Entropy and the Second and Third Laws of Thermodynamics Problem numbers in italics indicate thatthe solution is included in the Student Solutions Manual. Conceptual Problems Qs 2 asa ass 056 ‘Under what conditions is AS <0 fora spontaneous process? For a spontaneous process, AS+ ASueraange > 0. A process is spontaneous if AS <0 only if >|as}. ASrromaings > 0 and |ASyrouning WE AS sg Ad ASyrorsaton Always positive? son on ‘This is the case because AH joy 84 A Fypoyznion 80 always positive, In each of these transitions, attractive forces must be overcome. In both ofthese process, the disorder in the system inereases, ‘An ideal gas in thermal contact with the surroundings is cooled in an irreversible process at constant pressure. Are AS, ASyrrpundngss 80d AS Positive, negative, or 20? Explain your reasoning, 1 For const peste poses AS= HCpy aE and if AT <0,AS <0, For a proces that i Acta 0coms, AS > -THEt I, MSaemanti > 0. ‘The amplitude of a pendulum consisting of a mass on a long wit lly adjusted to have a very small value. The amplitude is found to decrease slowly with time. Is this process reversible? Would the process be reversible ifthe amplitude did not decrease with time? No, because dissipative forces (inthis case friction) are acting on the system, If the emplitude did not decrease, no dispersive forces act on the system and the oscillation is reversible in the limit of very small amplitudes. Ifthe amplitude did not decrease with time, no dissipative forces act on the system, and because the amplitude is very small, the process is reversible. ‘A process involving an ideal gas is cartied out in which the temperature changes at constant volume. Fora fixed value of A7, the mass of the gas is doubled. The process is repeated with the same initial ‘mass and AT’ is doubled. For which ofthese processes is AS’ greater? Why? AS is greater if the mass is doubled, because AS increases linearly with the amount of material. By contrast, S only increases as the logarithm of the temperature. This increase is much slower than a linear increase, ‘You ate told that AS = 0 for a process in which the system is coupled to its surroundings. Can you ‘conclude that the process is reversible? Justify your answer, 'No. The criterion for reversibility is AS + ASyumsundngs = O- To decide if this criterion is satisfied, AScurcundings must be known, 73 Copysight ©2013 Pearson Edtcaton, ne,74 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 987 ass 959 95:10 Q5.12 Qs.13 Q5.14 ‘Under what conditions does the equality AS = AH/T hold? oy Aromat, the equality holds if Adpmerbie = AH. This isthe case for a reversible process at Because dS ‘constant pressure, Is the following statement true of false? If itis false, rephrase it so that i is true. The entropy of a system cannot inoease in an adiabatic process, False. The entropy of a system cannot incease in a reversible adiabatic process, ‘Which of the following processes is spontaneous? &. The reversible isothermal expansion of an ideal gas. b. The vaporization of superheated water at 102°C and 1 bar. ¢ The constant pressure melting of ice at its normal freezing point by the addition of an infinitesimal quantity of heat 4. The adiabatic expansion ofa gas into a vacuum, @) is not spontaneous because the system and surroundings are in equilibrium during a reversible process. (©) is spontaneous because the equilibrium phase under the stated conditions isa gas, (©) isnot spontencous because the process is reversible ifthe amount is infinitesimal. (@ is spontaneous because at equilibrium, the density ofa gas is uniform throughout its container, One joule of work is done on a system, raising its temperature by one degree centigrade, Can this increase in ‘temperature be hammessed to do one joule of work? Explait 1No, because it would violate the second law of thermodynamics. Heat cannot be converted to work with 100% efficiency. ‘Your roommate decides to cool the kitchen by opening the refrigerator. Will this strategy work? Explain your reasoning. 1t will not work if the reftigerator is totally inside the room because cooling the room would require that the refrigerator takes up more energy than it releases. Becauso the efficiency ofthe refigerator i less than 100%, the net effect wil be to heat the room. However, if the refigerator is mounted in a window or door so thatthe heat is not released into the room, it is possible to cool the room in this way, ‘An deal gas undergoes an adiabatic expansion into a vacuum, Are AS, ASprnindnge» 04 AS xq postive nogatve, or zero? Explain your reasoning, y, = ion int = nk nL 7 Because AT = 0 forthe expansion of an idedl gas into a vasmum, AS = A In~L-> 0, Because ASrming 8 calculated using the actual heat flow into the surroundings, ASyroundings =0 for an adiabatic process. Sut = AS + ASpurcuntngs > 0: When a saturated solution of a salt is cooled, a precipitate crystallizes out. Is the entropy of the crystalline precipitate greater or less than the dissolved solute? Explain why this process is spontaneous. Forming the crystalline precipitate isa process for which AS < 0. However, ASyrrunngy 18 opposite in sign and ‘greater in magnitude so that AS + AS ureuméings > 0, making the process spontaneous. A gystem undergoes a change from one state to another along two different pathways, one of which is reversible ‘and the other of which is imeversible, What can you say about the relative magnitudes of Grneniie and roversibie? Because $ is a state function, AS’ is the same for a reversible and an irreversible path between the same initial and final states, However, a8 discussed in Section 5.6, AGrnneue -Aaq = TaS ~ di > 0. Copyright © 2013 Pearson Education, IncChapter 5 Entropy and the Second and Third Laws of Thermodynamics 15 QS.5 An idea! gas in a piston and cylinder assembly with adiabstic walls undergoes an expansion against a constant external pressure. Are AS, ASwurcundingy> ad ASiey positive, negative, or zero? Explain your reasoning. Because the process is adibatic, ASprmdngs = AS = Swat ~ ASerrmings 45 > 0. Because the process actually occurs, ASjyq) > 0. Because Q5A6 Is the equation , Y oe arg 18, TB Gar. (Lav =o, nits By, -y; J Far + J x ee”) valid fran ideal gas? ‘No. Because # and x are not independent of ¥ for an ideal gas, they can’t be taken out of the integral. Q5:17 Why is the efficiency of a Camot heat engine the upper bound to the efficiency ofan internal combustion engine? ‘This is the case because the maximum work that can be done on the surroundings inthe expansion of a gas isin a reversible process, Q5.18 Two vessels of equal volume, pressure, and temperature both containing Ar are connected by a valve. What is the change in entropy when the valve is opened, allowing mixing of the two volumes? Is AS the same if one of the volumes contained Ar, and the other contained Ne? If the same gas is on either side of the valve, AS = 0 because the individual atoms or molecules of the gas are indistinguishable. Howover, ifthe two gases are different, AS > 0 because of the mixing of the gases. 5.19 Without using equations, explain why AS fora li asboth P and change. It is useful to think of S = S(¥,7). Because V changes very litle with P for a liquid ot soli, entropy changes are dominated by changes in T rather than P for liquids and solids, uid or solid is dominated by the temperature dependence of S (520 Solid methanol in thermal contact with the surroundings is reversibly melted at the normal melting point at a pressure of I alin. ATC AS, ASyereundngy AX Sig) postive, negative, or zero? Explain your reasoning. SE fusion As = El > 0; Because the process is reversible, ASgy = 0. Q521 Can incandescent ightng be regarded as an example of cogeneration during the heating season? In a season where sir conditioning is required? It can be regarded as an exemple of cogeneration during the heating season because the waste heat from light production is used to heat the building, It isnot an example of cogeneration if air conditioning is used because the ‘waste heat reduces the effect ofthe airconditioning. Numerical Problems 5.1 Consider the formation of glucose from carbon dioxide and water, that i, the reaction of the photosynthetic process: 6C03(g) + 6H0(1) ~> Celi;20g(s) + 60,(2). ‘The following table of information will be useful in working this problem: T= 298K 60x) HOM Celhn06(s) 0416) ‘AH; a mot") 3935 “2858 =12731 00 891 molK"!) 2138 70.0 209.2 205.2 Cp Smol1K) 374 183 2192 294 Copyright © 2013 Pearson Edsetion, ne.16 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics Calculate the entropy and enthalpy changes for this chemical system at T= 298K and T = 310K. Caloulate also the entropy change of the surroundings and the universe t both temperatures, assuming that the system and surroundings are at the same temperature. At 298.15K, ASf = 209.2 1K mol"! + 6 205.25K™ mol" ~ 6 x 213.8) K“ mol” ~ 6 x 70.01 K™ mot AH = 1273.1 kd mol"! ~ 6% 393.5 ki mot — 6 285.8 kI mot = 2803 kJ mol! 9.4010 K™ mot! 240 x10? JK molt Sinners = ASeurcuntings + 4Sj = ~262.4 1K" mor — = -9.66 10? 1K mort To calculate AS for the system, the surroundings, and the universe at T= [310.K, we must take the heat ‘capacities into account. AG, ‘pm = 62941 K! mol! + 219.23 K mol — 637.1 K" mol — 6% 75.3) K mol 2788) K"! mot! 310.K 5(310.K) = AS yp ne ASR(BIO.K) = AS{(298.15K) + AC,» ln SO 310.K = 273.4157 mot 298.15K eee = 262.4 K mol" ~ 2788 K mot x ln AH{(G10.K) = AH4(298.15K) + AC, AT = 2802.7} mol"! ~ 278.8% 10" kI K~! mot" x (310.~ 298.15)K_ = 27994 mot"! Ae “AH (310.K) _ -2793.8 mol urodngs T 310K 903x109 1K“! mor! 273.41 mot ~ 9.03 x10? SK mot AScniverse = MSturcandinge + SS 230% 10? K+ mor P52 The Chalk Point, Maryland, generating station supplies electrical power to the Washington, D.C., ares. Units 1 and 2 have a gross generating capacity of 710. MW (megawatt). The steam pressure is 25%10°Pa, and the superheater outlet temperature (Ty) is 540.°C, The condensate temperature (T,) is 30.0°C, 4. What s the efficiency of a reversible Camot engine operating under these conditions? b, Ifthe efficiency of the boiler is 91.2%, the overall efficiency of the turbine, which includes the Camot ‘efficiency and its mechanical efficiency, is 46.7%, and the efficiency of the generator is 98.4%, what isthe efficiency ofthe total generating unit? (Another 5.0% needs to be subtracted for other plant losses.) © One of the coal burning units produces 355 MW. How many metric tons (Imetricton = 1%10° g) of coal per hour are required to operate this unit at is peak output if the enthalpy of combustion of coal is 29.010? KS kg"? @ e (b) The efficiency of the generating plant isthe product ofthe individual efficiencies. & = 0.912 0.467 x 0.984 x 0.95 = 0.398 ‘Copyright ©2013 Pearson Edvcaton, In.Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 71 36005 (©) The energy output per hour is given by 355 MW x: =1278% 10 Ihe. 1.278%10 the? 5 ‘The heat required ro ouput this energy is g = =. a 3211x109 She 12 yet ‘The numberof tons of coal needed is 22LLXIT IB = 140.7 on ne“, 29.010" J ton PS3 An electrical motor is used to operate a Carnot reffigerator with an interior temperature of 0.00°C. Liquid water at 0,00°C js placed into the reftigerator and transformed to ioe at 0.00°C. Ifthe room temperature is 300.K, what ‘mass of ice can be produced in one day by a 0.50-hp motor that is running continuously? Assume that the refrigerator is perfectly insulated and operates atthe maximum theoretical efficiency. ‘We need to find the amount of heat per unit time that can be removed from the interior of the reftigerator, 4 (2) Tea =) 0 TE) Toe Toa 273.15K, 300K -273.15K 46W 0.50 hp x: 6046 W = 6046554 ‘The number of grams of ice that can be frozen in one day by this amount of heat extraction is git, 604638 “BH futon 6008 S mol PSA An air conditioner isa reftigertor with the inside ofthe house acting asthe cold reserve and the ouside atmosphere acting asthe ot reservoir. Assume that nar condtoner consumes 1.70% 108 W of lecial powes, ‘and that it can be idealized as a reversible Carnot reftigerator. If the coefficient of performance of this device is 3.30, how much eat can be extracted from the hous in a ay? ny, = Tid. = 3.30; dogg = 3.300 do = 330170510? Lx 2EEOS 24 br = 48531083 PSS ‘One mole of H,0(/) is compressed from a state described by P = 1.00 bar and 7 = 350.K to a state described by P = $90, barand 7 = 750.K, In addition, 6 = 2.07%10~ K", and the density canbe assumed tobe constant at the value 997 kg m“°, Calculate AS for this transformation, assuming that x = 0. From Equation (5.24), % % ¢ 1 as lFe- jree = Cry in mB -F) y¢ 180210 kg mol Amol: OT kgm mol 753 mol 1K x In 750.K _ 350, 207 x10 Kx $89 bar x 10° Pa bar! = S7AIK7 ~ 0.22017 = 5721 K+ P5.6 2,25 moles of an ideal gas with Cy,,, = 3/2 R undergoes the transformations described in the following list from an intial state described by 7 = 310.K. end P = 1.00 bar, Calculate g,, AU,AH, and AS for each process. 8. The gas isheated to 675K ata constant extemal pressure of 1.00 bar, (Copyright © 2013 Pearson Bévcation, Ic,78 PS7 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics b. ‘The gas is heated to 675 K at a constant volume corresponding tothe initial volume. © The gas undergoes a reversible isothermal expansion at 310.K. until the pressure is one third of ts intial value, (@) The gas is heated to 675 K at a constant pressure of 1.00 bar. nig 4, = MRD, = 228 mol AS14 01K XHIOK 946-2? B 10° Pa F ¥, = Ly, = SBE x 540x107 m= 0.125 m? 7, 0x W = Parapet AV = “10° Pa x (0126m — 580% 10°? m*) = 6.83 x10° 3 x mot Kt AU = rpg AT = 225 mol ESI 3684 a 2,104 = AH = AU ~w = 102x10°54683%10° = 17.1x10°3 1, 3 14g 613K AS = nC pq nL = 2.25 molx $1)csai4 smart tcte = 36454 a G 310 (®) Tho gar is heated to 675K at a constant volume corresponding to the inital volume. w= 0 because av =0. 3x 8.3143 mol K7 AU = 4 = ny = 2.25 mab AMEN BOT 5654 102,10 1 AH = nCp AT = 225 malx SESE ET 5 565 = 1713108 7 Vic cece = iL = 2.5 2)xa. mol K~! x in = 21 ot 8 nygi = aecda( 2) std na IE a0 (©) The gas undergoes a reversible isothermal expansion at 310.K until the pressure is one third ofits intial value, AU = AH = 0 because AT = 0, ¥, mnt in Lo 225 mol 83145 mol KX 310.K xIn3 = 637 10°F 2, y =nRin-£ + nC, nL nan + ney 2smote totes aa ac 22smaa(S tts =2065K" Consider the reversible Camot eyele shown in Figure 5.2 with 1.25 mol of an ideal gas with Cy = $/2as the ‘working substance, The initial isothermal expansion occurs atthe hot reservoir temperature of Thy, = 740.K from an initial volume of 3.75 L (F,) to a volume of 12.81 (V;). The system then undergoes an adiabatic expansion Until the temperature fills to. Tag = 310.K. The system then undergoes an isothermal compression and a subsequent adiabatic compression until the inital state described by 7, = 740.K and V = 3.751 is reached, @ — Caloulate ¥, and Vy. (Copytight © 2013 Pearson Education, IcChapter 5 Entropy and the Second and Third Laws of Thermodynamics 79 bb. Calculate w for each step in the cycle and for the total cycle, % 1 lye pl28Le Way = -MRT, In “2. = 1.25 mot mot Kx nS ab ART ng 8314) a Me = Malle ~Th) = 125 mol «2.5%8314 J mol! Kx G10.K ~740,K) = 11.2% 1091 % hcg 33OL Mag = -MRTe INGE = 1.25 mol x 8314 Jmol! K x nISE = 3.96310" J Mae = "Cra Pa ~Ta) Wyott = ~9.44X 107 F-11210? J+ 3.96 x 107 F 411210? J = 5.49% 10°F ©. Caleulate ¢ and the amount of heat that is extracted from the hot reservoir to do 1.00 kJ of work in the surroundings, L7S mol x5» 8314 J mot" Kx (740.K ~ 310.K) = +112% 10° 5 10.K w HOK woset g=%= 740.K ar PS.8 The average heat evolved by the oxidation of foodstuffs in an average adult per hour per kilogram of body weight {is 7.2010 kg” hr"!, Assume the weight of an average adult is 62.0 kg. Suppose the total heat evolved by this ‘oxidation is transferred into the surroundings over a period lasting one week. Calculate the entropy change of the surroundings associated with this heat transfer. Assume the surroundings are at T= 293K. (per day, 62.0 kg) = 7.20 kg"! te“! x 24h day“! x 7 day week" x 62.0 kg 4.6% 10" kd week"! seit day Ag = 4 = MEXIA day = 956 43 Kt week"! 295K P59 Calculate AS, ASigeh a8 ASrrromaigs When the volume of 150.g of CO intially at 273K and 1.00 bar increases by a factor of two in (a) an adiabatic reversible expansion, (b) an expansion against Paayyy =, snd (©) an isothermal reversible expansion. Take Cp» t0 be consant atthe value 29.14,3 nol" K~! and assume ideal 403 bohavie. State whether each process is spontaneous. The temperature of the surroundings is 273 K. 8. Anatiabatic reversible expansion ASwyounings = 0 because q = 0. AS = }. The process isnot spontaneous. . Therefore AU = ‘because the process is reversible. Svat = 4S + AS recundigs = b. Anexpansion against Patemal = y, AS = nt In-L = 0-8 59.3144 mot! K> xin? = 309K" ¥, ~ 2801gmor 1 AT and w= 90.9 JK"! + 0 = 30.9 JK“, The process is spontaneous. Sut = AS + ASwerundags & —Anisothermal reversible expansion AT = 0, Therefore AU = 0. eenrt nth. 150.8 ES mol «8.314 mot! Kx 273 K « In 2 = 8.43 x 10? ¥) 2dtgmar™ ’ trate MOIS apg yt 8 T 2BK sis 9 _ 843x105 1 KIEL nok Samoans =F = ASixat = AS + AS, = 30.91 ~ 30.91 K = 0, The system and surroundings ae at equilibrium, otal Suro Copyright ©2013 Pearson Education, ine80 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics P5.10 The maximum theoretical efficiency of an intemal combustion engine is achieved in a reversible Camot eycle. Assume that the engine is operating in the Otto cycle and thet Cy, = 5/2R for the fuel-air mixture initlly at 273K (the temperature ofthe cold reservoir). The mixture is compressed by a factor of 69 in the adiabtic compression step ‘What is the maximum theoretical efficiency ofthis engine? How much would the efficiency increase ifthe compression ratio could be increased t 15? Do you see a probem in doing 20? ‘It would be difficult to avoid ignition of the fuel-air mixture before the compression was complete, PS11 2.25 moles of an ideal gas with Cy» = 5/2 is transformed from an initial state T = 680,K and P = 115 bar toc final state 7 = 298.K and P = 475 bar. Calculate AU, AH, and AS for this process. 5x8314 mol K 2 oe TXBSI4J mor AU = nCy AT = 2.25 mol x % (298K ~ 680.K) = 17.910" AH = np, AT = 225 mol > (298 K ~ 680.K) = 25.0% 10° 3 as Py Ty ~nRin=L + Cp y nL 7 1 MCPanln ot yyy 47S bat 7x8314J mor! K | 298K = 2.25 mol x 8314 J mol K~ x In + 2.25 mol x SSI T mor in 28K e “INT [Sbar 2 OK 265 1K ~ 403K =-8053K7 P5.12 1.10 moles of Np st 205°C and 6.20 bar undergoes a transformation to the state described by 215°C and 175 bar, Calculate AS if Ci Tmol K7 : : = mnat-usrea0 4 2399610 1016082 x ® x , » % AS = ne nL n [Pm ar Ao T = =110 mol x 83143 mol K7 x In ma . : + -d—JK~ 293.65 K = 163K 4/3081 In — 0.011872 4. 1.1984% 102 - 033921092 ret K K Ee K, Laee 1.6JK"4172IK7 — 2.547 + 2,00 K* (Copyright ©2013 Pearson Education Ine,Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 81 PS13 —Caleulate AS for the isothermal compression of 1.7Smol of Cu(s) from 2.15 bar to 1250.bar at 298K. B= 042x104 K, = 0.7810 bar”, and the density is 892 g cm”, Repeat the calculation assuming that x = 0, as =-ff'y0—aoypar 1.250" 63.55 x10 kg mol? ‘isni0* 89210 kgm 0765.1 Kt (= 0.78010" Pa“! x P)0.492x 10 K“laP Repeating the calculation for x= 0, we sce no change because 1 xP. 2PS.14 Calculate AS* for the reaction 3Hf(g) + Na(#) —> 2NHa(z) at 725K. Omit terms in the temperature-dependent heat capacities higher than 7/K?. From Table 2.4, Cla g) = 72065 4 438x107 Losss.c10 st mort - Chay g) = 3081~ 1187 107 F 4 239689109 3K ar CpONH, g) = 2929 + 1.103 x10 © ods 3K mot La 5 TO aca 4 ~|3081- 1.187 x10 22 + 2.3968 x10 3K! mor prime 40.21 — sors sane JK mol Soa s(NHs. 8) ~ Sigg.is(Nav 8) ~ 389g 15(Has 8) = 219285 K"! mot! ~191.6 5K mol ~ 3130.73 Kt mol 198.1) K7 mot T acy Sous J Par’ 40.21 - 0.0975 Ki } r 198.1) 7! mol! + d= 3K mot K avis 198.13 K mot! ~ 31.345 mot" ~ 41,62) K mol” + 84.28 1K mot? 191.2]. K mol Wsi8 Ung te expsin = Ear Ya, es doa i tempt tnt 1225 mks ‘water at 310, K and 1650. bar is brought to a final pressure of 1.30 bar in a reversible adiabatic process. Assume that x Copyright © 2013 Pearson auction, Ie,82 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics as = Dar -ypap As = [as = cpin Zk pce, —n) Because the process is reversible and adiabatic, AS = 0. 1, Vile, ~ A) + Cplnf, Cohn = vary — A) — tnt = VBR P+ Cola 7, Gp 18.02 x 107 kg 998 kg 2.04% LOK (1,30 x 10° Pe 55x10" Pa) + 75.3K7 mol x in3: 783K" mot = 5.72851 307K 25K ar PS.16 3.75 moles of an ideal gas with Cy, = 3/2.R undergoes the transformations described in the following list from ‘an initial state described by T = 298K and P = 450 bar. Calculate g, w, AU, AH, and AS for each process. 8 The gas undergoes a reversible adiabatic expansion until the final pressure is one third its initial value, £4)" -(2) (ey: (J- ay) 1% (a TO q Fy q Fy. TP, 2 298K x 3.0075 =192K ES ‘mol “a 3 =n gt = 29S mat BMH ae 98%) = 496%103 5x83145 mol K"! ; X (92K ~ 298K) = 8.26% 10°F ICpgAT = 3.75 mol x AS = 0 because drreritte = 0. b. ‘The gas undergoes an adiabatic expansion against a constant external pressure of 1.50 bar until the final pressure is one third its initia value. q = 0 because the process is adiabatic, Cy + 15383145 mor! Kt 4 83143 mol ET Ls bar — 298K x 4.50 bar Tepe ‘sxasiajmort et, 8314Imol Kx 150 bar Cont 15% 83145 mor! K+ 4 83143 mot KTx150 bar % 1.500 bar (Copyright © 2013 Pearson Edeaton Inc.Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 83 3x 8314S mol" K 2 5x8314 1 mol K’ 2 AU = 0 = 16) gh =3.15molx x (2185K ~298K) = -3.72%10° AM = nCpyAT = 3.15 mol x % (218.5K ~298K) = ~6.19 «108 J 2 y As =-ntla + npg nL i q = 375 molx8314 mot! Kx in 450M. + 3.75 mol SX8314 2m 450 bar 101K =343K7 425K" ©. The gas undergoes an expansion against a constant external pressure of zero bar until the final pressure is equal to one third ofits initial value. AT and w = 0. Therefore AU = AH =0 and g = AU ~w =0. As =3431K7 »; aR nt = 3.75 mol x 8.3141 molt K™ x In 150 bar P 45 0 bar PS.17 The interior ofa reftigerator is typically held at 36°F and the interior ofa freezer is typically held at 0.00°R. If the room temperature is 65°F, by what factor is it more expensive to extract the same amount of heat from the freczer than from the refrigerator? Assume that the theoretical limit forthe performance of a reversible refrigerator is valid in this case, From Equation (5.44) np Ta MT Tae Toa Tron = $(65—32) 4273.15 = 291.5K 3 Tpeene = 5 (0.00 ~ 32) + 273.15 = 2554K : 5 Tapiantr = 535 ~ 32) +273.15 = 2754K 2554K freezer n, = —— 2554 K__ Pocthe fees ty = S615 — 2554K 275.4K For the reftigerator 9, = See = ‘The freezer is more expensive to operate than the refrigerator by the ratio 17/7.1 = 4, PS.18 Using your results from Problem P5.7, calculate g, AU, and AH for each step in the cycle and for the total eycle described in Figure 5.2 ab AU = AH = 0 because AT =0 44x10°F be AU =w~=~1.12%10") because ¢ AM = AU + nRAT = -15.6%105 cd AU =AH=0 because AP = q=-w=-396x10 5 da AU =w=1.12%108) because ¢ =0 AH = AH + nRAT =15.6x10°3 ut = 944X109 5~3.96%10? = 549 10° 5 =~ pay AU pat = AH at = 9 Copyeight © 2013 Pearson Eduction, Ic.84 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics S19 _Attho anti temperature of 954°C, the enthalpy of transition from rhombic to monocins sulfur is 0.38 kJ mot! 2 Caloulate the entropy of transition under these conditions. b. At ts melting point, 119°C, the enthalpy of fusion of monoclinic sulfur is 1.23) mol", Celoulafe the entropy of fusion. ©. The values given in parts (2) and (b) are for 1 mol of sulfur; however, in crystalline and liquid sulfur, the molecule is present as S,. Convert te valves of the enthalpy and entropy of fusion in parts (a) and (b) to those appropriate for 5. 038 kI mor @ emer = 1.01K mort o 73.15 +954) K oi o = 3.1457 mort 273.15 +11) K (©) Each ofthe AS in parts (a) and (b) should be multiplied by 8. ASrenstion = 824.1K7 mol AS xin = 25.1 K“Imot P520 One mole of a van der Waals gas at 25.0°C is expanded isothermally and reversibly from an initial volume of 010m? to a final volume of 0.095m°, For the van der Waals gas, (3U/a/)p = ai¥2, Assume that 2 =0.556Pam® mol, and that b = 64.0%10" m? mot. Caleulateq, w, AU, AF, and AS forthe process. au (2) aw dw), Fora van der Waals gas AU = nol 1-1) gs shown in Example Problem 3.5 HV. 1 p-aphy) twa? = 971 doiOaF Oise ay = 0586740 mt 0.095 m? ~ 64> 10-* m? = mol 8.314 3 mol Kx 298,15 nS — 4210 (0.010 m? = 64x10 m serum mor4{— ty iat bone 595x107 J + 49.755 = 5.55% 10° J = RT _ ra _ 1molx8314 Imo! Kx 298.15K _1mol? x0556Pam® mol? ‘W-b W 0.010 m> ~ 64x10 m> 0.010m? = 244105 Pa ART _ ra _ 1molx 83143 mol” Kx 298.15K Sp pay pk to ae ¥-b WF 0.095 — 64x10 2.60104 Pa Copyright© 2013 Peuson Edveatcn, Ine.Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 85 AH = AU + A(PV) = AU + Py ~ BY, = 49.7 J + (2.60 x 10* Pa x 0,095 m? ~ 2.44 10% Pa x 0.010 m*) = 79.7 q=AU~w 9.75 +555x10° J =5.59x 10°F . = Seema, _ 859210) ae Tr 298.15K F521 From the following data, derive the absolute entropy of crystalline glycine at T= 300.K, You can perform the integration numerically using either a spreadsheet program or a curve-fiting routine and a graphing calculator (see Example Problem 5.9). Temperature(K) —_Cp(IK mol) 10. 03 20. 24 30, 70 40. 13.0 0. 25.1 80. 352 100. 2 120, 50.0 40, 560 160. 616 180. 670 200. no 20, 74 240, 28 260, 884 50 100 150 200 250 300 Temperature (K) ‘Copyright © 2013 Peeron Education Ine,86 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics ‘The line in the graph above of Cp, (Vertical axis) against is the best fit to the data of a polynomial of the form a+ be + ex? + de? given by ~9.4109 + 0.67903 x 0.0019301 x7 + 2.93185%10-* x, 300.0 K 9.4109 +- 0.679037 ~ 0.00193017? + 2.93188 x 10-7? ina eee eee = 104.537 mol (300.K) = We have integrated from 10 K rather than 0 K because the integrand is not well defined at O K and because the ‘contribution to $ below 10 K is very small. F522 Calculate AH and AS ifthe temperature of 1.75 moles of H(?) is increased from 0.00°C to 75.00°C at 1 bar, (Over this temperature range, Cp, = 30.093 ~ 4.94610 7 J mol" K>, Ai 7st fone 454i Sat! Mar .75 x (30.093(348.15 K — 273.15 K) ~ 2.472 x 102(348.15 K — 273.15 K)") J = 3.75x10°F 348.18 30,093 ~ 4.944 x 107 Jmot KT asta pri srr 211K 1, 75 x (sou 10°; 1) + 30.085 LIK 7523 Calulte AS ifthe temperate of 2.50 mol of an ideal gas with Cy = 5/2 is inceased fom 160.0 675K ‘under conditions of (a) constant pressure and (b) constant volume. a. at constant pressure Map nl = 2s0molx($+1) 8314 smot" xn EK i 1osiK+ 160.K as bat constant volume y, 5 os = nCy pla L = 2.50 mol x 2x 8314S mot! Kx In OK = 74g3K4 AS = nC pln f= 250 molx5 x8314 Tak P5.24 Beginning with Equation (5.5), use Equation (5.6) to eliminate ¥, and V, to arrive at the result Woes = MRT ~ Tet) IOV vy =a Wee = RCy (Tes ~The) Va naga nt Wea Was = ®CY Troe ~ Toot Tra = ToauaVf* and Teta¥E = Tha J Tua 2 ea Solving the last two equations for Tjcy and equating the results, wy yet Trot = Ty ve Toe = Tent atl ‘Therefore, Kekagkuk Ye Va Va Va ‘Copyright © 2013 Pearson Education, Ine,Chapter § Entropy and the Second and Third Laws of Thermodynamics 87 nd h % %, oy, ART yy WL — ART ayig 9 = —AR (Ty ~ yin ad = Tig A n= nh TG PS25 — Caleulaie AS, for the reaction Hy(g)+Cl,(g) > 2HCI(g) at 870. K. Omit terms in the ‘temperature- dependent heat capacities higher than 7*/K2, From Table 2.4, Cia, g) = 22.66 + 438% wEa1 0835 x wT K7 mort oT Pt matt = 22.85 + 6.54310? — 1.2517 x10 2, 3K mol K Kw ‘ soar 412.102 6a0sict04 atm K K? 2 [2s rso0s102f-ramsnio* Zito) rR wast 104 Zr mot - (2285+ seo" ace 2 aut 0.117 + 2.460% 10° 23+ mor K ro as Sea is(HICL, 8) ~ Stag s(Cly #) ~ Sioa a(t, 8) = 2x 186.9IK“ mol ~ 223,15 K mol! — 130.77 K" mol” = 20.05 K+? molt 7 4 ACS oe AS = AStonis + f “SP ar ans 2 op [tett-onrrg + 240ox10* Fe mt) i mort UK mort = 20.05K" mol oils F ag Ft mot x © 20.0 3K“! mol! + 15.113 K? mol ~ 66.91 K mol + 82.16 K! mol"! = 50.15 K"! mot! P526 A 22.0 g mass of ice at 273 K is added to 136 g of H,0(/) at 310 K at constant pressure, Is the final state of the system ice or liquid water? Calculate AS’ for the process. Is the process spontancous? ‘Assume initially that the final state is water. If this is not the case, the calculated temperature will be below 273 K, Calculate AS for the ice and water separately, and add them to get the overall AS forthe process. Mea ion * MCPs Up ~ T+ My oC PUT, ~ 1!) = 0 Mein TE + Mn oC PT? ~ Me sy _ T, neh + Mao sp Teta 78311 al 278 K+ OED 95.3 mo 1802 gicemot™ Fata g HO mer 310K —— 208 6010 mar iat ge mot 220 B88 5675.31 mot! +36 8HI0 7535 Kot! 18.02 g ice mol! 18,02 g H,0 mol 1, = 204K Copyright ©2013 Pearson Eduction, ine.88 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics AS Is calculated forthe ice. It consists of melting the ice at 273 K and heating the resulting water to 336 K. at 1 as = Allan npg aL Tyaion Tyson 0, hence the process is spontaneous. 5.27 Under anaerobic conditions, glucose is broken down in muscle tissue to frm lactic acid acording to the reaction: Clly0¢(s) > 2CH;CHOHCOOH(s). Thermodynamic data at 7 = 298 K for glucose and lati ac are given below, AH;0Smor) | Cp0K mor) | SOK mor) | Glucose(s) 1273.1 219.2 209.2 | Lactic Acid(s) 673.6 1276 192.1 Calculate AS for the system, the surroundings, and the universe at T = 325.K. Assume the heat capacities are constant between 7 = 298K and I’ = 330.K. At 298.15 = 2192.1 9K mot ~ 209.25 K mor = 175.0 K“ mor Alf = -2x 673.6 KI mol"! +1273.1kJ mol = ~74.2 kI mo ‘To calculate AS for the system, the surroundings, and the universe at T= 325K, we must take the heat capacities into account AC yyy = 2%127.6 5K mol 219.21 K7 mol! = 36.0) KY mot 325K ASRG25K) = AS$(298.15K) + AC, y In HGS K) = ASK D+ AC so8 ISK ati ot paar toe ig 325K = 175.05" mol" +36.01 K7 mot x 326 = 175K"! mot 0 Kot mot xn mot AHB25 K) = AH3(298.15K) + AC, AT = 74.1 kd mol! + 36.0 x10" kd K+! mol » 26.85 K = ~73,1k mot ~AHRGIO.K) _ 731k molt _ aaa Storming = AEG) = BAK MO 8 9955" pot ASinat = ASyunoantrgs + Si = 225K"! mol +175.1K"! mol = 400.9 K"! mo! 5.28 The amino acid glycine dimerizes to form the dipeptide glyeylalycine according to the reaction 2Glycinels) > Glyeylalycine(s) + H,00) Caleulate AS, ASyyomdngss 84 Syne A T = 298K. Useful thermodynamic data follow: Giycine Giyeyieiyeine Water [aa (ed mor “3372 =1460 ~285a SSK mar) 1035 1900 700 Copyright ©2013 Pearson Héveaton Tne.Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 89 -2x103.53K"! mot + 190.0]. K mot + 70.0 9K“ mol"! = 53.0 K~ mor 12.6 kJ mot Asp Alf = 2% 537.210 mol"! ~ 74643 mot"! ~ 285.81 mot"! it cal _ 42.61 mot faromings = = See 9K ASjoyqy = 142.95 K mol! + 53.0 K™ mol™ 143K mor 90.03 K mot PS29 One mole of H,0(/) is supercooled to ~3.75°C. at 1 bar pressure, The freezing temperature of water at this pressure is 0.00°C, The ransformation #10() ~> H,0(s) is suddenly observed to occur. By calculating AS, A Snemendys and ASigals vetify that this transformation is spontaneous at -3.75°C. The heat capacities are "piven by Com(Hz0(0) = 7531K mot and Cp q(l120(8)) = 377K mol, and AH pxog = 6.008 KI mol! at 000°C. Assume that the suroundings are at -3.75°C. (Hint. Consider the two pathways at 1 bar: (© H,O(, ~ 315°C) -> H,0(s, ~375°C) and (b) H,0(,-3.75°C) > H,0(I, 0.00°C) > H,0(s, 0.00°C) -> H0(3,-3.75°C). Because Sisa state function, AS’ must be the same for both pathways.) For pathway (b) HO, ~3.75%C) > H,O(, 000°C) > H,0(s, 000°C) -+ H,0(s, -375°C). 2BAsk AH, 26940K . — nA A tat 6 Cp (sn 22K a MnO 40K "TASK ‘en 273.15 K 1 gg TSK, 6008 J mol = tol 753 mol"! Kx In = 1 mol x 5008 L201 busee ec 269.40 K na 27B.1SK 26940 +1 mol x37.7 J mol" Kx in ne 2BASK = 10410 K! ~ 22.00 1K"! - 0.521 5K = ~21.48)K To caleulate ASyrpundngrs We first calculate Ap = g. AH(-3.75°C) = AH(0.00°C) + (Cp(solid) — Cp liquid) AT AH(-3.75°C) = 1 mol x{-6008 J mol + (37.73 mol! K — 753 J mol K7}) x (-3.75 K)] = -5867) = g i -4 58673 Somomares ~ 7. * 769.40 Taeroudings 21785 K+ ASiqat = 21.781 K ~ 21485 K' = 0.305 K™ > 0, The process is spontaneous. PS30 —Caloulale AS, ASyeraamtng 804 ASynpone er day for the ait condtioned house described in Problem 54, “Assume that the interior temperature is 65°F and the exterior temperature is 99°F. 32.0, 70.0, and 104 degrees Fahrenheit corespond 100, 21.1, nd 40.6 deprees Centigrade, respectively. duty = power X te = 330%1.70 10 35-4 «3600 $524 he day"! = 4,853 10° J 1 Set = ae ber) = caine 1 e ( 85x10? 8 = Hal = ASS 166x100 Samanta fh = SPILT aap KI AS + AS pangs = 1.66% 10° JK + 2.03 x108 1K = 3.723108 1K P31 Thefllovng et apy aa have eon repre for alee: it io Pa] | | am, | awe [vo [ an [0 amo [ en [C*nm GK mar") | 0.49 | 3.85 | 1745 | 30.99 | 42.59 | 52.50 | 68.93 | 83.14 | 96.14 | 109.6] 120.7 (Copyright © 2013 Pearson Education, Ic.90 532 5.33 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics By a graphical treatment, obtain the molar entropy of L-alanine at” = 300,K. You can perform the integration numerically using either a spread sheet program ora curve-fiting routine and a graphing caleulator (see Example Problem 5.9). ‘Tho data is graphed below with the heat capacity and temperature on the vertical and horizontal axes, respectively, ‘The best fit to the data has the form Coy = 960+ 0.77617 ~0.00198172 + 0.0000027647° 120 100 |- 80 60, Heat capacity/J K-! mort & 20) oo 50 100 150 200 250 300 ‘Temperature/K To obtain the entropy at 300. K, we evaluate the integral 2 2 son xy = 210 077617 900195 + comouzrEAT” 2 T = [0.77617 ~0.00097567? + 9.21310" 79 9.160 LogtrIReE = 131.13 mor kK We have neglected the contribution to S from temperatures below 10. K asthe data isnot available. This contribution is very small Calculate ASyromiings 824 ASiya fr the processes described in parts (a) and (b) of Problem PS.16. Which of the Processes is a spontaneous process? The state of the surroundings for each part is at 298 K, 1.50 bar ASuuvondinge = 0 for (a) and (b) because Sat = AS + ASprendnge = +0 =0. The process is not spontaneous, b. Sioa = AS + AS, 10.1 K+ 0 = 10.1. K“, The process is spontaneous. ot ‘recs A refrigerator is operated by a 0.25-hp (I hp = 746 watts) motor. Ifthe interior isto be maintained at 4.50°C and the room temperature is 38°C, what is the maximum heat leak (in watts) that can be tolerated? Assume that the ‘coefficient of performance is 50.% ofthe maximum theoretical value. What happens if the leak is greater than yout calculated maximum value? ‘The coeflicient of performance is $00 x —Teald__ = 0.500 277.65, TSK gag Thor Trott 31L1SK -277.65K CCopytight © 2013 Pearson Eéveston, neChapter Entropy and the Second and Third Laws of Thermodynamics 91 ‘The maximum heat that can be removed from the cold reservoir is given by 46 hp [Ifthe heat leak is greater than this value, the temperature inthe reftigerator will rise. Input power x coefficient of performance .25 hp x 4.14 = 723 W = 77355" P534 Using your results from Problems PS.18 and P57, calculate AS, ASprruning id AS for each step in the cyole and forthe total Camot cycle described in Figure 5.2. 9.44% 10°F a As, = Sema = SMO Sy g yt e ° AS = AS progr = “i Say k Saat = 0 bre AS = AS prramings = 0 BECASE Grenier =O Seu = 0 965108 J eod = Levrnrble - BOX ogy yt = > 4S = ~Synings = 20 ae Sea = 0 doa AS = ~ASprrantegs = 9 BECBISE Imrie = 0 Sui = 0 Forthe cycle, AS = ASywreimings = ASyaat = O- P5.35 Between 0°C and 100°C, the heat capacity of Hg(/) is given by Com(Hay D) IK mot 30.093 - 4944109 K Caloulate A and AS if2.25 moles of Ha) is aised in temperature from 0.00° to 88,0°C at constant P, sos AH =n f Crmd[TIK] wis = 2.25 mol x 30.093 x (361.15 ~ 273.18) - 2472x107 (361.15* ~ 273.182) mot"! = 565x103 28 =n eed (rik] aan | age x = 2.25 molx [soos ni aur to ass ~ma)p K+ mor! =1791K" P536 Calculate ASyreuniingr 814 AS for part (0) of Problem P5.6, 1s the process spontaneous? The state of the surroundings is T = 310.K, P = 0.333 bar. ‘The gas undergoes a reversible isothermal expansion at 310. K until the pressure is one third ofits initial value. y we <4 aR WEL = 295 ol x A916 al KT 310K xIn3 = 637 105 637x108 J rt Sree POET ao ssax a 310.K 2 1, 3 = -mkInZL+ nC py in aah =20551K7 Spot = AS + ASiuroundigs = 20.55 JK - 2055) K™ = 0 ‘There is no natural direction of change in this process because it is reversible, Copyright © 2013 Pearson Education, Ine.92 Chapter § Entropy and the Second and Third Laws of Thermodynamics PS37 —Caleulate the entropy of one mole of water vapor at 175°C and 0,625 bar using the information in the data tables. 2 78°C, 0625b) = S7Q98.15K)~ akIneL + npn = Limol x188.8JK~! mol" — 1 mol 83145 K7 mot! in 2-625 bar 448.15 K 298.15K + 1mol x33,581K" mol" x la = 206K P5.38 The heat capacity of a-quartz is given by Py sox r = 46.94 43431x109 2, 694 + 3431x109 ‘The coefficient of thermal expansion is piven by = 0.3530% 10" K™ and V = 22.6.0m* mot, Celeulate AS, forthe transformation a-quartz (15.0°C, latm) > @-quartz (420.°C, 925 atm). From Equations (5.23) and (5,24) 455 = [Con -VaKr, 2) i 4694+341x10°2—113x104(Z) sn3s| 46.94 + 34. K K F ype et ae IK mol" — VAR, ~ A) 2s re 693.15K 3 [46x neg tA SEXIO «(603.18 28818)] -5.65x10° x (693.15? ~ 288.1%) ° 5 = 220m mote 50.3530 10° Ki 92 a x HOESHIOY Pe io Sm = 41.20 K7 mol! + 13,896 K+ mol — 22.4551 K+ mot”) — 0.0746 7K"! mol? = 32.63 K7 mol 539s, Calculate AS if 1.00 mol of lguid water is hented from 0.00°C to 10.0% under constant pressure it Cy = 753K" mol, b, The melting point of water at the pressure of interest is 0.00% and the enthalpy of fusion is 6.010kJ mol”. The boiling point is 100.°C and the enthalpy ‘of vaporization is 40.65 kJ mol”. Calculate AS forthe transformation H1,0(s, 0.00°C) ~> H,0(g 100.20). (@) The heat inputs the same fora reversible and an ieversble process. = dapreie = MC py AT y AS = nf-2@ ar = nCpqinL Finan noah rt ycel p 283ISR = Lmolx 75.33 mol! Kin 2831S " Wisk 2niK7 5 an, > 60101 mol" pio, = Mtl = sl x60101 I 99 9994 Treen 273K AH, ‘mol 40680. mot"! “1 dn = Sopra, = 108.947 Si neeaeatel naa S7RISK ASiouat = ASjusion + SSyaporscton + ASheing = (22.00 + 108.94 + 2.71) JK" = 133.655 K7 tat = AS asin + AS por a Copyright © 2013 Pearson Bduestin, Ic,Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 93 Ps40 PAL S42 21.05 g of steam at 373 K is added to 415 g of H,O(0) at 298 K at a constant pressure of | bar. Is the final state of the system steam or liquid water? Calculate AS forthe process. ‘Assume that the final state is liquid water. If this is not the case, the calculated temperature will be greater than 373 K. ~amtsHforcaten + Masonry Ty ~T) + myoC He Ty ~ "°) = 0 10" + CHT? + Patt rn _ aan + he 2105 ge 955 4° mot t378 K+ AAS ENLOO 953 9" mo 258 Tia p10 mel | 2105 pean 18.02. g mol Tg 55 1K ar ROO 9595 mar 802g ml 7802 g11,0 mor Ty = 328K Paeon ti % 406503 mot”! ‘AS is calculated forthe steam. It consists of condensing the steam at 373 K and cooling the resulting water to 328 K. As AHaporttin 1 pStperster «ne, jy TL — Traportzaion ,05 gsteam 406503 mol 2105 gem 9554-1 ol xn BK 1802gmol? 373K *1802g steam mol” 373K 13863K"" ‘AS is calculated for the water. It consists of heating the water from 298 K to 328 K. 328K 753. 5K mol! x Ine = 164.7 K 208K AS = npn = 458 wT, ~ 18.02 ¢ mol” ASyyat = 164.7 Kt ~ 138,65 K = 26.05 K", The process is spontencous, Using your result from Problem 5.31, extrapolate the absolute entropy of L-alanine to physiological conditions, T = 310. K. Assume the heat capacity is constant between "= 300.K and T = 310.K. ‘We can either extrapolate the curve to 310. K using the same functional form or assume that the heat capacity is ‘constant at its 300. K value between 300, K and 310. K. 310.K -9.1602 + 0.776107 — 0.00195117? + 2.76403 x 10°67? ox T S°G10.K) = = 135214 mor S°@10.K) = S°G00.K)+ Conte 310.K = 135.1 K7 mor 300K = 1352541 mot! + 122.7 K+ mola: ‘The mean solar flux at the Earth's surface is ~2,00Jcm™ min“. In a nonfocusing solar collector, the ‘temperature reaches a value of 79.5°C. A heat engine is operated using the collector as the hot reservoir and a cold reservoir at 298K. Calculate the area of the collector needed to produce 1000. watts. Assume that the engine ‘operates at the maximum Camot efficiency. 298K 35265K 50155 Copyright © 2013 Pearson Education, Ine.94 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics ‘The area required for the solar panal is power 1000.9 s** = = 194m? efficiency x flux 0.155% 2.00 em min x1 min/60 x10" em? im? 5.43 An ideal gas sample containing 1,75 moles for which Cy», = 5/2R undergoes the following reversible cyclical Process from an initial state characterized by T = 275 K and P = 00 bar: Its expanded reversibly and adiabatically until the volume triples. ».__ Its reversibly heated at constant volume until increases to 275 K., ©. ‘The pressure i increased in an isothermal reversible compression until P ‘and AS for each step inthe cycle, and forthe total eycle. 00 bar. Calculate q, w, AU, AH, (@) The temperature atthe end of the adiabatic reversible expansion is calculated, er fei nan(Z] = 215K XQ) 3 =275KxGV% = 177K ‘and final volume and the final pressure are calculated, RE, _ 1.75 mol x 8314 J molK"'x 275 K y= ORE 2 =2.18%10~%m? B 10° Pa Vp =; = 655x109 m WT 17k P= PLS = 100barxty ZK — oa: ro ye mS DISK ae q = Obecause the expansion is adiabatic 5x 83143mor Kk AU = = ny gAT =175 molx x (77K 275 K) = -2.56%10°5 2 x Dest AH = nCpyAT = 175 mol (177K ~ 275K) = ~4.98 x 10°F AS = 0 because Jreserite = 0- ASyuroundngs = 0 because ¢ = 0. ASyyy) = 0. (&) w= Obecause AY = 0, 5x 8314 Jmol Fj 78314 Jmol"K 2 AU = 9 = MCAD = 175 mol x (215 K-17) = 356x107) (275 K ~177 K) = 498x105 AH = nCpyAT = 1.75 mol x ‘The pressure atthe end of the process is calculated in order to calculate AS. 275K. 1, Py = BL = 0215 bar x. 0.333 bar Tee 17K z 1, a-ak 4 Cp in 85 atin + nCpain gly jy O'333 bar 78314 3molK | 275K = A275 mol 8314 Jmol Kx In 0333 PH 175 mole ESM IME KA, 275K ogee eerie tor Oa tae 2 “OTK = ~639 1K" 4-22.38 1K7 = 160K ~4 3.56 10°F 1 AS eta = BSO009 _ 97K ro nang 25K Saat = AS + ASperamdnge #160 3K ~12.93K7 = 3.1K ‘Copyright ©2013 Pearson Edvetion, Ine,Chapter 5 Entropy and the Second and Third Laws of Thermodynamics 95 (©) 4H = AU =O because AT =, 0.333 .75 mol 8.314 Jmol“'K~ x 275 K x In- =440x10° 5 Fy 1.00 bar warn = xin AOObIE 60 54-1 a5 =-nint In AQOb reo AS,, —i1 4.40210" 160JK" srt Tes 2S Svat = ASrurountngs + AS = ~160 IK" 16,0 K~ = 0 Forth entre eyele, Wace = 356X109} +04 440% 105 = 8405 Goete = 0 + 3:56%10 J ~ 4.40% 10° = -840) Uae = 56X10 J +3.56x109140=0 Hoge = -498X10 J + 498x105 40 =0 ASgete = 04 16.05K7 = 16.03 K4 =0 ASerrourging ter = 0-12.93 K 416.05 K7 = 31K ASpratgete = 35K Ree 544 For potin denaturation, the exes entopy of denaturation ie dened as ASyy = [SCF cr, where Cf isthe i transition excess heat capac. The way in which BCI? canbe exacted ffom differential scanning calorimetry (DSC) data is discussed in Section 4.6 and shown in Figure 4.7, The following DSC data are for a protein mutant that denetures between 7; = 288K and 7, = 318K. Using the equation for AS, given previously calculate the excess entropy of dentuation. In your clelations, use the dashed curve asthe heat capacity base ine which defines 3Cf? as shown in Figure 48, Assume the molecular weight ofthe protein is 14000. rans, Apparent Heat Capacity 288 208 808 318 Temperature/k, ‘You can perform the integration numerically using either a spreadsheet program or a curvecftting routine and a graphing calculator (see Example Problem 5.9). Copyright ©2013 Peuson Education, Ic.96 Chapter 5 Entropy and the Second and Third Laws of Thermodynamics We breakup the area under the curve into rectangles and evaluat the aren which s Cp x AT, We then divide by ‘for each rectangle and sum the contributions and finally multiply by the molar mass. This estimate approaches the ‘value of the integral as the AT value approaches zero. The result is 620 mol”! K~!, % San = SE ar = [SE preys 0.031 3K ¢ a 0.062 1K"! g 0.083 1K g! 4 0125, Jkt gt +2 167 Kt gt DIK mK * aK 24K 25K 4 0295 gt 0334 KT 0480 Kl eT | 0627 Kg | 0.836 1K"! g 296K 298K 299K 300K = Mx| 4 hOtIK Eg 138K gp) 140K gt 133K gt 301K 303K 304K 305K i ct 0376 7K g 306K 307K 308K 309K 310K 4 0251IK 1g | 0.1677 K Tg | 0.084 7K" SUK 312K 33K 27 = 620 mol! Kt P5.45 The standard entropy of P(s) at 298.15 K is 64.80 1 K-! mol”. Assume that the hest capacity of Pb(s) is given by (Pb, s) - rare Z : ‘The melting point is 3274°C and the heat of fusion under these conditions is 4770.3 mol" Assume thatthe heat capacity of PB() is given by LemPOD 59 51- ooos012 TK mor K 4. Calculate the standard entropy of Pb() at 725°, . Calculate AA forthe transformation Pb(s, 250°C) -» Pb(?, 725°C), (2) Sy(Pb,1, 998.15 K) = $°(Pb, s, 298.15 K) ans Ajai Cp f CPx ate) + Mlaown 5 Sea ate] isl”) Traion eo ssl7K) = 64.80) mol K™ ass 5 =f 2 oonnfr | LORI gr gy 2s [re] 44770 Jmor"! 60055K 998.1539 51 — 0.00301[7! 32.51— OOP erg) wos IK] = 64.805 mol" K+ 20.40 Jmol K+ 7.94) mo K+ 15.3 Jmol! K> = 1085 Jmol! K+ 00s ms )— MMaat =f CR ALT] + AM pion +f CHAT AK] aves oss = 8.9210? Jmol + 4770.1 mol"! +11.97x10° J mol 25.7 10° Jmol! Copyright © 2013 Pearson Edusation nc,