solutions to Exercise,x sada chapter 1 1G= 22.64 + 6.28 x 1037 J mol1-1 © qT Entropy increase, AS — | o aT 7 Ty ae 22.64 + 6.28 x 10-37 oe AS300-1358 = | So 300 = 7300(22.64InT + 6.28 x 10-7] = 40.83 J mol "kK!MN Aly Schematic free energy pressure curves for pure Fe schematic free enetg, 1.3 From Equation 1.14 (d = AH \ai Jeo TAY Assuming AH and AV are independent of T and P for the range of interest, the equation may be rewritten as where AH =H" — HS = 13,050 J mol AV = V" — V5 = (8.0 —7.6) x 10-* m° T = (1085 +273) K Thus if ; 5 ie malig ee 10 kbar, ie, 10” N m~, the change in the equilibrium perature is given by the above equation as ; AT=42 K 4 Phases stabi (78) term hace ‘emperatures must have low enthalpies beot™* Le Pression for G becomes negligible. Phases stable *! higher entropies to." high tem, peratures, oy Sate for higher ce other hand, have! ] 7 and two white balls in a square is YS of atranging two Dak (Ne+Nw)! _ @+2y “NeNyl = soe =6 | | Six distinguishable configurations O Y 16 Dividing both sides of Equation 1.30 by the number of é (na + 1g) gives ' moles of solution 66 SF Te (natn) “A (ia tne) '® Gia +m) The left-hand side of this equation is the free energy change per mole of solution and can therefore be written dG. age (nat mp)yhase Transformations in Mey "8 ang 4 Al yn 1.3. ag Bqe ion ( paX HpXn G— paX b " AB dG G— paXa Ma : dXp B on dG Xp Ba erhaieg From the figure oe ; PR — Xp ) PQ = 0S = (os Le., point S, the extrapolation of the tangent to point R on the G-cu represents the quantity ju, Equation 1.6.1 gives : dG iy = Ba = Ba aXp ie, UV by = OS +—— B + us * But US =OT =1 Thus ie, poin Tepres © quantity ju, Point V presents the quanti Btion of Au = ; Mole fract Molar a folar entropy of — 248 jn 0.248 = 4.66 = 400) _g 3140: oealar free energy che (e) Molar free € AGmix = ~TAS Vee () pau=G ut RT In Xa = 0) + (8.314 - 773 = =8.96. Kj mols” pag = Gag + RT InXag 0+ (8.314 - 773 -In0.7 = -183 kj mol (g) For a very small addition of Au dG’ = 4, -ditau (T, P, ng constant At 500°C, au = —8.96 kJ mol? Avogadro's number = 6.023 x 1073 1eV=16x10 ~ 8.96 kj mol“! = __~8-96 x 10° _ eV atom 1.6 x 10-1 x 6.023 x 102 = -0.1 eV atom”! Addin, y —0.1 ev, 8 One atom of Au changes the free energy of soll!eo ution SP a ‘Ba 19 19 Free energy —~ae0 n + dG? =0 srium dG At equilit een A irdna + I ie, —PA p ie. bi simila BA A ane My for B, C et concentration cy 111 Fquilibrium vacan AGy XP =exP—-Ry7 ASy AH. Be a RD teV=l6x10 J + R=8.63 x 10° eV atom 1 3 0.8 ’ X5(983 K) = exp @) ep(s 63 x 10-5 x 933) = 3.58 x 10* pe —0.8 \ (298 K) = Sey be 3 a X<(298 K) = exp (2) - exp hes 10> 8) = 208 x0 1.12 Assume Xg=A exp — (Q/RT) vIn Xg =In ees At 550°C (823 K): In 1.25=In A — Q/(8.314 x 823) which can be solved to give Q= 49.45 kj mol A=17% Thus at 200°C (473 K) = 49.450 Xs, = 1721 . op-( or) =0.006 atomic’ According t | 'g to the phase diagram, the solubility should be slightly — OO aera te due to the long oe data is not available is such low temper Tequites to reach equilibri quilibrium.solutions to Exercises 3A sketch of the ral f } helpful in solving this pry Phase q iiy two figures, lem as gf and free AGa and AGp are as g a iN the figure ge"8Y Curves ig Since A and B are mutual ©) and (c), 2 curve G" at Xp = xE tually imm, But AGa and AGs can also be foul mes figures (b) and (c), from the relationships Sonnes: If Cs = CB, Equation 1.17 gives EB AG =>. AT or AG =AS, -AT430 (d) Schematic phase diagram T curves for pure A for pure B for the A-B system at Ty (a) () G- (¢) G-T curves (d) Free energy curves Thus AGa = ASmn( AGp = ASmn(B) - (Tm(B) — Te Finally therefore: Tms(A) - (Tm(B) — —RTgIn XE —RTgIn X§ or —8.314TgIn XE = 8.4(1500 — Tg ~ 8.314Tg In(1 — XR) = 8.4(1300 — Tg Solvi ving these equations numerically gives Xk = 0.44 X§ = 0.56 1.14 If solid oe Tg = 826 K a Sasas B *S Increased by an . ot radius r within a liquid, then its fees Ge 2a where % =~ (from Equation 1.58) Ci CG 's the molar free 1S the molar feeeue Of the sphere ‘ergy in the absence of interfacesolutions to Exercises Growth of the Sphere 431 Must lead to of the system, Le, gro 4 reduct;, Browth can ogo we Of the total free oh ler; Gi e i F See figure below Growth occurs spontaneously with 4 decrease in free energy 5 @ ' s i 8 ' aa € 7. s ee s = b ee [ieee ae ree a G. a Se a Ty a Substituting Equation 1.17 for Gt — GS. gives LAT _ 2yVin =o. IU r 2yVinTm rL ie, AT > Substituting the numerical values given AT(r = 1 pm) > 0.2 K AT(r = 1 nm) > 200 K 1.15 Composition = 40% A, 20% B, 40% C a= 80% A, 5% B, 15% C B=10% A, 70% B, 20% Cc y= 10% A, 20% B, 70% C | microstructure be Xq, in the final Let the mole fractions of a, B, and Y X,, and X,, respectively: a 20.4 = 0: - 0.2X, Balance on = 9.2 = 0.08%a + 0.7% - ; 7x, Balance on P: a 0a 0.2Xp + ° Balance on ~*~" 0.13; X, = 0.44 tions gives: Xe Solving these eq4@—_—_~ y se Transformations in Meta, Pha and 4 Al 432 * ind 1.43 we have pquation® 141 ar rom E« 6 Frot y= GatRTINY ~ ig the free enerBy of pure A at temperature T and pres, where Ga 57 own for a given temperature and pressurey, 2 | now 0a | suppose GA Ga(To-To Gh SadT + VmdP ie. ie, GA From Equation 1.9 for } mol of A aGc = —SadT + Vad sus if Sa and Vn are independent of 7 and P, changing a from Tp to T and pressure from Po to P will cause a total change in G, AGa = —Sa(T — To) + Vin(P — Po) Ga =G,+4G = G9 +Sa(To —T) + Vin(P = Po) and P) + Vin(P — Po) + RT InyaXa Ha = Ga + SalTo The accuracy of this equation decreases as (T - To) and (P— Po) increas Chapter 2 21 @) ee Sheet | Decarburizing gas 14 O15 Carbon concentration Thickness ©) Under st : fltsc 0, 24Y-state condi 4 i POUL Of the other ena son Aux of carbon atoms into oneios 4a 25x 10-0 0.92 7x Too diffusion Coefficient varies ling arly with carbon b¢ where a and b are constants that can be determined from tk ed from the date given. Fick’s first law then gives —o ] r+ 0c) ae or | Jax | + bC)dC J J Z wid bc* { 1 ie, —Jx=aC+—-+d fi 2 S ) where d is an integration constant. If we define C=C; atx=0 bo =-40,-59 Similarly, if C=C atx=1, the thickness of the sheet gives bapange 2h et | Se ae ts Gane bie c2 / ie = {a =) +3(G- @/ The constant a and b can be determined from le Cl D, =4at bCy D, =at 2 ie fom whichamie = a= Di - Biome andb=¢,-G1 1ee Transformations in Meta), Phase Transf als and ay, "ys 434 sions into the equation for 7 € BIVes pecuien of nese OF” BONES alte Subst! simplificatio p= 77x10 m8 Substituting: “1 ; Dp) =2.5% 10m’ s 1 i 4 60 kg m™ Ten Oe 0.15 + x 60 kg m™~ “2 08 2 p22 107? m J=24x10°% kg m™ | | ; —d gives Consider two adjacent (111) planes in an fec crystal. A vacancy in plane! can jump to one of three sites in plane 2. For the sake of generality, let is number of jumps be designed P (=3). In all there are 12 possible sites (nearest neighbors), If m and ny are the numbers of vacancies m~? in planes 1 and respectively, the number of jumps from 1 to 2 will be given by ek, = pln ms where T, is the j Lewis a frequency of the vacancies. re P = ic Tyna Therefore following the samy le arguments as in Section 2.2.1 sv Trois (Ep) aCe (Ze ry) bxsolutions to Exercises where d is the per r *Pendicular : ca ee SeParation of the adjacent p} Planes, ie, we D2 bate, Thess In fcc metals the jumps distance is given by a v2 where @ is the lattice Parameter. For (111) planes a 2 d=—=a,/2 Nc Putting P=3 gives Dy =seT, 1 6 For (100) planes, adjacent planes are in fact (200) ge ee 1 > + Dy =zale tiv! e y following equation ivity along the bar is described by the following The a Ap (- oa) Activity = P\" Dt where 4 Ao is the initial activity oe Dis the diffusion const tis the time bar on wi the disenee ama sgt tine of SOP 4D!) a avity) V8 71 3 ig known i: (activity. since Thus by plo’ im pe found ge produced, enablingphase Transfe mations in Metal, 4nd Aj = ai 50 2500 m) 664 " 8.74 247 activity 1 (activity 24+— a $1 0 1000 2000 From the graph: slope= —8.66 x 10-* pm. t 1 Hence: — @Dp~ = —8.66 x 10~ Since t=24 h D=334 x 10-5 m? 5-1 24 C=C Bysin(™) oxp—! For this equation t condition must be my, 2 oe 4 solution of Fick’s second Jaw, the following x xe oF sc See Eo wet £ I “7 Bx = Boexp—}. 7ay t } Ny exp. " i * nin mC Re | nT r) Y Oo” OF But » ! &¢ arc r dD i bt »5 (a) ACy eX ) C(x) oF ! shy 2+ Mex " 7 a+] where is the thickness of sheet Co is the initial concentration oi A \ / Nat / \ (x) | \ Ce / 0 : 1 0 1 : : 4 Beis » series are The first two terms of the serie Sax ! 4Co C(x) ax 1 + = sin sin +3 site. yes the curve plotted oppos! n for the range 0 <* < ee Oe we5 Plotting the sum ie eae 10k f -e concentra (b) If the surface cor a diffusion equation becom«ee Transformations in Metals ang 4 E Hoy yi 438 r obtained by puttin, t term (A1 Bx=1/9 tude of th first fet M2 ang e Aoi | a Dt A oF B term (Az) 18 obtained by putting x i "6 # of the second The amplitud! and |= 1 ber ie ae mh If Ar <0.05 At AC {—DF ACs | < 005 Pe Ff 7 | as hich gives t coro which gives t > 0.0*1'D 4 am? 57 ice., D(20°C) = 4.08 x 10 mm s for 1=10 mm; t;=19.2 h, for !=100 mm; t =1920h (80 days). Thus for != 7 =19.2 Bs et 48 (equilibrium) win equilibrium) ical ively the chemi , respective lation 1 and 2 of «and Pound Gregor At the initial compo in each ae jan ae id Bat {]lustrated. Potentials of A an energy Cv ct illus of the tangents to the diagram 4 ig Sides of the free energyDz, =5.1 x 1077 mm? Dé, =2.2 x 107 mm? s7) Exercises “yytions € SS ; a4 rhe expected variation of D5... De and py The € nr DE, 2 ne nee pelow : are shown schematical tically ams ae - “1 | 1 ie | b r I i | é Dou \ - | pee | f ———_|____, 47 cu Solubility limit for a Since Zn has a lower melting point than Cu, it diffuses faster of the two, and since increasing the zinc content reduces the liquidus temperature, all diffusivities can be expected to increase with increasing Zn concen- tration. 28mations in Metis aaa () a t a é se ee we fk Bulk composition (ii) So t g i « a (c) y