THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 110 Chapter 7 CHAPTER 7 [7.1] Using the Bi-Pb phase diagram in Appendix E, Figure E.8, calculate the activity of Bi in an equimolar liquid solution of Bi and Pb at 625 K. Assume regular solution behavior, Solution Since the activity of Biis de must be analyzed (Gi is data is obtained from the Bi-Pb phase diagram: Point on ‘Temperature wo Liquidus SGai 1K Bi 1) 125 398, 56 2) 175448. 70 3) 200 473 16 |, the high Bi liquidus side of the eutectic fined relative to pure liquid Bi). The following Using [7-5], regular solution, no solid solubility and data from Table A.2: (1-56 + 10,879 a) 398 = 20-58) +087 TBB144 In(56) + 20.00 (1~-70)" + 10,879 (2) 448 = “5.3144 In(0.7)+ 20.00 (1-76 cary —PiLta-20) 410.878 [85144 In(76)+20.00 Solving for 9 and averaging: (D Qt =-5167 (2) Qt =-8560} 0,, =-5875 (J/mol) (8) at = 5898} Substituting into (6-43), S875(1—.5)° +8.3144(625)n(5) =-S071=8.3144(625)hn(2y5) #m = 038 oh Note: From Kubaschewski and Alcock (1979, p. 411) Hi =—1109 J/mol and § Bi = 0.167 J/(mol-K). wtTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS fa, ay = 0.396. Although the regular solution model assumes 0, the agreement is within experimental error, [7.2] Using the results from Exercise Problem [7.1], calculate the equilib- rium Fo, gp Over an equimolar Bi-Pb liquid solution at 625 K. The Gibbs free eneigY of formation of dibismuth wioxide, Bi,O, is AG, = — 407,250 J/mol at 625 K (Wicks and Block, 1963, p. 21). Solution Q) Sc.Up 2B + 40,09) AS82 » 8,0, 25m lab AG, Ae, 2Bi (0) + 92.0, Cg) AMi2s 53: 0,66) (2) Sum Sage = 3) Substitute AGSas = — 407,250 Jno (given) = AGbs + AG, — AGeos - KAG, - 269" a0; =4RT ha (P,) 255! =2RTm (ay) Substituting into E AGy, =0, 407,250 ~ (68.314)(625)In{ Pp, )~2(8.3144)x(625)in (0:38) @) Solve P,, = 14x10-¥atm, 12 CHAPTER 7 it would be Note: The result indicates that Bi will oxidize from solution sit impossible to maintain such a low Po, [7.3] From Kubaschewski and Alcock (1979), solution data for a 70 a/o Bi- Pb solution (Exercise Problem {7.1)) are: Tgh'= ~70>4.184 =-292.9 I/mol and S3°= 0.03 x 4.184 = 0.1255 JAmolK). Using this data, esti- ‘mate the heat of fusion of Bi, Solution From Table A.2,T'= 544 K and AH, From [7-2], aa 92.9-+ aH| 1255~83144 In (0.7)+ ANG [548 Solving, aiff = 907Hm0} oF 13% ero, “The ero is atibuted wo reading err from the phase diagram and assump- tion tat AC, = 0. 10879 J/mol. [7.4] Repeat Exercise Problem [6.9] using the following solubility data esti- ‘mated from the Pb-Sb phase diagram in Appendix E, Figure E.9: X,, = 98 K and X,, = 0.2 at T = 533 K. Note thatthe solubility data is given at a much lower temperature than the refining temperature. Assume: (2) Calculated solution parameters hold atthe higher temperature, @) The process involves the reaction 256 + 3PbO(s) > 3P5 +Sb,05(9): (3) Sb behaves as a dilute solution component at these concentrations. Solution From Exercise Problem (6), approach 2 at 900°C, ag, = 0.013. If Sb acts as a dilute solution component at this temperature, 0.019=baXq or Xy= 2218 whore be, (dilute solution) = From [7-4], hy, and s, are determined and then b, is calculated: hg +19,876 Bq + 18.982+22001 aay 53 113THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. hy +19,876 Q) 598 = 4+ 10.01+22.01 Solving simultaneously, h, From [6-38], =3341- 1173-437) by = exp) NTH) ox 83144(1173) Substituting, o.o18 Xq= 2213 ~ o011~ 6500 ppm So, ‘Note: Assuming that Sb behaves ideally (Exercise Problem [6.9}-Method 2) yields a result 23% higher. 3341; 6, =~ 4.37. 17.5] For dilute solutions of carbon (graphite) in liquid sodium, solubility ¢0.C,(6) Q) Sum EAGy = 0= AG figs + AG, -AG,,.,— 24G, - AG, (3) Substitute AG Pigs =— 57,326 ~28.45T (Table A.4) AG, = AG, = 0 (pure condensed phases) AG yy, = 0 (equilibrium) 2AG, = 2(5272 -TI- 68.62 -8.3144In(X)}} ‘Substituting into LAG,, = 0, 0 = -57,326 -28.45(1193) -2(5272 — 1193[-68.62— 8.3144In(X) 1} 13.39 Xe = 15% 10+ or 0.80pm. [7.6] Using the following data from Kubaschewski and Alcock (1979, p. 386- 389) for Cu in a Ag-Cu liquid alloy at 1423 K: ee 00 [| 01] 03 | 05 | 07 | 09 H&! (mol) | 23,014 | 15,692] 7482 | 3766 | 1435 | 159 se DBAmolK)] | 5980 | 3.084] 0.456 | 0.100 | 0.084 | 0.004 @ Calculate GS. 115THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (6) Calculate ZS trom the results in Example Problem 7-5 and compare with pat (a. Solution @ Using (6-471, G& is calculated as follows: HE — 1Sgp = 23,014 - 1423(5.98) 4,504 J/mol Xq= 0.1 = GE = 15,692 - 1423(3.084) = 11,303 Xq,=0.3 = OS = 7482 1423(0.456) = 6833 5 = OE = 3766 -1423(0.1) = 3624 7 = GE = 1435 -1423(.084) = 1315 X.,=09 = GS = 159 1423(008) = 1583 Ans: Ko 00 7] ol | 03 | 05 07 [09 GE | 14504 | 11,303 | 6833 | 3624 | 131s [1533 G/mol) (b) Using [6-47], G& is calculated as follows: Xq2 0.0 => Gos = Hey =a! XP =12,889(1-0F = 12,889 Jmol Xq 20.1 = GE = 12,880(1-.1)2= 10,440 Xq,=0.3 = GE = 12,889(1-3*= 6316 X= 05 = GH = 12,889(1-5 = 3222 Xo,=0.7 = GS = 12,889(1-.7? = 1160 Xq,=0.9 = GE = 12,889(1-9F = 129, Ans: Xo oo [or [03 | 0s | o7 [09 G&S Gfmol) | 12,889] 10.440 | 6316 | 3222 1160. | 129 ‘These results differ from those of part (a) by 11-16%. See Example Problem 7-5 for further discussion, 116 CHAPTER 7 [7.7] Using the data from Example Problem 7-8 and Appendix B, Table B.1, predict the eutectic temperature shift resulting from a pressure increase from 1 to 1000.atm. Solution Using data from Example Problem 7-8 and Table B.1: 98, = 21,111 J/mol and 2, = 22,720 J/mol 6 “396° predict. Assuming Vg mrivariant boundary, se simteananty 17.10} Estimate the equilibrium vapor pressure of SO,(2) over $O,(0) at 265 K. State assumptions. Solution ‘The univariant equilibrium transformation is 80,0 > SO,(g) Using Table A.2 data, gssuming AHF ~ constant (AC, x 0) and integrating the Claussius-Clapeyron equation, [7-20] 119THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS "YSTEMS 24,937 8 _ aT 83144 Jao (PF [ane {7.11} Estimate the solid-tiquid isothermal transformation temperature of Au a 75 atm. State assumptions. Solution ‘The univariant equilibrium transformation is Au(s)— Au(1) ‘From the Clapeyron equation, [7-21]: ab aim | a? _ ava a? TAV T aH™ From Table B.1, 91197 ‘ao Vouw™ 77,9 7193 7 P38 em! From Table A.2, AH™ = 12,760 Jmol Integrating [7-21] while assuming AV and AH constant: 120 CHAPTER 8 Chapter 8 [8.1] Referring to Example Problem 5-6: (a) Find the equilibrium constant for the reaction and discuss the effect of increasing (b) total pressure and (c) temperature. Solution (@ SiCI(g) + 2H,(@) — Si(s) + 4HCI) Subst (5-4) and (62) inc [8-2} where a Ky YioPt Ma" T Ya ViiaPy = YE Yo, (b) Examination ofthis expression reveals that an inerease in total pressure has the effect of desteasing the yields of Si(3) and HCI(g). Yyq in the enpresion must decrease in order to maintain K,,consiant ° (©) Referring tothe Van't Hot equation, 8-7: InK,) = “RE 4, itis necessary to know whether the reaction is. endothermic or exothermic. From Table A.1 and assuming AC, = 0, AHS = 44H Yh nq - AHS sc, 4-92.32) - (- 662.81) =+293.53 kJ/mol. Since AH > 0, Ku inereass asthe temperature increases. [8.2] The decomposition of Fe,C(s) (decarburization) ina stel exposed to a hydrogen environment can result in the internal formation of CH,(g). Internal pressure created by accumulation of the CH, can lead 10 80 called hydrogen attack because CH, cannot diffuse from the lattice struc ture, Repeat Example Problem 8-3 for exposure to a mixture of H,(2) ‘and CH,(g) at 500°C and determine the maximum Poy, / Pj, ratio that ‘can exist without causing significant decarburization ‘and subsequent hydrogen attack. 121