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Maxwell, His Demon, and the Second Law of Thermodynamics: Maxwell saw the second law as statistical, illustrated this with his demon, but never developed its theory Author(s): Martin J. Klein Reviewed work(s): Source: American Scientist, Vol. 58, No. 1 (January-February 1970), pp. 84-97 Published by: Sigma Xi, The Scientific Research Society Stable URL: http://www.jstor.org/stable/27828933 . Accessed: 17/02/2012 13:22
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Martin

J. Klein

Maxwell, His Demon, and the Second Law of Thermodynamics

Maxwell saw the second law as statistical, illustrated thiswith his demon, but never developed its theory

By

the mid-sixties

it, in the words already describe a use James Clerk Maxwell would few years later, as "a science with secure foundations, clear defini tions, and distinct boundaries" (/). As one sign of one of of the the maturity subject, Rudolf Clausius, its creators, reissued his principal papers on thermo dynamics as a book efforts protracted general form of the second order to meet the need of the thermodynamic dealing with the variety to which the theory was to find in 1864 (2). He also set aside his the simplest and most

thermodynamics could turity. One

of the last century the science of had reached a certain level of ma

textbook" for use in his own classes (4, p. mentary to set the reason was Tait's desire iii). Another historical record ing the claims Joule and William straight, which for him meant urg of his compatriots, James Prescott Thomson (later Lord Kelvin), who had contributed

against along similar lines-?Julius Robert Mayer, Hermann von Helmholtz, and Clausius. Since Tait admitted in his preface that he might have taken "a somewhat too British point of view" (4, p. v), it is not surprising the center of a stormy contro that his book became versy, but that controversy is not our concern here

those of the Germans

in law of thermodynamics for convenient working forms forms suitable for equations, of experimental applied situations being (3).

(5).
Before Tait off to the publisher, sending his manuscript to Maxwell, wrote asking him to apply his to it. Tait was already critical powers expecting

Another

indication

the appearance Sketch of Thermodynamics

principles of thermodynamics. have written a comprehensive did make the basic to students. One of his concepts

(4). This consisted of a re on had already published in the theory the history of the recent developments of heat, supplemented by a brief treatment of the vision of two articles Tait Tait did not claim treatise, but his book and methods available

of the maturity of the subject was in 1868 of Peter Guthrie Tait5 s book,

trouble over his assignment of priorities and credit, had been sent and Helmholtz since both Clausius and had reacted an at (5a, pp. 216-17; 6). Maxwell the two men had been together was negatively old friend; school, at the

parts of the manuscript

to

and at Cambridge. of Edinburgh They University shared a variety of scientific interests and carried on a particularly lively and correspondence vigorous . It was not at all unusual for to read the Maxwell (7)

for writing the book was, in fact, his feeling of "the want of a short and ele

reasons

or proofs of his friends' books and to manuscripts "enrich them by notes, always valuable and often as Tait of the quaintest himself wrote character," This timeMaxwell (8) . provided his enrichment even before he saw Tait's book. Maxwell wrote Tait that he would he did be glad to see his not "know in a con

Martin teaches He

A graduate of Columbia, he holds a Ph.D. from M.I.T.

has worked mechanics, of physics on Planck, and on various problems most recently has

at Yale, J. Klein, of the History Professor of Physics both physics and the history of science at the University.

this winter. Address: dam), will appear Yale University, of Science and Medicine, Haven, Conn. 06520. 84 American Volume 58

in the nineteenth and twentieth centuries. His papers and others have appeared in a number of Einstein, Gibbs, His of Volume book, Paul 7, The Making Ehrenfest, journals. a Theoretical Amster Co., (North-Holland Physicist Publishing Department 56 Hillhouse of the History Avenue, New

in thermodynamics and statistical been studying the development

(7948).

manuscript, although troversial manner the history of thermodynamics" so was not to join his friend in waging and prepared the priority wars. "Any contributions I could make to that study," he went on, "are in the way of altering the point of view here and there for clearness or and picking holes here and there to ensure proceeded stability" (9). Maxwell

variety,

strength and

to

Scientist,

pick such a hole?in namics itself. Since memoir become

the second

law of thermody

in Sadi its original Carnot's appearance of 1824, the principle that would eventually the second law was always formulated as a statement, as free of exceptions general or his law of universal laws of motion Maxwell

completely as Newton's gravitation.

What

invariable universal, His challenge took the strange form of what we now call Maxwell's demon, an argument of the "quaintest character" indeed. This was Maxwell's way nature of ex

was just this challenged of the second law. validity

in the 1840s, the basis for clusively demonstrated Carnot's principle seemed to be lost (//). Caloric was not conserved and Carnot's proof no longer held. It was Clausius who saw that the of work equivalence and heat could be made with Carnot's compatible if the latter were modified principle, only slightly had said that heat, Q, must Carnot (12). Whereas be transferred from a hot body to a cold one when work, W, is done in a cyclic process, one could now from the say instead that when heat Q is absorbed hot body, only the difference, Q ? is rejected as heat to the cold body. This revised form of Carnot's

of the pressing his insight into the peculiar law of thermodynamics: it was not a law second to dynamics, that could be reduced ultimately but it expressed
molecules.

instead

the

statistical

systems composed

of unimaginably

regularity large numbers

of of

allowed for the equivalence of heat and assumption to Clausius, it could still serve work, and, according as the basis for a theorem. But proof of Carnot's more than the usual of something impossibility had perpetual motion to carry out the proof. to be invoked as a postulate

Maxwell's

views

on

the nature

of the second

law,

in brief passages and passing remarks, expressed were never developed into a systematic statistical but they show how clearly he saw to the mechanics, heart of the matter. character Clausius ings on character which that it was He was of the second insisting on the statistical law at a time when Rudolf were

indirect reasoning, prov repeated Carnot's his result that the converse ing by showing assuming led one to an evidently intolerable conclusion. For Carnot this had been the appearance of perpetual motion; for Clausius it was it processes "By repeating alternately would be possible, without any expenditure of force or any other change, to transfer as much heat as we please from a cold to a hot body, and this is not in accord with the other relations of heat, since it al dif ways shows a tendency to equalize temperature ferences and therefore to pass from hotter to colder bodies" Clausius (13). This was the new assumption needed on both based thermodynamics the equivalence of heat and work (the first and Carnot's He it more law) principle. phrased a can few never later: "Heat years pass compactly from a colder to a warmer body without some other for the creation of a these two something different.

Clausius

of the man that his mind thoroughly characteristic with could never bear to pass by any phenomenon out satisfying itself of at least its general nature and causes" (S, pp. 319-20).

in their fragmentary show, subject as well as in their penetration, that quality a in sentence: is "It summed Tait up this

and Ludwig Boltzmann a strictly mechanical

trying to show theorem. His writ

The
Carnot "The agents solely which

demon
motive

and molecular
his general power of heat to realize

statistics
result in these words of the is fixed :

formulated

indicates, Carnot was using (70). As the last word the caloric theory of heat, so that for him heat was a conserved fluid: as much as had heat was

employed of the bodies between by the temperatures is effected, finally, the transfer of the caloric"

is independent it; its quantity

in question is the performance of ex change" ternal work on the system, but these specifications were implicit in Clausius' statement. The point to be "other is the universality of word the presence "never," from Clausius. second quotation stressed here It was when here that Maxwell to Tait

therewith, occurring at the same change, connected time" Modern textbook of this formulations (14). are of law to second careful thermodynamics specify that cyclic processes are being considered and that the

low temperature been temperature, when work was performed by a cyclic use of the impossibility process. Carnot's proof made of perpetual that is, of the motion, impossibility, "an unlimited creation ofmotive sumption either of caloric ever" (70, p. 12). When the possibility or heat into work, power without or of any other agent what con

rejected at the at the high absorbed

of the statement, the for example, in the

chose in December

he wrote

of transforming work in a fixed proportion

was

into heat, con

by a fixed diaphragm.

way in which, gested a conceivable in contact, the hotter" could "take heat from the colder without external agency." Maxwell considered a gas in a vessel divided into two sections, A and B, The gas in A was assumed
1970

to "pick a hole" 1867. He sug "if two things are

to
85

January-February

be hotter

molecules well

than the gas in B, and Maxwell looked at the implications of this assumption from the molec a ular point of view. A higher temperature meant higher average value of the kinetic energy of the gas inA had shown

leads for the demon's actions, necessarily to spontaneous fluctuations fluctuations, including that take heat from a cold body to a hotter one. the basis Maxwell came a little closer to saying these things a few his argument

gas would velocities of all possible magnitudes. "Now," Max a finite being who knows the well wrote, "conceive by simple paths and velocities of all the molecules inspection but who can do no work except open and close open a hole without mass."

to those in B. But, as Max compared some years earlier, each sample of contain molecules necessarily having

he repeated explicitly when Strutt (later years later in a letter to John William This Lord Rayleigh). time he referred to the pos of all reversal of the motion sibility of a complete particles in which quite world thereby reversing the sequence events normally occur. This possibility was the assumption that "this consistent with in the world,

only when root mean He would the hole root mean These

in the diaphragm of a slide by means This to be would assigned being an in for A the hole molecule approaching that molecule had square velocity allow a molecule into A only when of a velocity less than the in B. the molecules

violation

is a purely dynamical system." In this time reversed state the trend would always be away from in flagrant would such behavior be equilibrium; of the second law. Maxwell that "the possibility of executing but he did not "think the 2nd more and

to pass through its velocity exceeded the from B of the molecules in A.

square velocity were to be carried out al two procedures so in A that the numbers of molecules ternately,

doubtful," feat to upset now

could be done more described

it requires such a It law of thermodynamics." easily with the help of the demon, graphically as "a

knew, of course, is this experiment

and B would

however, B diminished; that is, the hot system has got hotter and the cold colder and yet no work has been done, and neat only the intelligence of a very observant fingered being only deal with has employed." the molecules directly been If one could and individu

not change. As a result of this process, "the energy in A is increased and that in

very

doorkeeper exceedingly quick, with micro intelligent scopic eyes," who would be "a mere guiding agent, on a railway with perfectly acting like a pointsman one should send the express along switches who line and was the goods along another." The demon

ment

ally in the manner violate the second "not being

of this supposed being, one could law. "Only we can't," added Max enough" (9). talented little

well, This being

clever

argu introduced, however, by this sentence: "For if there is any truth in the dynamical theory of a in uniform of the different molecules gases, gas are temperature moving with very different veloci ties." That served was to make even thing; the demon only its implications transparently clear. from his drew an explicit "moral" the essential

is the first time

that Maxwell's

Maxwell discussion:

on paper. Thomson appeared immediately name him the gave "demon," by which he has been known ever since (5a, p. 214; used 75). Thomson this name only in and

natural

letter to Tait, Maxwell did not make suf probably reason clear his for this fanciful ficiently introducing construction. He described "the chief end" of his demon soon afterwards in these words: "to show that of thermodynamics tistical certainty" (5a, p. 215). He itwould an all hotter the 2nd law has meant only that while a sta

a super its original meaning, want not to did being, suggest any evil intentions on the part of this being who could reverse the common of nature. In his tendency

has "The 2nd law of thermodynamics the same degree of truth as the statement that if you throw a tumblerful of water into the sea, you cannot (76). get the same tumblerful of water out again" should

It is, after all, not surprising that Maxwell have been ready to take the consequences so seriously: he was distribution velocity who well gases had introduced became interested

of the the one

require the action of the demon observable flow of heat from a cold one,

is less significant existence sibility of the demon's than the actuality of the statistical distribution of in a gas at equilibrium. molecular velocities This statistical character enormous
86 American

this process is occurring spontaneously on a the time, scale. The pos submicroscopic

to produce body to a

he read Clausius' papers on the in the Philosophical Magazine (77). Clausius subject use of the idea of the average distance had made between traveled by a molecule its collisions with how the other molecules of the gas. It was Maxwell, in 1859 when ever, who showed how the theory could be subjected to experimental the relationships test, as he derived mean between Clausius' free path and the measur conductivity, re had Clausius Again, although marked the greatest pos several times that "actually sible variety exists among the velocities of the several and diffusion. able coefficients of viscosity, thermal

this concept into physics. Max in the molecular theory of

number
Scientist,

of an system composed of molecules, form which would

58

of a

Volume

molecules" average that an

the nature

no attempt to analyze in a gas, he made but simply used the of this "variety" saw at once molecular velocity. Maxwell of how molecular be fundamental velocities were to the develop

Boltzmann

was

physics, "tracing the simple laws of mechanics" law could

the pursuing the phenomena

classic

program of nature back Since the

of to first

analysis distributed would ment As

of the theory.

he had wrote to George 1859, Maxwell early as May Stokes about his work on the theory of gases, Gabriel "Of course my particles have not all commenting, the same velocity, to the according but the velocities formula are distributed the errors same as are must plain. The colder

(22). be clearly understood the by introducing of molecular not the second, energy motions, why too? Boltzmann himself that persuaded apparently achieved claims his success was state more but for all his sweeping limited. To evaluate itwe very was precisely what he trying to ex his goal,

statement

that "heat

can

never

distributed

was

presented law in his first paper on gases in 1860, pointing out that molecular collisions would alter continually individual the and that what he found velocities, average number of particles whose veloci ties lie between given limits after a great number of "the

in the theory of least squares" (18). He a derivation of this velocity distribution

with

body without an occurring" adequate first thermodynamic studies, but he felt that it was because we cannot "incomplete, therein, recognize had been sufficient theorem" another years

to a warmer

pass from a some other change basis for Clausius'

the real nature of the clearness, was more He satisfied with p. (74, 81). form which he deduced from this a few

among a great number of equal particles" even clearer in a new (19). This relationship became of the distribution derivation law that Maxwell collisions effect of collisions the on the distribution as law and

published in 1866 (20). This time he calculated the

found sta the equilibrium which would be law. This distribution unchanged that distribution

tionary velocity basis of all the calculations

by collisions?the distribution formed

then expressed in very compactly 1865, in a paper which might well have stimulated Boltzmann's work results were these: (3). Clausius' For every thermodynamic a func system there exists is a function of the tion, S, which thermodynamic state of the system. S, which he named the entropy, is defined by the differential relationship,

later and

of the properties of gases thatMaxwell carried out, and it is quite natural that it should also have been the basis for his criticism of law of thermodynamics. seemed natural approach Although to Maxwell, efforts this it to

dS=
reversible infinitesimal

dQ

(1)

the second statistical was

where dQ is the heat supplied to the system in a

very different from contemporary of the second law. probe into the meaning

Attempts
In

at mechanical

explanation

process and T is the absolute of the system. (The notation temperature dQ, not used by Clausius, that not an is emphasizes dQ exact differential.) For processes that are irreversible, one can only state the inequality,

a paper, 1866 Ludwig wrote Boltzmann "On the Mechanical of the Second Law of Meaning was It his first scientific Thermodynamics" (21). work of any significance and to give a general mechanical law. Boltzmann the first serious attempt of the interpretation

dS> dQ ^
In order planation, mechanical that expressions for all of the quantities

(2)
ap

to give the second law a mechanical ex Boltzmann would to find have had

trasting this with the first law, whose identity with the energy principle had been known "for a long time already." This time" was "long only about was only twenty-two fifteen years, but Boltzmann himself. He assurance announced of his age: "It his goal with all the self is the purpose of this article

by referring of the second law exceptional "peculiarly position" and to the "roundabout and uncertain methods" by which physicists had tried to establish it, con

second

began

to the

pearing in (1) and (2) and would have had to show

these mechanical molecular indeed the satisfied satisfy relationships by their thermo All of this should be done dynamic counterparts. for a mechanical character. system of very general coordinates functions quantities, and momenta, do of the

Boltzmann

discover
to it."

to give a purely analytical, completely of the second law of thermodynamics, the theorem in mechanics

had tried to do just these certainly was He least in successful with ir things. dealing reversible processes; his brief discussion of one par ticular example threw no light on the molecular basis for irreversibility.

general proof as well as to

that corresponds

Boltzmann idea, already

did

give

a detailed

expressed

for the justification by others, that temperature

January-February 1970 87

was

a measure

molecule. chanical

of least action, on the strength of which he claimed to have given a mechanical of the second explanation law. This theorem will be discussed

of the average kinetic energy of a a He also proved very interesting me of the principle theorem, a generalization

where

dL

represents

enough for the present to point out could prove it only under a very restrictive assump to limit himself to periodic had tion. He systems. For a system whose entire molecular configuration itself after a time, r, he found a mechanical to the entropy, S. Boltzmann's counterpart equation repeats for the entropy of such a system had the form,

it is later; that Boltzmann

total work dL was the sum of dl and work, /. The the usual external work, dW, or PdV.) It was (5) as saw that Clausius the ultimate thermodynamic formulation of the second law: "the effective of heat is proportional to the absolute temperature"

(Clausius U, of a system to be the sum of two terms, both state functions?the heat in the body, H> and the internal

ferential.

considered

the total work, an inexact dif the internal energy,

force

a mechanical Clausius5

which Clausius tried to find (25). And itwas (5) for

interpretation. first attempt, in 1870, did not succeed, but be called a failure since it led him to following year he was the problem, as he en of the Second the Reduction to General title sounds Mechanical

S = 2 ln(7?2 +
where the sum is over

constant,
The

(3)
absolute

it could hardly the virial theorem convinced

all molecules.

(25). The that he had solved

temperature, T, is the kinetic energy of one molecule averaged over the period,

titled his paper, "On of Thermodynamics Law This

(4)
the period, r, appears explicitly in the entropy equation one is inclined to guess that the periodicity of the system is an essential aspect of the theorem. Since tried to extend

like very much (26). Principles" and with of that of Boltzmann's 1866, paper good reason. Clausius the discovered had independently theorem

Boltzmann

his proof to nonperiodic orbits are not closed, the particle systems, where rather but his argument was not cogent. It concluded are not "if the orbits that the remark with lamely closed in a finite time, one may still regard them as closed in an infinite time" however, (It may be worth (23). the entropy, that one can evaluate

five years earlier. by Boltzmann published were the same, there were some results the Although had been look Boltzmann differences in approach. ing for a mechanical its properties, while

central position

de simply related, however, and the entropy Clausius for disgrega rived from his mechanical expression had found tion was identical with the one Boltzmann

interpretation of entropy and the Clausius gave disgregation two functions are in the theory. The

with the help of (3), for a very simplemodel of a

back and of particles collection gas?a bouncing the walls of a container of volume V, forth between all particles moving with the same speed, v. The re In (VT^2), sult does depend linearly on the quantity as it should for an ideal gas of point particles.)

noting,

directly (see (3) above).

Boltzmann siderable chanical wasted priority no time in pointing out his con in having this me established

Boltzmann reduce Rudolf ismuch he wrote

was

not had "the

the second Clausius

tried to the only physicist who law to a theorem in mechanics. been thinking about the second second law of thermodynamics

law since

1850; harder for the mind

once (3, p. 353). must be pointed follow the evolution of his ideas, but it a out that Clausius arrived at very particular way of looking at the second that he named concept law (24). He introduced

to grasp than the first," to is not the place This

is helping to spread the knowledge ius' reputation on work (27, p. 236). my thermodynamics" Clausius of course, had, had He memoir. overlooked moved to Bonn

of the second law (27). He showed analogue identical basic equations were that all of Clausius' with his own, apart from notation, reinforcing the the relevant pages of verbatim point by reproducing his earlier article. "I think I have established my concluded, adding, "I can only priority," Boltzmann an authority with Mr. Claus express my pleasure that of

Boltzmann's to in 1869, and on his time

total work, internal as well as external, done by a a in reversible process. This relationship was system fixed by the equation,

intended the disgregation, as a measure in which the molecules of "the degree It was to be a thermody of a body are dispersed." state function, denoted namic by Z, related to the

in 1867 and again W?rzburg demands" the resulting "extraordinary and energy had prevented him from keeping the literature mann's claim properly. to priority He

original

from Z?rich

obviously for all the results common

up with granted Boltz

dL = TdZ
88 American Scientist, Volume 58

(5)

matters

that to both papers, but Clausius was not convinced or as sound as were Boltzmann5s general arguments to discuss some of these as his own, and he proceeded in detail (28).

Limitations
Maxwell mechanical

of the second
this and

law
over "It the law with is rare

which

Maxwell after

treated

at

some

observed

interpretation no little amusement. detachment?and sport to see those learned Germans the priority of the discovery that

later disputes of the second

two years

the publication

(32).
In discussing that Carnot's the second

length, less than of Gibbs's paper

for contending the 2nd law of

a thing which was sug vis viva of one of its molecules, etc., but gested by the labours of Gay Lussac, Dulong, from dynamical first deduced statistical considera Hamiltonsche region the German

is theHamiltonsche 0Acs [thermodynamics] Princip," he wrote to Tait, "when all the time they assume that the temperature of a body is but another name for the

law, Maxwell emphasized does not follow from the principle first law, but must instead be deduced from an in a hence second law. He dependent assumption, and Clausius' versions of this law, quoted Thomson's both of which asserted, in effect, the impossibility of a cyclic process the heat of a body into converting work without to pass from that heat allowing body to a colder one. He advised the student to compare the various statements of the law so as "to make an him selfmaster of the fact which they embody, acquisi to him greater importance on which a demonstration constructed." Maxwell And to went

tions by dp/dt [i.e.Maxwell:

Icari flap their waxen wings in nephelo amid those cloudy forms which the igno coccygia rance and finitude of human science have invested with Queen The the incommunicable of Heaven" prize for which (29). "those learned Germans" were attributes

soars along in a the while, Princip, unvexed statistical while considerations, by

see Appendix]. The

tion which will be ofmuch

of the invisible

than any form of words or less compactly may be more then in his next two paragraphs the crux of the question.

contending dynamical
result.

was an illusion : the second law was not a theorem at all, but an essentially statistical

that a body contains energy in the form Suppose of heat, what are the conditions under which this or of it be removed from the energy any part may body? If heat to distinguish able these parts, and parts, and to guide and control their motions by our then by arranging any kind of mechanism, so as to lay hold of every apparatus part moving a of the body, we suitable train of could, by transfer the energy of the moving mechanism, of the heated parts body to any other body in the form of ordinary motion. The heated body would thus be rendered perfectly cold, and all its thermal be converted energy would tion of some other body. into the visible mo if we in a body were consists in a motion of its

Maxwell meaning

expressed of the second

some

of his law

own

ideas

on

the

published in 1871 (30). This book appeared as one of

a series, described of science adapted students as "text-books by the publisher for the use of artisans and of

in his Theory

of Heat,

meant

men, .. . reduced description. ably "more writings" elementary

in public and science schools." They were to be "within the comprehension of working and suited to their wants," with "every theory to the stage of direct

tion" (31). Maxwell's

Tait

thought that some of it was prob difficult to follow than any other of his it was "not an (!) and that as a whole book." and His

book did not quite fit this

and useful applica

Now

interesting, few knowable

know," men readily perceive between what is easy and what is hard. What he called hard, others would be in clined to call

did not things which Clerk-Maxwell he wrote, "was the distinction which most

of this fact was explanation accurate. "One of the probably

necessary dilution) of its varied contents" (8, p. 320). did not hesitate to include discussions Maxwell of the latest work editions audience thing of his book like Willard in thermodynamics in the successive ; one wonders what his intended and students" made of some surface, Gibbs's thermodynamic

As a con altogether unintelligible." book contained "matter enough sequence Maxwell's to fill two or three large volumes without undue we dilution should rather the with say, (perhaps

if the heat in the consists Hence, of its parts, the separate parts which move must be so small or so impalpable that we cannot in any way lay hold of them to stop them [30, motion pp. This 153-54].

discovered.

with the first law. The second law is to a denial therefore equivalent of our power to the either by a perform operation just described, or by any other method train of mechanism, yet

consistent

this supposition involves a direct contradic to tion the second law of thermodynamics, but is

of "artisans

so argument, simple in appearance, deceptively out the that had Boltzmann brought point escaped and Clausius, others. Those that among processes are declared to be impossible by the second law are the laws of mechanics. perfectly consistent with The second law must, some es therefore, express
January-February 1970 89

If it is to sentially nomiiechanical aspect of nature. receive an explanation at the molecular level, that must to refer the smallness of molecules, explanation to their enormous numbers. This or, equivalently, is really the same point of view that Maxwell had in his demon already expressed privately argument. made the connection himself in the last chapter of his book, which dealt briefly with the molecular In a section entitled "Limitation theory of matter. of the Second remarked as we of Thermodynamics," that this law "is undoubtedly Law Maxwell true as long and have no

the motions and are

so numerous, so small individually, and so that they quite escape irregular in their distribution, of observation; all our methods whereas when the are those of visible bod displacements ies consisting of great numbers of molecules moving the communication of energy is called altogether, and If one could that individual supposed be followed, as one would molecular work and theory, then heat would

and displacements which are concerned in the communication of heat are those of molecules,

motions

He

(7, p. 669). molecular motions have "the to do At

work"

only inmass, or of the separate mole power perceiving handling are cules of which status of the made they up." The second law would be very different if we had the powers of "a that he can Maxwell being whose faculties are so sharpened follow every molecule in its course." how described the second law could be one

can deal with bodies

in a dynamical distinction between themolecular

vanish."

level there is no mechanical

distinction to deduce

principles, be a "sufficient This second conclusion

between work and heat, and so no attempt law from purely dynamical the second however satisfactory it might appear, could explanation" has of this law (7, p. 671).

flouted by such a demon, just as he had described his letters to Tait and Strutt. As a consequence, had to be careful about

it in

a certain

Maxwell

extending conclusions "drawn from our experience of bodies consisting of an im mense number of molecules" to the "more delicate observations if individual handled. "compelled and and perceived that should become possible we were . . . the statistical method to adopt of to abandon and the strict dynamical be 328-29). experiments" molecules could that might be made

was probably quite law denies the possibility of the second kind: machines

it, and irony about aware of that. The of perpetual motion no matter how in

genious one of these devices may seem to be, one can be certain that in some way or other its existence had cast would violate the laws of nature. Maxwell in precisely the same form: no matter a purely dynamical how proof of the convincing second law might seem to be, it could not adequately his conclusion explain the limited convertibility of heat into work.

Unless

calculation, method" (30, pp.

The
Maxwell

inadequacy
returned

of mechanical
to he was Sketch these asked

explanation
a few the second

Maxwell

considerations to review

of Thermodynamics. Written fatal illness, this only a year or so before Maxwell's review contains his final reflections on the subject of in his most presented thermodynamics, in another style. (As Tait himself remarked tion, "No condensing few clear brilliant connec

years later, when edition of Tait's

did not?that might have observed?but one of the subjects for dispute between "those learned was precisely the proper way of describ Germans" ing work and heat at the molecular level. Boltzmann in which each 24-28) imagined a process amount same of was the supplied with

(27, pp. molecule

sentences than Maxwell" compact of Maxwell's review was devoted [8, p. 321]). Much to the second law, since he thought that the manner and in which an author handled of a this treatise "the touchstone

living man has shown a greater power of the whole marrow of a question into a

was his way energy, e. The sum of e for all molecules to the system, but he of representing the heat added gave no indication of how this ewas to be supplied to did have to require that Boltzmann each molecule. this energy went either into work done against ex ternal forces or into an increase of the kinetic energy

formed namics" The old

thorny subject on thermody

(7, p. 667). offered a new variation on Maxwell's

this average was no attempt made the individual

its of that particular molecule, explicitly excluding be to This molecules. other transfer might partial reasonable enough on the average, but the nature of never also Boltzmann analyzed. to clarify how the work done by

review

theme of the irreducibility of the second law to pure dynamics. The whole point of the second law on the distinction two modes between of depends communicating heat and work. Maxwell energy from one "According "the observed, body to themolecular to another, theory," between is that

molecules, only very represented was to to work done by the be related schematically, a in under the gas pressure. The piston displacing coordinate the gas, appeared Clausius not

of the piston, that is to say, the volume of never coordinate, being a molecular in his equations. criticized Boltzmann's treatment of

these two kinds

90 American

only of communication
Volume 58

difference

of energy

(28)

Scientist,

some of these points, and this was absolute not grant Boltzmann's mechanical derivation

the reason

he did

for the priority own law. His of the second

of the motion, the external work done by the A is In Aa. this case the change in energy, system just AE, is just the negative of the work done, and the com period plete variation slow variation so important the variation of the action, (6), still vanishes. This is the Ehrenfest adiabatic process,

the po way of treating the work involved making on a function depend tential energy parameter. from one which varied in This turn, parameter, orbit

to change uniformly to another, was assumed went as the particle with time through a complete like that Clausius, orbit. It must be remembered even make could precise reasonably Boltzmann, in closed the particles moved arguments only when was system. Boltzmann orbits, that is, for a periodic

still calls AAa heat

in the old quantum theory (35). When is not carried out at this very slow pace the right-hand side of (6) need not vanish. If one

to the system. supplied to the directly equation,

then it is proper to identify AE +

In

the work,

AW,

done

that case

AW with AQ, the

(6) leads

by

the system,

the laws not happy about Clausius' way of "allowing never this and with to nature of adopted vary time," of the in his later discussions problem procedure

2A(rT)
This is easily rewritten AQ

tAQ.

(8)

(33).
Perhaps the best of seeing the difficulty of way and heat in a mechanical theory is

in the form,

=Aln(7?2,

(9)

separating work of the clear exposition to look at the particularly Ehren Paul theorem Boltzmann-Clausius given by considers a system whose Lagrangian fest (34). One on a set of generalized q, the coordinates, depends a and param velocities, q, generalized corresponding in the case of a gas. eter, a, such as the volume to be periodic, and to remain The system is assumed in a variation (but with a changed period) periodic a orbit. This to orbit the from neighboring original in the is of the kind considered variation principle but the two i.e. nonsimultaneous, of least action, orbits are also assumed eter has the value a + to differ because Aa rather than a on the param the new Ehrenfest

which

is equivalent to (3), the Boltzmann-Clausius the when average kinetic energy is set equal result, to the temperature.

The with

argument the work

reason for this identification. The work compelling is the integral, fa ?+ AaAda, and this is not equivalent is of the order to A Aa when the time of the variation no or is obvious way There the less, than, of, period.

of AAa hinges on the identification done by the system, but there is no

two separate modes of energy of distinguishing is transfer as heat and work in such a process. This an illustration of Maxwell's mechanical never explanations no matter be adequate, appearance may be. statement general law of the second how impressive that can their

orbit. By the usual variational the equation, derived

procedures

(6)
The varia A represents the change in the generalized T is the kinetic energy, E is the tion just described. total energy, and r is the period of the system. The the equations, quantity A is defined by

outward

Boltzmann
Maxwell was mechanics

and
not that does

statistical mechanics
the one

(7)
force that must be ^4) is the generalized the system to hold the parameter, <z,con exerted In the standard A time is its and average. stant, treatment of the principle of least action there is no variation of a parameter, a, and the variation of the so that ? ( on

to develop the statistical law. He was second the explain to that "the have satisfied recognized apparently nature of a strong truth of the second law [is] of the . .not an absolute certainty" (7, p. 671), probability. on the un in an essential way that it depended that con of molecules large number imaginably was who Boltzmann It bodies. stitute macroscopic undertook make the task of creating a statistical clear just how a mechanical could show But work,

would

theory that system of

E. As a path is carried out at constant total energy, is just the of the action, which result the variation time integral of the kinetic energy, vanishes. When the parameter, 0, is varied slowly, so that the to the occurs during a time long compared

so many

thermodynamics. by the found his starting point inMaxwell's he had a profound admiration. At the time when Boltzmann

particles laws of

the behavior

required Boltzmann for which

variation

tried to account
January-February

for the
1970 91

second

law

or his law but did not mention Maxwell Clausius, of molecular velocities for the distribution (36). We was learning to read English know that Boltzmann at this time-?in order

parently on the theory of gases. When he quoted the relation the pressure of a gas and the velocities ship between and of itsmolecules, he referred to Kr?nig, Rankine,

in purely mechanical terms, he was ap had written unfamiliar with what Maxwell

mann

made

constant

use

of the statistical and

distribu the result

energies, to be a certainty and not supposed just a probability. The //-theorem of 1872 said that entropy would (47, p. 345). Boltz always increase mann did not revise this statement until 1877, when he asserted was Josef Loschmidt in its original tion of the molecules two senses are invariant pointed form (42). out Since that it was untenable of mo the equations the do not distinguish between

tion of molecular

velocities

to read Maxwell's papers on to He returned the (37). theory of electromagnetism gases in 1868, however, with fresh ideas prompted new analysis of the kinetic by his study ofMaxwell's on a series had embarked theory (38). Boltzmann in which the statistical descrip of lengthy memoirs central to his treat tion of the gas was absolutely

in which

time reversal legitimate

a con As of the equations. solution in the for of molecules motion which any sequence, one could the entropy of the gas increased with time, construct creased another motion with

time might flow (that is, they to the replacement of / by ?the is an equally of any actual motion

ment.

of the law, but this time it was a statistical rather than a mechanical, mechanical, proof (39). as This new proof dealt only with the equilibrium proof

was criticizing the fine By the time Clausius points of his mechanical of the second law, interpretation was already committed to the statistical Boltzmann In that same year, 1871, he offered a new approach.

in which the entropy de in to the contradiction time, apparent was in to law. It his Loschmidt's second only reply "how inti criticism that Boltzmann recognized mately the second and law is connected probability," only be described certain. He later that same that the increase

is, with the existence pect of the second law?that as a of the entropy state function re thermodynamic in the proper way, lated to heat and temperature through

the year, in which he formulated a of between the entropy relationship thermody con state and of molecular namic the number with that state (43). Entropy figurations compatible a measure of this "thermodynamic became simply probability." can be viewed legitimately as a of first the expressed by Max development insight well?an and quantitative de extended, detailed, Boltzmann's work of a brief qualitative velopment insight, to be sure, all the same. Neverthe but a natural development, seems to have taken little or no interest lessMaxwell in these papers He did by Boltzmann. Boltzmann's work of aspects follow some in statistical

as very highly probable, but not as this view in a major elaborated article

to the theory of in entropy can

equation distinguished with tion: roughly

in the molecular produced by a change potential a was work, whereas with fixed distribution energy heat was identified with a change in the energy due only to a change in the distribution. The exponential an im at equilibrium energy distribution played in the The essential features portant part analysis. of Boltzmann's have survived the transi argument to quantum tion from classical it is physics, and still to be found in textbooks on statistical mechanics

now and heat were (1). Work the help of the distribution func speaking, a change in the total energy

(40).
was able to provide a molec A year later Boltzmann ular basis for the other aspect of the second law, the increase of the entropy of an isolated system an irreversible process occurs whenever (47). This came as a by-product of an investigation into the Boltzmann's result, orem, was based on his analysis of how the distribu in time as a result of binary molecular tion evolved collisions. Although much more limited in its scope than his discussion of equilibrium, the //-theorem the first insight into the nature of irreversi uniqueness distribution. of the Maxwell-Boltzmann equilibrium the famous //-the

particular a Maxwell's last scientific work was mechanics; new analysis of the equipartition theorem, taking as its starting point and Boltzmann's 1868 memoir some of the presenting an alternate way of handling difficult aware William which was (44). Maxwell assumptions certainly of much of Boltzmann's other work. Henry Watson's little book on the kinetic version in 1876 (45), a modified followed

appeared methods and included mann's

theory, Boltzmann's of Boltz of an

first statistical derivation

of the existence

entropy function. Watson assistance" from Maxwell well where namics. also reviewed did Maxwell It

"much kind acknowledged in his Preface, and Max forNature (46). But no Boltzmann's statistical

the book discuss

offered bility.

mechanical Tait, where

theory of the second is not even mentioned it would have been

law of thermody in his review of completely ap

It must
92 American

be

emphasized,
Scientist, Volume

however,
58

that while

Boltz

propriate.

There

is no obvious

point. It is true that their styles hard found Maxwell very different. Boltzmann of his terseness (38, p. 49); because to understand found the great Maxwell length of Boltzmann's were discussions wanted never to be "an to reduce read one stumbling block" equal to "about of his papers memoirs 1877, the relationship of and six so

of intellectual mann at this one

explanation contact between

for the peculiar lack and Boltz Maxwell

version of what was, of course, an exaggerated Maxwell had originally said. He had looked for pos sible limitations of the second law, but he had never to intended it. Clausius, certainly destroy This used

lines" (47). It may well be thatMaxwell

Boltzmann's the pleasure tween entropy and probability. of seeing

and

simply
be

to Tait's and practiced in counter onslaughts a them with had proper answer to ing equal vigor, "I believe this new attack: I can summarize my in the brief remark that reply toMr. Tait's objection my law is concerned, not with what heat can do with the help of demons, but rather with what it can do no saw reason He itself" the existence (50). by why of fluctuations the average should be considered behavior described as contradicting by the second law.

missed

Fluctuations
Maxwell

and

the demon
as a way truth of giving not Maxwell's

life to the difficult idea that the second law of

is a statistical This idea and a certainty. circle. William on quickly

conjured

up his demon

thermodynamics dynamical inMaxwell's

caught Thomson incorporated it in a paper it into his own thinking and elaborated on the kinetic theory of energy dissipation. He went demons so far as to imagine an army of Maxwell's stationed of this "ideal

not essentially different. He the two very different ways of "The second law," thermodynamics. establishing he wrote, "must either be founded on our actual ex saw no conflict between perience in dealing with or else deduced real bodies from of sensible mag the molecular

own view was

member

cricket bat," and club, or, as it were, a molecular the variety of ways in which such an army described control molecular could processes (48). But even was playful enough though Thomson and arms and hands "with demon hands and ten fingers they had been raised suffice" called to endow

at the interface of a hot and a cold gas, each army" being armed with "a

nitude, theory that the behaviour of these bodies, on the hypothesis of molecules of bodies consisting of millions may be encounters of of the from the deduced pairs of theory of the relative molecules, frequency by supposing different cording Real kinds of encounters to be distributed ac to the laws of probability (/, pp. 669-70).

the

well why paper of 1874 which years

Loschmidt

later, and in much paradox,

the reversibility paradox with a few would confront Boltzmann that it was no real also showed

fingers?two knew very he (49), into being. Thomson's

ular

the way Boltzmann would. Thom of the probability son went further. He calculated that are an inescapable the fluctuations aspect of the statistical that while it was not im

critical opalescence, Brownian motion, tatively?the in colloidal fluctuations suspensions?and density for all of them. By the statistical theory accounted von Smoluchowski could give an in 1912, Maryan vited lecture with "Experimentally that Contradict the "revolutionary Molecular Verifiable

support for the statistical molec experimental come until the early years of not did theory this century, but then it came in strength. A whole was studied quanti series of fluctuation phenomena

title sounding" Phenomena

theory, showing one would find all the oxygen molecules that possible in a vessel of air in the left-most fifth of the container, the probability Tait of this event was staggeringly

small.

the statistical molecular approach to the second pointed out in his lectures that a colder to molecular processes taking energy from a a warmer going on, but on body are "constantly mass of a gas." This fact very limited scale, in every of Carnot's the validity did not interfere with also absorbed law. He theorem and could be for "the enor

(57). A Ordinary Thermodynamics" to have decade earlier "it would have been foolhardy formula of the traditional spoken so disrespectfully at least on the continent tion of thermodynamics," There was now good reason for taking of Europe. statistical approach Maxwell's seriously. completely law in the second had picked hole Maxwell The had become Smoluchowski's plainly visible (52).

brilliant

safely ignored mous number of particles in a cubic inch of even the also But Tait most rarefied gas" (15, pp. 119-20). a con be to fluctuations such of existence found the to beat his old antagonist, venient stick with which that the demon argument was Clausius, commenting fatal to Clausius' reasoning." "absolutely

showed phenomena tions of almost all the usual

analysis of the fluctuation viola that one could observe statements of the second

the impossibility of a perpetual of fluctuations, was of the second kind. No device could ever be motion
January-February 1970 93

law by dealing with sufficiently small systems. The the increase of entropy, trend toward equilibrium, and so on, could not be taken as certainties. The one statement that could be upheld, even in the presence

made scale.

that would For

vert heat stituted

to con the existing fluctuations on a work into macroscopic completely to be con have any such device would use and would therefore itself be

Appendix.
James friends

On Maxwell's
often

Signature

Clerk Maxwell as Thomson

of molecules

and

use the subject to the same chance fluctuations. To a one to construct would have fluctuations molecular device "Only
clever

whose we

not be action would as had Maxwell can't,"

limited by them. said, "not being

also used dp I dU He plume for the witty verses on scientific subjects that in Nature he published (53). It is not hard to guess that he was making private reference to an equation of the form

signed letters to such with the signature as a nom de derivative this Tait

enough."

f at
that dp/dt simply what was the equation, late D. K. as one of Maxwell's of so

dp

= JCM
his did

(Al)
initials. But it come from?

represented and where

The

C. MacDonald

Heat from the (54), derived by him in the Theoryof

geometry pp. isothermal now and adiabatic curves 165-69), equality of themixed and commonly second derivatives derived (30, from the

it recently described four thermodynamic relations

of the various

statement thermodynamic potentials. MacDonald's is technically correct but historically misleading. To in (Al) Maxwell the relationship the expressed second law of thermodynamics statement itself.

Carnot's

of his fundamental of heat

theorem

said

that the motive temperatures the working

mathematical A

power depends only on the between which heat is transferred in of an engine. This was translated into

slightly modified the following way. an

terms by Emile Clapeyron in 1834 (55). version of the argument runs in

Consider an

cycle consisting ot at temperature isothermal expansion (/ + dt) an adiabatic which cools the expansion system down to temperature isothermal at t, an compression a and final adiabatic t, temperature compression back to the initial state, all processes being carried out reversibly. Since the cycle is infinitesimal it can as a be represented in the pressure parallelogram area of this volume diagram. The is parallelogram the work, AW, done per cycle and it has the value Carnot

infinitesimal

AW = (dp) (dV)
where

(A2)

Carnot's motive

the difference in dp and dV are, respectively, between two the isotherms and the dif pressure ference in volume in either isothermal step. The ef ficiency of the cycle is the ratio of AW to AQ, where in the isothermal expansion. AQ is the heat absorbed that this efficiency, "the power of heat," depends only on the tempera tures t and t + that it can be ex dt, which means as dt is since infinitesimal. Here pressed C(t)dt is a universal function (the Carnot function) theorem states

C(t)
94 American Scientist, Volume 58

of

the

measured

/, this temperature, temperature on any arbitrary scale. If one

t, being introduces

Thomson equation

did

not

use called dp

this notation. (Al)

He

wrote

the

we have

in the form

the mechanical fact that heat

of heat, J, to allow for the equivalent in different and work were expressed Carnot's theorem

the equation units, expressing can be written in the form AW

i
where which function and

=M

(A6)
of temperature, function. The the equivalent inexact dif

= CM A

function juwas the universal Thomson called the Carnot /x incorporates is the integrating factor for

(A3)

the mechanical

The

of heat absorbed pro is, however, quantity so that extent to of the the dV, expansion, portional one has the equation

ferential dQ. Where, then, did Maxwell get the particular him of the Carnot allowed theorem which form to use

AQ
where heat M absorbed per unit

= M dV
of proportionality, in an volume change

(A4)
the iso

is the coefficient

dp/dtas his signature?The first use of C(t) in the formof (A3) and thefirstappearance of (Al) occur
together in that same Sketch of Thermodynamics which demon. It was Tait who called forth the Maxwell renamed the Carnot of

thermalexpansion.With thehelp of (A2) and (A4),

the efficiency equation now becomes

ihw)
or, with dp

/ x {dp) (dV) -c

(A5) (A1)
by Maxwell's represents the , ,

a slight rearrangement,

ft
This and is the basis Tait's second There

= JCM'
(Al) (56).

is correspondence men wrote sorts. of various Both joking well, and often playfully; both were sensitive to ques tions of terminology and notation. fortuitous. The Tait-Maxwell full of verbal Tait actually commented on his old friend's thermo scien to him

was namics (4, p. 91). It is not very likely that this

his C(t) the function, making absolute and who the temperature, reciprocal into the second law of thermody thereby put JCM

of the assertion made

that biographers law of thermodynamics a

is, however, that. It is obvious in an

little more

in (Al) express this result, but not all the notation com were was standard. Pressure and temperature on the by p and /. The quantities monly denoted had no standard designa other side of the equation tion. In his first papers on thermodynamics, William had used J for the mechanical Thomson equivalent, probably in honor of Joule, and M

pends

essential

that Maxwell's way on the notation

to the story than use of dp/dt de used

of his initials in the well by me from the occurrence Law of Thermody second known expression of the on establishment namics thoroughly (for whose

signature in his notice of Maxwell's dynamic tificwork: "This nom de plume was suggested

to

valid grounds he did somuch) dp/dt = JCM" p. 321).

first appearance

(8,

in the Maxwell of dp/dt to a on from Tait is Tait postcard correspondence Maxwell early in 1871 (59). Tait addressed Maxwell The as

then usually denoted by dQ/dV (57). But it is C

that is really interesting.

for the quantity

Clausius its universality. to establish of data that confirmed also and used C as Clapeyron had, ideal was to the C (58). In gas temperature equal and as used notation C(t), modern by Clapeyron to the absolute temperature. is proportional Clausius, kinds

first made explicit use of the universal Clapeyron is called for function of temperature whose existence theorem. He did call itC(t), but Clapey by Carnot's is essentially the reciprocal of the function ron's C(t) of this central defined by (A3). The importance was function universal by Clapeyron, recognized from several different it numerically who evaluated

of his Sketch in which to the paragraph (Al) for Tait, is the shorthand designation is stated. T; their famous was used to designate Thomson, just as T as and T' T to referred book being by the inner reference
circle.

"[= JCM (T"s Thermodynamics ? 162]." This is a

dp/dt, and

added

an

explanatory

parenthesis:

is, however, It occurs Maxwell.

There

an

even

earlier

use

in a

letter to Thomson

of dp/dt by in April

card pointing 1870 (60), almost a year before Tait's to JCM, but well over a out that dp/dt is equivalent book. This of Tait's sug year after the publication the equa noticed had already gests that Maxwell for his benefit tion that Tait redesigned probably and did not need to have it pointed out explicitly to him. He was certainly clever enough.
January-February 1970 95

Acknowledgments
This work was the National in part by a grant from supported Science I thank Dr. Foundation.

Motes
1. J. C. Maxwell, "Tait's Thermodynamics" Nature 17 (1878), 257. Reprinted in The Scientific James Clerk Maxwell, Papers of ed. W, D. Niven (Cambridge, 1890), Vol. 2, 660-71.
Quotation 2. R. 3. R. Clausius, from p. 662. Abhandlungen ?ber die mechanische f?r W?rmetheorie

Elizabeth Garber for many informative discussions on Maxwell, and my colleague Professor Derek J. de Solla Price for the use of his copy of the Cambridge collection ofMaxwell University correspondence.

(Braunschweig, 1864). W?rmetheorie," Pogg. Ann. 125 (1865), 353. 4. P. G. Tait, SketchofThermodynamics (Edinburgh, 1868).
5. For further discussion of this controversy see: (a) bequeme verschiedene "?ber Clausius, der Hauptgleichungen Formen die Anwendung der mechanischen

Peter Work of Guthrie Tait (Cambridge, Knott, Life andScientific 1911), 208-26. Referred to below as Knott, Tait, (b) M. J. Klein, "Gibbs on Clausius," Historical Studies in the Physical Sciences1 (1969), 127-49.
6. R.

C.

G.

(Braunschweig, 1879), 324-30.

7. Knott,

Clausius,

Die

Mechanische

Warmetheorie,

2d

ed. Vol.

8. 9. 10.

JamesClerk Maxwell (London, 1882). Life of

P. G.

contains extensive from this corre Tait, excerpts as well as a of the of Tait spondence description relationship and Maxwell. see L. Also and W. The Campbell Garnett, Tait, "Clerk-Maxwell's to P. G. Tait, 213-14. Reflections contains on the Motive Power Scientific 11 December Work," Nature 21

(1880), 321.
J. C. Maxwell Knott, Tait, S. Carnot,

1867. Reprinted of Fire, trans. R. H.

in

Thurston, ed. E. Mendoza

volume also sius. It is referred 11. See, e.g.,

references. 12. R.

M. J. (Leipzig, 1919), 269-71. Also see Klein, n. 5, forfurther

and R. Clau papers by E. Clapeyron to below as Mendoza reprint. E. Mach, Die der W?rmelehre, 3d ed. Principien

(New York,

1960), 20. This

die bewegende "?ber Kraft der W?rme, und Clausius, die Gesetze, welche sich daraus f?r die W?rmelehre selbst ableiten Trans, lassen," Pogg. Ann. 79 (1850), 368,500. by F. Magie W. in Mendoza see J. W. reprint. Also Gibbs, "Rudolf Julius

(1889), 458. Reprinted in The Scientific Papers ofJ. Willard Gibbs (NewYork, 1906),Vol. 2, 261,
13. R. 14. R. Clausius in Mendoza "On Clausius, mental Theorem reprint, 134. a Modified Form in the Mechanical Lectures Kelvin, on of the Second Theory Some Funda of Heat," Advances

Emanuel

Clausius,"

Proc.

Amer.

Acad.

16

Phil.Mag.
15. Also William 16. see

12 (1856), 86.
P. G. Tait,

in Physical Science, 2d ed. (London, 1876), 119, and Sir

Thomson, Baron Mathematical and Physical

Recent

Papers,Vol. 5 (Cambridge, 1911), 12,19.

J. C. Maxwell to J.W. Strutt,

inR. J. Strutt,Life ofJohnWilliam Strutt, Third Baron Ray leigh(Madison, 1968), 47. 17. R. Clausius, "The Nature of theMotion Which We Call Heat," Phil. Mag. 14 (1857), 108; "On theMean Lengths of thePaths Described by the Separate Molecules ofGaseous Bodies," Phil. Mag. 17 (1859), 81. Both are reprinted in S. G. Brush,KineticTheory, Vol. 1 (Oxford, 1965). 18. J. C. Maxwell toG. G. Stokes, 30 May 1859. Quoted by
Brush (n. 17), 26-27. 19.

6 December

1870. Reprinted

Gases," Phil. Mag.

Papers, Vol. 20. J. C. Maxwell,

J. C. Maxwell,

"Illustrations

1, 377-409. "On

19 (1860), 19; 20 (1860), 21. Scientific

Quotation the Dynamical from p. 380. Theory of Gases," Phil.

of the Dynamical

Theory

of

Mag.
Vol. L. 21.

2, 26-78.

32 (1866), 390; 35 (1868) 129, 185. Scientific Papers,

des Bedeutung Wiener Berichte 53 Wissenschaftliche

die mechanische "?ber Boltzmann, zweiten der W?rmetheorie," Hauptsatzes 195. Reprinted in L. Boltzmann, (1866),

96 American

Scientist,

Volume

58

Abhandlungen,ed. F. Hasen?hrl
9-33. This collection will be Abh., and page this reprint. 22. H. Hertz, trans. D. 1956), 23. references

to as Boltzmann, Wiss. are made to Boltzmann's to work referred Presented (Reprinted in a New New

(Leipzig,

1909), Vol.

1,

Wahrscheinlichkeitsrechnung

W?rmegleichgewicht,"
Wiss. Abk., Vol. 2,164-223. "On 44. J. C. Maxwell, Distribution Trans. 713-41. 45. H. W. 46. 47. Watson,

Wiener Berichte 76

respektive

den

S?tzen

?ber

das

(1877),

373.

Boltzmann's in a

The Principles E. Jones and Preface.

Mechanics of J. T. Walley

Form, York,

of Energy Cambr. Phil. Soc.

Author's

on the Theorem Average of Material System Points," 12 (1879), 547. Scientific Papers, Vol. 2 on theKinetic Theory of Gases," of Gases Nature in Knott, (Ox 16

Wiss. Some years later Boltz Boltzmann, Abh., Vol. 1, 30. mann that could systems nonperiodic proved (open orbits) not be handled these methods. See L. Boltzmann, by "Bemerkungen W?rmetheorie," Vol. 2,122-48. ?ber Probleme der mechanischen einige Wiener Berichte 75 (1877), 62, or Wiss. Abh., of to the the Theorem Internal Work of the of a

A Treatise "The to P. G.

ford,1876).
J. G. Maxwell, J. C. Maxwell Tait, 114. Nature 9 (1874), Kinetic Theory

(1877), 242. This isnot reprinted in theScientific Papers.

Tait, August 1873. Quoted

24.

R.

Clausius,

Mass ofMatter," Phil. Mag.

J. Klein (n. 5) and E. E.

Equivalence

the Application "On of Transformations Daub,

48. W. Thomson, "The Kinetic Theory of the Dissipation

Energy," 49. W. Vol. 50. R. 441. Papers, Demon Vol. 5, 13. Thomson, 5, 21. "The Sorting of Maxwell,"

of

24 (1862) 81, 201. Also seeM.

"Atomism Theorem and Thermo

Papers,

dynamics," Isis58 (1967), 293.

25. R. Clausius, "On 172-78. a Mechanical

Heat,"
Kinetic 26. R.

Phil. Mag.
"Uber

40

(1870),

122. Reprinted
des

Applicable

to

in Brush,
Haupt

Theory,

n. 6, p. 316. Clausius' comments on Maxwell's Clausius, are discussed demon "On the Foundations by L. Rosenfeld, of Statistical Acta Physica Polonica Thermodynamics,"

Clausius, satzes der

die Zur?ckf?hrung mechanischen W?rmetheorie Principien," Pogg. Ann. 142

zweiten auf

(1955), 37-38.
v.

14

mechanische 27. L.

(1871),

allgemeine 433.

51. M.

?blichen 52. A

Smoluchowski, Thermodynamik of analysis information

"Experimentell

W?rme 28. R. 29.

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the Campbell Maxwell,

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on ?. Clapeyron, "Memoir Mendoza reprint, pp. 73-105. ix-x. the Motive Power of Heat," in

(New

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son, Mathematical

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Hauptsatze

der

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zweiten und der

January-February

1970

97