In the Classroom
Stories to Make Thermodynamics and Related Subjects
More Palatable
Lawrence S. Bartell
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109; lbart@umich.edu
For more than 40 years I taught physical chemistry at
Iowa State University and the University of Michigan. Students
had invariably entered the course having heard horror stories
about how tedious and impossibly difficult thermodynamics
and physical chemistry can be. In fact, our student newspaper,
the Michigan Daily, once published an article on courses offered
by the University of Michigan and singled out physical
chemistry as the most difficult course in the entire university.
Naturally, that presented a real challenge of how to break
the ice. I found that the only way I could keep the students
alert and receptive to ideas in lectures on thermodynamics
and related fields was to tell them stories from time to time.
These stories illustrated aspects of principles, recounted the
personalities of some of the architects of thermodynamics and
related fields, or reviewed steps and missteps in the development
of these fields. Since it turned out that the stories were much
easier for students to remember than simple recitations of
principles and facts, they seemed a good idea. I also posed
several scientific puzzles (1), encouraging students to apply
their imagination about how they could be resolved using
the basic framework we had already established. Sometimes,
I even offered extra credit for correct answers. In student
evaluations of my teaching it was my stories that got the most
favorable mention.
It has now been over seven years since I last taught. But
some of my young colleagues come to me for suggestions
about teaching, and I have told them some of the stories that
illustrated the points they asked about. Several years ago
Roald Hoffmann and Dudley Herschbach lectured at a work-
shop on chemical education at the University of Michigan,
and both stressed the importance of telling stories (or, as
Herschbach put it, “parables”) to the students. All of this
prompted me to try to recall and record the stories I told.
Since most of them are true, however, they aren’t parables. For
what it is worth I offer the stories I remember, indicating
where in a course on thermodynamics and related subjects
they might fit. I also record several of the more interesting
paragraphs written by others that I read to the class.
Thermodynamics
Introduction.—Before launching into the principles of
thermodynamics it is a good idea to read to the students a few
classic passages to increase their appreciation of thermody-
namics as a topic well worth the trouble of studying. Even
though Einstein has been dead for a half-century, all students
still regard him as legendary and his opinions as profound.
The following remarks of Einstein are appropriate (2).
Consequently, these obituary notes can limit themselves
in the main to the communicating of thoughts which
have played a considerable role in my endeavors. … A
theory is the more impressive the greater the simplicity
of its premises, the more different the kinds of things it
JChemEd.chem.wisc.edu • Vol. 78 No. 8 August 2001 • Journal of Chemical Education
relates, and the more extended is its area of applicability.
Therefore, the deep impression which classical thermodynam-
ics made upon me. It is the only physical theory of universal
content concerning which I am convinced that, within the
framework of the applicability of its basic concepts, it will
never be overthrown (for the special attention of those who
are skeptics on principle).
The following is from the Preface to Thermodynamics,
by Lewis and Randall (3).
There are ancient cathedrals which, apart from their con-
secrated purpose, inspire solemnity and awe. Even the
curious visitor speaks of serious things, with hushed voice,
and as each whisper reverberates through the vaulted
nave, the returning echo seems to bear a message of mys-
tery. The labor of generations of architects and artisans
has been forgotten, the scaffolding erected for their toil
has long since been removed, their mistakes erased, or
have become hidden by the dust of centuries. Seeing only
the perfection of the completed whole, we are impressed
as by some superhuman agency. But sometimes we enter
such an edifice that is still partly under construction; then
the sound of hammers, the reek of tobacco, the trivial
jests bandied from workman to workman, enable us to
realize that these great structures are but the result of giv-
ing to ordinary human effort a direction and a purpose.
Science has its cathedrals, built by the efforts of a few
architects and of many workers. In these loftier monuments
of scientific thought a tradition has arisen whereby the
friendly usages of colloquial speech give way to a certain
severity and formality. While this may sometimes promote
precise thinking, it more often results in the intimidation
of the neophyte [aside to students—that’s you]. Therefore
we have attempted, while conducting the reader through
the classic edifice of thermodynamics, into the workshops
where construction is now in progress, to temper the cus-
tomary severity of the science in so far as is compatible
with clarity of thought.
How rare it is to encounter such prose in scientific writing!
First Law of Thermodynamics
Joule’s role in the formulation of the first law is invariably
covered in courses. A personal glimpse of his experience when
he introduced his radically new ideas on the nature of heat adds
a realistic note about the faltering way science tends to advance.
Joule’s classic talk (4).—When Joule was 28, having obtained
new and more precise results demonstrating the conservation
of energy, he forwarded a paper to be presented at the British
Association Meeting at Oxford in August 1847. But the
chairman suggested that, owing to the press of business, Joule
should not read the paper but instead give a verbal description
of his experiments. “This I endeavored to do,” Joule wrote
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 In the Classroom
later, “and, discussion not being invited, the communication
would have passed without comment if a young man had
not arisen in the Section, and by his intelligent observations
created a lively interest in the new theory.” So it was a 23-year-
old kid who made Joule’s paper the sensation of the meeting, as
well it should have been in the first place in view of its historic
importance. This bright young man was William Thomson,
later known as Lord Kelvin. Still, Thomson’s comments
persuaded few of those present, including Faraday, of the
correctness of the revolutionary new views, for they contra-
dicted Carnot and the long-entrenched caloric theory.
After the meeting Joule and Thomson chatted for awhile.
Joule didn’t mention that he was about to get married (why
should he?) and Thomson didn’t mention that he was about
to go to Switzerland on holiday (why should he?). Two weeks
later Thomson, while strolling along the valley of the
Chamonix, saw a young man coming toward him carrying
what looked like a long stick. On closer approach the man
turned out to be Joule, with a long thermometer, and he was
walking to the top of a neighboring waterfall. If his ideas were
right there would be a difference in temperature of the water
between the bottom and the top, due to the dissipation of
kinetic energy at the bottom of the fall. Evidently a honey-
moon could not interrupt Joule’s passion for science—first
things first, after all. This chance meeting cemented a warm
friendship between Joule and Thomson and led to a lifelong
collaboration. What Joule’s waterfall experiment yielded
besides a lasting friendship with a scientific genius is not
known. In any event, it is doubtful that a persuasive result
could have been derived in such a way.
On “established” ideas when insufficient facts are known (5).—
Lord Kelvin was such a brilliant scientist that he became per-
haps the principal authority in matters of the physical universe.
He applied the known laws of heat dissipation to the problem
of the earth’s temperature. From the known temperature increase
with distance below the surface, he deduced that the earth was
not nearly old enough for Darwin’s estimates of the duration of
certain geological processes or for his theory of the origin of
the species to operate. He also estimated the possible active
lifetime of the sun from its energy output, assuming that the
energy source was gravitational infall. The result was more or
less consistent with his conclusions about the age of the earth.
Late in Kelvin’s life radiochemists confirmed the antiquity
of the earth proposed previously by geologists. Kelvin remained
adamant that while the earth might perhaps be 20 million
years old and just possibly an order of magnitude older, it
could not possibly be billions of years old. What he had not
reckoned with, of course, was the steady evolution of heat
from the radioactive elements deep within the earth or the
nuclear reactions powering the sun. Kelvin also disputed
Maxwell’s theory of the electromagnetic nature of light, and
proclaimed that heavier-than-air aircraft were impossible. This
is not to disparage his genius and his enormous accomplish-
ments, or even his genuine modesty. Even such giants can
err, and that, itself, is a lesson worth learning.
Conservation of Matter and Energy
Earth older than the Universe?—When I was a university
student there was a strange paradox. According to radiochem-
ists in collaboration with geologists, the world was about 5
billion years old. But astrophysicists (Hubble et al.) found from
1060 Journal of Chemical Education • Vol. 78 No. 8 August 2001 • JChemEd.chem.wisc.edu
the rate at which the universe was expanding that it could
not have been expanding for more than about two billion
years. In other words, the big bang believed to produce the
universe occurred after the earth was born—the earth was
older that the universe in which it sat, if chemists were to be
believed! Many physicists, of course, were complacent about
this discrepancy because, after all, what is the opinion of a
chemist or geologist compared with that of a physicist?
But some physicists did worry, and that is the point of
this story. We all now take for granted the conservation of
energy and mass. But extraordinary facts call for extraordinary
ideas! The distinguished physicists Bondi, Gold, and Hoyle
proposed a steady-state universe that would look to astronomers
just like Hubble’s expanding universe but, in the steady-state
universe, matter would be generated spontaneously as the
universe expanded (6 ). In that way the expanding universe
could go on forever, always looking much the same, and the
earth could, indeed, be five billion years old. Later, astronomers
discovered that the Cepheid variable stars they used to judge
distances had been miscalibrated and the universe was actually
several times older than the earth. Moreover, other evidence
(microwave radiation, cosmic abundances of the elements,
etc.) is generally considered to confirm the big bang theory
and the antiquity of the universe. But the moral of the story
is that the conservation of mass was seriously challenged by
competent scientists even during the lifetime of scientists alive
today. Of course, the big bang itself is the quintessential
example of matter appearing out of nothingness.
Is conservation of energy only statistical?—Additional chal-
lenges to conservation were encountered in β emission by
radioactive atoms. It happens that some of a nuclide’s β-rays
are much more energetic than others even though all of the
nuclei are believed to be identical, before decay. To account for
this observation the prominent physicists Bohr, Kramers, and
Slater wrote a paper suggesting that energy is conserved, not
in individual events on the atomic scale but only statistically,
on the average (7). To Wolfgang Pauli this solution to the β
problem was so ugly that he postulated the emission of an-
other particle, later named the neutrino, which carried off
enough energy in each decay to balance the energy emitted
by the β-ray (8). It was supposed that the nearly massless,
uncharged neutrino was undetectable, which suggested to
many that it was pure fiction. Even Pauli felt a bit ashamed
at the time to postulate a solution that could not be tested.
But as everyone now knows, the neutrino has been detected
and several neutrino observatories exist around the world. So
it turns out that the laws of conservation of mass and energy
are more robust than many feared, even in comparatively
recent history.
Is mass conserved when an atom bomb explodes?—Yes!
See ref 1.
Can perpetual motion machines be built?—Backyard in-
ventors even today keep coming up with machines that they
claim produce more energy than it takes to run them. Several
years ago a couple of Ann Arbor self-educated inventors
announced such an invention and the Ann Arbor paper, to its
discredit, gave the inventors a long, uncritical feature article.
The U.S. Patent Office has an official policy of not
accepting for examination any applications for perpetual
motion machines. Neither will the National Bureau of Standards
(now called NIST) waste its time on such claims. Several years

ago, however, congressmen (who are considerably more at
home with common law than with the first law) forced the
Bureau of Standards to reverse its policy (9). A Mississippi
inventor, a backwoods high-school dropout with no formal
scientific training, claimed he had the solution to America’s
energy crisis. He had invented a machine that ran on elec-
tricity but, in the process, produced far more energy than it
consumed. He applied for a patent, was turned down, and sued
the U.S. Patent and Trademark Office. He was uncommonly
charismatic and persuasive, an appealing character that TV
news and talk shows could not resist featuring. He convinced
lawyers and congressmen that such a useful creation of Ameri-
can ingenuity should be rewarded and the Patent Office
should seriously consider his claim—despite its reactionary
policy. A federal judge then ordered the inventor to turn over
his perpetual motion machine to the Bureau of Standards for
tests of his claims. When the NBS found the machine to be
a very inefficient generator, using substantially more energy
than it produced, even that failed to silence the inventor.
Initially the inventor seems to have been genuinely
convinced he had discovered a new principle and that his
machine performed as he claimed it did. Nevertheless, after
conventional science had proved him wrong, he seems to have
evolved, in the words of Park (9) “from foolishness to fraud”,
hoping at least to fleece a lot of rich investors. He even
succeeded in convincing senators to reopen his case and hold
a special hearing about the abuse of power of the Patent Office.
Again, it was not testimony by scientists with impeccable
reputations that cost him his case. It was the disclosure, by
former astronaut John Glenn, of a conflict of interest in the
parties giving testimony in support of the inventor’s claims,
that killed it. However, it is worrying that such firmly estab-
lished principles as the laws of thermodynamics presented
by nationally recognized scientists and officials of trusted
government laboratories should be less persuasive to our law-
makers in Washington than charismatic quacks who appeal
to desires for a cheap solution to our energy problems.
Second Law and Equilibrium
On entropy and the teaching of thermodynamics.—An
interesting article by W. Brostow discusses the “myth” that
entropy is a name given to a quantitative measure of disorder
(10). Parts of it should be read to students after they have
had a bit of experience with entropy and its uses, not only or
not even mainly because it is helpful, scientifically. The prin-
cipal rationale for this diversion is that it delights students
since it (rightly) pokes fun at teachers of thermodynamics
and makes students feel less guilty about not mastering the
subject right away.
To set the stage I read from Cokcen’s Thermodynamics,
page 140 (although a large fraction of the other books on the
subject would serve as well): “An increase in the entropy of a
system is always accompanied by a corresponding increase in
the randomness of a system. Thus, a solid crystalline substance,
in which the atoms are arranged in some sort of geometric
pattern, becomes more random upon melting since molecules
can move more freely in the liquid.”
I show that the second sentence can be wrong by drawing
the phase diagram of 3He (Fig. 1). Helium is remarkable in
that it would not freeze at atmospheric pressure even if it
could be cooled to absolute zero. It can be crystallized at low
JChemEd.chem.wisc.edu • Vol. 78 No. 8 August 2001 • Journal of Chemical Education
In the Classroom
36
34
32
P / bar
30
28
26
24
0 0.1 0.2 0.3 0.4 0.5 0.6
T/K
Figure 1. Low-temperature phase diagram of 3He. The upper field
represents crystalline He and the lower, liquid He. Below about
0.3 K and above 30 bar, it can be seen that the liquid can be
frozen by heating it! Data from ref 12.
temperature, however, if it is subjected to a pressure of about
30 bar. For 3He at low T, the P-vs-T solid–liquid coexistence
line in the phase diagram curves downward for awhile before
beginning to increase (12). That means the solid exists at a
higher temperature than the liquid at a given pressure. There-
fore, it is clear that heat must be fed into the liquid to freeze it!
In other words, the crystalline phase has the higher entropy!
Then I read from Brostow (10), part of his section on “Entropy
and Disorder”:
We mean here, of course, the persistent myth that ‘entropy
is a name given to a quantitative measure of disorder.’
McGlashan [13] has explained that phrases like this are
meaningless, except in the three special cases of mixtures
of perfect gases, mixtures of isotopes, and crystals at
temperatures near thermodynamic zero.—And yet, even
today the myth seems to be still alive. The reason for this
seems to lie in the fact that one tries to connect an indeed
exact notion, entropy, with something called disorder,
which is loose and subjective and for which no defini-
tion exists.
The disorder story discussed above represents, unfortu-
nately, only one aspect of an otherwise grave problem:
bad textbooks of thermodynamics. At first glance, writing
a book on thermodynamics is a very easy task. This science
has existed for so long, and so many books have already
been written, that one can simply extract pieces from
several books and sell the compilation as a ‘new’ book.
This depressing hypothesis seems to be confirmed by (i)
the proliferation of books on thermodynamics; (ii) the
obsolescence of many of them—and (iii) the errors and
mistakes—there seems to be no other discipline of the
physical sciences, quoting McGlashan [13] so ‘incredibly
badly presented, for the most part by people who do not
understand it.’ The consequences are well known: the
frustration of students who, while suspecting some co-
herent structure and even beauty in thermodynamics, are
unable to comprehend it. A characteristic opinion of a
student is quoted by Andrews [14]:
‘To me, thermodynamics is a maze of vague quantities,
symbols with superscripts, subscripts, bars, stars, circles,
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 In the Classroom
etc., getting changed along the way, and a dubious method
of beginning with one equation and taking enough partial
differentials until you end up with something new and
supposedly useful (if that doesn’t work you try graphing).
I have the impression, however, that to other people, thermo-
dynamics is a logical study of the effects of temperature
and pressure on matter and on energy.’
By this time students are practically cheering!
I have to say that I think Brostow is too severe in his
rejection of the notion that entropy is related to disorder but,
to say it again, I included his remarks in my lectures because
it lifted the spirits of the students.
On Raoult’s law.—According to all physical chemistry
textbooks I know, two empirical auxiliary laws are invoked to
flesh out applications of the three principal laws of thermo-
dynamics. The two auxiliary laws are the ideal gas law and
the law of ideal solutions (Raoult’s law or Henry’s law, either
of which can be derived from the other via the Gibbs–Duhem
relation). Let us examine whether this characterization is
correct. First we review the validity of Raoult’s law. The fol-
lowing story is good at getting students indignant with “rigid,
unimaginative, authorities” but also at putting established
laws into perspective.
Many years ago one of my colleagues who was a brilliant
young thermodynamicist was studying activity coefficients
of components in various solutions. He discovered in an
aqueous solution of propyl alcohol that even in very dilute
solutions (the range in which Raoult’s law is supposed to
apply), Raoult’s law simply failed. Obviously this anomaly
deserved to be investigated because, if true, it would overthrow
a great deal of what had been written. So my colleague had
his students purify and repurify the alcohol by repeated frac-
tional distillations, and the anomaly remained, strong as ever.
Finally, after meticulous testing and retesting, having convinced
himself that the effect was reproducible and real—he wrote
a manuscript describing his findings and submitted it to a
standard journal in the field. He was dismayed to find it re-
jected at once by some referee. The referee said he didn’t know
what the mistake was but it was in my colleague’s work, not
in Raoult’s law, and that was that! My colleague was indignant.
Just because every crow you have seen has been black doesn’t
prove that the next one will also be black! Is it fair for estab-
lished authorities (probably men past their ability to think
creatively?) to play God with young people’s science?
Smarting from this attack on his competence, my colleague
went back to the laboratory, and this time, subjected the
alcohol to a battery of chemical purifications including treat-
ment with sulfuric acid. And what do you suppose he found?
Raoult’s law was now obeyed faithfully in the limit of dilute
solutions! Of course the authority was correct.
We can state this more strongly in the particular case of
Raoult’s law. All physical chemistry text books I am aware of
regard Raoult’s law as an empirical law, adopted as an auxiliary
law in addition to the ideal gas law. On the other hand, Fermi,
in his interesting little book on thermodynamics (15), proves
that Raoult’s law must be obeyed. The way he does it is to
evaporate a solution completely (any solution at all, heated to
whatever temperature and with whatever pressure lowering
might be required) and by the mathematical continuity of
thermodynamic functions, show that if the vapor is ideal,
Raoult’s law must hold for the solution. Now, we know that
1062 Journal of Chemical Education • Vol. 78 No. 8 August 2001 • JChemEd.chem.wisc.edu
the ideal gas law must hold for warm gases at low pressure and
we can derive the ideal gas law for gases under such conditions.
Therefore, we do not have to invoke two separate auxiliary
laws. One is sufficient. We can deduce that Raoult’s law is a
consequence of the ideal gas law, and the ideal gas law is
firmly founded on mechanical principles. So authorities must
not be dismissed lightly!
On Henry’s law.—When I joined the faculty of Iowa State
University, my colleagues quipped that I had better stress
Henry’s law when I taught. This was because our department
chairman had made a substantial amount of money after
noticing that carbon dioxide is significantly soluble in cream.
In accordance with Henry’s law, he found that the higher he
made the pressure of carbon dioxide over cream, the greater was
the amount of gas that dissolved in the cream. He discovered
this when he worked in the cow barns of a large state university
to put himself through college. Whatever led him to the
discovery is unclear, except that he was a very bright and
curious sort. Having observed the ability of CO2 under
pressure to dissolve in cream, he also discovered that, if he
released the pressure suddenly, the gas would quickly escape,
whipping the cream into as fine a froth as ever was produced
by the normal whipping process. Although he recognized the
commercial potential of this phenomenon of the self-whipping
of cream, he soon noticed that the carbonic acid in the cream
soured it. As a well-schooled chemist he knew that laughing
gas, N2O, had physical properties very like those of CO2 but
lacked the acidity and, moreover, was nontoxic. True to his
expectations, laughing gas worked perfectly. He had invented
“instant whip”. He even designed the container and nozzle
arrangement that produced whipped cream on demand.
To put the working of the world into perspective, how-
ever, I should point out that his commercial success was less
than he had hoped for. He was too poor to hire a good patent
attorney when he patented his product. An enterprising
scoundrel came out with a product that adulterated the
laughing gas with a bit of carbon dioxide—not enough to sour
the cream but enough to break the patent and take over the
lion’s share of the market.
On the volatility of tungsten.—When I first joined the
department of chemistry at Iowa State University, I was given
no start-up package and had no resources to begin a research
program (for political reasons I was not given an appoint-
ment in the Ames Laboratory of the U.S. Atomic Energy
Commission, a laboratory with lavish resources that supported
all of the other physical chemists). Therefore, it was suggested
that I join two physicists who were attempting, without
success, to evaporate tungsten and molybdenum on various
surfaces in order to study the optical properties of the pure
elements and mixed films of the two. I ultimately succeeded
in evaporating tungsten by switching from the original brass
furnace (!) to a heated tungsten filament in a high-vacuum
system, making sure that the filament did not come into
contact with any volatile material (16 ). In the process I found
just how extraordinarily nonvolatile tungsten really is, and
how marvelous the laws of thermodynamics are in allowing
one to relate something that is very difficult to measure to
something that is much easier. Indeed, this is the essence of the
power of thermodynamics. As it turned out, the best outcome of
this work was to provide a spectacular illustration of exactly
this point for students. The following story sets the stage.

When I was an undergraduate student with no longer
an attention span than most students, my mind wandered
during physical chemistry lectures and, staring at the water
faucet on the lecture bench, I daydreamed that if metal atoms
were as large as flies, I would be able to see them buzzing
around the faucet. It was only their truly small size, I supposed,
that kept the faucet from evaporating away perceptibly. But
when I began to study tungsten I was forced to a very different
conclusion! Suppose the faucet were made of tungsten. How
many atoms per liter do you imagine there are at the equi-
librium vapor pressure of tungsten at room temperature?
Better, how large a volume do you need in order to have just
one tungsten atom, on average, in equilibrium? One liter?
Guess again. One chemistry building? One Earth’s volume?
One solar system? No, much, much larger! Let us take the
radius of the visible universe to be 109 light years. That
represents a truly immense volume, but even that is not
enough to hold one gaseous tungsten atom in equilibrium
with the metal at room temperature.
I’ve forgotten the volume actually needed, but it is
something like 1016 universes. It is not a bad calculation for
students to do as a special exercise. How could one possibly
measure such a volume? There is no way to measure it, but
one can calculate it using the Clapeyron equation, knowing
the melting point, heat of fusion, boiling point, heat of
vaporization, and heat capacity. If an accurate answer is not
needed (of course, it would be useless), the simple Clausius–
Clapeyron equation should suffice, applied first to the liquid
and then to the solid to extrapolate to the vapor pressure at
room temperature. It is truly impressive how nonvolatile
tungsten really is! Which of course has something to do with
its use as filaments in light bulbs.
On the difficulty of teaching phase diagrams.—This story is
best told after teaching phase diagrams, a construction for which
I was all too often unsuccessful in conveying the meaning.
That this problem is not uncommon is illustrated by the fol-
lowing story.
One day, when I was a consultant to a major petroleum
corporation, I was discussing recent work with a small group
of Ph.D. scientists. In reviewing the properties of finely divided
tungsten–rhenium catalysts, the scientists wondered if the
individual particles were of the pure metals or were a solid
solution of the two. When it was suggested that the quickest
way to get an idea would be to look at the tungsten–rhenium
phase diagram, most of the scientists had forgotten what phase
diagrams are—as completely as my own students. This story
comforts students who find phase diagrams difficult and suggests
that we should try to find a better way to teach the subject.
Surface Science
Introduction.—I think it is unfortunate that all too many
physical chemistry teachers skip over the subject of surface
science during the term concentrating mainly on thermody-
namics. After all, surface science offers many nice examples
of applications of thermodynamics. Moreover, and quite apart
from the important technological applications of surface
science, there is the historical significance of the field. Science
taught without history is rather sterile. The reason for this
significance is that surface science gives a two-dimensional
view of the world, whereas the science of bulk material presents
JChemEd.chem.wisc.edu • Vol. 78 No. 8 August 2001 • Journal of Chemical Education
In the Classroom
a three-dimensional view. When the two sources of infor-
mation are played together, it becomes possible to learn the
approximate size of molecules and their range of interaction.
This was known by some scientists long before many well-
known scientists (including Mach and Ostwald) accepted the
reality of atoms and molecules!
I usually started surface science with a couple of stories. In
one, two patrons were enjoying a conversation over foamy mugs
of beer in a bar when one of them said “Bill, you’d better get
yourself to a doctor right away! You’ve got diabetes.” The
friend had noticed that every time Bill breathed onto his beer
the foam wilted away. That phenomenon illustrates surface-
active agents. The foam on beer (bubbles filled with carbon
dioxide) is stabilized by a beer protein film in much the same
way as soap bubbles are thin films of water stabilized by
monomolecular layers of soap. Surface-active agents that are
responsible for the foam stabilization are substances whose
molecules have polar groups (water-loving) and organic
groups (water-hating) and therefore tend to aggregate at the
surface of a solution. So, suds are thin water bubbles whose
surfaces are covered by a layer of molecules anchored to the
water by their “hydrophilic” groups. What is exposed to the
outside world (and also to the air inside the bubble) are or-
ganic groups. What has this to do with diabetes? Diabetics
may be in a state of ketosis in which they produce acetone by
metabolism, and this volatile substance is breathed out.
Acetone has fatty ends (methyl groups) and a polar carbonyl
group that is so water-loving it displaces the beer protein from
the foam surface. But acetone is unable, itself, to stabilize
foam. Fortunately, Bill did go to the doctor.
A closely related incident happened when I was on the
faculty of Iowa State University of Agriculture and the Me-
chanic Arts. In the spring there was a bad time when cows
ate alfalfa before it was suitable for cattle feed. The trouble
was that it started to ferment in the cows’ stomachs, and the
carbon dioxide liberated created a foam. This foam was sta-
bilized by protein from the immature alfalfa and caused cow
bloat, a serious condition in which the cow swells up like a
balloon! The only known treatment (and I used to get disgust-
ingly graphic when telling this story) was to take a sharp nail,
ram it through the cow’s side, and stand back as the rotten
gas spewed out. The agriculture people came to the chemists
to ask for advice. The surface chemists suggested feeding the
cows the dishwashing detergent ALL, a deliberately non-
foaming detergent designed to avoid filling a kitchen with suds
when a dishwasher is used. It might displace the alfalfa protein
in the cows’ stomachs and deflate them. Unfortunately, this
treatment hadn’t worked by the time I left the faculty.
On the size of molecules.—Who was the first person to
measure the size of molecules? Benjamin Franklin came very
close to that honor. His scientific prowess in other areas is
well known, and he is the first person of record to carry out
scientifically designed experiments that, with a quick calcu-
lation he did not make, could have given the first estimate of
molecular dimensions (17 ).
In fact, the world had to wait another century for the
answer. Franklin, like many before him, became interested
in the wave-calming effect that oil had when spread on wa-
ter. But what Franklin did, and published at the suggestion
of a clergyman, was to note just how far his oil (probably
olive oil or whale oil) spread on water. He was astonished to
1063
 In the Classroom
find that a teaspoon quickly spread over a half-acre of water,
then stopped spreading. The spreading gave a spectacular 107-
fold increase in area. Franklin could tell how far the oil spread
because of its calming effect on waves. He wrote “I think it a
curious inquiry, and I wish to understand whence it arises.”
The idea of molecules was not well developed at the time
but it was supposed by many that matter was particulate. If
Franklin had speculated that the oil spread until its thickness
was reduced to one molecule (which is the explanation), he
could have computed the length of a molecule from the thick-
ness of the film, since thickness times area equals volume, and
he knew the volume and area. His results yield about 20 Å,
a rather good estimate. Then, by making any plausible guess
about the shape of molecules, he could have estimated the
order of magnitude of how many molecules there are in, say,
a cubic centimeter of material. When Franklin was carrying
out his experiments, Avogadro had not yet formulated the
idea of moles and molecular weights. Therefore, Franklin
could not have estimated Avogadro’s number.
Oil films reveal their presence on water by greatly lowering
the surface tension. Because this has a very conspicuous effect
on the amplitude of waves in ponds and rivers, Franklin took
delight in playing tricks on his friends. He would tell them
he was going to cast a magic spell on the stream they were
walking beside, then would walk upstream many paces. When
he waved his cane as if it were a magic wand, lo and behold,
the stream suddenly became much smoother! Of course, in
the tip of his cane was a reservoir for a bit of oil.
A brief note to put Franklin into a historical context
that surprises many: he was born 50 years before Mozart. When
Franklin first went to England, he was promised a meeting
with Isaac Newton. This meeting never came about, though
Newton lived for about three years after Franklin’s visit. Most
people think of Franklin as a publisher and statesman of stature
but in his time, he was also considered a world-class scientist
by others, including his friends Priestley and Lavoisier. He was
a musician (he invented the “glass harmonica” an instrument
with an ethereal sound for which even Mozart wrote a small
composition) and a composer, as well. (In my opinion, how-
ever, Franklin’s musical compositions were pretty dreadful.)
A very rough estimate of Avogadro’s number can be made
from the surface tension, γ, and heat of vaporization, ∆Hv,
of a liquid. By dividing one mole of the liquid into N cubes
(for sake of example) and taking the cube edges to be L, the
area of the liquid is increased by 6NL 2. To separate the cubes,
the cost in work would be 6NL 2 γ. Note that NL 3 is the molar
volume of the liquid. Therefore, if one equates this energy
to the molar heat of vaporization, N becomes Avogadro’s
number, NA, and L, the molecular size. Both quantities can
be estimated crudely in this way.
As another example, let the force holding a cylinder or
“bar” of a liquid together be equated to the cross-sectional
area A times the internal pressure (available from the thermo-
dynamic equation of state). Then the work to separate the
“bar” into two pieces (so as to produce a new area A + A), is
2A γ = force × distance. Since everything is known except the
effective distance, this distance representing the range of
molecular forces can be calculated. It turns out to be of the
order of magnitude of several angstrom units. These two crude
but very simple estimates actually give the correct orders of
magnitude for the molecular properties!
1064 Journal of Chemical Education • Vol. 78 No. 8 August 2001 • JChemEd.chem.wisc.edu
Just how accessible to our mechanical sensibilities molecular
sizes really are can be brought home in laboratory experiments
with Langmuir–Blodgett layers on water. Students can deposit
a counted number of molecular layers on a slide. The number
of layers laid down can be counted by the number of times
the slide is withdrawn through the monolayer on water, then
put back and withdrawn again. Each withdrawal and each
insertion back through the film adds a layer of molecules. It
is easy to see the development of interference colors, from
which the thickness can be calculated. It is even possible to
build up a multilayer until the thickness of the deposit on
the slide can be measured with micrometer calipers, and hence
the length of the molecules can be measured by ordinary
devices.
There is another noteworthy story about Langmuir films
on water (17), films one molecule thick, as were Franklin’s
olive oil films, but whose areas are measurable in a small,
inexpensive “Langmuir trough”. Such films can be produced
by adding to the water surface droplets containing minute
amounts of oil dissolved in a volatile solvent.
A contemporary of Langmuir was Evert Gorter, a Dutch
M.D. who was not formally trained in physical chemistry.
Gorter was aware that membranes of living cells seemed to be
made of lipids (phospholipids, oils with polar groups somewhat
like Franklin’s oil). He and his assistant, Grendel, dissolved
the membranes of blood corpuscles in a volatile solvent, then
measured the area occupied by a monolayer on water corre-
sponding to corpuscle. What he found for blood corpuscles
from a variety of animals (including humans) was that the
area of the lipid per corpuscle spread on water was twice the
area of a blood cell. From this he correctly inferred that cell
membranes are bilayers, which present their polar groups to
the outside and inside of the cells. The lipid molecules in the
bilayer, then, are joined organic tail to organic tail. Although
he published this correct structure and composition of cell
membranes in 1925, it was approximately a half-century before
his findings were accepted by biological scientists (16 ).
In between a Ph.D. and an academic job, I was invited
by the Simonize Company to study their wax films manu-
factured for automobile polish (today’s automobile paint is
so much more durable that car wax is all but extinct). At the
time Simonize had little idea of how thick its films were or
what structure they had. Conventional surface-chemical tools
told them little.
After several fruitless tests by more conventional
techniques, I devised one of the first ellipsometers ever used
in surface chemistry. An ellipsometer is an optical device able
to measure film thicknesses to fractions of an angstrom unit.
It turned out that a really well buffed Simonize film was much
thinner than had been suspected. It was approximately the
length of the carnauba wax molecules used in the preparation!
Out of curiosity I deposited fatty ester molecules onto a
metal substrate by evaporation of a dilute solution and found
by diffracting electrons from the film that the long molecules
were standing up in the film. Then, when I stroked them
gently with Kleenex, I found that this made them lie down,
nearly parallel to the surface. It really gives one a feeling of
intimacy with molecules to see them obeying orders like a
pet dog.
But the most remarkable thing was the protection these
scant layers could give to lacquer films. In order to use the

ellipsometer with films on lacquer (automobile paints of the day
were sometimes lacquer) I had to prepare lacquer films about
100 Å (10 nm) thick on a metal surface because reflection
from the metal was essential for ellipsometry. These films were
so flimsy that they tore at the slightest touch by the gentlest
tissues available. But when just one layer of wax molecules was
deposited onto the thin lacquer films, you could rub as hard as
you wished with tissues without any damage to the underlying
lacquer film. Obviously one layer of soft wax molecules does
not provide an armor plate to protect the underlying film.
What was provided was lubrication. Remember that molecular
forces are very short in range, much less than one layer of
wax molecules. To the outside world, the surface is slippery
wax, not lacquer. The moral of the story is obvious. If we
somehow alter surfaces by just one molecular layer, we can
profoundly change the properties of a surface (friction, wetting,
catalytic properties, etc.) Changes can be beneficial or harmful
to properties of a product. Therefore the great importance
of surface science to industry.
Kinetic Theory
History of the kinetic theory (4).—Students learn about
Maxwell’s development of the kinetic theory of gases, but the
real story of the first formulation of the kinetic theory of gases
is more depressing than the one recorded in textbooks. John
Waterston (1811–1883), a brilliant but unknown young man,
worked out the essentials of the kinetic theory some 15 years
before Maxwell. His long manuscript was turned down as
nonsense by the referees of the prestigious journal he submitted
it to. Worse, it was his only copy, and the journal would not
return it. Authorities can be and often are reactionary and
unimaginative. This trouble so bothered Waterston that he
developed a contempt for scientific colleagues and dropped
out of science. His original paper was, however, archived by the
Royal Society so that its priority is verifiable. Much later, the
distinguished physicist Lord Rayleigh consulted the archives
and wrote at length on the important contents of Waterston’s
first paper, confirming the originality and ingenuity of his
approach. He then offered a cynical moral to the story: “The
history of this paper suggests that highly speculative investi-
gations, especially by an unknown author, are best brought
before the world through some other channel than a scientific
society, which naturally hesitates to admit into its printed
records matter of uncertain value. Perhaps one may go further
and say that a young author who believes himself capable of
great things would usually do well to secure the favorable
recognition of the scientific world by work whose scope is
limited, and whose value is easily judged, before embarking
upon higher flights.”
In this respect one thinks of the unknown young Indian
scientist Bose, whose manuscript treating electromagnetic
radiation by a strange new statistics was rejected by British
journals. His writings met with little success until he sent his
paper to Einstein. The rest is history. Einstein recognized the
genius of it, translated it from English into German, and had
it published in the Zeitschrift für Physik. He then generalized
the treatment (now referred to as Bose–Einstein statistics) to
the case of material gases, and predicted, among other things,
the Bose–Einstein condensation, which has recently burst so
spectacularly into the news.
JChemEd.chem.wisc.edu • Vol. 78 No. 8 August 2001 • Journal of Chemical Education
In the Classroom
Gas viscosity.—Experience with molasses in January and
high-viscosity oils and polymers leads students to an intuition
about effects of temperature, molecular length, and concen-
tration on viscosity that is contradicted by properties of gases.
The counterintuitive behavior of gas was predicted before it
was measured (18), helping to nail down the kinetic theory.
Unlike motor oil, a gas increases in viscosity when heated,
and the viscosity is decreased as molecular sizes increase. More-
over, increasing the gas density leaves the viscosity unchanged !
The charming way Moore in his early editions of Physical
Chemistry (19) introduced gas viscosity leads to a very easy
way to understand it, estimate it, and explain its somewhat
surprising properties. Without this charm and without
pointing out how differently gases respond to changes in
temperature, concentration, and molecular dimensions,
viscosity appears to be a dull subject. Since gas viscosity gives
us a measure of the collisional area of molecules per mole,
this can be played against the molar volume of the liquid to
estimate Avogadro’s number, another reason for the historic
importance of gas transport properties. Recall that, in the
early days of the kinetic theory, many of the most influential
scientists did not believe in molecules.
More Morals about Authority
The following stories cast interesting sidelights on scien-
tists when the advances in physical chemistry they introduced
are discussed.
Impact on Arrhenius.—When Arrhenius was a student,
he proposed his perceptive treatment of what we today call
ionic solutes. But many or most scientists of the time did
not believe that salts are composed of positive and negative
ions or that the interaction of a solvent with salts, acids, and
bases might produce ions in solution. This, despite earlier
definitive suggestions by Clausius to the contrary. Nevertheless,
the scholars on the committee of Arrhenius could not prove him
wrong. Besides, in his thesis, Arrhenius had been somewhat
vague and careless in his exposition (20). So the committee
compromised: their solution was to award him the lowest
passing grade. In reality, such a grade was a grave punishment,
for it prevented Arrhenius from being offered an academic
position in Sweden. Nevertheless, when it became clear that
the famous physical chemist in Germany, Wilhelm Ostwald,
was greatly impressed by the achievements of Arrhenius and
offered him a position, Sweden relented and admitted him
into the ranks of Swedish scientists, where he flourished. So
Arrhenius felt the sting of authority—until a higher authority
prevailed.
Impact on Einstein.—Another story involving authority
is about Albert Einstein. His performance in what we would
call graduate school was somewhat indifferent in the eyes of
his teachers because, as Einstein himself reports in his brief
autobiographical sketches (2), he hardly ever went to lectures.
Instead, he went to the library and studied the primary
literature. Therefore, he was not regarded as a really serious
scholar, and his performance on the few examinations given
to him was less than fully stellar. Consequently, the only
position he could find, and that through the special influence
of the family of a friend, was as patent office examiner.
In 1905, after he had been at the patent office for a few
years, he published an astonishing outburst of papers. In them
1065
 In the Classroom
he developed the special theory of relativity, the statistical
mechanical theory of fluctuations including the first quanti-
tative treatment of Brownian motion, and several seminal
ideas on the quantum theory of matter and radiation, includ-
ing the photoelectric law.
Because his contributions were so remarkable, Einstein
became well known quite soon, and within a few years he was
being nominated for the Nobel Prize by some of the most
famous scientists in the world. But the Nobel committee kept
turning him down, year after year. Finally some previous Nobel
laureates wrote that the failure to award Einstein the Prize
was becoming an embarrassment to the Nobel committee. Still
the committee refused to award Einstein the Prize. Some of
Einstein’s predictions were not yet confirmed, and some were
contested by less talented scientists. But the Nobel committee
finally found a compromise. It awarded Einstein the prize
for his contributions to theoretical physics, citing his photo-
electric law! And do you know who the committee member
was who kept vetoing Einstein’s award? It was Arrhenius! I
think there is a moral in this story somewhere….
On the reputation of Gibbs.—J. Willard Gibbs was a man
of independent means when he lectured (without pay) at Yale
University. He carried out research of extraordinary depth in
thermodynamics and statistical thermodynamics and invented
vector calculus in the bargain. He published mainly in the
Transactions of the Connecticut Academy. Although this journal
was not widely read, Gibbs submitted reprints to the most
distinguished European scientists of the time, including
Maxwell, who immediately recognized their importance and
beauty. In his later years Maxwell spent considerable time
carefully constructing, with his own hands, a model of Gibbs’s
thermodynamic surfaces, a cast of which, shortly before his
death, he sent to Gibbs.
At the time, American universities were just beginning to
try to build up their faculties in the sciences. Many chairmen
of physics and chemistry departments wrote to the best-known
scientists in Europe for advice on whom to import from
Europe for their departments. Often enough they received
the reply “Why don’t you consider the American, Gibbs? His
work is outstanding!” After awhile Gibbs began to receive
offers to move from Yale, and at attractive salaries. When the
New Haven townspeople heard of this state of affairs, they
got together a stipend to offer Gibbs if he stayed at Yale. And
so he did.
Vulnerability of and imperfections of true authorities.—
Troublesome controversies are mentioned above. The giants
Gibbs, Newton, and Einstein particularly suffered from this
vexing source of aggravation. When Gibbs developed vector
calculus he was subjected to savage attacks by those who pre-
ferred the more tedious methods of the day. This caused him
much anguish. Newton also encountered acrimonious criticism.
He wrote that, if he had known what a litigious lady natural
science was, he never would have entered the field. Einstein
said it more simply. He remarked that if he were beginning
again, he would become a plumber or peddler.
When covering gas laws, it might be remarked that the
springiness of air (its resistance to compression) was well known
to Newton, a contemporary of Boyle. Newton recognized that
he could calculate the speed of sound in air via the elasticity of
air. Gifted in abundance though he was, his calculated velocity
did not agree with experiments! We now realize that Newton
1066 Journal of Chemical Education • Vol. 78 No. 8 August 2001 • JChemEd.chem.wisc.edu
took the isothermal elasticity when he should have taken the
adiabatic elasticity. Otherwise his theory was correct.
Newton also outlined in his Principia (21) some “Rules
of Reasoning in Philosophy” His Rule II:
Therefore to the same natural effects we must, as far as pos-
sible, assign the same causes. As to respiration in a man
and in a beast; the descent of stones in Europe and in
America; the light of our culinary fire and of the sun.
Newton’s rule is an excellent one but his last example is some-
what misguided in the light of today’s knowledge.
On Boltzmann’s tomb is inscribed his statistical prescrip-
tion for entropy:
S = k log W
Boltzmann’s contributions to statistical science were enormous.
Yet he became regarded by many well-placed colleagues as a
has-been, a man whose science was of equivocal value. Even in
recent times a popular play in Germany was about a fumbling
old professor whose work was held in contempt, and the mis-
informed playwright based his character’s life on Boltzmann’s.
Today we regard Boltzmann as one of the most creative
founders of the science of statistical thermodynamics. But in
Boltzmann’s day he received more criticism than he could
bear—so much that he was driven to suicide.
Many of the above stories dealing with human nature
and human activities are unhappy ones. But not all stories
in chemistry are negative, of course. A wealth of happy stories
can be found, for example in the book Serendipity, by R. M.
Roberts (22).
Another (short) story about personalities. At a recent
physics seminar the speaker remarked that although Faraday
conceived of the existence of the “field” in electromagnetic
phenomena, he was unable to understand the mathematical
development of his concept by Maxwell “because of the fact
that he was the child of a blacksmith!” To this remark was
replied that humble beginnings do not preclude proficiency in
mathematics. The great mathematician Fourier was the 19th
child of a poor tailor! Now that Fourier has been mentioned,
his experience gives another example of how acknowledged
authorities often fail to recognize the virtue of important new
ideas. Fourier’s publication of his seminal work on Fourier
series and boundary value problems was delayed for 24 years
owing to hostile reviews by Lagrange.
Concluding Remarks
Motivated by the response of colleagues and students, I
submitted this collection of stories in the hope that it would
encourage teachers to tell more stories. Some teachers are so
gifted they can hold students spellbound. Lacking such
charisma, I found that stories are a useful substitute. Not only
do they offer an effective and relatively painless way to convey
ideas, they also make lecturing more fun for the teacher.
Literature Cited
1. Bartell, L. S. J. Chem. Educ. 2001, 78, 1067–1069.
2. Einstein, A. In Albert Einstein: Philosopher-Scientist, 3rd ed.;
Schilpp, A., Ed.; Cambridge University Press: Cambridge, 1969.
3. Lewis, G. N.; Randall, M. Thermodynamics and the Free Energy
of Chemical Substances; McGraw-Hill: New York, 1923.

4. Borse, H.; Motz, L. The World of the Atom; Basic Books: New
York, 1966; Vol. I.
5. Smith, C.; Wise, M. N. Energy and Empire. A Biographical
Study of Lord Kelvin; Cambridge University Press: Cambridge,
1989.
6. Bondi, H.; Gold, T. Mon. Not. R. Astron. Soc. 1948, 108, 252.
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CA, 1975; p 140.
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at Low Temperatures; Wiley: New York, 1984; p 18.
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In the Classroom
13. McGlashan, M. L. J. Chem. Educ. 1966, 43, 226.
14. Andrews, F. C. Thermodynamics: Principles and Applications;
Wiley-Interscience: New York, 1971; p 3.
15. Fermi, E. Thermodynamics; Dover: New York, 1959.
16. Bartell, L. S. Adv. Mol. Struct. Res. 1999, 5, 1–23.
17. Tanford, C. Ben Franklin Stilled the Waves; Duke University
Press: Durham, NC, 1989.
18. The Scientific Papers of James Clerk Maxwell; Niven, W. D., Ed.;
Dover: New York, 1952; Vol. 2, pp 1–78.
19. Moore, W. J. Physical Chemistry, 3rd ed.; Prentice Hall:
Englewood Cliffs, NJ, 1962; p 225.
20. Servers, J. W. Physical Chemistry from Ostwald to Pauling. The
Making of a Science in America; Princeton University Press:
Princeton, NJ, 1990.
21. Newton, I. Principia; Cajori, F., Translator; University of Cali-
fornia Press: Berkeley, 1943; p 398.
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Wiley: New York, 1989.
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