Secondlawofthermodynamics

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Thesecondlawofthermodynamicsstatesthatinanaturalthermodynamicprocess,thereisanincreaseinthe
sumoftheentropiesoftheparticipatingsystems.
Thesecondlawisanempiricalfindingthathasbeenacceptedasanaxiomofthermodynamictheory.
Thelawdefinestheconceptofthermodynamicentropyforathermodynamicsysteminitsownstateofinternal
thermodynamicequilibrium.Itconsidersaprocessinwhichthatstatechanges,withincreasesinentropydueto
dissipationofenergyandtodispersalofmatterandenergy.
Thelawenvisagesacompoundthermodynamicsystemthatinitiallyhasinteriorwallsthatconstraintransfers
withinit.Thelawthenenvisagesthataprocessisinitiatedbyathermodynamicoperationthatchangesthose
constraints,andisolatesthecompoundsystemfromitssurroundings,exceptthatanexternallyimposed
unchangingforcefieldisallowedtostaysubjecttotheconditionthatthecompoundsystemmovesasawhole
withinthatfieldsothatinnet,thereisnotransferofenergyasworkbetweenthecompoundsystemandthe
surroundings,andfinally,eventually,thesystemisstationarywithinthatfield.
Duringtheprocess,theremayoccurchemicalreactions,andtransfersofmatterandofenergy.Ineach
adiabaticallyseparatedcompartment,thetemperaturebecomesspatiallyhomogeneous,eveninthepresenceof
theexternallyimposedunchangingexternalforcefield.If,betweentwoadiabaticallyseparatedcompartments,
transferofenergyasworkispossible,thenitproceedsuntilthesumoftheentropiesoftheequilibrated
compartmentsismaximumsubjecttotheotherconstraints.Iftheexternallyimposedforcefieldiszero,thenthe
chemicalconcentrationsalsobecomeasspatiallyhomogeneousasisallowedbythepermeabilitiesoftheinterior
walls,andbythepossibilitiesofphaseseparations,whichoccursoastomaximizethesumoftheentropiesofthe
equilibratedphasessubjecttotheotherconstraints.Suchhomogeneityandphaseseparationischaracteristicof
thestateofinternalthermodynamicequilibriumofathermodynamicsystem.[1][2]Iftheexternallyimposedforce
fieldisnonzero,thenthechemicalconcentrationsspatiallyredistributethemselvessoastomaximizethesumof
theequilibratedentropiessubjecttotheotherconstraintsandphaseseparations.
Statisticalthermodynamics,classicalorquantum,explainsthelaw.
Thesecondlawhasbeenexpressedinmanyways.ItsfirstformulationiscreditedtotheFrenchscientistSadi
Carnotin1824(seeTimelineofthermodynamics).

Contents
1Introduction
2Variousstatementsofthelaw
2.1Carnot'sprinciple
2.2Clausiusstatement
2.3Kelvinstatement
2.4EquivalenceoftheClausiusandtheKelvinstatements
2.5Planck'sproposition
2.6RelationbetweenKelvin'sstatementandPlanck'sproposition
2.7Planck'sstatement
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2.8PrincipleofCarathodory
2.9Planck'sPrinciple
2.10Statementforasystemthathasaknownexpressionofitsinternalenergyasafunctionofits
extensivestatevariables
2.11Gravitationalsystems
3Corollaries
3.1Perpetualmotionofthesecondkind
3.2Carnottheorem
3.3ClausiusInequality
3.4Thermodynamictemperature
3.5Entropy
3.6Energy,availableusefulwork
4History
4.1Informaldescriptions
4.2Mathematicaldescriptions
5Derivationfromstatisticalmechanics
5.1Derivationoftheentropychangeforreversibleprocesses
5.2Derivationforsystemsdescribedbythecanonicalensemble
5.3Generalderivationfromunitarityofquantummechanics
6Nonequilibriumstates
7Arrowoftime
8Controversies
8.1Maxwell'sdemon
8.2Loschmidt'sparadox
8.3Poincarrecurrencetheorem
9Quotations
10Seealso
11References
11.1Bibliographyofcitations
12Furtherreading
13Externallinks

Introduction
Thefirstlawofthermodynamicsprovidesthebasicdefinitionofthermodynamicenergy,alsocalledinternal
energy,associatedwithallthermodynamicsystems,butunknowninclassicalmechanics,andstatestheruleof
conservationofenergyinnature.[3][4]
Theconceptofenergyinthefirstlawdoesnot,however,accountfortheobservationthatnaturalprocesseshave
apreferreddirectionofprogress.Thefirstlawissymmetricalwithrespecttotheinitialandfinalstatesofan
evolvingsystem.Butthesecondlawassertsthatanaturalprocessrunsonlyinonesense,andisnotreversible.
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Forexample,heatalwaysflowsspontaneouslyfromhottertocolderbodies,andneverthereverse,unless
externalworkisperformedonthesystem.Thekeyconceptfortheexplanationofthisphenomenonthroughthe
secondlawofthermodynamicsisthedefinitionofanewphysicalquantity,theentropy.[5][6]
Formathematicalanalysisofprocesses,entropyisintroducedasfollows.Inafictivereversibleprocess,an
infinitesimalincrementintheentropy(dS)ofasystemresultsfromaninfinitesimaltransferofheat(Q)toa
closedsystemdividedbythecommontemperature(T)ofthesystemandthesurroundingswhichsupplythe
heat.[7]

Thezerothlawofthermodynamicsinitsusualshortstatementallowsrecognitionthattwobodiesinarelationof
thermalequilibriumhavethesametemperature,especiallythatatestbodyhasthesametemperatureasa
referencethermometricbody.[8]Forabodyinthermalequilibriumwithanother,thereareindefinitelymany
empiricaltemperaturescales,ingeneralrespectivelydependingonthepropertiesofaparticularreference
thermometricbody.Thesecondlawallowsadistinguishedtemperaturescale,whichdefinesanabsolute,
thermodynamictemperature,independentofthepropertiesofanyparticularreferencethermometricbody.[9][10]

Variousstatementsofthelaw
Thesecondlawofthermodynamicsmaybeexpressedinmanyspecificways,[11]themostprominentclassical
statements[12]beingthestatementbyRudolfClausius(1854),thestatementbyLordKelvin(1851),andthe
statementinaxiomaticthermodynamicsbyConstantinCarathodory(1909).Thesestatementscastthelawin
generalphysicaltermscitingtheimpossibilityofcertainprocesses.TheClausiusandtheKelvinstatementshave
beenshowntobeequivalent.[13]

Carnot'sprinciple
ThehistoricaloriginofthesecondlawofthermodynamicswasinCarnot'sprinciple.Itreferstoacycleofa
Carnotengine,fictivelyoperatedinthelimitingmodeofextremeslownessknownasquasistatic,sothattheheat
andworktransfersarebetweensubsystemsthatarealwaysintheirowninternalstatesofthermodynamic
equilibrium.TheCarnotengineisanidealizeddeviceofspecialinteresttoengineerswhoareconcernedwiththe
efficiencyofheatengines.Carnot'sprinciplewasrecognizedbyCarnotatatimewhenthecalorictheoryofheat
wasseriouslyconsidered,beforetherecognitionofthefirstlawofthermodynamics,andbeforethemathematical
expressionoftheconceptofentropy.Interpretedinthelightofthefirstlaw,itisphysicallyequivalenttothe
secondlawofthermodynamics,andremainsvalidtoday.Itstates
TheefficiencyofaquasistaticorreversibleCarnotcycledependsonlyonthetemperaturesofthe
twoheatreservoirs,andisthesame,whatevertheworkingsubstance.ACarnotengineoperatedin
thiswayisthemostefficientpossibleheatengineusingthosetwo
temperatures.[14][15][16][17][18][19][20]

Clausiusstatement
TheGermanscientistRudolfClausiuslaidthefoundationforthesecondlawofthermodynamicsin1850by
examiningtherelationbetweenheattransferandwork.[21]Hisformulationofthesecondlaw,whichwas
publishedinGermanin1854,isknownastheClausiusstatement:
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Heatcanneverpassfromacoldertoawarmerbodywithoutsomeotherchange,connected
therewith,occurringatthesametime.[22]
ThestatementbyClausiususestheconceptof'passageofheat'.Asisusualinthermodynamicdiscussions,this
means'nettransferofenergyasheat',anddoesnotrefertocontributorytransfersonewayandtheother.
Heatcannotspontaneouslyflowfromcoldregionstohotregionswithoutexternalworkbeingperformedonthe
system,whichisevidentfromordinaryexperienceofrefrigeration,forexample.Inarefrigerator,heatflows
fromcoldtohot,butonlywhenforcedbyanexternalagent,therefrigerationsystem.

Kelvinstatement
LordKelvinexpressedthesecondlawas
Itisimpossible,bymeansofinanimatematerialagency,toderivemechanicaleffectfromany
portionofmatterbycoolingitbelowthetemperatureofthecoldestofthesurroundingobjects.[23]

EquivalenceoftheClausiusandtheKelvinstatements
SupposethereisanengineviolatingtheKelvinstatement:
i.e.,onethatdrainsheatandconvertsitcompletelyintowork
inacyclicfashionwithoutanyotherresult.Nowpairitwith
areversedCarnotengineasshownbythefigure.Thenetand
soleeffectofthisnewlycreatedengineconsistingofthetwo
enginesmentionedistransferringheat
fromthecoolerreservoirtothehotter
one,whichviolatestheClausiusstatement.Thusaviolation
oftheKelvinstatementimpliesaviolationoftheClausius
statement,i.e.theClausiusstatementimpliestheKelvin
statement.WecanproveinasimilarmannerthattheKelvin
statementimpliestheClausiusstatement,andhencethetwo
areequivalent.

Planck'sproposition

DeriveKelvinStatementfromClausiusStatement

Planckofferedthefollowingpropositionasderiveddirectlyfromexperience.Thisissometimesregardedashis
statementofthesecondlaw,butheregardeditasastartingpointforthederivationofthesecondlaw.
Itisimpossibletoconstructanenginewhichwillworkinacompletecycle,andproducenoeffect
excepttheraisingofaweightandcoolingofaheatreservoir.[24][25]

RelationbetweenKelvin'sstatementandPlanck'sproposition
Itisalmostcustomaryintextbookstospeakofthe"KelvinPlanckstatement"ofthelaw.Forexample,see.[26]
OnetextgivesastatementthatforalltheworldlookslikePlanck'sproposition,butattributesittoKelvinwithout
mentionofPlanck.[27]OnemonographquotesPlanck'spropositionasthe"KelvinPlanck"formulation,thetext
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namingKelvinasitsauthor,thoughitcorrectlycitesPlanckinitsreferences.[28]Thereadermaycomparethe
twostatementsquotedjustabovehere.

Planck'sstatement
Planckstatedthesecondlawasfollows.
Everyprocessoccurringinnatureproceedsinthesenseinwhichthesumoftheentropiesofall
bodiestakingpartintheprocessisincreased.Inthelimit,i.e.forreversibleprocesses,thesumof
theentropiesremainsunchanged.[29][30][31]

PrincipleofCarathodory
ConstantinCarathodoryformulatedthermodynamicsonapurelymathematicalaxiomaticfoundation.His
statementofthesecondlawisknownasthePrincipleofCarathodory,whichmaybeformulatedasfollows:[32]
IneveryneighborhoodofanystateSofanadiabaticallyenclosedsystemtherearestatesinaccessible
fromS.[33]
Withthisformulation,hedescribedtheconceptofadiabaticaccessibilityforthefirsttimeandprovidedthe
foundationforanewsubfieldofclassicalthermodynamics,oftencalledgeometricalthermodynamics.Itfollows
fromCarathodory'sprinciplethatquantityofenergyquasistaticallytransferredasheatisaholonomicprocess
function,inotherwords,
.[34]
ThoughitisalmostcustomaryintextbookstosaythatCarathodory'sprincipleexpressesthesecondlawandto
treatitasequivalenttotheClausiusortotheKelvinPlanckstatements,suchisnotthecase.Togetallthe
contentofthesecondlaw,Carathodory'sprincipleneedstobesupplementedbyPlanck'sprinciple,that
isochoricworkalwaysincreasestheinternalenergyofaclosedsystemthatwasinitiallyinitsowninternal
thermodynamicequilibrium.[35][36][37][38]

Planck'sPrinciple
In1926,MaxPlanckwroteanimportantpaperonthebasicsofthermodynamics.[37][39]Heindicatedtheprinciple
Theinternalenergyofaclosedsystemisincreasedbyanadiabaticprocess,throughouttheduration
ofwhich,thevolumeofthesystemremainsconstant.[35][36]
Thisformulationdoesnotmentionheatanddoesnotmentiontemperature,norevenentropy,anddoesnot
necessarilyimplicitlyrelyonthoseconcepts,butitimpliesthecontentofthesecondlaw.Acloselyrelated
statementisthat"Frictionalpressureneverdoespositivework."[40]Usinganowobsoleteformofwords,Planck
himselfwrote:"Theproductionofheatbyfrictionisirreversible."[41][42]
Notmentioningentropy,thisprincipleofPlanckisstatedinphysicalterms.Itisverycloselyrelatedtothe
Kelvinstatementgivenjustabove.[43]Nevertheless,thisprincipleofPlanckisnotactuallyPlanck'spreferred
statementofthesecondlaw,whichisquotedabove,inaprevioussubsectionofthepresentsectionofthis
presentarticle,andreliesontheconceptofentropy.

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ThelinktoKelvin'sstatementisillustratedbyanequivalentstatementbyAllahverdyan&Nieuwenhuizen,
whichtheyattributetoKelvin:"Noworkcanbeextractedfromaclosedequilibriumsystemduringacyclic
variationofaparameterbyanexternalsource."[44][45]

Statementforasystemthathasaknownexpressionofitsinternalenergyasafunctionof
itsextensivestatevariables
ThesecondlawhasbeenshowntobeequivalenttotheinternalenergyUbeingaweaklyconvexfunction,when
writtenasafunctionofextensiveproperties(mass,volume,entropy,...).[46][47]

Gravitationalsystems
Innongravitationalsystems,objectsalwayshavepositiveheatcapacity,meaningthatthetemperatureriseswith
energy.Therefore,whenenergyflowsfromahightemperatureobjecttoalowtemperatureobject,thesource
temperatureisdecreasedwhilethesinktemperatureisincreasedhencetemperaturedifferencestendtodiminish
overtime.
However,thisisnotalwaysthecaseforsystemsinwhichthegravitationalforceisimportant.Themoststriking
examplesareblackholes,whichaccordingtotheoryhavenegativeheatcapacity.Thelargertheblackhole,
themoreenergyitcontains,buttheloweritstemperature.Thus,thesupermassiveblackholeinthecenterofthe
MilkyWayissupposedtohaveatemperatureof1014K,muchlowerthanthecosmicmicrowavebackground
temperatureof2.7K,butasitabsorbsphotonsofthecosmicmicrowavebackgrounditsmassisincreasingsothat
itslowtemperaturefurtherdecreaseswithtime.
Forthisreason,gravitationalsystemstendtowardsnonevendistributionofmassandenergy.Theuniversein
largescaleisimportantlyagravitationalsystem,andthesecondlawmaythereforenotapplytoit.

Corollaries
Perpetualmotionofthesecondkind
BeforetheestablishmentoftheSecondLaw,manypeoplewhowereinterestedininventingaperpetualmotion
machinehadtriedtocircumventtherestrictionsofFirstLawofThermodynamicsbyextractingthemassive
internalenergyoftheenvironmentasthepowerofthemachine.Suchamachineiscalleda"perpetualmotion
machineofthesecondkind".Thesecondlawdeclaredtheimpossibilityofsuchmachines.

Carnottheorem
Carnot'stheorem(1824)isaprinciplethatlimitsthemaximumefficiencyforanypossibleengine.Theefficiency
solelydependsonthetemperaturedifferencebetweenthehotandcoldthermalreservoirs.Carnot'stheorem
states:
AllirreversibleheatenginesbetweentwoheatreservoirsarelessefficientthanaCarnotengineoperating
betweenthesamereservoirs.
AllreversibleheatenginesbetweentwoheatreservoirsareequallyefficientwithaCarnotengine
operatingbetweenthesamereservoirs.
Inhisidealmodel,theheatofcaloricconvertedintoworkcouldbereinstatedbyreversingthemotionofthe
cycle,aconceptsubsequentlyknownasthermodynamicreversibility.Carnot,however,furtherpostulatedthat
somecaloricislost,notbeingconvertedtomechanicalwork.Hence,norealheatenginecouldrealisetheCarnot
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cycle'sreversibilityandwascondemnedtobelessefficient.
Thoughformulatedintermsofcaloric(seetheobsoletecalorictheory),ratherthanentropy,thiswasanearly
insightintothesecondlaw.

ClausiusInequality
TheClausiusTheorem(1854)statesthatinacyclicprocess

Theequalityholdsinthereversiblecase[48]andthe'<'isintheirreversiblecase.Thereversiblecaseisusedto
introducethestatefunctionentropy.Thisisbecauseincyclicprocessesthevariationofastatefunctioniszero
fromstatefunctionality.

Thermodynamictemperature
Foranarbitraryheatengine,theefficiencyis:

whereAistheworkdonepercycle.ThustheefficiencydependsonlyonqC/qH.
Carnot'stheoremstatesthatallreversibleenginesoperatingbetweenthesameheatreservoirsareequally
efficient.Thus,anyreversibleheatengineoperatingbetweentemperaturesT1andT2musthavethesame
efficiency,thatistosay,theefficiencyisthefunctionoftemperaturesonly:
Inaddition,areversibleheatengineoperatingbetweentemperaturesT1andT3musthavethesameefficiencyas
oneconsistingoftwocycles,onebetweenT1andanother(intermediate)temperatureT2,andthesecondbetween
T2andT3.Thiscanonlybethecaseif

Nowconsiderthecasewhere
ThenforanyT2andT3,

isafixedreferencetemperature:thetemperatureofthetriplepointofwater.

Thereforeifthermodynamictemperatureisdefinedby

thenthefunctionf,viewedasafunctionofthermodynamictemperature,issimply

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andthereferencetemperatureT1willhavethevalue273.16.(Ofcourseanyreferencetemperatureandany
positivenumericalvaluecouldbeusedthechoiceherecorrespondstotheKelvinscale.)

Entropy
AccordingtotheClausiusequality,forareversibleprocess

Thatmeansthelineintegral

ispathindependent.

SowecandefineastatefunctionScalledentropy,whichsatisfies

Withthiswecanonlyobtainthedifferenceofentropybyintegratingtheaboveformula.Toobtaintheabsolute
value,weneedtheThirdLawofThermodynamics,whichstatesthatS=0atabsolutezeroforperfectcrystals.
Foranyirreversibleprocess,sinceentropyisastatefunction,wecanalwaysconnecttheinitialandterminal
stateswithanimaginaryreversibleprocessandintegratingonthatpathtocalculatethedifferenceinentropy.
Nowreversethereversibleprocessandcombineitwiththesaidirreversibleprocess.ApplyingClausius
inequalityonthisloop,

Thus,

wheretheequalityholdsifthetransformationisreversible.
Noticethatiftheprocessisanadiabaticprocess,then

,so

Energy,availableusefulwork
AnimportantandrevealingidealizedspecialcaseistoconsiderapplyingtheSecondLawtothescenarioofan
isolatedsystem(calledthetotalsystemoruniverse),madeupoftwoparts:asubsystemofinterest,andthesub
system'ssurroundings.Thesesurroundingsareimaginedtobesolargethattheycanbeconsideredasan
unlimitedheatreservoirattemperatureTRandpressurePRsothatnomatterhowmuchheatistransferredto
(orfrom)thesubsystem,thetemperatureofthesurroundingswillremainTRandnomatterhowmuchthe
volumeofthesubsystemexpands(orcontracts),thepressureofthesurroundingswillremainPR.

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WhateverchangestodSanddSRoccurintheentropiesofthesubsystemandthesurroundingsindividually,
accordingtotheSecondLawtheentropyStotoftheisolatedtotalsystemmustnotdecrease:

AccordingtotheFirstLawofThermodynamics,thechangedUintheinternalenergyofthesubsystemisthe
sumoftheheatqaddedtothesubsystem,lessanyworkwdonebythesubsystem,plusanynetchemical
energyenteringthesubsystemdiRNi,sothat:

whereiRarethechemicalpotentialsofchemicalspeciesintheexternalsurroundings.
Nowtheheatleavingthereservoirandenteringthesubsystemis

wherewehavefirstusedthedefinitionofentropyinclassicalthermodynamics(alternatively,instatistical
thermodynamics,therelationbetweenentropychange,temperatureandabsorbedheatcanbederived)andthen
theSecondLawinequalityfromabove.
Itthereforefollowsthatanynetworkwdonebythesubsystemmustobey

Itisusefultoseparatetheworkwdonebythesubsystemintotheusefulworkwuthatcanbedonebythesub
system,overandbeyondtheworkpRdVdonemerelybythesubsystemexpandingagainstthesurrounding
externalpressure,givingthefollowingrelationfortheusefulwork(exergy)thatcanbedone:

Itisconvenienttodefinetherighthandsideastheexactderivativeofathermodynamicpotential,calledthe
availabilityorexergyEofthesubsystem,

TheSecondLawthereforeimpliesthatforanyprocesswhichcanbeconsideredasdividedsimplyintoa
subsystem,andanunlimitedtemperatureandpressurereservoirwithwhichitisincontact,

i.e.thechangeinthesubsystem'sexergyplustheusefulworkdonebythesubsystem(or,thechangeinthe
subsystem'sexergylessanywork,additionaltothatdonebythepressurereservoir,doneonthesystem)mustbe
lessthanorequaltozero.
Insum,ifaproperinfinitereservoirlikereferencestateischosenasthesystemsurroundingsintherealworld,
thentheSecondLawpredictsadecreaseinEforanirreversibleprocessandnochangeforareversibleprocess.
Isequivalentto

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Thisexpressiontogetherwiththeassociatedreferencestatepermitsadesignengineerworkingatthe
macroscopicscale(abovethethermodynamiclimit)toutilizetheSecondLawwithoutdirectlymeasuringor
consideringentropychangeinatotalisolatedsystem.(Also,seeprocessengineer).Thosechangeshavealready
beenconsideredbytheassumptionthatthesystemunderconsiderationcanreachequilibriumwiththereference
statewithoutalteringthereferencestate.Anefficiencyforaprocessorcollectionofprocessesthatcomparesitto
thereversibleidealmayalsobefound(Seesecondlawefficiency.)
ThisapproachtotheSecondLawiswidelyutilizedinengineeringpractice,environmentalaccounting,systems
ecology,andotherdisciplines.

History
ThefirsttheoryoftheconversionofheatintomechanicalworkisduetoNicolas
LonardSadiCarnotin1824.Hewasthefirsttorealizecorrectlythatthe
efficiencyofthisconversiondependsonthedifferenceoftemperaturebetweenan
engineanditsenvironment.
RecognizingthesignificanceofJamesPrescottJoule'sworkontheconservation
ofenergy,RudolfClausiuswasthefirsttoformulatethesecondlawduring1850,
inthisform:heatdoesnotflowspontaneouslyfromcoldtohotbodies.While
commonknowledgenow,thiswascontrarytothecalorictheoryofheatpopular
atthetime,whichconsideredheatasafluid.Fromtherehewasabletoinferthe
principleofSadiCarnotandthedefinitionofentropy(1865).
Establishedduringthe19thcentury,theKelvinPlanckstatementoftheSecond
Lawsays,"Itisimpossibleforanydevicethatoperatesonacycletoreceiveheat
fromasinglereservoirandproduceanetamountofwork."Thiswasshowntobe
equivalenttothestatementofClausius.

NicolasLonardSadiCarnot
inthetraditionaluniformof
astudentofthecole
Polytechnique.

TheergodichypothesisisalsoimportantfortheBoltzmannapproach.Itsaysthat,
overlongperiodsoftime,thetimespentinsomeregionofthephasespaceofmicrostateswiththesameenergy
isproportionaltothevolumeofthisregion,i.e.thatallaccessiblemicrostatesareequallyprobableoveralong
periodoftime.Equivalently,itsaysthattimeaverageandaverageoverthestatisticalensemblearethesame.
Ithasbeenshownthatnotonlyclassicalsystemsbutalsoquantummechanicalonestendtomaximizetheir
entropyovertime.Thusthesecondlawfollows,giveninitialconditionswithlowentropy.Moreprecisely,ithas
beenshownthatthelocalvonNeumannentropyisatitsmaximumvaluewithaveryhighprobability.[49]The
resultisvalidforalargeclassofisolatedquantumsystems(e.g.agasinacontainer).Whilethefullsystemis
pureandthereforedoesnothaveanyentropy,theentanglementbetweengasandcontainergivesrisetoan
increaseofthelocalentropyofthegas.Thisresultisoneofthemostimportantachievementsofquantum
thermodynamics.
Today,mucheffortinthefieldisattemptingtounderstandwhytheinitialconditionsearlyintheuniversewere
thoseoflowentropy,[50][51]asthisisseenastheoriginofthesecondlaw(seebelow).

Informaldescriptions
Thesecondlawcanbestatedinvarioussuccinctways,including:
Itisimpossibletoproduceworkinthesurroundingsusingacyclicprocessconnectedtoasingleheat
reservoir(Kelvin,1851).
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Itisimpossibletocarryoutacyclicprocessusinganengineconnectedtotwoheatreservoirsthatwillhave
asitsonlyeffectthetransferofaquantityofheatfromthelowtemperaturereservoirtothehigh
temperaturereservoir(Clausius,1854).
Ifthermodynamicworkistobedoneatafiniterate,freeenergymustbeexpended.(Stoner,2000)[52]

Mathematicaldescriptions
In1856,theGermanphysicistRudolfClausiusstatedwhathecalledthe"second
fundamentaltheoreminthemechanicaltheoryofheat"inthefollowingform:[53]

whereQisheat,TistemperatureandNisthe"equivalencevalue"ofall
uncompensatedtransformationsinvolvedinacyclicalprocess.Later,in1865,
Clausiuswouldcometodefine"equivalencevalue"asentropy.Ontheheelsof
thisdefinition,thatsameyear,themostfamousversionofthesecondlawwas
readinapresentationatthePhilosophicalSocietyofZurichonApril24,in
which,intheendofhispresentation,Clausiusconcludes:

Theentropyoftheuniversetendstoamaximum.

RudolfClausius

Thisstatementisthebestknownphrasingofthesecondlaw.Becauseoftheloosenessofitslanguage,e.g.
universe,aswellaslackofspecificconditions,e.g.open,closed,orisolated,manypeopletakethissimple
statementtomeanthatthesecondlawofthermodynamicsappliesvirtuallytoeverysubjectimaginable.This,of
course,isnottruethisstatementisonlyasimplifiedversionofamoreextendedandprecisedescription.
Intermsoftimevariation,themathematicalstatementofthesecondlawforanisolatedsystemundergoingan
arbitrarytransformationis:

where
Sistheentropyofthesystemand
tistime.
Theequalitysignholdsinthecasethatonlyreversibleprocessestakeplaceinsidethesystem.Ifirreversible
processestakeplace(whichisthecaseinrealsystemsinoperation)the>signholds.Analternativewayof
formulatingofthesecondlawforisolatedsystemsis:
with
with thesumoftherateofentropyproductionbyallprocessesinsidethesystem.Theadvantageofthis
formulationisthatitshowstheeffectoftheentropyproduction.Therateofentropyproductionisavery
importantconceptsinceitdetermines(limits)theefficiencyofthermalmachines.Multipliedwithambient
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temperature

itgivesthesocalleddissipatedenergy

Theexpressionofthesecondlawforclosedsystems(so,allowingheatexchangeandmovingboundaries,butnot
exchangeofmatter)is:
with
Here
istheheatflowintothesystem
isthetemperatureatthepointwheretheheatentersthesystem.
Ifheatissuppliedtothesystematseveralplaceswehavetotakethealgebraicsumofthecorrespondingterms.
Foropensystems(alsoallowingexchangeofmatter):
with
Here istheflowofentropyintothesystemassociatedwiththeflowofmatterenteringthesystem.Itshould
notbeconfusedwiththetimederivativeoftheentropy.Ifmatterissuppliedatseveralplaceswehavetotakethe
algebraicsumofthesecontributions.
Statisticalmechanicsgivesanexplanationforthesecondlawbypostulatingthatamaterialiscomposedofatoms
andmoleculeswhichareinconstantmotion.Aparticularsetofpositionsandvelocitiesforeachparticleinthe
systemiscalledamicrostateofthesystemandbecauseoftheconstantmotion,thesystemisconstantlychanging
itsmicrostate.Statisticalmechanicspostulatesthat,inequilibrium,eachmicrostatethatthesystemmightbeinis
equallylikelytooccur,andwhenthisassumptionismade,itleadsdirectlytotheconclusionthatthesecondlaw
mustholdinastatisticalsense.Thatis,thesecondlawwillholdonaverage,withastatisticalvariationonthe
orderof1/NwhereNisthenumberofparticlesinthesystem.Foreveryday(macroscopic)situations,the
probabilitythatthesecondlawwillbeviolatedispracticallyzero.However,forsystemswithasmallnumberof
particles,thermodynamicparameters,includingtheentropy,mayshowsignificantstatisticaldeviationsfromthat
predictedbythesecondlaw.Classicalthermodynamictheorydoesnotdealwiththesestatisticalvariations.

Derivationfromstatisticalmechanics
DuetoLoschmidt'sparadox,derivationsoftheSecondLawhavetomakeanassumptionregardingthepast,
namelythatthesystemisuncorrelatedatsometimeinthepastthisallowsforsimpleprobabilistictreatment.
Thisassumptionisusuallythoughtasaboundarycondition,andthusthesecondLawisultimatelyaconsequence
oftheinitialconditionssomewhereinthepast,probablyatthebeginningoftheuniverse(theBigBang),though
otherscenarioshavealsobeensuggested.[54][55][56]
Giventheseassumptions,instatisticalmechanics,theSecondLawisnotapostulate,ratheritisaconsequenceof
thefundamentalpostulate,alsoknownastheequalpriorprobabilitypostulate,solongasoneisclearthatsimple
probabilityargumentsareappliedonlytothefuture,whileforthepastthereareauxiliarysourcesofinformation
whichtellusthatitwaslowentropy.Thefirstpartofthesecondlaw,whichstatesthattheentropyofathermally
isolatedsystemcanonlyincrease,isatrivialconsequenceoftheequalpriorprobabilitypostulate,ifwerestrict
thenotionoftheentropytosystemsinthermalequilibrium.Theentropyofanisolatedsysteminthermal
equilibriumcontaininganamountofenergyof is:

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where
isthenumberofquantumstatesinasmallintervalbetween and
.Here
isa
macroscopicallysmallenergyintervalthatiskeptfixed.Strictlyspeakingthismeansthattheentropydependson
thechoiceof
.However,inthethermodynamiclimit(i.e.inthelimitofinfinitelylargesystemsize),the
specificentropy(entropyperunitvolumeorperunitmass)doesnotdependon
.
Supposewehaveanisolatedsystemwhosemacroscopicstateisspecifiedbyanumberofvariables.These
macroscopicvariablescan,e.g.,refertothetotalvolume,thepositionsofpistonsinthesystem,etc.Then will
dependonthevaluesofthesevariables.Ifavariableisnotfixed,(e.g.wedonotclampapistoninacertain
position),thenbecausealltheaccessiblestatesareequallylikelyinequilibrium,thefreevariableinequilibrium
willbesuchthat ismaximizedasthatisthemostprobablesituationinequilibrium.
Ifthevariablewasinitiallyfixedtosomevaluethenuponreleaseandwhenthenewequilibriumhasbeen
reached,thefactthevariablewilladjustitselfsothat ismaximized,impliesthattheentropywillhave
increasedoritwillhavestayedthesame(ifthevalueatwhichthevariablewasfixedhappenedtobethe
equilibriumvalue).Supposewestartfromanequilibriumsituationandwesuddenlyremoveaconstraintona
variable.Thenrightafterwedothis,thereareanumber ofaccessiblemicrostates,butequilibriumhasnotyet
beenreached,sotheactualprobabilitiesofthesystembeinginsomeaccessiblestatearenotyetequaltotheprior
probabilityof
.Wehavealreadyseenthatinthefinalequilibriumstate,theentropywillhaveincreasedor
havestayedthesamerelativetothepreviousequilibriumstate.Boltzmann'sHtheorem,however,provesthatthe
quantityHincreasesmonotonicallyasafunctionoftimeduringtheintermediateoutofequilibriumstate.

Derivationoftheentropychangeforreversibleprocesses
ThesecondpartoftheSecondLawstatesthattheentropychangeofasystemundergoingareversibleprocessis
givenby:

wherethetemperatureisdefinedas:

Seehereforthejustificationforthisdefinition.Supposethatthesystemhassomeexternalparameter,x,thatcan
bechanged.Ingeneral,theenergyeigenstatesofthesystemwilldependonx.Accordingtotheadiabatic
theoremofquantummechanics,inthelimitofaninfinitelyslowchangeofthesystem'sHamiltonian,thesystem
willstayinthesameenergyeigenstateandthuschangeitsenergyaccordingtothechangeinenergyofthe
energyeigenstateitisin.
Thegeneralizedforce,X,correspondingtotheexternalvariablexisdefinedsuchthat
isthework
performedbythesystemifxisincreasedbyanamountdx.E.g.,ifxisthevolume,thenXisthepressure.The
generalizedforceforasystemknowntobeinenergyeigenstate isgivenby:

Sincethesystemcanbeinanyenergyeigenstatewithinanintervalof
thesystemastheexpectationvalueoftheaboveexpression:

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,wedefinethegeneralizedforcefor

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Toevaluatetheaverage,wepartitionthe
for

withinarangebetween and

energyeigenstatesbycountinghowmanyofthemhaveavalue
.Callingthisnumber

,wehave:

Theaveragedefiningthegeneralizedforcecannowbewritten:

Wecanrelatethistothederivativeoftheentropyw.r.t.xatconstantenergyEasfollows.Supposewechangex
tox+dx.Then
willchangebecausetheenergyeigenstatesdependonx,causingenergyeigenstatesto
moveintooroutoftherangebetween and
.Let'sfocusagainontheenergyeigenstatesforwhich
lieswithintherangebetween and

.SincetheseenergyeigenstatesincreaseinenergybyYdx,

allsuchenergyeigenstatesthatareintheintervalrangingfromEYdxtoEmovefrombelowEtoaboveE.
Thereare

suchenergyeigenstates.If,alltheseenergyeigenstateswillmoveintotherangebetween and
and
contributetoanincreasein .Thenumberofenergyeigenstatesthatmovefrombelow
toabove
is,ofcourse,givenby.Thedifference

isthusthenetcontributiontotheincreasein .NotethatifYdxislargerthan
therewillbetheenergy
eigenstatesthatmovefrombelowEtoabove
.Theyarecountedinbothand,thereforetheabove
expressionisalsovalidinthatcase.
Expressingtheaboveexpressionasaderivativew.r.t.EandsummingoverYyieldstheexpression:

Thelogarithmicderivativeof w.r.t.xisthusgivenby:

Thefirsttermisintensive,i.e.itdoesnotscalewithsystemsize.Incontrast,thelasttermscalesastheinverse
systemsizeandwillthusvanishesinthethermodynamiclimit.Wehavethusfoundthat:

Combiningthiswith

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Gives:

Derivationforsystemsdescribedbythecanonicalensemble
IfasystemisinthermalcontactwithaheatbathatsometemperatureTthen,inequilibrium,theprobability
distributionovertheenergyeigenvaluesaregivenbythecanonicalensemble:

HereZisafactorthatnormalizesthesumofalltheprobabilitiesto1,thisfunctionisknownasthepartition
function.Wenowconsideraninfinitesimalreversiblechangeinthetemperatureandintheexternalparameters
onwhichtheenergylevelsdepend.Itfollowsfromthegeneralformulafortheentropy:

that

Insertingtheformulaforforthecanonicalensembleinheregives:

Generalderivationfromunitarityofquantummechanics
Thetimedevelopmentoperatorinquantumtheoryisunitary,becausetheHamiltonianishermitian.
Consequently,thetransitionprobabilitymatrixisdoublystochastic,whichimpliestheSecondLawof
Thermodynamics.[57][58]Thisderivationisquitegeneral,basedontheShannonentropy,anddoesnotrequireany
assumptionsbeyondunitarity,whichisuniversallyaccepted.Itisaconsequenceoftheirreversibilityorsingular
natureofthegeneraltransitionmatrix.

Nonequilibriumstates
Thetheoryofclassicalorequilibriumthermodynamicsisidealized.Amainpostulateorassumption,oftennot
evenexplicitlystated,istheexistenceofsystemsintheirowninternalstatesofthermodynamicequilibrium.In
general,aregionofspacecontainingaphysicalsystematagiventime,thatmaybefoundinnature,isnotin
thermodynamicequilibrium,readinthemoststringentterms.Inlooserterms,nothingintheentireuniverseisor
haseverbeentrulyinexactthermodynamicequilibrium.[59][60]
Forpurposesofphysicalanalysis,itisoftenenoughconvenienttomakeanassumptionofthermodynamic
equilibrium.Suchanassumptionmayrelyontrialanderrorforitsjustification.Iftheassumptionisjustified,it
canoftenbeveryvaluableandusefulbecauseitmakesavailablethetheoryofthermodynamics.Elementsofthe
equilibriumassumptionarethatasystemisobservedtobeunchangingoveranindefinitelylongtime,andthat
therearesomanyparticlesinasystem,thatitsparticulatenaturecanbeentirelyignored.Undersuchan
equilibriumassumption,ingeneral,therearenomacroscopicallydetectablefluctuations.Thereisanexception,
thecaseofcriticalstates,whichexhibittothenakedeyethephenomenonofcriticalopalescence.Forlaboratory
studiesofcriticalstates,exceptionallylongobservationtimesareneeded.

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Inallcases,theassumptionofthermodynamicequilibrium,oncemade,impliesasaconsequencethatnoputative
candidate"fluctuation"alterstheentropyofthesystem.
Itcaneasilyhappenthataphysicalsystemexhibitsinternalmacroscopicchangesthatarefastenoughto
invalidatetheassumptionoftheconstancyoftheentropy.Orthataphysicalsystemhassofewparticlesthatthe
particulatenatureismanifestinobservablefluctuations.Thentheassumptionofthermodynamicequilibriumisto
beabandoned.Thereisnounqualifiedgeneraldefinitionofentropyfornonequilibriumstates.[61]
Nonequilibriumthermodynamicsisthenappropriate.Thereareintermediatecases,inwhichtheassumptionof
localthermodynamicequilibriumisaverygoodapproximation,[62][63][64][65]butstrictlyspeakingitisstillan
approximation,nottheoreticallyideal.Fornonequilibriumsituationsingeneral,itmaybeusefultoconsider
statisticalmechanicaldefinitionsofquantitiesthatmaybeconvenientlycalled'entropy'.Theseindeedbelongto
statisticalmechanics,nottomacroscopicthermodynamics.
Thephysicsofmacroscopicallyobservablefluctuationsisbeyondthescopeofthisarticle.

Arrowoftime
Thesecondlawofthermodynamicsisaphysicallawthatisnotsymmetrictoreversalofthetimedirection.
Thesecondlawhasbeenproposedtosupplyanexplanationofthedifferencebetweenmovingforwardand
backwardsintime,suchaswhythecauseprecedestheeffect(thecausalarrowoftime).[66]

Controversies
Maxwell'sdemon
JamesClerkMaxwellimaginedonecontainerdividedintotwoparts,AandB.
Bothpartsarefilledwiththesamegasatequaltemperaturesandplacednextto
eachother.Observingthemoleculesonbothsides,animaginarydemonguardsa
trapdoorbetweenthetwoparts.WhenafasterthanaveragemoleculefromA
fliestowardsthetrapdoor,thedemonopensit,andthemoleculewillflyfromA
toB.TheaveragespeedofthemoleculesinBwillhaveincreasedwhileinAthey
willhavesloweddownonaverage.Sinceaveragemolecularspeedcorrespondsto
temperature,thetemperaturedecreasesinAandincreasesinB,contrarytothe
secondlawofthermodynamics.
Oneofthemostfamousresponsestothisquestionwassuggestedin1929byLe
SzilrdandlaterbyLonBrillouin.SzilrdpointedoutthatareallifeMaxwell's
demonwouldneedtohavesomemeansofmeasuringmolecularspeed,andthat
theactofacquiringinformationwouldrequireanexpenditureofenergy.

JamesClerkMaxwell

Maxwell'sdemonrepeatedlyaltersthepermeabilityofthewallbetweenAandB.
Itisthereforeperformingthermodynamicoperations,notjustpresidingovernaturalprocesses.

Loschmidt'sparadox
Loschmidt'sparadox,alsoknownasthereversibilityparadox,istheobjectionthatitshouldnotbepossibleto
deduceanirreversibleprocessfromtimesymmetricdynamics.Thisputsthetimereversalsymmetryofnearlyall
knownlowlevelfundamentalphysicalprocessesatoddswithanyattempttoinferfromthemthesecondlawof

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thermodynamicswhichdescribesthebehaviorofmacroscopicsystems.Bothofthesearewellaccepted
principlesinphysics,withsoundobservationalandtheoreticalsupport,yettheyseemtobeinconflicthencethe
paradox.
Oneproposedresolutionofthisparadoxisasfollows.TheLoschmidtscenarioreferstoastrictlyisolatedsystem
ortoastrictlyadiabaticallyisolatedsystem.Heatandmattertransfersarenotallowed.TheLoschmidtreversal
timesarefantasticallylong,farlongerthananylaboratoryisolationoftherequireddegreeofperfectioncouldbe
maintainedinpractice.Inthissense,theLoschmidtscenariowillneverbesubjectedtoempiricaltesting.Alsoin
thissense,thesecondlaw,statedforanisolatedsystem,willneverbesubjectedtoempiricaltesting.Asystem,
supposedlyperfectlyisolated,instrictlyperfectthermodynamicequilibrium,canbeobservedonlyonceinits
entirelife,becausetheobservationmustbreaktheisolation.Twoobservationswouldbeneededtocheck
empiricallyforachangeofstate,oneinitialandonefinal.Whentransferofheatormatterarepermitted,the
requirementsofperfectionarenotsotight.Inpracticallaboratoryreality,therefore,thesecondlawcanbetested
onlyforsystemswithtransferofheatormatter,andnotforisolatedsystems.
Duetothisparadox,derivationsofthesecondlawhavetomakeanassumptionregardingthepast,namelythat
thesystemisuncorrelatedatsometimeinthepastor,equivalently,thattheentropyinthepastwaslowerthanin
thefuture.Thisassumptionisusuallythoughtasaboundarycondition,andthusthesecondLawisultimately
derivedfromtheinitialconditionsoftheBigBang.[54][67]

Poincarrecurrencetheorem
ThePoincarrecurrencetheoremstatesthatcertainsystemswill,afterasufficientlylongtime,returntoastate
veryclosetotheinitialstate.ThePoincarrecurrencetimeisthelengthoftimeelapseduntiltherecurrence,
whichisoftheorderof.[68]Theresultappliestophysicalsystemsinwhichenergyisconserved.TheRecurrence
theoremapparentlycontradictstheSecondlawofthermodynamics,whichsaysthatlargedynamicalsystems
evolveirreversiblytowardsthestatewithhigherentropy,sothatifonestartswithalowentropystate,thesystem
willneverreturntoit.Therearemanypossiblewaystoresolvethisparadox,butnoneofthemisuniversally
accepted.Themostreasonableargumentisthatfortypicalthermodynamicalsystemstherecurrencetimeisso
large(manymanytimeslongerthanthelifetimeoftheuniverse)that,forallpracticalpurposes,onecannot
observetherecurrence.

Quotations
Thelawthatentropyalwaysincreasesholds,Ithink,thesupreme
positionamongthelawsofNature.Ifsomeonepointsouttoyou
thatyourpettheoryoftheuniverseisindisagreementwith
Maxwell'sequationsthensomuchtheworseforMaxwell's
equations.Ifitisfoundtobecontradictedbyobservationwell,
theseexperimentalistsdobunglethingssometimes.Butifyour
theoryisfoundtobeagainstthesecondlawofthermodynamicsI
cangiveyounohopethereisnothingforitbuttocollapsein
deepesthumiliation.

Wikiquotehasquotations
relatedto:Secondlawof
thermodynamics

SirArthurStanleyEddington,TheNatureofthePhysical
World(1927)
Therehavebeennearlyasmanyformulationsofthesecondlawastherehavebeendiscussionsofit.
Philosopher/PhysicistP.W.Bridgman,(1941)
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Clausiusistheauthorofthesibyllicutterance,"Theenergyoftheuniverseisconstanttheentropy
oftheuniversetendstoamaximum."Theobjectivesofcontinuumthermomechanicsstopfarshort
ofexplainingthe"universe",butwithinthattheorywemayeasilyderiveanexplicitstatementin
somewaysreminiscentofClausius,butreferringonlytoamodestobject:anisolatedbodyoffinite
size.
Truesdell,C.,Muncaster,R.G.(1980).FundamentalsofMaxwell'sKineticTheoryofaSimple
MonatomicGas,TreatedasaBranchofRationalMechanics,AcademicPress,NewYork,
ISBN0127013504,p.17.

Seealso
ClausiusDuheminequality
Entropy:ANewWorldView
Fluctuationtheorem
Historyofthermodynamics
Jarzynskiequality
Lawsofthermodynamics
Maximumentropythermodynamics
ReflectionsontheMotivePowerofFire
Thermaldiode
Relativisticheatconduction

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MagazineandJournalofScience.4th2(VIII):121102119.Retrieved26June2012.
Clausius,R.(1854)."bereinevernderteFormdeszweitenHauptsatzesdermechanischenWrmetheorie"
(http://zfbb.thulb.unijena.de/servlets/MCRFileNodeServlet/jportal_derivate_00140956/18541691202_ftp.pdf).Annalen
derPhysik(Poggendoff).xciii:481.doi:10.1002/andp.18541691202
(https://dx.doi.org/10.1002%2Fandp.18541691202).Retrieved24March2014.TranslatedintoEnglish:Clausius,R.
(July1856)."OnaModifiedFormoftheSecondFundamentalTheoremintheMechanicalTheoryofHeat"
(http://www.biodiversitylibrary.org/item/20044#page/100/mode/1up).London,EdinburghandDublinPhilosophical
MagazineandJournalofScience.4th2:86.Retrieved24March2014.Reprintedin:Clausius,R.(1867).The
MechanicalTheoryofHeatwithitsApplicationstotheSteamEngineandtoPhysicalPropertiesofBodies
(http://books.google.com/books?
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nDQ&ved=0CDYQuwUwAA#v=onepage&q&f=false).London:JohnvanVoorst.Retrieved19June2012.
Eu,B.C.(2002).GeneralizedThermodynamics.TheThermodynamicsofIrreversibleProcessesandGeneralized
Hydrodynamics,KluwerAcademicPublishers,Dordrecht,ISBN1402007884.
Glansdorff,P.,Prigogine,I.(1971).ThermodynamicTheoryofStructure,Stability,andFluctuations,Wiley
Interscience,London,1971,ISBN0471302805.
Grandy,W.T.,Jr(2008).EntropyandtheTimeEvolutionofMacroscopicSystems
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cc=au&lang=en&).OxfordUniversityPress.ISBN9780199546176.
Greven,A.,Keller,G.,Warnecke(editors)(2003).Entropy,PrincetonUniversityPress,PrincetonNJ,ISBN0691
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Gyarmati,I.(1967/1970)NonequilibriumThermodynamics.FieldTheoryandVariationalPrinciples,translatedbyE.
GyarmatiandW.F.Heinz,Springer,NewYork.
Kondepudi,D.,Prigogine,I.(1998).ModernThermodynamics:FromHeatEnginestoDissipativeStructures,John
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Kondepudi,D.,Prigogine,I.(1998).ModernThermodynamics:FromHeatEnginestoDissipativeStructures,John
Wiley&Sons,Chichester,ISBN0471973939.
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(http://arxiv.org/pdf/condmat/9708200v2.pdf).PhysicsReports310:196.arXiv:condmat/9708200
(https://arxiv.org/abs/condmat/9708200).Bibcode:1999PhR...310....1L
(http://adsabs.harvard.edu/abs/1999PhR...310....1L).doi:10.1016/S03701573(98)000829
(https://dx.doi.org/10.1016%2FS03701573%2898%29000829).Retrieved24March2014.
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Thomson,W.(1851)."OntheDynamicalTheoryofHeat,withnumericalresultsdeducedfromMrJoule'sequivalent
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XX(partII):261268289298.AlsopublishedinThomson,W.(December1852)."OntheDynamicalTheoryof
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Furtherreading
Goldstein,Martin,andIngeF.,1993.TheRefrigeratorandtheUniverse.HarvardUniv.Press.Chpts.49
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containanintroductiontotheSecondLaw,oneabitlesstechnicalthanthisentry.ISBN978067475324
2
Leff,HarveyS.,andRex,AndrewF.(eds.)2003.Maxwell'sDemon2:Entropy,classicalandquantum
information,computing.BristolUKPhiladelphiaPA:InstituteofPhysics.ISBN9780585492377
Halliwell,J.J.(1994).PhysicalOriginsofTimeAsymmetry.Cambridge.ISBN0521568374.(technical).
Carnot,SadiThurston,RobertHenry(editorandtranslator)(1890).ReflectionsontheMotivePowerof
HeatandonMachinesFittedtoDevelopThatPower.NewYork:J.Wiley&Sons.(fulltextof1897ed.
(http://books.google.com/books?id=tgdJAAAAIAAJ))(html
(http://www.history.rochester.edu/steam/carnot/1943/))
StephenJayKline(1999).TheLowDownonEntropyandInterpretiveThermodynamics,LaCaada,CA:
DCWIndustries.ISBN1928729010.
Kostic,M.,RevisitingTheSecondLawofEnergyDegradationandEntropyGeneration:FromSadi
Carnot'sIngeniousReasoningtoHolisticGeneralizationAIPConf.Proc.1411,pp.327350doi:
http://dx.doi.org/10.1063/1.3665247.AmericanInstituteofPhysics,2011.ISBN9780735409859.
Abstractat:[1](http://adsabs.harvard.edu/abs/2011AIPC.1411..327K).Fullarticle(24pages[2]
(http://scitation.aip.org/getpdf/servlet/GetPDFServlet?
filetype=pdf&id=APCPCS001411000001000327000001&idtype=cvips&doi=10.1063/1.3665247&prog=n
ormal&bypassSSO=1)),alsoat[3]
(http://www.kostic.niu.edu/2ndLaw/Revisiting%20The%20Second%20Law%20of%20Energy%20Degrad
ation%20and%20Entropy%20Generation%20%20From%20Carnot%20to%20Holistic%20Generalization
4.pdf).

Externallinks
StanfordEncyclopediaofPhilosophy:"PhilosophyofStatisticalMechanics
(http://plato.stanford.edu/entries/statphysstatmech/)"byLawrenceSklar.
Secondlawofthermodynamics
(http://web.mit.edu/16.unified/www/FALL/thermodynamics/notes/node30.html)intheMITCourse
UnifiedThermodynamicsandPropulsion
(http://web.mit.edu/16.unified/www/FALL/thermodynamics/notes/notes.html)fromProf.Z.S.
Spakovszky
E.T.Jaynes,1988,"TheevolutionofCarnot'sprinciple,(http://bayes.wustl.edu/etj/articles/ccarnot.pdf)"in
G.J.EricksonandC.R.Smith(eds.)MaximumEntropyandBayesianMethodsinScienceand
Engineering,Vol1,p.267.
Caratheodory,C.,"Examinationofthefoundationsofthermodynamics,"trans.byD.H.Delphenich
(http://neoclassicalphysics.info/uploads/3/0/6/5/3065888/caratheodory__thermodynamics.pdf)
Retrievedfrom"http://en.wikipedia.org/w/index.php?title=Second_law_of_thermodynamics&oldid=645805496"
Categories: Conceptsinphysics Lawsofthermodynamics Nonequilibriumthermodynamics
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