Orn ess Ina cyclic process, the system returns to its intial state of , V and after doing work. since internal energy changes only when state variables change, therefore, in cyclic process [@=0]. Hence by first law of thermodynamics, [¢a=dW J. i.e,, whole of the heat supplied to the system is used up in doing work against external pressure. the area enclosed by the indicator-diagram of a cyclic process gives the work done by the Figure (a), W>0, because diagram is clockwise and hence the work is done by the system. In Figure (b), diagram is anticlockwise, so W <0 and hence work is done on the system. tl Clockwise P| Anticlockwise a) vo (bv Efficiency of a cycle Efficiency (n)of a cycle can be defined as Work doneby the working substanceduringacycle ) Heat supplied to the gas during the cylcle Creat 1a 0p _ 4 Ors 100] pa a There cannot be a cycle whose efficeincy is 100%. Hence, nis always less than 100%. Thus, Wreai * Ques x [Oa [yates mores We ings 1 Qe Thus, Qa Illustration 18: Two moles of helium gas undergo a cyclic process as shown in figure. Assuming the gas to be ideal calculate the following quantities in the process (a) the net work done (b) the net change in internal eniergy (c) the net change in heat energy (R = 8.32 /mol k) Solution : (a) Aswork done AW=[Pdv 2atn| t p Latm 300K T—> 400K So at constant pressure, AU = PIV,~ Vj] = HALT, - T] [as for ideal gas PV = RT; PV, and atconstant temperature RT, and PV, = RT.)\, 2 AW = RT log, =uRTlog, + Ca retails [as for constt. temperature, PV =constt,,ie., P.V,=PV, ie, (V/V) =(P/P.)} So work done for path AB, BC, CD and DA respectively will be AW, = URIT,- T] = 2.x R[400 - 300] = 200R AW, = URT log, (P/P,) = 2x Rx-400 log, 2 = 800R log, 2 AW,.= URIT,- 7) = 2.x R[300 - 400] =~ 200R AW,,= uRT log, (P,/P,) = 2x R x 300 log, (1/2) =- 600R log, 2 and hence, the work done in the complete cycle, AW = Wyy + Wet Wen + Woy = 200 R log, 2 = 200 x 8.32 x 0.693 = 1153! (b) As this is a cycle process, Ue u, So AU=U,-U,=0 (c) Now according to first law of thermodynamics, AQ=AU+AW So substituting the values AW and AU from parts (a) and (b) in the above, AQ=0+1153=1153) IMlustration 19. An ideal gas expands isothermally along AB and does 700 J of work. figure (i) How much heat does the gas exchange along AB? (i) The gas then expands adiabatically along 8C and does 400 J of work. When the gas returns to A along CA, if exhausts 100 J of heat to its surroundings. How much work is done on the gas along this path? Solution : (i) AB is an isothermal process. Hence, Ug =O and Qyy =Wg = 700) (i) BCs an adiabatic process. Hence, Q,,=0= W,, =400) (eiven) . Use =—Wh = ~400) ABCA is a cyclic process and internal energy is a state function, Therefore, (AU) au, ojcy =O= AUys + AUge + AU, and from first law of thermodynamics, Qay + Ope + Qe, = Wag + Wye + Wey Substituting the values, 700+ 0~ 100 = 700 + 400+ AW,,Negative sign implies that work is done on the gas. Different values in different processes. Process Qu) | wi) | AU) AB 700 | 700] 0 BC 0 | ano 400 cA | -a00 | -s00 | 400 Forcompletecycle | 600 | 600 | 0 HEAT ENGINE} Heat engine is a device which converts heat into mechanical work. Source 7, Working substance ‘heat engine absorbs heat (Q,) from a hot body, called reservoir or source, converts a part of itinto work (W and rejects the rest (0,) to a cold body, known as sink. The efficiency of a heat engine is sy Heat converted to wort, yp, oy qa x30 (1) Total heat absorbed Q = 2 oy ete a, Q, itis clear from the above expression that the efficiency of the heat engine is always less than 1 or 100%. Efficiency of Carnot engine : Carnot engine isa reversible engine which was suggested by James Sadi Carnot in an attempt to make a 100% efficient engine. Its efficiency is given by the relation x 100 (94), where T, mperature of the source and T, = temperature of the sink Itshould benoted that the efficiency of the engine depends upon the temperature of source and sink and the efficiency of two engines working between same source and sink is same * Steam Engine : Itis a heat engine which takes heat from steam and converts a part of it into mechanical motion of a piston which is then used to move heavy objects such as trains etc. It consists of a separate furnace to boil water and hence itis an external (not internal) combustion engine. is typically of the order of 3 to 10%.Internal Combustion Engine : The engines in which heat is produced in the main cylinder itself, are called internal combustion engines. Petrol engine and diesel engine are examples of internal combustion engine, The high temperature reservoir is provided by the combustion of the fuel-air mixture inside the cylinders. The low temperature reservoiris the outside air The fuel may be gasoline or petrol or diesel. The working substance is the mixture of air and burned fuel. Efficiency: f the mixture is compressed adiabatically from volume V, to V, then the efficiency Where r= 7° is called compression ratio. Clearly, greater the value ofr, more will be the efficiency, With r= 8, y= 1.4, 1 = 0.56 = 56%. This s the efficiency of a highly idealized model in which we neglect any kind of heat loss. In real practice a gasoline engine has efficiency around 20%. The value of r for a diesel engine may be 15 to 20, hence diesel engines are more efficient than gasoline engines or petrol engines. Note: Gasoline engine is also called Otto engine or petrol engine. i hey v, v, PV-diagram for an idealized PV-diagram for an idealized ‘gasoline engine diesel engine REFRIGERATORS AND HEAT PUMPS. Refrigerator Heat Pump : Refrigerator is an apparatus which takes heat from a cold body, work is done on it and the work done together with the heat absorbed is rejected to the source, Hot Reservior ]T, Working Wy substance (Cold Reserviorre “The working substance in the refrigetator is known as coolant, 8, liquid Ammonia, Freon, etc. The coefficient of performance of the refrigerator is _ The heat extracted by the refigerator from thecolé bodes in Work done on the refrigerator - B For Carnot refrigerator where T, is the temperature of source and T, isthe temperature of sink (cold bodies in the refrigerator). IF the temperature of the sink is zero kelvin, then b = 0, which is not possible. 4 Air Conditioner : It acts exactly on the principle ofa refrigerator. In this case the refrigerator box becomes.a room or an entire building, The evaporator coils are inside where they take heat from the room to make it colder and the condenser is outside where they give off heat. the coefficient of performance, Q,(heat removed) _H(heat current removed) W(work input) —-P(work input) Fora typical air conditioner, suppose heat removal rate H = 3000 W/ and the required electric power input = 1200 W 225 The actual value of b depends on the inside and outside temperatures, + Heat Pump :It also acts exactly onthe principle of refrigerator use to heat buildings by turning the refrigerator inside out. In this case evaporator coils are outside where they take heat from cold ai, and the condenser coils are inside, where they give off heat to warmer air Ilustration 20, The pV diagram of 0.2 mol ofan ideal diatomic gas used as working substance in heat engine is shown in figure. Process BC is adiabatic. The value of + for this gas is 1.4. 600 K he A 450K 300K V Ol (i) Find the pressure and volume at point A, B and C (i) Calculate AQ, AWand AUfor each of the three processes. (ii) Find the thermal efficient ofthe cycle, _(Take, 1 atm = 1.0 x 10° Ne’) Solution : (i) Given p, = p_= 1 atm = 1.01 x 105 Nev Process AB is an isochoric process.a 600 ( 5p) an) =20n. 2.02 x 10° Nm RT From ideal gas equation, V = e ©5.0x10"m? =5L nRT. (0, .2)(8.31)(455) v,=tee and P. fc 5) = 7.6 10°m? = 7.6L (1.01x10°) State pV A tatm a “8 atm SL C tatm 7a Se (i) Process AB is an isochorice process, Hence, AW,,=0, AQ,, =AU,, =nC,AT= 3 a “TW (29{?n400- azo Process BC is and adiabatic Process, Hence, 5 AU,, =nC,AT=nC, (7, -7,) = toa as ~ 600) = (022 }esueasp =-602) AW, =-AU,, = 602) Press CA isan isobrati Process, Hence, AQ, =rearar( Za, Tae (02) 7) 31)(300- 455) ~-902) & AU, =n¢,aT=A0c [1-2] YSolution: Solution : Illustration 21 : Illustration 22 : 902 =e -644) 14 2, AWy, = AQ, ~AU,, =~902)4+ 644)=-258) Process AQ{in) AW(inJ) Ulin) AB 1246 =O (1286 BCC CA 902-258 Total 34344 (i) Efficiency of the - n= ss x100= 4 ,100=27.6% [Rel 1246 An ideal refrigerator runs between -23°C and 27°C. Find the heat rejected to atmosphere for every joule of work input. Let the heat rejected to the atmosphere Q, and given W = LJ. Now Q, =Q, -W=x-1 Given, hot temperature T, = 273 +27 = 300K and cold temperature T, = 273 -23 = 250 k For an ideal refrigerator we know that, , Calculate the amount of work that must be done to freeze one gram of water at 0°C by means of an ideal refrigerator. Temperature of surrounding is 27°C. How much heat in Passed on the surroundings in this process. Latent heat of fusion L = 80 cal g*. Heat released during freezing, Q, =mL=1x80=80cal, T, =0°C =273K and 1, =27°c= 300K Oy = Since, Wa-@ 1 Q,{T,=7,) _ 80(300~273 ~. Work done, W = = ORE aie Tl" 2B => Heat pased to the surrounding, Q, =Q, + W=(80+ 7.91) =87.9icalStudent Task Las Qt Q2 Q3 a4 Qs Q6. A-system undergoes a cyclic process in which it absorbs Q,, heat and gives out (, heat. The efficiency of the process is Nand work done is W. Select the correct statemet. ll org (¢] Both (a) and (b) are correct, (4) Both (a) and (b) are wrong An ideal heat engine is opening between 227°C and 127°C . It absobs 10°) amount of heat at the higher temperature. The amount of heat converted into work is. {a} 20005 (b) 4000) (c) 8000 J (d) 5600 J The inside and outside temperatue of a refrigerator are 273 K and 303 K respectively. Assuming that refrigerator cycle is reversible for every joule of work done the heat delivered to the sur- rounding will be (a)104 (b) 20) (c)30) (a)50) Heat energy absorbed by a system in going through a cyclic process shown in figure is ——> Vin litre 1 30 ——> pinkPa (a) 10" (b) 10x (¢) 10° (4) 10° Ina cyclic process shown in the figure, an ideal gas is adiabatically taken from B to A, the work done on the gas during the process 8» A is 30 J, when the gas is taken from A» Bthe heat absorbed by the gas is 20 J. The change in internal energy of the gas in the gas A Bis. (a) 201 (b) 30 (0) 50J (a) 101 An ideal gas is taken through a cyclic thermodynamic process through four steps. The amounts of heat involved in these stepsare Q,, =59601,0 = -5585),0, =2980) and involved are W, = 2200, W, =-825 J, W, =-1100 J and W, respectively. What is the efficiency of the cycle (a)10.82% (b) 11.42% (0) 9.32% — (d) 5.82%Q7 _ Athermodynamic cycle on an ideal gas is shown in the V-T graph. Which of the following P-T graph Tepresents the same cycle Qs {a) Net work done is positive (b) The change in internal energy is zero (c)_ The work done is — FR -RI—M) (d) The work done is x(P, ~ P,) 1.(b) 2a) 3. (a) 4(c) 5.(b) 6(a) 7. (d)_8. (b) SECOND LAW OF THERMODYNAMICS} This is a law of nature which decides, whether a given process, allowed by the first law, will actually ‘take place or not. This law may be stated in various ways. The first law denies the possibility of creating or destroying energy ; the second law limits the availability of energy and ways in which it can be used and converted. The second law is not a deduction from the first but stands by itself as a separate law of nature. ‘The second law implies that no heat engine can have efficiency equal to 1 or no refrigerator can have coefficient of performance equal to infinity (i.e, W= 0) The statements of two forms of the second law of thermodynamics are given below. (i) Kelvin-Planck statement : “It is impossible for a self acting device, unaided by an external agency and acting in a cycle, to absorb heat from the source and convert whole of it into work”. In short, “there is no perfect engine”. (li) Clausius statement : “It is impossible to construct a machine which can transfer heat from a cold body to a hot body over a cycle without the help of any external agency. In short, “there is no perfect refrigerator’.REVERSIBLE AND IRREVERSIBLE PROCESSES Reversible Process ; A thermodynamic process is reversible if the process can be turned back such that the system passes through the same statesis reverse sequence. That is, the reverse is represented by the same curve as direct process (ito f), with the arrow inverted. Pp v A process can be reversible only if it satisfies two conditions, (a) It must be quasi-static (b) It must be non dissipative ice, friction, viscosity etc should be completely absent. All processs described in thermodynamics are assumed to be reversible un! less stated otherwise, Since actual processes are not eqasi-static, therefore, a reversible process is an idealization that can never be attained in the real world. Irreversible Processes : Those processes which are not reversible, are called irreversible processess, Thermodynamic processes that occur in nature are all irreversible processes. Such process can be turned back but the system does not pass through all the states of the direct process in reverse order. Heat flow through finite temperature drop is an irreversible process, CARNOTENGINE This acts on the principle described below. Carnot Cycle : It consists of two reversible isothermal and two reversible adiabatic processes. Q ‘av isotherm isotherm Vv Figure shows a Carnot cycle using as its working substance an ideal gas ina cylinder with a piston. It consists of the following steps : (i) The gas expands isothermally at temperature T, absorbing heat Q, (ab) (i) Itexpands adiabatically until temperature drops to T, (be) (i) It is compressed isothermally at T, rejecting heat Q, (cd) UW) Itis compressed adiabatically back to its inital state at temperature T, (da) y ¥, 2 y Here Q, = W,, = nRT, log, , -Q, = W., = nT, log, v= 7RT, log, 7 log, = Ai) <From adiabatic relation, Tv/"'=7,V" and TV; \ We get wo .. from (i), ae, «efficiency n = Carnot’s Theorem : “All reversible engines operating between the same two temperatures have equal efficiency and no engine operating between the same two temperatures can have an efficiency greater than this". Itisa consequence of the second law of thermodynamics. Remember that the maximum theoretical possible efficiency of a heat engine is 1 Although, this formula for h has been derived by using an ideal gas as its working substance, itis in fact valid for any Carnot engine, no matter what the working substance is. Similarly, it may be stated that “no refrigerator has a greater coefficient of performance than a Carnot refrigerator operating between the same two temperatures”. Entropy : Like pressure, volume, temperature, internal energy, etc. We have another thermodynamic variable of a system, named entropy. Itis related to the disorder of molecular motion of the system. Greater the randomness or disorder, greater is the entropy. The change in entropy 7 _Heat absorbedby thesystem _ AQ. ee Absolute temperature TThis realtion is also called mathematical form of second law of thermodynamics. Sl unit of As is J/K and dimensional formula is (MLT kK") Note : |we always define change in entropy rather than its absolute value. 4 Change in entropy for solids and liquids : (i) When heat is supplied to a solid and its state changes such that temperature remains constant, then Change in entropy. AS= 8 #-8. 7 Positive sign is used for heat absorption and negative sign is used for heat rejection, {i) When temperature ofa substance changes from T, to, then fat q) (1, =msin| 2 |. Ui ! T (sam mS t,(¢ > where, m = Mass of the substance = Specific heat of the substance llustration 23: Entropy of an ideal gas incerase with temperature on shown in the figure. Find the heat absorbed by the gas 200k |" 100 cal/k Solution AQ =[Tds = area under T-S graph = 5200+ 300)(50) = 500 x 25 = 12500 cal = 125 kcal Illustration 24: 200 gram of ice at 0°C is converted into water vapour at 100°C. Evaluate the change in entropy, Solution : Consider conversion of ice into water ice—>water orc orc Change in entropy during the conversionMlustration 25: Solution : Illustration 26: Solution : AQ_ml,. _200%80 | 2B Again consider rise of temperature of water from 0°C to 100°C. =58.6cal /k water —water Ore 100°c Change in entropy for this increase in temperature of the water J, (373 AS, =ms,hft 200x1sh| $7) = 200 In (1.4) cal/k water —>vapour Again consider conversion of water to vapour iqqe— 190°C change in entropy for this conservation is, AQ_ Mbp _200%540 Net change is entropy AS=AS, +45, +5, =58.6 + 200 In(i.4)+289.5 = 348.1 + 200 x 2.303 log,,(1.4) = 415.4 cal/k One ofthe most efficient engines ever developed operated between 2100 Kand 700K. Its actual efficiency is 40%, What percentage of its maximum possible efficiency is this? Here T,=2100Kand 7, =700K t-z AS, = 289.5¢al/K = 66.6% Given, Maca = 7 40 The % of maximum efficiency = “x10 = —x100~60% Thx 66.6 The efficiency of a Carnot cycles 1/6. Ifone reducing the temperature of the sink by 65°C, the efficiency becomes 1/3, ind the initial and final temperature between which the cycle is working IFT, and T, are the temperatures of source and sink respectively, then (ii) 3 Solving equations (i) and (ii), we get T,=390 k and T, = 325KIllustration 27; Solution : IMlustration 28: Solution : ACarnot engine whose heat sink is at 27°C has an. efficiency of 40%, By how many degrees should the temperature ofthe source be changed to increase the efficiency by 10% of the original efficiency? Here, T, = 273 + 27 = 300K - Weknow that =1-— 00 or 04=1-300 ; or, = 500K Increase in efficiency of engine = 10% of 40 = 4% Thus new efficiency of the engine becomes = 40 + 4 = 44% Let T," is the new temperature of the source, then oa4=1-2 Increase in temperature of the source =T,'=T,=535.7-500 =35.7K Two Carnot engines A and B operated in series, The first one A receives heat at 800 K and rejects toa reservoir at temperature TK. The second engine B receives the heat rejected by the first engine and in turn rejects toa heat reservoir at 300 K, Calcualte the temperature TK for the following cases : (i) When the outputs of the two engines are equal (ii) When the efficiencies of the two engines are equal For engine A: T, = 800 K and T, = Tk Qa 1 7, 800 Efficiency of the engine ‘We know that, =v thEfficiency of the engine Since the engine B absorbs the heat rejected by the engine A. So Q’ = Q, Now equation (i) becomes 300 w.-0(1-*F) (iv) Case (i) When outputs of the two engines are equal W,=W, ebshal-s| 800, T or After solving, we get, T= 550 K Case (ii) When the efficiencies are equal n= or 1-— 800 After solving, we get T= 489.9 K llustration 29: A mass of air is initially at 260°C and 700 KP, and occupies 0.028 m*. The air is expanded at constant pressure to 0,084 m’, A polytropic process with p = 1.5 is then carried our followed by a constant temperature process which completes a cycle. All the processes are reversible, Sketch the cycle in the PV diagram. Find (a) the heat required, (b) the heat rejected in the cycle, and (c] the efficiency of the cycle. (C, = 0.718 kl/kgk, R,, = 0.287 Ki/ kekSolution : The complete cycle is shown in figure. For m kg of the air we can write PY, _700%0.028 = = = 0.128 kg ie RT, 0.287533 A B ACA: PyFsk P,=700kPa V, = 0.028 m* PV = constant Ty 273 + 260 = 533K AtB P, = 700 kPa(As process isobaric from A to 8) V,= 0.084 m* Te? By equation of state Py _ Poe pope hs AC: As process CAs isothermal, so T,= 533K Vie vy, In the process Bto C, PVs = By equation of state, TY gg Pi | =k ry P) Pi Thus we have oe a) For the processA-»B: C,=C, y= m6, (T,— =137.43kI For the process B > C: and AU=U,-U,= mCJT,-T,) Q,,= AU+ W,. =mCJT_-T,)+mR,R, =m(T.- nfs -4] 0. zm] = 0.128 [533 - 1599] [one 2227 15-1 128 x (-1066) x 0.144 19.654) For process C-> A:T, 0, 2. AU=U,-U,=0 W,,= mR, Tyln A=mr, Tine Ye ia 2, = 0.128 x 0.287 x 533 x uo =) =- 64.53 k) (a) Heat received in the cycle, Q,, = 137.13kl (b) Heat rejected in the cyle, Q=19.59 + 64.53 = 54.12 KI (c) The efficiency of the cycle, Q 84.12 Tan 7g 7 03907 39% : : Illustration 30: Figure shows the variation in the internal energy U with the volume V of 2.0 mole of an ideal gas in a cyclic process abcda. The temperature of the gas at b and c are 500 K and 300 K respectively. Calculate the heat absorbed by the gas during the process. Solution : As AU=0, .. AT=0 or Tconstant w= [Pav aRT Wehave PV=nRT > cae 4 dv yy, He | Osh =nkT|inv| =nkTinwv, Weg =ARTyln—* = 28 x 500 fn = 1000 Rin? h and Tin 20 =28«300in = =-600REn2 2, 2 There is no volume changes from b to cand from d to a, so The work done in complete cycle W=W,,+W,+W+W,, = 1000 R /n2 +0-600R fn2 +0 = 400 8 (nd From first law of thermodynamics Q=AU+W =0+400R ind = 400 R fn2 Student Task Qt Q2 Q3 Q4 Ans: An ideal gas heat engine operates in a Carnot cycle between 227°C and 127°C. It absorbed 6.0.x 10 cal at the higher temperature. The amount of heat converted into work is equal to (a) 4.8% 10% cal (b)3.5x 10% calc) 1.6 x 10%cal (d) 1.2.x 10* cal Acarnot engine takes in 3000 kcal of heat from a reservoic at 627°C and gives it toa sink at 27°C. The work done by the engine is (a)4.2x 108) —(b)8.4x 10°) (c) 168x10°s (d) Zero For which combination of temperatures the efficiency of carnot's engine is highest? (a)80K,60K (b)100K,80K (c) 60k,40k (d) 40K, 20K Entropy of a system is related with (a) discorder of molecular motion of the system (b) volume of the system {c) pressure of the system (d) none of these 1.(b) 2a) 3. (4) 4. (a)