17.

Heat and the First Law of

Thermodynamics
17.1. Heat
Twobodiesbroughtinthermalcontactwillchangetheirtemperatureuntilthey
areatthesametemperature. Intheprocessofreaching thermalequilibrium, heatis
transferredfromonebodytotheother.
Suppose we have a system of interest at temperature T S surrounded by an
environment with temperature TE. If TS > TE heat flows from the system to the
environment. If TS < TE heat flows from the environment into the system. Heat,
presentedbythesymbolQandunitJoule,ischosentobepositivewhenheatflowsinto
thesystem,andnegativeifheatflowsoutofthesystem(seeFigure17.1).Heatflowisa
resultsofatemperaturedifferencebetweentwobodies,andtheflowofheatiszeroifT S
=TE.

Figure17.1.HeatFlow.
Heatisnottheonlywayinwhichenergycanbetransferredbetweenasystemand
itsenvironment.Energycanalsobetransferredbetweenasystemanditsenvironmentby
meansofwork(W).TheunitofworkistheJoule.
Anothercommonlyusedunitisthecalorie.Thecalorieisdefinedastheamount
ofheatthatwouldraisethetemperatureof1gofwaterfrom14.5Cto15.5C.The
Jouleandthecaloriearerelatedasfollows:1cal=4.1860J

17.2. Heat Capacity

 Whenheatisaddedtoanobject,itstemperatureincreases. Thechangeinthe
temperatureisproportionaltotheamountofheatadded

TheconstantCiscalledtheheatcapacityoftheobject.Theheatcapacityofanobject
dependsonitsmassandthetypeofmaterialofwhichitismade.Theheatcapacityofan
objectisproportionaltoitsmass,andtheheatcapacityperunitmass,c,iscommonly
used.Inthatcase

wheremisthemassoftheobject. The molarheatcapacityistheheatcapacityper

moleofmaterial.Formostmaterialsthemolarheatcapacityis25J/molK.
Inordertodeterminetheheatcapacityofasubstancewenotonlyneedtoknow
howmuchheatisadded,butalsotheconditionsunderwhichtheheattransfertookplace.
Forgases,addingheatunderconstantpressureandunderconstanttemperaturewilllead
toverydifferentvaluesofthespecificheatcapacity.

17.3. Heat of Transformation

Whenheatisaddedtoasolidoraliquid,thetemperatureofthesampledoesnot
necessarilyrise. Duringaphasechange(melting,boiling)heatisaddedtothesample
withoutanincreaseintemperature.Theamountofheattransferredpermassunitduring
aphasechangeiscalledthe heatoftransformation(symbolL)fortheprocess. The
amountofheatneeded/releasedisgivenby

wheremisthemassofthesample.
Problem28P
Whatmassofsteamof100Cmustbemixedwith150goficeat0C,ina
thermallyinsulatedcontainer,toproduceliquidwaterat50C?

Westartwithcalculatingtheheatrequiredtotransform150goficeat0Cto150
gofliquidat0C. Theheatoftransformationofwateris333kJ/kg(seeTable202,
page555).Thetransformationoficeintowaterthereforerequiresatotalheatgivenby

Theheatrequiredtochangethetemperatureof150gofwaterfrom0Cto50Cisgiven
by

Thetotalheatthatneedstobeaddedtothesystemisthereforeequalto81.5kJ.Thisheat
mustbesuppliedbythesteam.Heatwillbereleasedwhenthesteamistransformedinto
liquid,Theheatoftransformationforthisprocessis2260kJ/kg.Supposethemassof
thesteamism.Thetotalheatreleasedintheconversionofsteamintowaterisgivenby

Theheatreleasedwhenthesteamcoolsdownfrom100Cto50Cisgivenby

Thetotalheatreleasedbythecoolingofthesteamisthereforeequalto2470mkJ.The
totalheatrequiredis81.5kJ,andwethereforeconcludethatthemassofthesteammust
beequalto33g.

17.4. Work
Supposeasystemstartsfromaninitialstatedescribedbyapressurep i,avolume
Vi,andatemperatureTi.Thefinalstateofthesystemisdescribedbyapressurep f,a
volumeVf,andatemperatureTf. Thetransformationfromtheinitialstatetothefinal
statecanbeachievedinavarietyofways(seeforexampleFigure17.2).InFigure17.2a
bothpressureandvolumechangesimultaneously. InFigure17.2bthepressureofthe
system is first lowered while keeping the volume constant (this can for example be
achievedbycoolingthesample)andsubsequently,thevolumeisincreasedwhilekeeping
the pressure constant (this can be achieved by heating the gas while increasing the
volume).

Ifthepressureofagasincreasesitcanmoveapiston(thishappensinanengine).
Inthiscase,workisdonebythesystemastheexpandinggasliftsthepiston. Onthe
otherhand,ifweincreasetheweightofthepiston,workwillbedoneonthesystemas
thepistonfalls.TheforceexertedbythegasonthepistonisequaltopA,whereAisthe
areaofthepistonandpisthegaspressure.Ifthepistonisdisplacedbyadistanceds,the
amountofworkdonecanbecalculatedasfollows:

Figure17.2.Twopossiblewaystogetfromtheinitialstatetothefinalstate.
Thetotalworkdoneduringafinitedisplacementofthepistonisnoweasytocalculate

IfWispositive,workwasdonebythesystem(forexample,theexpandinggasliftsthe
piston).AnegativevalueofWtellsyouthatworkwasdoneonthesystem(thepistonis
presseddowninordertocompressthegas).
TheamountofworkdoneisequaltotheareaunderthecurveinthepVdiagrams
showninFigure17.2.Clearly,theamountofworkdonedependsonthepathchosen.
TheworkWforthepathshowninFigure17.2aissignificantlymorethantheworkWfor
thepathshowninFigure17.2b.Anychangeinthesysteminwhichthevolumedoesnot
changewillnotproduce/costanywork. TheworkdoneforthepathsshowninFigure
17.2canbecalculatedeasily

NoworkisdoneforthepathshowninFigure17.2bbetween(p i,Vi)and(pf,Vi)since
there is no change in volume. The work done to move from (p f, Vi) to (pf, Vf) is
calculatedeasily

Clearly,W2bisalwayslessthenW2a,andwecanmaketheamountofworkdoneassmall
oraslargeaswewant.Forexamplenoworkwouldbedoneifthetransitionfollowsthe
followingpath:
(pi,Vi)(0,Vi)(0,Vf)(pf,Vi)
Asystemcanbetakenfromagiveninitialstatetoagivenfinalstatebyaninfinite
numberofprocesses. Ingeneral,theworkWandalsotheheatQwillhavedifferent
values for each of these processes. We saythat heat and work are pathdependent
quantities.
From the previous discussion neither Q nor W represents a change in some
intrinsic properties of the system. Experimentally, however, it is observed that the
quantityQWisthesameforallprocesses.Itdependsonlyontheinitialandfinalstates
anditdoesnotmatteratwhatpathisfollowedtogetfromonetotheother.Thequantity
QWiscalledthechangeintheinternalenergyUofthesystem:
U=UfUi=QW
Thisequationiscalledthefirstlawofthermodynamics.Forsmallchangesthefirstlaw
ofthermodynamicscanberewrittenas
dU=dQdW

17.4.1. Adiabatic Processes

Ifasystemiswellinsulated,notransferofheatwilloccurbetweenitandits
environment.ThismeansthatQ=0,andthefirstlawofthermodynamicsshowsthat

U=W
Ifworkisdonebythesystem(positiveW)itsinternalenergydecreases.Conversely,if
workisdoneonthesystem(negativeW)itsinternalenergywillincrease.Forgases,the
internalenergyisrelatedtothetemperature:ahigherinternalenergymeansahigher
temperature. Adiabatic expansionof a gas will lower its temperature; adiabatic
compressionofagaswillincreaseitstemperature.

17.4.2. Constant Volume Processes

Ifthevolumeofasystemisheldconstant,thesystemcandonowork(W=0J).
Thefirstlawofthermodynamicsthenshowsthat
U=Q
Ifheatisaddedtothesystemitsinternalenergywillincrease;ifheatisremoved
fromthesystemitsinternalenergywilldecrease.

17.4.3. Cyclical Processes

Processeswhich,aftercertaininterchangesofheatandwork,arerestoredtotheir
initial state are called cyclical processes. In this case, no intrinsic properties of the
system are changed, and therefore U = 0. The first law of thermodynamics now
immediatelyyields
Q=W

17.4.4. Free Expansion

Freeexpansionisanadiabaticprocessinwhichnoworkisdoneonorbythe
system. This means thatQ = W = 0J,andthefirstlawofthermodynamics now
requiresthat
U=0J

17.5. Transfer of Heat

Thetransferofheatbetweenasystemanditsenvironmentcanoccurinavariety
ofways.Threedifferentmechanismsofheattransferwillnowbediscussed:conduction,
convection,andradiation.

17.5.1. Conduction
ConsidertheslabofmaterialshowninFigure17.3.Theleftendofthebeamis
maintainedatatemperatureTH;therightendofthebeamismaintainedatatemperature
TC.Asaresultofthetemperaturedifferenceheatwillflowthroughtheslab,fromitshot
endtoitscoldend. Experimentallyitisshownthattherateofheattransfer(Q/t)is
proportional to the crosssectional area of the slab, proportional to the temperature
difference,andinverselyproportionaltothelengthoftheslab

Here,kisthe thermalconductivity,whichisaconstantthatdependsonthetypeof
material.Largevaluesofkdefinegoodheatconductors.ThethermalresistanceRis
relatedtothethermalconductivitykinthefollowingmanner

Figure17.3.Conduction.
Thus,thelowerthethermalconductivityofthematerial,thehigherthethermalresistance
R.FromthedefinitionofRitimmediatelyfollowsthat

Consideracompositeslabismadeupoutoftwodifferentmaterials,withlengthL 1and
L2,andwiththermalconductivityk1andk2,isplacedbetweentwoheatbaths(seeFigure
17.4).SupposethatthetemperatureoftheinterfacebetweenthetwoslabsisequaltoT x.
TheamountofheatflowingfromTHtoTxisgivenby

TheamountofheatflowingfromTxtoTCisgivenby

Ofcourse,theheatflowingthroughslab1mustequaltheheatflowingthroughslab2.
Thus

Figure17.4.Heattransportthroughacompositeslab.
Thisequationcanbeusedtoobtainthetemperatureattheinterfacebetweenslab1and
slab2:

Theheatflowingthroughtheslabcannowbecalculatedeasily

Acomposite slabthereforehas athermal resistanceequaltothesumofthethermal

resistanceofeachoftheindividualslabs.

17.5.2. Convection
Heattransferbyconvectionoccurswhenafluid,suchasairorwater,isincontact
withanobjectwhosetemperatureishigherthanthetemperatureofitssurroundings.The
temperatureofthefluidincreasesand(inmostcases)thefluidexpands.Beinglessdense
thanthesurroundingcoolerfluid,itrisesbecauseofbuoyantforces. Thesurrounding
coolerfluidfallstotaketheplaceoftherisingwarmerfluidandaconvectivecirculation
issetup.

17.5.3. Radiation
Every object emits electromagnetic radiation. The energy spectrum of the
radiationemitteddependsonthetemperatureoftheobject;theaverageenergyincreases
withincreasingtemperature.
Problem57P
Acontainerofwaterhasbeenoutdoorsincoldweatheruntila5.0cmthickslab
oficehasformedonitssurface.Theairabovetheiceisat10C.Calculatetherateof
formationofice(incentimetersperhour)onthebottomsurfaceoftheiceslab.Takethe
thermalconductivityoficetobe0.0040cal/s.cm.Candthedensitytobe0.92g/cm3.
Thewaterattheboundarybetweenthewaterandtheicewillbeatatemperature
of0C.Theheattransportedthrough5cmoficeisequalto

Thisheatisreleasedwhenwateristransformedintoice.Theheatoftransformationof
thisprocessis79.5cal/g. Supposeamassmofwateristransformedeachsecondinto
ice.Thisproducesatotalheatequalto

H=79.5mcal/s
Thismustbeequaltotheheatflowthroughtheice:
79.5m=0.0080A
Amassmofice(coveringanareaA)willhaveathicknessd,wheredisgivenby

Combiningthelasttwoexpressionweobtainfortherateoficeformation: