The Conceptual Import of Carnot's Theorem to the Discovery of the Entropy

Author(s): Penha Maria Cardoso Dias, Simone Pinheiro Pinto and Deisemar Hollanda Cassiano
Source: Archive for History of Exact Sciences, Vol. 49, No. 2 (June 1995), pp. 135-161
Published by: Springer
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 The ConceptualImportof Carnoťs Theorem
to the Discoveryof the Entropy
Penha Maria Cardoso Dias, Simone Pinheiro Pinto,
& Deisemar Hollanda Cassiano

by C Truesdell
Communicated

Summary

Amongmanyotherthings,Carnot stateda principleand proveda theorem.

In 1850,Clausius correctedCarnot's theory,modifying it accordingto Joule's
principle.He mighthave considereda corollaryof the theoremas the math-
ematical formulationof Carnot's principle.We challenge the corollary:it is
based on hiddenassumptions,nor is it trueforall cycles.Clausius realizedthe
but on different
corollary'slack of generality, grounds.In 1854, he generalized
the theorem,and gave an (other)expressionto Carnot's principle.We analyze
Clapeyron's account of Carnot's theory,Thomson'saccount of 1849 and some
of Clausius' belated commentson his 1850 paper, as well Clausius' paper of
1854. We hope that theyshed lighton the corollary'stacit hypothesesand on
themeaningof Carnot's principle.It is our contention:Clausius took seriously
a contemporarymeaningof the principle,and looked for a conditionof inte-
grabilitythat could expressrecoveryof the initialconditionsof the reservoirs.
Furthermore, he seems to have had some prior knowledgeof the formthe
expressionof the principleshould take. Actually,this was the theory'snatural
candidate.

1. Introduction

1.1 In 1850,Rudolf Julius EmmanuelClausius publisheda paper in which

he establishedthe two laws of what he called the "generaltheoryof heat". This
theoryarose as a synthesisof two principles.One is JamesPrescott Joule's
principlethat heat is convertedinto workand conversely;the otheris Nicolas
Léonard Sadí Carnot's principle(1824) that the operationof heat engines
consistsin the"transportation"of caloricfroma hotterto a colderbody,and not
to a "consumption"of caloric. In 1854, Clausius published the expression
§dQf(T) (or Ys&ifiTi)), and,in 1865,he namedit entropy.
Carnot (1824) proves a theoremto the effectthat the efficiency
of a heat
engine obeying a closed, reversiblecycle of operationsis independent
of the

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136 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

workingsubstanceof the engine.From this theoremhe concludes that the effi-

ciency is a functionof only the temperatures of the two reservoirs.Besides
its theoreticalvalue, this theorem is also importanton historicalgrounds.
It is known that it was in his attemptto prove it that Clausius stated the
Second Law of Thermodynamics.
In his paper of 1850, Clausius recognizedtwo processesin the operationof
heat engines:"consumption" of heat (conversionof heat into work) and "trans-
portation"of heat froma hotterto a colder reservoir.Furthermore, he realized
thatin orderto prove Carnot's theoremhe had to introducea hypothesis:the
spontaneous flowofheat isfromhotterto colderbodies.Afterthat,Clausius used
so had done Carnot, Émile Clapeyron
the corollaryto calculate the efficiency;
(1834) and William Thomson (1848, 1849) beforehim.But it seemsthathe took
the corollaryto mean the veryprinciple,as suggestedby commentsin his paper
of 1854.
In his paper of 1854, Clausius generalizedCarnot's theoremand gave
another mathematicalformulationfor Carnot's principle.Initially,he defined
general mathematicalexpressionsto representthe two processes involved in
thermalengines.He named those mathematicalexpressionsequivalencevaluesof
a transformation. Next, he demanded that the transformations canceled each
other,so that the sum of both equivalence values was zero. Following this
strategy,he proved that in a closed cycle §Q/T ;> 0 (or Xôf/T, ^ °)- A11thisis
well known. Clausius' work has been discussed by historians of science
(Donald S. L. Cardwell, 1971; Peter M. Harman; Martin J. Klein; Clifford
A. Truesdell). Yet, thereis more to say about Clausius' motivations.

1.2 The purpose of this paper is threefold:

(1) We challengethe corollarythat the efficiency dependson the temperatures
only.We claim that the corollaryis not a straightforward consequence of the
theorem:obscure,tacithypothesesweremade (Section3.1). A motivationof our
paper is to findthe meaningof the tacitassumptionsin both theories,Carnot's
and Clausius'. Commentsby Clapeyron and by Clausius (in 1868) shed light
on the corollary'sproofand on its tacit hypotheses(Section3.2). A comparison
of Carnot's and Clausius' theories done by Philip Lervig (1972, 1976)
(Section3.3) togetherwith the discussion in Section3.2 gives a conceptual
frameworkin which the corollarycan be analyzed (Section3.4).
(2) The above mentionedcommentsby Clapeyron and Clausius (Section3.2)
lead to another point They indicate that Carnot's principleof heat transfer
had an interpretation that was not quite unknown;it had neverthelessbeen
misusedtill Clausius' paper of 1854. The interpretation was the foundationof
Carnot's own formulation of his as
principle, shown in a formerinvestigation
by one of us (Penha M. C. Dias)4 (Section2.4). In Section 4, we show that in

a Penha Maria Cardoso Dias is also a memberof Centrode Lògica, Epis-

Estadual de Campinas,UNICAMP,
temologiae Históriada Ciência,Universidade
Brazil

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 ImportofCaraoťsTheorem
Conceptual 137

his account in 1849 of Carnot's theory,Thomson was stronglycommittedto

the interpretation.
We hold thattheinterpretation beingdiscussedwas essentialto the heuristic
of the "discovery"of the concept of entropy.Accordingto this early meaning,
Carnot's principleof heat transfer is a conditionon thepossibilityof recoveryof
theinitialconditionsof operation;themathematical counterpartis thatit is to be
expressedby an integrablefunction(Section3.5). FollowingDonald S. L. Card-
well (1967), we shall referto this possibilityas a "recover ability"condition.1
Carnot, Clapeyron and Thomson (in 1848 and 1849) meant conservationof
the available heat,that is, the heat taken fromthe hot reservoirwas supposed
to be entirelydeliveredto the cold reservoir.Theirs is a condition on the
"recoverability"of theinitialconditionsof theworkingsubstance(in orderto start
a new operation).
(3) In Section5, we analyze Clausius' "discovery"of entropyin 1854. It is
knownthat his startingpoint to findthe expression§dQf(T) ^ 0 was a criti-
cism of the corollary.He claimed that Carnot's cycle was simple.As a conse-
quence, resultsobtained for the cycle,such as the theoremand its corollary,
needednot be general.Clausius, then,generalizedCarnot's theoremin a paper
publishedin 1854.
We claim that Clausius' strategyto generalizethe theoremcan be under-
stood as a search for an integrability conditionthat expresses"recoverability"
afterreversalof the cycle.He was not inventingthe idea of "recoverability", of
course.However Clausius took the hypothesesof the theoremof theirultimate
consequences:his was a conditionof "recoverability" of thestartingconditionsof
the reservoirs,afterreversal.
Furthermore, it seems that Clausius knew beforehandthat the integrable
functionhad to have the formdQf(T). We claim that thiswas but the natural
candidate at hand in the theory.

1.3 Before startingour investigation,we review, in Section2, Carnot's

theoremand the proofsgivenby Carnot and by Clausius. Mathematicaldetails
are givenin theAppendices,whichmightbe helpfulforunderstanding our paper.

2. Carnot's Theorem

2.1 The "categoriesof the science of heat" (Charles C. Gillispie, p. 367)

wereformulatedby Carnot in a littlebook, publishedin 1824,Réflexionssur la
Puissance Motrice du Feu. Among many new concepts and theorems,Carnot
stated a principle and proved a fundamentaltheorem. According to the
principle(p. 7):

1 Cardwell notes
that,in the late 18thand early 19thcenturies,
the important
conceptin water-power
technology was recoverability
of theinitialconditions
not re-
versibility.

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138 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

of motivepoweris, then,due in [heat engines]not to an actual

the production
froma warmbody to a cold body
consumptionof caloric,but to its transportation

Accordingto the theorem(p. 11):

themaximumof motivepowerresultingfromtheemploymentof steamis also the
maximumof motivepowerrealizableby any meanswhatever.

2.2 Carnot's ideas were not immediately spread (Martin J. Klein; Stephen
G. Brush; Cardwell, 1971). The book remainedunreadforten years,tillit was
re-written by Clapeyron. Another ten years elapsed, before Thomson came
across Clapeyron's book. This chance meetinginfluencedthe youngThomson
and the physicsthat came after.In particular,a new law of naturewas stated.
Thomson saw a contradictionbetweenJoule's experimentson the conver-
sion of workinto heat and Carnot's principle.Carnot reasonedin the context
of the caloric theory,although it is nowadays believed that he distrusted
it (Robert Fox, 1989). A basic tenetof the theoryis that caloric is conserved:
to the cold reservoir.
all of the heat taken fromthe hot reservoiris transported
Therefore, accordingto Thomson,eitherheat is "transported"- (Carnot) - or
it is transformed -
into work ("consumed") (Joule). Clausius understoodthat
therewas not a contradictionbetweenthe two principles,providedthat part of
the heat were "consumed", and part were "transported".Next, he proved
Carnot's theorem,takingthis modificationinto account.

2.3 Carnot's proof of the theorem is as follows. Suppose two engines

undergoinga Carnot cyclebetweenthe same two temperatures, and 7W
Thigh
Let one work in the directorder of operations,and the other,in the reversed
order of operations.The result of the operation of the directengine is the
"transportation" of a quantityof heat, g, fromthe hot reservoirat Thighto the
cold reservoirat Ti0Wy and the productionof a quantityof work W.
Now let the reversedenginebe such thatit "transports" the same quantityof
heat, Q, from the cold to the hot however
reservoir; assume that it uses
a quantityof work W. The theoremconsists in provingthat, whateverthe
workingsubstance,W = W.
To do so, suppose that they were not equal, say W <W. If it were
W > W, it would sufficeto reverseboth enginesto fall back into the former
situation.Let the enginesbe coupled,one workingafterthe other.At the end of
a complete cycle of both engines,the heat taken out of the hot reservoiris
taken back to it. However thereis a net work W - W > 0. Since no other
change occurs in the system,this work is obtained out of nothing.Carnot
claims that thisis impossible(energyperpetuum mobile).2An absurd conclusion
having been obtained, it followsthat W = W.

2 That Carnot refersto the energyas perpetuum

mobileis discussedby Lervig
(1972).

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 ImportofCarnoťsTheorem
Conceptual 139

SW (V »v
(Vo,Po)151' / (vb.Po). //W

Figure1. The cyclesof twoenginesworking

withdifferent are shown.It is
substances
giventhattheyworkbetweenthe same temperatures, and Tlow.According
Thigh to
Carnot's theorem,iftheytransportthesamequantity
ofheat,Qtrans,
theyproduce the
same amountof work,W.

Of course,the maximumpossible workdependson the substance.It suffices

to build the direct engine with one substance,and the inverseengine with
anothersubstance.If the work depended on the substance,one of the engines
would produce more work than the other,contraryto the theorem.
Accordingto Carnot's proof,the theoremis a consequence of Carnot's
principleand of a law of conservationof the "powersof nature":workcan not
be destroyednor createdout of nothing.
Carnot showsin a footnote
howthetheorem
is to be used.Thisfootnote
is
in
paraphrased Appendix 1.

2.4 One of us (Dias) showedthatCarnot'sprinciple can be based on two

concepts that arise in Carnot's own study of steam engines.One is what
Cardwell calls"recoverability" oftheinitialconditions,in orderto startopera-
tionsagain.The otheris Carnot's conceptof "economy".
The steamin steamenginesis condensed afterdoingwork.Therefore, before
beginning a new cycleof operations, steamhas to be createdanew.Carnot
understood thatcreationof steamrepresented a loss of motivepower.There-
fore,"economydemandsthattheworking substance be notdestroyed: thecycle
is to be completedusingthe same workingsubstancethathas been in the
engineat the beginning of operation.
"Recover is necessary
ability9 forthecycleto startonceagain.For theengine
to go back to its initialconditions,the heat (caloric)receivedfromthe hot
reservoirhas to be takenout oftheworking substance. Mechanicalcompression
ofthesubstance in contactwitha cold reservoir at itstemperature is Carnot's

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140 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

way to take heat (caloric) out of the substancewithoutdestroyingit. In this

reading,Carnot's principleof heat transferis a conditionof "recoverability"
of
the initial conditionsof the workingsubstance,in order that a new cycle of
operationsbe started.3

2.5 Initially,Clausius recognized two operations in the work of heat

engines: a transformationof heat into work ("consumed heat") and a
transformation of heat at a highertemperatureinto heat at a lowertemperature
("transportation").Suppose now two enginesundergoinga Carnot cycle be-
tween the same two temperatures,Thigh and Tiow.Let one work in the direct
order of operations,and the other,in the reversedorder of operations.The
resultof the operationof the directengineis as follows:it takes a quantityof
heat Qhighfromthe hot reservoirat Thigh,and produces a quantityof work
W (= Qw. "consumedheaf); accordingto Joule's principle,the quantityof heat
"transported" = Qhigh
to the cold reservoiris Qtrans - W.
Now let the work obtained by the direct engine be used to operate the
reversedengine. However assume that the quantities of heat involved are
Therefore,the operationof the reversedengineis as follows:it takes
different.
a quantityof heat Qtran&fromthe cold reservoirat TloMnand receivesa quantity
of work W at Thigh;according to Joule's principle,the quantity of heat
"transported"from the cold to the hot reservoiris Q'high = Q'trans
+ W. The
theoremconsistsin provingthat,whatever workingsubstance,Q^ans= Qtrans
the
= Qhigh).
(hence, Q'high
To do so, suppose that theywere different, for instanceQtrans> Qtrans- If it
were Q^s < Qtrans, it would sufficeto reversethe cycle of both enginesto fall
back into the formersituation.Let the enginesbe coupled, one workingafter
the other. At the end of a cycle of both engines,work is neitherused nor
- > 0 is
produced,it just getsbalanced. However a quantityof heat Q'trattsQtrans
transported from the cold reservoir to the hot Since
reservoir. there is no other
change in the the
system, transport of heat from the cold to the hot reservoir
happens out of nothing, that is, withoutexpendingwork.In orderto forbidthis
result,Clausius postulatesthat (1850, p. 134):
and
differences
[. . .] [heat] alwaysshows a tendencyto equalize temperature
therefore to pass fromhotterto colderbodies.

3 The evenaftertheywerecorrected byCLAUSIUS

argument appliesto theoperations
(Section2.5).The enginetakesheatfrom a hot reservoir.This heat eventuallywillhave
to be takenout oftheenginein orderforit to go backto itsinitialconditions. Ifall of
theheattakenin thefirstisothermal processwereto be converted intowork,thenthe
enginewouldhaveto spendan equal amountofworkto be compressed alongthesame
isotherm, to close the cycle;the net production of this is
engine nothing. But if only
a partoftheheatinitially transformed intoworkis allowedto remainas work,thenitis
possibleto closethecycle,usingthesamesubstance. thattheremaining
It is sufficient
workbe transformed againintoheat,by usingit to compress theworking substanceat
constanttemperature, beingby the same token delivered to the cold reservoir.

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 ImportofCarnoťsTheorem
Conceptual 141

V
Figure2. The cyclesof twoenginesworking withdifferent
substancesare shown.It is
giventhat theywork between the same temperatures, and
Thigh Tlow.Accordingto
Carnot's theoremmodified by Clausius, iftheyabsorbthesamequantity ofheat,Q,
theywill"transport"
thesamequantity and producethesameamountof
ofheat,Qtrans->
work, W = Q- Qtrans.

This is an independent,new law withoutwhich the conclusion of Carnot's

theoremcan not be inferred.

2.6 Using the two principlesinvolved in the operation of the engine,

Clausius deduces two mathematicalexpressions:
(1) Accordingto Joule's principle:
w = (Qhigh- Qtrans)
x (universalconstant).
It is a matterof course to derivefromthis principlethe law of conservation
of
energy:there exists an integrablefunctionof the thermodynamicvariables,
U - the internalenergy- such that

(2) FollowingCarnot, Clapeyron and Thomson,Clausius interprets Carnot's

theoremas meaning that the efficiency of an engine is a functionof the
temperaturesonly; for an infinitesimal
cycle,figure3, below:
6W _ dT
dQhU}h~C{TY
whereC(T) is Carnot's function,
an unknownfunctionof the temperatures only.
Clausius' proof of Carnot's theoremdoes indeed show that the law of
conservationof the "powers of nature" is still true,but in connectionwith

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142 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

Joule, not Carnot. His proofis insteadbased on a newlaw on the directionof

the spontaneousflow of heat.
Belated remarksby Clausius in his paper of 1854 (Section5.1) suggestthat
he thoughtthat Carnot's principlewas to be mathematically expressedby the
corollaryon the efficiency.

3. A Criticismof Carnoťs Theorem

3.1 Accordingto Carnot, the theoremproves that (Appendix1) the work

obtainedin thetransfer - betweentwo
of a unitofheat- thatis, the efficiency
fixedtemperaturesis independent of the substance.We do not challenge this
conclusion of the theorem.However,according to Carnot, a consequence is
that the efficiencyis a functionof the temperatures only.This resultdoes not
seem to be warrantedby the theorem,without furtherassumptions,tacitly
made by Carnot, Clapeyron, Thomson and Clausius (in 1850). We shall use
the notation of Appendix 1: u is the work done by the transferof a unit of
caloric,and e is the total transferredcaloric. The tacit assumptionsare, then:

(1) The unwarrantedresult is a straightforward consequence of another

assumption: òW = eòu, thatis, W is a homogeneous(of degree1) functionof e.
In principle,W could be a functionof both e and t, not necessarilyhomogene-
ous in e. In anotherwords,the generalassumptionis that W = T (e, t) = $e{t'
where there is a function $6 for each value of e; in particular,u =
r(e = i,t)= *,ml(ty
Homogeneityin Q is obviously true in Clausius' version of the theory:
into work It is apparentlyan
a fractionof the available heat is transformed
independenthypothesisin Carnot's theory.A motivationof our paper is just to
findits meaningin Carnot's theory.

(2) There is apparentlya non-sequiturbetweenthe proof that the efficiency is

independent of the workingsubstance,and the conclusionthat it is a functionof
the temperatures only.As Clapeyron cast the theorem(p. 85):
We have demonstrated that thisquantityof actiondevelopedis independent of
the agentwhichservesto transmit thesameforall gases,
theheat;it is therefore
neitherdoes it dependon themassof thebodyemployed; but thereis nothingto

of the temperature;
show thatit is independent of: efficiency
the denominator

dPdV = RdT 1 , r ,be !: t f ^ ç t,

= musttherefore equal to an unknown ot
function
dQ vdA-pd-Q
ÔV dP_
whichis thesame forall gases.
=
Accordingto Appendix 1, Clapeyron, afterCarnot, means that u &{t). The
point is that there seems to be "nothing to show that [the efficiency]is
independent"of the otherthermodynamic variables It
either. is not at all clear
whythe dependenceon the volumes and pressures attained duringthe various

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 ImportofCaraoťsTheorem
Conceptual 143

processesappears only throughQ. Clausius himselfproduces a threetemper-

ature cycle,forwhich the conclusionthat the efficiency depends solely on the
temperatures is false it
(Appendix3). Therefore, is more generalto assume that
u = r(e,t, V); it independsonly of the substance.But Carnot assumed that
7>,t,K) = <P(f);
Anothermotivationof our paper is to findthe meaningof this assumption
in both theories,Carnot's and Clausius'.4

3.2 In 1864, Clausius publisheda collectionof his papers. This collection

was translatedinto French in 1868 under the name ThéorieMécanique de la
Chaleur.5In this publicationof his paper of 1850, Clausius added a footnote
thatwas not in the originalpaper. This footnoteis placed immediatelyafterthe
conclusionthat the efficiency is given by Carnot's function.Perhaps Clausius
feltthatthe resultdid not followas a matterof course fromthe theorem.This
belated explanationhints at the deduction leading fromthe theoremto the
corollarythat the efficiencyis a functionof the temperatures only (1854, p. 55):
It willnot be out of place to givesomedevelopment to whatpreceded- When
a certainmatterundergoes a seriesof transformations formingan entirely closed
cycle,fromwhichresults: thata bodyA at temperature t losesheat,a partofwhich
is consumed in work,theotherpartpassesto a bodyB at temperature z; according
to thepreceding explanations, thislatterpartmusthave a determined ratioto the
magnitude oftheproducedwork(provided thisis a maximum);and thisrelationwill
notdependon anything butthetemperatures ofthetwobodiesA and B, noton the
natureof theintermediate matternoron thatofthetransformations. Therefore,it is
writtenan equationof theform:6

-producedwork
:- 7-: = p(t9t) .
transmitted
heat
Similar reasoningis also found in Clapeyron (p. 22):
In addition[themaximum is independent
effect] ofthechemicalnatureoftheliquid
or gas employed,of its quantityor itspressure;
so thatthemaximum quantityof
actionwhichthepassageofa givenquantity ofheatfroma cold to a hotbodycan
developis independent of the natureof theagentsused.7

4 That in Q is not a necessary of Carnot's principle

homogeneity consequence was
also noticedby Clifford A. Truesdell (1980,§ 51,p. 101).Henri Poincaré (1908,
§ 114,p. 140)also tooktheefficiencyto be a functionofthetemperatures,
ofthespecific
volumesand of thebody.We shallcome back to theiranalysesin note 10.
5 We
quote fromthe Frenchedition(Clausius, 1868),in freetranslation by the
authors.The book had an Englishedition, in 1879,The MechanicalTheoryofHeat.In
thatedition,thepaperswerenot just reprinted, but theywereeditedto giveto the
publication the styleof a teachingmanual,not of a collectionof papers.
6 Our italics.
Our italics.

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144 P. M. C. Dias,S. P. Pinto,& D. H. Cassiano

The references to the "natureof the transformation", to the "quantity"of

substance, and to the "pressure" make us suspectthatthe reasoningcan be as
follows:two different substances differby theirequationsofstate:theseequa-
tionsinvolvepressure, volumeand temperature, and constants thatmaydepend
on thesubstance. For instance, equal massesof two gasesobeydifferent
different
equations,due to different molecularweights; likewise, massesof the
different
samegas obeydifferent equations.8Consequently, equal massesoftwodifferent
gases,as well different quantitiesof the same gas, can not have identical
equationsfortheirisotherms and also fortheiradiabatics,in everycircum-
stance.Therefore, two Carnot cyclesbetweenthe same two temperatures, of
two different substances, whichdo the same work,and in whichthe same
quantity ofheatis receivedfromthehotreservoir, are in generalnotidentical.
According to the theorem, if different
substances producethesamework,they
"transport" the same quantityof heat between the same twotemperatures.Butif
thecyclesare notidentical, thedependence ofthework(enclosedarea)on path
can come only throughquantitiesthathave the same valuefor bothpaths
(cycles).This is probablythemeaningof Clapeyron'squotationin Section3.1.
Perhapsbecauseof it, homogeneity follows:W ocQ.9 Likewise,the factorof
proportionality mustdependonly quantitiesthathave thesame valuesin
on
bothpaths(cycles), buttheonlyremaining
respectively; variablesare- suppos-
edly - Thighand Tlow.

3.3. Philip Lervig(1972,1976)made a comparison betweenCarnot'sand

Clausius' theories.
According to Lervig,Carnot's theorycontains:

concept:an energyperpetuum
(1) A reversibility mobileis impossible.That is,
workcan notbe createdout ofnothing. processis described
An irreversible
by a "loss of work".Thereis thereforean integrable"workfunction", AA,
such thatAA+ AW^ 'dQf{T). For closedprocesses,AW ^ §dQf(T).
(2) A conservation law: heat is conserved.
Therefore,§dQ = 0.

3.4 The comments in Section3.2 and Section3.3 showa contextin which

thecorollaryon the can be discussed:
efficiency
(1) In Carnot's theory,Q is a path-independent of thestatevariables
function
= a
$ dQ 0. W is path-dependent
(or a state-function), functionof thestate
=
variables,such thatAW §dQf(T) 4= 0.

8 The equationof ideal gasesis PV = - r- 7" - ^T RT = (™mber°f moles)RT.

molecularweight
Therefore,onlywhenthesamenumberof molesis involvedare theequationsof two
ideal gases identical.
9 The availablevariablesin Carnot's a theoryare ß = Qtmns, and i u,w.
W9 Thigh
In Clausius' theory, 4= but thereis a W
constraint: = ß - Qtrans-
Therefore,
ß Qtrans,
theresultfollowsbecauseß is the onlyvariable,otherthan W, amongtheavailable
ones,thatinvolvesthestatevariablesV and P.

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 Conceptual ofCarnoťsTheorem
Import 145

On thebasisofLervig'sanalysis, itis possibleto explainhomogeneity in

Q as a of
consequence "reversibility". Work does not disappear nor does it
appear out ofnothing. Therefore,in each infinitesimalstepof thecycle,SW
is proportional to the theory'sonly"conservative" quantity, dQ; the pro-
portionality factor,l/f(T' is clearlythe integrating factorforthe work:
=
AW §dQf(T).
(2) In Clausius' theory, AW * 0 and jdQf(T) = 0. Of course,thepath-inde-
pendent, conservativequantityofthetheory, associatedwith"recoverability",
also takeson thesamevalueforall cyclesbetweenthesame temperatures,
and sameinitialstate.By the same tokenof Section3.2,it musthave the
formdQf(T)(f(T) is clearlyto be understood as an integrating factor).
However,in thenewtheory, independence ofpathturnsout to be a condi-
tionon theinternal energyand on theentropy. It is nota conditionon the
heat,as it is in Carnot's theory.We shall come back to thissubjectin
Section5.5,wherewe analyzeClausius' choicein 1854of Qf(T) as a legit-
imateexpression forthe equivalence values.
However the second objection raised in Section3.1 has not yet
been answered.As already mentionedin Section3.1, there still remains
the example of the three temperatureengine in Appendix 3. Had
Clausius solved it, he would have seen that the efficiency
depended,as a
generalresult,on (ratiosof) the volumes;onlybecausehe made a simplify-
ing hypothesis was the corollarytrue for that engine.Consequently, the
reasoningin Section3.2, leading to the corollary,can not be completely
correct.In Appendix3, we argue that the flaw lies in the listing,made
at the veryend of Section3.2, of the "remaining variables"on whichthe
factorofproportionalitydepends. onlyby chance- becausethe
Furthermore,
twotemperature -
engineis toosimple is theresultalwaystrueforit (Appen-
dix 2).

3.5 Howeverthereasoning in Section3.2 and Dias' investigations

mentioned
in Section2.4 hintat whatwas thecontemporary meaning of thetheorem
and
of Carnot's principle:Carnot's principleof heat transferis a conditionof
whichis to be expressedby an integrable
"recoverability function.
Thismeaningoftheprinciple is reinforced
by Thomson's accountin 1849of
Carnot's theory.He intentionallyassociatedwithCarnot's principlean inte-
grablefunction.Clausius' paper of 1850 showedthat Thomson'schoice of
a functionwas wrong.Actually, Thomsonmadea confusion betweenthefirst
and secondlaws,whichhe learnedfromClausius.
But Clausius' paperof 1850was notfreefrommistakes. Not onlybecause
oftheflawin theproofofthecorollary, butClausius also seemsto havetaken
thecorollaryto be the mathematical expressionof Carnot's principle,
as we
shallcomment upon in Section
5.1.This he and in 1854he criticized
recognized,
his formerexpression of Carnot's principle.
A contention of our paper is that in 1854 Clausius goes back to (a
corrected
modified, formof) theidea of "recoverability".
His generalizationin

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146 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

1854 of Carnot's theoremcan be describedas the search for an integrable

functionto express Carnot's principle.10

4. William Thomson's Interpretationof Carnoťs Theorem

4.1 As soon as Thomson read Clapeyron's account of Carnot's book, he

showed how Carnot's theoremcould be used to definean absolute thermo-
metricscale (1848). Afterthat,he wrotean account of Carnot's theory(1849).
This was the paper that directly influenced Clausius, as explained in

10 Truesdell makes a distinctionbetweenCarnot's General Axiom and Carnot's

Special Axiom: the formerstates,as we also claim,that W = r(Thigh9Tlow,Q), a non-
homogeneousfunctionof g; the latter states that W = [#(TZow)- <P(Thigh)~'Q and is
trueonly ifheat (caloric)is conserved(ScholiumI, § 5J).Truesdell (§ 9C) calls attention
to an importantresult obtained in 1851 by Ferdinand Reech: it followsfromthe
General Axiom that W = <P{Thigh, Tloyv)Q,that is, W is homogenousin Q, To see this,
considerany composed cycle,for instancethe one in Figure4: cycle 12345671 is com-
posed of cycles 12371 and 734567. Reech assumes that the cycles are reversiblealong
73, so thatthe workdone along 37 in cycle 12371 is canceledby the workdone along 73
in cycle734567. It followsthat work is additive:W11?>A561X = W12311+ W734567.Using
the General Axiom, this last equation can be written r(Thigh, Tiow,
Qhigh + Qint)= r(ThighiTl0W)Qhigh) + r(Thigh,Tlow,Qint).This is a functionalequation,
whose solutionis W = ${Thîgh,Tloyv)Q. Homogeneityarisesherefromthe reversibility of
73. However,our second criticismis not taken into account: the generalassumptionis
W = Y(T, V, 0, fromwhich the reasoningyields W = v(T, V)Q.
In PoiNCARÉ's analysis, homogeneity in Q appears as follows (§§ 115-116,
pp. 138-141): initially,the efficiency is a functionof the temperatures,the specific
volumes,and a variablec of the substance,F(Thigh,Tiow,vi9 v2, c' Again,two reversible
engines,built withdifferent substancesare considered,whichoperate in opposite senses
of the cycle.It is possible to make all of the heat taken fromthe hot source to go back
to it by choosingconvenientlythe limitsof the reversedcycle;but thereremainsa net
work (equal to the difference betweenthe works of the two engines),and a net heat
(equal to the difference of the heats successivelygiven to and taken fromthe lower
source). Unless the net work is deliveredto the engine,and not realized by it, there
would be work generatedfroma single source; the impossibilityof the conclusion is
another way of stating CLAUSIUS' postulate on the directionof the flow of heat.
Therefore,since the work of the reversedenginemust be greaterforthe same available
quantityof heat, the efficiencies are F(Thigh,Tlow,vl9 v2, c) ^ F(Thigh,Tiow,vi, v'2,c').
Now reverseboth engines;analogously,F(Thigh,Tlow,vu v2, c)^F(Thi^h, Tlow,vi, v'2,
c'). Obviously,F(Thigh,Tlow,vl5 v2s c) = F(Tkigh,Tlow,v'l5v'2,c'); this is interpretedto
mean that the efficiency is F{Thigk,Tlow).
Both analyses show that the possibilityof runningthe engines backwards without
losses (call it "reversibility")is the crucial step in the proof. The point made by
Clausius, which we here try to defend,is that the corollaryis not the appropriate
formulationof Carnot's principle.This is to be representedby the existenceof an
integrablefunction.Integrability imposes its formto be f(T)Q.

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 ImportofCarnoťsTheorem
Conceptual 147

Section2.2. In his statementof Carnot's theorem,Thomson calls attentionto

as an essential premiss(1849, p. 65):
reversibility

13. A perfect thermo-engineis such that,whateveramountof mechanicaleffect

it can derivefroma certainthermalagency,ifan equal amountbe spentin working
it backwards, an equal reversethermaleffect
willbe produced.

We do not thinkthat thereis too much on "reversibility"here.Thomson seems

to be just statingthe (overt)assumptionsmade to prove the theorem;he did
not take thisassumptionto its ultimateconsequences.The proofof the theorem
is leftfora laterparagraph,of number29. The aim is to findthe "effect"of an
engine.Thomson makes preliminary calculationsof the work,going as far as
possible without the theorem.His calculationsdo not add to what Carnot and
Clapeyron did. But he appended a footnotein which he presentswhat we
thinkis the clue to the theoremand to the principle.

4.2 The meaningof Carnot's principlegiven in the above mentionedfoot-

note, appended to paragraph 26 of his paper of 1849, is (p. 74n):

The generalprinciplemay be analytically terms:-

statedin the following if
1
- I dV' denote[s] the accessionof heat receivedby a mass of any kind,[...],
dVJr J
KdQ'
when the volume is increasedby [dV], the temperature
being kept constant,and
# I TTr) dT' denote[s] the amount of heat which must be supplied to raise
L'dVJy J
the temperature by [dT~', without any alteration of volume; then
F fàQ' 7dO' 1
'dQ(V,T) = [-^) dV+ [~) dT' mustbe thedifferential
ofa function
of[7]
L 'dVjT 'dTJy J
and [TJ

His intentionsare clear: the heat evolved (in an infinitesimal

process)is a total
of V and T (and does not depend on the process itself). The
differential
intentionis even more conspicuous in a note appended to the footnote,in
November 5, 1881 (p. 75n):

In thecorrecttheoryit is [L/] thatis a completedifferential,

not [ß].

Accordingto the footnote,Carnot's principlemeans that (1849, p. 74n):

That thereis sucha function [ß], of two independent
variables[F] and [T1],is
merely an analytical of
expression Carnoťs fundamental
axiom,as appliedto a mass
of air.

4.3 Accordingto Thomson, Carnot's principlestates the existenceof an

integrablefunction,Q:

dQ{V,T) = (|p) dV+ (|p) §dQ= 0 .

dT, where

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148 P. M. C. Dias, S. P. Pinto,& D. H. Cassiano

Isa b a _f b 2' _j_

'^-2''c" >1 û
4= d ^ **=*' c=3
3
h- AV- H I-- AV- H
P
1 II

V
Figure3. The parallelogram
1234represents cycle.Figure31showsthat,
an infinitesimal
1234can be approximated
sides,thearea of theparallelogram
forinfinitesimal by the
areaoftheparallelogramabed.Obviously,abedhas thesameareaas 1'2'3'4'(Figure311).
theworkdone in an infinitesimal
Therefore, Carnot cyclecan be approximated by
dVdP;

It means that heat is not lost, and expressesa law of conservation. In other
words,the workingsubstancegives up to the cold reservoirall of the heat it
received from the hot reservoir.Therefore,Carnot's principle,according to
Thomson,expresses"recoverability" of the initialconditionsof the substance,as
mentionedin Section3.5.

similarto Carnot's and Clapeyron's

4.4 The theoremgives the efficiency,
accounts. Following Clapeyron, the "parallelogramlike" figureof Carnot's
sides dV and dP, Figure3.
cycleis approximatedby a rectangleof infinitesimal
Let dQ be the heat evolvedduringthe expansionat constantpressure.This heat
is deliveredto the cold reservoirduringthe compressionat constantpressure.
Therefore(1849)
dV
x - dT;
bW = dPdV = (constant)
work(a secondorderdifferential):

(dQ'
dQ = -
heat(a firstorderdifferential): dV;
'dVJP
^ = (constant)
efficienCy
~/^JT-

4.5 AfterreadingThomson,Clausius wrotehis paper of 1850, establishing

the laws of the "general theoryof heat". He correctedthe theoryin the way
already explained in Section2.2. This led Thomson (1851) to write a new
account of the theory,correctinghis firstaccount by takingClausius' discover-
ies into consideration.The statementof the theoremis similarto its statement
of 1849 (1851, p. 111). However,Thomson learnedfromClausius (1851, p. 117)
that

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 ImportofCarnot'sTheorem
Conceptual 149

The simplestinvestigationof the consequencesof the firstproposition[Joule's

in thisapplication,
principle] whichoccurredto me,is thefollowing,beingmerely
themodificationofan analytical
expressionofCarnot'saxiomregarding theperma-
nenceofheat,whichwas givenin myformer paper,requiredto makeit not
express,
Carnoťsaxiom,but Joule's.

Continuingthe above quotation,and followingClausius, Thomson gives the

mathematicalexpressionof Joule's principleas the existenceof a total differen-
tial,whose integralhe calls themechanicalenergyof thefluidmass (1851, p. 118):

(GP),
-')"♦(&«••
Thomson learned fromClausius that the existenceof a differential
functionis
associated withJoule's principle,not withCarnot's principle.
The efficiency
is stillcalculatedas was doneabove,exceptthatP is seenas
a functionof T; accordingto the cycleof Figure3 (1851,p. 119):

={iP)rdTdv'
dpdv
=de
heat =(!f)/F'
= (-)
efficiency
gAdT;
'dv)T
accordingto the corollary(1851),

where'i is assumedto be a function

(lř)K=K^)/
of onlythetemperature.
This procedure
does not differfromwhatClausius did in 1850.

4.6 What,then,is made of Thomson'sfirstinterpretation of Carnot's

Fromourcomments
principle? in Section4.3,we see thatit was a condition
on
the"recoverability"oftheinitialconditionsoftheworking substance.According
to Thomson'sversionof the theoryin 1851,it is to remaina "recoverability"
condition(p. 109):
7. Accordingto an obviousprinciple,
firstintroduced,
however, intothetheoryof
the motivepowerof heat by Carnot,mechanicaleffect producedin any process
cannotbe said to have beenderivedfroma purelythermal unlessat the
reservoir,
end of the process all the materialsused are in preciselythe same
physical and
mechanicalcircumstances as theywere at the beginning.11

11 Our italics.

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150 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

However Thomson seems to give to "recoverabilitý"

the same wrongmean-
ing of 1849 (1851, p. 109):
In anysuchengine,theseriesof motionsperformed duringa period,at theend of
whichthematerialsare restored thesamecondition
to precisely as thatin whichthey
existedat the beginning,
constituteswhatwill be called a complete cycleof its
operations}1
The quotation clearlyrefersto the singlecycle.Therefore,Thomson seems to
his own statementof the theorem,accordingto whichCarnot's
have forgotten
principledemands recoveryafterreversal.

5. Clausius' Generalizationof Carnoťs Theorem

5.1 Clausius starts the paper of 1854 noting that the formof Carnot's
theoremgiven in 1850 can not be complete(p. 131):

[The primitiveformofCarnot's theorem] does notallowtherecognition, in a very

neatway, of the essence of the and
principle, its connectionwith the [law,of
first
Joule]; I thinkthat it is not to
useless it
give [to the secondlaw] another form that
suitsbetterto thisaim,and whichwillbe morecomfortable forapplications.13
The natureof Clausius' criticismis importantfor the recognitionof what the
"essence of the principle"is.
Initially,Clausius states what seems to be his formerinterpretation of
Carnot's principle,so far its "presentform".It expressesthe relationbetween
the two operations in heat engines; therefore,it is to be expressed by the
theoremand its corollary(1854, p. 137-138):
putin harmony
Carnot'sprinciple withthefirst a rela-
[Joule's] expresses
principle
tionbetweentwo kinds oftransformations:thetransformationof heatin work, and
thepassageofheatfroma hotterbodyto a coolerbody,whichcan be regarded as
of a quantity
a transformation of heatat a hightemperature intoheatat a lower
Underitspresent
temperature. form, can be enouncedin thefollowing
thisprinciple
terms:in all cases whena quantityof heat is transformed in workand the body that
operatesthis transformationgoes back to its initialstate, it is necessarythat at the
same timeanotherquantityof workpassesfroma hotterto a coolerbody;and theratio
betweenthis latterquantityof heat ["transportedheat"! and theformer["consumed
heat"] dependsonlyon the temperatures of the two bodies betweenwhichits passage
takes place, and not on the natureof the intermediate matter.

Clausius, however,criticizedthis interpretationof Carnot's principlein

1854. The targetof his criticismwas the corollarythat we challenge,but he
reasons.The point is that the corollaryis deduced for
criticizedit fordifferent
cycles with only two temperatures(1854, p. 138; 1879, p. 92):

12 Our italics.
13 Our italics.

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 ConceptualImportofCarnot'sTheorem 151

... thededuction
ofthisprinciple [Carnot's theoremand principle]
is foundedon
a verysimplephenomenon, in whichonlytwobodiesintervene, whichlose or gain
it is tacitlysupposedthattheheatthatis transformed
heat;consequently, intowork
comesfromone of thetwo bodiesbetweenwhichthepassageof heattakesplace.
But when thereare more than two temperatures involved,"transportation"and
"consumption" may happen at different The
temperatures. corollarydoes not
account forthissituation.Therefore,the theoremin its originalformis incom-
plete (1854, p. 138; 1879, p. 92):
In this way,it is made a verydefinite hypothesison the temperatureof heat
transformed intowork,therefore,
theinfluencethata changein thattemperature
will
produceon the ratioof the two quantitiesof heat remainsconcealed,and the
principleis, consequently, in thisform.
incomplete,
The pointis moreclearlymade in the editionof 1879 of his Mechanical Theory
of Heat (p. 92):
Now,in thefirstplaceas concerns thetransformationofheatat one temperature to
heatat another,
it is evidentat once thatthetwotemperatures, betweenwhichthe
transformation
takesplace,mustcomeunderconsideration. But thefurtherquestion
now arises,whether in thetransformation fromworkintoheat,or fromheatinto
work,thetemperature oftheparticularquantityofheatconcerned playsan essential
part,or whetherin this transformation the particulartemperature is matterof
indiffierence.
The problemin questionis whetherthe dependenceof the efficiency on the
temperature at which usefulwork is
("consumedheat") produced is a universal
resultor not. Therefore,what is needed is a generalizationof Carnot's theorem
(1854, p. 132):
... I thinkit is moreusefulto deduceimmediately
thegeneralformofthistheorem
fromthesameaxiom,whichhelpedme in [1850] to demonstrate Carnoťsmodified
theorem.

Next, Clausius considers the cycle of Figure4 (the cycle is discussed in

Appendix 3). In this cycle heat is transformedinto work at two different
temperatures,Thighand Tint,and given offto the cold reservoirat a third
temperature,Tlow.Clausius made a simplifying assumption:the heat trans-
formedinto work at the intermediatetemperature (Tint)is entirelytransformed
back into heat at the lower temperature (Tlow);consequently,work is generated
at a singletemperature In
(Thigh). the simplifiedcycle,the temperatures at which
the two processes occur are different. the is
Therefore, simplifiedcycle conve-
nientfor findingthe separate influences,in Carnot's theorem,of the temper-
atures involvedin each one of the two processes in Carnot's engine.

5.2 As mentionedmanytimesbefore,the threetemperature cycleshows that

thecorollaryon the efficiency
obtainedforthe two temperature cycle cannot be
general.The volumes do not disappear fromthe expressionfor the efficiency;
but withthe above simplifyingassumption,it is truethat the efficiencydepends

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152 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

7
y-^ X
' ^V 'Otrans

1/
cycleproposedbyClausius is shown.In thesimplified
Figure4. The threetemperature
cycle,duringthe expansionat Thigh,the engineproducesworkQw- W; the work
producedat Tintis entirely
convertedback intoheat at Tiow.

only on the temperatures(Appendix3). Clausius did not commenton this

specificpoint.We shall thereforeneverknow whetherhe knewit or not. On the
otherhand, it is hard to believe that he nevercalculated the efficiencyforthis
If
cycle. so, his criticismwould not be so formaland abstract,as it appears to
be in the way it stands.

5.3 Afterhis criticism,Clausius is ready to presentthe generalproof that

shows "the essence of the principle".The strategyof the proofhas two crucial
points:

(1) The introductionof a concept - equivalentoperations:

In a closed, reversiblecycle, the two processes - "consumption of heať
of heat into work) and of
"transportation heať - are
(transformation
equivalent,and cancel each other.
(2) The definitionof mathematicalexpressionsforeach operation- equivalence
value of an operation:
of heatintoworkat
equivalencevalue of the transformation
TMgh=- 'Qw'f(Thigh);
of heat at Tintintoheat at
equivalencevalue of thetransfer
Tiow = + 'Qtrans'F(Tint,Tlow'
where the sign conventionis:
intowork:- heattransported
heattransformed from
highertolowertemperature:
+
worktransformed from
intoheat:+ heattransported lowertohigher - .
temperature:

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 ImportofCarnoťsTheorem
Conceptual 153

The remainderof the proof is now:

(3) The "equivalence"of the two operationsimpliesthat theirequivalencevalues

cancel in eitherdirectionof the cycle:
- 'Qw'f(Thigh)+ 'Qtrans'F{TinU
Tlow)= 0. (2)
(4) Then it is proved that a necessaryconditionfor(2) to representa reversible
cycle is that (Appendix4):
F(Tint, Tlow)=f(Tlow) -f(Tinty (3)
(5) Therefore,in a closed, reversiblecycle,
- I U(Tl0W) -f(Tim)2 = 0;
+ | Qtrans' (4)
Qw'f{Thigh)
or

I Qif(T,) = 0.
t= l

(6) To completethe proof,an irreversiblestatementmust be established:

¿A/(Ti)>0. (5)
1=1

It is in thisstep that the axiom on the directionof the spontaneousflowof

heat enters.Similarlyto the formerproof,the axiom forbidsthe integralto
take on negativevalues.

Finally,Carnot's principlehas a mathematicalexpression(1879, p. 90):

Thisequation,whichwas firstpublishedbytheauthorin 1854(Pogg.Ann.vol. 93,
p. 50), formsa veryconvenientexpressionforthe secondmain Principleof the
MechanicalTheoryof Heat,as faras it relatesto reversible
processes.
To discoverthe "essence of the principle",which Clausius thoughthe had
shown by his new proof,two commentsare needed.

5.4 The firstcomment refersto the concept of "equivalent"operations.

Accordingto Clausius, "consumption"and "transportation"are equivalentopera-
tionsin the sense that theycan replace each other (1854, p. 144):
Of thetwotransformationswhichoccurin a closed,reversible
cycle,eithertakenin
reversesensecan replacethe other.
Clausius means the following:let heat be transformed into workat the temper-
ature Thigh of the hot reservoir,Jť. This operationcan be canceled by trans-
formingthe same quantityof work back into heat, at the same temperature;
however,forit to be accomplished,it is necessarythat some otherquantityof
heat be transportedfroma cold reservoir,#, at the lower temperature, Tiow,to
Jť, at the highertemperature, Thigh.Analogously,let heat be transportedfrom
Jť, at Thigh,to #, at Tlow.This operationcan be canceled by the transportation

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154 P. M. C. Dias, S. P. Pinto,& D. H. Cassiano

of the same quantityof heat from# to Žť; however,forit to be accomplished,

it is necessarythat work be transformed into heat at Thigh,and receivedby Jť.
the
Therefore, operationsreplace each other, in the sense that one has to occur
- in reversedsense - in order to cancel the other.
Therefore,accordingto Clausius, reversibility means"recoverability" of the
initialconditionsof the reservoirs, by reversal of operations: the hot reservoir
receivesback all of the heat taken fromit, while the cold reservoirgives back
all of the heat receivedby it.
Thereis a small point thatdeservesexplanation."Canceling",as givenby (2),
refersto the singleengine,not to the compound engine.But "recoverability" is
actuallya conditionon the operationof thecompoundengine,because thisis the
one that is able to recoverthe initialstate of the reservoirs. The strategyof the
proof in Section 5.3 consistsin finding the condition for "canceling"to occur,
afterreversal.This conditionis (3), whichis a "recoverability" condition,obtained
by considerationof the operationof the compoundengine.Afterinsertionof (3),
(2) does indeed represent"recoverability" afterreversal:it means that the single
engine has to satisfy some condition,if the compound engineis to recoverthe
initialstate; this conditionis "recoverability"of the entropyin the singlecycle.

5.5 The second commentrefersto the choice of the mathematicalexpres-

sions forthe equivalencevalues.Integrability is a necessaryand sufficient
condi-
tion for reversibility,in the sense given by Clausius, of recoverability of the
initial conditionsof the reservoirs.However the choice dQ f(T) rightat the
beginningof Clausius' proofseems to assume some previousknowledgeof the
formthat the integrablefunctionshould take. Furthermore,the equivalence
valuesare similarto an expressionencounteredmanytimesin the theory:ÔW =
dQf(T). We saw in Section3.3 that,in Carnot's theory,AW = §dQf{T) 4=0,
whichis consequentlynon-integrable. In Clausius' theory,dQf(T) is no longer
equal to ÕW, but why should it be "the" integrablefunction?
If we recall the analyses in Section3.2 and in Section3.4, dQ f(T) is the
expression,in the works of Carnot, Clapeyron and Thomson (in 1849), that
takeson thesame value forall cyclesoperatingon the same conditions.Clearly,
any conservativequantityis path-independent; consequentlyit has the same
value for all cycles operatingon the same conditions.What Clausius did was
simplyto make dQf(T) "the"conservative quantityassociatedwith"recoverabil-
ity"of the initialcondition of the insteadof makingit equal to SW,
reservoirs,
as did Carnot. Of course, this procedure makes the choice dQ f(T) no more
than a tentativechoice.

5.6 The commentsin Sections3.2, 3.4, 5.4 and 5.5 led us to suspect that
Clausius and contemporaryphysicistsknew that Carnot's principlewas a
ability".The mathematicalcounterpartis a conditionof
condition of "recover
With this much in hand, what Clausius did in his paper of 1854
integrability.
is betterdescribedas an answer to the followingproblem:can the operation
of heat engines be representedby a conditionof integrability of the form
in Section5.3 is the way to proveit.
§dQf(T) = W The strategy

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 ConceptualImportofCarnoťsTheorem 155

5.7 In 1865, Clausius published a comprehensivepaper on the theoryof

heat. By that time,both laws were integrability criteria.
The firstlaw is a "recoverability" condition.It says that the workingsub-
stancegoes back to its initialstate,recoveringits heat content,U (1865, p. 164):
For giveninitialand finalstates,thechangein theenergy is completely
determined
bythemwithout theneedof knowing how thetransition fromtheone stateto the
otherhas takenplace.Neitherthepathfollowed by thetransition northecircum-
stancewhether thetransitiontakesplacereversibly or irreversibly
has anyinfluence
on thechangein energy. Accordingly,iftheinitialstateand theenergy correspond-
ing to it are given,we can say that the energyis completely determinedby the
instantaneous stateof the body.
The second law is also a "recoverability" condition,but only afterreversal,
and is thusa reversibility condition.It says that the reservoirs
go back to their
initialstate,if the cycle is reversed,recoveringtheirheat content(1865, p. 185):

[CdQl
Ifindeed... theintegralG)- is alwayszerowhenever
thebodyperforms
a com-
pletecycleof arbitrary
processesback to its originalstate,thequantity
underthe
dQ
- , mustbe theperfect
sign,namely,
integral ofa quantity
differential thatdepends
onlyon thestatethebodyhappensto be in and notat all on thepathby whichit
got there.
Finally,the fundamentalconceptsof the theoryare integrablefunctionsof
P, V and T (1865, p. 187):
For thesake ofclarity letus stopto summarize thedifferentquantitiesdiscussedin
thecourseof thisarticle.Theseare quantities thathavebeennewlyintroduced by
themechanical theoryof heator havereceivedby thistheoryan alteredmeaning.
Theyhavethecommon characteristic
thattheyare determined by themomentarily
existingstateofthebodywithout depending on ourknowledge ofthewayin whichthe
bodyarrived at thisstate.Thereare thefollowing six quantities:
(1) theheatcontent
[H = averagekineticenergyof themolecules], (2) the work content [/ = internal
(conservative)workof themolecules], (3) the sum of theprevioustwo quantities,
called the energyof the body [17], (4) the transformation value of the heat
- , (5) thedisgregation,
whichis to be considered theexisting arrange-
[ITr~|

r dl-dWl
of body dZ =
mentof thecomponents , and (6) thesumof(4) and (5),
accordinglythe transformation
content of the body or the entropy
[V dQ dH + dl-dWl1*
dS ==- = .

Foridealgases:H = U,I = 0,dZ= = dU-dW»

dJ , äS=f
14 Our italics.
15 The
conceptofdisgregation
was introduced
in 1862.It is notrelevant
to ourpaper.

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156 P. M. C. Dias, S. P. Pinto, & D. H. Cassiano

Appendix1: Carnoťs Versionof the Two TemperatureCycle

Consider the cycle of Figure1. Accordingto Carnot, there is "transpor-

tation" of a quantity of heat Q from a reservoirat temperatureThighto
a reservoirat temperatureTlow.In theprocessof "transportation",a quantityof
work W is then
generated:the gas expands at Thigh, it is compressedat Ttow;
since Tiow< Thigh,thereis excess work. The calculation forthe whole process
was done by Carnot in a footnote.It is as follows:16
The equation of state was writtenPV = N(t + 267), wheret is the temper-
ature in centigrade,and N is a constant.Then

expansiondV = dw = N - - -
workdone duringisothermal ;

N
assuming W = 0, when V = 1, t = 0 and Po = - -,
integrating,
267

W = N{t + 267)lnV.
The work done, when heat is transportedfromí to í + di is
ÖW= NinVöt.
Now, Carnot defined:
of a unitof heat= u.
workdone by the transfer

Accordingto Carnot, the theoremsays that:

u = $(ř), where#(i) is a unknownfunction
of t.

Therefore,
d$
dt
If e units of heat are transferred,
SW = eôu
or
N'nV = e$(t);
hence

-(&>'■

is
The efficiency
SW = -NlnVôt = ^#...
Su = $'(t)St.

16 Our notation.

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 ImportofCarnot'sTheorem
Conceptual 157

Appendix2: The Two TemperatureCycle

Considerthecycleof Figure2.
Adiabaticprocesses:

- ■ (1)
v, vv
Closure:
i = r. (2)
Isothermalprocesses:

heattransformed = Qhigh
intoworkat Thigh In - ^ ;
= Thigh (3)

worktransformed = TlowIn -
intoheat at Tlow= Qtrans = TlowIn -~. (4)

Therefore,

- Tlow)ln~~,
consumedheat= Qw = (Thigh (5)

T
= 1-
efficiency (6)
-^-.
*■ high

It is an assumption
of the theoremthatQw has the same value forboth
--
Using(3) and (4), Qw= Thighln-
engines. Tlowln-^.Therefore,
by assump-

tion,-~ and -^ haveto be respectively

equal forbothengines.The corollary's
actualconclusion
is thattheefficiency
can dependonlyon quantities thattake
on thesamevalueforbothengines, it can in principle
Therefore,
respectively.
V V
dependon - and - . But the closurecondition and the adiabaticcondition

make- = -77-,
and thereremainsonlyone independent
ratioof volumes,say

~. Consequently, Qw is givenby (5), and involvesthe same ratioas Qhigh.

Clearly,the ratiocancelsout in the expression
fortheefficiency.

Appendix3: The Three TemperatureCycle

Considerthe cycleof Figure4.

Adiabaticprocesses:

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158 P. M. C. Dias, S. P. Pinto,& D. H. Cassïano

Closure:
7 = 7'. (2)
Isothermalprocesses:
intoworkat Thigh
heat transformed

=
= Qm9h = + (3)
Thighln^ Thigh(
-ln^ In-^J,
intoworkat Tint= Qint= Tintln- ,
heat transformed (4)

worktransformed = TiowIn - .
intoheat at Tlow= Qtrans (5)
*6

Therefore,

intowork= Qhigh
totalheattransformed - Tini)ln-
4- Qint= - (Thigh

+ (6)
Thighln^
V
- Tint)ln- V
- TIow)ln-
consumedheat= Qw = - (Thigh + {Thigh , (7)

- - -
w {Thigh Telily1 4-(Thigh Tlow)In-
= - - = - . (8)
efficiency
'Lhigh "t- '¿int x, -v 4 , -K 5
- /rr - rp In + Tw^ In
rp
(Tfc^fc T/nt)

is a functionof the volumes.

Clearly,the efficiency
Clausius made a simplification:
=
ßtni = Qtrans, SO that ß^ Qhigh]

in this case

i ^ow

= - ,
efficiency * /ow ■*low
-

1 high Ä int

a functionof the temperaturesonly. Actually,the adiabatic processesand the

closurerelationimpose conditionson the volumes,so that thereare only two
- and - . The simplification made by Clausius makes
independentratios,say
these ratios equal. Therefore,the volume cancels out, and disappearsfromthe
final result.

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 ImportofCarnoťsTheorem
Conceptual 159

The corollary'sactual conclusion is that the efficiency can depend only on

quantitiesthattake on the same values for the two However
engines,respectively.
an assumptionof the theoremis that the consumed heat (expression(7)) be
equal forboth engines,if theywork betweenthe same temperatures. Inspection
of (7) shows that this is true only if In - - and In- ^ are equal respectivelyfor
both engines.Therefore,the efficiencycan depend on these ratios. In another
words,our formercontention(Section3.1) that thereis nothingto show that
the efficiencyis independentof the thermodynamic variables other than the
is
temperature right.

Appendix4: Generalizationof Carnoťs Theoremfor the

Three TemperatureEngine

Consider two engines,one operatingin the directorder,the other in the

reversedorder,Figure4. Let the directenginetransform Qw into work at Thigh,
and let a quantityof heat Qnansbe transformed into work at Tint,and be
entirelytransformedback into heat at Tlow.Consideran engineoperatingin the
reversedorder, with the only differencethat a differentquantity of work
{"consumedheat"), Q'w, is produced at a different < Thigh.
temperature,Trhigh
Everythingelse is kept the same. "Cancelation"of operationsmeans, for the
directengine,
-
Tlow)= 0,
Qwf(Thigh)+ QtransF(Tint, (1)
and, for the reversedengine,
- QtransF(Tint,
+ Qrwf{Tfhi9h) Tlow)= 0. (2)
Summing(1) and (2),
~ = 0.
Qwf(Thigh)+ Q'wf(T 'high) (3)
The "transportation" of Qtrans from the reservoirat Tintto the reservoirat
Tiowis cancelled by the reversedoperation.Furthermore, by (3), the resultof
the operationof the directand reversedengines,one workingrightafterthe
other,is the transformation into workof a quantityof heat Qw at Thigh, and the
transformation into heat of a quantityof work Q'w, at T'high.However,if the
cold reservoirreceivesthe heat Q'w, and if the hot reservoirgives offthe heat
Qw, it means that a quantityof heat equal to Qw - Q'w is transformed into
work at Thigh. Consequently,the resultof thejoint operationof the enginesis
thatQw - Q'w is transformed into work at Thigh,
and Qw is "transported" from
Thighto T'high. That is, the compound engine behaves as a two temperature
engine;therefore,

-{Qw - Qw)f{Thigh)+ Q'wF{Thi9h, = 0.

Thigh) (4)

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160 P. M. C. Dias,S. P. Pinto,& D. H. Cassïano

Howeveradd and subtractQrwf

'Thigh)to (3):
~(Qw - Qw)f(Thi9h)
+ QwU(Tm9h)-/M] = 0. (3')
But (4) and (3') describethe same engine.Therefore,
= f(T fhigh)
T'high)
F(Thigh, -f(Thigh). (5)
Therefore, value,if the wholeclosed
(5) is the conditionon the equivalence
processis reversible.

Acknowledgement. PMCD thanksDr. Hero Joaquim DE Menezes forhis comments

on an earlier draftof this paper. His dissatisfactionwith Carnot's theoremwas our
motivation;we hope he feelshappier now.

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UniversidadeFederal do Rio de Janeiro

Brazil

(ReceivedAugust10, 1994)

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