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Vol 1 Ch 44 - The Laws of Thermodynamics

Vol 1 Ch 44 - The Laws of Thermodynamics

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Feynman Lectures on Physics
Feynman Lectures on Physics

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02/15/2014

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44
TheLaws
of
Thermodynamics
44-1Heatengines;thefirstlawSofarwehavebeendiscussingthepropertiesofmatterfromtheatomicpointofview,tryingtounderstandroughlywhatwillhappenifwesupposethatthingsaremadeofatomsobeyingcertainlaws.However,thereareanumberofrelation-shipsamongthepropertiesofsubstanceswhichcanbeworkedoutwithoutcon-siderationofthedetailedstructureofthematerials.Thedeterminationoftherelationshipsamongthevariouspropertiesofmaterials,withoutknowingtheirinternalstructure,isthesubjectof
thermodynamics.
Historically,thermodynamicswasdevelopedbeforeanunderstandingoftheinternalstructureofmatterwasachieved.Togiveanexample:weknowfromthekinetictheorythatthepressureofagasiscausedbymolecularbombardment,andweknowthatifweheatagas,sothatthebombardmentincreases,thepressuremustincrease.Conversely,ifthepistoninacontainerofthegasismovedinwardagainsttheforceofbombardment,theenergyofthemoleculesbombardingthepistonwillincrease,andconsequentlythetemperaturewillincrease.So,ontheonehand,ifweincreasethetemperatureatagivenvolume,weincreasethepressure.Ontheotherhand,ifwecompressthegas,wewillfindthatthetemperaturewillrise.Fromthekinetictheory,onecanderiveaquantitativerelationshipbetweenthesetwoeffects,butinstinctivelyonemightguessthattheyarerelatedinsomenecessaryfashionwhichisindepend-entofthedetailsofthecollisions.Letusconsideranotherexample.Manypeoplearefamiliarwiththisinterest-ingpropertyofrubber:Ifwetakearubberbandandpullit,itgetswarm.Ifoneputsitbetweenhislips,forexample,andpullsitout,hecanfeeladistinctwarming,andthiswarmingisreversibleinthesensethatifherelaxestherubberbandquicklywhileitisbetweenhislips,itisdistinctlycooled.Thatmeansthatwhenwestretcharubberbanditheats,andwhenwereleasethetensionofthebanditcools.Nowourinstinctsmightsuggestthatifweheatedaband,itmightpull:thatthefactthatpullingabandheatsitmightimplythatheatingabandshouldcauseittocontract.And,infact,ifweapplyagasflametoarubberbandholdingaweight,wewillseethatthebandcontractsabruptly(Fig.44-1).Soitistruethatwhenweheatarubberbanditpulls,andthisfactisdefinitelyrelatedtothefactthatwhenwereleasethetensionofit,itcools.Theinternalmachineryofrubberthatcausestheseeffectsisquitecomplicated.Wewilldescribeitfromamolecularpointofviewtosomeextent,althoughourmainpurposeinthischapteristounderstandtherelationshipoftheseeffectsindependentlyofthemolecularmodel.Nevertheless,wecanshowfromthemolec-ularmodelthattheeffectsarecloselyrelated.Onewaytounderstandthebehaviorofrubberistorecognizethatthissubstanceconsistsofanenormoustangleoflongchainsofmolecules,akindof"molecularspaghetti,"withoneextracompli-cation:betweenthechainstherearecross-links-likespaghettithatissometimesweldedtogetherwhereitcrossesanotherpieceofspaghetti-agrandtangle.Whenwepulloutsuchatangle,someofthechainstendtolineupalongthedirec-tionofthepull.Atthesametime,thechainsareinthermalmotion,sotheyhiteachothercontinually.
It
followsthatsuchachain,ifstretched,wouldnotbyitselfremainstretched,becauseitwouldbehitfromthesidesbytheotherchainsandothermolecules,andwouldtendtokinkupagain.Sotherealreasonwhyarubberbandtendstocontractisthis:whenonepullsitout,thechainsarelength-wise,andthethermalagitationsofthemoleculesonthesidesofthechainstend
44-1
44-1Heatengines;thefirstlaw44-2Thesecondlaw44-3Reversibleengines
44-4
Theefficiencyofanidealengine44-5Thethermodynamictemperature44-6Entropy
Fig.44-1.Theheatedrubberband.
 
Fig.
44-2.
Therubber-bandheatengine.
tokinkthechainsup,andmakethemshorten.Onecanthenappreciatethatifthechainsareheldstretchedandthetemperatureisincreased,sothatthevigorofthebombardmentonthesidesofthechainsisalsoincreased,thechainstendtopullin,andtheyareabletopullastrongerweightwhenheated.If,afterbeingstretchedforatime,arubberbandisallowedtorelax,eachchainbecomessoft,andthemoleculesstrikingitloseenergyastheypoundintotherelaxingchain.Sothetemperaturefalls.Wehaveseenhowthesetwoprocess,contractionwhenheatedandcoolingduringrelaxation,canberelatedbythekinetictheory,butitwouldbeatremendouschallengetodeterminefromthetheorythepreciserelationshipbetweenthetwo.Wewouldhavetoknowhowmanycollisionstherewereeachsecondandwhatthechainslooklike,andwewouldhavetotakeaccountofallkindsofothercomplica-tions.Thedetailedmechanismissocomplexthatwecannot,bykinetictheory,reallydetermineexactlywhathappens;still,adefiniterelationbetweenthetwoeffectsweobservecanbeworkedoutwithoutknowinganythingabouttheinternalmachinery!Thewholesubjectofthermodynamicsdependsessentiallyuponthefollowingkindofconsideration:becausearubberbandis"stronger"athighertemperaturesthanitisatlowertemperatures,itoughttobepossibletoliftweights,andtomovethemaround,andthustodoworkwithheat.Infact,wehavealreadyseenexperimentallythataheatedrubberbandcanliftaweight.Thestudyofthewaythatonedoesworkwithheatisthebeginningofthescienceofthermodynamics.Canwemakeanenginewhichusestheheatingeffectonarubberbandtodowork?Onecanmakeasillylookingenginethatdoesjustthis.
It
consistsofabicyclewheelinwhichallthespokesarerubberbands(Fig.44-2).Ifoneheatstherubberbandsononesideofthewheelwithapairofheatlamps,theybecome"stronger"thantherubberbandsontheotherside.Thecenterofgravityofthewheelwillbepulledtooneside,awayfromthebearing,sothatthewheelturns.Asitturns,coolrubberbandsmovetowardtheheat,andtheheatedbandsmoveawayfromtheheatandcool,sothatthewheelturnsslowlysolongastheheatisapplied.Theefficiencyofthisengineisextremelylow.Fourhundredwattsofpowerpourintothetwolamps,butitisjustpossibletoliftaflywithsuchanengine!Aninter-estingquestion,however,iswhetherwecangetheattodotheworkinmoreefficientways.Infact,thescienceofthermodynamicsbeganwithananalysis,bythegreatengineerSadiCarnot,oftheproblemofhowtobuildthebestandmostefficientengine,andthisconstitutesoneofthefewfamouscasesinwhichengineeringhascontributedfundamentallytophysicaltheory.AnotherexamplethatcomestomindisthemorerecentanalysisofinformationtheorybyClaudeShannon.Thesetwoanalyses,incidentally,turnouttobecloselyrelated.Nowthewayasteamengineordinarilyoperatesisthatheatfromafireboilssomewater,andthesteamsoformedexpandsandpushesonapistonwhichmakesawheelgoaround.Sothesteampushesthepiston-whatthen?Onehastofinishthejob:qstupidwaytocompletethecyclewouldbetoletthesteamescapeintotheair,forthenonehastokeepsupplyingwater.
It
ischeaper-moreefficient-toletthesteamgointoanotherbox,whereitiscondensedbycoolwater,andthenpumpthewaterbackintotheboiler,sothatitcirculatescontinuously.Heatisthussuppliedtotheengineandconvertedintowork.Nowwoulditbebettertousealcohol?Whatpropertyshouldasubstancehavesothatitmakesthebestpossibleengine?ThatwasthequestiontowhichCarnotaddressedhimself,andoneoftheby-productswasthediscoveryofthetypeofrelationshipthatwehavejustexplainedabove.Theresultsofthermodynamicsareallcontainedimplicitlyincertainappar-entlysimplestatementscalledthe
lawsofthermodynamics.
AtthetimewhenCarnotlived,thefirstlawofthermodynamics,theconservationofenergy,wasnotknown.Carnot'sargumentsweresocarefullydrawn,however,thattheyarevalideventhoughthefirstlawwasnotknowninhistime!Sometimeafterwards,ClausiusmadeasimplerderivationthatcouldbeunderstoodmoreeasilythanCarnot'sverysubtlereasoning.ButitturnedoutthatClausiusassumed,nottheconserva-
44-2
 
tionofenergyingeneral,butthat
heat
wasconservedaccordingtothecalorictheory,whichwaslatershowntobefalse.SoithasoftenbeensaidthatCarnot'slogicwaswrong.Buthislogicwasquitecorrect.OnlyClausius'simplifiedver-sion,thateverybodyread,wasincorrect.Theso-calledsecondlawofthermodynamicswasthusdiscoveredbyCarnotbeforethefirstlaw!
It
wouldbeinterestingtogiveCarnot'sargumentthatdidnotusethefirstlaw,butweshallnotdosobecausewewanttolearnphysics,nothistory.Weshallusethefirstlawfromthestart,inspiteofthefactthatagreatdealcanbedonewithoutit.Letusbeginbystatingthefirstlaw,theconservationofenergy:ifonehasasystemandputsheatintoit,anddoesworkonit,thenitsenergyisincreasedbytheheatputinandtheworkdone.Wecanwritethisasfollows:Theheat
Q
putintothesystem,plusthework
W
doneonthesystem,istheincreaseintheenergy
U
ofthesystem;thelatterenergyissometimescalledtheinternalenergy:Changein
U
=
Q
+
W.
(44.1)Thechangein
U
canberepresentedasaddingalittleheat
..:lQ
andaddingalittlework
dW:dU
=
.:lQ
+
dW,
(44.2)whichisadifferentialformofthesamelaw.Weknowthatverywell,fromanearlierchapter.44-2ThesecondlawNow,whataboutthesecondlawofthermodynamics?Weknowthatifwedoworkagainstfriction,say,theworklosttousisequaltotheheatproduced.Ifwedoworkinaroomattemperature
T,
andwedotheworkslowlyenough,theroomtemperaturedoesnotchangemuch,andwehaveconvertedworkintoheatatagiventemperature.Whataboutthereversepossibility?Isitpossibletoconverttheheatbackintoworkatagiventemperature?Thesecondlawofthermo-dynamicsassertsthatitisnot.
It
wouldbeveryconvenienttobeabletoconvertheatintoworkmerelybyreversingaprocesslikefriction.
If
weconsideronlytheconservationofenergy,wemightthinkthatheatenergy,suchasthatinthevibra-tionalmotionsofmolecules,mightprovideagoodlysupplyofusefulenergy.ButCarnotassumedthatitisimpossibletoextracttheenergyofheatatasingletemperature.Inotherwords,ifthewholeworldwereatthesametemperature,onecouldnotconvertanyofitsheatenergyintowork:whiletheprocessofmakingworkgointoheatcantakeplaceatagiventemperature,onecannotreverseittogettheworkbackagain.Specifically,Carnotassumedthatheatcannotbetakeninatacertaintemperatureandconvertedintowork
withnootherchange
inthesystemorthesurroundings.Thatlastphraseisveryimportant.Supposewehaveacanofcompressedairatacertaintemperature,andwelettheairexpand.
It
candowork;itcanmakehammersgo,forexample.
It
coolsoffalittleintheexpansion,butifwehadabigsea,liketheocean,atagiventemperature-aheatreservoir-wecouldwarmitupagain.Sowehavetakentheheatoutofthesea,andwehavedoneworkwiththecompressedair.ButCarnotwasnotwrong,because
wedidnotleaveeverythingasitwas.
Ifwerecompresstheairthatweletexpand,wewillfindwearedoingextrawork,andwhenwearefinishedwewilldiscoverthatwenotonlygotnoworkoutofthesystemattemperature
T,
butweactuallyputsomein.Wemusttalkonlyaboutsituationsinwhichthe
netresult
ofthewholeprocessistotakeheatawayandconvertitintowork,justasthenetresultoftheprocessofdoingworkagainstfrictionistotakeworkandconvertitintoheat.
If
wemoveinacircle,wecanbringthesystembackpreciselytoitsstartingpoint,withthenetresultthatwedidworkagainstfrictionandproducedheat.Canwereversetheprocess?Turnaswitch,sothateverythinggoesbackwards,sothefrictiondoesworkagainstus,andcoolsthesea?AccordingtoCarnot:no!Soletussupposethatthisisimpossible.
44-3

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