)
dT
=
1
T
2
thus
d lnP
d(1/T)
=T
2
d lnP
dT
=
T
2
P
dP
dT
we just need to plug in numbers into
L
0
=R
d lnP
d(1/T)
=R
0.7
2.710
5
= 5.110
4
J/mole
163
9.1.5 Latent Heat and Enthalpy
If we know the specic heat of something at constant pressure we can nd the latent heat of the material.
We will start with Gibbs free energy
G(N, P, ) = N(P, )
but sometimes we have multiple phases. Each phase will have its own chemical potential. More generally
we can write the Gibbs free energy as
G =
j
N
j
j
we can then write dow the thermodynamic identity
du = dPdV +
j
N
j
d
j
now we want to talk about the transformation from a liquid to a gas. Some number of molecules will
change from being a liquid to a gas
dN = dN
g
=dN
l
this is all valid in the coexistence curve. Therefore
du =dPdV +(
g
dN
g
+
l
dN
l
)
we can see that the last term vanishes in the coexistance state, thus
du =dPdV
therefore
L =d = du+PdV
but we know that the enthalpy is dened as
dH = d(u+PV) = du+PdV +VdP
but we know the pressure is constant, thus
L = dH = H
g
H
l
and also
C
p
=
_
_
P
9.2 Van der Waals Equation of State
The basic idea of this equation is to correct for both the volume and the pressure. We will look at the
volume correction rst
9.2.1 Volume correction
We can reduce the effective volume to a value
V
=V Nb
where V is the volume of the box and b is some other volume. The concentration is changed by
n
=
N
V
=
N
V Nb
in practice b is always measured empericaly.
164
9.2.2 Pressure correction
This arises from the fact that any atom or molecule has a weak attraction to any other atom or molecule,
i.e inert gas solid. This phenomenon is know as the van der Waals force. This is what is called the mean
eld value.This refers to the idea that we neglect uctuations. Lets suppose that we have a quantity (r)
which is the potential energy of the interaction between the two atoms seperated by a distance r. We have
a concentration n, the number of atoms per unti volume. The average potential energy of all other atoms
relative to one particular atom is written as
average value of all other atoms on one atom at position r = 0 =
Z

b
(r)ndV
we have assume that n is a constant value. The mean value eld implies that all the atoms or molecules
are always at their mean position, that is to say we neglect uctuations (using n
will give only a second

order correction). We can write the integral as
2na =
Z

b
(r)ndV
thus
Z

b
(r)ndV =2a
it is minus because it is an attractive intercation, attractive force. The factor of 2 is purely for convention
and convenience. We will now use the Helmholtz free energy, thus we consider
dF = dud d
where the second and third term are zero (constant temperature and entropy). Thus
dF = du
we can therefore say
dF = du =
N
2
(2na)
where the 1/2 comes from double counting. Thus
dF =
N
2
V
a
a is a second parameter that we have to gure out. The free energy of an ideal gas is
F =N[ln(n
Q
/n) +1]
we must correct this for the van der Waals gas
F
dW
=N[ln(n
Q
/n
) +1] =N
_
ln
_
n
Q
(V Nb)
N
_
+1
_
N
2
V
a
and the pressure is
p =
_
F
dW
V
_
,N
=
_
N
_
N
n
Q
(V Nb)
n
Q
N
_
+
N
2
V
2
a
_
=
N
V Nb
N
2
V
2
a
165
we nally get the following
_
p+
N
2
V
2
a
_
(V Nb) = N
this is the van der Waals equation for a gas. If you think of the interactions of atoms or molecules you nd
that at very low seperations there is a repulsive force which is usually modeled as 1/r
12
. On the other
hand if you start pulling the hydrogen molecule apart there will be an attraction given by 1/r
6
, which is
the van der Waals term. Where the 1/r
6
can be looked as the 1/V
2
term arising from the van der Waals
force. We can now use this equation to predict critical behavior.
9.2.3 Finding critical point
If we look at the p versus V plot we can see that we have three critical points for phase transitions. There
are a series of isotherms that can also be seen in the plot. Aobe some critical point we get what is called
a uid and this happens at the critical isotherm which occurs at
C
. These isotherms occur on the vapor
staturation curve. The thing that will enable us to nd the critical point is that
_
p
V
_
C
= 0
_
2
p
V
2
_
C
= 0
knowing that
p =
N
V Nb
N
2
V
2
a
thus
_
p
V
_
=
N
(V Nb)
2
+2
N
2
V
3
a = 0
2Na
V
3
=

(V Nb)
2
and
_
2
p
V
2
_
=
2N
(V Nb)
3
+6
N
2
V
4
a = 0
3Na
V
4
=

(V Nb)
3
If we devide the equations we nd
2V
C
3
=V
C
Nb
thus we have just found the critical volume. We get the following result
V
C
= 3Nb (9.1)
this is by far the most accurate way to get these parameters (a and b). If we take the previous expression
and insert into the rst equation we nd
C
=
2Na
27N
3
b
3
(2Nb)
2
=
8
27
a
b
(9.2)
we also want to nd p
C
from the van der Waals equation
p
C
=
4Na
27b
1
2Nb
N
2
a
9N
2
b
2
=
4
27
a
b
2
3
27
a
b
2
=
a
27b
2
(9.3)
hence V
C
and
C
dene a and b. We want to eliminate the three parameters a, b and N from the van der
Waals equations. If we start with
_
p+
N
2
V
2
a
_
(V Nb) = N
166
we can write
_
p+
_
V
C
3b
_
2
27b
2
p
C
V
2
_
_
V
V
C
3
_
=
V
C
3b
we still need to get rid of b, we can devide 9.3 with 9.2 we get
p
C
C
=
a
27b
2
27b
8a
=
1
8b
thus we nd
_
p+
_
V
C
3b
_
2
27b
2
p
C
V
2
_
_
V
V
C
3
_
=
8V
C
3
p
C
C
this is an equation that involves p,V and and p
C
,V
C
and
C
. We can divide through by the product p
C
V
C
thus
_
p
p
C
+3
_
V
C
V
_
2
_
_
V
V
C
1
3
_
=
8
3
C
where we are only left with the ratios of all these quantities. We can now introduce
p =
p
p
C
V =
V
V
C
=

C
which are rthe reduced values, thus we can write
_
p +
3
V
__
V
1
3
_
=
8
3

two gases with the same values of p

V and are said to be in corresponding states, i.e all gases look the
same in terms of these three variables. Lets go back to the previous expression and write it as
( p
V +3)
_
V
1
3
_
=
8
3

V
2
this is a general cubic expression in

V. This expression can be solved numerically, but in general a cubic
function gives an S shaped curve with two turning points. If you decrease the pressure and increase the
volume we come to a metastable state, and likewise if you decrease the volume and increase the pressure
also allow you to reach a metastable state. The turning point for the rst case is called superheating and
the second case is supercooling. This formalism breaks down when

V < 1/3. If we consider the line for
p
A
(lower left minimum) we can write the Gibbs freen energy as
dG =d +Vdp+dN
but at constant and N we nd
dG =Vdp
so as we go from the left minimum to the right maximum then the total change from this is given as
G =
Z
B
A
dG = 0
167
we can write down the integral in the following way
Z
B
A
Vdp =
_
Z
D
A
+
Z
C
D
+
Z
E
C
+
Z
B
E
_
Vdp
=
__
Z
C
D
Z
A
E
_
_
Z
E
B
Z
E
C
__
Vdp
where the rst two integrals is the area of ADC and the second set of integrals is the area of CBE and this
is all equal to 0. We dene p so that the areas are equal.
9.3 Nucleation of a Liquid Drop
This process is concerned with how rain is created, i.e how do you build liquid drops from gases. We are
talking about metastability. Lets us consider
=
g
l
where these refer to the bulk properties. If > 0 then gas condenses to liquids. For a drop, the surface
tension (energy) increases the chemical potential for the liquid and may prevent condensation and this
leads to the concept of the critical radius of the drop. If the drop is above this radius it can grow but if it
is below this area than it shrinks
R > R
c
grows
R < R
c
shrinks
recall that the Gibbs free energy is given as
G = N
and the change in the Gibbs free energy is given as
G = G
l
G
g
=
4
3
R
3
n
l
(
l
g
) +4R
2
where = G/A is the Gibbs free energy per unit area. The rst term dominates for large radius and the
second term dominates for small radius. To nd the critical radius we take the derivative
dG
dR
=4R
2
n
l
+8R = 0
thus the critical radius is given as
R
c
=
2
n
l
if we take the second derivative

d
2
G
dR
2
=8Rn
l
8 =16 +8 =8 < 1
thus this is a maximum. What is the height of the barrier?
G
b
=
4
3
R
3
c
n
l
+4R
2
c
168
substituting our expression for the critical radius we nd
G =
4
3
8
3
n
3
l
3
n
l
+4
4
2
n
2
l
=
_
16
32
3
_

3
n
2
l
2
G =
16
3
3n
2
l
2
Lets look at what the critical radius for a water droplet is. If we have a water droplet which is sorrounded
by vapor which applies a pressure p > p
bulk
and p() exceeds p
bulk
(), where the bulk case
l
=
g
. Recall
that
=ln
_
n
n
Q
_
= ln(Ap)
since we know that p n at xed . Thus
=
p
p(bulk)
=ln(Ap) ln(Ap
bulk
) =ln
_
p
p
bulk
_
we have related the change in chemical potential to the ratio of these two pressures. Putting some numbers
for water
= 300 K
p
p
bulk
= 1.1 n
l
=
610
23
18
=
10
23
3
cm
3
=
10
29
3
m
3
= 7.210
2
J m
2
thus
R
c
=
2
n
l
=
14.410
2
_
10
29
3
_
(1.410
23
300ln(1.1))
m = 10
8
m
9.4 Summary
The Clausius-Claperyin equation
dp
d
=
L
V
where
L =
Lt ht
molecule
and the pressure is given as
P = P
0
e
L
0
R
_
1
T
1
T
0
_
and
L
0
=
Lt ht
mole
and the van der Waals equation is given as
_
p+
N
2
V
2
a
_
(V Nb) = N
169
the critical point is given as
V
c
= 3Nb p
c
=
a
27b
2

c
=
8a
27b
and corresponding states
_
p +
3
V
__
V
1
3
_
=
8
3

9.5 Problems
Problem # 1 Entropy, energy, and enthalpy of van der Waals gas
a) Show that the entropy of the van der Waals gas is
= N
_
ln
_
n
Q
(V Nb)
N
_
+
5
2
_
We know that the free energy of the gas, with the van der Waals correction is given as
F
dW
=N
_
ln
_
n
Q
(V Nb)
N
_
+1
_
N
2
V
a
and we know that the entropy is dened as
=
_
F
_
V
=

_
N
_
ln
_
k
3/2
(V Nb)
N
_
+1
_
N
2
V
a
_
where k contains all of the constants that come with the quantum concentration. We know that
(AB) = B
A
+A
B
if we let
A =N B =
3
2
ln(k) +ln(V Nb) lnN +1
thus we nd
(AB) = N
_
3
2
ln(k) +ln(V Nb) lnN+1
_
N

_
3
2
ln(k)
_
= N
_
3
2
ln(k) +ln(V Nb) lnN+1+
3
2
_
= N
_
ln
_
n
Q
(V Nb)
N
_
+
5
2
_
thus the entropy is given as
= N
_
ln
_
n
Q
(V Nb)
N
_
+
5
2
_
b) Show that the energy is
U =
3
2
N N
2
a
V
170
We know that the total energy is given as
U = F +
thus
U = N
_
ln
_
n
Q
(V Nb)
N
_
+1
_
N
2
V
a+N
_
ln
_
n
Q
(V Nb)
N
_
+
5
2
_
=
3
2
N N
2
a
V
thus the total energy is given as
U =
3
2
N
N
2
V
a
c) Show that the enthalpy H =U + pV is
H(,V) =
5
2
N +N
2
b
V
2N
2
a
V
H(, p) =
5
2
N +Nbp2N
ap
All results are given to rst order in the van der Waals correctio terms a, b.
If we start with
_
p+
N
2
V
2
a
_
(V Nb) = N
expanding this equation gives
pV pNb+
N
2
V
a
N
3
V
2
ab = N
thus
pV = pNb
N
2
V
a+
N
3
V
2
ab+N
since all the results are given to rst order allows us to simplify
pV = pNb
N
2
V
a+N
thus the enthalpy is terms of the volume gives
H(,V) =U + pV =
5
2
N +N
2
b
V
2N
2
a
V
and since we know that p = N/V V = N/p and also N/V = p/, thus the enthalpy in terms of the
pressure give
H(, p) =
5
2
N +Nbp2N
ap
Problem # 2 Latent heat of magnesium

171
In the temperature range 700 to 730 K, the vapor pressure of magnesium can be approximately represented
by
log
10
p =
7, 500
T
+8.6
(p in mmHg, T in K). What is the molar latent heat of sublimation of magnesium in this temperature
range?
We know that the latent heat of is given as
L =(s
1
s
2
)
where s
1
and s
2
are the entropy for the specic phase of the subtance, thus the latent heat of fusion (solid
to liquid) is
L
f
=(s
l
s
s
)
the latent heat of vaporization is (liquid to gas)
L
v
=(s
g
s
l
)
and the latent heat of sublimation (solid to gas)
L
s
= (s
g
s
s
)
we also know that
ln p =
L
0
+constant
but we are given
log
10
p =
7, 500
T
+8.6
so it is just a matter of comparing these two equation and doing a change of base. We also know that
ln p = log
e
p =
log
10
p
loge
thus
log
10
p
loge
= ln p
and we nd
log
10
p =
7, 500
T loge
+
8.6
loge
and we can see that the latent heat is given by
L
0
=
7, 500k
B
loge
= 2.3810
19
J
K
= 1.4310
5
J
mole
and so
L
0
= 1.4310
5
J
mole
Problem # 3 Latent heat of neon
172
The latent heat of fusion and the latent heat of vaporization of neon at the triple point have values
335J/mole and 1810 J/mole respectively. The temperature of the triple point is 24.57 K. What is the latent
heat of sublimation of neon at the triple point? What is the change in entropy when one mole of liquid
neon at the triple point is vaporized?
Since we know that the latent heat of fusion (solid to liquid) is
L
f
=(s
l
s
s
)
the latent heat of vaporization is (liquid to gas)
L
v
=(s
g
s
l
)
and the latent heat of sublimation (solid to gas)
L
s
= (s
g
s
s
)
we can see that
s
s
= s
l
L
f
s
g
=
L
v
+s
l
thus we can see that the latent heat of sublimation is
L
s
= L
v
+L
f
thus we nd that the laten heat of sublimation is
L
s
= 2145
J
mole
and the change in entropy for vaporization is given by
s
g
s
l
=
L
v
=
L
v
k
B
T
mole
which is given by
= 5.3310
24
173
Chapter 10
Kinetic Theory
1. Maxwell distribution of speeds
2. Mean free path
3. Transport: Diffusion, thermal conductivity, self-diffusion
4. Ballistic regime- Knudsen gas
10.1 Maxwell distribution
We are only consrened with the magnitude of teh velocities and not direction. We must consider the
notion of quantized energy in a box. We can combine this with the probability that any one of these states
is occupied, i.e combine quantum energy levels with f (
l
), recall
f (
l
) =
n
n
Q
e
l
/
where
l
=

2
2m
_
l
L
_
2
we will conne our system to have only spin 0 atoms. We want to express the number of atoms with
quantum numbers between l and l +dl this goes as
N(
l
) = 1
1
8
4l
2
dl f (
l
) =

2
l
2
n
n
Q
e
l
/
dl
where 1 is for the spin 0 and
1
8
4
2
dl number of states in shell of octant we want to convert from quan-
tum numbers (l) to speed (v), thus
l
=
1
2
mv
2
=

2
2m
_
l
L
_
2
this is the important step that takes you from quantum numbers into speed
v
2
=

2
m
2
2
l
2
L
2
l =
ML
v
if we say that there are N molecules in a volume V and lets introduce a probability that a particle has a
velocity in a particular rangep(v) is the probability that molecules have speeds between v and v+dv, thus
Np(v)dv =
1
2
l
2
n
n
Q
e
l
/
dl
dv
dv
174
where
dl
dv
=
ML
putting this together we have

Np(v)dv =
1
2
n
n
Q
_
ML
_
2
v
2
e
Mv
2
/2
_
ML
_
dv
lets recall
n
n
Q
=
N
L
3
_
2
2
M
_
3/2
and putting everythign together we nd
Np(v)dv =

2
N
L
3
_
2
2
M
_
3/2
_
ML
_
3
v
2
e
Mv
2
/2
dv
we can see that a lot of terms cancel
p(v) = 4
_
M
2
_
3/2
v
2
e
Mv
2
/2
this is the famous Maxwell distribution for speeds of a classical ideal gas. We can now derive the RMS
speed for the distribution.
Three speed
The RMS speed is dened as follows
v
2
=
Z

0
v
2
p(v)dv = 4
_
M
2
_
3/2
Z

0
e
Mv
2
/2
v
4
dv
where we can write
4
_
M
2
_
3/2
=
4
2
_
M
2
_
3/2
thus
v
2
=
4
2
_
M
2
_
3/2
Z

0
e
Mv
2
/2
v
4
dv
we can set y = Mv
2
/2 thus
v =
_
2
M
_
1/2
y
1/2
dv =
_
2
M
_
1/2
1
2
y
1/2
and
v
4
dv =
1
2
_
2
M
_
5/2
y
3/2
dy
175
and nally we nd
v
2
=
4
1/2
_
M
2
_
3/2
_
2
M
_
5/2
Z

0
e
y
y
3/2
dy
=
3
2
2
M
=
3
M
therefore
_
v
2
=
_
3
M
this is the same result we derived in the equipartition theorem, i.e
1
2
mv
2
=
3
2
Lets now calculate the mean speed which is not zero, but we know that the maen velocity is zero. We can
write
v =
Z

0
vp(v)dv =
4
2
_
M
2
_
3/2
Z

0
e
Mv
2
/2
v
3
dv
making the same substitution as before gives
v
3
dv =
1
2
_
2
M
_
2
ydy
plugging this in gives
v =
4
1/2
_
M
2
_
3/2
_
2
M
_
2
Z

0
e
y
ydy
which yields
v =
_
8
M
_
1/2
thus this is still of the form /M, thus the maen speed is slightly different than the RMS speed. We can
now derive what the most probable speed. We can see that at low speeds, the distribution is quadratic, but
with increasing speed the exponential term will dominate. The maximum will give us the most probable
speed. The most probable speed can be derived by differentiating the previous expression
p(v) = Av
2
e
Mv
2
/2
where
dp(v)
dv
= A
_
2v
Mv
3
_
e
Mv/2
thus
v
2
MP
=
2
M
and nally
v
MP
=
_
2
M
this are the three speeds that gases can have. We can normalize to nd
v
v
MP
=
v
_
2/M
depending exactly on what the problem is, you will have to utilize one of these expression.
176
10.2 Mean Free Path
The mean free path is the average distance traveled by an atom between collisions. It is almost always
given as l. We can replace the fact that atoms of like kind have a diameter d which are all moving around in
different directions. We replace the previous picture by assuming that one atom has a diameter 2d (super
atom) and all other atoms are points. We can consider our super atom will move a distance l in a cylinder
with length l. On the average there is one atom in the cylinder of volume V = ld
2
, that is to say since
there is one atom in the cylinder
ld
2
= n = 1
where n is the number of atoms per unit volume, thus
l =
1
nd
2
how big is this number?
10.2.1 Estimate of l
Lets rst assume that we are in STP conditions. We also have the Loschmidt number
n =
Avegadros number
molar volume at 0 celsius and atm. pressure
=
6.0210
23
22.410
3
m
3
= 2.6910
25
m
3
we can now make an estimate of the mean free path
l =
1
2.6910
25
m
3
210
10
m
2
300 nm
how often does this collision occure? The mean free time is found by
t =
l
v
=
310
7
m
10
3
m/s
0.3 ns
lets take another limit, for example an ultra high vacuum system
p 10
13
atm
thus
l 310
7
m10
13
3000 km
the mean free path becomes really large under low pressures. This forces very different behaviors for
gases under different conditions. The mean free time in this system is
t 0.3 ns 10
13
1 hr
when the MFP > dimensions of the box is called the ballistic regime or Knudsen regime.
10.3 Transport
We will now talk about how atoms move through a medium this is know as transport. We are assuming
that we have particle diffusion when there is a gradient of concentration. This is in analogy to Ohms law.
177
10.3.1 Particle diffusion in a concentration gradient
Lets consider a resevoir with two cavities, a left and right cavity. Lets assume that the left cavity has a
higher concentration than the right, thus there is a steady ow of particles from the left to the right cavity.
We want to gure out the rate of motion of these particles depend on the speed and the mean free path.
There is a net ow from higher concetration to the lower concentration
l
>
r
. The ux of particles is
dened by Ficks law, which says
J
z
n
=D
dn
dz
where D is the diffusive constant (diffusivity), the minus sign comes from the fact that the gradient is
positive to the left but particles ow to the right. The ow is from high n to low n. We have dened l
z
as
the mean free path along the z axis and v
z
is the z component of the average velocity. At the plane z we
have the ux in the +z direction is given by
1
2
n(z l
z
) v
z
and the ux in the -z component is
1
2
n(z +l
z
) v
z
and the net ux is the difference between these two components
J
z
n
=
1
2
[n(z l
z
) n(z +l
z
)] v
z
we can write the term on the left, with a Taylor expansion
n(z +l
z
) n(z) +l
z
dn
dz
and likewise for the other term, thus
J
z
n
=
dn
dz
v
z
l
z
we have not taken into account for the fact that not all these atoms travel in the z direction, thus we must
take an angular average to account for this. Thus the projection on the z axis is given by
v
z
= vcos
and
l
z
= l cos
where l
z
is the projection of the MFP on the z axis. Recall that the solid angle is dened as
d= 2sind
we want
v
z
l
z
=
vl2
R
/2
0
cos
2
sind
2
R
/2
0
sind
where the denominator is for normalization. Thus we can see
v
z
l
z
=
vl
R
/2
0
cos
2
sind
R
/2
0
sind
= vl
_
1
3
cos
3
cos
_
/2
0
=
vl
3
178
thus the diffusion constant is
D =
vl
3
how big is this constant? Lets take a gas at STP. Recall that v 10
5
cm/s and l 3 10
5
cm and thus
D1 cm
2
/s. This is the basic problem of atoms diffusing in a gradient and thus this increases the entropy.
10.4 Thermal Conductivity
We want to replace the scenerio where we have a concentration gradient with one that has a temperature
gradient. Imagine that we have two reseviors with temperature
1
and
2
where
1
>
2
. Thus we now
have Fouriers law
J
z
=K
z
where K is known as the thermal conductivity. We want to write this as follows
J
z
u
=D
u
z
where
u
is the energy density, thus this is an exact analogy from what we wrote before, we can write
J
z
u
=D
z
=C
V
thus
J
z
u
=DC
V
z
and hence
K = DC
V
=
vl
3
C
V
this result shows us that the thermal conductivity is independent of the pressure of the gas, C
V
n and
l 1/n and hence K is independent of n and hence the pressure. This is provided that the mean free path
is still much less then the dimensions of the box. How big is it? At STP, the heat capacity is
C
V
=
3
2
k
B
n
3
2
310
19
cm
3
1.410
23
J/K10
3
J/K cm
3
and thus
K =C
V
D 10
3
J/Kcm
3
1 cm
2
/s 1 mW/cmK
179

Physics 112 Thermodynamics

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Physics 112: Thermodynamics

Served by Roger Grifth

where N is even and M = (n

)m = 2sm where the 2s = spin excess = n

of being and a probability of P

of being . we also know that P

. The probability of a conguartion with spin excess 2s is

. The probability of nding a magnetic moment M = (2s)m is given by the following

(i.e equally likely for spins to be or )

N root mean square

are the number of phone lines being used

where the probability of the number of lines being used is given by

and the Poisson curves are given by

= 0. We also know that the probability of this

N. It is the fractional width of

but we know that the temperature is dened as

this is related to the spin excess and the magnetic moment by

Problem # 3 Addition of entropy for two spin systems

If we raise both sides to the exponetial

and the trick we can use

and now we can write

this is because that we are assuming that

thus for > 0 then if is a maximum means that F

thus we can write

3.12 Equipartition Theorem

the Maxwell relations are given by

we then move on to the Equipartition theorem

we can do this by knowing that the free energy is dened

and the trick we can use

and now we can write

Thus the energy is given by

now we just need to nd

we can write the heat capacity as

but we know the energy is dened as

we plot M/nm vs mB/

the following relationship will be useful

and for N particles we nd

we know what Z is now we need to nd

the order of the secon derivatives do not matter and thus we nd

Problem # 8 Free energy of a photon gas

where is called the Debye temperature expressed as

if we now take exponetial of both sides we nd

what we see is that the average value of N is given by

we will also calculate the average energy. The mea energy

lets consider the following derivative

and we nd the average energy to be given as

a result from all this is for the uctuations

this is left as a homework assigment.

where is the grand sum

and the average energy is given as

and the uctuations are given by

thus we nd that the average number of particles is

in Chapter 6 we apply this result to the ideal gas to nd that

where we can see that

thus the heat capacity is

where is the grand partition function

what we see is that the average value of N is given by

but we know that

thus we must nd the partition function, which is given as

where the entropy is dened as

b) The isentropic and isothermal bulk moduli are dened as

Show that for an ideal gas B