Thermodynamics

EnricoFermi1938NobelLaureateinPhysics
June12,2011

Copyrightc1936byEnricoFermi.LauraFermi,CopyrightOwner.Allrightsreserved
underPanAmericanandInternationalCopyrightConventions.
PublishedinCanadabyGeneralPublishingCompany,Ltd.,30LesmillRoad,Don
Mills,Toronto,Ontario.
PublishedintheUnitedKingdombyConstableandCompany,Ltd.,10OrangeStreet,
LondonWC2.
theThisauthor(139received+x)pagehisLAT
NobelE
XeditionPrize.iswrittenThiseditionin2008,containsseventysomeyearsminorafter
changestofitthesettingsinLAT
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ii

Preface
THISbookoriginatedinacourseoflecturesheldatColumbiaUniversity,NewYork,during
thesummersessionof1936.
Itisanelementarytreatisethroughout,basedentirelyonpurethermodynamicshowever,
itisassumedthatthereaderisfamiliarwiththefundamentalfactsofthermometryand
calorimetry.Hereandtherewillbefoundshortreferencestothestatisticalinterpretationof
thermodynamics.Asaguideinwritingthisbook,theauthorusednotesofhislecturesthat
weretakenbyDr.LloydMotz,ofColumbiaUniversity,whoalsorevisedthefinalmanuscript
critically.Thanksareduehimforhiswillingandintelligentcollaboration.
E.FERMI

TheNobelPrizeforPhysicsin1938wasawardedtoEnricoFermiforhisdemonstrations
oftheexistenceofnewradioactiveelementsproducedbyneutronirradiation,andforhis
relateddiscoveryofnuclearreactionsbroughtaboutbyslowneutrons.
iii

Corrections
Within this edition, certain partsoftheoriginalworkwerechanged.Thisisespeciallyin the
cases whereby the error isobvious or insomeconventionswhich areno longerused. A
notable example is the unit for temper ature, kelvin, which was written as K by Enrico
Fermi.Now,theconventionistowritetheunitasjustK.

Copyright
Asfiftyormoreyearshavepassedsincethedeathoftheauthor,thisbookisnowinthe
publicdomainofMalaysia.
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Contents
Contentsvi
Introductionix
1ThermodynamicSystems 11.1 Thestate ofasystemanditstransformations..........
11.2Idealorperfectgases........................8
2 The First Law of Thermodynamics 11 2.1 The statement of the first law of
thermodynamics.......112.2Theapplicationofthefirstlawtosystemswhosestatescan
be represented on a(V,p)diagram.. .. .. . .. .. .. .. . 17 2.3The applicationof the
firstlawto gases. .. .. . . . .. .. .19 2.4Adiabatictransformationofagas................
23
3 The Second Law of Thermodynamics 27 3.1 The statement of the second law of
thermodynamics. . . . . 27 3.2 TheCarnotcycle. . . . . . . . . . . . . . . . . . . . . . . . .. 29 3.3
Theabsolutethermodynamictemperature. ..........323.4Thermalengines.............
.............39
4The Entropy414.1Somepropertiesofcycles....... ......... .....414.2Theentropy..
. .. .. .. ....................434.3Somefurtherpropertiesoftheentropy............
..484.4Theentropyofsystemswhosestatescanberepresentedon
a(V,p)diagram................ ......... ..524.5TheClapeyronequation.......
...............564.6TheVanderWaalsequation....................61
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5ThermodynamicPotentials695.1Thefreeenergy. .. .. .. .. . .................695.2
Thethermodynamicpotentialatconstantpressure. . ....735.3Thephaserule. .............
.............775.4Thermodynamicsofthereversibleelectriccell.........83
6Gaseous Reactions 876.1 Chemicalequilibriain gases. .. .. .. .. . .. ........876.2
TheVant Hoff reaction box.. . .. .. .............896.3Anotherproofoftheequationof
gaseous equilibria. . . . . . 95 6.4 Discussion of gaseous equilibria the principle of Le
Chatelier.97
7The Thermodynamics of DiluteSolutions1017.1Dilutesolutions.....................
. . . . . . 101 7.2 Osmoticpressure. . . . . . . . . . . . . . . . . . . . . . . . . . 106 7.3
Chemicalequilibriainsolutions. . . . . . . . . . . . . . . . . 110 7.4 The distribution of a solute
between two phases. . . . . . . . 113 7.5 The vapor pressure, the boiling point, and the
freezingpoint
ofasolution.............................116
8The EntropyConstant125 8.1TheNernsttheorem. .. .. .. .. . .. .. .. .. . .. ...1258.2
Nernsts theorem applied to solids. . . . . . . . . . . . . . .. 128 8.3 Theentropy constantof
gases. .. ................1328.4Thermalionizationofagas:thethermioniceffect.....
..135
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ll
Ill

ListofFigures
1.1 Expansion of gas using a piston. . . . . . . . . . . . . . . . . 5 1.2 Expansion ofgas in a
irregularshapecontainer.........61.3Transformationon(V,p)diagram...............
.61.4Acyclicaltransformation.....................7
2.1Joulesexperiment.........................202.2Adiabaticchange.............
.............24
3.1Carnotcycle.............................303.2Carnotprocess.................
..........31
4.1 Differenttransformations from Ato B. .. . ..........444.2Twopaths,IandII,fromA
toB..................444.3AreversiblepathRfromAtoBandanirreversiblepathI
fromBtoA.............................494.4Twodifferentpaths,IandII,from
stateAtoBona(V,p)
diagram. .. ............................544.5Isothermsofasubstanceona(V,
p)diagram..........564.6Isotherms,accordingtoVanderWaalsequation,ofasub
stanceona(V,p)diagram....................624.7Anisothermofasubstance
atsupersaturatedconditionson
a(V,p)diagram..........................63
5.1Phasediagramforwater......................81
6.1VantHoffreactionbox......................906.2Isothermaltransformationin
VantHoffreactionbox.....91
7.1 Osmoticpressure... ......... ......... .....1067.2Determiningosmoticpressure..
................1077.3Colligativepropertiesofasolution................117
8.1GraphofC(T)againstTforasolid...............128
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viii

Introduction
THERMODYNAMICS is mainlyconcerned withthe transformation ofheatintomechanical
workandtheoppositetransformationofmechanicalworkintoheat.
Only in comparatively recent times have physicists recognized that heat is a form of
energythatcan be changedinto otherformsofenergy.Formerly,scientisthadthoughtthat
heatwassomesortoffluidwhosetotalamountwasinvariable,andhadsimplyinterpreted
the heatingof a bodyand analogous process as consistingofthetransferofthisfluidfrom
one body to another. It is, therefore, noteworthy that on the basis of this heatfluid theory
Carnot was ablein the year1824,to arrive at a comparativelyclearunderstandingofthe
limitations involved in the transforma tion of heat into work, that is, ofessentially what is
nowcalledthesecondlawofthermodynamics(seeChapter4).
In1842,onlyeighteenyearslater,R.J.Mayerdiscoveredtheequivalenceofheatand
mechanicalwork,andmadethefirstannouncementoftheprincipleofconservationof
energy(thefirstlawofthermodynamics).Weknowtodaythattheactualbasisofthe
equivalenceofheatanddynamicalenergyistobesoughtinthekineticinterpretation,
whichreducesallthermalphenomenatothedisorderedmotionsofatomsandmolecules.
Fromthispointofview,thestudyofheatmustbeconsideredasaspecialbranchof
mechanics:themechanicsofanensembleofsuchanenormousnumberofparticles
(atomsofmolecules)thatthedetaileddescriptionofthestateandthemotionloses
importanceandonlyaveragepropertiesoflargenumbersofparticlesaretobe
considered.Thisbranchofmechanics,calledstatisticalmechanics,whichhasbeen
developedmainlythroughtheworkofMaxwell,Boltzmann,andGibbs,hasledtoavery
satisfactoryunderstandingofthefundamentalthermodynamicallaws.
But the approach in pure thermodynamicsis different.Here thefunda mental lawsare
assumedaspostulatesbased on experimentalevidence, and conclusionsaredrawnfrom
them without entering into the kinetic mechanism of the phenomena. This procedure has
theadvantageofbeing
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independent, to a great extent, of the simplifying assumptions that are of ten made in
statistical mechanical considerations. Thus, thermodynamical results are generally highly
accurate.On the otherhand,itis sometimesratherunsatisfactory toobtain results without
being able toseein detail howthings reallywork,sothat inmanyrespects it is very often
conve nient to complete a thermodynamical result with at least a rough kinetic
interpretation.
The first and second law of thermodynamics have their statistical foun dation in
classical mechanics. InrecentyearsNernsthasaddedathirdlawwhichcanbeinterpreted
statistically only in terms of quantummechan ical concepts. The last chapter ofthisbook
willconcernitselfwiththeconsequenceofthethirdlaw.
x