Thermodynamics

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ThermodynamicsWikipedia,thefreeencyclopedia
Thermodynamics
FromWikipedia,thefreeencyclopedia
Thermodynamicsisabranchofphysicsconcerned
withheatandtemperatureandtheirrelationto
energyandwork.Itdefinesmacroscopicvariables,
suchasinternalenergy,entropy,andpressure,that
partlydescribeabodyofmatterorradiation.Itstates
thatthebehaviorofthosevariablesissubjectto
generalconstraints,thatarecommontoallmaterials,
beyondthepeculiarpropertiesofparticular
materials.Thesegeneralconstraintsareexpressedin
thefourlawsofthermodynamics.Thermodynamics
describesthebulkbehaviorofthebody,notthe
microscopicbehaviorsoftheverylargenumbersof
itsmicroscopicconstituents,suchasmolecules.The
basicresultsofthermodynamicsrelyonthe
existenceofidealizedstatesofthermodynamic
equilibrium.Itslawsareexplainedbystatistical
mechanics,intermsofthemicroscopicconstituents.
Thermodynamicsappliestoawidevarietyoftopics
inscienceandengineering,especiallyphysical
chemistry,chemicalengineeringandmechanical
engineering.
Annotatedcolorversionoftheoriginal1824Carnot
heatengineshowingthehotbody(boiler),working
body(system,steam),andcoldbody(water),the
letterlabelsindicatethestoppingpointsinCarnot
cycle
Historically,thedistinctionbetweenheatand
temperaturewasstudiedinthe1750sbyJoseph
Black.CharacteristicallythermodynamicthinkingbeganintheworkofCarnot(1824)whobelievedthat
theefficiencyofheatengineswasthekeythatcouldhelpFrancewintheNapoleonicWars.[1]TheIrish
bornBritishphysicistLordKelvinwasthefirsttoformulateaconcisedefinitionofthermodynamicsin
1854:[2]
Thermodynamicsisthesubjectoftherelationofheattoforcesactingbetweencontiguous
partsofbodies,andtherelationofheattoelectricalagency.
Initially,thermodynamics,asappliedtoheatengines,wasconcernedwiththethermalpropertiesoftheir
'workingmaterials',suchassteam,inanefforttoincreasetheefficiencyandpoweroutputofengines.
Thermodynamicswaslaterexpandedtothestudyofenergytransfersinchemicalprocesses,suchasthe
investigation,publishedin1840,oftheheatsofchemicalreactions[3]byGermainHess,whichwasnot
originallyexplicitlyconcernedwiththerelationbetweenenergyexchangesbyheatandwork.Fromthis
evolvedthestudyofchemicalthermodynamicsandtheroleofentropyinchemical
reactions.[4][5][6][7][8][9][10][11]
Contents
1 Introduction
https://en.wikipedia.org/wiki/Thermodynamics
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1 Introduction
2 History
2.1 Etymology
3 Branchesofdescription
3.1 Classicalthermodynamics
3.2 Localequilibriumthermodynamics
3.3 Generalizedorextendedthermodynamics
3.4 Statisticalthermodynamics
4 Thermodynamicequilibrium
4.1 Quasistatictransfersbetweensimplesystemsarenearlyinthermodynamic
equilibriumandarereversible
4.2 Naturalprocessesarepartlydescribedbytendencytowardsthermodynamic
equilibriumandareirreversible
5 Nonequilibriumthermodynamics
6 Lawsofthermodynamics
7 Systemmodels
8 Statesandprocesses
8.1 Accountintermsofstatesofthermodynamicequilibrium
8.1.1 Equationofstate
8.2 Thermodynamicprocessesbetweenstatesofthermodynamicequilibrium
8.2.1 Dependentandindependentvariablesforaprocess
8.2.2 Changesofstateofasystem
8.2.3 Commonlyconsideredthermodynamicprocesses
8.3 Accountintermsofcyclicprocesses
9 Instrumentation
10 Conjugatevariables
11 Potentials
12 Axiomatics
13 Scopeofthermodynamics
14 Appliedfields
15 Seealso
15.1 Listsandtimelines
15.2 Wikibooks
16 References
17 Citedbibliography
18 Furtherreading
19 Externallinks
Introduction
Historically,thermodynamicsarosefromthestudyoftwodistinctkindsoftransferofenergy,asheatand
aswork,andtherelationofthosetothesystem'smacroscopicvariablesofvolume,pressureand
temperature.[12][13]Asitdeveloped,thermodynamicsbeganalsotostudytransfersofmatter.
Theplainterm'thermodynamics'referstoamacroscopicdescriptionofbodiesandprocesses.[14]
Referencetoatomicconstitutionisforeigntoclassicalthermodynamics.[15]Usuallytheplainterm
'thermodynamics'refersbydefaulttoequilibriumasopposedtononequilibriumthermodynamics.The
qualifiedterm'statisticalthermodynamics'referstodescriptionsofbodiesandprocessesintermsofthe
atomicorothermicroscopicconstitutionofmatter,usingstatisticalandprobabilisticreasoning.
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Thermodynamicequilibriumisoneofthemostimportantconceptsforthermodynamics.[16][17]The
temperatureofathermodynamicsystemiswelldefined,andisperhapsthemostcharacteristicquantity
ofthermodynamics.Asthesystemsandprocessesofinterestaretakenfurtherfromthermodynamic
equilibrium,theirexactthermodynamicalstudybecomesmoredifficult.Relativelysimpleapproximate
calculations,however,usingthevariablesofequilibriumthermodynamics,areofmuchpracticalvalue.
Manyimportantpracticalengineeringcases,asinheatenginesorrefrigerators,canbeapproximatedas
systemsconsistingofmanysubsystemsatdifferenttemperaturesandpressures.Ifaphysicalprocessis
toofast,theequilibriumthermodynamicvariables,forexampletemperature,maynotbewellenough
definedtoprovideausefulapproximation.
Centraltothermodynamicanalysisarethedefinitionsofthesystem,whichisofinterest,andofits
surroundings.[8][18]Thesurroundingsofathermodynamicsystemconsistofphysicaldevicesandof
otherthermodynamicsystemsthatcaninteractwithit.Anexampleofathermodynamicsurroundingisa
heatbath,whichisheldataprescribedtemperature,regardlessofhowmuchheatmightbedrawnfrom
it.
Therearefourfundamentalkindsofphysicalentitiesinthermodynamics:
statesofasystem,andthestatesofitssurroundingsystems
wallsofasystem,[19][20][21][22][23]
thermodynamicprocessesofasystem,and
thermodynamicoperations.
Thisallowstwofundamentalapproachestothermodynamicreasoning,thatintermsofstatesofa
system,andthatintermsofcyclicprocessesofasystem.
Athermodynamicsystemcanbedefinedintermsofitsstates.[17]Inthisway,athermodynamicsystem
isamacroscopicphysicalobject,explicitlyspecifiedintermsofmacroscopicphysicalandchemical
variablesthatdescribeitsmacroscopicproperties.Themacroscopicstatevariablesofthermodynamics
havebeenrecognizedinthecourseofempiricalworkinphysicsandchemistry.[9]Alwaysassociated
withthematerialthatconstitutesasystem,itsworkingsubstance,arethewallsthatdelimitthesystem,
andconnectitwithitssurroundings.Thestatevariableschosenforthesystemshouldbeappropriatefor
thenaturesofthewallsandsurroundings.[24]
Athermodynamicoperationisanartificialphysicalmanipulationthatchangesthedefinitionofasystem
oritssurroundings.Usuallyitisachangeofthepermeabilityofawallofthesystem,[25]thatallows
energy(asheatorwork)ormatter(mass)tobeexchangedwiththeenvironment.Forexample,the
partitionbetweentwothermodynamicsystemscanberemovedsoastoproduceasinglesystem.A
thermodynamicoperationthatincreasestherangeofpossibletransfersusuallyleadstoathermodynamic
processoftransferofmassorenergythatchangesthestateofthesystem,andthetransferoccursin
naturalaccordwiththelawsofthermodynamics.Butiftheoperationsimplyreducesthepossiblerange
oftransfers,ingeneralitdoesnotinitiateaprocess.Thestatesofthesystem'ssurroundingsystemsare
assumedtobeunchangingintimeexceptwhentheyarechangedbyathermodynamicoperation,
whereuponathermodynamicprocesscanbeinitiated.
Athermodynamicsystemcanalsobedefinedintermsofthecyclicprocessesthatitcanundergo.[26]A
cyclicprocessisacyclicsequenceofthermodynamicoperationsandprocessesthatcanberepeated
indefinitelyoftenwithoutchangingthefinalstateofthesystem.
Forthermodynamicsandstatisticalthermodynamicstoapplytoaphysicalsystem,itisnecessary
thatitsinternalatomicmechanismsfallintooneoftwoclasses:
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thosesorapidthat,inthetimeframeoftheprocessofinterest,theatomicstatesrapidlybring
systemtoitsownstateofinternalthermodynamicequilibriumand
thosesoslowthat,inthetimeframeoftheprocessofinterest,theyleavethesystem
unchanged.[27][28]
Therapidatomicmechanismsaccountfortheinternalenergyofthesystem.Theymediatethe
macroscopicchangesthatareofinterestforthermodynamicsandstatisticalthermodynamics,because
theyquicklybringthesystemnearenoughtothermodynamicequilibrium."Whenintermediateratesare
present,thermodynamicsandstatisticalmechanicscannotbeapplied."[27]Suchintermediaterateatomic
processesdonotbringthesystemnearenoughtothermodynamicequilibriuminthetimeframeofthe
macroscopicprocessofinterest.Thisseparationoftimescalesofatomicprocessesisathemethatrecurs
throughoutthesubject.
Forexample,classicalthermodynamicsischaracterizedbyitsstudyofmaterialsthathaveequationsof
stateorcharacteristicequations.Theyexpressequilibriumrelationsbetweenmacroscopicmechanical
variablesandtemperatureandinternalenergy.Theyexpresstheconstitutivepeculiaritiesofthematerial
ofthesystem.Aclassicalmaterialcanusuallybedescribedbyafunctionthatmakespressuredependent
onvolumeandtemperature,theresultingpressurebeingestablishedmuchmorerapidlythanany
imposedchangeofvolumeortemperature.[29][30][31][32]
Thepresentarticletakesagradualapproachtothesubject,startingwithafocusoncyclicprocessesand
thermodynamicequilibrium,andthengraduallybeginningtofurtherconsidernonequilibriumsystems.
Thermodynamicfactscanoftenbeexplainedbyviewingmacroscopicobjectsasassembliesofvery
manymicroscopicoratomicobjectsthatobeyHamiltoniandynamics.[8][33][34]Themicroscopicor
atomicobjectsexistinspecies,theobjectsofeachspeciesbeingallalike.Becauseofthislikeness,
statisticalmethodscanbeusedtoaccountforthemacroscopicpropertiesofthethermodynamicsystem
intermsofthepropertiesofthemicroscopicspecies.Suchexplanationiscalledstatistical
thermodynamicsalsooftenitisreferredtobytheterm'statisticalmechanics',thoughthistermcanhave
awidermeaning,referringto'microscopicobjects',suchaseconomicquantities,thatdonotobey
Hamiltoniandynamics.[33]
History
ThehistoryofthermodynamicsasascientificdisciplinegenerallybeginswithOttovonGuerickewho,
inabout1650,[35]builtanddesignedtheworld'sfirstvacuumpumpanddemonstratedavacuumusing
hisMagdeburghemispheres.GuerickewasdriventomakeavacuuminordertodisproveAristotle's
longheldsuppositionthat'natureabhorsavacuum'.ShortlyafterGuericke,thephysicistandchemist
RobertBoylehadlearnedofGuericke'sdesignsand,in1656,incoordinationwiththescientistRobert
Hooke,builtanairpump.[36]Usingthispump,BoyleandHookenoticedacorrelationbetweenpressure,
temperature,andvolume.Intime,theyformulatedBoyle'sLaw,whichstatesthatforagasatconstant
temperature,itspressureandvolumeareinverselyproportional.In1679,basedontheseconcepts,an
associateofBoyle'snamedDenisPapinbuiltasteamdigester,whichwasaclosedvesselwithatightly
fittinglidthatconfinedsteamuntilahighpressurewasgenerated.Laterversionsofthisdesign
implementedasteamreleasevalvethatkeptthemachinefromexploding.Bywatchingthevalve
rhythmicallymoveupanddown,Papinconceivedoftheideaofapistonandacylinderengine.Hedid
not,however,followthroughwithhisdesign.Nevertheless,in1697,basedonPapin'sdesigns,the
engineerThomasSaverybuiltthefirstengine,followedbyThomasNewcomenin1712.Althoughthese
earlyengineswerecrudeandinefficient,theyattractedtheattentionoftheleadingscientistsofthetime.
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Theconceptsofheatcapacityand
latentheat,whichwerenecessaryfor
developmentofthermodynamics,
weredevelopedbyProfessorJoseph
BlackattheUniversityofGlasgow,
whereJamesWattworkedasan
instrumentmaker.Wattconsulted
withBlackontestsofhissteam
engine,butitwasWattwho
conceivedtheideaoftheexternal
condenser,greatlyraisingthesteam
engine'sefficiency.[37]Allthe
previousworkledSadiCarnot,the
"fatherofthermodynamics",to
publishReflectionsontheMotive
PowerofFire(1824),adiscourseon
heat,power,energy,andengine
efficiency.Thepaperoutlinedthe
basicenergeticrelationsbetweenthe
Carnotengine,theCarnotcycle,and
motivepower.Itmarkedthestartof
thermodynamicsasamodern
science.[11]
Thethermodynamicistsrepresentativeoftheoriginaleightfounding
schoolsofthermodynamics.Theschoolswiththemostlastingeffect
infoundingthemodernversionsofthermodynamicsaretheBerlin
school,particularlyasestablishedinRudolfClausius's1865textbook
TheMechanicalTheoryofHeat,theViennaschool,whilethe
statisticalmechanicsofLudwigBoltzmann,andtheGibbsianschool
atYaleUniversity,ledbytheAmericanengineerWillardGibbs'1876
OntheEquilibriumofHeterogeneousSubstanceslaunchedchemical
thermodynamics.
Thefirstthermodynamictextbook
waswrittenin1859byWilliam
Rankine,originallytrainedasa
physicistandaprofessorofciviland
mechanicalengineeringatthe
UniversityofGlasgow.[38]Thefirst
andsecondlawsofthermodynamicsemergedsimultaneouslyinthe1850s,primarilyoutoftheworksof
WilliamRankine,RudolfClausius,andWilliamThomson(LordKelvin).
ThefoundationsofstatisticalthermodynamicsweresetoutbyphysicistssuchasJamesClerkMaxwell,
LudwigBoltzmann,MaxPlanck,RudolfClausiusandJ.WillardGibbs.
From1873to'76,theAmericanmathematicalphysicistJosiahWillardGibbspublishedaseriesofthree
papers,themostfamousbeing"Ontheequilibriumofheterogeneoussubstances".[4]Gibbsshowedhow
thermodynamicprocesses,includingchemicalreactions,couldbegraphicallyanalyzed.Bystudyingthe
energy,entropy,volume,chemicalpotential,temperatureandpressureofthethermodynamicsystem,
onecandeterminewhetheraprocesswouldoccurspontaneously.[39]Chemicalthermodynamicswas
furtherdevelopedbyPierreDuhem,[5]GilbertN.Lewis,MerleRandall,[6]andE.A.Guggenheim,[7][8]
whoappliedthemathematicalmethodsofGibbs.
Etymology
Theetymologyofthermodynamicshasanintricatehistory.Itwasfirstspelledinahyphenatedformas
anadjective(thermodynamic)in1849andfrom1854to1859asthehyphenatednounthermodynamics
torepresentthescienceofheatandmotivepowerandthereafterasthermodynamics.
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Thecomponentsofthewordthermodynamicarederivedfrom
theGreekwordstherme,meaning"heat,"and
dynamis,meaning"power"(Haynieclaimsthatthewordwas
coinedaround1840).[40][41]
ThetermthermodynamicwasfirstusedinJanuary1849by
WilliamThomson,laterLordKelvin,inthephraseaperfect
thermodynamicenginetodescribeSadiCarnot'sheat
engine.[42]:545InApril1849,Thomsonaddedanappendixtohis
paperandusedthetermthermodynamicinthephrasetheobject
ofathermodynamicengine.[42]:569
Thelifetimesofsomeofthemost
importantcontributorsto
thermodynamics
PierrePerrotclaimsthatthetermthermodynamicswascoinedby
JamesJoulein1858todesignatethescienceofrelationsbetweenheatandpower.[11]Joule,however,
neverusedthatterm,butdidusethetermperfectthermodynamicengineinreferencetoThomsons
1849phraseology,[42]:545andThomson'snoteonJoules'1851paperOntheAirEngine.
In1854,thermodynamics,asafunctionaltermtodenotethegeneralstudyoftheactionofheat,was
firstusedbyWilliamThomsoninhispaper"OntheDynamicalTheoryofHeat".[2]
In1859,theclosedcompoundformthermodynamicswasfirstusedbyWilliamRankineinAManualof
theSteamEngineinachapteronthePrinciplesofThermodynamics.[43]
Branchesofdescription
Thermodynamicsystemsaretheoreticalconstructionsusedtomodelphysicalsystemsthatexchange
matterandenergyintermsofthelawsofthermodynamics.Thestudyofthermodynamicalsystemshas
developedintoseveralrelatedbranches,eachusingadifferentfundamentalmodelasatheoreticalor
experimentalbasis,orapplyingtheprinciplestovaryingtypesofsystems.
Classicalthermodynamics
Classicalthermodynamicsaccountsfortheadventuresofathermodynamicsysteminterms,eitherofits
timeinvariantequilibriumstates,orelseofitscontinuallyrepeatedcyclicprocesses,but,formally,not
bothinthesameaccount.Itusesonlytimeinvariant,orequilibrium,macroscopicquantitiesmeasurable
inthelaboratory,countingastimeinvariantalongtermtimeaverageofaquantity,suchasaflow,
generatedbyacontinuallyrepetitiveprocess.[44][45]Inclassicalthermodynamics,ratesofchangearenot
admittedasvariablesofinterest.Anequilibriumstatestandsendlesslywithoutchangeovertime,whilea
continuallyrepeatedcyclicprocessrunsendlesslywithoutanetchangeinthesystemovertime.
Intheaccountintermsofequilibriumstatesofasystem,astateofthermodynamicequilibriumina
simplesystemisspatiallyhomogeneous.
Intheclassicalaccountsolelyintermsofacyclicprocess,thespatialinteriorofthe'workingbody'of
thatprocessisnotconsideredthe'workingbody'thusdoesnothaveadefinedinternalthermodynamic
stateofitsownbecausenoassumptionismadethatitshouldbeinthermodynamicequilibriumonlyits
inputsandoutputsofenergyasheatandworkareconsidered.[46]Itiscommontodescribeacycle
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theoreticallyascomposedofasequenceofverymanythermodynamicoperationsandprocesses.This
createsalinktothedescriptionintermsofequilibriumstates.Thecycleisthentheoreticallydescribed
asacontinuousprogressionofequilibriumstates.
Classicalthermodynamicswasoriginallyconcernedwiththetransformationofenergyinacyclic
process,andtheexchangeofenergybetweenclosedsystemsdefinedonlybytheirequilibriumstates.
Thedistinctionbetweentransfersofenergyasheatandasworkwascentral.
Asclassicalthermodynamicsdeveloped,thedistinctionbetweenheatandworkbecamelesscentral.This
wasbecausetherewasmoreinterestinopensystems,forwhichthedistinctionbetweenheatandworkis
notsimple,andisbeyondthescopeofthepresentarticle.Alongsidetheamountofheattransferredasa
fundamentalquantity,entropywasgraduallyfoundtobeamoregenerallyapplicableconcept,especially
whenconsideringchemicalreactions.Massieuin1869consideredentropyasthebasicdependent
thermodynamicvariable,withenergypotentialsandthereciprocalofthethermodynamictemperatureas
fundamentalindependentvariables.Massieufunctionscanbeusefulinpresentdaynonequilibrium
thermodynamics.In1875,intheworkofJosiahWillardGibbs,entropywasconsideredafundamental
independentvariable,whileinternalenergywasadependentvariable.[47]
Allactualphysicalprocessesaretosomedegreeirreversible.Classicalthermodynamicscanconsider
irreversibleprocesses,butitsaccountinexacttermsisrestrictedtovariablesthatreferonlytoinitialand
finalstatesofthermodynamicequilibrium,ortoratesofinputandoutputthatdonotchangewithtime.
Forexample,classicalthermodynamicscanconsidertimeaverageratesofflowsgeneratedby
continuallyrepeatedirreversiblecyclicprocesses.Alsoitcanconsiderirreversiblechangesbetween
equilibriumstatesofsystemsconsistingofseveralphases(asdefinedbelowinthisarticle),orwith
removableorreplaceablepartitions.Butforsystemsthataredescribedintermsofequilibriumstates,it
considersneitherflows,norspatialinhomogeneitiesinsimplesystemswithnoexternallyimposedforce
fieldssuchasgravity.Intheaccountintermsofequilibriumstatesofasystem,descriptionsof
irreversibleprocessesreferonlytoinitialandfinalstaticequilibriumstatesthetimeittakestochange
thermodynamicstateisnotconsidered.[48][49]
Localequilibriumthermodynamics
Localequilibriumthermodynamicsisconcernedwiththetimecoursesandratesofprogressof
irreversibleprocessesinsystemsthataresmoothlyspatiallyinhomogeneous.Itadmitstimeasa
fundamentalquantity,butonlyinarestrictedway.Ratherthanconsideringtimeinvariantflowsaslong
termaverageratesofcyclicprocesses,localequilibriumthermodynamicsconsiderstimevaryingflows
insystemsthataredescribedbystatesoflocalthermodynamicequilibrium,asfollows.
Forprocessesthatinvolveonlysuitablysmallandsmoothspatialinhomogeneitiesandsuitablysmall
changeswithtime,agoodapproximationcanbefoundthroughtheassumptionoflocalthermodynamic
equilibrium.Withinthelargeorglobalregionofaprocess,forasuitablysmalllocalregion,this
approximationassumesthataquantityknownastheentropyofthesmalllocalregioncanbedefinedina
particularway.Thatparticularwayofdefinitionofentropyislargelybeyondthescopeofthepresent
article,buthereitmaybesaidthatitisentirelyderivedfromtheconceptsofclassicalthermodynamics
inparticular,neitherflowratesnorchangesovertimeareadmittedintothedefinitionoftheentropyof
thesmalllocalregion.Itisassumedwithoutproofthattheinstantaneousglobalentropyofanon
equilibriumsystemcanbefoundbyaddingupthesimultaneousinstantaneousentropiesofits
constituentsmalllocalregions.Localequilibriumthermodynamicsconsidersprocessesthatinvolvethe
timedependentproductionofentropybydissipativeprocesses,inwhichkineticenergyofbulkflowand
chemicalpotentialenergyareconvertedintointernalenergyattimeratesthatareexplicitlyaccounted
for.Timevaryingbulkflowsandspecificdiffusionalflowsareconsidered,buttheyarerequiredtobe
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dependentvariables,derivedonlyfrommaterialpropertiesdescribedonlybystaticmacroscopic
equilibriumstatesofsmalllocalregions.Theindependentstatevariablesofasmalllocalregionareonly
thoseofclassicalthermodynamics.
Generalizedorextendedthermodynamics
Likelocalequilibriumthermodynamics,generalizedorextendedthermodynamicsalsoisconcernedwith
thetimecoursesandratesofprogressofirreversibleprocessesinsystemsthataresmoothlyspatially
inhomogeneous.Itdescribestimevaryingflowsintermsofstatesofsuitablysmalllocalregionswithin
aglobalregionthatissmoothlyspatiallyinhomogeneous,ratherthanconsideringflowsastimeinvariant
longtermaverageratesofcyclicprocesses.Initsaccountsofprocesses,generalizedorextended
thermodynamicsadmitstimeasafundamentalquantityinamorefarreachingwaythandoeslocal
equilibriumthermodynamics.Thestatesofsmalllocalregionsaredefinedbymacroscopicquantities
thatareexplicitlyallowedtovarywithtime,includingtimevaryingflows.Generalizedthermodynamics
mighttacklesuchproblemsasultrasoundorshockwaves,inwhichtherearestrongspatial
inhomogeneitiesandchangesintimefastenoughtooutpaceatendencytowardslocalthermodynamic
equilibrium.Generalizedorextendedthermodynamicsisadiverseanddevelopingproject,ratherthana
moreorlesscompletedsubjectsuchasisclassicalthermodynamics.[50][51]
Forgeneralizedorextendedthermodynamics,thedefinitionofthequantityknownastheentropyofa
smalllocalregionisintermsbeyondthoseofclassicalthermodynamicsinparticular,flowratesare
admittedintothedefinitionoftheentropyofasmalllocalregion.Theindependentstatevariablesofa
smalllocalregionincludeflowrates,whicharenotadmittedasindependentvariablesforthesmalllocal
regionsoflocalequilibriumthermodynamics.
Outsidetherangeofclassicalthermodynamics,thedefinitionoftheentropyofasmalllocalregionisno
simplematter.Forathermodynamicaccountofaprocessintermsoftheentropiesofsmalllocalregions,
thedefinitionofentropyshouldbesuchastoensurethatthesecondlawofthermodynamicsappliesin
eachsmalllocalregion.Itisoftenassumedwithoutproofthattheinstantaneousglobalentropyofanon
equilibriumsystemcanbefoundbyaddingupthesimultaneousinstantaneousentropiesofits
constituentsmalllocalregions.Foragivenphysicalprocess,theselectionofsuitableindependentlocal
nonequilibriummacroscopicstatevariablesfortheconstructionofathermodynamicdescriptioncalls
forqualitativephysicalunderstanding,ratherthanbeingasimplymathematicalproblemconcernedwith
auniquelydeterminedthermodynamicdescription.Asuitabledefinitionoftheentropyofasmalllocal
regiondependsonthephysicallyinsightfulandjudiciousselectionoftheindependentlocalnon
equilibriummacroscopicstatevariables,anddifferentselectionsprovidedifferentgeneralizedor
extendedthermodynamicalaccountsofoneandthesamegivenphysicalprocess.Thisisoneofthe
severalgoodreasonsforconsideringentropyasanepistemicphysicalvariable,ratherthanasasimply
materialquantity.Accordingtoarespectedauthor:"Thereisnocompellingreasontobelievethatthe
classicalthermodynamicentropyisameasurablepropertyofnonequilibriumphenomena,..."[52]
Statisticalthermodynamics
Statisticalthermodynamics,alsocalledstatisticalmechanics,emergedwiththedevelopmentofatomic
andmoleculartheoriesinthesecondhalfofthe19thcenturyandearly20thcentury.Itprovidesan
explanationofclassicalthermodynamics.Itconsidersthemicroscopicinteractionsbetweenindividual
particlesandtheircollectivemotions,intermsofclassicalorofquantummechanics.Itsexplanationisin
termsofstatisticsthatrestonthefactthesystemiscomposedofseveralspeciesofparticlesorcollective
motions,themembersofeachspeciesrespectivelybeinginsomesenseallalike.
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Thermodynamicequilibrium
Equilibriumthermodynamicsstudiestransformationsofmatterandenergyinsystemsatornear
thermodynamicequilibrium.Inthermodynamicequilibrium,asystem'spropertiesare,bydefinition,
unchangingintime.Inthermodynamicequilibriumnomacroscopicchangeisoccurringorcanbe
triggeredwithinthesystem,everymicroscopicprocessisbalancedbyitsoppositethisiscalledthe
principleofdetailedbalance.Acentralaiminequilibriumthermodynamicsis:givenasysteminawell
definedinitialstate,subjecttospecifiedconstraints,tocalculatewhattheequilibriumstateofthesystem
is.[53]
Intheoreticalstudies,itisoftenconvenienttoconsiderthesimplestkindofthermodynamicsystem.This
isdefinedvariouslybydifferentauthors.[48][54][55][56][57][58]Forthepresentarticle,thefollowing
definitionisconvenient,asabstractedfromthedefinitionsofvariousauthors.Aregionofmaterialwith
allintensivepropertiescontinuousinspaceandtimeiscalledaphase.Asimplesystemisforthepresent
articledefinedasonethatconsistsofasinglephaseofapurechemicalsubstance,withnointerior
partitions.
Withinasimpleisolatedthermodynamicsysteminthermodynamicequilibrium,intheabsenceof
externallyimposedforcefields,allpropertiesofthematerialofthesystemarespatially
homogeneous.[59]Muchofthebasictheoryofthermodynamicsisconcernedwithhomogeneoussystems
inthermodynamicequilibrium.[4][60]
Mostsystemsfoundinnatureorconsideredinengineeringarenotinthermodynamicequilibrium,
exactlyconsidered.Theyarechangingorcanbetriggeredtochangeovertime,andarecontinuouslyand
discontinuouslysubjecttofluxofmatterandenergytoandfromothersystems.[22]Forexample,
accordingtoCallen,"inabsolutethermodynamicequilibriumallradioactivematerialswouldhave
decayedcompletelyandnuclearreactionswouldhavetransmutedallnucleitothemoststableisotopes.
Suchprocesses,whichwouldtakecosmictimestocomplete,generallycanbeignored.".[22]Such
processesbeingignored,manysystemsinnaturearecloseenoughtothermodynamicequilibriumthat
formanypurposestheirbehaviourcanbewellapproximatedbyequilibriumcalculations.
Quasistatictransfersbetweensimplesystemsarenearlyinthermodynamic
equilibriumandarereversible
Itverymucheasesandsimplifiestheoreticalthermodynamicalstudiestoimaginetransfersofenergyand
matterbetweentwosimplesystemsthatproceedsoslowlythatatalltimeseachsimplesystem
consideredseparatelyisnearenoughtothermodynamicequilibrium.Suchprocessesaresometimes
calledquasistaticandarenearenoughtobeingreversible.[61][62]
Naturalprocessesarepartlydescribedbytendencytowardsthermodynamic
equilibriumandareirreversible
Ifnotinitiallyinthermodynamicequilibrium,simpleisolatedthermodynamicsystems,astimepasses,
tendtoevolvenaturallytowardsthermodynamicequilibrium.Intheabsenceofexternallyimposedforce
fields,theybecomehomogeneousinalltheirlocalproperties.Suchhomogeneityisanimportant
characteristicofasysteminthermodynamicequilibriumintheabsenceofexternallyimposedforce
fields.
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Manythermodynamicprocessescanbemodeledbycompoundorcompositesystems,consistingof
severalormanycontiguouscomponentsimplesystems,initiallynotinthermodynamicequilibrium,but
allowedtotransfermassandenergybetweenthem.Naturalthermodynamicprocessesaredescribedin
termsofatendencytowardsthermodynamicequilibriumwithinsimplesystemsandintransfersbetween
contiguoussimplesystems.Suchnaturalprocessesareirreversible.[63]
Nonequilibriumthermodynamics
Nonequilibriumthermodynamics[64]isabranchofthermodynamicsthatdealswithsystemsthatarenot
inthermodynamicequilibriumitisalsocalledthermodynamicsofirreversibleprocesses.
Lawsofthermodynamics
Thermodynamicsstatesasetoffourlawsthatarevalidforallsystemsthatfallwithintheconstraints
impliedbyeach.Inthevarioustheoreticaldescriptionsofthermodynamicstheselawsmaybeexpressed
inseeminglydifferingforms,butthemostprominentformulationsarethefollowing:
Zerothlawofthermodynamics:Iftwosystemsareeachinthermalequilibriumwithathird,they
arealsointhermalequilibriumwitheachother.
Thisstatementimpliesthatthermalequilibriumisanequivalencerelationonthesetofthermodynamic
systemsunderconsideration.Systemsaresaidtobeinthermalequilibriumwitheachotherif
spontaneousmolecularthermalenergyexchangesbetweenthemdonotleadtoanetexchangeofenergy.
Thislawistacitlyassumedineverymeasurementoftemperature.Fortwobodiesknowntobeatthe
sametemperature,decidingiftheyareinthermalequilibriumwhenputintothermalcontactdoesnot
requireactuallybringingthemintocontactandmeasuringanychangesoftheirobservablepropertiesin
time.[65]Intraditionalstatements,thelawprovidesanempiricaldefinitionoftemperatureand
justificationfortheconstructionofpracticalthermometers.Incontrasttoabsolutethermodynamic
temperatures,empiricaltemperaturesaremeasuredjustbythemechanicalpropertiesofbodies,suchas
theirvolumes,withoutrelianceontheconceptsofenergy,entropyorthefirst,second,orthirdlawsof
thermodynamics.[56][66]Empiricaltemperaturesleadtocalorimetryforheattransferintermsofthe
mechanicalpropertiesofbodies,withoutrelianceonmechanicalconceptsofenergy.
Thephysicalcontentofthezerothlawhaslongbeenrecognized.Forexample,Rankinein1853defined
temperatureasfollows:"Twoportionsofmatteraresaidtohaveequaltemperatureswhenneithertends
tocommunicateheattotheother."[67]Maxwellin1872stateda"LawofEqualTemperatures".[68]He
alsostated:"AllHeatisofthesamekind."[69]Planckexplicitlyassumedandstateditinitscustomary
presentdaywordinginhisformulationofthefirsttwolaws.[70]Bythetimethedesirearosetonumberit
asalaw,theotherthreehadalreadybeenassignednumbers,andsoitwasdesignatedthezerothlaw.
Firstlawofthermodynamics:Theincreaseininternalenergyofaclosedsystemisequaltothe
differenceoftheheatsuppliedtothesystemandtheworkdonebythesystem:U=QW
[71][72][73][74][75][76][77][78][79][80](Notethatduetotheambiguityofwhatconstitutespositivework,
somesourcesstatethatU=Q+W,inwhichcaseworkdoneonthesystemispositive.)
Thefirstlawofthermodynamicsassertstheexistenceofastatevariableforasystem,theinternal
energy,andtellshowitchangesinthermodynamicprocesses.Thelawallowsagiveninternalenergyof
asystemtobereachedbyanycombinationofheatandwork.Itisimportantthatinternalenergyisa
variableofstateofthesystem(seeThermodynamicstate)whereasheatandworkarevariablesthat
describeprocessesorchangesofthestateofsystems.
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Thefirstlawobservesthattheinternalenergyofanisolatedsystemobeystheprincipleofconservation
ofenergy,whichstatesthatenergycanbetransformed(changedfromoneformtoanother),butcannot
becreatedordestroyed.[81][82][83][84][85]
Secondlawofthermodynamics:Heatcannotspontaneouslyflowfromacolderlocationtoa
hotterlocation.
Thesecondlawofthermodynamicsisanexpressionoftheuniversalprincipleofdissipationofkinetic
andpotentialenergyobservableinnature.Thesecondlawisanobservationofthefactthatovertime,
differencesintemperature,pressure,andchemicalpotentialtendtoevenoutinaphysicalsystemthatis
isolatedfromtheoutsideworld.Entropyisameasureofhowmuchthisprocesshasprogressed.The
entropyofanisolatedsystemthatisnotinequilibriumtendstoincreaseovertime,approachinga
maximumvalueatequilibrium.
Inclassicalthermodynamics,thesecondlawisabasicpostulateapplicabletoanysysteminvolvingheat
energytransferinstatisticalthermodynamics,thesecondlawisaconsequenceoftheassumed
randomnessofmolecularchaos.Therearemanyversionsofthesecondlaw,buttheyallhavethesame
effect,whichistoexplainthephenomenonofirreversibilityinnature.
Thirdlawofthermodynamics:Asasystemapproachesabsolutezerotheentropyofthesystem
approachesaminimumvalue.
Thethirdlawofthermodynamicsisastatisticallawofnatureregardingentropyandtheimpossibilityof
reachingabsolutezerooftemperature.Thislawprovidesanabsolutereferencepointforthe
determinationofentropy.Theentropydeterminedrelativetothispointistheabsoluteentropy.Alternate
definitionsofthethirdlaware,"theentropyofallsystemsandofallstatesofasystemissmallestat
absolutezero,"orequivalently"itisimpossibletoreachtheabsolutezerooftemperaturebyanyfinite
numberofprocesses".
Absolutezerois273.15C(degreesCelsius),459.67F(degreesFahrenheit),0K(kelvin),or0R
(Rankine).
Systemmodels
Thethermodynamicsystemisanimportantconceptofthermodynamics.Itisapreciselydefinedregion
oftheuniverseunderstudy.Everythingintheuniverseexceptthesystemisknownasthesurroundings.
Asystemisseparatedfromtheremainderoftheuniversebyaboundary,whichmaybeactual,ormerely
notionalandfictive,butbyconventiondelimitsafinitevolume.Transfersofwork,heat,ormatter
betweenthesystemandthesurroundingstakeplaceacrossthisboundary,whichmayormaynothave
propertiesthatrestrictwhatcanbetransferredacrossit.Asystemmayhaveseveraldistinctboundary
sectorsorpartitionsseparatingitfromthesurroundings,eachcharacterizedbyhowitrestrictstransfers,
andbeingpermeabletoitscharacteristictransferredquantities.
Thevolumecanbetheregionsurroundingasingleatomresonatingenergy,asMaxPlanckdefinedin
1900itcanbeabodyofsteamorairinasteamengine,suchasSadiCarnotdefinedin1824itcanbe
thebodyofatropicalcyclone,asKerryEmanueltheorizedin1986inthefieldofatmospheric
thermodynamicsitcouldalsobejustonenuclide(i.e.asystemofquarks)ashypothesizedinquantum
thermodynamics.
Anythingthatpassesacrosstheboundaryneedstobeaccountedforinapropertransferbalance
equation.Thermodynamicsislargelyaboutsuchtransfers.
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Boundary
Typesoftransferspermitted
sectorsare
inathermodynamicprocess
ofvarious
foratypeofpartition
characters:
typeofpartition
typeoftransfer
rigid,
flexible,
Mass
fixed,
Work Heat
moveable,
andenergy
actually
restrictive,
permeabletomatter
andfictive
permeabletoenergybut
Adiagramofageneric
ornot
thermodynamicsystem
actually
impermeabletomatter
restrictive.
For
adiabatic
example,inanengine,afixedboundarysector
adynamicand
meansthepistonislockedatitspositionthenno
pressurevolumeworkisdoneacrossit.Inthat
impermeabletomatter
sameengine,amoveableboundaryallowsthe
pistontomoveinandout,permittingpressure
isolating
volumework.Thereisnorestrictiveboundary
sectorforthewholeearthincludingits
atmosphere,andsoroughlyspeaking,nopressurevolumeworkisdoneonorbythewholeearthsystem.
Suchasystemissometimessaidtobediabaticallyheatedorcooledbyradiation.[86][87]
Thermodynamicsdistinguishesclassesofsystemsbytheirboundarysectors.
Anopensystemhasaboundarysectorthatispermeabletomattersuchasectorisusually
permeablealsotoenergy,buttheenergythatpassescannotingeneralbeuniquelysortedintoheat
andworkcomponents.Opensystemboundariesmaybeeitheractuallyrestrictive,orelsenon
restrictive.
Aclosedsystemhasnoboundarysectorthatispermeabletomatter,butingeneralitsboundaryis
permeabletoenergy.Forclosedsystems,boundariesaretotallyprohibitiveofmattertransfer.
Anadiabaticallyisolatedsystemhasonlyadiabaticboundarysectors.Energycanbetransferred
aswork,buttransfersofmatterandofenergyasheatareprohibited.
Apurelydiathermicallyisolatedsystemhasonlyboundarysectorspermeableonlytoheatitis
sometimessaidtobeadynamicallyisolatedandclosedtomattertransfer.Aprocessinwhichno
workistransferredissometimescalledadynamic.[88]
Anisolatedsystemhasonlyisolatingboundarysectors.Nothingcanbetransferredintooroutof
it.
Engineeringandnaturalprocessesareoftendescribedascompositesofmanydifferentcomponent
simplesystems,sometimeswithunchangingorchangingpartitionsbetweenthem.Achangeofpartition
isanexampleofathermodynamicoperation.
Statesandprocesses
Therearefourfundamentalkindsofentityinthermodynamicsstatesofasystem,wallsbetween
systems,thermodynamicprocesses,andthermodynamicoperations.Thisallowsthreefundamental
approachestothermodynamicreasoningthatintermsofstatesofthermodynamicequilibriumofa
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system,andthatintermsoftimeinvariantprocessesofasystem,andthatintermsofcyclicprocessesof
asystem.
Theapproachthroughstatesofthermodynamicequilibriumofasystemrequiresafullaccountofthe
stateofthesystemaswellasanotionofprocessfromonestatetoanotherofasystem,butmayrequire
onlyanidealizedorpartialaccountofthestateofthesurroundingsofthesystemorofothersystems.
Themethodofdescriptionintermsofstatesofthermodynamicequilibriumhaslimitations.Forexample,
processesinaregionofturbulentflow,orinaburninggasmixture,orinaKnudsengasmaybebeyond
"theprovinceofthermodynamics".[89][90][91]Thisproblemcansometimesbecircumventedthroughthe
methodofdescriptionintermsofcyclicoroftimeinvariantflowprocesses.Thisispartofthereason
whythefoundersofthermodynamicsoftenpreferredthecyclicprocessdescription.
Approachesthroughprocessesoftimeinvariantflowofasystemareusedforsomestudies.Some
processes,forexampleJouleThomsonexpansion,arestudiedthroughsteadyflowexperiments,butcan
beaccountedforbydistinguishingthesteadybulkflowkineticenergyfromtheinternalenergy,andthus
canberegardedaswithinthescopeofclassicalthermodynamicsdefinedintermsofequilibriumstates
orofcyclicprocesses.[44][92]Otherflowprocesses,forexamplethermoelectriceffects,areessentially
definedbythepresenceofdifferentialflowsordiffusionsothattheycannotbeadequatelyaccountedfor
intermsofequilibriumstatesorclassicalcyclicprocesses.[93][94]
Thenotionofacyclicprocessdoesnotrequireafullaccountofthestateofthesystem,butdoesrequire
afullaccountofhowtheprocessoccasionstransfersofmatterandenergybetweentheprincipalsystem
(whichisoftencalledtheworkingbody)anditssurroundings,whichmustincludeatleasttwoheat
reservoirsatdifferentknownandfixedtemperatures,onehotterthantheprincipalsystemandtheother
colderthanit,aswellasareservoirthatcanreceiveenergyfromthesystemasworkandcandoworkon
thesystem.Thereservoirscanalternativelyberegardedasauxiliaryidealizedcomponentsystems,
alongsidetheprincipalsystem.Thusanaccountintermsofcyclicprocessesrequiresatleastfour
contributorycomponentsystems.Theindependentvariablesofthisaccountaretheamountsofenergy
thatenterandleavetheidealizedauxiliarysystems.Inthiskindofaccount,theworkingbodyisoften
regardedasa"blackbox",[95]anditsownstateisnotspecified.Inthisapproach,thenotionofaproperly
numericalscaleofempiricaltemperatureisapresuppositionofthermodynamics,notanotion
constructedbyorderivedfromit.
Accountintermsofstatesofthermodynamicequilibrium
Whenasystemisatthermodynamicequilibriumunderagivensetofconditionsofitssurroundings,itis
saidtobeinadefinitethermodynamicstate,whichisfullydescribedbyitsstatevariables.
Ifasystemissimpleasdefinedabove,andisinthermodynamicequilibrium,andisnotsubjecttoan
externallyimposedforcefield,suchasgravity,electricity,ormagnetism,thenitishomogeneous,thatis
say,spatiallyuniforminallrespects.[96]
Inasense,ahomogeneoussystemcanberegardedasspatiallyzerodimensional,becauseithasno
spatialvariation.
Ifasysteminthermodynamicequilibriumishomogeneous,thenitsstatecanbedescribedbyafew
physicalvariables,whicharemostlyclassifiableasintensivevariablesandextensive
variables.[8][33][97][98][99]
Anintensivevariableisonethatisunchangedwiththethermodynamicoperationofscalingofasystem.
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Anextensivevariableisonethatsimplyscaleswiththescalingofasystem,withoutthefurther
requirementusedjustbelowhere,ofadditivityevenwhenthereisinhomogeneityoftheaddedsystems.
Examplesofextensivethermodynamicvariablesaretotalmassandtotalvolume.Undertheabove
definition,entropyisalsoregardedasanextensivevariable.Examplesofintensivethermodynamic
variablesaretemperature,pressure,andchemicalconcentrationintensivethermodynamicvariablesare
definedateachspatialpointandeachinstantoftimeinasystem.Physicalmacroscopicvariablescanbe
mechanical,material,orthermal.[33]TemperatureisathermalvariableaccordingtoGuggenheim,"the
mostimportantconceptioninthermodynamicsistemperature."[8]
Intensivevariableshavethepropertythatifanynumberofsystems,eachinitsownseparate
homogeneousthermodynamicequilibriumstate,allwiththesamerespectivevaluesofalloftheir
intensivevariables,regardlessofthevaluesoftheirextensivevariables,arelaidcontiguouslywithno
partitionbetweenthem,soastoformanewsystem,thenthevaluesoftheintensivevariablesofthenew
systemarethesameasthoseoftheseparateconstituentsystems.Suchacompositesystemisina
homogeneousthermodynamicequilibrium.Examplesofintensivevariablesaretemperature,chemical
concentration,pressure,densityofmass,densityofinternalenergy,and,whenitcanbeproperlydefined,
densityofentropy.[100]Inotherwords,intensivevariablesarenotalteredbythethermodynamic
operationofscaling.
Fortheimmediatelypresentaccountjustbelow,analternativedefinitionofextensivevariablesis
considered,thatrequiresthatifanynumberofsystems,regardlessoftheirpossibleseparate
thermodynamicequilibriumornonequilibriumstatesorintensivevariables,arelaidsidebysidewithno
partitionbetweenthemsoastoformanewsystem,thenthevaluesoftheextensivevariablesofthenew
systemarethesumsofthevaluesoftherespectiveextensivevariablesoftheindividualseparate
constituentsystems.Obviously,thereisnoreasontoexpectsuchacompositesystemtobeina
homogeneousthermodynamicequilibrium.Examplesofextensivevariablesinthisalternativedefinition
aremass,volume,andinternalenergy.Theydependonthetotalquantityofmassinthesystem.[101]In
otherwords,althoughextensivevariablesscalewiththesystemunderthethermodynamicoperationof
scaling,neverthelessthepresentalternativedefinitionofanextensivevariablerequiresmorethanthis:it
requiresalsoitsadditivityregardlessoftheinhomogeneity(orequalityorinequalityofthevaluesofthe
intensivevariables)ofthecomponentsystems.
Though,whenitcanbeproperlydefined,densityofentropyisanintensivevariable,forinhomogeneous
systems,entropyitselfdoesnotfitintothisalternativeclassificationofstatevariables.[102][103]The
reasonisthatentropyisapropertyofasystemasawhole,andnotnecessarilyrelatedsimplytoits
constituentsseparately.Itistruethatforanynumberofsystemseachinitsownseparatehomogeneous
thermodynamicequilibrium,allwiththesamevaluesofintensivevariables,removalofthepartitions
betweentheseparatesystemsresultsinacompositehomogeneoussysteminthermodynamic
equilibrium,withallthevaluesofitsintensivevariablesthesameasthoseoftheconstituentsystems,
anditisreservedlyorconditionallytruethattheentropyofsucharestrictivelydefinedcompositesystem
isthesumoftheentropiesoftheconstituentsystems.Butiftheconstituentsystemsdonotsatisfythese
restrictiveconditions,theentropyofacompositesystemcannotbeexpectedtobethesumofthe
entropiesoftheconstituentsystems,becausetheentropyisapropertyofthecompositesystemasa
whole.Therefore,thoughundertheserestrictivereservations,entropysatisfiessomerequirementsfor
extensivitydefinedjustabove,entropyingeneraldoesnotfittheimmediatelypresentdefinitionofan
extensivevariable.
Beingneitheranintensivevariablenoranextensivevariableaccordingtotheimmediatelypresent
definition,entropyisthusastandoutvariable,becauseitisastatevariableofasystemasawhole.[102]
Anonequilibriumsystemcanhaveaveryinhomogeneousdynamicalstructure.Thisisonereasonfor
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distinguishingthestudyofequilibriumthermodynamicsfromthestudyofnonequilibrium
thermodynamics.
Thephysicalreasonfortheexistenceofextensivevariablesisthetimeinvarianceofvolumeinagiven
inertialreferenceframe,andthestrictlylocalconservationofmass,momentum,angularmomentum,and
energy.AsnotedbyGibbs,entropyisunlikeenergyandmass,becauseitisnotlocallyconserved.[102]
Thestandoutquantityentropyisneverconservedinrealphysicalprocessesallrealphysicalprocesses
areirreversible.[104]Themotionofplanetsseemsreversibleonashorttimescale(millionsofyears),but
theirmotion,accordingtoNewton'slaws,ismathematicallyanexampleofdeterministicchaos.
Eventuallyaplanetsuffersanunpredictablecollisionwithanobjectfromitssurroundings,outerspace
inthiscase,andconsequentlyitsfuturecourseisradicallyunpredictable.Theoreticallythiscanbe
expressedbysayingthateverynaturalprocessdissipatessomeinformationfromthepredictablepartof
itsactivityintotheunpredictablepart.Thepredictablepartisexpressedinthegeneralizedmechanical
variables,andtheunpredictablepartinheat.
Otherstatevariablescanberegardedasconditionally'extensive'subjecttoreservationasabove,butnot
extensiveasdefinedabove.ExamplesaretheGibbsfreeenergy,theHelmholtzfreeenergy,andthe
enthalpy.Consequently,justbecauseforsomesystemsunderparticularconditionsoftheirsurroundings
suchstatevariablesareconditionallyconjugatetointensivevariables,suchconjugacydoesnotmake
suchstatevariablesextensiveasdefinedabove.Thisisanotherreasonfordistinguishingthestudyof
equilibriumthermodynamicsfromthestudyofnonequilibriumthermodynamics.Inanotherwayof
thinking,thisexplainswhyheatistoberegardedasaquantitythatreferstoaprocessandnottoastate
ofasystem.
Asystemwithnointernalpartitions,andinthermodynamicequilibrium,canbeinhomogeneousinthe
followingrespect:itcanconsistofseveralsocalled'phases',eachhomogeneousinitself,inimmediate
contiguitywithotherphasesofthesystem,butdistinguishablebytheirhavingvariousrespectively
differentphysicalcharacters,withdiscontinuityofintensivevariablesattheboundariesbetweenthe
phasesamixtureofdifferentchemicalspeciesisconsideredhomogeneousforthispurposeifitis
physicallyhomogeneous.[105]Forexample,avesselcancontainasystemconsistingofwatervapour
overlyingliquidwaterthenthereisavapourphaseandaliquidphase,eachhomogeneousinitself,but
stillinthermodynamicequilibriumwiththeotherphase.Fortheimmediatelypresentaccount,systems
withmultiplephasesarenotconsidered,thoughformanythermodynamicquestions,multiphasesystems
areimportant.
Equationofstate
Themacroscopicvariablesofathermodynamicsysteminthermodynamicequilibrium,inwhich
temperatureiswelldefined,canberelatedtooneanotherthroughequationsofstateorcharacteristic
equations.[29][30][31][32]Theyexpresstheconstitutivepeculiaritiesofthematerialofthesystem.The
equationofstatemustcomplywithsomethermodynamicconstraints,butcannotbederivedfromthe
generalprinciplesofthermodynamicsalone.
Thermodynamicprocessesbetweenstatesofthermodynamicequilibrium
Athermodynamicprocessisdefinedbychangesofstateinternaltothesystemofinterest,combined
withtransfersofmatterandenergytoandfromthesurroundingsofthesystemortoandfromother
systems.Asystemisdemarcatedfromitssurroundingsorfromothersystemsbypartitionsthatmoreor
lessseparatethem,andmaymoveasapistontochangethevolumeofthesystemandthustransferwork.
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Dependentandindependentvariablesforaprocess
Aprocessisdescribedbychangesinvaluesofstatevariablesofsystemsorbyquantitiesofexchangeof
matterandenergybetweensystemsandsurroundings.Thechangemustbespecifiedintermsof
prescribedvariables.Thechoiceofwhichvariablesaretobeusedismadeinadvanceofconsiderationof
thecourseoftheprocess,andcannotbechanged.Certainofthevariableschoseninadvancearecalled
theindependentvariables.[106]Fromchangesinindependentvariablesmaybederivedchangesinother
variablescalleddependentvariables.Forexample,aprocessmayoccuratconstantpressurewith
pressureprescribedasanindependentvariable,andtemperaturechangedasanotherindependent
variable,andthenchangesinvolumeareconsideredasdependent.Carefulattentiontothisprincipleis
necessaryinthermodynamics.[107][108]
Changesofstateofasystem
Intheapproachthroughequilibriumstatesofthesystem,aprocesscanbedescribedintwomainways.
Inoneway,thesystemisconsideredtobeconnectedtothesurroundingsbysomekindofmoreorless
separatingpartition,andallowedtoreachequilibriumwiththesurroundingswiththatpartitioninplace.
Then,whiletheseparativecharacterofthepartitioniskeptunchanged,theconditionsofthe
surroundingsarechanged,andexerttheirinfluenceonthesystemagainthroughtheseparatingpartition,
orthepartitionismovedsoastochangethevolumeofthesystemandanewequilibriumisreached.
Forexample,asystemisallowedtoreachequilibriumwithaheatbathatonetemperaturethenthe
temperatureoftheheatbathischangedandthesystemisallowedtoreachanewequilibriumifthe
partitionallowsconductionofheat,thenewequilibriumisdifferentfromtheoldequilibrium.
Intheotherway,severalsystemsareconnectedtooneanotherbyvariouskindsofmoreorless
separatingpartitions,andtoreachequilibriumwitheachother,withthosepartitionsinplace.Inthisway,
onemayspeakofa'compoundsystem'.Thenoneormorepartitionsisremovedorchangedinits
separativepropertiesormoved,andanewequilibriumisreached.TheJouleThomsonexperimentisan
exampleofthisatubeofgasisseparatedfromanothertubebyaporouspartitionthevolumeavailable
ineachofthetubesisdeterminedbyrespectivepistonsequilibriumisestablishedwithaninitialsetof
volumesthevolumesarechangedandanewequilibriumisestablished.[109][110][111][112][113]Another
exampleisinseparationandmixingofgases,withuseofchemicallysemipermeablemembranes.[114]
Commonlyconsideredthermodynamicprocesses
Itisoftenconvenienttostudyathermodynamicprocessinwhichasinglevariable,suchastemperature,
pressure,orvolume,etc.,isheldfixed.Furthermore,itisusefultogrouptheseprocessesintopairs,in
whicheachvariableheldconstantisonememberofaconjugatepair.
Severalcommonlystudiedthermodynamicprocessesare:
Isobaricprocess:occursatconstantpressure
Isochoricprocess:occursatconstantvolume(alsocalledisometric/isovolumetric)
Isothermalprocess:occursataconstanttemperature
Adiabaticprocess:occurswithoutlossorgainofenergyasheat
Isentropicprocess:areversibleadiabaticprocessoccursataconstantentropy,butisafictional
idealization.Conceptuallyitispossibletoactuallyphysicallyconductaprocessthatkeepsthe
entropyofthesystemconstant,allowingsystematicallycontrolledremovalofheat,byconduction
toacoolerbody,tocompensateforentropyproducedwithinthesystembyirreversibleworkdone
onthesystem.Suchisentropicconductofaprocessseemscalledforwhentheentropyofthe
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systemisconsideredasanindependentvariable,asforexamplewhentheinternalenergyis
consideredasafunctionoftheentropyandvolumeofthesystem,thenaturalvariablesofthe
internalenergyasstudiedbyGibbs.
Isenthalpicprocess:occursataconstantenthalpy
Isolatedprocess:nomatterorenergy(neitherasworknorasheat)istransferredintooroutofthe
system
Itissometimesofinteresttostudyaprocessinwhichseveralvariablesarecontrolled,subjecttosome
specifiedconstraint.Inasysteminwhichachemicalreactioncanoccur,forexample,inwhichthe
pressureandtemperaturecanaffecttheequilibriumcomposition,aprocessmightoccurinwhich
temperatureisheldconstantbutpressureisslowlyaltered,justsothatchemicalequilibriumis
maintainedalltheway.Thereisacorrespondingprocessatconstanttemperatureinwhichthefinal
pressureisthesamebutisreachedbyarapidjump.Thenitcanbeshownthatthevolumechange
resultingfromtherapidjumpprocessissmallerthanthatfromtheslowequilibriumprocess.[115]The
worktransferreddiffersbetweenthetwoprocesses.
Accountintermsofcyclicprocesses
Acyclicprocess[26]isaprocessthatcanberepeatedindefinitelyoftenwithoutchangingthefinalstateof
thesysteminwhichtheprocessoccurs.Theonlytracesoftheeffectsofacyclicprocessaretobefound
inthesurroundingsofthesystemorinothersystems.Thisisthekindofprocessthatconcernedearly
thermodynamicistssuchasSadiCarnot,andintermsofwhichKelvindefinedabsolutetemperature,[116]
beforetheuseofthequantityofentropybyRankineanditsclearidentificationbyClausius.[117]For
somesystems,forexamplewithsomeplasticworkingsubstances,cyclicprocessesarepracticallynearly
unfeasiblebecausetheworkingsubstanceundergoespracticallyirreversiblechanges.[118]Thisiswhy
mechanicaldevicesarelubricatedwithoilandoneofthereasonswhyelectricaldevicesareoftenuseful.
Acyclicprocessofasystemrequiresinitssurroundingsatleasttwoheatreservoirsatdifferent
temperatures,oneatahighertemperaturethatsuppliesheattothesystem,theotheratalower
temperaturethatacceptsheatfromthesystem.Theearlyworkonthermodynamicstendedtousethe
cyclicprocessapproach,becauseitwasinterestedinmachinesthatconvertedsomeoftheheatfromthe
surroundingsintomechanicalpowerdeliveredtothesurroundings,withouttoomuchconcernaboutthe
internalworkingsofthemachine.Suchamachine,whilereceivinganamountofheatfromahigher
temperaturereservoir,alwaysneedsalowertemperaturereservoirthatacceptssomelesseramountof
heat.Thedifferenceinamountsofheatisequaltotheamountofheatconvertedtowork.[83]Later,the
internalworkingsofasystembecameofinterest,andtheyaredescribedbythestatesofthesystem.
Nowadays,insteadofarguingintermsofcyclicprocesses,somewritersareinclinedtoderivethe
conceptofabsolutetemperaturefromtheconceptofentropy,avariableofstate.
Instrumentation
Therearetwotypesofthermodynamicinstruments,themeterandthereservoir.Athermodynamic
meterisanydevicethatmeasuresanyparameterofathermodynamicsystem.Insomecases,the
thermodynamicparameterisactuallydefinedintermsofanidealizedmeasuringinstrument.For
example,thezerothlawstatesthatiftwobodiesareinthermalequilibriumwithathirdbody,theyare
alsointhermalequilibriumwitheachother.Thisprinciple,asnotedbyJamesMaxwellin1872,asserts
thatitispossibletomeasuretemperature.Anidealizedthermometerisasampleofanidealgasat
constantpressure.FromtheidealgaslawPV=nRT,thevolumeofsuchasamplecanbeusedasan
indicatoroftemperatureinthismanneritdefinestemperature.Althoughpressureisdefined
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mechanically,apressuremeasuringdevice,calledabarometermayalsobeconstructedfromasampleof
anidealgasheldataconstanttemperature.Acalorimeterisadevicethatmeasuresanddefinethe
internalenergyofasystem.
Athermodynamicreservoirisasystemsolargethatitdoesnotappreciablyalteritsstateparameters
whenbroughtintocontactwiththetestsystem.Itisusedtoimposeaparticularvalueofastate
parameteruponthesystem.Forexample,apressurereservoirisasystemataparticularpressure,which
imposesthatpressureuponanytestsystemthatitismechanicallyconnectedto.TheEarth'satmosphere
isoftenusedasapressurereservoir.
Conjugatevariables
Acentralconceptofthermodynamicsisthatofenergy.BytheFirstLaw,thetotalenergyofasystem
anditssurroundingsisconserved.Energymaybetransferredintoasystembyheating,compression,or
additionofmatter,andextractedfromasystembycooling,expansion,orextractionofmatter.In
mechanics,forexample,energytransferequalstheproductoftheforceappliedtoabodyandthe
resultingdisplacement.
Conjugatevariablesarepairsofthermodynamicconcepts,withthefirstbeingakintoa"force"applied
tosomethermodynamicsystem,thesecondbeingakintotheresulting"displacement,"andtheproduct
ofthetwoequallingtheamountofenergytransferred.Thecommonconjugatevariablesare:
Pressurevolume(themechanicalparameters)
Temperatureentropy(thermalparameters)
Chemicalpotentialparticlenumber(materialparameters).
Potentials
Thermodynamicpotentialsaredifferentquantitativemeasuresofthestoredenergyinasystem.
Potentialsareusedtomeasureenergychangesinsystemsastheyevolvefromaninitialstatetoafinal
state.Thepotentialuseddependsontheconstraintsofthesystem,suchasconstanttemperatureor
pressure.Forexample,theHelmholtzandGibbsenergiesaretheenergiesavailableinasystemtodo
usefulworkwhenthetemperatureandvolumeorthepressureandtemperaturearefixed,respectively.
Thefivemostwellknownpotentialsare:
Name
Symbol
Formula
Naturalvariables
Internalenergy
Helmholtzfreeenergy
Enthalpy
Gibbsfreeenergy
LandauPotential(Grandpotential)
where isthetemperature, theentropy, thepressure, thevolume, thechemicalpotential,

thenumberofparticlesinthesystem,and isthecountofparticlestypesinthesystem.
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Thermodynamicpotentialscanbederivedfromtheenergybalanceequationappliedtoathermodynamic
system.OtherthermodynamicpotentialscanalsobeobtainedthroughLegendretransformation.
Axiomatics
Mostaccountsofthermodynamicspresupposethelawofconservationofmass,sometimeswith,[119]and
sometimeswithout,[120][121]explicitmention.Particularattentionispaidtothelawinaccountsofnon
equilibriumthermodynamics.[122][123]Onestatementofthislawis"Thetotalmassofaclosedsystem
remainsconstant."[9]Anotherstatementofitis"Inachemicalreaction,matterisneithercreatednor
destroyed."[124]Impliedinthisisthatmatterandenergyarenotconsideredtobeinterconvertedinsuch
accounts.Thefullgeneralityofthelawofconservationofenergyisthusnotusedinsuchaccounts.
In1909,ConstantinCarathodorypresented[56]apurelymathematicalaxiomaticformulation,a
descriptionoftenreferredtoasgeometricalthermodynamics,andsometimessaidtotakethe
"mechanicalapproach"[79]tothermodynamics.TheCarathodoryformulationisrestrictedtoequilibrium
thermodynamicsanddoesnotattempttodealwithnonequilibriumthermodynamics,forcesthatactata
distanceonthesystem,orsurfacetensioneffects.[125]Moreover,Carathodory'sformulationdoesnot
dealwithmaterialslikewaternear4C,whichhaveadensityextremumasafunctionoftemperatureat
constantpressure.[126][127]Carathodoryusedthelawofconservationofenergyasanaxiomfromwhich,
alongwiththecontentsofthezerothlaw,andsomeotherassumptionsincludinghisownversionofthe
secondlaw,hederivedthefirstlawofthermodynamics.[128]Consequently,onemightalsodescribe
Carathodory'sworkaslyinginthefieldofenergetics,[129]whichisbroaderthanthermodynamics.
Carathodorypresupposedthelawofconservationofmasswithoutexplicitmentionofit.
SincethetimeofCarathodory,otherinfluentialaxiomaticformulationsofthermodynamicshave
appeared,whichlikeCarathodory's,usetheirownrespectiveaxioms,differentfromtheusual
statementsofthefourlaws,toderivethefourusuallystatedlaws.[130][131][132]
Manyaxiomaticdevelopmentsassumetheexistenceofstatesofthermodynamicequilibriumandof
statesofthermalequilibrium.Statesofthermodynamicequilibriumofcompoundsystemsallowtheir
componentsimplesystemstoexchangeheatandmatterandtodoworkoneachotherontheirwayto
overalljointequilibrium.Thermalequilibriumallowsthemonlytoexchangeheat.Thephysical
propertiesofglassdependonitshistoryofbeingheatedandcooledand,strictlyspeaking,glassisnotin
thermodynamicequilibrium.[133]
AccordingtoHerbertCallen'swidelycited1985textonthermodynamics:"Anessentialprerequisitefor
themeasurabilityofenergyistheexistenceofwallsthatdonotpermittransferofenergyintheformof
heat.".[134]AccordingtoWernerHeisenberg'smatureandcarefulexaminationofthebasicconceptsof
physics,thetheoryofheathasaselfstandingplace.[135]
Fromtheviewpointoftheaxiomatist,thereareseveraldifferentwaysofthinkingaboutheat,
temperature,andthesecondlawofthermodynamics.TheClausiuswayrestsontheempiricalfactthat
heatisconductedalwaysdown,neverup,atemperaturegradient.TheKelvinwayistoassertthe
empiricalfactthatconversionofheatintoworkbycyclicprocessesisneverperfectlyefficient.Amore
mathematicalwayistoasserttheexistenceofafunctionofstatecalledtheentropythattellswhethera
hypothesizedprocessoccursspontaneouslyinnature.AmoreabstractwayisthatofCarathodorythat
ineffectassertstheirreversibilityofsomeadiabaticprocesses.Forthesedifferentways,thereare
respectivecorrespondingdifferentwaysofviewingheatandtemperature.
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TheClausiusKelvinPlanckwayThiswayprefersideasclosetotheempiricaloriginsof
thermodynamics.Itpresupposestransferofenergyasheat,andempiricaltemperatureasascalar
functionofstate.AccordingtoGislasonandCraig(2005):"Mostthermodynamicdatacomefrom
calorimetry..."[136]AccordingtoKondepudi(2008):"Calorimetryiswidelyusedinpresentday
laboratories."[137]Inthisapproach,whatisoftencurrentlycalledthezerothlawofthermodynamicsis
deducedasasimpleconsequenceofthepresuppositionofthenatureofheatandempiricaltemperature,
butitisnotnamedasanumberedlawofthermodynamics.Planckattributedthispointofviewto
Clausius,Kelvin,andMaxwell.Planckwrote(onpage90oftheseventhedition,dated1922,ofhis
treatise)thathethoughtthatnoproofofthesecondlawofthermodynamicscouldeverworkthatwasnot
basedontheimpossibilityofaperpetualmotionmachineofthesecondkind.Inthattreatise,Planck
makesnomentionofthe1909Carathodoryway,whichwaswellknownby1922.Planckforhimself
choseaversionofwhatisjustabovecalledtheKelvinway.[138]ThedevelopmentbyTruesdelland
Bharatha(1977)issoconstructedthatitcandealnaturallywithcaseslikethatofwaternear4C.[131]
ThewaythatassumestheexistenceofentropyasafunctionofstateThiswayalsopresupposes
transferofenergyasheat,anditpresupposestheusuallystatedformofthezerothlawof
thermodynamics,andfromthesetwoitdeducestheexistenceofempiricaltemperature.Thenfromthe
existenceofentropyitdeducestheexistenceofabsolutethermodynamictemperature.[8][130]
TheCarathodorywayThiswaypresupposesthatthestateofasimpleonephasesystemisfully
specifiablebyjustonemorestatevariablethantheknownexhaustivelistofmechanicalvariablesof
state.Itdoesnotexplicitlynameempiricaltemperature,butspeaksoftheonedimensional"non
deformationcoordinate".Thissatisfiesthedefinitionofanempiricaltemperature,thatliesonaone
dimensionalmanifold.TheCarathodorywayneedstoassumemoreoverthattheonedimensional
manifoldhasadefinitesense,whichdeterminesthedirectionofirreversibleadiabaticprocess,whichis
effectivelyassumingthatheatisconductedfromhottocold.Thiswaypresupposestheoftencurrently
statedversionofthezerothlaw,butdoesnotactuallynameitasoneofitsaxioms.[125]Accordingtoone
author,Carathodory'sprinciple,whichishisversionofthesecondlawofthermodynamics,doesnot
implytheincreaseofentropywhenworkisdoneunderadiabaticconditions(aswasnotedby
Planck[139]).ThusCarathodory'swayleavesunstatedafurtherempiricalfactthatisneededforafull
expressionofthesecondlawofthermodynamics.[140]
Scopeofthermodynamics
Originallythermodynamicsconcernedmaterialandradiativephenomenathatareexperimentally
reproducible.Forexample,astateofthermodynamicequilibriumisasteadystatereachedafterasystem
hasagedsothatitnolongerchangeswiththepassageoftime.Butmorethanthat,forthermodynamics,
asystem,definedbyitsbeingpreparedinacertainwaymust,consequentoneveryparticularoccasion
ofpreparation,uponaging,reachoneandthesameeventualstateofthermodynamicequilibrium,
entirelydeterminedbythewayofpreparation.Suchreproducibilityisbecausethesystemsconsistofso
manymoleculesthatthemolecularvariationsbetweenparticularoccasionsofpreparationhave
negligibleorscarcelydiscernableeffectsonthemacroscopicvariablesthatareusedinthermodynamic
descriptions.ThisledtoBoltzmann'sdiscoverythatentropyhadastatisticalorprobabilisticnature.
Probabilisticandstatisticalexplanationsarisefromtheexperimentalreproducibilityofthe
phenomena.[141]
Gradually,thelawsofthermodynamicscametobeusedtoexplainphenomenathatoccuroutsidethe
experimentallaboratory.Forexample,phenomenaonthescaleoftheearth'satmospherecannotbe
reproducedinalaboratoryexperiment.Butprocessesintheatmospherecanbemodeledbyuseof
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thermodynamicideas,extendedwellbeyondthescopeoflaboratoryequilibrium
thermodynamics.[142][143][144]Aparcelofaircan,nearenoughformanystudies,beconsideredasa
closedthermodynamicsystem,onethatisallowedtomoveoversignificantdistances.Thepressure
exertedbythesurroundingaironthelowerfaceofaparcelofairmaydifferfromthatonitsupperface.
Ifthisresultsinrisingoftheparcelofair,itcanbeconsideredtohavegainedpotentialenergyasaresult
ofworkbeingdoneonitbythecombinedsurroundingairbelowandaboveit.Asitrises,suchaparcel
usuallyexpandsbecausethepressureisloweratthehigheraltitudesthatitreaches.Inthatway,the
risingparcelalsodoesworkonthesurroundingatmosphere.Formanystudies,suchaparcelcanbe
considerednearlytoneithergainnorloseenergybyheatconductiontoitssurroundingatmosphere,and
itsriseisrapidenoughtoleavenegligibletimeforittogainorloseheatbyradiationconsequentlythe
risingoftheparcelisnearenoughadiabatic.Thustheadiabaticgaslawaccountsforitsinternalstate
variables,providedthatthereisnoprecipitationintowaterdroplets,noevaporationofwaterdroplets,
andnosublimationintheprocess.Moreprecisely,therisingoftheparcelislikelytooccasionfriction
andturbulence,sothatsomepotentialandsomekineticenergyofbulkconvertsintointernalenergyof
airconsideredaseffectivelystationary.Frictionandturbulencethusopposetherisingofthe
parcel.[145][146]
Appliedfields
Atmosphericthermodynamics
Biologicalthermodynamics
Blackholethermodynamics
Chemicalthermodynamics
Equilibriumthermodynamics
Geology
Industrialecology(re:Exergy)
Maximumentropythermodynamics
Nonequilibriumthermodynamics
Philosophyofthermalandstatisticalphysics
Psychrometrics
Quantumthermodynamics
Statisticalthermodynamics
Thermoeconomics
Seealso
Entropyproduction
Listsandtimelines
Listofimportantpublicationsinthermodynamics
Listoftextbooksinstatisticalmechanics
Listofthermalconductivities
Listofthermodynamicproperties
Tableofthermodynamicequations
Timelineofthermodynamics
Wikibooks
EngineeringThermodynamics
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EntropyforBeginners
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Planck,M.(1923/1926).TreatiseonThermodynamics,thirdEnglisheditiontranslatedbyA.Ogg
fromtheseventhGermanedition,Longmans,Green&Co.,London.
Serrin,J.(1986).NewPerspectivesinThermodynamics,editedbyJ.Serrin,Springer,Berlin,
ISBN3540159312.
Sommerfeld,A.(1952/1956).ThermodynamicsandStatisticalMechanics,AcademicPress,New
York.
Tschoegl,N.W.(2000).FundamentalsofEquilibriumandSteadyStateThermodynamics,Elsevier,
Amsterdam,ISBN0444504265.
Tisza,L.(1966).GeneralizedThermodynamics,M.I.TPress,CambridgeMA.
Truesdell,C.A.(1980).TheTragicomicalHistoryofThermodynamics,18221854,Springer,New
York,ISBN0387904034.
Furtherreading
Goldstein,Martin,andIngeF.(1993).TheRefrigeratorandtheUniverse.HarvardUniversityPress.ISBN0
674753259.OCLC32826343.Anontechnicalintroduction,goodonhistoricalandinterpretivematters.
Kazakov,Andrei(JulyAugust2008)."WebThermoTablesanOnLineVersionoftheTRC
ThermodynamicTables"(PDF).JournalofResearchoftheNationalInstitutesofStandardsandTechnology
113(4):209220.doi:10.6028/jres.113.016.
Thefollowingtitlesaremoretechnical:
Cengel,YunusA.,&Boles,MichaelA.(2002).ThermodynamicsanEngineeringApproach.McGrawHill.
ISBN0072383321.OCLC45791449.
Fermi,E.(1956).Thermodynamics,Dover,NewYork.
Kittel,Charles&Kroemer,Herbert(1980).ThermalPhysics.W.H.FreemanCompany.ISBN071671088
26/27
5/21/2016
9.OCLC32932988.
Externallinks
ThermodynamicsData&PropertyCalculationWebsites(h
Wikiquotehasquotations
ttp://tigger.uic.edu/~mansoori/Thermodynamic.Data.and.Pr
relatedto:
operty_html)
Thermodynamics
ThermodynamicsOpenCourseWare(http://ocw.nd.edu/aer
ospaceandmechanicalengineering/thermodynamics)fromtheUniversityofNotreDame
Archived(https://web.archive.org/web/20110304160750/https://web.archive.org/web/2011030416
0750/http://ocw.nd.edu/aerospaceandmechanicalengineering/thermodynamics)March4,2011,
attheWaybackMachine.
ThermodynamicsatScienceWorld(http://scienceworld.wolfram.com/physics/topics/Thermodyna
mics.html)
BiochemistryThermodynamics(http://www.wiley.com/legacy/college/boyer/0470003790/review
s/thermo/thermo_intro.htm)
EngineeringThermodynamicsAGraphicalApproach(http://www.ent.ohiou.edu/~thermo/)
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Thermodynamics&oldid=715999458"
Categories: Thermodynamics Conceptsinphysics Engineeringthermodynamics
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where isthetemperature, theentropy, thepressure, thevolume, thechemicalpotential,

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