THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS 8) 98 STEMS CHAPTER 6 Chapter 6 [6.1] Derive an expression equivalent to Sievers law, (6-72b], for solution of hydrogen gas in an aqueous solution, Assume Henry’s law. Solution @) Setup. a = 4, (AAS Hy (Oy = Ky, = Cu) doz AG, Ace = ° ty (1) ASH, Can, = bx, 2 Sum TAG, = 0= AG? + AG, - AG,-AG, @) Substimte AG} = AHI - TAS$, AG, =O (equilibrium) AG, =RTIn(Cy, /CR,) 6, RtIn(%,) Substituting into FAG, = 0, O~ AH ~TaSe + RT In(C,, /Cz,)~ RT In (P,,) (4) Solve (en /O4)/Pa] Cat +759) Cy = # Bwhore constant k= Ci, -xpl(-aHlg + 7453)/ 27] [6.2] Sieven’s constant for solution of oxygen in liquid silver is k = 193.6 cem*atm®5/100 gm Ag at 1075°C (Darken and Gury, 1953, p. 513). Calculate the solubility of Ag at the same temperature if Fo, = 50 mm. Hg.THERMODYNAMIC LOOP APPLICATIONS IN MATERIAL Solution ‘STEMS Cyq= 193.6 (50/760) jem? 100 gm Ag [6.31 Referring to Example Problem 6-5, show from the Gibbs-Duhem equa- tion that 71%, = -20,083(1 -X,,)° J/mol, Solution Substituting HE, = -20,083(1-Xe,)* into (6-571, X,dL-20,083(1 X51 +X,, a7rg=0 aH =a 10,083(1-Xo,}"] Xia oe foo lg “aM, afi fe rat 1.166)(1- Xo, )aX, Xow =~ 7 (40,166) ‘His = ~20,083(1- X,)° J/mol. [64] Calculate the composition (fo) of a binary A- alloy in equilibrium with oxides A,O and BO at 627°C. Given AG? g= -15,000 cal/mol and AG3o= ~25,000 cal/mol. Assume solvent A'is ideal. Solute B is Henrian with 7 = constant = 1.15. The metallic phases are completely soluble in each other, whereas the oxides are insoluble. Solution () SetUp A,0 (e+ Ble) ASO» Bow + 20) AG AGs in 46, |246, 2.008) + B(s) AS Bee y ore) + 24 (5) @ sum ZAG, AGS +24G, + AG, ~ AG,— AG, AG, 100 CHAPTER 6 (3) Substitute Gay = 25,000 — (15,000) = -10,000 cal/mol 2AG, = 2GR = 2RTin(a,) = RTIN(X,2) ‘AG, = AG, = 0 (pure condensed phases) ‘AG oq =0 (equilibrium) AG,= GE =RT In (7,X,) = RMn(1.15%,) Substituting into ZAG, (0 = 10,000 + 1.987(900) In(X,2) - 0 ~ 1.987(900) In{1.15(1 -X,)] @) Solve 1788.3{1n(X,2) ~ In(1 -X,)] = 10,249.94 Xk TX, X,2+ 308.483X, ~ 308.483 = 0 X,=0.997 = 997 alo X,=0.003 = 03/08. = 308.483 [6.5] For the binary liquid alloy system Cu-Zn, the zine vapor pressure at 11060°C is given as a function of composition inthe Following partially completed table (Darken and Gury, 1953, p. 512): X%, 005 010 015 020 030 045 10 P,, (atm) 0.0289 0.0592 0.1184 0.2368 0.6000 1.2763 4.000* Ya c ces ine 2, + Value is high compared to data in Appendix A, Table A.5. (@) Complete the table (use metric units). (b) Does the system obey the ideal, Henrian, or regular solution moder? 101THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS 8) Solution EMS @ oy Ge, = YesXzq = Poy Poy = Pol Yoo You = Gal Kay Ga(smol) Ga = RTIn(a,,) = 11,083.1 In (a,,) GEX(smol) Gye! = Gh - Gin’ = RTIn(y,,Xp,) - RT In(X,) RT in(y,,) = 11,083.1 In(y,,) GX(vmol) Gg = GE, -G 7" = RTIn (y,,X;,) - RT In (7,,) = RT In(X,,) = 11,088.1 InX,,) 2, Gis = RTIn(y,,) = Cha — Gr! = Win - 13%, - C3 = Q,,(1—X,,) + RTIN%y) — RTIN(X%,) = In(¥zq) _ 11,088.11n(,) (1-%a) (Xn) X cos | oro | o1s | ov | 030 | 045 | 10 P,, aim) cocass | oosse | ones | 02068 | soo | 12763 | 40 a o.cores | 00148 | oces6 | o0sse | ots | 0319 | 10 % oxaaé | 0148 | o197 | 0296 | 0500 | 0709 | 10 Tasuimoy | -54,634 | -46,695 | -so,012 | ~31,300 | -21,026 | ~12,663 | 0.0 a mop | -21.422 | -21.175 | -1a005 | 10480 | -reee | sett | 00 Ge (umoiy_| -33,202 | 25,500 | -21,006 | -17,98 | -13,344| -s850_| 00 Dy, 26,608 | ~28,142 | -24sar | -21,082 | -15,678 | -12,600 | undet () B22 decreases as X,, > 1 hence, the solution becomes eal with respect to Zn, The solution is regular for approximately 0.05 0:30. Data is insufficient to compute the dilute solution activity coefficient although examination of the table suggests that Y,, approaches a constant value (hence the solution is Henrian) below X,, ~ 0.05. [6.6] One mole of solid A at 1200°C is added to a large quantity ofa liquid solution comprised of components A and B (X,, = 0.8). The liquid solu- tion is also at 1200°C. If A and B form ideal solutions, calculate the Gibbs free energy change resulting from the addition of solid to the mixture, Assume C* (liquid) = C* (solid) and CA is independent of temperature. a/1{ = 24,000 J/mol at 1800°C. 102 CHAPTER 6 Soluion Since solid A is added to the solution, the heat of fusion must be included in the final result. Note that the notation G' implies that pure A is inthe same state of aggregation as the solution. This is not the case here hence, the Gibbs. free energy of mixing cannot be computed directly from GR = (1) RTInCX,). Equations characterizing the addition of A to the solution are: (hats AM aGl = anf ~ Tash (2) Ae +A Gk -Ge =Gi -(RTIn(X,) The result of adding A is found by combining (1) and (2): @) a 5A Gk-Ge Gk - GOS = anf -T/ asf +(1)RTIn(X,) At T= 1800°C, solid A melts, hence A084 AM AGL =O AG, =0= aH{-T/As{ AHL _ 24,000 T2073 a3, 1.58 J/(mol-K) Since AC, =0 from the problem stement, AH and AS{ are constants Substituting into AG{ = AHL -TVAs{ Gi Gz? = 24,000 ~ 1473(11.58) + (1)8.3144(1473) In(0.8) =4210J/mal. [6.71 The molar heat of formation of liquid brass according tothe reaction (1 = X)Cu + XZn —> CuZn is given by Hm = ~7100X(1 ~ X) cal/mol (Upadhyaya and Dube, 1977, p. 139). Determine the expressions relat- ing the partial molar heats of mixing of copper and zinc in liquid brass to the alloy composition, Solution ‘Since Qis a solution constant, it is applicable to the partial properties of both ‘components. Hence, HE, =-11000 -X,.; Ha T100(1 ~X,,) 403 WWTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS [6.8] The solubility limit of component A in B is 1.5 w/o at 760°C. Ifan alloy contains 0.5 w/o A, calculate the activity of A. Assume Henrian solution behavior in the composition range. Solution From [6-34] and defining b in terms of w/o, a (1.5) = 213(w/0) 3) 4, = 2130.5) =0.3. 0 atthe solubility limit: [6.9] Antimony isremoved from lead during the refining process by selective oxidation (Darken and Gurry, 1953, p. 513). Estimate the Sb content obtained for air agitation ofthe bath at 1173 K. State assumptions and use the following data: AG{if =~ 417,600 I/mol Sb,O, and AGP, = ~ 395,000 J/mol S6,0, (Wicks and Block, 1963, p. 13). Solution ‘There are two approaches to the problem. The first approach assumes direct, oxidation of Sb in solution by O,. The second approach assumes Pb is oxidized to PbO which then oxidizes Sb in solution, Both approaches are presented and the results discussed. For the purpose of comparing ap- proaches, assuine that Sb behaves ideally at dilute concentration. Method 1 (1) Sex Up 236) +940,(g) SEU» Sb, 0, (8) ze fae ae cai [ee 25b1) +40, ASHB> sb, 0, (8) (2) Sum ZAG, = 0= AGIr3 + AG, — AG, —3/24G, - 263," 104 CHAPTER 6 @) Substinte AG, = 0 (pure condensed phase) 4G p= 0 (equilibrium) 324G, = RTIn(73/2) 2G5; = 2RTIn(ay,) = IRT In(K.) Tofind AGY,s, use AG? = AH -7AS¢ and the given data to calculate AF and AS@. Assume AH@ and AS9 are constant between 1100-1200 K. Sub- tracting: ~ 417,600 = aH - 1100482 = 395,000 = aH ~ 1200482 22,600 = 100 as9 => aS9 = 417,600 = AHg ~ 1100(-226) ‘AHS = ~ 666,200 ‘AG =~ 666,200-+ 226T ALIIT3 K, AG273 =~ 666,200 + 226(1173) = - 401,102 J/mol 226, Substituting into the first equation, ‘Substituting into ZAG, = 0, =~ 401,102 - RTIn(0.21)*#— 2RTINX,) @ Save 401,102 2.27 Xa on a 2 ) exp (19.43) Xq=3.65%107 From Example Problem 6-3, (6-5b], _ 365% 10+ x 121.76%100 (10) = 365% 108 x 121.76 + 1x 207.2 = 0.21% 106 wo =2 ppb Method 2. (1) SetUp 25b (L) + apbo ( “85 3PbWW+Sb,0, (5) ag bn tf 2SbW)+3Pb0(s) PETES apy (2) +Sb,0,(6) 105THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS @) Sum BAG, = = AGlins + AG, + 36% ~ AG yn BAG, 268! @) Substitute AG, = 3G, = 0 (pure condensed phases) 367 = 0 (X,, ~ 1.0) AG,,», = 0 (equilibrium) 26%! = 2RTIN(X,,) Assuming Table A.4 data for AG3¥,,, is accurate at ~1173 K, {Gfiy = — 401,102 — 3-299 930 -33.68(1173)og(1173) + 209.64(1173)] = - 85,262 J/mol Substituting into DAG, 0 =~ 85,262 - 2RTINX,,) @) Solve ORTIn(X,.) = — 85,262 ie BS,28Dia 15 0.8 w/o = 8000 Ae es 0.013 or QB nie — Swen Discussion: The answer using Method 1 appears unrealistically low. In practice, the rate of oxidation of Sb by direct contact with O, at the surface ‘would be low because of the very low Sb concentration. Method 2 seems ‘more realistic thermodynamically because both Pb and Sb readily oxidize in air. Agitation would rapidly promote contact between PbO and Sb throughout the solution, [6.10] Show for a regular binary solution that _ Rrin(y,) “(x) Solution () Gf Wf -75? =9,(1-x,P -7[-Rin(X,)] 106 CHAPTER 6 Equating (1) and 2) and rearranging, Q(X =RT In(yX) — RT In(X) oF (x)= RT ing) = 9, = TINY), (xy [6.11] Show that if a solution component i exhibits ideal behavior at constant temperature, Vo#= 0. Solution By analogy with 4-14), dG = Var —3ar. ‘Atconstant temperature, dG" = VJ"aP or ‘Substituting [6-26] for component i, ‘aMx,) wf 2 [6.12] During low temperature-high pressure metamorphism, the albite com- ‘ponent in the mineral plagioclase breaks down to form the mineral quartz. and jadeite, a component in the mineral omphacite, Quartz occurs as a separate phase during metamorphism, hence do, = 1. Referring to Exercise Problem [4.22]: (@) Calculate AG, as.a function of temperature, activity ofalbite, a, in plagioclase, and activity of jadeite, a,. in omphacite. (b) Assuming ideal mixing, determine AG, as a function of tempera- ture, X,y, and Xp ve nx, Soluion (An ieahema op suse slows: (1) Set Up NGAIS,0, (@) 22x NaATE,Q,()+Si0, ©) AG, AG, AG, Nal Sin0,e) AS=>NaAlsi,o, (+Si0, (8) 107‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ©) Sum EAGy, = AG3 +AG, + AG, -aG,- AG, @ Substime AG? (mol) = 53.21 x 10? - 2000.4T + 238.21TIN(T) ~10:349 x 10°T? + 3.791 10? +17.478 x LOTS + 2460.4 x 1057 ‘AG,= 0 (pure condensed phase) AG,= RTIn(@,,) ‘Substituting into DAG,, = 0, © =53.21 x 10° 2000.47 + 238.21Tin(T) ~ 70.349 x 109 T? +¥3.791 x 104T? + 17.478 x 10° TS + 24604 x 10T +RTin(a,,)- AG, —RTIn@a,) @) Solve AG, (J/mol) = 53.21 x 10° -2000.4T + 238.21Tin(T) ee 70349 1077+ 3.701 x 10D + 17478 CIT + 2460.4 x 1077 srr) () Assuming ideal mixing, a, = X,, and ay, = X,,, hence 8G,(J/mol); 53.21 x 10° -2000.4T + 238.21Tin(T) 70.349 x 10°T? + 3,791 x 10*T? + 17.478 x 10°T*S + nana ors omre{ [6.13] Plagioclase feldspar, one of the most common rock forming minerals, exhibits complete solid solution between the pure end members albite (Ab), NaAlSi,O,, and anorthite (An), CaAl,Si,O,. Solid solution min- ‘eral compositions are usually given in abbreviated form, such as ‘Abj-AN, Which denotes a plagioclase of composition 40 w/o albite and (60 w/o anorthite. Show that the partial pressure of anorthite over a ho- ‘mogencous liquid solution of Ab,,An,, at 1350°C is: 6 Gian ~383R 1623R 108 CHAPTER 6 where Gi. isthe standard Gibbs free energy change at 1623 K for the phase transformation An(!) —» An(g). The molecular weights of al- bite and anorthite are 262.23 and 278.21 respectively. State assumptions. Solution (2) SetUp Frat) SE2> Ans) ben a An (2) SEb22 > Ang) = AG ing + AG, ~ AG ep - AG, 3) Substitute 4G, =RTInP,.) AG jaa = 0 (equilibrium) 4G, = Gi =RTin(a,.) = RTIn(X,,), sssuming ideal mixing. x,-—ta_-__ na) sg 79 Pa + Man 20(zhas) +80(zabar) hence, AG, = RTIn(0.79) Substituting into ZAGy, = 0 0 = AGRay + RT In(Pa,)~ RT In(0.79) @) Solve RTin(P,,) — RTIn(0.79) = -AG Seas tn(p,) = ~BGthas + @623,i00.79)18 1623R i, mexpl AG 383K) : 2=9| “Tae |Sssuming anorthite is stable inthe gaseous state at 1350°C. 109