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Chapter5

SecondLawofThermodynamics

LimitationsofFirstLaw
Consider process of water fall from a hill Cooling a cup of hot tea by surrounding air All such spontaneous processes proceed in one direction only. First law of thermodynamics does not specify direction of the process. Resulting in second law of thermodynamics

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ThermalReservoirs (Ocean,river,atmosphere,industrialfurnaceetc.) Sourceandsink Conversionofworkintoheat

HeatEngine
Devices for conversion of heat into work Receive heat from high T source Convert part of this heat to work (usually in the form of a rotating shaft) Reject remaining waste heat to a low T sink Operate on a cycle with working fluid

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SteamPowerPlant
Qin =Heatsupplied tosteam Qout =heatrejected fromsteam Wout =workdelivered inturbine Win =workrequired tocompresswaterto boilerpressure

Networkoutputfrompowerplant, Wnet =Wout Win Writingenergybalanceforpowerplantworkingona cyclemode, Wnet =Qin Qout Always,Qout 0andWnet <Qin Efficiency()=Networkoutput/Totalheatinput =Wnet /Qin =Qin Qout /Qin =1 (Qout /Qin) Efficiencyisalwayslessthanone(e.g.0.25to0.6).

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SecondLawofThermodynamics
KelvinPlankStatement It is impossible for any device that operates on a cycle to receive i heat h t from f a single i l reservoir i and d produce d an equal l amount of work. Noheatenginecanhavea thermalefficiencyof100 percent. Inpowerplant,working fluidmustexchangeheat withenvironmentas wellasthefurnace.

Refrigerator
DeviceforheattransferfromlowTtohighT Refrigerantworkinginrefrigerationcycle

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CoefficientofPerformance(COPR)
COPR= Desiredoutput/Requiredinput =QL/Wnet,in PutWnet,in =QH QL with energybalance, =QL/(QH QL) =1/(QH/QL 1) COPR maybegreaterthanone Generally,COPR =1 3

HeatPumps

Workingprinciplesimilartorefrigeratorbutwith reverseobjective

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CoefficientofPerformanceofheatpump: COPHP = Desiredoutput/Requiredinput =QH/Wnet,in =QH /(QH QL) =1/(1 QL/QH) Here,COPHP >1 MostlyCOPHP =2 3 Example:Heatengine/Refri./HP

SecondLawofThermodynamics

Clausius Statement:
It is impossible to construct a device that operates in a cycle and produces no effect other than the transfer of heat from a lower temperature body to a higher temperature body.

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EquivalenceofKelvinPlankstatementwithClausius statement: Eitherstatementcanbeusedforsecondlawofthermo.

EquivalenceofClausius statementwithKelvinPlankstatement:

Q2

Any experiment violating KelvinPlank, violates Celsius statement also and vice verse.

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ReversibleandIrreversibleProcesses:
Noheatenginehas100%efficiency. Maximumefficiencyofaheatengine? Reversible Process: A reversible process is defined as a process that can be reversed without leaving any trace on the surroundings. That is, both the system and the surroundings are returned to their initial states at the end of the reverse process. Irreversible Process Factors responsible: Friction, unrestrained expansion, mixing of two fluids, heat transfer across a finite temperature difference, electric resistance, inelastic deformation of solids, and chemical reactions.

Reversible processes actually do not occur in nature. In reversible processes, workproducing devices such as car engines and steam turbine etc. deliver the maximum work, and workconsuming devices such as compressors, fans, and pumps etc. consume the minimum work, instead of irreversible ones. The more closely we approximate a reversible process, the more work delivered by a workproducing device or the less work required by a workconsuming device. What is need to study reversible processes?

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The concept of reversible processes leads to the definition of the second law efficiency for actual processes, which is the degree of approximation to the corresponding reversible processes. The better the design, the lower the irreversibility and the higher g the secondlaw efficiency. y

CarnotCycle
SuggestedbyaFrenchengineerSadi Carnotin1824 WorksonreversiblecycleandisknownasCarnotcycle. yfluidmay ybeusedtooperate p theCarnotcycle. y Any

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Assumptions used: (i) No friction during piston movement (ii) Walls of piston and cylinder are perfect insulators. (iii) The cylinder head is so arranged that it can be a perfect heat conductor or perfect heat insulator. (iv) Working medium is a perfect gas with constant specific heat. (vi) Compression and expansion are reversible. FourstagesinaCarnotCycle: R Reversible ibl isothermal i th l (T1) expansion i with ith heat h t addition dditi Q1 Reversible adiabatic expansion from T1 to T2 (T1 > T2) Reversible isothermal (T2) compression with heat rejection Q2 Reversible adiabatic compression from T2 to T1 (T1 > T2)

PVdiagramforCarnotcycle

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Letusassume,W=workdoneincompletecycle =AreaofclosedPVcycle Foraclosedcycle,W=Q1 Q2, Now,ThermalefficiencyofCarnotcycle(th)=output/input =Workdone/Heatsuppliedbysource =(Q1 Q2)/Q1 =1 (Q2/Q1) Putvaluesofisothermalheataddition(Q1)andrejection(Q2), =1 [ RT2 ln(v4/v3)]/[RT1 ln(v2/v1)] =1 [RT2 ln(v3/v4)]/[RT1 ln(v2/v1)]..(a) Foradiabaticprocesses23and41, v2/v3 =(T2/T1)1/( 1) and v1/v4 =(T2/T1)1/( 1)

Equatingthesetwo, v2/v3 =v1/v4 v2/v1 =v3/v4 Putabovevalueinequation(a), Wehave, th =1 (T2/T1)

or

th =1 (TL/TH)

Carnotcyclecannotbeperformedinpracticebecause: a) Impossible to perform a frictionless process b) Impossible to transfer the heat without temperature potential c) Variation of motion of the piston during the same stroke is not possible. Isothermal process (piston has to move very slowly) and adiabatic process (piston has to move very fast)

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CarnotTheorem
All engines operating between a given constant temperature source and a given constant temperature sink, none has a higher efficiency than a reversible engine.

LetHEA beaheatengineandHEB beareversibleheatengine, suchthatA >B andQ1A =Q1B =Q1, Since A >B, WA/Q1 >WB/Q1, WA >WB (a)

Now,letHEB bereversed.

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ThisviolatestheKelvinPlanckstatementofthesecondlaw. HencetheassumptionthatA >B iswrongandB A

COROLLARYOFCARNOTSTHEOREM The efficiency of all reversible heat engines operating between the same temperature levels is the same. Theefficiencyofareversibleengineisindependentofthenature oramountoftheworkingsubstance undergoingthecycle. EFFICIENCYOFTHEREVERSIBLEHEATENGINE rev. =max =1 (Q2/Q1)rev =1 (T2/T1) rev. ormax <1andincreaseswithT1()andT2(). Similarly, (COPref)rev =QL /[QH QL]=TL /[TH TL] (COPHP)rev =QH /[QH QL]=TH /[TH TL]

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PerpetualMotionMachineof2nd kind(PMM2)
Without violating the first law, a machine can be imagined which would continuously absorb heat from a single thermal reservoir and would convert this heat completely into work. work The efficiency of such a machine would be 100 per cent.

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