Solucionario Del Thermodinamic Loop Aplications in Materials Systems

PREFACE ‘This manual contains solutions to Exercise Problems presented at the end of ceach chapter in i ‘(Volume One). Although answers are given inthis book, the specific methods used to derive those answers are presented in this manual. Data not provided in problem statement canbe found in the book appendices. ‘Due to the difficulty in reading graphs or variations in the computational path used to obtain an answer, the reader may obtain slightly different numerical values (not regarded as incorrect) than those given. Likewise, certain assumptions made by the reader may yield somewhat more significant differences than those obtained using assumptions made in this manual. Again, such differences are not regarded as errors as long as the assumptions used can be justified. ‘Throughout the book, an attempt is made to avoid this difficulty by making plausible engineering assumptions wherever possible. As will be noted, data limitations are often the reason that thermodynamics cannot be applied in a given situation, ‘The authors have used great care to eliminate computational errors. How- ever, if any are found, we would be grateful to readers for information about such errors including misprints in both the book and the solutions manual. DONALD L, JOHNSON GLENN B. STRACHER (CHAPTER 1 Chapter 1 [1.1] Calculate the coefficient of thermal expansion, a, at 273 K for an ideal gas. BES RT [1.2] Consider the reversible expansion process represented by the straight line 1-2 in the figure below.The working substance is 1 mole of an ideal ‘gas, P; = 1 atm, P, = 2 atm, V2 = 2V; and 7; = 300 K. Find W for the rocess. p‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ae =2 7 Swe [Bir imts mar Pp GED. ney vy = DAS 104,617) pal = 36,926 em? aun, y, = RP _ 82.057 x 300 = 36,926 0.0242 4,184 a 7 = 3739 mol, 24,617 cm? /mol 7, = 300K [1.3] The generalized expression 6-4) ‘can be used to calculate C, ~C, for any substance. Show that C, ~C, = R for an ideal gas. [1.4] An ideal gas undergoes an isobaric change from an initial State A(P VT) to final State 2:(P,V9"T2). Prove V'- V;'= -T). CHAPTER 1 [1.5] Show that the total work performed during the reversible isothermal ‘expansion or compression of an ideal gas from a volume V;’to Vis ‘given by the equivalent expressions W’= nT In(V7V;‘) and W7= ‘MRT n(P fP,). W’ = ART in(P, /P,) [1.6] The reading on a pressure gauge relative to vacuum has to be added to ‘atmospheric pressure in order to determine absolute pressure, ie., absolute pressure = gauge pressure + atmospheric pressure. (@) Calculate the work done by 10 moles of an ideal gas expanding ro- versibly from 58.784 to 14.696 psig (Iby/in? gauge) in a piston-cylinder arrangement at a constant temperature of 125°F, Perform the calculation withow using numerical gas volumes at absolute pressure. Express the answer in joules. (b) Calculate the volume occupied by 10 moles of an ideal gas at 14.696 and 58.784 psig at a temperature of 125°F, (© Using the gas volumes obtained in (b), calculate the work done by 10 moles of an ideal gas expanding reversibly at a constant temperature of 125°F. Express the answer in joules. How does the an- ‘swer compare to the one in (a)? Why are they the same or different?THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution @) Absolute gas pressures can be calculated from Pass = Pange* Pan By in P, = 58.784 psig + 14.696 psi => P, =7a4eP ‘The work done by the gas is given by fom: ‘Since the calculation is to be done without using numerical gas volumes at absolute pressures, an expression for dV’ must be derived. Py = 14.696 psig + 14.696 psi => P, = 29.392 w Substituting for dV” in the work integral, Ps Ps PenrtP?)dP =—neT | 2 =—nerin| 22 a A % Converting 125°F to K, °C = 5/9(°F ~ 32) and K = °C + 273.16° =» K = 5/9(125°R - 32) + 273.16 324.83° Hence, 924.83 won 22) (©) From the solution to (a), Payuge= 14.696 psig, Paya= 29.392 Ibyfin? and Poroge™ 58.784 psig, Puy = 73.48 Ibyin? From the ideal gas law, PV’ = nRT = V’ = nRTP. (CHAPTER 1 comi(esma 2 Jonss%9 4448NY_1 107 em a ETS Vises = 0.133. m? aommen(s.3144 <7 \s2483%9) mm 4A48NY_lin (10? om nay Se a) m Vier = 9.053.m? (©) The work done by the gas is given by fox: ‘Since the calculation is to be done using numerical gas volumes at absolute pressure, an expression for P must be derived. w PV’ = nRT =5P = nRTWV’. Substivuting for P in the work integral, , “aye , 1 f''nRT, av" _ erin Ww j sont" RTI ) W’'= 24750. This isthe same answer asin part (a) because the path between identical initial and final states i the same. 11.7) Calculate the work done when the hydrostatic pressure on a cube of Cu measuring 2 em on an edge is increased reversibly and isothermally at (0°C from 1 10 100 atm. Assume a negligible change in V over the pressure intervalTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Solution ov: [eae Pav’ 16%10¢%8 om [2] “atm 7610-48 x40,000-1 =-0.904 em?-atm 0.304 em? atm -cal 41.32 em? -atm =-2.0815 4.184 Jieal w= 2031 em? ‘Sem? “896 gm ~~ mol = 0.027 Jmol, [18] Calculate the work done on the surroundings when one mole of liquid potassium expands to vapor reversibly and isothermally at 1000 K and (0.753 bar in a piston ~ cylinder arrangement. Solution w fav L_ 83148 39.10kg 753bar(2592 1493) gg 831K Me! eg WB 144L- bar ® ‘kg mol 127 Keg mol [1.9] Caleulate the work done (internal compression) when a 350 Ib mass of low carbon steel transforms from (austenite) to cr (ferrte) during an air quench. Given that V, = 0.0486 nm? and 2V/; = 0.0493 nm’, the basis for these volumes is 4 atoms of iron (one unit eell of y or two unit cells of a [Van Vlack, 1985, p. 76)). CHAPTER 1 weer [ ar” whee P=1 tr 008860 = 0088 on? ° 314s Aft! 10483 = 0.0886) amas “10 ram?” $3,057 em® bar 522410 atoms, 350 bg 4535 bg a9 ‘gm: mol, ‘55.85 gm/(gm-mol) [1.10] Calculate the isobaric temperature change necessary to produce a molar volume change of 0.02 cm/mol in a pyrope gamet, MgAlSi,032,crystal. Assume GV t,x i Constant over the temperature interval. Solution Tal) Vio08 \OT Jp AV = OV 95 AT = LK AP F910 em mor-R) SK where Vita. 298 = 113.18, OV, 290 = 2.98 10°, UL.11] Calculate the molar volume of the pyroxenoid wollastonite, CaSiO,, at ‘a pressure of 200 bar and temperature of 298 K. Assume IV yar 298. is ‘constant over the pressure interval. The inital pressure is 1 bar,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. V; =3993 cm'/mol-3.6x10-5 2 ? ol: bar (200~1bae 39.93 ~0.01 = 39.92 em? / mol where Vi 295 = 39.93, BV;295 = 3.6 x 1055, [1.12] Express (4P/@P)y in terms of the volume thermal expansion (a) and isothermal compressibility (B) coefficients of ammineral. Assume Accand 4B are negligible for small changes in P and T. Solution V=fPD) {1.13} Calculate the pressure on a crystal of spinel, MgAl;0,, heated cchorically from 273 to 308 K. The pressure at 273 K is 1 bar. Assume negligible changes in a and over the P-T interval, The volume re- ‘mains constant because of external constraint Solution Rearranging and substituting where a; a9¢= 1.03 x 103 em*moF-K), BV z94= 1.9 X 10°5 em*/(mol-bar) 1.0310" em?/(mol -K) 2 * 1.93107 em®/(mot-bar) OO8- 799% = 1+ 542,12 = 543bar. [1.14] A beam in a truss bridge is subject to uniaxial tension and compression (0) in such a manner that the beam undergoes infinitesimal changes from one thermodynamic equilibrium state (T;,0;) to another (T,0;). ‘The total differential of the dependent variable e involves two parameters known from experiments to be nearly constant for small temperature changes. These parameters are the coefficient of linear thermal expansion cand Young's Modulus £. Mathematical definitions and addi- tional experimental properties are as follows: a= (2). cis nearly independent of B= (22) forthe ease proportion ini a Jr (a) Write an equation of state forthe beam as a functional relationship, () Express the exact differential of ein terms of rand E. (© Show that if eis constant, (201d T)_= a. Solution (@)Since eis the dependent variable and 7 and o are independent variables,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS and substituting from the problem statement, 1 ae=oar+(2 (E)e0 ©de=0 oer (2 0 [1.15] Beginning with the expression P = f(V,7) (@) Express the total differential of P in terms of partial derivatives and ‘name the partial differentials. (b) Use the condition of exactness to demonstrate that dP is an exact differential, Solution (a) Applying the chain rule to P = f(V.7) (a), Se Sa (b) If dP is an exact differential, the condition for exactness must hold true, Applying the condition to a) (ae (Fee 42) 22(2)| -2-= ar|\ov J, |, av (ar), |, > stay — aver 10 CHAPTER 1 [1.16] Uniaxial tensile first cycle stress-strain loops for the magnesium alloy Dowmetal A-T4 are illustrated below. Small partial cycles beginning at the lower end of each loop are on a constant slope of modulus E = 6.5 x 10° ksi since the first part of each loop side isa line parallel to the origi- ‘nal modulus line. For each such partial cycle, assume total elastic return ‘upon the removal of stress, Compute the total work performed in ft- Iby ‘when a 10.0 in, long Dowmetal A-T4 cylinder of radius 2.50 in, under- {g0es the partial cycles for loops 1 and 2 shown. (@) Loop 1: 0 = 1 ksi, 02 = 5 ksi. (b) Loop 2: ¢; = 2000 pinvin, ¢, = 2500 pin/in, First cycle uniaxial tensile suess-strain curves for Dowmetal A-T' magnesium alloy. Loops 1 and 2 are labeled. MII = microinches/inch. (From M.H. Polzin 1951, Fig. 9 with modifications. Reprinted by permission of the Society for Experimental Mechan- ies, Inc, Bethel, CT.) Solution (@) Given 6; = 1 ksi, 0) = 5 ksi, B= 6.5 x 10° Ibyin? W, =~] ode (work per unit volume) thus w ~v fou (assume ¥”is approximately constant) "4THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS o s 1 Pen GS dea Fedo and thus 1 ~8(2.60 in)?(10 in) hy Wy = R250 indAC00 in) ff 499 Moe) * Barwa ° a) ( 021 wy Ibe (b) Given: e = 2000 pin/in, ¢, = 2500 pinvin, E = 6.5 x 106 Ibyfn? a Ws ~V foten-ve ft a VE, VB hs = -e#) vy sean, 65x10" Bex {(2500x 10-4) - (2000. rom Zt) 119.7 ft-Iby ‘The work is negative, hence work is done on the cylinder, 12 CHAPTER 2 Chapter 2 [2.1] Calculate the transformation enthalpy forthe isothermal transformation of Ti(B) to Ti(a) ifthe transformation occurs 200°C below the equilibrium transformation temperature during cooling. Solution (1) Sap AHt Tid p Treas? STi AH Ou, Aes p =1SeK Ti Sum My, == AM + Art, — ArT, ~ Ay = HT AHS = AMM, + AH, ~ AH 3) Substitute AH, = -3473 Himol 55 AH, = fe 09 +10.04 x10" T) dT = - 6536 J/mol 58 MM, = four = -$782 J/mol 155THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS: [2.2] Derive an expression for the heat of fusion of Si as a function of temperature at 1 atm pressure, Solution (1) SetUp Aut Sits) PFE SiC 2) AH, An, | Auf ; Si(s) Ft Si (2) @ Sum Ally, =0= AIL, + Al, ~ Blips ~ Ally AH, = AH, +H, ~ AH, ) Substitute i athe [assur 2ALSi0,6), Use the following information (all phases are Solids): (2) 28i0, + 3A1,0, > 1Si,0,, (@)2ALSi0,+AL0,>A1 $10, AH2g= Solution (@) 2810, + 3AL,0, -> ASLQ,. Miby =-226 (©) _R8i:O4y -» A140, + 2A1,5i0, Alig =394 75i0,()¥2A1,0,()-92A1,510,0) Aly =168 Wiad Aloe ki/mol SiO," [2.6] Calculate the standard enthalpy of formation of CaCO, at 298 K in ‘kcal/mol and kY/mol from the following data: (@) CAO) + COJg) > CACO) AHSy= -42.85 kcal/mol (b) Ca(s) + 1/20,(g) >» CaO(s) AHSf = -151.50 kcal/mol © CG) + 0,8) > CO) AHS = 94.05 kcal/mol Solution (aVTAOQ+EO2) > CaCO3(3)_ AM Sy =-42.85 kcal/mol (©) Cals) + 1/20 26) PE2OKQ) AIRE = -151,50 kcal/mol OCU) +020 > E0Q. AHS =~94.05 kcal/mol Cals) + C(s) +320 2(g) > CaCO3(s) AHBE =-288.4 kcal/mol AHSsf = 288.4 kcal/mol = 1207 ki/mol. [2.7] Given att}! =-1133 ky/mol O, forthe reaction GAB)AKS) + 0,(8) = (2/3)ALO,(s), (@) Show AHBf =—1133 ki/mol it AC, ~0. () Select the correct alternatives below for A/S 18 CHAPTER 2 (I) 4AI(6) +30,(@) = 241,09) AH = 1133 ki/mol O,, (2) 2AI(6) + G/2)O,(8)= ALO) AHP = -3399 kJ/mol AL (3)4Al(s) +30,(@) = 2A1,0/3) AH?! = 1700 kd/mol O, (4) 2AIG) + G2)O,e) = ALO,(s) AH}! =-850 kd /mol AL (5) 2AI(s) + 3/2)0,(@) = ALO,(s)— Hp! =-1700 kJ/mol AL Solution (a) Aue! = AHL + | AC,dT WAC, =0, AnD = ASL =-113313/mol O, AHS, = ~1133 kcal/mol O, ifAC, =0. (©) Reaction (1) = 3 x [4BANGs) + 0,(g) = 23A1,0,(5)] $0 for reaction (1), AH = 3(-1133 kU/3 mol O,) = -1133 kJ /mol O, Reaction (4) = 3/2[4/3AN(5) + 0,(2) = 2/3A1,0,(3)] so for reaction (4), AHP = 3/2(-1133 kI/2:mol Al) = 850 kI/mol Al. Correct alternatives: (1) and (4). [2.8] Fifty grams of the mineral ilmenite, FeTiO,, are heated in an insulated furnace and then quenched in a 500 gm copper vessel containing 200 gm of water. The temperature ofthe water and vessel both rise from 30°C to 65°C. To what temperature was the ilmenite heated prior to ‘quenching? Solution 1 mol 50 gm ilmenite = 50 ¢m (ieee) = 0.33 mol ilmenite sgn «tb eo(!22) «nomen Amol 500 gm Cu = 500 gm. (a2) = 7.87 molCu ‘The initial temperature of the water and Cu vessel is 30°C = 303 K. T= the initial temperature of the ilmenite, The final temperature of the water, Cu 19THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. vessel, and ilmenite is 65°C = 338 K. ‘The heat lost by ilmenite = heat gained by H,O and Cu vessel. [inl = Qiio + 2%. [info 8 fees 1661+ 18.24 x10°T — 20,04 x10°T*)aT a = 15,307.08 + (8.487 + 0.0037° + 661,320.07 Gio(D= [Mh r0y9s 44.40 =29,30830 y= [Berar -s6raexio*rssanxtor 1.0067 «10°7-°5)aT =630521 Equating [Qin] with fo and OG, 15,307.08 + (38.487 + 0.0037° +661,320.0/1) = (29,308.30 + 6:305.21), [2.9] Calculate the final temperature and enthalpy change of the mineral ga- Jena, Pos, when 253.62 gm of the mineral at 80°C are placed into 58.73 ‘gm of adiabatically contained water initially at a temperature of 27°C, Express the enthalpy change in cal/mol PbS. Solution 1 mol 253.62 gm galena = 258.62 em (55-557 = 1.06 mol Ps 1 mol 58.73 gm H,0(0 = 58.73 gm (zs) = 3.26 mol HOW) ‘The initial temperature of galena is 80°C (353 K) and of H,0 is 27°C (300K). Let 7, the final temperature of galena and HO, ~Gipteor = Viigo ‘Since for a constant pressure process Q’ = AW, CHAPTER 2 1 1 -foas mone er -[o 26 moh ar. Expanding, hss en 7 ~ [c00ysseasreaoxio*nar = [26crssnar hss ho o 216.611, + 8.20 10°7} = 86,369.67 Solving for 7, T= 38K = 36°C 09 Ms) =—MHaso9 Jo2osanar ue = Aili Ais 706 mol {2.10} Calculate the heat absorbed and standard enthalpy change at (a)373 K and (b) 373 K < T < 800 K resulting from the dehydration of the min. cal serpentine, Mg,Si,0,(OH),. i the presence of quart to form talc, Mg,Si,0,,(OF),, Use the heat capacity for H,0() in Appendix A, Table ‘ABA and the heat capacity for H,O(e) in Appendix A, Table A.3B. The reaction is: Még,Si,0,(OH),(3) + 2Si0,(6) -> Mg,$i,0,(OH),(s) + H,0). Serpentine o-Quartz Tale Solution (@) Incorporating the H,O phase change in an isobaric TL: () Setup Mgg Si, Os (OH),(8)* 25:0, (6) Stary Mg Si, (0H), (5) +4,0(9) Alls 20H, Aly Ally ney A tan Z Maggi, On(OH), 42810, 2) HIM, Si, 0n(01 (0+, O68)THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Sum YAM, =0= AH, + AM, + AH, + AH1,+AHl,~ AH, ~2AH,— AH, G) Substite Alte x = L nd ih x (Products) ¥ nA « Reactants) AH, (Ki/mol) = (1)(-5915.9) + 1(-285.90) - 1(-4361.66) —2(-910.7) -18.74 k/mol AH, = le par = [73 Aa = 5658 Ynot AH}, = 41.09 10° Hol alte [cf aro ait, <0 t= [oper = [Bosas-san actor 27290007 169.26 x10°T"* + 4021.1x10°T*)aP 1047.6 Yimol 20H, = [oper a2| aso m9six10°r-1oo1be10°T har = 7038.15 on 7 a= fcenar = = 144.76x10°F 1093210874 [legrar= PP ons0-1e.z6010°1 -o3s2x10%r ++449.99x10°T ar £22,031 Stool ‘Substituting the previous data intoZAM,,0, 0 = 18.74 x 10° + 5658 + 41.09 x 10° +0 + 3047.6 ~ ArT, —7238.1 ~ 22,031 @) Solve = A/D yg = 1787 Jno} (b) Applying a second isobaric TL: 22 CHAPTER 2 Q) SeLUp 4 gy Sig Og (08 (25:0, (8) > Maggi 0,(01,60 +109) Aly ZH, lan, (AH, an, Mas Sig Os (OW), +2 $10, ) 7% Mags Sig Oe (OH,6)* HG) Serpentine Quartz. Tale @ Sum EAHy, =0= AH, + AH, + AH, ~4H$~2AH, ~ aH, @) Substite |AET},~ 1787 Smo (from Part) ant,= [7 char = [(yacns21.assxt0 14811710777 43.6174 x10 TS — 22.316 x10°T*)dT 1603.9 x 10°F" 13,734 x 1047? + 7.3687 + 223,1607" + 723.487" 19,147 [p= [fos.s-snasio%rezrai09 169.26 x10°T-¥? + 4021.1 x10°T)aP or AH, = 909.7 x 10°7°-2635.85 x 10°7? + 5653.67 — 4021.1 x 10°71 1538527" natty [20g =afluasos 9sixi0°7- 19183408 )ar 2.AH,= 37.154 x 10°F? + 89.207 + 20,036 x 10°F" — 43,896,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Jr a. alt= [cpr = [(99.60~144.76x10°7 —1093210°7 9 bn hs $449.99 10° ya or AH, =~12.38 10°F + 899.607 - 499.99 x 10¢T* x10 ‘Substituting the above data into the expression for EAM, = 0, = 1787 +€-1603.9 x 107 + 13,734 x 10“P? + 7.3687 2231607 + 723A8P— 19,147) + (909.7 x 10°71? 2635.85 x 10°F? + 5653.67 ~ 4021.1 x10*T"— 153,8527°9) — AHP — (37.754 x 10°7* + 89.207 + 20,036 x 1057" 43,896) ~ (72.38 x 107° + 899,607 — 499.99 x 10°74 - 21,8647 + 108.85 x 109) 21,8647 + 108.85 (4) Solve Solving the expression above for A/12, AHS (mol) = ~69.42% 107 —2.597° + 4672.27 -3.10 x 107 131,2647°5 — 82,315 for 373 K < T < 800 K. [2.11] A high pressure mineral reaction occurring in some rocks buried to depths ‘of 30 km or more within the earth involves the decomposition of the ‘mineral albite (Ab) to form the minerals jadeite (Jd) and quartz. (Qz). Calculate the standard enthalpy change at 298 K for the albite decomposition reaction: NaAlSi,0,(s) > NaAlSiO,s) + Si0,(). ‘Ab i a-Qz ‘Alte = Endl Products) ~ ¥ nAHS Reactant) ‘Alfing (KI/mol) = 1(-910.7) + (1)(-3029.4) ~ (1)(-3935.12) = Sbimol, [2.12] Using the standard enthalpy change computed for the reaction in Exer- cise Problem {2.11}, calculate the standard enthalpy change of this reaction at T where 298 K < T'< 844 K, No phase changes occur. 24 CHAPTER 2 Solution () Set Up Na Al SigOg(s) ==> Na Alsi, O, (3)+ Si O,(s) ‘Ay Ah ‘AH, Na. Al Sig 0, (s) =S#PNa AISi, O6) + SiOz (s) Albite, Tadeite Quartz 2) Sum TAM, = AMS + AH, + AH,— AHP —AH,=0 AMS = AH, + AH, + Ali, — AH, Collecting terms and applying [2-16] and (2-17): ) Substinte 1 Hf m0) = B41 + fice +140.749.10-°7 —49,91«10°7? hes -227.22.x107T? + 43.692.x10°T* yar 980 ~ 238.217 + 70,986.58 + 70.37 x 107° 6249.54 + 49.191 x 10°T = 16507.05 ~ 75.74 x 10°77? + 8738472 @ Solve Up (Jimol) = 53.21 x 10? — 238.217 + 7.04 x 107? ~ 7.57 x 10P + 4.92% 107+ 8.74 x 107, [2.13] At 1356 K and 1 atm pressure, the following exothermic reaction occurs: 2Cuil) + (12)S,(8)—> H-Cu,S(9). Calculate the heat evolved and enthalpy of formation of #Cu,S(s) at 1356 K and 1 atm pressure, Use the heat capacity for $(g) in Appendix ‘A, Table A.3B. Hint: begin wih the reaction 2Cu(s) + (1)S,Ce) > Cu,S(@). 25‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution CHAPTER 2 [2.14] Calculate the standard enthalpy of formation of methane, CH,(g), at 298 K in ki/mol and kcal/mol from the following information: @ CH) + 20,(g)= CO,(g) + 2H,0(8) AHS, = -890.36 1d /mol ©)C@) +0,@) = CO) OH) + 1120) = 1,0) ANSE = -241.814 ki/mol Saup 2aMy ane 2eulebrgae? 2Ca+ 4 S,(g) —— FE $+ Can $0) Sars 2 any cu, AMscdisie DBs [any a custerette cused fas, ant 2Cu(s) +454) —— SH —____.cu, Sta) sure. ©) sum TAHy, = O= AHing + AH, + AM, + AH, + AH, + AH,~ AHO, 24H, — IaH, ~2aH1, hich upon rearranging gives AltSy + AH, + AH, + AH, + At, + A, 2d, 1P2AH, - 2AM, G) Substinte The data from Appendix A, Tables A.1, A.2, A3A, and A.3B is substituted in aH, above: AHR. =U1 mol(-80.15 ko) ~0.5 mol128.49 io) +fopsar.. 0809 smons [i eoomar 6 +1 (836.8 imo!) + ip 31 CSP aT ~2 (13.054 Kimo!) [Rescpean—[2ope @) Solve Upon intergrating and completing calculations, 5 am = Ale = 108 Ki/mol Solution (@)CO;(g)+2H,0(s) = CH4(s) = 20,(2) AH S55 = +890,36 kI/mol CLs) +05(6) =CO4(a) AHS = -393.51 ksimol 2% (c)2H(g)+05(g)=24,0(@) AHO = ~483,628 K3/mol Ce) 244(¢)= CH) AHO, 29 =13.22 Knol 2 yg =13.22-_ x 1eal__ 5 1p Keal ANG, aoe = 13.22 Tx Tagg = 32 An9f = 13.22 .ymot= 3.12 Kealimol, 12.15] The enthalpy increment for element A at two temperatures is given as follows: ics) HE — H%9(0 mel) 1000 1750 700 640 Determine the heat capacity of A which most accurately reflects the data given, Solution 2000 Eqn 1750= fe +o) 500 09 Eqn2 —640= | (a+ bru 500 1750 = a(1000 ~ 500) + (6/2{(1000)— (500)"1 {640 = a(700 ~ 500) + (62){(700}- (500}2} ‘Simultaneous SolutionTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. and expanding: a=20 103 2.02x10°7, Cf (dol) [2.16] Derive the formula 7 Ady, = AH, = | Acar where (@) Atty, and Atl, are the constant pressure molar enthalpy changes ‘of a teaction in staes 1 and 2 respectively. (B) No phase changes occur between states 1 and 2. (©) Allreaction components exist as one mole inthe balanced reaction, Solution () Sep Abr 1A +18 ——* > IC +10 {* a) ‘ate Paty IA +1B —aa_ > IC + ID State 2 (B12) STATE 1(P T,) Sum Elly, =0= Aly, + Ae + AH ~ Ally, = AH, ~ At Alig, = Ally, + MHe + AHy ~ AH, ~ Hy 3) Substitute 5 ek a, + [se [ea ferefer A ds a My wats [cp oe2 cfc B Let AC, = ZC; (Products) F.C (Resctants) My, 28 chapren2 Hence, AC, = NCE + «VC? -enck «nc @) Solve ; aig fee [2.17] Confirm the internal energy change for the transformation of potassium from liquid to vapor phase at 1000 K and 0.753 bar. Solution From [2-4] and Table D2, =Py Differentiating at constant pressure, ° Ih— Pdv — >t” du= Integrating, hp a= fas fn-o fis 4 ty dw 2760.4 ~ 812.6 ~ 0,753(2592 ~ 1.493) x 1/10 1753 kg, [2.18] A 20 kg mass falls 10 meters at constant velocity, thereby causing a ‘paddle wheel to stir 500 gm of adiabatically contained water initially at 25°C. Assume for the water a negligible change in volume and that C, = CG. (8 Find the internal energy change and temperature of the water after the weight has fallen 2, 4, 6,8, and 10 meters. (b) Plot both internal energy change and gravitational potential energy ‘versus temperature, What does the plot suggest?THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS \— Fricioless Pulley 1om—>| omy, 14 sabato Conainor 20 kg eee 500 gm #0 500 gm( e001) 27.78 moles HO Solution (@) Work-Energy Principal: As the 20 kg mass falls its gravitational potential ‘energy, £,, decreases and is converted into rotational kinetic energy of the paddle wheel, ‘The paddle rotates and does work on the water, thereby ‘changing the internal energy of the water as follows: AE 5.20 kgm =~ AUit,0 = + Wino (20 k)(9.81 m/s?)h= (196.2 Nh Ep = msl E.301 = (196.2 N\(10 m) = 1962.0 Distance Fallen = 2m: h= 8 m AE} = (196.2 NY(8 m)~ 1962.0 J = =392.4 J AU" = -Wyy = 382.43 105 )=3924= | non Mar= [Erma asanar Jo Ig 27.7875.444T 8, = 392.4] 30 CHAPTER 2 3924 (27.78)(75.44) or T=25,19°C +298 = 298.19 Distance Fallen = 4m: k= 6m AE, =(196.2 NX6 m)- 1962.0 J AU’ = —Wyy = T8A8J AUy ()= 7848 = Jer780 Aad 7848 =29837 TK) 20057728 2 oT = 2537°C Distance Fallen = 6 m: h=4m AE; = (196.2 NYA m)~ 1962.0 J=—117.2 5 AU’=-Way = 1177.2) 2 aU; =u1T12= [ar srs4yar 1177.2 298 =298: T(K) 20057" 8 56 or T= 25565 Distance Fallen = 8 m: h= 2m (196.2 N)(2.m)~ 1962.0 J 1569.65 Distance Fallen = 10 m: h=0m AEs = (196.2. NYO m)~1962.0 J = -1962.0 1 AU’ = —Waq = 1962.01 7 a, 0)=19020~ foraesaner 31THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 1962.0 2095.7 +298 = 298.94 's al 2D wma. 3a & Pistance Felten & (3) aut =~ wig (3) Te) oe 1962.0 0.0 25. ~ THE ig / 1370.0 2024 a: 3 wo re jaa 2. 2 yeas 790 3s. So 392.4 isto. 3s. 2¢ o:3 8420 38 ay eA. linear plot- consistent with Gya constant oo 32 CHAPTERS Chapter 3 [3.1] Prove that PV? is constant for an ideal gas. The process is adiabatic, Let 7= CC, Solution dU = 80-8W=-Pav 62=0 20) gy (at cau =rvsn-au(2) av (22) ar sic U = ol fran gas (22) = ns wv PAV =~ C,VaP = 6, 9)‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS yt ve RG ve G4 hence oY Ee FEMS = BS Vy oF (AEM 2H1,S(g) from 300 to 800 K in 100 K increments. Plot the entropy a.a function of temperature. What is the significance of the plot? Solution S,(6): Sta g( Amol 1] = 83.4, gat = 228.17 “f woe se 83 10 * (Sto Sanaa) 1 = 228.174 fosr0e 3.4459 x10 7 4 6.9404 x 1077? ss 2.3124 10°75 ~2.2639 x10°T?)a0 /T =228:17+47.0691o( 57.) 2.4850 10-(7-208) #8.4702% 10-"(T? ~ 2088) stesso de-gig)euanocie (ht) Substituting for Tin the above expression for SP 5 ¢). For S2(s): (motor sig) = 22839 IK (I mol) Sb (1m Sox) = 23798 (1 me) y— gg) = 257.71 (1 mol) 5(¢) = 245.70 34 CHAPTER 3 HB): Souq lI Amol 1] = Sane) * (Stent) ~ Saga) T copale) 130684 J oar Ps 130,68+ Joao + 11.07 1077 — 13.899 x 10777? 44.1017 x 1097-98 -51.041x107-)d7/7 10068 -1atean( Ee satenet0s-208)-6080010°% (r2~2988)-8.2094x 10 Gpr- aap) * 25521 107 Substituting for T in the above expression for 5? y,.y+ For Ha(g): 2mol)SSeny)=26LT4 IK (2m0I)Seoqnjq)= 27848 C@mol)Sgoqy4q)= 29152 EmoI Sin (2 mI)S25 44) =311-26 (2m01)S3on 4) = 391-12 1,$18): Si nagf9A01-K)]= Sony + (Shryng~ Sean) te) * (29374 1540%10°7 gee esa f (esesrsS 10ST -osin- oat Ig 08 a =205.80+ ann 2) 150% 10°(r-298). Substituting for Tin the above expression for 5° ys Forlt,S() (2rmol) Says) 412.08 IK (2 mol) Soci) “492.04 @ ee (201) Shay) =448.22 2H(e)+5(g) > 2H5(g): AS = 25} uy — Ship) 289,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘T=300K :as” 400K 600K :as“ =-92.36 WK ‘TOOK : AS“ =-94.83 500K :AS* =-89.00 800K :AS* = 96.62 ° AS‘eacion VS T CK) 1 3 if | ) - doe aL ees LL lL ‘800 TEMPERATURE ( K) —> ‘The plot shows that AS*™(reaction) decreases as the temperature increases (Since Vinéys < Vocus)» The volume effect on AS becomes less dominant. [3.3] Compute the standard molar volume change for the reaction in Exersise Problem [3.2] from 300 K to 800 K in 100 degree increments, Plot the {entropy change of the reaction as a function of molar volume change. ‘What isthe significance of the plot? Solution Assuming ideal gas, Pv Rr “Pr where V* is standard molar volume of an ideal gas. _ 82.057em? sa i ) mol-K (Tatm| 82.057em? rmal-K (1) CHAPTER 3 82.057 on? ‘mal-K 400K : V* = 82.057(400) = 32,823, 500K : V° = 82.057(500) = 41,029 600K : V° = 82.057(600) 00K : V° =82,057(700). 800K : V* = 82.057(800 (300 k)=24,6171 2 100K 2 2) + (a) 24, S18) A= i 94) MG) OB) 800K :aV* =-24,617em*/mal 400K :aV* =-92,28 500K :aV* =-41,029 ASRenction VS AV peaction 600K :AV® =~49,234em?/mol ft ¥ Bo} i 1 =e 5S 40 =30 =20 AY? (em¥mole) The plot shows that AS™(reaction) decreases as AV? (reaction) decreases. ‘This is consistent with the reduction in volume associated with the reaction as it proceeds in the direction indicated, [3.4] Use the entropy criteria to prove that liquid tantalum will solidify if the surroundings are at 20°C. Assume that the melt does not supercool. 37‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 24,588 3.02 7.56 + 88.92 = 76.36 J {mol- K) > hence, Ta will solid. [3.5] One mole of low carbon steel at 900 K is quenched and held in contact, with a large reservoir of liquid lead at 700 K. (2) What iA forthe steel, forthe reservoir, and forthe universe (AS,,)? Use Cp° and assume that the reservoir is sufficiently large to ‘maintain constant temperature, (b) If the steel had been quenched to an intermediate temperature of 800 K, then subsequently quenched to 700 K, what would AS, be for such a process? Note that during the quenching process the steel 1s placed in contact with reservoirs at consecutively lower temperatures. (© Explain how “equilibrium quenching” could be approached. Solution @85p, = A844 =f" Lar =o =-4.395 ~4.96 = -9.36 J /(mol K) » “tg, [9 -ousrar Po 5—— = 4,997 + 5.669 = 10.67 J Amol-K) 85qq 9901087 = 1.31, Ant 1) (ty, = [OEP op, PA =— 2.06 - 2.335 - 4.96 = — 935 CHAPTERS [Beers coarer [hans oarer 800 7 700 2180+ 2685+2490-2. 607-298 MSu = ASy, + Sy, =-9:95+ 9.98 mol-K) (©) From ») and b), its noted that one intermediate quenching reduces AS, by more than 0.6 J/(mol - K). By quenching through ar number of intermediate temperatures, equilibrium quenching (AS,.,= 0) could be achieved. In practice, this is an impossible process. Likewise, there is no practical reason to achieve “equilibrium quenching” since the objective in {quenching i to obtain a non-equilibrium microstructure. [3.6] Calculate AS,,,, AS,,,, and AS,., for the isothermal solidification of lithium at 453°K and T atm pressure. Assume T;,,= Ty 2929 TT 458 = CAH?) _ 2089 _, (mol 5p, = CS) _ 2888 — 6.47 sinol-K) 647+ 647=0) = 2647 JKmol-K) Swe [3.7] Calculate the entropy change of: (a) the system, (b) the surroundings, ‘and (¢) the universe (AS.,) for the isothermal solidification of 1 gram ‘alom of Al supercooled 130°C below its normal freezing point. Assume AC, = 0 over the supercooled interval. Is the process spontaneous? 39THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution (1) Set Up Applying one loop for AH and AS: Al) —Stem=-2H" Alley a33k t DSqq32 ASS t AH,2° Alo A520 As,0 | Altes = “anf AW FF Sake AL) ASqg= “Ast sum LAlly, = 0= Aggy + AM, ~ Allyy, ~ AH, Adgos = Ay35 = -10,461F / mol EAS, = O= ASiyy + AS, ~ ASyay— AS, ASso3 = ASy3 (3) & (4) Substitmte/Solve {3.8} | Repeat Exercise Problem (3.7) using heat capacity data from Appendix » Table A.3A. What isthe percent error in AS, assuming AC, = 0? Referring to the loop in Exercise Problem (3.71, EAH, = O= Allyg, + Alf, ~ AHyyy ~ AH. 2 = =-10,461~ f (2067+1239%10-%7)ar+ {202947 is es CHAPTER 3 10, 461~5483 + 3808 =—12,136.J/mol EASp, = 0 = ASyoy + AS, — ASyay - AS, aaa = ASys3 ~ AS, + AS, 9 (20.67 + 12.39 x10) 8, (8854 = ASgn =—t1.2t— [COTA PSO pF ag AP 11,59 + 16.11 ~3.58 imol-K) > 0 spontaneous 3.58-1.82 Tag *100~ 100%. 13.9] Calculate the entropy change for the vaporization of potassium at 950K and 0.447 bar. Illustrate calculations using two methods. Solution Method (1) KQ)K(v) ase = 2.08 kkg-K) Method (2) 950 = 2.08 kSMkg-K) [3.10] Use the entropy criteria to confirm that liquid and potas in equilibrium at 950 K and 0.447 bar. Solution BS = AS yy + 85,0, (2750. 950 4 = 4.8129 — 2.7313+- 71) ~0.THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS [3.11] A single crystal of the amphibole tremolite at 298 K undergoes a vol- ‘ume expansion of 105.5 x 10 cm"/mol during heating at P*= 1 alm, (@) Calculate the wemperature shift associated with the volume change, Assume Vy ayy 8 Constant over the temperature interval (©) Use the result from (a) to calculate the corresponding change in entropy. Solution oT (b) Since Pe = Sr -maKe1249 K=31009K s= ["oauesaesncor-iasea0r—rsesr* 3104 fin [3.12] A quartz sandstone with calcite cement is intruded by molten igneous rock as shown below. cowract METAMORPHOSED COUNTRY Rock; ‘ZONE QUARTZ SANDSTONE WITH CALCITE. CeMENT CHAPTER 3 “The country rock (sandstone) adjacent to the intrusion undergoes “contact metamorphism” as a consequence of heat transfer from the intra- sion. The contact metamorphic reaction is: Si0,(s) + CaCOJs) — CaSi0,8) + COe) a-Quartz Calcite Wollastonite ‘Calculate AS* for this reaction at 565°C. Solution ASkyg = Enh, (Products) - EnSq(Reactants) 82.01 + 2138-4146 ~ 88.7 = 165.65 J/(molK). () SetUp __ Si0,@) + Caco, ls) BF Casings) *C0,4) AS4 AS, AS, AS, S10, 4) +CaCda(e) “AS*zqg ? CASiO()+ CO,Q) 2) Sum EAS, (3) Substitute ACP = (Cp + (1}C pl) ap epSHsl) ay qpeeeOl)THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘The coefficients of C, are taken from Tables A.3A and A.3B in Appendix A and arranged as follows: a b ¢ a € coe) 12s | 14.373x103 | — | 0.169410 | 2779x104 cu) 87.820 | -2.6442« 107 | — | -9.9886%10 | 70.641 x10" =, ~44.60_|-37.754% 10° | — = 100.18 x 10" bee) 99.715 [-26920% 103 | — = 215.76% 10" a=54.755 | b=-529452 | — | d=-98192 | e= 108791 x10? xe x10 Hence, AC, [J{mol-K)] = 55.295 ~ 52.9452 x 10° T-9.8192x 10° T25 + 108.791 x 1o*T2, (4) Solve 8g 16568 | Bsans-sosusrxi0 °F -geisne1oer e108 791x108) 2 = 165,65 ~ 11,99 = 154, mol-K). [3.13] Calculate the standard entropy of formation for the reaction in Exercise Problem [2.13] at 1356 K. Solution (1) Soup, of SEBS acu t+ 45,() ——9>—_ cu, sts)srare2 204) SE teu + 45,66) 2 a SU0 are: Ss a0 8 cals) 2h5q | heASy asl AS, 4,50 OF cu,560 hs, (=) +. ast yOu SUA) STs neuter +45q——85_ 0 ares. CHAPTER 3 ©) Sum as ag = EASy, =0= Sh, + AS, +85, +88, +85, +85, — ASH, ~245, —2.AS, -2A8, \hich upon rearranging gives ASS = ASS +AS, + AS, + AS, + AS, +455 —205, AS, 288, substituted into ASR, ubove: AS{f = {1 mol[120-75 1A mol -K)]- 0Smol[228.175(molK)] 2 molf33.154/(mol-K)]} + [Gooye,oo Be (1m09(9849 Fimo) Jfomyc,ovee 2, cama 88 simot) 376K 3K - aT 13.054 kJ/mol one) FP _(2ypqif 12.054 Kn [fom 2 ema TE) 7 fos mole, 0) 32 “e mole, 22, ‘Upon integrating and completing all calculations, ASCifey = 1222.J1(mol-K), [3.14] Calculate the standard entropy change for the reaction in Exercise Prob- Jem [2.10] at temperature T where 373 K NoAlsi,Q.@ +5i0,( Albite Jadeite Qvarte 48 CHAPTER 3 (2) Sum EAS = 0= ASK, +AS, + AS, ~AS2— AS, oF ASP = ASS, +AS, + AS, — AS, Collecting like items and applying (3-16) and (2-17) : G) Substitute ‘AS3 = -92.47 -238.21In(T) + 238.21In(298) + 140.749 x 107 — 140.749 10-9(298) + 24.596 1087-4 ~ 24.596 x 105(298)~ 113.61 1077? + 113.615¢10°?(298°) 87.384 10° 7-1 + 87.384 «107(298-"2) JK (4) Solve. 45¢[J (mot K) 1762.2 288.211n(T) + 140.75%10°T ~113.61x 10°77? —87.3810°T"" + 24.60.1057 [3.16] Consider the hypothetical power cycle represented below. (@) Calculate actual and Camot efficiencies forthe process if T,= 600K. and 7, = 300K. (®) Ifa new alloy permits raising the maximum oper: to 750 K, calculate the resulting efficiencies. temperature 49THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS area23, ‘area a123b 1/2(7,- TS ~S,) VAT, - TS, -8,)+T(S,-5,) G, em [3.17] The Camot cycle efficiency is often used as a basis for estimating the effect of increasing operating input temperature and lowering rejection temperature on the efficiency of a power generating process, Curzon and Ahlbom (1975, p. 22-24) have shown that to achieve theoretical ‘Camot efficiency, heat transfer must take place through an infinitely ‘small temperature differential, which in turn, requires infinite time, They derived the following modification to Carnot efficiency, which takes into account the necessary temperature differential that must exist across the high and low temperature heat transfer boundaries if the cycle is going to be completed in a reasonable time interval: Nea. =~ JiTTa- Using the data given in Exercise Problem (3.16), calculate ne, and compare with 9 and n, obtained inthe same problem, Solution a) tea = 50 ae =0.293 or 20.3% 00 [EP 0293 or 35.8% RB142. cures ‘A comparison of Carnot efficiencies in Example Probleth (3.18) indicates that alloy modification increases predicted efficiency form 50 to 60% because of the higher allowable T,. This is a 20% increase (10/50 x 100% = 20%). ‘A.comparison of Curzon-Ahlbom efficiencies indicates that alloy modification increases predicted efficiency from 29.3 10 36.8% because ofthe higher allowable T,, This is a 25.6% increase (7.5/29:3 x 100% = 25.6%). The C.A. ‘equation gives an efficiency which is much closer to the actual value in [3.16] and provides a stronger case for alloy modification. {3.18} A small amount of Hg) in voleanic gxses promotes intense chemical ‘weathering of rock nthe vicinity ofa voleani vent. Calculate the stan- dardentropy of formation associated with the production of H,S(g) from its elements at 600 K and 1 atm in kJ/(mol-K) and cal/(mol-K). (@) 3H,(g) + $O,(g) 2H,0() + H,S(g) AS%p ==75.44 Jmol) i () S02) + W/2)8,02) + 0,0) S29 = 73.26 IKmolK) (© H,@)+ (120) > #,0@) AS =-51.30 JAmolK) Solution Hyg) +504(e) 9 24,08) 188) 1/284(6)+02(8) > 802(8) asa 2H, 0(g)—>2413(4)+02(s) ASkx = (-29-51.301 mot K)] H,(g)+1/283(8) > HaS(8) Asis 46.10, (mal K) ASQf =-46.10/sfmol-K)x1KI 1000) = ~46.10%10°9KI (mal). Also, AS9f = -46.10 J /(mot - K) x1 cal /4.184J = -11,02cal (mol K). Asfif =—46.110°9 1 f(mol-K) = -11.02cat (mol K). 51THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 13.19] Show that H,S() spontaneously forms at 600 K. Refer to Exercise Prob- Tem {3.18}. Assume the surroundings are at 600 K. Use the heat capacity for S,(g) in Appendix A, Table A.3B. ‘Solution () SetUp - Hyg) + 2S.) “PRE H, 509) (orate 2 slat, TabEOR) ay mt) as, Hog) + ¥2 S2@) Rag? HS) Cshate lt Lahm, Q) Sum Sn = (3) & (4) Substitute/Solve Collecting terms and applying [2-16] and [2-17] : 00 aif =-84 872+ f (95415 95%10°7 + 104288%107 77 = 294.5519 +521,729.5T?)dT =-87,936 / mol. " 52, = ase, 4 All ~(-87,936) AL O0OK,ASSy = B5%, + B52, = ASS, + 6.14 82536) Ts +600 1005 J/(mol-K)>0=> spontaneous 52 AH + Att, AH, —3 Atl All or AHS, = AHL + Art, 2 Ay CHAPTER 4 Chapter 4 [4.1] An ideal gas undergoes an isothermal process from an initial State 1 (P,\V;,T) to final State 2: (P2V>,1). Prove AGr=RT INP YP). Solution . dG=VaP - SdP,y = RTIP ae Hl gpasag, nt wip =Rrn(?,/4) [4.2] The initial state of one mole of a monatomic ideal gas is P, = 5 atm and T, = 300 K, Calculate the entropy change of the gas for: (a) an isothermal decrease in pressure to 1 atm. (b) a constant volume decrease in the pressure to 1 atm. Solution (@) Since the process is isothermal and the pressure change is known, use $= SPD) gle B- Ge 2) mie ass [s=-rfpr --aanerin02)=1338 JH K) sen Baieel ds aD), ) Ues=f0 Ene. “Ge Gae From [3-13] , ‘ 3 A896 fair 500 53‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘Where nar, =1/5x300=60 “0 ascsran arr 07 (mol-K). [43] Prove by two methods that at constant temperature, ‘Mem = 0 for an ideal gas, regardless of the pressure path. Solution ‘Method 1 Let H=U+PV dH =dU + dV) For an ideal gas, U= f(T) only, hence dU = 0 at constant temperature, Also, since PV = RT, (PV) = (RT) = 0. Substituting, i aP =Tds + VAP. Dividing by AP and holding T constant, u ug cy (2), +, sig 20, (o( 2), (2), +¥- rm et ec, a . 2) nr. sting ino ie exrsion shor, (22) =-rarror =o. rs, 54 CHAPTER 4 [4.4] Prove that at constant temperature, ASisaneanat = AR In(P2/P,) for n moles of an ideal gas, Solution Let S'=fiPT), o(Ele(E# From [4-23], (I, 7 (), Substituting the last expression into the equation for dS’ gives i a--()) arrest , an, ? a 7 ASI, -aR In} ~~ [4.5] Calcium boils at 1440°C. The standard free energy of vaporization of liquid caleium is given by AGF. (cal/mol) = 41,030 + 5.837 log(7) ~ 42.237, where log = logo (personal communication, 1959, R. Schuhmann, J, Department of Metallurgical Engineering, Purdue University, West Lafayete, Indiana), (@) Find the linear Gibbs free energy equation ofthe form G9 =a+bT ‘Which approximates the above equation as closely as possible near 1500 K, 55.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (b) Calculate the boiling point from the linear equation and compare with the actual value, Soluion @ AG? = 41,030 + 5.837 log(T)- 42.237 1,030-+ 2.537 In(T) ~ 42.237 From [4-25], ‘aaa? ‘aln(r) ar (4G) af 290), (2) Je 8° =-2.59f1+ In(7)]+ 42.28, 2.531n(7)~2.53 + 42.23 53In()+39.70 From (4-30), fase «ge {8p se-) or |, ar 41,030 , 2.53 Te (©) At the boiling point, iquid and vapor are at equilibrium, hence AG? = 0: 0=37,235 21.27 1756 1440-273 ) = 1U6 am a * 100 = 2.5% error re masa (iAP 100 -2.5%0rr) [4.6] Phosphorous bearing vanadium deposits ofthe western U.S, are a source of vanadium used in the steel industry as an alloy component. X-ray ‘examination of a representative sample of raw material from these de- ‘posits reveals that the major impurity present in the ore is iron in the form of Fe,P. A suggested method for removing the iron is to convert Fe,P to FeP and pure iron (ferrite) by vacuum distillation of the phos- ‘Phorous and remove the iron magnetically. Assuming the best vacuum. obtainable ina large scale operation is 10-?mm Hg, estimate the operating temperature of a vacuum furnace required to accomplish this distil. lation, CHAPTER 4 36,= RT Wf, )= 81447 (So AG, = AG, AG =0 (equilibrium) AG" is determined as follows: 4Fe+2 2=2P AFe+P,=2Fe,P A644 bt mol P, ‘AS? = 2(72.98) ~4(27.28)~ 218=~182.4 kJ /(mol P, -K). (4) Solve AG =0=-93.447 + 464,400 - 18247 T= 1684 Kor J411°C. [4.7] Estimate the pressure which must be applied to increase the melting point of pure Au by 20°C, Solution ‘Three TL's are used to solve this problem,‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘TLL - Pressure () Setup f Auts) 4a Au (LY aca I dP ¥) . ofa dp A ' f Auls) Geo Au (2) Molar volumes are obtained from literature data. AG is calculated from TL #2 and #3. ‘TL#2- Enthalpy of fusion at 1356 K (see Example Problem 2-6) () SaUp £ Au (s) AK Au(2) 135K 1356 1356 Ath= [pat “) Adz {cpaT 1336 | 1336 Auf 212,160 Auls see aud (2) & 3) Sum & Substitute EAH, =0 2,760+ {29.29aT - aif, -[ "(23-08-+ 519x107 TET = 12,760 + (29.29 x 20) - Alice ~ 613.6 @) Salve AH fg = 12,732 S/mol. CHAPTER 4 ‘TLA - Entropy of fusion at 1356 K (see Example Problem 3-5) () sexu co (2) Auls) ~~ 135K Aw {35te AS= {cpt 1336 é | | as =4s5 Aus) 133K Ault) 2) & G)Sum& Subsite as, =0-955+ [Ber atla- [ (Bssi0.00° jr Sling = 9.55 + 0.435 — 0.248 = 9.737 J/(mol-K) Calculating. aC from (4-8) Gly = 12,732 1356(9.737) = 471.4 Jmol Now, referring to TL 1: (2) & @) Sum & Substinte EAGny =-AT14 + Vjqu)[aP—0- Yona o M_1 vg ; Substituting jpg) = 2 = 5 #197 = 11.59 emia 1 3 Yaa = og *197= 10.207 em*/m, LAGy, = 0= ~471.4-[11.6XP - 1)-10.207(P -1)}x0.1018 ) Solve P=3370 atm,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS [48] Assuming that AH® and AS are independent of temperature, calculate the temperature at which solid HgO will dissociate into liquid Hg and x6) at 1 atm, Solution (Sap DUS Hgo (s) ST Hae Oth 0, (g) Als At, Paw, : | aoc AMES 15 (L) +2 deg (2) & @) Sum & Substitute . 4-0, f ayer, tons te so lyse da dn 0 298K. Lay, = (4) Solve AH2= 90.8 kifnol Applying the same TL in a similar manner for entropy: AS? = AS3y. = 75.91 + 1/2 (205.02) -70.: 108.12 JmoLK), Using [4-11] and setting AG? =0, AG? = 0 = AH, ~TAS!, 90,800 08.12 = Ali, ~ any = 899.8 K~ 567" [4.9] Thermodynamic analysis of the equilibrium state for carbon, chromium, and niobium carbide reveals that niobium is an effective alloying agent for limiting grain boundary precipitation of chromium carbide by pref- cerentially removing carbon as niobium carbide, (a) Write a single equation describing C-Nb-Cr equilibria neglecting solubility effects. (b)Confirm thermodynamically the alloying effect of Nb at 1200 K. 60 CHAPTER 4 Solution (@) GNb + CrxC, 7 46nd + 23, (b) From TL analysis: () SetUp 4G ON b+ Cre,Ce zek 7 NDC + 23Cr An ob a lob + ol. Cy BEEP Nb + 23Cr © Sum EAGy, = AG hy +294G, + 646, ~ AGiny - GAG, — AG, = 0 @) Substitute Al! pure components, no solid solubility, ‘AG, = AGy = AG, = AG, = 0 Gp, = BG ing = BAG ng ~ AG, AG ing = 6-130, 195 + 1.67(1200)] -6f-68,540-~6.44(1200] = 311,200 J/mol < 0 = NbC formation is favored. [4.10] Three equations for the oxidation of a metal M are given below. One of these equations i forthe oxidation of solid M, one is fr the oxidation ‘of liquid M, and one is forthe oxidation of gascous M. Using the AG? data given, identify the reaction and the state of the reactant metal. (@)2M+0,(g) > 2MO(s) AGP. = -290,400+ 46.1 ()2M+0,{) > 2MO(s) AG? = 358,754 + 102.67 (© 2M+ Ox(g) > 2MO(s) Solution From (4-27), entropies for each reaction are: 290400 46) 46.1 catmots)‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Reaction (b) (ae } gs = AC 358 7544100, le = 102.6 cal/(mol-K) a or AS? =-102.6 Reaction (o) aac? (298, 400+55.47)) _ Be (4) - 1° = AC 28400 5.47) ], = 954 eallmolx) AS = 55.4 From the discussion in section 3.5, ‘AS%gas) > AS"(liquid) > AS°Golid) hence, from the data above AS° reaction (a) is solid M AS° reaction (b) is gaseous M AS® reaction (c) is liquid M [4.11] For the reaction SIC{s) ~ Sil) + C(8), AG. = 19.770 — 1.667 cafmol from 298-1680 K. Using this data, determine: (a) AS® at 1000 K. (b) AH? at 1500 K. Solution From direct examination, the expression is identical to [4-11], hence AH® and AS® are constants over the applicable temperature range, (@) AS Sax = 1.66 calmol-K), (b) Axe 12,770 cal/(mel). [4.12] Using the general expression for C, ~ C, given in Exercise Problem 03} (@) Show that C,~ C, = @VTIB for any substance. (b) Use this expression to estimate C, ~ C, for pure copper at 298 K. Solution (@) From Exercise Problem [1.3]: ee) 5) Using [1-2], 1-3], and the transformation formula [4-18], 62 CHAPTER 4 wv (F)-” (2), eet OT Jy (OV/aP), BV (¢ a a), B Substituting ino the above expression, a@)_a°Vr Cp-S ~rev(S) B (0) From Table B.1 6, -c, = (185%104)* em? 298 K-atm pv 8.96 gm- 7.6% 10" 0.0012 atm-em*,_1mol-K__ 8.3144 ~“K-gm 82.057 atm-em? mol’ K [4.13] Use the data in Exercise Problom [3.8] and the Gibbs free energy erite- ria to confirm that solidification is spontaneous after supercooling. Solution AG=aH-Tas =-12, 136 - 809(-11.58) 877 Jmol <0 = spontaneous [4.14] (@) Starting with [4-13], use [4-27] and [4-30] 10 compute AS® and AH?, respectively, asa function of temperature, (©) Use the results from (a) and Appendix A, Table A.4 to obtain AH® and AS®as a function of temperature for the reaction 2CU(s) + (1/2)0a(~) ~> Cu,06) Compare the results at T = 298 K with the data in Appendix A, Table Al.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS B +yqoeTiMn)+er Asp = Bo [r-yT +tn(r)]+C B ~AS? = Zaoglt intr] +e as= 4 finyr)-1]-c (b) AS and ASg,: as; rable A.4 Derive ion (h Derived Equation) |, be = 75.74 J(mol-K) fase, = 99.94 - 2052" _ (83.35) eae 15.27 J (mol: K) ‘aH and AH 4H =~169,470+ 2.808 -169,470+7.127 = =167,350 J/mol (Table A.4: Derived Equation) } =1S7,350 Simo} (Table A.1) {4H3, = 167,380 Jmol. CHAPTER 4 [4.15] ‘The thermodynamics of SiO is important in many materials appica- tions because ofits high vapor pressure, Develo an expression forthe Gibbs free energy of formation of SiO), ACSA, asa function of temperature between 298-1700 K using the data in Appendix A, Table Aa Solution (1) (Si0,) + (S1)=2(810) G° = 697,539 + 53.987 log(T) -618.457 Jmol, 2) (Si0,)= (Si) +(0,) AG?! =881,235 +12.55TIog(T)-218.51T mol @=0)-@. (Si) + (02) > 2{Si0) AG™ = -183,696+ 41.37 log(T)- 3007 AGE, (3mol) = 91,848 + 20.727 lok T)— 1507, 14.16] One mole of a metal, m, at 1 atm pressure is heated at constant volume from 300 to 500 K. Calculate the hyédrostatic pressure that results from such a process. What is the work done? Assume G, is constant over the temperature interval. a,,= 5% 10° K+, and fi, = 8 x10 atm, Solution ‘Since the process is constant volume, the path may be expressed by the From (4-18), ap (aver), (2) = wnTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Expanding and intergrating, Fy 2p sx10" dp 8 fg = S200 [oP 5 far Fee em P,=1251am; wafers (4.17) Referring to Exercise Problem (4.16), caloulate the entropy change for the same process. Let C= 20.9 HimobK), V6 em ign mod, Solution s=fnP) 2-(8)-)- Using the differential form of [3-10] and applying [4-23], Where V (assumed) + f(P) sa). 5x10 66m 1955 stm) as. ra9n( 52 300, mol-K 5x10 x6em? 1251 atmxJ ‘mol-K 9,869 em? aim (0.64 I)(mol-K) 0.68 — = 10.68 ~0.03 [4.18] Use the Gibbs free energy criteria to confirm that liquid potassium and its vapor are in equilibrium at 950 K and 0.447 bar. 66 CHAPTER 4 Solution (rable D.2) ig = Mig Ty (2750.4~771.4) -950(4.8129 ~ 2.7818) ki kg 1979-1978 9. [4.19] Use {3-6] to confirm the value of u, ~ u, in Appendix D, Table D.2, at 900 K and 0.251 bar. Solution Jax-nfao-pfio su50499115-242)-£2590 90-1408) <1 pg (0). [4.20] Referring to Exercise Problems [4.16] and [4.17], estimate the enthalpy ‘change for the same process if Ve, = 10 cm*/mol, State any assumptions jn making the calculations. Solution From [4-33] , t=c, frov [i erue ge eee ee sangf™ ar 250, 2101, (ses pP ‘Since the functional dependence between T and P is unknown, a rigorous solution to the problem cannot be obtained. However, since Soom cel, pce by melectng te ast ‘At sano) 10x 101% 1280 = 5440 J/mol, V,,and o. are assumed constant. Note: Ifthe substance were an ideal gas for which the equation of state is known, the pressure term would disappear since (1-0(T) = (1-1) =0. In such a case, a rigorous solution is obtained. This illustrates the importance of identifying reasonable assumptions in determining thermodynamic properties of condensed states for which equations of state are empirical and limited in application. 67THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. [4.21] Using the standard enthalpy and entropy changes computed in Exercise Problems (2.10) and [3.14] for the reaction Miga$iz03(OH),(s) + 2Si0,(6) —> Mg,SigO,(OH,)(s) + H0(), calculate AGp at temperature T where 373 K NAAISi{04s) + SiOx), calculate AG? at temperature T where 298 K < 7 < 844 K. No phase changes oceur. Solution ‘4G (I/mol)= (53.21 x 10" 238.21T +7.04 x 10-21 7.57 x 101+ 4,92 x 10°T + 8,74 10°15) ~ (1762.21 ~ 238,21 In(T) + 140.749 x 10°97 — 113.61 x 10-71>— 87.384 x 10°T-*5 + 24.596 x 10°T?), Collecting like terms: G2 (Imol) = 53.21 x 103 2000.4T + 238.21 In(T) - 70.349 x 109724 3.791 x 109+ 17.478 x 10°95 + 24604 x 10°, [4.23] The soresilicate lawsonite, CaAl,Si,0,(OH),-H,0(),is common con- stituent of metamorphic rocks formed at low temperature and high pressure, Assuming the molar volume of this mineral is independent of pressure, calculate the molar isothermal Gibbs free energy change for Jawsonite subjected toa reversibly applied pressure increase from 1 105 ‘bar at 298 K. 68 CHAPTER 4 Solution Since & V ae eg dG=VaP- sit» dG VaP [de=v [de> AG=VaP, hence from B.2, ae 4.1845 am oo~(s01.2055 | ara cat ata) Tau br ) (omnia) AP =Abar: 4G «(10.125 J ‘mol-bar bas) = 405 Jmol [4.24] Using the standard enthalpy and entropy of formation computed in Exercise Problems [2.13] and (3.13] for the reaction 2Cul) + 128i) -> CUS, determine whether or not this reaction is spontaneous at 1356 K as wren, Solution (1) SetUp AG 2Cul) ae rs G) Se Cpe 2A6, BAG, AG, | Ace 2cult) + ¥2S2.64) Taseq> Cuz, S$ (0) 2) Sum 380 q =O AO 0,80 200,206, 60THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS: 3) Substitute Gang = AFD — 1356(AS 2g) 108,371 1356(122.244) 214, 260 Jimol AGyg = -274,260 Jmol <0 = spontaneous. [4.25] For the contact metamorphic reaction Si0,(@) + CaCOy) ~» CaSiOK) + COs), (@) Calculate the standard Gibbs free energy change at temperature 298K AG? = 0 = 88,670- 165.657%" => Ts 2855 K, ‘Spontaneous reaction =» AG? <0= 88,670— 165.657" <=> Te 535i Nonspontaneous reaction => AG? > 0 = 88,670~ 165.65T%=m= > 9 => Diem < 535) 70 (CHAPTER 4 AG, as a Function of T for the Reaction (SiO,), + ~r + CO, (9) AG (TAnsle) P= lahn, 45x10? 235x103 25x10? wsx10? POINT AT T= 844K 1S EXCLUDED [4.26] Show that the Gibbs free energy change for an isobaric chemical reaction occurring at a temperature Tis AG = AH, ~ TAS, when AC, = 0 in the temperature range between T; to 7. "THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Solution ‘Atconstant pressure, AG, = 4H, ~TAs, 7 AH, = Atty, + [scars =as, + Since ACp=0, AH, = AH, and AS, = AS,, Hence, 8G, = AH, ~TAS,,. [4.27] Derive [4-13] showing all steps. Solution 69 = auras? sutt= ait facjar it 0 7 AC, ee hence, AH? = Ai +a(7 -298) ASP = ASI, + a n(T/298) Substituting AM? and AS? into AGP, AGP = Al ~ 298a~ aT In(T)+T[a— AS, + ain(298)] Let A= Al1%q ~298a (all constants) aln(T/298) *Tog(T) C=a~ AS%q (all T terms) Substituting A,B, and C: AGP = A+B Tog(T)+Cr 2 CHAPTER 4 [4.28] Derive [4-14] and show that {$) =(%2 P), I), Solution Let =H-TS, H=U+PV,dU= 80~6W,0W = Pav, and dS=60/T dG = dH (TS) = aU + PY) -acTs) aG = dU + d(PV) -acTS) = 8Q- 5W+ a(PV) - A(T) TaS -PaV + PAV + VaP- TUS - ST. Hence, as wv was Pom .-(8) -(2). aa-ver-sir romts.-(2) -(2),‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 4 CHAPTER 5 Chapter 5 [5.1] An ideal gas mixture at pressure P,,., contains a gas component i of atomic fraction ¥, Show G,~ GP = RTUn(P,,..)+ IY). Solution From [5-6], G.-G? =RTIn(Y.P,) Rin, + nP,, [5.2] An isothermal ideal gas mixture changes pressure from Py ny 0 Pag ‘The mole fraction of gas iin the mixture is ¥, Prove AG,= RTP ul? re) Solution AG,=RTIn(YP,)-RT In(¥P,) [5.3] During carburization processing of stel at 870°C in a mixture of CO and CO,, surface oxidation of iron may prevent penetration of carbon if Peo, is too high. Calculate the equilibrium P,./ Poo, ratio, What effect does a higher than equilibrium ratio have on Oxidation? Use Appendix ‘A, Table A.4 data. Compare the results obtained with Figure E.2 in Ap- pendix E, Solution (1) SecUp Fels) + CO, (q) Seuss 5 Fe OG) + co le em ee en Fel + CO,Cq) SE FeO) +.COUq> 75THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. @ Sum ) Subsite AG, = 0 at equilibrium AG, = AG, = 0 for pure condensed phases 4G, =RT n(Feo,) 4G, =RT InP.) Substituting into the above, G85 = RTIn(Peo, /Poo) From Table A4, AGB«s = AGS + Go ~ AGE, = 111,723 ~ 87.66(1173) + {-259,600 + 62.55(1173)] ~ [-394,170 — 0.84(1173)) 5622 + In(Poo/Poo,) = 5622/18.3144(1173)] 516 Solve Poo/Peop = LLIB (compared to = 2.0 from Figure E.2) If Foo/Peo = 10.0 for example, then AG,,., = 22,461 ~ 5622 ‘hich is deoxidizing. The ratio should be held ator above 1.78, [54] Its difficult to prevent the formation of MnS during the steel making process. One possible technique in reducing MnS content isto getter or selectively remove S by adding an element to the liquid steel bath that forms a more stable sulfide than manganese, Use Figure E.3 in Appen- dix E to select a possible addition. Identify the parameters used in making the selection and state assum Solution Assuming the steel bath temperature is 1,400°C and neglecting solubility effects, four possible candidate element additions are obtained from Figure 3. These are Na, Mg, Ca, and Ce. Na and Mg are not suitable choices ‘because of their relatively low boiling points. Ca is preferred over Ce because Of the lower cost and availability of the former, 76 CHAPTER 5 [5.5] The Gibbs free energy change for the eaction given in Example Prob- lem 5-5 is provided by Wicks and Block (1963, p. 68): AGP. (cal/mol) =~ 47,000 + 12.47 In(T) - 11.36 x 1097? + 0.54 x 107+ 37.87 where 453 K LIZN@© (2) Sum TAGy, =0= AG +AG,— AG yq~ 1286, ~ 346, G) Subsite AG, = 3G, = 0 (assume all condensed phases are pure) AG,., = 0 (equilibrium) 12aG, = Rtn FY?) 4700+ 124T nT) ~1136x10° T+ 054x 10 T3787 = 1987T'In (AY?) -18,192 = 1.987800) in 72)THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. (4) Solve Py= 115%10-atm, ‘Since 0.005 vo (volume percent) is equivalent to $ x 10- atm, sziclthium nitide will fonm under experimental conditions. [5.8] Estimate the temperature at which SiO, and Si metal will react to boil off SiO ina vacuum furnace pumped to 10- atm (personal communication, 1959, R. Schuhmann, Jr, Department of Metallurgical Engineer- ing, Purdue University, West Lafayette, Indiana), Solution (2) Set Up : ; A S10, (2) + Silo) S25 25; O@) AG, Ae, 2d6, Si0,(8) +Si(s) “T4251 0) @) Sum 3G,= @) Substinue AG? = 697,540 + 53.987 log (T)-518.45T 2AG, = 8.3144T In( Rio) ‘AG, = AG, = 0 (pure condensed phases) (equilibrium) 0 = 697,540 + 53,98Tlog (1) - 518.45T + 83144T In (0.001) = AG? + 28G,- 6, ~ 46,6, @) Solve T= ISK. [59] In Exercise Problem [5.8], iis shown thatthe best vacuum obtainable is 10° atm at 1511 K when impure SiO, (containing excess Si is used as containment for heat treatment, annealing etc. Determine the best ‘vacuum obiainable when stoichiometrically pure SiO, is used for containment at the same temperature, crwerens Solution Using direct dissociation of (@) SexUp Sio, (2) 4E#1 Si0 (9) + 40, (9) Gz AG, BAG, ° Sid, @) Ei _,Si0 Cg) + % 0, 6g) @ Sum ZAG = G) Substitute Gy, = 0 (equilibrium) 4G, = 0 (pure condensed phases) 1/2AG, = 8.3144 (1511) In (73.7) AG, =8.3144(1511) InP) AGIs = AGH sow — SG 0,09 From Table A4, AGP Log) = -91,848 + 20.72Tlog (T) - 150T and AG#oyq) =~ 881,235 ~ 12.55Tlog (T) + 218.51T AGP. = 789,387 + 33.27Tlog(T) - 368.51T Gia, = 789,387 + 159,825 — 556,819 = 392,393 Jmol Gigy1 + 2G, + AG, ~ AG,,,, ~ AG, (4) Solve, 0 = 392,398 + 1511(8.3144) In (P* Pao) PoP? = 2.72% 10 Since Fo, = U/2Pyoy Pyg = 114 x 107 atm Po, =5.7 x 10aum P,= Peo + Posty = LZL10-tatm aeTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Comment: Comparing the results from Exercise Problems [5.8] and [5.9], high purity SiO, would allow for a six order of magnitude improvement in vacuum, [5.10] Refer to Exercise Problem [5.7]. In order to limit the formation of tri lithium nitride, the P., must be held below 1.15 10" atm. Since 0.005 vvlo (volume percent) N, in the inest gas is unacceptable, select a possible candidate metal over which the inert gas could be passed in order to reduce N, to an acceptable partial pressure before itis used to purge air prior to brazing. ‘metals are considered: Ti and Ca, zt + NAG) E> 2TiN isd ZAG, LG, 2AG; ASy 27 (0 + N,G)——=* > 2TiN (s) 2) Sum LAG, = 0= AG? +2AG, ~ AG; ~ AG, - 2AG, 3) Substitute 2G, = 2G, = 0 (pure condensed phases) AGr =0 (equilibrium) 4G, =8314¢TIn(1.15%10™) From Table A.4, ‘G3 =~ 671,600+ 185.87 0=~ 671,600 + 185.87" 8.31447 In(1.15% 10) ) Solve 786 K is above the transformation Ti (o) > Ti). CHAPTER 5 1a AG? =~ 676,620 + 190.20T 0+ 676,620-+190.207 8.31447 (1.15 10") 97 =178K. ‘T= 1778 K is above 1500 K given in Table A.4 for applicability of the data. However, the Ny ~Ti phase diagram shows that the B phase is stable up to the 1mekiing point of 1945 K (according to Table A.2, Tyg, = 1933 K), Hence, Tih) is one possibility Calcium is nother possibility, since it forms a stable nitride: Ca ) Setup. 3a. le) +N, 6) ASt ca NO BhGs AG AE, 2Ca.(2)+ Na (3) AEE Ga ana lo 2) Sum TAG, =0= AG?-+AG, -AG, -A6,~346, ) Substinute AG, = 34G, = 0 (pure condensed phases) AG, = 0 (equilibrium) AG, =RT in (1.15 x 10%) From Table A, AG? =~ 439,360 + 209.27, 0 = ~439,360 + 209.27 831447 In(L15 x 10°) @ Sove 439,360 uM 399.4 = 100K Note: The required temperature of 1100 K is just below the melting point (1123 K) of calcium, hence Ti (Bis the better choice, 83‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS: [5.11] According to Kane and Chakachery (1992), possible coating materials for carbon/carbon composites include oxidation resistant SiC and Si,N, ‘coatings as well a glass forming inhibitors such as boron carbide. The stability of these coatings in hydrogen environments is unknown although data for B,C and H, can be computed from information in the literature. Calculate equilibria for the B, C, H system at 0.03 MPa and 13.8 MPa and at a temperature of 815°C. Discuss. Solution (1) SetUp- ByC (3) + 24, GA 48) +CH4@) ey fase) Jose fae B4 C(O + 2H, 3) AS 46 (2) +cHy (q) (2) Sum 3AG,, =0= AG? + AG;+ 446, - AG, 240, -AG, G) Substitute 44G, = AG, (pure condensed phases) AG, = 0 (equilibrium) AG, = 8.3144 (1088)In (Pex, ) 2AG, = 8.3144 (1088)In (Zi, ) AG? = AGP Gt, ~ AGP,c. From Table A, AGP, = 69,126 + 51.26Tlog(T) - 65.367. AG rhe = Ath Acs, A534 4c. assuming AC, ~ 0, 51,100 ~ T(S$55,3,0 ~ Sios,c ~ 48$4,n) =-97,700 -T127.07 — 5.69 - 4(5.86)] =+57,100+ 2.06T. AGP. =~ 69,126 + 51.26Tlog(T) - 65.367 - (-57,700 + 2.061). AGiags = 84,577 Jmol 84,577 =~ 8.3144(1088)In (Pex, /A3,) 24 CHAPTER 5 @) Solve Pog, / PB, =8.7 x10 Assuming Py, +Pey, = Fr and substituting from above: Fy, +8:7x10° PR - Py =0 03 MPa = 03 atm. a1eJicioanao | is ae 1 Fa Tel Pox, 9.0001 aim Pry, /Pr, * 9.0003 Pya13.8MPa=136 aime wiv aT a2 dO™ Ps 28.7x10" Pox, ~ LS Pau /Pa, = 9012 9.2999 aim [344m A comparison of the data suggests that it would be more practical to maintain are 0(eH (2) 2) Sum EAG,, =0= AG%y + 246, - AG, —AG,~ 1/246, ~ 246, 1,= 0 (pure condensed phases) ium) 124G, = /2RTIn( Po, ) = 1/2(8.3144)(298)In(Po, ) AG fog = ENAG 94 (Products) ~ EnAG $34 Reactants) From Tables A.1 and A.4, AG $9 = ~239,706 J/mol. Substituting into ZAG, = 0, 0-= 239,706 -1/2(8.3144)(298)In (Fo, ) (4) Solve 239,706 1n(?o,) = aRfe-3144)398) 7o,= 10 aim, => gocthite is stable in ar at the surface where Py, ~ 0.22 aim,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (b) See problem statement, [5.14] In the absence of sufficient H,0, chemical weathering of arock containing iron-rich minerals will produce hematite, Fe,0,, instead of gocthite (refer to Exercise Problem [5.13]). Hematite imparts a red to reddish- brown color to rocks. (@) Calculate the minimum Po, tequired to form and stabilize hematite at 298 K. (©) Discuss the significance of (a) with respect tothe Po, cq) in air and the stability of hematite at the surface of the earth, Solution @ (1) SetUp 2FeO(s) + 1.0, (g) SS > Fe, Os (=) NN LAG, 4G, 2 Fe OCs) + 42.0, (g) AE oFe 05 (5) @) Sum TAG, = 0= AGS, +AG, ~ AGyy - 1/24G, - 246, (3) Substitute AG, = 2AG, = 0 (pure condensed phases) Gay = 0 (equilibrium) 1/286, = 1728.3144)(298)in(Po,) From Tables A.1 and A.4, AG ¥e = -260,395 J/mol Substituting into EAG,, 0 = 260,395 - 1/2(8.3144)(298) In (Po, ) CHAPTER 5 Sale 260,395 1n(Po,) = Taxeaiea aH 5x10 aim (b) See problem statement. [5.15] Chemical analysis of the reddish and yellow-brown weathering rind on ‘rock reveals that it contains both goethite and hematite. Based on the results of Exercise Problems [5.13] and [5.14], suggest how the above ‘mineral assemblage might occur. Solution (1) Localized area(s) of rock remain depleted in H,0, hence the mixture of minerals. (2) Zones of HO depletion may vary over time and promote dissociation of ‘goethite into hematite and H,0. (3) Changes in pH may also be a factor according to the Pourbaix diagram (see Exercise Problem [5.13)). ‘Combining reactions in Exercise Problems [5.13] and (5.14]: (@) 2F00 (s) + 120, (g) + 1,0 () — 2FeO(OH) (8) Gq = 239,706 J/mol (b) 2Fe0 (5) + 1/20, (g) -> Fe,0, (8) Reaction (b) ~ Reaction (a): 2FeOOH) (8) + 1,0 (1) + Fe,0, (6) Gog = -20,689 J/mol ‘The above reaction is independent of Fo, and favors the dissociation of FeO(OH) into Fe,0, with the release of H1,0. Regions that promote depletion ‘of H,O would favor this reaction since the removal of H, would shift the reaction from left to right. 89‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. [5.16] Brucite, Mg(OH),, is slowly heated in an atmosphere where the isobaric partial pressure of H,O vapor is 10° atm. At what temperature will brucite begin to decompose? Solution ‘woTL's ae employed inthis problem. The fists seo ind Ag, 3 hence, AG. The second is used to find P,,. (1) Set Up Mg (ov), (3) AiaASe Mgole Hol. on AHy €) AH io SA) AS Aes ees Mg(ot), (2) State, 4S, Myo (2) + H,0 (0) 2) Sum ‘TAH, =0= AM3, + AH, + AH + AH, + AH,— AH? — AH, TAS, =0= ASS, + AS, + AST + AS, + AS,— AS? — AS, ) Substitute AlZ34(S/mol) = EnaH. (Products) ~ EndHef (Reactants) = AHS + 2 ~ Sharan 285,900 ~601,800 —(-925,500) > 38,800 J/mol ASL, = ZnSi, (Products) ~ ZnS, Reactants) = Shasyo0 + Soameow ~ Stenger = 70.09 +27.41- 63.00 => S3, = $4.50 J/(mol *) 41.09 fmol AH} = 41.09 kino}, a5 = AZ = 41.09 ASH =110.16 Y(mol-K) = fisasyar =5658 riot aai={fooos1anvan rosea yr =307 +5.36x10°77 -0:33%10°7"1 1,847 CHAPTER 5 Aq, 7 Jle9e12000°7-sses0%rs}r 242597 +364 1097 +619 1071-15092 2 (15840-4076 x10 7 -10523«1087=1.1713«10°7-*)ar pe SRAT 2.038 1071+ 10523 x 107-2496 107 —10,14 Using the same C, and substituting into the general expression Od T AS, = 16.94 J(mol-K) 30In¢T) + 10.71 x 107-- 16,500 T3— 182.52 ‘AS, = 42,59In(T) + 7.28 x 10°T + 3.1 x 10° T2— 248.29 ‘AS, = 158.4In(T) — 4.08 x 10-°T + 5.26 10° T+ 2.34 10°T*S — 1042.83, (4) Solve Using the summation equations DAH, = 0 and EAS,, =, the following expressions for AM? and AS? are oblained: Aut2 (fmol) 68,223 ASP [GAmol-K)] = 22.07 x 10°T- 232,500T2 - 23407 ~ 85.81 In(T) + 713.62 85.81T + 10,86 x 103 T? — 46,3007" + 2342.61 + Substituting into [4-8], AG? (fmol) = -859.43T — 11.21 x 109T?~233,800T" + 4682.67 + 85.81T In(T) + 68,223 1THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Applying the second TL: () Sep Mg l0¥), (2) —SEX—> MgO (+ 420 () Aes Ae AG Malot Ce) AST Mg0 (2) +Hh.065) @ Sum TAG, =0= AG? +AG, + AG, - AG,- AG, @) Substitute AGP: Previously calculated AG, G/mol) = 8.3144 T In(10) = 9.577 AG, = AG, = 0 (pure condensed phases) AG, = 0 (equilibrium) Substituting into the summation equation, (0 = - 859.437 — 11.21 x 10°T ~233,800T* + 4682.67 + 85.81T In(T) + 68,233 + 9.57T (4) Solve Ts sik [5.17] Methane is produced when water saturated sedimentary rocks containing graphite are heated to elevated temperatures. Calculate the equilibrium Poo, «Pox, P,o ratio for the reaction 2C 55 + 2H,0(8) > CH,(g) + CO,(@) at T= 600°C and P, = 2 atm, What is the effect of an inerease in P,? Explain, Solution Elemental carbon in sedimentary rocks occurs only as grains of graphite or diamond, typically of organic origin. Sedimentary rocks heated to elevated temperatures (= 600°C) become textually and sometimes mineralogically transformed into metamorphic rocks. 92 CHAPTER 5 (1) SotUp, 2C(e) + 2H,0(g) SEE CH G)#C0, @) we, | 2heg AG |A6, ae 2Cls) + 2,00)? > CHK (g)+ CO, G) 2) Sum TAG,,=0= AGB, +46, +.4G,~ AG,,~2AG,-246, (3) Substitute 6, = 83144(873In(Po,) AG, = 8.3144(873)In (Fer, ) 2AG, = 2(8.3144)(873)In (Fo) 2AG, = 0 (pure condensed phase) ‘AGq5= 0 (equilibrium) AGhs = AGPLco, + AGY cx, ~2AGRL 4,0; from Table A.4, AGQ,, = 9511 ‘iol (using C, data from Appendix A and TL analysis, AGS, = 11,328 J/mol). Substituting into EAG,, = O and using AG2,, = 11,328, 0= 11,328 + 83144(873)In Poo, ) + 8.3144(873)In(Fox,,) ~ 2(8.3144)(873)In(Fi,0) (4) Solve Peo, Paxy/Pyg =O21 ‘Since 2 moles of H,0 (g) react to form 2 moles of gas, the reaction equilibrium is independent of pressure . This can also be shown by substituting the partial pressures into Dalton’s law: Pom. p, Pa 8) =021‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS [5.18] Using the ratio computed in Exercise Problem [5.17), calculate the partial pressures of each gas at 600°C and P,,= 2 atm. Solution (1) Assume, from the stoichiometry of the reaction, that 2 moles of C(s) and 2 moles of H,0(g) are initially available to react. (2) Lotn = the number of motes of H,O(g) that react with n moles of C(s) to form CH(g) and CO,(). G) Gas HOG) CH) CO(g) Initial Moles 2 0 0 ‘Moles Reacting or Produced a osm 050 ‘Moles Remaining 20 sn. 05n ‘The total number of moles of gas as a function of n are (2—n) + 0.51 +0.5n, =2 (check, intially n= 2). (4) Applying Dalton’s law: n+ 2in=21=0 POS) 29.478 aim, Note: Since the reaction is pressure independent, the partial pressures increase in direct proportion to total pressure. 94 CHAPTERS [5.19] The mineral siderite, FeCO, is found in low. temperature hydrothermal veins and low oxygenated continental waters where its associated with ‘lay and carbonaceous materials. Calculate the Pog, and Po, required to equilibrate siderite and magnetite, F,0,,at 300. ina CO,-C0 at ‘mosphere containing 662mole percent CO, Solution Atequilibrium, Fe,0,(s) + 2CO,(g) + CO(g) = 3FeCO,(s) From the stoichiometry of the reaction, Pog, = 2Pog. (1) SeUp Fes (D+ Roe a AST 33h O66) AG4 BAG, Fe,04 + Are an 22. sal 3s) AGE +346, - 46, AG,~ 246,46, G) Substitute From Table A.4, AG? = 220,915 + 46.947 from 298-700 K ~220,915 + 46,94(300) = -206,833 J/inol 3G, = AG, = 0 (pure condensed phases) AG, = 0 (equilibrium) AG, = RTIn(Pa9) 246, = RT In(F2,) Substituting into ZAG, = 0, 0 = -206,833 - RTin (Foo) ~ RTIn( Po, ) 95.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. @ Soe 2), _-206,833 In(Peo: Feb.) = Graaya00) Since Foo, = 2Peos 2) _ ~206,833 tle (hol) Sayan APGy = exp(~206,833/{(8.3144)(300)]) Poo = $.24x10-Hatm Poo, = 2Poo = 2(6.24 x 10" atm) = 12.48%10-atm ‘Note: Actual partial pressures may be modified by: (1) hydrothermal volatiles ‘associated with igneous processes or (2) decomposing organic matter. [5.20] ‘Thorium metal is used as an alloying addition in magnesium technol- ogy and is also used as a deoxidant for molybdenum, iron, and other ‘metals. However, thorium may corrode in water vapor to form thorium oxide and hydrogen and lose weight by spallation. Discuss the feasibil- ity of controlling the gas phase composition asa method for minimizing corrosion. The following data is provided (Wilkinson and Murphy, 1958, p. 213-215): ‘Th 2H,0(g) > ThO, + 2H,(@) AG = 171 kcal. Solution (1) Sap THE 4 24,0) AE#8—> Tho, @ +2449) AG ZAG, <0) AG, ZAG, The) + 2H,0l) SS8 5 Tho, (2)+24, 4) ao CHAPTER 5 = AGRy + 28G, + G,~ AG, ~246, AG, ) Substitute AGSog = -171 kcal/mol (given) 24G, = RtIn(7,) 3,= 0 (pure condensed phases) AG jg = 0 (equilibrium) 2AG, = RTIn(Ai,o) ‘Substituting into ZAG, = 0, 0= -171,000+ Rin( 7, -Rrn( 72.0) (4) Solve Inf Fa, 171,000, Fro) H9ENN 29 A, Pao ie = 5.1% 108 or HH = 2x10, Fi,o Fa, It would be impossible from a practical point of view to hold Fy,0 sufli- ciently low to shift the equilibrium from right to left.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. CHAPTER 6 Chapter 6 [6.1] Derive an expression equivalent to Sievert’s law, [6-72b], for solution of hydrogen gas in an aqueous solution. Assume Henry's law. Solution (1) St Up AG . = 4 (A y—AS> Hy (Qy= My =Ca) i Jes oe AG! 2 He (1) SH, Can, = bxy = GP) (2) Sum ZAG, =0= AG? + AG, -AG,- AG, G) Substituu y= AES 20, ora 46, =RTIn(Cy, /Ch,) AG, = RTIn (7, ) Substituting into ZAG, = 0, 0= ally ~T8S3 + RT In(C,, /C3,)~RT'In (P,) Solve nf, /0%,)/P,]= (ag +Tasy)/Rr Gu. = A Ray where constant k= Cf, exp(-atlg + 73s9)/ RT}. [6.2] Sievert’s constant for solution of oxygen in liquid silver is k = 193.6 ‘cm*.atm-*/100 gm Ag at 1075°C (Darken and Gurry, 1953, p. 513). Calculate the solubility of Ag atthe same temperature if 7, = 50 mm Hg. a iTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS: Solution Cy_= 193.6 (50/760) = 49.7em*/100 gm Ag. [6.3] | Referting to Example Problem 6-5, show from the Gibbs-Duhem equation that 77, = -20,083(1 -X,,? J/mol. Solution Substituting 778, = -20,083(1 —X,)° into [6-57], Xqdl-20,083(1 — X14 X,, a7%,=0 aH, i ] he Xu ye Xow Se “ame, =- [ro 7a 04 )166)(1—XeyJaXe --%2(40,166) Hi, = -20,08H(1- Xq,)° S/mol, [6.4] Calculate the composition (a/o) of a binary A-B alloy in equilibrium with oxides A,O and BO at 627°C, Given AGS o= —15,000 cal/mol and AGo= ~25,000 cal/mol. Assume solvent A's ideal. Solute B is ‘Henrian with % = constant = 1.15. The metallic phases are completely soluble in each other, whereas the oxides are insoluble. Solution ) SetUp 4,0 (2+ Bis) AS 5 Bolg + 2A (S) AG AG3 v) the. 246, A, O18) + Ble) ASB2e 5 ore) + 2A (5) @ Som AG, =0= AG%y +24G, + AG,~ AG AG; AG, 100 CHAPTER 6 10,000 cal/mol 2GR = 2RTin(a,) = RTIN,2) AG, = AG, = 0 (pure condensed phases) O (equilibrium) AG, = GF =RT In (¥,X,) = RTIN(L.ISX,) Substituting into ZAG, = 0, 0 = -10,000 + 1.987(900) In(X,2) ~ 0~ 1.987(900) Inf1.15(1 ~X,)} ) Salve 1788.3{In(X,2) - In(J — X,)] = 10,249.94 xt 7h mons Xj + 308.483X, ~ 308.483 =0 X,= 0997 => 7 0 1.003 => 0.3.40 B. [6.5] For the binary liquid alloy system Cu-Za, the zine vapor pressure at 1060°C is given as a function of composition in the following partially ‘completed table (Darken and Gurry, 1953, p. 512): X, 005 010 0.15 020 030 045 10 P,, (atm) 0.0289 00592 0.1184 0.2368 0.6000 1.2763. 4,000 cn Yn o Gas an » Value is high compared to data in Appendix A, Table A.S, (@) Complete the table (use metric units). (b) Does the system obey the ideal, Henrian, or regular solution ‘model? 401‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Solution @ Soy 5 = YoaXrg = Poof Ph, = Pl Ye You = Sad X om Gz(J/mol) G%, = RTin(a,,) = 11,083.1 In (a,,) GEE (mol) GH = GF, - TH = RTIn(y,,X,,) - RT InCX,,) = RT In.) = 11,083.1 In) GE (sol) ta = Gin ~ G9 = RTIn (y,.Xz,) -RT In (Y,,) = RT In(X,,) = 11,083.1 In(X,,) foe GH =RTIng,,) = G8, ~ Oi = WE, ~T9%, - Omi =0,(1-X,, + RTIN(X,,) —RTINX,) RT In(y7q) _ 11,088.11n(,,) = REIN zg) _ 13,088-1n( 74) ee (ora) se ees) x 015 | 02 | 050 | 045 | 10 Pfam) onres | 02258 | 600 | 127 | «0 & 0296 | oosee | oso | oso | 10 a e197 | 0296 | 0500 | 0709 | 10 Glue _| -54694 | 46.695 | ~soor2 | -31,900 | -21,006| -12669 | 00 G3** (imal | -21,492 | -21,175 | -18,005 } -19.493 | 7682 | -a11 | 00 GE tumoy | -39.202 | -25,520 | -21.06 | -17,938 | -13364| -2850_| 00 2,, 26,603 | -26,142 | -249et | -21,082 | -15,678 | -12600 | unt () BF decreases as X,, > I hence, the solution becomes ides} with respect to Zn. The solution is gular for approximately 0.05 0.30. Data is insufficient to compute the dilute solution coefficient although examination of the table suggests that 7, ‘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 of a Tiquid solution comprised of components A and B (X, = 0.8). The liquid solution is also at 1200°C. If A and B form ideal solutions, calculate the Gibbs free energy change resulting from the addition of solid A to the mixture. Assume C> (liquid) = C} (solid) and C} is independent of temperature, aH{ = 24,000 I/mol at 1800°C. 102 CHAPTER 6 Solution Since solid A is added to the solution, the heat of fusion must be the final result. Note that the notation G% implies that pure A is the 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 GX 1) RTINx,). Equations characterizing the addition of A to the solution are: (1) A°S 5 a" AG = anf -Thash Q) A* 4A" Gi Gt =Gh -(RTI“(X,) ‘The result of adding A is found by combining (1) and (2): @ AS oA, Tk- Ges Gk -GRS = anf - 11 as{ + (DRT In(Xq) ALT= 1800°C, solid A melts, hence A AM AGL =0 AG, =0= AHL —TVAs{ AH, _ 24,000 asi = 40h (mol if = ta = PG00 = 11.58 I(mol-K) Since AG, =O from the problem statement, A{ and AS{ are constants. Substtahg into a@i AH{-T’ast 4,000 — 1473(11.58) + (1)8.3144(1473) In(0.8) 4210I/ mal [6.7] The molar heat of formation of liquid brass according to the reaction (1 = X)Cu + XZn — CuzZn is given by Hm = ~7100X(1 — X) cal/mol (Upadhyaya and Dube, 1977, p. 139). Determine the expressions relat ‘ng the partial motar heats of mixing of copper and zinc in liquid brass to the alloy composition. Soluiion ‘Since Q is a solution constant, itis applicable to the partial properties of both components. Hence, HE, =-N00(1 -X,,?; His =-7100(1 -X,,).‘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, = 1.0 at the solubility li 1=b(1.5) b=2,(w/o) 5) =2/300.5) =033. 169] Antimony isremoved from lead during the refining process by selective ‘oxidation (Darken and Gury, 1953, p. 513). Estimate the Sb content obiained for ar agitation of the bath at 1173 K, State assumptions and use the following data: AGiif,=~ 417,600 J/mol Sb,O, and AG y= = 395,000 Jmol Sb,O, (Wieks 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 approaches, assume that Sb behaves ideally at dilute concentration. Method 1 () SetUp 25b(D +340,(g) ASU» $b, 0512) wy fn) foe ateun #26 0,¢9 SEtIny ss (2) @) Sum LAG, = 0= AGh73 + AG, — AG ~ 37286, ~ 265, 104 CHAPTER 6 ) Substitme AG, = 0 (pure condensed phase) un = 0 (equilibrium) 3728, = RTIn(73! 2G; = 2RTin(ay) = IT In(X,,) Tofind AGP75, use AG? = AH} ~ TAS? and the given data to calculate AH? and aS2. Assume AH and 489 are constant between 1100-1200 K. Sub- tracting: 417,600 = aHig- 1100 482 = 395,000 = alg - 1200 a82 =22,600= 100.a89 = ASP =~226, Substituting ino the first equation, 417,600 = Fg ~ 1100(-226) AH = ~ 666,200 GQ =~ 666,200 + 2267 ALLIT3 K, AGly3 = ~ 666,200 + 226(1173) =— 401,102 J/mol Substituting into ZAG,, = 0, =~ 401,102 — RTIn(0-21)"2 — RTINX,,) ) Solve X= exp 101102 ™ 2(8.3144)1173 exp (19.43) Xq 3.65% 10? From Example Problem 6-3, (6-5b], (fo) = 3.85210" 4121.76 «100 's = 3.65% 10 x 121.76 + 1x207.2 21x10" wlo=2 ppb Method 2. ) SetUp 25b (1) 4 aPto (© AEH> 3PbWU+Sb,0, (©) gt fon ©) aagt fae 2SbU)-+3PbOCe) E> 2Pb (2) +8k40,6) 105THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS @ Sum LAG, =0: G) Substitute AG, = 3AG, = 0 (pure condensed phases) 3G =0 (X= 1.0) 8G yyy = 0 (equilibrium) 265! = 2RTIn(X,) Assuming Table A.4 data for AG, is accurate AGFiq3 = — 401,102 ~ 3[-229,930 —33.68(1173)log(1173) + 209.64(1173)] = ~85,262 Y/mol = AGiins + AG, + 3G BS - AG,,,,—3AG, — 26%! =1173K, Substituting into ZAG, = 0, 0 =~ 85,262 - 2RTIN(X, @ Solve 2RTIn(X,,) =~ 85,262 Xqu= exp) 528262 | _ 013.07 28 wlo = 8000 ppm. n= XS STaa TTT) S8wlo = $000 pom. 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 _ Brin(y,) Ox) Solution () GP =H? 157 =9,(1-x,) -7f-Rin(X,)] (2) GF =RTIin(y,X;) 106 CHAPTER 6 Equating (1) and (2) and rearranging, QC-XP=RT GX) - RT in(X) or 0, (x)= RT In(y) => 9; = RTIn(Y) (rx) [6.11] Show that if a solution component i exhibits ideal behavior at constant temperature, V" Soluion By analogy with (4-14), dG?“ = VP“ap —3"“ar, Atconstant temperature, dG? = 77 ap or (F),, ‘Substituting [6-26] for component i, P, [6.12] During low temperature-high pressure metamorphism, the albite component inthe 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 dsiy, = 1. Referring to Exercise Problem (4.22): (@) Calculate AG, asa function of temperature, activity of albite, a, in lagioclase, and activity of jadeite, ay, in omphacite. (b) Assuming ideal mixing, determine AG, as a function of tempera- tetany, Solution (2)Antatemal ops sed flows (1) SetUp NGAIS,O, Ce) AS NoAISLG, (0)+S10, ©) AG, Ac, 46, | ° 50,68) ASE SNaAlSi,0, (O+Si0, (5) 407THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. 2) sum EAGy, |= AG? +AG, + AG, ~ AG, - AG, @) Substitute AG?.G/mol) = 53.21 x 10°- 2000.4T + 238.21TIn(T) 10349 x 1027+ 3.791 x 1047? 417478 x 10"T* + 2460.4 x 10°T* AG ;= 0 (pure condensed phase) AG,=RTIn(a,) Substituting into ZAG,, = 0, 0 = 53.21 x 10° 2000.47 + 238,21TIn(T) - 70,349 x 10° 43.791 x 104T* + 17.478 x 10°T°S + 2460.4 x 10°T -4#RTin(a,.)— AG, - RTIn(a,,) @) Solve. 4G, (Jmol) = 53,21 x 10° -2000.4T + 238.21TIn(T) $10,549 % 10-7T? + 3.791 x 10-*T? + 17.478 x 101 + eri{ 2) 2460.4 x 10°T- () Assuming ideal mixing, a, =X,, and a,, = X,,, hence 4G,(dImol)= 53,21 x 10° -2000.4T + 238.21TIn(T) 10,349 x 1057+ 3.791 x 104 T+ 17.478 LTS + 2860.4 x 107 snr( Zs) 16.13] Plagioctase feldspar, one of the most common rock forming minerals, exhibits complete solid solution between the pure end members albite (Ab), NaAISi,O,, and anorthite (An), CaAl,Si,0,. Solid solution min- ral compositions are usually given in abbreviated form, such as ‘AbjcAtjg, 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- ‘mogeneous liquid solution of Ab, An, at 1350°C is: Gling ~ 383 1623R race 108 CHAPTER 6 where AGln is the standard Gibbs free energy change at 1623 K for the phase trasformation An() > An(g) The molecular weight of bite and anorthite are 262.23 and 278.21 respectively. State assumptions. Solution (1) SetUp Bat) AS2> ancy) Gn 8 ACuz3 An(t) A222 5 Ang) @) Sum ZAG, = 0 = AG fans + AG, - AG, ~ AG, Q) Substitute AG, =RTIn®,.) Ges = 0 (equllibrium) AG, = TR = RTn(a,,) = RTIN(X,,), #88umng ideal mixing. X= tan. 80( atx) Mast an 20(cehes) + 80Ct) hence, AG, = RTIN(0.79) Substituting into FAG, = 0 BGs + RT IN(Pyy)— RT 10.79) @) Solve RTIn(P,,)—RTIN(0.79) = -AG Say ~AG ins + 1623)1N0.79)]8 = AG + 0623){in(0.79)]R wa) 1623R Pg, xp ~2Gos 3838 = 1623R SSS anorthite is table in the gascous state at 1350°C,‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. 410 ‘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 Bi is desired, the high Bi liquidus side ofthe eutectic ‘must be analyzed (GF, is defined relative to pure liquid Bi). The following data is obtained from the Bi-Pb phase diagram: Point on ‘Temperature wo Liquidus ‘cK Bi 1) 125 398 56 2) 175 448 70 3) 200 473, 16 Using (7-5], regular solution, no sotid solubility and data from Table A.2: 2¢(1- 56)’ + 10,879 BBLAE Ta(B6) + 20.00 2¢(1~.70) + 10,879 B.3144 1n(0.7) + 20.00 22¢(1-.76)" + 10,879 “8.8144 In(-76) +20.00 (1) 398 = @ais= Solving for 9 and averaging: 5167| 6560} 04, = -5875 (Jmol) ‘Substituting into [6-43], GB =-s8750 -.5)* + 8.3144(625)i(5) Note: From Kubaschewski and Alsock (1979, p.411) Tip = ).167 Jmol-K). mtTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Using this data, ay, = 0.396, Although the regular solution model assumes i = 0, the agreement is within experimental error. 17.2] Using the results from Exercise Problem (7.1], calculate the equilibrium Fo, qy 0veran equimolar Bi-P liquid solution at 625 K. The Gibbs free enefgy of formation of dibismuth trioxide, Bi,O,, is AGZio, = — 407,250 J/mol at 625 K (Wicks and Block, 1963, p. 21). ——S2_> Bi0,¢¢) 26 ab Ac, Ae, 2Bi (L)+ % 0, (9) AS25555 0,(6) (2) Sum YAGn = 0= AGL + AG, ~ AGias-KAG, -265" G) Substinute Gs =~ 407,250 Hol (given) AG, =0 (pure condensed phase) 8G eas =0 (equilibrium) Kae, =¥4RTn(P,) IH =2RT Ma (ay) Substituting into ZAG, 0 =~ 407,250 7(8.3144)(625) }-2(8.3144) x(625)ta (0.38) @) Solve P= 14x10-atm, 112 CHAPTER 7 Note: ‘The result indicates that Bi will oxidize from solution since it would be impossible to maintain such a low Pp, {7.3} From Kubaschewski and Alcock (1979), solution data for a 70 a/o Bi- Pb solution (Exercise Problem [7.1)) are: Hg'= 70x 4.184=-292.9 Imol and 533° = 0.03 x 4.184 = 0.1255 J/(mol-K). Using this data, esti- we hat of son ot Bt Solution From Table A.2, T'= 544 K and AH f, = 10,879 J/mol. From [7-2], -292.9+ Adify ~ 91255-83144 in (0.7)+ ANI a Solving, AH{, = 9507J/mol or 13% error. ‘The error is attributed to reading error from the phase diagram and assumption that AC, = 0. (7.41 Repeat Exercise Problem [6.9] nsing the following solubility data esti- ‘mated from the Pb-Sb phase diagram in Appendix E, Figure E.9: X,, = 03 at T= 598 K and X,,= 0.2 at T= 533 K.Notethat the solubility data is given ata much lower temperature than the refining temperature. ‘Assume: (1) Calculated solution parameters hold atthe higher temperature, (2) The process involves the reaction 256+ 3PbO(s) ~» 3P5 + Sb,05(s); (3) Sb behaves as a dilute solution component at these concentrations. Solution From Exercise Problem [6.9], approach 2 at 900°C, a, = 0,013. If Sb acts as a dilute solution component at this temperature, 0.013 4g =0.018=bgXq or X, where by, (dilute solution) = Ya, From [7-4], h, and s, are determined and then b,, is calculated: hy +19,876 () 933 = 515.982 + 22.01 413‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS hig +19,876 @) 598= 5 10.01+2201 Solving simultaneously, hy, From [6-38], ~3341-1173-437)]_| 83144173) | 3341: sy =-4.37. Substing, Xq= 2212 001126500 9m 5 ‘Note: Assuming that Sb behaves ideally (Exercise Problem [6.9]-Method 2) Yields result 255 higher [7.5] For dilute solutions of carbon (graphite) in liquid sodium, solubility GH = 3766 -1423(0.1) = 3624 Xj=0.7 9 GE = 1435 -1423(.084) = 1315 X,=0.9 = GE = 159 - 1423(,004) = 153.3 Ans: Xo (005) enO. Tea) g0e] ROS) o7 | 09 GE [aasor] 11303 | ess [seo [isis | as33 G/mol) (b) Using [6-47], Gee is calculated as follows: QN(1—X,,? =12,889(1-0)* 2,889 J/mol X= 00= GS = HM Xp,= 0.1 => GE = 12,889(1-.1)?= 10,440 X= 0.3 = GE = 12,889(1-.3)'= 6316 X= 05 = GS = 12,889(1-.5)? = 3222 12,889(1-.7? = 1160 12,889(1-.9)* = 129, Ans: Ka 00] 01 [0s | 05 | 07 [oo GE Timo!) | 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 [7.71 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 t0 1000 atm. Solution ‘Using data from Example Problem 7-8 and Table B. 141 - a xh, 7 7 be ual orm)" aa) 8, =21,111 mol and 28, = 22,720 I/mot 8354 896 predict. Assuming Vg < VB, < Vg, the maximum possible value of Vise, ming Va = V8.8, 92cm" mol. VB, is more difficult 10 10.284 em*/mol 1049 ‘Substituting into (7-256), 1 21,114(1-.952)" + (7.092 10.284¥9904.1018) -22,720(1~ 141)? s.a144in( 24E 48,6~-323- 16,765 See 1073K From Figure E.7, T,= 1053K. The eutectic temperature shift is a maximum of 220K. In realty the shift is less—depending upon the actual value of 2, (7.8] Refer to the eutectic phase diagram shown in Appendix B, Figure E.10. (@) Identify the components that constitute this system, (Is the system isobaric or isothermal? (©) Give the phase rule expression that is applicable to this diagram, (@) Label the diagram at phase assemblages that are: invariant (F =0), univariant (F = 1), and divariant (F = 2). 417‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (©) What is the equation (temperature) of the horizontal line through the eutectic point? (What is the equation (temperature) of the phase boundary between tridymite and cristobalite? Solution (@) Albite: NaAISisO, and Silica: SiO (b) Isobarig (©) F= F(Components) - @ (Phases) +1, since pressure is constant. (@) The degrees of freedom and corresponding numbers of phases and ‘components are labeled on the phase diagram illustrated below. |e Feo (E57 ei (225) unit Fe (E28) ty 30, wii 05 NaAlSi,0,-SiO, eutectic phase diagram. (From C. Klein and C.S. Hurlbut, ‘Jr, 1985, Manual of Mineralogy, Fig. 12.5. Reprinted by permission of John ‘Wiley and Sons, Inc., Copyright © 1985.) © T~ 1950 (0 T~ eee. [7.91 Using Figure E.11 in Appendix E, develop a temperature-dependent expression for the diamond-graphite phase boundary between 45-105 kbar, Is this boundary invariant, univariant, or divariant? See Exercise Problem [7.8]. Solution As illustrated below, the plot isa straight line from 1000 to 3000 K. Hence, its equation is P = mT + b where m is the slope and b is the P- intercept. 118 CHAPTER 7. 120 I Groghite 50004000 Temperature, (°K) Diamond-graphite univariant phase diagram. (From E,G. Ehlers, 1972, The Interpretation of Geological Phase Diagrams, Fig. 93, Reprinted by permission of W.H. Freeman and Company) at 1000 K, P = 36 kbar at 3000 K, P = 94 kbar 94=3000m+b 36= 1000m+b m= 0,029 kbar/K. = T kbar ‘The equation is P(kbar) = 0.029 x TK) +7 Fe P-O42=1-242=1 = univariant boundary } soe simutanconsty 17.10] Estimate the equilibrium vapor pressure of $O,(s) over SO,() at 265 K. State assumptions. Solution ‘The univariant equilibrium transformation is 80,0) + SO,(g) Using Table A.2 data, assuming AH™ ~ constant (AC, ~ 0), and integrating the Claussius-Clapeyron equation, [7-20] 119‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ui 24,937 > dT [fem = 2001( 1b de sO = ar sa P = 1.09 um : [7.11] Estimate the solid-liquid isothermal transformation temperature of Au at 75 atm, State assumptions. Solution ‘The univariant equilibrium transformation is Au(s) Aud) From the Clapeyron equation, [7-21]: dP _aH™ dT _aVdP ar Ta T an™ From Table B.1, 197197 = Vea Vougo = oe 222 w= 1.38 emn¥nol AV= Vag Vawo 7757 Tod = E38 em"mol From Table A.2, AH™ = 12,760 J/mol Integrating (7-21) while assuming AV and AH™ constant: 7 ar 138% hase P12, 76041 PAHO) or <1 or P= wi) aes) Pree RR 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 @ SiCL(g) +2F(@) -» Sit + 4r1CK@) Subsitatng (5-4) and (62 ino [8-2] where Ja = K,, es Keg =o Ma SEF You YigPy Ta-Tas (©) Examination of this expression reveals that an increase in total pressure hhas the effect of dectessing the yields of Si(s) and HCI(g). Yq in the expression must dorease in order t maintain K,, constant. AH? ME soins RT necessary to know whether the reaction is endothermic or exothermic, (©) Referring wo the Van't oft equation, (8-71: In.) From Table A.1 and assuming AC, = 0, AH = 40H 30 — SHB sic, =4(-92,32) ~ (- 662.81) =#293.53 ki/mol. ‘Since AH. > 0, Keg inereases as the temperature increases, [8.2] The decomposition of Fels) (decarburization) ina steel exposed toa hydrogen environment can result in the internal formation of CH,(g).. Intemal pressure created by accumulation of the CH, can lead to 90 called hydrogen attack because CH, cannot diffuse from te laice suc. ture. Repeat Example Problem 8-3 for exposure to a mixture of H(g) and CH,(@) at 500°C and determine the maximum Fey, / Ri, ratio that can exist without causing significant decarburization ‘and ‘subsequent hydrogen attack,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution Decarburization in hydrogen involves dissociation of Fe,C according othe reaction Fe,C(s) + 2g) -» 3Fe(s) + CH) Using (8-31, a SG Kg= Po, Pi on gt ‘From [4-9] and Table A.4, 869, = 40 %eq, 80 no =~ 69125 + 51.26(773) x 1og(773) — 65.36(773) ~ [26,700 - 24.77(773)] -12,761 J/mol. Pag [re wemy(__221S_ Hence, K,,= Fou, /i, (gsicnem 2.283 (maximum) atm, simultaneous solution with Fy, + Ze, = 1 yields 1692 aim, 308 atm, [8.3] Estimate the total enthalpy change associated with modified austempering of one gram mole of 1050 steel. Identify all assumptions made and source materials used. Solution ‘According to the Fe-Fe,C phase diagram, 7 (austenite) transforms to a (ferrite) and Fe,C (cementite) atthe eutcctoid temperature (1010 K) when cooling is slow. For quenching and isothermal hold (500°C) described in Exercise Problem (2.3, the problem becomes: (1) Calculating AH, for the > o. transformation. (2) Calculating AH® for the reaction 3F% + T -» Fe,C at 73K. Assume thatthe weight fractions of o. and Fe,C are identical to that calculated by the lever rule at just above 1010 K on the Fe-Fe,C phase diagram, ‘Also assume thatthe activity of carbon in austenite atthe austeitizing temperature will hold atthe quenching temperature. From Exercise Problem [2.3], AH Fig = — 6855 J/mol for the y —> or transformation, 122 CHAPTER 8 4H1,4¢ is calculated from TL analysis and application of the Gibbs- Helmholtz equation, [4-30] (Q) Sep so = AG. af + © —— > Fe,c sen |e AG, Ae, 3fe + C ——1 > Fe ,C 2) Sum = AG? + AG, - AG, - 38-30%, zing temperature of 800°C, the activity of carbon in 1050 steel (0.5 wo C) is a, = 0.0273/0.054 = 0.51, where, from Appendix A.6, 20.5 w/o C) = 0.0273 and a,(0.876 w/o C) = 0.054, (The solubility of carbon in austenite at 800°C is 0.876 wio C.) From Table A.4, AG $= 26,700 24.777 AG, = 0 (pure condensed phase) GE = 8.31447 In(0.51) =-S6T 3GR ~ 0, [RTIn(a,) = 0 as X,. -> 1] Substituting into $46, ~ 0. 0 = 26,700 24.771 - AG, + 5.6T (4) Solve AG, = 26,700 - 19.177 ‘Substituting into [4-30], 226.700-19:77)/7 _—alty a 7 26,700 _ a, ear oe ‘AH, = 26,700 Yel. 123‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (The same result can be obtained directly from the AG expression). Using the lever rule, the mass fractions of «& and Fe,C are: 07-05 "= 77002 078 fpejo = 140.36 = 0.64 Converting to mole fraction, x,=—— T+ Mee 0.36/55.85 0:36/55.85 + 0.64/179.6 = 0.044 Xjeso = 1 00644 = 0356 ‘Summing the respective enthalpy contributions: BH ropa, = 0.644(- 6855) + 0.356(26,700) 5091 mol, ‘The data suggests that heat absorption due to carbide formation is dominant [8.4] Manganese sulfide inclusions in steel are interfacial traps (sinks) for hydrogen and hence tend to increase the total or “effective” hydrogen solubility. Depending upon the distribution and size of the inclusions, they may increase the susceptibility ofthe steel hydrogen embrittlement or hydrogen environment cracking (HEC). (@) IF H,S(g) and H,(g) are present in the contacting atmosphere, what isthe critical ratio Py,¢ / Pg, above which MnS(s) and H,(g) form at 1500°C and 1 atm? (©) The calculated critical ratio in (a) for minimizing HEC in steel may not be confirmed experimentally. Name two factors that are not considered in these calculations. Solution (@ From Example Problem 5-4, Pp /Po, = B10 (B) Solid state Kinetics are normally slow and are not involved in thermodynamic caleulatons. The ealulated ratio doesnot ke into account solubility effec, 124 CHAPTER 8 [8.5] Referting to the data in Appendix A, Table A.S, show that In(, (atm) = — 40,349/7 — 1.21In(1) + 23.79. Solution Using in(78,) =2.303I0g,4() and 1 atm = 760 mm Hg: 17,520 log( P, mm Hg) = 1.21og(T) + 13.21 717,520 2.303log(760 Pj, (atm)) = 2.303 [- 349 1.2Mog(T) + 13.21] = 1.211n¢T) + 30.423 — In(760) 40,349 T =1.21In(T) + 23.79, [8.6] Referring to the paper by Iwai, Takahashi, and Handa (1986): (@) Confirm the data in the last three columns of Table II. (b) Equilibrium data are found in Tables Il and IT. Use the least means square treatment to derive the expression: AGRE (fmol) = ~ 68,270 + 8.237 where 1173 K $ T < 1573K. (© What assumption is implied but not directly mentioned in the ar- ticle? Solution (@) Column 3 AG? = -RTIn(K) = RTIn( Fey, /P2,) 8.3144(1173)In(47.4 x 104) 17.107 Jmol (check) Column 4 From Table A.4, AGM, = - 69,126 + 51.26Tlog(T) - 65.367 = ~ 69,126 + 51.26(1173)log(1173) ~ 65.36(1173) = 38,757 Yimol (check) 125‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS, Column 5 1) 2Mo + C->M0,C 2) 2H, +C9CH, @-@=6) @) 2Mo+ CH, > Mo,C + 2H, or (1) =) +@)=col. 4 + col.3 = 38,790 + (97,000) 10.Himol ( check) () Assume LMS linear correlation (see Fig. 2): AGRE c Ufmol) =~ 68,270 + 8.23T where 1173S T's 1573K © ac, “p™0. [8.7] The vapor pressure data in Appendix A, Table AS, ean be expressed in the form log,(P)=AT"+ Blog, (D) +D where C =0. (@) Starting with [7-20], develop the above expression forthe pressure (ofa vapor over its coexisting condensed phase at equilibrium. (b) What is the form of the equation if AC, = 0? Solution @ M6) > M@e) ap _ aH’ PRP Substituting (2-20} into [7-20] and integrating, [2-5/2 mat, a, , alo), In( Rr RT’ OR where I isan integration constant. Hence, logy9(P) = AT" + Blog,, (T) +D, where C= 0, (b) Substituting [2-19] into [7-20] and integrating, CHAPTER 8 ney = OP 4 mull RT or logio(P) = AT" +D. [8.8] Confirm that hydrogen dissolved in Ti(a) follows Sievert’ law. Use the following data given at 610°C by McQuillan (1950): Fargq (atm) Hydrogen Solubility in Ti(a) (ppm) 5.263 x 105 235 5.263 x 10+ 750 2.632 x 10° 1705 Solution From Sievert’s Law, [6-726], calculate k for each composition. Reasonable agreement of k values would confirm Seivert behavior. 28s 900! pe am? (6:263x10°) 130 * =3269x10 k= Gaax10)7 1705, =3323x10" b= Gar)” values are constant within experimental error, thereby confirming the law. [89] Repeating Example Problem 7-6 for carburization of alow carbon steel, ina mixture of CO and CO, at 900°C, calculate the carburizing potential required to develop 0.8 w/o C at the surface. Solution T +0,@) > 2c0(@) AG fy, Gimol) = 24G 2%, - AG, From Table A.4, AG fing = 2-111, 720 - 87,66(1173)] ~ [394,170 ~ 0.84(1173)] 8.3144(1173)In(K,) A w-sinse-snrmn Se) : ae 127THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS CHAPTERS All pot Lis AH9 =2113 x 2.308(83144)02) From Table A, = 20,920 Hol Hy 0.8 who C = a, = 0.048/0,0803 = 0.60 Substituting into the expression for AG, and solving forthe gas rato, AL2petLit AHS = 2797 x 2.303(8.3144)2) Py Poop = 19.466 = 107,114 Hino, Assuming Poo +Pco, = 1 atm, AL-3 pet Li: AH§ = 2889 x 2.303(8.3144)(2) By = 19.466(1 ~ Pas) = 110,638 Jinol H- 2p + 19.466 Peo 19.466 = 0 , Poti x? (fmol) Pay =0.953 atm a eae) tno = 19.485 check) 0 103,400 ivcmmaion 1 80,920 Note: Excess CO, (Foon > 0.047 atm drives the reaction from left to right, 5 ae hence CO, is deearburizing, 3 Ties 8.11] Referring to Exercise Problem [8.10], te dissociation of molecular hydrogen in liquid aluminum alloys is a two step process involving: (1) Dissociation of diatomic hydrogen into monatomic hydrogen and (2) Solution of atomic hydrogen in the metal. Using enthalpy data for the Al-I pet Lialloy, calculate A// for step 2if for step 1, Ally, = 419,500 J/mol H, Af, defined as the enthalpy of dissociation of diatomic hy- ‘drogen, is effectively constant over the temperature range of interest. [8.10] The solubility of hydrogen in liquid binary AI-Li alloys is given by “Anyalebechi, Talbot, and Granger (1988): Pure Al: log(s/s) - (1/2)log(P/P®) = -2700/T + 2.720 Ab Pet Li: log/s") ~ (/2)log(P/P®) = 2113/7 + 2.568 AL-2 Pet Li: logis!) ~ (1/2)log(P/P®) = 2797/1 + 3.329 AL-3 Pot Li: logs") (1/2)log(P/P®) = -2889/T + 3.508 where s*= I em*/100 gm metal at STP and P= 1.01325 x 10% Pa, ‘AH is the solute binding enthalpy for solution of monatomic hydrogen ‘The equations are valid from 913 to 1073 K and from 5.3 x 10*to 10.7 inthe mec, x 10*Pa, Determine the enthalpy of solution at each concentration. The Tast term in each expression includes an activity correction; hence, it Solution cannot be used to calculate AS3. (1) SetUp ‘From [6-72a] in Example Problem 6-9, ° ao as? H AHS = ane, AS 203K * 23088 Jog (Cy/CR) - 1/2 lot Fy, Comparing expressions, pee AHave® 7 A Lie 2.3048.3144)T Bit de ‘Ave AH = 2700 x 2.303(8.3144) 1,700 I/Y4 mole Hy 103,400 Simo! Hy 2H 128 129THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ©) Som YAH, =0= AH, + AH— AHS G) Substinuwe AH,,, = 419.500 J/mol H, ‘AH? = 80,920 /mol H, Substituting into LAH, = 0, (0 = 419,500 + AH — 80,920 (4) Solve AH = 338,580 J/mol H, 169,290 gm atom H. [8.12] Determine K,_ a8 a function of temperature forthe reaction in Exercise Problem [4.23 Solution From [8-3], AG}. =-RTIn(K,,) at equilibrium. Substituting the ideal gas constant R = 8.3144 J(mol-K) and AGS from -Exercise Problem [4.22], Ky = EXD(-455.96 X 109T?+ 8.46 x 10°T 2102.14 x TS — 6399.77 => 295.92 x 10°F? -28.65in(T) + 240.59) where T= TKK). [8.13] Referring to Exercise Problem [5.17] (2), What isthe equilibrium constant forthe reaction? (@) In which direction will the reaction shift i Ja increases? If Ja decreases? (©) What would cause the equilibrium constant to change? Solution (@) 2C(s) + 2H,0(@) -> CH(@) + CO,@) From (8-2) withJa=K,,, a! (Products) Kq= Par deans Heme Kye Fe, 88 Flo 121 190 CHAPTER 8 () According to LeChatelier’s Principle, If Ja increases, the reaction shifts to the Jeft until equilibrium is eestab- lished Ja=K,). If Jadecteases, the reaction shifts to the right until equilibrium is reestab- lished Ga=K,). (© The equilibrium constant would change in response toa change in sempertare 131

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