CHAPTER 2 Chapter 2 [2.1] Calculate the transformation enthalpy for the isothermal transformation of Ti(B) to Ti(@) if the transformation occurs 200°C below the equilib- rium transformation temperature during cooling. Solution @) Se.Up Te Atoes p TT RasKe? STI AH, Ou, Aue p Te? TI) Q) Sum Elly, = O= Alig + At ~ AH, ~My ae — ante Higgs = A195 + OH, ~ BF, ©) Substitute AMT, =-3473 Jmol 5s AH, = | (22.09 + 10.04 x 10 TdT = - 6536 J/mol 33 Ath = fa 9dr =-5182 Hino ss (4) Solve tT, = 4227 JmolTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS [22] Derive an expression forthe heat of fusion of $i as a function oft perature at 1 atm pressure. Solution () SewUp " H Sits) Tota? Si (W) AHy An, L aut F Si(s) — Si (2) 2) Sum Ally, =0= AM, + Blt ~Atifins ~AFly AHS, = AH\,, + 4H, - AH, G) Substitue 093 Au, fpscur = 43,358 25.617! by ‘AHfoys = 50,630 Jmol 1695 AH,= | (24.10+2.43%109 7 +.4.56x10°T?)ar rr 4.56x10° Aliy= 43,885 ~ 24.17 0.0011 717? + 4 CHAPTER 2 (4) Solve Ault, =$0,630+43,885~ 24.17! -o901171!2+ ~ 43,385 +25.6177 DUE ¢(S/mol) =51,157+1.51T! 0.001171"? +. 4,56%10° 77 4.56 x10° 1 [23] Modified austempering isan isothermal transformation heat treatment used to produce bainite and pearlite (a mixture of ferrite (a) and cc- ‘mentite Fe,C). The process involves austenitizing the stel to 100% aus- tenite (7) and then quenching to a temperature slightly below the nose of the “I-T” curve and holding at that temperature until the transforma- tion is complete. Estimate the transformation enthalpy for the transition ‘of a 1050 steel at the austempering temperature, Refer to the -T dia- gram for 1050 steel, Appendix E, Figure E.1, to select an austempering temperature, Assume carbon solubility has a negligible effect on the result in either phase. Do not include Fe,C in the calculations. Solution Review of the iron-iron carbide equilibrium diagram reveals that the 5-ycrtrans- formation tarts at=1038 K and ends at =1010 K, the eutectoid temperature. AS result of quenching, transformation is delayed and occurs isothermally atthe ‘quenching temperature. Based on the I-T diagram, a quenching temperature of 500°C is consistent with austempering, @ Seuup Since the computation of AH, x is path independent, any one of 3 loops might bbe selected. The outermost loop is selected because AHN is known from Table A2. 18SYSTEMS THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS AH,+ AH, — BHT ~ AH, H3,= AHY, +H, — AH, (3) Substitute AH = — 669 J/mol 0 Ad, Jornrsnonar = 3188 + 7907 = 11,095 J/mot 187 AH, = | 17494 24.77%10° Var ns = 7241 + 10,040 = 17,281 S/mol @ Solve ‘AH, =~669 + 11,095 17,281 855 Jmol. [2.4] The results of constant volume motar heat capacity calculations for sev- ‘ral solids are illustrated in Figure 2.6. For each substance, C, approaches zero as the absolute temperature approaches zero, In addition, C, as- "ymptotically approaches a constant value of 6 cal/(mol-°C) as tempera- ture increases, This constant, known as the Dulong and Petit value, is ‘best approximated for each solid in a different temperature range. For ead this temperature range begins at about 180 K and for Cat about 16 CHAPTER? yy do ia i Sai ey i i Ra i de rr a Kelvin teperstre Figure 2.6 Variation of C, of solids with Kelvin temperature. (From M.W. Zemansky and H.C. Van Ness, 1966, Basic Engineering Thermodynamics, Fig. 11.16, Reprinted by permission of McGraw Hill, Inc., New York.) ‘Calculate the molar heat transferred to or from the surroundings and the molar internal energy change occurring at constant volume when: (2) Cu undergoes a temperature increase from 600 to 700 K. (©) Pb undergoes a temperature decrease from 210 to 180 K. Solution 709 7100 @ Q=AU,=|car= | 6ar io oo where C, asymptotically approaches a constant value of = 6 calmol -K). Q,= AU, = 600 cal/mol Cu, from surroundings. 0 10 () Q,=AU,= feree- fox ° a0 Bt 0, = AU, = 6(180 210) = -180 cal/mol Pb, to surroundings. 7THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYS [2.5] Calculate the enthalpy change at 968 K for the reaction ‘2Si0,(s) + 2AI,0,s) — 2A1,SiO,(s), Use the following information (all phases are solids): (@) 2Si0, + 31,0, > ALSi,0, — Arffeq=-22.6 KY/mol (0) 2ALSiO, + ALO, > ALSi,0,, AHS Solution (@) 2810, +3A10, ASQ, (0) _rrg5i:0y + A140, +2A1,5i0, Hy =394 WSi0,(@)+2AL0s(9) 2AL,SI0,@) ly =168 inal Alig =8.4 kI/mol SiO. [2.6] Calculate the standard enthalpy of formation of CaCO, at 298 K in ‘kcal/mol and kJ/mol from the following data: (@) Ca0() + CO,(g) > CaCO) AM yg= 42.85 kcal/mol (b) Ca(s) + 1/20,(g) + Ca0(s) © CG) +04) + CO.) AHSh-= -94.05 kcal/mol Solution (a)C2OG) + COQ) > CaCO3(8) AM ig = 42.85 kcal/mol (b) Ca(s) + 1/20 269) Ea) HRS = 151.50 kcal/mol OCG) +0, > COa Ca(s) + C(s) + 3/20 2@ — CaCO(s) AHSSh =-288.4 kcal/mol AHS, = 288.4 keatmol= 1207 tno). [2.7] Given A? =-1133 ki/mol O, for the reaction PAIS) + O,(8) = (2/3)A1,0,(8), (@ Show anf = 1133 ki/mol if AC, = 0. (b) Select the correct alternatives below for AH; 18 Hf =-94.05 team! CHAPTER 2 (1) 4A) + 30,4) = 241,06) (2) 2Alls) + G2)0,(8) = ALO) (3) 4Al(s) + 30,(2) = 2A1,0,(3) (4) 2AU(s) + (3/2)0,(g) = ALO,(s) (S) 2AK(s) + (3/2)0,(8) = ALO,(5) Solution 7 @ Ane = AHMs + | AC,aT 28 IAC, =0, =1133 ki/mol O, 33 kcal/mol O, ifAC, 3x [4/3AM(s) + O,(g) = 2/3A1,0,(9)] so for reaction (1), AH9Y = 3(-1133 K1/3 mol O,) = -1133 KI /mol O,. Reaction (4) = 3/214/3AI(8) + O,(4) = 2/3A1,0,6)] 80 for reaction (4), AH9Y = 3/2(-1133 KJ/2 mol Al) = -850 ki/mol Al Correct altematives: (1) and (4). {28} Fifty grams of the mineral ilmenite, FeTIO,, are heated in an insulated furnace and then quenched in a $00 gm copper vessel containing 200 gm of water. The temperature of the water and vessel both rise from 30°C to 65°C. To what temperature was the ilmenite heated prior to ‘quenching? Solution 50 gm ilmenite = 50 gm ( 200 gm H,0() = 200 em (325) = 11.10 mol H,0() 1 mel 500 gm Cu = 890m (<2) 7.57 mole ‘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 19THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS. STEMS cl, and ilmenite is 65°C = 338 K. ‘The heat lost by ilmenite = heat gained by H,O and Cu vessel. eink = 2.0 8 (0.33)(116.61 + 18.24 x10 7 — 20,04 x 10°7*)aT 15,307.08 + (38.487 + 0.0037? + 661,320.0/7) 98 Gyo) [ 01.10\75.44)aP = 29,308.30 oot 8.)= [Eisnarses +1614 10°F 434111077? 1.0067 x 10°75 ar = 6,305.21 Equating [Qj,| with Qfi,0 and Qo, 15,307.08 + (38.487 + 0.0037? +661,320.0/1) = (29,308.30 + 6,305.21). Solving for T, T= 197K = 924°C. [2.9] Calculate the final temperature and enthalpy change of the mineral ga- Jena, Pbs, when 253.62 gm of the mineral at 80°C are placed into 58.73 ‘gm of adiabatically contained water initially ata temperature of 27°C. Express the enthalpy change in cal/mol PbS. Solution 1 mol 253,62 gm galena = 258.62 gm (wes) = 1.06 mol Pbs ste) 58.73 gm H,O() = 58.73 ¢m _ 26 mol HOD ‘The initial temperature of galena is 80°C (353 K) and of H,0 is 27°C (300K). Let T,= the final temperature of galen + and H,0, Que = Qir,0- Since for a constant pressure process Q’ = AM, Allis) = AMlio@)- CHAPTER 2 % i - fe 06 molyCMar = | (3.26 moh! ar’. Expanding, sa 0 % % “ dnoxst0 640° rar- f G26q%s4nar ssa soo on 216.617, + 8.20 x 10°73 = 86,369.67 Solving for 7, Ty= 20K = 166 20 AH i000 = J (3.26)(75.48)ar 00 [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- ‘eral serpentine, Mg,Si,0,(OH), in the presence of quartz to form tale, Mg,Si,0,(OH),, Use the heat capacity for H,O(D in Appendix A, Table A.3A and the heat capacity for H,O(g) in Appendix A, Table A.3B. ‘The reaction is: Mg,Si,0,OH),(9)+ 2106) + Mg,Si0,fH),6) + #,0(). Serpentine a-Quartz Tale Solution (@) Incorporating the H,O phase change in an isobaric TL: (1) Setup Mags Si, Og (OH),(6)* 2Si0, (6) aes Mga Sig o(OH), (5) +H,0(9) Als 20My Aly Aly org Mga SiyQo(OH), (2) +44,069) Ay ZAH3 an, [AH Mj Sig Og (OW), #2510, “245 Mg, Si, O, OMY) HOG) ‘Serpentine Quartz. Te Q) Sum DA, = AHS, + AH, + 4H, ~ AH} 24H, - aH, 3) Substitute ‘AH34= 1787 Sfmol (from Part (@)) 7 [7 cphowan= [0768421468107 48,1710" 43.6174 1087-95 29,316.10 2)4P = 1603.9 x 107% 13,734 x 1047? + 7.3687 + 223,1607"' + 723.487" — 19,147 1 7 abla = [" ops = f(5053.6-sar1 x0? P+ 2729121077 ~169.26x10°T-Y? + 4021.1 x10?) or AH, = 909.7 x 10°1?2635.85 x 10°7? + 5653.67 — 4021.1 x 107 — 153.8527 > 1 aati, [f 203%ar -afuca-siasexi09 sore F or 2 Aly= 37.754 x 10°T? + 89.207 + 20,036 x 10°T* - 43,896THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEM ogra = [499.60 -144.76 210 P-109.32x10° 4419.99x10'T ya All, =~12.38 x 107° + 899.607 — 499.99 x 10*T - 21,8647? + 108.85, x1P Substituting the above data into the expression for ZAM, = 0 0= 1787 +{-1603.9 x 10°7° + 13,734 x 10T> + 7.3687 + 223.1607 723.48T2— 19,147) + (909.7 x 10°T? ~2635.85 x 107? + 5653.67 ~ 4021.1 x1OT# - 153,8527°) — AH? - 37.754 x 1037? + 89.207 + 20,036 x 10T* 43,896) ~ (72.38 x 107 + 899.607 - 499,99 x 10° ~ 21,8647 + 108.85 x 10) © Solve ‘Solving the expression above for AH, 8 Ghmol) = 69.42 x 1047 — 2,597? + 4672.27 - 3.70% 10°T — 131,2647°S — 82,315 for 373 K NaAlSiO(s) + Si0,6). Ab id oe Solution AllSy = ¥ nAHSS (Products) — F mbH (Reactant) Alling (Sol) 1(-910.7) + (1)(-3029.4) - (1)(-3935.12) Pein {2.12} Using the standard enthalpy change computed for the reaction in Exer- cise Problem [2.11], calculate the standard enthalpy change of this reac- tion at T where 298 K < T < 844 K. No phase changes occur. 24 CHAPTER 2 Solution (1) SetUp Na Al Si,0,(s) “E> Na AlSi, O, (8+ $1 0,05) Alls At AH, Na, Al Sig 0,(s) 21H? Na AISi, OL + 5106s) Albite Tadeite. Quartz. @) Sum Collecting terms and applying [2-16) and (2-17): @) Substinue 7 AH? (mol) = AH 2y_ + foe + 140.749 x10 7 — 49,191 x 1057 ase 22.22.10 T? + 43.692 x10°T°5 dT = 4,980 ~ 238.217 + 70,986.58 + 70.37 x 1O°T? — 6249.54 + 49.191 x 1057" = 16507.05 ~ 75.74 x 10°97? + 8738.47 @) Solve Ad1P(Jimol) = 53.21 x 10° ~ 238.217 + 7.04 x 10°78 ~ 7.57 x 104P + 4.92% 10T* + 8.74 x 10, [2.13] At 1356 K and I atm pressure, the following exothermic reaction oc- curs: 2Cu(l) + (12)8,(4) > ¥-CUS6). Calculate the heat evolved and enthalpy of formation of +Cu,S(s) at 1356 K and 1 atm pressure, Use the heat capacity for S,(g) in Appendix A, Table A.3B. Hint: begin with the reaction 2Culs) + (U2)S,(#) > Cu,S(0). 25‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEM Solution (1) Set Up 2AM ante am m Sf" cassis) sx cul 2Btes 2cwlt+ S,(Q): — Conse) sue 2 Ag cu,3 Asc. sue) Zon, |4AH7 Cust Cu 80 fa, ane (9)4459 ——#°_5cu, Sea state 2Cu(6) +4 5,69) a Seo sure: 2) Sum ‘TAHy, = 0= AHigy + AH, + AH, + AH, + AH, + AH,— AHS, — 20H, — ad, 20H, which upon rearranging gives And, = Ald + AH, + 4H, + AH,+OH,+ AH, ~2AH,— 1/2AH, 2AM, @) Substinte ‘The data from Appendix A, Tables A.1, A.2, A.3A, and A.3B is substituted in AH®S, above: AH 2fe = U1 mol(-80.115 kSfmol) ~0.5 mol(128.49 K/mod) +fiegsear es ous unos [oper #16368 soa) « [7% c680ar-2 3654 Wino) Jos opar— [Reepeun. @) Solve ‘Upon intergrating and completing calculations, 2, um, = AHA, = -108 kJ/mol 26 CHAPTER 2 [2.14] Calculate the standard enthalpy of formation of methane, CH,(g), at 298 K in kJ/mol and kcal/mol from the following information: @) CH) + 20,(g) = CO,@) + 2H,0(8) A114, = -890.36 ki/mot ©) C() + 0,@) = COYe) AHBL =-393.51 kI/mol (© H,@) + (1/2)0,() = H,0(2) AHS = -241814 kJ/mol Solution (2)00,(s) +2H,0(8) =CH1(s)=20,(8) Al = 4890.36 kifmol (EUs) + O4(6)= CO,(6) Aig =-393.51 KIfmol 2(€}2H,3(@) + 04(e)=2H,0(8) AH = 483.528 txymol C(s) + 2H3(8) = CHale) Sf pa teal keal AMC, aoe = 13.22 mol 4.184] ~" “mol anit = 1322 8yimol= 3.12 Keay, [2.15] The enthalpy increment for element A at two temperatures is given as follows: x) HY —H&(J mot) 1000 1750 700 640 Determine the heat capacity of A which most accurately reflects the data given. Solution 100 Eqn 110- fas era 50 | simutaneous Satin m2 oio= [iesonar 7 1750 = a(1000 ~ 500) + (b/2){(1000}*— (500)"] {640 = a(700 ~ 500) + (b/2){(700} - (500)4), arTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS 8YOTE and expanding: a=20 b=2x109 CA (mol) = 2.042% 1027, [2.16] Derive the formula AH, t ai fica where (@ A, and Affy, are the constant pressure molar enthalpy changes ‘of a reaction in states 1 and 2 respectively. (b) No phase changes occur between states 1 and 2. (©) Allreaction components exist as one mole in the balanced reaction. Solution (1) Set Up a A+B 29 1c + 1D state 2 (BT) ye fa.) ae 1A +1B an, IC + ID STATE 1 CBT) Ady, + AH + Ally ~ AH, ~ AH, ~ Sy ‘Ady, = MH, + He + Ally ~ AH, ~ Ally (3) Substitute a= [fare fezer- er fige T ry in tl ts AH; = ath,» [cg +eB-ch-chyr %, Let AC, = Ln4Cy (Products) ~ ¥nC (Reactants) 28 CHAPTER 2 Hence, ac, (4) Solve INCE + (NCP NEE — (CF A= ty « [ya at x [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, u=h-Py Differentiating at constant pressure, ° du= dh Pdv ~ dP” Integrating, pope au= fase foro fin on = 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 whee! to stir 500 gm of adiabatically contained water intially at 25°C. Assume for the water a negligible change in volume and that C, = Ge @) Find the intemal 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 ‘Adiabatic Container 27.78 moles HO (@) Work-Energy Principal: As the 20 kg mass falls, its gravitational potential energy, E,, 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}.20 xgmane =~ AUi,0 = + Wha t,0 Distance Fallen = 2m: h= 8m Bp = (196.2 NB m)—1962.0 AU’ =—Way = 392.43 392.4 J AU rad frontMe 7.787544) (27.78X75.A4)T og = 3924I 30 CHAPTER 2 T(k)= 24 __ 998 = 298.19 (2.78)(75.44) or T= 25.19°C Distance Fallen = 4m: = 6m AE =(196.2 NX6 m)- 1962.0 5 AU’ = —Wyg = 284.83 AUy (= 7848 = [OT eKISADET THA | 999 298.37 Distance Fallen = 6 m: k= 4m AB; = (196.2 NY(4 m) — 1962.0 AU’ =-Wag = 1177.23 706) = 212 . 98 = 298.56 2095.7 or T=25,56°C Distance Fallen = AEs AU’ = (196.2 N)(2.m)—1962.0 J = -1569.6 1 Waa = 1502.6 " AUy @=15696= [ar7E.sanar 1569.6 2095.7 or T =25.75°C +298= 298.75 Distance Fallen = 10m: h=0m 196.2. N)(O m)— 1962.0 1962.01 Uy @)=19620= f2r.7ex 75447 34THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SVOTENO 1962.0 T(R) = eg + 298 = 298.94 or T = 25.94°C. (b) Linear plat is consistent with C, = constant. seb. ovles) Av 3 Distance ralien (J) AU' = - Wy (3) (°C) i962. i570. un 704 392 0 0.0 39214 Teele uri 1570.0 i962:0 18. gy J Ener, Ep g g linear plot- consistent with Gy= constant 5 25 ‘eo 32