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1824 N. L. S.

Carnot (1796~1832) q1 W q2

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Carnot cycle (Carnot cycle) (cyclic loop) (isothermal)(adiabatic) T1T2 =- wcyc / q1 = 1 T2

T1

rev irrev
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CH03 Fig3.13
Carnot Heat Engine: On one cycle the engine receives heat |q1| from the high T1 reservoir, rejects heat to the low temperature sink, and does work |w| on its surroundings.

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CH03 Fig3.14

Plot of P versus V for the working fluid in a Carnot engine. Heat |q1| is absorbed in the isothermal expansion at T1, and heat |q2| is evolved in the isothermal compression at T1. The other two steps are adiabatics.

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Carnot cycle

Step 1, isothermal reversible expansion at the Th. Step 2, reversible adiabatic expansion in which the temperature falls from Th to Tc . Step 3, isothermal reversible compression at Tc, Step 4, adiabatic reversible compression, which restores the system to its initial state at the Th.

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Carnot cycle Step 1, isothermal expansion at the Th: w1 = - nRThln(VB/VA); U1 = q1+w1 = 0 Step 2, adiabatic expansion from Th to Tc : q2 = 0; U2 = w2 = n Cv (Tc Th); Step 3, isothermal reversible compression at Tc, w3 = - nRTcln(VD/VC); U3 = q3+w3 = 0 Step 4, adiabatic compression, from Tc to Th : q4 = 0; U4 = w4 = n Cv (Th Tc); 0 = Ucyc = wcyc + qcyc; qcyc = - wcyc
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Carnot cycle qcyc = - wcyc , that is q1 + q3 = -(w1 + w2 + w3 + w4) = nRThln(VB/VA) - nCv(Tc -Th) + nRTcln(VD/VC) - nCv(Th Tc) = nRThln(VB/VA) nRTcln(VC/VD) For two adiabatic steps 2 and 4: (VC/VB) = (Th/Tc)Cv/R; (VD/VA) = (Th/Tc)Cv/R So, VC/VB = VD/VA or VC/VD = VB/VA - wcyc = q1 + q3 = nR (Th-Tc) ln(VB/VA) q1 = - w1 = nRTh ln(VB/VA) = - wcyc / q1 = (Th-Tc) /Th = 1 (Tc /Th)
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A general cycle can be divided into small Carnot cycles. The match is exact in the limit of infinitesimally small cycles. Paths cancel in the interior of the collection, and only the perimeter, an increasingly good approximation to the true cycle as the number of cycles increases, survives. Because the entropy change around every individual cycle is zero, the integral of the entropy around the perimeter is zero too.
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all

qrev = T

perimeter

qrev =0 T

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Thermodynamic Temperature
For a reversible engine working between a hot source Th and a cold sink at temperature T, then T = (1 - ) Th This expression enabled Kelvin to define the thermodynamic temperature scale in terms of the efficiency of a heat engine, a purely mechanical basis.

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-5

Suppose an energy qh (for example, 20 kJ) is supplied to the engine and qc is lost from the engine (for example, qc = -15 kJ) and discarded into the cold reservoir. The work done by the engine is equal to w=-(qh + qc); for example, -[ 20 kJ + (-15 kJ) ]= -5 kJ . The efficiency is the work done divided by the heat supplied from the hot source. = - w / qh All reversible engines have the same efficiency regardless of their construction.
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When energy leaves a cold reservoir as heat, the entropy of the reservoir decreases. When the same quantity of energy enters a hotter reservoir, the entropy increases by a smaller amount. Hence, overall there is an decrease in entropy and the process is spontaneous. Relative changes in entropy are indicated by the sizes of the arrows.

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The flow of energy as heat from a cold source to a hot sink is not spontaneous. As shown here, the entropy increase of the hot sink is smaller than the entropy DECREASE of the cold source, so there is a net decrease in entropy.
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The process becomes feasible if work is provided to add to the energy stream. Then the increase in entropy of the hot sink can be made to cancel the entropy decrease of the COLD source.

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Carnot cycle

rev irrev BAThTcTh qhTcqc qc: wB=qh-qc wA=qh-qc A B

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Suppose two reversible engines are coupled together and run between the same two reservoirs.

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Carnot cycle A > B wA > wB B A wB w = wA wB Th Tcqc-qcw=wA - wB Kelvin wA wB I R AB ThTcA , B > A. B B < A. A = B .

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The demonstration of the equivalence of the efficiencies of all reversible engines working between the same thermal reservoirs is based on the flow of energy represented in this diagram. If engine A is more efficient than engine B, not all the work that A produces is needed for B to work.
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The net result is the cold sink unchanged, hot source lost some energy |qh qh|, and work has been produced (w). The net effect of the processes is the conversion of heat into work without there being a need for a cold sink: this is contrary to the Kelvin statement of Second Law.
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The process is spontaneous if overall the entropy of the global, isolated system (the system plus its surroundings) increases, so that of the surroundings must increase in order for the process to be spontaneous, which means that energy must pass from the system to the surroundings as heat. Therefore, less work than U can be obtained.
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In this process, the entropy of the system increase; hence we can afford to lose some entropy of the surroundings. That is, some of their energy may be lost as heat to the system. This energy can be returned to them as work. Hence the work done can exceed U.

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