CHAPTER 4 Chapter 4 [4.1] An ideal gas undergoes an isothermal process from an intial State 1: (P,,V.) 0 a final State 2: (P2,Va,). Prove AGr= RT In(PyP,) Solution ° dG = var - S4P,V = RT/P to= "Ear so,onrf yr a Tin(P, 1). [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: (@) an isothermal decrease in pressure to 1 atm. (b) constant volume decrease in the pressure to 1 atm. Solution (@) Since the process is isothermal and the pressure change is known, use $= PD) «(Soe ats. (53), Gp), =” as [ds=-n{ ap/p =-sr44imo2)=18.8 J imal K) ey aah et A (b) Use $= F (VY) =a From (3-13), Ss ts fes-as-cs fer sy sco 53THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 4S=3/2R | dr/T [4.3] Prove by two methods that at constant ‘temperature, i Mra = 0 for an ideal gas, regardless of the Pressure path, Soluion ‘Method 1 Let H-U+PV dH = dU + d(PV) For an ideal gas, U = f(T) only, hence dU = 0 at constant temperature, Allso, since PV = RT, (PV) = (RT) = 0. Substituting, Hs fo =AH=0. i | dP = Tds+ VP. Dividing by dP and holding T constant, RB ( {8 = 1F), +V. Substituting [4-23], xy R18 wv (%) +V. From the ideal gas equation, Ip ag = R/P. Substituting into the expression above, TR/P+V 1. Hence, ag CHAPTER 4 fora =0 f a ] Prove that at constant temperature, ASiatemar =-AR In(P2/P\) for n moles of an ideal gas. Solution Lets'=fPT), wE)e( 98° From (4-23), &) ‘Substituting the last expression into the equation for dS’ gives w-(¥) ap. Foran ideal gas, v'="82. and therefore oO Jp e : 11 (22), -2(22), 8 mame Ban fas = core , . el OT )p TP ip P [45] Calcium boils at 140°C. The standard free energy of vaporization of liquid calcium is given by ‘AG? (calfmol) = 41,080 + 5.837 log(t) - 42.237, ‘here log = logy (personal communication, 1959, R. Schuhmann, I, Department of Metallurgical Engineering, Purdue University, West Lafayette, Indiana). (@ Find the linear Gibbs free energy equation of the form AGS =a46T hich approximates the above equation as closely as possible near 1500 K.‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (b) Calculate the boi with the actual value, Solution point from the linear equation and compare (@ aa? 1.030 + 5.837 log(T) ~ 42.237 1,030+2.537 In(7)— 42.237 From (4-25), (26) =a <20fr(280) re) Jee Se =-2.59 14 In(Z)]+ 42.29 =-2.53In(T)~2.53+42.23 2.53 In(T) + 39.70 From [4-30], 41,030 qa0*rT)) sare Ee ~ +2581n(7)~42.29) a, w 1,030 , 2.53 TT AS4|gx= 21.2 AG¢(eal/ mol (b) At the boiling point, liquid and vapor are at equilibrium, hence AG® = 0: O= 37,235 -21.2T = aaa (55280-29092) [4.6] Phosphorous bearing vanacium 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 do- 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 FesP and pure iron (ferrite) by vacuum distillation of the phos- pPhorous and remove the iron magnetically. Assuming the best vacuum obtainable in a large scale operation is 10-?mm Fig, estimate the operat- ing temperature of a vacuum furnace required to accomplish this distil lation, 56 CHAPTER 4 246, 4 AG, i aes: ae p AS 4Fe + ® sum TAGy, G) Substiture Pr waar) smar( AG? + 8G, +48, — AG-20G, AG, = AG, =0 AG =0 (equilibrium) AG? is determined as follows: 4Fe+2P = 2Fe,P B=2P 4Fe+P,=2Fe,P AS = 2(72.38)—4(27.28) 21 @) Solve AG=0=-93.447 + 464,400 -182.4T T= 1684 Kor ]A1°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. 87rN AT APLIGATIONS IN MATERIALS SYSTEMS TLL - Pressure () Sctup Ago Auls) sare > Au (LY eo Aye Aes Naio dp ¥) asieacad P 1 | ' act | AuwlS)) Bere? 4u (2) Molar volumes ae obtained from literature data. AGF is calculated from TL oo at 1356 K (see Example Problem 2-6) £ Au (s) =e Au(L) aucfece SS) ye Sar 1336 ; y 1336 Auf = 12 760 alee Auls) S5en Au (2) 2) & G) Sum & Substinte EAHy, =0=12,760+ [232000 srt a [eayos+s 19x10 Ter = 12,760 + (29.2920) - AH cg - 613.6 4) Solve AH fxg = 12,732 Jeno). CHAPTER 4 ‘TL#3 - Entropy of fusion at 1356 K (see Example Problem 3-5) () SatUp ast re) Au(s) ~ 135k Awl 35 (260 assa0{CCp/aT as¢ {led 1320 ¢ | Ia =4. Au(s) SSSA u(Q) @ &@) Sum& Subsite - os asp <0=958+ [Bar ashy- [ (BEesso.00°}r ise 1336 og Sly, =9.55 +0.495-0.248 = 9.737 Ji(mol-K) = 4,83 Caleulating AG, from [4-8 ’ ‘AQhg, = 12,732-1356(9.797)=-A71.4 Jmol = — Ngo © Now, referring toTL# 1: s 9,53 2) & @) Sumé& Substitute LAG, ANAGV gf P-0-Vuy [aP=0 1 Sats VME = 2 197 = 1.69 en 197= 10.207 em*/mol, — 471.4+[11.59(e -2)- 10:207(P- 10.1013 59TEMIMOUTAMIG LOOP APPLICATIONS IN MATERIALS SYSTEMS {4.81 Assuming that /1° and AS® are independent of temperature, calculate the temperature at which solid H]gO will dissociate into liquid Hg and O,(g) at 1 atm, Solution () Setup Hg0(s) — > 4, () +% 0, (9) t t ah Als re PA, ngoce) Staats, 1 (0) +% deg) (2) & (3) Sum & Substitute a Since AC,=0, | AC, =0, hence, the solution only requires standard data 38 298K, Eddy, = 0= ANS — anit ) Solve AHP = 90.8 13/mol “Applying the same Tin similar manner for cauopy: ASP = AS, = + 122 (205.02) -70.3 = 108. 12 J(molK). Using (4-11) and sting 4G = 0, 4G? = 0 = AH, - 145%, 90,800 = 20,800 rs a Toate 7899.8 K= 567°C, [49] Thermodynamic analysis ofthe equilibrium state for carbon, chromium, and niobium carbide reveals that niobium isan effective alloying agent for limiting grain boundary precipitation of chromium carbide by pref. érentally removing carbon as niobium carbide. (@ Write a single equation deseribing C-Nb-Cr equilibria neglecting solubility effects, (b)Confirm thermodynamically the alloying effect of Nb at 1200 K, 60 CHAPTER 4 Solution (@) ONb + CrxCy 92" 5 6NDC + 23Cr, (b) From TL analysis: Q) Soup 8 +23C) ON bt Cros Ce 1z00K GNbC re é de ey G oe re AG? loNb + Cron Cy “zeok? @NBC + 23Cr (2) Sum LAG, = AGL +280, + 6AG, — AG xy ~ 64G, - 4G, = 0 (3) Substitute All pure components, no solid solubility, AG, = AG, = AG, = AG, =0 BG yy = BC yg = CAG ao AC, [-130, 138+ 1.67(1200)]~6f- 68,5406 44(1200] -=811,200 J/mol <0=3 NbC formation is favored. i iven below. One of [4.10] ‘Three equations for the oxidation of a metal M are given bel e : these equations is for the oxidation of solid M, one is for the oxidation Of liquid M, and one is for the oxidation of gaseous M. Using the AG? data given, identify the reaction and the state of the reactant metal (@2M+ 0x2) 2M0) AGP =-290,400 + 46.1 (b) 2M + O2(g) > 2MO(s) AGP, = -358,754 + 102.67 (6) 2M + Og) > 2MO(s) AG? = ~298,400 + 55.47 ‘Solution From [4-27], entropies for each reaction are: Reaction (a) 9G?) 0 = A290.400+ 46.17) 46 catfinolK) ar}, or , 46.1 etTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS ‘Reaction (b) 9° = ASSETS NOS 996 carota) aac?’ mJy AS? = -102.6 Reaction) (#) AS? = 55.4 0 _ (-298, 400 + 55.47) As’ semen ssa From the discussion in section 3.5, ‘AS°(gas) > AS*Cliquid) > AS*(solid) hhence, from the data above ‘AS® reaction (a) is solid M_ AS° reaction (b)is S° reaction (e) is liquid M [4.11] For the reaction SiC(3) + Si(s) + C(s), AG? = 12,770 - 1.667 cal/mol from 298-1680 K. Using this data, determine: (@) 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 far = 1.66 cal mol-K), (©) AH Ssox= 12,770 cal(mol). [4.12] Using the general expression for C, ~ C, given in Exercise Problem 03}: (@) Show that Cy— C, = o2VT/B for any substance, (©) Use this expression to estimate C, ~ C, for pure copper at 298 K. Solution (a) From Exercise Problem [1.3]: co 42) Using (1-2), [1-3], and the transformation formula [4-18], 62 CHAPTER 4 Gi ‘Substituting into the above expression, ‘a)_ oP opnos-nr()- 2 (b) From Table B.1 Op-Op= ‘K? 8.96 gm-7.6x 10° 0012 tm-em?,, _1mol-K - K-gm = 0.01 5/(mol-K). [4.13] Use the data in Exercise Problem [3.8] and the Gibbs free energy crite- ria to confirm that solidification is spontaneous after supercooling. Solution 4G = 4H -TAS =-12, 136 80(-11.53) 1877 Jimol < 0= spontaneous. {4.14} (@ Starting with [4-13], use [4-271 and [4-30] to compute AS® and AH, respectively, asa function of temperature, ; (b) Use the results from (a) and Appendix A, Table A.4 to obtain AH® and AS® asa function of temperature for the reaction 2Culs) + (1/2)02(g) > Cuz0(5). 1 ‘Compare the results at T = 298 K with the data in Appendix A, Table Ad. 63THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution a) ASS: AG? =A +3 ripy (@ O85: AGp=As TT in() sor »._B ‘dacs (=), ASE = Sapgl? VT +in(T)]+C = Halt mnj+c [in(yr)-1]-¢ AGe B rears B intr) +c acs/r) an any Ce i ee an? = a-5F_ (©) ASp and As3,: AS§=— J o5lin(yr) -3]- 123.44 =7.2in(7)- 116.3 (Table A.4: Derived Equation) /4 Ji{mel-K) AS, = 93.94~ 2052", 2(89.95) $275.27 J(mol-K) (Table A.1) 64 CHAPTER 4 [4.15] ‘The thermodynamics of SiO is important in many materials applica- tions because ofits high vapor pressure. Develop an expression for the Gibbs free energy of formation of SiO@, AGsiéc. a8 a function of temperature between 298-1700 K using the data in Appendix A, Table Aa. Solution ) (Si0,) + (Si) = 2(8i0) ‘8G® = 697,539 453.987 log(T)-518.457 Jmol, @ (6:0, =(Si)+(0,) AG! =881,235 +12.5STlog(T)-218.51T J/mol @=0)-@. (Si)+ (02) > 2(Si0) AGS =~183,696+41 37 log(T)- 3007 ‘OSL, (Jmol) = -91,848 + 20.727 log(T) — 1507, [4.16] One mole of a metal, m, at 1 atm pressure is heated at constant volume from 300 to 500 K. Calculate the hydrostatic pressure that results from such a process. What isthe work done? Assume C, is constant over the temperature interval. @,, = 5% 10° K", and Bi, = 8 x10 atm Solution ‘Since the process is constant volume, the path may be expressed by the parti ove (22) AV=0 From (4-18), ‘@P (av/aT) re 65"THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS Systems Expanding and intergrating, tp 8 [Fr 20% ap (200) sao Pepsin weJeav {4.17] Referring to Exercise Problem [4.16], calculate the er ‘chan; te same process. Let Cp = 209 IAmoK), Vass Geman moh Solution S=/(T,P) as-(% Using the differential form of [3-10] and applying {4-23}, as PT, (3) =2 T lar), S)-B)- fe 7 Le eV onan) 240 $00) _ 5x10" x6en* 48=203910{ 500) _ 5210" xem er) 5x10 x6em*, 1251 ams mol-K “9.869 em* atm = 10.64 J/(mol-K).. 0.68 [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, CHAPTER 4 Solution (rable D2) Mey = Mg —T5, (27150.4— 771.4) ~-950(4.8129 — 2.7313) kI/kg =1979-1978=9. [4.19] Use [3-6] o confirm the value of u, - win Appendix D, Table D2, at 900 K and 0.251 bar. Jeu faepf.an ‘= 904.9175 ~2.6974)- 22510 (7180 ~1.438) [4.20] Referring to Exercise Problems (4.16] and [4.17], estimate the enthalpy ‘change for the same process if Vm = 10 em*/mol. State any assumptions in making the calculations. ‘Solution From [4-33], an =o, [arev [i ore eno ars 10cm? 210 a ssa0-T HP “mol em?-atm Since the functional dependence between T and P is unknown, a rigorous solution to the problem cannot be obtained. However, since 5x 10°T " =VaP or [da=v[dp => do=vaP or flo-v)3 ‘8G=VAP, hence from B.2, 4.1845 atm we 713223 em? - atm ) 1.01826 bar, ‘mol bar ap atone: a= (10.257 — \a bar) = 405 Jima it of formation computed in 4.24] Using the standard enthalpy and entropy (428) nae Problems (213) and [3.13] forthe reaction 2Cu(h) + 1/2828) > Cu), determine whether or not this reaction is spontaneous at 1356 K as written, ‘Solution @) SerUp 135K 2s 4e_, | Cus (6) 2Cult) 4% S,(g) BSR> cups) eee 2A6, ie 2culd) + % S204) Tasek Sum i EAGy, =0= AG hag +40, —A0ray - 2 AG, 246, 69‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS (3) Substitute Gg = AHS, ~ 1356(AS 2) 108,271 1856(122.244) 274,260 Jimol AG, = AG, = 4G, =0 @) Solve Gye =-274, 260 J/mol < 0 = spontaneous. [4.25] For the contact metamorphic reaction SiO,(a) + CaCO,(s) > CaSiO,6s) + COx(g), (a) Calculate the standard Gibbs free energy change at temperature 298 K 535K; ‘Nonspontancous reaction => AGS > 0 = 86,670 ~ 165.657%~r= > 0 = Diewm < 535K, 70 CHAPTER 4 AG", as a Funetion of T for the Reaction (SiO,), + > + CO,(9) { AC CTAnele) Plat. | TUR) POINT AT Tadd IS EXCLUDED [4.26] Show that the Gibbs free energy change for an isobaric chemical reac- tion occurring at a temperature Tis Gy = Ally, TAS, ‘when AC, = 0 in the temperature range between T; to T. mn‘THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS Solution Atconstant pressure, AG, = AH,~ TAS, , aie at facut asians, ear fs Sinesacp= Alf, = AB, and AS, =, Hace oG-al, -1, [4.27] Derive [4-13] showing all steps. Solution AG? = a1? ras? AN = A113 f Acar ass : 2c AS? = Ase ff “ear. Assume a=86, = constant, ba hence, AH? = AH2, +a(7- 298) AS? = AStog + an(T/298) Substituting 4/72 and As? into AG2, AG? = AHS, = 298a~ aT In(r)+T[a~A5%_ +a1n(298)] Let A= Aljpq ~ 298a (all constants) pa rtln(t/208) Tog(T) C=a~ AS3g (all T terms) Substituting A, B, and C: AGR= A+B Tlog(r)+Cr. 72 CHAPTER 4 [4.28] Derive [4-14] and show that a (¥) le), (ar), U+ PV, dU = 60 - 5W, dW = Pav, and dS=80/T @G saath) =u + Pv)“ dG = dU + (PV) - d(T) = 50-W + d(PV)— ATS) = TaS - PaV + PaV + VAP TdS ~ SAT. Hence, a) (a azove-ser matis.-(2) =(2), 73