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Introduction

In this course we will cover selected topics in thermodynamics and statistical mechan-

ics. Since we only have twelve weeks, the selection is necessarily limited. You will probably

need to take a graduate course in thermal physics or do studying on your own in order to

gain a thorough knowledge of the subject.

Classical (or maybe “conventional” is better) thermodynamics is an approach to ther-

mal physics “from the large.” Statistical mechanics approaches the subject “from the

small.” In thermodynamics, one is concerned with things like the pressure, temperature,

volume, composition, etc., of various systems. These are macroscopic quantities and in

many cases can be directly observed or felt by our senses. Relations between these quan-

tities can be derived without knowing about the microscopic properties of the system.

Statistical mechanics takes explicit account of the fact that all systems are made

of large numbers of atoms or molecules (or other particles). The macroscopic properties

(pressure, volume, etc.) of the system are found as averages over the microscopic properties

(positions, momenta, etc.) of the particles in the system.

In this course we will tend to focus more on the statistical mechanics rather than

the thermodynamics approach. I believe this carries over better to modern subjects like

condensed matter physics. In any case, it surely reﬂects my personal preference!

Some History (mostly taken from Reif)

As it turns out, thermodynamics developed some time before statistical mechanics.

The fact that heat is a form of energy was becoming apparent in the late 1700’s and early

1800’s with Joule pretty much establishing the equivalence in the 1840’s. The second law

of thermodynamics was recognized by Carnot in the 1820’s. Thermodynamics continued

to be developed in the second half of the 19

th

century by, among others, Clausius, Kelvin

and Gibbs.

Statistical mechanics was developed in the late 19

th

and early 20

th

centuries by Clau-

sius, Maxwell, Boltzmann, and Gibbs.

I ﬁnd all of this rather amazing because at the time of the initial development of

thermodynamics, the principle of energy conservation hadn’t been ﬁrmly established. Sta-

tistical mechanics was developed when the existence of atoms and molecules was still being

debated. The fact that macroscopic properties of systems can be understood in terms of

the microscopic properties of atoms and molecules helped convince folks of the reality of

atoms and molecules.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-2

Still more amazing is the fact that the foundations of statistical mechanics were de-

veloped before quantum mechanics. Incorporating quantum mechanics did make some

changes, especially in the counting of states, but the basic approach and ideas of statisti-

cal mechanics remained valid. I suspect that this is a reﬂection of both the strength and

weakness of statistical methods. By averaging over many molecules you derive results that

are independent of the detailed properties of individual molecules. The ﬂip side is that

you can’t learn very much about these details with statistical methods.

Some Thermodynamic Concepts

From mechanics, we’re familiar with concepts such as volume, energy, pressure (force

per unit area), mass, etc. Two new quantities that appear in thermodynamics are tem-

perature (T) and entropy (S).

We will ﬁnd that temperature is related to the amount of energy in a system. Higher

temperature means greater internal energy (usually). When two systems are placed in

contact, energy in the form of heat ﬂows from the higher temperature system to the lower

temperature system. When the energy stops ﬂowing the systems are in thermal equilibrium

with each other and we say they are at the same temperature. It turns out if two systems

are in thermal equilibrium with a third system, they are also in thermal equilibrium with

each other. (This is sometimes called the zeroth law of thermodynamics.) So the concept

of temperature is well deﬁned. It’s even more well deﬁned than that as we will see later in

the course.

Two systems can exchange energy by macroscopic processes, such as compression or

expansion, or by microscopic processes. It is the microscopic process that is called heat

transfer. Consider a collision among billiard balls. We think of this as a macroscopic

process and we can determine the energy transfer involved by making measurements of

a few macroscopic parameters such as the masses and velocity components. If we scale

down by roughly 24 orders of magnitude, we consider a collision between molecules, a

microscopic process. A very large number of collisions occur in any macroscopic time

interval. A typical molecule in the atmosphere undergoes ∼ 10

10

collisions per second. All

these collisions result in the exchange of energy and it is the net macroscopic transfer of

energy resulting from all the microscopic energy transfers that we call heat.

Recall that the ﬁrst law of thermodynamics is

dU = dQ+dW ,

where dU is the change of (internal) energy of a system, dQ is energy added to the system

via a heat transfer, and dW is energy added by doing work on the system.

Aside: you will often see the heat and work written as ¯ dQ and ¯ dW. This is a reminder

that these quantities are not perfect diﬀerentials, just small changes. A system (in equi-

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-3

librium) has a well deﬁned internal energy U(P, V, . . .) which can be diﬀerentiated with

respect to P, V , . . ., but there is no such thing as the heat or work content of a system.

The heat and work refer to energy transfers during a change to the system.

So the ﬁrst law really boils down to a statement of energy conservation. You can

change the energy of a system by adding energy microscopically (dQ) or macroscopically

(dW).

While we’re at it, the second law of thermodynamics can be stated in many ways,

but one way (without worrying too much about rigor) is: it’s impossible to turn heat

completely into work with no other change. So for example, if you build a heat engine

(like a power plant) you can’t turn all the heat you get (from burning coal) completely

into electrical energy. You must dump some waste heat. From this law, one can derive the

existence of entropy and the fact that it must always increase. (Or you can deﬁne entropy,

and state the second law in terms of the increase in entropy).

Entropy

Earlier, we mentioned that temperature is related to internal energy. So, a picture

we might carry around is that as the temperature goes up, the velocities of the random

motions of the molecules increase, they tumble faster, they vibrate with greater amplitude,

etc. What kind of picture can we carry around for entropy? Well that’s harder, but as the

course goes along we should develop such a picture.

To start, we might recall that the change in entropy of a system is the heat added to

the system divided by the temperature of the system (all this is for a reversible process,

etc.):

dS = dQ/T .

If a dQ > 0 is added to one system, −dQ must be added to a second system. To ensure

that entropy increases, T

1

< T

2

; the ﬁrst system is cooler than the second system. The

molecules in the ﬁrst system speed up and the molecules in the second system slow down.

After the heat is transfered (in a direction which makes entropy increase) the distribution

of molecular speeds in the two systems is more nearly the same. The probability that a

fast molecule is from system 1 has increased while the probability that a fast molecule

is from system 2 has decreased. Similarly, the probability that a slow molecule is from

system 2 has increased and the probability a slow molecule is from system 1 has decreased.

In other words, as a result of the increase of entropy, the odds have become more even. So

increasing entropy corresponds to a leveling of the probabilities.

Higher entropy means more uniform probability for the possible states of the system

consistent with whatever constraints might exist (such as a ﬁxed total energy of the sys-

tem). So entropy is related to the number of accessible states of the system and we will

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-4

ﬁnd that maximizing the entropy is equivalent to assuming that each accessible state is

equally likely.

The ﬁrst law of thermodynamics can be written as

dU = dQ+dW = T dS −p dV or dS = dU/T +p dV/T ,

where we’ve assumed that the number of particles in the system is constant and the work

done on the system results from pressure acting while the volume changes. Suppose the

system is an ideal gas. Then the energy depends only on temperature

dU = nC

V

dT ,

where n is the number of moles and C

V

is the molar speciﬁc heat at constant volume which

we take to be constant. The equation of state is

pV = nRT or p/T = nR/V ,

where R is the gas constant. We plug these into the ﬁrst law and obtain

dS = nC

V

dT

T

+nR

dV

V

,

which can be integrated to give

S

f

−S

i

= nC

V

log

T

f

T

i

+nRlog

V

f

V

i

.

So, we have an expression for the entropy diﬀerence between any two states of an ideal

gas. But how can we relate this to what’s going on at the microscopic level? (Note, unless

otherwise stated, by log, I mean a natural logarithm, log

e

.)

First, let’s make a distinction between the macroscopic state and the microscopic

state. The macroscopic state is completely speciﬁed (at equilibrium!) by a small number of

parameters such as p, V , n, etc. Classically, the microscopic state requires the speciﬁcation

of the position and velocity of each particle

r

1

, v

1

, r

2

, v

2

, . . . , r

N

, v

N

,

where N is the number of particles. N is usually a huge number, comparable to Avogadro’s

number, the number of particles in a mole, N

0

= 6.02 × 10

23

. Since there is such a large

ratio of microscopic to macroscopic parameters, it must be that many microscopic states

may produce a given macroscopic state.

How many microscopic states are there? Why do we want to know? The idea is that

the macroscopic state which is generated by the most microscopic states is the most likely.

Suppose we say that

S ∝ log g ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-5

where g is the number of microstates corresponding to the macrostate.

This deﬁnition has the desirable property that if we have two non-interacting systems

with states g

1

and g

2

, and we bring them together, the entropy is additive.

S = S

1

+S

2

.

Since the systems are non-interacting, bringing the systems together does not change the

states available to either system, and any microstate of system 1 may be combined with

any microstate of system 2 to yield a microstate of the combined system. This means that

there are a total of g

1

· g

2

states altogether. By deﬁning the entropy with a logarithm, we

ensure that it’s additive (at least in this case!).

So let’s count states. At ﬁrst sight, you might think there are an inﬁnite number of

states because r and v are continuous variables. Well, perhaps if you change them only

slightly, you don’t really get a new state.

Example: Ideal Gas Entropy

Consider one mole of ideal gas at STP. Its volume is V = 22.4 L = 2 ×10

4

cm

3

and it

contains N

0

= 6 ×10

23

molecules. How big is a molecule? Answer: about 1

˚

A = 10

−8

cm.

A molecular volume is V

m

≈ 10

−24

cm

3

. Imagine dividing our total volume V into cells the

size of a molecule. There are M = V/V

m

= 2 ×10

28

cells. Let’s specify the micro-position

state by stating which cells have molecules in them. That is, we are going to specify the

positions of the molecules to a molecular diameter. How many states are there? Pick a cell

for the ﬁrst molecule. This can be done in M ways. Pick a cell for the second molecule.

This can be done in M − 1 ≈ M ways. For the third molecule, there are M − 2 ≈ M

ways. Continue to the N

th

molecule for which there are M −N ≈ M ways to pick a cell.

Altogether there are about

g ≈ M

N

≈

10

28

10

24

,

ways to distribute the molecules in the cells. The fact that we get M

N

rather than a

binomial coeﬃcient depends on the fact that M ≈ 10

28

≫ N ≈ 10

24

. Also, we should

probably divide by N! to account for permutations of the molecules in the cells (since we

can’t distinguish one molecule from another), but leaving this out won’t hurt anything at

this point.

As an example, consider a two dimensional gas containing N = 10 molecules and

M = 100 cells. The ﬁgure shows a couple of the possible position microstates of this gas.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-6

There are

M!/N!(M −N)! = 1.7 ×10

13

distinct states. Our approximation gives 10

20

states; the diﬀerence is mostly due to ignoring

the 10! in the denominator.

Knowing the number of states, we have

S ∝ N log M ,

= N log

V

V

m

,

= N log V

volume term in entropy

−

constant for given amount of gas

N log V

m

.

The N log V

m

term is a constant for a given amount of gas and disappears in any calculation

of the change in entropy, S

f

− S

i

. Similarly, the N! correction would also disappear. So

a lot of the (really awful?) approximations we made just don’t matter because things like

the size of a molecule drop out as long as we only consider entropy diﬀerences.

The N log V term is the volume term in the ideal gas entropy. By considering the

microstates in velocity, we would obtain the temperature term (and we will later in the

term!).

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-7

What Those Large Numbers Mean

The key aspect of all this is the large number of states! Suppose we have a gas in

equilibrium in a container of volume 2V . Why doesn’t the gas, by chance, wind up in

one-half the container with volume V ? How many states are there in each case?

g

1

=

V

V

m

N

, g

2

=

2V

V

m

N

.

And,

g

2

g

1

= 2

N

,

= 2

Avogadro’s Number

,

= 2

6×10

23

,

= 10

2×10

23

,

= 1 000 · · · 000

2×10

23

zeros

.

Such a state might be legal, but it’s extremely!!! unlikely. The fact that a system in

equilibrium has the maximum possible entropy is nothing more than the fact that the

normal equilibrium state has so many more ways to occur than an obviously weird state,

that the weird state just never occurs.

Quantum Mechanics and Counting States

You might be thinking that’s it pretty ﬂaky to assert that we need only specify a

molecular position to a molecular diameter. We’ve shown that as long as it’s small, the

resolution has no eﬀect on our calculation of changes in the entropy, so this is OK for

classical mechanics.

If we consider quantum mechanics, then we ﬁnd that systems are in deﬁnite states.

There are many ways to see this. An example is to consider a particle in a box and ﬁt the

wave functions in.

Another way is to consider the uncertainty principle,

∆p

x

∆x ≥ ¯h/2 .

If the state of the system is speciﬁed by a point in the x p

x

diagram (phase space), then

one can’t tell the diﬀerence between states which are as close or closer than the above. So

we can divide up this phase space into cells of ¯ h/2 and we can specify a state by saying

which cells are occupied and which are not.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Sep-2004 1-8

As a numerical example, consider air (N

2

) at room temperature. m

N

2

= 28m

p

=

28 × 1.7 × 10

−24

g = 4.8 × 10

−23

g. A typical kinetic energy is mv

2

/2 = 3kT/2 with

T = 300 K and k = 1.38 × 10

−16

erg/K, then E ∼ 6 × 10

−14

erg, v ∼ 5.1 × 10

4

cm/s,

p ∼ 2.4 ×10

−18

g cm/s. The molecular size is about r ∼ 1

˚

A = 10

−8

cm, so

p r = 2.4 ×10

−26

g cm

2

/s > ¯h = 1 ×10

−27

erg s .

Thus, at room temperature, one can specify the momentum of a molecule to a rea-

sonable fraction of a typical momentum and the position to about the molecular size and

still be consistent with quantum mechanics and the uncertainty principle. That is, room

temperature air is classical, but not wildly separated from the quantum domain. If we

consider lower temperatures or higher densities, electrons in metals, etc. quantum eﬀects

will be more important.

The ideal gas at STP is a “low occupancy” system. That is, the probability that any

particular state is occupied is extremely small. This means that the most likely number

of occupants of a particular state is zero, one occurs very rarely, and we just don’t need

to worry about two at all. This is the classical limit and corresponds to the Boltzmann

distribution.

If we have higher occupancy systems (denser and/or colder), then states occupied

by two or more particles can become likely. At this point quantum mechanics enters.

There are two kinds of particles: integer spin particles called bosons (such as photons or

other particles that we associate with waves) and half-integer spin particles called fermions

(protons, electrons, particles that we associate with matter). An arbitrary number of

bosons can be placed in a single quantum state. This leads to Bose-Einstein statistics and

the Bose distribution. At most one fermion can be placed in a quantum state. This leads

to Fermi-Dirac statistics and the Fermi distribution.

A lot of what we do this term will be learning about and applying the Boltzmann,

Bose, and Fermi distributions!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-1

Reading

This week, you should read the ﬁrst two chapters of K&K.

Entropy and the Number of States

As we discussed last time, in the statistical view, entropy is related to the number

of “microstates” of a system. In particular, the entropy is the log of the number of

states that are accessible to the system when it has speciﬁed macroscopic parameters

(its “macrostate”).

The fact that entropy always increases is just a reﬂection of the fact that a system

adjusts its macroscopic parameters, within the allowed constraints, so as to maximize the

number of accessible states and hence the entropy.

So, a large part of statistical mechanics has to do with counting states and another

large part has to do with deriving interesting results from these simple ideas.

Why is the Number of States Maximized?

Good question. We are going to take this is an axiom or postulate. We will not

attempt to prove it. However, we can give some plausibility arguments.

First, remember that we are typically dealing with something like Avogadro’s number

of particles, N

0

= 6.02 × 10

23

. As we discussed last time, this makes the probability

distributions very sharp. Or put another way, improbable events are very improbable.

The other thing that happens with a large number of particles has to do with the

randomness of the interactions. Molecules in a gas are in continual motion and collide with

each other (we will see later in the term, how often). During these collisions, molecules

exchange energy, momentum, angular momentum, etc. The situation in a liquid is similar,

one of the diﬀerences between a liquid and gas has to do with the distance a molecule

travels between collisions: in a gas, a molecule typically travels many molecular diameters;

in a liquid, the distance between collisions is of the order of a molecular diameter. In a

solid, molecules tend to be conﬁned to speciﬁc locations, but they oscillate around these

locations and exchange energy, momentum, etc. with their neighbors.

OK, molecules are undergoing collisions and interactions all the time. As a result, the

distribution of molecular positions and speeds is randomized. If you pick a molecule and

ask things like where is it located, how fast is it going, etc., the answers can only be given

in terms of probabilities and these answers will be the same no matter which molecule you

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-2

pick. (Provided you pick the same kind of molecule - you’ll probably get diﬀerent answers

for a N

2

molecule and an Ar atom, but you’ll get the same answers for two N

2

molecules.)

Sticky point: suppose we assume that the world is described by classical mechanics.

Also suppose we know the interactions between molecules in some isolated system. Suppose

we also know all ∼ N

0

positions r

i

and momenta p

i

(and whatever else we might need to

know to specify the system, perhaps the angular momenta of the molecules, etc.). Then in

principle, the equations of motion can be solved and the solution tells us the exact state

of the system for all future times. That is, there is nothing random about it! How do we

reconcile this with the probabilistic view espoused in the preceding paragraphs?

So far as I know, there are reasonable practical answers to this question, but there are

no good philosophical answers. The practical answers have to do with the fact that one

can’t really write down and solve the equations of motion for ∼ N

0

particles. But we can in

principle! A somewhat better answer is that we can only know the initial conditions with

some precision, not inﬁnite precision. As we evolve the equations of motion forward, the

initial uncertainties grow and eventually dominate the evolution. This is one of the basic

concepts of chaos which has received a lot of attention in recent years: small changes in

the initial conditions can lead to large changes in the ﬁnal result. (Have you ever wished

you could get a 10 day or 30 day weather forecast? Why do they stop with the 5 day

forecast?)

Of course, the fact that we cannot measure inﬁnitely precisely the initial conditions nor

solve such a large number of equations does not mean (still assuming classical mechanics)

that it couldn’t be done in principle. (This is the philosophical side coming again!) So

perhaps there is still nothing random going on. At this point one might notice that it’s

impossible to make a totally isolated system, so one expects (small) random perturbations

from outside the system. These will disturb the evolution of the system and have essentially

the same eﬀect as uncertainties in the initial conditions. But, perhaps one just needs to

include a larger system!

If we recognize that quantum mechanics is required, then we notice that quantum

mechanics is an inherently probabilistic theory. Also, I’m sure you’ve seen or will see in

your QM course that in general, uncertainties tend to grow with time (the spreading out

of a wave packet is a typical example). On the other hand, the system must be described

by a wave function (depending on ∼ N

0

variables), whose evolution is determined by

Schroedinger’s equation . . ..

As you can see this kind of discussion can go on forever.

So, as said before, we are going to postulate that a system is equally likely to be in

any state that is consistent with the constraints (macroscopic parameters) applied to the

system.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-3

As it happens, there is a recent Physics Today article on exactly this subject: trying to

go from the reversibility of classical mechanics to the irreversibility of statistical mechanics.

It’s by G. M. Zaslavsky and is called, “Chaotic Dynamics and the Origin of Statistical

Laws,” 1999, vol. 52, no. 8, pt. 1, p. 39. I think you can read this article and get a feel for

the problem even if some of it goes over your head (as some of it goes over my head).

Aside—Entropy and Information

In recent times, there has been considerable interest in the information content of

data streams and what manipulating (computing with) those data streams does to the

information content. It is found that concepts in information theory are very similar

to concepts in thermodynamics. One way out of the “in principle” problems associated

with classical entropy is to consider two sources of entropy: a physical entropy and an

information or algorithmic entropy. This goes something like the following: if we had

some gas and we had the knowledge of each molecule’s position and momentum, then the

physical entropy would be zero (there’s nothing random about the positions and momenta),

but the algorithmic entropy of our list of positions and momenta would be large (and

equal to the physical entropy of a similar gas whose positions and momenta we hadn’t

determined). What is algorithmic entropy? Essentially, the logarithm of the number of

steps in the algorithm required to reproduce the list.

In 1998, Toby Marriage wrote a JP on this topic. You can ﬁnd it at

http://physics.princeton.edu/www/jh/juniors fall98.html .

One of our criteria for junior papers is that other juniors should be able to understand the

paper; so I think you might get something out of this paper as well!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-4

Macroscopic Parameters

We will be most concerned with systems in equilibrium. Such a system can usually

be described by a small number of macroscopic parameters. For example, consider a gas.

If the density of the gas is low enough, it can be described quite well by the ideal gas law

when it’s in equilibrium:

pV = NkT = nRT ,

where p is the pressure, V is the volume, N is the number of molecules, n is the number of

moles, k = 1.38×10

−16

erg K

−1

is Boltzmann’s constant or the gas constant per molecule,

R = 8.31 ×10

7

erg mole

−1

K

−1

= N

0

k is the gas constant per mole, and T is the absolute

temperature.

Notice that some parameters depend on how much gas we have and some don’t. For

example, if we replicate our original system, so we have twice as much, then V , N, U

(internal energy), and S (entropy) all double; p, and T stay the same. We are ignoring the

contribution of any surface interactions which we expect to be very small. Can you think

why? Parameters which depend on the size of the system are called extensive parameters.

Parameters that are independent of the size of the system are called intensive parameters.

Note that the gas law is not the whole story. If more than one kind of molecule is in

the gas, we need to specify the numbers of each kind: N

1

, N

2

, . . .. Also, the gas law does

not say anything about the energy of the gas or its entropy. The gas law is an equation of

state, but it needs to be supplemented by other relations in order that we know everything

there is to know about the gas (macroscopically, that is!). For systems more complicated

than a gas, other parameters may be needed.

Another thing to notice is that not all parameters may be speciﬁed independently. For

example, having speciﬁed N, T, and V , the pressure is determined. Thus there is a certain

minimum number of parameters which specify the system. Any property of the system

must be a function of these parameters. Furthermore, we can often change variables and

use a diﬀerent set of parameters. For a single component ideal gas, we might have

p = p(N, V, T), U = U(N, V, T), S = S(N, V, T) .

We might imagine solving for T in terms of N, V , and U, and we can write

p = p(N, V, U), T = T(N, V, U), S = S(N, V, U) .

Anything that depends only on the equilibrium state of the system can be expressed as

a function of the parameters chosen. Which parameters are to be used depends on the

particular situation under discussion. For example, if the volume of a system is under our

control, we would likely use that as one of the independent parameters. On the other hand,

many processes occur at constant pressure (with the volume adjusting to what it needs to

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-5

be). In this case, using p rather than V as the independent parameter will probably be

more convenient.

The Temperature

As we remarked, the entropy is the logarithm of the number of microstates accessible

to a system. The number of states must be a function of the same macroscopic parameters

that determine the macrostate of the system. Let’s consider a system described by its

internal energy U, its volume V , and the number of each kind of constituent particle N

a

,

N

b

, . . .. For the moment, we ignore the possibility of reactions which can change particles

of one kind into another kind. This means that our expressions will have the same form for

N

a

, N

b

, etc., so we’ll just assume a single kind of particle for the time being and assume

we have N of them. Then the number of microstates is

g = g(U, V, N) .

If we have two systems, that we prevent from interacting, then the number of mi-

crostates of the combined system is

g(U, V, N, U

1

, V

1

, N

1

) = g

1

(U

1

, V

1

, N

1

)g

2

(U

2

, V

2

, N

2

) ,

with

U = U

1

+ U

2

, V = V

1

+ V

2

, N = N

1

+ N

2

.

This is straightforward. Any microstate in system 1 can be paired with any microstate in

system 2, so the total number of microstates is just the product of the number for each

system. Also, we have speciﬁed the macrostate in terms of extensive parameters, so we

can write the parameters of the combined system as the sum of those for the individual

systems as well as one set of the individual system parameters.

Following K&K, the dimensionless entropy is just

σ(U, V, N, U

1

, V

1

, N

1

) = log g(U, V, N, U

1

, V

1

, N

1

) = log g

1

g

2

= log g

1

+ log g

2

= σ

1

(U

1

, V

1

, N

1

) + σ

2

(U

2

, V

2

, N

2

) .

So far, we haven’t really done anything. We’ve just written down some deﬁnitions

twice. We have prevented the two systems from interacting, so nothing exciting can hap-

pen. Now let’s suppose we allow the systems to exchange energy. In other words, we allow

U

1

and U

2

to vary, but any change in U

1

has a compensating change in U

2

so that U is

constant. In addition, we prevent changes in volume and numbers of particles, so that V

1

,

V

2

, N

1

, and N

2

remain constant.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-6

We’re placing the systems in thermal contact, but preventing changes in volume or

particle number. We know what will happen: energy ﬂows from the hotter system to the

cooler system until they come to thermal equilibrium at the same temperature. We know

this from our intuitive understanding of the second law: heat ﬂows from a hot object to a

cold object.

But, what about our postulate that a system maximizes the number of accessible

microstates? In this case, it means that the system adjusts U

1

and U

2

to maximize the

entropy. So,

∂σ

∂U

1

V,N

= 0 since σ is maximized

=

∂σ

1

∂U

1

V,N

+

∂σ

2

∂U

1

V,N

=

∂σ

1

∂U

1

V,N

+

∂σ

2

∂U

2

V,N

∂U

2

∂U

1

=

∂σ

1

∂U

1

V,N

−

∂σ

2

∂U

2

V,N

since ∆U

1

= −∆U

2

.

This means

∂σ

1

∂U

1

V,N

=

∂σ

2

∂U

2

V,N

,

after equilibrium has been established.

So at equilibrium, the rate of change of entropy with respect to energy is the same for

the two systems. If we started out with the two systems and we allowed them to exchange

energy and nothing happened, then we know that ∂σ/∂U was already the same. If system

1 and system 2 are in equilibrium with respect to energy exchange and we allow system

1 to exchange energy with a third system and nothing happens, then ∂σ

3

/∂U

3

must also

have the same value and nothing will happen if systems 2 and 3 are allowed to exchange

energy. Thus, ∂σ/∂U has properties very similar to those we ascribe to temperature. In

fact, we can deﬁne the temperature as:

1

τ

=

∂σ

∂U

V,N

.

This makes τ an intensive quantity (it’s the ratio of two extensive quantities), and it makes

the energy ﬂow in the “correct” direction.

This can be seen as follows: if the two systems are not in equilibrium when we allow

energy to ﬂow, then the entropy of the combined systems must increase: The increase in

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-7

entropy after a very small amount of energy has been transferred is

δσ > 0

= δσ

1

+ δσ

2

=

1

τ

1

δU

1

+

1

τ

2

δU

2

=

1

τ

1

−

1

τ

2

δU

1

.

So if τ

1

< τ

2

, δU

1

> 0, which means energy ﬂows from the high τ system to the low τ

system.

Finally, if you remember your elementary thermodynamics, recall that dU = T dS −

p dV which agrees with this deﬁnition of temperature.

Units: from our deﬁnitions σ is dimensionless and τ has the dimensions of energy. You

recall that temperature T has the dimensions of Kelvins and entropy S has the dimensions

of ergs per Kelvin. As it turns out,

S = kσ ,

τ = kT .

Boltzmann’s constant is really just a scale factor which converts conventional units to the

fundamental units we’ve deﬁned above.

It’s often said that we measure temperature in Kelvins or degrees Celsius or Fahren-

heit because the measurement of temperature was established before the development of

thermodynamics which in turn took place before the connection to energy was fully ap-

preciated. What would you think if you tuned in to the weather channel and found out

that the high tomorrow was expected to be 4.14 ×10

−14

erg or 0.0259 eV??? (If I did the

arithmetic correctly, this is ∼ 80

◦

F.)

Actually, to measure a temperature, we need a thermometer. Thermometers make use

of physical properties which vary with temperature. (That’s obvious I suppose!) The trick

is to calibrate the thermometers so you get an accurate measure of the thermodynamic

temperature, τ/k. A recent Physics Today article discusses some of the diﬃculties in

deﬁning a good practical scale for τ/k < 1 Kelvin. (Soulen, Jr., R. J., and Fogle, W. E.,

1997, Physics Today, vol. 50, no. 8, p. 36, “Temperature Scales Below 1 Kelvin.”)

One other thing to point out here: You’ve no doubt noticed the V, N subscripts. When

you read a thermodynamics text, you’ll often ﬁnd the statement that this a reminder that

V and N are being held ﬁxed in taking the indicated partial derivative. Well, this is true,

but since we have a partial derivative, which already means hold everything else ﬁxed, why

do we need an extra reminder? Answer: since there are so many choices of independent

variables, these subscripts are really a reminder of the set of independent variables in use.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Sep-2004 2-8

Note that we can add energy to a gas keeping the volume and number of particles ﬁxed. In

this case the pressure and temperature rise. Alternatively, we can keep the pressure and

number of particles ﬁxed. In this case the volume and temperature increase. Furthermore,

∂σ

∂U

V,N

=

∂σ

∂U

p,N

.

When it’s obvious from the context which set of independent variables are in use, I will

probably be lazy and omit the subscripts.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-1

Pressure

Last lecture, we considered two systems with entropy as a function of internal energy,

volume and number of particles,

σ(U, V, N, U

1

, V

1

, N

1

) = σ

1

(U

1

, V

1

, N

1

) + σ

2

(U

2

, V

2

, N

2

) .

We allowed them to exchange internal energy (that is, they were placed in thermal con-

tact), and by requiring that the entropy be a maximum, we were able to show that the

temperature is

1

τ

=

∂σ

∂U

V,N

.

Suppose we continue to consider our two systems, and ask what happens if we allow

them to exchange volume as well as energy? (We’re placing them in mechanical as well as

thermal contact.) Again, the total entropy must be a maximum with respect to exchanges

of energy and exchanges of volume. Working through similar mathematics, we ﬁnd an

expression for the change in total entropy and insist that it be zero (so the entropy is

maximum) at equilibrium,

0 = δσ

=

∂σ

1

∂U

1

δU

1

+

∂σ

2

∂U

2

δU

2

+

∂σ

1

∂V

1

δV

1

+

∂σ

2

∂V

2

δV

2

=

∂σ

1

∂U

1

−

∂σ

2

∂U

2

δU

1

+

∂σ

1

∂V

1

−

∂σ

2

∂V

2

δV

1

,

from which we infer that at equilibrium,

∂σ

1

∂U

1

=

∂σ

2

∂U

2

,

which we already knew, and

∂σ

1

∂V

1

=

∂σ

2

∂V

2

.

This last equation is new, and it must have something to do with the pressure. Why?

Because, once the temperatures are the same, two systems exchange volume only if one

system can “push harder” and expand while the other contracts. We deﬁne the pressure:

p = τ

∂σ

∂V

U,N

.

We will see later that this deﬁnition agrees with the conventional deﬁnition of pressure as

force per unit area.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-2

Chemical Potential

Well, there’s one variable left, guess what we’re going to do now! Suppose we allow

the two systems to exchange particles as well as energy and volume. Again, we want to

maximize the entropy with respect to changes in all the independent variables and this

leads to,

0 = δσ

=

∂σ

1

∂U

1

δU

1

+

∂σ

2

∂U

2

δU

2

+

∂σ

1

∂V

1

δV

1

+

∂σ

2

∂V

2

δV

2

+

∂σ

1

∂N

1

δN

1

+

∂σ

2

∂N

2

δN

2

=

∂σ

1

∂U

1

−

∂σ

2

∂U

2

δU

1

+

∂σ

1

∂V

1

−

∂σ

2

∂V

2

δV

1

+

∂σ

1

∂N

1

−

∂σ

2

∂N

2

δN

1

.

So, when the systems can exchange particles as well as energy and volume,

∂σ

1

∂N

1

=

∂σ

2

∂N

2

.

The fact that these derivatives must be equal in equilibrium allows us to deﬁne yet another

quantity, µ, the chemical potential

µ = −τ

∂σ

∂N

U,V

.

If two systems are allowed to exchange particles and the chemical potentials are unequal,

there will be a net ﬂow of particles until the chemical potentials are equal. Like temperature

and pressure, chemical potential is an intensive quantity. Unlike temperature and pressure,

you probably have not come across chemical potential in your elementary thermodynamics.

You can think of it very much like a potential energy per particle. Systems with high

chemical potential want to send particles to a system with low potential energy per particle.

Note that we can write a change in the entropy of a system, speciﬁed in terms of U, V ,

and N as

dσ =

1

τ

dU +

p

τ

dV −

µ

τ

dN ,

or rearranging,

dU = τ dσ −p dV + µdN .

Which is the conservation of energy (ﬁrst law of thermodynamics) written for a system

which can absorb energy in the form of heat, which can do mechanical pV work, and which

can change its energy by changing the number of particles.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-3

First Derivatives versus Second Derivatives

You will notice that the quantitites deﬁned by ﬁrst derivatives are not material speciﬁc.

For example, whether it’s nitrogen gas or a block of steel, the rate of change of energy

with entropy (at constant volume and particle number) is the temperature.

We’ll eventually deﬁne Helmholtz and Gibbs free energies and enthalpy (diﬀerent

independent variables) and it will always be the case that the ﬁrst derivatives of these

quantities produce other quantities that are not material speciﬁc.

To get to material speciﬁc quantities, one must go to second derivatives. For example,

suppose we have a block of steel and nitrogen gas inside a container that is thermally

insulating, ﬁxed in volume, and impermeable. Then at equilibrium,

∂U

steel

∂V

steel

S,N

=

∂U

nitrogen

∂V

nitrogen

S,N

= −p .

If we make a change to the volume of the container, we might be interested in

∂p

∂V

= −

∂

2

U

∂V

2

.

This quantity is related to the compressibility of the material. Nitrogen gas is much more

compressible than steel and most of the volume change will be taken up by the gas, not

the steel. In other words, the material speciﬁc quantity (second derivative) is diﬀerent for

the two materials.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-4

Probability

Here, we will introduce some basic concepts of probability. To start with, one imagines

some experiment or other process in which several possible outcomes may occur. The

possible outcomes are known, but not deﬁnite. For example, tossing a die leads to one

of the 6 numbers 1, 2, 3, 4, 5, 6 turning up, but which number will occur is not known

in advance. Presumably, a set of elementary outcomes can be deﬁned and all possible

outcomes can be speciﬁed by saying which elementary outcomes must occur. For example,

the tossing of the die resulting in an even number would be made up of the elementary

events: the toss is 2 or the toss is 4 or the toss is 6. A set of elementary events is such

that one and only one event can occur in any repetition of the experiment. For example,

the events (1) the toss results in a prime number and (2) the toss gives an even number

could not both be part of a set of elementary events, because if the number 2 comes up,

both events have occurred!

One imagines that a very large number of tosses of the die take place. Furthermore,

in each toss, an attempt is made to ensure that there is no memory of the previous toss.

(This is another way of saying successive tosses are independent.) Then the probability

of an event is just the fraction of times it occurs in this large set of experiments, that

is, n

e

/N, where n

e

is the number of times event e occurs and N is the total number of

experiments. In principle, we should take the limit as the number of trials goes to ∞.

From this deﬁnition it is easy to see that the probabilities of a set of elementary events

must satisfy

p

i

≥ 0 ,

and

¸

i

p

i

= 1 ,

where p

i

is the probability of event i and i is an index that ranges over the possible

elementary events.

The above deﬁnition is intuitive, but gives the sense of a process occurring in time.

That is, we throw the same die over and over again and keep track of what happens.

Instead, we can imagine a very large number of dice. Each die has been prepared, as nearly

as possible, to be identical. Each die is shaken (randomized) and tossed independently.

Again, the probability of an event is the fraction of the total number of trials in which

the event occurs. This collection of identically prepared systems and identically performed

trials is called an ensemble and averages that we calculate with this construction are called

ensemble averages.

You are probably thinking that for the die, the probabilities of each of the six elemen-

tary events 1, 2, 3, 4, 5, 6 must be 1/6. Well, they could be, but it’s not necessary! You’ve

heard of loaded dice, right? All that’s really necessary is that each p

i

be non-negative

and that their sum be 1. Probability theory itself makes no statement about the values of

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-5

the probabilities. The values must come from somewhere else. In general, we just assign

probabilities to the elementary events. Often we will appeal to symmetry or other argu-

ments to assign the probabilities. For example, since a die is a symmetric cube, no face

can be distinguished (mechanically) from any other face and we can plausibly argue that

the probabilities should be equal.

Aside: well, the dots have to be painted on, so the die isn’t perfectly symmetric.

Presumably, diﬀerences in the amount and pattern of paint on each face make a negligible

diﬀerence in the mechanical properties of the die (such as cm, moment of inertia, etc.) so

it’s a very good approximation to regard the die as symmetric. However, some dice have

rather large indentations for each dot. I’ve occasionally wondered if this might make a

detectable diﬀerence in the probabilities.

In our discussion of the entropy, we postulated that a system is equally likely to be

in any microscopic state consistent with the constraints. This amounts to assigning the

probabilities and is basically an appeal to symmetry in the same way that assigning equal

probabilities to each face of a die is an appeal to symmetry!

Averages

Assuming there is some numeric value associated with each elementary event, we can

calculate its average value just by adding up all the values and dividing by the total number

of trials—exactly what you think of as an average. So, if event i produces the value y

i

,

then its average value is

y =

1

N

(y

1

+ y

1

+· · · y

1

. .. .

n

1

times

+y

2

+ y

2

+· · · y

2

. .. .

n

2

times

+· · ·)

=

1

N

(n

1

y

1

+ n

2

y

2

+· · ·)

=

¸

i

y

i

p

i

.

Quantities like y, whose value varies across an ensemble, are called random variables.

After the average, we will often be most interested in the variance (often called the

square of the standard deviation.) This is just the average value of the square of the

deviation from the average.

var(y) = σ

2

y

=

(y −y)

2

,

where σ

y

is the standard deviation in y, not the entropy! The standard deviation is a

measure of the spread about the average.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-6

Probabilities for Continuous Variables.

Rather than giving one of a ﬁnite (or inﬁnite) number of discrete outcomes, an ex-

periment might result in the measurement of a random variable which is continuously

distributed over some ﬁnite (or inﬁnite) range. In this case we deal with a probability

density rather than discrete probabilities. For example, we might make a measurement of

a continuous variable x. Then the probability that the measurement falls in a small range

dx around the value x is

Prob(x < result < x + dx) = p(x) dx ,

where p(x) is the probability density. Just as for discrete probabilities, the probability

density must satisfy

p(x) ≥ 0 ,

and

allowed range of x

p(x) dx = 1 .

We can simply deﬁne p(x) = 0 when x is outside the allowed range, so the normalization

becomes

+∞

−∞

p(x) dx = 1 .

The average of any function of x, y(x) is deﬁned by

y =

+∞

−∞

y(x)p(x) dx .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-7

The Binomial Distribution

As an example of working with probabilities, we consider the binomial distribution.

We have N trials or N copies of similar systems. Each trial or system has two possible

outcomes or states. We can call these heads or tails (if the experiment is tossing a coin),

spin up or spin down (for spin 1/2 systems), etc. We suppose that each trial or system is

independent and we suppose the probability of heads in one trial or spin up in one system

is p and the probability of tails or spin down is 1 − p = q. (Let’s just call these up and

down, I’m getting tired of all these words!)

To completely specify the state of the system, we would have to say which of the N

systems are up and which are down. Since there are 2 states for each of the N systems,

the total number of states is 2

N

. The probability that a particular state occurs depends on

the number of ups and downs in that state. In particular, the probability of a particular

state with n up spins and N −n down spins is

Prob(single state with n up spins) = p

n

q

N−n

.

Usually, we are not interested in a single state with n up spins, but we are interested in all

the states that have n up spins. We need to know how many there are. There is 1 state

with no up spins. There are N diﬀerent ways we have exactly one of the N spins up and

N −1 down. There are N(N −1)/2 ways to have two spins up. In general, there are

N

n

**diﬀerent states with n up spins. These states are distinct, so the probability of getting any
**

state with n up spins is just the sum of the probabilities of the individual states. So

Prob(any state with n up spins) =

N

n

p

n

q

N−n

.

Note that

1 = (p + q)

N

=

N

¸

n=0

N

n

p

n

q

N−n

,

and the probabilities are properly normalized.

To illustrate a trick for computing average values, suppose that when there are n up

spins, a measurement of the variable y produces n. What are the mean and variance of y?

To calculate the mean, we want to perform the sum,

y =

N

¸

n=0

n

N

n

p

n

q

N−n

.

Consider the binomial expansion

(p + q)

N

=

N

¸

n=0

N

n

p

n

q

N−n

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Sep-2004 3-8

and observe that if we treat (for the moment) p and q as independent mathematical

variables and we diﬀerentiate both sides of this expression with respect to p (keeping q

ﬁxed), we get

N(p + q)

N−1

=

N

¸

n=0

n

N

n

p

n−1

q

N−n

.

The RHS is almost what we want—it’s missing one power of p. No problem, just multiply

by p,

Np(p + q)

N−1

=

N

¸

n=0

n

N

n

p

n

q

N−n

.

This is true for any (positive) values of p and q. Now specialize to the case where p+q = 1.

Then

Np =

N

¸

n=0

n

N

n

p

n

q

N−n

= y .

A similar calculation gives

var(y) = Npq .

The fractional spread about the mean is proportional to N

−1/2

. This is typical;

as the number of particles grows, the fractional deviations from the mean of physical

quantities decreases in proportion to N

−1/2

. So with ∼ N

0

numbers of particles, fractional

ﬂuctuations in physical quantities are ∼ 10

−12

. This is extremely small. Even though the

macroscopic parameters in statistical mechanics are random variables, their ﬂuctuations

are so small that they can usually be ignored. We speak of the energy of a system and

write down a single value, even though the energy of a system in thermal contact with a

heat bath is properly a random variable which ﬂuctuates continuously.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-1

Example—A Spin System

In the last lecture, we discussed the binomial distribution. Now, I would like to add

a little physical content by considering a spin system. Actually this will be a model for a

paramagnetic material. This system is also a trivial subcase of the Ising model.

We’ll consider a large number, N, of identical spin 1/2 systems. As you know, if

you pick an axis, and measure the component of angular momentum of a spin 1/2 system

along that axis, you can get only two answers: +¯ h/2 and −¯h/2. If there’s charge involved,

then there’s a magnetic moment, m, parallel or antiparallel to the angular momentum. If

there’s a magnetic ﬁeld, B, then this deﬁnes an axis and the energy m· B of the spin

system in the magnetic ﬁeld can be either −mB if the magnetic moment is parallel to the

ﬁeld or +mB if the magnetic moment is anti-parallel to the ﬁeld. To save some writing,

let E = mB > 0 so the energy of an individual system is ±E.

In this model, we are considering only the energies of the magnetic dipoles in an

external magnetic ﬁeld. We are ignoring all other interactions and sources of energy. For

example, we are ignoring magnetic interactions between the individual systems, which

means we are dealing with a paramagnetic material, not a ferromagnetic material. Also,

we are ignoring diamagnetic eﬀects—eﬀects caused by induced magnetic moments when

the ﬁeld is established. Generally, if there is a permanent dipole moment m, paramagnetic

eﬀects dominate diamagnetic eﬀects.

Of course, there must be some interactions of our magnets with each other or with

the outside world or there would be no way for them to change their energies and come to

equilibrium. What we’re assuming is that these interactions are there, but just so small

that we don’t need to count them when we add up the energy. (Of course the smaller they

are, the longer it will take for equilibrium to be established. . .)

Our goal here is to work out expressions for the energy, entropy, temperature, in terms

of the number of parallel and antiparallel magnetic moments.

If there is no magnetic ﬁeld, then there is nothing to pick out any direction, and

we expect that any given magnetic moment or spin is equally likely to be parallel or

antiparallel to any direction we pick. So the probability of parallel should be the same

as the probability of antiparallel should be 1/2: p = 1 − p = q = 1/2. If we turn on

the magnetic ﬁeld, we expect that more magnets will line up parallel to the ﬁeld than

antiparallel (p > q) so that the entire system has a lower total energy than it would have

with equal numbers of magnets parallel and antiparallel.

If we didn’t know anything about thermal eﬀects, we’d say that all the magnets should

align with the ﬁeld in order to get the lowest total energy. But we do know something

about thermal eﬀects. What we know is that these magnets are exchanging energy with

each other and the rest of the world, so a magnet that is parallel to the ﬁeld, having energy

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-2

−E, might receive energy +2E and align antiparallel to the ﬁeld with energy +E. It will

stay antiparallel until it can give up the energy 2E to a diﬀerent magnet or to the outside

world. The strengths of the interactions determine how rapidly equilibrium is approached

(a subject we will skip for the time being), but the temperature sets an energy scale and

determines how likely it is that chunks of energy of size 2E are available.

So suppose that n of the magnets are parallel to the ﬁeld and N −n are antiparallel.

K&K deﬁne the “spin excess”, as the number parallel minus the number antiparallel,

2s = n −(N −n) = 2n −N or n = s +N/2. The energy of the entire system is then

U(n) = −nE + (N −n)E = −(2n −N)E = −2sE .

The entropy is the log of the number of ways our system can have this amount of energy

and this is just the binomial coeﬃcient.

σ(n) = log

N

n

= log

N!

(N/2 +s)! (N/2 −s)!

.

To put this in the context of our previous discussion of entropy and energy, note that

we talked about determining the entropy as a function of energy, volume, and number of

particles. In this case, the volume doesn’t enter and we’re not changing the number of

particles (or systems) N. At the moment, we are not writing the entropy as an explicit

function of the energy. Instead, the two equations above are parametric equations for the

entropy and energy.

To ﬁnd the temperature, we need ∂σ/∂U. In our formulation, the entropy and energy

are functions of a discrete variable, not a continuous variable. No problem! We’ll just send

one magnet from parallel to anti-parallel. This will make a change in energy, ∆U, and a

change in entropy, ∆σ and we simply take the ratio as the approximation to the partial

derivative. So,

∆U = U(n −1) −U(n) = 2E ,

∆σ = σ(n −1) −σ(n)

= log

N

n −1

−log

N

n

= log

¸

N!

(n −1)! (N −n + 1)!

n! (N −n)!

N!

= log

n

N −n + 1

= log

n

N −n

1 can’t matter if N −n ∼ N

0

= log

N/2 +s

N/2 −s

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-3

where the last line expresses the result in terms of the spin excess. Throwing away the 1

is OK, provided we are not at zero temperature where n = N.

The temperature is then

τ =

∆U

∆σ

=

2E

log(N/2 +s)/(N/2 −s)

.

At this point it’s convenient to solve for s. We have

N/2 +s

N/2 −s

= e

2E/τ

,

and with a little algebra

2s

N

= tanh

E

τ

.

The plot shows this function—fractional spin excess versus E/τ. To the left, thermal

energy dominates magnetic energy and the net alignment is small. To the right, magnetic

energy dominates thermal energy and the alignment is large. Just what we expected!

Suppose the situation is such that E/τ is large. Then the magnets are all aligned. Now

turn oﬀ the magnetic ﬁeld, leaving the magnets aligned. What happens? The system is

no longer in equilibrium. It absorbs energy and entropy from its surroundings, cooling the

surroundings. This technique is actually used in low temperature experiments. It’s called

adiabatic demagnetization. Demagnetization refers to removing the external magnetic ﬁeld

and adiabatic refers to doing it gently enough to leave the magnets aligned.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-4

The Boltzmann Factor

An additional comment on probabilities: When the spin excess is 2s, the probabilities

of parallel or antiparallel alignment are:

p =

1

2

+

s

N

, q =

1

2

−

s

N

.

The ratio of the probabilities is

q

p

=

1 −2s/N

1 + 2s/N

= e

−2E/τ

.

This is a general result. The relative probability that a system is in two states with an

energy diﬀerence ∆E is just

Probability of high energy state

Probability of low energy state

= e

−∆E/τ

= e

−∆E/kT

.

This is called the Boltzmann factor. As we’ve already mentioned, this says that energies

∼

<

kT are “easy” to come by, while energies > kT are hard to come by! The temperature

sets the scale of the relevant energies.

The Gaussian Distribution

We’ve discussed two discrete probability distributions, the binomial distribution and

(in the homework) the Poisson distribution. As an example of a continuous distribution,

we’ll consider the Gaussian (or normal) distribution. It is a function of one continuous

variable and occurs throughout the sciences.

The reason the Gaussian distribution is so prevalent is that under very general con-

ditions, the distribution of a random variable which is the sum of a large number of

independent, identically distributed random variables, approaches the Gaussian distribu-

tion as the number of random variables in the sum goes to inﬁnity. This result is called

the central limit theorem and is proven in probability courses.

The distribution depends on two parameters, the mean, µ, (not the chemical poten-

tial!) and the standard deviation, σ (not the entropy!). The probability density is

p(x) =

1

√

2πσ

2

e

−

(x −µ)

2

2σ

2

.

You should be able to show that

1

√

2πσ

2

+∞

−∞

e

−

(x −µ)

2

2σ

2

dx = 1 ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-5

x =

1

√

2πσ

2

+∞

−∞

x e

−

(x −µ)

2

2σ

2

dx = µ ,

var(x) =

1

√

2πσ

2

+∞

−∞

(x −µ)

2

e

−

(x −µ)

2

2σ

2

dx = σ

2

.

Appendix A of K&K might be useful if you have trouble with these integrals. One can

always recenter so that x is measured from µ and rescale so that x is measured in units of

σ. Then the density takes the dimensionless form,

p(x) =

1

√

2π

e

−x

2

/2

.

Sometimes you might need to integrate this density over a ﬁnite (rather than inﬁnite)

range. Two related functions are of interest, the error function

erf(z) =

2

√

π

z

0

e

−t

2

dt = 2

1

√

2π

√

2z

0

e

−x

2

/2

dx ,

and the complementary error function

erfc(z) =

2

√

π

∞

z

e

−t

2

dt = 2

1

√

2π

∞

√

2z

e

−x

2

/2

dx ,

where the ﬁrst expression (involving t) is the typical deﬁnition, and the second (obtained

by changing variables t = x/

√

2 rewrites the deﬁnition in terms of the Gaussian probability

density. Note that erf(0) = 0, erf(∞) = 1, and erf(z) + erfc(z) = 1.

The Gaussian density is just the “bell” curve, peaked in the middle, with small tails.

The error function gives the probability associated with a range in x at the middle of

the curve, while the complementary error function gives probabilities associated with the

tails of the distribution. In general, you have to look these up in tables, or have a fancy

calculator that can generate them. As an example, you might hear someone at a research

talk say, “I’ve obtained a marginal two-sigma result.” What this means is that the signal

that was detected was only 2σ larger than no signal. A noise eﬀect this large or larger will

happen with probability

1

√

2π

∞

2

e

−x

2

/2

dx =

1

2

erfc

2

√

2

= 0.023 .

That is, more than 2 percent of the time, noise will give a 2σ result just by chance. This

is why 2σ is marginal.

We’re straying a bit from thermal physics, so let’s get back on track. One of the

reasons for bringing up a Gaussian distribution is that many other distributions approach

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-6

a Gaussian distribution when large numbers are involved. (The central limit theorem

might have something to do with this!) For example, the binomial distribution. When

the numbers are large, we can replace the discrete distribution in n with a continuous

distribution. The advantage is that it is often easier to work with a continuous function.

In particular, the probability of a spin excess, s, is

p

s

=

N!

(N/2 +s)! (N/2 −s)!

p

N

2

+s

q

N

2

−s

.

We need to do something with the factorials. In K&K, Appendix A, Stirling’s approxima-

tion is derived. For large N,

N! ∼

√

2πNN

N

e

−N

.

With this, we have

p

s

∼

2πN

2π(N/2 +s) 2π(N/2 −s)

N

N

(N/2 +s)

(N/2+s)

(N/2 −s)

(N/2−s)

p

N/2+s

q

N/2−s

=

1

2πN (1/2 +s/N) (1/2 −s/N)

p

N/2+s

q

N/2−s

(1/2 +s/N)

(N/2+s)

(1/2 −s/N)

(N/2−s)

=

1

2πN (1/2 +s/N) (1/2 −s/N)

pq

pq

p

N/2+s

q

N/2−s

(1/2 +s/N)

(N/2+s)

(1/2 −s/N)

(N/2−s)

=

1

2πNpq

p

1/2 +s/N

(N/2+s+1/2)

q

1/2 −s/N

(N/2−s+1/2)

.

Recall that the variance of the binomial distribution is Npq, so things are starting to look

promising. Also, we are working under the assumption that we are dealing with large

numbers. This means that s cannot be close to ±N/2. If it were, then we would have a

small number of aligned, or a small number of anti-aligned magnets. So, in the exponents

in the last line, N/2 ±s is a large number and we can ignore the 1/2. Then

p

s

=

1

2πNpq

p

1/2 +s/N

(N/2+s)

q

1/2 −s/N

(N/2−s)

.

This is a sharply peaked function. We expect the peak to be centered at s = s

0

= s =

n−N/2 = Np−N/2 = N(p−1/2). We want to expand this function about its maximum.

Actually, it will be easier to locate the peak and expand the function, if we work with its

logarithm.

log p

s

= A+

N

2

+s

¸

log p −log

1

2

+

s

N

+

N

2

−s

¸

log q −log

1

2

−

s

N

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-7

where

A =

1

2

log

1

2πNpq

.

To locate the maximum of this function, we take the derivative and set it to 0

d log p

s

ds

= log p −log

1

2

+

s

N

−1 −log q + log

1

2

−

s

N

+ 1 .

We note that this expression is 0 when s/N = p − 1/2, just as we expected. So this is

the point about which we’ll expand the logarithm. The next term in a Taylor expansion

requires the second derivative

d

2

log p

s

ds

2

= −

1

N/2 +s

−

1

N/2 −s

= −

1

Np

−

1

Nq

= −

1

Npq

,

where, in the last line, we substituted the value of s at the maximum. We can expand the

logarithm as

log p

s

= A−

1

2

1

Npq

(s −s

0

)

2

+· · ·

where s

0

= N(p − 1/2) is the value of s at the maximum. Finally, we let σ

2

= Npq,

exponentiate the logarithm, and obtain,

p(s) ∼

1

√

2πσ

2

e

−(s −s

0

)

2

/2σ

2

,

where the notation has been changed to indicate a continuous variable rather than a dis-

crete variable. You might worry about this last step. In particular, we have a discrete

probability that we just converted into a probability density. In fact, p(s) ds is the prob-

ability that that the variable is in the range s →s +ds. In the discrete case, the spacing

between values of s is unity, so we require,

p(s)

(s + 1) −s

= p

s

,

which leads to p(s) = p

s

. Had there been a diﬀerent spacing there would be a diﬀerent

factor relating the discrete and continuous expressions.

All this was a lot of work to demonstrate in some detail that for large N (and not too

large s), the binomial distribution describing our paramagnetic system goes over to the

Gaussian distribution. Of course, expanding the logarithm to second order guarantees a

Gaussian!

In practice, you would not go to all this trouble to do the conversion. The way

you would actually do the conversion is to notice that large numbers are involved, so the

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 17-Sep-2004 4-8

distribution must be Gaussian. Then all you need to know are the mean and variance

which you calculate from the binomial distribution or however you can. Then you just

write down the Gaussian distribution with the correct mean and variance.

Returning to our paramagnetic system, we found earlier that the mean value of the

spin excess is

s

0

=

N

2

tanh

E

τ

.

We can use the Gaussian approximation provided s is not too large compared to N/2 which

means E

∼

<

τ. In this case, a little algebra shows that the variance is

σ

2

= Npq = N

1

2

sech

E

τ

2

.

For given E/τ, the actual s ﬂuctuates about the mean s

0

with a spread proportional to

√

N and a fractional spread proportional to 1/

√

N. A typical system has N ∼ N

0

, so the

fractional spread is of order 10

−12

and the actual s is always very close to s

0

.

While we’re at it, it’s also interesting to apply Stirling’s approximation to calculate

the entropy of our paramagnetic system. Recalling Stirling’s approximation for large N,

N! ∼

√

2πNN

N

e

−N

.

Taking the logarithm, we have

log N! ∼

1

2

log 2π +

1

2

log N +N log N −N .

The ﬁrst two terms can be ignored in comparison with the last two, so

log N! ∼ N log N −N .

Suppose our spin system has s

0

≈ 0. Then the entropy is

σ ≈ log

N!

(N/2)! (N/2)!

∼ N log N −N −2

(N/2) log(N/2) −(N/2)

= N log N −N log(N/2)

= N log 2

= 4.2 ×10

23

(fundamental units)

= 5.8 ×10

7

erg K

−1

(conventional units) ,

where the last two lines assume one mole of magnets.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-1

Reading

K&K, Chapter 3. Also, for a little culture, there is a handout which is a one page

article from Science, 1997, G. Bertsch, vol. 277, p. 1619. It describes melting in clusters

consisting of 139 atoms! So 1/

√

N ≈ 10%, quite a bit larger than the one part in a trillion

we’ve been talking about when there is a mole of particles! One might expect things to be

less well deﬁned, and sure enough, these clusters seem to melt over an appreciable range

in temperature (rather than a single T). This may be a case where statistical mechanics

is just on, or just past the edge!

The Boltzmann Factor

Let’s imagine we have an object which is isolated from the rest of the world, so its

energy, entropy, and so on are constant. Furthermore, it has come to equilibrium, so all

parts of the object are at the same temperature, pressure, and so on. We imagine dividing

this object into two pieces: a small piece, called the system; and a large piece called the

heat bath or heat reservoir (or just bath or reservoir). The system is supposed to be

suﬃciently small that it’s useful to think of it as being in a single (quantum) state. A

system might be a single atom or molecule, but it could be a larger entity if such an entity

can be described as being in a single state. The remainder of the object, the bath, is

supposed to be very large and might consist of a very large number of similar atoms or

molecules. (In principle, we should let N → ∞, where N is the number of molecules in

the bath.) The system and the bath interact so that the system is in a particular state

only with some probability. We are going to calculate this probability. We want to speak

of the system as having energy E. This means that the interaction between the system

and the bath must be weak in order that we can ascribe a deﬁnite energy to the system.

Consider two states of the system, 1 and 2, with energies E

1

and E

2

. When the system

is in state 1, the bath has energy U − E

1

, where U is the total (ﬁxed) energy of the bath

plus system. The number of states that correspond to this energy in the system is

g(U −E

1

) ×1 = exp

σ(U −E

1

)

×1 .

Where the ﬁrst factor is the number of states in the bath and the second factor is the

number of states (just 1) of the system. To have the factor 1 here is the reason that we

insisted the system be in a single state. Similarly, the number of states in the case that

the system has energy E

2

is

g(U −E

2

) ×1 = exp

σ(U −E

2

)

×1 .

Our fundamental assumption is that each state (of the system plus bath together)

that is compatible with the constraints is equally probable. So, the ratio of the probability

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-2

that the system is in state 2 to the probability that it is in state 1 is

P(state 2)

P(state 1)

=

g(U −E

2

)

g(U −E

1

)

= e

σ(U −E

2

) −σ(U −E

1

)

.

Now, E is an energy on the scale of an energy of a single molecule while U is an energy

typical of a mole. So we can expand σ in a tailor series around E = 0,

σ(U −E) = σ(U) −E

∂σ

∂U

+· · · = σ(U) −

E

τ

+· · · .

Note that The ﬁrst term on the right is ∼ N times larger than the second term, and we

expect that the ﬁrst omitted term will be another factor of ∼ 1/N smaller. Inserting this

expansion into our expression for the probability ratio, we have

P(state 2)

P(state 1)

= e

σ(U) −E

2

/τ −σ(U) + E

1

/τ

= e

−(E

2

−E

1

)/τ

.

The probability ratio is an exponential in the energy diﬀerence divided by the temperature.

As noted when we discussed the model paramagnetic system, this is called the Boltzmann

factor, and we’ve just shown that this is a general result.

It may seem we got something for nothing: we made a few deﬁnitions, did some

mathematical hocus-pocus and voila, out pops the Boltzmann factor. A key ingredient

is our postulate that all states which satisfy the constraints are equally probable. The

number of states goes up with increasing energy U. The rate of increase (in the logarithm)

is measured by the temperature, τ. When the system is in a state with energy E, it

necessarily received that energy from the heat bath. The more energy the heat bath gives

to the system, the fewer states it “has left.” This is what makes higher energy states of

the system less probable.

In principle, we should consider an ensemble of identically prepared heat baths and

systems. An ensemble in which the probability follows the Boltzmann form (∝ exp(−E/τ))

is called a canonical ensemble.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-3

Systems with Several Forms of Energy

A single system in a canonical ensemble might have several ways to store energy. For

example, if the system is a gas molecule, it has energy associated with translation of the

center of mass, rotation about the center of mass, and various forms of internal energy such

as vibration or other electronic excitations and interactions among spins. If the energies

can be assigned independently, then the probabilities are independent. For example, if we

want to know the probability that a molecule is in a particular rotational state, with energy

E

rot

, we can think of the bath as including the translational and internal motions of the

molecule under consideration as well as all the motions of all the other molecules. Similarly,

if we consider the translational motion, with energy E

tran

, all other forms of energy in this

molecule and all other molecules may constitute the heat bath. The probabilities are

P(E

tran

) ∝ e

−E

tran

/τ

,

P(E

rot

) ∝ e

−E

rot

/τ

,

· · · .

These probabilities are independent, so the probability that our molecule has a total energy

E

tot

= E

tran

+ E

rot

+· · · is just the product,

P(E

tot

) ∝ e

−(E

tran

+ E

rot

+· · ·)/τ

= e

−E

tot

/τ

.

Caveat 1: this is the probability for a single state of the system having the speciﬁed

total energy. If the system has several diﬀerent ways of distributing E

tot

among its sub-

systems, then each way has the same probability (our assumption that each state has the

same probability) and the probability of being in any state with that E

tot

is just the sum.

Caveat 2: it may not always be true that the energies can be distributed independently.

For example, the moment of inertia, and hence the rotational energy levels, may depend

on the amplitude of vibration.

In (older) thermo texts, you will often see expressions like

P(energy 2)

P(energy 1)

=

g

2

g

1

e

−(E

2

−E

1

)/τ

,

where g

1

and g

2

are called statistical weights. The statistical weight of states with energy

E is just the number of distinct states with that energy. This expression agrees with the

statement above that the probabilities of the independent states add. Note the diﬀerence

between the probability of a single state with energy E versus the probability of any state

with energy E.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-4

Diversion: the Maxwell Velocity Distribution

Consider a low density gas. Generally, the forces between molecules are only large

when the molecules are within a few molecular diameters of each other. The mean separa-

tion is many molecular diameters. We expect that a molecule in a low density gas satisﬁes

our deﬁnition of a system which is weakly interacting with its heat bath (all the other

molecules in the gas).

We consider only the translational energy of a molecule. The probability that a

molecule is in a particular state with energy E = mv

2

/2 is just

P(E) ∝ e

−E/τ

= e

−mv

2

/2τ

,

where m is the mass and v is the velocity of the molecule. Now we have a problem. This

expressions applies to a particular state. Usually we think of the energy of translation

and the velocity as continuous variables. What constitutes a particular state? Let’s post-

pone the counting of states for a bit and see how far we can get with some reasonable

assumptions.

First of all, if we want to treat the energy and velocity as continuous variables, we

should be talking about a probability density, where the probability that the energy lies in

the range E → E + dE is given by p(E) dE. This will be the probability of getting E no

matter how many diﬀerent states have this E, and this probability must be proportional

to the Boltzmann factor and to the number of states that have this E. In other words,

p(E) dE = Ce

−E/τ

n(E) dE ,

where C is a constant whose value is adjusted to ensure that

p(E) dE = 1, and n(E),

usually called the density of states, is the number of distinct states per unit energy with

energy E. That is, we’ve put our ignorance of the number of states into this function!

We note that the Boltzmann factor, written in terms of velocities, is

P(E) ∝ e

−mv

2

/2τ

= e

−m(v

2

x

+ v

2

y

+ v

2

z

)/2τ

.

This strongly suggests that each component of the velocity is normally distributed. We

might expect this on other grounds as well. For example, if we pick a molecule and measure

the x component of its velocity, we note that v

x

is a random variable and its value is

determined by the previous history of collisions the molecule has undergone. These are

the kinds of conditions that give rise to Gaussian distributions although proving it in this

case might be painful. We expect that v

x

= 0. Otherwise, our sample of gas would have

a non-zero velocity in the x direction and we are considering a sample at rest (of course!).

Also, the mean square value of v

x

contributes to the energy and we would expect this to be

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-5

related to the temperature as the Boltzmann distribution suggests. Finally (among things

that we expect), there is no reason to prefer one direction over another, so the probability

distributions for v

x

, v

y

, and v

z

should be the same. In fact, the probability of any velocity

component should be the same which means that the joint probability should depend only

on the magnitude and not on the direction of the velocity.

Putting all this together, we guess that the joint probability that the x, y, and z

components of the velocity are in the ranges v

x

→ v

x

+ dv

x

, v

y

→ v

y

+ dv

y

, and v

z

→

v

z

+ dv

z

, is

p(v

x

, v

y

, v

z

) dv

x

dv

y

dv

z

=

1

2πτ/m

e

−mv

2

x

/2τ

dv

x

×

1

2πτ/m

e

−mv

2

y

/2τ

dv

y

×

1

2πτ/m

e

−mv

2

z

/2τ

dv

z

,

=

1

2πτ/m

3

2

e

−mv

2

/2τ

dv

x

dv

y

dv

z

.

This is called the Maxwell velocity distribution. Now let’s change variables from Cartesian

components to spherical polar components, v, θ, φ where

v

x

= v sin θ cos φ ,

v

y

= v sin θ sin φ ,

v

z

= v cos θ .

This is just like changing coordinates from x, y, z to r, θ, φ. The result is

p(v, θ, φ) dv dθ dφ =

1

2πτ/m

3

2

e

−mv

2

/2τ

v

2

sin θ dv dθ dφ .

Just as we expected, the probability is independent of direction, so we can integrate over

direction (θ and φ) to obtain the probability density for the velocity and any direction.

The integral over directions gives 4π and we have,

p(v) dv = 4π

1

2πτ/m

3

2

e

−mv

2

/2τ

v

2

dv .

Let’s change variables one more time, back to the energy E = mv

2

/2,

p(E) dE = 2π

1

πτ

3

2

e

−E/τ

E

1

2

dE .

Comparing this with our earlier expression, we conclude that the number of states per unit

energy, n(E) must be proportional to

√

E.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-6

To recap: knowing that the probability of a state with energy E is proportional

to exp(−E/τ), we argued that it was reasonable to expect the velocity components to be

normally distributed. We used symmetry arguments to specify the form of the distribution

and we used the probability distribution in energy to set the variance. We made some

changes in variables to convert our guessed probability density in velocity to a probability

density in energy from which we concluded that the number of kinetic energy states per

unit energy is ∝ E

1/2

.

Aside—the Gamma Function

I kind of side-stepped the gamma function last week when we were using Stirling’s

approximation. But I think I should at least introduce the function as it’s necessary for

some of the integrals you might need to do. For example, to verify that p(E) above is

properly normalized, you will have to integrate over the energy and this is most naturally

written as a gamma function. Deﬁne the gamma function by an integral:

Γ(z) =

∞

0

t

z−1

e

−t

dt .

Using integration by parts,

Γ(z) =

∞

0

t

z−1

e

−t

dt ,

= −t

z−1

e

−t

∞

0

+(z −1)

∞

0

t

z−2

e

−t

dt (z ≥ 1) ,

= (z −1)

∞

0

t

z−2

e

−t

dt ,

= (z −1) Γ(z −1) .

The gamma function satisﬁes a recursion relation. It is straightforward to show that

Γ(1) = 1 and with the recursion relation, one has

n! = Γ(n + 1) .

This relation can be used to extend the deﬁnition of factorial to non-integers!

The next most interesting arguments of the gamma function after the integers are half

integers. Using the recursion relation, these can be found if one knows

Γ(1/2) =

√

π .

Can you show this?

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-7

For completeness, I should mention the incomplete gamma functions. (I couldn’t

resist, sorry!) These arise when the range of integration does not include the entire interval

[0, ∞).

The Partition Function

We’ve had a diversion and an aside, so maybe it’s time to get back to thermal physics.

Consider the function

Z(τ) =

¸

s

e

−E

s

/τ

,

where the sum extends over all states s. Among other things, this function normalizes the

probabilities,

P(E

s

) =

e

−E

s

/τ

Z(τ)

;

¸

s

P(E

s

) = 1 .

Z is called the partition function. We’ve written it as a function of temperature, but it’s

also a function of the energies of all the states which might be functions of macroscopic

parameters of the system.

The average energy of a member of the ensemble is

E =

¸

s

E

s

P(E

s

) .

Consider the derivative of Z with respect to temperature (the energies of the states, E

s

,

do not depend on temperature),

∂Z

∂τ

=

∂

∂τ

¸

s

e

−E

s

/τ

,

=

¸

s

e

−E

s

/τ

∂

∂τ

−E

s

τ

,

=

¸

s

e

−E

s

/τ

E

s

τ

2

,

=

1

τ

2

¸

s

E

s

e

−E

s

/τ

,

=

Z

τ

2

1

Z

¸

s

E

s

e

−E

s

/τ

,

=

Z

τ

2

E ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 20-Sep-2004 5-8

from which we deduce that

E = τ

2

∂ log Z

∂τ

.

Our discussion followed K&K except that we use E rather than ε and K&K appear

to change the deﬁnition of U in midstream from the energy of heat bath to the average

energy of a state of a single system.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-1

Entropy and Probabilities

We’ve been using the idea that the entropy is the logarithm of the number of states

accessible to the system. We’ve also said that each state is equally likely. At this point, I’d

like to make the connection between entropy and probability. This allows one to construct

an expression for the entropy of a system that isn’t in equilibrium. It should also improve

our intuition about the entropy and the partition function.

We might expect that an expression for entropy can be written in terms of the prob-

abilities that a system is in a particular state. If there are g states, and the probabilities

are p

1

, p

2

, . . . , p

g

, then we would like to write

σ = σ(p

1

, p

2

, . . . , p

g

) .

One of the things that will guide us in our selection of the function is that the entropy

should be additive (i.e., an extensive parameter). If we have two non-interacting systems

with total numbers of states g

1

and g

2

, entropies σ

1

and σ

2

, and probabilities p

1i

and p

2j

(the ﬁrst index is the system, the second index is the state), we can also think of it as a

single system with g = g

1

g

2

states, σ = σ

1

+ σ

2

and, since any state in system 1 can be

combined with any state in 2, the probability of a state in the combined system must be

p

ij

= p

1i

p

2j

.

Since the probabilities multiply, while the entropies add, we might expect that the

entropy should involve the log of the probability. The ﬁrst guess might be

σ

1

= −

¸

i

log p

1i

wrong .

Since p

1i

≤ 1, the minus sign is inserted to make the entropy positive. Why doesn’t this

expression work? There are several reasons. First, suppose one has a totally isolated

system. Then only states with the exact energy of the system are allowed. Disallowed

states have p

1i

= 0 and this will lead to problems with the logarithm. In addition, with

the above expression, the entropy is not additive. To ﬁx up the problem with p

1i

= 0, we

might try multiplying by p

1i

since in the limit x → 0, x log x → 0. Does this make the

entropy additive? Consider

σ = −

¸

i,j

p

1i

p

2j

log p

1i

p

2j

,

= −

¸

i,j

p

1i

p

2j

log p

1i

−

¸

i,j

p

1i

p

2j

log p

2j

,

= −

¸

i

p

1i

log p

1i

−

¸

j

p

2j

log p

2j

,

= σ

1

+σ

2

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-2

We used the fact that

¸

i

p

1i

=

¸

j

p

2j

= 1. We adopt the following expression for the

entropy in terms of the probabilities.

σ = −

¸

i

p

i

log p

i

,

where we can include or omit states with probability 0 without aﬀecting the value of the

entropy.

What set of probabilities maximizes the entropy? The answer depends on the condi-

tions under which we seek a maximum. Suppose we are dealing with a completely isolated

system. Then a state can have non-zero probability only if it has the required energy (and

any other conserved quantities). So let’s limit our sum to allowed states. (Here, we’re

doing this for convenience, not because our expression might blow up!) The other thing

we know is that the probabilities of the allowed states sum to 1. The problem we want to

solve is maximizing the entropy under the constraint that the probabilities sum to 1. How

do we maximize with a constraint? Lagrange multipliers! So we seek to maximize

X(p) = σ(p) +λ

1 −

¸

i

p

i

,

= −

¸

i

p

i

log p

i

+λ

1 −

¸

i

p

i

.

We set the derivative of X with respect to p

i

to zero,

0 =

∂X

∂p

i

= −log p

i

−1 −λ .

This gives

p

i

= e

−(λ + 1)

,

so the probabilities of all allowed states are the same when the entropy is a maximum. We

also set the derivative of X with respect to λ to 0 which recovers the condition that the

probabilities sum to 1. Solving for λ, we ﬁnd λ = log g − 1. (g is the number of allowed

states and the number of terms in the sum.) Finally,

σ = −

¸

i

1

g

log

1

g

= −log

1

g

= log g ,

as we had before.

Now suppose we consider a system which is not isolated, but is in equilibrium thermal

contact with a heat bath so that the average value of its internal energy is U. Again, we

sum only over allowed states. This time states with energies other than U are allowed,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-3

provided the average turns out to be U. We want to ﬁnd the probabilities that maximize

the entropy under the constraints that the probabilities sum to 1 and average energy is U.

We ﬁnd the maximum of

X(p) = −

¸

i

p

i

log p

i

+λ

1

1 −

¸

i

p

i

+λ

2

U −

¸

i

p

i

E

i

,

where E

i

is the energy of state i. We want

0 =

∂X

∂p

i

= −log p

i

−1 −λ

1

−λ

2

E

i

.

It follows that

p

i

= e

−1 −λ

1

−λ

2

E

i

.

You are asked to show in the homework that λ

2

= 1/τ. So, the probabilities wind up with

a Boltzmann factor!

Consider an ensemble of systems. The case in which the energy of each system is

identical and equal probabilities are assigned is known as the micro-canonical ensemble.

The case in which the energies vary and the probabilities are assigned with Boltzmann

factors is known as the canonical ensemble.

Heat Capacity

In general, the amount of energy added to a system in the form of heat, dQ, and the

rise in temperature dτ resulting from this addition of heat are proportional,

dQ = C dτ ,

where C is “constant” of proportionality. Why is constant in quotes? Answer: the bad

news is that it can depend on just about everything. The good news is that over a small

range of temperature it doesn’t vary too much, so it can be treated as a constant.

One of the things it obviously depends on is the amount of material in the system. To

remove this dependence, one often divides by something related to the amount of material

and then speaks of the speciﬁc heat. For example, dividing by the mass of the system gives

the heat capacity per unit mass, c = C/m. Of course, this is only useful if one is dealing

with a homogeneous material. That is you might speak of the speciﬁc heat of aluminum

and the speciﬁc heat of water, but for boiling water in an aluminum pan you would be

concerned with the heat capacity (which you could calculate from the masses of the pan

and the water and the speciﬁc heats from the Handbook of Chemistry and Physics). In the

case of gasses, the amount of material is usually measured in moles and the heat capacity

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-4

is divided by the number of moles to give molar speciﬁc heat or molar heat capacity. This

is usually a number of order the gas constant. In statistical physics, we often speak of the

heat capacity per molecule. This is usually a number of order Boltzmann’s constant.

All the above is mainly bookkeeping. Of more signiﬁcance is the fact that heat ca-

pacities can depend on the manner in which the heat is added to a system. Heat added

to a system whose volume is kept constant will result in a diﬀerent temperature rise than

the same amount of heat added to an identical system whose pressure is kept constant.

The heat capacities in these cases are often written C

V

, constant volume, or C

p

, constant

pressure. Of course, one can think of more complicated way in which heat may be added,

and these can lead to additional deﬁnitions of heat capacity.

After a while, you might get the idea that we are overly ﬁxated on heat capacities.

Measurements of heat capacities, aside from their engineering utility, are also a good way

to test theories of atomic and molecular structure and interactions, A theory will predict

the energy levels of a molecular system, and statistical mechanics relates the microscopic

energy levels to macroscopic quantities. Heat added and temperature rise are relatively

easy macroscopic quantities to measure, so these can provide tests of microscopic theories.

For the moment, we will consider the addition of heat at constant volume and particle

number. Then the internal energy changes only because of the addition of the heat. (No

change due to work done, no change due to adding particles.) Then,

C

V

=

dQ

dτ

=

τdσ

dτ

= τ

∂σ

∂τ

V

=

∂U

∂τ

V

,

where we can use dU for τ dσ since we are considering a constant volume (as indicated

by the subscript) and constant particle number process. Changing to partial derivatives is

just a clean up of the mathematical notation.

It should be noted that in our fundamental units, heat capacities are dimensionless.

However, in conventional units the dimensions are energy per Kelvin.

As an example, we can apply the formalism of the partition function to the param-

agnetic spin system we discussed in lecture 4. Recall, we worked that system out starting

from the entropy. The Boltzmann factor showed up when we considered the numbers of

aligned and anti-aligned magnets. Now we are going to use the partition function (the

sum of Boltzmann factors) to work out the energy from the temperature. An individual

magnetic dipole has energy −E when aligned with the ﬁeld and +E when anti-aligned.

(This is a slight diﬀerence in the deﬁnition of E used in the discussion of the partition

function, but it’s the same as we used in the discussion of the paramagnetic system.) Then

Z(τ) = e

+E/τ

+e

−E/τ

= 2 cosh(E/τ) .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-5

We use the earlier expression to get the average energy per magnet and multiply by N to

get the total energy in the system,

U = Nτ

2

∂ log Z

∂τ

,

= Nτ

2

sinh E/τ

cosh E/τ

∂

∂τ

E

τ

,

= Nτ

2

tanh E/τ

−E

τ

2

,

= −NE tanh E/τ ,

as before! The heat capacity is ∂U/∂τ, so

C

V

= −NE

∂

∂τ

tanh E/τ ,

= −NE sech

2

E/τ

∂

∂τ

E

τ

,

= +N

E

τ

sech

E

τ

2

.

At high and low temperatures the heat capacity goes to zero because of the τ

−2

dependence

and the exponential dependence, respectively. When the temperature is low, it’s very hard

for the bath to get together enough energy to ﬂip a magnet, so increasing the temperature

of the bath has little eﬀect on the total energy of the system. When the temperature is

high, the magnets are 50% aligned and 50% anti-aligned and the system cannot be made

more random by adding energy.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-6

Reversible Processes

We’ve glossed over the fact that adding heat is a process, not a state of the system. So

exactly what happens when we add heat depends on just how we do it. In particular, we

consider reversible processes. For such a process, the “driving force” is inﬁnitesimally small,

the process occurs inﬁnitely slowly, and an inﬁnitesimal change in the driving force can

make the process run equally well in the reverse direction. While the process is underway,

the state of the system (and heat bath) is not an equilibrium state. Because things are

happening so slowly, we can imagine that the system is arbitrarily close to an equilibrium

state. A reversible process can be thought of as a continuous sequence of equilibrium states

carrying the initial state of the system to its ﬁnal state.

In the case of heat transfer, the driving force is the temperature diﬀerence. To obtain

an approximation to a reversible process the temperature diﬀerence between the system

and the source of heat must be very small. The process must be carried out slowly so the

system has time to get close to equilibrium (for the heat energy to be carried to all parts

of the system). Furthermore, the system must not lose any energy by unwanted thermal

conduction through the boundaries. (In actual practice, this means you want to perform

the heat transfer as quickly as possible, before an appreciable amount can leak away!) In

any case, a reversible process is a convenient idealization much like (and related to) the

idealization of frictionless mechanical systems.

Food for thought: Do you suppose there’s a connection between the “direction of the

ﬂow of time” and the increase of entropy in irreversible processes?

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-7

Pressure

Recall in lectures 2 and 3, we maximized the entropy with respect to changes in energy,

volume, and particle number and made some deﬁnitions and came up with

dU = τ dσ −p dV +µdN ,

with

1

τ

=

∂σ

∂U

V,N

,

p

τ

=

∂σ

∂V

U,N

, −

µ

τ

=

∂σ

∂N

U,V

.

Observe that if σ and N are constant, then the pressure is

p = −

∂U

∂V

σ,N

.

What does it mean to keep σ and N constant? N is easy, we just keep the same number

of particles. σ requires a bit more thought. If the entropy doesn’t change, the number of

states doesn’t change. If we perform a volume change at constant entropy, we are changing

the volume without changing the microstates of the system. In other words, the energy

change produced by a change in volume at constant entropy is purely a mechanical energy

change, not a thermal energy change, We know mechanics: the work done (and energy

supplied) when the volume is increased by dV is just −p dV , where p is the ordinary

mechanical pressure, force per unit area. This argument supports our identiﬁcation of

p = τ

∂σ

∂V

U,N

,

as the conventional mechanical pressure.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-8

Pressure in a Low Density Gas, I

Suppose we have some gas in equilibrium at low density. By low density, we mean

that the molecules spend most of the time well separated from each other so that they are

weakly interacting. Occasionally, there are collisions between molecules and these serve

to randomize the velocities and maintain thermal equilibrium. To the extent that we can

treat molecules as point masses and ignore their interactions, we have a model for an ideal

gas.

We are going to relate the pressure to the motions of the gas molecules. To start

with, consider a wall of the container holding the gas. The wall is perpendicular to the x

direction. There is a force on this wall because gas molecules are bouncing oﬀ it. If the

mass of a molecule is m, and the x component of its velocity is v

x

, then the change in

momentum experienced by this molecule if it makes a perfectly elastic, perfectly reﬂecting

collision from the wall is ∆P

x

= −2mv

x

, and of course, the wall experiences an equal and

opposite change in momentum.

A perfectly elastic and perfectly reﬂecting collision is one in which v

x

changes sign

and v

y

and v

z

are unchanged. In other words, the angle of reﬂection equals the angle of

incidence and the kinetic energy is unchanged by the collision. Do we really think that all

collisions between molecules and walls are like this? Of course not. A gas molecule doesn’t

collide with a “wall,” it collides with one, or a small number, of molecules that are part

of the wall, and this collision is just as “randomizing” as collisions between gas molecules.

On the average, there can be no net change in v

y

or v

z

or the gas would start moving in

the y or z directions. In the same way, there can be no net change in the energy caused by

collisions with the wall or the gas would heat up or cool down, contrary to the assumption

of thermal equilibrium. So as a convenience, which is consistent with the average behavior,

we treat the collisions as perfectly elastic and reﬂecting.

The change in momentum of the wall in one collision is

2mv

x

. Consider a time interval ∆t and an area of the wall

∆A, and consider molecules with velocities in the range v

x

→

v

x

+ dv

x

, v

y

→ v

y

+ dv

y

, v

z

→ v

z

+ dv

z

. If, at the beginning

of the time interval, such a molecule is headed in the positive

x direction and contained within the parallelepiped indicated

schematically in the ﬁgure, it will collide with the wall during

the time interval. The change in momentum caused by such

molecules is

δP

x

=

¸

N

V

[v

x

∆t∆A] [p(v

x

, v

y

, v

z

) dv

x

dv

y

dv

z

] [2mv

x

] ,

where the ﬁrst factor is the number of molecules per unit vol-

ume, the second factor is the volume, the third gives the frac-

tion of molecules which have the speciﬁed velocity, and the last

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-9

is the change in momentum per collision. Note that p(v

x

, v

y

, v

z

) is the probability density

for the velocities and is most likely the Maxwell velocity distribution, but all we require

is that it be independent of direction. We ﬁnd the total change in momentum during the

time interval by adding up the contribution of all molecules

∆P

x

=

+∞

0

dv

x

+∞

−∞

dv

y

+∞

−∞

dv

z

p(v

x

, v

y

, v

z

)

N

V

2mv

2

x

∆t ∆A,

where the integral over v

x

includes only v

x

> 0 since we want the molecules that are about

to collide with the wall, not those which have just collided. Pressure is the rate of change

of momentum per unit area, so

p =

∆P

x

∆t ∆A

=

N

V

+∞

−∞

+∞

−∞

+∞

−∞

p(v

x

, v

y

, v

z

) mv

2

x

dv

x

dv

y

dv

z

=

N

V

mv

2

x

.

Since the distribution is independent of direction, we dropped the factor of two and ex-

tended the range of integration to v

x

< 0. Also since the distribution is isotropic, we have

mv

2

x

= mv

2

y

= mv

2

z

=

1

3

mv

2

=

2

3

E

tran

, where E

tran

is the average translational

kinetic energy per molecule. Finally,

pV =

2

3

NE

tran

=

2

3

U

tran

,

where U

tran

is the translational kinetic energy of all the gas molecules. If, in fact, the prob-

ability density for the velocities is the Maxwell density, then E

tran

= 3τ/2 (homework!)

and

pV = Nτ = NkT = nRT ,

where n is the number of moles and R is the gas constant.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 22-Sep-2004 6-10

Pressure in a Low Density Gas, II

Look inside a gas, and consider molecules with velocity components in dv

x

dv

y

dv

z

≡

d

3

v at (v

x

, v

y

, v

z

) = v, these molecules have an x momentum density (momentum per unit

volume) of

δP

x

δV

=

N

V

mv

x

p(v) d

3

v .

All this momentum is carried in the x direction at speed v

x

. Note that positive momentum

is carried in the positive direction while negative momentum is carried in the negative

direction; both contribute to a momentum ﬂux in the x direction. In fact, the ﬂux of x

momentum in the x direction (momentum per unit area perpendicular to x per unit time)

is

δP

x

δAδt

=

N

V

mv

2

x

p(v) d

3

v .

To get the total ﬂux of momentum, we integrate over all velocities and come up with the

same thing we had before. Momentum per unit area per second which is force per unit

area which is pressure is

p =

N

V

d

3

v mv

2

x

p(v) =

N

V

mv

2

x

.

So, why did we bother with this? For one thing, we don’t have to introduce a wall to talk

about pressure. Pressure exists throughout a ﬂuid. Secondly, it’s a ﬁrst introduction to

calculation of transport phenomena.

In the preceding we considered the transport of x momentum in the x direction. Of

course, y momentum is transfered in the y direction and z momentum in the z direction.

These are usually numerically equal to the ﬂux of x momentum in the x direction and we

have an isotropic pressure. One can also transport x momentum in the y and z directions,

y momentum in the x and z directions and z momentum in the x and y directions. For

the simple gas we’ve been considering, these ﬂuxes are zero (can you see why?). However,

in more complicated situations, they might not be zero; they correspond to viscous forces.

In general, we need a nine component object to specify the transport of momentum (a

vector) in any of three directions. This is a second rank tensor, usually called the stress

tensor.

Summary: For an ideal gas, we’ve found an expression relating pressure, volume and

translational kinetic energy. We related the energy to the temperature using the Maxwell

velocity distribution, which was motivated by the Boltzmann factor. However, in writing

down the Maxwell distribution, we “ﬁnessed” the issue of counting the states, so we haven’t

really derived the ideal gas law.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-1

States of a Particle in a Box.

In order to count states, we will use quantum mechanics to ensure that we have

discrete states and energy levels. Let’s consider a single particle which is conﬁned to a

cubical box of dimensions L × L × L. You might think that this is artiﬁcial and wonder

how the physics could depend on the size of a box a particle is in? It is artiﬁcial and it’s

a trick to make the math easier. Once a box is big enough, the physics doesn’t depend on

the size of the box, and the physics we deduce must not depend in any critical way on the

box size when we take the limit of a very big box. (Of course, the volume of a system is

one of the extensive parameters that describes the system and it’s OK for the volume to

enter in a manner like it does in the ideal gas law!) In what follows, we’ll ignore rotational

and internal energy of the particles and drop the “tran” subscript.

As you probably know, particles are described by wave functions

in quantum mechanics. The de Broglie relation between wavelength

(λ) and momentum (P) is P = h/λ, where h is Planck’s constant.

The wave function for a particle in a box must be zero at the walls of

the box (otherwise the particle might be found right at the wall). In

one dimension, suitable wave functions are ψ(x) ∝ sin(n

x

πx/L) where

0 ≤ x ≤ L and n

x

is an integer. This amounts to ﬁtting an integer

number of half wavelengths into the box. (If you recall the Bohr model

of the atom, the idea there is to ﬁt an integral number of wavelengths in

the electron’s orbit.) The momentum is P

x

= ±n

x

h/2L = ±n

x

¯hπ/L.

The ± sign on the momentum indicates that the wave function is

a standing wave that is a superposition of travelling waves moving in

both directions. The ﬁrst three wave functions are shown in the ﬁgure. In three dimensions,

we have

ψ(x, y, z) ∝ sin(n

x

πx/L) sin(n

y

πy/L) sin(n

z

πy/L) ,

which corresponds to ﬁtting standing waves in all three directions in the box. The mo-

mentum is

P =

π¯h

L

(±n

x

, ±n

y

, ±n

z

) .

The energy is

E =

P

2

2m

=

π

2

¯h

2

2mL

2

n

2

x

+n

2

y

+n

2

z

.

Now we are getting close to being able to count states. Consider a three dimensional

coordinate system with axes n

x

, n

y

, n

z

(regarded as continuous variables). There is a

state at each lattice point (n

x

, n

y

, n

z

integers) in the octant where all are non-negative.

Because ¯h is so small, and also because we usually deal with a large number of particles,

we will be concerned with energies where the quantum numbers (the n’s) are large. How

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-2

many states are there with energy < E? Answer:

N(< E) =

1

8

4π

3

E

π

2

¯h

2

/2mL

2

3

.

This is just the volume of an octant of a sphere with radius given by the square root above.

It’s the number of states because each state (lattice point) occupies unit volume. For a

large number of states, we don’t care about the small errors made at the surface of the

sphere. The number of states with energy less than E is the integral of the density of

states, n(E),

N(< E) =

E

0

n(E

′

) dE

′

,

where E

′

is the dummy variable of integration. Diﬀerentiate both sides with respect to E

using the previous result for N(< E),

n(E) = 2π

√

E

√

2mL

2π¯h

3

.

Recall that when we discussed the Maxwell distribution, we concluded that the density

of states had to be proportional to

√

E in order to give the Maxwell distribution. Sure

enough that’s what we get. All the other factors get absorbed into the overall normalization

constant.

It will be instructive to work out a numerical value for the number of states for

a typical case. So let’s suppose that E = 3kT/2 where T = 273 K and the volume

L

3

= 22 × 10

3

cm

3

. That is, we consider an energy and volume corresponding to the

average energy and molar volume of a gas at standard temperature and pressure. For m

we’ll use a mass corresponding to an N

2

molecule. The result is about 4 × 10

30

states,

more than a million times Avogadro’s number.

We have been working out the states for one particle in a box. If we have more

than one particle in the box, and they are non-interacting, then the same set of states is

available to each particle. It the particles are weakly interacting, then these states are a

ﬁrst approximation to the actual states and we will usually just ignore the interactions

when it comes to counting states. With this approximation, and with a mole of particles

in the box, we’ve found that less than one in a million of the available states are occupied.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-3

Partition Function for a Single Particle in a Box

We can use the same states we’ve just discussed to evaluate the partition function for

a single particle in a box. We have

Z(τ) =

¸

n

x

,n

y

,n

z

exp

−

π

2

¯h

2

2mL

2

τ

n

2

x

+n

2

y

+n

2

z

.

We will make a negligibly small error by converting the sums to integrals,

Z(τ) =

∞

0

dn

x

∞

0

dn

y

∞

0

dn

z

exp

−

π

2

¯h

2

2mL

2

τ

n

2

x

+n

2

y

+n

2

z

,

=

√

2mτ

π¯h

3

L

3

∞

0

dx

∞

0

dy

∞

0

dz exp(−x

2

−y

2

−z

2

) ,

(rescaling variables)

=

1

8

4π

√

2mτ

π¯h

3

L

3

∞

0

dr r

2

e

−r

2

,

(changing to spherical coordinates and integrating over angles)

=

1

8

4π

√

2mτ

π¯h

3

V

1

2

Γ

3

2

,

=

V

(2π¯h

2

/mτ)

3/2

(Γ(3/2) =

√

π/2) ,

= n

Q

V .

The volume of the system is V = L

3

and the quantity that occurs in the last line, n

Q

has the dimensions of an inverse volume or a number per unit volume. mτ is the square

of a typical momentum. So ¯ h

2

/mτ ∼ λ

2

, and the volume associated with n

Q

is roughly

a cube of the de Broglie wavelength. This is roughly the smallest volume in which you

can conﬁne the particle (given its energy) and still be consistent with the uncertainty

principle. K&K call n

Q

the quantum concentration. A concentration is just a number per

unit volume, and n

Q

can be thought of as the concentration that separates the classical

(lower concentrations) and quantum (higher concentrations) domains. For a typical gas

at STP, the actual concentration n = N/V is much less than the quantum concentration

(by the same factor as the ratio of the number of states to the number of molecules we

calculated earlier), so the gas can be treated classically.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-4

Partition Function for N Particles in a Box

If we have N non-interacting particles in our box, all with the same mass, then (see

the homework) the partition function for the composite system is just the product of the

partition functions for the individual systems,

Z

N

(τ) = Z

1

(τ)

N

wrong!

where Z

N

is the N-particle partition function and Z

1

is the 1-particle partition function

calculated in the previous section.

Why is this wrong? Recall that the partition function is the sum of Boltzmann

factors over all the states of the composite system. Writing Z

N

as a product includes

terms corresponding to molecule A with energy E

a

and molecule B with energy E

b

and

vice versa: molecule A with E

b

and molecule B with E

a

. However, these are not diﬀerent

composite states if molecules A and B are indistinguishable! The product overcounts the

composite states. Any given Boltzmann factor appears in the sum roughly N! times more

than it should because there are roughly N! permutations of the molecules among the

single particle states that give the same composite state.

Why “roughly?” Answer, if there are two or more particles in the same single particle

state, then the correction for indistinguishability (what a word!) is not required. However,

we’ve already seen that for typical low density gasses, less than one in a million single

particle states will be occupied, so it’s quite safe to ignore occupancies greater than 1. (If

this becomes a bad approximation, other quantum eﬀects enter as well, so we need to do

something diﬀerent, anyway!)

To correct the product, we just divide by N!,

Z

N

(τ) =

1

N!

Z

N

1

=

1

N!

(n

Q

V )

N

.

To ﬁnd the energy, we use

U = τ

2

∂

∂τ

log Z

N

,

= τ

2

∂

∂τ

(−log N! +N log n

Q

+N log V ) ,

= τ

2

∂

∂τ

(N log n

Q

) ,

(derivatives of N! and log V give 0)

= τ

2

∂

∂τ

N log

mτ

2π¯h

2

3/2

,

=

3

2

Nτ ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-5

which expresses the energy of an ideal gas in terms of the temperature. We’ve obtained this

result before, using the Maxwell distribution. Note that our correction for overcounting of

the microstates does not appear in the result.

In lecture 6, we noted that

p = −

∂U

∂V

σ,N

,

and we remarked that keeping the entropy constant while changing the volume of a system

means keeping the probability of each microstate constant. The average energy is

E =

¸

s

E

s

P(E

s

) ,

and keeping the probabilities of the microstates constant means that P(E

s

) doesn’t change.

Thus, changing the volume at constant entropy changes the energy through changes in

energies of the individual states. For each single particle state,

E

s

∝

1

L

2

∝ V

−2/3

,

which means

dU

U

=

dE

s

E

s

= −

2

3

dV

V

,

all at constant σ. Then the pressure is

p = −

∂U

∂V

σ,N

=

2

3

U

V

.

Again, this is a result we’ve seen before.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-6

Helmholtz Free Energy

Recall the expression for the conservation of energy,

dU = τ dσ −p dV ,

where we have omitted the chemical potential term, since we won’t be contemplating

changing the number of particles at the moment.

If we have a system whose temperature is ﬁxed by thermal contact with a heat bath,

it is convenient to eliminate the diﬀerential in the entropy in favor of a diﬀerential in the

temperature. For this we use a Legendre transformation—exactly the same kind of trans-

formation used in classical mechanics to go from the Lagrangian, a function of coordinates

and velocities, to the Hamiltonian, a function of coordinates and momenta.

Deﬁne the Helmholtz free energy by

F = U −τσ .

Not all authors use the symbol F for this quantity—I believe some use A and there may

be others. In any case,

dF = dU −τ dσ −σ dτ = τ dσ −p dV −τ dσ −σ dτ = −σ dτ −p dV .

If a system is placed in contact with a heat bath and its volume is ﬁxed, then its free

energy is an extremum. As it turns out, the extremum is a minimum. To show this, we

show that when the entropy of the system plus reservoir is a maximum (so equilibrium is

established), the free energy is a minimum.

σ = σ

r

(U −U

s

) +σ

s

(U

s

) ,

= σ

r

(U) −U

s

(∂σ

r

/∂U) +· · · +σ

s

(U

s

) ,

= σ

r

(U) −U

s

/τ +σ

s

(U

s

) ,

= σ

r

(U) −(U

s

−τσ

s

(U

s

)) /τ ,

= σ

r

(U) −F

s

/τ .

In the above, the subscripts r and s refer to the reservoir and system and U is the ﬁxed

total energy shared by the reservoir and system. Note that unlike our derivation of the

Boltzmann factor, the system here need not be so small that it can be considered to be

in a single state—it can be a macroscopic composite system. However, it should be much

smaller than the reservoir so that U

s

≪ U. Also, the partial derivatives above occur at

ﬁxed volume and particle number. Since σ

r

(U) is just a number, and τ is ﬁxed, maximizing

σ requires minimizing F.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-7

From dF = −σ dτ −p dV , we see

σ = −

∂F

∂τ

V

and p = −

∂F

∂V

τ

.

Substituting F = U −τσ in the right equation above,

p = −

∂U

∂V

τ

+τ

∂σ

∂V

τ

.

This shows that at ﬁxed temperature, if a system can lower its energy by expanding, then

it generates a “force,” pressure, that will create an expansion. This is probably intuitive,

since we are used to the idea that the equilibrium state is a minimum energy state. If the

system can increase its entropy (at ﬁxed temperature) by expanding, this too, generates a

“force” to create an expansion.

Note that

∂σ

∂V

τ

= −

∂

2

F

∂V ∂τ

= −

∂

2

F

∂τ∂V

=

∂p

∂τ

V

.

The outer equality in this line is called a Maxwell relation. These occur often in thermody-

namics and result from the fact that many thermodynamic parameters are ﬁrst derivatives

of the same thermodynamic “potential,” such as the free energy in this case.

The Free Energy and the Partition Function

Consider F = U −τσ and σ = −(∂F/∂τ)

V

. Putting these together, we have

U = F +τσ ,

= F −τ

∂F

∂τ

V

,

= −τ

2

∂(F/τ)

∂τ

.

Recall the expression for energy in terms of the partition function

U = τ

2

∂ log Z

∂τ

.

Comparing with the above, we see

F

τ

= −log Z +C ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 24-Sep-2004 7-8

where C is a constant independent of τ. In fact, the constant must be zero in order to give

the correct entropy as τ → 0. If τ is suﬃciently small, only the lowest energy (E

0

) state

enters the partition function. If it occurs g

0

diﬀerent ways, then log Z → log g

0

− E

0

/τ

and σ = −∂F/∂τ → ∂(τ log g

0

− E

0

− τC)/∂τ = log g

0

− C. So C = 0 in order that the

entropy have the correct zero point. Then

F = −τ log Z or Z = e

−F/τ

.

Remembering that the Boltzmann factor is normalized by the partition function to yield

a probability, we have

P(E

s

) =

e

−E

s

/τ

Z

= e

(F −E

s

)/τ

.

Just for fun, let’s apply some of these results using the partition function for the ideal

gas we derived earlier.

F = −τ log Z ,

= −τ log((n

Q

V )

N

/N!) ,

= −τ(N log n

Q

+N log V −N log N +N) (Stirling’s approx.) ,

= −τN log

(mτ/2π¯h

2

)

3/2

(V/N)

−τN .

With p = −∂F/∂V , we have

p = τN/V ,

the ideal gas law again. For the entropy, σ = −∂F/∂τ,

σ = N log(n

Q

V/N) + (3/2)N +N ,

= N

log

n

Q

n

+

5

2

,

where n = N/V is the concentration. This called the Sackur-Tetrode formula. Note that

if one considers the change in entropy between two states of an ideal gas,

σ

f

−σ

i

=

3

2

N log

τ

f

τ

i

+N log

V

f

V

i

,

a classical result which doesn’t contain Planck’s constant. However, to set the zero point

and get an “absolute” entropy, Planck’s constant does enter since it determines the spac-

ing between states and their total number. The overcounting correction does not make

any diﬀerence in the pressure above, but it does enter the entropy—as might have been

expected. A ﬁnal note is that these expressions for an ideal gas do not apply in the limit

τ →0. (Why?)

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-1

Reading

This week, we’ll concentrate on the material in K&K chapter 4. This might be called

the thermodynamics of oscillators.

Classical Statistical Mechanics

Recall that statistical mechanics was developed before quantum mechanics. In our

discussions, we’ve made use of the fact that quantum mechanics allows us to speak of

discrete states (sometimes we have to put our system in a box of volume V ), so it makes

sense to talk about the number of states available to a system, to deﬁne the entropy as

the logarithm of the number of states, and to speak of maximizing the number of states

(entropy) available to the system. If one didn’t know about quantum mechanics and didn’t

know about discrete states, how would one do statistical mechanics?

Answer: in classical statistical mechanics, the phase space volume plays the role of

the number of states. We’ve mentioned phase space brieﬂy. Here’s a slightly more detailed

description. In classical mechanics, one has the Lagrangian, L(q, ˙ q, t) which is a function

of generalized coordinates q, their velocities, ˙ q, and possibly the time, t. The equations of

motion are Lagrange’s equations

d

dt

∂L

∂ ˙ q

−

∂L

∂q

= 0 .

Note that q might be a single variable or it might stand for a vector of coordinates. In

the latter case, there is one equation of motion for each coordinate. The Hamiltonian is

deﬁned by a Legendre transformation,

H(q, p, t) = p ˙ q −L(q, ˙ q, t) ,

where

p =

∂L

∂ ˙ q

,

is called the momentum conjugate to q (or the canonical momentum). The equations of

motion become (assuming neither L nor H is an explicit function of time)

˙ q =

∂H

∂p

, ˙ p = −

∂H

∂q

,

so that each second order equation of motion has been replaced by a pair of ﬁrst order

equations of motion.

If p and q are given for a particle at some initial time, then the time development of p

and q are determined by the equations of motion. If we consider a single pair of conjugate

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-2

coordinates, p and q (i.e., a one-dimensional system), and we consider a space with axes q

and p, then a point in this space represents a state of the system. The equations of motion

determine a trajectory (or orbit) in this space that the system follows. The q-p space is

called phase space. If we consider a 3-dimensional particle, then three coordinates and

three momenta are required to describe the particle. Phase space becomes 6-dimensional

and is a challenge to draw. If we consider N 3-dimensional particles, then phase space

becomes 6N-dimensional. Or, one might draw N trajectories in a 6-dimensional space.

As an example of a phase space that we might actually be able to draw, consider two

1-dimensional particles moving along a common line. Suppose they are essentially free

particles. The phase space coordinates are q

1

, p

1

, q

2

, and p

2

. (Subscripts refer to particles

1 and 2.) The ﬁgure shows an attempt at drawing a trajectory in the 4-dimensional phase

space. Since we have free particles, p

1

and p

2

are constants and q

1

and q

2

are linear

functions of time, for example, q

1

= p

1

t/m

1

. The ﬁgure shows a trajectory for q

1

and for

q

2

. As shown, q

1

has a positive momentum, so its trajectory is from left to right, while

q

2

has a negative momentum, so its trajectory is from right to left. Each point on the

trajectory of q

1

corresponds to exactly one point on the trajectory of q

2

—the points are

labeled by time and points at the same time are corresponding points. If we could draw

in four dimensions, there would be a single line representing both particles and we would

not have to point out this correspondence.

Note that at some time, both particles are at the same physical place in space and

simply pass through each other as we’ve drawn the trajectories above. Instead of passing

through each other, suppose they have a collision and “bounce backwards.” This might be

represented by the diagram shown in the next ﬁgure. This has been drawn assuming equal

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-3

masses, equal and opposite momenta, and an elastic collision. I’m sure you can work out

diagrams for other cases.

Suppose we are considering a low density gas (again!). We certainly would not want

to try to draw a phase space for all the particles in the gas and we certainly wouldn’t

want to try to draw all the trajectories including collisions. In the two particle case we’ve

been considering, suppose we blinked while the collision occurred. What would we see?

The answer (for a suitable blink) is shown in the next ﬁgure. We’d see particles 1 and 2

moving along as free particles before we blinked and again after we blinked, but while we

blinked, they changed their momenta. We’ve already mentioned that in a low density gas,

the molecules travel several molecular diameters between collisions while collisions occur

only when molecules are within a few molecular diameters of each other. One way to treat

a low density gas is to treat the molecules as free particles and to try to add in something

to account for the collisions. By looking at the drawing of the collision (where we blinked),

we can see that one way is to say that the particles follow phase space trajectories for a

free particle, except every now and then a trajectory ends and reappears—at random—

somewhere else. The disappearance and reappearance of phase space trajectories does not

really happen; it’s an approximate way to treat collisions.

All this is motivation for the idea that collisions randomize the distribution of particles

in phase space. Of course the randomization must be consistent with whatever constraints

are placed on the system (such as ﬁxed total energy, etc.) In general, if a system is

in thermal contact with another system, we would expect that the exchanges of energy,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-4

required for thermal equilibrium, would result in randomization of the phase space location.

The classical statistical mechanics analog of our postulate that all accessible states

are equally probable is the postulate that all accessible regions of phase space are equally

probable. In other words, a point in phase space plays the role of a state. The leveling

of the probabilities is of course accomplished by the collisions and energy transfers we’ve

just been discussing. It shouldn’t be too hard to convince yourself that any concept we’ve

discussed that doesn’t explicitly require Planck’s constant can just as easily be done with

classical statistical mechanics as with quantum statistical mechanics. Even in cases where

we used ¯h, if there is a reasonable mapping of quantum states to phase space volume, the

classical treatment will give the same results as the quantum treatment (but of course,

lacking an ¯ h).

As an example, suppose we consider a single free particle in a box of volume V in

thermal contact with a reservoir at temperature τ. Our derivation of the Boltzmann factor

did not depend on quantum mechanics, so the probability of ﬁnding this particle in a state

with energy E is exp(−E/τ), just as before. The partition function is no longer a sum

over states, but an integral over phase space volume,

Z

C

=

+L/2

−L/2

dx

+L/2

−L/2

dy

+L/2

−L/2

dz

+∞

−∞

dp

x

+∞

−∞

dp

y

+∞

−∞

dp

z

exp

−(p

2

x

+p

2

y

+p

2

z

)/2mτ

,

where Z

C

stands for the classical partition function, and the volume is taken to be a cube

of side L for convenience. The integrals over the coordinates give V and each integral over

a momentum gives

√

2πmτ. The result is

Z

C

= V (2πmτ)

3/2

.

Recall our previous result for the free particle partition function,

Z

Q

= V (2πmτ)

3/2

1

h

3

,

where the subscript Q indicates the “quantum” partition function. Note that the expres-

sion includes h, not ¯ h. So, in this case, the classical and quantum partition functions are

the same except for a factor of h

−3

. Mostly, we use the logarithm of the partition function.

This means that many results that we derive from the partition function will not depend

on whether we use Z

C

or Z

Q

. For example, the energy is τ

2

∂(log Z)/∂τ, so the h

3

factor

has no eﬀect on the energy. An important exception is the entropy. The entropy is missing

an additive constant. This has no eﬀect on relative entropy, but it does matter for absolute

entropy. (How would you measure absolute entropy?) By comparing the two expressions

one sees that for each pair of conjugate phase space coordinates, such as x and p

x

, one

should assign the volume h to a single state. Using classical considerations, we can (at

least for a low density gas) reproduce the quantum results simply by using

dx dp

x

h

dy dp

y

h

dz dp

z

h

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-5

as the appropriate volume in phase space. This works in general provided the average

occupancy is very low.

We see that the Maxwell velocity distribution falls out of the classical approach and

the h

−3

even if included, would get erased in the normalization factor for the probability

density.

A Classical Harmonic Oscillator

Now suppose we have a one dimensional harmonic oscillator, whose Hamiltonian is

H =

p

2

2m

+

kq

2

2

=

1

2m

p

2

+m

2

ω

2

q

2

,

where ω

2

= k/m is the natural frequency of the oscillator, Suppose this oscillator is in

thermal equilibrium at temperature τ. What is the mean value of its energy? One way

we can work this out is to take the Boltzmann factor as the probability density in phase

space. So

P(E) dq dp = C exp

−(p

2

+m

2

ω

2

q

2

)/2mτ

dq dp ,

where uppercase P is used for probability density to distinguish if from momentum. The

normalization constant, C, is set by requiring that the integral of the probability density

over phase space be unity. The position and momentum integrals can be done separately

and lead to normalization factors mω/

√

2πmτ for the position coordinate and 1/

√

2πmτ

for the momentum coordinate. To get the average energy of this oscillator, we have

E = C

+∞

−∞

dq

+∞

−∞

dp

1

2m

p

2

+m

2

ω

2

q

2

exp

−(p

2

+m

2

ω

2

q

2

)/2mτ

,

=

mω

√

2πmτ

+∞

−∞

dq

m

2

ω

2

q

2

2m

e

−m

2

ω

2

q

2

/2mτ

+

1

√

2πmτ

+∞

−∞

dp

p

2

2m

e

−p

2

/2mτ

,

=

τ

2

1

√

2π

+∞

−∞

dx x

2

exp(−x

2

/2) +

τ

2

1

√

2π

+∞

−∞

dy y

2

exp(−y

2

/2) ,

=

τ

2

+

τ

2

= τ .

Of course, we could obtain the same result by calculating the partition function and going

from there. Note that the harmonic oscillator has two ways to store energy: as kinetic

energy or as potential energy. Each of these can be considered a degree of freedom and

each stores, on the average, τ/2 = kT/2. This is an example related to equipartition of

energy discussed by K&K in chapter 3.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-6

Classical Cavity Radiation

We’re familiar with the idea that hot objects radiate energy. There are the expressions

“red hot” and “white hot” denoting very hot objects. The color comes from the appear-

ance of the objects and is the color of the electromagnetic energy radiated by the object.

Allowing two objects to exchange radiation is a way to place them in thermal contact. For

ordinary temperatures this may not be a very eﬃcient method of heat exchange compared

to conduction or convection, but at high temperatures (in stars, for example) it can become

the dominant method of energy transfer. Also, when working at cryogenic temperatures,

one needs to shield the experiment from direct exposure to room temperature radiation

because this can be an important heat load on the cold apparatus.

How can we make a perfect absorber of radiant energy? If we could, what would it

look like? If it absorbed all the radiation that hit it, then nothing would be reﬂected back,

so we couldn’t see anything and it would appear black. A perfect absorber is called a

blackbody. We could make a perfect absorber by making a large cavity with a small hole

connecting the cavity to the outside world. Then, as seen from the outside, any radiation

hitting the hole, passes through the hole and bounces around inside the cavity until it is

absorbed. By making the cavity suﬃciently big and the hole suﬃciently small, we can

make the chances of the radiation coming back out the hole before it’s absorbed as small

as we like. (Of course, when the wavelength of the radiation is comparable to or larger

than the size of the hole, then we have to worry about diﬀraction...)

A cavity containing a hole must also radiate energy. If not, it would heat up to arbi-

trarily high temperatures (and of course, this violates the second law of thermodynamics

by transferring heat from a cold object to a hot object with no other change). So when a

cavity is in thermal equilibrium with its surroundings, It must radiate energy out through

the hole at the same rate that energy is absorbed through the hole. A hole has no proper-

ties, so the radiated spectrum (energy at each frequency or wavelength or color) can only

depend on the temperature. This spectrum is called the blackbody (or thermal or cavity)

radiation spectrum. A real physical object which is a perfect absorber must radiate the

same spectrum. We can place a physically black object into thermal contact with a cavity

radiator. In order to avoid violating the second law, the energy absorbed must equal the

energy radiated. If we consider a ﬁlter which is perfectly transparent in some frequency

range and perfectly reﬂecting outside this range and we insert this ﬁlter between the two

objects, then we conclude that the perfect absorber and the cavity radiator must radiate

the same spectrum (the same amount of energy at each frequency). Finally, real absorbers

are not perfect. If in equilibrium, a fraction a of the incident radiation is absorbed, with

the rest being reﬂected, then it must be the case that it emits the fraction a of the ideal

blackbody radiation, otherwise we can arrange to violate the second law. Finally, by using

our ﬁlter again, we conclude that if it absorbs the fraction a(ω) at frequency ω, it must

radiate the same fraction e(ω) = a(ω) of the ideal blackbody radiation spectrum. Jargon:

a is called the absorptivity and e is called the emissivity.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-7

The upshot of all this is that there is a universal radiation spectrum that depends

only on temperature and is called the blackbody, thermal or cavity radiation spectrum.

Let us try to calculate this spectrum.

The spectrum is produced by electromagnetic ﬁelds inside the cavity. These ﬁelds

contain energy and they are in equilibrium with the walls of the cavity at temperature τ.

To make life simple, let’s suppose our cavity is a cube of side L. You may recall from your

studies of electromagnetism that the ﬁelds in the cavity can be divided into modes with

each mode oscillating like a harmonic oscillator. Electromagnetic energy oscillates back

and forth between the electric ﬁeld (like the position coordinate in a standard harmonic

oscillator) and the magnetic ﬁeld (like the momentum coordinate).

Each mode can store energy independently, so each mode contributes a harmonic os-

cillator term to the Hamiltonian of the cavity. Diﬀerent modes have diﬀerent frequencies

and this is where the spectrum comes from. So we are getting close: we’ve already calcu-

lated the average energy in a harmonic oscillator; all we have to do now is enumerate the

modes and their frequencies and we’ll have the calculation of the blackbody spectrum.

As you may know, the electric ﬁeld for a given mode in a perfectly conducting cavity

has components of the form

E

z

= E

0

sin(ωt) sin(n

x

πx/L) sin(n

y

πy/L) cos(n

z

πz/L) ,

where E

0

is the amplitude of the mode (an electric ﬁeld, not an energy!), ω is the frequency

of oscillation, and n

x

, n

y

, and n

z

are integers. The cavity is assumed to run from 0 to L in

each coordinate. The sine terms ensure that electric ﬁeld component parallel to a perfectly

conducting wall is zero at the wall. (Electric ﬁeld is always perpendicular to the surface

of a perfect conductor). The cosine term ensures that the magnetic ﬁeld (related to the

E-ﬁeld by Maxwell’s equations) has no perpendicular component at the wall. The integers

n

x

, n

y

, n

z

are related to the number of half wavelengths that ﬁt in the cavity. Maxwell’s

equations tell us that

ω

2

=

π

2

c

2

L

2

n

2

x

+n

2

y

+n

2

z

.

We can think of a mode as a wave bouncing around inside the cavity and when it has

bounced around once, it must be in phase with the original wave in order to have resonance

and a mode. This is another way of seeing how the integers arise. We also know that any

electromagnetic wave in a vacuum has two polarizations. So for each set of positive integers

there are two independent oscillators. And each oscillator has average energy τ according

to our earlier calculation.

To calculate the spectrum, we need to know how many sets of integers correspond to

a given range in ω. We start by considering the number that correspond to a frequency

less than a particular ω. If we consider a three dimensional space with axes n

x

, n

y

, and

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 27-Sep-2004 8-8

n

z

, then the number is the number of lattice points in this space in the positive octant

with

n

2

x

+n

2

y

+n

2

z

< r = ωL/πc. This is just the volume of 1/8 of a sphere of radius r,

N(< ω) = 2

1

8

4π

3

ωL

πc

3

,

where the factor of 2 accounts for the two polarizations. This should be reminding you

very strongly of what we did when counting the states of a particle in a box. The number

of oscillators in the frequency range ω →ω +dω is found by diﬀerentiating the above, and

n(ω) dω =

V ω

2

π

2

c

3

dω ,

where V has been inserted in place of L

3

.

Now, each oscillator has average energy τ, so the energy per unit frequency in the

cavity is

dU

dω

dω =

V ω

2

τ

π

2

c

3

dω ,

and the total energy in the cavity is found by integrating over all frequencies,

U =

+∞

0

dω

V ω

2

τ

π

2

c

3

= ∞!!!

This says there is an inﬁnite energy in the cavity and this can’t be right! Also the energy

per unit frequency result says that the energy is concentrated towards the high frequencies

in proportion to ω

2

. This is called the ultraviolet catastrophe. It says that if you made a

cavity and put a small hole in it to let the radiation out, you’d be instantly incinerated by

the ﬂux of X-rays and gamma rays! Of course, we’re all still here, so this doesn’t happen.

Where did we go wrong? This is the same question physicists were asking themselves in

the latter part of the nineteenth and the early part of the twentieth century.

The answer is, we didn’t go wrong, at least as far as classical physics is concerned. Ev-

erything we did leading up to inﬁnite energy density in a cavity is perfectly legal according

to classical physics. It is one of the many contradictions that arose around the turn of the

century that led to the development of quantum mechanics. One of the things to note is

that cavity radiation could be measured and at low frequencies it gave results in agreement

with what we’ve just derived. That is, the spectral density (1/V ) dU/dω is proportional

to τ and to ω

2

. For higher frequencies the measured result falls far below our calculation.

The ω

2

region is called the Rayleigh-Jeans part of the spectrum. What’s needed to cure

our calculation is a way to keep the high frequency modes from being excited. We shall see

that it is the discreteness of the energy levels provided by quantum mechanics that keeps

these modes quiescent.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-1

A Quantum Harmonic Oscillator

The quantum harmonic oscillator (the only kind there is, really) has energy levels

given by

E

n

= (n + 1/2)¯ hω ,

where n ≥ 0 is an integer and the E

0

= ¯ hω/2 represents zero point ﬂuctuations in the

ground state. We are going to shift the origin slightly and take the energy to be

E

n

= n¯hω .

That is, we are going to ignore zero point energies. The actual justiﬁcation for this is a

little problematic, but basically, it represents an unavailable energy, so we just leave it out

of the accounting.

The partition function is then

Z =

∞

n=0

e

−n¯hω/τ

=

1

1 −exp(−¯hω/τ)

=

exp(¯ hω/τ)

exp(¯ hω/τ) −1

.

(Thus is just an inﬁnite series

x

n

with x = exp(−¯hω/τ).) We calculate the average

energy of the oscillator

E = τ

2

∂ log Z

∂τ

=

¯hω

exp(¯ hω/τ) −1

.

It’s instructive to consider two limiting cases. First, consider the case, that ¯hω ≪τ. That

is, the energy level spacing of the oscillator is much less than the typical thermal energy.

In this case, the denominator becomes

e

¯hω/τ

−1 ≈ 1 +

¯hω

τ

+· · · −1 =

¯hω

τ

.

If we plug this into the expression for the average energy, we get

E →τ , (¯ hω ≪τ) ,

just as we found for the classical case. On the other hand, if ¯ hω/τ ≫1, then the exponential

in the denominator is large compared to unity and the average energy becomes

E →¯hω e

−¯hω/τ

, (¯ hω ≫τ) .

In other words, the average energy is “exponentially killed oﬀ” for high energies. Recall

that we needed a way to keep the high energy modes quiescent in order to solve our cavity

radiation problem!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-2

Quantum Cavity Radiation

Now that we have given a treatment of the quantum harmonic oscillator, we can return

to the cavity radiation problem. Note that our counting of states is basically the counting

of electromagnetic modes. These came out quantized because we were considering standing

electromagnetic waves. That is, classical considerations gave us quantized frequencies and

quantized modes. With quantum mechanics, we identify each mode as a quantum oscillator

and realize that the energies (and amplitudes) of each mode are quantized as well.

In addition, with quantum mechanics, we know that particles have wave properties and

vice-versa and that quantum mechanics associates an energy with a frequency according

to E = ¯ hω. So given that we have a mode of frequency ω, it is populated by particles

with energy ¯ hω. We can get the mode classically by considering standing waves of the

electromagnetic ﬁeld and we can get it quantum mechanically by considering a particle

in a box. Either way we get quantized frequencies. With quantum mechanics we also

ﬁnd that the occupants of the modes are particles with energies ¯hω, so we get quantized

energies at each quantized frequency. When you take a course in quantum ﬁeld theory,

you will learn about second quantization which is what we’ve just been talking about!

The particles associated with the electric ﬁeld are called photons. They are massless

and travel at the speed of light. They carry energy E = hν = ¯ hω and momentum p =

h/λ = hν/c = ¯ hω/c, where ω and λ are the frequency and wavelength of the corresponding

wave. Note that the frequency in Hertz is ν = ω/2π.

When ¯ hω ≪τ, so the thermal energy is much larger than the photon energy, we have

E

¯hω

→

τ

¯hω

≫1 , (¯ hω ≪τ) .

The average energy divided by the energy per photon is the average number of photons

in the mode or the average occupancy. We see that in the limit of low energy modes,

each mode has many photons. When quantum numbers are large, we expect quantum

mechanics to go over to classical mechanics and sure enough this is the limit where the

classical treatment gives a reasonable answer. At the other extreme, when the photon

energy is high compared to the thermal energy, we have

E

¯hω

→e

−¯hω/τ

≪1 , (¯ hω ≫τ) .

In this limit, the average occupancy is much less than 1. This means that the mode is

quiescent (as needed) and also that quantum eﬀects should be dominant. In particular,

the heat bath, whose typical energies are ∼ τ has a hard time getting together an energy

much larger than τ all at once so as to excite a high energy mode.

Perhaps a bit of clariﬁcation is needed here. When discussing the ideal gas, consisting

of atoms or molecules, we said that a low occupancy gas was classical and a high occupancy

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-3

gas needed to be treated with quantum mechanics—apparently just the opposite of what

was said in the previous paragraph! When a large number of particles are in the same

state, they can be treated as a classical ﬁeld. Thus at low photon energies, with many

photons in the same mode, we can speak of the electromagnetic ﬁeld of the mode. At high

photon energies, where the occupancy is low, the behavior is like that of a classical particle

but a quantized ﬁeld.

Let’s calculate the cavity radiation spectrum. The only change we need to make from

our previous treatment is to substitute the quantum oscillator average energy in place of

the classical result. The number of modes per unit frequency is the same whether we count

the modes classically or quantum mechanically. However, since the average energy now

depends on frequency, we must include it in the integral when we attempt to ﬁnd the total

energy. The energy per unit frequency is

dU

dω

dω =

V ω

2

π

2

c

3

¯hω

exp(¯ hω/τ) −1

dω ,

and the total energy in the cavity is,

U =

+∞

0

dω

V ω

2

π

2

c

3

¯hω

exp(¯ hω/τ) −1

.

It is convenient to divide the energy per unit frequency by the volume and consider the

spectral density u

ω

, where

u

ω

=

1

V

dU

dω

=

¯hω

3

π

2

c

3

(exp(¯ hω/τ) −1)

.

This is called the Planck radiation law. It is simply the energy per unit volume per unit

frequency at frequency ω inside a cavity at temperature τ. For convenience, let x = ¯ hω/τ.

Then x is dimensionless and we have

u

ω

=

τ

3

π

2

¯h

2

c

3

x

3

e

x

−1

,

The shape of the spectrum is given by the second factor above which is plotted in the ﬁgure.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-4

Changing the temperature shifts the curve to higher frequencies (in proportion to τ) and

multiplies the curve by τ

3

(and constants). At low energy the spectrum is proportional to

ω

2

in agreement with the classical result. At high energy there is an exponential cut-oﬀ.

The exponential behavior on the high energy side of the curve is known as Wien’s law.

To ﬁnd the total energy per unit volume we have

u =

+∞

0

dω u

ω

,

=

+∞

0

dω

¯hω

3

π

2

c

3

(exp(¯ hω/τ) −1)

,

=

τ

4

π

2

¯h

3

c

3

∞

0

x

3

dx

e

x

−1

,

=

τ

4

π

2

¯h

3

c

3

π

4

15

(looking up the integral) ,

=

π

2

15¯ h

3

c

3

τ

4

.

The fact that radiation density is proportional to τ

4

is called the Stefan-Boltzmann law.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-5

We can also calculate the entropy of radiation. We have

U = V u =

π

2

15¯ h

3

c

3

V τ

4

.

We know that τ dσ = dU when the volume is constant, so

dσ =

1

τ

4π

2

15¯ h

3

c

3

V τ

3

dτ =

4π

2

15¯ h

3

c

3

V τ

2

dτ .

We integrate this relation setting the integration constant to 0, (why?) and obtain

σ =

4π

2

45¯ h

3

c

3

V τ

3

.

It is sometimes useful to think of blackbody radiation as a gas of photons. Some of

the homework problems explore this point of view as well as other interesting facts about

the blackbody radiation law.

One application of the blackbody radiation law has to do with the cosmic microwave

background radiation which is believed to be thermal radiation left over from the hot big

bang which started our universe. Due to the expansion of the universe, it has cooled

down. This radiation has been measured very precisely by the FIRAS instrument on

the COBE satellite and is shown in the accompanying ﬁgure which was put together by

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-6

Lyman Page mostly from data collected by Reach, et al., 1995, Astrophysical Journal,

451, 188. The dashed curve is the theoretical curve and the solid curve represents the

measurements where the error bars are smaller than the width of the curve! Other curves

on the plot represent deviations in the curve due to our motion through the background

radiation (dipole), irregularities due to ﬂuctuations that eventually gave rise to galaxies and

physicists (anisotropy) and sources of interfering foreground emission. The temperature

is 2.728 ± 0.002 K where the error (one standard deviation) is all systematic and reﬂects

how well the experimenters could calibrate their thermometer and subtract the foreground

sources.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-7

More on Blackbody Radiation

Before moving on to other topics, we’ll clean up a few loose ends having to do with

blackbody radiation.

In the homework you are asked to show that the pressure is given by

p =

π

2

τ

4

45¯ h

3

c

3

,

from which one obtains

pV =

1

3

U ,

for a photon gas. This is to be compared with

pV =

2

3

U ,

appropriate for a monatomic ideal gas.

In an adiabatic (isentropic—constant entropy) expansion, an ideal gas obeys the re-

lation

pV

γ

= Constant ,

where γ = C

p

/C

V

is the ratio of heat capacity at constant pressure to heat capacity at

constant volume. For a monatomic ideal gas, γ = 5/3. For complicated gas molecules with

many internal degrees of freedom, γ →1. A monatomic gas is “stiﬀer” than a polyatomic

gas in the sense that the pressure in a monatomic gas rises faster for a given amount of

compression. What are the heat capacities of a photon gas? Since

U =

π

2

15¯ h

3

c

3

V τ

4

,

C

V

=

∂U

∂τ

V

=

4π

2

15¯ h

3

c

3

V τ

3

.

How about the heat capacity at constant pressure. We can’t do that! The pressure

depends only on the temperature, so we can’t change the temperature without changing

the pressure. We can imagine adding some heat energy to a photon gas. In order to keep

the pressure constant, we must let the gas expand while we add the energy. So, we can

certainly add heat at constant pressure, it just means the temperature is constant as well,

so I suppose the heat capacity at constant pressure is formally inﬁnite!

If one recalls the derivation of the adiabatic law for an ideal gas, it’s more or less

an accident that the exponent turns out to be the ratio of heat capacities. This, plus

the fact that we can’t calculate a constant pressure heat capacity is probably a good sign

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-8

that we should calculate the adiabatic relation for photon gas directly. We already know

σ ∝ V τ

3

∝ V p

3/4

, so for an adiabatic process with a photon gas,

pV

4/3

= Constant ,

and a photon gas is “softer” than an ideal monatomic gas, but “stiﬀer” than polyatomic

gases. Note that γ = 4/3 mainly depends on the fact that photons are massless. Consider

a gas composed of particles of energy E and momentum P = E/c, where c is the speed

of light. Suppose that particles travel at speed c and that their directions of motion are

isotropically distributed. Then if the energy density is u = nE, where n is the number

of particles per unit volume, the pressure is u/3. This can be found by the same kind of

argument suggested in the homework problem. The same result holds if the particles have

a distribution in energy provided they satisfy P = E/c and v = c. This will be the case

for ordinary matter particles if they are moving at relativistic speeds. A relativistic gas is

“softer” than a similar non-relativistic gas!

On problem 3 of the homework you are asked to determine the power per unit area

radiated by the surface of a blackbody or, equivalently, a small hole in a cavity. The result

is (c/4)u where the speed of light accounts for the speed at which energy is transported by

the photons and the factor of 1/4 accounts for the eﬃciency with which the energy gets

through the hole. The ﬂux is

J =

π

2

τ

4

60¯ h

3

c

2

=

π

2

k

4

60¯ h

3

c

2

T

4

= σ

B

T

4

where the Stefan-Boltzmann constant is

σ

B

=

π

2

k

4

60¯ h

3

c

2

= 5.6687 ×10

−5

erg

cm

2

s K

4

.

We saw that the Planck curve involved the function x

3

/(exp(x) −1) with x = ¯ hω/τ.

Let’s ﬁnd the value of x for which this curve is a maximum. We have

0 =

d

dx

x

3

e

x

−1

,

=

3x

2

e

x

−1

−

x

3

e

x

(e

x

−1)

2

,

=

(3x

2

−x

3

)e

x

−3x

2

(e

x

−1)

2

or

0 = (x −3)e

x

+ 3 .

This transcendental equation must be solved numerically. The result is x = 2.82144. At

maximum,

2.82 =

¯hω

max

τ

=

h

k

ν

max

T

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-9

or

T

ν

max

=

h

2.82k

= 0.017

Kelvin

Gigahertz

.

So the above establishes a relation between the temperature and the frequency of the

maximum energy density per unit frequency.

You will often see u

ν

which is the energy density per unit Hertz rather than the energy

density per unit radians per second. This is related to u

ω

by the appropriate number of

2π’s. You will also see u

λ

which is the energy density per unit wavelength. This is found

from

u

λ

|dλ| = u

ω

|dω| .

This says that the energy density within a range of wavelengths should be same as the

energy density within the corresponding range of frequencies. The absolute value signs are

there because we only care about the widths of the ranges, not the signs of the ranges. We

use ω = 2πc/λ and dω = (2πc/λ

2

)|dλ|,

u

λ

= u

ω

dω

dλ

,

=

¯h(2πc/λ)

3

π

2

c

3

(exp(2π¯hc/λτ) −1)

2πc

λ

2

,

=

8πhc

λ

5

(exp(hc/λτ) −1)

,

=

8πτ

5

h

4

c

4

x

5

e

x

−1

,

where x = hc/λτ. At long wavelengths, u

λ

→ 8πτ/λ

4

, and at short wavelengths u

λ

is

exponentially cut oﬀ. The maximum of u

λ

occurs at a wavelength given by the solution of

(x −5)e

x

+ 5 = 0 .

The solution is x = 4.96511 . . .. From this, we have

λ

max

T =

hc

4.97k

= 0.290 cmK.

This is known as Wien’s displacement law. It simply says that the wavelength of the

maximum in the spectrum and the temperature are inversely related. In this form, the

constant is easy to remember. It’s just 3 mmKelvin. (Note that the wavelength of the

maximum in the frequency spectrum and the wavelength of the maximum in the wavelength

spectrum diﬀer by a factor of about 1.6. This is just a reﬂection of the fact that wavelength

and frequency are inversely related.)

Let’s apply some of these formulae to the sun. First, the peak of the spectrum is in

about the middle of the visible band (do you think this is a coincidence or do you suppose

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-10

there’s a reason for it?), at about λ

max

≈ 5000

˚

A = 5 ×10

−5

cm. Using the displacement

law (and assuming the sun radiates as a blackbody), we ﬁnd T

sun

≈ 5800 K. The luminosity

of the sun is L = 3.8 ×10

33

erg s

−1

. The radius of the sun is r = 7.0 ×10

10

cm. The ﬂux

emitted by the sun is J = L/4πr

2

= 6.2 ×10

10

erg cm

−2

s

−1

. This is about 60 Megawatts

per square meter! We equate this to σ

B

T

4

and ﬁnd T

sun

≈ 5700 K, very close to what we

estimated from the displacement law.

Problem 17 in chapter 4 of K&K points out that the entropy of a single mode of

thermal radiation depends only on the average number of photons in the mode. Let’s see

if we can work this out. We will use

σ =

∂ τ log Z

∂τ

V

,

where Z is the partition function and the requirement of constant volume is satisﬁed by

holding the frequency of the mode constant. We’ve already worked out the partition

function for a single mode

Z =

1

1 −e

−¯ hω/τ

.

The average occupancy (number of photons) in the mode is

n =

1

e

¯ hω/τ

−1

,

from which we ﬁnd

n + 1

n

= e

¯hω/τ

, or

¯hω

τ

= log

n + 1

n

.

Now let’s do the derivatives to get the entropy

σ =

∂

∂τ

(τ log Z) ,

= log Z −τ

∂

∂τ

log

1 −e

−¯ hω/τ

,

= log

1

1 −e

−¯ hω/τ

−τ

1

1 −e

−¯ hω/τ

−e

−¯ hω/τ

−

¯hω

τ

−

1

τ

,

= log

1

1 −n/(n + 1)

+

¯hω

τ

e

−¯ hω/τ

1 −e

−¯ hω/τ

,

= log(n + 1) + log

n + 1

n

n/(n + 1)

1 −n/(n + 1)

,

= log(n + 1) +nlog

n + 1

n

,

= (n + 1) log(n + 1) −nlog n ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 29-Sep-2004 9-11

Which is the form given in K&K. This is another way of making the point that the ex-

pansion of the universe does not change the entropy of the background radiation. The

expansion redshifts each photon—stretches out its wavelength—in proportion to the ex-

pansion factor, but it does not change the number of photons that have the redshifted

wavelength—the number of photons in the mode. So, the entropy doesn’t change. (This

assumes that the photons don’t interact with each other or with the matter. Once the

universe is cool enough (≤ 4000 K) that the hydrogen is no longer ionized, then the inter-

actions are very small.)

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-1

Johnson Noise

This is another application of the thermal equilibrium of electromagnetic modes. Con-

sider an ideal transmission line, like a long piece of lossless coaxial cable. Suppose its

length is L and suppose it is shorted out at each end. Then any wave that travels along

the line is reﬂected at each end and to have an appreciable amplitude, the length of the

line must contain an integral number of half wavelengths. In other words this is just a

one-dimensional cavity of length L. There are modes of the electromagnetic ﬁelds, most

conveniently represented by the potential diﬀerence between the inner and outer conduc-

tors. V

n

= V

n,0

sin(ωt) sin(nπx/L), where n is any positive integer. V

n

and V

n,0

represent

the potential diﬀerence and the amplitude of the potential diﬀerence. The ﬁelds must

satisfy Maxwell’s equations, so ω = nπc/L. Actually, if the coax is ﬁlled with a dielectric,

the speed of propagation can be diﬀerent from c, let’s assume it’s ﬁlled with vacuum. If

this line is in thermal equilibrium at temperature τ, each mode acts like an oscillator and

has average energy ¯hω/(e

¯ hω/τ

− 1). Let’s consider the low frequency limit so the average

energy in each mode is just τ. The number of modes per integer n is just 1. Then the

number of modes per unit frequency is

n(ω) dω =

L

πc

dω .

The energy per unit length per unit frequency is then

u

ω

=

τ

πc

,

at low frequencies.

As you may know, all transmission lines have a characteristic impedance, R. If a

resistor R is connected across the end of the line, then a wave traveling down the line is

completely absorbed by the resistor. So, let’s take a resistor, in equilibrium at temperature

τ, and connect it to the end of the line. Since the resistor and the line are at the same

temperature, they are already in thermal equilibrium and no net energy transfer takes

place. Each mode in the line is a standing wave composed equally of traveling waves

headed in both directions. The waves traveling towards the resistor will be completely

absorbed by the resistor. This means that the resistor must emit waves with equal power

in order that there be no net transfer of energy. The energy in the frequency band dω per

unit length headed towards the resistor is τ dω/2πc. This is traveling at speed c, so the

power incident on the resistor is τ dω/2π which is also the power emitted by the resistor,

What we’ve established so far is that the line feeds power τ dω/2π into the resistor

and vice-versa. This means that a voltage must appear across the resistor. This will

be a ﬂuctuating voltage with mean 0 since it’s a random thermal voltage. However, its

mean square value will not be zero. Let’s see if we can calculate this. As an equivalent

circuit, we have a resistor R, a voltage generator (the thermally induced voltage source),

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-2

a ﬁlter (to limit the frequencies to dω), and another resistor of resistance R representing

the transmission line. Then the current is I = V/2R. The average power delivered to the

resistor is then I

2

R = V

2

/4R = τ dω/2π. In the lab, one measures frequencies in Hertz

rather than radians per second, ν = ω/2π. Finally

V

2

= 4Rτ dν .

This relates the mean square noise voltage which appears across a resistor to the temper-

ature, resistance, and bandwidth (dν). Of course, this voltage results from ﬂuctuations

in the motions of electrons inside the resistor, but we calculated it by considering electro-

magnetic modes in a one-dimensional cavity, a much simpler system! This thermal noise

voltage is called Johnson noise.

Debye Theory of Lattice Vibrations

A little thought will show that sound waves in a solid are not all that diﬀerent from

electromagnetic waves in a cavity. Further thought will show that there are some important

diﬀerences that we must take into account.

The theory of lattice vibrations that we’ll discuss below applies to the ion lattice in

a conductor. In addition, one needs to account for the thermal eﬀects of the conduction

electrons which behave in many respects like a gas. We’ll consider the electron gas later

in the term. For now, we imagine that we’re dealing with an insulator.

We will treat crystalline solids. This is mainly for conceptual convenience, but also

because we want reasonably well deﬁned vibrational modes.

As a model, suppose the atoms in a solid are arranged in a regular cubic lattice. Each

atom vibrates around its equilibrium position. The equilibrium and the characteristics

of the vibrations are determined by interactions with the neighboring atoms. We can

imagine that each atom is connected to its six nearest neighbors by springs. At ﬁrst

sight, this seems silly. But, the equilibrium position is determined by a minimum in

the potential energy, and the potential energy almost surely increases quadratically with

displacement from equilibrium. This gives a linear restoring force which is exactly what

happens with a spring. So our solid is a large number of coupled oscillators. In general,

the motion of a system of coupled oscillators is very complex. You probably know from

your classical mechanics course, that the motion of a system of coupled oscillators can be

resolved into a superposition of normal modes with the motion of each mode being simple

harmonic in time. So, we can describe the motion with the N vectors r

i

which represent

the displacement of each atom from its equilibrium position, or we can describe the motion

with 3N normal mode amplitudes. For those of you that know about Fourier transforms,

the normal modes are just the Fourier transforms of the position coordinates.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-3

These normal modes represent elastic vibrations of our solid. They are standing elastic

waves, or standing sound waves. In this respect, they are similar to the cavity modes we

discussed earlier. There are two main diﬀerences. First, there are three polarizations:

there are two transversely polarized waves (as we had in the electromagnetic case) and

one longitudinally polarized wave (absent in the electromagnetic case). Second, there is a

limit to the number of modes. If our solid contains N atoms, there are 3N modes. In the

electromagnetic case, there is no upper limit to the frequency of a mode. High frequency

modes with ¯hω ≫ τ are not excited, but they are there. In the elastic case, frequencies

which are high enough that the wavelength is shorter than twice the distance between

atoms do not exist.

For simplicity, we are going to assume that the velocity of sound is isotropic and is

the same for both transverse and longitudinal waves. Also, we’ll assume that the elastic

properties of the solid are independent of the amplitude of the vibrations (at least for the

amplitudes we’ll be dealing with).

We’ll carry over as much stuﬀ from the electromagnetic case as we can. A typical

mode will look something like

displacement component = Asinωt sin

n

x

πx

L

sin

n

y

πy

L

sin

n

z

πz

L

,

where the sine factors might be cosines depending on the mode, A represents an amplitude,

and for convenience, the solid is a cube of side L. The frequency and mode numbers are

related by the speed of sound, v,

ω

2

=

π

2

v

2

L

2

n

2

x

+n

2

y

+n

2

z

.

If the solid contains N atoms, the distance between atoms is L/N

1/3

. The wavelength

must be longer than twice this distance. More precisely

2L

n

x

>

2L

N

1/3

,

with similar relations for n

y

and n

z

. In other words, the mode numbers n

x

, n

y

, and n

z

are

integers within the cube N

1/3

×N

1/3

×N

1/3

. This lower limit on the wavelength (upper

limit on the frequency) is an example of the Nyquist limit discussed later in these notes.

The number of modes per unit frequency is just as it was for the electromagnetic case

except that we must multiply by 3/2 to account for the three polarizations instead of two,

n(ω) dω =

3V ω

2

2π

2

v

3

dω .

This works for frequencies low enough that the corresponding n’s are within the cube.

It’s messy to deal with this cubical boundary to the mode number space. Instead, let’s

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-4

approximate the upper boundary as the surface of a sphere which gives the same number

of modes. In other words, there will be an upper limit to the frequency, called ω

D

, such

that

3N =

ω

D

0

n(ω) dω =

3V

2π

2

v

3

ω

D

0

ω

2

dω =

V

2π

2

v

3

ω

3

D

,

which gives

ω

D

=

6π

2

N

V

1/3

v .

Each mode acts like a harmonic oscillator and its energy is an integer times ¯hω. The

quanta of sound are called phonons. A solid contains a thermally excited phonon gas. The

average energies of these oscillators are just as they were in the electromagnetic case. We

ﬁnd the total energy by adding up the energies in all the modes,

U =

3V

2π

2

v

3

ω

D

0

ω

2

¯hω

exp(¯ hω/τ) −1

dω ,

=

3V

2π

2

¯h

3

v

3

τ

4

x

D

0

x

3

dx

e

x

−1

,

where

x

D

=

¯hω

D

τ

=

6π

2

N

V

1/3

¯hv

τ

=

kθ

kT

=

θ

T

,

where θ is called the Debye temperature and is given by

θ =

6π

2

N

V

1/3

¯hv

k

.

The Debye temperature is not a temperature you can change by adding or removing

heat from a solid! Instead, it’s a characteristic of a given solid. The way to think of it is

that a vibration with phonon energy equal to kθ is the highest frequency vibration that

can exist within the solid. Otherwise the wavelength would be too short. (The weird factor

of 6π

2

occurs because we replaced a cube with a sphere!) Typical Debye temperatures are

a few hundred Kelvin.

The limit of integration depends on the temperature, so in general, we can’t look up

the integral. Instead, we have to numerically integrate and produce a table for diﬀerent

values of x

D

= θ/T. Such a table is given in K&K.

There are two limiting cases where we can do the integral. The ﬁrst case is very low

temperature (T ≪ θ). In this case x

D

is very large and we can replace x

D

by ∞. Then

the integral is π

4

/15 and we have

U =

π

2

V

10¯ h

3

v

3

τ

4

=

3π

4

N

5k

3

θ

3

τ

4

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-5

The heat capacity at constant volume is then

C

V

=

12

5

π

4

Nk

T

θ

3

.

So a prediction of this theory is that at low temperatures, the heat capacities of solids

should be proportional to T

3

. This is borne out by experiment!

The other limit we can consider is very high temperature (T ≫ θ). In this case, we

expect all modes are excited to an average energy τ, so the total should be U = 3Nτ. Is

this what we get? At very high temperatures, x

D

≪1, so we can expand the exponential

in the denominator of the integrand,

U =

3V

2π

2

¯h

3

v

3

τ

4

x

D

0

x

3

dx

e

x

−1

,

=

3V

2π

2

¯h

3

v

3

τ

4

x

D

0

x

2

dx ,

=

V

2π

2

¯h

3

v

3

τ

4

x

3

D

,

=

V

2π

2

¯h

3

v

3

τ

4

¯h

3

v

3

τ

3

6π

2

N

V

,

= 3Nτ ,

as expected. Actually, we picked ω

D

so this result would occur “by construction.” The

heat capacity goes to 3Nk in this limit.

In one of the homework problems you are asked to come up with a better approxima-

tion in the limit of small x

D

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-6

The Nyquist Frequency

We imagine that we have a function of time that we sample periodically, every T

seconds. Then the Nyquist frequency is the frequency corresponding to a period of two

samples. ω

N

= 2π/2T = π/T. Consider a sine wave at some frequency ω,

y(t) = sin(ωt +φ) .

Since we are sampling, we don’t have a continuous function, but a discrete set of values:

y

m

= sin(ωmT +φ) .

Suppose the frequency is larger than the Nyquist frequency. Then we can write it as

an even integer times the Nyquist frequency plus a frequency less than the the Nyquist

frequency:

ω = 2nω

N

+ Ω = 2πn/T + Ω ,

where −ω

N

≤ Ω ≤ +ω

N

. Then

y

m

= sin(2πnm+ ΩmT +φ) = sin(ΩmT +φ) .

In other words, when we sample a sine wave periodically, waves with frequencies greater

than the Nyquist frequency look exactly the same as waves with frequencies less than the

Nyquist frequency. This is illustrated in the ﬁgure. The arrows along the bottom indicate

the times at which the signal is sampled. A signal at the Nyquist frequency would have

one cycle every two sample intervals. The high frequency wave has 3.7 cycles every two

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 01-Oct-2004 10-7

sample intervals or a phase change of 3.7π = (4 − 0.3)π every sample. We can’t tell how

many multiples of 2π go by between samples, so the high frequency wave looks exactly

like a low frequency wave with −0.3 cycles per two samples. The points show the value of

the signal (either wave) at each sampling interval. Of course the application to the Debye

theory of lattice vibrations is that the Nyquist spatial frequency is the highest frequency

a periodic lattice can support.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-1

Reading

This week we’ll work on chemical potential and the Gibbs distribution which is covered

in K&K chapter 5.

Parting Shot on Oscillators

Before we get to the main part of this week’s material, let’s have a quick recap on

oscillators.

If we have an oscillator of frequency ω, its energy levels are spaced by ¯hω. If this

oscillator is in thermal equilibrium at temperature τ, then if ¯ hω < τ, its average energy is

τ. If ¯ hω > τ, its average energy is exponentially “killed oﬀ” and it’s not too gross of an

approximation to say that it’s 0. This happens because of the quantized states. Energy

can only be exchanged with the oscillator in units of ¯ hω and when this is larger than a

thermal energy, the heat reservoir almost never gets enough energy together to excite the

oscillator.

We know the energy of the oscillator, and all we have to do is count up how many

oscillators there are in order to ﬁnd the total energy of the system.

For blackbody radiation, the number of modes is proportional to ω

3

(

ω

2

dω), and all

these modes are excited up to the maximum ω where ¯hω = τ. So the energy in blackbody

radiation is proportional to τ

4

.

In the case of lattice vibrations, we again have a number of modes proportional to ω

3

,

but there are a ﬁnite number, so if we run out of modes before we reach the maximum

ω of an excited oscillator, then every mode has energy τ and the total energy is 3Nτ

(where 3N is the number of modes). If we don’t run out of modes before we reach the

maximum ω of an excited oscillator, then the situation is just like that with blackbody

radiation and the energy is proportional to τ

4

. These two cases correspond to high and

low temperatures and give heat capacities which are constant or proportional to τ

3

for

high and low temperatures. By the way, the fact that molar heat capacities of solids are

usually 3R at room temperature (R is the gas constant) is called the law of Dulong and

Petit.

Finally, when we considered Johnson noise in a resistor, we made use of a one dimen-

sional cavity, where the number of modes is proportional to ω (

dω) and we considered

the low temperature limit and found the energy proportional to τ dω.

Basically, we know the energy of the modes and we count the modes. All the factors

of π, ¯ h, etc., come out as a result of the proper bookkeeping when we do the counting.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-2

Integrals Related to Planck’s Law

Judging by experience with previous classes, some (maybe many) of you are wondering

just how one goes about doing the integral

∞

0

x

2

dx

exp(x) −1

.

The ﬁrst thing to note is that doing integrals is an art, not a science. You’ve probably

learned a number of techniques for doing integrals. However, there is never a guarantee

that an arbitrary expression can be integrated in closed form, or even as a useful series.

Some expressions you just have to integrate numerically!

Let’s see what we can do about

I

n

=

∞

0

x

n

dx

exp(x) −1

,

where n need not be an integer, but I think we’ll need n > 0. The ﬁrst thing to do is to

try and look it up! I like Dwight, Tables of Integrals and other Mathematical Data, 4

th

edition, 1964, MacMillan. (Actually, I bought mine when I was an undergraduate in the

late 60’s. It seems that they were coming out with a new edition every 10 years, so maybe

it’s up to the seventh edition by now!) Anyway, in my edition of Dwight, there is entry

860.39:

∞

0

x

p−1

dx

e

ax

−1

=

Γ(p)

a

p

¸

1 +

1

2

p

+

1

3

p

+· · ·

=

Γ(p)

a

p

ζ(p) ,

and this is basically the integral we’re trying to do.

We’ve talked about the gamma function, Γ(z), see lecture 5. The Riemann Zeta

function is

ζ(s) =

∞

¸

k=1

1

k

s

,

where Re(s) > 1. The function can be deﬁned for other values of s, but this series

requires Re(s) > 1. A good reference book for special functions is Abramowitz and Stegun,

Handbook of Mathematical Functions with Formulas, Graphs, and Mathematical Tables,

US Government Printing Oﬃce. If you look up the zeta function in this handbook, you’ll

ﬁnd lots of cool stuﬀ. For example,

ζ(s) =

¸

primes p

1

1 −1/p

s

.

The zeta function establishes a connection between number theory and function theory!

Other things you’ll ﬁnd in A&S are various integral representations, representations in

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-3

terms of Bernoulli and Euler polynomials (if you don’t know what these are, they’re also

discussed in A&S), special values, and tables of values. For example ζ(0) = −1/2, ζ(1) =

∞, ζ(2) = π

2

/6, and ζ(4) = π

4

/90. ζ(3), needed for the integral at the top of the page,

does not have a simple value. Instead, we ﬁnd it in a table, ζ(3) = 1.2020569 . . ..

Can we write I

n

in the form suggested by Dwight?

I

n

=

∞

0

x

n

dx

exp(x) −1

,

=

∞

0

x

n

e

−x

dx

1 −e

−x

,

=

∞

0

x

n

e

−x

∞

¸

m=0

e

−mx

dx ,

=

∞

0

x

n

∞

¸

m=0

e

−(m+1)x

dx ,

=

∞

¸

m=0

∞

0

x

n

e

−(m+1)x

dx ,

=

∞

¸

m=0

1

(m+ 1)

n+1

∞

0

((m+ 1)x)

n

e

−(m+1)x

d ((m+ 1)x) ,

=

∞

¸

m=0

1

(m+ 1)

n+1

∞

0

y

n

e

−y

dy ,

=

∞

¸

m=0

1

(m+ 1)

n+1

Γ(n + 1) ,

= Γ(n + 1)

∞

¸

m=1

1

(m)

n+1

, (m now starts at 1)

= Γ(n + 1) ζ(n + 1) ,

in agreement with Dwight.

If you need to numerically evaluate ζ(s), you can just start summing the series. Sup-

pose you’ve summed the inverse powers from 1 to M − 1. You should be able to show

(make some sketches) that

∞

M

dx/x

s

= 1/[(s − 1)M

(s−1)

] is less than remainder of the

sum and

∞

M

dx/(x − 1)

s

= 1/[(s − 1)(M − 1)

(s−1)

] is greater than the remainder of the

sum. You can use the average of these two integrals as an estimate of the remainder of the

sum and half their diﬀerence as a bound on the numerical error. (Actually the error will

be quite a bit smaller!). As an example, consider ζ(2) = π

2

/6 = 1.64493 . . .. The sum of

the ﬁrst 10 terms, 1+1/4+1/9+1/16+· · · +1/100 = 1.5497677 . . .. The two integrals are

just 1/11 = 0.09090909 . . . and 1/10 = 0.1. Their average is 0.09545454 . . . and half their

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-4

diﬀerence is 0.004545 . . ., so numerically we can be pretty sure that the value is within

0.00455 of 1.64522. In fact, we actually miss by only 0.00028!

The Chemical Potential

Recall in lectures 2 and 3 we discussed two systems in thermal (microscopic exchange

of energy), volume (macroscopic exchange of energy), and diﬀusive (exchange of particles)

equilibrium. By requiring that the entropy be a maximum, we found that

dσ =

1

τ

dU +

p

τ

dV −

µ

τ

dN ,

where µ is the chemical potential and N is the number of particles.

In other words,

µ = −τ

∂σ

∂N

U,V

.

We can also rewrite the diﬀerential relation above in the form

dU = τ dσ −p dV +µdN ,

from which we deduce

µ =

∂U

∂N

σ,V

.

Adding a particle to a system changes its energy by µ.

Of course, the entropy is not a completely natural variable to work with as a dependent

variable. To get around this, we use the Helmholtz free energy which we’ve previously

deﬁned as a function of temperature and volume. We now extend the deﬁnition to include

particle number. In particular, consider the free energies of two systems in contact with

a reservoir at temperature τ. We allow these two systems to exchange particles until

equilibrium is established. The free energy of the combined system is

F = F

1

+F

2

,

where the subscripts refer to the individual systems. The free energy will be a minimum

at constant temperature and volume. The change in free energy due to particle exchange

is

dF = dF

1

+dF

2

=

∂F

1

∂N

1

τ,V

dN

1

+

∂F

2

∂N

2

τ,V

dN

2

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-5

We want dF = 0 at minimum and, since the total number of particles is constant, we have

dN

1

= −dN

2

which means that

∂F

1

∂N

1

τ,V

=

∂F

2

∂N

2

τ,V

= µ .

This constitutes yet another deﬁnition of the chemical potential. Is it the same chemical

potential we’ve already deﬁned? Yes, provided the free energy continues to be deﬁned by

F = U −τσ .

Then when the particle number changes, we have

dF = dU −τ dσ −σ dτ ,

= τ dσ −p dV +µdN −τ dσ −σ dτ ,

= −σ dτ −p dV +µdN ,

and it’s the same chemical potential according to either deﬁnition.

By the way we deﬁned the chemical potential, it must be the same for two systems in

diﬀusive and thermal contact, once they’ve reached equilibrium. What if the two systems

in diﬀusive contact do not have equal values of the chemical potential? Since

dF = dF

1

+dF

2

= µ

1

dN

1

+µ

2

dN

2

,

there will be a ﬂow of particles in order to minimize F. If µ

1

> µ

2

, then dN

1

< 0 and

dN

2

= −dN

1

> 0, so particles ﬂow from the system with the higher chemical potential to

the system with the lower chemical potential.

To summarize,

µ = −τ

∂σ

∂N

U,V

=

∂U

∂N

σ,V

=

∂F

∂N

τ,V

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-6

Getting a Feel for the Chemical Potential

The chemical potential is another one of those thermodynamic quantities that seems

to appear by magic. In order to gain intuition about the chemical potential, you will

probably have to see it in action and work with it for a while.

To start this process, note that adding a particle to a system requires that the energy

of the system be changed by µ while the entropy and volume are kept constant. Better

yet, the free energy changes by µ while the temperature and volume are kept constant.

Why might adding a particle to a system change the system’s energy? There are

at least two reasons. There might be macroscopic ﬁelds around (such as gravitational or

electromagnetic ﬁelds) in which the particle has an ordinary potential energy (mgh or eΦ

for example). In addition when a particle is added to a system at temperature τ, it must

acquire a thermal energy which depends on τ and other parameters of the system. In other

words the change in energy upon adding a particle can be due to both macroscopic ﬁelds

and microscopic thermal eﬀects.

The distinction made in K&K between the external, internal and total chemical po-

tentials is just a division into the macroscopic, microscopic, and total contributions to the

energy upon adding a particle.

Let’s ﬁnd the chemical potential of the classical, ideal, monatomic gas. Recall in

lecture 7, we found,

U =

3

2

Nτ ,

F = −Nτ

log

n

Q

n

+ 1

,

σ = N

log

n

Q

n

+

5

2

,

n

Q

=

mτ

2π¯h

2

3/2

,

n =

N

V

.

Of the thermodynamic potentials U, F, and σ above, only F is expressed in terms

of its natural independent variables τ, V , and N. Let’s ﬁnd µ by diﬀerentiating F with

respect to N while keeping τ and V constant.

µ =

∂F

∂N

τ,V

=

∂

∂N

−Nτ

log

n

Q

V

N

+ 1

,

= −τ

log

n

Q

V

N

+ 1

+τ ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-7

= −τ log

n

Q

V

N

,

= τ log

n

n

Q

.

Note that for a typical gas, the concentration n is quite small compared to the quantum

concentration, n

Q

, perhaps a part in 10

6

to a part in 10

5

. So we expect µ = −14τ to −11τ.

If µ gets close to zero, then the concentration is approaching the quantum concentration

and the classical treatment is no longer valid.

Suppose we wanted to calculate the chemical potential by diﬀerentiating the entropy.

We express the entropy in terms of its natural independent variables U, V , and N,

σ = N

log

n

Q

n

+

5

2

,

= N

log

mτ

2π¯h

2

3/2

V

N

+

5

2

,

substitute τ = 2U/3N,

= N

log

mU

3π¯h

2

3/2

V

N

5/2

+

5

2

.

Now diﬀerentiate with respect to N, multiply by −τ, and replace U with 3Nτ/2,

µ = −τ

∂σ

∂N

U,V

,

= −τ

∂

∂N

¸

N

log

mU

3π¯h

2

3/2

V

N

5/2

+

5

2

¸

,

= −τ

¸

log

mU

3π¯h

2

3/2

V

N

5/2

+

5

2

−

5

2

¸

,

= −τ log

n

Q

V

N

,

= τ log

n

n

Q

,

the same as we obtained before.

Since we’re having so much fun playing with the mathematics, suppose we wanted to

ﬁnd the chemical potential by diﬀerentiating the energy. This should be done at constant

entropy and volume. The Sackur-Tetrode formula for the entropy is fairly messy to solve

for the temperature, so we may not want to rewrite the energy in closed form as a function

of the entropy, volume and number of particles. Instead, we can write the energy as a

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 04-Oct-2004 11-8

diﬀerential involving dN and dτ and ﬁnd the relation between these diﬀerentials which

makes the entropy change vanish. This will be left as a homework problem. Needless to

say, one gets the same expression for the chemical potential that we’ve already derived.

As an example of a macroscopic contribution to the chemical potential, consider our

atmosphere which exists in the gravitational ﬁeld of the Earth. Suppose the atmosphere

consists of a single kind of atom of mass m, is isothermal, and is in equilibrium. Then the

chemical potential must be the same everywhere in the gas. At height h above the zero

level for the gravitational potential, there is a contribution mgh from the gravitational

ﬁeld. This means

µ = Constant = τ log

n

n

Q

+mgh ,

or

n(h) = n(0)e

−mgh/τ

.

so the concentration decreases exponentially with altitude. With the ideal gas law, p/τ =

N/V = n, so the pressure also decreases exponentially with altitude. We can write

p(h) = p(0)e

−h/h

0

,

where h

0

= τ/mg = kT/mg = RT/Mg, is called the scale height of the atmosphere.

R is the gas constant, and M is the molar mass. If we take, T = 300 K, M = 28 g

(appropriate for Nitrogen molecules), and g = 980 cms

−2

, we ﬁnd h

0

≈ 9 km. There are

several problems with this simple model. First, the atmosphere is stirred by winds, so it is

not in equilibrium. However, this is important only in the ﬁrst few miles above sea level.

At higher altitudes, the atmosphere is approximately isothermal, but with a considerable

colder temperature, about 230 K according to the plot in K&K. Also, each molecule should

have a slightly diﬀerent scale height, with the lighter molecules having a large scale height

(and being more likely to completely evaporate from the Earth).

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-1

The Gibbs Factor

In lecture 5, we divided up a large object into a system and a heat reservoir and we

considered what happens when the system and reservoir exchange energy. This led us to

the Boltzmann factor and the partition function. Now let’s consider the what happens if

we divide up the large object into the system and a reservoir except this time we allow

the exchange of particles as well as energy. The total energy is U

0

and the total number

of particles is N

0

(which is not Avogadro’s number during this discussion!). What is

the probability that the system is in the single state 1 with N

1

particles and energy E

1

compared to the probability that it’s in the single state 2 with N

2

particles and energy

E

2

? The ratio is

P(N

1

, E

1

)

P(N

2

, E

2

)

=

g(N

0

−N

1

, U

0

−E

1

) ×1

g(N

0

−N

2

, U

0

−E

2

) ×1

,

where g(N

R

, U

R

) is the number of states available to the reservoir when it contains N

R

particles and has energy U

R

. We are just applying our postulate that the probability is

proportional to the number of available states. We have

P(N, E) ∝ g(N

0

−N, U

0

−E) ,

∝ e

σ(N

0

−N, U

0

−E)

,

∝ e

σ(N

0

, U

0

) −N

∂σ

∂N

−E

∂σ

∂U

,

∝ e

(σ(N

0

, U

0

) +Nµ/τ −E/τ)

,

∝ e

σ(N

0

, U

0

)

×e

(Nµ/τ −E/τ)

,

∝ e

(Nµ/τ −E/τ)

,

where we dropped the ﬁrst factor since it’s a constant for any given reservoir. The proba-

bility

P(N, E) ∝ e

(Nµ −E)/τ

,

is called the Gibbs factor. A probability distribution described by Gibbs factors is called

the grand canonical distribution.

Consider the sum

Z =

All N, E

e

(Nµ −E)/τ

,

where the sum is over all numbers of particles N, and for each N, all possible states of

N particles with energies E. Or, one can sum over all energies ﬁrst, and then over all

numbers of particles with that energy. Basically it’s a sum over all possible states which

are parameterized by number of particles and energy. Z is called the Gibbs sum, the grand

sum, or the grand partition function. K&K use a kind of cursive Z symbol for this sum.

I don’t seem to have that in my T

E

X fonts, so we’ll use Z.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-2

The grand partition function is used to normalize the probabilities:

P(N, E) =

1

Z

e

(Nµ −E)/τ

.

With the normalized probability distribution, we can compute mean values. For example,

the mean number of particles in the system is

N =

1

Z

All N, E

N e

(Nµ −E)/τ

,

= τ

1

Z

All N, E

N

τ

e

(Nµ −E)/τ

,

= τ

1

Z

∂Z

∂µ

,

= τ

∂ log Z

∂µ

.

The mean energy is slightly more complicated. If we diﬀerentiate Z with respect to 1/τ,

it will pull down a term with the energy in it, but we’ll also get the number of particles

again.

Nµ −E =

1

Z

All N, E

(Nµ −E) e

(Nµ −E)/τ

,

=

1

Z

∂Z

∂(1/τ)

,

=

∂ log Z

∂(1/τ)

,

E = Nµ −

∂ log Z

∂(1/τ)

,

= µN −

∂ log Z

∂(1/τ)

,

= µτ

∂ log Z

∂µ

−

∂ log Z

∂(1/τ)

,

= µτ

∂ log Z

∂µ

+τ

2

∂ log Z

∂τ

.

K&K deﬁne the activity as

λ = e

µ/τ

.

The grand partition function can be rewritten in terms of the activity as

Z =

All N, E

λ

N

e

−E/τ

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-3

from which it follows that the average number of particles is

N = λ

∂ log Z

∂λ

.

Example: Binding of N Molecules

This example is related to the myoglobin example discussed in K&K and also to K&K,

chapter 5, problem 14. The example system is a hemoglobin molecule which can bind zero

to four oxygen molecules. A hemoglobin molecule is similar to four myoglobin molecules,

each of which can bind zero or one oxygen molecule.

We will work out an expression for the average number of molecules as a function of

the partial pressure of oxygen in the atmosphere. We will assume that each successive

molecule binds with same energy (relative to inﬁnite separation), ǫ < 0. This is not quite

right as successive oxygen molecules are bound more tightly than the ﬁrst oxygen molecule.

Also, we will start by assuming that 0 to M molecules may be bound, and specialize to the

case of four molecules later. Finally, we will assume that there is only one state in which

N molecules are bound. This corresponds to assuming that the molecules are bound to

hemoglobin in a deﬁnite order. We will let the activity be λ = exp(µ/τ). Then the grand

partition function is,

Z = 1 +λe

−ǫ/τ

+

λe

−ǫ/τ

2

+· · · +

λe

−ǫ/τ

M

,

=

1 −

λe

−ǫ/τ

M+1

1 −λe

−ǫ/τ

,

log Z = log

1 −

λe

−ǫ/τ

M+1

−log

1 −λe

−ǫ/τ

.

Now we diﬀerentiate with respect to λ in order to ﬁnd the average number of bound

molecules,

N = λ

∂ log Z

∂λ

,

= −

(M + 1)

λe

−ǫ/τ

M+1

1 −

λe

−ǫ/τ

M+1

+

λe

−ǫ/τ

1 −λe

−ǫ/τ

,

= λe

−ǫ/τ

1 −(M + 1)

λe

−ǫ/τ

M

+M

λe

−ǫ/τ

M+1

1 −

λe

−ǫ/τ

M+1

1 −λe

−ǫ/τ

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-4

In the case that M = 1, which corresponds to myoglobin which can bind one molecule,

the expression becomes

N =

λe

−ǫ/τ

1 +λe

−ǫ/τ

.

Now, λ = exp(µ/τ), and in order for our system to be in equilibrium with atmospheric

oxygen it must have the same chemical potential as atmospheric oxygen. This means that

λ = n/n

Q

= p/τn

Q

, where p is the partial pressure of oxygen, τ is the temperature of

atmospheric oxygen (presumably room temperature), and n

Q

is the quantum concentration

evaluated at temperature τ and for the mass of an O

2

molecule. So λ can be evaluated

numerically for any desired partial pressure of oxygen. If we look at the curve for myoglobin

in ﬁgure 5.12 of K&K, it appears that the average number of bound molecules is about 1/2

when the partial pressure of oxygen is about 5 mm of Hg. (One atmosphere is 760 mm of

Hg and oxygen is about 20% of the atmosphere, so the maximum partial pressure is roughly

150 mm of Hg. Let λ

1/2

be the activity when the number of bound molecules is 1/2. From

our expression above, we see that this means λ

1/2

exp(−ǫ/τ) = 1 or exp(−ǫ/τ) = 1/λ

1/2

.

Let’s plug this into the formula for hemoglobin (M = 4) and express the result as a fraction

of the maximum number of bound molecules. The result is

f =

N

4

=

x

4

1 −5x

4

+ 4x

5

(1 −x

5

)(1 −x)

=

x

4

1 + 2x + 3x

2

+ 4x

3

1 +x +x

2

+x

3

+x

4

,

where x = λ/λ

1/2

. This curve is shown in the ﬁgure. Binding more molecules, all with the

same binding energy, causes a sharper transition from “empty” to “full!”

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-5

More on the Chemical Potential—Energy to Add a Particle

This section is based on the discussion in K&K in pages 250–252.

As you recall, the chemical potential is the amount of energy required to add one par-

ticle to a system. Also, we learned that the chemical potential for an ideal monatomic gas

is µ = τ log(n/n

Q

) which is about −14 to −11τ for a typical gas under typical conditions.

It appears that if we add one more particle to a gas, we’re not required to spend energy,

but we get back some energy! This must be wrong, but what’s the explanation?

The answer has to do with where the particle came from. There’s also an energy

involved in removing the particle from its original location before we add it to the gas.

Suppose we have two containers of the same gas at the same temperature, τ. Suppose

the chemical potentials are diﬀerent with µ

2

> µ

1

. Then the concentrations must be

diﬀerent, or equivalently, the pressures are diﬀerent with p

2

> p

1

. If we remove a molecule

from container 1 and add it to container 2, we receive energy µ

1

from container 1 but must

give energy µ

2

to container 2. The total amount of energy that must be supplied by an

external agent to move this molecule is µ

2

−µ

1

> 0. What does this turn out to be?

∆E = µ

2

−µ

1

,

= τ log

n

2

n

Q

−τ log

n

1

n

Q

,

= τ log

n

2

n

1

.

Now suppose we have N molecules of a gas at temperature τ and we isothermally com-

press it from volume V

1

down to volume V

2

or, equivalently, from concentration n

1

up to

concentration n

2

. How much mechanical work is required?

∆W =

V

2

V

1

−p dV ,

= −Nτ

V

2

V

1

dV

V

,

= −Nτ log

V

2

V

1

,

= Nτ log

V

1

V

2

,

= Nτ log

N/V

2

N/V

1

,

= Nτ log

n

2

n

1

.

So the energy per molecule required to isothermally change the concentration from n

1

to

n

2

is just the energy required to move one molecule from a gas at concentration n

1

to a

gas at concentration n

2

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-6

In fact, we could imagine doing the following: Isothermally compress the gas in con-

tainer 1 from concentration n

1

to concentration n

2

. This requires spending an energy

Nτ log(n

2

/n

1

). Move the molecule from container 1 to container 2. This requires no en-

ergy since the concentrations and the chemical potentials are now the same. Expand the

gas in container 1 back to concentration n

1

. This recovers an energy (N −1)τ log(n

2

/n

1

),

so the net expenditure of energy is τ log(n

2

/n

1

) = µ

2

− µ

1

. Recall that the internal en-

ergy of an ideal monatomic gas depends only on its temperature (U = 3Nτ/2). Before

and after we moved the molecule from container 1 to container 2, the temperature of all

the gas was τ, so the internal energy of the gas did not change! Where did the energy

τ log(n

2

/n

1

) go??? Hints: has the free energy of the combined systems changed? What

about the entropy?

Example: Chemical Potential and Batteries

Surprise: chemical potential might actually have something to do with chemistry!

An example has to do with batteries—or better, voltaic cells. K&K have a discussion of

the lead acid battery used in cars on pages 129–131. However, I’ve been told that this

discussion is not quite right. In particular see Saslow, W., 1996, PRL, 76, 4849.

By the way, did you know that Princeton subscribes to many of the on-line journals?

This means if you access the web from a Princeton address, you’ll be allowed to read the

journals on-line. In particular, you can ﬁnd Physical Review and Physical Review Letters

on-line and the article cited above can be downloaded and printed out.

Rather than discuss the lead acid battery, let’s look at a simpler (I hope) system:

the Daniell cell. This is discussed by the same author in 1999, AJP, 67, 574. (True

confession: I have not read the article in the American Journal of Physics, but rather, the

preprint that used to be on the author’s web site. But the TAMU physics web site has

been revamped and I can’t ﬁnd the preprint anymore!) The Daniell cell is also discussed

in chemistry textbooks, such as the one I used many years ago, Pauling, L., 1964, College

Chemistry, (San Francisco:Freeman), p. 354. The following discussion is based on both of

these sources.

The ﬁgure shows a schematic of the cell. It has a solution of zinc sulfate (ZnSO

4

)

surrounding a zinc electrode and a copper sulfate (CuSO

4

) solution surrounding a copper

electrode. The two solutions are in contact. The zinc electrode is the negative electrode

or cathode and the copper electrode is the positive electrode or anode.

Chemical reactions occur at the electrodes. At the copper electrode, the reaction is

Cu

++

+ 2e

−

→Cu .

The copper ion was in solution and the electrons come from the electrode. The neutral

copper atom “plates out” on the copper electrode.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-7

At the zinc electrode, the reaction is

Zn →Zn

++

+ 2e

−

.

Zinc atoms in the electrode go into solution as zinc ions and leave behind two electrons on

the cathode.

If a wire is connected between the two

electrodes, the electrons left behind by the

zinc can travel through the external circuit

to the copper electrode where they join up

with the copper ions to plate out the copper

atoms. (Of course, electrons go in one end

and diﬀerent electrons come out the other

end. . ..) Charge is transfered inside the cell,

through the electrolyte, by sulfate ions. That

is, one can think of CuSO

4

dissociating into

Cu

++

and SO

−−

4

at the positive electrode,

the Cu

++

plates out leaving behind a spare

sulfate ion which diﬀuses over to the negative

electrode to join up with a zinc ion and form

ZnSO

4

. (Of course, sulfate ions don’t go all

the way across the electrolyte; ions go in one

end and diﬀerent ions come out the other end. . ..) Essentially all the current in the

electrolyte is carried by the ions and none by electrons.

If we actually have a complete circuit, current will ﬂow until one of the consumables

is exhausted. If all the copper is plated out of solution or if the zinc electrode is completely

dissolved, that will be the end of the cell. When operated in this mode, the cell converts

chemical potential energy into electrical energy.

Our methods apply to equilibrium situations, so we’ll discuss the situation when

there is no current ﬂowing in the external circuit and the system has reached equilibrium.

(Actually, a non-uniform distribution of electrolytes is also not an equilibrium situation, so

we are really assuming that the time for the electrolytes to diﬀuse is long compared to the

time for the reactions at the electrodes to complete.) As zinc goes into solution and copper

plates out, the electrodes acquire charges and electric potentials. When the the potentials

are large enough the reactions stop. When the reactions stop, the chemical potentials of

the atoms/ions must be the same whether they are in solution or on the electrodes.

Let V

a

, V

s

, and V

c

be the electric potentials (voltages) of the anode, solutions, and

cathode. Note that we assume the electrolytes (solutions) are equipotentials. If not, there

would be a current ﬂow until a uniform potential is established. The voltage of the cell

(e.g., measured by a voltmeter placed across the anode and cathode) is

V

cell

= V

a

−V

c

= (V

a

−V

s

) + (V

s

−V

c

) .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 06-Oct-2004 12-8

Consider a zinc ion in the cathode. When equilibrium has been established, the chemical

potential of the zinc in the cathode must be the same as that of zinc in solution. The

chemical potential is made of two parts: the internal chemical potential and the potential

energy of the ion in macroscopic electric potential of the cathode or the solution:

µ

ci

(Zn

++

) + 2eV

c

= µ

si

(Zn

++

) + 2eV

s

,

or

µ

ci

(Zn

++

) −µ

si

(Zn

++

) = 2e(V

s

−V

c

) ,

where e > 0 represents the magnitude of the charge on an electron and µ

ci

and µ

si

represent

the internal chemical potentials in the cathode and the solution. Note that I have shown

the zinc as zinc ions on the cathode as well as in solution. This is mainly for clarity and

can be justiﬁed by noting that the conduction electrons in a metal are not localized to

any particular atom. The diﬀerence of internal chemical potentials is determined by the

chemical reaction. It is customary to divide this by the magnitude of the electric charge

and the number of charges involved and tabulate as a potential diﬀerence. So, for example,

my 1962 edition of the Handbook of Chemistry and Physics has a table titled “Potentials

of Electrochemical Reactions at 25

◦

C in which one ﬁnds +0.7628 V listed for the reaction

Zn →Zn

++

+ 2e

−

. This means that V

s

−V

c

is about 0.76 V.

At the anode, with no current ﬂowing, we have

µ

ai

(Cu

++

) −µ

si

(Cu

++

) = −2e(V

a

−V

s

) .

The Handbook lists the electric potential of the reaction Cu →Cu

++

+2e

−

as −0.3460 V.

Thus V

a

−V

s

= 0.35 V and the open circuit cell potential is V

cell

= 1.11 V.

Comments: the potentials associated with reactions that occur at the cathode or

anode are called half cell potentials. If this reminds you of redox reactions in chemistry,

it should! The Handbook contains a table titled “Electromotive Force and Composition

of Voltaic Cells” which gives the composition and voltage of selected cells. The half cell

voltages are determined by deﬁning a standard half cell (a platinum electrode over which

hydrogen ions are bubbled) as a standard with zero half cell potential. Then all other half

cells are measured relative to the standard. Recall: only potential energy diﬀerences are

important! Finally, by now you should be getting a feel for why it’s called the chemical

potential!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-1

Example: Magnetic Particles in a Magnetic Field

Recall the paramagnetic spin system we discussed in lecture 4. In this system, there

are magnets with orientations parallel or antiparallel to a magnetic ﬁeld. In the parallel

orientation, the energy is −mB = −E, where m is the magnetic moment and B is the

magnetic ﬁeld. In the antiparallel orientation the energy is +mB = +E. In lecture 4,

we worked out the relative numbers of parallel and antiparallel magnets and found that it

depended on the ratio of thermal to magnetic energies.

Following the discussion in K&K, pages 127–129, suppose that we have the same kind

of system, but in addition, the magnetic particles are free to move, so the aligned magnets

will be attracted to regions of high ﬁeld strength while the antiparallel magnets will be

repelled from regions of high ﬁeld strength. Of course, in the regions of high ﬁeld, one

would expect to ﬁnd a greater fraction aligned even if the particles couldn’t move. . . Let n

↑

be the concentration of parallel and n

↓

be the concentration of antiparallel systems. Just

as with an ideal gas, we expect that microscopic or internal contribution to the chemical

potential should depend on the concentration,

µ

↑,int

= τ log

n

↑

n

Q

and µ

↓,int

= τ log

n

↓

n

Q

.

We assume that we can treat the parallel and antiparallel magnets as distinct kinds of

“particles.” To the internal chemical potential must be added the external potential due

the energy in the magnetic ﬁeld,

µ

↑

= τ log

n

↑

n

Q

−mB ,

µ

↓

= τ log

n

↓

n

Q

+mB .

Now, the parallel and antiparallel magnets are in thermal equilibrium with each other and

can be changed into one another. That is, one can remove a particle from the parallel

group and add it to the antiparallel group and vice-versa. When the system has come to

equilibrium, at temperature τ, the free energy must be stationary with respect to changes

in the particle numbers which means the chemical potentials of the two kinds of particles

must be the same. Furthermore, we are allowing the particles to diﬀuse to regions of higher

or lower ﬁeld strength, and the chemical potential must be independent of ﬁeld strength.

So,

µ

↑

= µ

↓

= Constant.

This relation together with the previous equations are easily solved to yield

n

↑

(B) =

1

2

n(0)e

+mB/τ

and n

↓

(B) =

1

2

n(0)e

−mB/τ

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-2

where we’re explicitly showing that the concentrations depend on B and n(0) is the com-

bined concentration where B = 0. The combined concentration as a function of B is

n(B) = n

↑

(B) +n

↓

(B) = n(0) cosh(mB/τ) = n(0)

1 +

m

2

B

2

2τ

2

+· · ·

.

These relations show both eﬀects we mentioned earlier. The higher the ﬁeld strength,

the greater the fraction of aligned magnets (as we already knew from lecture 4) and the

greater the concentration of magnets. The magnetic particles diﬀuse to regions of high

ﬁeld strength.

In ﬁgure 5.6, K&K show a plot of chemical potential versus concentration for sev-

eral diﬀerent ﬁeld strengths. In problem 5 of chapter 5, we are asked for what value of

m/τ was this ﬁgure drawn. The key datum to extract from the plot is that at a given

chemical potential, the concentration increases by two orders of magnitude as B is in-

creased from 0 to 20 kG. We can plug this directly into the previous expression to get

m/τ = 5.30/(20000 G) = 0.000265 G

−1

. Note that we had to use the cosh form of the

expression, not the series, because mB/τ > 1. Problem 5.5 also asks how many Bohr

magnetons must be contained in each particle. A Bohr magneton (roughly the magnetic

moment of an electron) is µ

B

= e¯h/2mc where e and m are the charge and mass of an

electron. µ

B

= 0.927 ×10

−20

erg G

−1

. Doing the arithmetic, we obtain about 1200 mag-

netons. The particles must contain 1200 paramagnetic molecules with a spin of ¯ h/2 and

a magnetic moment of µ

B

. They could also contain a more or less arbitrary number of

non-magnetic molecules.

Example: Impurity Ionization

In pages 143–144, K&K discuss an impurity atom in a semiconductor. The atom may

lose a valence electron and become ionized. The energy required to remove an electron

from the donor atom is I. The model for this impurity atom is a three state system:

the ionized state has energy 0 and no electron is present. There are two bound states,

both have energy −I and both have one electron present. One has the electron with spin

up along some axis and the other has the electron with spin down. The grand partition

function is

Z = 1 +e

(µ +I)/τ

+e

(µ +I)/τ

,

where the ﬁrst term comes from the ionized state and the second and third terms account

for the spin up and spin down bound states. The average number of (bound) electrons

and the average energy are

N =

e

(µ +I)/τ

+e

(µ +I)/τ

1 +e

(µ +I)/τ

+e

(µ +I)/τ

=

2e

(µ +I)/τ

1 + 2e

(µ +I)/τ

,

E =

−Ie

(µ +I)/τ

−Ie

(µ +I)/τ

1 +e

(µ +I)/τ

+e

(µ +I)/τ

=

−2Ie

(µ +I)/τ

1 + 2e

(µ +I)/τ

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-3

The probability that the impurity atom is ionized is

P(N = 0) =

1

1 + 2e

(µ +I)/τ

.

If we don’t know the value of µ, we can’t actually calculate any of these averages or this

probability. What sets the value of µ? Answer: µ is determined by the electron distribution

in the rest of the semiconductor. (A subject we’ll get to in a few weeks!) Although we don’t

know µ at this point, we’re used to the idea that µ increases with increasing concentration.

In the above expressions we see that increasing µ increases the mean number of particles

in the system, decreases the mean energy (energy goes down for a bound particle), and

decreases the probability of being ionized. All this is reasonable and might have been

expected. The higher the concentration of electrons in the semiconductor, the harder it is

for the atom to give an extra electron to the semiconductor and become ionized!

Example: K&K, Chapter 5, Problem 6

In this problem we are asked to work with a 3 state system. The states are: (1) no

particle, energy is 0; (2) one particle, energy is still 0: (3) one particle, energy is ǫ, so

a particle can be absent, present with zero energy, or present with energy ǫ. The grand

partition function is

Z = 1 +λ +λe

−ǫ/τ

,

where λ = exp(µ/τ). The three terms in this sum correspond to the three states enumerated

above. The thermal average occupancy is just the average number of particles in the system

and is

N =

1

Z

0 · 1 + 1 · λ + 1 · λe

−ǫ/τ

=

λ +λe

−ǫ/τ

1 +λ +λe

−ǫ/τ

.

Of course, this result can also be obtained using N = λ(∂/∂λ) log Z. Just as in the

previous example, increasing µ (λ) makes it harder for the system to give the particle

to the reservoir (which determines µ) and the system is more likely to contain a bound

particle. The thermal average occupancy of the state with energy ǫ is

N(E = ǫ) =

λe

−ǫ/τ

Z

=

λe

−ǫ/τ

1 +λ +λe

−ǫ/τ

.

Here we see that in the limit of very large µ (λ) the system always contains a particle, and

the relative probability that the particle is in the high energy state is just the Boltzmann

factor, exp(−ǫ/τ). The average energy is

E =

ǫλe

−ǫ/τ

Z

=

ǫλe

−ǫ/τ

1 +λ +λe

−ǫ/τ

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-4

Finally, we are asked to calculate the grand partition function in the event that a

particle can exist in both the zero energy state and the state with energy ǫ simultaneously.

In other words, there is a fourth state of the system; it contains two particles and has

energy ǫ. We have

Z = 1 +λ +λe

−ǫ/τ

+λ

2

e

−ǫ/τ

= (1 +λ) · (1 +λe

−ǫ/τ

) .

In this case, Z can be factored. K&K point out that this means that the system can

be treated as two independent systems. This is an example of a general rule that for

independent (but weakly interacting) systems, the grand partition function is the product

of the grand partition functions for each independent system, just as the partition function

of independent systems is a product of the individual partition functions (Homework 2,

problem 4).

Fermi-Dirac and Bose-Einstein Distributions

When we considered a low density gas in lecture 7, we considered the single particle

states of a particle conﬁned to a box. To treat more than one particle, we imagined that

the particles were weakly interacting, so we could, to some level of approximation, treat

each particle as though it occupied a single particle state. In the limit of no interactions

between particles, this would be exact (but it might be hard to achieve thermal equilib-

rium!). For typical gases at room temperature and atmospheric pressure we found that the

concentration was very low, so that the chance that any single particle state was occupied

was very small, maybe one part in a million. We just didn’t have to worry about the

chances of ﬁnding two particles in a state.

Now we want to consider the distribution when there’s a good chance of ﬁnding single

particle states occupied. We are going to assume that we have non-interacting particles in

which each particle in the system can be said to be in a single particle state. There are

two kinds of particles, fermions, which have half integer spins (spin angular momentum

is a half integer times ¯ h), and bosons which have integral spins. fermions obey the Pauli

exclusion principle: at most one particle may occupy a single state. On the other hand, an

unlimited number of bosons may be placed in any given state. Since we have independent

single particle states, the grand partition function for all the states is the product of the

grand partition function for the individual states. So to start with, let’s calculate the grand

partition function for an individual state of energy ǫ.

In the case of fermions, there are two possibilities: no particle present with energy 0

and one particle present with energy ǫ. Then

Z = 1 +e

(µ −ǫ)/τ

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-5

The average number of particles in this state of energy ǫ is denoted by f(ǫ)

f(ǫ) = N =

e

(µ −ǫ)/τ

1 +e

(µ −ǫ)/τ

=

1

e

(ǫ −µ)/τ

+ 1

.

This is called the Fermi-Dirac distribution and fermions are said to obey Fermi-Dirac

statistics. If ǫ = µ, then the average number of particles in the state is 1/2. If ǫ < µ, the

average occupancy is bigger than 1/2 and approaches 1 as ǫ →−∞. If ǫ > µ, the average

occupancy is less than 1/2 and approaches 0 as ǫ →+∞. This distribution starts at 1 at

very low energies, winds up at 0 at very high energies and makes the transition from 0 to

1 in the neighborhood of µ. The temperature controls the width of the transition. At very

low temperatures the transition is sharp. At high temperatures, the transition is gradual.

For bosons, the possibilities are no particles present with energy 0, 1 particle present

with energy ǫ, 2 particles present with energy 2ǫ, 3 particles present with energy 3ǫ, and

so on. The grand partition function is

Z = 1 +e

(µ −ǫ)/τ

+e

2(µ −ǫ)/τ

+e

3(µ −ǫ)/τ

+· · · =

1

1 −e

(µ −ǫ)/τ

.

Note that µ < ǫ if the sum is to converge. The average occupancy is

f(ǫ) = τ

∂ log Z

∂µ

=

e

(µ −ǫ)/τ

1 −e

(µ −ǫ)/τ

=

1

e

(ǫ −µ)/τ

−1

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-6

This is called the Bose-Einstein distribution and bosons obey Bose-Einstein statistics.

Again, note that µ < ǫ if the distribution function is to make sense. In fact, if we have

weakly interacting particles occupying states of several diﬀerent energies, they all have

the same chemical potential which must therefore be less than the lowest energy of any

available state. In other words

µ < ǫ

minimum

.

The minimum energy is often set to zero, and then µ < 0, but the real constraint is just

that µ be lower than any accessible energy. The Bose-Einstein distribution diverges as

ǫ →µ. As ǫ →+∞ the distribution goes exponentially to zero. The average occupancy is

1 when ǫ −µ = τ log 2. At lower energies there is more than one particle in the state and

at higher energies there is less than one particle in the state.

The Bose-Einstein distribution, with µ = 0, is exactly the occupancy we came up

with for photons in blackbody radiation. Photons have spin 1, so they are bosons and

obey Bose-Einstein statistics. There is no lower limit on the wavelength, so the lowest

conceivable energy is arbitrarily close to zero which means µ ≤ 0.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 08-Oct-2004 13-7

At large energies both the Fermi-Dirac and Bose-Einstein distributions become

f(ǫ →+∞) →e

(µ −ǫ)/τ

.

In this limit the average occupancy is small and quantum eﬀects are negligible; this is the

classical limit. The classical distribution is called the Maxwell-Boltzmann distribution.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-1

Reading

K&K chapter 6 and the ﬁrst half of chapter 7 (the Fermi gas).

The Ideal Gas Again

Using the grand partition function, we’ve discussed the Fermi-Dirac and Bose-Einstein

distributions and their classical—low occupancy—limit, the Maxwell-Boltzmann distribu-

tion.

In lecture 7, we considered an ideal gas starting from the partition function. We

considered the states of a single particle in a box and we used the Boltzmann factor and

the number of such states to calculate the partition function for a single particle in a box.

Then we said the partition function for N weakly interacting particles is the product of N

single particle partition functions divided by N!,

Z

N

(τ) =

1

N!

Z

N

1

=

1

N!

(n

Q

V )

N

.

We introduced the factor of N! to account for the permutations of the N particles among

the single particle states forming the overall composite state of the system.

The introduction of this N! factor was something of a “fast one!” We gave a plausible

argument for it, but without a formalism that includes the particle number, it’s hard to

do more. Now that we have the grand partition function we can reconsider the problem.

In addition to cleaning up this detail, we also want to consider how to account for

the internal states of the molecules in a gas, the heat and work, etc., required for various

processes with an ideal gas, and also we want to consider the absolute entropy and see how

the Sackur-Tetrode formula relates to experiment.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-2

The N Particle Problem

The factor of N! in the ideal gas partition function was apparently controversial in

the early days of statistical mechanics. In fact, in Schroedinger’s book on the subject, he

has a chapter called “The N Particle Problem.”

I think this is kind of amusing, so let’s see what the N particle problem really is.

The free energy with the N! term is

F

C

= −τ log Z ,

= −τ log((n

Q

V )

N

/N!) ,

= −τ(N log n

Q

+N log V −N log N +N) ,

= −τN log

(mτ/2π¯h

2

)

3/2

(V/N)

−τN ,

where the subscript C denotes the “correct” free energy. Without the N! term, the “in-

correct” free energy is

F

I

= −τ log Z ,

= −τ log(n

Q

V )

N

,

= −τ(N log n

Q

+N log V ) ,

= −τN log

(mτ/2π¯h

2

)

3/2

V

**For the entropy, σ = −∂F/∂τ,
**

σ

C

= N log(n

Q

V/N) + (3/2)N +N ,

= N

log

n

Q

V

N

+

5

2

,

and

σ

I

= N log(n

Q

V ) + (3/2)N ,

= N

log(n

Q

V ) +

3

2

.

With a given amount of gas, the change in entropy between an initial and ﬁnal state is

given correctly by either formula,

σ

Cf

−σ

Ci

= σ

If

−σ

Ii

=

3

2

N log

τ

f

τ

i

+N log

V

f

V

i

.

But what happens when we change the amount of gas?

Note that N and V are both extensive quantities; the concentration, n = N/V , is an

intensive quantity. σ

C

is proportional to an extensive quantity. On the other hand, σ

I

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-3

contains an extensive quantity times the logarithm of an extensive quantity. This means

that the (incorrect) entropy is not proportional to the amount of gas we have!

For example, suppose we have two volumes V , each containing N molecules of (the

same kind of) gas at temperature τ. Then each has σ

I

= N(log(n

Q

V ) +3/2), for a total of

2N(log(n

Q

V )+3/2). We can imagine a volume 2V divided in half by a removable partition.

We start with the partition in place and the entropy as above. We remove the partition.

Now we have 2N molecules in a volume 2V . The entropy becomes σ

I

= 2N(log(2n

Q

V ) +

3/2) which exceeds the entropy with the partition in place by ∆σ

I

= 2N log 2! But did

anything really change upon removing the partition? What kind of measurements could

we make on the gas in either volume to detect whether the partition were in place or not???

Note that the total σ

C

is the same before and after the partition is removed.

We might consider the same experiment but performed with two diﬀerent kinds of

molecules, A and B. We start with N molecules of type A on one side of the partition and

N molecules of type B on the other side of the partition. Before the partition is removed,

we have

σ

C

= N

log

n

QA

V

N

+

5

2

+N

log

n

QB

V

N

+

5

2

,

where the two kinds of molecules may have diﬀerent masses and so might have diﬀerent

quantum concentrations. Now we remove the partition. This time we have to wait for

equilibrium to be established. We assume that no chemical reactions occur—we are only

waiting for the molecules to diﬀuse so that they are uniformly mixed. Once equilibrium

has been established, each molecule occupies single particle states in a volume 2V and the

entropy is

σ

C

= N

log

2n

QA

V

N

+

5

2

+N

log

2n

QB

V

N

+

5

2

,

which is 2N log 2 greater than the initial entropy. This increase is called the entropy of

mixing.

In the experiment with the same gas on both sides of the partition, the incorrect

expression for entropy gave an increase which turns out to be the same as the entropy

of mixing if we start out with two diﬀerent gases. This emphasizes the point that the

incorrect expression results from over counting the states by treating the molecules as

distinguishable.

In the mixing experiment, we can make measurements that tell us whether the par-

tition has been removed. If we sample the gas in one of the volumes and ﬁnd all the

molecules are type A, then we’re pretty sure that the partition hasn’t been removed! If we

ﬁnd a mixture of type A and type B, then we’re pretty sure that it has been removed.

Finally, note that if we go back to the case of the same gas, and reinsert the partition,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-4

then σ

I

decreases by 2N log 2. This is a violation of the second law!

The Ideal Gas From the Grand Partition Function

An ideal gas is the low occupancy limit of non-interacting particles. In this limit, both

the Fermi-Dirac and Bose-Einstein distributions become the Maxwell-Boltzmann distribu-

tion which is

f(ǫ) = e

(µ −ǫ)/τ

,

where f(ǫ) ≪1 is the average occupancy of a state with energy ǫ. The chemical potential,

µ, is found by requiring that the gas have the correct number of molecules,

N =

All states

e

(µ −ǫ)/τ

,

= e

µ/τ

All states

e

−ǫ/τ

,

= e

µ/τ

Z

1

,

= e

µ/τ

n

Q

V ,

where Z

1

is the single particle partition function we discussed earlier. Then

µ = τ log

n

n

Q

,

as we found earlier.

The free energy satisﬁes

∂F

∂N

τ,V

= µ(N, τ, V ) ,

so

F =

N

0

µ(N

′

, τ, V ) dN

′

,

=

N

0

τ log

N

′

n

Q

V

dN

′

,

= τ

N

0

(log N

′

−log(n

Q

V )) dN

′

,

= τ

N

′

log N

′

−N

′

−N

′

log(n

Q

V )

N

0

,

= Nτ

log

n

n

Q

−1

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-5

Of course, this is in agreement with what we had before. The N! factor that we previously

inserted by hand, comes about naturally with this method. (It is responsible for the N in

the concentration in the logarithm and the −1 within the parentheses.)

As a reminder, the pressure is found from the free energy by

p = −

∂F

∂V

τ,N

,

which gives the ideal gas equation of state

p =

Nτ

V

.

The entropy is found by diﬀerentiating with respect to the temperature,

σ = −

∂F

∂τ

V,N

,

which gives the Sackur-Tetrode expression,

σ = N

log

n

Q

n

+

5

2

.

The internal energy is most easily found from

U = F +τσ =

3

2

Nτ .

The energy of an ideal gas depends only on the number of particles and the temperature.

Since

dU = τ dσ −p dV +µdN ,

the change in energy at constant volume and particle number is just τ dσ. Then the heat

capacity at constant volume is

C

V

= τ

∂σ

∂τ

V,N

,

which for the case of an ideal gas is

C

V

=

3

2

N =

3

2

Nk ,

where the last expression gives the heat capacity in conventional units. The molar speciﬁc

heat at constant volume is (3/2)N

0

k = (3/2)R where R is the gas constant. The heat

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-6

capacity at constant pressure can be found by requiring that dV and dτ be such that p

doesn’t change.

C

p

= τ

∂σ

∂τ

p,N

=

∂U

∂τ

p,N

+p

∂V

∂τ

p,N

.

Since U depends only on N and τ,

∂U

∂τ

p,N

= C

V

.

With the ideal gas equation of state, V = (N/p)τ,

p

∂V

∂τ

p,N

= N ,

so

C

p

= C

V

+N , or C

p

= C

V

+Nk (in conventional units) .

For the molar heat capacities, we have

C

p

= C

V

+R ,

and for the ideal monatomic gas, these are

C

V

=

3

2

R , and C

p

=

5

2

R .

The ratio of speciﬁc heats is usually denoted by γ, which for an ideal monatomic gas is

γ =

C

p

C

V

=

5

3

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-7

Internal Degrees of Freedom

There are several corrections we might make to our treatment of the ideal gas. If

we go to high occupancies, our treatment using the Maxwell-Boltzmann distribution is

inappropriate and we should start from the Fermi-Dirac or Bose-Einstein distribution

directly.

We have ignored the interactions between molecules. This is a good approximation

for low density gases, but not so good for higher densities (but these higher densities can

still be low enough that the MB distribution applies). We will discuss an approximate

treatment of interactions in a few weeks when we discuss phase transitions.

Finally, we have ignored any internal structure of the molecules. We will remedy this

omission now. We imagine that each molecule contains several internal states with energies

ǫ

int

. Note that int is understood to be an index over the internal states. There may be

states with the same energy and states with diﬀering energies. In our non-interacting

model, the external energy is just the kinetic energy due to the translation motion of the

center of mass, ǫ

cm

. Again, cm is to be understood as an index which ranges over all states

of motion of the cm. Although we are considering internal energies, we are not considering

ionization or dissociation. When a molecule changes its internal state, we assume the

number of particles does not change.

Let’s consider the grand partition function for a single state of center of mass motion.

That is, we’re going to consider the grand partition function for single particle states—with

internal degrees of freedom—in a box. The energy of the particle is ǫ

cm

+ ǫ

int

. Then the

grand partition function is

Z = 1 +e

(µ −ǫ

cm

−ǫ

int,1

)/τ

+e

(µ −ǫ

cm

−ǫ

int,2

)/τ

+· · ·

+ two particle terms + three particle terms +· · · ,

= 1 +e

(µ −ǫ

cm

)/τ

int

e

−ǫ

int

/τ

+ two particle terms + three particle terms +· · · ,

= 1 +e

(µ −ǫ

cm

)/τ

Z

int

+ two particle terms + three particle terms +· · · ,

= 1 +e

(µ −ǫ

cm

)/τ

Z

int

+e

2(µ −ǫ

cm

)/τ

Z

2

int

2!

+e

3(µ −ǫ

cm

)/τ

Z

3

int

3!

+· · · ,

where Z

int

is the partition function for the internal states. The above expression is strictly

correct only for bosons. For fermions, we would need to be sure that the multiple particle

terms have all particles in diﬀerent states which means that the internal partition functions

do not factor as shown above.

However, we really don’t need to worry about this because we’re going to go to the

classical limit where the occupancy is very small. This means we can truncate the sum

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 11-Oct-2004 14-8

above after the second term,

Z = 1 +e

(µ −ǫ

cm

)/τ

Z

int

.

The mean occupancy of the center of mass state, whatever the internal state, is

f(ǫ

cm

) =

e

(µ −ǫ

cm

)/τ

Z

int

1 +e

(µ −ǫ

cm

)/τ

Z

int

≈ e

(µ −ǫ

cm

)/τ

Z

int

,

which is just the Maxwell-Boltzmann distribution with an extra factor of the internal

partition function, Z

int

.

Now we should modify our previous expressions to allow for this extra factor of Z

int

.

Recall that we chose the chemical potential to get the correct number of particles. In

that calculation, exp(µ/τ) must be replaced by exp(µ/τ)Z

int

, and everything else will go

through as before. Then our new expression for µ is

µ = τ log

n

n

Q

Z

int

= τ

log

n

n

Q

−log Z

int

.

The free energy becomes

F = F

cm

+F

int

= Nτ

log

n

n

Q

Z

int

−1

,

where F

cm

is our previous expression for the free energy due to the center of mass motion

of molecules with no internal degrees of freedom, and

F

int

= −Nτ log Z

int

,

is the free energy of the internal states alone. The expression for the pressure is unchanged

since in the normal situation, the partition function of the internal states does not depend

on the volume. (Is this really true? How do we get liquids and solids? Under what

conditions might it be a good approximation?) The expression for the entropy becomes

σ = σ

cm

+σ

int

,

where σ

cm

is our previous expression for the entropy of an ideal gas, the Sackur-Tetrode

expression, and

σ

int

= −

∂F

int

∂τ

V,N

=

∂(Nτ log Z

int

)

∂τ

V,N

= N log Z

int

+Nτ

∂(log Z

int

)

∂τ

V,N

.

The energy, U, and therefore the heat capacities, receive a contribution from the internal

states. The extra energy is

U

int

= F

int

+τσ

int

= F

int

−τ

∂F

int

∂τ

V,N

= −τ

2

∂

∂τ

F

int

τ

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-1

Examples of Z

int

We have been discussing how to modify our treatment to allow for the internal states

and energies of molecules in, for example, an ideal gas To make further progress, we need

to consider some speciﬁc examples of internal structure that can give rise to Z

int

. Suppose

the molecules are single atoms but these atoms have a spin quantum number S. Then

there are 2S +1 internal states that correspond to the 2S +1 projections of the spin along

an arbitrary axis. In the absence of a magnetic ﬁeld, all these states have the same energy

which we take as ǫ

int

= 0. Then Z

int

= 2S + 1 and

F

int

= −Nτ log(2S + 1) ,

σ

int

= N log(2S + 1) ,

U

int

= 0 ,

so the entropy is increased over that of a simple ideal gas, but the energy doesn’t change.

The increase in entropy is easy to understand. What’s happening is that each atom has

2S + 1 times as many states available as a simple atom with no internal structure. The

entropy, the logarithm of the number of states, increases by log(2S + 1) per atom.

That was a fairly trivial example. Here’s another one: Suppose that each molecule

has one internal state with energy ǫ

1

. Then Z

int

= exp(−ǫ

1

/τ) and

F

int

= −Nτ log Z

int

= +Nǫ

1

,

σ

int

= 0 ,

U

int

= Nǫ

1

,

and

∆µ = −τ log Z

int

= +ǫ

1

.

In this example, we didn’t change the entropy (each molecule has just one state), but we

added ǫ

1

to the energy of each molecule. This change in energy shows up in the chemical

potential as a per molecule change and it shows up in the free energy and energy as N

times the per molecule change. This example is basically a small test of the self-consistency

of the formalism!

More realistic examples include the rotational and vibrational states of the molecules.

Single atoms have neither rotational nor vibrational modes (they do have electronic exci-

tations!). A linear molecule (any diatomic molecule and some symmetric molecules such

as CO

2

, but not H

2

O) has two rotational degrees of freedom. Non-linear molecules have

three rotational degrees of freedom. Diatomic molecules have one degree of vibrational

freedom. More complicated molecules have more degrees of vibrational freedom. If the

molecule has M atoms, 3M coordinates are required to specify the locations of all the

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-2

atoms. The molecule thus has 3M degrees of freedom. Three of these are used in specify-

ing the location of the center of mass. Two or three are used for the rotational degrees of

freedom. The remainder are vibrational degrees of freedom.

You might be uncomfortable with 0 or two degrees of rotational freedom for point

or linear molecules. To make this plausible, recall that an atom consists of a nucleus

surrounded by an electron cloud. The electrons are in states with angular momentum,

and to change the angular momentum one or more electrons must be placed in an excited

electronic state. This is possible, but if there is an appreciable thermal excitation of such

states, the atom has a fair chance of being ionized. If the atom is part of a molecule, that

molecule has probably been dissociated as molecular binding energies are usually small

compared to atomic binding energies. The upshot of all this is that such excitations are

not important unless the temperature is high enough that molecules are dissociating and

atoms are ionizing!

Rotational energy is the square of the angular momentum divided by twice the moment

of inertia. (Ignoring things like the fact that inertia is a tensor!) Since angular momentum

is quantized, so is rotational energy. This means that at high temperatures, we expect

an average energy of τ/2 per rotational degree of freedom, but at low temperatures we

expect that the rotational modes are “exponentially frozen out.” In this case, they do not

contribute to the partition function, the energy, or the entropy. The spacing between the

rotational energy levels sets the scale for low and high temperatures.

Similarly, for each vibrational degree of freedom, we expect that the corresponding

normal mode of oscillation can be treated as a harmonic oscillator and that at high tem-

peratures there will be an average energy of τ per vibrational degree of freedom (τ/2 in

kinetic energy and τ/2 in potential energy). At low temperatures the vibrational modes

are exponentially frozen out and do not contribute to the internal partition function, the

energy or the entropy. ¯ h times the frequency of vibration sets the scale for low and high

temperatures.

As an example, consider a diatomic gas. At low temperatures, the energy will be

3Nτ/2, the entropy will be given by the Sackur-Tetrode expression and the molar heat

capacities will be C

V

= 3R/2 and C

p

= 5R/2 with γ = 5/3. As the temperature is raised

the rotational modes are excited and the energy becomes 5Nτ/2 with molar speciﬁc heats

of C

V

= 5R/2 and C

p

= 7R/2 and γ = 7/5. If the temperature is raised still higher the

vibrational modes can be excited and U = 7Nτ/2, C

V

= 7R/2, C

p

= 9R/2, and γ = 9/7.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-3

Ideal Gas Processes

We will consider various processes involving a ﬁxed amount of an ideal gas. We

will assume that the heat capacities are independent of temperature for these processes.

(In other words, the temperature changes will not be large enough to thaw or freeze the

rotational or vibrational modes.) We will want to know the work done, heat added, the

change in energy and the change in entropy of the system.

Note that work and heat depend on the process, while energy and entropy changes

depend only on the initial and ﬁnal states. For the most part we will consider reversible

processes.

Consider a constant volume process. About the only thing one can do is add heat! In

this case, p

f

/p

i

= T

f

/T

i

.

Q = nC

V

(T

f

−T

i

) ,

W = 0 ,

∆U = nC

V

(T

f

−T

i

) ,

∆S =

nC

V

dT

T

= nC

V

log

T

f

T

i

,

where Q is the heat added to the gas, W is the work done on the gas, n is the number of

moles, C

V

and C

p

are the molar heat capacities in conventional units and T and S are the

temperature and entropy in conventional units.

Consider a constant pressure (isobaric) process. In this case, if heat is added, the gas

will expand and V

f

/V

i

= T

f

/T

i

Q = nC

p

(T

f

−T

i

) ,

W = −

V

f

V

i

p dV = −nR(T

f

−T

I

) ,

∆U = nC

V

(T

f

−T

i

) ,

∆S = nC

p

T

f

T

i

dT

T

= nC

p

log

T

f

T

i

= nC

V

log

T

f

T

i

+nRlog

V

f

V

i

.

Consider a constant temperature (isothermal) process. Heat is added and the gas

expands to maintain a constant temperature. The pressure and volume satisfy p

f

/p

i

=

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-4

(V

f

/V

i

)

−1

.

W = −

V

f

V

i

p dV = −nRT

V

f

V

i

dV

V

= −nRT log

V

f

V

i

,

∆U = 0 ,

Q = −W = nRT log

V

f

V

i

,

∆S = nR

V

f

V

i

dV

V

= nRlog

V

f

V

i

.

Consider a constant entropy process. This is often called an adiabatic process. How-

ever, adiabatic is also taken to mean that no heat is transfered. Since it is possible to

change the entropy without heat transfer, the term isentropic can be used to explicitly

mean that the entropy is constant. It is left as an exercise to show that in an isentropic

process with an ideal gas, pV

γ

= constant. Then

W = −

V

f

V

i

p dV = −p

i

V

γ

i

V

f

V

i

dV

V

γ

=

p

i

V

γ

i

γ −1

1

V

γ−1

f

−

1

V

γ−1

i

= −

nRT

i

γ −1

1 −

V

i

V

f

γ−1

,

Q = 0 ,

∆U = W = −

nRT

i

γ −1

1 −

V

i

V

f

γ−1

,

∆S = 0 .

Finally, let’s consider an irreversible process. Suppose a gas is allowed to expand from

a volume V

i

into a vacuum until its volume is V

f

. This is called a free expansion. No

work is done to the gas and no heat is added, so the energy and temperature don’t change.

The initial and ﬁnal states are the same as in the reversible isothermal expansion, so the

entropy change is the same as for that case,

Q = 0 ,

W = 0 ,

∆U = 0 ,

∆S = nRlog

V

f

V

i

.

This is an adiabatic, but not isentropic, process. Note that if a gas is not ideal, then it may

be that the energy depends on volume (or rather, concentration) as well as temperature.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-5

Such a deviation from the ideal gas law can be uncovered by measuring the temperature

of a gas before and after a free expansion.

The Gibbs Paradox Revisited

Last lecture’s treatment of the N particle problem might have engendered some un-

easiness; especially the example with two volumes of gas that were allowed to mix. Recall

that we had two volumes, V , each containing N molecules of gas at temperature τ, and

separated by a partition. We considered two cases: the same gas on both sides of the

partition and diﬀerent gases, A and B, on the two sides of the partition. When the parti-

tion is removed in the same gas case “nothing happens,” the system is still in equilibrium

and the entropy doesn’t change—according to the correct expression which included the

N! over counting correction in the partition function. When the partition is removed in

the diﬀerent gas case, we must wait a while for equilibrium to be established and once

this happens, we ﬁnd that the entropy has gone up by 2N log 2.This is called the entropy

of mixing. The incorrect expression for the entropy (omitting the N! over counting cor-

rection in the partition function) gives the same entropy of mixing in both cases. This

manifestation of the N particle problem is called the “Gibbs paradox.”

The fact that we have to wait for equilibrium to be established means that the mixing

of the two diﬀerent gases is a non-reversible process. Entropy always increases in non-

reversible processes! On the other hand, removing the partition between identical gases

is a reversible process (in the limit of a negligible mass, frictionless partition. . .). In a

reversible process, total entropy (system plus surroundings) does not increase, and there is

obviously no entropy change in the surroundings when the partition is removed from the

identical gases.

The question of measuring the entropy has come up several times. There is no such

thing as an entropy meter that one can attach to a system and out pops a reading of the

entropy! Changes of the entropy can be measured. Recall that dσ = ¯ dQ/τ for a reversible

process. So if we can take a system from one state to another via a (close approximation

of a) reversible process and measure the heat ﬂow and temperature, we can deduce the

entropy diﬀerence between the two states. To measure the absolute entropy of a state, we

must start from a state whose absolute entropy we know. This is a state at τ = 0! We will

see how this goes in the comparison of the Sackur-Tetrode expression with experimental

results.

Aside: the fact that we can only measure changes in entropy should not be that

bothersome. At the macroscopic level, entropy is deﬁned by an integral (

dQ/τ). There

is always the question of the constant of integration. A similar problem occurs with

potential energy. It is potential energy diﬀerences that are important to the dynamics and

only diﬀerences can be measured. For example, consider a mass m on the surface of the

Earth. If we take the zero of gravitational potential energy to be at inﬁnite separation of

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-6

the mass and the Earth, then the potential energy of the mass-Earth system is −GMm/R

when the mass sits on the surface of the Earth at distance R from the center. I’m sure we’re

all happy with this, right? But, there is no potential energy meter that you can attach to

the mass and out pops a potential energy value. Instead, −GMm/R is a calculated value

much like the entropy of mixing is a calculated value. What can we actually measure in

the gravitational case? We can measure the force required to change the height (distance

from the center of the Earth) of the mass and so measure

**F · dr. That is, we can measure
**

the change in gravitational potential energy between two states. Of course, we have to

be careful that there is no friction, that F = −mg, that there is negligible acceleration

of the mass, etc. In other words, we have to approximate a reversible process! Reversible

processes aren’t just for thermodynamics! I suspect they’re easier to visualize in other

branches of physics, so they don’t cause as much comment and concern. What about

measuring the “absolute” gravitational potential? This requires measuring the changes in

potential energy between the state whose potential we know (inﬁnite separation) and the

state whose potential we want to know (mass on the surface of the Earth). I suppose if we

had enough money, we might get NASA to help with this project! Of course, by calculation

we can relate the “absolute” gravitational potential to other quantities, for example, the

escape velocity, that can be more easily measured. This is one of the arts of theoretical

physics.

Back to our mixing example: Can we think of a reversible process which would allow

us to mix the gases? Then we could calculate the entropy change by keeping track of the

heat added and the temperature at which it was added. Also, if we knew of such a process.

we could use it—in reverse!—to separate the gases again. The process I have in mind uses

semi-permeable membranes. We need two of them: one that passes molecules of type A

freely but is impermeable to molecules of type B, and a second which does the opposite.

It passes type B molecules and blocks type A molecules. We can call these “A-pass”

and “B-pass” membranes for short. Do such membranes actually exist? Semi-permeable

membranes certainly exist. The molecules that are passed may not pass through “freely,”

but if we move the membrane slowly enough, it should be possible to make the friction

due to the molecules passing through the small holes in the membrane negligibly small.

The possibility of ﬁnding the desired membranes depends on the molecules in question and

almost certainly is not possible for most pairs of molecules. However, the fact that semi-

permeable membranes do exist for some molecules would seem to make this a reasonable

thought experiment (if not an actually realizable experiment).

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-7

The ﬁgure is a schematic of our mix-

ing apparatus. The volume 2V is in equi-

librium with a thermal bath at tempera-

ture τ. At the center of the volume and

dividing it into two sections of volume V

are the two membranes. The A-pass mem-

brane conﬁnes the N type B molecules to

the right volume and the B-pass mem-

brane conﬁnes the N type A molecules

to the left volume. The next two ﬁgures

show the situations when the gases are

partially and fully mixed. The membranes

are something like pistons and are moved

by mechanical devices that aren’t shown.

These devices are actually quite impor-

tant as each membrane receives a net force

from the gases. The mechanical devices

are used to counteract this force and do work on the gases as the membranes are moved

slowly and reversibly through the volume.

What is the force on a membrane due

to the gases? Consider the A-pass mem-

brane. A molecules pass freely through

this membrane so there is no interaction

of this membrane with the A molecules.

The B molecules are blocked by this mem-

brane, so the B molecules are bouncing oﬀ

the membrane as though it were a solid

surface. Since there are B molecules on

the right side of this membrane and not on

the left, there is a pressure (only from the

B molecules) which is just Nτ/V

B

where

V

B

is the volume occupied by B molecules

to the right of the A-pass membrane. The

net force from this pressure points to the

left. So as we move the membrane to the

left, the B molecules do work on it. This

comes from the energy, U

B

of the B molecules. The B molecule system would cool, ex-

cept it is in contact with the heat bath, so heat ﬂows from the bath to make up for the

work done on the membrane and keep τ and hence U

B

constant. The same thing happens

with the B-pass membrane and the A gas. It is the heat transfered (reversibly) from the

reservoir to each gas that increases the entropy of the gas.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 13-Oct-2004 15-8

By now, you’re convinced that the A

molecules can be treated as a gas occu-

pying the volume to the left of the B-

pass membrane without worrying what’s

going on with the B molecules and vice-

versa. We’ve arranged this “by construc-

tion.” Our model for an ideal gas is based

on non-interacting molecules (well, weakly

interacting, but only enough to maintain

thermal equilibrium). We’ve also made

the membranes so they interact only with

A or B molecules but not both. So the A

molecules interact strongly with the walls

of the container and the B-pass membrane

and interact weakly (→ 0) with every-

thing else including other A molecules. So

when the B pass membrane is moved all

the way to the right, the A molecules undergo an isothermal expansion from V to 2V . We

apply our ideal gas results for an isothermal expansion and ﬁnd

∆σ

A

=

2V

V

dQ

τ

=

2V

V

p dV

τ

=

2V

V

N

dV

V

= N log

2V

V

= N log 2 .

Of course, a similar result applies to the B molecules when the A pass membrane is moved

all the way to the left. The total change of entropy in this process is

∆σ = 2N log 2 ,

which is what we had obtained before by applying the Sackur-Tetrode expression to the

initial and ﬁnal states of the irreversible process.

Aside: suppose we have several ideal gases occupying the same volume. p

i

= N

i

τ/V

is called the partial pressure of gas i and is the pressure that the same N

i

molecules of the

gas would have if they occupied the volume by themselves (no other gases present). Then

the total pressure is the sum of the partial pressures: p =

i

p

i

. This is called Dalton’s

law. It falls out of our ideal gas treatment “by construction.” Since the gases are non-

interacting, the presence of other gases cannot aﬀect the rate of momentum transfer by a

given gas! So, Dalton’s law seems trivial, but it probably helped point the way towards a

non-interacting model as a good ﬁrst approximation.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-1

The Sackur-Tetrode Entropy and Experiment

In this section we’ll be quoting some numbers found in K&K which are quoted from

the literature.

You may recall that I’ve several times asked how one would measure absolute entropy?

I suspect that I pretty much gave it away (if you hadn’t ﬁgured it out already) in the last

section. The answer is you have to measure heat transfers from a state of known absolute

entropy to the desired state so that you can calculate

**dQ/τ. What is a state of known
**

entropy? Answer, at absolute 0, one expects the entropy to be very small and we can take

it to be 0. Actually, there is the third law of thermodynamics (not as famous as the ﬁrst

two!) which says that the entropy should go to a constant as τ →0.

At absolute 0, a reasonable system will be in its ground state. In fact the ground state

might not be a single state. For example if we consider a “perfect crystal,” its ground

state is clearly unique. But real crystals have imperfections. Suppose a crystal is missing

a single atom from its lattice. If there are N atoms in the crystal there are presumably N

diﬀerent sites from which the atom could be missing so the entropy is log N. Also, there’s

presumably an energy cost for having a missing atom, so the crystal is not really in its

ground state. But this might be as close as we can get with a real crystal. The point is

that the energy and the entropy are both very small in this situation and very little error

is made by assuming that σ(0) = 0. (Compare log N with N log(n

Q

/n) when N ∼ 10

23

!)

In fact, a bigger problem is getting to very low temperatures. In practice, one gets as

low as one can and then extrapolates to τ = 0 using a Debye law (assuming an insulating

solid). So to measure the entropy of a monatomic ideal gas such as neon, one makes heat

capacity measurements and does the integral

**C(τ) dτ/τ. The heat capacity measure-
**

ments go to as low a τ as needed to get a reliable extrapolation to 0 with the Debye law.

According to K&K, the calculation goes like this: solid neon melts at 24.55 K. At the

melting point, its entropy (by extrapolation and numerical integration) is

S

melting

−S

0

= 14.29

J

mol K

.

To melt the solid (which occurs at a constant temperature) requires 335 J mol

−1

so the

entropy required to melt is

∆S

melt

= 13.65

J

mol K

.

Again, a numerical integration is required to ﬁnd the entropy change as the liquid neon is

taken from the freezing point to the boiling point at 27.2 K. This is

S

boiling

−S

freezing

= 3.85

J

mol K

.

Finally, 1761 J mol

−1

is required to boil the neon at the boiling point, and

∆S

boil

= 64.74

J

mol K

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-2

Now we have a gas to which we can apply the Sackur-Tetrode expression. Assuming

S

0

= 0, the total is

S

vapor

= ∆S

boil

+ (S

boiling

−S

freezing

) + ∆S

melt

+ (S

melting

−S

0

) = 96.40

J

mol K

,

σ = 6.98 ×10

24

/mol ,

where I have quoted the sum from K&K which diﬀers slightly from the sum you get by

adding up the four numbers presumably because there is some round-oﬀ in the input

numbers. (For example, using a periodic table on the web, I ﬁnd the melting and boiling

points of neon are 24.56 K and 27.07 K.) According to K&K, the Sackur-Tetrode value

for neon at the boiling point is

S

Sackur−Tetrode

= 96.45

J

mol K

,

which is in very good agreement with the observed value.

When I plug into the Sackur-Tetrode expression I actually get,

S

Sackur−Tetrode

= 96.47

J

mol K

,

still in very good agreement with the observed value. Why did I get a slightly diﬀerent

value than that quoted in K&K? I used

S = R

¸

log

¸

mkT

2π¯h

2

3/2

p

kT

¸

+

5

2

¸

,

Everything can be looked up, but I’m using p/kT instead of N

0

/V , which assumes the

ideal gas law is valid. However, this expression is being applied right at the boiling point,

so it’s not clear that the ideal gas law should work all that well.

Some other things to note. (1) If we had left out the N! over counting correction, We

would have to add

R(log N

0

−1) = 447

J

mol K

,

to the above. This swamps any slight problems with deviations from the ideal gas law or

inaccuracies in the numerical integrations! (2) The Sackur-Tetrode expression includes ¯h

which means it depends on quantum mechanics. So this is an example where measurements

of the entropy pointed towards quantum mechanics. Of course, ¯ h occurs inside a logarithm,

so it might not have been so easy to spot!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-3

The Ideal Fermi Gas

Consider a metal like sodium or copper (or the other metals in the same columns in the

periodic table). These metals have one valence electron—an electron which can be easily

removed from the atom, so these atoms often form chemical bonds as positively charged

ions. In the solid metal, the valence electrons aren’t bound to the atoms. How do we know

this? Because the metals are good conductors of electricity. If the electrons were bound to

the atoms they would be insulators. Of course, there are interactions between the electrons

and the ions and between the electrons and other electrons. But, as a ﬁrst approximation

we can treat all the valence electrons as forming a gas of free (non-interacting) particles

conﬁned to the metal.

Let’s do a little numerology. First, let’s calculate the quantum concentration for an

electron at room temperature,

n

Q

=

m

e

kT

2π¯h

2

3/2

,

=

(9.108 ×10

−28

g) (1.380 ×10

−16

erg K

−1

) (300 K)

2π (1.054 ×10

−27

erg s)

2

3/2

,

= 1.26 ×10

19

cm

−3

,

=

1

43

˚

A

3

.

In other words, the density of electrons is equal to the room temperature quantum con-

centration if there is one electron every 43

˚

A. Now consider copper. It has a density of

8.90 g cm

−3

and an atomic mass of 63.54 amu. So the number density of copper atoms is

n

Cu

= 8.44 ×10

22

cm

−3

=

1

2.3

˚

A

3

.

The number of electrons in the electron gas (assuming one per copper atom) exceeds the

quantum concentration by a factor of 6700. For copper the actual concentration and the

quantum concentration are equal at a temperature of about 100,000 K (assuming we could

get solid copper that hot!).

The upshot of all this is that we are deﬁnitely not in the classical domain when dealing

with an electron gas in metals under normal conditions. We will have to use the Fermi-

Dirac distribution function. Low energy states are almost certain to be ﬁlled. When this

is true, the system is said to be degenerate. Furthermore, the electron gas is “cold” in the

sense that thermal energies are small compared to the energies required to conﬁne them

to high densities. (This is most easily seen from an uncertainty principle argument.)

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-4

So as a ﬁrst approximation, we can use the Fermi-Dirac distribution at zero temper-

ature. This means we will ignore thermal energies altogether. At zero temperature, the

Fermi-Dirac distribution becomes,

f(ǫ) =

1

e

(ǫ −µ)/τ

+ 1

→

1, ǫ < µ ;

0, ǫ > µ .

Imagine a chunk of copper in which all the valence electrons have been removed (it would

have a rather large electric charge . . .). Add back one valence electron remembering that

the temperature is 0. This electron goes into the lowest available state. Add another

electron, it goes into the state with the next lowest energy. Actually it’s the same center

of mass state and the same energy, but the second electron has its spin pointing in the

opposite direction from the ﬁrst. The third electron goes in the state with the next lowest

energy. And so on. What we are doing is ﬁlling up states (with no gaps) until we run out

of valence electrons. Since we have the lowest possible energy, this conﬁguration must be

the ground state (which is the state the system should be in at 0 temperature!).

We must choose the chemical potential so that our metal has the correct number

of valence electrons. To do this, we need to know the number of states. Since we are

considering free electrons, we are dealing with single particle states in a box. This is the

same calculation we’ve done before. The number of states with position vector in the

element d

3

x and momentum vector in the element d

3

p is

dn(x, p) = 2

d

3

x d

3

p

8π

3

¯h

3

,

where the factor of 2 arises because there are two spin states for each center of mass state.

When the number of states is used in an integral, the integral over d

3

x just leads to the

volume of the box, V . The element d

3

p = p

2

dp dΩ and the solid angle may be integrated

over to give 4πp

2

dp. Finally, the independent variable may be converted from momentum

to energy with p

2

/2m = ǫ, and we have

dn(ǫ) =

V

2π

2

2m

¯h

2

3/2

√

ǫ dǫ .

It’s customary to write this as the density of states per unit energy

D(ǫ) dǫ =

V

2π

2

2m

¯h

2

3/2

√

ǫ dǫ .

Now we’re ready to calculate µ. At zero temperature, the occupancy is 1 up to µ and

0 above µ, so the total number of electrons is

N =

µ

0

D(ǫ) dǫ .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-5

Before we do this integral, a bit of jargon. The energy of the highest ﬁlled state at zero

temperature is called the Fermi energy, ǫ

F

. So µ(τ = 0) = ǫ

F

. Then

N =

ǫ

F

0

V

2π

2

2m

¯h

2

3/2

√

ǫ dǫ =

V

3π

2

2m

¯h

2

3/2

ǫ

3/2

F

,

or

ǫ

F

= (3π

2

n)

2/3

¯h

2

2m

,

where n = N/V is the concentration. One also speaks of the Fermi temperature deﬁned by

τ

F

= kT

F

= ǫ

F

. This is not actually the temperature of anything, but is a measure of the

energy that separates degenerate from non-degenerate behavior. The Fermi temperature

is a few tens of thousands of Kelvins for most metals, so the electron gas in typical metals

is cold. Having determined the Fermi energy, we can determine the total energy of the

gas. We just add up the energies of all the occupied states

U

0

=

ǫ

F

0

ǫ

V

2π

2

2m

¯h

2

3/2

√

ǫ dǫ =

V

5π

2

2m

¯h

2

3/2

ǫ

5/2

F

=

V

5π

2

(3π

2

n)

5/3

¯h

2

2m

=

3

5

Nǫ

F

,

where the subscript on U indicates the ground state energy.

In the ground state, the average energy of an electron is 3/5 the Fermi energy. Also

note that the concentration contains V

−1

which means U

0

∝ V

−2/3

which means that as

the system expands, the energy goes down which means it must be exerting a pressure on

its container. This is called degeneracy pressure. In fact,

p = −

∂U

0

∂V

σ,N

=

2

3

U

0

V

,

so

pV =

2

3

U

0

,

just as for an ideal gas. Note that the derivative is to be taken at constant entropy. We

are dealing with the ground state, so the entropy is constant at 0.

As a point of interest, using the concentration for copper that we calculated earlier,

we ﬁnd

ǫ

F

= 7.02 eV and T

F

= 81, 500 K,

and the electron gas in copper really is “cold” all the way up to the point where copper

melts! (1358 K)

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-6

Heat Capacity of a Cold Fermi Gas

In the preceding section we considered the Fermi gas in its ground state. This does

not allow us to consider adding heat to the gas because the gas would no longer be in the

ground state. To calculate the heat capacity, we need to expand our treatment a bit.

What we need to do is calculate the energy of the gas as a function of temperature. We

will calculate the diﬀerence between the ground state energy and the energy at temperature

τ and we will make use of the fact that the gas is cold.

With a cold gas, all the action occurs within τ of µ. That is the occupancy goes from

1 to 0 over a range of a few τ centered at µ. Since we have a cold gas, this is a relatively

narrow range.

The diﬀerence in energy between the gas at temperature τ and the gas in the ground

state is

∆U(τ) =

∞

0

D(ǫ)f(ǫ)ǫ dǫ −U

0

,

=

∞

0

D(ǫ)f(ǫ)(ǫ −ǫ

F

) dǫ +

∞

0

D(ǫ)f(ǫ)ǫ

F

dǫ −U

0

,

=

∞

0

D(ǫ)f(ǫ)(ǫ −ǫ

F

) dǫ +Nǫ

F

−U

0

.

Now, we diﬀerentiate with respect to τ to get the heat capacity.

C

V

=

∂∆U

∂τ

,

=

∞

0

D(ǫ)

df(ǫ)

dτ

(ǫ −ǫ

F

) dǫ .

So far, everything is “exact,” now we start making approximations. At τ = 0, the distribu-

tion is a step function, so its derivative is a delta function (a very sharply peaked function

in the neighborhood of the step). This means that the main contribution to the integral

occurs (even if τ is not 0) when ǫ is very close to µ. So we will ignore the variation in the

density of states, evaluate it at µ and take it out of the integral. What about µ? At τ = 0,

µ = ǫ

F

. As τ increases, µ decreases, but when τ ≪ǫ

F

, the change in µ is negligibly small

(plot some curves!), so we will take µ = ǫ

F

. Then we have

C

V

= D(ǫ

F

)

∞

0

df(ǫ)

dτ

(ǫ −ǫ

F

) dǫ .

Now,

df

dτ

=

d

dτ

1

e

(ǫ −ǫ

F

)/τ

+ 1

=

ǫ −ǫ

F

τ

2

e

(ǫ −ǫ

F

)/τ

e

(ǫ −ǫ

F

)/τ

+ 1

2

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 15-Oct-2004 16-7

At this point, we change variables to x = (ǫ −ǫ

F

)/τ and we have

C

V

= τD(ǫ

F

)

+∞

−∞

x

2

e

x

dx

(e

x

+ 1)

2

,

where the actual lower limit of integration, −ǫ

F

/τ, has been replaced by −∞ since all the

contribution to the integral is in the neighborhood of x = 0. It turns out that the integral

is π

2

/3, so

C

V

=

π

2

3

D(ǫ

F

)τ ,

a surprisingly simple result! If we plug in the expression for the density of states, we have

D(ǫ

F

) =

3N

2ǫ

F

,

and

C

V

=

π

2

2

N

τ

ǫ

F

=

π

2

2

N

τ

τ

F

.

In conventional units,

C

V

=

π

2

2

Nk

T

T

F

.

Some comments. This is proportional to T which means that the energy of the electron

gas is U

0

+ constant · τ

2

. Can we see how this happens? In going from 0 to τ, we are

exciting electrons in the energy range from ǫ

F

−τ →ǫ

F

by giving them a thermal energy of

roughly τ. The number of such electrons is roughly Nτ/ǫ

F

, so the added energy is roughly

Nτ

2

/ǫ

F

. The Fermi gas heat capacity is quite a bit smaller than that of a classical ideal gas

with the same energy and pressure. This is because only the fraction τ/τ

F

of the electrons

are excited out of the ground state. At low temperatures, heat capacities of metals have

a linear term due to the electrons and a cubic term due to the lattice. Some experimental

data may be found in K&K.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-1

Reading

Finish K&K chapter 7 and start on chapter 8. Also, I’m passing out several Physics

Today articles. The ﬁrst is by Graham P. Collins, August, 1995, vol. 48, no. 8, p. 17,

“Gaseous Bose-Einstein Condensate Finally Observed.” This describes the research leading

up the ﬁrst observation of a BE condensate that’s not a superﬂuid or superconductor. The

second is by Barbara Goss Levi, March, 1997, vol. 50, no. 3, p. 17, “Bose Condensates are

Coherent Inside and Outside an Atom Trap,” describing the ﬁrst “atom laser” which was

based on a BE condensate. The third is also by Levi, October, 1998, vol. 51, no. 10, p. 17,

“At Long Last, a Bose-Einstein Condensate is Formed in Hydrogen,” describing even more

progress on BE condensates.

In addition, there is a recent Science report on an atomic Fermi Gas, DeMarco, B.,

and Jin, D. S., September 10, 1999, vol. 285, p. 1703, “Onset of Fermi Degeneracy in a

Trapped Atomic Gas.”

Bose condensates and Fermi degeneracy are current hot topics in Condensed Matter

Research. Searching the preprint server or “Googling” with appropriate keywords is bound

to turn up many more articles.

More on Fermi Gases

So far, we’ve considered the zero temperature Fermi gas and done an approximate

treatment of the low temperature heat capacity of Fermi gases. The zero temperature

Fermi gas was straightforward. We simply said that all states, starting from the lowest

energy state, are ﬁlled until we run out of particles. The energy at which this happens

is called the Fermi energy and is the same as the chemical potential at 0 temperature,

ǫ

F

= µ(τ = 0). Basically, all we had to do was determine the density of states, a problem

we’ve dealt with before.

Working on the low temperature heat capacity required an approximate calculation

of the energy versus temperature for a cold Fermi gas. In this calculation we assumed

that the density of states near the Fermi energy is constant and this allows one to pull

the density of states out of the integral and also to set the chemical potential to its 0

temperature value.

These approximations work quite well for the electron gas in metals at room tempera-

ture because the Fermi temperature for these electron is typically several tens of thousands

of Kelvins.

To calculate the energy, etc., at arbitrary temperatures, one must numerically inte-

grate the Fermi-Dirac distribution times the density of states to obtain the number of

particles. Then the chemical potential is varied until the desired number of particles is

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-2

obtained. Knowing the chemical potential, one can integrate the density of states times

the Fermi-Dirac distribution times the energy to get the energy at a given temperature.

All of this requires numerical integration or approximate techniques.

Figure 7.9 and tables 7.2 and 7.3 of K&K demonstrate that the low temperature heat

capacities (low enough that the Debye lattice vibrations are accurately following a T

3

heat

capacity) have a component proportional to the temperature and list the proportionality

constants for various metals. One thing you will notice is that the proportionality constants

agree with the calculations to only ∼ 30% and up to a factor of 2 in at least one case. This

is most likely due to the fact that the electrons are not really a non-interacting gas. Also,

there are eﬀects due to the crystal structure such as energy bands and gaps.

Other Fermi Gases

In addition to the conduction electron gas in metals, Fermi gases occur in other

situations.

In heavy elements, the number of electrons per atom becomes large enough that a

statistical treatment is a reasonable approximation. This kind of treatment is called the

Thomas-Fermi (or sometimes the Fermi-Thomas) model of the atom.

Also in heavy elements, the number of nucleons (neutrons and protons) in the nucleus

is large and, again, a statistical treatment is a reasonable approximation. The radius of a

nucleus is

R ≈ (1.3 ×10

−13

cm) · A

1/3

,

where A is the number of nucleons. The coeﬃcient in this relationship can vary by a

tenth or so depending on just how one measures the size—scattering by charged particles,

scattering by neutrons, eﬀects on atomic structure, etc. Aside: the unit of length 10

−13

cm

which is one femtometer is called the Fermi in nuclear physics. The volume of a nucleus is

V =

4π

3

2.2 ×10

−39

A cm

3

,

and the number density or concentration is

n

nuc

=

A

V

= 1.1 ×10

38

cm

−3

.

The nuclear density (with this number of signiﬁcant digits, the mass diﬀerence between

neutrons and protons is negligible) is

ρ

nuc

= 1.8 ×10

14

g cm

−3

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-3

Basically, all nuclei have the same density. Of course, this is not quite true. Nuclei have a

shell structure and “full shell” nuclei are more tightly bound than partially full shell nuclei.

Also, the very lightest nuclei show some deviations. Nevertheless, the density variations

aren’t large and it’s reasonable to speak of the nuclear density.

The neutron to proton ratio in nuclei is about 1 : 1 for light nuclei up to about 1.5 : 1

for heavier nuclei. Assuming the latter value, then it is the neutrons whose Fermi energy

is important.

ǫ

F

=

¯h

2

2m

n

3π

2

(0.6 · n

nuc

)

2/3

= 5.2 ×10

−5

erg = 32 MeV .

This is a little larger than K&K’s number because it’s computed for a nucleus with 40% pro-

tons and 60% neutrons, instead of equal numbers. Since the average kinetic energy in a

Fermi gas is 3ǫ

F

/5, the average kinetic energy is about 19 MeV in a heavy nucleus. The

experimentally determined binding energy per nucleon is about 8 MeV. This varies some-

what, especially for light nuclei; it reaches a peak at

56

Fe. To the extent that the binding

energy per nucleon and the kinetic energy per nucleon are constant, the potential energy

per nucleon is also constant. This reﬂects the fact that the nuclear force is the short range

strong force and nuclei only “see” their nearest neighbors. The strong force is about the

same between neutrons and protons, between protons and protons and between neutrons

and neutrons. But, the protons have a long range electromagnetic interaction. As the

number of particles goes up the “anti-binding” energy of the protons goes up faster than

the number of protons (can you ﬁgure out the exponent?) so the equilibrium shifts to

favor neutrons in spite of the fact that they are slightly more massive than protons.

The Fermi temperature for neutrons in a heavy nucleus is

T

F

= ǫ

F

/k = 3.8 ×10

11

K,

so nuclei (which are usually in their ground state) are very cold!

In a star like the Sun, gravity is balanced by the pressure of a very hot, but classical,

ideal gas. The Sun has a mass about 300,000 times that of the Earth and a radius about

100 times that of the Earth, so the average density of the Sun is somewhat less than that

of the Earth (it’s about the density of water!). The temperature varies from about 20

million Kelvins at the center to about 6000 K at the surface. So it’s completely gaseous

and the electrons are non-degenerate throughout. Since the sun is radiating, it is cooling.

Energy is supplied by nuclear reactions in the Sun’s core.

A typical white dwarf star has about the mass of the Sun but the radius of the Earth.

It’s the degeneracy pressure of the electrons that balances gravity in a white dwarf. White

dwarves shine by cooling. There are no nuclear reactions in the core, so after they cool

enough, they become invisible. White dwarves are discussed in K&K, so let’s move on to

neutron stars which are not discussed in K&K.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-4

Neutron Stars

In a neutron star it’s the degeneracy pressure of the neutrons that balances gravity.

A typical neutron star has a mass like the Sun (M

⊙

= 2 × 10

33

g) but a radius smaller

than New Jersey, let’s say R ≈ 10 km. Let’s assume that the mass in a neutron star is

uniformly distributed. What’s the density?

ρ = M/V = 4.8 ×10

14

g cm

−3

,

about three times nuclear density. (Of course, the density in a star is not uniform and it

may exceed 10 times nuclear density in the center, but we’re just trying to do a back of

the envelope calculation here.) In terms of the concentration of neutrons, this corresponds

to

n

0

= 2.9 ×10

38

cm

−3

.

The Fermi energy for these neutrons is

ǫ

F,0

≈ 86 MeV ,

and the Fermi temperature is

T

F

= 10

12

K.

Neutron stars are nowhere near this hot. Otherwise they would be very strong sources of

gamma rays. Instead they are thought to have temperatures of millions of degrees and

radiate X-rays. I believe there are some observations which indicate this. Also, due to

having a magnetic ﬁeld and rotating, they can radiate electromagnetic energy and are

observed as pulsars. In any case, the neutrons in a neutron star are cold!

An interesting question is why is a neutron star made of neutrons? (Well, if it weren’t,

we probably wouldn’t call it a neutron star, but besides that?) In particular, what’s

wrong with the following? Let the star be made of protons and electrons, each with the

concentration we’ve just calculated. Then the star is electrically neutral because there

is a sea of positively charged protons and a sea of negatively charged electrons. But the

protons have a slightly lower mass than the neutrons and this is true even if one adds in

the mass of the electron, so this conﬁguration would seem to be energetically favored over

the neutron conﬁguration. In fact, a free neutron decays according to

n →p +e

−

+ ¯ ν

e

,

where ¯ ν

e

is the electron anti-neutrino. The half life is about 15 minutes. Neutrinos are

massless (or very nearly so) and for our purposes we can ignore them. That is, we can

assume that the neutrons are in equilibrium with the protons and electrons. If we need to

change a neutron into a proton and electron, the above reaction will do it. If we need to

change a proton and electron into a neutron, there is

p +e

−

→n +ν

e

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-5

What would be the Fermi energies of the protons and electrons in our hypothetical

star? The Fermi energy for the protons would be very nearly the same as that for the

neutrons above (because the concentration would be the same and the mass is nearly the

same). On the other hand, the Fermi energy of the electrons would be larger by the ratio

of the neutron mass to the electron mass, a factor of 1838, so the electron Fermi energy

would be about 160,000 MeV, enough to make about 170 nucleons! Remember that the

chemical potential (the Fermi energy since all the gases are cold) is the energy required to

add a particle to a system. If neutrons are in equilibrium with protons and electrons, then

the chemical potential of the neutrons equals the chemical potential of the protons plus

the chemical potential of the electrons minus the energy diﬀerence between a neutron and

a proton plus electron. In other words

ǫ

F,n

= ǫ

F,p

+ǫ

F,e

−(m

n

−m

p

−m

e

)c

2

.

Denote the concentrations of the neutrons, protons, and electrons by n

n

, n

p

, and n

e

. Then

n

p

= n

e

,

for charge neutrality and

n

p

+n

n

= n ,

where n is the concentration of the nucleons, which is not changed by the reactions above.

To simplify the notation a bit, let

x =

n

p

n

=

n

e

n

, 1 −x =

n

n

n

.

Each of the Fermi energies can be written in terms of the concentrations

ǫ

F,n

=

¯h

2

2m

n

(3π

2

n

n

)

2/3

= ǫ

F,0

n

n

0

2/3

(1 −x)

2/3

,

ǫ

F,p

=

¯h

2

2m

p

(3π

2

n

p

)

2/3

= ǫ

F,0

n

n

0

2/3

m

n

m

p

x

2/3

,

ǫ

F,e

=

¯h

2

2m

e

(3π

2

n

e

)

2/3

= ǫ

F,0

n

n

0

2/3

m

n

m

e

x

2/3

,

where

ǫ

F,0

=

¯h

2

2m

n

(3π

2

n

0

)

2/3

,

is the Fermi energy for a pure neutron gas at the concentration n

0

we calculated previously.

We plug these energies into the energy equation to obtain

ǫ

F,0

n

n

0

2/3

(1 −x)

2/3

= ǫ

F,0

n

n

0

2/3

m

n

m

p

+

m

n

m

e

x

2/3

−E ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 1-Nov-2004 17-6

where E = (m

n

−m

p

−m

e

)c

2

= 0.783 MeV is the mass energy excess of a neutron over a

proton and electron. If we rearrange slightly, we obtain

(1 −x)

2/3

=

m

n

m

p

+

m

n

m

e

x

2/3

−

E

ǫ

F,0

n

0

n

2/3

,

or

(1 −x)

2/3

= (1.0014 + 1838.7) x

2/3

−

0.783

86

n

0

n

2/3

,

or

x

2/3

= 0.000544

(1 −x)

2/3

+ 0.0091

n

0

n

2/3

.

If n is in the neighborhood of n

0

, then x is small, we can ignore x on the right hand side,

and we ﬁnally obtain

x ≈ 1.3 ×10

−5

.

At higher concentrations x will get slightly smaller and at lower concentrations x will grow

slowly. The concentration of neutrons, protons, and electrons are equal (x = 0.5) when

n = 2.2 ×10

−8

n

0

= 6.4 ×10

30

cm

−3

.

Such low concentrations will be attained only very near the surface of the neutron star.

Caveats: (1) The Fermi energy of the electrons works out to be about 87 MeV, so the

electrons are extremely relativistic, so we really shouldn’t be using our non-relativistic

formula for the electron Fermi energy. One of this week’s homework problems gives you a

chance to modify the treatment to allow for relativistic electrons. (2) With an electron and

proton instead of a neutron, the pressure changes, so the equilibrium condition that we

set up is not quite right. Nevertheless, this calculation gives the ﬂavor of what’s involved

and points to the correct conclusion: For most of its volume a neutron star is almost pure

neutrons!

Of course, we can turn the earlier question around: how is it that nuclei have any

protons??? Haven’t we just shown that at nuclear densities, the nucleons must exist as

neutrons, not protons???

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-1

Bose-Einstein Gases

An amazing thing happens if we consider a gas of non-interacting bosons. For suf-

ﬁciently low temperatures, essentially all the particles are in the same state (the ground

state). This Bose-Einstein condensation can occur even when the temperature is high

enough that one would naively expect that higher energy states should be well populated.

In addition, properties of the gas change when it is in this state, so something like a phase

transition occurs.

Note that photons obey Bose statistics so they constitute a non-interacting gas of

bosons. We’ve already calculated their distribution (which has µ = 0). It’s just the

Planck distribution and this distribution does not have a Bose-Einstein condensation. The

diﬀerence between photons and the situation we’re about to discuss is that there is no

ﬁxed number of photons. If a photon gas is cooled, the number of photons per unit volume

decreases. This is related to the fact that photons are massless. It’s possible to create or

destroy a photon of arbitrarily small energy. The gases we’ll be considering will contain a

ﬁxed number of matter particles. One can’t create or destroy these bosons without doing

something about the rest mass energy (and perhaps other conserved quantum numbers)!

So let the gas contain N particles. The Bose-Einstein distribution is

f(ǫ) =

1

e

(ǫ −µ)/τ

−1

,

and the sum of this distribution function over all states must add up to N. For convenience,

we adjust the energy scale so that the lowest energy state has ǫ = 0.

When τ →0, all the particles must be in the ground state,

lim

τ→0

1

e

−µ/τ

−1

= N ,

lim

τ→0

e

−µ/τ

−1 =

1

N

,

lim

τ→0

e

−µ/τ

= 1 +

1

N

,

lim

τ→0

1 −

µ

τ

+· · ·

= 1 +

1

N

,

lim

τ→0

−µ

τ

=

1

N

,

lim

τ→0

µ = −

τ

N

.

Recall that µ must be lower than any accessible energy for the Bose-Einstein distribution

and here we have µ < 0 in agreement with this constraint, although it converges to 0 as

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-2

τ →0, but this is to be expected as all the particles must pile up in the ground state when

τ →0. It’s instructive to evaluate µ for a mole of particles at a temperature of 1 K. The

result is

µ(1 K) = −2.3 ×10

−40

erg .

If we consider a mole of

4

He and treat it as an ideal gas with p = 1 atm and T = 1 K, then

its volume would be V = 82 cm

3

. This would be equivalent to a cube of side L = 4.3 cm.

Recall that the energies of single particle states in a cube are

ǫ(n

x

, n

y

, n

z

) =

π

2

¯h

2

2mL

2

(n

2

x

+n

2

y

+n

2

z

) .

The ground state has n

x

= n

y

= n

z

= 1 and in the ﬁrst excited state one of these quantum

numbers is 2. Using the L we just calculated and the mass of

4

He, we ﬁnd

ǫ(1, 1, 1) = 1.34 ×10

−31

erg , ǫ(2, 1, 1) = 2.68 ×10

−31

erg .

Actually, the ground state energy is supposed to be adjusted to 0, so we need to subtract

ǫ(1, 1, 1) from all energies in the problem. Then the ground state energy is 0 and the ﬁrst

excited state energy is

ǫ

1

= 1.34 ×10

−31

erg = 5.8 ×10

8

|µ| ,

at T = 1 K. The key point is that even though the energy of the ﬁrst excited state is

incredibly small, and you might think such a small energy can have nothing to do with any

macroscopic properties of a system, this energy (or more properly, the diﬀerence in energy

between the ground state and the ﬁrst excited state) is almost nine orders of magnitude

bigger than µ (at the temperature and density we’re considering). Under these conditions,

what is the population of the ﬁrst excited state?

N

1

=

1

e

(ǫ

1

−µ)/τ

−1

,

=

1

e

−5.8 ×10

8

µ/τ

−1

,

=

1

1 −5.8 ×10

8

µ/τ +· · · −1

,

=

1

−5.8 ×10

8

µ/τ

,

=

1

5.8 ×10

8

/N

,

=

N

5.8 ×10

8

,

so the occupancy of the ﬁrst excited state is almost 9 orders of magnitude smaller than the

occupancy of the ground state. Essentially all the particles are in the ground state even

though kT is much larger than the excitation energy!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-3

Now we want to do a proper sum of the occupancy over the energy states. We might

try to write

N =

∞

0

f(ǫ)D(ǫ) dǫ ,

where

D(ǫ) =

V

4π

2

2m

¯h

2

3/2

√

ǫ ,

is the same density of states we used for the Fermi-gas except there’s a factor of two missing

because we’re assuming a spin 0 boson gas. (If the spin were diﬀerent from 0, we would

include a factor 2S + 1 to account for the multiplicity of the spin states.) The expression

above has the problem that it fails to count the particles in the ground state. We have had

this problem in previous calculations but it never mattered because there were only a few

(2 or less) in the ground state and ignoring these particles makes absolutely no diﬀerence

to any quantity involving the other ∼ 10

23

particles.

However, we are expecting to ﬁnd many, and in some cases, most of the particles in

the ground state. It would not be a good idea to ignore them in the sum! So we write the

sum as

N = N

0

+

∞

0

f(ǫ)D(ǫ) dǫ ,

where the ﬁrst term is the number of particles in the ground state and the second term

accounts for all particles in excited states. This term still makes an error in the low

energy excited states (since we’re integrating rather than summing), but when these states

contain a lot of particles, the ground state contains orders of magnitude more, so errors

in the occupancies of these states are of no concern. In the case that these states don’t

contain many particles, it means that the occupancies of all states are small, and again we

make no appreciable error if we miss on the occupancies of a few of the low energy excited

states.

So, the number of particles in the ground state is

N

0

=

1

e

−µ/τ

−1

,

and the number of particles in excited states is

N

e

=

∞

0

f(ǫ)D(ǫ) dǫ ,

=

∞

0

1

e

(ǫ −µ)/τ

−1

V

4π

2

2m

¯h

2

3/2

√

ǫ dǫ ,

=

V

4π

2

2m

¯h

2

3/2

∞

0

1

e

(ǫ −µ)/τ

−1

√

ǫ dǫ ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-4

=

V

4π

2

2m

¯h

2

3/2

∞

0

1

e

ǫ/τ

−1

√

ǫ dǫ (since |µ|/τ ≪ǫ/τ) ,

=

V

4π

2

2m

¯h

2

3/2

τ

3/2

∞

0

1

e

x

−1

√

xdx (x = ǫ/τ) ,

=

V

4π

2

2m

¯h

2

3/2

τ

3/2

Γ(3/2)ζ(3/2) ,

= 1.306

√

π

V

4π

2

2m

¯h

2

3/2

τ

3/2

,

= 2.612V

mτ

2π¯h

2

3/2

,

= 2.612V n

Q

,

where n

Q

is the quantum concentration again.

The major approximation we made in the above calculation was ignoring the chemical

potential. As long as there are an appreciable number of particles in the ground state,

then |µ| must be much smaller then the energy of any excited state and this is a good

approximation. With the numerical example we worked out before, |µ| will be closer to

0 than to the ﬁrst excited state energy provided the ground state contains about 10

15

or

more particles which means the excited states must contain about 6×10

23

−10

15

= 6×10

23

particles. In other words, our approximation for N

e

above should be valid all the way to

the point where N

e

= N. This means that the N

e

∝ τ

3/2

. We deﬁne the proportionality

constant by deﬁning the Einstein condensation temperature, τ

E

, such that

N

e

= N

τ

τ

E

3/2

,

so

τ

E

=

2π¯h

2

m

N

2.612V

2/3

,

and we expect the expression for N

e

should be valid from τ = 0 up to τ = τ

E

. Then the

number in the condensate is

N

0

= N

1 −

τ

τ

E

3/2

.

Numerically, the Einstein temperature is

T

E

=

115

V

2/3

m

m

,

where T

E

is in Kelvins, V

m

is the molar volume in cm

3

and m is the molar weight in

grams. For liquid

4

He, with a molar volume of 27.6 cm

3

, this gives T

E

= 3.1 K. There

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-5

is actually a transition in liquid helium at about 2.17 K. Below this temperature, liquid

4

He develops a superﬂuid phase. This phase is most likely a Bose-Einstein condensation,

but it is more complicated than the simple theory we have worked out because there are

interatomic forces between the helium atoms. We know this because there must be forces

that are responsible for the condensation of helium gas to liquid helium at T = 4.2 K and

one atmosphere.

If you read the articles referenced at the beginning of these notes, you’ll see that a

major problem faced by the experimenters in creating BE condensates in other systems is

getting the atoms cold enough and dense enough to actually form the condensate. In the

case of helium, the attractive interactions help to get the density high enough to form the

condensate at more accessible temperatures!

Superﬂuid Helium

As mentioned, the transition of

4

He at 2.17 K at 1 atm is believed to be the conden-

sation of most of the helium atoms into the ground state—a Bose-Einstein condensation.

That this does not occur at the calculated temperature of 3.1 K is believed to be due to

the fact that there are interactions among helium atoms so that helium cannot really be

described as a non-interacting boson gas! Above the transition temperature, helium is

refered to as He I and below the transition, it’s called He II.

K&K present several reasons why thinking of liquid helium as a non-interacting gas

is not totally oﬀ the wall. You should read them and also study the phase diagrams for

both

4

He and

3

He (K&K ﬁgures 7.14 and 7.15).

The fact that something happens at 2.17 K is shown by the heat capacity versus tem-

perature curve (ﬁgure 7.12 in K&K) which is similar to the heat capacity curve for a phase

transition and also not all that diﬀerent from the curve you’re going to calculate for the

Bose-Einstein condensate in the homework problem (despite what the textbook problem

actually says about a marked diﬀerence in the curves!). In addition to the heat capacity,

the mechanical properties of

4

He are markedly diﬀerent below the transition temperature.

The liquid helium becomes a superﬂuid which means it ﬂows without viscosity (that is,

friction).

The existence of a Bose-Einstein condensate does not necessarily imply the existence

of superﬂuidity.

To understand this we need to examine the mechanics of friction on a microscopic

level. Without worrying about the details, friction must be caused by molecular collisions

which transfer energy from the average motion (represented by the bulk velocity) to the

microscopic motion (internal energy).

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-6

If our Bose-Einstein condensate were really formed from a gas of non-interacting

particles, then it would be possible to excite any molecule in the condensate out of the

ground state and into the ﬁrst excited state simply by providing the requisite energy (and

momentum). Previously, we calculated that under typical conditions, the energy diﬀerence

between the ground state and the ﬁrst excited state was about 10

−31

erg, an incredibly

small amount of energy that would be very easy to provide given that thermal energies are

about 10

−16

erg.

In order to have superﬂuid behavior, it must be that there are interactions among

the molecules such that it’s not possible to excite just one molecule out of the condensate

and into the ﬁrst excited state. A better way to say this is that due to the molecular

interactions, the single particle states are not discrete energy states of the superﬂuid.

We need to consider the normal modes of the ﬂuid—the longitudinal oscillations or the

sound waves. In particular, we can consider travelling sound waves of wave vector k

and frequency ω. (Rather than the standing waves which carry no net momentum.) A

travelling wave carries energy in units of ¯ hω and momentum in units ¯ hk. The number of

units is determined by the number of phonons or quasiparticles in the wave.

Now imagine an object of mass M moving though a stationary superﬂuid with velocity

V

i

. In order for there to be a force on the object, there must be a momentum transfer

to the superﬂuid. In order to do this, the object must create excitations in the ﬂuid

which contain momentum (the quasiparticles in the travelling waves we just discussed).

Of course, if quasiparticles already exist, the object could “collide” with a quasiparticle

and scatter it to a new state of energy and momentum. (This can also be viewed as the

absorption of one quasiparticle and the emission of another.) We will assume that there

are not very many existing quasiparticles and consider only the creation (emission) of a

quasiparticle.

So, let’s consider this emission process. Before the event, the object has velocity V

i

and afterwards it has velocity V

f

. We must conserve both energy and momentum,

1

2

MV

2

i

=

1

2

MV

2

f

+ ¯ hω ,

and

MV

i

= MV

f

+ ¯ hk .

We can go through some algebra with the goal of solving for V

i

· k. The momentum

equation can be rewritten as

MV

i

−¯hk = MV

f

,

squared and divided by 2M,

1

2

MV

2

i

−¯hV

i

· k +

1

2M

¯h

2

k

2

=

1

2

MV

2

f

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-7

Subtract from the energy equation to get

¯hV

i

· k = ¯ hω +

1

2M

¯h

2

k

2

,

or

V

i

·

k

k

=

¯hω

¯hk

+

¯hk

2M

.

What we really want to do is place a lower limit on the magnitude of V

i

. This means we

can drop the term containing M on the right hand side. The smallest value will occur

when V

i

is parallel to k/k, the unit vector in the k direction. This corresponds to emission

of the quasiparticle in the forward direction. Thus

V

i

>

¯hω

¯hk

.

I’ve left the ¯ h’s there in order to emphasize that the right hand side is the ratio of the

energy to the momentum of an excitation,

Suppose the excitations are single particle states with momentum ¯ hk and energy

¯h

2

k

2

/2m. This is the travelling wave analog to the standing wave particle in a box states

we’ve discussed many times. Then the right hand side becomes ¯hk/2m which goes to

zero as k → 0. Thus, an object moving with an arbitrarily small velocity can produce

an excitation and feel a drag force—there is no superﬂuid in this case. (Note: k must be

bigger than ∼ 1/L, where L is the size of the box containing the superﬂuid, but as we’ve

already seen the energies corresponding to this k are tiny compared to thermal energies.)

Suppose the excitations are sound waves (as we’ve been assuming) and the phase

velocity is independent of k. Then

V

i

>

ω

k

= v

s

,

where v

s

is the phase velocity of sound in the ﬂuid. This means that if an object ﬂows

through the ﬂuid at less than the velocity of sound, the ﬂow is without drag! That is, the

ﬂuid is a superﬂuid.

In fact, the v

s

is not independent of k and what sets the limit is the minimum phase

velocity of any excitation that can be created by the object moving through the ﬂuid.

Figure 7.17 in K&K shows that this minimum is about 5000 cms

−1

for the low lying

excitations in

4

He. K&K point out that Helium ions have been observed to travel without

drag through He II at speeds up to about 5000 cms

−1

!

Comment 1: It appears that we’ve shown that any ﬂuid should be a superﬂuid as

long as we don’t move things through it faster than its speed of sound. In our derivation,

we made an assumption that doesn’t apply in most cases. Can you ﬁgure out which

assumption it was?

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 3-Nov-2004 18-8

Comment 2: As a general rule, superﬂuidity or superconductivity requires the conden-

sation of many particles into a single (ground) state and a threshold for creating excitations.

The minimum velocity required to create an excitation is the threshold for non-viscous ﬂow.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-1

Heat and Work

Now we want to discuss the material covered in chapter 8 of K&K. This material might

be considered to have a more classical thermodynamics rather than statistical mechanics

ﬂavor. We’ve already discussed a lot of this material in bits and pieces throughout the

term, so we will try to focus on the material not yet covered and just hit the highlights of

the remaining material.

Heat and work occur during processes. They are energy transfers. Work is an energy

transfer by macroscopic means and heat is an energy transfer by microscopic means. We’ve

discussed reversible processes several times and we’ll assume reversible processes unless

we explicitly state otherwise. When work is done to or by a system, the macroscopic

parameters of the system are changed—for example changing the volume causes p dV

work to be performed. Performing work changes the energy, U, of a system. But work

does not change the entropy. Heat transfer changes the entropy as well as the energy:

dU = ¯ dQ = τ dσ .

A very important activity in any modern society is the conversion of heat to work.

This is why we have power plants and engines, etc. Basically all forms of mechanical or

electrical energy that we use involve heat to work conversion. Not all of them involve fossil

fuels, and in some cases it may be hard to see where the heat enters. For example, what

about hydro-electric power? This is the storage of water behind a dam and then releasing

the gravitational potential energy of the water to run an electric generator. Where is the

heat supplied? Heat is supplied in the form of sunlight which keeps the weather going

which provides water in the atmosphere to make rain to ﬁll the lake behind the dam. Of

course, the economics of this process are quite diﬀerent from the economics of an oil ﬁred

electrical generating plant.

It was the steam engine (conversion of heat, obtained by burning coal, into work)

that allowed the industrial revolution to proceed. The desire to make better steam engines

produced thermodynamics!

With an irreversible process you can turn work completely into heat. Actually, this

statement is not well deﬁned. What we really mean to say is that with an irreversible

process we can use work to increase the internal energy of a system and leave that system

in a ﬁnal conﬁguration that would be exactly the same as if we had reversible heated the

system. For example, consider a viscous ﬂuid in an insulating container. Immersed in

the ﬂuid is a paddle wheel which is connected by a string running over various pulleys

and whatever to a weight. The weight is allowed to fall under the inﬂuence of gravity.

Because the ﬂuid is so viscous, the weight drops at a constant slow speed. Once the weight

reaches the end of its travel, we wait for the ﬂuid to stop sloshing and the temperature and

pressure in the ﬂuid to become uniform. Thus essentially all of the mechanical gravitational

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-2

potential energy is converted to internal energy of the ﬂuid. We can take the ﬂuid from

the same initial state to the same ﬁnal state by heating slowly (reversibly!) until we have

the same temperature rise.

There is no known way to convert (reversibly or non-reversibly) heat (more properly,

internal energy, U) entirely into work with no other change. This is one of the ways of

stating the second law of thermodynamics.

It is certainly possible to convert heat into work. (I’m getting tired of trying to say it

exactly correctly, so I’ll just use the vernacular and you know what I mean, right?) The

constraints are that you can’t convert all of it to work or there must be some permanent

change in the system or both. For example, suppose we reversibly add heat to an ideal gas

while we keep the volume constant. Then we insulate the gas and allow it to reversibly

expand until its temperature is the same as when we started. Then the internal energy

of the gas is the same as when we started, so we have completely converted the heat into

work, but the system is not the same as when we started. The gas now occupies a bigger

volume and has a lower pressure.

The problem is that when we reversibly add heat to a system we add internal energy

dU = ¯ dQ and we also add entropy dσ = ¯ dQ/τ, but when we use the system to perform work,

we remove only the energy dU = ¯ dW and leave the entropy! If we want to continue using

the system to convert heat to work, we have to remove the entropy as well as the energy,

so there is no accumulation of entropy. The only way to remove entropy (reversibly) is to

remove heat. We want to remove less heat than we added (so we have some energy left

over for work) so we must remove the heat at a lower temperature than it was added in

order to transfer the same amount of entropy.

To make this a little more quantitative, consider some time interval (perhaps a com-

plete cycle of a cyclic engine) during which heat Q

h

is transfered into the system at

temperature τ

h

, heat −Q

l

is transfered into the system at temperature τ

l

, and energy −W

in the form of work is transfered into the system. (So heat Q

l

> 0 leaves the system and

work W > 0 is performed on the outside world.) At the end of this time interval we want

the system to be in the same state it was when we started. This means

∆U = 0 = Q

h

−Q

l

−W ,

and

∆σ = 0 =

Q

h

τ

h

−

Q

l

τ

l

.

We ﬁnd

Q

h

Q

l

=

τ

h

τ

l

,

and

η

C

=

W

Q

h

= 1 −

τ

l

τ

h

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-3

The ratio of the heat input and output is the same as the ratio of the temperatures of

the input and output reservoirs. The energy conversion eﬃciency or just eﬃciency, η is

deﬁned as the work output over the heat input, W/Q

input

. For the ideal engine we’ve

been considering, the eﬃciency is η

C

, the Carnot eﬃciency, and is the upper limit to the

eﬃciency of any real (i.e. non-reversible) engine operating between temperature extremes

τ

h

and τ

l

. Carnot might be called the father of thermodynamics. He worked in the early

1800’s and understood the second law. This was before heat was recognized as a form of

energy!

Of course, this deﬁnition of eﬃciency is motivated by the fact that if you’re an electric

power company, you can charge your customers based on W but you have to pay your

suppliers based on Q

h

and you want to maximize proﬁts!

We live on the surface of the Earth and any engine must dump its waste heat, Q

l

,

at what amounts to room temperature, about 300 K. This is roughly the equilibrium

temperature of the surface of the Earth and is set by radiation equilibrium between the

Sun and Earth and between the Earth and space (T = 3 K). See problem 5 in chapter 4 of

K&K. Aside: are you surprised that room temperature and the surface temperature of the

Earth are about the same? Anyway, the waste heat goes into the environment and usually

generates thermal pollution. There may come a time when a cost is associated with Q

l

.

In this case it’s still desirable to maximize η, because that minimizes Q

l

.

Because waste heat must be dumped at room temperature, improving the Carnot

eﬃciency requires increasing the high temperature, τ

h

. But this is not so easy to do,

especially in an economically viable power plant that’s supposed to last for many years,

Comment 1: no real engine is reversible, so all real engines operating between tem-

perature extremes τ

h

and τ

l

will have an eﬃciency less than the Carnot eﬃciency.

Comment 2: many practical engines are designed in such a way that heat is exchanged

at intermediate temperatures as well as the extremes. Such engines, even if perfectly

reversible, frictionless, etc. have an eﬃciency less than the Carnot eﬃciency. However, if

one assumes a perfect, reversible engine operating according to the speciﬁed design, one

can calculate an eﬃciency (lower than the Carnot eﬃciency) which is the upper limit that

can be achieved by that engine design.

A reversible refrigerator uses work supplied from the outside to remove heat from

a low temperature reservoir and deposit that heat plus the work used as heat in a high

temperature reservoir. Such a refrigerator is basically the reversible engine just discussed,

but run backwards! The signs of Q

h

, Q

l

, and W all change but anything involving their

ratios remains the same. (Note if you wanted to “derive” refrigerators you could start

from the same idea we used with the engine—entropy is only transfered when there’s a

heat transfer and entropy must not be allowed to accumulate in the refrigerator.) With

refrigerators, one uses a coeﬃcient of performance, this is deﬁned as the ratio of the heat

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-4

removed from the low temperature reservoir to the work required. This is

γ =

Q

l

W

,

and for a reversible refrigerator operating between temperatures τ

l

and τ

h

, the Carnot

coeﬃcient of performance is

γ

C

=

τ

l

τ

h

−τ

l

,

and this is an upper limit to the performance of any refrigerator operating between the

same temperature extremes.

Aside: If you go to a department store and look at air conditioners, you will ﬁnd

something called an energy eﬃciency rating (EER) which is basically the coeﬃcient of

performance. But, I believe these are given in BTU per hour per watt. That is they have

dimensions instead of being dimensionless! To convert to a dimensionless number you must

multiply by

1055 Joules

1 BTU

·

1 Hour

3600 Seconds

= 0.29

J Hour

BTUs

.

A typical EER you’ll ﬁnd on an air conditioner is roughly 10, so the “real” γ is about 3!

Note that all reversible engines operating between the same two temperature reservoirs

must have the same eﬃciency. Similarly, all reversible refrigerators operating between the

same two temperature reservoirs must have the same coeﬃcients of performance.

To see this, suppose that one has two reversible engines operating between the same

two temperature reservoirs but they have diﬀerent eﬃciencies. Run the high eﬃciency

engine for some time, taking heat Q

h

from the high temperature reservoir, producing

work W, and dumping heat Q

l

= Q

h

− W in the low temperature reservoir. Now run

the other engine in reverse (it’s reversible!) as a refrigerator removing heat Q

l

from the

low temperature reservoir, so the low temperature reservoir is exactly the same as when

we started. To do this, the refrigerator is supplied with work W

′

and it dumps heat

Q

′

h

= Q

l

+W

′

to the high temperature reservoir. Since this is the less eﬃcient of the two

reversible engines, W

′

< W. So the net eﬀect of running the two engines is to extract heat

from the high temperature reservoir and turn it completely into work. This is a violation

of the second law of thermodynamics, and it does not happen. Therefore all reversible

engines operating between the same two reservoirs must have the same eﬃciency.

Similar kinds of arguments can be used to show that all reversible refrigerators op-

erating between the same two reservoirs must have the same coeﬃcients of performance,

that reversible engines are more eﬃcient than irreversible engines, and that reversible

refrigerators have higher coeﬃcients of performance than irreversible refrigerators.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-5

The Carnot Cycle

We’ve mentioned the Carnot eﬃciency and we’ve talked about heat engines, but how

would one make a heat engine that (were it reversible) would actually have the Carnot

eﬃciency? Simple, make an engine that uses the Carnot cycle.

The Carnot cycle is most conveniently plotted on a

temperature-entropy diagram. We plot the entropy of

the “working substance” in an engine on the horizontal

axis and the temperature of the working substance on

the vertical axis. The working substance might be an

ideal gas. It’s whatever component actually receives the

heat and undergoes changes in its entropy and internal

energy and performs work on the outside world. There

are four steps in a Carnot cycle. In step ab, the tem-

perature is constant at τ

h

while the entropy is increased

from σ

1

to σ

2

. This is the step in which the system is in

contact with the high temperature reservoir and heat Q

h

= τ

h

(σ

2

−σ

1

) is added to the sys-

tem. If the system is an ideal gas, then it must expand to keep the temperature constant,

so it does work on the outside world. In step bc, the temperature is lowered at constant

entropy. No heat is exchanged, the gas expands and does more work on the outside world.

In step cd, entropy is removed at constant temperature by placing the system in contact

with the low temperature reservoir. The heat removed is Q

l

= τ

l

(σ

2

− σ

1

). In this step,

the gas is compressed in order to maintain constant temperature, so the outside world does

work on the gas. In step da, the system is returned to the starting temperature, τ

h

, by

isentropic compression, so more work is done on the system. The hatched area within the

path followed by the system is the total heat added to the system in one cycle of operation,

Q = Q

h

−Q

l

=

τ dσ .

Since the system returns to its starting conﬁguration (same U) this is also the work done

in one cycle.

Whatever the working substance, a Carnot cycle al-

ways looks like a rectangle on a τσ diagram. (It has two

isothermal segments and two isentropic segments.) Given a

working substance we can plot the Carnot cycle on a pV di-

agram. The ﬁgure shows the Carnot cycle for a monatomic

ideal gas. The vertices abcd in this diagram are the same

as the vertices abcd in the τσ diagram. So paths ab and

cd are the constant temperature paths with τ = τ

h

and

τ = τ

l

. Along these paths pV = const. Paths bc and da

are the constant entropy paths with σ = σ

2

and σ = σ

1

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-6

Along these paths pV

5/3

= const. The work done on the outside world in one cycle is the

hatched area within the path,

W =

p dV .

The arrows on the paths indicate clockwise traversal. In this direction, the Carnot

cycle is a Carnot engine producing work and waste heat from high temperature input heat.

If the cycle is run in reverse—counterclockwise—one has a Carnot refrigerator using work

to move heat to a higher temperature reservoir.

As an example of a non-Carnot cycle, suppose we

have a monatomic ideal gas which is the working sub-

stance of a reversible engine and it follows the rectangu-

lar path on the pV diagram shown in the ﬁgure. Along

da, heat is added at constant volume V

1

. On ab, heat is

added at constant pressure. p

2

, and work is performed.

On bc heat is removed at constant volume, V

2

, and on

cd, heat is removed at constant pressure, p

1

, while the

outside world does some work on the system. As before

the total work done on the outside world is the area

within the path and in this case,

W = (p

2

−p

1

)(V

2

−V

1

) .

The heat added is

Q

in

=

3

2

N(τ

a

−τ

d

) +

5

2

N(τ

b

−τ

a

) ,

=

3

2

(p

2

V

1

−p

1

V

1

) +

5

2

(p

2

V

2

−p

2

V

1

) ,

=

5

2

p

2

V

2

−p

2

V

1

−

3

2

p

1

V

1

.

The actual eﬃciency of this reversible engine is

η =

W

Q

in

=

p

2

V

2

−p

2

V

1

−p

1

V

2

+p

1

V

1

5

2

p

2

V

2

−p

2

V

1

−

3

2

p

1

V

1

,

while the Carnot eﬃciency is

η

C

= 1 −

p

1

V

1

p

2

V

2

.

These formulae aren’t all that illuminating so let’s consider a numerical example: suppose

p

2

= 2p

1

and V

2

= 2V

1

. Then the temperature at the hottest (upper right) vertex is 4

times the temperature at the lowest (lower left) vertex, so the Carnot eﬃciency is

η

C

=

3

4

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-7

The actual eﬃciency is

η =

2

13

.

If you’re actually trying to build a heat engine that operates on this cycle, then as you

improve the engine by reducing friction, heat losses, etc., you will approach an eﬃciency

of 2/13 and this should be your goal, not the Carnot eﬃciency.

If you want to approach the Carnot eﬃciency, you must redesign the cycle to be more

like a Carnot cycle. In the cycle shown, the extreme temperatures are reached only at the

upper right and lower left vertices. Most heat transfers are at less extreme temperatures

and this is why the actual eﬃciency is so much less than the Carnot eﬃciency .

Other Thermodynamic Functions

We have concentrated on the internal energy, U, in the preceding discussion. If we

consider a constant temperature process, then the work done on the system is the change

in the Helmholtz free energy. This is because at constant temperature, d(τσ) = τ dσ, so

¯ dW = dU −d(τσ) = dF (constant temperature) .

Many processes occur at constant pressure, such as all processes open to the atmo-

sphere. If a process occurs at constant pressure, then we are letting the system adjust it’s

volume “as necessary,” so we cannot really use or supply any p dV work performed by or

on the system. The p dV work “just happens.” If the system can perform work in other

ways, then we can divide the work into the p dV work and other work,

¯ dW = ¯ dW

other

+ ¯ dW

pV

,

and

¯ dW

other

= dU −¯ dW

pV

−¯ dQ,

= dU +p dV −¯ dQ,

= dU +d(pV ) −¯ dQ,

= dH −¯ dQ (constant pressure),

where

H = U +pV ,

is called the enthalpy. In any constant pressure process the heat added plus the non-p dV

work done is the change in enthalpy. In particular, if there is no non-p dV work done,

the change in enthalpy is just the heat added. Note that ¯ dW

other

is what K&K call the

“eﬀective” work in a constant pressure process.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 5-Nov-2004 19-8

In the event that we have a reversible process that occurs at constant temperature

and constant pressure, the Gibbs free energy is useful. This is deﬁned as

G = F +pV = H −τσ = U +pV −τσ .

It should be clear that

¯ dW

other

= dG (constant temperature and pressure) .

Also, a system which is allowed to come to equilibrium at constant temperature and

pressure will come to equilibrium at a minimum of the Gibbs free energy.

As an example of the use of the Gibbs free energy, consider a system (cell) of two

noninteracting electrodes in an electrolyte consisting of sulfuric acid dissolved in water.

The sulfuric acid becomes two hydrogen ions and one sulfate ion,

H

2

SO

4

↔2H

+

+ SO

−−

4

.

When current is forced through the system in the direction to supply electrons to the

cathode, the reaction at the cathode is

2H

+

+ 2e

−

→H

2

,

and the reaction at the anode is

SO

−−

4

+ H

2

O →H

2

SO

4

+

1

2

O

2

+ 2e

−

,

and the net reaction is

H

2

O →H

2

+

1

2

O

2

.

If the current is passed through the cell slowly and the cell is open to the atmosphere and

kept at constant temperature, then the process occurs at constant τ and p. The “other”

work is electrical work.

W

other

= G(H

2

O) −G(H

2

) −

1

2

G(O

2

) ,

where the Gibbs free energies can be looked up in tables and it is found that the diﬀerence

is

∆G = −273, 000 J mol

−1

.

The other work done is electrical work equal to the charge times the voltage. Since we

have two electrons per mole,

W

other

= −2eN

0

V

0

,

or

V

0

= −

∆G

2N

0

e

= 1.229 Volts ,

where N

0

is Avogadro’s number and e is the charge on an electron. V

0

is the voltage

that is established with no current ﬂowing. At higher voltage, current ﬂows and the cell

liberates hydrogen and oxygen (electrolysis). If these gases are kept in the cell and allowed

to run the reactions in reverse, one obtains a fuel cell in which the reaction of hydrogen

and oxygen to form water generates electricity “directly.”

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-1

Reading

K&K chapter 9 and start on chapter 10. Also, some of the material we’ll be discussing

this week is taken from Mandl, chapter 11.

Gibbs Free Energy

As we discussed last time, the Gibbs free energy is obtained from the energy via two

Legendre transformations to change the independent variables from entropy to temperature

and from volume to pressure,

dU(σ, V, N) = +τ dσ −p dV +µdN

ւ ց

F = U −τσ H = U +pV

dF(τ, V, N) = −σ dτ −p dV +µdN dH(σ, p, N) = +τ dσ +V dp +µdN

↓ ↓

G = F +pV G = H −τσ

G = U −τσ +pV

dG(τ, p, N) = −σ dτ +V dp +µdN.

There are a couple of general points to make here. First of all, if the system has other ways

of storing energy, those ways should be included in all these thermodynamic functions. For

example, if the system is magnetic and is in a magnetic ﬁeld, then there will have to be

an integral of the magnetization (magnetic dipole moment per unit volume) times the

magnetic ﬁeld times the volume element to account for the magnetic energy. The second

point is that if the system contains several diﬀerent kinds of particles, then µdN is replaced

by

¸

i

µ

i

dN

i

, where the index i runs over the particle types. (We will be doing this shortly!)

The above way of writing the energy, the Helmholtz free energy, F, the enthalpy, H, and

the Gibbs free energy, G are really just shorthand for what might actually have to be

included.

As remarked earlier, the Gibbs free energy is particularly useful for situations in which

the system is in contact with a thermal reservoir which keeps the temperature constant,

dτ = 0, and a pressure reservoir which keeps the pressure constant, dp = 0. Then if the

number of particles doesn’t change, the Gibbs free energy is an extremum dG = 0, and in

fact, it must be a minimum (because the entropy enters with a minus sign!).

Another thing to note is that τ, p, and µ are intensive parameters while σ, V , N, and

G itself are extensive parameters. This means that for ﬁxed temperature and pressure,

G must be proportional to the number of particles. Or, G = Nf(τ, p) where f is some

function of the temperature and pressure. If we diﬀerentiate with respect to N, we have

∂G

∂N

τ,p

= f(τ, p) .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-2

If we compare this with the earlier expression for dG, we see that f(τ, p) = µ(τ, p). In

other words, the chemical potential of a single component system depends only on the

temperature and pressure. Furthermore,

G(τ, p, N) = Nµ(τ, p) .

What happens when there is more than one kind of particle in the system? In this

case, we can show that

G(τ, p, N

1

, N

2

, . . .) =

¸

i

N

i

µ

i

,

We must have for any λ,

G(τ, p, λN

1

, λN

2

, . . .) = λG(τ, p, N

1

, N

2

, . . .) ,

as this just expresses the fact that G and the N

i

are extensive parameters. Now, set

x

i

= λN

i

and diﬀerentiate with respect to λ,

¸

i

∂G

∂x

i

∂x

i

∂λ

= G(τ, p, N

1

, N

2

, . . .) .

Note that ∂x

i

/∂λ = N

i

and when λ →1, then x

i

→N

i

, and ∂G/∂N

i

= µ

i

, so

G(τ, p, N

1

, N

2

, . . .) =

¸

i

N

i

µ

i

,

but it is not necessarily true that µ

i

depends only on τ and p.

As an example, We can write down the Gibbs free energy for a classical ideal gas. We

worked out the Helmholtz free energy in lecture 14. For a single component ideal gas, it is

F = Nτ

log

n

n

Q

Z

int

−1

,

so

G = Nτ

log

n

n

Q

Z

int

−1

+pV ,

= Nτ

log

N/V

n

Q

Z

int

−1

+Nτ ,

= Nτ log

p

τn

Q

Z

int

,

where we used the ideal gas law to replace Nτ with pV and N/V with p/τ. Of course,

we could also have obtained this result with our expression for µ that we worked out in

lecture 14! Note that, as advertised, µ is a function only of p and τ.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-3

If we have a multicomponent ideal gas, the situation is slightly more complicated.

Starting from the Helmholtz free energy again, we have

G =

¸

i

¸

N

i

τ

log

n

i

n

i,Q

Z

i,int

−1

+pV ,

=

¸

i

¸

N

i

τ log

N

i

/V

n

i,Q

Z

i,int

−

¸

i

N

i

τ +pV ,

=

¸

i

¸

N

i

τ log

(N

i

/N)(N/V )

n

i,Q

Z

i,int

−

¸

i

N

i

τ +pV ,

=

¸

i

¸

N

i

τ log

x

i

p

τ n

i,Q

Z

i,int

−Nτ +pV ,

=

¸

i

N

i

τ log

x

i

p

τ n

i,Q

Z

i,int

,

where x

i

is the fractional concentration of molecules of type i, x

i

= N

i

/N = n

i

/n. Also,

x

i

p = p

i

, the partial pressure of molecules of type i. The quantum concentrations are

given a molecular subscript since they depend on the masses of the molecules as well

as the temperature. The Gibbs free energy is of the form,

¸

i

N

i

µ

i

, and the chemical

potentials depend on pressure, temperature, and the intensive parameters x

i

.

The derivation of G in the above paragraph hides an important issue in the internal

partition functions, Z

i,int

. This is the fact that all energies in the system must be measured

from the same zero point. In particular, if we have molecules that can undergo chemical

reactions (which is where we’re headed), then we might have a reaction like

A + B ↔C .

If C is stable, then the reaction of A and B to produce C gives up some binding energy ǫ

b

,

so the ground state energy for Z

C,int

is lower than zero by ǫ

b

. In other words, the internal

energy states of the molecules are

A : 0, ǫ

A,1

, ǫ

A,2

, ǫ

A,3

, . . . ,

B : 0, ǫ

B,1

, ǫ

B,2

, ǫ

B,3

, . . . ,

C : −ǫ

b

, −ǫ

b

+ǫ

C,1

, −ǫ

b

+ǫ

C,2

, −ǫ

b

+ǫ

C,3

, . . . .

When we compute the internal partition function for molecule C we need to include −ǫ

b

as part of the energy in every term in the sum. This extra energy will factor out and we

will have

Z

C,int

= e

+ǫ

b

/τ

Z

0,C,int

,

where Z

0,C,int

is the usual partition function with the ground state at 0. Since the logarithm

of the partition function occurs in the chemical potential, the net eﬀect is to add −ǫ

b

to µ

C

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-4

and −N

C

ǫ

b

to the Gibbs free energy. The message is that energies must be measured on

a common scale. We will sometimes assume the internal partition functions are calculated

with the internal ground state energy set to 0 and explicitly add any binding energies to the

chemical potentials. Other times, we will assume that all binding energies are incorporated

into the internal partition functions!

Chemical Equilibrium

Suppose we have a chemical reaction which takes place at constant temperature and

pressure. Then, we know that the Gibbs free energy is a minimum. But in addition to

this condition, we also have the constraint imposed by the reaction. In particular, we can

write any chemical reaction as

ν

1

A

1

+ν

2

A

2

+ν

3

A

3

+· · · +ν

l

A

l

= 0 ,

where A

i

stands for a particular compound and ν

i

denotes the relative amount of that

compound which occurs in the reaction. For example, the formation of water from hydrogen

and oxygen is typically written,

2H

2

+ O

2

→2H

2

O.

This becomes

2H

2

+ O

2

−2H

2

O = 0 ,

with

A

1

= H

2

, A

2

= O

2

, A

3

= H

2

O,

ν

1

= 2 , ν

2

= 1 , ν

3

= −2 .

If the reaction occurs, the change in numbers of molecules is described by ν

i

,

dN

i

= ν

i

dR ,

where dR is the number of times the reaction occurs in the direction that makes the left

hand side. Then the change in the Gibbs free energy is

dG =

¸

i

µ

i

dN

i

=

¸

i

µ

i

ν

i

dR =

¸

i

µ

i

ν

i

dR.

This must be an extremum which means that there is no change in G if the reaction or

the inverse reaction occurs (dR = ±1), so

¸

i

µ

i

ν

i

= 0 ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-5

when a reaction occurs at constant temperature and pressure.

Note 1: the expression we’ve just derived also holds if the temperature and volume

are held ﬁxed. This is most easily seen by noting that when the temperature and pressure

are held ﬁxed, the reaction proceeds until

¸

i

µ

i

ν

i

= 0 at which point the system has

some particular volume determined by the total amount of reactants, the pressure and

temperature. If we start with the temperature ﬁxed and some particular volume, the

reaction proceeds to equilibrium at which point the system has some pressure. Now imagine

that one had started with this pressure, and allowed the reaction to proceed at constant

pressure. Assuming there are not multiple minima in G, the reaction will wind up at the

same place and have the same volume!

Note 2: the expression we’ve just derived holds for a single chemical reaction. If there

are several reactions going on but the net reaction can be reduced to a single reaction,

the above holds. For example, if the reaction is catalyzed by another molecule via an

intermediate step, the reaction rate might diﬀer with and without the catalyst, but the

equilibrium will be the same.

Note 3: the ν

i

are ﬁxed. It is the chemical potentials which adjust to satisfy the

equilibrium condition. Other constraints may need to be satisﬁed as well. For example,

in the water reaction above, the equilibrium condition provides one equation for the three

unknown chemical potentials. Two other conditions might be the total amount of hydrogen

and the total amount of oxygen.

Note 4: if there is more than one reaction, there may be several equations similar to

¸

i

µ

i

ν

i

= 0 which must be satisﬁed at equilibrium. As an example, consider

N

2

+ O

2

↔2NO.

The equilibrium condition,

¸

i

µ

i

ν

i

, can be written

µ

N

2

+µ

O

2

= 2µ

NO

.

In other words, we just substitute the appropriate chemical potentials for the chemicals in

the reaction equation. If we also have

2N ↔N

2

, 2O ↔O

2

, N + O ↔NO,

then we also have the additional relations among the chemical potentials (at equilibrium),

2µ

N

= µ

N

2

, 2µ

O

= µ

O

2

, µ

N

+µ

O

= µ

NO

.

Note that there are ﬁve kinds of molecules. There must be a total amount of nitrogen

and a total amount of oxygen (two conditions), and there are four conditions of chemical

equilibrium. There are six conditions for ﬁve chemical potentials. However, the four

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-6

equilibrium conditions are not all independent. For example, the last one can be derived

from the previous three.

The Law of Mass Action

We’ve seen that for chemical equilibrium, the chemical potentials adjust to satisfy the

equilibrium condition,

¸

i

µ

i

ν

i

= 0. Among other things, the chemical potentials depend

on the concentrations of the molecules. To bring this out, we’ll consider the case that all

molecules participating in a reaction can be treated as an ideal classical gas. (This, of

course, works for low density gases, but also for low concentration solutes.) Then

µ

i

= τ log

n

i

n

i,Q

Z

i,int

= τ log n

i

−τ log n

i,Q

Z

i,int

= τ log n

i

−τ log c

i

,

where

c

i

= n

i,Q

Z

i,int

,

and c

i

depends on the characteristics of molecule i through its mass in the quantum

concentration and its internal states in the partition function, but otherwise c

i

depends

only on the temperature. Note that in this expression, we’re assuming that any binding

energies are included in the internal partition function.

The equilibrium condition can be written

¸

i

ν

i

log n

i

=

¸

i

ν

i

log c

i

,

¸

i

log n

ν

i

i

=

¸

i

log c

ν

i

i

,

log

¸

i

n

ν

i

i

= log

¸

i

c

ν

i

i

,

¸

i

n

ν

i

i

=

¸

i

c

ν

i

i

,

¸

i

n

ν

i

i

= K(τ) .

The last line is known as the law of mass action. The quantity K(τ) is known as the

equilibrium constant and is not a constant but depends on temperature. In terms of

molecular properties, it’s given by

K(τ) =

¸

i

c

ν

i

i

=

¸

i

(n

i,Q

Z

i,int

)

ν

i

.

Note that at a given temperature, measurement of all the concentrations allows one to

determine the equilibrium constant at that temperature. For complicated situations it is

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-7

easier to determine the constant experimentally than to calculate it from the molecular

properties!

Application: pH

Water can undergo the reaction

H

2

O ↔H

+

+ OH

−

.

In water at room temperature a very small fraction of the water molecules are dissociated

into hydrogen and hydroxyl ions. The equilibrium concentrations satisfy

[H

+

][OH

−

] = 10

−14

mol

2

l

−2

.

The notation [whatever] denotes the concentration of whatever. This is almost in the form

of the law of mass action. We need to divide by the concentration of H

2

O to place it in

the proper form. However, the concentration of water in water is about 56 mol/l and it

doesn’t change very much, so we can treat it as a constant, and then the law of mass action

takes the form of the above equation. Note that in pure water, the concentrations must

be equal, so

[H

+

] = [OH

−

] = 10

−7

mol l

−1

.

The pH of a solution is deﬁned as

pH = −log

10

[H

+

] .

The pH of pure water is 7. If an acid, such as HCl is dissolved in water, the increased

availability of H

+

shifts the equilibrium to increase [H

+

] and decrease [OH

−

], but the

product stays constant. When H

+

goes up, the pH goes down. Similarly, adding a base,

such as Na OH, increases the concentration of [OH

−

] and increases the pH.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 8-Nov-2004 20-8

Other Ways of Expressing the Law of Mass Action

We have written the law of mass action in terms of the particle concentrations, n

i

=

N

i

/V . The partial pressure of component i is p

i

= N

i

τ/V , or n

i

= p

i

/τ. If we substitute

these forms in the law of mass action and rearrange slightly, we have

¸

i

p

ν

i

i

=

¸

i

τ

ν

i

K(τ) = τ

¸

ν

i

K(τ) = K

p

(τ) ,

where the equilibrium constant is now called K

p

(τ), depends only on temperature, and is

the product of K(τ) and the appropriate power of the temperature.

We can also write the law of mass action in terms of the fractional particle concentra-

tions, x

i

= N

i

/N = p

i

/p, introduced earlier. We simply divide each partial pressure above

by p (or each concentration by the overall concentration n = N/V and we have

¸

i

x

ν

i

i

=

τ

p

¸

ν

i

K(τ) = K

x

(τ, p) ,

where the equilibrium constant is the product of K(τ) and the appropriate power of τ/p.

In this case, the equilibrium constant is a function of pressure as well as temperature.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-1

The Direction of a Reaction

Suppose we have a reaction such as

A + B ↔C ,

which has come to equilibrium at some temperature τ. Now we raise the temperature.

Does the equilibrium shift to the left (more A and B) or to the right (more C)?

The heat of reaction at constant pressure, Q

p

, is the heat that must be supplied to the

system if the reaction goes from left to right. If Q

p

> 0, heat is absorbed and the reaction

is called endothermic. If Q

p

< 0, heat is released and the reaction is called exothermic.

For a reaction at constant pressure, the heat is the change in the enthalpy of the

system, Q

p

= ∆H. We have

H = G + τσ ,

and

σ = −

∂G

∂τ

p,N

i

,

so

H = G−τ

∂G

∂τ

p,N

i

= −τ

2

∂

∂τ

G

τ

p,N

i

.

What we actually want to do is to change the temperature slightly. Then the system is

no longer in equilibrium and the reaction (in the forward or reverse direction) will have

to occur in order to restore equilibrium. When the reaction occurs from left to right, the

change in particle number is ∆N

i

= −ν

i

and the change in G is

∆G = −

i

µ

i

ν

i

.

If this is 0, we have the equilibrium condition (but we’ve taken it out of equilibrium by

changing the temperature). The change in H is

Q

p

= ∆H = −τ

2

∂

∂τ

∆G

τ

p,N

i

= +τ

2

∂

∂τ

i

µ

i

ν

i

τ

p,N

i

.

The chemical potential is

µ

i

= τ log

x

i

p/τ

n

i,Q

Z

i,int

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-2

We substitute into our expression for Q

p

and obtain,

Q

p

= τ

2

∂

∂τ

i

(ν

i

log (x

i

p) −ν

i

log (τ n

i,Q

Z

i,int

)) ,

= −τ

2

∂

∂τ

i

(ν

i

log (τ n

i,Q

Z

i,int

)) ,

= −τ

2

∂

∂τ

i

(log (τ n

i,Q

Z

i,int

)

ν

i

) ,

= −τ

2

∂

∂τ

log

i

(τ n

i,Q

Z

i,int

)

ν

i

,

= −τ

2

∂

∂τ

log K

p

(τ) .

We’ve related the heat of reaction to the equilibrium constant! This is called van’t Hoﬀ’s

equation. A note on signs: I’ve assumed that the ν

i

are positive on the left hand side of

the reaction and negative for the right hand side of the reaction. Mandl (who provides the

basis for this section) assumes the opposite, so we wind up with our equilibrium constants

being inverses of each other and opposite signs in the van’t Hoﬀ equation.

In any case, our law of mass action has the concentrations of the left hand side

reactants in the numerator and the right hand side reactants in the denominator. So an

increase in the equilibrium constant means the reaction goes to the left and a decrease

means the reaction goes to the right. We see that if Q

p

is positive (we have to add heat

to go from left to right, an endothermic reaction), then our equilibrium constant decreases

with temperature. This means increasing the temperature moves the reaction to the right.

Rule of thumb: increasing the temperature causes the reaction to go towards whatever

direction it can absorb energy. We’ve just shown that increasing the temperature drives

an endothermic reaction to the right. It will drive an exothermic reaction to the left.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-3

Application: the Saha Equation

This section is related to K&K, chapter 9, problem 2. Consider the ionization of

atomic hydrogen,

p

+

+ e

−

↔H .

Ionizing hydrogen from its ground state requires an energy of 13.6 eV, and as the above

reaction is written, it’s exothermic from left to right. If we are considering low density

gases, we can treat them as classical ideal gases and apply our law of mass action:

[p

+

][e

−

]

[H]

=

(n

p,Q

Z

p,int

)(n

e,Q

Z

e,int

)

n

H,Q

Z

H,int

exp(I/τ)

,

where the partition function for the hydrogen atom is to be computed with the ground state

at the zero of energy, as we’ve taken explicit account of the binding energy I = 13.6 eV.

This (or more properly, some of the forms we will derive below) is called the Saha equation.

Some of the factors in the equilibrium constant are easy to calculate and others are

hard to calculate! Let’s do the easy ones. First of all, the mass of a proton and the mass of

a hydrogen atom are almost the same, so the quantum concentrations of the proton and the

hydrogen are almost the same and we can cancel them out. The quantum concentration

of the electron is

n

e,Q

=

m

e

τ

2π¯h

2

3/2

.

The internal partition functions for the electron and proton are both just 2, since each has

spin 1/2. This leaves us with the internal partition function of the hydrogen atom. This is

complicated. First of all, the electron and proton each have two spin states, so whatever

else is going on there is a factor of four due to the spins.

Aside: in fact the spins can combine with the orbital angular momentum to give a

total angular momentum. In the ground state, the orbital angular momentum is zero

and the spins can be parallel to give a total angular momentum of 1¯ h with 3 states or

anti-parallel to give a total angular momentum of 0 with 1 state. The parallel states are

slightly higher in energy than the anti-parallel state. Transitions between these states are

called hyperﬁne transitions and result in the 21 cm line which is radiated and absorbed

by neutral hydrogen throughout our galaxy and others. In any case, the energy diﬀerence

between these states is small enough to be ignored in computing the internal partition

function for the purposes of the Saha equation.

When all is said and done, we have

[p

+

][e

−

]

[H]

= 4

m

e

τ

2π¯h

2

3/2

e

−I/τ

1

Z

H,int

,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-4

where the factor of four accounts for the two spin states of the proton and the two spin

states of the electron (there is a factor of four in the hydrogen partition function as well).

If the temperature is small compared to the binding energy of hydrogen (which means it’s

small compared to the diﬀerence between the ﬁrst excited state and the ground state),

then we might as well approximate the partition function as 4. This gives,

[p

+

][e

−

]

[H]

≈

m

e

τ

2π¯h

2

3/2

e

−I/τ

.

If we have only hydrogen and ionized hydrogen, [p

+

] = [e

−

] and

[e

−

] ≈

[H]

m

e

τ

2π¯h

2

3/4

e

−I/2τ

.

Some points to note: the fact that the exponential has −I/2τ indicates that this is a

mass action eﬀect, not a Boltzmann factor eﬀect. If there is another source of electrons (for

example, heavier elements whose outer electrons are loosely bound), the reaction would

shift to favor more hydrogen and fewer protons. The Saha equation applies to gases in

space or stars as well as donor atoms in semi-conductors (modiﬁed for the appropriate

physical characteristics of the atom and the medium).

In fact, we can do a little more with the Saha equation. Let’s consider an atom which

has several electrons, and ask about the ionization equilibrium between the ions that have

been ionized i times and those that have been ionized i + 1 times,

n

i+1

[e

−

]

n

i

=

(n

i+1,Q

Z

i+1,int

)(n

e,Q

Z

e,int

)

n

i,Q

Z

i,int

exp(I

i+1,i

/τ)

,

where n

i+1

and n

i

are the concentrations of the two ions, n

i+1,Q

and n

i,Q

are the quantum

concentrations of the two ions which are essentially the same, so we cancel them out,

Z

i+1,int

and Z

i,int

are the internal partition functions of the two ions, and I

i+1,i

is the

diﬀerence in binding energy between the two ions. That is, I

i+1,i

is the energy required to

remove an electron from ion i and produce ion i +1. Now, each ion will have some internal

structure and energy levels. We let ǫ

i+1,j

be the energy (relative to 0 for the ion ground

state) of the j

th

state of ion i + 1. This state has multiplicity g

i+1,j

. (If there is more

than one state at a given energy we say that energy is degenerate and the multiplicity

is the number of such states. Sometimes the multiplicity is called the degeneracy or the

statistical weight.) Similarly, ǫ

i,k

and g

i,k

are the energy and multiplicity of the k

th

state

of ion i. The fraction of ions i + 1 which are in state j is given by a Boltzmann factor,

n

i+1,j

n

i+1

=

g

i+1,j

e

−ǫ

i+1,j

/τ

Z

i+1,int

.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-5

If we substitute this expression into the Saha equation, and also substitute the quantum

concentration of the electrons and the internal partition function of the electrons (2), we

get

n

i+1,j

[e

−

]

n

i,k

=

2g

i+1,j

g

i,k

m

e

τ

2π¯h

2

3/2

e

−(I

i+1,i

+ ǫ

i+1,j

−ǫ

i,k

)/τ

.

This form of the Saha equation connects the concentration of ions in various energy levels

to the electron concentration and the temperature. Note that we managed to get rid of the

internal partition functions. Of course, now we have a relation connecting concentrations

of states of a given energy level rather than concentrations of ions of a given ionization.

We can apply the above expression to hydrogen (again!). There are only two ionization

states. We let i = 0 and k = 0, so n

i,k

is the concentration of hydrogen atoms in the ground

state (which has multiplicity g

0,0

= 4 and energy ǫ

0,0

= 0. The ionized state is just a proton

which has a multiplicity of 2, and no excited states. So

[p

+

][e

−

]

n

0,0

=

m

e

τ

2π¯h

2

3/2

e

−I/τ

,

which is essentially the same equation we had before except that now it includes only

hydrogen atoms in the ground state and it is “exact.”

Phase Transitions

Phase transitions occur throughout physics. We are all familiar with melting ice and

boiling water. But other kinds of phase transitions occur as well. Some solids, when heated

through certain temperatures, change their crystal structure. For example, sulfur can exist

in monoclinic or rhombic forms.

When iron is cooled below the Curie point, it spontaneously magnetizes. The Curie

point of iron is T

c

= 1043 K. A typical chunk of iron has no net magnetization because it

magnetizes in small domains with the direction of the magnetic ﬁeld oriented at random.

The magnetization, even in the small domains, disappears above the Curie temperature.

The transition between the normal and superﬂuid states of

4

He is a phase transition

as are the transitions between normal and superconducting states in superconductors.

You’ve probably heard about the “symmetry breaking phase transitions” that might

have occurred in the very early universe, as the universe cooled from its extremely hot

“initial” state. Such transitions “broke” the symmetry of the fundamental forces causing

there to be diﬀerent couplings for the strong, weak, electromagnetic, and gravitational

force. The latent heat released in such a transition might have driven the universe into a

state of very rapid expansion (inﬂation).

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-6

The spontaneous magnetization of iron as it’s cooled below the Curie temperature is

an example of a symmetry breaking transition. Above the Curie point, the atomic magnets

(spins) are oriented at random (by thermal ﬂuctuations). So any direction is the same as

any other direction and there is rotational symmetry. Below the Curie point (and within

a single domain) all the atomic magnets are lined up, so a single direction is picked out

and the rotational symmetry is broken.

This is not an exhaustive list of phase transitions! Even so, we will not have time to

discuss all these kinds of phase transitions. We will start with something “simple” like the

liquid to gas transition.

Phase Diagrams

Suppose we do some very simple experiments.

We place pure water inside a container which keeps

the amount of water constant and doesn’t allow any

other kinds of molecules to enter. The container is

in contact with adjustable temperature and pressure

reservoirs. We dial in a temperature and a pressure,

wait for equilibrium to be established, and then see

what we have. For most pressures and temperatures

we will ﬁnd that the water is all solid (ice), all liquid,

or all vapor (steam). For some temperatures and

pressures we will ﬁnd mixtures of solid and vapor, or

solid and liquid, or liquid and vapor. The ﬁgure shows a schematic plot of a phase diagram

for water. I didn’t put any numbers on the axes—which is why it’s schematic. (Also, there

are several kinds of ice which we’re ignoring!) K&K give a diagram, but it doesn’t have

any resolution at the triple point.

Note that the ﬁrst ﬁgure (which we’ll talk about

some more in a minute) is something like a map: it

says here we have vapor, there we have solid, etc.

The second ﬁgure is a schematic of a pV diagram

showing an isotherm. For an ideal gas, we would

have a hyperbola. For the isotherm as shown, we

have pure liquid on the branch to the left of point

a, pure vapor to the right of point b and along the

segment from a to b we have a mixture of liquid and

vapor. If we move along this isotherm from left to

right, we are essentially moving down a vertical line

in the pτ diagram. To the left of point a we are moving to lower pressures, with liquid

water. from a to b we are stuck at the line in the pτ diagram that divides the liquid from

the vapor region, and to the right of b we are moving down in the vapor region. So the

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-7

entire transition from all liquid to all vapor which is a to b in the pV diagram happens

in a single point in the pτ diagram. At this point, the water has a ﬁxed temperature

and pressure, and what adjusts to match the volume is the relative amounts of liquid and

vapor.

Now, at each location in the pτ diagram, we ﬁx the temperature and pressure and let

the system come to equilibrium. The equilibrium condition is that the Gibbs free energy

is minimized. Ignoring for the moment the fact that the water can be a solid, the Gibbs

free energy is

G(p, τ, N

l

, N

v

) = N

l

µ

l

(p, τ) + N

v

µ

v

(p, τ) ,

where the subscripts l and v refer to the liquid and vapor and we’ve made use of the

fact that for a single component substance the chemical potential can be written as a

function of p and τ only. There are several ways we might minimize G. First of all,

if µ

l

(p, τ) < µ

v

(p, τ), then we minimize G by setting N

l

= N and N

v

= 0 where N is

the total number of water molecules. In other words, the system is entirely liquid. If

µ

v

(p, τ) < µ

l

(p, τ), we minimize the free energy by making the system entirely vapor.

Finally, if µ

l

(p, τ) = µ

v

(p, τ), we can’t change the free energy by changing the amount of

vapor and liquid, so we can have a mixture with the exact amounts of liquid and vapor

determined by other constraints (such as the volume to be occupied).

So, what we’ve just shown is that where liquid and vapor coexist in equilibrium, we

must have

µ

l

(p, τ) = µ

v

(p, τ) ,

which is exactly the same condition we would have come up with had we considered the

“reaction”

H

2

O

liquid

↔H

2

O

vapor

.

This is a relation between p and τ and it describes a curve on the pτ diagram. It’s called

the vapor pressure curve.

With similar arguments, we deduce that solid and vapor coexist along the curve deﬁned

by

µ

s

(p, τ) = µ

v

(p, τ) ,

which is called the sublimation curve, and solid and liquid coexist along the curve

µ

s

(p, τ) = µ

l

(p, τ) ,

which is the melting curve.

If we have all three chemical potentials equal simultaneously,

µ

s

(p, τ) = µ

l

(p, τ) = µ

v

(p, τ) ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 10-Nov-2004 21-8

we have two conditions on p and τ and this deﬁnes a point. This unique (for each substance)

point where solid, liquid, and vapor all coexist is called the triple point. For water,

T

t

= 273.16 K , p

t

= 4.58 mmHg .

Actually, this is now used to deﬁne the Kelvin scale.

If a substance has more than three phases, it can have more than one triple point.

For example, the two crystalline phases of sulfur give it four phases, and it has three triple

points.

The vapor pressure curve eventually ends at a point called the critical point. At this

point, one can’t tell the diﬀerence between the liquid phase and the vapor phase. We’ll

say more about this later, but for now, consider that as you go up in temperature, you

get suﬃciently violent motions that binding to neighboring molecules (a liquid) becomes

a negligible contribution to the energy. As one goes up in temperature, the heat of va-

porization decreases. At the critical point it is zero. The critical point for water occurs

at

T

c

= 647.30 K , p

c

= 219.1 atm .

Another way to think of the phase diagram and the coexistence curves is to imagine

a 3D plot. Pressure and temperature are measured in a horizontal plane, while µ(p, τ) is

plotted as height above the plane. This deﬁnes a surface. In fact we have several surfaces,

one for µ

s

, µ

l

, and µ

v

. We take the overall surface to be the lowest of all the surfaces—

remember we’re trying to minimize G. Where µ

v

is the lowest, we have pure vapor, etc.

Where two surfaces intersect, we have a coexistence curve.

Of course, the phase diagram corresponds to equilibrium. It is possible to have liquid

in the vapor region (superheated), or solid region (supercooled), etc., but these situations

are unstable and the system will try to get to equilibrium. Whether this happens rapidly

or slowly depends on the details of the particular situation.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-1

First Order and Second Order Phase Transitions

In the phase diagram we’ve been discussing, as we cross a coexistence curve, G is

continuous, but its slope changes discontinuously. This is true whether we cross the curve

by changing temperature or by changing pressure. This means that the entropy and volume

have step discontinuities. Recall,

dG = −σ dτ + V dp + µdN ,

so

σ = −

∂G

∂τ

p,N

, V = +

∂G

∂p

τ,N

, µ = +

∂G

∂N

p,τ

.

The situation is sketched in the left pair of plots in the ﬁgure which shows the change

in entropy resulting from the phase transition. Such a transition is called a ﬁrst order

transition—the ﬁrst derivatives of G have discontinuities.

Second order transitions have discontinuities in the second derivatives. So things

like the entropy and volume are continuous, but their slopes change suddenly. This is

illustrated in the righthand pair of plots.

Since there is a discontinuous change in the entropy in a ﬁrst order transition, heat

must be added, and

∆σ = L/τ ,

where L is the heat required for the system to go from completely liquid to completely

vapor at temperature τ. This is called the heat of vaporization (or sometimes the latent

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-2

heat of vaporization). Similarly, there are heats of melting (fusion) and sublimation. In a

ﬁrst order transition, the heat capacities dQ/dτ are δ-functions!

The Clausius-Clapeyron Equation

Now we are going to return to a ﬁrst order transition, like the liquid–vapor transition

in water and see if we can say something about the functional form of the coexistence

curve. The vapor pressure curve is given by

µ

l

(p, τ) = µ

v

(p, τ) .

Let’s move a short distance along the curve in which τ changes by dτ and p changes by

dp. As we move along the curve, the chemical potentials change as well. If we remain on

the curve, the change in both chemical potentials must be the same. We have

dµ

l

(p, τ) = dµ

v

(p, τ) ,

∂µ

l

∂p

τ

dp +

∂µ

l

∂τ

p

dτ =

∂µ

v

∂p

τ

dp +

∂µ

v

∂τ

p

dτ ,

+

∂µ

v

∂p

τ

dp −

∂µ

l

∂p

τ

dp = −

∂µ

v

∂τ

p

dτ +

∂µ

l

∂τ

p

dτ ,

dp

dτ

=

−

∂µ

v

∂τ

p

+

∂µ

l

∂τ

p

+

∂µ

v

∂p

τ

−

∂µ

l

∂p

τ

.

Now, what are all these partial derivatives?

−

∂µ

v

∂τ

p

= −

∂G

v

/N

v

∂τ

p,N

v

,

= −

1

N

v

∂G

v

∂τ

p,N

v

,

= +

1

N

v

σ

v

=

σ

v

N

v

= s

v

,

where s

v

is the entropy per particle in the vapor phase. The other partial derivative in

the numerator gives the entropy per particle in the liquid phase, s

l

, while the partials in

the denominator give the volumes per particle in the vapor and liquid phases, v

v

and v

l

,

respectively. Altogether, we have

dp

dτ

=

s

v

−s

l

v

v

−v

l

.

This is called the Clausius-Clapeyron equation.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-3

Some comments on this equation are in order. First of all, dp/dτ is the slope of

the vapor pressure curve (it has nothing directly to do with the equation of state of the

substance). Secondly, we have the entropy per particle and the volume per particle. Since

we have a ratio, the equation remains true if we use the entropy per mole and volume per

mole, or the entropy per gram and volume per gram, etc. In words, the equation says

the slope of the vapor pressure curve is the ratio of the change in speciﬁc entropy to the

change in speciﬁc volume between the vapor and liquid phases. A similar equation applies

to each coexistence curve. We just need to put in the right quantities. For example, the

melting curve would have

dp

dτ

=

s

l

−s

s

v

l

−v

s

.

A ﬁnal comment is that the speciﬁc entropies and volumes are to be evaluated at the

temperature and pressure at the point on the coexistence curve for which the slope is

desired.

The Clausius-Clapeyron equation is often written in other forms. In particular, the

change in entropy can be immediately related to the latent heat.

dp

dτ

=

ℓ

τ ∆v

,

where ℓ is the speciﬁc latent heat and ∆v is the change in speciﬁc volume. We can apply

this to the melting of ice and the change in melting temperature with pressure. We start

with what happens at 1 atm and 0

◦

C = 273.15 K. The speciﬁc latent heat of fusion is

3.35 ×10

9

ergs g

−1

. The speciﬁc volumes of ice and liquid water are

v

s

= 1.09070 cm

3

g

−1

, v

l

= 1.00013 cm

3

g

−1

.

Remember, water expands as it freezes! The result is

dp

dT

= −1.35 ×10

8

dyne cm

−2

K

−1

= −134 atmK

−1

.

The slope is negative! This accounts for the fact that the melting curve of water leaves the

triple point headed up and slightly to the left. Most materials (which expand on melting!)

have a melting curve which leaves the triple point headed up and slightly to the right. That

is, a large positive slope instead of a large negative slope. This unusual property of water is

often said to be the reason why we can have ﬁgure skating and ice hockey and why glaciers

can ﬂow. As a glacier meets up with an obstruction, the pressure at the point of contact

with the obstruction increases until the ice melts and the liquid water can ﬂow around the

obstruction and refreeze on the other side. Similarly, ice skates can melt ice and the liquid

water helps lubricate the skate. This sounds good, but the numbers don’t work out. For

example, one needs about 10 meters of ice to generate a pressure of one atmosphere; to get

a 10 degree change in melting temperature, we would need a 13 km thick glacier. A 50 kg

skater on a pair of 20 cm by 0.1 mm (very sharp) skates would produce about a 1 degree

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-4

change in melting temperature. Although this eﬀect may play a role, it is probable that

surface eﬀects are more important. For example, a water molecule on the surface forms

bonds with fewer neighbors than a molecule in the interior of the solid. Also, it may be

attracted to the material in contact with the surface making it easier to “melt.”

Now let’s look at what happens at the normal boiling point of water and the liquid–

vapor transition. This occurs at 1 atm and 100

◦

C = 373.15 K. The latent heat of va-

porization is 2.257 × 10

10

ergs g

−1

and the speciﬁc volumes of the liquid and the vapor

are

v

l

= 1.043 cm

3

g

−1

, v

v

= 1673 cm

3

g

−1

.

This gives

dp

dT

= 3.62 ×10

4

dyne cm

−2

K

−1

= 0.036 atmK

−1

.

On Mauna Kea in Hawaii at an altitude of about 14,000 ft, the pressure is about 60% of

sea level pressure. That is, the pressure has decreased by 0.4 atm. Using the slope we just

calculated, we ﬁnd that the boiling point of water decreases by 11

◦

C to 89

◦

C.

Up to this point, we haven’t made any approximations in dealing with the Clausius-

Clapeyron equation. When we deal with the vapor pressure curve, we can usually neglect

the volume of the liquid compared to the gas (as we’ve just seen). Also, we can use the

ideal gas law to get volume in terms of the pressure and temperature (of course, if the

substance is making the transition between liquid and gas, the ideal gas law may not apply

all that well!). Recall, we need the speciﬁc volume, so if we have the latent heat per unit

mass, then we can write v = RT/pM, where R is the gas constant (per mole) and M is

the molecular weight (mass per mole). Then we have

dp

dT

=

ℓ

T(RT/pM)

= p

Mℓ

RT

2

.

This is yet another form of the Clausius-Clapeyron equation. Note that if we evaluate the

slope at the normal boiling point with this expression, we get

dp

dT

= 3.54 ×10

4

dyne cm

−2

K

−1

= 0.035 atmK

−1

,

within 3% of what we had with the exact expression.

We can rewrite the approximate form of the Clausius-Clapeyron equation as

dp

p

=

Mℓ

R

dT

T

2

.

If we now assume that the ℓ does not depend on temperature or pressure, we can integrate

this expression.

log p = −

Mℓ

RT

+ constant ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-5

or

p = p

0

e

−Mℓ/RT

.

What this says is that a semi-log plot of the vapor pressure against T

−1

should be a straight

line. K&K ﬁgure 10.3 shows that this is not all that bad of an approximation. Of course,

we know that the latent heat isn’t constant and it goes to zero at the critical point. Part

of the reason the plot in K&K doesn’t look all that bad is that the scale is very coarse

and covers 8 orders of magnitude in pressure. Even though the latent heat isn’t constant,

it’s a good approximation to assume it is for a small range of the curve and for a small

range, the pressure is well approximated by an exponential of 1/τ. (One can think of the

integration constant, p

0

, as changing from one small range to the next.)

The van der Waals Equation of State

If we want to have an atomic model for a liquid–vapor transition, we will need to model

the gas as something more than non-interacting point particles. A reasonably successful

approach models the gas molecules as having an attractive force for separations larger than

some distance (roughly the equilibrium separation in the solid). The attractive force gets

weaker and goes to zero as the separation is increased. If the molecules get too close, a

strong repulsive force arises. We can approximate this force by thinking of the molecules as

“hard spheres” which can get as close as twice their radii, but no closer. K&K, ﬁgure 10.7

shows a schematic of the potential energy curve of the interaction between two molecules.

(Remember the force is the negative of the slope of this curve.) Fortunately, we don’t need

to know the details of this curve. It’s only described to this extent in order to motivate

the van der Waals equation of state.

The van der Waals equation of state is

p + a

N

2

V

2

(V −bN) = Nτ ,

where a and b are constants that depend on the gas molecules. b is related to the hard

sphere repulsion and a is related to the longer range attraction. This equation of state

can be obtained by starting with the Helmholtz free energy of an ideal gas and making

corrections to account for these eﬀects.

The ideal gas free energy is

F = −Nτ (log(n

Q

/n) + 1) .

If each molecule occupies a volume b then the eﬀective volume available is V −bN, so the

concentration should be replaced by N/(V −bN). Of course, this is not entirely legitimate,

but if each molecule has a volume b, then you would expect the pressure to diverge if the

density reaches 1 molecule per volume b. This is exactly what this correction provides.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-6

Since there is an attractive force between the molecules, there is a net negative con-

tribution to the energy produced by every pair of molecules. We will evaluate this in an

approximate way. Suppose φ(r) is the potential energy between two molecules separated by

r. The potential energy of one molecule due to its interactions with all the other molecules

is

u =

∞

r

min

n(r)φ(r) dV ,

where r

min

corresponds to the minimum distance set by b and n(r) is the concentration at

distance r from the given molecule. The simplest thing we can do is to assume n(r) = n =

const. This is called the mean ﬁeld approximation. We assume that each molecule moves

in the average ﬁeld of all the other molecules and does not aﬀect the density of the other

molecules. Of course, since there is an attractive force, the concentration of molecules

around any given molecule will be higher than it is at a randomly chosen point. That

is, the molecular positions are correlated. The mean ﬁeld approximation ignores these

correlations. So, we have

u = n

∞

r

min

φ(r) dV = −2na ,

which is really just the deﬁnition of a. The factor of two is included for computational

convenience. Due to its interactions with all the other molecules, a given molecule has, on

the average, a change to it’s energy of −2na. There are N molecules, so the total change

in energy due to the attractive part of the van der Waals interaction is

∆U = −2a

N

2

V

,

However, this double counts the interaction energy since each molecule is counted twice:

once while contributing to the mean ﬁeld and once while being acted upon by the mean

ﬁeld. So we need to divide by a factor of two (why we put 2 in to start with!). So

∆U = ∆F = −a

N

2

V

.

Our ﬁnal approximate expression for the free energy of a van der Waals gas is

F = −Nτ

log

n

Q

(V −bN)

N

+ 1

−a

N

2

V

.

We diﬀerentiate with respect to the volume to get the pressure,

p = −

∂F

∂V

τ,N

=

Nτ

V −bN

−a

N

2

V

2

,

which can be rearranged to

p + a

N

2

V

2

(V −bN) = Nτ .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 12-Nov-2004 22-7

We can put the van der Waals equation of state into dimensionless form if we deﬁne

p

c

= a/27b

2

, V

c

= 3bN , τ

c

= 8a/27b .

Then

p

p

c

+

3

(V/V

c

)

2

V

V

c

−

1

3

=

8

3

τ

τ

c

.

This equation is plotted for several values of τ in the ﬁgure. For large τ, it approaches

the ideal gas equation of state, but for small τ there are large deviations from the ideal

gas equation of state. We will explore these deviations and see what they have to do with

phase transitions next time!

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

10-Sep-2004 1-2

Still more amazing is the fact that the foundations of statistical mechanics were developed before quantum mechanics. Incorporating quantum mechanics did make some changes, especially in the counting of states, but the basic approach and ideas of statistical mechanics remained valid. I suspect that this is a reﬂection of both the strength and weakness of statistical methods. By averaging over many molecules you derive results that are independent of the detailed properties of individual molecules. The ﬂip side is that you can’t learn very much about these details with statistical methods.

Some Thermodynamic Concepts From mechanics, we’re familiar with concepts such as volume, energy, pressure (force per unit area), mass, etc. Two new quantities that appear in thermodynamics are temperature (T ) and entropy (S). We will ﬁnd that temperature is related to the amount of energy in a system. Higher temperature means greater internal energy (usually). When two systems are placed in contact, energy in the form of heat ﬂows from the higher temperature system to the lower temperature system. When the energy stops ﬂowing the systems are in thermal equilibrium with each other and we say they are at the same temperature. It turns out if two systems are in thermal equilibrium with a third system, they are also in thermal equilibrium with each other. (This is sometimes called the zeroth law of thermodynamics.) So the concept of temperature is well deﬁned. It’s even more well deﬁned than that as we will see later in the course. Two systems can exchange energy by macroscopic processes, such as compression or expansion, or by microscopic processes. It is the microscopic process that is called heat transfer. Consider a collision among billiard balls. We think of this as a macroscopic process and we can determine the energy transfer involved by making measurements of a few macroscopic parameters such as the masses and velocity components. If we scale down by roughly 24 orders of magnitude, we consider a collision between molecules, a microscopic process. A very large number of collisions occur in any macroscopic time interval. A typical molecule in the atmosphere undergoes ∼ 1010 collisions per second. All these collisions result in the exchange of energy and it is the net macroscopic transfer of energy resulting from all the microscopic energy transfers that we call heat. Recall that the ﬁrst law of thermodynamics is dU = dQ + dW , where dU is the change of (internal) energy of a system, dQ is energy added to the system via a heat transfer, and dW is energy added by doing work on the system. Aside: you will often see the heat and work written as dQ and dW . This is a reminder ¯ ¯ that these quantities are not perfect diﬀerentials, just small changes. A system (in equiCopyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

10-Sep-2004 1-3

librium) has a well deﬁned internal energy U (P, V, . . .) which can be diﬀerentiated with respect to P , V , . . ., but there is no such thing as the heat or work content of a system. The heat and work refer to energy transfers during a change to the system. So the ﬁrst law really boils down to a statement of energy conservation. You can change the energy of a system by adding energy microscopically (dQ) or macroscopically (dW ). While we’re at it, the second law of thermodynamics can be stated in many ways, but one way (without worrying too much about rigor) is: it’s impossible to turn heat completely into work with no other change. So for example, if you build a heat engine (like a power plant) you can’t turn all the heat you get (from burning coal) completely into electrical energy. You must dump some waste heat. From this law, one can derive the existence of entropy and the fact that it must always increase. (Or you can deﬁne entropy, and state the second law in terms of the increase in entropy).

Entropy Earlier, we mentioned that temperature is related to internal energy. So, a picture we might carry around is that as the temperature goes up, the velocities of the random motions of the molecules increase, they tumble faster, they vibrate with greater amplitude, etc. What kind of picture can we carry around for entropy? Well that’s harder, but as the course goes along we should develop such a picture. To start, we might recall that the change in entropy of a system is the heat added to the system divided by the temperature of the system (all this is for a reversible process, etc.): dS = dQ/T . If a dQ > 0 is added to one system, −dQ must be added to a second system. To ensure that entropy increases, T1 < T2 ; the ﬁrst system is cooler than the second system. The molecules in the ﬁrst system speed up and the molecules in the second system slow down. After the heat is transfered (in a direction which makes entropy increase) the distribution of molecular speeds in the two systems is more nearly the same. The probability that a fast molecule is from system 1 has increased while the probability that a fast molecule is from system 2 has decreased. Similarly, the probability that a slow molecule is from system 2 has increased and the probability a slow molecule is from system 1 has decreased. In other words, as a result of the increase of entropy, the odds have become more even. So increasing entropy corresponds to a leveling of the probabilities. Higher entropy means more uniform probability for the possible states of the system consistent with whatever constraints might exist (such as a ﬁxed total energy of the system). So entropy is related to the number of accessible states of the system and we will

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

. . How many microscopic states are there? Why do we want to know? The idea is that the macroscopic state which is generated by the most microscopic states is the most likely. n. Suppose we say that S ∝ log g . Princeton University Physics Department. where n is the number of moles and CV is the molar speciﬁc heat at constant volume which we take to be constant. where we’ve assumed that the number of particles in the system is constant and the work done on the system results from pressure acting while the volume changes. Since there is such a large ratio of microscopic to macroscopic parameters. Ti Vi dT dV + nR . The equation of state is pV = nRT or p/T = nR/V . The macroscopic state is completely speciﬁed (at equilibrium!) by a small number of parameters such as p. The ﬁrst law of thermodynamics can be written as dU = dQ + dW = T dS − p dV or dS = dU/T + p dV /T . . let’s make a distinction between the macroscopic state and the microscopic state. Copyright c 2004. Suppose the system is an ideal gas. it must be that many microscopic states may produce a given macroscopic state. vN . by log. unless otherwise stated. . loge . I mean a natural logarithm. Edward J.) First. But how can we relate this to what’s going on at the microscopic level? (Note. v1 . Groth . we have an expression for the entropy diﬀerence between any two states of an ideal gas. where N is the number of particles. the number of particles in a mole. rN . the microscopic state requires the speciﬁcation of the position and velocity of each particle r1 . T V So. Then the energy depends only on temperature dU = nCV dT . We plug these into the ﬁrst law and obtain dS = nCV which can be integrated to give Sf − Si = nCV log Tf Vf + nR log . V .02 × 1023 . where R is the gas constant.Physics 301 10-Sep-2004 1-4 ﬁnd that maximizing the entropy is equivalent to assuming that each accessible state is equally likely. etc. comparable to Avogadro’s number. Classically. r2 . N0 = 6. v2 . N is usually a huge number.

A A molecular volume is Vm ≈ 10−24 cm3 . bringing the systems together does not change the states available to either system. but leaving this out won’t hurt anything at this point. there are M − 2 ≈ M ways. you might think there are an inﬁnite number of states because r and v are continuous variables. we should probably divide by N ! to account for permutations of the molecules in the cells (since we can’t distinguish one molecule from another).Physics 301 where g is the number of microstates corresponding to the macrostate. There are M = V /Vm = 2 × 1028 cells. ways to distribute the molecules in the cells. Edward J. Altogether there are about g ≈ M N ≈ 1028 1024 . Since the systems are non-interacting. Let’s specify the micro-position state by stating which cells have molecules in them. Imagine dividing our total volume V into cells the size of a molecule. we are going to specify the positions of the molecules to a molecular diameter. So let’s count states.4 L = 2 × 104 cm3 and it contains N0 = 6 × 1023 molecules. That is. and any microstate of system 1 may be combined with any microstate of system 2 to yield a microstate of the combined system. Also. Its volume is V = 22. The fact that we get M N rather than a binomial coeﬃcient depends on the fact that M ≈ 1028 ≫ N ≈ 1024 . and we bring them together. 10-Sep-2004 1-5 This deﬁnition has the desirable property that if we have two non-interacting systems with states g1 and g2 . Well. This can be done in M ways. How big is a molecule? Answer: about 1 ˚ = 10−8 cm. By deﬁning the entropy with a logarithm. Groth . perhaps if you change them only slightly. This means that there are a total of g1 · g2 states altogether. S = S1 + S2 . For the third molecule. This can be done in M − 1 ≈ M ways. As an example. The ﬁgure shows a couple of the possible position microstates of this gas. Continue to the N th molecule for which there are M − N ≈ M ways to pick a cell. consider a two dimensional gas containing N = 10 molecules and M = 100 cells. Pick a cell for the second molecule. How many states are there? Pick a cell for the ﬁrst molecule. the entropy is additive. you don’t really get a new state. we ensure that it’s additive (at least in this case!). Princeton University Physics Department. At ﬁrst sight. Copyright c 2004. Example: Ideal Gas Entropy Consider one mole of ideal gas at STP.

volume term in entropy The N log Vm term is a constant for a given amount of gas and disappears in any calculation of the change in entropy. = N log Vm constant for given amount of gas = N log V − N log Vm . Knowing the number of states. Similarly.7 × 1013 distinct states. Sf − Si . V . Groth . Edward J. Our approximation gives 1020 states. By considering the microstates in velocity. we have S ∝ N log M . we would obtain the temperature term (and we will later in the term!). The N log V term is the volume term in the ideal gas entropy. Copyright c 2004.Physics 301 10-Sep-2004 1-6 There are M !/N !(M − N )! = 1. So a lot of the (really awful?) approximations we made just don’t matter because things like the size of a molecule drop out as long as we only consider entropy diﬀerences. Princeton University Physics Department. the N ! correction would also disappear. the diﬀerence is mostly due to ignoring the 10! in the denominator.

g2 = 2V Vm N . Edward J. g1 = 2Avogadro’s Number . h If the state of the system is speciﬁed by a point in the x px diagram (phase space). wind up in one-half the container with volume V ? How many states are there in each case? g1 = And. V Vm N . 2×1023 zeros 23 23 Such a state might be legal. then one can’t tell the diﬀerence between states which are as close or closer than the above. = 26×10 . Copyright c 2004. but it’s extremely!!! unlikely. If we consider quantum mechanics. the resolution has no eﬀect on our calculation of changes in the entropy. We’ve shown that as long as it’s small. An example is to consider a particle in a box and ﬁt the wave functions in. The fact that a system in equilibrium has the maximum possible entropy is nothing more than the fact that the normal equilibrium state has so many more ways to occur than an obviously weird state.Physics 301 What Those Large Numbers Mean 10-Sep-2004 1-7 The key aspect of all this is the large number of states! Suppose we have a gas in equilibrium in a container of volume 2V . There are many ways to see this. Groth . that the weird state just never occurs. Quantum Mechanics and Counting States You might be thinking that’s it pretty ﬂaky to assert that we need only specify a molecular position to a molecular diameter. g2 = 2N . Why doesn’t the gas. = 1 000 · · · 000 . so this is OK for classical mechanics. = 102×10 . by chance. Another way is to consider the uncertainty principle. So we can divide up this phase space into cells of h/2 and we can specify a state by saying ¯ which cells are occupied and which are not. ∆px ∆x ≥ ¯ /2 . then we ﬁnd that systems are in deﬁnite states. Princeton University Physics Department.

but not wildly separated from the quantum domain. At most one fermion can be placed in a quantum state.4 × 10−26 g cm2 /s > ¯ = 1 × 10−27 erg s . so A p r = 2. room temperature air is classical. and Fermi distributions! Copyright c 2004.1 × 104 cm/s. consider air (N2 ) at room temperature. the probability that any particular state is occupied is extremely small.Physics 301 10-Sep-2004 1-8 As a numerical example. etc. That is. This is the classical limit and corresponds to the Boltzmann distribution. Groth . A typical kinetic energy is mv 2 /2 = 3kT /2 with T = 300 K and k = 1. particles that we associate with matter). electrons in metals. mN2 = 28mp = 28 × 1. Edward J. That is.7 × 10−24 g = 4. If we have higher occupancy systems (denser and/or colder). The ideal gas at STP is a “low occupancy” system. This leads to Bose-Einstein statistics and the Bose distribution. If we consider lower temperatures or higher densities. quantum eﬀects will be more important. electrons. one can specify the momentum of a molecule to a reasonable fraction of a typical momentum and the position to about the molecular size and still be consistent with quantum mechanics and the uncertainty principle.38 × 10−16 erg/K. A lot of what we do this term will be learning about and applying the Boltzmann. at room temperature. one occurs very rarely. then states occupied by two or more particles can become likely. p ∼ 2. An arbitrary number of bosons can be placed in a single quantum state. Bose.4 × 10−18 g cm/s. At this point quantum mechanics enters. This leads to Fermi-Dirac statistics and the Fermi distribution.8 × 10−23 g. There are two kinds of particles: integer spin particles called bosons (such as photons or other particles that we associate with waves) and half-integer spin particles called fermions (protons. v ∼ 5. then E ∼ 6 × 10−14 erg. h Thus. and we just don’t need to worry about two at all. Princeton University Physics Department. This means that the most likely number of occupants of a particular state is zero. The molecular size is about r ∼ 1 ˚ = 10−8 cm.

so as to maximize the number of accessible states and hence the entropy. remember that we are typically dealing with something like Avogadro’s number of particles.. Or put another way. First. within the allowed constraints. you should read the ﬁrst two chapters of K&K. the distribution of molecular positions and speeds is randomized. In a solid. etc. the entropy is the log of the number of states that are accessible to the system when it has speciﬁed macroscopic parameters (its “macrostate”). a molecule typically travels many molecular diameters. The other thing that happens with a large number of particles has to do with the randomness of the interactions. etc. the answers can only be given in terms of probabilities and these answers will be the same no matter which molecule you Copyright c 2004. momentum. how often). Why is the Number of States Maximized? Good question. Edward J.Physics 301 Reading This week. As a result. N0 = 6. 13-Sep-2004 2-1 Entropy and the Number of States As we discussed last time. Princeton University Physics Department. The fact that entropy always increases is just a reﬂection of the fact that a system adjusts its macroscopic parameters. momentum. Molecules in a gas are in continual motion and collide with each other (we will see later in the term. one of the diﬀerences between a liquid and gas has to do with the distance a molecule travels between collisions: in a gas. We will not attempt to prove it. in the statistical view. molecules tend to be conﬁned to speciﬁc locations. If you pick a molecule and ask things like where is it located. how fast is it going. Groth . So. As we discussed last time. with their neighbors. in a liquid. improbable events are very improbable. a large part of statistical mechanics has to do with counting states and another large part has to do with deriving interesting results from these simple ideas. this makes the probability distributions very sharp. molecules are undergoing collisions and interactions all the time. During these collisions.02 × 1023 . but they oscillate around these locations and exchange energy. the distance between collisions is of the order of a molecular diameter. However. we can give some plausibility arguments. OK. entropy is related to the number of “microstates” of a system. molecules exchange energy. In particular. The situation in a liquid is similar. etc. We are going to take this is an axiom or postulate. angular momentum.

Then in principle.. Princeton University Physics Department. so one expects (small) random perturbations from outside the system. etc. But we can in principle! A somewhat better answer is that we can only know the initial conditions with some precision.Physics 301 13-Sep-2004 2-2 pick. As we evolve the equations of motion forward. but there are no good philosophical answers. I’m sure you’ve seen or will see in your QM course that in general. the fact that we cannot measure inﬁnitely precisely the initial conditions nor solve such a large number of equations does not mean (still assuming classical mechanics) that it couldn’t be done in principle. . Groth . the system must be described by a wave function (depending on ∼ N0 variables). On the other hand. but you’ll get the same answers for two N2 molecules. uncertainties tend to grow with time (the spreading out of a wave packet is a typical example). (This is the philosophical side coming again!) So perhaps there is still nothing random going on.) Sticky point: suppose we assume that the world is described by classical mechanics.). At this point one might notice that it’s impossible to make a totally isolated system. Edward J. as said before. we are going to postulate that a system is equally likely to be in any state that is consistent with the constraints (macroscopic parameters) applied to the system. This is one of the basic concepts of chaos which has received a lot of attention in recent years: small changes in the initial conditions can lead to large changes in the ﬁnal result. . Suppose we also know all ∼ N0 positions ri and momenta pi (and whatever else we might need to know to specify the system.you’ll probably get diﬀerent answers for a N2 molecule and an Ar atom. Also. perhaps one just needs to include a larger system! If we recognize that quantum mechanics is required. Copyright c 2004. These will disturb the evolution of the system and have essentially the same eﬀect as uncertainties in the initial conditions. perhaps the angular momenta of the molecules. So. then we notice that quantum mechanics is an inherently probabilistic theory. As you can see this kind of discussion can go on forever. (Provided you pick the same kind of molecule . the initial uncertainties grow and eventually dominate the evolution. The practical answers have to do with the fact that one can’t really write down and solve the equations of motion for ∼ N0 particles. whose evolution is determined by Schroedinger’s equation . there is nothing random about it! How do we reconcile this with the probabilistic view espoused in the preceding paragraphs? So far as I know. Also suppose we know the interactions between molecules in some isolated system. there are reasonable practical answers to this question. the equations of motion can be solved and the solution tells us the exact state of the system for all future times. That is. (Have you ever wished you could get a 10 day or 30 day weather forecast? Why do they stop with the 5 day forecast?) Of course. not inﬁnite precision. But.

M. You can ﬁnd it at http://physics.Physics 301 13-Sep-2004 2-3 As it happens. Aside—Entropy and Information In recent times. then the physical entropy would be zero (there’s nothing random about the positions and momenta). “Chaotic Dynamics and the Origin of Statistical Laws. In 1998. One of our criteria for junior papers is that other juniors should be able to understand the paper. there is a recent Physics Today article on exactly this subject: trying to go from the reversibility of classical mechanics to the irreversibility of statistical mechanics. It is found that concepts in information theory are very similar to concepts in thermodynamics. p. pt. I think you can read this article and get a feel for the problem even if some of it goes over your head (as some of it goes over my head).html . Princeton University Physics Department. no. there has been considerable interest in the information content of data streams and what manipulating (computing with) those data streams does to the information content. Groth . It’s by G. 52. vol.edu/www/jh/juniors fall98. 39. One way out of the “in principle” problems associated with classical entropy is to consider two sources of entropy: a physical entropy and an information or algorithmic entropy. the logarithm of the number of steps in the algorithm required to reproduce the list. but the algorithmic entropy of our list of positions and momenta would be large (and equal to the physical entropy of a similar gas whose positions and momenta we hadn’t determined). 1.” 1999. so I think you might get something out of this paper as well! Copyright c 2004. What is algorithmic entropy? Essentially.princeton. This goes something like the following: if we had some gas and we had the knowledge of each molecule’s position and momentum. Toby Marriage wrote a JP on this topic. Zaslavsky and is called. 8. Edward J.

V. and T is the absolute temperature. N . For example. T = T (N. V is the volume. V. consider a gas. The gas law is an equation of state. other parameters may be needed. U ). T ). U ). For example. T ). and we can write p = p(N. Can you think why? Parameters which depend on the size of the system are called extensive parameters. and T stay the same. that is!). Another thing to notice is that not all parameters may be speciﬁed independently. V. we might have p = p(N. R = 8.. Note that the gas law is not the whole story. Thus there is a certain minimum number of parameters which specify the system. . Any property of the system must be a function of these parameters. and U . Also. we can often change variables and use a diﬀerent set of parameters. For a single component ideal gas. . U (internal energy). n is the number of moles. the gas law does not say anything about the energy of the gas or its entropy. but it needs to be supplemented by other relations in order that we know everything there is to know about the gas (macroscopically. and S (entropy) all double. Notice that some parameters depend on how much gas we have and some don’t.38 × 10−16 erg K−1 is Boltzmann’s constant or the gas constant per molecule. it can be described quite well by the ideal gas law when it’s in equilibrium: pV = N kT = nRT .Physics 301 Macroscopic Parameters 13-Sep-2004 2-4 We will be most concerned with systems in equilibrium. and V . U ) . Parameters that are independent of the size of the system are called intensive parameters. We might imagine solving for T in terms of N . Which parameters are to be used depends on the particular situation under discussion. T ) . N is the number of molecules. V. S = S(N. p. having speciﬁed N . Anything that depends only on the equilibrium state of the system can be expressed as a function of the parameters chosen. U = U (N. On the other hand. Such a system can usually be described by a small number of macroscopic parameters. if we replicate our original system. Princeton University Physics Department. . T . the pressure is determined. where p is the pressure. Groth . we need to specify the numbers of each kind: N1 . Furthermore. N2 . many processes occur at constant pressure (with the volume adjusting to what it needs to Copyright c 2004. For systems more complicated than a gas. V. so we have twice as much. We are ignoring the contribution of any surface interactions which we expect to be very small. we would likely use that as one of the independent parameters.31 × 107 erg mole−1 K−1 = N0 k is the gas constant per mole. if the volume of a system is under our control. If more than one kind of molecule is in the gas. Edward J. k = 1. then V . S = S(N. For example. If the density of the gas is low enough. For example. V. V .

V1 . N1 . V1 . we prevent changes in volume and numbers of particles. V2 . N1 ) = log g(U. V. and N2 remain constant. .. U1. N. U1. we ignore the possibility of reactions which can change particles of one kind into another kind. Also. So far. N2 ) . N = N 1 + N2 . V. V. so we can write the parameters of the combined system as the sum of those for the individual systems as well as one set of the individual system parameters. Nb . then the number of microstates of the combined system is g(U. If we have two systems. with U = U1 + U2 . N1 ) + σ2 (U2 . Nb . V = V1 + V2 . Copyright c 2004. Groth . V2 . N2 ) . so we’ll just assume a single kind of particle for the time being and assume we have N of them. etc. In this case. In addition. Following K&K. We’ve just written down some deﬁnitions twice. Any microstate in system 1 can be paired with any microstate in system 2. we allow U1 and U2 to vary. that we prevent from interacting. In other words. Then the number of microstates is g = g(U. N1 ) = log g1 g2 = log g1 + log g2 = σ1 (U1 . V1 . and the number of each kind of constituent particle Na . V1 . We have prevented the two systems from interacting. so that V1 . Let’s consider a system described by its internal energy U . we have speciﬁed the macrostate in terms of extensive parameters. The number of states must be a function of the same macroscopic parameters that determine the macrostate of the system. its volume V . so the total number of microstates is just the product of the number for each system. N. V1 . For the moment. V2 . . This is straightforward. N ) . N. Princeton University Physics Department. . N1 ) = g1 (U1 . The Temperature As we remarked. V. so nothing exciting can happen. Now let’s suppose we allow the systems to exchange energy. N1 )g2 (U2 . This means that our expressions will have the same form for Na . Edward J. we haven’t really done anything. the entropy is the logarithm of the number of microstates accessible to a system..Physics 301 13-Sep-2004 2-5 be). but any change in U1 has a compensating change in U2 so that U is constant. using p rather than V as the independent parameter will probably be more convenient. U1. the dimensionless entropy is just σ(U.

We know this from our intuitive understanding of the second law: heat ﬂows from a hot object to a cold object.N V. but preventing changes in volume or particle number. we can deﬁne the temperature as: 1 = τ ∂σ ∂U . ∂σ ∂U1 =0 V. Thus. then we know that ∂σ/∂U was already the same.N + V. If we started out with the two systems and we allowed them to exchange energy and nothing happened.N This makes τ an intensive quantity (it’s the ratio of two extensive quantities). V. Princeton University Physics Department. But. it means that the system adjusts U1 and U2 to maximize the entropy. So at equilibrium.N = = = This means ∂σ2 ∂U1 ∂σ2 ∂U2 ∂σ2 ∂U2 V.Physics 301 13-Sep-2004 2-6 We’re placing the systems in thermal contact. V.N ∂U2 ∂U1 since ∆U1 = −∆U2 . Groth .N after equilibrium has been established. − V. We know what will happen: energy ﬂows from the hotter system to the cooler system until they come to thermal equilibrium at the same temperature. and it makes the energy ﬂow in the “correct” direction. then ∂σ3 /∂U3 must also have the same value and nothing will happen if systems 2 and 3 are allowed to exchange energy. ∂σ/∂U has properties very similar to those we ascribe to temperature. This can be seen as follows: if the two systems are not in equilibrium when we allow energy to ﬂow. then the entropy of the combined systems must increase: The increase in Copyright c 2004. If system 1 and system 2 are in equilibrium with respect to energy exchange and we allow system 1 to exchange energy with a third system and nothing happens. In fact.N ∂σ1 ∂U1 = V. Edward J. the rate of change of entropy with respect to energy is the same for the two systems. So.N since σ is maximized ∂σ1 ∂U1 ∂σ1 ∂U1 ∂σ1 ∂U1 + V.N ∂σ2 ∂U2 .N V. what about our postulate that a system maximizes the number of accessible microstates? In this case.

It’s often said that we measure temperature in Kelvins or degrees Celsius or Fahrenheit because the measurement of temperature was established before the development of thermodynamics which in turn took place before the connection to energy was fully appreciated.14 × 10−14 erg or 0. Physics Today. 8. “Temperature Scales Below 1 Kelvin. which means energy ﬂows from the high τ system to the low τ system. Well. W. 1997. you’ll often ﬁnd the statement that this a reminder that V and N are being held ﬁxed in taking the indicated partial derivative. A recent Physics Today article discusses some of the diﬃculties in deﬁning a good practical scale for τ /k < 1 Kelvin. 36. E. τ /k. Units: from our deﬁnitions σ is dimensionless and τ has the dimensions of energy. Edward J. Finally. δU1 > 0.. but since we have a partial derivative. 50.Physics 301 entropy after a very small amount of energy has been transferred is δσ > 0 = δσ1 + δσ2 1 1 = δU1 + δU2 τ1 τ2 1 1 − δU1 . τ = kT . Princeton University Physics Department. recall that dU = T dS − p dV which agrees with this deﬁnition of temperature. Boltzmann’s constant is really just a scale factor which converts conventional units to the fundamental units we’ve deﬁned above. why do we need an extra reminder? Answer: since there are so many choices of independent variables. = τ1 τ2 13-Sep-2004 2-7 So if τ1 < τ2 . Thermometers make use of physical properties which vary with temperature.. N subscripts.. As it turns out. this is ∼ 80◦ F. no. to measure a temperature. if you remember your elementary thermodynamics. we need a thermometer. this is true. p.”) One other thing to point out here: You’ve no doubt noticed the V. Jr. What would you think if you tuned in to the weather channel and found out that the high tomorrow was expected to be 4. and Fogle.) Actually. vol. (That’s obvious I suppose!) The trick is to calibrate the thermometers so you get an accurate measure of the thermodynamic temperature. R. Groth . When you read a thermodynamics text. S = kσ . J. (Soulen. You recall that temperature T has the dimensions of Kelvins and entropy S has the dimensions of ergs per Kelvin. Copyright c 2004.0259 eV??? (If I did the arithmetic correctly. which already means hold everything else ﬁxed. these subscripts are really a reminder of the set of independent variables in use.

∂σ ∂U = V.Physics 301 13-Sep-2004 2-8 Note that we can add energy to a gas keeping the volume and number of particles ﬁxed. I will probably be lazy and omit the subscripts. we can keep the pressure and number of particles ﬁxed. Furthermore. p. Princeton University Physics Department. Alternatively. In this case the volume and temperature increase. In this case the pressure and temperature rise.N When it’s obvious from the context which set of independent variables are in use.N ∂σ ∂U . Copyright c 2004. Groth . Edward J.

N Suppose we continue to consider our two systems. and ∂σ2 ∂σ1 = . We allowed them to exchange internal energy (that is. two systems exchange volume only if one system can “push harder” and expand while the other contracts. σ(U. ∂V1 ∂V2 This last equation is new. Princeton University Physics Department.N We will see later that this deﬁnition agrees with the conventional deﬁnition of pressure as force per unit area. volume and number of particles. U. We deﬁne the pressure: p=τ ∂σ ∂V . we ﬁnd an expression for the change in total entropy and insist that it be zero (so the entropy is maximum) at equilibrium. ∂U1 ∂U2 which we already knew. Edward J. and by requiring that the entropy be a maximum. N. we were able to show that the temperature is 1 ∂σ . Groth . V2 . N1 ) + σ2 (U2 . = ∂U1 ∂U2 ∂V1 ∂V2 from which we infer that at equilibrium. Working through similar mathematics. Copyright c 2004. U1. they were placed in thermal contact). Why? Because. N1 ) = σ1 (U1 .Physics 301 Pressure 15-Sep-2004 3-1 Last lecture. V1 . V. 0 = δσ ∂σ1 ∂σ2 ∂σ1 ∂σ2 = δU1 + δU2 + δV1 + δV2 ∂U1 ∂U2 ∂V1 ∂V2 ∂σ2 ∂σ1 ∂σ2 ∂σ1 − δU1 + − δV1 .) Again. the total entropy must be a maximum with respect to exchanges of energy and exchanges of volume. once the temperatures are the same. we considered two systems with entropy as a function of internal energy. = τ ∂U V. and ask what happens if we allow them to exchange volume as well as energy? (We’re placing them in mechanical as well as thermal contact. N2 ) . and it must have something to do with the pressure. V1 . ∂σ1 ∂σ2 = .

Note that we can write a change in the entropy of a system. 0 = δσ ∂σ1 ∂σ2 ∂σ1 ∂σ2 ∂σ1 ∂σ2 = δU1 + δU2 + δV1 + δV2 + δN1 + δN2 ∂U1 ∂U2 ∂V1 ∂V2 ∂N1 ∂N2 ∂σ2 ∂σ1 ∂σ2 ∂σ1 ∂σ2 ∂σ1 − δU1 + − δV1 + − δN1 . dU = τ dσ − p dV + µ dN . the chemical potential µ = −τ ∂σ ∂N . = ∂U1 ∂U2 ∂V1 ∂V2 ∂N1 ∂N2 So. Edward J. and which can change its energy by changing the number of particles. guess what we’re going to do now! Suppose we allow the two systems to exchange particles as well as energy and volume. Princeton University Physics Department. you probably have not come across chemical potential in your elementary thermodynamics. τ τ τ or rearranging. Systems with high chemical potential want to send particles to a system with low potential energy per particle. we want to maximize the entropy with respect to changes in all the independent variables and this leads to. Copyright c 2004. U. Like temperature and pressure. speciﬁed in terms of U . µ.V If two systems are allowed to exchange particles and the chemical potentials are unequal. ∂N1 ∂N2 The fact that these derivatives must be equal in equilibrium allows us to deﬁne yet another quantity. Groth . there will be a net ﬂow of particles until the chemical potentials are equal. when the systems can exchange particles as well as energy and volume. which can do mechanical pV work. and N as 1 p µ dσ = dU + dV − dN . Which is the conservation of energy (ﬁrst law of thermodynamics) written for a system which can absorb energy in the form of heat. Unlike temperature and pressure. Again. V .Physics 301 Chemical Potential 15-Sep-2004 3-2 Well. chemical potential is an intensive quantity. You can think of it very much like a potential energy per particle. there’s one variable left. ∂σ2 ∂σ1 = .

Princeton University Physics Department. Nitrogen gas is much more compressible than steel and most of the volume change will be taken up by the gas. one must go to second derivatives. not the steel. Groth . Edward J. We’ll eventually deﬁne Helmholtz and Gibbs free energies and enthalpy (diﬀerent independent variables) and it will always be the case that the ﬁrst derivatives of these quantities produce other quantities that are not material speciﬁc. For example. ∂V ∂V 2 This quantity is related to the compressibility of the material. To get to material speciﬁc quantities. whether it’s nitrogen gas or a block of steel. ∂Usteel ∂Vsteel = S. S. In other words.N ∂Unitrogen ∂Vnitrogen = −p . suppose we have a block of steel and nitrogen gas inside a container that is thermally insulating. Then at equilibrium. Copyright c 2004. the material speciﬁc quantity (second derivative) is diﬀerent for the two materials. and impermeable. we might be interested in ∂p ∂2U =− . the rate of change of energy with entropy (at constant volume and particle number) is the temperature. ﬁxed in volume.Physics 301 First Derivatives versus Second Derivatives 15-Sep-2004 3-3 You will notice that the quantitites deﬁned by ﬁrst derivatives are not material speciﬁc.N If we make a change to the volume of the container. For example.

but gives the sense of a process occurring in time. the tossing of the die resulting in an even number would be made up of the elementary events: the toss is 2 or the toss is 4 or the toss is 6. Well. To start with. Each die has been prepared. Princeton University Physics Department. 3. (This is another way of saying successive tosses are independent. in each toss. For example. In principle. This collection of identically prepared systems and identically performed trials is called an ensemble and averages that we calculate with this construction are called ensemble averages. to be identical. that is. but not deﬁnite. You are probably thinking that for the die.) Then the probability of an event is just the fraction of times it occurs in this large set of experiments. Instead. Presumably.Physics 301 Probability 15-Sep-2004 3-4 Here. both events have occurred! One imagines that a very large number of tosses of the die take place. 4. For example. they could be. A set of elementary events is such that one and only one event can occur in any repetition of the experiment. where ne is the number of times event e occurs and N is the total number of experiments. 6 must be 1/6. the events (1) the toss results in a prime number and (2) the toss gives an even number could not both be part of a set of elementary events. That is. 5. we will introduce some basic concepts of probability. The above deﬁnition is intuitive. and pi = 1 . 4. we throw the same die over and over again and keep track of what happens. as nearly as possible. we can imagine a very large number of dice. 2. Furthermore. ne /N . i where pi is the probability of event i and i is an index that ranges over the possible elementary events. Edward J. the probability of an event is the fraction of the total number of trials in which the event occurs. 5. an attempt is made to ensure that there is no memory of the previous toss. the probabilities of each of the six elementary events 1. tossing a die leads to one of the 6 numbers 1. 3. Groth . Again. Each die is shaken (randomized) and tossed independently. From this deﬁnition it is easy to see that the probabilities of a set of elementary events must satisfy pi ≥ 0 . For example. 2. because if the number 2 comes up. one imagines some experiment or other process in which several possible outcomes may occur. Probability theory itself makes no statement about the values of Copyright c 2004. but it’s not necessary! You’ve heard of loaded dice. right? All that’s really necessary is that each pi be non-negative and that their sum be 1. a set of elementary outcomes can be deﬁned and all possible outcomes can be speciﬁed by saying which elementary outcomes must occur. The possible outcomes are known. we should take the limit as the number of trials goes to ∞. but which number will occur is not known in advance. 6 turning up.

if event i produces the value yi . moment of inertia. Presumably. After the average. we just assign probabilities to the elementary events. The values must come from somewhere else. diﬀerences in the amount and pattern of paint on each face make a negligible diﬀerence in the mechanical properties of the die (such as cm. So. the dots have to be painted on. I’ve occasionally wondered if this might make a detectable diﬀerence in the probabilities. not the entropy! The standard deviation is a measure of the spread about the average. Groth . some dice have rather large indentations for each dot. Edward J. whose value varies across an ensemble.) This is just the average value of the square of the deviation from the average.Physics 301 15-Sep-2004 3-5 the probabilities. However. etc. no face can be distinguished (mechanically) from any other face and we can plausibly argue that the probabilities should be equal. we postulated that a system is equally likely to be in any microscopic state consistent with the constraints. Often we will appeal to symmetry or other arguments to assign the probabilities. are called random variables. so the die isn’t perfectly symmetric. Aside: well. we can calculate its average value just by adding up all the values and dividing by the total number of trials—exactly what you think of as an average. In our discussion of the entropy. 2 var(y) = σy = (y − y )2 . For example. where σy is the standard deviation in y. Copyright c 2004. Princeton University Physics Department. This amounts to assigning the probabilities and is basically an appeal to symmetry in the same way that assigning equal probabilities to each face of a die is an appeal to symmetry! Averages Assuming there is some numeric value associated with each elementary event. then its average value is y = 1 (y1 + y1 + · · · y1 + y2 + y2 + · · · y2 + · · ·) N n1 times n2 times 1 = (n1 y1 + n2 y2 + · · ·) N = yi pi . In general.) so it’s a very good approximation to regard the die as symmetric. since a die is a symmetric cube. we will often be most interested in the variance (often called the square of the standard deviation. i Quantities like y.

Groth . Princeton University Physics Department. Then the probability that the measurement falls in a small range dx around the value x is Prob(x < result < x + dx) = p(x) dx . We can simply deﬁne p(x) = 0 when x is outside the allowed range. −∞ The average of any function of x. where p(x) is the probability density. In this case we deal with a probability density rather than discrete probabilities.Physics 301 Probabilities for Continuous Variables. y(x) is deﬁned by +∞ y = −∞ y(x)p(x) dx . the probability density must satisfy p(x) ≥ 0 . we might make a measurement of a continuous variable x. 15-Sep-2004 3-6 Rather than giving one of a ﬁnite (or inﬁnite) number of discrete outcomes. Copyright c 2004. Edward J. and allowed range of x p(x) dx = 1 . For example. an experiment might result in the measurement of a random variable which is continuously distributed over some ﬁnite (or inﬁnite) range. so the normalization becomes +∞ p(x) dx = 1 . Just as for discrete probabilities.

n and the probabilities are properly normalized.Physics 301 The Binomial Distribution 15-Sep-2004 3-7 As an example of working with probabilities. We suppose that each trial or system is independent and we suppose the probability of heads in one trial or spin up in one system is p and the probability of tails or spin down is 1 − p = q. we would have to say which of the N systems are up and which are down. Since there are 2 states for each of the N systems. but we are interested in all the states that have n up spins. the probability of a particular state with n up spins and N − n down spins is Prob(single state with n up spins) = pn q N−n . To illustrate a trick for computing average values. N y = n=0 n N n N−n p q . we are not interested in a single state with n up spins. etc. Each trial or system has two possible outcomes or states. In particular. We need to know how many there are. (Let’s just call these up and down. Usually. In general. there are N n diﬀerent states with n up spins. We can call these heads or tails (if the experiment is tossing a coin). n N = n=0 N n N−n p q . suppose that when there are n up spins. These states are distinct. There is 1 state with no up spins. What are the mean and variance of y? To calculate the mean. the total number of states is 2N . Edward J. we consider the binomial distribution. I’m getting tired of all these words!) To completely specify the state of the system. spin up or spin down (for spin 1/2 systems). We have N trials or N copies of similar systems. so the probability of getting any state with n up spins is just the sum of the probabilities of the individual states. Princeton University Physics Department. we want to perform the sum. Groth . So Prob(any state with n up spins) = Note that 1 = (p + q) N N n N−n p q . a measurement of the variable y produces n. There are N (N − 1)/2 ways to have two spins up. n Copyright c 2004. n Consider the binomial expansion N (p + q) N = n=0 N n N−n p q . There are N diﬀerent ways we have exactly one of the N spins up and N − 1 down. The probability that a particular state occurs depends on the number of ups and downs in that state.

Physics 301

15-Sep-2004 3-8

and observe that if we treat (for the moment) p and q as independent mathematical variables and we diﬀerentiate both sides of this expression with respect to p (keeping q ﬁxed), we get

N

N (p + q)

N−1

=

n=0

n

N n−1 N−n p q . n

The RHS is almost what we want—it’s missing one power of p. No problem, just multiply by p, N N n N−n p q . N p(p + q)N−1 = n n n=0 This is true for any (positive) values of p and q. Now specialize to the case where p+q = 1. Then N N n N−n p q = y . Np = n n n=0 A similar calculation gives var(y) = N pq . The fractional spread about the mean is proportional to N −1/2 . This is typical; as the number of particles grows, the fractional deviations from the mean of physical quantities decreases in proportion to N −1/2 . So with ∼ N0 numbers of particles, fractional ﬂuctuations in physical quantities are ∼ 10−12 . This is extremely small. Even though the macroscopic parameters in statistical mechanics are random variables, their ﬂuctuations are so small that they can usually be ignored. We speak of the energy of a system and write down a single value, even though the energy of a system in thermal contact with a heat bath is properly a random variable which ﬂuctuates continuously.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 Example—A Spin System

17-Sep-2004 4-1

In the last lecture, we discussed the binomial distribution. Now, I would like to add a little physical content by considering a spin system. Actually this will be a model for a paramagnetic material. This system is also a trivial subcase of the Ising model. We’ll consider a large number, N , of identical spin 1/2 systems. As you know, if you pick an axis, and measure the component of angular momentum of a spin 1/2 system along that axis, you can get only two answers: +¯ /2 and −¯ /2. If there’s charge involved, h h then there’s a magnetic moment, m, parallel or antiparallel to the angular momentum. If there’s a magnetic ﬁeld, B, then this deﬁnes an axis and the energy m · B of the spin system in the magnetic ﬁeld can be either −mB if the magnetic moment is parallel to the ﬁeld or +mB if the magnetic moment is anti-parallel to the ﬁeld. To save some writing, let E = mB > 0 so the energy of an individual system is ±E. In this model, we are considering only the energies of the magnetic dipoles in an external magnetic ﬁeld. We are ignoring all other interactions and sources of energy. For example, we are ignoring magnetic interactions between the individual systems, which means we are dealing with a paramagnetic material, not a ferromagnetic material. Also, we are ignoring diamagnetic eﬀects—eﬀects caused by induced magnetic moments when the ﬁeld is established. Generally, if there is a permanent dipole moment m, paramagnetic eﬀects dominate diamagnetic eﬀects. Of course, there must be some interactions of our magnets with each other or with the outside world or there would be no way for them to change their energies and come to equilibrium. What we’re assuming is that these interactions are there, but just so small that we don’t need to count them when we add up the energy. (Of course the smaller they are, the longer it will take for equilibrium to be established. . .) Our goal here is to work out expressions for the energy, entropy, temperature, in terms of the number of parallel and antiparallel magnetic moments. If there is no magnetic ﬁeld, then there is nothing to pick out any direction, and we expect that any given magnetic moment or spin is equally likely to be parallel or antiparallel to any direction we pick. So the probability of parallel should be the same as the probability of antiparallel should be 1/2: p = 1 − p = q = 1/2. If we turn on the magnetic ﬁeld, we expect that more magnets will line up parallel to the ﬁeld than antiparallel (p > q) so that the entire system has a lower total energy than it would have with equal numbers of magnets parallel and antiparallel. If we didn’t know anything about thermal eﬀects, we’d say that all the magnets should align with the ﬁeld in order to get the lowest total energy. But we do know something about thermal eﬀects. What we know is that these magnets are exchanging energy with each other and the rest of the world, so a magnet that is parallel to the ﬁeld, having energy

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

17-Sep-2004 4-2

−E, might receive energy +2E and align antiparallel to the ﬁeld with energy +E. It will stay antiparallel until it can give up the energy 2E to a diﬀerent magnet or to the outside world. The strengths of the interactions determine how rapidly equilibrium is approached (a subject we will skip for the time being), but the temperature sets an energy scale and determines how likely it is that chunks of energy of size 2E are available. So suppose that n of the magnets are parallel to the ﬁeld and N − n are antiparallel. K&K deﬁne the “spin excess”, as the number parallel minus the number antiparallel, 2s = n − (N − n) = 2n − N or n = s + N/2. The energy of the entire system is then U (n) = −nE + (N − n)E = −(2n − N )E = −2sE . The entropy is the log of the number of ways our system can have this amount of energy and this is just the binomial coeﬃcient. σ(n) = log N n = log N! . (N/2 + s)! (N/2 − s)!

To put this in the context of our previous discussion of entropy and energy, note that we talked about determining the entropy as a function of energy, volume, and number of particles. In this case, the volume doesn’t enter and we’re not changing the number of particles (or systems) N . At the moment, we are not writing the entropy as an explicit function of the energy. Instead, the two equations above are parametric equations for the entropy and energy. To ﬁnd the temperature, we need ∂σ/∂U . In our formulation, the entropy and energy are functions of a discrete variable, not a continuous variable. No problem! We’ll just send one magnet from parallel to anti-parallel. This will make a change in energy, ∆U , and a change in entropy, ∆σ and we simply take the ratio as the approximation to the partial derivative. So, ∆U = U (n − 1) − U (n) = 2E , ∆σ = σ(n − 1) − σ(n) N N − log n n−1 n! (N − n)! N! = log (n − 1)! (N − n + 1)! N! n = log N −n+1 n 1 can’t matter if N − n ∼ N0 = log N −n N/2 + s , = log N/2 − s = log

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

We have N/2 + s = e2E/τ . Now turn oﬀ the magnetic ﬁeld. thermal energy dominates magnetic energy and the net alignment is small. Groth . N/2 − s and with a little algebra 2s E = tanh . Throwing away the 1 is OK. It’s called adiabatic demagnetization. This technique is actually used in low temperature experiments. cooling the surroundings. leaving the magnets aligned. magnetic energy dominates thermal energy and the alignment is large. Copyright c 2004. ∆σ log(N/2 + s)/(N/2 − s) At this point it’s convenient to solve for s. Just what we expected! Suppose the situation is such that E/τ is large. What happens? The system is no longer in equilibrium. It absorbs energy and entropy from its surroundings. To the left. Then the magnets are all aligned. The temperature is then τ= ∆U 2E = . Demagnetization refers to removing the external magnetic ﬁeld and adiabatic refers to doing it gently enough to leave the magnets aligned. Princeton University Physics Department.Physics 301 17-Sep-2004 4-3 where the last line expresses the result in terms of the spin excess. N τ The plot shows this function—fractional spin excess versus E/τ . Edward J. To the right. provided we are not at zero temperature where n = N .

(x − µ)2 − 2σ 2 dx = 1 . As an example of a continuous distribution. The distribution depends on two parameters. the mean. Edward J. The reason the Gaussian distribution is so prevalent is that under very general conditions. σ (not the entropy!). the probabilities of parallel or antiparallel alignment are: p= The ratio of the probabilities is 1 − 2s/N q = = e−2E/τ . identically distributed random variables. this says that energies < kT are “easy” to come by. e Copyright c 2004. Princeton University Physics Department. 1 s + . the distribution of a random variable which is the sum of a large number of independent. p 1 + 2s/N This is a general result. µ. we’ll consider the Gaussian (or normal) distribution. approaches the Gaussian distribution as the number of random variables in the sum goes to inﬁnity. the binomial distribution and (in the homework) the Poisson distribution. As we’ve already mentioned. Probability of low energy state This is called the Boltzmann factor. The relative probability that a system is in two states with an energy diﬀerence ∆E is just Probability of high energy state = e−∆E/τ = e−∆E/kT .Physics 301 The Boltzmann Factor 17-Sep-2004 4-4 An additional comment on probabilities: When the spin excess is 2s. while energies > kT are hard to come by! The temperature ∼ sets the scale of the relevant energies. 2 N q= 1 s − . (not the chemical potential!) and the standard deviation. 2 N The Gaussian Distribution We’ve discussed two discrete probability distributions. It is a function of one continuous variable and occurs throughout the sciences. The probability density is p(x) = √ You should be able to show that √ 1 2πσ 2 +∞ −∞ 1 2πσ 2 − e (x − µ)2 2σ 2 . Groth . This result is called the central limit theorem and is proven in probability courses.

Then the density takes the dimensionless form. 2π Sometimes you might need to integrate this density over a ﬁnite (rather than inﬁnite) range. and the second (obtained √ by changing variables t = x/ 2 rewrites the deﬁnition in terms of the Gaussian probability density. We’re straying a bit from thermal physics. while the complementary error function gives probabilities associated with the tails of the distribution. As an example.” What this means is that the signal that was detected was only 2σ larger than no signal. peaked in the middle. more than 2 percent of the time. In general. The error function gives the probability associated with a range in x at the middle of the curve. Note that erf(0) = 0. or have a fancy calculator that can generate them. so let’s get back on track. One of the reasons for bringing up a Gaussian distribution is that many other distributions approach Copyright c 2004. you might hear someone at a research talk say. One can always recenter so that x is measured from µ and rescale so that x is measured in units of σ. (x − µ)2 2σ 2 dx = σ 2 . noise will give a 2σ result just by chance. erf(∞) = 1. The Gaussian density is just the “bell” curve. x = √ 1 var(x) = √ 2πσ 2 − (x − µ)2 e Appendix A of K&K might be useful if you have trouble with these integrals. This is why 2σ is marginal.Physics 301 1 2πσ 2 +∞ −∞ +∞ −∞ 17-Sep-2004 4-5 − xe (x − µ)2 2σ 2 dx = µ . Princeton University Physics Department. and the complementary error function 2 erfc(z) = √ π ∞ z 2 1 e−t dt = 2 √ 2π ∞ √ 2z 2 e−x /2 dx . with small tails. Groth . “I’ve obtained a marginal two-sigma result. you have to look these up in tables. and erf(z) + erfc(z) = 1. Edward J. 2 1 p(x) = √ e−x /2 . the error function 2 erf(z) = √ π z 0 1 e−t dt = 2 √ 2π 2 √ 2z 0 2 e−x /2 dx . Two related functions are of interest. A noise eﬀect this large or larger will happen with probability 1 √ 2π ∞ 2 2 1 2 e−x /2 dx = erfc √ = 0. where the ﬁrst expression (involving t) is the typical deﬁnition.023 . 2 2 That is.

is ps = N! N N p 2 +s q 2 −s . N/2 ± s is a large number and we can ignore the 1/2. the probability of a spin excess. Groth . The advantage is that it is often easier to work with a continuous function. so things are starting to look promising. (N/2 + s)! (N/2 − s)! We need to do something with the factorials. Then ps = 1 2πN pq p 1/2 + s/N (N/2+s) q 1/2 − s/N (N/2−s) . For large N . or a small number of anti-aligned magnets. the binomial distribution. We expect the peak to be centered at s = s0 = s = n −N/2 = N p−N/2 = N (p−1/2). When the numbers are large. We want to expand this function about its maximum. √ N ! ∼ 2πN N N e−N . Actually. Recall that the variance of the binomial distribution is N pq. then we would have a small number of aligned. (The central limit theorem might have something to do with this!) For example. in the exponents in the last line. So. This is a sharply peaked function. log ps = A + N +s 2 log p − log 1 s + 2 N + N −s 2 log q − log 1 s − 2 N . Princeton University Physics Department. If it were. Edward J. In particular.Physics 301 17-Sep-2004 4-6 a Gaussian distribution when large numbers are involved. if we work with its logarithm. we are working under the assumption that we are dealing with large numbers. s. Also. we can replace the discrete distribution in n with a continuous distribution. Stirling’s approximation is derived. This means that s cannot be close to ±N/2. With this. In K&K. it will be easier to locate the peak and expand the function. Copyright c 2004. Appendix A. we have ps ∼ = = = 2πN NN pN/2+s q N/2−s (N/2+s) (N/2 − s)(N/2−s) 2π(N/2 + s) 2π(N/2 − s) (N/2 + s) 1 pN/2+s q N/2−s 2πN (1/2 + s/N ) (1/2 − s/N ) (1/2 + s/N )(N/2+s) (1/2 − s/N )(N/2−s) 1 2πN (1/2 + s/N ) (1/2 − s/N ) 1 2πN pq p 1/2 + s/N pq pN/2+s q N/2−s pq (1/2 + s/N )(N/2+s) (1/2 − s/N )(N/2−s) q 1/2 − s/N (N/2−s+1/2) (N/2+s+1/2) .

Groth . All this was a lot of work to demonstrate in some detail that for large N (and not too large s). and obtain. Edward J. In particular. The next term in a Taylor expansion requires the second derivative 1 1 d2 log ps =− − 2 ds N/2 + s N/2 − s 1 1 1 =− − =− . So this is the point about which we’ll expand the logarithm. p(s) ds is the probability that that the variable is in the range s → s + ds. just as we expected. p(s) (s + 1) − s = ps .Physics 301 where A= 17-Sep-2004 4-7 1 log 2 1 2πN pq . exponentiate the logarithm. so we require. expanding the logarithm to second order guarantees a Gaussian! In practice. you would not go to all this trouble to do the conversion. we take the derivative and set it to 0 d log ps = log p − log ds s 1 + 2 N − 1 − log q + log 1 s − 2 N +1. which leads to p(s) = ps . we substituted the value of s at the maximum. You might worry about this last step. we let σ 2 = N pq. Of course. in the last line. we have a discrete probability that we just converted into a probability density. p(s) ∼ √ 1 2πσ 2 2 2 e−(s − s0 ) /2σ . The way you would actually do the conversion is to notice that large numbers are involved. In fact. In the discrete case. Np Nq N pq where. the binomial distribution describing our paramagnetic system goes over to the Gaussian distribution. where the notation has been changed to indicate a continuous variable rather than a discrete variable. the spacing between values of s is unity. We note that this expression is 0 when s/N = p − 1/2. We can expand the logarithm as 1 1 (s − s0 )2 + · · · log ps = A − 2 N pq where s0 = N (p − 1/2) is the value of s at the maximum. so the Copyright c 2004. Finally. Princeton University Physics Department. To locate the maximum of this function. Had there been a diﬀerent spacing there would be a diﬀerent factor relating the discrete and continuous expressions.

= 5. the actual s ﬂuctuates about the mean s0 with a spread proportional to √ N and a fractional spread proportional to 1/ N . Princeton University Physics Department. Then the entropy is σ ≈ log N! (N/2)! (N/2)! ∼ N log N − N − 2 (N/2) log(N/2) − (N/2) = N log N − N log(N/2) = N log 2 = 4. Copyright c 2004. a little algebra shows that the variance is σ = N pq = N 2 E 1 sech 2 τ 2 .8 × 107 erg K−1 where the last two lines assume one mole of magnets. so the fractional spread is of order 10−12 and the actual s is always very close to s0 . it’s also interesting to apply Stirling’s approximation to calculate the entropy of our paramagnetic system.Physics 301 17-Sep-2004 4-8 distribution must be Gaussian. we found earlier that the mean value of the spin excess is N E s0 = tanh . √ N ! ∼ 2πN N N e−N . Recalling Stirling’s approximation for large N . 2 τ We can use the Gaussian approximation provided s is not too large compared to N/2 which < means E ∼ τ . Edward J. so log N ! ∼ N log N − N .2 × 1023 (fundamental units) (conventional units) . Then you just write down the Gaussian distribution with the correct mean and variance. Groth . While we’re at it. Returning to our paramagnetic system. Suppose our spin system has s0 ≈ 0. Taking the logarithm. A typical system has N ∼ N0 . 2 2 The ﬁrst two terms can be ignored in comparison with the last two. Then all you need to know are the mean and variance which you calculate from the binomial distribution or however you can. we have log N ! ∼ 1 1 log 2π + log N + N log N − N . In this case. For √ given E/τ .

A system might be a single atom or molecule. for a little culture. The system is supposed to be suﬃciently small that it’s useful to think of it as being in a single (quantum) state. we should let N → ∞.) The system and the bath interact so that the system is in a particular state only with some probability. Consider two states of the system. where N is the number of molecules in the bath. and so on are constant. or just past the edge! The Boltzmann Factor Let’s imagine we have an object which is isolated from the rest of the world. We are going to calculate this probability. and sure enough. Furthermore. Similarly. To have the factor 1 here is the reason that we insisted the system be in a single state. called the system. 277. Princeton University Physics Department. the ratio of the probability Copyright c 2004. We want to speak of the system as having energy E. where U is the total (ﬁxed) energy of the bath plus system. Chapter 3. This means that the interaction between the system and the bath must be weak in order that we can ascribe a deﬁnite energy to the system. so its energy. there is a handout which is a one page article from Science. This may be a case where statistical mechanics is just on. and so on. entropy. and a large piece called the heat bath or heat reservoir (or just bath or reservoir). Also.Physics 301 Reading 20-Sep-2004 5-1 K&K. so all parts of the object are at the same temperature. Groth . vol. We imagine dividing this object into two pieces: a small piece. So. G. 1619. √ Bertsch. Edward J. When the system is in state 1. The remainder of the object. p. these clusters seem to melt over an appreciable range in temperature (rather than a single T ). the number of states in the case that the system has energy E2 is g(U − E2 ) × 1 = exp σ(U − E2 ) × 1 . The number of states that correspond to this energy in the system is g(U − E1 ) × 1 = exp σ(U − E1 ) × 1 . 1997. Our fundamental assumption is that each state (of the system plus bath together) that is compatible with the constraints is equally probable. with energies E1 and E2 . the bath. Where the ﬁrst factor is the number of states in the bath and the second factor is the number of states (just 1) of the system. It describes melting in clusters consisting of 139 atoms! So 1/ N ≈ 10%. is supposed to be very large and might consist of a very large number of similar atoms or molecules. quite a bit larger than the one part in a trillion we’ve been talking about when there is a mole of particles! One might expect things to be less well deﬁned. but it could be a larger entity if such an entity can be described as being in a single state. 1 and 2. pressure. (In principle. the bath has energy U − E1 . it has come to equilibrium.

τ . and we expect that the ﬁrst omitted term will be another factor of ∼ 1/N smaller. it necessarily received that energy from the heat bath. Edward J. we should consider an ensemble of identically prepared heat baths and systems. The number of states goes up with increasing energy U . the fewer states it “has left. and we’ve just shown that this is a general result.Physics 301 that the system is in state 2 to the probability that it is in state 1 is P (state 2) g(U − E2 ) = = eσ(U − E2 ) − σ(U − E1 ) . P (state 1) g(U − E1 ) 20-Sep-2004 5-2 Now. σ(U − E) = σ(U ) − E E ∂σ + · · · = σ(U ) − + · · · . this is called the Boltzmann factor.” This is what makes higher energy states of the system less probable. P (state 1) The probability ratio is an exponential in the energy diﬀerence divided by the temperature. Princeton University Physics Department. The more energy the heat bath gives to the system. ∂U τ Note that The ﬁrst term on the right is ∼ N times larger than the second term. Copyright c 2004. An ensemble in which the probability follows the Boltzmann form (∝ exp(−E/τ )) is called a canonical ensemble. did some mathematical hocus-pocus and voila. When the system is in a state with energy E. E is an energy on the scale of an energy of a single molecule while U is an energy typical of a mole. Inserting this expansion into our expression for the probability ratio. The rate of increase (in the logarithm) is measured by the temperature. A key ingredient is our postulate that all states which satisfy the constraints are equally probable. we have P (state 2) = eσ(U ) − E2 /τ − σ(U ) + E1 /τ = e−(E2 − E1 )/τ . As noted when we discussed the model paramagnetic system. Groth . It may seem we got something for nothing: we made a few deﬁnitions. In principle. So we can expand σ in a tailor series around E = 0. out pops the Boltzmann factor.

if the system is a gas molecule. For example. Note the diﬀerence between the probability of a single state with energy E versus the probability of any state with energy E. so the probability that our molecule has a total energy Etot = Etran + Erot + · · · is just the product. you will often see expressions like P (energy 2) g2 = e−(E2 − E1 )/τ . P (energy 1) g1 where g1 and g2 are called statistical weights. Edward J. with energy Erot . rotation about the center of mass. and various forms of internal energy such as vibration or other electronic excitations and interactions among spins. ··· . For example. if we consider the translational motion. then the probabilities are independent. Groth .Physics 301 Systems with Several Forms of Energy 20-Sep-2004 5-3 A single system in a canonical ensemble might have several ways to store energy. Princeton University Physics Department. For example. then each way has the same probability (our assumption that each state has the same probability) and the probability of being in any state with that Etot is just the sum. This expression agrees with the statement above that the probabilities of the independent states add. we can think of the bath as including the translational and internal motions of the molecule under consideration as well as all the motions of all the other molecules. the moment of inertia. Copyright c 2004. The probabilities are P (Etran ) ∝ e−Etran /τ . Caveat 2: it may not always be true that the energies can be distributed independently. with energy Etran . and hence the rotational energy levels. P (Etot ) ∝ e−(Etran + Erot + · · ·)/τ = e−Etot /τ . may depend on the amplitude of vibration. if we want to know the probability that a molecule is in a particular rotational state. If the system has several diﬀerent ways of distributing Etot among its subsystems. P (Erot ) ∝ e−Erot /τ . all other forms of energy in this molecule and all other molecules may constitute the heat bath. If the energies can be assigned independently. The statistical weight of states with energy E is just the number of distinct states with that energy. These probabilities are independent. it has energy associated with translation of the center of mass. Similarly. Caveat 1: this is the probability for a single state of the system having the speciﬁed total energy. In (older) thermo texts.

is 2 2 2 2 P (E) ∝ e−mv /2τ = e−m(vx + vy + vz )/2τ . This will be the probability of getting E no matter how many diﬀerent states have this E. These are the kinds of conditions that give rise to Gaussian distributions although proving it in this case might be painful. First of all. usually called the density of states. our sample of gas would have a non-zero velocity in the x direction and we are considering a sample at rest (of course!). We might expect this on other grounds as well. we’ve put our ignorance of the number of states into this function! We note that the Boltzmann factor. This expressions applies to a particular state. where C is a constant whose value is adjusted to ensure that p(E) dE = 1. the mean square value of vx contributes to the energy and we would expect this to be Copyright c 2004. What constitutes a particular state? Let’s postpone the counting of states for a bit and see how far we can get with some reasonable assumptions. the forces between molecules are only large when the molecules are within a few molecular diameters of each other. written in terms of velocities. we note that vx is a random variable and its value is determined by the previous history of collisions the molecule has undergone. where m is the mass and v is the velocity of the molecule. Princeton University Physics Department. Now we have a problem. and this probability must be proportional to the Boltzmann factor and to the number of states that have this E. p(E) dE = Ce−E/τ n(E) dE . We consider only the translational energy of a molecule. Otherwise. we should be talking about a probability density. where the probability that the energy lies in the range E → E + dE is given by p(E) dE. We expect that a molecule in a low density gas satisﬁes our deﬁnition of a system which is weakly interacting with its heat bath (all the other molecules in the gas). Also. is the number of distinct states per unit energy with energy E. This strongly suggests that each component of the velocity is normally distributed. In other words. Edward J. and n(E). Generally. We expect that vx = 0. For example. That is. if we want to treat the energy and velocity as continuous variables.Physics 301 Diversion: the Maxwell Velocity Distribution 20-Sep-2004 5-4 Consider a low density gas. The probability that a molecule is in a particular state with energy E = mv 2 /2 is just 2 P (E) ∝ e−E/τ = e−mv /2τ . Groth . if we pick a molecule and measure the x component of its velocity. Usually we think of the energy of translation and the velocity as continuous variables. The mean separation is many molecular diameters.

y. Princeton University Physics Department. p(v) dv = 4π 1 2πτ /m 3 2 2 e−mv /2τ v 2 dv . This is called the Maxwell velocity distribution. vz = v cos θ . 2πτ /m 1 2πτ /m 3 2 2 e−mv /2τ dvx dvy dvz . In fact. φ where vx = v sin θ cos φ . vy . we conclude that the number of states per unit √ energy. so the probability distributions for vx . φ. The result is p(v. the probability is independent of direction. φ) dv dθ dφ = 1 2πτ /m 3 2 2 e−mv /2τ v 2 sin θ dv dθ dφ .Physics 301 20-Sep-2004 5-5 related to the temperature as the Boltzmann distribution suggests. Finally (among things that we expect). Putting all this together. Now let’s change variables from Cartesian components to spherical polar components. p(E) dE = 2π 1 πτ 3 2 1 e−E/τ E 2 dE . Copyright c 2004. vy . and vz → vz + dvz . so we can integrate over direction (θ and φ) to obtain the probability density for the velocity and any direction. θ. vy → vy + dvy . The integral over directions gives 4π and we have. This is just like changing coordinates from x. Just as we expected. back to the energy E = mv 2 /2. n(E) must be proportional to E. Groth . y. there is no reason to prefer one direction over another. the probability of any velocity component should be the same which means that the joint probability should depend only on the magnitude and not on the direction of the velocity. Let’s change variables one more time. v. we guess that the joint probability that the x. Comparing this with our earlier expression. θ. vy = v sin θ sin φ . vz ) dvx dvy dvz = = 2 1 e−mvx /2τ dvx × 2πτ /m 2 1 e−mvy /2τ dvy × 2πτ /m 2 1 e−mvz /2τ dvz . and vz should be the same. θ. and z components of the velocity are in the ranges vx → vx + dvx . z to r. is p(vx . Edward J.

Deﬁne the gamma function by an integral: ∞ Γ(z) = 0 tz−1 e−t dt . We made some changes in variables to convert our guessed probability density in velocity to a probability density in energy from which we concluded that the number of kinetic energy states per unit energy is ∝ E 1/2 . we argued that it was reasonable to expect the velocity components to be normally distributed. For example. these can be found if one knows Γ(1/2) = Can you show this? Copyright c 2004. you will have to integrate over the energy and this is most naturally written as a gamma function. Using the recursion relation. tz−2 e−t dt . ∞ ∞ = −tz−1 e−t = (z − 1) 0 0 ∞ +(z − 1) 0 tz−2 e−t dt (z ≥ 1) . Using integration by parts. one has n! = Γ(n + 1) .Physics 301 20-Sep-2004 5-6 To recap: knowing that the probability of a state with energy E is proportional to exp(−E/τ ). The gamma function satisﬁes a recursion relation. . But I think I should at least introduce the function as it’s necessary for some of the integrals you might need to do. Princeton University Physics Department. We used symmetry arguments to specify the form of the distribution and we used the probability distribution in energy to set the variance. ∞ Γ(z) = 0 tz−1 e−t dt . = (z − 1) Γ(z − 1) . to verify that p(E) above is properly normalized. It is straightforward to show that Γ(1) = 1 and with the recursion relation. Aside—the Gamma Function I kind of side-stepped the gamma function last week when we were using Stirling’s approximation. Groth √ π. Edward J. This relation can be used to extend the deﬁnition of factorial to non-integers! The next most interesting arguments of the gamma function after the integers are half integers.

so maybe it’s time to get back to thermal physics. P (Es ) = 1 . τ2 Copyright c 2004. Edward J. Princeton University Physics Department. We’ve written it as a function of temperature. s where the sum extends over all states s. s ∂ e−Es /τ ∂τ Es e−Es /τ 2 . e−Es /τ P (Es ) = . I should mention the incomplete gamma functions. The average energy of a member of the ensemble is E = s Es P (Es ) . ∞). = s 1 = 2 τ = = Es e−Es /τ . Groth . s Z 1 τ2 Z Es e−Es /τ . Consider the function Z(τ ) = e−Es /τ . Consider the derivative of Z with respect to temperature (the energies of the states. The Partition Function We’ve had a diversion and an aside. Among other things. this function normalizes the probabilities. Es . s Z E . τ −Es τ . ∂ ∂Z = ∂τ ∂τ = s e−Es /τ . but it’s also a function of the energies of all the states which might be functions of macroscopic parameters of the system. (I couldn’t resist. sorry!) These arise when the range of integration does not include the entire interval [0. Z(τ ) s Z is called the partition function. do not depend on temperature).Physics 301 20-Sep-2004 5-7 For completeness.

Princeton University Physics Department. Copyright c 2004. Groth . ∂τ Our discussion followed K&K except that we use E rather than ε and K&K appear to change the deﬁnition of U in midstream from the energy of heat bath to the average energy of a state of a single system. Edward J.Physics 301 from which we deduce that E = τ2 20-Sep-2004 5-8 ∂ log Z .

the second index is the state). If we have two non-interacting systems with total numbers of states g1 and g2 . If there are g states. while the entropies add.j i. It should also improve our intuition about the entropy and the partition function.. pg ) . then we would like to write σ = σ(p1 . . with the above expression. .Physics 301 Entropy and Probabilities 22-Sep-2004 6-1 We’ve been using the idea that the entropy is the logarithm of the number of states accessible to the system. we might expect that the entropy should involve the log of the probability. and the probabilities are p1 . and probabilities p1i and p2j (the ﬁrst index is the system. At this point. . Does this make the entropy additive? Consider σ=− i. To ﬁx up the problem with p1i = 0. an extensive parameter). entropies σ1 and σ2 . Since p1i ≤ 1.j p1i p2j log p1i p2j . σ = σ1 + σ2 and. p1i log p1i − j = σ1 + σ2 . We might expect that an expression for entropy can be written in terms of the probabilities that a system is in a particular state. The ﬁrst guess might be σ1 = − i log p1i wrong . Why doesn’t this expression work? There are several reasons. Groth . Copyright c 2004. . Princeton University Physics Department. pg . . we can also think of it as a single system with g = g1 g2 states. suppose one has a totally isolated system. p2 . . Since the probabilities multiply.j =− =− i p1i p2j log p2j . since any state in system 1 can be combined with any state in 2. the probability of a state in the combined system must be pij = p1i p2j . In addition. Edward J. . we might try multiplying by p1i since in the limit x → 0. This allows one to construct an expression for the entropy of a system that isn’t in equilibrium. Disallowed states have p1i = 0 and this will lead to problems with the logarithm. p2 . the minus sign is inserted to make the entropy positive. p2j log p2j . Then only states with the exact energy of the system are allowed. One of the things that will guide us in our selection of the function is that the entropy should be additive (i. I’d like to make the connection between entropy and probability. We’ve also said that each state is equally likely.e. p1i p2j log p1i − i. the entropy is not additive. . First. x log x → 0.

we’re doing this for convenience. Again. The problem we want to solve is maximizing the entropy under the constraint that the probabilities sum to 1. Then a state can have non-zero probability only if it has the required energy (and any other conserved quantities). Groth . We set the derivative of X with respect to pi to zero. How do we maximize with a constraint? Lagrange multipliers! So we seek to maximize X(p) = σ(p) + λ 1 − i pi . 0= This gives pi = e−(λ + 1) . so the probabilities of all allowed states are the same when the entropy is a maximum.) Finally.Physics 301 22-Sep-2004 6-2 We used the fact that i p1i = j p2j = 1. pi i =− i pi log pi + λ 1 − . Copyright c 2004. So let’s limit our sum to allowed states. σ=− i ∂X = − log pi − 1 − λ . Princeton University Physics Department. Solving for λ. What set of probabilities maximizes the entropy? The answer depends on the conditions under which we seek a maximum. we ﬁnd λ = log g − 1. Suppose we are dealing with a completely isolated system. This time states with energies other than U are allowed. we sum only over allowed states. where we can include or omit states with probability 0 without aﬀecting the value of the entropy. g g g as we had before. (Here. ∂pi 1 1 1 log = − log = log g . Edward J. We also set the derivative of X with respect to λ to 0 which recovers the condition that the probabilities sum to 1. σ=− i pi log pi . Now suppose we consider a system which is not isolated. not because our expression might blow up!) The other thing we know is that the probabilities of the allowed states sum to 1. (g is the number of allowed states and the number of terms in the sum. but is in equilibrium thermal contact with a heat bath so that the average value of its internal energy is U . We adopt the following expression for the entropy in terms of the probabilities.

this is only useful if one is dealing with a homogeneous material. Heat Capacity In general. c = C/m. In the case of gasses. where Ei is the energy of state i. dividing by the mass of the system gives the heat capacity per unit mass. Why is constant in quotes? Answer: the bad news is that it can depend on just about everything. We want 0= It follows that ∂X = − log pi − 1 − λ1 − λ2 Ei . one often divides by something related to the amount of material and then speaks of the speciﬁc heat. You are asked to show in the homework that λ2 = 1/τ . We ﬁnd the maximum of X(p) = − i pi log pi + λ1 1− i pi + λ2 U− i pi Ei . so it can be treated as a constant. the amount of energy added to a system in the form of heat. The case in which the energy of each system is identical and equal probabilities are assigned is known as the micro-canonical ensemble. So. Of course. That is you might speak of the speciﬁc heat of aluminum and the speciﬁc heat of water. the probabilities wind up with a Boltzmann factor! Consider an ensemble of systems. One of the things it obviously depends on is the amount of material in the system. Princeton University Physics Department. ∂pi pi = e−1 − λ1 − λ2 Ei . We want to ﬁnd the probabilities that maximize the entropy under the constraints that the probabilities sum to 1 and average energy is U . where C is “constant” of proportionality. The good news is that over a small range of temperature it doesn’t vary too much. To remove this dependence. the amount of material is usually measured in moles and the heat capacity Copyright c 2004. dQ. The case in which the energies vary and the probabilities are assigned with Boltzmann factors is known as the canonical ensemble. but for boiling water in an aluminum pan you would be concerned with the heat capacity (which you could calculate from the masses of the pan and the water and the speciﬁc heats from the Handbook of Chemistry and Physics). Groth .Physics 301 22-Sep-2004 6-3 provided the average turns out to be U . Edward J. and the rise in temperature dτ resulting from this addition of heat are proportional. For example. dQ = C dτ .

and these can lead to additional deﬁnitions of heat capacity. or Cp . CV = dQ τ dσ ∂σ = =τ dτ dτ ∂τ = V ∂U ∂τ .Physics 301 22-Sep-2004 6-4 is divided by the number of moles to give molar speciﬁc heat or molar heat capacity. A theory will predict the energy levels of a molecular system. An individual magnetic dipole has energy −E when aligned with the ﬁeld and +E when anti-aligned. After a while. Then the internal energy changes only because of the addition of the heat. constant pressure. Measurements of heat capacities. aside from their engineering utility. As an example. Now we are going to use the partition function (the sum of Boltzmann factors) to work out the energy from the temperature. (No change due to work done. All the above is mainly bookkeeping.) Then. The heat capacities in these cases are often written CV . we worked that system out starting from the entropy. (This is a slight diﬀerence in the deﬁnition of E used in the discussion of the partition function. This is usually a number of order Boltzmann’s constant. heat capacities are dimensionless. we will consider the addition of heat at constant volume and particle number. V where we can use dU for τ dσ since we are considering a constant volume (as indicated by the subscript) and constant particle number process. but it’s the same as we used in the discussion of the paramagnetic system. The Boltzmann factor showed up when we considered the numbers of aligned and anti-aligned magnets. Changing to partial derivatives is just a clean up of the mathematical notation. constant volume.) Then Z(τ ) = e+E/τ + e−E/τ = 2 cosh(E/τ ) . Heat added and temperature rise are relatively easy macroscopic quantities to measure. Of course. in conventional units the dimensions are energy per Kelvin. For the moment. Groth . This is usually a number of order the gas constant. you might get the idea that we are overly ﬁxated on heat capacities. It should be noted that in our fundamental units. Recall. In statistical physics. Copyright c 2004. and statistical mechanics relates the microscopic energy levels to macroscopic quantities. are also a good way to test theories of atomic and molecular structure and interactions. However. we can apply the formalism of the partition function to the paramagnetic spin system we discussed in lecture 4. one can think of more complicated way in which heat may be added. no change due to adding particles. Princeton University Physics Department. Of more signiﬁcance is the fact that heat capacities can depend on the manner in which the heat is added to a system. we often speak of the heat capacity per molecule. Heat added to a system whose volume is kept constant will result in a diﬀerent temperature rise than the same amount of heat added to an identical system whose pressure is kept constant. Edward J. so these can provide tests of microscopic theories.

respectively. so CV = −N E ∂ tanh E/τ . Edward J. sech = +N τ τ At high and low temperatures the heat capacity goes to zero because of the τ −2 dependence and the exponential dependence. ∂τ ∂ E = −N E sech2 E/τ . U = Nτ2 ∂ log Z . so increasing the temperature of the bath has little eﬀect on the total energy of the system. Princeton University Physics Department. . ∂τ sinh E/τ ∂ E = Nτ2 cosh E/τ ∂τ τ −E = N τ 2 tanh E/τ 2 . it’s very hard for the bath to get together enough energy to ﬂip a magnet. the magnets are 50% aligned and 50% anti-aligned and the system cannot be made more random by adding energy. When the temperature is low. τ = −N E tanh E/τ . When the temperature is high. Copyright c 2004.Physics 301 22-Sep-2004 6-5 We use the earlier expression to get the average energy per magnet and multiply by N to get the total energy in the system. as before! The heat capacity is ∂U/∂τ . Groth . ∂τ τ 2 E E .

For such a process. In the case of heat transfer. not a state of the system. So exactly what happens when we add heat depends on just how we do it. While the process is underway. and an inﬁnitesimal change in the driving force can make the process run equally well in the reverse direction. before an appreciable amount can leak away!) In any case. the state of the system (and heat bath) is not an equilibrium state. Furthermore. a reversible process is a convenient idealization much like (and related to) the idealization of frictionless mechanical systems. the process occurs inﬁnitely slowly. Princeton University Physics Department. the driving force is the temperature diﬀerence. we can imagine that the system is arbitrarily close to an equilibrium state. Because things are happening so slowly.Physics 301 Reversible Processes 22-Sep-2004 6-6 We’ve glossed over the fact that adding heat is a process. (In actual practice. we consider reversible processes. The process must be carried out slowly so the system has time to get close to equilibrium (for the heat energy to be carried to all parts of the system). the system must not lose any energy by unwanted thermal conduction through the boundaries. A reversible process can be thought of as a continuous sequence of equilibrium states carrying the initial state of the system to its ﬁnal state. Food for thought: Do you suppose there’s a connection between the “direction of the ﬂow of time” and the increase of entropy in irreversible processes? Copyright c 2004. Groth . In particular. Edward J. the “driving force” is inﬁnitesimally small. To obtain an approximation to a reversible process the temperature diﬀerence between the system and the source of heat must be very small. this means you want to perform the heat transfer as quickly as possible.

N − . the number of states doesn’t change. force per unit area.N Copyright c 2004.N . Princeton University Physics Department. we maximized the entropy with respect to changes in energy. In other words. not a thermal energy change. with 1 = τ ∂σ ∂U p = τ ∂σ ∂V µ = τ ∂σ ∂N . σ.Physics 301 Pressure 22-Sep-2004 6-7 Recall in lectures 2 and 3. and particle number and made some deﬁnitions and came up with dU = τ dσ − p dV + µ dN . U. U. If we perform a volume change at constant entropy. We know mechanics: the work done (and energy supplied) when the volume is increased by dV is just −p dV . the energy change produced by a change in volume at constant entropy is purely a mechanical energy change. If the entropy doesn’t change. we just keep the same number of particles. This argument supports our identiﬁcation of p=τ as the conventional mechanical pressure. ∂σ ∂V .V Observe that if σ and N are constant. then the pressure is p=− ∂U ∂V . we are changing the volume without changing the microstates of the system. where p is the ordinary mechanical pressure. volume. U. Groth . Edward J. V. σ requires a bit more thought.N What does it mean to keep σ and N constant? N is easy.

The change in momentum of the wall in one collision is 2mvx . perfectly reﬂecting collision from the wall is ∆Px = −2mvx . vy . and the last Copyright c 2004. which is consistent with the average behavior. consider a wall of the container holding the gas. If. To the extent that we can treat molecules as point masses and ignore their interactions. A gas molecule doesn’t collide with a “wall. there are collisions between molecules and these serve to randomize the velocities and maintain thermal equilibrium. Occasionally. A perfectly elastic and perfectly reﬂecting collision is one in which vx changes sign and vy and vz are unchanged. Edward J. By low density. If the mass of a molecule is m. and consider molecules with velocities in the range vx → vx + dvx . V where the ﬁrst factor is the number of molecules per unit volume. Consider a time interval ∆t and an area of the wall ∆A. there can be no net change in the energy caused by collisions with the wall or the gas would heat up or cool down. there can be no net change in vy or vz or the gas would start moving in the y or z directions. of molecules that are part of the wall. we treat the collisions as perfectly elastic and reﬂecting. We are going to relate the pressure to the motions of the gas molecules. and of course. or a small number. then the change in momentum experienced by this molecule if it makes a perfectly elastic. In other words. Princeton University Physics Department. Do we really think that all collisions between molecules and walls are like this? Of course not. the third gives the fraction of molecules which have the speciﬁed velocity. it will collide with the wall during the time interval. vz → vz + dvz . vy → vy + dvy . To start with. So as a convenience. and the x component of its velocity is vx . In the same way. contrary to the assumption of thermal equilibrium. On the average. vz ) dvx dvy dvz ] [2mvx ] . at the beginning of the time interval. There is a force on this wall because gas molecules are bouncing oﬀ it.Physics 301 Pressure in a Low Density Gas. and this collision is just as “randomizing” as collisions between gas molecules. the second factor is the volume.” it collides with one. I 22-Sep-2004 6-8 Suppose we have some gas in equilibrium at low density. The wall is perpendicular to the x direction. such a molecule is headed in the positive x direction and contained within the parallelepiped indicated schematically in the ﬁgure. Groth . the wall experiences an equal and opposite change in momentum. we mean that the molecules spend most of the time well separated from each other so that they are weakly interacting. The change in momentum caused by such molecules is δPx = N [vx ∆t∆A] [p(vx . the angle of reﬂection equals the angle of incidence and the kinetic energy is unchanged by the collision. we have a model for an ideal gas.

If. we have 1 2 2 2 m vx = m vy = m vz = 3 m v 2 = 2 Etran . We ﬁnd the total change in momentum during the time interval by adding up the contribution of all molecules +∞ +∞ +∞ ∆Px = 0 dvx −∞ dvy −∞ dvz p(vx . Edward J. vy . Copyright c 2004. then Etran = 3τ /2 (homework!) and pV = N τ = N kT = nRT . vz ) N 2 2mvx ∆t ∆A . in fact. Pressure is the rate of change of momentum per unit area. V Since the distribution is independent of direction. so N ∆Px = p= ∆t ∆A V +∞ −∞ +∞ −∞ +∞ 2 p(vx . Princeton University Physics Department. not those which have just collided. vy . vz ) mvx dvx dvy dvz = −∞ N 2 m vx . where Etran is the average translational 3 kinetic energy per molecule. we dropped the factor of two and extended the range of integration to vx < 0. where n is the number of moles and R is the gas constant.Physics 301 22-Sep-2004 6-9 is the change in momentum per collision. the probability density for the velocities is the Maxwell density. Finally. Also since the distribution is isotropic. 3 3 where Utran is the translational kinetic energy of all the gas molecules. pV = 2 2 N Etran = Utran . V where the integral over vx includes only vx > 0 since we want the molecules that are about to collide with the wall. vz ) is the probability density for the velocities and is most likely the Maxwell velocity distribution. but all we require is that it be independent of direction. vy . Groth . Note that p(vx .

they correspond to viscous forces.Physics 301 Pressure in a Low Density Gas. This is a second rank tensor. Note that positive momentum is carried in the positive direction while negative momentum is carried in the negative direction. These are usually numerically equal to the ﬂux of x momentum in the x direction and we have an isotropic pressure. Edward J. we integrate over all velocities and come up with the same thing we had before. Momentum per unit area per second which is force per unit area which is pressure is p= N V 2 d3 v mvx p(v) = N 2 m vx . they might not be zero. these ﬂuxes are zero (can you see why?). Pressure exists throughout a ﬂuid. which was motivated by the Boltzmann factor. Summary: For an ideal gas. However. In general. vz ) = v. we need a nine component object to specify the transport of momentum (a vector) in any of three directions. δA δt V To get the total ﬂux of momentum. Secondly. In the preceding we considered the transport of x momentum in the x direction. δV V All this momentum is carried in the x direction at speed vx . V So. Groth . these molecules have an x momentum density (momentum per unit volume) of δPx N = mvx p(v) d3 v . in writing down the Maxwell distribution. we’ve found an expression relating pressure. However. II 22-Sep-2004 6-10 Look inside a gas. Princeton University Physics Department. We related the energy to the temperature using the Maxwell velocity distribution. in more complicated situations. both contribute to a momentum ﬂux in the x direction. why did we bother with this? For one thing. In fact. volume and translational kinetic energy. and consider molecules with velocity components in dvx dvy dvz ≡ d3 v at (vx . vy . the ﬂux of x momentum in the x direction (momentum per unit area perpendicular to x per unit time) is δPx N 2 = mvx p(v) d3 v . For the simple gas we’ve been considering. it’s a ﬁrst introduction to calculation of transport phenomena. so we haven’t really derived the ideal gas law. we “ﬁnessed” the issue of counting the states. y momentum in the x and z directions and z momentum in the x and y directions. Of course. usually called the stress tensor. we don’t have to introduce a wall to talk about pressure. y momentum is transfered in the y direction and z momentum in the z direction. Copyright c 2004. One can also transport x momentum in the y and z directions.

which corresponds to ﬁtting standing waves in all three directions in the box. (If you recall the Bohr model of the atom. y. we have ψ(x. In one dimension. suitable wave functions are ψ(x) ∝ sin(nx πx/L) where 0 ≤ x ≤ L and nx is an integer. Because ¯ is so small. 24-Sep-2004 7-1 In order to count states. Consider a three dimensional coordinate system with axes nx . ±ny . Princeton University Physics Department. The ﬁrst three wave functions are shown in the ﬁgure. h The ± sign on the momentum indicates that the wave function is a standing wave that is a superposition of travelling waves moving in both directions. the volume of a system is one of the extensive parameters that describes the system and it’s OK for the volume to enter in a manner like it does in the ideal gas law!) In what follows. the idea there is to ﬁt an integral number of wavelengths in the electron’s orbit. ±nz ) . How Copyright c 2004.Physics 301 States of a Particle in a Box.) The momentum is Px = ±nx h/2L = ±nx ¯ π/L. we will use quantum mechanics to ensure that we have discrete states and energy levels. nz (regarded as continuous variables). the physics doesn’t depend on the size of the box. The momentum is π¯ h (±nx . P = L The energy is P2 π2¯ 2 h E= = n2 + n2 + n2 . The de Broglie relation between wavelength (λ) and momentum (P ) is P = h/λ. z) ∝ sin(nx πx/L) sin(ny πy/L) sin(nz πy/L) . As you probably know. Edward J. particles are described by wave functions in quantum mechanics. (Of course. y z 2m 2mL2 x Now we are getting close to being able to count states. we’ll ignore rotational and internal energy of the particles and drop the “tran” subscript. h we will be concerned with energies where the quantum numbers (the n’s) are large. where h is Planck’s constant. Once a box is big enough. and also because we usually deal with a large number of particles. nz integers) in the octant where all are non-negative. This amounts to ﬁtting an integer number of half wavelengths into the box. Let’s consider a single particle which is conﬁned to a cubical box of dimensions L × L × L. In three dimensions. There is a state at each lattice point (nx . and the physics we deduce must not depend in any critical way on the box size when we take the limit of a very big box. Groth . You might think that this is artiﬁcial and wonder how the physics could depend on the size of a box a particle is in? It is artiﬁcial and it’s a trick to make the math easier. The wave function for a particle in a box must be zero at the walls of the box (otherwise the particle might be found right at the wall). ny . ny .

Edward J. That is. It the particles are weakly interacting. Recall that when we discussed the Maxwell distribution. we consider an energy and volume corresponding to the average energy and molar volume of a gas at standard temperature and pressure. Princeton University Physics Department. more than a million times Avogadro’s number. then these states are a ﬁrst approximation to the actual states and we will usually just ignore the interactions when it comes to counting states. Diﬀerentiate both sides with respect to E using the previous result for N (< E). For a large number of states. This is just the volume of an octant of a sphere with radius given by the square root above. Sure enough that’s what we get. We have been working out the states for one particle in a box. √ n(E) = 2π E √ 2mL 2π¯ h 3 . If we have more than one particle in the box. All the other factors get absorbed into the overall normalization constant. we concluded that the density √ of states had to be proportional to E in order to give the Maxwell distribution. and they are non-interacting. and with a mole of particles in the box.Physics 301 many states are there with energy < E? Answer: 1 4π N (< E) = 8 3 E 2 ¯ 2 /2mL2 π h 3 24-Sep-2004 7-2 . Groth . So let’s suppose that E = 3kT /2 where T = 273 K and the volume L3 = 22 × 103 cm3 . The number of states with energy less than E is the integral of the density of states. Copyright c 2004. It’s the number of states because each state (lattice point) occupies unit volume. n(E). where E ′ is the dummy variable of integration. E N (< E) = 0 n(E ′ ) dE ′ . For m we’ll use a mass corresponding to an N2 molecule. we don’t care about the small errors made at the surface of the sphere. The result is about 4 × 1030 states. It will be instructive to work out a numerical value for the number of states for a typical case. then the same set of states is available to each particle. we’ve found that less than one in a million of the available states are occupied. With this approximation.

(rescaling variables) 3 √ ∞ 2 2mτ 1 dr r 2 e−r . mτ is the square of a typical momentum. L3 = 4π 8 π¯ h 0 (changing to spherical coordinates and integrating over angles) 3 √ 2mτ 1 3 1 . Copyright c 2004. We have Z(τ ) = nx . and the volume associated with nQ is roughly ¯ a cube of the de Broglie wavelength. V Γ = 4π 8 π¯ h 2 2 = V (2π¯ /mτ )3/2 h = nQ V . A concentration is just a number per unit volume. For a typical gas at STP. and nQ can be thought of as the concentration that separates the classical (lower concentrations) and quantum (higher concentrations) domains.ny . so the gas can be treated classically. The volume of the system is V = L3 and the quantity that occurs in the last line. This is roughly the smallest volume in which you can conﬁne the particle (given its energy) and still be consistent with the uncertainty principle. ∞ ∞ ∞ Z(τ ) = 0 dnx √ 2mτ π¯ h 0 3 dny 0 ∞ π2¯ 2 h 2 n2 + n2 + nz dnz exp − y 2mL2 τ x ∞ ∞ . So h2 /mτ ∼ λ2 . K&K call nQ the quantum concentration. 2 (Γ(3/2) = √ π/2) .Physics 301 Partition Function for a Single Particle in a Box 24-Sep-2004 7-3 We can use the same states we’ve just discussed to evaluate the partition function for a single particle in a box. nQ has the dimensions of an inverse volume or a number per unit volume. the actual concentration n = N/V is much less than the quantum concentration (by the same factor as the ratio of the number of states to the number of molecules we calculated earlier). Princeton University Physics Department. Groth . Edward J.nz exp − π2¯ 2 h 2 n2 + ny + n2 z 2mL2 τ x . We will make a negligibly small error by converting the sums to integrals. = L 3 0 dx 0 dy 0 dz exp(−x2 − y 2 − z 2 ) .

Why “roughly?” Answer. Edward J. However. these are not diﬀerent composite states if molecules A and B are indistinguishable! The product overcounts the composite states. all with the same mass. then the correction for indistinguishability (what a word!) is not required. so it’s quite safe to ignore occupancies greater than 1. = 3 Nτ . Groth . we’ve already seen that for typical low density gasses. ZN (τ ) = Z1 (τ )N wrong! where ZN is the N -particle partition function and Z1 is the 1-particle partition function calculated in the previous section. less than one in a million single particle states will be occupied. Any given Boltzmann factor appears in the sum roughly N ! times more than it should because there are roughly N ! permutations of the molecules among the single particle states that give the same composite state. Why is this wrong? Recall that the partition function is the sum of Boltzmann factors over all the states of the composite system.Physics 301 Partition Function for N Particles in a Box 24-Sep-2004 7-4 If we have N non-interacting particles in our box. anyway!) To correct the product. N! N! N log mτ 2π¯ 2 h 3/2 . then (see the homework) the partition function for the composite system is just the product of the partition functions for the individual systems. (If this becomes a bad approximation. ∂τ ∂ = τ2 (N log nQ ) . if there are two or more particles in the same single particle state. Princeton University Physics Department. ∂τ (derivatives of N ! and log V give 0) ∂ =τ ∂τ 2 1 N 1 Z1 = (nQ V )N . we use U = τ2 ∂ log ZN . Writing ZN as a product includes terms corresponding to molecule A with energy Ea and molecule B with energy Eb and vice versa: molecule A with Eb and molecule B with Ea . we just divide by N !. so we need to do something diﬀerent. 2 Copyright c 2004. other quantum eﬀects enter as well. ZN (τ ) = To ﬁnd the energy. However. ∂τ ∂ = τ2 (− log N ! + N log nQ + N log V ) .

using the Maxwell distribution. Groth . σ. U Es 3 V all at constant σ. The average energy is E = s Es P (Es ) . changing the volume at constant entropy changes the energy through changes in energies of the individual states. this is a result we’ve seen before.N 2 U . Thus. For each single particle state. Princeton University Physics Department. 2 L dEs 2 dV dU = =− . In lecture 6. Then the pressure is p=− Again. Es ∝ which means 1 ∝ V −2/3 . we noted that p=− ∂U ∂V . Edward J. 3 V Copyright c 2004. We’ve obtained this result before.Physics 301 24-Sep-2004 7-5 which expresses the energy of an ideal gas in terms of the temperature.N and we remarked that keeping the entropy constant while changing the volume of a system means keeping the probability of each microstate constant. Note that our correction for overcounting of the microstates does not appear in the result. ∂U ∂V = σ. and keeping the probabilities of the microstates constant means that P (Es ) doesn’t change.

it is convenient to eliminate the diﬀerential in the entropy in favor of a diﬀerential in the temperature. the extremum is a minimum. Deﬁne the Helmholtz free energy by F = U − τσ . In the above. to the Hamiltonian. = σr (U ) − Us /τ + σs (Us ) . Edward J. Note that unlike our derivation of the Boltzmann factor. Also. dU = τ dσ − p dV . = σr (U ) − Us (∂σr /∂U ) + · · · + σs (Us ) . the partial derivatives above occur at ﬁxed volume and particle number. Groth . maximizing σ requires minimizing F .Physics 301 Helmholtz Free Energy Recall the expression for the conservation of energy. However. then its free energy is an extremum. As it turns out. Princeton University Physics Department. For this we use a Legendre transformation—exactly the same kind of transformation used in classical mechanics to go from the Lagrangian. Copyright c 2004. the free energy is a minimum. the system here need not be so small that it can be considered to be in a single state—it can be a macroscopic composite system. In any case. dF = dU − τ dσ − σ dτ = τ dσ − p dV − τ dσ − σ dτ = −σ dτ − p dV . To show this. = σr (U ) − Fs /τ . we show that when the entropy of the system plus reservoir is a maximum (so equilibrium is established). since we won’t be contemplating changing the number of particles at the moment. a function of coordinates and velocities. the subscripts r and s refer to the reservoir and system and U is the ﬁxed total energy shared by the reservoir and system. σ = σr (U − Us ) + σs (Us ) . a function of coordinates and momenta. If a system is placed in contact with a heat bath and its volume is ﬁxed. Since σr (U ) is just a number. = σr (U ) − (Us − τ σs (Us )) /τ . 24-Sep-2004 7-6 where we have omitted the chemical potential term. and τ is ﬁxed. If we have a system whose temperature is ﬁxed by thermal contact with a heat bath. it should be much smaller than the reservoir so that Us ≪ U . Not all authors use the symbol F for this quantity—I believe some use A and there may be others.

that will create an expansion. This is probably intuitive. τ Copyright c 2004. ∂τ V ∂(F/τ ) .” pressure. Edward J. = −τ 2 ∂τ =F −τ Recall the expression for energy in terms of the partition function U = τ2 Comparing with the above. V The outer equality in this line is called a Maxwell relation. τ Substituting F = U − τ σ in the right equation above. we see σ=− ∂F ∂τ and V 24-Sep-2004 7-7 p=− ∂F ∂V . These occur often in thermodynamics and result from the fact that many thermodynamic parameters are ﬁrst derivatives of the same thermodynamic “potential. τ This shows that at ﬁxed temperature. we have U = F + τσ . if a system can lower its energy by expanding. ∂F . this too. Groth ∂ log Z . generates a “force” to create an expansion. Note that ∂σ ∂V ∂ 2F ∂ 2F =− = ∂V ∂τ ∂τ ∂V ∂p ∂τ =− τ . p=− ∂U ∂V +τ τ ∂σ ∂V . then it generates a “force.” such as the free energy in this case. ∂τ . Putting these together. If the system can increase its entropy (at ﬁxed temperature) by expanding. Princeton University Physics Department. since we are used to the idea that the equilibrium state is a minimum energy state. The Free Energy and the Partition Function Consider F = U − τ σ and σ = −(∂F/∂τ )V .Physics 301 From dF = −σ dτ − p dV . we see F = − log Z + C .

we have p = τ N/V . A ﬁnal note is that these expressions for an ideal gas do not apply in the limit τ → 0. For the entropy. but it does enter the entropy—as might have been expected. Groth . the ideal gas law again. = −τ (N log nQ + N log V − N log N + N ) = −τ N log (mτ /2π¯ 2 )3/2 (V /N ) − τ N . (Stirling’s approx.) . h With p = −∂F/∂V . let’s apply some of these results using the partition function for the ideal gas we derived earlier.Physics 301 24-Sep-2004 7-8 where C is a constant independent of τ . where n = N/V is the concentration. The overcounting correction does not make any diﬀerence in the pressure above. Planck’s constant does enter since it determines the spacing between states and their total number. So C = 0 in order that the entropy have the correct zero point. F = −τ log Z . σ = N log(nQ V /N ) + (3/2)N + N . = −τ log((nQ V )N /N !) . 2 τi Vi a classical result which doesn’t contain Planck’s constant. =N log 5 nQ + n 2 . (Why?) Copyright c 2004. σf − σi = 3 τf Vf N log + N log . In fact. then log Z → log g0 − E0 /τ and σ = −∂F/∂τ → ∂(τ log g0 − E0 − τ C)/∂τ = log g0 − C. σ = −∂F/∂τ . to set the zero point and get an “absolute” entropy. Remembering that the Boltzmann factor is normalized by the partition function to yield a probability. If τ is suﬃciently small. If it occurs g0 diﬀerent ways. Edward J. Princeton University Physics Department. Then F = −τ log Z or Z = e−F/τ . Note that if one considers the change in entropy between two states of an ideal gas. the constant must be zero in order to give the correct entropy as τ → 0. we have e−Es /τ P (Es ) = = e(F − Es )/τ . This called the Sackur-Tetrode formula. only the lowest energy (E0 ) state enters the partition function. Z Just for fun. However.

there is one equation of motion for each coordinate. p. The Hamiltonian is deﬁned by a Legendre transformation. In our discussions. If p and q are given for a particle at some initial time. Princeton University Physics Department. we’ll concentrate on the material in K&K chapter 4. and possibly the time. If one didn’t know about quantum mechanics and didn’t know about discrete states.Physics 301 Reading 27-Sep-2004 8-1 This week. t) = pq − L(q. ∂q ˙ is called the momentum conjugate to q (or the canonical momentum). ∂q so that each second order equation of motion has been replaced by a pair of ﬁrst order equations of motion. In classical mechanics. ∂p p=− ˙ ∂H . so it makes sense to talk about the number of states available to a system. the phase space volume plays the role of the number of states. q. then the time development of p and q are determined by the equations of motion. their velocities. we’ve made use of the fact that quantum mechanics allows us to speak of discrete states (sometimes we have to put our system in a box of volume V ). q. Groth . ∂q Note that q might be a single variable or it might stand for a vector of coordinates. Here’s a slightly more detailed description. We’ve mentioned phase space brieﬂy. In the latter case. q. Edward J. Classical Statistical Mechanics Recall that statistical mechanics was developed before quantum mechanics. L(q. This might be called the thermodynamics of oscillators. where p= ∂L . ˙ ˙ H(q. one has the Lagrangian. t) . The equations of ˙ motion are Lagrange’s equations d dt ∂L ∂q ˙ − ∂L =0. to deﬁne the entropy as the logarithm of the number of states. The equations of motion become (assuming neither L nor H is an explicit function of time) q= ˙ ∂H . If we consider a single pair of conjugate Copyright c 2004. and to speak of maximizing the number of states (entropy) available to the system. how would one do statistical mechanics? Answer: in classical statistical mechanics. t. t) which is a function ˙ of generalized coordinates q.

q1 has a positive momentum. then a point in this space represents a state of the system. Groth . The equations of motion determine a trajectory (or orbit) in this space that the system follows. The ﬁgure shows a trajectory for q1 and for q2 . consider two 1-dimensional particles moving along a common line. q1 = p1 t/m1 . If we consider N 3-dimensional particles. Instead of passing through each other. p1 and p2 are constants and q1 and q2 are linear functions of time. and p2 . The phase space coordinates are q1 . then phase space becomes 6N -dimensional. Note that at some time. one might draw N trajectories in a 6-dimensional space. If we consider a 3-dimensional particle. while q2 has a negative momentum.Physics 301 27-Sep-2004 8-2 coordinates. As an example of a phase space that we might actually be able to draw. The q-p space is called phase space. Edward J. and we consider a space with axes q and p. Each point on the trajectory of q1 corresponds to exactly one point on the trajectory of q2 —the points are labeled by time and points at the same time are corresponding points. for example. then three coordinates and three momenta are required to describe the particle. q2 . both particles are at the same physical place in space and simply pass through each other as we’ve drawn the trajectories above. a one-dimensional system). As shown..) The ﬁgure shows an attempt at drawing a trajectory in the 4-dimensional phase space. Since we have free particles. p1 . (Subscripts refer to particles 1 and 2. This has been drawn assuming equal Copyright c 2004. so its trajectory is from left to right. so its trajectory is from right to left. If we could draw in four dimensions. there would be a single line representing both particles and we would not have to point out this correspondence. suppose they have a collision and “bounce backwards. Suppose they are essentially free particles. Or. p and q (i.e. Princeton University Physics Department.” This might be represented by the diagram shown in the next ﬁgure. Phase space becomes 6-dimensional and is a challenge to draw.

We’d see particles 1 and 2 moving along as free particles before we blinked and again after we blinked. I’m sure you can work out diagrams for other cases. All this is motivation for the idea that collisions randomize the distribution of particles in phase space. Of course the randomization must be consistent with whatever constraints are placed on the system (such as ﬁxed total energy. and an elastic collision. suppose we blinked while the collision occurred. In the two particle case we’ve been considering. Princeton University Physics Department.) In general. Groth . we can see that one way is to say that the particles follow phase space trajectories for a free particle. the molecules travel several molecular diameters between collisions while collisions occur only when molecules are within a few molecular diameters of each other. except every now and then a trajectory ends and reappears—at random— somewhere else.Physics 301 27-Sep-2004 8-3 masses. they changed their momenta. but while we blinked. We’ve already mentioned that in a low density gas. etc. We certainly would not want to try to draw a phase space for all the particles in the gas and we certainly wouldn’t want to try to draw all the trajectories including collisions. Copyright c 2004. One way to treat a low density gas is to treat the molecules as free particles and to try to add in something to account for the collisions. it’s an approximate way to treat collisions. Edward J. Suppose we are considering a low density gas (again!). if a system is in thermal contact with another system. we would expect that the exchanges of energy. By looking at the drawing of the collision (where we blinked). The disappearance and reappearance of phase space trajectories does not really happen. What would we see? The answer (for a suitable blink) is shown in the next ﬁgure. equal and opposite momenta.

so the probability of ﬁnding this particle in a state with energy E is exp(−E/τ ). +L/2 +L/2 +L/2 +∞ +∞ +∞ ZC = dx −L/2 dy −L/2 dz −L/2 dpx −∞ dpy −∞ dpz exp −(p2 + p2 + p2 )/2mτ . the h classical treatment will give the same results as the quantum treatment (but of course. but an integral over phase space volume. we can (at least for a low density gas) reproduce the quantum results simply by using dx dpx dy dpy dz dpz . lacking an h). such as x and px . where the subscript Q indicates the “quantum” partition function. The result is ZC = V (2πmτ )3/2 . if there is a reasonable mapping of quantum states to phase space volume. but it does matter for absolute entropy. Groth . not h. h h h Copyright c 2004. In other words. The entropy is missing an additive constant.Physics 301 27-Sep-2004 8-4 required for thermal equilibrium. ¯ As an example. Recall our previous result for the free particle partition function. one should assign the volume h to a single state. Princeton University Physics Department. the classical and quantum partition functions are ¯ the same except for a factor of h−3 . in this case. The leveling of the probabilities is of course accomplished by the collisions and energy transfers we’ve just been discussing. For example. Even in cases where we used ¯ . This has no eﬀect on relative entropy. Mostly. just as before. and the volume is taken to be a cube of side L for convenience. The classical statistical mechanics analog of our postulate that all accessible states are equally probable is the postulate that all accessible regions of phase space are equally probable. the energy is τ 2 ∂(log Z)/∂τ . would result in randomization of the phase space location. ZQ = V (2πmτ )3/2 1 h 3 . Using classical considerations. Note that the expression includes h. The integrals over the coordinates give V and each integral over √ a momentum gives 2πmτ . An important exception is the entropy. x y z −∞ where ZC stands for the classical partition function. So. The partition function is no longer a sum over states. Our derivation of the Boltzmann factor did not depend on quantum mechanics. we use the logarithm of the partition function. a point in phase space plays the role of a state. It shouldn’t be too hard to convince yourself that any concept we’ve discussed that doesn’t explicitly require Planck’s constant can just as easily be done with classical statistical mechanics as with quantum statistical mechanics. so the h3 factor has no eﬀect on the energy. suppose we consider a single free particle in a box of volume V in thermal contact with a reservoir at temperature τ . Edward J. (How would you measure absolute entropy?) By comparing the two expressions one sees that for each pair of conjugate phase space coordinates. This means that many results that we derive from the partition function will not depend on whether we use ZC or ZQ .

The normalization constant. This is an example related to equipartition of energy discussed by K&K in chapter 3. =√ 2m 2πmτ −∞ 2πmτ −∞ 2m +∞ +∞ τ 1 τ 1 = √ dx x2 exp(−x2 /2) + √ dy y 2 exp(−y 2 /2) . is set by requiring that the integral of the probability density over phase space be unity. 2 2π −∞ 2 2π −∞ τ τ = + =τ. where uppercase P is used for probability density to distinguish if from momentum. Note that the harmonic oscillator has two ways to store energy: as kinetic energy or as potential energy. Groth . This works in general provided the average occupancy is very low. Suppose this oscillator is in thermal equilibrium at temperature τ . we have +∞ +∞ E =C dq −∞ dp −∞ +∞ 1 p2 + m2 ω 2 q 2 exp −(p2 + m2 ω 2 q 2 )/2mτ . 2m +∞ m2 ω 2 q 2 −m2 ω 2 q 2 /2mτ p2 −p2 /2mτ 1 mω dq dp e +√ e . + = 2m 2 2m where ω 2 = k/m is the natural frequency of the oscillator. τ /2 = kT /2. Copyright c 2004. Princeton University Physics Department. To get the average energy of this oscillator. we could obtain the same result by calculating the partition function and going from there. Edward J. A Classical Harmonic Oscillator Now suppose we have a one dimensional harmonic oscillator.Physics 301 27-Sep-2004 8-5 as the appropriate volume in phase space. C. What is the mean value of its energy? One way we can work this out is to take the Boltzmann factor as the probability density in phase space. So P (E) dq dp = C exp −(p2 + m2 ω 2 q 2 )/2mτ dq dp . on the average. The position and momentum integrals can be done separately √ √ and lead to normalization factors mω/ 2πmτ for the position coordinate and 1/ 2πmτ for the momentum coordinate. whose Hamiltonian is H= p2 kq 2 1 p2 + m2 ω 2 q 2 . Each of these can be considered a degree of freedom and each stores. We see that the Maxwell velocity distribution falls out of the classical approach and the h−3 even if included. would get erased in the normalization factor for the probability density. 2 2 Of course.

when the wavelength of the radiation is comparable to or larger than the size of the hole. the energy absorbed must equal the energy radiated. it would heat up to arbitrarily high temperatures (and of course. any radiation hitting the hole. If we consider a ﬁlter which is perfectly transparent in some frequency range and perfectly reﬂecting outside this range and we insert this ﬁlter between the two objects. Princeton University Physics Department. passes through the hole and bounces around inside the cavity until it is absorbed. then it must be the case that it emits the fraction a of the ideal blackbody radiation. we can make the chances of the radiation coming back out the hole before it’s absorbed as small as we like. By making the cavity suﬃciently big and the hole suﬃciently small. In order to avoid violating the second law.. Copyright c 2004. but at high temperatures (in stars. one needs to shield the experiment from direct exposure to room temperature radiation because this can be an important heat load on the cold apparatus. How can we make a perfect absorber of radiant energy? If we could. then nothing would be reﬂected back. Finally. Jargon: a is called the absorptivity and e is called the emissivity. it must radiate the same fraction e(ω) = a(ω) of the ideal blackbody radiation spectrum.Physics 301 Classical Cavity Radiation 27-Sep-2004 8-6 We’re familiar with the idea that hot objects radiate energy. this violates the second law of thermodynamics by transferring heat from a cold object to a hot object with no other change).) A cavity containing a hole must also radiate energy. We can place a physically black object into thermal contact with a cavity radiator. when working at cryogenic temperatures. (Of course. Edward J. by using our ﬁlter again. A hole has no properties. as seen from the outside. A perfect absorber is called a blackbody. then we have to worry about diﬀraction. otherwise we can arrange to violate the second law. The color comes from the appearance of the objects and is the color of the electromagnetic energy radiated by the object. for example) it can become the dominant method of energy transfer. This spectrum is called the blackbody (or thermal or cavity) radiation spectrum. so we couldn’t see anything and it would appear black. So when a cavity is in thermal equilibrium with its surroundings. real absorbers are not perfect.. a fraction a of the incident radiation is absorbed. Allowing two objects to exchange radiation is a way to place them in thermal contact. so the radiated spectrum (energy at each frequency or wavelength or color) can only depend on the temperature. There are the expressions “red hot” and “white hot” denoting very hot objects. Finally. For ordinary temperatures this may not be a very eﬃcient method of heat exchange compared to conduction or convection. It must radiate energy out through the hole at the same rate that energy is absorbed through the hole. We could make a perfect absorber by making a large cavity with a small hole connecting the cavity to the outside world. If not. with the rest being reﬂected. Also. Groth . we conclude that if it absorbs the fraction a(ω) at frequency ω. then we conclude that the perfect absorber and the cavity radiator must radiate the same spectrum (the same amount of energy at each frequency). Then. A real physical object which is a perfect absorber must radiate the same spectrum. If in equilibrium. what would it look like? If it absorbed all the radiation that hit it.

We also know that any electromagnetic wave in a vacuum has two polarizations. (Electric ﬁeld is always perpendicular to the surface of a perfect conductor). so each mode contributes a harmonic oscillator term to the Hamiltonian of the cavity. The sine terms ensure that electric ﬁeld component parallel to a perfectly conducting wall is zero at the wall. and nz are integers. ny . and Copyright c 2004. If we consider a three dimensional space with axes nx . ny . To make life simple. and nx . To calculate the spectrum. As you may know. Groth . nz are related to the number of half wavelengths that ﬁt in the cavity. The spectrum is produced by electromagnetic ﬁelds inside the cavity. These ﬁelds contain energy and they are in equilibrium with the walls of the cavity at temperature τ . Diﬀerent modes have diﬀerent frequencies and this is where the spectrum comes from. where E0 is the amplitude of the mode (an electric ﬁeld. The cavity is assumed to run from 0 to L in each coordinate. Princeton University Physics Department. Maxwell’s equations tell us that π 2 c2 ω 2 = 2 n2 + n2 + n2 . This is another way of seeing how the integers arise. You may recall from your studies of electromagnetism that the ﬁelds in the cavity can be divided into modes with each mode oscillating like a harmonic oscillator. Edward J. not an energy!). The cosine term ensures that the magnetic ﬁeld (related to the E-ﬁeld by Maxwell’s equations) has no perpendicular component at the wall. thermal or cavity radiation spectrum. So we are getting close: we’ve already calculated the average energy in a harmonic oscillator. We start by considering the number that correspond to a frequency less than a particular ω. it must be in phase with the original wave in order to have resonance and a mode. all we have to do now is enumerate the modes and their frequencies and we’ll have the calculation of the blackbody spectrum. ny . And each oscillator has average energy τ according to our earlier calculation. Let us try to calculate this spectrum.Physics 301 27-Sep-2004 8-7 The upshot of all this is that there is a universal radiation spectrum that depends only on temperature and is called the blackbody. x y z L We can think of a mode as a wave bouncing around inside the cavity and when it has bounced around once. Each mode can store energy independently. the electric ﬁeld for a given mode in a perfectly conducting cavity has components of the form Ez = E0 sin(ωt) sin(nx πx/L) sin(ny πy/L) cos(nz πz/L) . we need to know how many sets of integers correspond to a given range in ω. ω is the frequency of oscillation. let’s suppose our cavity is a cube of side L. So for each set of positive integers there are two independent oscillators. The integers nx . Electromagnetic energy oscillates back and forth between the electric ﬁeld (like the position coordinate in a standard harmonic oscillator) and the magnetic ﬁeld (like the momentum coordinate).

It is one of the many contradictions that arose around the turn of the century that led to the development of quantum mechanics. π c where V has been inserted in place of L3 . dω π c and the total energy in the cavity is found by integrating over all frequencies. This is just the volume of 1/8 of a sphere of radius r. This is called the ultraviolet catastrophe. For higher frequencies the measured result falls far below our calculation. so the energy per unit frequency in the cavity is dU V ω2 τ dω = 2 3 dω . Edward J. This should be reminding you very strongly of what we did when counting the states of a particle in a box. Where did we go wrong? This is the same question physicists were asking themselves in the latter part of the nineteenth and the early part of the twentieth century. The answer is. One of the things to note is that cavity radiation could be measured and at low frequencies it gave results in agreement with what we’ve just derived. we didn’t go wrong. Groth . x y z 1 4π N (< ω) = 2 8 3 ωL πc 3 . and V ω2 n(ω) dω = 2 3 dω . so this doesn’t happen. It says that if you made a cavity and put a small hole in it to let the radiation out. where the factor of 2 accounts for the two polarizations. each oscillator has average energy τ . we’re all still here. What’s needed to cure our calculation is a way to keep the high frequency modes from being excited. Copyright c 2004. +∞ U= 0 dω V ω2τ = ∞ !!! π 2 c3 This says there is an inﬁnite energy in the cavity and this can’t be right! Also the energy per unit frequency result says that the energy is concentrated towards the high frequencies in proportion to ω 2 . Everything we did leading up to inﬁnite energy density in a cavity is perfectly legal according to classical physics. Now. The number of oscillators in the frequency range ω → ω + dω is found by diﬀerentiating the above. the spectral density (1/V ) dU/dω is proportional to τ and to ω 2 . That is. you’d be instantly incinerated by the ﬂux of X-rays and gamma rays! Of course. at least as far as classical physics is concerned. Princeton University Physics Department. The ω 2 region is called the Rayleigh-Jeans part of the spectrum. We shall see that it is the discreteness of the energy levels provided by quantum mechanics that keeps these modes quiescent.Physics 301 27-Sep-2004 8-8 nz . then the number is the number of lattice points in this space in the positive octant with n2 + n2 + n2 < r = ωL/πc.

consider the case. so we just leave it out of the accounting. h (¯ ω ≫ τ ) . Princeton University Physics Department. In this case. Recall that we needed a way to keep the high energy modes quiescent in order to solve our cavity radiation problem! Copyright c 2004. we get E →τ. the average energy is “exponentially killed oﬀ” for high energies. We are going to shift the origin slightly and take the energy to be En = n¯ ω . really) has energy levels given by En = (n + 1/2)¯ ω . τ τ If we plug this into the expression for the average energy.) We calculate the average h ∂ log Z h ¯ω = . that ¯ ω ≪ τ . First. The partition function is then ∞ Z= n=0 h e−n¯ ω/τ = 1 exp(¯ ω/τ ) h = . h just as we found for the classical case. On the other hand. (¯ ω ≪ τ ) . then the exponential ¯ in the denominator is large compared to unity and the average energy becomes h E → ¯ ω e−¯ ω/τ . h In other words.Physics 301 A Quantum Harmonic Oscillator 29-Sep-2004 9-1 The quantum harmonic oscillator (the only kind there is. the denominator becomes h ¯ω h ¯ω h e¯ ω/τ − 1 ≈ 1 + +···−1 = . 1 − exp(−¯ ω/τ ) h exp(¯ ω/τ ) − 1 h (Thus is just an inﬁnite series energy of the oscillator xn with x = exp(−¯ ω/τ ). ∂τ exp(¯ ω/τ ) − 1 h E = τ2 It’s instructive to consider two limiting cases. h where n ≥ 0 is an integer and the E0 = hω/2 represents zero point ﬂuctuations in the ¯ ground state. Groth . we are going to ignore zero point energies. Edward J. if hω/τ ≫ 1. That h is. h That is. The actual justiﬁcation for this is a little problematic. the energy level spacing of the oscillator is much less than the typical thermal energy. but basically. it represents an unavailable energy.

When discussing the ideal gas. h ¯ω h ¯ω (¯ ω ≪ τ ) . we identify each mode as a quantum oscillator and realize that the energies (and amplitudes) of each mode are quantized as well. it is populated by particles ¯ with energy hω. So given that we have a mode of frequency ω. With quantum mechanics we also ﬁnd that the occupants of the modes are particles with energies ¯ ω. When hω ≪ τ . In particular. We see that in the limit of low energy modes. When quantum numbers are large. consisting of atoms or molecules. This means that the mode is quiescent (as needed) and also that quantum eﬀects should be dominant. Either way we get quantized frequencies. Edward J. the heat bath. the average occupancy is much less than 1. each mode has many photons. so we get quantized h energies at each quantized frequency. At the other extreme.Physics 301 Quantum Cavity Radiation 29-Sep-2004 9-2 Now that we have given a treatment of the quantum harmonic oscillator. where ω and λ are the frequency and wavelength of the corresponding ¯ wave. we have ¯ E τ → ≫1. you will learn about second quantization which is what we’ve just been talking about! The particles associated with the electric ﬁeld are called photons. Note that the frequency in Hertz is ν = ω/2π. We can get the mode classically by considering standing waves of the ¯ electromagnetic ﬁeld and we can get it quantum mechanically by considering a particle in a box. we know that particles have wave properties and vice-versa and that quantum mechanics associates an energy with a frequency according to E = hω. That is. h In this limit. With quantum mechanics. Princeton University Physics Department. with quantum mechanics. In addition. They carry energy E = hν = hω and momentum p = ¯ h/λ = hν/c = hω/c. so the thermal energy is much larger than the photon energy. Note that our counting of states is basically the counting of electromagnetic modes. These came out quantized because we were considering standing electromagnetic waves. when the photon energy is high compared to the thermal energy. h ¯ω (¯ ω ≫ τ ) . h The average energy divided by the energy per photon is the average number of photons in the mode or the average occupancy. classical considerations gave us quantized frequencies and quantized modes. we can return to the cavity radiation problem. When you take a course in quantum ﬁeld theory. we have E h → e−¯ ω/τ ≪ 1 . They are massless and travel at the speed of light. we expect quantum mechanics to go over to classical mechanics and sure enough this is the limit where the classical treatment gives a reasonable answer. Perhaps a bit of clariﬁcation is needed here. whose typical energies are ∼ τ has a hard time getting together an energy much larger than τ all at once so as to excite a high energy mode. Groth . we said that a low occupancy gas was classical and a high occupancy Copyright c 2004.

we must include it in the integral when we attempt to ﬁnd the total energy.Physics 301 29-Sep-2004 9-3 gas needed to be treated with quantum mechanics—apparently just the opposite of what was said in the previous paragraph! When a large number of particles are in the same state. they can be treated as a classical ﬁeld. +∞ U= 0 dω V ω2 h ¯ω . However. Groth . The energy per unit frequency is dU V ω2 h ¯ω dω = 2 3 dω . let x = hω/τ . For convenience. It is simply the energy per unit volume per unit frequency at frequency ω inside a cavity at temperature τ . The only change we need to make from our previous treatment is to substitute the quantum oscillator average energy in place of the classical result. where the occupancy is low. Thus at low photon energies. with many photons in the same mode. 2 c3 exp(¯ ω/τ ) − 1 π h It is convenient to divide the energy per unit frequency by the volume and consider the spectral density uω . we can speak of the electromagnetic ﬁeld of the mode. where h ¯ ω3 1 dU = 2 3 . π 2 ¯ 2 c3 ex − 1 h The shape of the spectrum is given by the second factor above which is plotted in the ﬁgure. Let’s calculate the cavity radiation spectrum. the behavior is like that of a classical particle but a quantized ﬁeld. since the average energy now depends on frequency. dω π c exp(¯ ω/τ ) − 1 h and the total energy in the cavity is. The number of modes per unit frequency is the same whether we count the modes classically or quantum mechanically. uω = V dω π c (exp(¯ ω/τ ) − 1) h This is called the Planck radiation law. Copyright c 2004. Edward J. ¯ Then x is dimensionless and we have uω = τ3 x3 . Princeton University Physics Department. At high photon energies.

π 2 ¯ 3 c3 0 ex − 1 h τ 4 π4 (looking up the integral) . At low energy the spectrum is proportional to ω 2 in agreement with the classical result. Groth . At high energy there is an exponential cut-oﬀ. = π 2 ¯ 3 c3 15 h π2 τ4 . Edward J. Princeton University Physics Department.Physics 301 29-Sep-2004 9-4 Changing the temperature shifts the curve to higher frequencies (in proportion to τ ) and multiplies the curve by τ 3 (and constants). To ﬁnd the total energy per unit volume we have +∞ u= 0 dω uω . 2 c3 (exp(¯ ω/τ ) − 1) π h 0 ∞ x3 dx τ4 = . Copyright c 2004. +∞ = ¯ ω3 h . = 15¯ 3 c3 h dω The fact that radiation density is proportional to τ 4 is called the Stefan-Boltzmann law. The exponential behavior on the high energy side of the curve is known as Wien’s law.

Edward J.Physics 301 We can also calculate the entropy of radiation. (why?) and obtain σ= 4π 2 3 3 3 Vτ . it has cooled down. τ 15¯ c h 15¯ c h We integrate this relation setting the integration constant to 0. Due to the expansion of the universe. Groth . 45¯ c h It is sometimes useful to think of blackbody radiation as a gas of photons. Some of the homework problems explore this point of view as well as other interesting facts about the blackbody radiation law. so dσ = 1 4π 2 4π 2 2 V τ 3 dτ = 3 3 3 3 V τ dτ . This radiation has been measured very precisely by the FIRAS instrument on the COBE satellite and is shown in the accompanying ﬁgure which was put together by Copyright c 2004. We have U =Vu= π2 4 3 3 Vτ . 15¯ c h 29-Sep-2004 9-5 We know that τ dσ = dU when the volume is constant. Princeton University Physics Department. One application of the blackbody radiation law has to do with the cosmic microwave background radiation which is believed to be thermal radiation left over from the hot big bang which started our universe.

The dashed curve is the theoretical curve and the solid curve represents the measurements where the error bars are smaller than the width of the curve! Other curves on the plot represent deviations in the curve due to our motion through the background radiation (dipole). et al. Edward J. 451. The temperature is 2. Astrophysical Journal.728 ± 0. 1995.Physics 301 29-Sep-2004 9-6 Lyman Page mostly from data collected by Reach. 188. Copyright c 2004. Groth . irregularities due to ﬂuctuations that eventually gave rise to galaxies and physicists (anisotropy) and sources of interfering foreground emission. Princeton University Physics Department..002 K where the error (one standard deviation) is all systematic and reﬂects how well the experimenters could calibrate their thermometer and subtract the foreground sources.

so we can’t change the temperature without changing the pressure. In order to keep the pressure constant. So. This is to be compared with pV = pV = appropriate for a monatomic ideal gas. In the homework you are asked to show that the pressure is given by p= from which one obtains π2τ 4 .Physics 301 More on Blackbody Radiation 29-Sep-2004 9-7 Before moving on to other topics. we can certainly add heat at constant pressure. We can imagine adding some heat energy to a photon gas. Groth . where γ = Cp /CV is the ratio of heat capacity at constant pressure to heat capacity at constant volume. γ = 5/3. γ → 1. an ideal gas obeys the relation pV γ = Constant . For complicated gas molecules with many internal degrees of freedom. 45¯ 3 c3 h 1 U. Princeton University Physics Department. it just means the temperature is constant as well. We can’t do that! The pressure depends only on the temperature. A monatomic gas is “stiﬀer” than a polyatomic gas in the sense that the pressure in a monatomic gas rises faster for a given amount of compression. This. 2 U. 3 In an adiabatic (isentropic—constant entropy) expansion. we’ll clean up a few loose ends having to do with blackbody radiation. 15¯ 3 c3 h How about the heat capacity at constant pressure. What are the heat capacities of a photon gas? Since U= ∂U ∂τ π2 4 3 3Vτ . Edward J. so I suppose the heat capacity at constant pressure is formally inﬁnite! If one recalls the derivation of the adiabatic law for an ideal gas. 15¯ c h = V CV = 4π 2 V τ3 . 3 for a photon gas. we must let the gas expand while we add the energy. plus the fact that we can’t calculate a constant pressure heat capacity is probably a good sign Copyright c 2004. it’s more or less an accident that the exponent turns out to be the ratio of heat capacities. For a monatomic ideal gas.

Princeton University Physics Department. ¯ Let’s ﬁnd the value of x for which this curve is a maximum. Then if the energy density is u = nE.82144. equivalently. The same result holds if the particles have a distribution in energy provided they satisfy P = E/c and v = c. dx ex − 1 3x2 x3 ex = x − x . a small hole in a cavity. The result is x = 2. so for an adiabatic process with a photon gas. e − 1 (e − 1)2 (3x2 − x3 )ex − 3x2 = (ex − 1)2 or 0 = (x − 3)ex + 3 . Edward J. h νmax h ¯ ωmax = . Suppose that particles travel at speed c and that their directions of motion are isotropically distributed.6687 × 10 2 s K4 cm 60¯ c h We saw that the Planck curve involved the function x3 /(exp(x) − 1) with x = hω/τ . At maximum. This transcendental equation must be solved numerically. This can be found by the same kind of argument suggested in the homework problem. but “stiﬀer” than polyatomic gases. We have 0= d x3 . the pressure is u/3. A relativistic gas is “softer” than a similar non-relativistic gas! On problem 3 of the homework you are asked to determine the power per unit area radiated by the surface of a blackbody or. Note that γ = 4/3 mainly depends on the fact that photons are massless. pV 4/3 = Constant .Physics 301 29-Sep-2004 9-8 that we should calculate the adiabatic relation for photon gas directly. and a photon gas is “softer” than an ideal monatomic gas. We already know σ ∝ V τ 3 ∝ V p3/4 . Consider a gas composed of particles of energy E and momentum P = E/c. where n is the number of particles per unit volume.82 = τ k T Copyright c 2004. 2. This will be the case for ordinary matter particles if they are moving at relativistic speeds. The result is (c/4)u where the speed of light accounts for the speed at which energy is transported by the photons and the factor of 1/4 accounts for the eﬃciency with which the energy gets through the hole. The ﬂux is J= π2τ 4 π 2 k4 4 4 = 3 2 3 2 T = σB T 60¯ c h 60¯ c h where the Stefan-Boltzmann constant is π 2 k4 erg −5 σB = . where c is the speed of light. 3 2 = 5. Groth .

uλ = uω dω . π c (exp(2π¯ c/λτ ) − 1) λ2 h 8πhc . = 4 4 x h c e −1 where x = hc/λτ . From this. This is related to uω by the appropriate number of 2π’s..290 cm K .017 . Groth . and at short wavelengths uλ is exponentially cut oﬀ. not the signs of the ranges. .Physics 301 or 29-Sep-2004 9-9 T νmax = h Kelvin = 0. Princeton University Physics Department. uλ → 8πτ /λ4 . 4. the peak of the spectrum is in about the middle of the visible band (do you think this is a coincidence or do you suppose Copyright c 2004.) Let’s apply some of these formulae to the sun. we have λmax T = hc = 0. You will often see uν which is the energy density per unit Hertz rather than the energy density per unit radians per second. . = 5 λ (exp(hc/λτ ) − 1) 8πτ 5 x5 . the constant is easy to remember. You will also see uλ which is the energy density per unit wavelength. The absolute value signs are there because we only care about the widths of the ranges. Edward J. 2. It’s just 3 mm Kelvin.97k This is known as Wien’s displacement law. The solution is x = 4. We use ω = 2πc/λ and dω = (2πc/λ2 )|dλ|. In this form. This says that the energy density within a range of wavelengths should be same as the energy density within the corresponding range of frequencies.96511 . It simply says that the wavelength of the maximum in the spectrum and the temperature are inversely related. This is just a reﬂection of the fact that wavelength and frequency are inversely related. (Note that the wavelength of the maximum in the frequency spectrum and the wavelength of the maximum in the wavelength spectrum diﬀer by a factor of about 1.6. At long wavelengths. First. The maximum of uλ occurs at a wavelength given by the solution of (x − 5)ex + 5 = 0 .82k Gigahertz So the above establishes a relation between the temperature and the frequency of the maximum energy density per unit frequency. This is found from uλ |dλ| = uω |dω| . dλ h ¯ (2πc/λ)3 2πc = 2 3 .

V where Z is the partition function and the requirement of constant volume is satisﬁed by holding the frequency of the mode constant.2 × 1010 erg cm−2 s−1 . Let’s see if we can work this out.Physics 301 29-Sep-2004 9-10 ˚ there’s a reason for it?). h 1 − n/(n + 1) τ 1 − e−¯ ω/τ n/(n + 1) n+1 . We’ve already worked out the partition function for a single mode 1 Z= . very close to what we estimated from the displacement law. we ﬁnd Tsun ≈ 5800 K. h 1 − e−¯ ω/τ The average occupancy (number of photons) in the mode is n= from which we ﬁnd n+1 h = e¯ ω/τ . Using the displacement law (and assuming the sun radiates as a blackbody). The luminosity of the sun is L = 3. Groth . We will use σ= ∂ τ log Z ∂τ . Princeton University Physics Department. = log(n + 1) + n log n = (n + 1) log(n + 1) − n log n . at about λmax ≈ 5000 A = 5 × 10−5 cm. Edward J. The ﬂux emitted by the sun is J = L/4πr 2 = 6. = log Z − τ ∂τ 1 1 h −τ −e−¯ ω/τ = log −¯ ω/τ h h 1−e 1 − e−¯ ω/τ h 1 h ¯ ω e−¯ ω/τ + . ∂τ ∂ h log 1 − e−¯ ω/τ . This is about 60 Megawatts per square meter! We equate this to σB T 4 and ﬁnd Tsun ≈ 5700 K.8 × 1033 erg s−1 . = log Copyright c 2004. Problem 17 in chapter 4 of K&K points out that the entropy of a single mode of thermal radiation depends only on the average number of photons in the mode. − h ¯ω τ − 1 τ . = log(n + 1) + log n 1 − n/(n + 1) n+1 . The radius of the sun is r = 7. Now let’s do the derivatives to get the entropy σ= ∂ (τ log Z) .0 × 1010 cm. n or h ¯ω n+1 = log . τ n 1 ¯ ehω/τ −1 .

So. This is another way of making the point that the expansion of the universe does not change the entropy of the background radiation.Physics 301 29-Sep-2004 9-11 Which is the form given in K&K. but it does not change the number of photons that have the redshifted wavelength—the number of photons in the mode.) Copyright c 2004. the entropy doesn’t change. Edward J. Groth . Princeton University Physics Department. Once the universe is cool enough (≤ 4000 K) that the hydrogen is no longer ionized. then the interactions are very small. The expansion redshifts each photon—stretches out its wavelength—in proportion to the expansion factor. (This assumes that the photons don’t interact with each other or with the matter.

The number of modes per integer n is just 1. then a wave traveling down the line is completely absorbed by the resistor. Vn = Vn. Vn and Vn. Since the resistor and the line are at the same temperature. Let’s consider the low frequency limit so the average h energy in each mode is just τ . all transmission lines have a characteristic impedance. This means that a voltage must appear across the resistor. The waves traveling towards the resistor will be completely absorbed by the resistor. its mean square value will not be zero. we have a resistor R. Suppose its length is L and suppose it is shorted out at each end. Actually. where n is any positive integer. So. Edward J.Physics 301 Johnson Noise 01-Oct-2004 10-1 This is another application of the thermal equilibrium of electromagnetic modes. This means that the resistor must emit waves with equal power in order that there be no net transfer of energy. The ﬁelds must satisfy Maxwell’s equations. Copyright c 2004. each mode acts like an oscillator and ¯ has average energy ¯ ω/(ehω/τ − 1). Each mode in the line is a standing wave composed equally of traveling waves headed in both directions. in equilibrium at temperature τ . What we’ve established so far is that the line feeds power τ dω/2π into the resistor and vice-versa. R. As you may know. If this line is in thermal equilibrium at temperature τ . a voltage generator (the thermally induced voltage source). This is traveling at speed c. This will be a ﬂuctuating voltage with mean 0 since it’s a random thermal voltage. Then any wave that travels along the line is reﬂected at each end and to have an appreciable amplitude. The energy in the frequency band dω per unit length headed towards the resistor is τ dω/2πc. As an equivalent circuit.0 represent the potential diﬀerence and the amplitude of the potential diﬀerence. πc The energy per unit length per unit frequency is then uω = at low frequencies. Consider an ideal transmission line. the speed of propagation can be diﬀerent from c. There are modes of the electromagnetic ﬁelds. let’s take a resistor. In other words this is just a one-dimensional cavity of length L. Groth τ . like a long piece of lossless coaxial cable. so the power incident on the resistor is τ dω/2π which is also the power emitted by the resistor. If a resistor R is connected across the end of the line. Then the number of modes per unit frequency is n(ω) dω = L dω . Princeton University Physics Department. Let’s see if we can calculate this. the length of the line must contain an integral number of half wavelengths. and connect it to the end of the line. most conveniently represented by the potential diﬀerence between the inner and outer conductors.0 sin(ωt) sin(nπx/L). let’s assume it’s ﬁlled with vacuum. πc . they are already in thermal equilibrium and no net energy transfer takes place. so ω = nπc/L. if the coax is ﬁlled with a dielectric. However.

one measures frequencies in Hertz rather than radians per second. For now. Edward J. In the lab. You probably know from your classical mechanics course. resistance. We can imagine that each atom is connected to its six nearest neighbors by springs. This relates the mean square noise voltage which appears across a resistor to the temperature. that the motion of a system of coupled oscillators can be resolved into a superposition of normal modes with the motion of each mode being simple harmonic in time. Then the current is I = V /2R. In general. Groth . this voltage results from ﬂuctuations in the motions of electrons inside the resistor. suppose the atoms in a solid are arranged in a regular cubic lattice. At ﬁrst sight. This is mainly for conceptual convenience. but we calculated it by considering electromagnetic modes in a one-dimensional cavity. we imagine that we’re dealing with an insulator. the motion of a system of coupled oscillators is very complex. Of course. and bandwidth (dν). The equilibrium and the characteristics of the vibrations are determined by interactions with the neighboring atoms. For those of you that know about Fourier transforms. We will treat crystalline solids. one needs to account for the thermal eﬀects of the conduction electrons which behave in many respects like a gas. This gives a linear restoring force which is exactly what happens with a spring. or we can describe the motion with 3N normal mode amplitudes. So our solid is a large number of coupled oscillators. the equilibrium position is determined by a minimum in the potential energy. Each atom vibrates around its equilibrium position. The theory of lattice vibrations that we’ll discuss below applies to the ion lattice in a conductor. Debye Theory of Lattice Vibrations A little thought will show that sound waves in a solid are not all that diﬀerent from electromagnetic waves in a cavity.Physics 301 01-Oct-2004 10-2 a ﬁlter (to limit the frequencies to dω). But. this seems silly. As a model. Copyright c 2004. We’ll consider the electron gas later in the term. but also because we want reasonably well deﬁned vibrational modes. So. a much simpler system! This thermal noise voltage is called Johnson noise. and another resistor of resistance R representing the transmission line. the normal modes are just the Fourier transforms of the position coordinates. Further thought will show that there are some important diﬀerences that we must take into account. we can describe the motion with the N vectors ri which represent the displacement of each atom from its equilibrium position. Finally V 2 = 4Rτ dν . The average power delivered to the resistor is then I 2 R = V 2 /4R = τ dω/2π. and the potential energy almost surely increases quadratically with displacement from equilibrium. Princeton University Physics Department. ν = ω/2π. In addition.

the mode numbers nx . and nz are integers within the cube N 1/3 × N 1/3 × N 1/3 . Princeton University Physics Department. Edward J. It’s messy to deal with this cubical boundary to the mode number space. Second. Instead. In the electromagnetic case. they are similar to the cavity modes we discussed earlier. let’s Copyright c 2004. there is a limit to the number of modes. They are standing elastic waves. A represents an amplitude. ω2 = π2v2 2 nx + n2 + n2 . The frequency and mode numbers are related by the speed of sound. but they are there. y z L2 If the solid contains N atoms. Also. there is no upper limit to the frequency of a mode. we’ll assume that the elastic properties of the solid are independent of the amplitude of the vibrations (at least for the amplitudes we’ll be dealing with). In this respect. ny . This lower limit on the wavelength (upper limit on the frequency) is an example of the Nyquist limit discussed later in these notes. In the elastic case. nx N with similar relations for ny and nz . the solid is a cube of side L. First. If our solid contains N atoms. High frequency modes with ¯ ω ≫ τ are not excited. A typical mode will look something like displacement component = A sin ωt sin nx πx ny πy nz πz sin sin . The wavelength must be longer than twice this distance. 2π 2 v 3 This works for frequencies low enough that the corresponding n’s are within the cube. We’ll carry over as much stuﬀ from the electromagnetic case as we can. or standing sound waves. n(ω) dω = 3V ω 2 dω .Physics 301 01-Oct-2004 10-3 These normal modes represent elastic vibrations of our solid. v. In other words. More precisely 2L 2L > 1/3 . L L L where the sine factors might be cosines depending on the mode. For simplicity. we are going to assume that the velocity of sound is isotropic and is the same for both transverse and longitudinal waves. the distance between atoms is L/N 1/3 . Groth . there are 3N modes. frequencies h which are high enough that the wavelength is shorter than twice the distance between atoms do not exist. There are two main diﬀerences. and for convenience. The number of modes per unit frequency is just as it was for the electromagnetic case except that we must multiply by 3/2 to account for the three polarizations instead of two. there are three polarizations: there are two transversely polarized waves (as we had in the electromagnetic case) and one longitudinally polarized wave (absent in the electromagnetic case).

τ kT T where θ is called the Debye temperature and is given by 1/3 θ= ¯v h . The way to think of it is that a vibration with phonon energy equal to kθ is the highest frequency vibration that can exist within the solid. Such a table is given in K&K. τ4 ex − 1 2π 2 ¯ 3 v 3 h 0 where xD h ¯ ωD = = τ 6π 2 N V 6π 2 N V 1/3 h ¯v kθ θ = = . we can’t look up the integral. we have to numerically integrate and produce a table for diﬀerent values of xD = θ/T . k The Debye temperature is not a temperature you can change by adding or removing heat from a solid! Instead. Then the integral is π 4 /15 and we have 3π 4 N 4 π2V 4 τ = 3 3τ . it’s a characteristic of a given solid. Otherwise the wavelength would be too short.Physics 301 01-Oct-2004 10-4 approximate the upper boundary as the surface of a sphere which gives the same number of modes. We ﬁnd the total energy by adding up the energies in all the modes. (The weird factor of 6π 2 occurs because we replaced a cube with a sphere!) Typical Debye temperatures are a few hundred Kelvin. U= 5k θ 10¯ 3 v 3 h Copyright c 2004. Edward J. The h quanta of sound are called phonons. In other words. In this case xD is very large and we can replace xD by ∞. 2v3 2π exp(¯ ω/τ ) − 1 h 0 xD 3V x3 dx = . The ﬁrst case is very low temperature (T ≪ θ). such that ωD ωD 3V V n(ω) dω = 3N = ω 2 dω = ω3 . Princeton University Physics Department. Instead. Groth . 2v3 2π 2π 2 v 3 D 0 0 which gives 1/3 6π 2 N ωD = v. called ωD . V Each mode acts like a harmonic oscillator and its energy is an integer times ¯ ω. there will be an upper limit to the frequency. The average energies of these oscillators are just as they were in the electromagnetic case. so in general. The limit of integration depends on the temperature. A solid contains a thermally excited phonon gas. There are two limiting cases where we can do the integral. U= ωD h ¯ω 3V ω2 dω .

Edward J. Princeton University Physics Department. τ4 0 xD τ 4 x3 . we picked ωD so this result would occur “by construction. Copyright c 2004. τ3 V 4 as expected.” The heat capacity goes to 3N k in this limit. U= 3V 2π 2 ¯ 3 v 3 h 3V = 2π 2 ¯ 3 v 3 h V = 2π 2 ¯ 3 v 3 h V = 2¯ 3v3 2π h = 3N τ . So a prediction of this theory is that at low temperatures. In one of the homework problems you are asked to come up with a better approximation in the limit of small xD . we expect all modes are excited to an average energy τ . D ¯ 3 v 3 6π 2 N h τ . so the total should be U = 3N τ . Actually. ex − 1 x2 dx . This is borne out by experiment! The other limit we can consider is very high temperature (T ≫ θ). Is this what we get? At very high temperatures. In this case.Physics 301 The heat capacity at constant volume is then 12 4 CV = π Nk 5 T θ 3 01-Oct-2004 10-5 . xD ≪ 1. so we can expand the exponential in the denominator of the integrand. the heat capacities of solids should be proportional to T 3 . Groth . τ4 0 xD x3 dx .

but a discrete set of values: ym = sin(ωmT + φ) . when we sample a sine wave periodically. Princeton University Physics Department. Then ym = sin(2πnm + ΩmT + φ) = sin(ΩmT + φ) . Since we are sampling. Then we can write it as an even integer times the Nyquist frequency plus a frequency less than the the Nyquist frequency: ω = 2nωN + Ω = 2πn/T + Ω . every T seconds. we don’t have a continuous function. where −ωN ≤ Ω ≤ +ωN . Edward J. Consider a sine wave at some frequency ω. y(t) = sin(ωt + φ) .7 cycles every two Copyright c 2004.Physics 301 The Nyquist Frequency 01-Oct-2004 10-6 We imagine that we have a function of time that we sample periodically. A signal at the Nyquist frequency would have one cycle every two sample intervals. Then the Nyquist frequency is the frequency corresponding to a period of two samples. Suppose the frequency is larger than the Nyquist frequency. The high frequency wave has 3. Groth . waves with frequencies greater than the Nyquist frequency look exactly the same as waves with frequencies less than the Nyquist frequency. ωN = 2π/2T = π/T . The arrows along the bottom indicate the times at which the signal is sampled. This is illustrated in the ﬁgure. In other words.

so the high frequency wave looks exactly like a low frequency wave with −0.7π = (4 − 0. Copyright c 2004. The points show the value of the signal (either wave) at each sampling interval. Edward J.3 cycles per two samples. Princeton University Physics Department. Groth .Physics 301 01-Oct-2004 10-7 sample intervals or a phase change of 3. Of course the application to the Debye theory of lattice vibrations is that the Nyquist spatial frequency is the highest frequency a periodic lattice can support.3)π every sample. We can’t tell how many multiples of 2π go by between samples.

Finally. We know the energy of the oscillator. If we don’t run out of modes before we reach the maximum ω of an excited oscillator. Princeton University Physics Department. In the case of lattice vibrations. let’s have a quick recap on oscillators. we made use of a one dimensional cavity. etc. Parting Shot on Oscillators Before we get to the main part of this week’s material. Energy can only be exchanged with the oscillator in units of hω and when this is larger than a ¯ thermal energy. we know the energy of the modes and we count the modes. we again have a number of modes proportional to ω 3 . but there are a ﬁnite number. Basically. ¯ Copyright c 2004. If this h oscillator is in thermal equilibrium at temperature τ . where the number of modes is proportional to ω ( dω) and we considered the low temperature limit and found the energy proportional to τ dω. h. then every mode has energy τ and the total energy is 3N τ (where 3N is the number of modes). These two cases correspond to high and low temperatures and give heat capacities which are constant or proportional to τ 3 for high and low temperatures. and all we have to do is count up how many oscillators there are in order to ﬁnd the total energy of the system. the number of modes is proportional to ω 3 ( ω 2 dω).. its energy levels are spaced by ¯ ω. If hω > τ . For blackbody radiation. the fact that molar heat capacities of solids are usually 3R at room temperature (R is the gas constant) is called the law of Dulong and Petit. and all these modes are excited up to the maximum ω where ¯ ω = τ . If we have an oscillator of frequency ω. come out as a result of the proper bookkeeping when we do the counting. So the energy in blackbody h radiation is proportional to τ 4 . By the way.Physics 301 Reading 04-Oct-2004 11-1 This week we’ll work on chemical potential and the Gibbs distribution which is covered in K&K chapter 5. then the situation is just like that with blackbody radiation and the energy is proportional to τ 4 . so if we run out of modes before we reach the maximum ω of an excited oscillator. This happens because of the quantized states. when we considered Johnson noise in a resistor. All the factors of π. Edward J. its average energy is exponentially “killed oﬀ” and it’s not too gross of an ¯ approximation to say that it’s 0. then if hω < τ . Groth . the heat reservoir almost never gets enough energy together to excite the oscillator. its average energy is ¯ τ .

1964. Edward J.39: ∞ p−1 x dx Γ(p) 1 1 Γ(p) = p 1 + p + p + · · · = p ζ(p) . However. and Mathematical Tables. Princeton University Physics Department. The ﬁrst thing to do is to try and look it up! I like Dwight. (Actually. some (maybe many) of you are wondering just how one goes about doing the integral ∞ 0 x2 dx . You’ve probably learned a number of techniques for doing integrals. Γ(z). Groth . so maybe it’s up to the seventh edition by now!) Anyway. ζ(s) = ks k=1 where Re(s) > 1. Handbook of Mathematical Functions with Formulas. The function can be deﬁned for other values of s. there is entry 860. not a science. MacMillan. you’ll ﬁnd lots of cool stuﬀ. We’ve talked about the gamma function. 1 − 1/ps The zeta function establishes a connection between number theory and function theory! Other things you’ll ﬁnd in A&S are various integral representations. ζ(s) = primes p 1 . ax − 1 e a 2 3 a 0 and this is basically the integral we’re trying to do. Some expressions you just have to integrate numerically! Let’s see what we can do about ∞ In = 0 xn dx . but this series requires Re(s) > 1. exp(x) − 1 The ﬁrst thing to note is that doing integrals is an art. representations in Copyright c 2004. Graphs. there is never a guarantee that an arbitrary expression can be integrated in closed form. 4th edition. US Government Printing Oﬃce. in my edition of Dwight. For example. Tables of Integrals and other Mathematical Data. but I think we’ll need n > 0. or even as a useful series. If you look up the zeta function in this handbook. exp(x) − 1 where n need not be an integer. A good reference book for special functions is Abramowitz and Stegun. The Riemann Zeta function is ∞ 1 . see lecture 5. I bought mine when I was an undergraduate in the late 60’s. It seems that they were coming out with a new edition every 10 years.Physics 301 Integrals Related to Planck’s Law 04-Oct-2004 11-2 Judging by experience with previous classes.

64493 . Can we write In in the form suggested by Dwight? ∞ In = 0 ∞ = 0 ∞ xn dx . (m + 1)n+1 m=0 1 . Their average is 0. If you need to numerically evaluate ζ(s). exp(x) − 1 xn e−x dx . e−(m+1)x dx . = 0 ∞ xn = m=0 ∞ 0 m=0 ∞ n −(m+1)x x e dx . ((m + 1)x) e−(m+1)x d ((m + 1)x) . Groth .. . special values. and tables of values. . ζ(1) = ∞.09545454 . ζ(3). consider ζ(2) = π 2 /6 = 1.1. we ﬁnd it in a table. Instead.. (m)n+1 m=1 ∞ = Γ(n + 1) (m now starts at 1) = Γ(n + 1) ζ(n + 1) . needed for the integral at the top of the page. The two integrals are just 1/11 = 0.5497677 . n = = = 1 (m + 1)n+1 m=0 1 (m + 1)n+1 m=0 ∞ ∞ ∞ 0 ∞ y n e−y dy .Physics 301 04-Oct-2004 11-3 terms of Bernoulli and Euler polynomials (if you don’t know what these are. . ζ(2) = π 2 /6. .. they’re also discussed in A&S). Princeton University Physics Department. . ζ(3) = 1. (Actually the error will be quite a bit smaller!). does not have a simple value. and 1/10 = 0. . . in agreement with Dwight. You should be able to show ∞ (make some sketches) that M dx/xs = 1/[(s − 1)M (s−1) ] is less than remainder of the ∞ sum and M dx/(x − 1)s = 1/[(s − 1)(M − 1)(s−1) ] is greater than the remainder of the sum. and half their Copyright c 2004. The sum of the ﬁrst 10 terms. Edward J. Suppose you’ve summed the inverse powers from 1 to M − 1.09090909 . you can just start summing the series. As an example.2020569 . . . 0 1 Γ(n + 1) . and ζ(4) = π 4 /90. 1 − e−x ∞ = 0 ∞ xn e−x m=0 ∞ e−mx dx . For example ζ(0) = −1/2. 1 + 1/4 + 1/9 + 1/16 + · · ·+ 1/100 = 1. . You can use the average of these two integrals as an estimate of the remainder of the sum and half their diﬀerence as a bound on the numerical error.

Physics 301

04-Oct-2004 11-4

diﬀerence is 0.004545 . . ., so numerically we can be pretty sure that the value is within 0.00455 of 1.64522. In fact, we actually miss by only 0.00028!

The Chemical Potential Recall in lectures 2 and 3 we discussed two systems in thermal (microscopic exchange of energy), volume (macroscopic exchange of energy), and diﬀusive (exchange of particles) equilibrium. By requiring that the entropy be a maximum, we found that dσ = 1 p µ dU + dV − dN , τ τ τ

**where µ is the chemical potential and N is the number of particles. In other words, µ = −τ ∂σ ∂N .
**

U,V

We can also rewrite the diﬀerential relation above in the form dU = τ dσ − p dV + µ dN , from which we deduce µ= ∂U ∂N

.

σ,V

Adding a particle to a system changes its energy by µ. Of course, the entropy is not a completely natural variable to work with as a dependent variable. To get around this, we use the Helmholtz free energy which we’ve previously deﬁned as a function of temperature and volume. We now extend the deﬁnition to include particle number. In particular, consider the free energies of two systems in contact with a reservoir at temperature τ . We allow these two systems to exchange particles until equilibrium is established. The free energy of the combined system is F = F1 + F2 , where the subscripts refer to the individual systems. The free energy will be a minimum at constant temperature and volume. The change in free energy due to particle exchange is ∂F2 ∂F1 dN1 + dN2 . dF = dF1 + dF2 = ∂N1 τ,V ∂N2 τ,V

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

04-Oct-2004 11-5

We want dF = 0 at minimum and, since the total number of particles is constant, we have dN1 = −dN2 which means that ∂F1 ∂N1 =

τ,V

∂F2 ∂N2

=µ.

τ,V

This constitutes yet another deﬁnition of the chemical potential. Is it the same chemical potential we’ve already deﬁned? Yes, provided the free energy continues to be deﬁned by F = U − τσ . Then when the particle number changes, we have dF = dU − τ dσ − σ dτ , = τ dσ − p dV + µ dN − τ dσ − σ dτ , = −σ dτ − p dV + µ dN , and it’s the same chemical potential according to either deﬁnition. By the way we deﬁned the chemical potential, it must be the same for two systems in diﬀusive and thermal contact, once they’ve reached equilibrium. What if the two systems in diﬀusive contact do not have equal values of the chemical potential? Since dF = dF1 + dF2 = µ1 dN1 + µ2 dN2 , there will be a ﬂow of particles in order to minimize F . If µ1 > µ2 , then dN1 < 0 and dN2 = −dN1 > 0, so particles ﬂow from the system with the higher chemical potential to the system with the lower chemical potential. To summarize, µ = −τ ∂σ ∂N =

U,V

∂U ∂N

=

σ,V

∂F ∂N

.

τ,V

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 Getting a Feel for the Chemical Potential

04-Oct-2004 11-6

The chemical potential is another one of those thermodynamic quantities that seems to appear by magic. In order to gain intuition about the chemical potential, you will probably have to see it in action and work with it for a while. To start this process, note that adding a particle to a system requires that the energy of the system be changed by µ while the entropy and volume are kept constant. Better yet, the free energy changes by µ while the temperature and volume are kept constant. Why might adding a particle to a system change the system’s energy? There are at least two reasons. There might be macroscopic ﬁelds around (such as gravitational or electromagnetic ﬁelds) in which the particle has an ordinary potential energy (mgh or eΦ for example). In addition when a particle is added to a system at temperature τ , it must acquire a thermal energy which depends on τ and other parameters of the system. In other words the change in energy upon adding a particle can be due to both macroscopic ﬁelds and microscopic thermal eﬀects. The distinction made in K&K between the external, internal and total chemical potentials is just a division into the macroscopic, microscopic, and total contributions to the energy upon adding a particle. Let’s ﬁnd the chemical potential of the classical, ideal, monatomic gas. Recall in lecture 7, we found, 3 U = Nτ , 2 nQ +1 , F = −N τ log n nQ 5 σ = N log , + n 2 mτ nQ = 2π¯ 2 h N n= . V

3/2

,

Of the thermodynamic potentials U , F , and σ above, only F is expressed in terms of its natural independent variables τ , V , and N . Let’s ﬁnd µ by diﬀerentiating F with respect to N while keeping τ and V constant. µ= ∂F ∂N =

τ,V

∂ ∂N

−N τ log

log

nQ V +1 N

,

= −τ

nQ V +1 +τ , N

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

the concentration n is quite small compared to the quantum concentration. and N . We express the entropy in terms of its natural independent variables U . Edward J. σ=N =N substitute τ = 2U/3N . volume and number of particles. Instead. Groth . If µ gets close to zero.V log mU 3π¯ 2 h mU 3π¯ 2 h 3/2 3/2 V N 5/2 + 5 2 + 5 2 5 2 . V N 5/2 + . we can write the energy as a Copyright c 2004. V . N n . = τ log nQ = −τ log the same as we obtained before. =N log mU 3π¯ 2 h 3/2 log log nQ 5 + n 2 mτ 2π¯ 2 h . suppose we wanted to ﬁnd the chemical potential by diﬀerentiating the energy. = τ log nQ = −τ log 04-Oct-2004 11-7 Note that for a typical gas. This should be done at constant entropy and volume. N n . nQ . and replace U with 3N τ /2. µ = −τ = −τ = −τ ∂σ ∂N ∂ N ∂N log . Princeton University Physics Department. Since we’re having so much fun playing with the mathematics. Now diﬀerentiate with respect to N . . So we expect µ = −14τ to −11τ . U. then the concentration is approaching the quantum concentration and the classical treatment is no longer valid. Suppose we wanted to calculate the chemical potential by diﬀerentiating the entropy. perhaps a part in 106 to a part in 105 . V N 5/2 − nQ V . multiply by −τ . The Sackur-Tetrode formula for the entropy is fairly messy to solve for the temperature.Physics 301 nQ V . 3/2 V N + 5 2 5 2 . so we may not want to rewrite the energy in closed form as a function of the entropy.

Physics 301 04-Oct-2004 11-8 diﬀerential involving dN and dτ and ﬁnd the relation between these diﬀerentials which makes the entropy change vanish. with the lighter molecules having a large scale height (and being more likely to completely evaporate from the Earth). Suppose the atmosphere consists of a single kind of atom of mass m. With the ideal gas law. so the pressure also decreases exponentially with altitude. T = 300 K. However. and is in equilibrium. Edward J. R is the gas constant. Needless to say. Princeton University Physics Department. At higher altitudes. Copyright c 2004. This means n µ = Constant = τ log + mgh . the atmosphere is stirred by winds. is called the scale height of the atmosphere. This will be left as a homework problem. each molecule should have a slightly diﬀerent scale height. nQ or n(h) = n(0)e−mgh/τ . consider our atmosphere which exists in the gravitational ﬁeld of the Earth. If we take. Groth . First. Then the chemical potential must be the same everywhere in the gas. where h0 = τ /mg = kT /mg = RT /M g. At height h above the zero level for the gravitational potential. we ﬁnd h0 ≈ 9 km. As an example of a macroscopic contribution to the chemical potential. the atmosphere is approximately isothermal. and g = 980 cm s−2 . there is a contribution mgh from the gravitational ﬁeld. but with a considerable colder temperature. is isothermal. so the concentration decreases exponentially with altitude. so it is not in equilibrium. M = 28 g (appropriate for Nitrogen molecules). one gets the same expression for the chemical potential that we’ve already derived. p/τ = N/V = n. this is important only in the ﬁrst few miles above sea level. There are several problems with this simple model. and M is the molar mass. about 230 K according to the plot in K&K. We can write p(h) = p(0)e−h/h0 . Also.

K&K use a kind of cursive Z symbol for this sum. A probability distribution described by Gibbs factors is called the grand canonical distribution. ∝ eσ(N0 − N. The probability P (N. Groth ∂σ ∂σ −E ∂N ∂U . and then over all numbers of particles with that energy. σ(N0 . where we dropped the ﬁrst factor since it’s a constant for any given reservoir. all possible states of N particles with energies E. e(N µ − E)/τ . E where the sum is over all numbers of particles N . the grand sum. or the grand partition function. ∝ eσ(N0 . The total energy is U0 and the total number of particles is N0 (which is not Avogadro’s number during this discussion!). U0 − E) . one can sum over all energies ﬁrst. U0 ) − N ∝e ∝ e(σ(N0 . Z is called the Gibbs sum. is called the Gibbs factor. Or. P (N2 . E) ∝ g(N0 − N. U0 ) + N µ/τ − E/τ ) . we divided up a large object into a system and a heat reservoir and we considered what happens when the system and reservoir exchange energy. Edward J. U0 − E2 ) × 1 where g(NR . so we’ll use Z. U0 − E) . Copyright c 2004. Consider the sum Z= All N . Basically it’s a sum over all possible states which are parameterized by number of particles and energy. We have P (N. What is the probability that the system is in the single state 1 with N1 particles and energy E1 compared to the probability that it’s in the single state 2 with N2 particles and energy E2 ? The ratio is P (N1 .Physics 301 The Gibbs Factor 06-Oct-2004 12-1 In lecture 5. Now let’s consider the what happens if we divide up the large object into the system and a reservoir except this time we allow the exchange of particles as well as energy. I don’t seem to have that in my TEX fonts. UR ) is the number of states available to the reservoir when it contains NR particles and has energy UR . and for each N . ∝ e(N µ/τ − E/τ ) . E1 ) g(N0 − N1 . E) ∝ e(N µ − E)/τ . We are just applying our postulate that the probability is proportional to the number of available states. E2 ) g(N0 − N2 . This led us to the Boltzmann factor and the partition function. U0 ) × e(N µ/τ − E/τ ) . Princeton University Physics Department. U0 − E1 ) × 1 = . .

E 1 ∂Z =τ . Z With the normalized probability distribution. it will pull down a term with the energy in it. For example. ∂(1/τ ) ∂ log Z . = µτ ∂µ ∂τ K&K deﬁne the activity as λ = eµ/τ . Princeton University Physics Department.Physics 301 The grand partition function is used to normalize the probabilities: 06-Oct-2004 12-2 1 (N µ − E)/τ e . The grand partition function can be rewritten in terms of the activity as Z= All N . Z ∂(1/τ ) ∂ log Z = . Edward J. but we’ll also get the number of particles again. we can compute mean values. Z τ All N . E = Nµ − ∂(1/τ ) ∂ log Z . Groth λN e−E/τ . E) = N = 1 Z N e(N µ − E)/τ . the mean number of particles in the system is P (N. If we diﬀerentiate Z with respect to 1/τ . Nµ − E = 1 Z (N µ − E) e(N µ − E)/τ . ∂µ ∂(1/τ ) ∂ log Z ∂ log Z + τ2 . All N . All N . =τ ∂µ The mean energy is slightly more complicated. =µ N − ∂(1/τ ) ∂ log Z ∂ log Z = µτ − . E Copyright c 2004. . Z ∂µ ∂ log Z . E 1 N (N µ − E)/τ =τ e . E 1 ∂Z = .

and specialize to the case of four molecules later. We will let the activity be λ = exp(µ/τ ). ∂λ 06-Oct-2004 12-3 Example: Binding of N Molecules This example is related to the myoglobin example discussed in K&K and also to K&K. ǫ < 0. This is not quite right as successive oxygen molecules are bound more tightly than the ﬁrst oxygen molecule. We will assume that each successive molecule binds with same energy (relative to inﬁnite separation). Groth . Z = 1 + λe−ǫ/τ + λe−ǫ/τ 1 − λe−ǫ/τ = M +1 2 + · · · + λe−ǫ/τ M . Also. Princeton University Physics Department. Copyright c 2004. We will work out an expression for the average number of molecules as a function of the partial pressure of oxygen in the atmosphere. This corresponds to assuming that the molecules are bound to hemoglobin in a deﬁnite order. The example system is a hemoglobin molecule which can bind zero to four oxygen molecules. ∂λ (M + 1) λe−ǫ/τ =− 1 − λe−ǫ/τ = λe−ǫ/τ M +1 M +1 + λe−ǫ/τ . Now we diﬀerentiate with respect to λ in order to ﬁnd the average number of bound molecules. we will assume that there is only one state in which N molecules are bound. 1 − λe−ǫ/τ . Edward J. problem 14. chapter 5. A hemoglobin molecule is similar to four myoglobin molecules. 1 − λe−ǫ/τ M 1 − (M + 1) λe−ǫ/τ 1 − λe−ǫ/τ + M λe−ǫ/τ 1 − λe−ǫ/τ M +1 M +1 . Then the grand partition function is. N =λ ∂ log Z . each of which can bind zero or one oxygen molecule. M +1 log Z = log 1 − λe−ǫ/τ − log 1 − λe−ǫ/τ .Physics 301 from which it follows that the average number of particles is N =λ ∂ log Z . Finally. we will start by assuming that 0 to M molecules may be bound.

which corresponds to myoglobin which can bind one molecule. λ = exp(µ/τ ). If we look at the curve for myoglobin in ﬁgure 5. so the maximum partial pressure is roughly 150 mm of Hg. This means that λ = n/nQ = p/τ nQ . Groth .12 of K&K. and nQ is the quantum concentration evaluated at temperature τ and for the mass of an O2 molecule. 4 4 (1 − x5 )(1 − x) 4 1 + x + x 2 + x3 + x4 where x = λ/λ1/2 . 1 + λe−ǫ/τ Now. it appears that the average number of bound molecules is about 1/2 when the partial pressure of oxygen is about 5 mm of Hg. where p is the partial pressure of oxygen. Let λ1/2 be the activity when the number of bound molecules is 1/2. we see that this means λ1/2 exp(−ǫ/τ ) = 1 or exp(−ǫ/τ ) = 1/λ1/2 . So λ can be evaluated numerically for any desired partial pressure of oxygen. Binding more molecules. (One atmosphere is 760 mm of Hg and oxygen is about 20% of the atmosphere. Edward J. all with the same binding energy. Let’s plug this into the formula for hemoglobin (M = 4) and express the result as a fraction of the maximum number of bound molecules. and in order for our system to be in equilibrium with atmospheric oxygen it must have the same chemical potential as atmospheric oxygen. Princeton University Physics Department. The result is N x 1 − 5x4 + 4x5 x 1 + 2x + 3x2 + 4x3 f= = = .Physics 301 06-Oct-2004 12-4 In the case that M = 1. the expression becomes λe−ǫ/τ N = . From our expression above. τ is the temperature of atmospheric oxygen (presumably room temperature). causes a sharper transition from “empty” to “full!” Copyright c 2004. This curve is shown in the ﬁgure.

V1 V1 . If we remove a molecule from container 1 and add it to container 2. The total amount of energy that must be supplied by an external agent to move this molecule is µ2 − µ1 > 0. V2 = −N τ V1 dV . n2 n1 = τ log − τ log . we learned that the chemical potential for an ideal monatomic gas is µ = τ log(n/nQ ) which is about −14 to −11τ for a typical gas under typical conditions. from concentration n1 up to concentration n2 . but we get back some energy! This must be wrong. It appears that if we add one more particle to a gas. Groth . Edward J. = N τ log n1 So the energy per molecule required to isothermally change the concentration from n1 to n2 is just the energy required to move one molecule from a gas at concentration n1 to a gas at concentration n2 . the pressures are diﬀerent with p2 > p1 . N/V1 n2 . Then the concentrations must be diﬀerent. There’s also an energy involved in removing the particle from its original location before we add it to the gas.Physics 301 06-Oct-2004 12-5 More on the Chemical Potential—Energy to Add a Particle This section is based on the discussion in K&K in pages 250–252. the chemical potential is the amount of energy required to add one particle to a system. Princeton University Physics Department. n1 Now suppose we have N molecules of a gas at temperature τ and we isothermally compress it from volume V1 down to volume V2 or. Copyright c 2004. As you recall. but what’s the explanation? The answer has to do with where the particle came from. or equivalently. Also. we’re not required to spend energy. What does this turn out to be? ∆E = µ2 − µ1 . Suppose we have two containers of the same gas at the same temperature. V = −N τ log = N τ log V2 . Suppose the chemical potentials are diﬀerent with µ2 > µ1 . equivalently. V2 N/V2 = N τ log . we receive energy µ1 from container 1 but must give energy µ2 to container 2. τ . nQ nQ n2 = τ log . How much mechanical work is required? V2 ∆W = V1 −p dV .

Rather than discuss the lead acid battery. voltaic cells. (True confession: I have not read the article in the American Journal of Physics. Pauling. Recall that the internal energy of an ideal monatomic gas depends only on its temperature (U = 3N τ /2). This requires spending an energy N τ log(n2 /n1 ). so the internal energy of the gas did not change! Where did the energy τ log(n2 /n1 ) go??? Hints: has the free energy of the combined systems changed? What about the entropy? Example: Chemical Potential and Batteries Surprise: chemical potential might actually have something to do with chemistry! An example has to do with batteries—or better. But the TAMU physics web site has been revamped and I can’t ﬁnd the preprint anymore!) The Daniell cell is also discussed in chemistry textbooks. did you know that Princeton subscribes to many of the on-line journals? This means if you access the web from a Princeton address. However. 574. 76. 1996. you’ll be allowed to read the journals on-line. Chemical reactions occur at the electrodes. This is discussed by the same author in 1999. College Chemistry. The ﬁgure shows a schematic of the cell. W. Move the molecule from container 1 to container 2. we could imagine doing the following: Isothermally compress the gas in container 1 from concentration n1 to concentration n2 . The neutral copper atom “plates out” on the copper electrode. PRL. (San Francisco:Freeman). the reaction is Cu++ + 2e− → Cu . let’s look at a simpler (I hope) system: the Daniell cell. 1964..Physics 301 06-Oct-2004 12-6 In fact. Before and after we moved the molecule from container 1 to container 2. Edward J. 67. so the net expenditure of energy is τ log(n2 /n1 ) = µ2 − µ1 . 4849. the temperature of all the gas was τ . L. In particular see Saslow. This recovers an energy (N − 1)τ log(n2 /n1 ).. Expand the gas in container 1 back to concentration n1 . In particular. Copyright c 2004. The following discussion is based on both of these sources. Princeton University Physics Department. At the copper electrode. 354. This requires no energy since the concentrations and the chemical potentials are now the same. p. I’ve been told that this discussion is not quite right. The copper ion was in solution and the electrons come from the electrode. The zinc electrode is the negative electrode or cathode and the copper electrode is the positive electrode or anode. such as the one I used many years ago. the preprint that used to be on the author’s web site. but rather. It has a solution of zinc sulfate (ZnSO4 ) surrounding a zinc electrode and a copper sulfate (CuSO4 ) solution surrounding a copper electrode. K&K have a discussion of the lead acid battery used in cars on pages 129–131. AJP. Groth . By the way. you can ﬁnd Physical Review and Physical Review Letters on-line and the article cited above can be downloaded and printed out. The two solutions are in contact.

) Charge is transfered inside the cell. the reaction is Zn → Zn++ + 2e− . . (Of course. so we’ll discuss the situation when there is no current ﬂowing in the external circuit and the system has reached equilibrium. one can think of CuSO4 dissociating into Cu++ and SO−− at the positive electrode. current will ﬂow until one of the consumables is exhausted. the electrons left behind by the zinc can travel through the external circuit to the copper electrode where they join up with the copper ions to plate out the copper atoms. The voltage of the cell (e. Princeton University Physics Department. When the reactions stop. 06-Oct-2004 12-7 Zinc atoms in the electrode go into solution as zinc ions and leave behind two electrons on the cathode. Copyright c 2004. by sulfate ions. the electrodes acquire charges and electric potentials. through the electrolyte. When operated in this mode.. the chemical potentials of the atoms/ions must be the same whether they are in solution or on the electrodes.) As zinc goes into solution and copper plates out. so we are really assuming that the time for the electrolytes to diﬀuse is long compared to the time for the reactions at the electrodes to complete. Edward J. solutions. ions go in one end and diﬀerent ions come out the other end. .g. 4 the Cu++ plates out leaving behind a spare sulfate ion which diﬀuses over to the negative electrode to join up with a zinc ion and form ZnSO4 .. If we actually have a complete circuit. and Vc be the electric potentials (voltages) of the anode. If not.. there would be a current ﬂow until a uniform potential is established. When the the potentials are large enough the reactions stop. a non-uniform distribution of electrolytes is also not an equilibrium situation. . If a wire is connected between the two electrodes. Groth . (Of course. If all the copper is plated out of solution or if the zinc electrode is completely dissolved. the cell converts chemical potential energy into electrical energy. that will be the end of the cell. measured by a voltmeter placed across the anode and cathode) is Vcell = Va − Vc = (Va − Vs ) + (Vs − Vc ) . That is. Let Va . . Our methods apply to equilibrium situations. sulfate ions don’t go all the way across the electrolyte. electrons go in one end and diﬀerent electrons come out the other end.) Essentially all the current in the electrolyte is carried by the ions and none by electrons. (Actually. and cathode.Physics 301 At the zinc electrode. Note that we assume the electrolytes (solutions) are equipotentials. Vs .

Recall: only potential energy diﬀerences are important! Finally. The chemical potential is made of two parts: the internal chemical potential and the potential energy of the ion in macroscopic electric potential of the cathode or the solution: µci (Zn++ ) + 2eVc = µsi (Zn++ ) + 2eVs . If this reminds you of redox reactions in chemistry. or µci (Zn++ ) − µsi (Zn++ ) = 2e(Vs − Vc ) . with no current ﬂowing. by now you should be getting a feel for why it’s called the chemical potential! Copyright c 2004. Thus Va − Vs = 0. my 1962 edition of the Handbook of Chemistry and Physics has a table titled “Potentials of Electrochemical Reactions at 25◦ C in which one ﬁnds +0. Groth . for example. Then all other half cells are measured relative to the standard. The diﬀerence of internal chemical potentials is determined by the chemical reaction. the chemical potential of the zinc in the cathode must be the same as that of zinc in solution. This is mainly for clarity and can be justiﬁed by noting that the conduction electrons in a metal are not localized to any particular atom. It is customary to divide this by the magnitude of the electric charge and the number of charges involved and tabulate as a potential diﬀerence.Physics 301 06-Oct-2004 12-8 Consider a zinc ion in the cathode.7628 V listed for the reaction Zn → Zn++ + 2e− .76 V.35 V and the open circuit cell potential is Vcell = 1.11 V. This means that Vs − Vc is about 0. When equilibrium has been established. Princeton University Physics Department. The half cell voltages are determined by deﬁning a standard half cell (a platinum electrode over which hydrogen ions are bubbled) as a standard with zero half cell potential. we have µai (Cu++ ) − µsi (Cu++ ) = −2e(Va − Vs ) . So. Edward J. where e > 0 represents the magnitude of the charge on an electron and µci and µsi represent the internal chemical potentials in the cathode and the solution. At the anode. Note that I have shown the zinc as zinc ions on the cathode as well as in solution.3460 V. The Handbook lists the electric potential of the reaction Cu → Cu++ + 2e− as −0. it should! The Handbook contains a table titled “Electromotive Force and Composition of Voltaic Cells” which gives the composition and voltage of selected cells. Comments: the potentials associated with reactions that occur at the cathode or anode are called half cell potentials.

so the aligned magnets will be attracted to regions of high ﬁeld strength while the antiparallel magnets will be repelled from regions of high ﬁeld strength. µ↑. So. Groth . pages 127–129. µ↑ = µ↓ = Constant. Let n↑ be the concentration of parallel and n↓ be the concentration of antiparallel systems. one would expect to ﬁnd a greater fraction aligned even if the particles couldn’t move. Furthermore. Of course. we are allowing the particles to diﬀuse to regions of higher or lower ﬁeld strength. . Just as with an ideal gas. In the antiparallel orientation the energy is +mB = +E. Princeton University Physics Department. nQ µ↑ = τ log Now. the energy is −mB = −E. there are magnets with orientations parallel or antiparallel to a magnetic ﬁeld. n↑ − mB .” To the internal chemical potential must be added the external potential due the energy in the magnetic ﬁeld. Following the discussion in K&K. and the chemical potential must be independent of ﬁeld strength.int = τ log n↓ . the parallel and antiparallel magnets are in thermal equilibrium with each other and can be changed into one another. nQ n↓ µ↓ = τ log + mB . In this system.Physics 301 Example: Magnetic Particles in a Magnetic Field 08-Oct-2004 13-1 Recall the paramagnetic spin system we discussed in lecture 4. in the regions of high ﬁeld. one can remove a particle from the parallel group and add it to the antiparallel group and vice-versa. When the system has come to equilibrium. suppose that we have the same kind of system. but in addition. In lecture 4. the magnetic particles are free to move. This relation together with the previous equations are easily solved to yield n↑ (B) = 1 n(0)e+mB/τ 2 and n↓ (B) = 1 n(0)e−mB/τ . Edward J. That is. we expect that microscopic or internal contribution to the chemical potential should depend on the concentration.int = τ log n↑ nQ and µ↓. . we worked out the relative numbers of parallel and antiparallel magnets and found that it depended on the ratio of thermal to magnetic energies. 2 Copyright c 2004. nQ We assume that we can treat the parallel and antiparallel magnets as distinct kinds of “particles. the free energy must be stationary with respect to changes in the particle numbers which means the chemical potentials of the two kinds of particles must be the same. In the parallel orientation. where m is the magnetic moment and B is the magnetic ﬁeld. at temperature τ .

A Bohr magneton (roughly the magnetic moment of an electron) is µB = e¯ /2mc where e and m are the charge and mass of an h electron. The average number of (bound) electrons and the average energy are N = 2e(µ + I)/τ e(µ + I)/τ + e(µ + I)/τ = . The key datum to extract from the plot is that at a given chemical potential. both have energy −I and both have one electron present. They could also contain a more or less arbitrary number of non-magnetic molecules. K&K show a plot of chemical potential versus concentration for several diﬀerent ﬁeld strengths. Edward J. The model for this impurity atom is a three state system: the ionized state has energy 0 and no electron is present. The particles must contain 1200 paramagnetic molecules with a spin of h/2 and ¯ a magnetic moment of µB . not the series. The atom may lose a valence electron and become ionized. Note that we had to use the cosh form of the expression. The grand partition function is Z = 1 + e(µ + I)/τ + e(µ + I)/τ . There are two bound states. These relations show both eﬀects we mentioned earlier. The magnetic particles diﬀuse to regions of high ﬁeld strength.5 also asks how many Bohr magnetons must be contained in each particle. we obtain about 1200 magnetons. the concentration increases by two orders of magnitude as B is increased from 0 to 20 kG. K&K discuss an impurity atom in a semiconductor. the greater the fraction of aligned magnets (as we already knew from lecture 4) and the greater the concentration of magnets. The higher the ﬁeld strength. We can plug this directly into the previous expression to get m/τ = 5. Groth . we are asked for what value of m/τ was this ﬁgure drawn. Problem 5. µB = 0.Physics 301 08-Oct-2004 13-2 where we’re explicitly showing that the concentrations depend on B and n(0) is the combined concentration where B = 0. Example: Impurity Ionization In pages 143–144. The energy required to remove an electron from the donor atom is I. Princeton University Physics Department. because mB/τ > 1. The combined concentration as a function of B is n(B) = n↑ (B) + n↓ (B) = n(0) cosh(mB/τ ) = n(0) 1 + m2 B 2 +··· 2τ 2 . Doing the arithmetic. 1 + e(µ + I)/τ + e(µ + I)/τ 1 + 2e(µ + I)/τ −2Ie(µ + I)/τ −Ie(µ + I)/τ − Ie(µ + I)/τ = .6. E = 1 + e(µ + I)/τ + e(µ + I)/τ 1 + 2e(µ + I)/τ Copyright c 2004.000265 G−1 .927 × 10−20 erg G−1 . One has the electron with spin up along some axis and the other has the electron with spin down. where the ﬁrst term comes from the ionized state and the second and third terms account for the spin up and spin down bound states. In ﬁgure 5.30/(20000 G) = 0. In problem 5 of chapter 5.

= Z 1 + λ + λe−ǫ/τ Copyright c 2004. The average energy is E = ǫλe−ǫ/τ ǫλe−ǫ/τ . Chapter 5. The higher the concentration of electrons in the semiconductor. exp(−ǫ/τ ). this result can also be obtained using N = λ(∂/∂λ) log Z. Groth . Problem 6 In this problem we are asked to work with a 3 state system. The thermal average occupancy of the state with energy ǫ is N (E = ǫ) = λe−ǫ/τ λe−ǫ/τ . (µ + I)/τ 1 + 2e 08-Oct-2004 13-3 If we don’t know the value of µ. where λ = exp(µ/τ ). energy is ǫ. The states are: (1) no particle. or present with energy ǫ. All this is reasonable and might have been expected. and the relative probability that the particle is in the high energy state is just the Boltzmann factor. decreases the mean energy (energy goes down for a bound particle). energy is still 0: (3) one particle. The grand partition function is Z = 1 + λ + λe−ǫ/τ . The thermal average occupancy is just the average number of particles in the system and is λ + λe−ǫ/τ 1 0 · 1 + 1 · λ + 1 · λe−ǫ/τ = .Physics 301 The probability that the impurity atom is ionized is P (N = 0) = 1 . increasing µ (λ) makes it harder for the system to give the particle to the reservoir (which determines µ) and the system is more likely to contain a bound particle. and decreases the probability of being ionized. the harder it is for the atom to give an extra electron to the semiconductor and become ionized! Example: K&K. (2) one particle. we can’t actually calculate any of these averages or this probability. we’re used to the idea that µ increases with increasing concentration. Just as in the previous example. The three terms in this sum correspond to the three states enumerated above. so a particle can be absent. energy is 0. = Z 1 + λ + λe−ǫ/τ Here we see that in the limit of very large µ (λ) the system always contains a particle. Edward J. N = Z 1 + λ + λe−ǫ/τ Of course. present with zero energy. (A subject we’ll get to in a few weeks!) Although we don’t know µ at this point. What sets the value of µ? Answer: µ is determined by the electron distribution in the rest of the semiconductor. In the above expressions we see that increasing µ increases the mean number of particles in the system. Princeton University Physics Department.

problem 4). let’s calculate the grand partition function for an individual state of energy ǫ. Groth . Princeton University Physics Department. the grand partition function for all the states is the product of the grand partition function for the individual states. we considered the single particle states of a particle conﬁned to a box. Then Z = 1 + e(µ − ǫ)/τ . and bosons which have integral spins. Since we have independent single particle states. there is a fourth state of the system. K&K point out that this means that the system can be treated as two independent systems. fermions obey the Pauli ¯ exclusion principle: at most one particle may occupy a single state. Edward J. an unlimited number of bosons may be placed in any given state. this would be exact (but it might be hard to achieve thermal equilibrium!). which have half integer spins (spin angular momentum is a half integer times h). treat each particle as though it occupied a single particle state. So to start with. In this case. the grand partition function is the product of the grand partition functions for each independent system. This is an example of a general rule that for independent (but weakly interacting) systems. so that the chance that any single particle state was occupied was very small. To treat more than one particle. We are going to assume that we have non-interacting particles in which each particle in the system can be said to be in a single particle state. we are asked to calculate the grand partition function in the event that a particle can exist in both the zero energy state and the state with energy ǫ simultaneously. Now we want to consider the distribution when there’s a good chance of ﬁnding single particle states occupied. For typical gases at room temperature and atmospheric pressure we found that the concentration was very low. On the other hand. there are two possibilities: no particle present with energy 0 and one particle present with energy ǫ. We have Z = 1 + λ + λe−ǫ/τ + λ2 e−ǫ/τ = (1 + λ) · (1 + λe−ǫ/τ ) . so we could. we imagined that the particles were weakly interacting. just as the partition function of independent systems is a product of the individual partition functions (Homework 2. to some level of approximation. fermions. maybe one part in a million. Fermi-Dirac and Bose-Einstein Distributions When we considered a low density gas in lecture 7. Copyright c 2004. There are two kinds of particles. In the case of fermions.Physics 301 08-Oct-2004 13-4 Finally. Z can be factored. it contains two particles and has energy ǫ. In the limit of no interactions between particles. In other words. We just didn’t have to worry about the chances of ﬁnding two particles in a state.

the transition is gradual. then the average number of particles in the state is 1/2. 2 particles present with energy 2ǫ. Princeton University Physics Department. If ǫ > µ. 1 particle present with energy ǫ. If ǫ < µ. = 1 + e(µ − ǫ)/τ e(ǫ − µ)/τ + 1 This is called the Fermi-Dirac distribution and fermions are said to obey Fermi-Dirac statistics. Edward J. At very low temperatures the transition is sharp. the average occupancy is bigger than 1/2 and approaches 1 as ǫ → −∞. For bosons. = = ∂µ 1 − e(µ − ǫ)/τ e(ǫ − µ)/τ − 1 Copyright c 2004. the possibilities are no particles present with energy 0.Physics 301 08-Oct-2004 13-5 The average number of particles in this state of energy ǫ is denoted by f (ǫ) f (ǫ) = N = e(µ − ǫ)/τ 1 . This distribution starts at 1 at very low energies. The grand partition function is Z = 1 + e(µ − ǫ)/τ + e2(µ − ǫ)/τ + e3(µ − ǫ)/τ + · · · = 1 . winds up at 0 at very high energies and makes the transition from 0 to 1 in the neighborhood of µ. Groth . the average occupancy is less than 1/2 and approaches 0 as ǫ → +∞. and so on. The temperature controls the width of the transition. 3 particles present with energy 3ǫ. At high temperatures. If ǫ = µ. The average occupancy is f (ǫ) = τ 1 e(µ − ǫ)/τ ∂ log Z . 1 − e(µ − ǫ)/τ Note that µ < ǫ if the sum is to converge.

Groth .Physics 301 08-Oct-2004 13-6 This is called the Bose-Einstein distribution and bosons obey Bose-Einstein statistics. The minimum energy is often set to zero. with µ = 0. As ǫ → +∞ the distribution goes exponentially to zero. At lower energies there is more than one particle in the state and at higher energies there is less than one particle in the state. so they are bosons and obey Bose-Einstein statistics. is exactly the occupancy we came up with for photons in blackbody radiation. so the lowest conceivable energy is arbitrarily close to zero which means µ ≤ 0. In other words µ < ǫminimum . The Bose-Einstein distribution diverges as ǫ → µ. The Bose-Einstein distribution. Princeton University Physics Department. if we have weakly interacting particles occupying states of several diﬀerent energies. In fact. note that µ < ǫ if the distribution function is to make sense. Again. Copyright c 2004. but the real constraint is just that µ be lower than any accessible energy. Photons have spin 1. There is no lower limit on the wavelength. they all have the same chemical potential which must therefore be less than the lowest energy of any available state. The average occupancy is 1 when ǫ − µ = τ log 2. and then µ < 0. Edward J.

Princeton University Physics Department.Physics 301 08-Oct-2004 13-7 At large energies both the Fermi-Dirac and Bose-Einstein distributions become f (ǫ → +∞) → e(µ − ǫ)/τ . Edward J. Copyright c 2004. Groth . In this limit the average occupancy is small and quantum eﬀects are negligible. The classical distribution is called the Maxwell-Boltzmann distribution. this is the classical limit.

Now that we have the grand partition function we can reconsider the problem. etc. Then we said the partition function for N weakly interacting particles is the product of N single particle partition functions divided by N !. N! N! We introduced the factor of N ! to account for the permutations of the N particles among the single particle states forming the overall composite state of the system. Edward J. Princeton University Physics Department. the Maxwell-Boltzmann distribution. it’s hard to do more. we’ve discussed the Fermi-Dirac and Bose-Einstein distributions and their classical—low occupancy—limit. required for various processes with an ideal gas. and also we want to consider the absolute entropy and see how the Sackur-Tetrode formula relates to experiment. The introduction of this N ! factor was something of a “fast one!” We gave a plausible argument for it. the heat and work..Physics 301 Reading K&K chapter 6 and the ﬁrst half of chapter 7 (the Fermi gas). We considered the states of a single particle in a box and we used the Boltzmann factor and the number of such states to calculate the partition function for a single particle in a box. we considered an ideal gas starting from the partition function. Copyright c 2004. In addition to cleaning up this detail. In lecture 7. we also want to consider how to account for the internal states of the molecules in a gas. Groth . ZN (τ ) = 1 N 1 Z1 = (nQ V )N . but without a formalism that includes the particle number. 11-Oct-2004 14-1 The Ideal Gas Again Using the grand partition function.

the concentration. σC = N log(nQ V /N ) + (3/2)N + N .” I think this is kind of amusing. = −τ log((nQ V )N /N !) . σ = −∂F/∂τ . the change in entropy between an initial and ﬁnal state is given correctly by either formula. is an intensive quantity. = −τ (N log nQ + N log V ) . =N log(nQ V ) + 3 2 . n = N/V . = −τ N log (mτ /2π¯ 2 )3/2 V h For the entropy. = −τ log(nQ V )N . Groth . σCf − σCi = σIf − σIi = 3 Vf τf + N log . N log 2 τi Vi But what happens when we change the amount of gas? Note that N and V are both extensive quantities. the “incorrect” free energy is FI = −τ log Z . The free energy with the N ! term is FC = −τ log Z . so let’s see what the N particle problem really is. Edward J. With a given amount of gas. = −τ (N log nQ + N log V − N log N + N ) . in Schroedinger’s book on the subject. he has a chapter called “The N Particle Problem. σC is proportional to an extensive quantity. In fact. h where the subscript C denotes the “correct” free energy.Physics 301 The N Particle Problem 11-Oct-2004 14-2 The factor of N ! in the ideal gas partition function was apparently controversial in the early days of statistical mechanics. On the other hand. = −τ N log (mτ /2π¯ 2 )3/2 (V /N ) − τ N . σI Copyright c 2004. Princeton University Physics Department. Without the N ! term. σI = N log(nQ V ) + (3/2)N . =N and log nQ V 5 + N 2 .

Once equilibrium has been established. We assume that no chemical reactions occur—we are only waiting for the molecules to diﬀuse so that they are uniformly mixed.Physics 301 11-Oct-2004 14-3 contains an extensive quantity times the logarithm of an extensive quantity. This means that the (incorrect) entropy is not proportional to the amount of gas we have! For example. We remove the partition. Finally. then we’re pretty sure that the partition hasn’t been removed! If we ﬁnd a mixture of type A and type B. for a total of 2N (log(nQ V )+3/2). Now we have 2N molecules in a volume 2V . and reinsert the partition. A and B. Now we remove the partition. Copyright c 2004. Groth . Princeton University Physics Department. We might consider the same experiment but performed with two diﬀerent kinds of molecules. We can imagine a volume 2V divided in half by a removable partition. This time we have to wait for equilibrium to be established. each molecule occupies single particle states in a volume 2V and the entropy is 2nQB V 5 5 2nQA V + N log . This emphasizes the point that the incorrect expression results from over counting the states by treating the molecules as distinguishable. the incorrect expression for entropy gave an increase which turns out to be the same as the entropy of mixing if we start out with two diﬀerent gases. we have nQA V nQB V 5 5 σC = N log + N log . In the mixing experiment. We start with the partition in place and the entropy as above. then we’re pretty sure that it has been removed. Before the partition is removed. In the experiment with the same gas on both sides of the partition. + + N 2 N 2 where the two kinds of molecules may have diﬀerent masses and so might have diﬀerent quantum concentrations. This increase is called the entropy of mixing. each containing N molecules of (the same kind of) gas at temperature τ . We start with N molecules of type A on one side of the partition and N molecules of type B on the other side of the partition. The entropy becomes σI = 2N (log(2nQ V ) + 3/2) which exceeds the entropy with the partition in place by ∆σI = 2N log 2! But did anything really change upon removing the partition? What kind of measurements could we make on the gas in either volume to detect whether the partition were in place or not??? Note that the total σC is the same before and after the partition is removed. If we sample the gas in one of the volumes and ﬁnd all the molecules are type A. Edward J. suppose we have two volumes V . + + σC = N log N 2 N 2 which is 2N log 2 greater than the initial entropy. Then each has σI = N (log(nQ V ) + 3/2). we can make measurements that tell us whether the partition has been removed. note that if we go back to the case of the same gas.

Groth . τ log 0 N = =τ 0 N′ dN ′ . e−ǫ/τ . This is a violation of the second law! 11-Oct-2004 14-4 The Ideal Gas From the Grand Partition Function An ideal gas is the low occupancy limit of non-interacting particles. Copyright c 2004. V ) dN ′ . Then µ = τ log as we found earlier. Princeton University Physics Department. Edward J. nQ V (log N ′ − log(nQ V )) dN ′ .V F = 0 N µ(N ′ . µ. All states = eµ/τ = eµ/τ Z1 . nQ = µ(N. where Z1 is the single particle partition function we discussed earlier. τ. is found by requiring that the gas have the correct number of molecules. V ) . = Nτ log n −1 nQ . = eµ/τ nQ V . both the Fermi-Dirac and Bose-Einstein distributions become the Maxwell-Boltzmann distribution which is f (ǫ) = e(µ − ǫ)/τ . τ. The chemical potential. N= All states e(µ − ǫ)/τ .Physics 301 then σI decreases by 2N log 2. N = τ N ′ log N ′ − N ′ − N ′ log(nQ V ) 0 . where f (ǫ) ≪ 1 is the average occupancy of a state with energy ǫ. The free energy satisﬁes ∂F ∂N so N n . τ. In this limit.

V ∂F ∂V . The molar speciﬁc heat at constant volume is (3/2)N0 k = (3/2)R where R is the gas constant. ∂F ∂τ . comes about naturally with this method. The N ! factor that we previously inserted by hand. Edward J. V.) As a reminder. V. σ=N log nQ 5 + n 2 . this is in agreement with what we had before. τ. The heat Copyright c 2004.Physics 301 11-Oct-2004 14-5 Of course.N The entropy is found by diﬀerentiating with respect to the temperature. Since dU = τ dσ − p dV + µ dN . the pressure is found from the free energy by p=− which gives the ideal gas equation of state p= Nτ . Then the heat capacity at constant volume is CV = τ which for the case of an ideal gas is CV = 3 3 N = Nk . Groth . the change in energy at constant volume and particle number is just τ dσ. σ=− which gives the Sackur-Tetrode expression.N where the last expression gives the heat capacity in conventional units. 2 The energy of an ideal gas depends only on the number of particles and the temperature. (It is responsible for the N in the concentration in the logarithm and the −1 within the parentheses. 2 2 ∂σ ∂τ . Princeton University Physics Department.N The internal energy is most easily found from U = F + τσ = 3 Nτ .

or Cp = CV + N k (in conventional units) .N The ratio of speciﬁc heats is usually denoted by γ. ∂U ∂τ = CV .N ∂τ p. these are CV = 3 R. For the molar heat capacities. Groth . CV 3 Copyright c 2004. ∂τ p. which for an ideal monatomic gas is γ= Cp 5 = . Princeton University Physics Department. p. V = (N/p)τ . p. we have Cp = CV + R .Physics 301 11-Oct-2004 14-6 capacity at constant pressure can be found by requiring that dV and dτ be such that p doesn’t change. Edward J. p so Cp = CV + N .N With the ideal gas equation of state. 2 and Cp = 5 R.N Since U depends only on N and τ . ∂σ ∂U ∂V Cp = τ = +p . and for the ideal monatomic gas.N ∂τ p. 2 ∂V ∂τ =N.

Again. The energy of the particle is ǫcm + ǫint . Edward J. However. Princeton University Physics Department. We will discuss an approximate treatment of interactions in a few weeks when we discuss phase transitions. We imagine that each molecule contains several internal states with energies ǫint . When a molecule changes its internal state. we assume the number of particles does not change. Let’s consider the grand partition function for a single state of center of mass motion. Z Z = 1 + e(µ − ǫcm )/τ Zint + e2(µ − ǫcm )/τ int + e3(µ − ǫcm )/τ int + · · · . we would need to be sure that the multiple particle terms have all particles in diﬀerent states which means that the internal partition functions do not factor as shown above. but not so good for higher densities (but these higher densities can still be low enough that the MB distribution applies). Finally. For fermions. our treatment using the Maxwell-Boltzmann distribution is inappropriate and we should start from the Fermi-Dirac or Bose-Einstein distribution directly. Although we are considering internal energies. we’re going to consider the grand partition function for single particle states—with internal degrees of freedom—in a box.Physics 301 Internal Degrees of Freedom 11-Oct-2004 14-7 There are several corrections we might make to our treatment of the ideal gas. 2! 3! where Zint is the partition function for the internal states. we have ignored any internal structure of the molecules. Then the grand partition function is Z = 1 + e(µ − ǫcm − ǫint. we are not considering ionization or dissociation. We have ignored the interactions between molecules. This means we can truncate the sum Copyright c 2004. This is a good approximation for low density gases. we really don’t need to worry about this because we’re going to go to the classical limit where the occupancy is very small. We will remedy this omission now. That is. = 1 + e(µ − ǫcm )/τ e−ǫint /τ int + two particle terms + three particle terms + · · · . ǫcm . the external energy is just the kinetic energy due to the translation motion of the center of mass. cm is to be understood as an index which ranges over all states of motion of the cm. In our non-interacting model. = 1 + e(µ − ǫcm )/τ Zint + two particle terms + three particle terms + · · · .1 )/τ + e(µ − ǫcm − ǫint. Groth 2 3 . Note that int is understood to be an index over the internal states. If we go to high occupancies. The above expression is strictly correct only for bosons.2 )/τ + · · · + two particle terms + three particle terms + · · · . There may be states with the same energy and states with diﬀering energies.

U . where σcm is our previous expression for the entropy of an ideal gas. int which is just the Maxwell-Boltzmann distribution with an extra factor of the internal partition function. (Is this really true? How do we get liquids and solids? Under what conditions might it be a good approximation?) The expression for the entropy becomes σ = σcm + σint . exp(µ/τ ) must be replaced by exp(µ/τ )Zint. whatever the internal state. and σint = − ∂Fint ∂τ = V. the partition function of the internal states does not depend on the volume. and everything else will go through as before. n =τ nQ Zint log n − log Zint nQ . V. where Fcm is our previous expression for the free energy due to the center of mass motion of molecules with no internal degrees of freedom. Then our new expression for µ is µ = τ log The free energy becomes F = Fcm + Fint = N τ log n −1 nQ Zint . Now we should modify our previous expressions to allow for this extra factor of Zint . Copyright c 2004. In that calculation. Edward J. 11-Oct-2004 14-8 The mean occupancy of the center of mass state. Z = 1 + e(µ − ǫcm )/τ Zint . and therefore the heat capacities. Zint . is the free energy of the internal states alone. receive a contribution from the internal states. is f (ǫcm ) = e(µ − ǫcm )/τ Zint 1 + e(µ − ǫcm )/τ Z ≈ e(µ − ǫcm )/τ Zint . Groth . the Sackur-Tetrode expression.N ∂(N τ log Zint ) ∂τ = N log Zint + N τ V. The extra energy is Uint = Fint + τ σint = Fint − τ ∂Fint ∂τ = −τ 2 V.N ∂ ∂τ Fint τ .Physics 301 above after the second term.N ∂(log Zint ) ∂τ . Recall that we chose the chemical potential to get the correct number of particles. Princeton University Physics Department. The expression for the pressure is unchanged since in the normal situation. and Fint = −N τ log Zint .N The energy.

all these states have the same energy which we take as ǫint = 0. 3M coordinates are required to specify the locations of all the Copyright c 2004. Here’s another one: Suppose that each molecule has one internal state with energy ǫ1 . an ideal gas To make further progress. In this example. The increase in entropy is easy to understand. we need to consider some speciﬁc examples of internal structure that can give rise to Zint . so the entropy is increased over that of a simple ideal gas. Suppose the molecules are single atoms but these atoms have a spin quantum number S. Single atoms have neither rotational nor vibrational modes (they do have electronic excitations!). Diatomic molecules have one degree of vibrational freedom. The entropy. Uint = 0 . the logarithm of the number of states. for example. increases by log(2S + 1) per atom. If the molecule has M atoms. Princeton University Physics Department. Edward J. σint = N log(2S + 1) . Uint = N ǫ1 . A linear molecule (any diatomic molecule and some symmetric molecules such as CO2 . What’s happening is that each atom has 2S + 1 times as many states available as a simple atom with no internal structure. we didn’t change the entropy (each molecule has just one state). This example is basically a small test of the self-consistency of the formalism! More realistic examples include the rotational and vibrational states of the molecules. Non-linear molecules have three rotational degrees of freedom. That was a fairly trivial example. Then Zint = 2S + 1 and Fint = −N τ log(2S + 1) . More complicated molecules have more degrees of vibrational freedom. Then Zint = exp(−ǫ1 /τ ) and Fint = −N τ log Zint = +N ǫ1 .Physics 301 Examples of Zint 13-Oct-2004 15-1 We have been discussing how to modify our treatment to allow for the internal states and energies of molecules in. and ∆µ = −τ log Zint = +ǫ1 . In the absence of a magnetic ﬁeld. Groth . but we added ǫ1 to the energy of each molecule. but the energy doesn’t change. Then there are 2S + 1 internal states that correspond to the 2S + 1 projections of the spin along an arbitrary axis. σint = 0 . but not H2 O) has two rotational degrees of freedom. This change in energy shows up in the chemical potential as a per molecule change and it shows up in the free energy and energy as N times the per molecule change.

Two or three are used for the rotational degrees of freedom. The spacing between the rotational energy levels sets the scale for low and high temperatures. Princeton University Physics Department. At low temperatures. recall that an atom consists of a nucleus surrounded by an electron cloud. Similarly. the atom has a fair chance of being ionized. If the atom is part of a molecule. the energy will be 3N τ /2. and γ = 9/7. Edward J. but at low temperatures we expect that the rotational modes are “exponentially frozen out.” In this case. The molecule thus has 3M degrees of freedom. Groth . The electrons are in states with angular momentum. we expect an average energy of τ /2 per rotational degree of freedom. This means that at high temperatures. The remainder are vibrational degrees of freedom.Physics 301 13-Oct-2004 15-2 atoms. This is possible. they do not contribute to the partition function. At low temperatures the vibrational modes are exponentially frozen out and do not contribute to the internal partition function. Three of these are used in specifying the location of the center of mass. the entropy will be given by the Sackur-Tetrode expression and the molar heat capacities will be CV = 3R/2 and Cp = 5R/2 with γ = 5/3. (Ignoring things like the fact that inertia is a tensor!) Since angular momentum is quantized. or the entropy. the energy. h times the frequency of vibration sets the scale for low and high ¯ temperatures. so is rotational energy. Copyright c 2004. The upshot of all this is that such excitations are not important unless the temperature is high enough that molecules are dissociating and atoms are ionizing! Rotational energy is the square of the angular momentum divided by twice the moment of inertia. that molecule has probably been dissociated as molecular binding energies are usually small compared to atomic binding energies. but if there is an appreciable thermal excitation of such states. consider a diatomic gas. we expect that the corresponding normal mode of oscillation can be treated as a harmonic oscillator and that at high temperatures there will be an average energy of τ per vibrational degree of freedom (τ /2 in kinetic energy and τ /2 in potential energy). As an example. the energy or the entropy. To make this plausible. and to change the angular momentum one or more electrons must be placed in an excited electronic state. You might be uncomfortable with 0 or two degrees of rotational freedom for point or linear molecules. CV = 7R/2. for each vibrational degree of freedom. If the temperature is raised still higher the vibrational modes can be excited and U = 7N τ /2. Cp = 9R/2. As the temperature is raised the rotational modes are excited and the energy becomes 5N τ /2 with molar speciﬁc heats of CV = 5R/2 and Cp = 7R/2 and γ = 7/5.

Tf ∆S = nCp Ti Tf Vf Tf dT = nCV log + nR log . Q = nCV (Tf − Ti ) .) We will want to know the work done. the gas will expand and Vf /Vi = Tf /Ti Q = nCp (Tf − Ti ) . = nCp log T Ti Ti Vi Consider a constant temperature (isothermal) process. (In other words. ∆U = nCV (Tf − Ti ) . Consider a constant volume process. Heat is added and the gas expands to maintain a constant temperature. the change in energy and the change in entropy of the system. dT Tf ∆S = nCV . n is the number of moles. if heat is added. while energy and entropy changes depend only on the initial and ﬁnal states. The pressure and volume satisfy pf /pi = Copyright c 2004. Note that work and heat depend on the process. heat added. W is the work done on the gas. Groth . For the most part we will consider reversible processes. About the only thing one can do is add heat! In this case. = nCV log T Ti where Q is the heat added to the gas.Physics 301 Ideal Gas Processes 13-Oct-2004 15-3 We will consider various processes involving a ﬁxed amount of an ideal gas. Princeton University Physics Department. ∆U = nCV (Tf − Ti ) . Vf W =− Vi p dV = −nR(Tf − TI ) . We will assume that the heat capacities are independent of temperature for these processes. the temperature changes will not be large enough to thaw or freeze the rotational or vibrational modes. Consider a constant pressure (isobaric) process. CV and Cp are the molar heat capacities in conventional units and T and S are the temperature and entropy in conventional units. pf /pi = Tf /Ti . In this case. Edward J. W =0.

concentration) as well as temperature. then it may be that the energy depends on volume (or rather. so the energy and temperature don’t change. V Vi Consider a constant entropy process. Finally. the term isentropic can be used to explicitly mean that the entropy is constant.Physics 301 (Vf /Vi )−1 . However. 1 Vfγ−1 − 1 Viγ−1 =− nRTi γ −1 γ−1 Q=0. Then Vf W =− Vi p dV = −pi Viγ 1− Vi Vf Vf Vi dV pi Viγ = Vγ γ−1 . This is called a free expansion. Since it is possible to change the entropy without heat transfer. Note that if a gas is not ideal. Edward J. nRTi ∆U = W = − γ−1 ∆S = 0 . so the entropy change is the same as for that case. but not isentropic. Vf Vf 13-Oct-2004 15-4 W =− Vi p dV = −nRT Vi dV Vf . It is left as an exercise to show that in an isentropic process with an ideal gas. The initial and ﬁnal states are the same as in the reversible isothermal expansion. adiabatic is also taken to mean that no heat is transfered. Suppose a gas is allowed to expand from a volume Vi into a vacuum until its volume is Vf . pV γ = constant. Vi ∆S = nR Vi Vf dV = nR log . No work is done to the gas and no heat is added. process. Princeton University Physics Department. Copyright c 2004. Q = −W = nRT log Vf Vf . 1− Vi Vf γ−1 . ∆U = 0 . ∆S = nR log Vf . This is often called an adiabatic process. = −nRT log V Vi ∆U = 0 . let’s consider an irreversible process. Q=0. W =0. Vi This is an adiabatic. Groth .

At the macroscopic level. A similar problem occurs with potential energy. A and B. So if we can take a system from one state to another via a (close approximation of a) reversible process and measure the heat ﬂow and temperature. Recall that dσ = dQ/τ for a reversible ¯ process. and there is obviously no entropy change in the surroundings when the partition is removed from the identical gases. Groth . The question of measuring the entropy has come up several times. The Gibbs Paradox Revisited Last lecture’s treatment of the N particle problem might have engendered some uneasiness.” The fact that we have to wait for equilibrium to be established means that the mixing of the two diﬀerent gases is a non-reversible process. . . Princeton University Physics Department. frictionless partition. each containing N molecules of gas at temperature τ . especially the example with two volumes of gas that were allowed to mix.). To measure the absolute entropy of a state. we can deduce the entropy diﬀerence between the two states. Recall that we had two volumes. It is potential energy diﬀerences that are important to the dynamics and only diﬀerences can be measured. and separated by a partition. on the two sides of the partition.This is called the entropy of mixing. The incorrect expression for the entropy (omitting the N ! over counting correction in the partition function) gives the same entropy of mixing in both cases. There is always the question of the constant of integration. When the partition is removed in the same gas case “nothing happens. total entropy (system plus surroundings) does not increase. Edward J. Entropy always increases in nonreversible processes! On the other hand. For example. V . We considered two cases: the same gas on both sides of the partition and diﬀerent gases. This manifestation of the N particle problem is called the “Gibbs paradox. we must wait a while for equilibrium to be established and once this happens. we ﬁnd that the entropy has gone up by 2N log 2. If we take the zero of gravitational potential energy to be at inﬁnite separation of Copyright c 2004. Aside: the fact that we can only measure changes in entropy should not be that bothersome. we must start from a state whose absolute entropy we know. When the partition is removed in the diﬀerent gas case. entropy is deﬁned by an integral ( dQ/τ ). consider a mass m on the surface of the Earth. This is a state at τ = 0! We will see how this goes in the comparison of the Sackur-Tetrode expression with experimental results. In a reversible process. removing the partition between identical gases is a reversible process (in the limit of a negligible mass.” the system is still in equilibrium and the entropy doesn’t change—according to the correct expression which included the N ! over counting correction in the partition function.Physics 301 13-Oct-2004 15-5 Such a deviation from the ideal gas law can be uncovered by measuring the temperature of a gas before and after a free expansion. There is no such thing as an entropy meter that one can attach to a system and out pops a reading of the entropy! Changes of the entropy can be measured.

I’m sure we’re all happy with this. that F = −mg. We need two of them: one that passes molecules of type A freely but is impermeable to molecules of type B. we have to approximate a reversible process! Reversible processes aren’t just for thermodynamics! I suspect they’re easier to visualize in other branches of physics. the escape velocity. we can measure the change in gravitational potential energy between two states. Also. Copyright c 2004. That is. Instead. Princeton University Physics Department. we could use it—in reverse!—to separate the gases again. The molecules that are passed may not pass through “freely. Of course. for example.Physics 301 13-Oct-2004 15-6 the mass and the Earth. so they don’t cause as much comment and concern. Back to our mixing example: Can we think of a reversible process which would allow us to mix the gases? Then we could calculate the entropy change by keeping track of the heat added and the temperature at which it was added. etc. if we knew of such a process. This is one of the arts of theoretical physics. we might get NASA to help with this project! Of course. However.” but if we move the membrane slowly enough. that can be more easily measured. It passes type B molecules and blocks type A molecules. What about measuring the “absolute” gravitational potential? This requires measuring the changes in potential energy between the state whose potential we know (inﬁnite separation) and the state whose potential we want to know (mass on the surface of the Earth). What can we actually measure in the gravitational case? We can measure the force required to change the height (distance from the center of the Earth) of the mass and so measure F · dr. I suppose if we had enough money. there is no potential energy meter that you can attach to the mass and out pops a potential energy value. we have to be careful that there is no friction. by calculation we can relate the “absolute” gravitational potential to other quantities. and a second which does the opposite. Groth . that there is negligible acceleration of the mass. −GM m/R is a calculated value much like the entropy of mixing is a calculated value. the fact that semipermeable membranes do exist for some molecules would seem to make this a reasonable thought experiment (if not an actually realizable experiment). it should be possible to make the friction due to the molecules passing through the small holes in the membrane negligibly small. The possibility of ﬁnding the desired membranes depends on the molecules in question and almost certainly is not possible for most pairs of molecules. Edward J. then the potential energy of the mass-Earth system is −GM m/R when the mass sits on the surface of the Earth at distance R from the center. Do such membranes actually exist? Semi-permeable membranes certainly exist. In other words. The process I have in mind uses semi-permeable membranes. right? But. We can call these “A-pass” and “B-pass” membranes for short.

Physics 301

13-Oct-2004 15-7

The ﬁgure is a schematic of our mixing apparatus. The volume 2V is in equilibrium with a thermal bath at temperature τ . At the center of the volume and dividing it into two sections of volume V are the two membranes. The A-pass membrane conﬁnes the N type B molecules to the right volume and the B-pass membrane conﬁnes the N type A molecules to the left volume. The next two ﬁgures show the situations when the gases are partially and fully mixed. The membranes are something like pistons and are moved by mechanical devices that aren’t shown. These devices are actually quite important as each membrane receives a net force from the gases. The mechanical devices are used to counteract this force and do work on the gases as the membranes are moved slowly and reversibly through the volume. What is the force on a membrane due to the gases? Consider the A-pass membrane. A molecules pass freely through this membrane so there is no interaction of this membrane with the A molecules. The B molecules are blocked by this membrane, so the B molecules are bouncing oﬀ the membrane as though it were a solid surface. Since there are B molecules on the right side of this membrane and not on the left, there is a pressure (only from the B molecules) which is just N τ /VB where VB is the volume occupied by B molecules to the right of the A-pass membrane. The net force from this pressure points to the left. So as we move the membrane to the left, the B molecules do work on it. This comes from the energy, UB of the B molecules. The B molecule system would cool, except it is in contact with the heat bath, so heat ﬂows from the bath to make up for the work done on the membrane and keep τ and hence UB constant. The same thing happens with the B-pass membrane and the A gas. It is the heat transfered (reversibly) from the reservoir to each gas that increases the entropy of the gas.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

13-Oct-2004 15-8

By now, you’re convinced that the A molecules can be treated as a gas occupying the volume to the left of the Bpass membrane without worrying what’s going on with the B molecules and viceversa. We’ve arranged this “by construction.” Our model for an ideal gas is based on non-interacting molecules (well, weakly interacting, but only enough to maintain thermal equilibrium). We’ve also made the membranes so they interact only with A or B molecules but not both. So the A molecules interact strongly with the walls of the container and the B-pass membrane and interact weakly (→ 0) with everything else including other A molecules. So when the B pass membrane is moved all the way to the right, the A molecules undergo an isothermal expansion from V to 2V . We apply our ideal gas results for an isothermal expansion and ﬁnd

2V

∆σA =

V

dQ = τ

2V V

p dV = τ

2V

N

V

dV 2V = N log = N log 2 . V V

Of course, a similar result applies to the B molecules when the A pass membrane is moved all the way to the left. The total change of entropy in this process is ∆σ = 2N log 2 , which is what we had obtained before by applying the Sackur-Tetrode expression to the initial and ﬁnal states of the irreversible process. Aside: suppose we have several ideal gases occupying the same volume. pi = Ni τ /V is called the partial pressure of gas i and is the pressure that the same Ni molecules of the gas would have if they occupied the volume by themselves (no other gases present). Then the total pressure is the sum of the partial pressures: p = i pi . This is called Dalton’s law. It falls out of our ideal gas treatment “by construction.” Since the gases are noninteracting, the presence of other gases cannot aﬀect the rate of momentum transfer by a given gas! So, Dalton’s law seems trivial, but it probably helped point the way towards a non-interacting model as a good ﬁrst approximation.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 The Sackur-Tetrode Entropy and Experiment

15-Oct-2004 16-1

In this section we’ll be quoting some numbers found in K&K which are quoted from the literature. You may recall that I’ve several times asked how one would measure absolute entropy? I suspect that I pretty much gave it away (if you hadn’t ﬁgured it out already) in the last section. The answer is you have to measure heat transfers from a state of known absolute entropy to the desired state so that you can calculate dQ/τ . What is a state of known entropy? Answer, at absolute 0, one expects the entropy to be very small and we can take it to be 0. Actually, there is the third law of thermodynamics (not as famous as the ﬁrst two!) which says that the entropy should go to a constant as τ → 0. At absolute 0, a reasonable system will be in its ground state. In fact the ground state might not be a single state. For example if we consider a “perfect crystal,” its ground state is clearly unique. But real crystals have imperfections. Suppose a crystal is missing a single atom from its lattice. If there are N atoms in the crystal there are presumably N diﬀerent sites from which the atom could be missing so the entropy is log N . Also, there’s presumably an energy cost for having a missing atom, so the crystal is not really in its ground state. But this might be as close as we can get with a real crystal. The point is that the energy and the entropy are both very small in this situation and very little error is made by assuming that σ(0) = 0. (Compare log N with N log(nQ /n) when N ∼ 1023 !) In fact, a bigger problem is getting to very low temperatures. In practice, one gets as low as one can and then extrapolates to τ = 0 using a Debye law (assuming an insulating solid). So to measure the entropy of a monatomic ideal gas such as neon, one makes heat capacity measurements and does the integral C(τ ) dτ /τ . The heat capacity measurements go to as low a τ as needed to get a reliable extrapolation to 0 with the Debye law. According to K&K, the calculation goes like this: solid neon melts at 24.55 K. At the melting point, its entropy (by extrapolation and numerical integration) is Smelting − S0 = 14.29 J . mol K

To melt the solid (which occurs at a constant temperature) requires 335 J mol−1 so the entropy required to melt is J . ∆Smelt = 13.65 mol K Again, a numerical integration is required to ﬁnd the entropy change as the liquid neon is taken from the freezing point to the boiling point at 27.2 K. This is J Sboiling − Sfreezing = 3.85 . mol K Finally, 1761 J mol−1 is required to boil the neon at the boiling point, and J . ∆Sboil = 64.74 mol K

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

mol K to the above. However.56 K and 27.98 × 1024 /mol . Groth . Why did I get a slightly diﬀerent value than that quoted in K&K? I used S = R log mkT 2π¯ 2 h 3/2 p kT + 5 2 .Physics 301 15-Oct-2004 16-2 Now we have a gas to which we can apply the Sackur-Tetrode expression. this expression is being applied right at the boiling point. SSackur−Tetrode = 96. mol K J . using a periodic table on the web. Some other things to note.07 K.45 J . Assuming S0 = 0. When I plug into the Sackur-Tetrode expression I actually get. mol K which is in very good agreement with the observed value. the Sackur-Tetrode value for neon at the boiling point is SSackur−Tetrode = 96.40 σ = 6. h occurs inside a logarithm. mol K still in very good agreement with the observed value.47 J . so it’s not clear that the ideal gas law should work all that well. So this is an example where measurements of the entropy pointed towards quantum mechanics. Edward J.) According to K&K. Princeton University Physics Department. (1) If we had left out the N ! over counting correction. This swamps any slight problems with deviations from the ideal gas law or inaccuracies in the numerical integrations! (2) The Sackur-Tetrode expression includes ¯ h which means it depends on quantum mechanics. I ﬁnd the melting and boiling points of neon are 24. (For example. ¯ so it might not have been so easy to spot! Copyright c 2004. which assumes the ideal gas law is valid. We would have to add J R(log N0 − 1) = 447 . where I have quoted the sum from K&K which diﬀers slightly from the sum you get by adding up the four numbers presumably because there is some round-oﬀ in the input numbers. but I’m using p/kT instead of N0 /V . the total is Svapor = ∆Sboil + (Sboiling − Sfreezing ) + ∆Smelt + (Smelting − S0 ) = 96. Everything can be looked up. Of course.

) Copyright c 2004. Of course.54 amu. So the number density of copper atoms is nCu = 8. But. Princeton University Physics Department. nQ = = me kT 2π¯ 2 h 3/2 . 3/2 (9. For copper the actual concentration and the quantum concentration are equal at a temperature of about 100. = .054 × 10−27 erg s) 1 43 ˚ A 3 2 . If the electrons were bound to the atoms they would be insulators. the electron gas is “cold” in the sense that thermal energies are small compared to the energies required to conﬁne them to high densities. the system is said to be degenerate. The number of electrons in the electron gas (assuming one per copper atom) exceeds the quantum concentration by a factor of 6700. These metals have one valence electron—an electron which can be easily removed from the atom. let’s calculate the quantum concentration for an electron at room temperature. In the solid metal. Now consider copper. Furthermore. = 1.108 × 10−28 g) (1.380 × 10−16 erg K−1 ) (300 K) 2π (1.44 × 10 22 cm −3 = 1 2. Edward J.90 g cm−3 and an atomic mass of 63. Low energy states are almost certain to be ﬁlled. First. Groth . It has a density of A 8. How do we know this? Because the metals are good conductors of electricity. so these atoms often form chemical bonds as positively charged ions. (This is most easily seen from an uncertainty principle argument.3 ˚ A 3 .000 K (assuming we could get solid copper that hot!). The upshot of all this is that we are deﬁnitely not in the classical domain when dealing with an electron gas in metals under normal conditions. We will have to use the FermiDirac distribution function. When this is true. the density of electrons is equal to the room temperature quantum concentration if there is one electron every 43 ˚. the valence electrons aren’t bound to the atoms. In other words.Physics 301 The Ideal Fermi Gas 15-Oct-2004 16-3 Consider a metal like sodium or copper (or the other metals in the same columns in the periodic table). Let’s do a little numerology.26 × 1019 cm−3 . as a ﬁrst approximation we can treat all the valence electrons as forming a gas of free (non-interacting) particles conﬁned to the metal. there are interactions between the electrons and the ions and between the electrons and other electrons.

ǫ<µ. and we have dn(ǫ) = V 2π 2 2m h ¯2 3/2 √ ǫ dǫ . 8π 3 ¯ 3 h where the factor of 2 arises because there are two spin states for each center of mass state. Since we have the lowest possible energy. f (ǫ) = 1 → e(ǫ − µ)/τ + 1 1. Groth . we can use the Fermi-Dirac distribution at zero temperature. this conﬁguration must be the ground state (which is the state the system should be in at 0 temperature!). it goes into the state with the next lowest energy. . the independent variable may be converted from momentum to energy with p2 /2m = ǫ. the Fermi-Dirac distribution becomes. We must choose the chemical potential so that our metal has the correct number of valence electrons. This is the same calculation we’ve done before. This means we will ignore thermal energies altogether. Finally. p) = 2 d 3 x d3 p .Physics 301 15-Oct-2004 16-4 So as a ﬁrst approximation. Edward J. And so on. Add back one valence electron remembering that the temperature is 0. we need to know the number of states. Princeton University Physics Department. At zero temperature.). To do this. At zero temperature. Since we are considering free electrons. 0. Copyright c 2004. . It’s customary to write this as the density of states per unit energy D(ǫ) dǫ = V 2π 2 2m h ¯2 3/2 √ ǫ dǫ . V . The element d3 p = p2 dp dΩ and the solid angle may be integrated over to give 4πp2 dp. ǫ>µ. we are dealing with single particle states in a box. the occupancy is 1 up to µ and 0 above µ. the integral over d3 x just leads to the volume of the box. What we are doing is ﬁlling up states (with no gaps) until we run out of valence electrons. Actually it’s the same center of mass state and the same energy. Imagine a chunk of copper in which all the valence electrons have been removed (it would have a rather large electric charge . When the number of states is used in an integral. The number of states with position vector in the element d3 x and momentum vector in the element d3 p is dn(x. Add another electron. so the total number of electrons is µ N= 0 D(ǫ) dǫ . This electron goes into the lowest available state. but the second electron has its spin pointing in the opposite direction from the ﬁrst. The third electron goes in the state with the next lowest energy. Now we’re ready to calculate µ.

and the electron gas in copper really is “cold” all the way up to the point where copper melts! (1358 K) Copyright c 2004. the energy goes down which means it must be exerting a pressure on its container. so the entropy is constant at 0. Edward J. The Fermi temperature is a few tens of thousands of Kelvins for most metals. p=− so ∂U0 ∂V = σ.Physics 301 15-Oct-2004 16-5 Before we do this integral. This is not actually the temperature of anything. pV = As a point of interest. We just add up the energies of all the occupied states ǫF U0 = 0 ǫ V 2π 2 2m h ¯2 3/2 √ ǫ dǫ = V 5π 2 2m h ¯2 3/2 ǫF 5/2 = V 3 h ¯2 (3π 2 n)5/3 = N ǫF . a bit of jargon. In the ground state. 3/2 or ǫF = (3π 2 n)2/3 where n = N/V is the concentration. Princeton University Physics Department. 2m 2m h ¯2 3/2 ǫF . so the electron gas in typical metals is cold. Groth . but is a measure of the energy that separates degenerate from non-degenerate behavior. 3 just as for an ideal gas. In fact. One also speaks of the Fermi temperature deﬁned by τF = kTF = ǫF . Having determined the Fermi energy. Note that the derivative is to be taken at constant entropy. The energy of the highest ﬁlled state at zero temperature is called the Fermi energy. we can determine the total energy of the gas. using the concentration for copper that we calculated earlier. We are dealing with the ground state. So µ(τ = 0) = ǫF . Also note that the concentration contains V −1 which means U0 ∝ V −2/3 which means that as the system expands. This is called degeneracy pressure.02 eV and TF = 81. Then ǫF N= 0 V 2π 2 2m h ¯2 3/2 √ V ǫ dǫ = 3π 2 h ¯2 . 2 5π 2m 5 where the subscript on U indicates the ground state energy. 500 K . 3 V 2 U0 .N 2 U0 . the average energy of an electron is 3/5 the Fermi energy. we ﬁnd ǫF = 7. ǫF .

What about µ? At τ = 0. The diﬀerence in energy between the gas at temperature τ and the gas in the ground state is ∞ ∆U (τ ) = 0 ∞ ∞ D(ǫ)f (ǫ)ǫ dǫ − U0 . dτ So far. so we will take µ = ǫF . D(ǫ)f (ǫ)(ǫ − ǫF ) dǫ + N ǫF − U0 . With a cold gas. That is the occupancy goes from 1 to 0 over a range of a few τ centered at µ. Edward J. so its derivative is a delta function (a very sharply peaked function in the neighborhood of the step). ∂τ ∞ D(ǫ) df (ǫ) (ǫ − ǫF ) dǫ . So we will ignore the variation in the density of states. the change in µ is negligibly small (plot some curves!). CV = = 0 ∂∆U . evaluate it at µ and take it out of the integral. we need to expand our treatment a bit. This means that the main contribution to the integral occurs (even if τ is not 0) when ǫ is very close to µ. but when τ ≪ ǫF . all the action occurs within τ of µ. D(ǫ)f (ǫ)(ǫ − ǫF ) dǫ + 0 ∞ 0 = = 0 D(ǫ)f (ǫ)ǫF dǫ − U0 . Since we have a cold gas. µ = ǫF .” now we start making approximations. This does not allow us to consider adding heat to the gas because the gas would no longer be in the ground state. d df = dτ dτ 1 e(ǫ − ǫF )/τ + 1 = . this is a relatively narrow range. As τ increases. Copyright c 2004. Now. To calculate the heat capacity. Groth . At τ = 0. dτ ǫ − ǫF τ2 e(ǫ − ǫF )/τ e(ǫ − ǫF )/τ + 1 2 Now. the distribution is a step function.Physics 301 Heat Capacity of a Cold Fermi Gas 15-Oct-2004 16-6 In the preceding section we considered the Fermi gas in its ground state. µ decreases. We will calculate the diﬀerence between the ground state energy and the energy at temperature τ and we will make use of the fact that the gas is cold. What we need to do is calculate the energy of the gas as a function of temperature. Princeton University Physics Department. everything is “exact. Then we have ∞ CV = D(ǫF ) 0 df (ǫ) (ǫ − ǫF ) dǫ . we diﬀerentiate with respect to τ to get the heat capacity.

It turns out that the integral is π 2 /3. Groth . At low temperatures. we have D(ǫF ) = and CV = In conventional units. Copyright c 2004. has been replaced by −∞ since all the contribution to the integral is in the neighborhood of x = 0. so π2 D(ǫF )τ . −ǫF /τ . CV = 3 a surprisingly simple result! If we plug in the expression for the density of states. This is because only the fraction τ /τF of the electrons are excited out of the ground state. Some experimental data may be found in K&K. 2 TF 3N . so the added energy is roughly N τ 2 /ǫF .Physics 301 At this point. The Fermi gas heat capacity is quite a bit smaller than that of a classical ideal gas with the same energy and pressure. we are exciting electrons in the energy range from ǫF −τ → ǫF by giving them a thermal energy of roughly τ . (ex + 1) where the actual lower limit of integration. 2ǫF π2 τ π2 τ N = N . Can we see how this happens? In going from 0 to τ . This is proportional to T which means that the energy of the electron gas is U0 + constant · τ 2 . heat capacities of metals have a linear term due to the electrons and a cubic term due to the lattice. 2 ǫF 2 τF Some comments. The number of such electrons is roughly N τ /ǫF . Edward J. Princeton University Physics Department. CV = π2 T Nk . we change variables to x = (ǫ − ǫF )/τ and we have +∞ 15-Oct-2004 16-7 CV = τ D(ǫF ) −∞ x2 ex dx 2 .

17. “Onset of Fermi Degeneracy in a Trapped Atomic Gas. In this calculation we assumed that the density of states near the Fermi energy is constant and this allows one to pull the density of states out of the integral and also to set the chemical potential to its 0 temperature value. Groth . “At Long Last. The third is also by Levi. “Gaseous Bose-Einstein Condensate Finally Observed. B. 48. To calculate the energy.Physics 301 Reading 1-Nov-2004 17-1 Finish K&K chapter 7 and start on chapter 8. The ﬁrst is by Graham P. etc. DeMarco. at arbitrary temperatures. vol. Basically. 1703. More on Fermi Gases So far. In addition. Also.” describing the ﬁrst “atom laser” which was based on a BE condensate. vol. October. vol. no.. p. p. 50. a Bose-Einstein Condensate is Formed in Hydrogen. September 10. and Jin. Princeton University Physics Department. 10. We simply said that all states.. Edward J. 1998.. 8. Collins. The zero temperature Fermi gas was straightforward. S.” Bose condensates and Fermi degeneracy are current hot topics in Condensed Matter Research. starting from the lowest energy state. p. we’ve considered the zero temperature Fermi gas and done an approximate treatment of the low temperature heat capacity of Fermi gases. 17. there is a recent Science report on an atomic Fermi Gas. ǫF = µ(τ = 0). D. 1999. “Bose Condensates are Coherent Inside and Outside an Atom Trap. p.” describing even more progress on BE condensates. Working on the low temperature heat capacity required an approximate calculation of the energy versus temperature for a cold Fermi gas. no.” This describes the research leading up the ﬁrst observation of a BE condensate that’s not a superﬂuid or superconductor. no. 1997. 51. 285. Then the chemical potential is varied until the desired number of particles is Copyright c 2004. Searching the preprint server or “Googling” with appropriate keywords is bound to turn up many more articles. The second is by Barbara Goss Levi. one must numerically integrate the Fermi-Dirac distribution times the density of states to obtain the number of particles. These approximations work quite well for the electron gas in metals at room temperature because the Fermi temperature for these electron is typically several tens of thousands of Kelvins. 3. all we had to do was determine the density of states. The energy at which this happens is called the Fermi energy and is the same as the chemical potential at 0 temperature. a problem we’ve dealt with before. August. I’m passing out several Physics Today articles. are ﬁlled until we run out of particles. 1995. March. 17. vol.

Edward J. The coeﬃcient in this relationship can vary by a tenth or so depending on just how one measures the size—scattering by charged particles. 3 and the number density or concentration is nnuc = A = 1. Copyright c 2004. where A is the number of nucleons. a statistical treatment is a reasonable approximation. Other Fermi Gases In addition to the conduction electron gas in metals.2 × 10−39 A cm3 . Aside: the unit of length 10−13 cm which is one femtometer is called the Fermi in nuclear physics. In heavy elements. Figure 7. This kind of treatment is called the Thomas-Fermi (or sometimes the Fermi-Thomas) model of the atom. there are eﬀects due to the crystal structure such as energy bands and gaps. Princeton University Physics Department. Fermi gases occur in other situations.Physics 301 1-Nov-2004 17-2 obtained. one can integrate the density of states times the Fermi-Dirac distribution times the energy to get the energy at a given temperature. scattering by neutrons. V The nuclear density (with this number of signiﬁcant digits.9 and tables 7. etc. The volume of a nucleus is V = 4π 2.3 of K&K demonstrate that the low temperature heat capacities (low enough that the Debye lattice vibrations are accurately following a T 3 heat capacity) have a component proportional to the temperature and list the proportionality constants for various metals.3 × 10−13 cm) · A1/3 . Groth .8 × 1014 g cm−3 . Also in heavy elements. again.2 and 7. One thing you will notice is that the proportionality constants agree with the calculations to only ∼ 30% and up to a factor of 2 in at least one case.1 × 1038 cm−3 . the number of electrons per atom becomes large enough that a statistical treatment is a reasonable approximation. Knowing the chemical potential. eﬀects on atomic structure. Also. the mass diﬀerence between neutrons and protons is negligible) is ρnuc = 1. The radius of a nucleus is R ≈ (1. All of this requires numerical integration or approximate techniques. the number of nucleons (neutrons and protons) in the nucleus is large and. This is most likely due to the fact that the electrons are not really a non-interacting gas.

Physics 301

1-Nov-2004 17-3

Basically, all nuclei have the same density. Of course, this is not quite true. Nuclei have a shell structure and “full shell” nuclei are more tightly bound than partially full shell nuclei. Also, the very lightest nuclei show some deviations. Nevertheless, the density variations aren’t large and it’s reasonable to speak of the nuclear density. The neutron to proton ratio in nuclei is about 1 : 1 for light nuclei up to about 1.5 : 1 for heavier nuclei. Assuming the latter value, then it is the neutrons whose Fermi energy is important. ǫF = h ¯2 3π 2 (0.6 · nnuc ) 2mn

2/3

= 5.2 × 10−5 erg = 32 MeV .

This is a little larger than K&K’s number because it’s computed for a nucleus with 40% protons and 60% neutrons, instead of equal numbers. Since the average kinetic energy in a Fermi gas is 3ǫF /5, the average kinetic energy is about 19 MeV in a heavy nucleus. The experimentally determined binding energy per nucleon is about 8 MeV. This varies somewhat, especially for light nuclei; it reaches a peak at 56 Fe. To the extent that the binding energy per nucleon and the kinetic energy per nucleon are constant, the potential energy per nucleon is also constant. This reﬂects the fact that the nuclear force is the short range strong force and nuclei only “see” their nearest neighbors. The strong force is about the same between neutrons and protons, between protons and protons and between neutrons and neutrons. But, the protons have a long range electromagnetic interaction. As the number of particles goes up the “anti-binding” energy of the protons goes up faster than the number of protons (can you ﬁgure out the exponent?) so the equilibrium shifts to favor neutrons in spite of the fact that they are slightly more massive than protons. The Fermi temperature for neutrons in a heavy nucleus is TF = ǫF /k = 3.8 × 1011 K , so nuclei (which are usually in their ground state) are very cold! In a star like the Sun, gravity is balanced by the pressure of a very hot, but classical, ideal gas. The Sun has a mass about 300,000 times that of the Earth and a radius about 100 times that of the Earth, so the average density of the Sun is somewhat less than that of the Earth (it’s about the density of water!). The temperature varies from about 20 million Kelvins at the center to about 6000 K at the surface. So it’s completely gaseous and the electrons are non-degenerate throughout. Since the sun is radiating, it is cooling. Energy is supplied by nuclear reactions in the Sun’s core. A typical white dwarf star has about the mass of the Sun but the radius of the Earth. It’s the degeneracy pressure of the electrons that balances gravity in a white dwarf. White dwarves shine by cooling. There are no nuclear reactions in the core, so after they cool enough, they become invisible. White dwarves are discussed in K&K, so let’s move on to neutron stars which are not discussed in K&K.

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301 Neutron Stars

1-Nov-2004 17-4

In a neutron star it’s the degeneracy pressure of the neutrons that balances gravity. A typical neutron star has a mass like the Sun (M⊙ = 2 × 1033 g) but a radius smaller than New Jersey, let’s say R ≈ 10 km. Let’s assume that the mass in a neutron star is uniformly distributed. What’s the density? ρ = M/V = 4.8 × 1014 g cm−3 , about three times nuclear density. (Of course, the density in a star is not uniform and it may exceed 10 times nuclear density in the center, but we’re just trying to do a back of the envelope calculation here.) In terms of the concentration of neutrons, this corresponds to n0 = 2.9 × 1038 cm−3 . The Fermi energy for these neutrons is ǫF,0 ≈ 86 MeV , and the Fermi temperature is TF = 1012 K . Neutron stars are nowhere near this hot. Otherwise they would be very strong sources of gamma rays. Instead they are thought to have temperatures of millions of degrees and radiate X-rays. I believe there are some observations which indicate this. Also, due to having a magnetic ﬁeld and rotating, they can radiate electromagnetic energy and are observed as pulsars. In any case, the neutrons in a neutron star are cold! An interesting question is why is a neutron star made of neutrons? (Well, if it weren’t, we probably wouldn’t call it a neutron star, but besides that?) In particular, what’s wrong with the following? Let the star be made of protons and electrons, each with the concentration we’ve just calculated. Then the star is electrically neutral because there is a sea of positively charged protons and a sea of negatively charged electrons. But the protons have a slightly lower mass than the neutrons and this is true even if one adds in the mass of the electron, so this conﬁguration would seem to be energetically favored over the neutron conﬁguration. In fact, a free neutron decays according to n → p + e− + νe , ¯ where νe is the electron anti-neutrino. The half life is about 15 minutes. Neutrinos are ¯ massless (or very nearly so) and for our purposes we can ignore them. That is, we can assume that the neutrons are in equilibrium with the protons and electrons. If we need to change a neutron into a proton and electron, the above reaction will do it. If we need to change a proton and electron into a neutron, there is p + e− → n + νe .

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

Physics 301

1-Nov-2004 17-5

What would be the Fermi energies of the protons and electrons in our hypothetical star? The Fermi energy for the protons would be very nearly the same as that for the neutrons above (because the concentration would be the same and the mass is nearly the same). On the other hand, the Fermi energy of the electrons would be larger by the ratio of the neutron mass to the electron mass, a factor of 1838, so the electron Fermi energy would be about 160,000 MeV, enough to make about 170 nucleons! Remember that the chemical potential (the Fermi energy since all the gases are cold) is the energy required to add a particle to a system. If neutrons are in equilibrium with protons and electrons, then the chemical potential of the neutrons equals the chemical potential of the protons plus the chemical potential of the electrons minus the energy diﬀerence between a neutron and a proton plus electron. In other words ǫF,n = ǫF,p + ǫF,e − (mn − mp − me )c2 . Denote the concentrations of the neutrons, protons, and electrons by nn , np , and ne . Then np = ne , for charge neutrality and np + nn = n , where n is the concentration of the nucleons, which is not changed by the reactions above. To simplify the notation a bit, let x= np ne = , n n 1−x= nn . n

**Each of the Fermi energies can be written in terms of the concentrations ǫF,n = ǫF,p = ǫF,e where ǫF,0 = h ¯2 (3π 2 nn )2/3 = ǫF,0 2mn ¯2 h (3π 2 np )2/3 = ǫF,0 2mp n n0 n n0 n n0
**

2/3

(1 − x)2/3 ,

2/3

mn 2/3 x , mp mn 2/3 x , me

h ¯2 (3π 2 ne )2/3 = ǫF,0 = 2me

2/3

h ¯2 (3π 2 n0 )2/3 , 2mn

is the Fermi energy for a pure neutron gas at the concentration n0 we calculated previously. We plug these energies into the energy equation to obtain ǫF,0 n n0

2/3

(1 − x)

2/3

= ǫF,0

n n0

2/3

mn mn + mp me

x2/3 − E ,

Copyright c 2004, Princeton University Physics Department, Edward J. Groth

. so we really shouldn’t be using our non-relativistic formula for the electron Fermi energy. 0.0 n0 n 2/3 . At higher concentrations x will get slightly smaller and at lower concentrations x will grow slowly. so the electrons are extremely relativistic. protons. this calculation gives the ﬂavor of what’s involved and points to the correct conclusion: For most of its volume a neutron star is almost pure neutrons! Of course. Nevertheless. we obtain (1 − x)2/3 = or (1 − x)2/3 = (1.2 × 10−8 n0 = 6. Caveats: (1) The Fermi energy of the electrons works out to be about 87 MeV. Princeton University Physics Department. Edward J. One of this week’s homework problems gives you a chance to modify the treatment to allow for relativistic electrons.3 × 10−5 . Groth .0014 + 1838. Such low concentrations will be attained only very near the surface of the neutron star. then x is small. we can ignore x on the right hand side.7) x2/3 − or x2/3 = 0. If we rearrange slightly. we can turn the earlier question around: how is it that nuclei have any protons??? Haven’t we just shown that at nuclear densities. The concentration of neutrons.4 × 1030 cm−3 . and we ﬁnally obtain x ≈ 1. the nucleons must exist as neutrons. not protons??? Copyright c 2004. If n is in the neighborhood of n0 .783 n0 86 n n0 n 2/3 2/3 . (2) With an electron and proton instead of a neutron.000544 (1 − x)2/3 + 0.Physics 301 1-Nov-2004 17-6 where E = (mn − mp − me )c2 = 0.0091 mn mn + mp me x2/3 − E ǫF. the pressure changes.5) when n = 2.783 MeV is the mass energy excess of a neutron over a proton and electron. so the equilibrium condition that we set up is not quite right. and electrons are equal (x = 0.

For sufﬁciently low temperatures. It’s just the Planck distribution and this distribution does not have a Bose-Einstein condensation. We’ve already calculated their distribution (which has µ = 0). One can’t create or destroy these bosons without doing something about the rest mass energy (and perhaps other conserved quantum numbers)! So let the gas contain N particles. The gases we’ll be considering will contain a ﬁxed number of matter particles. so something like a phase transition occurs. we adjust the energy scale so that the lowest energy state has ǫ = 0. Princeton University Physics Department. Note that photons obey Bose statistics so they constitute a non-interacting gas of bosons. essentially all the particles are in the same state (the ground state). lim τ →0 τ N τ lim µ = − . 1 =N. The Bose-Einstein distribution is f (ǫ) = 1 . Edward J. This is related to the fact that photons are massless. For convenience. Groth . the number of photons per unit volume decreases. lim e−µ/τ = 1 + τ →0 N µ 1 lim 1 − + · · · = 1 + .Physics 301 Bose-Einstein Gases 3-Nov-2004 18-1 An amazing thing happens if we consider a gas of non-interacting bosons. When τ → 0. τ →0 N 1 . This Bose-Einstein condensation can occur even when the temperature is high enough that one would naively expect that higher energy states should be well populated. τ →0 N lim Recall that µ must be lower than any accessible energy for the Bose-Einstein distribution and here we have µ < 0 in agreement with this constraint. although it converges to 0 as Copyright c 2004. all the particles must be in the ground state. e(ǫ − µ)/τ − 1 and the sum of this distribution function over all states must add up to N . If a photon gas is cooled. It’s possible to create or destroy a photon of arbitrarily small energy. properties of the gas change when it is in this state. In addition. τ →0 τ N 1 −µ = . τ →0 −µ/τ e −1 1 lim e−µ/τ − 1 = . The diﬀerence between photons and the situation we’re about to discuss is that there is no ﬁxed number of photons.

8 × 108 so the occupancy of the ﬁrst excited state is almost 9 orders of magnitude smaller than the occupancy of the ground state. If we consider a mole of 4 He and treat it as an ideal gas with p = 1 atm and T = 1 K. at T = 1 K. what is the population of the ﬁrst excited state? N1 = = = = = = 1 . but this is to be expected as all the particles must pile up in the ground state when τ → 0. Recall that the energies of single particle states in a cube are π2¯ 2 2 h ǫ(nx . 8 e−5. 1.8 × 108 /N N . The key point is that even though the energy of the ﬁrst excited state is incredibly small. It’s instructive to evaluate µ for a mole of particles at a temperature of 1 K. Using the L we just calculated and the mass of 4 He. and you might think such a small energy can have nothing to do with any macroscopic properties of a system. 1. 1) = 1. y z 2mL2 x The ground state has nx = ny = nz = 1 and in the ﬁrst excited state one of these quantum numbers is 2.8 × 10 µ/τ − 1 1 . Groth . 5.3 cm. the diﬀerence in energy between the ground state and the ﬁrst excited state) is almost nine orders of magnitude bigger than µ (at the temperature and density we’re considering).8 × 108 |µ| . so we need to subtract ǫ(1. ny . Then the ground state energy is 0 and the ﬁrst excited state energy is ǫ1 = 1. Edward J. 1) = 2. the ground state energy is supposed to be adjusted to 0. 5. e(ǫ1 − µ)/τ − 1 1 .3 × 10−40 erg .68 × 10−31 erg . nz ) = (n + n2 + n2 ) .34 × 10−31 erg . −5.8 × 108 µ/τ 1 .8 × 108 µ/τ + · · · − 1 1 .34 × 10−31 erg = 5. ǫ(2. Actually. 1) from all energies in the problem. Under these conditions. The result is µ(1 K) = −2. Princeton University Physics Department. This would be equivalent to a cube of side L = 4. Essentially all the particles are in the ground state even though kT is much larger than the excitation energy! Copyright c 2004. then its volume would be V = 82 cm3 . we ﬁnd ǫ(1. 1 − 5.Physics 301 3-Nov-2004 18-2 τ → 0. this energy (or more properly. 1.

it means that the occupancies of all states are small. we would include a factor 2S + 1 to account for the multiplicity of the spin states. However. 3/2 where V D(ǫ) = 4π 2 2m h ¯2 √ ǫ. It would not be a good idea to ignore them in the sum! So we write the sum as ∞ N = N0 + 0 f (ǫ)D(ǫ) dǫ . the number of particles in the ground state is N0 = 1 . Princeton University Physics Department. is the same density of states we used for the Fermi-gas except there’s a factor of two missing because we’re assuming a spin 0 boson gas. e(ǫ − µ)/τ − 1 Copyright c 2004. Groth . the ground state contains orders of magnitude more. V = 4π 2 √ 1 ǫ dǫ . so errors in the occupancies of these states are of no concern.Physics 301 3-Nov-2004 18-3 Now we want to do a proper sum of the occupancy over the energy states. So. We might try to write ∞ N= 0 f (ǫ)D(ǫ) dǫ . Edward J. where the ﬁrst term is the number of particles in the ground state and the second term accounts for all particles in excited states. In the case that these states don’t contain many particles. most of the particles in the ground state. We have had this problem in previous calculations but it never mattered because there were only a few (2 or less) in the ground state and ignoring these particles makes absolutely no diﬀerence to any quantity involving the other ∼ 1023 particles. we are expecting to ﬁnd many. and in some cases.) The expression above has the problem that it fails to count the particles in the ground state. but when these states contain a lot of particles. 1 V 2 e(ǫ − µ)/τ − 1 4π 2m h ¯2 3/2 0 ∞ = 0 2m h ¯2 3/2 √ ǫ dǫ . and again we make no appreciable error if we miss on the occupancies of a few of the low energy excited states. (If the spin were diﬀerent from 0. This term still makes an error in the low energy excited states (since we’re integrating rather than summing). e−µ/τ − 1 and the number of particles in excited states is ∞ Ne = 0 ∞ f (ǫ)D(ǫ) dǫ .

τE .Physics 301 = V 4π 2 2m h ¯2 2m h ¯2 2m h ¯2 3/2 0 3/2 ∞ 3-Nov-2004 18-4 √ 1 ǫ dǫ eǫ/τ − 1 ∞ 0 3/2 (since |µ|/τ ≪ ǫ/τ ) . Princeton University Physics Department. such that Ne = N so τE = 2π¯ 2 h m τ τE 3/2 . τ 3/2 .612V nQ . Groth . 2/3 N 2. the Einstein temperature is TE = 115 Vm m 2/3 1− τ τE 3/2 . . V = 4π 2 = V 4π 2 τ 3/2 1 √ x − 1 x dx e τ 3/2 Γ(3/2)ζ(3/2) . Vm is the molar volume in cm3 and m is the molar weight in grams. (x = ǫ/τ ) .6 cm3 . We deﬁne the proportionality constant by deﬁning the Einstein condensation temperature. where nQ is the quantum concentration again. and we expect the expression for Ne should be valid from τ = 0 up to τ = τE .1 K. with a molar volume of 27. |µ| will be closer to 0 than to the ﬁrst excited state energy provided the ground state contains about 1015 or more particles which means the excited states must contain about 6×1023 −1015 = 6×1023 particles.612V 2π¯ 2 h = 2. The major approximation we made in the above calculation was ignoring the chemical potential. In other words.612V .306 π 2 4π mτ = 2. . our approximation for Ne above should be valid all the way to the point where Ne = N . For liquid 4 He. 2m h ¯2 3/2 3/2 √ V = 1. this gives TE = 3. then |µ| must be much smaller then the energy of any excited state and this is a good approximation. where TE is in Kelvins. With the numerical example we worked out before. There Copyright c 2004. As long as there are an appreciable number of particles in the ground state. This means that the Ne ∝ τ 3/2 . Edward J. Then the number in the condensate is N0 = N Numerically.

Groth . To understand this we need to examine the mechanics of friction on a microscopic level. In the case of helium. In addition to the heat capacity. the attractive interactions help to get the density high enough to form the condensate at more accessible temperatures! Superﬂuid Helium As mentioned. Below this temperature.17 K at 1 atm is believed to be the condensation of most of the helium atoms into the ground state—a Bose-Einstein condensation.14 and 7.2 K and one atmosphere.1 K is believed to be due to the fact that there are interactions among helium atoms so that helium cannot really be described as a non-interacting boson gas! Above the transition temperature. friction must be caused by molecular collisions which transfer energy from the average motion (represented by the bulk velocity) to the microscopic motion (internal energy). That this does not occur at the calculated temperature of 3. it’s called He II. The fact that something happens at 2. Copyright c 2004. but it is more complicated than the simple theory we have worked out because there are interatomic forces between the helium atoms. helium is refered to as He I and below the transition.15). liquid He develops a superﬂuid phase.17 K. If you read the articles referenced at the beginning of these notes. The liquid helium becomes a superﬂuid which means it ﬂows without viscosity (that is.12 in K&K) which is similar to the heat capacity curve for a phase transition and also not all that diﬀerent from the curve you’re going to calculate for the Bose-Einstein condensate in the homework problem (despite what the textbook problem actually says about a marked diﬀerence in the curves!). K&K present several reasons why thinking of liquid helium as a non-interacting gas is not totally oﬀ the wall. Without worrying about the details. This phase is most likely a Bose-Einstein condensation. the transition of 4 He at 2.17 K is shown by the heat capacity versus temperature curve (ﬁgure 7. the mechanical properties of 4 He are markedly diﬀerent below the transition temperature. The existence of a Bose-Einstein condensate does not necessarily imply the existence of superﬂuidity. Princeton University Physics Department. We know this because there must be forces that are responsible for the condensation of helium gas to liquid helium at T = 4. Edward J. You should read them and also study the phase diagrams for both 4 He and 3 He (K&K ﬁgures 7. you’ll see that a major problem faced by the experimenters in creating BE condensates in other systems is getting the atoms cold enough and dense enough to actually form the condensate. friction).Physics 301 3-Nov-2004 18-5 4 is actually a transition in liquid helium at about 2.

then it would be possible to excite any molecule in the condensate out of the ground state and into the ﬁrst excited state simply by providing the requisite energy (and momentum). 1 1 M Vi2 = M Vf2 + hω . (This can also be viewed as the absorption of one quasiparticle and the emission of another. if quasiparticles already exist. In order to have superﬂuid behavior. In order to do this. the object could “collide” with a quasiparticle and scatter it to a new state of energy and momentum. The number of ¯ ¯ units is determined by the number of phonons or quasiparticles in the wave. In particular. Princeton University Physics Department. Groth . 2 2M 2 Copyright c 2004. Now imagine an object of mass M moving though a stationary superﬂuid with velocity Vi . Before the event. Of course. ¯ 2 2 and M Vi = M Vf + h k . the object must create excitations in the ﬂuid which contain momentum (the quasiparticles in the travelling waves we just discussed). In order for there to be a force on the object. the energy diﬀerence between the ground state and the ﬁrst excited state was about 10−31 erg. The momentum equation can be rewritten as M Vi − ¯ k = M Vf .) A travelling wave carries energy in units of hω and momentum in units hk. there must be a momentum transfer to the superﬂuid. A better way to say this is that due to the molecular interactions. we can consider travelling sound waves of wave vector k and frequency ω. We must conserve both energy and momentum. Edward J.) We will assume that there are not very many existing quasiparticles and consider only the creation (emission) of a quasiparticle. it must be that there are interactions among the molecules such that it’s not possible to excite just one molecule out of the condensate and into the ﬁrst excited state. So. Previously. we calculated that under typical conditions. the single particle states are not discrete energy states of the superﬂuid. ¯ We can go through some algebra with the goal of solving for Vi · k. h squared and divided by 2M . let’s consider this emission process. 1 2 2 1 1 M Vi2 − ¯ Vi · k + h h ¯ k = M Vf2 .Physics 301 3-Nov-2004 18-6 If our Bose-Einstein condensate were really formed from a gas of non-interacting particles. We need to consider the normal modes of the ﬂuid—the longitudinal oscillations or the sound waves. the object has velocity Vi and afterwards it has velocity Vf . (Rather than the standing waves which carry no net momentum. an incredibly small amount of energy that would be very easy to provide given that thermal energies are about 10−16 erg.

where L is the size of the box containing the superﬂuid. we made an assumption that doesn’t apply in most cases.) Suppose the excitations are sound waves (as we’ve been assuming) and the phase velocity is independent of k. Groth . This corresponds to emission of the quasiparticle in the forward direction. Edward J. the unit vector in the k direction. k where vs is the phase velocity of sound in the ﬂuid. but as we’ve already seen the energies corresponding to this k are tiny compared to thermal energies. Figure 7. the ﬂow is without drag! That is. k h ¯k 2M What we really want to do is place a lower limit on the magnitude of Vi . The smallest value will occur when Vi is parallel to k/k. This means that if an object ﬂows through the ﬂuid at less than the velocity of sound. (Note: k must be bigger than ∼ 1/L. Princeton University Physics Department.Physics 301 Subtract from the energy equation to get h ¯ Vi · k = hω + ¯ or 1 2 2 h ¯ k . This means we can drop the term containing M on the right hand side. the vs is not independent of k and what sets the limit is the minimum phase velocity of any excitation that can be created by the object moving through the ﬂuid. 2M 3-Nov-2004 18-7 h ¯ω h ¯k k = + . Thus Vi · Vi > h ¯ω . h ¯k I’ve left the h’s there in order to emphasize that the right hand side is the ratio of the ¯ energy to the momentum of an excitation. Thus. Suppose the excitations are single particle states with momentum hk and energy ¯ h ¯ 2 k 2 /2m. an object moving with an arbitrarily small velocity can produce an excitation and feel a drag force—there is no superﬂuid in this case. In our derivation.17 in K&K shows that this minimum is about 5000 cm s−1 for the low lying excitations in 4 He. This is the travelling wave analog to the standing wave particle in a box states we’ve discussed many times. Can you ﬁgure out which assumption it was? Copyright c 2004. K&K point out that Helium ions have been observed to travel without drag through He II at speeds up to about 5000 cm s−1 ! Comment 1: It appears that we’ve shown that any ﬂuid should be a superﬂuid as long as we don’t move things through it faster than its speed of sound. In fact. Then Vi > ω = vs . the ﬂuid is a superﬂuid. Then the right hand side becomes ¯ k/2m which goes to h zero as k → 0.

Physics 301 3-Nov-2004 18-8 Comment 2: As a general rule. superﬂuidity or superconductivity requires the condensation of many particles into a single (ground) state and a threshold for creating excitations. Edward J. Princeton University Physics Department. Copyright c 2004. The minimum velocity required to create an excitation is the threshold for non-viscous ﬂow. Groth .

Where is the heat supplied? Heat is supplied in the form of sunlight which keeps the weather going which provides water in the atmosphere to make rain to ﬁll the lake behind the dam. of a system. They are energy transfers. The weight is allowed to fall under the inﬂuence of gravity. obtained by burning coal. Once the weight reaches the end of its travel. The desire to make better steam engines produced thermodynamics! With an irreversible process you can turn work completely into heat. What we really mean to say is that with an irreversible process we can use work to increase the internal energy of a system and leave that system in a ﬁnal conﬁguration that would be exactly the same as if we had reversible heated the system. etc. When work is done to or by a system. Of course. so we will try to focus on the material not yet covered and just hit the highlights of the remaining material. This material might be considered to have a more classical thermodynamics rather than statistical mechanics ﬂavor. and in some cases it may be hard to see where the heat enters. U . Performing work changes the energy. This is why we have power plants and engines. Basically all forms of mechanical or electrical energy that we use involve heat to work conversion. this statement is not well deﬁned. Edward J. we wait for the ﬂuid to stop sloshing and the temperature and pressure in the ﬂuid to become uniform. Princeton University Physics Department. consider a viscous ﬂuid in an insulating container. ¯ A very important activity in any modern society is the conversion of heat to work. For example. Immersed in the ﬂuid is a paddle wheel which is connected by a string running over various pulleys and whatever to a weight. Because the ﬂuid is so viscous. Heat and work occur during processes. But work does not change the entropy. Actually.Physics 301 Heat and Work 5-Nov-2004 19-1 Now we want to discuss the material covered in chapter 8 of K&K. It was the steam engine (conversion of heat. what about hydro-electric power? This is the storage of water behind a dam and then releasing the gravitational potential energy of the water to run an electric generator. the macroscopic parameters of the system are changed—for example changing the volume causes p dV work to be performed. Heat transfer changes the entropy as well as the energy: dU = dQ = τ dσ . Groth . the economics of this process are quite diﬀerent from the economics of an oil ﬁred electrical generating plant. Not all of them involve fossil fuels. For example. We’ve discussed reversible processes several times and we’ll assume reversible processes unless we explicitly state otherwise. the weight drops at a constant slow speed. Thus essentially all of the mechanical gravitational Copyright c 2004. We’ve already discussed a lot of this material in bits and pieces throughout the term. into work) that allowed the industrial revolution to proceed. Work is an energy transfer by macroscopic means and heat is an energy transfer by microscopic means.

¯ ¯ we remove only the energy dU = dW and leave the entropy! If we want to continue using ¯ the system to convert heat to work. (I’m getting tired of trying to say it exactly correctly. U ) entirely into work with no other change. Ql τl ηC = τl W =1− . right?) The constraints are that you can’t convert all of it to work or there must be some permanent change in the system or both. τh τl τh Qh = . Edward J. This means ∆U = 0 = Qh − Ql − W . we have to remove the entropy as well as the energy. and energy −W in the form of work is transfered into the system.Physics 301 5-Nov-2004 19-2 potential energy is converted to internal energy of the ﬂuid. There is no known way to convert (reversibly or non-reversibly) heat (more properly. This is one of the ways of stating the second law of thermodynamics. Groth . The problem is that when we reversibly add heat to a system we add internal energy dU = dQ and we also add entropy dσ = dQ/τ . Princeton University Physics Department.) At the end of this time interval we want the system to be in the same state it was when we started. Then we insulate the gas and allow it to reversibly expand until its temperature is the same as when we started. (So heat Ql > 0 leaves the system and work W > 0 is performed on the outside world. The only way to remove entropy (reversibly) is to remove heat. but when we use the system to perform work. To make this a little more quantitative. so we have completely converted the heat into work. It is certainly possible to convert heat into work. internal energy. Qh τh and Copyright c 2004. so I’ll just use the vernacular and you know what I mean. Then the internal energy of the gas is the same as when we started. We want to remove less heat than we added (so we have some energy left over for work) so we must remove the heat at a lower temperature than it was added in order to transfer the same amount of entropy. and ∆σ = 0 = We ﬁnd Qh Ql − . For example. The gas now occupies a bigger volume and has a lower pressure. heat −Ql is transfered into the system at temperature τl . so there is no accumulation of entropy. but the system is not the same as when we started. consider some time interval (perhaps a complete cycle of a cyclic engine) during which heat Qh is transfered into the system at temperature τh . We can take the ﬂuid from the same initial state to the same ﬁnal state by heating slowly (reversibly!) until we have the same temperature rise. suppose we reversibly add heat to an ideal gas while we keep the volume constant.

even if perfectly reversible. this deﬁnition of eﬃciency is motivated by the fact that if you’re an electric power company. have an eﬃciency less than the Carnot eﬃciency. W/Qinput . improving the Carnot eﬃciency requires increasing the high temperature. so all real engines operating between temperature extremes τh and τl will have an eﬃciency less than the Carnot eﬃciency. Such engines. He worked in the early 1800’s and understood the second law. Ql . For the ideal engine we’ve been considering. because that minimizes Ql . etc. and is the upper limit to the eﬃciency of any real (i. However. τh . The energy conversion eﬃciency or just eﬃciency. one uses a coeﬃcient of performance. A reversible refrigerator uses work supplied from the outside to remove heat from a low temperature reservoir and deposit that heat plus the work used as heat in a high temperature reservoir. Princeton University Physics Department.Physics 301 5-Nov-2004 19-3 The ratio of the heat input and output is the same as the ratio of the temperatures of the input and output reservoirs. non-reversible) engine operating between temperature extremes τh and τl . and W all change but anything involving their ratios remains the same. There may come a time when a cost is associated with Ql . Ql . if one assumes a perfect. but run backwards! The signs of Qh . Edward J. In this case it’s still desirable to maximize η. you can charge your customers based on W but you have to pay your suppliers based on Qh and you want to maximize proﬁts! We live on the surface of the Earth and any engine must dump its waste heat. about 300 K. This is roughly the equilibrium temperature of the surface of the Earth and is set by radiation equilibrium between the Sun and Earth and between the Earth and space (T = 3 K). one can calculate an eﬃciency (lower than the Carnot eﬃciency) which is the upper limit that can be achieved by that engine design. Aside: are you surprised that room temperature and the surface temperature of the Earth are about the same? Anyway. this is deﬁned as the ratio of the heat Copyright c 2004. (Note if you wanted to “derive” refrigerators you could start from the same idea we used with the engine—entropy is only transfered when there’s a heat transfer and entropy must not be allowed to accumulate in the refrigerator. But this is not so easy to do.) With refrigerators. Such a refrigerator is basically the reversible engine just discussed. Carnot might be called the father of thermodynamics. Groth . Comment 2: many practical engines are designed in such a way that heat is exchanged at intermediate temperatures as well as the extremes. Comment 1: no real engine is reversible. η is deﬁned as the work output over the heat input. Because waste heat must be dumped at room temperature. the waste heat goes into the environment and usually generates thermal pollution. especially in an economically viable power plant that’s supposed to last for many years. the Carnot eﬃciency. frictionless.e. the eﬃciency is ηC . See problem 5 in chapter 4 of K&K. at what amounts to room temperature. This was before heat was recognized as a form of energy! Of course. reversible engine operating according to the speciﬁed design.

Similar kinds of arguments can be used to show that all reversible refrigerators operating between the same two reservoirs must have the same coeﬃcients of performance.Physics 301 5-Nov-2004 19-4 removed from the low temperature reservoir to the work required. τh − τl and this is an upper limit to the performance of any refrigerator operating between the same temperature extremes. Copyright c 2004. Run the high eﬃciency engine for some time. Therefore all reversible engines operating between the same two reservoirs must have the same eﬃciency. That is they have dimensions instead of being dimensionless! To convert to a dimensionless number you must multiply by 1 Hour J Hour 1055 Joules · = 0. To do this. Now run the other engine in reverse (it’s reversible!) as a refrigerator removing heat Ql from the low temperature reservoir. To see this. W ′ < W . and that reversible refrigerators have higher coeﬃcients of performance than irreversible refrigerators. the Carnot coeﬃcient of performance is τl γC = . so the low temperature reservoir is exactly the same as when we started. suppose that one has two reversible engines operating between the same two temperature reservoirs but they have diﬀerent eﬃciencies. I believe these are given in BTU per hour per watt. W and for a reversible refrigerator operating between temperatures τl and τh . taking heat Qh from the high temperature reservoir. But. you will ﬁnd something called an energy eﬃciency rating (EER) which is basically the coeﬃcient of performance. producing work W .29 . Princeton University Physics Department. so the “real” γ is about 3! Note that all reversible engines operating between the same two temperature reservoirs must have the same eﬃciency. Aside: If you go to a department store and look at air conditioners. that reversible engines are more eﬃcient than irreversible engines. Groth . Edward J. 1 BTU 3600 Seconds BTU s A typical EER you’ll ﬁnd on an air conditioner is roughly 10. all reversible refrigerators operating between the same two temperature reservoirs must have the same coeﬃcients of performance. This is γ= Ql . This is a violation of the second law of thermodynamics. the refrigerator is supplied with work W ′ and it dumps heat Q′ = Ql + W ′ to the high temperature reservoir. So the net eﬀect of running the two engines is to extract heat from the high temperature reservoir and turn it completely into work. and it does not happen. and dumping heat Ql = Qh − W in the low temperature reservoir. Similarly. Since this is the less eﬃcient of the two h reversible engines.

In step bc. Along these paths pV = const. So paths ab and cd are the constant temperature paths with τ = τh and τ = τl .) Given a working substance we can plot the Carnot cycle on a pV diagram.Physics 301 The Carnot Cycle 5-Nov-2004 19-5 We’ve mentioned the Carnot eﬃciency and we’ve talked about heat engines. the temperature is lowered at constant entropy. The vertices abcd in this diagram are the same as the vertices abcd in the τ σ diagram. Paths bc and da are the constant entropy paths with σ = σ2 and σ = σ1 . It’s whatever component actually receives the heat and undergoes changes in its entropy and internal energy and performs work on the outside world. entropy is removed at constant temperature by placing the system in contact with the low temperature reservoir. so more work is done on the system. then it must expand to keep the temperature constant. We plot the entropy of the “working substance” in an engine on the horizontal axis and the temperature of the working substance on the vertical axis. by isentropic compression. The hatched area within the path followed by the system is the total heat added to the system in one cycle of operation. the system is returned to the starting temperature. In step cd. The working substance might be an ideal gas. The ﬁgure shows the Carnot cycle for a monatomic ideal gas. the gas expands and does more work on the outside world. There are four steps in a Carnot cycle. Q = Qh − Ql = τ dσ . (It has two isothermal segments and two isentropic segments. Edward J. Princeton University Physics Department. This is the step in which the system is in contact with the high temperature reservoir and heat Qh = τh (σ2 −σ1 ) is added to the system. so it does work on the outside world. make an engine that uses the Carnot cycle. If the system is an ideal gas. The heat removed is Ql = τl (σ2 − σ1 ). τh . the temperature is constant at τh while the entropy is increased from σ1 to σ2 . No heat is exchanged. so the outside world does work on the gas. the gas is compressed in order to maintain constant temperature. Since the system returns to its starting conﬁguration (same U ) this is also the work done in one cycle. In step ab. In step da. Whatever the working substance. Copyright c 2004. Groth . a Carnot cycle always looks like a rectangle on a τ σ diagram. In this step. The Carnot cycle is most conveniently plotted on a temperature-entropy diagram. but how would one make a heat engine that (were it reversible) would actually have the Carnot eﬃciency? Simple.

Groth . suppose we have a monatomic ideal gas which is the working substance of a reversible engine and it follows the rectangular path on the pV diagram shown in the ﬁgure. W = (p2 − p1 )(V2 − V1 ) . Along da. The arrows on the paths indicate clockwise traversal. W = p dV . If the cycle is run in reverse—counterclockwise—one has a Carnot refrigerator using work to move heat to a higher temperature reservoir. so the Carnot eﬃciency is ηC = 3 . p2 V2 These formulae aren’t all that illuminating so let’s consider a numerical example: suppose p2 = 2p1 and V2 = 2V1 . 4 Copyright c 2004. On ab. while the outside world does some work on the system. V2 . the Carnot cycle is a Carnot engine producing work and waste heat from high temperature input heat.Physics 301 5-Nov-2004 19-6 Along these paths pV 5/3 = const. Then the temperature at the hottest (upper right) vertex is 4 times the temperature at the lowest (lower left) vertex. The work done on the outside world in one cycle is the hatched area within the path. The heat added is 5 3 N (τa − τd ) + N (τb − τa ) . As an example of a non-Carnot cycle. p1 . Princeton University Physics Department. heat is added at constant volume V1 . Edward J. heat is removed at constant pressure. p2 . In this direction. and on cd. On bc heat is removed at constant volume. As before the total work done on the outside world is the area within the path and in this case. = 5 Qin p V − p2 V1 − 3 p1 V1 2 2 2 2 p1 V1 . 2 2 3 5 = (p2 V1 − p1 V1 ) + (p2 V2 − p2 V1 ) . and work is performed. heat is added at constant pressure. 2 2 The actual eﬃciency of this reversible engine is Qin = η= while the Carnot eﬃciency is ηC = 1 − p2 V2 − p2 V1 − p1 V2 + p1 V1 W . 2 2 3 5 = p2 V2 − p2 V1 − p1 V1 .

¯ = dU + d(pV ) − dQ . If a process occurs at constant pressure. you must redesign the cycle to be more like a Carnot cycle.. where H = U + pV . Other Thermodynamic Functions We have concentrated on the internal energy. Copyright c 2004. 13 If you’re actually trying to build a heat engine that operates on this cycle. so dW = dU − d(τ σ) = dF ¯ (constant temperature) . Most heat transfers are at less extreme temperatures and this is why the actual eﬃciency is so much less than the Carnot eﬃciency .” If the system can perform work in other ways. In any constant pressure process the heat added plus the non-p dV work done is the change in enthalpy.Physics 301 The actual eﬃciency is 5-Nov-2004 19-7 2 . the extreme temperatures are reached only at the upper right and lower left vertices. U . Groth . you will approach an eﬃciency of 2/13 and this should be your goal. etc. In the cycle shown. ¯ ¯ ¯ and dWother = dU − dWpV − dQ . dW = dWother + dWpV . the change in enthalpy is just the heat added. This is because at constant temperature. such as all processes open to the atmosphere. Edward J. not the Carnot eﬃciency. In particular. is called the enthalpy. ¯ = dH − dQ ¯ (constant pressure). then the work done on the system is the change in the Helmholtz free energy. Note that dWother is what K&K call the ¯ “eﬀective” work in a constant pressure process. heat losses.” so we cannot really use or supply any p dV work performed by or on the system. d(τ σ) = τ dσ. then we are letting the system adjust it’s volume “as necessary. Princeton University Physics Department. if there is no non-p dV work done. η= If you want to approach the Carnot eﬃciency. then we can divide the work into the p dV work and other work. If we consider a constant temperature process. ¯ ¯ ¯ = dU + p dV − dQ . then as you improve the engine by reducing friction. in the preceding discussion. Many processes occur at constant pressure. The p dV work “just happens.

Groth and the net reaction is or . The sulfuric acid becomes two hydrogen ions and one sulfate ion. 1 Wother = G(H2 O) − G(H2 ) − G(O2 ) . current ﬂows and the cell liberates hydrogen and oxygen (electrolysis). Princeton University Physics Department. If these gases are kept in the cell and allowed to run the reactions in reverse. At higher voltage. 2 If the current is passed through the cell slowly and the cell is open to the atmosphere and kept at constant temperature. V0 is the voltage that is established with no current ﬂowing. consider a system (cell) of two noninteracting electrodes in an electrolyte consisting of sulfuric acid dissolved in water. The other work done is electrical work equal to the charge times the voltage. the Gibbs free energy is useful. As an example of the use of the Gibbs free energy. 4 2 1 H2 O → H2 + O2 . 000 J mol−1 . then the process occurs at constant τ and p.” V0 = − Copyright c 2004. Edward J. ∆G = 1. 2N0 e where N0 is Avogadro’s number and e is the charge on an electron. H2 SO4 ↔ 2H+ + SO−− . Also. a system which is allowed to come to equilibrium at constant temperature and pressure will come to equilibrium at a minimum of the Gibbs free energy. one obtains a fuel cell in which the reaction of hydrogen and oxygen to form water generates electricity “directly. The “other” work is electrical work.229 Volts . It should be clear that dWother = dG ¯ (constant temperature and pressure) . Wother = −2eN0 V0 . Since we have two electrons per mole.Physics 301 5-Nov-2004 19-8 In the event that we have a reversible process that occurs at constant temperature and constant pressure. and the reaction at the anode is 1 SO−− + H2 O → H2 SO4 + O2 + 2e− . 2 where the Gibbs free energies can be looked up in tables and it is found that the diﬀerence is ∆G = −273. This is deﬁned as G = F + pV = H − τ σ = U + pV − τ σ . 4 When current is forced through the system in the direction to supply electrons to the cathode. the reaction at the cathode is 2H+ + 2e− → H2 .

Groth . V. if the system has other ways of storing energy. N ) = −σ dτ − p dV + µ dN dH(σ. we have ∂G ∂N = f (τ. Then if the number of particles doesn’t change. some of the material we’ll be discussing this week is taken from Mandl. First of all. the Gibbs free energy is an extremum dG = 0. Or. Princeton University Physics Department. and G itself are extensive parameters. τ. and a pressure reservoir which keeps the pressure constant.p Copyright c 2004. N . G must be proportional to the number of particles. H. those ways should be included in all these thermodynamic functions. the Gibbs free energy is obtained from the energy via two Legendre transformations to change the independent variables from entropy to temperature and from volume to pressure. The second point is that if the system contains several diﬀerent kinds of particles. p) where f is some function of the temperature and pressure. Another thing to note is that τ . dτ = 0.Physics 301 Reading 8-Nov-2004 20-1 K&K chapter 9 and start on chapter 10. p. then µ dN is replaced by i µi dNi . V. V . This means that for ﬁxed temperature and pressure. where the index i runs over the particle types. There are a couple of general points to make here. and the Gibbs free energy. it must be a minimum (because the entropy enters with a minus sign!). then there will have to be an integral of the magnetization (magnetic dipole moment per unit volume) times the magnetic ﬁeld times the volume element to account for the magnetic energy. F . For example. chapter 11. If we diﬀerentiate with respect to N . the enthalpy. the Helmholtz free energy. N ) = −σ dτ + V dp + µ dN . p. and in fact. G = N f (τ. p. the Gibbs free energy is particularly useful for situations in which the system is in contact with a thermal reservoir which keeps the temperature constant. dU (σ. (We will be doing this shortly!) The above way of writing the energy. As remarked earlier. p) . if the system is magnetic and is in a magnetic ﬁeld. Edward J. N ) = +τ dσ − p dV + µ dN ւ ց F = U − τσ H = U + pV dF (τ. N ) = +τ dσ + V dp + µ dN ↓ ↓ G = F + pV G = H − τσ G = U − τ σ + pV dG(τ. dp = 0. G are really just shorthand for what might actually have to be included. Gibbs Free Energy As we discussed last time. and µ are intensive parameters while σ. Also.

As an example. p. We can write down the Gibbs free energy for a classical ideal gas. Now. p. p) = µ(τ. N1 .) = i We must have for any λ. p.) . Of course. Copyright c 2004. λN2 . Furthermore. λN1 .) = λG(τ. . . . . . and ∂G/∂Ni = µi . . we can show that Ni µi . as this just expresses the fact that G and the Ni are extensive parameters. p. G = Nτ n − 1 + pV .Physics 301 8-Nov-2004 20-2 If we compare this with the earlier expression for dG. N1 . it is F = Nτ so log n −1 nQ Zint . N2 . . Groth . . p) . . . For a single component ideal gas. . N1 . N2 . G(τ. we could also have obtained this result with our expression for µ that we worked out in lecture 14! Note that. N2 . We worked out the Helmholtz free energy in lecture 14. we see that f (τ. τ nQ Zint log where we used the ideal gas law to replace N τ with pV and N/V with p/τ . G(τ. . as advertised. . but it is not necessarily true that µi depends only on τ and p. G(τ. In other words.) = i Ni µi . = N τ log nQ Zint p = N τ log . N1. Princeton University Physics Department. set xi = λNi and diﬀerentiate with respect to λ. so G(τ. N ) = N µ(τ. Edward J. . nQ Zint N/V − 1 + Nτ . p). . N2 . ∂xi ∂λ i Note that ∂xi /∂λ = Ni and when λ → 1. then xi → Ni . the chemical potential of a single component system depends only on the temperature and pressure. µ is a function only of p and τ . What happens when there is more than one kind of particle in the system? In this case. p.) . p. ∂G ∂xi = G(τ.

int is lower than zero by ǫb . ǫB. This extra energy will factor out and we will have ZC. This is the fact that all energies in the system must be measured from the same zero point. Since the logarithm of the partition function occurs in the chemical potential.Q Zi. Edward J.int . Starting from the Helmholtz free energy again. then the reaction of A and B to produce C gives up some binding energy ǫb . Ni τ + pV . i Ni µi . xi = Ni /N = ni /n. −ǫb + ǫC. The derivation of G in the above paragraph hides an important issue in the internal partition functions. The Gibbs free energy is of the form.int = e+ǫb /τ Z0.C.int Ni τ log Ni τ + pV .1 .C.Q Zi.int .. Ni τ log τ ni. the internal energy states of the molecules are A: B: C: 0.int i = i (Ni /N )(N/V ) Ni τ log − ni. xi p = pi . where Z0.2 . ǫB. Also.int xi p . When we compute the internal partition function for molecule C we need to include −ǫb as part of the energy in every term in the sum. ǫB.1 . and the intensive parameters xi . 0.3 . In particular. ǫA. we have G= i Ni τ log ni −1 ni.int is the usual partition function with the ground state at 0. . . Princeton University Physics Department.2 . so the ground state energy for ZC. the partial pressure of molecules of type i. .. τ ni. the situation is slightly more complicated. If C is stable. ǫA. In other words. then we might have a reaction like A+B↔C. − ǫb . Groth . ǫA. .int + pV .int where xi is the fractional concentration of molecules of type i. = i Ni τ log Ni /V − ni.Q Zi. Zi. −ǫb + ǫC..Q Zi.. The quantum concentrations are given a molecular subscript since they depend on the masses of the molecules as well as the temperature.3 .Q Zi.Physics 301 8-Nov-2004 20-3 If we have a multicomponent ideal gas.. .1 . the net eﬀect is to add −ǫb to µC Copyright c 2004. . temperature.3 . −ǫb + ǫC.2 . and the chemical potentials depend on pressure. if we have molecules that can undergo chemical reactions (which is where we’re headed).. i = i = i xi p − N τ + pV .

The message is that energies must be measured on a common scale. We will sometimes assume the internal partition functions are calculated with the internal ground state energy set to 0 and explicitly add any binding energies to the chemical potentials. A3 = H2 O . This must be an extremum which means that there is no change in G if the reaction or the inverse reaction occurs (dR = ±1). Then the change in the Gibbs free energy is dG = i µi dNi = i µi νi dR = i µi νi dR . Princeton University Physics Department. Other times. Edward J. If the reaction occurs. ν2 = 1 . For example. ν1 = 2 . This becomes 2H2 + O2 − 2H2 O = 0 . the formation of water from hydrogen and oxygen is typically written. we can write any chemical reaction as ν1 A1 + ν2 A2 + ν3 A3 + · · · + νl Al = 0 . so µi νi = 0 . where dR is the number of times the reaction occurs in the direction that makes the left hand side. we also have the constraint imposed by the reaction. we will assume that all binding energies are incorporated into the internal partition functions! Chemical Equilibrium Suppose we have a chemical reaction which takes place at constant temperature and pressure. ν3 = −2 . A2 = O2 .Physics 301 8-Nov-2004 20-4 and −NC ǫb to the Gibbs free energy. Groth . Then. But in addition to this condition. we know that the Gibbs free energy is a minimum. In particular. dNi = νi dR . with A1 = H2 . 2H2 + O2 → 2H2 O . where Ai stands for a particular compound and νi denotes the relative amount of that compound which occurs in the reaction. i Copyright c 2004. the change in numbers of molecules is described by νi .

Assuming there are not multiple minima in G. Note 4: if there is more than one reaction. If we also have 2N ↔ N2 . if the reaction is catalyzed by another molecule via an intermediate step. Note 3: the νi are ﬁxed. then we also have the additional relations among the chemical potentials (at equilibrium). the above holds. Note that there are ﬁve kinds of molecules. and there are four conditions of chemical equilibrium. the reaction proceeds to equilibrium at which point the system has some pressure. µN + µO = µNO . the equilibrium condition provides one equation for the three unknown chemical potentials. It is the chemical potentials which adjust to satisfy the equilibrium condition. The equilibrium condition. in the water reaction above. the four Copyright c 2004.Physics 301 when a reaction occurs at constant temperature and pressure. the pressure and temperature. there may be several equations similar to µi νi = 0 which must be satisﬁed at equilibrium. can be written µN2 + µO2 = 2µNO . the reaction proceeds until i µi νi = 0 at which point the system has some particular volume determined by the total amount of reactants. There are six conditions for ﬁve chemical potentials. Edward J. consider i N2 + O2 ↔ 2NO . Now imagine that one had started with this pressure. If we start with the temperature ﬁxed and some particular volume. Other constraints may need to be satisﬁed as well. 8-Nov-2004 20-5 Note 1: the expression we’ve just derived also holds if the temperature and volume are held ﬁxed. 2µO = µO2 . Groth . N + O ↔ NO . In other words. There must be a total amount of nitrogen and a total amount of oxygen (two conditions). Two other conditions might be the total amount of hydrogen and the total amount of oxygen. the reaction rate might diﬀer with and without the catalyst. If there are several reactions going on but the net reaction can be reduced to a single reaction. 2µN = µN2 . and allowed the reaction to proceed at constant pressure. we just substitute the appropriate chemical potentials for the chemicals in the reaction equation. For example. i µi νi . Princeton University Physics Department. For example. but the equilibrium will be the same. 2O ↔ O2 . the reaction will wind up at the same place and have the same volume! Note 2: the expression we’ve just derived holds for a single chemical reaction. However. As an example. This is most easily seen by noting that when the temperature and pressure are held ﬁxed.

(This. and ci depends on the characteristics of molecule i through its mass in the quantum concentration and its internal states in the partition function. we’ll consider the case that all molecules participating in a reaction can be treated as an ideal classical gas. the chemical potentials depend on the concentrations of the molecules. Among other things. i i = i cνi i . For complicated situations it is Copyright c 2004. Note that at a given temperature. but otherwise ci depends only on the temperature. The equilibrium condition can be written νi log ni = i i ni = τ log ni − τ log ni.Q Zi.Q Zi. For example. ni. of course. Princeton University Physics Department. but also for low concentration solutes. i i log nνi i i = = log log i n νi i n νi i i cνi .int νi log ci .) Then µi = τ log where ci = ni. i i The last line is known as the law of mass action. we’re assuming that any binding energies are included in the internal partition function. In terms of molecular properties. it’s given by K(τ ) = i cνi = i i (ni. Note that in this expression. the chemical potentials adjust to satisfy the equilibrium condition. To bring this out.Q Zi. The quantity K(τ ) is known as the equilibrium constant and is not a constant but depends on temperature. The Law of Mass Action We’ve seen that for chemical equilibrium.int ) νi . works for low density gases. Groth . measurement of all the concentrations allows one to determine the equilibrium constant at that temperature. Edward J. the last one can be derived from the previous three.Physics 301 8-Nov-2004 20-6 equilibrium conditions are not all independent. nνi = K(τ ) .Q Zi.int . log cνi . i µi νi = 0.int = τ log ni − τ log ci .

Groth . the concentrations must be equal. Copyright c 2004. The notation [whatever] denotes the concentration of whatever. However. the pH goes down.Physics 301 8-Nov-2004 20-7 easier to determine the constant experimentally than to calculate it from the molecular properties! Application: pH Water can undergo the reaction H2 O ↔ H+ + OH− . If an acid. so [H+ ] = [OH− ] = 10−7 mol l−1 . The equilibrium concentrations satisfy [H+ ][OH− ] = 10−14 mol2 l−2 . adding a base. Note that in pure water. Similarly. but the product stays constant. Princeton University Physics Department. the concentration of water in water is about 56 mol/l and it doesn’t change very much. the increased availability of H+ shifts the equilibrium to increase [H+ ] and decrease [OH− ]. such as Na OH. The pH of a solution is deﬁned as pH = − log10 [H+ ] . We need to divide by the concentration of H2 O to place it in the proper form. so we can treat it as a constant. When H+ goes up. increases the concentration of [OH− ] and increases the pH. such as H Cl is dissolved in water. This is almost in the form of the law of mass action. In water at room temperature a very small fraction of the water molecules are dissociated into hydrogen and hydroxyl ions. and then the law of mass action takes the form of the above equation. The pH of pure water is 7. Edward J.

In this case. and is the product of K(τ ) and the appropriate power of the temperature. Princeton University Physics Department. where the equilibrium constant is the product of K(τ ) and the appropriate power of τ /p. we have pνi = i i i τ νi K(τ ) = τ νi K(τ ) = Kp (τ ) . Edward J. depends only on temperature. Copyright c 2004.Physics 301 Other Ways of Expressing the Law of Mass Action 8-Nov-2004 20-8 We have written the law of mass action in terms of the particle concentrations. We can also write the law of mass action in terms of the fractional particle concentrations. The partial pressure of component i is pi = Ni τ /V . p) . ni = Ni /V . where the equilibrium constant is now called Kp (τ ). xi = Ni /N = pi /p. If we substitute these forms in the law of mass action and rearrange slightly. Groth . introduced earlier. the equilibrium constant is a function of pressure as well as temperature. or ni = pi /τ . We simply divide each partial pressure above by p (or each concentration by the overall concentration n = N/V and we have xν i i i = τ p νi K(τ ) = Kx (τ.

Ni Copyright c 2004. Qp = ∆H. Princeton University Physics Department. p.int . the change in particle number is ∆Ni = −νi and the change in G is ∆G = − i µi νi . Groth .Ni ∂ ∂τ i µi νi τ . 10-Nov-2004 21-1 which has come to equilibrium at some temperature τ . If Qp > 0. The change in H is Qp = ∆H = −τ 2 The chemical potential is µi = τ log xi p/τ ni. ∂ ∂τ ∆G τ = +τ 2 p.Q Zi. Then the system is no longer in equilibrium and the reaction (in the forward or reverse direction) will have to occur in order to restore equilibrium. and σ=− so H =G−τ ∂G ∂τ ∂G ∂τ . heat is released and the reaction is called exothermic. is the heat that must be supplied to the system if the reaction goes from left to right. For a reaction at constant pressure.Ni What we actually want to do is to change the temperature slightly. Qp . If this is 0.Physics 301 The Direction of a Reaction Suppose we have a reaction such as A+B↔C. p.Ni ∂ ∂τ G τ . p. heat is absorbed and the reaction is called endothermic.Ni = −τ 2 p. Does the equilibrium shift to the left (more A and B) or to the right (more C)? The heat of reaction at constant pressure. If Qp < 0. We have H = G + τσ . When the reaction occurs from left to right. Now we raise the temperature. the heat is the change in the enthalpy of the system. we have the equilibrium condition (but we’ve taken it out of equilibrium by changing the temperature). Edward J.

Q Zi. Groth .Q Zi. In any case. i ν ∂ log ∂τ (τ ni. We’ve just shown that increasing the temperature drives an endothermic reaction to the right. ∂ log Kp (τ ) . Qp = τ 2 ∂ ∂τ (νi log (xi p) − νi log (τ ni. so we wind up with our equilibrium constants being inverses of each other and opposite signs in the van’t Hoﬀ equation.int )) .int ) i νi . our law of mass action has the concentrations of the left hand side reactants in the numerator and the right hand side reactants in the denominator.int )) .int ) i ) . Princeton University Physics Department. Copyright c 2004.Q Zi. i 10-Nov-2004 21-2 ∂ = −τ 2 ∂τ = −τ 2 = −τ 2 = −τ 2 ∂ ∂τ (νi log (τ ni. Mandl (who provides the basis for this section) assumes the opposite. Edward J. A note on signs: I’ve assumed that the νi are positive on the left hand side of the reaction and negative for the right hand side of the reaction. ∂τ We’ve related the heat of reaction to the equilibrium constant! This is called van’t Hoﬀ’s equation. then our equilibrium constant decreases with temperature. i (log (τ ni.Physics 301 We substitute into our expression for Qp and obtain. We see that if Qp is positive (we have to add heat to go from left to right. It will drive an exothermic reaction to the left. So an increase in the equilibrium constant means the reaction goes to the left and a decrease means the reaction goes to the right. an endothermic reaction).Q Zi. Rule of thumb: increasing the temperature causes the reaction to go towards whatever direction it can absorb energy. This means increasing the temperature moves the reaction to the right.

int )(ne. and as the above reaction is written. Edward J. Ionizing hydrogen from its ground state requires an energy of 13.int ) = . In any case. When all is said and done. the electron and proton each have two spin states. we have [p+ ][e− ] =4 [H] me τ 2π¯ 2 h 3/2 e−I/τ 1 ZH. p+ + e− ↔ H . The quantum concentration of the electron is 3/2 me τ .int . If we are considering low density gases. This is complicated.Q Ze. we can treat them as classical ideal gases and apply our law of mass action: [p+ ][e− ] (np. some of the forms we will derive below) is called the Saha equation. since each has spin 1/2. Copyright c 2004.6 eV.Q ZH. First of all.Q Zp. the orbital angular momentum is zero and the spins can be parallel to give a total angular momentum of 1¯ with 3 states or h anti-parallel to give a total angular momentum of 0 with 1 state. as we’ve taken explicit account of the binding energy I = 13. Some of the factors in the equilibrium constant are easy to calculate and others are hard to calculate! Let’s do the easy ones. so the quantum concentrations of the proton and the hydrogen are almost the same and we can cancel them out. so whatever else is going on there is a factor of four due to the spins. This leaves us with the internal partition function of the hydrogen atom.Q = 2π¯ 2 h The internal partition functions for the electron and proton are both just 2. The parallel states are slightly higher in energy than the anti-parallel state.int exp(I/τ ) where the partition function for the hydrogen atom is to be computed with the ground state at the zero of energy. the energy diﬀerence between these states is small enough to be ignored in computing the internal partition function for the purposes of the Saha equation. Groth . Transitions between these states are called hyperﬁne transitions and result in the 21 cm line which is radiated and absorbed by neutral hydrogen throughout our galaxy and others. Princeton University Physics Department. Aside: in fact the spins can combine with the orbital angular momentum to give a total angular momentum. In the ground state. the mass of a proton and the mass of a hydrogen atom are almost the same. it’s exothermic from left to right. ne. Consider the ionization of atomic hydrogen. chapter 9.Physics 301 Application: the Saha Equation 10-Nov-2004 21-3 This section is related to K&K. problem 2.6 eV. [H] nH. This (or more properly. First of all.

) Similarly. and Ii+1.i is the diﬀerence in binding energy between the two ions. Zi+1. each ion will have some internal structure and energy levels. Sometimes the multiplicity is called the degeneracy or the statistical weight. Princeton University Physics Department.int Copyright c 2004.int exp(Ii+1.j = . We let ǫi+1. gi+1. then we might as well approximate the partition function as 4.k and gi. The fraction of ions i + 1 which are in state j is given by a Boltzmann factor. If the temperature is small compared to the binding energy of hydrogen (which means it’s small compared to the diﬀerence between the ﬁrst excited state and the ground state). ni ni. The Saha equation applies to gases in space or stars as well as donor atoms in semi-conductors (modiﬁed for the appropriate physical characteristics of the atom and the medium).j /τ ni+1.j e−ǫi+1. [p+ ][e− ] ≈ [H] me τ 2π¯ 2 h 3/2 e−I/τ . This gives. [p+ ] = [e− ] and [e− ] ≈ [H] me τ 2π¯ 2 h 3/4 e−I/2τ .int and Zi.j be the energy (relative to 0 for the ion ground state) of the j th state of ion i + 1. In fact.Q are the quantum concentrations of the two ions which are essentially the same.Q Zi+1. That is. If we have only hydrogen and ionized hydrogen.Physics 301 10-Nov-2004 21-4 where the factor of four accounts for the two spin states of the proton and the two spin states of the electron (there is a factor of four in the hydrogen partition function as well). ni+1 Zi+1. Groth .Q Zi.Q and ni.int ) ni+1 [e− ] = .int are the internal partition functions of the two ions. ni+1. heavier elements whose outer electrons are loosely bound).i /τ ) where ni+1 and ni are the concentrations of the two ions.k are the energy and multiplicity of the k th state of ion i. Now. (ni+1. and ask about the ionization equilibrium between the ions that have been ionized i times and those that have been ionized i + 1 times. Edward J. Ii+1. If there is another source of electrons (for example. Some points to note: the fact that the exponential has −I/2τ indicates that this is a mass action eﬀect.int )(ne.j . Let’s consider an atom which has several electrons. we can do a little more with the Saha equation.Q Ze. (If there is more than one state at a given energy we say that energy is degenerate and the multiplicity is the number of such states. not a Boltzmann factor eﬀect. This state has multiplicity gi+1. ǫi.i is the energy required to remove an electron from ion i and produce ion i + 1. so we cancel them out. the reaction would shift to favor more hydrogen and fewer protons.

Such transitions “broke” the symmetry of the fundamental forces causing there to be diﬀerent couplings for the strong.0 me τ 2π¯ 2 h 3/2 e−I/τ . even in the small domains. There are only two ionization states.j me τ = e−(Ii+1. Groth .Physics 301 10-Nov-2004 21-5 If we substitute this expression into the Saha equation. 2 ni. For example. We are all familiar with melting ice and boiling water. When iron is cooled below the Curie point. The Curie point of iron is Tc = 1043 K. disappears above the Curie temperature.0 = 4 and energy ǫ0. and no excited states. The transition between the normal and superﬂuid states of 4 He is a phase transition as are the transitions between normal and superconducting states in superconductors. as the universe cooled from its extremely hot “initial” state. Some solids. A typical chunk of iron has no net magnetization because it magnetizes in small domains with the direction of the magnetic ﬁeld oriented at random.j − ǫi. we get 3/2 ni+1. We can apply the above expression to hydrogen (again!). The ionized state is just a proton which has a multiplicity of 2. change their crystal structure. Of course. The latent heat released in such a transition might have driven the universe into a state of very rapid expansion (inﬂation). when heated through certain temperatures. which is essentially the same equation we had before except that now it includes only hydrogen atoms in the ground state and it is “exact. Copyright c 2004.k gi.k 2π¯ h This form of the Saha equation connects the concentration of ions in various energy levels to the electron concentration and the temperature.k )/τ . You’ve probably heard about the “symmetry breaking phase transitions” that might have occurred in the very early universe. and gravitational force. it spontaneously magnetizes. so ni.i + ǫi+1. now we have a relation connecting concentrations of states of a given energy level rather than concentrations of ions of a given ionization.k is the concentration of hydrogen atoms in the ground state (which has multiplicity g0. Note that we managed to get rid of the internal partition functions. electromagnetic. sulfur can exist in monoclinic or rhombic forms. and also substitute the quantum concentration of the electrons and the internal partition function of the electrons (2). So [p+ ][e− ] = n0. But other kinds of phase transitions occur as well.j [e− ] 2gi+1. weak. Princeton University Physics Department. We let i = 0 and k = 0.” Phase Transitions Phase transitions occur throughout physics. The magnetization.0 = 0. Edward J.

Groth . all liquid. we are essentially moving down a vertical line in the pτ diagram. but it doesn’t have any resolution at the triple point. so a single direction is picked out and the rotational symmetry is broken. etc. and then see what we have. from a to b we are stuck at the line in the pτ diagram that divides the liquid from the vapor region. the atomic magnets (spins) are oriented at random (by thermal ﬂuctuations). Note that the ﬁrst ﬁgure (which we’ll talk about some more in a minute) is something like a map: it says here we have vapor. This is not an exhaustive list of phase transitions! Even so. For an ideal gas. So any direction is the same as any other direction and there is rotational symmetry. with liquid water. or all vapor (steam). wait for equilibrium to be established. or liquid and vapor. there are several kinds of ice which we’re ignoring!) K&K give a diagram. For some temperatures and pressures we will ﬁnd mixtures of solid and vapor. We place pure water inside a container which keeps the amount of water constant and doesn’t allow any other kinds of molecules to enter. If we move along this isotherm from left to right. we have pure liquid on the branch to the left of point a. Princeton University Physics Department. We dial in a temperature and a pressure. Phase Diagrams Suppose we do some very simple experiments.Physics 301 10-Nov-2004 21-6 The spontaneous magnetization of iron as it’s cooled below the Curie temperature is an example of a symmetry breaking transition. Edward J. The container is in contact with adjustable temperature and pressure reservoirs. So the Copyright c 2004. (Also. we will not have time to discuss all these kinds of phase transitions. For most pressures and temperatures we will ﬁnd that the water is all solid (ice). For the isotherm as shown. I didn’t put any numbers on the axes—which is why it’s schematic. The ﬁgure shows a schematic plot of a phase diagram for water. or solid and liquid. we would have a hyperbola. and to the right of b we are moving down in the vapor region. Below the Curie point (and within a single domain) all the atomic magnets are lined up. To the left of point a we are moving to lower pressures. We will start with something “simple” like the liquid to gas transition. there we have solid. Above the Curie point. pure vapor to the right of point b and along the segment from a to b we have a mixture of liquid and vapor. The second ﬁgure is a schematic of a pV diagram showing an isotherm.

where the subscripts l and v refer to the liquid and vapor and we’ve made use of the fact that for a single component substance the chemical potential can be written as a function of p and τ only. Princeton University Physics Department. at each location in the pτ diagram. and what adjusts to match the volume is the relative amounts of liquid and vapor. τ ) = µv (p. τ ) . which is called the sublimation curve. τ ). At this point. then we minimize G by setting Nl = N and Nv = 0 where N is the total number of water molecules. the Gibbs free energy is G(p. τ. which is the melting curve. τ ) = µl (p. First of all. if µl (p. what we’ve just shown is that where liquid and vapor coexist in equilibrium. Ignoring for the moment the fact that the water can be a solid. τ ) = µv (p. τ ) . so we can have a mixture with the exact amounts of liquid and vapor determined by other constraints (such as the volume to be occupied). τ ) . τ ). It’s called the vapor pressure curve. This is a relation between p and τ and it describes a curve on the pτ diagram. which is exactly the same condition we would have come up with had we considered the “reaction” H2 Oliquid ↔ H2 Ovapor . Now. Nl .Physics 301 10-Nov-2004 21-7 entire transition from all liquid to all vapor which is a to b in the pV diagram happens in a single point in the pτ diagram. τ ) = µv (p. we can’t change the free energy by changing the amount of vapor and liquid. if µl (p. τ ) . Edward J. τ ) < µl (p. So. the water has a ﬁxed temperature and pressure. we must have µl (p. If we have all three chemical potentials equal simultaneously. Copyright c 2004. τ ) < µv (p. we deduce that solid and vapor coexist along the curve deﬁned by µs (p. the system is entirely liquid. τ ) = µv (p. τ ). and solid and liquid coexist along the curve µs (p. τ ) = µl (p. τ ) . With similar arguments. In other words. we minimize the free energy by making the system entirely vapor. There are several ways we might minimize G. Nv ) = Nl µl (p. µs (p. Groth . The equilibrium condition is that the Gibbs free energy is minimized. If µv (p. we ﬁx the temperature and pressure and let the system come to equilibrium. Finally. τ ) + Nv µv (p.

At this point. etc. This deﬁnes a surface. liquid. For example. The critical point for water occurs at Tc = 647. Tt = 273.1 atm . Princeton University Physics Department. As one goes up in temperature. and it has three triple points. Where two surfaces intersect. Of course. we have pure vapor.58 mm Hg . or solid region (supercooled).30 K . pc = 219. you get suﬃciently violent motions that binding to neighboring molecules (a liquid) becomes a negligible contribution to the energy. In fact we have several surfaces. If a substance has more than three phases. while µ(p. It is possible to have liquid in the vapor region (superheated). τ ) is plotted as height above the plane. pt = 4. Where µv is the lowest. Copyright c 2004. etc. Actually. and vapor all coexist is called the triple point. one can’t tell the diﬀerence between the liquid phase and the vapor phase. We’ll say more about this later. Whether this happens rapidly or slowly depends on the details of the particular situation. Another way to think of the phase diagram and the coexistence curves is to imagine a 3D plot. This unique (for each substance) point where solid. the heat of vaporization decreases. but these situations are unstable and the system will try to get to equilibrium. and µv . but for now. this is now used to deﬁne the Kelvin scale. consider that as you go up in temperature. one for µs . For water. The vapor pressure curve eventually ends at a point called the critical point.. At the critical point it is zero. Pressure and temperature are measured in a horizontal plane. Edward J. µl . the phase diagram corresponds to equilibrium. the two crystalline phases of sulfur give it four phases. We take the overall surface to be the lowest of all the surfaces— remember we’re trying to minimize G. it can have more than one triple point. Groth .16 K .Physics 301 10-Nov-2004 21-8 we have two conditions on p and τ and this deﬁnes a point. we have a coexistence curve.

p.τ The situation is sketched in the left pair of plots in the ﬁgure which shows the change in entropy resulting from the phase transition. and ∆σ = L/τ . Since there is a discontinuous change in the entropy in a ﬁrst order transition. This means that the entropy and volume have step discontinuities. This is illustrated in the righthand pair of plots. Groth . So things like the entropy and volume are continuous. p.Physics 301 First Order and Second Order Phase Transitions 12-Nov-2004 22-1 In the phase diagram we’ve been discussing. so σ=− ∂G ∂τ ∂G ∂p ∂G ∂N . Recall. dG = −σ dτ + V dp + µ dN . Such a transition is called a ﬁrst order transition—the ﬁrst derivatives of G have discontinuities. but its slope changes discontinuously. Edward J. but their slopes change suddenly. τ. G is continuous. Princeton University Physics Department.N V =+ . Second order transitions have discontinuities in the second derivatives. This is true whether we cross the curve by changing temperature or by changing pressure. as we cross a coexistence curve.N µ=+ . where L is the heat required for the system to go from completely liquid to completely vapor at temperature τ . heat must be added. This is called the heat of vaporization (or sometimes the latent Copyright c 2004.

Princeton University Physics Department. The other partial derivative in the numerator gives the entropy per particle in the liquid phase. Nv ∂τ p. the change in both chemical potentials must be the same. The vapor pressure curve is given by µl (p. what are all these partial derivatives? − ∂µv ∂τ =− p p τ + − ∂µl ∂τ ∂µl ∂p .Nv 1 σv =+ σv = = sv . there are heats of melting (fusion) and sublimation. Nv Nv where sv is the entropy per particle in the vapor phase. the chemical potentials change as well. In a ﬁrst order transition. Edward J. Similarly. respectively. sl . p. As we move along the curve. = dτ vv − vl This is called the Clausius-Clapeyron equation. like the liquid–vapor transition in water and see if we can say something about the functional form of the coexistence curve. We have dµl (p. If we remain on the curve. p − dp = dτ + Now. while the partials in the denominator give the volumes per particle in the vapor and liquid phases. ∂µl ∂µv dτ = dp + ∂τ p ∂p τ ∂µl ∂p dp = − τ ∂µl ∂p + ∂µv ∂p dp + τ ∂µv ∂τ ∂µl ∂τ p τ dτ . we have dp sv − sl . the heat capacities dQ/dτ are δ-functions! The Clausius-Clapeyron Equation Now we are going to return to a ﬁrst order transition. τ ) . vv and vl . p dp − τ ∂µv ∂τ ∂µv ∂τ ∂µv ∂p dτ + p dτ . Altogether. ∂Gv /Nv ∂τ . τ ) = dµv (p. τ ) = µv (p.Nv =− ∂Gv 1 . Groth . τ ) .Physics 301 12-Nov-2004 22-2 heat of vaporization). Copyright c 2004. Let’s move a short distance along the curve in which τ changes by dτ and p changes by dp.

We start with what happens at 1 atm and 0◦ C = 273. First of all. dτ τ ∆v where ℓ is the speciﬁc latent heat and ∆v is the change in speciﬁc volume. That is. the melting curve would have dp sl − ss = . one needs about 10 meters of ice to generate a pressure of one atmosphere. dT The slope is negative! This accounts for the fact that the melting curve of water leaves the triple point headed up and slightly to the left. dτ vl − vs A ﬁnal comment is that the speciﬁc entropies and volumes are to be evaluated at the temperature and pressure at the point on the coexistence curve for which the slope is desired. For example. Since we have a ratio.Physics 301 12-Nov-2004 22-3 Some comments on this equation are in order. Edward J.1 mm (very sharp) skates would produce about a 1 degree Copyright c 2004. In words. A similar equation applies to each coexistence curve. For example. A 50 kg skater on a pair of 20 cm by 0. but the numbers don’t work out. As a glacier meets up with an obstruction.09070 cm3 g−1 . Most materials (which expand on melting!) have a melting curve which leaves the triple point headed up and slightly to the right. the pressure at the point of contact with the obstruction increases until the ice melts and the liquid water can ﬂow around the obstruction and refreeze on the other side. We just need to put in the right quantities. Remember. dp/dτ is the slope of the vapor pressure curve (it has nothing directly to do with the equation of state of the substance). ice skates can melt ice and the liquid water helps lubricate the skate.35 × 109 ergs g−1 . a large positive slope instead of a large negative slope. Secondly. or the entropy per gram and volume per gram. the change in entropy can be immediately related to the latent heat. The speciﬁc latent heat of fusion is 3. The Clausius-Clapeyron equation is often written in other forms. the equation says the slope of the vapor pressure curve is the ratio of the change in speciﬁc entropy to the change in speciﬁc volume between the vapor and liquid phases. Groth . This unusual property of water is often said to be the reason why we can have ﬁgure skating and ice hockey and why glaciers can ﬂow. the equation remains true if we use the entropy per mole and volume per mole. we would need a 13 km thick glacier. In particular. vl = 1.15 K.35 × 108 dyne cm−2 K−1 = −134 atm K−1 . dp ℓ = .00013 cm3 g−1 . We can apply this to the melting of ice and the change in melting temperature with pressure. The speciﬁc volumes of ice and liquid water are vs = 1. This sounds good. water expands as it freezes! The result is dp = −1. Similarly. we have the entropy per particle and the volume per particle. Princeton University Physics Department. etc. to get a 10 degree change in melting temperature.

we need the speciﬁc volume. Note that if we evaluate the slope at the normal boiling point with this expression. Using the slope we just calculated. the pressure is about 60% of sea level pressure. The latent heat of vaporization is 2.035 atm K−1 . When we deal with the vapor pressure curve.15 K.043 cm3 g−1 . we can usually neglect the volume of the liquid compared to the gas (as we’ve just seen). log p = − RT Copyright c 2004. we can integrate this expression. Recall. dp = 3. p R T2 If we now assume that the ℓ does not depend on temperature or pressure. dT On Mauna Kea in Hawaii at an altitude of about 14.Physics 301 12-Nov-2004 22-4 change in melting temperature. then we can write v = RT /pM . where R is the gas constant (per mole) and M is the molecular weight (mass per mole).” Now let’s look at what happens at the normal boiling point of water and the liquid– vapor transition. We can rewrite the approximate form of the Clausius-Clapeyron equation as dp M ℓ dT = . dT within 3% of what we had with the exact expression. dT T (RT /pM ) RT 2 This is yet another form of the Clausius-Clapeyron equation. we get dp = 3. it is probable that surface eﬀects are more important. Also. Also. This occurs at 1 atm and 100◦ C = 373. a water molecule on the surface forms bonds with fewer neighbors than a molecule in the interior of the solid. so if we have the latent heat per unit mass. the pressure has decreased by 0. Then we have ℓ Mℓ dp = =p .000 ft.54 × 104 dyne cm−2 K−1 = 0. we ﬁnd that the boiling point of water decreases by 11◦ C to 89◦ C.257 × 1010 ergs g−1 and the speciﬁc volumes of the liquid and the vapor are vl = 1. the ideal gas law may not apply all that well!). we haven’t made any approximations in dealing with the ClausiusClapeyron equation.036 atm K−1 . That is. vv = 1673 cm3 g−1 .4 atm. Groth This gives . Although this eﬀect may play a role. For example. Mℓ + constant . it may be attracted to the material in contact with the surface making it easier to “melt. Edward J. Princeton University Physics Department.62 × 104 dyne cm−2 K−1 = 0. Up to this point. if the substance is making the transition between liquid and gas. we can use the ideal gas law to get volume in terms of the pressure and temperature (of course.

Princeton University Physics Department. it’s a good approximation to assume it is for a small range of the curve and for a small range.Physics 301 or 12-Nov-2004 22-5 p = p0 e−M ℓ/RT .3 shows that this is not all that bad of an approximation. Part of the reason the plot in K&K doesn’t look all that bad is that the scale is very coarse and covers 8 orders of magnitude in pressure. but no closer. as changing from one small range to the next. This equation of state can be obtained by starting with the Helmholtz free energy of an ideal gas and making corrections to account for these eﬀects. The attractive force gets weaker and goes to zero as the separation is increased. Groth . Of course.) The van der Waals Equation of State If we want to have an atomic model for a liquid–vapor transition. we don’t need to know the details of this curve.) Fortunately. The van der Waals equation of state is p+a N2 V2 (V − bN ) = N τ . K&K ﬁgure 10. the pressure is well approximated by an exponential of 1/τ . This is exactly what this correction provides.7 shows a schematic of the potential energy curve of the interaction between two molecules. ﬁgure 10. then you would expect the pressure to diverge if the density reaches 1 molecule per volume b. Copyright c 2004. where a and b are constants that depend on the gas molecules. but if each molecule has a volume b. b is related to the hard sphere repulsion and a is related to the longer range attraction. Even though the latent heat isn’t constant. (One can think of the integration constant. The ideal gas free energy is F = −N τ (log(nQ /n) + 1) . we will need to model the gas as something more than non-interacting point particles. We can approximate this force by thinking of the molecules as “hard spheres” which can get as close as twice their radii. so the concentration should be replaced by N/(V −bN ). (Remember the force is the negative of the slope of this curve. a strong repulsive force arises. If each molecule occupies a volume b then the eﬀective volume available is V − bN . What this says is that a semi-log plot of the vapor pressure against T −1 should be a straight line. p0 . If the molecules get too close. Of course. A reasonably successful approach models the gas molecules as having an attractive force for separations larger than some distance (roughly the equilibrium separation in the solid). Edward J. we know that the latent heat isn’t constant and it goes to zero at the critical point. K&K. It’s only described to this extent in order to motivate the van der Waals equation of state. this is not entirely legitimate.

where rmin corresponds to the minimum distance set by b and n(r) is the concentration at distance r from the given molecule. a change to it’s energy of −2na. a given molecule has. this double counts the interaction energy since each molecule is counted twice: once while contributing to the mean ﬁeld and once while being acted upon by the mean ﬁeld. V However. The mean ﬁeld approximation ignores these correlations. Suppose φ(r) is the potential energy between two molecules separated by r. We will evaluate this in an approximate way. There are N molecules. on the average.Physics 301 12-Nov-2004 22-6 Since there is an attractive force between the molecules.N Copyright c 2004. This is called the mean ﬁeld approximation. there is a net negative contribution to the energy produced by every pair of molecules. V Our ﬁnal approximate expression for the free energy of a van der Waals gas is F = −N τ log nQ (V − bN ) N2 +1 −a . p=− which can be rearranged to p+a N2 V2 (V − bN ) = N τ . Groth . The potential energy of one molecule due to its interactions with all the other molecules is ∞ u= rmin n(r)φ(r) dV . the molecular positions are correlated. V − bN V τ. Of course. So ∆U = ∆F = −a N2 . That is. We assume that each molecule moves in the average ﬁeld of all the other molecules and does not aﬀect the density of the other molecules. Princeton University Physics Department. N V We diﬀerentiate with respect to the volume to get the pressure. the concentration of molecules around any given molecule will be higher than it is at a randomly chosen point. so the total change in energy due to the attractive part of the van der Waals interaction is ∆U = −2a N2 . ∂F ∂V Nτ N2 = −a 2 . So we need to divide by a factor of two (why we put 2 in to start with!). Edward J. Due to its interactions with all the other molecules. The factor of two is included for computational convenience. since there is an attractive force. So. The simplest thing we can do is to assume n(r) = n = const. which is really just the deﬁnition of a. we have ∞ u=n rmin φ(r) dV = −2na .

but for small τ there are large deviations from the ideal gas equation of state. 3 τc p 3 + pc (V /Vc )2 = This equation is plotted for several values of τ in the ﬁgure. Then Vc = 3bN .Physics 301 12-Nov-2004 22-7 We can put the van der Waals equation of state into dimensionless form if we deﬁne pc = a/27b2 . it approaches the ideal gas equation of state. 1 V − Vc 3 τc = 8a/27b . For large τ . 8τ . We will explore these deviations and see what they have to do with phase transitions next time! Copyright c 2004. Groth . Edward J. Princeton University Physics Department.

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