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3/7/2017 HeatEngines,Entropy

iePhysics

HeatEngines&Entropy
thermodynamics
byWilliamDietsch2006

HeatEnergy(Q)

Theenergy,whichflows,fromonebodytoanotherbecauseoftheirtemperaturedifference.Iftwo
bodieshavethesametemperatureasathird,theywillbeinthermalequilibriumwitheachotherandno
heatwillflow.Thisfactisoftenrefereedtoasthezerothlawofthermodynamics.+Qreferstoheat
whichflowsfromasystemandQindicatesheatflowintoasystem.

InternalEnergy(U)

Referstothetotalenergycontentofasystem.Itisthesumofallthekinetic,potential,electrical,nuclear
andallotherformsofenergypossessedbythemoleculesofasystem.Theinternalenergyofanideal
gasispurelykineticanddependsonlyonthetemperatureofthegas.

WorkDoneByASystem(W)

Whenasystemdoesworktoitssurroundings,Whasapositivesign.Ifthesurroundingsdoworkona
system,Whasanegativesign.

TheFirstLawOfThermodynamics

Thefirstlawisastatementoftheprincipleofconservationofenergy.Itstatesthatifanamountof
heatenergy(Q)flowsintosystem,thenthisenergymustappearasanincreaseintheinternalenergy
(U)andorwork(W)donebythesystemonitssurroundings.(preferableunitsareJoules)

Q=U+W

IsobaricProcess

Aprocesscarriedoutataconstantpressure.Seebelow.

Isochoric(Isovolumetric)Process

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Aprocesscarriedoutataconstantvolume.Whenagasundergoessuchaprocess,anyheat,whichflows
intothesystem,appearsasanincreaseintheinternalenergyofthesystem,i.e.,Q=U.Seebelow.

IsothermalProcess

Aconstanttemperatureprocess.Inthecaseofanidealgas,U=0.Thisinnottrueforallsystems.
Forexample,whenicemeltsthechangeininternalenergyisnotequaltozerobecausethechangeof
staterequiresenergyinputtotheicetochangeitsstate(latentheatoffusion).Foranidealgasunder
isothermalconditions,(i.e.,U=0)allworkinputisequaltoanincreaseinthethermalenergy.(Q=
W).Seebelow.

AdiabaticProcess

Oneinwhichnoheatenergyistransferredtoorfromasystem.Q=0).Anyworkdonebythesystem
isdoneattheexpenseoftheinternalenergy(0=Q=U+W).

TheEfficiencyOfAHeatEngine

Theidealefficiencyofaheatengineisdefinedas:=workoutput/workinput.

TheCarnotcyclebyNicolasLonardSadiCarnot(b1796inParis,d1832)isthemostefficientcycle
possibleforaheatengine.Anengineinaccordancetothiscycleoperatesbetweenahotreservoir(at
temperatureTh)andacoldreservoir(attemperatureTc).(Thetemperaturesareabsolute,preferably
expressedinKelvin.)Theefficiency,=1Tc/Th.

TheCarnotCycle:

ABThegasisfirst(thisisacycle,soourstartisarbitrary)
expandedisothermallybytheadditionofheatQh.

BCThegasthenexpandsadiabatically.Noheatentersor
leavesthesystembutthetemperaturedropsfromThtoTc.

CDThegasiscompressedisothermally(constant
temperatureTc)andheatflowsoutQc.

DAThegasiscompressedadiabatically.Noheatentersorleavesthesystem,butthetemperature
increasestotheoriginalmeasure.

Theareaencompassedbytheenclosedcurvesonthegraphrepresentstheworkdonebytheengine.

Ifthefirstandthirdstepsaredoneinfinitelyslowlytheprocessistheoreticallyreversible.

Arealprocessontheotherhandisnotcompletedslowlyandthereforeresultsinanirreversibleprocess.
Inpracticalapplications,heatcanbesuppliedbyafuelandexternalworkperformed.Orthecyclecan
bereversedusinganexternalsourceofwork,pumpingheatoutintothewarmerenvironmentasina
refrigerator.

SecondLawOfThermodynamics
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Heatflowsspontaneouslyfromahottertoacolderobject,butnotviceversa.ThisistheClausius
statementofthesecondlaw.

Nodeviceispossiblewhosesoleeffectistotransformagivenamountofheatcompletelyintowork.
ThisistheKelvinPlanckstatementofthesecondlaw.

Ifasystemundergoesspontaneouschange,itwillchangeinsuchawaythatitsdisorderwillincrease,or
atbestremainthesame.

Ifasystemundergoesspontaneouschange,itwillchangeinsuchawaythatitsentropywillincrease,or
atbestremainthesame.

Thesecondlawtellsusthedirectionaspontaneouschangewillfollow,whilethefirstlawtellswhether
ornotthechangeispossibleaccordingtoenergyconservation.Sometimesthesecondlawisusedto
determinetimesarrow.Thatis,theincreaseofentropyanddecreaseofavailableenergyinasystemis
anindicatorofthespontaneousprocessesthatweusetomeasurethepassageoftime.

Entropy(S)

Entropyisastatevariableforasystematequilibrium.Thismeansthattheentropy(S)isalwaysthe
sameforasystematequilibrium.Whenheat(Q)entersasystematabsolutetemperatureT,thenthe
changeinentropyis:S=Q/T.Areversiblechangeisoneinwhichthevaluesofp,V,T,andUare
welldefinedduringthechange.Iftheprocessisreversedthenthevaluesofp,V,T,andUwillfollow
thesamevaluesbutinreverseorderthoroughthechange.

EntropyIsAMeasureOfDisorder

Anotherfullyequivalentdefinitionofentropycanbegivenfromadetailedmolecularanalysisofthe
system.Ifasystemcanachievethesamestateindifferentways(differentarrangementofthe
moleculesetc.)thentheentropyofthesystemcanbeexpressed:S=kln.WherekisBoltzmanns
constant(1.38X1023J/K)andlnislogarithmtothebasee.

Asystemthatcanoccurinonlyonestate(onlyonearrangementofthemoleculesforexample)hasa
highstateoforderandalowstateofentropy.Toassociateanumberwithdisorder,thedisorderofthe
systemisproportionalto(thenumberofpossiblewaysthatstatecanoccur).Spontaneousprocessesin
systemscontainingmanymoleculesalwaysproceedfromastateofordertoastateofdisorder.
Entropyneverdecreasesinaspontaneousprocessitalwaysincreasesorstaysthesame.

MostProbableState

Isthatstateofasystem,inwhichtheentropyhasamaximumvalue.Itisthestatewiththemaximum
disorderandthestatethatcanoccurinthelargestnumberofways.

LudwigBoltzmann(b1844,d1906)madeacleardistinctionbetweenthegrosspropertiesofasystem
suchaspressure,temperature,andvolume(macrostate),andthemicrostateofthesubstance.The
microstateofthesubstancewouldbeascertainedbydeterminingthepositionandvelocityofallofthe
moleculesmakingupthatsystem.Therearelotsofmicrostates,whichcanyieldthesame
macrostate.Considerthepossiblemicrostatesinwhichonlyfourcoinsaretossedasshowninthe
followingtable.

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Macrostate PossibleMicrostates Numberofmicrostates,


H=headsT=tails

4heads HHHH 1

3heads,1tail HHHT,HHTH,HTHH,THHH 4

2heads,2tails HHTT,HTHT,THHT,HTTH,THTH,TTHH 6

1head,3tails TTTH,TTHT,THTT,HTTT 4

4tails TTTT 1

Belowisatablefor102tossedcoins.Afternotingthenumberofmicrostatesforahundredcoins,
considerthevastnumbersofmicrostatestothelocationsofmoleculesinaballoonofgas(recallamoleof
gascontains6x1023 molecules).Thissuggeststhatthesecondlawisessentiallyastatisticalone.Itis
theoreticallypossibletotoss100coinsandhavethemallcomingoutheads,buttheprobabilityofthis
happeningisextremelylow.Intermsofprobability,thesecondlawclaimsthatentropyalways
increases.Moreprecisely,itstatesthatthisisthemostprobableoutcomeofanyphysicalchange.Itis
theoreticallypossibleforentropytospontaneouslydecrease,butforanysystemwithalargenumberof
entities,itishighlyimprobable.

Numberofmicrostates
Macrostate
(notemanyrowshavebeenomitted)

Heads Tails

100 0 1

99 1 1.0x102

90 10 1.7x1013

80 20 5.4x1020

60 40 1.4x1028

55 45 6.1x1028

50 50 1.0x1029

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45 55 6.1x1028

40 60 1.4x1028

20 80 5.4x1020

10 90 1.7x1013

1 99 1.0x102

100 0 1

EntropyAsAMeasureOfInformation

PierreSimon,marquisdeLaPlace(b1749d1827)inthenineteenthcenturyproposedaformof
scientificdeterminism.Brieflystated,hesurmisedthatasufficientlyadvancedsciencewouldbeableto
determinetheexactvelocityandpositionofalloftheparticlesintheuniverse.Usingthisinformationa
person,intheorycouldpredictallfutureevents.WernerHeisenberg's(b1901d1976)uncertainty
theorymadethisformofdeterminismimpossible.Quantumdeterminismissimilarinthatitcanpredict
thefuturebehaviorofquantizedmatter.Extrapolatingthistoasuperadvancedcivilization,itisonce
againpossibletopredictthefuturemathematically.

Informationisdeemedbysometobeameasureofentropy.Asingleletterorbitofbinarycarriesvery
littleinformationandassuchhasverylowentropy.Asmoreinformationiscontainedwithinabody
(suchasmass,velocity,quantumwavefunctionsetc.),theentropycontainedwithinthatbodyalso
increases.Complexsystemscontainagreatdealofinformationandassuchhavelargeamountsof
entropy.Somephysicistslookatallmatterandenergyasmerelyinformationcarriedbythewave
functionsoftheconstituentpartsofthebody.

EntropyInBlackHoles

Blackholesarelocationsinwhichthegravitationofacollapsedstarissogreatitwarpsspacetothe
pointwhereitcreatesasingularityofinfinitedensity.Theblackholehasonlymass,charge,angular
momentumandentropy.Allofthecomplexityandattendantinformation(entropy)containedinthe
uncollapsedstarisreducedtotheabovesimpleproperties.AccordingtoStephenHawking(b1942)
andJacobD.Bekenstein(b1947),theentropyoftheblackholeonlydeterminestheareaoftheevent
horizon,nothingelse.ThisisthenohairtheoremproposedbyRogerPenrose(b1931).Wherehasall
oftheinformationoriginallycontainedwithinthestargone?Hasthesecondlawofthermodynamics
beenviolatedinthatentropyislostforever,causingtheentropyoftheuniversetodecrease?

Hawkinghasproposedthatblackholesarentsoblackastheyradiateenergyattheeventhorizondue
toquantumfluctuations.Doesthisradiationcontaintheinformationcarriedbythecollapsingstarand
anythingelse,whichhasfallenintotheblackhole?Iftheinformationisonlythermalthentheansweris
no.TheHawkingradiationcausedtheblackholetoeventuallyevaporate(overanunbelievablylong
periodoftime).IftheHawkingradiationdoesnotcarrytheinformationitislostforeverandthesecond
lawisviolated.
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Supposeyoutossedabookintoablackhole?Thebookwouldbelostforeverandaddtotheareaofthe
eventhorizon,howevertheinformationcontainedwithinthebookisirretrievable.Thispresentsabig
problemtothosewhobelievethesecondlawofthermodynamicsisinviolate.It'scertainlypossiblethat
theentropyofmatterfallingintoablackholecanbetracedasthemattercrossesthehorizonopinionson
thisdiffer.But,firstofall,youarenotgoingtogetenoughentropytoaccountforthe(enormous!)
BekensteinHawkingentropyoftheblackholeaveryhighentropyblackholecanbeformedfrom
verylowentropymatter.Ifyouwanttoaccountforblackholeentropythisway,there'sasensethatyou
can,buttodothatyouhavetocountupallofthedifferentpossiblewaystheblackholecouldhave
formed,notjusttheparticularwayitdid.Theinformationlossparadoxisaquantummechanicalone:
youcan,itseems,formablackholefromapurequantumstate,andthenhaveitevaporatebyHawking
radiationintoamixedstate.Suchatransitionfromapurestatetoamixedstateviolatesthestandard
rulesofquantummechanics.It'scalled``informationloss''because,basically,youloseinformationabout
thequantumstateoftheuniverse.

TheComplexityCompromise*

Theconceptofcomplexityismoredifficulttopindown.Aphysicalsystemthatweconsidertobe
'complex'representsadelicatecompromisebetweenmindlesssimplicityandpurerandomness.Thisidea
canbestbeillustratedgraphically.Intheleftbox,thepointsarearrangedinaregularlyspacedgrid
(likeacrystal).Thissimplearrangementcarrieswithitlittleinformationandcanbedescribedbya
singlenumberspecifyinggridspacing.Ifnewpointsweretobeadded,oneknowsexactlywheretoput
them.

Theoppositeextremeisthemiddlepattern,whichdepictsarandomcollectionofpoints.This
arrangementofpointsrequiresagreatdealofinformationtodescribe.Becausethelocationofeach
pointisrandomandunrelatedtoanyother,thexandycoordinatesofeachandeverypointmustbe
specifiedtodefinethepattern.Sucharandompatterncarriesthemaximumamountofinformation.If
apointistobeaddedtothepattern,onehasnoideawherethepointshouldbeplaced.

Thepatternontherightillustratesamoreinterestingpattern,onethatissimultaneouslymorestructured
thanrandompointsandencodesmoreinformationthanthesimplegridatthetop.Ifanewpointistobe
addedonewouldhavesomeideawhereitmightfall,andyetitisnotcompletelyspecifiedinadvanceas
inthesimplegrid.Complexandinterestingpatternsnegotiatethepropercompromisebetween
simplicityandrandomness.

*ByphysicistFredAdams,withthehelpofillustratorIanSchoenherr,OurLivingMultiverse2004,
PiPress(NewYork)andOriginsofExistence2006

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createdand2006byWilliamDietsch
posted&edited4February2008byDTrapp

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