Milton Burton

University of Notre Dame A Second Lecture in Thermodynamics

Notre Dame, Indiana

Classical thermodynamics is perhaps the experience is wholly that of some select group who have
first mathematically elegant branch of science to which a strange power of entrfi into realms which are forbidden
most chemistry students are exposed. Consequently, to students until after they have been exposed to the
many of them gain the impression that it cannot be mysteries of thermodynamics.
understood except in mathematical terms and never Teachers of physical chemistry are well aware that
within the framework of their early experience and the subject is not merely a discipline in itself but is also
intuition. This is precisely the attitude which should the basic background of all of chemistry. Thus, there
be dissipated in an opening lecture if the students are to
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is an increasing effort in universities to introduce the

gain an aesthetic appreciation as well as a quantitative subject at a sufficiently early stage in the study of
grasp of thermodynamics and are to enjoy it rather chemistry that it may assist in the acquirement and
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than to fear it. Once the student knows what energy correlation of chemical knowledge. The objective is
is—and the idea can be put across in one lecture—he is to introduce the subject as soon as the students have
ready to grasp the meaning of the three laws in a single adequate tools. With the reorganization of mathemat-
following lecture. The first law may be taught in the ical teaching it now frequently happens that students
form that we must assume that mathematics itself is can profitably begin the study of physical chemistry at.
conservative if we are to have any system in science at the sophomore level. In many presentations of the
all. The second is taught as a genuine law of experi- subject, thermodynamics is the first area studied. It is
ence (of the student, not merely of his teacher) regard- important not only that such studies have long-term
ing the meaning of temperature. Entropy is then re- values but that the student acquires, not a fear, but an
lated to that experience and defined, and finally the easy familiarity with the subject. In this case, we
relation between entropy and probability is explained. need not fear that familiarity breeds contempt. In a
Thereupon, the relationship S k In W is introduced
=
subject as delightful as thermodynamics, familiarity be-
ad hoc and the third law is shown to follow as an comes the forerunner of a great and lasting respect—
intuitive concept regarding a single lowest energy state. like that, of a good farmer for his fertile land. Our
At this point, it should be indicated that an operational objective is to make the student continuously aware of
form of the law is more suitable for science. both the charm and the utility of thermodynamics so
This presentation has been repeatedly made in the that he can expand its usefulness in self-study.
second lecture on thermodynamics on both elementary Properly expounded, t.he first course should eliminate
and advanced levels and serves to prepare the students the necessity for the student ever taking another course
for the analysis of meaning, and the development of in classical thermodynamics, even on the graduate
consequences, of the laws which will occupy the rest of level. The objective is worthy and the result, if
the term. Past experience, aesthetic appreciation and achievable, is, at the very least, time-saving.
mathematical elegance may be thus made part of a The First Lecture. Like many others. I find it con-
single enjoyable pattern. venient and desirable to limit the first lecture in thermo-
dynamics to definition and classification of the more
Proposition familiar terms of energetics. I find it convenient to
For many students thermodynamics is the first speak briefly of the nature of science and the scientific
demonstration of the power of mathematical rigor in method, of the nature of “explanation” in science, of
science. Frequently, it is the first application of any law, theory, hypothesis and test, of experience and
branch of mathematics exceeding arithmetic, elemen- intuition, and of “exact definitions” of terms (i.e., in
tary geometry or simple algebra in subtlety or com- this early approach, definitions in terms of greater
plexity. As a result, many of the students become so familiarity). I speak of energy, work, the intereon-
obsessed with details of symbolism and proof that they vertibility of energy as a fact of experience, and of the
lose sight of the fact that the subject is concerned to a use and utility of intensity and extensity factors in ex-

very high degree with immediate experience. Indeed, pression of our concepts of energy. I explain what is
although we habitually expound the second law as a meant by an isolated system. I give the customary ex-
“law of experience” most students assume that the amples and resort in the casual way, so common in all
our presentation, to the use of symbols in the expres-
Presented as part of the Symposium on the Teaching of Thermo- sion of ideas. And, of course, I speak of total energy of a
dynamics before the Division of Chemical Education at the Mist system as the sum of all kinds of energy, some of which
Meeting of the American Chemical Society, Washington, D. C., can be readily differentiated into known intensity and
March, 1062. This contribution comes from the Department of
Chemistry and the Radiation Laboratory of the University of extensity terms and others of which we cannot so
Notre Dame. The Radiation Laboratory is operated under con- differentiate (e.g., “internal energy”) or which we
tract with the U. S. Atomic Energy Commission. must examine carefully t,o recognize these attributes.

500 / Journal of Chemical Education

 The Second Lecture. The second lecture is intended Maxwell and ask the class to define temperature. The
to create an atmosphere of amiable familiarity with the first answers are more or less sophisticated. Motion of
subject matter of classical thermodynamics, with the molecules is introduced and I reject it. Indeed, 1

range of its contents, and with the direction in which emphasize to the class by repeated rejection of all
its study naturally develops. This report does not subtle notions that their ideas of temperature have
pretend to be an exact copy of any one such lecture. preceded most of the knowledge they have. Indeed, I
It is an abbreviated paraphrase in which I attempt to recall to them that they learned at a very early stage
present the flavor of the approach rather than its de- that very hot things might be uncomfortable to touch.
tails. It is based upon my conviction that any intelli- (What child has failed to touch a hot stove, hot lamp,
gent person of college years has the capacity to under- or hot radiator!) Here begins sympathetic apprecia-
stand the province of classical thermodynamics {i.e., tion of the problem and I ultimately (and very quickly)
“what thermodynamics is about”) without detailed learn, as a product of the students’ growing exaspera-
mathematics. I further maintain that this understand- tion, precisely what Maxwell taught: that a body is hot
ing of the basic matter of thermodynamics (i.e., the because it feels hot, that it is cold because it feels cold.
nature of its laws) should precede, not follow, study. You know instinctively that the intensity of heat in
In the beginning of my second lecture on thermody- the hot body is greater than in you.
namics, I describe it as the science of superficialities, of Now, we are ready for sophistication. The body is
external appearances, and attempt to impress the stu- hot because it feels hot to you; ergo, you are colder.
dent with the power of exact (i.e., mathematical) What happens that makes it feel hot? Heat flows
thought when applied to apparent trivialities. Un- from it to you. What is at the higher temperature?
fortunately, I am forced to use intuition, rather than The hotter body.
exact, provable statements, in such a first, approach In which direction does heat flow spontaneously?
because otherwise we might (to very good purpose for a Heat flows spontaneously from the condition of higher
really advanced scholar) confine our examination to the temperature to the condition of lower temperature.
exact meanings of the concepts themselves and never Is this a definition of temperature? Yes; temperature
advance in the direction of application. This is a fact is that intensity factor which determines the direction
which should, in complete honesty, be made clear to of the spontaneous flow of heat in an isolated system.
the student at once so that he may, if he so wishes, re- Well, then, what is heat? Heat is that form of energy
turn to these questions at some later date in his career which flows spontaneously from a higher temperature
and thus increase the precision of his ideas and his to a lower temperature.
reasoning. However, at this stage, the important Well, so far, we have introduced a difficulty inherent
point to make is that the experience he has already in our experience. We have defined heat in terms of
acquired, indeed acquired at a very early stage in his temperature or we define temperature in terms of
can
development as a personality, is useful, powerful, heat. Either definition is a statement of the second
stimulating, indeed even exciting. law. They are equivalent, derivable one from an-
other, but, unprovable. They are stated as learned and
The First Law true facts of repeated personal experience but they
cannot be proved. They have the true attributes of a
All the students have been exposed to the concept, of law. Let us try to see what else such facts mean.
conservation of mass-energy so that a brief, historical
Entropy, Let us perform an Aristotelian experiment
review of the development of this idea evokes a sense of and take a pail of water out of the ocean. Evidently,
familiarity, indeed, of intimate remembrance. Having the ocean contains more heat than the pail, even if we
set up this situation, 1 now state that the first law is
can’t measure it. Now, if we place the bottom of the
in reality a statement of confidence in arithmetic, a
pail in the ocean, the contents of the pail do not change
statement that simple arithmetic applies in science, in temperature. Heat flows neither in nor out.. Since
that mathematics (including arithmetic) is conservative there is no temperature difference to determine the
and, when employed properly, introduces and loses no direction of the flow of heat, there is no resultant heat
terms not present in the original set-up. This idea is, flow. Total heat content (i.e., quantity of heat) has
of course, not trivial. Were I to present it properly in
nothing to do with direction of flow of heat.
systematic, logical fashion, we would stay with the There is more heat in the ocean than in your indi-
idea too long. Instead, I emphasize this statement, of vidual body. However, the ocean feels colder than your
confidence in arithmetic as a conservative subject, as a
body when you swim in it; why? Because its tempera-
product of experience, the “proof,” in the primitive ture is lower. Heat does not flow spontaneously in the
sense of “test,” of which has already appeared in its
direction of decreasing quantity but in the direction of
repeated utility for the student in his personal develop- decreasing temperature. Temperature is not a measure
ment. A denial of the first law is essentially a denial of quantity. It is itself a record of an intensity factor;
of the validity of arithmetic in the study of science. heat flows in the direction of decreasing intensity. Let
Such a denial is untenable. Without the acceptance of
Ti be your body temperature and 7\ the temperature
the validity of arithmetic in science, the systematic of the ocean. Because 7k > Th heat flows spontan-
study of science is impossible. This view the student eously in such an isolated system (i.e., the ocean plus
already holds; we proceed without difficulty. your body) in the direction
The Second Law 7k— r,

Temperature and Heat. The second law is intro- Let the amount of heat which flows be represented by a
duced in another way. I resort to the method of quantity factor, Q.
Volume 39, Number 10, October 1962 / 501
then -(h =
Qi We know the real direction of the flow of time.
Time flows in such a direction that the probability of
where Qa represents heat loss1 by your body and Qi
—

the resultant situation increases in any spontaneous

heat gain by the ocean. If it is a cold day, particularly and isolated process. Time flows in such a direction
if T2 » Ti you get out of the ocean in a hurry so that,
that the entropy of an isolated system increases spon-
although a measurable amount of heat has flowed, the
taneously with time. We shall see later that it is more
temperatures T-, and 1\ remain substantially constant; convenient for the situation common in a laboratory to
i.e., for practical purposes (convenient for our immedi- introduce another term (the Gibbs free energy) which
ate mathematical convenience) both your body and the
describes the direction of change in the more general
ocean are “infinite heat reservoirs.’'
case of a non-isolated system. However, one thing is
Now, heat itself, like any other energy term, is the already clear. We see that a statement of the direc-
product of two factors: an intensity factor, T, which tion of the flow of time (in either of two forms) is also a
we have already identified as temperature, and an
statement of the second law.
associated extensity factor which we may symbolize as
Resume. We have seen that the second law may be
S and which is called entropy. At the higher constant
stated in anyone of a variety of forms each of which
temperature the heat change (a loss) is have co-equal validity, for they are a product of per-
Q! =
TV AS), sonal experience and are unprovable either individually
or in toto. The second law is either or all of the
Because Q, =
Q\, it follows that
—

following:
-TV AS), =
TV AS),
A definition of temperature
and, because T% > Tl} it is equally true that A definition of heat
(From both of which a definition of entropy comes)
-(AS), < (AS,) A statement concerning entropy change and its relation to
spontaneous heat flow
or, more conveniently, A statement of the relation between probability change and the
|(AS),| < |(AS,)] direction of flow of time
A statement of the relation between entropy change and the di-
Thus, the total change'in entropy of the isolated system rection of the flow of time
ocean plus your body is the sum of the entropy changes A statement of the invariable direction of the flow of time
in both; i.e.,
A particularly charming and related form of the
AS =
(AS), -(- (AS), Second Law which emphasizes probability or entropy
and is a positive quantity because, although (AS)2 as a measure of mix-uppedness and which students are
is negative, it is numerically smaller than (AiS'),.2 unlikely to forget is “If you think things are mixed up
We can now say as a product of our own experience, now, just wait a little while,”
when we try to go swimming in too cold an ocean that Third Law
heat is that form of energy which, in an isolated system,
flows spontaneously in such a direction as to increase Entropy arid Probability. It is important now to
entropy. Or, put differently, entropy is the extensity speak more quantitatively about probability. A con-
factor associated with heat; the direction of spontane- venient, device is to describe the game of dice (vulgarly
ous change associated with heat flow, in an isolated called “craps”), which is sometimes known to some of
system is the direction which yields an increase of the members of the class. For those who are unac-
entropy. quainted with the game, the nature of a "die” can be
Probability and the Flow of Time. Now, entropy it- readily explained and the probability of throwing a two
self, may be associated with another well-known (“snake eyes” for the cognoscenti) or a twelve (“box
characteristic which we know increases spontaneously cars”) as compared with throwing a six or a seven can
with time. If wc watch a movie of a graceful dive from be readily expounded. Even the least educated of the
a spring-board, all is familiar. The diver springs, the students quickly learns that the a priori probability of
board vibrates; he rises, bends, straightens, cleaves the throwing snake eyes is only unity (IE 1) compared
=

water gracefully and creates in symmetric array around with the a priori probability of throwing a seven (IE
himself a fountain of drops which as gracefully rise and =
6).3 Whether the lesson is usefully learned, I
then fall into a pool of gently subsiding ripples. Then, cannot state. The important point that they should
in a fit of cuteness, someone reverses the film and all the learn is that large-scale events take place in the direc-
reverse phenomena occur, in precisely reversed sequence tion of increasing probability and that that probability
and all according to exactly the same mechanical forces, can be numerically expressed.

acting in reverse. No one is fooled although some are We now introduce, without proof, a statement derived
amused. The whole thing is wrong because it defies by Helmholz, which follows from statistical mechanics,
probability; only that (macroscopic) phenomenon oc- and which shows the numerical relationship between
curs spontaneously which involves an increase in the entropy and the probability of a system.
probability with time. S « k In W
The term k is recognized as the gas constant R (in small
1
At this stage we introduce our first mathematical “complex- calories) divided by the Avogadro number. When IE
ity.” I quietly note that, because heat loss occurs, Q-> has a is equal to unity (as it is for “snake eyes”), jS 0. In =

negative value and that, conversely, Qi has a positive value.

2
This presentation is made more thoroughly here than in my
usual lecture. I am content to have the class accept the conclu- s
Here, the lecturer can take a moment to teach a little Ger-
sion (as it usually does) even before I complete the argument. man; i.e., W —
Wahrscheinlichkeit.

502 / Journo/ of Chem/ca/ Educaf/on

chemical usage W represents the number of equivalent grounds) and the consequent fact that in this form the
arrangements of one mole of a substance in a particular third law is experimentally useless because it is 11011-
energy state. operational. Later in the term, I inform my class, we
Intuitive Form. We are now ready to consider an will reexpress the third law in a more restricted, but
intuitive notion, namely that below a certain limiting operational, form which follows directly from experi-
energy state it is impossible to extract any more heat ment and is, thus, both subject to experimental test
from a system. To put it differently we can say that and experimentally useful. For the present, I want
we can imagine that for any system there is a lowest them to known that without any grand notions they
energy state, a state lower in energy than that of any have arrived at the central idea of the third lav- purely
other arrangement in which we can put the system. on the basis of intuition grounded in experience.
Here, as before, I am treading lightly on dangerous
Promise for the Future
ground but 1 watch my step and avoid difficulties by
admitting the existence of subtleties which may limit The remainder of the series of lectures in thermody-
the precision of my statements. However, I do state namics, I inform my class at the end of this second lec-
that, if the state is recognizable only by its difference ture, will be devoted to exposition of the same ideas with
from other states (by a difference which is in the final increasing rigor, with examination of the consequences,
analysis an energetic difference), then the lowest energy and with application of the ideas (in mathematical
state must be unique, its a -priori probability is unity form) both to familiar systems which they have not
and its entropy is zero. We can now express an intui- well understood and to unfamiliar systems whose
tive form of the third law, namely that a chemical properties and behavior they may construct or calculate
system can be conceived as existing in a lowest attain- by rigorous development and application of the three
able energy state and in that state (which we can laws. And I conclude by the statement that the sub-
describe as at the temperature of 0°K) its entropy is ject is inherently mathematically simple because it in-
zero. volves no mathematics more complicated than simple
Reservations. I conclude this portion of the discus- calculus. In brief, I tell them that for the remainder
sion by indicating the impossibility of achievement of of this lecture series we will amuse ourselves by “ringing
the lowest energy state or absolute zero (e.g., on kinetic the changes” on the three laws of thermodynamics.

•f

Volume 39, Number ) 0, October ? 962 / 503