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Chapter6

Entropy

Clausius Inequality
ForaCarnotcycleorareversibleengine, Q1/Q2 =T1/T2 Q1/T1 =Q2/T2 Q1/T1 Q2/T2 = 0 =0 Q1/T1 +Q2/T2 =0 Qi /Ti =0.(a)

(useofalgebraicsum)

Now let us consider an irreversible engine which absorbs energy as heat (Q1) from a reservoir at T1 and rejects energy as heat (Q2) to a reservoir at T2. Now, irreversible < reversible or, 1 Q2/Q1 < 1 Q2/Q1 1 Q2/Q1 < 1 T2/T1 Q2/Q1 > T2/T1 Q2/T2 > Q1/T1

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Q1/T1 Q2/T2 <0 Q1/T1 +Q2/T2 <0 (usealgebric sum) Qi /Ti <0(b) Fromaboveequations(a)and(b),itcanbestatedthat, Qi /Ti 0 or (Clausius inequality) The Clausius inequality states that whenever the system undergoes a cyclic change, however complex the cycle may be (as long as it i l involves h t and work i t heat d ( l k interactions), th algebraic ti ) the l b i sum of all the heat interactions divided by the absolute temperature at which the heat interactions are taking place considered over the entire cycle is less than or equal to zero. The equality sign holds for reversible and inequality for irreversible.

Entropy
Qualitative judgement of feasibility of a process by IInd law Quantitative judgement of feasibility of a process by clausius inequality. Clausius introduced a property called entropy which stipulates feasibility of a process. Consider a reversible cycle,

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ApplyingtheClausius inequalitytoabovecycle,

dQ/ T has same value for path IA2 or 1B2, irrespective of path as long as path is reversible. So, (dQ / T)Rev is an exact differential of some function which we now identify as entropy.

Therefore,theentropyisdefinedas, S2 S1 =S So,dS (dQ/T) So, dS =(dQ/T)R forareversibleprocessonly. for a reversible process only.

Changeinentropyforairreversibleprocess=? CalculationofEntropychange?

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Entropychangeforheatinteractionwithareservoir

Suppose a certain amount of heat is added to a reservoir. Heat addition may be reversible or irreversible with contact with another reservoir or by performing work. Actual irreversible process may be replaced by an imaginary reversible path. Entropy change of the reservoir, S = (dQ/T)R = Q / T

Entropychangeforheatingorcoolingofamatter
Considerheatingofmatterbybringingitintocontactwitha bodyathighertemperature(irreversibleprocess) Replaceirreversibleprocesswithimaginaryreversibleprocess withsameinitialandfinalconditions. Heatingmaybecarriedoutatconstantpressureorconstant volumeorcombinationofboth Forconstantpressureprocess, Sp =(dQ/T)R =(dH/T)R =mCPdT/T=mCPln(T2/T1)

(IfCp isconstant)

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otherwise,IfCP =a+bT +CT2 Sp =mCPdT/T=m(a+bT +CT2)dT/T Also,forconstantvolumeprocess, SV =(dQ/T)R =(dU/T)R (dQ/T) (dU/T) =mCVdT/T=mCVln(T2/T1) otherwise,IfCV =a+bT +CT2 SV =mCVdT/T=m(a+bT +CT2)dT/T Totalentropychangeforheatingofmatteratconstant pressurefollowedbyconstantvolume, S=Sp +SV

(IfCV isconstant)

EntropychangeforPhasechange
PuresubstancephasechangeatconstantTandP. Phase change are generally at finite temperature differences Phasechangearegenerallyatfinitetemperaturedifferences (irreversible) Replacewithaimaginaryreversibleprocess Solidtoliquidentropychange=Ssf =(dQ/T)R =hsf /Tsf q py g ( Q/ ) / Liquidtogasentropychange=Sfg =(dQ/T)R =hfg /Tfg

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EntropychangeforAdiabaticmixing
Hotsubstanceisadiabaticallymixedwithacoldone. (Irreversiblesystem) Hotsubstancecoolsdownandcoldsubstanceheatup. Determinefinaltemperaturewithenergybalance Calculateentropychangeforeachsubstancewithuseof S=(dQ/T)R Totalentropychange=S=S1 +S2

Entropychangeforanidealgas
Consideranidealgasundergoesastatechangefrom(P1,v1,T1) to(P2,v2,T2). Replaceprocesswithareversiblepath(1a2or1b2etc.)

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Considerpath1a2(1a:reversibleconstantpressureheating anda2:reversibleisothermalcompression) s1a =dq/T=CPdT/T=CP ln(T2/T1) sa2 =dq/T=dw/T=Pdv/T=Rln(v2/va) Since,P2v2 =Pava =P1va So,sa2 = Rln(P2/P1) or v2/va =P1/P2

Therefore,molarentropychange,s = s1a+sa2 =CP ln(T2/T1) Rln(P2/P1) Or CV ln(T2/T1)+Rln(V2/V1)

MixingofNonidenticalidealgases
Supposearigidandinsulatedcontainerisdividedintotwo compartmentsbyapartition. Partition is removed and gases are allowed to mix Partitionisremovedandgasesareallowedtomix. Replaceactualprocesswithaimaginaryreversibleprocess

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ForgasA,entropychangeinisothermalexpansion, (S1)A =dQ/T=dW/T=PdV/T=nARdV/V =nARln(Vf/Vi)=nAR ln(P/PA)= nAR ln(PA/P) SimilarlyforgasB,(S = Similarly for gas B (S1)B = nBR ln(PB/P) Where,PA=[nA/(nA +nB)]P=XAPandPB =XBP XA andXB =molefractionsofAandBinfinalmixture HenceS1 = nAR ln(XA) nBR ln(XB)= niR ln(Xi) Also,S2 =0 l Therefore,Totalentropychangeaftermixing S =S1 +S2 = niR ln(Xi) (S>0,asXi <1) or molarentropychange= XiR ln(Xi)

PrincipleofEntropyIncrease
Considerastatechangeasfollowing, AandB:reversiblepaths C:irreversiblepath p WritingClausius inequalityfor reversiblecycle1A2B1,

AgainClausius inequalityfor1A2C1,

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Fromequation(a)and(b),wehave,

Sinceprocess2B1isreversible,replaceabovewith,

So,Wehave

Ingeneralonecanwrite, (Foraprocessofanysystem) Equalityforreversibleandinequalitysignforirreversible.

Whatisentropychangeofuniversewhenasysteminteractwith itssurroundingsandexchangesheatwithsurroundings? LetTsys andTsur =temperatures(Tsur >Tsys ) dQ =heattransfer(Irreversible) Then,dSsys =dQ/Tsys dSsur = dQ/Tsur dSuni =dSsys +dSsur =dQ/Tsys dQ/Tsur >0 Suni >0 Ifthesystemisnotinteractedwith surroundings,Then,Suni =0

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Therefore,

S>=0

(Foranisolatedsystem)

The entropy of an isolated system either increases or remains constant. The equality sign holds good when the process undergone by system is reversible; The inequality sign holds good if there is any irreversibility present in the process. This statement is called principle of entropy increase. This principle dictates the direction of a spontaneous process process. If S < 0, process is not possible.

SecondlawAnalysisofaControlVolume
Weknowthatthechangeinentropyofasystemisgivenby, dS dQ/T Thiscanbeexpressedas, S=dQ/T+SG Where SG represents entropy generation in the system such that Where,S representsentropygenerationinthesystemsuchthat SG=0forreversibleprocessandSG>0foranirreversibleprocess. Consideracontrol volume,

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Attimet,theentropyofthesystem= Attime(t+dt),theentropyofthesystem=

Then,

Thiscanalsobestatedas, [Rateofaccumulationofentropy]=[Rateofentropyinflow] [Rateofentropyoutflow]+[Rateofentropygeneration]

Steadystateflowprocesses Atsteadystateconditions,dS/dt =0, Thenaboveequationreducesto,

Foranadiabaticprocess, However,ifprocessisadiabaticandreversible, Theseprocessesareknownasisentropic.

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