2 PROBLENS IN METALLURGICAL THERMODYNAMICS AND KINETICS sowte 2A Celculate the standard entropy change for the reaction 4 KO = 2c + 3(60) at 25% (290 x), . Given: S298 + *1.38 cal/deg/mole (5.69 s/k/not). 298, = 5.68 cal/deg/mole (23.76 J/R/not). $°298,(co) 47-3 cal/deg/nole (197.80 3/k/not). Solution: The standard entropy change of the given reaction at 25°C can be written as On = 289, +392 - 3° 39 ‘Seas * * Sava.cers* 2 S'r50,(c0) ~ S%208,crs0,p ~ 3 S50, * Putting the appropriate values in the above equation, #893 = (2x5.68) + (3447.3) - 19.4 - (31.36) = 129.78 cal/deg. |Exarple_ 2, Calculate the standard entropy of solid copper at 1073°C (1366 following data: So0, a (22.63 + 6.27 x 10° 7 J/x/mol). Solution: Applying &9.(2.7), 1346 c 300 o. or St346, F i 230 ; wee of Bitter ies Putting the appropriate values in the above, sf = 9956 | (S86 240s ers Wl 1023, {2n} 298 1o23 of Liar 4 693—(«iT = 9.95 + 5.35 ( In 693 - In 298) + 2.40 x 1073 (693 ~ 298) + 2.51 + 7.50 ( In 1023 = In 693) = 20.05 cel/deg/aote‘The Second Law of Thermodynamics : Entropy and Free Energy 7 Bzople 2.0 ‘The phase transformation in pure iron may be represented as follows: 1033k 1183k 1673k 1e12k —+ ——+ ey-Fe> ——> —— (Fe). Calculate the standard entropy of pure iron at 1627°C (1900 x) if its standard entropy at 25°C (298 X) 1s 6.50 cal/deg/mole (27.20 J/K/not). Given: “P Spey-Fe> “py °p, (Fed 4.18 + 5.92 x 1079 T cal/deg/nole (17.49 # 24.77 x 10° 7 a/K/mot). 9.0 cal/deg/mole (37.86 J//mot) 1.86 4 4.65 x 107 T cal/deg/mole (7.70 + 19.50 x 10% 8 J/k/rol). 10.50 cal/deg/mole (43.93 J/X/mol). 10.0 cal/deg/mole coFer — cbf 5 Aiygy = —+ {Fe} yy, “033, (cf) 96 ca-Fes . T 10331183 ¢ > Pushy 1033 1673 Putting the appropriate values in the above, ° $1900, (Fe) 1033 ves [ [Besse aa vere = 6.5 + 4.18 ( In 1033 - + 0.63 + 9 ( In 1183 - (1m 1673 = 10 1183) + PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS © «Stas, ou 1183 aye. Me73, Gs 1673 Moe cesta 660 1,033, 1. Bs Pes cco oer vas In 298) + 5.92 x 10° (1033 - 298) Tn 1033) +0.18 + 1.84 4.66 x 10° (1673 - 1183) + 0.10 + 10.5 ( In 1812 ~ In 1673) + 2.02 + 10.0 (In 1900 - In 1812) = 24.41 cal/deg/mole.The Second Law of Thermodynamics : Entropy and Free Energy 39 Eeaple _2.E ‘Smal droplets of gold have been observed to supercool by a maximum amount of approximately 230°C, What is the entropy change associated with the iso~ ‘thermal solidification of 1 g-atom of such supercooled gold? What is the entropy change of the surroundings if they are assumed to remain at the same ‘temperature as the supercooled gold? Also, calculate the total entropy ‘change. Given: Gp ays, * 9.0 cal/deg/mole (20.92 J/K/mot). Cp ayy ~ 7.0 cal/deg/nole (29.29 J/K/mol). MeIting point of gold = 1063°% (2336 K). Heat of fusion of gold, Aly = 3,050 cal/nole (12,767 ¢/not). Solution: This is an example of irreversible process.’ The entropy change of ‘the system can be calculated by considering @ series of reversibie steps “= Jeading from a supercooled gold at 1063 - 230 = 633°C. One such series might be as follows: (1) Supercooled quid gold is transformed reversibly from 833° to 1063°C (welting point of gold). {au} at 833°C + {Au} at 1063°Cs aS). (2) At 1063C, liquid gold 4s transformed reversibly to solid gold. (Au) at 1063°C —~ at 1069%C; a (3) The solid gold is brought from 1063°C to 833°C. hum at 106% — chu» at 800°C; 05, (On adding (1), (2) and (3), we get the required reaction, f.e. {hu} at 833°C + at 633°C; (2.6.4) BS = BS, + AS, + AS340 PROBLEMS IN METALLURGICAL THERMODYNAMICS ANO KINETICS 137 mud aS, = [ -Eathud gy 1106 1336 1106 = 1.32 cal/deg. = Enthaly change of the reaction (2 (1,063 + 273) a (leat of fusion of gold) 7,336 4s, 73,050 1,336 ~2.28 cal/deg. 106 «, ib wo [Sete 1106 1336 0.98 cal/deg. 5 BS) + OS, + AS, = 1.32 - 2.28 - 0.04 = 1.90 cal/eea. Now consider the surroundings.* The irreversible process is able to transfer hheat reversibly to the isothermal reservoir. The temperature of the surrounde ings is the same as that of the supercooled gold i.e. 833°C. = Heat absorbed by the surroundings | 4s, Surromdings " “Tenperature of the surroundingsThe Second Law of Thermodynamics + Entropy and Free Energy a Now, total heat evolved from the system = Ay + tH, + OMa, where AH, and bit, are the heats of reaction of (1), (2) and (3), and can be calculated as follows: 1336 aye %p tau) ros 1336, = 70 at 1106 1,610 cal. 3,050 cal. vos aly, = eres vhs "oe 2) som 1336 a = -1,150 cal. «Total heat evolved from the system = 1,610 - 3,050 - 1,150 =2,590 cal. Hence, the heat absorbed by the surroundings is equal to 2,590 cal 24590 os “Scurroundings ” T7106 Total entropy change of the reaction (2.6.1) as, ASiy, * “Ssysten * "Ssurroundings = 1,90 + 2.38 = 0.44 cal/deg. Sehe Second Law Of Thermodynenics + Entropy and Free ergy (AT mearple_2.P Calculate the standard free eneray change of the reaction “ ° Mo0g> + (Hy) = Hor + 3(11,0) at 727° (2,000 k) and 1 abn pressure from the following datas. © $00, ao,» * “120,000 catfmote 502,080 mot. © 4p00,cH0) “#50500 calnote (180,572 mot). Also, comment on the possibility of reducing MoO, by Hp at 727°C and 1 atm pressure. wee Solution: From the 48a. 62599, 4 (Hy) = atts + (H,0); 06° = -559 = 10.18 T cal (2,301 - 42.59 7 3). etree + (Hy) Aer + (HO); 46° = 30,250 ~ 7.33 T cal (128,866 ~ 30.67 7 3). + (Wy) = + (4,0). (2.6.1) kcr7037 + (Wh) = 4c + (4,0). (2.6.2) shir + (10) = ior + (HL). 2eCr> + 3100) = at 327°C (600 K) from the following data:‘The Second Law of Thermodynanics + Entropy and Free Energy 51 Atego * “87800 cal/mole (-240,580 J/no0). SBopents 7 7o12 caV/deg/nole (22.79 s/t/mol). 33o,(05) = 49.02 cal/deg/mole (205.09 J/X/mol). 2 Bog cutds 9-10 c21/deg/nole (38.07 /K/not). Chenin * 8:08 + 10.84 x 10°? = 2.8 x 10°° T eal/éen/mole (28.28 + 43.6810 — 10,48 x10 7 /k/nol) , (0) 7 TSS 10x Wo"? T- 0.6 x 105 1° cat/ees/note (29.098 + 4.18 x10°¢8 ~ 1.87 x10° 3° /k/mol). op, io» 12.91 caV/deg/nole (54.01 J/t/mot). Solution: + 4(0,) © (2.4.1) HBo8,(2.H.1) * 299,00» = -57,500 ca? 15259,c2.4.1) 7 9:10= 7.12 = 26.51 = -22.53 cal/deg. Ap = 12.91 = (6.03 + 10.44 x 10°6 12 - 2.50 x 10°31) “407.16 + 1.0 x FT - 0.8 x 108 12) = (3.90 = 10.40 x 10° 72 «2.6 x WIT 4 0.2 x 18° Te) cal/ees. ‘The scheme of calculation would be as follows: (1) cateutate a o0,¢2.n.1) 17 8Bo8,¢2.H.1) 24 Ap, c2..1) Values82 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS (2) Catcutate as? (3) Calculate ace, ° “M600, (2.H.1) Similarly, 85600 ,(2.4.1) ©, 600,(2.H.1) f° *S°o55,¢2.4.1) M4 8Cr,(2.4,1) YATUeS- B00,(2.H.1) #708 (1) and (2) using E9.(2.12). econ? | Seen 28 600 -57,500 + | (3.30-10.44 x10 1? 42.0 x10 31 288 50.2 x 10 Tar * + Sca0%- 2963 ~87,500 + 3.90(600 = 29) - 20.44 x 10 (600"- 298") 3 + 20x10 (6002 - 2987) 2 56,858 cal. SP sep ce.n.ty ° . z *S296,(2.H.1) al e 690 22.53 + J ox = 10.46 x 106 + 2a + 2.0 x 109 + 0.2 x 10 T -22.53 + 3.30 ( In 600 - In 298) - (600° - 298%) + 2.0 x 10°? (690 298) ott [2 _i) 00" 298°) -20.96 cal /deg. Putting the appropriate values in the equation 6°, = ai’; -T as,a ‘the Second Law of Thermodynamics : Entropy and Pree Energy 53 0 A6Cyg = -£6,858 + 600 x 20.95 = A282 cal Beargle 2.7 Calculate the standard free energy change of the reaction {Pb} + 3(0,) = at 527°C (800 K) from the following data: Aig eppost ~Ses4OD eal/note (278,268 0/A/not). Soa, ~ 15-50 cal/deg/mole (64.85 J/K/nol). S$08,(0,) = 49.02 cal/deg/mole (205.09 J/K/mol). Cp, cppon * 10.604 4.0K107T cal/deg/note (44.86 416.74 11077 4/t/not). Cp cpp, * 5:6342.33x109T cal/deg/mole (23.55 49.75 x10" > J/K/mol). 31 cal/deg/mole (32.43 - Spycppy 7-75-0741 7 a/k/mot). Cp,(og) 7 T1B+T.OXISPT - 0.8 x10° 1 cat/deg/mote (29,96 + 4.186 108 P= 1.67 x 105 1 a/K/nol).54 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Helting point of bit, = 327% (600 0. Latent heat of fusion of PbyL~ = 1,150 cal/mole (4,812 J/mol). Solution: The problem basically consists of calculating the standard free energy change of the reaction ‘ (Po) + 4(0,) = (2.1) 45° and ACp values of the reaction + (0) © (2.1.2) at 25°C. This problem is similar to the previous one, except for the fact that a transformation, i.e. melting, fs taking place in one of the reactants, i.e. Pb, at 327°C, and proper correction terms must be included. The scheme of calculation would be as follows: ° 1) Calculate ating, ¢2.1.1)* ° (2) Catewtate A5h09, (2.1.1). (3) Cotevtate e665 cp 4.4) fram (1) and (2)s using E9.(2.12). ‘MGo0,c2.1.1) 2h be calculated sinflar to that ‘Mustrated in Example (2.4). Thus, 600 ° ° Meo0.(2.1.1) ~ Heoe,(2.t.2) * cao 258 tet ob eevennay 1.3) Cr ca.t.2y #‘the Second Law of Thermodynamics + Entropy and Free Energy 55 Ap (2.1.2) (10-60+4,0x1097) ~ (5.63+2.33x167T) = (7.16 + 1.0 x 103 T 0.4 x 10° 2) (1.39 + 1.17 «103 T+ 0.2 x 108 17%) cat/deg, anda ¢9,4,1) + (10.60 6 4,0 x 10°? T) = (7.75 - 0.74 x 10° 7) = (7.16 + 1.0.x 109 T ~ 044 x 10° 12) (-0.73 + 4.26 x 1079 T + 0.2 x 10° 17) cat/deg. Putting the appropriate values in Eq.(2.1.3), 690 = 52,4004 f (1.394 1.17 x 10°98 T+ 0.2 x 1081 2)ar 298 ° ‘M00, (2.1.1) = 1,150 + r (-0.73 + 4.24 x 10°74 0.2 x 108 1) ot 600 3 600? = £2,400 + 1,39(600 ~258) ¢ 21721 (600 -298) B14 = 0.2 x 108¢1 Ly ~ 4,150 - 0.73800 - x 105 ~ Ly = 1,180 - 0.73(800 - 600) + 4.24 169 (000 600%) - 0.2 2 10° (gly - hy] ° Similarly, as’ can be calculated, 900,(2.1.1) 600 00 eS 2 BC, £ ho e.ta) * Soot. | °, 2. a othe { P(2T.1) op T (2.1.4)56 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Now, 98990,(2.1.2) = 16-2 ~ 15.5 ~ 4(49.02) = -23.81 cal/deg, Putting the appropriate values in the'Eq.(2.1.4), 690 23ho0,(2.t.1) = 723804 | (1.39714 1.17 x 10°F 40.2109 Par 298 so = 10804 OP (oo.ra rT egzt nid 40,20 108 har poe 600 = 23.81 + 1.39 ( In 600 ~ In 298) + 1.17. 10°? (600 - 298) 02x17 1 1) | 1150 2 [at we) * “Ss = 23.67 cal/deg. Putting the values of MZo9,c2.1.1) and” #58, ¢2,1,1) 1h Ee. (2.12), 86500,(2.1.1) * ~S20482 - 800 x (-23.67) 546 cal.Exaple 2.0 Calculate the standard enthalpy and entropy changes at 25°C (298 X) for the reaction 20> + HO,) = s 86° = 40,500 - 3.92 T log T + 29.5 T cal (-109,452 - 16.40 7 log 2 + 128.45 7 J). Solution: a6? = -40,500 = 3.92 x 0.4343 T In T + 29.5 T = 40,500 = 1.702 T In T + 29.5 T, (2.3.1) or B62, _ 40,500 _ 1.702 1n T + 29.5. T T Differentiating, ac’S'/t) , 40,500 _ 1.702 ar ? T Fron Eq.(2.31), aH 40,500 _ 1.702 eT 2Cy PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS or aH? = -40,500 + 1.702 T. at 28%, o “98 Differentiating (2. 3.06° aT From Eq.(2.26), = -40,500 + 1.702 x 298 = 39,993 cal = 239.99 keal IMs = -1,702 - 1,702 In T + 29.5 - = 27.798 - 1.702 In T. = 08° = 27.798 - 1.702 In T. at 25%, ° O8$gg = -27.798 + 1.702 In 298 = 218.10 cat/deg, . Example _2.% 46° for the reaction at 25% r298 x) 1s fron the following 2298 Pent + 4(0,) = ) 2 50,786 cal (-212,489 J). Calculate 46° at 327% (000 x) dati = -87,500 cal/mole (-240,580 J/mol) = 6.03 + 10.48 x 1076 1? ~ 2.50 x 1079 T cat/deg/mole (28.23 + 43.68 x 10 2? ~ 10,48 x 10°? J/K/mol).‘The Second Law of Thermodunanics : Entropy and Free Energy a Cp.cq,) * 7-18 + 1.0 x 10 T- 0.4 x 10° 1? cal/deg/nole wht! (29,96 + 4,184 x 1078 7 1.67 x 20° 2°? a/t/mot). Cp,ation * 12.97 cal/deg/note (54,01 J/k/not). Solution: Applying the Gibbs-Helnholtz equation to the reaction under ‘question, i or ac (2.21) 4 a But ane faye + flee - Gar - Fay) J v2.99 = (6.02 10.48 x 10°F? - 2.50 « 11) ) at = 7.16 41.0 x 03 TF -0.4 x 10° T [ co. 0. SP 2.0 Wre02 a ret 63 . a0 7 - Rata, 2 ean = 0.2x10°1" "43H, (2x2) where AH, fs an integration constant. At 25°C, the standard enthalpy change of the reaction 48 -57,500 cal/nole. Putting this value in (2.K.2), 8 2053 257,500 = 3.30 x 298 - WAL XI R288 4 1.9 x 1079 x 208 6 2 x 10' 02 x10”. ay 298 ° = 913 + BHyy62 ‘PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS or aH, = -57,500 = 913 = 58,413, Putting the value of AH) in (2.K.2), 0 aH = 3.907 - 3.48 x 10% TF 4 1.0 x 10° 7? 0.2 x 108 150,413, = 3.48 x 10 T+ 1.0 x 1079 - 0.2 x 10 1°3-59,413 F Substituting the value of SP tn (2.k.1), . t te? a ot fom tls auener soni oz hsyearha 6 é . +1 [3.30 mr = 2B” Teton er + B22 y2 4 58813 1 : [- 3.30 T nT 4 1.76 x10 19 7.0 x 1073 12 ~ 0.1 x 8 TT = 58,413 - rT], (2.k.3) where I 4s an integration constant, At 25°C, the standard free energy change of the reaction under question is -50,785 cal. Substituting this value in the above equation, 780,786 =~ 3,30 x 298 x In 298 + 1,76 x 10°F x 2989 - 1.0 x 1079 x 2982 1x10 § 238 = = 64,091.85 - 298 1, = 58,413 - 298 1‘Me Second Law of Thermodmmantes + Rrtropy and Pree Enersy 6 or 298 1 =~ 64,091.85 + 50,785 = = 13,308.85, or T= = 46.65. Putting the value of I fn (2.K.3), m6 = = 3.30T In T+ 1.78 x 10° TF 1.0 x 10° - 0.1 x 08 TT = 58,413 + 44,65 T = 58,413 + 1,74 x 10% 13 - 1.0 x 10°F T? = 3.30 T In T +44.65 T 0.1 x 108 1), 268yq =~ 58,613 + 1.74 x 107% x 600° x 600% = 3.30 x 600 0.1 x 108 600 x In 600 + 44.65 x 600 - = -44,290 cal.