CHAPTER 1 THE FIRST LAW OF THERMODYNAMICS The first law of thermodynamics has been expressed in many ways. Most of the definitions consist of a statement about ‘energy’ and its conservation, and the law could be stated as: Energy can neither be created nor destroyed in a system of constant mass, although it may be converted from one form to another. iy st Consider a mass of gas contained in a cylinder fitted with a frictionless piston, and let the internal energy of this gaseous system be denoted by U. Suppose some external energy, q, in the form of heat or other energy is Supplied to the system which, while absorbing this energy, performs the amount of work wm. Then W=g-w, JSk! (1) where AU is the increase in the internal energy of the system. The above equation can be regarded as the mathematical expression of the first law of ‘thermodynamics. The internal energy is a state function or state property. Therefore the change in the internal energy is characteristic of the initial and final states of the systen, and does not depend on the path taken to bring about the change. 1,1 Heat Content or Enthalpy If the volume of the system is maintained constant, then the system does no work, and Eq. (1.1) becomes aU = q. (1.2) For an infinitesimal change of state, Eq. (1.2) can be written as dU = &q. (1.3)2 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS If the pressure, P, is maintained constant, Eq. (1.1) becomes aU = q - Pav, (1.4) where 4V is the volume change in the system. If the initial and final states of the above gaseous system are denoted by A and B respectively, Eq. (1.4) can be written as = P(Va = Wade or @ = (Ug + Pg) - (Up + PVp). (1.5) ‘a The term (U + PV) is called ‘heat content’ or ‘enthalpy’, H, so that (Uy + Py) and (Uy + PV,) Hence, from Eq. (1.5), we have or qe (1.6) For an infinitesimal change of state, Eq. (1.6) becomes oq (1.7) From Eq. (1.4) and (1.6) we have aH = aU + Pav (1.8) at a constant pressure. ‘indicates the differential element of a state function, while 's! indicates the differential element of some quantity which is not a state function.The First Law of Thermodynamics i oe Gu yt Enthalpy is an extensive property of the system, depending upon the amount of substances present in the system, If the reaction is exothermic AH is negative, and if the reaction is endothermic AH is positive. This sign convention has been used in this book. Also, like internal energy, enthalpy is a state function. 1.2 Heat Capacity ie ya The heat capacity, C, of a system may be expressed as where q is the amount of heat added to or withdrawn from the system resulting in a temperature change of AT. If the temperature change is infinitesimally small, then (1.9) At constant volume, £q. (1.9) becomes v2 Gy: (1.19) From Eq. (1.3) and (1.10) we have _ (ot 2 ay, = Hh, = Gy qa.) At constant pressure, Eq. (1.9) becomes Cpe Bp (1.12) From Eq. (1.7) and (1.12) we have dH) ju! Cp QP, = Gp: (1.13) The above equation is called Kirchhoff's equation. At this point we must differentiate between the extensive property of the4 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS entire system and per mole of the systen. For a system containing n moles, the value of the extensive property Z (such as H.C, etc.) for the entire system will be denoted as Z', and for one mole as Z. Thus vo= nw and the Eq. (1.11) and (1.13) can be rewritten as Ve OY cy oH, or cy . (1.14) ' ai" cy = . and »* CH, or = FH, (1.15) The heat capacity is also an extensive property of the system, depending on the amount of the substances present in the system. Usually, ft is more convenient to use molar heat capacity. 1.3. Thermochemistry and its Application in Metallurgy Thermochemistry is the study of heat effects accompanying chemical reactions, the formation of solutions and changes in the state of matter such as melting or vaporization, and other physico-chemical processes. ay Heat of Reaction ea The heat of reaction is the heat evolved or absorbed when the reactants react completely to produce products. It could be expressed in terns of either per mole of any reactant or any product. (2) Heat of Formation The heat of formation per mole of a compound is the heat evolved or6 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Since the enthalpy change of reaction (1.16) is also equal to the heat of formation of one mole of Ni0, we have ° ° AH" 298, Thus, the heat content of a compound or alloy in the standard state is equal to its standard heat of formation, (3) Heat of Combustion Alea Heat of combustion of a substance is the enthalpy change when one mole of the substance is completely burnt in oxygen. (4) Heat of Solution Dh id hen one substance dissolves in another, there will be a change in enthalpy. This is called the heat of solution, and depends on the concentration of the solution, Exowle 1A Sul Ulgu Calculate the standard heat of reaction at 25°C (296 x) and] atm pressure of 3 = + &Fe> in terms of per mole of Al,0, formed, per mole of Fe formed, per mole of Fed reacted, per mole of Al reacted and per g of Fe formed. ° Given: AH ogg, creo> = 763-3 kcal/mole (-264.84 /not). ° ta on 298, <1, 7 400.0 kcal/mole (-1673.6 ki/nol). Atomic weight of Fe = 56. Solution: 3 + 2cAl> = + &Fe>. (ALN)The First Law of Thermodynamics 7 The standard heat of reaction of (1.A.1) at 25°C and 1 atm pressure, Hogg, (1.8.1)? can be written as ° ° ° 4H 298,(1.0.1) * "4 298,product ~ 7 298 reactant ° ° ° *"798, ~ 298, ° ~2H 298 Since the standard heat content of a pure element is zero and the standard heat content of a compound is equal to its standard heat of formation, we have rm) ° = ay? ~ an? “Wp98,(1.0.1) = H'298,<01,0,> ~ "298, 400.0 = (3x - 63.3) =210,1 keal. Thus, the standard heat of reaction of (1.4.1) is -210.1 keal. In other words, when 3 moles of solid FeO react with 2 moles of solid Al at 25°C and | atm pressure, to form | mole of solid A1p0, and 3 moles of solid Fe at 25°C and 1 atm pressure, the heat of reaction is -210.1 kcal/mole of A120, formed, Since 3 moles of Fe are formed, the heat of reaction is -210.1/3 = 70,03 kcal/mole of Fe formed. Similarly, the heat of reaction is -70.03 kcal/mole of FeO reacted and -105,05 kcal/mole of Al reacted, In order to calculate the heat of reaction per g of Fe formed, the heat of reaction per mole of Fe formed should be divided by its atomic weight. Hence, the heat of reaction is -70.03/56 = -1.255 kcal/g of Fe formed, 1.4 Hess's Law et _ yas The law states that the heat content change in a chemical reaction is the same HSther NT tNtakesN place in OnerOrseveralstages!, provided the temperature and either pressure or volume remain constant. The subsequent example illustrates the application of Hess's law in calculating the standard heat of formation of WO3.8 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Example 1.5 the: heat of formation of solid WO; from solid W and 0, gas at 25% (296 X) and 1 atm pressure from the following data at 25°C (298 K) and 1 atm pressure: 5 SH 59g = -134 keal (-560.66 kJ). 3WO,> + (0,) = < + Hogg = -131-5 kcal (-550. 20 ky). « : ¢ aM. = = os W305? + 402) = WOE i SH g9 66.5 kcal (276.24 ki). Solution: The problem consists of calculating the standard heat of the following reaction at 25°C and 1 atm pressure: + (05) = <0. and + 1(0,) = 3W0,>, (1.8.4) Adding (1.8.2), (1.8.3) and (1.8.4), we get the following: 3 si + H40,) = 3eao,p. (1. B.5) According to Hess's law, i o98,¢1.8.2) * “H°298,(1.8.3) * °298,(1.8.4) 1 798,(1.8.5) = = (3x-134.0) + (-131.5) + (-66.5) = -600.0 keal.The First Law of Thermodynamics 9 Dividing the heat of reaction of &q. (1.8.5) by 3, we get the heat of reaction of Eq. (1.8.1). Thus 0 OH 298,(1.8.1) = -200.0 kcal. Therefore, the standard heat of formation of solid WO3 at 25°C and 1 atm pressure is -200.0 kcal/mole. 1.5 Variation of Enthalpy Change with Temperature The standard enthalpy change of a reaction can be easily calculated at 25°C from the available data; but the kinetics of many reactions are not fast enough at 25°C for the changes to be complete in a measurable period of time. Therefore it often becomes necessary to find out the enthalpy change of the reactions at a higher temperature. Applying Eq. (1.5) for a chemical reaction occurring at a constant pressure, we nave d(H°) a) (1.18) On integrating the Eq. (1.18) between the values of oy, and or at y and Tp K, we have ° AH 1% Tp d(aH?) = | acy aT, ou, n or = ae on, = (1.19)4 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS -3 = -0.73(800 - 600) + S2heto (800" - 600}, = 455.93. Putting the appropriate values in Eq. (1.0.4), we have 500,(1.0.1) = 752400 + 612,20 - 1150 + 455.93 = 52,482 cal. Jul Gy ps 1.6 Maximum Reaction Temperature : Flame Temperature It is possible to consider a reaction taking place under adiabatic conditions so that no heat enters or leaves the system. For a constant pressure, this means that the enthalpy change will be zero. In such a reaction, the temper- ature of the system will change, so that the products will be at a different temperature from that of the reactants. If the enthalpy change is positive, i.e. heat is absorbed, the temperature of the adiabatic system will fall. In case the enthalpy change is negative, the temperature will rise during the course of the reaction. From a knowledge of heat of reaction and the variation of the heat capacities of the reactants and products with tempera- ture, it is possible to calculate the final temperature of the system. Such a type of treatment is useful in calculating the maximum flame tenpera- ture in connection with the combustion of fuels. Assuming that the process is adiabatic, the Coibustfon ofa fuel jeanbelrepresentedrasvhe First Law of Thermodynamics 15 spat alge (1), Fuel +Oxidant (at 298 K) + Combustion products (at 298 K). (2) Combustion products (at 298 K) > Conbustion products (at T,): The reaction represented in step (1) will be always exothermic. The available thermal energy is then used to heat up the combustion products from 298 K to their final temperature T,. Using Eq. (1.13), we have Tn ae { 2p product 7+ (12a) 298 where q is the heat evolved in step (1) which can be found out from the standard enthalpy change value, and Tp product is the sum of the heat capacity at constant pressure of the conbustion products. However, the actual flame temperature will be somewhat lower than that obtained by Eq. (1.21), because of heat losses. Exanple The combustion of acetylene fuel with nitrous oxide as oxidant at 25°C (298 X) is widely performed in flame emission spectrophotometry. Calculate the maxinun temperature attained if the best mixture corresponds to the reaction (CoH) + 3(N90) = 2(CO) + (HO) + 3(Mp). Assume that water is undissociated. Given: 298, (cai) = 54.23 kcal/mole (286.90 hl /mol). AH ogg (0) = 19:70 keal/mole (82,42 B1/not), (Naf a O98, (co) * ~26-42 keal/mole(—120, 64 kd/not), an? 298, (N10) -57.80 kcal /mole(-242, 84 il/mol).20 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS 1.4 The reduction of iron oxide in the blast furnace proceeds according to the following reactions: 3Fe,0, + CO ie Fe,0, + CO 0 AH 98 Fe + CO OH oog FeO, + 00,5 712.7 kcal (-55.1 kel). 3Fe0 + C055 #9.8 keal (+ 41.0 kai). Fe + (0,3 “4.4 keal (-18.4 Kd). Calculate AH°49q for the reaction Fea0y + 300 = Fe + 260). ue ge 1.5 Calculate the heat of reaction of the Hall-Heroult process, viz. A105 + 30 30 + 2A1 at 25°C (298 K) from the following data: a 2m + 30, ° OH" 298 c+ 40, ° OH" 208 Atomic weights of AT A12035 -7,400 cal (~80,962 J) per g of Al reacted co; 2,250 cal (-9,414 J) per g of C reacted. and C are 27 and 12 respectively.The First Law of Thermodynamics 21 ald Spe ‘1,6 Calculate (a) the enthalphy of NiO at 1707%C (2980 x), (b) the heat required to raise the temperature of 1 mole of Nif from 25°C (296 x) to 1707°C (1960 K). Given: aH ogg nig = 757-5 kcal/mole (-240.6 kJ/mol). pio 7 12-91 cal/deg/mole (54.02 J/K/mol). 1.7 Calculate the heat of reaction of chlorination of zirconium oxide at 25°C (298 X) and 777°C (1050 XK), according to the following reaction: 0, + 21, +O = Orth + 0p. Given: For ZrCly : aW°ogg = -234.7 kcal/mole (987.98 t.!/mol). Cp = 31.92 = 2.91 x 10° T? cal/deg/nole (733.55 = 12.18 x 10° 3? g/x/net). For co, t AH o98 = -94.05 kcal/mole (-393.50 kJ/mol) Cp = 10.55 + 2.16 x 1079 T - 2.05 x 10° T eat deg/mole (44,1449,04 x10. *n - 8,58 x10°9 *s/K/mol). For 110, : AH°yqg = -259.5 kcal/mole (-2,085.75 kJ/mol). Cp = 16.68 + 1.80 x 10°? T - 3.36 x 10° T cat deg/mole (09,0247.58 x10 87 - 14,06 x10°% *s/K/mol). For Clp: Cp = 8.82,- 0.06 x 10°? T - 0.68 x 10° T? cals deg/nole (38.90-0.25 x10 87 = 2.85 x10°1"*5/x/mot). For Cs Cp = 4.10 + 1.02 x 10°F - 2.10 x 10° T cary deg/nole (17,1564.27 10°82 = 8.79 «10°F °5/K/mol).22 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS ire 1.8 The mean molar heat capacities at constant pressure of hydrogen, oxygen and water vapour in the temperature range from 25°C (298 x) to 100°C (a73 x) are 6.92, 7.04 and 8.03 cal/deg/mole(28.95, 29.4 and 33.€0 J/X/mot) respect- ively. Calculate the heat of formation of water vapour at 100°C (373 x), if AH? 493 for water is -57.80 kcal/mole (242.84 Ka /nol). 1.9. In the dead roasting of zinc sulphide, the reaction occurs as 2EnS + HW, = 2Zn0 + 2505. With the help of the following da’ 25°C (298 x) and 827°C (1100 x): find the standard heat of reaction at For ZnS : A459 = Cp = 12.16 + 1.24 x 1079 - 1.36 x 10° T cal/deg/nole (50.88 + 6.19 x10 2 - 6.69 x 10° F* 3/K/mol). 48.2 kcal/mole (-201.67 kel /mol). = 7.16 + 1.0 x 107? T- 0.4 x 10° T? cal/deg/mole (29,98 + 4,104 x 10% - 1,67 x 10° F* a/efol). For 05: For ZnO: AH°59g = -83.2 kcal/mole (348.11 k//nol). Cp = W.71 + 1,22 x 10°? T - 2.18 x 10 T? cal/deg/mote (48.99 + 8.10 x 10 9 - 9.12 x 10° 2? B/tfrod). For $0, 70.95 kcal/mole (296.85 hl/mol). Gp = 10.38 + 2.56 x 10°? T - 1.42 x 10° T? cal/deg/nole (43.43 + 10,83 x 1078 9 - 5.94 x 10° F? s/tfmol). 1.10 Find a general formula for the heat of the following reaction in terms of temperature + 70 +C = In+ CO.“i The First Lav of Thermodynamics 23 Given: For Zn : AH°4qq = -83.2 kcal/mole (-348.11 kJ/mol). Cp = 11.71 + 1.22 x 1079 T - 2.18 x 10° Teal /deg/mole (48.99 + 5.10 x 10° - 9,12 x 10° F? a/Kfmod). For C: Cp = 4.10 + 1.02 x 107° T - 2.10 x 10° T*cal/deg/mole (17.18 + 4.27 x 108 7 ~ 8.79 x 10° T°? 3/R/nol). For In: Cp = 5.35 + 2.40 x 10° T cal/deg/mole (22.88 + 10.04 x 10° 7 d/k/mol), For CO : AH 9g = -26.4 kcal/mole (-110.46 ki/mol). 298 Cp = 6.80 + 1.0 x 10°? T - 0.11 x 10° T cat/deg/mote (28.45 + 4.184 x 1075 7 = 0.48 x 10° T° B/K/mol). eee SSIS 1,11 In an investigation of the thermodynamic properties of a-manganese, the following heat contents were determined: H 99 - H 98 = 2,895 cal/g-atom (12,113 J/g-atom). ° ° Wio007 H2qg = 52450 cal/g-atom (22,803 J/g-atom). Find 2 suitable equation for (H°, - H°49) and also for Cy as a function of temperature in the form (a+ bT). Assume that no structural transformation takes place in the given temperature range. . 1.12 Calculate the heat of vaporization of liquid silver at 1000°C (7273 x) and heat of fusion of solid silver at 900°C (7173 x). Given: ob = § cal/deg/mole (20,92 J/K/mol). © (Ag) = 7,3 cal/deg/mole (30.54 J/X/mol). fy (Ag) 7 5 cal/deg/mole (20,92 J/K/mol).CHAPTER 2 THE SECOND LAW OF THERMODYNAMICS: ENTROPY AND FREE ENERGY The first law of thermodynamics provides no universally applicable criterion as to whether a particular reaction will occur or not. However, it could be deduced from it that a chemical reaction is feasible at constant temperature and pressure if the change in enthalpy is negative. Many spontaneous reactions satisfy the above criterion, but there are also many spontaneous reactions with positive values of AH. For example, the enthalpy change for the reaction % (2.3)The Second Law of Thermodynamics : Entropy and Free Energy = spontaneous change in the system: Jus Sa) (i) OTF AStotal = 0, the system is at equilibrium and no spontaneous change will occur. (ii) TF ASiogqy? 0» the reaction will tend to occur spontaneously from state A to state B. (411) TF OSp5¢7 <0) the reaction will tend to occur spontaneausly in the reverse direction, f.e. fron state B to state A. It must be remembered that the above statements apply for the total entropy change, i.e. that of system and of its surroundings. Sue UN ge ample 2.8 F solid copper at 1073°C (z3¢e x) fron the Calculate the standard entropy o' following data: 300, ~ °300, — eS 300 8.0 + 5.41 ( In 1346 = In 300) + 1.50 x 1079 (1346 - 300) or 3}. 1 cal/deg/mol36 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Si Ng Zinc melts at 420°C (€93 X) and its standard entropy at 25°C (292 x) is 9.95 cal/deg/nole (42.63 ¢/X/not). Caleulate: the standard entropy of zinc at 750°% (1098 x). - Given: Heat of fusion of Zn at the melting point, ane = 1.74 kcal/mole (7.28 kJ/mol). Sp eas 7 8-38 + 2.40 x 10°9 T cal/deg/nole 3 (22,38 + 10.04 10° J/K/mol). Cp can} = 7-80 cel/deg/mole (32.38 3/8/not). Solution: There is @ phase change at 420°C, and hence in order to calculate the standard entropy of zinc at 750°C, the entropy change of this phase change, i.e. melting,at 420°C must be considered. Applying Eat), 693 O 0 ‘P $1023, {Zn} 98, * { ae Ts = 0 \ KM 1023 my +f Beamer toate 693 s ( Putting the appropriate values in the above, MN 2) 3 693 ° = 9.954 | $3 5 2.40 x 10 3a ts LI 1023, {Zn} T 693 1923 {250 ar 63 «T = 9.95 + 5.35 ( In 693 - In 298) + 2.40 x 107? (693 - 298) + 2.51 + 7.50 ( In 1023 - In 693) 20.85 cal/deg/mole. “42 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Ja Gy 2.7 Free Eneray Chemical reactions are rarely studied under conditions of constant energy, and therefore the criterion of spontaneity based on the entropy change is not of much practical use. Most reactions of chemical and metallurgical interest are performed at constant pressure and temperature. Some reactions operating at constant volume and constant temperature are also studied. A system under these conditions, i.e. constant P and T, or constant V and T, is called a ‘closed system’ and 1s characterized by the fact that no mass can be trans- ferred across the boundary of the syste, but the transfer of energy is allowed. [t is most desirable, therefore, to obtain a criterion for spontan- eity based on a thermodynamic function which is applicable under the above conditions. Such a criterion can be established by the use of ‘Free Energy! functions - Gibbs free energy and Helmholtz free eneray. The Gibbs free energy, G, and Helmholtz free eneray, A, of a system are defined as 6 = H-TS, (2.10) and A = U-TS, (2.11) respectively. The free energy change for a reaction is the difference between the sum of the free energies of the products and of the reactants. Thus, for a reaction at temperature T, the Gibbs free energy change, AG, is given as AG = TG oauct 7 >Sreactant {*#oroduct ~ T ©Sproduct} ~(*Hreactant” 7? Speactant) (F¥oroduct ~ "Mreactant} ~ T(*Sproduct ~ *Sreactent] =aH = TAS, (2.12) where AH and AS are the enthalpy and entropy change of the reaction at temperature T. Nore precisely, the above equation should be written asThe Second Law of Thermodynamics : Entropy and Free Energy 43 But more frequently, the subscript is not written, and it generally follows that AG, 4H and AS refer to temperature, T. Similarly, the Helmholtz free energy change, SA, can be written as SA = WU - TAS. (2.13) 2.8 Criterion of Spontaneity Based on Free Energy For a reaction at constant volume and constant temperature, the following criteria have been established: (i) If QA is zero, the system is in equilibrium. (ii) If aA is negative, the reaction tends to proceed spontaneously. (iti) If aA is positive, the reaction will occur spontaneously in the opposite direction. Similarly, for a reaction at constant pressure and constant temperature, the following criteria have been established: (i) If 4G is zero, the system is in equilibrium. (ii) If a6 is negative, the MSRtTeRTtendsitoTpreceedlspentanesusTy! LAS! (iii) If 46 is positive, the reaction will occur spontaneously in the opposite direction. If the reactants and products are present in their standard states, AG will be replaced by AG° - the standard Gibbs free energy change.The Second Law of Thermodynamics : Entropy and Free Energy 8 Sa id! ‘The free energies of the stable form of the elements at 25°C and 1 atm pressure are arbitrarily assigned a zero value. The free energies of formation of compounds are calculated on the basis of the above assumption and the value is described as the standard free energy of reaction or the standard free eneray of formation, The standard free energy of formation of a compound is the free energy change accompanying the reaction by which it is formed from its elements when al1 reactants and products are in their standard states, and it is expressed in terms of cal/ mole (or J/not). This quantity fs generally reported at 25°C, and for a compound, say MO, it would be written as 6 ca Na* Thus, for example, the standard free energy of formation of solid NiO "at 25°C is ~50,78€ cal/mole. It follows that the standard free enerqy change of the reaction + 4(0)) = 8 at 25°C is -50,786 cal(-222, 490 J). In the same way as the enthalpy change, the free enerqy change of a system depends upon he initial and final states of the system, and does not depend on the path taken to bring about the change. Also, it is an extensive property of the systen - depending upon the amount of substances present in the system, The free energy changes of reactions can be added or subtracted. Thus, for instance, the free energy changes of the two reactions at 25°C are given below. = eNi> + 3(0Q): (2.14) 0 ‘ G29n,(2.14) = 504786 cal. (H20) = (Hp) + 4(05)5 (2.15) ° AG3on, (2.15) 944996 cal. When (2.15) is subtracted from (2.14), the following equation is obtained: + (Hy) = + (HAO), (2.16) 2 2The Second Law of Thermodynamics : Entropy and Free Energy 47 ty JHE JNgu Calculate the standard free energy change of the reaction Mod, + 3H) = Mor + 3(H,0) at 727°C (1,000 x) and 1 atm pressure from the following data: 6900, cMoOg> ~ 71204000 cal/mole (-602,080 J/ro2). Oy A699, (1440) = 7454500 cal/mole (-290, 878 F/nod). ll Also, comment on the possibility of reducing MoO, by H, at 727°C and 1 etm pressure. Solution: Fron the data AGIa99, yoq,> = ~120,900 cal/mole, it follows that the standard free energy change of thé reaction Mor + pu) = Mod» (2.F.1) at 727°C (1,000 X) and 1 atm pressure is -120,000 cal. Similarly, the stan- dard free energy change of the reaction (Hg) (09) = (HO) (2.F.2) at 727°C and 1 atm pressure is -45,500 cal. 8To00, (Fay 7 -120,000 cal, 0 and 61000, (2.7.2) = -45,500 cal. Since free energy change is an extensive property, for the reaction 3(Hy) + (0) = 3(H,0), 0 . 9 “81000, (2.F.3) * 3 * “toon, (2.F.2) = 3 x(-45,5N0) = 136,500 cal.48 PROBLEMS IM METALLURGICAL THERMODYNAMICS AND KINETICS On subtracting (2.F.1) from (2.F.3), we have 05> + 3(H,) = Mo> + 3(H,0). (2.F 4) Since the free energy changes of the reactions can be added or subtracted, 9 - 881000,(2.F.4) ~ “Yoo0,(2.F.3) ~ **fo00, (2.F.1) = 136,500 - (-120,000) 716,500 cal. Since the standard free eneray change of (2.F.4) is negative at 727°C and 1 atm pressure, it follows that it is possible to reduce MoO, by Hy at that temperature and pressure. Beample 2.6 Given the following data, determine which metal has the greater probability of oxidation in steam at 927°C (7100 X) and 1 atm pressure + (Hp) = ellis + (Hy0)5 6 = -559 - 10.18 T cal (2,501 - 42.59 Td). i + (Hy) = 2Cr> + (H0)s AG" = 30,250 - 7.33 T cal (126,566 - 30.67 Td). Solution: sNi0> + (Hy) = stir + (H,0). (2.6.1) AcCry03> + (Hy) eictr> + (H,0). (2.6.2) + (HH,0) = + (Hy). (2.6.3) zero + 3(H0) = + 3(Hh)- (2.6.4)58 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS and ee, =v. (2.25) fq. (2.24) suggests thot thelsTopelonlalblotionmucmeesiisttirineives the C'* ‘entropy change AS with the opposite sion. €qs.(2.24) and (2.25) are also valid for aG° provided the other thermodynamic properties are referred to the standard state. For example, °, ee) = = 48°. (2.28) aT 'p 2.12 SibbS=HenNiorEanERUaLION 46 = AH-T AS. Substituting Eq.(2.24) in the above equation, AG aG = A+ TE). (2.27) es] 1 an) This is known as the Gibbs-Helmholtz equation, and could also be written in the following form: a(t) > aH [aca | << (2.28) 8 SB Ue - f or | ae ean asl (2.29) Lally) ‘The Gibbs-HeImholtz equation permits the calculation of ad for areaction at any temperature from its value at another temperature. Similar equations can also be written for aG°. For example,The Second Lav of Thermodynanics + Entropy and Free Energy 59 °, aco = aH 4 7 PAE) (2.30) Fir P 06°74)- ° ae ete (2.31) The application of the Gibbs-Helmholtz equation is illustrated in Examples (2.3) and (2.K). Eeample 2.0 itd Sh gus " Calelate the standard enthalpy and entropy thanges at 25°C (298 x) for the reaction 2eCur + 3(0,) = s aG° = -40,500 - 3.92 T log T + 29.5 T cal (-169,452 - 16.40 T log T + 125.435 Td). Solution: AG° = -40,500 - 3.92 x 0.4343 T In T 4 29.5 T = 40,500 - 1.702 T InT 429.5 T, (2.9.1) ac? 40,500 on A 7 SBD 1702 nT + 29.8. Differentiating, Ac? aCS'/t) _ 40,800 _ 1.702 ar = T From Eq.(2.31), _ AH? _ 40,500 _ 1.702 ep rt60 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS or ao = -40,500 + 1.702 T. At 25°C, ote Sop = 404500 + 1.702 x 298 = =39,993 cal = 739,99 kcal Differentiating (2.0.1), 306° aT = 1.702 - 1.702 In T + 29.5 = 27.798 - 1.702 In T. From Eq. (2.26), + as° = 27,798 - 1.702 InT. At 25°C, 859g = “27.798 + 1.702 In 298 = -18.10 cal/deg Example _2.K 86° for the reaction + 2(0y) = o at 26°C (298 K) is -50,786 cal (-222,499 7). Calculate 6° at 327°C (600 x) from the following data: AH398, ~ ~87%500 cal/mole (240,580 J/not) . = 6.03 + 10.44 x 10° 7? ~ 2.50 x 107? T cal/deg/mole q Py (25.23 + 43.68 x 20° 9 ~ 10,48 x 10° a/X/mot),The Second Law of Thermodynamics : Entropy and Free Energy 63 or 298 1 = - 64,091.85 + 50,786 = + 13,305.85, or Tos - 44.65. Putting the value of I in (2.K.3), 6? = - 3.30T In T 4 1.74 x 106 T? - 1.0 x 109 ~ 0.1 x 108 Tt ~ 58,413 + 44.65 T =~ 58,413 + 1.74 x 1076 13 - 1,0 x 1079 1? - 3,307 In T + 44.65 T - 0.1 x 108 7), 262, = = 58,813 + 1.74 x 10° x 600? - 1.0 x 107? x 6007 ~ 3.30 x 600 600 a x In 600 + 44.65 x 600 ~ 2-1 10° 600 = 44,290 cal. Exercises 2.1 The reversible transformation of grey tin to white tin occurs at 13°C (286 K) and 1 atm, and the heat of transformation is 500 cal/mole (2092 J/mol). Calculate the entropy change. Hn du 2.2 Calculate the changes in heat content and entropy associated with the reduction of the oxides of iron and aluminium at 25°C, according to the following reactions:64 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Fe,0, + = 2Fe + 300. Alg0, + 3 = 2Al + 300, Comment on the result. Given: 2Fe +30, = Fey03 aHeoe = -200,000 cal (-23¢,800 a). ZA +50, = AlgOs5 Aeog = ~404,000 cal (-1,690, 330.4). C(graphite) + 30, = CO; Ane Sa = -25,000 cal (-104,600 3). Entropies of CO, Al, Fe, Alz0,, Fe,0, and C(graphite) at 25°C are 47.3, 6.7, 6.5, 12.8, 21.5, and 1.39 cal/deg/mole (197.9, 28.0, 27.2, 53.6, 89.9, and 5.8 J/K/mol), respectively. ps gets Ngee UB gu 2.3 ‘The heat capacity of solid magnesium at 1 atm pressure in the tempera~ ture range from 0° to 560°C (273 to 833 K) is given by the expression Cp = 6.20 + 1.33 x 10° T+ 6.78 x 10% T7caI/deg/mole (25.04 + 6.66 x 209 9 + 20.37 x 108 2? J/tymol). Determine the increase of entropy per mole for an increase of temperature from 27° to 527°C (300 to £00 K) at 1 atm (101325 H/m*) pressure. SU Ogu ; Two identical copper ingots, one at 600°C (773 K) and the other at 300°C (573K) are placed in an insulated enclosure. Heat flows from the hot ingot to the cold ingot until the temperature of both ingots is the same (400°C). Calculate the total entropy change accompanying this process,The Second Law of Thermodynamics : Entropy and Free Energy 65 assuming that the transfer of heat from the ingots to the material of constr- uction of the enclosure is negligible. Comment on whether the process is spontaneous or not. Given: Cp ecu = 5:41 + 1.50 x 1079 T cal/deg/mole : -3 (22.64 + 6.28 x 10° 2 J/K/mol). tn Ne 2.8 Calculate the standard entropy change of the following reaction at 727° (1000 K) 2M + 20, = A1,035 18098 = -T4.87 cal/deg/mole (-323.28 J/K/mol). Given: Melting point of aluminium = 659°C (932 x). Heat of fusion of Al at the mp. = 2,500 cal/mole(10,460 ¢/mot). “p, = 25.14 cal/deg/mole (105.19 //k/mot). c = 7.57 cal/deg/mole (31.67 J/K/mol). Px (D9) Cp cate = 6.76 cal/deg/mole (28.28 J/K/mot). “p tan = 17.00 cal/dea/mole (28.29 I/X/mot) Oe 2.6 Calculate the entropy change of the system and the surroundings for ‘the isothermal freezing of one mole of supercooled liquid copper at 900°C @,173 K) when the surroundings are also at the same temperature. Assume that Cp for liquid copper also holds good for supercooled liquid copper. Given: Melting point of copper = 1,083°C (2,35¢ x). Heat of fusion of copper at m.p. = 3,100 cal/mole (12,970 J/mot).66 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS Cp coy = 5-41 + 1.80 x 1079 T cal/deg/mole (28.64 + 6.26 x 107 7 d/t/not). Cp icy = 7-50 cal/deg/mole (51.38 /K/mot). te Sg Bef Calculate the entropy changes of the system and surroundings for the case of isothermal freezing of one mole of supercooled liquid silver at 850°C, when the surroundings are also at the same temperature. Given: Melting point of silver = 961°C (2284 KJ. Heat of fusion of silver at 961°C = 2,690 cal/mole (12,255 J/mol). Cp eagy = 5.09 + 2.08 x 107? T cal/deg/mole (21.50+8.54x107° 9 a/k/rol). & (Ag) 7.30 cal/deg/mole (30.54 J/K/mol). AH digs 2.8 Using the Following values, calculate the standard free energy change per mole of the metal at 727°C (1,000 X) for the reduction of molybdic oxide and chromic oxide by hydrogen: 'Sho00, = -120.0 kcal/mole (-502.0 kJ/mol). o i 487000, (1,0) = -45.5 kcal/mole (-190.4 kd /mol). Conment on your result. 2.9 Determine the termperature above or below which reduction of MnO by carbon becones thernodynamically feasible at 1 atm pressure (101,326 i/n®). Given: 2_ + (0p) = 2(C0)s68 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS AG° = -174,750 + 49.09 T cal (-757,15¢ + 205.39 7 J). we Ne 2.13 Chromium and carbon present in stainless steel form chromium carbide at 600°C (273 K). Show by thermodynamic calculation which of the metals among Si, Ti, and WV should be alloyed to stainless steel, so as to prevent the formation of chromium carbide. Given: 3r+2C = Cr. A6° = -20,800 - 4.0 T cal (-87,027 - 16.74 7 J). Si+ C = Sits a6° = -12,770 + 1.66 T cal (- 53,430 + 6.95 TJ). vVo+e+C = Wy; 46° = -20,000 + 1.6 T cal (-63,680 + 6.69 7 J). Ti+ C = TICS AG° = -45,000 + 2.8 T cal (-788,280 + 21.71 7 J). ee de 23284 Sa ge 2.14 Suggest whether the decomposition of NbC by Nb,0, at 1 atm pressure is possible at 1500°C (2773 K). . 0 2 Given: 489773, cub, -269.0 kcal/mole (-2,225.5 kJ/mol). 303773, =~ 30-8 kcal/mole (-228.87 kJ/mol). set773, (co) = -64.0 kcal/mole (-267.77 kJ/mol).CHAPTER 3 THE THIRD LAW OF THERMODYNAMICS 3.1 Statement of the Law op 8a ly 9 ‘The third law of thermodynamics is stated as “Siren, ee nmme du dye ‘Amore general statement of the third Tow is Aldaall AS y The entropy of a system at absolute zero in a ate of thermodynamic equilibrium is zero. 3.2 Application One of the important applications of this law is to determine the absolute value of entropy, S, at any temperature, provided that the heat capacities are known within the range of temperature under consideration and that the substance is crystalline at absolute zero. Since Cp a = far. Integrating the above equation from absolute zero to a temperature T, a, (3.1) or s;- 8 * {The Third Law of Thernodynanics n where S; and S, are the entropies of the system at T and 0K respec- tively. Since according to the third Taw S, is zero, we have 7: op Ss * za. (3.2) ° Following Einstein's idea, Debye\/showed|/that/at lover! temperatures; /about joa, CA (3.3) where a is a constant. £q.(3.3) is known as Debye's equation. Splitting the integral in Eq.(3.2) in two parts, from 0 to T’ and from T’ to T, where T' is an intermediate temperature between 0 and TK, we have (3.4) If 1 (3.5) where Cp cw) is the heat capacity at constant pressure at T' K,7 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS The value of the integral in Eq.(3.5) is given by the area under the curve of Cp/T versus T between the values of T = T' and T=T. Alternatively, the value of the integral is also given by the area under the curve of Cp versus In T between the values of In T corresponding to T=T' and Te)T. However, in deriving Eq.(3.5), it has been assumed that there is no phase change between the temperature 0 and TK. If there is any transformation say, at temperature T, intermediate between T' and T, we have T, t ct L ro 1 t & 3 = $e |, =H + iy + ! —d, (3.6) t where : . Cp = heat capacity at constant pressure fron T' to Ty. Ly = latent heat of transformation, and cp = heat capacity at constant pressure fron T, to T. ‘The application of the third law of thermodynamics in calculating the absolute: ValueNGflentronyloMaMeEAD is illustrated in the following example. weal lye zeample 3.A The molar heat capacities at constant pressure of silver in the temperature range -258°C to 27°C (15 - 300 K) are given below. Tenp. °C 258 -253 -243 -223 -203 -183 -123 0 -230(27 Cyscal/deg/mole : 0.16 0.40 1.14 2.78 3.90 4.56 5.48 $.90 6.10 (Temp. , K : 16 280 30 80 70 90 180 250 300 Cpw/k/mod + 0.6? 1.67 4,72 11,63 16.32 19,08 22.93 24.69 25,52)CHAPTER 4 THE CLAUSIUS-CLAPEYRON EQUATION 4.1 Introduction The Clausius-Clapeyron equation is of great importance for calculating the effect of change of pressure (P) on the equilibrium transformation temperature (T) of a pure substance, and may be represented as Pp ee g ~ mn ena (4.1) where 4H is the heat of transformation and 4Y jis the volume change assoc- jated with the transformation. However, care should be taken in selecting the units of the quantities in Eq.(4.1). If AH and AV are expressed in cal and cubic centimeter respectively, then #héllVallUéletilldP/aTimobeatrad wil NIbE in cal/e.c./deg. Ih order to convert the value of 4P/dT from this unit to ‘the more convenient unit of atm/deg, the following factor is used: Teal = 41.293 c.c, ate. eA 4.2 Application of Clausius-Clapeyron Equation to Phase Changes The Clausius-Clapeyron equation is applicable to any phase change-fusion, vaporization, sublimation, allotropic transformation, etc. 4.2.1 Liguid-Vapour (Vaporization) Equilibria Applying Eq.(4.1) to a liquid-vapour equilibrium, we have AH, 4-7: (4.2) a Wap “Vig 7778 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS where aH, is the molar heat of vaportzation or latent heat of evaporation, Vyap 18 the molar volume of vapour, and V,,_ is the molar volume of liquid. Since the molar volume of vapour is very much larger than the molar volune of Tiquid, Vygq 18 negligible as compared to V4.4 and hence AH, oP ’ at” TWap isa) Assuming that the vapour behaves as an ideal gas, the volume Vyap may be related to RL Wap = Pe (4.4) Substituting the value of Vgq in Eq.(4.3), (4.8) The equation can be rearranged in the most generally used differential form ain) _ Hy a me’ (4.6) If we assume as an approximation, however, that over the interval in question 4H, remains constant, then integration of Eq.(4.6) yields InP Ny ¢ InP s -—t + Ci, (4.7) + ony or log P = ——“—ec, (4.7b) 2.303 RT where C’ and C are integration constants.The Clausius-Clapeyron Equation 9 It is evident from Eq.(4.7b) that if log P for any liquid metal is plotted against 1/T, the plot should be a straight line. The slope (m) of the straight line will be given by and the intercept of the line with Y-axis will give the value of constant C. From the slope of line, the heat of vaporization of liquid may be calculated. However, the heat of vaporization of a liquid metal calculated in this way will be the mean value over the temperature interval concerned. £q.(4.6) may also be integrated between the limits Py and Py correspond- ing to temperatures 1) and T, respectively. Assuming that the tempera- ture range is small enough so that AH, is independent of temperature, integration of Eq. (4.6) yields 2 2 iH, | d(in P) 2 fel a. P. ey 1 1 ak te Jue Sige ot P, ~ AH. 2 aegis a ¢-t 4. or 1S ¢: 2.903 R (12 Al ea) Eq.(4.8) may be used to calculate the vapour pressure at any temperature if the vapour pressure at another temperature and the wean heat of vaporization over that temperature range are known. The following example illustrates the application of the Clausius-Clapeyronco} PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS equation to liquid-vapour equilibria. Example _4.A The vapour pressure of THQUTMMtitantimatl2227%C (2500 K) is 1.503 mm Hg (200 t/n®), The heat of vaporization at thalnornalllboilinalpointlor ‘ERESHTUMTSMIOANKER Abe (435.24 kJ/mol). Calculate its normal boiling point. Solution: Let us assume that the normal boiling point of titantun is T,. At this temperature, the vapour pressure is equal to 1 atm, or 760 mn Hg. Putting the appropriate values in Eq. (4.8), 760. , 104009 tes is * “ars | ol SMA al- On simplification, b 7 58K = 3288". Thus the normal boiling point of titanium is 3285% However, a more accurate integration of £q.(4.6) can be carried out if the variation of heat of vaporization with temperature is taken into account. Using Kirchhoff's equation at constant pressure, AH, (23) - 1G or ays [tp ar + he (4.9)84 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS that discussed earlier. If a is the stable form above the transition temperature, and @ is the stable form below the transition temperature T, then according to Eq.(4.1), # oHee T° ao TW, TV =v on at, Wa" Me) dP MH where AH,, {8 the molar heat of transition, V, and V, are the molar volumes of the indicated forms, all measured at temperature T. 4.3 Trouton's Rule ul iy at Trouton's rule states that the ratio of latent heat of evaporation to the temperature of normal boiling T, is constant for all liquids, and is approx imately 21 cal/deg/mole, i.e, oH i Ft + 2 cal/deg/nore, Jud! > The rule is only an approximate one, and is not followed by all liquid metals. However, this rule may be used to derive an approximate value for latent heat of evaporation.‘the Clausius-Clapeyron Equation 85 ‘Frample 4.0 th SI gue The normal boiling point of zinc is 907°C (2260 x). Celeulate its vapour pressure at 800°C (1073 K), assuming that zinc follows Trouton's rule. Solution: According to Eq.(4.7b), the vapour pressure of Viquid zine may be expressed as -tH log P = sagher +c. (4.0.1) Since zinc follows Trouton's rule, the molar heat of vaporization is given by m= 21 T, = 21 x 1180 = 24,780 cal/nole. Substituting the value of 4H, in €q.(4.C.1), Jog Pp = 24280 | 5, (4.0.2) 4.5757 The value of C can be cbteined by putting boundary conditions, The vapour pressure at the normal boiling point 907°C (2160 x) is 1 atm, and hence we have =24,780 wo 780 tool = eve x 160 * & or C= 4.59. Substituting the value of ¢ in Eq.(4.C.2),86 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS ~24,,780 log P 3 4.575 T + 4.59 (4.0.3) where P is in atm. From £q.(4.C.3), the vapour pressure of liquid at 800°C (1072 x) is given as 724,780 TogP = ——"_ + 4.59 4,575 x 1073 = 0.4580, or P = 0.3483 atm = 264.7 nm Ha. Thus, the vapour pressure of zinc at 800°C is 264.7 mm Hg. Exercises 4.1 Calculate the mean heat of vaporization of palladium from the following vapour pressure data: 134 1357 1568 Temp. V.P., mm Hg. 7.516 x 10? 1.614 x 10 5,625x 107 (Temp., K 1597 1624 1841 VPLs Wn? 1,002 x 10% — 815 % 10 750.x 10The Clausius-Clapeyron Equation 87 4,2 The vapour pressures of liquid thorium tetraiodide at 800°C (7073 x) and 825°C (1098 X) are 468 mm Hg (62,395 W/m?) and 660am Hg (87,993 N/m") respectively. Calculate its mean heat of vaporization, ith ge 4.3. The heat of evaporation of copper at its normal boiling point is 74.5 kcal/mole (311.71 %J/mol). The vapour pressure of copper at 1500°C (1773 x) is 0.256 mm Hg (3¢ Wh). Calculate the boiling point of copper. 4.4 The vapour pressure of liquid zinc as a function of temperature is given as Jog P (mmHg) = = sce = 1.255 log T + 12.34. Calculate the heat of vaporization of zinc at its boiling point 907°C (1180 K). aS Shaw 4.5 The densities of liquid and solid bismuth are 10.0 g/c.c. (10x20 kg/m) and 9.673 g/c.c. (9,673 x 107 kg/m) respectively at the normal melting point 270°C (543 K), The heat of fusion is 2.633 kcal/mole (21.02 ki/mot). Calculate the melting point of bismuth under a pressure of 100 atm (207,326 x 10° N/n’). Atomic weight of bismuth is 209. ald SN gus 4.6 The melting point of cadmium at 1 atm (102,326 N/m’) is 321°C (soe x) and its heat of fusion is 13.66 cal/g (&7.15 x10" d/kg). The volume change on the melting of cadnium is +0.0064 ¢.c./g (+0,0004 x10°9 m°/kg). Calculate the melting point of cadmium, (a) at 2 atm (202,050 W/n’) pressure, and (b) in vacuo.88 PROBLEMS IN METALLURGICAL THERMODYNAMICS AND KINETICS 4.7. Mercury melts at -38.879C (254.15 K) at 1 atm (101,526 W/n?) pressure. The densities of liquid and solid mercury are 13.69 g/c.c. (15.69 x 10° kgfn®) and 14.19 G/c.c. (14.19 x 10° kg/m®) respectively at the normal melting point. The heat of fusion of mercury is 2.33 cal/g (9.75 x 10° J/kg). Calculate the change in melting point of mercury per atmosphere change in pressure. iE Ne 4.8 The vapour pressure, P, (measured in mm Hg) of liquid arsenic, is given by tooP = - 260 4 6.69, and that of solid arsenic by log P = - a + 10.8. Calculate the temperature at which the two forms of arsenic will have the same vapour pressure. 4.9 The densities of ice and liquid water at 1 atm (101,325 Wn?) and 0°C (273 X) are 0.917 g/c.c. (0.917 x 10° kg/m) and 0.9998 9/c.c. (0.9998 x 10" J/kg) respectively. The heat of fusion of water is 80 cal/g (234.72 x 10° J/kg). Calculate the melting point of ice at 0.5 atm (50,6¢2.5 N/n’) and 101 atm (102,338 x 10° N/m’). 4.10 The heat of the reaction en dlns Sn (grey) = Sn (white) is 500 cal/mole (2,092 J/nol) at the transition temperature of 13°C (2es K). The atomic weight of tin is 118.7 and the densities of grey and white tin are 5.78 g/c.c. (5.75 x 10° kg/m3) and 7.28 g/c.c. (7.28 x10° kg/m?) respectively.CHAPTER 5 FUGACITY, ACTIVITY AND EQUILIBRIUM CONSTANT 5.1 Fugacity. The conbined statement of the first and second laws of thermodynamics for a system doing work against pressure is og = VdP = SdT. (5.1) At constant temperature, Eq.(5.1) reduces to dG = ve. (5.2) For one mole of an ideal gas, Eq.(5.2) reduces to d= RT din, (5.3) If the gas is not ideal, Eq.(5.3) takes the form Ce ae (5.4) where the function 'f' is called ‘fugacity’ of the gas. For an ideal gas, the fugacity is numerically equal to the pressure at all pressures. Non-ideal (or real) gases approach ideal behaviour as the pressure is decreased, i.e. as P*0, f*P. Thus, for anon-ideal gas, fugacity and pressure will be numerically equal at low pressures. Fugacity can be regarded as an idealised measure of the pressure of a gas, aecyertgss) dubia 5.2 Activity The activity of a substance may be defined as the ratio of fugactty of the substance to its fugacity in its standard state. Mathematically, 9094 PROBLENS IN METALLURGICAL THERMODYNAMICS AND KINETICS Exarpte 5.4 uld Siu Zr, = Zr+0,3 AG° = 259,940 + 4.33 T log T - 59.12 T cal as (2,087,580 + 18,12 7 log 7 - 247,30 7 J), ual at 1727°C (2000 ¥), Also, predict the possibility of decomposing a pure zirconia crucible under a vacuum of 107° mm Hg (233 x 20° N/m®) at that temp= erature. Solution; The standard free energy change for the reaction ZrO, = art 5 (5.8.1) at 1727°C (2000 K) is given by 10° 5000 = 259,940 + 4.33 x 2000 x log 2000 - 59.12 x 2000 = 170,330 cal. The equilibrium constant of reaction (5.8.1) can be calculated with the help of Eq.(5.13), and thus the value of K at 1727°C is given by 170,330 Jog k = - 4.575 x 2000 = -18.61. 2.455 x 10°19, Taking antilogs, k The equilibrium constant of reaction (5.8.1) is 87-802 ®Zr02Fugacity, Activity, and Equilibrium Constant 95 where 87,5 %, and az,o, are the activities of Zr, 02 end ZrO, respec- tively. Assuming that the gases behave ideally, the activity of oxygen may be replaced by its partial pressure, i.e. a2 yP ZrFO5, x " 2; ZrO, where pp, is the partial pressure of oxygen in equilibrium with Zr and ZrO. Pressure in the expression for K is in fact a ratio of the partial pressure of the gas (expressed in atm) to the standard pressure, i.e. 1 atm, and hence has no units. The magnitude of the pressure term in the expression for K is, therefore, equal to the partial pressure of the gas expressed in atm. Since both Zr and ZrO, are pure, and hence their activities may be taken as unity, it follows that KM, (5.A.2) Putting the value of K in Eq.(5.A.2), 2.455 x 107"? atn Por 760 x 2.455 x 107'9 mm Hg 1.865 x 10 mm Hg. Thus, the partial pressure of oxygen in equilibrium with Zr and ZrO at 1727°C is 1.865 x 1071 mm Hg. In other words, if the partial pressure of oxygen in the system is below this value at 17279C, then zirconia will decompose. In the present problem, the vacuum is of the order of 10° mm Hg, which is equivalent to a partial pressure of oxygen of 0.21 x 10° am Hg €ssuming that air contains 21% oxygen on volume basis), and this value is greater than the equilibrium partial pressure of oxygen in contact with Zr and Zr0, at 1727°C. Hence, there is no possibility of the decomposition ofFugacity, Activity, and Equilibrium Constant 103 5 if | 5.4 Wan't Hoff Equation Sud Vig Drive van ‘t Hoff equation The Gibbs-Helmholtz equation at constant pressure is represented as d(460/T} ° aqvry = SH Substituting the value of aG? from Eq.(5.12), ay? ten = > (5.14) (5.18) or ct He re” Jui! The above equation is commonly called the Van't Hoff equation. 5.4.1. Integration of Van't Hoff Equation From Eq.(5.14) it follows that -Rd(In k) = aH? dQ), (5.16) AH? is not independent of temperature; hence, in order to integrate the above equation, it must be converted to a form in which there is no term dependent on temperature. ince (28H) s Since ( ark Cpe Assuming that Cp is expressed in the form Cp = a+ bT =cT we have,Fugacity, Activity, and Equilibrium Constant m AG° = 88,720 + 10.35T logT - 103,33T cal (871,204 + 43,307 log? - 482,337 J), Assume that the reaction is carried out in a closed retort containing no air. 5.7 Evaluate the partial pressure of Mg vapour at 1200°C (2473 x) for the following reaction: 2 + 2 + = 2(Ma) + <2Ca0-Si0,>, Given: 2eMgD> + = 2(Mg) + 5 46° = 152,600 + 11.37T logT = 99.18T cal (638,478 + 47.577 log? - 414.977 J). 2< Can>+ = <2 Cad “S10, >; 46° = -30,200 - 1.2 Teal (128,357 - §.027 J). 5.8 In a copper converter, the following reaction is believed to occur in the latter stages: {Cus} + 20Cu0} = 6 {Cu} + (802) 5 a6 = -87 - 5.13Tcal (-364 ~ 21.4874). Calculate the equilibrium partial pressure of SO, at 1250% (1523 K). Assume that both Cu,S and Cu,0 exist as pure melts. 8s JLB Sg Will a magnesia crucible decompose at 1000°C (1275 x) in a vacuum of 0.01 atm (1013 4/n?) ?