Second Law of Thermo- dynamics: Entropy 7.1 Conversion of heat into work and its converse When two pieces of stones are rubbed together say under water, the work done against friction gets converted into internal energy that tends to increase the temperature of the stones. As the temperature tends to rise above that of the surrounding water, there is a heat flow info the water. If the amount of water is too large or if it is flowing continually, there will hardly be any rise in its temperature. It then acts as a heat reservoir. In the process of rubbing, the initial state of the stones is the same as that at the end of the process which only converts the mechanical work into heat. In a like manner, if an electric current is maintained in a resistor placed under fiowing water or water of very large mass, the electric work done will get transformed into heat and there will be no change in the thermodynamic state of the wire of the resistor. There could be other examples as well. : 267268 THERMAL PHYSICS In general, work of any kind W may be done upon a system in contact with a heat reservoir giving rise to a flow of heat Q, with no change in the state of the system which simply functions as an intermediary. The first law of thermodynamics dictates that [w=a] Thus, the entity work can be converted completely into heat and further it can be continued indefinitely. The next question that arises is extremely significant : Is the converse also true? To answer it, we must first have a process or a series thereof, for such a conversion to continue indefinitely without any change in the state of any system. It appears, at first sight; that an isothermal expansion of an ideal gas could be an appropriate process for the conversion of heat into work. As the temperature is constant in an isothermal process, there is no change in internal energy, and so from the first law if thermodynamics, Q = W, implying that heat could as well be converted completely into work. But the process involves a change of state of the gas: the volume increases, the pressure decreases, and as-the atmospheric pressure is reached, the process also gets halted. So it involves a change in the state of the system and also cannot be continued indefinitely. 7.2 Heat engines In the light of the above, what is needed for a continuous conversion of heat into work is a series of processes by which a system would be brought back to its initial state, that is, a cycle. In a cycle, each of the processes may involve a flow of heat into or from the system, and the performance of work by or upon it. Let, in a cycle, @1 = amount of heat absorbed by the system, Q2 = amount of heat rejected by it, and W = net work performed by the system. If Q1 > Qe (Q1, Q2 are defined as pbsitive numbers), and if W is work done by the system, then the mechanical device that causes the system to undergo the cyclical change is called a heat engine, schematically shown in Fig. 7.1. We thus define a heat engine as a system operating in a cyclic process that converts heat into work. Its sole purpose is to deliver work continuously to outside by performing the same cycle repeatedly. The system used is called the working substance, the net work done in the cycle is known as the output of the engine and the heat : absorbed by the working substance is the input. 2, Te owoaliy dia ‘Thermal efficiency — The thermal efficiency 1 of a heat m engine engine is defined as the ratio of the net work done (work output)chapter » Second Law of Thermodynamics: Entropy 269 to the net heat absorbed (heat inpui) during one complete cycle of the heat engine. Work output ‘Heat input Since, on completion of a cycle, the working substance returns to its original state, there is no change in its internal energy. That is, AU = 0. From the first law of thermodynamics applied to a complete cycle, therefore, U = (Qi -Q2)-W=0 > W=A-% (7.2.2) where Q: and Qo are respectively the heat absorbed and rejected, and W the work done per cycle. : ~W_Q-%_,_ & Thermal efficiency, n = mee 1-3, (7.2.3) "ae Q using (7.2.1) and (7.2.2), Expressed in percentage, Qa =(1-%) x 100 1.2.4 n% (2 2) x] (7.2.4) The relation (7.2.3) indicates that the efficiency 7 will always be less than unity. Why? Is it due to irreversibility of the thermal processes? However, it is desirable to device a heat engine that would deliver mazimum possible efficiency. To understand how this could be done, we should consider such questions as: (i) under what conditions should a heat engine operate? (ii) has the working substance to play any role in it? It was the work of Sadi Carnot who for the first time conceived an idealised engine — the Carnot engine — and solved the problem of maximum attainable thermal efficiency by a heat erigine. He recognised that for mazimum efficiency, a heat engine should be thermodynamically reversible. The simplest reversible cycle is due to Carnot. We shall discuss, in the following section, the matter in greater details. 7.3 Carnot’s cycle : its efficiency ‘The essential parts of the idealised Carnot engine are the following. 1. A source (or heat reservoir) of heat of infinite capacity at some constant temperature Tj, from which heat is absorbed. Absorption of heat from it does not decrease its temperature. 2. A sink (or a similar heat reservoir) at some lower constant temperature Th, to which heat is rejected. Rejection of heat to it does not increase its temperature. 3. A cylinder of perfectly insulated walls but of perfectly conducting bottom, filled with a frictionless non-conducting piston. 4. A working substance ~ an ideal gas, say ~ enclosed in the cylinder by the piston, 5. A perfectly insulating pad or stand for the cylinder.270 THERMAL PHYSICS Operations — This hypothetical engine, never to be realised in practice, operates in eycles; each cycle consists of four stages shown schematically in Fig. 7.2. To simulate the working of the engine, we consider the following reversible sequence. Step 1. The working substance undergoes .a reversible isothermal expansion represented on the indicator or p-V diagram (Fig.7.2) by AB which is an isotherm at temperature T,, The substance expands from a volume Va to a volume Vz. The heat absorbed from the source in this step is Q; and the work done is Wi. Step 2. In this step, the working substance undergoes a reversible adiabatic expansion from the volume Vp to Vo, represented by the adiabat BC on the indicator diagram, resulting t in the drop of temperature from Ty,‘ to that of the sink, T(T, > Tp). During the process Q = 0 and the work ‘done is Wo. Step 3. In this, the working substance is com- pressed reversibly and isothermally at temperature Ty from volume Ve to volume Vp. It is represented by the isotherm CD. The compression generates heat Qo which is rejected to the sink so that the : , ake: ie uizitly ioothetmal, (The work dete is Ws, Fig 7-2 Carnot’s cycle on _Which is negative since work is done upon the gas. a p-V diagram "Step 4. This is the last step to get the cycle completed and consists in an adiabatic and reversible compression of the working substance from volume Vp to Va, temperature increasing from Tp to T;. The working substance is thus restored to the initial condition and becomes ready to resume the next cycle. In this step, Q = 0 and the work done is W4, which is negative since it is done on the gas. The adiabat DA represents the step. . Va Yo Ve Vo v—> If all the changes are quasistatic, and if there is no friction, then and then only the cycle is reversible. © The Carnot cycle consists of two isotherms and two adiabats and they alternate each other. Since the cycle is reversible, it may start from D to run as DCBAD. © An innovation of paramount importance in the operation of Carnot engine is the concept of reversibility. At one stroke, it eliminates the complications arising out of friction, turbulence, acceleration, heat conduction, radiation etc. from the discussion, These factors reduce the efficiency of heat engines so that the maximum attainable efficiency is that of Carnot. We shall be back to this point while discussing Carnot’s theorem. Calculation of efficiency — The net effect of the cycle is that we have extracted heat Q) at T; and rejected heat Q2 at T:. In the process the total work done W is given by W= SOW = Wit Wot Wet Ws