+ + * CHAPTER FIVE The Second Law of Thermodynamics and Power Cycle Analysis 5.1 Concepts of the Second Law as Applied to Cycles To this point chapter discussions have mostly been about energy forms, th: and transition of energy and the processes a system undergoes. It has been prese the law of conservation of mass together with energy balance analysis is used to predi change in state of a system, with such changes showing the relation in the transfer o energy in the form of heat and work or other spontaneous internal changes. It may have appeared to the student that energy forms (heat and work) are mutually interchangesbie. In this chapter, the inter-convertibility of such quantities is explored, with the purpose of determining any possible limitations and to express such limitations quantitatively. As example of such inter-convertibility, consider that a falling object heats up as It fails and hits the ground; but will the object leap up once it has cooled down to the temperature of the surroundings? Also consider, an abject pushed along a rough horizontal plane, it is evident that work is being dane on the body. All this work shows up as heat in the interface between the object and the plane. This situation clearly shows that work was converted into heat, but can the heat generated in this process be converted into an equivalent amount of work? The aforementioned examples apparently show that work can be converted into neat, but the conversion of heat into useful work may not always be possible. Although the first law states that energy must be conserved, it does not provide the necessary information to show that energy has become unavailable, which leads one to conclude that the first law is insensitive to the direction of the process. ‘The second law of thermodynamics gives a sense of direction to energy-transfer processes, and shows that energy forms are not necessarily equivalent in their ability to perform useful work. For the purpose of cycle analysis the following statements will serve to express the second law. Clausius Statement It is impossible to operate a cyclic device whose sole effect is to transfer heat from a cold body to a hot body. Kelvin-Planck Statement It is impossible to operate a cyclic device whose sole effect is the exchange of heat, with single reservoir and the production of an equal amount of work. 5.2 Cycle Analysis 5.21 Introduction A cycle is simply defined as a series of processes that a system undergoes, whereby the systems starting state is also its final state. Thermodynamic cycles contain some sort of working substance, usually in the liquid ‘or vapor phase, which flows through a device whose effect, is some sort of energy conversion, 5.22 Elements of a Cycle: (for Heat Engines or Power Cycles) > a) Working Substance ~ a fluid that undergoes several state changes; the substance used to receive and reject heat and to produce the net work output. 5-1> b) Heat Source or Heat Reservoir — the hot body from which the working substance receives heat. > ¢) Heat Sink or Heat Receiver — a cold body to which heat is rejected by the working substance, > d) Engine ~ a component of the cycle wherein the working substance performs work. 5.23 Evaluation of Cycle Performance: From the definition of a thermodynamic cycle, where the system returns to its initial state, it follows that for 2 cyclic operation there is no change in stored energy. Since a power cycle provides for the continuous conversion of heat to work, applying the first law of thermodynamics: Ein = AE surea* Eom» BU AB gee =9 << Bin = Ena Qin + Win = Qous* Wor : ie ~ Qour= Won Win Quer = Wve (5-1) To determine how effective power is being produced, one must determine how well the cycle converts heat into work. The efficiency of such a performance is dasignated as the cycle thermal efficiency, ey. where: Hr Pin = Qo _ owe (52) ‘ On Qn Qin The mean effective pressure, mep, is another parameter used to determine the net work of a cycle. On the pV diagram shown in Fig, 5-1 the net cycle work is the area enclosed by the cycle process curves, 1-2-3-4-1. This same area may be represented by a rectangle whose length is the volume displaced in one stroke of the piston, Vp, and whose height is the pressure, mep, which is the average pressure that will produce the net work of the cycle, through one stroke of the piston. 1 | ik | PA gt | ‘ “a2 | NON mop = Mat G3) t Wat KX | VD 4 i work per cycle a piston displacement per stroke <— Yo vi where :Vp =Vina ~Viie (64) 5-25.24 The Carnot Cycle, Nicholas Leonard Sadi Carnot (1796-1832) The Carnot cycle is a reversible cycle defined by two isothermal and two isentropic Drocesses. It is the most efficient cycle conceivabie, whose efficiency may be equaled but never surpassed by any other cycle, Ts isentropic processes helng reversible are adiebatic. Thus, the only energy transfer in the form of heat to the working substance occurs during tne isothermal processes. By providing a piston-cylinder arrangement (that is, applying the closed system approach), and by plotting the pV and TS diagrams (Fig. 5-2), one could end with the following equations: Pp Th Qin tw 4 1 2 | | ‘en: x StaSe S2.S3 a Fig. 52 From the T-S diagram, consider the isothermal processes 1-2 and 3-4, with the cvcle operating between the high temperature (Ty) neat source and low or cold temperature T.) heat sink. |, TdS = 1,,(8,~8,)= area 12XY¥I (5-5) uu = fra =T,(S,—S,)=-T{S,—8,)=area 43X¥4 (56) The equations presented for Q indicate whether heat is added (+) or rejected (-). However, for cycles, it is known beforehand whether heat enters or leaves as indicated by the subscripts in or out; hence the negative sign (-) for Qou is best dropped. Q ou = Ts (85-80) Qin — Que = Ts (S281) ~ Ty, (8y~84) =(Ta~T1) (S1-S1) since: S;-S;, We (7) G9)where: Tur cycle high (source) temperature T., cycle low (sink) temperature 5.25 The Stirling Cycle, Robert. ‘Stirling (1790-1878) The Stirling cycle is another reversible cycle, which has come of interest lately. ‘This Cycle offers the possibility of reaching the ideal Carnot cycle efficiency. These systems employ ait, helium or some other gas in a closed cycle. Systems operating on the Stiing Cycle receive heat from an external burner, a nuclear reactor or some other heat source, rejection of heat to a colder region is done through an appropriate heat exchanger. One Practical application of the cycle is providing heart power, where a radioisotope pile at 650°C is implanted with super insulation in the abdominal cavity, with the bloodstream acting as the cyde coolant. ‘The processes for this cycle are shown in Fig 5-3. It consists of isothermal expansion 4-2, Isometric cooling 2-3, isothermal compression 3-4, and isometric heating 4-1. P Fig. 5-3 For a Stirling cycle with perfect regeneration, the following equations hold true: W(S2-S1) 5 Qo = Te (Ss- Se) ~ Qeue= (Ta T (S2-8)) since: (S181) = (Ss~ Si) note: V;=V; and V,=V, Heat Transferred in Regenerator, V=C Qp.1= Qs-1= m6e,(Tq~T1) (5-9) 5-45.26 The Ericson Cycle, John Ericson (1803-1889) The Ericson cycle consists of two reversible constant temperature heat addition and heat rejection processes and two constant pressure processes occurring in the regenerator. The process for this cycle as shown in Fig. 5-4 includes isothermal expansion 1-2, where heat is added. The working substance is then forced through the regenerator at constant pressure 2-3. In the regenerator the working substance is then progressively cooled, with the thermal energy stored in the regenerator. In 3-4 heat is rejected isothermally causing a decrease in volume. The working substance then reenters the * regenerator, and at 4-1 all the thermal energy stored in the regenerator is transferred back to the working substance at constant pressure, 7 1% Pa=Ps Fig. 5-4 For an Ericson Cycle with perfect regeneration, the following equations apply: Qin= Ts (S2- Sd ; a= Tr (Ss Sd) Wa= On ~ Qour = (TH Te) (S2—Si) since: (S;~S) =(Ss- Sd eo ut 2 * On mep =" Vy Heat Transferred in Regenerator, p=C Q2-3= Qp se mmey (TT) (5-10) 5.27 Regeneration The use of regeneration in the Stirling and Ericson cycles causes the efficiency of these cycles to approach or equal the efficiency of a Carnot cycle, the external irreversibility between the source Ty and the sink T, temperatures is generally checked by the regenerator, where the thermal energy in the cooling process 2-3 is used to heat the substance in process 4-1. Thermodynamic cycle analysis indicates that this internal interchange of energy does improve the efficiency of the cycle. 5-55.28 Reversible Cycles Tt can.be stated that, reversible engines operating between particular temperature limits are the most efficient heat engines conceivable. Reversible cycles are those which do not result in the degradation of energy both internally and externally, For two reversible cycles operating between the same temperature limits it is evident that their thermal efficiencies would be equal, as may result from: Ty-T./ Ty, which is the highest conceivable thermal efficiency for a heat engine. 5.29 Three — Process Power Cycles A thermodynamic cycle that undergoes three types of processes is called a three- Process cycle, Such cycles have never been used, and are designed primarily for thermodynamic practice, Problem solutions for three-process power cycles are based primarily on the pV and TS diagrams. When plotting the pV and TS diagrams process curves shown of Fig. 4-1 will be most helpful. Also, it will always be true that such cycles follow a clockwise sense on both the pV and TS planes. Note that: heat is added if there is an increase in entropy for the process and rejected if the entropy decreases, work is delivered if there is an increase in volume for the process and received if there is a decrease in volume. To aid the student in analyzing such cycles, sample problems 5.9 to 5.11 are best. tudied in detail, 5.30 Comments The thermal efficiency equation for a reversible Carnot, Stirling and Ericson cycle is basically the same, since the heat addition and rejection process occurs isothermally for all three cycles. Hence, if such cycles operate between the same temperature limits their thermal efficiencies would be equal. Sometimes problems would indicate a ratio for expansion or compression; these is defined as a ratio of maximum volume divided by minimum volume for the specified process, such as; ry, fs and r,. Subscripts ts and p indicating an isothermal, an isentropic and an isobaric process, respectively. Solved Problems: 5.1 A gas for a Carnot engine receives 48 kJ of heat at 45K. Heat is rejected at 298 K with the displacement volume equal to 0.485 m? Determine a) the mep b) the net power produced if the engine makes 305 rpm. Solution: pkPaa TKA 1 L1%, 445 298: , © Qo SL Vm > SK/Kbut (53 ~S,) = (S;- $,) Qn _ Tu(S2~S,) Qae TAS: -5;) ou = 2,{ = 48 ae = 32.14kI 298 Wee = Qn ~ Qnue = (48 - 32.14)KI = 15.86 kT — Moe _ (15.8514) me eT 0.485m? = 52.7 kPa b) PWR = A(Wree )= 305 124 (15.8640 / rev pi Jes) = 60.62kW 5.2 Air is used in a Carnot cycle, the heat supplied is 75 kJ and the adiabatic ‘expansion ratio is 14:1. Determine a) the thermal efficiency; b) the heat rejected; c) the work. Solution; pkPaa 1 TK 4 ts pve ti “aefl? LP Vim SKI K 4) consider process 2-3, pV* =C Pov = PVs! 3k = 1.4; MRT, |, « _[ MRT; | —~+ Vv," =| — v, Pek eb Teh = TV," 1yvet =|4) =0.34708 4 | ~ 0.34798 = 0.65202 = 65.202% 5-765202(75 KI) = 48.9 kI (75 — 48.9) kI= 26.1 KI 5.3. A four-cylinder Carnot engine having a 90x120-mm bore and stroke operates between 420°C and 30°C. The engine rejects 20 kJ of heat to the atmosphere while running at 320 rpm. Determine a) the heat received by the engine; b) the power produced; c) the mep. Solution: p,kPaa SKK Q= Qeut 20kd = ee SA 1-e,. (0.5628) B) Whee = Qn ~ Qase = 45:75 — 20 = 25.75 KI 1 (Wee) = (320 BN 25.75 EN BRET) = 137.33 kW ©) bore — is the cylinder diameter. stroke ~ is the distance the piston travels in one direction. Vy = as (0.09m)’ (0.12m) = 3.054 x10? m? Wag. (2575OK) _ gy 574P0 Vp 3.054107 m? mep = 5-85.4 A Carnot cycle operating on 2 kg of methane, have the following properties given at the beginning of isothermal expansion; p=2070 kPaa, t=280°C. The ratio of isothermal expansion r.=1.8 and of isentropic compression . Find a) the volume and pressure at each corner of the cycle; b) the change in entropy during the isothermal process; c) the heat supplied and rejected by the cycle; d) the thermal efficiency and mean effective pressure Solution: pkPaa 2070 S,K/K a) R= 0.51845 Kiko. K = 1321 T= Ty = Ty = 280 + 273 = 553K MRT, _ 2kg(0.51845 KI / kg. KY 553K Ye Py 2070KN / m* = 0.277m? consider process1 ~ 2; pV = C Ye Va yO Vy Vy = 1.8(0.277m") = 0.499m? Pv; = Pele Y fi = p,| | = 2070kPa} 1150kPaa ne alt | Fl consider process 2-3; pv* =C % Ms 7 Ks , V, = 7.2(0.499m7) = 3.593m* pil = Ps Ps -al | - sso4rd 4] = 84.75 kaa 5-9consider process 3-4, pV = C Ma vy =18 3.5937 V, = 7227" = 1.996m? "18 = PMs = Daly De = of} = 84.75 kPaal 1.8] = 152.55kPaa / V, MR In—2 a "iy, Sz -S, = 2kg(0.51845kI / kg.K)In(t.8) = O.61kI / K b) S,-S,=me, In ©) Qn =Ty(S2 -S,)= 553K (O.61kI / K) = 337.04kI 7, Pals _(G475kN /m? (3.593? {ee ) setae 7 "mR 2ko(0.51845kT / kg.K) Que =Ti(53 - $4) = 7,(S, - S,) = 293.67K (0.61ks / K) = 179,140 F) Wroe = Qry ~ Qoue = (837.04 - 179,14)kI = 157.9kI Woe _ 157.9 = 0.4685 ~ 46.85% foe = 337.04 Wooe mep = —2. ‘D V> 5.5 Nitrogen is made to pass through a Stirling cycle. At the beginning of isothermal expansion; p=7.25 bar, V=58 L and t=320°C. The Isothermal compression ratio is 1.8 and the minimum cycle temperature is 27°C. Calculate a) AS; b) Wrets ©) Cnci_d) mep. Solution: p.kPaa 725 Vm5.6 G, = 0.7442 _ oy, 2st /m? esvh gla) “RT, (0.296864 / kg.KX593K) 0 if, mR ing = 0.239 kg(0.29686 KI / kg.K)In(L.8) = 0.04k9 / K = 0.239kg a) AS = me, In B) Wray = (Tu ~ TAS) = ( (o2- 300\K (0.04 / K) = 11.72KI TyaT _ $93 = 300 _ 9 404s - 40.41% Ty 593 oD Cg d) mep LEV, - 11,72 10 ( Mp) 252.59kPa (ayze-1 ‘An engine operating on the Stirling cycle uses air as the working fluid, The pressure and temperature at the beginning of isothermal compression are 750 kPaa and 115°C respectively. The engine has a compression ratio of 3 and a mean effective pressure of 1 Mpa. Determine a) the heat transfer to the regenerator per kg; b) the power requirement per 0.25 kg of air and an engine speed of 150 rpm: Solution: pkPaa 4 ; Vom S.KJIK Ty = Ty = 1, = 115 + 273 = 388K Vs Vs poe ZnF aE y ce G, = 0.7186 kgK R = 0.287 5412) pws = RTs __ RT, _ (O.278K / kg KY 338K Yee? Ps Z5OKN / mn? v2 =V5 1.148? / kg mep = “8. V2 “Vy Wee = V2 imp = |v, "men (0.148m° / kg\1000kN / m? Wr = Gs) = 98.6719 / kg Oo 4s =¢,nf +Rin 6 = (0.287k0 / kg.K)Inl3) = 0.31540 / kg. 1 : Wace = (Ty ~T. HAS) Woe, 98.67KI / kg 7 aE +Th= 031517 7 kg.K + 388K = 701.23K heat transfer to Regenerator; Qe-3 = Q41* Queg Qa = Gy (Ta ~ Ti) = 0.7186 KI / kg .K (701.23 ~ 368)K = 225.1KI/ kg 4) PWR = mn (Wye) = 0.25 kgl150, ) (98.67 KI / kg)(p8_N Mk.s ) = 61.67 RW 5.7 An Ericson Cycle with an isothermal compression ratio of 7.5 and an isobaric compression ratio of 3.25 operates with a cycle low pressure and temperature of 98 kPaa and 30°C. If the cycle uses air as its working substance, find a) the cycle high pressure and temperature; b) the isobaric expansion ratio; c) the cycle thermal efficiency; d) the cycle mep. Solution: kPa Di 98 Vy, ms Ti = Ta = Tr = 30 + 273 = 303 K S.kKd/KVv; Vv, tapers fon yp 73.28 4) consider process 3- 4; pV =C Pi: = DWM, Pa Pa) Z| = 98KPaa7.5) = 735 kPaa ‘s consider process 2-3; p=C,V/T =C 303K [3.25] = 994.25K ty = 984,75 — 273 =71L75°C Pu = Pai by =tz >) consider process 4-1 and 2-3,p=C W/T =C MMe. Vt Ty TT Vy 1,7, ETE — 503, Ty 984.75 O) bye =U = 0.6923 = 69.23% 4) Waa = aT X88) =] Rint Y, | = (984.75 - 303)K (0.287kI/kg.K)In 7.5. = 394,24k7 Akg © py=RT, veRE Pp — RT, _ (0.287 kd / kg.K 984.25 KYM) 2.864m3/, P> IBKN / mn Akg ). 287 | kg Kee v, = BE. 028700 / kg. \s0sK YG) | oem 4 735K / im (kg kg (tun _22424ke/ ia (M4) = 142,53kPa re Y2-Vs (2.8840, 41g)m Veg 5.8 An engine operating on the Ericson cycle has the following properties at the start of isothermal expansion; 700 kPaa, 0.13 m? and 285°C. For an Isothermal expansion ratio 5-13Or 2 and overall expansion ratio of 4, determine a) AS for the isothermal process; b) the cycle thermal efficiency; ¢) Quy Qos aNd Wyee; d) the mep for the cycle. Solution: pkPaa TK Qa 700 1 th 568 I Pe Vm? qt = Ty = 285 + 273 = 558K Te Yee % ‘a Ve _ aw, V; 2) AS = mR In = PED py ) many 7 Oy, 4s | Z00KW / m? 0.13? lm? (oe 1 eae |e 2 = O.113K/K D te=tyoh consider process 4-1; p =CVW/T=C \, TM ©) Qn = Ty(4S) = 558K (0.113KI / K) - 63,057 e. = Qn-Qae en Qaue = Qn ~ Cyc Qh = 63.05 - 0.5(63.05) = 31,525k7 Wroe = Qin — Qout = (63.05 — 31.525 = 31,525 kJ DVo = ti, = 2(0.13m") = 0.26m? 2 v= M2 026m _ 9 g6 5 m2 ‘fe 4 FL 525 KIM V,-V, (026 mep 5-14and the specific heat and gas constant of a gas mixture are Viet VG t PQs (3-31) pt + Vilp2 + Vp (3-32) =yiRy + yRs + VaR, (3-33) Table 3 -1 Gas Constants; Specific Heat Gas M ¢, c R | k Kg/mol Ka/kg.K KO/kg.K Ki/kg.K (Gof) Acetylene(C,H.) 26.036 1.6971 4.3772 0.31942 1,232 Air 28.970 1.0062 0.7186, |_0.28708 dt Ammonia(NH3) 17.032 2.0920 1.6015 0.48831 1.304 Argon(A) 39.950 0.5215, 0.3132 0.20817, 1,666 n-Butane (CyHyo), 58.120 1.6799 1.5365 0.14341 1.093 Carbon Dioxide(CO,) 44.010 | 0.8452 0.6561 | 0.18806 | 1.288 {Carbon Monoxide(CO) 28.010 1.0426 0.7454 0.29692 1.399 Chlorine(Cl,) 70.914 0.4796 0.3622 0.11728 1.324 Cyanogen(C,N,) 52.038 1.0942 0.9341 0.15984 1.172 | | Ethane(C;H,) 30.068 1.7549 1.4782 0.27658 1.187 Ethylene (C;Hs) 28.052 isa 12351 0.29649 1.240 Flourine (F2) 38.000 0.8259 0.6066 }_ 0.21888 1.36 Helium(He) 4.003 | 5.2028 3.1233 | 2.07767 | 1.666 { Hydrazine(NoHs) 32.048 1.6476 1.3834 0.25952 2.195 Hydrogen(H.) 2.016 "14.3338 | 10.2043 |~4.12552_| 1.40 | Hydrogen Peroxide(C;H») 34.016. 1.2703 1.0225 0.24450 1.239} Hydrogen Sulfide(H,S) 34.086 1.0049 0.7542 0.24396 | 1.321 | Hydroxyl(OH) 17,008 1.7650 1.2708 0.48899 | 1.383 | Mercury(Hg) 200.610 0.1039 0.0624 0.04145 | 1.666 Methane(CH;) 16.043 21377 | 1.6187 0.51845 | __ 1321 Methanol(CH<0) 32.042 1.4086 [| 1.1487 0.25957 1.226 Neon(Ne) 20.183 | 1.0313 0.6188 | 0.41210 | 1.666 Nitric Oxide(NO) 30.008 0.9969 0.7194 0.27715 1.386, Nitrogen(No) 28.016, 1.0414 0.7442 0.29686 1,399 Nitrogen Dioxide(NO,) 46.008 0.8054 0.6242 0.18078 1.29 Nitrous Oxide(NzO) 44.016 0.8791 0.6901 0.18896 1.274 i n-Octane(CsH 5) 114.224 1,6568 1.5839 0.07282 1.046 Oxygen(02) 32.000 | 0.9198 0.6595 | 0.25990 | 1.395 ‘Ozone(©,) 48.000 | 0.8192 0.6456 | “0.17327 | 1.269 Propane(CsHa) __ [44.094 | 1.6707 1.4820 | 0.18864 | 1.127 Sulfur Dioxide(SOa) 64.070 | 0.6234 0.4934 | 0.12081 1.263) Water Vapor(H,0) 18.016 1.8673 1.4053 0.46161 1.329 Xenon(xe) 131.300 0.1585 0.0952 0.06334 1,666 37