CHAPTER 8 Chapter 8 [8.1] Referring to Example Problem 5-6: (a) Find the equilibrium constant forthe reaction and discuss the effect of increasing (b) total pressure and (¢) temperature. (@ SiCI(g) + 2H, — SiG) + 4HCK) ‘Substituting [5-4] and (6-2) into (8-2] where Ja= K,,, Yiu? STE Yoo = pee Ya, Ya, (b) Examination of this expression reveals that an increase in total pressure has the effect of decreasing the yields of Si(s) and HCI(g). Yqaq in the expression must decrease in order to maintain K,. constant. ane (© Referring othe Van't Hoff equation, (8-7): Ink) = “SUE +C, tis necessary to know whether the reaction is endothermic or exothermic. From Table A.1 and assuming AC, = 0, AH? = 40H hua ~ SHB si, =4(-92.32) - € 662.81) =+293.53 kJ/mol. Since AH? > 0, Key increases as the temperature increases. 18.2] The decomposition of Fe,C(s) (decarburization) in a steel exposed to a hydrogen environment can result in the internal formation of CH,(g). Internal pressure created by accumulation of the CH, can lead 10 so called hydrogen attack because CH, cannot diffuse from the lattice struc ture, Repeat Example Problem 8-3 for exposure to a mixture of H,(2) ‘and CH,(g) at 500°C and determine the maximum Poy, / F, Tatio that can exist without causing significant decarburization ‘and subsequent hydrogen attack. 121THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution ‘Decarburization in hydrogen involves dissociation of Fe,C according to the reaction Fe,C(5) + 2H,(@) — 3Fe(9) + CH(g) Using (8-3), nna ih cont Ke Patt, =o gt ‘From [4-9] and Table A.4, G2, = AG hea, - AG pee =~ 69,126 + 51.26(773) x ‘og(773) — 65.36(773) ~ (26,700 - 24.77(773)] 12,761 Y/mol . 2 12,761 Hows a= en [R= 20 ayers) = 128 (maximum) 1 atm, simultaneous solution with Py, + Pew, = 1, yields 0.692 atm, 308 atm. ALP, Pau, Fa, [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, y (austenite) transforms to (ecrte) and Fe,C (cementite) at the eutectoid 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 7 — 0 transformation. @ Calculating AH® forthe reaction 3Fe + C > Fe,C at 773K. ‘Assume thatthe weight fractions of a and Fe,C are identical to that calcu- lated by the lever rule at just above 1010 K on the Fe-Fe,C phase diagram. Also assume that the activity of carbon in austenite at the austenitizing temperature will hold at the quenching temperature From Exercise Problem (2.3), AHF, = ~ 6855 J/mol for the y —> or transformation. 122 CHAPTER 8 dl ;a¢ is caleulated from TL analysis and application of the Gibbs- Helmholtz equation, (4-30): () SetUp af +E > Fee LD 3G |S, AG, A 3fe + C pas Q) Sum TAG, =0= AG$ + 4G,-AG,~ 02-30% G) Subsite Aan austnitizing temperature of 800°C, the activity of carbon in 1050 steel (05 w/o ©) isa, = 0.0273/0.054 = 0.51, where, from Appendix A.6, 305 wwlo C) =0.0273 and a,(0.876 wio C) = 0054, (The solubility of earbon in austenite at 800°C is 0.876 wio C) From Table A, AG$ = 26,700 - 24.777 AG, = 0 (pure condensed phase) 31447 in(0.51) =-5.6T GR =0, [RTIn(@,)~0 8 X,,— 1) Substituting into SAG, = 0, 0 =26,100- 24.77T -AG, + 5.61 (4) Solve AG, = 26,700 - 19.17T Substituting into [4-30], 3{26.100-19.71)1 7 _-Aty 26,700 _ -AFh Tra. oe AH, = 26,100 Simol. 123,THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (CThe same result can be obtained directly from the AG expression). Using the lever rule, the mass fractions of or and Fe,C are 077-05 = 0.77=0.02 frac = 1+ 0.36=0.64 Converting to mole fraction, 036 jomellmne Tat hege = 0.36/55.85 *036/55.85+0.64/1795 = 0.644 0.644 = 0.356 Xne Summing the respective enthalpy contributions: AHL, = 0.644(- 6855) + 0.356(26,700) = 5091 Yo, “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 ste! to hydrogen embrittlement or hydrogen environment cracking (HEC). (@) IFH,S(g) and H,(g) are present in the contacting atmosphere, what is the critical ratio Py,s / Pa, above which MnS(s) and H,(g) form ‘at 1500°C and I atin? (b) The calculated critical ratio in (2) for minimizing HEC in steel may not be confirmed experimentally. Name two factors that are not con- sidered in these calculations, Solution (@) From Example Problem 5-4, Pas /Py, = 5102 (b) Solid state kinetics are normally slow and are not involved in thermody- namic calculations. The calculated ratio does not take into account solubility effects. 124 CHAPTER 8 18.5] Referring to the data in Appendix A, Table A.5, show that In(P, ) atm) = ~ 40,349/7 — 1.211n(T) + 23.79. Solution Using In(P,) = 2.303l0g,,(78,) and 1 atm = 760 mm Hg: 17,520 Jog( Fé, Meum Hg) ~ 1.21log(T) + 13.21 T 2.303I0g1760 Pf, (atm = 2.303 {12520 -1.21log(T) + 13.21) sf, = 222 _2uinc1) + 30.423 — In(760) -1.21In(T) + 23.79. [8.61 Referring to the paper by Iwai, Takahashi, and Handa (1986): (@) Confirm the data in the ast three columns of Table TL (b) Equilibrium data are found in Tables II and Ill. Use the least means square treatment to derive the expression: AGS ¢ G/mol) = - 68,270 + 8.23T where 1173K MO,C 2) 2H, +C—9CH, G) 2Mo+ CH, > Moc + 2H, or (1) = (3) + (2)= col. 4+ col. 3 38,790 + (97,000) = 58,210 J/mol ( check) (©) Assume LMS linear correlation (see Fig. 2: AGyid,¢ U/mol) = — 68,270 + 8.237 where 1173 M@) ‘Substituting [2-20] into [7-20] and integrating, AH, +0(T aff MD I WAHY af, | alot oh at a Rr RT’ R ‘where Tis an integration constant. Hence, gt?) =AT" + Blog,,(T) +D. where C= 0. (b) Substituting [2-19] into [7-20] and integrating, CHAPTER 8 [8.8] Confirm that hydrogen dissolved in Ti(o) follows Sievers law. Use the following data given at 610°C by McQuillan (1950) Pac (atm) ‘Hydrogen Solubility in Ti(a) (ppm) 5.263 x 105 235 5.263 x 10+ 750 2.632 10° 1705 Solution From Sievert’s Law, [6-726], calculate k for cach composition. Reasonable agreement of k values would confirm Seivert behavior. Bs = 3.23910" ppm atm"? (28x10) k, 2 Eee 526310) a =3.323x10¢ k= Gamn0™ ‘values are constant within experimental crror, thereby confirming the law. [8.9] Repeating Example Problem 7-6 for carburization of a low carbon steel] ina mixture of CO and CO, at 900°C, calculate the carburizing poten- tial required to develop 0.8 w/o C at the surface. Solution @+co,g) > 2c0@) AGP (mol) = 246% - AG 84, From Table A.4, 8G Pry = 2{-111, 720 ~ 87.66(1173)] — [-394,170 - 0.84(1173)] 83144(1173)iN(K,.) Pio 33,935 =— ssmaarroya( me ) 127THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS From Table A.6, 08 w/oC = a, = 0.048/0.0803 = 0.60 ‘Substituting into the expression for AGP, , and solving for the gas ratio, Roo | Foo, = 19.465 Assuming Poo +Peo, Pig = 19.466(1-P..) Po + 19.466 Poy — 19.466 = 0 953 atm .047 atm| Js Pay, = 19.466 (check) Note: Excess CO, (Feo, > 0.047 atm) drives the reaction from left to right, hhence CO, is decarburizing. [8.10] The solubility of hydrogen in liquid binary AI-Li alloys is given by Anyalebechi, Talbot, and Granger (1988): ure Al: log(si) ~ (1/2)log(PIP®) = ~2700/T + 2.720 Al-1 Pet Lis log(s/s?)— (1/2)log(P/P®) = -2113/T + 2,568 AL-2 Pct Li: log(s/s*)— (U/2)log(P/P*) = -2797/T + 3.329 AL3 Pet Lit log( s/s?) — (1/2)log(P/P*) = -2889/T + 3.508 where = 1 cm’/100 gm metal at STP and P°= 1.01325 x 10° Pa. ‘The equations are valid from 913 to 1073 K and from 5.3 x 10* to 10.7 X 10*Pa, Determine the enthalpy of solution at each concentration. The last term in each expression includes an activity correction; hence, it cannot be used to calculate 483. Solution From (6-72a] in Example Problem 6-9, ano, ast 8) tog hy, e- Hee § Jos Gu /C8) ~ U2 tog Py) =~ Se + Comparing expressions, Pure Al <=. ov00yr 2303(8.3148)T AH = 2700 x 2.303(8.3148) = 51,100 3/34 mote Hy = 103,400 Jhnol Hy CHAPTER 8 ‘Adel potLit AH =2113 x 2.303(8.3144)(2) £0,920 nol Hy AL2 pet Li: AH = 2797 x 2.303(8.3144)(2) 107,114 Jmol Hy ALS pot Li: AH = 2889 x 2.303(8.3144\2) = 110,638 yma Pai ‘2 (fmol) 0 103,400 £ 80,920 2 107,114 3 110,638 [8.11] Referring to Exercise Problem [8.10], the dissociation of molecular hy- drogen in liquid aluminum alloys is a two step process involving Dissociation of diatomic hydrogen into monatomic hydrogen and (2) Solution of atomic hydrogen in the metal. Using enthalpy data for the AL- pet Li alloy, calculate AH for step 2 if for step 1, AH, = 419,500 ‘I/mol H,, AH,,., defined as the enthalpy of dissociation of diatomic hy- drogen, is effectively constant over the temperature range of interest. {MH is the solute binding enthalpy for solution of monatomic hydrogen in the metal. Solution ) SetUp Hy AHS = 129THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS @ Sum DAH, @) Subsite ‘H,,, = 419,500 J/mol H, AH = 80,920 Jmol H, Substituting into EAH, = 0, (0 =419,500 + AH ~ 80,920 (4) Solve AH = ~338,580 J/mol H, = 169,290 Iam atom H. AH, AH aH? [8.12] Determine K,, as a function of temperature for the reaction in Exercise Problem (4.22). Solution From (8-3), AG? =—RTIn(K,) at equilibrium, Hence a) ‘Substituting the ideal gas constant R = 8.3144 J/(moF-K) and AG from Exercise Problem (4.22), = exp(-455.96 x 10-°T? + 8.46 x 10°T-2102.14 x T-3 — 639.787 => 295.92 x 10°T* ~28.65In(T) + 240.59) where T= TUK). [8.13] Referring to Exercise Problem [5.17 (@_ What is the equilibrium constant for the reaction? (b) In which direction will the reaction shift if Ja increases? If Ja de- creases? (©) What would cause the equilibrium constant to change? Solution (@) 2066) + 2,0) > CH(@) + COa) From [8-2] with Ja = K,. a (Products) Ka= [] ah teactansy Hence, Rah = Hh = 0.21 Ka" aE Pho CHAPTER 8 (0) According to LeChatelier’s Principle, 1 Jainereases, the reaction shifts to the Jefj until equilibrium is roestab- lished Ja=K,). If Ja decreases, the reaction shifts tothe right until equilibrium is reestab- lished (Ja = K,.). (© The equilibrium constant would change in response to a change in temperature 131